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WHC-EP-0708Revision 1

UC-600

Quality Assurance ProjectPlan for Waste Tank VaporCharacte rizat ion

I

!

C. D. Suydam

DatePublishedDecember 1993

Prepared for the U.S. Department of EnergyOffice of Environmental Restoration andWaste Management

Westinghouse P.O. Box 1970Hanf0rdCompanyRichland, Washington 99352

HanfordOperationsand EngineeringContractorfor theU.S. Departmentof Energy underContractDE-ACO6-87RL10930

Approved for Public Release ,_, :0 i _._11

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" T_tte qual,,ityAssurance Program Project Plan for Wa.s.te i Unctassified Category

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BD-7600-062 (08/91) WEF074 Part I

j,t,,'/./cz.. >,ID NLmber

,,.

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C. D. Suydam,Jr. 373- SI-571754

or" Lead "' ' etc _') " 'P'rojec1: Program Org Code Sponsor Agency (DOE, DOT, NRC, USGS,

Tank Vapor IssueResolutionProgram 7A300Editor Phone MSIN DOE/HQ Program (DP, EH, EM, NE, etc.)

, ,

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BD-7600-062 (08/91) WEF074 Part2

, WHC-EP-0708 REV. I

EXECUTIVESUMMARY

This QualityAssuranceProjectPlan, WHC-SD-WM-QAPP-013,appliesto four

separatevapor samplingtasks associatedwith Phases I and 2 of the Tank Vapor

Issue ResolutionProgramand supportof the RotaryMode Core DrillingPortable

ExhausterPermit. These tasks focus on employeesafetyconcernsand tank j4.

ventilationemissioncontroldesign requirements.

Previouscharacterizationeffortsand studiesare of insufficient

accuracyto adequatelydefine the problem. It is believedthat the technology

and maturityof samplingand analyticalmethodscan be sufficientlydeveloped

to allow the characterizationof the constituentsof the tank vapor space.

The goals of this effort are as follows"

Phase I

I. Identifyanalytescollectedby the samplingsystemsand obtain rough

quantitativedata describingthe constituentsof the vapor space of

tank 241-C-I03.

2. Selectthe best samplingand analyticalprocess/methodologyfor

vapor characterization.

These will be accomplishedthroughobtaininga betterunderstandingof

the tank vapor space by applyingvalidatedsampling/analyticalprocedures,

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WHC-EP-0708 REV. I

identifyingthe performance(accuracyand precision)of those methods,

understandingwhich of the methodsare best applicableto the effort,and

establishingthe samplingprotocol.

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3. From the resultsof I. (above),and in consultationwith the Tank

Vapor Conferenceand the ToxicologyPanel, revisethe list of

analytesof concernand analytesof interestfor targetedanalysis.

Phase 2

I. Fully characterizevolatilecomponentsof concernand interestin

the vapor phase of tank 241-C-I03,both qualitativelyand

quantitatively.

2. Specifymodificationsto the characterizationprocess/methodology

that will allow the vapor spacesof all HanfordSite waste tanks to

be characterized.

This will be accomplishedby developmentof a sitewidevapor verification

program,Tank AdvisoryPanel approval,and sufficientcharacterizationof the

tank vapor space contents (hazardous,flammable,and permanentgases/vapors)

to permit the cost effectiveengineeringof a mitigationor remediationsystem

for tank 241-C-I03. The Projectshall apply validatedvapor samplingand

analyticalproceduresto specifiedwaste tanks, and supportthe RotaryMode

Core Samplingprogram. This programrequiresthe qualitativeand quantitative

characterizationof analytesof concernand interestfor the permittingof a

portableexhausterto be operatedduring rotarymode core sampling.

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. WHC-EP-0708 REVoI

CONTENTS

1.0 INTRODUCTION............................ I-i

2.0 PROJECTDESCRIPTION........................ 2-I2.1 PROJECTTASKBREAKDOWN.................... 2-I2.2 SAMPLEANALYSlSTECHNOLOGIES................. 2-I2.3 QAOVERSIGHT......................... 2-2

3.0 PROJECTORGANIZATIONAND RESPONSIBILITY.............. 3-I3.1 WASTETANKSAFETYPROGRAMS.................. 3-I3.2 INDUSTRIALHYGIENEANDSAFETY ................ 3-I3.3 WHCPROCESSINGANDANALYTICALLABORATORIES(PAL) ....... 3-I3°4 325/329 PNL ANALYTICALLABORATORIES............. 3-23.5 OREGONGRADUATEINSTITUTE (OGI) ............... 3-23.6 TANKFARMSOPERATIONSANDMAINTENANCE............ 3-23.7 HEALTHPHYSlCS........................ 3-23.8 TWRSQUALITYASSURANCE.................... 3-23.9 ENVIRONMENTALDIVISION .................... 3-3

4.0 QUALITYASSURANCEOBJECTIVESFORMEASUREMENTDATA ......... 4-I4.1 INTRODUCTION......................... 4-i4.2 MINIMUMQUANTITATIVELIMITS ................. 4-24.3 PROCEDUREVALIDATION ..................... 4-24.4 ACCURACY........................... 4-44.5 PRECISION .......................... 4-54.6 COMPLETENESS......................... 4-54.7 REPRESENTATIVENESS...................... 4-54.8 COMPARABILITY ........................ 4-6

5.0 VALIDATIONOF PROCEDURES .................... 5-I5.1 ORGANICANALYSISBY SUMMACANISTERANDGC/MSORGC/FID .... 5-I5.2 ORGANICANALYSISBY DIRECTGC/FID .............. 5-25.3 AMMONIAANDHCNBY BUBBLERANDSIE .............. 5-25.4 WATER BY SILICA SORPTIONAND GAVIMETRY 5-25.5 TRITIUMBY SILICA SORPTIONAND LIQUIDSCINTiLATiONi i i i i i 5-3

6.0 SAMPLINGPROCEDURESAND SAMPLEPREPARATION ............ 6-I6.1 INTRODUCTION......................... 6-I

" 6.2 CHAIN-OF-CUSTODY....................... 6-i6.3 FIELD BLANKS ......................... 6-2

7.0 CALIBRATIONPROCEDURESAND FREQUENCY ............... 7-I

8.0 ANALYTICALPROCEDURES....................... 8-i

9.0 DATA REDUCTION,VALIDATION,AND REPORTING............. 9-I9.1 DATA REDUCTION........................ 9-I9.2 DATA VALIDATION ....................... 9-I9.3 DATA REPORTING........................ 9-I

WHC-EP-0708 REV. I

CONTENTS(cont i nued)

I0.0 INTERNALQUALITYCHECKSAND CORRECTIVEACTION ........... 10-II0.I INTRODUCTION......................... i0-I10.2 ACCURACYRELATEDQCCRITERIA ................. I0-I10.3 PRECISIONRELATEDQCCRITERIA ............... 10-I10.4 CONTAMINATIONRELATEDQCCRITERIA .............. 10-3

11.0 PERFORMANCEAND SYSTEMAUDITS ................... II-i

12.0 PREVENTATIVEMAINTENANCE..................... 12-I

13.0 QUALITYASSURANCEREPORTSTO MANAGEMENT.............. 13-I

14.0 REFERENCES............................ 14-I

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, WHC-EP-0708 REV. i

LIST OF TABLES

2-A Analytesof Concern ........................ 4-3

2-B Analytesof Interest ....................... 4-4

: 3 LaboratoryData ValidationSteps ................. 9-2

4 QC Sample Definitions....................... 10-2

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WHC-EP-0708 REV. I

LIST OF TERMS

AMS AnalyticalMeasurementSystemDOE U.S. Departmentof EnergyDQO Data QualityObjectivesEPA EnvironmentalProtectionAgencyFID Flame IonizationDetectionGC Gas ChromatographyGC/FID Gas Chromatography/FlameIonizationDetectionGC/MS Gas Chromatography/MassSpectrometryGC/TC Gas Chromatography/ThermalConductivityDetectorIC Ion ChromatographyMSA Matrix Spike AdditionMS Mass SpectrometryMZG Moist Zero GasNIOSH National Institutefor OccupationalSafety and HealthNIST National Instituteof Scienceand TechnologyOGI Oregon GraduateInstitutePNL PacificNorthwestLaboratoriesQA QualityAssuranceQAM QualityAssuranceManualQAPP QualityAssuranceProjectPlanQC QualityControlRSD RelativeStandardDeviationSandiaNL SandiaNationalLaboratoriesSIE Specific Ion ElectrodeTLV/TWA ThresholdLimit Value/TimeWeightedAverageTQL TargetQuantitativeLimitTWRS Tank Waste RemediationSystemWHC/PAL WestinghouseHanfordCompany/Processingand Analytical

Laboratories

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WHC-EP-0708 REV. i

QUALITYASSURANCEPROJECTPLAN FOR WASTETANK VAPOR CHARACTERIZATION

1.0 INTRODUCTION

This QualityAssuranceProjectPlan (QAPP)identifiesprocedures,describesapplicablequalitycontrol(QC) and qualityassurance(QA)methods,and documentsinformationthat will be used to supportvapor samplingandanalysisfor the characterizationof waste tank vapor spaces. The plan islimitedto the developmentaleffortto accomplishobjectivesoutlinedinSection2.0. WestinghouseHanfordimpactlevel 3SQ is assignedto this effortuntil the evaluationof the resultsindicatesthe need for anotherlevel.

Data qualityobjectives(DQO) are being developedto supportthedecisionsto be made using the data obtainedfrom this effort. Thesedecisionsinvolvethe chemicalconstituentscontainedin waste tank vaporspaces,and will be developedfrom samplingeffortsperformedontank 241-C-I03. The objectivesdo not includeestablishingthe mechanismofvapor formationand do not includethe characterizationof any medium otherthan the tank vapor space.

The initialobjectivesof Phase I will be to selectthe bestprocess/methodologyof tank vapor space characterizationand to obtainpreliminarymeasurementsof the vapor space constituentsin the specifiedtanks.

The ultimateobjectivesof Phase 2 are to establisha tank vapor spacecharacterizationprogramthat can be appliedto any HanfordSite waste tankand to characterizethe vapor space of any waste tank. Includedin thischaracterizationwill be an identificationof flammabilitypotentialand ahealthhazard determinationresultingfrom identificationof toxic and/ornoxiousvapor and gaseousconstituents. The detailsof the DQOs for the vaporspace characterizationeffortare subjectto evaluationand refinement. Allnumericallimitscontainedherein are tentativeand subjectto change.

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• WHC-EP-0708 REV. 1

2.0 PROJECTDESCRIPTION

2.1 PROJECTTASK BREAKDOWN

The purposeof this documentis to provideinterimQA/QC guidanceforsamplingand analyzingthe vapor space accordingto the followingtasks:

• Obtain triplicateSUMMA canistervapor samplesfor qualitativeanalysisof a specificset of organicanalytesusing a heated sample

" probe at a singlelevel in tank 241-C-I03accordingtoWHC-SD-WM-WP-198(WHC,1993).

• Obtain SUMMA canisterand solid sorbentvapor samplesfor thedevelopmentof quantitativeanalysismethodsusing a heated probe ateach of three levels in tank 241-C-I03accordingto WHC-SD-WM-WP-223(WHC,1993).

• Sample and analyzethe vapor in the tank C-I03 accordingtoWHC-SD-WM-WP-174(WHC 1992).

2.2 SAMPLEANALYSISTECHNOLOGIES

In general,the samplestaken from these tanks will be analyzedunder theQA/QC requirementsdescribedin this document. The effortwill involvetheuse of four independentsamplingand analysistechniquesin Phases1 and 2.These techniquesare:

• SUMMAI canistersamplingfol!owedby GC/MS2 or GC/FID3 organicanalysis

• SorbentTubes4

• GC/FID or GC/TC organicvapor space'analysiseither (1) after directsamplingor (2) solid sorbentsamplingof the vapor

- IStainlesssteel samplingcontainerwith electropolishedinteriorwallsand certifiedto a cleanlinessof 12 #g/m3 or 20 ppb.

2Gaschromatographicseparationof organicvaporsfollowedby massspectrometricidentificationand quantificationof elutingcompounds.

3Gas chromatographicorganicvapor separationfollowedby quantificationof the elutingcompoundsusing a monitor having a flame ionizationdetector

4pencil-likeglass or metal tubes filledwith sorbentmaterial

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WHC-EP-0708 REV. I

• Midget impingers(bubblers)I for inorganicvapor analysis.

2.3 QA OVERSIGHT

During samplingQA will performsurveillances,where applicable,inaccordancewith Section 10.4 of the QualityAssuranceManual (QAM),WHC-CM-4-2(WHC, 1988),and MRP-5.50of the ManagementRequirementsand Procedures(MRP),WHC-CM-I-3(WHC, 1988). Specificinspectionsby QC shall be based upon workpackagesand shall be documentedon a QA SurveillancePlan. Additionally,acalibrationcheck shall be performedto ensure the accuracyof the instrumentsbeing used to monitor flammablegas.

The QA requirementsfor all onsitelaboratorieswill be implementedinaccordancewith QAMS-O05/80(EPA,1983) and applicableQAPPs. Work performedby the subcontractorsshall be implementedby a QA Programthat satisfiestherequirementsof this QAPP. WestinghouseHanfordQA will performoversightandsurveillanceof offsitesubcontractoractivitieson vapor analysis.

It is intendedthat the data collectionand analysisof this effortwillsatisfyseveralobjectives. These include"

• Establishsampling/analysismethod validationprocedure(s)that willproviderequiredvapor analysismethod evaluationdata.

• Allow the selectionof the best process/methodologyfor waste tankvapor space characterization.

• Characterizevapor space of waste tank 241-C-I03perWHC-SD-WM-WP-174(WHC,1992), "EngineeringWork Plan forTank 241-C-103Phase I Vapor Phase Characterization,"includingtheidentificationof the vapor space hazardsposed by flammableandnoxious/toxicconstituents.

• Establisha vapor space analysisprogramthat can be modifiedtomeet specificcharacterizationneeds in the tank farms.

• Establishanalysesfor the radiologicalreleaseof samples.

• Modificationof existinganalyticalmethodologiesto fit thetargetedanalytesand their concentration.

IA glass cylindercontaininga small volume (15-25mL) of absorbingsolutionthroughwhich a vapor streamis bubbled.

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WHC-EP-0708 REV. I

To accomplishthese objectives,the followingprojecttasks have beenidentified:

• Publishwork plans,qualityassuranceplans,and samplingandanalysisproceduresthat are both method specificand integrated.

• Validatethe sampling/analysisprocedures.

• Evaluatevalidatedsampling/analysisprocedures.

• Design,fabricate,and installrequiredsamplinghardware.

• Performsampling/analysisReadinessReview,where required.

• Sampletank vapor space.

• Ship requiredsamplesto subcontractors.

• Prepareand analyzerequiredsamples.

• Verify and report sample analysisresults.

• PublishVapor ConferenceCommitteefindingsand recommendations.

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WHC-EP-0708 REV. I

3.0 PROJECTORGANIZATIONAND RESPONSIBILITY

The major organizationsinvolvedand their responsibilitiesin the vaporanalysisprojectare identifiedbelow:

: 3.1 WASTETANKSAFETYPROGRAMS

• Provides program direction and interfacing with customers such as,: U.S. Departmentof Energy (DOE),WashingtonState, Environmental

ProtectionAgency (EPA),etc.

• Evaluatesresultsand determinesprojectdirectionand milestonetrackingfor internalcontrol

• Performsprogramintegrationwith other waste tanksafety/characterizationprojects

• Calculatesand _'_#ortsthe resultsof vapor samplingprojects.

3.2 INDUSTRIALHYGIENEAND SAFETY

• Providesoversightfor the health and safely of workers and guidanceof the tank samplingper safety requirement:;.

3.3 WHC PROCESSINGAND ANALYTICALLABORATORIES(PAL)

• Recommendssamplingtechniques,procedures,and equipmentnecessaryto ensurethe DQOs of sampling.

• Responsiblefor the in-fieldactivitiesincludingequipmentassemblyand testing,samplecollection,chain of custody,sampletransport,validationof water vapor and radiologicalanalysis,and releaseforoffsiteanalysis. Sampleswill be transportedto the PAL, PNL 325,and PNL 329 laboratories. PAL will also have responsibilityforrefrigeratedsamplestorage,refrigeratedsamplearchiving,samplehandlingand disposal,procurementof new/modifiedsampling

o equipment,and trainingpersonnelon the samplersystem.

° Responsiblefor interfacingwith Tank Farm Operation.s& Maintenanceto supportrequiredsamplingequipmentfabrication.

• Returnsanalyticalresultsto Waste Tank Safety Programspoint ofcontact.

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WHC-EP-0708 REV. I

3.4 325/329 PNL ANALYTICALLABORATORIES

• Performsvalidationstudies,sample containerpreparation(whenrequired),and sample analysesof specifiedorganicand inorganiccompounds. Analysesare performedto PNL impact level2 or 3criteria,under the the projectQA Program.

• Returnsanalyticalresultsto Waste Tank Safety Programspoint ofcontact.

3.5 OREGON GRADUATE INSTITUTE(OGI)

• Performsmethod and equipmentvalidationstudiesper this document.

• Performsmethod and equipmentmodificationsto analyzeselectedC-I03 organicvapors.

• Performssurvey analysisof tank vaporswith best availablemethodologiesincludingestimationsof uncertainty.

• Documentactivitiesas requiredby this document (QAPP-013).

• Preparationand certificationof SUMMA canisters.

• In cooperationwith SandiaNL, return analyticalresultsto WasteTank Safety Programspoint of contact.

3.6 TANK FARMS OPERATIONSAND MAINTENANCE

• Responsiblefor the safetyof in-farmactivitiesincludinginstallationof the samplingequipmentat the tank, providingapprovedcoordinationof the samplingwith other in-tankactivities,schedulingin-farmactivities,and ensuringall documentationis inplace for sampling.

3.7 HEALTH PHYSICS

• Providesradiologicalsafetyand supportfor activitiesin the tankfarms.

3.8 TWRS QUALITYASSURANCE

• Providesprogramand projectsupportfor in-fieldactivity,plusoversightfor complianceto requirementsfor protectionofpersonnel,environment,and facilitysafety.

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WHC-EP-0708 REV. I

• Performs project assessments and documents compliance with controlsto meet regulatory requirements. The QArole on in-fieldinstruments used to monitor the gas is to ensure that their use,care, and maintenance (including calibration) comply with WHCrequirements and manufacturer information.

• 3.g ENVIRONMENTALDIVISION

• Providespoint of contactto evaluateFederal,State, and DOE• environmentalcompliancerequirementsand operationalguidelines.

• Submitsdocumentationon the programfor complianceto NationalEnvironmentalProtectionAct. Issuessite-widereportsforcomplianceto environmentalrequirements.

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• WHC-EP-0708 REV. I

4.0 QUALITYASSURANCEOBJECTIVESFOR MEASUREMENTDATA

4.1 INTRODUCTION

In additionto the usual QA topics that must be addressedin a QAPP per: QAMS-O05/80(EPA, 1983),the procedurevalidationmust also be addressed. The

followingtopicsmust be definedand discussed"

• Accuracy• Precision

Validation• Completeness• Comparability• Representativeness.

Chemicalanalyticaldata can be broadlygrouped into two categories;namely, quantitative,and qualitative. Qualitativedata determinesthepresenceor absenceof a compound,element,or ion. Qualitativedata usuallyconnotesa bias of greaterthan 50%. Quantitativedata defines the amountofa particularspecies. Modern analyticalchemistryis overwhelminglyaquantitativescienceand will be appliedto the tank targetedcharacterization.

Errors occur in the quantitationprocess. They may be bias (systematic)and affect accuracyand, if known,and are not too large and consistent,canbe used to correctraw data. The errorsmay be randomwhich affectstheprecision.Any resultingdata will have an uncertaintydue to this type oferror. These errorscan occur in sampling,samplestorageor manipulation,and analyticalseparationand analysis. Systematicand randomerrors tend toincreasewith decreasingamountsof analyte.

Accuracyis determinedby the analysisof standards. The standardsusedto determineaccuracyshall be preparedand verifiedindependentfrom thosestandardsused for calibrationpurposes.

It is the objectof this programto determinethe vapor concentrationofthe targetedanalytesto a known level of accuracyand precision(certainty).This means that both the random and systematicerrors shall be determined,as

, best as practicallypossible,with statisticalcompleteness.

The reductionof quantitativedata to qualitativedata is based on dataimportanceand the size of both types of errors. For example,quantitativedata is frequentlyidentifiedwith an error bias of no more than 50%. Biascan be the differencebetweenpercentrecoveryof a known analyteand 100.The conceptof bias is differentfrom error in that bias, when sufficientlyconsistent,allowsthe correctionof raw data for this effect. Qualitativedata usuallyconnotesa bias of greaterthan 50%. Qualitativedata allowsthereport of major, minor, and trace samplecomponents. A major componentwouldaccountfor 10-99%of the composition. A minor componentwould apply to the0.1-10%concentrationrange. Typicallya trace componentrepresents1000 ppmor less. As bias approachesand increasesbeyond50%, it generallybecomes

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WHC-EP-0708 REV. i

less consistentand appearsmore like random error. In circumstanceswherethe methodsof analysisare being developedfor complexmatricesand/or lowlevel target analytes,data qualityparameters,developedfrom initialsamples,shall be reportedregardlessof bias level.

4.2 MINIMUMQUANTITATIVELIMITS

The targetquantitativelimit (TQL) is the desiredconcentrationthat maybe reliablyquantifiedto meet the needs of this characterizationprogramwithregardsto vapor toxicityand flammability. TQL's have been establishedfortoxicityrelatedcompounds. Initially,this value has been set at(0.1)X[ThresholdLimit Value/8hour Time WeightedAverage (TLV/TWA)for thatcomponent]. The value is chosen to allow a margin of error to compensateforinaccuraciesand imprecisionin the sampleanalysisand collection. Table 2Aand 2B list the analytesthat are currentlyof highestpriority. The tablesalso show flammability,toxicity,and expecteddetectionlimits.

The actual quantitationlimitswill depend on the vapor characterizationtechnologiesused. At present,due to the number and type of compoundsto beanalyzed,three samplecollectiontechniqueswill be used. These are(I) SUMMA canister,(2) sorbenttubes, and (3) midget impingers(or bubblers).Severaltypes of sorbenttubes are neededto collectHydrogenCyanide (HCN),Ammonia,and Water (bothnormal and tritiated)vapors. The choice of sorbenttype is dependenton the component(s)of interest. Initially,an impingercollectionprocedurewill be used to samplefor HCN and Ammonia. Finallytheapplicablequatitationlimitswill dependon the measurementprocessused.Organicswill be separatedby gas chromatography(GC) followedby measurementwith eitherflame ionizationdetection(FID)or mass spectrometry(MS).Furthermore,inorganiccomponentswill be measuredby gravimetry,ionchromatography(IC), or specificion electrode(SIE).

4.3 PROCEDUREVALIDATION

Whenevera samplingand/oran analysisprocedureis proposedfor a newapplication,there is a chance that the proceduremay not providethe samequalitydata as in a proven application. Differentsamplematricescanadverselyaffect samplingand analyticalmeasurementefficiencies. Thus,proceduresneed to be validatedfor new applications. This projecthasadoptedthe validationprocedureused by the National InstituteforOccupationalSafety and Health (NIOSH). This procedureexaminesthe accuracyand precisionvalues providedby the sampling/analyticalprocedurefor 4-5concentrationswithin a specifiedvapor concentrationrange for a fixed set ofsamplingconditions. Ideally,the accuracyand precisionvalues areconsistentover the testedconcentrationrange.They all meet prescribedacceptancecriteria. NIOSH insiststhat their procedures,purportingtoprovidequantitativeresults,furnishresultsthat are within 25% of the trueconcentrationfor 95% of the measurements. To meet this accuracyobjective,the precisionof the measurementsmust have a RelativeStandardDeviation(RSD) of less than 0.105. To developthe requiredstatistics,a minimumoftriplicatesamplesare run at each concentrationlevel tested.

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Table 2-A Analytes of Concern.

Compound LFLa (ppm) TLV/TWAb (ppm) MDL: (ppm)

Dodecane - - -

Tridecane - - -, ,, ,,,,,,,

• Ammonia 16000 25 2.5,,, ,,,

NO, N20, and NO2 - - -

• Hexone 14000 50 5.0

Vinyl Acetate 26000 i0 I0,,, ,,,,

Methylene Chloride 8100 50 1.0

I,I Dichl ororethane - 200 20,,

Tributyl Phosphate - - -,, ,,

Toluene 12000 I00 100, ,,,,

Benzene 14000 O.I 5.0

Aliphatic Nitriles - - -

l-Butanol 14000 50 5.0

Acetone 21500 750 75,,,,

aLFL : Lower Flammab lity LimitbTLV = Toxicity based on Threshold Limit ValueCMDL: Method Detection Limit

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WHC-EP-0708 REV. I

Table 2-B. Analytesof Interest.

Compounds LFL (ppm) TLV/TWA (ppm) MDL (ppm).,,

Water N/A N/A N/A, ,,,

HCN - - -, ,...,, ,, i

Carbon Tetrachloride N/A 5 0.5 •,,..,,,

Hydrogen - - -,.,,,, , ,, ,,

Tritium N/A N/A N/A "......... ..,, ,

Samplingefficiencywill be determinedseparatelyfrom analyticalmeasurementefficiency. Samplingefficiencyincludesboth samplecollection/sorptionefficiencyand sampledesorptionefficiency. The VaporIssue ResolutionPrograminitiallyexpectsa consistentminimumof 75%samplingefficiency. In addition,and where justified,sample resultsshallbe correctedfor samplingefficienciesthat are less than 90%.

l

4.4 ACCURACY

SW-846, (EPA, 1986) definesaccuracyin terms of the nearnessof ameasurementto a true value and evaluatesaccuracyby determiningthe percentrecoveryof a referencesample. Althoughthere have been severalattemptstoprovidesimulatedreferencestandardsfor mixed waste samples,a suitablereferencestandarddoes not exist. Thus, accuracymust be evaluateddifferently. For the Vapor Issue ResolutionProgram,accuracyis evaluatedimplicitly. By using simplereferencestandards,relevantanalyticalmeasurementsystemsare provento be as error-freeas is practicallypossible.This error-freeconditionof the analyticalmeasurementsystem is documentedfor each batch of samples. No vapor samplesmay be processedunlesstheanalyticalmeasurementsystem (AMS) has been proven "in control"by providingan acceptablepercentrecoveryof a simple referencestandard. AMS controlmust be documentedfor each batch of samples. Analyticalaccuraciesfor somemethodswill be ensuredby a Method of StandardAdditionwhich ideallyeliminatesmatrix interferences.When used, the spikeadded must increasetheconcentrationof the selectedanalytesto a concentrationthat is (I)approximatelydouble the originalanalyteconcentrationand (2) within thelinear range of measurement.The minimizationof assignablelaboratoryerrorsshall be used to controlthe analyticaldata error. In the data qualityevaluation,the error attributableto matrix interferencesshall be reportedin terms of a matrix spike analysis.

There is a specialQA concernassociatedwith solid sorbentvaporsampling. Unless care in testingdesign is taken, it is easy to exceed thecapacityof _ sorbenttube and loose sampledue to breakthrough. Becauseofthis each sample in the test arraywill have a back-upsorbenttube in serieswith the primarysample tube to prove the adequacyof the test design. Thetestn design is evaluatedby measuringthe breakthroughof the analytein theback-uptube relativeto the total amountof analyterecovered. It is

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expectedthat no more than 20% of each analyteshall be found in the backuptube. The breakthroughshall be documentedas part of the data qualityevaluation.

4.5 PRECISION

: SW-846,(EPA, 1986) definesprecisionas the agreementbetweena set ofreplicatemeasurementsand evaluatesprecisionusing duplicateor replicatesample analysis. The conceptof precisionacknowledgesthat several

: measurementsof a single concentrationare expectedto occur over a range ofvalues. Ideally,the range of valueswill be narrow- the more narrow therange, the more precisethe measurement. As discussedabove in Section4.2,this requireslimitingthe RSD to about0.1 or the RelativePercentDifference(RPD)to 20.

Each test design will includeat least one replicatesamplewhich willdocumentprecisionfor the test. Some designsrequiretriplicatesamples,othersrequireduplicatesamples. Where vapor samplesare collectedatdifferentlevelswithin a tank, replicatesampleswill be taken for eachlevel. Whereverpossiblereplicatesampleswill be collectedin parallel,i.e., at the same time, or immediatelyafter one another,at the very least.

4.5 COMPLETENESS

The QA requirementof completenessrefers to what extent a projectdeliveredall of the analyticaldata requiredby the statementof work for agiven samplingjob. The Vapor Issue ResolutionProgramwill provideanunconditionalminimumof 90% completeness. The term "unconditional"meansthat all conditionscontributingto the failureof meetingthe completenessobjectivemust be discussedas part of the data qualityevaluation.

4.7 REPRESENTATIVENESS

This objectiveconsidersand uses sampleextractionand sample handlingprocedureswhich minimizechangesto the compositionof the tank vaporsbetweenthe time of sampleextractionand analysis. There are practicalconsiderationsthat can adverselyaffectthe representativenessof the vapor

, sample. For instance,horizontalvapor compositionvariationswill not bemeasuredas sampleswill be extractedfrom only one riser. Since verticalvapor compositionvariationsare more probable,early vapor samplesshall be

, drawn from three levels in each tank and verticalvariationsevaluated. Timeand turbulenceis expectedto eliminateany significantlayeringof the vapor.Once extractedthe vapor compositionmay change in the samplingmedium as afunctionof time or temperature. This shall be evaluatedas part of themethod validationstudies. Becauseof these studies,specialsample holdingtimes (betweensamplingand analysis)and/or samplestorageconditionsmayneed to be specified. Initiallyand until validationstudiesindicateotherwise,holdingtimes will be set at 60 days. All samplingprocedureswill includeprovisionsfor adequatepurgingof samplinglines. Purgingwillensurethe sample lines containonly extractedtank vapor.

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4.8 COMPARABILITY

The comparabilityrequirementassuresthat there will be an acceptable,minimumdifferencebetweenany two organizationsprovidingvapor samplingdatafrom the same source. One way to evaluatecomparabilityis to comparereplicateresultsfrom the two organizationsand accept some maximumRPDcalculatedfrom the mean correspondingto the replicatedata. The targetvalue for the RPD for the Vapor Samplingprojectis ±20.

Both PNL and OGI have been given responsibilityfor organicanalyticalmethod development. While there are no currentplans to transferanalyticaltechnologyto the 222-S Laboratory,acceptablecomparabilityis expectedsince(I) the programrequirescompletedocumentationof procedurevalidationandinstructions,and (2) analyticalprocedureswill be based on existing,standardlab measurementpractices,such as SpecificIon Electrode(SIE), IonChromatography(IC), etc.

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5.0 VALIDATIONOF PROCEDURES

The validationtest proceduresmust be consideredseparatelyfor each ofthe technologiesproposedto satisfythe applicablescope of this QAPP.Validationtest resultsmay vary with:

• • Changes in major componentsof the vapor

• Changes in samplingtechnique,i.e., impingerversus sorbenttube or: SUMMA canister

• Changes in samplingconditions,i.e., sampleflow rate andtemperature

• Changes in the way the sample is presentedto the measurementsystem, i.e. as a mixtureversus by separatedcomponentsor as aconcentratedvolumeversusdilutedby some carriergas

• Changes in measurementsystem,i.e., Ion Chromatographyversus MassSpectrometryor SpecificIon Electrode

• Changes in samplemanipulation,i.e., concentrationor dilution,etc.

The five technologiesto be discussedare as follows:

• Analysisof organicvapors

- Samplecollectionby SUMMA canisterfollowedby GC/MS or GC/FIDanalysis

- Direct GC/FIDor GC/TC analysis

• Analysisof inorganicvapors

- Ammoniaand HCN--Samplecollectionby midget bubbler followedDy SIE or IC analysis

- Water--Samplecollectionby sorbenttrap (SilicaGel) and: analysisby Gravimetry

- Tritium--Samplecollectionby sorbenttrap (SilicaGel) and. analysisby LiquidScintilationcounting

. 5.1 ORGANICANALYSISBY SUMMA CANISTERAND GC/MS OR GC/FID

The samplecollectionefficiencyfor SUMMA canistersis 100%, but thereare well documentedsampledesorptionprcblems. It is well known that polarcow,poundsadsorbonto the interiorsurfaceof the SUMMA and are notquantitativelyreleasedwhen sample volumesare extracted. Becauseof thissampledesorptionefficiencymust be addressedin the validationprocedure.Anothersampledesorptionprobkemis that surfaceadsorbedcompoundshave been

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known to undergochemicaltransformations,involvinghydrationand oxidation,that change the compositionof the vapor as a functionof time in thecanister. This time effectmust also be checkedas part of the validationprocess. Becauseof these sampledesorptionproblems,therequiredanalyticalquantitationshall depend on multipleMatrix Spike Addition (MSA) insteadof aseriesof calibrationgas mixtures. In this procedure,spikesof chemicallyrepresentativecompoundsat increasinglevelswill be added to determinetherequiredresponsefactorsexclusiveof any samplematrix effects. Thus,Validationstudiesshall addressthe followingSUMMA canistersamplingand °analysiseffects"

• Time in the canister• Temperatureof desorption• Water vapor contentof vapor sample• Sampleconcentratingmethods• Level of spike addition• Equipmentoperatingconditions.

5.2 ORGANICANALYSISBY DIRECTGC/FID

There are no samplecollection/desorptionefficiencyproblemsto beaddressedin the validationproceduresince the samplingof vapors is direct.The requiredanalyticalquantitationwill depend on eitherMSA or by a set ofsimulated,multi-concentrationlevel,vapor calibrationstandards. Suchstandardsare readilypreparedin specialplasticsamplebags using a singlecalibrationliquidmixture and the appropriateliquid and gas mixture.Validationstudiesshall addressthe followinganalyticaleffects:

• Water vapor contentof vapor sample• Sample concentratingmethods• Level of spike additionconcentrationrange of standards• Instrumentoperatingconditions.

5.3 AMMONIAAND HCN BY BUBBLERAND SIE

Both of these gases will be absorbedin a specialsorbentsolutionas thevapor sampleis passedthrougha midget impinger,or bubbler. Ti,econditionsfor samplecollectionare part of a publishedNIOSH procedure. The vaporsamplingfor Ammoniaand HCN need not be validatedif the NIOSH samplingconditionsand proceduresare used. The requiredanalyticalquantitationwilldependon MSA.

5.4 WATER BY SILICA SORPTIONAND GAVIMETRY

While this is not a NIOSH publishedprocedure,it is well documented.Aslong as the samplingconditionsconformto establishedlimits,no additionalvalidationis required.

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5.5 TRITIUMBY SILICASORPTIONAND LIQUIDSCINTILATION

While this is not a NIOSH publishedprocedure,it has been validatedbythe 222-S Laboratory. As long as the samplingconditionsconformtoestablishedlimits,no additionalvalidationis required.

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6.0 SAMPLINGPROCEDURESAND SAMPLE PREPARATION

6.I INTRODUCTION

This sectionof the QAPP concernsthe QA aspectsof two differentsamplingconfigurations: (I) a vapor/aerosolsamplingusing a portablesample

• collectiondevice and an in-tankbubblerarray or SUMMA sampletube and (2) amobile samplingvehicle,designatedDMLI, capableof collectingSUMMA, solidsorbentor bubblersamplesat up to three tank vapor levels. Includedin this

. document is the requirementfor proceduresthat describethe specificsamplingtechniquesoutlinedin Section2.0. These proceduresshall be subjecttorevisionas knowledgeand experiencewith the techniquesis gained over time.Proceduralguidanceis availablefrom NIOSH publicationsand ASTM ambientairsamplingprocedures,such as ASTM D 1357 (ASTM,1989) and D 3614 (ASTM, 1990).

Samplingprocedureswill document both the pre- and post-samplingactivities. The followingsamplingactivitieswill be addressedfor each ofthe samplingtechnologiesapplicableto this QAPP:

l

• Cleaningand cleanlinesstestingof SUMMA canisters

• Reagentpreparationand fillingof solid sorbenttubes

• Reagentpreparationand fillingof bubblers

• Cleaningand cleanlinesstestingof samplingtubing

• Vacuum testingof samplingsystem

• Applicablesampleholdingtime limit prior to analysis

• Sampleline flushing,testingand flushingacceptancecriteria

• Sampledata recordingand calculationrequirements

• Field and reagentblank preparation

• Set-up,samplecollection,and shut-downoperationof portablesamplecollectiondevice

|

• Set-up,samplecollection,and shut-downoperationof DMLI

, • Post-samplehandling,chain-of-custodyactivities,and sampleradioactivitylimit verification/documentationfor all samplingevents.

6.2 CHAIN-OF-CUSTODY

As noted above, samplecustodywill be verifiedfrom the samplecollectionin the field throughreceiptof the samplesby using WHC approvedchain-of-custodyforms. These forms recordthe identityof personsin custodyof the samples,sample identity,and time and date of transferof custody.

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The form shall accompanythe samplewhile it is being transported. To verifycustody,samplesshall be within sight of the personsassignedcustodyunlessthe samplesare containedin a lockedor securedarea.

6.3 FIELD BLANKS

A final samplingrelatedQA concernmust be addressed- field blanks.Field blanksdocumentthe absenceof samplecontaminationfrom samplecontainersor reagentsbroughtto the field. Every test plan will includeatleast one unexposed,compositeReagentBlank for each set of vapor samples.The term "composite"refersto the followingthree potentialsourcesofcontamination. A set of samplesare those samplesrequiredby both the workplan and this QAPP for a given tank. The ReagentBlank is unexposedin thefield. The purposeof the ReagentBlank is to demonstratethat the sorbentmedia used in the samplingdevices is not contaminated(I) as receivedfromthe supplier,(2) by the samplecontainer,(3) or by handlingduringpreparationor field activities. The ReagentBlanksmust be unexposedtoeliminatesourcesof contaminationeither from the samplevapor or thesamplinglocationambientair. The ReagentBlanks for liquid sorbentmediaare analyzeddirectlywithoutextraction. The ReagentBlank for solid sorbentmedia are analyzedafter extraction. Thus, the expectedanalyticalresultsshall be either (I) below the methoddetectionlimit for the analyteinquestionor (2) below some statisticallyderivedmaximumconcentration. TheReagentBlank for SUMMA canistersshall also be unexposedin the field. Thelaboratorywill be filledwith moist zero gas (MZG) prior to analysis. SeeprocedureT014 (EPA, 1988) for the definitionof MZG. The maximum allowedlimitsfor the ReagentBlank shall be statisticallyderived. Each reportinglaboratoryis requiredto develop,document,and apply acceptancecriteriatothe ReagentBlank.

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7.0 CALIBRATIONPROCEDURESAND FREQUENCY

This sectionaddressesthe QA requirementsfor the calibrationof vaporsamplingand analysisequipment. The relevantequipmentincludes(I) samplingtemperatureand pressuregages and (2) analyticalmeasurementsystems. Ingeneralall calibrationsmust be verifiedas currentbefore sampleanalysis

• can be performed. All equipmentrequiringcalibrationwill be uniquelyidentifiedand log books,or other suitabledocumentation,will be maintainedto recordcalibrationdata and, where appropriate,the next required

. calibrationdate. CalibrationFrequenciesfor analyticalmeasurementsystemsthat differ from the manufacturer'srecommendationswill be determinedby astatisticalanalysisof calibrationcheck sampleresults. As long as checkstandardsare within the pre-establishedacceptancelimits,the previouscalibrationis valid. Reportinglaboratoriesare requiredto develop,document,and apply acceptancecriteriato calibrationcheck results. Anytime the systemconfigurationchangesfor maintenance,the systemcalibrationwill be repeatedand documented.

ProceduresT012 (EPA, 1988) and T014 (EPA, 1988) provideusefulguidancefor GC/MS and GC/FID calibrationinformation. Applicablecalibration,calibrationchecking,and calculationprocedureguidance is also containedinASTM (ASTM,1986) and NIOSH publicationssuch as (Taylor,Kupel, 1977),(Busch,Taylor, 1981).

The purityof water and reagentsfor standardsand workingsolutionsshouldbe describedin standardoperatingprocedures,or as part of theanalysisreport. Data producersare requiredto purchasestandardstraceableto the NationalInstituteof Scienceand Technology(NIST),where possible,and to have on file certificatesof traceability,where available.

Standardsfrom commercialsourcesshall be replacedno later than theexpirationdate suppliedby the manufacturer. Reportinglaboratoriesshalldevelop,document,and apply shelf life and storagelimitationsto allcalibrationstandards.

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8.0 ANALYTICALPROCEDURES

The analysisof all vapor sampleswithin the scope of this QAPP shall beimplementedin accordancewith the procedureswrittenand approvedby thelaboratoryperformingthe analysis. These proceduresshall meet the followinggeneralcontentrequirements:

• Scope• Applicablereferencedocuments• Method summary• Applicability• Interferences• Requiredequipment• Reagentsand materials• Safetyprecautions• Calibrationand standardization• Analysisproceduresteps• Calculations• Bias (fromvalidationstudy)and Precision.

Laboratoriesand samplingoperationsshall maintaina list of all currentprocedures,either temporaryor permanent,that are being used for thesamplinganalysisof tank vapor. Temporaryproceduresneed not be detailedorformalized. Projectreportswill containnotificationof proceduresrevisedduring the samplingand/or analysisof relatedvapor samples.

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g.o DATA REDUCTION,VALIDATION,AND REPORTING

9.1 DATA REDUCTION

All calculationsand unit conversionsare confirmedby recomputationand/orreview by a second,technicallyknowledgeablepersonwho did not

: generatethe data. No blank corrections,averagingof duplicates,or othermanipulationof data are performedin the laboratory. Any raw laboratorydatawhich is convertedfrom instrumentreadingsto concentrationunits,by

: comparisonto a standardcurve, is accompaniedby the standardcurve analysisand correlationcoefficient,if used. The concentrationof standardsolutionsand instrumentreadoutsare correlatedto the desiredfinal reportconcentrationunits, so that a minimumof unit conversionsis necessary.

Data transcriptionsare reviewedand confirmedby the responsiblescientistin the laboratoryand/orby the managerprior to releaseof theFinal data report.

g.2 DATA VALIDATION

Laboratorydata validationis a continuousprocessperformedat each stepof the analyticalmethod. The analyst,responsiblescientist,manager,and QAofficerall participatein the data validation. The analyticaldatavalidationprocessstartswith the verificationof sample receiptandcontinuesthroughapprovalof the final report. The general steps utilizedinlaboratorydata validationfor this project,and the responsiblestaff,areshown in Table 3.

The validateddata report that the laboratorysupplysat the completionof the sampleanalysiswill includethe informationfrom the validationreviewas well as the analysisresults.

9.3 DATA REPORTING

The report packageis preparedafter all laboratoryanalyticaldata hasbeen compiledand validated. The compositionof the completedata packagedependson the activitiesassignedto the reportingunit. The originalof the

' data packageis retainedby the reportingunit and a legiblecopy is sent tothe data requestor. The compositionof the data packageshall includethefollowing,as applicable:

n

• Chain-of-custodyrecordsand any field samplingobservationsanddata sheets

° Summaryof all non-QC sampleanalysisresults including:

- Sample identification

- ppmv analyteconcentration

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- Analytebreakthroughreport

- Completenessreport.

• QA/QC report confirmingthat:

- Recoveryof calibrationcheck standardscorrespondingto: reporteddata met establishedacceptancecriteria.

- Fresh calibrationcheck standardswere preparedat a frequency" consistentwith establishedcriteria.

- Calibrationcheck standardchemicalswere stored underconditionsconsistentwith establishedcriteria.

- Recoveryof lab controlstandardscorrespondingto reporteddata met establishedacceptancecriteria.

- Fresh lab controlstandardswere preparedat a frequencyconsistentwith establishedcriteria.

- Lab controlstandardschemicalswere stored under conditionsconsistentwith establishedcriteria.

- Blank(s)analysesmet establishedacceptancecriteria.

- Sampling,analysis,calculationsand method detectionlimitswere performedor determinedby existing(temporaryorpermanent)writtenprocedures.

• Reportexplainingnecessaryproceduredeviationsand analyticalproblems

• Reportlistingmethod detectionlimit for each reportedanalyte

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• 10.0 INTERNALQUALITYCHECKS AND CORRECTIVEACTION

10.I INTRODUCTION

Internalqualitycheckswill be performedon the samplingand analyticalsystemsby preparingand analyzingspecialsamplesas specifiedin Section4.0

: of this QAPP. These samplesincludefield blanks,calibrationchecks,duplicates(or matrix spikeduplicates),and matrix spikes. To promoteaconsistentinterpretationof QC sampleterminology,Table 4 lists the QC

- sampledefinitionsused in this QAPP. The analyticalresultsof these samplesdeterminethe qualityof th.=vapor samplingresults. Each set of vaporsampleswill have a sub-setof correspondingQC samples. The evaluationofthese QC sampleresultsdeterminethe qualityof the correspondingvaporsampleresults. Thus, vapor sampleresultsmay be evaluatedas "quantitative"measurementsor "qualitative"estimates. The vapor sampleresults,whose QCsamplessatisfy establishedacceptancecriteria,are considered"quantitative."

10.2 ACCURACYRELATEDQC CRITERIA

As noted above in Section4.0 of this QAPP, prior to the analysisof anyvapor sample,the analyticalmeasurementsystemmust be corfirmedto be "incontrol." This is demonstratedby verifyingthat the analyticalmeasurementsystemrespondsas expectedto (I) lab controlstandardand (2) a typicalcalibrationstandard. The lab controlstandardis preparedin deionized(DI)water,or other suitablesolventmatrix, and has no expectedsamplematrixinterferences.The inabilityto obtain an acceptablerecoveryfrom thisstandardstronglyindicatesa seriousproblemwith the analyticalmeasurementsystem. Any problem(s)must be investigatedand resolvedprior to using theanalyticalmeasurementsystemto measurevapor samples. "Thesecond checkstandardverifiesthat the initial,or last, calibrationis still valid.Failureto confirmthe calibrationstatus,requiresrecalibrationof theinstrumentprior to quantitativeanalysisof vapor samples.

If the analyticalmeasurementsystem can be shown to be "in control,"the matrix spike recoverycan be used as a measureof the method accuracy.

, 10.3 PRECISIONRELATEDQC CRITERIA

Data precisionis the secondhalf of data qualityevaluation. Where- vapor samplesare extractedfrom severallevelswithinthe tank vapor space,

replicate,even duplicate,sampledata can be used to calculate(I) the totalanalyticalvariance,(2) the total spatialvarianceand (3) the total varianceof the mean. The analyticalvarianceis relatedto all the processesthattake place in the field and laboratory. The spatialvarianceis relatedtoany existingvapor layeringin the tank. The varianceof the mean is relatedto the combinedeffectof both the analyticaland spatialvariances. Thesevariancesneed to be calculatedfor each reportedanalyte.

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Table 4. QC SampleDefinitions.

QCSample Name Definition

Reagent BLank This is an artificial sample designed to confirm the absence ofcontamination introduced from the sampling container and the samplingmedium. The sample is unexposed to tank vapors but is field handledduring sample Labeling activities. SUMMAcanisters shall be filledwith moist zero air prior to analysis. Each reporting Lab is requiredto develop, document, and apply statistical acceptance criteria forthe evaluation of this special sample.

Preparation BLank This is an artificial sample designed to confirm the absence ofcontamination from sample preparation chemicals, i.e., solvents,reagents, etc. This sample is prepared by the analyzing Laboratory andis required to develop; document, and apply statistical acceptancecriteria for the evaluation of this special sample.

Field _urrogate This is an artificial sample designed to determine the effect of timeand sample storage conditions on anatyte concentration once extractedfrom the tank vapor. The sample is prepared by the analyzingLaboratory by adding a concentration of anatyte to the absorbingmediumand determining the recovery of the added anatyte when thesamples return from the field. Consistent recovery data can be used tocorrect calculated results.

Calibration CheckStandard This is calibration solution or gas mixture that is designed to verifythat the instrument response factor for a given anatyte has notchangedsignificantly since the-Last complete calibration. Eachreporting Lab is required to develop, document, and apply statisticalacceptance criteria for the evaluation of this special sample. Failureto meet the acceptance criteria requires a complete recatibration.

Lab Control Standard This is an artificial sample designed to confirm that the analyticalmeasurementsystem is "in control", i.e., can accurately measure erelevant anaLyte in a simple solution or gas mixture free of matrixinterferences. Typically, these solutions contain one or a fewanatytes in a commonsolvent (DI Water, Methanol, air, etc.). Eachreporting Lab is required to develop, documentand apply statisticalacceptance criteria for the evaluation of this special sample. Failureto meet the acceptance criteria requires a shut down of the analyticalmeasurement system for troubleshooting and/or repairs.

Matrix Spike This is an artificial sample designed to measure the analytical errordue to matrix interferences. The sample is prepared by adding a knownamountof anatyte to an aliquot of a field sample. The percentrecovery of the added anatyte is determined and reported. Bycontrolling the non-matrix error (See above), the percent recovery ofthis special sample is used as a measure of the methocl accuracy.

Matrix Spike Duplicate This is an artificial sanNoledesigned to measure the method precision.This sample is • duplicate of the matrix spike sang,re. A conl}arison ofthe two matrix spike percent recovery values provides the requiredevaluation of method precision.

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WHC-EP-0708 REV. I

10.4 CONTAMINATIONRELATEDQC CRITERIA

Field and PreparationBlanks are preparedand analyzedto evaluatethepresenceof contaminationfrom incompletelycleanedsamplecontainersor fromimproperlypreparedreagents. See Section6.3 for details. By verifyingtheabsenceof contamination,via acceptableField and PreparationBlanks,the useof Matrix Spike Recoveryas a measureof method accuracyis furtherjustified.

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11.0 PERFORMANCEAND SYSTEMAUDITS

Vapor samplingwill be performedaccordingto the activitiesfound inWHC-SD-WM-WP-174(WHC, 1992). Tank Farms Environmentalor ProcessEngineeringand QC shall have personnelperiodicallyin the field to ensurethat thesamplingis performedper the procedureswritten as part of the experiencegained in Phase i of this project. In addition,QA personnelmay conductq

additionalsurveillanceactivitiesfor both on and offsitelaboratoriesinaccordancewith CM-4-2 (WHC,1988). The purposeof these surveillanceswill

: be to verify conformanceto unreportedQAPP requirementsand performanceaccordingto establishedprocedures.

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12.0 PREVENTATIVEMAINTENANCE

The most significantpiecesof equipmentinvolvedin this effortare thegas chromatographs,the mass spectrometer,and the samplingsystem purge pump.The rest of the onsite equipmentconsistsmainly of hot water heated sampletubing,electricallyoperatedvalves,calibratedgages and meters,and other

equipmentwhich can be easilyrepaired,fabricated,or obtained. Groupsresponsiblefor major equipmentsystemswill developa spare parts list andmaintainthe listed spares. A 48-houravailabilityfor these spares is

: required.

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13.0 QUALITYASSURANCEREPORTSTO MANAGEMENT

Qualityassurancewill be documentedin the data report. This data willmeet all data qualityobjectivespresentedin this QAPP or it will bequalifiedwith an accompanyingexplanationof any variances.

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14.0 REFERENCES

ASTM, 1986,RecommendedPracticefor Planningthe Samplingof the AmbientAtmosphere,ASTM ProcedureD 1357-82,Volume 11.03,AmericanSocietyforTestingand Materials,Philadelphia,Pennsylvania.

_ ASTM, 1986,Practicefor EvaluatingLaboratoriesEngaged in SamplingandAnalysisof Atmospheresand Emissions,ASTM ProcedureD 3614-81,Volume 11.03,AmericanSocietyfor Testingand Materials,Philadelphia,

; Pennsylvania.

ASTM, 1986, Qualificationof MeasurementMethodsby a Laboratorywithin theNuclearIndustry,ASTM C 1068,AmericanSocietyfor TestingandMaterials,Philadelphia,Pennsylvania.

Busch,K. A., and D. G. Taylor, 1977, ChemicalHazardsof the Workplace;ACSSymposiumSeries 149, AmericanChemicalSociety,Washington,D.C.

EPA, 1983, InterimGuidelinesand Specificationsfor PreparingQualityAssurancePlans, QAMS-O05/80,U.S. EnvironmentalProtectionAgency,Washington,D.C.

EPA, 1986, Test Methodsfor EvaluatingSolid Waste, SW-846 Rev. O,U.S. EnvironmentalProtectionAgency,WashingtonD.C.

EPA, 1988, Compendiumof Methodsfor the Determinationof Toxic OrganicCompoundsin AmbientAir, EPA/600/4-89/017,U.S. EnvironmentalProtectionAgency,ResearchTrianglePark, North Carolina.

Taylor,D. G., R. E. Kupel,and J. M. Bryant,1977, Documentationof the NIOSHWlidation Tests,DHEW (NIOSH)PublicationNo. 77-185,Cincinnati,Ohio.

WHC, 1988,ManagementRequirementsand Procedures,WHC-CM-I-3,WestinghouseHanfordCompany,Richland,Washington.

WHC, 1988, QualityAssuranceProgramManual,WHC-CM-4-2,WestinghouseHanfordCompany,Richland,Washington.

WHC, estimated1992, EngineeringWork Plan for Tank 241-C-103Phase ] Vapor, Phase Characterization,WHC-SD-WM-174,Rev. O, WestinghouseHanford

Company,Richland,Washington.

B

WHC, 1993,EngineeringWork Plan for Aerosoland VaporSample CollectioninTank 241-C-I03,WHC-SD-WM-WP-198,Rev. O, WestinghouseHanfordCompany,Richland,Washington.

WHC, 1993, EngineeringWork Plan for Tanks 241-BY-I04,105, 106 Vapor PhaseCharacterization,WHC-SD-WM-WP-223,Rev. O, WestinghouseHanfordCompany,Richland,Washington.

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DISTRIBUTION

Number of copies

OFFSITE

2 U.S. Departmentof Enerqy° 1000 IndependenceAve SW

EM-36Washington,D.C. 20585e

Kenneth LangCharles O'Dell

I U.S. Department of Enerqy1000 IndependenceAve SWEM-35Washington,D.C. 20585

M. Corn

32 CharlesS. Abrams1987 VirginiaIdaho Falls, ID 83404

David O. Campbell (I)102 Windham RoadOak Ridge, TN 37830

Fred N. Carlson (I)6965 North 5th WestIdaho Falls, ID 83401

i Air Products and Chemicals7201 Hamilton BlvdAllentown, PA 18195-1501

George E. Schmauch$

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OFFSlTE

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i Harvard School of Public Health665 Huntington AveBldg I, Rm G-IBoston, MA 02115

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I Waste Policw Institute555 Quince Orchard RoadGaithersburg, Maryland 20872-1437

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I NUCON7000 Huntley RoadP.O. Box 29151Columbus, OH 43229

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I Northwest Instrument Systems, Inc.3100 George Washington WayRichland, WA 99352

M. Story

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DISTRIBUTION(continued)

OFFSlTE

I Oak Ridge National LaboratoryP. O. Box 2008MS-6495

Oak Ridge, TN 37831

, Charles W. Forsberg

i Oregon Graduate Institute of Science &Technoloqy19000600 NWVon NeumanBeaverton, OR97006

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I Oak Ridge National LaboratoryAnalytical Chemistry DivisionP.O. Box 2008Oak Ridge, TN 37831

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DISTRIBUTION (continued)

ONSITE

I0 U.S. Department of Enerqy,Richland Operations Office

R. F. Christensen (8) A4-02R. E. Gerton A4-02Public Reading Room AI-65 "

9 Pacific Northwest Laboratory

T. R. Clauss P8-08J. S. Fruchter K6-96S. C. Goheen P8-08B. M. Johnson (3) KI-78B. D. Lerner P8-08R. B. Lucke P8-08PNL Technical Files K]-II

33 Westinqhouse Hanford Company

H. Babad R2-31J. R. Bell R3-09M. L. Bell T6-16R. J. Blanchard RI-17B. Conrad H5-09C. DeFigh-Price B4-55J. C. Fulton R2-31K. A. Gasper R2-08J. M. Grigsby H5-32D. J. Hart R3-54J. L. Huckaby R2-78M. N. Islam R3-08C. A. Kuhlman B3-30T. L. Moore H5-09

6

J. W. Osborne (10) R2-78I. E. Reep R2-08T. P. Rudolph R3-54 .M. H. Shannon H5-30C. D. Suydam SI-57

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