96-0003338

Department of EnergyRichland Operations Office

P.O. Box 550Richland, Washington 99352

AUG 19 1996

96-WSD-154

Mr. John T. Conway, ChairmanDefense Nuclear Facilities Safety Board625 Indiana Avenue, N.W., Suite 700Washington, D.C. 20004

Dear Mr. Conway:

TRANSMITTAL OF THE U.S. DEPARTMENT OF ENERGY, RICHLAND OPERATIONS OFFICE (RL),QUARTERLY REPORT FOR THE DEFENSE NUCLEAR FACILITIES SAFETY BOARD (DNFSB)RECOMMENDATION 90-7, PERIOD APRIL 1, 1996, THROUGH JUNE 30, 1996

Enclosed for your information and use are two copies of the RL approved statusreport entitled IIQuarterly Report on the Ferrocyanide Safety Program for thePeriod Ending June 30, 1996,11 WHC-EP-0474-21, dated July 1996. This reportreviews the progress of work activities described in the IIProgram Plan forResolution of the Ferrocyanide Waste Tank Safety Issue at the Hanford Site,1IDOE-RL-94-110, 1994, Revision 1, including work addressing the six parts ofDNFSB Recommendation 90-7.

We appreciate your continued interest and support in the resolution of all theHanford radioactive waste tank safety issues.

If you have any questions, please contact me or your staff may contactJackson Kinzer, Assistant Manager for Tank Waste Remediation System on(509) 376-7591.

Sincerely,

WSD:WFH

Enclosure

cc wjencl:R. Guimond, EM-2J. Tseng, EM-4H. Calley, EM-38M. Hunemuller, EM-38S. Trine, RL DNFSB LiaisonM. Whitaker, S-3.1

~!rManager

861 3,33 8

WHC-EP-0474-21

Quarte~yR~porton.thE!FerrocyanideSafe~ Prog~amfor the Period EndingJune 30, 1996

Prepared for the U.S. Department of EnergyOffIce of Envi~onmentalRestoration andWaste Management

@w~. ••. Hanford Company Richland, Washington

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

Approved for public release, distribution is unlimited

---_.._._----------

LEQAL DISa.AlMER _

This report was prepared Il8 an account of work sponeored byan agency of 1M United States Government. Neither theUnited States Government nor any agency thereof, nor any oftheir employees, nor any of their contractors, subcontractorsor their employe•• milk.. any warrllnty, expre68 or implied,or assume. any leglllliability or responsibility for theaccuracy, cOl'f1)letene68, or any third PIlny'S use or the resulteof 8lJch use of any infonnation, apparatus, product, or procelldilClosed, or represente tl'Jat ite use would not infringepriviltely owned rights. Reference herein tOllnyspecificcommercial product, process. or seMce by trade name,trademark, manufacturer. or otherwise, does not necessarilyconstitute or imply ite endorsement, recommendation, orfllvoring by the United States Government or any agencythereof or its contractol'8 or llUbcontractors. The ~ews andopinions of authors expressed herein do not neoessarily Bteteor r.floot thoae of the United States Government or enyagency thereof.

Thi. report has been reproduced from the best available copy.Available in paper copy and microfiche.

Available to the U.S. Department of Energyand its contractors frolTlU.S. Department of EnergyOffice of Scientific and Technieallnfonnation (OSTI)P.O. Box 62Ollk Ridge, TN 3783116151 576-8401

Available to the public from the U.S. Department of CommerceNational Technicatlnformation SIMel (NTIS)5285 Port Royal RoadSpringfield, VA 22161(703) 487-~650

Printed in IN United Stal. of America

CISCLM-l.CHP (8-95)

9 6 / 3,33 8

WHC-EP-Q474-21

Quarterly Report on theFerrocyanide Safety Programfor the Period EndingJune 30, 1996

G. T. DukelowR. J. CashJ. E. Meacham

Date Published

July 1996

Prepared for the U.S. Department of EnergyAssistant Secretary for Environmental Management

@ Westinghouse P.o Box 1970- Hanford Company Richland, Washington

Management and OperatioN Contractor for theU.S. Department of Energy under Contract DE-AC06-87RL10930

Approved for public release; distribution is unlimited

'1

,"

RELEASE AUTHORIZATION

Document Number: WHC-EP-0474-21

Document Title: Quarterly Report on the Ferrocyanide Safety Programfor the Period Ending June 30, 1996

Release Date: 7/31/96

This document was reviewed following theprocedures described in WHC-CM-3-4 and is:

APPROVED FOR PUBLIC RELEASE

WHC Information Release Administration Specialist:

+~July 31, 1996

Kara M. Brol

A-6001-400 (07/94) WEF256

WHC-EP-0474-21

QUARTERLY REPORT ON THE FERROCYANIDE SAFETY PROGRAMFOR mE PERIOD ENDING JUNE 30, 1996

G. T. DukelowR. J. Cash

J. E. Meacham

ABSTRACT

This is the twenty-first quarterly report on the progress ofactivities addressing the

Ferrocyanide Safety Issue associated with Hanford Site high-level radioactive waste tanks.

Progress in the Ferrocyanide Safety Program is reviewed, including work addressing the six

parts ofDefense Nuclear Facilities Safety Board Recommendation 90-7 (FR 1990). All work

activities are described in the revised program plan (DOE 1994b), and this report follows the

same format presented there. A summary of the key events occurring this quarter is

presented in Section 1.2. More detailed discussions ofprogress are located in Sections 2.0

through 4. O.

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CONTENTS

1.0 INTR.ODUCTION 1-11.1 PURPOSE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-11.2 QUARTERLY HIGHLIGHTS 1-11.3 REPORT FORMAT 1-21.4 BACKGROUND 1-2

2.0 FERROCYANIDE SAFETY DOCUMENTATION 2-1

3.0 ACTIONS TO COMPLETE DNFSB RECOMMENDATION 90-7 3-13.1 ENHANCED TEMPERATURE MEASUREMENT 3-1

3.1.1 Instrument Trees . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-13.1.2 Upgrades to Existing Temperature Monitoring Instrumentation ..... 3-23.1.3 Hot Spot Thermal Modeling . . . . . . . . . . . . . . . .. . . . . . . . . . 3-23.1.4 Infrared Scanning System 3-33.1.5 Cooling System Requirements ',' 3-3

3.2 CONTINUOUS TEMPERATURE MONITORING 3-43.3 COVER GAS MONITORING 3-5

3.3.1 Interim Flammable Gas Monitoring 3-53.3.2 Continuous Gas Monitoring 3-5

3.4 FERROCYANIDE WASTE CHARACTERIZATION 3-63.4.1 Ferrocyanide Tank Waste Sampling and Analyses 3-73.4.2 Estimation of Water Content 3-103.4.3 Moisture Retention Properties of Ferrocyanide

Sludge and Saltcak:e Simulants . . . . . . . . . . . . . . . . . . . . . . . . 3-133.5 CHEMICAL REACTION STUDIES 3-14

3.5.1 Chemical Reaction Studies at Pacific Northwest National Laboratory 3-143.5.2 Preparation and Characterization of Ferrocyanide Simulants 3-18

3.6 EMERGENCY RESPONSE PLANNING 3-18

4.0 IMPLEMENTATION OF THE WYDEN AMENDMENT 4-14.1 THE WATCH LIST .4-14.2 TEMPERATURE MONITORING 4-34.3 PRESSURE MONITORING 4-4

5.0 PROGRAM SCHEDULES AND MILESTONES 5-1

6.0 REFERENCES 6-1

APPENDIX

A FERROCYANIDE TANK INFORMATION SUMMARY A-I

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LIST OF FIGURES

3-1 Ammonia Production and Reproducibility in the Hydrolysis of In-Farm-1BSimulant in 25 mL of 2 M NaOH at 90°C and 1 x 1()5 rad/h 3-15

5-1 Ferrocyanide Waste Tank Safety Schedule 5-2

LIST OF TABLES

3-1 Cyanide Mass Balance 3-17

3-2 Aging Rates as a Function of Temperature for Waste SimulantExperiments .... 3-17

vi

cal/gDNFSBDOEDOE-RLDQOEAEMIFAIFSARFTIRFYg.:molGAOIRISBJ/gkWLANLLOWNASANIRPNNLppmvppmrad/hSASEMSSTTCTCRTMACSTOCUSQWHCwt%

WHC-EP-0474-21

LIST OF TERMS

calories per gramDefense Nuclear Facilities Safety BoardU.S. Department of EnergyU.S. Department of Energy, Richland Operations Officedata quality objectivesenvironmental assessmentelectromagnetic inductionFauske and Associates, Inc.Final Safety Analysis ReportFourier transform infrared spectroscopyfiscal yeargram-moleU. S. General Accounting Officeinfraredinterim safety basisJoules per gramkilowattLos Alamos National Laboratoryliquid observation wellNational Aeronautics and Space Administrationnear infraredPacific Northwest National Laboratoryparts per million by volumeparts per million by weightRads per hoursafety assessmentscanning electron microscope/microscopysingle-shell tankthermocoupletank characterization reportTank Monitor and Control Systemtotal organic carbonunreviewed safety questionWestinghouse Hanford Companyweight percent

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1.0 INTRODUCTION

1.1 PURPOSE

This quarterly report provides a status of activities underway on the Ferrocyanide SafetyIssue at the Hanford Site, including actions in response to Defense Nuclear Facilities SafetyBoard (DNFSB) Recommendation 90-7 (FR 1990). In March 1991, a DNFSBimplementation plan (Cash 1991) responding to the six parts of Recommendation 90-7 wasprepared and sent to the DNFSB. A ferrocyanide safety program plan addressing the totalFerrocyanide Safety Program, including the six parts of DNFSB Recommendation 90-7, wasreleased in October 1994 (DOE 1994b). Activities in the program plan are underway or arecompleted, and the status of each is described in Sections 2.0 and 3.0 of this report.

1.2 QUARTERLY mGHLIGHTS

• Final approval was received (Kinzer 1996) from 'the U.S. Department ofEnergy (DOE), Richland Operations Office (DOE-RL) on June 25, 1996 toremove the four C-Farm Ferrocyanide tanks (241-C-108, C-109, C-111, andC-1l2) from the Wyden Amendment Watch List (public Law 101-510, 1990).

• The technical basis safety document for removal of the remaining 14ferrocyanide tanks from the Wyden Amendment Watch List, and for finalresolution of the Ferrocyanide Safety Issue (WHC-SD-WM-SARR-038,Revision 1), was completed and submitted to DOE-RL on July 3, 1996(Bacon 1996c, Meacham et al. 1996). Approval to remove the remaining 14tanks by DOE will resolve the Ferrocyanide Safety Issue and complete theFerrocyanide Safety Program.

• The final aging report (pNNL-1l211) was issued on June 28, 1996 andsummarizes all work completed to date on aging studies (Lilga et al. 1996). Theinformation was key to completing the technical basis safety document,WHC-SD-WM-SARR-038, Rev. 1.

• The final analytical report was completed for ferrocyanide tank 241-BY-104 thisquarter (Benar 1996b). The final results were incorporated into the technicalbasis safety documentation.

• The final analytical report was completed for 241-BY-110 this quarter and thetank characterization report (TCR) is in preparation with a scheduledAugust 1996 issuance date (Schreiber 1966). No sample obtained had meanexothermic reactions (on a dry weight basis) exceeding the Ferrocyanide Data

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Quality Objectives (DQO) (Meacham et al. 1995) limit of 480 Joules per gram(Jig). In addition, the observed cyanide concentrations were well below theferrocyanide IJQO limit.

1.3 REPORT FORMAT

Progress reports for activities under each of the six parts of DNFSB Recommendation 90-7are arranged in the same order as the program plan (DOE 1994b). The arrangement alsofollows the same order provided in Recommendation 90-7. To report on progress, each partof the recommendation is repeated in italics, followed by paragraphs explaining the scope ofwork on each part or subpart of the recommendation. Subheadings for each task activityreport the following:

• Progress During Reporting Period• Planned Work for Subsequent Months• Problem Areas and Action Taken• Milestone Status.

1.4 BACKGROUND

Since the mid-1940's, various high-level radioactive wastes from defense operations haveaccumulated at the Hanford Site in underground storage tanks. During the 1950's, additionaltank storage space was required to support the defense mission. To obtain this additionalstorage volume within a short time period, and to minimize the need for constructingadditional storage tanks, Hanford Site scientists developed a process to scavenge 137CS. and90Sr from tank waste liquids. In implementing this process, approximately 140 metric tons(154 tons) of ferrocyanide were added to waste that was later routed to a number of HanfordSite single-shell tanks (SSTs) (Sloat 1954, 1955).

In the presence of oxidizing material such as sodium nitrate and/or nitrite, ferrocyanide canbe made to react exothermically by heating it to high temperatures or by applying anelectrical spark of sufficient energy (Cady 1993). However, fuel, oxidizers, and temperatureare all important parameters. If fuel, oxidizers, or high temperatures (initiators) are notpresent in sufficient amounts, then a runaway or propagating reaction cannot occur.

In 1990, little was known about the potential hazards of a ferrocyanide-nitrate/nitrite reactionin Hanford Site SSTs. The existing safety analysis report (Smith 1986) and subsequentanalyses such as the 1987 environmental impact statement (DOE 1987) did not adequatelydefine the conditions necessary to preclude propagating reactions in the ferrocyanide waste.

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Because the safety envelope was not adequately defined by existing analyses, an inadequacyexisted in the authorization basis*, and an unreviewed safety question (USQ) was declared(Deaton 1990).

Based on the knowledge gained from simulant studies, theoretical analyses, and analyses ofactual waste samples, safety criteria were defined for the ferrocyanide waste(postma et al. 1994a). These criteria were reviewed and accepted by outside reviewers andreviewers within DOE. The USQ was closed on March 1, 1994 by the DOE AssistantSecretary for Environmental Restoration and Waste Management (Sheridan 1994b).

In September 1990, an ad hoc task force report (Kress et al. 1990) recommended that studiesbe performed to provide information on (1) the potential for a ferrocyanide-nitrate/nitriteexplosion; (2) the conditions necessary in the tanks to initiate an explosion; and (3) thepotential consequences of such an occurrence. The U.S. General Accounting Office (GAO)advised the Secretary of Energy to implement these recommendations (peach 1990).A closeout report addressing all three GAO recommendations was submitted to DOE inJune 1994 (payne 1994b). The closeout report summarizes the progress made ondetermining the potential for ferrocyanide reactions in Hanford Site ferrocyanide tanks, andthe conditions necessary to sustain an exothermic ferrocyanide reaction.

In March 1989, based on process knowledge, process records, transfer records, and logbooks, 22 Hanford Site tanks were identified as potentially containing 1,000 gram-moles(g-mol)** (211 kg [465 Ib]) or more of ferrocyanide as the Fe(CN>t anion (Nguyen 1989).Two additional ferrocyanide tanks were identified in January 1991 (Borsheim andCash 1991), increasing the number of ferrocyanide tanks to 24. To avert possible injury topersonnel and damage to the facility or environment, strict controls were identified for theseand other safety issue tanks in Operating Specifications for Watch List Tanks (WHC 1990).Tanks identified by this document (see WHC 1996 for the latest revision) have beencommonly referred to as Watch List tanks. In October 1990 (Deaton 1990), theFerrocyanide Safety Issue was declared a USQ (see Section 2.1) because the safety envelopefor these tanks was no longer considered to be bounded by the existing safety analysis report(Smith 1986). '

The DOE authorization basis characterizes the facility design basis and operationalrequirements for each nuclear facility. The authorization basis is described in documentssuch as facility safety analysis reports and other safety analyses, hazard classificationdocuments, technical· safety requirements, DOE-issued safety evaluation reports, andfacility-specific commitments such as safety assessments for specific tank operations and theInterim Safety Basis (ISB) (Wagoner 1993).

*The 1,000 g-mol criterion has since been replaced with a 115 calories per gram (cal/g)(480 Jig) fuel concentration criterion. See Section 4.1 for discussion.

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In November 1990, the Wyden Amendment was enacted (public Law 101-510, 1990). Thislaw required the identification of Hanford Site tanks that may have a serious potential forrelease of high-level waste (see Section· 4.0). In February 1991, the 24 ferrocyanide tankswere among the tanks identified (Harmon 1991), and were included in the subsequent July1991 report to Congress that responded to the Wyden Amendment (Watkins 1991).However, re-examination of the historical records indicated that 6 of the 24 tanks did notcontain the requisite 1,000 g-mol of ferrocyanide (Borsheim and Simpson 1991). Therefore,these six tanks should not have been included on the Watch List nor identified in theresponse to the Wyden Amendment. The six tanks were subsequently removed from theWatch List (Anttonen 1993, Sheridan 1994b).

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2.0 FERROCYANIDE SAFETY DOCUMENTATION

The USQ process depends on an authorization basis that describes those aspects of thefacility design basis and operational requirements relied on by DOE to authorize operation.The authorization basis is described in documents such as facility safety analysis reports andother safety analyses, hazard classification documents, technical safety requirements,DOE-issued safety evaluation reports, and facility-specific commitments such as safetyassessments (SAs), the ISB, and the Final Safety Analysis Report (FSAR) that is scheduledfor completion in November 1996. The potential hazards of a ferrocyanide.;.nitrate/nitritereaction were discovered to represent an inadequacy in the authorization basis (Smith 1986).The Ferrocyanide USQ was closed on March 1, 1994 by the DOE Assistant Secretary forEnvironmental Restoration and Waste Management (Sheridan 1994a). Progress on theremaining safety documentation for resolving the Ferrocyanide Safety Issue is reviewed inthis section.

Safety and Environmental Assessments. SAs are documents prepared to provide thetechnical basis for assessing the safety of a proposed activity and to provide proper controlsto maintain safety. The SA and the accompanying environmental assessment (EA) for thatoperation provide the basis for DOE authorization of the proposed activities. SAs have beenapproved for headspace sampling of all ferrocyanide tanks, waste surface sampling,pUSh-mode and rotary-mode core sampling, thermocouple (TC)/instrument tree installation insound and assumed-leaker tanks, and removal of pumpable liquid (interim stabilization).A generic EA covering all proposed operations in the tank farms was approved and a Findingof No Significant Impact was issued by DOE (Gerton 1994). Approval of the generic EAprovides adequate National Environmental Policy Act coverage for the planned FerrocyanideSafety Program activities.

The authorization basis for intrusive tank operations was combined into one document, theISB, which was approved in November 1993 (Wagoner 1993). Safety documentationconcerning the ferrocyanide hazard was updated to reflect the approved ferrocyanide safetycriteria and closure of the Ferrocyanide USQ. This information is also being incorporatedinto the draft FSAR that will replace the ISB when approved by DOE.

Hazard Assessment. A report assessing the ferrocyanide waste tank hazards was issued inJuly 1992 (Grigsby et al. 1992). The report reviewed the understanding of the ferrocyanidehazard at that time, and presented an integrated evaluation and interpretation of historicaldata and then-available information. Additional data are now available on the potential forexothermic ferrocyanide reactions in Hanford Site SSTs.

The ferrocyanide hazard assessment document, Assessment of the Potential for FerrocyanidePropagating Reaction Accidents, WHC-SD-WM-SARR-038, Revision 0 (Grigsbyet al. 1996a), was transmitted to DOE-RL on January 31, 1996. Minor comments wereincorporated into the document as Revision OA and the document was retransmitted toDOE-RL on March 19, 1996 (Grigsby et al. 1996b). Revision OA was subsequently

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forwarded to the DNFSB by DOE-RL on April 10, 1996 (Trine 1996). The documentprovided the technical basis for removal of the four C-Farm ferrocyanide tanks (241-C-108,C-I09, C-ll1, and C-112j from the Watch List. Approval fOJ;" their removal from the WatchList was received from DOE-RL on June 25, 1996 (Kinzer 1996).

Revision 1 of the document (Meacham et al. 1996) was completed this quarter, addressing all18 ferrocyanide tanks, and the document was transmitted to DOE-RL on July 3, 1996. Thetransmittal letter (Bacon 1996c) requested approval to remove the remaining 14 ferrocyanidetanks from the Watch List and for final resolution of the Ferrocyanide Safety Issue based onRevision 1 of the document. The Chemical Reaction Subpanel of the Tanks Advisory Panelreviewed the document in June 1996, and their comments were addressed and incorporated.Technical information from all Ferrocyanide Safety Program tasks was compiled into thisdocument, and following DOE approval, the ISB and draft FSAR will be revisedaccordingly.

Ferrocyanide Program Pian. A ferrocyanide program plan was submitted to the DNFSB inDecember 1994 (O'Leary 1994). The program plan outlines activities planned to addressDNFSB Recommendation 90-7, to meet the Wyden Amendment requirements (PublicLaw 101-510, 1990), and to remove the remaining ferrocyanide tanks from the Watch List.All ferrocyanide program activities are scheduled to be completed by the end of fiscal year(FY) 1997. However, an increased understanding of radiolytic and chemical degradation(aging) of ferrocyanide indicates that little ferrocyanide remains, and core sampling of all thetanks is not required. Core sampling and analyses of only those tanks that bound aging (i.e.,tanks with conditions least conducive to aging) could result in resolution of the FerrocyanideSafety Issue much earlier and at a substantially reduced cost. Ferrocyanide tanks that havenot been sampled to date will eventually be sampled as part of other safety issues or DQOs,such as the Organic Safety Program or the Safety Screening, Historical, or Retrieval DQOs(Dukelow et al. 1995, Simpson and McCain 1996).

• Milestone Status

January 31, 1996. Westinghouse Hanford Company issues documentationsupporting safety issue resolution for the four C-Farm tanks andrecommends their removal from the Wyden Amendment Watch List(Public Law 101-510, 1990). The Assessment of the PotentialforFerrocyanide Propagating Reaction Accidents, WHC-SD-WM-SARR-038,Revision 0, was transmitted to DOE-RL as scheduled (Bacon 1996a,Grigsby et al. 1996a). All four C-Farm tanks were sampled earlier anddata interpretation reports have been completed for these tanks.

The report was revised to incorporate informal comments received fromDOE-RL and reissued with the same title, as WHC-SD-WM-SARR-038,Revision OA (Grigsby et al. 1996b). The revised report was transmitted toDOE-RL with a letter requesting that the four C-Farm tanks be removed

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from the Watch List on March 19, 1996 (Bacon 1996b). The report wassubsequently forwarded to the DNFSB Staff on April 10, 1996(Trine 1996).

July 31,1996. Westinghouse Hanford Company receives DOE approvalto remove the four C-Farm ferrocyanide tanks from the Watch List.Approval was received from DOE on June 25, 1996, ahead of schedule(Kinzer 1996).

July 31, 1996. Westinghouse Hanford Company prepares and submits thefmal ferrocyanide hazard assessment for DOE approval, providing thetechnical basis for removing all 18 ferrocyanide tanks from the Watch List,and resolution of the Ferrocyanide Safety Issue. The official due date forthis milestone is August 30, 1996, with an enhanced date of July 3, 1996.The final ferrOcyanide hazard assessment, (WHC-SD-WM-SARR-038,Revision 1 Meacham et al. 1996), was prepared and submitted for DOEapproval on July 3, 1996 (Bacon 1996c).

September 30, 1997. Westinghouse Hanford Company receives DOEapproval for the Ferrocyanide Safety Issue resolution. It is anticipated thatDOE will approve this request by September 30, 1996, based on earlysubmittal of the final hazard assessment document.

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3.0 ACTIONS TO COMPLETE DNFSB RECOMMENDATION 90-7

This section follows the format of the program plan (DOE 1994b) and describes all workassociated with the Ferrocyanide Safety Program. Where applicable, each task activity isdescribed relative to the DNFSB Recommendation (90-7.1 through 90-7.6). The specificpart of the recommendation is given, followed by a summary of activities underway torespond to that part of Recommendation 90-7 (if not already closed out).

3.1 ENHANCED TEMPERATURE MEASUREMENT

"Immediate steps should be taken to add instrumentation as necessary to the SSTs containingferrocyanide that will establish whether hot spots exist or may develop in the future in thestored waste. The instrumentation should include, as a minimum, additional thermocoupletrees. Trees should be introduced at several radial locations in all tanks containingsubstantial amounts offerrocyanide, to measure the temperature as a function ofelevation atthese radii. The use of infrared techniques to survey the surface ofwaste in tanks shouldcontinue to be investigated as a priority matter, and on the assumption that this method willbe found valuable, monitors based on it should be installed now in the ferrocyanide bearingtanks. "

3.1.1 Instrument Trees

All new instrument trees planned for the ferrocyanide tanks have been installed and thisaction was completed in August 1995. Originally, several new temperature measurementinstruments were to be installed into each tank. This plan was modified to ensure that atleast one instrument tree with replaceable temperature-sensing elements was in eachferrocyanide tank. The new trees have at least two operational temperature-sensing elementsin the waste to ensure a true temperature measurement, and one or more elements in theheadspace. The number of temperature sensing elements in the new trees is typically six, butsome tanks with larger inventories of waste contain up to eight elements.

The decision to put only one new tree into each tank was based on the following: (I) manyof the TC elements in the existing trees were returned to service in FY 1992, and measuredtemperatures are as expected (Bussell 1992); (2) thermal modeling (McLaren 1994a, 1994b)and an enhanced understanding of waste properties show that formation of hot spots inferrocyanide tanks is not credible (Dickinson et al. 1993, Epstein et al. 1994); and (3) newcalculations of tank heat content based on tank temperatures show lower values than previousestimates (Crowe et at. 1993, McLaren 1994a, 1994b).

There are two instrument trees in all but three ferrocyanide tanks (241-BY-I06, BY-UI,and BY-112). The instrument tree in tank 241-BY-I06 already had replaceable temperaturesensing elements, and tanks 241-BY-Ill and BY-112 previously had no operable instrument

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trees. The instrument trees in the ferrocyanide tanks are monitored continuously by the TankMonitor and Control System (TMACS). The older instrument trees are expected eventuallyto fail in a manner such that they cannot be repaired, and they will not be replaced. Thehighest temperatures recorded in each of the tanks for the quarter ending March 31, 1996 arelisted in Appendix A, Table A-I.

• Status. The last of 16 new instrument trees were installed in the 18 ferrocyanidetanks in August 1995. A total of 33 working instrument trees and a TC elementin each liquid observation well (LOW) of tanks 241-BY-lll and BY-I12 arecontinuously monitored by TMACS. All work is complete for this task andDNFSB Recommendation 90-7.1 is closed.

3.1.2 Upgrades to Existing Temperature Monitoring Instrumentation

This task determined the operability and accuracy of previously installed TC elements in theoriginal 24 ferrocyanide Watch List tanks. The original and newly-installed instrument treesprovide temperature measurements for each of the ferrocyanide tanks.

Field measurements were taken in 1991 on each TC element in the then-existing trees todetermine the resistance and voltage across the junction, and across each lead to ground.The exact condition of each TC element was determined by resistance and voltagemeasurements (Bussell 1992). This work was completed in FY 1991 with a total of 265 TCelements evaluated. Work in FY 1992 focused on repair and recovery of 92 TC elementsthat were found to be failed or marginal in performance. This task was completed inFY 1992 for the Ferrocyanide Safety Program.

• Status. This task is complete for the Ferrocyanide Safety Program.

3.1.3 Hot Spot Thermal Modeling

Radioactive materials decaying in Hanford Site waste tanks generate heat. An early concern,raised when the ferrocyanide tanks first became a safety issue, was whether an exothermicexcursion and local propagation could occur within the ferrocyanide waste if a sufficientconcentration of ferrocyanide and a high enough temperature were present. This taskexamined the available temperature data from the ferrocyanide tanks in order to determinethe heat load and temperatures as a function of depth and radial location. Sensitivity andparametric analyses were included to determine the magnitude of a hot spot that would haveto exist for the waste to reach propagation temperatures.

Heat load analyses and thermal characteristics were completed for all ferrocyanide tanks inFY 1994 (McLaren 1994a, 1994b). The maximum heat load of any ferrocyanidetank, assuming worst-case conditions for soil moisture and thermal conductivity, was below4.2 kilowatts (kW). Nominal heat loads calculated in 1994 (McLaren 1994a, 1994b)

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compared very favorably with those calculated independently in 1993 (Crowe et al. 1993).A dryout analysis was also completed and released in FY 1994 (Epstein et al. 1994). Thereport concluded that ferrocyanide sludge could not dry sufficiently to be chemically reactiveduring interim storage, either globally or locally. Dryout mechanisms evaluated includedglobal evaporation, removal of liquid by leakage or pumping, boiling as a result of hot spots,and enhanced surface evaporation from hot spots. All activities were completed for this taskin FY 1994.

• Status. This task is complete.

3.1.4 Infrared Scanning System

Infrared (IR) scanning systems are commercially available from numerous vendors. Thesesystems are sensitive to changes of ± 0.3 °C or less under ideal conditions, and offerpromise for mapping surface temperature profiles in the ferrocyanide tanks. Thermalmodeling performed on ferrocyanide tank 241-BY-l04 suggested that if hot spots withtemperatures of concern are possible, surface temperature differences might be great enoughto be detected by IR mapping (McLaren 1993).

A position paper on the credibility of hot spots and the need for further IR scanning wasissued in April 1993 (Dickinson et al. 1993). Further analyses have been performed toassess potential dryout of the ferrocyanide waste (Epstein et al. 1994). These reportsexamined potential mechanisms for forming hot spots. Analyses indicate that hot spots arenot credible in ferrocyanide tanks. Based on these analyses, Westinghouse HanfordCompany recommended that no further planning be pursued for IR scans for the purpose ofdetecting hot spots. Work on this Ferrocyanide Safety Program task was concluded at theend of FY 1993.

• Status. This task is complete.

3.1.5 Cooling System Requirements

The program plan for resolution of the Ferrocyanide Safety Issue (DOE 1994b) providedactions that would be taken to cool the ferrocyanide tanks if it were found that such coolingwas necessary. Several tentative milestones, identified below, were established for use if acooling system(s) were required. The concern at the time was that increasing temperaturescould lead to loss of moisture within the ferrocyanide waste matrix. Immediate emergencyactions that would be taken if increased temperatures were to occur are described in theAction Plan for Response to Abnormal Conditions in Hanford Site Radioactive Waste TanksContaining Fe"ocyanide (WHC-EP-0407, Revision 2 [Fowler 1994]). Types of coolingsystems might include, but are not limited to, the following: (1) forced ventilation of thetank, using an existing or new exhauster system; (2) air conditioning the air to the tank;(3) adding humid air or mist;' and (4) adding water to the tank.

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Based on the historical databaset analytical data on samples from ferrocyanide tanks, andresults from the Pacific Northwest National Laboratory (pNNL) aging test activity, none ofthe 18 ferrocyanide tanks oontain a high enough concentration of ferrocyanide for apropagating reaction to occur. Because dryout of the waste under the present storageconditions is not crediblet a special cooling system for the ferrocyanide tanks is not,considered necessary (Epstein et al. 1994).

• Status. This task is complete.

3.2 CONTINUOUS TEMPERATURE MONITORING

"The temperature sensors referred to above [Recommendation 9O-7.1J should have continuousrecorded readouts and alarms that would signal at a permanently manned location anyabnormally high temperatures and any failed temperature instrumentation. "

This task provided continuous monitoring of presently installed (and operable)temperature-sensing elements for the ferrocyanide tanks. New instrument trees wereconnected to TMACS shortly after they were installed into each tank, resulting in continuoustemperature monitoring in the ferrocyanide tanks. All data are collected automatically at thecontinuously manned Computer Automated Surveillance System Operator Control Station.The monitoring system is independent of the Computer Automated Surveillance System anddisplays data to an operator on request. Trend data on selected points are available fordisplay in numeric or graphic form.

The TMACS system, which became operational in September 1991, provides alarms for achange in the value of any temperature point. Alarms, if they occur, trigger an audibleannunciator and are logged immediately to hard copy. An alarm summary display provides alist of the most recent alarms in order of occurrence. Each alarm can be identified by pointand time of occurrence. Operator acknowledgement of the alarm will silence the audibleannunciator. Signal conditioning and multiplexing are performed locally at each tank,eliminating the need to transmit low-level signals tathe tank farm boundary and reducingcable runs. Electronic noise, extension wire corrosion, and thermal gradients are alsoreduced.

• Status. Temperatures measured by 33 instrument trees and two TC elements inLOWs in the ferrocyanide tanks are being monitored continuously by TMACS.This work was completed in August 1995, and DNFSB Recommendation 90-7.2is closed. The highest temperatures recorded in each of the tanks for the quarterending June 30, 1996 are listed in Appendix A, Table A-I. This task iscomplete.

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3.3 COVER GAS MONITORING

"Instrumentation should aiso be installed to monitor the composition of cover gas in thetanks, to establish ifflammable gas is present. "

3.3.1 Interim Flammable Gas Monitoring

Flammable and toxic gas monitoring and analyses in the ferrocyanide tanks and otherHanford Site waste tanks are continuing. This effort was transferred to the Tank VaporMonitoring Program, which is coordinating interim gas monitoring of the ferrocyanide tanksand tanks involved with the tank vapor program. Tank headspaces are measured forflammability using a commercial combustible gas monitor (calibrated with pentane gas), andare monitored for potential toxic gases using an organic vapor monitor and Drager* tubes.Headspace characterization of all the Hanford Site high-level waste tanks is continuing usingsorbent tubes placed on the end of tubes lowered into the headspace, and SUMMA**canisters that collect gas samples topside. The initial headspace sampling was·done inseveral tank locations (Le., from two widely separated risers) and at three elevations in theheadspace. Reviews of sampling data and modeling (Wood 1992, Claybrook andWood 1994, Postma et al. 1994b) indicate that the headspace is well mixed and that samplingfrom one riser at one elevation is adequate.

• Status. Headspace sampling of all 18 ferrocyanide tanks as required for this taskwas completed in May 1995. The results are summarized in Appendix A,Table A-2. Headspace sampling of the ferrocyanide tanks and other HanfordSite high-level waste tanks will continue on a periodic basis as part of the TankVapor Monitoring Program. DNFSB Recommendation 90-7.3 is closed.

3.3.2 .Continuous Gas Monitoring

The possibility that localized concentrations or stratification of gases exist in the tanks wasevaluated. A modeling study was conducted to determine airflow patterns in the headspaceof tank 241-C-I09, and to evaluate the amount of mixing and the local gas concentrationsthat could occur. Since the study revealed that the gases in the tank are well mixed andfollow Graham's law for gaseous diffusion, an analysis of a second tank was consideredunnecessary (Wood 1992). Studies completed since that time also confirm that conclusion(Claybrook and Wood 1994, Postma et al. 1994b).

*Trademark of Dragerwerk Aktiengesellschaft, Inc., Lubeck, Germany; also NationalDraeger, Inc., Pittsburgh, Pennsylvania.

**Trademark of Molectrics, Inc., Cleveland, Ohio.

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The need for continuous gas monitoring was addressed in a report that also assessed thepotential for cyclic venting and the possibility of accumulating flammable gases (Fowler andGraves 1994). The repon concluded that continuous flammable gas monitoring inferrocyanide tanks was not warranted based on (1) the low concentration of flammable gasesfound to date; (2) anticipated low ferrocyanide concentrations because of waste aging;(3) analytical results from tanks 241-C-I09 and C-112 showing that the fuel concentration inthe tanks is much lower than postulated by flowsheet values and operating records; and(4) calculations of hydrogen accumulation using realistic generation values and passiveventilation assumptions. Vapor sampling of all 18 ferrocyanide tanks has corroborated thatflammable gas concentrations in the ferrocyanide tanks are too low to be of concern. Nofurther activities are planned for this task.

• Progress During Reporting Period. This task is complete. DOE has concurredthat no continuous gas monitoring is required (O'Leary 1994).

3.4 FERROCYANIDE WASTE CHARACTERIZATION

"The program ofsampling the contents of these tanks should be greatly accelerated. Theproposed schedule whereby analysis of two core samples from each single-shell tank is to becompleted by September 1998 is seriously inadequate in light of the uncertainties as to safetyof these tanks. Furthermore, additional samples are required at several radii and at a rangeof elevations for the tanks containing substantial amounts offerrocyanide. "

Characterization of the wl;lste in the ferrocyanide tanks is necessary to (1) guide furtherchemical reaction studies with the ferrocyanide waste simulants, if necessary; (2) determineactual chemical and physical properties of the waste; (3) determine how the ferrocyanidewaste can be safely stored until retrieval and disposal actions are completed; and (4) applythe study results to the final remediation (exhumation and vitrification) of the waste. Thisinformation will be used to resolve the Ferrocyanide Safety Issue.

The important reactive materials that may be present in the ferrocyanide tanks are fuel(ferrocyanides, sulfides, and reduced carbon species such as organic complexants), oxidants(nitrates and nitrites), and inerts or diluents (including phosphates, aluminates, sulfates,carbonates, oxides, hydroxides, and most importantly water). The location of fissionproducts such as l37Cs and 90Sr is important because these products are heat sources andpotential source terms in postulated radiological releases from a hypothetical ferrocyanidereaction. The water content of the waste is very important because the high heat capacityand heat of vaporization of water make it an effective inerting material. Water can prevent asustained combustion or a propagating reaction if sufficient fuel is present; wet ferrocyanidematerial would require drying before it could react or propagate.

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3.4.1 Ferrocyanide Tank Waste Sampling and Analyses

Tank Sampling. Rotary-mode and push-mode sampling capabilities, auger surfacesampling, and grab sampling (primarily for liquids) are used to obtain waste samples fromthe Watch List tanks. Tanks without saltcake and with relatively soft waste solids can besampled by the push-mode method. If a hard saltcake or sludge layer is present,rotary-mode sampling is used. Auger sampling may also be used if the depth of waste isnominally less than 60 cm. Grab sampling is used for tanks containing supernatant and softsludge waste and has not been employed in the ferrocyanide tanks.

Each core consists of several 48-cm segments (or portions thereof) depending on the depth ofthe waste in the tank. The sludge layer in these cores is normally divided into four 12-cmsubsegments if a full 48-cm segment is obtained; otherwise the sample is subdivided into oneor more subsegments that are at least 12 cm in length. If the tank contains a saltcake layer,the saltcake segments are divided into only two subsegments. Segments that contain bothsludge and saltcak:e are divided such that the two types of waste are separated into separatesamples. Process flowsheet knowledge, tank historical data, and results obtained from testswith ferrocyanide sludge simulants are used to supplement the analytical results from coresampling.

The priority for sampling ferrocyanide tanks was changed to reflect the need to determine thereactive properties of the contents. In response to DNFSB Recommendation 93-5 to expeditesampling and analyses required to address safety issues in the Hanford Site Watch List tanks(DOE 1994a), the analysis plans for future ferrocyanide tank core samples (and the plans forother Watch List tanks) were revised. The Watch List tanks were given priority for coresampling, and the number of required analytes was reduced. Analyte selection was refocusedprimarily on safety-related properties. .

• Progress During Reporting Period. Analytical analyses were completed forferrocyanide tank 241-BY-I04, and the final laboratory report was issued onJune 25, 1996 (Benar 1996b). Results were tabulated in the previous quarterlyreport (Cash and Meacham 1996). Samples obtained met the requirementsspecified in the Ferrocyanide DQO document (Meacham et al. 1995). The45-day analytical report (Benar 1996a) was issued the previous quarter. TheTCR for this tank is scheduled for release next quarter.

Samples from the attempts to perform push-mode core sampling of tanks241-BY-I05 (riser 12A/core 108) and BY-106 (riser 5/core 121) continued to beanalyzed even though the sampling event did not meet the Ferrocyanide DQOrequirements. These two tanks were sampled during the fIrst quarter of FY 1996but no sludge segments were recovered because the downforce limit was reachedand sampling was stopped. The fInal analytical reports for tanks 241-BY-105and BY-106 will be issued next quarter. Since neither of these cores extended tothe sludge portion of the tank waste, no tabular results will be presented in thisreport. Some exotherms were detected, two of which exceeded the 480 Jig

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exceeded the 480 Jig notification limit. However, corresponding total organiccarbon (TOC) values were also significant (ranging from 0.07-0.19%) and totalcyanide values were very low (5-10 parts per million [ppm]).

The final analytical report was completed for 241-BY-1I0 on May 24, 1996(Schreiber 1996), and the TCR is now being prepared with a scheduled issuanceof August 1996. None of the samples obtained had mean exothermic reactions(on a dry weight basis) exceeding the Ferrocyanide DQO limit of 480 Jig. Thesamples that demonstrated some energetics were at least 25 percent water, whicheliminates the potential for a propagating reaction. In addition, the observedcyanide concentrations were well below the ferrocyanide DQO limit. Nickelconcentrations compared favorably with historical estimates and indicate thatferrocyanide has substantially decomposed.

• Planned Work For Subsequent Months. There are no present plans to applythe Ferrocyanide DQO (Meacham et al. 1995) to the unsampled ferrocyanidetanks presently on the Watch List; however some of these tanks will be sampledfor other issues as mentioned in Section 2.0. The ferrocyanide hazardassessment document has presented the case that further sampling of ferrocyanidetanks is not necessary.

The final analytical reports and TCRs for tanks 241-BY-I04, BY-105, BY-106and BY-lIO are scheduled to be issued next quarter.

• Problem Areas and Actions Taken. There are none, assuming the hazardassessment document, WHC-SD.,.WM-SARR-038, Revision 1(Meacham et al. 1996), is approved by DOE.

• Milestone Status.

December 31, 1995. Westinghouse Hanford Company obtains coresamples from five additional ferrocyanide tanks. Only one ferrocyanidetank, 241-BY-I04, was successfully sampled in November 1995. Attemptsto obtain pUSh-mode core samples from tanks 241-BY-I05 and BY-I06were discontinued when the downforce limit was reached for the drillstring. There are currently no plans to sample additional ferrocyanidetanks for resolving the Ferrocyanide Safety Issue. This milestone has beensuperseded by the final hazard assessment document(WHC-SD-WM-SARR-038, Revision 1), which was issued July 3, 1996(Meacham et al. 1996).

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March 31, 1996. Westinghouse Hanford Company completes datainterpretation reports, available for public release, for five ferrocyanidetanks. This milestone date was not met because of the delays encounteredin rotary-mode sampling of the tanks. Assuming the final hazardassessment document is accepted, completion of this milestone is notnecessary to resolve the Ferrocyanide Safety Issue. TCRs will be issuednext quarter for the four ferrocyanide tanks (241-BY-I04, BY-105,BY-1O,6, and BY-llO) most recently sampled.

July 31, 1996. Westinghouse Hanford Company obtains core samplesfrom the remaining ferrocyanide tanks. This milestone is not required forresolution of the Ferrocyanide Safety Issue, assuming the hazardassessment document is accepted.

October 31, 1996. Westinghouse Hanford Company completes datainterpretation reports, available for public release, for the remainingferrocyanide tanks. This milestone is not required for resolution of thesafety issue, assuming the hazard assessment document is accepted.

Infrared Spectroscopy Analyses. The collection of near-infrared (NIR) spectra fromarchived waste tank core samples, with various chemical matrices using a Fourier transforminfrared spectrometry (FTIR)-based fiber optics method, was completed in FY 1995.

Final reports summarizing IR work were issued at the end of FY 1995 (Rebagay et al. 1995,Reich et al. 1995, Douglas and Reich 1995).

• Status. This task was completed in FY 1995. No further work is planned inthis area in support of the Ferrocyanide Safety Program.

MOssbauer Spectroscopy. A small task on Mossbauer spectroscopy, previously supportedby the Ferrocyanide Safety Program, is investigating the physical and chemical nature of ironwithin tank waste. The National Aeronautics and Space Administration (NASA) hasdeveloped a miniaturized Mossbauer spectrometer that is small enough to perform elevationscans within the LOWs of the Hanford Site waste tanks. Iron is a major constituent offerrocyanide waste, and information about its location and composition in the tanks supportssafe interim storage and eventual retrieval of the waste. The Mossbauer program representsa cooperative venture between Westinghouse Hanford Company, DOE, and NASA. Thecontact at NASA is Dr. Richard Morris at the Johnson Space Center in Houston, Texas.

A decision was made in January 1996 to delete the scope of work in this task from theFerrocyanide Safety Program, and a financial change request was approved at that time.

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The task is continuing at the Hanford Site under a funding source different from theFerrocyanide Safety Program. Progress will no longer be reported in the quarterly reports.

• Status. Funding from the Ferrocyanide Safety Program for this task wasterminated in January 1996 when a financial change request was approved byWestinghouse Hanford Company and DOE-RL. The task was deleted from thescope of the Ferrocyanide Safety Program because completion of the effort is notrequired to resolve the Ferrocyanide Safety Issue (planned by the end ofFY 1996). The Mossbauer spectrometer task is continuing under a separatefunding source and no further progress will be reported in the ferrocyanidequarterly reports.

Scanning Electron Microscopy. Scanning electron microscopy (SEM) is a small task that isinvestigating the chemical and physical properties of waste stored in the Hanford Sitehigh-level waste tanks. Studies to further refine what is known about the chemical andphysical properties of ferrocyanide tank waste could continue if they were necessary forresolving the Ferrocyanide Safety Issue. However, it has been shown with confidence thatthe ferrocyanide concentration in the tanks has significantly degraded (aged) to the pointwhere the fuel value is much too low to support a propagating reaction. The task now is toprepare a final technical basis safety document that will resolve the Ferrocyanide Safety Issueby September 1996, so that the 18 tanks can be removed from the Watch List.

A decision was made in January 1996 to delete the scope of work in this task from theFerrocyanide Safety Program and a financial change request was approved at that time. Thetask is continuing at the Hanford Site under a funding source different from the FerrocyanideSafety Program. Progress will no longer be reported in the quarterly reports.

• Status. Funding from the Ferrocyanide Safety Program for this task wasterminated in January 1996 when a financial change request was approved byWHC and DOE-RL. The task was deleted from the scope of the FerrocyanideSafety Program because completion of the effort is not required to resolve theFerrocyanide Safety Issue (planned by the end of FY 1996). The SEM task iscontinuing under a separate funding source and further progress will not bereported in the ferrocyanide quarterly reports.

3.4.2 FSimation of Water Content

Methods for determining water concentrations in Hanford Site waste tanks are beingdeveloped using sample data analyses and state-of-the-art surveillance systems. This workwas originally sponsored by the Ferrocyanide Safety Program, but it was transferred to theOrganic Safety Program at the beginning of FY 1996. Two in situ moisture monitoringtechnologies are currently under development: neutron diffusion and electromagneticinduction (EMI). Initial development of NIR spectroscopy for determining the water contentof Hanford Site tank waste was completed in FY 1994 at the University of Washington

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Center for Process Analytical Chemistry (Reich et ale 1994), and by Westinghouse HanfordCompany in FY 1995 (Rebagayet ale 1995, Reichet ale 1995). A report examiningmoisture-monitoring technologies was completed in April 1993 (Meacham et ale 1993).

The water content of reactive waste can be an extremely important factor 'in ensuring thesafety of the Hanford Site tank waste. The water concentration within the waste willdetermine whether or not it will react and propagate. If sufficient water is present, achemical reaction cannot start. Recent work by Fauske and AssoCiates, Inc. (FAI) hasshown that as little as 5 wt% unbound water in a stoichiometric reactive mixture will preventthe mixture from igniting and burning when a significant ignition source is applied(Fauske 1996). Water may become the prime safety factor for the organic waste tanks toensure that the waste is stored safely. For the ferrocyanide tanks it has been shown that theferrocyanide content is insufficient for the waste to propagate, so the presence of waterbecomes a second safety barrier ensuring that the tanks are safe.

Neutron Diffusion. Well-logging techniques, coupled with computer modeling, weredeveloped and applied to an existing neutron probe to determine information about the waterconcentrations, material interfaces, and other waste characterIstics in the ferrocyanide tanks.Using the knowledge gained from computer modeling, in situ measurements, andexperimental calibration data with the current in-tank liquid level neutron probe(Watson 1993), prototype moisture measurement neutron probes were developed. Thissystem consists of three neutron probes: a near-field thermal neutron probe, a far-fieldthermal neutron probe, and a far-field epithermal neutron probe. This improved systemwould primarily be used to determine the axial moisture concentration profile within theferrocyanide tanks.

Moisture measurement using neutron diffusion is an established technology. The techniqueuses a neutron source and one or more neutron detectors. The thermal neutrons reaching adetector originate as fast neutrons from the source and are slowed or absorbed by themedium. Because hydrogen atoms are effective at slowing down neutrons, the detectorresponse is a strong function of the surrounding moisture concentration.

Two methods are generally used in the measurement of moisture concentration around wellsusing neutron diffusion. The 'first method, the moisture gauge, has a short source-to-detectorspacing on the order of 0 to 10 cm (near-field). The response of a moisture gauge ischaracterized by an increase in detector response with increasing moisture concentration ofthe surrounding medium. The second method, the neutron log, often has two detectors withlonger source-to-detector spacings on the order of 20 to 50 em (far-field). The detectors in aneutron log arrangement exhibit a decreased response to increased moisture concentrations.The detector placed at the shorter spacing is used to correct the response of the longer-spaceddetector for borehole effects.

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Tank moisture measurements are taken from within LOWs. The LOWs are permanentlyinstalled sealed pipes that extend from the riser top through the tank waste to near the tankbottom. The LOWs allo", axial information about the surrounding waste materials to beobtained using certain detectors.

The initial design and prototype tests were completed for a new surface moisturemeasurement neutron probe in FY 1995, and results and progress on this task were reportedin Watson (1993), Finfrock et al. (1994), and (Lipke 1995). This effort was transferred tothe Organic Safety Program, and no additional development work will be conducted for theFerrocyanide Safety Program.

• Status. This task was transferred to the Organic Safety Program at the end ofFY 1995, and progress on this ongoing task will no longer be reported in theferrocyanide quarterly reports.

Electromagnetic Induction Probe. The purpose of this task is to deploy the EMI probe inthe LOWs or on top of the waste surface, to measure moisture concentration. EMI probesoperate by creating a magnetic field that induces current in a'conductive medium. Thisinduced current can be measured and is related to the media conductivity. The higher theelectrical conductivity, the higher the free moisture content in the tank waste.

The EMI probe is designed with four separate coils of wire that can be either exciting coilsor sensing coils. The present configuration uses one coil as the exciting coil and three coilsas the sensing coils. This configuration allows three different depths of penetration duringone scan. The electronics can be programmed to lise four frequencies during one scan, sothe information acquired will be four frequencies at three different coil spacings. Thisinformation will be useful in separating the environment near the LOW from the environmentfar from the LOW. Two different EMI probes have been built, with different coil spacingand turns per coil, to determine in-tank responses.

EMI probes were deployed in tanks 241-BY-I04, BY-106, BY-107, BY-llI, BY-112,TY-I03, TX-1l8, TX-1l4 (3 LOWs), 8-105, and 8-106. Observations of the in-tankacquired data allowed some conclusions about EM! to be made: (1) the system is sensitive toloss of hydraulic conductivity, which occurs at approximately 0.08 to 0.12 volume fractionof liquid (depending on porosity); (2) the scan can interrogate multiple depthssimultaneously; (3) EM! is sensitive to small changes in material properties; (4) the EM!method measures conductivity directly, while moisture interpretation requires someassumptions; (5) EM! results are affected by temperature, so compensation is required; and(6) the EM! method is strongly affected by ferromagnetic items. Reports have been issuedon this work (Crowe and Wittekind 1995, Wittekind and Crowe 1996). The remainingdevelopment effort was transferred to the Organic Safety Program at the end of FY 1995.

• Status. This task was transferred to the Organic Safety Program at the end ofFY 1995, and progress on this ongoing task will no longer be reported in theferrocyanide quarterly reports.

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3.4.3 Moisture Retention Properties of Ferrocyanide Sludge and Saltcake Simulants

The water content of ferr~yanide sludge, if sufficient, will prevent exothermicferrocyanide/nitrate-nitrite reactions. Studies were completed to evaluate the water retentionproperties of ferrocyanide tank sludge and saltcake simulants as they relate to possible wastetank leaks, tank stabilization by pumping, and possible evaporation from exposed surfaces.Previous work has shown that ferrocyanide sludge cannot dry sufficiently to be chemicallyreactive during interim storage, either globally or locally (Epstein et al. 1994). Dryoutmechanisms evaluated included global evaporation, removal of liquid by leakage or pumping,boiling as a result of hot spots, and enhanced surface evaporation from hot spots. Recentwork focused on water retention in saltcake material, especially after a tank has beeninterim-stabilized. This work was supported by the Ferrocyanide Safety Program until theend of FY 1995, but was transferred to the Organic Safety Program at the beginning ofFY 1996.

Modeling calculations were performed to estimate the water-retaining capability offerrocyanide waste in typical Hanford Site tank systems. The effort focused on evaluatingthe impact of consolidation and surface evaporation processes. Computer models were usedto estimate retention of water within the matrix and to determine surface drying of sludgeand saltcake waste. To accomplish these objectives, the hydraulic properties of actualsludges and saltcake porous media were compared with tested waste simulants, and theirphysical properties were correlated.

Modeling was also performed to examine the resistance of saltcake waste to gravity drainageand surface evaporation. Under the influence of gravity, saturated saltcake will drain whenliquid is pumped out and when a tank is stabilized. In contrast, sludge does not readily drainand the interstitial liquid must be expelled by consolidation, usually caused by anoverburden. Because saltcake drains when stabilized, it is more subject to potential drying atthe surface as a result of water evaporation.

• Status. Modeling of the water retention properties of saltcake and sludge wastewas completed and documented in September 1995 (Simmons 1995). Waterretention modeling for the Ferrocyanide Safety Program has been completed.However, additional saltcake modeling continues for the Organic SafetyProgram.

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3.5 CHEMICAL REACTION STUDIES

"The schedule for the proJ5ram on study of the chemical properties and explosive behavior ofthe waste in these tanks is indefinite and does not reflect the urgent need for a comprehensiveand definitive assessment of the probability of a violent chemical reaction. The study should

.be extended to other metallic compounds offe"ocyanide that are known or believed to bepresent in the tanks, so that conclusions can be generalized as to the range of temperatureand other properties needed for a rapid chemical reaction with sodium nitrate. "

Chemical reaction studies on ferrocyanide waste simulantshave been conducted byWestinghouse Hanford Company, FAI, PNNL, and Los Alamos National Laboratory(LANL). Only the PNNL program was on-going during this quarter; all the other programshave been completed. Both Westinghouse Hanford Company and PNNL have producedflowsheet simulant materials for testing and characterization. Earlier, FAI conductedadiabatic calorimetry and propagation tests on these same flowsheet materials and onstoichiometric mixtures of pure sodium nickel ferrocyanide and sodium nitrate/nitrite. Thetest program at LANL evaluated the sensitivity of ferrocyanide reactions to shock, friction,and thermal aging (Cady 1993) and was completed in FY 1993.

3.5.1 Chemical Reaction Studies at Pacific Northwest National Laboratory

Chemical reaction studies are nearing completion at PNNL using flowsheet simulantmaterials. Waste studies addressing DNFSB Recommendation 90-7.5 have been conducted todetermine the following: (1) aging effects (hydrolysis and radiolysis) from more than 35 yrof storage in the tanks; (2) reaction kinetics and properties of various mixtures offerrocyanide with sodium nitrate and/or sodium nitrite; (3) comparison of waste simulant andactual waste properties; and (4) modeling calculations to predict the moisture-retainingcapability of ferrocyanide waste in a typical tank system. All of these tasks are completeexcept for the aging effects studies.

• Progress During Reporting Period.

Aging Studies. Experiments to test the reproducibility of aging results werecompleted this quarter. In the reproducibility experiments, vessel/gamma accesstube combinations were systematically varied to investigate the effects of vessel,gamma access tube, and sample preparation and analysis techniques.Experiments were all conducted with the In-Farm waste simulant in 2 M NaOHat 90 °C and 1 x HY rad/h for 12 d, except for controls that were not irradiated.These conditions duplicate conditions for Experiment H-1, the first agingexperiment. Ammonia production data for Experiment H-1 and thereproducibility experiments are shown in Figure 3-1. The concentrations plottedare those observed in solution and do not take into account the amount ofammonia lost to radiolysis. Also shown are the least squares regression fit,assuming zero-order ammonia production, and the 95 % confidence limits.

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Figure 3-1. Ammonia Production and Reproducibility in the Hydrolysis of In-Parm-lBSimulant in 25 mL of 2 M NaOH at 90°C and 1 x 1()5 rad/h.

I

15

0.08

7il 0.06Q) .(5

E 0.04........('II")

:::cz 0.02-

oo 5 10

Time, days

•

20

- - 95% ConfidenceA Duplicates

- Regression

• Hi Control

• Hi, Gamma

" Dup. Control

The data have a percent-relative standard deviation of 8%. The data show that,within the experimental error, the zero-order approximation adequately describesthe global aging process, up to at least the approximately 80% aging thatoccurred in Experiment H-l. The results of the reproducibility experiments alsoshow that there was very little error associated with sample preparation andanalysis. More error was introduced when different vessels were used in thesame gamma tube than when the same vessel was used in different gamma tubes.

The relative sensitivity to vessel likely arises from slight differences intemperature control rather than variations in gamma dose rate or samplepreparation and analysis.

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Atomic absorption (AA) analyses of reaction solutions aged under a variety oftemperature and gamma dose rate conditions showed that both soluble iron andnickel species were present. FTIR was used to identify the soluble iron asFe(CN)t and soluble nickel as Ni(CN)i Concentrations detemiined by FfIRwere nearly identical to the concentrations from AA, showing that essentially allof the soluble iron and nickel were present as the cyano complexes.Quantification of these cyano species allowed a determination of the approximatecyanide balance. The sum of the moles of cyanide bound to nickel and ironusing FTIR results, combined with the moles of ammonia measured, accounts forthe starting cyanide (percent cyanide that was found ranges from 89-109 %) forthe 11 samples analyzed (see Table 3-1). The amount of ammonia destroyed byradio1ysis is not included in these calculations. The good mass balance showsthat ammonia is an appropriate indicator of the extent of aging.

The fmal Aging Studies report was completed this quarter (Lilga et al. 1996).The report summarizes work on the Aging Studies Task from FY 1992 toFY 1996. Extensive experiments were conducted to determine how aging isaffected by pH, dose rate, and temperature.

The experiments showed that the rate of thermal ferrocyanide aging does notincrease at higher pH when the pH exceeds nine (Lilga et al. 1996). Theprecipitation of sodium nickel ferrocyanide was done at slightly alkalineconditions (pH = 8.0 - 10). However, the ferrocyanide tanks were used for avariety of waste management operations that exposed the tanks to alkaline waste(Anderson 1990). Review of the available historical pH and hydroxide datacollected for the ferrocyanide tanks shows that all the tanks had pH valuesgreater than nine (Wodrich et al. 1992). Consequently, waste pH was not alimiting factor for ferrocyanide waste aging in Hanford Site tanks.

The results of experiments at various dose rates (0 to lOS rad/h) were revealingsince the rate of aging is only noticeably affected at the highest dose rate(lOS rad/h). There was little impact from dose rate observed for dose ratesbetween 0 and 1,000 rad/h; all the points essentially fall on the same curve.Dose rates in the ferrocyanide waste tanks were calculated to be in the1,000 rad/h range, and none approached 10,000 rad/h (parra 1994).Consequently, dose rates in the ferrocyanide tanks had only a second order effecton the rate of aging.

Experiments on waste simulants show that the rate of aging was strongly affectedby temperature (Lilga et al. 1996). As shown in Table 3-2, the rate of agingincreased dramatically with increasing temperature. The experiments show thatthe extent of ferrocyanide aging in Hanford Site tanks was primarily determinedby the individual tank temperature histories.

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Table 3-1. Cyanide Mass Balance.

Sample Total [NH3] [Fe(CN)~] [Ni(CN)42] Total %

Number [CN-] mollL moUL mollL [CN-] FoundPresent FoundmollL mollL

Hl-C2 0.0996 0.0150 0.0154 0.0 0.1074 108

HI-54 0.0996 0.0410 0.0385 0.00850 0.0981 99

HI-56 0.0996 0.0684 0.0104 0.0212 0.1000 100

H4-C2 0.0996 0.0110 0.0160 0.0 0.1070 107

H4-S6 0.0996 0.0383 0.00605 0.00806 0.1068 107

HS-C2 0.0996 0.00910 0.0165 0.0 0.1081 109

HS-S5 0.0996 0.0152 0.0132 0.00210 0.1028 103

HlO-C1 0.0960 0.00087 0.0155 0.0 0.0939 98

H10-56 0.0960 0.0205 0.00390 0.00970 0.0827 86

Hll-C2 0.1032 0.0413 0.0114 0.0 0.1097 106

Hll-S2a 0.1032 0.0375 0.00557 0.00716 0.0995 96

Table 3-2. Aging Rates as a Function of Temperaturefor Waste Simulant Experiments.

Temperature Reaction Rate°C (OF) g N~NiFe(CN)J1oo g dry solids/yr

40 (104) 0.04

50 (122) 0.19

60 (140) 0.90

70 (158) 3.9

80 (176) 15.5

90 (194) 57

• Status. All work is complete for this task and DNFSB Recommendation 90-7.5is closed.

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3.5.2 Preparation and Characterization of Ferrocyanide Simulants

Earlier in the Ferrocyanid~ Safety Program, various ferrocyanide waste simulants wereprepared and analyzed to determine their chemical reaction properties as a functiontemperature and water present in the mixture. Other tests were conducted with pure sodiumnickel ferrocyanide, a stoichiometric amount of oxidizer (sodium nitrate/nitrite), and water.These latter. tests were conducted by FAI to defme the margin of safety between thetheoretical and experimental propagation limits for ferrocyanide. These tests are run in theFA! reactive systems screening tool. These tests and previous tests with simulants (alongwith analyses of actual tank waste samples, waste tank monitoring,· and waste modeling),provide information to characterize with a large degree of conservatism the safety concernsrelating to the ferrocyanide sludge originally added to 18 of the Hanford Site waste tanks.

• Status. A financial change request was approved the previous quarter thatdeleted further chemical reactivity work at FAI on the Ferrocyanide Safety Issue.Further work is not required because previous chemical reaction studies andresults obtained by sampling nine of the ferrocyanide tanks show that the fuelvalue of ferrocyanide has degraded (aged) to levels too low to be of concern.No further work is planned in this area.

• Milestone Status.

September 30, 1996. Complete FAI support for Ferrocyanide. Safety Issueresolution and conclude chemical reactivity studies of chemical waste.This milestone was deleted by the financial change request approved lastquarter.

3.6 EMERGENCY RESPONSE PLANNING

"The Board had recommended (that an action plan be developed for the measures to be takento neutralize the conditions that may be signaled by alarms.' Two types ofmeasures areimplied: actions to respond to unexpected degradation ofa tank or its contents, and actionsto be taken if an explosion were to occur. Your implementation plan stated that (the currentcontingency plans ... will be reviewed and revised ifneeded.' We do not consider that thisproposed implementation of the Board's recommendation is adequately responsive. It isrecommended that a written action plan founded on demonstrated principles be prepared assoon as possible, that would respond to indications ofonset ofabnormal temperatures orother unusual conditions in a ferrocyanide-bearing tank, to counter any perceived growth inhazard. A separate emergency plan should be formulated and instituted, covering measuresthat would be taken in event ofan explosion or other event leading to an airborne release ofradioactive material from the tanks, and that would protect personnel both on and off theHanford Site. The Board believes that even though it is considered that the probability issmall that such an event will occur, prudence dictates that steps be taken at this time toprepare the means to mitigate the unacceptable results that could ensue. II

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WHC-EP-0474-21

The original Action Plan for Response to Abnormal Conditions in Hanford Radioactive WasteTanks Containing Ferrocyanide (Cash and Thurman 1991) was prepared in response toDNFSB Recommendation 90-7.6. The·plan describes the steps to be taken if atemperature-increase trend above the tank temperature baseline is measured in any of theferrocyanide tanks. The document was revised to include the monitoring criteria andresponses for abnormal levels of flammable and toxic gases, as well as the reportingrequirements, if established criteria are exceeded (Cash and Thurman 1992). The secondrevision of the plan was released in June 1994 (Fowler 1994).

The Tank Farm Stabilization Plan For Emergency Response, WHC-SD-PRP-TI-OOl,Revision 0 (WHC 1991) was issued in March 1991. If a radioactive release from aferrocyanide tank were to occur, it would be detected by one or more radiation monitoringsystems. Significant airborne or ground surface releases that spread beyond the immediatetank or tank farm would be detected by the tank farm area radiation detectors. Thesemonitoring systems are on all tank. farms. An emergency involving an undergroundradioactive waste storage tank is a unique event with potentially serious consequences bothonsite and offsite. The stabilization plan provides quick, preplanned actions that can be usedto stabilize an emergency event at an underground radioactive waste storage tank.

All actions with respect to emergency planning, emergency event recognition, protectiveaction recommendations, and emergency response procedures have been completed. Furtherrevisions and occasional validation exercises will be accomplished as part of the normalWestinghouse Hanford Company and DOE emergency planning efforts. No further reportingon these issues is planned, and this part of DNFSB Recommendation 90-7.6 is consideredcomplete and closed.

DOE considers this recommendation to be closed with the provisos that the abnormalconditions response plan and emergency plans are reviewed on a periodic basis and revisedand updated as required to incorporate any additional controls determined appropriate by theongoing Waste Tank Safety Program investigations. The Action Plan for Response toAbnormal Conditions in Hanford Site Radioactive Waste Tanks Containing Ferrocyanide wasupdated and released in June 1994, (Fowler 1994); and validation exercises for various wastetank accident scenarios are conducted periodically (exercises for the tank farms are conductedevery two years).

• Status. As noted in previous reports, all of the planned milestones for this taskhave been completed.

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4.0 IMPLEMENTATION OF THE WYDEN AMENDMENT

The Wyden Amendment (Public Law 101-510, 1990) requires that:

"... the Secretary of Energy shall identify which single-shelled or double-shelled high-levelnuclear waste tanks at the Hariford Nuclear Reservation, Richland, Washington, may have aserious potential for release ofhigh-level waste due to uncontrolled increases of temperatureor pressure. After completing such identification, the Secretary shall determine whethercontinuous monitoring is being carried out to detect a release or excessive temperature orpressure at each tank so identified. Ifsuch monitoring is not being carried out, as soon aspracticable the Secretary shall install such monitoring, but only if a type ofmonitoring thatdoes not itself increase the danger ofa release can be installed. "

4.1 TIlE WATCH LIST

In March 1989, using process knowledge, process records, transfer records, and log books,Westinghouse Hanford Company identified 22 Hanford Site tanks as potentially containing1,000 g-mol (211 kg or 465 lb) or more of ferrocyanide as the Fe(CN)~ anion (Nguyen1989). To avert possible injury to personnel and damage to the facility or environment,strict controls were identified for these and other tanks with safety issues. These controlswere described in Operating Specifications for Watch List Tanks, OSD-T-151-00030,Revision 0 (WHC 1990). Tanks identified by this document have been commonly referred toas Watch List tanks (see WHC 1996 for latest revision). Two additional ferrocyanide tankswere identified in January 1991 (Borsheim and Cash 1991), increasing the total number offerrocyanide tanks to 24.

In November 1990, the Wyden Amendment (public Law 101-510, 1990) was enacted. Thislaw required the identification of Hanford Site tanks that may have a serious potential forrelease of high-level waste. In February 1991, the 24 ferrocyanide tanks were among thetanks identified (Harmon 1991), and were included in the subsequent July 1991 report toCongress that responded to the Wyden Amendment (Watkins 1991). However,re-examination of the historical records indicated that six of the 24 tanks did not contain therequisite 1,000 g-mol of ferrocyanide (Borsheim and Simpson 1991). Therefore, these sixtanks should not have been included on the Watch List or been identified in the response tothe Wyden Amendment. The six tanks were subsequently removed from the Watch List(Anttonen 1993, Sheridan 1994b). Since these tanks do not contain greater than 8 wt%Na2NiFe(CN)6' they should not be on the Watch List for this reason also.

As part of the overall safety screening module being conducted by Westinghouse HanfordCompany Tank Waste Remediation System, all of the Hanford Site SSTs will becore-sampled and characterized. Fourteen ferrocyanide tanks are currently on the WatchList, and no additional ferrocyanide tanks are expected to be added to the Watch List.

4-1

WHC-EP-0474-21

Work conducted since 1991 on ferrocyanide reactions has resulted in a change of thecriterion used for placing ferrocyanide tanks on the Watch List. The 1,000 g-mo1 inventorycriterion has now been reylaced with a. fuel concentration criterion of 115 callg of dry sample(this is an energy equivalent to a concentration of 8 wt% N~NiFe(CN)6 in the waste). Thisfuel concentration criterion more accurately reflects the risk associated with ferrocyanidetanks. Ferrocyanide tanks with concentrations less than an energy equivalent of 8 wt%Na2NiFe(CN)6 cannot support a propagating reaction, and are categorized as safe. Detailedrationale for the 115 cal/g of dry fuel concentration criterion is presented in FerrocyanideSqfety Program: Safety Criteria for Ferrocyanide Watch list Tanks, WHC-EP-0691(postma et al. 1994).

Core sampling and characterization efforts will determine the ferrocyanide concentration forthose tanks that bound aging (see Sections 2.2 and 3.4). After adequate characterization, ifthese tanks contain concentrations less than 8 wt% NazNiFe(CN)6 (Le., the fuel value of themaximum concentration is less than 115 cal/g), then a request will be made by WestinghouseHanford Company for DOE concurrence to remove all of the ferrocyanide tanks from theWatch List.

Since some sample bias and analytical error are unavoidable, confidence intervals have beenestablished to specify when it is appropriate to conclude that a ferrocyanide tank containsconcentrations less than an energy equivalent of 8 wt% NazNiFe(CN)6' An 80% confidenceinterval was chosen for tanks with a fuel concentration of 8 wt% N~NiFe(CN)6' That is, iffive ferrocyanide tanks contain exactly an energy equivalent of 8 wt% N~NiFe(CN)6'

statistically, four tanks would remain on the Watch List and one tank would be removed.The possibility of removing a ferrocyanide tank from the Watch List decreases substantiallyas the fuel concentration increases. The confidence intervals increase to 95% and 99% atNa2NiFe(CN)6 concentrations of 12 % and 15 wt%, respectively. Detailed discussions onhow sample bias and analytical error are factored into determining the actual fuelconcentrations in a ferrocyanide tank are given in the Ferrocyanide DQO(Meacham et al. 1995).

• Planned Work To Complete Program. DOE-RL has approved removal of thefour C-Farm ferrocyanide tanks from the Watch List. Documentation is beingidentified to make the change and the required actions will be transmitted toDOE-RL. As indicated earlier, submittal of the final technical basis safetydocument to DOE-RL on July 3, 1996, has provided the basis for and resolutionof the Ferrocyanide Safety Issue (Meacham et al. 1996) and removal of the final14 ferrocyanide tanks from the Watch List.

Work on the Ferrocyanide Safety Program is continuing to draw to a rapid closeand sampling of additional tanks is not necessary to resolve the safety issue.A fmal report on the aging test program at PNNL was completed. All six partsof DNFSB Recommendation 90-7 have been adequately addressed, and inMarch 1996 a letter was transmitted to the Chairman of the DNFSB by DOEHeadquarters, that requested closure of the recommendation (Guimond 1996).

4-2

WHC-EP-0474-21

• Milestones.

January 31, 1996. Westinghouse Hanford Company issues documentationsupporting safety issue resolution for the four C-Farm tanks andrecommends their removal from the Wyden Amendment Watch List(Public Law 101-510, 1990). The Assessment o/the Potential/orFerrocyanide Propagating Reaction Accidents, WHC-SD-WM-SARR-038,Revision 0, was transmitted to DOE-RL as scheduled (Bacon 1996a,Grigsby et al. 1996a). All four C-Farm tanks were sampled earlier anddata interpretation reports were completed for these tanks.

The report was revised to incorporate informal comments received fromDOE-RL and reissued with the same title as WHC-SD-WM-SARR-038,Revision OA, (Grigsby et al. 1996b). The revised report was transmittedto DOE-RL on March 19, 1996, with a letter requesting that the fourC-Farm tanks be removed from the Watch List (Bacon 1996b). The reportwas subsequently forwarded to the DNFSB Staff on AprillO, 1996 .(Trine 1996).

July 31, 1996. Westinghouse Hanford Company receives DOE approvalto remove the four C-Farm ferrocyanide tanks from the Watch List.Approval was received from DOE-RL on June 25, 1996 to remove thesetanks from the Watch List.

March 31, 1997. Westinghouse Hanford Company preparesdocumentation to support removal of the last 14 ferrocyanide tanks fromthe Watch List and recommends final resolution of the Ferrocyanide SafetyIssue. This milestone was accelerated to July 3, 1996, and the fmal safetydocument, WHC-SD-WM-SARR-038, Revision 1, (Meacham et al. 1996)was transmitted to DOE-RL on July 3, 1996 (Bacon 1996c).

September 30, 1997. Westinghouse Hanford Company receives DOEapproval to remove the remaining 14 ferrocyanide tanks from the WatchList and to declare the Ferrocyanide Safety Issue resolved. This actionwill complete the Ferrocyanide Safety Program. DOE-RL expects tocomplete this action by September 30, 1996.

4.2 TEMPERATURE MONITORING

The installation of temperature monitoring capabilities is discussed in Sections 3.1.2.1 and3.2.2. Installation of instrument trees and continuous temperature monitoring are consideredprudent waste management practices. Therefore, new instrument trees will be installed in

4-3

WHC-EP-0474-21

ferrocyanide tanks, even though the ferrocyanide waste has aged and little fuel valueremains. Instrument trees have been installed in all ferrocyanide tanks and are continuouslymonitored by TMACS. .

• Status. This task is complete.

4.3 PRESSURE MONITORING

The ferrocyanide tanks were initially identified as having "a serious potential for release" andwere placed on the Watch List because insufficient data were available on the probability forferrocyanide-nitrate/nitrite reactions. Pressure monitoring instrumentation is not presentlyinstalled on the ferrocyanide tanks. It would take several years to install pressure monitoringinstrumentation because of the capital project time cycle. Ferrocyanide waste has probablydegraded (aged) significantly, and all of the tanks may now contain less than the 8 wt%NC\:lNiFe(CN)6 fuel concentration specified for the safe category (postma et al. 1994a). Thiseliminates the need for continuous pressure monitoring for offgases from a ferrocyanidereaction.

The rationale for not installing pressure monitors in ferrocyanide tanks was prepared andsubmitted to DOE in July 1994 (payne 1994a). Low gas generation rates (Fowler andGraves 1994) and the low potential for exothermic ferrocyanide reactions(postma et al. 1994a) indicated that continuous pressure monitoring is not warranted.

• Planned Work For Subsequent Months. No additional work is planned in thisarea, because DOE has concurred that pressure monitoring is not required asstated in the revised Ferrocyanide Safety Issue Program Plan (O'Leary 1994).

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WHC-EP-0474-21

5.0 PROGRAM SCHEDULES AND MILESTONES

Schedules are presented in this section (see Figure 5-1). The schedules review milestones forFY 1994, through the expected end of the program in FY 1997. The sequence andanticipated completion dates of the major milestones leading to resolution of the FerrocyanideSafety Issue are presented. Closure of DNFSB recommendations are indicated on theschedule as diamonds, and completion of interim milestones are indicated as triangles. Theschedules are statusedthrough June 30, 1996.

5-1

Ferrocyanide Waste Tank Safety Program Schedule

o""'"N'-"

'..., "T1: DOE Approval to ~.

Remove Remaining Tanks (l)

From Watch List VI, I-I I t

: : : : I

, ,Recomend Safe~ ,: Issue Resolution, ' roE Approval to ReCorMnd ~afetY

: ,,~r C Fil T;n!s; ~e~o~~=~~Li:~kS:F:::~:~~~~~:sInstall Trees in All , , "'" • , ,

~e":ocranid! T~n~ (T~A):

I I : :! t I :

! ! I

, ,,,,,, ,, ,, ,, ,, ,,,,,,,

,,,,,,, ,

Connection of Ne"; 1Ferrocyanide Instrument ,Trees to TMACs (TPA)

Initial Installation ofMoisture Monitoring

7qUiP~nt, I, In-Tank: Demonstration"

" of EMI

, VaPor Sample'AII: Ferrocyanide Tanks: (TPA)

,,,

,,,

.,oecision on Need for:,C~nng,S~st~m,

Temperature Criteria: Report (TPA) :

,,,,,

,,,,,,,,,

: ~,,,,,,,,,, ,

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I I I I I II I I I I II I I I I,

Neutron Probe

Activities

EMI

Resolution of Safety Issue(Section 2.0)

Install Thermocouple Trees(Sections 3.1.1)

Continuous Gas Monitoring(Section 3.3.2)

Install ContinuousTemperature Monitoring(Section 3.2)

Cooling SystemRequirements

Gas Monitoring(Section 3.3.1)

Estimation of WasteMoisture Content(Section 3.1.2)

'\l Interim MilestonesoClosure 01 DNFSB MilestonesJune 30, 1996

29504077.1 Rev. Date 6130196

Ferrocyanide Waste Tank Safety Program Schedule

Activities

I,,I, I

: :,: Core sample: 4Tanks"

, Core sample ': , I Core lampf8 : i :: ,:,, . +5T!"k\ ; ; , : ; : ;e;'~i~O~n~ntirp~t~ti~n:. I I I :

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t f I , t I I I I I

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: :: ::::: FReport :I I I I I I'I I I I I I I I II I I I 1 I I I I I

:::::,::: Report:I f I I I f I I t I II I t I I \ I I I I tI I I I I I I i I I I I I

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; : ; : i : ; ! i "RePort :I I It. t I I II I • I I 1 I I I II I I I j I j I I I I It I • It. I' I II I I 1 I • I. I I I I

: : : : lpr~p~g~ti~n~.: : : ::: I: Conditions : :

I t::Re,p0rt: ::::! I f I I I f I I I I I II I I I f I I Iff I I II I' I I I I I I I

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I I tit I I I t I I I II I I I I \ I I I I I I II I 1 I 1 I I I I I

I l " 1 I t I I II I I t I I I I I I I I ,I I I I I t I I I ! I I II I I I I I 1 I I

Solubility Studies

Aging Studies

Cyanide Speciation

Comparison of Waste

Tank Pressure Monitoring(Section 4.3)

FAI Studies(Section 3.5.2)

Waste Simulants(Section 3.4.2)

PNNl Studies

Core Sampling(Section 3.4.1)

Waste Analysis UsingInfrared Spectroscopy(Section 3.4.3)

VI,w

c--···'"

,!';~,i,•

V Interim MilestonesoClosure of DNFSB Milestones

June 30, 199629504077.2 Rev. Date 6130/96

WHC-EP-0474-21

This page intentionally left blank.

5-4

WHC-EP-0474-21

6.0 REFERENCES

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

Anttonen, J. H., 1993, Resolution of Unreviewed Safety Question (USQ) for FourFerrocyanide Tanks, (letter 9304645B/93-CAB-223 to T. M. Anderson, President,Westinghouse Hanford Company, July 9), U.S. Department of Energy, Richland.Operations Office, Richland, Washington.

Bacon, R. F., 1996a, Ferrocyanide Safety Program: Request for Removal of14Ferrocyanide Tanks from the Watch List and Resolution of the Ferrocyanide SafetyIssue, (letter 9652982 to J. E. Kinzer, DOE-RL, July 3), Westinghouse HanfordCompany, Richland, Washington.

Bacon, R. F., 1996b, Ferrocyanide Safety Program: Request for Resolution of theFerrocyanide Safety Issue and Deletion from the Watch List for Four C-Farm Tanks,(letter 9651198 to J. E. Kinzer, DOE-RL, March 19), Westinghouse HanfordCompany, Richland, Washington.

Bacon, R. F., 1996c, Ferrocyanide Safety Program: Request for Removal of14 Ferrocyanide Tanks from the Watch List and Resolution of the Ferrocyanide SafetyIssue, (letter 9652982 to J. W. Kinzer, DOE-RL, July 3), Westinghouse HanfordCompany, Richland, Washington.

Benar, C. J., 1996a, 45-Day Safety Screening Results for Tank 241-BY-I04, Rotary Mode{in Push Mode] Cores 116 and 117, WHC-SD-WM-DP-l64, Rev. 0, WestinghouseHanford Company, Richland, Washington.

Benar, C. J., 1996b, Final Reportfor Tank 241-BY-I04, Rotary Mode Cores {in Push Mode]116 and 117, WHC-SD-WM-DP-I64, Rev. 1, Westinghouse Hanford Company,Richland, Washington.

Borsheim, G. L., and R. J. Cash, 1991, Unusual Occurrence - Addition of Two Tanks to Listof Unreviewed Safety Question Tanks Containing Ferrocyanide,WHC-91-0096-TFARM, February 13, Westinghouse Hanford Company, Richland,Washington.

Borsheim, G. L., and B. C. Simpson, 1991, An Assessment of the Inventories ofFerrocyanide Watch List Tanks, WHC-SD-WM-EP-133, Rev. 0, WestinghouseHanford Company, Richland, Washington.

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WHC-EP-0474-21

Bussell, J. H., 1992, Engineering Evaluation of Thermocouples in Ferrocyanide Watch ListTanks, WHC-SD-WM-ER-134, Rev. 0 and Rev. OA, Westinghouse Hanford Company,Richland, Washington.

Cady, H. H., 1993, Evaluation ofFerrocyanidelNitrate Explosive Hazard, LA-12589-MS,Los Alamos National Laboratory, Los Alamos, New Mexico.

Cash, R. I., 1991, Implementation Plan for the Defense Nuclear Facilities Safety BoardRecommendation 90-7, WHC-EP-0415, Rev. 0, Westinghouse Hanford Company,Richland, Washington.

Cash, R. J., and J. E. Meacham, 1996, Quarterly Report on the Ferrocyanide SafetyProgram for the Period Ending March 31, 1996, WHC-EP-0474-20, WestinghouseHanford Company, Richland, Washington.

Cash, R. I., and I. M. Thurman, 1991, Action Plan for Response to Ab1Wrmal Conditions inHanford Site Radioactive Waste Tanks Containing Ferrocyanide, EP-0407, Rev. 0,Westinghouse Hanford Company, Richland, Washington.

Cash, R. J., and J. M. Thurman, 1992, Action Plan for Response to Ab1Wrmal Conditions inHanford Site Radioactive Waste Tanks Containing Ferrocyanide, EP-0407, Rev. 1,Westinghouse Hanford Company, Richland, Washington.

Claybrook, S. W., and S. A. Wood, 1994, Organic Evaporation in Waste Tank C-103,WHC-SD-WM-ER-344, Rev. 0, Westinghouse Hanford Company, Richland,Washington.

Crowe, R. D., M. Kummerer, and A. K. Postma, 1993, Estimation ofHeat Load in WasteTanks Using Average Vapor Space Temperatures, WHC-EP-0709, Rev. 0,Westinghouse Hanford Company, Richland, Washington.

Crowe, R. D., and W. D. Wittekind, 1995, Ferrocyanide Safety Program: In-TankApplication ofElectromagnetic Induction (EM!) Moisture Measurements - FY 1995Report, WHC-SD-WM-ER-520, Rev. 0, Westinghouse Hanford Company, Richland,Washington.

Deaton, D. E., 1990, Unusual Occurrence - Unreviewed Safety Questions Regarding TanksContaining Ferrocyanide, WHC-90-BOO3-Rl (Update 10-22-90), WestinghouseHanford Company, Richland, Washington.

Dukelow, G. T., J. W. Hunt, H. Babad, and J. E. Meacham, 1995, Tank Safety ScreeningData Quality Objective, WHC-SD-WM-SP-004, Rev. 2, Westinghouse HanfordCompany, Richland, Washington.

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WHC-EP-0474-21

Dickinson, D. R., J. M. McLaren, G. L. Borsheim, and M. D. Crippen, 1993, FerrocyanideSafety Program: Credibility ofDrying Out Ferrocyanide Tank Waste by Hot Spots,WHC-EP-0648, Rev. 0, Westinghouse Hanford Company, Richland, Washington.

DOE, 1987, Final Environmental Impact Statement, Disposal ofHariford DefenseHigh-Level, Transuranic and Tank Waste, Hanford Site, Richland, Washington,DOElEIS-01l3, Vol. 1 through 5, U.S. Department of Energy, Washington, D.C.

DOE, 1994a, Recommendation 93-5 Implementation Plan, DOEIRL 94-0001,U.S. Department of Energy, Richland Operations Office, Richland, Washington.

DOE, 1994b, Program Plan for Resolution of the Ferrocyanide Waste Tank Safety Issue atthe Hanford Site, DOEfRL-94-110, Revision 1, U.S. Department of Energy, RichlandOperations Office, Richland, Washington.

Douglas, I. G., and F. R. Reich, 1995, Summary Report ofFY 1995 Raman SpectroscopyTechnology Development, WHC-SD-TD-TI-003, Rev. 0, Westinghouse HanfordCompany, Richland, Washington.

Dukelow, G. T., J. W. Hunt, H. Babad, and 1. E. Meacham, 1995, Tank Safety ScreeningData Quality Objective, WHC-SD-WM-SP-004, Rev. 2, Westinghouse HanfordCompany, Richland, Washington.

Epstein, M., H. K. Fauske, M. D. Crippen, D. R. Dickinson, I. D. McCormack,R. J. Cash, J. E. Meacham, and C. S. Simmons, 1994, FerrocyanideSa[ety Program:An Assessment o/the Possibility 0/Ferrocyanide Sludge Dryout, WHC-EP-0816,Rev. 0, Westinghouse Hanford Company, Richland, Washington.

Fauske, H. K., 1996, Assessment of Chemical Vulnerabilities in the Hariford High-LevelWaste Tanks, WHC-SD-WM-ER-543, Rev. 0, Westinghouse Hanford Company,Richland, Washington.

FR, 1990, "Implementation Plan for Recommendation 90-3 at the Department of Energy'sHanford Site, Washington, tI Federal Register, Defense Nuclear Facilities Safety BoardRecommendation 90-7, Vol. 55, No. 202, pp. 42243 - 42244.

Finfrock, S. H., H. Toffer, and W. T. Watson, 1994, Potential Tank Waste MaterialAnomalies Located Near the Liquid Observation Wells: Model Predicted Responses 0/a Neutron Moisture Detection System, WHC-EP-0809, Westinghouse HanfordCompany, Richland, Washington.

Fowler, K. D., 1994, Action Plan/or Response to Abnonnal Conditions in Hariford SiteRadioactive Waste Tanks Containing Ferrocyanide, WHC-EP-0407, Rev. 2,Westinghouse Hanford Company, Richland, Washington.

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Fowler, K. D., and R. D. Graves, 1994, Decision Analysis for Continuous Cover GasMonitoring ofFerrocyanide Watch List Tanks, WHC-EP-0743, Rev. 0, WestinghouseHanford Company, Richland, Washington.

Gerton, R. E., 1994, Environmental Assessment (EA) and Finding ofNo Significant Impact(FONSIJfor the Waste Tank Safety Program at the Hanford Site, (DOE/EA-0915),(letter 9402034B/94-SST-053 to President, Westinghouse Hanford Company, March 8),u.s. Department of Energy, Richland, Washington.

Grigsby, J. M., A. K. Postma, R. J. Cash, J. E. Meacham, M. A. Lilga, H. K. Fauske, andM. Epstein, 1996a, Assessment of the Potential for Ferrocyanide Propagating ReactionAccidents, WHC-SD-WM-SARR-038, Rev. 0, Westinghouse Hanford Company,Richland, Washington.

Grigsby, J. M., A. K. Postma, R. J. Cash, J. E. Meacham, M. A. Lilga, H. K. Fauske, andM. Epstein, 1996b, Assessment of the Potential for Ferrocyanide Propagating ReactionAccidents, WHC-SD-WM-SARR-038, Rev. OA, Westinghouse Hanford Company,Richland, Washington.

Grigsby, J. M., D. B. Bechtold, G. L. Borsheim, M. D. Crippen, D. R. Dickinson,G. L. Fox, D. W. Jeppson, M. Kummerer, J. M. McLaren, J. D. McCormack,A. Padilla, B. C. Simpson, and D. D. Stepnewski, 1992, Ferrocyanide WasteTank Hazard Assessment--Interim Repon, WHC-SD-WM-RPT-032, Rev. 1,Westinghouse Hanford Company, Richland, Washington.

Guimond, R. J., 1996, [Closure ofDefense Nuclear Facilities Safety BoardRecommendation 9O-7J, (letter to J. T. Conway, Chairman, DNFSB, March 13),U.S. Department of Energy, Washington, D.C.

Harmon, H. D., 1991, Safety Measures for Waste Tanks at Hanford Site, Richland,Washington, (letter 9059124~1 to R. E. Gerton, DOE-RL, February 8), WestinghouseHanford Company, Richland, Washington.

Kinzer, J. E., 1996, Authorization to Remove Four Ferrocyanide Tanks, 241-C-I08,241-C-I09, 241-C-ll1, and 241-C-112from the Watch List, (letter 9601578BI96-WSD-116 to A. L. Trego, President, Westinghouse Hanford Company, June 25),u.s. Department of Energy, Richland Operations Office, Richland, Washington.

Kress, T., K. Bandyopadhyay, P. d'Entremont, S. Slezak, and M. Reich, 1990, Risk of aFerrocyanide Explosion in the Hanford Waste Tank Farm, (memorandum toJohn Tseng, DOE-HQ, September 20), Ad Hoc Task Force formed byU.S. Department of Energy to evaluate the ferrocyanide safety concerns at the HanfordSite, Oak Ridge National Laboratory, Oak Ridge, Tennessee.

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Lilga, M. A., R. T. Hallen, E. V. Alderson, M. O. Hogan, T. L. Hubler, G. L. Jones,D. J. Kowalski., M. R. Lumetta, W. F. Riemath, R. A. Romine, G. F. Schiefelbein,and M. R. Telander, 1996, Ferrocyanide Safety Project: Ferrocyanide Aging StudiesFinal Report, PNNL-1l21l, Pacific Northwest National Laboratory, Richland,Washington.

Lipke, E. J., 1995, Ferrocyanide Safety Program: Completion ofMilestone Report on TankMoisture Data Interpretation Computer Program, (letter 9554603 to R. E. Gerton,DOE-RL, August 30), Westinghouse Hanford Company, Richland, Washington.

McLaren, J. M., 1993, Ferrocyanide Safety Program: Updated Thermal Analysis ModelforFerrocyanide Tanks with Application to Tank 241-BY-I04, WHC-EP-0669, Rev. 0,Westinghouse Hanford Company, Richland Washington.

McLaren, J. M., 1994a, Ferrocyanide Safety Program: Thermal Analysis ofFerrocyanideTanks, Group I, WHC-EP-0729, Rev. 0, Westinghouse Hanford Company, Richland,Washington.

McLaren, J. M., 1994b, Ferrocyanide Safety Program: Thermal Analysis ofFerrocyanideWatch List Tanks, Group II, WHC-EP-0794, Rev. 0, Westinghouse Hanford Company,Richland, Washington.

Meacham, J. E., H. Babad, and H. Toffer, 1993, Moisture Monitoring ofFerrocyanideTanks: An Evaluation ofMethods and Tools, WHC-EP-0658, Rev. 0, WestinghouseHanford Company, Richland, Washington.

Meacham, J. E., R. J. Cash, B. A. Pulsipher, and G. Chen, 1995, Data Requirements forthe Ferrocyanide Safety Issue Developed Through the Data Quality Objectives Process,WHC-SD-WM-DQO-OO7, Rev. 1, Westinghouse Hanford Company, Richland,Washington.

Meacham, J. E., R. J. Cash, D. R. Dickinson, F. R. Reich, J. M. Grigsby, A. K. Postma,and M. A. Lilga, 1996, Assessment of the Potential for Ferrocyanide PropagatingReaction Accidents, WHC-SD-WM-SARR-038, Rev. 1, Westinghouse HanfordCompany, Richland, Washington.

Nguyen, D. M., 1989, Data Analysis of Conditions in Single-Shell Tanks Suspected ofContaining Ferrocyanide, (internal memorandum 13314-89-025 toN. W. Kirch,March 2), Westinghouse Hanford Company, Richland, Washington.

O'Leary, H. R., 1994, /Transmittal of "Program Plan for Evaluation of the FerrocyanideWaste Tank Safety issue at the Hanford Site," DOE/RL-94-110], (letter to J. T.Conway, Chairman, Defense Nuclear Facilities Safety Board, December 2),U.S. Department of Energy, Washington, D.C.

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Parra, S. A., 1994, Integrated Beta and Gamma Radiation Dose Calculations forFerrocyanide Waste Tanks, WHC-SD-WM-TI-634, Rev. 0, Westinghouse HanfordCompany, Richland, Washington. [July 1994]

Payne, M. A., 1994a, Ferrocyanide Safety Program: Continuous Pressure Monitoring inFerrocyanide Watch List Tanks, (letter 9455175 to R. E. Gerton, DOE-RL, July 29),Westinghouse Hanford Company, Richland, Washington.

Payne, M. A., 1994b, Ferrocyanide Safety Program: Transmittal ofGeneral AccountingOffice Closeout Repon, (letter 9454280 to R. E. Gerton, DOE-RL, June 16),Westinghouse Hanford Company, Richland, Washington.

Peach, 1. D., 1990, Consequences ofExplosion ofHanford's Single-Shell Tanks areUnderstated, (letter B-241479 to M. Synar, Chairman, Environment, Energy, andNatural Resources Subcommittee, Committee on Government Operations, House ofRepresentatives, October 10), GAO/RCED-91-34, U.S. General Accounting Office,Washington, D.C.

Postma, A. K., J. E. Meacham, G. S. Barney, G. L. Borsheim, R. J. Cash, M. D. Crippen,D. R. Dickinson, J. M. Grigsby, D. W. Jeppson, M. Kummerer, J. M. McLaren,C. S. Simmons, and B. C. Simpson, 1994a, Ferrocyanide Safety Program: SafetyCriteria for Ferrocyanide Watch List Tanks, WHC-EP-0691, Westinghouse HanfordCompany, Richland, Washington.

Postma, A. K., D. B. Bechtold, G. L. Borsheim, J. M. Grigsby, R. L. Guthrie,M. Kummerer, M. G. Plys, and D. A. Turner, 1994b, Safety Analysis ofExothermicReaction Hazards Associated with the Organic Liquid Layer in Tank 241-C-103,WHC-SD-WM-SARR-OOl, Rev. 0, Westinghouse Hanford Company, Richland,Washington.

Public Law 101-510, Section 3137, 1990, Safety Measures for Waste Tanks at HanfordNuclear Reservation, U.S. Congress, Washington, D.C. [Also referred to as theWyden Amendment]

Rebagay, T. V., R. J. Cash, D. A. Dodd, C. T. Narquis, F. R. Reich, andW. D. Winkelman, 1995, Remote Characterization ofMixed Waste by FourierTransform Infrared Spectroscopy, WHC-SD-WM-RPT-192, Rev. 0, WestinghouseHanford Company, Richland, Washington.

Reich, F. R., R. E. Johnson, B. L. Philipp, J. B. Duncan, and G. L. Schutzenhofer, 1994,Summary ofFiscal Year 1994 Near-Infrared Spectroscopy Moisture Sensing Activities,WHC-EP-0839, Westinghouse Hanford Company, Richland, Washington.

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Reich, F. R., T. V. Rebagay, D. A. Dodd, T. Lopez, and J. K. Watts, 1995, Summary 0/FY 1995 NIR Moisture Measurement Development and Implementation Activities,WHC-SD-WM-RPT-191, Rev. 0; Westinghouse Hanford Company, Richland,Washington.

Schreiber, R. D., 1996, Final Report/or Tank 241-BY-110 Rotary Mode Cores 92, 95, 101,103, 106, 107, 109, 96, and 113, WHC-SD-WM-DP-153, Rev. 1, WestinghouseHanford Company, Richland, Washington.

Sheridan, T. R., 1994a, Closure of the Ferrocyanide Unreviewed Safety Question,(letter 9401180/94-SST-052 to A. L. Trego, President, WestinghouseHanford Company, March 4), U.S. Department of Energy, Richland OperationsOffice, Richland, Washington.

Sheridan, T. R., 1994b, Approval to Remove Two Ferrocyanide Tanks, 241-BX-102 and241-BX-106, from the Watch List, (letter 9406684/94-SST-205 to A. L. Trego,President, Westinghouse Hanford Company, November 17), U.S. Department ofEnergy, Richland Operations Office, Richland, Washington.

Simmons, C. S., 1995, Modeling Water Retention of Tank Waste, PNL-10831, PacificNorthwest Laboratory, Richland, Washington.

Simpson, B. C., and D. J. McCain, 1996, Historical Model Evaluation Data ReqUirements,WHC-SD-WM-DQO-018, Rev. 1, Westinghouse Hanford Company, Richland,Washington.

Sloat, R. J., 1954, TBP Plant Nickel Fe"ocyanide Scavenging Flowsheet, HW-30399,General Electric Company, Richland, Washington.

Sloat, R. I., 1955, In-Farm Scavenging Operating Procedure and Control Data, HW-38955,General electric Company, Richland, Washington.

Smith, D. A., 1986, Single-Shell Tank Isolation Safety Analysis Report, SD-WM-SAR-006,Rev. 2, Westinghouse Hanford Company, Richland, Washington.

Trine, S. L., 1996, Document Provided to Defense Nuclear Facilities Safety Board (DNFSB),(letter 96-PAD-079 to R. Tontodonato, DNFSB, April 10), U.S. Department ofEnergy, Richland Operations Office, Richland, Washington.

Wagoner, J. D., 1993, Approval ofHanford Site Tank Farm Facilities Interim Safety Basis,(letter 93-TOB-209 to T. M. Anderson, President, Westinghouse Hanford Company,November 18), U.S. Department of Energy, Richland Operations Office, Richland,Washington.

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WHC-EP-0474-21

Watkins, I. D., 1991, Report to United States Congress on Waste Tank Safety Issues at theHanford Site, Oetter to D. Quayle, President of the Senate, July 16), U.S. Departmentof Energy, Washingwn, D.C.

Watson, W. T., 1993, Proof of Principle Reportjor In-Tank Moisture Monitoring Using anActive Neutron Probe, WHC-EP-0695, Westinghouse Hanford Company, Richland,Washington.

WHC, 1990, Operating Specifications for Watch List Tanks, OSD-T-151-00030, Revision 0,Westinghouse Hanford Company, Richland, Washington.

WHC, 1991, Tank Farm Stabilization Plan for Emergency Ressponse, WHC-SD-PRP-TI-001,Rev. 0, Westinghouse Hanford Company, Richland, Washington.

WHC, 1996, Operating Specifications for Watch List Tanks, OSD-T-151-00030,Revision B-20, Westinghouse Hanford Company, Richland, Washington.

Wittekind, W. D., and R. D..Crowe, 1996, Electromagnetic Induction Probe CalibrationforElectrical Conductivity Measurements and Moisture Content Determination ofHanfordHigh Level Waste, WHC-SD-WM-ER-531, Rev. 0, Westinghouse Hanford Company,Richland, Washington.

Wodrich, D. D., G. S. Barney, G. L. Borsheim, D. L. Becker, W. C. Carlos,M. J. Klem, R. E. Van der Cook, and J. L. Ryan, 1992, Summary ofSingle-ShellWaste Tank Stability, WHC-EP-0347, Supplement, Westinghouse Hanford Company,Richland, Washington.

Wood, S. A., 1992, Gas Space Analysis For Tank C-109, WHC-SD-WM-ER-183, Rev. 0,Westinghouse Hanford Company, Richland, Washington.

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APPENDIX A

FERROCYANIDE TANK INFORMATION SUMMARY

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Table A-1. Summary of Contents and Status of Ferrocyanide Tanks.-

Total wasteFeCNb Heat load

MaximumStatus of

Tank volume(1,000 g-mol) (kWY

temp. Riser No.tanksd

(1,000 L) (0C) (OF)

BY-103 1510 66 1.6 26 79 1 NS;AL26e 80 5

BY-104 1540 83 3.3 f 51e 123 1 IS; Sound44 111 lOB

BY-105 1900 36 4.9f 47 116 1 NS;AL44 112 10C

BY-106 2430 70 4.7f 51 123 1 NS;AL

BY-107 1010 42 2.6 35 95 1 IS; AL37e 98 5

BY-108 863 58 2.7 42e 107 3 IS; AL41 106 8

BY-110 1510 71 3.3 f 47 116 1 IS; Sound41e 105 lOA

BY-111 1690 6 2.1 f 31g 87 1 (LOW) IS; Sound28e 83 14

BY-112 1100 2 2.4f 32e 89 2 IS; Sound28g 82 15 (LOW)

C-108 250 25 2.9f 23e 74 1 IS; Sound22 71 5

C-109 250 6.8h 3.0f 25e 77 3 IS; Sound25 76 8

C-111 216 33 2.5 f 23 73 5 IS; AL22e 71 6

C-112 394 11.5h 3.3f 26 79 I IS; Sound26e 79 8

T-107 681 5 1.2f 17 63 4 NS;AL17e 63 5

TX-118 1310 <3 1.4 24e 75 I IS; Sound24 75 3

TY-101 447 23 1.1 f 18e 64 3 IS; AL17 63 4

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WHC-EP-0474-21

Table A-I. Summary of Contents and Status of Ferrocyanide Tanks.·

Total wasteFeCN' Heat load

MaximumStatus of

Tank volume(1,000 g-mol) (kW)c temp. Riser No.

tanksd

(1,000 L) (OC) (OF)

TY-I03 613 28 1.5 20 68 4 IS; AL21C 69 7

TY-I04 174 12 0.9 17C 62 3 IS; AL17 62 4

Notes:

• Reflects removal of four ferrocyanide tanks from the Watch List in July 1993 andtwo additional tanks in October 1994. Note: tanks 241-C-I08, C-I09, C-111, andC-112 were removed from the Watch List in June 1996 (Kinzer 1996).Tank information as of June 1996; temperatures are -the highest recorded duringthe quarter ending June 30, 1996.

b Original tank inventories (Borsheim and Simpson 1991).C Heat load values from Table 7-1 in Crowe et al. (1993).d IS - Interim-Stabilized Tank; NS - Not Stabilized; AL - Assumed Leaker Tank;

Sound - Non-Leaking Tank.e Readings from new instrument trees; tank 241-BY-105 already had two trees.f New data taken from Crowe et al. 1995.g Temperature reading from a single thermocouple in the LOW.b Calculated as ferrocyanide [Fe(CN)64

] based on the total cyanide values reported inSimpson et al. (1993a, 1993b).

A-4

Table A-2. Perrocyanide Tank Vapor Sampling Summary . (2 Sheets)Tank Date Flamm. Organic NH3 NH3 HCN NO+N02 TNMOC H2 N20 CO CO2 Water

Sampled (% LEL)b Vapor (ppmv)d (ppmvt (ppmv)d (ppmv)d,& (mg/m3)f (ppmv)B (ppmv)B (ppmv)& (ppmv)& Content(Type)- (ppmv)C %RH eC)h

BY-I03 05/05/94 (2) <1 1.2 25 30.7 <0.005' <0.3 5.2 21.4 49.2 <1 - -11101194 (3) _J - -- 26 - <0.2 -- <99 16.5 <12 126 49 (25.5°C)

BY-I04 04/22/94 (2) <1 26 200 285 <0.005' <0.3 56 204 305 <1 - -06/24/94 (3) -- -- -- 248 -- <0.4 61 295 201 1 10.5 58 (26 ~C)

BY-105 05/09/94 (2) <1 4.9 40 57 <0.005' <0.1 17.8 85 122 0.5 - -07/07/94 (3) -- -- -- 43 -- <0.2 12.7 48 50 0.4 94 61 (26 ~C)

BY-I06 05/04194 (2) <1 5.7 60 87 <0.01-- <0.2 6.3 46 94 -- -- --07/08/94 (3) -- -- -- 74 <0.2 9.9 46 71 0.5 47.6 57 (27°C)

BY-I07 03/25/94 (2) 3-4 67 97 -- -- -- 173 692 802 <5 - --10/26/94 (3) -- -- -- 972 -- <0.2 150 267 621 <20 94 36 (3:U°C)

BY-108 03/28/94 (2) 1 97 700 -- -- <0.5 594 644 757 <5 -- --10/27/94 (3) -- -- -- 1040 -- <0.1 510 400 641 <76 224 56 (25.rC)

BY-110 09/27/92 (1) <1 350 612 -- <2 <0.5 -- -- -- - - --11/11/94 (3) -- -- -- 401 -- <0.2 29 <160 103 <76 229 31 (27°C)

BY-HI 05/11194 (2) <1 8.9 60 -- -- -- -- -- -- <I -- --11/16/94 (3) -- -- -- 59 -- <0.2 9.6 67 99 <1 219 27 (27 ~C)

BY-l12 03/26/93 (1) <1 5.9 10 -- <2 <0.5 -- -- -- - - -11/18/94 (3) -- -- -- 63 -- <0.2 5.8 <94 40 <12 121 53 (23.3~C)

C-108 07/23/93 (**) <1 1.2 <2 -- <2 <0.5 -- .- -- I - --07/07/94 (2) -- -- -- - <0.0002i -- <0.4 -- -- -- - --08/05/94 (3) -- -- -- 2.7 -- <0.3 <1.4 15.3 344 0.1 16.3 76 (25°C)

C-I09 06/23/94 (2) <1 1 4 - -- -- -- -- -- - - -08/09/94 (3) -- -- -- 10.1 -- <0.6 0.65 125 369 0.4 3 79 (27°C)

C-111 08/10/93 (**) <1 <0.2 <2 -- <0.041< <0.5 <0.3 16 39 0.1 -- --06/20/94 (2) <1 <0.2 <2 0.1 <O.Ol i <0.2 0.18 -- -- - _. --09/13/94 (3) -- -- -- 5.6 .- s;,0.7 <0.6 12.4 99 0.1 198 86 (27°C)

C-112 06/24/94 (2) <1 <0.2 4 _0 -- - _0 - -- -- - -08111194 (3) -- -- -- 22.7 - <0.7 3.4 204 544 0.9 102 82 (28°C)

T-107 10/22/92 (l) <1 24 203 _0 <2 <0.5 -- -- .- - - -01118/95 (3) -- -- -- 125 - <0.1 1.4 <94 42 <12 75 82 (l7.ZOC)

Table A-2. Ferrocyanide Tank Vapor Sampling Summary. (2 Sheets)Tank Date Flamm. Organic NH3 NH3 HCN NO+N02 TNMOC H2 N20 CO CO2 Water

Sampled (% LEL)b Vapor (ppmv)d (ppmv)e (ppmv)d (ppmv)d,B (mg/m')f (ppmv)B (ppmv)B (ppmv)& (ppmv)B Content(Type)" (Ppmv)e %RH eC)h

TX-118 07/28/93 (**) <1 0.3 10 -- <2 <0.5 - -- -- -- - --09/07/94 (2) <1 7.8 28 -- <0.02 <0.5 9.3 97 17 2.5 54 -12/16/94 (3) -- -- -- 33 - -- - <94 29 <12 98 42 (21.5°C)

TY-I0l 08/04/94 (2) <1 4 12 16 <0.01 <0.2 -- -- - -- -- --04/06/95 (3) -- -- -- 16 - <0.2 1.0 <93 98 <12 83 77 (l5.6°C)

TY-I03 08/04/94 (2) <1 5 30 31 <0.01 <0.1 -- -- -- -- -- --04/11/95 (3) -- - -- 49 -- <0.2 60 <93 159 <12 121 85 (l5.9°C)

TY-I04 08/05/94 (2) <1 2.5 24 50 -- <0.2 -- -- -- -- - --04/27/95 (3) -- -- -- 61 - SO.2 3 <49 98 <23 <23 88 (15.6°C)

• Sample Type:

**Vapor samples taken from in-tank, non-heated tubes using a vapor sampling cart (SUMMATM only - no NH3).

1 Monitoring performed by Industrial Hygiene technicians using three varying length, non-heated sampling tubes into the tank headspace toevaluate for flammability and toxic vapors; this method is no longer used.

2 In Situ Sampling (ISS) - Sampling is performed by lowering special sorbent traps into the tank headspace that are connected topside to a portablehandcart.

3 Sampling involves the mobile vapor sampling system, heated transfer lines, and installation of a water-heated sampling probe into the tankheadspace. All ferrocyanide tanks are scheduled for resampling using this method.

b Measured using a combustible gas meter; LEL = Lower Explosive Limit.e Measured using an Organic Vapor Monitor (OVM). OVM readings are affected by ammonia; OVM ammonia response is approximately 13:1, so that

13 ppmv of ammonia is indicated as 1 ppmv of organic vapors (p1M (vol) = parts per million by volume).d For Type 1 sampling only; value is measured using colorimetric (Drager™) tubes (values are estimated, and not quantitative).e Analyses of ammonia sorbent trap samples.fTotal non-methane organic compound (TNMOC) concentrations measured for SUMMATM canister samples.J Analyses of SUMMATM canister samples from Type **, and 3 sampling methods.h % RH is the percent relative humidity calculated from measured headspace water content (mg/L), temperature and atmospheric pressure. Temperature

of headspace gas in °C is listed in parentheses.i HCN determinations obtained in selected tanks using a special sorbent trap; values shown are below detection limit of the measurement technique.j -- Data not yet available or not obtained by this type of sampling.k This HeN number was < 0.04 parts per billion vapor as determined by a special sodium hydroxide bubbler.

WHC-EP-0474-21

APPENDIX REFERENCES

Borsheim, G. L., and B. C. Simpson, 1991, An Assessment of the Inventories ofFerrocyanide Watch List Tanks, WHC-SD-WM-EP-133, Rev. 0, WestinghouseHanford Company, Richland, Washington.

Crowe, R. D., M. Kummerer, and A. K. Postma, 1993, Estimation ofHeat Load in WasteTanks Using Average Vapor Space Temperatures, WHC-EP-0709, Rev. 0,Westinghouse Hanford Company, Richland, Washington.

Crowe, R. D., D. P. Maassen, and S. A. Parra, 1995, Calculated Heat Load/or WatchlistSingle-Shell Waste Tanks Using the Average Vapor Space Temperatures, (letter reportattached to internal memorandum from H. Toffer to R. J. Cash, September 29),Westinghouse Hanford Company, Richland, Washington.

Kinzer, J. E., 1996, Authorization to Remove Four Ferrocyanide Tanks, 241-C-I08,241-C-I09, 241-C-1l1, and 241-C-112from the Watch List, (letter 9601578B/96-WSD-1l6 to A. L. Trego, President, Westinghouse Hanford Company, June 25),U.S. Department of Energy, Richland Operations Office, Richland, Washington.

Simpson, B. C., G. L. Borsheim, and L. Jensen, 1993a, Tank Characterization Report:Tank 241-C-I09, WHC-EP-0688, Westinghouse Hanford Company, Richland,Washington.

Simpson, B. C., G. L. Borsheim, and L. Jensen, 1993b, Tank Characterization Data Report:Tank 241-C-112, WHC-EP-0640, Rev. 1, Westinghouse Hanford Company, Richland,Washington.

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WHC-EP-0474-21

DISTRIBUTION (Continued)

Sandia National LaboratoriesP.O. Box 5800Albuquerque, NM 87185

Dana A. Powers, MS-0744Scott E. Slezak, MS-0741

Science Awlications International Corporation20300 Century Blvd, Suite 200-BGermantown, MD 20874

Paul Hogroian (3)

State of Washington - Department of Ecology

Robert C. KingP. O. Box 47600Olympia, WA 98504-7600

Alex B. Stone1315 W. 4th AvenueKennewick, WA 99336

Waste Policy Institute555 Quince Orchard Road, Suite 600Gaitherburg, MD 20878-1437

Donald T. Oakley

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DISTRIBUTION (Continued)

ONSITE

9 D,S, Department of Ener~y,Richland Operations Office

W, F, Hendrickson (2) S7-54D, H, Irby S7-54A, G, Krasopoulos A4-81J. K. McClusky S7-50J. C. Peschong S7-53Public Reading Room H2-53RL Docket File (2) Bl-17

4 Pacific Northwest LabOratory

J. W, Brothers K5-22R. T. Hallen P8-38M, A. Lilga P8-38Hanford Technical Library P8-55

26 Westin~house Hanford CompanY

H, Babad 87-30J. B. Billetdeaux S7-15R. J. Cash (2) 87-14M, D, Crippen L5-31R. D. Crowe HO-38M, L, Dexter Rl-51D. R. Dickinson L5-31G. T, Dukelow (2) 87-14S. J. Eberlein R2-12J. M. Grigsby A3-37M. N, Islam R3-08D. W. Jeppson L5-31N, W, Kirch R2-11C. A. Kuhlman B3-30

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DISTRIBUTION (Continued)

Westinghouse Hanford CompanY (Continued)

J. E. Meacham (2)N. J. MillikenS. R. MorenoF. R. ReichB. C. SimpsonCentral FilesCorrespondence ProcessingEDMCDPC

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S7-14H4-65B3-06L5-55R2-12A3-88A3-0lH6-08A3-94