draft status report for temporal water column …

612.141

DRAFTSTATUS REPORT

TEMPORAL WATER COLUMN MONITORING PROGRAM

HUDSON RIVER PROJECT

GENERAL ELECTRIC COMPANY

CORPORATE ENVIRONMENTAL PROGRAMS

FAIRFIELD, CONNECTICUT

October 2,1991

O'BRBEN & GERE ENGINEERS, INC.5000 BRITTONFIELD PARKWAYSYRACUSE, NEW YORK 13221

312391

GENERAL ELECTRIC COMPANYHUDSON RIVER PROJECT


SECTION 1 - INTRODUCTION

1.01 OBJECTIVESThe principal objective of the Temporal Water Column Monitoring Program is to provide highfrequency and high resolution PCB monitoring data for the Upper Hudson River.

1.02 SCOPE OF WORKThe Temporal Water Column Monitoring Program includes the collection and analysis of waterborn PCB according to methods employed by the U.S. Geological Survey (USGS) during the 1970sand 1980s to provide consistency with the historical water column data base. Four of the eightmonitoring stations employed during this study are used by the USGS to monitor water columnPCB. Water column samples are being analyzed for PCB according to procedures historicallyemployed by the USGS as well as congener specific methods. Conventional parameters are alsobeing monitored as part of this program.

SECTION 2 - SAMPLING LOCATIONS AND PROCEDURES

2.01 SAMPLING LOCATIONSWater samples are being obtained from eight stations on the river. Four of these stations arelocated on the bridges utilized as the historical USGS sampling stations in Fort Edward,Schuylerville, Stillwater, and Waterford. Additional stations include the abandoned bridge adjacentto Bakers Falls near Hudson Falls, New York, the western end of the Thompson Island Dam, andthe Hoosic River and Batter Kill. Approximate station locations are illustrated on Figure 1.

Samples are collected from near the center of the channel off bridges, with the exception of theThompson Island Dam, Hoosic River, and Batten Kill stations which are collected from shore

O'Brien & Gere Engineers, Inc. 1 October 2,1991

312392

Temporal Water Column Monitoring Program

locations (the center of the channel at these stations are not accessible by land). Samples at theThompson Island Dam station are collected from the west wing wall of the dam. Hoosic River andBatten Kill stations are located approximately 0.5 miles upstream of their confluence with theHudson River.

2.02 SAMPLE COLLECTION FREQUENCYThe following sampling schedule is being followed for the program:

April 1 to June 30, 1991

July 1, 1991 toFebruary 28, 1992

3 times per week

1 time per week

2.03 SAMPLE COLLECTION PROCEDURESSamples collected from the bridges are vertically stratified composites made up of discrete aliquotscollected at 3-foot intervals throughout the water column. Samples are collected with a stainlesssteel Kemmerer bottle at each station. The Kemmerer bottle sampler is a 1.2 liter cylinderequipped with closeable stoppers at each end. The sampler is lowered to the desired depth in thewater column in the open position. A messenger is sent down the suspending cable to close thesampler and a discrete aliquot is collected. Upon retrieval, the sampler is discharged into a stainlesssteel compositing container. Subsequent aliquots are placed in the container to form the verticallystratified composite.

Upon collection, the composite sample are poured from the stainless steel compositing containerinto appropriate containers, chilled to 4°C, and transported to the laboratory for analysis. Eachsample is assigned a unique sample designation, identifying sample location, date, and time.Standard chain of custody procedures are being followed. The kemmerer bottle sampler is beingthoroughly decontaminated between stations. Decontamination procedures are specified in theQuality Assurance/Quality Control section of this report.

At shore stations, water samples are being collected in dedicated, precleaned 1 gallon glass


312393


containers which are submerged to the desired depth, allowed to fill, and retrieved.

2.04 ANALYTICAL TESTINGWater samples collected as part of the Temporal Water Column Monitoring Program are beinganalyzed for the following parameters:

•total dissolved solids,•conductivity,•alkalinity,•total suspended solids,•total organic carbon, and•total PCB by USGS and "Green Bay" congener specific methods.

Analytical methods and protocols are briefly defined in the Quality Assurance/Quality Controlsection of this report. PCB analyses are being performed by Northeast Analytical, Inc. Otheranalyses are being performed by OBG Laboratories, Inc.

SECTION 3 - QUALITY ASSURANCE/QUALITY CONTROL

Essential components of the Quality Assurance/Quality Control (QA/QC) procedures beingemployed during the Temporal Water Column Monitoring Program are summarized below.

3.01 FIELD DOCUMENTATIONWater column sampling procedures are being verified in a daily log maintained by samplingpersonnel. Daily entries into the logbook include: date, weather conditions, time of samplecollection, depths of aliquot collection, and other pertinent observations such as barge traffic,surface debris, and physical appearance of the water column.

3.02 FIELD QA/QC SAMPLES^

In order to evaluate data quality, field QA/QC samples are being collected. The types andminimum frequencies of QA/QC samples are as follows: field duplicates (5%), laboratory duplicates(5%), matrix spikes (5%), field blanks (5%), method blanks (10%), external QC check samples(5%), and spiked blanks (5%).


312394


3.03 DECONTAMINATION PROCEDURESSampling equipment, including the Kemmerer bottle sampler and the stainless steel compositingcontainer, are decontaminated after the collection of each composite sample. To complete thedecontamination procedure, the sampling equipment is rinsed with acetone, then hexane, thenallowed to completely air dry, and finally rinsed with distilled water.

3.04 SAMPLE CUSTODY

Sample custody is being maintained through strict adherence to chain of custody procedures, asdefined by the U.S. EPA guidance document: A Compendium of Superfund Reld OperationsMethods (U.S. EPA 600/2-80-018). These procedures include the maintenance of a field logbookin conjunction with a chain of custody form. The chain of custody form accompanies the samplesfrom the field to the laboratory and include a sample description, date and time of collection,sample matrix and type, number and size of sample containers filled, and the type of analysisrequested. Sample custody is being maintained by the receiving laboratory throughout the analyticalprocedure.

3.05 ANALYTICAL METHODSThe analytical methods being performed during this program comply with the requirements of thefollowing methodologies.

•Congener specific PCB analytical methodologies adhere to procedures outlined inNortheast Analytical, Inc. Method NEA-608CAP , Rev. 2.0, 8/89 (Attachment 1). Themethod includes guidelines set forth in the document: Quality Assurance Plan. Green BayMass Balance Study. I.PCBs and Dieldrin. U.S. EPA Great Lakes National Program Office.prepared by Deborah L. Swackhamer, Quality Assurance Coordinator, Field and AnalyticalMethods Committees, University of Minnesota, December 11, 1987. •"

•Packed column total PCB data is being generated according to USGS methodologies. TheUSGS method consists of procedures consistent with EPA Method 608 with total PCBcalculated by dividing the total area of the samples identified PCB peaks by the area of allpeaks for an Aroclor standard. A standard consisting of two Aroclors is used for quantifyingPCB in samples which appear to contain less than 60 percent of a single Aroclor.

•Other laboratory analyses, analytical QA/QC and data reporting requirements adhere toguidelines outlined in: Methods for Chemical Analysis of Water ana Wastes. U.S. EPA -


312395


600/4-79-020, Revised 1983. New York State Department of Environmental Conservation.Analytical Services Protocol. NYSDEC, September 1989.

Specific methodologies are summarized in Table 1.

3.06 DATA REPORTINGAnalytical data packages are being provided for each analysis. Data report forms are securelybound and all pages are being sequentially numbered. The analytical data reports include thefollowing information:

•case narrative,•date of sampling,•case file,•description of samples,•description of sample extraction and clean-up procedures,•indication of analytical method,•analytical results of all samples plus trip blank, field blank, and method blank,(including tentatively identified compounds, if applicable),•analytical results of QA/QC sample analyses,•summarized calibration data,•detection limits for parameters analyzed,•QA/QC data summaries (i.e. MS results and summaries),•copy of completed chain-of-custody forms,•notebook accountability record,•appropriate raw instrument outputs (e.g. GC/MS spectral printouts), and•example calculations for each analysis.


312396


SECTION 4 - WATER COLUMN MONITORING RESULTS

4.01 GENERALPreliminary water column monitoring data which has been received from the laboratories andincorporated into the data management system are presented in attached tables (Tables 2, 3, and4). In some instances, data for PCB have been received without the corresponding conventionaldata. Where this has occurred, the conventional fields of Table 2 contain -a period (.).

The data appearing in the attached tables have not been validated and should be considered aspreliminary only. Laboratory contamination problems appear to have effected PCB results onseveral days. These data have been omitted from this report. The laboratory contamination issuewill be fully explored and documented during data validation.

4.02 ANALYTICAL TESTING RESULTSTotal PCB data generated by the USGS procedure along with conventional parameter testing resultsare contained in Table 2. Table 3 contains a summary of the congener specific testing results. PCBdata appearing in Table 3 are presented as the weight percent of each homolog group and the totalPCB concentration calculated from the sum of the individual congeners. Specific congener dataare being filed in hard copy and electronic format. Table 4 contains the number of observations,range, mean, and standard deviations for PCB data generated by the USGS methodology.


312397

TABLE 1HUDSON RIVER PROJECT


ANALYTICAL METHODS

PARAMETER

Total suspended solids (TSS)Total Dissolved Solids (TDS)

Total Organic CarbonSpecific ConductivityAlkalinityTotal PCBsCongener Specific PCBs

METHOD NUMBER AND REFERENCE

160.2 (1)

160.1 (1)

415.1 (1)

120.1 (1)

310.1 (1)

608 (2)

NEA-608CAP (3)

(1) Methods for Chemical Analysis of Water and Wastes, U.S. EPA-600/4-79-020, Revised1983.

(2) 40 CFR 136, Appendix A, Methods for Organic Chemical Analysis of Municipal andIndustrial Wastewater, Method 608, Organochlorine Pesticides and PCBs.

(3) Standard Operating Procedure - Laboratory Method NEA-608CAP, NortheastAnalytical, Inc., Revision 3, June 1990 (Appendix A).

312398

of 5

Table 2Hudson River Project

Temporal Water Column Monitoring ProgramUSGS Total PCB and Conventional Parameter Results*

October 2, 1991

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04/08/9104/08/9104/08/9104/08/9104/08/9104/08/9104/10/9104/10/9104/10/9104/10/9104/10/9104/10/91

04/1279104/12/9104/12/9104/12/9104/12/9104/12/91

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Temporal Water Column Monitoring ProgramUSGS Total PCB and Conventional Parameter Results'"

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312403

of 2

RAFT Table 3Hudson River Project

Temporal Water Column Monitoring ProgramSummary of Congener Specific PCS Results

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Temporal Water Column Monitoring ProgramSummary of Congener Specific PCB Results

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-

-----

-

-0.00.00.00.0

_

-

0.0---

iiiiiii-

0.00.00.00.00.0

-------

-0.00.00.00.0

_

-0.0

---

AFT Table 4Hudson River Project

Temporal Water Column Monitoring ProgramSummary of Total PCB Results*

October 2,1991

|l||llpiltiii|I||l|

BAKERS FALLSBRIDGE

ROUTE 197 BRIDGE

THOMPSON ISLANDDAM

ROUTE 29BRIDGE

STILLWATERBRIDGE

ROUTE 4 BRIDGE

Ill iillllllliiiliiliiilll28

28

28

28

28

28

lilliillllll

1

3

7

4

3

4

;liijlililfil;li

20

42

51

99

46

50

liiiitiiifii!7

16

24

25

23

18

4.4

10.0

10.9

20.4

13.6

10.6

* Generated by USGS methodologies** Below method detection limit of 11 ppt

312406

u>Htorf*O-4

NEW YORK STATENOT TO SOLE

FIGURE 1

Temporal Water ColumnA Monitoring Program

Sampling Locations

GENERAL ELECTRICHUDSON RIVER PROJECT

HUDSON RIVERRIVER LOCATION MAP

T = S MILES

MAY 1991

OBRIBiaOBtEE N G I N E E R S . INC.

ATTACHMENT 1

STANDARD OPERATING PROCEDURE

LABORATORY METHOD NEA-608CAP

312408

NORTHEAST ANALYTICAL. INC.301 NOTT STREET

SCHENECTADY. NEW YORK 12305(518) 346-4592

STANDARD OPERATING PROCEDURE

LABORATORY METHOD NEA-608CAP

REVISION 3 (6/90)

312409

Northeast Analytical. Inc. -1- NEA-608CAP Rev. 2.0 JJ/89)

Lab Method NEA-608CAP

Congener-Specific Polvchlorinated Biohenvl (PCB) Analysis

Method for Congener-Specific Polychlorinated Biphenyl (PCB)Quantification and Identification by Capillary Column/Gas

Chromatography with Electron Capture Detection

1.0 Scope

1.1 This method is applicable in the determination and quantification ofPolychlorinated Biphenyls (PCB) in sediments and soils. This method is___a_congener-specific_ determioa.ti.ori,_._empjqying .a_ high _resolution...Jus.ed-silica

"capillary chromatographic column. The method includes guidelines set forthin the document: 'Quality Assurance Plan, Green Bay Mass Balance Study, I.PCBs and Dieldrin, US EPA Great Lakes National Program Office', preparedby Deborah L. Swackhamer, Quality Assurance Coordinator, Field and AnalyticalMethods Committees, University of Minnesota, December 11, 1987. Thisdocument outlines quality assurance and quality control, .procedures to be"followed by la15^1jtffigis^Dj*rfffii5¥^^ Bay Mass Balance Study.Where__apjpncablet North^a^'^Anatyticar. Inc., will incorporate and utilize thisinforniatToTTTnl quality_control of data "generated. Instrumental analysis andconditions (Mullin, M.D., 1985, PCB Workshop, US EPA Large Lakes ResearchStation, Grosse He, Ml, June.) cited in the Green Bay Mass Balance Studydocument will be refined to be applicable to an in-house data managementsoftware package.

1.2 This method will be applied specifically to the determination of PCBst by congener, in sediments. The results of these analyses will be used in

studies related to biodegradation of PCBs. Highly sensitive techniques, willgenerally not be required, since samples will contain appreciable quantities

10M

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Northeast Analytical, Inc. -2- NEA-608CAP Rev. 2.0 8/89

of PCBs. Capillary coIlumn_ mejhods will be used to effectively^ jseparate upto TTT or mo re peaks representing 187 PCB " c o n g e n e r s " " " '

2.0 Summary of Method

2.1 This method provides detailed instructions for gas chromatographicconditions, sample extraction, and sample clean-up techniques for analysis ofPCBs by capillary gas chromatography.

2.2 This method utilizes a mixed Ar-clor standard (1232/1248/1262 in theratio of 25:18:18) for calibration. Method detection limit and practicalquantitation limit will be established experimentally using the procedure inUSEPA 40 CFR, Part 136, Appx. B.

2.3 In general, samples are first extracted with a pesticide-grade solvent.The extracts are further processed by concentrating or diluting, depending onthe concentration of PCB, and carried through a series of clean-uptechniques. The sample is then analyzed by direct liquid injection onto thegas chromatographic column and detected by an electron capture detector.This method should be performed by a skilled chemist or by an analysttrained in the quantification of trace organics by gas chromatography.

1 2.4 A key component of this method is the importance placed on thechromatographic separation that must be achieved for this congener specifictechnique. A total of 117 chromatographic peaks are detected, containing187 PCB congeners in various ratios. This allows an almost complete profileof environmentally occurring PCBs.

2.5 Safe laboratory practices should be followed by the analyst at alltimes when conducting work in the lab. The analyst should refer to thereference file of material safety data sheets to familiarize himself with thehazards of handling the compounds used for standards and samplesthemselves.

3.0 Interference

3.1 One of the major sources of interference in the analysis of PCBsis that organochlorine pesticides are coextracted from the samples. A fewof these ECO responding pesticides can be separated cleanly from the PCBprofile by the resolving characteristics of the capillary column. Several of thecommonly found pesticides and degradation products (DOT, DDE, ODD) overlapthe PCB profile envelope and co-eiute with several of the minor PCBcongeners found in environmental samples. The analyst must be careful inchromatographic pattern review and flag peaks that are suspected of beingcontaminated so that they are not included in total PCB values -generated.

< 3.2 There are several clean-up protocols available that can be used tofractionate PCBs from organochlorine pesticides found in environmentalsamples. These techniques and there effectiveness will be described in the

HMDSX*UB 312411


sample preparation and clean-up section of this manual. Other separationand clean-up techniques will be included in the section describing proceduresto handle samples that contain oil and grease, hydrocarbons, and elementalsulfur.

3.3 Laboratory contamination can occur by introduction of plasticizers(phthalate esters) into the samples through the use of flexible tubing.Samples and extracts should not be exposed to plastic materials. Phthalateesters give response on electron capture detectors, usually as late elutingpeaks, and can interfere in PCB quantification.

4.0 Sample Archiving

4.1 Extracts and sediment samples will be retained after analysis. Thesolvent extracts will be stored in a freezer, while the dry sediment samplescan be stored at room temperature, protected from the light.

5.0 Equipment and Apparatus

5.1 Gas Chromatooraph: Complete system for high resolution, capillaryv column capability and all required accessories. Northeast Analytical, Inc. will.-' use a Varian Model 3400 gas chromatograph, equipped with capillary on-

column injection (Septum Programmable Injector), temperature programmableoven, Model 8000 automatic sampler, and fast time constant electron capturedetector. A data system (Dynamic Solutions, Maxima Workstation) forchromatographic operations and integration of detector signal is interfaced tothe gas chromatograph.

5.1.1 Column: The gas chromatograph column to be used for analysiswill be a JDjjM (J&W Company), bonded polydimethylsilicone, 30 meterfused silica capillary column with an internal diameter of 0.25 mm andphase coating thickness of 0.25 microns. This column is capable ofresolving 117 chromatographic peaks from the full spectrum of all PCBcongeners that' could be expected in an environmental sample. Refer toAppendix A and Appendix B for a complete description of PCB congenersidentified in each GC chromatographic peak and achievable analyticalseparations.

5-2 ChromatoaraDh Data System; A data system for measuring peakheight and peak area. A Maxima 820 workstation (Dynamic Solutions). PC-based data system, will be employed to record detector response and digitallystore the chromatographic information on the computer hard disk. Thissystem will allow for chromatographic review of data from the gaschromatograph, electronic peak integration for precise calculations, data basestructuring of the analytical information, and archival capabilities-

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Northeast Analytical. Inc. -4- NEA-608CAP Rev. 2.0 8/89

5.3 Soxhlet Extractor: Complete system for use in extracting PCBs fromsoils, and sediments. The soxhlet extractor consists of a water cooledcondenser, a 250 mL, or 500 mL round bottom flask, soxhlet repetitiveflushing unit, appropriate heating mantle and controller.

5.4 Kuderna-Danish (K-D) apparatus: Complete system to evaporateextraction solvent and concentrate sample extract. The K-D apparatusconsists of a concentrator tube (10 mL), evaporation flask (500 mL), and 3-ball snyder column.

5.5 Boiling Chips: Solvent extracted, silicon carbide or equivalent.

5.6 Volumetric Flasks: 10, 25, 50, and 100 mL, ground-glass stopper.For standards and sample dilutions.

5.7 Microsvrinae: 10, 25, 100, 250, 500 uL for standard preparation.

5.8 Vials: Glass, 10, and 20 mL capacity for sample 'extracts.

5.9 Bottles: Glass, 50 and 100 mL capacity for sample storage.

5.10 Sample Concentrator: An evaporator unit that utilizes a stream ofpurified nitrogen gas to gently evaporate solvent from samples.

6.0 Reagents

6.1 Solvents: Pesticide grade or nano-grade quality. Hexane, acetone,toluene, methylene chloride, methanol, diethyl ether, dimethylformamide, andpentane.

6.2 Magnesium Sulfate: Anhydrous, suitable for pesticide analysis.

6.3 Sodium sulfate: Anhydrous, suitable for pesticide analysis.

6.4 Sulfuric acid: Concentrated, ACS reagent grade.

6.5 Mercury: Triple distilled.

6.6 Magnesium silicate (Ftorisil): 60-100 mesh, activated at 650 degreesC., reagent grade suitable for pesticide analysis.

6.7 Glass Wool: Silane treated, solvent washed to remove impurities.

6.8 Silica Gel: 100-200 mesh, grade 923, Aldrich, deactivated to 7.5%with water.

6.9 Potassium Hydroxide: Pellets, reagent grade.

6.10 Octachloronaphthalene: Obtained from Ultra Scientific (Hope. Rl), witha purity greater than 95%.

312413


6.11 Polvchlorinated biohenvls: Neet commercial material for standardpreparation. These materials are multi-component mixtures of PCS congenersand are the actual materials that were used in products such as transformersand capacitors. Monsanto was the largest producer of PCB formulations andsold them under the tradename Arocior. These standards should be comparedto EPA PCB reference materials to verify commercial materials, to be usedas standards, have the same pattern and congener distribution.

6.12 Stock Standard Solutions:

6.12.1 Stock standards are prepared from individual Arociorformulations by weighing approximately 0.025 g to the nearest 0.1 mg,and dissolving and diluting to volume in a 25 mL volumetric flask. Thiswill give a stock concentration of 1,000 ppm.

6.12.2 The stock standard is transferred into screw-cap vials andstored in a freezer, protected from light. Stock standards should bechecked at frequent intervals for signs of evaporation, especially justprior to preparing calibration standards.

"*- 6.12.3 Stock PCB standards must be replaced after one year, orsooner if comparison with EPA certified check standards indicate a

i problem.

6.12.4 Stock standards for the following are prepared by theabove procedure:

Arocior 1232Arocior 1248Arocior 1262

6.13 Calibration Standard: The calibration standard is prepared bycombining Arocior 1232. Arocior 1248, and Arocior 1262 in a 25:18:18 ratiowith a final mixture concentration of 2.5 ug/mL, 1.8 ug/mL, and 1.8 ug/mLrespectively (total • 6.1 ug/mL). The final concentration of the mixedstandard may vary to accommodate instrument sensitivity or more closelyrepresent sample concentrations, but the same ratio values must bemaintained. These ratios are strictly maintained so that the percentcomposition data remains applicable, since it was developed for use underthese fixed mixture parameters.

6.13.1 Using a 500 uL microsyringe, accurately add 0.25 mL ofstock Arocior 1232 standard (1,000 ppm) to a 100 mL volumetric flask.Add 0.18 mL of stock Arocior 1248 and Arocior 1262 to the same 100mL of stock volumetric flask. Add the internal standard to the 100 mL

•"""-•• volumetric flask as outlined in Section 6.14, and make volume to the100 mL mark with hexane.

••* 6.13.2 Store calibration standard in the refrigerator at 4 degreesC. in a tightly capped bottle. Calibration standards must be replaced

312414


after six months, or sooner, if comparison with ERA check standardsindicate a problem.

6.13.3 Since the instrument calibration is based on a single pointcalibration standard, concentration of PCBs in the sample extracts mustbewithin a factor of five of the calibration standard value. Sample extractsthat fall outside this range should be diluted or concentrated to bewithin the accepted concentration range. To facilitate in meeting theestablished concentration range for samples, sample extracts are to bescreened by packed column gas chromatography with electron capturedetection to determine their approximate concentrations. Sample extractsolution concentrations for this screening procedure will be calculated byusing a mixed Aroclor standard (Aroclor 1242 and 1260) with instrumentcalibration based on the peak weight percent method of Webb andMcCall. This concentration data is necessary so that the extractconcentration can be adjusted to match (within a factor of five) theconcentration of the three Arocior calibration mixture. Besides assessingthe PCS extract concentration, the packed column screen will supplyinformation on possible contamination and interfering co-extractabies whichwould indicate further sample clean-up is necessary.

X—N 6.14 Internal Standard; The internal standard used for capillary gaschromatography of PCBs will be octachloronaphthalene (OCN). Weigh, to the

; nearest 0.1 mg, solvent, quantitatively transfer the OCN using six successive2 mL washings to a 50 ml volumetric flask. Be sure to rinse the 10 mLvial walls carefully so that all OCN is completely transferred to the 50 mLvolumetric flask. Make the solution to volume using toluene and mix theinternal standard solution by shaking the flask several times. This will givea concentration of OCN of 200 ppm. Calculate the exact concentration ofOCN based on the amount weighed. Carefully transfer the internal standardsolution to 10 mL vials, tightly cap, and store in a freezer.

6.14.1 The OCN internal standard is added to all calibrationstandards, performance check standards, blanks, samples, and QCsamples at an amount to give the same concentration as the major PCBsfound in standards and samples. In most cases this will be achievedby spiking 9 uL of OCN internal standard solution to 10 mL of standardor sample extract to give an concentration of 0.1818 ppm.

6.14.2 The internal standard will be added to calibrationstandards, sample extracts, blanks, and QC samples iust prior to gaschromatographic analysis. Thus, the internal standard is used as aquantification spiking standard and will eliminate sample injection andinstrument variations, but will not correct for analytical losses duringsample preparation.

6.15 Performance Check Standard: A performance check-standard isprepared from quality assurance/quality control standards obtained from theUSEPA Environmental Monitoring and Support Laboratory (EMSL), Cincinnati,Ohio. The performance standard is a mixed Aroclor standard of Arocior 1232,1248, and 1262 in the fixed ratio used to prepare the calibration standard

312415


and must be strictly adhered to. The performance standard is made to aconcentration at the lower end of the range that sample PCB extractconcentrations must fall into (a factor of five of the calibration standard).

6.15.1 The performance standard is composed of: 0.50 ug/mL Aroclor1232, 0.36 ug/mL Aroclor 1248, and 0.36 ug/mL Aroclor 1262, a total of1.22 ug/mL PCB. This mixture is prepared from a concentration of 5,000ug/mL in isooctane. The USEPA standards are diluted to 50 ug/mL bypipetting 0.5 ml of standard into a 50 mL volumetric flask and dilutingto volume with hexane.

6.15.2 Using a 500 JL microsyringe transfer 500 uL of 50 ug/mLAroclor 1232, 360 uL of 50 ug/mL Aroclor 1248, and 360 uL of 50ug/mL Aroclor 1262 to a 50 mL volumetric flask. Using a 100 uLmicrosyringe, add 45 uL of OCN internal standard (final concentration of0.1818 ug/mL). Dilute to volume with hexane and mix well by shakingand inverting flask several times. The prepared performance checksolution will contain a total of 1.22 ug/mL PCB (0.5 ug/mL Arocior 1232,0.36 ug/mL Aroclor 1248, and 0.36 ug/mL Aroclor 1262).

6.15.3 Transfer the performance check standard to 10 mL vials,cap tightly, and store in a freezer. A new performance check standardmust be prepared every three months.

6.16 Matrix Soike Standard: The matrix spike standard is prepared in thesame manner as the calibration standard outlined in Section 6.13. The onlychange is that the internal standard is not added to the matrix spikestandard. The matrix spike standard is used in quality control to determinepercent recoveries of the analytical sample procedures. The matrix spikestandard is added at a concentration of the same magnitude as theconcentrations exhibited by the samples.

6.16.1 Using the Aroclor stock standards, prepare a stock matrixspike standard as follows. Accurately pipette 12.5 mL of 1,000 ug/mLAroclor 1232, 9.0 mL of 1,000 ug/mL Aroclor 1248, and 9.0 mL of 1,000ug/mL Arocior 1262 into a 50 mL volumetric flask. Dilute to 50 mL withhexane, and mix by inverting the flask several times. The matrix spikestandard will contain a total of 610.0 ug/mL PCB (250 ug/mL Arocior1232, 180 ug/mL Aroclor 1248, and 180 ug/mL Aroclor 1262).

6.16.2 Transfer the matrix spike standard to 10 mL vials, captightly, and store in a freezer. A new matrix spike standard must beprepared every six months, or sooner, if comparison with calibrationstandards indicate a problem.

312416

r/a/wswsise


7.0 Procedure

7.1 Calibration:

7.1.1 Gas Chromatooraphic Operation Parameters: Establish thegas chromatographic operation parameters as follows:

GC Column: OB-1 (J&W, bonded polydimethylsilicone), 30 meters,0.25 mm internal diameter, 0.25 micron phase coating.

Oven Temperature Program: 50 degrees C. for 0.08 min hold time,50 degrees C. to 220 degrees C. at 6.0 degrees C./min, holdat 220 degrees C. for 32 min.

-t GC Column Velocity: 30 cm/sec, Helium.

Detector: Electron Capture Detector (ECD), attenuation 1, range 10,autozero on.

Detector Temperature: 250 - 300 degrees C.

Injector Temperature Program: 45 degrees C. for 0.04 min holdtime, 45 degrees C. to 250 degrees C. at 250 degrees C./min,hold at 250 degrees C. for 62.0 min.

Detector Make-up Gas: 30 mL/min, Nitrogen.

Auxiliary Temperature: 300 degrees C.

Autosampler: Multi-vial mode, 0.5 uL sample volume, Fast injectionrate (4.0 uL/sec.), 0.0 min injection time, 3 purge pulses.

7.1.2 Initial GC Calibration: Prior to running samples the systemmust be calibrated and the system performance must be verified.

7.1.2.1 Establish the gas chromatographic operation parametersoutlined in Section 7.1.1 and prepare the calibration standardcomposed of a mixture of Aroclors 1232, 1248, and 1262 as outlinedin Section 6.13.

7A.2.2 Load the gas chromatograph autosampier with a vialcontaining the calibration standard, bracketed by 2 wash vialscontaining acetone and proceed with the chromatographic analysis.During the chromatographic analysis, GC data acquisition should beperformed for future peak integration and data manipulation.

7A.2.3 Our laboratory will use a computer .based dataacquisition workstation (Dynamic Solutions, Maxima 820 workstation),interfaced to the gas chromatograph. The workstation processes thedetector signal, performs an analog to digital conversion, and storesthe digitized chromatograms on the computer hard disk. All data

312417


analysis will be done on the computer specialized software packageincluding peak integration, calculating calibration curves/responsefactors, report generation, chromatogram hardcopies, and archival ofdata.

7.1.2.4 Calculate the response factor for each separated andidentified peak. Appendix A identifies which congener and orcongeners compose each resolvable GC peak in the calibrationstandard, along with the amount that each congener or co-elutinggroup of congeners are represented in the calibration standard.Throughout this document the IUPAC PCS numbering system will beused for congener identification, unless otherwise stated. AppendixB is an example of an acceptable chromatogram of the calibrationstandard, along with peak congener labels for cross reference todata in Appendix A. Chromatographic resolution should be sufficientso as to separate congeners 17 and 18 into two peaks with avalley less than half height of congener 17. Response factors arecalculated relative to the internal standard by the following equation:

RRF - (Ax/Ais)x(Cis/Cx)

Where: RRF = Relative response factor of congener(s).Ax - Area of peak for the cogener(s).Ais = Area of peak for the internal standard.Cx = Concentration of the cogener(s).Cis = Concentration of the internal standard.

7.1.2.5 For congeners that are not found in the mixed Aroclorstandard and do not have amount values in the Appendix A table,the following calibration scheme will be employed. Response factorsfor these additional 19 Chromatographic peaks will be adapted fromthe tabulated data of response factors and relative retention timesof all the 209 PCB congeners found in Mullin et al, 1984 (seereference 9.10). These relative response factors will be adjusted forthe specific data analysis and quantification employed in thisdocument, based on the calculated response factors generated fromthe mixed Aroclor standard used for instrument calibration.

7.2 On-going Calibration:

7.2.1 Chromatoaraphic Resolution:

7.2.1.1 Chromatographic resolution should be sufficient so asto separate congeners 17-and 18 into two peaks with a valley lessthan the half height of congener 17. If this separation is not met,install a new GC column or adjust instrument conditions to achievestated separation. —

312418


7.2.2 Response Factors:

7.2.2.1 The relative response factors calculated from thecalibration standard will be verif ied on each working day byanalyzing the performance standard, calculating the selected congenerconcentrations and comparing to their known concentration. Asubset of six congeners will be used to verify the relative responsefactors before samples are processed. The six congeners include:

#6 and #205 • representing low level peaks in standard

#61 and #181 • representing medium level peaks in the standard#44 and #180 • representing high level peaks in the standard.

7.2.3 After the performance standard is analyzed, calculate theamount for these six congeners and compare those values to the knownconcentrations by the following equation:

Percent Difference *= [Amt(1)-Amt(2)]/Amt(2) x 100

Where: Amt(1)= Amount calculated for congener.^—x Amt(2) = Known amount for congener.

i 7.2.4 A percent difference greater than ±30% for the two low levelpeaks (#6 and #205) indicates an instrument problem or unacceptablerelative response factors. A percent difference greater than ±10% forthe medium level (#61 and #185) and high level (#44 and #180) peaksalso indicates an instrument problem or unacceptable relative responsefactors. If any of the evaluation congeners fail to meet the percentdifference acceptance criteria, the calibration standard must be re-analyzed and new relative response factors generated.

7.2.5 The performance standard must be analyzed again and valuescalculated using the new relative response factors. If the performancestandard fails to meet the percent difference criteria after re-calibration,sample analysis must not proceed until the problem is found andcorrected (i.e., GC gas leak, autosampler lines plugged, broken injectorliner).

7.3 Sample Preparation:

7.3.1 Soil and Sediment Samples:

7.3.1.1 To provide guidance to the analyst, as muchinformation about the samples received for analysis should beobtained from the generator and included in the sample log-in

__^ records. This may provide information on the expected levels ofcomponents being determined and whether dilution of the sample willbe necessary.

raaoSAQ61SB

312419


7.3.1.2 Reler to Section 7.1 for gas chromatographicconditions before running any samples. The instrument calibrationperformance criteria must be met (see Section 7.2).

7.3.1.3 Sample Preparation:

7.3.1.3.1 Process the sample by first decanting water fromthe top of the sediment. Transfer the sample to a clean pyrextray and remove any sticks, stones, and other foreign material,if present.

7.3.1.3.2 Allow the sample to dry at room temperature byplacing in a chemical hood for 24 to 48 hours. Frequently mixthe drying sample with a spatula and break up any clumps bycrushing. The sample is ready for extraction when the samplehas reached a free flowing consistency.

7.3.1.4 Extraction:

7.3.1.4.1 Weigh 5 to 20 grams of the air dried sampleinto a tared cellulose extraction thimble (Whatman 33 mm x 94mm) and record the weight. Add a plug of silanized glasswool to the top of the thimble.

7.3.1.4.2 Add 200 ml_ of 1:1 mixture of Hexane andAcetone (1:1 Hexane/Acetone) to a 250 ml round bottom flask.Add several boiling chips to the round bottom flask.

7.3.1.4.3 Turn on the cooling water to the condenser unitsthat will be used to condense the extraction solvent during thesoxhlet extraction of the sample.

7.3.1.4.4 Place the sample filled thimble into the soxhletextractor and attach the soxhlet to the 250 ml round bottomflask and condenser unit.

7.3.1.4.5 Place the 250 ml round bottom onto a heatingmantle and set the controller to a value of 5 to 6. Once thesolvent begins to boil, adjust the controller to achieve a solventflushing action of once every two to three minutes.

7.3.1.4.6 Extract the sample overnight for a minimum of16 hours. Turn the heating mantle off and allow the apparatusto cool to room temperature. Once cool, rinse the watercooled condenser with several disposable pipette volumes ofhexane. Separate the condenser from the soxhlet extractor andrinse the ground glass joint with several disposable pipettevolumes of hexane.

7/MO**«B 312420


7.3.1.4.7 Move the soxhlet extractor and attached 250 mlround bottom flask into a chemical hood. Flush the remainingsolvent from the soxhlet extractor by tipping the unit tofacilitate the syphon action. Using forceps, remove theextraction thimble and allow residual solvent to drain intosoxhlet chamber. Rinse the soxhlet chamber with severaldisposable pipette volumes of hexane, adding enough solventto be able to flush the soxhlet extractor by tipping to start thesiphoning action. Disconnect the soxhlet extractor from the 250mL round bottom flask and rinse the ground glass joint withseveral disposable pipette volumes of hexane.

7.3.1.4.8 Add several fresh boiling chips to the roundbottom flask and attach a 3-ball snyder condensing column tothe round bottom flask. Prewet the snyder column with 2 mlof hexane.

7.3.1.4.9 Using a heating mantle, evaporate the solventto approximately 5 mL. Make sure gentle boiling is takingplace and that the snyder column sections are not becomingflooded with solvent. Once the extract reaches approximately5 mL (do not go to dryness or loss of PCBs can occur),remove from heat source and quickly rinse the snyder columnwith 2 mL of hexane. Allow the glassware to cool to roomtemperature. Loosen the glass joint between the snyder columnand 250 mL round bottom flask and rinse the joint into theround bottom flask with 2 mL of hexane.

7.3.1.4.10 Quantitatively transfer the sample extract to a20 mL vial with three 2 mL hexane rinses. After the samplehas been transferred, rinse the disposable transfer pipette with0.5 mL of hexane into the 20 mL vial.

7.3.1.4.11 Evaporate the solvent with a gentle stream ofpurified nitrogen gas using a Pierce Reacti-therm block equippedwith a 9 port syringe needle gas manifold. Gentle heating canbe applied (40-50 degrees C.) to facilitate solvent evaporation.The extract should be concentrated to 0.2 to 0.3 mL, but neverallow extract to go to dryness (PCB losses can occur). Thisconcentration step removes the final traces of acetone, whichneeds to be removed before clean-up procedures are performed.

7.3.1.4.12 At this point the sample can be processed ineither of three ways:

1) If the sample is known to be free of interferences, thesample extract volume can be adjusted to 10 mL and andscreened by the GC packed column qualitative analysis todetermine PCB concentration and necessary sample extractdilution or concentration for final GC capillary quantificationanalysis.

312421


2) If the exact and nature of interfering co-extractablesin the sample is unknown, the sample must be analyzed by theGC packed column qualitative procedure to determineappropriate clean-up procedures. The sample extract isadjusted to 10 ml and analyzed by packed columnchromatography. After review of the chromatogram, the sampleextract is processed using applicable clean-up techniques. Aftersample clean-up the extract is re-analyzed by GC packedcolumn chromatography to determine PCB concentration andnecessary extract dilution or concentration for final GC capillaryquantitative analysis.

3) If prior knowledge and information exists on whattypes of interfering substances will be co-extracted with thePCBs, proceed directly with the necessary clean-up procedures.After sample clean-up, the extract is adjusted to 10 ml andanalyzed by GC packed column chromatography to determinePCB concentration for final GC capillary quantitative analysis.

7.3.1.4.13 Refer to Section 7.4 for sample extract clean-up procedures.

7.3.1.4.14 After the sample extract has been analyzed bythe GC packed column qualitative screening protocol, the sampleis prepared for final analysis by capillary gas chromatography.Dilute or concentrate the sample extract so that the PCBconcentration is within the established concentration range (seeSection 6.13.3). Spike this sample extract with the internalstandard (OCN) as close to the same level that it exists in thecalibration standards (typically 0.1818 ug/mL). Place the sampleinto an autosampler vial and proceed with the capillary gaschromatography analysis.

7.3.1.4.15 Refer to Section 7.5 for the calculations of PCBconcentration in the sample.

7.3.1.4.16 Section 8.0 outlines the necessary quality control(QC) samples to be included with each sample analysissequence. QC samples are prepared and analyzed along withthe samples being measured, and must meet defined acceptancecriteria for the sample data to be valid. The QC data istabulated or plotted on control charts and archived by thelaboratory and is available for inspection by the individualrequesting the analysis.

7.4 Sample Clean-up —

7.4.1 Most extracts of environmental samples that are to beanalyzed for PCBs by gas chromatography with electron capture detection

312422

i Northeast Analytical, Inc. -14- NEA-608CAP Rev. 2.0 8/89

have co-extracted xenobiotics and other interfering substances that mustbe removed before accurate quantification can take place.

7.4.2 Not all clean-up procedures need to be performed on everysample and several are sample matrix specific. It is the experience andknowledge of the analyst combined with the sampling site history thatshould guide the selection of which clean-up procedures are necessary.

7.4.3 Hexa n e/Di me thvlform amide partition:

7.4.3.1 This procedure is similar to the hexane/acetonitrilepartition procedure, but affords quantitative recover of PCBs. Thisclean-up technique effectively removes iipids and oils from thesample extracts. When necessary, this procedure should be carriedout prior to Flcrtsil clean-up.

7.4.3.2 Quantitatively transfer the sample extract to a 30 mlvial and adjust the sample volume to 15 mL with hexane. Extractthe sample four times with 5 ml of dimethylformamide saturated withhexane.

"v.

7.4.3.3 Transfer each dimethylformamide extract to a 150 mlseparatory funnel. Rinse the transfer pipette with a 0.5 mL ofdimethylformamide saturated with hexane into the separatory funnel.Add 100 mL of water containing 2% sodium chloride to theseparatory funnel.

7.4.3.4 Extract the dimethylformamide/water mixture with 20 mLof hexane. Allow the phases to separate for 5 minutes aftervigorously shaking for 30 seconds.

7.4.3.5 Decant the dimethylformamide/water phase (lower) intoa 250 mL beaker. Transfer the hexane phase to a columncontaining 3 inches of anhydrous sodium sulfate and elute hexanecontaining PCBs into a 250 mL round bottom flask.

7.4.3.6 Transfer the dimethylformamide/water fraction back tothe 150 mL separatory funnel and extract a second time with 20 mLof hexane. Decant the dimethylformamide/water phase back into the250 mL beaker and add the 20 mL hexane extract to the anhydroussodium sulfate drying column.

7.4.3.7 Repeat Section 7.4.3.6 for a total of three hexaneextractions.

7.4.3.8 Rinse the separatory funnel into the sodium sulfatecolumn with several disposable pipette volumes of hexane. Rinsethe column with several disposable pipette volumes of hexane. Elute

* the column with an additional 50 mL of hexane to remove all thePCBs. Finally, rinse the drain tube of the column stopcock into theround bottom.

IM. 312423U061SB


7.4.3.9 Add several boiling chips to the 250 mL round bottomflask and rinse the neck of the round bottom with severaldisposable pipette volumes of hexane. Attach a 3-ball snyderdistilling column to the 205 mL round bottom flask and prewet thesnyder column with 2 mL of hexane.

7.4.3.10 Using a heating mantle, evaporate the solvent toapproximately 5 mL. Make sure gentle boiling is taking place andthat the snyder column sections are not becoming flooded withsolvent. Once the extract reaches approximately 5 mL (do not goto dryness or loss of PCB., can occur), remove from heat sourceand quickly rinse the snyder column with 2 mL of hexane. Allowthe glassware to cool to room temperature. Loosen the glass jointbetween the snyder column and 250 mL round bottom flask with 2mL of hexane.

7.4.3.11 Quantitatively transfer the sample extract to a 15 mLvial with three 2 mL hexane rinses. After the sample has beentransferred, rinse the disposable transfer pipette with 0.5 mL ofhexane into the 15 mL via'.

7.4.3.12 Evaporate the solvent with a gentle stream of purifiednitrogen gas using a Pierce Reacti-therm heating block equipped witha 9 port syringe needle gas manifold. Gentle heating can beapplied (40-50 degrees C.) to facilitate solvent evaporation. Theextract should be concentrated to 0.2 to 0.3 mL, but never allowextract to go to dryness (PCB losses can occur).

7.4.3.13 Quantitatively transfer the sample to a 10 mLvolumetric flask and proceed with the packed column GC analysis.

7.4.4 Sulfuric Acid Wash:

7.4.4.1 The concentrated sulfuric acid treatment removeshydrocarbons and other colored biogenic compounds which are co-extracted with the environmental PCB residues. The sulfuric acidwash should be done first if a florisil clean-up is also being appliedto the sample.

7.4.4.2 Quantitatively transfer the sample extract to a 20 mLvial and adjust the volume to approximately 5 mL.

7.4.4.3 Add 2 mL of concentrated sulfuric acid to the sampleextract and shake vigorously for 30 seconds. Centrifuge sampleson low speed (2) using a bench top centrifuge. Transfer thehexane upper layer to a 20 mL vial. _

•j 7.4.4.4 Wash the sulfuric acid three times with 2 to 3 mL of' hexane. Shake each wash vigorously and centrifuge to aid in phase

separation. Transfer all three hexane washes to the 20 mL vial.

T/MO*»t» 312424


Make sure to rinse the transfer pipette with 0.5 ml of hexane intothe 20 mL vial.

7.4.4.5 Evaporate the solvent with a gentle stream of purifiednitrogen gas using a Pierce Reacti-therm heating block equipped witha 9 port syringe needle gas manifold. Gentle heating can beapplied (40-50 degrees C.) to facilitate solvent evaporation. Theextract should be concentrated to 0.2 to 0.3 mL, but never allowextract to go to dryness (PCB losses can occur).

7.4.4.6 If the sample is to be analyzed at this point,quantitatively transfer the extract to a 10 mL volumetric and proceedwith the packed column GC screening analysis.

7.4.4.7 If the sample needs further clean-up, proceed to thenext clean-up procedure.

7.4.4.8 Caution must be taken in performing the sulfuric acidwash when high amounts of lipid (i.e., fish samples) or water remainin the sample extract. These types of samples may produceexcessive heat due to the exothermic reaction of the sulfuric acidwith these materials. The rise in sample temperature can causesulfonation of the lower chlorinated PCB congeners and thereforelosses of PCB from the sample. If high amounts of lipids andwater are suspected, cool the sample in an ice bath. Also coolthe concentrated sulfuric acid in an ice bath before addition to thesample. Gently shake the sample extract and keep the sample inthe ice bath while treating it with the sulfuric acid.

7.4.4.9 The pesticides dieldrin and endrin are destroyed bythe suifuric acid treatment. If these pesticides are to be measuredthey must be fractionated (i.e., silica column) from the PCBs.

7.4.5 Florisil Adsorption Chromatooraphy:

7.4.5.1 The florisil chromatography separates PCBs and certainpesticides (i.e., DOT and analogs) from other co-extracted, polarcompounds. The procedure outlined below is for collection of thefraction that contains PCBs and certain organochlorine pesticidesonly. Additional fractions, eluted by stronger polarity solventmixtures can be collected if other pesticides are to be determined.

7.4.5.2 Adjust the sample extract volume to 0.2 to 0.3 mL,so that the sample is applied to the florisil column in a smallchromatographic band.

7.4.5.3 Prepare a micro florisil column in the following manner.Cut the top of a 5 mL disposable pipette at approximately 1 inchfrom the end of the pipette. Insert a small plug of silanized glasswool into the pipette and position at the 9 mL mark. Dry pack the5 mL pipette with 100% deactivated Florisil to make a column of

312425


1 ml in height. Make sure the Florisil is well settled by tappingthe column with a spatula. Rinse the micro column with 10 ml ofhexane and after elution of the 10 ml, rinse the outside tip of thepipette column, with 1 ml_ hexane. Place a 20 mL vial under themicro column for collection of the elute.

7.4.5.4 Quantitatively transfer the sample extract to the Florisilmicro column and rinse the sample container with 3 successive 0.5mL hexane volumes. Rinse the disposable transfer pipette into themicro column with 0.5 mL of hexane. Carefully rinse the microcolumn with 1 mL of hexane and then elute the sample to a totalvolume of 20 mL with hexane. After collection of the sample rinsethe outside tip of the micro column into the collection vial.

7.4.5.5 Evaporate the solvent wth a gentle stream of purifiednitrogen gas using a Pierce Reacti-therm heating block equipped witha 9 port syringe needle gas manifold. Gentle heating can beapplied (40-50 degrees C.) to facilitate solvent evaporation. Theextract should be concentrated to 0.2 to 0.3 mL, but never allowextract to go to dryness (PCS losses can occur).



7.4.6 Sulfur Removal:

7.4.6.1 Elemental sulfur is soluble in the extraction of solventsused for sediment and soil samples. It is almost always found asan interferant in these types of samples. Large amounts of sulfurcan cause the electron capture detector to signal saturate for longperiods during the elution envelope of PCBs. Even small amountsof sulfur can interfere with PCB measurement by co-eluting as achromatographic peak with certain PCB congeners.

7.4.6.2 Sulfur removal clean-up should be routinely done onsoil and sediment samples due to its ubiquitous nature. The sulfurremoval should be done prior to sulfuric acid and columnchromatography clean-up techniques.

7.4.6.3 Quantitatively transfer the sample extract to a 20 mLvial and adjust the volume to approximately 5 mL.

7.4.6.4 Add 0.3 to 0.5 mL of elemental mercury to. the sampleextract and vigorously shake for 1 minute. The sulfur is convertedto mercuric sulfide and precipitates out of the sample extract.

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Northeast Analytical, Inc. -18- NEA-608CAP Rev. 2.0 B/89

7.4.6.5 Quantitatively transfer the sample extract to a 20 mlvial by using three successive 1.0 ml_ hexane rinses. Rinse thedisposable transfer pipette into the vial with 0.5 mL of hexane.

7.4.6.6 The precipitated sulfur can be removed from thesample by performing a sulfuric acid clean-up or Florisil adsorptioncolumn clean-up.

7.4.6.7 After removal of the sulfur precipitate by either methodlisted in section 7.4.6.6, quantitatively transfer the sample extract toa 10 mL volumetric flask and proceed with the packed column GCscreening analysis.


7.4.7 Silica Gel Adsorption Chcomatooraphv:

7.4.7.1 Co-extracted organochlorine pesticides can interferewith PCS identification and quantification. A separation of PCBsfrom organochlorine pesticides can be accomplished by silica geladsorption chromatography, allowing the analysis of both PCBs andpesticides as separate fractions.

7.4.7.2 Adjust the sample volume to 0.2 to 0.3 mL withhexane. Prepare a column of 7.5% deactivated silica gel (100-200mesh, Grade 923, Aldrich), packed with 11.5 g of the silica gel.Rinse the column with 50 mL of methylene chloride followed by 50mL of pentane. Rinse the stopcock drain tube with 1.0 mL ofpentane. Place a 250 mL round bottom under the column to collectthe sample eiuate.

7.4.7.3 Quantitatively transfer the sample to the silica columnusing three successive 0.5 mL pentane rinses. Rinse the disposabletransfer pipette into the column with 0.5 mL pentane. Rinse thecolumn walls with several disposable pipette volumes of pentane.Elute the silica gel column with 50 mL of pentane. Rinse thestopcock drain tube with 1.0 mL of pentane. This fraction willcontain the PCBs.

7.4.7.4 Place a 50 mL bottle under the silica gel column.Elute the silica gel column with 36 mL of 20% methylene chloridein pentane. This second fraction will contain the organopesticidesand polychromatic hydrocarbons. This fraction can be stored in arefrigerator and analyzed at a later date if pesticide determinationis requested.

7.4.7.5 To the round bottom flask containing the PCB fractionadd several boiling chips and rinse the neck of the round bottomflask with several disposable pipette volumes of hexane. Attach a

312427


3-ball snyder distilling column to the 250 mL round bottom flask andprewet the snyder column with 2 ml ot hexane.

7.4.7.6 Using a heating mantle, evaporate the solvent toapproximately 5 ml_. Make sure gentle boiling is taking place andthat the snyder column sections are not becoming flooded withsolvent. Once the extract reaches approximately 5 mL (do noi goto dryness or loss of PCBs can occur) , remove from heat sourceand quickly rinse the snyder column with 2 mL of hexane. Allowthe glassware to cool to room temperature. Loosen the glass jointbetween the snyder column and 250 mL round bottom flask andrinse the joint into the round bottom flask with 2 mL of hexane;

7.4.7.7 Quantitatively transfer the sample extract to a 15 mLvial with three 2 mL hexane rinses. After the sample has beentransferred, rinse the disposable transfer pipette with 0.5 mL ofhexane into the 15 mL vial.

7.4.7.8 Evaporate the solvent with a gentle stream of nitrogengas using a Pierce Reacti-therm heating block equipped with a 9port syringe needle gas manifold. Gentle heating can be applied(40-50 degrees C.) to facilitate solvent evaporation. The extractshould be concentrated to 0.2 to 0.3 mL, but never allow extractto go to dryness (PCB losses can occur).



7.5 Calculations:

7.5.1 External Standard Calibration (Packed GO:

7.5.1.1 The packed column GC screening analysis will be doneby the external standard calibration technique. Calibration andsample quantification will be performed by a commercial GC softwarepackage installed on a personal computer. The GC will bestandardized by using Arocior 1242 and Aroclor 1260. These twoAroclor formulations incorporate most environmental PCBs found insample extracts and provide a good estimate of PCB amount forfinal dilution or concentration for capillary analysis. A multi-levelcalibration curve will be developed based on 1 ppm and 10 ppmstandards. Weight percent data (Webb and McCall) will be used togenerate standard peak amounts. __

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j Northeast Analytical, Inc. -20- NEA-608CAP Rev. 2.0 8/89

7.5.1.2 The calibration curves for each calibrated PCB peakwill be calculated using the following formula:

Calibration factor*" Amount fuo^ of componentTotal area of anaiyte peak

The calibration curve will be fitted to the calculated calibrationfactors by a cubic equation to give the best line for all calibrationpoints.

7.5.2 Sample Calculations (Packed GC1

7.5.2.1 The concentration of each identified PCB peak in asample will be calculated based on the extract volume (not thesample weight or volume) to supply solution concentration valuesthat show if the extract needs to be diluted or concentrated forfinal capillary GC analysis. The solution concentration of eachstandardized PCB peak in a sample is calculated as follows:

Concentration (ug/mL) « (Ax) x (CF)

" Where: Ax«Area of peak of interest in sampleCF«Calibration factor from peak in standard.

7.5.3 Internal Standard Calibration (Capillary GC)

7.5.3.1 The capillary column GC analysis will be done by theinternal calibration technique. Calibration and sample quantificationwill be performed by a commercial GC software package installedon a personal computer. The capillary GC will be standardized byusing an Aroclor mixture that encompasses all the possible PCBcongeners present in environmental samples. Refer to Section 6.13for details on the calibration standard and Aroclor ratios.

7.5.3.2 Response factors for each separated and identifiedpeak in the standard will be calculated using the following formula:

RRF m (Ax/Ais)x(Cis/Cx)

Where: RRF - Relative response factor of congener(s).Ax » Area of peak for the congener(s).Ais « Area of peak for the internal standard.Cx « Concentration of the congener(s).Cis « Concentration of the internal standard.

--. 7.5.3.3 For the 19 chromatographic peaks that_will utilizeresponse factors from tabulated data found in Mullin et at, 1984(see Section 7.1.2.5), numbers will be manually entered into thePeak calibration table used for sample quantification. Allcalculations will proceed exactly as outlined above for peaks that

ram"*m 312429


have response factors generated from amount information containedin Appendix A.

7.5.4 Sample Calculations (Capillary GO

7.5.4.1 The concentration of each identified PCS peak in asample will be calculated based on the sample air dried weight.

7.5.4.2 The sample PCB concentration of each standardizedPCB peak is calculated as follows:

Concentration fna/Ql«ffAxUCisUD^[(Ais)(RRF)(Ws)j

Where: Ax = Peak area for congener(s) being measured.Cis * frngfrunt of internal standard added to sample extractD « Dilution factor, if sample was diluted prior to analysis.Ais « Peak area of added internal standard.RRF = Relative response factor for congener(s) being

measured,as determined in Section 7.5.3.2.Ws » Air dried weight of sample.

The dilution factor (D) is based on a final extract volume of 1 mL.Typically, the sample is extracted with about 200 mL which is thencleaned up and concentrated to a final volume of 10 mL. If nofurther volume adjustment is required, then D«10. If furtherdilutions are required, the D«=10 x (dilution #1) x (dilution #2) x...

7.5.5 Data Output and Reporting Format:

7.5.5.1 Several specialized software routines have beendeveloped for high resolution PCB analysis to aid the researcher inunderstanding and organizing the complex data generated from thisextremely detailed analysis. Appendix C contains examples of thesample hard copy format that will be used in reporting sampleinformation.

8.0 Quality Control

8.1 Table 3 lists the Quality Control requirements and required recordingformat that will be applied to the capillary gas chromatographic analysis ofPCBs in soils and sediments.

312430S9061SB

312431

\


Table 3 - Quality Control Requirements

QC Sample Reporting Format^ Frequency

Lab Blank Tabulation Daily, or with each sample analysissequence (up to 20 samples).

Performance check Tabulation Performance check sample analyzed priorto each sample analysis sequence (upto 10 samples).

Duplicate Analysis Tabulation One duplicate analysis per 10 fieldsamples, or monthly if less than 10samples/month are analyzed.

Matrix Spike Tabulation One matrix spike per 10 field samples.

8.1.1 Sample Records: AH samples that arrive at the lab should beaccompanied by a chain of custody document. The following pertinentinformation should be documented for all samples:

1) Unique label that identifies sample.

2) Location of sample collection site.

3) Date and time of collection.

4) Project name and/or ID number.

5) Field personnel at sampling.

6) Required analysis.

The sample information will be recorded in the Lab Log Books and eachsample will be assigned a unique Lab ID Number. The sample analysiswill be archived by computer using the Lab ID Number.

8.1.2 Laboratory Blank: The laboratory blank will monitor and assessif the contamination of excessive interference is occurring from laboratorysolvents, reagents, and glassware used in processing samples foranalysis. The laboratory blank is taken through the sample extractionand clean-up procedures to include all manipulations exposed to actualsamples (required volume of solvents, concentration steps, clean-upprocedures, etc.). If the laboratory blank is positive for PCBcontamination, the source of the contamination must be traced down andeliminated before samples can be processed and analyzed. If non-PCBcontamination occurs that interferes with PCB quantification,-it too mustbe traced down and eliminated before proceeding with sample analysis.

The laboratory blank will consist of sandbox sand, purchased at a localhardware store, which has been baked at 250 degrees C. in a vacuum

1000SBOfitSB


oven for 24 to 36 hours and allowed to cool and store in glasscontainers. This is the same procedure used to prepare material whichis supplied to EPA's contract laboratories by EMSL/Cincinnvti, for use asclean solid matrix.

8.1.2.1 Samples analyzed after a positive laboratory blankshould be considered unreliable. If a laboratory blank is positivefor PCBs, the source of contamination shall be located andeliminated. If the contamination occurred during the extractionprocedure, the samples will require re-extraction and re-analysis. Ifthe contamination occurred after this step, then re-extraction is notappropriate and the existing extracts will be reanalyzed. Anyaliquots of the extracts (i.e., injection vials) which could havebecome contaminated will be discarded.

8.1.3 Performance Check Standard: As outlined in section 7.2. aperformance check standard will be analyzed on each working day priorto sample analysts and at an interval of one performance standard pereach sample analysts sequence (up to 10 samples). The performancecheck standard must meet the acceptance criteria established in Section7.2. If the performance check standard fails to meet the acceptancecriteria, the calibration standard must berlanalyzed and new responsefactors generated.

8.1.3.1 The performance check standard must be analyzedagain and compared to the acceptance criteria. If the performancecheck standard fails to meet the acceptance criteria after re-calibration, sample analysts must not proceed until the problem iscorrected. A typical analytical sequence is as follows:

1) Performance check standard.2) Method blank.3 thru 11) Samples (including duplicates, MS).12) Performance check standard.13 thru 21) Samples (including duplicates, MS).22) Performance check standard.

8.1.3.2 All samples that were analyzed after the performancecheck standard exceeded established criteria must be re-analyzed.

8.1.4 Duplicate Analysis: Duplicate analysts of the same sampleare performed to assess method precision. The percent relative standarddeviation of the two measurements on the sample is calculated on totalPCS concentration by the following equation:

RSD = (DUP1 - DUP2)/AVG x 100

Where: RSD - Percent relative standard deviation.DUP1 sr the greater of the measured values.DUP2 « the lesser of the measured values.AVG « average of the two analyses.

312432

312433


8.1.4.1 The percent relative standard deviation must be lessthan or equal to 25% if the concentration of PCB in the sample isgreater than or equal to 0.5 ppm. The percent relative standarddeviation must be less than or equal to 50% if the concentrationof the PCB in the sample is less than 0.5 ppm.

8.1.5 Matrix Spike: Spiked sample matrix data are analyzed toassess analytical accuracy. Thus the sample is spiked and carriedthrough sample analytical procedures including extraction, clean-up, andGC analysis. Matrix spike duplicates are not required for this project.

8.1.5.1 If a sample matrix previously analyzed to be free ofPCB is available, spike this sample with matrix spike standard (seeSection 6.16) at a concentration similar to sample concentrations.Extract and analyze this spiked sample following procedures usedfor actual sample analysis. Calculate the percent recovery of thematrix spike by the following:

P = A/T x 100

Where: P = Percent recovery, %.A = Concentration of analyte in the spiked sample aliquot.T-Known true value of the spike concentration added to the

sample aliquot.

8.1.5.2 If an uncontaminated sample is not available, thematrix spike can be performed on a sample previously analyzed.There must be sufficient sample for re-analysis as a matrix spikeand the sample must be homogeneous in PCB distribution for validdata to be produced. Preferably a sample of low level should beused in this case. Spike the sample with the matrix spike standard(see Section 6.16) at a concentration similar to sampleconcentrations. Extract and analyze this spiked sample followingprocedures used for actual sample analysis. Calculate the percentrecovery of the matrix spike by the following:

P = (A-B)/T x 100

Where: P«Percent recovery, %.A=Concentration of analyte in the spiked sample aliquot.T»Known true value of the spike concentration added to the

sample aliquot.B = Background concentration of PCB in the unspiked sample

aliquot.

8.1.5.3 The percent recovery for a spiked matrix .sample mustbe greater than or equal to 70% and less than or equal to 130%,based on the total PCB concentration. If a matrix spike recoverysample does not meet the acceptance criteria the cause must befound and corrected. All data collected on samples after the spiked

7/MOSMS1U

Northeast Analytical. Inc. -25- NEA-608CAP Rev. 2.0 B/89

recovery sample failed to meet the acceptance criteria should beconsidered unreliable and samples must be re-extracted andanalyzed. If additional sample is unavailable, then the data mustbe flagged as such.

8.1.6 Retention Time Windows

8.1.6.1 The GC system should be checked by the analyst tomake sure it is functioning properly before establishing retention timewindows. Make three analytical measurements of the standardmixture containing the compounds of interest of a minimum of a 72-hour period.

8.1.6.2 Calculate the standard deviation resulting f rom thevariation in retention times for each component from three analyticalruns.

8.1.6.3 The retention time window is defined as plus or minusthree times the standard deviation of the three retention timedeterminations.

8.1.6.4 If the standard deviation for a particular componentis zero, substitute the standard deviation of a close elutingcompound found in the standard solution.

8.1.6.5 Besides using the retention time window to assignpeaks for quantification, the analyst should also rely on hisexperience in pattern recognition of multi-residue sample analysis.

8.1.6.6 After the daily performance check standard has beenanalyzed, establish the daily retention time window for each analytefrom the retention time of the standard just analyzed. The dailyretention time window equals the absolute retention time of theperformance check standard (midpoint of the window for the day)plus or minus three times the standard deviation determined inSection 8.1.6.2.

8.1.7 Qualitative Compound Identification/Confirmation: Theidentification of specific congeners in a PCS mixture is done bycomparing the retention time of each peak with the retention times ofthe peaks in a known standard. The standard, consisting of a specifiedmixture of three Aroclors (1232, 1248, and 1262), has been completelycharacterized by workers at EPA's Large Lakes Research Station (seeMuHin, 1985). Repeated injections of the standard are used to establishan acceptable 'retention time window* for each peak. It should benoted, also, that the experience of the analyst plays a significant rolein the recognition of PCS patterns. The Laboratory Director-of NortheastAnalytical, Inc., Robert Wagner, has over 8 years of experience inperforming congener-specific analysis of PCBs. Comparative studies usingGC/MS and GC-HECD detector analytical techniques have confirmed thevalidity of this method.

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Northeast Analytical, Inc. . -26- NEA-608CAP Rev. 3.0 6/90

Potential interferences to the PCB analysis are minimized by a numberof mechanisms. These include:

1. The EC detector is largely specific to chlorinated compounds.2. Rigorous clean-up steps are performed to remove specific

interferants, including pesticides, sulfur, lipids and oils,hydrocarbons and biogenic matter. The analyst will strive toproduce an extract which is free of interferences.

9.0 References

9.1 US EPA 40 CFR Part 136, 'Guidelines Establishing Test Procedureslor the Analysis of Pollutants', July, 1988.

9.2 Standard Methods for the Examination of Water and Wastewater, 16thEdition, Published by: American Public Health Association, American WaterWorks Association, Water Pollution Control Federation, 1985.

9.3 US EPA SW-846, 'Test Methods for Evaluating Solid Waste; Volume1B Laboratory Manual Physical/Chemical Methods', Off ice of Solid Waste andEmergency Response, 3rd Edition, 1986.

9.4 New York State Department of Health, 'Environmental LaboratoryApproval Program Certification Manual', Wadsworth Center for Laboratories andResearch, 1988.

9.5 Mullin, M.D. 1985. PCB Workshop, US EPA Large Lakes ResearchStation, Grosse lie, Ml, June.

9.6 James L. Lake. Communication, Silica Gel S.O.P., US EPAEnvironmental Research Laboratory, Narragansett, Rl, 1989.

9.7 Q. Seidl, K. Ballschmiter, Isolation of PCBs from Vegetable Oils:Recovery and Efficiency of 'Clean-up' Methods, Chemosphere, No. 5, pp 363-366, 1976.

9.8 M. Zell, K. Ballschmiter, Baseline Studies of the GLobal Pollution,III. Trace Analysis of Polychlorinated Biphenyls (PCB) by ECD Glass CapillaryGas Chromatography in Environmental Samples of Different Trophic Levels,Fresenius Z. Anai. Chem., 304, 337-349, 1980.

9.9 R.G. Webb, A.C. McCall, Quantitative PCB Standards for ElectronCapture Gas Chromatography, J. CHem. Sci., Vol. II, 366-373, 1973.

9.10 M.D. Mullin. C.M. Pochini, S. McCrindle, M. Romkes, S.H. Save,•High-Resolution PCB Analysis: Synthesis and Chromatographic Properties ofAll 209 PCB Congeners', Environ. Sci. Technol., Vol. 18, No. 6, pp 468-476,1984.

312435

Appendix A

Congener Composition of Aroclor Calibration Mixture (6.1 ppm)

(Aroclors 1232, 1248, 1262 in a ratio of 25:18:18)

PeakNumber

1o345678910111213141516171819202122232425262728293031323334353637383940414243

RRT

0.32430.35360.35400.36850.38870.39410.39800.41020.41060.41330.42200.42450.42690.42850.43390.43890.44360.44850.44950.45170.45300.45640.45730.46310.46700.47070.47460.47530.47900.47980.48250.48440.48540.48970.49150.49150.49360.49900.50260.50410.50310.50850.5094

Amount( nK/mL )

430*260282242500*10**9.2130748.8131**1.82310166214168,5116.727*14*129.1905040**15088163*.*33*5

Congene rTD

001002003004,007,006005.014019030Oil012 .015,017024.016,023034 ,029026025031028,020,022,045036046039043,049047048,062,035044,037,041,068096040057.067,

010009

008

013018

027032

054

050021, 033, 053051

.052, 073

075065

104042, 059064, 071, 072

_

103100

312436

PeakNumber

4445464748495051525354555657585960616263646566676869707172737475767778798081828384858687888990919293

RRT

0.51190.51450.51640.51820.52270.52740.53080.53240.53460.53370.54210.54370.54720.55000.55280.55490.55700.56300.56370.56880.57140.57270.57390.57700.57750.58330.58580.58750.59450.59750.60010.61000.61060.61210.61630.61930.62370.62740.63150.63790.64300.64390.64680.64970.65290.65830.66510.67240.67780.6838

Amount( ng/mL )

7.4812102721418043348231.83.61933.2211471*1357222.233.3*145*8.50.911668.04147.96*5254.62.5

• 13.889812334*61504.7771 .1221105736.9

CongenerID

058.074 ,061 ,066,055,056,084 ,089090,099112,.083,086,081,085,136077,154082151124,144107,123106,139,114,122,146,105,153168141179130137,138,158129178166175182,128183167185174,177156.

063094070,093,091,060092,

101

119,109097,087 ,116

110

135

108,

118,140134,131,161132

176160,

187

183

171

076095098

155

150

152111 . 115

147

149

143133, 142

163, 164

—

312437

PeakNumbe r

949596979899100101102103104105106107108109110111112113114115116117

RRT

0.68890.69190.69280.69960.70450.71040.71410.71900.72510.73230.75540.76110.76770.77790.78260.70360.81710.84840.85830.87740.90580.92411.02711.0838

Amount( ng /mL )

3.31*1.27320.69719.22.18240144.51091.129.90.46.71501701 .855.924.94.8694420.95

CongenerID

202157173200172197180193191199170190169198201196189195208207194205206209

, 204, 192

,203

RRT= Relative Retention Time to internal standard OCN= 1.0000r Refer to Section 7.125 for descriptfor congeners with no amount values.

* Refer to Section 7.125 for description of peak quantification

312438

Appendix B

DB-1 Capillary GC Chromatogram of Arocior Mixture

(Aroclors 1232. 1248, 1262 in a ratio of 25:18:18)

312439

Japli: 1212/1241/12(2 Ckuitl: dittctor 1icqiirri: 27-JUI-IJ 13:11 It t hod: C:\IU\GC1\1M

x 1O"1 volts

PilutH: 1324IS2Op«rator: tn

IZ5» 4I.S2

': 49.60

1^> 53.H

Or\7

—' '***'-

_„: 55.13 — O

312440

Appendix C

Format of sample reports and specialized

data handling and data reduction reports.

312441

IUIIKA lc)I9{7 Dyoiuc Solution, Dmsiot of Hilhpore

KUIIU 120 CUSTOM tEPOtT

Priatsd: 27-JUL-19I9 15:31:58

SIMPLE SED1MEIT, SECTIOI (1717 it Method: 1ICI 1ES 1IOCLOI QU1IT.

ACQUIIB: 20-WH9I9 10:34late: 5.0 poiBti/iee

Duratioa: 70.000 mgtetOperator: in

ORECTOt:

Ul

25(7I

1014151(1719212223242526272931323337313941424344454(4149505153545556575159(0

detector 1

Ml

479

101112131415If17It192021222324252627212930323334353(373140414243444546474149SO99

IETEITIOI TIMEUifiutes)

17.4119.1920.1121.2421.4522.1323.0223.0923.3123.6624.0624.3424.4224. (024.(424.9925.1625.3725.6125.1636.0126.102U92(.(026.1927.0327.1127.3127.4927.5927.7227.9721.1721.4221.(221.1221.9129.2329.3129.5025.6629.1154.22

PEU I1HE(ebloriat to.)

2 Ql5 (4,1§l( 17,9)7 10I (5,1!10 (b;14 (15,11115 (17)H (24,27)17 116,32119 (34.54121 12022 125)23 (31)24 (21,50)25(20,21.33,53)2( (22.51)27 (45)29 (4031 (52,73)32 (49)33 (47)37 (44,104!31 (37,42.59)39!41,(4,71,72141 (9042 (40143 (57.103)44 1(7,100)45 (5M3)46 (74,94141 166,93,95)49 (55,91,91)50 (56,60)51 (14,92,155)53 (90,101)54 (99)55(112,115,150)S( (13.109) -57 (16,97,152)SI tl7,m,115]59 (15,110I.J. IOCI)

Peak iru

1(122.59405(.94219.99915.7

45470.5S9917.(21477.313372.2

31411. i5020.4

27177.2107}.34(27.372(9.37115.21349.

4313.73220.1

S401I.571911.791751.120(73.323516.237421.51237. (2516.7

11719.710141.3222.

13739.35057.311(5.10320.urn.

iwse.

TOT1L

I103.(11519.227(94.532043.9

456(121.9

20271027.1

me: ranhftrmit: GC2

rilDUE: 19001lidei: Disk

Dilitiot: 4.1(70.500

1MODR JOOLTIOI___ I

0.052(30'0.1(4031!1.0017250.0041791.0203051.0270930.0115410.0057140.0131120.0075990.001119'0.0050510.0045110.00(1470.0090230.0014210.0031430.0010290.0014290.01SS208.0156360.0170150.003103O.OOS2900.0041030.002223*0.0004070.002115*0.001917*0.000525*0.0011390.0050170.0070350.0013760.0107030.02(1(10.0112440.00223M0.0011290.002S030.0030210.002t790.202000

0.49676

SAMPLE 1MOUITJ

0.431(2*1.3(709!0.014310.034130.1(9220.225790.09(240.047(20.115(90.0(3330.00933*0.042150.031240.057060.075200.070240.032030.001510.011910.1293S0.130310.142390.031(90.044090.040030.01153'0.003390.017(3*0.01(S(*0.00437*0.015330.042390.051(30.011460.019200.223920.093710.011(3*0.015250.020K0.025110.02399

4.14000

312442

IUJIKA (:)19I7 (paiic Solutions, Divisioo of lillipore 312443

KillSi 120 CUSTOH lEPOtT

Phtted: 27-Ml-1919 16:35:41

SAMPLE: SEDIIER, JECTIOI 11717 IB lettod: IIGI IES ItOCLOt QUIT.

ACQUItQ: 20-;UI-19I9 10:34Ute: 5.0 poists/tee

Duntios: 70.000 tioitei

DBTECTOl:

1DI

1012131415H1121222324253621293031323334353(31394041434445414741 -4950515253565751

detector

Kl

51525354555(575159(0(1(2(3(4(((7(1(970717273747576777179181112S314151617II19

•». •929394959(979199

Operator: IEI

1

IBTERIOI TIKE mi HIEliinotes)

29.9230.0430.3030.4030. (930.1230.9631.1731.5131.7932.0932.2632.3932.9733.3633.4433.6933.1134.1134.4534.7134.9435.1035.2735.5735.943(.3436.6<3(.9737.2437.1537.1331. 0931.6231.1939.2339.1240.1141.1143.1142.3?42.9544.2445.9(49.1050.1054.22

(ebloritt BO.)

(0 (130(1 (77,11011(2 (1541i) 1121H (151)(5 (124,13!)(7(107.101,147)(9(10(.lll,149)71(114,134,143)72(122,31,33,4273 (14(,1(1)74 1105,132175 (153)77 (141110 (137)11 (17012(131,1(0,3,4)13 (151)14 (129115 [171117 (175)II (112,117)19 (121)90 (113)91 (1(7)92 (115)93 (174,111)94 (177)95 1156,171)97 (157)91 1173199 (200,204)100 (172.192)102 (110)103 (193)104 (191)105 (199)106 (170)1C7 (190)101 (191)109 (201)110 (1)6,203)111 (119)112 (195)US (194)IK (2051!.S. (OCX)

Pea Area

W34.7

13529.74714.(

131715.3yios.i91570.7

571125.7205)1.915905.492194.3

111195.432(473.311779(.24B(71.(32099.3

404734.743052.27992.3

54400.312024.6

240(12.939935.1

134422.314(93.54(459.0

247191.1143527.11C70II.I20714.4

5934.715595.057179.2

5(7316.032(53.31319(.S22311.4

31(544.(73521.310419.1

147371.5193149.1

12121.2195965.6

7(74.14566121.9

TYPE: UHIItstriKit: GC2

FILEliJE: 1)001Index: Dirt

DilBtios: 4.1(7iBOBBt: 0.500

AIOUIT SOUWIOI(ug/il )

0.0109190.01(1)10.002472'0.0004(90.0201110.0074020.0143730.0111530.0023790.001914'0.0131310.0091470.0751660.0079360.00(1510.002073'0.0(03710.003(250.0001790.0073130.0021(0'0.0352140.0027(10.0111410.002JT70.0031930.0291(40.01(1530.0095790.0032200.000200'0.001545'0.0057130.0(09070.001519*0.000(39*0.001327*0.0233930.0041530.000479*0.0111010.014JW0.000379*0.0053040.0107020.000275'0.202000

S1IPLE ANOUIT

0.0)100t.140130.020(0'0.003910.1(7(70.0(1(90.119790.740500.019130.01595'0.109490.07(230.63227

0.055430.01721'0.503130.530210.007330.0(0950.01100'0.293470.023010.151110.022310.032450.243050.140460.079130.02(130.001((*0.01211'0.041200.507(00.01324'0.00533'0.0110C0.194)60.040450.00400*0.091350.119120.00316'0.044200.019190.00229*

TOTAL 0.620012' 5.15711'

NDRTHQST INC.

301 K7TT SIKEET, NV 12305

(518) 346-4592

PCB OKZXEK AfCUNT and NANOCLE RETORT

JO FH£ NVE: 89001.MX

CUSTOd: ___ J. EPA ___SAMPLE EESCRUnCK: SEDIMENT, £U.'i'KJK 617

SAMPLE SSXEZ) DiVUOMKOL AL3H«nai

TYPE FCR MIXED PEAK SECONOJITSJ^ S

FBUCNO.•H

256781014151617IS21222324252627293132333738394142434445464849

JCUCOUW VT.

188.70223.10223.10223.10223.10257.50249.00257.50257.50257.50267.90257.50257.50257.50257.50259.50258.70292.00292.00292.00292.00292.00292.00272.40292.00326.40292.00298.90298.90292.00292.00293.50324.70•xn nn

JDOUNr KazcBQleB/gftBl} Sanple

0.43862 2.324431.36709 6.127700.01438 0.064460.03483 0.156120.16922 0.758490.22579 0.876850.09624 0.386510.04762 0.184930.11569 0.449280.06333 0.245940.00933 0.034830.04215 0.163690.03824 0.148500.05706 0.221590.07520 0.292040.07024 0.270670.03203 0.123810.00658 0.02938O.OUS1 0.040790.12935 0.442980.13031 0.446270.14239 0.487640*03169 0.106530.04409 0.161860.04003 0.137090.01853 0.056770.00339 0.011610.01763 0.058980.01656 0.055400.00437 0.014970.01533 0.052500.04239 0.144430.05863 0.18057n mitf. f> mm* 312444

535455565758596061626364656769717273747577808182838485878889909192939495979899100102103104105106107108109110in112115116

326.40326.40326.40326.40326.40326.40326.40360.90315.80360.90326.40360.90350.50336.80337.50347.80336.80360.90347.80360.90360.90360.90395.30360.90360.90360.90395.30395.30395.30360.90395.30360.90394.30394.30394.30382.20360.90395.30429.80395.30395.30395.30395.30429.80395.30395.30429.80429.80429.80395.30429.80429.80429.80

0.223920.093710.018630.015250.020660.025180.023990.091000.140830.020600.003910.167670.061690.119790.740500.019830.015950.109490.076230.632270.066140.055430.017280.503130.030210.007330.060950.018000.293470.023010.151180.022310.032450.243050.140460.079830.026830.001660.012880.048200.507600.013240.005330.011060.194960.040450.004000.098350.113820.003160.044200.089190.00229

0.686030.287100.057080.046720.063910.077140.073500.252150.445950.057080.011980.464590.176010.355672.194070.057020.047360.303380.219181.751930.183260.153590.043711.394100.083710.020310.154190.045540.742400.063760.382440.061820.082300.616410.356230.208870.074340.004200.029970.121931.284090.033490.013480.025730.493200.102330.009310.228830.278780.007990.102840.207520.00533

312445

vo

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iôjodcicjr jdf- idodddooodor- ir - i f - ioooooooooooc

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+to

*?s 8a8 !P «""« - in • "~

? ?i** a9 Fl»»• *, • * » % • < » » * *iqiAîn* » • S8J8SB585hnnî3nN»fifiFi

• . ^f*Q*tfO*^QjQt^f lPf l&if lQ«Ht^SfgjPte*l>O^ lO<frC' iOQt** 'M I ^T^c^gpgO^rBggjQCNQgtf f tQQ^MOui tQrHr^fn^g^lO)SS I ^ r iMiCiCtQQQiQ^f iSzJSSQQEivar j^ iOyiy i^HwQftO'B6 I rH v<i v* vf Pfl C*| f*l •*) 1*9 **i f*l f*| <*i ^p ^ 4^ y p ^p ^* ^fi *f u) I

M u, §§ 8 a giS §gg g iig§§§§§§§§§g§§8g|gS§gg§§s§§gi

O »* «n n n «M *>» t-i r-i «n «n•• *; •• »• •• •• •• •• •• •• ••c« •* «r«iî •* •* ^ • ^ • m m£ 8 Jj Tl CJ'Tj ^ ^ 71 CJ ^J J J 7l !S i ^J VJ 7J Vi TJ ?I CJ C? CJ ^1 J J ^ ^* *^ •** "^ *^'I (ft B y r4C4C«rir4r)Piriri<n<noortrir)rt<«|i4i«J^4i>iKri4iiinî>iKin4i<4i>«fi

s K

53545556575859£06162€364656769717273747577808182838485878889909192939495979899100102103104105106107108109110111112115116

28.8228.9829.2329.3129.5029.6629.8129.9230.0430.3030.4030.6930.8230.96n.1731.5831.7932.0932.2632.3932.9733.3633.4433.6933.8834.1134.4534.7834.9435.1035.2735.5735.9436.3436.6436.9737.2437.4537.8338.0938.6238.8939.2339.6240.8841.1842.1142.3742.9544.2445.9649.1050.10

5:25:26:4 5:25:26:4 5:25:25:26:44:0 5:26:35:26:36:3 5:15:1 6:36:3 5:16:3 5:15:1 6:36:26:3 5:16:26:26:27:46:26:26:27:37:37:36:27:36:17:37:37:37:3 6:16:17:38:47:27:27:27:28:47:27:2:3:3:3:1:3:2:2

101 090099150 112083 109152097087 Ul085 116136077 110154 .082151135 124107 108149 US134 143122 131146161132 105153141137176138 163158129178175187 182128183167185174 181177171156157173200 204172 192180193191199170190198201196 203189195194205

.5814

.5880

.5969

.6029

.6062

.6175

.6224

.6257

.6295

.6349

.6453

.6499

.6563

.6628

.6672

.6796

.6871

.6955

.7035

.7036

.7203

.7329

.7305

.7403

.7429

.7501

.7537

.7611

.7653

.7761

.7720

.7814

.7848

.7965

.8031

.8105

.8184

.8152

.8197

.8278

.8362

.8397

.8447

.8494

.8740

.8740

.8845

.8875

.8935

.9142

.9321

.9620

.9678

22'34'5 ; 22*455'22'44'522'34'66' ; 233'56 ; 23'44'22*33*5 ; 233'4622'3566' ; 22'345 ; 22'3'4522*345* ; 233*55* ; 2344'622*344* 1 23456?22*33'66'33*44* ; 233*4*622'44'56'22*33*422'355'622*33*56* ; 2*344*5233*4'5 ; 233'45' ; 22'34t522*34*5*6 ; 23*44*5 ; 233'422*33*56' ; 22'3456'; 2344'2*33*45; 22*33*46;22*33*55>

22t34'55' ; 233'45'622*33'46* ; 233*44*22*44f55'22*3455'22'344'522'33'466'22'344*5* ; 233*4*56 ; +2233'44'622'33'4522*33'55'622*33*45'622'34'55I6 ; 22*344'56'22'33'44'22'344'5'623*44*55'22'3455'622 '33 '456' ; 22 '344 '5622f33f4'5622'33'44'6 ; 233 '44 '5233'44'5'22'33'45622f33'45'66' ; 22'344'566'22'33'455' ; 233'455'622'344>55<

233'4f55'6233'44'5'622*33 '4566'22'33'44'5233'44'5622'33'455'6r'BM'ss-e22'33'44'5*6 ; 22'344*55I6233*44'55'22'33144'5622'X'W&233'44'55>6

6

f>&5+

2.4071.0070.2000.1640.2240.2710.2580.9781.5140.2210.0421.8030.6631.2887.9610.2130.1711.1770.8206.7970.7110.5960.1865.4090.3250.0790.6550.1943.1550.2471.6250.2400.3492.6131.5100.8580.2880.0180.1380.5185.4570.1420.0570.1192.0960.4350.0431.0571.2880.0340.4750.9590.025

2.2260.9320.1850.1520.2070.2500.2390.8181.4470.1850.0391.5080.5711.1547.1200.1850.1540.9840.7115.6850.5950.4980.1424.5240.2720.0660.5000.1482.4090.2071.2410.2010.2672.0001.1560.6780.2410.0140.0970.3964.1670.1090.0440.0841.6000.3320.0300.7430.9050.0260.3340.6730.017

* 9.302

TOOL XKXKUS * 0.0308

AVDUGE KUCOLM W2GHT » 301.8

MWEER CF CXLEWOTD FEME PDDNIN

312447

NORTHEAST ANALYTICAL, INC.

301 NOTT.STREETSCHENECTADY, NY 12305(518) 346-4592

PCB SUMMARY REPORT

NEA FILE NAME: 89001.HOM

CUSTOMER: J. EPASAMPLE DESCRIPTION: SEDIMENT, SECTION 617COMMENT: SAMPLE SHOWED ENVIRONMENTAL ALTERATION

Total PCBs in Sample- 9.30

PCB Homolog Distribution

Homolog Series Percent in Sample

MonoDiTriTetraPentaHexaHeptaOctaNonaDeca

4.7217.309.316.73

14.9723.2919.584.100.000.00

\5

Ortho Cl / biphenyl Residue « 1.99

Meta •*• Para Cl / biphenyl Residue * 2.30

TOTAL Cl / biphenyl Residue =4.29

312448

TABLE OF CONTENTS

1.0 Scope

2.0 Summary of Method

3.0 interference

4.0 Sample Archiving

5.0 Equipment and Apparatus

6.0 Reagents

7.0 Procedure

8.0 Quality Control

9.0 References

Paoe Number

1

2

2

3

3

4

7

21

25

r/MOSBOStSB 312449

/*"•Vluplc: 1232/1241/12(2 Cinitl: detector 1

Icqiirri: 27-JU1-I9 13:11 i«Uod: C:\KAI\GC1\11UPiltuit: 1324112Opiritor: IEI

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i: 1232/1241/12(2 Ckmil: detector 1Icqiirri: 27-JUI-H 13:11 Ittkod: C:\UX\Kl\llll

rilnau: 13241(2Operator: ESI

WbC

x 1O"1 volts

ooI

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49.60 —

312455

draft status report for temporal water column …

Documents