NCD980557656_19970509_NC State University (Lot 86 Farm Unit 1)_FRCBERCLA SAP QAPP_Quality Assurance Project Plan Volume II of II (Revision 0)-OCR

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QUALITY ASSURANCE PROJECT PLAN
LOT 86 SUPERFUND SITE
RALEIGH, NORTH CAROLINA
Volume II ofll
Submitted to:
North Carolina State University
Environment, Health & Safety Center
Campus Box 8007
Raleigh, North Carolina 27695
7721 Six Forks Road, Suite 136
Raleigh, North Carolina 27615
[phone]
Revision 0
May 9, 1997
Project 97191
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APPENDIX A
Laboratory Quality Assurance Plan
Pace Analytical Services, Inc.
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Prepared by Pace Analytical Services, Inc.
1710 Douglas Drive North
Minneapolis, Minnesota 55422
[phone]
LABORATORY QUALITY
ASSURANCE PLAN
Pace Approval
/ -1/'.2 .;,_ /7.S
Date
Date: 12/22/95
Section 1.0
Revision 0.01
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All rights reserved. No part of this manual may be reproduced or used in any form or by any means -graphic, elec!ronic, meci1anic:al, including photocopying, recording, taping, or information storage and retrieval systems -without permission of the publisher.
Copy __ issued to:
Name
Affiliation
Date
This is/ is not a controlled document (control status must be circled before release).
An E,ual Opportunity Employer
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1 . 1 FOREWORD
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Pace Analytical Services, Inc. is a privately held, full service environmental testing firm operating a system of 7 laboratories and multiple service centers nationwide. The Pace Minnesota laboratory was established in Minneapolis, Minnesota, on. August 3, 1978. Since its inception, Pace has provided analytical services for clients ranging from federal and municipal government to industrial firms and private consulting groups. As an independently owned environmental laboratory company, with Pace, there is never the question of conflict of interest. Since the foundation of its first laboratory, Pace has always retained quality as its primary objective.
Pace Analytical Services, Inc. offers extensive services, including: bioassay for aquatic toxicity, air toxics, explosives, field services and mobile laboratory capabilities. The Pace system offers extensive capacity, and the ability to transfer work within the integrated system of laboratories assures that tum-around times are met. And, perhaps most importantly, geographic expansion has brought to Pace many valued and dedicated employees, with diverse interests and areas of expertise. There are nearly 400 people who contribute daily to the success of Pace.
Over the years, Pace has developed and continues to develop a strict system of QNQC protocols, originally modeled after the USEPA Contract Laboratory Program (CLP) requirements. In addition, Pace has developed an advanced data management system, which is highly efficient and allows for flexible data reporting. Together, the two systems insure data reliability and timeliness.
The advances have not been limited to the company itself. Pace and Pace employees have been instrumental in the development of the environmental testing industry. Pace employees are among the founders and board members of the industry's two major associations: the American Council of Independent Laboratories (ACIL}, and the International Association of Environmental Testing Laboratories (IAETL). Pace employees have delivered papers and published articles on laboratory management, Quality, and, most recently, on the newly developed model laboratory contract.
Today, Pace is not only keeping stride with the evolving industry, but is actively engaged in that evolution. Pace is operating a high productivity environmental testing laboratory in northern California near San Francisco. The laboratory was designed with process efficiency and quality as its major objectives. The results in enhancements to analytical, quality, and data management systems will be replicated in other Pace laboratories.
The strength of our company comes from how we are organized. We understand how important it is to develop long-term, on-going communication with our clients. Wrth the client at the center, we have an integrated local support team which revolves around the client. The national system provides the local team with additional capacity, specialty services, and additional experts in all areas of the business, in order to ensure that requirements are met.
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1.2
1.3
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Our goal is to continuously combine our expertise in the laboratory with customized
solutions to meet the specific needs of our clients. By providing the right chemistry and the right solution, Pace has become known as a leader in the industry with satisfied, long-term clientele.
CORPORATE PHILOSOPHY
The criteria for selecting an analytical laboratory have changed significantly in recent
years. Increased environmental liabilities have altered the attitudes of users and providers
of laboratory services. Quality is now the primary criterion.
Our philosophy at Pace, as it always has been, is to provide clients with the standards of service they require and deserve. It is a philosophy dedicated to providing:
Uncompromising Quality
Service Responsive to Clients' Needs
A Single Source of Comprehensive Services
Since the company's inception, Pace professionals have worked diligently to meet these goals. Our continued commitment to these standards remains the top priority at Pace.
THE MISSION OF PACE ANALYTICAL SERVICES, INC.
To be your Preferred Choice for Environmental Analytical Services in the Laboratory and in the Field
For our clients:
by consistently meeting our commitments
by delivering responsive service, on time, with high value
by assuring data quality and technical excellence
For our employees:
by offering equal opportunity for professional development
by providing stimulating, participative, and safe work environments
by valuing personal worth; encouraging excellence through recognition and
reward
For our shareholders:
by generating a return on investment which meets our obligations and
promotes company objectives
For our suppliers:
by offering long term relationships to those who support Pace's quality and business objectives
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1.4
For our communities:
by being environmentally responsible and a good corporate citizen
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Pace strives to be the preferred choice for all its stakeholders, by providing quality services with the highest level of professional and ethical standards.
CODE OF ETHICS
In carrying out its Corporate Mission, Pace requires its employees to abide by the highest professional, ethical standards. Employees will conduct their tasks according to the highest professional, technical and ethical standards applicable· to their area of expertise. As such, Pace requires a commitment from all staff to abide by the principles set forth by the Company. This applies to all procedures, documented and undocumented, executed by employees. The following information summarizes the essential standards of ethical behavior required of Pace employees.
Simply stated, Pace's fundamental ethical principles are as follows:
• Each Pace emp.loyee is responsible for the propriety and consequences of his or her actions.
• Each Pace employee must conduct all aspects of Company business in an ethical and strictly legal manner, and must obey the laws of the United States and of all localities, states and nations where Pace does business or seeks to do business.
• Employee conduct on behalf of the Company with clients, suppliers, the public and one another must reflect the highest standards of honesty, integrity and fairness.
Strict adherence by each Pace employee to this Code and to the Standards of Conduct is essential to the continued vitality of Pace. Therefore, compliance with and effective enforcement of the Code and Standards are key responsibilities of Pace management and will be addressed as elements of each employee's regular performance evaluation.
Failure to comply with the Code or Standards will result in disciplinary action up to and including termination and referral for civil or criminal prosecution where appropriate. An employee will be notified of an infraction and given an opportunity to explain as prescribed under current disciplinary procedures.
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Section
No.
1.0
2.0
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2.0 TABLE OF CONTENTS
Section Name
No. of
Pages
Title Page 4 1.1 Forward
1.2 Corporate Philosophy
1.3 The Mission of Pace Analytical Services, Inc.
1.4 Code of Ethics
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Table of Contents 9 12/22/95 0.01 2.1 List of Tables
2.2
5.1 Quality Control Objectives: Methods 801 OB & 8020A 5.2 Quality Control Objectives: Purgeable Petroleum
Hydrocarbon Analysis
5.3 Quality Control Objectives: Extractable Petroleum
Hydrocarbon Analysis
5.4 Quality Control Objectives: Methods 8080A & CLP SOW 5.5 Quality Control Objectives: Methods 8240B & CLP SOW 5.6 Quality Control Objectives: Methods 8270B & CLP SOW 5.7 Quality Control Objectives: Metals by SW846 & CLP SOW 5.8 Quality Control Objectives: General Chemistry
6.1 Sampling and Preservation Requirements -
Water
6.2 Sampling and Preservation Requirements -
Soil
6.3 Sampling and Preservation Requirements -
Air
8.1 Summary of Calibration Requirements
8.2 Summary of Routine Calibration Requirements
9.1 Analytical Protocols
9.2 List of Analy1ical Methods
9.3 BFB Key Ions & Ion Abundance Criteria
9.4 DFTPP Key Ions & Ion Abundance Criteria
11.1 Summary of Calibration and Quality Control Procedures
13.1 Scheduled Maintenance Procedures and Representative
Spare Parts for Major Instrumentation
List of Figures
4.1 Pace Analytical Services, Inc. Organizational Structure
4.2 Pace Analytical Services, Inc. Laboratory
Organizational Structure
6.1 Presampling Communication, Sample
Collection and Holding Schematic
Section
No.
3.0
4.0
No. of
Section Name Pages
7 .1 Chain of Custody
7.2 Sample I.D. and Condition Form
7.3 Discrepancy Report Form
7.4 Internal Chain of Custody
7 .5 Client Sample Return Letter
7.6 Sample Disposition Form
7.7 Hazardous Sample Disposal Option Form
10.1 Analytical Data Review Process
11.1 Spike Recovery Control Chart
11.2 RPO (Duplicate) Control Chart
15 .1 Corrective Action Form
2.3 LQAP Distribution List
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Introduction 12 12/22/95 0.01 3.1 Program Objectives
3.2 Statement of Policy
3.3 Purpose and Scope
3.4 Quality Assurance Documents
3.4.1 QA Manual
3.4.2 Standard Operating Procedures Manuals
3.4.3 Project QA Manuals
3.4.4 Document Control, Distribution and Revision
3.5 Terms and Definitions
Laboratory Organization and Responsibility 10 12/22/95 0.01 4.1 Laboratory Organization
4.2 Description of Responsibilities
4.2.1 Corporate Quality Assurance Officer
4.2.2 Laboratory General Manager
4.2.3 Laboratory Project Manager
4.2.4 Quality Assurance Officer
4.2.5 Operations Manager
4.2.5 Supervisors
4.2.7 Analysts
4.2.8 Sample Custodian
4.3 Training and Orientation
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Section
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5.0
6.0
7.0
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4.4
4.5
Section Name
Laboratory Safety
Security and Confidentiality
Quality Assurance Objectives
5. 1 Level of QA Effort
5.2 Accuracy and Precision
5.3 Completeness
5.3.1 Random Error
5.4 Representativeness
5.5 Comparability
5.6 Traceability
No. of
Pages
12
5. 7 Quality Assurance Project Plan Exceptions
5.8 Personnel Quality Objective
Sampling Procedures 8
6.1 Introduction
6.2 Sampling Services
6.2.1 Ground Water Monitoring
6.2.2 Waste Water Monitoring
6.2.3 Hazardous Waste Sampling
6.2.4 Flow Monitoring
6.2.5 Soil & Soil Gas Sampling
6.2.6 PCB Services
6.2. 7 Ambient Air Monitoring and Stack
Emission Testing
6.3 Field Support
6.4 Preservation
6.5 Sample Bottles
6.6 Sample Receipt Schedule
Sample Custody 20
7 .1 Sample Receipt
7.2 Chain-of-Custody
7 .3 Sample Verification
7.4 Sample Log-In
7.5 When Samples are Received with no Paperwork
7.6 Responsibilities for Sample Log-In
7.7 Sample Storage
7.8 Sample/Data Access and Internal
Chain-of-Custody
7.9 Subcontracting Analytical Services
7.10 Sample Disposal
7.11 Excess Sample Disposition
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9.0
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Section Name
Calibration Procedures and Frequency
8.1 Standards and Traceability
8.2 General Calibration Procedures
8.2.1 Analytical Balances
8.2.2 Thermometers
8.2.3 pH/Electrometers
8.2.4 Spectrophotometers
8.3 GC/MS Calibration Procedures
8.4 Non GC/MS Chromatography Calibration
Procedures
8.5 Calibration of ICPs and AAs
No. of
Pages
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Analytical Procedures 31 12/22/95 0.00 9.1 Analytical Methods·
9.2 Sample Preparation Methods
9.3
9.2.1 Digestion of Aqueous Samples for
Metals -Method 3005A
9.2.2 Digestion of Aqueous Samples for
Metals -Method 3010A and the CLP sow
9.2.3 Digestion of Aqueous Samples for
Metals -Method 3020A and the CLP sow
9.2.4 Digestion of Solid Samples for Metals -
Method 3050A and the CLP SOW
9.2.5 Separatory Funnel Extraction -Method 35108
9.2.6 Continuous Liquid/Liquid Extraction -
Method 3520A
9.2.7 Soxhlet Extraction -Method 35408
9.2.8 Sonication Extraction -Method 3550A
9.2.9 Waste Dilution -Method 3580A
9.2.10 Purge-and-Trap Sample Introduction -
Method 5030A
9.2.11 Extraction Procedure Toxicity Test (EP-TOX) -
Method 131 0A
9.2.12 Toxicity Characteristic Leaching
Procedure (TCLP) -Method 1311
9.2.13 California Assessment Manual Waste
Extraction Test (CAM WET)
Calibration and Analysis Procedures for
Organics
9.3.1 Halogenated Volatile Organics -
Method 80108
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Section
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Section Name Pages
9.3.2 Aromatic Volatile Organics -Method
8020A
9.3.3 Organochlorine Pesticides and PCBs -
Method 8080A and the CLP SOW
9.3.4 Volatile Organics -Method 8240B and
the CLP SOW
9.3.5 Semivolatile Organics -Method 8270A
and the CLP SOW
9.3.6 Purgeable Petroleum Hydrocarbons
9.3. 7 Extractable Petroleum Hydrocarbon
9.4 Representative Calibration and Analysis
Procedures for lnorganics
9.4.1 Metals by ICPS -Method 601 DA and
the CLP SOW
9.4.2 Metals by GFM-Methods 7060A, 7421,
7740, 7841 and the CLP SOW
9.4.3 Mercury by CVM -Methods 7470,
7471A and the CLP SOW
9.4.4 Total and Amenable Cyanide -
Methods 9010N9012 and the CLP SOW
9.4.5 Anions -Method 300.0
9.4.6 pH -Method 150.1
9.4.7 Non-Filterable Residue -Method 160.1
9.4.8 Filterable Residue -Method 160.2
9.4.9 Nitrate-Nitrite -Method 353.2
9.4.10 Total Organic Carbon (TOC) -
Methods 9060 and 415.1
9.4.11 Oil and Grease -Methods 9070/9071
and413.1
9.4.12 Oil and Grease-Method 413.2
9.4.13 Total Recoverable Petroleum
Hydrocarbons (TRPH) -
Method 418.1
9.5 Method Validation
9.6 Method Detection Limits
9.7 Compliance
9. 7 .1 Definition
9. 7 .2 Understanding the Regulatory
Framework
9.7.3 Commitment
9.7.4 Resolving Compliance Contradictions
and Hierarchies
9.7.5 Disclosure of Noncompliance
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11.0
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Section Name
Data Reduction, Validation and Reporting
10.1 Data Reduction
10.2 Data Validation
10.3 Data Report
10.4 Data Archive
10.5 Response to Inquiries
Quality Control Procedures
11.1 Organic Analysis
11.2 Metals Analysis
11.2.1 Accuracy
11.2.2 Precision
11.2.3 Limits
11.3 Standards
11.4 Method Detection Limit
11 . 5 Control Charts
_11.5.1 Field Blanks
11.5.2 Trip Blanks
11.5.3 Equipment Rinsate Blanks
11.5.4 Matrix Spike/Matrix Spike Duplicate
Samples
11.6 Laboratory Control Samples
11.6.1 GC Methods
11.6.2 GC/MS Methods
11.6.3 Metals Analysis
11.6.4 Cyanide Analysis
11.6.5 Anion Analysis
11.6.6 Fluoride Analysis
11.6.7 Total Organic Carbon Analysis
11.6.8 Oil and Grease Analysis
No. of
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41
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11.6.9 Total Recoverable Petroleum Hydrocarbons
(TRPH) Analysis
11.6. 10 California Assessment Manual Waste Ex1raction
Test (CAM WEntEx1raction Procedure Toxicity
Test Method (EP-Tox)/Toxicity Characteristic
Leaching Procedure (TCLP)
Quality Assurance Audits and Performance 7
Evaluations
12.1 Internal Audits
12.1.1 Quality Assurance Auditor
12.1.2 Scope and Frequency of Internal Audits
12.1.3 Internal Audit Report and Corrective
Action Plans
12.2 External Audits
12/22/95 0.01
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Section
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14.0
15.0
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Section Name
12.3 Total Quality System Audit
No. of
Pages
12.4 Performance Evaluation Audits
12.4.1 Pace PE Samples
12.4.2 EPA WP and WS Studies
12.4.3 Other PE Studies
Preventive Maintenance 6
13. 1 Maintenance Responsibilities
13.2 Maintenance Schedules
13.2.1 Preventive Maintenance -GC/MS
13.2.2 Preventive Maintenance -GC
13.2.3
13.2.4
Preventive Maintenance -ICP
Preventive Maintenance -AA
Graphite Furnace
13.2.5 Preventive Maintenance -Mercury
Analyzer
13.2.6 Preventive Maintenance -General
Laboratory Areas
13.3
13.4
13.2. 7 Preventive Maintenance -

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Refrigerators, Ovens and Balances
Maintenance Documentation
Spare Parts
Assessment of Precision, Accuracy, Completeness
14.1 Precision
14.2 Accuracy
14.3 Control Charts
14.3.1 Warning Limits
14.3.2 Control Limits
14.3.3 Utilization of Acceptance Limits
14.4 Representativeness
14.5
14.6
Completeness
Comparability
7
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Corrective Action 13 12/22/95 0.00 15.1 Non-Conformance Memo
15.2 Out of Control Events
15.2.1 Volatile Organic Analyses
15.2.2 Semivolalile Organic Analyses
15.2.3 Gas Chromatography Analyses
15.2.4 Metals Analyses
15.3 Out-of-Statistical-Control Blank Spike Control
Chart Data
15.3.1 Out-of-Control Blank Spike Recovery Data
15.3.2 Out-of-Statistical-Control Conditions
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17.0
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15.4
No. of
Section Name Pages
15.3.3 Corrective Action for Out-of-Statistical
Control Conditions
Unusual Occurrences
Quality Assurance Reports to Management 2
16.1 Quality Assurance Auditor
16.2 Quality Assurance Officer
16.3 Management Review of the Quality
Assurance Program
16.4 Quarterly Quality Reports to Management
Summary of Revisions 1 17.1 Revision Designation
17.2 Summary of Revisions
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LQAP DISTRIBUTION LIST
Date: 12/22/95
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Individual copy distribution of this document may originate at any Pace facility
and from the Corporate Office. When a copy of the Quality Assurance Plan is released, a designation is made on the cover as to whether the document is a controlled copy. Recipients of controlled copies will automatically be issued an
updated version whenever revisions are made to the existing document. _Each
Pace location which distributes copies of this plan shall maintain a record of the
name of the individual receiving the document, their affiliation, the number of the copy issued and the control status (i.e., controlled vs. uncontrolled).
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3.1
3.2
3.0
PROGRAM OBJECTIVES
INTRODUCTION
Date: 12/22/95
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The Pace Laboratory Quality Assurance Plan (LQAP) presents in specific terms the policies, organization, functions, and specific quality assurance (QA) and quality control (QC) requirements designed to achieve the data quality goals required for clients of Pace Analytical Services, Inc .. The U.S. Environmental Protection Agency's (U.S. EPA) QA policy requires a written and approved Quality Assurance Project Plan (QAPP) for every monitoring and measurement project mandated or supported by the U.S. EPA through regulations, contracts, or other formalized means not currently covered by regulation. Guidelines followed in the preparation of this plan are set forth in the document entitled "EPA Requirement for Quality Assurance Project Plans for Environmental Data Operations", EPA QA/R-5, Draft Interim Final (August 1994). Other documents that have been referenced for this plan include U.S. EPA Region IX Guidance for Preparing Quality Assurance Project Plans for Superfund Remedial Projects (September 1989); U.S. EPA's Guidance on Remedial Investigations Under CERCLA (June 1985); Guidance on Feasibility Studies Under CERCLA (June 1985); Compendium of Superfund Field Operations Methods (September 1987); Data Quality Objectives for Remedial Response Activities (March 1987); and Guidelines for Assessing and Reporting Data Quality for Environmental Measurements (January 1983).
This detailed plan has been prepared for use by contractors who perform environmental
services to ensure that the laboratory produces data that are scientifically valid and defensible. The establishment and documentation of these procedures will also ensure that the data are collected, reviewed, and analyzed in a consistent manner.
STATEMENT OF POLICY
Pace Analytical Services, Inc. is committed to providing the highest quality product to our clients. The validity and reliability of the data generated are ensured by the adherence to rigorous quality assurance/quality control (QA/QC) protocols and a Total Quality Management (TQM) system. Pace emphasizes the application of sound QA/QC principles beginning with the initial planning of the project, through all the field and laboratory activities, and ultimately to the generation of the final report. The principles of concise data quality objectives, representativeness, completeness, comparability, precision and accuracy are applied.
The major elements of the overall Laboratory Quality Assurance Program at Pace are summarized below:
The use of appropriate methodologies by technically competent, well-trained
personnel with state-of-the-art instrumentation and equipment.
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Adherence to well-defined standard operating procedures with emphasis on good laboratory and measurement practices.
Analysis and assessment of quality control samples including (but not limited to) matrix spike samples, matrix spike duplicate samples, duplicate samples, blanks and independent laboratory control standards.
Successful participation in external quality evaluation programs.
Accreditation by state, federal, and other applicable agencies for the work performed.
Internal and external auditing to ensure compliance to protocols and provide assessment of the analytical methods.
Pace is committed to providing the resources, including facilities, equipment and personnel, to ensure the adherence to these rigorous quality assurance/quality control protocols. Pace's quality assurance policy is based on the definition of quality as conformance to requirements; and further, on the premise that the requirements are governed by Company policies, government regulations and standard operating procedures. This commitment recognizes the need for data to be representative of the environmental conditions under consideration, and for data to be generated within a system of functions that is designed to meet applicable regulatory compliance criteria. To this end, Pace has developed a Quality Assurance (QA) Plan and maintains an ongoing QA Program. Our Quality Assurance Program contains provisions for establishing, maintaining and executing protocols which lead to results of known, appropriate and acceptable quality; documentation of these activities is an integral part of the QA program. No other concern will be permitted to interfere with the quality of data Pace provides to clients.
This manual describes the set of policies and principles which guide day-to-day operations. Specific protocols are included by reference and are contained in a series of volumes cited.in Section 9.0 of this document.
This document describes ongoing laboratory operations for routine analyses performed at Pace. As such, the material contained within is subject to change. Changes may be based on specific project requirements or procedural system modifications geared towards operational process and quality improvements. At a minimum, this document is reviewed and updated on a yearly basis.
PURPOSE AND SCOPE
This manual details the quality assurance program in effect at all Pace Analytical Laboratories. It is meant to be a teaching tool and source of information for laboratory personnel. The Manual is divided into logical sections, each dealing with a different phase
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3.4
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of laboratory operation, yet all sections overiap and function together to form a complete quality assurance program. The Manual is based on Good Laboratory Practices, common sense, and industry-accepted standard analytical practices ..
The Manual must be read and understood by all laboratory personnel as part of their training program. The Manual should also be referred to regularly as a source of information. A system of continuous updating is built into the Manual to allow it to change as laboratory conditions change or as new regulations are promulgated. This manual is a controlled document, which means that its identity, development, distribution, and status must be known and traceable at all times. All Pace laboratory personnel have access to a controlled copy.
Whenever a technician or analyst is in doubt as to proper procedures in a specific circumstance, the Manual should be consulted. Omissions or errors should be immediately reported to the Quality Assurance Officer, for corrective action. IT IS THE RESPONSIBILITY OF EACH LABORATORY WORKER TO ENSURE THAT THE PROVISIONS OF THIS MANUAL ARE FOLLOWED. Disagreement with specific requirements or knowledge of changes causing deviation from the procedures should be discussed with the immediate supervisor before further work is completed. Laboratory personnel are encouraged to comment on the Manual and make recommendations for more efficient procedures. ·
The latest revision of each section of the Manual is the applicable rule. Therefore,
revisions will be announced to all laboratory personnel. An uncontrolled copy of the Manual is offered to clients and regulatory agencies as the definitive quality assurance program used at Pace.
QUALITY ASSURANCE DOCUMENTS
3.4.1 QA Manual
This document describes management policies related to operation of the analytical laboratories. It provides overall guidance regarding acceptable practices
and discusses each element of the Quality Assurance Program. It functions as the Project QA Manual where no other Quality Assurance Project Plan, Statement of Work or other contractually mandated project plan has been specified. Adherence to the practices described in this manual is required of all employees. This manual
may be revised and/or superseded only with the written authority of Vice President of Quality/Technical Director. Copies of this manual are controlled and distribution
is administered by the Corporate Quality Office.
3.4.2 Standard Operating Procedures Manuals
All procedures related to sample collection, storage, preparation, analysis,
disposal, data validation, data reporting and employee training and safety shall be contained in written Standard Operating Procedures (SOPs). Each SOP shall
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contain the elements outlined in the Pace Corporate SOP ALL-P-001-A, Guidance Document for Pace Analytical Services, Inc. for the Preparation of Standard Operating Procedure Documents. All sections shall be structured in a step-wise manner using numbered sections. All record-keeping requirements shall be described at each step in the SOP. Examples of forms used shall be included as tables or figures and referenced within the text. Preparation of SOPs which have company-wide application will be the responsibility of the Corporate QAO. Analytical and evidentiary SOPs which are unique to an operating facility shall be prepared by designated personnel (e.g., analytical-section supervisor; evidentiary-laboratory QAO). SOPs shall be assigned a number from the Inventory List for SOPs maintained by the Corporate Quality Office or the Quality Assurance Department of the individual lab, as applicable. This number shall become part of the document control number when the SOP is accepted for implementation by Pace management. Laboratory SOPs shall be reviewed and approved by the relevant Section Supervisor (and Operations Manager for all SOPs related to analytical procedures) and the QA Officer, and submitted by the QA Department to the Operations Manager and the General Manager for approval prior to implementation.
3.4.3 Project QA Manuals·
Project QA Manuals shall be implemented as required. These shall include such documents as Quality Assurance Project Plans (QAPPs). For those projects which require specific QNQC criteria, a QAPP which has been approved by a regulatory agency, usually the EPA, is provided to Pace by the client. Often the analytical section of a QAPP is written by Pace for the client. In this instance, the QAPP is reviewed and approved by the appropriate Pace Quality Assurance Officer and the Pace Operations Manager.
3.4.4 Document Control, Distribution and Revision
In order that this document achieve the goals outlined in Section 3.2, it is necessary that each Pace laboratory employee be familiar with the current provisions of this document. It is also necessary that this document represent a consensus among Pace management and operational personnel as to the quality level desired and the means to that end.
Prior to its publication as a controlled document, this manual must be approved by the Vice President of Quality/Technical Director. To obtain such approval, the document proceeds through an iterative process of review and revision, involving the affected managers and their designated representatives. The signature page at the beginning of the manual represents acceptance.
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Each time a revision is made to this manual, it must also be approved. The Vice
President of QualityfTechnical Director must approve each revision.
3.5 TERMS AND DEFINITIONS
Accuracy:
Aliquot·
Analyte:
Batch·
Blind Sample:
CRDL
CRQL
Calibration-
Calibration Check:
Comparability:
Completeness·
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The degree of agreement between a measured value and the true or
expected value.
A measured portion of a sample taken for analysis.
The specific entity an analysis seeks to determine.
A grouping of no more than twenty samples of similar matrix which are
prepared and/or analyzed together with the same method and the same
lots of reagents within the same time frame. A sample may be analyzed in
a different analytical batch than the one with which it was prepared.
A blank is an artificial sample designed to detect and/or monitor the
contribution of analyte and non-analyte contamination, instrumental
background and sample processing to the measurement system.
A sample submitted for analysis whose composition is known to the
submitter but unknown to the analyst.
Contract required detection limit.
Contract required quantitation limit.
The process of establishing the relationship between instrument response
and known, traceable quantities of analytes of interest.
Verification of the ratio of instrument response to analyte amount, a
calibration check, is done by analyzing for analyte standards in an
appropriate solvent. Calibration check solutions are made from a stock
solution which is different from the stock used to prepare standards.
Comparability is a qualitative parameter expressing the confidence with
which one data set can be compared to another. Comparable data are
produced through the use of standardized procedures and techniques.
Measure of the amount of valid data obtained from a measurement
system compared to the amount that was expected to be obtained under
correct normal conditions. The equation for completeness is:
# of data points obtained X 100 = % completeness
# of data points expected
Continuing
Calibration:
Control Chart:
Control Limit:
Detection
Lim.it
Dry Weight
Duplicate
Analysis·
· Duplicate
Sample:
Environmental
Sample:
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The process of analyzing standards periodically to verify the maintenance
of calibration of the analytical system.
A graphical plot of test results with respect to time or sequence of measurement, together with limits within which they are expected to lie when the system is in a state of statistical control.
A range within which specified measurement results must fall to signify compliance. Control limits may be mandatory, requiring corrective action if exceeded, or advisory, requiring that nonconforming data be investigated and flagged.
The minimum concentration ·of a substance that can be measured and reported with 99% confidence that the analyte concentration is greater than zero.
The weight of a sample based on percent solids. The weight after drying in an oven.
A second measurement made on the same sample extract or digestate to assist in the evaluation of precision of analysis.
A second aliquot of the same sample that is treated the same as the original sample in order to determine the precision of the method.
An environmental sample or field sample is a representative sample of any material (aqueous, nonaqueous, or multimedia) collected from any source for which determination of composition or contamination is requested or required. Environmental samples can generally be classified as follows:
Surface Water and Ground Water
Drinking Water • Delivered (treated or untreated) water
designated as potable water.
Water/Wastewater • Raw source waters for public drinking
water supplies, ground waters, municipal influents/effiuents,
and industrial influents/effiuents.
Sludge • Municipal sludges and industrial sludges.
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Equipment
llifil)k
Fjeld Blank·
Field Sample·
Holding Time:
Homogeneity·
Instrument
Detection Limit-
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Soil Predominately inorganic matter ranging in
classification from sands to clays.
Waste -Aqueous and nonaqueous liquid wastes, chemical
solids, and industrial liquid and solid wastes.
Special type of field blank used primarily as a check on equipment decontamination procedures. After decontamination, the sampling equipment is rinsed with DI water and the water collected for analysis.
A quality control sample that is used to assess the contamination effects on accuracy due to the combined activities of sampling and analysis. Typically, it is composed of analyte free matrix (e.g., deionized water) prov_ided by the laboratory.
A portion of material received by the laboratory to be analyzed, that is contained in single or multiple containers and identified by a unique field ID number.
The elapsed time expressed in days from the date of sample collection by the field personnel until the date of its processing/analysis. For the Contract Laboratory Program, holding times start at the Verified Time of Sample Receipt by the laboratory. Holding time requirements are dictated by the method or QAPP.
The degree to which a property or substance is evenly distributed
throughout a material.
The minimum concentration of a substance that can be measured and reported on a specific analytical instrument with 99% confidence that the analyte concentration is greater than zero. The instrument detection limit is determined by replicate analyses of a standard solution prepared at the
instrument. The instrument detection limit is generally more sensitive than the method detection limit because its determination does not include sample preparation steps.
Initial
Calibration-
Internal
Standards·
Laboratory Control
Sample:
LIMS·
J.Qt
MB.Q;
Matrix:
Matrix Spike:
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The process of analyzing standards, prepared at specified concentrations, to define the quantitative response, linearity and dynamic range of the instrument to the analytes of interest. Initial calibration is performed whenever the results of a continuing calibration do not confonm to the re-quirements of the method in use or at a frequency specified in the method.
Analytes added to every standard, blank, job control sample, matrix spike, matrix spike duplicate, and sample at a known concentration, prior to analysis for the purpose of adjusting the response factor used in quantitating target analytes. Internal standards are used as the basis for quantitation of the target compounds, and are generally applicable to or-ganic analyses.
A control sample of known composition spiked with a known concentration of analytes of interest. Aqueous and solid laboratory control samples are analyzed using the same preparation, reagents, and analytical methods employed for field samples.
Laboratory Information Management System, the Pace company-wide LIMS, has been identified as Environmental Project Information Controller (EPIC).
A quantity of bulk material of similar composition processed or manufactured at the same time.
Method Requirements Documents are written guidelines which outline a consistent definition of work perfonmance for basic method compliance. The documents serve to interpret and define the subjective (vague) portions of the EPA's method for company-wide application. Each MRD is intended to establish a company-wide, baseline level of consistency for a single regulatory-derived method.
The predominant material of which the sample to be analyzed is composed.
Aliquot of sample fortified (spiked) with known quantities of specified target compounds or analytes and subjected to the entire sample preparation and analysis procedure in order to assess the appropriateness of the method for the sample matrix by measuring recovery.
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Matrix Spike
Duplicate:
Method Blank·
Method
Detection
Limit·
Pace Reporting
Limit·
Performance
Audit or
Evaluation:
Precision:
Protocol:
!:QI.:
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A second aliquot of the sample that is treated the same as the original
matrix spike sample. The relative percent difference between the matrix spike and matrix spike duplicate is calculated and used to assess analytical
precision.
An analytical control consisting of a blank matrix containing all reagents,
internal standards .and surrogate standards, that is carried through the entire analytical procedure. The method blank is used to define the level of laboratory background and contamination, and to demonstrate that this
level does not exceed acceptance limits. Acceptable levels of
contamination are defined by project specific data quality objectives:
The minimum concentration of a substance that can be measured and
reported with 99% confidence that the ana\yte concentration is greater than zero. Method Detection Limits are determined using replicate spike samples prepared by the lab and taken through all preparation and analysis
steps of the method. The method detection limit is calculated using the
appropriate Student's !-parameter times the standard deviation of a series
of spiked samples.
PRLs were developed in conjunction with analysis codes (A-codes) for the
EPIC LIMS. PRLs create uniformity across the company by establishing a
standardized reporting limit by method to be utilized by all Pace
laboratories. The PRL has been defined as the highest statistically derived·
MDL value for a particular method found at any of the Pace laboratory
operations which are performing the method.
A process to evaluate the proficiency of an analyst or laboratory by
evaluation of the results obtained on test materials in either a known, single
or double-blind fashion.
The measurement of agreement of a set of replicate results among
themselves without any prior information as to the true result. Precision is assessed by means of duplicate/replicate sample analysis.
A stated plan that clearly defines the objectives, methods and procedures
for accomplishing a task.
The practical quantitation limit (PQL) is the lowest level that can be reliably
achieved within specified limits of precision and accuracy during routing
laboratory operating conditions.
QAPP:
Quality
Assurance:
Quality
Control:
Reagent Grade:
Replicate
· Samples:
Reporting
Limit.
Rounding
~
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A Quality Assurance Project Plan or QAPP is a project specific document that describes the policies, organization, objectives, functional activities,
and specific QA and QC activities designed to achieve the data quality goals of a specific project.
A system of policies and procedures whose purpose is to ensure, confirm and document that the product or service rendered fulfills the requirements of Pace and its client. Quality Assurance includes quality planning, quality
control, quality assessment (auditing), quality reporting and corrective
action.
A system of checks and corrective measures, integrated with the activities that directly generate the product or service, that serves to monitor and adjust the process to maintain conformance to predetermined
requirements.
Analytical reagent (AR) grade, ACS reagent grade, and reagent grade are synonymous terms for reagents which conform to the current specifications of the Committee on Analytical Reagents of the American Chemical
Society.
A second, separate sample collected at the same time, from the same
place, for the same analysis, as the original sample in order to determine precision between the two samples.
The level at which method, permit, regulatory and client specific objectives
are met. The reporting limit may never be lower than the statistically determined MDL, but may be higher based on any of the above considerations. Reporting limits are corrected for sample · amounts, including the dry weight of solids, unless otherwise specified. Reporting limits are often set according to action or cleanup levels for a particular site or project which have been established in accordance with Data Quality Objectives (DQOs) under which the analytical work is to be processed.
If the figure following those to be retained is less than 5, the figure is dropped, and the retained figures are kept unchanged. As an example, 11.443 is rounded to 11.44. If the figure following those to be retained is greater than 5, the figure is dropped, and the last retained figure is raised
by 1. As an example, 11.446 is rounded to 11.45. If the figure following those to be retained is 5, and if there are no figures other than zeros
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Sample Delivery
Group <SPGJ:
Sensitivity·
Split Sample·
Standard:
Standard Blank:
Standard Curve:
Standard
Operating
Procedure:
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beyond the five, the figure 5 is dropped, and the last-place figure retained is
increased by one if it is an odd number or it is kept unchanged if an even
number. As an example, 11.435 is rounded to 11.44, while 11.425 is
rounded off to 11.42. If a series of multiple operations is to be performed
(add, subtract, divide, multiply), all figures are carried through the
calculations. Then the final answer is rounded to the proper number of
significant figures.
A unit within a single project that is used to identify a group of samples for
delivery. An SDG is a group of 20 or fewer field samples within a project,
received over a period of up to 14 calendar days. Data from all samples in
an SDG are reported concurrently. A Sample Delivery Group is generally
defined by one of the following, whichever occurs first:
• All samples within a project; or
• Every set of 20 field samples within a project; or
• All samples received within a 14-day calendar period
Samples may be assigned to Sample Delivery Groups by matrix (i.e., all
soil samples in one SDG, all water samples in another), at the discretion of
the laboratory. Clients may establish different SDG classifications to meet
project specific requirements.
Capability of methodology or instrumentation to discriminate between
samples having differing concentrations or containing differing amounts of
an analyte.
A portion or subsample of a total sample obtained in such a manner that is
not believed to differ significantly from _other portions of the same sample.
A substance or material, the properties of which are known with sufficient
accuracy, to permit its use to evaluate the same property in a sample.
A calibration standard consisting of the same solvent/reagent matrix used
to prepare the calibration standards without the analytes. It is used to
construct the calibration curve by establishing instrument background.
A standard curve is a curve which plots concentrations of known analyte
standard versus the instrument response to the analyte.
A procedure adopted for repetitive use when performing specific
measurement or sampling operation. It may be an industry accepted
standard method or one developed by the user.
Surrogates:
Systems Audit:
Traceability:
Trip Blank:
Validation:
Warning Limits:
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When employed, these are compounds added to every blank, sample,
matrix spike, matrix spike duplicate, lab control sample, and standard prior
to any processing or preparation; used to evaluate analytical efficiency by
measuring recovery. Surrogate compounds are not .expected to be
detected in environmental media, but are similar to the analytes of interest.
Surrogates are generally utilized for organic analyses.
An on-site inspection or assessment of a laboratory's quality control
system.
The ability to trace the source and accuracy of a material (i.e. standard) to
a recognized primary reference source such as the National Institute of
Standards and Technology (NIST) or USEPA. Also, the ability to
independently reconstruct and review all aspects of the measurement
system through available laboratory notebooks and documentation and
reach the same results.
This blank is used to detect sample contamination from the container and
preservative during transport and storage of the sample. A cleaned sample
container is filled with laboratory pure water: any preservative used in the
sample is added; and then the blank is stored, shipped, and analyzed with
its group of samples.
The process by which a sample, measurement, method, or piece of data is
deemed useful for a specified purpose as based upon the DQOs
established for quality control measurements such as accuracy, precision,
representativeness, and completeness.
The limits (typically 2 standard deviations either side of the mean) shown
on a control chart within which most results are expected to lie (within a
95% probability) while the system remains in a state of statistical control.
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I 4.0 QA ORGANIZATION AND PERSONNEL
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Pace Analytical Services, Inc. is a privately held, full service environmental testing firm operating an integrated system of seven laboratori~s. plus multiple service centers nationwide. Each laboratory within the system is set up as an !individual entity with local management, but all share common systems and receive support from the corporate office. The chief function of the corporate office is to assist the system laboratories. The corporate office centralizes company wide accounting, business development, fin~ncial management, human resources development, information systems, marketing and quality activities. The organizational structure of the corporation is provided in Figure 4.1. ·
For efficient laboratory operation, it is important that all laboratory employees understand the operational structure, specific areas of respohsibility and lines of authority within the organization.
It is equally important for laboratory personlnel to understand that the structures of the Quality Organization may be separate from other ikboratory operations but that the quality function is totally integrated into every aspect of laboratory operation. All laboratory personnel are responsible for knowing and following pro'per methods and standard operating procedures; recording quality control information require'd by those procedures in the proper location; and suspending analyses when quality control cri/eria are not met.
The organizational structure of a Pace Anal~ical Services, Inc. analytical chemistry laboratory is provided in Figure 4.2. The laboratory is managed by the General Manager. The Client Services (Sample and Project Management) and Quality Assurance Groups report directly to the General
Manager. I
Under the direction of the Laboratory Operations Manager, the technical staff of the laboratory is generally organized into the following function~! groups:
Sample Preparation -Organic
Sample Preparation -Metals
Wet Chemistry
Metals Analysis
GCAnalysis
GC/MS Volatiles Analysis
GC/MS Semivolatiles Analysis
Reporting/Data Validation
In some laboratory operations the Laboratory Operations Manager position may not exist; in such a case, the responsibilities of the position a1re distributed between the Organic and Inorganic Department Managers. Each group is headed by a Group Leader or Section Supervisor who is responsible for operations on a daily basit Environmental chemists, analysts, laboratory technicians and laboratory assistants report to \he Group Supervisors.
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4.1 LABORATORY ORGANIZATION
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It is the individual responsibility of each analyst and technician to perform their assigned
tasks according to the applicable SOPs, QA Project Plans, Study Protocols, and Work
Plans. This responsibility includes performing quality control analyses as specified in the method SOP and entering the QC data in the appropriate method control file system. The analyst shall report out-of-control results to the Group Supervisor/Leader.
Group Supervisors/Leaders shall ensure that analysts and technicians are instructed in the requirements of the Pace Laboratory QA Manual, site-specific QA Project Plans, SOPs, Protocols, and Work Plans for the analytical method or other procedure. Group
Supervisors/Leaders shall review sample QC data at frequent intervals designed to ensure
that QC analyses are being performed at the required frequency, that data are
documented in the method control file system and that established corrective action procedures for out-of-control situations are followed and the results documented. It is the responsibility of the Group Supervisor/Leader to ensure that data have been validated and reported· to the Operations Manager. Group Supervisors/Leaders shall report to the
appropriate Manager.
The Operations Manager shall take overall responsibility for technical conduct, evaluation
and reporting of all analytical tasks associated with each study. The Operations Manager ensures that approved procedures are documented and followed, that all data are recorded and verified and that all deviations from approved procedures are documented.
The Operations Manager shall ensure that Group Supervisors/Leaders are instructed in the requirements of the Pace Laboratory QA Manual, study-specific QA Project Plans,
SOPs, Protocols, and Work Plans. The Operations Manager provides guidance and
assistance in the development of laboratory quality control procedures; approves quality · control limits for methods; works with supervisors to bring out-of-control methods back to
within established acceptance limits; and assists supervisors in correcting analytical
problems revealed in QA audits. The Operations Manager shall report to the General
Manager.
The Quality Assurance Department, under the direction of the Quality Assurance Officer, shall be responsible for conducting systems audits and inspections for compliance with
this manual, SOPs and QA Project Plans or other project-specific protocols, maintaining
the archives, maintaining historical files of all QA documents, reviewing QC charts, documenting findings and corrective actions, and reporting findings to management. The Quality Assurance Officer shall report directly to the General Manager of the Pace facility.
The Pace General Manager shall designate and replace if necessary, the Operations
Manager, and is responsible for managing all activities related to laboratory services,
including the Quality Assurance Program. The Pace General Manager shall ensure that
there is a Quality Assurance Department, that personnel and other resources are
adequate, that personnel have been informed of their responsibilities, that deficiencies are reported to the Operations Manager and that corrective actions are taken and
documented. Any significant changes to written SOPs shall be authorized in writing by
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4.2
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either the General Manager or the Operations Manager and the Quality Assurance Officer
of the Pace location.
DESCRIPTION OF RESPONSIBILITIES
Individuals involved with implementing procedures outlined in the LQAP have the following
quality related duties and responsibilities:
4.2.1 Pace's Vice President of Quality is responsible for assisting in the development,
implementation and monitoring of quality programs for the company.
Responsibilities include:
1. Review and direct implementation of appropriate analytical Standard
Operating Procedures.
2. Formulate and implement analytical product deliverables.
3. Provide technical direction to laboratories regarding existing and new
analytical operations.
4. Provide leadership and direction to the laboratory Quality Assurance
Officer.
5. Perform laboratory and project specific audits.
6. Assist in development, implementation, and monitoring of appropriate
training programs.
4.2.2 The Pace Laboratory General Manager is responsible for overall laboratory
operations. Specific responsibilities that relate to quality assurance are:
1. Implement the QA Program within the specific laboratory.
2. Regularly determine the effectiveness of the QA program.
3. Supervise quality control activities.
4. Approve laboratory-specific attachments to the QA manual and
project-specific Quality Assurance Project Plans.
5. Recommend changes in the QA Program to the laboratory Quality
Assurance Officer.
6. Maintain a current distribution list for QAPPs and generic LQAP.
7. Approval oversight for all reports issued by the laboratories.
8. Serve as the focal point for the reporting and disposition of all
nonconformances.
9. Maintain a current laboratory organization chart.
4.2.3 The Pace Laboratory Proiect Manager is the lead person within the laboratory
for direct oversight of all aspects of a specific project. Specifically, some of the
project manager's responsibilities are:
1. Establishing direct dialogue with the client pertaining to project
requirements, including methodology, TAT, technical information, etc.
2. Arranging bottle orders and shipment of sample kits to client.
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3.
4.
5.
6.
7.
8.
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Verifying log-in information relative to project requirements and field
sample chain of custodies.
Interfacing with laboratory operations staff to update and set job priorities.
Updating clients on job status.
Providing verbal and facsimile results to clients.
Assisting laboratory staff with report preparation.
Working with clients, laboratory staff, and other appropriate Pace staff to develop project statements of work or resolve problems of data quality,
turnaround, or completeness.
4.2.4 The Pace laboratory Quality Assurance Officer (QAO) reviews all aspects of QA/QC for the laboratory. The duties of the laboratory QAO are to:
1. Assist the project manager in specifying QA/QC procedures to be used during the project.
2. Execute QC procedures and techniques to ensure that the laboratory
achieves established standards of quality.
3. Evaluate data quality and maintain records on related QC charts and
other pertinent information.
4. Monitor laboratory activities to determine conformance with authorized
QA policy, and to implement appropriate steps to ensure adherence to
QA programs.
5. Coordinate with the client's representative concerning external audits.
6. Review performance evaluation results.
7. Assist in development and implementation of appropriate training
programs.
4.2.5 The Operations Manager oversees day-to-day production and quality activities
of both inorganics and organics laboratory section providing wet chemistry,
metals prep, metals, pesticide/PCB, volatiles and semivolatiles analyses. The
specific duties of the Operations Manager are:
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1. Provide supervision of laboratory operations.
2. Implement the laboratory quality assurance plan.
3. Ensure proper scheduling and execution of testing programs.
4. Ensure that quality assurance and quality control criteria of analytical
methods and projects are satisfied.
5. Assess data quality and take corrective action when necessary.
6. Notify the project team of specific laboratory nonconformances and
changes.
7. Approve and release technical and data management reports.
8. Ensure that analysts and technicians maintain sample custody in the laboratory.
9. Approve project specific laboratory quality assurance plans.
10. Coordinate management of projects through technical supervisors.
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Date: 12/22/95
Section 4.0
Revision 0.01
Page 5 of 10
4.2.6 Group Supervisors/Leaders affect data quality by fulfilling responsibilities to:
1. Serve as the lead analyst within the specific sections.
2. Lead the training of analysts in laboratory operations and analytical
procedures.
3. Organize and schedule analyses with consideration for sample holding times.
4. Implement data verification procedures.
5. Assign duties to analysts as data validators.
6. Prepare data summaries for review by the Laboratory Operations Manager.
7. Evaluate instrument performance and supervise instrument calibration and preventive maintenance programs.
8. Report noncompliance situations in regard to the project to the Laboratory Managers or laboratory Quality Assurance Officer, as appropriate.
4.2.7 Analysts are responsible for tasks identified in the scope of work. They perform the laboratory technical activities within these tasks. The duties of analysts are to:
1. Assist in planning for each phase of their tasks and in defining objectives and activities.
2. Respond to work plan revisions related to their tasks.
3. Advise the project manager of progress, needs, and potential problems of their tasks.
4. Train and qualify alternate analysts in specified laboratory QC and analytical procedures.
5. Verify that laboratory QC and analytical procedures are being followed as specified.
6. Review sample QC data at least daily. This includes examination of raw data such as chromatograms (and checking of calculations for a minimum of 10% of the samples analyzed) as well as an inspection of reduced data, calibration curves, and laboratory notebooks.
7. Inform project managers if the daily review indicates a decline in data quality and implement corrective action.
4.2.8 The Sample Custodian serves as sample coordinator for the entire laboratory.
:\lqapreva\sect4 .doc
Responsibilities are to:
1. Sign for incoming field samples and verify the data entered on the chain-of-custody forms.
2. Enter the sample information into the computerized Laboratory
Information Management System for tracking and reporting. 3. Generate computerized sample analysis and data entry form_s (SADEF).
4.3
4.4
Date: 12/22/95
Section 4.0
Revision 0.01
Page 6 of 10
4. Transfer samples and tracking forms to laboratory project analysts.
TRAINING AND ORIENTATION
Each new permanent employee receives a four part orientation: a human resources orientation, a safety department orientation, a quality assurance department orientation, and a supervisory orientation. The human resources orientation involves matters of immediate personal concern such as benefits, salary, and company policies. The safety department orientation is an in-depth examination of the Pace Chemical Hygiene Plan and safety program, which are consistent with the requirements of OSHA's Hazard Communication Program (29 CFR 1910.1200). The Quality Assurance orientation provides the new employee with information on the Pace QA program through a brief introduction to the QA manual and SOPs, acceptable record keeping practices, and the individual's responsibility with respect to the quality assurance program. The new employee's Group Supervisor provides the employee with a basic understanding of the · role of the laboratory within the structure of Pace, Inc. and the basic elements of that individual's position within the laboratory.
Temporary employees receive the same orientation as permanent staff with the exception of the Human Resources orientation. The training of a new employee concentrates on his/her scientific background and work experience to provide the employee with a level of competence so that the individual will be able to function within the defined responsibilities of his/her position ASAP. Training is a process used to assist laboratory personnel in their professional development. The training techniques utilized include:
On-the-job training
Lectures
Programmed learning
Conferences and seminars
Short courses
Specialized training by instrument manufacturers
• Participation in check-sample or proficiency sample programs.
Group Supervisors shall be responsible for providing documentation of training and proficiency for each employee under their· supervision. The Training Documentation File indicates what procedures (SOPs) a technician is capable of performing either
independently or only with supervision. The files shall also include examples demonstrating performance of passing QC samples. The Group Supervisor is responsible for keeping a training documentation file for each person under their supervision which is updated and current. The QA department shall maintain a file for each technical employee.
These files shall include a current curriculum vitae or resume.
LABORATORY SAFETY
Sample receiving areas and laboratories shall be equipped with suitable hoods, respirators, protective clothing and eye wear, gloves, barrier creams and or other
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4.5
Date: 12/22/95
Section 4.0
Revision 0.01
Page 7 of 10
measures to prevent or m1rnm1ze staff contact with hazardous substances. Safety equipment such as eyewash stations, drench showers, spill adsorbents and neutralizers, fire extinguishers, first aid materials, and breathing oxygen shall be available.
As a matter of policy, Pace shall not accept known initiator explosives, known dioxin-contaminated materials or unusual biohazard materials except where a specific Pace facility has been designed to safely handle high hazard samples. Pace shall accept nitroaromatics and nitroamines providing that the client makes provisions for disposal of samples with a positive explosive identification.
A• laboratory staff member shall be designated as Safety Manager by the General Manager. The Safety Manager prepares and maintains safety-related SOPs, conducts safety and occupational health orientation, training and review sessions as required, and maintains up to date familiarity with safety and occupational health issues pertinent to the laboratory.
The Safety Manager prepares and maintains educational programs as required to comply with state and federal "right to know" legislation.
The Safety Manager or his designee shall conduct an orientation session with each new staff member to familiarize him/her with routine and emergency safety procedures and equipment. Eye protection and a lab coat shall be issued to the employee. A respirator will be issued, as required, after respiratory protection training. A tour of the laboratory shall be conducted. During the tour, needs for eye, skin, and respiratory protection shall be discussed as well as the use of safety glasses, face shields, goggles, partial and full-face respirators, ventilated work areas, fume hoods, gloves, barrier creams, and Tyvek coveralls. The location of eye wash stations, drench showers, fire extinguishers, and first aid equipment shall be shown to the employee and their use shall be described or demonstrated. Fire and spill notification, emergency procedures, and evacuation stations shall be taught during this . session. The orientation concludes with an introduction to potential chemical hazards and the Material Safety Data Sheets (MSDS). MSDS shall be made available for review.
Employees shall be responsible for their own safety. The Operations Manager and Group Supervisors may require that certain levels of protective equipment be worn when in their judgment it is appropriate. Failure of an employee to wear required protective equipment will result in immediate disciplinary action.
SECURITY AND CONFIDENTIALITY
Three tiers of security shall be maintained within Pace for the purpose of controlling external influences on samples, analytical processes, and data. These security
procedures help ensure the completeness, representativeness, accuracy, and precision of analytical results.
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Date: 12/22/95
Section 4.0
Revision 0. O 1
Page 8 of 10
The first tier of security maintained shall be controlled access to laboratory buildings. Exterior doors to laboratory buildings shall remain either locked or continuously monitored by a Pace staff member. Keyless door-lock combinations (and computer access codes/logins) shall be changed every time an employee terminates employment at Pace. Posted signs shall direct visitors to the reception office and mark all other areas as off limits to unauthorized personnel. All visitors to the facilities must sign the Visitor's Logbook maintained by the receptionist. All visitors shall be accompanied by a staff member during the duration of their stay on the premises. The staff member shall escort the visitor back to the reception area at the end of his/her visit where he/she shall sign out in the Visitor's Logbook. Prior to departure of the last staff member at the close of each· day, all windows shall be locked and all doors checked and locked by the last staff member.
The second security level shall be within the facility and may be designated as required by the Operations Manager in consultation with the General Manager. Individual Operations Manager or Group Supervisors may close specific areas under their responsibility to entry by unauthorized persons. A list of authorized persons shall be prepared and signed by the General Manager. "Closed Areas" shall be designated by prominent postings at all points of access.
The final tier of security shall be comprised of specific secure areas for sample, data and client report storage which shall be lockable within the facilities, and to which access shall be limited to specific individuals or their designees. Security of sample storage areas shall be the responsibility of the Sample Manager. Security of samples and data during analysis and data reduction shall be the responsibility of Group Supervisors and Operations Manager. Security of client report archives shall be the responsibility of the Quality Assurance Officer or an appropriate designee. These secure areas will be locked whenever these individuals or their designees are not present in the facility.
Designated laboratory sample storage locations are designed to limit access to authorized personnel only, and provisions for lock and key access shall be provided. No samples are to be removed without authorization, which consists of having a work list requesting analysis on an aliquot. No samples are to be removed without filling out the associated chain-of-custody records.
Standard business practices of confidentiality shall apply to all documents and information regarding client analyses. Specific protocols for handling confidential documents are described in Pace SOPs. Additional protocols for internal identification of samples and data by number only shall be implemented as required under contract-specific Quality Assurance Project Plans.
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Figure 4.1
Date: 12/22/95
Section 4.0
Revision 0.01
Page 9 of 10
Pace Analytical Services, Inc. Organizational Structure
Chairman of
the Board
I
PresidenUCEct
I I Corporate Offic: I Laboratories I I
Quality Assuran ie
Human Quality & Office r-
Resources >--Technical Oirecti n
Sales & Information Inorganic Organic Marketing r-r-Systems Laboratory ,--Laboratory
Finance Field Marketing & -Services ,-,-Client Servicei
Support la{ Accountin Services -
Client Services
:\lqapreva\sect4 .doc
Figure 4.2
Pace Analytical Services, Inc. Laboratory
Organizational Structure
General Manager
QA Officer
Operations Manager
Group Services
Analysts and
Technicians
Field Services
Date: 12/22/95
Section 4.0
Revision 0.01
Page 10 of 10
Support Services
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5.0 QUALITY ASSURANCE OBJECTIVES
Date: 12/22/95
Section 5.0
Revision 0.01
Page 1 of 12
The purpose of this Quality Assurance Plan is to define procedures for the documentation, evaluation, validation, and reporting of data. The objective is to provide a uniform basis for sampling, sample handling, instrument maintenance and calibration, methods control, performance evaluation and analytical data generation and reporting. Specific procedures to be used for sampling, chain of custody, calibration of field instruments (pH, conductivity meters, etc.), laboratory analysis, reporting, internal quality control, audits, preventive maintenance, and corrective actions are described in specific sections of this plan. This section addresses the objectives of precision, accuracy, representativeness, completeness, and comparability (PARCC) which are used to assess whether the data meet the established DQOs (Data Quality Objectives), that are based upon the intended end use of the data.
The quality assurance objective of the laboratories is to provide data of known and documented quality. Data quality is assessed by precision, accuracy, representativeness, completeness, and comparability. The QA protocols used in the laboratories for the majority of analyses performed are taken from the following sources: EPA Contract Laboratory Program's Statement of Work (Organics and lnorganics), 40 CFR 136 methodologies, and SW 846 methodologies which contain detailed descriptions of the quality control measures routinely employed by Pace Analytical Services, Inc ..
As stated, the objective of the Quality Assurance Program for the laboratory is to provide data of known quality. To accomplish this, Pace will:
5.1
• Maintain an effective, on-going QNQC program that measures and verifies laboratory performance.
• Provide a quality organization independent of the pressures of project performance with the responsibility and authority for auditing and recommending corrective action. • Provide a quality organization with clear paths of communication with management. • Provide sufficient flexibility to allow controlled changes in routine methodology to meet client specific data requirements contained in project-specific quality plans. • Recognize as soon as possible and provide correction for any factors which adversely affect data quality.
• Monitor operational performance of the laboratory on a routine basis and provide corrective action as needed.
• Maintain complete records of sample submittal, raw data, laboratory performance, and completed analyses to support reported data.
LEVEL OF QA EFFORT
The reliability of data generated in the laboratory will be evaluated at the 99% confidence level (mean +/-3 standard deviations) for control and at the 95% confidence level (mean +/-2 standard deviations) for warnjng. Precision of analyses will be evaluated using sample duplicates and matrix spike duplicates. Analytical accuracy will be monitored using recovery of analytes from surrogate spikes, matrix spikes, EPA reference check standards (when available) and/or lab control samples, and Performance Evaluation (PE) samples.
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5.2 PRECISION AND ACCURACY
Date: 12/22/95
Section 5.0
Revision 0.01
Page 2 of 12
Precision measures the reproducibility of repetitive measurements. It is strictly defined as the degree of mutual agreement among independent measurements. as the result of repeated application of the same process under similar conditions. Analytical precision is a measurement of the variability associated with duplicate (two) or replicate (more than two) analyses of the same sample in the laboratory and is determined by analysis of laboratory duplicates. Total precision is a measurement of the variability associated with the entire sampling and analysis process. It is determined by analysis of duplicate or replicate field samples and incorporates variability introduced by both the laboratory and field operations. Precision data must be interpreted by taking into consideration these possible sources of variability. Duplicate (two) samples or spiked samples are analyzed to assess field and analytical precision as required under certain programs (e.g., Air Force tasks), and the results are assessed using the relative percent difference (RPO) between duplicate measurements. Precision objectives are presented for each analytical method in the corresponding Pace Standard Operating Procedure (SOP).
Accuracy is a statistical measurement of correctness and includes components of random
error (variability due to imprecision) and systematic error. It therefore reflects the total error associated with a measurement. A measurement is accurate when the value reported does not differ from the true value or known concentration of the spike or standard. Analytical accuracy is typically measured by determining the percent recovery of known target analytes that are spiked into a field sample (a surrogate or matrix spike) or reagent water (laboratory control sample [LCS] or QC check sample). Surrogate compound recovery is reported and is used to assess method performance for each sample analyzed for volatile and semivolatile organic compounds. The stated accuracy objectives apply to spiking levels at least five times the method detection limi_ts (MDLs) or background concentration.
Both accuracy and precision are calculated for analytical batches, and the associated sample results must be interpreted by considering these specific measures. Calculation of precision and accuracy to measurement sample results is discussed in the QC section of each SOP.
The QA objectives for precision and accuracy are to achieve the QC acceptance criteria specified in the proposed analytical procedures. For the organic and inorganic procedures, the precision and accuracy guideline requirements are specified in the individual methods. ·
Field blanks and duplicates are collected and analyzed to assess field sampling activities. The results check procedural contamination and/or ambient conditions at the site.
Due to the extensive number of organic parameters and potential matrices, the development of precision and accuracy objectives and control limits for every matrix is difficult. This is typically done with (1) matrix spike and matrix spike duplicate compounds which are added to selected samples before extraction and analysis, and/or
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5.3
Date: 12/22/95
Section 5.0
Revision 0.01
Page 3 of 12
(2) surrogate spike compounds which are added to every sample, before extraction and
analysis. Although the surrogate and matrix spike analyses do not provide statistically
valid statements about precision and accuracy for every compound in a sample, they do
give the data reviewer enough information to make judgments about precision and
accuracy on a sample-by-sample basis.
Inorganic precision and accuracy data are determined by using duplicate or matrix spike
duplicate samples {precision}, matrix spike and laboratory control samples (accuracy).
The following procedure is used:
For a duplicate (or matrix spike duplicate) sample analysis, at least one duplicate
(or MSD) sample is analyzed per sample matrix type (e.g., water, soil) and
concentration (e.g., low, medium) per batch of samples or for each 20 samples
received, whichever is more frequent, or as specified by state/project
requirements. Samples identified as field blanks can NOT be used for duplicate
(or MSD) samples analyses. If two analytical methods are used to obtain the
reported values for the same element for a batch of samples (i.e., ICP, GFAA},
duplicate samples will be run by each method. The relative percent difference
(RPD) for each component is calculated for later use during data assessment.
The QC limits for accuracy and precision are developed based upon laboratory derived
data. When applicable, interlaboratory control limits established by the EPA CLP are used to judge acceptability of data generated by the laboratories. Where EPA
acceptability criteria does not exist for a given method being utilized for the first time, the
laboratories will establish control limits derived from a minimum of four data points. Until
verified by a statistically significant data population, the control limits will be considered
as advisory limits only and will not automatically initiate a rerun or reanalysis criteria if they are not met.
Representative QC objectives for selected organic parameters are listed in Tables 5.1 to
5.6. Similarly representative QC objectives -for selected metal and inorganic parameters
are listed in Tables 5.7 to 5.8. Generally, QC acceptance limits are laboratory specific,
having been statistically derived from an individual laboratory's data. QC objectives for
a specific laboratory will be included in a project specific QAPP or for general
information as a facility specific addendum to this document.
COMPLETENESS
Completeness is a measure of all information necessary for a valid scientific study. For
completeness, it is expected that the methodology proposed for chemical
characterization of the samples collected will provide data meeting QC acceptance
criteria following standard laboratory data review and validation for at least 95% of all
samples collected. Completeness may also be defined as a comparison of the number
of tests successfully completed (with acceptable QC) to the number of tests requested.
Discrepancy reports are completed to provide explanation when QC criteria are not met.
Every attempt will be made to generate completely valid data. However, it is recognized
that some samples will exhibit highly contaminated matrices necessitating multiple
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5.4
5.5
Date: 12/22/95
Section 5.0
Revision 0.01
Page 4 of 12
analyses and/or extensive dilutions. As a result of these atypical applications, recoveries and MDLs or Rls, as applicable, may be deemed questionable based on internal QC results by the ex1ernal data validation process. The objective will be to have 95% completeness on samples unaffected by matrix interferences. For uncontaminated background samples and first time samples not showing interferences, completeness should be 100% with a mandatory requirement for reanalysis of these critical samples if objective is not met.
5.3.1 Random Error
EPA has established (preamble to 40 CFR Part 136, Vol. 49, No. 209, October 26, 1984) that there is a 5% probability that the results obtained for any one analyte will exceed the control limits established for the test due to random error. As the number of compounds measured increases in a given sample, the probability for statistical error also increases.
The number of compounds present in numerous EPA methods (e.g., GC/MS methods 82408 and 82708, and metals included in ICP method 6010A) increases the probability that one or more analytes will not meet acceptance criteria to significantly more than the 5% per analyte frequency. The number of target analy1es included in these tests can be used to show that a minimum of four to seven target analy1es will exceed the control limits established for these methods due to the statistical probability for random error. The establishment of QC criteria that are not consistent with the measurement of the quality objectives for which they are intended should be discouraged.
REPRESENTATIVENESS
Representativeness is a qualitative element that is related to the ability to collect a sample that reflects the characteristics of that part of the environment that is to be assessed. Sample representativeness is dependent on the sampling techniques used and is considered individually for each project. It is specifically addressed in the work plan.
Representativeness is a measure of how closely the measured results reflect the actual concentration or distribution of the chemical compounds in the sample. Sample handling protocols (e.g., collection, storage, preservation and transportation) have been developed to preserve the representativeness of the samples. Proper documentation will establish that protocols have been followed and sample identification and integrity assured. Every attempt will be made to ensure that the aliquots taken for analysis are homogeneous and representative of the samples received.
COMPARABILITY
Comparability is also considered during preparation of a site specific work plan. The objective of comparability is to ensure that results of similar activities conducted by different parties are comparable. This often involves the use of two independent laboratories on a project or site, whereby the second laboratory is used to confirm a pre-
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5.6
5.7
Date: 12/22/95
Section 5.0
Revision 0.01
Page 5 of 12
established percentage of sample analyses. Pace uses EPA-approved or-other methods and procedures to ensure comparability with data from previous or following studies. Pace participates in external and interlaboratory performance evaluation (PE) studies as additional means of establishing comparability in the laboratory.
TRACEABILITY
Traceability is the extent to which results can be substantiated by hard-copy documentation. Traceability documentation exists in two forms: that which links final numerical results to authoritative measurement standards, and that which explicitly describes the history of each sample from collection to analysis. Refer to the sections
on sample custody and records management for more specifics on Pace procedures.
QUALITY ASSURANCE PROJECT PLAN EXCEPTIONS
Due to the unknown nature of environmental samples prior to analysis, Pace has minimal
control over analytical and quality control complications which arise from unique sample matrix conditions. These conditions may include such items as: highly concentrated
samples containing target compounds of interest and/or non-target components; extremes in sample pH, viscosity, and solubility; and high organic content (both natural and synthetic). Each of these conditions presents a variety of challenges to the laboratory.
Most often these extremes in sample matrix composition necessitate the laboratory to employ dilution techniques in order to change the sample state into one which can be analyzed by the desired protocol. Unfortunately, dilution techniques raise reporting limits (Rls) and often adversely impact the surrogate standard and matrix spiking acceptance
criteria.
The laboratory has the responsibility to clearly identify cases where matrix interferences preclude the generation of "compliant" data. This is done by demonstrating through reproducibility (i.e., reanalysis of the affected sample) that the quality control measurement failure resulted from unique sample matrix conditions beyond the control of laboratory, and not as a result of laboratory error. For example, in situations where the surrogate standard recoveries fall outside of control limits, samples are re-extracted and/or re-analyzed. Similar "non-compliant" results in the reanalysis indicate that it is something inherent to the sample which prevented the laboratory from reporting results deemed method compliant under data validation criteria.
Analytical projects containing particularly "dirty" samples (i.e., highly contaminated) will often fail to meet pre-established QA completeness goals (set forth in the QAPP) when prior site history does not reveal the potential for excessive values. Again, while the laboratory perfomns all analytical testing by the prescribed protocols, the results obtained may not meet validation criteria as a result of elevated Rls or the frequency at which surrogate and matrix spikes failed to meet acceptance limits. In cases where the laboratory is unable to meet QC criteria because of sample matrix complications beyond their control, results which are fiagged "qualified" or "rejected" by data validation guidelines are often still "useable" by the end user of the data.
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5.8
Date: 12/22/95
Section 5.0
Revision 0.01
Page 6 of 12 ·
Pace is committed to adhering to method requirements and program quality control applications as established by our client and will work rigorously to provide data which is of the highest quality possible. However, the uncertainties associated with environmental samples do not allow Pace to assume responsibility for conditions beyond our reasonable control which directly impact the "validity" versus the usability of the associated analytical data generated.
PERSONNEL QUALITY OBJECTIVES
Pace is committed to the philosophy that quality operations result from quality planning, design, and work performance by skilled operational personnel. Pace's policy is to perform its varied types of technical work in accordance with standard quality assurance practices such as Good Laboratory Practices (GLP) and the EPA Contract Laboratory Program (CLP),· as well as other appropriate regulatory agency guidelines and requirements. Each laboratory within Pace has a Quality Assurance Officer responsible for maintenance of standard operating procedures, laboratory audits, performance evaluations, federal and state certifications and quality assurance documentation.
Each laboratory worker is responsible for checking standard operating procedures when necessary; following these procedures during routine analyses; recording quality control information required by those procedures in the proper location, and taking appropriate corrective action including suspending analyses when quality control criteria are not met.
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Table 5.1
Date: 12/22/95
Section 5.0
Revision 0.01
Page 7 of 12
Representative Spike Recovery Acceptance Criteria for.
Volatile Organic Analysis by Methods 80108 and 8020A
MS¾R LCS¾R
(SW-846) (Statistical)*
Analyte Water/Soil Water SQl!
Method 8010A
1, 1-Dichloroethene 28-167 63-145 47-137
Chloroform 49-133 70-137 66-140
Carbon tetrachloride 43-143 72-138 63-143
1,2-Dichloroethane 51-147 74-138 60-157
Trichloroethene 35-146 75-147 63-152
Tetrachloroethene 26-162 79-134 72-138
Chlorobenzene 38-150 76-126 65-136
1,4-Dichlorobenzene 42-143 70-123 64-127
Method 8020
Benzene 39-150 74-135 43-156
Chlorobenzene 55-135 74-130 80-126
1,4-Dichlorobenzene 42-143 70-125 75-120
¾R
(Statistical)*
Surrogate Water SQl!
· Bromochloromethane 54-115 60-109
1,4-Bromofluorobenzene 70-125 68-112
• Statistically derived acceptance limits will vary by individual laboratory operation.
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Table 5.2
Date: 12/22/95
Section 5.0
Revision 0.01
Page 8 of 12
Representative Spike Recovery Acceptance Criteria for
Purgeable Petroleum Hydrocarbon Analysis
(California LUFT Method)
Analyte
Benzene
Toluene
Ethylbenzene
Xylene
Surrogate
Bromofluorobenzene
MS¾R
(SW-846)
Water/Soil
LCS¾R
(Statistical)*
Wru.er Soil
39-150
46-148
32-160
32-160
80-110
80-110
83-113
83-113
¾R
(Statistical)*
Wfiler S.oi.l
70-113 51-120
Table 5.3
49-103
49-103
52-106
56-104
Representative Spike Recovery Acceptance Criteria for
Extractable Petroleum Hydrocarbon Analysis
(California LUFT Method)
Analyte
Diesel
Surrogate
2-Fluorobiphenyl
o-Terphenyl
MS¾R
(Advisory)
Water/Soil
50-150
LCS¾R
(Statistical)*
Ware! Soil
62-122 57-123
¾R
(Statistical)*
Wi!.te..r S.oi.l
53-131
41-149
38-128
37-169
• Statistically derived acceptance limits will vary by individual laboratory operatio_n.
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Table 5.4
Date: 12/22/95
Section 5.0
Revision 0.01
Page 9 of 12
Representative Spike Recovery Acceptance Criteria for
Pesticides/PCB Analysis by Method 8080A and CLP SOW
MS¾R
(SW-846)
Water/Soil
MS¾R
(CLP)
LCS¾R
(Statistical)*
Analyte Water 5_oj_) Ws!.te.r 5_oj_)
Aldrin
gamma-BHC
DDT
Dieldrin
Endrin
Heptachlor
Surrogate
Tetrachloro-m-xylene
Decachlorobiphenyl
42-122
32-127
25-160
36-146
30-147
34-111
40-120
56-123
38-127
52-126
56-121
40-131
¾Recovery
(SW-846 Statistical)*
Water Soil
31-121
29-153
32-108
56-125
Table 5.5
34-132
46-127
23-134
31-134
42-139
35-130
32-128
33-135
39-135
37-139
42-138
34-130
¾Recovery
(CLP Advisory)
Water Soil
60-150
60-150
60-150
60-150
Representative Spike Recovery Acceptance Criteria for
Volatile Organic Analysis by Method 82408 and CLP SOW
32-104
31-103
23-125
36-108
37-115
34-106
Analyte
MS¾R
(SW-846)
Water/Soil
MS¾R
(CLP)
LCS¾R
(Statistical)*
Ws!.te.r 5_oj_) Water 5_o.i.!
1, 1-Dichloroethene
Trichloroethene
Chlorobenzene
Toluene
Benzene
Surrogate
59-155
71-157
37-160
47-150
37-151
Toluene-d8
4-Bromofluorobenzene
1,2-Dichloroethane
61-145
71-120
75-130
76-125
76-127
¾Recovery
(SW-846)
Water Soil
88-110
86-115
76-114
81-117
74-121
70-121
59-172
62-137
60-133
59-139
66-142
63-123
77-119
81-117
79-115
83-119
¾Recovery
(CLP)
Watfil: Soil
88-110
86-115
76-114
84-138
59-113
70-121
• Statistically derived acceptance limits will vary by individual laboratory operation.
:\lqapreva\sect5.doC
54-126
77-113
85-115
84-114
83-119
Table 5.6
Date: 12/22195
Section 5.0
Revision 0.01
Page10of12
Representative Spike Recovery Acceptance Criteria for
Semivolatile Organic Analysis by Method 8270B and CLP SOW
MS¾R MS¾R LCS¾R
(SW-846) (CLP) (Statistical)*
Analyte Water/Soil ~ w ~ fuill
1 , 2, 4-Trichlorobenzene 44-142 39-98 38-107 53-95 29-103 Acenaphthene 47-145 46-118 31-137 65-101 45-98 2,4-Dinitrotoluene 39-139 24-96 28-89 63-96 46-92 Pyrene 52-115 26-127 35-142 56-111 49-100 N-Nitroso-di-n-propylamine D-230 41-116 41-126 67-103 40-101 1.4-Dichlorobenzene 20-124 36-97 28-104 48-84 22-95 Pentachlorophenol 14-176 9-103 17-109 40-139 43-123 Phenol 5-112 12-110 26-90 51-105 34-102 2-Chlorophenol 23-134 27-123 25-102 54-106 36-100 4-Chloro-3-methylphenol 22-147 23-97 26-103 64-106 47-99
4-Nitrophenol D-132 10-80 11-114 40-130 49-108
%Recovery %Recovery
(SW-846) (CLP)
Surrogate ~ S.Qil ~ Soil
2-Fluorophenol 21-100 25-121 21-110 25-121
Phenol-d5 10-94 24-113 10-110 24-113
Nitrobenzene-d5 35-114 23-120 35-114 23-120
2-Fluorobiphenyl 43-116 30-115 43-116 30-115
2,4,6-Tribromophenol 10-123 19-122 10-123 19-122
Terphenyl-d,. 33-141 18-137 33-141 18-137
* Statistically derived acceptance limits will vary by individual laboratory operation.
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Date: 12/22/95 I Section 5.0
Revision 0.01
Page 11 of12 I
Table 5.7
I Representative Spike Recovery Acceptance Criteria for
Metals Analysis by SW-846 and CLP SOW
I
LCS¾R
I (Statistical)* earn meter MetbQd Analyte MS¾R ~ ~ Metals-I CPS 6010A/CLP Aluminum 75-125 85-114 51-149
Antimony 75-125 66-135 17-183 I Arsenic 75-125 89-116 48-152 Barium 75-125 87-109 68-132 Beryllium 75-125 75-111 63-137 I Boron 75-125 75-116
Cadmium 75-125 82-123 59-141
Calcium 75-125 88-113 67-133 I Chromium 75-125 88-116 60-140 Cobalt 75-125 90-113 63-137 Copper 75-125 90-112 61-139 I Iron 75-125 86-125 62-138
Lead 75-125 88-116 55-145
Magnesium 75-125 89-111 62-138 I Manganese 75-125 91-112 68-132
Molybdenum 75-125 88-113 61-139 Nickel 75-125 90-119 59-141 I Potassium 75-125 80-115 64-136
Selenium 75-125 85-115 50-150 Silver 75-125 79-120 43-157 I Sodium 75-125 86-112 52-148 Strontium 75-125 80-120
Thallium 75-125 91-120 48-152 I Tin 75-125 80-120
Titanium 75-125 80-120
Vanadium 75-125 90-113 66-134 I Zinc. 75-125 93-121 55-145
Metals-GFM 7041/CLP Antimony 75-125 80-120 17-183
I 7060A/CLP Arsenic 75-125 74-126 48-152 7421/CLP Lead 75-125 74-127 55-145 7740/CLP Selenium 75-125 68-119 50-150
I 7841/CLP Thallium 75-125 79-130 48-152 7470A/CLP Mercury 75-125 75-118 52-148
I Other Metals 7196A Chromium(VI) 75-125 87-116 86-115 CADHS Organic lead 75-125 60-145 71-128
• Statistically derived acceptance limits will vary by individual laboratory operation . !I
:\lqapreva\sectS.doc
Example
Table 5.8
Date: 12/22/95
Section 5.0
Revision 0.01
Page 12 of 12
Representative Spike Recovery Acceptance Criteria for
General Chemistry Analyses
Analyte MS%R
Cyanide 75-125
Total alkalinity (titration} 75-125
Total alkalinity (Automated) 75-125
Bromide (IC) 75-125
Chloride (IC) 75-125
Chloride (Automated) 75-125
Fluoride (ISE) 75-125
MBAS (colorimetric) 75-125
Nitrate (IC) 75-125
Nitrate (Automated) 75-125
Nitrite (IC) 75-125
Nitrite (Automated) 75-125
Nitrate/Nitrite (Automated) 75-125
Oil & grease 75-125
Total phenolics (Automated) 75-125
a-Phosphate (IC) 75-125
a-Phosphate (Automated) 75-125
Total phosphate (Automated)75-125
Sulfate (IC) 75-125
TKN 75-125
TRPH 75-125
LCS¾R
(Statistical}*
Water Soil
76-125
85-117
78-110
86-108
81-112
79-127
84-122
79-114
81-110
83-119
79-116
92-110
85-117
63-121
67-127
77-115
75-125
85-114
86-113
75-125
69-125
41-159
• Statistically derived acceptance limits will vary by individual laboratory operation.
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6.1
6.2
6.0 SAMPLING PROCEDURES
INTRODUCTION
Date: 12/22/95
Section 6.0
Revision 0. O 1
Page 1 of 9
Obtaining representative samples and maintaining their integrity are critical parts of any monitoring program. Analytical methods have been standardized but the results of analyses are only as good as the sampling and the sample preservation methods.
Defining the magnitude and the nature of an environmental problem requires collecting
representative samples for laboratory analysis and data evaluation. The careful collection
of samples is key to obtaining an accurate assessment of the site's environmental impact, and to developing the appropriate remedial solution. Defining in detail the numerous available sampling procedures and their associated quality elements applicable to
environmental testing is beyond the scope of this document. Quality elements required to
meet the DQOs for a given sampling event must be contained in a project specific
sampling plan or within an overall site work plan. The plans should present the best approved techniques currently available for sampling and sample preservation.
In sampling, the objective is to remove a small portion of an environment that is
representative of the entire body. Once the sample is taken, the constituents of the · sample must stay in the same condition as when collected. The length of time that these
constituents will remain stable is related to their character and the preservation method
used. Since preservation methods relate to the parameters to be analyzed, these
techniques are classified by parameter.
SAMPLING SERVICES.
Various Pace locations provide a variety of sampling services. A well-defined communication mechanism is critical to obtaining samples which are representative of site
conditions. Figure 6.1 lists minimum elements which must be established, communicated,
and followed during each phase of the sampling and analysis project. Listed below are the
types of sampling events for which Pace can provide services.
6.2.1 Ground Water Monitoring
Collection and analysis of grourid water samples from sanitary landfills, Superfund
sites, abandoned hazardous waste dumps and spill sites involves the use of an
extensive array of state-of-the-art sampling equipment with the ability to pre-pump
and sample wells of all sizes, to depths of more than 200 feet.
6.2.2 Waste Water Monitoring
Collection of samples for routine wastewater monitoring; special compliance
monitoring for metals, cyanide and total toxic organics (TTO); NPDES permit
application monitoring; and more, as required by local, state of federal agencies.
:\lqapreva\sect6.doc
; ,-
6.3
6.2.3 Hazardous Waste Sampling
Date: 12/22/95
Section 6.0
Revision 0.01
Page 2 of 9
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Pace can conduct an inventory, collect and analyze samples, and repackage and II properly label hazardous waste for shipment. U
6.2.4 Flow Monitoring
Monitoring flow in most types of discharges through installation of wiers or flumes
and also determine flow using fluormetric dye tracing methods.
6.2.5 Soil & Soil Gas Sampling
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Technicians statistically develop soil sampling programs to identify pollution I
problems. Typically this involves collecting soil samples for volatile and semi-
volatile organics, inorganics, hazardous waste constituents and most other I chemical parameters of concern. Also collecting and analyzing soil gas samples.
6.2.6 PCB Services
Collection of samples from transformers, electrical switches and capacitors to be -
tested for the presence of P~Bs. Handling of PCB-related spills includes the
collection and analysis of wipe, swab or soil samples.
6.2.7 Ambient Air Monitoring and Stack Emission Testing
Pace has experience in providing sampling as specified in the Toxic Organic
(TO method series) protocols for ambient air monitoring, along with NIOSH and
AIHA specified applications. FuH capability stack sampling and testing (e.g.,
VOST, impinger, etc.) is av_ailable for process optimization and emission
monitoring.
FIELD SUPPORT
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Pace provides shipping containers, custody documents, custody seals, sample bottles, I labels, chemical preservatives for water samples, "blue ice" packs to maintain thermal preservation, and trip and field blanks to support field sampling events. Tables 6.1, 6.2
and 6.3 list sample container types, preservatives and holding times. Certain Pace I locations can provide pick up and delivery services to their clients.
Upon receipt of the field samples at the laboratory, Pace ensures that sample bottles I are maintained according to preservation requirements and that sample storage
conditions do not contribute to the presence of test analytes in the samples.
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6.4
6.5
6.6
Pace Shipping Containers
Date: 12/22/95
Section 6.0
Revision 0.01
Page 3 of 9
Pace typically uses commercial coolers for the transport of environmental samples from the field to the laboratory. Chain-of-custody seals and forms, employed for each cooler packed at Pace ensure complete documentation and provide evidence of unbroken custody of the cooler contents. Coolers meet or exceed all protocol requirements (i.e., DOT, USEPA, ASTM) for shipping. Coolers are prepared at the laboratory to provide the client with all of the sample containers needed for the analyses required by a project.
PRESERVATION
Pace provides the required chemical preservatives for water samples and "blue ice" packs, for thermal preservation when the samples are shipped back to the lab. High quality, reagent grade chemical preservatives are used. The ice packs are supplied pre-frozen or at ambient temperatures based upon the client's needs. It is the responsibility of those collecting the samples to properly use these materials and ensure that proper preservation techniques are performed and preservative requirements are met.
Upon receipt of samples at the laboratory, the temperature of each cooler is measured. and recorded on the chain of custody documents. Similarly, the pH of bottles to which chemical preservative was added is measured (with the exception of sample collected for volatile organic compounds), and the check recorded. A disposable pipette is used to remove an aliquot of the sample for the pH check. When deviations from the required chemical or thermal preservation are noted, the project manager is notified, and clients may become involved in determining a course of action to follow.
Water samples for GC and GC/MS volatile aromatics determinations are monitored for pH just prior to analysis, at which time the pH of each individual sample bottle used is checked. The portion of sample used for the analy1ical determination is removed from the vial prior to checking the sample's pH. Sample pH measurements are recorded on laboratory chronicles as they are taken.
SAMPLE CONTAINERS
Pace provides precleaned sample containers in the shipping containers for sample collection. Used sample bottles are never used by the laboratory. Vendor prepared (certified contaminant-free) containers can be provided as projects necessitate.
SAMPLE RECEIPT SCHEDULE
Samples are normally delivered to the Pace facility during normal business hours within one day following field sampling unless different arrangements are made in advance with an authorized Pace representative. Shipping containers received at the laboratory
on business holidays, weekends or after normal work hours will be placed in the walk-in refrigerator and opened on the next regular business day unless prior arrangements are made in advance for that day's receipt and log-in.
:\lqapreva\sect6.doc
Client
Appro-.e safTl)ting
schedule. o-.ersee
project plan
~
Conm.micate safll)ling
requirerrents, rate of
sample de~-.ery, etc.
M:>nitoc corrm.inication
betv.een tab & fiek1
personnel, remlin Informed
on project rela~ issues
:\lqapreva\sect6.doc
Figure 6.1
Date: 12/22/95
Section 6.0
Revision 0.01
Page 4 of9
Pre-Sampling Communication
Pace Sampling Personnel or Client
Pace Laboratory Personnel Performing Sampling
I Estabish Available I Capacity & Resources
Sample Collection & Holding
Pre-cleaned san-ple bottles presen.ed,
labelled. packaged & sealed '°'
shiprreot to site. Bottle shipping
manifest form initiated and inluded
t
I Sclfl1)1e Bottle coolers I I Sarrples coDected I shipped to site I I presen.ed & packaged
+ I Chain of Custxty Initiated j
+
I Receipt In laboratory I I Shipment of satll)les I I to laboraby
+
J eon,,1ete Chain of Custody j
I E>camine sartl)le for condition I
t
Project Mgr. comrunicates I Estabish Available discrepancies on COC: broken I Capacity & Resources sa"l)te bottles, etc. '
I SarrpleStorage I t I Re\itew hok::ling times, I prioritize in sal11'.)le stream
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TABLE 6.1
NAME
Inorganic Tests:
Acidity
Alkalinity
Ammonia
Biochemical oxygen
demand
Bromide
Biochemical oxygen
demand, carbonaceous
Chemical oxygen demand
Chloride
Chlorine, total residual
Color
Cyanide, total amenable to
chlorination
Fluoride
Hardness
Hydrogen ion (pH)
Kjeldahl and organic
nitrogen
Metals:
Chromium VI
Mercury (SW846)
Mercury (CLP, 200 series)
Metals, except chromiumVI
and mercury
Nitrate
N itra te-n itrite
Nitrite
Oil and grease
Organic carbon
Orthophosphate
Phenols
Phosphorus ( elemental)
Phosphorus, total
Residue, total
Residue, filterable
Residue, nonfilterable
(TSS)
Residue, Settleable
Residue, volatile
Silica
:\lqapreva\sect6.doc
Date: 12/22/95
Section 6.0
Revision 0.01
Page 5 of 9
List of Containers, Preservatives and Holding Times for Inorganic and Organic
Analyses of Aqueous Samples:
CONTAINER' PRESERVATION" MAXIMUM HOLDING TIME"
Cool, 4°C P,G 14 days
P,G Cool. 4°C 14 days
P,G cool, 4°c, H,so, to pH<2 28 days
P,G Cool, 4°C 48 hours
P,G None Required 28 days
P,G . Cool, 4°C 28 days
P,G Cool. 4°C, H,so, to pH<2 28 days
P,G None Required 28 days
P,G None Required Analyze immediately
P,G Cool, 4°C 48 hours
P,G Cool, 4°C, NaOH to pH>12 14 days
0.6g ascorbic acid4
p None Required 28 days
P,G HNO3, to pH<2, H2SO, to 6 months
pH<2
P,G None Required Analyze immediately
P,G Cool, 4°C, H2SO, to pH<2 28 days
P,G Cool, 4°C 24 hours
P,G HNO3 to pH<2 38 days in glass
P,G HNO3 to pH<2
13 days in plastic
28 days
P,G HNO3 to pH<2 6 months
P,G Cool, 4°C 48 hours
P,G Cool, 4°c, H,so, to pH<2 28 days
P,G Cool, 4°C 48 hours
G Cool, 4°C, H,so, to pH<2 28 days
P,G Cool, 4°c, H2SO, to pH<2 28 days
P,G Filter immediately, 48 hours
Cool, 4°C
G only Cool, 4°C, H2SO4 to pH<2 28 days
G Cool, 4°C 48 hours
P,G Cool, 4°C, H2SO, to pH<2 28 days
P,G Cool, 4°C 7 days
P,G Cool, 4°C 7 days
P.G Cool, 4°c 7 days
P,G Cool, 4°C 48 hours
P,G Cool, 4°C 7 days p Cool, 4°C 28 days
Date: 12/22/95
Section 6.0
Revision 0.01
Page 6 of 9
TABLE 6.1 (cont.) List of Containers, Preservatives and Holding Times for Inorganic and
Organic Analyses of Aqueous Samples·
NAME CONTAINER' PRESERVATION' MAXIMUM HOLDING TIME' /norganics Continued:
Specific conductance P,G Cool, 4°C 28 days Sulfate P,G Cool, 4°C 28 days Sulfide P,G Cool, 4°C, add zinc 7 days
acetate & sodium
hydroxide to pH>9
Sulfite P,G None Required Analyze immediately Surfactants P,G Cool. 4°C 48 hours Turbidity P,G Cool, 4°C 48 hours
Organic Tests:
Oil and Grease G Cool, 4°C, HCI or H2SO4 28 days
to pH<2
Organic carbon, Total P,G Cool, 4°C. HCI or H,so, 28 days (TOC) to pH<2
Purgeable Halocarbons G,Teflon-lined Cool, 4°C. 0.008% 14 days
septum Na,s,o,'
Purgeable Aromatic G,Teflon-lined Cool, 4°C, 0.008% 14 days Hydrocarbons septum Na S O 4 HCl5'6 2 2 J I Acrolein and acrylonitrile G,Teflon-lined Cool, 4°C, 0.008% 14 days
septum Na2S203 • .A~just pH to 4-5
Phenols G, Teflon-lined cap Cool, 4 C, 0.008% 7 days until extraction, 40 days after
Na,s,o, • extraction
Benzidines G,Teflon-lined cap Cool, 4°C. 0.008% 7 days until extraction, 40 days after
Na,s,oi' extraction
Phthalate esters G,Teflon-lined cap Cool,4 7 days until extraction, 40 days after
extraction
Nitrosamines G,Teflon-lined cap Cool, 4°C, store in dark, 7 days until extraction, 40 days after
0.008% Naas,o,' extraction
PCBs G,Teflon-lined cap Cool, 4 C 7 days until extraction, 40 days after
extraction
Nitroaromatics and cyclic G, Teflon-lined cap Cool, 4°C, store in dark, 7 days until extraction, 40 days after ketones 0.008% Na,s,o,' extraction
Poly nuclear aromatic G,Teflon-lined cap Cool, 4°C, 0.008% 7 days until extraction, 40 days after hydrocarbons Nao'.s20,' extraction
Haloethers G,Teflon-lined cap Cool, 4 C, 0.008% 7 days until extraction, 40 days after . . extraction Na,s,o,
Chlorinated Hydrocarbons_ G,Teflon-lined cap Cool, 4°C, HCI or H2SO4 7 days until extraction, 40 days after
extraction
Dioxins and Furans G,Teflon-lined cap Cool, 4°C, 0.008% 7 days until extraction, 40 days after
Na,s,o,' extraction
Total organic halides (TOX) G, Teflon-lined cap Cool, 4°C, HCI or H,so, 28 days
Pesticides G,Teflon-lined cap
to pH <2
Cool, 4°C 7 days until extraction, 40 days after
pH 5-9 extraction
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Table Footnotes:
1 Polyethylene (P) or glass (G) 2 Sample preservation should be performed immediately upon sample collection. 3 Holding times are based upon from time of sample collection.
' Should only be used in the presence of residual chlorine. 5 Free chlorine must be removed prior to addition of HCI by the appropriate addition of No2S20 3 6 Sample receiving no pH adjustment must be analyzed within seven days of sampling.
:\lqapreva\sect6.doc
Date: 12/22/95
Section 6.0
Revision 0.01
Page 7 of 9
Table 6.2
NAME
Semivolatile
Organics/Organoch/orine
Pesticides/PCBs and
Herbicides
Concentrated waste
samples
Liquid samples, no residual
Chlorine present
Residual Chloride, present
Soil/sediments and sludges
Volatile Organics
Concentrated waste
samples
Liquid samples. no residual
Chlorine present
Residual Chlorine, present
Acrolein & Acrylonitrile
Soil/sediments and sludges
Date: 12/22/95
Section 6.0
Revision 0.01
Page 8 of9
Required Containers, Preservation Techniques, and Holding Times for Aqueous, Non-Aqueous, Soil or Solid Matrices (as specified in SW-846):
CONTAINER PRESERVATION MAXIMUM HOLDING TIME
8 oz. wide mouth None 14 days until extraction, 40 days glass w/Tefion liner after extraction
1 gal. or 2 1/2 gal. Cool, 4°C Samples must be extracted within 7 amber glass w/Tefion days & extracts analyzed within 40 liner days
1 gal. or 2 1/2 gal. Add 3ml 10% sodium Samples must be extracted with in 7 amber glass w/T efion thiosulfate days & extracts analyzed within 40 liner days
8 oz. wide mouth Cool, 4°C 14 days until extraction, extracts
glass w/Tefionlliner analyzed within 40 days:
8 oz. wide mouth None 14 days
glass w/Tefionlliner
3x40 ml vials Cool, 4°C2 14 days
w/Tefion lined septum
caps
3x40 ml vials Collect sample in a 4 oz. 14 days
w/Tefion lined septum soil VOA container which
caps has been pre-preserved
w/4 drops of 10% sodium
thiosulfate. Gently mix
sample & transfer to a
40ml VOA vial2. Cool to
4°C
3x40 ml vials Adjust to pH 4-5, Cool to 14 days
w/Tefion lined septum 4°c
caps
Cool to 4°C 4 oz. (120ml), wide 14 days
mouth glass w/Teflon
liner or wide mouth
glass container
sealed w/a septum
' Holdrng trmes are based upon from trme of sample collectron. 2 Adjust pH<2 w/H2SO4, HCI or solid NaHSO4
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Table 6.3
TEST
TO1
TO2
VOST
TO4
TO1O
TO11
TO13
Date: 12/22/95
Section 6.0
Revision 0.01
Page 9 of9
Required Containers, Preservation, and Technical Hold Times for Air Methods:
MEDIA PRESERVATION MAXIMUM HOLDING TIME '
Tenaxtubes Freezer -20°C 14 days
Carbo Sieve Cool to 4°C 14 days
Tenaz/Tenaz-Cool to 4°C 14 days
charcoal
Puf 3" long, 60mm Freezer -10°C or below Extracted 7 days after collection
diameter
Puf 10cm long, 20mm Cool to 4°C Extracted 7 days after collection diameter
Absorbent cartridge Cool to 4°C 30 days Puf XAD/XAD Extracted 7 days after collection Holding times are based upon from time of sample collection.
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7.1
7.2
7.0 SAMPLE CUSTODY
SAMPLE RECEIPT
Date: 12/22/95
Section 7.0
Revision 0.01
Page 1 of 19
Sample shipments are received at the sample receiving area. Sample custodians verify the number of shipping containers received against the numbers listed on the shipping manifesVchain-of-custody. Any damage to the shipping containers or other discrepancy observed is noted on the chain-of-custody before signing it or on the sample receiving non-conformance report. A copy is filed for future reference.
When practical, the external chain-of-custody must be signed by the carrier for relinquishment of samples and signed by sample custodian personnel for sample receipt. The actual chain-of-custody may be supplied by Pace (Figure 7.1 ), or may be the client's own form. The chain-of-custody remains in the project file at all times.
CHAIN OF CUSTODY
Chain-of-Custody encompasses three major elements: field sampling, laboratory analysis and final data file. A Chain-of-Custody (COC) document may be the means in some types of legal proceedings by which evidence of custody of samples from time of receipt to completion of analysis is proven in the courts. Pace has implemented standard operating procedures to ensure that sample custody objectives of traceability and responsibility are achieved for every project. This section covers quality related activities from the receipt of samples at the laboratory through the issuance of final analytical data and the storage of data in its final data file.
The National Enforcement Investigations Center (NEIC) of EPA defines evidence of custody in the following manner:
1.
2.
3.
4.
It is in your actual possession, or
It is in your view, after being in your physical possession, or
It was in your possession and then you locked or sealed it up to prevent tampering, or
It is in a secure area.
Samples may be physical evidence and should be handled according to certain procedural safeguards. Field personnel or Client representatives complete a Chain-of-Custody Form for all samples. Samples are received by the laboratory accompanied by these forms.
The sampler should provide the following information:
• . Client project name
Project location
• Field sample number/identification
Date and time sampled
Sample type
:\lqapreva\sect7 .doc
7.3
Preservative
Analysis requested
Sampler signature
Signature of person relinquishing samples
Date and time relinquished
Sampler remarks
Custody Seal Number (if applicable)
Date: 12/22/95
Section 7.0
Revision 0.01
Page 2 of 19
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The record is filled out completely and legibly. Errors are corrected by drawing a single line I
through and initialing and dating the error. The correct information is then recorded with
indelible ink. All transfers of samples except to and from commercial couriers must be II
recorded on the Chain-of-Custody via the "relinquished" and "received by" sections. All II
information except signatures may be printed.
SAMPLE VERIFICATION
7.3.1 Upon arrival of a sample shipment, sample control personnel perform sample
inspection. Pace's Sample I.D. and Condition Sheet or equivalent (Figure 7.2)
serves as a check-off list of procedures to follow and as documentation of the •
following:
1. Presence/absence of custody seals or tapes of the shipping containers
and the condition of the seals (i.e., intact, broken).
2. Presence/absence of chain-of-custody; (if present, is it complete?)
3.
4.
5.
Presence/absence of sample tags; (if present, an~ they removable?)
Agreement/non-agreement between the sample tags, chain-of-custody,
and any client documentation.
Condition of the samples when received, including:
• Sample temperature
• Intact, broken/leaking
• Headspace in VOA vials
• Sample holding time
• Sample pH when required
If discrepancies are found, the Pace project manager is contacted immediately
(verbally and by using a Discrepancy Report Form or equivalent (Figure 7.3). If
the project manager is not available, the QAO is contacted for further directions.
A copy of the Discrepancy Report Form is attached to the project data package.
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7.4
Date: 12/22/95
Section 7.0
Revision 0.01
Page 3 of 19
SAMPLE LOG-IN
7.4.1 General Policies
a.
b.
C.
d.
e:
f.
Upon completing sample receipUcustody procedures, all sample and
analysis data must be complete and documented on the chain of custody
or accompanying forms for input into the Laboratory Information
Management System (LIMS).
Sample.and analysis data must include:
1.
2.
3.
4.
5.
6.
7.
Client name and contact
Client number
Pace project number
Pace project manager
Sample descriptions
Due date
List of analyses requested
Sample and requested analyses data are input into the LIMS.
All samples received are logged into the LIMS on the day of receipt.
A Sample and Analysis Data Entry Form (SADEF) or equivalent (Figure
7.5) is generated immediately by the LIMS.
Distribution of SADEE:
To the Pace Project Manager with a photocopy of the chain-of-custody
form. (Include a copy of the Discrepancy Report if applicable).
To the QC project file with the original chain of custody.
Photocopy to the Organic or Inorganic Department Manager as it applies
for RUSH samples.
To the client.
SADEF is to be reviewed against the chain of custody.
Sample containers are labeled with the corresponding sample number and
the stamped date of receipt.
g. Samples are ready for storage.
:\lqapreva\seci7 .doc
7.5
7.6
7.7
Date: 12/22/95
Section 7.0
Revision 0.01
Page 4 of 19
WHEN SAMPLES ARE RECEIVED WITH NO PAPERWORK
7.5.1. If delivered by a client: Client is asked if previous arrangements were made for
analysis (and with whom). The client completes a chain of custody and/or request
for analysis, relinquishes samples to sample custodian personnel, and is given a
copy of the COC.
7.5.2. If received by courier or shipping the following ordered steps are taken:
1.
2.
3.
4.
5.
6.
Routine Client File is checked
Anticipate Sample Alert File is checked
Sampling Kit Request File is checked
Pace key client contact is consulted
QC department manager is consulted to determine the designated Pace
project manager
Information is requested from the Pace project manager
7.5.3. If analysis information cannot be determined on the day of sample receipt, sample
data entry personnel proceed to assign sample numbers and put samples on hold. ·
Follow-up with project manager occurs until the analyses are determined and
samples can be properly logged in.
RESPONSIBILITIES FOR SAMPLE LOG IN
7.6.1. Sample Custodian
•
•
Has the primary responsibility of ensuring that sample information is input
into the LIMS as described in the SOP.
Has the responsibility to make recommendations to the QC manager for
revising the SOP.
7.6.2. Sample Management Officer
• Has the overall responsibility for ensuring that this procedure is
implemented for all samples received into the laboratory.
• Has overall responsibility for ensuring that samples are logged in
correctly (given that appropriate information has been supplied).
SAMPLE STORAGE
7.7.1. General Procedures
Samples are stored immediately upon receipt to prevent sample
degradation.
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Date: 12/22/95
Section 7.0
Revision 0.01
Page 5 of 19
7.7.2. Refrigerated Storage Area Maintenanc_e
All refrigerated storage areas are maintained at 4°C (+/-2°C). The temperature
is monitored and recorded each work day (certain programs may require more
frequent monitoring; e.g., twice daily). If the temperature fails outside the limits
of 2°-6°C, corrective action is to be taken as follows and appropriately
documented.
1. Temperature is monitored at 60 minute intervals with the
refrigerator door closed.
2. QAO is notified if the problem persists longer than one hour.
3. Samples are relocated to a proper storage environment if
temperature cannot be maintained after corrective actions are
implemented.
7.7.3. Routine Sample Storage
1. General Samples
Samples within each project are stored in sample number order. Waters
and soils are generally stored on labeled separate shelves and in
separate refrigerated units.
7. 7.4. Specific Procedures
1. Volatiles
2.
3.
:\lqapreva\sect7 .doc
Samples within a project are stored in numerical order in vial containers.
The holders are then stored where space permits in one of the
designated volatile organic refrigerated storage areas.
Semi-Volatiles
Samples within a project are stored in numerical order in a designated,
refrigerated storage area.
Hazardous Materials
Pure product or potentially heavily contaminated samples are tagged as
"hazardous" and stored within a secured area, separate from other
samples. This area is used only for hazardous samples and is labeled
per Occupational Health and Safety Administration (OHSA)
requirements.
7.8
4.
Date: 12/22/95
Section 7.0
Revision 0.01
Page 6 of 19
Special Projects
• Volatiles
Samples within a project are stored in sample number order in vial
containers. The holders are then stored as space permits in the
Special Project Volatiles (VOA) refrigerated storage area.
7.7.5. Responsibilities for Sample Storage
1. Sample Management Officer has direct responsibility for ensuring that the
Standard Operating Procedure (SOP) is followed, samples are stored
properly upon receipt, and refrigerated storage area temperatures are
maintained.
2. Sample custodians are responsible for storing all samples upon receipt into
the appropriate storage area, maintaining high level security for those
samples under custody, and for keeping a current custody sample inventory.
3. Sample management personnel have the responsibility of daily sample
storage area maintenance, disposal of old samples, and providing space for
incoming samples in routine storage areas.
4. Assigned individuals are responsible for maintaining and documenting: (a)
refrigerated storage area temperatures, and (b) corrective actions.
SAMPLE/DATA ACCESS AND INTERNAL CHAIN-OF-CUSTODY
7.8.1. General Policies and Procedures
Pace has implemented standard operating procedures to assure the integrity of
samples and data so that they are not degraded or disclosed to unauthorized
personnel. In order to ensure that this policy is maintained, the laboratory
facilities are operated under controlled access. Only employees are allowed into
the laboratory facilities; visitors must register at the front desk.
-
Samples are removed from their proper location by designated personnel and
returned to the storage area immediately after the required sample quantity has
been taken. This procedure minimizes unnecessary time spent searching for
samples and helps prevent matrix degradation from prolonged exposure to room
temperature. After the final report is sent and clients are allowed adequate time
to review the results, the samples are properly discarded or returned to the
client.
Upon client request, additional and more rigorous chain-of-custody protocols for
samples and data can be implemented. For samples involving a high degree of
confidentiality or potential litigation, Pace has developed extensive sample and
data handling protocols to ensure the scientific and legal defensibility of the
:\lqapreva\.sect7 .doc
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7.9
Date: 12/22/95
Section 7.0
Revision 0.01
Page 7 of 19
report submitted. These protocols include those specified by the USEPA
Contract Laboratory Program.
Analysts and technicians follow strict internal chain-of-custody procedures to further ensure the validity of all data. All samples are signed out in a sample custody log book when they are removed for analysis. The sample ID, date, time, analyst, and lab of analysis is recorded in the sample custody log (Figure
7.4) or equivalent. Samples are signed back in noting date, time, and storage location, upon return.
7.8.2. Responsibilities for SOP Compliance
1. The QAO has the overall responsibility for ensuring that the SOP is implemented and followed.
2.
3.
Sample custodian personnel have the responsibility for ensuring that the SOP is properly followed, and to notify the QAO of problems.
All employees checking out samples are required to follow procedures.
SUBCONTRACTING ANALYTICAL SERVICES
Every effort is made to perform chemical analyses for Pace clients within a Pace laboratory. There are, however, instances where subcontracting of analytical services is necessary. Should subcontracting be necessary, samples are generally placed at other labs within the Pace integrated system of laboratories if at all possible. Currently, the following analyses are processed by specialty laboratories within Pace:
• Air Analyses
• Bioassay
• Explosives
When subcontracting becomes necessary, a preliminary verbal communication with an appropriate laboratory is undertaken. Work performed under specific protocols may involve special consideration, for instance, work involving NFESC samples may be subcontracted only to NFESC approved laboratories. The contact and preliminary arrangements and terms of agreement are made between the Pace Project Manager and the appropriate subcontract laboratory personnel (i.e., Laboratory Manager, customer services contact, or the appropriate laboratory section manager). The specific terms of the subcontract laboratory agreement should include (when applicable):
• Method (EPA or otherwise) of analysis
• Number and type of samples expected
• Project specific QNQC requirements
• Deliverables required
• Applicable laboratory certification status
• Price per analysis
• Tum around time requirements
:\lqapreva\sect7 .doc
Date: 12/22/95
Section 7.0
Revision 0.01
Page 8 of 19
Chain-of-Custody forms must be generated for samples which require subcontracting to
other laboratories. The sample management personnel repackage the samples for
shipment, create a transfer chain-of-custody form and record the following information:
• Pace Laboratory Number
• Matrix
• Requested analysis
• Special instructions (quick tum around, required detection or reporting limits, ·
unusual information known about the samples or analytical procedure).
• Signature in "Relinquished By"
All subcontracted sample data reports are sent to the Pace Project Manager. The Project
Manager sends the report to the appropriate Pace laboratory manager for review.
Any Pace work sent to other labs within the Pace network is handled as subcontracted
work. All of the conditions and considerations noted in Section 7 .10 and 7 .11 apply.
7.10 SAMPLE DISPOSAL
After completion of sample analysis and submission of the analytical report, unused
portions of samples are retained by the laboratory for a minimum of 2 weeks. After 2
weeks, samples will be disposed of according to the nature of the samples. The
Hazardous Waste Manager receives a copy of the data report and uses that information
to select the appropriate waste stream for the samples. The samples are considered
hazardous waste, then they will be disposed of by state and federally licensed hazardous
waste disposal finns.
Upon disposal of samples, a computer spreadsheet is maintained by the Hazardous
Waste Manager listing the sample number, inherent waste stream and date disposed.
This data file is updated on a weekly basis and is kept on file by the Hazardous Waste
Manager and Sample Management.
7.11 EXCESS SAMPLE DISPOSITION
Samples not consumed during the analyses are returned to the client or disposed of
by Pace. It is the project manager's responsibility to ensure that proper disposal has taken
place. If the sample is detennined to be non-hazardous by the project manager, it may
then be disposed of by Pace via a non-manifested process.
7.1.1. Notification of Sample Return
:\lqapreva\sect7 .doc
The project manager and client receive written notification at the time of project
initiation in the following manner:
1. The project proposal states the following paragraph in its Conditions and
Tenns Statement:
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2.
3.
Date: 12/22/95
Section 7.0
Revision 0.01
Page 9 of 19
"Pace Analytical Services, lnc.'s Standard Operating Procedure is to return
all samples of hazardous materials to the client at project completion, and
Pace Analytical Services, Inc. reserves the right to return or dispose of all
samples at its discretion unless contractually agreed otheiwise."
The Sample and Analysis Data Entry Form (or equivalent) states the
following:
"Pace Analytical Services, Inc. reserves the right to return all samples at
our discretion."
This form is printed by the LIMS at sample check-in.
The Sample and Analysis Data Entry Form cover letter contains the
following paragraph:
1. "Pace Analytical Services, lnc.'s Standard Operating Procedure is
to return all samples of hazardous materials or wastes to the client
at project completion. Pace Analytical Services, Inc. reserves the ·
right to return or dispose of all samples at our discretion" (Figure
7.5). This is a pre-printed cover letter that accompanies the
Sample and Analysis Data Entry Form.
4. The Sample and Analysis Data Entry Form and cover letter (or equivalents)
are generally sent to the client by the project manager depending upon
project requirements.
7.11.2 Sample Return and Disposal
If samples are to be returned to the client or held longer than 60 days, a sample
disposition form is generated. Otheiwise, samples are disposed of a minimum of
two weeks after project completion. ·
a. The example Sample Disposition Form (Figure 7.6) contains the following
information:
1.
2.
3.
4.
5.
Client name, address, and contact
Pace project number
Client project identification number
Pace sample identification number
Pace project manager name
This form may vary by location
7.11.3 Procedure for Use of the Sample Disposition /SD} Form /or equivalent)
:\lqapreva\sect7 .doc
1.
2.
:\lqapreva\sect7 .doc
Date: 12/22/95
Section 7.0
Revision 0.01
Page 10 of 19
The project manager separates the sample disposition form from the report
package, signs the form, and routes it to the sample custodian. If the
project requires, the hazardous waste manager may hold the form for a
required amount of time before return or disposal.
It is important that this form be used and not discarded. It is part of the
internal Chain of Custody and is filed with the project report
The hazardous waste manager or designee will use action codes such as:
1 = Return to client
C = Clean
2 = In house disposal
D = Dirty
As a general rule, soil samples will be returned and water samples will be
disposed of in-house. Water samples which are highly contaminated will
be returned. If a sample has an extremely high level of contamination, the
contaminant will be noted by the project manager on the SD form.
For In-House Sample Disposal
All preserved -Non-hazardous-Neutralize/sink
Hazardous-Toxic waste
Unpreserved water-Non-hazardous-Sink
Hazardous-Toxic waste
Soil/Sludge-Non-hazardous-Refuse Disposal
Hazardous-Toxic waste
All VOA's-Non-hazardous-Neutralize/sink
Hazardous-Toxic waste
AH Extracted samples
CAM Extracts -Non-hazardous -Neutralize/sink
Hazardous -Acid metals waste
Other Extracts -Hazardous waste
Liquid/Unknown Miscellaneous -Project manager specify
Subsequent to receipt of the Sample Disposition Form by the sample
custodian, samples will be removed from storage using the information
provided on the form.
If the Sample Disposition Form indicates "disposed," the Sample Custodian
will remove samples from storage and place them at a sample disposal
station for proper disposal. The process of disposal is performed by the
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3.
Date: 12/22/95
Section 7.0
Revision 0.01
Page 11 of 19
sample custodian or appropriate laboratory staff. The Sample Disposition
Form is signed and dated by the sample custodian then routed to the
project manager for filing with other project information.
If samples are to be returned, the Sample Custodian removes them from
storage, initials and dates the Sample Disposition Form. The samples,
Sample Disposition Form, and a copy of the client's chain of custody are
then delivered to the shipping clerk by the sample custodian for return to
the client.
Upon receipt of the samples and Sample Disposition Form, the shipping
clerk signs and dates the form.
The Sample Disposition Form is copied and the original form with the
samples is returned to the client, along with a copy of the client's chain of
custody. A copy of the Sample Disposition Form and the original chain of
custody is routed to the file clerk for filing with other project information (QC
file).
The shipping clerk labels the box with an appropriate hazard label and
ships the samples back to the client.
4. Sample Disposition Forms are filed in project files.
7.11.4 Hazardous Material/Waste Sample Disposition Option
:\lqapreva\sect7 .doc
The preferred method for disposition of hazardous samples is to return the excess ·
sample to the client. It may not be feasible to return samples in all cases or the
client may require Pace to dispose of excess samples. Pace will dispose of
excess samples when required and will charge a disposal fee to recover costs for
management and disposal.
Procedure for Disposal Option for Excess Hazardous Material/Waste Samples:
1. When analyses are complete, the project manager indicates disposal as
the option on the Sample Disposition Form and completes and attaches
Hazardous Sample Disposal Option Form (Figure 7.7) or equivalent. An
entry must be made in all fields of this form as it will determine the basis for
lab packing and disposal.
2. The project manager routes the Disposal Option Form to sample check in.
3.
4.
The project manager is responsible for billing the client for disposal.
The sample custodian is responsible for maintaining a file of Disposal
Option Forms for all samples awaiting disposal. Hazardous material/waste
samples are stored in a safe manner and segregated by compatibility
groups as indicated by the hazardous waste disposar SOP.
5.
:\lqapreva\sect7 .doc
Date: 12/22/95
Section 7.0
Revision 0.01
Page12of19
The hazardous waste manager is responsible for reviewing accumulated
samples awaiting disposal and initiating the disposal process when
warranted. The Field Services, Inorganic, Organic, and Environmental
Services Departments cooperate and participate in the disposal process.
(For compatibility and compositing, see the Hazardous Waste Disposal
SOP.)
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--
Clienc
Address
Phone
Sampled By {PAINT):
Samplo:tf Sign.ah.lie
2
3
4
5
6
7
8
Additional Commonls
--- --
0
Oa11 Sampled w > ~ w ~ w ~ ~ z ~
-
Ao To:
P.O., I BIiiing Relerence
P,ojoct Name I No.
0 cS i" < z 0 z >
- -
I!!!!!!!-I!!!!!!! I!!!!!!!
3?3R75
CHAIN-OF-CUSTODY RECORD
Analytical Request
P.ac.o C~en1 No.
PiaCI ProjKt Man.age,
REMARKS
SEE .REVERSE SIDE FOR INSTRUCTIONS
I!!!!!!
-u .,
n
(1)
)> :, .,
-<" ~-n .,
en
(1) < ff (1)
Ill 'TI
-(0· ~ :, C: .,
p ~ 3
(") .... ""£. :::c )> :.... (1)
z
6 .,,
h
C en --t 0
0 -< .,,
0 ;u
l!: -u ;o (/) 0
Ill (ti ct> ru t0<n~
CD c,;· 5· ~ 5' :, _.. w ::J .....,~
0 a· N :: a a t::!
U) _.. ~
Client: _______ _
Project No.: ______ _
Date Received: ____ _
FIGURE 7.2
SAMPLE I.D. AND CONDITION FORM
(Format may vary by location)
Date: 12/22/95
Section 7.0
Revision 0.01
Page 14 of 19
SAMPLE CONDITION UPON RECEIPT CHECKLIST
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Complete checklist (A) during sample receipt. If any items are marked "NO," complete section (B) of this
form. Otherwise, go to record samples. I
(A)
(B)
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
Are there custody seals or tapes on the shipping container?
Are custody seals on the shipping container intact?
Is there a completed Chain-Of-Custody (C-0-C)?
Do the numbers of samples received and the sample
matrices agree with C-O-C?
Are there tags attached to each sample?
Are sample tags, sample containers and C-O-C all
in agreement?
Is the C-O-C complete with requested analyses?
Are the samples preserved correctly?
Is there enough sample to do all analyses?
Do the samples have the proper temperature?
Are the sample containers intact (e.g., not broken, leaking)?
Are VOA vials head-space free?
Are all samples within the holding times for requested analyses? _
Is pH recorded for non-VOA's?
YES l'1.Q
Explain "NO" item here:. ______________________ _
Send a copy of this form to Project Manager with Discrepancy Report
Form. Copy of both forms remain in the QC file.
Custodian Signature: ___________ _
:\lqapreva\sect7 .doc
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FIGURE 7.3
Pace Analytical Services, Inc.
DISCREPANCY REPORT FORM
(Format may vary by location)
Urgency Level: 1 (_) Requires immediate attention
2(_) Requires attention today
3(_) Requires attention this week
Date: 12/22/95
Section 7.0
Revision 0.01
Page 15 of 19
Initiator _______________ Client: ___________ _
Date: _______ _
Project# ______ _
Sample(s) # _____________ _
Discrepancy (if more space needed, use the back of this form): ___________ _
To QC Manager. Date: _________________ _
Client Notified? YES ( ) NO ( ) Date & Time: _______________ _
Project Manager Notified? YES ( ) NO ( ) Date & Time:. _____________ _
QC Response:. ____________________________ _
Project Manager Response: _______________________ _
Cause and Resolution (proposed or carried out): Completed by:. ___________ _
Manage~s Initials:
PM Signature: ________ Date:. _________________ _
QC Signature: ________ Date:. _________________ _
cc: Project File
:\lqapreva\se_ct7 .doc
Project
Date Created
Initials
RELEASED
SDG CLOSED
A
B
C
D
E
SAMPLES OUT
Initials
Datemme
:\lqapreva\sect7 .doc
F
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FIGURE 7.4
Pace Analytical Services, Inc.
Internal Chain of Custody
(Format may vary by location)
Date: 12/22/95
Section 7.0
Revision 0.01
Page 16 of 19
Fractions Available
Potentially Radioactive? r Yes r No
SAMPLES
K p u
L Q V
M R w
N s X
0 T y
Which Where is it IN Any Totally Comments
Fraction Going? Initials Consumed?
Datemme
I Page:
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May 24, 1995
Dear Valued Client:
FIGURE 7.5
Pace Client Letter
SAMPLE
Date: 12/22/95
Section 7.0
Revision 0. O 1
Page 17 of 19
A new policy has been implemented in the Sample Receiving Department of Pace Analytical
Services, Inc. We hope that this policy will be helpful to you.
Upon acceptance of samples into the laboratory, the Sample Custodian completes a Sample and
Analysis Data Entry Form. This form is designed to accommodate a short description of the
samples received (sample name and/or sample reference), the type of container, and a list of the
analyses requested to be performed on each sample. A copy of this form will be sent to the
Client.
Enclosed is a copy of the Sample and Analysis Data Entry Fonm relevant to the samples we
recently received from you. Please compare the information on the fonm to assure that it is
consistent with your request. If there is any inconsistency or if you have any questions on your
project, please call the Pace Contact indicated on the Sample and Analysis Data Entry Form. The
Pace Contact has primary responsibility for monitoring the progress of your project through the
laboratory.
It is also part .of Pace Analy1ical Services, lnc.'s Standard Operating Procedure to return all
samples pertaining to the infonmation attached that are hazardous materials or hazardous wastes
to the client at project completion. Pace Analy1ical Services, Inc. reserves the right to return or
dispose of all samples at our discretion.
We have implemented this procedure to better serve our clients, and would appreciate any
comments you may have.
Sincerely,
:\lqapreva\sect7 .doc
Date removed: ----Initials: ______ _
Date shipped: ___ _
Initials: ______ _
FIGURE 7.6
SAMPLE DISPOSITION FORM
(Format may vary by location)
RE: Client Project ID: ______________ _
Pace Project No.: _______________ _
Sample ID
Dear
Date: 12/22/95
Section 7.0
Revision 0.01
Page 18 of 19
All requested analyses of the samples for the above referenced project have been completed.
Enclosed are the remaining portions of the samples which are being returned to you for final
disposition.
If you have any questions, please call me.
Sincerely,
Project Manager
:\lqapreva\sect7 .doc
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Pace Project #
Project Manager
Pull Sample Date
Sample# Matrix
Remarks: 1 = Return to Client
2 = In House Disposal
FIGURE 7.7
HAZARDOUS SAMPLE
DISPOSAL OPTION FORM
(Format may vary by location)
Location Disposal Method
C = Clean
D = Dirty
Removed from· Refrigerator (initial/date)
Date: 12/22/95
Section 7.0
Revision 0.01
Page 19 of 19
Charge
Returned to Client (initial/date) ________________ _
Disposed of Samples (initial/date _______________ _
:\lqapreva\sed7.doc
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Date: 12/22/95
Section 8.0
Revision 0.01
Page 1 of 9
8.0 CALIBRATION PROCEDURES AND FREQUENCY
All instruments and equipment used in the laboratory must follow a well defined calibration routine. Calibration may be accomplished by laboratory personnel using certified standard reference materials traceable to the National Institute of Standards and Technology (NIST) or EPA certified materials or by external· standardizing bodies or commercial standard manufacturers. The
discussion presented here is general in nature because the requirements for calibration are instrument (or equipment) and method specific. Details of calibrations can be found in Pace Standard Operating Procedures, analytical methods, and instrument operations manuals. In
addition to the summary calibration information pertaining to general analysis categories
contained in the following subsections, Tables 8.1 and 8.2 list detailed calibration information for representative methods and applications most frequently performed at Pace.
8.1 STANDARDS AND TRACEABILITY
Analytical standards are prepared from pure compounds or are purchased as neat chemicals or diluted standard solutions from reputable vendors. They are used to prepare·
serial dilutions from which calibration and spiking standards are prepared. Each laboratory
section is responsible for the preparation, storage and disposal of its standards. The
preparation information is recorded into section specific Standards Notebooks in order to document traceability of prepared standards to their source material(s).
Each standard is given an internal identification number. The preparation of all stock
standards shall be documented in a Standards Notebook which is used to record the date
of preparation, analyst's initials, the source of the reference material, standard
components, amounts used, final volume, final concentration(s), solvent used, expiration
date of prepared standard, and the serial reference number of that stock solution. All standards shall be labeled with the standard serial reference number and expiration date
(small glass ampules), and if space permits, with the name, concentration, date of
preparation and initials of preparer. All diluted working standards not consumed during an analytical session shall be labeled fully, including the serial reference number of any stock standard used in its preparation.
If no expiration date has been assigned by the manufacturer, then an expiration date of one year from the date of preparation ( or the date first opened in the case of sealed ampules) is reported unless degradation prior to this date is observed. To help determine
if a standard has degraded, one must note inconsistencies. For instance, very poor
recoveries from newly prepared quality control spikes or abnormally low instrument
response to a specific standard are indications of possible standard degradation.
However, for some standards, degradation is more easily noted. For instance, DDT breaks down to form DOD and ODE. Here one can visually note, on a chromatogram, the degradation of DDT by the increased concentrations of ODD and ODE. If degradation is
observed before the default expiration date, it should be noted in the Standard Notebook
for that standard and the standard removed from service.
:\lqapreva\sect8.doc
8.2
Date: 12/22/95
Section 8.0
Revision 0.01
Page 2 of 9
Before any set of standards can be utilized in a calibration curve they must be verified
either externally by the standard supplier or internally by a secondary source process:
•
•
Analysis of qualified QC Check Sample (e.g., A2LA approved), or
Analysis of an independently prepared check standard prepared either from a
. different manufactured lot for the same vendor supplying the calibration standard
or from a second supplier.
GENERAL CALIBRATION PROCEDURES
Calibration standards for each parameter are chosen to bracket the expected
concentrations of those parameters in the sample and to operate within the linear response range of the instrument. Samples that fall outside the calibration range are diluted until bracketed by the calibration standards. A low level standard is routinely analyzed to verify the reporting limit. Calibration standards are prepared typically at a
minimum of three concentration levels, usually chosen at two to five times, five to ten
times, and up to twenty times the estimated method detection limit plus a calibration blank,
with the exception of most organic analyses which do not require a calibration blank. Either an internal standard or external standard quantification technique can be utilized.
The reporting limit is verified by analysis of a standard at the reporting limit.
Calibration standards are prepared from materials of the highest available purity. To establish instrument calibration, working standards are prepared from more concentrated
working stock solutions. All organic standards are refrigerated or frozen. Inorganic
standards are refrigerated as necessary. Standard preparation information is recorded
within each laboratory section in designated Standards Notebook.
Instrumental responses to calibration standards for each parameter are subjected to an
appropriate statistical test of fitness (least squares linear regression, quadratic equation, or
relative standard deviation of response factors) or as required by the method or QAPP. The calibration must reflect an acceptable correlation of data points or linearity to be acceptable. Point-to-point curve fitting shall not be used for establishing initial calibration correlation acceptance. In cases where the calibration data are outside these criteria, the
analyst must rerun the calibration standards (meeting the same criteria) and/or prepare a
new curve, changing instrumental conditions as necessary.
For analyses which are performed frequently and for which substantial calibration data is available, a complete recalibration is not required each time an analysis is performed
providing that the following criterion is met: one calibration standard is analyzed at the
beginning of the analysis which may vary from the expected response (based on the most recent initial calibration curve) by~ 25% difference or as specified by the method, SOP or
QAPP. If this criterion is not met, a complete recalibration is necessary.
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Date: 12/22/95
Section 8.0
Revision 0.01
Page 3 of 9
During the course of analysis, calibration standards are routinely analyzed to ensure that
the instrumental response has not changed. The continuing calibration criteria stipulated
in each method or SOP are used by the analyst to determine whether the instrument must
be recalibrated or the instrument conditions further optimized.
The accuracy of prepared standards is periodically checked by comparison with a
standard from an independent source.
Certain equipment such as balances, pH meters, and turbidity meters are normally
calibrated with NIST traceable standard reference material.
8.2.1 Analytical Balances
Every 12 months, calibration of the entire analytical range shall be checked by a
qualified service technician. The calibration of each balance is checked each day
the balance is used with weights traceable to NIST. Calibration weights are ASTM
Class 1 (replaces Class S designation) and are recertified every two years. If
balances are calibrated by an external agency, verification of their weights shall be
provided. All information pertaining to balance maintenance and calibration is·
recorded in the individual balance logbook and/or is maintained on file in the QA
department.
8.2.2 Thermometers
Certified, or reference, thermometers are maintained for checking calibration of
working thermometers. Reference thermometers are provided with NIST
traceability for initial calibration and are recertified every year with equipment
directly traceable to the NIST.
Working thermometers are compared with the reference thermometers every 12
months; digital working thermometers are verified for accuracy on a quarterly
. frequency. Each thermometer is tagged and individually numbered. In addition,
working thermometers are visually inspected by laboratory personnel prior to use.
Calibration temperatures and acceptance criteria are based upon the working
range of the thermometer and the accuracy required for its use. Laboratory
. thermometer inventory and calibration data are maintained in the QA department
or designated area.
8.2.3 pH/Electrometers
The meter is calibrated before use each day, and once after each four hours of
continuous use, using fresh buffer solutions.
8.2.4 Spectrophotometers
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8.3
Date: 12/22/95
Section 8.0
Revision 0.01
Page 4 of9
During use, spectrophotometer performance is checked at established frequencies
in analysis sequences against initial calibration verification (ICV) and continuing
calibration verification (CCV) standards. The instrument operating capability is
also evaluated annually (more frequently if required by certification agencies} by
qualified laboratory personnel or by an outside instrument maintenance service.
GC/MS CALIBRATION PROCEDURES
The minimum operations necessary to satisfy analytical requirements associated with the
determination of organic compounds in water and soil/sediment samples are listed below.
The following operations should be performed routinely in the laboratory:
• Documentation of GC/MS mass calibration and abundance pattern
• Documentation of GC/MS response factor stability
• Internal standard response and retention time
Prior to initiating data collection, it is necessary to establish that a given GC/MS meets the
standard mass spectral abundance criteria. This is accomplished through the analysis of • decafluorotriphenylphosphine (DFTPP} for base/neutral and acid (BNA} compounds or p-
bromofluorobenzene (BFB} for volatile compounds. Each GC/MS system used for analysis of volatile or semivolatile organic compounds must be tuned to meet method or program specific ion abundance criteria before analysis of standards, blanks, or samples
can proceed.
Prior to the analysis of samples and after tuning criteria have been met, the GC/MS
system must be initially calibrated with a minimum of five concentrations of each
compound being analyzed to determine the linearity of response. USEPA criteria specify
both the concentration levels for initial calibration and the specific internal standard to be used on a compound-by-compound basis for quantitation. The response factor (RF} for
each compound at each concentration level is calculated using the following Equation 8.1:
RF=
Where:·
* (8.1)
As Cx
= area of the characteristic ion for the compound to be measured
= area of the characteristic ion for the specific internal standards
= concentration of the internal standard (mg/ml)
= concentration of the compound to be measured (ng/ul}
Using the RF from the initial calibration, the percent relative standard deviation (¾RSD} for compounds identified as Calibration Check Compounds (CCCs} is calculated using
Equation 8.2:
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Where:
s
%RSD = X 100
X
RSD = relative standard deviation
(8.2)
Date: 12/22/95
Section 8.0
Revision 0.01
Page 5 of 9
s = standard deviation of initial five response factors (per compound). x = mean of initial five response factors (per compound).
The % RSD for each individual CCC must be ~ than 30% or as specified by the
method. This criterion must be met for the initial calibration to be valid.
A calibration check standard containing all compounds of interest as well as all required surrogates, is performed each day of analysis. The RF data from the standard is
compared each day against the average RF from the initial calibration for a specific
instrument. If the response to a calibration check standard differs from the initial calibration by more than ±20% or as specified by the method, then investigation and corrective action must be performed, including a complete recalibration if necessary.
8.4 NON GC/MS CHROMATOGRAPHY CALIBRATION PROCEDURES
· Initially, a three or five point calibration curve, consisting of all compounds of interest (plus
a calibration blank for certain analyses such as VOCs), is established to define the usable range of the instrument. Calibration may be accomplished as best-fit line, quadratic equation, or average RF. The curve is determined to be linear if the correlation coefficient
is .:". 0.995. Linearity may also be determined using response factors. Response factors
are calculated for each compound at each concentration level. These RFs will be
averaged to generate the mean RF for each compound over the range of the standard
curve. The curve is determined to be linear if the RSD of the response factors is <20%. The mean response factor will be used to calculate the sample concentration of the
compound of interest. When sample responses exceed the range of the standard curve,
the sample will be diluted to fall within the range of the standard curve and be reanalyzed.
The results of the daily GC standardization will be tabulated and filed with the corresponding sample analyses. Daily full calibration is not necessary if a calibration
check standard validates the initial calibration curve. If the response to a calibration check
standard differs from the initial calibration by more than ±15% for any analyte being
quantitated or as specified by the method, then investigation and corrective action will be performed, including complete recalibration, if necessary.
Continuing Calibration is checked as described in Pace SOPs or methods.
8.5 Calibration of Inductively Coupled Argon Plasma Spectrometer (ICP) and Atomic Absorption Spectrophotometer (AAS)
The ICP and AAS are standardized for the metal of interest by the analysis of a set of
calibration standards prepared by diluting a stock solution of known concentration.
Working standards are prepared by dilution of the stock standard. For the AAS, the concentration of the calibration standards is chosen so as to cover the working range of
:\lqapreva\sectB.doc
Date: 12122/95
Section 8.0
Revision 0.01
Page6of9
the instrument. For ICP, a standard is analyzed as a sample to determine the upper limit of the calibration. Subsequently, all sample measurements are performed within this working range. After the working standards have been prepared, they are analyzed on the ICP or AAS and the instrument response is calibrated to provide a direct readout in concentration.
The calibration is accomplished by entering the metal concentration equivalent to the readout in absorbance units (or emission intensity) during analysis of the working standards.
After the initial calibration, the analysis of the working standards is repeated during sample
analysis to standardize instrument response during analysis and to confirm the calibration settings. A typical analysis sequence is presented below.
Working standards are prepared by dilution of a stock standard solution of the
metal of interest.
A calibration curve within the working range of the instrument is established by . analysis of three to five working standards.
An independent standard is analyzed to confirm the calibration settings. If the calibration settings are not confirmed, the instrument is recalibrated.
The samples are analyzed for the metal of interest.
During sample analysis, a check standard is analyzed to monitor instrument.
stability. If the analysis indicates that instrument calibration has changed by more
than .±10% for ICP or more than ±20% for AAS, the instrument is recalibrated and the analysis is repeated.
Following completion of the sample analyses, the check standard is reanalyzed to confirm calibration settings. If calibration settings are confirmed, the analysis is completed. However, if the calibration settings are not confirmed, the problem is corrected, and the analyses are repeated.
Written records of all calibrations shall be filed with the raw data.
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Instrument
GC/MS (8270B)
GC/MS (8240B)
Gas Chromatograph
(8080A)
:\lqapreva\sect8.doc
TABLE 8.1 Summary of Calibration Requirements
Calibration Standards
Used, Initial and
Pally Minimum
Tune: DFTPP
Initial: 5 level
(20,50,80, 120,160, ppb)
Daily: 1 level (50)
(every 12 hours)
Tune: BFB
Initial: 5 level
(10,20,50, 100,200 ppb)
Daily: 1 level (50)
(every 12 hours)
Initial: 5 level
(cone. based upon instr.
response)
Mid level DDT/Endrin
standard
Acceptance Limits
Meets criteria
RSD <30% for RFs
of CCCs
RF ~ 0.050 (SPCC)
% Difference
<20% of the average five-
point RF (CCC)
Meets Method Criteria
RSD <30% for RFs
of CCCs
RF~ 0.300 (0.250 for
bromoform) (SPCC)
% Difference <20% of the
average five-point RF (CCC)
Std curve or calibration
factor (CF) if% RSD .'.': 20
DDT/Endrin breakdown < 20%
Date: 5/22/95
Section 8.0
Revision 0.00
Page 7 of 9
Corrective Actions
Re-tune instrument
Repeat DFTPP analysis
Repeat Calibration
Evaluate system
Repeat Calibration
Evaluate system
Take corrective action
Repeat Calib. Check; see Lab
Supervisor
Re-tune instrument
Repeat BFB Analysis
Repeal Calibration
Evaluate System
Repeal Calibration
Evaluate System
Take Corrective Action
Repeal Calib. Check;
See Lab Supervisor
Make new standards
or establish new
calibration curve.
Rerun standard once
Perform col. maint.
Instrument
Gas
Chromatograph
(herbicides)
Inductively
Coupled Plasma
Emission
Spectrometer
TABLE 8.1 Summary of Calibration Requirements (continued)
Calibration Standards
Used, Initial and
Pally Minimum
Daily: 1 level of check
standard (midrange)
Std check every 10 samples
Initial: 5 levels
( cone. based upon instr.
response)
Daily: 1 level of check
standard (midrange)
Std check every 1 0 samples
Initial: high standard +
blank
Daily: instrument check
standard and calibration
std. & blank every 1 0 samples
Acceptance Limits
CF < ± 15% of initial
calibration
CF± 15% of daily calibration
(< ± 20% for confirmation).
Retention times within
retention time windows.(For
methods using retention time
windows.)
Standard curve or calibration
factor (CF) if% RSD < 20
CF < ± < 15% of initial
calibration
CF± 15% of daily calibration
(< ± 20% for confirmation).
Retention times within
retention time windows. (For
methods using retention
time windows.)
ICV: < 90-110%
CCV: < 80-120%
Date: 5/22/95
Section 8.0
Revision 0.00
Page 8 of 9
Corrective Actions
Repeat initial
calibration
Reanalyze samples
that were analyzed
after standard that
failed criteria and
before next standard
that passes criteria
Make new standards or
establish new
calibration curve
Rerun samples that
were analyzed between
standards failing
criteria
Recalibrate.
Repeat twice; if
outside control
limit, then
recalibrate making
new stds if necessary
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Instrument
Atomic
Absorption
Spectrophoto-
meter
pH Meter
UV-Visible
Spectra-
photometer
Instrument
Analytical Balance
Thermometers
:\lqapreva\sect8.doc
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TABLE 8.1 Summary of Calibration Requirements {continued)
Calibration Standards
Used, Initial and
Daily Minimum Acceptance Limits
Initial: 5 levels + blank Linear regression correlation
Daily: 1 check standard coefficient :::_0.995;
(midrange) & blank ICV: 90-110%
per 10 samples CCV: 80-120%
Daily: 2 levels +0.05 pH unit
Bracket sample range
Initial: 5 levels + blank Linear regression correla-
Daily: check standard tion coefficient > 0.995;
ICV: 90-110%
TABLE 8.2 Summary of Routine Calibration Requirements
Calibration Standards
Used, Initial and
Daily Minimum
Daily: Sensitivity (with ASTM
Class "1" weight)
Annually; Calibrate in
constant temperature baths
at two temperatures
against precision
thermometers certified against
an NIST thermometer
Acceptance Limits
±0.001 gm (varies by method)
±0.1 to ±_0.5 C (depending
upon method) .
Date: 5/22/95
Section 8.0
Revision 0.00
Page 9 of 9
Corrective Actjons
Make new standards or
establish new
calibration curve
Clean or replace
electrode; recalibrate
Recalibrate services
Correctjve Actions
Adjust sensitivity. re-level
Tag and remove from
service, replace
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9.0 ANALYTICAL PROCEDURES
Date: 2/28/97
Section 9.0
Revision 2.0
Page 1 of 27
Pace Analytical laboratories are capable of analyzing the full range of environmental samples from
all media, including surface and groundwater, soil, sediment, tissue, and waste. Refer to Table 9.2
for a representative listing of specific Pace Analytical capabilities. Methodologies are employed
with guidance from agencies such as EPA, ASTM, USGS, NIOSH and, in certain instances, state
regulatory agencies. In some situations, Pace Analytical develops and validates methodologies
which are more applicable to a specific problem or objective.
Analytical procedures are detailed descriptions of any and all processing, preparation and analysis
of samples In the laboratory. In some instances, data format, presentation and delivery are also
described. All analytical procedures shall be conducted in strict adherence with written Standard
Operating Procedures manuals which have been reviewed and approved by the Laboratory
Operations Manager, the Pace QA Officer and the Pace General Manager. Documents from
which SOPs are developed include the references listed in Table 9.1. Additional SOPs may be
adapted from other sources or generated in-house as project needs require.
9.1 ANALYTICAL METHODS
Numerous sources of information are available to offer guidance in analytical methods.
Selection of the appropriate method is dependent upon data usage and the regulatory
requirements during the analysis. Table 9.1 describes the analytical references routinely
used by Pace Analytical. Pace Analytical may modify existing methods based on the
following considerations: 1) In order to meet project specific objectives; 2) in order to
incorporate modifications or improvements in analytical technology; 3) In order to comply
with changing regulations and requirements: 4) in order to address unusual matrices not
covered in available methods.
Pace Analytical will make every effort to disclose to its clients any instances in which
modified methods are being used in the analysis of samples.
The following subsections contain method synopses for representative methods most
frequently performed at Pace Analytical laboratories. For clarity purposes, c1;rtain method
summaries also contain calibration criteria, several of which have been previously detailed
in Section 8.
9.2 SAMPLE PREPARATION METHODS
9.2.1 Digestion of Aoueous samples for Metals -Method 3005A
This method is an acid digestion procedure used for the preparation of water
samples for metals analysis. The digested samples can· be analyzed for dissolved
and total recoverable metals by flame (FAA) or furnace (GFM) atomic absorption
spectrophotometry or by inductively coupled argon plasma emission spectroscopy
(!CPS). Method .3005A may be used to prepare samples for analysis of the
following metals:
:llqaprevalsect9.do<:
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Date: 2128/97
Section 9.0
Revision 2.0
Page 2 of 27
For the analysis of total recoverable metals, the entire sample is acidified at the
time of collection with nitric acid (HN03). Sample preparation involves heating the
sample with acid and concentrating to a specified volume. The sample is not
allowed to boil because some of the elements are in a volatile state and may be
easily lost. The digestate is then filtered (if necessary) and diluted to the desired
concentration for analysis.
For the analysis of dissolved metals, the samples are filtered through a 0.45-um
filter immediately upon collection and prior to acidification with nitric acid. In the
lab, the sample is heated with acid and the volume is reduced. The digestate is
filtered again (if necessary) and diluted to volume.
9.2.2 Digestion of Aqueous Samples to(Metals • Method 3QJOA and the CLP sow
These methods describe the preparation of aqueous sampjes for total metals
determination by flame atomic absorption spectrophotometry (FM) and by
inductively coupled argon plasma emission spectroscopy (ICPS). By method
301 OA. samples are vigorously digested with nitric acid. By CLP protocol. samples
are digested with a mixture of nitric acid and hydrochloric acid.
9.2.3 Digestion of Aqueous Samples tor Metals -Method 3020A and the CLP sow
These methods describe the preparation of aqueous samples for total metals
determination by graphite furnace atomic absorption spectroscopy (GFM). By
method 3020A, samples are vigorously digested with nitric acid. By CLP protocol,
samples are digested wlth a mixture of nitric acid and hydrogen peroxide.
9.2.4 Digestion of So/id samples for Metals -Method 3050A and the CLP sow
These methods are applicable to the preparation of sediment, sludge, and soil
samples for metals determination by FAA or GFM or by ICPS. One gram of solid
sample is digested with nitric acid and hydrogen peroxide. The digestate is then
refluxed with nitric or hydrochloric acid, depending on the analysis performed.
When using hydrochloric acid as the final refluxing acid, the digestates may not be
boiled because antimony is in a volatile state and may be easily lost. A separate
sample aliquot is dried to determine the percent moisture in the sample.
9.2.5 separatocy Extraction -Method 351 PB
Method 3~1 OB is designed to quantitatively extract nonvolatile and sernivolatile
organic compounds from liquid samples using separatory funnel techniques.
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Date: 2/28/97
Section 9.0
Revision 2.0
Page 3 of 27
The sample and extracting solvent must be immiscible in order to yield recovery of
target compounds. Subsequent cleanup and detection methods are described in
the organic analytical method that will be used to analyze the extract. Samples are
pH-adjusted and serially extracted by vigorous shaking for 1-2 minutes with the
appropriate solvent for the analytical method. Samples are extracted three times,
the combined extracts are dried with anhydrous sodium sulfate and concentrated
in a Kuderna-Danish apparatus.
9.2.6 continuous Uguld/Uguid Extraction -Method 3520B
Method 3520B is designed to quantitatively extract nonvolatile and semivolatile
organic compounds from liquid samples using continuous liquid-liquid extractors.
The sample and extracting solvent must be immiscible in order to yield recovery of
target compounds. Subsequent cleanup and detection methods are described in
the organic analytical method that will be used to analyze the extract. Samples are
pH-adjusted and extracted with the appropriate solvent for the analytical method.
Samples are extracted for 18 to 24 hours, the extracts are dried with anhydrous
sodium sulfate, and then concentrated in a Kudema-Danish apparatus.
9.2.7 Soxh!et Extraction -Method 35408
Method 3540B is a procedure for extracting nonvolatile and semivolatile organic
compounds from solids such as soils and sludges. The So:xhlet extraction process
ensures intimate contact of the sample matrix with the extraction solvent.
Extraction Is accomplished by mixing the solid sample with anhydrous sodium
sulfate, placing it in an extraction thimble or between two plugs of glass wool, and
extracting it with an appropriate solvent in the Soxhlet extractor for 18 to 24 hours.
The extract is dried and concentrated and then treated using a cleanup method or
analyzed directly _by the appropriate measurement technique.
9.2.B Sonicatioo Extraction -Method 3550A
Method 3550A is a procedure for extracting nonvolatile and semivolatile organic
compoundl> from solids such as soils and sludges. The Sonication process
ensures intimate contact of the sample matrix with the extraction solvent. A
weighed sample of the solid waste is mixed with sodium sulfate, then dispersed
into the solvent using sonication. The extract is dried with anhydrous sodium
sulfate and concentrated with a Kuderna-Danish apparatus. The resulting solution
may then be cleaned up or analyzed directly using the appropriate technique.
9.2.9 Waste Pllutioo -Method 3580A
Method 35B0A is a technique for solvent dilution of non-aqueous waste samples
prior to sample cleanup and/or analysis. It is designed for wastes that may contain
organic constituents at concentrations greater than 20,000 ug/kg and that are
soluble in the dilution solvent.
:~qaprevalsect9.doc
9,3
9.2.1 o Purge-and-Trai;, Sample Introduction -Method 5030A
Date: 2/28/97
Section 9.0
Revision 2.0
Page 4 of 27
Method 5030A is used to determine the concentration of volatile organic
compounds in a variety of liquid and solid waste matrices using a purge and trap
gas chromatographic procedure. The success of this method depends on the level
of interferences in the sample. Results may vary due to the large variability and
complexity of various matrices.
Inert gas is bubbled through a 5-ml or 25-mL aqueous sample aliquot at ambient
temperature to transfer the volatile components to the vapor phase. The vapor is
swept to a sorbent column where the volatile components are trapped. After
purging is completed, the sorbent column is flash heated and backflushed with
inert gas to desorb and transfer the volatile components onto the head of a GC
column. The column is heated to elute the volatile components. which are
detected by the appropriate detector for the analytical method used.
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Solid samples may be analyzed using one of two techniques. For Low level soil I
analysis, 5 g of solid sample is dispersed into 5 ml of Contaminant-free laboratory
water and the sample is purged as described above. This technique is referred to
as the direct purge method. For medium level soil analysis, an aliquot of solid I
sample is dispersed in methanol to dissolve the volatile constituents and a portion
of the methanol extract is combined with contaminant-free laboratory water and
purged as described above. I
9.2.11 Extraction Procedure To:r;icity Test IEP-Tox} -·Method 1310A
This method is used to determine whether a waste exhibits the characteristics of I
extraction procedure (EP) toxicity. If a representative sample of the waste contains
>0.5% solids, the solid phase of the sample is ground to pass a 9,5 mm sieve and
extracted with deionized (DI) water that is pH adjusted with acetic acid. Wastes I
containing <0,5% solid material are extracted and analyzed as a single phase.
9.2.12 Toxicity Characteristic Leaching Procedure CTCLP} -Method 1311
This method is used to determine whether a waste exhibits toxicity leaching
characteristics. The procedure includes a leaching extraction for semivolatile
compounds and metals and a zero-headspace extraction for volatile compounds.
9. 2.13 California Assessment Manual Waste Extraction Test /CAM WED
This waste extraction test, described in the California Administrative Code, Title 22,
Article 11, Section 66700, can be used to determine the amount of extractable
substance in a waste or other material.
CALIBRATION AND ANALYSIS PROCEDURES FOR ORGANICS
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9.3.1 tJalogenated Volatile Organics -Method so, PB I
Halogenated volatile organics in water and soil samples are analyzed using
I
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Date: 2/28/97
Section 9.0
Revision 2.0
Page 5 of27
method 801 OB, which is a gas chromatography (GC) method using purge and trap
sample introduction (method 5030A). An inert gas is bubbled through a water
matrix to transfer the volatile halocarbons from the liquid to the vapor phase.
Volatile halocarbons are collected on a sorbent trap, then flash thermally desorbed
and transferred to a GC column. Target analytes are detected with an electrolytic
conductivity detector (ELCO). Soil samples may be heat purged directly in reagent
water or are extracted with methanol; if extracted in methanol an aliquot of sample
extract is added to blank reagent water for purge and trap GC analysis.
Positive results are confirmed by GC analysis using a second GC column of
dissimilar phase. When second column analysis is performed, peak retention
times (RTs) on both columns must match expected RTs within the calculated RT
windows. Also, calculated quantitations from each column should be in agreement
with one another (generally they should match within a factor of two) for the
presence of an analyte to be considered confirmed.
Cafjbration • Calibration standards are prepared and analyzed at five i:oncentration
levels. A linear calibration curve not forced through the origin is developed for
each analyte of interest. This function is used for the calibration curve if the
correlation coefficient (r) for that analyte is ~0.995, otherwise, a curve function is
used that meets this criterion. Each working day, the calibration is verified with the
analysis of a continuing calibration standard at the beginning and end of the run
sequence and after every 10 analyses. The calibration factor for each analyte to
be quantitated must not exceed a 15% difference when compared to the initial
standard of the analysis sequence, When this criterion is exceeded. inspect the
GC system to determine the cause and perform whatever maintenance is
necessary before recalibrating and proceeding with sample analysis. All samples
that were injected after the standard exceeding the criterion must be reinjected to
avoid errors in quantitation, if the initial analysis indicated the presence of the
specific target analytes that exceeded the criterion.
9.3.2 Aromatic VOiatiie Organics -Method B02QA
Aromatic VQlatile organics in water and soil samples are analyzed using method
8020A, which Is a gas chrornatography (GC) method using purge and trap sarnple
introduction (method 5030A). An inert gas is bubbled through a water matrix to
transfer volatile aromatic hydrocarbons from the liquid to the vapor phase. Volatile
aromatics are collected on a sorbent trap, then flash thermally cJesorbed and
transferred to a GC column. Target analytes are detected using a photoionization
detector (PIO). Soil samples may be heat purged directly in reagent water or are
extracted with methanol; if extracted with methanol an aliquot of sample extract is
added to blank reagent water for purge and trap GC analysis.
Positive results are confirmed by GC analysis using a second GC column of
dissimilar phase. When second column analysis is performed, peak RTs on both
columns must match expected RTs within the calculated RT windows. Also,
calculated quantilations from each column should be in agreement with one
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another (generally they should match within a factor of two) for the presence of an
analyte to pe considered confirmed.
Calibration -Calibration standards are prepared and analyzed at five concentration
levels. A linear calibration curve not forced through the origin is developed for
each analyte of interest. This function is used for the calibration curve if r ~0.995
for that analyte; otherwise, a curve function is used that meets this criterion. Each
working day, the calibration is verified with the analysis of a continuing calibration
standard at the beginning and end of the run sequence and after every 1 O ·
analyses. For each analyte of interest, the %D of the response in the continuing
calibration standard must agree with the expected response by ~15% in order for
the run sequence to continue.
9.3.3 Organochlorine Pesticides and PCBs -Method BOBOA and the CLP sow
Organochlorine pesticides and PCBs are analyzed by gas chromatography
following either method 8080A or the CLP Organic SOW. Each of these analyses
involves solvent extraction of the sample followed by analysis by gas chromato-
graphy with electron capture detection (GC-ECD).
Positive results are confirmed using a second GC column of dissimilar phase. For
an analyte to be considered confinned, the peak RTs on both columns must match
the expected RTs. Also, the calculated quantitations between the two columns
should be in agreement with one another (generally they should match within a .
factor of two) for the presence of the analyte to be considered confirmed by
method BOBOA. For analysis by CLP protocol, the results are flagged with a "P" if
the two quantitations differ by more than 25%. In addition, the breakdown of 4,4'-
DDT and endrin is monitored. If the breakdown cif either of these compounds is
found to exceed 20%, the analytical sequence must be discontinued. For analysis
by CLP protocol. the combined breakdown must also not exceed 30%.
Calibraljon for Method BOSOA -Calibration standards are prepared and analyzed at
five concentration levels. A linear calibration curve not forced through the origin is
developed for each analyte of interest. This function is used for the calibration
curve if r ~0.995 for that analyte; otherwise, a curve function is used that meets
this criterion. Each working day, the calibration is verified with the analysis of a
continuing calibration standard at the beginning and end of the run sequence and
after every 1 O analyses. For each analyte of interest, the %D of the response in
the continuing calibration standard must agree with the expected response by
!:15% in order for the run sequence to continue.
Calibration foe the CLP SOW -Calibration and analysis are performed in strict
accordance with the CLP Organic SOW.
9.3.4 \/Qlatile Organics -Method 8240B and the CLP sow
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Samples may be analyzed for volatile organics by gas chromatography/mass
spectrometry (GC/MS) following the procedure described in method 8240B or the
CLP Organic SOW. Analyte identification and quantitation are a=mplished using
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response factors and retention times generated from a five-point calibration curve,
relative to the closest eluting internal standard. The three internal standards used
for these methods are:
•
• •
Bromochloromethane
1,4,Difluorobenzene
Chlorobenzene-d5
If requested by the client, non-target analytes are reported as tentatively identified
compounds (TICs), when an acceptable match is obtained between the spectrum
of the analyte and a spectrum found by library search. Unidentified TICs are
labeled "unknown". The TICs are quantitated using response factors of 1 relative
to the nearest eluting internal standards.
Instrument Performance Check -The mass spectrometer is tuned daily and after
every 12 hours of operation to yield an acceptable spectrum for
p-bromofluorobenzene (BFB). Relative ion abundance criteria for BFB are given in
Table 9.3.
CaUbratjon for Method 8240B -· After passing the instrument perfon11ance check
criteria and prior to analyzing samples, a 5-point initial calibration is performed.
From that calibration, the calibration check compounds (CCCs) must meet the
RSD criteria of !:30% and the system performance check compounds (SPCCs)
must meet the minimum RRF criteria given in the method. A continuing calibration
standard is analyzed after every 12 hours of operation. In that standard, the CCC
compounds must meet the %D criteria of !:20% and SPCC compounds must meet
the minimum RRF criteria listed in the method.
Caljbrajjon for the CLP SOW -After passing the instrument performance check
criteria and prior to analyzing samples, a 5-point initial calibration is performed.
From that calibration, the compounds listed in Table 2 of Exhibit D, Section IV
r,./OA) of the CLP sow must meet the RSD criteria of !:20,5% and the minimum
RRF criteria listed in the method. A continuing calibration standard is analyzed
after every 12 hours of operation. In that standard, the Table 2 compounds must
meet the %D criteria of !:25% and the minimum RRF criteria listed in the method.
9.3.5 Semivo!atile organics -Method 8270B and the CLP sow
Semivolatile extracts are analyzed by gas chromatography/mass spectrometry
following method 8270B or the CLP Organic SOW. All samples are prepared
following extraction methods described in the applicable protocol. Identification
and quantitation is performed using response factors and retention times
generated from a five-point calibration curve, relative to the closest eluting of six
internal standards, The six internal standards are:
• 1,4-Dichlorobenzene-cL.
• Naphthalene-de
• Acenaphthene-d10
• Phenanthrene-d10
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If requested by the client, non-target analytes are reported as tentatively identified
compounds (TICs), when an acceptable match Is obtained between the spectrum
of the analyte and a spectrum found by library search. Unidentified TICs are
labeled "unknown". The TICs are quantitated using response factors of 1 relative
to the nearest eluting internal standards.
Instrument Performance Check • The mass spectrometer is tuned daily and after
every 12 hours of operation to give an acceptable spectrum for DFTPP. DFTPP
ion abundance criteria are given in Table 9-4.
Caljbratjon for Method 8270B -After passing the instrument performance check
criteria and prior to analyzing samples, a 5-point initial calibration is performed.
From that calibration, the CCC compounds must meet the RSD criteria of :::30%
and the SPCC compounds must meet the minimum RRF criteria given in the
method. A continuing calibration standard is analyzed after every 12 hours of
operation. In that standard, the CCC compounds must meet the %D criteria of
::,20% end SPCC compounds must meet the minimum RRF criteria listed in the
method,
Calibration for the CLP SOW -After passing the instrument performance check
criteria and prior to analyzing samples, a 5-point initial calibration is performed.
From that calibration, the compounds listed in Table 5 of Exhibit D, Section IV (SV)
of the CLP SOW must meet the RSD criteria of .:;20.5% and the minimum RRF
criteria listed in the method. A continuing calibration standard is analyzed after
every 12 hours of operation. In that standard, the Table 5 compounds must meet
the ¾D criteria of ::,25% and the minimum RRF criteria listed in the method.
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9.3.6 purgeab\e Petroleum Hydrocarbons I
Gasoline and volatile aromatic compounds, including benzene, toluene,
ethylbenzene, and the xylenes (BTEX), are analyzed by a modified method 8015A
using the direct purge technique described above for method 5030A. Analysis is I
performed on a GC equipped with a photoionization detector (PIO) and a flame
ionization detector (FID) connected in series. If BTEX compounds are found
without the associated presence of gasoline, confirmation analysis is performed 1 with a second GC column of dissimilar phase and retention characteristics in
accordance with the requirements of method 8020A.
Caljbratjon -Calibration standards are prepared and analyzed at five concentration
levels. A linear calibration curve not forced through the origin is developed for
each analyte of interest. This function is used for the calibration curve if r ~0.995
for that analyte; otherwise, a curve function is used that meets this criterion. Each
working day, the calibration is verified with the analysis of a continuing calibration
standard at the beginning and end of the run sequence and after every 1 O
analyses. For each analyte of interest, the %D of the response in the continuing
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calibration standard must agree with the expected response by ~15% in order for
the run sequence to continue.
9.3.7 Extractable Petroleum Hydrocarbons
Aqueous samples analyzed for diesel, kerosene, jet fuel, and motor oil are
prepared using method 35108 (separatory funnel liquid/liquid extraction) or method
35208 (continuous liquid/liquid extraction). Solid samples are prepared using
method 3540B (Soxhlet extraction), method 3550 (sonication extraction), or wrist
action shaker extraction (California LUFT method). One liter of water or 30 g of
soil/sludge are extracted and concentrated to a volume of 1 ml. Analysis is
performed by a modified method 8015A on a GC equipped with a capillary or
megabore column and an FID detector.
Cafjbratjon -Calibration standards a~prepared and analyzed at five concentration
levels. A linear calibration curve not forced through the origin is developed for
each analyte of interest. This function is used for the calibration curve if r ?.0.995
for that analyte; otherwise, a curve furaction is used that meets this criterion. Each
working day, the calibration is verified with the analysis of a continuing calibration
standard at the beginning and end. of the run sequence and after every 1 O
analyses. For each analyte of interest. the %D of the response in the continuing
calibration standard must agree with the expected response by ~15% in order for
the run sequence to continue.
REPRESENTATIVE CALIBRATION AND AN!A.LYSIS PROCEDURES FOR INORGANICS
9.4.1 Metals by !CPS -Method 601 OA and the CLP sow
These methods describe the simultaneous or sequential determination of metal
elements using !CPS. The method measures element-emitted light by optical
spectromet,y. Samples are nebu\ized and the resulting aerosol is passed through
a plasma torch, Element-specific atomic-line emission spectra are prnduced which
are dispersed by a grating spectrometer and monitored for intensity by
photomultiplier tubes.
Calibration -n,e calibration procedl!lres for !CPS are detailed in method 6010A
and the CLP lnorganics SOW. Prior :10 the analysis of samples, an initial multipoint
calibration is analyzed for all elements of interest. The initial calibration is checked
with an initial calibration verification. standard (ICV). For each element, the ICV
responses must agree with the initia'I calibration within ±10% for the calibration to
be verified. Following the ICV and after the analysis of every 10 samples, a
continuing calibration verification standard (CCV) is analyzed. The response for
each element in the CCV must agree within :!:20% of the expected value for the
analysis to continue.
9.4.2 Metals by GFM -Methods 70601\ 7421, 7740, 7841 and the CLP sow -
Graphite furnace atomic absorption (GFAA) techniques may be used for the
determination of arsenic, lead, selenium, thallium, and other mete1ls depending
upon the sensitivity required. Following sample digestion, an aliquot of sample is
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placed in a graphite tube in the furnace, evaporated to dryness, charred, and
atomized, The sample is placed in the light path of an atomic absorption
spectrophotometer. The absorption cf light by the atomized metal is measured
with a photomultiplier tube.
Ca!ibratjon -Calibration procedures for the GFAA analyses are detailed in the
respective methods in SW-846 and the CLP SOW. For the element of interest. a
m1,1ltipoint initial calibration is performed. The calibration correlation coefficient
must be ?,0.995 to be acceptable. The initial calibration is verified by the analysis
of an !CV standard prepared from a source independent of the calibration
standards. The response of the ICV must agree with the expected response within
±10% in order for the calibration to be verified. A CCV check standard is analyzed
following the analysis of the !CV and after the analysis of every 10 samples. The
response of the CCV must agree with the expected value within ±20¾ in order for
the analysis to contin\.le.
9.4.3 Mercury by CVAA -Methods 7470. 7471A and the CLP sow· Cold-vapor atomic
absorption (CVAA) techniques are used for the determination of mercury. Sample
preparation is specified in the method. Following dissolution, mercury in the
sample is reduced to the elemental state and aerated from solution in a closed
system. The mercury vapor passes through a cell positioned in the light path of an
atomic absorption spectrophotometer.
Ca/lbratjon • The calibration procedure is detailed in SW-846 and the CLP SOW.
Prior to the analysis of samples, a multipoint Initial calibration is performed. The
calibration correlation coefficient must be ?,0. 995 to be acceptable. The initial
calibration is verified by the analysis of an ICV standard prepared from a source
independent of the calibration standards. The response of the ICV must agree
with the expected response within ±20¾ In order for the calibration to be verified.
A CCV check standard is analyzed following the analysis of the ICV and after the
analysis of every 1 O samples. The response of the CCV must agree with the
expected value within ±20% in order for the analysis to continue.
9.4.4 Total and Amenable Cyanide -Method so1owso12 and the CLP sow
These methods are 1,1sed to determine the concentration of inorganic cyanide in
aqueous or solid samples. These methods are 1,1sed to determine values for both
total cyanide and cyanide amenable to chlorination. Cyanide, as hydrocyanic acid
(HCN). is released by refluxing the sample with strong acid and distilling the HCN
into an absorber-scrubber containing sodium hydroxide solution. The cyanide ion
In the absorbing solution is then determined by UV spectrophotometry.
Calibration -Prior to sample analysis, a multipoint initial calibration is performed,
The calibration correlation coefficient must be ?,0. 995 to be acceptable. The initial
calibration is verified by the analysis of an !CV standard prepared from a source
independent of the calibration standards. The response of the ICV must agree
with the expected response within ±10% for the calibration to be verified. A CCV
check standard Is analyzed following the analysis of the !CV and after the analysis
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of every 10 samples, The response of the CCV must agree with the expected
value within ±10% for analysis to continue.
9.4.5 Anions -Method 300.o
Method 300.0 may be used to analyze anions. including chloride. nitrite. nitrate. o-
phosphate. bromide, and sulfate. in aqueous samples by ion chromatography (IC).
A volume of sample Is injected into the ion chromatograph. The anions of interest
are separated and measured using a chromatography system consisting of a
guard column, separator column, suppressor device and conductivity detector.
Samples must be refrigerated at 4 °C and analyzed within 48 hours of sample
collection if nitrate, nitrite, and/or o-phosphate are analyzed. or within 28 days of
sample collection if chloride, bromide and/or sulfate are analyzed.
Calibration -Prior to sample analysis. a multipoint initial calibration is analyzed.
The calibration correlation coefficient must be :c:_0.995 to be acceptable. The initial
calibration is verified by the analysis of an !CV standard prepared from a source
independent of the calibration standards. The response of the !CV must agree
with the expected response within :t.10% for the calibration to be verified. A CCV
check standard is analyzed following the analysis of the !CV and after the analysis
of every 1 n samples. The response of the CCV must agree with the expected
value within ±15% for analysis to continue.
9.4.6 pH· Methods 1501. 9040. & 9045A
Methods 150.1 and 9040 are used to measure the pH of aqueous and multiphase
samples where the aqueous phase constitutes at least 20% of the total sample
volume. The pH of the sample is determined electrometrically using either a glass
electrode in combination with a reference potential or a combination electrode.
Method 9045A is used to determine the pH in soil samples.
CaJjbratjon -The pH meter is calibrated with three standard buffer s1Jlutions. The
reading must be within +0.05 to ±0.1 pH units (depending upon the instrument) of
the true value of each buffer solution.
9.4,7 Non-Filterable Residue -Method 160.1
This method is applicable to drinking, surface and saline waters, and domestic and
industrial wastes. A well mixed sample is filtered through a glass fiber filter. The
residue that passes through the filter is dried and measured gravimetrically.
CaHbra!jon -The analytical balance must be checked each day of use with ASTM
Class 1 weights. Balance readings must read within ±D.001 g of the true weight.
9.4.8 Filterable Residue -Method 1so,2
This method is applicable to drinking, surface and saline waters. and domestic and
industrial wastes. A well mixed sample is filtered through a glass fiber filter. The
residue on the filter is dried and measured gravimetrically.
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Caljbratlon -The analytical balance must be checked each day of use with Class S
weights. Balance readings must read within ±0.001 g of the true weight.
9.4.9 Nitrate-Nitrite -Method 353.2
Method 353.2 is used to determine the concentrations of nitrate and nitrite in
aqueous samples. Nitrite concentration is determined by diazotization with
sulfanilamide and complexation with N-(1-naphthyl)-ethylenediamine
dihydrochloride to form a highly colored azo dye which is measured
colorimetrically. Combined nitrate-nitrite concentration is determined by first
carrying out a copper-cadmium reduction step. A filtered sample is passed
through a column containing granulated copper and cadmium to reduce nitrate to
nitrite. Nitrate concentration is determined from the difference of the nitrate-
reduced nitrite value and the nitrite value. Samples must be preserved with
sulfuric acid to pH -9 and refrigerated at 4°C. If analysis for N02 or N03 only is
desired. no preservative should be used.
Calibration -Prior to sample analysis, a multipoint initial calibration is analyzed.
The calibration correlation coefficient must be ~0.995 to be acceptable. The initial
calibration Is verified by the analysis of an ICV standard prepared from a source
independent of the calibration standards. The response of the ICV must agree
with the expected response within ±15% for the calibration to be verified. A CCV
check standard is analyzed following the analysis of the ICV and after the analysis
of every 10 samples. The response of the CCV must agree with the expected
value within ±15% for analysis to continue.
9.4.10 Total Organic Carbon rroc1 -Methods soso and 415,1
Methods 9060 and 415.1 are used to determine the concentration or total organic
carbon In samples. TOC Is analyZed by combustion of organic material in the
sample to carbon dioxide, followed by infared ( IR) detection of the carbon dioxide.
Caljbration -The instrument is calibrated by analyzing four replicates of a single
concentration standard. The initial calibration is verified by the analysis of an ICV
standard prepared from a source independent of the calibration standards. The
response of the ICV must agree with the expected response within ±15% for the
calibration to be verified. A CCV check standard is analyzed following the analysis
of the ICV and after the analysis of every .15 samples. The response of the CCV
must agree with the expected value within ±20% for analysis to continue.
9.4.11 Oil and Grease -Methods 9070/9071A and 413,1
Methods 9070 and 413.1 are used to determine the concentration of oil and grease
in waters and wastes. The aqueous sample is acidified with HCI to pH <2 and
extracted with Freon•TF (1,1,2-trichloro-1,2,2-trifluoroethane) in a separatory
funnel. Sample extracts are evaporated to dryness and measured gravimetrically
on an analytical balance. Method 9071A is used to prepare solid samples for
gravimetric analysis of oil and grease. By this method, solid samples are Soxhlet
extracted with Freon-TF and the extracts are evaporated to dryness and measured
gravimetrically on an analytical balance.
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Calibration -

A

balance calibration check is performed at the beginning and end of
each analytical sequence with 1 g and 100 g ASTM Class 1 weights.
Measurements must agree to within ,±0.001 g of the true weight.
9.4.12 Oil and Grease -Method 413.2
This method is used to determine the concentration of oil and grease in waters and
wastes. Samples are acidified with HCI to pH <2 and extracted with Freon-TF in a
separatory funnel. Sample extracts are analyzed by infrared (IR)
spectrophotometry.
Calibration -Prior to sample analysis, a multipoint initial calibration is performed.
The calibration correlation coefficient (r) must be ::.0.995 for the calibration to be
acceptable. A continuing calibration standard is analyzed after the analysis of
every 1 O samples. The continuing calibration must agree with the initial calibration
within ±20%.
9.4.13 Total Recoverable Petroleum Hydrocarbons CTBPH) -Method 41 B,1
This method is used to determine the concentration of total petroleum
hydrocarbons in waters and wastes. The sample is acidified with HCI to pH <2 and
extracted with Freon-TF in a separatory funnel. Extracts are shaken with silica gel
to remove interferences, then the extracts are analyzed by infrared (IR)
spectrophotometry.
Ca/jbratjon -Prior to sample analysis. a multipoint initial calibration is performed.
The calibration correlation coefficient (r) must be ::.0. 995 for the calibration to be
acceptable. A continuing calibration standard is analyzed after the analysis of
every 10 samples. The continuing calibration must agree with the initial calibration
within ,±20%.
9.5 METHODVALIDATION
9.6
When non-promulgated methods (i.e. methods other than EPA, NIOSH, ASTM, AOAC,
etc.) are required for specific projects or analytes of interest, or when the laboratory
develops a method, the laboratory establishes the validity of the method prior to applying it
to client samples. Method validity is established .by meeting certain criteria for precision
and accuracy as established by the data quality objectives specified by the end user of the
data.
METHOD DETECTION LIMITS
Method detection limit studies are performed for each method in use at least annually and
after any procedural or configurational change. ·
Method detection limits are determined at Pace Analytical for analyses done on samples
originating under Safe Drinking Water Act (SDWA) and Clean Water Act (CWA)
provisions by using replicate spiked analyte-free water samples. A minimum of seven
replicates of a sample spiked for the purpose are processed through the entire analytical
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method. The concentration of the detection limit sample should be between 2 and 5 times
the anticipated detection limit.
The laboratory calculates the detection limit as the Student's t(n-1) value (e.g., t value=
3.143 for seven replicate determination) times the standard deviation of 7 replicate spiked
sample measurements. The reader is referred to 40 CFR Part 136, Appendix B for further
discussion.
For samples which are analyzed by methodology approved under the Resource,
Conservation and Recovery Act (RCRA}, the MDL Is determined by multiplying the
appropriate one-sided 99% I-statistic by the standard deviation obtained from a minimum
of three analyses of a matrix spike containing the analyte of interest at a concentration
three to live times the estimated MDL, where the !-statistic is obtained from standard
references. Estimate the MDL by obtaining the concentration value that corresponds to:
a) an instrument signal/noise ratio within the range of 2.5 to 5.0, or b) the region of the
standard curve where there is a significant change in sensitivity (i.e., a break in the slope
of the standard curve). The reader is referred to SW-846, Third Edition, Chapter One,
Volume 1A for further discussion.
IT IS IMPERATIVE TO NOTE THAT METHOD DETECTION LIMITS ARE HIGHLY
MATRIX DEPENDENT. LIMITS DETERMINED BY PACE ANALYTICAL MAY NOT BE
ACHIEVABLE IN ALL MATRICES.
9.7 COMPLIANCE
9. 7 .1 Definition -Compliance is the proper execution of recognized, documented
procedures which are either approved or required, Adherence to these procedures
is required in order to provide data products acceptable to a regulatory body of
competent jurisdiction in a specific regulatory context. Compliance is separate
from, but not inconsistent with, technical scientific quality. Pace Analytical accepts
compliance as part of the Pace Analytical corporate definition of quality; "Quality is
the fulfillment of expectations and needs in all activities, demonstrated by the
satisfaction of those we serve." Pace Analytical understands that the expectations
of our clients commonly include the assumption that data and reports will satisfy a
regulatory purpose and will be found acceptable and compliant with regulatory
requirements for the performance of tests and generation of data.
9.7.2 Understanding the Regulatory Framework -Compliance is not likely to be achieved
in the absence of an understanding of the regulatory framework. Pace Analytical
will attempt to ascertain, prior to beginning a project, what regulatory jurisdiction
(USEPA, NJDEPE, etc.) pertains to a project; within the regulatory jurisdiction,
what body of regulation is meant to be satisfied (RCRA, SDWA, 21 E, etc.); and
finally, within this context, what protocols are required/expected (CLP, AFCEE,
NFESC, ASP, etc.). Pace Analytical will work with its clients to come to a mutual
understanding of all requirements.
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9.7.3 Commitment -Experience has shown that the complexity of 1mvironmental
regulations and their overlapping Jurisdiction can result in conflicting DQOs to be
established for a project or site by local, state and federal regulatory agencies. As
a result of these types of complicating factors, clients and intermediaries working
on their behalf may, but often do not, fully understand their compliance needs.
Clients may sometimes fail to communicate their compliance requirements to Pace
Analytical. Nevertheless, Pace Analytical Services, Inc., in defining quality as in
9.7.1 above, has accepted much responsibility for compliance.
Pace Analytical makes the following commitments to its clients:
Pace Analytical will proactlvely attempt to identify and understand the
regulatory context of clients' needs.
Pace Analytical will strive to be expert in understanding and executing the
regulatory requirements for compliance.
Pace Analytical will idenUfy and disclose to clients instances of non-
compliance in a forthright fashion.
9.7.4 Beso\yjng Compliance Contradjctjons and Hierarchies -It is a common occurrence
that multiple regulatory jurisdictions overlap in a specific case. This causes
uncertainty or even contradictions to arise in a work plan. Pace Analytical will
make every effort to detect such inconsistencies, and will communicate them to
clients so that an informed decision can be made by the client regarding execution
of the project. Similarly, methods and protocols will often be prescribed in a scope
of work or QAPP which either will not achieve stated or implied DQOs or which are
in conflict with the regulatory requirements. Pace Analytical will attempt to detect
these inconsistencies, and upon detection, disclose same to our client. Pace
Analytical voluntarily accepts a responsibility to provide advice to clients, however,
the primary responsibility forthis issue remains with the client.
9. 7.5 Disclosure of Noncompliance -As stated previously, it is Pace Analytical policy to
disclose in a forthright manner any detected noncompliance that may effect the
usability of data produced by Pace Analytical. It is not within our expertise to
predict the manner in which a specific regulator or regulatory body will interpret the
rules governing analysis; therefore, Pace Analytical is unable to guarantee
compliance. It is Pace Analytical policy that our responsibility begins with a bona
fide and competent attempt to evaluate potential compliance issues and ends with
disclosure of any findings that may be useful to our client in their making the final
judgment.
:llqapreval<ect9.doo
•
•
•
•
•
•
•
•
•
:\lqapreva\sect9.doc
TABLE 9.1
ANALYTICAL PROTOCOLS
Date: 2/28/97
Section 9.0
Revision 2.0
Page 16 of 27
', ::..·:
"Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the
Clean Wat~r Act." Federal Register, 40 CFR Part 136, October 26, 1984.
"Test Methods for Evaluating Solid Wastes: Physical/Chemical Methods," SW-
846. 2nd edition, 1982 (revised 1984), 3rd edition and 1st Update, Update II and
IIA, 1994, Office of Solid Waste and Emergency Response, U.S. EPA.
"Methods for Chemical Analysis of Water and Wastes", EPA 600/4-79-020, 1979
Revised 1983, U.S. EPA
U.S. EPA Contract Laboratory Program Statement of Work for Organic Analysis,
SOW 2188, OLM01 .8, 8/91, OLM02.0, and OLM03.0.
U.S. EPA Contract Laboratory Program Statement of Work for Inorganic Analysis,
SOW No. 788, ILM01 .0. 3/90 through ILM03.0.
"Standard Methods for the Examination of Water and Wastewater'', 15th, 16th,
17th and 18th editions, 1980, 1985, 1969, 1992. APHA-AWJVA-WPCF.
"Annual Book of ASTM Standards", Section 4: Construction, Volume 04.04: Soil
and Rock; Building Stones. American Society for Testing and Materials, 1987.
"Annual Book of ASTM Standards", Section 11: Water and Environmental
Technology, American Society for Testing and Materials, 1987.
"NIOSH Manual of Analytical Methods", Third Edition, 1984, U.S. Department of
Health and Human Services, National Institute for Occupational Safety and Health.
"Methods for the Determination of Organic Compounds in Finished Drinking Water
and Raw Source Water'', U.S. EPA, Environmental Monitoring and Support
Laboratory -Cincinnati (September 1986).
New York Stale Department of Environmental Conservation. Analytical Services
Protocol, September, 1989 (revised December 1991 ).
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Table 9.2
UST OF ANALYTICAL METHODS
1 Organic Analyses
Halogenated Volatile Organics
Non-Halogenated Volatile
Organics
Purgeable Aromatics and
Unsaturated Organics
Acrolein and Acrylonitrile
GC
GC
GC
GC
Organochlorine Pesticides and GC
Polychlorinated Biphenyls
Polynuclear Aromatic GC
Hydrocarbons
Chlorinated Hydrocarbons GC
Base/Neutrals & Acids GC/MS
Organophosphorus Pesticides GC
Chlorinated Herbicides GC
Volatile Organic Compounds GC/MS
Fuel Hydrocarbons and BTEX GC or IR
Alachlor, Atrazine GC
Chlordane, Heptachlor, GC
Heptachlor Epoxide, Lindane,
Methoxychlor
Carbofuran HPLC
Endothall
Total Petroleum Hydrocarbons
:\lqopreva\sect9.doc
GC
IR
503/5022
508
1613
525
515.1
524.2
531.1
548
601
602
603
608/608.1
608.2
612
625
614/622
615/608.1
608.2
624
602/418.1
619/645
608/617
418, 1
Date: 2/28/97
Section 9.0
Revision 2.0
Page 17 of 27
8010A
8015A
8020NB021A
8030A
---
8080A Mod 8080
8270B
8120A
8270B
8140
8150B
8240B/ 8260A
8015A
8080N8140
8080A
2. Inorganic Analyses
Alkalinity
Biochemical Oxygen
Boron
Bromide
Chemical Oxygen
Demand
Chloride
Chloride
Chlorine, Residual
Color
Cyanide, Total
Amenable
Fluoride, Total
Fluoride, Dissolved
Hardness, Total
:\lqapreva\sect9.doc
Table 9.2 (cont)
Potentiometric
Titration
5-Day, 20°c
ICP
Ion
Chromatography
Dichromate Reflux
(High)
Dichromate
Reflux (Low)
Mercuric Nitrate
Ion
Chromatography
Titration
Colorimetric
Visual
Comparison
Pyrtdlne-Barbituric
Acid, Colorimetric
Chlorination-
Colorimetric
Distillation-
Electrode
Electrode Ion
Chromatography
EDTA Titration
Calculation
2320
5220
5220
4500-CI"
4500-CI"
4500-Cr
2120
4500-CN"
4500-CN.
4500-F
4500-F
2340
.
310.1
405.1
200,7
300.0
410.1
410.2
325.3
300.0
330.5
110.2
110.3
335.2
335.1
340.2
340.2
300.0
130.2
Date: 2/28197
Section 9.0
Revision 2.0
Page 18 of27
D1067
D1252
D512
D512
D2036
D2036
D1179
01179
D1179
01126
6010
9252
9010A
9012
9010A
9012
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Hardness, Calcium
Hardness, Calcium
Calculation
lodine(ide)
Nitrogen, Ammonia
Kjeldahl
Nitrate
Nitrite
Nitrite
Organic
Oil and Grease
pH (Hydrogen Ion)
Phenol
Phosphorus
Total
Ortho
Silica,
Dissolved
I :\lqaprevalsect9.doc
Table 9.2 (cont.)
EDTA Titration
Ion Chromatography
Distillation Titration
Potentiometric
Digestion/Distillation
Automated Cadmium
Brucine Sulfate
Ion Chromatography
Automated Cadmium
Ion Chromatography
Spectrophotometric
Kjeldahl-NH3
Kjeldahl-
Potentiometric
Soxhlet
Partition-Gravimetric
IR
Electrode
Distil)ation-Extraction
Colorimetric
Persulfate Digestion
Ascorbic Acid Reduc.
Ascorbic Acid Reduc.
Molybdosilicate
ICP
3111
4500-NH3
4500-N organic
4500-N03
4500-N03
4500-N02
4500-N organic
55208
55208
4500-H+
4500-P
4500-P
4500-S1
242.1
200.7
300.0
350.2
350.3
351.3
353.2
352.1
300.0
353.2
300.0
354.1
351.3
351.4
413.1
413.2
150, 1
420.1
365.2
365.2
370.1
200.7
Date: 2/28/97
Section 9.0
Revision 2.0
Page 19 of27
D511
D3590
D3867
D091
D3867
D3590
D1293
D1783
D515
D515
D859
9200
9070
9071
9040A
9065
Table 9.2 (cont.)
Specific Conductance Meter 2510
Sulfate Ion Chromatography 4500-S04
2"
Turbidimetric
Sulfide Colorimetric 4500°S2"
Titration 4soo-s2•
Sulfite Titration 4500-sot
Surfactants Methylene Blue 5540
(MBAS)
Turbidity Meter 2130
:~qaprevalsect9.doc
120.1
300.0
375.2
375.4
376.2
377.1
425.1
180.1
Date: 2/28/97
Section 9.0
Revision 2.0
Page 20 of 27
D1339
D2330
D1889
9030A
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Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium,
Total (Hexavalent)
Cobalt
Copper
Iron
:~qapreva\soct9.doc
Table 9.2 (cont.)
AA-Direct Aspiration 3111
AA-Furnace 3113
ICP-AES
AA-Direct Aspiration 3113
AA-Furnace 3113
ICP-AES
AA-Furnace 3313
ICP-AES
AA-Direct Aspiration 3110
AA-Furnace 3113
ICP-AES
AA-Direct Aspiration 3110
AA-Furnace 3113
ICP-AES
AA-Direct Aspiration 3110
AA-Furnace 3113
ICP-AES
AA-Direct Aspiration 3110
AA-Furnace 3500-Ca
ICP-AES
AA-Direct Aspiration 3110
AA-Furnace 3113
ICP-AES
Colorimetric 3500-Cr
MIBK Extraction
AA-Direct Aspiration 3110
AA-Furnace 3113
ICP-AES
AA-Direct Aspiration 3110
AA-Furnace 3113
ICP-AES
I
AA-Di~ect 3110
AA-Furnace 3113
ICP-A$S
!
Date: 2/28/97
Section 9.0
Revision 2.0
Page 21 of 27
202.1
202.2
200.7
204,1
204.2
200.7
206.2
200.7
208.1
208.2
200.7
210.1
210.2
200.7
213.1
213.2
200.7
215.1
215.2
200.7
218.1
218.2
200.7
219.1
219.2
200.7
220.1
220.2
200.7
236.1
236.2
200.7
7020
60·10A
' 7040
7041
6010A
7060A
6010A
7080A
7081
6010A
7090
7091
6010A
7130
7131A
6010A
7140
6010A
7190
7191
6010A
7196A
7197
7200
7201
6010A
7210
7211
6010A
7380
7381
6010A
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Potassium
Selenium
Silica
Silver
Sodium
Strontium
:\fqapreva\sed9.doc
Table 9.2 (cont.)
AA-Direct Aspiration
AA-Direct Aspiration
ICP-AES
AA-Direct Aspiration
AA-Furnace
ICP-AES
AA-Cold Vapor
Automated Cold Vapor
AA-Direct Aspiration
AA-Furnace
AA-Direct Aspiration
AA-Furnace
ICP-AES
AA-Direct Aspiration
ICP-AES
AA-Furnace
ICP-AES
ICP-AES
AA-Direct Aspiration
AA-Furnace
ICP-AES
AA-Direct Aspiration
ICP-AES
AA-Direct Aspiration
ICP-AES
3500-Li
3111
3111
3113
3112
3111
3113
3111
3113
3111
3113
303A
3113
3111
3111
Date: 2/28/97
Section 9.0
Revision 2.0
Page 22 of 27
242.1
200.7
243.1
243.2
200.7
245.1
245.2
246.1
246.2
249.1
249.2
200.7
258.1
270.2
200.7
200.7
272.1
272.2
200.7
273.1
200.7
200.7
6010A
7450
6010A
7460
7461
6010A
7470A
7471A
7480
7481
7520
6010A
7610
6010A
7741A
7740
6010A
6010A
7760A
7761
6010A
7770
6010A
7780
6010A
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Thallium
Tin
Titanium
Vanadium
Zinc
:llqaproval.sect9.doc
Table 9.2 (conl)
AA-Direct Aspiration
AA-Furnace
ICP-AES
AA-Direct Aspiration
AA-Furnace
ICP-AES
AA-Direct Aspiration
AA-Furnace
ICP-AES
AA-Direct Aspiration
AA-Furnace
ICP-AES
AA-Direct Aspiration
AA-Furnace
ICP-AES
3111
3113
3111
3113
3111
3113
3111
3113
3111
3113
Date: 2/28/97
Section 9.0
Revision 2.0
Page 23 of 27
279.1
279.2
200,7
282.1
282.2
200.7
283,1
283,2
200.7
286.1
286,2
200.7
289,'I
289,;!
200.7
7840
7841
6010A
7870
6010A
6010A
7910
7911
6010A
7950
7951
6010A
3. Wastes & Oil Analysis
%Ash
Density
Flash Point
Closed Cup
Free Liquids
Leach Test. EP
Toxicity
Sulfide, Total
Reactive
pH
Specific Conductance
Specific Gravity
Cyanide, Total
Amenable
Reactive
TCLP
:~qapreva\sect9.doc
Gravimetric
Gravimetric
TAG
Paint Filter
Extraction
ntration
Titration
Electrode
Meter
Mass &
Displacemen
t
Distill -Color
Chlorination-
Colorimetric
Purge-Color
Leach
Table 9.2 (cont)
2540
2710
2710
D93-80
261.23
261.23
40CFR268
Date: 2128/97
Section 9.0
Revision 2.0
Page 24 of27
1010
9095
1310A
9030A
Chapter 7-7.3.4.2
9040A
9050/9045B
9010A
9010A
Chapter 7-7.3.3.2
1311
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Table 9.2 (cont.)
6. Ust of sample Preparation Methods
1311 TCLP
1312 Synthetic precipitation leaching procedure
3015 Microwave dig. aqueous
3051 Microwave dig. sludges, oil soil
3510 Separatory Funnel Liquid -Extraction
3520 Continuous Liquid -Extraction
3540 Soxhlet Extraction
3541 Automatic soxhlet extraction
3550 Sonication Extraction
3640 Gel Permeation Chromatography
3580 Waste Dilution
3630 Silica gel
3660 Sulfur clean up
5050 Bomb combustion. method for T. Halides
5080 Purge and Trap
Date: 2/28/97
Section 9.0
Revision 2.0
Page 25 of 27
3005 Acid Digestion of Waters for Total Recoverable or Dissolved Metals
for Analysis by
Flame AA or ICP
3010 Acid Digestion of Aqueous Samples and Extracts for Total Metals
for Analysis by
Flame AA or ICP
3020 Acid Digestion of Aqueous Samples and Extracts for Total Metals
by Furnace AA
3050 Acid Digestion of Sediments, Soils, and Sludges
7. Screening Methods
3810 Headspace
3820 Hexadecane extraction and screening of purgeable organics
8. Qllm
40 CFR 261
40 CFR 261
40 CFR 261
40 CPR 261
NIOSH 0600
NIOSH 0500
NIOSH 7500
Characteristic of lgnitability
Characteristic of Corrosivity
Characteristic of Reactivity
TCLP
Nuisance Dust, Respirable
Nuisance Dust, Total
Respirable Silica (XRD)
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Table 9.2
References
Date: 2/28/97
Section 9.0
Revision 2.0
Page 26 of27
1. Handbook for Analytical Quality Control in water and Wastewater Laboratories. u.s. EPA
· 600/4-79-019, March, 1979.
2. Federal Register, 40 CFR Part 136, October 26, 1984.
3, Test Methods for Evaluating Solid Waste. Physical/Chemical Methods. SW-846. 3rd
Edition & Final Updates One and Two, U.S. EPA, revised Sept., 1994.
4. Quality Assurance of Chemical Measurements, Taylor, John K.; Lewis Publishers. Inc.
1987.
5. standard Methods for the Examination of Water and wastewater, APHA, AWWA, WPCF:
18th Edition, 1992.
6. N!OSH Manual of Analytical Methods, U.S. Department of Health, Education, and Welfare;
Second Edition. 1977.
7. Methods for Non-conventional Pesticides Chemicals Analysis of Industrial and Municipal
Wastewater, Test Methods, EPA-440/1-83/079-C.
8. Methods for Chemical Analysis of Water and Wastes. EPA-600/4-79--020, 1983,
9. The Determination of Inorganic Anions In Water by Ion Chromatography -Method 300.0
Test Method, EPA-600/4-84-017. March, 1984.
10. Environmental Measurements Laboratory <EMU Procedures Manual-HASL-300, us
DOE, February, 1992.
11. Requirements for Quality Control of Analytical Pata. HAZWRAP, DOE/HWP-65/R1, July.
1990.
12. Requirements for Quality Control of Analytical Data for the Environmental Restoration
Program. Martin Marietta, ES/ER/TM-16. December. 1992.
13. Quality Assurance Manual for Industrial Hygiene Chemistry. AIHA, 1988.
:~qapreva\sect9.doc
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Date: 2/28/97
Section 9.0
Revision 2.0
Page 27 of 27
Table 9.3 BFB Key Ions and Ion Abundance Criteria
Mass SW-846, Method 8240B
50 15-40% of mass 95
75 30-60% of mass 95
95 base peak, 100% of rel. abundance
96 5-9% of mass 95
173 less than 2% of mass 174
174 greater than 50% of mass 95
175 5-9% of mass 174
176 95-101 % of mass 174
177 5-9% of mass 176
CLP Statement of Work -VOA
8-40% of mass 95
30-66% of mass 95
base peak, 100% rel. abundance
5-9% of mass 95
less than 2% of mass 17'4
50-120% of mass 95
4-9% of mass 17 4
93-101% of mass 174
5-9% of mass 176
Table 9.4 DFTPP Key Ions and Ion Abundance Criteria
Mass SW-846, Method 8270B
51 30-60% of mass 198
68 <2% of mass 69
69 N/A
70 <2% of mass 69
127 40-60% of mass 198
197 <1% of mass 198
198 base peak, 100% rel. abundance
199 5-9% of mass 198
275 10-30% of mass 198
365 <1 % of mass 198
441 Present but less than mass 443
442 <40% of mass 198
443 17-23% of mass 442
CLP Statement of Work -SV
30-80% of mass 198
<2% of mass 69
Present
<2% of mass 69
25-75% of mass 198
<1% of mass 198
base peak, 100% rel. abundance
5-9% of mass 198
10-30% of mass 198
<D.75 of mass 198
Present but less than mass 443
40-11-% of mass 198
15-24% of mass 442
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10.0 DATA REDUCTION, VALIDATION AND REPORTING
Date: 12/22/95
Section 1 o. O
Revision 0.01
Page 1 of 8
Data reduction, validation and reporting describes the processes that result in the delivery of quantitative analytical data to the data user. These processes include calculation of raw data into final concentration units, reviewing results for accuracy and assembly of the technical report contents for delivery to the data user.
All analytical data generated within the Pace laboratories undergo a well-defined, well-documented multi-tier review process before being reported to the client. The following describes procedures employed at Pace for translating raw analytical data into accurate, finished sample reports and data storage. Figure 10.2 shows schematically the sample flow through the laboratory. while Figure 10.3 shows the parallel flow of information concerning the sample analysis and reporting.
10.1 DATA REDUCTION
When primary analytical data, otherwise known as "raw data." are manually generated, the data are recorded either in bound logbooks with prenumbered pages or on preprinted forms. Records of analysis indicate the method used, raw data, calculations, and final· results. Entries are made in black ink and are initialed and dated by the individual who makes the entry. It is acceptable to initial and date once for an entire page. Errors are corrected by drawing a single line through the entry; this change is initialed and dated by the individual who makes the change. Raw data may not be obscured in any way. The use of white-out is prohibited on all raw data. including instrumental hardcopy.
All data generated by Pace are reviewed by designated, trained personnel. The analysts who acquire the data are responsible for initial on-line checks for compliance to the analytical requirements. After a sample batch is acquired, the data review procedure includes data interpretation and quantitation, inspection of quality control data against criteria, data reduction, narrative or comments writing, and ensuring that the data package includes all required analytical and quality control results, raw data an_d laboratory chronicles. The analyst who completes the analysis assembles all relevant raw data and results together with chromatograms, strip chart recordings, instrument settings and other information essential to data interpretation. For data which are reduced by manual calculations, the calculations are documented in a laboratory notebook or on an analyst's · worksheet. The results are transferred to a standardized laboratory reporting form which has been approved by the appropriate Group Supervisor and Laboratory Operations Manager. Reporting forms include at a minimum the sample identification number, the date analyzed. the result expressed per unit volume, the method reference and the analyst's initials. From the reporting forms, the results are entered into the LIMS.
10.2 DATA VALIDATION
Data validation is the process of examining data and accepting or rejecting it based on pre-defined criteria. Pace data review personnel use the following .. criteria to validate laboratory data:
:\Jqapreva\sect1 O.doc
• Use of approved analytical procedures.
• Use of properly operating and calibrated instrumentation.
Date: 12/22/95
Section 1 O. O
Revision 0.01
Page 2 of 8
• Precision and accuracy comparable to that achieved in similar analytical programs.
Analysts performing the analysis and subsequent data reduction have the primary responsibility for the quality of the data produced. The primary analyst initiates the data validation process by reviewing and accepting the data, provided QC criteria have been
met for the samples being reported. Data review checklists may be used to document the
data review process.
The completed data package is then sent to the Group Supervisor or designated reviewer.
The Group Supervisor provides a technical assessment of the data package and technical review for accuracy according to methods employed and laboratory protocols. This
involves a quality control audit for use of the proper methodology and detection limits,
compliance to quality control protocol and criteria, presence and completeness of required
deliverables, and accuracy of calculations and data quantitation. Group Supervisors also review analyst generated calculations.
For data which are reduced via computer, calculations are checked by the analyst (or·
designee) assigned to this task at a frequency designed to assure that the data manipulations are valid. This data validation step is documented by the analysts' initials on the hardcopy of the raw data. The results are either manually transferred to a standard
reporting form or reported via computer generation of forms.
Once the data have been technically reviewed and approved, authorization for release of the data from the analytical section is indicated by initialing and dating the data review
checklist or otherwise initialing and dating the data. The Group Supervisor drafts any
narrative comments if required by the Quality Assurance Project Plan, and forwards the
report and the data package to the Reporting Department.
Each data package is reviewed by designated reporting personnel to ensure compliance
with client orders by reviewing on-line input in the Pace computer tracking system. The
laboratory data are assembled in the client's technical reports. Reports are reviewed for completion prior to copying and binding. Figure 10.1 provides a summary listing of staff responsibilities concerning data generation, review, validation and reporting. The Reporting Department assembles the data with other data from the sample set, generates
the final report, checks for transcription errors, and provides the final report to either the
Laboratory Operations Manager, Project Manager, or an appropriate designee for final
signature.
The Operations or Project Manager examines the report for method appropriateness,
detection limits and whether or not QC criteria were satisfied. Any deviations from the
referenced methods are checked for documentation and validity, and QC corrective
actions are reviewed for successful resolution. The Operations or Project Manager or an appropriate designee signs the completed report prior to its release to the client.
:\lqapreva\sect1 O.doc
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Date: 12/22/95
Section 10.0
Revision 0.01
Page 3 of 8
The Operations Manager may delegate the final review and signing of reports as
necessary.
Use of checklists ensure that all data are systematically handled and no steps are omitted.
Checklists are reviewed and are retained and accessible should they need to be
referenced at a later date. The data and deliverables are checked and signed during
processing procedures and then systematically filed by reference identification numbers.
10.3 DATA REPORTING
All data segments pertaining to a particular Pace Laboratory Number are channeled to the
Reporting Department for assembly into the final report format and generation of the
analy1ical narrative. All points mentioned during technical and QC review are included in
the narrative if it is deemed to impact the quality of the data.
The final report is given to either the Laboratory Operations Manager, Project Manager or
an appropriate designee for final review and release. After verifying the report's
completeness and accuracy, the Operations or Project Manager signs the cover letter or
authorization line within report indicating acceptance of the report.
Technical reports are prepared to include the components or level of deliverables that are
requested by clients for samples or projects, or contractually required. The standard Pace
commercial report to the client consists of the following sections:
1) A cover letter
2) A technical narrative (when necessary)
3) Sample receipt condition report (information may be included on C.O.C. form)
4) Sample ID table
5) Sample results
6) Chain-of-Custody forms
The narrative briefly describes the condition of the samples upon receipt, sample holding
time performance, instrument calibration information, and the quality control results. Any
discrepancies discovered and matrix problems encountered are also addressed in this
section.
The sample results are tabulated by sample number and parameter. Pace number, client
identification, and dates of sample preparation and analysis are presented along with the
observed concentrations for each parameter analyzed and corresponding reporting limits.
Pace prepares technical reports that include full data deliverables for validation purposes,
and lesser, abbreviated reports. Full deliverables include all raw and processed data
applicable to the analyses performed. Pace prepares single sample technical reports or
multi-sample report packages. The multi-sample technical reports contain results for a
sample delivery group (SDG) or other client or laboratory defined sample set. Pace
recommends multi-sample reports when full deliverables packages are required.
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Section 10.0
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The Pace laboratory prepares electronic data deliverables (EDD) as required for contracts
and upon client request.
10.4 DATA ARCHIVE
Each data report which supports the analytical process for all samples received by the
laboratory is thoroughly reviewed for completeness and accuracy. After the technical
review it is routed to the Reporting Department for assembling the final report for
submission ·to the client. The report is approved, signed, and submitted.
Sufficient records are retained to recreate analytical events at the laboratory. Pace will
retain analytical data for five years and financial data for three years relating to services
performed following the transmittal of the final report to the client. Certain contractual
arrangements or regulatory requirements for specific projects may shorten or extend the
records retention period stated here. Records are catalogued and maintained in limited
access areas. Data archive and storage is managed by designated individuals who
control the access to stored information. One copy of the report remains with all the raw
data which is stored in the data archives under the control of the QA Department or other
designated group.
All information retained at the Pace facility is stored in secured areas. The Data Archivist
has oversight responsibility for the data archive ensuring the continued integrity of all
documentation generated in support of laboratory analyses. All hard-copy information is
stored on-site at the laboratory or off-site at a commercial document storage facility
equipped with a professional security system. All electronic data is stored on-site at the
laboratory or off-site at a commercial document storage facility equipped with a
professional security system and a controlled environment suitable for storage of magnetic
media.
The archive room is a secure storage area· with limited access to non-authorized
personnel. Sign-out procedures are in place where every document removed from the
archive room must be signed out by authorized personnel.
A copy of the report or summary of samples classified as hazardous is forwarded to the
Hazardous Waste Coordinator or designee for use in characterizing the samples for
ultimate disposal.
Pace reserves the right to transfer hard-copy information onto microfilm or write-
protected electronic media. Pace reserves the right to store information in hard-copy
files, on magnetic media and/or microfilm. The information is retained and accessible
for a minimum of seven years unless otherwise specified through a client specific
contract.
10.5 RESPONSE TO INQUIRIES
The Pace laboratory which conducted analyses for the client recognizes the importance
of its timely response to inquiries regarding the laboratory's work for samples and
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Section 10.0
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projects. The laboratory will respond to inquiries as rapidly as possible as part of its
corrective action plan. The Pace laboratory which originally received samples from the
client should be considered the primary contact for all data inquiries when subcontract
or other Pace laboratories are used for analyses.
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FIGURE 10.1
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Section 10.0
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Analytical Data Review Process, Pace Analytical Services, Inc.
Analyst
Supervisor
Manager
Data Review/Reporting
Quality Assurance Office
Project Manag_er
Responsibilities
Sample analysis LIMS* entry and generation
Data review -1st level (bench)
Control charting -real time
Narrative notes
Discrepancy initiation
Provide copies of log books, as necessary
Oversee daily analytical activities
Review control chart comments daily
LIMS data entry and validating
Draft and review of narrative
Supervise contractual and technical compliance
Discrepancy review
Review quality control daily (calibrations, etc.)
Sign-off case narrative
Ensure program compliance
Review discrepancies requiring manager resolution
Technical conference calls with client
Ensure technical validity of data
Generate forms package
Final data review and validation
Prepare package and paginate
Electronic deliverables generation
Maintain data package files
10 percent contractual compliance review (data packages)
C_ustody when required;
Calculations;
-Methods criteria;
QC criteria;
Forms; and
Control charting.
Review narratives for accuracy
Review packages for completeness and quality
Cover letter
Collate organic and inorganic packages
Client/laboratory liaison
Deliver package to client
Note: *Laboratory Information Management System
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FIGURE 10.2
Laboratory Sample Flow Schematic
Samples 4 ---
Samples In ~~ ...----------
Storage (Cooler) ~
~ Sample Prep.
I Check-In J
Sample Analysis
~---'-----~.--'---~
Data Production I Control Ch rts I
_,,,om D:::noy ac ""z___/ I a . ~
Data A/9 Entered Into LOMS • • \
Data Validation I Quality Assurance Officer I
Mll!yst/SuperviSOI' Valida!H Both QC & Sample Resits
Report Generation
Report Review
Project Manager/Dept Manager Review/Sign
~---'---~....-----...i-------~ Report Sent to Client j Samples Returned to Client
"--....1 Sample Disposal I
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FIGURE 10.3
Information Flow Schematic
Samples4' '-.... ~--~ Real . I Check-In I ~
/I ~
Samples In g_ ~ ~-·-~ Project Manaoe, Storage (Cooler) ~ NIGHTL y Clienl File
Modified
U>MS
To Pel'fom,
Analyt,is
Subsets
Outstanding
Analysis
Sutm,ts
Permanent Rll<Xlfd Bench Analyst (available Maf\llQ8fflenl ·-..:a A)~.SIS RESULTS
TolFrom Storage L . t ~
RelUlts Entry ,.-:-... _.,_--· VIDEO DISPLAY
Validation List Outstanding
Analysis
Another Bench Analyst
(available on request• 2ncl shift)
Subsets
Management
Valicsate Results ~ RES UL TS (NigN!y OnlrJ _...,. N-/Changed A<:coun1ing
Batch LOMS (NoontNighl)
v""'"" Lid
Cloud _,
DISK Projects ~
-------.._I ,_""' I ·-lt•m• =11"1-.oidnQ
"""""' ,_ ........ -Nllt,tkll ,.,_., o.ta Pl'Odudlon Refl(lrtS control Ub lnwldng Clltrt OP Rcpon, Ult, ln-.oidng Cltrt.
(Nlglllyont,) Con1rOI (Nlgf'CIJ~
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11.0 QUALITY CONTROL PROCEDURES
Date: 12/22/95
Section 11
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A quality control (QC) program is a systematic process that controls the validity of analytical results by measuring the accuracy and precision of each method and matrix, developing expected control limits, using these limits to detect errors or out-of-control events, and requiring corrective action measures to prevent or minimize the recurrence of these, events. QC procedures are implemented to ensure that sample data meet the quality objectives of the laboratory and the client. An effective QC program must be able to control the quality of the data through the monitoring of QC indicators. Criteria frequently applied to environmental QC data include measurements of accuracy and precision. Precision measures the randomness associated with an analytical measurement and reflects the inherent variability in that measurement system. Accuracy reflects the degree to which the measured value approximates the actual or "true" value for a given parameter and reflects the influence of systematic biases in the measurement. Thus, the "quality" of QC data can be said io be a measure of both the randomness and biases in a specific measurement system.
This section addresses the specific QC procedures applied to representative analytical methods performed at Pace. Table 11.1 presents method-specific information about QC procedures, acceptance criteria, and required corrective actions for the various analysis types.
11.1 ACCURACY AND PRECISION MEASUREMENT CONVENTIONS
The results of quality control samples created in the laboratory represent estimates of accuracy and precision for the preparation and analysis steps of sample handling. This section describes the quality control information provided by each of these analytical measurements. Information on the procedures to follow in preparation of the samples or spiking solutions is described for each method and matrix in the respective method Standard Operating Procedure.
Method Blank
A method blank is a volume of deionized and/or distilled laboratory water for water samples, or a purified solid matrix for soil/sediment samples, carried through the entire analytical procedure. The volume or weight of the blank must be approximately equal to the sample volume or weight processed. Analysis of the blank verifies that method interferences caused by contaminants in solvents, reagents, glassware, and other sample processing hardware are known and minimized. Optimally, a method blank should contain no greater than five times (5X) the method detection limit, or reporting limit where applicable, for common laboratory solvents and phthalate esters; less than the detection (or reporting) limit for all other parameters unless otherwise specified in the method or project QA plan. Results of method blank analyses are maintained with other QC data in the respective laboratories. If requested by the client, this data will be included in the report.
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Method Blank Frequency
Organics: The laboratory shall prepare and analyze QM laboratory reagent blank
(method blank) for each group of samples of a similar matrix (for water
or soil samples), extracted by a similar method (separatory funnel,
continuous liquid-liquid extraction, or sonication), and a similar
concentration level (when low vs. medium level analyses are available)
for:
• every 20 samples, or
• whenever samples are extracted
-whichever is more frequent.
lnorganics: At least QM preparation blank (method blank), consisting of blank
reagent water processed through each sample preparation and analysis
procedure, shall be prepared and analyzed with every group of 20
samples, or with each batch (a group of samples prepared at the same
time, e.g. daily) of samples digested, extracted, prepared or directly
analyzed, whichever is more frequent.
Accuracy Measurements
Laboratory Control Samples (LCS) consist of aliquots of laboratory blank matrices · (water, sand, etc.) spiked with analytes of interest. LCSs for methods with extensive
lists of analytes that may interfere with one another may include a limited number of analytes, but the analytes included must be representative of as many analytes as is practical. In the case of metals analysis, all analytes of interest must be included. Laboratory pure water is used to prepare most LCSs for methods for analysis of water.
Highly characterized solids, where available, are used for LCSs for methods for analysis of solids. Where no such solid LCS is available, spiked laboratory pure water
or spiked reagent blanks may be substituted. LCSs provide an estimate of bias based
on recovery of the compounds from a clean, control matrix. They provide evidence that the laboratory is performing the method within accepted guidelines without
potential non-matrix interferences. They are prepared at a rate of one per batch of twenty or fewer samples.
For tests that are performed infrequently, an LCS shall be analyzed at least monthly if
the number of samples is less than 20. This monthly requirement shall NOT apply to
low-volume tests for which state certification is not sought, or for tests expected to be
performed solely as part of a special project, or for tests involving study specific
matrices other than water, soil, sludges and oils.
Matrix Spikes/Matrix Spike Duplicates are similar to Laboratory Control Samples except the analytes used for spiking are added to a second and third separate aliquot from the same container of selected client samples in a batch of analyses. They
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enable one to assess sample matrix effects and field conditions. MS/MSDs are routinely prepared at a frequency of 5% (one set per twenty samples) when adequate sample volume is provided or once every 14 days, which ever is more frequent. An LCS/LCSD pair shall be substituted when sufficient sample volume is not available to prepare an MS/MSD sample set.
Surrogates provide an estimate of bias based on recovery of chemically similar compounds which are not expected to be in the sample, to the compounds of interest for each sample, incorporating sample matrix effects and field conditions. Surrogates are added to all samples analyzed by GC/MS and certain GC analyses prior to sample preparation.
An Internal standard is an analyte that has the same characteristics as the surrogate, but is added to each sample in a batch, just prior to analysis and is used for quantitation. It corrects for bias or change in instrument performance from sample to sample, incorporating matrix effects associated with the analytical process only.
Accuracy is expressed as % Recovery. For LCSs, Surrogate, and Blank Spike samples, percent recovery (%R) is calculated as:
Where:
%R =(SR/ SA) x 100
SR is the concentration determined
SA is the concentration spiked
For the matrix spike samples, the percent recovery is calculated as:
Where:
%R = (SSR-SR)/SA x 100
SSR is the spiked sample determined result
SR is the original sample determined result
SA is the amount of spike added (expected)
Precision Measurements
A Sample Duplicate is a sample that has been homogenized and split into two equal portions before the method sample preparation process. It measures sample precision associated with the preparation through analysis and is prepared and analyzed at a rate of one per batch or one per twenty samples or once every 14 days whichever is greater in the inorganic laboratories. For organic analyses the MS/MSDs fulfill this function and provide a measure of overall precision.
The comparison of the values determined for a sample and its duplicate (MS/MSD) is expressed as relative percent difference (RPO). This calculation is as follows:
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IS-DI
RPD = ---x 100
[(S+D)/2]
Date: 12/22/95
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The vertical bars in the above equation indicate the absolute value of the difference,
hence RPO is always expressed as a positive value.
11.2 CONTROL CHARTS
Control charts are quality control tools which graphically display the QC parameters
over time. Accuracy (Figure 11.1) and precision (Figure 11.2) control charts are
generally maintained for each method; however, for certain methods tabulated control
limits are used to monitor acceptability of quality control measurements. Each chart
can be broken into three parts: sample identification, sample response/calculation,
and graphic representation (the plot).
11.2.1
11.2.2
Accuracy
Accuracy charts are maintained for Surrogate and Laboratory Control
Sample recovery. Each sample is identified by the date it was analyzed
and its Pace sample number.
The percent recovery is plotted onto the graph where:
The x-axis is the sample ID.; and
• The y-axis is the range of percent recoveries.
Precision
In cases where precIsIon charts are maintained, the relative percent
difference is plotted on the graph where:
The median, zero, represents 0% difference
• The x-axis is the number of data points per chart; and
• The y-axis is the range of relative percent differences.
Both samples are identified by the date(s) analyzed and their Pace number.
11.2.3 · Limits
:\lqapreva\sect11.doc
Both upper and lower warning limits and upper and lower control limits are
established to interpret performance. Warning limits express a _narrower
confidence interval and are used to warn the analyst or supervisor of
possible system inconsistencies or failures, before an out-of-control event
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occurs. Control limits express the outer limits of accepted method
variability. Control limits and warning limits are reviewed periodically
against performance. Based on statistical considerations, an evaluation is
made to determine whether the control limits need to be revised.
warning Limits
When not othe_rwise mandated by the method, Pace adopts warning limits
to be the mean +/-2 standard deviations or a 95% confidence interval,
where:
1 n
Mean X = L Xi
n I= 1
Standard Deviation
n n
z: X; 2 -(Z:X,)2/n
i=1 i=1
s = or
:\lqapreva\sect11.doc
n -1
In this equation,
control Limits
n -1
= population size
= ith observation in the sample
= sample mean
Unless otherwise stipulated in a particular method or program, acceptance
limits (control limits) will be statistically derived from laboratory generated
data. Control limits will be based upon +/-3s (i.e., 99% confidence interval)
from the mean and warning limits established at +/-2s from the mean (i.e., 95% confidence interval). All data used to generate these limits will
undergo a Dixon Outlier test to reject outlier data points. The use of
hardcoded limits nonstatistically derived from current laborato,y generated
data (e.g., CLP limits) shall be limited to programs which specifically permit
their application. Control limits shall be updated annually at a minimum and
at a maximum interval of once every 20 data points generated. At a
minimum, tabulated control limits shall be available and followed by all
analysts performing the associated test. However, control charts are the
preferred mechanism for monitoring quality control measurements on a real
11.3
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time basis. Where interlaboratory expected ranges have been determined, Pace's goal is for their control limits to fall within these multi-laboratory expected ranges for that method.
Suspicious/Out-of-Control Events
Plotting and connecting successive data points on control charts enables the laboratory to detect many types of suspicious and out-of-control situations. These events can be caught by monitoring the following: outliers (suspicious and out-of-control), runs (suspicious), trends (suspicious), and periodicity (suspicious).
Excursions
There are two types of excursions: any particular point that falls outside the control limits or any point that falls outside the warning limits. A point that falls outside the control limits is classified as an out-of-control event; a point that falls outside the warning limits is classified as a suspicious event.
Runs
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A run is defined as a series of points that line up on one side of the central I line (the mean). Any run that has a length of seven points is indicative of a potential abnormality in the process, a suspicious event. A run can suggest 1 several potential problems such as a leak in the system, elevated contamination, or incorrect dilutions of standards.
Trends I
A trend is defined as a series of points that are marked by an unbroken rise II or fall. Any trend with a length of five points (may vary up to seven points) II is classified as a suspicious event. A trend may indicate a change in instrument sensitivity due to a dirty source or injection port or standard degradation, to name a few. I
Periodicity
Periodicity is a term used to describe a recurring pattern of change over equal intervals. This occurrence may be of any length or amplitude; thus, · careful observation of the control chart is necessary.
QC BATCH DEFINITION
Organics: The laboratory will perform:
I
• One spiked sample analysis (matrix spike), and
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• One duplicate spiked sample analysis (matrix spike duplicate)
for each group of samples of a similar matrix (for water or for soil samples) and
concentration level (when low vs. medium level analyses are available) for:
every 20 samples, or .•
each 14 calendar day period during which field samples were received
(said period beginning with the receipt of the first sample by the
laboratory),
whichever is more frequent.
• One spiked laboratory control sample (LCS) must be processed each time
a group of 20 samples or less are extracted, prepared, or directly analyzed
(Note: an organic LCS is processed at the same frequency as a laboratory
reagent blank (method or prep blank).
lnorganics: The laboratory will perform:
• One spiked sample analysis (matrix spike), and
• One straight sample duplicate analysis {duplicate)
for each group of samples of a similar matrix (for water or for soil samples) and
concentration level (when low vs. medium level analyses are available) for:
every 20 samples, OR
each 14 calendar day period during which field samples were received
(said period beginning with the receipt of the first sample by the
laboratory),
whichever is more frequent.
.• One spiked laboratory control sample (LCS) must be processed each time
a group of 20 samples or less are digested, extracted, prepared, or directly
analyzed (Note: an inorganic LCS is processed at the same frequency as a
laboratory reagent blank (method or prep blank).
The frequencies listed above for matrix spiking applications are to be followed
regardless of whether or not clients have committed to "paying for QC." Laboratory
operations must make a conscious effort to periodically request or collect as part of a
field sampling event (i.e., sampling performed by Pace personnel) sufficient quantities
of samples for those analyses (e.g., method 418.1 TPH) that are routinely analyzed
under QC batches that do not contain matrix spike applications because "insufficient
sample vol4me was received." Samples selected for QC which contain limited volume
or quantity should be evaluated based upon the type of analysis to be performed to
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Section 11
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establish whether modifications can be made to allow for using smaller initial sample
size than normally applied. For example, most organic extraction procedures require
that a 1 liter sample size be analyzed for .aqueous samples. However, often only a
single 1 liter sample bottle remains following the extraction of the safT]ple thus leaving
insufficient volume to perform both an MS and MSD on the sample because each
normally require a full liter of sample. In most cases, the usability of the QC data for
assessing the accuracy and precision of the analysis is not adversely impacted if the
remaining liter of sample is split into two 500 ml aliquots, spiked and carried through
the procedure. While following this modification would result in a two fold increase in
MDLs, since the spiked compounds are present at concentrations which are close to
the midpoint of the calibration curve, the elevated MDLs will have no effect on
determining recovery and RPO values. In this example, a further method modification
of concentrating the final volume of the MS/MSD extracts to 0.5 ml (versus the normal
1.0 ml final volume) would provide the 1000 fold concentration requirement of the
method. Any options, such as the example given above, contemplated for use to
overcome limited sample size when applying QC applications must be discussed with
clients prior to their implementation. Finally, for methods in which no similar technical
justification can be made for decreasing the initial sample size or changing the analysis ·
process, when none of the associated samples in a QC batch contain sufficient sample
volume or quantity to permit matrix spiking to be performed, laboratory control samples
should be analyzed in duplicate (LCS/LCSD) to afford assessment of both the
accuracy and precision of the test.
11.4 UTILIZATION OF QUALITY CONTROL DATA
The purpose for preparing and analyzing quality control samples is to demonstrate,
through the known entities, how accurate and precise the investigative sample data
are. Table 11-1 summarizes the quality control assessment criteria by matrix for the
most commonly used methods by Pace. Different criteria may be dictated by different
methods or by project QA plans.
11.5 SAMPLING QUALITY CONTROL
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Quality ·control is an integral part of sample collection as well as laboratory operations. I
Sample collection protocols must include checks to ensure that the sample collected is
representative of the site from which it was collected and free from collection-related
contamination or biases. Although different laboratory procedures will be used to I
analyze for the various parameters of interest, certain general QC procedures are
applicable to most sampling methods. QC procedures frequently applied in the field are
described below. The analysis types and frequency of collection for each of these field I
QC samples are detailed in each project's sampling and analysis plan (SAP).
11.5.1 Fjeld Blanks -Field blanks are QC samples consisting of blank water that are
prepared in the field. This type of QC sample serves to check for potential
contamination that may be present in the environment where field samples
are collected.
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11.5.2
11.5.3
11.5.4
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Trip Blanks -Trip blanks are similar to field blanks except that they are prepared in the laboratory before the sampling event. These blank samples accompany the other sample containers to the field and then accompany the collected samples back to the lab. Trip blanks serve to check for potential contamination that samples and sample containers may be exposed to during transportation to and from the field.
Equipment Rinsate Blanks -These field QC samples consist of rinsates of the equipment used to collect field samples using blank water provided by the laboratory. Equipment rinsate blanks serve to check the adequacy of equipment cleaning between successive sample collections. · Inadequate cleaning of sample collection equipment after the collection of a sample could result in the contamination of the next sample collected.
Matrix Spike/Matrix Spike Duplicate Samples -At a minimum frequency of one set per 20 samples, split sample volumes are collected to be used for matrix spike (MS) and matrix spike duplicate (MSD) analyses by the · laboratory.
11.6 LABORATORY QUALITY CONTROL
In addition to the sampling-related QC procedures described above, additional QC procedures are performed in the laboratory as part of routine analytical protocol. These procedures are described below for representative analytical methods.
11.6.1
'.\lqapreva\sect11.doc
GC Methods
Analytical quality control procedures for GC analyses are described in Method 8000A of SW-846, 3rd Edition, Final Update 1 and 2, and the EPA CLP Organic SOW. They include the following:
• Initial demonstration of proficiency
• Retention time window determination
• Surrogate spiked sample analysis
• Method blank analysis
• Matrix spike/matrix spike duplicate analysis
• Laboratory control sample analysis
The application of each of these analyses is described below.
Initial Demonstration of Proficiency {SW-846) -Before sample analysis can begin, the laboratory must perform a one-time demonstration of the ability to generate data with acceptable accuracy and precision. This is accomplished by analyzing four aliquots of a QC check sample by the same procedure used to analyze samples. The calculated average recovery and standard deviation
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for each analyte of interest are compared to acceptance criteria provided in the specific SW-846 method. If the calculated accuracy and precision data are within acceptance limits, analysis of samples may proceed. If not, remedial action must be taken to improve system performance and the proficiency test must be repeated.
Retention Time Window Determination -Retention time (RT) windows are calculated for each target analyte peak(s) and for each GC column used for sample analysis. To establish RT windows, the laboratory measures the RTs of each analyte peak (or of each selected peak for multi-component analytes) from three analyses of the continuing calibration standard over a 72-hour period. The RT window is determined as .±3 times the standard deviation of the three measured RTs. Daily RT windows are established for each analyte peak using the RT in the daily calibration verification standard as the centerpoint of the window determined above. In successive continuing calibration standards, the RT of each analyte peak must fall within the prescribed RT window for the analysis sequence to continue. RT windows must be recalculated whenever a new GC column is installed.
Surrogate Spiked Sample Analysis -Surrogates are compounds that have similar chemical properties to analytes of interest except that they are not expected to occur naturally in environmental samples. The use of surrogate
compounds may be project dependent and limited by the ability to select a suitable surrogate for a particular analytical method. Representative surrogate compounds and surrogate recovery acceptance limits for GC methods are given in Section 5, Tables 5.1 to 5.4. For these methods, corrective action must be taken if the surrogate spike recoveries in any analysis fall outside the prescribed acceptance limits. Corrective actions include:
•
•
•
•
Checking for errors in the calculation or preparation of the surrogate
or standard solutions.
Checking instrument performance .
Recalculating the data and/or reanalyzing the sample or extract if any
of the above checks reveal a problem.
Re-extracting and reanalyzing the sample if none of the above are determined to be the problem.
Method Blank Analysis -For analysis by purge-and-trap methods, a method blank must be analyzed each day of analysis. For extraction methods (including methanol extraction of volatiles for purge-and-trap analysis), at least one method blank must be extracted and analyzed for each batch or sub-batch of samples extracted to demonstrate that both the extraction and analytical systems are free from contamination. Blank samples are carried through all stages of sample preparation and analysis. Lack of contamination is demonstrated if no target analytes are present at concentrations at or
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Section 11
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above their reporting limits (or contract required quantitation limits (CRQLs)
for CLP).
Holding Blanks -Holding or refrigerator blanks are prepared in the laboratory
and stored in the refrigerators where VOA samples reside. Holding blanks
are analyzed each week and are used to monitor the potential of laboratory
contamination.
Matrix Spike/Matrix Spike Duplicate Analyses -At a minimum frequency of one set per batch of up to 20 samples of similar matrix, replicate aliquots of one of the samples are spiked with a mix of target analytes and the resulting
matrix spike (MS) and matrix spike duplicate (MSD) samples are analyzed to evaluate the percent recovery of the spiked compounds. Representative
limits for percent recovery are shown in Section 5, Tables 5.1 to 5.4.
Recovery data falling outside the acceptance limits may indicate a problem in sample preparation or in the analytical system, or may be due to sample matrix interference. Analysis of laboratory control samples (LCSs) in
conjunction with MS/MSD samples aids in determining whether or not the · problem is sample matrix related. Acceptable recoveries of LCS spike analytes indicate that the analytical system is in control and that problems
with associated recoveries in the MS and MSD samples are likely due to
sample matrix interference.
Laboratory Control Sample Analysis -The laboratory control sample (LCS)
consists of a subset of target analytes of interest (typically the same as in the MS and MSD samples) spiked at concentrations in the mid-calibration range.
The LCS is prepared along with the samples for analysis and is used to verify that the analytical system is in control. LCS recovery data are plotted on blank spike control charts to monitor the analytical system for trends or
events that indicate a change in method/instrument performance.
11.6.2 GC/MS Methods
:\Jqapreva\seci11.doc
Analytical quality control procedures for GC/MS analyses are described in
methods 8000A, 8240B, and 8270B in SW-846 or in the EPA CLP Organic
SOW. They include the following:
• Initial demonstration of proficiency
• Mass spectrometer sensitivity check
• Daily GC/MS performance test
• Surrogate spiked sample analysis
• Method blank analysis
• Matrix spike/matrix spike duplicate analysis
• Laboratory control sample analysis
The application of each of these analyses is described below.
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I nitjal Demonstration of Proficiency (SW-846) -Before sample analysis can begin, the laboratory must perform a one-time demonstration of the ability to generate data with acceptable accuracy and precision. This is accomplished
by analyzing four aliquots of a QC check sample by the same procedure used to analyze samples. The calculated average recovery and standard deviation for each analyte of interest are compared to acceptance criteria provided in the specific SW-846 method. If the calculated accuracy and precision data are within acceptance limits, analysis of samples may proceed. If not, remedial action must be taken to improve system performance and the proficiency test must be repeated.
Mass Spectrometer Sensitivity Check -If the extracted ion current profile (EICP) area for any internal standard changes by more than a factor of two compared to the daily calibration verification standard, the mass spectrometer
must be inspected for malfunctions and corrective action taken. Samples analyzed while the system was malfunctioning must be reanalyzed.
Daily GC/MS Performance Tests -Each day that analyses are performed, the GC/MS system must be checked using bromofluorobenzene (BFB) for volatiles analysis or decafluorotriphenylphosphine (DFTPP) for semivolatiles analysis. The acceptance criteria presented in Section 9 must be met prior to performing any sample analyses. If all criteria are not met, the instrument must be retuned and the test repeated until all criteria are met.
Surrogate Spjked Sample Analysis -All samples are spiked with surrogate standards as described in the specific methods in SW-846 and the CLP SOW. The surrogate compounds and representative surrogate recovery
acceptance lim~s for GC/MS methods are shown in Tables 5.5 and 5.6. If the surrogate spike recovery in any analytical run is not within limits, the following
steps must be taken:
• Check for errors in the calculation or preparation of the surrogate or
standard solutions.
• Check instrument performance.
• Recalculate the data and/or reanalyze the sample or extract if any of
the above checks reveal a problem.
• Re-extract and reanalyze the sample if none of the above are
determined to be the problem.
Method Blank Analysis -For volatiles analysis by GC/MS, a method blank must be analyzed within each 12 hour run sequence. For semivolatiles analysis, at least one method blank must be prepared and analyzed for each batch or sub-batch of samples extracted, to demonstrate that both the extraction and analytical systems are free from contamination. Blank samples are carried through all stages of sample preparation and analysis.
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11.6.3
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Lack of contamination is demonstrated if no target analytes (with the exception of common laboratory solvents) are present at concentrations at or above their reporting limits (CRQLs for CLP). For volatile analyses, common laboratory contaminants, such as methylene chloride, acetone, 2-butanone, and toluene, must not exceed five times the CRQL for CLP or five times the reporting limit for SW-846. For semivolatile analyses, the concentrations of the most commonly encountered laboratory contaminants, phthalate esters, must not exceed five times the reporting limit or CRQL.
Holding Blanks -Holding or refrigerator blanks are prepared in the laboratory and stored in the refrigerators where VOA samples reside. Holding blanks are analyzed each week and are used to monitor the potential of laboratory contamination.
Matrix Spike/Matrix Spike Duplicate Analysis -

A

minimum of one set of matrix spike (MS) and matrix spike duplicate (MSD) samples is prepared for each analytical batch of up to 20 samples of similar matrix. Acceptance limits for percent recovery are shown in Section 5, Tables 5.5 and 5.6. Recovery data· falling outside the prescribed acceptance limits may indicate a problem in sample preparation or the analytical system, or may be due to sample matrix interference. Analysis of laboratory control samples (LCSs) in conjunction with MS/MSD samples aids in determining whether or not the problem is sample matrix related. Acceptable recoveries of LCS spike compounds indicate that the analytical system is in control and that problems with associated recoveries in the MS and MSD samples are likely due to sample matrix interference.
Laboratory Control Sample Analysis -The laboratory control sample (LCS) consists of a subset of the target analytes (typically the same as in the MS and MSD samples) spiked at concentrations in the mid-calibration range. The LCS is prepared along with the samples for analysis and is used to verify that the analytical system is in control. LCS recovery data are plotted on blank spike control charts to monitor the analytical system for trends or events that indicate a change in meth_od/instrument performance.
Metals Analysis
The quality control procedures applied to metals analysis by ICPS are described in SW-846 Method 6010A and in the CLP Inorganic SOW. Quality control procedures for atomic absorption analyses are described in SW-846 Method 7000 series and the CLP Inorganic SOW. These procedures include the analysis of:
• An initial calibration blank
• A continuing calibration blank
• A preparation blank
:\lqapreva\sect11.doc
• MS/MSD/duplicate samples
• An instrument check standard
• A laboratory control sample
• An interference check standard
Each of these analyses is described below.
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Initial Calibration Blank Analysis -Following the analysis of the initial calibration verification standard (ICV) and prior to the analysis of samples, an initial calibration blank (ICB) is analyzed to demonstrate that the analytical system is free from contamination. This blank analysis must be free from all elements of interest at or above the reporting limits (CRDLs for analysis by CLP protocol), or the instrument must be recalibrated before sample analysis may begin.
Continuing Calibration Blank Analysis -Following the analysis of each continuing calibration standard (CCV) in an analytical sequence, a continuing · calibration blank (CCB) is analyzed to demonstrate that the analytical system · is free from contamination throughout the course of that sequence. This blank analysis must be free from all elements of interest at or above the reporting limits (CRDLs for analysis by CLP protocol), or sample analysis must be discontinued and the previous 10 samples must be reanalyzed under a new calibration.
Preparaljon Blank Analysis -

A

preparation blank, containing all of the reagents and volumes used in the processing of samples and carried through the complete preparation and analysis procedure, is analyzed at a minimum
frequency of one per sample batch or sub-batch.· The preparation blank is analyzed to demonstrate that the sample preparation procedure is free from contamination. This blank must be free of all elements of interest at or above
the reporting limits (CRDLs for analysis by CLP protocol), or the entire sub-batch of samples must be reprepared and reanalyzed.
Laboratory Control Sample Analysis -Control samples may be obtained from commercial vendors or prepared from suitable reference materials, but must be prepared independently from the calibration standards. The LCS is prepared along with the samples for analysis and is used to verify that the analytical system is in control. LCS recovery data are plotted on blank spike control charts to monitor the analytical system for trends or events that indicate a change in method/instrument performance.
Matrix Spike/Matrix Spike Duplicate or Sample Duplicate Analysis -For each analytical batch and sample matrix type, a matrix spike sample and either a matrix spike duplicate sample or duplicate matrix sample are analyzed at a minimum frequency of one set per batch. Matrix spike recoveries should fall within 75-125% (or within lab derived limits if applicable) (or within lab
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11.6.4
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derived limits of applicable of the spike concentration for water and soil matrices. If the spike is not recovered within the specified limits, the data should be flagged as suspect due to sample matrix effects. Depending upon the project, provisions should be established to determine when the method of standard addition (MSA) should be employed to compensate for matrix effects.
Interference Check Standard Analysis OCPS\ -The inte,ference check standard is analyzed at the beginning and end of the analytical sequence and at intervals during the sequence. This standard contains the analytes of interest at minimal concentrations and by known concentration of interfering elements. If results exceed ±20% of the expected value, the instrument must be recalibrated before sample analysis may proceed.
Cyanide Analysis
Inorganic cyanide is detenmined colorimetrically by method 9010A, method 9012 or the CLP Inorganic SOW. Quality control procedures for this analysis include the analysis of:
• A preparation blank
• A laboratory control sample
• A matrix spike sample
• A matrix spike duplicate or sample duplicate
Each of these analyses is described below.
Preparation Blank Analysis -

A

preparation blank, containing all of the reagents and volumes used in the processing of samples and carried through
the complete preparation and analysis procedure, is analyzed at a minimum frequency of one per sample batch or sub-batch. The preparation blank is analyzed to demonstrate that the sample preparation procedure is free from contamination. This blank must be free of cyanide at or above the reporting limit (CRDL for analysis by CLP protocol), or the entire sub-batch of samples must be reprepared and reanalyzed.
Laboratory Control Sample Analysis -Control samples may be obtained from commercial vendors or prepared from suitable reference materials, but must be prepared independently from the calibration standards. The LCS is prepared along with the samples for analysis and is used to verify that the sample preparation and analysis steps are in control. LCS recovery data are plotted on blank spike control charts to monitor the analytical system for trends or events that indicate a change in method/instrument performance.
Matrix Spike/Matrix Spike Duplicate or Sample Duplicate Analysii, -For each analytical batch and sample matrix type, a matrix spike sample and either a matrix spike duplicate sample or duplicate matrix sarriple are analyzed at a
11.6.5
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Section 11
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minimum frequency of one set per batch. Matrix spike recoveries should fall
within 75-125% (or within lab derived limits if applicable) (or within lab
derived limits if applicable) of the spike concentration for water and soil
matrices. If the spike is not recovered within the specified limits, the data should be flagged as suspect due to sample matrix effects.
Anion Analysis
Anions, including chloride, nitrite, nitrate, a-phosphate, bromide, and sulfate,
may be analyzed by ion chromatography as described by Method 300.0.
Quality control procedures for this method include the analysis of:
• A preparation blank
• A laboratory control sample
• A matrix spike sample
• A matrix spike duplicate or sample duplicate
Each of these analyses is described below.
Preparation Blank Analysis -

A

preparation blank, containing all of the
reagents and volumes used in the processing of samples and carried through
the complete preparation and analysis procedure, is analyzed at a minimum
frequency of one per sample batch or sub-batch. The preparation blank is
analyzed to demonstrate that the sample preparation procedure is free from
contamination. This blank must be free of the anions being measured at or above the reporting limits, or the entire sub-batch of samples must be reprepared and reanalyzed.
Laboratory Control Sample Analysis -Control samples may be obtained from a commercial vendor or prepared from suitable reference materials, but must be prepared independently from · the calibration standards. The LCS is
prepared along with the samples for analysis and is used to verify that the
sample preparation and analysis steps are in control. LCS recovery data are plotted on blank spike control charts to monitor the analytical system for trends or events that indicate a change in method/instrument performance.
Matrix Spike/Matrix Spike Duplicate or Sample Duplicate Analysis -For each analytical batch and sample matrix type, a matrix spike sample and either a
matrix spike duplicate sample or duplicate matrix sample are analyzed at a · minimum frequency of one set per batch. Matrix spike recoveries should fall
within 75-125% (or within lab derived limits if applicable) (or within lab derived limits if applicable) of the spike concentration for water and soil matrices. If the spike is not recovered within the specified limits, the data
should be flagged as suspect due to sample matrix effects. Duplicate
analyses should agree within 20% RPO.
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11.6.6
11.6.7
:\lqapreva\sect11.doc
Fluoride Analysis
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Fluoride is determined potentiometrically by method 340.2. Quality control procedures include the analysis of:
• A preparation blank
• A laboratory control sample
• A matrix spike sample
• A matrix spike duplicate or sample duplicate
Each of these analyses is described below.
Preparation Blank Analysis -A preparation blank, containing all of the reagents and volumes used in the processing of samples and carried through the complete preparation and analysis procedure, is analyzed al a minimum frequency of one per sample batch or sub-batch. The preparation blank is analyzed to demonstrate that the sample preparation procedure is free from contamination.· This blank must .be free of fluoride at or above the reporting · limit, or the entire sub-batch of samples must be reprepared and reanalyzed.
Laboratory Control Sample Analysis -Control samples may be obtained from commercial vendors or prepared from suitable reference materials, but must be prepared independently from the calibration standards. The LCS is prepared along with the samples for analysis and is used to verify that the sample preparation and analysis steps are in control. LCS recovery data are plotted on blank spike control charts to monitor the analytical system for trends or events that indicate a change in method/instrument performance.
Matrix Spike/Matrix Spike Duplicate or Sample Duplicate Analysis -For each analytical batch and sample matrix type, a matrix spike sample and either a matrix spike duplicate sample or duplicate matrix sample are analyzed at a minimum frequency of one set per batch. Matrix spike recoveries should fall within 75-125% (or within lab derived limits if applicable) of the spike concentration for water and soil matrices. If the spike is not recovered within the specified limits, the data are flagged as suspect due to sample matrix effects. Duplicate analyses should agree within 20% RPO.
Tota\ Organic Carbon Analysis
Combustion of organic carbon and detection of carbon spectrometry is performed by method 9060 or 415.1.
procedures include the following analyses:
• A preparation blank
• A laboratory control sample
• A matrix spike sample
dioxide by IR
Quality control
• A matrix spike duplicate or sample duplicate
Each of these analyses is described below.
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Preparation Blank Analysis -

A

preparation blank, containing all of the reagents and volumes used in the processing of samples and carried through the complete preparation and analysis procedure, is analyzed at a minimum frequency of one per sample batch or sub-batch. The preparation blank is analyzed to demonstrate that the sample preparation procedure is free from contamination. This blank must be free of organic carbon at or above the reporting limit, or the entire sub-batch of samples must be reprepared and reanalyzed.
Laboratory Control Sample Analysis -Control samples may be obtained from a commercial vendor or prepared from suitable reference materials, but must be prepared independently from the calibration standards. The LCS is prepared along with the samples for analysis and is used to verify that the sample preparation and analysis steps are in control. LCS recovery data are plotted on blank spike control charts to monitor the analytical system for trends or events that indicate a change in method/instrument performance.
Matrix Spike/Matrix Spike Duplicate or Sample Duplicate Analysis -For each analytical batch and sample matrix type, a matrix spike sample and either a matrix spike duplicate sample or duplicate matrix sample are analyzed at a minimum frequency of one set per batch. Matrix spike recoveries should fall within 75-125% (or within lab derived limits if applicable) of the spike concentration for water and soil matrices. If the spike is not recovered within the specified limits, the data are flagged as suspect due to sample matrix effects. Duplicate analyses should agree within 20% RPO. ·
11.6.8 OH and Grease Analysis
:\lqapreva\sect11.doc
Total oil and grease is determined gravimetrically by methods 9070/9071A and 413.1 and spectrophotometrically (IR) by method 413.2. Quality control procedures include the following analyses:
• A preparation blank
• A laboratory control sample
• A matrix spike sample
• A matrix spike duplicate sample
Each of these analyses is described below.
Preparation Blank Analysis -

A

preparation blank, containing all of the reagents and volumes used in the processing of samples and carried through the complete preparation and analysis procedure, is analyzed at a minimum
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11.6.9
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frequency of one per sample batch or sub-batch. The preparation blank is analyzed to demonstrate that the sample preparation procedure is free from contamination. This blank must be free of oil and grease at or above the reporting limit, or the entire sub-batch of samples must be r,3prepared and reanalyzed.
Laboratory Control Sample Analysis -Control samples may be obtained from a commercial vendor or prepared from suitable reference materials, but must be prepared independently from the calibration standards. The LCS is prepared along with the samples for analysis and is used to verify that the sample preparation and analysis steps are in control. LCS recovery data are plotted on blank spike control charts to monitor the analytical system for trends or events that indicate a change in method/instrument performance.
Matrix Spike/Matrix Spike Duplicate Analysis -For each analytical batch and sample matrix type, a matrix spike sample and a matrix spike duplicate sample are analyzed at a minimum frequency of one set per batch. Matrix spike recoveries should fall within 75-125% (or within lab derived limits if· applicable) of the spike concentration for water and soil matrices. If the spike is not recovered within the specified limits, the data are flagged as suspect due to sample matrix effects. Duplicate analyses should agree within 20% RPO.
Total Recoverable Petroleum Hydrocarbons (TRPHl Analysis
TRPH is determined spectrophotometrically (JR) by method 418.1. Quality control procedures include the following analyses:
• A preparation blank
• A laboratory control sample
• A matrix spike sample
• A matrix spike duplicate sample
Each of these analyses is described below.
Preparation Blank Analysis -

A

preparation blank, containing all of the reagents and volumes used in the processing of samples and carried through the complete preparation and analysis procedure, is analyzed at a minimum frequency of one per sample batch or sub-batch. The preparation blank is analyzed to demonstrate that the sample preparation procedure is free from contamination. This blank must be free of TRPH at or above the reporting limit, or the entire sub-batch of samples must be reprepared and reanalyzed.
Laboratory Control Sample Analysis -Control samples may be obtained from·. commercial vendors or prepared from suitable reference materials, but must
be prepared independently from the calibration standards. The LCS is
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prepared along with the samples for analysis and is used to verify that the sample preparation and analysis steps are in control. LCS recovery data are plotted on blank spike control charts to monitor the analytical system for trends or events that indicate a change in method/instrument performance.
Matrix Spike/Matrix Spike Duplicate Analysis -For each analytical batch and sample matrix type, a matrix spike sample and a matrix spike duplicate sample are analyzed at a minimum frequency of one set per batch. Matrix spike recoveries should fall within 75-125% (or within lab derived limits if applicable) of the spike concentration for water and soil matrices. If the spike is not recovered within the specified limits, the data are flagged as suspect due to sample matrix effects. Duplicate analyses should agree within 20% RPO.
11.6.1 o California Assessment Manual Waste Extraction Test /CAM WED/Extraction Procedure Toxicity Test Method /EP-Tox}/Toxicity Characteristic Leaching Procedure <ICLPl
Waste extraction is performed according to the procedure described in the appropriate waste extraction regulation. Quality control procedures include the following analyses:
• A preparation blank
• A duplicate sample
Each of these analyses is described below.
Preparation Blank Analysis -A minimum of one method blank per sample batch of up to 20 samples is analyzed to demonstrate the absence of contamination above reporting limits.
Duplicate Sample Extraction -A duplicate sample extraction is performed with each batch of up to 20 samples. Results of analyses of the duplicate extracts are used to estimate overall measurement variability and generally should agree within 20% RPD.
11.7 STANDARDS
The term standard shall apply to any analyte solution of known concentration which is traceable to a certified reference material. This includes calibration standards, spiking solutions and laboratory control samples.
Upon receipt, all purchased standard reference materials (neat and stock solutions) are recorded into section-specific standards logbooks. Standard logbook entries include Pace unique ID, name of the neat compound or solution, manufacturer, manufacturer's lot number, certified purity, and expiration date. Subsequent
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preparations of stock, intermediate, and working solutions are also documented in the standards logbooks. These entries must include all discrete measurements· made during preparation, sources of materials, solvent(s} and a Pace ID numb,~r.
The standard vial should have a reference label affixed containing the following information (if sPace permits):
Standard ID number
Name of standard
Preparation date
Preparer's initials
Solvent
Preservation, if applicable
Expiration date
The Standard Operating Procedure (#MN-P-004-B) "Standards Traceability in Laboratory and Field" contains further instructions for assigning unique ID numbers,
shelf life of standards, and good laboratory practices.
All primary reference standard and standard solutions are purchased from reliable commercial sources. Standards traceable to NIST are preferred; however, ASTM or equivalent specifications are acceptable. Certification records of all standards received are retained.
Second source reference standards and standard solutions are purchased from a different supplier than ·the primary standard or from a different manufactured lot from the same vendor. If a second supplier is not available, the second source standard can be prepared from a different lot number of the same composition from the same supplier.
Newly prepared standard solutions (surrogate, internal, calibration, spiking) are verified against another known standard prepared from another source prior to utilization. The verification data is maintained on file in the respective area. In place of performing in-house standard verification, laboratories can purchase verified second source standards from a vendor which supplies a data package demonstrating verification.
11.8 SOLVENT LOT/ACID LOT VERIFICATION
All laboratory extraction solvents utilized are at least Pesticide Grade or better. Prior to accepting a solvent lot from the supplier, a quantity of the solvent is analyzed either by Pace or by the primary vendor under a National Qualified Materials (NQM) program
to access the purity. The NQM verification program is administered by the Pace Corporate office for use by all laboratory locations. If the lot is determined to meet purity standards/requirements, the lot is sequestered for Pace laboratories. The quality of organic extraction solvents is constantly monitored through the .analysis of method blanks.
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Acid lots are verified for purity prior to utilization for digestion of samples. If the acid lot is determined to meet purity criteria, the acid may be used for sample preparation digestion.
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:\lqapreva\sectl 11
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APPLICABLE
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Purgeable
Halocarbons
Purgeable
Aromatics
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TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL
CHECK
Initial 5-point
calibration
Continuing calibration
Method blank
Surrogate spikes
Matrix spike &
Matrix spike duplicate
Laboratory control
sample (LCS)
Second column
confirmation
Initial 5-point
calibration
Contim.iing calibration
Method blank
FREQUENCY
As needed -
Refer to method
Daily & every 10 samples
1 per batch & sub-batch
Every analysis
1 set per batch
1 per batch & sub-batch
100% for positive results
:::. reporting limit
As needed
Refer to method
Daily & every 1 0 samples
1 per batch & sub-batch
ACCEPTANCE
CRITERIA
r :::.0.995
%D .:,15% (except
gases and 2-CEVE)
All analytes < reporting limit
Bromochloromethane
(See Table 5.1)
Method 8010B limits
(See Table 5.1)
Statistical limits
(See Table 5.1)
Qualitative confirmation
r :::_0.995
%D ~15%
All analytes <
reporting limit
lilillil liiliiil
Date: 12/22/95
Section 11
Revision 0.01
Page 27 of 42
liiiliil
CORRECTIVE
ACTION
Repeat calibration
1. Repeat test
2. Recalibrate
iliil
Clean system & reanalyze sub-
batch
Reanalyze sample
Narrate in report
Correct problem & reanalyze
sub-batch
N/A
Repeal calibration
1. Repeat test
2. Recalibrate
Clean system & reanalyze
sub-batch
-
ANALYTICAL
METHOD
8080A
CLP SOW
:\lqaprevaUectl 11
--
APPLICABLE
PARAMETER
Organochlorine
Pesticides and
PCBs
-11111
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL
CHECK
Surrogate spikes
Matrix spike &
Matrix spike duplicate
Laboratory control
sample (LCS)
Second column
Initial calibration:
3-point (CLP)
5-point (8080A)
Continuing calibration
Breakdown check
(Endrin and DDT)
Method blank
Surrogate spikes
FREQUENCY
Every analysis
1 set per batch
1 per batch and
100% for positive results
confirmation
As needed
Refer to method
Every 12 hours (CLP)
Daily & every 10 samples
(8080A)
Every 12 hours (CLP)
Daily (8080A)
1 per batch & sub-batch
All analyses
11111111 r:::.lm
ACCEPTANCE
CRITERIA
1,4-Bromofluorobenzene
(See Table 5.1)
Method 8020A limits
(See Table 5.1)
Statistical limits
(See Table 5.1)
Qualitative confirmation
:!. reporting limit
r ?.0.995
(See method for CLP)
¾D .:,25% (CLP)
¾D .:,15% (8080)
:::::20% for each compound
(& .:,30% total for CLP)
All analytes < CRQL (CLP)
< Reporting limits (8080A)
Tetrachloro-m-xylene
Decachlorobiphenyl
(See Table 5.4)
-
Date: 12/22/95
Section 11
Revision 0.01
Page 28 of 42
CORRECTIVE
ACTION
Reanalyze sample
Narrate in report
Correct problem and renanalyze
sub-batch
NIA
Repeat calibration
1. Repeat test
2. Recalibrate
1. Correct problem
2. Recalibrate
Re-extract & reanalyze
sub-batch
Flag data (CLP)
Reanalyze sample (8080A)
-----
- -
ANALYTICAL
METHOD
California
LUFT Manual
:\lqapreva\sea 111
--
APPLICABLE
PARAMETER.
Purgeable
Petroleum
Hydrocarbons
- -
l!!!!!I l!!!!l!!!!I l!!!!!I l!!!!!!I ==
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL ACCEPTANCE
CHECK FREQUENCY CRITERIA
Matrix spike & 1 set per batch Method limits
Matrix spike duplicate (See Table 5.4)
Laboratory control 1 per batch & sub-batch Statistical limits
sample (LCS) (See Table 5.4)
Second column 100% for positive results qualitative confirmation
confirmation ~ reporting limit
Initial 5-point As needed r :::_0.995
calibration Refer to method
Continuing calibration Daily & every 10 samples %05:15%
Method blank 1 per batch & sub-batch All analytes <
reporting limit
Surrogate spikes Every analysis 1,4-Bromofluorobenzene
(See Table 5.2)
Matrix spike & 1 set per batch Method 8020A limits
Matrix spike duplicate (See Table 5.2)
Laboratory control 1 per batch & sub-batch Statistical limits
sample (LCS) (See Table 5.2)
Second column 100% for BTEX results Qualitative confirmation
confirmation :::. reporting limit if
no gasoline present
Date: 12/22/95
Section 11
Revision 0.01
Page 29 of 42
ail
CORRECTIVE
ACTION
Flag data (CLP)
Narrate in report (8080A)
Re-extract & reanalyze
sub-batch
NIA
Repeat calibration
1. Repeat test
2. Recalibrate
Clean system and reanalyze
sub-batch
Reanalyze sample
Narrate in report
Correct problem and reanalyze
sub-batch
N/A
liillii .
ANALYTICAL
METHOD
California
LUFT Manual
82408
CLP SOW
.\lqap,eva\seci 111
-
APPLICABLE
PARAMETER
Extractable
Petroleum
Hydrocarbons
Volalile Organics
byGC/MS
liiiililil liiBlil
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL
CHECK
Initial 5-point
calibration
Continuing calibration
Method blank
Matrix spike &
Matrix spike duplicate
Laboratory conlrol
sample (LCS)
Mass scale calibration
using PFTBA
Mass spectral ion intensity
check using BFB
Initial 5-point
calibration
-ail
FREQUENCY
As needed
Refer to melhod
Daily & every 1 0 samples
1 per batch & sub-batch
1 set per batch
1 per batch & sub-batch
Daily
Every 12 hours
As needed
Refer to method
1111111
ACCEPTANCE
CRITERIA
r "'.0.995
%0 ~15%
All analy1es <
reporting limil
Statistical limits
(See Table 5.3)
Statistical limits
(See Table 5.3)
N/A
Refer to method
RSD :,20.5% & min. RRF
for Table 2 compounds (CLP),
RSD :,30% for CCC & min.
RRF for SPCC compounds
(8240B)
-
Date: 12/22/95
Section 11
Revision 0.01
Page 30 of 42
CORRECTIVE
ACTION
Repeal calibration
1. Repeat test
2. Recalibrate
Re-extract & reanalyze
sub-batch
Narrate in report
Re-extract & reanalyze
sub-batch
NIA
1. Retune instrument
2. Repeal BFB analysis
Repeat calibration
-----
- - - - - -
11!!1 l!!!!!!!I! !!!!!!I l!!!!!I 1!!!!11
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
ANALYTICAL APPLICABLE QUALITY CONTROL ACCEPTANCE
METHOD PARAMETER CHECK FREQUENCY CRITERIA
Continuing calibration Every 12 hours %0 ~25% & min. RRF for
Table 2 compounds (CLP),
%0 ~20% for CCC & min.
RRF for SPCC compounds
(82408)
Method blank Every 12 hours All analytes < CRQL, < 5X
CRQL for common solvents
(CLP); < Reporting limit,
< 5X reporting limit for
common solvents (82408)
Surrogate spikes Every analysis Method limits
(See Table 5.5)
Internal standard Every analysis -50% to +100% area count
of continuing calibration
RT shift <30 sec. for ISs
in daily std.
Matrix spike & 1 set per batch Method limils
Matrix spike duplicate {See Table 5.5)
Laboratory control 1 per batch & sub-batch Statistical limits
sample (LCS) (See Table 5.5)
82708 Semivolatile Mass scale calibration Daily N/A
CLP SOW Organics using PFT8A
by GC/MS
:\lqapre~a\secl 111
a.a liiiiiii
Date: 12/22/95
Section 11
Revision 0.01
Page 31 of 42
liilil
CORRECTIVE
ACTION
1. Repeat test
2. Recalibrate
Clean system & reanalyze
sub-batch
Reanalyze sample
Reanalyze sample
Narrate in report
liill
Correct problem and reanalyze
sub-batch
N/A
ANALYTICAL
METHOD
:\lqapreva\sedl 11
-
APPLICABLE
PARAMETER
-liilii
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL
CHECK
Mass spectral ion inlensity
check using OFTPP
Initial 5-point
calibration
Continuing calibration
Method blank
Surrogate spikes
Internal standard
llllill
FREQUENCY
Every 12 hours
As needed
Refer to method
Every 12 hours
1 per batch & sub-batch
Every analysis
Every analysis
ACCEPTANCE
CRITERIA
Refer to method
RSO :,20.5% & min. RRF
for Table 5 compounds (CLP).
RSO :,30% for CCC & min.
RRF for SPCC compounds
(82708)
%0 :,25% & min. RRF for
Table 5 compounds (CLP),
%0 :,20% for CCC & min.
RRF for SPCC compounds
(82708)
All analytes < CRQL, < 5X
CRQL for phthalates (CLP);
< Reporting limit, < 5X
reporting limit for phthalates
(82708)
Method limits
(See Table 5.6)
•50% to +100% area count
of continuing calibration
RT shift <30 sec. for ISs
in daily std.
-
Date: 12/22/95
Section 11
Revision 0.01
Page 32 of 42
CORRECTIVE
ACTION
1. Retune instrument
2. Repeat OFTPP analysis
Repeat calibration
1. Repeal test
2. Recalibrate
Re-extract & reanalyze
sub-batch
Re-extract & reanalyze sample
Reanalyze sample
-----
--
ANALYTICAL
METHOD
6010A
CLP SOW
:\lqapreva\seci 111
--
APPLICABLE
PARAMETER
Trace Metals
By ICPS
- -
I!!!!! l!!m ==
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL ACCEPTANCE
CHECK FREQUENCY CRITERIA
Matrix spike & 1 set per batch Method limils Matrix spike duplicate (See Table 5.6)
Laboratory control 1 per batch & sub-batch Statistical limits sample (LCS) (See Table 5.6)
Initial calibration Daily Refer to method
Initial calibration Daily 90-110% of true value verification (ICV)
Initial calibration Daily All elements_<; CRDL (CLP) blank (ICB) < Reporting limit (601 0A)
Interference check Beginning & end of 80-120% of true value (A, AB) run sequence
CRDL check (CLP) Beginning & end of NIA
run sequence
Continuing calibration Every 10 samples 90-110% of true value verification (CCV)
Continuing calibration Every 10 samples All elements _<; CRDL (CLP) blank (CCB) < Reporting limit (601 0A)
Method blank 1 per batch & sub-batch All elements .'.: CRDL (CLP)
< Reporting limit (601 0A)
liiliiiil Eliiiiil
Date: 12/22/95
Section 11
Revision 0.01
Page 33 of 42
CORRECTIVE
ACTION
Narrale in report
Re-extract & reanalyze
sub-batch
Refer to method
Recalibrate
Recalibrate
Recalibrate (Initial)
Reanalyze samples (Final)
NIA
1. Recalibrate
2. Reanalyze samples
1. Recalibrate
2. Reanalyze samples
Redigest & reanalyze
sub-batch
iai
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
Date: 12122195
Section 11
Revision 0.01
Page 34 of 42
ANALYTICAL
METHOD
7041 (Sb)
7060A (As)
7740 (Se)
7421 (Pb)
7841 (Tl)
7470A(Hg)
7471A (Hg)
CLP SOW
:\lqapreva\sect11t
APPLICABLE
PARAMETER
Trace metals
byGFAA
and CVAA
QUALITY CONTROL
CHECK
Laboratory control
sample (LCS)
Replicate exposures
Matrix spike
Matrix spike duplicate
(6010A)
Duplicate analysis (CLP)
Serial dilution
Initial multipoint
calibration
Initial calibration
verification (ICV)
Initial calibration
blank (ICB)
CRA standard (CLP)
Continuing calibration
verification (CCV)
FREQUENCY
1 per batch & sub-batch
Every analysis
1 per batch
1 per batch
1 per batch
1 per batch
Daily
Daily
Daily
Daily
Every 10 samples
--liiiilil li!iil -.. .. -==
ACCEPTANCE
CORRECTIVE CRITERIA
ACTION
80.120% recovery (CLP) Redigest & reanalyze Statistical limits sub-batch (See Table 5. 7, 601 0A)
RSD:5.20% Reanalyze sample
75-125% recovery Narrate in report
75-125% recovery Narrate in report
RPD :5.10% Flag data
90-110% of undiluted value Flag data (CLP)
r ;!0.995 Repeat calibration
90.110% (GFAA)
80.120% (CVAA) Recalibrate
5. CRDL (CLP) Recalibrate < Reporting limit (7000)
NIA NIA
90.110% (GFAA) 1. Recalibrate 80-120% (CV AA) 2. Reanalyze samples
-------

-

-
--
ANALYTICAL
METHOD
7196A
:\lqapceva\s&cl I It
--
APPLICABLE
PARAMETER
Hexavalent
Chromium
- -
l!!l!!I l!!!!!!!!I !!!!!I l!!!l!I I!!!!!!!
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL ACCEPTANCE
CHECK FREQUENCY CRITERIA
Continuing calibration Every 10 samples :;.CRDL (CLP) blank (CCB) < Reporting limit (7000)
Method blank 1 per batch & sub-batch :;_ CRDL (CLP)
< Reporting limit (7000)
Laboratory control 1 per batch & sub-batch 80-120% recovery (CLP) sample (LCS) Statistical limits .
(See Table 5.7, 7000)
Matrix spike 1 per batch 75-125% recovery
Matrix spike duplicate 1 per batch 75-125% recovery (7000)
Duplicate analysis (CLP) 1 per batch RPD:;.20%
Analytical spike (GFAA) Every sample Refer lo method
(CLP)
Initial multipoint Daily r ::_0.995
calibration
Initial calibration Daily 90-110% of true value verification (ICV)
Initial calibration Daily < Reporting limit blank (ICB)
liiiiiil
Date: 12/22195
Section 11
Revision 0.01
Page 35 of 42
--
CORRECTIVE
ACTION
1. Recalibrate
2. Reanalyze samples
Redigest & reanalyze
sub-batch
Redigesl & reanalyze
sub-batch
Flag data (CLP)
Narrate in report (7000)
Narrate in report
Flag data
Refer lo method
Repeal calibration
Recalibrate
Recalibrate
-
ANALYTICAL
METHOD
9010N9012
CLP SOW
:\lqapreva\sea11 I
-
APPLICABLE
PARAMETER
Cyanide
illill
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL
CHECK
Continuing calibration
verification (CCV)
Continuing calibration
blank (CCB)
Method blank
Malrix spike &
Matrix spike duplicate
Laboratory control
sample (LCS)
lnilial multipoint
calibration
Initial calibration
verification (ICV)
Initial calibration
blank (ICB)
Continuing calibration
verification (CCV)
Method blank
1111111
FREQUENCY
Every 10 samples
Every 10 samples
1 per batch & sub-batch
1 set per batch
1 per batch & sub-batch
Daily
Daily
Daily
Every 10 samples
1 per batch & sub-batch
mm
ACCEPTANCE
CRITERIA
90-110% of true value
< Reporting limit
< Reporting limit
75,.125% recovery
Statistical limits
(See Table 5.8)
r ,:0.995
85,.115% of true value
:; CRDL (CLP)
< Reporting limit (9010N9012)
85,.115% of true value
:; CRDL (CLP)
< Reporting limit (9010N9012)
---
Date: 12/22/95
Section 11
Revision 0.01
Page 36 of 42
CORRECTIVE
ACTION
1. Recalibrate
2. Reanalyze samples
1. Recalibrate
2. Reanalyze samples
Reprep & reanalyze
sub-batch
Narrate in report
Reanalyze sub-batch
Repeat calibration
Recalibrate
Recalibrate
1. Recalibrate
2. Reanalyze samples
Reprep & reanalyze
sub-batch
-----
- -
ANALYTICAL
METHOD
300.0
:\lqaprevalsect 111
--
APPLICABLE
PARAMETER
Anions by Ion
Chromatography
--l!!!!!!!I I!!!!! I!!!! . !!!!I . -i==s ==
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL
CHECK
Laboratory control
sample (LCS)
Matrix spike
Matrix spike duplicate
(9010A/9012)
Duplicate analysis (CLP)
Initial multipoint
calibration
Initial calibration
verification (ICV)
Initial calibration
blank (ICB)
Continuing calibration
verification (CCV)
Continuing calibration
biank (CCB)
Method blank
FREQUENCY
1 per batch & sub-batch
1 per batch
1 per batch
1 per batch
Daily
Daily
Daily
Every 10 samples
Every 10 samples
1 per batch & sub-batch
ACCEPTANCE
CRITERIA
80-120% recovery (CLP)
Statistical limits
(See Table 5.8)
75-125% recovery
75-125% recovery
RPD.'.,20%
r ,:0.995
90-110% of true value
All analytes <
reporting limit
85-115% of true value
All analytes <
reporting limit
All analytes <
reporting limit
aiiil
Date: 12/22/95
Section 11
Revision 0.01
Page 37 of 42
lililil
CORRECTIVE
ACTION
Reprep & reanalyze
sub-batch
Flag data (CLP)
Narrate in report (9012)
Narrate in report
Flag data
Repeat calibration
Recalibrate
Recalibrate
1. Recalibrate
2. Reanalyze samples
1. Recalibrate
2. Reanalyze samples
Reanalyze sub-batch
iiil _ lliiii_ .
ANALYTICAL
METHOD
120.1
130.2
150.1
:\lqapreva\sect11t
-
APPLICABLE
PARAMETER
Conductance
Hardness
pH
liiilliill lillil
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL ACCEPTANCE
CHECK FREQUENCY CRITERIA
Matrix spike & 1 sel per batch 75-125% recovery
Matrix spike duplicate s20%RPD
Laboratory control 1 per batch & sub-batch Statistical limits
sample (LCS) (See Table 5.8)
Multipoint calibration Daily 98-102% of true value
for each ·standard
Calibration verification Daily 90-110% recovery
Duplicate analysis 1 per batch RPD~20%
Laboratory control 1 per batch & sub-batch Statistical limits
sample (LCS) (See Table 5.8)
Method blank 1 per batch & sub-batch < Reporting limit
Duplicate analysis 1 per batch RPD~20%
2 to 3-point calibration Daily ±0.05 to>
:t0.1 pH units
Calibration verification Daily ±0.05 to>
:t0.1 pH units
Duplicate analysis 1 per batch ±0.05 to>
:t0.1 pH units
iiiliil -Elllllil ma --
Date: 12/22/95
Section 11
Revision 0.01
Page 38 of 42
CORRECTIVE
ACTION
Narrate in report
Reanalyze sub-batch
Repeat calibration
1 . Re peat check
2. Recalibrate
3. Reanalyze batch
Narrate in report
1. Restandardize titrant
2. Reanalyze sub-batch
Reanalyze batch
Narrate in report
Repeat calibration
1. Recalibrate
2. Reanalyze batch
Narrate in report
-----
- -
ANALYTICAL
METHOD
160.1
160.2
310.1
340.2
:\Jqapreva\sect11l
--
APPLICABLE
PARAMETER
Total Dissolved
Solids
Total Suspended
Solids
Carbonate/
Bicarbonate
Fluoride
- --l!l!!!!I ~ !!!!!! !!!!!I _ ll!!S ==
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL
CHECK
Method blank
Duplicate analysis
Method blank
Duplicate analysis
3-point calibration
Calibration verification
Method blank
Duplicate analysis
Matrix spike &
Matrix spike duplicate
Multipoint calibration
Calibration verification
Method blank
FREQUENCY
1 per batch & sub-batch
1 per batch
1 per batch & sub-batch
1 per batch
Daily
Daily
1 per batch & sub-batch
1 per batch
1 set per batch
Daily
Daily
1 per batch & sub-batch
ACCEPTANCE
CRITERIA
±0.5 mg
RPD:::20%
:t0.5 mg
RPO :::20%
±0.05 to
±0.1 pH units
85-115% recovery
< Reporting limit
RPO :::20%
75-125% recovery
r ~0.995
90-110% recovery
< Reporting limit
l:iiiiiil liiiiiiiii
Date: 12/22/95
Section 11
Revision 0.01
Page 39 of 42
liiliii
CORRECTIVE
ACTION
Reprep and reanalyze batch
Narrate in report
Reprep and reanalyze batch
Narrate in report
Repeat calibration
1. Recalibrate
2. Reanalyze batch
Reanalyze batch
Narrate in report
Narrate in report
Repeat calibration
Recalibrate
Reanalyze batch
ANALYTICAL
METHOD
350.3
:\lqapreva\sect 111
--
APPLICABLE
PARAMETER
Ammonia
lilllil
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL
CHECK
Matrix spike &
Matrix spike duplicate
or Duplicate
Laboratory control
· sample (LCS)
Multipoint calibration
Calibration verification
Method blank
Matrix spike &
Matrix spike duplicate
or Duplicate
Laboratory control
sample (LCS)
FREQUENCY
1 set per batch
1 per batch & sub-batch
Daily
1 per batch
1 per batch & sub-batch
1 set per batch
1 per batch & sub-batch
ACCEPTANCE
CRITERIA
75-125% recovery
RPO $20%
Statistical limils
(See Table 5.8)
r::.0.995
85-115% recovery
< Reporting limit
75-125% recovery
RPO $20%
Statistical limits
(See Table 5.8)
--
Date: 12/22/95
Section 11
Revision 0.01
Page 40 of 42
CORRECTIVE
ACTION
Narrate in report
Reanalyze batch
Repeat calibration
1. Recalibrate
2. Reanalyze batch
Reanalyze batch
Narrate in report
Reanalyze batch
-----
--
ANALYTICAL
METHOD
9060
415.1
9070/9071
413.1
413.2
.\lqapreva\sed111
- -
APPLICABLE
PARAMETER
Total Organic
Carbon
Oil & Grease
Gravimetric
Oil & Grease
by IR
- -
I!!!!!! !!!!! !!!!!!I == ==
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL
CHECK
Initial calibration
(4 replicates of 1 point)
Calibration verification
Method Blank
Duplicate analysis
Matrix spike
Laboratory control
sample (LCS)
Balance calibralion
check at 1 g & 100 g
Method blank
Matrix spike &
Matrix spike duplicate
or Duplicate
Laboratory control
sample (LCS)
Initial 5-point
calibration
FREQUENCY
Daily
Daily
1 per batch & sub-batch
1 per batch
1 set per balch
1 per batch & sub-balch
Beginning & end of
analytical sequence
1 per batch & sub-batch
1 set per batch
1 per batch & sub-batch
Daily
ACCEPTANCE
CRITERIA
1125-1875 average raw
instrument reading
85-115% of true value
< Reporting limit
RPO :,50%
75-125% recovery
Statistical limits
(See Table 5.8)
±0.001 g of true weight
< Reporting limil
75-125% recovery
RPO "20%
Statistical limits
(See Table 5.8)
r ,:0.995
lliililil liiliii lliiil
Date: 12/22/95
Section 11
Revision 0.01
Page 41 of42
CORRECTIVE
ACTION
Reprep standard &
recalibrate
Recalibrate
Reanalyze batch
Narrate in report
Narrate in report
Reanalyze balch
Recalibrate balance
1. Redesiccate & reweigh samples
2. Re-extract sub-batch
Narrate in report
Re.extract & reanalyze
sub-batch
Repeat calibration
ANALYTICAL
METHOD
418.1
:\lqapreva\sect 111
--
APPLICABLE
PARAMETER
Total Petroleum
Hydrocarbons
bylR
liiiilii
TABLE 11.1 SUMMARY OF CALIBRATION AND QUALITY CONTROL PROCEDURES
QUALITY CONTROL
CHECK
Continuing calibration
Method blank
Matrix spike &
Matrix spike duplicate
or Duplicate
laboratory control
sample (lCS)
Initial 5-point
calibration
Continuing calibration
Method blank
Matrix spike &
Matrix spike duplicate
or Duplicate
laboratory control
sample (lCS)
lili'II -
FREQUENCY
Every 10 samples
1 per batch & sub-batch
1 set per batch
1 per batch & sub-batch
Daily
Every 1 D samples
1 per batch & sub-batch
1 set per batch
1 per batch & sub-batch
ACCEPTANCE
CRITERIA
80-120% of true value
< Reporting limit
75-125% recovery
RPO !>20%
Statistical limits
(See Table 5.8)
r ~0.995
80-120% of true value
< Reporting limit
75-125% recovery
RPO !>20%
Statistical limits
(See Table 5.8)
--
Date: 12/22/95
Section 11
Revision 0.01
Page 42 of 42
CORRECTIVE
ACTION
1. Repeat test
2. Recalibrate
1. Clean system & recheck
2. Re-extract & reanalyze
sub-batch
Narrate in report
Re-extract & reanalyze
sub-batch
Repeat calibration
1. Repeat test
2. Recalibrate
1. Clean system & recheck
2. Re-extract & reanalyze
Narrate in report
Re-extract & reanalyze
sub-batch
-----
I
I
m
I
I
D
D
D
I
I
I
I
I
I
I
I
12.0 QUALITY ASSURANCE AUDITS AND
PERFORMANCE EVALUATIONS
Date: 12/22/95
Section 12
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Integral to Pace's quality assurance program is a program of internal audits designed to provide feedback about the effectiveness and completeness of the various quality control and quality assurance systems in the laboratory. This section describes the types of audits conducted at Pace and discusses the roles and_responsibilities of Pace personnel related to these audits.
12.1 INTERNAL AUDITS
12.1.1
12.1.2
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Quality Assurance Auditor
The QA auditor is responsible for designing and/or perfonming QA performance and systems audits. Since QA audits represent an independent assessment of laboratory functions, the auditor must be functionally independent from laboratory operations to ensure objectivity. However, the auditor must be familiar enough with the objectives, principles, and procedures of laboratory operations to be able to perform a thorough and effective evaluation. The auditor's ability to identify components of systems that are critical to overall data quality is especially important.
Internal audits are typically conducted by the laboratory QA Officer, who may be assisted by other laboratory personnel. The QA Officer reports directly to the Laboratory General Manager, and therefore is independent of laboratory operations. The QA Officer evaluates audit observations and verifies the completion of corrective actions.
Scope and Frequency of Internal Audits
Internal systems audits are conducted at a minimum frequency of one per quarter. The scope of these audits may include the examination of the operations of a specific analy1ical department or may focus on the evaluation of a specific quality-related system as applied throughout the laboratory. ·
Examples of system-wide elements which can be audited include:
• Standard operating procedures, including system of review, issue, filing, maintenance, training, understanding, documentation of deviations and implementation of SOPs.
• Adherence to standard operating procedures, the QAP and regulations. Personnel and training files, including job descriptions, resumes, documented training and training file maintenance.
General laboratory safety, including appropriate clothing, waste disposal, health and safety plan review, obvious safety concerns.
Labeling of reagents, solutions, standards, and associated documentation. Equipment and instrumentation documentation, calibration/
maintenance records, operating manuals.
•
•
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Sample handling, storage and disposal including storage locations, security, tracking/chain-of-custody, disposal practices and records, labeling
and retention.
Documentation of sample analysis, methodologies, quality control requirements.
Documentation of discrepancy reports and corrective action .
General procedures for data security, review, documentation, reporting and archiving.
When the operations of a specific department are evaluated, a number of functions are reviewed, such as:
Documentation of technical training and analyst proficiency
• Method detection limit studies
Internal chain-of-custody documentation
Nonconformance documentation
Documentation of standard preparations
Instrument maintenance documentation
• Standard operating procedures
Control charts
Documentation of sample preparation and analysis
Documentation of data review
As required on specific projects, internal audits are performed to ensure laboratory conformance to site workp/ans, sampling and analysis plans, QAPP,
etc. Project audits can include review of the following items of concern:
Sample log-in and chain-of-custody records
Sample storage procedures and records
Sample preparation and analysis procedures
• Method validation (where applicable)
Conformance to QAPP
Control charts (if applicable)
Precision and accuracy assessment
Method blanks, reagent blanks, duplicates, check samples, fortifications,
surrogates, etc.
Calibration
• Data packages
• Analyst qualifications
Data validation and reporting
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12.1.3 Internal Audit Reports and Corrective Action Plans I A full description of the audit, including the identification of the department or operation audited, the date(s) on which the audit was conducted, the specific systems examined, and the observations made during the course of the audit, are I summarized in an internal audit report. Although other personnel may assist with
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the performance of the audit, the QA Officer writes and issues the internal audit
report. The QA Officer identifies which audit observations are deficiencies that require corrective action.
Once completed, the internal audit report is issued jointly to the laboratory general manager and the manager(s)/supervisor(s) of the audited departrnent(s) or operation(s). The responsible manager(s)/supervisor(s) respond with a plan to correct all of the deficiencies cited by the due date specified in the audit report.
Each response must include timetables for completion of all proposed corrective
actions.
The QA Officer reviews and accepts the audit responses. If !he response is
accepted, the QA Officer uses the action plan(s) and timetable(s) as a guideline
for verifying completion of the corrective action(s). If the QA Officer determines
that the audit response does not adequately address the correction of cited deficiencies, the response will be returned for modification.
To complete the audit process, the QA Officer performs a re-examination of the
areas where deficiencies were found to verify that all proposed corrective actions· have been implemented. An audit deficiency is considered closed once implementation of the necessary corrective action has been verified. If corrective action cannot be verified, the associated deficiency remains open until that action
is completed.
12.2 EXTERNAL AUDITS
Pace is audited as required by regulatory agencies to maintain laboratory certifications, and by various commercial clients. External audits include those by state laboratory certification agencies, USEPA, Army Environmental Center (AEC), Army Corps of Engineers, and other appropriate federal, state and private agencies (e.g., MITRE).
Audit teams external to the company review the laboratory to assess the existence of systems, implementation of the systems, and degree of technical expertise. QA staff host the audit team and collect notes during the audit process. These notes are communicated
to the General Manager, Laboratory Manager and the supervisor. Generally, the auditors will prepare a formalized audit report listing deficiencies observed and follow-up requirements for the laboratory. In some cases, in lieu of an official report, items of concern are discussed during a debriefing convened at the end of the on-site review process. · The laboratory staff and supervisors develop corrective action plans to address any deficiencies with the guidance of the QAO. The laboratory manager provides the necessary resources for staff to develop and implement the corrective action plans. The QAO collates this information and provides a written report to the audit team. The re port contains the corrective action plan and expected completion dates for each element of the plan. QAO staff follow-up with the laboratory staff to ensure that corrective actions are implemented.
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12.3 TOTAL QUALITY SYSTEM AUDIT
The Corporate Quality Office coordinates on-site audits of each laboratory facility. The corporate audit is conducted by the Vice President of Quality with the assistance of Pace QAO's. This audit is designed to evaluate all aspects of facility operations and is not limited to only laboratory operations. Audits may either be system related or technical in nature, depending on the type of information needed for making quality improvements.
Assessment of quality/technical practices within laboratory operations involves three types of review.
1.
2.
3.
Documentation -On-going monitoring of quality issues in laboratory offices requires that the corporate quality office receive the following hardcopy information on an "as released' basis, supplied as part of the Quarterly Quality Report to management. ·
PE scores (e.g., WP, WS, CLP, COE, AEC, EML, EMSL, NIOSH, etc.) Certification/parameter list approvals
• External audit reports and responses
lnternai audit reports
• Copies of all newly developed SOPs (also critical for the MRD program)
Periodic data validation report reviews
Pre-audit Documentation
•
Verify methods capability matrix infonmation ( completed for each method routinely perfonmed in the laboratory)
Sample report for each reporting deliverable level used by the facility
Facility and equipment inventory
Current organization chart
LIMS sample management reports
Facility Audit Process
•
..
•
Checklist approach with minimal textual report
Objective scoring system based on checklist results
Technical review based upon compliance to MRDs and associated SOPs, published methods, federal program requirements
"GLP' documentation trail (retrace the path of a sample through the laboratory)
Non-analytical documentation (e.g., training logs, discrepancy/corrective
action reports, preventative maintenance, standards traceability, etc.) Review of QA procedures (relative to the Pace Generic Quality Assurance
Plan)
Credential/certification verification
Instrumentation and facility utilization (e.g., automation, workflow)
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Health and safety, waste disposal programs (reviewed in conjunction with technical audit)
Debriefing meeting
Issue final audit report and establish corrective action schedule
12.4 PERFORMANCE EVALUATION AUDITS
12.4.1 Pace PE Samples
Double blind performance evaluation (PE) samples are submitted periodically to all Pace laboratories to evaluate all areas of the laboratory. The program is identified as the Pace lnterlaboratory Testing Survey (PITS). Results from
internal PE sample analyses are processed by the analy1ical departments and
reported to the responsible Project Manager. The Project Manager issues a standard analytical report to a fictitious client (PE vendor) in a manner identical to that done for all other client work orders.
Evaluated PE results are given to the laboratory for review. For parameters
where the reported results fall within the defined acceptance limits, no further
action is required. For parameters where the reported results fall outside· acceptance limits, the responsible Department Manager/Supervisor must investigate in an effort to find the root cause of each problem. For each missed
quantitation, the Manager/Supervisor summarizes the findings of their
investigation in a PE investigation report. Each report must include a description
of the corrective action(s) that will be taken to prevent recurrence of the problem.
Completed reports are passed to the QA Officer for review, then forwarded to Pace's corporate quality office. The internal auditing process is. used to verify
implementation of corrective actions.
12.4.2 EPA WP and ws PE Studies .
Pace labs routinely participate in EPA's Water Pollution (WP) and Water Supply (WS) round-robin PE studies. Each of these studies is conducted twice per year.
Generally, all analy1ical sections of the laboratory participate in the WP and WS PE -studies. Examples of parameters analyzed under each study are listed below.
Satisfactory perfonnance on these studies is essential as they are a fundamental
requirement of state accreditation programs.
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• EPA Performance Evaluations -Water Supply -Semiannual (April and
September)
•
Trace Metals
Nitrate/Nitrite/Fluoride
Insecticides
Herbicides
PAHs
Adipate/Phthalates
Trihalomethanes (THMs)
Volatile Organic Compounds
Turbidity
Total Filterable Residue
Calcium (as CaCO3)
pH
Alkalinity
Corrosivity
Sodium
Sulfate
Total Cyanide
EPA Performance Evaluations -Water Pollution -Semiannual (February and August) ·
Trace Metals
Minerals
Nutrients
Demand
PCBs
PCBs in Oil
Pesticides
Volatile Halocarbons
Volatile Aromatics
Total Cyanide
Non-Filterable Residue
Oil and Grease
Total Phenolics
For PE quantitations evaluated as being outside the acceptance ranges, investigations must be performed by the responsible Manager(s)/Supervisor(s)
and reports must be completed as described above for the Pace PE samples. The reports are reviewed by the QA Officer, then forwarded to the various state accreditation agencies for their review.
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12.4.3 Other PE Studies
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Other PE samples may be performed by Pace in conjunction with a specific
program or contract. Examples include:
PE samples distributed by the US Army Corps of Engineers, Missouri River
Division, as part of their laboratory evaluation process
Quarterly blind (QBs) PE samples distributed to laboratories participating in
EPA's Contract Laboratory Program
In addition, clients may arrange for PE samples to be analyzed, either as part of a laboratory evaluation process or as a periodic performance check.
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13.0 PREVENTIVE MAINTENANCE
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The objective of Pace's preventive maintenance program is to establish a system of instrument care that prevents the loss of analytical quality control and results in a minimum of lost productivity due to instrument failure. This program includes a system for documenting all routine and non-routine instrument maintenance and repairs.
Pace maintains service contracts for mo_st major analytical equipment including chromatographic instruments. balances, atomic absorption. and inductively coupled plasma instruments. All equipment and instruments generating analytical results have calibration and maintenance records.
13.1 MAINTENANCE RESPONSIBILITIES
The Laboratory Operations Manager and Supervisors are responsible for providing technical leadership to all staff involved with chemical analysis. This leadership role includes serving as a technical resource to help solve equipment and method problems, evaluating and recommending investments in new technologies, improvin~1 efficiency, and coordinating instrument repair and maintenance.
The primary responsibility for the maintenance of instruments and equipment rests with each analytical Department Manager/Supervisor. The Department Manager/Supervisor is further responsible for developing procedures and schedules for maintaining each major instrument or piece of equipment and for delegating specific maintenance responsibilities to department staff.
13.2 MAINTENANCE SCHEDULES
The effectiveness of the maintenance program relies heavily on adherence to prescribed schedules for maintaining each instrument or piece of equipment. A schedule is established for all routine maintenance. Other maintenance activities may also be identified as requiring attention on an as-needed basis. Manufacturers' recommendations provide· the primary basis for developing these schedules, and manufacturers' service contracts provide primary maintenance for some major instruments.
To minimize downtime and interruption of analytical work, preventive maintenance is routinely performed on each analytical instrument. SOPs are written for each instrument that cover basic operation and maintenance procedures. The following are brief summaries of maintenance for each type of major instrumentation. This information is also listed by major instrumentation system in Table 13.1.
13.2.1 Preventive Maintenance -GC/MS
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Regularly performed maintenance includes, but is not limited to the following for GC/MS instrumentation:
13.2.2
13.2.3
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Hard tune with calibration gas (pftba)
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Removal of 2-3 inches from the injection end of the capillary columns
Replacement of 2-3 inches of column packing from the injection end of
packed columns
Injection port liner replacement
Replace injection port septum
Clean ion source as needed
Check vacuum pump oil level
Check carrier gas tanks
Replace or recondition vent traps
Preventive Maintenance -GC
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Regularly performed maintenance includes, but is not limited to the following 1 for extractable GC instrumentation:
Removal of 5-10 inches of guard column (if applicable) and 2-3 inches from 1 the injection end of the capillary columns
Replacement of 2-3 inches of column packing from the injection end of · packed columns
Injection port liner and RP seal replacement I Replacement of septum
Fill solvent rinse bottles in auto sampler
Check carrier and support gases I NRC wipe test ECO
Regularly performed maintenance includes, but is not limited to, the following for volatile organics GC instrumentation:
Clean and bake sparge tubes
• Replace trap as needed
Check carrier and support gases
• Replace transfer line as needed
• Replace nickel tube as needed
• Clean or replace PIO as needed
Preventive Maintenance -ICP
Check liquid argon tank level
• Change pump tubing
• Clean nebulizer and spray chamber as needed
• Replace and realign plasma torch when required
Check cooling system water level
• Empty waste reservoir when full
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13.2.4
13.2.5
13.2.6
13.2.7
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Preventive Maintenance -AA Graphite Furnace
Check and align source lamps
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Clean and inspect graphite tube, replacing when surface appears
excessively burnt or cracked
Clean and inspect contact ring, replacing when excessively worn
Clean mirrors for optical sensor and sample compartment windows
Check autosampler injector alignment and deposition
Preventive Maintenance -Mercury Analyzer
Check and align source lamp
• Remove and clean sample cell and connecting tubes
• Check sparger for proper operation
Clean sample compartment windows
Preventive Maintenance -General Laboratory Areas
Calibrate automatic pipets and burets monthly
Clean, check, calibrate to manufacturers specifications all pH, DO,
conductivity and, turbidity meters, and spectrophotometers annually
• General housekeeping: keep counter tops, hoods, and floors clean and
keep safety equipment accessible
Check airflow in hoods once a quarter
Preventive Maintenance
Thermometers, Refrigerators, Ovens and Balances:
Laboratory thermometers are calibrated against NIST traceable thermometers
annually. Digital thermometers are calibrated quarterly. 1he results are
recorded in a logbook specific to that purpose. Correction factors are recorded
on the thermometer tags, along with the unique thermomet,3r identification
number and calibration date, and are used by Pace personnel to correct actual
temperature measurements. The correction factor is applied to each reading
until the thermometer is calibrated again. Use of thermometers with a
correction of> 5° C is avoided. Pace minimizes the need to apply corrections
by utilizing the correct media, thermometers and procedures during calibration.
Refrigerators, freezers and ovens are monitored once or twice daily or ·as used,
dependent upon the function of the unit. Logbooks are maintained for
documentation of readings and corrective actions. If a unit fails acceptance
criteria, monitoring is continued until the temperature stabilizes within the range
or appropriate corrective actions are taken. Monitoring occurs at one hour
intervals for a . maximum four hour period; if the reading following the
temperature control adjustment is out, the unit is considered "out of order", and
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is emptied and serviced. It is not put back into service until shown to be stable
at the required temperature range.
Analytical balances are calibrated annually (or more frequently if required
under a specific program) by an outside service. A dated sticker, certifying the
calibration, is placed on each balance. Records for balance
calibration/servicing are maintained in Pace QA files. Multi and single point calibration checks are regularly performed to ensure the accuracy of each balance. The results are recorded in dedicated logbooks that are maintained
at each balance location. Balances that do not satisfy specifications are taken
out of service for replacement or repair. ASTM Class "1" weights must be verified/calibrated every two years.
13:3 MAINTENANCE DOCUMENTATION
All routine and non-routine instrument maintenance is documented in maintenance
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logbooks assigned to each instrument. To provide a clear and complete history of repairs I and maintenance associated with each instrument, each maintenance entry must include the following elements:
1.
2.
3.
An explanation of the reason for the maintenance or repair, e.g., was this action taken to fix a problem or was it part of routine instrument maintenance
A full description of the maintenance or repair actions taken
A description of how the analyst demonstrated that the analytical system was operating in control after completion of the maintenance actions, but before the resumption of sample analysis
When maintenance is performed to repair an instrument problem, the entry should include a description of the symptoms or problem that precipitated the maintenance actions. Depending on the initial problem, demonstration of return to control may be satisfied by the successful analysis of a reagent blank or continuing calibration standard. The entry must include a summary of the results of that analysis and a verification by the analyst that the instrument has been returned to an in-control status. In addition, each entry must include the initials of the analyst making the entry, the dates the maintenance actions were performed, and the date the entry was made in the maintenance logbook, if different from the date(s) of the maintenance.
13.4 SPARE PARTS
Along with the development of maintenance schedules, an adequate inventory of spare parts is required to minimize equipment downtime. This inventory should emphasize those parts and supplies that:
are subject to frequent failure,
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have limited useful lifetimes, or
cannot be obtained in a timely manner should failure occur.
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Department Manager/Supervisors are responsible for maintaining an adequate inventory of necessary spare parts for all major instruments and equipment items. Examples of spare parts maintained for major instrumentation systems are listed in Table 13.1.
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TABLE 13.1
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Scheduled Maintenance Procedures and Representative Spare Parts
for Major Instrumentation
INSTRUMENT MAINTENANCE PROCEDURE SPARE PARTS Gas Chromatography 1. Change septa and inserts as 1. Syringes Mass Spectrometry needed 2. Septa and inserts (GC/MS) 2. Clip column 3. GC columns 3. Replace pump oils as needed 4. Various electronic components 4. Change gas line dryers as 5. Plumbing supplies -tube needed fittings
5. Clean source as needed
6. Replace electron multiplier as
needed
Gas Chromatography (GC) 1. Change septa and inserts as 1. Syringes
needed 2. Septa and inserts
2. Clip column 3. GC columns 3. Change gas line dryers as 4. Various electronic components needed 5. Plumbing supplies -tube 4. Leak check when installing fittings
new analytical column
5. Check inlet system for residue
buildup periodically
Purge and Trap Sample 1. Replace trap as needed 1. Spare traps Concentrator 2. Decontaminate system as 2. Various electronic components required by blank analysis and circuit boards 3. Leak check system 3. Plumbing supplies -tube 4. Measure flowrates for each fittings
sparging position monthly
Inductively Coupled Argon 1. Clean torch assembly and 1. Spare torch and mixing Plasma Spectrometer (ICP) mixing chamber when dis-chamber
colored or after 8 hours of 2. Spare coil
running high dissolved solids 3. Plumbing supplies -tube samples fittings
Graphite Furnace Atomic 1. Change graphite contact rings 1. Contact rings Absorption as needed 2. Graphite cups and electrodes Spectrophotometer 2. . Clean quartz windows as 3. Autosampler tubing
needed
Hg Analyzer 1. Clean tubing and quartz cell 1. Quartz cells
as needed 2. Aspirator
2. Clean aspirator as needed 3. Plumbing supplies 3. Replace drying tube media
daily
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14.0 DATA QUALITY ASSESSMENT
Date: 12/22/95
Section 14.0
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Data quality assessment requires the review of quality control samples for precision, accuracy, representativeness, completeness, and comparability. Precision and accuracy data are used to determine the acceptability of analytical results. Standard operating practices require the use of a minimum of 20 tabulated precision or accuracy data points to prepared quality control charts. However, preliminary control limits can be established using as few as four data points. The Shewhart technique is the statistical method used to construct the charts. These quality control charts provide a quick visual means for monitoring the daily performance of the laboratory and identifying nonconformance trends.
For every batch of samples analyzed, a series of quality control samples are analyzed to assess the precision, accuracy and validity of the analysis. These data are reviewed before release of the data. All QC data are stored at Pace and are useable for determination of method precision and accuracy. Pace makes every effort to meet or exceed the accuracy and precision data as defined within specific methodologies. However, for actual matrices these data may not be comparable.
To estimate accuracy, spiked blank samples (laboratory control samples) and matrix spike sample recoveries are evaluated. This allows for the determination of both method and actual sample batch accuracy. Precision is measured and monitored in two ways: using range control for duplicate pairs and relative percent differences. Pace uses the formulas presented in Standard Methods, SW 846 and the USEPA Quality Assurance handbooks for calculations of precision and accuracy. This section illustrates calculations for determining data quality in terms of precision and accuracy. In addition to calculations concerning precision and accuracy, those which pertain to representativeness, completeness, and comparability are used to ascertain the level at which DQOs have been satisfied. Calculations for these other data quality indicators are included as well.
14.1 PRECISION
Precision is the degree to which the measurement is reproducible. Precision can be assessed by duplicate measurements of a laboratory control sample or an environmental sample. The precision of laboratory analytical data can be expressed using one of several statistical determinations, including: 1-standard deviation, 2-range, 3-relative standard deviation, also known as the coefficient of variation, and 4-relative percent difference.
Standard deviation is a measure of the variance of individual observations from the mean. It is usually denoted as "s" and is defined as:
n n
EX/-(D</tn
i=1 i=1
s = or
n -1
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In this equation, n
X;
X
= population size
= ith observation in the sample
= sample mean
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Standard deviation can be used to determine variation among several RPO values for duplicate pairs and establish statistical limits for duplicate RPO. Range control may also be used.
Range is the largest observation in a data set minus the smallest observation in the data set, often denoted as "R".
Where:
R= A-B
X= A..±-6
R
X
A
B
n
n
= Range of a pair of results
= Average of a pair of results
= Duplicate value 1
= Duplicate value 2 =: 2 (represents a single duplicate pair)
To graphically represent the data of numerous duplicate pairs on control _charts, the following calculations are performed using statistical numbers.
Where:
X= the sum of X / n
R = the sum of R / n
X
R
X
R
n
= Grand Mean
= Average Range
= Average of a pair of results
= Range of a pair of results
= 2 (represents a single duplicate pair)
Control limits for ranges (R -bar chart):
CL= 3.27 (R)
WL = R + 2/3 (3.27 R-R)
Where: R = Average Range
CL = Control Limit
WL = Warning Limit
To determine if the proper range control chart is being used for evaluation of a duplicate pair of results, the X control chart may be used.
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Control limits for averages (X -bar chart):
Where:
UCL = X + 1.88 (R)
LCL = X-1.88 (R)
UWL = X + 2/3 (1.88 R)
LWL = X -2/3 (1.88 R)
X
R
UCL
LCL
UWL
LWL
= Grand Mean
= Mean Range
= Upper Control Limit
= Lower Control Limit
= Upper Warning Limit
= Lower Warning Limit
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Relative standard deviation (RSD), or coefficient of variation (CV), is a commonly used measure of variability that is adjusted for the magnitude of the values in the sample:
RSD = Standard Deviation x 100%.
Mean
RSD is used most often when the size of the standard deviation changes with the size of the mean. Individual measurements of RSD or CV can be combined (pooled) to give an overall measure of variability for a given type of analysis or measurement:
Pooled CV=
In this equation,
n
2 ~ DF1
i=1
Xi = CV of data set i
DF1 = degrees of freedom from data set i (k; -1)
n = number of data sets
k; = number of data points in set i
= data set 1, 2, 3 ... n
Relative percent difference (RPO) is another commonly used measure of variability that is adjusted for the magnitude of the measured values. It is used only when the sample
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contains two observations. The results of the duplicate analyses are computed and the absolute RPO is calculated using the following equation:
Where:
RFD= Ix, -x,I xlOO
x1 +x2
2
= Relative Percent Difference
= first sample value (original)
= second sample value (duplicate)
For duplicate results RPO is directly related to RSD by:
RPO= )2RSD
The RPDs are tabulated, the average RPO and standard deviation are calculated, and a control chart constructed. Formulas for control limit are:
14.2 ACCURACY
UCL = B.E.Q+ 35
UWL = RPO +25
LCL always equals 0
Accuracy measures the degree of difference between observed and true values. The actual test result is compared to the theoretical result of 100% recovery and the percent
recovery calculated. The accuracy of sample data can be assessed using the laboratory
control spike, the environmental sample spiked with target analytes (matrix spike), or surrogate standards. Accuracy data are evaluated against established control limits. The percent recovery is computed using the following equation:
Where:· M
B
T
M-B %R=--xl00
T
= Measured concentration of analyte in spiked sample
= Background concentration of unspiked sample
= Target value (known concentration of analyte in spike)
The percent recovery data for a compound or parameter are tabulated, the average percent recovery and standard deviation calculated, and a control chart constructed.
The accuracy of laboratory analytical data can also be presented in terms of: 1-percent relative error, and 2-confidence intervals at the 95% level.
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Date: 12/22/95
Section 14.0
Revision 0.01
Page 5 of 7
Percent Relative Error = Measured Value -Actual Value x 100%
Actual Value
95% Confidence Interval =
In this equation, X
s
n
a·
X +
= sample mean
= sample standard deviation
= sample size
= risk level (0.025 for 95% confidence
interval)
= value of the tabulated student's "t"
distribution for n-degrees of freedom
and risk level a
Percent recovery is related to percent relative error by:
% Recovery = % Relative Error + 100
The correlation coefficient, "r'' is used to determine the acceptability of multi-point initial calibration data. The correlation coefficient value reflects the degree of fit of the calibration data with a linear or other curve function and is calculated as:
n(Exy) -(Ex) (Ey)
r =
In this equation, x = concentration of the standard
y = instrument response (peak area)
n = number of calibration points (x,y data pairs)
14.3 CONTROL CHARTS
Once a minimum of 20 QC data points are tabulated, an accuracy control c:hart can be constructed as follows:
Compute the mean value of the tabulated points.
Where:
:\lqapreva\sect14.doc
p
P;
n
"p P=L., I
n
= Mean Value
= Sample result
= Total number of results in data set
Date: 12/22/95
Section 14.0
Revision 0.01
Page 6 of?
Using the mean (P), compute the standard deviation (SD) of the data set.
Where: SD
X
p
n
SD=
=
=
=
=
I(x-P)'
(n-1)
Standard deviation
Sample result
Mean value
Total number of results in data set
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Employing the mean and standard deviation of the data set, determine the upper and I lower warning and control limits are determined as described in 14.3.1 and 14.3.2.
14.3.1
14.3.2
Warning Limits I
Warning limits represent the 95% confidence interval and are equal to the ii mean value for the control sample plus or minus two standard deviations ti
(2SD). Exceeding these limits is warning that the analy1ical system may be
approaching an out-of-control situation and should be inspected for possible
sources of error. The warning limits are calculated with the following equation: I
Where:
Control Limits
WL= P±2SD
WL
p
SD
=
=
Warning limits
Mean
Standard deviation
Control limits represent the 99% confidence interval and are equal to the mean
value of the control sample, plus or minus three standard deviations (3SD).
Exceeding these limits indicates that the analy1ical system is out-of-control.
Control limits are calculated using the following equation:
Where:
CL= P±3SD
CL
p
SD
=
=
=
Control limits
Mean
Standard deviation
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14.3.3 Utilization of Acceptance Limits
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Once the warning and control limits are established, a control chart is
constructed.
To verify the control chart, the initial data points are checked against the newly
generated limits for statistical outliers. Subsequently generated QC sample
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Section 14.0
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data are then plotted on the chart. The plotted points must fall within the control limits for the result to be accepted and the associated sample data validated. Outliers are evaluated for corrective action measures. Control charts are prepared for each required parameter, the limits updated at least annually and graphs produced for identification of trends. ·
The laboratory must also review control charts for out-of-statistical control trends. Any of the following trends is considered an out-of-control trend
occurrence.
• Any three consecutive points are outside warning limits.
• Any seven consecutive points are on the same side of the mean of the central line.
• Any six consecutive points are such that each point is larger (smaller) than its immediate predecessor.
• Any obvious cyclic pattern in the points.
14.4 REPRESENTATIVENESS
Representativeness is a qualitative element related to the ability to collect a sample that reflects the characteristics of that part of the environment being assessed. Sample representativeness is dependent on the sampling techniques used and is considered individually for each project site. It is specifically addressed in each work plan.
14.5 COMPLETENESS
Completeness is a measure of the amount of valid data obtained from a measurement system compared with the amount that was expected to be obtained unde,r normal conditions. It is expected that laboratories should provide data meeting QC acceptance criteria for 95% or more of the requested determinations. It is necessary for data users to identify any sample types which require 100% completeness. The mathematical formula is as follows:
Where:
14.6 COMPARABILITY
C=½xIOO
C
V
T
=
=
=
Percent completeness
Number of measurements jud!Jed valid
Total number of measurements
Comparability expresses the confidence with which one data set can be compared to another data set measuring the same property. For example, the use of EPA approved methods and procedures ensure comparability with other data from previous of following studies using the same methods.
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15.0 CORRECTIVE ACTION
Date: 2/28/97
Section 15
Revision 0. 02
Page 1 of 13
This section describes the quality assurance system at Pace Analytical, established to address
the documentation and correction of problems encountered during sample handling and analysis.
In many instances. the accurate and timely communication of sample handling and analysis
problems to laboratory Managers/Supervisors, Project Managers, and/or the QA Officer can mean
the difference between a situation that is corrected with little or no impact to sample data quality
and one that results in resampling.
When a problem arises, action to correct the problem must be taken promptly. For example,
laboratory Managers/Supervisors must initiate corrective action whenever QC results for control
parameters fail to stay within acceptance limits. In many situations, input from the client is
important in deciding how problems are to be resolved.
When errors, deficiencies, unusual occurrences, or out-of control situations exist, the QA program
provides systematic procedures, called "corrective actions", to resolve problems and restore
proper functioning to the analytical system. Within Pace Analytical, a distinction is made between
"out-of-control events" and "unusual occurrences" for the purposes of requiring corrective actions.
An out-of-control event is any event which is beyond the acceptance limits established for
laboratory operation by Pace Analytical SOPs, EPA methods, or client specific contracts or
protocols. This can be due to data which are outside of the accepted bounds for accuracy and/or
precision, method contamination, improper instrument calibration or maintenance, or deviations
from the contract or SOP detected by a QA audit.
An unusual occurrence is a situation in which the analytical system is, strictly speaking, compliant
with the protocol or SOP and therefore in control but an atypical or undesirable incident has
occurred which warrants further investigation. Such an occurrence could be a holding blank
which is contaminated or differences in the pattern of non-spiked target compounds between a
spiked and unspiked aliquot of a sample used as the matrix spike.
Both out-of-control events and unusual occurrences are formally documented. Within Pace
Analytical, the formal documentation report is identified under the following designations:
Corrective Action Report (CAR); Non-conformance Memo (NCM); or Discrepancy Report (DR).
Each of these reports serves the same purpose (because of this, the names are used inter-
changeably) of documenting whenever either type of event is noted. A representative report form
is illustrated in Figure 15.1.
15.1 NON-CONFORMANCE MEMO
The primary tool for documenting deficiencies and problems is the nonconformance memo
(NCM). NCMs may be initiated by an analyst, laboratory Manager/Supervisor, Project
Manager, or other laboratory personnel. The NCM is used to document a specific problem
or deficiency noted during sample handling or analysis. Depending on the specific
problem or deficiency, corrective actions may be taken by the Analyst, laboratory
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Date: 2/28/97
Section 15
Revision 0.02
Page 2 of 13
Manager/Supervisor, Project Manager, or other laboratory personnel. Since problems
encountered with sample analysis often have the potential to impact data quality,
appropriate corrective action is frequently determined in communications between the
laboratory Project Manager and the client.
Each NCM requires the initials of the person documenting the problem as well as those of
any person documenting additional information or corrective action. Each NCM is then
reviewed and initialed by the department Manager/Supervisor. If the deficiency or problem
impacts client sample data, the department Manager/Supervisor passes the NCM directly
to the appropriate Project Manager for their review and followup. If the nonconformance
does not directly impact sample data quality or integrity, the department
Manager/Supervisor passes the NCM to the QA Officer.
The NCM must describe the actions taken at each step of the review process. Where an
NCM documents an analytical event that is judged to be out-of-control, evidence of return
to control must also be documented. Once documentation of the problem, corrective
action, and return to control is complete, the NCM is forwarded to the QA Officer for QA
review. QA review is documented with the QA Officer's initials and the completed original
NCM is either passed back to the appropriate Project Manager to be filed in the client
project file or is filed in the QA files, depending on the nature of the nonconformance.
15.2 OUT OF CONTROL EVENTS
Out-of-control events associated with the statistical analysis and review of data are
straight forward to identify. The Analyst generating the data is responsible for checking
the results against the established limits. Any deviations are immediately addressed. If
data are outside accepted limits, the Analyst immediately notifies the responsible Section
Supervisor. If the situation can not be corrected to prevent an out-of-control condition, the
Section Supervisor shall notify the Operations Manager and the Quality Assurance Officer.
The Operations Manager and Group Supervisors are respo.nsible for identifying the source
of the problem and initiating corrective action. Completion of corrective action should be
evidenced by the return of data to prescribed acceptable limits.
Events which do not cause an immediate obvious effect on data quality are more difficult
to identify. Such events could be samples stored at an incorrect temperature or held
beyond prescribed holding times, or improper maintenance of records. Everyone in the
laboratory is responsible for reporting "system" problems. Analysts should report out-of-
control events to their Group Supervisor, who should then in turn report the situation to the
Operations Manager. Corrective action is again the responsibility of the Operations
Manager and the Group Supervisors. They shall review and approve the action taken.
If an out-of-control event does occur during analysis, for instance an LCS recovery falls
outside the expected range, the analyst must describe on the corrective action report the
event, the investigative and corrective actions taken, the cause of the event, and notify the
QA Officer. In some cases, investigation of an out-of-control event will reveal no
problems. In such cases, only the event and the investigative action is recorded.
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Date: 2/28/97
Section 15
Revision 0.02
Page 3 cl' 13
The investigative action taken is somewhat dependent on the analysis and the event.
However, listed below is a progression of steps which may be taken to find the cause of an
out-of-control event:
Check calculations to ensure there are no errors
• Check standard and spiking solutions for degradation or contamination
Check instrument performance
If the problem is with the standards or instrument performance, the analyst must
recalibrate or retune the instrument before reanalyzing the sample extracts affected. If the
out-of-control condition is still not remediated, the samples may require reextraction and
reanalysis or data qualification.
It is occasionally necessary to qualify data when the accompanying quality control data are
not within established performance criteria. The qualifying of data alert the data end user
to the fact that the analysis was, to some degree, flawed and that the precision and
accuracy of the data produced may not fulfill the data quality objectives (DC!Os) for that
particular project. Based on the project DQOs, analytical data with qualifiers may not be
appropriate for the intended use.
15.2.1 Volatile Organic Analyses
:\lqapreva\sect15.doc
Method Blanks
If target compounds are detected in the method blank above the detection limit
(or reporting limit if different from the detection limit) (above 5 times the detection
and/or reporting limit for methylene chloride, acetone, toluene, and 2-butanone)
the corrective action consists of checking the calculations, reanalyzing the blank,
qualifying the associated sample data, and investigating the source of the
problem to implement corrective action for .the future. When target list
compounds are detected in a method blank, the following condition applies:
When any target compound is detected in a method blank above the action
levels listed earlier, but not in associated samples, then no qualifier is
applied.
Surrogates
The % recovery of each surrogate is calculated for each sample, blank, and
LCS. Corrective action is taken whenever one (or more) surrogate recovery is
outside the acceptance criteria. The following corrective actions are taken when
required as stated above:
Check calculations to assure there are no errors;
:\lqapreva\sect15.doc
•
•
•
•
Date: 2/28/97
Section 15
Revision 0.02
Page 4 of 13
Check internal standard and surrogate solutions for degradation,
contamination, etc., and check instrument performance;
If instrument failure is indicated, reanalyze the sample;
If a method blank surrogate is outside of acceptance criteria, then the
problem must be corrected before proceeding with sample analysis. This
may include reanalysis, reextraction or recalibration;
If the surrogate could. not be measured because the sample required a
dilution, no corrective action is required. The recovery of the surrogate is
recorded with the note "surrogate diluted out".
If all QC associated with the sample is within acceptance limits (the method
blank surrogate recovery and LCS spike recovery}, the problem may be
attributed to a matrix effect. To identify the matrix as the problem,
reanalyze the sample. Samples exhibiting a matrix effect will be qualified
and discussed in the report narrative.
Laboratory Control Samples
The % recovery of each spiked analyte in the Laboratory Control Sample (LCS)
is calculated. Corrective action is taken whenever the % recovery is outside the
established acceptance criteria for that analyte. The following corrective actions
are taken when required as stated above:
•
•
Check calculations to assure there are no errors;
Check internal standard and spiking standard solutions for degradation,
contamination, etc., and check instrument performance;
Reanalyze samples associated with a failed LCS, if available;
If that does not correct the problem, then the data is reported and a
qualifying statement included in the report narrative.
For Matrix Spike and Matrix Spike Duplicates, if all QC associated with a sample
is within acceptance limits (method blank and LCS spike recoveries), the
problem may be attributed to a matrix effect. Samples exhibiting a matrix effect
will be qualified and discussed in the report narrative as appropriate.
Calibration
For an initial 5 point calibration curve to be valid, the % relative standard
deviation of the individual relative response factors (RRF) for the Calibration
Check Compounds (CCC) shall be less than or equal to 30%. If this criteria is
not met, then the calibration curve shall be reanalyzed.
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15.2.2
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Date: 21;18197
Section 15
Revision 0.02
Page 5 ol' 13
For continuing calibration checks to be valid, the relative response factor for each
of the System Performance Check Compounds (SPCC) should be at least 0.300
(0.250 for Bromoform) and the RRF for each of the CCC should be .:::20%
different from the average RRF from the initial calibration. If these criteria are not
met, then the following corrective actions should be taken:
Check internal standard and standard solutions for degradation,
contamination, etc.,
Check instrument for contamination at the injection port inlet and front end
of the column;
If no source of the problem is identified, then a complete 5 point initial
calibration must be performed.
The SPCC and CCC for Volatiles are:
~
Chloromethane
1, 1-Dichloroethane
Bromoforrn
1, 1,2,2-Tetrachloroethane
Chlorobenzene
Semivolatile Organic Analyses
Method Blanks
CCC
Vinyl Chloride
1, 1-Dichloroethene
Chloroform
1,2-Dichloropropane
Toluene
Ethylbenzene
If target compounds are detected in the method blank above the detection limit
(or reporting limit if different from the detection limit) (above 5 times the detection
limit and/or reporting for phthalate esters) the corrective action consists of the
following:
• Checking the calculations;
•
•
Reanalyzing the blank;
Flagging the associated sample data;
Investigating the source of the problem to implement corrective action for
the future.
:\lqapreva\sect15.doc
Date: 2/28/97
Section 15
Revision 0.02
Page 6 of 13
When target list compounds are detected in a method blank, the following data
condition applies:
• When any target compound is detected in a method blank above the action
levels listed earlier but not in associated samples, then no flag is applied.
Surrogates
The % recovery of each surrogate is calculated for each sample, blank, and
standard. Corrective action is taken whenever one (or more) surrogate recovery
from either the base/neutral or acid fraction is outside the acceptance criteria.
The following corrective actions are taken when required as stated above:
Check calculations to assure there are no errors;
Check internal standard and surrogate solutions for degradation,
contamination, etc., and check instrument performance;
If instrument failure is indicated, reanalyze the sample;
If more than one method blank surrogate is outside of acceptance criteria
or if one surrogate yields less than 10% recovery, then the problem must
be corrected before proceeding with sample analysis. This may include
reanalysis, reextraction or recalibration;
• If the surrogate could not be measured because the sample required a
dilution, no corrective action is required. The recovery of the surrogate is
recorded with the note "surrogate diluted out";
If all QC associated with the sample is within acceptance limits {the method
blank surrogate recovery and LCS spike recovery), the problem may be
attributed to a matrix effect. If any one surrogate yields less than 10%
recovery or if more than one surrogate in a fraction fails, reanalyze the
sample to demonstrate matrix interference. Samples exhibiting a matrix
effect will be qualified and discussed in the report narrative.
Laboratory Control Samples
The % recovery of each spiked analyte in the Laboratory Control Sample is
calculated. Corrective action is taken whenever recovery is outside the
acceptance criteria. The following corrective action is taken when required as
stated above:
Check calculations to assure there are no errors;
Check internal standard and spiking standards solutions for degradation,
contamination, etc., and check instrument performance;
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Reanalyze all associated samples, if available;
Date: 2/28/97
Section 15
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Page 7 of 13
If that does not correct the problem, then the data is reported and a
qualifying statement regarding the laboratory control sample is included in
the report narrative.
For Matrix Spike and Matrix Spike Duplicates, if all QC associated with a sample
is within acceptance limits (the method blank and LCS/LCS dup spike recovery),
the problem may be attributed to a matrix effect. Samples exhibiting a matrix
effect will be qualified arid discussed in the report narrative as appropriate.
Calibration
For an initial 5 point calibration curve to be valid, the % relative standard
deviation of the individual relative response factors (RRF) for the Calibration
Check Compounds (CCC) should be less than or equal to 30%. If this criteria is
not met, then the calibration curve should be reanalyzed.
For continuing calibration checks to be valid, the relative response factor for each
of the System Performance Check Compounds (SPCC) should be at least 0.050
and the RRF for each of the CCC should be :o. 20% different from the average
RRF from the initial calibration. If these criteria are not met, then the following
corrective actions should be taken:
Check internal standard and standard solutions for degradation,
contamination, etc.,
Check instrument for contamination at the injection port inlet and front end
of the column;
If no source of the problem is identified, then a complete 5 point initial
calibration must be performed.
The SPCC and CCC for Semivolatiles are:
.secc
n-Nitroso-di-n-propylamine
Hexachlorocyclopentadiene
2,4-Dinitrophenol
4-Nitrophenol
Acenaphthene
1,4-Dichlorobenzene
Hexachlorobutadiene
n-Nitroso-di-phenylamine
Di-n-octylphthalate
Fluoranthene
Benzo(a)pyrene
Date: 2/28/97
Section 15
Revision 0.02
Page 8 of 13
4-Chloro-3-methylphenol
2,4-Dichlorophenol
2-Nitrophenol
Phenol
Pentachlorophenol
2,4,6-Trichlorophenol
15.2.3 Gas Chromatography Analyses
Method Blanks
:\lqapreva\sect15.doc
If target compounds are detected in the method blank above the detection limit
(or reporting limit if different from the detection limit) the corrective action consists
of the following:
• Checking the calculations;
Reanalyzing the blank;
Flagging the associated sample data;
Investigating the source of the problem to implement corrective action for
the future.
When target compounds are detected in a method blank, the following conditions
apply:
When any target compound is detected in a method blank above the action
levels listed earlier, but not in associated samples, then no flag is applied.
Surrogates
The % recovery of each surrogate is calculated for each sample, blank, and
standard. Corrective action is taken whenever one (or more) surrogate recovery
is outside the acceptance criteria. The following corrective action is taken when
required as stated above:
• Check calculations to assure there are no errors;
Check standard and surrogate solutions for degradation, contamination,
etc., and check instrument performance;
If instrument failure is indicated, reanalyze the sample;
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Section 1S
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If the surrogate could not be measured because the sample required a
dilution, no corrective action is required. The recovery of the surrogate is
recorded with the note "surrogate diluted out";
If all QC associated with the sample is within acceptance limits (the method
blank surrogate recovery and LCS spike recovery), the problem may be
attributed to a matrix effect. Samples exhibiting a matrix effect will be
qualified and discussed in the report narrative.
Laboratory Control Samples
The % recovery of each spiked analyte in the Laboratory Control Sample is
calculated and corrective action is taken whenever recovery is outside the
acceptance criteria. The following corrective action is taken when required as
stated above:
Check calculations to assure there are no errors;
Check standard and spiking standard solutions for degradation,
contamination, etc., and check instrument performance;
• If that does not correct the problem, then the data is reported and a
qualifying statement regarding the laboratory control sample is included in
the report narrative.
Calibration
For an initial 5 point calibration curve to be valid, the responses for each
compound should be linear over the calibration range (generally linearity is
defined as having an RSD :s; 20%). If this criteria is not met, then the calibration
curve should be reanalyzed.
For continuing calibration checks to be valid, the % difference in the calibration
factor for each compound in calibration should not exceed 15% from the initial
calibration. If these criteria are not met, then the following corrective actions
should be taken: ·
• Check standard solutions for degradation, contamination, etc.,
• Check instrument for contamination at the injection port inlet and front end
of the column;
If no source of the problem is identified, then a complete 5 point initial
calibration must be performed.
Date: 2/28/97
Section 15
Revision 0.02
Page 10 of 13
15.2.4 Metals Analyses
Method Blanks
:\lqapreva\sect15.doc
If target analytes are detected in the method blank above the reporting limit the
corrective action consists of the following:
•
•
•
Checking the calculations;
Reanalyzing the blank;
Investigating the source if the problem to implement corrective action for
the future;
Redigesting and reanalyzing the associated samples if the analyte
concentration in the samples is less than 5 times the blank concentration
and greater than the reporting limit.
Data that cannot be regenerated acceptably is flagged as non-compliant.
When target analytes are detected in a method blank, the following data
condition applies:
When any target analyte is detected in a method blank above the action
levels listed earlier but not in associated samples, then no flag is applied.
Laboratory Control Samples
The % recovery of each spiked analyte in the Laboratory Control Sample is
calculated. Corrective action is taken whenever recovery is outside the
acceptance criteria. The following corrective action is taken when required as
stated above:
• Check calculations to assure there are no errors;
Check standard and spiking standard solutions for degradation,
contamination, etc., check instrument performance;
Redigest and reanalyze samples if there is no indication of failure in any of
the above;
• If that does not correct the problem, then the data is reported and a
qualifying statement regarding the laboratory control sample is included in
the report narrative.
For Matrix Spike, Matrix Spike Duplicates and Sample Duplicates, if all QC
associated with a sample is within acceptance limits (method blank and LCS
spike recoveries), the problem may be attributed to a matrix effect. Samples
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Section 15
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exhibiting a matrix effect will be qualified and discussed in the report narrative as
appropriate.
An exception to this criteria is allowed for matrix spike samples when the sample
concentration exceeds the spike concentration by a factor or 4 or more. In that
instance, the data is reported unqualified.
Calibration
For an initial and continuing instrument calibration to be valid, the responses for
each analyte must be linear over the calibration range and the accuracy of
calibration, as determined by analysis of an independent check standard, must
be within ±10% of the true value for ICP analysis and within ±20% for cold vapor
and graphite furnace AA analyses. If these criteria are not met, then the
following corrective actions taken:
Check standard solutions for degradation, contamination, etc.,
Check instrument for contamination, incorrect operating conditions, etc.;
If no source of the problem is identified, then a complete instrument
calibration must be performed.
OUT-OF-STATISTICAL-CONTROL BLANK SPIKE CONTROL CHART DATA
In accordance with the requirements of certain federal programs (Navy's NFESC [formerly
NEESA]. HAZWRAP), blank spike control charts are maintained for all analyses performed
for that program. Control chart data consist of recovery values derived from blank spike
(LCS) data. Each control chart has five lines representing a statistical analysis of a set of
percent recoveries from previously analyzed LCS samples:
1.
2.
3.
4.
5.
arithmetic mean
upper warning limit (+2 standard deviations from the mean)
lower warning limit (-2 standard deviations from the mean)
upper control limit (+3 standard deviations from the mean)
lower control limit (-3 standard deviations from the mean)
Plotted blank spike recovery data are evaluated against these limits to monitor for out-of-
control and out-of-statistical-control conditions.
15.3.1 Out-of-Control Blank Spike Recovery Pata
For a specific parameter and matrix, the laboratory process is considered out of
control if any one blank spike recovery value is outside the control limits on the
respective blank spike control chart. Except where LCS control limits are defined
by the client, excursions of the blank spike control limits equate to LCS
recoverie_s falling out of control.
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Section 15
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15.3.2 Out-of-Statistical-Control Conditions
For a specific parameter and matrix, the laboratory process is considered out of
statistical control whenever one or more of the conditions described below is
demonstrated by control chart monitoring:
1. Any three consecutive points are outside the warning limits
2. Any eight consecutive points are on the same side of the centerline
3. Any six consecutive points are such that the value of each is larger ( or
smaller) than its immediate predecessor
4. Any obvious cyclic pattern is seen in the points
The blank spike control charts serve as a mechanism both to note excursions
from the prescribed control limits and for recognizing trends that may represent a
degradation of an analytical system's quality control. They are valuable as an
early warning indicator that corrective action is needed to prevent more serious
loss of quality control.
15.3.3 Corrective Action for Out-of-Statistical-Control Conditions
In the course of plotting blank spike recovery data, if a condition is observed that
meets one or more of the criteria described above as an out-of-statistical-control
condition, corrective action must be taken. An NCM must be initiated that
identifies the trend causing the out-of-statistical-control condition. Where known,
the NCM should describe the root cause of the trend or excursion and the
actions taken to prevent recurrence.
For some statistical trends, such as eight or more points on one side of the
mean, the initial required corrective action may be no more than to continue
monitoring future blank spike recovery d_ata. If, however, the out-of-statistical-
control condition persists, or if the condition recurs repeatedly, further corrective
action, such as instrument maintenance or recalibration, must be performed
before sample analysis may resume.
15.4 UNUSUAL OCCURRENCES
Whereas out-of-control events involve occurrences outside of pre-established acceptance
windows, unusual occurrences are more subjective and involve incidents which may be
compliant with the assessment criteria but still warrant investigation. Many of these
investigations will be the result of the professional judgement of the analyst, auditor or data
reviewer that the analysis was not typical or reasonable. Another example of this type of
investigation is an inquiry or questioning of data received from a client or from the results
of performance evaluation samples.
:\lqapreva\sect15.doc
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FIGURE 15.1
Example
PACE CORRECTIVE ACTION REPORT
Revision 2 -3/94
Date: 2/28/97
Section 15
Revision 0.02
Page13of13
CLP_ NEESA_ SW846_ NPDES_ Drinking water_ AFCEE_ ACOE_
Sample ID Number(s) Involved and QC batch#.: _____________________ _
Type of Event: ·· Out-of Control Event ·· Attachments ·· Unusual Occurrence
Disposition of Samples:
1) Description of Event:
.. 1. LCS Failure
Contamination
·· 2. Blank Contamination
Failure
·· 3. Poor Precision
Reprepped ·· Reanalyzed ·· Narrated
·· 4. Prep Error ·· 7. Detection Limit
.. 5. Hold Time ·· 8. Calibration Failure
·· 6. Login Error ·· 9. Retention Time Window
·· 10. Linearity
·· 11. Sample
·· 12. Surrogate
··13_ Malrix Spike
Failure
··14.Other
(Describe Below)
2) Discussion of Known or Suspecled Cause.: ________________________ _
3) Corrective Action(s) Taken (include date, person and action): __________________ _
4) Return to Control:---------------------------------
Initial and Date below please
1) Reported by_~--2) Corrective Action Taken By· .. __ _,__ 3) Corrective Action Approved. __ ~
4) Documented Return to Control 5) Supervisor, __ .L__ 6) QA __ /
:\lqapreva\sect15.doc
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Date: 12/22/95
Section 16
Revision 0.01
Page 1 of 2
16.0 QUALITY ASSURANCE REPORTS TO MANAGEMENT
The objective of the Pace quality assurance program is to ensure that an operational system is in place which enables management to determine the quality of all data produced within the laboratory system. An essential component of the system is the communication pathways and feedback mechanisms which ensure that management obtains quality information promptly and consistently. To achieve·this objective, Pace employs informal and formal reporting processes to ensure that management is informed of operational quality. This information enables Pace to take corrective action promptly when required. Reporting occurs at the following frequency.
Daily meetings to discuss possible quality assurance problems and proposed solutions.
Weekly meeting with upper management to discuss laboratory performance, upcoming audits, certification programs, and past audit performances.
Quarterly written status reports to ·upper management; inclusion of all qualify assurance concerns and pertinent laboratory issues.
As required, internal departmental audit reports with observations and suggested corrective action procedures.
The Quality Assurance Officer and Quality Assurance Auditor are responsible for preparing reports to management indicating effectiveness of the laboratory Quality Assurance Program.
16.1 QUALllY ASSURANCE AUDITOR
Results of audits perfonmed by the QA staff are detailed in fonmal, written audit reports. These reports are distributed to the audited personnel, section supervisor, Laboratory Operations Manager, QA Officer, and General Manager for review and appropriate action. These and other QA-related reports are distributed as produced, with no set scl1edule.
Auditor reports will include, but not be limited to:
•
•
•
Results of internal laboratory review activities
Results of internal data review activities
Results of Proficiency Evaluation studies
Results of state certification applications
Summary of holding time exceedence and data qualification
Method detection limit study status
To demonstrate management review, the audit report will contain a page which will be signed and dated by the QA Officer and General Manager acknowledging that they have received the report and have reviewed its contents, and taken the necessary action dictated by their position.
:ILOAPREVA\SECT15.DOC
16.2 QUALITY ASSURANCE OFFICER
Date: 12/22/95
Section 16
Revision 0.01
Page 2 of 2
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The Quality Assurance Officer will issue a report of QA activities and findings on a regular I basis to the General Manager. The status report will include:
Results of internal systems or performance audits I Corrective Action recommendations
Discussion of QA issues raised by laboratory users
Results of third party or external audits I Status of laboratory certifications
Other significant events
Perfonmance Evaluation Sample Results I
16.3 MANAGEMENT REVIEW OF THE QUALITY ASSURANCE PROGRAM
Review of the appropriateness and adequacy of the Quality Assurance Program is ongoing. At anytime, any laboratory employee, through the Laboratory Operations Manager, may present recommended changes to the Quality Assurance Officer.
During system audits, the Quality Assurance Program should be discussed. The audif report will document recommendations made by either the Laboratory Operations Manager or the auditor for revision.
16.4 QUARTERLY QUALITY REPORTS TO MANAGEMENT
Quarterly reports are provided by the Quality Assurance Office staff to the Corporate Quality Office and the General Manager. The report summarizes quality assurance activities including details of corrective actions recommended or implemented, internal and external audit results, status of performance evaluation samples, certification status, and the status of internal procedure (evidentiary and technical) documents.
:\LQAPREVA\SECT15.DOC
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17.0 SUMMARY OF REVISIONS
Date: 12/22/95
Section 17. 0
Revision 0.01
Page 1 of 1
On November 10, 1995, a business transaction was consummated which created a new company, Pace Analytical Services. Inc., consisting of seven laboratories of PACE Incorporated. At the time of the transaction, in order to ensure an efficient transition to forming the new company, quality systems (e.g., QA plan, SOPs, etc.) which were previously in place at each of the laboratories remained intact.
This document describes a new consolidated quality assurance program including (as appropriate) key elements of each facility's previous quality control practices. As such, this document has been designated as Revision 0.01, representing the first revision of the former QA plan of PACE Incorporated.
17.1 REVISION DESIGNATION
Revision numbers are designated by an integer followed by two decimal places. At a minimum, this document will be reviewed in its entirety on an annual basis. Annual, document-wide review/revisions are tracked by incrementing the integer by one (e.g., Rev. 0.00 issued 5/22/95 will be revised no later than 5/22/96 and designated as Rev.· 1.00). The decimal places are used to track individual section or page revisions which occur in the interim between annual revisions. For example, when a section is initially revised independently of any other, the revision number indicated in the header will be listed as _.01 while the unrevised sections would remain at _.00. Subsequent
revisions of the same section or page would incrementally increase the decimal designation (e.g., 0.02, 0.03, 0.04, etc.) The cover page revision number will always reflect the total number of individual revisions performed between annual revisions. At the time of the annual revision, all individual section and/or page revision numbers are returned to an initial _.00 designation, which initiates a new overall revision number.
17.2 SUMMARY OF REVISIONS
This section will provide a historical chronology of all future revisions. The listing will contain the date of the revision, the section or page revised and the new revision number.
:ILQAPREVAISECT17.DOC
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Pace Analytical Services, Inc.
Minnesota Laboratory
Method Detection Limits,
Pace Reporting Limits
and
Quality Control Limits
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PACE Analytical Services, Inc.
Minnesota Laboratory
Method.
160.1
160.2
160.3
180.1
300.0
300.0
300.0
300.0
310.1
325.2
340.2
350.3
351.4
353.2
353.2
353.2
354.1
365.2
365.2
375.4
376.1
410.2
410.4
413.1
5310
. 5210B
SM3500-Cr D
200.7
General Chemistry
MDLs and PRLs
WATER
Component MDL (mg/L)
Total Dissolved Solids NA
Total Suspended Solids NA
Total Solids NA
Turbidity NA
Fluoride 0.013
Chloride 0.011
Bromide 0.035
Sulfate 0.028
Alkalinity 1.5
Chloride 0.36
Fluoride 0.0066
Ammonia Nitrogen 0.056
Total Kjeldahl Nitrogen 0.057
Nitrate as Nitrogen 0.035
Nitrite as Nitrogen 0.035
Nitrate + Nitrite as Nitrogen 0.035
Nitrite as Nitrogen 0.035
Phosphorus 0.012
Orthophosphate-P 0.0073
Sulfate 1.1
Sulfide 0.1
Chemical Oxygen Demand 1.5
Chemical Oxygen Demand 4.1
Oil & Grease 2.1
Total Organic Carbon 0.28
BOD 5-Day NA
Hexavalent Chromium 0.0013
Hardness (sum Mg & Ca C03) NA •·•···•·•/Method) •/· C::omponent''.,r· ........ -··. :-:::,.-:;/ ., ... ··.·-:.,,,.·.··:·:·.::·,:<',··:-:=.;·::r:::, I<.••·MDL••(ug/L)f
335.2 Cyanide 2.1
420.1 Phenol, Total 7.3
Page 1
·.:, PRL (ing/L)
10
10
10
0.5
0.1
1
1
1
5
1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.05
0.02
5
10
10
50
5
1
6
0.01
1
§\ if ~i:(1igi()i<
10
50
3/96
Pace Analytical Services, Inc.
Minnesota Laboratory
1::/i Method
No.
160.1
160.2
,160:3
160.4
180.1
300.0
335.2
420.1
310.1
325.2
340.2
350.2
351.3
353.2
365.2
365.2
370.1
375.4
· 376.2
410.2
410.4
413.1
418.1
425.1
5210B
5210B
5310
Sum of Ca &
Mg as CO3
... ,,· · ..... •<:\::.··
Analyte/
Component
Filterable Residue
Nonfilterable Residue
Total Residue·
Volatile Residue
Turbidity
Bromide
Chloride
Fluoride
Sulfate
Cyanide
Phenols, Total
Alkalinity
Chloride
Fluoride
Ammonia Nitrogen
Total Kjeldahl Nitrogen
Nitrate+Nitrite Nitrogen
Nitrate Nitrogen
Nitrite Nitrogen
Phosphorus
Orthophosphate-P
Silica
Sulfate
Sulfide
COD
COD
Oil and Grease
TRPH
MBAS
BOD 5-Day
CBOD 5-Day
TOC
Total Hardness
21nterim limits until statistically derived limits determined -------
General Chemistry
Quality Control Limits
· ... ;Ac_curacy:,,. precision-'.'
MS/MSD Recov. (%) MS/MSD RPD (¾)
Water Solid Water Solid
NA NA 20' NA
NA NA 20' NA
NA NA 20' NA
NA NA 20' NA
NA NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125! NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' NA 20" NA
75-125' NA 20' NA
75-125' NA 20' NA
75-1252 NA 20' NA
75-1252 NA 20' NA
75-125' NA 20' NA
75-125' NA 20' NA
75-125' 75-125' 20' 20'
75-1252 NA 20' NA
75-125' NA 20 1 NA
75-125' NA 20 2 NA
75-1252 NA 20 2
75-125' NA 20' NA
Page 1 ----
I : . Accuracy Precision
LCS Recovery('%) LCS/LCSD RPD (%)
Water Solid Water Solid
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20" NA
80-1202 NA 20' NA
80-120' NA 20-, NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20..., NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20' NA
80-120' NA 20 2 NA
80-120' NA 20 2 NA
80-120' NA 20 2 NA
80-120' NA 20 2 NA
80-120' NA 20 2 NA
80-120' NA 20' NA
80-120' NA 20 2 NA
80-120' NA 20 2 NA
80-120' 80-120' 20 2 20 2
80-120' NA 20 2 NA
80-1202 NA 20 2 NA
80-1202 NA 20 2 NA
80-1202 84-119 20..., 17
80-120' NA 20' NA
Rev.2 8/96 -----liiillll
------------------~ Pace Analytical Services, Inc.
Minnesota Laboratory
ICP-AES Water
Method , Analyte i•'• ·.·,. < \ MDL (ug/L)
6010 Aluminum 18
Antimony 21
Arsenic 79
Barium 3.1
Beryllium 1.2
Boron 17
Cadmium 3.2
Calcium 83
Chromium 4.7
Cobalt 5.3
Copper 2.5
Iron 11
Lead 37
Magnesium 21
Manganese 2.2
Molybdenum 10
Nickel 15
Potassium 420
Selenium 93
Silver 2.3
Sodium 69
Thallium 110
Vanadium 4.9
Zinc 5.1
Metals
MDLs and PRLs
PRL (ug/L) ··Method·
50 6010
50
90
5.0
5.0
100
5.0
200
5.0 . Method
10 7041
5.0 7060
25 7091
40 7131
30 7191
5.0 7201
20 7211
20 7421
2000 249.2
100 7740
5.0 7761
100 7841
220
10
20 IV!ethod
7470
Page 1
ICP-AES SuperTrace Water
Arialyte · MDL (ug/L) · PRL (ug/L)
Antimony 2.7 5.0
Arsenic 3.7 5.0
Cadmium 0.36 0.50
Lead 1.4 3.0
Selenium 2.8 5.0
Thallium 1.5 5.0
GFAA Water
Analyte MDL (ug/L) PRL (ug/L)
Antimony 2.4 5.0
Arsenic 2.1 5.0
Beryllium 0.058 0.20
Cadmium 0.042 0.10
Chromium 1.0 1.0
Cobalt 1.0 1.0
Copper 1.1 2.0
Lead 0.92 3.0
Nickel 2.5 5.0
Selenium 1.3 5.0
Silver 0.45 0.50
Thallium 2.8 5.0
CVAAWATER
Analyte MDL (ug/L) · PRL (ug/L)
Mercury 0.030 0.20
Rev.2 8/96
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APPENDIXB
Standard Operating Procedures
GEi Consultants, Inc.
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1 · . "-. ,' ·..,,.~·.
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SOP No. RE-OCH
Page 1 of 3
Objective
FIELD NOTEBOOK
Revision No. 0
Date: 2s6-95
The field notebook is intended to serve as a record of significant field activities performed
or observed by GEL The field notebook will serve as a factual basis for preparing field
observation reports. if required, and reports to clients and regulatory agencies ..
Procedure
l. Use a separate bound notebook for each site/location/project number.
2. Write neatly using black or blue ink (or note if field conditions (i.e., cold or wet
weather require use of pencil).
3. Write the project name, project number, and book number (i.e., I of 3) on the front
cover. On the inside cover, identify the project name, project number, and "Return
Book to" GEI's address.
4. Number all of the pages of the field book starting with the first entry.
5. Record activities as they occur.
6. Neatly cross out mistakes using a single line and initial them. Erasures are not
permitted.
7. Sign or initial and date the bottom of every page with an entry. Cross out unused
portions of a page.
8. Record the following information upon each arrival at the site:
a) Date/time/weather/project number
b) GEi personnel
c) Purpose of visit/daily objectives
9. Record conversations with: [Reco=endation -If possible, record telephone numbers
of individual contacts for the site in the field notebook.}
a) Contractors
b) Clients
c) Visitors (include complete names, title, affiliations, whenever possible).
d) GEi office staff
SOP No. RE-0()1
Page 2 of 3
Landowners (site or abutters)
Revision No. 0
Date: 2-6-95
e)
f) Note time of arrival and departure of individuals visiting the site.
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10. Examples of the field information to be recorded includes and time of occurrences. I
a)
b)
c)
d)
e)
f)
g)
h)
i)
j)
General site work activities
Subcontractor's progress
Type and quantity of monitoring well construction materials used
Use of field data sheets (i.e., boring logs, monitoring well sampling logs, etc.)
Ambient air monitoring data
Locations of sampling points
Surveying data (including sketches with north arrows)
Changes in weather
Rationale for critical field decisions
Recommendations made to the client representative and GEI PM.
11. Record the following information upon departure:
a) Include a site sketch of conditions at the end of the day.
b) Time
·c) Summarize work completed/work remaining
d) Place a diagonal line though and sign portions of pages not used or skipped.
Precautions
• Only record facts. Do not record opinions.
• Do not fail to record an observation because it does not appear to be relevant at that
time.
• Identify conditions or events which could effect[rmpede your ability to observe
conditions.
• Do not use spiral notebooks because pages can be easily removed.
References
1. ASFE Model Daily Field Report (1991), ASFE, Inc.
Attachment
Example Field Notebook
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----------
--.k~:}£-ii Ye . . L• ~pl~-!--<'
\'Ylc;,11 t,., '· () ~' , I.
!l:':i;y1f''"".,·1 ""'.J c[:1,,..,,i cJ 01 j'),,/i<,:.
_Q (lt1(r/ c,700
0 ?(iO i:0:1 Lr.:·\\:. d ,! • ",1 "( l. cl Bl i.=., . .. .
__ .. _ . . _ . Len f, 11 ! 1 r J Cc ! • l h, 5 , d, I Sq p. /.,;.,
___ , e~~'l ,5. frt· ~''.>"''.':i c::!. . .j'' :Sf2/.:J-
_________ .S[?frn ~•rnr/ r.
-·----· ........ ,;:<,"('le --H_,...1_ ~.+-e~l--_-_·-y_f:!)__
µ
! . i '"
I J l r
I:· P'
:;! :,
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SOP No. RE-002
Page 1 of 6
Objective
FIELD OBSERVATION REPORT
Revision No. 0
Date: 2-6-95
To accurately summarize the activities, observations, and decisions made during the day's
field work. The daily field observation report may serve as a permanent record of the day's
activity for the Project Manager, IHC, and client.
Procedures
At the close of the day's field work, a Field Observation Report must be prepared by the
individual responsible for the field notebook. This report must be completed before leaving
work for the day. Contents of the report should include, at a minimum, the following
information:
1. A record of person(s) present at the site, time of arrival, departure times (e.g., GEi,
contractor(s), client, etc.).
2. A record of the daily objective(s) and the activities performed (e.g., drilled five
borings in the overburden).
3. A summary of deviation(s) from the field plan or objectives.
4. A summary of field decision(s) made, who made it/them, and the basis for such
decision(s).
5. A diagram, sketch, and/or map showing the location and extent of the work or other
significant observation(s) made during the day.
6. Any recommendations that may result from field observations and any actions that
resulted from those recommendations
7. A summary listing and field sketch showing location(s) of field activity
8. Submit a draft report to the PM/IHC for review and editing related to the clarity and
conciseness of the report. Complete any editorial changes, sign, date, and submit the
report to PM/IHC for approval/signature. Field Observations Reports should be
written neatly. They need not be typed unless specifically requested by the PM.
SOP No. RE-002
Page 2 of 6
Precautions:
• Not all projects require daily field observation reports.
Revision No. 0
Date: 2-6-95
• The Field Observation Report should be based sole! y upon factual information not
opinions. Any speculation should be clearly noted in the report as such.
The Field Observation Report should never be released to anyone other than the
PM/IHC prior to review and sign-off unless explicitly authorized by the PM/IHC.
References
I. GEI Technical Manual, dated July, 1987
Attachment
Example Field Observation Report.
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FIELD OBSERVATION REPORT Date 0] /J 819?
PROJECT ABC Industries Buildinq Demolition Report No. 8
CLIENT Checkmore Development Project No. 99709
CONTRACTOR Demolition Brothers Page _-±-of .
TIME OF ARRIVAL '"" " DEPARTURE 1 ISA IS
WEATHER C:••-----~ ~" l:'
PERSONS CONTACTEDlAFFILIATION GEi REPRESENTATIVES
Reporter: Gerry E. Inline
Tom Tuttle/ Demolition Inc.
Joe Robinson/ Checkmore Development
Gary Bark/ Checkmore Development
Fran Garman I Checkmore Development
OBSERVATIONS
1. Pur12ose of Site Visit: The purpose of the site visit was
to observe the excavation of No. 2 fuel oil contaminated
soil from beneath and adjacent to the southwest corner of
the former ABC Industries (ABC) building and to collect
confirmatory soil samples from the bottom and sidewalls
of the excavation for DEF-certified laboratory testing.
on March 5, 1991, a release of No. 2 fuel oil was
observed upon removal of an underground storage tank
(UST) for the ABC. contaminated soil beneath and
adjacent to southwest corner of the ABC was left in place
during the initial clean up in the spring of 1991. The
ABC was demolished during December 1991 and January 1992
to allow for the construction of Parking Deck D5.
The figure on page 5 shows the location of the former
UST, the ABC building and the limits of contaminated
soil removed in the spring of 1993.
2 • Demolition of ABC: Wreckem Inc. demolished and removed
the majority of the ABC building before I arrived on
site. The basement wall and footing in the southwest
corner of the building (in the vicinity of the
contaminated soil) was left in place.
3 • Removal of Conci;:ete Floor Slab: Demolition Inc. removed
the floor slab in the southwest corner of the ABC
building. Concrete which was oil
on plastic.
stained was stockpiled
q) GEI Consultants. Inc. By-J:/ <a:::,,, £ · 1,::2l&£ ·M App'd ,
FIELD OBSERVATION REPORT
Date Ql/78(92
PROJECT ABC Building Demolition Report No. R __.,__ __ _
Project No. 93295
CONTRACTOR Demolition Brothers, Inc. Page 2 of
4. Excavation and Stockpiling of Soil: Demo!ition Brocners
excavated soil with a Komatsu excavator and stockpiled the
soil on site, north of the Mall building adjacent to Thurber
Construction's field trailer.
I collected samples of the excavated soil for jar headspace
screening for volatile organic compounds (VOCs). I screened
the samples using Massachusetts Department of Environmental
Procection's (DEF) Jar Headspace Method (DEF Policy #WSC-
400-89, Attachment I) using an organic vapor meter (OVM).
Demolition Bros. stockpiled the excavated soil on plastic in
three separate stockpiles based on the following criteria:
Stockpile 1:
Stockpile 2:
Stockpile 3:
voe levels greater than 100 parts per
million (ppm) and/or visible oil staining.
voe levels between 50 and 100 ppm without
visible oil staining.
voe levels less than 50 ppm without
visible oil staining.
The table on Page 3 shows the results of the jar headspace
screening. The figure on Page 6 shows the excavation limits
and the soil sample locations.
4
~l===============s"'=========================I
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I FIELD OBSERVATION REPORT Date 0l('.18('.92
I PROJECT ABC Industries Building Demolition Report No. 8
CLIENT Checkmore Development Company Project No. 99709
I CONTRACTOR Demolition Brothers, Inc. . Page 3 of 4
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Sample OVM
Location Sample Number Reading2 co=ents
Number1 (ppm)
l 99709-14N-45E-1613 0
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2 99709-0N-29E-160.5 19
3 99709-4N-35E-159 352
I 4 99709-3S-35E-157 475
5 99709-l0N-27E-158 406
I 6 99709-3N-34E-156.5 16 at groundwater table
7 99709-15N-31E-158 91
I 8 99709-13N-36E-156.5 28 at groundwater table
9 99709-12N-40E-158 389
I 10 99709-3S-55E-161 86 adjacent to concrete
floor slab
11 99709-10N-35E-157 67
I 12 99709-10N-35E-156.5 37 at groundwater table
Tested for TPlf'
I Notes: l. Sample locations shown on page 4.
2. DEP Jar Headspace Method #WSC-400-89, Attachment I.
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3. Sample No. 99709-14N-45E-161 is 24 ft. north and 55
ft. east of the center of Parking Deck D footing
Dl6/17 at elevation 161.
4. Sample delivered to a DEF-certified laboratory for
I TPH testing.
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FIELD OBSERVATION REPORT
ABC Industries Building Demolition PROJECT __________________ _
Checkmore Development company CLIENT ___________________ _
CONTRACTOR
Demoltion Brothers, Inc.
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Report No. 8
Project No. 99709
Page 4 of
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SOP No. SS-005
Page 1 of 2
Revision No. 0
Date: 2-6-95
MONITORING WELL DEVELOPMENT
Objective
The objective of this SOP is to standardize the development of monitoring wells for
environmental investigations. The purposes of developing a monitoring well are to remove
fluids introduced during drilling and to maximize the movement of water into the well by
reducing the fines which may be trapped in the sand pack around the screen, in order to
reduce siltation during sampling.
Procedure
1. Decontaminate all development equipment prior to use (see Equipment
Decontamination SOP).
2.
3.
4.
5.
6.
7.
Calculate or estimate the amount of water introduced to the borehole during drilling.
At a minimum, this is the amount of water that must be removed during development
In addition, compute the volume of water in the monitoring well.
Place a 12-volt submersible pump ( or grundfos pump) attached to a power source into
the borehole or use a manual sampling device such as a bailer or wate,rra pump.
Collect a sample of the standing water in the borehole and record the physical
properties (color, turbidity, etc.). Then, at a mioim11m, remove the greater of the
following two amounts of ground water:
a) ten well volumes
b) the amount of water introduced during drilling
Pump the ground water into a 5-gallon pail so that the volumetric flow rate and water
volume from the pump or bailer can be calculated.
Monitor the ground water level in the well as the water is being pumped to determine
if the pumping rate is sufficient to create a drawdown in the well. The "over-
pumping" development method requires that the well be developed/stressed at a faster
rate than the well would normally be pumped or bailed for sample collection.
Collect ground water samples every few well volumes during the pumping and record
the physical properties (color, turbidity, etc.) (see respective SOPs).
Once half the desired volume of water has been pumped, request that the drillers
attach surge blocks on a rod into the well. This surge block apparatus may be
operated by hand or be attached to the drill stem on the drill rig and is operated by
the driller. Slowly move the surge block up and down in the upper portion of the
well. Start at a slow pace and progress to a faster surging action further clown the
well screen.
SOP No. SS-005
Page 2 of 2
Revision No. 0
Date: 2-6-95
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8. During surging, remove the surge block periodically to pump more water from the I
well to remove accumulated fines.
9. Monitor the turbidity and color of the water during this procedure. The well is
considered fully-developed when all of the following criteria have been met:
a) the volume of water introduced during drilling has been removed
b) the water removed from the well is relatively free of fine-grained materials.
10. Record the final amount of water removed and the physical properties (color, turbidity)
of the well water.
Precautions
At all times, follow safety procedures as defined in the site-specific Health & Safety
Plan.
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• Always remove ground water with fines from the well before surging, as these fines 1 may be forced into the well screen otherwise by the surging action.
• If the ground water in the monitoring well is contaminated, the water removed during
well development will need to placed in a properly-labelled drum (see IDW SOP). I
• If the soils around the well screen are composed of fine-grained silts. and clays, over-
pumping and mechanical surging is not reco=ended since these more vigorous
techniques can cause mixing of the fines into the filter pack. To develop these wells,
use of a bailer is recommended.
References
1. Standard Practice for Design and Installation of Ground Water Monitoring Wells in
Aquifers (October 1990), American Society for Testing and Materials [ASTM] D5092-
90.
2. Nielsen, D.M. (1993), "Correct Well Design Improves Monitoring," Environmental
Protection, July. pp. 38-49.
3. "The Methods & Mechanics of Well Development, Part 2 of 5," National Drillers
Buyers Guide, March 1993, p. 17.
4. Standard References for Monitoring Wells (April 1991), Commonwealth of
Massachusetts Department of Environmental Protection, WSC-310-91.
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SOP No. SA-002
Page 1 of 4
Objective
GROUND WATER SAMPLING
Revision No. 0
Date: 2-6-95
To outline a method to collect ground water samples which accurately and precisely
represent the aquifer conditions.
Procedures
1. Record all activities in the field notebook (see Field Notebook SOP) and on the
Ground Water Sampling Form (attached). Use a separate form for each sampling
location and evenL
2. Calibrate PID, pH/temperature, and specific conductance (SC) meters (see respective
SOPs).
3. Purge Well
a) Unlock well cap and, if required by the Health & Safety Plan. measure organic
vapor concentration in the well pipe (see H&S Monitoring for VOCs SOP).
b) Measure (water level probe and/or oil water interface probe) depth to water and
overall well depth to the nearest 0.01 foot from the top of casing and the highest
point (or "V" notch) on the PVC. If the top of casing cannot be used, note the
reference location. Mark the datum point with an indelible marker and note
reference location in field book.
c) Calculate one well volume. V = 7t r2 h or use conversions on ground water
sampling form.
d) Purge well to remove stagnant water from sampling zone. Generally, water
should be drawn down from the upper portion of the water column in high
formations and the bottom of the water column in low yield formations. Record
the volume purged.
e) Monitor and record the ground water parameters (pH, temperature, and SC) from
the first bailer and after each well volume (see SOPs).
f) Purging is complete when one of the following has been achieved:
i) A minimmn of three well volumes have been purged or on the reference
ground water parameter has stabilized.
(±0.2 for pH, ± 0.1 for temp., ±<).1 for SC); or
SOP No. SA-002
Page 2 of 4
ii) The well has been pumped/purged dry.
g) Dispose of purge water according to the field plan.
Revision No. 0
Date: 2-6-95
h) Collect samples as soon as the volume of water is sufficient to fill the intended
sample containers.
4. Collect Samples
a) Begin sampling at the least contamioatP.d well and work toward the most
contaminated well.
b) To achieve comparable results, use a similar method to collect all samples
whenever possible.
c) Lower sampling device slowly into ground water to the middle of the screened
interval or water depth. Determine sampling location based upon project
specifics.
d) Fill sample containers directly from the sampling device in order of decreasing
volatility (see Sampling Handling SOP).
e) Remove sampling device and decontamioatP. (see Equipment Decontamination
SOP).
f) Store samples in cooler between 2°C and 6°C for transport to the laboratory.
g) Secure well cap.
Precautions
• At all times, follow safety procedures as defined in the site-specific Health & Safety
Plan.
• Prior to departure for the field, obtain available on information on well construction
for use in field investigation (i.e., screen and riser material, well diameter and depth,
and screened interval).
• When purging a well with a pump, the pump may require lowering to the middle of
the screened interval to obtain a reasonable flow on the basis of operational
requirements of the pump. If possible, the pumping rate should match the natural
aquifer yield rate.
• Measure ground water elevation twice.
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SOP No. SA-002
Page 3 of 4
Revision No. 0
Date: 2-6-95
• Be aware of any preservatives in the sample bottles and handle with care, in
accordance with the Health & Safety Plan.
References
1. Characterization of Hazardous Waste Sites -A Methods Manual: Volume II
(December 1984). U.S. EPA (EPA-600/4-84-076).
2. Draft Ground Water Monitoring Guidance for Owners and Operators of Interim Status
Facilities (1983), U.S. EPA.
3. Procedures Manual for Groundwater Monitoring at Solid Waste Disposal Facilities
(December 1980), U.S. EPA, (EPA-530/SW-611).
4. Test Methods for Evaluating Solid Waste (1986). U.S. EPA (SW-846).
5. Barcelona, Michael J.; Gibb, James. P.; and Miller, Robin A., A Guide to the
Selection of Materials for Monitoring Well Construction and Ground Water Sampling
(August 1983), Illinois State Water Survey Contract Report (ISWS) #327 (EPA
Contract No. EPA CR-809966-01).
6. Standard Reference for Monitoring Wells (April 19, 1991), Massachusetts DEP,
DEP Publication #WSC-310-91.
7. Groundwater Sampling Procedures Guidelines (1987), Wisconsin Department of
Natural Resources (WR-153-87).
;-J\ Project I Date
Well ID I Start nme
_.-:: Weather I I End nme
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Sampling Personnel
' Well Construction Water Level Well Volume
Well Diameter Well Depth 7 Conversion
: Roadbox Water Depth . Diam. Factor
• Top of Casing Water Height = linl lnaVftl
Top of Screen Conversion Factor X 1.5 0.09
Bottom of Screen One Well Volume = 2 0.16 .· . Bottom of Well 4 0.65
Place 1 for 1 sl step, 2 for 2nd step, etc. Volume Purged I I 6 1.5
• Decontamination Calibration Dates Eauioment Used Pur□e Sample
Ethyl Alcohol PID Teflon Bailer
Deionized Water S.C. Meter PVC Bailer
Alconox & DI H,0 pH/Temp. Submersible Pump
Tap Water Other: Peristaltic Pump
Solvent Tubing
Other: Other:
~ Check the equipment which applies.
: D -dedicated equipment.
Field Analysis Data
VOA Screening (ppm as Benzene): Ambient Air I I Well Mouth
• Well Purae Data
Volume Evacuated gal gal gal gal gal
Temperature (C)
:
pH (std units)
Specific Cond. (umho/cm)
WellVOAs (ppm)
EH (mV)
Dissolved Oxygen (ppm)
Other: ( )
·•
·. Samples Collected for Laboratory Analysts
' Samnles Collected Sample Bottle ID
VOA8240
VOA 8010 Time Sampled I I
.-TPH
ABN Color I
PCB
ALK/COD/BOD Turbidity I
Metals TYee of filter membrane
' Other: Filtered in Field ? I ~es I no I I ;
! Additional Observations:
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SOP No. SA-005
Page 1 of 2
Objective
SAMPLE HANDLING
Revision No. 0
Date: 2-6-95
Sampling Handling involves the collection and shipping of environmental samples to a
laboratory for chemical analysis. The overall objective of Sample Handling is to ensure:
• samples are properly labelled and documented;
• samples are proper! y preserved;
• samples are properly packaged; and
• samples are proper! y transported to laboratories.
Procedures
l. Label all laboratory glassware prior to collecting samples. The label should have an
adhesive and be placed on the jar or bottle, not on the cap.
2. Record the following information on the label and in the field notebook (See Field
Notebook SOP): project number, sample identification (i.e., MW201 or SS-2), date
and time of collection, samplers initials, and preservative, if present
3. At each sampling location, samples must be collected in order of volatility, most
volatile first Samples collected for volatile analysis must be placed in sample
containers immediate! y upon retrieval of the sample.
4. Aqueous samples for volatile analysis must be collected without air bubbles. Soil
samples for volatile analysis should be compacted to eliminate as much heads pace as
possible. Other laboratory glassware should also be filled when possible.
5. If compositing of samples is performed in the field, specify basis for composite
(i.e., volume, weight, spoon recovery, etc.) and record procedure for composing
sample in the field book.
6. Once samples have been collected, place samples in a cooler with ice or a blue pack
and start the chain-of-custody (See Chain-of-Custody SOP). See comment No. 1.
7. For shipping, individually wrap each sample bottle with "bubble packing" or suitable
packing material and place the wrapped bottles in the cooler with sufficient packing
material between samples to avoid breakage.
8. Place a layer of packing material above and below the sample bottles. Place blue ice
packs or ice bags on top of the packing material. Fill the remaining space in th,e cooler
with packing material to eliminate the possibility of vertical movement of samples.
SOP No. SA-005
Page 2 of2
Revision No. 0
Date: 2-6-95
9. Fill out the appropriate shipping or courier forms and attach to the top of the cooler.
If necessary, place the proper shipping labels on the cooler. Place a custody seal on
the cooler.
Precautions
• At all times, follow safety procedures as defined in the site-specific Health & Safety
Plan.
• Field personnel must be aware of analyses which have short holding times and
schedule sampling events and shipping accordingly. Shipment of samples for analyses
with short holding times must be planned in advance.
• In general, glassware for aqueous samples contains preservatives, i.e., HN03 or HO.
When collecting the sample, take care not to overfill the container, thus flushing the
preservative out of the bottle.
• Never composite samples for VOCs in the field. Collect individual aliquots and direct
laboratory to perform compositing.
• Collection of aqueous samples should not be performed over the opening of a
monitoring well. Preservatives from overfilling, a marker pen or other objects could
fall into the well.
• If the recharge volume for a monitoring well is low, completely fill all volatile vials
. and then collect the minimum sample volume required for each remaining analysis.
• During subsurface soil sampling, if the recovery from the split-spoon sample is
inadequate, if appropriate, resample the bottom of the borehole to obtain proper
sample volume.
• Laboratories will homogenize and test the contents of the sample container, unless
directed otherwise. Samples should not contain rocks, twigs, leaves, etc. unless these
materials are of interest
References
l. Manual of Ground-Water Quality Sampling Procedures (September 1981), U.S. EPA
Office of Research and Development (EPA-600/2-81-160).
2. Soil Sampling Quality Assurance User's Guide {March 1984), U.S. EPA Office of
Research and Development Environmental Monitoring Systems Laboratory,
Cooperative Agreement CR 810550-01 (EPA-600/4-84-043).
3. Standard References for Monitoring Wells (January 1991), Massachusetts Department
of Environmental Protection, DEP Publication# WSC-310-91.
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STANDARD OPERATING PROCEDURE
-SAMPLE CUSTODY -
PREPARED: March 15. 1991
REVISION: O ~ ~:.-::==-
PREPARED BY~~~ 1_ , DATE:
APPROVED BY: ~~..!(..,-,.,~ DATE:
1. PURPOSE
Revision_0_
Date March 15, 1991
Due to the potential evidentiary nature of samples collected as part of environmental
investigations at GEI Consultants. Inc., (GEI) possession must be traceable from the
time of collection until disposal or archival of the samples. This SOP details the
procedures and responsibilities for the GEi staff for maintaining and documenting
custody of the samples from the time of collection until shipment to the laboratory or
disposal.
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-2-
2. POUCY
Revision_Q_
Date March 15, 1991
It is GEi's policy that all samples collected as pan of an environmental investigation be
maintained under custody. A sample is under custody if:
1. It is in your possession, or
2. It is in your view, after being in your possession, or
3. It was in your possession and then you locked it up to prevent tampering, or
4. It is in a designated secure area.
-3-
3. PROCEDURE
Revision.JL
Date March 15, 1991
The custody procedures defined are for field and GEi storage activities until the time
of sample shipment to a laboratory or disposal.
3.1 Field Custody
Samples collected in the field are the responsibility of each sampler until the samples
are transferred to a person designated as the field sample custodian. Custody, as
defined above, must be maintained by the sampler.
The sampler is personally responsible for:
1. Labeling each sample in waterproof ink;
2. Recording the information on the label in a field notebook;
3. Proper sample preservation and storage of the sample until transferring the
sample to the field sample custodian; and
4. Maintaining sample custody.
The field sample custodian, who may be the same person as the sampler, is personally
responsible for:
1. Completion of the chain-of-custody form (Fig. l);
2. Checking and maintaining proper sample preservation and storage;
3. Maintaining sample custody;
4. Properly packaging the samples for transfer to the GEI facility or the laboratory
for analysis;
5. Signing and dating the chain-of-custody records when the samples are relinquished
and including the original chain-of-custody in the shipping container;
6. Maintaining a copy of the chain-of-custody form(s);
7. Sealing the shipping containers with chain-of-custody seals prior to shipment; and
8. Arranging shipment or delivery of the samples.
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3.2 Custody at the GEi Facility
Revision_O_
Date Marcin 15. 1991
Samples may be stored at GEI following field activities prior to shipment to a
laboratory. In addition, samples for screening may also be delivered 10 the GEI
laboratory.
3.2.1 Sample Storage
Samples may be delivered to the GEI facility by the field sample
custodian/sampler, courier service, or other delivery service. Sample receipt and
storage at the GEI facility is controlled by a limited number of GEI employees,
each of whom may be designated as facility sample custodian. Control is
established by possession of keys that permit access to the sample s10rage
refrigerawrs. The employees with keys are listed in Table 1.
The field sample custodian, who may be the same person as the sampler, is
personally responsible for:
1. Relinquishing the samples under chain-of-custody to one of the GEI
employees listed on Table l; and
2. Signing and dating the chain-of-custody forms.
In the event that none of the facility sample custodians are available at the time
of sample delivery, the shipping container must be stored in a secure area with
custody seals to prevent tampering until such time that a facility sample custodian
can be notified.
The facility sample custodian is personally responsible for:
1. Verifying that the information on the sample labels matches that on the
chain-of-custody record;
2. Noting any discrepancies between the sample labels and the chain-of-custody
on the chain-of-custody form;
3. Signing the chain-of-custody form, thus establishing cuswdy of the samples;
4. Logging the samples into the GEI sample refrigerator log (Fig. 2); and
5. Placing the samples in the refrigerator and locking the refrigerator.
-5-
Revision_Q_
Date March 15, 1991
In addi!icn, when samples are requested by another GEI employee for shipment
to an outside laboratory or disposal, the facility sample custodian is personally
responsible for:
1. Completing the GEI sample refrigerator log;
2. Having the person receiving the samples sign the log; and
3. Relocking the refrigerator.
3.2.2 GEi Screening
GEI operates a sample screening program. If samples are delivered by the field
sample custodian for sample screening, they should be delivered to the sample
screening laboratory.
The field sample custodian, who may be the same person as the sampler, is
personally responsible for:
1. Relinquishing the samples under chain-of-custody to one of the GEi
employees listed on Table 1; and
2. Signing and dating the chain-of-custody forms.
In the event that none of the screening laboratory personnel are available at the
time of sample delivery, the shipping container must be stored in a secure area
with custody seals to prevent tampering until such time that the screening
laborat0ry personnel can be notified.
The screening laboratory personnel are personally responsible for:
1. Verifying that the information on the sample labels matches that on the
chain-of-custody record;
2. Noting any discrepancies between the sample labels and the chain-of-custody
on the chain-of-custody form;
3. Signing the chain-of-custody form, thus establishing custody of the samples;
4. Logging the samples into the GEI screening refrigerator log (Fig. 2); and
5. Placing the samples in the refrigerator and locking the refrigerator.
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4. STORAGE AND DISPOSAL
Revision_!)_
Date March 15. 1991
Samples will be stored in refrigerator's maintained at 4 • C (.±.2 C). The temperature
will be recorded on a daily basis on all working days. These records will be maintained
and available for review upon request.
Samples will be stored for 30 days from sample receipt. At that time, the facility
sample custodian will notify the project manager that the storage period has expired and
will request direction for final sample disposal. Samples will be disposed of at the
direction of the project manager and the disposal will be recorded in the GEi sample
refrigerator log.
TOTAL P.08
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APPENDIXC
Standard Operating Procedure No. 7
Turner Hart & Hickman, P.C.
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No. 7 HYDROGEN, GC/RGD, FIELD LABORATORY
1.0 SCOPE AND APPLICATION
I. I This procedure is used to identify and determine the concentration of hydrogen in groundwater
samples
2.0 SUMMARY OF METHOD
2.1 Samples are introduced into the GC using direct injection of the gas stripped from a
continuous flow of ground water. Detection is achieved by a reducing gas detector (RGD).
3.0 INTERFERENCES
3. I Impurities in the gases, either those used in the GC system or other gases stripped from the
ground water with the hydrogen, account for the majority of contamination problems. The
analytical system must be demonstrated to be free from contamination under the conditions
of the analysis by running laboratory reagent blanks. The use of non-TFE plastic coating,
non-TFE thread sealants, or flow controllers with rubber components should be avoided.
3 .2 Samples can be contaminated by cross-contamination between sampling locations. Sampling
equipment must be throughly decontaminated between locations.
4.0 APPARATUS AND MATERIALS
4.1 Gas chromatograph
4. I. I Gas Chromatograph -Analytical system complete with gas chromatograph suitable for
gas sampling and/or on-column injections and all required accessori.es, including
detectors, column supplies, recorder, gases, and syringes. A data system for measuring
peak heights and/or peak areas is recommended.
4.1.2 Columns -the following column is recommended, however, alternative columns may be
employed as long as 60"/o resolution is demonstrated for target analytes: J&W Scientific
GS-Molesieve Capillary Column, 0.53 mm I.D. x 30 m.
4.1.3 Detector -Reducing gas detector (RGD).
4 .2 Syringes - A variety of Luerlok glass hypodermic syringes, gas-tight, with and without shutoff
valves.
27
5.0 REAGENTS
5.1 Ultra-pure gases shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the
American Chemical Society, where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its
use without_ lessening the accuracy of the determination.
5.2 Organic-free reagent water -All references to water in this method refer to organic-free
reagent water, as defined in Chapter One ofSW-846.
5.3 Methanol, CHJ0H. Pesticide quality or equivalent. Store away from other solvents.
5 .4 Stock standards -Stock solutions will be purchased as certified solutions or gases.
5.5 Secondary dilution standards -Using stock standards, prepare secondary dilution standards.
The secondary dilution standards should be prepared at concentrations such that the calibration
standards prepared in Section 5.6 will bracket the working range of the analytical system.
Secondary standards should be checked frequently for signs of degradation, especially just
prior to preparing calibration standards from them.
5.6 Calibration standards -Calibration standards at three (for screening level data) to five (for
definitive level data) concentrations are prepared by inert gas dilution of purchased gas
standards. One of the concentrations should be at a concentration near, but below, the
expected reporting detection limit. The remaining concentrations should correspond to the
expected range of concentrations found in real samples or should define the working range of
the GC.
6.0 SAMPLE COLLECTION, PRESERVATION,AND HANDLING
6.1 Sample collection is accomplished using a proprietary gas stripping system. A standard gas
sampling bulb is configured such that a continuous stream of water is stripped for 15 minutes
at a rate of500 ml/minute (other combinations of flow rate and time are possible). A gas tight
syringe is used to collect a sample of the stripped.gas once an equilibrium condition is reached
in the bulb. Samples are collected in duplicate. Generally, field analyses will be performed
within one hour of sample collection but storage for as long as 24 hours is possible in a cool,
dark, and dry location.
7.0 PROCEDURE
7. I Samples are introduced into the gas chromatograph in the same manner as calibration
standards.
7.2 Follow the instrument manufacturers instructions for initial setup and testing. Establish initial
instrument operating conditions based on those instructions. Run a series of test samples and
review the data for adequate response and resolution. Adjust gas flow rates, temperature
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programs, or other instrument operating parameters as required to establish mid level
calibration standard response at approximately 50% of scale and resolution between all
analytes of interest of at least 60%.
7.3 Calibration
7.3. I Prepare calibration standards at three to five concentrations (refer to QAPjP for
guidance) by introducing an inert gas through a dilution nozzle. One of the external standards
should be at a concentration near, but below, the reporting detection limit. The other
concentrations should correspond to the expected range of concentrations found inreal
samples or should define the working range of the detector.
7.3.2 Inject each calibration standard using the technique that will be used to introduce the
actual samples into the gas chromatograph (e.g. direct injection, sample loop, etc.). Tabulate
peak height or area responses against the mass injected. The results can be used to prepare a
calibration curve for each analyte. Alternatively, for samples that are introduced into the gas
chromatograph using a syringe, the ratio of the response to the amount injected, defined as the
calibration factor (CF), can be calculated for each analyte at each standard concentration. If
the percent relative standard deviation (¾RSD) of the calibration factor is less than the
requirements given in the QAPjP corresponding to the application over the working range,
linearity through the origin will be assumed, and the average calibration factor can be used in
place of a calibration curve.
Total Area of Peak
Calibration factor =
Mass injected (in nano grams)
7.3.3 The working calibration curve or calibration factor must be verified on each working day
by the injection of one or more calibration standards. The frequency of verification is
established in the QAPjP. If the response for any analyte varies from the predicted response
by more than the specification of the QAPjP, a new calibration curve must be prepared for that
analyte.
RI -R2
Percent Difference = X 100
RI
where:
RI = Calibration Factor from first analysis.
R2 = Calibration Factor from succeeding analyses.
7.4 Gas chromatographic analysis
7.4. I Introduce samples into the gas chromatograph using a technique consistent with the
initial calibration as described above.
29
7.5 Retention time windows
7.5.1 Using the data from the initial calibration of the instrument, establish retention time
windows as follows.
7. 5 .1.2 Calculate the standard deviation of the absolute retention times for each
component.
7.5.1.2 Plus or minus three times the standard deviation of the absolute retention times
for each standard will be used to define the retention time window; however, the
experience of the analyst should weigh heavily in the interpretation of chromatograms.
7.5.1.3 In those cases where the standard deviation for a particular standard is zero, the
laboratory must substitute the standard deviation of a close eluting, similar compound
to develop a valid retention time window.
7. 5. 3 The laboratory must calculate retention time windows for each standard on each GC
column and whenever a new GC column is installed. The data must be retained by the
laboratory.
7.6 Start each day of analysis with the injection of a media blank. Analyze a calibration
verification standard, establish daily retention time windows, and verify that retention times
and response are consistent. Retention times should not shift more than 2. 0% for packed
columns, 0.3% for narrow bore capillary columns, or 1.5% for wide bore capillary columns.
Response must meet the criteria given in section 7.3.3. If these conditions are not met, the
analyst should review instrument operating conditions and rerun the standard once. If
appropriate retention times and responses are not observed, a new initial calibration must be
performed.
7 .6.1 Tentative identification of an analyte occurs when a peak from a sample extract falls
within the daily retention time window. Confirmation will be performed on an alternate
column only if required by the QAPjP.
7. 7 Record the sample volume purged or injected and the resulting peak sizes (in area units or
peak heights).
7.7.1 Calculate raw analytical results by directly reading the·result from the calibration curve,
or by multiplying the measured response times the calibration factor established in section ·
7 .3 .3. The raw analytical result must be modified to produce a reportable result by means of
Henry's law.
Concentration ofX in air (or gas) (ug/1) =
{[A(x)/(CF)]/[Vg]} • 0.81 (Henry's constant for hydrogen)
where:
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CF= Calibration factor from section 7.3.2.
V g = Volume of gas presented to the GC in liters, adjusted for dilution.
7. 9 If analytical interferences are suspected, or for the purpose of confirmation, analysis using the
second GC column is possible.
7. IO If the response for a peak is off-scale, prepare a dilution of the sample. The dilution must be
performed on an aliquot of the sample which has been properly sealed and stornd prior to use.
8.0 QUALITY CONTROL
8.1 Quality assurance requirements are presented in the QAPjP.
9.0 METHOD PERFORMANCE
9.1 Each analyst that performs the method must demonstrate the ability to meet the precision and
accuracy requirements of the QAPjP prior to performing these analyses. At a minimum,
duplicate spikes must produce percent recoveries and relative percent differences that meet the
precision and accuracy goals as defined in the QAPjP.
10.0 REFERENCES
IO. I SW-846 Methods 8000A, 8010B.
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I APPENDIX D
I Standard Operating Procedures
Pace Analytical Services, Inc.
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Pace Analytical
Pace Analytical Services. Inc.
9800 !(incey Avenuf:, Suite 100
Huntersville, NC 28078
Tel: [phone]
Fax:"704-875-9091
STANDARD OPERATING PROCEDURE
The Determination of Volatile Organic Compounds
by Gas Chromatography/ Ma:is Spectrometry
Reference Method: SW846 Method 8260A
SOP NUMBER:
EFFECTIVE DATE:
SUPERSEDES:
APPROVAL
-S'D{i,,-,_~(,~
Operations Manager
Quality Assurance Officer (
CA:./
General Manager
CONTROLL.EO COPY
NC!-O-017 COPY NO._ 3
April 15, I 997
Draft SOP
Date
/rlp-97
Date
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I. PURPOSE -The purpose of this Standard Operating Procedure (SOP) is to determine
the concentration of volatile organic compounds in a variety of solid waste matrices by
purge-and-trap GC/MS following SW-846 Method 8260A. This method is applicable to
nearly all types of samples, regardless of water content. Common matrices are ground
water, wastewater and aqueous sludges.
II. SCOPE AND APPLICATION
A.
C.
D.
Analytes -Volatile organic compounds that have boiling points below 200°C and
that are insoluble or slightly soluble in water. Volatile water-soluble compounds
may be included in this analytical technique. However, for the more soluble
compounds, quantitation limits are approximately ten times higher because of poor
purging efficiency. (i.e. ketones) See list of individual compounds in calibration
standards in section XIII.
Summary -The volatile compounds are introduced into the gas chromatography
by the purge-and-trap method. Purged sample components are trapped in a tube·
of sorbent materials. When purging is complete, the sorbent tube is heated and
backflushed with helium to desorb trapped components. The analytes are
desorbed onto a capillary column. The column is temperature programmed to
separate the analytes which are then detected with a mass spectrometer.
Interferences -Interfering contamination may occur when a sample containing
low concentrations of volatile organic compounds is analyzed immediately after or
on an autosampler port which previously contained a sample containing high
concentrations of volatile organic compounds. The preventive technique is rinsing
the purging apparatus and sample syringes with two portions of organic free water
between samples. Analyze one or more method blanks to check for cross
contamination prior to sample analysis. Special precautions must be taken to
analyze for methylene chloride. The analytical and sample storage area should be
isolated from atmospheric sources of methylene chloride. Chromatography gas
lines should be constructed from stainless steel or copper tubing. Laboratory
clothing previously exposed to methylene chloride fumes during extraction
procedures can contribute to sample contamination.
Hazards and Precautions
The toxicity and carcinogenicity of standards and reagents used in this method
have not been precisely defined. Each chemical compound should be treated as a
potential health hazard. Reduce exposure by the use of gloves, lab coats and
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safety glasses. Material Safety Data Sheets(MSDSs) are on file in the library and
available to all personnel. Standard solutions should be prepared in a hood.
ill. RESPONSIBILITIES
IV.
A.
B.
Analysts
I. Analysts are responsible for adherence to the SOP.
2. All laboratory personnel are responsible for notifying their supervisor of
any required revisions to the SOP.
Operations Manager
I.
2.
The Operations Manager is responsible for ensuring adherence to this SOP.
The Operations Manager is responsible for performing an annual review of
the SOP.
C. Quality Assurance Officer (QAO)
D.
I. The QAO is responsible for conducting laboratory audits to monitor
adherence to this SOP. Results of the audit will be reported to the
Operations Manager, General Manager and Corporate Quality.
2. The QAO is responsible for coordinating annual reviews of this SOP with
the operations manager and the general manager.
3. The QAO is responsible for ensuring that all revisions to the SOP are
implemented.
4. The QAO is responsible for monitoring distribution of and maintaining
document control for this SOP.
General Manager (GM)
I. The GM is responsible for the overall implementation of and adherence to
this SOP.
2. The GM is responsible for reviewing of this SOP with the QAO and the
operations manager
REVISIONS/REVIEWS
A. This SOP will be reviewed on an annual basis at a minimum by the operations
manager, general manager and the quality assurance officer.
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B. The revised SOP will be distributed to all appropriate personnel and the
superseded version replaced.
V. DISTRIBUTION
VI.
Distribution of this SOP will be determined by the QAO.
APPARATUS AND MATERIALS
A. Reagents, Glassware and Materials
B.
I. Organic-free reagent water(OFW)
2. Methanol -purge and trap quality. (P&T MeOH)
3. 5 rnL volumetric flasks
4. 1 rnL amber vials
5. 4 rnL amber vials with Teflon lined screw caps
6. Teflon minninert valves for lrnL and 4rnL amber vials
7. 5 rnL Hamilton gas-tight syringe with shut-off valve
8. Gas-tight syringes: I rnL, S0uL, 25uL and I 0uL
9. Dispensing bottle for OFW
10. Teflon dispensing bottle for Methanol
Instrumentation
1. Purge and Trap:
Automatic Liquid Sampler -Tekmar Model ALS-2016
Liquid Sample Concentrator -Tekmar Model LSC-2000
Purge and Trap parameters:
Trap: Supelco -Vocarb 3000
Standby Temp.: 39°C
Purge: IO min. at 40 rnL/min.
Dry Purge: 6 min.
Desorb preheat: 245°C
Desorb: 2.0 min. @ 250°C
Bake: 8 min. @ 260°C
Auto Drain: OFF
Bake Gas Bypass: ON
BGB Delay: 120 seconds
Valve: 130°c
Line: 130°C
Mount: 4o•c
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C.
2.
3.
2016 Valve:
2016 Line:
13o•c
13o•c
GAS CHROMATOGRAPH -Hewlett Packard 5890
Column: HP-VOC 90m x 0.53mm id x 3.0um
Carrier gas: Helium
GC Temperature Programs: BFB VOA
Initial Temp: 100°c 40°c
Hold: 1 min 5 min
Ramp: 6°C/min 8 °C/min
Final Temp: 200°c 200°c
Hold: 0 min 4min
Run Time: 1433 min 29 min
Mass Spectrometer -Hewlett Packard 5970 Mass Selective Detector (MSD)
GC/MS Temperatures:
Injection Port: 250°C
Detector B(Inter.): 300°C
Detector A(Jet): 220°C
Mass Spec. Parameters:
Scan Range: 3 5-300
Multiplier Voltage: Variable
Threshold: 500
Sampling #: 3
AID Samples: 8
Standards:
All standards are prepared using purge and trap methanol and stored in amber vials
with Teflon lined screw caps or rnininert valves at 4°C. Gas standards must be
replaced one month after the ampule is cracked. All other standards must be
replaced 6 months after the ampule is cracked. Replace sooner if the standards
show signs of degradation. As each standard, from the vendor is opened, record
all pertinent information in the stock standard logbook. Record all standard
preparations in the working standard logbook.
I. Stock Solutions and Neat Standards: {As listed or equivalent source.)
(For list of individual compounds in each standard, see section XII.)
Supelco 8260 IS Mix@ 2000ug/mL Cat.# 4-8958
Supelco 8260 SS Mix@ 2000ug/mL Cat.# 4-8959
Supelco VOC Mix 1 @ 2000ug/mL Cat.# 4-8775
Supelco VOC Mix 2@ 2000ug/mL Cat.# 4-8777
Supelco VOC Mix 3 @ 2000ug/mL Cat.# 4-8779
Supelco VOC Mix 4@ 2000ug/mL Cat.# 4-8786
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2.
3.
Supelco VOC Mix 5 @ 2000ug/mL
Supelco VOC Mix 6 @ 2000ug/mL
Supelco 8240B Cal. Std. Mix 2 @ 2000ug/mL
Aldrich: 2-chloroethylvinyl ether (neat)
Aldrich: vinyl acetate (neat)
Aldrich: Acrolein (neat)
Aldrich: Acrylonitrile (neat)
Aldrich: trans-I, 4-dichloro-2-butene ( neai)
Aldrich: carbon disulfide (neat)
Aldrich: iodomethane (neat)
Adrich: Freon I 13(112-trichlorotrifluoroethane)
OC Standards(Altemate source):
Cat.# 4-8797
Cat.# 4-8799
Cat.# 4-7364
Cat.# 10,998-3
Cat.# V 150-3
Cat.# 11,022-1
Cat.# 11,021-3
Cat.# 32,451-5
Cat.# 34,227-0
Cat.# I 850-7
Cat.# 17,282-0
Cat.# M-502A-R-I OX
Cat.# M-502B-l OX
AccuStandard M-502A-R-l0X@2.0mg/mL
AccuStandard M-502B-l0X @ 2.0mg/mL
AccuStandard M-8260ADD-l OX@ 2.0mg/mL
Aldrich: Acrolein (neat)
Cat.# M-8260-ADD-l0X
Cat.# 11,022-1
Aldrich: Acrylonitrile (neat)
Aldrich: trans-1,4-dichloro-2-butene (neat)
Adrich: Freon I 13(112-trichlorotrifluoroethane)
Internal Standard (IS) @ 25ug/mL
Cat.# 11,021-3
Cat.# 32,451-5
Cat.# 17,282-0
-Halffill a 5mL volumetric flask with P&T MeOH and add:
-62.5uL Supelco 8260 IS Mix@ 2000ug/mL
-Dilute to 5mL with P&T MeOH. Stopper and invert 3 times to mix.
-Transfer to a 4mL amber vial with a Teflon minninert valve.
Internal/ Surrogate Standard Mix (IS/SS) @ 25ug/mL
-Halffill a 5mL volumetric flask with P&T MeOH and add the following:
-62.5uL Supelco 8260 IS Mix@ 2000ug/mL
-62.5uL Supelco 8260 SS Spike Mix@ 2000ug/mL
·c Dilute to 5mL with P&T MeOH. Stopper and invert 3 times to mix.
-Transfer to a 4mL amber vial with a Teflon minninert valve.
4. · Misc. 8260 Stds. (from neats)@2000/4000/10,000/20,000ug/mL
-Half fill a 5mL volumetric flask with P&T MeOH and add the following:
Density Final Cone.
9.5uL 2-chloroethylvinyl ether
21. 4uL vinyl acetate
@ l.048mg/uL 2000ug/mL
@ 0.934mg/uL 4000ug/mL
62uL Acrylonitrile @0.806mg/uL 10,000ug/mL
l 20uL Acrolein @ 0.839mg/uL 20,000ug/mL
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8.4uL trans-1,4-Dichloro-2-butene
7.9uL carbon disulfide
4.4uL iodomethane
6.4uL Freon 113
@ l.183mg/uL
@ l.266mg/uL
@ 2.280nig/uL
@ l.57mg/uL
2000ug/rnL
2000ug/rnL
2000ug/mL
2000ug/rnL
-Dilute to SmL with P&T MeOH. Stopper and invert 3 times to mix.
-Transfer to a 4mL amber vial with Teflon lined screw cap.
5. 8260 Calibration Stock Solution@ 100/200#/500*/l000**ug/L
-Transfer 350uL P&T MeOH to a lmL amber vial and add the following:
-SOuL Supelco 8260 SS Mix@ 2000ug/mL
-SOuL Supelco VOC Mix l @ 2000ug/mL
-S0uL Supelco VOC Mix 2 @ 2000ug/mL
-S0uL Slipelco VOC Mix 3 @ 2000ug/mL
-S0uL Supelco VOC Mix 4 @ 2000ug/mL
-S0uL Supelco VOC Mix 5 @ 2000ug/mL
-50uL Supelco VOC Mix 6 @ 2000ug/mL
-250uL Supelco 8240B Cal. Std. Mix 2 @ 2000ug/mL
-50uL Misc. 8260 Stds. @2000/4000#/10,000*/20,000**ug/mL
-Cap and invert 3 times to mix. (Final Volume = 1 mL)
(# vinyl acetate, • isobutanol, acetone, 2-butanone, 2-hexanone, 4-methyl-2-
pentanone and acetonitrile, • • acrolein and acrylonitrile)
6. 8260 Calibration Dilution@ 10/20#/50*/l00**mg/mL
-Transfer 900uL P&T MeOH to a lmL amber vial and add:
- 1 0OuL Calibration Stock Solution
-Cap and invert 3 times to mix. (Final Volume = l mL)
(# vinyl acetate, • isobutanol, acetone, 2-butanone, 2-hexanone, 4-methyl-2-
pentanone and acetonitrile, •• acrolein and acrylonitrile)
7. Misc. 8260 OC Stock Std. (from neats)@ 2000/20,000ug/mL.
-Half fill a SmL volumetric flask with P&T MeOH and add the following:
Density Final Cone.
124uL Acrylonitrile @0.806 20,000ug/mL
120uL Acrolein @ 0.839mg/uL 20,000ug/.mL
8.4uL trans-l,4-Dichloro-2-butene @ l.183mg/uL 2000ug/mL
6.4uL Freon 113 @ l.57mg/uL 2000ug/mL
-Dilute to 5mL with P&T MeOH. Stopper and invert 3 times to mix.
-Transfer to a 4mL amber vial with Teflon lined screw cap.
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8. 8260 LCS Solution@ 10/20*/l OO**ug/rnL
-Half fill a SrnL volumetric flask with P&T MeOH and add:
-25uL AccuStandard M502AR-I0X @2000ugirnL
-25uL AccuStandard M502B-10X @2000ugirnL
-50uL AccuStandard M8260 ADD-I OX @2000ugirnL
-25uL Misc. 8260 QC Stds. @ 2000/20,000ugirnL
-Dilute to SrnL with P&T MeOH. Stopper and invert 3 times to mix.
-Transfer to a 4ml amber vial with a Teflon minninert valve.
(* isobutanol acetone, 2-butanone, 2-hexanone, 4-methyl-2-
pentanone and acetonitrile, • • acrolein and acrylonitrile)
9. 8260 Matrix Spike Solution@50/I00*/500**uglrnL
-Halffill a 5rnL volumetric flask with P&T MeOH and add:
-62.5uL AccuStandard M502AR-I0X @2000ugirnL
-62.5uL AccuStandard M502B-1 OX @ 2000ugirnL
-125uL AccuStandard M8260 ADD-l0X @2000ugirnL
-62.5uL Misc. 8260 QC Stds. @2000/20,000ugirnL
-Dilute to 5ml with P&T MeOH. Stopper and invert 3 times to mix.
-Transfer to a 4ml amber vial with a Teflon minninert valve.
(* isobutanol, acetone, 2-butanone, 2-hexanone, 4-methyl-2-pentanone,
and acetonitrile, •• acrolein and acrylonitrile)
VII. TUNING I CALIBRATION
A. Tune Standard -50ng 4-Bromofluorobenzene(BFB) -Analyzed daily, BFB must
pass the key m/z abundance criteria as defined below prior to sample analysis. Tune
period = l 2hours.
BFB Key m/z abundance criteria from table 4 of Method 8260A
Mass
50
75
95
96
173
174
175
176
177
m/z Abundance criteria
15 to 40% of mass 95
30 to 60% of mass 95 ·
base peak, 100% relative abundance
5 to 9"/o of mass 95
less than 2% of mass 17 4
greater than 50% of mass 95
5 to 9"/o of mass 174
greater than 95% but less than 101% of mass I 74
5 to 9"/o of mass 176
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B. Initial Calibration -The method requires calibration with a minimum of five
concentration levels. The lowest calibration standard must be at the reporting limit as
required by the state ofNorth Carolina. The other levels should correspond to the
range of concentrations expected to be found in real samples. The instrument data
system calculates a response factor (RF) for each analyte. In addition the data system
generates a calibration report displaying the average response factor and percent
relative standard deviation for each analyte in the series of calibration standards.
Instrument calculations are listed below.
Response Factor (RF) = (A,C;,) I (A;,C.)
A, = Area of characteristic ion for the compound being measured.
A;, = Area of characteristic ion for the specific internal standard.
C;, = Concentration of the specific internal standard.
C. = Concentration of the compound being measured.
Average RF (RF) = sum of all RF's(across the calibration range) for "X''
# of calibration levels
Percent Relative Standard Deviation (¾RSD) = SD
---X 100
mean
The percent relative standard deviation(¾RSD) for the calibration check compounds
(CCC's) must be <30% and the average minimum response factors for the system
performance check compounds (SPCC's) are listed below. If the% RSD of any
compound is greater than I 5%, construct calibration curves of area ratio (AJA;,)
versus concentration using first or higher order regression fit of the five calibration
points.
SPCC's {minimum RF)
Chloromethane (0. I)
I, I 0Dichloroethane (0.1)
Bromoform (>O. I)
I, 1,2,2-Tetrachloroethane (0.3)
Chlorobenzene (0.3)
CCC's {¾RSD <30%)
I, 1-Dichloroethene
Chloroform
1,2-Dichloropropane
Toluene
Ethylbenzene
Vinyl Chloride
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C. Continuing Calibration -The Calibration curve must be verified each day by analysis
of a mid-range calibration standard. We currently analyze the standard at SOugiL. The
percent difference from the calibration for the calibration check compounds(CCC's)
must be <20% and the minimum response factors for the system performance check
compounds (SPCC's) must meet the criteria listed below. Internal Standard areas must
be within-SO% and +100% from the last daily standard. Internal standard retention
times must be within 30 seconds from the last daily standard.
SPCC's (minimum RF)
Chloromethane (0.1).
1, 1-Dichloroethane (0. 1)
Bromoform (>0.1)
1, 1,2,2-Tetrachloroethane (0.3)
Chlorobenzene (0.3)
CCC's (¾Difference <20%)
1, 1-Dichloroethene
Chloroform
1,2-Dichloropropane
Toluene
Ethylbenzene
Vmyl Chloride
% Difference = RF (from initial calibration) -RF (from continuing calibration)
RF (from initial calibration)
VIII. PROCEDUDRE:
A
B.
C.
All samples and standards must be allowed to warm to ambient temperature before
analysis. Verify and document that all samples are properly preserved. After a portion
of sample is poured into a SmL syringe (Step D-7), test the remaning sample with pH
paper and KI starch paper. The pH paper should read <2 and there should be no
residual chlorine detected on the KI starch paper (paper turns blue in the presence of
chlorine). Document results in the injection log.
Set up the purge-and-trap system and the GC/MS as outlined in section
IV-B.
The GC/MS system must be hardware-tuned using perfluorotributylarnine(PFTBA).
In the manual tune program of the instrument, adjust the MS parameters to obtain the
following mass ratios.
Mass
69
131
219
Relative Abundance
100%,
30-40%
35-45%
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D.
E.
F.
For best results, the abundance of219 should be slightly higher than the 131. Mass
fragments associated with air and water (m/z 18, 28 & 32) should be less than 10% of
the 69 ion. Print out a tune report displaying the profile scan and the spectrum scan.
Clean the auto sampler ports. When the Tekmar is in the purge ready mode, press the
[F2] key to get to the autosampler screen. Note the current ALS position. Press the
[DRAIN] key.
L
2.
3.
4.
Open the valve on the current ALS port. Water will be forced out the top of
the port. Catch the waste water in a beaker.
Rinse the port two times with SmL of OFW, discard rinse water. If the port is
contaminated (contained analytes above the calibration range), rinse with SmL
ofMeOH prior to rinsing with water.
Press the [STEP] key to advance to the next port.
Repeat steps 1-3 for each position. When all ports are clean, press the
[DRAIN] key to turn off the drain.
Generate a sequence to run a batch of samples. The typical batch should include the
following:
BFB Tune Standard
Calibration Standards or Continuing Calibration Standard
Method Blank
Laboratory Control Sample
20 samples
Matrix Spike/Matrix Spike Duplicate
Duplicate (Sample Duplicate or MSD every 10 samples)
Note: The BFB tuning criteria and GC/MS calibration verification criteria must be met
before analyzing samples. See section VII.
Load the autosampler with standards and samples for the batch created above.
I. BFB
-SmLOFW
-2uL IS/SS mix@ 25ugimL.
-Fill a SmL gas tight syringe with SmL OFW and add 2uL IS/SS mix. Load
onto the appropriate ALS position.
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Calabration
Standard
I
2
3
4 '
5
6
2. Initial Cahbration Standards
-Prepare six calibration standards by filling 5 mL gas-tight syringes with
OFW and add the appropriate amount of calibration solution and IS as
indicated below. Load onto the autosampler.
Vol. of Stock Cone.of Stock Final Final Solvent
Solution Solution Volume Cone. (ug/L)
(uL) (ug/mL) (mL)
2.5uL Cal. Di!. 10/20#/50•/
100 .. 5 5/10#/25•150•• OFW
IOuL IS 25 50
5.0uL Cal. Di!. 10/20#/50•/ 10/20#/50•/
100•• 5 100•• OFW
IOuL IS 25 50
lOuL Cal. Di!. 10/20#/50•/ 20/40#/JOO•t
100•• 5 200•• OFW
IOuL IS 25 50
2.5uL Cal. Stock 100/200#/500•/ 50/100#/250•/
1000•• 5 500 .. OFW
lOuL IS 25 50
5.0uL Cal. Stock 100/200#/500•/ 100/200#/500*/
1000•• 5 1000•• OFW
lOuL IS 25 50
lOuL Cal. Stock 100/200#/500*/ 200/400#/1000*/
1000•• 5 2000•• OFW
IOuL IS 25 50
(# vinyl acetate, • isobutanol, acetone, 2-butanone, 2-hexanone, 4-methyl-2-pentanone and
acetonitrile, • • acrolein and acrylonitrile)
3.
4.
5.
Continuing Calibration Standard -Mid-range calibration Standard
Final Cone.
-5mLOFW
-2.5uL Cal. Stock
-lOuL IS@25ug/mL
Method Blank
-5mLOFW
-1 OuL IS/SS @ 25ug/mL
Laboratory Control Sample
-5mLOFW
-1 OuL LCS Solution
-1 OuL IS/SS @ 25ug/mL
50/100#/200*/500**ug/L
50ug/L
Final Cone.
50ug/L
Final Cone.
20/40*/200**ug/L
50ug/L
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IX.
6.
7.
(• isobutanol, acetone, 2-butanone, 2-hexanone, 4-methyl-2-
pentanone and acetonitrile, • • acrolein and acrylonitrile)
Matrix Spike/Matrix Spike Duplicate Final Cone.
-5mL Sample
-!OuL Matrix Spike Solution 50/I0o•t5oo••ug/L
-I OuL IS/SS mix @ 25ugimL 50ug/L
(• isobutano~ acetone, 2°butanone, 2-hexanone, 4-methyl-2-
pentanone and acetonitrile, • • acrolein and acrylonitrile)
Samples
-5mL Sample
Final Cone.
-1 OuL IS/SS mix @ 25ugimL 50ugiL
Sample Dilution
I :2
1:5
I: IO
1:20
1:25
1:50
I: 100
1:1000
Volume of Sample to dilute to 5mL with OFW
2.5mL
I.0mL
0.5mL
250uL
200uL
I0OuL
50uL
5uL
G. Analyze all standards, QC samples and samples from above a=rding to the
instrument parameters as outlined in section IV. All QC samples must pass QC
requirements as outlined in section VlI.
CALCULATIONS (Quantitative Analysis):
A. Concentration (ug/L) -The instrument will automatically calculate the concentration
of each analyte in terms of ugiL. This is our final reporting unit. Therefore, no further
calculations are necessary unless a dilution of the sample has been analyzed.
ug/L (as calculated by the instrument) = (A,C;,) I (A.,RF)
A. = Area .of characteristic ion for the compound being measured.
A;, = Area of characteristic ion for the specific internal standard.
C;. = Concentration of the specific internal standard.
RF = Average response factor from initial calibration
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Reported Concentration = ug/L x Dilution Factor
B. Surrogate Recovery:
C.
D.
% Recovery =
LCS Recovery:
% Recovery =
Cone. Reported( ug/L)
True Value ( 50 ug/L)
Cone. Reported (ug/L)
True Value (ug/L)
X 100
X 100
Matrix Spike Recovery:
% Recovery = Cone. of spiked sample -Cone. of sample
True Value Spiked
X 100
E. Duplicate Results -Relatvie Percent Difference (RPD):
RPO = Difference x 100
Mean
= (Cone. I -Cone. 2) x I 00
(Cone. I + Cone. 2) / 2
X. QUALITATIVE ANALYSIS (Data Interpretaion):
A.
B.
Retention Time Comparison:
The sample component relative retention tirne(RRT) must compare within+/-.0.06
RRT units of the RRT of the component in the continuing calibration standard. For
reference, the standard must be run within the same 12 hours as the sample.
Mass Spectrum Comparison:
1. All ions present in the standard mass spectra at a relative intensity greater than
10"/o (most abundant ion in the spectrum equals 100"/o) must be present in the
sample spectrum).
2. The relative intensities of the ions greater than 10"/o must agree within+/-20%
between the standard and sample spectra.
XL QUALITY CONTROL
A. Method Blank -To be analyzed daily with each batch of samples. The method
blank must not contain any target analytes at or above the reporting limit.
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The Detennination of Volatile
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15 ofl9
B.
C.
D.
E.
F.
G.
Laboratory Control Sample(LCS) -Analyze one LCS daily. Spike 5mL ofOFW
with all compounds being reported resulting in a final concentration of20ug!L for each
analyte. Spiked compounds must pass the QC acceptance criteria as outlined in Table
6 of Method 8240(see LCS form in Appendix I). In-house limits to be determined.
Matrix Spike/ Matix Spike Duplicate (MS/MSD) -Analyze one MS/MSD pair
every 20 samples. Spike 5mL of a sample with all compounds such that the resulting
concentration is 50ug!L for each analyte. The QC limits below were taken from the
Contract Laboratory Program (CLP) -Statement ofWork 3/90.
QC Limits
¾Recovery RPD
I, 1-Dichloroethene 61-145 14
Benzene 76-127 14
Trichloroethene 71-120 11
Toluene 76-125 13
Chlorobenzene 75-130 13
Note: The state of NC requires that we spike the MS/MSD with all compounds.
Duplicates -The state ofNC requires that we analyze one MSD or sample
duplicate every IO samples.
Surrogate Standards -To be added to all samples, spikes, control samples and
method blanks, prior to purge-and-trap, to monitor method accuracy. Spike each 5mL
portion of sample with surrogates such that the resulting concentration is 50ug!L for
each surrogate. Surrogate recoveries must be within the following limits as outlined in
table 9 of Method 8260A
Dibromofluoromethane
Toluene-d8
4-Bromofluorobenzene
¾Recovery
86-118
88-110
86-115
Internal Standards -Internal standard areas must be within a factor of two (-50% to
+100%) compared to the associated continuing calibration standard. Internal standard
retention times must be within 30 seconds from the retention times in the associated
continuing calibration standard.
Precision and Accuracy Study (P&A) -Prior to analysis of samples each analyst must
establish the ability to generate acceptable accuracy and precision. Analyze 4 replicates
of a QC standard @ 20 ug!L. Calculate the average recovery in ug!L and the standard
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H.
L
J.
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deviation of the the recovery in ug/L, for each analyte using the four results. Compare
results to tables 7 and 8 in the method. Similar results should be obtained.
Method Detection Limit (MDL) -A MDL study must be conducted annually.
Analyze 7 replicates of a QC standard @ 5ug/L. Calculate a concentration for each
analyte. Calculate the mean and standard deviation(S) of measurements for each
analyte. Calculate the MDL as follows:
MDL= t(n-1, a= .99) x S
t(n-1, a = . 99) is the statistical t-value appropriate for the number of samples used to
detennine the standard deviation at the 99 percent confidence level.
Pace Reporting Limit (PRL) -Sug/L for most compounds.
Sample Preservation: HCl to pH <2. Cool, 4°C.
Sample Holding Time -14 days.
XII. LIST OF STANDARDS:
A.
B.
C.
Internal Standard:
Supelco 8260 IS Mix @ 2000ug/mL
pentafluorobenzene
I, 4-difluorobenzene
I, 4-dichlorobenzene-d4
chlorobenzene-d5
Surrogate Standard:
Supelco 8260 SS Mix @ 2000ug/mL
I dibromofluoromethane
toluene-d8
4-bromofluorobenzene
Calibration Standards:
Supelco VOC Mix I @ 2000ug/mL
propylbenzene
1,2-dichlorobenzene
I, 4-dichlorobenzene
o-xylene
2-chlorotoluene
tert-butylbenzene
chlorobenzene
1,3-dichlorobenzene
isopropylbenzene
p-xylene
sec-butyl benzene
4-chlorotoluene
Cat.# 4-8958
Cat.# 4-8959
Cat.# 4-8775
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File Name: NC1O017
Apr. 15, 1991
I 7 of 19
Date:
Page:
Supelco VOC Mix 2@2000ug/mL
I ,3, 5-trimethylbenzene
1,2, 4-trichlorobenzene
styrene
p-isopropyltoluene
bromobenzene
1,2, 4-trimethylbenzene
toluene
naphthalene
ethylbenzene
m-xylene
n-butylbenzene
1,2,3-trichlorobenzene
benzene
Supelco VOC Mix 3 @ 2000ug/mL
Cat.# 4-8777
Cat.# 4-8 779
1,2-dichloroethane
I, I ,2,2-tetrachloroethane
cis-1,3-dichloropropene
1,2-dibromoethane(ED B)
trichloroethylene
I, I, 1,2-tetrachloroethane
I ,3-dichloropropane
I, 1,2-trichloroethane
1,2-dichloropropane
trans-1,3-dichloropropene
hexachlorobutadiene
1,2-dibromo-3-chloropropane(DBCP)
I, 1-dichloropropene
1,2,3_ -trichloropropane
Supelco VOC Mix 4 @ 2000ug/mL
I, I, I-trichloroethane
bromoform
bromochloromethane
2,2-dichloropropane
chloroform
I, 1-dichloroethane
tetrachloroethylene
dibromomethane
carbon tetrachloride
Cat.# 4-8786
Supelco VOC Mix 5 @ 2000ug/mL Cat.# 4-8797
I, 1-dichloroethylene methylene chloride
trans-1,2-dichloroethylene cis-1,2-dichloroethylene
bromodichloromethane dibromochloromethane
Supelco VOC Mix 6 @ 2000ug/mL Cat.# 4-8799
vinyl chloride chloromethane
bromomethane chloroethane
trichlorofluoromethane dichlorodifluoromethane
Supelco 8240B Cal. Std. Mix 2 @ 2000ug/mL
isobutanol acetone
2-butanone
4-methyl-2-pentanone
acrylonitrile
2-hexanone
acetonitrile
Cat.# 4-73 64
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D.
Aldrich: 2-chloroethylvinyl ether (neat)
Aldrich: vinyl acetate (neat)
Aldrich: Acrolein (neat)
Aldrich: Acrylonitrile (neat)
Aldrich: trans-1.4-dichloro-2-butene (neat)
Aldrich: carbon disulfide (neat)
Aldrich: iodomethane (neat)
Aldrich: Freon I 13 (I 12-trichlorofluoroethane)
QC Standards(Alternate source):
Cat.# 10.998-3
Cat.# Vl50-3
Cat.# I I. 022-I
Cat.# I 1.021-3
Cat.# 32.451-5
Cat.# 34.227-0
Cat.# I850-7
Cat. #17,282-0
AccuStandard M-502A-R-I0X@ 2.0mg/mL Cat.# M-502A-R-I OX
benzene bromobenzene
bromochloromethane bromodichloromethane
bro mo form n-butylbenzene
sec-butylbenzene tert-butylbenzene
carbon tetrachloride chlorobenzene
chloroform 2-chlorotoluene
4-chlorotoluene dibromochloromethane
1.2-dibromo-3-chloro-propane(DBCP)
I .2-dibromoethane(ED B)
1,2-dichlorobenzene
I. 4-dichlorobenzene
I ,2-dichloroethane
cis-I ,2-dichloroethene
1,2-dichloropropane
2,2-dichloropropane
cis-1,3-dichloropropene
ethylbenzene
isopropylbenzene
methylene chloride
n-propylbenzene
1, 1, 1,2-tetrachloroethane
tetrachloroethene
dibromomethane
I ,3-dichlorobenzene
I, 1-dichloroethane
I, 1-dichloroethene
trans-1.2-dichloroethene
1,3-dichloropropane
I, 1-dichloropropane
trans-1,3-dichloropropene
hexachlorobutadiene
p-isopropyltoluene
naphthalene
styr~ne
1, 1,2,2-tetrachloroethane
toluene
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The Determination of Volatile
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NCl-O-017
1,2,3-trichlorobenzene
1,3, 5-trimethylbenzene
m-xylene
File Name:
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1,2, 4-trimethylbenzene
o-xylene
p-xylene
NC1O017
Apr. 15, 1997
19 of 19
Accustandard M-502B-10X @2.0mg/mL Cat.# M-502B-10X
bromomethane chloroethane
chloromethane
trichlorofluoromethane
dichlorodifluoromethane
vinyl chloride
Accustandard M-8260ADD-l0X@2.0mg/mL Cat.# M-8260-ADD-l0X
acetone 2-butanone
carbon disulfide 2-chloroethylvinyl ether
2-hexanone iodomethane
4-methyl-2-pentnaone vinyl acetate
Aldrich: Acrolein {neat) Cat.# 11,022-1
Aldrich: Acrylonitrile (neat) Cat.# 11,021-3
Aldrich trans-1,4-dichlioro-2-butene {neat) Cat.# 32,451-5
Aldrich: Freon I 13 (112-trichlorofluoroethane) Cat. # 17,282-0
XIII. APPENDIX 1: GC/MS Forms attached.
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DATE:
VOLATILE GC/MS DAILY QC CHECKLIST
SW846 -Method 8260A {Revision 1, September 1994)
--------ANALYST: _____ _
9FB TUNE REPORT (Present and criteria from Table 4 is met)
_INITIAL CALIBRATION REPORT (A minimum of 5 standards are present and the following criteria is met)
SPCC's lminim\lm RF! CCC's I%RSD < 30% *l
Chloromethane (0.1) 1, 1 -Dichloroethene
1, 1-Dichloroethane (0.1) Chloroform
Bromoform ( > 0. 1 I 1,2-Dichloropropane
1, 1,2,2-Tetrachloroethane (0.3) Toluene
Chlorobenzene (0.3) Ethylbenzene
Vinyl Chloride
*Note: If the %RSD of any compound is greater than 15%, construct calibration curves of area ratio(Area of
compound/ Area IS) versus concentration using first or higher order regression fit of the five calibration points.
_CONTINUING CALIBRATION REPORT (A midpoint calibration standard is present and the following criteria is
met)
SPCC's {minimum RF!
Chloromethane (0. 1)
1, 1-Dichloroethane (0. 11
Bromoform ( > 0. 1)
1, 1 ,2,2-Tetrachloruethane (0.31
Chlorobenzene (0.3)
CCC's 1%RSD <20%•1
1, 1 -Dichloroethene
Chloroform
1 ,2-Dichloropropane
Toluene
Ethyl benzene
Vinyl Chloride
-Internal standard areas must be within 50% from:the last daily standard.
-Internal standard retention times must be within 30sec. from the last daily std.
•Note: If the CCC's are not analytes required by the permit, then all required analytes must be within 20%.
__ METHOD BLANK -(Present)
-must be analyzed daily
__ MATRIX SPIKE/ MATRIX SPIKE DUPLICATE (Present and Method criteria is met)
-analyze a MS and a MSD every 10 samples.
-Concentration = 50ug/L
__ LABORATORY CONTROL SAMPLE (Present and method criteria is met)
-analyze one LCS every l O carn~loo. UC\.~ .
-Concentration = 20ug/L
SURROGATE RECOVERY LIMITS:
-Dibromofluoromethane
-Toluene-dB
-4-Bromofluoromethane
86-118%
88-110%
86-115%
QC Outliers (Footnoted in report): ______________________________ _
I(.·_-------------
1
Reviewed by: ________ _ Date reviewed: --------
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SUBSET:
from
previous SAMPLE ID BATCH ID
batch# QC Samples
Blank
Sample Dup
MS
MSD
LCS
date LCSD
proiect
due SAMPLES PROJECT#
Date Entered:. ___ _
By Analyst:, __
MATRIX: Batch 92----------
DATAFILE(S) DATE(S) ANALVZED
DATAFILE(S) DATE(S) ANALYZED
'
Date Reviewed & Validated:. ___ _
By Analyst: __
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1.
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Pace Analytical
Pace Analytical Services, Inc.
1700 Elm Street • Suite 200
Minneapolis, MN 55414
Tel: 612-617:6400
Fax: [phone]
STANDARD OPERATING PROCEDUREr.::rci\/ED
APR 2 , 1997
Methane in Water by
GC FID
SOP NUMBER MN-O-526-A
AUTHOR Bob Schnobrich
EFFECTIVE DA TE April 24, 1997
SUPERSEDES First Issue
Control Copy Number:
APPROVAL
. ' . , W1JL .<}ha (JO.Ip/) ~ Labratory Manager
. S\%vvv1-N ~.y-Lf~
Quality Assurance Officer
L/1)._Lf /ci1-
Date
G2l CC:: :S'..U' cc:.;co~~· .....
METHANE IN WATER
BY GCFID
MN-O-526-A
FILENAME:
DATE·:
PAGE:
MNO526A.DOC
April 23, 1997
I of 11
I.
II.
PURPOSE
1bis method is used for the determination of methane in water by headspace techniques, utilizing a GSQ
column for separation of target compound with subsequent quantitation by a flame ionization detector
(FID).
SCOPE AND APPLICATION
A. CONCENTRATION RANGES
B.
C.
The range of methane starts at its practical quantitation limit (PQL) and ends at the
concentration of the high level standard in the initial calibration curve. Method detection limits
(MDL) (as determined by 40 CFR136, Appendix B, July l, 1987 and Chapter One, SW-846
Final Update n will be on file to support the PQL's for this analyte on each instrument used to
report data.
METI-IOD DETECTION LIMITS
The method detection limit (MDL) is the minimum concentration of a compound that can be
measured and reported with 99% confidence that the value is above zero. The MDL actually
achieved in a given analysis will vary depending on instrument sensitivity and matrix effects;
therefore, quantitation limits have been set. The quantitation limits are higher than the MDL
and have been chosen to account for contamination from the sample preparation area and for
some inherent instrument and matrix effects.
HAZARDS AND PRECAUTIONS
The toxicity or carcinogenicity of each reagent used in this method has not been precisely
defined; however, each chemical compound should be treated as a potential health hazard.
Exposure to these chemicals must be reduced to the lowest possible level by whatever
means available (i.e., gloves, lab coats, goggles, and masks). Reference files of OSHA
regulations and MSDS's are available to all personnel involved in the analysis. Additional
references to laboratory safety have been identified and are available for inspection by the
analyst.
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METHANE IN WATER
BYGCFID
MN-O-526-A
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April 2:3, 1997
2 of 11
III. SUMMARY OF METHOD
IV.
V.
A. MATRIX
I. This method is applicable to aqueous matrices.
B. DESCRJPTION
I. Methane is determined by heating a I OmL sample volume and injecting 3 cc of the
volatilized gas into a gas chromatograph equipped with a column which allows for the
separation of methane from other gaseous constituents. Methane is then detected using
a flame ionization detection system.
INTERFERENCES
A. Impurities in the purge gas and organic compounds outgassing from the plumbing ahead of
the trap may cause contamination problems. The analytical system must be demonstrated
to be free from contamination by running method blanks under the condition of analysis.
B. Samples can be contaminated by diffusion of volatile organics through the sample
container septum during shipment and. Trip blanks, cooler blanks, and method blanks are
prepared with organic-free water and used to check for this contamination.
C. Contamination by carry-over can occur whenever high level and low level samples are
sequentially analyzed. A DI blank should be run after highly contaminated samples.
RESPONSIBILITIES
A.
B.
PERSONNEL
1. All personnel involved with sample preparation and analysis are responsible for
adherence to this SOP.
2. Personnel are responsible for ensuring that any deviations to this SOP are
reported.
3. All personnel are responsible for notifying the laboratory manager and section
supervisor of any required revisions to the SOP.
LABORATORY MANAGER/SECTION SUPERVISOR
METHANE IN WATER
BYGCFID
MN-0-526-A
FILENAME:
DATE:
PAGE:
MN0526A.DOC
April 23, 1997
3 of 11
VI.
C.
I. The laboratory manager and section supervisor are responsible for ensuring
adherence to this SOP.
2. The laboratory manager and section supervisor are responsible for performing an
annual review of the SOP and reporting any required revisions to the Quality
Assurance Office.
QUALITY ASSURANCE OFFICE (QAO)
I. The QAO is responsible for conducting laboratory audits to monitor adherence to
this and other SOPs. Results of the audit will be reported to Management.
2. The QAO is responsible for ensuring that all revisions to the SOP are
implemented.
3. The QAO is responsible for determining distribution of and maintaining document
control for this SOP.
REVIEWS/REVISIONS
A. This SOP will be reviewed on an annual basis at a minimum.
B. At the time of review, any required revision will be incorporated.
C. The revised SOP will be distributed to all appropriate personnel and the superseded
version replaced.
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METHANE IN WATER
BY GCFID
MN-0-526-A
VII. DISTRIBUTION
FILE NAME:
DATE:
PAGE:
MN0526A.DOC
April 23, 1997
4 of 11
A. A controlled copy of this SOP will be available to all laboratory staff. The original copy
will be maintained in a centralized laboratory location.
B. The original of this SOP will be retained by the QAO.
C. Distribution records will be retained by the QAO.
VIII. APPARATUS AND MATERIALS
A. GLASSWARE AND EQUIPMENT
B.
I. Sampling Containers:
a) Water -20-mL vial ,vith Teflon-lined septum and crimp top cap. These vials
are purchased pre-cleaned from a vendor.
2. Syringes: 5-mL gas tigbt glass hypodermic with Luerlock tip.
3. Microsyringes: I 0, 25, 50, I 00, 250, 500 and l000 u, gas tigbt
4. Volumetric flasks, Class A -10 mL
5. Graduated cylinder
INSTRUMENTS
I. Gas chromatographs
a)
b)
Hewlett Packard 5890 Series II GC (or equivalent)
Hewlett Packard 3396A integrator (or equivalent)
METHANE IN WATER
BYGCFID
MN-0-526-A
FILENAME:
DATE:
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April 23, 1997
5 of 11
IX.
X.
2. Headspace Sampler
a) Hewlett Packard 19395A head space analyzer (or equivalent)
3 . Detectors
4.
a) OI Flame Ionization Detector (or equivalent)
Detector temperature is 250°C.
All detector settings are typical. Analysts may make adjustments as required
to optimize overall detector performance.
Columns
a) GSQ fused silica capillary column -30m x 0.53 mm ID, 0 urn film thickness
(or equivalent).
REAGENTS
A. Reagent water: water in which there are no interferences at or above the reporting limit of
the parameters of interest. A Culligan water pretreatment system is used to deionize the
tap water. It is then sent through a polishing carbon filter to remove any organic
contamination.
B. Calibration Standard Solutions
I. Standards are purchased at certified amounts in nitrogen.
SAMPLE HANDLING AND STORAGE
A. Aqueous Samples
B.
C.
I. Samples are collected in 20 mL glass vials. The vials are filled with approximately I 0
mL of sample. The vial is inunediately sealed with a teflon-lined septum and a crimp
top.
The samples must be refrigerated at 4°C (+,-2°C) from the time of collection.
All samples must be analyzed within 14 days from the date of collection.
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BYGCFID
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FILENAME:
DATE·:
PAGE:
MNO526A.DOC
April 23, 1997
6 of 11
XI.
XII.
GENERAL POLICIES AND PROCEDURES
A. Compliant initial calibration for the analytes of concern is required before sample analysis
may begin.
B. Continuing calibration standards must meet established method criteria before proceeding
with sample analysis. Using any calibrations not specifically meeting the established
method criteria must be technically supported, and justification included in a narrative to
the client.
C. Quality control results must meet established method criteria before proceeding with
sample analysis. Reporting any quality control results not specifically meeting the
established method criteria must be technically supported, and justification included in a
narrative to the client.
CALIBRATION
A.
B.
METIIOD START-UP AND VALIDATION
I. To demonstrate the capability of the laboratory to generate valid data, the
following steps need to be performed.
a)
b)
c)
d)
e)
Calibration standards are analyzed at a minimum of 3 concentrations.
A calibration curve is established for each compound.
The method detection limit is calculated by analyzing seven replicates
prepared in blank water at 1 to 5 times higher than the estimated detection
limit.
Method detection levels are calculated according to 40 CFR 136,
Appendix B (July I, 1987) and Chapter One, SW-846 Final Update I.
The data are evaluated and, if acceptable, the method can be utilized on a
routine basis. Any changes in laboratory preparation or chromatography
that may effect the detection of the compounds requires that the MDL
study be repeated.
INITIAL CALIBRATION
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DATE:
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April 23, 1997
7 of 11
I.
2.
3.
Standard Preparation (See Section IX.B.)
Instrument Calibration
a) Calibration standards are prepared from the calibration gas standard in
organic-free reagent water. One of the concentration levels should be at
a concentration at or below the Pace Reporting Limit (PRL). The
remaining concentrations will determine the working range of the system.
The calibration levels used are 20, 100, l000 and l0000 ppm. The calibration
range can be extended, but the high standard will determine the upper end of the
calibration before dilution and reanalysis are required. The initial
calibration is submitted for a technical review.
b) The response factor for each compound is calculated by the data system
for each level of calibration utilizing Equation I. The average response
factor from these calibration standards is used to quantitate target analyte
concentrations.
Analysis of Calibration Data
a) Tabulate peak area responses against concentration for each compound
and internal standard and calculate response factors (RF) for each
compound by using Equation I.
Equation 1: Response Factor
where:
=
=
response for analyte of concern
concentration of analyte of concern
The percent relative standard deviation (¾RSD) for the response factors must
be <20% to determine that the calibration is linear
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METHANE IN WATER
BY GCFID
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FILENAME:
DATE:
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April 23, 1997
8 of 11
C. DAILY (CONTINUING) CALIBRATION
l. Standard Preparation
a) Daily standards (midpoint concentrations of the calibration curve) are to
be prepared in the same manner that the ICAL standards were prepared.
b) The analysis of this standard must be repeated after each set of I 0
environmental samples. Method blanks and Laboratory control samples
are not considered environmental samples.
2. Instrument Calibration
a)
b)
c)
d)
The calibration factor for each analyte to be monitored must not exceed
15% difference when compared to the average response factor from the
initial calibration. !fa check standard fails to meet the 15%D criteria, all
associated samples ,vill require reanalysis .. Repeated analyte failures
require an inspection of the GC system to determine the cause. Perform
necessary maintenance before recalibration and resuming sample analysis.
After the standards have been run, and are in control, a laboratory blank
is analyzed to check the analytical system for interferences.
The blank should contain less than the quantitation level of each analyte of
interest before sample analysis can start.
After calibration has been completed and the system is free of
interferences, sample analysis can start.
METHANE IN WATER
BYGCFID
MN-0-526-A
FILE !'/AME:
DATE:
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April 23, 1997
9 of 11
XIII. PROCEDURE
A.
B.
C.
GAS CHROMATOGRAPHY
I. Detectors
a) Flame Ionization Detector
Detector temperature ; 25 0°C
2. Column
• Restek GSQ fused silica capillary column 30m x 0.53 mm ID, 0 um film
thickness
• Column flow: IO mIJminute of Helium
• Initial temperature: 40°C; hold for 5 minutes
• Rate: 24°C/minute to 200°C
• Final Hold: 15 minutes
Note: All instrument conditions listed are examples. Analysts are expected to optimize
instrument perfomiance and make changes as needed. All standards, blanks, samples and QC
will be analyzed with the same conditions for the entire batch of samples.
TROUBLESHOOTING
1. Preventative maintenance that is performed does not correct all problems
associated with volatile organic analyses. Equipment malfunctions and samples
with very high concentrations can cause a variety of problems that are difficult to
diagnose. Each problem may require a combination of correction actions before
acceptable data may be generated.
2. All corrective actions should be documented in the instrument specific
maintenance logbook.
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FILE J','AME:
DATE:
PAGE:
MNOS26A.DOC
April 23, 1997
IO of 11
XIV. QUALITY CONTROL
A.
B.
Method Blank
I. Before processing any samples, the analyst should demonstrate through the
analysis of a method blank, that all glassware and reagents are interference free.
2. The method blank should be reanalyzed if these criteria are not met. All samples
that contain a positive hit for analytes also found in the blank will be footnoted
with a "B" flag.
Laboratory Control Sample
I.
2.
The continuing calibration verification standards will be reported as the laboratory
control sample.
If statistically generated control limits are not being utilized, the acceptance
criteria of ±20% from' the true value will be followed.
3. !fan LCS recovery falls outside of the limits, perform the following steps:
a)
b)
c)
Check to be sure there are no errors in calculations, standards preparation
and spiking of the LCS solution, or problems with the instrument
performance.
For cases where the LCS recovery is above the QC limits, the decision
can be made to accept the data if affected target analytes is not detected in
the associated sample(s).
Reanalyze the LCS once if the above steps failed to reveal or correct a
problem. If the LCS recovery is within limits in the reanalysis, accept the
associated sample data.
METHANE IN WATER
BYGCFID
MN-0-526-A
d)
XV. REFERENCES
FILE )',AME:
DATE:
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April 23, 1997
11 of 11
If the recovery is outside of the limits after reanalysis, reprepare and
reanalyze the LCS· and all associated samples when raw sample is
available. If the LCS recovery is within limits in this analysis, accept the
second set of data. When sufficient sample is not available to reanalyze
samples after an LCS failure, the associated samples must be flagged in
the final report.
A. Test Methods for Evaluating Solid Waste, PhysicaVChemical Methods, SW-846, 3rd Edition,
Final Update I, Method 3810.
B. 40 CFR Part 136, Appendix B, July I, 1987.
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Pace Analytical
Pace Analytical Services, Inc.
9800 Kincey Avenue, Suite 100
Huntersville. NC 28078
Tel: [phone]
fax: [phone]
STANDARD OPERATING PROCEDURE
INDUCTIVELY COUPLED PLASMA ATOMIC
EMISSION SPECTROSCOPY
Reference Methods: EPA 200.7 / SW846 6010A
SOP NUMBER:
EFFECTIVE DATE
SUPERSEDES:
APPROVAL
~r0 ,...,1¢='.i ch l \ ~ ::::.i
Operations Manager
~()__II\. fl11lcfl'--
QuaJity Assurance Offic
Fc,Q_General Manager -=
NCI-1-002
April I 0, 1997
MN-1-313-B
CONTROLILED COP{c. :\
COPY NO.. 'f Ge:I)
t)/10/~1
Date
1-J/JO /er;
Date
INDUCTIVELY COUPLED PLASMA A TO MIC
EMISSION SPECfROSCOPY
File Name: NC11002
Date: April IO, 1997
NCI-1-002 Page: ·· 2 of 15
I. PURPOSE
u.
The; purpose of this Standard Operating Procedure (SOP) is to establish a procedure for the
determination of metals by inductively coupled plasma atomic emissions spectroscopy.
SCOPE/APPLICATION
A.
B.
Scope: Inductively coupled plasma atomic emission spectroscopy (ICP-AES) is
utilized for the determination of metals in solution. The method is applicable to a large
number of matrices. All matrices, including ground water, aqueous samples, leachates,
industrial wastes, soils, sludges, sediments, and other solid wastes, require digestion
prior to analysis.
Analytes: Elements for which this method is applicable are listed in Table I.
C. Hazards and Precautions
Concentrated acids are corrosive and should be used in a laboratory hood when
possible. Protective clothing and safety glasses must be worn when working with
concentrated acids.Each reagent and chemical used in this method should be treated
as a potential health hazard. Reduce exposure by the use of gloves, lab coats,
safety glasses and ventilation hoods. Material Safety Data Sheets(MSDSs) are on
file in the library and available to all personnel.
ID. RESPONSIBILITY
A. Analysts
· I. Analysts are responsible for adherence to the SOP.
2. All laboratory personnel are responsible for notifying the section
supervisor/manager of any required revisions to the SOP.
B. Operations Manager
I. The operations manager is responsible for ensuring adherence to this SOP.
2. The operations manager is responsible for performing an annual review of the
SOP.
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INDUCTIVELY COUPLED PLASMA ATOMIC
EMISSION SPECTROSCOPY
File Name: NC11002
Date: April 10, 1997
NCl-I-002 Page: 3 of 15
C. Quality Assurance Officer (QAO)
I. The QAO is responsible for conducting laboratory audits to monitor adherence
to this SOP. Results of the audit are reported to Laboratory Management
and Corporate Quality.
2. The QAO is responsible for coordinating annual reviews of this SOP with the
general manager and the operations manager. More frequent reviews may
be required.
3. The QAO is responsible for ensuring that all revisions to the SOP are
implemented.
4. The QAO is responsible for determining distribution of and maintaining
document control of this SOP.
D. General Manager (GM)
I. The GM is responsible for the overall implementation of and adherence to this
SOP.
2. The GM is responsible for reviewing of this SOP with the QAO and the
operations manager.
IV. REVISIONS/REVIEWS
A. This SOP will be reviewed on an annual basis at a minimum, by the operations
manager, general manager and quality assurance officer.
B. At the time of review, any required revision will be incorporated.
C. The revised SOP will be distributed to all appropriate personnel and the superseded
version replaced.
V. DISTRIBUTION
A. Distribution of this SOP will be determined by the QAO.
INDUCTIVELY COUPLED PLASMA ATOMIC
EMISSION SPECTROSCOPY
File Name: NCII002
Date: April IO, I 997
4 of 15 NCI-1-002 Page:
VL
VII.
SUMMARY OF METHOD
A.
B.
C.
Prior to analysis, samples must be solubilized or digested using appropriate sample
preparation methods.
This method describes the simultaneous multielemental detennination of elements by
ICP. The method measures element-emitted light by optical spectrometry. Samples
are nebulized and the resulting aerosol is transported to the plasma torch. Element-
specific atomic-line emission spectra are produced by a radio-frequency inductively
coupled plasma. The spectra are dispersed by a grating spectrometer, and the
intensities of the lines are monitored by photomultiplier tubes.
Background correction may be required. Background is measured adjacent to analyte
lines on samples during analysis. The position selected for the background-intensity
measurement, on either or both sides of the analytical line, will be detennined by the
complexity of the spectrum adjacent to the analyte line. The position used should be
free of spectral interference and reflect the same change in background intensity as
occurs at the analyte wavelength measured. Background correction is not required in
cases ofline broadening where a background correction measurement would actually
degrade the analytical result. The possibility of additional interferences named in
Section VIII should also be recognized and appropriate corrections made as necessary.
INTERFERENCES
A. SPECIAL INTERFERENCES are caused by:
I. Overlap of a spectral line from another element;
2.
3.
4.
Unresolved overlap of molecular band spectra;
Background contribution from continuous or recombination phenomena.
Stray light from the line emission of high-concentration elements. Spectral
overlap can be compensated for by computer-correcting the raw data after
monitoring and measuring the interfering element. Background contribution
and stray light can usually be compensated for by a background correction
adjacent to the analyte line. Interelement correction factors are used on the
simultaneous ICP.
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File Name: NCII002
Date: April 10, 1997
5 of 15 NCl-I-002
B.
Page:
PHYSICAL rNTERFERENCES
I. These are effects associated with the sample nebulization and transport
processes. Changes in viscosity and surface tension can cause significant
inaccuracies, especially in samples containing high levels of dissolved solids or
high acid concentrations. If physical interferences are present, they may be
reduced by diluting the sample. Another problem that can occur with high
dissolved solids is salt buildup at the tip of the nebulizer, which ,effects aerosol
flow rate and causes instrument drift. The problem can be controlled by
wetting the argon prior to nebulization, or diluting the sample.
vm. APPARATUS AND MATERIALS
A. INSTRUMENTATION
B.
C.
D.
E.
F.
G.
I.
2.
Thermo Jarrell Ash -

T

J A 61 E.
Liquid argon
BALANCE
1. Analytical balance, accurate to at least IO mg.
BEAKERS
1. 150 mL or other appropriate vessel with watch glass covers.
FILTER PAPER
I. Whatman No. 41 or equivalent.
VOLUMETRIC FLASKS
· I. Assorted Class A volumetric flasks.
PIPETS
I.
2.
Assorted Class A.
Automatic pipets with disposable tips.
HOTPLATES
INDUCTIVELY COUPLED PLASMA ATOMIC
EMISSION SPECTROSCOPY
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Date: April 10, 1997
NCl-1-002 Page: 6 of 15
IX. REAGENTS
A
B.
C.
D.
E.
F.
G.
Hydrogen peroxide, 30%
Hydrochloric acid, Cone., trace metals grade.
Hydrochloric acid, (1 :I). Add 500mL cone. HCI to 400mL DI water and dilute to 1 L.
Concentrated Nitric Acid (HN03), trace metals grade, or equivalent.
Nitric Acid (I: I) Add 500mL cone. HN03 to 400mL DI water and dilute to IL.
Deionized Water (DI)
Standard Stock Solutions, purchased (NIST Traceable).
I.
2.
3.
Mixed Calibration Standard Solutions:
a. Prepare mixed calibration standard solutions by combining appropriate
volumes of the stock solutions in volumetric flasks (see Table II for
appropriate concentrations and element compatibility). Add 5 mL
concentrated HN03 and dilute to I 00 mL with Type II water. Care
should be taken when preparing the mixed standards to ensure that the
elements are compatible and stable together. Fresh mixed standards
should be prepared as needed, or if older than 180 days. Verify
calibration standards using a second source standard. Some typical
calibration standard combinations are listed in Table II.
Spiking Solutions:
a. A suitable spiking solution can be prepared from stock solutions by
utilizing specified volumes and concentrations outlined in Table ill.
Calibration Verification Standard:
a. If the instrument was calibrated using the standards in Table n, a
suitable verification standard would contain 1.0 mg/L of all listed
constituents (10.0 mg/L of Potassium).
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X. SAMPLE PRESERVATION AND HOLDING TIMES
A. SAMPLE PRESERVATION
B.
I. Water Sample Preservation
2.
a. Measurement Parameter: Metals or dissolved metals. Samples are
filtered through a 0.45 micron filter immediately on-site by the sampler
before adding preservatives.
b. Container: polyethylene or glass.
c. Preservation: Sample preservation is performed by the sampler
immediately upon sample collection. Use HN03 to bring the pH to <2.
Soil and Sediment Preparation
a. Soils/sediment will be maintained at 4° C ± 2 until analysis.
HOLDfNG TIMES FOR WATER AND SOII.JSEDIMENT SAMPLES
!. The maximum sample holding time for metals is 180 days from sample receipt.
XL SAMPLEPREPARATION
A. Refer to SW-846, 3000 series, sample preparation procedures and the corresponding
PACE SOP.
XII. INSTRUMENT AL ANALYSIS
A.
B.
C.
Consult instrument manufacturer's user's manuals for specific operational instructions.
See Table IV for an example run sequence.
fNSTRUMENT CALIBRATION
I. Instrumental calibration is to be performed in accordance with the
manufacturer's specifications.
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EMISSION SPECfROSCOPY
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Date: April 10, 1997
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2.
Page:
Instruments must be calibrated once every 24 hours and each time the
instrument is set up. The instrument standardization date and time must be
included in the raw data.
xm. QA/QC REQUIREMENTS
A. The QA/QC requirements for the analysis are listed below:
B.
C.
1.
2.
3.
4.
5.
6.
Instrument Calibration
Analysis of calibration standards
Initial Calibration Verification (!CV) and Continuing Calibration Verification
(CCV)
Initial Calibration Blank (ICB), Continuing Calibration Blank (CCB) and
Method Blank (MB)
Laboratory Control Sample (LCS)
Matrix Spike Sample (MS) and Matrix Spike Duplicate (MSD)
7. Interelement Corrections for ICP (ICSA, ICSAB)
8. Serial Dilution Analysis (L)
ANALYSIS OF CALIBRATION ST AND ARDS
1. Each calibration standard should be analyzed after calibration. The results
must agree with 5% of the accepted value. If the results are not within 5%, the
analysis should be terminated, the problem corrected and the instrument
recalibrated.
INITIAL CALIBRATION VERIFICATION (ICV) AND CONTINUING
CALIBRATION VERIFICATION (CCV)
1. Initial Calibration Verification (!CV)
a. The Initial Calibration Verification Solution(s) should be obtained from
a different source than the calibration standards.
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9 of 15 NCl-1-002
C.
D.
b. Immediately after the calibration standards have been analyzed, the
accuracy of the initial calibration shall be verified and documented for
every analyte by the analysis ofan Initial Calibration Verification
Solution(s) at each wavelength used for analysis. When measurements
exceed the control limits of 5% the analysis should be terminated, the
problem corrected, the instrument recalibrated and the calibration
reverified.
CONTINUING CALIBRATION VERIFICATION (CCV)
I.
2.
To ensure calibration accuracy during each analysis run, a continuing
calibration verification must be analyzed for each analyte, at a frequency of
10% during an analytical run. The standard must also be analyzed after the last
analytical sample. The analyte concentrations in the continuing calibration
standard should be at or near the mid-range levels of the calibration curve. The
ICV solution can be utilized as the CCV.
If the deviation of the continuing calibration verification is greater than the
control limits of± 10% (± 5% for Method 200.7-Wastewater), the instrument
must be recalibrated and the preceding analytical samples reanalyzed since the
last acceptable calibration verification must be reanalyzed.
INITIAL CALIBRATION BLANK (ICB), CONTINUING CALIBRATION
BLANK (CCB) AND METHOD BLANK (MB)
I.
2.
Initial Calibration Blank (ICB) and Continuing Calibration Blank (CCB)
a. A calibration blank must be analyzed at each wavelength used for
analysis immediately after every initial and continuing calibration
verification, at a frequency of I 0%.
Method Blank (MB) Analysis
a. At least one method blank (or reagent blank), consisting of DI water
must be prepared and analyzed with each group of samples digested. If
the concentration in the MB is greater than 3X the MDL, the samples
associated with that MB must be reprepped. No elements should be
present at a concentration greater than the Pace Reporting Limit
(PRL).
INDUCTIVELY COUPLED PLASMA ATOMIC
EMISSION SPECTROSCOPY
File Name: NC11002
Date: April 10, 1997
NCl-1-002
E.
F.
Page: 10 of 15
LABORATORY CONTROL SAMPLE (LCS)
I. Laboratory Control Samples (LCS) must be analyzed for each analyte using the
same sample preparations, analytical methods and QA/QC procedures
employed for the samples received. One aqueous LCS must be prepared and
analyzed for every batch of samples digested.
2. If the percent recovery for the LCS falls outside the control limits of 90-110%
( exception: Ag and Sb), the analyses should be terminated, the problem
corrected, and the samples associated with that LCS redigested and reanalyzed.
MATRIX SPIKE SAMPLE (MS)
The matrix spike sample analysis is designed to provide information about the
effect of the sample matrix on the digestion and measurement methodology. ·
The spike is added before the digestion (i.e., prior to the addition of other
reagents). At least one spiked sample must be analyzed for each batch of
samples of a similar matrix spike type (i.e., water, soil) at a minimum frequency
of 5%. Spiking levels are listed in Table ill.
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The percent recovery of the spike is calculated from the following equation: I
G
% Recovery= (SSR-SR) • 100 I
ST
Where: SSR =
SR =
ST =
Spike sample result, mg/L or mg/kg dry
Sample result, mg/L or mg/kg dry
Spike target, mg/L or mg/kg dry
2. When sample concentration is less than the instrument detection limit, let
SR= 0 only for calculating percent recovery.
· MATRIX SPIKE DUPLICATE ANALYSIS
l.
2.
One matrix spike duplicate sample must be analyzed from each batch of
samples of a similar matrix type (i.e., water, soil).
This analysis will be performed at a minimum frequency of 5%. The relative
percent differences can be calculated as follows:
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INDUCTIVELY COUPLED PLASMA ATOMIC
EMISSION SPECfROSCOPY
File Name: NC!.1002
Date: April 10, I 997
11 of 15 NCl-1-002
H.
RPD=
Where:
RPD
s
D
(S-D) • (100)
(S+D)/2
= Relative Percent Difference
Page:
= Original Spiked Sample Value, mg/Lor mg/kg dry
= Second Spiked Sample Value, mg/Lor mg/kg dry
INTERELEMENT CORRECTIONS FOR SIMULTANEOUS ICP
I. Interelement correction factors must be determined annually. Correction
factors for spectral interference due to Al, Ca, Fe, and.Mg must be determined
for all ICP instruments at all wavelengths used for each analyte reported by
ICP. Correction factors for spectral interference due to analytes other than Al,
Ca, Fe, and Mg must be reported if they were applied.
2. If the instrument was adjusted in any way that may affect the ICP interelement ·
correction factors, the factors must be redetermined.
XIV. DOCUMENTATION
A.
B.
RAW DAT A FILES/ MAINTENANCE
I. Each daily folder must contain the sample sequence, all calibration data and
raw data for samples and QC samples. Maintenance should also be recorded
as performed and logged into the appropriate maintenance logbook.
· ST AND ARD PREPARATION LOG BOOK
I. Record the necessary information (volumes, manufacturer, lot number, etc.) in
the standard logbooks.
XV. REFERENCES
A.
B.
Test Methods for Evaluating Water and Solid Waste, SW-846 3rd Edition, final
Update L Method 6010A
USEPA Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020,
March 1983.
D
INDUCTIVELY COUPLED PLASMA ATOMIC File Name: NC11002 I
EMISSION SPECfROSCOPY Date: April 10, 1997
NCl-1-002 Page: 12 of 15 I
TABLE I I TARGET ANALYTE LIST
Wavelength' MDLb PRLC PRLC I Element (run) (mg/L) (mg/L) (mg/kg)
Waters Soils
Aluminum Al 308.216 0.0052 0. IO 10 I
Antimony Sb 206.838 0.020 0.20 20
, -Krsenic:. As 189.042 0.026 0.50 so I
. Baiium· Ba 493.409 0.0066 0.01 1.0
Beryllium Be 313.042 0.0001 0.01 1.0
Boron B 182.640 0.070 0.10 JO I
< Cadrniull_l. Cd 228.802 0.0022 0.01 1.0
Calcium Ca 317.933 0.022 0.10 JO I Chromium Cr 267,716 0.0016 0.01 1.0
Cobalt Co 228.616 0.0024 0.01 1.0
Copper Cu 324.754 0.0014 0.01 1.0 I Iron Fe 259.940 0.0016 0.05 5.0
Lead-Pb 220.353 0.017 0.10 10
--. ··--
Magnesium Mg 279.079 0.033 0.20 20 I Manganese Mn 257,610 0.0006 0.01 1.0
Molybdenum Mo 202.030 0.0074 0.05 5.0
Nickel Ni 231.604 0.0097 0.05 5.0 I Potassium K 766.491 0.27 1.0 100
SeleniuJll Se 196.026 0.037 0,5 50
.. ··sijye( Ag 328.068 0.0019 0.05 5.0 I Sodium Na 588.995 0.027 0.20 20
Thallium TI 190.864 0.18 0.50 so
Tin Sn 283.999 0.048 0.20 20 I
Titanium Ti · 334.941 0.0009 0.01 1.0
Vanadium V 292.402 0.0023 0.01 1.0
Zinc Zn 213.856 0.0026 0.01 1.0 I
Footnotes: I • The wavelengths listed are recommended because of their sensitivity and overall acceptance .
b The method detection limits (MDL) shown are approximate. Actual detection limits are
instrument specific and matrix dependent. The above limits were generated from replicate I analysis of spiked DI-water.
C The Pace Reporting Limits (PRLs) shown are based on method requirements, regulatory
requirements and client specifications. I
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I INDUCTIVELY COUPLED PLASMA ATOMIC File Name: NCH002
EMISSION SPECTROSCOPY Date: April 10, 1997
I NCl-I-002 Page: 13 of 15
I TABLE II
CALIBRATION STANDARD CONCENTRATIONS
I
Calibration Standard -Mix A Calibration Standard -Mix B
I Blank Level 1 Level 2 Level 3 Level 1 • Level 2 Level 3
Element ~ ~ ~ !!!filk ~ ~ mg/L
I
I As 0 2 5
Al 0 2 5
Ba 0 I 2 5
I Be 0 2 5
B 0 I 2 5
Cd 0 I 2 5
I Ca 0 I 2 5
Cr 0 2 5
Co 0 I 2 5
I Cu 0 I 2 5
Fe 0 I 2 5
Pb 0 I 2 5
I Mg 0 I 2 5
Mn 0 2 5
Mo 0 I 2 5
I Ni 0 I 2 5
K 0 10 20 50
Sb 0 I 2 5
I Se 0 I 2 5
Ag 0 2 5
I Na 0 I 2 5
Tl 0 I 2 5
Sn 0 I 2 5
I Ti 0 I 2 5
V 0. 2 5
Zn 0 I 2 5
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INDUCTIVELY COUPLED PLASMA ATOMIC
EMISSION SPECTROSCOPY
File Name: NC1I002
Date: April 10, 1997
14 of 15 NCl-l-002 Page:
TABLE ID
ICP SPIKING SOLUTION
mLsof Cone. of Spike Target
Element Stock Solution ( I) Spiking Solution (ppm)(]) (ppm) (2)
Al l.0 5000 50
Ag 1.0 500 5
As l.O 500 5
Ba 1.0 500 5
Be 1.0 100
B l.O 100
Ca l.O 10,000 100
Cd 1.0 100
Co 1.0 100
Cr l.O 100
Cu l.0 100
Fe l.O 5000 50
Mg l.O 5000 50
Mn l.O 100
Mo 1.0 100
Ni 1.0 100 I
K 1.0 10,000 100
Pb 1.0 500 5
Se l.O 500 5
Na 1.0 5000 50
Sb l.O 500 5
Tl 1.0 500 5
Sn 1.0 100
Ti 1.0 100
V 1.0 100
Zn l.O 100
(1) The spiking solution is made to a final volume of 1000 mL in 5% cone HNOJ.
(2) Spike targets are the result of adding 1.0 mLs of spiking solution to I 00 mLs of sample.
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INDUCTIVELY COUPLED PLASMA ATOMIC
EMISSION SPECTROSCOPY
File Name: NC11002
Date: April 10, 1997
15 of 15 NCl-I-002
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TABLE IV
TYPICAL SAMPLE RUN SEQUENCE
Calibration Standards
ICY
ICB
MDL Check Standard
Independent Check Standard
ICSA-Initial
ICSA-Initial
Nickel Std@0.02mg/L (Only for Drinking Water Samples)
MB
LCS/LCSD
Sample 1
Sample 2
Sample 2 -Matrix Spike
Sample 2 -Matrix Spike Duplicate
Sample3
CCVI
CCBl
Sample 4
Sample 4 -Duplicate
Sample 5
Sample6
Sample 7
Sample 8
Sample 9
Sample 10
ICSA-Final
ICSAB-Final
CCV2
CCB2
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Pace Analytical
Pace Analytical Services, Inc.
9800 Kincey Avenue. Suite I 00
Huntersville. NC 28078
Tel: [phone]
Fax: [phone]
STANDARD OPERATING PROCEDURE
Mercury (Hg) -Waters
Reference Methods: EPA 245.l / SW846 -7470A
vr111
.C // i,
SOP NUMBER:
EFFECTIVE DATE:
NCl-1-031
April 24, I 997
Draft SOP SUPERSEDES
APPROVAL
Quality Assurance Officer
General Manager
CONTROLL.ED COPY
COPY NO._.-=~--
1,.-f-Z'<-91--
Date
Date
Date
Mercury-Hg Waters File Name: NCII028
Apr. 24, 1997
2 of7
EPA 245.1 / SW846 7470A
NCI-I-028
Date:
Page:
L
II.
m.
PURPOSE
The purpose of this standard operating procedure (SOP) is to determine the concentration
of mercury in drinking, surface, saline and ground waters, domestic and industrial wastes.
SCOPE/APPLICATION
A. Summary -Samples are prepared for analysis by an acid digestion procedure.
Digested samples are analyzed by a cold-vapor atomic absorption technique based
on the absorption of radiation at 253. 7 run by mercury vapor.
B. Hazards and Precautions
Each reagent and chemical used in this method should be treated as a potential
health hazard. Reduce exposure by the use of gloves, lab coats, safety glasses and
ventilation hoods. Material Safety Data Sheets(MSDSs) are on file in the library .
and available to all personnel.
RESPONSIBILITY
A.
B.
C.
Analysts
I. Analysts are responsible for adherence to the SOP.
2. All laboratory personnel are responsible for notifying the section
supervisor/manager of any required revisions to the SOP ..
Operations Manager
2.
The operations manager is responsible for ensuring adherence to this SOP.
The operations manager is responsible for performing an annual review of
the SOP.
Quality Assurance Officer (QAO)
1. The QAO is responsible for conducting laboratory audits to monitor
adherence to this SOP. Results of the audit are reported to Laboratory
Management and Corporate Quality.
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Mercury-Hg Waters File Name: NC!I028
Apr. 24, 1997
3 of 7,
EPA 245.1 / SW846 7470A
NC!-I-028
Date:
Page:
IV.
V.
D.
2. The QAO is responsible for coordinating annual reviews of this SOP with
the general manager and the operations manager. More frequent reviews
may be required.
3. The QAO is responsible for ensuring that all revisions to the SOP are
implemented.
4. The QAO is responsible for determining distribution of and maintaining
document control of this SOP.
General Manager (GM)
1.
2.
The GM is responsible for the overall implementation of and adherence to
this SOP.
The GM is responsible for reviewing of this SOP with the QAO and the
operations manager.
REVISIONS/REVIEWS
A. This SOP will be reviewed on an annual basis at a minimum, by the operations
manager, general manager and quality assurance officer.
B. At the time of review, any required revision will be incorporated.
C. The revised SOP will be distributed to all appropriate personnel and the
superseded version replaced.
DISTRIBUTION
A. Distribution of this SOP will be determined by the QAO.
Mercury-Hg Waters File Name: NCII028
Apr. 24, 1997
4of7
EPA 245.1 / SW846 7470A
NCI-I-028
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VI. APPARATUS AND MATERIALS
A.
B.
Apparatus / Equipment
I.
2.
3.
4.
5.
Water Bath, capable of maintaining 95 degree Celsius.
Pipettes: 100, 1000, 2500 and 10,000 uL
Test Tubes: 13 x 100 with caps
25 ml volumetric flask, class A (Clean flask with I: I HNO3)
Mercury Analyzer -Leeman PS200 or equivalent
Reagents / Standards
I.
2.
3.
4.
5.
6.
7.
8.
9.
IO.
II.
12.
Deionized water (DI-H2O)
Hg Stock Solution ( 1000 mg(L). Reagents Inc. or equivalent.
Alternate Source -Hg Stock Solution ( 1000 mg(L). to be used for LCS
and matrix spike.
Primary Hg Solution (I 0mg(L): Fill a 25 mL volumetric flask half way with
DI-H2O. Pipette 37.5 uL HNO3 and 250 uL of the Hg Stock Solution into
flask and dilute to mark. Store at 4°C.
Alternate Source -Primary Hg Solution (I 0mg(L): Fill a 25 mL volumetric
flask halfway with DI-H2O. Pipette 37.5 uL HNO3 and 250 uL of the
Alternate Source -Hg Stock Solution into flask and dilute to mark. Store
at 4°C.
Working Hg Solution (0.1 mg(L or I00ug(L): Fill a 25 mL volumetric flask
halfway with reagent water. Pipette 37.5 uL HNO3 and 250 uL Primary
Mercury Solution into flask and dilute to mark. Prepare daily.
LCS -Working Hg Solution (0.1 mg(L or I00ug/L): Fill a 25 mL
volumetric flask halfway with reagent water. Pipette 37.5 uL HNO3 and
250 uL Alternate Source -Primary Hg Solution into flask and dilute to
mark. Prepare daily.
Nitric Acid; HNO3 cone.
Sulfuric Acid; H2SO, cone.
Potassium Permanganate Solution: Dissolve 50 g KMnO, in 800 mL
reagent water and dilute to I liter.
Potassium Persulfate Solution (K2S2O8): Dissolve 50 g K2S2Os in 800 mL
reagent water and dilute to I liter.
Note: You may need to heat solution to dissolve completely.
Sodium Chloride-Hydroxylarnine Solution: Dissolve 120 g NaCl and 120 g
(NH2OH2)*H2SO4 in 800 mL reagent water and dilute to I liter.
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Mercury-Hg Waters File Name: NC1I028
Apr. 24, 1997
5 of7
EPA 245.l / SW846 7470A
NCl-I-028
Date:
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VII. PROCEDURE
A. Preparation of Calibration Standards:
I.
2.
Make Working Hg Solution@ 100 ug/L.
Using 25 mL volumetric flasks, prepare calibration standards by diluting
aliquots of the. working mercury solution as indicated in the chart below.
Calibration Volume of Cone. of Final Final
Standard Hg Solution Hg Solution Volume (mL) Cone.
Blank
I
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3
4
5
B.
C.
(mL) (ug/L) (ug/L)
0 -25 0
0.05 100 25 0.2
0.25 100 25 1.0
0.50 100 25 2.0
1.25 100 25 5.0
2.5 100 25 10.0
3. Transfer 8 mLs of each standard to separate test tubes to be digested.
Preparation of LCS and Matrix Spike:
I. Make LCS -Working Hg Solution@ 100 ug/L.
2. Using 25 mL volumetric flasks, prepare the QC samples as follows:
a. LCS -Fill a 25mL volumetric flask halfway with DI-H2O. Add
0.5 mL of the LCS -Working Hg Solution. Dilute to mark.
b. Matrix Spike -Fill a 25mL volumetric flask half way with a sample
designated to be used as the matrix spike. Add l.25mL of the
LCS -Working Hg Solution. Dilute to mark.
3.. Transfer 8 mLs of each QC sample to separate test tubes to be digested.
Digestion:
I. Turn on and fill water bath with reagent water. Adjust temperature to
95•c.
2.
3.
4.
5.
Pipette 8 mLs ofDI-H2O into a test tube to be used as a method blank.
Pipette 8 mLs of each sample into separate test tubes.
Gather test tubes for calibration standards and QC samples prepared in
steps A and B above.
Add 400 uL H2SO., 200 uL HNO3, and 1200 uL KMnO. to each test tube
(Including the calibration standards, method blank, and QC samples
Mercury -Hg Waters File Name: NC1I028
Apr. 24, 1997
6of7
EPA 245.1 / SW846 7470A
NCI-I-028
Date:
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D.
6.
5.
6.
7.
8.
Let stand for 15 minutes. If purple color does not persist, add more
KMnO4 or dilute sample.
(Note: If you add more KMnO4 to sample, make sure to add the same
amount to the calibration standards, QC samples and all other samples.)
After I 5 minutes pipette 650 uL K2S2O 8 into sample, cap and invert twice.
Place in water bath for 2 hours.
After samples have cooled to room temperature pipette 480 uL of
(NH2OH2)*H2SO4 and mix until purple color turns clear.
Samples are ready for analysis by the Cold Vapor method.
Analysis:
1. Transfer the test tubes to the Mercury Analyzer autosampler.
2. Foil ow the manufacturers instructions for operation and calibration of the
Mercury Analyzer.
3. The instrument must be calibrated every day. The correlation coefficient of _
the calibration curve must be~ 0.995.
4. Verify the reporting limit by reanalyzing calibration standard 1 @ 0.2ug/L
after the instrument is calibrated. The results must be within +/-25%.
5. The instrument will print out a report of the concentration of Hg in each
sample.
VIlI. QUALITY CONTROL
A.
B.
C.
Method Blank: To be run daily with each batch of samples. Mercury should not
be detected at or above the reporting limit of0.2 ug/L.
Duplicate: NC requires a duplicate every IO samples. A matrix spike duplicate
may count as a sample duplicate. The relative percent difference(RPD) must be
'.520%. Special consideration must be made for concentrations less than ten times
the reporting limit.
RPD = Difference x I 00
Mean
= (Cone. 1 -Cone. 2) x 100
(Cone. 1 + Cone. 2) / 2
Spike: A matrix spike must be analyzed every batch of20 samples for wastewater
and every 10 samples for drinking water. Spike so that the resulting concentration
is equal to 5.0ug/L. The percent recovery must be within+/-20% for wastewater
and +/-10% for drinking water.
% Recovery = (Spiked Sample Value -Sample Value) x 100
True Value
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Mercury -Hg Waters File Name: NC!I028
Apr. 24, 1997
7 of7
EPA 245.1 / SW846 7470A
NCI-I-028
Date:
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D.
E.
F.
G.
Laboratory Control Sample(LCS): To be analyzed with each batch of20
samples. Spike so that the resulting concentration is equal to 2.0ug/L. The percent
recovery of the LCS must be within 10% of the expected value.
% Recovery = Reported Value x I 00
True Value
Pace Reporting Limit (PRL): 0.2 ug/L
Sample Preservation: HNOi to pH <2.
Holding Time: 28 days.
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STANDARD OPERATING PROCEDURE
Total Organic Carbon
by Persulfate-Ultraviolet Oxidation Method
Standard Method 5310 C
SOP Number
Author
Effective Date
Supersedes
Quality Assurance Officer
General Manager
Approval
L
ASV-I-105
Robin K Blankenbaker
April 2, 1997
All previous editions
L.f-(D-i7
Date
Date
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TOC
1. Scope/Application
ASV-I-105
April 2, 1997
Page 1 of 4
1.1. The persulfate-ultraviolet method is a rapid, precise method for the
measurement of trace levels of organic carbon in water. This is important for
industries where even trace levels of organic compounds may be detrimental
to the process for which the water is being utilized.
1.2 Concentrations of 0.05mg carbon/L can be measured if close attention is
given to minimizing sample contamination and method background. The
combustion-infared method should be used for high concentrations of TOC.
2. Summary of Method
2.1 Organic carbon is oxidized to CO2 by persulfate in the presence of
ultraviolet light. The CO2 produced can be measured directly by a
nondispersive infrared analyzer, be reduced to methane and measured
by a flame ionization detector, or be chemically titrated.
2.2 Samples are introduced into a reactor by autosampler or injected
manually. The resulting CO2 is sparged continuously from the solution and
carried in the gas stream to an infrared analyzer specifically tuned to the
absorptive wavelength of CO2.
2.3 The instrument's microprocessor calculates the area of the peaks
produced by the analyzer, compares them to the peak area of the calibration
standard stored in it's memory, and prints out a calibrated organic carbon
value in mg/L.
3. Interferences
3.1 Excessive acidification of sample, producing a reduction in pH of the
persulfate solution to 1 or less, can result in slow or incomplete oxidation of
organic carbon.
3.2 Highly turbid samples may not be completely oxidized due to the UV's
inability to penetrate the sample. Also, very large or complex organic
compounds may be oxidized slowly.
3.3 If the sample has a chloride concentration greater than 0.1 %, oxidation
of organic matter may be inhibited completely. Mercuric nitrate should be
added to the persulfate solution to eliminate the chloride.
3.4 Sample contamination during handling, sampling, or analysis is a
potential problem in any organic carbon measurement. Take extreme care
with the samples.
TOC
4. Sample Handling and Preservation
ASV-I-105
April 2, 1997
Page 2 of 4
Samples are collected and stored in 250ml plastic bottles and preserved at
4C with minimal exposure to light. Samples may be acidified to pH of~ with
sulfuric acid.
5. Safety
Safety glasses, lab coats, and gloves should be worn at all times. As sample
constituents are not known, all samples should be treated as hazardous.
6. Apparatus
a. A total organic carbon analyzer (Xertex-Dohrmann DC-80 or equivalent).
b. Syringes: 0 to S0µL, 0 to 250µL, and 0-1 ml capacity fitted with blunt
tipped needle.
7. Reagents
a. Reagent water: Prepare blanks and standard solutions from carbon-free
water; preferably use carbon filtered, redistilled water.
b. Phosphoric acid, cone. Alternatively use sulfuric acid, but never use
hydrochloric acid
c. Organic carbon stock solution: A pre-made standard is purchased for the
TOC analysis and diluted for use as working standards. A separate standard
with a different lot number is diluted for use as check standard.
e. Carrier gas: Purified oxygen or air, CO2-free and containing less than
1ppm hydrocarbon (as methane)
f. Purging gas: any gas free of CO2 and hydrocarbons.
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TOG
8. Procedure
8.1 Instrument Operation:
ASV-I-105
April 2, 1997
Page 3 of 4
Follow manufacturer's instructions for operation of analyzer.
8.2 Sample Preparation:
If a sample contains gross particles or inorganic matter, homogenize
until a representative portion can be drawn through a syringe needle or
autosampler tubing.
8.4 Standard curve preparation:
Prepare an organic carbon standard series over the range of organic
carbon concentrations in the samples. Inject standards and blanks and
record analyzer's response. Before injecting samples, replicate injections
of a midrange standard should be injected. If their measured
concentrations differ by more than 10%, take corrective action, and
reinject.
8.3 Sample injection:
Withdraw a portion of prepared sample using a syringe fitted with a
blunt-tipped needle. Select sample volume according to manufacturer's
direction. Stir samples containing particulates with a magnetic stirrer.
Select needle size consistent with sample particulate size. Inject
samples and standards into analyzer according to manufacturer's
directions and record response.
9. Calculations
9.1 Instrument printout will provide the analyst with concentrations. To
these concentrations, a dilution factor, if any, should be applied.
TOG
10. Quality Assurance/Quality Control
ASV-I-105
April 2, 1997
Page 4 of 4
10.1 At least one sample in every 10 must be analyzed in duplicate. If less
than 10 samples are analyzed per month, at least one sample each month
should be analyzed in duplicate.
For concentrations of 1-10mg/L, the duplicate acceptance range is±
0.39mg/L. For concentrations of 11-40mg/L, the range is ±4.2mg/L, and for
concentrations greater than 40mg/L, the range is ±10% based on three times
the standard deviation for the method. Any duplicates not meeting this
criteria must be reanalyzed or a specific reason determined why the duplicate
did not work. This reason must be written on the benchsheet.
10.2 A mid range reference standard must be analyzed every day samples
are run and at least once for every 10 samples analyzed. It's value must be
within ±10% of the true value.
10.3 A spike must be run with every ten samples, it's value should be within
±25% of it's actual value.
10.3 All data are reviewed by the inorganics department group leader, lab
supervisor, and project manager prior to release.
11. References
Standard Methods, 18th Edition, Method 5310-C.
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Pace Analytical
Pace Analytical Services, Inc.
9800 Kincey Avenue, Suite 100
Huntersville, NC 28078
Tel: [phone]
Fax: [phone]
STANDARD OPERA TING PROCEDURE
Chloride
Reference Method: EPA 325.3
SOP NUMBER:
AUTHOR:
NCI-I-003
Barney Kesler
CONTROLLEt copv .. ,-\
COPY NO.~, G-(;_L)
EFFECTIVE DATE: Februrary 28, I 997
Other chloride SOPs SUPERSEDES:
APPROVAL
Qu~ty Assurance Office a.c_
General Manager Date
Chloride
EPA325.3
NCI-1-003
File Name:
Date:
Page:
NCII003
·Feb. 28, 1997
2 of6
I.
II.
PURPOSE
.The purpose of this Standard Operating Procedure (SOP) is to measure the concentration
of chlorides in drinking, surface, and saline waters, domestic and industrial wastes ..
SCOPE/APPLICATION
A.
B.
C.
Summary -An acidified sample is titrated with mercuric nitrate in the presence of
mixed diphenylcarbozonebromophenol blue indicator. The end point of the
titration is the formation of the blue-violet mercury diphenylcarbozone complex.
Interferences
I. Anions and cations at concentrations normally found in surface waters do
not interfere.
2. Sulfite interference can be eliminated by oxidizing the l 00mLs of sample
solution with 1.0 to 2.0 mL of hydrogen peroxide.
Hazards and Precautions
Each reagent and chemical compound used in this method should be treated as a
potential health hazard. Reduce exposure by the use of gloves, lab coats, safety
glasses and ventillation hoods. Material Safety Data Sheets(MSDSs) are on file in
the library and available to all personnel.
III. RESPONSIBILITY
A.
B.
Analysts
2.
Analysts are responsible for adherence to the SOP.
All laboratory personnel are responsible for notifying the section
supervisor/manager of any required revisions to the SOP.
Department Manager
1. Managers are responsible for ensuring adherence to this SOP.
2. Managers are responsible for performing an annual review of the SOP.
6
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Chloride
EPA325.3
NCI-I-003
C.
D.
File Name:
Date:
Page:
NCII003
Ft!b.28, 1997
3 of6
Quality assurance officer (QAO)
I. The QAO is responsible for conducting laboratory audits to monitor
adherence to this SOP. Results of the audit are rep·orted to Laboratory
Management and Corporate Quality.
2. The QAO is responsible for coordinating annual reviews of this SOP with
the regional director and the organics department manager. More frequent
reviews may be required.
3.
4.
The QAO is responsible for ensuring that all revisions to the SOP are
implemented.
The QAO is responsible for determining distribution of and maintaining
document control of this SOP.
General Manager (GM)
1.
2.
The GM is responsible for the overall implementation of and adherence to
this SOP.
The GM is responsible for reviewing of this SOP with the QAO and the
department manager.
IV. REVISIONS/REVIEWS
V.
A.
B.
C.
This SOP will be reviewed on an annual basis at a minimum, by the department
manager, general manager and quality assurance officer.
At the time of review, any required revision will be incorporated.
The revised SOP will be distributed to all appropriate personnel and the
superseded version replaced. ·
DISTRIBUTION
A. Distribution of this SOP will be determined by the QAO.
Chloride
EPA325.3
NCI-I-003
File Name:
Date:
Page:
NCII003
Feb. 28, 1997
4 of6
VI. APPARATUS AND MATERIALS
VII.
A.
B.
Apparatus
I. !0mL Buret with 0.05mL increments
2. 250mL Erlenrnyer flasks
3. Magnetic Stirrer and magnetic stir bars
4. Transfer pipets
Reagents / Standards
I. Deionized Water {DI-H,O)
2. Standard Sodium Chloride (Prernade) -Lab Chern Inc. Cat. #LC13010-l.
3. LCS Spike Solution (Prernade) -I000pprn Chloride Standard,
lmL = 1mg Cr, Lab Chern Inc. Cat. #LC13000-l.
4. Matrix Spike Solution (Prernade)-0.0141N Chloride Standard,
lmL = 500pprn, RICCA Chemical Co. Cat. #1950-16.
5. 0. IN Nitric Acid {HNO,) Solution -3mLs HNO3 to 997mLs Dl-H2O.
6. 0. IN Sodium Hydroxide (NaOI:D Solution -!0g NaOH to I Liter Dl-H2O. ·
(Discard after 6 months)
7. Hydrogen Peroxide (30%), H2O2 -Fisher Cat. #MK-V340-500.
8. Mercuric Nitrate Titrant (0.14 IN) -Fisher Cat. #LC 16660-4, Standardize
before each use. See section VII ~ A
9. Mercuric Nitrate Titrant (0.025N) -Fisher Cat. #LC!6657-2; Standardize
before each use. See section VII -A
10. Mercuric Nitrate Titrant (0.014 IN) -Fisher Cat. #LC16650-4, Standardize
before each use. See section VII -A.
11. Diphenylcarbazone Brornophenol Blue Mixed Indicator Solution -
Lab Chern Inc. Cat. #LC13680-l
PROCEDURE
A. Standardization of Mercuric Nitrate Titrant
1. Add SmLs of0.0141N Standard Sodium Chloride Solution to 95mLs of
DI-H2O in a 250mL Erlenmeyer flask
2. · Titrate following steps B, 1-7, omitting step B6.
3. Record mLs of titrant used calculate the normality of the titrant as follows:
mLs of Standard N~CI (5) x Normality of NaCl {0.0141) = Normality ofHg(NO3)2
mLs ofHg(NO3)2 titrant used
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Chloride
EPA325.3
NCI-I-003
B.
C.
File Name:
Date:
Page:
Titration
NCII003
Feb. 28, I 997
5 of6
I. Fill a buret with 0.0141N mercuric nitrate solution and zero the buret.
2. Measure I 00mLs of sample in a graduated cylander and transfer to a
250mL erlenmeyer flask.
a. Method Blank -Use !00mLs ofDI-H2O.
b. Matrix Spike -Dilute lmL of Matrix Spike solution to I00mLs of
sample. Final concentration = 5 mg/L
c. Laboratory Control Sample -Dilute 2 mLs of LCS solution to
100 mLs ofDI-H2O .. Final concentration= 20 mg/L
d. Dilutions -Measure an aliquot of sample and dilute to IO0mLs
with DI-H2O.
3. Add a magnetic stir bar and place on a magnetic stirrer place under the
buret. Tum on the stir plate to a moderate speed.
4. Using a transfer pi pet add 5 to IO drops of mixed indicator solution to the
sample.
a. If a blue violet or red color appears on the addition of the mixed
indicator, add 0. IN nitric acid one drop at a time until the color
changes to yellow.
b. If a yellow or orange color forms immediately on the addition of the
mixed indicator, add 0. IN sodium hydroxide solution one drop at a
time until the color changes to blue-violet: then add 0.1 N nitric
acid solution one drop at a time until the color changes to yellow.
5. Add l.0mL excess 0. IN nitric acid.
6. To eliminate the interference of sulfite ions, add l.0mL of hydrogen
peroxide (3 0%) solution to the sample and mix for I minute.
7. Titrate with the appropriate mercuric nitrate titrant (usually 0.0141N).
Record in the logbook the mis in the buret before you start the titration.
Add titrant to the sample until you get a dark purple color. Continue
adding titrant one drop at a time until the color does not change. Record
the mis in the buret at the endpoint. Record the total mLs used to titrate
the sample and the adjusted mis (blank corrected).
Calculation:
where:
mg chloride/ L = (A-B) N x 35450
mLs of sample
A= ml of titrant used for sample
B = ml of titrant used for blank
N = normality of the mercuric nitrate titrant used
Chloride
EPA325.3
NCl-1-003
File Name:
Date:
Page:
NC11003
Feb. 28, 1997
6of6
VIlI. QUALITY CONTROL
A.
B.
C.
D.
E.
F.
Method Blank: To be run with each batch,
Duplicate: A duplicate sample must be analyzed with each batch of samples. In
addition, NC requires a duplicate every IO samples. The relative percent
difference(RPD) must be ~20%. Special consideration must be made for
concentrations less than ten times the reporting limit.
RPO = Difference x I 00
Mean
= {Cone. 1 -Cone. 2) x 100
(Cone. 1 + Cone. 2) / 2
Spike: A matrix spike must be analyzed with each batch of samples. The
percent recovery must be within+/-15%.
% Recovery = {Spiked Sample Value -Sample Value) x 100
True Value
Laboratory Control Sample(LCS): To be analyzed with each batch of samples.
The percent recovery of the LCS must be within 10% of the expected value.
% Recovery = Reported Value x 100
True Value
Sample Preservation: None required.
Holding Time: 28 days
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Pace Analytical
Pace Analytical Services. Inc.
9800 Kincey Avenue. Suite 100
Huntersville. NC 28078
Tel: [phone]
Fax: [phone]
STANDARD OPERATING PROCEDURE
Sulfate -S04
Reference Method: EPA 375.4
SOP NUMBER: NCI-1-025
AUTHOR: Barney Kesler
EFFECTIVE DATE: April I 5, 1997
Bench SOP SUPERSEDES:
APPROVAL
-cc,~ c.b. kl ~~
Operations Manager
Quality Assurance-Officer
C0NTROLILED COPY
COPY N0 .. __,;;;;3;;:____
Date
°'~dfC !~fr ~7
Oat
Sulfate -S04
EPA375.4
NCI-I-025
File Name:
Date:
Page:
NCII025
Apr. I 5, 1997
2 ofS
I.
Il.
PURPOSE
The purpose of this Standard Operating Procedure (SOP) is to measure the concentration
of sulfate in groundwater, drinking water, surface waters, domestic and industrial wastes.
SCOPE/APPLICATION
A.
B.
C.
D.
Summary: Sulfate ion is converted to a barium sulfate suspension under
controlled conditions. The resulting turbidity is by a nephelometer (Turbidimeter),
filter photometer cir spectrophotometer and compared to a curve prepared from
standard sulfate solutions.
Concentration Ranges: This method is suitable for all concentration ranges of
sulfate (SO4·2); however, in order to obtain reliable readings, use a sample aliquot
containing not more than 40 mg SOJL. The minimum detectable limit is
approximately I mg/L sulfate.
Interferences:
I. Suspended matter and color interfere. Correct by running blanks from
which the barium chloride has been omitted.
2. Silica in concentrations over 500mg/L will interfere.
Hazards and Precautions
Each reagent and chemical used in this method should be treated as a potential
health hazard. Reduce exposure by the use of gloves, lab coats, safety glasses and
ventilation hoods. Material Safety Data Sheets(MSDSs) are on file in the library
and available to all personnel.
Ill. RESPONSIBILITY
A.
B.
Analysts
I. Analysts are responsible for adherence to the SOP.
2. All laboratory personnel are responsible for notifying the section
supervisor/manager of any required revisions to the SOP.
Operations Manager
I. The operations manager is responsible for ensuring adherence to this SOP.
D
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Sulfate -S04
EPA375.4
NCI-I-025
File Name:
Date:
Page:
NCII025
Apr. I 5, 1997
3 of5
IV.
V.
C.
D.
2. The operations manager is responsible for performing an annual review of
the SOP.
Quality Assurance Officer (QAO)
I.
2.
3.
The QAO is responsible for conducting laboratory audits to monitor
adherence to this SOP. Results of the audit are reported to Laboratory
Management and Corporate Quality.
The QAO is responsible for coordinating annual reviews of this SOP with
the general manager and the operations manager. More freque:nt reviews
may be required.
The QAO is responsible for ensuring that all revisions to the SOP are
implemented.
4. The QAO is responsible for determining distribution of and maintaining
document control of this SOP.
General Manager (GM)
I.
2.
The GM is responsible for the overall implementation of and adherence to
this SOP.
The GM is responsible for reviewing of this SOP with the QAO and the
operations manager.
REVISIONS/REVIEWS
A. This SOP will be reviewed on an annual basis at a minimum, by the operations
manager, general manager and quality assurance officer.
B. At the time of review, any required revision will be incorporated.
C. The revised SOP will be distributed to all appropriate personnel and the:
superseded version replaced.
DISTRIBUTION
A. Distribution of this SOP will be determined by the QAO.
Sulfate -SO4
EPA375.4
NCI-I-025
File Name:
Date:
Page:
NCII025
Apr. 15, 1997
4 of5
VI. APP ARA TVS AND MATERIALS
VII.
A. . Apparatus/ Equipment
I. Magnetic Stirrer, variable speed, use identical shape and size stir bars.
2. Photometer: one of the following which are given in the order of
preference.
a. Turbidimeter (nephelometer)
b. Spectrophotometer for use at 420nm with light path of 4-5cm.
c. Filter photometer with a violet filter having a miximum near 420
nm and a light path of 4 to 5cm.
3. Stopwatch
4. Beakers
B. Reagents
I. ASTM Type II Water (Deionized Water)
2. Hach Sulfaver Powder (Barium Chloride Mix)
Proprietary reagents, such as Hach Sulfaver or equivalent, are acceptable.
3. Sulfate Calibration Standard @ I 000ppm, Ricca Cat.# 8 I 12° I 6 or
equivalent.
4. Sulfate LCS Standard@ I00ppm (Alternate Source), Lab Chem
Cat. # LC25 500-1 or equivalent.
5. Sulfate Spiking Standard@ I00ppm, Ricca Cat.# 8110-16 or equivalent.
PROCEDURE
A.
B.
_Standardize the trurbidity meter according to manufacturers specifications.
Preparation of calibration standards: The calibration curve must be composed of a
minimum of a blank and 3 standards. Standards should be in the range of
0-40 mg/L at 5 mg/L increments. (Note: Above 50mg/L, accuracy decreases and
the suspensions lose stability.) Prepare calibration standards in DI-Water using the
Ricca Sulfate solution at I 000ppm. Transfer 25 mLs of each standard to a beaker
and add a small magnetic stirring bar.
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Sulfate -S04
EPA 375.4
NCl-I-025
File Name:
Date:
Page:
NCII025
Apr. 15, 1997
5 of5
Calibration Volume of Cone. of Final Final
Standard so. Solution SO. Solution Volume (mL) Cone. (ppm)
C.
D.
E.
F.
G.
H.
I.
J.
K.
1
2
3
4
5
6
7
8
(mL) (oom)
0.25 1000 so 5
0.50 1000 so 10
0.75 1000 50 15
1.0 1000 so 20
1.25 1000 so 25
I.SO 1000 so 30
I. 75 1000 50 35
2.0 1000 so 40
Open pack of Hach Sulfaver Powder and add to each beaker. Begin timing for 1.0
min. while stirring at a constant speed.
Transfer standards to a turbidity cell if using Turbidimeter or large absorbance cell
if using spectrophotometer. Calibrate the instrument according to manufacturers
specifications.
Preparation of Samples: Place 25 mLs of sample into beaker and add a. small
magnetic stir bar. Prepare QC samples as follows and add a stir bar.:
-Method Blank -25 mL DI-Water
-LCS -25 mL DI-Water+ 0.S0mL SO4 LCS Standard@ l00ppm
(Final Cone.= 2 mg/L)
-Matrix Spike -25 mL Sample+ lmL SO4 Spiking Standard@ I00ppm
(Final Cone.= 4 mg/L)
Open pack of Hach Sulfaver Powder and add to each beaker. Begin timing for I. 0
min. while stirring at a constant speed.
Transfer samples to a turbidity cell if using Turbidimeter or large absorbance cell if
using spectrophotometer.
Measure turbidity at 30 second intervals for 4 minutes.
Record the maximum reading obtained in the 4 minutes. Dilute samples if they are
more concentrated than the highest standard
Correction for sample color and turbidity.
I. Run a sample blank using 6.3 without the addition of barium chloride mix
(Hach powder)
Calculation:
I. Read from linear curve
NTUS or absorbance vs. mg/L x dilution factor.
Sulfate -SO4
EPA 375.4
NCl-I-025
File Name:
Date:
Page:
NC1I025
Apr. 15, 1997
6 ofS
VIII. QUALITY CONTROL
A. Method Blank: To be run daily with each batch of samples.
B. Duplicate: A duplicate sample must be analyzed with each batch of samples. In
addition, NC requires a duplicate every 10 samples. The relative percent
difference(RPD) must be ::,20%. Special consideration must be made for
concentrations less than ten times the reporting limit.
C.
D.
E.
F.
RPO = Difference x I 00
Mean
= (Cone. I -Cone. 2) x I 00
(Cone. I + Cone. 2) / 2
Spike: A matrix spike must be analyzed every 20 samples for wastewater and
every 10 samples for drinking water. The percent recovery must be within+/-
20% for wastewater and +/-I 0% for drinking water.
% Recovery = (Spiked Sample Value -Sample Value) x 100
True Value
Laboratory Control Sample(LCS): To be analyzed with each batch of samples.
The percent recovery of the LCS must be within 10% of the expected value.
% Recovery = Reported Value x 100
True Value
Sample Preservation: Store cool@ 4°C.
Holding Time: 28 days.
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Pace Analytical
Pace Analytical Services. Inc.
9800 Kincey Avenue. Suite 100
Huntersville. NC 28078
Tel: 704•875•9092
. Fax: [phone]
STANDARD OPERATING PROCEDURE
Nitrate -Cadmium Reduction
(Manual and Automated)
Reference Methods: 18th Edition SM 4500-NO3 E. & F. / EPA 353.3 & 353.2
SOP NUMBER:
AlITHOR:
EFFECTIVE DATE:
SUPERSEDES:
NCl-1-016
D.C. Coffey
April I 5, I 997
Draft SOP
APPROVAL
-1'1~\ij /~~
Operations Manager J
· ty Assurance Officer i a, c ______
General Manager
CONTROLLEB, COPY
COPY NO.__,-j-'----
Nitrate -NO3 File Name: NCII0!6
Apr. 15, 1997
2 of7
SM 4500-NO3 E. & F. / 353.3 & 353.2
NCI-I-016
Date:
Page:
I.
II.
ill.
PURPOSE
The purpose of this Standard Operating Procedure (SOP) is to measure the amount of
nitrite and nitrate combined in drinking waters, surface waters, domestic and industrial
wastes.
SCOPE/APPLICATION
A. Summary -A filtered sample is passed through a column containing granulated
copper-cadmium to reduce nitrate (NO3") to nitrite (NO 2"). The combination of
nitrite and reduced nitrate is determined by diazotizing with sulfanilamide and
coupling with N-(1-naphthyl)-ethylenediamine dihydrochloride to form a highly
colored azo dye which is measured colorimetrically. A correction may be made for
any nitrite present in the sample by analyzing the sample without the reduction
step. (See SOP for Nitrite.)
B. Interferences:
I. Suspended matter in the column will restrict sample flow. Samples may be
filtered prior to analysis.
2. Concentrations of iron, copper and other metals above several milligrams
per liter lower reduction efficiency. Add EDT A to samples to eliminate the
interference from metals present in the sample.
3. Oil and grease will coat the cadmium surface. Remove by pre-extraction
with an organic solvent.
4. Sample color that absorbs at ~540 nm interferes. Diluting the sample may
resolve the interference.
C. Hazards and Precautions
Each reagent and chemical used in this procedure should be treated as a potential
health hazard. Reduce exposure by the use of gloves, lab coats, safety glasses and
ventilation hoods. Material Safety Data Sheets(MSDSs) are ori file in the library
and available to all personnel.
RESPONSIBILITY
A. Analysts
I. Analysts are responsible for adherence to the SOP.
D
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Nitrate -N03 .File Name: NC1I016
Apr. 15, 1997
3 of7
SM 4500-NO3 E. & F. / 353.3 & 353.2
NCI-I-016
Date:
Page:
IV.
V.
2. All laboratory personnel are responsible for notifying the section supervisor
or operations manager of any required revisions to the SOP.
B. Operations Manager
C.
D.
I.
2.
The Operations manager is responsible for ensuring adherence to this SOP.
The Operations manager is responsible for performing an annual review of
the SOP.
Quality assurance officer (QAO)
I. The Q AO is responsible for conducting laboratory audits to monitor
adherence to this SOP. Results of the audit are reported to Laboratory
Management and Corporate Quality.
2. The QAO is responsible for coordinating annual reviews of this SOP with
the general manager and the operations manager. More frequent reviews
may be required.
3. The QAO is responsible for ensuring that all revisions to the SOP are
implemented.
4. The QAO is responsible for determining distribution of and maintaining
document control of this SOP.
General Manager (GM)
2.
The GM is responsible for the overall implementation of and adherence to
this SOP.
The GM is responsible for reviewing of this SOP with the QAO and the
department manager.
REVISIONS/REVIEWS
A This SOP will be reviewed on an annual basis at a minimum, by the operations
manager, general manager and quality assurance officer.
B. At the time of review, any required revision will be incorporated.
C. The revised SOP will be distributed to all appropriate personnel and the
superseded version replaced.
DISTRIBUTION
A. Distribution of this SOP will be determined by the QAO.
Nitrate -NO3 File Name: NCII016
Apr. 15, 1997
4 of7
SM 4500-NO3 E. & F. / 353.3 & 353.2
NCI-I-016
Date:
Page:
VI.
VII.
APPARATUS AND MATERIALS
A. Equipment
I. Cadmium Reduction column: Prepurchased
2. Colorimetric Equipment:
a. Manual Method -Spectrophotometer for use at 543nm, providing a
light path of I cm or longer.
b. Aut_omated Method -Quick Chem AE LACHAT Automated
Analyzer for use at 520 nm., with computer, printer, autosampler,
and pump with tubing.
B. Reagents
I. Nitrate-free DI-Water: The absorbance ofa reagent blank prepared with
this water should not exceed 0.01. Use for all solutions and dilutions.
2. Copper-cadmium granules: Wash 25 g Cd granules with 6N HCl and rinse
with water. Swirl Cd with I 00 mL 2% CuSO. solution for 5 min or until
blue color partially fades. Decant and repeat with fresh CuSO. until a
brown precipitate begins to develop. Gently flush with water to remove all
precipitated Cu.
3. Color reagent: To 800 mL of DI-Water add 100 mL 85% phosphoric acid
and IO g sulfanilamide. After dissolving sulfanilamide completely, add g
N-(I -naphthyl) -ethylenediamine dihydrochloride (N.E.D.). Mix to
dissolve and dilute to I liter with DI-Water. Solution is stable for about a
4.
5.
6.
7.
8.
9.
10.
month when stored in amber bottle in refrigerator.
Ammonia chloride (NfuCl} -EDTA solution: Dissolve 13 g NH.Cl and
1.7 g disodium ethlenediamine tetraacetate in 900 mL DI-Water. Adjust to
pH 8.5 with cone. NH.OH and dilute to I liter.
Dilute NH.Cl -EDT A solution: Dilute 300 mL NH.CL-EDT A solution to
500 mL with DI-Water.
Hydrochloric Acid, HCl -6N: Carefully dilute 500 mL cone. HCl to 500
mL with DI-Water.
Copper sulfate solution, 2%: Dissolve 20 g CuSO,.5H20 in 500 mL DI-
Water and dilute to I liter. ·
Stock Nitrate Solutions, JOO & 1000 mg/L.
Calibration solution, 5 mg/L : Dilute 0. 5 mL ( 1000 mg/L) stock to I 00 mL
with DI-Water.
LCS/Spike Solution, 5 mg/L: Dilute 5 mL (100mg/L) stock to 100 mL
with DI-Water.
PROCEDURE
A. Preparation of reduction column:
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Nitrate -NO3 file Name: NC1IOl6
SM 4500-NO3 E. & F. / 353.3 & 353.2
NCl-I-016
Date:
Page:
Apr. 15, I 997 .
5 of7
B.
C.
I.
2.
Manual Method: Insert a glass wool plug into bottom of reducl:ion column
and fill with water. Add sufficient Cu-Cd granules to produce a. column
18.5 cm long for the manual method. Maintain water level above Cu-Cd
granules to prevent entrapment of air. Wash column with 200 mLs dilute
NH4Cl-EDTA solution. Activate column by passing at least 100 mL ofa
solution composed of25% 1.0 mg/L nitrate solution and 75% NH4CJ -
EDT A solution.
Automated Method: Insert a glass wool plug into the bottom of the
LACHAT reduction column and fill with water. Add sufficient Cu Cd
granules to fill the column. Fill the reagent reservoirs on the LACHAT
with appropriate reagent solutions. Set up the LACHAT system to
automatically wash and activate the column.
Preparation of Calibration standards: Prepare a series of calibration standards
by using the calibration solution @ 5 mg/L.
Std. Cone.
0.05 mg/L
0.10 mg/L
0.20 mg/L
0.50 mg/L
1.0 mg/L
Final Volume
25 mL
25 mL
25 mL
25 mL
25 mL
mLs of Cal. Solution
0.25 mL (250 uL)
0.5 mL (500 uL)
1.0 mL (1000 uL)
2.5 mL (2500 uL)
5.0 mL (5000 uL)
Treatment of sample:
I.
2.
3.
Turbidity Removal -Colorimetric methods require an optically clear
sample. Filter turbid samples through 0.45 um pore diameter membrane
filter.
pH Adjustment -Adjust pH of the samples to between 7 and 9, as
necessary, using dilute HCL or NaOH.
Sample Volume:
Method Blank -25 mLs DI-Water
LCS -25 mLs DI-Water+ 0.5 mLs ofLCS/Spike Solution
Spike -25mLs Sample+ 0.5 mLs ofLCS/Spike Solution
Samples -25 mLs Sample
D. Sample Reduction and Color Development:
I. Manual Method -To a 25 mL portion of sample or a portion diluted to 25
mL, add 75 mL NH.Cl -EDTA solution and mix. Pour mixed sample
through column discarding first 25 mL. Collect the rest in original sample
Nitrate -NO3 File Name:
SM 4500-NO3 E. & F. / 353.3 & 353.2
NCI-I-016
Date:
Page:
NCII016
Apr. 15, 1997
6 of7
E.
2.
flask. There is no need to rinse column between samples, but if column is
not to be reused for several hours or longer, pour 50 mL dilute NH4C I -
EDTA solution on top and let pass through the system. Store Cu -Cd
column in this solution and never let it dry. After the sample has passed
through column, add 2 mLs color reagent to 50 mLs of sample and mix.
After IO min measure absorbance
Automated Method -Transfer a portion of standards and samples, as
measured in step 3, to a LACHAT sample cell. The LACHAT system will
automatically perform the sample reduction and color development
procedures.
Measurement: Obtain a standard curve by plotting the absorbance vs.
concentration.
VIII. QUALITY CONTROL
A. Method Blank: Analyze one daily.
B.
C.
D.
E.
Spike: A matrix spike must be analyzed every 20 samples for wastewater and
every IO samples for drinking water. The percent recovery must be within +/-
20% for wastewater and +/-10% for drinking water.
% Recovery = (Spiked Sample Value -Sample Value) x 100
True Value
Laboratory Control Sample(LCS): The percent recovery of the LCS must be
within I 0% of the expected value. Analyze one LCS daily and then every 20
samples.
% Recovery = Reported Value x 100
True Value
Duplicate: Analyze a sample duplicate or matrix spike duplicate every I 0
samples. The relative percent difference(RPD) must be .:::20%. Special
consideration must be made for concentrations less than ten times the reporting
limit.
RPO = Difference x I 00
Mean
= (Cone. I -Cone. 2) x I 00
(Cone. I + Cone. 2) I 2
Sample Preservation: Cool, 4°C, H2SO, to pH<2
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Nitrate -NO3 .File Name:
SM 4500-NO3 E. & F. / 353.3 & 353.2
NCl-1-016
Date:
Page:
NC11016
Apr. l 5, l 997
7 of7
F.
G.
Holding Time: 48 hours if unpreserved, 28 days if preserved with H2S0,.
Column Efficiency: Analyze a 0.1 mg/L NO2-N Standard and a 0.1 mg/L NO3-N
Standard that have passed through the reduction column. Calculate the column
efficiency as indicated below. The column needs repacking if the effici,:ncy falls
below 75%.
Column Efficiency = NOi-N Results x 100
NOi-N Results
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Pace Analytical
Pace Analytical Se1Vices. Im:.
54 Ravensao~ Drive
AsneviUe. NC 28801
STANDARD OPERATING PROCEDURE
Tel: [phone]
Fax: 704-2S2-4618
Alkalinity
Reference Methods: EPA 310.1 I SM 2320 B.
SOP Number
Author
Effective Date
Supersedes
Quality Assurance Officer
General Manager
Approval .
ASV-I-106
Robin K Blankenbaker
April 18, 1997
All previous editions
Date
Date
Alkalinity
I. PURPOSE
04-24-97 09:lSA P,03
ASV-I-106
April 18, 1997
Page 1 of 5
The purpose of this Standard Operating Procedure (SOP) is to measure the
alkalinity of groundwater, drinking water, surface waters, domestic and
industrial wastes.
II. SCOPE/APPLICATION
A. Summary: An unaltered sample is titrated to an electrometrically
determined endpoint of pH 4.5. The sample must not be filtered. diluted.
concentrated, or altered in any way.
8. Concentration Ranges: This method is suitable for all concentration
ranges of alkalinity; however, appropriate aliquots should be used to avoid a
titration volume greater than 50ml.
C. Interferences:
1. Salts of weak organic and inorganic acids. if present in large amounts,
may cause interference in the pH measurement.
2. Oil and grease, by coating the pH electrode, may also interfere,
causing sluggish response.
D. Safety: Safety glasses, lab coats, and gloves should be worn at all
limes. As sample constituents are not known, all samples should be
treated as hazardous. MSDSs are on file and available to all personnel.
Ill. RESPONSIBILITY
A. Analysts
1. Analysts are responsible for adherence to the SOP.
2. All laboratory personnel are responsible for notifying the section
supervisor/ manager of any required revisions to the SOP.
B. Operations Manager
1. The operations manager is responsible for ensuring adherence to this
SOP.
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04-24-97 09:1aA P.04
ASV-I-106
April 18, 1997
I -A=lk=a=l=in=it,;..y====-==~=~-=~~=====P=a=g"-e~2_o_f_:i~~~
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2. The operations manager is responsible for performing an annual review
of the SOP.
C. Quality Assurance Officer (CAO)
1. The QAO is responsible for conducting laboratory audits to mo11itor
adherence to this SOP. Results of the audit are reported to Laboratory
Management and Corporate Quality.
2. The QAO is responsible for coordinating annual reviews of this SOP
with the general manager and the operations manager. More frequent
reviews may be required.
3. The QAO is responsible for determining distribution of and maintaining
document control of this SOP.
4. The QAO is responsible for determining distribution of and maintaining
document control of this SOP.
D. General Manager (GM)
1. The GM is responsible for the overall implementation of and adherence
to this SOP.
2. The GM is responsible for reviewing this SOP with the QAO and the
operations manager.
IV, REVISIONS/REVIEWS
A. This SOP will be reviewed on an annual basis at a minimum, by the
operations manager, general manager and quality assurance officer.
B. At the time of review, any required revision will be incorporated.
C. The revised SOP will be distributed to all appropriate personnel and the
superseded version replaced.
V. DISTRIBUTION
A. Distribution of this SOP will be determined by the QAO.
Alkalinity
VI. Apparatus
ASV-I-106
April 18, 1997
Page 3 of 5
04-24-97 09:t8A P,05
A. A pH meter that can be read lo 0.05 pH units. Standardize and calibrate
according lo manufacturer's instructions. If automatic temperature
compensation is not provided, make titration at 25 ±2C.
B. A vessel of appropriate size to keep the air space above the solution at a
minimum.
C. Magnetic stirrer (Teflon coated), pipettes, flasks and other standard
laboratory equipment.
0. Burets. Pyrex 50, 25, and 10ml
VII. Reagents
A. Sodium carbonate solution, approximately 0.0SN.
B. Sulfuric acid 0.1 N.
C. Standard acid (sulfuric or hydrochloric}, 0.02N.
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Alkalinity
VIII. Procedure
A. Sample Size:
ASV-I-106
April 18, 1997
Page 4 of 5
a. Use a sufficiently large volume of titrant (>20ml in a 50ml buret) to
obtain good precision while keeping volume low enough to permit sharp
end point.
b. For< 1000mg CaC03/L use 0.02N titrant
c. A preliminary titration is helpful.
B. Place 100ml of sample in flask by pouring near bottom of flask.
C. Measure pH of sample
D. Titrate H2SO• into sample until pH is 4.5. Record volume of titrant.
IX. Calculations
Alkalinity, mg/L CaCOJ =Ax N x 50,000
ml of sample
Where: A = ml standard acid
N = normality standard acid
X. QUALITY CONTROL
A. Method Blank: To be run daily with each batch of samples.
B. Duplicate: A duplicate sample must be analyzed with each batch of
samples. In addition, NC requires a duplicate every 10 samples. The
relative percent difference (RPO) must be ~20%. Special consideration must
be made for concentrations less than ten times the reporting limit.
RPO = Difference x 100 = (Cone. 1 -Cone. 2) x 100
Mean (Cone 1 + Cone. 2) / 2
Alkalinity
ASV-I-106
April 18, 1997
Page 5 of 5
04-24-97 09;19A P,07
C. Laboratory Control Sample (LCS): To be analyzed with each batch of
samples. The percent recovery of the LCS must be within 10% of the
expected value.
%Recovery = Reported Value x 100
True Value
D. Sample Preservation: Store cool @ 4C.
E. Holding Time: 14 days.
F. References: EPA 310.1 and SM 2320 B
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