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Home My WebLink About20080915 Ver 1_Quality Assurance Project Plan_20081021JW Duke IEnergys Carolinas October 20, 2008 HYDRO LICENSING AND LAKE SERVICES Duke Energy Carolinas, LLC 526 South Church St. Charlotte, NC 28202 Mailing Address: EC12K / PO Box 1006 Charlotte, NC 28201-1006 -DwQ # pg - o 9 (5 North Carolina Division of Water Quality Attention: John Dorney Wetlands Program Development Unit Parkview Building 2321 Crabtree Blvd. Suite 250 Raleigh, NC 27604 Re: FERC 401 Water Quality Certification Application Quality Assurance Project Plan Catawba-Wateree Hydroelectric Project FERC Project No. 2232 Dear Mr. Dorney: OCT 2 1 2008 DEW - WATER QUAD f Y y?LANDS AND STORMWATER BRpNCN On June 5, 2008, Duke Energy Carolinas, LLC (Duke) filed with both the North Carolina Division of Water Quality (NCDWQ) and the South Carolina Department of Health and Environmental Control (SCDHEC) application packages for Section 401 water quality certifications of the Catawba-Wateree Hydroelectric Project (Project), which is licensed as Federal Energy Regulatory Commission (FERC) Project No. 2232. The subject of these certifications is the continued operation of the Project under a new FERC-issued license that is consistent with applicable sections of the Catawba-Wateree Comprehensive Relicensing Agreement (CRA). On August 19, 2008 SCDHEC requested additional information for the Quality Assurance Project Plan (QAPP). In order that the QAPP remain consistent throughout the Catawba-Wateree Project, Duke now files the attached revised QAPP with SCDHEC and NCDWQ in both CD and hardcopy formats. All other parts of the application and Supplemental Information Package previously filed remain unchanged at this time. If there are questions or if further information is required, please contact Mark Oakley (704-382-5778; emoakley(aD-duke-energy.com) or Tami Styer (704-382-0293; tsstyerP.d uke-energy. com). Sin rely, E. Mark Oakley, P. E. Catawba-Wateree Relicensing Project Manager Hydro Licensing and Lake Services Duke Energy Carolinas, LLC EMO/em Enclosure QP. oapm P 0 C T 2 1 2008 DERR - MfER QUALM WETLANDS AND STORMWATER BRANCH www.duke-energy.com CATAWBA-WATEREE TAILWATER DISSOLVED OXYGEN MONITORING FERC PROJECT NO. 2232 QUALITY ASSURANCE PROJECT PLAN (QAPP) Effective Date: October 20, 2008 Revision #0 Document Control #I of 12 P Duke (Energy. QUALITY ASSURANCE PROJECT PLAN CATAWBA-WATEREE PROJECT, FERC No. 2232 Al - Title and Approval Sheet Catawba-Wateree Hydroelectric Project Location: North Carolina - McDowell, Burke, Caldwell, Alexander, Catawba, Iredell, Mecklenburg, Lincoln, and Gaston Counties South Carolina - York, Chester, Lancaster, Fairfield, and Kershaw Counties Lead Organization: Duke Energy Carolinas, LLC Preparer: Tamara Styer, Duke Energy Carolinas, LLC Contact Information: 526 South Church Street, Mail Code EC12Y Charlotte, NC 28202 704.3 82.0293 Preparation Date: October 20, 2008 Document Approval: George A. Galleher, Compliance Engineer Duke Energy, Hydro Operations and Compliance Signature Date Carol Goolsby, Vice President Hydro Fleet Duke Energy, Fossil-Hydro Generation Signature Date John Dorney, Program Development North Carolina Division of Water Quality Signature Date Rusty Wenerick, Director, Environmental Health Manager South Carolina Department of Health and Environmental Control Signature Date ii Nydia Burdick, State Quality Assurance Management Office South Carolina Department of Health and Environmental Control Signature Date Penny Franklin, Director Scientific Services Duke Energy, Corporate Environment, Health, and Safety (EHS) Signature Date E. Mark Oakley, Project Manager II Duke Energy, Hydro Licensing and Lake Services Signature Date iii Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 A2 - TABLE OF CONTENTS GROUP A - PROJECT MANAGEMENT A3.0 Distribution List ......................................................................... ..........................................1 A4.0 Project Organization .................................................................. ..........................................2 A5.0 Problem Definition/Background ................................................ ..........................................5 A6.0 Project Task Description ............................................................ ..........................................7 A7.0 Data Quality Objectives and Criteria ......................................... ..........................................9 A8.0 Special Training/Certification .................................................... ........................................10 A9.0 Documents and Records ............................................................ ........................................11 GROUP B - DATA GENERATION AND ACQUISITION 131.0 Sampling Process (Study) Design ................................................................................ ......13 B2.0 Sampling Methods ....................................................................................................... ......36 B3.0 Sample Handling and Custody ..................................................................................... ......39 B4.0 Analytical Methods ...................................................................................................... ......39 B5.0 Quality Control ............................................................................................................ ......39 B6.0 Instrument/Equipment Testing, Inspection, and Maintenance (discussed in SOP) ..... ......40 B7.0 Instrument/Equipment Calibration and Frequency ...................................................... ......41 B8.0 Inspection/Acceptance of Supplies and Consumables ................................................. ......43 B9.0 Non-Direct Measurements ........................................................................................... ......43 1310.0 Data Management ........................................................................................................ ......43 GROUP C - ASSESSMENT AND OVERSIGHT C1.0 Assessment and Response Actions ....................................................................................44 C2.0 Reports to Management .....................................................................................................45 GROUP D - DATA VALIDATION AND USABILITY D1.0 Data Review, Verification, and Validation ........................................................................46 iv Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 D2.0 Verification and Validation Methods .................................................................................46 D3.0 Reconciliation with User Requirements ............................................................................48 REFERENCES ..............................................................................................................................49 APPENDICES APPENDIX A-QAPP - Standard Operating Procedures for In Situ Hach MS5 Multiprobe APPENDIX B-QAPP - Example Quality Control Chart Demonstrating Oxygen Sensor Drift APPENDIX C-QAPP - Supplemental Trout Habitat Monitoring v Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 LIST OF TABLES Table 1 Contacts Receiving Duke Energy Catawba-Wateree QAPP ........................................ 1 Table 2 Water Quality Monitoring Schedule ............................................................................. 7 Table 3 Record Location, Archival and Disposal .................................................................... 12 Table 4 Summary of Project Assessment Activities ................................................................ 45 LIST OF FIGURES Figure 1 Project Organization Chart (Bold Text refers to Project Titles, Italics Text refers to Duke Position Titles) ................................................................................................. ... 4 Figure 2 Catawba-Wateree Project Location Map ................................................................... ... 6 Figure 3 Flow Chart Summarizing Duke Energy's Tailrace Dissolved Oxygen Monitoring Process (including Decision Points) .......................................................................... ... 8 Figure 4 Schematic Drawing of the Catawba River ................................................................. . 15 Figure 5 Bridgewater Water Quality Monitoring Location ...................................................... . 17 Figure 6 Rhodhiss Water Quality Monitoring Location .......................................................... . 19 Figure 7 Oxford Water Quality Monitoring Location .............................................................. . 20 Figure 8 Lookout Shoals Water Quality Monitoring Location ................................................ . 22 Figure 9 Cowans Ford Water Quality Monitoring Location .................................................... . 23 Figure 10 Mountain Island Water Quality Monitoring Location ............................................... . 25 Figure 11 Wylie Water Quality Monitoring Location ................................................................ . 26 Figure 12 Fishing Creek Water Quality Monitoring Location ................................................... . 28 Figure 13 Great Falls-Dearborn Water Quality Monitoring Location - Diversion Dam ........... . 29 Figure 13 (cont'd) Great Falls-Dearborn Water Quality Monitoring Location - Headworks.... . 30 Figure 13 (cont'd) Great Falls-Dearborn Water Quality Monitoring Location - Main Dam.... . 31 Figure 14 Cedar Creek Water Quality Monitoring Locations .................................................... . 33 Figure 15 Wateree Water Quality Monitoring Locations .......................................................... . 34 Figure 16 System Overview - this configuration will be installed at each hydro facility ......... . 37 Vi Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 GROUP A - PROJECT MANAGEMENT A3.0 Distribution List This Quality Assurance Project Plan (QAPP) will be distributed to the following agencies and entities with an interest or role in water quality monitoring conducted by Duke Energy Carolinas, LLC (Duke or Licensee) for the Catawba-Wateree Hydroelectric Project (FERC No. 2232). Table 1 Contacts Receiving Duke Energy Catawba-Wateree QAPP QAPP ORGANIZATI DOC RECIPIENTS ON ORGANIZATION PHONE EMAIL CONTROL TITLE NO. George Compliance Duke Energy, Hydro 704.382.5236 gagalleherAdukeenerg y com 1 of 12 Galleher Engineer Generation _ Scott Holland Manager, Hydro Duke Energy, Hydro 704.382.9013 sdhollandAdukeenergy com 2 of 12 Operations Generation Brenda Technical Duke Energy, Hydro Systems Operations 704.382.5257 bdmottemAdukeenergy com 3 of 12 Mottern Manager Project Manager Duke Energy, Hydro emoakle dukeenergcom Mark Oakley 11 Licensing and Lake 704.382.5778 4 of 12 Services Penny Franklin Director Duke Energy, 704.875.5209 pcfranklin@dukeenergy.com 5 of 12 Corporate EHS EHS Manager Duke Energy, jsvelteAdukeenergy com John Velte Corporate EHS 704.875.5237 6 of 12 Scientist III Duke Energy, smreidAdukeenergy com Sherry Reid 704.875.5457 7 of 12 Corporate EHS Debbie Nispel EHS Manager Duke Energy, 317.838.1957 Debbie.nispelAdukeenergy com 8 of 12 Corporate EHS Environmental NC Division of John Dorney Program Water Quality 919.733.9646 John.domeyAncmail.net 9 of 12 Supervisor III Director, Water SC Dept of Health Rusty Quality Division and Environmental 803.898.4266 weneriwe@dhea.sc.gov 10 of 12 Wenerick Control QA Management SC Dept of Health Nydia Burdick Office and Environmental 803- 641-7670 burdicdf@dhec.sc.gov 11 of 12 Control Ben West Hydro Licensing US EPA 404-562-9643 west.benjamin@epa.gov 12 of 12 Coordinator Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 A4.0 Project Organization The Duke Energy Carolinas, LLC (Duke) Hydro Operations Compliance Engineer, George Galleher, will serve as the Project Manager (PM) and is responsible for overseeing all aspects of the continuous dissolved oxygen (DO) monitoring program for the Catawba-Wateree Project tailwaters, including oversight of the laboratory collecting the data in accordance with the Water Quality Monitoring Plan (WQMP) for the Project and this QAPP. The Duke PM is responsible for the final review of documentation for the QA/QC file and that data collection is consistent with this QAPP. The Duke PM is also responsible for reporting data to the North Carolina Division of Water Quality (NCDWQ) and the South Carolina Department of Health and Environmental Control (SCDHEC). In addition, the Project Manager is responsible for maintaining the QAPP, distributing the QAPP, and preparation of updates and/or revisions and redistribution as necessary. The Duke PM does not directly supervise any of the areas of responsibility identified below. The Duke Energy Corporate Environmental Health and Safety, (EHS) laboratory organization is certified by the NC Division of Water Quality (Certification Number 5193) and the SC Department of Health and Environmental Control (Certification Number 99046004) for water analysis. John Velte, Manager Scientific Services Chemical/Physical EHS, will be the Field Monitoring Manager responsible for directly overseeing and supervising the Monitoring Field Staff. The Field Monitoring Manager is responsible for the day-to-day coordination of field data collection and equipment maintenance in accordance with this QAPP, the Water Quality Monitoring Plan (WQMP) and all associated Standard Operating Procedures (SOPS). The Field Monitoring Manager is also responsible for reporting any equipment/calibration issues to the Duke PM and for taking corrective action related to equipment/calibration issues encountered by Monitoring Field Staff. At the end of the monitoring season, the Field Monitoring Manager also provides an annual database derived from PI (plant information) data, field data, validation data, backup files, etc to the Project Manager and Corporate EHS Water Management Group. This annual database will form the basis of the annual report. The Field Monitoring Manager is also responsible to take any corrective action resulting from internal or external audits. The Monitoring Field Staff (Duke Energy EHS personnel assigned by the Field Monitoring Manager) are responsible for maintaining functioning instruments, performing calibration procedures as required, collecting and downloading data, and maintenance of field logbooks in accordance with this QAPP, the WQMP and all associated SOPS. Field Staff are responsible for reporting any equipment/calibration issues to the Field Monitoring Manager. Sherry Reid, Scientist (EHS), will be the Quality Assurance (QA) Manager responsible for conducting internal audits and maintaining Quality Assurance/Quality Control (QA/QC) files of the field data collection process. Debra Nispel, of the Corporate EHS Water Management Group, is responsible for producing the annual report from the final database produced by the Field Monitoring Manager and the documentation received from Hydro Operations. The annual report is submitted to both NCDWQ and SCDHEC. 2 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Scott Holland, the Duke Hydro Operations Manager, and his direct reports are responsible for the day-to-day operations of the hydroelectric stations. They take the information provided in real- time by the tailrace monitor and/or data supplied by the PI database and take appropriate action (turbine aeration) to maintain compliance to state water quality standards. The hydro operations staff is responsible for observing the tailrace monitor for proper functioning or suspicious data and informing the Field Monitoring Manager and/or the Data Processor Manager for possible troubleshooting of the monitoring system. The Technical Services Manager, Brenda Mottern, will serve as the Data Processor / QA Manager. She and her direct reports are responsible for the data that are received from the tailrace monitor and into the SCADA wave radio, and finally processed into the PI database. The Data Processing function maintains the PI database, performs needed calculations from PI made available to the operators, and provides for an annual database and electronic spreadsheets used for the annual report. The Data Processor is responsible for software support and maintaining the interface between the instruments and the receiving station, for reviewing selected portions of the individual data files. 3 Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 Figure I Project Organization Chart (Bold Text refers to Project Titles, Italics Text refers to Duke Position Titles) Duke Project Manager Hydro Operations Compliance Engineer George Galleher EHS QA Officer Scientist Sherry Reid Duke Field Monitoring Manager EHS Manager John Velte Duke Field Monitoring Staff John Velte's Direct Reports Duke Hydro Operations Manager Manager Hydro Operations Scott Holland Duke Hydro Operations Staff Scott Holland's Direct Reports Data Processing / QA Manager Technical Systems Manager Brenda Mottern Duke Project Report Preparation Manager EHSManager Debra Nisbel 4 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 A5.0 Problem Definition/Background A5.1 Background Duke Energy Carolinas, LLC (Duke) has applied for a new operating license from the Federal Energy Regulatory Commission (FERC) for the Catawba-Wateree Hydro Project (all eleven impoundments and thirteen powerhouses are included in the Catawba-Wateree License, see Figure 2). Along with development of its license application, Duke and stakeholders have developed a Comprehensive Relicensing Agreement (CRA) along with stakeholders to address many Project-related issues and stakeholder interests. One of the proposed license articles in the Application for New License stipulates a Flow and Water Quality Implementation Plan (FWQIP) to enhance the aquatic resources by improving flow conditions for fish and wildlife and by meeting state dissolved oxygen standards. Even though Duke has previously modified many of the turbines to increase the capacity to aerate the downstream releases, additional plant modifications are necessary to enhance the aeration capacity and/or meet the minimum flow requirements stipulated in the CRA. The FWQIP describes the additional physical modifications, the schedule for completion of the modifications, and any interim measures prior to the physical installation of the equipment (Table 4 of the 401 Water Quality Certification Application). An additional proposed article for the new license is the Water Quality Monitoring Plan (WQMP). This proposed article describes a monitoring program at each hydroelectric station. The WQMP discusses two major activities for water quality monitoring. The first activity is the measurement and reporting of dissolved oxygen concentrations (DO) for the duration of the license (this activity is the focus of this QAPP). The second activity is the measurement of temperature and flow downstream of the Bridgewater project to verify the computer modeling used to establish the flow release patterns into the bypassed reach and the downstream river channel (discussed in Appendix C-QAPP). In accordance with the CRA, this supplemental monitoring is not used for compliance purposes, but rather to determine if now reductions are needed in the Catawba River Bypassed Reach (CRA, Appendix F, Section 3.0). The purpose of this QAPP is to provide a quality assurance/quality control program for the proposed DO monitoring. This QAPP documents the data collection procedures, the equipment, and data management activities to ensure that valid data are used by Duke, NCDWQ, and SCDHEC to evaluate compliance to state dissolved oxygen (DO) standards. This QAPP was developed in accordance with the USEPA guidance document "Guidance for Quality Assurance Project Plans, EPA QA/G-5" dated December 2002 and the "SCDHEC Guidance Document for Preparing Quality Assurance Project Plans (QAPP) for Environmental Monitoring Projects/Studies" Revision 1, dated October 2007. 5 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Figure 2 Catawba-Wateree Project Location Map I t x LENOIR LAKE HICKORY LOOKOUT SHOALS LAKE LAKE JAMES MORGANTON HICKORY' LAKE RHODHISS LAKE NORMAN ?.' MOORESVILLE LINCOLNTON 11 MTN. ISLAND LAKE NORTH CAROLINA GASTONIA SOUTH CAROLINA CHARLOTTE LAKE WY LIE FORT MILL ROCK HILL NORTH CAROLINA SOUTH CAROLINA LANCASTER CHESTER FISHING CREEK LAKE GREAT FALLS LAKE ( Ii(OCKY CREEK LAKE LAKE WATEREE 6 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 A5.2 Problem Statement The goal of the Catawba-Wateree QAPP/WQMP is to provide accurate, real-time dissolved oxygen (DO) and temperature data for the project releases. This real-time data will be used by operators to adjust hydro operations to maintain compliance with state DO standards and the requirements of the FERC license (see Section B 1 for geographical references). In addition, this data will be used for reporting compliance, and/or non-compliance events to appropriate agencies, as well as conducting on-going evaluations regarding equipment performance and operational guidelines. A6.0 Project Task Description A6.1 Schedule Duke's Field Monitoring Staff will collect DO and water temperature data in accordance with the WQMP. Table 2 summarizes the tasks anticipated to occur under the WQMP and this QAPP. The QAPP will become effective upon (1) obtaining all approval signatures in Section Al, (2) issuance of the final 401 Water Quality Certification by NCDWQ and SCDBEC, and (3) issuance of a New License for the Catawba-Wateree Project by the FERC and the closure of all appeals and legal challenges. The following is a general schedule for the monitoring activities discussed here: Table 2 Water Quality Monitoring Schedule Task Timeframe Notes Water Quality 12 months after FERC approves At several locations, the installation of water quality Monitor the FWQIP (subject to approval monitors will precede the installation of the equipment installation in NC and SC 401 Water modifications necessary to achieve compliance. In Quality Certification) per CRA, these cases, the monitors will assist Duke in the Appendix M implementation of interim measures per the FWQIP. However, these monitor results are not suitable for compliance assessments until the necessary equipment modifications have been implemented (refer to CRA Section 13.2) DO April I - November 30 Each year for the term of the license, per Monitoring WQMP/FWQIP Temperature April I- November 30 Each year for the term of the license, per Monitoring WQMP/FWQIP Annual Report March 30 The annual report will reflect previous year's data; Submitted annual reports submitted for the term of the license A6.2 Summary of Project Tasks and Decision Points A summary and flow chart of the various tasks as they relate to decisions and reporting for the project are presented in Table 3. 7 Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 Figure 3 Flow Chart Summarizing Duke Energy's Tailrace Dissolved Oxygen Monitoring Process (including Decision Points) (Dashed lines indicate EHS responsibility, light solid lines indicate hydro generation responsibility, heavy solid lines represent information included in annual report) ---------------------------------------------------------------------------------------------------- Starting Point ' i Dedicated Tailrace Monitor ' Database for 15-minute data Station PI Field Records Computer Database i Combine QC Data Plot of -------- W ? Field Records and PI Accuracy Check Real Time Calculate Database Calculations Display to Daily Ave DO - - - - - - 10 to Check Operators Hourly Ave DO Provide Final Database ' i Accuracy for Annual Report of Monitor Field Records of with Field Data Verification, Validation Validation, and Instrument Actions Real Time Ave ' Daily DO >5 l Yes i Hour y DO > 4 - - - - - within Yes Specs Annual ' N Turbine Aeration No o Report i Documentation of Replace Monitor Non-compliance Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 A7.0 Data Quality Objectives and Criteria The objective of water quality monitoring in the hydro tailraces is to provide accurate, real-time, continuous temperature and dissolved oxygen information to hydro operators to ensure compliance with applicable state water quality standards and FERC license requirements and to provide historical information to operators for continuous improvement of procedures and operations. Sensors to monitor temperature and dissolved oxygen will be deployed in the tailrace of each hydro station (see Section B I.0 for specific locations). Continuous monitoring data will be collected every 15 minutes and provided real-time to the hydro station operators. The hydro operators will aerate the turbine releases to comply with state standards as needed. Calibrated and well-maintained water quality sensors are the key to provide accurate readings within the precision and bias criteria (see Section B5). Temperature probes rarely loose their calibration and are not usually subject to fouling. The temperature sensors are routinely checked when the instrument is calibrated. However, the DO probes are prone to fouling (biological and chemical), which typically results in readings of lower DO concentrations than actually exist. The rate of oxygen sensor fouling (hence inaccuracy) is usually seasonally variable and dependent upon water quality. The measurement trends and tracking of the deviations from accuracy of the deployed tailrace monitor will drive the frequency of monitor replacement. The method of validating probe accuracy will rely on a second calibrated sensor to compare readings to the deployed tailrace monitor on site. The precision between the instruments will be compared to a standard range of acceptable error (see section B5.1 for precision and bias measurements), and, if the difference between the two instruments is greater than the acceptable error, the deployed tailrace monitor will be replaced with a freshly calibrated monitor. The specific location of each sensor (see section B 1) is based upon previous work (Duke Energy, 2006) to document hydro operations on downstream water levels and dissolved oxygen concentrations. The results of these studies illustrated the comparability of various sites and the need to measure water released from the hydro, rather than downstream changes. Based upon these previous investigations, the specific locations of continuous monitoring were based upon the following considerations: ¦ representative of water quality conditions during all Project operations and flows; ¦ security (minimize probability of equipment vandalism and theft); ¦ accessible for maintenance and trouble shooting within a range of flows i; ¦ within a distance downstream to achieve the smallest possible time-lag between changes in Project operations and monitor response, and; ¦ line-of-sight for radio transmission ¦ safety of Field Monitoring Staff The requirement for accurate, real-time dissolved oxygen concentrations in order for the operators to maintain state water quality standards will require immediate maintenance if the ' Accessibility to the monitor at all generation flows and some spill flows, extreme flooding (spill) may result in unsafe conditions to service the monitor. 9 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 system does not provide the data or the data appear to be erroneous. Employee call-out to troubleshoot the sensor will be made if the operators observe the following: ¦ a sudden drop or spike in the dissolved oxygen concentration which does not change with or after turbine aeration ¦ the dissolved oxygen concentrations are not those expected after aeration ¦ no change of concentration observed by the operators ¦ suspicion of monitor errors based upon operators experience ¦ loss of data Duke Energy will respond to a call-out within 24 hours. The Field Monitoring Manager will be notified and Field Staff dispatched. The trouble shooting protocol will follow these steps: • Power supplies and cable connections checked and verified, • Monitor communication and calibration, • Check SCADA radio communications to station computer, station computer transmitting to PI database Faulty probes will routinely be replaced within 24 hours or within the next business day. Loss of equipment related to radio communications will be replaced as soon as possible and all actions from the call-out will be documented and communicated to the Field Monitoring Manager. Monitoring data will be stored on the station computer until the radio signal is restored. A8.0 Special Training/Certification All activities required by the Laboratory Certification issued by the NC Division of Water Quality (Certification Number 5193) and the SC Department of Health and Environmental Control (Certification Number 99046004) shall be performed. The laboratory certification shall be maintained as required by both agencies. All personnel responsible for field monitoring must be familiar with this QAPP and will be qualified to perform the Standard Operating Procedure (SOP # 3210.3, Appendix A). The Field Monitoring Manager is responsible to verify appropriate state lab certification requirements necessary for the implementation of the tailrace monitoring project. In addition, the Field Monitoring Manager will review requirements, and, if necessary, train the Monitoring Field Staff prior to each monitoring season. The training will consist of: ¦ Current field procedures and SOPS, ¦ Changes, if any, from previous years, and ¦ Continuous improvement items identified from past data analysis. The Field Monitoring Manager will observe the field techniques of the Field Staff at periodic intervals throughout the monitoring season. Any issues with technique will be corrected at that time and documented in the appropriate field logbook. All personnel responsible for field monitoring must complete safety training as required by regulating agencies and Duke. Completion of this training will be required on an annual basis and will be documented. All training records will be maintained by the EHS QA Manager. 10 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 A9.0 Documents and Records All personnel with a role in implementing the WQMP will receive the most recently approved QAPP and associated documents. These documents will be updated as necessary by the Duke PM and distributed to all parties listed in Section A3. Any revisions to the QAPP will be noted on the title page with the revision number and effective date. Only the Duke PM and QA Manager will have access to making revisions to the electronic copy of the QAPP, Duke's PM is also responsible for obtaining appropriate revision approvals by NCDWQ and SCDHEC and retention of all revisions to the QAPP. Revisions to the QAPP may include but are not limited to the following: ¦ Procedural changes due to continuous improvement activities identified throughout the course of monitoring, ¦ Procedural changes due to technological or safety-related changes and/or improvements, ¦ FERC License revisions or requirements, and ¦ Water quality agency revisions or requirements. As specified in the SOP, during the monitoring season, the Monitoring Field Staff will: ¦ Maintain records of calibration, ¦ Maintain records of maintenance, ¦ Maintain records of instrument failure, ¦ Maintain records of corrective action, and ¦ Maintain any other field notes/information in field logbooks. The field staff will transfer these records electronically to the Field Monitoring Manager on a regular basis as specified by the Field Manager. The Field Monitoring Manager will archive all field records and any non-PI system temperature and DO monitoring data throughout the monitoring season. These records, in conjunction with PI-system records, will be reviewed by the Field Manager and transferred to a dedicated database for temperature and DO records. This database will be periodically reviewed by the Project Manager and EHS QA officer throughout the monitoring season, including the status of data flags to be posted based on field records. All original raw data records (paper and electronic) collected by the field staff during the monitoring season will be transferred to the Duke PM at the end of the monitoring season. The Duke PM will maintain copies of these records in the QA/QC files for this monitoring project for the term of the Catawba-Wateree Project FERC License. The Field Monitoring Manager will maintain scans of all forms and all data files in electronic format for five years. Access to these files is controlled by the Field Monitoring Manager. Details of electronic data management are further described in Section B 10 of this QAPP. All communications regarding non-compliance and annual compliance reports submitted to NCDWQ and SCDHEC will be maintained in hard copy and electronic format by the Duke Project Manager for the term of the new License. 11 Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 Table 3 Record Location, Archival and Disposal Item Produced Hardcopy Storage Archived Disposal By or Location Time Electronic DO and PI Data Electronic On PI database 1 year Life of new Temperature Processor server (OSI license Data software) Calibration EHS Field Hardcopy EHS files and 1 year 5 years Records Staff and QA Manager Electronic files Maintenance EHS Field Hardcopy EHS files and 1 year 5 years Records Staff and QA Manager Electronic files Corrective EHS Field Hardcopy EHS files and 1 year 5 years Action Staff and QA Manager Electronic files Annual EHS Water Hardcopy EHS files, QA 1 year Life of new Reports Management and Manager files license Group Electronic PM Files An annual report will be submitted to both North and South Carolina agencies according to Table 2 and consist of the following formats: North Carolina Annual Catawba-Wateree Tailrace Monitoring Report Purpose and Scope Temperature Monitoring Dissolved Oxygen Monitoring Instantaneous Dissolved Oxygen Concentrations in the Tailrace Bridgewater Rhodhiss Oxford Lookout Shoals Cowans Ford Mountain Island Daily Average Dissolved Oxygen Concentrations in the Tailrace Bridgewater Rhodhiss Oxford Lookout Shoals Cowans Ford Mountain Island Monitor Maintenance and Calibration Records Summary of Assessment and Response Actions 12 Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 Conclusions Summary of Compliance Proposed / Implemented Corrective Action Recommendations for Continuous Improvement Recommended Changes to the QAPP (if needed) References South Carolina Annual Catawba-Wateree Tailrace Monitoring Report Purpose and Scope Temperature Monitoring Dissolved Oxygen Monitoring Instantaneous Dissolved Oxygen Concentrations in the Tailrace Wylie Fishing Creek Dearborn / Great Falls Cedar Creek / Rocky Creek W ateree Daily Average Dissolved Oxygen Concentrations in the Tailrace Wylie Fishing Creek Dearborn / Great Falls Cedar Creek / Rocky Creek W ateree Monitor Maintenance and Calibration Records Summary of Assessment and Response Actions Conclusions Summary of Compliance Proposed / Implemented Corrective Action Recommendations for Continuous Improvement Recommended Changes to the QAPP (if needed) References GROUP B - DATA GENERATION AND ACQUISITION B1.0 Sampling Process (Study) Design The purpose of monitoring temperature and dissolved oxygen in the water released from the hydro is to ensure that the DO concentration in that water meets or exceeds applicable state WQ standards. The study design was based upon the work by Wagner et al. (2000) and modified to meet specific monitoring objectives described in the License Application (Duke Energy, 2006). The tailrace data will be collected between April 1 and November 30 each year, with an annual report available March 30 of the following year. This monitoring period was selected based upon the 10-year monitoring history presented in the License Application. At no time were dissolved oxygen concentrations less than 5 mg/l during the period December through March (Duke Energy, 2006). Historic temperatures were always less than state water quality standards. 13 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 The primary purpose of this program is to meet temperature and dissolved oxygen water quality standards in the tailrace of the Catawba-Wateree Hydros and to document and report compliance to state water quality standards. The only tailrace data that is of concern is whether temperatures are lower than state standards and whether dissolved oxygen concentrations are higher than state standards. Cause-and-effect relationships of data variability are not pertinent to this program. In summary, permanent tailrace monitors (temperature and dissolved oxygen Hach MS5 Multiprobes) will be placed in the tailraces of the Catawba Hydros. The data is recorded every 15-minutes, hourly averages are calculated from the 15-minute data (4 points per hour) and compared to the instantaneous DO standard of 4 mg/1. Midnight to midnight hourly averages (24 hours per day) are used to obtain daily average DO and compared to 5 mg/ daily average standard. The first criterion for the placement of the water quality monitors reflects the criterion of the Catawba-Wateree Comprehensive Relicensing Agreement. A schematic of the Catawba River (Figure 4) illustrates the various developments, water release points, and the flows requiring monitoring. 14 Duke Energy Carolinas, LLC Quality Assurance Project Plan Figu Catawba River / Linville River Catawba Arm of L k Lake James Linville Arm of L k a e a e Catawba Paddy Ck Paddy Ck Bridgewater Linville Dam' Dam Spillway' Powerhouse Dam Paddy Creek Linville River ------------- ------------ Catawba River Bypassed Reach Muddy 7 Creek River catawba Lake Rhodhiss Rhodhiss Rhodhiss Dam' Powerhouse Notes: 1. Overflow spillway 2. Gated spillway LEGEND Powerhouse release Recreation release Continuous release Regulated reach or River tributary inflow - - - Bypassed reach Lake Resrevoir Dam Structure Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 Lake Hickory Oxford Oxford Powerhouse Dame Catawba River Lookout Shoals Lake Lookout Lookout Shoals Dam' Shoals PH Lake Norman Cowans Cowans Ford PH Ford Dame Mountain Island Lake Mountain Mountain Island PH Island Dam' (Continued on Figure 2) I-C IF ou11C111atic Ifluawlllg U1 LIIC %,atawua INivel 15 Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 (Continued ) South Fork Catawba Mountain Island Lake River Mountain Mountain \ Island PH Island Dam' Lake Wylie Notes: 1. Overflow spillway Wylie Wylie 2. Gated spillway Dal mz Powerhouse 3. With flash boards Fishing Creek Catawba River Fishing Creek Lake Fishing Fishing Creek PH Creek Dame Great Falls Reservoir Rocky Creek Cedar Creek Reservoir Rocky Creek PH Rocky Crk Dam' Z Cedar Creek PH Lake Wateree Wateree Powerhouse Wateree Dam' Wateree River Great Falls Great Falls Dearborn Great Falls Great Falls Powerhouse Dam Powerhouse Headwork' 3 Diversion' 3 + Short Bypass .' Long ' i Bypass V 16 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 The second criterion for the specific placement of the water quality monitors represents the best location to satisfy all of the stipulations presented in Section A7, describing Data Quality Objectives and Criteria. Of utmost consideration is the specific placement of the monitor to be able to capture the variability of the dissolved oxygen released from the hydro. The instruments are designed to accurately measure the expected temperature and DO concentrations and will adequately characterize the water quality of the turbine flows to enable the operators to adjust turbine aeration to meet state water quality standards. The following figures show the proposed locations and discuss the rationale of the monitoring equipment location at each of the Catawba-Wateree Developments. (Note: one of the criterion is that the monitor shall be accessible at all generation flows and some spill flows, extreme flooding (spill) may result in unsafe conditions to service the monitor). Figure 5 Bridgewater Water Monitoring Location 17 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Approximate Map Data Recommended Distance Comments Data Collection Location Location Downstream (miles) Bypassed Reach Wireless Telemetry I Minimum Catawba Dam 0 00 Flow sensor at to Station Computer Continuous . flow release valve and Staff Gage for Flows Visual Minimum Continuous Downstream of Flows I't Bridge at USGS Gage USGS Gage and 2 Recreational Powerhouse 0.65 (New Gage) Turbine Generation Flows Road Records Project Hourly Flows I't Bridge at Powerhouse In Situ - Pipe and Temperature Road Instruments on Wireless Telemetry 3 Dissolved Linville River 0.25 Bridge to Station Computer Oxygen Downstream of (NCDOT Bridgewater approval required) Hydro Reservoir Bridgewater e rent Device on Wired to Station 4 Levels Forebay n/a th Intake Computer Struc ture Device Location Rationale The valve at the Catawba Dam will be designed to supply seasonal minimum continuous flows in the Catawba River Bypassed Reach (Location 1). A sensor in the flow pipe or valve, calibrated for flow, will provide a continuous reading of the flow being released into the Catawba River Bypassed Reach. Since the sensor is located directly on the valve or flow pipe, which is on the dam, the sensor should be secure from vandals. The channel configuration at the proposed site for the new USGS gage is ideally suited for the expected range of flows originating from the Linville Dam. The site is located on private property providing a measure of security. The previous water quality monitoring site was located on the downstream side of the powerhouse. Even though that site adequately represented the turbine now water quality, the future configuration of the Bridgewater Powerhouse is not known, and, therefore, the recommendation for the future water quality monitoring location is at the first downstream bridge (on Powerhouse Road). The bridge provides an existing structure to place the water quality monitor in the center of the narrow river channel. The temporary monitors placed at this site during the Bridgewater downstream investigations (Knight 2003) illustrated similar water quality values to the tailrace monitor at all flows except the 50 cfs leakage flows that will be replaced by 75, 95 or 145 cfs minimum continuous flows in the future depending on the month. This site will represent the water quality conditions of any combination of hydro unit flow (including minimum flow). In addition, the site would be accessible under all Project flows, and 18 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 would provide a rapid response at the station to water quality conditions. Security from vandals is a concern at this site. F!igure 6 Rhodh_ iss Water Map Location Data Recommended Location Approximate Distance Downstream (miles) Comments Data Collection In Situ - Pipe in Temperature Rhodhiss Road Center of Channel Wireless 1 Dissolved Bridge 0 35 and Instruments Telemetry to Oxygen Downstream of . Mounted on Station Rhodhiss Hydro Bridge (NCDOT Computer approval required) Reservoir Rhodhiss Device on Wired to Station 2 Levels Forebay n/a the Intake Computer Structure Device Location Rationale The previous water quality monitoring site was located on the south corner on the downstream side of the powerhouse. That site adequately represented the water quality of the turbine flow when all the units were identical, however, the turbine venting tests (Duke Energy, 2005a), 19 Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 indicated that this location was not representative of the combined flows from units with differing aeration capability. Therefore, the monitor should be moved to the center of the river channel at the downstream bridge (Location 1). The bridge not only provides an existing structure to place the water quality monitor in the center of the channel, but this site represents the water quality conditions of any combination of hydro unit flows (Duke Energy, 2005a). This site is accessible under all Project flows, and may provide a rapid response at the station to water quality conditions. Security from vandals may be a slight concern at this site. Figure 7 !Oxford Water Quality Monitoring Location y F N ( F ?Jv w ` 41 a? ?? Proposed WQ Monitor ?. Buttress Proposed Flow Valve_ Monitor Reservoir Level; Monitor ''•? ® ` - ;?? X. i-IV 1 K ,? T 0 Proposed USGS type Staff gage Irv T r.'. . e 7. 20 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Map Data Recommended Approximate Comments Data Collection Location Location Distance Downstream (miles) In Situ - Pipe Highway 16 South Channel Wireless Temperature Bridge and Instruments Telemetry to 1 Dissolved Downstream of 0.15 Mounted on Station Oxygen Oxford Hydro Bridge Computer (NCDOT approval required) Minimum Wireless 2 Continuous Oxford Dam 0 00 Flow sensor at Telemetry to Flows . flow release valve Station Computer Recreational Staff Gage for Flows Riverbend Park USGS-Type Plate Visual and 3 Project Hourly 0.30 Gage Turbine Flows Generation Records Reservoir Current Device on Wired to Station 4 Levels Oxford Forebay n/a the Intake Computer Structure Device Location Rationale An aerating flow valve will be designed to supply and measure a constant minimum continuous flow in the downstream channel (Location 2). A sensor in the discharge pipe or valve, calibrated for flow, will provide a continuous reading of the flow being released into the river channel. Since the sensor is located directly on the valve or flow pipe, which is on the dam, the sensor should be secure from vandals. The flow valve will provide the minimum continuous flow during periods of no hydro unit generation. Generation and recreational flow requirements will be recorded from the generation records for each turbine. A manually read, USGS type plate staff gage will be placed at the boat put-in at Riverbend Park (Location 3) for independent verification. The previous water quality-monitoring site was located in the corner of the powerhouse and wingwall. That site adequately represented the water quality of the turbine flow when all the units were identical and prior to the recent installation of the tailrace buttresses. However, this site would probably not be representative of the combined flows from hydro units with differing aeration capability and the buttresses would effectively prevent Unit 2 water from reaching the sensor when Unit 1 was generating. Therefore, the monitor should be moved to the Highway 16 Bridge immediately downstream of the turbines (Location 1). The bridge not only provides an existing structure to place the water quality monitor in the channel, but this site will represent the water quality conditions of any combination of hydro unit flows. This site will be accessible under all Project flows, and will provide a rapid response of the station to water quality conditions. Security from vandals may be a concern at this site. 21 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Approximate Map Data Recommended Distance Comments Data Collection Location Location Downstream (miles) Temperature East Wingwall - In Situ - Pipe, Wired to Station 1 Dissolved Tailrace 0.01 Monitor Location Computer Oxygen Unchanged Minimum Continuous Turbine 2 Flows n/a n/a n/a Generation Project Hourly Records Flows Reservoir Lookout Current Device on Wired to Station 3 Levels Forebay n/a the Computer Structure Device Location Rationale The minimum continuous flow will be provided by either one of the small auxiliary hydro units (Location 2) during periods when the larger hydro units are not operating. The configuration of the Lookout Shoals tailrace (large pool upstream of first downstream hydraulic control) exhibits very little stage change with or without the auxiliary hydro unit generation. In addition, the 22 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 elevation of the tailrace is also a function of Lake Norman's reservoir level (at full pond, the reservoir level extends upstream of the hydraulic control). Therefore, the minimum continuous flow and hourly flow rates would be best monitored by the individual generation records of each hydro unit at Lookout Shoals Hydro. The previous water quality monitoring site was located on the east wingwall downstream of Unit 1. That site adequately represented the water quality of the turbine flow when all the hydro units were identical. The nearest downstream structure to place a monitor in the center of the channel is the I-40 Bridge which is 1.3 miles downstream. The I-40 Bridge site is strongly influenced by Lake Norman's reservoir level, and the long travel time of the minimum flow would influence the water quality at minimum flow. Therefore, the I-40 Bridge location is not preferred for water quality monitoring. Since no other downstream structure exists to place a monitor in the center of the river, the wingwall site (Location 1) represents the best logistical option available for water quality monitoring. This wingwall site will be accessible under all Project flows, and will provide a rapid response of the station to water quality conditions. The monitor will be secure since it is located inside the security fence. Fi ure 9 Cowans Ford Water Location ',T y y r 23 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Map Location Data Recommended Location Approximate Distance Downstream (miles) Comments Data Collection In Situ - Pipe Railroad Bridge West Channel and Wireless Temperature Downstream of Instruments Telemetry to 1 Dissolved Cowans Ford 0.50 Mounted on Station Oxygen Hydro Bridge Computer approval required) 2 Reservoir Cowans Ford n/a Current Device on Wired to Station Levels Forebay Intake Structure Computer Device Location Rationale Even though the previous monitor was placed on the tail-deck of the hydro, this location probably represented the water quality of the released flow. However, under multi-unit operation, the monitor would only record data from the hydro unit flows adjacent to the monitor. In addition, security at the Cowans Ford Hydro facility is controlled by the McGuire Nuclear site (Nuclear Regulatory Commission guidelines) and is difficult to enter when operators are not present. This security issue limits maintenance accessibility. Therefore, the recommended site for the future temperature and dissolved oxygen monitoring is at the railroad bridge 0.5 miles downstream (Location 1). This site would enable the monitor to measure water quality from the high-volume hydro unit flow as well as provide a somewhat secure and accessible site. Location of the monitor just west of the downstream tip of the island would insure that the monitor would be out of the influence of the wastewater discharge from McGuire Nuclear Station. 24 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Map Data Recommended Approximate Comments Data Collection Location Location Distance Downstream (miles) Temperature Tail Deck - In Situ - Pipe, Wired to Station 1 Dissolved Tailrace 0.00 Monitor Location Computer Oxygen Unchanged 2 Reservoir Mt. Island n/a Current Device on Wired to Station Levels Forebay Intake Structure Computer Device Location Rationale Even though the present monitor is on the tail-deck of the hydro (Location 1), this location probably represents the water quality of the released flow. However, under multi-unit operation, the monitor would only record data from the hydro unit flows adjacent to the monitor. Since no other structure, (e.g., bridge), exists in the center of Mountain Island's tailrace, this tail-deck location represents the best logistical location available. It is secure and provides ready access for maintenance. 25 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Map Location Data Recommended Location Approximate Distance Downstream (miles) Comments Data Collection Approx. 1/2 mile Flow-Through Temperature Downstream System Auto Wireless 1 Dissolved from Hydro 0.50 Calibration Sensor Telemetry to Oxygen (pier on Ferrell (Island property ' Station Island) owner s approval Computer required) USGS Gage USGS Gage and Minimum Highway 21 0.00 (Catawba River Turbine 2 Continuous USGS Gage 3.60 near Rock Hill, Generation Flows SC) Records (02146000) 26 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Map Data Recommended Approximate Comments Data Collection Location Location Distance Downstream (miles) Recreational USGS Gage USGS Gage and Flows Highway 21 0.00 (Catawba River Turbine 3 Project Hourly USGS Gage 3.60 near Rock Hill, Generation Flows SC) Records (02146000) Reservoir Current Device on Wired to Station 4 Levels Wylie Forebay n/a the Intake Computer Structure Device Location Rationale The USGS gage at the Highway 21 Bridge (Location 2/3) is well established and will be used for verification of minimum continuous flow, recreational flows, and hourly Project flows. In addition, generation records will be used to supplement the USGS data. The previous water quality-monitoring site was located in the corner of the powerhouse and wingwall. Extensive monitoring of dissolved oxygen concentrations in the Wylie tailrace was conducted during the 2002 turbine-venting test (Duke Energy, 2005a). These results indicated that the proposed monitoring location was the closest point to the hydro that best represented the water quality of the multi-unit flows (Location 1). This test included detailed water quality sampling along several downstream transects, as opposed to just at the monitoring site. Furthermore, the Wylie tailrace is very complicated since the island immediately downstream of the powerhouse splits the water released from the hydro. The flow, from either a single unit or multiple unit operation, moves around the island and finally merges just upstream of the small island across the channel from the proposed monitoring location. Use of this location is contingent on being able to get permission for access from the property owner and on obtaining any necessary easements. Security from vandals is of some concern at this site. 27 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Location ro- ai•• 0 Map Location Data Recommended Location Approximate Distance Downstream (miles) Comments Data Collection In Situ - Pipe Highway 97/200 West Channel Temperature Bridge and Instruments Wireless 1 Dissolved Downstream of 0 15 mounted on Telemetry Oxygen Fishing Creek . Bridge to Station Hydro (SCDOT Computer approval required) Reservoir Fishing Creek Existing Device Wired 2 Levels Forebay N/A on the Intake to Station Structure Computer Device Location Rationale The previous water quality-monitoring site was located on the wingwall, west of the Fishing Creek Powerhouse. That site adequately represented the water quality (temperature and dissolved oxygen) of the turbine flow when all the hydro units were identical and prior to the recent installation of the tailrace buttresses. However, this site would probably not be representative of the combined flows from hydro units with differing aeration capability since 28 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 the flows will be directed downstream due to the newly installed buttresses. Therefore, the monitor will be moved to the Highway 97/200 Bridge immediately downstream of the turbines (Location 1). The bridge not only provides an existing structure to place the water quality monitor in the channel, but this site will represent the water quality conditions of any combination of hydro unit flows. This site is accessible under all Project flows and is in close proximity to the station. Security from vandals may be a concern at this site. Fi ure 13 Location - Diversion Dam Great Falls-Dearborn Water 29 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Figure 13 (cont'd) Great Falls-Dearborn Water Quality Monitoring Location - HeadworksT w CiX'r {? ?? r%Y S?Y?t r?`9 T'd,`. 11 -lip '.J. , 3 0 ?4 R y . t? M r `vim? R? ¦ 30 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Map Location Data Recommended Location Approximate Distance Downstream (miles) Comments Data Collection Pressure Sensor calibrated to Bypassed correspond to Wireless Reaches Diversion Dam minimum Telemetry Minimum Long Bypassed continuous to Station 1 Continuous Reach 0.25 mi. from flow pond Computer Flows Downstream of Fishing Creek Dam level. Pressure and Recreational Fishing Creek Sensor Staff Gage for Flows Hydro calibrated to visual correspond to recreational flows and pond level. Bypassed Headworks Gate Position Wireless Reaches Short Bypassed 1 95 mi from Sensor Telemetry 2 Minimum Reach . . Fishing Creek Dam calibrated to to Station Continuous Downstream of gate opening Computer Flows Fishing Creek corresponding and 31 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Map Data Recommended Approximate Comments Data Collection Location Location Distance Downstream (miles) Recreational Hydro to minimum Staff Gage for Flows continuous visual flow. Pressure Sensor calibrated to correspond to recreational flows and pond level. Temperature Duke Bridge 0.1 mi. from Great In Situ - Pipe, 3 Dissolved Downstream of Falls - Dearborn Monitor Wired to Station Oxygen Hydros Dam Location Computer Unchanged Existing Wired Reservoir Great Falls NSA Device to Station L? Levels Forebay on the Intake Computer _ Structure Device Location Rationale Ideally, measurement of the minimum continuous flows and recreational flows in the Great Falls Long and Short Bypassed Reaches would be taken directly in the respective channels. However, the irregular channel configuration in both reaches prevents accurate flow measurements from stage changes. In addition, the difficult access to the bypassed reaches poses substantial personnel safety limitations to the calibration and maintenance of the gages. Therefore, the best measurement of the flow in the bypassed reaches is at the source of the flows (Locations 1 and 2). Although the exact design of the minimum continuous flow delivery mechanism has not been completed, the measurement of flow will be a stage-discharge relationship between the pond level and the flow being delivered. Continuous flow monitoring for the Long Bypass will be located at the Great Falls Diversion Dam immediately downstream of Fishing Creek Hydro (Location 1). The continuous flow monitoring for the Short Bypassed Reach will be provided at the Great Falls Headworks spillway, both upstream and downstream of the headworks structure (hence a flow measurement system upstream and downstream of the headworks) (Location 2). Recreational flows will be provided as spill over the Great Falls Diversion Dam and the Great Falls Headworks. Again, the water level over the spillways will be measured and stage- discharge equations will relate stage to flow. Manually read, new USGS type plate staff gages will be placed at the Great Falls Diversion Dam and upstream of the Great Falls Headworks. 32 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 The previous water quality monitor mounted on the Duke Energy bridge immediately downstream of Great Falls and Dearborn Hydros is ideally located since it is in the center of the channel (Location 3). This position captures the water quality (temperature and dissolved oxygen) from both hydros and is in a secure location. Cedar Creek Water Quality Monitoring Locations Map Data Recommended Approximate Comments Data Collection Location Location Distance Downstream (miles) 1 Temperature Downstream 0.00 In Situ - Pipe, Wired to Station Dissolved Face of Cedar Monitor Location Computer Oxygen Creek Unchanged Powerhouse 2 Reservoir Cedar Creek n/a Current Device on Wired to Station Levels Forebay the Intake Computer Structure Device Location Rationale The previous water quality monitor is located in the center of the Cedar Creek tailrace. It was mounted directly on the powerhouse. Since the hydro units at Cedar Creek were identical, the 33 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 temperature and dissolved oxygen monitor adequately measured the water quality released from Cedar Creek Powerhouse (Location 1). The water quality of the Cedar Creek hydro flow represents the overall tailrace water quality since: • Cedar Creek Powerhouse flow is significantly greater than Rocky Creek Powerhouse flow and dominates the downstream flow (capacity of Cedar Creek units is three times the capacity of the Rocky Creek units). • Rocky Creek Hydro is operated infrequently; it is operated only after Cedar Creek Reservoir pond level cannot be maintained by Cedar Creek Hydro (three Units at Cedar Creek). • Both hydros draw water from the same forebay and the water quality is similar. Thus, no water quality monitoring device is necessary at the Rocky Creek Hydro. Unlike Great Falls-Dearborn, there is no structure downstream of Cedar Creek Powerhouse to mount a water quality monitor in the center of the channel. Monitoring Locations Q• r NAs Y+ 34 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Map Data Recommended Approximate Comments Data Collection Location Location Distance Downstream (miles) 1 Temperature West Platform - 0.02 Probably Flow- Wired to Station Dissolved Tailrace Through System Computer Oxygen Auto Calibration Sensor 2 Minimum Highway 1/601 7.4 USGS Gage USGS Gage and Continuous USGS Gage (Wateree River Turbine Flows near Camden, SC) Generation (02148000) Records 3 Recreational Highway 1/601 7.4 USGS Gage USGS Gage and Flows USGS Gage (Wateree River Turbine Project Hourly near Camden, SC) Generation Flows (02148000) Records 4 Reservoir Wateree n/a Current Device on Wired to Station Levels Forebay the Intake Computer Structure Device Location Rationale The USGS gage at Highway 1/601(Location 2/3) is well-established and will be used for verification of minimum continuous flow, recreational flows, and hourly Project flows. Generation records will be used to supplement the USGS data. The Wateree tailrace is a relatively simple channel, with the flows from the various hydro units moving directly downstream. However, the tailrace does not lend itself to simple water quality monitoring due to the various aeration capabilities of the individual hydro units and subsequent multi-unit flow patterns (Duke Energy, 2005a). Moving the monitor location downstream to capture a multi-unit flow is not an option because, at flows greater than provided by 2-3 unit operations, a significant volume of water flows out of the main channel to the east within a few hundred yards of the powerhouse. The existing monitor location (Location 1) was built to extend a short distance into the tailrace with the goal of better measurements than at the face of the powerhouse. The existing monitor location is the best logistical location available to measure water quality because no structure exists in the center of the channel, nor is the east side of the channel a viable option because that area is heavily used by fisherman (creating damage and security issues) and is prone to flooding and further potential damage or loss. The next available location at the Highway 1/601 Bridge is not suitable because of its distance from the Powerhouse and the presence of aquatic plants and shoals between the Powerhouse and bridge that significantly influence the DO levels. 35 Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 B2.0 Sampling Methods All dissolved oxygen and temperature data will be measured in situ using a submerged MS5 Hach Multiprobe. The instrument will be calibrated in the laboratory using Standard Operating Procedure (SOP) # 3210.3 (Appendix A, also see Section B7) and placed in a standpipe attached to a permanent structure. The MS5 will be powered by an external power source and the data transmitted to the station computer. The temperature and dissolved oxygen concentration is measured and updated every 15 minutes (continuous data collection at 15-minute intervals). The data are available in real-time for operational decisions regarding aeration as well as stored in a database for future operating and reporting requirements. 36 Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 Figure 16 System Overview - this configuration will be installed at each hydro facility Located in the Tailrace Lightening Rod Dashed Lines Indicate the Field Validation Instrument Used to Periodically Validate the Accuracy and the Need to Replace the Tailrace Monitor 12v Power Supply i i Field I I Data Logger) - I I I i Underwater Cable -i Freshly Calibrated Field Validation Instrument Perforated Standpipe Deployed Tailrace Water Quality Monitor Located in Charlotte (Hydro Central) Pi Database Programs for: • Operational Decisions • Compliance Reporting SCADA Wave Radio Located at the Hydro S Statiofl- Underwater SCADA OperatiWave CompuRadio Cable 37 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Component Description Tailwater Water Quality Monitor (see Sections A4, A5, A6, and A7 for SOP'S) The DO sensor utilizes the most current, practical technology to measure dissolved oxygen. Currently, a luminescence quenching sensor (Hach LDO®) is planned to measure dissolved oxygen. This type of sensor is the latest technology that drastically reduces the frequency of maintenance and calibration of the DO electrode (contrasted to the traditional Clark Cell). The monitor also has a temperature sensor. The monitor has a Modbus communication protocol for direct connection to the SCADA wave radio (no additional programming is necessary). Perforated Standpipe This 6-inch diameter, PVC pipe is attached to a structure (concrete wall, bridge piling, etc.) to provide a permanent housing for the sensor. This pipe, perforated on the lower end, allows for free exchange of water and protects the sensor and cables from physical damage, vandalism, and lightening. Tailwater Sensor Cables (see section 136) Standard, off-the-shelf, cables are supplied by the sensor vendor. These cables allow power to be supplied to the instrument as well as data transmittal to the SCADA wave radio. Each cable end has a specified fitting for the designated mated end. These cables were chosen (in lieu of custom fabrication of wiring components) to allow rapid troubleshooting and replacement (if necessary). Solar Powered Battery, 12 v (see section 136) A solar panel will recharge the battery, which supplies power to SCADA wave radio and sensors. SCADA Wave Radio This is the standard Duke radio link to send and receive data. The SCADA radio transfers data from remote sensors to the station computer. Line of sight clearance is required between radio links. Station Computer The tailrace water quality monitoring data is received by the current operating program at all Catawba Hydros, which receive sensor input (all plant sensors) and displays the readings. The tailrace water quality monitoring data is integrated into plant operations and is part of the display utilized by operators. In addition, the station computer serves as a backup storage for the data. PI (Plant Information) Database (see section B 10) This is the database currently used by Duke for storing all generation data from all facilities. PI has the ability to record and store data at specified intervals. Standard software extracts data from PI to be used in display formats for operators and/or reporting. 38 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Data validation is discussed in sections 135 and D2. The averaging methods of the 15-minute data are discussed in section B I. Duke Energy Environmental Laboratories, located at the McGuire Nuclear site, will provide the support facilities (chemical inventories, equipment parts storage, back-up equipment, etc.). Tailrace Monitor problems, troubleshooting, and corrective action are discussed in section A7. B3.0 Sample Handling and Custody No samples will be collected, transported, or stored since all dissolved oxygen and water temperature measurements will be measured and recorded in situ. B4.0 Analytical Methods No samples will be collected; therefore, laboratory analyses of samples are not needed. However, instrument maintenance and calibration will be performed in the laboratory and discussed in sections 136 and 137, respectively. B5.0 Quality Control In addition to the general quality control protocols regarding calibrations discussed in the Duke SOP # 3210.3 (Appendix A), two major quality control activities are conducted during this project to measure the performance of the various MS5 multiprobes. The first major quality control activity is to determine the precision of dissolved oxygen measurements between instruments and the bias associated with those measurements. This precision is measured between all instruments prior to the field season and is used as the criteria to delineate monitor replacement (see section 137.4). The second major quality control activity tracks the differences in dissolved oxygen measurements between a freshly calibrated field validation instrument and deployed tailrace monitors. The tracking of the mean difference and upper and lower control limits (see Appendix B for example quality control chart) are used to evaluate frequency of monitor validation, procedural changes, and water quality variability influencing monitor behavior. B5.1 Annual Determination of Precision and Bias ¦ In the laboratory, each instrument to be used for the tailrace monitoring is calibrated to water saturated air as described in SOP 3210.3 (Appendix A) ¦ After calibration, all instruments are placed in a tank3 containing water about 80% saturated with DO. 2 Temperature tolerances are given in Standard Operating Procedure 3210.3; temperature checks, both routine and annual tests are part of the SOP and are not discussed further (see section B6). 3 The calibration tank is fitted with submersible pumps to circulate the water in both horizontal and vertical patterns. Gas dispersion stones are placed on the bottom of the tank to allow for either nitrogen gas introduction (to purge oxygen from the water) or oxygen addition (to add oxygen to the water). By controlling the gas flow from either source, the dissolved oxygen concentration in the tank may be altered without changing the chemical properties of the water. 39 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 ¦ After the instruments have equilibrated to tank conditions, the DO readings from all the instruments are recorded. The dissolved oxygen concentration is then adjusted to a new target DO concentration4 by bubblings an oxygen free gas, e.g. nitrogen to reduce the oxygen, or by bubbling a gas with oxygen, e.g. compressed air or oxygen, to increase the DO level. After the new target concentration is reached, and after the instruments have equilibrated, the DO readings from all the instruments are recorded. This process is repeated until all target concentrations were sampled. ¦ Any instruments not within a 95 % confidence interval (simple t-test), are rejected and either repaired or returned to the manufacturer (any new instrument received during the monitoring season will be subjected to the precision calculations prior to use). ¦ The precision (measured as ± 2 times the standard deviation about the mean equals the 95% confidence interval) and bias (measured as difference from zero) of dissolved oxygen recordings are calculated over the tested range of dissolved oxygen. These control limits set the expected range of the differences between Field Validation Instrument readings and the Tailrace Monitor reading if the Tailrace monitor remains calibrated (further discussed in Section B7.4). If the field measurements exceed the upper or lower control limits, the tailrace monitor should be replaced. B5.2 Routine Tracking of Tailrace Monitor Performance Quality control charts (see Appendix B for example QC chart) will be used to evaluate the performance (measured as the oxygen concentration of the deployed monitor compared to a Field Validation Instrument) of the deployed tailrace monitor for any given tailrace, for any given procedural change, for any given criteria used in the documentation process. ¦ Routine calculation at each tailrace - calculate the mean and ± 2 times the standard deviation about the mean of the last 4 tailrace monitor dissolved oxygen differences. Plot the mean and upper and lower 95% confidence interval. ¦ Evaluate improvements in the program methodology by tracking the trend of the mean towards zero and a narrowing of the confidence interval. B6.0 Instrument/Equipment Testing, Inspection, and Maintenance (discussed in SOP) The Field Monitoring Manager is responsible for establishing the proper procedures for testing, inspection, and maintenance of all water quality instruments. The procedures will include a thorough evaluation of instrument performance including instrument response times to large concentration differences. Records will be maintained for each instrument (tracked by serial number) for repairs, sensor replacements, battery replacements, response times, and factory repair over the lifetime of the instrument. These records will be used to evaluate the suitability of instrument deployment. All maintenance and servicing of instruments will be recorded by the Field Staff in a maintenance logbook and in an established electronic format. 4 Minimal tank DO concentrations must include conditions at or near saturation, and also concentrations that are in the range of 0 to 2 mg/L, 2 to 4 mg/L, and 4-6 mg/l. s Unlike adding a chemical reducing agent, bubbling a gas does not change the chemical properties of the test water 40 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 B6.1 Annual and Routine Maintenance ¦ Annual maintenance - to be performed prior to field season o Replace the internal lithium battery in each instrument (Hach, 2005) o Replace the LDO sensor cap (Hach, 2005) o Protect and lubricate Electrical cables (Hach, 2005) o Clean Standpipe with rope, chain, and swabbing cloth o Test and verify internal logging capability o Document replacements on Instrument Maintenance Form ¦ Routine Maintenance (Immediately after Deployments) o Clean the Multiprobe housing using a clean brush, soap, and water (protect the sensors with the calibration cup), rinse the instrument with clean tap water (no more than 50 °C) o Clean sensors with soap and water, rinse with clean tap water, rinse with ethanol or isopropyl alcohol (as necessary) to remove residual grease, rinse with clean tap water o Store with calibration cup containing pH 4 buffer at room temperature (z 20°C) B6.2 Annual Temperature Testing, Prior to Field Season ¦ Refer to SOP # 3210.3 for annual temperature testing ¦ If the instrument fails the test, it is returned to Hach for repair ¦ Document test on Instrument Maintenance Form B6.3 Annual Dissolved Oxygen Testing, Prior to Field Season ¦ Refer to section B5 to establish Precision Limits ¦ If the instrument oxygen concentrations are significantly different than the others, it is returned to Hach for repair ¦ Document test on Instrument Maintenance Form B7.0 Instrument/Equipment Calibration and Frequency In addition to the initial calibration of the instruments, this section also details the process of validation of the accuracy of the deployed tailrace monitor and, if necessary, replacement of the deployed instrument with a freshly calibrated and programmed monitor. B7.1 Calibration of MS5 Multiprobes ¦ The number of instruments to be calibrated is equal to the number of tailrace monitors checked during one day ¦ In the laboratory, calibrate each instrument according to Standard Operating Procedure # 3210.3 (Operating Procedure for the Hydrolab water quality analyzers, Appendix A) o Set the instrument to GPS time (also cell phone time) o Dissolved oxygen will be air calibrated (# 3210.3, section 2.2) 41 Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 o Temperature readings will be checked (# 3210.3, section 6.2) ¦ Complete the modified Field Sampling Calibration Data Form for calibration documentation B7.2 Transport and Storage of Calibrated Instruments to Tailrace ¦ After calibration, place '/2 inch of de-ionized water in the calibration cup of each instrument. Seal the calibration cup to the MS5 multiprobe for transport ¦ Each instrument shall be placed in an insulated container for transport ¦ The instruments (in their insulated containers) should be kept out of direct sunlight while being transported B7.3 Field Check of Field Validation Instrument6 ¦ Select one calibrated MS5 multiprobe to check the tailrace monitor ¦ Set-up the instrument for a water-saturated air calibration as per SOP # 3210.3 ¦ From the temperature, dissolved oxygen mg/l, and the barometric pressure, calculate the percent saturation, if the resultant % sat is greater than 97% and less than 104 % (ASTM, 2005), calibration is verified and may be used to check the tailrace monitor's accuracy. ¦ Document all activities on the modified Field Sampling Calibration Data Form B7.4 Check and Document Tailrace Monitor Accuracy ¦ Connect to the Tailrace monitor, check the MS5 multiprobe time. If the monitor's internal clock is different from GPS time (cell phone time; to the nearest minute), re-set the monitor time. ¦ Lower the Field Validation Instrument so it is adjacent to the Deployed Tailrace Monitor, after readings have stabilized from the Field Validation Instrument, record the dissolved oxygen concentration from both the Field Validation Instrument and the Tailrace Monitor, and calculate the concentration difference. If the difference is less than the established precision (see section 135), document the difference on the Field Sampling Calibration Data Form and continue using the same tailrace monitor. ¦ If the concentration difference is greater than the established precision, replace the tailrace monitor with a freshly calibrated monitor. ¦ Refer to section D1 for a discussion of raw data that will be flagged as a result of monitor validation B7.5 Back-up File? for Tailrace Monitor ¦ Program the tailrace monitor for an internal logging file to record the temperature, dissolved oxygen, and battery voltage at 15-minute intervals with a stop date of at least a month from the present time. 6 To keep the nomenclature consistent, the MS5 multiprobe that is in the standpipe continuously recording data in the tailrace is called the `Tailrace Monitor'; the MS5 multiprobe used to check the accuracy of the tailrace monitor is called the `Field Validation Instrument' ' This file is created as a back-up system in the event that communication and/or power are lost from the SCADA wave radio to the station computer. The station computer would serve as a data back-up in the event that the link between the station computer and the Pi database was lost. 42 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 ¦ If present in the internal memory, download the previous back-up file set-up at an earlier date. Back-up file is stored on the dedicated field storage database. Quality control charts shall be used to record all sensor validations (see section 135). These charts shall be available for individual instruments and individual hydros. Initially, field validations will be conducted approximately weekly. However, over time the quality control charts will be used to adjust validation frequency, especially if the luminescence sensors require less maintenance than Clark Cell technology. B8.0 Inspection/Acceptance of Supplies and Consumables The Field Monitoring Manager approves all orders for supplies required for instrument maintenance and calibration. Upon receipt, all supplies will be inspected for damage. All supplies and equipment ordered will be stored and documented in accordance with Duke's Chemical Inventory and approved through Duke's chemical approval process. B9.0 Non-Direct Measurements Measurement data not obtained directly under the WQMP and this QAPP, including hydro plant generating data, reservoir elevation data, National Weather Service weather data, and/or U.S. Geological Survey (USGS) gage stream flow data, may be used in the annual report to identify instances that would aid operators in future aeration applications. These data may also help identify continuous improvement procedures. These data, collected by regulatory and/or other governmental agencies, may be used and considered as valid data since these agencies have independent QA/QC programs. Catawba- Wateree Project generation data will be acquired through Duke Energy's Hydro Fleet Operations. B10.0 Data Management The continuous DO and water temperature data are collected and monitored on a real time basis. As the sensor detects the concentrations, the data is automatically transmitted to the PI data system via the station computer. The PI SystemTM is used to manage the operational and environmental data gathered from many different sources in the stations. The process brings the data from the sensors into a single system that can deliver it to users at all levels of the company. The PI System provides real-time management, retrieval and archiving of volumes of data. In addition, the system keeps all critical operating data online and available in a specialized time-series database so the data is always available. The PI System functionality incorporates many features for analyzing, contextualizing, and visualizing real-time PI data. This PI System uses software developed by OSI that provides the following: 43 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 Displays real-time data in intervals specified for specific applications. It also provides a graphics package that enables users to create dynamic, interactive graphical displays. DataLink establishes a direct connection between the PI System and Microsoft Excel to create and publish reports and perform complex data analysis. PI Notifications provides access to the configuration, management, delivery, acknowledgement, and visualization of notifications. The PI database provides for permanent records storage while the station computer temporarily stores the data should the transfer link to the PI system fail. Once in the PI data system, the data, is provided to Duke's Hydro Operations Center real-time (see Section A6.2 Table 3, B2 Figure 3). The protocol for data transmission, storage, and retrieval is controlled by the Plant Information (PI) database management team (see section A4). Data files are stored for the duration of the project on the PI data server, which is backed up electronically on a daily basis. GROUP C - ASSESSMENT AND OVERSIGHT CLO Assessment and Response Actions The Duke Field Monitoring Manager will verify laboratory certification renewal schedules and maintain certification as required. In addition, the Duke Field Monitoring Manager will review and verify field monitoring quality assurance activities including documentation of performance of field procedures, data back-up, back-up data logging, monitor replacement, monitor status (including callouts), and any other notes impacting the quality of the data. The Field Monitoring Manager will observe the field techniques of the Field Staff at periodic intervals throughout the monitoring season. Any issues with technique will be corrected at that time and documented in the appropriate field logbook. The Field Monitoring Manager and the Duke EHS QA Officer will conduct a field sampling technical system audit prior to the monitoring season. The audit will review current QAPP requirements for sampling, instrumentation, calibration, tracking, and data management activities, especially noting any potential changes to the QAPP. The Duke EHS QA Officer provides oversight through the review of the QA/QC records generated for the continuous DO and water temperature monitoring program. The Duke Hydro Generation Data Processing / QA Manager will review any corrections or revisions to data files and any subsequent documentation in the QA/QC file. In addition, an annual review of the QAPP will be performed for accuracy and /or changes identified from past audits. The Duke Project Manager will review the QAPP prior to the field season and verify its applicability and accuracy. A summary of these activities is presented in Table 4 44 Duke Energy Carolinas, LLC Quality Assurance Project Plan Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 C2.0 Reports to Management The process for reporting significant issues will follow a chain of command structure. All project managers will report problems, documents, and audit results to the Duke Project Manager for problem resolution and corrections. The Duke Project Manager will receive annual reports, copies of logbooks, and calibration forms for review and will ensure that these records are maintained in a designated QA/QC file. Project Manager will report to Duke Management will be made as requested. Table 4 Summary of Project Assessment Activities Assessment Activity Frequency Responsibility Duke Field Monitoring Manager SC DHEC Office of Environmental Laboratory Certification SCDHEC and Laboratory Certification NCDWQ NC Division of Water Quality, schedules Office of Environmental Laboratory Certification. Field Sampling Technical Annually, Prior to Duke Field Monitoring Manager System Audit Monitoring Season Interim Procedure Assessment Twice during Field Monitoring Manager Monitoring Season Once during Monitoring Season Review of Field Monitoring And EHS QA Officer QA/QC Records Prior to Annual Report Once during Review of PI Database Monitoring Season Hydro Generation Compliance Documentation And Data Processing / QA Manager QA/QC Records Prior to Annual Report Review of QAPP Annually, Prior to Duke Project Manager (documenting any changes) Monitoring Season 45 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 GROUP D - DATA VALIDATION AND USABILITY D1.0 Data Review, Verification, and Validation The major purpose of the dissolved oxygen enhancements in the Catawba-Wateree Hydro tailraces is to increase the dissolved oxygen concentration to at least state water quality standards. Critical to this objective is real-time dissolved oxygen data available to the operators to enable a quick response to low DO concentrations by adding oxygen via turbine aeration. A secondary objective is data reporting and QC documentation to ensure compliance with standards and procedures. Therefore, pursuant to the primary objective, the operators must initially assume the data to be valid in order to make real-time aeration decisions. If questions arise, the operators may request that the monitor readings should be validated (see Section A7). However, for purposes of reporting tailrace temperatures and oxygen concentrations, the data stored in the PI database will be reviewed and validated by the Field Manager for annual reporting. No data will be considered as invalid and rejected from analysis, but rather data will be flagged if (1) the monitor was found not to be responding, (2) the deployed monitor DO concentrations exceeded the established performance criteria (see section A7 and 135). The actual performance of the tailrace sensor is validated and documented either by the routine checks (see section B) or by non-routine call-outs requested by the operators (see section A7). If data were missing, the database available for the annual report would have data from the backup files replacing the missing values. In addition, in the case of the monitor exceeding the performance criteria, the original PI data would be flagged as exceeding the precision criteria and presented along with the data adjusted for the difference between the Field Validation Instrument and the deployed monitor. In addition, hourly averages (15-minute data averaged from the beginning to the end of an hour) will eliminate periodic transients (electrode spikes, very short periods of low oxygen concentrations during initial unit start-up and other short transients in water quality. The frequency and magnitude of transients will be reviewed as part of the data analysis for the annual report. D2.0 Verification and Validation Methods D2.1 Data Verification The Field Monitoring Manager, or a qualified QA/QC Auditor appointed by the Field Monitoring Manager, will perform an annual (after the field monitoring season) self-assessment of the QA program to ensure the QA/QC records are complete and accountable. These assessments are based primarily on the field data sheets, maintenance records, quality control charts, and back-up files provided by the Field Staff. The self-assessment results will be documented and provided to the Duke EHS QA Manager for the project QA/QC files. Any corrective actions, as required, will be implemented and documented. The Field Monitoring Manager shall review these actions and provide recommendations to the Project Manager for potential revisions to the program and revisions to the procedures and/or QAPP. 46 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 After each field season, the Hydro Operations Manager shall review the process of obtaining information from the PI database, obtaining the field monitoring data as needed, the process of call-outs, the information needed to assess monitor performance, and non-compliance trends (if any). The self-assessment results will be documented and provided to the Duke Hydro Generation QA Manager and the Duke Data Processor manager for evaluation. Any corrective actions, as required, will be implemented and documented. The Hydro Operations Manager shall review these actions and provide recommendations to the Project Manager for potential revisions to the program and revisions to the procedures and/or QAPP. The Duke Project Manager will ensure coordination of activities, data processing, data review, and revisions to the program between EHS and Hydro Generation. D2.2 Data Validation PI Database (see section B 10) Throughout the monitoring season, the Duke Data Processor Manager will periodically transfer a sample of data from the PI system to spreadsheets designed to perform provisional data summaries and trend analysis. The PI data will be compared to the back-up data retrieved from the tailrace monitors (see section B7.5) by checking for missed data, data that does not match for the same time stamp, and hourly and daily averages calculated in PI and manually calculated in the spreadsheet. If errors are found in the PI database, the source of the problem shall be immediately investigated by the Duke Data Processor Manager. Documentation of the data comparison shall be retained in the QA records. Calibration Checks The Field Monitoring Manager shall check and validate the calculation for percent saturation used by the Field Monitoring Staff for the calibration checks of the MS5 multiprobe while in the field (see section B7.3). Limits of Precision Prior to the field season, the Field Monitoring Manager will review the test data to determine the instrument precision criteria, approval of the Field Monitoring Manager will be documented and retained in the EHS QA records. Annual Report Database At the end of the field season, the Field Monitoring Manager will provide the Duke Project Manager a copy of the final annual database. This database will include all hourly and daily averages, as determined from the PI database as a primary source, with calibration data points, and any flagged data resulting from monitor errors. In addition, data missing from the PI database will be added to the final annual database from the back-up files. The Field Monitoring Manager will transfer the final annual database, all supporting calibration forms and field records, maintenance records, and instrument precision measurements to the Duke Project Manager prior to writing the annual report. Throughout the entire monitoring season, the database is archived systematically to ensure no loss of data and to guarantee database integrity. At the end of the field monitoring season, all 47 Duke Energy Carolinas, LLC Catawba-Wateree Project No. 2232 Quality Assurance Project Plan Revision No. 0 Revision Date: 10/20/2008 forms, original data, and the database will be archived in electronic format on digital media; and stored in an electronic storage format as well as by the Duke Project Manager. D3.0 Reconciliation with User Requirements As mentioned in section D1, data collected during the Catawba-Wateree Compliance Monitoring program will be used by hydro operations personnel to comply with the requirements of the 401 Water Quality Certification and the FERC license, provide water quality data for reporting compliance and/or non-compliance events to appropriate agencies, and conduct on-going evaluations regarding equipment performance and operational guidelines. To minimize operator errors, the real time data will be available in the Hydro Operating Center, which will be displayed with real-time computation of hourly and daily average DO values. The real time presentation allows for quick identification of instrument and or operational issues with the data and allows for immediate problem identification and resolution. Additionally, dissolved oxygen data is not collected with the intention of cause-and-effect analysis, nor to make correlations with lake or station operations; but used for determination of compliance to state water quality standards. The uncertainty of the data is correlated with the accuracy of the dissolved oxygen monitor, which the primary focus of the decision is making process. In the event that anomalies are found in the data, the Duke Project Manager will review the field notes taken by the Field Monitoring Manager and look for storm events or unusual watershed conditions and assess their effects on data. Data collected for each monitoring season will be put in report form and provided to NCDWQ, SCDHEC, Duke and FERC, as well as archived in the PI system. Any anomalies and analysis for any peaks or changes in data throughout the year will be documented in the reports provided by the Field Manager to the Duke Project Manager. Any field monitoring modifications will be considered only after consultation with NCDWQ/SCDHEC. 48 Duke Energy Carolinas, LLC Quality Assurance Project Plan REFERENCES Catawba-Wateree Project No. 2232 Revision No. 0 Revision Date: 10/20/2008 American Society for Testing and Materials (ASTM). 2005. D888-05, Standard Test Methods for Dissolved Oxygen in Water. ASTM. West Consholocken, PA. Duke Energy. 2005a. Catawba Hydros - Existing Aeration Capability and Downstream Aeration Tests, Technical Report Series, Catawba-Wateree License. FERC No. 2232, Charlotte, NC. Duke Energy. 2006. Cataw ba- Wateree Project FERC # 2232 Application for New License Exhibit E Water Quantity, Quality, and Aquatic Resources, Study Reports. Duke Energy. Charlotte, NC. Hach Environmental. 2005. Instruction Sheet, Hach LDOTm Sensor. Hach Environmental Corp., Loveland, CO. Knight, Jon, 2003. Dissolved Oxygen Concentrations and Water Temperature from Bridgewater Hydroelectric Station. Duke Power Company. United States Environmental Protection Agency. 2001. EPA Requirements for Quality Assurance Project Plans. EPA QA/R-5, EPA/240/B-01/003. USEPA, Office of Environmental Information, Washington D.C. Wagner, R. J., H. C. Mattraw, G. F. Ritz, and R. A. Smith. 2000. Guidelines and Standard Procedures for Continuous Water-Quality Monitors: Site Selection, Field Operation, Calibration, Record Computation, and Reporting. U. S. Geological Survey, Water- Resources Investigations Report 00=4252. Reston, Virginia. 49 APPENDIX A-QAPP Standard Operating Procedures for In Situ Hach MS5 Multiprobe PROCEDURE 3210.3 OPERATING PROCEDURE FOR THE HYDROLAB WATER QUALITY ANALYZERS 1. INTRODUCTION A. Purpose This procedure applies to groundwater, surface water, and domestic and industrial wastewaters. Parameters measured depend on instrument-specific set-up and monitoring requirements. Routine measurement capabilities, including temperature, dissolved oxygen (DO), percent dissolved oxygen saturation, pH, specific conductance, oxidation-reduction potential (redox, or ORP), and depth are covered in this procedure. Additional parameters, including, salinity, total dissolved gas, light transmissivity, turbidity, chlorophyll a, and a variety of ion-selective parameters, (i.e., ammonium, nitrate, and chloride) are not included in the procedure, but are described in specific instrument manuals and other relevant references. B. Summary of Method 1. General Capabilities Hydrolab instruments may be deployed in either attended or unattended mode. Deployment in attended mode requires the instrument be cabled to either a Hydrolab display unit (e.g., Surveyor 4) or a field-portable computer running appropriate communications software. In unattended mode, Hydrolab instruments are programmed to log data into internal memory at user-specified intervals. Data are subsequently downloaded to a Hydrolab display unit (e.g., Surveyor 4) or more typically, a field-portable computer after the Hydrolab sonde is retrieved. The instruments may be configured either for waterbody surface sampling and/or vertical water column profiling from a boat or platform, moored to a buoy or other stationary object (unattended mode), or configured with a flow-through cell for groundwater monitoring or similar applications. Maximum depth for deployment is typically 100 m (consult individual instrument and/or sensor specifications in operator manuals for further details). NOTE: In the event Hydrolab instruments are to be used to collect reportable National Pollution Discharge Elimination System (NPDES) compliance data, instrument measurement subsystems (including, as applicable, temperature, DO pH, and specific conductance) shall be calibrated on no less than a daily basis, using the techniques described herein. 3210.3 A- I Nominal specifications for measurement performance of the subsystems may differ slightly between instrument models and subsystem upgrades. The user should consult the specific instrument manual or applicable product literature in determining applicable parameter measurement specifications for each Hydrolab instrument. 2. Measurement Subsystems 2.1 Temperature Subsystem A thermistor is mounted in the sensor probe. Resistance to an electrical current transmitted through this thermistor changes with temperature. The thermistor output is transmitted through a Wheatstone bridge and converted to a linear temperature-proportional signal displayed in degrees Celsius. The temperature subsystem is checked with each use at a single temperature, and annually at a series of temperatures, against an NIST-traceable thermometer. There are no provisions for user adjustments to the temperature subsystem, which is factory calibrated. No specific interferences have been encountered with this subsystem. It is recommended that Hydrolab temperature analyses be determined only in-situ, or with the use of a flow-through cell (e.g., for groundwater applications). Measurement of temperature from discrete samples is not recommended because it introduces an additional and possibly substantial error associated with heat transfer between the sample water, the collection device and Hydrolab sonde. 2.2 Dissolved Oxygen Subsystem The DO subsystem DataSonde 4a or MiniSonde Series 4a and earlier Hydrolab instruments incorporates a membrane-covered, passive Clark polarographic cell. The cell consists of two electrodes (an outer, gold cathode and an inner, silver anode), and a small cylindrical electrolyte-filled cavity, which is sealed with a gas-permeable membrane. Voltage is applied between the two electrodes so that the cathode is about 800 mV negative with respect to the anode. When the cell is energized, all molecular oxygen inside the electrode is electrochemically reduced at the cathode (02 + 4e 20 consuming molecular oxygen in the cell, and reducing the cell's internal partial pressure of oxygen to zero. If the oxygen partial pressure outside the cell is not zero, oxygen will diffuse through the membrane into the cell at a rate proportional to the external (i.e., sample) partial pressure. As the diffusing oxygen is reduced at the cathode, a current is generated in the cathode-anode circuit that is proportional to the diffusion rate and therefore, to the partial pressure of oxygen outside the cell. Two thermistors 3210.3 A-2 are mounted in the DO probe. One thermistor corrects for the difference in membrane permeability due to temperature. Signals from the second thermistor are used to calculate a DO solubility coefficient for the sample water. The coefficient and sample water partial pressure are multiplied to obtain the DO concentration in mg/L. The DO subsystem on DataSonde 5 and MiniSonde Series 5 and later Hydrolab instruments incorporates a luminescent sensing probe (LDO sensor). The luminescent DO sensor's optical components consist of a pair of blue and red light-emitting diodes (LEDs) and a silicon photodetector. The LDO sensor cap is coated with a platinum-based luminophor that is excited by the light from the blue LED. The luminophor is coated on the outside with a carbon black polystyrene layer for optical insulation, providing protection against photobleaching from external light sources when the sensor cap is attached to the sensor. The blue excitation LED is sinusoidally modulated at a frequency related to the luminophor's luminescence period and the upper and lower periods of analytical interest. The measured parameter of interest from the LDO electrode is the phase delay (time delay) between the exciting blue LED signal and the detected red emission from the luminophor, with the phase delay inversely related to the amount of dissolved oxygen in the surrounding water. The blue and red LEDs are alternatively switched between measurement cycles, allowing the red LED to provide an internal reference for the optical and electronic signal paths. This internal reference provides measurement stability by correcting for temperature or time-induced changes in the phase measurement electronics. The DO subsystem can be calibrated in water vapor-saturated air, or in water with a known DO concentration as determined by the modified-azide Winkler method. Care must be taken to ensure that thermal and gaseous equilibrium has been established in the calibration vessel prior to calibration. Broad variations in the kinds and concentrations of salts in water samples can interfere with membrane permeability, although this is not generally a problem in fresh water. Certain other compounds (SO2 and Cl2 gases, nitrogen oxides and organic mercaptans) will attack the polarographic cell -Ar membrane and cause erroneous readings. Water containing low or depleted DO concentrations may form hydrogen sulfide and interfere with polarographic DO measurements. Elevated hydrogen sulfide concentrations interfere with the ability of oxygen to undergo reduction at the sensor cathode and with prolonged exposure, can poison the polarographic electrodes, causing permanent damage. Other potential interferences (for polarographic sensors) include circulator malfunctions and air bubbles under the membrane. In either case, erratic and erroneously low DO readings will result. 3210.3 A-3 It is recommended that Hydrolab DO analyses be determined only in-situ, or with the use of a flow-through cell (e.g., for groundwater applications). The measurement of DO from discrete samples is not recommended due to potential errors introduced though sample collection (i.e., under-saturated samples will be aerated upon exposure to the atmosphere, while supersaturated samples will tend to lose DO following collection). Further potential error in DO measurements taken from discrete samples is associated with changes in DO solubility resulting from thermal changes in the sample. Sampling personnel shall clearly document in field records instances where DO was measured from a grab sample. 2.3 pH Subsystem The pH of a solution is a measure of hydrogen ion activity in the solution. The pH value is expressed as the logarithm of the reciprocal of hydrogen ion activity expressed in moles per liter at a specific temperature. Values range from pH 0 (extreme acidity) to pH 14 (extreme basicity), where pH 7 is neutral. A glass, pH-sensitive silver/silver chloride probe and reference probe supply a signal that is proportional to the pH of the sample water. The signal is continuously compensated for sample temperature deviations from 25 °C, as measured by the temperature probe. Both the glass pH probe and the reference probe have been modified to operate in the high-pressure environment of subsurface sampling. Films of oil or particulate matter can impair the response of a pH electrode; however, proper cleaning and routine maintenance can minimize these interferences. pH reference electrodes of the refillable type are normally used and recommended, as opposed to the non-serviceable, low ionic strength (LIS), KCl crystal-impregnated plastic variety. However, for pH measurements in low conductivity (low ionic strength) waters or for unattended deployments exceeding 3 continuous weeks, an instrument equipped with an LIS reference probe may provide more reliable service. f Refillable reference electrodes require routine replenishment (i.e., replacement) of the internal electrolyte (saturated KCl) solution (including KCL crystals which ensure saturation), at a frequency depending on instrument usage patterns. Reference electrode tips, which include a permeable Teflon junction, are replaced on an as needed basis, depending on whether or not blockage of the junction is noted during the electrolyte refilling operation. Non-serviceable LIS reference probes should be capped between uses with a tight-fitting plastic cover containing reference filling solution. 3210.3 A-4 The pH subsystem is routinely calibrated using two certified NIST-traceable buffers in a two-point calibration. A third buffer is then used to check for linearity of probe response. To test for potential errors associated with use in low ionic strength environments and the potential degradation of the reference probe, the user should consider occasionally re-checking the pH subsystem after conventional calibration using a special low ionic strength buffer, such as are commercially available (e.g., Orion" ). Hydrolab pH analyses should be determined in-situ, or with the use of a flow-through cell (e.g., for groundwater applications). The measurement of pH from discrete samples is not recommended due to potential errors introduced though sample collection (e.g., primarily changes in sample dissolved gas concentrations that affect the carbonate-bicarbonate equilibrium and subsequently, the sample pH). 2.4 Conductivity Subsystem Hydrolab instruments utilize a variety of conductivity sensor designs, including cells with nickel or graphite electrodes. In all cases, the signal from the conductivity cell is continuously compensated for sample temperature deviations from 25°C by the temperature probe, enabling the measure of specific conductance. Salinity (in ppt) and/or total dissolved solids (in mg/L) can be directly calculated from Hydrolab specific conductance values using one of several user-selectable functions. The conductivity subsystem is routinely calibrated using NIST-traceable standard KCl solutions. The most common interferences are caused by foreign substances (i.e., biofilms or mud) or air bubbles within the sensor chamber, resulting in erroneous readings. Whenever possible, Hydrolab specific conductance analyses should be determined in-situ, or with the use of a flow-through cell (e.g., for groundwater applications). Discrete samples for specific conductance should be analyzed as soon as practical following collection but may be held at 0 to 4 °C up to 28 days before analysis. Ample sample volume (e.g., A0 500 mL) must be collected to allow adequate rinsing of the instrument probes between analyses. 2.5 Redox Subsystem The redox (also, oxidation-reduction potential, or ORP) subsystem measures the oxidative or reductive potential of a solution. The redox potential of a solution is dependent upon the nature of the dissolved substances in solution, proportions of the oxidized and reduced constituents, and the solution temperature. A platinum electrode (typically mounted on the glass 3210.3 A-5 pH probe) is utilized in conjunction with the silver/silver chloride reference electrode. The silver/silver chloride electrode has a standard potential of about +200 millivolts with respect to the standard hydrogen electrode. Redox values are displayed in millivolts and are continuously corrected for sample temperature deviations from 25 °C. The redox subsystem may be calibrated with quinhydrone solution or alternate redox standards prepared per Standard Methods (Reference C.1). Highly corrosive solutions, such as Light's Solution (Reference C.1) should be avoided, however. Since relative redox values are most often of interest in water column profiles, rather than absolute voltage potentials, the redox subsystem may not require calibration routinely. Specific study plans should be consulted regarding the need to calibrate this subsystem. Interferences in redox readings can result from mud or other material accumulating on the redox probe, causing abnormally low or negative readings. Hydrolab redox analyses should be determined in-situ, or with the use of a flow-through cell (e.g., for groundwater applications). The measurement of redox from discrete samples is not recommended due to potential errors introduced though sample collection (e.g., primarily changes in sample dissolved gas concentrations that affect constituent solubility, and therefore, the sample redox potential). 2.6 Depth Subsystem The depth subsystem utilizes a strain gauge-type pressure transducer requiring conversion of an output in volts to a reading in meters of fresh or salt water. The conversion factor (or slope setting) for systems that operate in seawater is about 3% lower than fresh water. Interferences include mud or silt clogging the sensor access port. The depth sensor will operate accurately only for battery voltages of >_ 9.5 volts. The depth sensor is routinely calibrated by setting the zero (with the sonde in air) at the deployment site. 2.7 Other Subsystems Consult appropriate Hydrolab manuals or other product literature for information on other available measurement subsystems, including turbidity or chlorophyll probes and the various available ion-selective electrodes. C. References American Public Health Association; American Water Works Association; Water Environment Federation. 1998. Standard Methods for the Examination of Water and Wastewater. 20th Edition. Methods: 2510 Conductivity; 2550, Temperature; 3210.3 A-6 2580, Oxidation-Reduction Potential (ORP); 4500-H+, pH Value. American Public Health Association, Washington DC. 2. American Society for Testing and Materials (ASTM). 2005. D 888-05, Standard Test Methods for Dissolved Oxygen in Water. August 2005. ASTM. West Conshohocken, PA. 3. Duke Power Company. 2005. Iodometric / azide modification for Winkler titration in determining dissolved oxygen. Procedure 3200.Xi. 4. Hach Corporation. 2006. Hydrolab DSSX, DS5, and MS5 Water Quality Multiprobes User Manual. February 2006, Edition 3. Hach Company, Loveland, CO. 5. Hydrolab Corporation. 1998. DataSonde 4 and MiniSonde Water Quality Multiprobes User's Manual. Revision E, April 1998. Hydrolab Corp., Austin TX. 6. . 1998. Welcome to Profiler TM Beta for Series 4 Instruments. Draft Manual, January 1998. Hydrolab Corp., Austin TX. 7. . 1995. DataSonde 3 Multiprobe Logger Operating Manual. Revision H, April 1995. Hydrolab Corp., Austin TX. 8. Mitchell, Thomas O. 2006. Luminescence based Measurement of Dissolved Oxygen in Natural Waters. Hach Company, Loveland, CO. 9. US Environmental Protection Agency (USEPA). 1983. Methods for the Chemical Analysis of Water and Wastes. Environmental Monitoring and Support Lab, Office of Research and Development. Cincinnati, OH 10. . 2006. Notice of Region 4 Interim Approval of ASTM International Method D 888-05 for measuring dissolved oxygen in the National Pollution Discharge Elimination System (NPDES) discharges. June 1, 2006. USEPA, Region 4, Science and Ecosystem Support Division, Athens, Georgia. Web site: http://www. epa. gov/regi on4/sesd/oqa/atp-method-d-888-05- (accessed June 27, 2006) II. MATERIALS A. Equipment 1. Hydrolab sonde unit, with appropriate sensors, cables (including PC serial port interface), and accessories ' An ".X" following a reference to a procedure number shall equate to the most recent approved revision of the referenced procedure. 3210.3 A-7 2. Portable computer with appropriate communications software and formatted diskettes or flash drive and hard drive storage 3. Power supply: Gel cell battery (12 VDC), 2 ea. w/ connectors and cables for Hydrolab and computer, or gas-powered 110 VAC generator with inverter for 12- VDC output (for instrument cables that enable an external DC power source) 4. Battery charger, 12 VDC (if Gel cells are used) 5. Computer power supply (110 VAC; or 12 VDC with inverter) 6. Calibration kit, with the following materials: 6.1 Calibration cup with cap 6.2 Flow-through cell (may be required for groundwater monitoring) 6.3 Calibration / field notes document & pen (Note: information may be stored in electronic form on field PC) 6.4 NIST-traceable thermistor or thermometer 6.5 Winkler titration equipment (not required if air-calibrating DO) 6.5.1 Calibration vessel (e.g., bucket) 6.5.2 200-mL volumetric flask 6.5.3 500-mL Erlenmeyer flask 6.5.4 300-mL BOD bottle w/ cap 6.5.5 Scissors 6.6 Barometer (or NOAA broadcast receiver / Internet access, and calculator) (required if air-calibrating DO) 7. Lint-free laboratory wipes or cloth 8. Electrode maintenance supplies (including Teflon DO membranes, LDO probe caps, reference cell junctions, cotton swabs, and spare o-rings) 9. Precision controlled temperature water bath (for annual temperature and thermal compensation testing) B. Reagents (refer to Safety, Section V, prior to handling the listed reagents) 1. Calibration kit (continued), with the following reagents: 1.1 pH buffers, NIST-traceable (pH 7.00, pH 4.00 pH 10.0) (e.g., Fisher Scientific pH 7.0 Buffer, Duke MSDS.net No. 16772; Fisher Scientific pH 4.0 Buffer, Duke MSDS.net No. 15291; Fisher Scientific pH 10.0 Buffer, Duke MSDS.net No. 15454) 1.2 KCl specific conductance standard(s), NIST-traceable (e.g., Biopharm Conductivity Standards, Duke MSDS.net No. 411963) Select a standard exceeding the highest anticipated specific conductance to be measured during sampling. A specific conductance standard recommended for a given monitoring program should be specified in study plan documents. 1.3 Winkler titration reagents: (not required for air calibration) 1.3.1 Manganous sulfate dry reagent (e.g., Hach Co., Duke MSDS.net No. 1096) 1.3.2 Alkaline iodide azide dry reagent (e.g., Hach Co., Duke MSDS.net No. 50) 1.3.3 Sulfamic acid dry reagent (e.g., Hach Co., Duke MSDS.net No. 10712) 3210.3 A-8 1.3.4 Sodium thiosulfate solution, 0.025N, (e.g., Hach Co., Duke MSDS.net No. 21088) in refillable (25-mL X 0.1 mL graduation) buret 1.3.5 Starch solution, 0.5%, (e.g., Fisher Scientific., Duke MSDS.net No. 13080) in dropper or dispenser bottle 1.3.6 Potassium bi-iodate solution, 0.025N, (e.g., Hach Co., Duke MSDS.net No. 1473) in dropper bottle 1.4 Quinhydrone (e.g., Acros Organics, Duke MSDS.net No. 23928) standard(s) or alternate redox standards prepared per Standard Methods (if necessary; see Enclosure B) 1.5 DO electrolyte solution, 2 M potassium chloride with 1% Triton X-100 (e.g., Ricca Chemical Co., Duke MSDS.net No. 25255); required if polarographic DO probe maintenance is required 1.6 pH reference electrode filling solution, saturated KCl with < 1% silver chloride (e.g., Ricca Chemical Co., Duke MSDS.net No. 25254); required if pH reference electrode maintenance is required, or for LIS reference probe storage 1.7 Demineralized water (e.g., Milli-Q® water polished by final filtration through a 0.2 ? m filter) III. METHOD NOTE: The manufacturer's operating manual should be referenced for specific instructions regarding instrument or software operation for the various Hydrolab models. Instruments are often similar in principle and require only differences in keystrokes or menu selections to operate and calibrate. Use the appropriate instrument owner's manual and software documentation to guide through the specific keystrokes for instrument operation and calibration. A. Instrument Preparation 1. If required, service and re-assemble Hydrolab measurement systems (consult appropriate manufacturer literature) prior to the pre-calibration deployment. Service of the DO subsystem for instruments equipped with a polarographic sensor (e.g., replacement of DO sensor membrane and electrolyte) should preferably precede instrument calibration by at least 24 hours. However, in the event that emergency repairs are the only available option, tests conducted near room temperature have shown that readings may be collected reliably approximately 30-45 minutes following DO probe servicing. Be sure to document the servicing of equipment (including technician name or initials, date, equipment serial number, etc.) in the equipment history records. 2. If the DO subsystem is to be air calibrated, it is recommended that the sonde be stored overnight at room temperature with the lower portion of the sonde sealed tightly in a polyethylene bag containing both room temperature air at atmospheric pressure and approximately 100-150 mL water. If DO is to be 3210.3 A-9 calibrated using a Winkler titration, a calibration container must be filled with enough water so that the DO and temperature sensors will be completely immersed when the sonde unit is placed into the container. Allow ample time for water in the calibration container to achieve thermal and gaseous equilibrium before placing the sonde inside and proceeding with calibration. When calibrating the DO probe in the field, take care to shield the calibration cup from thermal heating effects by using a sun-shield or other method of ensuring temperature stability in the calibration cup throughout the duration of the probe calibration. Attach communication and power-supply cables to the appropriate connectors for the specific instrument(s) being used and establish communication to the instrument via an appropriate software interface. 4. If the instrument has a LIS reference probe, remove and store the plastic protective storage cap and rinse away any residual KCl from the probes and sonde. 5. Record on a calibration form (Enclosure A; and/or log via calibration software) pertinent information to document the calibration, including user name(s) or initials, date, time, project description, and instrument serial numbers. B. Subsystem Pre-Sampling Calibration 1. Recommended Calibration Sequence A /% If the DO subsystem is to be air-calibrated, the measurement subsystems should be calibrated in the order listed in the left column, below. If the DO subsystem is to be Winkler-calibrated, the measurement subsystems should be calibrated in the order listed in the right column, below. Order for AIR CALIBRATION Order for WINKLER CALIBRATION DO Conductivity Conductivity Turbidity (if applicable) Turbidity (if applicable) pH pH Redox (if applicable) Redox (if applicable) Ion-selective electrode (if applicable) Ion-selective electrode (if applicable) Chlorophyll a (if applicable) Chlorophyll a (if applicable) DO Temperature Temperature Depth Depth 2. Dissolved Oxygen Calibration 2.1 The DO subsystem may be calibrated either by exposing the measuring electrode to water vapor-saturated air, or to water of known (from 3210.3 A-10 Winkler titration) DO concentration. Prior to calibration, it is critical that the instrument and the surrounding calibration medium be allowed to reach thermal and atmospheric equilibrium. Equilibrium is generally indicated when the pre-calibration DO concentrations read from the instrument become stable over time. Due to the greater potential errors associated with DO field calibration in air (section 2.2), Winkler calibration (section 2.3) is the recommended technique where calibrations are to be performed at the sampling site. 2.2 Air DO Calibration 2.2.1 The sonde must have been stored overnight indoors with the lower portion of the sonde placed and sealed tightly in a polyethylene bag containing approximately 100-150 mL water, and air at room temperature and atmospheric pressure. 2.2.2 Observe that no water droplets are adhering to the DO membrane or LDO sensor cap. If droplets are observed, they may be removed by shaking the sonde or by gently teasing them off by touching the sonde while in a horizontal orientation with the inner surface of the polyethylene bag. The sonde should be left stationary during the calibration sequence. 2.2.3 Allow sufficient time for the DO readings to stabilize (allowing the instrument to remain in this the polyethylene bag while readings are observed over 30 minutes is normally recommended). 2.2.4 Prior to calibration, obtain the unadjusted local barometric reading (in units of mm Hg). Note that the reading should not be adjusted to sea level, as most barometric readings supplied by public weather services typically are. The source for the barometric reading might be a digital barometer calibrated to a known standard, or the local public weather service reading with appropriate corrections applied for site elevation. 2.2.5 From the instrument calibration menu, select DO % Saturation (or LDO % Saturation) as the parameter to be calibrated. Enter the appropriate barometric pressure value. This will calibrate the DO subsystem to the appropriate value corresponding to 100% water-saturated air at the given temperature and partial pressure of oxygen in air. Record the adjustment, including the pre- adjustment reading, on the calibration form (electronic file or paper calibration form). Removed the plastic bag from the sonde unit at the completion of the air calibration 3210.3 A- I I 2.3 Winkler DO Calibration (See Safety, Section V) NOTE: Field temperature checks are routinely performed and documented in conjunction with the DO subsystem Winkler calibration (see III.B.6.2). 2.3.1 Attach the stirrer (if necessary for the instrument) and ensure the stirrer is functioning properly when energized. Place the instrument into a calibration container (e.g., bucket) containing equilibrated water and allow the DO reading to stabilize. 2.3.2 Perform duplicate Winkler titrations from water collected from the calibration container, as specified in Procedure 3200.X, and record both results on the calibration form. If the Winkler- determined DO concentrations agree within 0.2 mg/L, compute the average to the nearest 0.05 mg/L and record on the calibration sheet as the value to which the instrument will be calibrated. If the values do not agree within 0.2 mg/L, perform additional titrations as necessary and/or investigate potential causes relating to reagents, equipment, etc. until values within 0.2 mg/L are obtained. 2.3.3 Select DO:mg/L (or LDO:mg/L) from the calibration menu and adjust the instrument to reflect the average Winkler value. (When calibrating to a Winkler-determined concentration, it is not mandatory to change the barometric pressure software setting from the last-entered value; however, to improve the overall accuracy of DO saturation values, if their collection is desired, the actual local barometric pressure in mm Hg should be entered at the software prompt. If DO saturation values are only to be used for field reference, such as in evaluating algal distributions .! or hypoxia, an elevation-adjusted standard barometric pressure (e.g., 740 mm for most Piedmont Carolinas sites) can be entered as a default value) Consult the applicable study plan for more specifics, if any. Record the DO calibration adjustment, including the pre-adjustment reading, on the calibration form (electronic file or paper calibration form). 3. Specific Conductance Calibration 3.1 Select an appropriate NIST-traceable conductivity standard based on study plan recommendations and/or representative historical data for the locations to be monitored. The solution used to standardize the instrument should have a specific conductance greater than the maximum anticipated specific conductance during sampling. For best accuracy, standards should be near 25 °C (or at approximate room 3210.3 A-12 temperature). When monitoring a new site or a highly variable source such as a wastewater-dominated stream, a pre-calibration reading taken from a site may be helpful in ensuring that an appropriate standard will be selected. For routine water quality sampling, specific conductance standards below about 70 pS/cm are not recommended for instrument standardization due to the increased risk of error associated with their use. 3.2 Place a calibration cup onto the Hydrolab sonde. Note and record the specific conductance "zero" reading with the unwetted electrode in air. If the reading is greater than 2 µ&cm, try carefully wiping the probe dry, followed by re-checking the zero. Failure to obtain a reading near zero will require that the zero point be re-calibrated (possible on some instruments), a more involved cleaning of the probe be undertaken, and/or the parameter be reset to factory specifications. Record any actions taken. 3.3 Rinse the electrodes with three separate aliquots of an appropriate specific conductance standard, thoroughly emptying the calibration cup between rinses. 3.4 Pour the standard solution into the calibration cup, completely immersing the conductivity electrodes. Ensure that no air bubbles are trapped within the probe openings or adhering to the electrode surfaces. 3.5 Allow the specific conductance reading to stabilize and adjust the instrument to reflect the nominal value of the conductivity standard. Record the adjustment, including the pre-adjustment reading, on the calibration form (electronic file or paper calibration form). 3.6 Although no instrument adjustments should be made, additional specific conductance standards may be used to check the instrument for linearity within the measurement range. Any additional standard checks shall be recorded on the calibration form (electronic file or paper calibration form). 4. pH (2-Point) Calibration 4.1 Select an appropriate NIST-traceable pH buffer (e.g., pH 4.00 or 10.00) that along with a pH 7.00 buffer will best serve to bracket pH values anticipated at the sample site. For typical Southeastern Piedmont lakes and reservoirs, a pH 4.00 buffer is frequently suitable as a second (calibration slope adjustment) buffer; although for more alkaline waterbodies (e.g., some ash basins, or more biologically productive waterbodies) the use of a pH 10 secondary buffer is most appropriate. When monitoring a new site or a highly variable source such as a 3210.3 A-13 wastewater-dominated stream, ash basin, etc., a pre-calibration reading taken from the site may be helpful in ensuring the most appropriate selection of buffers. Following the two-point calibration, a third buffer (e. g., pH 10.00 or 4.00; whichever will not be used for to calibrate pH subsystem slope) is used to quantify pH electrode linearity outside the calibrated range. For best accuracy, buffers used for calibration should be maintained at a common temperature, within or near the range of water temperatures expected during sampling. While use of buffer nominal (25 °C) values (e.g., 7.00, 4. 00, and 10.00) is routine for laboratory calibrations, during field calibrations, the use of appropriate temperature-adjusted buffer values (see lower-right table on Enclosure A) should be used as calibration set points. 4.2 Pre-rinse the probes with two aliquots of pH 7.00 buffer, empty the calibration cup, refill to completely immerse the pH and reference probes, and allow the temperature and pH reading to stabilize. 4.3 Adjust the instrument to reflect the nominal or temperature-adjusted pH value, as appropriate, of the buffer. Record the adjustment on the calibration form (electronic file or paper calibration form). 4.4 Repeat above steps 4.2 and 4.3 using the second (pH slope setting) 4.00 or 10.00 buffer. Record the adjustment on the calibration form (electronic file or paper calibration form). 4.5 Repeat above step 4.2 using the third buffer (i.e., pH 10.00 or 4.00) and record the "as found" reading along with the nominal or temperature- adjusted pH value, as appropriate; but make no instrument adjustment. Failure of the instrument to yield a reading within 0.2 pH units of the buffer value indicates a potential problem (non-linear response) and should be investigated before proceeding with the instrument, potentially including a re-check of all buffer values. 5. Redox Calibration (See Safety, Section V) NOTE: Redox subsystem calibration method and frequency are specified in study plans where applicable. For best accuracy, control the A0 temperature of standard redox solutions per Enclosure B. 5.1 Thoroughly rinse the sensors and calibration cup with 2 aliquots of demineralized water, discarding the rinse water. 5.2 Taking care to avoid wetting the DO probe membrane with redox standard, rinse the sensors and calibration cup with a small portion of an appropriate prepared redox standard (usually a pH 4-buffered quinhydrone solution, or a commercial preparation of Zobell's solution; 3210.3 A-14 see Enclosure B or Reference C.1, respectively). Discard the rinse and refill the calibration cup with solution to a point below the top of the DO sensor. 5.3 Allow the reading to stabilize and adjust the instrument to reflect the nominal solution redox value (mV). (See Enclosure B for quinhydrone solution standard values.) Record the adjustment on the calibration form (electronic file or paper calibration form). 5.4 If checking the redox subsystem response for linearity is desired, repeat above steps 5.1 through 5.3 (without adjusting the redox value) with an alternate standard (e.g., a pH 7 buffered quinhydrone solution, or an alternate commercially available Zobell's solution; see Reference C.1). 6. Temperature Calibration Checks 6.1 General Guidance While it is generally not possible for a user to re-calibrate the temperature subsystem on Hydrolab instruments, the accuracy of the temperature subsystem is normally assessed on site with each use of the instrument. Additionally, more rigorous thermal tests at multiple temperatures are conducted annually in a laboratory controlled temperature water bath. Since temperature data are also used in internal calculations by a number of measurement subsystems, failure to discover erroneous temperature data in a timely manner may have far- reaching implications. Instruments that do not provide accuracy within 0.2 °C of an NIST-certified device during laboratory thermal bath testing shall be tagged as to clearly indicate an out-of-tolerance condition, and the instrument shall be removed from service and/or returned to the manufacturer for repair. 6.2 Temperature Calibration Check (Each-Use) NOTE: Temperature checks are routinely performed and documented in conjunction with the DO subsystem Winkler calibration (see III.B.2.3), if applicable, with each use of the instrument. A 6.2.1 Attach the stirrer (if necessary for the instrument) and ensure the stirrer is functioning properly when energized. Place the instrument into a calibration container (e.g., bucket) containing equilibrated water and allow the temperature reading to stabilize. 6.2.2 Position the sensor of an NIST-traceable thermometer or thermistor adjacent to the Hydrolab sonde-mounted thermistor, taking care to avoid contacting the stirrer. 3210.3 A-15 6.2.3 After both sensors have achieved thermal equilibrium, record the reading of each device where indicated on the calibration form (electronic file or paper calibration form). Also record the NIST- traceable device certificate number. 6.2.4 Failure of the Hydrolab to yield a reading within ±0.3 °C of the NIST-traceable device temperature indicates a potential problem with the temperature subsystem and should be investigated before proceeding with the instrument. Inability of a Hydrolab unit to achieve temperature readings within ±0.3 °C of an NIST- certified device during a field check shall require further investigation of both instruments under more carefully controlled conditions in the laboratory (i.e., temperature bath testing), as detailed in section III.F. 7. Depth Calibration NOTE: Depth calibration is not required when using a flow-through cell, but should be routinely checked, and if needed, adjusted for all other types of sampling. 7.1 While on site, place the instrument sensors in air, or into water at an independently verified depth. 7.2 Allow the depth reading to stabilize and adjust the instrument to the corresponding depth (e.g., 0.0 if sensors are in air). C. Sampling 1. General Precautions Throughout sampling, the user must remain alert and attend to appropriate diagnostic, maintenance or troubleshooting guidance if any anomalous conditions including unusual parameter responses or battery voltage drops occur. In such an event, consult the references listed in this procedure or other materials available from the instrument manufacturer. 2. Collection of Water Column Profile Data 2.1 Unless dictated otherwise in a specific study plan, water column profile data shall be collected from the water surface (typically - 0.3 m) downward to just above (i.e., 0.1 to 0.5 m above, depending on conditions) the bottom. Exceptions occur where sondes are outfitted with certain sensors that limit sampling depth due to pressure constraints on sensor operability (e.g., ammonium sensors should not be submerged below 15 meters). Each study 3210.3 A-16 plan normally specifies both the precise parameters and interval of depths to be sampled. 2.2 The DO subsystem stirrer (if present on the instrument used) should always be checked prior to initiating each water column profile. Lower the instrument sequentially to each desired sample depth, allowing all measured parameters to equilibrate prior to capturing data. 2.3 Always ensure that data has been successfully captured and saved onto electronic media, as appropriate, before continuing to the next sample location 2.4 Maintain the instrument sensors in a protected, wetted state between sample locations. On a boat, the sonde is usually placed into a bucket containing site water. During over-road transport, it is recommended that the instrument sensors be capped with the sensor storage cup partially filled with clean tap water, or site water. 3. Collection of Unattended Logging Data 3.1 To ensure the best chances for quality data, it is strongly recommended that all sonde alkaline internal batteries be replaced prior to any significant unattended deployment. For extended monitoring, general sensor maintenance should be considered, particularly the replenishment of the polarographic DO sensor electrolyte and membrane, as well as the serviceable pH reference electrode solution, as applicable for the instrument used. Sensor maintenance should be accomplished a day in advance of the pre-deployment calibration of the instruments. Inspection for proper stirrer operation (if included on the instrument) should also be made during pre- sampling maintenance and calibration. 3.2 Instruments must be programmed using instrument-specific communications software in order to log data. Programming is typically completed at the time of pre-deployment calibration. Consult the specific study plan for details, including logging file name conventions, desired parameters, log sequence start and stop dates and times, logging interval frequency, instrument warm-up, stirrer activation interval setting, and deployment location(s) and depth(s). 3.3 During transport to the field location and up until the time that instruments are actually deployed, handle sondes with extreme care to prevent unnecessary physical trauma that might increase the risk of drift from initial calibration set points. Precautions include preventing exposure of sonde units to physical shock or temperature extremes. 3210.3 A-17 3.4 Upon retrieval from the field site, instrument calibration may be checked at that time, (recommended if practical, especially for the DO subsystem) or may be stored for subsequent calibration checks in the lab, or some combination thereof. Post-monitoring calibration checks, whether performed in the field or in the lab, must be completed prior to initiating maintenance or cleaning of the instrument sensors. Consult the specific project study plan for guidance. 4. Collection of Data using a Flow-Through Cell 4.1 Some applications such as routine groundwater monitoring may require the use of a flow-through cell. A flow-through cell replaces the sensor guard on an instrument and incorporates inflow and discharge ports. This set up is designed for pumping water continuously into a flow cell to completely immerse the sensors. 4.2 When using a flow-through cell, the water should inflow at the bottom of the cell, with the discharge near the top of the cell. The sonde should be oriented in an upright position (sensors down) to allow the displacement of any air bubbles from the flow cell. It is important to visually check the specific conductivity sensor to ensure air bubbles are not present. 4.3 If dissolved oxygen is being measured using a flow through cell, the stirrer (for polarographic electrode-equipped instruments) should be activated. 4.4 Typically, when using a flow-through cell, the stabilization of parameters will be noted after a given elapsed time or flow-through volume. Specific study plans should be consulted to determine if readings are to be taken only after specific time intervals or after a pre-defined volume of water (such as a multiple of calculated well volume) has been pumped through the cell. D. Post- and Intermediate Sampling Calibration NOTE: A post-sampling calibration may not be required in limited circumstances where all Hydrolab data collection is completed within a very short duration (e.g., less than one hour) following the initial in-field calibration and sampling commenced immediately following field calibration of the instrument. Consult the applicable study plan for further guidance on post-sampling calibration requirements. Except as described immediately above, following the completion of sampling, a post-sampling check of all standards used in the pre-sampling calibrations shall be made and documented. Generally, the actual re-adjustment of instrument parameters to the calibration standard values is omitted from the post-sampling calibration check. Otherwise, the post-sampling calibration shall proceed as outlined in section III.B. Record the final calibration standard values and the 3210.3 A-18 instrument readings on the calibration form (electronic file or paper calibration form). A general summary of post- and intermediate calibration tolerances for Hydrolab parameters is provided in Enclosure D. Specific study plans may also address modifications to these general specifications. 2. When a sampling effort spans a substantial span of time (e.g., a full day), it is recommended that sampling be periodically suspended so that one or more intermediate calibrations may be performed on the instrument. Intermediate calibration(s) can be useful in ascertaining that the instrument continues to provide accurate data. Any additional specifics regarding the need for intermediate calibrations shall be detailed in specific study plans. Record the intermediate calibration standard values and the instrument readings, along with any needed re-adjustments to calibration standard values on the calibration form (electronic file or paper calibration form). 3. If instruments were stored after data logging or sampling for a subsequent lab calibration check, take extreme precaution to prevent exposure of the sonde units to physical shock or temperature extremes. Where units have been retrieved following a data logging deployment, it is recommended the sensor storage cup be filled with only about 1 cm water during return transport in order to preclude excessive washing of biofilms from the sensors (particularly the DO sensor) during travel (which might substantially alter the final calibration check offsets). E. In-Field Hydrolab Electronic Data Management 1. Provide each electronically saved data capture file with a unique file name in accordance with data management guidelines and procedures, ensuring that existing data are not overwritten. 2. Data shall be backed up while on site. The backup process shall require that a second copy of data capture files is written to electronic media so that the data exist in two physical locations, e.g., on PC hard drive as well as on removable media such as a diskette or USB "flash" or "jump" drive. 3. Prior to disconnecting the instruments from the computer during field collections, always ensure the integrity of saved data files. F. Annual Temperature Checks NOTE: Hydrolab temperature subsystems shall be tested, at a minimum, annually in the laboratory under controlled conditions, as described below. Normally, a number of Hydrolabs are tested sequentially at each water bath temperature setting. 1. Set up a circulating precision temperature water bath, thermally controlled to provide one of the testing temperatures listed on Enclosure C. Set up the Hydrolab for data collection and immerse both the Hydrolab sonde unit thermistor 3210.3 A-19 and an NIST-traceable temperature device (certified thermometer or thermistor) in the water bath. 2. After allowing adequate time for the bath and both instruments to achieve thermal equilibrium, record the thermal test data from both the NIST-traceable device and the Hydrolab. Be sure to apply any know temperature corrections to the data from the NIST-certified device. From the two readings, determine and record the offset of the Hydrolab from the NIST device reading. Repeat the process for other Hydrolab instruments, as needed. 3. Re-set the temperature bath to another test temperature (see Enclosure 3) and repeat the above steps 1 and 2 until all instruments and have been evaluated at each indicated test temperature. 4. Failure of a Hydrolab to consistently yield readings within ±0.2 °C of the NIST- traceable device temperature under controlled water bath conditions indicates a problem with the temperature subsystem. In this event (multiple measurements out of tolerance), the instrument should be tagged and not used further until it can be repaired at the factory. Hydrolabs not meeting the ±0.2 °C criterion at a single temperature at either extreme of the tested temperature range shall be clearly tagged to advise any potential users of the finding. Such instruments may be used, as necessary, on a restricted basis, in circumstances where the anticipated out-of-tolerance temperature will not be encountered. Thermal testing data shall be reviewed so that any potential impacts to prior monitoring using a non- conforming instrument can be evaluated. G. Instrument Maintenance and Storage 1. Avoid the practice of placing demineralized or ultra-pure water in the sensor storage cup during storage, as this serves to reduce the useful life of the reference electrode. For extended storage, addition of pH 4 buffer solution to the storage cup is recommended in order to both lengthen the serviceability of the pH measuring subsystem, and to retard the growth of biological films on the sensors. 2. For instruments to be stored long-term, all alkaline batteries should be removed to prevent potential damage to the sonde interior. 3. Senor caps on LDO probes should be replaced routinely every 12 months. Ideally, replacement should be performed and documented at the time other routine scheduled maintenance and testing is performed. 4. Internal sonde DO polarizing and calendar/clock batteries require periodic replacement, depending to some degree on usage patterns of each instrument. It is recommended that these internal batteries be replaced at least once every 2 years. Also, internal desiccants should be inspected and if necessary, replaced, at the time internal batteries are accessed. Consult manufacturer specifications for 3210.3 A-20 battery types, and record internal battery or desiccant replacements in the instrument maintenance records. QUALITY CONTROL A. Personnel must confirm that calibration standard solutions have not exceeded their shelf life prior to use. B. It is strongly recommended that historical, seasonal Hydrolab water quality data (data listings and/or graphics) for the site(s) being sampled be available for comparative purposes, as necessary, during the data collection process. C. When using low-flow sampling for groundwater, the use of ProfilerTM, Hydras 3 LT, (or an equivalent real-time graphical trending software package) is recommended. D. A project scientist shall be notified of, and shall evaluate circumstances where any calibration criteria were not met (see Enclosure D), including the need to re-sample sites or locations and disposition of any data collected. V. SAFETY A. Several reagents used to calibrate the various Hydrolab measurement subsystems present various chemical-specific hazards, including contact hazards (quinhydrone), and corrosivity (sulfamic acid). The applicable Material Safety Data Sheets (referenced via Duke MSDS.net; see section II.B) for each reagent should be consulted prior to handling any chemical, and proper personal protective gear shall be available for use. B. The sampling crew should be familiar with and adhere to the guidelines outlined in the Duke Power Safe Work Practices manual, with particular reference to the sections on: • Water safety • Vehicle safety • Hazardous materials VI. ENCLOSURES A. Enclosure A - Example of a Field Sampling Calibration Data Form B. Enclosure B - Preparation of Quinhydrone Calibration Standards for Redox Subsystem C. Enclosure C - Example of a Form Used to Document Annual Temperature Bath Hydrolab Thermal Testing 3210.3 A-21 D. Enclosure D - General Hydrolab Calibration Acceptance Criteria Parameter Standard Calibration Acceptance Criteria Temperature NIST-traceable device Each use on-site comparison: ±0.3 °C of certified device temperature Annual temperature bath comparison: ±0.2 °C of certified device temperature DO Azide-modified Winkler ±0.2 mg/L of average Winkler value Specific NIST-traceable KCl standard ±5% of standard value Conductance pH NIST-traceable buffers ±0.2 pH units of buffer value ?A Y 4? l ?O 4 3210.3 A-22 Enclosure A. Example of a Field Sampling Calibration Data Form FIELD SAMPLING CALIBRATION DATA FORM STUDY: DATE(S): WEATHER CONDITIONS: COLLECTORS: SURFACE UNIT READER: HYDROLAB SERIAL #: COMPUTER: OTHER EQUIPMENT: ? Peristaltic pump ? SS bucket SURVEYOR SERIAL #: ? Kemmerer ? Van Dorn Procedure Number 3210-3 Calibration Time Date: Time Date: Time Date: Time (DO Air Calibration) Instrument Maintenance Barometric. Press mmHg mmHg Temperature Subsystem Parameter Calib. Std. Instrument Standard Value Value Instrument Standard Value Value ? Cleaned Thermistor ? Tested - OK ? See Notes Temp Device Ce No. rt. DO Subsystem ? Replaced Teflon Membrane TEMP NIST / -- > / -- > ? Replaced DO Electrolyte (deg C) NIST / -- > / -- > ? Cleaned Electrodes ? Tested - OK ? See Notes DO (mg/1) W W AW > > pH Subsystem ? Cleaned Electrodes ? Replaced Ref. Electrode KCI ? Replaced Ref. Electrode Tip pH B - 7.0 > > ? Tested - OK ? See Notes (units) B > > Conductance Subsystem B > > ? Cleaned Electrodes ? Tested - OK ? See Notes SP COND SS > 0.00 > 0.00 ORP Subsystem (us/cm) SS > > ? Cleaned Electrode SS > > ? Tested - OK ? See Notes Turbidity Subsystem ORP SS > > ? Cleaned Electrode & Wiper (mV) SS > > ? Tested - OK ? See Notes Ammonium Subsystem TURBIDITY SS > 0.00 > 0.00 ? Cleaned Electrode Tip (ntu) SS > > ? Installed New Electrode ? Removed Electrode / Installed Plug AMMONIUM SS > 5.00 > 5.00 ? Tested - OK ? See Notes (mg/L) SS > 50.00 > 50.00 Depth Subsystem ? Reset/Cal. ? See Notes KEY: B = Buffer W = Winkler NA = Not Applicable SS = Standard Solution AW = Average Winkler -- -- > = Adjusted To -- / -- > = Not Adjusted To 1 0 5 4.01 3.99 7.13 10.34 7.10 10.26 10 15 4.00 3.99 7.07 10.19 7.05 10.12 20 25 4.00 4.00 7.02 10.06 _ 7.00 10.00 30 4.01 6.99 9.94 35 4.02 6.98 9.90 40 4.03 6.97 9.85 Buffer corrections from Fisher Scientific 3210.3 A-23 Enclosure B. Preparation of Quinhydrone Calibration Standards for Redox Subsystem Redox Standard Preparation MV at 20°C (for Ag/AgCI Electrodes MV at 25°C (for Ag/AgCI Electrodes Dissolve 2 g/L pH Buffer 7.0 Solution quinhydrone into 1000 ML 92 86 NIST-traceable pH 7.0 buffer Dissolve 2 g/L pH Buffer 4.0 Solution quinhydrone into 1000 ML 268 263 NIST-traceable pH 4.0 buffer 7 ?O 4 2 Quinhydrone calibration standards must be saturated solutions (i.e., must include undissolved reagent). Although ASTM standard D1498 (see Reference 1. C.2) specifies the solutions be prepared from 8 g quinhydrone per liter, Hydrolab recommendations and past experience has demonstrated that reliable, saturated quinhydrone redox standard solutions can be prepared using 2 g/L. 3210.3 A-24 Enclosure C. Example of a Form Used to Document Annual Temperature Bath Hydrolab Thermal Testing Hydrolab Datasonde Temperature Calibration Records Hydrolab Water Bath Hydrolab Certified Serial Hydrolab Calibrated Temperature Temperature Temperature Operator Certified Number Model Due Date Date (°C) (°C) (°C) Offset (°C) Notes Initials Device ID 14847 DS3 Jan-07 1/5/2007 5.0 4.76 4.96 -0.20 GAL 4124 14847 DS3 Jan-07 1/5/2007 12.5 12.40 12.60 -0.20 GAL 4124 14847 DS3 Jan-07 1/5/2007 25.0 25.50 25.46 0.04 GAL 4124 14847 DS3 Jan-07 1/5/2007 32.0 32.13 32.07 0.06 GAL 4124 14847 DS3 Jan-07 1/5/2007 40.0 39.91 39.84 0.07 GAL 4124 19859 DS3 Jan-07 1/5/2007 5.0 4.80 4.95 -0.15 GAL 4124 19859 DS3 Jan-07 1/5/2007 12.5 12.48 12.60 -0.12 GAL 4124 19859 DS3 Jan-07 1/5/2007 25.0 25.39 25.42 -0.03 GAL 4124 19859 DS3 Jan-07 1/5/2007 32.0 32.07 32.10 -0.03 GAL 4124 19859 DS3 Jan-07 1/5/2007 40.0 39.96 39.94 0.02 GAL 4124 22261 DS3 Jan-07 1/5/2007 5.0 4.74 4.94 -0.20 GAL 4124 22261 DS3 Jan-07 1/5/2007 12.5 12.83 12.58 0.25 Within additive test tolerance GAL 4124 22261 DS3 Jan-07 1/5/2007 25.0 25.32 25.45 -0.13 GAL 4124 22261 DS3 Jan-07 1/5/2007 32.0 32.02 32.11 -0.09 GAL 4124 22261 DS3 Jan-07 1/5/2007 40.0 39.89 39.94 -0.05 GAL 4124 34785 DS4 Jan-07 1/5/2007 5.0 4.94 4.95 -0.01 GAL 4124 34785 DS4 Jan-07 1/5/2007 12.5 12.61 12.60 0.01 GAL 4124 34785 DS4 Jan-07 1/5/2007 25.0 25.43 25.44 -0.01 GAL 4124 34785 DS4 Jan-07 1/5/2007 32.0 32.06 32.08 -0.02 GAL 4124 34785 DS4 Jan-07 1/5/2007 40.0 39.94 39.94 0.00 GAL 4124 34786 DS4 Jan-07 1/5/2007 5.0 5.11 4.95 0.16 GAL 4124 34786 DS4 Jan-07 1/5/2007 12.5 12.73 12.60 0.13 GAL 4124 34786 DS4 Jan-07 1/5/2007 25.0 25.32 25.41 -0.09 GAL 4124 34786 DS4 Jan-07 1/5/2007 32.0 32.08 32.09 -0.01 GAL 4124 34786 DS4 Jan-07 1/5/2007 40.0 34.93 34.94 -0.01 GAL 4124 38273 DS4a Jan-07 1/19/2007 5.0 4.66 4.80 -0.14 GAL 4124 38273 DS4a Jan-07 1/19/2007 12.5 12.50 12.39 0.11 GAL 4124 38273 DS4a Jan-07 1/19/2007 25.0 24.98 24.95 0.03 GAL 4124 38273 DS4a Jan-07 1/19/2007 32 0 31 92 31 87 0 05 GAL 4124 . . . . 38273 DS4a Jan-07 1/19/2007 40.0 40.02 39.94 0.08 GAL 4124 38274 DS4a Jan-07 1/5/2007 5.0 4.86 4.95 -0.09 GAL 4124 38274 DS4a Jan-07 1/5/2007 12.5 12.47 12.59 -0.12 GAL 4124 38274 DS4a Jan-07 1/5/2007 25.0 25.38 25.45 -0.07 GAL 4124 38274 DS4a Jan-07 1/5/2007 32.0 32.02 32.09 -0.07 GAL 4124 38274 DS4a Jan-07 1/5/2007 40.0 39.92 39.93 -0.01 GAL 4124 38701 MiniSond Jan-07 1/4/2007 5.0 4.77 4.93 -0.16 GAL 4124 38701 MiniSond Jan-07 1/4/2007 12.5 12.26 12.40 -0.14 GAL 4124 38701 MiniSond Jan-07 1/4/2007 25.0 25.09 25.14 -0.05 GAL 4124 38701 MiniSond Jan-07 1/4/2007 32.0 32.09 32.10 -0.01 GAL 4124 38701 MiniSond Jan-07 1/4/2007 40.0 39.74 39.73 0.01 GAL 4124 38702 MiniSond Jan-07 1/4/2007 5.0 4.74 4.94 -0.20 GAL 4124 38702 MiniSond Jan-07 1/4/2007 12.5 12.28 12.39 -0.11 GAL 4124 38702 MiniSond Jan-07 1/4/2007 25.0 25.09 25.14 -0.05 GAL 4124 38702 MiniSond Jan-07 1/4/2007 32.0 32.07 32.13 -0.06 GAL 4124 38702 MiniSond Jan-07 1/4/2007 40.0 39.70 39.72 -0.02 GAL 4124 39032 DS4a Jan-07 1/19/2007 5.0 4.89 4.78 0.11 GAL 4124 39032 DS4a Jan-07 1/19/2007 12.5 12.35 12.36 -0.01 GAL 4124 39032 DS4a Jan-07 1/19/2007 25.0 24.91 24.98 -0.07 GAL 4124 39032 DS4a Jan-07 1/19/2007 32.0 31.91 31.87 0.04 GAL 4124 39032 DS4a Jan-07 1/19/2007 40.0 39.97 39.87 0.10 GAL 4124 39033 DS4a Jan-07 1/19/2007 5.0 4.72 4.79 -0.07 GAL 4124 39033 DS4a Jan-07 1/19/2007 12.5 12.27 12.38 -0.11 GAL 4124 39033 DS4a Jan-07 1/19/2007 25.0 24.98 24.98 0.00 GAL 4124 39033 DS4a Jan-07 1/19/2007 32.0 31.81 31.87 -0.06 GAL 4124 39033 DS4a Jan-07 1/19/2007 40.0 39.96 39.90 0.06 GAL 4124 3210.3 A-25 Enclosure D. General Hydrolab Calibration Acceptance Criteria3 Parameter Standard Calibration Acceptance Criteria Temperature NIST-traceable device Each use on-site comparison: ±0.3 °C of certified device temperature Annual temperature bath comparison: ±0.2 °C of certified device temperature DO Azide-modified Winkler ±0.2 mg/L of average Winkler value Specific NIST-traceable KCl standard ±5% of standard value Conductance pH NIST-traceable buffers ±0.2 pH units of buffer value 7*7 04 ' The general calibration acceptance criteria shown are based on manufacturer specifications and may in special cases be modified by study plan-specific criteria. Consult the applicable study plan for further details. 3210.3 A-26 APPENDIX B-QAPP Example Quality Control Chart Demonstrating Oxygen Sensor Drift Example Quality Control Chart used to evaluate the performance of the deployed tailrace monitor Tailrace Monitor Quality Control Chart _ 1.00 6) E 0 0 T 0.50 0 Q 0 m 0 E 0.00 0 .m -0.50 3 m 0 U C N N 1.00 t Mean - m Upper Precision Limit - - Lower Precision Limit ? Monitor Replacement ,70 , 7S, 10 , ?S "O, vs 9,s ?g 79, ?v, 19 'S, , 94 94 94 94 94 eQ eQ Se e Se S'e 9?8 9?8 9?8 9?8 9?8 06 019 X 08 X 08 X 08 X 08 Date B-1 APPENDIX C-QAPP Supplemental Trout Habitat Monitoring Bridgewater Development Supplemental Trout Habitat Monitoring The Catawba River Bypassed Reach and Bridgewater minimum continuous flows have been selected and evaluated to provide flows and water temperatures suitable for protection and enhancement of mussels in the bypassed reach and the maintenance of a stocked trout fishery downstream of Bridgewater Hydro. The volume of warm water flows provided to the Catawba River Bypassed Reach to maintain mussel habitat are balanced against the coldwater minimum flow from the Linville Dam to maintain suitable temperatures for trout downstream of the confluence of the Catawba River Bypassed Reach and the Linville River. The flows and temperatures provided to each channel to achieve the desired, but conflicting temperature requirements were analyzed by the CE-QUAL-W2 reservoir model and the River Modeling System (RMS). The results of these computer models were evaluated by the Aquatics/Terrestrial and Water Quality Resource Committees. Bypassed Reach and Linville Dam minimum continuous flows stated in the CRA are the result of the recommendations from the evaluations by the resource committees. Monitoring Due to the hydraulic complexity and apparent conflicts of resource management interests (differing trout and mussel temperature preference) in this area, supplemental monitoring will be used to support future evaluations of whether trout management goals in the main stem Catawba River continue to be supported. This supplemental trout habitat monitoring will commence after the Bridgewater Powerhouse has been replaced with either a new powerhouse or valve system and compliance operations have begun. This measurement and evaluation will continue through the next cycle of NCDWQ Catawba River Basinwide Assessment period, but not beyond Year 2019. Results of this monitoring are not intended to be used for water quality certification compliance purposes, but for continued aquatic resource assessments. These monitoring results may be used to determine if now reductions need to be made in the Catawba River Bypassed Reach. Sensor Locations The temperature and level logger placement is designed to be able to record temperatures, flow (level logger with stage-discharge relationship) from the inflows, and empirically determine the temperatures at the appropriate downstream river reaches. An additional temperature and level logger will be provided at the Watermill Bridge (RM 271.7) in Glen Alpine, NC which is in the middle of the primary trout habitat. C-1 Bridgewater Supplemental Trout Habitat Monitoring System Requirements Level loggers (devices to record river stage from which a stage-discharge relationship may be developed to calculate flow) and temperature loggers will be placed in the river and periodically downloaded to obtain the respective data. Stage-discharge curves will be developed at the level logger sites. Reporting Requirements Annual reports will be provided to NCDWQ and NCWRC (30 April) for the duration of the supplemental trout habitat monitoring detailing the previous calendar year's temperatures and levels. Flow-weighted temperatures will be calculated for the downstream sites. C-2