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DISTRIBUTIONSHEETo To From Page ] of 2

,_ Distribution Characterization Plans and Date 03/23/95_!i',i Reports

ProjectTitle/Work Order EDT No. EDT-610409F

,,i WHC-SD-WM-TP-311,Rev. 0, "Tank 241-U-204 Tank Characterization ECN No."*' P1an"

,: _' Name i MSIN I _iltlhAttach. _ Only0NS_

U,5, Department of Energy," RichlandFieldO.f_flce

W. Ltou S7-54 XN, W. Willis $7-54 X

J. P. Haney $7-73 X

Pac!fic Northwest Lab0cato_ies

S. G. McKinley P7-22 X

WestjnqhouseHanfor..dCom_!!3J6

R. Akita T6-20 XK. E. Bell T6-06 XR. N. Campeau $7-04 XK. K. Cutsforth $I-57 XT. F. Dale T6-20 X$. J. Eberlein R2-12 XG. D. Forehand $7-31 XR. K. Fuller T6-31 XV. W. Hall H4-19 X

, W.J. Kennedy $7-03 XJ. G. Kristofzski T6-06 XJ. S. Lee $7-03 X

A. D. Olguln S7-04 XA. D. Rice T6-06 XP. Sathyanarayana(2) R2-12 XR. D. Schreiber R2-12 XR. H. Stubbs $7-12 XC. L. Thomas H4-19 XT. C. Trible SI-57 XD. A. Turner S7-15 XM. D. Webb H4-25 XCentralFiles L8-04 XO.S.T.I. (2) L8-07 X

A-6000-135 (01/93) I_F067

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DISTRIBUTION SHEET

, To ] From Page 2 of 2IDistribution Characterization Plans and Date 03/23/95LReports

ProjectTitle/Work Order EDT No. EDT-610409

WHC-SD-WM-TP-311,Rev. 0, "Tank 241-U-204 Tank Characterization ECN No.P1an" mim

Name MSIN I _ltlh I Appendix Only

I Attach. J Only

U. ). Departmentof Enerqv- HeadquartersOfficeof EnvironmentalRestorationandWaste Management EM-56312800MiddlebrookRoadGermantown,MD 20874

K. T. Lang XJ. A. Poppiti X

LosAlamos Te.chn.icalAssociates750 Swift,Suite 14Richland,WA 99352

A. T. Dicenso XC. J. Lindquist XT. T. Tran XG. P. Westleigh X

_I A-6OO0-i_ (0i193)_F067

_

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RELEASE AUTHORIZATIONI

Document Number: WHC-SD-WM-TP-311, REV.O

Document Title: Tank 241-U-204 Tank Characterization Plan

Release Date: March 28, 1995

This document was reviewed following the

, procedures , described in WHC-CM-3-4 and is"

APPROVED FOR PUBLIC RELEASE

WHC Information Release Administration Specialist:

il _,_('_-F_ :c I=_' ; ,-- March 2 , 1995

' Vicky Birkl and/

TRADEMARK DISCLAIMER. Reference herein to any specific cocnrp_rcialproduct, process, or service by tradename, trademark, manufacturer, or otherwise, does not necessarily constitute or in_olyits endorsement,recommendation, or favoring by the United States Goverr_nentor any agency thereof or its contractors orsubcontractors.

This report has been reproduced from the best available copy. Available in paper copy and microfiche.Printed in the United States of America. Available to the U.S. Department of Energy and its contractorsfrom:

U.S. Department of EnergyOffice of Scientific and Technical Information (0STI)| P.O. Box 62

Oak Ridge, TN 37831

I Telephone: (615) 576-8401U

Available to the _blic frm: U=S. Department of CommerceNational Technical Information Service (NTIS)5285 Port Royal RoadSpringfield_ VA 22161Telephone: (703) 487-4650

A-6001-400.2 (09/94) WEF256,,

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SUPPORTING DOCUMENT j _. Tot.t,.=.. 3J¢II IIII I .... il i =l _ f I I I II.

2. TitLe 3. Humber 4. Rev He.

'Tank241-U-204 Tank Characterization Plan k'HC-SD-WIH-TP-311 05. Key Words 6. At_thor

Tank 241-U-204, Tank U-204, U-204, Tank ,,_: Kevtn E. Bell

Characterization Plan, TCP, Characterization, Plan _.:I_.."_'" _i' -_._.-f'_Slgnature l "

, Organization/Charge code 8E480/MDR217. Abstract.

, N/A

:+

8. RELEASESTAMP

DISCLAIMER ...................................................

,.,+,. .... _,., • .....,:, ",ff_ _This report was preparedas an account of work spon_red by an agency of the United States J °. " "...... " .......

" ,'. t'. 'Government.Neither the United StatesGovernmentnorany agencythereof,norany of their _:P '" ....

employees,makes any warrant,, express,orimplied, or assumesany legal liability or resl>onsi- _:'+,!\','t_ 2 7 1995 'bility for the accuracy,completeness,or usefulnessof any information, apparatus,product, orprocessdisclosed,or representsthat its usewouldnot infringeprivatelyownedrights, Refer- ,enc¢hereinto any specificcommercialproduct,process,or _ervic¢by tradename,trademark, /.: q ,manufacturer,or otherwisedoesnot necessarilyconstituteor imply its endorsement,recom- ' _ ' ---.-_mendation, or favoring by the United States Government or any agencythereof. The viewsand opinions of authors expressed herein do not necessarily state or reflect those of theUnited States Governmentor any agency thereof.

|l, u

A-6400-0_ (08/94) WEF124

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4

WHC-SD-WM-TP-311Revision 0

Tank 241-U-204Tank Charac,terization Plan

Prepared for the U.S. Department of Energy: Office of Environmental Restoration!11

: and Waste ManagementI

by

Los Alamos Technical Associates

8633 Gage BoulevardKennewick, Washington 99336

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WHC-SD-WM-TP-311,Rev. 0

, TABLEOFCONTENTS

.,,: 1.0 INTRODUCTION ............................... 1

2.0 DATAQUALITYOBJECTIVESAPPLICABLETO TANK241-U-204 ........... I,,+

+', 2.1 SAFETYSCREENINGDATAQUALITYOBJECTIVES .............. I2.2 ORGANICDATAQUALITYOBJECTIVES ............ 2

+_+ 2.3 FUGITIVEVAPOR EMISSIONDATA QUALITY'OBJECTIVE 2

+ 3.0 TANKHISTORICALINFORMATION................ '......... 23.1 JANUARY1995TANK STATUS ..................... . . 23.2 TANK CONFIGURATION ......................... 33.3 TANK HISTORY ........................ 33.4 EXPECTEDTANK CONTENTS .......... .............. 3

4.0 TANK U-204 SCHEDULEDSAMPLINGEVENTS . . . ......... 5, ,

5.0 REFERENCES ........................ .......... 7J(

APPENDICES

, A SAMPLINGAND,ANALYSISPLANFORCORESAMPLINGIN FISCAL,YEAR1995 .... A-i

LIST OF TABLES

Fable I' Tank U-204 Solid CompositeInventoryEstimate............ 5Table 2" IntegratedDQO Requirements..................... 6

LIST OF FIGURES

Figure I' FillHistoryof Tank 241-U-204.................... 4

LIST OF ABBREVIATIONS

DOE U.S. Departmentof EnergyDNFSB DefenseNuclearFacilitiesSafetyBoard

' DQO Data Quality ObjectiveDST Double-Shell TankHEPA High-Efficiency Particulate Air FilterRCRA Resource Conservation and Recovery Act of 1976SST Single-Shell TankTCP Tank Characterization PlanTOC Total Organic CarbonTPA Federal Facility Agreement and Consent Order (Tri-Party Agreement)TWRS Tank Waste Remediation SystemU-204 Tank 241-U-204WHC Westinghouse Hanford Company

ii

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WHC-SD-WM-TP-311,Rev. 0

' I.0 INTRODUCTION

The DefenseNuclearFacilitiesSafetyBoard (DNFSB)has advisedthe U.S.Departmentof Energy(DOE)to concentratethe near-termsamplingand analysisactivitieson identificationand resolutionof safety issues(Conway1993). Thedata qualityobjective(DQO)processwas chosenas a tool to be used to identifysamplingand analyticalneeds for the resolutionof safety issues. As a result,arevisionin the FederalFacilityAgreementand ConsentOrder (Tri-PartyAgreementorTPA) milestoneM-44 has been made, which statesthat "A Tank CharacterizationPlan(TCP)will be developedfor each double,shelltank (DST)and single-shelltank (SST)using the DQO process... Developmentof TCPs by the DQO processis intendedtoallow users (e.g.,HanfordFacilityusergroups;regulators)to ensuretheir needswill be met and that resourcesare devotedto gainingonly necessaryinformation"(Ecologyet al. 1994). This documentsatisfiesthat requirementfor tank 241-U-204(U-204)sampling activities.

2.0 DATA QUALITYOBCIECTIVESAPPLICABLETO TANK 241-U-204

The samplingand analyticalneeds associatedwith the HanfordSite undergroundstoragetanks on one or more of the four Watch Lists (ferrocyanide,organic,flammablegas, and high heat) and the safetyscreeningof all 177 tanks have beenidentifiedthroughthe DQO process. A DQO identifiesthe informationneededby aprogramgroup concernedwith safety issues,regulatoryrequirements,tank wasteprocessing,or the transportof tank waste. The DQOs that have been completedandapply to tank U-204 as of January1995 are discussedin the followingparagraphs.

2.I SAFETY SCREENINGDATA QUALITYOBaECTIVES

The Tank SafetyScreeningData QualityObjective(Babadand Redus 1994)describesthe samplingand analyticalrequirementsthat are used to screenwastetanks for unidentifiedsafety issues. Both Watch List and non Watch List tanks willbe sampledand evaluatedto classifywaste tanks in one of three categories(SAFE,CONDITIONALLYSAFE, or UNSAFE). The safetyscreeningDQO identifiesthe guidelinesto determineto which classificationa tank bel.ongsbased on analysesthat indicateif Certainmeasurementsare within establishedparameters. If a specifiedparameteris exceeded,furtheranalysesmay be requiredto classifya tank. The primaryanalyticalrequirementsfor the safetyscreeningof a tank are energetics,totalalpha activity,moisture,and flammablegas concentration.A tank can be removed

- from a Watch List if it is classifiedas SAFE.

This DQO requiresthat a verticalprofileof the tank waste be obtainedfromat least two widely spacedrisers. This verticalprofilemay be obtainedusingcore, auger,or grab samples. The safetyscreeninganalysesshall be appliedto allcore samples,DST ResourceConservationand RecoveryAct (RCRA)samples,and augersamples,except those taken exclusivelyto assessthe flammablegas crust burnissue.

2.2 ORGANICDATA QUALITYOBaECTIVES

As indicatedby the presentstatusof the tank, the Watch List DQO applicableto tank U-204 is the Data QualityObjectiveto SupportResolutionof the Organic

i I

I|1

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J

WHC-SD-WM-TP-311,Rev. 0 "

Fuel Rich Tank Safety Issue (BabadeL al. 1994). The organicsafetyissue arisesdue to wastes addedto SSTs containingquantitiesof compiexantsused in wastemanagementoperations,as well as degradationproducts,of the complexantsand,solventsused in fuel reprocessingand metal recoveryoperations. These waste tanksalso containa presumedstoichiometricexcess of sodiumnitriteand sodiumnitrate

! that are sufficientto exothermallyoxidizethe organiccompoundsin the tank, The' relevantsafety issuesthat are of concernfor tanks on the OrganicWatch List are', as follows:

r

.' • The potentialfor an exothermicreactionoccurringfrom the flammable. mixture of organicmaterialsand nitrate/nitritesalts that could result

in a releaseof radioactivematerial.

• The possibilitythat other safetyissuesmay exist for the tank.l

Samplingand analyticalrequirementsfor the OrganicFuel Rich Tank SafetyIssueDQO includestwo widely spacedcore samplesa_Idprimaryanalysesfor organiccarbon,moisturecontent,tank temperature,and presenceof a free organicliquid.

2.3 FUGITIVEVAPOR EMISSIONDATA QUALITYOBaECTIVES

The TankVapor IssueResolutionProgramwas initiatedin 1992 to resolvethehealthand safetyissuesassociatedwith the high levelwaste tanks at the HanfordSite. The two main issuesrelatedto this programare I) an insufficientunderstandingof reportedexposuresof tank farm personnelto unacceptablelevelsofnoxiousvapors and 2) the risks to workerhealthand safetycan not be determineduntil the vapors in the waste tanks are well characterized.Tank U-204 is one ofthe 36 tanks on the "SuspectTank List" (Osborneand Huckaby1994b). This list iscomposedof 20 FerrocyanideWatch List tanks,9 OrganicWatch List tanks (oneofwhich is also on the FerrocyanideWatch List),and 8 tanks with a historyof vaporincidents. WestinghouseHanfordCompany (WHC)standardsafetypracticesdictatethat any flammablecomponentsin the headspace.ofany Watch List tank must bedeterminedand quantifiedbeforeintrusivework can be conductedon these tanks.The DQO applicable'Lohead space vapor samplingis Data QualityObjectivesforGenericIn-TankHealth and Safety Vapor IssueResolution(Osborneet al. 1994).

A nitrogengas purgewill be used to clear and cool the drill bit during4B

rotarycore sampling. This purge gas exhaustsintothe waste tank head space anda over the operatingperiodcould potentiallypressurizethe head space resultingin•. an uncontrolledreleaseof pollutants. A portablemodularunit has been developed| to exhaustthe tank head spaceduringrotarycore sampling. This modularunitwill

removeairborneparticlesthroughhigh efficiencyparticulate(HEPA)fiIL_._rs,but isnot designedor equippedto treat or removetoxic vapors, lt is equippedwithinstrumentsto monitorand alarm for total organiccarbon(TOC) and ammoniavapors.The tank head spacemust be characterizedto confirmthat the modular unit can besafelystartedand to establishacceptableTOC and ammonialevelsfor safeoperation. The applicableDQO for rotarycore samplingis Rotary Core VaporSamplingData QualityObjective(Price1994).

3.0 TANK HISTORICALINFORMATION

This sectionsummarizesthe availablehistoricalinformationfor tank U-204.Includedare the age of the tank, processhistory,and the expectedcontentsof the

2

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s

WHC-SD-WM-TP-311,Rev. 0

' tank basedon historical.information.The fill history'informationis availableinA Historyof the 200 Area Tank Farms(Anderson1990).

q

3.I OANUARY1995 TANK STATUS

Tank U-204 is on the OrganicWatch List and is passivelyventilatedwithinterim stabilizationcompletedin 1979. The tank is classifiedas sound andintrusionpreventionmeasureswere completedin 1982. Approximately11,400liters(3,000gallons) consistingof 7,600 liters (2,000gallons)of sludgeand 3,790liters (1,000gallons)of supernatantwith no pumpableliquidremainingarecontainedin thetank. The surfacelevel is monitoredmanuallyeach day throughriser I and the waste measuresabout 46 centimeters(18 inches)in depth. Thelatest photographwas taken in June 1989 and shows a dark yellow supernatantsurfacesurroundedby a light yellow sludgepepperedwith dark material.The highesttemperaturereadingis 68°F (20°C)(Hanlon1994).

3.2 TANK CONFIGURATION

Single shell tank U-204 was constructedas a type I tank between1943 and 1944and is locatedin the 200 West Area. Tank U-204 is 6 meters (20 feet) in diameterand has a capacityof 208,000liters (55,000gallons). The tank is not in a cascadeflow systembut does cascadeto a junctionbox. A cascadesystemconsistsof tanksconnectedin seriesby pipes. When the primarytank in the systembecamefull, thewaste would then flow to the secondarytanks in the system. Tank U-204 has 8risers;three 31 centimeters(12 inch)risers(#2, #3, and #6) are availableforuse,

3.3 TANKHISTORY

, During 1956, tank U-204 was filledwith REDOX supernatantand secondcycledecontaminationwaste. This wastewas pumpedto an unknowndestinationin 1977.Tank U-204 was removedfrom servicein 1978 and placedon the OrganicWatch List inMay 1994 due to an estimatedTotalOrganicCarbon (TOC)contentgreaterthan 3 dryweight percent. The fill historyinformationis availablein A Historyof the 200Area TankFarms (Anderson1990). FigureI summarizesthe influxand effluenthistoryof tank U-204.

3.4 EXPECTEDTANKCONTENTS_

Tank U-204 contentsare expectedto consistof supernatantand sludge layerswith no liquidcapableof being pumpedremainingin the sludge. The organlccontentreportedin HistoricalTank CharacterizationEstimatesfor the SW Quadrantof theHanford200 East Area (Brevick1994) is inconsistentwith the predicted3.01 weightpercentfrom a PacificNorthwestLaboratorystudy (Tothet al 1994). Table Isummarizesthe expectedtank contents.

3

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WHC-SD-WM-TP-312,Rev. 0

, Table I: Tank U-204 Soiid CompositeInventoryEstimateI

" Phys i cal Data Valuc

T-otalSolid Waste 11,700kg (2,000gallons) ___ , ,

_eat Load 0 (0 BTU/br)

D_.ee_nsi ty 1.54 g/ml-- ,,, ,, ,,, , , _: --

VoidFraction 0.65

Weight% Water 55.61, , --. __

T_OOC_(WetWeight%) 0 _ -_Analytes #g/g #g/ml

Ha+ 17,300 26,600± ,,, , --

_1+3 101'000 _ 156,000,, , , ,_,,,,

NO_" 21,200 _ 32,600

NO2" 5,5].0 8,490-- ,,, ,., ,,.,,,, --

CO_"2 2,570 3,960....__ _ ..i, _ , ,,, , ,,. ,. --

)H" 195,000 300,000 ., , ,, ,,, --

Radi onucl ides #Ci/9 #Ci/ml_u 2.53 3.90

:: ,:i, ,,, ,, ' "I;', ,, _,,

1(Brevick 1994)

4.0 TANKU-204 SCHEDULEDSAMPLINGEVENTS

Head space vapor sampling and core sampling in fiscal year 1995 are currentlyscheduled for tank U-204. No other sampling is scheduled through fiscal year 1997(Stanton 1994). The head space vapor sampling shall be conducted in accordance withData Quality Objectives for Generic In-Tank Health and Safety Vapor Issue Resolution(Osborne et al. 1994). Vapor sampling will satisfy part of the requirementspecified in TPA Milestone M-40-08 to complete the vapor sampling of all Watch Listtanks (Osborne and Huckaby 1994b).

Sampling shall be conducted following the Tank Safety Screening Data QualityObjective (Babad and Redus1994) and the Data Quality Objective to SupportResolution of the Organic Fuel Rich Tank Safety Issue (Babad et al. 1994). Therecommendedmethod of sampling tank U-204 is with push-mode core sampling. Thistank has approximately 24 inches of waste in the bottom. This depth should beverified with a "zip" cord prior to sampling. The most recent in-tank photos fromthis tank shows pooled liquid in the center of the tank. The pool does not extendto the edges of the tank. The risersthat will be used to samplewill probablyhavesolid materialbeneaththe opening. In addition,a core sampleis neededto satisfythe organicDQO.

NHC-SD-WM-TP-311,Rev. 0

The samplingand analyticalrequirementsfrom these DQOs are summarizedinT_ble ?. A more completelist of analyticalrequirementsare given,as an appendedrevision,in the appropriatesamplingand analysisplan.

Table 2: IntegratedD(_,L)Requirementsi

,,,

' PrimaryAnalyticalSampling ApplicableDQO Sampling RequirementsEver,t Requirements

Vapor • GenericIleaith , 6 SUMMA® Canisters • Flammability& SafetyVapor , 12 TripleSorbent • ToxicityIssueResolution Traps

, 6 SorbentTrap' Systems

Core • Tank Safety Samplesfrom a minimum • EnergeticsScreening of 2 risersseparated. • TOC

radiallyto the maximum • MoistureContent• OrganicFuel extent possible • Total AlphaRich Tank SafetyIssue

SUMMA is a registeredtrademarkof The OregonGraduateInstituteof Scienceand

i Technology!

!il!11

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WHC-SD-WM-TP-311,Rev, 0

. 5.0 REFERENCES

Anderson, J. D., 1990, A History of the 200 Area Tank Farms, WHC-MR-0132,Westinghouse Hanford Company, Richland, WA.

Babad, H., S. M. Blacker, and K.S. Redus, 1994, Data Quality Objective to SupportResolution of the Organic Fuel Rich Tank Safety Issue, WHC-SD-WM-DQO-O06,Rev.O, Westinghouse Hanford Company, Richland, WA.

Babad, H. and K. S. Redus, 1994, Tank Safety Screening Data Quality Objective,WHC-SD-WM-SP-O04,Westinghouse Hanford Company,Richland, WA.

Brevick, C. H., L A. Gaddis, and W. W. Pickett, 1994, Historical Tank ContentEstimate for the SWQuadrant of the Hanford 200 East Area, WHC-SD-WM-ER-352,Rev. O, IFC Kaiser Hanford Company, Richland, WA.

Carothers, K. G., 1994, Data Quality Objectives for the Waste CompatibilityProgram, WHC-SD-WM-DQO-O01,Westinghouse Hanford Company,Richland, WA

Conway, J. T., Letter to H.R. O'Leary, DOE, "DNFSBRecommendation93-5 to theSecretary of Energy," 9400070, dated July 19, 1993.

=

Ecology, EPA, and DOE, 1994, Hanford Federal Facility Agreement and Consent Order,Fourth Amendment, Washington StaLe Department of Ecology, U.S. Environmental

: Protection Agency, and U.S. Department of Energy, Olympia, WA.

: Hanlon, B. M., 19_4, Waste Tank Summaryfor Month Ending November 30, 1994,WHC-EP-OI82-80, Westinghouse Hanford Company, Richland, WA.

Osborne, J. W., J,L. Huckaby, E.R. Hewitt, C.M. Anderson, D.D. Mahlum, B.A.Pulsipher, 8.Y. Young, 1994, Data Quality Objectives for Generic In-Tank

Health and Safety Vapor Issue Resolution, WHC-SD-WM-DQO-O02,Rev. O,Westinghouse Hanford Company, Richland, WA.

Osborne, J. W., anQ J.L. Huckaby, 1994b, Program Plan for the Resolution of TankVapor Issues, WHC-EP-0562,Rev. I, May 1994, Westinghouse Hanford Company,Rich.land, WA.

Price, D. N., 1994, Rotary Core Vapor Sampling Data Quality Objective,WHC-SD-WM--SP-O04,Westinghouse Hanford Company, Richland, WA.

Stanton, G. A., 1995, Baseline Sampllng Schedule, Revision 4.1, (Internal Memo74320-95-01, todistribution, February 2), Westinghouse Hanford Company,

, Richland, WA.I_" Toth, J. J., P.G. Heasler, C.E. Willingham, P.E. Whitney, 1994, Organic Carbon in

Hanford Single-Shell Tank Waste, PNL-9434, Pacific Northwest Laboratory,Richland, WA.

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WHC-SD-HH-TP.311,Rev. 0

L

APPENDIX A

SAMPLING AND ANALYSIS PLAN

FOR CORE SAMPLING IN FISCAL YEAR 1995

i

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WHC-SD-WM-TP-311,Roy. 0

' CONTENTS

'j,

:,,, "SAMPLINGEVENTA: CORESAMPLINGIN FISCALYEAR]995

.!, AI.O SPECIFIC TANKODJECTIVES .................... .... A-I,_ AI.I RELEVANTSAFETYISSUES . ................. .... A-I'_ A1.1.I TankU-204 Characterization Objectives . . _ .. ..... A-I

AI,1.2 Safety Screening and Organic Data Quality Objectives . . . A-2AI.1.3 Data Quality Objectives Integration ............ A-2

A2.0 TANKSTATUSANDSAMPLINGINFORMATION..... , . . . ......... A-2A2.1 TANK STATUS .................. A-2A2.2 SAMPLINGINFORMATION....................... A-3

A3.0 SAMPLEEXTRUSIONANDBREAKDOWNINSTRUCTIONS............... A-3" A3.1 TANK-SPECIFICANALYTICALPROCEDURES ' . ....... A--3' A3.2 INSUFFICI,ENT SAMPLERECOVERY .................. A-6

A3.3 PRIORITIES OF REQUESTEDANALYSES ................. A-6

P,4.0 SPECIFIC ANALYTE,QUALITYASSURANCE,ANDDATACRITERIA ......... A-lOA4.1 SPECIFIC METHODSANDANALYSES................... A-lOA4.2 QUALITYASSURAI_CE......................... A-lO

A4.2.1 Laboratory Operations ................... A-lOA4.2.2 Sample Collection ..................... A-lOA4.2.3 Sample Custody ...................... A-11

. A5.0 ORGANIZATION.............................. A-16

A6.0 EXCEPTIONS,CLARIFICATIONS,ANDASSUMPTIONS............... A-16A6.1 EXCEPTIONSTO DQOREQUIREMENTS.................. A-16A5.2 CLARIF!CATIONSANDASSUMPTIONS.................. A-17

! A7.0 DELIVERABLES . ............................. A-18' A7.1 PROGRESSREPORTS..... , .................... A-18

A7.2 FORMATI REPORTING. ....................... A-19A7.3 FORMATIll REPORTING....................... A-19A7.3 FORMATIV REPORTING........................ A-19

AS.0 CHANGECONTROL............................. A-20

Ag.0 REFERENCES............................... A-21

A-ii

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i

WHC-SD-WM-TP-311,Rev. 0

LIST OF TABLESFORAPPENDIXA

Table A-I' U-204 Chemical,Radiological,and PhysicalAnalyticalRequirements ............................. A-12

Table A-2' Tank U-204 ProjectKey PersonnelList ............... A-16

LIST OF FIGURESFOR APPENDIXA

FigureA-I' Solid AnalysisFlow Chart .................... A-7FigureA-2: LiquidAnalysisFlowChart .................. A-8Figur,eA-3' SampleAnalysisand ReportingFlow Chart ........... A-9

LISTOF ABBREVIATIONSFOR APPENDIXA _,

ACL AnalyticalChemistryLaboratoryU-204 Tank 241-U-204DOE Departmentof EnergyDQO Data QualityObjectiveDSC DifferentialScanningCalorimetryDST Double-ShellTank,GEA Gamma EnergyAnalysisHPGE/MCA High PurityGermanium-multichannelanalysisIC Ion ChromatographyICP InductivelyCoupledPlasma- atomicemissionspectroscopyLIMS LaboratoryInformationManagementSystemsRCRA ResourceConservationand RecoveryAct of 1976RSST ReactiveSystemScreeningTool

' SARP Safety and AnalysisReportfor PackagingSAP Samplingand AnalysisPlanSST Single-ShellTankTCP Tank CharacterizationPlanTGA ThermogravimetricAnalysisTOC Total OrganicCarbonTWRS Tank Waste RemediationSystemUSQ Unreviewed Safety Question

| WHC Westinghouse Hanford Company

qlA-iii

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WHC-SD-WN-TP-311,Rev. 0

. AI.O jSPECIFIC TANKOBJECTIVESI

i

, J' There are four Watch List !',ankclassifications(ferrocyanide,organic

hydrogen/flammablegas, and highheat. load) Theseclassificationscover tl_esixsafety issuesrelatedto public and workerhealththat have been associatedwith theHanfordSite undergroundstoragetanks. These safety issuesare as follows:ferrocyanide,flammablegas, organic,criticallty,high heat, and vapor safetyissues (Babad1992). Tank 241-U-204is.one of 20 tanks on the OrganicSalts WatchList. This Samplingand AnalysisPlan (SAP)will identifycharacterizationobjectivespertainingto samplecollection,hot cell samplebreakdown,andlaboratoryanalyticalevaluationand reportingrequirementsin accordancewith theappropriateDQO documents.

A1.1 RELEVANTSAFETY,ISSUES

The organicsafety issue arisesdue to wastes added to SSTs containingquantitiesof complexantsused in wastemanagementoperations,as well asdegradationproductsof the complexantsand solventsused in fuel reprocessingandmetal recoveryoperations. These waste tanks also containa presumedstoichiometricexcessof sodiumnitriteand sodiumnitratethat are sufficientto exothermallyoxidizethe organiccompoundsin the tank.

The relevantsafety issuesthat are of coDcernfor tanks on the OrganicWatchList are as follows'

• The potentialfor an exothermicreactionoccurringfrom the flammablemixtureof organicmaterialsand nitrate/nitritesaltsthat could resultin a releaseof radioactivematerial.

• The possibilitythat other safetyissuesmay exist for the tank.i

AI.1.1 Tank U-204 CharacterizationObjectives

The characterizationefforts applicableto this Samplingand AnalysisPlanare focusedon the relevantsafetyissueslistedabove.The OrganicSafetyProgramhas identifiedtwo key safetyquestionsthat shouldbe answeredfrom analyticaldataon tank U,204 waste are as follow_'

• Is the tank SAFE and or does it belongon the OrganicSalts Watch List?

• Is the tank CONDITIONALLYSAFE OR UNSAFE?

Based on the answersto these two questions,actionswill be identifiedandq implementedto mitigateor remediatethe conditionsthat resultedin classifyingthea tank as UNSAFE (Babadet al. 1994).I

To satisfyother objectivesof this Samplingand Analysiseffort,the tankcontentsshall be safetyscreenedin orderto identifyany other potentialsafetyissuesRssociatedwith tank II-204,and to ensurethat the tank shouldnot be placedon additionalWatch Lists.

I

A-I

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WHC_SD-WM-TP-311,Rev.0

AI.I.2 Safety Screeningand OrganicData QualityObjectives

The samplingand analyticalneeds associatedwith organicsaltstanks, as wellas the safety screeningof all tanks,have been identifiedthroughthe data qualityobjective(DQO)process. Additionaldata needs associatedwith tank U-.204may beidentifiedin subsequentDQO efforts,whichmay then be incorporatedinto_futuresamplingand analysisplans.Pertinentdocumentsto this effort includethefollowing'

(I) Tank Safety ScreeningData QualityObjective(Babadand Redus 1994)describesthe samplingand analyticalrequirementsfor screeningwaste tanks forunidentifiedsafetyissues. The criteriafor placinga tank on a particularWatch List are enumeratedin that document.

(2) Data QualityObjectiveto SupportResolutionof the OrganicFuel Rich Tank. Safety Issue (Babadet al. 1994),which describesthe samplingand analytical

requirementsfor tanks on the OrganicsSalts Watch List, includingtank U-204.

AI.1.3 Data QualityObjectivesIntegration

The organicand the safetyscreeningDQO effortshave compatiblesamplingrequirements. At a minimum,two cores samplesfrom widelyspaced riserslocatedapproximately180° apart and near the outer edge of the tankmust be taken.

The analyticalrequirements'Forthe safetyscreeningof a tank specifysampleanalysesto be performedon half-segments,as doesthe organicDQO. Since theo_,'ganicDQO specifieshomogenizedhalf-segments,_he aliquotsfor safetyscreeningwill be also be hsinogenized.

The analytesidentifiedin the safetyscreeningDQO for the varioussafetyissuesare a subsetof the suite of the analysesidentifiedin the organicDQO withthe exceptionof analytesmeasuredfo','the criticalitysafetyissue. Ifnotificati.onlimitsfor immediate'!y,-eportingof analytesidentifiedin the DQOeffortswere conf'lictingithe most stringentlimitsof the DQO effortswere used inthis Samplingand AnalysisPlan.

A2.0 TANK STATbSAND SAMPLINGINFORMATION

A2.1 TANK STATUS

Tank U-204 currentlycontains11,400liters (3,000gallr..s)consistingof7,600 liters (2,000gallons)of sludgeand 3,800 liters (1,000gallons)ofsupernatant. This volumeof waste correspondsto approximately46 centimeters(18 inches)of waste. Tank U-204 is presentlyon the OrganicWatch List and ispassivelyventilatedwith interimstabilizationcompletedin 1979. The tank isclassifiedas sound and intrusionpreventionmeasureswere completedin 1982. Thelatestphotographwas taken in June 1989 and sho_vsa dark yellow supernatantsurfacesurroundedby a lightyellow sludgepeppe_'edwith dark material.The hi}hesttemperaturereadingis 68°F(2(]°C)as of October1994, (Hanlon1994).

A-2

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WHC-SD-WM-TP-311,Rev, 0

A2.2 SAMPLINGINFORMATIONo

Tank U-204 is scheduledto be sampledby the core samplingmethod. One coresampleshall be taken from Riser 2 and one core sampleshallbe taken from Riser 6.If a differentriser is necessaryto meet the samplingand analysisrequirements,this changemust be recordedand approvedby the cognizantengineerbeforesampling.The risersused may be recordedon a permanentdata sheet or recordeddirectlyin awork package. Based on currentrecords,one segmentis expectedfrom each core, andis expectedto containapproximately46 cm (IB inches)of waste material,lt shouldbe noted that the samplingobjectiveis to obtaina verticalprofileof the waste;therefore,more or less seg_ents.mayneed to be taken dependingon the accuracyofthe volumeestimates. For detailedinformatidnregardingthe samplingactivities,refer to work packageWS-95-034. This documentcontainsoperatingproceduresandthe chain of custodyrecordsfor this samplingevent.

Hydrostatichead fluid (HHF)with lithiumbromide(LiBr)as a tracermay beused to aid in the collectionof core samples. If so, this must be recordedon thechain of custodyform and an HHF blank must be preparedas part of the samplingprocedure. The blank shallconsistof a containerfilledwith HHF (withLiBrtracer)from the same batchof HHF usedduring the core sampling, lt shall beanalyzedfor Li (and Br, if the Li notificationlimit is exceeded)in order todeterminethe concentrationof the tracer at the time the core was taken. If HHF isused duringthe samplingevent,only one HHF blankper tank would be required. Thisblank is required in additionto the field/tripblank (samplerfilledwith water)_For specificinformationconcerningsamplehandling,custody,and transport,referto the qualityassurance/qualitycontrolrequirementsin SectionA4.2.

A3.0 SAMPLEEXTRUSIONAND BREAKDOWNINSTRUCTIONS

lt shouldbe noted that, in accordancewith the Safetyand AnalysisReportforPackaging(SARP),core samplesfromtank U-204 must be ventedevery 47 days from thetime of the cask sealingto allow any retainedgas to escape.

A3.1 TANK-SPECIFICANALYTICALPROCEDURES

A flowchartdepictingthe sample breakdownand analysisscheme is presentedinFiguresA-I, A-2, and A-3. These steps are describedin detail to providethe hotcell and laboratorychemistswith guidancefor the breakdownof the samplesand maybe alteredas appropriateby the performinglaboratory. SeveralanalyseslistedinTable A-I requirea 45 day reportingtime, as noted. The 45-day reportingformat,

; Format III, is explainedin SectionA7.3.

Any decisions,observations,or deviationsand justificationsmade to thiswork plan or during the samplebreakdownshall be documentedin writing. Thesedecisionsand observationsshall also be reportedin the data report. The reportingformatsfor analysesare containedin Table A-I. If the steps in this flowchartcannot be performeddue to insufficientsample,the CharacterizationProgram,CharacterizationSupport,and the OrganicSafetyProgramshall be notifiedforfurtherdirection.

A-3

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WHC-SD-WM-TP-311,Rev. 0

Step i Receive core segments at the laboratory in accordance with approvedprocedures.

Step 2 Conduct the follewing on the material from each segment:i

• Perform a visual examination of the segment(s)

• Record observations. This may include a sketch of the sample inaddition to written documentation of pertinent descriptiveinformation such as color, texture, homogeneity, consistency.

• Note color and clarity of any drainable liquid.

• Report sample recovery results to the Organic Safety Program withinone working day of sample breakdown.

i • Take color photographs and/or a videotape to visually document thesample.

Step 3A Does the sample contain any drainable liquid?

Yes' Proceed to Step 3BNo' Proceed to Step 5

Step 3B Is the sample 100%drainable liquid?

Yes. Proceed to Step 11No' Proceed to Step 4

Step 4 Separate any drainable liquid from the solids. Measure and record thevolume. Retain drainable liquids for further processing.

• SOLIDSPATH

| Step 5 Divide each core sample into two subsegments (i.e., half segments).

I Step 6 Homogenize each subsample using the appropriate approved procedure.

i Step 7 Will a homogenization test be performed ?

Yes: Proceed to Step 8No: Proceed to Step 9

NOTE" One subsample per core, at a minimum, should be used if ahomogenization test is to be performed, Additional testsmay be performed at the laboratory's discretion.

Step 8 Conduct the homogenization test by taking I to 2 g aliquot from widelyseparated locations of the homogenized subsample. Conduct thehomogenizationtest in accordancewith Bell (1993).

Step 9 Collectsufficientaliquotsfrom each homogenizedsubsampleto performthe appropriatepreparationsand analyseslistedin Table A-I,

A-4

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kJ

WHC-SD-WM-TP-311,Rev, 0

, Step 10 Removeat least 20 mL and up to 40 mL of each l,omogenizedsubsampleforthe archivesample (Bratzel1994).

_

LIQUIDSPATH

Step 11 Closelyinspectthe liquidsamplefor the presenceand approximatevolumeof any potentialorganiclayers, Does the samplecontainany

',, immiscible(potentiallyorganlc)layers?

Yes: Proceedto Step 12ANo' Proceedto Step 13

Step 12A Reportany visuallyobservedimmiscible(potentialorganic)layerimmediatelyby the early notificationsystem(see SectionA7.2).

Step 12B Separateand retain the potentialorganiclayer for possiblefuture, analysis.

NOTE: Steps 13 through 17 shall be performed on the remaining(probable aqueous) liquid layer on]y,

Step 13 Filter the remaining liquid sample through a 0,45 micron filter,

Step 14 Is there greater than I gram of solid on the filter?

Yes: Proceed to Step 15No: Proceed to Step 16

Step 15 Archive the solids for possible future analysis (Bratzel 1994),

Step 16 Removesufficient aliquots from the liquid sample to perform theappropriate analyses listed in Table A-I in duplicate.

Step 17 Archive at least 20 mL and up to 40 mL of the drainable liquid as the_j liquidarchive(Bratzel1994).

am

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'I

A-5

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4

WHC-SD-WM-TP-311,Rev. 0

PRIMARYANALYSISPATH

Step 1B Perform primary analyses as listed in Table A-l,

Step 19 Compare the primary analysis data with no¢ification limits.

Step 20A Do the results exceed the 'notification limits (Table A-I)?

Yes: Proceed to Step 2OB,No: Proceed to Step 23,

Step 20B Report results exceeding the notification limits using Format Ireporting deliverable requirements as listed in Section A7.2.r

SECONDARYANALYSISPATH

Step 21 Perform secondary analyses as listed inTable A-I,,,

Step 22A Do the secondaryanalysesexceedthe notificationlimits?

Yes: Proceedto Step 22BNo: Proceed to Step 23

Step 22B Report results exceeding the notification limits using Format Ireporting deliverable requirements as listed in Section A7,2.

Step 23 Report results as listed in Section A7,

A3.2 INSUFFICIENTSAMPLERECOVERY

If the amountof materialrecoveredfrom samplestaken from tank U-204 isinsufficientto performthe analysesrequestedand to permit a minimum10 mL archiveper sample,the "laboratoryshallnotifythe Tank CognizantEngineer,theCharacterizationProgramoffice,and the OrganicSafetyProgramwithinone workingday (See Table A-2). A prioritizationof the analysesrequested"inthis documentisgiven in SectionA3.3. Any analysesprescribedby this document,but not performed,shall be identifiedin the appropriatedata report,with justificationfornon-performance.

A3.3 PRIORITIESOF REQUESTEDANALYSES

=I Confirmationof prioritizationlevelsor revisionof samplebreakdownproceduresmay be providedto the laboratoryby the CharacterizationProgrambased

ulon the samplerecovery,readilyobservablephysicalpropertydistinctionswithint e sample,and the requestedsamplebreakdownproceduresas providedin SectionA3.I, The priorityof an analysisis specifiedby its designationas a primaryorsecondaryanalysis. Furtherprioritizatlonwill be determinedby the programon aDQO basis.

A-6

, WHC.SD._bTP,311,REV, 0

Step I .

Receive /

samples,

li ii

Step 2Conduct visual ....... -

examanatton,

YES "_/'i

/,_ .......

/Ntep 3B_

\ d_al.able/ \ _,-,,,1

NO

N°,IStep 4

Separate and retain

drainable liquids andnleasure weight anti

volume,

Step 5 SOLID ANALYSIS PA'FIt

Divide

the sludge sample _ . . -- - I _ ?,,qinto halt:segments.

. ii - 1

-s_tepl_ ,, " Step8Homogenize ' Conduct [ r.,,T,_"_

each suhsample. _ homogenization t st.

NO "_ ,,,Step 9

Collect allquotst'ro_ each

subsample to

pertbrm analyseslisted In]'able A.I,

I .

Step i0

Remove material tbr

solid samplearchive,

. m __

' Figure A-I: Solid Analysis Flow Chart

i A-7i

t

WHC-SD-WM-TP-311,REV.0

LIQUID PATH

-- stepl2A -- -i Step 12B

/ Does the sample X YES Report I i Separate and( contain potential _-,--[ immediately _ retain potential

organic wf i usingearly ] ] organic layer,

, \ ,_yo_7/ I _no,t_.,lo.I I |

NO_ ,,

I........ Isystem, 1m

iiii

i

,

Step 13Filter the

remaining liquid

sample through

0,45p filter,

Archive solids' obtained from

Step 13,

i ii i --

NO ],

Step 16

Remove aliquots

from liquid

sample andperform analyses

listed in

Table A- 1,

I

.... IStep 17

Archive from

liquid sample,

Figure A-2: Liquid Analysis Flow Chart

A-8

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WHC-SD-WM-TP-311,REV, 0

ANALYSIS AND REPORTING PATH _''&'i_;_,;

.... ___ u Y,L

Step 18 _Perform primary '_

analyses as listedin

Table A., I,

E

Step 19

Compare Step 20A Step 20B Step 21 ,,,primary analysis Do the re:;ults Report primary Perfbrm

data with exceed the analysis results secondary

notification notification using Format I analyses,limits, _ limits'? deliverables,

NO

Step 22A Step 22BGo To Do secondary Report secondau'Step 23 analysis results YES analysis result.q

exceed using Format 1 :

notification deliverables,

limits?

NO

Step 23 Go To

Report using Step 23 -deliverables inSection A7,0,

it

Figure A-3' Sample Analysis and Reporting Flow Chart

A-9

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'r WHC-SD'WM-TP-311,Rev. 0

A4.0 SPECIFIC ANALYTE,QUALITYASSURANCE,ANDDATACRITERIA

A4.1 SPECIFIC METHODSANDANALYSES

The analysesin Table A-I to be performedon the tank U-204 samplesare basedon the safety screeningand organicDQOs referencedin SectionAI.O. The laboratoryprocedure numbers,which shall be used for the analyses,are includedin this table.

A4.2 QUALITYASSURANCE

A4.2.1 LaboratoryOperations

The 222-S Laboratoryhas a qualityassuranceprogramplan (Meznarich1994)anda qualityassuranceprojectplan (Taylor1993)that shallprovidethe primarydirectionfor the qualityassuranceof avdalyzingthe waste tank samplesat the 222-SLaboratory. Additionally,the HanfordAnalyticalServicesQualityAssurancePlan(DOE1994),when implemented(scheduledfor August 1995),shall be used as qualityassurancerequlrements.

Method specificqualitycontrolsuch as calibrationsand blanksare also foundin the analyticalprocedures. Samplequalitycontrol(duplicates,spikes,standards)are identifiedin Table A-I. If no criteriaare providedin Table A-I,z

the performinglaboratoryshall performto its qualityassuranceplan(s).

A4.2.2 SampleCollectionJ

q Two core samples, with an expected one segment each, are to be taken from tank| U-204 and shipped to the performing laboratory by Sampling Operations in accordancem with work packageWS-95-034. That work packageshall also initiatethe

chain-of-custodyfor the samples. Approvedwork procedureT0-080-090("Load/TransportSample Cask(s)")is to be used duringthe samplingevent. Samplesshallbe identifiedby a uniquenumberbeforebeing shippedto the performinglaboratory. The samplingteam is responsiblefor documentingany problemsandproceduralchangesaffectingthe validityof the samplein a fieldnotebook.SamplingOperationsshall enterthis informationin the commentsectionof thechain-of-custodyform for additionto the data reports.

SamplingOperationsshouldtransporteach samplecollectedto the performinglaboratorywithin I workingday of removingthe samplefrom the tank, but musttransporteach samplewithin3 calendardays. The fieldblank shall count as asegment. SamplingOperationsis responsiblefor verballynoLifyingthe 222-SLaboratory(373-2435)at least 24 hours in advanceof an expectedshipment.

I

A-lO

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WHC-SD-Wl_-TP-311,Rev. 0

. A4.2.3 Sample Custodyi

_' The chain-of-custody form is initiated by the sampling team as described inwork package WS-95-034. Samples are shipped in a cask and sealed with a Waste TankSample Seal.

t,

:o WASTETANKSAMPLE

Supervisor" Sample No. :i

' Date of Sampling" Time of Sampling"

Shipment No.' Serial No.'

The sealed and labeled samples are shipped to the laboratory along with thechain-of-custody form. The receipt and control of samples in the WHC222-SLaboratory are described in laboratory proceQure L0-090-I01.

i

i,

A-11

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WHC-SD-WM-TP-311,Rev. 0

, AS.0 ORGANIZATION

_' l'heorganizationand responsibilityof key personnelinvolvedwith this tankU-204 characterizationprojectare listedin TableA_2.

,,{" Table A-2: Tank U-204 ProjectKey PersonnelList

..... _ ' '" ,. , ,__L_ ' _,. ' '"' -- . _ .... ' ' . "' , ' , ' I i ' , L '

Individual...... Organization Responsibility .TWRS Tank U-204 Tank

K E Bell CharacterizationPlans CharacterizationPlan Cognizant, ' ' and Reports Engineer- -- . . , , . Li , _ ,.,,. m

E J Lipke WHC Characterization SafetyScreeningPoint of Contact,. ' ..' ............ Pro_Iram .... ....

D A Turner OrganicTanks Safety OrganicSBfety ProgramManageri ..'. ProBr.am .......

Managerof AnalyticalServicesJ, L. Deichman AnalyticalServices ProgramManag..ementand Integration._,.. , , , J ,, ,,. , , , ,,

West Tank Farm 200 West Tank Farm Point of ContactOperations Tank Farm Operations if Action Limit is ExceededShift._4anager................ (.373-3475)

AS.O EXCEPTIONS,CLARIFICATIONS,AND ASSUMPTIONS

A6.I EXCEPTIONSTO DQO REQUIREMENTS

In the safetyscreeningDQO, it is specifiedthat cyanideanalysesare _o berun on a quarter-.samplelevel and that the notificationlimit for the DSC analysisis 523 J/g (125cal/g), However,the revisedferrocyanideDQO has changedthe

. requirementssuch that the cyanideanalysisis now to be run on a half-segmentleveland the DSC notification'limitis 115 cal/g(dry weightbasis). This changewill bemade to the safetyscreeningDQO when it is revised(currentlyin progress),Therefore,althoughthisSamplingand AnalysisPlan uses the currentsafetyscreeningDQO, it specifiesthat cyanideis to be run on a half-segmentbasis andthat notificationshallbe made if the DSC valueexceeds481 J/g (115 cal/gdryweight basis).

In the organicDQO (Babadet al.1994),IZTCsand 9°Sron half-segmentsareI requestedas seco_pdaryanalyses. However,there are no primaryanalysesthat would| require _37Csor _uSrto be conductedshoulda notificationlimit be exceeded,

th_ Safety Programand theTherefore,it has been decidedJ_yboth OrganicCharacterizationProgramthat 1_'Csand 9oSr on a half-segmentlevel shouldnot beanalyzed.

In the organicDQO, the method of analysesfor principalorganicspecies,equ,Jibriummoisturecontent,and Cr and Mn oxidationstateshas not been developedat this point. Therefore,if it is necessary!;oanalyzethese secondaryconstituents,archivedsampleswill be used for analysesat a later date,

A-16

i

WHC-SD-WH-TP-311,Rev. 0

A6.2 CLARIFICATIONSANDASSUMPTIONS

A numberof clarificationsand assumptionsrelatingto the notificationlimitsor decisionthresholdsidentifiedin the applicableDQO effortsneed to be made withrespectto the analysesin Table A-I. Each of these issuesare discussedbelow.

• Any exotherm(in cal/gor J/g) determinedby DSC must be reportedon a dryweight basis as shown in equation(I) using the w:ight percentwaterdeterminedfrom thermogravimetricanalysis.

Exotherm (drywt) = [exOtherm (wet_jt)x i00]....(16o- wa ez) (I)

NOTE: If there is greaterthan 90 percentwater in a sample,convertingto a dry weightbasis may lead to a largeerror in the DSC value.However,the conversionis still required.

• The safetyscreeningDQO (Babadand Redus 1994)requiresthat additionalanalysesbe performedif total alpha activitymeasuresgreaterthan I g/L,However,total alpha is measuredin #Ci/g by the laboratoryratherthan g/L.

' To convertthe notificationlimit for total alpha into a numbermore readilyusable by the laboratory,it was assumedthat all alpha decay originatesfrom

. Pu-239. The notificationlimit may then be calculatedasshown in equation(2):

10"_mL density g 1 ..q 1 Ci " = ' .._/ (2)) densJ ty g

NOTE: If a densityof 1.5 g/mL is assumedfor solld material,thenotification limit becomes41 #Ci/g.

• Neither the safety screening nor the organic DQOs,upon which the analyses inTable A-I are based, sufficiently addresses the analyses of any drainableliquid present. In order to characterize the tank waste adequately, allanalyses performed on the solids for the safety screening and organic DQOs,with the exception of total alpha analyses, shall also be performed on anydrainable liquids and the field blank.

• None of the DQOs, upon which the analysesin TableA-I are based,addresstheanalysesperformedon the field blank. To adequatelydetermineifcontaminationof the samplematerialhas occurred,the field blank shall beanalyzedfor those analysesdone on the segmentlevel liquidsamples.

!

A-17

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, • In the organicDQO it is unclearas to when secondaryanalysesare to be run.Whether'or not a secondaryDQO is run dependson the coinparisonbetween thevalue of the energyequivalentfor TOC, "X", and the DSC energeticsvalue.The energy equivalentof TOC is given in equation(3).

X = (Wt% TOC dry weight basis), 151 cal/g. (3)5

,'

NOTE: 151 cal/g representsthe energyequivalentof 5 wt% TOC (basedonsodiumacetateaverageenergeticsstandard),

Secondaryanalysesfor the OrganicSafety Programare run on half-segmentsbased on this equatior. Thereforethe followingrules apply:

If X by hot persulfate'is_ 75% of the DSC value,run TOC by furnacecombustionon the half-segment.

, If X by hot persulfateis > 125% of the DSC value,run nitrite,nitrate,and hydroxideanalyseson the half-segment.

, If X by furnacecombustionis _<75% of the DSC, analyzefor the presenceof Mn and Cr on the half-segment.

A7.0 DELIVERABLES

All analysesof tank U-204 waste materialshall be reportedas FormatsI, IIIor IV as indicatedin Table A-I. Additionalinformationregardingreportingformatsis given in Schreiber(1994a).

A7.1 PROGRESSREPORTS

Each laboratoryperforminganalyseson tank U-204 waste materialfrom,thissamplingprojectshall providemonthlystatusreportst.othe CharacterizationProgram. This report shall containI) a summaryof the activitieson the analysisof tank U-204, 2) preliminaryresultsto the program,and 3) scheduleand costinformationon a DQO basis.

Monthlyand accumulativecosts will be comparedto the base as,partof theProgressreport. Monthlyvariancesgreaterthan 10% ar,d $10,000,ana accumulativevariancesgreaterthan $50,000from the estimatedcosts or schedulemust beexplainedIn the report. Cost reportingshall consistof the following:

I. budgetedcost of work scheduled2. monthlycost (actualcost of work performed)_3. year-to-datecosts (actualcost of work performed)

Schedulereportingshallconsistof the following:

I. monthlyschedule2. year-to-dateschedule

A-18

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A7.2 FORMATI REPORTING '

Table A-I contains the notification limits for each analyte. Any resultsexceeding their notification limits shall be reported by calling the West Tank FarmOperations Shift Manager at 373-3475 and the Characterization Program Office(Schreiber 1994b). This verbal_notification must be followed within I working dayby written communication, documenting the observations, to the Organic SafetyProgram, Characterization Plans and Reports, the Characterization Program Office,Safety Screening Representative, and Process Control. Points of contact within eachprogram/projectare definedby Schreiber(1995), Additionalanalysesforverificationpurposesmay be contractedbetweenthe performinglaboratoryand thecontactsabove by a revisionto this documentor by a memorandumof understanding,

A7,3 FORMATIII REPORTING

A Format III report,reportingthe resultsof the primarysafetyscreenanalysesshall be issuedto the SafetyScreeningRepresentative,CharacterizationProgramOffice,Los AlamosTechnicalAssociates(LATA), Tank CharacterizationResourceCenter,Waste Tanks ProcessEngineering,and the Tank CharacterizationDatabaserepresentativewithin 45 days of receiptof the last segmentof the lastcore sample at the laboratoryloadingdock. The DSC and TGA scans have beenrequesteddue to the interpretivenatureof the analysis, If analysesfor thesafety screeningsecondaryanalytesare required,these resultsshallbe providedwithin 90 days of receiptof the last sampleat the laboratoryloadingdock, Nocalibrationdata are requestedfor these reports, Detailedinformationregardingthe contentsof this reportingformatare given in (Schreiber1994a),

Al.3 FORMAT IV REPORTING

Analyticalresultsrequestedfor the characLerizationprojectof tank U-204shall be compiledinto a Format IV type data package. The data packageshall beprovidedto AnalyticalServices,OrganicSafetyProgram,Los AlamosTechnicalAssociates,the Tank CharacterizationResourceCenter,and the CharacterizationProgramwithin 216 days of the samplingevent, Detailedinformationregardingthecontentsof this reportingformatare given in (Schreiber1994a).

In additionto this data package,an electronicversionof the analyticalresultsshall be provided to the Tank CharacterizationDatabaserepresentative.The data must be availableto the WashingtonState Departmentof Ecologywithin 216days of the samplingevent, so this electroniccopy must be sent at the time of datapackagedeliveryor within 209 days of the samplingevent,whicheveris earlier,toallow time for data entry. The electronicversionshall be in the standardelectronicformatspecifiedin (Bobrowski1994).

A.-19

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WHC-SD-HM-TP-311,Rev, 0L

J

AB,O CHANGECONTROL

, Under certain circumstances, it may becomenecessary for the performing" , laboratory to make decisions concerning a sample wtthout review of the data by the. customeror the CharacterizationProgram. 'Thesechangesshall be documentedthrough

the use of internalcharacterizationchangenoticesor analyticaldeviationreportsfor minor low-impactchangesand documentedin applicablelaboratoryreports. Allsignificantchanges(suchas changes,in scope)shall be documentedby

, CharacterizationSupportvia an EngineeringChangeNotice to this TankCharacterizationPlan. All changesshall also be clearlydocumentedin the finaldata report,

Additionalanalysisof samplematerialfrom this characterizationprojectatthe requestof the CharacterizationProgramshallbe performedaccordingto arevisionof this Tank CharacterizationPlan,

A-20

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A9,0 REFERENCES

Babad,w_ and K. S, Redus,1994 Tank Safety.ScreeningData QualityObjective,SD-WM,SP.-O04,Westlng_ouseHanfordCompany,Richlano,Washington,

Babad,H,, S M. Blacker,and K. s. Redus, 1994,Data _ualltyObjectiveto Sup_portResolutionof the OrganicFuel Rich Tank Safety.Issue.WHC-SD-WM-DQO-O06,Rev O, westinghouseHanfordCompany,Richland,Washington.

Bell, K. E,, 1994, Tank Waste .RemediationSystemTank Waste CharacterizationPlan,WHC-SD-WM-PLN-047,Rev, I, WestinghouseHanfordCompany,Richland,Washington.

Bobrowski,S. F,, S. J, Harris,and J, D. Schwab.1994,"StandardElectronicFormatSpecificationfor Tank CharacterizationDatabaseLoader,Version2,0", PacificNorthwestLaboratory,Richland,Washington (Transmittedby PNL LetterTCD-94-O02,June 16, 1994, S. F. Bobrowski,PNL,to C, S, Hailer,WHC).

Bratzel,D, R., Letterto S. M. Joyce, "ArchivingRequirements",7E720-94..125,datedJune 23, 1994,

Conwayz J, T., Letterto H;,R. O'Leary,DOE, "DNFSBRecommendation93-5 to the_ecretaryof Energy, 9400070,dated July, 1993.

DOE, 1994,HanfordAnalyticalServicesOua,l_tyAssurancePlan DOE/HL-94-55,Rev. O,U. S, DepartmentoT Energy,Richlana ieldOffice,Richland Washington,

Hailer,C. S., 1994, Fiscal Year 1995Tank Waste RemediationSystemTank WasteAnalysTsPlan, WHC-SD-WM-PLN-091,Rev. 0 WestinghouseHanfordCompanyRichland,Washirlgton.

Hanlon,B, M. 1994, Waste TankSummaryfor Month EndinWHC-.EP-OIB2-BOWestinghouseHanfordCompany,RichlN°vember

q 30, 1994,, and, Washington.

Hill,J. G.. W. J. Winters,and B, C. Simpson,1991, Waste CharacterizationPlanfor the HanfordSite Single-ShellTanks,WHC-EP-0210,Rev. 3, WestinghouseHanfordCompany,Richland,Washington.

Meznarich,H, K., 1994,QualityAssuranceProgramPlan for LaboratoryAnalysisandProcess Testing,WHC-SD-CP-QAPP-O03,Hey. I, WestinghouseHanfordCompany,Richland,Washlngton,

Schreiber,R. D., 1994a,Letterto C. S. Hailer,"RevisedInterimTankCharacterizationPlan Guidance",7E720-94-121,datedMay 13, 1994.

Schreiber,R. D.Ic,,Igg4bLetterto J. G, Kristofzski,"FormatI ReportingRequiremen _ 7E7_0-94 28, dated August 15, 1994.

Schreiber.R. Di, 1995, Letterto _i G. Kristofzski,"REVISION:Point ofContact/ stributionList , 520-95-108,dated March 15, 19954.

Taylor,L. H., 1993,QualityAssuranceProjectPlan for ChemicalAnalysisof HighlyRadioactiveMixed Waste Samplesin Supportof EnvironmentalActivitieson theHanfordSTte, WHC-SD-CP-QAPP-O02Rev. OA, WestinghouseHanfordCompany,Richland,Washington.

Whelan/_/_nE., et al,, 1994, TWRS CharacterizationProgramQuali_iAs.s'uranceProgramWHC-SD-WM-QAPP-025,Rev.O, WestinghouseCompany,Ri and, Washington.

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