Waste Characterization Plan for the Hanford Site Single-Shell Tanks

WHC-EP--0210-Rev. 3-App. D

DE92 008571

Waste Characterization Planfor the Hanford SiteSingle-Shell TanksAppendix D - Quality Assurance ProjectPlan for Characterization of Single-ShellTanks

J. G. HillW. I. WintersB. C. SimpsonWestinghouse Hanlord Company

J. W. BuckP. J. ChamberlainV. L. HunterPacific Northwest Laboratory

Date Published

September 1991

Preparedfor the U.S.Departmentof Energy _{_Officeof EnvironmentalRestoration _._ [" _andWasteManagement

(_ Westinghouse P.O.Box1970HanfordCompanyRichland,Washington99352

Hanford Operations and Engineering Contractor for theU,S, Department of Energy under Contract DE-AC06-87RL10930 ,,

_C__ _,(,

Approved for Public Release ,...,.._

LEGALDISCLAIMER

Thisreportwaspreparedas anaccountof worksponsoredbyan agencyof theUnitedStatesGovernment,NeithertheUnitedStatesGovernmentnorany agencythereof,norany oftheiremployees,norany oftheircontrectors,subcontractorsor theiremployees,makesanywarranty,expressor implied,or assumesany legal liabilityor responsibilityfor theaccuracy,completeness,or any third party's useor the resultsof suchuGeof any information,apparatus,product,or processdisclosed,or reprer,ents that itsusewould notinfringeprivatelt'owned rights, Referenceherein toanyspecificcommercialproduct,process,or serviceby tradename,trademark,manufacturer,or otherwise,doesnot necessarilyconstitUteor imply its endorsement,recommendation,orfavoring by the United StatesGovernmentoranyagencythereofor itscontractorsor subcontractors.The viewsandopinionsof authorsexpressedhereindo not necessarilystateor reflect thoseof the UnitedStatesGovernmentor anyagencythereof.

This reporthasbeen reproducedfromthe bestavailablecopy.

Availablein papercopyandmicrofiche.IIFAvailableto Ihe U.S. Departmentof Energy

andits contractorsfromOfficeof Scientificand TechnicalInformationP,O.Box 62Oak Ridge,TN 37831(615) 576-8401

Availableto the public fromthe U.S. DepartmentofCommerceNationalTechnical InformationService5285 Port Royal RoadSpringfield,VA22161(703) 487-4650

Pdnled in the United States oi America

OlSCLM-I.CHP (1-91)

WHC-EP-0210REV 3

QUALITYASSURANCEPROJECTPLANFOR CHARACTERIZATIONOF

SINGLE-SHELLTANKS

APPENDIXD

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CONTENTS

1.0 INTRODUCTION........................... DI-I

2.0 PROJECTDESCRIPTION ...................... D2-I

3.0 PROJECTORGANIZATIONAND RESPONSIBILITY ............ D3-I

4.0 QA OBJECTIVESFOR MEASUREMENTDATA ......... ...... D4-I

5.0 SAMPLINGPROCEDURES ...................... D5-I(

6.0 SAMPLECUSTODY .................. D6-I6.1 SAMPLEBREAKDOWNAND'SUB½AMPLING ............. D6-I

7.0 CALIBRATIONPROCEDURESAND FREQUENCY. . • ........... D7-I

8.0 ANALYTICAl.PROCEDURES ..................... D8-I

9.0 DATA REDUCTION,VALIDATION,AND REPORTING ........... D9-I

10.0 INTERNALQUALITYCONTROL ........... DI0-II0._ GENERALDISCUSSIONOF SiNGLE-½HELLTANK

QUALITYCONTROLOBJECTIVES................ DI0-I10.2 SAMPLINGQUALITYCONTROL ............. DI0-410.3 SAMPLE BREAKDOWNQUALITYCONTROL ............. D10-510.4 METAL CHEMICALPARAMETERS .......... DI0-6

10.4.1 Metals--InductivelyCoupiedPlasmaOpticalEmissionSpectroscopy....... DI0-6

10.4.2 Metals--GraphiteFurnaceAtomicAbSorption.... DI0-810.4.3 Metals--HydrideAtomicAbsorption ........ • DI0-I010.4.4 Metals--ColdVapor AtomicAbsorption ....... DI0-I010.4.5 Metals--Fluorimeter............... DI0-I010.4.6 Metals--UltravioletSpectrophotometry....... DI0-11

10.5 ANION CHEMICALPARAMETERS ............ • DI0-1110.5.1 Anions-lonChromatography............. DI0-1110.5.2 Anions--Spectrophotometry............. DI0-1110.5.3 Anions--SelectiveIon Electrode ......... DI0-1110.5.6 Anions--Distillation............... G!0-1210.5.7 Anions--pH ................... DI0-1210.5.8 Anions--TotalInorganicCar_on .......... DI0-1210.5.9 Other Methods--NH3, Fe(CN)6TM .......... DI0-13

10.6 ORGANICPARAMETERS.................... DI0-1310.6.1 Organic--TotalOrganicCarbon (TOC) ........ _I0-i310.6.2 Organic--Total/Extractable

OrganicHalides (TOX/EOX)............. DI0-1310.6.3 Organic--Complexants ....... DI0-1310.6.40rganic--GC/MS (VolatiieOrganicsby Purge and

Trap and SemivolatileOrganicsby CapillaryColumns) ............... DI0-14

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#

CONTENTS (continued)

10.7 RadiochemicalParameters ............. DI0-15I0.7.1 Radionuclldes--AlphaDiO_1510.7.2 Radionuclides--Beta.......... DI0-171o.7.3Radionuclides--Beta/LiquidS intiliation..... DIO-IB10.7.4 Radionuclides--GammaEnergyAnalysis ....... DI0-1810.7.5 Radionuclides--MassSpectrometry .......... DI0-19

I0.8 PHYSICALMEASUREMENTSPARAMETERS ........ DI0-1910.8.1 PhysicalMeasurements--BulkDensity ........ DI0-19I0.8.2 PhysicalMeasurements--ParticleSize ....... DI0-2010.8.3 PhysicalMeasurements--Penetrometer. .... DI0-2010.8.4 PhysicalMeasurements--Viscosityand Rheology , . . DI0-2010.8.5 PhysicalMeasurements--Porosityand Compressive

Strength ........... DI0-2010.8.6 PhysicalMeasurement_-DS6/TGA .......... DI0-2010.8.7 PhysicalMeasurement--wt%Water .......... DI0-2010.8.8 PhysicalMeasurement--Other............ DI0-21

10.9 CHARACTERISTICSPARAMETERS................ DI0-2110.9.1 TCLP .................... DI0-2110.9.2 Chemical Oxygen Demand .............. 010-21

11.0 LABORATORYPERFORMANCEAND SYSTEMAUDITS ........... 011-I

12.0 PREVENTIVEMAINTENANCE..................... D12-I

13.0 DATA ASSESSMENTPROCEDURES .................. D13-I

14.0 CORRECTIVEACTION ....................... D14-I

15.0 QUALITYASSURANCEREPORTSTO MANAGEMENT............ D15-I

16.0 REFERENCES .......................... D16-I

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LIST OF FIGURES

D-I Field Chain-of-CustodyRecord .................. D6-2

D-2 325-A Hot Cell Chain-of-Custody ................. D6-3

D-3 ALO Chain-of-Custody....................... D6-4

D-4 222-S TravelerCard ........................ D6-5

D-5 Sample CheckoutList ....................... D6-6

D-6 Data and InformationFlow at 222-S Laboratory .......... D9-5

D-7 Data and InformationFlow at 325 Laboratory . .......... D9-6

LIST OF TABLES

D-I Matrix of TestingObjectivesand Data Users ............ D4-3

D-2 Summaryof Data QualityObjectives ................ D4-6

D-3 Data QualityObjectivesand LaboratoryCapabilities ....... D4-17

D-4 Assessmentof AnalyticalDetectionLimits ............ D4-27

D-5 Sample BreakdownProcedures ................... D6-7

D-6 QualityControlGuidelinesfor Characterizationof Single-ShellTank Wastes .................. DI0-33

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LOCATORPAGE

, ,,, ,,, ,li ,, , ,, ,,, '

QAPjP Element supportin9 Document Section(s)i I [ I

Project DOE/RL 89-16 1.0 and 2.0Description WHC-EP-02I0

Project WHC--EP-O2g4 4.0Organization QAPjP NO. SA-O01 (PNL) 4.0

WHC-SD-CP-QAP,.P-O02 2.0

QA Objectiyes QAPP No.SA-O01 5.0WHC-SD-CP-QAPP-O02 3.0

Sampling WHC-EP-0210(Rev 2) 3.0Procedures 3.I

3.2i

Sample Custody QAPjP No. SA-O01 (PNL) 5.0WHC-SD-CP-QAPP-O02 7.0

Calibration QAPjP No. SA-O01 (PNL) 8.0

Procedures WHC-SD-CP-QAPP-O02 6.0

Analytical QAPjP No. SA-O01 (PNL) 9.0Procedures WHC-SD-CP-QAPP-O02 7.0

WHC-EP-0210 5.0

Data Reduction QAPjP No. SA-O01 (PNL) 10.0Validationand WHC-SD-CP-QAPP-O02 8.0Reporting WHC-CM-5-3 2.0

2.2

InternalQuality QAPjP No. SA-O01 (PNL) 11.0ControlChecks WHC-SD-CP-QAPP-O02 g.o

Performanceand QAPJP No. SA-O01 (PNL) 12.0SystemAudits WHC-SD-CP-QAPP-O02 I0.0

Preventive QAPJP No. SA-O01 (PNL) 13.0Maintenance WHC-SD-CP-QAPP-O02 11.0

Data Assessment QAPjP No. SA-O01 (PNL) 14.0Procedures ' WHC-SD-CP-QAPP-O02 12.0

CorrectiveAction QAPjP No. SA-O01 (PNL) 15.0WHC-SD-CP-QAPP-O02 13.0

QualityAssurance QAPjP No. SA-O01 (PNL) 16.0

Reports WHC-SD-CP-QAPP-O02 14.0

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QUALITYASSURANCEPROJECTPLANFORCHARACTERIZATIONOF SINGLE-SHELLTANKS

1.0 INTRODUCTION

This sectionof the single-shelltank (SST) Waste CharacterizationPlandescribesthe qualitycontrol (QC) and qualityassurance(QA)proceduresandinformationused to supportdata that is collectedin the characterizationofSST wastes. The sectionaddressesmany of the same topicsdiscussedinlaboratoryQA projectplans (QAPJP)(WHC 1989, PNL 1989) and is responsivetothe requirementsof QA programplans (QAPP)(WHC 1990) associatedwith thecharacterizationof the waste in the SSTs. The level of QC for the projectdependson how the data is used.

Data qualityobjectives(DQOs)are being developedto supportdecisionsmade using this data. lt must be recognizedthat the decisionsandinformationrelatedto this part of the SST programdeal with the materialscontainedwithin the tank only and not what may be in the environment/areasurroundingthe tanks. The informationderived from this activitywill beused to determinewhat risks may be incurredby the environmentbut are notused to definewhat actual constituentsare containedwithin the soilsurroundingthe tanks. The phases definedwithin the DQOs on this WasteCharacterizationPlan followthe generalguidanceof ComprehensiveEnvironmentalResponseCompensationand LiabilityAct (CERCLA)yet arepertinentto analysisof the contentsof the tanks and not the environment.

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2.0 PROaECTDESCRIPTION

The overallprojectobjectivesare describedin the Draft Single-ShellTanks SystemClosure/CorrectiveAction Work Plan (DOE/RL89-16). The SSTwaste characterizationprojectis responsiblefor samplingand analyzingthewaste in HanfordSite's 149 SSTs to supportregulatory,safety (wastereactivity)evaluation,performanceassessment,waste retrievaland treatmenttechnologydevelopment,supplementalenvironmentalimpactstatement(EIS),andclosureplan activities. The purposeof Phase I of the waste characterizationprojectis to obtain informationas quicklyas possibleon all 14g tanks tosupport the planningand developmentof the above activities. If thisinformationis insufficientto supportan activity,then additionalwastecharacterizationwill be performedin Phase II with a revisedQAPJP to meetany new objectives. The projectaddressesonly characterizationof the wastein the tanks and not the soils or the ancillaryequipmentassociatedwith thetank system. Data from this programwill be used to perform risk assessmentsand to evaluatedisposalalternativesto supportpreparationof a supplementalenvironmentalimpactstatementfor the final EIS for the disposal of theHanfordSite defensehigh-leveltransuranicwaste (DOE 1988). Initialdatawill be used to help developDQOs to permitpreliminarysortingdecisionsabout those tanks wastes that may be treatedin place and those that may beretrieved. These data permitthe projectto identifyand evaluateadditionalcharacterizationand waste treatmentrequirements. The project also willprovidedata to supportregulatoryand safetyevaluationsfor storageandtreatmentof the waste.

The SST waste characterizationproject is only one part of a largerprogramto developa system for final dispositionof SST waste. Data fromtheSST characterizationprojectwill be used to supportth_ developmentof finaldisposalalternatives. The developmentof these alternativeshas beendescribedin severalsystemengineeringdocuments(Aikenet al. 1990;Garfield[a]1990; Garfield[b]1990; Boomer et al. 1990)which also identifypotentialdata users and their interactions. Furtherdetails on objectivesfor samplingand analyzingwastes in the tanks will be includedin futuretestplans for characterizingthe SSTs.

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3.0 PROJECTORGANIZATIONAND RESPONSIBILITY

Projectorganizationsand responsibilitiesare describedin theQA ProgramPlan for SST characterization(WHC 1990),the 222-S t.aboratoryQAprojectplan (WHC 1989),and the 325 LaboratoryQA projectplan (PNL 1989) forthe project. The WestinghouseHanfordCompanyorganizationalstructureinvolvedin characterizingSST waste is outlinedin the QA ProgramPlan(WHC 1990). However,the organizationsdescribedin these programplans andthe responsibilitiesof these organizat,ionsare expectedto changesignificantlyin FiscalYear 1992. The_sechangesare currentlypendingapprovalfrom the U.S. Departmentof Energyand will be formalizedafter theissuanceof this document. The samplingand analysisof SST waste samplesaredescribedwith the _ollowingmajor operations:

!, Plan and requestsampling.

2. Samplewaste tanks.

3. Transportand receivesample.

4. Break down (extrude)and prepare(homogenizeand composite)samplesfor analysis.

5. Analyzesamples.

6. Verify and report results.

7. Validatedata packages.

The Tank Waste CharacterizationTechnologySectionunder WasteManagementTechnologyis responsiblefor identifyingthe waste tanks to besampled,for providinginstructionsto Tank Farm Plant Engineeringforsamplingthe tanks;and to the Office of SampleManagementfor analyzingthesamples. The Office of SampleManagement(OSM) decideswhich Laboratory(222-Sor 325) will do the work and providesinstructionto the laboratorythrougha statementof work request.

Samplesare taken by the Tank Farm SurveillanceOperationsgroup andtransportedto the designatedlaboratory. The Tank Farm SurveillanceOperationsgroup initiatesthe chain-of-custodyprocedureand preparesthefield blanks. Samplesare receivedin either the WestinghouseHanford222-S Laboratoryor the PacificNorthwestLaboratory(PNL) 325 Laboratorywhere the samplecustodiancompletesthe chain-of-custodyprocess and logs thesample into the laboratory. Subsamplingof extrudedcore segmentsisperformedby the ProcessDevelopmentSupportUnit of the 222-S Laboratoryandthe AnalyticalLaboratoryOperationsgroup at PNL. These groups areresponsiblefor loggingin the samplesand preparingthe instructions(travelers)for samplebreakdownand analysis.

Samplesare brokendown and extrudedby the hot cell operatorsin theProcessChemistryLaboratorygroup for WestinghouseHanford and the A Hot Cell

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operatorsfor the 325 Laboratory. These hot cell groups performvisual andphysicalmeasurementson the extrudedsamples,homogenizethe samples,andpreparesubsamplesto be dispensedto the analyticalchemistrygroups foranalysis. The subsamplesfor inorganicand radiochemicalanalysesare givento the 222-S ProcessDevelopmentSupportUnit for analysis. Additionalsubsamplesare providedto other members of the ProcessChemistryLaboratorygroup for physicalanalysessuch as differentialscanningcalorimetry(DSC)and particlesize. Subsamplesfor organicand rheologyanalysisfrom222-S Laboratorytank samplesare sent to PNL for analysissince the222-S Laboratorydoes not have this capabilityat this time. Thesecapabilitiesare plannedto be added in FY 1991.

Subsamplesfrom the A Hot Cells at 325 Laboratoryare provided tospecificanalyticalteams at PNL for analysis. Samplesfrom the A Hot Cell in325 Laboratoryare transferredto the B Hot Cell for analyticalpreparationprocedures.

Each analyticalteam (inorganic,radiochemical,organic) is responsiblefor analyzingthe samplesand verifyingthe data quality in accordancewithstatementof work and the QC criteriafor the projectdescribedin this QAPjP.

Data packagesfor segmentand core compositeanalysesare preparedbythe analyticalgroups of both laboratoriesand submittedto the Office ofSample Managementfor data validationbefore releaseto the data users.

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4.0 QAOBJECTIVESFORMEASUREMENTDATA

Data obtainedin the waste characterizationprojectwill be used tosupportmany activitiesand users. Some of these are identifiedbelow:

User ActivitvWestinghouseHanford

• RegulatoryAnalysis Preliminaryregulatoryevaluation

• RCRA Permitting/NEPAGroup Supplementalenvironmentalimpactstatement,and closure/postclosure plans

• Waste ManagementTechnology Evaluationof disposalalternatives,treatmenttechnologydevelopment,preliminarysortingof tanks,characterizationplanning

• EnvironmentalTechnology Developmentof performanceandrisk assessment

• Systems Engineering Designof waste retrievalequipment

• Waste Tank Safety,Operations Evaluationof tank safetyand Remediations conditions

PacificNorthwestLaboratory

• Waste TechnologyCenter Supportstudieson aboveactivities

WashingtonState Oversightand evaluationof dataand Departmentof Ecology decisionswith respectto

WashingtonAdministrativeCodes.

U.S. Departmentof Energy Oversiteand evaluationof dataand decisionswith respecttostate and federalrequirements

Each of these primaryusers may have additionalsecondaryusers withdifferentdata requirementssuch as the differenttechnologiesbeing studiedfor treatmentand retrieval, lt is the responsibilityof these users todevelopdata qualityobjectivesfor the data used from the wastecharacterizationprogramto ensureth:t the requiredinformationwith thedesiredaccuracyis obtainedto solve their problem, lt is the responsibilityof the waste characterizationteam in Waste ManagementTechnologyto collect

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these data objectivesfrom the users and optimizea samplingand analysisdesign for characterizingthe waste to meet as many of the data users needs aspossiblewithin the constraintsof the samplingand analysiscapabilities.Section4.0 of the Waste CharacterizationPlan (WCP) (WHC-EP-0210)discussesthe variousparametersfor analysisand the rationalefor their selection.Potentialuses of the data are summarizedin Table 4-14 of the WCP based onpreviousknowledgeof regulationsor existingtreatmentprocesses.

Table D-I providesa guidelinefor test being performedand the user ofthe data. In some cases the users have not specifiedtheir data requirements(none identified). These areas are expectedto becomebetter definedas theseprogramsprogress.

Inventorymeasurementsof inorganicchemicalsand radiochemicalsreceivesthe most wide-spreaduse. Even though pre-treatmentusers have not specifiedtheir requirements,it is anticipatedthey will be interestedin analytesthatproducemost of the risk or analytesthat may impact the performanceof thetreatmentprocess. The inventoryestimatesare of interestto Ecologytoevaluatewaste designationusing the toxic equivalentconcentrationcalculation(TEC)which is a weighted sum of waste constituentsbased on theirtoxicity. This is the primaryreason for performingregulatoryorganicanalyses. Some of the analyteresultsobtained in inventorymeasurementswillbe used to assessthe potentialreactivityof the waste. Even though nospecificanalyteshave been identifiedit is anticipatedthat oxidantsandreducedcarbon will be of interest.

Physicalpropertymeasurementsare primarilyof interestto the groupsdevelopingretrievaltechnology. Waste hardness and viscosityare importantin designingmechanicalsystemsto removethe waste. The presenceofdrainableliquid is of regulatoryinterest.

Waste designationtests are primarilyperformedto satisfyregulatoryrequirements. The reactivityof the waste is a requirementof regulatorywaste designationproceduresand to tank farm operationsfor assessmentofsafetyconcernsin storingand samplingwaste.

The determinationof solubilityand adsorptioncoefficientconstantsforthe waste is primarilyimportantto long term releaserisk performanceassessmentstudies. These studieswill impactcharacterizationplanningandtank sortingdecisions. The informationalso will be used to evaluatethe noaction alternativefor the supplementalenvironmentalimpactstatementfor theSSTs.

The samplingand performingof tests in duplicatesis importanttoestablishingthe uncertaintyin the test results. This uncertaintyneeds tobe known to evaluatethe significanceof resultsand the accuracyofdecisions. This informationshouldbe importantto most users.

As describedearlier one of the primarypurposesof Phase Icharacterizationwas to perform a preliminarysortingor rankingof the tanksinto those whose waste should be retrievedand those whose waste may betreatedin place. Since this problemrequiresthe use of both performance

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A

assessmentand regulatoryrequirementsin the decisionmaking process, it isexpectedto requirethe most comprehensiveand restrictivedata requirements.The data qualityobjectivesdescribedin this appendixwill be the objectivesneededto meet the most demandinguser requirement. The processfor arrivingat the data qualityobjectivesfor the tank sortingproblemare describedbelow.

Data qualityobjectivesfor preliminarysortingor rankingof tanks fortreat-in-placeand retrievedecisionsare being developedusing informationfrom a computermodel (TRAC)of tank contents (Morgan1988) and initia_informationfrom Phase IA and IB. The analyteprioritiesreport (Wegeng19g0)describeshow data qualityobjectivesare being developedfor the project.The DQO processhas been describedin severalreports (EPA 1987Neptune 1990",Neptune Iggob). The DQO logic processis provided below andthe generalDQO processfor SST characterizationis outlinedin Table D-2.This table addressesthe questionsrecommendedby EPA for the developmentofDQOs. In most instances,referenceis made to sectionsof this documentorother documentswhere responseto the questionis addressed. Titlescorrespondingto the documentnumbersare stated in the legend at the end ofthe table.

DQOLogic Process

1. State the problem.2. Identify a decision that addresses problem.3. Identify inputs affecting decision.4. Specifydomain of decision.5. Developlogic statement.

_v

6. Establishconstraintson uncertainty.7. Optimizedesign for obtainingdata.

The domain of the presentprojectfocuseson establishingthe totalinventoryfor chemicaland radiochemicalconstituentsin the tank. Someverticalsamplingand analysesare plannedto identifylayering in the tanksfor some analyticaland physicalparameters. The domain for this work isfurtherdefinedin the scenariofor releasein the MultimediaEnvironmentalPollutantAssessmentSystem (MEPAS)model which is an enhancedversionof theRemedialAction PrioritySystem (RAPS) (Droppoet al. 1989). Thecharacterizationproblembeing addressedis sortingthe tanks into preliminarytreat-in-placeand retrievecandidates. Major factorsaffectingthis decisionhave been identifiedas: long-termreleaserisk (LTRR),short-termintruderrisk (STIR),and waste classification(CLASS)based on both Nuclear RegulatoryCommission(NRC) low level waste (LLW) classificationlimits,and on Ecologytoxic equivalentconcentrationcriteria (TEC).

The model RAPS/MEPAS(Droppo198g)was used to identifythe constituentsmost importantfrom a long-termrisk perspective. This preliminaryscreenused TRAC information(constituentsand concentrations)as a basis forassessment. The model was also used to establishpreiiminarywasteconcentrationthresholds(concentrationthresholdlimits [CTL]).Concentrationthresholdsare definedas the concentrationof a constituentinthe waste that producesI% of the total risk index. These CTLs help to definedetectionlimit requirementsfor the project. Decisionsimulation

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calculationsare in progressthat will help define the numberof samplesandduplicatesneededto make confidentdecisions. These initialevaluationsarebased on TRAC estimatesand unverifiedestimatesof solubilitiesand soil

adsorptioncoefficients(Rd)which need to be substantiatedwith evaluationsusing actual analysesof tank waste and verifiedsolubilityand Rddata. Thiswork will lead to a logic statementand an optimizeddesign for obtainingdata.

, The developmentof the DQOs is an interactiveprocessandwill improveasb_tter and more representativeestimatesof tank inventoriesand performanceassessmentparametersare obtained. The DQOs for the projectshould be drivenby the decisionrequirementsand not by analyticalcapabilities.

Table D-3 identifiesthe constituentsthat are expectedto contributetothe long-term(LTRR)and short-termrisk (STIR)and classification(CLASS)criteria. Analytesthat contributebetween1.0 and 99% of the cumulativeriskindex are classifiedas Type I. Analytesthat contributefrom 0.01 to 1.0% ofthe risk index are identifiedas Type II. Analytesthat contributeto lessthan 0.01% of the cumulativerisk index are Type III analytes. The proceduresused to selectthese analytesare describedin the analyteprioritiesreport(Wegeng1990). For comparisonpurposes,the analyticalproceduresfor theseparametersand their capabilitiesalso are provided. In many cases TBD (to bedetermined)has been denoted for many values. These valueswill be identifiedafter Phase IA and IB data have been completelyanalyzedand will be used asthe baselinefor analyticalcapability. Qualitycontrol informationwill be

e gatheredduring Phase IC and will make analyticalcapabilityestimatesmorerepresentativefor all the tanks.

Most of the metals in Table D-3 are performedby inductivelycoupledplasma opticalemission spectroscopy(ICP) analysis;however,the table also

J includesother more sensitiveatomicabsorption(AA) and fluorometricmethodsfollowingthe ICP method. Even though Type II and Type III parametersmay notbe as importantto the decisioncriteriaas Type I, they are includedwhenthey are obtainedautomaticallywith multi-elementtechniquessuch as ICP.Other elementssuch as cobalt,copper,magnesium,manganese(VII),selenium,tin, thallium,and zinc, which were not consideredor found importantin theRAPS/MEPASevaluationhave been includedbecausethey are importanttoregulatorystandardsand can be estimatedwith ICP analysis. Thorium analysisis includedbecauseit can be determinedby ICP easier than by radiochemicalmethods,and is used to verifythat this is not a major componentin thewaste. The detectionlimits in Table D-3 are based on what can be measured inthe sample,i.e. instrumentdetectionlimitsmultipliedby applicabledilutionfactorsfor the normal preparationmethod. However,they do not accountformatrix interferencesand backgroundsthat may vary betweensamples. Thedetectionlimits in Table D-3 are based on preliminaryassumptionsforanalyticalproceduresbeing used and may change when more accuratedetectionlimit informationis available. The concentrationsthresholdlimits are thoseconcentrationsderivedin the analyteprioritiesdocument (Wegeng1990) basedon quantitiesthat would produceI% of the c,mulativerisk index. Some of theconcentrationthresholdvalues are based on regulatorylimits (sulfide),onlimitsestablishedin the WCP (NH],organics)and on specificationsby theuser (physicalmeasurements). The analyteprioritystudy (Wegeng1990)recommendsdetectionlimit goals based on the CTLs and on the source (LTRR,

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Table D-2. Summaryof Data QualityObjectives (DQO).

DQO Questions Responses/ReferenceDocuments

I. STATE PROBLEM Final dispositionof the SST s_stem.

la) How was site used WHC-EP-0210Section2historically? DOE/RL-8g-16SectionsI and 2

WHC-EP-0338SectionIi J

Ib) What were emergency DOE/RL-89-16Section7remedialresponseoractionstaken:• What actions• When

• How accomplished?

Ic) Based on currentobser- Phase IA, IB samplingresults,whichvationsof site conditions, are still under evaluationanddoes site differ from future Phase I samplingresults,conceptualmodels? If so, will indicateif tank inventorieshow has it changed? differ from TRAC estimates.

Reference: TBD.

ld) What are the known and See responseto la above.suspectedsourcesof DOE/RL-89-16Section4contamination? WHC-EP-0352Section2

WHC-EP-0338Section2

le) What is the initiallist of See responseto ld above.known and suspectedsite-relatedcontaminants?

If) What concentrationsof See responseto ld above. Actualknown and suspectedcontam- samplinginsideof tanks is part ofinateshave been measured Phase I and II waste

at the site? characterizationprogram.

Ig) What are the available WAC 173-303ARARs for the known and WHC-EP-0338Section 2suspectedcontaminants? PNL-7426Section8

Above documentslist currentlyknownapplicablerequirements. Additionalrequirementsmay need to bedevelopedin the future. Therecould also be mutually conflictingrequirementswhich need to beresolved.

lh) By what routes might Tank Leaks.contaminatemigrate DOE/RL-S9-16Sections2, 4, and 8offsite?

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Table D-2. Summaryof Data Qualitj/Objectives(DQO).L

DqOquestions Responses/ReferenceDocuments

Ii) What populationis TBD.potentiallyexposedtoknown and suspectedsite-relatedcontaminates?

tj) Based on available TBD.information,state thepotentiallysignificantreasonablemaximumexposurepathwayscenariosyou wouldlike to test.

Ik) Describesourcesof TBD.informationused to define

problem.

Z. IDENTIFYA DECISIONTHAT In-situdisposalor retrievalADDRESSESTHE PROBLEM alternatives.

2a) What are the alternative DOE/RL-89-16Section 10actionsto addressthe WHC-EP-0338Section I

potentialproblem?

2b) What is the decisionthat The resultsof the survey will notwill be the focus of this directlyaffect the decisionbetweensurvey? the above disposalalternatives.

However,they will be used todevelopmethodologiesforestablishingtank inventorieswhichis a prerequisitefor decisionmaking,irrespectiveof thealternativechosen.

3. IDENTIFYINPUTSAFFECTINGTHEDECISION

3a) Is it safe to assumethat The politicaland socialenvironmentaldata is considerationare factorsin theimportantfor decision TPA. The considerationsaffectingmaking or political/social the disposaldecisionsare: long-considerationsare also term releaserisk (LTRR),short-termimportant? intruderrisk (STIR),regulatory

waste classification,and cost,/scheduleconsiderations.WHC-EP-0210Appendix D, Section4PRR, PNL-7573DOE/RL-S9-16Section 10

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Table D-2. Summaryof Data qualit_Objectives(DQO).

DqOQuestions Responses/ReferenceDocuments

3b) What questionsabout the LTRR, STIR, and regulatorywaste+ environmentmust be classification. See 3a above_

answeredto make thedecision?

3c) Will action levels Yes. Performanceassessmentswill(decisioncriteriafor be preformed.determiningif a problem PRR, PNL-7573exists)for contaminatesbe WHC-EP-0338SectionI, Figure I-2.determinedby risk-basedcalculations?

4. SPECIFYDOMAIN OF THE DECISION The domain is each individualtank.

4a) What are the receptor For the short term of the wastepopulationsfor which risk characterizationprogram, it is theassessmentwill be site workers. There are nocalculatedfor preliminary trespassersbecauseof the security.action levels? PRR_ PNL-7573

4b) What are the currentand Currentlya Federalreservation;itfuture land uses? will continueto be so for the

foreseeablefuture.

4c) What are the anticipatedor DOE/RL-89-16Section10.4known receptorpopulationactivitypatternsassociatedwith currentandfuture land use?

4d) What is the smallestarea Restrictedaccesslimitedto siteover which a receptormight workers.limit its activitiesduringthe period over whichexposureis possible?

4e) If site consistsof A decisionwill apply to eachmultiple exposureunits, individualtank.will decisionsbe made ondiscreteareas or entiresite?

4f) Are you interestedin a No. The entire tank is one uniformscale of resolutionsmaller exposureunit.than an exposureunit?

4g) Does site historical N/A. See responseto 4f above.informationallow

estimationof hot spots?

4h) What is the minimumsize of N/A. See responseto 4f above.hot...spot?

D4-8

WHC-EP-0210REV 3

Table D-2. Summaryof Data qualityObjectives(Dqo).,.....

DqO questions Responses/ReferenceDocuments

4i) When will data be collected WHC-EP-0210Section3and what timeframewill it

represent? 1

5. DEVELOPLOGIC STATEMENT

Sa) How will data collectedat PRR, PNL-TS73this tank be summarizedforuse in answeringthe mainque_tlon?

5b) If ARARs or RfDs are to be WHC-EP-0210,AppendixFused, what are the PRR, PNL-7573thresholdsof potential The samplingof initialtanks inconcern? Phase IC is to determinethe

presenceor absenceof certainanalytesof preestablishedpriorities, lt is not intendedtodeterminewhetherthese analytes areabove or below established

............... regulatorythresholdlevels.

5c) If risk based criteriaare Risk based criteriawill be used forused, the following selectingfinal disposaloptions butquestionsmust be answered not during waste characterizations.(apportioningrisk, targetdaily intakes,etc.).

Sd) Clarifyinitialkey Quantitativedecisioncriteriawillquestionsincorporatingthe be establishedduring Phase IIspecificdomain,decision sampling. ReferenceEP-0338criteria,and summary SectionI for decisionlogic ofstatistic, disposalalternatives.

5e) Createlogic statement(s) See responseto 5d above.in if/thenterms thatexplainwhat actionswillbe taken under whatcircumstances.

6. ESTABLISHCONSTRAINTSONUNCERTAINTY

6a) What are the potential N/A. See responsesto 2b and 5bconsequencesof incorrectly above.decidingthe site is not a PRR, PNL-7573problem (falsenegative).

D4-9

WHC-EP-0210REV 3

Table D-2. Summar_of Data quallt_Objectives(DqO).

OqOquestions Responses/ReferenceDocuments

6b) What are the potential See responseto 6a above.consequencesof incorrectlydecidingthe site is aproblem.(falsepositive).

6c) For t,ch potential See responseto 6a above.consequence,what is thequalitativedl_cG_fortofmakin_ the error?

6d) What concentrationof site- See responseto 6a above.relatedcontaminatesofpotentialconcerncorrespondto followingincrementsof risk levels.

6e) Translatequalitative See responseto 6a above.levels to quantitativevalues--forfalse negative.

6f) As above,for false See responseto 6a above.positive.

6g) Specifytrue values for See responseto 6a above.which either decision errorcan be tolerated.

7. OPTIMIZEDESIGN FOR OBTAININGDATA

i

7a) What are the estimated The purposeof the wastevariablesand distribution characterizationis to answerthisof site-related specificquestion. The samplingofcontaminatesof potential tanks in Phase lC is part of theconcern? waste characterizationeffort.

7b) What is the lowestcost WHC-EP-0210Sections3, 4, and 5;samplingplan to achieve AppendixesD and Fdesiredconstraintson PRR, PNL-7573uncertainty?

D4-10

WHC-EP-0210REV 3

Table D-2. Summar_ of Data.qualit7 Objectives(DQO).I

DQO questions I Responses/ReferenceDocuments

LEGEND

WHC-EP-0210 Waste characterizationplan for the HanfordSite Single-Shelltanks (this document).

DOE/RL-89-16(Draft)Single-ShellTanks System Closure/CorrectionActionWork Plan.

WHC-EP-0338 Functionalrequirementsbaselinefor the closureof Single-' Shell Tank.

WHC-EP-0352

WAC-173-303 WashingtonState Departmentof Ecology,DangerousWasteRe_. "89."

PNL-7426 System analYsisof alterrativefor final dispositionof theSingle-ShellTank S_stem on the HanfordSite.

PNL-7573 PreliminaryRecommendationson the Design of theCharacterizationProgramfor the HanfordSite Single-ShellTanks--ASTstemAnal_/sis.

STIR or CLASS) of the most restrictiveCTL. This report recommendsdetectionlimits 100 times less than the CTL for LTRR sensitiveanalytes and 10 timesless than the CTL for STIR and CLASS sensitiveanalytes. Table D-4 assessesthe presentestimateddetectionlimits for each analyteagainstthesecriteria. Based on this evaluationimproveddetectionlimits for the

_ll°1_ingc,analY1_sma_ be needed: As, Al, Be, Bi, Cr, Pb, Sb, NO._,NO_,F'," WTc, I, Cs and the actinides. Since Al, Bi, Cr, NO_,NO2, F',and 137Cswill probablybe presentin many of the wastes at high levels,thedetectionlimits for these analytesmay not be an issue. The concentrationthresholdlimitscould change if the solubilityand transport(Rd)propertiesof the elements are differentfrom those used in the model. Furtherevaluationof the performanceassessmentmodel based on actualwasteconcentrationsand transportpropertiesmay be requiredbefore the importanceof improvingthe detectionlimits can .bedetermined.

Most of the radionuclidedetectionlimitsare about equal to theconcentrationthreshold_imitsusing normalsample sizes and countingtimes.The methods for I_91and "Tc may requiresignificantimprovementsto meetCTLs. Furtherevaluationof the radiochemicalmethodsand the CTLs are neededto identifydevelopmentneeds.

Most of the anion methodsdo not have detectionlimits 10 times below theCTLs except for sulfate;however,most of the anion detectionlimits are belowor near the concentrationthresholdlimits.

Other analyticalmethodsthat need to be developedare" ferrocyanidespeciation,X-ray diffraction,polarizedlightmicroscopy,determiningthecoefficientof thermalexpansion,specificheat, chemicaloxygen demand,

D4-11,.

WHC-EP-0210REV 3

thermalc_nductivity,and thermalconductivityof the frozen sludge. DQOs anddetectionlimits for these procedureshave yet to be determined.

Analyticalmethodsfor determiningthe concentrationof complexantshavenot been developed. AdditionallymeetingCTLs based on total organic carbon(TOC) analysesand high performanceliquid chromatography(HPLC)methods isexpectedto be inadequatebecauseof the sensitivityor selectivityof themethods. Other analyticalmethodsthat need to be developedare:FerrocyanideSpeciation,Coefficentof ThermalExpansion,SpecificHeat,ChemicalOxygen Demand,X-ray Diffraction,PolarizedLight Microscopy,ThermalConductivity,and ThermalConductivityof frozen sludge. DQOs and detectionlimitshave yet to be determined.

Data qualityobjectiveaccuracyand precisionrequirementswill bedeterminedfrom decisionsimulationstudiesnow in progress. Completeevaluationof these DQOs will not be availableuntil allthe Phase IA/IB datahave been analyzed. Analyticalcapabilityinformationwill be used untilbetterguidance is available.

Since solid laboratorystandardsare not available,accuracyfor solidswill be monitoredusing spike recoveryperformance. Laboratoryaccuracyforliquid sampleswill be establishedfrom the analysisof laboratorycontrolstandards(LCSs). Values for these accuraciesare initiallybased onPhase IA/IB results and updatedwith routinequalitycontrolresults.Precisionsfor the laboratorycapabilitieswill be based on 3a limits foranalysisof duplicatesample aliquotsof solids and on repeatedsingleanalysesof LCSs for liquids.

Completenessis estimatedto be 90% for all analyses. However, sinceType II and III resultsare not as importantas Type I in making decisions,completenesscriteriafor these parametershave been set to 75_ and 50%,respectively,to indicatethe level of importanceof these parameters. Thisindicatesthat failureto achievea 90% goal of valid data for theseparametersdoes not requirethe same responseas for Type I constituents. Forexample,occasionallyone of the many channelson a direct reading ICP mayfail to produceadequatedata. If this channel is for a Type I parameter,analysesshall be suspendedand the conditioncorrectedto meet the 90%completenessgoal. However, if the channelis a Type II or Type IIIparameter,suspendingthe analysesmay not be requiredor even worthwhile.

All data shall be reported in /Jg/gor #Ci/g of dry sample weight for allsolids and #g/mL or #Ci/mL for liquid samples. The weight percentwatercorrectionfactor used to correctthe data from wet weight to dry weight shallbe includedwith each batch of data. Toxic characteristicleach procedure(TCLP)resultsshall be reportedas mg/L of the extract.

Single-shelltanks will containrelativelyhigh concentrationsof waterin the sludgeor crystallinematrix. Becauseof the potentialfor water lossduring handlingin highly ventilatedradiationfacilities,the weight percentwater and the preparationfor the analysisshall be performedin the same timeframe to providethe best comparability. If over 30 days elapsesbetweendeterminingthe weight percentwater and preparingan aliquotfor analysis,the weight percentwater shall be rerun providingadequatesample is

D4-12

WHC-EP-0210REV 3

available. Resultsof this analysiswould then be used to correctany lateranalysesto a dried weight basis. The laboratoryshall make every effort tokeep the time the sample and subsamplealiquots are open to the atmosphereat

o i,

a minlmum and to keep them sealed to preventwater loss.

I_ D4-i3rl ....

WHC-EP-0210 REV 3

Table D-3. Data Quality Objectives and LaboratoryCa ilities 1 of 10)

o o

u

_,_._.,_=_ _ _ _ _ _ _ _ .._o.o__-...o___UO _ _ _ _ _ _ _ _ _ _ _

g_

-_ .

0 0

Z II I0 II II II II II I| II II II II

(z _= _= (= (= <= (= _= (= (= (= _=

ao 0 ao a ao o ao a ao ao o

_ P _ P5 _3 _5 P5 P5 P5 _ _5 P5_z ,_z _z _z _ _ _z _z _z _z _z _

u

_ _ u u _ _ u _ u u u u

D4-14

WHC-EP-0210 REV 3

Table D-3. Data Quality Objectives and LaboratoryCa illties sheet 4 of I0

,,.........

_' ......... i

I--I-- I-"I-- ,I--I-- I,,-I-- I--l-, l--

.J

n

0 0_0 _U_ _-" _-" (:_

z

v) ek" I_ (_ ,_ _ ,_, _ _) _) (_)).-

,, , i ,,,

......... C_O_

g ,s =s =s s-s s-_ =s =s-si. U'_ i U"t * _ * L/'_ * i._ * lpr i i._ i I._ i Lf_ i _ ,

L. N _{: _ I-- N

m ¢_. r_ _. U U U U U ..J (.JQ. (..1 U U *-* _ *-_

D4-17

WHC-EP-0210 REV 3

Table D-3. Data Quality Objectives and Laboratory

D4-18

WHC-EP-0210 REV 3

Tabl'eD-3. Data QualityObjectivesand LaboratoryCapabilities. (sheet7 of 10)

, , ,,, i ii

_a.

,,. I.- i-. --I-. I-- I-- I-- I-- I-- I-- I-. --I.- l--P- -- l-.P-

l

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o '_w,#

o i t I_

.....

k-

-s s Ts-s-' rs s s s_, _ _, _, _,_ _ _ _ _. _,_n o o I,d"_ O I,l_l o 1,1_ o

I ..,,I o ..,I o _ o .,,,,.I I ,,.,,,I

L _ '.I' Z P" _ N- fW.

&. ¢_ (/1 (OI U} ._

D4-20

WHC-EP-02]O REV 3

Table D-3. Data Quality Objectives and LaboratoryCapabilities. (sheet8 of I0)

....

VI

, ,, i i , , , ,, , ,

- ... ..

,-_= _ _ _ _ _I_

°_'+..' ' i,,- 0 A

,- ,_ _ _

•-, .-, .-, T m T T T

VI

p',. ^ [

" _

+ _m-+ • + +II.VI Ill VI VI '_ (#__

_

D4-21

WHC-EP-0210 REV 3

"TableD-3. Data QualityObjectivesand Laboratory

Ca abilities: (sheet10 of i0)

... L,

_,,- _ (11E 0J.... l.J -_ _= _ 4_

i! °°° o+oIrlVI +,- "CI_=t C.

F- _- M- _- F- 0,-" (3. _ L V)

'"_, _1 W II '5

......... I.+ II .31_I:: VIU1 **,"

1%1(/)(411 1:: II *'0 X ._

_'i +m +m _ m m m ,._+_ ,_ ,._,....... _I: I. 1".-+ G.(_I {=.LA

¢3 ¢:: U*-- _ C. G._ O_ u_

+! _ + _ +, + m ,.+.,,,,,,,,.,+..=,:oo=,,,,_._+._ _ .,+Iml f',J._ t_ 0 ,_,m II3 Ota L. II ,,--I--. I--" I--' I"-- OJ t,. t,. _ t,,_ *,- II I.,+ +,_ V)

+ +.,o,,.o,...o,.,::,.+++"..+,+-" _L +,- O-J &-tIJ _ U UC. 0 C "

_++_ +"++"+_ _ '-_ ++"'°"°'+=°°++°°°'_++i;,, ,+,,+++++-' ..-+ _.m ¢_ e+' 0 • ,_ _ ', ,, (J (II--.+ I.+ B (110_ lIJL OJ 0...,*0

.-+ ,,,o..,<.+_,,.,..oooo,,,-_.+ -,+,+-+ +++'+ _ "+"++"°°": "+'+"+ +._ m,-=m'+ m _ +

+ mm °'mm +,,m+,.., ++ +++ ,,,,,, o:,,,,,, +_,+ o+,,,.+-+ ++= ++.,+-+++:.+

_- _ ,-_.... _,+(/i .... II_ ,,-

_+ +_+ -m ,.,,.. ,,, ,,, ,F_.,8.+..++=+, ,. _,

o _=+_'___._ +.., +., _ +-' _ +-' .-,,+ "+-++ + ++_ ,.- ,.. ,.. ,... ,...

,.. ,_++,+'+,,+,+.,,=+,+.+..... X + = ': + + _ + 1+

I-- IX '_

.+,+. + + L+.+++.+ +++ ++-++ =+ ++ +++ xo ++m -' +" '_ u o-_ u_, ++ +_U U _ (3=

,,.. ,_- ILl li

,.... ,. ,- _ ... _ o.,=

° _L" o .+ +-+ ++-++._+=•lC: (/1 r_ _*_ _. *'-

..........

D4-23

WHC-EP-0219REV 3

Table D-4. Assessment of Analytical Detect on Limits,

DL DL DL BasisAnalyte <CTL <0, ICTL <O.OICTL

As Y-HYAA N N LTRR.......,, , ,,,,,

Ag Y-ICP Y-ICP N STIR,, ,,

Al Y-ICP N N STIR, .,.,

Ba Y-IcP Y-ICP N STIR, ,

Be Y-ICP N N LTRR, , ,,,,

Bi Y-ICP N N STIR,,,, ,,,

Ca Y-ICP Y-ICP Y-ICP STIR

Cd Y-ICP Y-ICP N STIR........ I .,,

Ce Y-ICP Y-ICP Y-ICP STIR, ..,,

Cr Y-ICPa N N STIR,,

Fe Y-ICP Y-ICP N CLASS

, Hg Y-CVAA Y-CVAA" Y-cvAA" LTRRi

'K Y-ICP Y-ICP Y-ICP" CLASS! , , ,,,

La Y-ICP Y-ICP Y-ICP CLASS

Mn Y-ICP Y-ICP Y-ICP STIR

Na Y-ICP Y-ICP Y-ICF CLASS, i

Ni Y-ICP Y-ICP N CLASS

Pb Y-ICP Nb N STIR

Y-HYAA Y-HYAA N STIRSe Y-GFAA

Sb Nb N N LTRR

Si Y-ICP Y-ICP N STIR

Sn Y-ICP Y-ICP Y-ICP STIR

U Y-FLUOR Y-FLUOR Y-FLUOR LTRR,,

V Y-ICP Y-ICP Y-ICP LTRR

Zr Y-ICP Y-ICP Y-ICP STIR

NO_ Y-IC N N LTRR,

NO_ N N N LTRR

D4-24

WHC-EP-O21gREV 3

Table D-4. Assessment of Analytical Detect on Limits.....

DL DL DLAnalyte <CTL <O,ICTL <O.OICTL Basis

F" Y-IC Y-IC N LTRR

SO_2' ' , Y-ic ........Y-iC Y-iC STIR, , , , , ,,,, ,,,, ,,,

PO__ Y-IC Y-IC N STIR

CI" Y-IC Y-IC N LTRR

CN N N N LTRR

C032 Y-TIC Y-TICa N STIR,. ., ,, ,.,, , ..,

NH3 Y-SlE Y-SlEc N REG.

14C Y-LS Y-LS N LTRR

9°Sr 'Y-Beta ....Y-Beta N STIR,,, , ,,,,, , , ,, ,,, , , ,,,,,

99Tc N N N LTRR

1291 N N N LTRR

137Cs Y-GEA N N CLASS

23SU Y-FLUOR Y-FLUOR Y-FLUOR LTRR

23SU Y-FLUOR Y-FLUOR Y-FLUOR LTRR,, ,.. .. i ,.,

237Np N N N CLASS, , • .,

23Bpu239pu N N N CLASS24Opu

, ,,,,

241Am244Cm N N N CLASS

.....

Note: Assessmentis based on preliminaryestimatesof analyticaldetectionlimits,

aPNLdetectionlimit above CTL,

bBasedonly on ICP.

c222-S Lab detection limit above CTL.

Y = Yes-analytical technique

N = No

D4-25

WHC-EP-0210REV3

This page intentionally left blank.J

D4-26

WHC-EP-0210REV 3

5.0 SAMPLINGPROCEDURES

A discussionof the SST samplingprocedureshas been providedinSection3.2 of the Waste CharacterizationPlan. The samplesare taken by theTank Farm Operationsgroup in accordancewith Plant OperatingProcedure(POP)T0-020-450"PerformCore Sampling." The waste characterizationplan describesthe samplingequipmentand the problemsencounteredwith preservationandholdingtimes when analyzinghighlyradioactivesamples. The samplingPOPidentifiesrecordstaken during samplingand initiatesthe chain-of-custodyfor samples. Samples are identifiedby a unique number. Samplesshall not beallowedto stand in the field for over 48 h before shippingto the laboratory.The samplesare shippedto the HanfordSite laboratoriesin accordanceto POPTO-OSO-OgO"ShipCede Samples." The procedurealso addressesthe completionof the chain-of-custodyform and obtainingthe necessarysignaturesfor samplereceipt. The samplingteam is responsiblefor documentingany problems andproceduralchangesaffectingthe validityof the sample in a field notebook.Copiesof the pages describingthe problemsand identifyingthe questionablesamples(ID numbers)shall be forwardedto the laboratoryfor addition to thedata packagefor that sample.

D5-I

WHC-EP-0210REV 3


D5-2

WHC-EP-0210REV 3

6.0 SAMPLECUSTODY

The chain-of-custodyform is initiatedby the samplingteam as describedin POPsT0-020-450and TO-O80-ogo. The sample is shippedin a cask, andsealedwith a paper seal containingthe informationshown below:

WASTE TANK SAMPLESEAL

Supervisor SampleNo.

Date of Sampling Time of Sampling

ShipmentNo. SerialNo.

Becauseof the cask size and truck limitations,only three samplescan beshippedat a time. The sealed and labeledsamplesare shippedto thelaboratoryalong with the chain-of-custody.An exampleof the fieldchain-of-custodyform is shown in Figure D-I. Examplesof forms in thisdocumentmay not be the most recent version;therefore,the original and mostrecentdocumentationshall be referredto for any changes.

The receiptand controlof samplesin WestinghouseHanford222-S Laboratoryand PNL 325 Laboratoryare describedin the laboratoryQAPjPs(WHC-SD-CP-QAPP-O02,QAPjP No. SA-O01)and labcratoryoperatingproceduresL0-090-I01and PNL-ALO-010,respectively. The 325 Laboratoryuses twoadditionalin_ernalchain-of-custodyforms (FiguresD-2 and D-3) whereas the222-S Laboratoryuses travelercards and a samplecheckoutlist (FiguresD-4and D-5) for trackingsamplecustody in the laboratory. Both laboratoriesarelocatedin securedareas that have controlledaccess and that requirephotoidentification(badging)to be permittedin the area.

A portionof the samplewill be saved as an archivesample until the datahave been analyzedto allow verificationof questionableresultsand tocarry-outmethod development. Archivedsampleswill not be disposedofwithoutconcurrenceof the Tank Waste CharacterizationTechnologySection.

6.1 SAMPLEBREAKDOWNANDSUBSAMPLING

After the samplesare receivedin the laboratorythey are extruded,physicalobservationsare recorded,and subsamplestaken for the otherparameters. Table D-5 providesa list of the PNL and Westinghouseprocedurescoveringthese operations. These proceduresincludehomogenizationandcompositingoperations.

D6-1

WHC-EP-0210REV 3

FigureD-I. Field Chain-of-CustodyRecord,

CHAIN-OF-CUSTODY RECORD FOR CORE SAMPLING

(I) Sh_ipmentNumber (2) Sample Number (3) SuperviSor'

(4) Tank (5) R0ter (6) Segment (7) Cote _4_ (8) CaskSerialNumber

Rad,at,onS.,,.yO,,, C.,,,LO ,.)L.,O.,O,,1101Shi'_'ent._',ipti_n

Over lop DoseRate A g ,

S,deDoseRate a Catk5e___r i

8ottom Dose Rate _ _Sampler_diber Uted'$mearable Contam,r,at,on -"_l_'aate ,ta'_i;_imeSampler Unseated

(aMh,II , (_Ip_l E, quldCon|e t

jVF,..°,,.dso,,Coo,n,

_pr. (r.gnal_.r.) npr' _i' __llrG..... Dote Rate Through Drill String•- ......._ It_}M :_pe(,edSampleL,.g_h(111 INFORMATION (IncludesIalemenlolldbocalorylesll ' "_ ' _ "

{t2) F=elclComments. 1211Laboratory Comments

(t'J) POiNt OF ORIGIN (t4) $1NOIR NAME ' " ,tiling' (16)DAlI RILIA$1O (t||O|$|IN&TION (:lO) RICIPliNI NAMi (2l) OAtl RICIIVIO

(I$)$INO|RtlGN&IURI" " (t?)rlMI _iL|A$|O (It)RiCIPI|NItlGNAtURI' |l'l) TINt[R|¢|IVID ......

(191SealIntact Upon Release? (24) SealInr,art Upon Re(e*l:)l:t (25) Seal Data Cons,)t.entwith th,_Record}Sh,preenSNo CaskSealNo SampleNo

J"JYet ['1 No [-1 Yes J-1No J"JYet J-1No J-'lYet [] No [] Yes Q No

DISIRIIIUIION _41ltHe-O_eo¢Sa_M,je,'t_¢_" Yellem -Ref,tp_nll'o_$amplaR 3((_c_) ],)):oJ

K-W,- Prr.._e_r_i_;oeenn 9 a.. $. Gov_n_;¢_ - I_F_em Ol.enilv, nt r_.O"

D6-2

_

WHC-EP-0210REV 3

FigureD-2. 325-A Hot Cell Chain-of-Custody.

Chain oF Custody Number _ ,,

I II II I II II I I I I II II '

t

_25-A HOT CgLL CHAIII-0F-CUSTOOY

DATE OF TRANSFER

SEtlDER .......... ':

I

RECEIVER ............ • ,,

WHC SAM FICATION NUMBER ..............

Original - ALO Project Support OFFiceCo_y - ]25-A HoL CellCopy - _ZS-B Hot Cell

D6-3

WHC-EP-0210REV 3

FigurBD-3. ALO Chain-of-Custody.

Page..._oF._.. ALO CHAINOF CUSTODY COC Number

AL"O$_PL{ NUMBER - ANAL_YglS'REQUI,:SI'ED--_aAMPL(D(SCIIIPTION-- °

S_NOER ....................... _TE

RECEIVER .............DATE

V....... ,=, ,, , ,I ,,,|,,11 IRI II ii I • IIII I I III I II I

ALO SAHI (R -:ANALYSISREQUESTEO' sAHPLEDESCRIPTION....

SENOER, .............OATE

RECEIVE_ ................OAiE '

' ALOSAMP'LENUM6ER' -NtALY$'tSR(QU(ST_B-J S_PLE OESC_TLON

SENOER __

.................. OAr( ..... !

RCC(XVCR I........... OATE ........

i ii i ii i i i iii ii iii ' i i i i i i i i i

Original - ALOProjec= Suppor_ Of Ftca Applicable Tes_ InstructionCopy - SenderCopy - Receiver i ii J L i i

D6-4,e

WHC-EP-0210REV 3

Figure D-4. 222-S TravelerCard.

D6-5

O

• . -,w

WHC-EP-0210REV 3

Figure D-5. Sample Checkout List.

" ,,' ,A'.^_ENT:

"_' ' , Sampl. Ch.c_, Our. Sho.t,SAMPLEC]IECXOUTLIST

...............

" s,._1.,zo T.c,.oloqi,_ s,.pl.., s,._1,ouTlo.t./T1..,.. i , i ii i i i ii, .i i i i , ,.

6

i ii |i . H.

_,_ .......

__ _ , ,, , ,_ _, ........,__'__

I I_llvailiiiBimiDm

. , __. _"_i_

,m im i

" ' ,.... _I,

ii i i i i] i . i ..nimmm _

lJ |im

"I "'

- ' i)•.o ..... 0.

LO'090- l O! , ., .....---I

D6-6

WHC-EP-0210REV 3

Table D-5. Sample BreakdOwnProcedures.

WestinghouseHanfordProcessChemistryLaboratoriesDesk Instructionsi,ll i , in, i lw , llJ, il i ............................

Number Title

T038 A-O0 712F SamplerExtruderOperationsand Sample Breakdowni i ,,i, l

TO3g A-O0 712F Core Sample Cask Disassemblyand SamplerLoadinginIE-2 Hot Cell

ii ,,. .. , i , i ., , .......

TO40 A-O0 712F Core SamplerCask Receipt

T046 A-O0 712F SegmentBreakdownand AnalyticalSampleSchedule

PacificNorthwestLaboratoryProcedure

PNL-ALO-010(RevO) 325 LaboratorySingle-ShellTank Sample Receivingand Subsample/AnalysisNumberingSystem

325-A-2g (RevO) Receivingof Waste Tank Samplesin Onsite TransferCask

• PNL-ALO-130(RevO) Receiptand Inspectionof SST Samples

325-EXT-I(Rev O) Receiptand Extrusionof Core Samplesat 325AShieldedFacility

PNL-ALO-135(RevO) Homogenizationof Solutions,Slurries,and Sludges

D6-7

WHC-EP-0210REV 3


D6-8

WHC-EP-0210REV 3

7.0 CALIBRATIONPROCEDURESAND FREQUENCY

Calibrationfrequencyrequirementsfor the WHC and PNL laboratoriesarelisted in Table D-6. Detailedcalibrationproceduresfor methods andinstrumentsshall be in accordancewith proceduresliste_ in Table D-3. Thesesame proceduresdescribe the standardsand their sources. Sourcesforpurchasedstandardsand standardizationmethods and resultsshall bedocumented. Any systemwhose calibrationverificationstandardis outside its3_ limit shall be checkedmore thoroughlyand recalibratedas necessary.Samplesanalyzedon systemsout of calibrationshall be reanalyzed. However,if data must be obtainedfrom systemswith performanceoutsidethe calibrationlimit, the data shall be flagged,the calibrationproblemdescribed,and therecoveryfor the calibrationcheck standardprovidedin data reports, Anexamplewhere operatinga systemout of calibrationmay be acceptableis whena Type III analyteis out of controlon the ICP and recalibrationandrerunningthe samplefor this low priorityanalyteis not justified.

D7-I

WHC-EP-0210REV 3


D7-2

WHC-EP-0210REV 3

8.0 ANALYTICALPROCEDURES

The analysisof all SST waste characterizationsamplesand relateddatashall be implementedin accordancewith WHC and PNL procedureslisted inTable D-3 as specifiedin the laboratorystatementof work (SOW) initiatedbythe OSM. These proceduresshall meet the specificrequirementsdescribedinthe laboratoryQA projectplans (WHC 198g, PNL 198g). The proceduresapplicableto SST waste characterizationare identifiedin Table D-3Laboratoriesand samplingoperationsshall maintaina list of all currentproceduresand latest revisionsthat are being used for SST wastecharacterization.

A summarydescriptionof the deviationsfrom SW 846 test methodsaredescribedin Section5.0 of the Waste CharacterizationPlan. Such deviationsfrom SW 846 have been incorporatedin those analyticalprocedureslisted inTable D-3. Analysisof SST waste materialsshall be in accordancewithprocedureslisted in Table D-3 and includeapplicablequalitycontrolchecksdescribedin Section 10.0with a descriptionof the basis for establishingdetectionlimitsand for performingand verifyipgcalibrations.

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9.0 DATA REDUCTION,VALIDATION,AND REPORTING

Data reduction,validationand reportingpoliciesand requirementsaredescribedin the 222-S Laboratoryand 325 LaboratoryQA projectplans(WHC 1989, PNL 1989). Data reductionmethodsand equationsshall be includedin each analyticalprocedure.

Criteriato validatedata are discussedin the two QA projectplansgoverningthis work. The followingare some of the validationareas common tothe methods.

I. Sample recovery (percentof samplewhich is obtainedbased on whatwas expected)will be used to evaluatethe samplingprocess.Partialor empty segmentswill increasethe uncertaintyin therepresentativenessof the sample and limit the scope of testingthatcan be done. A 75% or greaterrecoveryof the sample is consideredto be an acceptablecriteria.

2. Samplereceiptand trackingdocumentssha_l be completeto ensurethat the sample has been shippedand processedin a timeframeandmanner that would not introducesignificanterrors. Meetingholdingti.r,lesand preservation(refrigeration)requirementsfor constituentsin highly radioactivesampleswill not be possibleduring Phase I.However,efforLswill be made to minimize analysistimes for theseconstituents.

3. All data shall be gatheredwith systemscalibratedin accordancewith applicableprocedures. Data reportedwith out of controlcalibrationconditionsshall be flagged.

4. Field,hot cell, and analyticalmethod blankswill be evaluatedtoensurecontaminationis not a factor in the final results. Datacollectedor reportedunder high blank conditionswill beidentified.

5. The relativepercentagedifferencesfor duplicateanalysesofsampleswill be used to evaluatehomogenizationand core compositingprocedures. Replicateanalysesof digestionswill be used toevaluateprocedureperformance. Data outsidethe controllimitswill be identifiedin the data reportsto OSM and explanationsofthe data provided.

6. Matrix spike recoverieswill be used to evaluatethe applicabilityof the procedureto the matrixand will be reportedfor applicableconstituents. Data consideredto be questionablebecauseof poorspike recoverieswill be flagged.

7. Detectionlimits and the basis for determiningthe limits for eachanalytewill be reportedfor comparisonto DQOs.

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8. Estimatesof precisionand accuracyinformationfor each parameterwill be collectedfor the sampleresultsand laboratorycontrolstandards. This informationwill be used to verify the analyticalsystemperformancebased on controllimits establishedfromhistoricaldata.

FiguresD-6 and D-7 summarizethe data flow through the 222-S and325 Laboratories. Data packageswill be preparedfor each segmentanalyzedinthe core and the core composite. The data pack_geshall includethe followincgeneral itoms:

• Identificationof proceduresused

• Summaryof results

• Chain-of-custodyrecords

• Field samplingobservations

• Hot cell breakdownand preparationobservations

• Analyticalresultsfor inorganics,radionuclides,organics,physicalanalysesand characteristictests

• Qualitycontrolresultsfor each test

• Calibrationand standardsdocumentationfor each test Q

• Supportinginformation.

- Chromatograms

- Interelementcorrections

- Detectionlimits

- Worksheetsand travelers.

- Laboratorynotebookrecordsof proceduredeviationsorproblems. J

The report also shall identifyand discussany problems encounteredinthe sampling,breakdown,and analysisoperationsand the impact these problemsmay have had on the results. The reportshall be prepared and approvedasdescribedin laboratoryQAPjPs and procedures.

The data reductionequationsfor analysisof each parameterare describedin each procedure.

The principalcriteriathat will be used to validatedata integrityduring collectionis summarizedin Table D-6 and described in Section10.0 ofthis QAPjP. The primarycriteriaare: calibrationverification,blank

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Figure 0-6. Data and Information Flow at 222-S Laboratory.

Sample ReceivingSample Custodian

Analytical

Lab Leader's Office Laboratories

ii i tPreparation of Laboratory ....Travelers

L ' Result Calculation < .....Q.C. Standards Verifiedt

Chemist Review

Manager Review

Bl II II I ! I I

II

III I I I I I I[ I

Data Reporting Uniti i i i ,

I ._ Report Compiling I _ Laboratoryi v Typing Q.A. OfficerDuplicating _ , !

i

- iii iii iI i • •

1Data Reported to Customer 29012027.1

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Figure O-7. Data and Information Flow at 325 Laboratory.

i i i i ii i i|11

I

Samples Arrive in Laboratory, I

Checked by Sampl, Cuatodlan i± ii

i ii i • i ii iiii iiI

Samples Received, Logged and IAssigned Completionpate by iSmp,.C._od,=.

.... i. i _ ii i i

Sample Sets Assigned toAnalystsby Technical Leader

i i ii i

i

!,o oon0oo-0"n IData, (:uaiity Control Data

Reviewed by Technical Leader

I Data Reviewed by ProjectManageror Designee

i ] • iii

I_ Level IV, V Data

Reviewed by QPRepresentative

i i i i ,,

I Data Approved byProjectManager

illl lUll

,,,,,.,,, iiI Data Reportedto Client !

iii _P_ i i iiii

........... 29012027.2

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evaluations,laboratorycontrolstandardperformance,duplicateanalysesresults,matrix spike results,and detectionlimits. In addition,tests toevaluatethe homogenizationand compositingprocedurereproducibilityandperformancewill be performedfor each tank. Criteriafor validatingdatapackages is describedin Sections2.0 and 2.2 of the WestinghouseHanfordOffice of SampleManagement,SampleManagementAdministrationManual,WHC-CM-5-3.

Data for the principalcriteriashall be collectedand analyzedtomeasurethe standarddeviationso that ±30 controllimits can be established.For calibrationverification,laboratorycontrolstandardsand matrix spikes amean recoveryand 3o limitsshall initiallybe determinedand updatedat leastevery 3 months (if the programhas been active)or after the analysisof eachbatch of tanks. After a sufficientdatabasehas been establishedcontrollimitsmay be updatedless frequently. For duplicates,matrix spikeduplicates,homogenizationtests, and core compositetests historicalinformationwill be collectedfor each tank and the averagerelativepercentdifferencein resultsand its±3o limit shall be used to identifyunusualconditionswhen testingnew tanks. Outlierswill be identifiedby usingcontrolcharts,tabulateddata or computeranalysisof data. Outlierswill beflaggedand the cause of the outlierevaluatedand documentedby reanalysisofthe sample,standards,or other appropriateaction dependingon the analysisas discussedin the next Section10.0.

Controlof softwarefor data reductionand reportingare addressedin theDefenseOperationsDivisionLaboratories,operatinginstructions(WHC-CM-5-4)and in 222-S LaboratoryproceduresLC-400-005,LaboratoryComputerControlandLC-400-006SpreadsheetDocumentationGuidelines. The PNL proceduresforcalculatingICP and ion chromatographyresultsare provided in the procedurePNL-ALO-218,ICP/lCData Calculations. Generalcomputerand softwarecontrolrequirementsare describedin the PNL QualityAssuranceManual PNL-MA-70.

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10.0 INTERNALQUALITYCONTROL

10.1 GENERALDISCUSSIONOF SINGLE-SHELLTANKQUALITYCONTROLOBJECTIVES

Qualitycontrol (QC) guidelinesare describedin the 222-S and325 LaboratoriesQA projectplans (WHC 1989, PNL 1989). Laboratoryqualitycontrolrequirementsare based on reguirementsof the SW-846 and EPA ContractLaboratoryProgram (CLP)procedures. The frequencyof the QC checks for theseroceduresare specifiedfor a batch or set of samples. Batch sizes forighly radioactivesamplesmay be small (I to 5) comparedto nonradioactivesamples(10 to 20) becauseof the need to controlpersonnelexposure andcontamination.This can result in a high proportionof QC checks. Therequirementsdescribedin this sectionapply to the characterizationof allSSTs unlessmodified in the test plan for a specificset of tanks.

To controlcost and exposurebut still ensure that adequatecontroldatais obtained,the test plan for samplingand analysisof each tank or a groupof tanks will includeQC elementsthat may redefinethe number of duplicatesand other QC checks that are describedin this section. Since the number ofsamples(segments)will vary with waste depth, and the number of cores neededwill depend on decisionrequirementsbeing developed,the total number ofanalysescould vary significantlybetweentanks, particularlyif a largenumberof parametersmust be determinedon segments. The test plan will bedesignedon the premisethat all the samples(segmentsand core composites)from the tank constitutea tank batch or set of samplesfrom the tank. ManyQC checks such as calibration,laboratorycontrolstandards,and blanks areused to supportthe resultsfor the analyticalbatch and must be performedeach time samplesare analyzed. Other QC checks such as duplicatesand matrixspikes are performedto measurethe performanceof methodson a particularsamplematrix or tank batch. The objectivesof the test plan must be: (I) toensure that the analyticalsystem is in controlduring measurements,(2) thatsufficientduplicatesare performedon each tank to permiterror estimatesthat meet DQOs, and (3) that sufficientmatrix spikes are performedto ensurethat method performanceis adequatefor that matrix to meet DQOs. Table D-6has been preparedto summarizethese checks for each parameterand establishminimumQC guidelinesfor the SST characterization.A discussionof theQC guidelinesfor each parameteris provided. These guidelinesmay bemodifiedin each test plan or increasedby operationswhen conditionsindicatea higher level of QC may be required. Qualitycontrolcharts,tabulateddataand reportswill be used to evaluatethe performanceof the samplingandanalysissystemof each tank and betweentanks. The followingparagraphsprovidea generaldiscussionof the column headingsto Table D-6.

Calibrationverificationand laboratorycontrolstandardsmay be usedinterchangeablyfor some parameters. Calibrationverificationstandardsareindependentstandards(differentsourcethan those used for calibration)thatare not normallyprocessedthroughthe preparationsteps but are used only forinstrumentcontrol. Laboratorycontrolstandards,on the other hand, shall becarriedthroughboth the preparationand analysissteps and are used tomonitorthe performanceof the analyticalsystem for the entiremethod.

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Preparingstable and accuratestandardsin SST waste matrices is extremelydifficult;therefore,the laboratorycontrolstandardmay be prepared in asimplermatrix similarto the calibrationverificationstandard. TheEnvironmentalProtectionAgency (EPA) or other referencestandardscould beused for the laboratorycontrol standard;however,these standardsnormallydonot resembleSST matrices or containall the parametersof interest. Forcalibrationblanks and verificationstandards,the analysisbatch is a set ofsamplesanalyzedon the instrumentas a unit under identicalcontrolconditionsor requiredfrequencyperiod. Laboratorycontrolstandardsandpreparationblanks are generatedfor each preparationbatch which is definedas the set of samplespreparedas a unit under the same controlconditions.

Spikes and duplicatesfor RCRA and CLP programsare normallybased on onein every twenty samples. For SST tanks the frequencyhas been set toestablishan indicationof method reproducibilityand accuracyfor thematerial in each tank. Therefore,the specificationfor duplicatesand spikesare the same for most parameters. RecentlyRCRA and CLP have beenincorporatingthe use of matrix spike duplicates(MSD) in the analyses. Theadvantageof this approachis that precisioninformationis obtained for everyspike parameterin the samplematrix even if that parametermay not bepresent. Duplicateinformationfor parametersat "less than" concentrationsare not usefulfor making precisionestimates. The disadvantagesof MSDs arethat they requirean additionalpreparationif unspikedduplicatesalso areperformedand do not provideactual samplereproducibilityif unspikedduplicatesare not performed. If only MSDs are used it may be more difficultto evaluatesamplehomogeneity. The MSDs have been specifiedonly for organicanalyses.

There are many ways to establishdetectionlimits and the methodsmaydiffer with each parameter. ResourceConservationand RecoveryAct (RCRA)detectionlimit requirementsare based on determiningthe 'limitin the samplematrix. However,for SST matricesthis could be difficultsince it is

necessaryto find samplesthat do not containthe parametersof interest.This approachmay be needed in Phase II to prove that a parameterIs below alimit but is not needed in Phase I for generalcharacterization.For stableinstrumentsand analyticalsystemsthe detectionlimit may be determinedorverifiedless frequentlythan for less stablesystems. The detectionlimitfor each parametershouldbe specifiedfor each segmentand core composite

• data packagebased on the normal samplesize, preparationand analyticalmethod, and operatingconditionsused. These conditionsshould be specifiedfor each detectionlimit provided. The methodsfor determiningdetectionlimits and the frequencyof evaluationshall be documentedfor each applicableparameter.

Acceptancecriteria for most parametersare based on SW-846 proceduresthat considersa value 3 standarddeviations(3a) outsidethe mean as beingout of control. Calibrationverificationstandardsmay be specifiedabsolutely(gO to 110%) for some parametersrather than by standarddeviationsor performance. The analytetype may also impactthe acceptancecriteriasince lower priorityanalytes(Type III) shouldnot requireas high a level ofperformanceas Type I and II analytes.

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Blanks are used to assess contamination levels in the field, hot cellsand laboratory. A system for collectingblank data and settingguidelinesforacceptingor rejectingdata based on the level of contaminationin the blankshall be established. A historicalmean and three sigma limit shall bedeterminedfor the field blank, hot cell blank,preparation(method)blank andcalibrationblank. The blank resultsfor a parametershall be comparedto itsconcentrationthresholdor regulatorylimit to determineif the blank resultwould affectevaluationof sampleresultsat these concentrations. If theblank is less than 10 times these limitsor 10 times less than theconcentrationof the analytein the sampleJt is probably insignificantandeffortsto removethe contaminationsourcewill not be as important.Additionalexperienceand data will be needed in Phase IC to evaluateblanklevels and blank controlfor the high level of inorganicsalts found in SSTsludgescomparedto soils and waters.

Duplicateanalysisacceptancecriteriawill depend on the concentrationlevels in the sampleand on the heterogeneityof the sample, lt will alsodepend on the effectivenessof the homogenizationmethod. Both CLP andSW-846 proceduresset relativepercentdifference(RPD) criteria for ICP andAA duplicatesat 20% when the analyteconcentrationis 5 times the contractrequireddetectionlimit (CRDL)for CLP or 10 times the instrumentdetectionlimit for SW-846. The 20% limit is a goal that duplicateanalysisofSST waste should attemptto achieve. However,it may not be achievableforthese complexwastes that are difficultto homogenize;therefore,the RPD ofresultsshould be comparedto the historicalmean and +3o limits to determineif the performanceof the methods have changedsignificantlyfor that tank.The method reproducibilityalso must be evaluatedbased on the DQOrequirements. If confidentdecisionscannot be made from the data becauseofthe reproducibility,better homogenizationand analysismethodswill have tobe developed. Data whose reproducibilityis questionableshould be identifiedand explained. Matrix spike duplicatesmay be implementedin the futuretoreduce the effectof low concentrationlevels.

Matrix spike acceptancecriteriaalso is difficultto establish. Matrixspike recoverycriteriafor CLP and SW-846,ICP and AA methods are set atbetween75 to 125%; however,severalfactorscan keep a sample from meetingthis specification. If the spike concentrationis only a fraction (25% forCLP) of the sampleconcentration,variationsin the sample concentrationwillimpactthe spike recovery. Normallyspikesfor analytes>0.1 wt% are notevaluatedfor this reason. Instead,a serialdilution is made that shouldagree within_+lO_of the originalanalysis. When spikes are added to aseparatedigestionaliquotthe sampleheterogeneitybecomesa factor in thespike evaluationsince the spike aliquotmay containsignificantlymore orless of the constituentthanthe originalaliquot.

The laboratoriesshall make an effort to determineif a matrixinterferenceexist and identifythe cause of the interference. If the spikerecoveryresultsare not between75 and 125_,they shouldbe comparedto themean spike recovery±30 limitsto evaluateif this sample representsasignificantchange in performance. If the resultsappear to be significantlydifferentthan normal,the analyticalgroup should attemptto identifyif theproblemis one of heterogeneityor a matrix effecton the method by using

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techniques such as additional duplicate analyses, or post digestion spikes,Results outside the normal spike performance or post adjustment spikes outside50 to 150% should be identifiedand follow-upwork and recommendationsdescribed, lt is importantin the early stagesof Phase lC to identifymatrixinterferencesand procedureproblemsso that they may be corrected. The goalof the project is to have methodsthat providespike recoveriesbetween75 and125% for all analytes;however,this may not be importantfor the DQOs for allanalytesand for all users of the data. The QC performedon SST samplesmaybe restrictedby the amountof sample available The amount of exploratorywork to evaluatematrix interferencesshall be iimitedso that schedulesandcosts to completethe analysesare not significantlyimpacted.

10.2 SAMPLINGQUALITYCONTROL

A minimumof one field blank per tank will be taken. This blank will beused to monitor cleanliness of equipment and transportation effects, An emptysampler will be filled with deionized water in the field and transported tothe laboratory where it will be emptied outside the hot cell and analyzed.Initially,the field blank will be analyzedfor the followingcomponents:

• Total alpha/beta/GEA

• InductivelyCoupledPlasma

• Ion Chromatography

• Organics (GasChromatography/MassSpectrometry)

• Total OrganicCarbon

• Atomic Absorption(arsenic,selenium,and mercury).

This list may be reducedif experienceshows that some of the parametersare not significant. This blank will act as a field,equipment,and tripblank. If significantcontaminationis found, individualblanks will bepreparedto identifythe sourceof contamination. If the sampling for a tankextendsover two weeks, a field blank shall be taken near the beginningandnear the end of samplingor one every two weeks. If the tank samplingwillinvolvea large number of samples(>20),the field blank frequencyshall be5% of the samplersused. The field blank levels shall be monitoredandcomparedto DQOs, regulatorylimits and sample concentrationlevels. If theblank is significantthen the source of contaminationshouldbe identifiedandremoved. If the contaminateis a Type III analyteor its concentrationthresholdlimit is large or it is less than 10% of the concentrationfound inthe samplethe importanceof removingthe contaminatewill be less.

In Phase IA and IB two cores were taken from the same riser to evaluatethe samplingerror. This samplingerror is made up of errors caused by thesamplingtechniqueand variancescaused by heterogeneityin the waste. Thesemisolidcharacterof the waste makes taking two identicalsamplesfrom thesame riser locationdifficultsince taking the first core may disturb the

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waste and affect the abilityto take the second core. In addition,taking thecore from a differentriser would providemore useful informationon wasteheterogeneityand inventory_therefore,this type of duplicatefield sampleisnot plannedin Phase IC unless resultsfrom Phase IA/IB indicateit may beuseful. The programplans to take at least two cores from the same tank butdifferentrisets.

10,3 SAMPLEBREAKDOWNQUALITYCONTROL

A minimumof I hot cell blank per tank or I for every 10 segmentsextrudedshall be prepared. This blankwill be preparedby rinslng theprecleanedreceivingtray and aliquotingequipmentwith deionizedwater andcollectingit in a normal segmentstoragecontainer. The storagecontainerwith the rinse water is removedfrom the hot cell and analyzedfor thefollowingcomponents:

• Total alpha/beta

, Gamma EnergyAnalysis

• InductivelyCoupledPlasma

• Ion Chromatography

• Total OrganicCarbon

• Atomic Absorption(arsenic,selenium,mercury)

• Organics (GasChromatography/MassSpectrometry).

This list may be reducedif experienceindicatesthat no significantquantitiesof the constituentsare found. This blank will monitor thecleanlinessof equipmentused to receive,store, and subsamplethe segmentsamplesin the hot cell. Criteriafor the hot cell blank is the same as forthe field rinse blank.

Extensivesample homogenizationtests were performedin Phase IA and IBin which effortswere made to measureindividualhomogenizationand analyticalerrors. In Phase IC the homogenizationand analyticalerror will be monitoredbyanalyzing at least one segmentper core in duplicatefor ICP and GEA. Twoaliquotswill be taken from two extreme (top/bottomor left/right)locationsin a homogenizedsample. The two aliquotswill be analyzedin duplicateusingthe standardICP acid digestionand analyzingthe final solutionfor metals byICP and Cs-137 by GEA. The numberof homogenizationtests may be increasedifsegmentsare found that are more heterogenousthan normalor the wastesphysicalnature is expectedto cause homogenizationproblems. If possible,segmentsselectedfor homogenizationtestingshould be chosen so that theyrepresentthe differenttypes of wastes in the tank not just wastes with thesame consistency.

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Reproducibility of compositing segment samples (core composites) will beevaluated on at least one core per tank by preparing two core composites fromone set of segment samples. This will monitor how well segment subsamples canbe taken, weighted, and homogenized to form a composite. The duplicate corecomposites will be analyzed in duplicate for the full set of core compositeparameters. Acceptance criteria for the homogenization and compositing errorswill be based on the historical mean of the relative percent differences (RPD)and its ±3G limit.

10.4 METALCHEMICALPARAMETERS

10.4.1 Metals--Inductively Coupled PlasmaOpttcal Emission Spectroscopy

The determination of metals by ICP will be used to measure 30 metals ofinterest. The inductivelycoupledplasma (ICP) equipmentis relativelyunstableand it must be calibratedfrequently. The calibrationrequirementsin Table D-6 are based on SW-846 and CLP requirements. Calibrationverificationincludesan initialcalibrationverificationfollowedbycalibrationchecksevery 10 sampleswith an independentverificationstandard.The calibrationverificationstandardand laboratorycontrol standardcan bethe same standardprovidingit is preparedfrom a differentsourcefrom thecalibrationstandardand checks all 30 metals. The ICP equipmentmay alsomeasureanother10 to 20 metals dependingon its configuration. However, theQC for tBese metalsdoes not have to be controlledat the levelsdescribedinTable D-6. The instrumentshouldbe calibratedfor thesemetals _o that ifthey are present,their concentrationscan be estimated. If significantquantitiesof one of these other metals are found in the tanks, they will beincludedin the primaryanalysisset.

The preparationblank monitorsthe acid, water, and equipmentto prepareICP samplesfor possiblecontamination.The blank shall be preparedusing adifferentset of equipment (i.e.,beaker,volumetricware) each time.A preparationblank shall be preparedwith each acid digestion,fusion orwater preparationbatch.

The laboratorycontrolstandard (LCS)and continuingcalibrationverificationstandardcan be the same standard(s). This standard(s)shallcontainall the metals of interest. The LCS shall be carriedthroughthe samedigestionprocessto evaluateerrors associatedwith digestionandICP instrumenterrors. The CLP requiresthat one duplicatebe analyzedfromeach group of samplesof a similarmatrix type (soil,water) and concentration(low high). ProposedRCRA guidelines(EPA 1989) statesthat the frequencyofduplicatesshall be based on DQOs for the data collectionactivity. Duringthe early stagesof Phase lC when the DQOs are being developedthe frequencyof duplicatesmay be greater than when the DQOs are finallydefined. At leasttwo sets of duplicateICP resultsshouldbe collectedfor each tank to permitcomparisonof errors associatedwith analysis(homogenization,measurement)and errorscaused by tank waste heterogeneity. The objectiveof the analysisprogram is to controlmeasurementerrors so that they are a minor componentof

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the overallvariabilityof tank measurementsand do not impactDQOs. BecauseICP will be used to evaluatehomogenizationprocedures,the ICP duplicatescanbe performedon segmentsor core composites. The ICP duplicatesshouldbeperformed on the acid, water, and fusiondigestionaliquots.

The CLP spike frequencyrequirementsare definedthe same way as theduplicatesdescribedabove. The proposedRCRA guidance (EPA 1989) requiresamatrix spike with each batch of samples. Batch is definedas a group ofsamplesthat behave similarly,have the same matrixchemical propertiesandare processedas a unlt. If the numberof samplesin a group is greaterthan20, then each group of 20 samplesor less is handledas a separatebatch. TheSW-B46 ICP method 6010 recommendsmatrix spike duplicates(MSD) at a 20_frequency. Matrix spike duplicatesare not specifiedfor CLP inorganicanalyses. Matrix spike duplicatespermitboth precisionand accuracyerrorsto be determinedfor the matrix. If the metal concentrationis low (less thanvalue),precisionestimatesfrom normalduplicatesare not possible.

The QC plan in Table D-6 assumesthat each core representsa differentmatrix;thereforea spike is requiredfor each core. When the samplematrixvisuallychangessignificantlybetweensegments,additionalmatrix spikesmaybe requestedif ICP analysisof segmentsis being performed. The hot celloperationspersonnelextrudingthe segmentsshould identifythese segmentsanddiscussthe optionof runningadditionalspikeswith the projectmanagerortechnicalleader. The overallobjectiveis to establishthat the methodperformsproperlyfor the differentmatricesfound in the tank. If a metal ispresentat >0.1 wt% concentration,spikingis not required;however,matrixeffectsfor these parametersshall be evaluatedusing a serialdilution.Spikes for ICP analysisof fused samplesare not required since this analysisis capableof only measuringmetals at relativelyhigh concentrations. Metalspikes shouldnot be added beforethe water digestion.

Spikes shall be added to samplesbefore the acid digestion. Poor spikerecoveriesmay resultfrom the digestionprocess,sample heterogeneity,instrumentinterferences,or too small a spike comparedto sampleconcentrationfor the parameter. If spike recoveriesare outsidecontrollimits,a post digestionspike (spikeadded to a portionof unspikedsampleafter digestion)shall be used to determineif the problemis associatedwithdigestion,sample heterogeneityor an instrumenteffect. One additionalsetof duplicatesshouldbe run to furtherevaluatethe sample heterogeneityif itis believedto be the cause of poor spike recovery. If sample heterogeneityis the problem it shall be identifiedwith the data. Decisionson the spikeevaluationwill dependon the amount of sampleavailableand shal_ be directedby the technicalleader.

Detectionlimits shall be determinedevery three months or wheneverchanges in the instrumentcould result in a change in performance. Detectionlimits shall be reportedwith each data package. The CLP procedurefordeterminingdetectionlimitsrequiresmaking seven consecutivemeasurementsfor the parametersat concentrations3 to 5 times the estimatedinstrumentdetectionlimit for three nonconsecutivedays. New proposedRCRA procedures(EPA 1989) requiredeterminingmatrix-specificdetectionlimits for

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demonstratingcompliancewith a regulation,DQO or other study objectiveforany value reported less than a specificregulatorythreshold. This procedurerequiresmaking three post-digestionmatrix spikes additionsfor theparametersof interestat concentrationsof 3 to 5 times the estimateddetectionlimits, This approachalso requiresfindingsamplesthat do notcontainany of the parametersof interest. For 20 to 30 parameters,this canbe difficultto do; therefore,the CLP approachwill be used during Phase lC.The matrix-specificapproachmay be required in Phase II to verify valuesreportedbelow regulatorylimits. i

For matrices such as inorganicsludges, interelementeffectscan affectthe accuracyand detectionlimitsof ICP results. Both CLP and RCRAproceduresrequire interelementcorrectionfactorsto be checked before andafter the end of an analyticalrun or twice during every B-hour work shift,The CLP defines the analytesand interferentsand their concentrationlevp,sfor the interferencecheck sample. The SW-846 procedure6010 is not as welldefinedand addressesa wider range of analytesand interferents. The SSTinterelementcorrectionfactorsshouldconsiderall the major metals(>0.1wt%) found in SST waste as interferents. These will normally includesodium,aluminum,iron, bismuth,anduranium. Uraniumis particularlyimportantbecauseof its numerouslines and complexspectra. Some SST wastemay containsignificantquantitiesof rare earthswhich also have complexspectra. If rare earths or other metals are found in the analysisat>0.1 wt% concentrationsthe interelementcorrectionsfor these componentsmustbe checkedand if necessaryadded to the interferencecheck sample for thattank. All the metals in the DQO list in Table D-3 shall be evaluatedforintarferencefrom these major components. When positiveresults are obtained

for a metal not believedto be possiblein the SST waste, interferencefromanotherwaste componentshouldDe evaluated.

The CLP procedureuses a contractrequireddetectionlimit (CRDL)standard (CRA) to verifythe linearityof the ICP system near the detection ,._limit. The standardis made up of all analytesexcept aluminum,barium,calcium,iron, mercury,sodium,and potassiumat two times the CRDI.or twotimes the instrumentdetectionlimit whicheveris the largest. A similarstandardshall be used for evaluatingSST waste ICP analysesfor trace metals.In additionto the metals mentionedabove,metals silicon,zirconium,thorium,and uraniumdo not need to be includ(;d.The CLP criteriafor these standardsis not established;therefore,CRA standardswill initiallybe used forevaluationrather than controlpurposes.

10.4.2 Metals--GraphiteFurnace AtomicAbsorption

The GFAA qualitycontrolrequirementsfor the SST waste characterizationare based on CLP and RCRA (SW-846)procedures. Metals routinelyanalyzedbyGFAA (As, Se, Sb) were identifiedas Type II or III anal)tee in the analyteprioritiesreportwhen they were assumedto be presentat I wt% concentrationin the waste. In actualitytheir concentrationis expectedto be at least anorder of magnitudeless. Therefore,the qualityof these resultswill not beas criticalto long-termreleaserisk evaluationsas Type I analytes. On the

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other hand, these metals are of regulatoryinterest. Therefore,sufficientqualitycontrolis requiredto providedata with known uncertaintyand toevaluatemethodperformanceon the waste matrix. Lead (Pb),which is a Type Ianalyteis occasionallyanalyzedby GFAA to verify ICP resultsor to obtainbetterdetectionlimits.

The calibrationrequirementsfor GFAA analysesare essentiallythe sameas for ICP analyses. The singlecalibrationper day is based onCLP procedures. The RCRA (SW-846)proceduresrecommendhourlycalibrationsfor arsenicand selenium. This wasnot adoptedbecauselong drying and ashingtimes for some matricescould severelylimit the analysisthroughput. Morefrequentcalibrationverificationchecksshall be used to identifywhenrecalibrationis needed if instrumentstabilityis a problem. The calibrationshall includea blank and at least three standards. If the instrumentis notdesignedfor these standardsin the calibration,calibrateaccordingto theinstrumentmanufacturer'srecommendationsand use the additionalstandardstoverifythe calibration. If the recoveriesare outsidegO_ to 110_, thecalibrationshall be repeated. A ca'fibrationblank shall be run at leastevery I0 samplesto ensureno memoryeffectsare occurring. If memory effectsare noted, the conditionshall be correctedand the calibrationblankfrequencyincreased.

A preparationblank shall be run with each dlgestionbatch. Two sets ofduplicateGFAA results (example: duplicatefor each of 2 composites)shall becollectedfor each analytefor each tank unless more sets are specifiedin theDQOs or test plan. The CLP procedurerequiresduplicateinjectionsfor eachsampleto evaluatethe reproducibilityof the injectionand furnacesystem forthe matrix. This resultsin fastergraphitetube deteriorationand reducesanalysisefficiency. For SSTs at least one duplicateinjectionfor every fivesamplesnr one per batch shall be done to evaluate instrumentreproducibility.If the RPD exceeds20_, the problemshouldbe correctedand/orthe frequencyof duplicateinjectionsincreased.

The GFAA analysisby CLP proceduresrequiresthe use of both predigestionand post digestionspikes and a complicatedschemeof spike evaluation. Thislevel of control is not considerednecessaryfor Phase I analysisof Type IIanalytes. In the SST characterizationprogram at least one predigestedspikeshouldbe performedon each core or with significantmatrix changeswithin thetank. The hot cell operationsgroup shall have the lead in identifyingwhensignificantmatrix changesoccur and additionalspikesare needed. Eachsample (exceptthe predigestedspike sample)shall be analyzedwith a postdigestionspike. If the spike recoveryresultsare not between50% and i50%,the data shall be flaggedand the problemdocumented If appropriatethemetF_odof standardadditionsshouldbe used to evaluate sampleswith spikerecoveriesoutsidethese limits.

The method of standardadditions(MSA)may providemore accurateanalysesfor some types of matrix interferences;however,it is not effectiveforspectralinterferences. The technicalleader is responsiblefor deciding ifMSA shouldbe used dependingon such factorsas the potentialsource of error,the magnitudeof the error and the concentrationlevel and priorityof theanalyte.

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The CLP proceduresuse contractrequireddetectionlimit (CRDL)standardsto evaluatethe instrumentperformancenear the detectionlimit. SinceGFAA metals are expectedto be low or near detectionlimits,a CRDL standardshall be analyzedtwice in an 8-hour operationperiod. Detectionlimits shallbe determinedevery 3 months and reportedwith all data during that period.

10.4.3 Metals--Hydride Atomic Absorption

Hydrideatomic absorptionanalysesalso may be used to analyzeforarsenic,selenium,and antimony. The QC requirementsfor HYAA are based onSW-846procedures. The HYAA systemshall eitherbe calibratedhourlyusing ablank and three standardsor data shouldbe bracketedwith calibrationverificationstandards. A calibrationverificationor laboratorycontrolstandardand a preparationblank shall be run with each batch of samples. Ifspike recoveriesroutinelyfall outsidethe 50% to 150% range, an attempttoidentifythe cause of the error shall be made by evaluationof sampleheterogeneityor if appropriatethe method of standardadditions(MSA)applied. Detectionlimits shall be determinedand reportedon a quarterlybasis.

10.4.4 Metals--ColdVapor Atomic Absorption

Mercuryis the only metal analyzedby cold vapor atomicabsorption(CVAA)techniques. The QC is based on SW-846 procedureswhich requireshourlycalibrationswith a blank and three standards. The CLP requires a dailycalibrationfrequency. If hourly calibrationimpactsanalysisefficiency,daily calibrationcan be used providedthe data is bracketedwith calibrationverificationstandardsin the same range as the sample. If the calibrationverificationstandardrecoveriesare outsideof 80% to 120%, the instrumentmust be recalibratedand the samplesreanalyzed. The method of standardadditions(if appropriate),method changes,or heterogeneityeffectsshall beevaluatedif spike recoveriesare outside50% to 150%. Detectionlimits shallbe determinedand reportedon a quarterlybasis.

10.4.5 Metals--Fluorimeter

Total uraniumis determinedusing a laser fluorimetertechniquebased ona single standardaddition;therefore,the instrumentis calibratedwith eachsample. At least one calibrationblank shall be run with each batch ofsamplesanalyzedon the fluorimeterto _nsurecells are being properlycleaned, If the blank is greaterthan 5% of the sampleconcentrationlevel,the previoussamplesshall be reanalyzed. Preparationblanks are used tocheck for contaminationin the fusionprocedure. The method detectionlimitshall be definedand the basis for determiningthe limit documented. Thedetectionlimit shall be reestablishedanytimethe equipmentor procedurechangesoccur that may impactthe method performance.

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10.4.6 fletals--Ultraviolet Spectrophotometry

ChromiumVI may be determinedby using spectrophotometry.This equipmentand method are more stablethan ICP and AA techniquesand do not requireasfrequentcalibrations. This approachis supportedin new guidelinesdiscussedby EnvironmentalProtectionAgency personnel(Friedman1990). Calibrationsshall be checkedafter equipmentmaintenanceor reagentchanges. A reagentblank is run with each batch of samples. The calibrationshall be checkedwith each batch of samplesusing either an independentcalibrationverificationstandardor a laboratorycontrolstandard. The method detectionlimit shall be definedand the basis for determiningthe limits documented.The detectionlimitsshall be reestablishedany time equipmentor procedurechangesoccur that may impactthe methods performance.

10.5 A)IIONCHEMICALPARAMETERS

10.5.1 Anions-lonChromatography

The QC requirementsfor ion chromatographyare based on "TheEnvironmentalSurveyManual"(DOE 1987) and EPA Test Method 300.0-I(EPA 1989). After initialcalibration,the calibrationverificationstandardor laboratorycontrol standardshall be used beforeand after a set ofanalysesand at least after every 10 samples. The instrumentmust berecalibratedwhen the eluent is changedor when the calibrationor controlstandardrecoveriesare outsidethe 90% to 110% limits. A calibrationblankshouldbe analyzedafter every 10 samplesto ensurethe columnsare beingadequatelyflushedbetweensamples. The retentiontime shall be checkedwitheach calibrationverification. If the retentiontime has shiftedby more thanI0% from the expectedvalue,the run shall be stoppedand the cause of theshift identifiedand a new calibrationpreparedif required. The detectionlimits for each anion shall be defined and the basis for determiningthelimitsdocumented. The detectionlimits shall be reestablishedany timeequipmentor procedurechangesoccur that may impactthe methods performance.

10.5.2 Anions--Spectrophotometry

Nitrite is determinedby spectrophotometryin the 222-S facilitywithQC requirementsessentiallythe same as those for Cr(VI) under metals.Becausenitrite is easilyoxidizedby air, standardsshall be preparedon afrequentbasis (at least weekly).

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10.5.3 Anions--SelectiveIon Electrode

The PNL 325 Laboratorypersonneldeterminefluorideby selectiveionelectrode(SIE). The instrumentis calibratedbefore analysisof each batchof samples. Calibrationmay be done graphicallyusing at least threestandardsor direct concentrationmeasurementsusing two standards. Analysis

O of samplesmust be bracketedby the standards. The calibrationshall be

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checkedusing the calibrationverificationstandardor the laboratorycontrolstandardonce every 10 samplesand after each batch. The detectionlimits forSIE shall be establishedwith each new electrodeand any procedurechange thatmay affect its response.

10.5.6 Anions--Distillation

Cyanideand sulfideare determinedby distillationand final measurementusing spectrophotometry,titration,or selectiveion electrode.Thedistillationof these anionsrequiresa long periodof time and limits thethroughputof analyses;therefore,they are performedwith reducedQC for someareas. The calibrationrequirementsfor cyanideare essentiallythe same asfor Cr(VI) and nitrite. The calibrationblank is a reagentblank for thespectrophotometer.A preparationblank is a check on the distillationequipmentand reagentsused for distillation. One of these shall be preparedat the end of each day (8 hours). The preparationblank shall be preparedusing a differentdistillationsystemeach time so that all systemsarecontinuallycheckedfor contamination. The verificationstandardis astandardthat is not carriedthroughthe distillationbut is analyzedwitheach batch of spectrophotometricsamples. The laboratorycontrolstandard iscarriedthroughthe distillationto verify its operationalefficiency. Atleast one laboratorycontrolstandardshall be run every 8 hours usingdifferentdistillationsystemsin the same manner as the preparationblank.If a microdistillationsystemthat can distillmultiple (10 or more) samplesis used, a preparationblank and laboratorycontrol standardsshall beanalyzedwith each distillationbatch.

10.5.7 Anions--pH

The determinationof pH is calibratedeach time using two standardbuffersbefore making measurements. The pH calibrationshall be verifiedevery 10 samplesor after each batch of analysesto ensure the electrodehasnot drifted. If the pH of the standardhas driftedby more than _+0.05,theelectrodeshall be recalibratedand the samplesrerun. Calibrationandpreparationblanksare not requiredsince the pH of the samples is notexpectedto be affectedby the pH of the deionizedwater used to preparethesample. Matrix spikes and detectionlimits are not applicable.

10.5.8 Anions--TotalInorganicCarbon

Carbonates are determined using TIC/TOC equipment. The carbon dioxidegas release is either measured by nondispersive infrared (NIR) analyzer or bycoulometric titration. Since calibration procedures vary with each type ofinstrument, the calibration shall be performed according to the instrumentmanufacturer. The NIR systems normally are calibrated with several standardsbefore each batch of analyses with verification performed during analysis ofsamples (1 per 10 samples) and at the end of the run. Verification standardrecoveries shall be within 90% to 110%or the instrument recalibrated andsamples rerun. The coulometric titration systems require only a verification

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standardrun before,during (I r,er 10 samples),and after analysessincecoulometryis a primarystandardizationtechnique. The method detectionlimitshall be definedand its basis documented. The detectionlimit shall bereestablishedany time equipmentand procedurechangesoccur that impactthemethodsperformance.

10.5.9 Other Methods--NHz, Fe(CN)6"4

Ammonia is determinedby distillationand titrationat the222-S Laboratory. No calibrationor calibrationblank is necessarybut alaboratorycontrolstandardshall be used to verifythe distillationequipmentand titrationreagentsproduceacceptableresults. At least one laboratorycontrolstandardand preparationblank (distillationblank) shall be preparedevery 8 hours like the cyanidesystems. The PNL 325 Laboratoryuses SIE todetermineammoniawithoutthe need for distillation. The QC requirementsforthis procedureare the same as those for fluoride.

The method for ferrocyanidespeciationis still under development,thereforeQC requirementsfor the instrumentsand procedurecannot beestablished.

10.6 ORGANICPARAHErERS

10.6.1 Organic--Total Organic Carbon (TOC)

The TOCQC requirements are essentially the same as those for carbonateor TIC.

10.6.2 Organic--Total/Extractable Organic Halides (TOX/EOX)

The coulometric chloride analyzer calibration on the TOX/EOXsystem shallbe checked daily using a chloride standard. If the calibration does not agreewithin ±2% the instrument parameters shall be adjusted according to theinstrument manufacturer. The performance of the entire TOX/EOXsystem shallbe checked by triplicate injections of an independent check standard afterevery 10 samples. The standard recovery should be within 80 to 120% and thestandard deviation of the injections shall be <±10%. A preparation blank (EOXextractan+_) and laboratory control standard shall be analyzed with each batchof samples. The method detection limit shall be defined and its basisdocumented. The detection limit shall be reestablished any time equipment orprocedure changes occur that may impact the methods performance.

10.6.3 Organtc--Complexants

The method for determining organic complexants has not been determined;therefore, QC requirements for the instrument and procedure cannot beestablished.

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10.6.4 Organic--Ge/Hs (Volatile Organics by Purge and Trap andSemtvolattle Organics by Capillary Columns)

The volatileorganicanalysisQC requirementsare based on the mostrecent CLP Statementof Work (SOW) (EPA 1990). The EPA is in the processoftrying to developone set of methods and QC requirementsfor both CLP andRCRA programs. Since the CLP SOW representsthe most recent change inprocedures,it is assumedthat it is the directionthe EPA is going. TheQC requirementsfor GC/MS analysisof volatilesand semivolatilesare verydetailedand will not be provided in this document. For details the CLP SOWand applicableRCRA (8240,8270) proceduresshouldbe consulted Table D-6and this discussionprovidegeneralguidelinesfor the QC of these methods.Calibrationsmust be checkedevery 12 hours with a one point standard. Beforecalibrationsare performed,the GC/MS must be tuned accordingto the CLPprocedure. Before analyzingsamplesthe systemperformancecheck compounds(SPCCs)and calibrationcheck compounds(CCCs)must be run and meet CLPperformancecriteria. The CCCs and SPCCs are also includedin the initialcalibration. These same check compoundsand preparationblank must beanalyzed every 12 hours. Each blank, standard,and sample are analyzedwith asurrogatestandardand an internalstandard. Since the CLP and RCRAproceduresrequireat least one matrix spike and one matrix spike duplicatefor every 20 samples,only one set (ratherthan two) has been specifiedpertank. Duplicates(withoutspikes)are not requiredby CLP and RCRA GC/MSprocedures;however,one duplicateper tank shouldbe performedto evaluatesampleheterogeneity. Spikedduplicatesmay overshadowsample heterogeneityeffects.

There appearsto be two major QC differencesin CLP and RCRA procedures.Since each sample is spikedwith known surrogatesand internalstandards,theCLP proceduredoes not requirea laboratorycontrolstandard. The RCRAprocedurerequiresa qualitycontrolcheck standard (laboratorycontrolstandard)with each batch. The other area, which is different, is theacceptancecriteriafor these controlchecks. The CLP procedurehas specifiedthe acceptancecriteria,whereasRCRA allowsthe lab to establish its owncriteriabased on the actualvariancesobserved. The goal of the analysisshall be to meet the CLP criteria;however,the laboratorie_shall collectstatisticalinformationto set 3a limits for the standard,duplicate,andspike measurementsto evaluatethe method performanceon SST matrices and forcomparisonto CLP and SW-846 performancespecifications.The varyingNPHcontaminationand matrix uncertaintiesare expectedto produceproblemswithsurrogateand matrix spike recoveries. If largersamples (lOg) are needed tomeet the requiredDQOs, such as TCLP compoundlimits and Ecologyguidelinesof10#g/g for organics,there may be insufficientsamplefor all QC tests. Oneset of duplicatesand matrix spike duplicatesrequireat least 40g of samplefor each type of organicanalysis. If inadequatesample is available,theduplicateand then the matrix spike duplicateshall be droppedfrom analysis,in that order, dependingon sample quantitiesavailable.

The primary objectiveof these organic analysesis to prove thatsignificantquantitiesof organicsare present in the wastes and if any of theorganicsare of regulatoryinterest,or could contributeto the overallrisksin the tank. Since the objectiveis not to prove that the organics are below

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regulatorylevels,the level of QC for the analysesin Phase I does not needto be as high as in Phase II. Laboratoriesshall make reasonableattemptstomeet CLP requirementsand documentthe resultswhen these requirementscannotbe met.

10.7 Radiochemical Parameters

10.7.1 Radionuclides--Alpha

The QC requirementsfor radionuclidesis based on the EPA HandbookforAnalyticalQualityControlin RadioanalyticalLaboratories(EPA 1977). Thealpha countersused in the WestinghouseHanfordand PNL laboratoriesareeitherwindow or windowlessgas-flowproportionalcountersor zinc sulfidescintillationcounters. These detectionsystemsnormallyare stable afterinitialcalibrationand only need to be checkedto ensure they are operatingproperly. All radiochemicalcalibrationsshall be done with standardstraceableto National Instituteof Standardsand Technology(NIST).Calibrationsshall be checkedfollowingany maintenanceactivitiesthat couldmodify equipmentperformance.

If alpha energy analysis (AEA)systemsare used for determiningabsolutealpha concentrations(not just ratios)the same calibrationconditionsapply.In addition,the alpha energy peak locationsshall be checked and adjustedasrequiredby the operatingprocedure,unless the equipmentperforms a selfcalibrationof alpha energieswith each measurement. Backgroundsmust beacquiredfor each detectorsystemon a regularbasis. The recommendedfrequencyfor taking the backgrounddependson the normalcounting time usedfor analysisof samplesas noted below:

Count Time BackgroundFreQuency0 - I hour I per 8 hoursI - 8 hours i per 24 hours>8 hours I per week

These frequenciesmay vary dependingon if the countingroom operatesona single8 hr shift or three B hour shifts. At least one backgroundshall bedeterminedper day unlesscount times exceed 8 hour. These same conditionsapply to check standardfrequency.

If the backgroundcount is outsidethe _±3o controllimit, recounttoconfirmit is out of controland clean the detector. Samplesbetweenthe lastgood backgroundand out of controlbackgroundshall be recountedusing the newbackgroundlevel. If the count rate for the samplesare high enough that thechange in backgroundwill not significantly(+20%)affectthe result,recountingthe samples is not necessary. Example: The backgroundshifts from0.1 to 1.0 c/m but the sample count rate is 100 c/m, recountingis notrequired. However, if the samplecount is 5 c/m or less, it shall berecountedusing a cleaneddetector. Alpha energy systemsnormally requirelonger count times becauseof their lower efficiency;therefore,backgroundsshall be taken at least once per week. The calibrationof the alpha system

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shall be verifiedwith a check standardat least once every 24 hours when theequipmentis in operation. The check standardcount rate is normallyhighenough that long count times are not required. Also it shouldbe high enoughconcentrationto have countingerrorsat <5%. If the check standardisoutsideits 3a limit, it shall be recountedto verify the out-of-controlcondition. If it is confirmedthat the system is out of control,it shall berecalibratedand the prior samplesrecounted.

A preparationblank is preparedfor each digestion(fusion)batch andprocessedwith the samplesto evaluatecontaminationin the analyticalsystem.If contaminationis found that is significantly(F+3o)over the background,the cause of the contaminationshall be identifiedand removed. Mostradiochemicalanalysesare performedwith disposableequipmentto eliminatethe potentialfor contamination.

A laboratorycontrol standardis processedwith each batch of samples.If adequatestandardisotopequantitiesare available,a mixed isotopiclaboratorycontrolstandardshall be preparedat concentrationshigh enough topermit accurate(±2 to 5%) countingrates after fusion,digestionseparation,and mounting. If there is insufficientisotopicstandards,the laboratorycontrolstandardis preparedat a lower concentrationand carriedonly throughthe separationmethod. If the laboratorycontrolstandardis outside the3a controllimit, the out-of-controlconditionsh_ll be verified the reasonidentifiedand currected,and samplesin the batch reanalyzed. If theconditioncannot be correctedthe data should be flaggedand the standardrecoverynoted.

Matrix spikesare not requiredfor radiochemicalanalysesif an isotopictracer is used in the analysis. Since these tracersare becomingdifficulttoobtain they must be used in limitedquantities. Therefore,they are used onlyto determinethe yield for the chemicalseparationportionof the procedures.2_pu or_6pu are used as tracersfor plutonium. Americium-243is used as atracer for Am-241 and curium isotopes. The tracersfor Pu and Am can bedistinguishedfrom the isotopebeing analyzedby AEA and thereforedo notrequirea separatealiauotfor analysis. Neptunium-23g,a gamma emitter, isused as a tracer for ZPNp. lt requirescountiji_gon both alpha and gammasystemsand becauseof the short half-lifeof _'Np the resultsmust be decaycorrectedfor each analysis. The laboratoriesshall report the percentrecoveryfor each isotopictracer. If an isotopictracer is not availableornot used, a matrix spike on a separatesample aliquotusing the same isotopethat is being analyzedmust be used. The matrix spike shall be at aconcentrationof at least 5 to 10 times the sample isotopeconcentrationsothat samplereproducibilityeffectsare minimized. Isotopictracersmust bestandardizedand maintainedas high qualitystandardssince any variationinthe tracer will be reflectedin the final results. The goal of the programrequiresprocedureswith tracer recoveries>50%. To evaluatespikerecoveries,historicalspike data will be maintainedand developmenttaskswill be identifiedfor procedureswith <50% yields. A matrix spike for totalalpha shouldbe used to evaluatesolidsabsorptioneffectson the results.Spikes shouldbe made at least 5 to 10 times the sample concentration. If theabsorptioneffectsof the solids exceeds20_, the sampleswill be diluted (ifpossible)and reanalyzed.

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Detectionlimits for countingmethodsdepend on many variablesDetectionlimitsfor the radiochemicalanalysison SST waste shall be reportedbased on the normal sample size, preparationmethod,separationmethod,counttime, detectorefficiency,and background. These conditionsshall bespecifiedfor each isotopedetectionlimit. These must be reportedwith eachdata packageor wheneverconditions,methods,or detectionlimitschangesignificantly(+25_). In additionto detectionlimits the 2a countingerrorshall be reportedfor each radioisotopeand each analysis. This providesinformationon the minimum reproducibilityerror for the analysisandindicateshow confidentthe data can be used.

A plateauand operatingvoltagefor alpha countersshall be determinedatleast every 12 months. The sensitivityof the alpha countersto countingbetas is importantfor SST analysessince the ratio of beta activityto alphaactivityis normallyvery large. The sensitivityof alpha countersto betashall be determinedby counting a high activitybeta sourceon alpha countingequipmentat least every month. If the beta counts are significant(couldresult in reportingfalse TRU >100nCi/glevels),the operatingvoltageshallbe adjustedaccordinglyor the detectorshall be limitedto counting sampleswith low beta activity.

10.7.2 Radionuclides--Beta

Radionuclides--Beta.The QC for determiningbeta emitting isotopesisessentiallythe same as for alpha isotopes. The major differencesare in theuse of matrix spikes and the evaluationof beta purity. Rather than isotopictracersmost beta isotopemethodsuse non-radioactivecarriersof the sameelementto determinethe chemicalyield throughthe separationprocedure.Carriersare added only for the separationmethod not at the digestion(fusion)stage. Thea_arrier recoveriesfor the _sotopeshall be reporteaforeach analysis. The °SSrtracermay be used for "USranalysis;however,present63 _9 _,proceduresuse a Sr carrie_, Ni, I, and Se all use carriers_ therespectiveelements. The "_Tcisotopemay be used as a tracer for "Tc;however,since it may not be_vailable and since there are no non-radioactivecarriers,a matrix spike of _Tc at concentrationsat least 5 to 10 times the

sampleconcentrationshall be.used,No Total beta resultsshall be reportedbased on "uSrYbeta efficiency matrix spike is requiredfor total betaresultssince absorptioneffectsare less than alpha, large dilutionsarenormallyrequired,and the total beta resultsare used only for an indicationof total activity.

129 _ _ 63Analysisof minor ( I, Se, Tc, Ni) isotopesin SST waste represents

of the most difficultprublemsbecauseof the high levels of _SrY ands, which can potentiallyinterferein the other analyses,if efficientisotopicseparationsare not obtained. The beta purityof the separationforeach procedureshouldbe establishedon SST matricesto show that no otherbeta isotopeis contributingto the result. This is particularlyimportantfor isotopesthat exceed the thresholdlimits. Beta purity may be verified bymultipleabsorbertechniquesin which a samplecontainingadequatebeta countsis countedrepeatedlywith increasingdensityabsorbers. Gamma energyanalysis (GEA) analysesof the beta mount also can be used to indicatethe

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presenceof other isotopessuch as IZTCs. Beta puritymeasurementsare notrequiredfor each determinationbut should be performedon a few samplesfromtanks in each operableunit. Once it is documentedthat the proceduresbeingused have no other beta interferencesbeta puritymeasurementscan beeliminated.

10.7.3 Radionuclldes--Beta/Liquld Scintillation

Beta isotopesalso may be determinedby liquid scintillationcounting.Tritium(H-3) and carbon-14(C-14)are the most common isotopesanalyzedby

liquid scintillation. The technologyfor liquid scintillationvariessignificantlybetweenmanufacturers,therefore,calibrationproceduresshallbe based on manufacturerrecommendations.Liquid scintillationcountersnormallyuse automaticsamplechangersthat count a backgroundandverificationstandardswith each batch of samples. The preparationblankevaluatescontaminationfrom the analysissteps and shall be preparedwitheach batch of samplesdigested. Carbon-14and H-3 matrix spikes shall beadded to the distillationsteps to estimatethe efficiencyfor distillation.Carriersmay be used to evaluatethe yield for other isotopesanalyzedbyliquid scintillationas describedfor beta countingmethods. Liquidscintillationsystemsshall providefor quenchcorrectionof the results (whenapplicable)based on manufacturerrecommendationsor operatinginstructionsBeta purity on some l'iquidscintillationsystemscan be evaluatedby printingout a beta spectrum. This shall be done wheneverSST sampleswith differentisotopiccompositionsor from differentoperableunits are analyzed. Thecheckingof the liquid scintillationsamplesby GEA may be used to verifypurity.

10.7.4 Radionuclides--Gamma Energy.Analysis

Gamma energy analysissystemsmust be calibratedfor each geometry usedand over the gamma energy range of all the isotopesanalyzed. TheGEA instrumentsare normallystable and do not requirerecalibrationunlessthe check standardindicatesthe system is out of control. The energyefficiencycurve shall be determinedannuallyfor each detector and geometrywith a multienergyreferencestandard(s)traceableto NIST standards. Thedetectorbackgroundshall be checkedat least every 24 hours when the systemis in operation. Less frequentbackgroundsmay be taken for longer counttimes as discussedin the alpha section. A check standardwith multiplegammaenergiesover the range of interestshall be run at least once every 24 hoursduring operation. The check standardneeds to be evaluatedfor efficiency(quantitativerecovery)and for energy linearity.The check standardmustincludepeaks in the low energy regionwhere linearityis the most critical.The check st_ndardshall be used to make any adjustmentsnecessaryin energypeak locationsto normalizethe instrumgntto calibrationconditions. If thecheck standardrecoveryor linearityis outsidethe 30 limits,the systemmustbe evaluatedfurtherand recalibratedif necessary. Samplesshall not beanalyzedon a systemthat is out of control. All samplesanalyzedon an outof control systemwill be reanalyzed,

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The laboratory control standard shall be processed through the digestion,dilution, and mounting steps if sufficient standard quantities are available.If sufficient standards are not available, the control standard shall beprocessed through only the dilution, mounting, and analysis steps. No matrixspike is needed for GEAanalysis since no separation steps are involved andabsorption effects are not significant, Low energy photon spectroscopy (LEPS)gammadetection sy._.temsare._sed for analysis of low energy (X-ray) emittingisotopes such as "'I. For '"I cold iodine carrier or a matrix spike shall beused to determine separation yield and evaluate matrix effects. Carrier orspike recoveries shall be reported for each analysis, Detector resolutionshould be checked and documentedat least once per month.

10.7.5 Radionuclides--Mass Spectrometry

Uranium and plutonium isotopes are determined by thermal ionization massspectrometry. This technique is used to establish the relative concentrationsof each tsotol_,_.(isotol_,i,c ratios) which is then used with alpha Pu informationto dete_tne <'uPu and <"Puisotooic concentrations and with total U by laser2_ 2]5 238fluorometry to determine U, _ and U isotopic concentrations. A NewBrunswick Laboratory (NBL) plutonium and uranium isotopic standard is analyzedwith each batch of samples to calibrate and verify the mass spectrometerperformance. A preparation blank is analyzed with each batch to check forcontamination in the system. A matrix spike is not required since onlyisotopic ratios are being measured. A detection limit shall be specified forthe normal sample size, separation and instrument. This limit is used only toevaluate if plutonium and uranium concentrations are high enough to allowisotopes to be determined on the waste and, therefore, only needs to bereported when it changes significantly.

Inductively coupled plasma mass spectrometry_(ICP-MS)lz_ay be used todetermine long-lived isotopes such as actinides, Tc and I. Procedures forthis new technology are in the process of being developed and should addressthe major qualitycontrolareas outlinedin Table D-6. EnvironmentalProtectionAgency methodsforICP-MS are expectedin the future and shall beused as guidancefor QC proceduresfor SST waste analyses.

10.8 PHYSICALMEASUREMENTSPARAMETERS

10.8.1 Physical Measurements--Bulk Density

This measurement has no calibration requirements. Balances used in themeasurement shall be calibrated at least annually. If the balance has aninternal check weight, it shall be checked before each batch of weighings.Volumetric equipment must be accurate to +_2%. Duplicate data is gathered toevaluatethe variabilityin the test unless it is determinedfrom weight anddimensionsor there is insufficientsample. Other QC areas such as matrixspikesand detectionlimitsare not applicable.

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i0.8.2 Phystcal Measurements--Particle Stze

•Equipmentshall be calibratedaccordingto the instrumentmanufacturer.A laboratorycontrolstandardor calibrationverificationstandardshall berun with each batch. Blanks are not requiredfor SST samples.

10.8.3 Physical Measurements--Penetrometer

The man,al mechanical penetrometer is a crude device used to determine ifthe waste is dllatantor cohesive;therefore,the QC requirementsare minimalTwo readingper segmentshall be taken to evaluatethe reproducibilityof thesystem unless it is obviousthe waste is so soft that only less than readingswill be obtainedor sample size and configurationpermitsonly one reading.The penetrometermechanicalconditionshall be evaluatedvisuallyto ensurethat corrosionof the spring or pistonhave not become excessive. If thesystem is showingsigns of deterioration,the penetrometershall be replaced.

10.8.4 Phystcal Measurements--Viscosity and Rheology

Rheologysystemsshall be calibratedin accordancewith manufacturerrecommendedprocedures. Blanks are not applicableto rheologymeasurements.A calibrationverificationstandardshall be run with each batch of samplesorat a frequencyrecommendedby the manufacturer. No laboratorycontrolstandardss,_mulatingwaste rheologyare available. No standardshave beenidentifiedfor shear strengthmeasurements. Duplicatesamplesshall be run ifsufficientsamplesare available. Replicaterheologyreadingsshall be takenfor a single sample. Presentrheologymethodsuse 50-I00gof sample,whichmay limit the number of duplicates. Duplicatesshall not be run if sample isneeded for additionaltests.

10.8.5 Physical Measurements--Porosity and Compressive Strength

These measurementsare intendedonly for hard saltcakesand sludges.Methodsmust be developedbefore the QC requirementscan be defined.

10.8.6 Physical Measurement--DSC/TGA

The DSC/TGAequipmentshall be calibratedaccordingto the ma,ufacturersrecommendationsor once per quarter. The equipmentscalibrationfortemperature,heat and weight measurementshould be checkedwith each batch ofsamples. Any sampleexhibitingan exothermshall be analyzed in at leastduplicateto verifythe results.

10.8.7 Physical Measurement--wt% Water

The weight percentwater shall be determinedin duplicatefor each sampleimmediatelyprior to subsamplingand analysisof each sample (segmentor core

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composite). The weight percentwater analysisshall be repeatedbefore anyother analysis is performedon a samplestoredfor 30 d or more. A laboratorycontrol standardshall be analyzedwith each batch of samples.

10.8.8 Physical Measurement--Other

Severalphysicalmeasurementshave been identifiedas part of thenecessarycharacterizationinformationfor tanks involvingUnresolvedSafetyQuestions, The measurementsneeded for the high heat tanks are thermaloutput,coefficientof thermalexpansion,specificheat, thermalconductivityand thermalconductivityof the frozen sludge. In gas generatingtanks, ameasurementdeterminingdeliquescencehas been identifiedas being necessarycharacterizationinformation.

10.g CHARACTERISTICSPARAMETERS

10.9.1 TCLP

A blank extractionis preparedwith each batch of samples l'roma tank.The ICP and AA analysesare performedusing the same guidelinesas the normalproceduresexcept spikesare added only to the TCLP extractand ILO!theoriginalsample beforeTCLP extraction.

10.9.2 Chemical Oxygen Demand

The method for determiningchemicaloxygendemand has not yet beendeveloped;therefore,QC requirementsfor the method cannot be established.

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Table D-6. QualityControlGuidelinesfor Characterizationof Sing e-ShellTank Wastes. (sheet6 of 6)

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11.0 LABORATORYPERFORMANCEANDSYSTEMAUDITS

Audits shall be precededby a specificsequenceof steps that identifyth_ appropriateperformancecriteria. This in turn establishesthe basis forthe audit requirements. The itemsthat verify these steps shall be in placeprior to the performanceof any EnvironmentalQualityAssurance(EQA) audit.These items are as follows:

I. The statementof work (SOW)--hasbeen agreed to by the laboratoryand by the customerwho has need for the analysisinformation.

2. The proceduresto be used in the performanceof work by thelaboratory--havebeen submitted,reviewed,and acceptedby thecustomerfor compliancewith the SOW.

Each laboratoryperformingwork for the singleshell tanks projectshallhave its own internalguidancefor performanceand system auditswhich shallbe in compliancewith the SOW. WestinghouseHanfordLaboratories(WHC) andBattelleLaboratories(PNL)have developedquality assuranceand controlforthis oversightas describedin their respectivequalityassuranceprojectplans. Audits shall be performedby EnvironmentalQualityAssurance (EQA) toverifythe laboratoryqualityprogramsare effective.

Environn_ntalQualityAssuranceauditingof WHC, PNL, or subcontractlaboratorieswill follow two basic formatsand will be applieduniformlytoeveryone. The only significantdifferencebetweenthe requirementsforinternaland externalaudits is in the authority,which is definedby WHCpolicyguidance for internalauditsand within the procurementcontract forexternalaudits.

Systemsaudits as definedin QAMS 005/80 part 5.12 shall be thecontinuingmeans of demonstratingcomplianceof systemsto the requirementsofthe SOW. These auditsshall be performedin accordancewith WHC-CM-4-2,QI 10.4, SURVEILLANCEto evaluateperformanceof individualsystems. Thesystemsaudit shall be performedinitiallywhen a system specifiedin the SOWbecomesoperationaland then on a randombasis in accordancewith a schedulepreparedand maintainedby EQA after receiptof the approvedSOW.

A performanceaudit as definedin QAMS 005/80 part 5.12 shall be thebasis to determinethe complianceof the laboratoryto the SOW. This auditshall be performedafter systemsare operationaland generatingdata andbiannuallythere after. The audit shall be controlledin accordancewithWHC-CM-4-8,QAI 18.1, PLANNING,PERFORMING,REPORTING,FOLLOW-UP,AND CLOSUREOF QUALITYASSURANCEAUDITS. Creditmay be taken for other auditqualificationof the laboratoryif it establishesreasonableconfidencein theperformanceof analysisfor this project. DefenseWaste Technologyshall berequiredto review and acceptthe audit resultsbefore the start of work.

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12.0 PREVENTIVEMAINTENANCE

Preventivemaintenancepoliciesfor the laboratoriesare describedintheir respectiveQAPJPs (WHC 1989, PNL IgBg).

The samplingoperationand each"laboratoryshall have a preventivemaintenanceprogramto ensure samplingand analysisequipmentis kept inproper workingorder. Maintenancelogs shallbe maintainedfor each majorpiece of equipmentto track equipmentproblemsand down times. Adequate spareparts for major equipmentshall be maintainedto preventexcessiveoown timesfor normal repairs.

Since most analyticalequipmentis based on electronicratherthanmechanicalsystems,preventivemaintenanceis minimal or not normallyrequiredfor most systems. Instrumentproblemsare normally identifiedwith the dailycontrolrequirementsof settingup the equipmentand analyzingsamples. BothWestinghouseHanfordand PNL have accessto in-houseinstrumentrepairgroupswho are capableof troubleshootingand handlingmany routinerepairs.

Calibrationand instrumentperformanceshall be checkedbefore resumingsample analysisfollowingany maintenanceactivitythat may affect the data.

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13.0 DATAASSESSMENTPROCEDURES

The data assessmentproceduresfor the laboratoriesare describedintheir respectiveQAPJPs (WHC 1989, PNL 1989). Accuracy for the SST programshall be assessedby trackingand collectingpercentrecoverydata(for allType I and Type Ii analytes)on laboratorycontrolstandards. The calibrationverificationresultsshall be assessed(tabulatedor plotted)by the analystor chemistin chargeof the analysis. The mean recoveryand relative standarddeviationof this data shall be determined,trackedby tabulatingor controlchartswith 2a warning limitsand 3o out-of-controllimits,and updatedon aregularfrequency. Method performance(accuracy)on the samplematrix shallbe assessedin the samemanner using matrix spikes.

The precisionof the data resultsshall be assessedby the relativepercentagedifferences(RPD)of duplicateanalysesor matrix spike duplicatesfor all Type I and Type II analytes. If the duplicatesample analytesresultsare less than five times the methoddetectionlimit, they are subjectto largedifferencesbecauseof procedurelimitations. This data should be analyzedseparatelyand used to evaluatemethod precisionnear the detectionlimit. Theother data would representthe variabilityat or above a reasonablequantitationlevel. The data shall be collected,trackedby tabulatioI_orcontrolcharts,and updatedregularly(afteranalysisof each batch of tanks).If one of the duplicateresultsis a less than value, the data is reportedbutthe data are not used to calculatethe RPD and is not plottedon the control

charts. The use of matrix spike duplicatesensuresthat duplicatedata abovedetectionlimits are obtained.

Controlcharts or tabulateddata shall be used to track the backgroundlevelsof analytesthat generat:_,l_ositivevaluesmost frequentlyfor sampling,hot cell, calibration,and prepalationblanks. Radiochemicalinstrumentbackgroundsshall be recorded,plotted,and analyzedfor each detector. Forsingleparameterdetectorsthe mean and standarddeviationshall be determinedand used to set up controllimits for identifyingchangingand out-of-controlconditions. For multiple isotopedetectors,isotopesthat most frequently

13rCscontri_bg.t_eto the backgroundshall be trackedsuch as for GEA systemsand _"'_'uPufor AEA systems. Controlcharts (or tabulations)and statisticalevaluationsshall be performedon other qualitycontrol informationthat maybe specificto a techniquesuch as CRBL standardsfor ICP and GFAA and SPCCand CCC standardsfor organicanalysis.

Controlcharts (or tabulations)and statisticallimitsshall beestablishedto assess the reproducibilityof homogenizationand compositingprocedures. This requiresthe determinationof the RPD for the duplicatesandmonitoringthe mean and standarddeviationof the data to evaluate theperformanceof these procedureson differentwaste types.

Standard statisticalmethods shall be used to establishthe mean and3a limits for SST Kaste characterizationdata.

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Data will be evaluatedand validatedby the Office of Sample Managementusing the criteriaariddata flags describedin the procedure"Data Validationfor RCRA Analyses"found in the SampleManagementAdministrativeManual,WHC-CM-5-3.

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14,0 CORRECTIVEACTION

The correcLiveactionproceduresare definedin the respectivelaboratoryQAPJPs (WHC 1989 PNL 198g). Limits for data acceptabilitywill beestablishedbased on DQOs and laboratoryperformance. These criteriawill bespecifiedin this documentas DQOs are developedand as the laboratoryperformancedatabaseis established. These criteriashall be evaluatedon acontinuousbasis duringthe characterizationprogramto ensure that thelaboratorycapabilitiesmeet the DQOs. Criteriafor each measurementarameterhave been definedin Section10 and Table D-6. Correctiveactionsave been describedin the text of this section. Fundamentallythe following

guidelinesshall be used in correctingSST characterizationdata.

• Systemsfound to be out of calibrationshall be shut down andrecalibratedbeforererunningthe samplesanalyzed in the batchprior to the problemand before runningany other samples. Anexceptionto this guide may be permissiblefor multielementtechniquesin which only one elementis out-of-controland it is alow priorityanalyte. Any exceptionmust be authorizedby theTechnicalLeader,the data flagged,and documentedincludinganestimateof the bias causedby the system.

• DuplicateRPD resultsfor type I and II analytesthat oxceed limitsshall be evaluatedwith respectto nearnessto detectionlimit andsample heterogeneity. If the sampleconcentrationis greaterthan5 times the method detectionlimit, the duplicateshould be rerun(providingenough sample is available)to determine if the problemis an analyticalerror or sampleheterogeneity. Data from the rerunshouldbe reportedwith each batch and an explanationprovided. Ifthe analyteconcentrationis less than 5 times the detectionlimitno action is required.

• Spike resultsfor type I and II analytesthat exceed limits _hall beevaluatedwith respectto the relativeconcentrationof the spikeconcentrationto the sampleconcentrationand sampleheterogeneity.If the duplicatedata indicatesthat the sample is homogeneousapost digestionspike (whenapplicable)shall be used to evaluateinstrumentinterferences. If no duplicatedata is availableaduplicatesample shall be run to evaluatesample heterogeneity. Ifthe ratio of spike to sample is too small the spikedsample shall be

rerun with a larger spike if practicalor anothertechniquesuch asserialdilutionwill De used to evaluatethe potentialinterference.All evaluationdata shall be includedwith the batch andexplanationsfor the resultsdocumented.

• High blank resultswhich significantlyimpact an analysisshallrequireidentifyingthe sourceof the high blank and removing itwhen practical. If sampleresultsare impactedby greaterthan 20%becauseof the high blank they shall be rerun with a lower blank.If data with lower blank valuescannot be obtainedthe data shall beidentifiedin the results.

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• Other measurementsystems,proceduresor plan correctionsthat maybe requiredas a resultof routinereviewprocessq_sshall beresolvedas requiredby governingproceduresor shall be referredtothe TechnicalLead for resolution, Copies of ali surveillance,audit and correctiveaction documentationshall be consideredprojectQA recordsupon completionor closure.

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15.0 QUALITYASSURANCEREPORTSTO MANAGEMEHT

The QA reportingproceduresfor the laboratoriesare describedin theirrespectiveQAPjPs (WHC 1989, PNL 1989). It_addition,EQA will provide reportsto managementas describedin the QAPP (WHC 1990).

•

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16.0 REFERENCES

Aitken,E. A., 1990, SystemsAnalysisof AlternativesforFinal Dispositionofthe Single-ShellTank System on the HanfordSite, PNL-7426.

Boomer,K. D., 1990, FunctionalRequirementsBaselinefor the ClosureofSingle-ShellTanks,WHC-EP-0338,WestinghouseHanfordCompany, Richland,Washington.

DOE, 1987, The EnvironmentalSurveyManual,DOE/EH-O053,Volume 3, AppendixD,U.S. Departmentof Energy.

DOE, 1988, Record of Decisionfor the Final EnvironmentalImpact Statementforthe Disposalof HanfordDefenseHigh-LevelTransuranicWaste,53 FR 12449,Office of the Federalregister,NationalArchives andRecordsAdministration,Washington,D.C.

DOE, 1989, (Draft)Single Shell Tanks System ClosureCorrectiveAction WorkPlan, DOE/RL 89-16,September1989, U.S. Departmentof Energy,Richland,Washington.

Droppo,J. G., J. S. Wilbur,D. L. Strenge,M. D. Freshley,1989, SingleShellTank ConstituentRankingsfor use in PreparingWaste CharacterizationPlans, PNL-7572,PacificNorthwestLaboratory,Richland,Washington.

EPA, 1977, Handbookfor AnalyticalQualityControlin RadioanalyticalLaboratories,EPA-600/7-7-77-088,U.S. EnvironmentalProtectionAgency,Washington,D..C.

EPA, 1987, Data QualityObjectivesfor RemedialResponseActivities,DevelopmentProcess,EPA ContractNo. 68-01-6939,U.S. EnvironmentalProtectionAgency,Neptuneet al. 1990.

EPA, 1989, Report on MinimumCriteria to Assure Data Quality,EPA/530-SW-90-021,U.S. EnvironmentalProtectionAgency,Washington,D.C.

EPA, 1989, Test Method,The Determinationof InorganicAnions in Waster by IonChromatographyMethod300.0, John D. Pfaff,Carol A. Brockhoff,and JamesW. O'Dell,December1989, USEPA, Environmentaland SystemsLaboratory,Cincinnati,Ohio.

EPA, 1990, U.S. EnvironmentalProtectionAgency ContractLaboratoryProgramStatementof Work for OrganicAnalysisMulti-MediaMulti-Concentration,U.S. EnvironmentalProtectionAgency,Washington,D.C.

Fr edman,D., 1990, New Directionsin Method Development,EnvironmentalLab,Volume 2, Number 4, 1990.

Garfield,J. S., 1990a,Single-ShellTank SystemsEngineeringStudy Work Plan,WHC-EP-9321,WestinghouseHanfordCompany,Richland,Washington.

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Garfield,J. S., 1990b,Single-ShellTank SystemsAnalysisDescription,WHC-EP-O333,WestinghouseHanfordCompany,Richland,Washington.

Morgan,L.G., 19B8, W. W. Schulz,M. R. Adams, and K. W. Owens, 1988, Summaryof Single-ShellTank Waste Characterization:1985-1987, WHC-EP-O075,WestinghouseHanfordCompany,Richland,Washington.

Neptune,Dean, 1990a, EugeneP. Brantly,MichaelJ. Messner,DanielJ. Michael,QuantitativeDecisionMaking inSuperfund: A DataQualityObjectivesCase Study, HazardousMaterialControl,May/June 1990,p 18-27.

Neptune,Dean, 1990b,Austin L. Moorehead,Daniel J. Michael,StreamliningSuperfundSoil Studies: Using the Data QualityObjectivesProcess forScoping. ProceedingsSixth Annual Waste Testingand QualityControl

Symposium,Volume I, p 52, July 1990. _,,'i

PNL, 1989,QualityAssuranceProjectPlan for AnalyticalActivities in theMaterialsand ChemicalSciencesCenter inSupport of the Tri-PartyAgreement,QAPP No. SA-O01,PacificNorthwestLaboratory,Richland,Washington.

Wegeng,R. S., J. W. Buck, S. T. Hwang, M. S. Peffers,1990,PreliminaryRecommendationson the Design of the CharacterizationProgramfor the _I_Hanford Site Single-ShellTanks ,-A System Analysis,Volume II -- Closu_'eRelatedAnalyte Priorities,ConcentrationThreshold,and Goals forAnalyticalLaboratoryDetectionLimits,PNL-7573,PacificNorthwestLaboratory,Richland,Washington.

WHC, 1989,QualityAssuranceProjectPlan for ChemicalAnalysis of HighlyRadioactiveMixed Waste Samplesin Supportof EnvironmentalActivitiesonthe HanfordSite, WHC-SD-CP-QAPP-O02,WestinghouseHanfordCompany,Richland,W_shington.

WHC, 1990,QualityAssuranceProgramPlan for 200 Area Single Shell TankCharacterizationand Assessment,WHC-EP-0294,WestinghouseHanfordCompany,Richland,Washington.

WHC, 1990,QualityAssuranceProgramPlan for the ChemicalAnalysis Performedby the 222-S/RCRALaboratoryin Supportof EnvironmentalActivitiesonthe HanfordSite, WHC-SD-CP-QAPP-O03.WestinghouseHanfordCompany,Richland,Washington.

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GLOSSARY

Accuracy The closenessof agreementbetweenan observedvalue and anacceptedreferencevalue. When,appliedto a set ofobservedvalues,accuracywill be a combinatl,on of a randomcomponentand of a common systematicerror (or bias)component.

Batch A group of sampleswhich behave Similarlywith respecttothe testingproceduresbeing employedand which areprocessedas a unit. For QC purposes,if the number ofsamplesin a group is greaterthan 20, then each group of20 samplesor less will _e handledas a separatebatch.For SSTs all the segmentstaken from a tank plus the corecompositespreparedfrom the segmentsrepresenta "tankbatch" (i.e. for each batch one samplingequipmentrinseblank, one hot cell blank, one spike per core, and oneduplicateper core will be prepared). For a set of samplesdigested,fused or preparedas a unit a "preparationbatch"will require a method (preparation)blank, a laboratorycontrolstandardand may includea spikedor duplicatesample along with the samplesprepared at that time. For aset of samplesanalyzedas a unit an "analysisbatch"willrequirea reagentor calibrationblank,calibrationverificationstandardplus any samples,spikes,duplicates,standardsand blanksgeneratedin the other operations.

Calibration Analysisof an independent(differentfrom calibration)Verification standardprior to analysisof samplesand at a set

frequencyto check instrumentcalibrationand performance.

Calibration Analysisof reagentsused in preparationof the calibrationBlank which are not processedthroughthe preparationprocedure.

For example" The acid-watermixture used in ICP dilutions.

Carrier A non-radioactivespike of known concentrationadded in aradiochemicalseparationto aid in separating(precipitating)the isotopeof interestand used to correctfor incompleterecoveriesof the isotopein the separation.

Concentration The point at which an analytebegins to make a significantThresholdLimit contributionto a risk or waste classificationcalculation.

For the currentanalysisa "significantcontribution"isthe level of analytethat providesat least I% of the totalrisk index or classificationcalculation.

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Data Quality Statementsof the level of uncertaintythat a decisionObjective maker is willing to acceptin resultsderived from(DQOs) environmentaldata. This is qualitativelydistinctfrom

qualitymeasurementssuch as precision,bias, and detectionlimits.

Duplicate Two subsamplesor aliquotstaken from the same segmentorcore compositesample_that are analyzedto documenttheprecisionof a method in a given samplematrix.

Field Blank A blank sample preparedin the field to evaluatepotentialcontaminationfrom the samplinglocation,sampleequipmentor transportationoperation.

Hot Cell Blank A blank sample preparedin the hot cell to evaluatepotentialcontaminationfrom the hot cell environment,extrusionequipmentand sample storagecontainers.

Instrument The instrumentdetectionlimit is the point wheretheDetectionLimit measuredvalue is largerthan the uncertaintyassociated(IDL) with it. This point is defined as 3 times the standard

deviationof the measurementas the concentration

approacheszero (3So). For an instrumentthe So may bebased on the standarddeviationof the blank or thebackgroundnoise level. The CLP program for ICP and AAdeterminesthe IDL by multiplyingby 3 the averagestandarddeviationfor 7 consecutivemeasurementson a standardcontaininganalytesat 3 to 5 times the instrumentmanufacturerssuggestedIDL for 3 non-consecutivedays.

Completeness A measureof the amountof valid data obtainedfrom ameasurementsystemcomparedto the amount that was expectedto be obtainedunder correctnormal conditions.

Check S_andard A check standardis a radiochemicalstandardthat is notpreparedwith each batch of analysesbut is a standardusedover an extendedperiodof time to monitor (check)theperformanceof a radiochemicaldetector and measurementsystem on a daily basis.

ControlLimits A range within which specifiedmeasurementsmust fall to becompliant. Controllimitsmay be mandatory,requiringcorrectiveaction if exceeded,or advisory,requiringthatnon compliantdata be flagged. For SW--846(RCRA)measurementscontrollimitsare normallyset at 3 times thestandarddeviationof the measurementparameter.

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Laboratory A laboratorycontrolstandard(LCS) is a standardthat isControl carriedthroughthe entire preparationand analysisstepsStandard of the procedure. The standardmay be a liquid,similar

but independentfrom a calibrationstandard,or a liquid orsolid standardcontainingmatrix components. Forradiochemicalmethodswhere isotopeavailabilityislimited,the LCS may be carriedonly through the separationand measurementprocedures.

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Long Term Long term releaserisk concernsare based on health risksReleaseRisk to the publicover a time periodgreaterthan a single(LTRR) life-time(70 yr) to determinepotentialhealth effectsto

currentand futuregenerations. The LTRR scenarioconsidersrelease,transportand toxicityparametersincomputingpotentialrisk indexesthat can be used to rankanalytesaccordingto their potentialhealth risks to thepublic.

Matrix This is the minimumconcentrationof a substancethat canDetectionLimit be measuredand reportedwith 99% confidencethat the

analyteconcentrationis graterthan zero and is determinedfrom analysisof a sample in a given matrix containingtheanalyte.

RCRA (SW-846)proceduresdefine this as the methoddetectionlimit and is determinedby multiplyingby 7 thestandarddeviationobtainedfrom triplicateanalysesof amatrix spike containingthe analyteof interestat aconcentration3 to 5 times the estimatedmethod detectionlimit.

The estimatedmethod detectionlimit is on (1) aninstrumentsignalto noise ratiowithin the range of 2.5 to5.0 or (2) the region of the standardcurve where there isa significantchange in sensitivity;i.e., a break in theslope of the standardcurve.

Matrix Spike An aliquotof sample spikedwith a known concentrationofthe analyte(s)being measured. For chemical parameterswhere the efficiencyof the digestionis being evaluatedthe spike is added prior to digestion. For radiochemicalanalytesspikingprior to digestionmay not be practicalbecauseof the availabilityof spiking isotopes. In whichcase the matrix spike is added prior to the isotopeseparationprocedureto evaluatethe efficiencyof theseparationand analyticalprocedures. A matrix spike isused to documentthe bias of a method in a given samplematrix.

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MatrixSpike Intralaboratorysplit samplesspikedwith identicalDuplicate concentrationsof the analyte(s)being measured. They are

used to documentthe precisionand bias of a method in agiven samplematrix.

Method This is the minimumConcentrationthat can be detected in aDetectionLimit sample after it has undergoneall routinesample

preparationand analysissteps, lt is determinedbymultiplyingthe instrumentdetectionlimit by all thenormal dilutionfactors. The method detectionlimits arereportedas /_gor /_Ciper gram of sample. The methoddetectionlimit does not accountfor any changes insensitivityor backgroundcaused by the samplematrix.

Methodof The additionof multiple (3) incrementsof a standardStandard solution (spikes)to sample aliquotsof the same size.Additions Measurementsare made on the originaland after each

addition. The slope,x-interceptand y-interceptaredeterminedby least-squareanalysis. The analyteconcentrationis determinedby the absolutevalue of the x-intercept. Spike volume is maintainedlow (< 10%) of thesample volume. Standardadditionsmay counteractmatrixeffects;however,it will not counteractspectraleffects.

Post Digestion A spike added after a sample has been digested or leachedSpike to evaluatemethod performancein which the subsamplingand

digestion/leachprocedurereproducibilityis not a factorin spike recovery. Normallyused for TCLP and waterleaches. Also used to help differentiatebetween sampleheterogeneityand instrumentor analysismatrix problems.

Preparation The preparationblank is a test utilizingno sample,orBlank deionizedwater that is carriedthroughthe entire

measurementsystem (i.e.,sample digestion,analyteseparationand finalmeasurementprocedure), lt is used toassess contaminationlevels in the analyticalprocess.This blank is often referredto as a method blank in RCRAprocedures,

Sample The operationof loadingSST samplesin the hot cell,Breakdown extruding,homogenizingand compositingthe samplesand

preparingsubsamplesfor subsequentanalyses.

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Short Term STIR is therisk associatedfrom the possibilityofIntruderRisk individualscoming into contactwith the toxic or(STIR) radioactiveconstituentthat may pose a threat to personal

health. The U.S. NuclearRegulatoryCommission(NRC)outlinedthree genericintruderscenarios. The Intruder-ConstructionScenario,the Intruder-DiscoveryScenarioandthe Intruder-AgricultureScenario. Exposureroutes forthese scenariosare ingestion,inhalationand radiologicalground exposure.

Surrogate An organiccompoundwhich is similarto the targetanalyte(s)in chemicalcompositionand behaviorin theanalyticalprocess,but which is not normallyfound inenvironmentalsamples.

Tracer A tracer is a radiochemicalspike which is a differentisotopeof the same elementthat is added to a sample in aknown quantityto determinethe efficiencyor yield of theanalyticalseparationand analysis. Since the tracerisotopehas differentradiologicalpropertiesthan theisotopeof interestthe spike recovery and isotopeanalysisare performedon the same sample aliquot. A "matrixspike"of the same isotopebeing analyzedwill requiretwo samplealiquots.

Traveler Documentationthat accompaniesa samplethat is used to:(I) provide informationto the analystsfor performingaproceduresuch as samplenumber, analyteand procedure,sample size etc., and (2) documenttime, date, analystname, resultsand observationsmade during performanceofthe procedure.

Waste Waste classificationrefersto a systemof rankinganalytesClassification based on regulatoryguidelinesfor disposalof radioactive(CLASS) and chemicallyhazardouswaste. The system is based on the

WashingtonState Departmentof Ecologymethod fordeterminingtoxic equivalentconcentrationsand on the U.S.NuclearRegulatoryCommissionlow-levelradioactivewasteclassification.

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Waste Characterization Plan for the Hanford Site Single-Shell Tanks

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