20070812 Ver 2_AIR Response_20090309

HUNTON HUNTON & WILLIAMS LLP
POST OFFICE BOX 109
WHIIAMS
RALEIGH, NORTH CAROLINA 27602
TEL 919 •899.3000
FAX [phone]
CRAIG A. BROMBY
DIRECT DIAL: 919-899-3032
EMAIL: [e-mail]
March 9, 2009 FILE NO: 65215.000006
DOC NO: 26929035.V4

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John R. Dorney
Wetland Program Development Unit
Division of Water Quality
Parkview Building
2321 Crabtree Blvd.
Raleigh, NC 27604
Re: Response to Additional Information Request - Items 2, 3, 4, 6, and 7
401 Water Quality Certification -- APGI Yadkin Project
DWQ #2007-0812 version 2
Davidson, Rowan, Montgomery and Stanly Counties
Dear Mr. Dorney:
Alcoa Power Generating Inc. ("APGI") offers the following responses to items outlined in the
February 24, 2009, request by the Division of Water Quality ("DWQ") for additional
information. The items in the additional information request will be referred to as AIRS,
numbered to correspond with the February 24 letter.
AIR #1 - Dissolved oxygen sag - Commenters from the public hearing have asked whether
sufficient sampling is being done or is being planned (after turbine upgrades) along river
transects below the dams to detect any DO sag which may reduce the effectiveness of turbine
improvements. Please clarify where DO samples were taken and are planned to be taken
downstream of the dams to address this issue.
APGI is still compiling data and information in response to this request, and will respond to
this AIR in a separate submittal.
AIR #2 - As you know, the Department of Health and Human Services has released their recent
study offish tissue analysis for PCBs in Badin Lake. In order to address whether these
HLNTON
WUIJAMS
John R. Dorney
March 9, 2009
Page 2
concentrations of PCBs are related to a discharge, staff of the Division of Solid Waste
Management in DENR will be comparing congeners of the PCBs in sediment found at the old
Alcoa site. Unitl this analysis is done, this information is not available for the director's
decision and therefore the application will remain on hold until that information is available
and DWQ has the opportunity to review it in the context of our 401 Water Quality Certification
decision.
It is APGI's understanding that no information is being requested which is in APGI's custody
or control. However, APGI notes that concentrations of PCB in fish tissue in Narrows
Reservoir are unrelated to the discharge, and not necessary to the Director's decision. PCBs
are ubiquitous in the environment and are especially prevalent in the more developed portions
of the watershed. For example, fish tissue sample collection by DWQ in September 2004 near
Mocksville in the Yadkin River showed PCB levels comparable to those measured in the most
recent sampling undertaken in Narrows Reservoir, demonstrating that PCB levels in fish tissue
upstream of the Yadkin Project do not vary significantly from PCB levels in fish tissue in
Project reservoirs.I
The fact that PCBs have been detected in very low concentrations in sediments in the Narrows
Reservoir near Alcoa Inc.'s Badin Works does not signify PCB contamination of the discharge
from the Narrows Dam from those sediments. PCBs apparently can also be found in sediments
in other parts of the reservoir and in sediments upstream of the reservoirs.2
i For reasons that are unclear and unexplained, the Department of Health and Human
Services elected not to issue a fish consumption advisory based on the 2004 sampling event,
but did issue such an advisory in 2008 based on similar results from samples taken from the
2008 sampling event in Narrows Reservoir.
2 Furthermore, the analytical methodology utilized in the 2008 fish tissue data
collection is significantly more sensitive than analytical methodology used for previous data
collections. The method had lower limits of detection and analyzed for a broader range of
congeners. Values for total PCBs included all congeners reported instead of limiting the total
to the narrower range of aroclors reported under the previous methodology, thereby inflating
reported values. Additionally, the fish tissue consumption advisory was issued based on values
measured in individual specimens, and not, as was previously the policy of the Department of
Health and Human Services ("DHHS"), issued on an average of all individuals within the same
species. In other words, the fish tissue consumption advisory for the Narrows Reservoir was
issued using significantly more stringent guidelines than previously relied upon by the DHHS.
HUNTON
WILLIAMS
John R. Dorney
March 9, 2009
Page 3
Moreover, APGI and Alcoa Inc. are separate corporate entities. APGI is not liable for any
environmental cleanup obligations that the sediments near the Badin Works may impose on
Alcoa Inc. any more than it is liable for obligations in connection with mercury which may be
found in sediments near the Duracell plant upstream of the High Rock Reservoir, or nutrient
loadings from upstream wastewater treatment plants. Any obligations relating to the sediments
near Alcoa's Badin Works are addressed by a sister agency of DWQ in DENR to Alcoa Inc.,
and it is inappropriate and outside the scope of the 401 Certification to try to impose them in a
401 Certification issued to APGI.
AIR #3 - As you know, the division plans to conduct some water and sediment sampling from
the discharges from the dams. Until that sampling is done and analyzed, that information is
also not available to the director and the application will remain on hold until that information
is available and DWQ has the opportunity to review it in the context of our 401 Water Quality
Certification decision.
With respect to AIR #3, APGI also understands that no information or data is being requested
from APGI. However, APGI notes in this regard that the data being sought in DWQ's
proposed water and sediment sampling is duplicative of data already submitted to DWQ, at
DWQ's request. Therefore, it is not accurate to claim that the information is not available to
the Director, irrespective of whether it is necessary to the Director's decision. There has been
no supportable contention that the data submitted by APGI are not accurate. In fact, details on
the methodology used are included with this submittal. APGI does not object to DWQ's
collection of data in this regard, nor to splitting samples with opponents of the Project, but it
wishes to note for the record that the data requested is already within the possession of DWQ,
so it cannot fairly be characterized as information necessary to the Director's decision which is
unavailable.
AIR #4 - A question has arisen during the review of the water sample from Badin Lake
discharge as to how the water sample was handled for processing after the sample was taken.
Please clarify how the sample was handled during preservation and provide documentation on
sample preparation.
Sample Collection
Narrows discharge sampling was conducted in accordance with a sampling plan that was
approved by DWQ in a letter dated July 31, 2008. Sampling was conducted on August 13,
2008. Sample bottles were received from Columbia Analytical Services (CAS) and Prism
Laboratories, and the coolers were opened to inspect the conditions of the sample bottles, to
ensure they were double-bagged, and to take inventory. The coolers were then re-sealed and
left untouched until samples were collected on August 13, 2008.
HIINTON
WII.LIAMS
John R. Dorney
March 9, 2009
Page 4
Upon reaching the Narrows tailrace, metals sampling, including mercury, was conducted in
accordance with EPA Method 1669 (Clean Hands/Dirty Hands - Appendix A), while all other
samples were collected using a grab sampling technique. All samples were taken facing
upstream. For metals sampling, the "clean hands" sampler, the only one allowed to touch the
sample bottles and the inside bag, collected samples by rapidly submerging the bottles into the
water. For those sample bottles that were pre-preserved, clean, unpreserved bottles provided
by the laboratories were used as grab sampling devices. Upon collection, the samples were
immediately transferred to the proper sample bottles. Because no preservatives were used for
the mercury, SVOC, and PCB samples, the sample bottles were directly submerged into the
water.
After each metals sample was taken, the "clean hands" sampler carefully placed the bottle
within the inside bag and sealed it, and then the "dirty hands" sampler sealed the outer bag and
immediately placed the sample in a cooler. After the metals samples were collected and
handled according to EPA Method 1669 (including field blanks), and all other samples were
collected, additional ice was added to the coolers, which were then sealed and then shipped to
the contract laboratories the next morning. Samples were received by the laboratories within
prescribed hold times and within acceptable temperature ranges.
Sample Preservation and Analysis
Two laboratories were contracted to analyze the Narrows discharge samples: Prism
Laboratories conducted the mercury analysis, while Columbia Analytical Services (CAS)
conducted the VOC, SVOC, metals, and PCB analyses. Both laboratories provided the sample
bottles to AECOM. For those analyses that required preservation, CAS provided pre-preserved
bottles (metals samples required nitric acid and VOCs required hydrochloric acid). Mercury
sample bottles were not pre-preserved because the samples were oxidized within the sample
bottles using bromine chloride and as such, did not require preservation for 28 days (Appendix
B). For these analyses, neither the field crew, CAS nor Prism Laboratories filtered any of
the samples.
To analyze samples for metals and trace elements by inductively coupled-mass spectrometry
(ICP-MS), CAS used EPA Method 200.8 (Appendix Q. Samples were preserved in the field
with nitric acid, and further prepared/digested in accordance with method 3020A (Appendix
D).
For PCB analysis, CAS analyzed the samples in accordance with EPA Method 608 (Appendix
E), while SVOCs were analyzed using EPA Method 625 (Appendix F). Both these analytes
were prepared using method 3520 (Appendix G) which dictates that samples be stored at 4±2
°C, extracted within 7 days of sampling, and the extracts analyzed within 40 days of extraction.
HiINTON
Wfi T.TAMS
John R. Dorney
March 9, 2009
Page 5
VOC samples were analyzed and preserved according to EPA Method 624 (Appendix H). The
samples were preserved with hydrochloric acid and upon receipt, were stored on ice and
analyzed within 14 days of the sample collection date.
Prism Laboratories, Inc. was contracted to perform mercury analyses in aqueous samples
collected from the Narrows discharge using EPA Method 1631E (Appendix B). The analysis
for total mercury allows for no preservation up to 28 days because samples were oxidized with
bromine chloride.
AIR #S - Please provide data and a map showing all known locations of PCBs at the Alcoa site
and in the nearby cove of Badin Lake.
APGI is working with Alcoa staff to compile the requested data and maps, and will respond to
this AIR in a separate submittal.
AIR #6 - Please provide copies of the lab sheets for the sediment sampling in Badin Lake.
The requested lab sheets for sediment sampling that was conducted by URS and reported in
February 2009 are provided on the enclosed CD.
AIR #7 - Please provide copies of the 2007 and 2008 dissolved oxygen data that you reference
in your response to the public hearing.
Continuous dissolved oxygen (DO) and temperature data collected by APGI between May and
November of 2007 and 2008 in both the Narrows and Falls tailwaters are provided on the
enclosed CD.
AIR #8 Please address the following questions related to the discharge sampling from Badin
lake -
a. What was the depth of the water withdrawal from the lake when the sample was taken?
b. What is the approximate zone of influence from the withdrawal? In other words when
the sample was taken, what is your estimate of the area from which the water was being
withdrawn?
c. What is the depth of sediment that has accumulated at the dam and what are it's
characteristics with respect to approximate particle sizes?
APGI is still compiling data and information in response to this request and will respond in a
separate filing.
HUNTON
WHLJAMS
John R. Dorney
March 9, 2009
Page 6
In closing, we would reiterate that APGI considers some of the information requested in the
AIRs as irrelevant to the current proceeding. We also note that DWQ's proposed additional
sampling is identical to what was already conducted by APGI at DWQ's request, and the data
from this sampling have already been submitted to DWQ. APGI is still gathering or
developing information in response to AIRs #1, 5, and 8. APGI will deliver its responses
covering these items in a separate letter that will be filed with DWQ on or before March 17,
2009. APGI will endeavor to deliver responsive information as it is gathered and developed in
order to facilitate and expedite your review of the information requested.
Please feel free to contact me with any questions or comments.
Sincerely yours,
Craig A. Bromby
CAB/psb
Enclosures
cc: Gene Ellis
Coralyn Benhart
David R. Poe
4. A question has arisen during the review of the water sample from the Badin Lake
discharge as to how the water sample was handled for processing after the sample was
taken. Please clarify how the sample was handled during preservation and provide
documentation on sample preparation.
Sample Collection
Narrows discharge sampling was conducted in accordance with a sampling plan that was
approved by DWQ in a letter dated July 31, 2008. Sampling was conducted on August
13, 2008. Sample bottles were received from Columbia Analytical Services (CAS) and
Prism Laboratories and the coolers were opened to inspect the conditions of the sample
bottles, to ensure they were double-bagged, and to take inventory. The coolers were then
re-sealed and left untouched until samples were collected on August 13, 2008.
Upon reaching the Narrows tailrace, metals sampling, including mercury, was conducted
in accordance with EPA Method 1669 (Clean Hands/Dirty Hands - Appendix A), while
all other samples were collected using a grab sampling technique. All samples were
taken facing upstream. For metals sampling, the "clean hands" sampler, the only one
allowed to touch the sample bottles and the inside bag, collected samples by rapidly
submerging the bottles into the water. For those sample bottles that were pre-preserved,
clean, unpreserved bottles provided by the laboratories were used as grab sampling
devices. Upon collection, the samples were immediately transferred to the proper sample
bottles. Because no preservatives were used for the mercury, SVOC, and PCB samples,
the sample bottles were directly submerged into the water.
After each metals sample was taken, the "clean hands" sampler carefully placed the bottle
within the inside bag and sealed it, and then the "dirty hands" sampler sealed the outer
bag and immediately placed the sample in a cooler. After the metals samples were
collected and handled according to EPA Method 1669 (including field blanks), and all
other samples were collected, additional ice was added to the coolers which were then
sealed and then shipped to the contract laboratories the next morning. Samples were
received by the laboratories within prescribed hold times and within acceptable
temperature ranges.
Sample Preservation and Analysis
Two laboratories were contracted to analyze the Narrows discharge samples: Prism
Laboratories conducted the mercury analysis, while Columbia Analytical Services (CAS)
conducted the VOC, SVOC, metals, and PCB analyses. Both laboratories provided the
sample bottles to AECOM. For those analyses that required preservation, CAS provided
pre-preserved bottles (metals samples required nitric acid and VOCs required
hydrochloric acid). Mercury sample bottles were not pre-preserved because the samples
were oxidized within the sample bottles using bromine chloride and as such, did not
require preservation for 28 days (Appendix B). For these analyses, neither the field crew,
CAS nor Prism Laboratories filtered any of the samples.
To analyze samples for metals and trace elements by inductively coupled-mass
spectrometry (ICP-MS), CAS used EPA Method 200.8 (Appendix Q. Samples were
preserved in the field with nitric acid, and further prepared/digested in accordance with
method 3020A (Appendix D).
For PCB analysis, CAS analyzed the samples in accordance with EPA Method 608
(Appendix E), while SVOCs were analyzed using EPA Method 625 (Appendix F). Both
these analytes were prepared using method 3520 (Appendix G) which dictates that
samples be stored at 4±2 °C, extracted within 7 days of sampling, and the extracts
analyzed within 40 days of extraction.
VOC samples were analyzed and preserved according to EPA Method 624 (Appendix H).
The samples were preserved with hydrochloric acid and upon receipt, were stored on ice
and analyzed within 14 days of the sample collection date.
Prism Laboratories, Inc. was contracted to perform mercury analyses in aqueous samples
collected from the Narrows discharge using EPA Method 1631E (Appendix B). The
analysis for total mercury allows for no preservation up to 28 days because samples were
oxidized with bromine chloride.
Appendix A
EPA Method 1669
Method 1669
Sampling Ambient Water for Trace Metals at EPA Water Quality
Criteria Levels
July 1996
U.S. Environmental Protection Agency
Office of Water
Engineering and Analysis Division (4303)
401 M Street S.W.
Washington, D.C. 20460
Method 9669
Acknowledgments
This sampling method was prepared under the direction of William A. Telliard of the Engineering and Analysis
Division (EAD) within the U.S. Environmental Agency's (EPA's) Office of Science and Technology (OST).
This sampling method was prepared under EPA Contract 68-C3-0337 by the DynCorp Environmental
Programs Division, with assistance from Interface, Inc.
The following researchers contributed to the philosophy behind this sampling method. Their contribution is
gratefully acknowledged:
Shier Berman, National Research Council, Ottawa, Ontario, Canada;
Nicholas Bloom, Frontier Geosciences Inc, Seattle, Washington;
Eric Crecelius, Battelle Marine Sciences Laboratory, Sequim, Washington;
Russell Flegal, University of California/Santa Cruz, California;
Gary Gill, Texas A&M University at Galveston, Texas;
Carlton Hunt and Dion Lewis, Battelle Ocean Sciences, Duxbury, Massachusetts;
Carl Watras, Wisconsin Department of Natural Resources, Boulder Junction, Wisconsin
Additional support was provided by Ted Martin of the EPA Office of Research and Development's
Environmental Monitoring Systems Laboratory in Cincinnati, Ohio and by Arthur Horowitz of the U.S.
Geological Survey.
This version ofthe method was prepared after observations of sampling teams from the University of California
at Santa Cruz, the Wisconsin Department of Natural Resources, the U.S. Geological Survey, and Battelle
Ocean Sciences. The assistance of personnel demonstrating the sampling techniques used by these institutions
is gratefully acknowledged.
Disclaimer
This sampling method has been reviewed and approved for publication by the Analytical Methods Staff within
the Engineering and Analysis Division of the U.S. Environmental Protection Agency. Mention of trade names
or commercial products does not constitute endorsement or recommendation for use.
Further Information
For further information, contact:
W.A. Telliard
Engineering and Analysis Division (4303)
U.S. Environmental Protection Agency
401 M Street, SW
Washington, DC 20460
Phone: [phone]
Fax: [phone]
July 1996
Method 9669
Introduction
This sampling method was designed to support water quality monitoring programs authorized under the Clean
Water Act. Section 304(a) of the Clean Water Act requires EPA to publish water quality criteria that reflect
the latest scientific knowledge concerning the physical fate (e.g., concentration and dispersal) of pollutants, the
effects of pollutants on ecological and human health, and the effect of pollutants on biological community
diversity, productivity, and stability.
Section 303 ofthe Clean Water Act requires states to set a water quality standard for each body of water within
its boundaries. A state water quality standard consists of a designated use or uses of a waterbody or a segment
of a waterbody, the water quality criteria that are necessary to protect the designated use or uses, and an
antidegradation policy. These water quality standards serve two purposes: (1) they establish the water quality
goals for a specific waterbody, and (2) they are the basis for establishing water quality-based treatment controls
and strategies beyond the technology-based controls required by Sections 301(b) and 306 of the Clean Water
Act.
In defining water quality standards, the state may use narrative criteria, numeric criteria, or both. However,
the 1987 amendments to the Clean Water Act required states to adopt numeric criteria for toxic pollutants
(designated in Section 307(a) of the Act) based on EPA Section 304(a) criteria or other scientific data, when
the discharge or presence of those toxic pollutants could reasonably be expected to interfere with designated
uses.
In some cases, these water quality criteria are as much as 280 times lower than those achievable using existing
EPA methods and required to support technology-based permits. Therefore, this sampling method, and the
analytical methods referenced in Table 1 of this document, were developed by EPA to specifically address state
needs for measuring toxic metals at water quality criteria levels, when such measurements are necessary to
protect designated uses in state water quality standards. The latest criteria published by EPA are those listed
in the National Toxics Rule (57 FR 60848) and the Stay of Federal Water Quality Criteria for Metals (60 FR
22228). These rules include water quality criteria for 13 metals, and it is these criteria on which this sampling
method and the referenced analytical methods are based.
In developing these methods, EPA found that one of the greatest difficulties in measuring pollutants at these
levels was precluding sample contamination during collection, transport, and analysis. The degree of difficulty,
however, is highly dependent on the metal and site-specific conditions. This method, therefore, is designed to
provide the level of protection necessary to preclude contamination in nearly all situations. It is also designed
to provide the procedures necessary to produce reliable results at the lowest possible water quality criteria
published by EPA. In recognition of the variety of situations to which this method may be applied, and in
recognition of continuing technological advances, the method is performance-based. Alternative procedures
may be used, so long as those procedures are demonstrated to yield reliable results.
Requests for additional copies of this method should be directed to:
U.S. EPA NCEPI
11029 Kenwood Road
Cincinnati, OH 45242
513/489-8190
July 1996 iii
Method 9669
Note: This document is intended as guidance only. Use of the terms "must," "may," and "should"
are included to mean that EPA believes that these procedures must, may, or should be followed in
order to produce the desired results when using this guidance. In addition, the guidance is intended
to be performance-based, in that the use of less stringent procedures may be used so long as neither
samples nor blanks are contaminated when following those modified procedures. Because the only
way to measure the performance of the modified procedures is through the collection and analysis
of uncontaminated blank samples in accordance with this guidance and the referenced methods, it is
highly recommended that any modifications be thoroughly evaluated and demonstrated to be
effective before field samples are collected.
iv July 1996
Method 1669
Sampling Ambient Water for Determination of Metals at EPA Water Quality
Criteria Levels
1.0 Scope and Application
1.1 This method is for the collection and filtration of ambient water samples for subsequent determination
of total and dissolved metals at the levels listed in Table 1. It is designed to support the
implementation of water quality monitoring and permitting programs administered under the Clean
Water Act.
1.2 This method is applicable to the metals listed below and other metals, metals species, and elements
amenable to determination at trace levels.
Chemical Abstract Services
Analyte Symbol Registry Number (CASRN)
Antimony (Sb) 7440-36-0
Arsenic (As) 7440-38-2
Cadmium (Cd) 7440-43-9
Chromium (III) Cr+3 16065-83-1
Chromium (VI) Cr+6 18540-29-9
Copper (Cu) 7440-50-8
Lead (Pb) 7439-92-1
Mercury (Hg) 7439-97-6
Nickel (NO 7440-02-0
Selenium (Se) 7782-49-2
Silver (Ag) 7440-22-4
Thallium (TI) 7440-28-0
Zinc (Zn) 7440-66-6
1.3 This method is accompanied by the 1600 series methods listed in Table 1. These methods include the
sample handling, analysis, and quality control procedures necessary for reliable determination oftrace
metals in aqueous samples.
1.4 This method is not intended for determination of metals at concentrations normally found in treated
and untreated discharges from industrial facilities. Existing regulations (40 CFR Parts 400-500)
typically limit concentrations in industrial discharges to the mid to high part-per-billion (ppb) range,
whereas ambient metals concentrations are normally in the low part-per-trillion (ppt) to low ppb range.
This guidance is therefore directed at the collection of samples to be measured at or near the levels
listed in Table 1. Actual concentration ranges to which this guidance is applicable will be dependent
on the sample matrix, dilution levels, and other laboratory operating conditions.
1.5 The ease of contaminating ambient water samples with the metal(s) of interest and interfering
substances cannot be overemphasized. This method includes sampling techniques that should
maximize the ability of the sampling team to collect samples reliably and eliminate sample
contamination. These techniques are given in Section 8.0 and are based on findings of researchers
performing trace metals analyses (References 1-9).
July 1996
Method 9669
1.6 Clean and Ultraclean-The terms "clean" and "ultraclean" have been used in other Agency guidance
to describe the techniques needed to reduce or eliminate contamination in trace metals determinations.
These terms are not used in this sampling method due to a lack of exact definitions. However, the
information provided in this method is consistent with summary guidance on clean and ultraclean
techniques (Reference 10).
1.7 This sampling method follows the EPA Environmental Methods Management Council's "Format for
Method Documentation" (Reference 11).
1.8 Method 1669 is "performance-based"; i.e., an alternate sampling procedure or technique may be used,
so long as neither samples nor blanks are contaminated when following the alternate procedures.
Because the only way to measure the performance of the alternate procedures is through the collection
and analysis of uncontaminated blank samples in accordance with this guidance and the methods
referenced in Table 1, it is highly recommended that any modifications be thoroughly evaluated and
demonstrated to be effective before field samples are collected. Section 9.2 provides additional details
on the tests and documentation required to support equivalent performance.
1.9 For dissolved metal determinations, samples must be filtered through a 0.45 pm capsule filter at the
field site. The filtering procedures are described in this method. The filtered samples may be
preserved in the field or transported to the laboratory for preservation. Procedures for field
preservation are detailed in this sampling method; procedures for laboratory preservation are provided
in the methods referenced in Table 1. Preservation requirements are summarized in Table 2.
1.10 The procedures in this method are for use only by personnel thoroughly trained in the collection of
samples for determination of metals at ambient water quality control levels.
2.0 Summary of Method
2.1 Before samples are collected, all sampling equipment and sample containers are cleaned in a laboratory
or cleaning facility using detergent, mineral acids, and reagent water as described in the methods
referenced in Table 1. The laboratory or cleaning facility is responsible for generating an acceptable
equipment blank to demonstrate that the sampling equipment and containers are free from trace metals
contamination before they are shipped to the field sampling team. An acceptable blank is one that is
free from contamination below the minimum level (ML) specified in the referenced analytical method
(Section 9.3).
2.2 After cleaning, sample containers are filled with weak acid solution, individually double-bagged, and
shipped to the sampling site. All sampling equipment is also bagged for storage or shipment.
NOTE: EPA has found that, in some cases, it may be possible to empty the weak acid solution from
the bottle immediately prior to transport to the field site. In this case, the bottle should be refilled
with reagent water (Section 7.1).
2.3 The laboratory or cleaning facility must prepare a large carboy or other appropriate clean container
filled with reagent water (Section 7.1) for use with collection of field blanks during sampling activities.
The reagent-water-filled container should be shipped to the field site and handled as all other sample
containers and sampling equipment. At least one field blank should be processed per site, or one per
every ten samples, whichever is more frequent (Section 9.4). If samples are to be collected for
determination oftrivalent chromium, the sampling team processes additional QC aliquots are processed
as described in Section 9.6.
2 July 1996
Method 9669
2.4 Upon arrival at the sampling site, one member of the two-person sampling team is designated as "dirty
hands"; the second member is designated as "clean hands." All operations involving contact with the
sample bottle and transfer of the sample from the sample collection device to the sample bottle are
handled by the individual designated as "clean hands." "Dirty hands" is responsible for preparation
of the sampler (except the sample container itself), operation of any machinery, and for all other
activities that do not involve direct contact with the sample.
2.5 All sampling equipment and sample containers used for metals determinations at or near the levels
listed in Table 1 must be nonmetallic and free from any material that may contain metals.
2.6 Sampling personnel are required to wear clean, nontalc gloves at all times when handling sampling
equipment and sample containers.
2.7 In addition to processing field blanks at each site, a field duplicate must be collected at each sampling
site, or one field duplicate per every 10 samples, whichever is more frequent (Section 9.5). Section
9.0 gives a complete description of quality control requirements.
2.8 Sampling
2.8.1 Whenever possible, samples are collected facing upstream and upwind to minimize
introduction of contamination.
2.8.2 Samples may be collected while working from a boat or while on land.
2.8.3 Surface samples are collected using a grab sampling technique. The principle of the grab
technique is to fill a sample bottle by rapid immersion in water and capping to minimize
exposure to airborne particulate matter.
2.8.4 Subsurface samples are collected by suction of the sample into an immersed sample bottle or
by pumping the sample to the surface.
2.9 Samples for dissolved metals are filtered through a 0.45 pm capsule filter at the field site. After
filtering, the samples are double-bagged and iced immediately. Sample containers are shipped to the
analytical laboratory. The sampling equipment is shipped to the laboratory or cleaning facility for
recleaning.
2.10 Acid preservation of samples is performed in the field or in the laboratory. Field preservation is
necessary for determinations of trivalent chromium. It has also been shown that field preservation can
increase sample holding times for hexavalent chromium to 30 days; therefore it is recommended that
preservation of samples for hexavalent chromium be performed in the field. For other metals,
however, the sampling team may prefer to utilize laboratory preservation of samples to expedite field
operations and to minimize the potential for sample contamination.
2.11 Sampling activities must be documented through paper or computerized sample tracking systems.
3.0 Definitions
3.1 Apparatus-Throughout this method, the sample containers, sampling devices, instrumentation, and
all other materials and devices used in sample collection, sample processing, and sample analysis
activities will be referred to collectively as the Apparatus.
July 1996
3
Method 9669
3.2 Definitions of other terms are given in the Glossary (Section 15.0) at the end of this method.
4.0 Contamination and Interferences
4.1 Contamination Problems in Trace Metals Analysis
4.1.1 Preventing ambient water samples from becoming contaminated during the sampling and
analytical process is the greatest challenge faced in trace metals determinations. In recent
years, it has been shown that much of the historical trace metals data collected in ambient
water are erroneously high because the concentrations reflect contamination from sampling
and analysis rather than ambient levels (Reference 12). Therefore, it is imperative that
extreme care be taken to avoid contamination when collecting and analyzing ambient water
samples for trace metals.
4.1.2 There are numerous routes by which samples may become contaminated. Potential sources
of trace metals contamination during sampling include metallic or metal-containing sampling
equipment, containers, labware (e.g. talc gloves that contain high levels of zinc), reagents, and
deionized water; improperly cleaned and stored equipment, labware, and reagents; and
atmospheric inputs such as dirt and dust from automobile exhaust, cigarette smoke, nearby
roads, bridges, wires, and poles. Even human contact can be a source of trace metals
contamination. For example, it has been demonstrated that dental work (e.g., mercury
amalgam fillings) in the mouths of laboratory personnel can contaminate samples that are
directly exposed to exhalation (Reference 3).
4.2 Contamination Control
4.2.1 Philosophy-The philosophy behind contamination control is to ensure that any object or
substance that contacts the sample is nonmetallic and free from any material that may contain
metals of concern.
4.2.1.1 The integrity of the results produced cannot be compromised by contamination of
samples. Requirements and suggestions for controlling sample contamination are
given in this sampling method and in the analytical methods referenced in Table 1.
4.2.1.2 Substances in a sample or in the surrounding environment cannot be allowed to
contaminate the Apparatus used to collect samples for trace metals measurements.
Requirements and suggestions for protecting the Apparatus are given in this sampling
method and in the methods referenced in Table 1.
4.2.1.3 While contamination control is essential, personnel health and safety remain the
highest priority. Requirements and suggestions for personnel safety are given in
Section 5 of this sampling method and in the methods referenced in Table 1.
4.2.2 Avoiding contamination-The best way to control contamination is to completely avoid
exposure of the sample and Apparatus to contamination in the first place. Avoiding exposure
means performing operations in an area known to be free from contamination. Two of the
most important factors in avoiding/reducing sample contamination are (1) an awareness of
potential sources of contamination and (2) strict attention to work being performed.
Therefore, it is imperative that the procedures described in this method be carried out by well
4 July 1996
Method 9669
trained, experienced personnel. Documentation of training should be kept on file and readily
available for review.
4.2.2.1 Minimize exposure-The Apparatus that will contact samples or blanks should only
be opened or exposed in a clean room, clean bench, glove box, or clean plastic bag,
so that exposure to atmospheric inputs is minimized. When not being used, the
Apparatus should be covered with clean plastic wrap, stored in the clean bench or in
a plastic box or glove box, or bagged in clean, colorless zip-type bags. Minimizing
the time between cleaning and use will also reduce contamination.
4.2.2.2 Wear gloves-Sampling personnel must wear clean, nontalc gloves (Section 6.7)
during all operations involving handling of the Apparatus, samples, and blanks. Only
clean gloves may touch the Apparatus. If another objector substance is touched, the
glove(s) must be changed before again handling the Apparatus. If it is even suspected
that gloves have become contaminated, work must be halted, the contaminated gloves
removed, and a new pair of clean gloves put on. Wearing multiple layers of clean
gloves will allow the old pair to be quickly stripped with minimal disruption to the
work activity.
4.2.2.3 Use metal-free Apparatus-All Apparatus used for metals determinations at the
levels listed in Table 1 must be nonmetallic and free of material that may contain
metals. When it is not possible to obtain equipment that is completely free of the
metal(s) of interest, the sample should not come into direct contact with the
equipment.
4.2.2.3.1 Construction materials-Only the following materials should come
in contact with samples: fluoropolymer (FEP, PTFE), conventional
or linear polyethylene, polycarbonate, polysulfone, polypropylene,
or ultrapure quartz. PTFE is less desirable than FEP because the
sintered material in PTFE may contain contaminants and is
susceptible to serious memory effects (Reference 6). Fluoropolymer
or glass containers should be used for samples that will be analyzed
for mercury because mercury vapors can diffuse in or out of other
materials, resulting either in contamination or low-biased results
(Reference 3). Metal must not be used under any circumstance.
Regardless of construction, all materials that will directly or
indirectly contact the sample must be cleaned using the procedures
described in the referenced analytical methods (see Table 1) and
must be known to be clean and metal-free before proceeding.
4.2.2.3.2 The following materials have been found to contain trace metals and
must not be used to hold liquids that come in contact with the
sample or must not contact the sample, unless these materials have
been shown to be free of the metals of interest at the desired level:
Pyrex, Kimax, methacrylate, polyvinylchloride, nylon, and Vycor
(Reference 6). In addition, highly colored plastics, paper cap liners,
pigments used to mark increments on plastics, and rubber all contain
trace levels of metals and must be avoided (Reference 13).
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Method 9669
4.2.2.3.3 Serialization-Serial numbers should be indelibly marked or etched
on each piece of Apparatus so that contamination can be traced, and
logbooks should be maintained to track the sample from the
container through the sampling process to shipment to the
laboratory. Chain-of-custody procedures may also be used if
warranted so that contamination can be traced to particular handling
procedures or lab personnel.
4.2.2.3.4 The Apparatus should be clean when the sampling team receives it.
If there are any indications that the Apparatus is not clean (e.g., a
ripped storage bag), an assessment of the likelihood of
contamination must be made. Sampling must not proceed if it is
possible that the Apparatus is contaminated. If the Apparatus is
contaminated, it must be returned to the laboratory or cleaning
facility for proper cleaning before any sampling activity resumes.
4.2.2.3.5 Details for recleaning the Apparatus between collection of individual
samples are provided in Section 10.0.
4.2.2.4 Avoid sources of contamination-Avoid contamination by being aware of potential
sources and routes of contamination.
4.2.2.4.1 Contamination by carryover-Contamination may occur when a
sample containing low concentrations of metals is processed
immediately after a sample containing relatively high concentrations
of these metals. At sites where more than one sample will be
collected, the sample known or expected to contain the lowest
concentration of metals should be collected first with the sample
containing the highest levels collected last (Section 8.1.4). This will
help minimize carryover ofinetals from high- concentration samples
to low- concentration samples. If the sampling team does not have
prior knowledge of the waterbody, or when necessary, the sample
collection system should be rinsed with dilute acid and reagent water
between samples and followed by collection of a field blank (Section
10.3).
4.2.2.4.2 Contamination by samples-Significant contamination of the
Apparatus may result when untreated effluents, in-process waters,
landfill leachates, and other samples containing mid- to high-level
concentrations of inorganic substances are processed. As stated in
Section 1.0, this sampling method is not intended for application to
these samples, and samples containing high concentrations ofinetals
must not be collected, processed, or shipped at the same time as
samples being collected for trace metals determinations.
4.2.2.4.3 Contamination by indirect contact-Apparatus that may not directly
contact samples may still be a source of contamination. For
example, clean tubing placed in a dirty plastic bag may pick up
contamination from the bag and subsequently transfer the
contamination to the sample. Therefore, it is imperative that every
6 July 1996
Method 9669
piece of the Apparatus that is directly or indirectly used in the
collection of ambient water samples be cleaned as specified in the
analytical method(s) referenced in Table 1.
4.2.2.4.4 Contamination by airborne particulate matter-Less obvious
substances capable of contaminating samples include airborne
particles. Samples may be contaminated by airborne dust, dirt,
particulate matter, or vapors from automobile exhaust; cigarette
smoke; nearby corroded or rusted bridges, pipes, poles, or wires;
nearby roads; and even human breath (Section 4.1.2). Whenever
possible, the sampling activity should occur as far as possible from
sources of airborne contamination (Section 8.1.3). Areas where
nearby soil is bare and subject to wind erosion should be avoided.
4.3 Interferences-Interferences resulting from samples will vary considerably from source to source,
depending on the diversity of the site being sampled. If a sample is suspected of containing substances
that may interfere in the determination of trace metals, sufficient sample should be collected to allow
the laboratory to identify and overcome interference problems.
5.0 Safety
5.1 The toxicity or carcinogenicity of the chemicals used in this method has not been precisely determined;
however, these chemicals should be treated as a potential health hazard. Exposure should be reduced
to the lowest possible level. Sampling teams are responsible for maintaining a current awareness file
of OSHA regulations for the safe handling of the chemicals specified in this method. A reference file
of Material Safety Data Sheets should also be made available to all personnel involved in sampling.
It is also suggested that the organization responsible perform personal hygiene monitoring of each
sampling team member who uses this method and that the results of this monitoring be made available
to the member.
5.2 Operating in and around waterbodies carries the inherent risk of drowning. Life jackets must be wom
when operating from a boat, when sampling in more than a few feet of water, or when sampling in
swift currents.
5.3 Collecting samples in cold weather, especially around cold water bodies, carries the risk of
hypothermia, and collecting samples in extremely hot and humid weather carries the risk of
dehydration and heat stroke. Sampling team members should wear adequate clothing for protection
in cold weather and should carry an adequate supply of water or other liquids for protection against
dehydration in hot weather.
6.0 Apparatus and Materials
NOTE: Brand names, suppliers, and part numbers are for illustration only and no endorsement is implied.
Equivalent performance may be achieved using apparatus and materials other than those specified here.
Meeting the performance requirements of this method is the responsibility of the sampling team and
laboratory.
6.1 All sampling equipment and sample containers must be precleaned in a laboratory or cleaning facility,
as described in the methods referenced in Table 1, before they are shipped to the field site.
July 1996
7
Method 9669
Performance criteria for equipment cleaning is described in the referenced methods. To minimize
difficulties in sampling, the equipment should be packaged and arranged to minimize field preparation.
6.2 Materials such as gloves (Section 6.7), storage bags (Section 6.8), and plastic wrap (Section 6.9), may
be used new without additional cleaning unless the results of the equipment blank pinpoint any ofthese
materials as a source of contamination. In this case, either a different supplier must be obtained or the
materials must be cleaned.
6.3 Sample Bottles-Fluoropolymer (FEP, PTFE), conventional or linear polyethylene, polycarbonate,
or polypropylene; 500 mL or 1 L with lids. If mercury is a target analyte, fluoropolymer or glass
bottles should be used. Refer to the methods referenced in Table 1 for bottle cleaning procedures.
6.3.1 Cleaned sample bottles should be filled with 0.1% HCl (v/v). In some cases, it may be
possible to empty the weak acid solution from the sample bottle immediately priorto transport
to the field site. In this case, the bottle should be refilled with reagent water (Section 7.1).
6.3.2 Whenever possible, sampling devices should be cleaned and prepared for field use in a class
100 clean room. Preparation of the devices in the field should be done within the glove bag
(Section 6.6). Regardless of design, sampling devices must be constructed of nonmetallic
material (Section 4.2.2.3.1) and free from material that contains metals. Fluoropolymer or
other material shown not to adsorb or contribute mercury must be used if mercury is a target
analyte; otherwise, polyethylene, polycarbonate, or polypropylene are acceptable.
Commercially available sampling devices may be used provided that any metallic or metal-
containing parts are replaced with parts constructed of nonmetallic material.
6.4 Surface Sampling Devices-Surface samples are collected using a grab sampling technique. Samples
may be collected manually by direct submersion of the bottle into the water or by using a grab
sampling device. Examples of grab samplers are shown in Figures 1 and 2 and may be used at sites
where depth profiling is neither practical nor necessary.
6.4.1 The grab sampler in Figure 1 consists of a heavy fluoropolymer collar fastened to the end of
a 2-m-long polyethylene pole, which serves to remove the sampling personnel from the
immediate vicinity of the sampling point. The collar holds the sample bottle. A fluoropolymer
closing mechanism, threaded onto the bottle, enables the sampler to open and close the bottle
under water, thereby avoiding surface microlayer contamination (Reference 14).
Polyethylene, polycarbonate, and polypropylene are also acceptable construction materials
unless mercury is a target analyte. Assembly of the cleaned sampling device is as follows
(refer to Figure 1):
6.4.1.1 Thread the pull cord (with the closing mechanism attached) through the guides and
secure the pull ring with a simple knot. Screw a sample bottle onto the closing device
and insert the bottle into the collar. Cock the closing plate so that the plate is pushed
away from the operator.
6.4.1.2 The cleaned and assembled sampling device should be stored in a double layer of
large, clean zip-type polyethylene bags or wrapped in two layers of clean
polyethylene wrap if it will not be used immediately.
6.4.2 An alternate grab sampler design is shown in Figure 2. This grab sampler is used for discrete
water samples and is constructed so that a capped clean bottle can be submerged, the cap
July 1996
Method 9669
removed, sample collected, and bottle recapped at a selected depth. This device eliminates
sample contact with conventional samplers (e.g., Niskin bottles), thereby reducing the risk of
extraneous contamination. Because a fresh bottle is used for each sample, carryover from
previous samples is eliminated (Reference 15).
6.5 Subsurface Sampling Devices-Subsurface sample collection maybe appropriate in lakes and sluggish
deep river environments or where depth profiling is determined to be necessary. Subsurface samples
are collected by pumping the sample into a sample bottle. Examples of subsurface collection systems
include the jar system device shown in Figure 3 and described in Section 6.5.1 or the continuous-flow
apparatus shown in Figure 4 and described in Section 6.5.2.
6.5.1 Jar sampler (Reference 14)-The jar sampler (Figure 3) is comprised of a heavy
fluoropolymer 1-L jar with a fluoropolymer lid equipped with two 1/4 in. fluoropolymer
fittings. Sample enters the jar through a short length of fluoropolymer tubing inserted into one
fitting. Sample is pulled into the jar by pumping on fluoropolymer tubing attached to the other
fitting. A thick fluoropolymer plate supports the jar and provides attachment points for a
fluoropolymer safety line and fluoropolymer torpedo counterweight.
6.5.1.1 Advantages of the jar sampler for depth sampling are (1) all wetted surfaces are
fluoropolymer and can be rigorously cleaned; (2) the sample is collected into a sample
jar from which the sample is readily recovered, and the jar can be easily recleaned;
(3) the suction device (a peristaltic or rotary vacuum pump, Section 6.15) is located
in the boat, isolated from the sampling jar; (4) the sampling jar can be continuously
flushed with sample, at sampling depth, to equilibrate the system; and (5) the sample
does not travel through long lengths oftubing that are more difficult to clean and keep
clean (Reference 14). In addition, the device is designed to eliminate atmospheric
contact with the sample during collection.
6.5.1.2 To assemble the cleaned jar sampler, screw the torpedo weight onto the machined bolt
attached to the support plate of the jar sampler. Attach a section of the 1/4 in. o.d.
tubing to the jar by inserting the tubing into the fitting on the lid and pushing down
into the jar until approximately 8 cm from the bottom. Tighten the fitting nut
securely. Attach the solid safety line to the jar sampler using a bowline knot to the
loop affixed to the support plate.
6.5.1.3 For the tubing connecting the pump to the sampler, tubing lengths of up to 12 in have
been used successfully (Reference 14).
6.5.2 Continuous-flow sampler (References 16-17)-This sampling system, shown in Figure 4,
consists of a peristaltic or submersible pump and one or more lengths of precleaned
fluoropolymer or styrene/ethylene/butylene/ silicone (SEBS) tubing. A filter is added to the
sampling train when sampling for dissolved metals.
6.5.2.1 Advantages ofthis sampling system include (1) all wetted surfaces are fluoropolymer
or SEBS and can be readily cleaned; (2) the suction device is located in the boat,
isolated from the sample bottle; (3) the sample does not travel through long lengths
of tubing that are difficult to clean and keep clean; and (4) in-line filtration is
possible, minimizing field handling requirements for dissolved metals samples.
July 1996
Method 9669
6.5.2.2 The sampling team assembles the system in the field as described in Section 8.2.8.
System components include an optional polyethylene pole to remove sampling
personnel from the immediate vicinity of the sampling point and the pump, tubing,
filter, and filter holder listed in Sections 6.14 and 6.15.
6.6 Field-Portable Glove Bag-12R, Model R-37-37H (nontalc), or equivalent. Alternately, a portable
glove box may be constructed with a nonmetallic (PVC pipe or other suitable material) frame and a
frame cover made of an inexpensive, disposable, nonmetallic material (e.g., athin-walled polyethylene
bag) (Reference 7).
6.7 Gloves-Clean, nontalc polyethylene, latex, vinyl, or PVC; various lengths. Shoulder-length gloves
are needed if samples are to be collected by direct submersion of the sample bottle into the water or
when sampling for mercury.
6.7.1 Gloves, shoulder-length polyethylene-Associated Bag Co., Milwaukee, WI, 66-3-301, or
equivalent.
6.7.2 Gloves, PVC-Fisher Scientific Part No. 11-394-10013, or equivalent.
6.8 Storage Bags-Clean, zip-type, nonvented, colorless polyethylene (various sizes).
6.9 Plastic Wrap-Clean, colorless polyethylene.
6.10 Cooler-Clean, nonmetallic, with white interior for shipping samples.
6.11 Ice or Chemical Refrigerant Packs-To keep samples chilled in the cooler during shipment.
6.12 Wind Suit-Pamida, or equivalent.
NOTE: This equipment is necessary only for collection of metals, such as mercury, that are known to have
elevated atmospheric concentrations.
6.12.1 An unlined, long-sleeved wind suit consisting of pants and jacket and constructed of nylon or
other synthetic fiber is wom when sampling for mercury to prevent mercury adsorbed onto
cotton or other clothing materials from contaminating samples.
6.12.2 Washing and drying-The wind suit is washed by itself or with other wind suits only in a
home or commercial washing machine and dried in a clothes dryer. The clothes dryer must
be thoroughly vacuumed, including the lint filter, to remove all traces of lint before drying.
After drying, the wind suit is folded and stored in a clean polyethylene bag for shipment to the
sample site.
6.13 Boat
6.13.1 For most situations (e.g., most metals undermost conditions), the use of an existing, available
boat is acceptable. A flat-bottom, Boston Whaler-type boat is preferred because sampling
materials can be stored with reduced chance of tipping.
10 July 1996
Method 9669
6.13.1.1 Immediately before use, the boat should be washed with water from the
sampling site away from any sampling points to remove any dust or dirt
accumulation.
6.13.1.2 Samples should be collected upstream of boat movement.
6.13.2 For mercury, and for situations in which the presence of contaminants cannot otherwise be
controlled below detectable levels, the following equipment and precautions may be necessary:
6.13.2.1 A metal-free (e.g., fiberglass) boat, along with wooden or fiberglass oars.
Gasoline- or diesel-fueled boat motors should be avoided when possible
because the exhaust can be a source of contamination. If the body of water
is large enough to require use of a boat motor, the engine should be shut off
at a distance far enough from the sampling point to avoid contamination, and
the sampling team should manually propel the boat to the sampling point.
Samples should be collected upstream of boat movement.
6.13.2.2 Before first use, the boat should be cleaned and stored in an area that
minimizes exposure to dust and atmospheric particles. For example, cleaned
boats should not be stored in an area that would allow exposure to
automobile exhaust or industrial pollution.
6.13.2.3 The boat should be frequently visually inspected for possible contamination.
6.13.2.4 After sampling, the boat should be returned to the laboratory or cleaning
facility, cleaned as necessary, and stored away from any sources of
contamination until next use.
6.14 Filtration Apparatus-Required when collecting samples for dissolved metals determinations.
6.14.1 Filter-0.45 µm, 15 mm diameter or larger, tortuous-path capsule filters (Reference 18),
Gelman Supor 12175, or equivalent.
6.14.2 Filter holder-For mounting filter to the gunwale of the boat. Rod or pipe made from plastic
material and mounted with plastic clamps.
NOTE: A filter holder may not be required if one or a few samples are to be collected. For these cases, it
may only be necessary to attach the filter to the outlet of the tubing connected to the pump.
6.15 Pump and Pump Apparatus-Required for use with the jar sampling system (Section 6.5. 1) or the
continuous-flow system (Section 6.5.2). Peristaltic pump; 115 V a.c., 12 V d.c., internal battery,
variable-speed, single-head, Cole-Parmer, portable, "Masterflex L/S," Catalog No. H-07570-10 drive
with Quick Load pump head, Catalog No. H-07021-24, or equivalent.
NOTE: Equivalent pumps may include rotary vacuum, submersible, or other pumps free from metals and
suitable to meet the site-specific depth sampling needs.
6.15.1 Cleaning-Peristaltic pump modules do not require cleaning. However, nearly all peristaltic
pumps contain a metal head and metal controls. Touching the head or controls necessitates
July 1996 11
Method 9669
changing of gloves before touching the Apparatus. If a submersible pump is used, a large
volume of sample should be pumped to clean the stainless steel shaft (hidden behind the
impeller) that comes in contact with the sample. Pumps with metal impellers should not be
used.
6.15.2 Tubing-For use with peristaltic pump. SEBS resin, approximately 3/8 in. i.d. by
approximately 3 ft, Cole-Parmer size 18, Cat. No. G-06464-18, or approximately 1/4 in. i.d.,
Cole-Parmer size 17, Catalog No. G-06464-17, or equivalent. Tubing is cleaned by soaking
in 5-10% HCl solution for 8-24 hours, rinsing with reagent water in a clean bench in a clean
room, and drying in the clean bench by purging with mercury-free air or nitrogen. After
drying, the tubing is double-bagged in clear polyethylene bags, serialized with a unique
number, and stored until use.
6.15.3 Tubing-For connection to peristaltic pump tubing. Fluoropolymer, 3/8 or 1/4 in. o.d., in
lengths as required to reach the point of sampling. If sampling will be at some depth from the
end of a boom extended from a boat, sufficient tubing to extend to the end of the boom and
to the depth will be required. Cleaning of the fluoropolymer can be the same as cleaning the
tubing for the rotary vacuum pump (Section 6.15.1.2). If necessary, more aggressive cleaning
(e.g., concentrated nitric acid) may be used.
6.15.4 Batteries to operate submersible pump-12 V, 2.6 amp, gel cell, YUASA NP2.6-12, or
equivalent. A 2 amp fuse connected at the positive battery terminal is strongly recommended
to prevent short circuits from overheating the battery. A 12 V, lead-acid automobile or marine
battery may be more suitable for extensive pumping.
6.15.5 Tubing connectors-Appropriately sized PVC, clear polyethylene, or fluoropolymer "barbed"
straight connectors cleaned as the tubing above. Used to connect multiple lengths of tubing.
6.16 Carboy-For collection and storage of dilute waste acids used to store bottles.
6.17 Apparatus-For field preservation of aliquots for trivalent chromium determinations.
6.17.1 Fluoropolymer forceps-1 L fluoropolymer jar, and 30 mL fluoropolymer vials with screw-
caps (one vial per sample and blank). It is recommended that 1 mL of ultrapure nitric acid
(Section 7.3) be added to each vial prior to transport to the field to simplify field handling
activities (See Section 8.4.4.6).
6.17.2 Filters-0.4 µm, 47 mm polycarbonate Nuclepore (or equivalent). Filters are cleaned as
follows. Fill a 1 L fluoropolymer jar approximately two-thirds full with 1 N nitric acid.
Using fluoropolymer forceps, place individual filters in the fluoropolymer jar. Allow the
filters to soak for 48 hours. Discard the acid, and rinse five times with reagent water. Fill the
jar with reagent water, and soak the filters for 24 hours. Remove the filters when ready for
use, and using fluoropolymer forceps, place them on the filter apparatus (Section 6.17.3).
6.17.3 Vacuum filtration apparatus-Millipore 47 mm size, or equivalent, vacuum pump and power
source (and extension cords, if necessary) to operate the pump.
6.17.4 Eppendorf auto pipet and colorless pipet tips (100-1000 µL)
6.17.5 Wrist-action shaker-Burrel or equivalent.
12 July 1996
Method 9669
6.17.6 Fluoropolymer wash bottles-One filled with reagent water (Section 7.1) and one filled with
high- purity 10% HCl (Section 7.4.4), for use in rinsing forceps and pipet tips.
7.0 Reagents and Standards
7.1 Reagent Water-Water in which the analytes of interest and potentially interfering substances are not
detected at the Method Detection Limit (MDL) of the analytical method used for analysis of samples.
Prepared by distillation, deionization, reverse osmosis, anodic/cathodic stripping voltammetry, or other
techniques that remove the metal(s) and potential interferent(s). A large carboy or other appropriate
container filled with reagent water must be available for the collection of field blanks.
7.2 Nitric Acid-Dilute, trace-metal grade, shipped with sampling kit for cleaning equipment between
samples.
7.3 Sodium Hydroxide-Concentrated, 50% solution foruse when field-preserving samples forhexavalent
chromium determinations (Section 8.4.5).
7.4 Reagents-For field-processing aliquots for trivalent chromium determinations
7.4.1 Nitric Acid, Ultrapure-For use when field-preserving samples for trivalent chromium
determinations (Sections 6.17 and 8.4.4).
7.4.2 Ammonium Iron (II) Sulfate Solution (0.01M)-Used to prepare the chromium (III)
extraction solution (Section 7.4.3) necessary for field preservation of samples for trivalent
chromium (Section 8.4.4). Prepare the ammonium iron (II) sulfate solution by adding 3.92
g ammonium iron (II) sulfate (ultrapure grade) to a 1 L volumetric flask. Bring to volume
with reagent water. Store in a clean polyethylene bottle.
7.4.3 Chromium (III) extraction solution-For use when field-preserving samples for trivalent
chromium determinations (Section 8.4.4). Prepare this solution by adding 100 mL of
ammonium iron (II) sulfate solution (Section 7.4.2) to a 125 mL polyethylene bottle. Adjust
pH to 8 with approximately 2 mL of ammonium hydroxide solution. Cap and shake on a
wrist-action shaker for 24 hours. This iron (III) hydroxide solution is stable for 30 days.
7.4.4 Hydrochloric acid-High-purity, 10% solution, shipped with sampling kit in fluoropolymer
wash bottles for cleaning trivalent chromium sample preservation equipment between samples.
7.4.5 Chromium stock standard solution (1000 µg/mL)-Prepared by adding 3.1 g anhydrous
chromium chloride to a 1 L flask and diluting to volume with 1% hydrochloric acid. Store in
polyethylene bottle. A commercially available standard solution may be substituted.
7.4.6 Standard chromium spike solution (1000 µg/L,)-Used to spike sample aliquots for matrix
spike/matrix spike duplicate (MS/MSD) analysis and to prepare ongoing precision and
recovery standards. Prepared by spiking 1 mL of the chromium stock standard solution
(Section 7.4.5) into a I L flask. Dilute to volume with 1% HCl. Store in a polyethylene
bottle.
7.4.7 Ongoing precision and recovery (OPR) standard (25 µg/L)-Prepared by spiking 2.5 mL of
the standard chromium spike solution (Section 7.4.6) into a 100 mL flask. Dilute to volume
with 1% HCI. One OPR is required for every 10 samples.
July 1996 13
Method 9669
8.0 Sample Collection, Filtration, and Handling
8.1 Site Selection
8.1.1 Selection of a representative site for surface water sampling is based on many factors
including: study objectives, water use, point source discharges, non-point source discharges,
tributaries, changes in stream characteristics, types of stream bed, stream depth, turbulence,
and the presence of structures (bridges, dams, etc.). When collecting samples to determine
ambient levels of trace metals, the presence of potential sources of metal contamination are
of extreme importance in site selection.
8.1.2 Ideally, the selected sampling site will exhibit a high degree of cross-sectional homogeneity.
It may be possible to use previously collected data to identify locations for samples that are
well mixed or are vertically or horizontally stratified. Since mixing is principally governed
by turbulence and water velocity, the selection of a site immediately downstream of a riffle
area will ensure good vertical mixing. Horizontal mixing occurs in constrictions in the
channel. In the absence of turbulent areas, the selection of a site that is clear of immediate
point sources, such as industrial effluents, is preferred for the collection of ambient water
samples (Reference 19).
8.1.3 To minimize contamination from trace metals in the atmosphere, ambient water samples
should be collected from sites that are as far as possible (e.g., at least several hundred feet)
from any metal supports, bridges, wires or poles. Similarly, samples should be collected as
far as possible from regularly or heavily traveled roads. If it is not possible to avoid collection
near roadways, it is advisable to study traffic patterns and plan sampling events during lowest
traffic flow (Reference 7).
8.1.4 The sampling activity should be planned to collect samples known or suspected to contain the
lowest concentrations of trace metals first, finishing with the samples known or suspected to
contain the highest concentrations. For example, if samples are collected from a flowing river
or stream near an industrial or municipal discharge, the upstream sample should be collected
first, the downstream sample collected second, and the sample nearest the discharge collected
last. If the concentrations of pollutants is not known and cannot be estimated, it is necessary
to use precleaned sampling equipment at each sampling location.
8.2 Sample Collection Procedure-Before collecting ambient water samples, consideration should be given
to the type of sample to be collected, the amount of sample needed, and the devices to be used (grab,
surface, or subsurface samplers). Sufficient sample volume should be collected to allow for necessary
quality control analyses, such as matrix spike/matrix spike duplicate analyses.
8.2.1 Four sampling procedures are described:
8.2.1.1 Section 8.2.5 describes a procedure for collecting samples directly into the sample
container. This procedure is the simplest and provides the least potential for
contamination because it requires the least amount of equipment and handling.
8.2.1.2 Section 8.2.6 describes a procedure for using a grab sampling device to collect
samples.
14 July 1996
Method 9669
8.2.1.3 Section 8.2.7 describes a procedure for depth sampling with ajar sampler. The size
of sample container used is dependent on the amount of sample needed by the
analytical laboratory.
8.2.1.4 Section 8.2.8 describes a procedure for continuous-flow sampling using a
submersible or peristaltic pump.
8.2.2 The sampling team should ideally approach the site from down current and downwind to
prevent contamination of the sample by particles sloughing off the boat or equipment. If it
is not possible to approach from both, the site should be approached from down current if
sampling from a boat or approached from downwind if sampling on foot. When sampling
from a boat, the bow of the boat should be oriented into the current (the boat will be pointed
upstream). All sampling activity should occur from the bow.
If the samples are being collected from a boat, it is recommended that the sampling team
create a stable workstation by arranging the cooler or shipping container as a work table on
the upwind side of the boat, covering this worktable and the upwind gunnel with plastic wrap
or a plastic tablecloth, and draping the wrap or cloth over the gunnel. If necessary, duct tape
is used to hold the wrap or cloth in place.
8.2.3 All operations involving contact with the sample bottle and with transfer of the sample from
the sample collection device to the sample bottle (if the sample is not directly collected in the
bottle) are handled by the individual designated as "clean hands." "Dirty hands" is responsible
for all activities that do not involve direct contact with the sample.
Although the duties of "clean hands" and "dirty hands" would appear to be a logical separation
of responsibilities, in fact, the completion of the entire protocol may require a good deal of
coordination and practice. For example, "dirty hands" must open the box or cooler containing
the sample bottle and unzip the outer bag; clean hands must reach into the outer bag, open the
inner bag, remove the bottle, collect the sample, replace the bottle lid, put the bottle back into
the inner bag, and zip the inner bag. "Dirty hands" must close the outer bag and place it in
a cooler.
To minimize unnecessary confusion, it is recommended that a third team member be available
to complete the necessary sample documentation (e.g., to document sampling location, time,
sample number, etc). Otherwise, "dirty hands" must perform the sample documentation
activity (Reference 7).
8.2.4 Extreme care must be taken during all sampling operations to minimize exposure of the
sample to human, atmospheric, and other sources of contamination. Care must be taken to
avoid breathing directly on the sample, and whenever possible, the sample bottle should be
opened, filled, and closed while submerged.
8.2.5 Manual collection of surface samples directly into the sample bottle.
8.2.5.1 At the site, all sampling personnel must put on clean gloves (Section 6.7) before
commencing sample collection activity, with "clean hands" donning shoulder-length
gloves. If samples are to be analyzed for mercury, the sampling team must also put
their precleaned wind suits on at this time. Note that "clean hands" should put on the
July 1996 13
Method 9669
shoulder-length polyethylene gloves (Section 6.7. 1) and both "clean hands" and "dirty
hands" should put on the PVC gloves (Section 6.7.2).
8.2.5.2 "Dirty hands" must open the cooler or storage container, remove the double-bagged
sample bottle from storage, and unzip the outer bag.
8.2.5.3 Next, "clean hands" opens the inside bag containing the sample bottle, removes the
bottle, and reseals the inside bag. "Dirty hands" then reseals the outer bag.
8.2.5.4 "Clean hands" unscrews the cap and, while holding the cap upside down, discards the
dilute acid solution from the bottle into a carboy for wastes (Section 6.16) or discards
the reagent water directly into the water body.
8.2.5.5 "Clean hands" then submerges the sample bottle, and allows the bottle to partially fill
with sample. "Clean hands" screws the cap on the bottle, shakes the bottle several
times, and empties the rinsate away from the site. After two more rinsings, "clean
hands" holds the bottle under water and allows bottle to fill with sample. After the
bottle has filled (i.e., when no more bubbles appear), and while the bottle is still
inverted so that the mouth of the bottle is underwater, "clean hands" replaces the cap
of the bottle. In this way, the sample has never contacted the air.
8.2.5.6 Once the bottle lid has been replaced, "dirty hands" reopens the outer plastic bag, and
"clean hands" opens the inside bag, places the bottle inside it, and zips the inner bag.
8.2.5.7 "Dirty hands" zips the outer bag.
8.2.5.8 Documentation-After each sample is collected, the sample number is documented
in the sampling log, and any unusual observations concerning the sample and the
sampling are documented.
8.2.5.9 If the sample is to be analyzed for dissolved metals, it is filtered in accordance with
the procedure described in Section 8.3.
8.2.6 Sample collection with grab sampling device-The following steps detail sample collection
using the grab sampling device shown in Figure 1 and described in Section 6.4.1. The
procedure is indicative of the "clean hands/dirty hands" technique that must be used with
alternative grab sampling devices such as that shown in Figure 2 and described in Section
6.4.2.
8.2.6.1 The sampling team puts on gloves (and wind suits, if applicable). Ideally, a sample
bottle will have been preattached to the sampling device in the class 100 clean room
at the laboratory. If it is necessary to attach a bottle to the device in the field, "clean
hands" performs this operation, described in Section 6.4.2, inside the field-portable
glove bag (Section 6.6).
8.2.6.2 "Dirty hands" removes the sampling device from its storage container and opens the
outer polyethylene bag.
8.2.6.3 "Clean hands" opens the inside polyethylene bag and removes the sampling device.
16 July 1996
Method 9669
8.2.6.4 "Clean hands" changes gloves.
8.2.6.5 "Dirty hands" submerges the sampling device to the desired depth and pulls the
fluoropolymer pull cord to bring the seal plate into the middle position so that water
can enter the bottle.
8.2.6.6 When the bottle is full (i.e., when no more bubbles appear), "dirty hands" pulls the
fluoropolymer cord to the final stop position to seal off the sample and removes the
sampling device from the water.
8.2.6.7 "Dirty hands" returns the sampling device to its large inner plastic bag, "clean hands"
pulls the bottle out of the collar, unscrews the bottle from the sealing device, and caps
the bottle. "Clean hands" and "dirty hands" then return the bottle to its double-bagged
storage as described in Sections 8.2.5.6 through 8.2.5.7.
8.2.6.8 Closing mechanism-"Clean hands" removes the closing mechanism from the body
of the grab sampler, rinses the device with reagent water (Section 7. 1), places it inside
a new clean plastic bag, zips the bag, and places the bag inside an outer bag held by
"dirty hands." "Dirty hands" zips the outer bag and places the double-bagged closing
mechanism in the equipment storage box.
8.2.6.9 Sampling device-"Clean hands" seals the large inside bag containing the collar, pole,
and cord and places the bag into a large outer bag held by "dirty hands." "Dirty
hands" seals the outside bag and places the double-bagged sampling device into the
equipment storage box.
8.2.6.10 Documentation-After each sample is collected, the sample number is documented
in the sampling log, and any unusual observations concerning the sample and the
sampling are documented.
8.2.6.11 If the sample is to be analyzed for dissolved metals, it is filtered in accordance with
the procedures described in Section 8.3.
8.2.7 Depth sampling using a jar sampling device (Figure 3 and Section 6.5. 1)
8.2.7.1 The sampling team puts on gloves (and wind suits, if applicable) and handles bottles
as with manual collection (Sections 8.2.5.1 through 8.2.5.4 and 8.2.5.6 through
8.2.5.7).
8.2.7.2 "Dirty hands" removes the jar sampling device from its storage container and opens
the outer polyethylene bag.
8.2.7.3 "Clean hands" opens the inside polyethylene bag and removes the jar sampling
apparatus. Ideally, the sampling device will have been preassembled in a class 100
clean room at the laboratory. If, however, it is necessary to assemble the device in
the field, "clean hands" must perform this operation, described in Section 6.5.2, inside
a field-portable glove bag (Section 6.6).
8.2.7.4 While "dirty hands" is holding the jar sampling apparatus, "clean hands" connects the
pump to the to the 1/4 in. o.d. flush line.
July 1996 17
Method 9669
8.2.7.5 "Dirty hands" lowers the weighted sampler to the desired depth.
8.2.7.6 "Dirty hands" turns on the pump allowing a large volume (>2 L) of water to pass
through the system.
8.2.7.7 After stopping the pump, "dirty hands" pulls up the line, tubing, and device and
places them into either a field-portable glove bag or a large, clean plastic bag as they
emerge.
8.2.7.8 Both "clean hands" and "dirty hands" change gloves.
8.2.7.9 Using the technique described in Sections 8.2.5.2 through 8.2.5.4, the sampling team
removes a sample bottle from storage, and "clean hands" places the bottle into the
glove bag.
8.2.7.10 "Clean hands" tips the sampling jar and dispenses the sample through the short
length of fluoropolymer tubing into the sample bottle.
8.2.7.11 Once the bottle is filled, "clean hands" replaces the cap of the bottle, returns the
bottle to the inside polyethylene bag, and zips the bag. "Clean hands" returns the
zipped bag to the outside polyethylene bag held by "dirty hands."
8.2.7.12 "Dirty hands" zips the outside bag. If the sample is to be analyzed for dissolved
metals, it is filtered as described in Section 8.3.
8.2.7.13 Documentation-After each sample is collected, the sample number is documented
in the sampling log, and any unusual observations concerning the sample and the
sampling are documented.
8.2.8 Continuous-flow sampling (Figure 4 and Section 6.5.2)-The continuous-flow sampling
system uses peristaltic pump (Section 6.15) to pump sample to the boat or to shore through
the SEBS-resin or PTFE tubing.
8.2.8.1 Before putting on wind suits or gloves, the sampling team removes the bags
containing the pump (Section 6.15), SEBS-resin tubing (Section 6.15.2), batteries
(Section 6.15.4), gloves (Section 6.7), plastic wrap (Section 6.9), wind suits (Section
6.12), and, if samples are to be filtered, the filtration apparatus (Section 6.14) from
the coolers or storage containers in which they are packed.
8.2.8.2 "Clean hands" and "dirty hands" put on the wind suits and PVC gloves (Section
6.7.2).
8.2.8.3 "Dirty hands" removes the pump from its storage bag, and opens the bag containing
the SEBS-resin tubing.
8.2.8.4 "Clean hands" installs the tubing while "dirty hands" holds the pump. "Clean hands"
immerses the inlet end of the tubing in the sample stream.
8.2.8.5 Both "clean hands" and "dirty hands" change gloves. "Clean hands" also puts on
shoulder length polyethylene gloves (Section 6.7.1).
18 July 1996
Method 9669
8.2.8.6 "Dirty hands" turns the pump on and allows the pump to run for 5-10 minutes or
longer to purge the pump and tubing.
8.2.8.7 If the sample is to be filtered, "clean hands" installs the filter at the end of the tubing,
and "dirty hands" sets up the filter holder on the gunwale as shown in Figure 4.
NOTE: The filtration apparatus is not attached until immediately before sampling to prevent
buildup of particulates from clogging the filter.
8.2.8.8 The sample is collected by rinsing the sample bottle and cap three times and
collecting the sample from the flowing stream.
8.2.8.9 Documentation-After each sample is collected, the sample number is documented
in the sampling log, and any unusual observations concerning the sample and the
sampling are documented.
8.3 Sample Filtration-The filtration procedure described below is used for samples collected using the
manual (Section 8.2.5), grab (Section 8.2.6), or jar (Section 8.2.7) collection systems (Reference 7).
In-line filtration using the continuous-flow approach is described in Section 8.2.8.7. Because of the
risk of contamination, it is recommended that samples for mercury be shipped unfiltered by overnight
courier and filtered when received at the laboratory.
8.3.1 Set up the filtration system inside the glove bag, using the shortest piece of pump tubing as
is practicable. Place the peristaltic pump immediately outside of the glove bag and poke a
small hole in the glove bag for passage of the tubing. Also, attach a short length of tubing to
the outlet of the capsule filter.
8.3.2 "Clean hands" removes the water sample from the inner storage bag using the technique
described in Sections 8.2.5.2 through 8.2.5.4 and places the sample inside the glove bag.
"Clean hands" also places two clean empty sample bottles, a bottle containing reagent water,
and a bottle for waste in the glove bag.
8.3.3 "Clean hands" removes the lid of the reagent water bottle and places the end of the pump
tubing in the bottle.
8.3.4 "Dirty hands" starts the pump and passes approximately 200 mL of reagent water through the
tubing and filter into the waste bottle. "Clean hands" then moves the outlet tubing to a clean
bottle and collects the remaining reagent water as a blank. "Dirty hands" stops the pump.
8.3.5 "Clean hands" removes the lid of the sample bottle and places the intake end of the tubing in
the bottle.
8.3.6 "Dirty hands" starts the pump and passes approximately 50 mL through the tubing and filter
into the remaining clean sample bottle and then stops the pump. "Clean hands" uses the
filtrate to rinse the bottle, discards the waste sample, and returns the outlet tube to the sample
bottle.
8.3.7 "Dirty hands" starts the pump and the remaining sample is processed through the filter and
collected in the sample bottle. If preservation is required, the sample is acidified at this point
(Section 8.4).
July 1996 19
Method 9669
8.3.8 "Clean hands" replaces the lid on the bottle, returns the bottle to the inside bag, and zips the
bag. "Clean hands" then places the zipped bag into the outer bag held by "dirty hands."
8.3.9 "Dirty hands" zips the outer bag, and places the double-bagged sample bottle into a clean, ice-
filled cooler for immediate shipment to the laboratory.
NOTE: It is not advisable to reclean and reuse filters. The difficulty and risk associated with
failing to properly clean these devices far outweighs the cost of purchasing a new filter.
8.4 Preservation
8.4.1 Field preservation is not necessary for dissolved metals, except for trivalent and hexavalent
chromium, provided that the sample is preserved in the laboratory and allowed to stand for
at least two days to allow the metals adsorbed to the container walls to redissolve. Field
preservation is advised for hexavalent chromium in order to provide sample stability for up
to 30 days. Mercury samples should be shipped by overnight courier and preserved when
received at the laboratory.
8.4.2 If field preservation is required, preservation must be performed in the glove bag or in a
designated clean area, with gloved hands, as rapidly as possible to preclude particulates from
contaminating the sample. For preservation of trivalent chromium, the glove bag or
designated clean area must be large enough to accommodate the vacuum filtration apparatus
(Section 6.17.3), and an area should be available for setting up the wrist-action shaker
(Section 6.17.5). It is also advisable to set up a work area that contains a "clean" cooler for
storage of clean equipment, a "dirty" cooler for storage of "dirty" equipment, and a third
cooler to store samples for shipment to the laboratory.
8.4.3 Preservation of aliquots for metals other than trivalent and hexavalent chromium-Using a
disposable, precleaned, plastic pipet, add 5 mL of a 10% solution of ultrapure nitric acid in
reagent water per liter of sample. This will be sufficient to preserve a neutral sample to pH
<2.
8.4.4 Preservation of aliquots for trivalent chromium (References 8-9).
8.4.4.1 Decant 100 mL of the sample into a clean polyethylene bottle.
8.4.4.2 Clean an Eppendorf pipet by pipeting 1 mL of 10% HCl (Section (7.4.4) followed by
1 mL of reagent water into an acid waste container. Use the rinsed pipet to add 1 mL
of chromium (III) extraction solution (Section 7.4.3) to each sample and blank.
8.4.4.3 Cap each bottle tightly, place in a clean polyethylene bag, and shake on a wrist action
shaker (Section 6.17.5) for one hour.
8.4.4.4 Vacuum-filter the precipitate through a 0.4 µm pretreated filter membrane (Section
6.17.2), using fluoropolymer forceps (Section 6.17. 1) to handle the membrane, and
a 47 mm vacuum filtration apparatus with a precleaned filter holder (Section 6.17.3).
After all sample has filtered, rinse the inside of the filter holder with approximately
15 mL of reagent water.
20 July 1996
Method 9669
8.4.4.5 Using the fluoropolymer forceps, fold the membrane in half and then in quarters,
taking care to avoid touching the side containing the filtrate to any surface. (Folding
is done while the membrane is sitting on the filter holder and allows easy placement
of the membrane into the sample vial). Transfer the filter to a 30 mL fluoropolymer
vial. If the fluoropolymer vial was not pre-equipped with the ultrapure nitric acid
(Section 7.4.1), rinse the pipet by drawing and discharging 1 mL of 10% HCl
followed by 1 mL of reagent water into a waste container, and add 1 mL of ultrapure
nitric acid to the sample vial.
8.4.4.6 Cap the vial and double-bag it for shipment to the laboratory.
8.4.4.7 Repeat Steps 8.4.4.4-8.4.4.6 for each sample, rinsing the fluoropolymer forceps and
the pipet with 10% high-purity HCl followed by reagent water between samples.
8.4.5 Preservation of aliquots for hexavalent chromium (Reference 20).
8.4.5.1 Decant 125 mL of sample into a clean polyethylene bottle.
8.4.5.2 Prepare an Eppendorf pipet by pipeting 1 mL of 10% HCl (Section 7.4.4) followed
by 1 mL of reagent water into an acid waste container. Use the rinsed pipet to add
1 mL NaOH to each 125 mL sample and blank aliquot.
8.4.5.3 Cap the vial(s) and double-bag for shipment to the laboratory.
9.0 Quality Assurance/Quality Control
9.1 The sampling team shall employ a strict quality assurance/ quality control (QA/QC) program. The
minimum requirements of this program include the collection of equipment blanks, field blanks, and
field replicates. It is also desirable to include blind QC samples as part of the program. If samples
will be processed for trivalent chromium determinations, the sampling team shall also prepare method
blank, OPR, and MS/MSD samples as described in Section 9.6.
9.2 The sampling team is permitted to modify the sampling techniques described in this method to improve
performance or reduce sampling costs, provided that reliable analyses of samples are obtained and that
samples and blanks are not contaminated. Each time a modification is made to the procedures, the
sampling team is required to demonstrate that the modification does not result in contamination of field
and equipment blanks. The requirements for modification are given in Sections 9.3 and 9.4. Because
the acceptability of a modification is based on the results obtained with the modification, the sampling
team must work with an analytical laboratory capable of making trace metals determinations to
demonstrate equivalence.
9.3 Equipment Blanks
9.3.1 Before using any sampling equipment at a given site, the laboratory or equipment cleaning
contractor is required to generate equipment blanks to demonstrate that the equipment is free
from contamination. Two types of equipment blanks are required: bottle blanks and sampling
equipment blanks.
9.3.2 Equipment blanks must be run on all equipment that will be used in the field. If, for example,
samples are to be collected using both a grab sampling device and the jar sampling device,
July 1996 21
Method 9669
then an equipment blank must be run on both pieces of equipment.
9.3.3 Equipment blanks are generated in the laboratory or at the equipment cleaning contractor's
facility by processing reagent water through the equipment using the same procedures that are
used in the field (Section 8.0). Therefore, the "clean hands/dirty hands" technique used during
field sampling should be followed when preparing equipment blanks at the laboratory or
cleaning facility. In addition, training programs must require must require sampling personnel
to collect a clean equipment blank before performing on-site field activities.
9.3.4 Detailed procedures for collecting equipment blanks are given in the analytical methods
referenced in Table 1.
9.3.5 The equipment blank must be analyzed using the procedures detailed in the referenced
analytical method (see Table 1). If any metal(s) of interest or any potentially interfering
substance is detected in the equipment blank at the minimum level specified in the referenced
method, the source of contamination/interference must be identified and removed. The
equipment must be demonstrated to be free from the metal(s) of interest before the equipment
may be used in the field.
9.4 Field Blank
9.4.1 To demonstrate that sample contamination has not occurred during field sampling and sample
processing, at least one field blank must be generated for every 10 samples that are collected
at a given site. Field blanks are collected before sample collection.
9.4.2 Field blanks are generated by filling a large carboy or other appropriate container with reagent
water (Section 7.1) in the laboratory, transporting the filled container to the sampling site,
processing the water through each ofthe sample processing steps and equipment (e.g., tubing,
sampling devices, filters, etc.) that will be used in the field, collecting the field blank in one
of the sample bottles, and shipping the bottle to the laboratory for analysis in accordance with
the method(s) referenced in Table 1. For example, manual grab sampler field blanks are
collected by directly submerging a sample bottle into the water, filling the bottle, and capping.
Subsurface sampler field blanks are collected by immersing the tubing into the water and
pumping water into a sample container.
9.4.3 Filter the field blanks using the procedures described in Section 8.3.
9.4.4 If it is necessary to acid clean the sampling equipment between samples (Section 10.0), a field
blank should be collected afterthe cleaning procedures but before the next sample is collected.
9.4.5 If trivalent chromium aliquots are processed, a separate field blank must be collected and
processed through the sample preparation steps given in Sections 8.4.4.1 through 8.4.4.6.
9.5 Field Duplicate
9.5.1 To assess the precision of the field sampling and analytical processes, at least one field
duplicate sample must be collected for every 10 samples that are collected at a given site.
9.5.2 The field duplicate is collected either by splitting a larger volume into two aliquots in the glove
box, by using a sampler with dual inlets that allows simultaneous collection of two samples,
22 July 1996
Method 9669
or by collecting two samples in rapid succession.
9.5.3 Field duplicates for dissolved metals determinations must be processed using the procedures
in Section 8.3. Field duplicates for trivalent chromium must be processed through the sample
preparation steps given in Sections 8.4.4.1 through 8.4.4.6.
9.6 Additional QC for Collection of Trivalent Chromium Aliquots
9.6.1 Method blank-The sampling team must prepare one method blank for every ten or fewer
field samples. Each method blank is prepared using the steps in Sections 8.4.4.1 through
8.4.4.6 on a 100 mL aliquot of reagent water (Section 7.1). Do not use the procedures in
Section 8.3 to process the method blank through the 0.45 µm filter (Section 6.14.1), even if
samples are being collected for dissolved metals determinations.
9.6.2 Ongoing precision and recovery (OPR)-The sampling team must prepare one OPR for every
ten or fewer field samples. The OPR is prepared using the steps in Sections 8.4.4.1 through
8.4.4.6 on the OPR standard (Section 7.4.7). Do not use the procedures in Section 8.3 to
process the OPR through the 0.45 pm filter (Section 6.14.1), even if samples are being
collected for dissolved metals determinations.
9.6.3 MS/MSD-The sampling team must prepare one MS and one MSD for every ten or fewer
field samples.
9.6.3.1 If, through historical data, the background concentration of the sample can be
estimated, the MS and MSD samples should be spiked at a level of one to five times
the background concentration.
9.6.3.2 For samples in which the background concentration is unknown, the MS and MSD
samples should be spiked at a concentration of 25 µg/L.
9.6.3.3 Prepare the matrix spike sample by spiking a 100-mL aliquot of sample with 2.5 mL
of the standard chromium spike solution (Section 7.4.6), and processing the MS
through the steps in Sections 8.4.4.1 through 8.4.4.6.
9.6.3.4 Prepare the matrix spike duplicate sample by spiking a second 100-mL aliquot of the
same sample with 2.5 mL of the standard chromium spike solution, and processing
the MSD through the steps in Sections 8.4.4.1 through 8.4.4.6.
9.6.3.5 If field samples are collected for dissolved metals determinations, it is necessary to
process an MS and an MSD through the 0.45 pm filter as described in Section 8.3.
10.0 Recleaning the Apparatus Between Samples
10.1 Sampling activity should be planned so that samples known or suspected to contain the lowest
concentrations of trace metals are collected first with the samples known or suspected to contain the
highest concentrations of trace metals collected last. In this manner, cleaning of the sampling
equipment between samples in unnecessary. If it is not possible to plan sampling activity in this
manner, dedicated sampling equipment should be provided for each sampling event.
July 1996 23
Method 9669
10.2 If samples are collected from adjacent sites (e.g., immediately upstream or downstream), rinsing ofthe
sampling Apparatus with water that is to be sampled should be sufficient.
10.3 If it is necessary to cross a gradient (i.e., going from a high-concentration sample to a low-
concentration sample), such as might occur when collecting at a second site, the following procedure
may be used to clean the sampling equipment between samples:
10.3.1 In the glove bag, and using the "clean hands/dirty hands" procedure in Section 8.2.5, process
the dilute nitric acid solution (Section 7.2) through the Apparatus.
10.3.2 Dump the spent dilute acid in the waste carboy or in the waterbody away from the sampling
point.
10.3.3 Process 1 L of reagent water through the Apparatus to rinse the equipment and discard the
spent water.
10.3.4 Collect a field blank as described in Section 9.4.
10.3.5 Rinse the Apparatus with copious amounts of the ambient water sample and proceed with
sample collection.
10.4 Procedures for recleaning trivalent chromium preservation equipment between samples are described
in Section 8.4.4.
11.0 Method Performance
Samples were collected in the Great Lakes during September-October 1994 using the procedures in
this sampling method.
12.0 Pollution Prevention
12.1 The only materials used in this method that could be considered pollutants are the acids used in the
cleaning of the Apparatus, the boat, and related materials. These acids are used in dilute solutions in
small amounts and pose little threat to the environment when managed properly.
12.2 Cleaning solutions containing acids should be prepared in volumes consistent with use to minimize the
disposal of excessive volumes of acid.
12.3 To the extent possible, the Apparatus used to collect samples should be cleaned and reused to minimize
the generation of solid waste.
13.0 Waste Management
13.1 It is the sampling team's responsibility to comply with all federal, state, and local regulations governing
waste management, particularly the discharge regulations, hazardous waste identification rules, and
land disposal restrictions; and to protect the air, water, and land by minimizing and controlling all
releases from field operations.
13.2 For further information on waste management, consult The Waste Management Manual for
Laboratory Personnel and Less is Better Laboratory ChemicalManagementfor Waste Reduction,
24 July 1996
Method 9669
available from the American Chemical Society's Department of Government Relations and Science
Policy, 1155 16th Street NW, Washington, DC 20036.
14.0 References
1. Adeloju, S.B. and Bond, A.M. "Influence of Laboratory Environment on the Precision and Accuracy
of Trace Element Analysis," Anal. Chem. 1985, 57, 1728.
2. Berman, S.S. and Yeats, P.A. "Sampling of Seawater for Trace Metals," CRC Reviews in Analytical
Chemistry 1985, 16.
3. Bloom, N.S. "Ultra-Clean Sampling, Storage, and Analytical Strategies for the Accurate
Determination of Trace Metals in Natural Waters." Presented at the 16th Annual EPA Conference on
the Analysis of Pollutants in the Environment, Norfolk, VA, May 5, 1993.
4. Bruland, K.W. "Trace Elements in Seawater," Chemical Oceanography 1983, 8, 157.
5. Nriagu, J.O., Larson, G., Wong, H.K.T., and Azcue, J.M. "A Protocol for Minimizing Contamination
in the Analysis of Trace Metals in Great Lakes Waters," J Great Lakes Research 1993, 19, 175.
6. Patterson, C.C. and Settle, D.M. "Accuracy in Trace Analysis," in National Bureau of Standards
Special Publication 422; LaFleur, P.D., Ed., U.S. Government Printing Office, Washington, DC,
1976.
7. "A Protocol for the Collection and Processing of Surface-Water Samples for Subsequent
Determination of Trace Elements, Nutrients, and Major Ions in Filtered Water"; Office of Water
Quality Technical Memorandum 94.09, Office of Water Quality, Water Resources Division, U.S.
Geological Survey, Reston, VA, Jan. 28, 1994.
8. Standard Operating Procedure No. 4-54, Revision 01, SOP for Concentration and Analysis of
Chromium Species in Whole Seawater; Prepared by Battelle Ocean Sciences, Duxbury, MA for the
U. S. Environmental Protection Agency Office of Marine Environmental Protection, Ocean Incineration
Research Program, 1987.
9. Cranston, R.E. and Murray, J.W. "The Determination of Chromium Species in Natural Waters,"
Anal. Chem. Acta 1978, 99, 275.
10. Prothro, M.G. "Office of Water Policy and Technical Guidance on Interpretation and Implementation
of Aquatic Life Metals Criteria"; EPA Memorandum to Regional Water Management and
Environmental Services Division Directors, Oct. 1, 1993.
11. "Format for Method Documentation"; Distributed by the EPA Environmental Monitoring Management
Council, Washington, DC, Nov. 18, 1993.
12. Windom, H.L., Byrd, J.T., Smith, R.G., Jr., and Huan, F. "Inadequacy of NASQAN Data for
Assessing Metal Trends in the Nation's Rivers," Environ. Sci. Technol. 1991, 25, 1137.
13. Zief, M. and Mitchell, J.W. "Contamination Control in Trace Metals Analysis," Chemical Analysis
1976, 47, Chapter 6.
July 1996 23
Method 9669
14. Phillips, H., Shafer, M., Dean, P., Walker, M., and Armstrong, D. "Recommendations for Trace
Metals Analysis ofNatural Waters"; Wisconsin Department ofNatural Resources: Madison, WI, May
1992.
15. Hunt, C.D. In Manual of Biological and Geochemical Techniques in Coastal Areas, 2nd ed.;
Lambert, C.E. and Oviatt, C.A., Eds.; Marine Ecosystems Research Laboratory; Graduate School of
Oceanography; The University of Rhode Island: Narragansett, RI, MERL Series, Report No. 1,
Chapter IV.
16. Flegal, R. Summer 1994 San Francisco Bay Cruise, apparatus and procedures witnessed and
videotaped by W. Telliard and T. Fieldsend, Sept. 15-16, 1994.
17. Watras, C. Wisconsin DNR procedures for mercury sampling in pristine lakes in Wisconsin,
witnessed and videotaped by D. Rushneck and L. Riddick, Sept. 9-10, 1994.
18. Horowitz, A.J., Kent A.E., and Colberg, M.R. "The Effect of Membrane Filtration Artifacts on
Dissolved Trace Element Concentrations," Wat. Res. 1992, 26, 53.
19. EngineeringSupportBranchStandardOperatingProceduresandQualityAssuranceManual:1986;
U.S. Environmental Protection Agency. Region IV. Environmental Services Division: Athens, GA.
20. Grohse, P. Research Triangle Institute, Institute Drive, Building 6, Research Triangle Park, NC.
21. Methods 1624 and 1625, 40 CFR Part 136, Appendix A.
15.0 Glossary of Definitions and Purposes
These definitions and purposes are specific to this sampling method but have been conformed to
common usage as much as possible.
15.1 Ambient Water-Waters in the natural environment (e.g., rivers, lakes, streams, and other receiving
waters), as opposed to effluent discharges.
15.2 Apparatus-The sample container and other containers, filters, filter holders, labware, tubing, pipets,
and other materials and devices used for sample collection or sample preparation, and that will contact
samples, blanks, or analytical standards.
15.3 Equipment Blank-An aliquot of reagent water that is subjected in the laboratory to all aspects of
sample collection and analysis, including contact with all sampling devices and apparatus. The
purpose of the equipment blank is to determine if the sampling devices and apparatus for sample
collection have been adequately cleaned before they are shipped to the field site. An acceptable
equipment blank must be achieved before the sampling devices and Apparatus are used for sample
collection.
15.4 Field Blank-An aliquot of reagent water that is placed in a sample container in the laboratory,
shipped to the field, and treated as a sample in all respects, including contact with the sampling devices
and exposure to sampling site conditions, filtration, storage, preservation, and all analytical
procedures. The purpose of the field blank is to determine whether the field or sample transporting
procedures and environments have contaminated the sample.
26 July 1996
Method 9669
15.5 Field Duplicates (FD 1 and FD2)-Two identical aliquots of a sample collected in separate sample
bottles at the same time and place under identical circumstances using a duel inlet sampler or by
splitting a larger aliquot and treated exactly the same throughout field and laboratory procedures.
Analyses of FD I and FD2 give a measure of the precision associated with sample collection,
preservation, and storage, as well as with laboratory procedures.
15.6 Matrix Spike (MS) and Matrix Spike Duplicate (MSD)-Aliquots of an environmental sample to
which known quantities of the analytes are added in the laboratory. The MS and MSD are analyzed
exactly like a sample. Their purpose is to quantify the bias and precision caused by the sample matrix.
The background concentrations of the analytes in the sample matrix must be determined in a separate
aliquot and the measured values in the MS and MSD corrected for background concentrations.
15.7 May-This action, activity, or procedural step is optional.
15.8 May Not-This action, activity, or procedural step is prohibited.
15.9 Minimum Level (ML)-The lowest level at which the entire analytical system gives a recognizable
signal and acceptable calibration point (Reference 21).
15.10 Must-This action, activity, or procedural step is required.
15.11 Reagent Water-Water demonstrated to be free from the metal(s) of interest and potentially interfering
substances at the MDL for that metal in the referenced method or additional method.
15.12 Should-This action, activity, or procedural step is suggested but not required.
15.13 Trace-Metal Grade-Reagents that have been demonstrated to be free from the metal(s) of interest at
the method detection limit (MDL) of the analytical method to be used for determination of this
metal(s).
The term "trace-metal grade" has been used in place of "reagent grade" or "reagent" because acids and
other materials labeled "reagent grade" have been shown to contain concentrations of metals that will
interfere in the determination of trace metals at levels listed in Table 1.
July 1996 27
Method 9669
TABLE 1. ANALYTICAL METHODS, METALS, AND CONCENTRATION LEVELS
APPLICABLE TO METHOD 1669
Method Technique Metal MDL (gg/L)' ML (gg/L) z
1631 Oxidation/Purge & Mercury 0.0002 0.0005
Trap/CVAFS
1632 Hydride AA Arsenic 0.003 0.01
1636 Ion Chromatography Hexavalent 0.23 0.5
Chromium
1637 CC/STGFAA Cadmium 0.0075 0.02
Lead 0.036 0.1
1638 ICP/MS Antimony 0.0097 0.02
Cadmium 0.013 0.1
Copper 0.087 0.2
Lead 0.015 0.05
Nickel 0.33 1
Selenium 0.45 1
Silver 0.029 0.1
Thallium 0.0079 0.02
Zinc 0.14 0.5
1639 STGFAA Antimony 1.9 5
Cadmium 0.023 0.05
Trivalent 0.10 0.2
Chromium
Nickel 0.65 2
Selenium 0.83 2
Zinc 0.14 0.5
1640 CC/ICP/MS Cadmium 0.0024 0.01
Copper 0.024 0.1
Lead 0.0081 0.02
Nickel 0.029 0.1
'Method Detection Limit as determined by 40 CFR Part 136, Appendix B.
'Minimum Level (ML) calculated by multiplying laboratory-determined MDL by 3.18 and rounding
result to nearest multiple of 1, 2, 5, 10, 20, 50, etc., in accordance with procedures used by EAD and
described in the EPA Draft National Guidance for the Permitting, Monitoring, and Enforcement of
Water Quality-Based Effluent Limitations Set Below Analytical Detection/Quantitation Levels, March
22, 1994.
28 July 1996
Method 9669
TABLE 2. ANALYTES, PRESERVATION REQUIREMENTS, AND CONTAINERS
Metal Preservation Requirements Acceptable Containers
Antimony
Arsenic
Cadmium
Copper
Lead
Nickel
Selenium
Silver
Thallium
Zinc
Add 5 mL of 10% HN03 to 1-L
sample; preserve on-site or
immediately upon laboratory receipt.
500 mL or 1 L fluoropolymer, conventional
or linear polyethylene, polycarbonate, or
polypropylene containers with lid
Chromium
(111)
Add I mL chromium (III) extraction
solution to 100 mL aliquot, vacuum
filter through 0.4 pm membrane, add
1 mL 10% HN03; preserve on-site
immediately after collection.
Chromium Add 50% NaOH; preserve
(IV) immediately after sample collection
Mercury Total: Add 0.5% high-purity HCl or
0.5% BrCI to pH < 2;
Total & Methyl: Add 0.5% high-
purity HCL; preserve on-site or
immediately upon laboratory receipt
500 mL or 1 L fluoropolymer, conventional
or linear polyethylene, polycarbonate, or
polypropylene containers with lid
500 mL or 1 L fluoropolymer, conventional
or linear polyethylene, polycarbonate, or
polypropylene containers with lid
Fluoropolymer or borosilicate glass bottles
with fluoropolymer or fluoropolymer-lined
caps
July 1996 29
Method 9669

30 July 1996
Method 9669
Figure 2 - Grab Sampling Device
cm PVC
?T
ROD
5-I .cm
PVC P` IPE
3m
PVC
T
1
PVC
PLATE
fe
HBa?r?+

July 1996 31
Row.
Method 9669
Figures 3 - Jar mpfing Device
?iprtspsai
(Tone)
in We%
i/4` TOIns
To Surfaes
Pump
(Tone")
Tenon
Support
p1alo
t
I L Tenon
Jar
Teflon Torpedo
Yoi=ht
32 July 1996
Method 9669
FOR 4 .. SwO Pumping System
Teflon ; hro* Tubing
TAV C.FW Pump Adaptor
Tubing
Filter
Cartridge
Clamp
r

July 1996 33
Appendix B
Mercury - Method 1631
PRISM LABORATORIES, INC.
STANDARD OPERATING PROCEDURE
TITLE: MERCURY IN WATER BY OXIDATION, PURGE AND TRAP, AND COLD VAPOR ATOMIC FLUORESCENCE
SPECTROMETRY BY EPA METHOD 1631 E
NUMBER: MET-CVA002-01 PAGE 8 OF 16
8.2.5 Spiking standards (MS/MSD)
The 100 ppt standard solution is used as the spiking solution
Place a 50-ml disposable digestion vessel on the balance and tare it. Add 6.Og of the 100
ppt standard solution. Complete to 50.Og with the sample to be spiked (44.0 g). The final
spike concentration is 12 ppt.
9.0 SAMPLES COLLECTION, PRESERVATION AND STORAGE
Aqueous samples are collected in 500ml mercury-free glass containers, which are purchased certified pre-
cleaned. The samples are collected using the dirty/clean hands technique.
Samples must be preserved or analyzed within 48 hours of collection. If a sample is oxidized in the sample
bottle, the time to preservation can be extended to 28 days.
The samples are oxidized in the sample bottle by adding 2.5 ml of BrCI solution. Before analyzing the
samples, a yellow color should be present (or starch iodide indicator paper turns purple); otherwise, more
BrCI solution should be added and a corresponding method blank prepared to account for the excess of
BrCI. For turbid samples add 5.0 mL BrCI and allow more time for oxidation.
Samples not analyzed within the designated holding time must be flagged and the data are considered
minimum values. For regulatory reporting the sample must be recollected and reanalyzed within the
designated holding time.
Container blanks must be analyzed to verify that no mercury is present a levels above the reporting limit. To
check the container blank, 2.5 mL of BrCI solution is added to a sample bottle that contains 500 of DI water.
The bottles are purchased from a commercial vendor and certified clean. 5% of the bottles from each lot are
tested as container blanks. If mercury is present above the reporting limit, the batch must be rejected or the
bottles re-cleaned.
10.0 PROCEDURE
10.1 INSTRUMENT SET-UP
10.1.1 Instrument Conditions
Concentration Range 1.0 - 50 t 0.5 - 50 t
Purge Volume 8 mL
...... ......... ................................................_..._............
......-............ 28 mL
....... ..._...._..._..._.......
__._.._............._....._.._..............__........_...
Gas Flow
.................................._.................... _.... ..._...........
..... .... 0.5 L P M
............... _..................... _..... ............ ........... .............-.._.........
..........-........ 0.5 L P M
......._....._...._..................-......_._...........--._.............. ........
__.._._.....
Pump Speed_ .......... .................................. _......._. _.
.... 5 mL/min
................_.................._....................._..............._....................
.................... 7 min
................. ............... .........._..................._..__......................_.......
Rinse
......................................... _.-........ _...... ...-
_... 10 secs
.............. ......... _......... ............................................._._...... ......
_.................. 10 secs
............... ._............. --..---.............................-_....... --
_Uptake.._.._....._ ...................._....._-._..._....._............,. _ ._. _ . 96 secs-.-..................................... ........ ..._240_secs---........ ..._..... .................... --
Fluorescence Method......-- ...._... .... ..._CVAFS with trap. ........._......._ .... .................... ..._CVAFS with tra.P...._..................
Replicates
.......................... _ ._.......... ...... -_... --
-... 1
......- . ........................ _. ................ . ...........
.............. 1
................. ...... -...... _ ................_._..-
Full Scale
_._....._....... _....... ........... ............... ........ _................ _..............
--- 15
......... ._.........................._........_. --._................... ..... .
................... 15
....... ...................................... ........... __......................... ...._...
Integration _............. ....._....... ........ -._.... .. _.
.... 0.70 secs
...- ............................................................... ..-............. ............ .
........... .._.... 0.70 secs
.............. .._._................... ............. ---_.._.......................... _---..
_Fumace..-1...-Temp.......-...._...-....-- ....... ..... ..._450._ .............................................
............._.............
...._.._........ 450
.................. _..... -............ _................ __........... _....... _.........
Fumace_2 Tem.P...... .................................... ---. --450._....................-. 450
Dp?Time.-..................................... __..._. 5secs .......... ........ ----- ..... ............ . ..._5_secs.._.... _.._..........._..... _.............. -.
Desorption Time _
... ..
...._... 70 secs
........ ...._.. .......................... .......... ........ .._ -.............._._.....
................... 70 secs
._..............................,....._._....-...._...._.._..........._.._?...
Stabalize Time 10 secs 10 secs
?aF N1 A TRW Michael-F. Easley, Governor
William G. Ross Jr., secretary
7 North Carolina Department of Environment and Natural Resources
> Alan W. Klimek, P.E., Director
p Division of Water Quality
August 12, 2003
Subject: NPDES Mercury Requirement- EPA Method 1631
Additional Information
Dear NPDES Permittee:
In a previous letter dated August 30, 2002, your facility was notified of being subject to a new low-level mercury
analysis (EPA Method 1631) for NPDES monitoring requirements, beginning September 1. 2003. The notification
letter was mailed to 155 subject facilities.. Si;ice that mailing, the Division has participated in several Mercury 1631
Workshops to provide the regulated community with information on the new analytical requirements and clean
sampling recommendations. Based on comments received at these workshops, the following items are intended to
clarify certain NPDES requirements for the 155 subject facilities.
1. Mercury Sampling and Compliance. It is recommended that facilities collect some effluent samples for Method
1631 analysis prior to the 9/ 1 /2003 effective date, in order to gain experience with the recommended clean
sampling techniques as well as the analysis requirements. NPDES compliance will be judged using the new
method results beginning 9/l/2003.
2. What Samples are Subject to Method 1631. Beginning 9/ 1 /2003, all effiuent samples collected for mercury
from the subject facility are required to perform low level mercury analysis. This includes effluent samples
collected for any of the following requirements: a) monitoring specified in your "Effluent Limitations and
Monitoring Requirements" page of your NPDES permit; b) monitoring specified in your NPDES Pretreatment
Short Term Monitoring Plan (STMP) or Long Term Monitoring Plan (LTMP)-, and c) NPDES permit renewal
requirements. The effluent samples must be analyzed by a laboratory certified by the Division for Method
1631, and effluent results must be submitted with the applicable monthly Discharge Monitoring Report (DMR).
3. Grab Sampling. The Environmental Protection Agency (EPA) currently recommends that mercury samples for
Method 1631 analysis be collected as grab samples, since automatic composite samplers may be more subject
to contamination. Therefore, the Division will allow permittees to collect single grab samples directly into lab-
provided sample bottles for permit requirements, even though the NPDES permit may specify "composite"
samples for mercury. The grab sample must be representative of the discharge.
4. Laboratory Reporting Level. Based on the Division's review of commercial laboratories currently performing
Method 1631, a majority of labs were reporting a minimum level of quantitation (ML) of either 1.0 ng/1 or less.
The Division will require an ML of 1 ng/1 beginning 9/1/2003, which is considered reasonable and
economically achievable.
5. Field Blank Collection. Method 1631 requires that a minimum of one field blank accompany each set of
samples collected from the same site at the same time. The field blank is used to identify contamination during
sample collection and transport activities. If mercury is present in the field blank at levels that would
compromise reliable measurement of mercury in the wastewater sample, you should assume that the effluent
sample was contaminated during collection or transit, and you will need to eliminate any source of
contamination that has been identified. The permittee shall report all effluent sample results on the applicable
monthly DMR. If a field blank fails to meet quality control criteria, the permittee should note that fact in the
DMR Comments Section, and append the lab sheet for that field blank. For those facilities sampling for
mercury under a limited monitoring frequency (quarterly or less, such as Pretreatment LTMP/STMP
monitoring), you must resample if the field blanks are outside quality control criteria. However, for those
facilities with more frequent effluent monitoring requirements (i.e., monthly or more frequent), resampling is
not required if field blank quality control criteria are not achieved for a given sample event. Refer to Method
1631, Revision E (Section 9.4.5.2- Quality Control- Field Blanks), for specific quality control criteria regarding
field blank acceptability and effluent sample reliability.
6. Field Blank Subtraction. Method 1631 provides for subtraction of field blanks (provided they meet quality
control criteria defined above) from the effluent sample result if deemed appropriate by a regulatory agency.
Upon review, the Division will not allow field blank subtraction from effluent samples for reporting purposes.
Based on a recent study using Method 1631 for wastewater samples collected at 38 wastewater treatment
plants, field blank concentrations were generally below the method quantitation level. Therefore, beginning
9/l/2003, the permittee shall report the result of the effluent sample as provided by the certified lab, without
field blank subtraction, on the monthly DMR submission. In the event of a mercury limits violation, the
permittee retains the option to request remission of any penalty. If the permittee believes that the violation
N. C. Division of Water Quality 1617 Mail Service Center Raleigh, NC 27699-1617 [phone]
Customer Service 1 800 623-7748 N?' . `
NPDES Mercury Requirement
Page 2 of 2
resulted from background contamination as indicated by the field blank, the permittee will need to document
that fact with field blank quality control data.
7. Sample Preservation/Holding Times. Samples for total mercury analysis by Method 1631 must be collected in
tightly-capped fluoropolymer or glass bottles and preserved with BrCI or HCI. within 48 hours of sample
collection. The time to sample preservation may be extended to 28 days if a sample is oxidized in the sample
bottle. Samples must be analyzed within 90 days of sample collection.
If you have any questions about the contents of this letter, please contact the applicable Division staff listed below:
Mercury Method:
Certified Labs for Method 1631
NPDES Permitting:
NPDES Compliance:
NPDES Pretreatment:
Roy Byrd
Fred Bone
Tom Belnick
Vanessa Manuel
Dana Folley
919-733-3908, ext 213
919-733-3908, ext 273
919-733-5083, ext 543
919-733-5083, ext 532
919-733-5083, ext 523
Sincerely,
original signed by Dave Goodrich for
Alan W. Klimek, P.E.
cc (hardcopy): CLANC, c/o Lew Hicks, Environmental Chemist Inc., 6602 Windmill Way, Wilmington, NC 28405
DWQ Regional Offices, Water Quality
cc (email): EPA Region 4, Madolyn Dominy, Marshall Hyatt
DWQ Water Quality Section; Regional Office Supervisors
DWQ Laboratory Section; Steve Tedder, Larry Ansley, Jim Meyer, Roy Byrd, Fred Bone
DWQ Modeling/TMDL, Michelle Woolfolk
DWQ NPDES Compliance, Vanessa Manual
DWQ Pretreatment Unit
DWQ NPDES Unit
NC League of Municipalities, Anita Watkins
NC Labs Certified for Method 1631e
Appendix C
Metals - Method 200.8
SOP NO,: MET-ICPMS
Revision: 12
Date: 5/21/07
Page: I of 19
STANDARD OPERATING PROCEDURE
for
DETERMINATION METALS A TRACE ELEMENTS Y INDUCTIVELY
COUPLED-TMA S SPEC. ,IFT Y (IC -N S) - METHOD 200.8

May 21, 2007
Approved by:
Supervisor
COLUMBIA ANALYTICAL SERVICES, INC.
1317 South 13th Avenue
Kelso, Washington 98626
O Columbia Analytical Services, Inc. 2007
1
SOP NO.: MET-ICPM
Revision: 12
Date: 5/21/07
Page: 2 of 19
E ° I' METALS A T ACE I -T- S Y IN UC'TIV I,
C - S S SPECTROMETRY (ICP-MS) - ` EJ11 D W8
1. SCOPE AND A 7___ _ ? ' `i"I
1.1. This procedure describes the steps taken for the analysis of soil, sludge, sediment and water
digestates using EPA Method 200.8 for a variety of elements. This SOP is intended to be
used in conjunction with the EPA method as a guide to ICP-MS analysis. The complexity
of the technique gene ally requires outside study of appropriate literature as well as
)eels "zed ` ir'r a cn ilified sp. u1 )scopist. Tlx: scope of this do .rn: it do. ; not
sc< c pri d for
rg i1m_, (m:Ls) nor c w:n,., 1. The
reported L may t v adjusted if required for spe( project re, (ir i. ,, ' c,} ever, the
capability of achieving other reported MRLs must be demonstrated. Method Detection
Limits (s) which have been achieved are listed in Table 1. These may change as
annual studies are performed.
2. METHOD SUMMARY
2.1, Prior to analysis, sir nroprlate sample preparation methods.
The digestate is analy; :1 ntc i ;ing ICP spectrometry.
2.3. Deviations from the reference method(s): This SOP contains no deviations from the
reference methods,
DEFINITIONS
3.1. Analysis e --- . - Samples are analyzed in a set referred to as an analysis sequence. The
sequence begir ; with instrument calibration followed by sample digestates interspersed
with calibration standards.
SOP N,: MET-ICMS
Revision: 12
Date: 5/21/07
Page: 3 of 19
3.2. Indel Calibration Verification (ICV) - ICV solutions are made from a stock
solution G ich is different from the stack used to prepare calibration standards and is used
to verify the validity of the standardization.
3.3. Matrix Spike (MS) - In the matrix spike analysis, predetermined quantities of standard
solutions of certain analyses are added to a sample matrix prior to sample digestion and
analysis. The purpose of the matrix spike is to evaluate the effects of the sample rnatrix on
the methods used for the analyses. Percent recoveries are calculated for each of the analytes
detected.
3. l1 CJSD) - In i)e mat x spike c . nlic. le, anal ;is, predetermined
I. or to
ie
ca I(" Jr E of 'me J , "e' `,?e ., a, l r 1 -,,ve u- peen the
M A spikes is ctelculated and used to assess t alytic. I precisi n.
17. C( c - , .-j Standard (C CV) - A standard analyzed at specified
i t----. A used to verify t' -:e ongoing validity of the instrument calibration,
3.8. Instrument : (C CB) - The instrument blank (also called continuing calibration blank)
is a volume of blank reagent of cornposition identical to the digestates. The purpose of the
CCB is to determine the levels of contamination associated with the instrumental analysis.
4. INTERFERENCES
5. SAFETY
5.1. All appropriate safety precautions for handling solvents, reagents and samples must be
taken when performing this procedure. This includes the use of personnel protective
equipment, such as, safety glasses, lab coat and the correct gloves.
5.2. Chemicals, reagents and standards must be handled as described in the CAS safety policies,
al a- 1 is is and in MS- -3-s whc °e avail;°' `cr to the CAS - :iviron ental,
z {. .:o bel ' :.ninl
rely
rot- _V c n me =nc ! while
pouring ac as. F c- safety gig ses should be .: orn while .: uz i?ilr un the solutions. Lab
coat and gloves s onid always be worn while worldng with, thUse solutions.
5.4. High Voltage - The generator supplies up to 2000 watts to maintain an 1CP. The power
is transferred through the load coil located in the torch box. Contact with the load coil
while generator is in operation N.:!1 likely result in death. When performing maintenance on
the RF generator, apl ro -'`e ; ndi. n r " all "TV capacitors must be performed as per
manufacturer.
5.5. 1_,T V Light - The pl isr u. -ce c. I emission, and must not be viewed with
the naked eye. Protecti•.? lenses are in place o-i the instrument. Glasses with special
protective lenses are available when direct viewing of the plasma is necessary.
6. SAMPLE COLLECTION, CONTAINERS, PRESERVATION, AND sToIZACE
6.L Samples are prepared using methods 3020A or 3050B (CAS SOPsM-ET-3020A and i "T-
3050B). Samples are generally received in the ICP-MS laboratory as 1% Nitric Acid
digestates, Samples are stored in the appropriate volumetric containers.
62. Each time water samples are preserved after arrival at the lab, hold the samples for a
minimum of 16 hours and verify the p11<2 prior to digestion.
63. Di gestates originating from soil samples with greater than 60% solids are diluted prior to
instrumental analysis by a factor of 5. This allows the analysis to achieve maximum
sensitivity which results in optimum Method Reporting Limits (MRL). Following
analysis, digestates are stored until all results have been reviewed. Digestates are brought
to 3< pH<12 and disposed of through the sewer system 2 weeks after data is reviewed.
SOP NO.: ET-ICPMS
Revision: 12
Date: 5121/07
Page. 5 of 19
ry
STANDARDS, REAGENTS, CONSUMABLE MATERIALS
c .
1 A' p' ?C 1 e : 1 ,C l.t: L.-& is p r -l ?. Prep,

8.1.1.I.Stock Standard Solutions: The manufacturer, lot number, and expiration
date of each stack standard is recorded in a bound logbook located in the
room 113 of the Metals Department, Additionally each stock standard is
given a unique, identifying name. Stack standards are typically purchased
at 1000 m-!L concentr-bons.
8.1.1.2.Inte r diate mixed stock solutions are
made clc rds described above. The individual
co po'- d soluti? . is recorded in a bound logbook located
in the h `aoratc r and m' .c d solution is given a unique, identifying
name.
8.1,1.22A second source intermediate stock standard is prepared from
three premixed solutions purchased from Inorganic Ventures;
QCP-CICV-1, QCP-CICV-2, and QCP-CICV-3. A 100 rnL Class
A volumetric flask is partially filled with reagent water and 5.0 mL
of L ltrex nitric acid. Add 2.0 mL of QCP-CICV-1, and 1.0 mL
2:. C is f ;3ar( A 1.00
iall water
nixed
(}. n L1 i, i ,,C and
di _ v _D vow -re with gr_ t water.
8.1.1.3.2.The working ICV solution is prepared by first partially filling a
100 mL Class A volumetric flask with reagent water and 1.0 rnL of
U)tr(-x nitric acid. Add 0.5 mL of the ICV intermediate stock and
di. to volume with reagent water. The expiration dates foi- the
o" iry [C%7 solutions are the earliest date of the
n{ded, add internal standards after
:4i .:.e _rEP bottle. The ICV/QCS should be
f d to me data-duality needs and a fresh solution
shout,' be p ;par J quart 'y or more frequently as needed.
8.1.1 Internal. Standards Stock Solution - Prc.:: -. 10 p,g/mL solutions by making
appropriate dilution of stock standards wig.; reagent water, and store in a FEP
bottle. Use this solution for addition to blanks, calibration standards and samples,
or dilute by an appropriate amount using, 1% (v/v) nitric acid, if the internal
standards are being added by peristaltic pump.
PREVENTIVE MAINTENANCE
9.1. All maintenance is documented in the instrument logbook. CAS/Kelso maintains a service
contract with the instrument manufacturer that allows for an unlimited number of service
calls and full reimbursement of all parts and labor.
9.2. Most routine maintenance and troubleshooting is performed by CAS staff. Preventive
maintenance activities listed below should be performed when needed as determined by
instrument performance (i.e, stability, sensitivity, etc.) or by visual inspection. Other
maintenance or repairs may, or may not require factory service, depending on the nature
of the task,
SOP NO,: MET-1cPMS
Revision: 12
Date: 5/21/07
Page: 7 of 1
?-
10. -S
??, :nd to
e
res4..v atu pert by persuan. i in tw,u _ t ?A he i- iatu l ability' to
generate accep esults utilizing this SOP. This clemo?- -,t .,]on i ; in accordance with
the training program of the laboratory. Final review and sign-off of the data is performed
by the department supervisor/manager or designee.
10.2. It is the responsibility of the department supervisor/manager to document analyst training.
Documenting method p---"icienc', as dc,c.'be' the applicable EPA method, is also the
responsibility of the c .
11. PROCEDURE
11.1. The following parametc?-._ are monitored to assure awareness of changes in the
instrumentation that serve as signals that optimum performance is not being achieved, or
as indicators of the physical condition of certain consumable components (i.e. EMT and
cones).
11.1.1. Multiplier Nigh Voltage
Record I-IT2 setting. As the EMT ages, the voltage applied wi" to be
increased to maintain sensitivity. See instrument manual for details.
Record HTI setting. CAS does not utilize the low sensitive detection mode
(analog) controlled by the HT1 setting. Proper setting of the voltage, however, is
necessary due to the interaction of the two. When H.T2 adjustment becomes
necessary, the HT1 adjustment should also be performed at the same time.
The PQ Excell and Y-Series instruments use a dual mode detector (pulse
count/analog). These detectors are adjusted by the instrument software.
11.2. Optimization
SOP NO.: MET-ICPMS
Revision: 12
Date: 5/21/07
Page: S of 19
11.2.1. Gas Flows
11.2.1.1.Allow a period of not less than 30 minutes for the instrument to warm-
up.
11.2.1.2.Aspirate a mixed element tune solution into the plasma and monitor the
instrument output signal at mass In 1.15 on the ratemeter. Adjust the
nebulizer and auxiliary flows to obtain maximum signal. Adjust the
tension screw on the peristaltic pump to obtain minimum noise in the
analytical signal. Record flow rates and note any large variances.
3 , _ in evil` of _ . -ferent
.-en b n {.
W mile om, oring the output signal of a tune ,elution at ass In 115 on the
ratemeter, adjust the ion lenses to obtain maximum sensitivity. Refer to the
instrument manual for details on performing the adjustments.
11.2.3. Mass Calibration
Aspirate a s id U using the Mass Calibration
program it ments identified in the program as the
points used f ? ?. D the instrument manual for details
pertaining to the m; s cantarL__'on procedu-e.
11.2.4. Resolution Check
Using the spectra created during the mass calibration procedure, check the
resolution. The resolution must be less than I AML; at 5% of peak height, but
should be set at approximately 0.75 AMU at 5% of the peak height. The PQ
Excell instrument checks the resolution at 10% peak height which is more
rigorous than at 5%.
11.2.5. Stability Check
Using the mixed element solution form the mass calibration check (25 ppb for the
P, 1 ppb for the ExCell) perform a short-term stability check. Instrument
stability must be demonstrated by running the tuning solution a minimum of five
times with resulting relative standard deviations of absolute signals for all analytes
of less than 5%.
11.3. Internal Standards
SOP O.: MET-ICPMS
Revision: 12
Date: 5/21/07
Page: 9 of 19
1.1.3.2. The internal standards used will vary depending on the sample matrix, known
interferences, and other factors. For full mass range scans a rninimum of three
internal sta-d,,,,°ds n-,r,st he used. The concenlr"aticui of the 3nterital stand ird is set
such that good precision is obtained in the it _ urement of t' e isotone tsed for
Corr ion : t:,rna]
an
_ I bs_
Intemal Standard Mass Cone a .I
6Lithium 6 50
Scandium 5 50
Yttrium 89 50
Rhodium 1.03 50
Indium 115 50
Terbium 1
Holmium
Lutetium
Bismuth 5(p
c ;c 'ble 1,imit '.ton
a
polyatomic ion interference
a,b
isobaric interference by n
a
a - May be present in environmental samples.
b - In some instruments Yttrium may form measurable amounts of YO' (105 ama) and
YOH' (106 amu). If this is the case, care should be taken in the use of the cadmium
elemental correction equation.
11.3.3. Calibration using internal standards and internal standard ratios is performed by
the instrument software using calculations shown in Attachment A.
1.1.4. Analytical Run
11.4.1. Select the correct method.
11.4.2. Nebulize Standard 0 (Blank) into the plasma. Allow 1-2 minutes for system to
equilibrate prior to establishing baseline.
11.4.3. Follow directions on computer screen to perform standardization. Operator will
sign and date the first page of standardization.
Note; For AECEE projects, the CRA stand rd concen' pions v ill be equal to the
project MRI..s.
12.
QA/QC REQUIREMENTS
12.1. Initial Demonstration of Prrformr-ice ( t')
12.1.1. Acceptable - . . _.. L)e demonstrated before analysis of
samples l,eb' changes to the procedures have been
made.
12.1.I.I.The accuracy and precision of the procedure is validated by preparing and
analyzing four LCS aliquots.
12.1.1.2.The average percent recovery must be 85-115% (for water, and within
LCS limits for soils) and the RSD< 30%12.1.2. Initial Demonstration of Performance must be performed by each analyst.
performing sample analysis and documented in laboratory records.
12.4. Method 13eiection Limits
12.4.2. Calculate the u: /,rage concc.-:tration foL..id (x) and the standard deviation of the
concentrations for each analyte. Calculate the MDL for each anaiyte using the
correct T value for the number of replicates. MDL's must be performed annually
or whenever there is a significant change in the background or instrument
response.
12.5. Ongoing C Samples required are described in the CAS-Kelso Quality Assurance
Manual and in the SOP for Sample Batches. In general, these include:
12.5.1. A Continuing Calibration Verification (CCV) and Continuing Calibration Blank
(CCB) are analyzed after every 10 samples. The control limit for CCV recoveries
is x-10%. if the control limits are exceeded, the instrument will be recalibrated
and the previous 10 samples reanalyzed.
12.5.2. As per method 200.8, a digested duplicate and matrix spike are analyzed at a
frequency of one per 10 samples (or one per batch if fewer than 10 samples). The
matrix spike recovery and relative percent difference will be calculated while
analysis is in progress. The control limit for matrix spikes is 70-130% as
specified by method 200.8, duplicate RPD limits are 20% for waters and 30% for
1.2.5.3. Laboratory Control Samples are analyzed at a frequency of 5%G or one per b,_ 1,
whichever is greater. The control limits for aqueous LCS recoveries is 85-115 o,
soil control limits are specific to the reference material being used. Client specific
C criteria may supercee these limits. the control lirnits are exceeded, the
sampl-s will be redigested and reanalyzed.
12.7. Instrument Detection Limits (IDL) and linear ranges are performed quarterly, Method
Detection Limits ( Ls) are performed annually. These will be calculated and made
available to the IC -MS operator.
12.9. Note that the nomenclature of certain C samples in the method differs from that of
CAS, but the function of those samples is equivalent in both cases.
SOP NO.: MET-ICPMS
Revision: 12
Tate: 5121107
Pale: 13 of 19
13. DATA REDUCTION, REPORTING, AND REVIEW
13.1. Using the results of integrations for applicable masses, the instrument software calculates
the measured (instrument) sample concentration using an internal standard calibration
algorithm (Attachment A). This calculation includes appropriate interference corrections.
13.1.1. Target analyzes are corrected by internal standardization via three possible
scenarios. The analysis record (raw data) will indicate the IS masses and target
element masses used for quantitation.
If the mass of the target analyte is less than the mass of the first internal
s andard ie IS o to est mass) e ' ,.rg(anah re-( ences t?iis ,.7 rnal
rner,
_ rc:,
ta. E ? ,.` n ces c e sta i -. tr ,iation
as descr )ed in Attachment A.
If the mass of the target analyte is greater than the mass of the last internal
standard (the IS of highest mass) the target analyte references this internal
standard alone using the algorithm described in Attachment A.
EXCEPTION: ,aar" ." '_. q„ yin,. ,es must use the technique of internal
internal standard (rather than
standard nc: m'-
interpolation).
13.1.2. Typical intern st.im __i _ _:r.,rences when using internal standard normalization by
referencing a single internal standard are listed below.
Internal Internal
Standard Standard
Analyt.e Reference Analyte Reference
Aluminum Li-6 Manganese Ga-71
Antimony In-I 1.5 Molybdenum In-115
Arsenic Ga-71 Nickel Ga-71
Barium Lu-175 Selenium Ga-71
Beryllium Li-6 Silver In-115
Cadmium In-I15 Thallium Lu-175
Chromium Ga-71 Uranium Bi-209
Cobalt Ga-71. Vanadium Ga-71
Copper Ga-71 Zinc Ga-71
Lead Lu-175
III Calculate sample results for each analyte using the data system printouts (showing
instrument concentrations) and digestion information. The digestion and dilution
information is entered into the data system. The data system then uses the calculations
below to generate a sample result.
Aqueous samples are reported in lg/L.:

Solid samples are reported in mg/Kg:
mglKg (Sample) = C?j __ Pc-,-` Dig.-:;tion P,
Digestion Vol. (ml) I mg
4^
1L 100og
10001111 I ,kg
S, .iple wt. (g) I00oug
where: C - C instrument in ug/L, (in digestate).
F=L t f
13.4. Data Review and Reporting
1.3.4.1. Production
Tier IR or higher type deliverables require a diskette of the ICP-MS data to he
generated. The file is also stored on the hard drive of the ICI'-M until the data.
package has been generated.
13.4.2. Non-production
1 4. CONTENGENCIES HANDLING ~ OUT-OF-CONTROL OR UNACCEPTABLE
DATA
Corrective action measures applicable to specific analysis steps are discussed in the applicable
section of this (and other applicable) OP(s). Also, refer to the SOP for Nonconformity and
CorVe-°tr„- Ac*r`on for co-ect p-ocedures for identifying and documenting; such dat1. Procedures
for, )nlvincr & `a nuali` erc nr? described in 1'ia fine fnr , 1- -t C net ,017, or in nrnif'of-speclflc
re.
1 ..
"- ;s method was validated through single laboratory studies of ace s y and re ';icon, Refer to
the reference method for additional available method performance data,
The method detection limit (MDL) is established using the procedure described in the SOP for
The Determination of Method Detection Limits (ADM-MDL), Method Reporting Limits are
established for this method based on MT:'-' s',:-.dies n nd as ~secified in the CAS Quality Assurance
Manual.
16. POLLUTION _ ' VE T ' w
It is the laboratory's practice to i linimi .- the amount of solvents and reagents used to perform this
method wherever technically sound, feasibly possible and within method requirements. Standards
are prepared in volumes consistent with the laboratory use in order to minimize the volume of
expired standards to be disposed of. The threat to the environment from solvents andlor reagents
used in this method may be minimized when recycled or disposed of properly.
1. WASTE MANAGEMENT
IT L The laboratory will comply with all Federal, State and local regulations governing waste
management, particularly the hazardous waste identification rules and land disposal
restrictions as specified in the CASE S Manual.
17.1 This method uses acid. Waste acid is hazardous to the sewer system and to the
environment. All acid waste must be neutralized to a pH of 5-9 prior to disposal down the
drain. The neutralization step is considered hazardous waste treai -nt and must be
documented on the treatment by generator record. See the CAS L- '. Manual for details.
18® „ siG
SOP NO.: MET-ICPMS
Revision: 12
Date: 5/21/07
Page: 16 of 19
18.1. Refer to the SOP for Documentation of Training for standard procedures.
18.2. A minimum of two senior level spectroscopists are to be maintained on staff at all times.
Senior spectroscopists are defined as individuals with a riumi um of ten years combined
education and experience in, or related to atomic spectroscopy. Of those ten years, a
minimum of two years of ICP- S experience is required.
18.3. To maintain expertise in current technology, senior staff members are encouraged to
attend technical seminars containing significant information relevant to ICP-MS as they
are available. In addition, senior spectroscopists are also encouraged to attend training
se.-ssions o''frred periodically by the ICI-)-MS instrument manuf.-sturr:-s.
rop y p1, _ on to
- - s r, .: ; ve data
.ed by
hanus-oai oper aia t ie lnsu -meF.o idW az.
1.8.5. Training outline
18.5.1. Review literature (see references section). Read and understand the SOP. Also
review the applicable MSDS for all reagents and standards used. Following these
reviews, obse~ve 'lie proce ':ire perfo: -d by ari experienced analyst at least
three times.
18.5.2. The next ' 4 . procedure under the guidance of an
experienced a_e: pev oL, !ie analyst is expected to transition from
a role of assi,," v, z 1 ( i g the I rocedure with minimal oversight from an
experienced analyst.
18.5.3. Perform initial precision and recovery (IPR) study as described above for water
samples. Summaries of the IPR arc reviewed and signed by the supervisor.
Copies may be forwarded to the employee's training file. For applicable tests,
IPR studies should be performed in order to be equivalent to NE1.AC's Initial
Demonstration of Capability.
18.6. Training and proficiency is documented in accordance with the SOP ADM-TRANDOC,
19. REFERENCES
19.1. Then-no Elemental Instrument Manuals
19.2. USEPA, Methods for Determination of Metals in Environmental Samples, Method 200.8,
Revision 5., May 1.994.
SOP NO.: ME'I,-ICPI~F%IS
Revision: 12
Date: 5/21/07
Page: 17 of 19
TABLE 1
to orti i its d Metiod eection Li its
'e'ater bag/L) Water (ag/L) Soii/Sedintent Tip ;ne (rnglkg)
(n_,;/kg)
CLP Digestion EPA 3020A ur" 305013 Digestion
Digestion 3tion
Analyte MRL MDL MRL MDL
Al-rm-..m 0.5 5 0, A
n o
...... .. ..........
Arser . .......... ... ...... ....

Bariu ....... . .. ....... . ....... ....... ...........
Beryl' UM 0-2 0 o,c,a
Boron 0.5 0" 10 9 1.: 0.' S?
Cadmium 0.05 0.02 0.05 0.05 0.05 0.01 0.05
Chromium 0.2 0.05 0.2 0.06 0.2 0,05
Cobalt 0.02 0.01 0.05 0.03 0.02 0.01 0.
0.02
0.04
0.02
Copper 0.1 0.03 0.2 0.2 0.1 0.01 .1 0.03
Lead 0.02 0.006 0.1 0.05 0.05 0.02 0.G,? 0.01.
Manganese 0.05 0.02 0.1 0 - 0.02 0.05 0.02
Molybdenurn 0.05 0.02 ;5 0.01 0.05 0.01
Nickel 0.2 0.03 _ 0.2 0.02 0.2 0.03
Selenium 1.0 0.4 { 1.0 _
Silver 0.02 0.007 -2 0.01 0.02 0.01 0.02 0.02
't'hallium 0.02 0.01 0.02 0 01 0.02 0.01 0.02 U l
Tin 0.1 0.02 0.1 0.04 - - 0.1 0.01
Uranium 0.02 0.003 0.02 0.01 0.02 0.01 0.02 0.01
Vanadium 0.2 0.05 0.2 0.03 0.2 0.02 0.2 0.02
Zinc 0.5 0.2 0.5 0.2 0.5 0.05 0.5 0.08
MDL
0.5
.`?2.
jj
02
02
SOP O.: MET-ICPM
Revision: 12
Date: 5/21/07
Page: 18 of 19
Attachment A
Internal Standard Calibration Calculations
M
nents
The actual concentration is not important but, ideally, the internal
standard should be within the mid--range of the anticipated
concentrations. Internal standard correction is achieved by
normalising the integral counts to the first sample defined in the
Procedure file.
1. - integrated counts for the first sample at the mass of the
internal standard.
In = integrated counts for sample n at the : pass of the intern;
standard.
VG PlasniaQuad Software Manual E-14 Issue 3

-
I„ - integrated counts for the first sample at the mass of the
first internal standard.
I _ integrated counts for sample n at the mass of the first
internal standard,
Fc . rr: . _s ...

Issue 3 ,Amendment I E-15 VG PlasaQuad Software Manual

if, ments
The slope of the graph (F) defined by the two normalisation factors
is given by:
FS `FRl2 ® FMI)
(m2 - m)
The normalisation factor for a sample at mass x is given by:
°V
I - :.it - ints for first sample at the ma : of me
refemce Un. rnal stanc_rd.
I? - integrated counts for sample at the mass of the reference
internal standard.
V PlasmaQuad Software Manual E-16 Issue 3 Amendment t

J :® - - ........
Table of Contents
Table of Contetnts................................................................................ ...........................................................1.
1. Calculation Methods .................................................................. ............................................................2
1.1 Integration ........................................................................ ............................................................3
1.1.1 Scale to count rate .............................................................. ............................................................3
1.1.2 Dead time correction ........................................................... ...........................................................3
1. 13 Detector Cross Calibration .................................................. ...........................................................3
I.IA Simultaneous Detector Data ................................................ ...........................................................4
1. L5 Integration .......................................................................... ............................................................4
1,2 Interference Correction .................................................... ............................................................5
1.3 Internal Standard Correction.......... ....
.......................
....................................................
....... 6
1.3.1 Internal standard analytes .................................................... ...........................................................6
1.3." Analy: ; whi a; not inrn,l. :anc s ........................... ...........................................................7

1.. >i, . si . ....... .....
1.5.3 3 ii-quantltaifve Rs onse Curves ................................... .......................................................... 11
1.6 Blank Subtraction.. ..... __ ... _ .......... .........
...................................
_ .... ....... ......... 13
1.7 Concentration Calculations.
..............................
.............................................
....... ...... 14
1.7.1 Fully-quantitative analysis .................................................. .........................................................14
1.7.2 Standard addition analysis ................................................... .........................................................14
1.7.3 Semi-quantitative analysis....... ... ......
........
...................................
......... ........ ...... 15
I'S Externa I: fft Correction ................................................. ..........................................................16
19 Spe , , aubtraction ................................................ ..........................................................17
2. Time resolN U Analys;i (T ..................................................18
2.1 Profile TRA (PIRA).. ......................................................18
3, I, I Integration 18
3,1.2 Interference Correction. ........ ......................................................... i 8
3,1.3 Internal Standard Correcti,: .............................................. ..........................................................19
3.1.4 Baseline Correction ............................................................ ..........................................................19
3.1.5 Calibration ........................................................................... .........................................................1.9
3.1.6 Blank Subtraction ................................................................ .........................................................19

..................
3.1.7 Concentrations. ... _ .......
........................
................. ... __ ... ___20
11.8 Dilution Correction ............................................................ ..........................................................20
3.2 Transient TRA (TTRA} .................................................... ..........................................................21
3.2.1 Integration .......................................................................... ..........................................................21
3.2.2 Interference Correction ....................................................... ..........................................................21
3.2.3 Timeslice Internal Standard Correction .............................. ..........................................................21
3.2.4 TTRA Integration ............................................................... ..........................................................21
3.2.5 Transient Internal Standard Correction .............................. ..........................................................23
3.2.6 Calibration .......................................................................... ..........................................................23
3.2.7 Blank Subtraction.. ....... ................ ... __ ... ...... .....
..............
. ....... ................ ....... ...... 23
3.2.8 Concentrations .................................................................... ..........................................................24
3.2.9 Dilution Correction ............................................................ ..........................................................24
1. Calcu' --A Methods
The calculations pea Formed on continuous acquisition experiments are split up into the following
sections:
1. Integration
2. Interference correction
3. Internal standard correction
4. Internal dilution correction
5. Calibration
6. Blank subtraction
7. Concentration calculation
. External drift correction
. Special blank, jbtraction
2

In an acquired run, an integrated value is calculated for every amu for which data has been
collected as follows:
The measured number of counts for each channel (C) is converted into a cou t rate (CR) by
dividing the measured counts by the dwell time (T)
(i) C = C / T
. 1.2 Dead time correcj'77%?..
This is a correction applied to p sc Tf detector dead time. It is applied
to the acquired pulse counting c : a iollo_.
(ii) CPSPC = CRPC / ( 1 - ( CRPC * D ) )
Where CPSP, is the dead time corrected channel countrate and D is the (user defined) dead time
correction factor (in seconds).
. Cross 1.3 Detector Calibration
This is a correction factor applied to analogue data (CPSan) to scale it relative to pulse counting
data (CPSpj. The correction is obtained from a detector cross calibration lookup table and a
detector offset and is applied to the analogue integrated count rate (ICPS) as follows
(iii) CPSa„ = (( CRa„ -- Qdetector ) * X(m) )
Where CPSan is the cross calibration corrected count rate, O is the detector offset and X(m) is the
cross calibration factor at mass m.
is used.
1a 1 ---)us Detector Data
When data is collected on a simultaneous detector, a decision must be made as to which data is
valid. The detector (analogue or pulse counting) used to measure the data is determined by
examining the status of the detector gating trips to see which data is valid. (The detector gating
trips are hardware controlled and flagged in the raw data.)
. -.'on
Peak jump scan data is averaged over all points acquired for the peak. For continuous scan data
the integrated value is the sum of all the channels contained between the peak edges. There are
two methods of determininv ?A here the edges of the neak are when an dvsinn continrfnl_` SCa-
dr I in v i(' in. .a.
4
1.2 Interference
s
1.3 Internal r Correction
All samples which have internal standards defined are internal standard (I) corrected. Every
acquired peak has an IS correction factor (ISCF) calculated (this may be 1. if there are no
internal standards defined or I correction is not required for the analyte). This ISCF value is then
multiplied by the interference corrected [CPS value of the peak to produce the I corrected [CPS
value (ISICPS).
(I) ISICPS = ICICPS * ISCF

r r r-"^ ,t n ISCF ' calr lat: d .,:> a ra",
s? t
where ur and t dente the reference serFsitiv,wy and target analyte sensitivity respectively.
The sensitivity of the target analyte is given by
(iii) St = ICICPS,1 Cd
where Cd is the defined concentration.
The reference sensitivity is obt W" ;ethods, in order of priority:
i) A reference inte,. - -an(- - :; r th- reference sample.
The reference sample is the first sample in the preceding calibration block. If the
corresponding analyte in the reference sample is defined as an internal standard and it
has a valid mean ISICPS value then it is used to obtain the reference sensitivity which is
given by
(iv) Sr = mean IICPSr / Cdr
Where Cdr is the defined concentration of the internal standard in the reference sample.
(Note - this means that, ideally, the set of internal standards in the reference sample
should contain all the internal standards that are to be used in any subsequent samples.)
ii) A reference calibration.
If a reference is not found in (I) the reference calibration may be used. The reference
calibration is the analyte calibration in the preceding calibration block If the calibration is
valid then the reference sensitivity is given by the slope of the calibration (C l), (see
section 1.4)
(v) Sr = C,
(Note - for calibration standard samples that form the calibration black, the internal
standard corrected value is used to construct the calibration curve. The calibration curve
cannot therefore be used as an internal standard reference point for these samples. If an
internal standard within these samples has no corresponding internal standard in the
reference sample (i) then the internal standard will just reference itself (iv).)
iii) semi-quantitative response curve.
If a reference is not found in (i) or (ii) the reference semi-quantitative response curve may
be used. The semi-quantitative response curve from the preceding calibration block may
be used to obtain an estimate of an analyte's sensitivity (Ssq) (see section 1.5.3). This
may then be used as the reference sensitivity (as noted in (ii) calibration standards may
not be corrected using this method).
(vi) Sr = S5q
iv) c.,rf °efem
G ,c _ n 1 ?irenr in (i} r
hin tar,
lei`. # ; . Jles ' s DE C e i, 1,; a )f 1C.
which will then be used as a reference for subsequent samples.)
(vii) Sr = mean ICICPS,1 Cd
1.3.2 s •-
Analytes which are not defined s ; >nal ^nc c! have an IS(F calculated from the ISCF of
the internal standard analytes w lethod of calculating the ISCF
may be selected from the follo`°
I) Reference
For analytes with internal standard correction by reference, the ISCF is set to the same
value as a valid selected internal standard analyte within the run.
(viii) ISCF = ISCFr
ii) Interpolation
If the IS correction method is interpolation, the ISCF of the target analyte derived by
interpolation from the bracketing internal standard analytes (by mass). Using the mass
() of the target analyte, the ISCF is derived from
(viiii) ISCF = ISCF1 + ( ISCF2 - ISCF, )(( M - M, ) l ( M2 - M1 ))
where ISCF, and ISCF2 are the respective correction factors of the bracketing internal
standards at a lower mass (,) and higher mass (2).
(Note - analytes not bracketed by internal standards (e.g. at a lower mass than the first
internal standard or a higher mass than the last internal standard) will have the ISCF set
equal to the first or last internal standard respetively.)
iii) None

If this option is chosen (or there are no valid internal standards in the run) no internal
standard correction is performed.
{x} ISCF = 1.0
1.3.31 _ 'ard cc -.i, 7 of survey data
(0 C f lr" . n l .'CI -
8
1.4 '-i_ Dilution Correction
In the same way that each sample can have a set of internal standards defined, each sample
may also have a single internal dilution standard defined. This is to correct for any errors in
diluting the sample.
The dilution correction is performed in a similar way to internal standard correction with the
dilution standard being referenced to the corresponding dilution standard in the reference sample
or to the calibration (see section 1.3.1). This then gives an internal standard dilution factor (ISDF)
which is used to correct the ISICPS value:
1.5 Calibration
The calibrations for an analysis are calculated from the calibration blocks of standard samples. A
set of calibration curves is produced for each block. A calibration is required for every analyte
which has been defined as being analysed in either a fully-quantitative (FO) or a standard
addition (SA) analysis. The calibrations must have sufficient points (standard samples) included
to produce a valid curves. The minimum number of points is two however with the `force through
origin' option a valid calibration may be constructed using only one point (one standard sample).
The calibration curves in each block are then used to produce a semi-quantitative (SQ) response
curve.
The calibration curves are equations of the mean internal standard corrected counts (ISICP)
against defined concentration. If a point has been excluded or is invalid, the analyte has been
defined as an internal standard within the sample or the standard concentration is defined as
NULL th+_ i it will not be used in the generation of the curve. every standard sample in a block
al' ation arve
.yte:
onl 'al
pu,;_ose_ of g: ;ati% uui _ _s of deri4,i a jtan(,-,d u__._on
Fully-quantitative analyses may r tions of 1 form:
(ii} IDICP = do + ajC + a2 C2
1.5.1 Fully-quantitative analysis
For each block, a calibration curve is produced for every analyte defined as using FQ calibration.
The curve is constructed from the mean ISICS results for the analyte from each sample
(standard or blank) in the block. If the calibration block contains a blank, then this will be included
on the curve as a point at zero concentration. The following options are available for each curve:
Lure fit
• 1" order
2" d order
Intercept
None (normal intercept)
• Force through blank (the curve is forced through the blank point if there is a blank in the
calibration block)
• Force through origin
10
Weighting
None
• Standard deviation (each point is weighted by standard deviation of the analyte over the runs
in the sample)
• Relative standard deviation (each point is weighted by standard deviation of the analyte over
the runs in the sample relative to the mean value)
1.5 ," - f i jc , - j
For each block, a 1 st order calibr `ion curve is produced for every analyte defined as using A
calibration. The curve is constructed from the mean ISICPS results for the analyte from each SA
standard sample in the block (if there is a blank sample in the block it is not used to generate the
curve). The following options are available for each curve:
Inter,°ent
(r: T: r
s ft _ ed ere
gr. r9
N,)ne
Standard deviation (each point is weighted by standard deviation of the analyte over the runs
in the sample)
• Relative standard deviation (each point is weighted by standard deviation of the analyte over
the runs in the sample relative to the mean value)
The SA curve generated is then used to calculate the original concentration of the analyte in the
standard samples. Since the slope of the curve (a,) is the analyte sensitivity, the measured
concentration (C,,) is given by
C,n = IDICPSO / a,
If the calibration block includes a blank sample then the concentration is given by
(iv) CM = ( IDICPSQ - IDICPSa) / a,
where IDICPSb is the mean internal dilution corrected counts in the blank sample.
1.5. _. . '- e Response Curves
(v} sq = a, / RF
If the concentrations are defined per element rather than per isotope, the sensitivity is also
11
abundance corrected (S curves are always defined in terms of isotopic sensitivity).
(vi) S$4 = (a, SF) / Ai..... pe
where Asotap, is the isotopic abundance of the analyte.
The semi-quart sensitivities and masses of the analytes are then used to produce a 2" d order
calibration of the form:
(vii) sq = do + b,M + b2 M2
where bo, b, and b2 are constants and M is the isotopic mass.
12
1.6 Blank Subtraction
There are two methods of blank subtraction (BS):
• subtraction by blank sample
• subtraction by calibration curve intercept {only for fully-quantitative analysis )
TIC S = InlC S - I ICPghank
13
1.7 Concentration __. ' __
Concentrations are calculated depending on the analysis method selected. Concentrations for
survey scan data are always calculated using semi-quantitative analysis. Concentrations for main
scan data may use fully-quantitative (FQ), standard addition (SA) or semi-quantitative (SQ)
analysis.
Each sample in the list is associated with a calibration block (if there is one in the experiment.)
which will be the last block acquired before the sample. (The samples within the block will be
associated with the block to which they belong). The concentration of each analyte in each run is
calculated using the corresponding analyte calibration in the block.

For a order calibrations the measured concentration (Cm) is calculated by solving the
calibration equation 1.5.ii using a `: ,.vton-R -: hson method
Currently (due .w
calibration is shift, I tE. G.t'
used to get the concentration. TI, - i\ for the
chemist expect the 2',a order caiibration to of :'
`r? rn?????'??n???? f??` ?? i??9 fn??n?n?????'?? inn??n??nn r>??? fn?? f?a?t?? ; fn??'?
The actual concentration (Ca) is calculated by scaling the measured concentration by the dilution
factor (D):
(iii) Ca = C, /
If there is no FQ calibration block associated with a sample, or the analyte FO calibration is not
valid then concentrations will be calculated using SQ.
s Standard "-, , inalysis
Concentrations in standard addition analyses are calculated in the same way as 5t or rfully-
quantitative calibration (see 1.641).
14
1. 7.3 Semi-qu - JS
All survey scan peaks and analy' ;s defined as using SQ analysis (or analytes defined as using
FQ or SA analysis which have no valid calibration curve) have concentrations calculated from the
calibration block associated SQ response curve.
{V) S = S sq • 1= . Aisotope
f n r r fU 7x a
15
1.8 External Drift Correction
16
1.9 Special Blank Subtraction
A sample may have a `special blank' sample associated with it. This may be any other sample in
the experiment. The concentration results (sample mean values) for each analyte in the special
blank are subtracted from the corresponding analyte concentration values in each run in the
target sample. The special blank corrected concentration result (C,) is given by:
0) Cr = Ca ® C.b
where Csb is the mean concentration in the special blank sample.
(Note - if an analyte in a special blank sample is defined as an internal standard then special
blank subtr-ction not performed for t.".at analyte.)
,r a ;e, P al arr ;u ng bE re th i
I San is
t
17
® ( r
resolved ana,ysis (TRA) acquisition experiments are set up and calculated in essentially the
same way as continuous acquisition experiments (as detailed in section 2). The sample types,
calibration blocks, analytes and calculation methods are all defined in the same fashion. Each
acquired run consists of a number of timeslices which are the equivalent of a single, one point per
peak, peak jump run in continuous scan acquisitions. Each analyte has a value for every timeslice
in a run. Survey scans can not be acquired in TRA acquisitions.
The experiment may be defined as (or interchanged between) profile T RA (PIRA) or transient
TRA (TTR ). The following sections describe the differences in the calculations for the two types
of TRA acquisition compared to the calculations for the continuous acquisition.
ca.lulair:. ns l " j-neu ii, . T. ri exp urlm( s ai e sl_:' ` i) tv the i _..v-na
1. Inte ratioi;
2. Interference correction
3. Internal standard correction
. Baseline subtraction
5. Calibration
6. Blank subtraction
7. Concentration calculation
8. Dilution correction
L-' 1
Integration is the same as for continuous scan acquisitions (see 2.1) with an [CPS value
produced per analyte, per timeslice with the same correction methods used.
3. 1. 4:: 4 swence Correction
Interference correction is performed as in continuous acquisitions (see 2.2) with integrated ICPS
values being corrected against the interference corrected ICPS values of interfering analytes in
is
the same timeslice.
3.1.3 Internai Standard Cori
I _?gions within a sample may be defined as baseline regions. Any othE cn-bc 3E ne rr lion may
be set up to use any baseline region within the same sample for baseline correction. If a region
has a baseline defined then, for each analyte, the IS corrected result (mean value) for the
baseline region is subtracted from each IS corrected timeslice value within the region being
corrected.
11.5 Ca, F
. ., _' .. Subtraction
Blank subtraction is performed as in continuous acquisitions (se 2.6) using the PTRA baseline
corrected values rather than IS corrected values. For analytes using `blank subtraction by blank",
as in the calibration stage, the non-baseline regions within the blank sample are combined to
produce a single, average, blank value per analyte. This is then subtracted, per analyte, from
each timeslice baseline corrected value.
19
Concentrations
Concentrations are calculated from the calibration curves, as in continuous acquisitions (see 2.7),
for each tieslice blank subtracted value.
3.1- _ _ _. Correction
As in continuous acquisition (see 2.).
20
Transient 3.2 For TTRA each analyte may has a number of transient analytes defined for it. The results
produced are the average values for the transient analytes over the runs in the sample
The calculations performed on PTRA experiments are split up into the following sections: 1 In r

Integration is the same as for continuous scan acquisitions (see .1) with an ICPS value
produced per anaiyte, per timeslice.
c - - ; r
Interference correction is performed as in cone .uous acquisitions (see 2.2) with integrated ICPS
values being corrected against the interference corrected ICPS values of interfering analytes in
the same timeslice.
fi l Correction
Timeslice IS correction is similar to continuous acquisition (see 2.3)IS correction except that it
only corrects for drift within a single acquired run ( rather than over the whole experiment ). For all
analytes defined as internal standards an IS correction factor is calculated for each timeslice
using as a reference value the interference corrected ICPS of the anaiyte in the first timeslice of
the run. As in PTRA, non-IS analytes are then corrected with reference to IS analytes within the
same timeslice.
. . r ,....... r l
21
For each transient in the experiment, an area [CPS (AICPS) value is calculated which is the sum
of the timeslice internal standard corrected (TSISC) values of the anafyte over the width of the
transient peak. Each timeslice has an acquisition time and transients are defined in terms of time
from the start of the acquired run. All the transient peaks found in the run are integrated whether
they have been defined or not.
3.2.4.1 Defined transients
fo; ,V i`, a :s avr::.'ale.
Auto baseline
Auto integration
Integration of a run is only done once the whole run has been acquired. The first time a run is
integrated, the default (user defined) transient parameters are used. The integration routine
creates a new record with the default parameters, which are then edited by the peak search
routines, for each transient in the run. These parameters are then used for any subsequent
integration and may be edited by th user.
The data for each anafyte is fir - a done for each transient peak.
The position of the peak is de. me um signal found within the region
retention time +- half th :o:. v?
(If no maximum of a sufficient level is found then the transient position is left at the retention
time.) The transient retention time is then set to this new position and the retention window is set
to zero to fix the peak.
If auto integration is selected, a routine is then a called to determine the peak edges (pre and
post transient integration limits). These are set either side of the peak centre position where the
signal has fallen to less than 10% of the peak centre level or has started to increase. The signal
level at both edges must have dropped to less than 80% of the peak centre level or the routine
fails and the integration limits are left unchanged, If the routine succeeds then the pre and post
transient integration limits are set to the peak edges.
If auto baseline is selected then the pre and post transient baseline positions are set to the peak
edges (pre and post transient integration limits) and the pre and post transient baseline widths
are set to 1.
If a baseline has been defined (at least one of the baseline widths is non-zero) then the TSISC
values within the peak are baseline corrected. Both a pre transient and a post transient baseline
value is calculated by taking the average TSISC value over the baseline width number of
timeslices around the baseline position. Using a straight line fit of baseline value against time
between the two positions, a baseline correction is calculated and applied to each timeslice
TSISC value within the peak. If only one baseline position has been defined then that value is
22
used as the correction for each timeslice.
The integrated (AICPS) value is then calculated by summing the baseline corrected TISC value
in each timeslice within the region:
3.2.5 Transient Internal Standard Correction
Transient IS correction, as in continuous acquisition integration I correction (see 2.3), corrects
for drift throughout the experiment n.nd is apniied to the integrated transient (AICPS) values. The
method is the same as for cant! ;i transient internal standards
being referenced back to the s: - : determine a correction factor,
Since transients may arrive at _ try ants are only corrected by
reference to an IS transient w7 -a. ti ®rpolatio-, i-y not be used).
3.2.6 Calibration
Calibration is the same as for continuous acquisitions with calibration response curves being
derived for defined transients as opposed to analytes (see 2.).
ubtraction
Blank subtraction is the same as for continuous acquisitions with the transient results (mean
values) in the blank being subtracted from the corresponding transient values in all samples using
the blank. As in continuous acquisitions, transients using fully-quantitative methods may blank
subtract using the calibration response curve intercept.
23

Concentrations are calculated from the calibration curves, as in continuous acquisitions (see 2.7),
for each defined transient.
. . - _ - Correction
As in continuous acquisition (see .).
24
SO NO.: i LT--ICPMS
Revision: 12
Date. `5/21/07
Page. 19 of 19
Attachment B
Isobaric Interference Corrections
:..: ? ?i?'?::: x.. ;.. ... i'F; i ?..
:" ;., '
.., .,. i
Appendix D
Metals Extraction - Method 3020A
SOP No.: MET-3020A
Revision: 12
Date: 9/26/07
Page: 1 of 9
STANDARD OPERATING PROCEDURE
Approved by:

for
METALS DIGESTION
SOP No.: MET-3020A
Revision: 12
September 26, 2007
1
Supervisor
s.,. Ml pager
Laboratory Manager
COVITMRIA ANAT YTIC'A1. CF12V1CFC INC"
1317 South 13th Avenue
Kelso, Washington 98626
© Columbia Analytical Services, Inc. 2007
Annual review of this SOP has been performed
and the SOP still reflects current practice.
Initials: Date: AI JOK
Initials: Date:
Initials: Date:
I
SOP No.: MET-3020A
Revision: 12
Date: 9/26/07
Page: 2 of 9
METALS DIGESTION
1. SCOPE AND APPLICATION
This procedure uses techniques described in Method 3020A for acid digestion used to prepare
aqueous samples, EP and mobility-procedure extracts, and wastes that contain suspended solids
for analysis by furnace atomic absorption spectroscopy (see SOP MET-GFAA for methods and
target elements) or ICP-MS (see SOPS MET-ICPMS and MET-6020 for methods and target
elements). This procedure is used to determine total metals.
2. METHOD SUMMARY
Nitric acid is added to a representative aliquot of sample and refluxed in a beaker. This step is
repeated until the digestate is light in color or until the color has stabilized. After the digestate
has been brought to a low volume, it is cooled and diluted to final volume containing
approximately 6`x/0 (v/v) nitric acid.
3. DEFINITIONS
3.1. Laboratory Control Sample (LCS): A laboratory blank that has been fortified with target
analyte and used to determine that the analysis is in control.
3.2. Matrix Spike (MS) Analysis - In the matrix spike analysis, predetermined quantities of target
analytes are added to a sample matrix prior to sample preparation and analysis. The percent
recovery is calculated. The MS is used to evaluate the effects of the sample matrix on the
method used for the analysis. The concentration of the spike should be at three to five times
the sample result or at levels specified by a project analysis plan.
3.3. Duplicate Sample (DUP) - A laboratory duplicate. The duplicate sample is a separate field
sample aliquot that is processed in an identical manner as the sample proper. The relative
percent difference between the samples is calculated and used to assess analytical precision.
3.4. Method Blank (MB) - The method blank is an artificial sample composed of analyte-free water
or solid matrix and is designed to monitor the introduction of artifacts into the analytical
process. The method blank is carried through the entire analytical procedure.
4. INTERFERENCES
Refer to the determinative method for a discussion of interferences.
5. SAFETY
SOP No.: MET-3020A
Revision: 12
Date: 9/26/07
Page: 3 of 9
5.1. All appropriate safety precautions for handling solvents, reagents and samples must be taken
when performing this procedure. This includes the use of personnel protective equipment,
such as, safety glasses, lab coat and the correct gloves.
5.2. Chemicals, reagents and standards must be handled as described in the CAS safety policies,
approved methods and in MSDSs where available. Refer to the CAS Environmental, Health
and Safety Manual and the appropriate MSDS prior to beginning this method.
5.3. Nitric Acid is used in this method. These acids are extremely corrosive and care must be taken
while handling them. A face shield should be used while pouring acids. And safety glasses
should be worn while working with the solutions. Lab coat and gloves should always be worn
while working with these solutions.
6. SAMPLE, COLLECTION, PRESERVATION AND STORAGE
Samples are typically collected in plastic containers. Aqueous samples are preserved with nitric
acid (pH<2), then refrigerated at 4 ± 2°C from receipt until analysis.
7. APPARATUS AND EQUIPMENT
7.1. Borosilicate glass beakers, 150 mL
7.2. Borosilicate watch glasses, ribbed
7.3. Hot Plates: "Thermolyne Cimerac 3", calibrated to maintain 90-95°C
7.4. Polypropylene graduated cylinders, 50 mL
7.5. Evergreen disposable tubes, 50 mL. Check tubes for accuracy on a per batch basis by
filling a tube to the 50 mL mark and measuring the water's mass. The measured mass
must be accurate to ± 3%; if not obtain a. new lot of ttihes and retest. Refer to the SOP
for Checking Pipet Calibration (ADM-CPIP), section 8.1 for detailed instructions on
performing the accuracy test.
8. STANDARDS AND REAGENTS
8.1. Reagent water: ASTM Type I water (resistivity >18 NTQ-cm, conductivity <0.056 uS/em).
8.2. Concentrated Nitric Acid: J.T. Baker "Instra-analyzed", Trace Metals Grade
8.3. Metals Spiking solutions: Matrix spikes are prepared using the ICP-MS intermediate stock
solutions which are prepared as follows:
SOP No.: MET-3020A
Revision: 12
Date: 9/26/07
Page: 4 of 9
8.3.1. A 1000 ug/L intermediate mixed stock standard containing the 200.8 list of metals,
less silver, is first prepared. Add 1.0 mL of each purchased, single element, 1000
mg/L stock standard to a 1000 mL Class A volumetric flask filled approximately
three quarters full with reagent water and 10 mL of Ultrex nitric acid. After all the
additions are made the flask is diluted to volume with reagent water. A separate
1000 ug/L silver intermediate stock is prepared in the same fashion and stored in
an amber flask.
8.3.2. Store in a sealed Teflon bottle at room temperature. The expiration date for the
intermediate standards in the earliest expiration date of the individual component
stock solutions.
9. PREVENTIVE MAINTENANCE
9.1. Routine cleaning of the digestion glassware is necessary. Refer to the SOP for Metals
Laboratory Glassware Cleaning.
9.2. Hotplates temperatures must be monitored and documented on a monthly basis.
9.3. Record all maintenance and monitoring activities in a lab notebook.
10. RESPONSIBILITIES
10.1. It is the responsibility of the analyst to perform the analysis according to this SOP and to
complete all documentation required for data review. Analysis and interpretation of the
results are performed by personnel in the laboratory who have demonstrated the ability to
generate acceptable results utilizing this SOP. This demonstration is in accordance with the
training program of the laboratory. Final review and sign-off of the data is performed by
the department supervisor/manager or designee.
10 .1 Tt k the recnnnsihility of the dt-nartment yinen,,icnr/manager to document- analvct training
11. PROCEDURE
11.1. Record all digestion and sample information on the applicable benchsheet. To assist the
analyst, a brief description of the procedure is given on the back side of the benchsheet.
See Attachments for benchsheet.
11.2. Shake the sample to mix. Measure 50 mL aliquot, using a class B Polypropylene
graduated cylinder, into a 150 mL beaker. At this point, add the appropriate spiking
solutions directly onto the designated spike sample prior to addition of water or other
reagents.
SOP No.: MET-3020A
Revision: 12
Date: 9/26/07
Page: 5 of 9
11.3. Add 1.5 ml of concentrated HNO3, cover with a ribbed watchglass, place beaker on hot
plate and evaporate to a low volume (2.5 ml), making certain the sample does not boil and
that no portion of the bottom of the beaker is allowed to go dry. Cool the beaker, add
another 1.5 ml portion of HNO3, cover with a watch glass and heat so that a gentle reflux
action occurs. (CAUTION: Do not allow sample to go dry. Should this occur discard
sample and reprepare.) Continue refluxing until digestion is complete. (Additional acid
may be required). Reduce the sample volume to 1.5 ml. Remove the beaker and add
approximately 10 ml of water and continue warming for 10 to 15 minutes to solubilize any
residue.
Note: When digesting USACE HTRW project samples, the 95°C hotplate temperature
must be monitored and documented on a per-batch basis.
11.4. Remove the beaker from the hot plate and allow to cool. Rinse down the sides of the
beaker and the watch glass with reagent water. Transfer the digestate to a centrifuge tube.
Dilute to the 50 mL mark on the centrifuge tube with reagent water. (Note: The 50 mL
graduation on the Evergreen disposable centrifuge tubes are checked for accuracy on a per
batch basis). If any insoluble material is present, let the material settle or centrifuge before
analysis. If immediate analysis is necessary the digestates may be centrifuged to remove
insoluble material.
12. QA/QC REQUIREMENTS
111. Verify hotplate temperatures on a monthly basis. Using mineral oil in a beaker, check the
temperature after equilibration. The temperature should be 95 ± 3°C. If the hotplate
cannot be adjusted into range, report to the lab manager for further corrective action.
12.2. Digest one laboratory control sample with each batch. Use the appropriate dilution of
Inorganic Ventures ICV solutions or the liquid laboratory control sample (LCSW). Refer
to the determination procedure for the concentration specified for the analysis. LCSW
samples are prepared as follows:
1.0 mL of the ICP-MS Intermediate Mixed Stock and 1.0 mL of the ICP-MS
Silver Intermediate Stock are added to 50 mL of reagent water in a 150 mL beaker
and digested as per the procedure. (Refer to section 12.5 for the preparation and
composition of these intermediate stocks.)
12.3. Digest one preparation blank (with each samples matrix). Prepare one blank per digestion
batch, or per 20 samples, or per EPA SDG group, whichever is more frequent. Use D.I.
water and follow the digestion procedures.
12.4. Digest one duplicate and one spiked sample with each sample matrix. Prepare one
duplicate and spike sample per each digestion batch, or per twenty samples, whichever is
SOP No.: MET-3020A
Revision: 12
Date: 9/26/07
Page: 6 of 9
more frequent. At times, specific samples will be assigned as duplicates or spikes
depending on client requirements.
12.5. Water spikes are prepared by adding 0.5 ml of the appropriate spiking solution (refer to
the determination procedure for the concentration specified for the spike analysis). Fill
out a spiking data sheet and keep it with the digestion data sheets. Spiking solutions
expiration dates are determined by the earliest expiration date of any single component in
the solution and solutions are verified by ICP analysis. Matrix spike samples are prepared
as follows:
1.0 mL of each ICP-MS Intermediate Mixed Stock solution is added to the 50 mL
aliquot designated for the matrix spike prior to the addition of acids. The matrix
spike sample is then digested as per the procedure.
13. REPORTING
13.1. Digestion data sheets including volumes used are completed and a batch lot number is
assigned and attached to the data sheet. The Manufacturer's lot numbers for the reagents
used are added to the digestion data sheet (see Attachments).
13.2. Spiking sheets are completed including all spike data and volumes of spiking solutions
used (see Attachments).
14. CORRECTIVE ACTION
14.1. Refer to the SOP for Nonconformity and Corrective Action for procedures for corrective
action. Personnel at all levels and positions in the laboratory are to be alert to identifying
problems and nonconformities when errors, deficiencies, or out-of-control situations are
detected.
14.2. Handling out-of-control or unacceptable data
14.2. 1. On-the-spot corrective actions that are routinely made by analysts and result in
acceptable analyses should be documented as normal operating procedures, and no
specific documentation need be made other than notations in laboratory maintenance
logbooks, runlogs, for example.
14.2.2. Documentation of a nonconformity must be done using a Nonconformity and
Corrective Action Report (NCAR) when: a) corrective action is not taken or not
possible b) corrective action fails to correct an out-of-control problem on a
laboratory QC or calibration analysis c) reanalysis corrects the nonconformity but is
not a procedurally compliant analysis.
SOP No.: MET-3020A
Revision: 12
Date: 9/26/07
Page: 7 of 9
15. POLLUTION PREVENTION
It is the laboratory's practice to minimize the amount of solvents, acids and reagent used to perform
this method wherever feasible. Standards are prepared in volumes consistent with methodology and
only the amount needed for routine laboratory use is kept on site. The threat to the environment
from solvent and reagents used in this method can be minimized when recycled or disposed of
properly.
16. WASTE MANAGEMENT
16.1. The laboratory will comply with all Federal, State and local regulations governing waste
management, particularly the hazardous waste identification rules and land disposal
restrictions as specified in the CAS EH&S Manual.
16.2. This method uses acid. Waste acid is hazardous to the sewer system and to the
environment. All acid waste must be neutralized to a pH of 2.5-12 prior to disposal down
the drain. The neutralization step is considered hazardous waste treatment and must be
documented on the treatment by generator record. See the CAS EH&S Manual for details.
17. METHOD PERFORMANCE
Available method performance data is given in the reference method. In addition, this procedure
was validated through single laboratory studies of accuracy and precision as in the determinative
procedure. The method detection limit(s) and method reporting limit(s) are established for the
determinative procedure.
18. TRAINING
18.1. Training outline
18.1.1. Review literature (see references section). Read and understand the SOP. Also
review the applicable MSDS for all reagents and standards used. Following these
reviews, observe the procedure as performed by an experienced analyst at least
three times.
18.1.2. The next training step is to assist in the procedure under the guidance of an
experienced analyst. During this period, the analyst is expected to transition from
a role of assisting, to performing the procedure with minimal oversight from an
experienced analyst.
18.1.3. Perform initial precision and recovery (IPR) study as described above for water
samples. Summaries of the IPR are reviewed and signed by the supervisor. Copies
may be forwarded to the employee's training file. For applicable tests, IPR studies
SOP No.: MET-3020A
Revision: 12
Date: 9/26/07
Page: 8 of 9
should be performed in order to be equivalent to NELAC's Initial Demonstration
of Capability.
18.2. Training is documented following the SOP for Documentation of Training.
NOTE: When the analyst training is documented by the supervisor on internal training
documentation forms, the supervisor is acknowledging that the analyst has read and understands this
SOP and that adequate training has been given to the analyst to competently perform the analysis
independently.
19. REFERENCES
Test Methods For Evaluating Solid Waste, Physical/Chemical Methods. EPA SW-846, 3rd
Edition, Final Update 1, Method 3020A, July 1992.
SOP No.: MET-3020A
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Date: 9/26/07
Page: 9 of 9
Attachments
Benchsheet
Metals Spike Form
Columbia Analytical Services
Metals Digestion Sheet
Service Request Number(s)
'tar Dims Run 1o.:
Method : CLP 3010A 3020A Analysis for : 1CP ICP-MS GFAA
3005A 3050B CLP Hot Block Other- Flame AA Other
Sample Initial Weight (g) Dry Wet initial Volume(ml) Final Volume (ml) Matrix
Time Digestion Started:
Lot # Acids Used: HNO3 HCI
LCSS (circle appropriate) ERA CLP Soil Lot # D045540 Other:
G FAA v CS CM CqW MFT1-52-W. mis. added
ICPLCSW - CLP-CV-1, MET]-52-A, cols. added
QCP CICV-2, MET]-51-T, mis. added
QCP CICV-3, METI-51-U, mis. added
SS6, METI-52-Y, mis. added
SPIKE INFO
SSI-METI-52-Z, mis added
SS5-METI-54-G, mis added
SS6-METI-54-E, mis added
Additional
Comments:
H2O2
TCLP Spike/LOSE
TSSI METI-47-C mis. added
SS4-METI-48-A, mis added
200.8 1000ppb Stock (MS9-85-A)_ mis added
Ag I000ppb Stock (MS10-10-A) mIs added
Analyst Date
Reviewer Date
metdig.xls
Method #
GFAA
Digestion Procedures
CLP Water Shake sample, Aliquot 50 mis into beaker
Add 0.5 mis. HN03
Add 2 ML 30% H202
Cover with ribbed watchglass
Heat without boiling for 2 hrs (volume = 0.5x orginal Vol.)
Cool sample, Dilute to 50 mis. with DI water
EPA 3010A
SW-846
TCLP Ext.
USACOE
EPA 3020A Shake sample and measure 50 ml into beaker
SW-846 Add 1.5 ml of HN03, cover with ribbed watchglass
TCLP Ext. Evaporate to 5 ml. Do Not let go DRY
USACOE Cool, Add 1.5 ml of HN03, Cover and reflux
until digestate is light color or color has
stabilized
Reduce volume to 5 mis, Cool
Add 10 ml DI water, reflux 10-15 min.
Dilute to 50 mis with DI water.
EPA 3050B Mix sample, weigh out 1.00 g dry weight.
Add spike solution to sample.
Add 5 ml DI water and 5 ml HN03. Reflux 15 min.
Cool. Add 5 ml HN03. Cover. Reflux 30 min.
NOTE: If brown fumes are generated, repeat the
addition of 5 mis of HN03 after 30 min of reflux.
Reflux for 2 hrs. or to vol of 5 mIs.
Cool sample and add 2 mis H2O & 3 mis 30%H202
Cover and heat until effervescence subsides
Repeat H202 adds twice until effervescence is minimal.
Don't add > 10 mis. R202
Heat to vol. of 5 mis. Dilute to I00mis with DI water.
ICP-OES
same
same
Add 2.5 mis Concentrated HCI instead of H202
Cover with ribbed watchglass
same
same
Shake sample and measure 50 ml into beaker
Add 1.5 ml of HN03, cover with ribbed watchglass
Evaporate to 5 ml. Do Not let go DRY
Cool, Add 1.5 ml of HN03, Cover and reflux
until digestate is light color or color has
stabilized
Reduce volume to 5 mis, Cool
Add 2.5 mis Concentrated HCI. Cover and reflux for 15 mi
Dilute to 50 mis with DI water.
same
same
same
same
Add 10 ml of Concentrated NCI, Reflux for 15 min.
Dilute to 100 mis. (to 50 mis for Flame)
GFA A NOTE: For SW-846 analysis prepare n tiiPastate frnm Tvlethnrl 1020B for Ph &T] analvsis & a digestate
from the CLFAA for As & Se. c
R Suggested Sample Aliquot Weights
Solids Aliquot Wet Weight Range
>80 % 1.00 g
70-80% 1.20 g
60-70% 1.40 g
50-60% 1.80 g
40-50% 2.20 g
30-40% 2.70 g
Spike Solution Chart
GFAA soil - 2mis SS # 4
ICP-OES soil - 2mis SS# I & I ml SS # 5 & 6
ICP-MS soil - 2mis SS# 1, & I nil SS # 5 & 6
ICP-OES water- 0.5mis SS# 1,5,6
GFAA water - 0.5 ml SS # 4
ICP-MS water - I ml 200.8 stock sol'n & I ml Ag sol'n
Method #
GFAA
Digestion Procedures
CLP Water Shake sample, Aliquot 50 mis into beaker
Add 0.5 mis. HN03
Add 2 ML 30% H202
Cover with ribbed watchglass
Heat without boiling for 2 hrs (volume = 0.5x orginal Vol.)
Cool sample, Dilute to 50 mis. with DI water
EPA 3010A
SW-846
TCLP Ext.
USACOE
EPA 3020A Shake sample and measure 50 ml into beaker
SW-846 Add 1.5 ml of HN03, cover with ribbed watchglass
TCLP Ext. Evaporate to 5 ml. Do Not let go DRY
USACOE Cool, Add 1.5 ml of HN03, Cover and reflux
until digestate is light color or color has
stabilized
Reduce volume to 5 mis, Cool
Add 10 ml DI water, reflux 10-15 min.
Dilute to 50 mis with Di water.
EPA 3050B Mix sample, weigh out 1.00 g dry weight.
Add spike solution to sample.
Add 5 ml DI water and 5 ml HN03. Reflux 15 min.
Cool. Add 5 ml HN03. Cover. Reflux 30 min.
NOTE: If brown fumes are generated, repeat the
addition of 5 mis of HN03 after 30 min of reflux.
Reflux for 2 hrs. or to vol of 5 mis.
Cool sample and add 2 mis H2O & 3 mis 30%H202
Cover and heat until effervescence subsides
Repeat H202 adds twice until effervescence is minimal.
Don't add > 10 mis. R202
Heat to vol. of 5 mis. Dilute to 100mis with DI water.
ICP-OES
same
same
Add 2.5 mis Concentrated HCI instead of H202
Cover with ribbed watchglass
same
same
hake sample and measure 50 ml into beaker
dd 1.5 mi of HN03, cover with ribbed watchglass
vaporate to 5 ml. Do Not let go DRY
ool, Add 1.5 ml of HN03, Cover and reflux
until digestate is light color or color has
stabilized
educe volume to 5 mis, Cool
dd 2.5 mis Concentrated HCl. Cover and reflux for 15 mi
iiute to 50 mis with DI water.
same
same
same
same
same
same
same
same
same
same
Add 10 mi of Concentrated HCI, Reflux for 15 min.
Dilute to 100 mis. (to 50 mis for Flame)
GFAA NOTE: For SW-846 analysis prepare a digestate from Method 3020B for Ph & TI analysis & a digestate
from the CLFAA for As & Se.
* Suggested Sample Aliquot Weights
% Solids Aliquot Wet Weight Range
>80 % 1.00 g
70-80% 1.20 g
60-70% 1.40 g
50-60 % 1.80 g
40-50% 2.20 g
30-40% 2.70 g
Spike Solution Chart
GFAA soil - 2mis SS # 4
ICP-OES soil - 2mis SS# I & I ml SS # 5 & 6
ICP-MS soil - 2mis SS# 1, & I ml SS # 5 & 6
ICP-OES water- 0.5mis SS# 1,5,6
GFAA water - 0.5 ml SS # 4
ICP-MS water - Iml 200.8 stock sol'n & I mi Ag sol'n
Appendix E
PCB - Method 608
SOP NO. S C-608
Revision 5
Date: 7/23/07
Page 1 of 17
STANDARD OPERATING PROCEDIJRE
ORGANOCHLORINE PESTICIDES AND A T -I, PCBS)
. V --608
{
Aiy ..
Approved y: f ='
Su )ervisor
ANALYTICAL COLUMBIA -.
1317 South 13th Avenue
Kelso, Washington 98626
C Columbia. Analytical Services, Inc. 2007
Da':e
2
Date
Ra ?
Da.
SOP NO. S -608
Revision 5
Date: 7/23/07
Page 2 of 17
POLYCHLORINATED ORGANOCHLORINE PESTICIDES AND _ ( )
1. 1SCOPE AND APPLICATION
1. This Standard Operating Procedure (SOP) describes the procedure used by Columbia
^l? *; r!'r°v4-,'--,. for +I-- --alyr4s of rZ-ochlori e Pesticic??s end 1"C Bs i.,°;- E"A
N nd CiOR '1'-hla l 1°-ta falzrtac wt hp Wmined by this rnr: 14a 1; 'le
1.G. '1 is r ?ri11Ga[':', to me ,1 oI a-:,1ec n ;iin
grou w,A -, and surface water. Reporting and deter o-1;r, s --e based o non-`nal
volumes of I L for the sample used and 2mL for the final (extract) volume. The reported
L may be adjusted if required for specific project requirements, however, the capability of
achieving other reported NIRLs must be demonstrated.
-Y OF METHOD
procedure provides C 7- go e appropriate sample extraction
techniques. A 1-3 [d portion of equipped with electron capture
detectors (EC D). Identificat` :)n -1e :_ i two dissimilar columns. uantitation
is done by external standard tec'zn due. If t ",,_-nces r-vynt detection of the analytes, extract
cleanups using Florisil copper, carbon, sulfuric acid or G PC may be used.
3. DEFINITIONS
3.1. Analysis Sequence - Samples a - a ',,znd in a set referred to as an analysis sequence. The
sequence begins with instrument c- 'ibratio followed by sample extracts interspersed with
calibration standards. The sequence ends when the set of samples has been injected or
when qualitative and/or quantitative C criteria are exceeded.
S NO. S C-608
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14. c+^,r-4 -r,? Curve - A r-mdr -d r ve is a c ? ??ra+;?., curve wl?-., plots conner+-cor , of a
lr rz?Tn i?r:= r -d r x»c rt rn , ? to tl
_. 1
.::: . .. oa .? .
iTmeteye rd
a .rsis of sa These cor >o nds are spiked into -' s, standar„ . 7 ;)': ?s, and
sp'"ed samples prior to analysis. Percent recoveries are c _-1 _ ? for each surrogate.
3.6. Method lank - The method blank is an artificial sample designed to monitor introduction
of artifacts into the process. The method blank is, carried through the entire analytical
procedure.
3.7. Continuing Calibration r5.id-level standard injected into the
instrument at specified e initial calibration.
3.8. Instrument Blank (CCB'q - The i = _ement dank (,.';o called continuing calibration blank) is
a volume of clean solvent analyzed on each GC cc' ----and instrument used for sample
analysis. The purpose of the instrument blank is to v utermine the levels of contamination
associated with the instrumental analysis it4elf, particularly with regard to the carry-over of
analytes from standards or highly cor. - Tted samples into other analyses.
4. INTERFERENCES
4.1. Solvents, reagents, glassware, and other sample roc(--n;-;; hardware may yield discrete artifacts
and/or elevated baselines, causing misinterpretation of ?e chromatograms, All of these materials
must be demonstrated to be free from interferences, uem_er the conditions of the analysis, by
running method blanks.
4.2. Interferences from phthalate esters introduced during sample handling can pose a problem
with pesticide determinations. These can be removed using GPC cleanup. The presence of
elemental sulfur will result i peaks interfering with early eluting pesticides. Cleanup via
method 3660 is used for the removal of sulfur if GPC cleanup is inadequate. Other co-
extractables such as lipids, waxes, etc., can be removed via G PC cleanup.
SOP NO. S C-608
Revision 5
Date: 7/23/07
Page 4 of 17

5.1. The toxicity or carcinogenicity of each compound or reagent used in this method has not
been precisely determined; however, each chemical compound should be treated as a
potential health hazard. Exposure to these compounds should be reduced to the lowest
possible level. A reference file of material safety data sheets is available to all personnel
involved i these analyses.
5.. '_'_ appropriate safety precautions for handling solvents, reagents and samples must be
wl-Ti errormi„n + ,is procedure. b;s ;nr;l„deg the two- of verso el p-Accxive
ac Q,: °'ntv (ri ?? rr a rnr =rt ^loV c
. xea, . ai S, `.ty _ _ut i t _ o 1 )r ue4 1`ng
tl
6. SAMPLE COLLECTION, CONTAINERS, -- -'- Y,TION, AND STORAGE
62. Water samples must be iced or refrigerated at ± 2'C from time of collection until extraction.
63. Water samples must be extracted within 7 days of sampling and the extracts analyzed within 0
days of extraction.
7. STANDARDS, REAGENTS AND EQUIPMENT
7.1. Reagents
7.1.1. Stock Standard Solutions
Commercially prepared stock standards, certified by the manufacturer, are
purchased from Ultra Scientific, Accutanard, Absolute, or equivalent vendors.
SOP N S C-608
Revision 5
Date: 7/23/07
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7.1.2. Working Solutions
Diloro° prey d ,.. u ,etc ?. e
solution is stored in the refrigerator for l to six monff . r:- _B is the pri -y
surrogate, however, both surrogates are monitored.
7.1.4. matrix spike solution at 4 ppm is prepared by diluting the stock solution in
1` e H. This solution is stored in the refrigerator for'up to two weeks. The matrix
spike solution is added #o 9 r, i.. r.yii °s €-d h7 control samples.
7.1 Solvents
7.2.1. Acetone, pesticit
7.12. Hexane, pesticide grade.
7.2.3. Methanol, pesticide grade.
8. EQUIPMENT
8.1. GC Instrumentation (Equivalent may be used)
8.1.1. Gas Chromatograp, equipped with cool-on-column or split/splitless injection port
and dual EC s, Hewlett Packard 5890, 6890, or equivalent. See Table 2 for run
conditions.
8.1.2. A tosampler, capable of reproducible 1-3 p injections Hewlett Packard 7673.
8.1.3. Data system compatible with detectors and capable of measuring peak areas and
retention times, IIP Enviroquant or Target (PCBs).
8.1.4. Columns O&W or equivalent)
S NO. SOC-608
Revision 5
Date: 7/23/07
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8.1.4.1 Pesticides
Column I - B 30m x 0.32mm I , .5 qm df or equivalent
Column 2 d -35 30mi x 0.32 mm, ID, .25 µ f or equivalent
8.1.4.2 PCBs
Column 1: DB-35M.S 30m x .53mm I
Colh1mn 2 D -XLB 30m x 0.53m I
C . ,. -d Co . m 3 _ EAC'' 5 x 0.53m I

... rug ?--- ter, ac. v- s am- r coi-c
92. Carrier gas - Inline purifiers or scrubbers should be i place for all sources of carrier gas. These
are selected to remove water, oxygen, and hydrocarbons. Purifiers should be changed as
recommended by the supplier.
93. Gas C o atograph
93.2. Clipping off a small portion of the head of the cola often improves chromatographic
performance, e cutting o any portion of the column, make sure the cut is straight
and "clean" (uniform, without fragmentation) by using the proper column cutting tool.
9.3.3. Over time, the column will exhibit poorer overall perfo ance, as contaminated sample
matrices are analyzed. The length of time for this to occur will depend on the samples
analyzed. When a noticeable decrease i cola performance is evident and other
maintenance options do not result i improvement, the column should be replaced. This
is especially true when evident in conjunction with calibration difficulties.
10. RESPONSEBELITIEES
10.1. It is the responsibility of the analyst to perform the analysis according to this SOP and to
complete all documentation required for data review. Analysis and interpretation of the results
SO NO. S C-608
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Page 7 of 17
are performed by personnel in the laboratory who have demonstrated the ability to g
acceptable results utilizing this SOP. This demonstration is in accordance with the training
program of the laboratory. The department supervisor/manager or designee erfo s final
review and sign-off of the data.
10.2. It is the resi )r_. .`.j o the department supervisor/manager to document analyst training.
Documenting r . rod proficiency is also the responsibility of the department
supervisor/ manager.
11. PROCEDURE
1 c

Note: If method 3520 or 3535 is used to prepare samples, the report should list the method as
608 Modified.
11.2 Calibration
Note: Refer to the CAS ?r- ",)r C ? 1 ryame' .s for Organic
Chromatographic AnCy? es and guidelines. For this procedure,
the calibration race L_-e
11.11 Check for degrade on o 4,4'-I-:'-)T and nc" 'n by injecting a standard containing
only 4,4'-DDT at 100 ppb and endrin at 50b.
Total DDT degr, _)n freak area (J)DE DDD)
%Breakdc x 100
7btal DDT pet ' rrea (DDT -- DDF, + DDD)
% Breakdoufn --
Total endrin degradation peak area
endrin aldehyde - endrin Ketone
x100
Total endrin peak area
endrin - endrin aldehyde I endrin Ketone
If degradation of either DDT or endrin exceeds 15%, perform any
maintenance necessary before proceeding with calibration.
SOP NO. S C-608
Revision 5
Date: 7/23/07
Page of 17
11 .2,2 After determining that degradation is within acceptance criteria, a minimum of three
calibration standards for single response pesticides, Toxapene, and Chlordane are
analyzed. When performing PCB analyses, analyze a minimum of three calibration
standards for each of the reported Aroclors.
SCm mgr C :: o° i - arr. iv= C
acceptance c ' -ia for alternative fits and c J )n ?:c ?3 levee- needed use tl.:se
calibration models.
11.5 Sa ple Analysis
11.5.1 Table 2 indicates the typical operating conditions for the . Setup the analysis
sequence of samples and C samples.
S NO. S C-608
Revision 5
Date: 7/23/07
Page 9 of 17
11.6 Identification of alytes
11.6.1 1 ,nt`'i a s-: ° corn c a by cc isc ofits ?t tic n time to the t to c time of
' c A
e 1 t' ,i : o fir cc npouni' c t cc:.: atory °ctor r he
retention time indo v c system.
11,63 Confirmation of all tentative hits must be made. Confirmation is made by injecting
the sample extract on two col -G with dissimilar phases simultaneously. If the
retention time matches on both colrrr..ns, then the hit for the analyze is considered a
confirmed hit. { _ Co anon of Organic alytes.
11.6.4 For each u; c selected that are as unique to that
analyze as pos 'b a s; : - wts is performed by comparing the
average area of rep 'due pe to tl :^ averal J area of the same 3-5 peaks i the
appropriate reference mater--1 The average of each peak should match in both
retention time as well as pattern.
11.7 Perforin all necessary calculations as described in Sections 1 and 13.
12. QUALITY CONTROL
12.1. Initial recision and Recovery Validation
12.2. Method Detection Limits
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1.2.2.1. A method detection limit (M L) study must be undertaken before analysis of
samples can begin. Refer to the SOP fo r the DetL ,n - :-- %jn cif Method I)e1ec°tion
Limits and Limits ref Detection. Spike seven 1L tap ater samples with L
spiking solution at a level below the MRL.
12.2.2. Calculate the average concentration found (x) in pg/ , and the standard
deviation of the concentrations (s) in pg/ for each nalyte. Calculate the
Z.L for each analyte. The L study must be done annually.
12.3. Ongoing C Samples required are described in the CAS-Kelso Quality Assurance Manual
:.ral tl .use memode:

Cdr : Give , r"_.o s 1. ,c
reextrctlo and rer aGlysls, w
12.11 lab control sample (LCS) must be extracted and analyzed with every batch o
10 samples. The LCS is prepared by adding a known amount of the matrix spike
solution to Of water.

Where 'y+- recovered
L .Y value of u ou-IL sped
Current CAS C acceptance criteria for the LCS are listed in Attachment A. If
the LCS fails acceptance criteria, corrective action must be taken. Corrective
action includes recalculation, reanalysis, or re-extraction and reanalysis.
1111 A matrix spike (MS) and duplicate matrix spike ( S) must be extracted and
analyzed with every batch of 10 samples. The S/ S is prepared by adding
the same volume of the matrix spike solution to the sample as listed for the LCS,
then proceeding with Section . Calculate percent recovery (%R) as:
lR X - XI x 100
TV
Where X = Concentration of the analyte recovered
X1 - Concentration of nspiked analyte
TV = True value of amount spiked
SOP N. S C-608
Revision 5
Date: 7/23/07
Page 11 of 17
Calculate Relative Percent Difference (RPD) as:
i,r,- - C,^ S C -c ert---1e cri±-ria for AXIS/ NdS are lysted in ,att-r. kment A.
1 ' Nfq/ T ?rnwrr r r rrf ; -, :t<,ra Jim",. fr -,asons n1' ,r rl
V
ea
12._ A. ? o67,. e ., 2 -, A ? every sr le, _ie' r u )n.
Two s rrog :'es, tetrachloro-m-xyle (C X) and dec :..,1.1orob°*_7enyl, „e
added to each sample; however, only one need be calculated for recovery. The
surrogate is used to monitor extraction efficiency and reter ' 1< during C
analysis. Calculate surrogate percent recovery (%R) as:
/ x 100
it of Q, rrogate recovered
Ie _ ;d/_inal volume
Current CAS "_ acc+ a1 :ce':` nits fo,. rc ire __ste in Attachment A. If
both surrogate recoveries are o `de of acct rnce lir ' ; for reasons other than
matrix effects, corrective action --ast be taken. Corrective actions include
recalculation, reanalysis, or re-extraction and reanalysis.
13. DATA REDUCTION, REVIEW, AND REPORTING
13.1. Both detectors are used as primary and/or confirmatory systems when not interfered with by
the sample matrix,
13.2. uatitatio of aalytes i sample extracts is performed by comparing total area of residue
peaks to total area or peaks from the appropriate reference materials.
13.3. uantitation of multi-response analyzes:
13.3.1. The quantitation of Toxaphe ; ' ol`rer multi-response analyzes is
accomplished by comparison of ` - sample chromatogram to that of the
S NO. S C-608
Revision 5
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Page 12 of 17
authentic standard. All calibration acceptance criteria as described in section
11 must be et before reporting any results.
I lc C):
The co cer.Lration of each analyte in the sample extract (Cex) is co np tvd i pg/ units
using the calibration factor or calibration curve. The concentration of analytes in the
original samples is computed using the following equations:
C oncentratic#-° (: ) 'f? (1))
Where Cex
Vf
Vs
1.3.5. Data Review
= v;c. 'i i•1 es t in pg/m
Fin,' volu.: of extr ;t in
Dilution factor
- Volume of sample extracted, liters
Following primary data interpretation and calculations, all data is reviewed by a secondary
analyst. Following generation of the report, the report is also reviewed. Refer to the SOP
for Laboratory Data Review Process for details.
13.6. Reporting
13.6.1, epos are generated using the STEALTH data -eporting syste which
compiles the S Login information. This cc r `c-i is then transferred to a
file, which STEALTH uses to generate a repor (. The forms generated may be
SOP NO. S C-608
Revision 5
Date: 7123107
Page 13of17
CAS standard reports, DOD, or client-specific reports. The compiled data from
STEALTH is also used to create E s.
13.6.2. As an alternative, reports are generated using Excel® templates located in
:\SVG\forms. The analyst should choose the appropriate form and C pages
t correspond to required tier level and deliverables requirements. The detected
analytes, surrogate and matrix spikes are then transferred, by hand or
electronically, to the templates.
13.7. Sar )le concentrations are reported when all C criteria for the analysis has been met or the
re= , s are :i'?f ed with an appropriate foc is .e.
14. {
i ac( ie spr ac laiy
section of this (anu ' -
v: Gt i_, ucable) i... k5). ALSO, l ciui to ,?Iji ivi I vest l l rr r::: zy a
Corrective Action for cor;-ect proce r,; for identifying and ocur. ; Ming such ci-,-. raced res
for applying data qualifiers are described in the S for Refxart Generation or in project-specific
requirements.
15. METHOD PERFORMANCE
15.1. This method was vat da : .dies of accuracy and precision,
efer to the reference r. ')rmance data available.
15.2. The method detection lire, fir' DL) is established usi ig the procedure described in the SOP
for The Determination cif Method Detection L hvits and Limits of Detection (AD - D L)
.
Method Reporting Limits are established for this method based on MDL, studies and as
specified in the CAS Quality Assurance Manual.
16. POI,LUTION PREVENTION
It is the laboratory's practice to minimize the amount of solvents, acids and reagent used to
perform this method wherever feasible. Standards are prepared in volumes consistent with
methodology and only the amount needed for routine laboratory use is ___pt on site. The threat to
the environment from solvent and reagents used in this method can _ e r--ized when recycled or
disposed of properly.
17. WASTE MANAGEMENT
17.1. The laboratory will comply with all L "., State and local regulations governing waste
management, particularly the hazardous W as,c identification rules and land disposal
restrictions as specified in the CASE S Manual.
SOP NO. SOC-608
Revision
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17.2. This method uses non-halogenated solvents and any waste generated from this solvent
must be placed in the collection cans in the lab. The solvent will then be added to the
hazardous waste storage area and disposed of in accordance with Federal and State
regulations.
18. i I
18.1. The following items provide guidelines for training analysts.
18.1.1. Review a plicab : l° -e (method references, etc.) and this '. ,-w the
S for J z l? sis.
_L. r
Methods for Organic Chemical A,:, ' A"` c pal an 1, gdustrial ante ater. Method 608-
Qrganochlorine Pesticides and PCBs.
S NO. S C-608
Revision 5
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TABLE 1
o 1,...; s^ Polychlorinated i e ys (PCBs)
Target Analyt,;s, ?..?,. ,;;,: ti Limits a a t _o Detection its
MRL u
Compound (µg/L) ([g/L)
Alpha- C 0.01 0.0016
Ga a- HC (Lindane) 0.01 0.0011
-'3C 0.01 0.015

1

E ausu 0.01 0.00074
4,4'-L::A__ 0.01 0.00045
ielrin 0.01 0.0013
Endrin 0.01 0.00084
4,4'-DDD 0.01 0.0012
Endosulfan 11 0.01 0.0017
4,4'-DDT 0.01 0.0013
ndrin Aldehyde 'X59
Endosulan Sulfate 0025
Toxahen 1.044
Chlordane 0.2 0.11
PCBs: Aroclor 1016 1 0.045
oclor 1221 1 0.095
oclor 1232 1 0.061
oclor 1242 1 0.023
Aroclor 1248 1 0.0068
Aroclor 1254 1 0.036
Aroclor 1260 1 0.051
SOP NO, S C-608
Revision 5
Date: 7/23/07
Page 16 of 17
TABLE2
Pesticide columns:
Gas Chromatograph Operating Conditions
Oven "l erg Gare 1`rograrn: 50°C for .5 iniri., 50-150°C at 40'hn ., ra ,1p 13°,?? .. co 320°C, ; Id 192
min.
Detector Tf_ , , °ire: 325°C
PCB ccolumns:
Column 1: 35 30m x.53
Column 2: DB-YLB 30 x 0.53 ar
and Column: IP FACT 5m x 0.53 __
Gas Croatograp: /Agilet 5890 or equivalent
Injection Port Temperature: 300°C
Injection Volume: 1 lL
Oven Temperature Program: 160°C for 0.5 min., 30°/min, to 210°C; 1.0°/min. to 300°C, hold 11.03 min.
Detector Temperature: 350°C
Carrier Gas: Helium
Auxiliary Gas: Argo ethane
Data System: Enviroquant or Target
The above instrument temperatures may be modified when determining additional single response or multi-
response pesticides.
SO .5 C;-608
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Page 17 of 17
ATTACHMENT A
QC Acceptance Cr'''_,
I S IV LATIL ORGANICS ANALYSES

Prep
Method

Matrix

Anal yte LCS
Accuracy
(% Rec.) 1 latrix
e
)
608 3520C Water 4,4`-DDD 65-122 10-159
608 35200 Water 4,4"-DDE 57-122 10-151
608 35200 Water 4,4'-DDT 67-129 10-157
608 35200 Water Aidrin 30-125 10-126
668 35200 Water alpha-I3HC 58-114 38-119
608 35200 Water alpha-Chlordane 29-159 70-130
608 35200 Water Aroclor 1016 70-130 70-130
608 3520' Water Aroclor 1260 70-130 70-130
608 35200 Water beta-BHC 55-141 19-142
608 3520C Water Chlordane 70-130 70-130
608 35200 Water delta-131 IC 67-125 22-141
608 35200 Water Dieldrin 63-113 10-147
608 35200 Water Endosulfan I 46-105 10-129
608 35200 Water Endosulfan E 52-110 10-133
608 35200 'A - F loss, in Sulfate
_ 66-119
....... 10-148
60

(A. .? i

3 ?,Gi)C
]
eA - auna-Chloru, e i 5-1 , -4 " .
608 35200 V at? Heptachlor 35-126
608 35200 Water Heptachlor Epoxide 62-114 10-144
608 3520' Water Methoxychlor 55-159 70-130
608 35200 Water Toxaphene 70-130 70-130
"39 3520C Water ? nyl (Surr.}
Decachlorobip 10-138 NA NA

"
35200
Water _
Tetrachiol - - Skmm)
{ 1
20-122
1 NA
NA 1
Appendix F
SVOC - Method 625
P No.: C-- 2
Revision 5
Date: 111.2/09
Page 1 of 23
STANDARD OPERATING PROCEDURE
Approved y:
_ COMPOUNDS 1
v' ethod 625

L; ,:;...Leary nG ;er
CO-
a° .?1 11C ES, INC.
1311 Soufl ' 3th Av, e
also, W- -,n 98626
° Columbia p _ - _ - I Services, Inc. 2006
I)ate
Date -
DOCUMENT C NTR C -
NU :
;¢..
S(7 No.: S C-625
Revision 5
Flat ?: 1 / 12/09
P , 2 of 23
SEN111VOLATILE ORGANIC CC - ti, /a
Method 62,
L SCOPE AND APPLICATION
2. METHOD SUMMARY
2.2. The followin - compounds may require special t ~t when being dete mine ` by this
method, Le v can be subject to oxidative ios :?s during solvent concen a d the
chro atograp: , for this compound is poor. exachlorocyclopentadiene is subj, _ to thermal
decomposition in the inlet of the gas chro atoraph, to a chemical reaction in acetone, and
S No.: C-625
Revision 5
Date: 1/ 12/09
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3. DEFINITIONS
3. . Analysis, Sequence - Samnles are. analyzed in a set referred to ps an 5v 'ysis senvipnr'e. The
secs r ce i s v :' ?cti( of 1 -caf )rotrir)hc v' ,hoc e W_- 11 -11 lni at
ca
3.3. Standard Curve - stanar plots concentrations of a
known analyte standard v+ 7s . .. e analyte.
3.4. Surrogate - Surrogates are orgy v K::c which a.,- similar to analytes of interact '-
chemical composition, extractio c1_ro atography, but which are not no al_y _3 e
envirnn rental cn niece The p,,;rpn • of thy s'.irrogates is to -aluate 'the A-
analysis of samples. These compounds are spiked into a" '- :: ' s, standards, c r pies and
spiked samples prior to analysis. Percent recoveries are calc.. rted for each surrogate.
3.5. Method lan - rethod blank is `al. sample design-?' to monitor introduction of
artifacts into the pwocess. The method bla:l"; is carried throuL- mire analytical
procedure.
3.. Continuing Calibration Verification .1(CCV) - A id-level standard injected into the
instrument at specified intervals anti is L Cd to verify the validity of the initial calibration.
3. i . T__1 r`iderrt Calibration. Verification Standard (CV) - A id--level standard injected into the
instrument after the calibration curve from a different source than the standards in the curve
and is used to verify the validity of the initial calibration. Also known as Second Source
Calibration Verification (SSV).
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ate : 111.2109
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4. INTERFERENCES
.1. Raw GC/ MS data from all blanks, samples, and spikes must be evaluated for interferences.
et ° -1 if the source of interferenc- e . in the preparation o the samples. Corrective action
should taken to eliminate the infi _ ;s.
c a- occwr ,. ?c . yr l _ :.on
s iples a.': tially _ __Iyzed. To re(,e carryon ?l_- imege eavr be `:ISed
out between samples with solvent. Whenever a 'y c4 e prated sample is
encountered, it should be followed by the analysis c' solvent to check for cross
contamination,
. SAFETY
5.1. All appropriate safety preca4 :agents and samples must be taken
when performing this procec °e. v? personal protective equipment,
such as, safety glasses, lab cc ere_ gee)ves.
5.2. Chemicals, reagents and standards must be handled as described i the CAS safety policies,
a roved methods and. In P, where available T?efer to the C4 AC Pn'Tirnnmental ljo ilt
i i LLY, B.A.t iYYLYf
and Safety Manual and the appropriate MS DS prior to beginning this method.
53. This method uses Me1' Chloride, a -nown human carc;niNgen. Vit- brand gloves
should be used while rips-n-, pouring or transferring the solvent
SAMPLE COLLECTION, CONTAINERS, PRESERVATION,
AND STORAGE
SOP No.: S C-625
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6.2. Sample containers ' be filled with care so as to prevent any portion of the collected
sample coming in coni a_ - with the sampler's gloves, thus causing contamination. Samples
should not be collected or stored in the presence of exhaust fumes. If the sample comes in
contact with the sampler (e.g., if an automatic sampler is used), run reagent water through the
sampler and use the as a field blank.
6.3. Water samples must be iced or refrigerated at 4 ± °C from time of collection until extraction.
6.4. Water sa nles must be extracted within 7 days and the extracts alyzed within 40 days
. C}.`?:'-d 1 It 7?
C.X a -10.
7.
7.1. s C' o to( /Ma:; --ic xr yste
7.1.1. Gas C ..o atc raph - An analytical system cc ' : with a temperature-programmable
gas c1 sRiitable for splitless injection a--1 all re !red accessories, including
syringes, u ! ,al columns, and gases. The capillary col y s iould be directly coupled
to the source.
7.1.2. Column: tx-5 S - si'_lcone-coated
fused-silica capillary -5 MS wit 11Eegra-guard,
cat-log #12623-124, ! .
7.1.3. ;s Spectro f '-,r - Cc-`°°ble of sc_? p ma g from 35 to 500 amu every 1 second or less,
using 7 volts '-- l) electron energy in the electron impact ionization ode. The
mass sner.trnrneter r USt he onnnhln of nrnriiaoi a n mass cn otnim fir
deca uorotriphenylphosphine ( ) which meets all of the criteria in Table 2 when
1.0 /CL of the GUMS tuning standard is injected through the GC (50 g of DFTP ).
7.1.4. GUMS Interface - Any GC-to-MS interface that gives acceptable calibr, 'ion points at
50 ng per injection for each compound of interest and achieves acceptab
performance criteria may be used.
7.1.5. Data System - A computer system must be i ' to the ass spectrometer, The
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scan-number limits. The most recent version of the A/ST Mass Spectral Library
should also be available.
7.2. Appropriate analytical balance (0.0001 ), volumetric flasks, syringes, vials, and be for
standards preparation.
STANDARDS, REAGENTS, AND CONSUMABLE a t l UALS
.1. Solvents: Acetone, yl-ne chloride, ethanol, and other appropriate solvents. Solvents
must be of sufficiea r _ d to permit tacage without lessening the accuracy of the
detf, .1 zr , aon c per' ? :es.
8. {
8.2.2. Transfer the stock ww_? _ Tv Jr yaled crimp-top vials. Store at -1.0°C
and protect from light, or store recd__l__:en e by the manufacturer, Stock standards
should . e checked frequently for signs of degradation or evaporation, especially just prior
to r i ctnnrinrric from them
8.2.3. Stock standard solutions must be replaced after one year, or sooner, if comparison with
check standards or samples indicates a problem.
.4. GC/ MS Tuning Standard (See Table 1) - A lee chloride solution containing 50 ng/[L
of decafluorotriphenylphosphine (DFT P). _ eer_Jard should also contain 50 ng/µL, of
be idine, DDT, and pentachloropenol, to ver' , ion port inertness and C column
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performance. Store at -1° or le s - -iot being used, or store according tot the
manufacturer's recommendations.
.. Calibration Standards (See Table 2)
IS.
:e a e : soo a c ®{ vw a r Jblr-'.
8.5.2. The daily calibration standard (CCV) is prepari ' corresponds to the mid level of
the curve from stock solutions. T. CCV is prepare ?' ., and can be stored at °C ±
°C, or as recommended by - e acturer. The " 'P standard may be combined
with this standard (main _L concentration) providing tuning verification and
calibration verification c, o -it `-at f_ es.
8.6. C Standards (Attach ei
8.6.1. Surrogates: Prepare a -a : a.:: -1 containing 2- uoro henol, phenol-
d6, and 2,4,6-tribro op__e__ol ?« L _' _,g/µL, and i-trobe c -d5, 2-fluorobip enyl, and
to henyl-d14 at 100 ng/ L. Aliquots of the solution a r into all extracted
sae nit-.q hNnk,' anti tomc sa, nl es according to the extracti SOP I pti
1-1 8.6.2. Matrix Spike Standards: °e a working so, '- r i-_ -o1 containing all analytes
of interest ("fry '.st sp.1__,9 100 ng/;?L. A a. its cif thv ; lUtro21 ure spiked into the
selected C a ° i acc J the extractio° SOP used..
8.6.3. Note: The spiking level of surrogate and spike may need to be adjusted according to
project requirements, if dilutions are expected due to high levels of extracted components,
or if a lower calibration range is used.
9. PREVENTIVE MAINTENANCE
9.1_. All maintenance activities are recorded in a maintenance logbook kept for each instrument.
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.. Carrier gas - nline purifiers or scbers should be in place for all sources of carrier gas.
These -- : selects to remove water, oxygen, and hydrocarbons. Purifiers should be changed
as r _ ?c - ided by the supplier.
9.3. Gas hromatograp
9.3.1. Whenever maintenance is performed, care should be taken to minimize the
intro&ction of air or oxygen into the column. Injection port maintenance includes
chan---. x tt-e injection port liner, seal, washer, o-ring, septum, column ferrule, and
as tr ,r gyrin-P, as npedfvi. Liners nri Si-a fi -,holild hi- changers wbpn rf-cpnt sa !ple
a t arcs le.:: ' c c r >: r ra ic erfo .-nTnce. In some c,-: .s 4 d
pc, on of L,ie c .
and n, it Cation) by usi g '1e
er cc c'
As the column length is reduced, column head pressure should be adjusted to ma c
proper flow rates.
9.3.3. Over time, the column all ex' 1 "y poorer o 1 contaminated sample
matrices are analyzed. T'- ? len`. of ti__Ze fo occur "" depend o the samples
analyzed. When a notic r ants is evident and other
maintenance options c'o °* cola should be replaced. This
is especially true whe°° al :)ration difficulties.
9.4. Mass Spectrometer
9.1.1. - - the.?.5 as Headed to result .r. consi "..scent and acc y? e performance 117hrch meets
FTP ion abundance criteria described in Table 1.
9.4.2. For units =under service contract, certain rkra' ; .0 per 1110Liulretit
sc rvice staff, including pump oil changed, vacuuming boards, et( , as recommended by
lafacturer.
9.4.3. S source cleaning should be performed as needed, depending on the performance of
the unit. This may be done by the analyst or by instrument service staff.
10. RESPONSIBILITIES
10.1 it is the responsibility of the analyst to perform t .e analysis according to this SOP and to
complete all docume `.r Lion required for data review. Analysis and interpretation of the results are
performed by pens,--- the laboratory who h? e c istrated the ability to generate acceptable
results utilizing this SG P. Th s stration is in accordance with the training program of the
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laboratory. Final review and sign-off of the data is performed by the department
supervisor/manager or designee.
10.2 It is the respc- ibility of the department supervisor/manager to doc yst
training. oci g aethod proficiency, as described in 625, is also the _ ?sl- ty of
the department su ervisor/ anager.
MPROCEDURE
11.1. Samnle. reparation
1 ' . SA AS
ai _ ex ract
cold storage unit. E)_ uc _g f < yzed .. ' 'un 'J days of e) : :,tic ° .
11.1 Sample analysis
°". Refer to the SO for Ca" `" )ration c n - ; for Organics Chromatographic A rxild __1y sus
- *r '. calibration policies. c r- ,e(,; < A options chosen must follow the
CAS SOP. The specific ca"' r,
r.
11.2.1. The recd _ic. _ ns:
Final time: 32.0 in.
Equilibration time; 0.20 in.
Temperature ramp: Initial temp
amp rate
Final temp
pressure profile. Transfer pr(
150°C
8 0 1-/,
3G,,OC
,ssure 10 psi
Transfer time 1.50 in.
initial pressure 8.83 psi
Final pressure 38.50 psi
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Split flow:
Sample volume:
Carrier gas:
11.2.2. Initial Calibration
3.0 / in, at initial
1.0 ftL
helium at 35 cm/sec
11.2.2.1. Prior to calibratio~, '1Ize the GUMS tuning standard using instrument
conditions used for call'61 ? : .
11.2.2.2. Evaluate the spectrum obtained for DFT against the tuning criteria in Ta 1e 1
11.2.2.3. The internal st ??r3 should 1:< r---st c' the components of interest in the
11.2.2.4. Analyze 1.0 gL of each calibration standard (containing internal standards) and
tabular 1 e area of the primary characteristic ion against concentration for each
con-,,c,
f
11.2.2.5. Calculate response factors ( s) for each compound relative to one of the
internal standards as follows:
(A.Ci,)/(Ai,C,)
where:
A,, = Area of the characteristic ion for compound being measured.
A15 = Area of thi ( utracteristic ion for specific internal standard.
C; = Concert i' the specific internal standard (ng/ L).
C, = Concentratic of the compound being measured (ng/µL).
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11.2.2.6. Calculate the percent relative s leviation (% S ) for the response
factors.
AS'L) _ 1°. _ )2
N- 1
=t
w ,° 1:
%IZSD SD 100
W,
where:
S r," '.,e n4 , 1^vi^*io .
a compound.
S (,.-age s for a compound.
11.2.2.7. If the F value c e c,.; ' -°ation range is a constant (< 3 %c RS D), the
can 1 r su ed to be invariant and the average F can be used for calculations.
Al' rel the results can he used to plot a caliratinn carve rising a tir?ear
re ----sk n or quadratic calibration (refer to SO S C-CAL for procedure and
criteria).
11.2.2.8. Following initial c, jai ion, analyze an ICV standard. The ICV .,-.ic, w_. ;t
11.2.3. Cc,___: .. Caliration
11. A calibration standard, or standards, , A -co- -`on `on (See Table 2)
containing all target analytes, FTP , and u_ regt.i . •ogates, must be analyzed
every 2 hours during analysis. The ust ,.. :.a a ass spectra (see
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625, Section 12.3 for guidance) which meets the criteria given i Table I. The
re tailing factor must be less than 3, and the pentachlorohenol tailing factor
be less than (see 625 Section 12.4, 12.5). These criteria must be
nonstrated each day before any blanks, samples, or standards are analyzed.
Note: enzi in is analyzed, and the e idie tailing factor calculated, only when
it is to be reported in the associated samples.
11.2.12. If the response for any parameter varies from the predicted response (calculated
as % rift) by more than 207®, the test must be repeated using a fresh calibration
a-&-.! . C plc `.ate `le P- -cc sing:
r
where:
C, = Calibration Check Compound sta a d concentration.
C, = Measured concentration using sc c A uantitation method.
11.23.3. If a CCV ar ~'` 7t;-al sequence fails to meet
acceptance criteri and a second CCV may be
analyzed. If the s ialysis may continue. the second
CCV fails to c,E stopped, corrective action is to be
taken and docu en"v:. 1.. case, , y has to either demonstrate
performance after corrective action w` _.. _: co-- (ecutive successful calibration
verifications, or a new initial Y1SiY lYYC l alttTlc 14t?L U ?3GIIUIIIIGU. 11 C11
laboratory has not demonstrated acceptable perf- ance, sample analyses shall not
occur until a new initial calibration curve is established and approved.
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analyzed while the system was malfunctioning is required. Update the r- "-,rence
spectra and retention times in the quanitiation database as needed. Th ;
calibration average or calibration curve is then used in the quanitiatic A
sub; - _ nalyses.
11.2.3.5. via (method blank, C blank, or solvent blank) may be analyzed after the
C to prove the system is free of contaminants. If contaminants are found in a
method blank or G PC blank, then a solvent blank should be ran to help isolate the
source of contamination.
11.2.,:. GC/? TS r-'vF, .
..
11.,.4.- ilorr it ne
intern' solution ' wa falc„t to analysis. Use t__e s:: me ofer `-g c(.-c--ions
as were used for initial calibration.
11.2.4.3. If the response for any c -.tic-- 'on exceeds the initial calif °r ion curve
of the GC/MS system... e-: = must take place. °c al internal
t
-andard must - i e ' ``1 ) r aintain the r qui 40 ng/ItL of
each internal sta ie diluted extract must be
reanalyzed.
11.2.4.4. Store the er tr__va . -16 u y i rc,, :::; Aro light in vials equipped with
unpierced Teflon li, -_! septa. Arcl:' Je extra--* 3 in freezer for 3 months after analysis
in the instrument/date specific storage boxes.
QA/QC 12. F`_'_
12.2. Method Detection Limits
12.2.1. A method detection limit (MDL) study roust be undertaken before analysis of
samples can begin. To establish detection limits that are precise and accurate, the analyst
must perform the following procedure. Spike a minimum of seven blank reel icate.,; with a
MDL spiking solution (at a level below the L) for each target analyse, extras, _
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analyze. The MDL studies should be done for each matrix, prep method, and instrument.
Refer to the CAS S for e Determination of Method Detection Limits a Limits of
Detection.
12.2.2. Calculate the average concentration found (x) in the sample concentration, and
the standard dee,°^tion of the concentrations for each analyte. Calculate the MDL for
each analyte u,° - tae correct T value for the number of replicates. The MDL study
should be dor v , .;:ally.
12.3. Ongoing C Samples required are described in the CAS- Kelso Quality Assurance
a a t ---' i -ie S ::) "?_. le ' s. I g(t_ _ se lade:
c4
12.3.2. A lab control sa-_---le (LCS) tri-:1- be extracted and analyzed with ---- f tch of
2 or fear- samples. T"e ? ! S is sp'°°_-®a blank with the aLrin_ 4 Jive
solution, r d going thrc .:° ! °4 :alysis. Calculate perceiit recovery
(%R) a; '-c /s:
% = X/V x
Where X - Concentration of the analyte recovered
TV - Tree value of amount -,nilpd
Acceptance criteria for lab control samples are listed in Attachment A. If the lab control
sampl- - e (11-CS) 'fails ar.c?.eptanre limits for any of the co pousinds t e analyst ii'tist evaluate
f. j...,.. J ixu..s' x c..
the system and calibration. If no problem s are found, corrective action must be taken.
12.3.3. A matrix spike/duplicate matrix spike ( S/I)Nm-J) must be extracted and analyzed with
every batch of 20 or fewer samples. The S is ;d by spiking a sample aliquot
with the matrix spike solution, and going tf--o°_ e _ -itire extraction and analysis.
Calculate percent recovery (%R) as follows:
X_ X1
/1 11 - x 100
ly
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Where - Cc '.on of e analyte recover
1 = Cone- ration of i- -d analyte
T - True value of amount spiked
Calculate Relative Percent Difference ( ) as:
RI - R2
D - x 100
(RIfiR2)12
R! = !C 1'eCO-°* V r 11 Q
1.11-1 r+_ ,,ove-j of acc _ nor -,asou a m , ,crs, cc ,.r: ive ac`` )n
must be U'-,en.
12.3.4. The acceptance hunts for the su °c, - re given in A clinient A. 11' surrogate
recovery is outside acceptance criteria, the s, nple data must be closely evaluated for
possible matrix interferences. If none are present, then corrective action must be
identified.
12.4. Additional QA/ QC , s, mg of C sample results.

13.1.1. The intensities of the ch..--eteristic ions of a compound maximize in the same
scan or within one scan of eac'? c ,t r. Selection of a peak by a data system target
compound sea -ch routine where ti, search is based on the presence of a target
chro atog - 'c )eak containing ions specific for the target compound at a co pound-
specific Me1!L cr time will be accepted as meeting this criterion.
13.1.2. The T of the sample component is within ± 0.06 T units of the T of
the standard component.
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13.1.3. The relative intensities of the characteristic ions agree within 20% of the relative
-,iti rs of these ions in the reference spectrum.
13.1.4. Structural isomers that produce very similar ass spectra should be identified as
in(' -v* -1 °so ers if they have sufficiently different C retention times. Sufficient C
resoi, .-,)n is achieved if the height of the valley between two isomer peaks is C 25 % of
the S .n of the 2 peak heights. Otherwise, structural isomers are identified as isomeric
pairs.
13.1.5. m enti
^?n
:le
13.1.6. For s---'--- co Mr _ ~g cc?°e° r::c:is - ~)t , --ciate with the calibration
standards, a lil' l- of tentative identification. Refer
to echo 625 for :.Ajpo nd (TIC) identification and
quantification.
13.2. ua titation and Calculations
1,(T)F-' i
ISTD I(? X,I
Where: C,,x = the concentration in the sample extract (pin);
espx = the peak area of the a lyres of intl : rt;
eSPISTD = the peak area of the associate standard;
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ArWISTD : the a _ -t, i ppm, of internal standard added
IU"- = the avc-°age response from the initial calibration.
13.2.2. The concentration of analyzes In the original sample is computed using the
following equations:
1.1 . ?. Sc. tu44 le fvl ,3,7,8-Ituaciiforod" ,;, lzo-p-d ,,,3,7,8' Cam., ?
13.3.1. From Enviroquant draw art Extracted Ion Chromatogram for ins 320,322,324
from IS minutes to the end of e run. Print the chromatogram. The possible
presence of 2,3,7,8-TC D ' r ,d if all three asses exhibit s tr ;ous
peaks at any point in the extrac';d ° m profiles.
13.3.2. Screening r _S S1 . See method 625, Section
17 for L '.o tal info
13.3.3. Conclusive res® !ts of the r-7,- .r ;e and co.tion of 2,3,7,8-TC can be
obtained only from a properly equipped laboratory rough the use of EPA
Method 613 or other approved alternate test procedures.
13.4. Data Review
Following primary data interpretation and calculations, all data is reviewed by a
secondary analyst. Following generation of the report, the report is also reviewed.
Refer to the S for Laboratory t Review Process (A EV) for details.
13.5. Reporting
Reports are generated i the CAS L S by compiling the SI\/aJ login, s r prep
database, instrument,, r' and client-specified report rent s (when , scifed). This
compilation is then -Ire to a file which the Stealth repoi rer_g system uses to generate
a report. The forms generated may be CAS standard reports, DOD, or client-specific
reports. The compiled data from LI S is also used to create E s.
14. CONTINGENCIES FOR HANDLING OUT-OF- CONTROL OR UNACCEPTABLE DATA
SOP No. S -625
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Corrective action measures applicable to specific analysis steps are discussed in the applicable
section of this (and other applicable) S (s). Also, refer tote y -.1P for Nonconfonnity and
Corrective Action for correct procedures for identifying and e )c- ``ng such data. roc -('
for applying data qualifiers are described in the S for Repo, , tfft--,,u,,ation or in project-speL c
re--4--r-,- ants.
15.,. .__v
15.1. This method was validated through single laboratory studies of accuracy and precision.
Refer to i - -'t --let' ;a '. fc )n l me -'-o:-. erfo -a__.e da{ a avail, le.
_ e
is h: dc:
1 -_
It is the laboratory's practice to r the am-'-nt of sol - "nd reagents used to perforr- this
met".o wherever technically set .'-,1ra» lethod requirements. Sta - ~4-
,rp ared in volumes consi anini ize the volume of exf`re%A'
st -ards to be disposed of. T olvents and/or reagents user hi
t ` ; nethod may be mini izo 1 v -- i o_ 1-d .-roperly.
17. WASTE MANAGEMENT
The laboratory Y Will CO p1V With all F-' State and loyal r ulatinnc governm,a waste
management, particularly the hazardom .paste identification rules and land disposal restrictions as
specified in the CAS EH&S Manual.
od uses ethylene Chloride and any waste generated from this solvent iust be placed in
tti c :tion cans in the lab. The solvent will then be added to the hazardous waste storage area
and i ' iff site.
18. TRAIN.i 1%'%-T OUTLINE
18.1. The following items provide guidelines for training analysts.
18.1.1. Review applicable literature (method references, etc.) and this SOP. Review the
a S S for all chemicals used in the analysis.
1.1.2.Observe the procedure as performed by an experienced analyst at least three times.
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DFTPP KEY IONS 1 val., --

27S
36 1
441 Present but less did ass 443
442 > 40% of mass 1.95
443 17-2 % of ass 442
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TABLE2
625 STANDARDS
ecoi_ ended: Supelco catalog #(or 'ent from other venders*):
Equity CL SV ix, 1000 pp
Equity Cal ix , 2 pprr
Equity -Nitro- ),' ` °-iyla- 500 p
city e idii -s 200C,,
Accustandard 8270 surrogate rnix, 400 p
Pr 1 { c a
Cc i
ICV
use he San: ,l'utions that were useu i^vr U-21. calibrau%jll %uidc' aitu the toilewiilg:
Accustandard (recommended) catalog #(or ( 'Talent from othe va *):
6250-3-1 1 nil 25 mg/ml F PP
Prepare 1 ml of 50 pp 8270 CCV standard, place ` autosa ple vial and cap i red crirr p. 50pp
is the nominal concenira ion.
Expiration date is ' ` , - er CCV was prepared.
INJECTING
Store the _g sioc . zsofu ons in I u l inner inert vial. Expiration date is one year after ampule is
opened o?. 6 expiration daik; on the a pie, which ever is earlier. Order when down to one unopened
ampule.
* Vendor must be LA and/or IS09000 certified.
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.,.
g ? ? 1
QC 47
625 to
Using the same source as the calibration curve, the ampules containing the surrogates are used to
prepare a surrogate x in methanol at 100 pp for the /N s ggogates and 150 pp for the acid
surrogates.
froree date. p,, -?-d = 3 of '] a
s ,
U; ` v the same &_ _iree as d_:, standards used to prepare the cL e jr?_ ? cx a df i sc: anon in
ethanol is prepared.
Stan(' Js Expiration. Unopened = 6 months from preparation dat pen = 3 months from
of original 6 months, lever is first. When breaki o an unopened bottle,
1 w expiration dal c 1e %1 d i the lc, of k, with initial and date.
Exp ire' m are to be s they are r' vrt y used.
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TABLE3
SETWVOLATILE INTERNAL T' .-.
ASSIGNED FOR N 7lL -
Nitrot -
Nitrottenz le
Isophorone
B `2-chloroethoxy)Lnethane
e,Y
2.4-Dichlorophenol
4-Chloro-3- e ' -)I
-ie Pluorene
2,= 4-:: itrophenol
2 : 2,4,6-Trichlorophenol
D' 2,4-Dinitrophenol
4-Chlorophe..a ; ::rnyl -d.er 2,4,6= I'ribromophenol (surrogate)
1,2-Dipheny1hydrazine
Pnenanthrene-dI0 Internal Standard
?IN-Nitrosodiphenylamine Phenanthre'ne Pluoranthene
4-Bromophenyl Phenyl Ether Anthracene 2-Methyl-4,6-dinitrophenol
Ilexachlorobenzene Di-n-butyl Phthalate Pentachlorophenol
Chrysene-c `; Si udard
Pyrene 3,3'-Dichlorobenzidfi Chrysene
Butylbenzyl Phthalate , Benz(a)anthracene Terphenyl-d14 (surrogate)
Benzidine Bis(2-ethy1hexy1) Phthalate
Perylene-d'" ` Standard
Di-n-octVyl Phthalate Benzo(a)pyrene Benzo(g,h,i)perylene
Benzo(b)fluoranthene lndeno(1,2,3-c-,d)pyrene
Benzo(k)ftuoranthene Dibenz(a,h)anthracene
SOP No.: C-625
Revision 5
Date: 1 / 12/09
Page 23 of 23
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Appendix G
PCB/SVOC Extraction - Method 3520
SOP No.: EXT-3520
Revision: 11
Date: 4/30/07
Page: l of 12
STANDARD OPERATING PROCEDURE
For
CONTINUOUS LIQUID ITT EXTRACTION
Approved by:
Date
/'-
Date
'D at
COLUMBIA ANALYTICAL SERVICES, INC.
1317 South 13th Avenue
Kelso, Washington 98626
o Columbia Analytical Services, Inc. 2007

DOCUMENT CONTROL
NUMBER:
" i'`ials: ate:
SOP No.: ET-3520
Revision: 11
Date: 4/30107
Page: 2 of 12

1. SCOPE AND.' "CATION
1.1. This procedure uses techniques described in EPA Methods 352013 and 35200 for extracting
nonvolatile and semi-volatile organic compounds from aqueous samples.
1.2. This method is applicable to the isolation and concentration of water insoluble and slightly
water soluble organics in preparation. for a variety of determinative methods which use
' :o' a:':),- °c,)f proced.: -s. P'efer to C e deter -.-in..,'..ive prod-;du; •e ro do - .1---e 'f . e this
1 ' ori
)r_. .:)i . o sciblc
soivents. ilie soivc ee I- IL SC . US __X Lt densate irom a LC_U] CC; :IX.
SUMMARY
2. METHOD 2.1. A measured volume of sample is placed in a continuous liquid-liquid extractor, pFI adjusted
(if necessary), and extracted wit! ^n organic solvent for a determined period of time. In this
procedure, the extrace`?r- sole. a density than that of the aqueous solution
being extracted, a0_ N. ng solvent to be diverted through
the sample, extract ~g o- ,ack into the boiling flask.
2.1 The extract is dried, con( and (_f nece,_:wry) exchanged to an appropriate solvent
for the determinative procedure. i e extract may undergo additional cleanup steps defined
in other procedures.
3. ".
3.1. Reflux Condenser: An auxiliary vessel for a distillation column that condenses vapors and
returns liquid to the column.
3.2. Total Reflux: A distillation column is said to be operating under total reflux when all of
the vapor leaving the column is condensed and returned. No products are withdrawn from
the system. The reflux ratio is infinity.
3.3. Reflux Ratio: The quantity of liquid reflux per unit quantity of product removed from the
process unit, such as a distillation tower or extraction column..
SAFETY
SOP No.: EXT-3520
Revision: 11
Date: 4/30/07
Page: 3 of 12
4.1. All appropriate safety precautions for handling solvents, reagents and samples must be
taken when performing this procedure. This includes the use o personnel protective
equipment, such as, safety glasses, lab coat and the correct gloves.
4.2. Chemicals, reagents and standards must be handled as described in the CAS safety policies,
approved methods and in MSDSs w' -? available. Refer to the CAS Environmental,
Health and Safety Manual and the appropri4-v MS DS prior to beginning this method.
4.3. This method uses Methylene Chloride, a known hurnan carcinogen. Viton brand gloves
should be used while rinsing, pouring or transferring the solvent
. 4
a -y
o? r... ; . :tr&c
5.1 Rinse all glass sutaces involved in unc extraction process iijoroughly with CH2CIr (reagent
grade or re-distilled). Three rinses is usually adequate.
6. RESPONSIBILITIES
It is the responsibility of the a--C,. Tst to pr% : :i the analysis according to this SOP and to complete
r
7. SAMPLE COLLECTION, PRESERVATION, AN W-'-.
7.1. Refer to the applicable section in the determinative SOP for sample collection, preservation,
and holding times.
7.2. The extract holding time is 40 days from sample preparation to analysis.
APPARATUS A N iA : f
8.1. Continuous liquid/liquid extraction body
82 500 ml round bottom flask, with green Deck clip
8.3. Graduated cylinder, 1 liter, Class A, TC.
8.4. Stir rod and pH paper
SOP No.: ENT-3520
Revision: 1.1
Date: 4130107
Page: of 12
.5. Allihn condenser
8.6. ''c 7-, ?s - Pre-cleaned via Soxhlet extraction, approximately 10/40 mesh (silicon
carbide; o-- equivalent).
8.7. Graduated pipets, 1, 2 and 5n1L. Pipets are pre-tested by lot for accuracy.
9. REAGENTS
9.1. Mr ylr__e C Lori - "es" "de grade or rec -,__lled if L.tch testing do -,s that the

93. 2-rro anc'
p° ?M- .0ri. Pesticide qua. qty ar equlva eni.
9.4. Acetonfirile, CH3CN. Pesticide quality or equivalent.
9.5. lso-octane (C113)3CCI 12CH(Cl13)2. Pesticide quality or equivalent.
9.6. Acetone CH3COCH3 - PI.- or "V" I(
9.7. Sodium hydroxide 1() g NaO in organic-free reagent
water and dilute to 10(`
9.8. Sodium sulfate (granular, anhydrous), Na2S0 . Purify by heating at 400°C for 4 hours in a
shallow tray.
9.9. Sulfuric acid solution (1:1 vlv), I1?SO4. Slowly add 50 ml of H2SO4 (sp. gr. 1.84) to 50 nil
of organic-free reagent water.
10. . , T '. ?, TE A CE
Routine cleaning of the extraction glassware is necessary. Refer to the :SOP for Organic Extractions
Glassware Cleaning.
It. PROCEDURE
11.1. Test-specific benchsheets are attached. fhhese benchsheets list such information as solvents,
solvent exchanges, weights, and volumes specified for the determinative method. Use the
correct benchsheet and record all extraction and sample information. To assist the analyst, a.
brief description of the procedure is given on the backside of the benchsheet.
SCUP No.: E XT-3520
Revision: 1.
Date: 4/30/07
Page: 5 of 12

NOTE: he v nouth of the extractor odd, be
careful not ) r siphon. When measuring out the
correct vole:-i? be -r: neasure the volume for the LCS and
the MB prior t me 5 triple. In this manner less glassware will be generated for the
glasswasher.
11.3.2. Samples with settled solid material or sediment.
11.3.2. Llf the sample contains a small amount of material, shake the sample to mix
the material into the sample and analyze the entire sample.
SOP No.: E XT-3520
Revision: 11
Date: 4/30107
Page: 6 of 12
IL 3.4. Check the pH of the sample with wide-range pH paper and adjust the pH, if
m : e, y, to 1.1e pH i-dic -_ ?d b - low, using ' :1 (v/v) :.ulf r? `c acid or 10 N
t ac ! `lc tc 101 ?d r< , : .
er

G IIIAL
E--RAC t11
ti -'ONL)A1iY
iAGHON Pi-
ORGANOCHLORINE PESTI(',IDFS (8081)
PCBS AS AROCLORS (8082)
ORGANOPIIOSPHORUS PESTICIDES (8141
)
SO('s BY GGIMS (8:70)
5-9
5-9
As received
<2
none
11o11e
11011e
>I1
11.3.5. Adjust the , v: r v r each the cycling volume point, with
extracting soly leer: 'e a 1 of 300 ml of CH2C1.2 in the boiling
flask. If not, add additio Dl A _ter).
11.3.6. Make sure that each continuous liquid - liquid extractor is cycling properly. Check
the chiller for proper temperature and operation. For proper operation, the water
flow must be continuous from the top outlet of the condensers and the condenser
must be cold to the touch before extraction begins.
11.3.7. Cycle the unit for an 18-24 hour time period. Method 8270 and 625 anbalyses are
light-sensitive, cover the extraction flasks with aluminum foil.
11.3.8. After the cycling period is completed, shut off all of the temperature controls and.
allow the unit to cool completely. Remove the reflux condenser from the extractor
body and clamp securely to the gr'J af__iratus. 12: ove the extractor body from the
grid apparatus by removing the r ' ' ' : 7 ch,- ' upper snap ring from the drying
flask, being careful not to spill the extram t in the 11 sk.
11.3.9. Method 8270 and 625 analyses only: Cap and store the initial extract. Repeat
sections 11.3.3 through 11.3.7 using a new aliquot of extraction solvent and making
SOP No.: E XT-3520
Revision.: 1 1.
Date: 4/30107
Page: 7 of 12
the secondary pH adjustment (plI >11) as specified in the method (see Table 1 of
EPA Method 3520C for 8270).
11.3.1 O.Deeant off the remaining extraction solvent from the body of the extractor into the
correct waste disposal container, and dump the remaining sample into a collection
bucket/sink for neutralization.
11.3.11.Rinse the body of the extractor thoroughly in hot tap water before returning to the
glasswasher.
11.3. 12.Pot : le e- t act from 'ie 500 ml E. ..3k into a p 'used K-D r:> via
u
)di 1 SL' C e K-
iVi:::: and 625 analysE,,-, C'ory' Poll. tw .t icj Ulai;_-J11 (first)
aid sec(,. du: y extract (second) through a mc,da --I u.t. cl contairti.rg sods lni sulfate
into a K-D apparatus.
.4. Concentrate the extract to approximately 5-10 m1s.Remove the K- apparatus from the S-
11.5. Solvent exchange is required for certain analyses in order to obtain a final extract in a
solvent compatible with the analytical system used. Exchange solvents are used as fisted
below.
Determinative Method
8081
8082
8141
8270
Hexane
Hexane
TBE
none
Exchange Solvent
et uired for Cleanu
Hexane
Hexane
Hexane
11.6. Nitrogen 131owdown Technique
11.6.1. Place the concentrator tube in a war water bath (approximately 35°C) and.
evaporate the solvent volume to the required level using a gentle stream of clean,
dry nitrogen (filtered through a column of activated carbon). Do not let the sample
go dry.
SOP No.: ET-3520
Revision: 11
Date: 4130107
Page: 8 of 12
CAUTION: o not use plasticized tubing between the carbon trap and the
sample.
1.1.6.2. The internal tivall of the tube must be rinsed doom several tunes with the appropriate
solvent during the operation. During evaporation, the solvent level in the tube must
be positioned to prevent water from condensing into the sample (i.e., the solvent
level should be below the level of the water bath). Under normal operating
conditions, the extract should not be allowed to become dry.
"'X,: ', , n a r
: vc e o.. E it is reduced below 1 ' c the
;r r e
extrau« t _ys _ to y now be ar J Zed -JI iitc ?c4 rtai, u, t::., appr( r: M.
deti..iiiimative tcciinique. The exu7act holding tliuk is 43 days fi, iii sample Vieparation to
analysis.
12. QUALITY CONTROL
12.1. Refer to the SOP for the ---iir Ao Id SOP for Analytical Batches and
Analytical Sequences
12.2. Any reage '.,: a' ix spike samples should be
subjected to exactly th.. s;.: le anal, sICL-- procedure- is those used. can actual samples.
13. CORRECTIVE ACTION
13.1. Refer to the SOP for Nonconformity and Corrective Action for procedures for corrective
action. Personnel at all levels and positions i the laboratory are to be alert to identifying
problems and nonconfor ities when errors, deficiencies, or out-of-control situations are
detected.
13.2. F . g out-of-control or unacceptable data
13.2.1. On-the-spot corrective actions that are routinely made by analysts and result in
acceptable analyses should be documented as normal operating procedures, and no
specific documentation need be made other than notations in laboratory
maintenance logbooks, nlogs, for example.
13.2.2. Documentation of a nonconformity must be done using a Nonconformity and
Corrective Action Report (NCA ) when: a) corrective action is not taken or not
possible b) corrective action fails to correct an out-of-control problem on a
SOP No.: E XT-3520
Revision.: I 1
Date: 4130107
Page: 9 01'12
laboratory C or calibration analysis c) reanalysis corrects the nonce ity but
is not a procedurally c, *t analysis.
14. POLLUTION PREVENTION
P ; the laboratory's practice to -;-e the -t c,f solvents, acids, and reagents used to
p?r?or this method wherever feat, , possible. .-urds are prepared in volumes consistent
iethodology and only the a oL_lt needed for rc,utine laboratory use is kept on site. The
t it to the environment from solvents ?c i - its used in this method can be minimized
%. ) ecycled or disposed of p _A 'y.

PL
res "o s as spec ied in the CAS E )viromae :1 IT d S,, NT Ll.
15.4. This method uses acid. Waste acid is hazardous to the sewer system and to the
environment. All acid waste must be neutralized to a p of 5-9 prior to disposal down
the drain. The neutralization step is considered hazardous waste treatment and must be
documented on the treatment by generator record. See the CASE S Manual for
details.
15.5. This method uses a base. Waste base is hazardous to the sewer system and to the
environment. All waste must be neutralized to a pH of 5-9 prior to disposal down the
drain. The neutralization step is considered hazardous waste treatment and must be
documented on the treatment by generator record. See the CAS EH&S Manual for
details
16. ii ' - t ?ORMANCE
Available method performance data is given in the reference method. In addition, this procedure
was validated through single laboratory studies of accuracy and precision as specified in the
determinative procedures.
SOP No.: EXT-3520
Revision: l l
Date: 4130107
Page: 10 of 12
1. I 4 NG
17.1. Training outline
17.1.1. Review literature (see references section). React and understand the SOP. Also
review the applicable MSDS for all reagents and standards used. Following these
reviews, observe the procedure as performed by an experienced analyst at least
three times.
17.1.2. 'The next training step is to assist in the procedure under the guidance of an
cxperier :e anal) ` L s n od, " ,e analy, is expecte,' to ' °ansit' 3n __om
of ia]. a
st_-i1J-.N. O :I-narits L: thy; l Fr, are reviel au ;.:u sit :e-,u ay i sup( ®sor.
Copies ii-my be forwarded to the empiVycv's traiinor, f,Ac. FGc tippllcrxiiie tests,
IPR studies should be performed in order to be equivalent to NELAC's Initial
Demonstration of Capability,
17.2. Training is documented following the SOP./br Documentation cif Training.
NOTE: When the t upervisc>r on internal training
documentation fort that the ana<Jve has read and
underLdands this SO s been given a lyst to
col 1 T perform t' i r s , e ldently.
18. REF E E CE
18.1. EPASW846, Test Methods For Evaluating Solid Waste, Third Edition, Update 11,
September 1994, Method 35208, Revision 2
18.2. EPASW846, Test Methods For Evaluating Solid Waste, Third Edition, Update III,
December 1996, Method 35200, Revision 3
SOP No.: E XT-3520
Revision: 11
Date: /30/07
Page: 1 l of [2
-, i' LEI
APPLICABLE EL' e
CONGENER-SPECIFIC DL"ZF:I2N1IN,h`I'I(}N OF F'CF3S BY GCi;F.C13 SC)C'-8082C
D -ERN.11NA'FION OF NITROGEN OR III IOSPI IORUS CON'T'AINING PESTICIDE S SOC-R I :I
OR ,ANOCHI.OR? v PESTICIDES BY GAS Cl IROMATOGR API IY: C'U'll 1,ARY COI IIMN TECI INIQUE S
` ''S AC AROU' ?r_gn r:
IM
_:1 Ge_J.1Nl? - Y t:. A : )WI: S: MIVOLATILE ORGANIC (") IOC `'DS - V GUMS v_ -L?CT. ION MONITORING SOC 7{ `
SOP No.: E XT-3520
Revision: 1 1.
Date: 4130/07
Page: 12 of 12

Additional Prey Information For EPA 3520
Service C Lot Acid Lot

Continuous Start, (Time/Date/Initial):
Continuous Stopl (Time/Date/Initial):
Continuous Start2 (Time/Date/Initial):
CC :oL
-evap Temp
Initial/ ate:
Initial/Date:
Base Lot
x e Lot
r r
COLUMBIA ANALYTICAL SERVICES, INC.
Appendix from EXT-3520
for Extracting Compounds in N titer by
EPA Method 35200
Procedure:
Vote a) Any Acids iir Buses used in this procedure must he checked for contamination prior to use.
(See CAS SOP)
h) All :urhydrous sadbou sulfate (.Na2S04t) used in this procedure crust be tharoug*hly rinsed with
methylene chloride (DC1l'1).
Steps 1 - 5 /f EYT be three in a fume hood
lieornu0h, rinse contimlous ttrr;CioTS and conc:ense .s a+ili; DChf
A, enXinnateir nis - sods
" ac' t 'f I hire :Intents : _. e i - to n- x ic.wd, mar ti e level
01 Ile 1. l-.r_ ;on - I. E_--actas-
etJJ ti;a contents the ract„r onup r t to allow w: -ert, mite ,r -- r l.-i dint; flask _ (7 his cube
cfn by tilting; the c. i-U W "off slov?ly u,nvn - - + t - tram-- ;md s ,+m ithunc ih=e cxtraeLnr 1-niwara toAaw
=nr eI'_ayivr to flow it the 'i .. tr,,sL) it nec t.,;ary, add L__it..... water _(] [nc,,rxtrmtar to ens srr n- , Cr penaion Use i i,ser
?f lsed D! water r th d LL'S_
looted tinder or with 5nmis off W K4 u1 adtl tc tb,,
6_ Acid sur on rna m (r;s. .' by a trained limflyst)
hc; it( ,flat t a:xi ,i tir
-one extr acts m! .11 ! -. apparatus nse:nniecl it ; a , kcal I nnel (to it :t up
with a sr 1 ping ai _ is ot, then anh -c _ Almys pour the primary extract first. Apply vacuum to
comptede the transi>r
I '! . Concentrate the extracts on an .'. vvalr arh the tc,.)pc,ature set netweeu 7(..'75`0 Remove tht l.D when hwe,.nlvent levei is low mouizh to
remove the collector- Etxt Brno ; )n must be used to rnsuie that the s I-apse cl;tie not concentaste too iow or an drynctss-
i4 isastel on sample; analysis and - rid I st, determine cleanup direction to Lake. See ch t
l y 7.t- c C ,tree;., is p „i rz„ed, cif - mi extract IS retained Thereioro the exvacL must h- . ncerkrui ..i to ;!? the tine: volume -n
ncisieve s.he connect "calculated" al I ie -
--,. Con enuate the ext acts to ' .mutate i ?. s, nil the '-L:vap na a m of r_ - •r I aperature not
cxc e cling 215'. Extreme caution mut , u - +nt tha' .. r.' , ?..r . to- ?w, l css.
1 7. Brm>; ex[raUS t i < r rt+1„ntr,;llirrn% vnuuun ;n] - - - y
18. Do -`.I. scree in (see CAS SOl') i salt.
9. -omnlcte^ all necessary, n4pnrwoik, on surrorai C,dculai.ed
slee _ Color Cleamus
Amount _ Pitrd VoiuruL,
8 270?635 I Lilei AP/hul h2' "i m€, dear GK'!ifnaeded
sit
8270 LL I ltle*, P,l'Mid <2 N!A. 2lid ainher tfneeded
:I ea
5270 TCLP alt l AP/l+=.d, o I',, oc[, ;e! w ,
ua- , ?z^_ if needed
unl,+ 50}d i
.. .
SEMI-PIIBN I l.,iler AP/2%d Phmict.s/200n1. N/A Unit, red none
SLIM-I'AII / Ii. ueded Silica
- fatter ,41 /ill}il °A };l ' 1 N/A 5lni. reer?
SIM-AI,KII 8 Gel'
SIA4-PiU-l- H!5 Liter AP!20p1 i?il+ N/ A Stnl. TBCB ?P:'ifeie.ecled
PCP i- `
I'Il2}I P Dc ts0µi PP, /5i ;s1 -= 1 I A 2 nil alnbtl &[Jca pl /
SWIlirm, AC1d
- -0 nil = u,1. clear no
1'tt112. I Lifer -
uh
(SDP.A r,;l 5A-I t.L );?. - 2n;L ?, .._
Berizklitis(Cas
I Liter Ai•Ci,;L Ganz dureSU, -7.i 'JIA lint ;m?fser
c31si)
MISC. t-'
cml!,:rzol , i m, 111r , Ornpmin d !1'.c! ur'o iIw .v r';cc s;ct io ;iPr` -
Additional Prep Information For PCB Water UL
Service Request
Type glassware used:
Solvents/Reagents se :
C Lot #
Hexane Lot
Continuous Start (Time/ ate/I itial):
Continuous Stop (Tim e/Date(Initial):

Additional Clean-u #
Vial:
Archived Extract Storage:
Comments/Observations:
Vial Storage:
Cher
-ev;
D `Iii srtmpics _1 so
all samples ? some sa ies
Work Group # :
STANDARD I
PCBs I
Ultra-Low-Lev- 1 ' [_ a
Method 3520
RASWVlA ditional Prep info Shoe ta\Additional Prep 1nlorinettionPCBWaterC,L,doa
Additional e Information For Pc-',',,! --'i3 Water
Service Request
Work Group # Pest:_
C :
olve is ease is used:
D-
C M Lot #
Hexane Lot 4
Continuous Start (Time/Date/Initial):
Continuous Step (Time/Date/initial):
Solvent Exchanged To F (Date/Initial) `] yes:
r s:

Cl -,`t
Pest Vial:
C Vial:
'Uri IVI
S-Evap Temp:
s .:_ .
" s-.:- -s J
Archived Extract Storage:
C o ,e /0 b serva io s:
Vial Storage:
Vial Storage:
R!AS?-'G\Additiumat Prep I'do Sheets\Additional Prep Infea-inxtioiiPestPCBW tter.doc
r I Prep Information For Pest/PCB Water
service Request 4
Solvents/ Reagents is sec :
DCI Lot #
exane Lot #
Continuous Start (Time/Date/Initial):
Continuous Stop (Time/ a etlnitial):
Work Group 4 Pest:_
PCB:
Solvent Exc anged To Hexane ( ate/Initial) 1 yes:
CIcanups:
r.
C
Clea::-we: #
Pest Vial:
C Vial:
alma ".? 'S
Archived Extract Storage:
Co e ts/ se-vato s:
!, s \

Vial Storage:
Vial Storage:
S-Evan Temp:
R.aS`,IG\Adclitionnl Prep Info Sheets\Additional Prey ii?1"ormataoa7PestP0I3\?%aier.doc
Additional PLO lot(- mation For 8141 Water
Service Request 9
Solvent/Reagents used:
Ctrl Got #
Continuous Start (Tiinet aellnitial):
Continuous Stop (Tii-ne/Dateflnitial):
Work Group # :
T Lot #
20ml- of hhos ate buffer solution added to each sample:
50ml. of saturated muffled NaCl W rtion added to each sainple:
r t rte.
Extra,-' , . ,
.. . ..
iij C e«x,-u p 42
Vial:
Archived Extract Storage:
Comments/Observations:
S-F I ° Temp:_
all s ? s, - a m- es
Vial Storage:
R:ASVOGAdditional Prep Info Shoet,;A ddi'tionail Prep InformitionOPWater.doe
STANDARD OPERATING PROCEDURE EXTRACTION
Organophoshorus Pesticides in Water
Methods 8141(3520
8. r _ t :`: (if
y® _ -Ah
9. Solvent exchange the extracts into MTBE on the s-evap at 75°C. When extracts are at about 10 mL, squirt about 10 mL
of MTBE down top of Snyder column, keeping collector in the hot wafer of the bath. If the extracts are allowed to cool,
it will be necessary to add another boiling chip to the extract. Let the extracts solvent exchange on the S-Evap (75°C)
into MTBE until extract is less than 10 mL, do not let the extracts go dry. *Special Note: IVITBE evaporates
a a temperature close to DCM, s watch it closely.
10. Evaporate to <1 mL on the N-Evap, keening temperature <39°C.
11. Take to 1mL final volume in MTE--
12. Note: Some Organophos E; are ligr sensitive. Cover all glassware if
extract is to stored overnight.
R.'SVG\Additicjlal Prep filfo Slreet.;AA(1diti017al Pren I3ri'orxnatiot3C)Pwxter.cfoc
1
s
Information For F C
L ....
Service Request 4
V o ve is . E ` is
C t,ot. 4 Hexane Lot 9.
Cc ;'tart (i e/ ate/Initial):
Continuous Stop (Tinge/ ate/Initial):
Solve Rnged To Hexane ( :e/ } yes:
Cleanups:
,. 11 -les)

Vial Storage:
S-Eva Temp:
Work Grow # •
1) Infoi
Service Request 9
. ole ;C is use :
C Lot #
Hexane Lot 9
Work Group # :
Continuous Start {Ti of ate/In itial):
Continuous Stop {Tinae/Datefinitial):
Solvent Exchanged To exane (Date/Initial) L--] yes:

-h: :n ... s.
Vial Storage:
S- { va Temp:
Appendix H
VOC - Method 624
SOP No-: VOC'-624
Revision: 9
Date: 8/28/08
Pa=ge: 1 of 22
Approved by

Supervisor,

COLUMBIA ANAL y ? NC.
17 S rruti1 113 tp Avenu
Vashin ion 98626
-' L Services, 11-1e. M08

1s: Date:
SOP No.: VOC-624
Revision: 9
Date: 8!28/08
Page: 2 of 22

1

SCOPEANDMs N
This procedure is used to deteii m ation of volatile organic compounds In water matrices
sing U ,A e`,:7d 62 >o t ca ' C. t -,rmine by `°iv n tl > hn
71- - V. J
V SUM '_01Y
I l This procedure give's E chMom, l ? rc-. ;tnc ( - 1 S) condltio, or the
detection of parts per ? - A- - compounds. A sample aliquot is
infected into the gas t t. ap method gar by di3 J. l
injection. i c c capillary column.
compoun which gives both qualitative; ;
well as qt1.
23 The sensitivity i i ethic- of background contamination (i.e,
interferences) rail c i in! l li t` i
Tll : .
Ana NN
lyss m _ - w l tl r ; F 'Flit 12 hour window
begins 014th tthe ---s e method
specific criteria, E !?
initial calibration or c is Jr- i verification i. run, followed by a method blank. If
_ ?_ new both pass their specifi r a, t" _ a. - nin un it flu: ne limit ends. A new window must
then b opened and the sc fence repeat '.
SCUP No.: VOC-624
evisiora: 9
t ?. 3 of 22

Internal St-, - - N !s - In - ? ;r rt,r -;.milar to the a alytes of
interest but A ,,..-e r I i ids are used to help
calibrate the ir-_-- _rrr.enfs -Al ' _: _?rrtt __ s for v wr:w. pure efficiency from
sample to sd .ple.
I etc Claf -if tion of the ratio of instrument response to
analyte ; aunt, a cr")rati( is I?Iyzlr for an(--'- standards in an appropriate
solvent, lC4 solutions arc _: om solutiori ?:h", is ca _rrt from the stack used to
prepare calibration stanclards.
-
si , 3 es is cr:,( z us t j _ se i:rec,- - s _rtrnon of -ire Ljk re°ould be
at five to ten tunes the MR L ? or at level
? y y a a?roir ti : s p±an.
C urve - f_ l r i ;alibration cur 11 oncentrations of a known
ar w d
t € the 2I c v .''.
Surrogate - r f interest in Chem' cal
composition, emn . din environ 1e
samples. The pur o sis of samples. These
compounds are 4. a s? -)r to analysis. Percent
recove,4es are c
.1 )loride c cause
pro(, of -ild be free of these
solvulds.
4.2 t i{
pur
fie[ uury
plume _ -ales, corx"ar. Jc-n in.
trap ti ses.
SAFETY
SOP ,No.: C;-624
Revision.- 9
D-',: 8/28%J8
of 22
5.1 All approt Q ?,-Wns re, --rnples must be taken
when 1 ,edge. ;:_:.v ;f` wr;sc rotective equipment
such as, safe'." 1 ,s Al coat are t e c rr I
52 Chemicals, 'wilards triast law ;r :d its the CAS safety policies,
approve. d y Ore t_;AS pn?,?ironmental Health
and S tid the a prior to I ._..l_ is ethod.
6 SAMPLE C'O RAGE
6.1 d ' irled precle red s` tple

62 Collect altnpl; ur her of sample
bottles prior to tl tti„s tc? werflowing, taking care
not he Scal the bottles with
PFFE li 5 l t to l entriineC. 'r bubbles.
63 Preservatior11
63.1 :--t sto-p biological
is. is for the full 624
{tstirtg the PH of the
J m1s, is required to
on ice and ship to the
6.4 All 1 i o, collection. State
and/or 11,11ple, North
Carolll.AA,
S , ... .:j.: 'H'OC-624

D, of'22
7 __,,AATUS_
7.1 Gas Chronialover aphv"M c ` .
7.3 .1 Each 1 _Jr ,t r suOamblent cooling of
thw Iless steel (or glass) jet
sel) tllti C 1 ---effaced with the MSD.
fD _s, 1, 135, ;1 . 011fined with an 5890
7.1.2 _- to ` ?? j..• i. a a - ?litl ;ejector and

7.2 'urge-any > . ;.. n? 1
Each ( -' ? e sample onto the GC
column. 00 purge and -ap has an

,..
aro ? ?tc

a
d n1in
led for
XJ )erioo Lmpler is used for automated
011.
_
ope
-y
7.J y
'?
C 1.olun-, s
7.x.1
1 :0.25 n and fused.
3. ? 6 ! - ? E. mm and fused
7.3.= ??.?_trnm i fused silica
7.3.E

1s.,
all

3q ntl `br rd d 32nrn ad fused silica
TANLP ?..
.1 olven=
8.2 Reaj'.... l m 2 hours prior to
use
- I` O_, OC -624
14".-, ision:9
F 8128108
I ._ 6 of 22
83 Stock Star-l-rd Solutions
Co . X000 r it l , 1,sed routinely for all
the meths checked against an
independent ?l .. All such stock
standard inixture- : ictu er i ust be replaced after
one year, or sooner it° h t° t; < andard indicates a problem.
.4 Yv o 1 - cliGards Cr oiutic prepare at concentrations
f tt2 :Lrd_ t
_.ior standards, etc.).
Tye

lowest
C_ r I lin t. w rs ruining
leN WI working fine ra e stern.
5.2 TI,
a levels t I,
1 ) n 5 nil sample size. Poor
d `" l° ; , 5 c0 100, 00, ?OQm and
_. i t 4tf
0
8.5.3 by "T" 20 ? 1 of a
re, . -g in a 20ppb
tern
8.6 Interna`
There r idards are
tluorob a ids are
dibro floc c nethane is
evaluat eve a calibration
standard € - 2,. a 5 nil
sarn
Dote: o TLtbl, -M tc t ir?id? 1d?,et ,
8.7 Starch R
9 PRE.
9.1 All tr f'r each instrument.
VOC-624
F u. i of 2?
92 Carrier H be in place for all sources of carrier gas.
These and hydr F car bons, Purifiers should be
changed a r
9.3 Purge anc
93. l it, puq: , r. l daily as needed,
9.3.2 .eplace the tra 2 f performance de er' ;
9.4 Gas ; p
_ _, sing _e
c ?{
pr fl c 1.
9.4.2 O _ 0 i. ance, as contaminated
this to occur will depend on
COr t [nn neriorniance is
uit it improv( neat, the column
ident in ;unction with
c.
9.5 Mass Spcl,
9, 5.1 T'tflie t: eed l t 6 ccz performance (see
t 1.
section
9.5." 1 lent
as
9.5.3 Y' performance
A_ staff.
ES 1
10.1 It is the _ ... * is SC1? and to
con .' _ion of the
results red the ability to
generat or Lion is i ccordance with
the trai_? A sic n onT ;3a is nerf?srmed
by t'','; i' -
S'.-)I` No.. V C-624
`tn. 1
(28i4
_ of 22
10.2 It is the IJ1. levar:. Went super € vr to docunient analyst training,
IDocum s d c I? for Documentation of Training,
is also tl lent sup'' -,anage?.
PROC EDURE
11.1 Sample 1rep4E ; °,°
11.1.1 1 g, ian dilation with reagent
ran -e. thus, the analyst
r IL: Jt is purged.
ld to

tee'
M' ;; ,
11.2 CxC`lMS
lea or bration, and analysis.
Recc--,
11.3 Genera'
11.3. 1 v s 4 typically as
c-'- : ,r V th the lowest

1132 A
11,33
a <;
11. _R . d a mcentration range. She
TT . _i _. ( i amounts).
11.3.3 ?dtieIC p)must be
wit _ jisaent.
1 I . .ti ot N. changed. If an
-AL Can continue
on to reject an IC AL
ri l]R C an WAL is rejected it
.: VOC-624
m 9
31231€3
of 22
11. qr standard prior to
?h time the calibration
,o=id source standard
the most concentrated
11.3.3
t 3. 1 1 in ')er or calibration levels
to be
v.n-€I
so
--ru
pted
-+A rd have a
u. the other
r :ther than an
11, 3.9 . ,, :; fthe si , tdard has been
hours). If
t i-:- )re than once,
c-;r alitted.
11.3.10 ig - .,mz c -.ch analyte, a
be verified
L-andard for
t
.;;cussed in the
prt cd
V 9C.-624
08
t F.22
F,01 ,-str aced to allow for
accu -( " v dual analyses should
demos le nalytical column and at
lea Lion cok In. If '.equate resolution
ca, 1 c d Ain separate
may be reported
L on both primary
11.3.12, ?5:-"WO, ICAL, for the
,Ls IA, not o€ !pitted.

L_ W criteria
.one criteria, analyses
n t res
11.42 (',1',,,"R%,1/
1. ,:,.',ion must be n.
log vest level, analyze
the cl• Lracteristic
-z_ds and
_d i surrogate
. o- the
added.
sun-rogate from the
r _ :nt relative standard
No : ?'??iC-624
P
n: 9
l of 22
`III )' t .
cori ecUve action should be
t _i ,. u_rl.te or surrogate is less
V, 1 the (RP' for each
y t' ° results can
h t
A. :ig a linear
rr i,. nA)0,

an
:urce
_.v "oit.'on
seco ,d source
s W solution (prepared
on standards) may
b
Ic" SI t,`w for
11.4.4 and the
- - ?r, be analyzed.
ti
v,,)en n set of
,
11.4.5 Cc
i? -
`3 and
c 'ipound
compound is
l'n Table 5
E concentration
1' -1_ )rte if the
the accq tame rangy:
";_. srrective action is
--pr spar ation,
still rails to
the
11.5 Sample an`y-,is

12 Q
p. OC-62
-/28/08
12 of 22
X p An action taken and
return to method
%?i, or a new initial
fE r to
0
111 Analysis,. ?... ?o C"_i
i2. t. Y A"
shin the prescin
-bed
any: v eetina the ' ne and
C -,-)c E IS pair
_ system's
ndows must have at
12.1.2 'i'i, ceptale BFB
s12.2 ?ttlethod T
- mples begins.
Refer i t :nd limits of
Detecti i it perform
the fi-Alc >piki
solutiot ' _. ;. The he M DL
studies
Calculat
standard
deviatlr i-"'ing the
correct E Y
12.3 Ongoing -.,,,urance Manual and
i the SOP e,)r
VOC-624
11: 9
/28/08
'. ; _' of 22
123. samples to
_)d blank
sh taken.
C( - Cr e
12.3.2 Aiab ,?r _ ''0 or fewer
sanikl _ ' y adding 20 L
of the C AL w
ter,
M N? a
are percent
1_ ?h=# ? compounds,
a`.,ci.. : 7 9 _. u ® unto E? asi i3
or
12.3.3 - 1 A with
t i amount
O w I,h

--her than matrb,
I Lv Include
S-I? ul o.: VOC -624
xf . q
14 of 22
12,14 (,' nrio to ana'Iysis.
Cs / ??( ha 1 'l 0

lA € ! . r -easons other than
M, 4.?tion ; a include
rep ?
1
2.L rr -
1' 5 Additional A11 _
DAT 10-'re
The day; caw ° , a
sample Is, ? fter
they fivhed for all calibrated
analyte, . e primary characteristic
quantity results calculated.
If there - a% and the ass
spectra r -Li d is "°not found".
112 C'alc g
1.3.2.:1 - 1 -.; the
culated as

ndard;
= d 'ded; and
s point calibration
o.: OC-624
/28/08
E 5 of 22
13.3 Data e>,
Followin by a secondary
analyst. - fer to the SOP
13.4 Reporting
1341 Refer reports are
i e. Enviroe r? - ' data

and ,1 r t' n iJ tl
14 2,
T _
CONTE. a AT
1
Corrective i US S?ci f i 'Ic applicable
section of apt ! i.- : if( unity and
Corrective Act Procedures
for applying d : sect-specific
re-ire en`s.
15 1 y' -I-
This method we ne r n. R c?f'pr to
the reference .c
The metha' E the SOP for
The Detern L_ its are
e= t< ')li hed -ane
?A
16 PC _L' r.
It is the labora 'xQ1e.d to perform
thiq method 4 - .. E`144Yr fW1 3.4?+&dt.3.
Standards are e the volume
of expired sta :ts and/or
reagents used i
fi WASTE MA?
18.1 C C' '* r , r , ,1 ( r
T7.7.

1ZS.J 1 _ :. 9 1. !A
503{
WY
T
1
of 22
4

„."r. - -I
s.
vt2A
/08
_ ? t 22
21

Neat Chemicals

Opened ampules ( i
concentration, >500k,
concentration 1000 .. _ :
concentration c 1000 1
CO---:ell ration < 200 ppm
tal Stanch /
I year from
oplis.-'s
jr I
i date.
vtion date.
1 11 oil clefs.
_ ;"at on elate.
IirE`ion date.
Note: flyst pe e F Autlon
reactivit„ ti cc -pending on use
and storage, t
SOP N(ti.. OC-624
tevi3', E,
Date: _ y, t? 3
lea<.ze: ,1'22
m? J
Purge&Trap: ra
: r . - 2,40"" b, " ? 10
10
Gas Chro--iL-rograph: 0. t r _ c el
Injection AIL Temperature:
Oven _ rC r ln. nol 5.2 n,
Detector Temperature.
MS Scanning:
Carrier Gas: e m a, 2a , 1 rz i tt ;v.' pr essul"e
SOP VOC-624
'R e " ' er
:Page: 20 o 22
l
c.: IOC-624
F22
. u 1 ACr ;u
o POUH
Chlorc,i
.
Vinvl C'..,.
rornc
Chloroet'-
(- -)ro_
1,1,1-Triclei c i
Carbon Tetrak,hlc,
Benzene
1,2-Dichloroc th nc
Trichloroethene (TC 7)
1,2--Dicnloropri
Brornodichlo~ -
2-ChloroeChx,,l Vir
r? ' r } fi t
Trans-1,3)
Toluene
CIS-l t?-?.'
Tetra.:,'' lei
Dibren
Chlorot
Etl-lb
Bro--.-
1,1,2..2- ! -
1,3, -ichlord
1,4-l icliic
1,2-Dicl;.lc `
A -- CC`i'
2 . 7..,
7. -
9.(..:1
1
1 ' - 2,
i
_iM1 ?Z -7
F 26.t)
4 8
r ?,

VOC:-624
9
108
_-2 0-F-22

C ` -
LIDS j 1 " `trix
Ira Acenrar 'lo Precision
Method (% Rec.) cc.) (RPD)
624 to--_.r (T(." 69-137 76-126 30
624 N ... W 61-140 34-166 30
624 M: t:A 1 r, 1,12-Ilichlora an?e- 75-117 74-117 30
624 Method Water- 1,1-Dichloroethan,e -?- - 17-126 75-125 30
624 Method 'G er 1,1-Dichlor h ze ---- 85-132 82-133 30
624 Method V r- 1,2 " - 81-109 80-108 30
624 Method. V. r. _.r 1,2_D?.,1 1 70-133 70-130 30
624 Method \k r 1 -, -? 79.120 79-119 30
624 Method V r (,)-111 78-111 30
-- = --- ----- --
624 N rc ' V 1 '-L I 80-108 79-109 30
624 655127 67-130 30
624 53-137 10-161 30
624 ,v 56-123 39-167 30
624 N/ 4- 04-'21 1-124 30
6s _ 30
r 30
30
30
E -_ - 30
......
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