## Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbons Sampling Program 2007 Addendum

Prepared for:



## U.S. Environmental Protection Agency Engineering and Analysis Division Office of Water 1200 Pennsylvania Avenue, NW Washington, DC 20460

Prepared by:



## Eastern Research Group, Inc. 14555 Avion Parkway Suite 200 Chantilly, VA 20151-1102

July 9, 2007

EPA Contract No . 68-C2-095 Work Assignment 4-18ADDENDUM July 2007 Page 1 of 7

This addendum describes changes to the Final Quality Assurance Project Plan for the Chlorine and Chlorinated Hydrocarbon Sampling Program (Sampling QAPP) dated May 4, 2006 for the 2006 CCH sampling program as well as changes that will be implemented for the 2007 CCH sampling program. ERG followed most of the May 2006 plan for the 2006 CCH sampling program. However, based on the results of the initial 2006 data collection activities (not including the results for Episode 6540), ERG is amending Section 3.5 (Q uality Control) as

described in this addendum. All other secti ons of the Sampling QAPP remained unchanged.

Changes Made for the 2006 CCH Sampling

Bottle field blanks were collected in the staging area on Day 2 of the sampling episodes instead of prior to any sample collectio n, as specified in the May 4, 2006 version of the CCH QAPP. This change was ma de to collect data on potential contamination in the staging area during the sampling event, rather than before it began.

Changes Planned for the 2007 CCH Sampling

Element B.4: Analytical Methods

Table 1 at the end of this document lists the analytical methods to be used to characterize CCH waste stream samples. The table lists the methods specified for the 2006 sampling, the method used at the laboratory, the method update rule (MUR) method, and the method that will be used for the 2007 sampling.

Element B.5: Quality Control

The CCH sampling program will include th e collection of field quality control samples. The site-specific sampling plans will specify the quantities a nd types of blanks andADDENDUM July 2007 Page 2 of 7

duplicate samples to be collected during each episode. EPA is amending the methodology used for the following quality control samples:

 Trip blanks;

 Equipment field blanks;

 Bottle field blanks; and,

 Source water.

This addendum does not change the procedures used for the bottle blank or duplicates. ERG’s bottle blank (only one required fo r the entire CCH sampling progr am) was analyzed for dioxins and furans and PCBs during the 2006 sampling progr am and no pollutants were detected. This indicates that contamination from sampli ng equipment (bottles) is not likely.

Trip Blanks

ERG prepares one trip blank for eac h sampling episode. The laboratories typically analyze these samples only for volatil e organic compounds. However, EPA elected to

have the laboratories also test for dioxins and PCBs for the 2006 CCH sampling program since these compounds are of particular interest to the CCH program. Based on the initial sampling

results which did not detect vol atile organics, dioxins and fura ns, or PCBs, EPA believes that sample transport, handling, and st orage are not likely to cause sa mple contamination. For the 2007 CCH sampling program, trip blanks will be analyzed for volatile organic compounds only.

Purpose: To monitor volatile or ganic contamination of samples during transport, field handling, and storage.

Recommended One trip blank per ep isode for volatile organic compounds. Frequency:ADDENDUM July 2007 Page 3 of 7

The sampling crew will prepare a trip blank in ERG’s sample room before the start of the sampling episode by pouring an analyte-free matr ix (typically HPLC water) into the sample bottles. ERG will preserve the samples and transpor t them unopened to the facility. Trip blanks are stored at the sampling staging area thr oughout the sampling episode. The sampling crew will place the samples on ice during the last day of sampling and ship the samples unopened to the laboratory.

Equipment Field Blanks

As specified in the May 2006 Sampling QAPP, the sampling crew will collect equipment field blanks for all sampling techniques used by the sampling staff and for any special equipment used during the sample collection, such as cooling coils, ISCO composite samplers, tubing, funnels, etc. The equipment field blank ev aluates any contamination of the sample from either the equipment used or ambient conditi ons at the site. During the 2006 CCH sampling program, ERG used cooling coils, composite containe rs, and funnels to colle ct the samples. The cooling coils are typically used only for the collection of vol atile organic samples. The composite containers and funnels are used fo r the collection of Group I, Group II, BOD, and

metals. The collection of dioxin/furan and PCBs typically use no equipment other than bottles because the lab composites the sample results. ERG plans to use the same sampling methods for the 2007 CCH sampling program. To collect field blanks, ERG pours HPLC water directly into sample bottles or composite containers at th e sample point location. ERG uses the same technique for compositing, packing, and shipping the equipment field blank as for all other samples.

Generally, field blanks are analyzed on ly for trace metals. The CCH sampling program is not collecting trace metals samples but opted to collected field blanks for volatile and semivolatile organic compounds, dioxins and fura ns, and PCBs since we determined these

parameters were most critical to the study.ADDENDUM July 2007 Page 4 of 7

Based on the initial 2006 CCH sampli ng program results, EPA has reason to believe that sampling equipment and techniques and the sample point ambient conditions will not contaminate the samples with nonvolatile compounds. Indeed, results for the equipment field blanks in the 2006 CCH samp ling program did not show any de tects for dioxins and furans, volatile organics, or semivolatile organics. On ly, one PCB congener was detected in one field equipment blank at a concentrati on less than one tenth of the mi nimum level. Thus, for the 2007 CCH sampling program, EPA will only analyze equipm ent field blanks for volatile organics to verify that organic vapors pres ent at the sampling site do no t contaminate the sample.

Purpose: To monitor any contamination from sampling techniques (equipment used or am bient conditions).

Recommended: ERG will support EPA in determining the number of Frequency: equipment field blanks needed at each site. At least one blank will be collected for each type of sampling technique or special equipment used. Equipment field blanks will be collected for volatile organic compounds.

Bottle Field Blanks

During the 2006 CCH Sampling, ERG colle cted bottle field blanks at the sampling staging area at each site to determine if sampling activities conducted at the sampling staging area contribute volatile and semivolatile organic compounds, total metals, dioxins and furans, and PCBs to the sample.

The CCH sampling program is not colle cting trace metals samples and is collecting bottle field blanks for volatile a nd semivolatile organic compounds, total metals, dioxins and furans, and PCBs since we determined these parameters were most critical to the study.ADDENDUM July 2007 Page 5 of 7

Based on the initial 2006 CCH sampli ng program results, EPA has reason to believe that the staging area ambient conditions will not contaminate the samples and thus do not need to be measured for quality control. Indeed , initial results for the bottle field blanks in the 2006 CCH sampling program did not show any dete cts for dioxins and furans, or semivolatile organics. Only sodium (metal) and acetone (a common lab contaminant) were detected. Both compounds were detected at con centrations less than ten times the minimum level. Thus, for the 2007 CCH sampling program, ERG will not collect bot tle field blanks. Instead, ERG will collect only equipment field blanks to evaluate contam ination from ambient conditions at the sample points.

Source Water

The ERG sampling crew will collect a grab sample of the source water used in CCH operations prior to its use to monitor for co ntaminants in the source water. During the 2006 CCH sampling program, source water samples were monitored for all analytes except

HEM/SGT-HEM. Since most CCH sites use trea ted river water as their process water, EPA expects some contaminants to be present in source water. However, sites would need to remove any contaminants prior to treatment regardless of the source of contamination. Some facility personnel have stated that the source water may be contributing to their ov erall dioxin loads. Thus, for the 2007 CCH sampling program, the sour ce water will be analyzed for dioxins and furans only to evaluate source water as a potential source of dioxins.ADDENDUMJuly 2007Page 6 of 7Table 1. Analytical Methods Used in the CCH Sampling ProgramAnalyteMethod Specified inCCH SamplingPlans for Episodes6531, 6532, and6540Method Used atLaboratory for6531 and 6532Method UpdateRule MethodaMethod Specifiedfor 2007 CCHSamplingAdditional NotesTotal Suspended Solids(TSS)160.2 160.2 160.2Total Dissolved Solids(TDS)160.1 160.1 160.1Sulfate 300.1, Rev 2.1 300.0, Rev 2.1 300.0, Rev 2.1 300.0 Rev 2.1Chloride 300.1, Rev 2.1 300.0, Rev 2.1 300.0, Rev 2.1 300.0, Rev 2.1Alkalinity SM2320B SM2320B SM2320B SM2320BTotal Kjeldahl Nitrogen(TKN)SM4500-Norg B orC351.2 SM4500-Norg B orC351.1, 351.2,SM4500-Norg B orCAmmonia SM4500-NH3 B,F SM 4500-NH3 B,G SM4500-NH3 B,F SM4500-NH3 B,F EPA’s SCC did not allow the use of SM 4500-NH3B, G on the delivery order.Nitrate/Nitrite 300.1, Rev 2.1 353.2 300.0, Rev 2.1 300.0, Rev 2.1 EPA’s SCC informed ERG that AnalyticalLaboratory Services, Inc. recommended reinstitutingthe old analytical methodfor nitrate (353.2) tohandle chloride interferences better. The currentmethod listed on the sampling plan is EPA 300.00Rev 2.1. EPA approved the use of 353.2.Phosphorus 365.2 or 365.4 365.1 365.3 or SM4500PB(5) E365.1, 365.3, 365.4or SM4500P B(5) EBiochemical OxygenDemand (BOD)SM5210B SM5210B SM5210B SM5210BChemical OxygenDemand (COD)410.4, Rev 2 HACH 8000 410.4, Rev 2 410.4, Rev 2 orHACH 8000ADDENDUMJuly 2007Page 7 of 7Table 1. (Continued)AnalyteMethod Specified inCCH SamplingPlans for Episodes6531, 6532, and6540Method Used atLaboratory for6531 and 6532Method UpdateRule MethodaMethod Specifiedfor 2007 CCHSamplingAdditional NotesTotal Organic Carbon(TOC)SM5310C SM5310B SM5310C SM5310B orSM5310CHexane ExtractableMaterial (HEM) andSilica Gel TreatedHexane ExtractableMaterial (SGT-HEM)1664A 1664A 1664AMetals 200.7, 200.8, 200.9 200.7, 200.8, 200.9 200.7, 200.8, 200.9 200.7, 200.8, 200.9 CCH sampling also uses 245.1 for mercury.Volatile OrganicCompounds (VOC)1624C 1624C 1624C 1624CSemivolatile OrganicCompounds1625C 1625C 1625C 1625CChlorinated BiphenylsCongeners (PCBs)1668A 1668A 1668A 1668A CCH is not pH preserving PCBs per direction fromEPA and EPA’s SCC.Tetra- Through OctaChlorinated Dioxins andFurans (D/F)1613B 1613B 1613B 1613BaBased on information provided by CSC.