ML20024G983

Waste Form Qualification Program for Cement Solidification of Sludge Wash Liquid.

ML20024G983
Person / Time
Site:	West Valley Demonstration Project
Issue date:	05/14/1991
From:	ENERGY, DEPT. OF
To:
Shared Package
ML20024G982	List: ML20024G981 ML20024G983
References
REF-PROJ-M-32 PROC-910514, NUDOCS 9105160312
Download: ML20024G983 (127)

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O WASTE FORM OUALIFICATION PROGRAM FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUID WVNS-TPL-70-li Test Plan for the Waste Form Qualification Procram for Cement Solidifica. ion of Sludoe p Wash Liould S]P 91-01 LWTS/ CSS Inteorated Test Extra Tab Test Results Report on WVNS-TPL-70-il Extra Tab Test Results Report on SIP 91-01 Extra Tab Future Reference Document (s)

WVNS-TRO-025 Test Recuest for Development of the Nominal Recipe for Cement Solidification of Sludoe Wash Liouids WVNS-TP-025 Proceoure for Development of the Nominal Recipe for Cement Solidification of Sludoe Wash Liquids WVNS-TSR-025 Test Summary Report on WVNS-TRO-02S WVNS-TRQ-026 Test Recuest for Waste Form Qualification Work f or the Nominal Recioe f or Cement Solidification of Sludge Wash Liquids WVNS-TP-026 Procedure for Qualification of the Nominal Recipe f or Cement Solidification of Sludge Wash Lioulds

• WVNS-TSR-026 Test Summary Report on WVNS-TRO-026 WVNS-TRO-028 Test Recuest for Development of the Process Control Parameters for Cement Solidification of Sludge Wash Liouids WVNS-TP-028 Procedure for Develcoment of Process' Control Parameters for Cement Solidification of Sludge Wash Liouids WVNS-TSR-028 Test Summary Report on-WVNS-TRO-028 WVNS-TRO-029 Test Recuest for Production of Cement Product from Actual Sludoe Wash miouid WVNS-TP-029 Not issued WVNS-TP-029A Procedure for Production of Cement Product from Actual Sludge Wash Liouid 9105160312 PDR 910514 PROJ M-32 PDR

WVNS-TSR-029 Test Summary Report on WVNS-TRQ-029 WVNS-TRO-O O Test Recuest for Full-Scale Confirmation of the Nominal Recioe for Cement Solidification of Sludoe Wash Liquids WVNS-TP-030 Test Plan [PrG .edurel f or Full-scale Confirmation of the Nominal Rec.iDe of Sludge Wash Liouids WVNS-TSR-030 Test Summary Reece t an WVNS-TRQ-030 Sxtra Tab Extra Tab Extra Tab Extra Tab O

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West Valley Doe. Nuoer xvNS m .10.,,

O Demonstration Project neviaien Nu=er 0 Revision Date 03-25-91 Engineering Release #2044 TEST PLAN FOR THE WASTE FORM QUALIFICATION PROGRAM FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUID PREPARED BY Akhw M. N. Baker Cognizant Engineer APPROVED BY , a f( ) h // b D. C. Meess (ogniz' ant Systeq Design Manager APPROVED BY M, \)cJd P. J Valenti Faci %tyRepresentative APPROVED BY M t/h i e '/. -; :i r/. / '

'D. L. Shugars Quality Agourance Manager APPROVEDBYf/ [ f.

- [ D. J, Harward

' Radiation & "p'rety Manager /

APPROVED BY kel. w J. C. Cwynar IRT$ Procesd Control Engineering West Valley Nuclear Services Co., Inc.

P.O. Box 191

[ SAJ0062: 3RM West Valley, NY 14171-0191 WV-1816. Rev.1

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WNS TPL.7011 Rev. O RECORD OF REVISION a

'. PROCEDURE If there are changes to the procedure, the revision number increases by one.

], These changes are indicated in the left margin of the body by an arrow (>) at the beginning of the paragraph that contains a change, i

i Example:

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WNS TPL-70 11 Rev, O RECORD OF REVISION (CONTINUATION SHEET)

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VVNS-TPL 70 11 O TEST PLAN FOR THE VASTE FORM QUALIFICATION PROGRAM FOR CEMENT SOLIDIFICATION OF SLUDGE VASH LIQUID REV. 0 1.0 PURPOSE The purpose of this test plan is to describe the Waste Form Qualification 3

Program for Cement Solidification of Sludge Wash Liquid. The plan specifien the testing required to develop and qualify a stable waste form in accordance with the requirements of 10 CFR 61, Code of Federal Regulations, Title 10 " Licensing Requirements for Land Disposal of Radioactive Waste" and the USNRC Branch Technical Position on Vaste Form, i Revision 1 draft dated December 1990.

I j 2.0 APPLICABILITY This program applies to the qualification testing required to demonstrate that the waste form developed herein for the Sludge Wash waste stream meets the waste stability criteria of 10CFR61.56. The scope includes the experimental work performed from vaste characterization through full-scale testing in the Cement Solidification System (CSS).

3.0 CENERAL REQUIREMENTS 3.1 All procedures for conducting tests and documenting and evaluating (p) test results will be prepared, reviewed, and approved in accordance with the requirements of the VVNS Policy and Procedure Manual.

Engineering Procedures EP-11 001, EP-11-003, and SOP 00-2, 3.2 Test requirements will be as specified in Test Requests (TRQ) issued by the IRTS Process Control Engineering organization in accordance

, with EP ll-003.

3.3 Testing in response to the Test Resquests shall be performed in

accordance with the Test Procedures (TP) issued by the Analytical &

Process Chemistry Laboratory in accordance with EP-11003.

l' 3.4 Operation of the Cement Solidification System (CSS) will be by qualified CSS Operations personnel =in accordance with SIP 91-1 and existing Standard Operating Procedures (SOP's).

3.5 Lab testing will be performed by qualified Analytical & Process Chemistry Technicians using Analytical Chemistry Methods (ACM's).

3.6 All data collection, reporting, and documentation will be performed in accordance with EP-ll-001 and EP-11-003 as applicable.

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WVHS Tpt 70 11 Rev. O

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4.0 SCOPE 3

j_ ~D(,,/ 4.1 The scope of the qualification program will be as described in ,

3 documents summarized _in the flowchart (Figure 1).

i l 4.2 Nominal Recipe Development (WVNS TRQ 025)

I Development of the " nominal" recipe will include determination of the " nominal" Water to Cement Ratio, as well as the " nominal"

addition rates for the recipe enhancers

calcium Nitrate, Antifoam, i ano Sodium Silicate.

4.3 Waste Form Qualification (WVNS TRQ.026) i j Qualification of the " nominal" recipe will include _ establishing a-l curve of compressive strength vs. . time, determination of the maximum practical compressive strength, verification of compressive strength j after thermal cycling, determination of resistance of leaching of radionuclides, and verification of compressive strength after i

immersion.

b 4.4 Full-Scale Verification (WVNS-TRQ 030) i

Full-scale verification of the " nominal" recipe will take place

{ af ter curing of the full scale drums processed under SIP 91 1. The j drums will be core drilled, and the cores will be-evaluated for_  ;

compressive strength, as-well as compressive stren5th after 4

immersion.

] 4.5 Development of Process Control Parameters (WVNS-TRQ 028) i i Recipe boundaries will.be determined for the following parameters, j as a minimum: Total Dissolvad Solids (TDS) in the waste stream,

! Water-to Cement Ratio, variations in the Cement / Calcium Nitrate

! Blend, amount of Antifoam recipe enhancer, and the amount of Sodium

! Silicate recipe enhancer.

l The effects of variations in the waste - stream will be evaluated for j the following parameters: Aluminum content, _ Sodium content, j Organics, Sulfates, pH, Nitites, and Phosphates.

4.6 Confirmatory Testing (VVNS-TRQ 029) i For this test, a quantity of actual High Level Waste Tank Sludge l- -will be decontaminated in the laboratory, and the resulting liquid-

. will be solidified using the " nominal" recipe. The compressive _

l- strength of the solidified sample will be determined.

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i WVNS TPL 70 11 Rev. 0

5.0 DESCRIPTION

() 5.1 Mixing of lab scale specimens shall be performed unt which duplicate the full scale mixing conditions mixer speed, mix conditions time, etc., to the maximum extent practical, as discussed in the-Branch Technical Position Appendix A.III.A.

5.2 Curing of lab scale specimens 'shall be performed under conditions -

which duplicate the full scale curing conditions to the maximum extent practical, as discussed in the Branch Technical Position, Appendix A.III.B. The centerline temperature vs. time of a full.

scale drum will be established, and this profile will be followed to the maximum extent practical. >

5.3 Compressive strength testing of 2" x 2' x 2" cubes will be performed in accordance with the applicable steps of ASTM Standard C 109, 5.4 Compr essive strength testing of cylinders (both cast and core-dril' ed) will be performed in accordance with the applicable steps of ASTM Standard C 39 and the Branch Technical Position.

( Appendix A.II.B.

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! 5.5 Testing of thermal stability will be performed in accordance with i the applicable sections of ASTM Standard B 553 as discussed in the l Branch Technical Fosition, . Appendix A.II.C.

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5.6 Resistance to leaching of radionuclides will be performed in

! accordance with section C.2.e of the main body of-ANSI /ANS 16.1, as 4v discussed in the Branch Technical Position, Appendix' A.II.F. Prior to leach testing, the most aggressive leachant, deionized water or synthetic sea water will be determined by a 24 hour2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> test.

, 5.7 Development of process control parameters will be performed in

! accordance with existing ACM's, and as discussed in the Branch

Technical Position, Appendix A.VI.A.

j. 5.8 Immersion testing will be performed in accordance with the Test

! Procedures (TP's) for that work, and as discussed in the Branch i Technical Position, Appendix A.II.G. The immersion testing will be j- performed using the most aggret2ive leachant (delonized water or synthetic sea water) as determined in section 5.6 above. Immersion

, testing may take place for up to 180 days, as discussed in the i Branch Technica1' Position.

i l 5.9 Waste test specimens shall have less than 0.5 percent by volume of -

the waste specimen as free liquid as discussed in the Branch j Technical Position, Appendix A.II.H. Any free liquid encountered j shall have a pH greater than or equal to 9.

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VVNS.TPL 70 11 Rev. O i 5.10 Sufficient samples shall be tested to provide enough data to establish a mean and a standard deviation, as discussed in the i

Branch Technical Position, Appendix A.IV

{ b.11 Irradiation testing of the waste form will NOT be performed, because l no ion exchange resins or other organic media are contained in the waste stream, as discussed in the Branch Technical Position,-

Appendix A.II.D.

5.12 Biodegradation testing of the waste form will NOT be performed, because the waste liquid contains no carbonaceous materials, as discussed in the Branch Technical Position, Appendix A.II.E.

6.0 REFERENCES

i I 6.1 10CFR61: Code of Federal Regulations, Title 10, Part 61,

" Licensing Requirements for Land Disposal of Radioactive Vaste"

! 6.2 ASTM C 39: Standard Test Method for Compressive Strength of Cylindrical Concrete Specimens j

j 6.3 ASTM C 109: Standard test Method for Compressive Strength of Hydraulic Cement Mortars Using 2 inch or 50 mm Cube Specimens

6.4 ASTM B 553

Test Method for Thermal Cycling of Elsetroplaced Plastics

, 6.5 ASTM C 617: Standard Practice for Capping Cylindrical Concrete Specimens 6.6 ANSI /ANS 16.1: Standard Measurement of the Leachability of

, Solidified Low-Level Radioactive Vastes by a Short term Procedure 1 .

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'5UBKIT DATA SHEET (S)*

O UNCONTROLED COPY Applicable Field Changes DO NOT USE FOR WORK SIP 91 01 LWTS/ CSS INTF ' TEST Rev, O Approved ikdd Approved

• b b' - - 0 =m IRTS(Operations Manager Pdbcess Condrol Engineering Manager Date 4-te-9/ Date 4f 30 )91 Approved A Jn [ M ,$* Approved . (A 4th e "bp' N RacfiaHon and Safety Qi. li,ty Assurance Manager Date @/~[/ Date /

THIS PROCEDURE EXPIRES 07/31/91 . AFTER THIS DATE, DISCARD EXCEPT FOR MASTER FILE AND COMPLETED WORK COPY System Quality Level C l System Safety Class C The estimated accumulated doso for the work described in this document is less than 100 mrem, WEST VALLEY NUCLEAR SERVICES CO,, INC, May,-- 1991 I Prepared by: M/fMA -

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SIP 91 01 Rev. 0 1

I RECORD OF REVISION PROCEDURE If there are changes to the procedure, the revision number increases by one,

, These changes are indicated in the left margin of the body by an arro,w (>) at j the begint.ing of the paragraph that contains a change.-

i j Example:

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Procedure No. SIP 91 01, Rev. O Date: May 1991 a

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j TABLE OF CONTENTS

, Step Description Page 4

1.0 SC0PE........................................................... 1 I

2.0 DEFINITIONS AND ABBREVIATIONS................................... 2 i

! 2.1 Definitions................................................. 2 3

2.2 Abbreviations.............................................. 2

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3.0 RESP 0NSIBILITIES................................................ 3

!. 4.0 TOOLS, EQUIPMENT, COMPONENTS AND REFERENCES..................... 4 4

4.1 Tools and Equipment......................................... 4 4.2 Components................................................. 4 4.3 References................................................. 4 5.0 CENERAL INFORMATION............................................. 7

, 6.0 PROCEDURE....................................................... 8 N/ 6.1 Prerequisites.............................................. 8 6.2 Simulant Preparation....................................... 8 4

6.3 CSS Operation.............................................. 9-6.4 Thermocouple-Equipped Drum................................. 10 6.5 Sampling................................................... 11 6.6 Test Completion............................................ 12

7.0 ATTACHMENTS..................................................... 13 7.1 Attachment A - Prerequisites & Test Completion..............A-1

' Data Sheet No. 1 7.2 Attachment B - Data Sheet No. 2.............................B-1 7.3 Attachment C - Drum Sampling Locations . . . . . . . . . . . . . . . . . . . . . . C-1 i

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SIP 91-01 .

Rev. O j FULL SCALE VERIFICATION TEST 1

1.0 SCOPE a

The objectives of the full-scale verification test of CSS are:

j 1.1 Verify that the full scale vaste forms produced from simulated

{ sludge wash solutions in the CSS meet the requirements of waste T

l stability per 10 CRF 61.56 by checking for free liquid, fill level, and penetration resistance per SOP 70-40.

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1.2 Verify that the CSS consistently operates within the limits set by WVNS-TRQ 028, " Test Request for Development of the Process Control i

Parameters for Cement Solidification of Sludge Wash Liquids."

;O 1.3 Verify the ability of the process instrumentation to measure and document process control parameters.

J 1.4 Verify that test results for specimens obtained by core sampling full-scale products correlate with test results for laboratory

] scale specimens produced during the Qualification Test Program, j WVNS-TRQ 026.

i correlation will be. accomplished by performing (1) compressive

strength testing on as-cured material (cured a minimum of 28 days) l and (2) 90-day immersion tests that include pre- and post-immersion compressive strength tests in accordance with the USNRC Branch Technical Position on Waste Form, (reference 4.3.36) section C.2.h, and appendix A.

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SIP 91-01 Rav. O i

1.5 Verify that the full-scale waste forms demonstrate the stab,ility requirements of the USNRC Branch Technical Position on Waste Form,

( (reference 4.3.36) appendix A, and VVNS-TRQ 030 i

1.6 Produce test specimens (40 cubes 2"x 2"x 2" and 50 cylinders 4

3" Diameter x 6" long) 1.7 This SIP will be conducted in accordance with WVNS-PCP 001, Rev. 4.

)

2.0 DEFINITIONS AND ABBREVIATIONS l 2.1 Definitions 2.1.1 Programmable Logic Controller - Logic Controller that controls the automatic operation of the CSS using program logic rather than hardwired logic.

a j 2.1.2 Data Acquisition System - Computer basad system which

!( ) monitors and records the outputs of selected CSS instrumentation.

1 2.1.' s1 Dissolved Solids - concentration of dissolved salts

. ally expressed as parts per million (ppm) or weight percent (w/o or vt. %).

l 2.2 Abbreviations A&PC - Analytical and Process Chemistry WDV -

Waste Dispensing Vessel CSS -

Cement Solidification System DAS -

Data Acquisition System 4 IWP -

Industrial Work Permit LWTS -

Liquid Waste Treatment System PCE -

Process Control Engineer

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SIP 91 01 Rov. O RWP - Radiation Work Permit ,

/N R&S - Radiation and Safety U SSS - Start-up Shift Supervisor

. TDS - Total Dissolved Solids

3.0 RESPONSIBILITIES i

3.1 Integrated Radwaste Treatment System (IRTS) Operations performs the

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testin5 required by this procedure and completes the data sheet to

, document the procedure.

i l 3.2 IRTS Support Engineering provides technical support as necessary, 1

1 3.3 Process Control Engineering (PCE) provides technical direction

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during testing and checkout, compares the test generated data to Test Plan VVNS TPL-70-011, and issues Test Results Reports.

3.4 QA provides' surveillance to assure that the requirements of this 4

() procedure are satisfied, and signs to indicate verification of work performed and data collected.

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3.5 The Radiation and Safety Department (R&S) monitors radiation and contamination levels.

3.6 Equipment is repaired as necessary according to EP-11 001, or by

SOP 002 as applicable.

3.7 Waste Management Operations performs filled drum movements to the drum cell and core-boring per WVNS-TP-030, 3.8 A&PC analyze and verify satisfactory simulant chemical makeup.

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j 4.0 TOOLS, EQUIPMENT, COMPONENTS AND REFERENCES u

! 4.1 Tools And Equipment i

i. Intercom 'ystem 1

l Solid Sample (s) Transport Container (s)

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Forney Compressive Strength Testing Equipment i

Lifting and rigging equipment r

J Disposable Plastic 2" x 2" x 2" Cube Sample Molds 3

1 j Plastic 3" dia. X 6" high cylinder sample- molds 1

1 1

! Controlled Temperature Chamber 1

i 4.2 Components

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,. CSS - All Cement / Waste mixing equipment fully operational I

! 4.3 References i

l 4.3.1 SOP 70-1 Waste Transfer to the Cement Solidification System i

j 4.3.2 SOP 70-3 Automatic Solidification Operation i

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4.3.3 SOP 70-4 CSS Manual Solidification with the Process Logic:

} Controller Operational 1 b

[ -4.3.4- SOP-70-5 Cravimetric Feeder Operation j 4.3.5 SOP 70-6 Bulk Cement Transfer to Day Bin

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SIP 91-01 Rev. 0 4.3.6 SOP 70-7 Cement Truck Unioading ,

'-- 4.3.7 SOP 70-8 Clean Drum Handling for Cement Solidification System 4.3.8 50P 70-9 Automatic Drum Processing Operation 4.3.9 SOP 70-10 Full Drum Handling For CSS a

4.3.10 SOP 70-11 Cement Solidification System Manual Operation with Process Logic Controller Non-operational 4.3.11 SOP 70-12 CSS Mixer System Flush Operation 4.3.12 SOP 70-17 Manual Drum Operations for the CSS 4.3.13 SOP 70-18 Alarm Procedure for Cement Solidification System 4.3.14 SOP 70-19 CSS Emergency Procedure - Emergency Shutdown 4.3.15 SOP 70-30 CSS Stack Sampler and Monitor System Operation

• 4.3.16 SOP 70-31 ATI System Alarm Responses 4.3.17 SOP 70-32 Operation of the CSS Silo Air Dryer 4.3.18 SOP 70-33 Data Acquisition System Operation 4.3.19 SOP 70-34 operation of the 01-14/ CSS Process Room 4-Ton Bridge Crane 4.3.20 SOP 70-35 Operation of Maintenance 2-Ton Bridge Crane 4.3.21 SOP 70-36 Drum Cell Crane Operation 4.3.22 SOP 70-37 Smear Robot Operation q

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SIP 91-01 Rev. 0 4.3.23 SOP 70-39 Draining and Flushing the VDV 4.3,24 SOP 70-40 CSS Drum Sampling Station Operation 4.3.25 SOP 70-41 CSS Preventive Maintenance Program 4.3.26 SOP 70 42 CSS Safe Shutdown During an Emergency Situation 1

4. 3. '!7 SOP 70 43 Emergency Emptyin5 of CSS Mixers 4

4.3.28 SOP 70-45 Waste Classification j 4.3.29 SOP 70-46 Operation of the Sodium Silicate Delivery System 4.3.30 SOP 002 Ouidelines for the Preparatio" of Facilities Work Instruction Documents

, 4.3.31 SOP 004 Lock and Tag Procedure d

4.3.32 EP 11-001 Test Control i

4.3.33 W-222 Trouble Records 4.3.34 TPL 70-11 Test Plan for the Waste Form Qualification

Program for Cement Solidification of Sludge Wash Liquid 4.3.35 WNS-PCP-001 Process Control Plan for Cement Solidification of Decontaminated Supernatant 4.3.36 DOE ORDER 5820.2 (a), Radioactive Waste Management 4.3.37 US NRC Branch Technical Position on Waste Form, Rev. 1 dated January,1991 i

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SIP 91 01 Rov.- 0 4.3.38 WNS TP-026, Test Procedure for Waste Form Qualification of

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the Nominal Recipe for Cement Solidification of Sludge Wash- j Liquid-  !

4.3.39 WNS TP 030, Test Procedure for Full Scale Verification of the Nominal Recipe for Cement Solidification of Sludge Wash Liquid 5.0 CENERAL INFORMATION 5.1 Simulant mixed for this testing shall be transferred to the WDV in the CSS for solidificat'on.

5.2 This Waste Stream shall be solidified in the CSS using recipes developed at Analytical and Process Chr.ai%try, and listed in WNS-PCP-001, Rev. 4. All operations shall be conducted per System 70 SOPS.

5.3 Cube samples and cast cylinders will be obtained from these drums j and destructively tested. This testing will be performed in accordance with WNS-TP-026.

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5.4 Core samples obtained from these drums after curing a minimum of 28 i

L days will be destructively tested in accordance with WNS-TP-030.

i 5.5 OPERATORS SHOULD PERFORM FREQUENT. CHECKS ON SYSTEMS.THAT ARE TURNED ON OR SHUT DOWN TO ASSURE -THAT THE SYSTEM DOES WHAT IS. EXPEC'irD, I.E., WATER FLOWS, PRESSURE RISES, LEVEL INDICATORS, ETC. #

IF THE REQUIRED ACTION THAT IS SUPPOSED TO HAPPEN DOES:NOT HAPPEN, l- (1) STOP - DO NOT ATTEMPT TO PERFORM THE NEXT STEP, (2) SECURE ' W,;

I SYSTEM IN A SAFE MODE, AND (3) NOTIFY SHIFT SUPERVISOR IMMEDIATELY. -

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i i 6.0 PAOCEDURE ,  ;

l AIL STEPJ 7N THIS PROCEDURE THAT EBQUIRE AN INSPECTION, THE RECORDING OF DATA, OR A SIGN-OFF WII.1, SE DDKTTED BY A [+] IN THE LEFT HAND MARGIN.

THE INSPECTION RESUI.TS. DATA, OR SIGN OFF VIII BE RECORDED ON THE APPROPRIATE PROCEDURE DATA SHEET (S).

6.1 Prerequisites _  !

[+] 6.1.1 Notify PCE and QA prior to performing any testing. Obtain ,

an RW and IWP to perform drum testing.  !

[+] .6.1.2 Shift Supervisor or Shift Engineer verify SOPS listed in  !

Section 4.3 are current.

[+] 6.1.3 Record Serial Number and Calibration Data for Scales-used ,

in Section 6.2 on attachment A.

6.2 Mimulant Preparation 6.2.1 Mix cold test chemicals in accordance with the followink simulant recipe:

Chemical Symbol Weight Source Sodium Nitrate NANO 3 286.3# P.O. 49405 Sodium Nitrite nan 0g 272# P.O. 49408 i

Sodium Sulphate Na2S v4- 169.9# P.O. 49871 Potassium Nitrate KNO 17.9 P.O. 49406 Sodium Carbonate' Na2 0 3 48.4 . 'P.O. 49406 Sodium Hydroxide Na0 .

1,77 P.O.'49409 Sodium B1 chromate Na2C r04 2.48 P.O. 49871 - -

Sodium Chloride Nacl 1.88 .

From VIT..

Sodium Phosphate NaPO 4 1.53 P.O. 49409 l Sodium Holybdate Na Mo04 0.33 P.O. 49871 Sodium Tetraborate Na. B0 3 0.19 P.O. 49871 l Citric Acid - 0.26 .

' P.O.-49920 Oxalic Acid - -

0.26 P.O. 49920-Tartarie Acid -

10.26 P.O. 49920 4 Demineralized Vater HO 2 200 gallons

-BELOO19:8RM ,. -8

m, SIP 91 01 Rev. O 6.2.2 Mix the chemicals and water in the tank and piping ' setup O erected under separate work order (Wo.9100084).

[+] 6.2.3 Obtain a sample of the simulant. Record lab analysis number on attachment A. A&PC verify satisfactory.

6.3 CSS operation 6.3.1 Load the gravity feed conveyors with a minimum of 2$ square drums per SOP 70 8. Repeat as necessary to keep CSS supplied with empty drums.

6.3.2 input the required data to the Data Acquisition System per SOP 70 33. .

6.3.3 Use the mix tank pump to fill the Waste Dispensing Vessel.

6.3.4 Repeat step as required to keep the VDV liquid level above O the low level set point ( 35 gallons).

6.3.5 Use SOP 70 3, to operate the CSS automatically.

6.3.6 When the last batch of vaste being processed is in the mix cycle, s..tch the progrca selector to "A" to automatically stop the program when the batch is complete.

4 j 6.3.7 Use SOP 70 12 to flush the mixers. ,

i i 6.3.8 Use SOP 70 39 to drain and flu.n the WDV if required. _,

6.3.9 Hold the completed drums in .the Drum Londout Area, j Transporter, or Process cell as required.

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SIP 91 01 Rev. O

[+] 6.3.10 Select ten (10) drutas for sampling. The ten drums,shall be specified by Engineering and QA prior to the production run, and shall be spread out to cover the entire production rua. Record drum numbers on attachment B.

[+] 6.3.11 For 6ach drum selected, determine through review of production data if cement /vante mixture was produced within tolerances specified in recipe data sheets and record results on Data Shnet No. 2.

6.4 Thermocouple Eauipped Drum i:

l 6.4.1 Equip the first drurn processed with thermuouples and j temperature recorder as follows:

i i

6.4.2 Insert three (3) thermocouples 10", 20", 30" long through the waste along the drum centerline.

6.4.3 Connect wires to a Holytek recorder i

j a. Program the recorder to print the temperature at

! 10 minute intervals i

} b. Plug the recorder into a 115VAC receptacle in the Drum l Loadout Area  ;

l l

c. Locate the recorder near the drum c .,

l 6.4.4 Equip one (1) of the cylinders cast via step 6.5 with a 6" long K thermocouple (Inconel 600) (no recorder). The -

instrument that this thermocouple will be connected to must be calibrated,to accurately. display and/or record .

temperature sensed by thermocouple.

i 1

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I SIP 91 01 Rov. O

a. This cylinder will be used as a control cylinder during thermal. cycling testing per WNS.TP.026 6.4.5 Hold the thermocouple.equippd drum in the Drum Loadout Area until the drum conterline temperature returns to ambient. >.

6.5 S atepling 6.5.1 After the drum to be sampied is completed, enter the Process Cell and obtain 2" x 2" x 2" cube samples:

a. With the drum at Fill Station M 15, RAISE the fill nozzle

b. Move the drip tray IN

c. Place the cube molds on a towel wipe O d. Scoop the cement / waste product from the drum and fill the cube molds

• F1LL THE MOLDS AS FULL AS POSSIBLE *

e. Place the molds in a poly bag containing wipes

f. Label the bag with the drum number, date, and time 6.5.2 Obtain 3" diameter x 6" long cylindrical samples as follows:

a. Place the cylinder molds on a towel wipe

b. Scoop the cement / waste product from the drum and fill the cylinder molds b

O BEL 0019:8RM 11

j SIP 91 01 Rev. 0 I

!

• FILL THE MOLDS AS FULL AS POSSIBLE * .

l c. Place the molds in a poly bag containing wipes i

d. Label the bag with the drum number, date, and time i i

1

6.5.3 Repeat for a total of forty (40) cubes from up to ten (10)

. drums.

}

j

• DO NOT OBTAIN MORE THAN TEN (10) CUBES FROM A DRUM

• l j 6.5.4 Repeat for a total of fifty ($0) cylinders from up to ten l (10) drums.

• DO NOT OBTAIN MORE THAN TEN (10) CYLINDERS FROM A DRUM * -

q 6.$.5 Release the bagged samples for transfer to the

controlled-temperature chamber for curing in accordanca

() with WVNS TP.026. *

! 6.6 Test Completion i

6.6.1 Flush the remaining simulant and chemicals from the mixing j tank to the vaste disponsinh vessel.

6.6.2 When the last batch of simulant has been processed, flush tne mixera per SOP 70-12, and shut down the CSS.

[+] C.6.3 Shift r.ngineer verify all open items TRs and TEs have been '

closed out.

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[+] 6.6.4 QA representative verify. ,

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I 7.0 ATTACl!MENTS ,

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7.1 Attaciunent A

Prerequisites and Test Completion . Data Sheet No. 1  ;

j l 7.2 Attaciunent B: Data Sheet No. 2 l t-r i

1 7.3 Attachment C: Core Sampling Locations  ;

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SIP 91 01 Rev. O ATTACHMENT A .

PREREQUISITES AND TEST COMPLETION Data Sheet No. 1 Step Number Description Initials /Date 6.1.1 Engineering Notified Time QA Notified Time RWP Obtained IVP Obtained ,

6.1.2 SOPS Current Y/N 6.1.3 Calibration Data Item, _ Serial No. Last Calibration 6.2.3 Simulant Sample Results:

, Sampled by

. Operator /Date I

Sample Results

! ~

Lab Analysis No. . ,.'

. 4

! Results Acceptable , ,

A6PC/Date 6.6.2 Shift Engineer verify all test exceptions, trouble records, open *

-. s . . r --.

items are closed out

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Engineer /Date -

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j 6.6.3 QA Verification j, QA Representative /Date BEL 0019:8RM A1

I SIP 91 01 l Rev. O t

i ATTACHMENT B .

Data Sheet No. 2 1

I I I l -l I 6.3.10 Drum Number i I i 1 l l l l l l l l 5 Waste Type i I I I I I -

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, 6.3.11 Drum Weight From M 15 (1bs) l I I I I i j l l l l l 1

} Drum Weight From Mixer l l l l l .I ,

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Load cell (1bs) l I I I I l i

j l l l l l l l Waste Within Tolerance. l l l l l l l (Yes/No) l l l l l l _.

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O Demonstration Project """"""""

Revision Date 04/30/91 Engineering Release #2074 TEST REQUEST DEV ELOPMENT OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS PREPARED DY jfW M ~ M. N. Baker Cognizant Engineer i APPROVED BY _

/ g cogn'Tnnt System Design Manager D. C. Meeso APPROVED BY '/ ( C ch'C ^ h.L.Shugars Quality Ag*urance Manager A

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4 D. J. Harward ritsdiation ay Tarety Hanpfer APPROVED BY k. b C-xv w.~ 4f i 9 lq l J. C. Cwynar Prodess Contrdi Engineering ~

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West Valley Nuclear Services Co., Inc.

P.O. Box 191 West Valley, NY 141710191 WV-1816, Rev.1

WNS TRQ.025 Rev, 0 l

RECORD OF Rf"JISION PROC EDL'R E If there are changes to the procedure, the revision nwnber increases by one.

These changes are indicated in the left margin of the body by an arrow (>) at i the beginning of the paragraph that contains a change.

Example: '

> The arrow in the margin indicates a change.

Revision On Rev. No. Description of Changes Page(s) Dated

O Original Issue All 04/10/91 i

W 1807 Rev. 1 i BEL 0046:3RM

- m WNS TRQ.025 Rev. O RECORD OF REVISION (CONTI! NATION SHEET)

Rev, No. Revision on Description of Changes Page(s) Dated l

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W 1807, Rev, 1 11 BELOO46:3RM

WNS TRQ 025 Rev. O DEVELOPMENT OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS

1.0 INTRODUCTION

This work is required to develop a stable waste form for cement solidification of Sludge Wash Liquids which meets the characteristics required by 10 CTR 61, Code of Regulations. Title 10. " Licensing Requirements for Land Disposal of Radiosctive Waste," and the USNRC Branch Technical Position on Waste Form, Revision 1, dated January 1991.

1.1 All work will be performed in accordance with WNS TPL 70 011, the Test Plan for the Waste Form Qualification Prograqi for Cement  ;

Solidification of Sludge Wash Liquid (reference 7.3) and related test procedures.

1.2 All work will be performed with a " nominal" simulant representing i the actual waste liquid. The composition of the " nominal" simulant j was identified by Analytical and Process Chenistry based on Sludge y

Vash Experimentation (reference 7.1) and Mass Balance Modeling Calculation (reference 7.2). The composition of the " nominal" waste simulant is shown in table 1.

l 2.0 OBJECTIVE 2.1 Using the simulant liquid, and the existing recipe for supernatant l solidification, develop the " nominal" recipe as follows:

] a. Characterize the solids in the waste liquids: sulfates, l nitrates / nitrites, aluminum, organics, etc.

1

b. Determine the " nominal" percent solids (by weight) in the waste 11 quid.

c. Determine the " nominal" range of Calcium Nitrate recipe enhancer to be blended with Portland Type I cement.

l d. Determine the " nominal" water to cerrent ratio. Note that this ratio is to be calculated as follows:

(weight of waste) x (1 solids fraction) l WC - (1 Calcium Nitrate fraction) x (weight of cement) i

e. Determine the " nominal" amount of Antifoam (CE AF9020) recipe enhancer to be added to each batch.

f. Determine the " nominal" amount of Sodium Silicate recipe enhancer.

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WVNS TRQ.025 Rev. 0 2.2 At a minimum, slurry density, gol time, free liquid, penetration resistance and compressive strength shall be determine for each O specimen.

2.3 The compressive >,trength of the encapsulated waste shall achieve the maximum practical compressive strength, as required by the Branch Technical Position, appendix A.II.B. A mean compressive strenach in excess of 500 psi is rtquired. Lab. scale specimens will be 2" x 2" x 2" cubes in accordance with the applicable steps .c ASTM Standard C 109.

• 2.6 Mixing of the lab. scale specimens shall be performed under conditions approximating the full scale equipment. Results of lab.

scale tests shall be correlated to full scale test results as described in the Branch Technical Position. appendix A.II.I.

Correlation may be limited to compressive strength test results and immersion tests, as discussed in VVNS.TRQ 026.

2.5 Lab scale specimens shall be cured at 88 C 12 C, for 6118 hours0.0708 days <br />1.699 hours <br />0.0101 weeks <br />0.00233 months <br />, the same conditions as full scale products, as described in the Branch Technical Position, appendix A.III.B.

• 2.6 Test specimens shall be kept in sealed containers during curing and storage. to prevent loss of water that might affect the performance of the waste form specimens during subsequent testing, as discussed in the Branch Technical Position, appendix A.III.C.

3.0 SAFETY 3.1 Industrial hygiene practices will be as described in the WVNS

Hygiene & Safety Manual, WVDP.011.

3.2 Radiological work will be performed in accordance with the VVDP

{ Radiological Controls Manuals, VVDP.010.

t 3.3 Work in the Analytical & Process Chemistry lab will be performed in j accordance with existing A&PC methods (ACM's) .

l i 4.0 EQUIPMENT CONFIGURATION 4.1 All lab equipment will be set up in accordancs with UVNS.TP.025, and as directed by the cognizant A&PC scientist or qualified A&PC technician, 4

5.0 SAMPLING FREQUENCY 5.1 A minimum of ten (10) cube specimens will be produced using the-i

" nominal" recipe as specified by the cognizant A&PC scientist.

i O BELOO46:3RM 2 l

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VVHS TRQ.02$

Rev. 0 6.0 PERSONNEL QUALIPICATION,

() 6.1 Testin6 will be performed by qualified Analytical 6 Process Chemistry techricians in accordance with VVNS TP 025 and using Analytical Chemistry Methods (ACM's) under the cognizance of an A6PC Scientist,

a. Radiochemistry "B" Technicians qualified to VVNS-QS 014.

b. Radiochemistry "A" Techniclans qualified to VVHS-QS 016.

6.2 Surveillance activities will be performed by qualified Quality j Assurance personnel, t

7.0 REFERENCES

t i 7.1 "Vhite Paper on Extraction of Plutentum froin Alkaline High Level Liquid Waste." L. A, Bray, F. T. Hara, and T. T. Karmierczak, Draft C, dated Dec6mber 21, 1990.

7.2 " Preliminary Flowsheet: Sludge Wash with Existing 8D 2 Heet,"

letter EK:91:0047, dated March 7, 1991.

7.3 VVHS TPL Oll, Test Plan for the Waste form Qualification Program for Cement Solidification of Sludge Wash Liquids, M. N. Baker, dated March 25, 1991.

8.0 REPORTINC t

i 8.1 The test procedure (VVNS TP 02$) for conducting tests in accordance with this test request shall be issued by the A6PC laboratory.

l 8.2 A Test Summary Report (TSR) will be issued by the Cognizant Engineer or Cognizant ALPC scientist documenting the results of testin6 in accordance with Engineering Procedure EP 11+003.

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l WVNs-IA0-v25 r< e v . u TABLE 1: Salt Concentrations for the " Nominal" Recloe ,

Based on 120.5" Heel Constituent Formula Weloht Sodium Nitrate NANO 3 35.62 Sodium Nitrate NANO 2 33.04 Sodium Sulfate Na2SO4 21.13 Sodium Bicarbonate NaHCO3

• Potaantuin Ni tra te KNO3 2.23 k Sodium CarDonate Na2CO3 e.02 l Sodium Hydroxide NaOH 0.22 l Sodium Chromate Na2Cr04 0.300 '

Sodium Chloride Nacl 0.234

! Sodium Phosphate Na3PO4 0.190 bodlum Molybdate Na2Mo04*2H2O 0.040

] : Sodium Borate Na2D407 0.024 4

Citric Acid C6H807 0.032

Caalic Acid C2H204 0.032 li Tartaric Acid C4H606 0.032 r

l Water H2O 203.03

]

j tota 1 Weloht 302.982 l

Weight of Solids 99.952 Weloht Percent Solids 33*/.

8 Notet Sodium Bicarbonate does not apDear as NaHNO3 J

at elevated pH s l

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West Valley o " ~ w "s-tac-o:1 Demonstration Project '

Revision Date 05/01/91 Engineering Release #2077 TEST REQUEST A ASTE FORM QUALIFIC AT!ON WORK FOR THE NOMIN AL RE"'!PE J FOR CEMENT SOLIDIFICATION OF OLUDGE WASH LlOUIDS i

l 1

l PREPARED BY 7//# d e k _M. N. Ba ke r' Cogni zant Engineer M

APPROVED BY U D. C . M e es s Cogni zant System Desi gn Manager k APPROVED BY [/ c,'/ Mv ph 4 I / < D. L. Shugars Quality Aspurance ManaEer AP B Y,. r, , kD. J. Harward

, , adi ation af Saf ety Manag APPROVED BY . b - (w w- Nfi9 [9l J . C . C w yn ar' Process Contrd) Engineering I

1

/

West Valley Nuclear Services Co., Inc.

P.O. Box 191 B E LOO 47 : 3RM West Valley, NY 14171-0191 WV 1816, Rev.1

WNS.TRQ.02 6 Rev. O RECORD OF REVISION PROCEDURE O If there are changes to the procedure, the revision nwnber increases by one.

These changes are indicated in the left margin of the body by an arrow (>) at the beginnin6 of the paragraph that contains a change.

i Example: ,

> The arrow in the margir indicates a change.  ;

I Revision On Rev. No. Description of Changes Page(s) Dated -

0 Original Issue All 05/01/91-1 J

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l WNS.TRQ.026 j Rev. 0

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RECORD OF REVISION (CONTINUATION SilEET) ,

t 9 Rev No. Description of changes Revision)on Page(s Dated 5

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VVHS TRQ 026 j Rev. O f VASTE FORM QUALIFICATION VORK FOR THE NOMINAL RECIPE

] FOR CEMENT SOLIDIFICATION OF SLUDCE WASH LIQUIDS

1.0 INTRODUCTION

i 1.1 This work is required to demonstrate the stability of the " nominal * '

I waste form recipe developed under Test Request VVNS-TRQ 025.

]. Characteristics which will be tested are required by the 10 CFR 61, ,

Code of Federal Regulations, Title 10, " Licensing Requirements for Land Disposal of Radioactive Waste " and the USNRC Branch Technical Position on Vaste Form, revision 1, dated January,1991, 1 1.2 This work is performed as a part of VVNS TPL 70 011.

1

! 1.3 Vork will be performed with a simulant representing the actual waste j liquid. The simulant is shown in Table 1 and will be verified uader j VVHS.TRQ 025.

! 1.4 Vork will be performed usin6 both 2" x 2" x 2" cubes and 3" diameter

] x 6" long cylinders cast from full scale drums processed in the j Cement Solidification System (CSS) under SIP 91 1. The purpose of this is to establish a correlation between the full scale cylinders, full scale cubes, and lab scale cubes. 14ach testing specimens will J

be 1" diameter x 3" high cylinders prepared in the A6PC laboratory j using the lab scale mixer. Leach specimens will be " spiked" with j appropriate radionuclides.

1.5 Test Procedure VVNS TP 026, providing instructions for testing in l accordance with this Test Request shall be issued by Analytical and f

Process Chemistry per EP 11003, j 1.6 Test Summary Report, WVNS TSR 026, documenting the results of this l testing, will be issued by the Cognizant En6 neer 1 per EP 11 003.

l 2.0 OBJECTIVES l

l 2.1 A curve of compressive strength vs. cure time will be established j for both cubes and cylinders. The cure time which produces a j compressive strength within 75 percent of maximum shall be l determined.

1 2.2 The compressive strength of the was*e form as required by the Branch Technical Position, appendix A.II.S will be verified at cure times

, of 7, 14, 21, 28, 35, and 42 days. A mean compressive strength in i

excess of 500 psi after 28 days is required.

, 2.3 Thermal cycling stability of the waste form will be tested in j

accordance with ASTM Standard B 553, and the Branch Technical Position, appendix A.II.C.

(

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VVNS TRQ.026  !

Rev. 0 2.4 Resistance to leaching of radionuclides will be performed using a simulant liquid " spiked" with Cesium.137, Strontium 90, and O Plutonium 241. Leaching will be performed in accordance with the Branch Technical Position, appendix A.II.F, and ANS/ ANSI procedure 16.1. Preliminary testing will be performed to identify ~ the leachant as deionized water or synthetic sea water.

A Leachability Index, calculated in accordance with ANS/ ANSI 16.1, greater than 6.0 is required.

25 Immersion testing shall be performed in accordance with the Branch Technical Position, appendix A.II.G. After curing for a minimum of 28 days or the cure time as indicated by the compressive strength vs. time testing in paragraph 2.2 above, at least three (3) cylinders will be immersed for a period of 90 days. Foilowing immersion, the specimens shall be subjected to compressive strength testing. A mean post immersion compressive strength not less than 75% of the pre immersion mean compressive strength (paragraph 2.2 above) is required. If the mean post immersion compressive strength is less than 75% of the pre immersion mean compressive strength, the immersion testing intarval shall be extended (using different specimens) to 120, 1$0, and 180 days. This testing is required to establish that the compressive strengths level off and do not continue to decrease with time.

2.6 For one (1) specimen, the leachability of the following " heavy metal" shall be evaluated in accordance with the Toxicity Characteristics Leaching Procedure (TCLP):

O 3.0 SAFETY Chromium.

\

3.1 Industrial hygiene practices will be as described in the WVNS Hygiene & Safety Manual, WVDP 011, 3.2 Radiological work will be performed in accordance with the WVDP Radiological Controls Manual, WVDP.010.

l 3.3 Work in the Analytical & Process Chemistry lab will be performed in accordance with existing A&PC methods (ACM's),

4.0 EQUIPMENT CONFIGURATION 4.1 All lab equipment will be set up in accordance with WVNS TP 026 and l

as directed by the cognizant A&PC scientist or qualified A&PC technician, 4.2 Mixing will be performed in a manner which duplicates, to the extent

, practical, the full scale mixing equipment, including mixing speed.

{ order of addition, mixing time, energy introduced to the mixture, i

etc., as discussed in the Branch Technical Position, appendix A.III.A.

O BEL 0047:3RM 2

VVNS TRQ 026 Rev 0 4.3 Curing of the samples will be performed in a manner which duplicates, to the extent practical, the curing temperature profile (f-~)s encountered in the full scale drum, as discussed in the Branch Technical Position, appendix A.III.B. A temperature controlled chamber will be utilized.

4.4 Calibration of compressive strength testing equipment will be in accordance with the applicable steps of ASTM Method C 39, C 109, and VVNS-Q1P 027.

5.0 SAMPLING FREQUENCY 5.1 A total of 40 cubes 2" x 2" x 2" will be required.

! 5.2 A total of 50 cylinders 3" diameter x 6" high will be required.

5.3 A total of three (3) cylinders 1" diameter x 3" high will be required for Leach testing, i

6.0 PERSONNEL QUALITTCATION 6.1 Laboratory testing will be perf ormed by qualified Analytical &

Process Chemistry Technicians in accordance with VVNS TP 026 and Analytical Chemistry Methods (ACM's) under the co6nizance of an A6PC Scientist.

a) Radiochemistry "B" Technicians qualified to VVHS-QS 014.

b) Radiochemistry "A" Technicians qualified to VVNS-QS 016.

6.2 Compressive strength testing of cylinders will be performed by Quality Services personnel trained in the requirements of QIP 27.

7.0 DATA rep 0RTING 7.1 A Test Summary Report (VVNS TSR 026) documenting the results of testing performed per this test request shall be issued by the Cogni: ant Test Engineer.

(3 BELOO47:3RM 3

WVNS-TRO-026 Rev. U l TABLE la Salt Concentrations for the " Nominal" Recios Dased on 129.5" Heel Constituent Formula Weight Sodium Nitrate NANO 3 35.62 Sodium Nitritte nan 02 33.94 Sodium Sulfat@ Na2SO4 21,13 Scdium Bicarbonate NaHCO3

• Potassium Nitrate KNO3 2.23 Sodium Carbonate Na2CO3 6.02 1 Sodium Hydroxide NaOH 0.22 Sodium Chromate Na2CrO4 0.000 Sodium Chloride Nacl 0.234 Sodium Phosphate Na3PO4 0.190 i bodium Molybdate Na2 moo 4 2H2O 0.040 Sodium Borate Na2B407 0.024 I Citric Acid C6H807 0.032 I

Ovalic Acid C2H204 0.032 Tartaric Acid C4H606 0.032 Water H2O 203.03 i

Total Weight 302.982 l Weight of Solids 99.952 Weight Percent Solids 33y, i

s

• Notel Sodium Bicarbonate does not appear as NaHNO3 i at elevated pH s i'

BELOO47:3RM 4

e O west valley

" "- "='" "" $ " 2 6

. Revision Number 0 Demonstration Proj. ect Revision Date 05/02/91 Engineering Release #2079 TEST PROCEDURE PROCEDt.'RE FOR QUALIFICATION OF DIE FCMIliAL RECIPE FOR CLMENT SOLIDIFICATION OF SI.UDGE VASil LIQUIDS PREPARED BY M , d . Ib d u /( M c_ M. N. Baker Cognizant Engine'et' APPROVED BY 46s # D. C. Meess cognizant Systern Design Manager APPROVED BY emw 2.., _ D. L. Shugars Quah'tf Ashur'atEe' Managfi ' "

APPROVED BY %dbWh\k Rad (ajion and Safety Manager D. J. Harward APPROVED BY S d, Om aa _

J. C. Cvynar ProVess Contrbl Engineering West Valley Nuclear Services Co., Inc.

P.O. Box 191 BELOO48:3RM s

West Valley, NY 14171-0191 WV 1816, Rev.1

WNS TP.026 Rev. O RECORD OF REVISION PROCEDURE If there are changes to the procedure, the revision number increases by one.

These changes are indicated in the left margin of the body by an arrow (>) at the beginning of the paragraph that contains a change, gample_:

> The arrow in the margin indicates a change.

Revision On Rev. No, Desc'.*1ption of Changes Dated PaSe(s) 0 Original Issue All 05/02/91 O

W 1807. Rev. 1 i BELOO48:3RM

WNS TP 026 Rev, O RECORD OF REVISION (C0tiTI!NATIOli SHEET)

O Rev. No. Description of Changes "faghYE) "

Dated s

O W 1807. Rev. I ti BELOO48:3RM

WVNS.TP.026 PROCEDURE FOR QUALIFICATION OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS Rev. 0 1.0 SCOPE 1.1 This work is required to demonstrate the stability of the

" nominal" waste form recipe developed under Test Request VVNS.TRQ.025. Characteristics which will be tested are required by 10 CTR 61, Code of Federal Regulations. Title 10, " Licensing  ;

Requirements for Land Disposal of Radioactive Waste." and the .

USNRC Branch Technical Position on Waste Form, revision 1, dated January , 1991. This work is part of WVNS.TPL.70 11. " Test Plan for the Waste Form Qualification Program for Cement Solidification of Sludge Wash Liquid."

1 1.2 Vork will be performed with a simulant representing the actual i vaste liquid. After all tests have been performed, a small sample of the actual slud6e wash product will be solidified using the qualified recipe. This sample will be subjected to compressive j strength testing. This work will be performed under VVNS.TRQ.029.

a i

1.3 Work will be performed using both cubes (2"x2"x2") and cylinders

(3" diameter x 6" long) cast from full scale drums processed in the Cement Solidification System (CSS). The purpose of duplicate i tests is to establish a correlation between the full scale l cylinders, full scale cubes, and lab. scale cubes, 1

2 1.4 A curve of compressive strength vs. cure time will be established

, for both cubes and cylinders. ,

1

1.5 The maximum practical compressive strength of the waste form will be verified at cure times of 7, 14, 21, 28, 35, and 42 days.

i 1.6 Thermal cycling stability of the waste form will be tested in

accordance with ASTM Standard B.553, section 3.1.

i 1.7 Resistance to leaching of radionuclides will be performed using a simulant liquid " spiked" with Cesium.137, Strontium 90, and Plutonium.241, in accordance with the Branch Technical Position, appendix A.II.F. and ANSI /ANS Standard 16.1. Preliminary testing

, will be performed to identify the leachant as deionized water or l synthetic seawater.

{ 1.8 After curing for a minimum of 28 days, as indicated by the compressive strength vs. time testing _in paragraph 1,4 above, at-least three (3) cylinders _will be immersed for a period of

i. 90 days. Following immersion, the specimens shall be subjected to compressive strength testing. A mean post immersion l()

compressive strength not less than 75 percent of tha mean' ,

!V I

BEL 0048:3RM 1 l

WVNS.TP 026 Rov. O compressive strength (paragraph 1.4 above) is required. If the ,

O mean post immersion compressive strength is less than 75 peicent of the mean pre-immersion compressive strength, the immersion interval shall be extended (using different specimens) to 120, i

150, and 180 days. This testing is required to establish that the compressive strengths level off and do not continue to decrease with time.

1.9 Por one (1) specimen, the leechability of the chromium shall be evaluated in accordance with the Toxicity Characteristic Leaching Procedure (TCLP) .

2.0 DEFINITIONS AND ABBREVIATIONS 2.1 Definitions Cement - Dry Portland Type 1 cement in accordance with ASTM Standard C.150 85 Cement Blend A homogenous mixture of Portland Type I cement with 5.7 1 1.7 percent technical grade flake or granular form calcium nitrate with NO ammonium nitrate.

Cast . A cube or cylinder specimen produced in the mixer, then scooped into the mold Cube A 2"x2"x2" cast specimen produced either in a lab mixer or O the full scale mixer cylinder - A cast epecimen 3" diameter x 6" long produced in the full scale mixer.

Demineralized Water water having a conductivity less than 5 micromho/cm at 25 degrees Celsius and a total organic carbon content less than 3 parts /million.

i l Synthetic Seawater a combination of various inorganic compounds as follows:

i Sodium chloride 23.497 grams Magnesium Chloride 4.981 grams

Sodium Sulfate 3.917 grams Calcium Chloride 1.102 grams Sodium carbonate 0.192 grams Potasium Bromide 0.096 grams Demineralized Water 965.551 milliliters i

l O

l' BELOO48:3RM ,

UVNS TP 026 Rev 0 2.2 Abbreviations ACM - Analytical Chemistry !!ethod A&PC Analytical & Process Chemistry ACP - Analytical Chemistry Procedure CSS Cement Solidification System DAS - Data Acquisition System IVP - ~ Industrial Work Permit IRTS Integrated Radwaste Treatment System LWTS Liquid Waste Treatment System PCE - Process Control Engineering QA - Quality A-surance R&S - Radiation and Safety SIP - Special Instructions Procedure SOP - Standard Operating Procedure TDS Total Dissolved Solids 3.0 RESPONSIBILITIES 3.1 Integrated Radwaste Treatment System (IRTS) Operations personnel an~r.te the Cement Solidification System (CSS) in accordance with a- 41-01 and WVNS-PCP-001 to produce the full scale drums of d dified simulant liquid required for this test procedure.

1_ IP.T5 Support Engineering provides technical support as necessary, g 3.1 t'rc,c is Control Engineering (PCE) provides technical direction,

, and compares the test data to the Test Request requirements.

3.4 Quality Services provides surveillance to ensure that the requirements of this test procedure are satisfied, and verifies tha; portions of the test (where independent verification is required) were performed.

3.5 Quality Services performs compressive strength testing of cylinders in accordance with Q1P-027.

3.0 Analytical & Process Chemistry performs the following; a) chemical analyses required to confirm that the test liquid accurately simulates the sludge wash liquid; b) perform TCLP leach testing for radionuclides; c) perform TCLP leach testing chromium; d) perform thernal cycling test; e) perform immersion test; f) perform compressive strength tests on cubes and cylinders.

3.7 Radiation and Safety (R/S) monitors radiation and contamination levels, r

BEL 0048:3RM __ _ _ _ _ _ _

WNS TP 026 Rov. 0 4.0 TOCLS, EQUIPMENT, COMPONENTS, AND REFERENCES 4.1 Tools and Equipment 2" x 2" x 2" ne'.y cube molds 3" diameter 4 6" long cylinder molds per ASTM Standard C 470 poly bags solid sample (s) transport container (s) 5 gallon high density reelyethlene pails with lida 20 Liters Demineralized Water 20 Liters Synthetic Seawater recording thermometer readable to +/ 0.5 degree Celsius J 4.2 Components CSS equipment fully operational Despatch Series 16000 Environmental Chamber fully operational Forney Model ET-40-DR Compressive Strength Testin5 Unit fully operational 4.3 References l 4.3.1 CSS (System 70) Standard Operating Procedures 4.3.2 EP 11 001, Test Control i

4.3.3 EP 11-003, Development Test Control

4.3.4 WNS-TPL-70 011, Test Plan for Waste Form for Cement i Solidification of Sludge Wash Liquid 4.3.5 WNS-TRQ 026, Test Request for Waste Form Qualification j Work for the Nominal Recipe for Cement Solidification of Sludge Wash Liquid 4.3.6 WDP-010, WNS Radiation Controls Manual 4.3.7- WDP 011,- WNS Industrial Hygiene & Safety Manual

_4.3.8 USNRC Branch Technical Position on Waste Form, Revision 1, dated January, 1991 l

BEL 0048:3RM i

WNS TP 026 Rov 0 4.3.9 ASTM C 109 Standard Test method for Compressive Strength of Hydraulic Cement Mortars (Using 2 in, or 50 mm Cube s Specimens) 4.3.10 ASTM C 39 Standard Test Method for Compressive Strength of Cylindrical Concrete Specimens 4.3.11 ASTM B 553 Star.dard Test Method for Thermal Cycling of Electroplated Plastics 4.3.12 ANSI /ANS 16,1 American National Standard Measurement of the Leachability of Solidified Low Level Radioactive Wastes by a Short term Procedure 4.3.13 SIP 91 01 LWTS/ CSS Integrated Test 4,3 14 QIP 027 Quality Inspection Procedure for Compressive Strength Testing of Cement Cylinders 4,3.15 WVNS TRQ 029. Test Procedure for Production of Cement Product from Actual Sludge Wash Liquid 4.3.16 WNS TRQ 025, Test Request for Development of the Nominal Recipe for Cement Solidification of Sludge Wash Liquids 4.3.17 WNS-TP 025, Test Procedure for Development of the Nominal Recipe for Cement Solidification of Siudge Wash-Liquids 4.3.18 ACP 7,2, Administrative Control Procedure for Laboratory Safety 4,3.19 ACM 4701, Analytical Chemistry Method for Destructive Test of Cement Specimens 4.3,20 ACM-4801, Analytical Chemistry Method for Cement Test Cube Preparation Met)-'d 4.3.21 ACM 5901, Analytical Chemistry Method for Toxicity 4

Characteristics Leachin& Procedure (TCLP) 4,3.22 ACM 6200, Analytical Chemistry Method for Operation of Despatch Environmental Chamber 4.3.23 ACM 6300, Analytical Chemistry Method for Leach Index of

Cement Specimens 4.3.24 ACM-6400, Analytical Chemistry Method for Immersion Testing of Cement Specimens O

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BELOO48:3RM l t

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WVNS-TP 026 Rev. 0 5.0 GENERAL INFORMATION 5.1 The nominal recipe being qualified by this teet procedure will be developed under Test Request WVNS-TRQ-025, and ast Procedure VVNS TP 025.

5.2 Resulta of this testing will be compared to the results obtained under WVNS-TRQ 025.

5.3 Quality Assurance should be notified prior to the start of this work.

5.4 OPERATORS SHOULD PERFORM FREQUENT CHECKS ON SYSTEMS THAT ARE TURNED ON OR SHUT DOWN TO ASSURE THAT THE SYSTEM DOES WHAT IS EXPECTED, I.E. , WATER FLOWS , PRESSURE RISES , ETC. IF THE REQUIRED ACTION THAT IS SUPPOSED TO HAPPEN DOES NOT HAPPEN, (1) STOP DO NOT PERFORM THE NEXT STEP, (2) - SECURE THE SYSTEM IN A SAFE MODE, AND (3) - NOTIFY THE COGNIZANT A&PC SCIENTIST OR COGNIZANT EFGINEER IMMEDIATELY.

6.0 EMERGENCY RESPONSE 6,1 For emergencies in the A&PC Lab, responses will be as directed by ACP 7.2 and WVDP 010, 6.2 For emergencies elsewhere in the plant, responses will be as directed by WVDP 010.

7.0 COMPRESSIVE STRENGTH VS. TIME

. 7.1 After curing 7 days in the controlled temperature chamber and at room temparature as discussed in section 13.1 below, a total of

, three (3) cubes will be subjected to compressive strength testing i per applicable steps of ASTM Standard C-109 and the applicable steps of ACM 4801.

7.2 After curing 14 days in the controlled-temperature chamber and at

room temperature as discussed in section 13.1 below, a total of three (3) cubes will be subjected to compressiva strength testing

! per applicable steps of ASTM Standard C 109 and the applicable l steps of ACM-4801.

7.3 After curing 21 days in the controlled-temperature chamber and at room temperature as discussed in section 13,1 below, a total of three (3) cubes will be subjected to compressive strengen testing per applicable steps of ASTM Standard C 109 and the applicable steps of ACM-4801.

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BEL 0048:3RM 6-l

i WVNS-TP-026 Rsv. 0 7.4 After curing 28 days in tha cor, trolled temperature chamber and at i room temperature as discussed in section 13.1 below, a total of ten (10) cubes will be subjected to compressive strength testing per applicable steps of ASTM Standard C-109 and the applicable steps of ACM 4801. A compressive strength greater than 500 psi is desired. Refer also to the Branch Technical Position, appendix A.II.B.

i i 7.5 After curing 35 days in the controlled temperature chamber and at room temperature as discussed in section 13.1 below, a total of 4 three (3) cubes will be subjected to compressive strength testing

per applicable steps of ASTM Standard C-109 and the applicable steps of ACM-4801.

7.6 After curing 42 days in the controlled-temperature chamber and at room temperature as discussed in section 13.1 below, a total of three (3) cubes will be subjected to compressive strength testing per applicable steps of ASTM Standard C-109 and the applicable steps of ACM 4801.

8.0 THERMAL CYCLING 8.1 The heating / cooling chamber shall conform to the description given in ASTM Standard B 553. The thermal cycling test shall ba 4

performed in accordance with ACM 6200, 8.2 Because ASTM Standard B 553 addresses thermal cycling of

[\

\~-

electroplaced plastics, some modifications to the test wethod are required. Testing will be performed on " bare" (i.e., not in a container) cylinders.

.i 8.3 After a cure time of at least 28 days, or longer, as identified in

section 7 above, unbagged cylinders should be placed in the test

! chamber, and a series of thermal cycles shall be carried out in accordance with sections 5.4.1 through 5.4.4 of ASTM Standard B 553, with the additional provision that the specimens should be allowed to come to thermal equilibrium at the high (60 degrees C) and low (-40 degrees C) temperature limits. Thermal equilibrium

should be confirmed by measurements of the centerline temperature of at least one (1) specimen per test group.

8.4 Three (3) cylinders should be subjected to the thermal cycling tests.

8.5 Following exposure of 30 thermal cycles, the cylinders should be i

examined visually, and found to be free of any evidence of

, significant cracking, spalling, or bulk disintegration. The specimens should be photographed at this time, as a record of the

'\

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BELOO48:3RM l l

l

- .n.,- , . - , - _ . - .. . ,- --

WVNS TP 026 Rsv. O cylinder condition without assessing whether the defects'are si gnificant. Visible evidence of significant degradation would be indicative of a failure of the test.

8.6 If there are NO significant defects, the test cylinders shall be

subjected to compressive strengen testing per QIP 27 or ACM-4701

and applicable sections of ASTM Standard C 39. A mean compressive

! strength greater than 500 psi is desired.

8.7 Quality Assurance may perform a surveillance of the thermal cycling, inspection process, or compressive testing.

] 9.0 LEACH TESTING OF RADIONUCLIDES

! 9.1 For this test, a cylinder will be prepared in the A&PC Lab, using 4

simulant " spiked" with Cesium-137, Strontium-90, and Plutonium 241.

9.2 After curing, the cylinder will be immersed in either deionized

, water or synthetic sea water for a period of 5 days, as discussed in the Branch Technical Position, appendix A.II.F.

9.3 The most aggressive leachant (deionized water vs. synthetic sea water) will be identified by performing 24-hour (or longer) leaching measurements on both leachants, and the leachant which exhibits the lowest leach index (highest leach rate) will be used for the remaining tests.

1 O 9.4 Leach testing will be performed in accordance with the Branch Technical Position, appendix A.II.F, and ANS/ ANSI Procedure 16.1, and ACM-6300. The cylinder will be immersed in a measured volume of water, which is changed at intervals of 2, 7, 24, 48, 72, 90, and 120 hours0.00139 days <br />0.0333 hours <br />1.984127e-4 weeks <br />4.566e-5 months <br />. Upon removal of the cylinder (in accordance with j

ANSI /ANS 16.1, section 2.3) the leachant will be analyzed for Cesium-137, Strontium-90, and Plutonium-241 concentration. Each

) concentration is expressed as an "L" value for that leaching 4

interval. The "L" value is the logarithm of the inverse of the i

effective diffusivity for each isotope. The "Leachability Index" is the arithmetic mean of the "L" values. The Leachability Index, as calculated in accordance with ANS/ ANSI lf.1, should be greater

! than 6.0.

I 10.0 IMMERSION TESTING 10.1 No " Standard Method of Test" for immersion testin6 has been adopted for low-level radioactive waste. The test, however, is discussed in the Branch Technical Position, appendix A.II.G. and shall be performed in accordance with ACM-6400.

10.2 After a cure time of 28 days, or as indicated by the compressive strength vs. cure time testing performed in section 7.0 above, at least three (3) cylinders will be immersed for a period of 90 days.

4 BEL 0048:3RM _ _ _ . .

WVNS TP 026 Rav 0 10.3 The immersion liquid shall be either deionized water or synthetic sea water. The immersion liquid will be selected during the leach testing described in section 9.3 above.

$ 10.4 Following immersion, the cylinders should be examined visually, and should be free of any evidence of cracking, spalling, or bulk

disintegration. The specimens should be photographed at this 4

time.

t 10.5 If there is no evidence of significant degradation, the specimens shall be subjected to compressive strength testing per QIP-27 or ACM-4701 and applicable sections of ASTM Standard C-39. Post-l tmmersion mean compressive strengths should be greater than or equal to 500 psi, and not less than 75 percent of the pre-immersion (as-cured) mean compressive strength.

)' 10.6 If the post immersion mean compressive strength is less chan 75 percent of the as-cured specimens' pre-immersion mean compressive strength, but not less than 500 pai, the immersion testing interval should be extended (using additional specimens) to a

, minimum of 180 days. For these cases, compressive strength testing should be conducted after 120, 150, and 180 days of immersion to establish that the compressive strengths level off and do not continue to decrease with time.

10.7 Quality Assurance may perform surveillance of the immersion, post-immersion inspection, and compressive strength testing processes.

. 11.0 LEACH TESTING FOR HEAVY METALS

, 11.1 One (1) cured sample specimen will be used for Toxicity Characteristic Leaching Procedure (TCLP) testing for Chromium.

11.2 A total of 100 grams of the sample material will be crushed and t

extracted in accordance with ACM-5901.

. 11.3 The resulting extract liquid will be analyzed for the presence of

! chromium,

! 11,4 A Chromium concentration less than the regulatory limit of 5.0 mg/L is required.

12.0 SAMPLING j 12.1 Lab scale (cube) samples will be produced in accordance with L

ACM 4701.

12.2 Full-scale cube and cylinder samples will be produced in accordance with SIP 91-01.

O BELOO48:3RM ,

-m- w

WNS -TP-026 Rov. 0 12.3 A total of forty (40) cubes and fifty (50) cylinders will be

required in accordance with Table 1.

( 13.0 CURING 13.1 Lab scale cube specimens, full scale cube specimens, and full-j scale cylindrical specimens will be cured, to the extent i practical, at the same conditions as full scale drums, as j discussed in the Branch Technical Position, appendix A.III.B.

13.2 When processing full-scale drums under SIP 91 01, a drum will be equipped .rith thatuocouples and a temperature re corder. The drum j centerline temperature will be plotted as a function of time.

j This temperature profile will be duplicated, to the extent j practical, for all samples cured outside of the drum, l 13.3 For this procedure, the samples will be bagged and cured in a l controlled temperatura chamber for a period of time equivalent to the peak hydration period. This period is taken to be that required for the drum centerline temperature to decrease to 30 degrees celsius.

I 13.4 The chamber will be equipped with a calibrated thermometer, and continuous temperature recorder, 13.5 All samples will be kept in sealed containers and/or poly bags during curing and storage, as discussed in the Branch Technical

Position, appendix A.III.C. This is intended to simulate the

'g environment in a sealed drum.

14.0 COMPRESSIVE STRENGTH TESTING OF CYLINDERS t

i 14.1 The maximum practical compressive strength of the waste form will be evaluated as discussed in the Branch Technical Position, appendix A.II.B.

(

14.2 Capping of cylindrical specimens shall be performed in accordance with the applicable steps of ASTM Standard C-39 and QIP-27.

14.3 Compressive strength testing of cylinders shall be performed in accordance with the applicable steps of ASTM Standard C-39 and QIP-27.

l 14.4 A minimum of ten (10) cylinders shall be tested.

14.5 A mean compressive strength in excess of 500 PSI is required.

14.6 Cylinders shall be bagged prior to compressive strength testing, in accordance with QIP 27.

f 4

s BEL 0048:3RM I

WVNS TP 026 Rsv. O TABLE 1 j Ih Sample Schedule for Qualification of the Nominal Recipe hb'l for Cement Solidification of Sludge Wash Liquids Elapsed Event Cubes Cylinders Days O Cast cubes / cylinders 40 50 Begin cure 7 7-day compressive 3 3 strength 14 14-day compressive 3 3 strength 21 21-day compressive 3 3 strength 28 28-day compressive 10 10 strength 28 immersion starts (BELOW) (BELDW) 23 thermal cycling - 4 4

s 28 TCLP -

1 35 35-day compressive 3 3 strength 42 42-day compressive 3 3 strength 118 Post-immersion 3 3 Compressive Strength 148 Post-immersion 3 3 Compressive Strength 178 Post-immersion 3 3 Compressive Strength 208 Post-immersion 3 3 Compressive Strength TOTAL 37 42 tp).

s--

BELOO48:3RM WNS TP-026 i Rav, O i

TMM 2 I -

Salt Concentrations for the " Nominal" Simulant Recipe Based on 128.5" Heel Constituent Formula Weight a

1 Sodium Nitrate 35,62 f' NANO 3 Sodium Nitrite NANO 2 33*00

{ Sodium Sulfate Na2SO 4 21,13 Sodium Bicarbonate NaHCO 3

• a j Potassium Nitrate KNO 3 2.23 Sodium Carbonate Na2CO 3 6.02 Sodium Hydroxide NaOH 0,22 i Sodium Chromate Na2C ro4 0.308 Sodium Chloride NaC11 0,234 Sodium Phosphate Na3PO4 0.190 Sodium Holybdate Na'2Ho04 0.040 Sodium Borate Na230 47 0.024 Citric Acid 0,032 CH0687

Oxalic Acid C0H 242 0,032 '

l Tartaric Acid CH0 466 0,032 Vater HO2 203.03 Total Weight 302,982 1

, Weight of Solids 99.952 i

1 Weight Percent Solids 33%

i 4

i

,vh)

• Note: Sodium Bicarbonate does not appear as NaHCO3 at elevated pH BELOO48:3RM _

WrB-TP-026

'Rav. O' O

Figure 1: Despatch Series 16000 Environmental Chamber with MRC 7000 Controller p (Oven Fan@ rear)

Oven Chamber located cli Mnnocouple Port -

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_(

MO - Recording Chart i m ]N,

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! Power Switch'-

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West Valley Doc. N e er WynS-TRO-m e Demonstration Project Revialon " = ec o Revision Date 04-05-91 Engineering Release #2055 TEST REQUEST DEVELOPMENT OF THE PROCESS CONTROL P ARAMETERS FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS PREP ARED BY 894 @ M- _ M. N. Baker Cognisant Engineer APPROVED BY / D. C. Meess Cognizant System Design Manager APPROVED BY b'J N Chv M/' *D. L. Shugars Quality Asf urance Manager AP ROVE BY m # D. J. Harward I Ka'dilti dnd Saf et'y Map'iger 4 f1/9 I J. C . C wyn ar APPROVED BY 4 6 Coe l

IRW) Process \) Control Engineering West Valley Nuclear Services Co.,Inc.

P.O. Box 191 BEL 0050 :3RM West Valley, NY 14171-0191 WV-1816, Rev.1

~..-._. -- - - .~. - - .-----. - .- . .- -

)

WNS TRQ.028

j. Rev. 0 -

RECORD OF REVISION 1

I j PROCEDURE I

If there are chanBes to the procedure, the revision number increases by one.

I These changes are indicated in the left margin of the body by an arrow (>) at

! the beginning of the paragraph that contains a change, i

a

{ Example; i

l > The arrow in the margin indicates a change.

I l _

Revision On 1 Rev. No. Description of Changes Page(s) Dated i

1 0 Original Issue All 04-05 e l

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W-1807, Rev. 1- 1 l BELOO50:3RM i-P 9

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i WNVS TRQ 028 Rev 0 1

DEVELOPMENT OF THE PROCESS CONTROL PARAMETERS FOR CEMENT l SOLIDIFICATION OF SLUDGE WASH LIQUIDS 4

1 7

1.0 INTRODUCTION

i

! 1.1 This work is required to demonstrate the stability of the vaste form 1 at variable cement recipe and waste parameters. The characteristics l which will be tested are required by 10 CFR 61, Code of Federal Regulations, Title 10. " Licensing Requirements for Land Disposal of j Radioactive Waste " and the USNRC Branch Technical Position on Waste

Form, Revision 1, draft dated December 1990.

I

1.2 Work will be performed with a simulant representing the actual vaste liquid.

1.3 Work will be performed using 2" x 2" x 2" cubes prepared in the A&PC Laboratory.

1.4 Work will include the formulation of a series of solutions

, representing variations in the waste liquid, which will be mixed 1

with the cement blend and other additives. The effect of variations in additives will also be evaluated, as discussed in the Branch

. Technical Position. Appendices A.V. and A. VI.

l 1.5 Single-component as well as multi variant tests will be performed.

, The test matrices are shown in Tabres 1 and 2.

i 1.6 Test Procedure WVNS-TP-028, providing instructions for testing in

accordance with this Test Request shall be issued by Analytical &

l Process Chemistry per EP 11 003, l 1.7 A Test Summary Report documenting the results of this testing shall l be issued by the Cognirant Test Engineer per EP 11-003.

! 2.0 OBJECTIVES

2.1 Single-Variant Testing l The effects of variations in the following waste stream constituents will be evaluated

i 2.1.1 The " nominal" Sludge Wash simulant with high and low amounts

, of Sulfates.

, 2.1.2 The " nominal" Sludge Wash simulant with high and low amounts

of Organics.

l 4

d BEL 0050:3RM 1 d

VVNS TRQ 028 .

Rev. 0 l i

i 2.1.3 The " nominal" Sludge Wash simulant with high and low amounts of Aluminum, 2.1.4 The " nominal" Sludge Wash simulant with a hic,h Nitrate-to Nitrite ratio as well as a low Nitrate to Nitrite ratio, f 2.1.5 The " nominal" Sludge Wash simulant will be mixed with the

" nominal" cement recipe as a baseline. A minimum acceptable

{

! compressive strength for all tests is 500 PSI as discussed in j the Branch Technical Position Appendix A.II.B. The

}

" nominal" Sludge V&sh simulant composition and " nominal"

! cement recipe are shown in Tables 3 and 4, respectively.

i The single variant test matrix is shown in Table 1.

t 2.2 Multi Variant Testing The effects of variations in the following recipe parameters will be evaluated:

j. 2.2.1 The maximum as well as the minimum water to-cement ratio.

2.2.2 The maximum as well as the minimum Total Dissolved Solids j (TDS) in the vaste stream.

! 2.2.3 The msximum as well as the minimum anticipated Borate content 4 in the vaste stream; noting that Borates are present in the waste stream only in trace amounts, and are not expected to affect the performance of the vaste form.

l y

2.2.4 The maximum as well as the minimum range of Calcium Nitrate j

recipe enhancer in the ceanent blend.

4

2.2.5 The maximum as well as the minimum anticipated pH of the i waste stream.

3

! 2.2.6 The maximum as well as the minimum anticipated Phosphate content in the waste stream; noting that Phosphates are I present in the waste stream only in trace amounts, and are not expected to affect the performance of the waste form, j 2.2.7 The maximum as well as the minimum range of antifoam recipe enhancer to be added to the waste.

2.2.8 -The maximum as well as the minimum range of. Sodium Silicate

! recipe enhancer to be added to the waste.

i 2.2.9 The maximum as well as the minimum anticipated mix time in

] -the-process.

The multi-variant test matrix is shown in Table 2.

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WVNS TRQ 028 Rev. 0 4

3.0 SAFETY It 3.1 Industrial safety practices shall be as described in the WVNS Hygiene & Safety Manual, VVDP 011.

j

] 3.2 Radiological work will be performed in accordance with the VVDP j Radiological Controls Manual, WVDP 010 j 3.3 Safety practices specific to the A&PC Laboratory will be as j described in ACP 7.2, Safety Practices for the Analytical & Process

! Chemistry Department.

I i 4.0 EQUIPMENT CONFIGURATION 3

4.1 All lab equipment will be set up in accordance with Test Procedure VVNS-TP 028 as directed by the Cognizant A&PC scientist or Cognizant

]

A&PC technician.

]'

l 4.2 Balances and other wei6 hing equipment accurate to 0.01 gram will be i calibrated prior to use in accordance with ACP 7.1.

1 l 4.3 Mixing will.be performed in a manner which duplicates, to the extent practical, the full scale mixing equipment, including mixing speed,

, order of addition, mixing time, energy introduced to the mixture, l etc., as discussed in the Branch Technical Position.

I appendix A.III.A. .

( 4.4 Curing of the samples will be performed in a manner which i duplicates, to the extent practical, the curing temperature profile

encountered in the full-scale drum, as discussed in the Branch d

Technical Position, appendix A,III.B. A temperature-controlled chamber will be utilited.

i 4.5 Calibration of compressive strength testing eqttpment will be in l accordance with ASTM Method C-39 and C-109.

i l 5.0 SAMPLING l 5.1 Samples will be produced in the quantities and frequencies specified

in VVNS TP 028.

i 5.2 The test matrix is shown in Tab),es 1 and 2. Each test will be conducted with the variables adjusted to the maximum (shown by a

"1") or the minimum value (shown by a "0"). Independent as well as

. dependent variables will be evaluated.

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SEL0050:3RM 3 4

. - - , , , - - , ., - - ,,,,,,.-n,., , , - - , --, ,-,n-,r-,- - - , - - -

k'VNS TRQ-028 j Rev, O

}

i i . 6.0 PERSONNEL QUALIFICATION l

{- 6.1 Testing will be performed by qualified Analytical & Process Chemistry Technicians using Wl;S-TP-028 and approved Analytical j Chemistry Methods (ACM's) under the cognizance of an A&PC scientist.

i

a. Radiochemistry "B" Technicians qualified to WNS-QS 014 f b, Radiochemistry "A" Technicians -qualified to WNS-QS 016 1 .,

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yr .v..v- e v - , , , .,-.m ~r ,

e e,, > ... .,,,-., ..m.,n.,,,m.,,.., .,c.,., ,., , - . , .y e f r m w , . .r y v,-,

__. . _ _ . _ ~ . - . _ . . . _ _ . . . - . _ _ _ . . - . . - . _ . -

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J WVNS-TRG-02t1

• Rev. C' f

]

TABLE 1: Single-variant Test Matrix 4

l'

.i Aluminum Oroanics Hioh/ Low Sulfates Nitrites / Nitrates i

4

• Test 1 Nominal Nominal Nominal Nominal 2 1 0 0 0 1

3 0 1 0 0 s

4 Q O 1 O

{

t

5 O O o 1 KEY

1 = Variant added at maximum value

! 0 = Variant added at minimum value k

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Rev. 0 4

TABLE 2: MULTI-VARIANT TEST MATRIX Test Total Water to calcium Mix Anti Sodium

, Number Solide Cement Nitrate pH Time foam Silleate phosphate Dorates 1 1 1 1 1 1 0 1 0 0 lI i 2 1 0 0 1 0 1 1 1 1 3 0 1 1 1 0 0 0 0 1

, 4 0 1 1 0 1 0 1 1 1 1 5 1 0 1 0 0 1 1 0 1 6 1 0 1 1 1 0 0 0 0 7 1 0 0 0 0 0 0 0 1 8 1 0 0 0 1 0 0 1 0

! 9 0 0 1 1 1 0 1 0 0

, 10 1 1 1 0 0 1 0 0 1 11 1 0 1 0 1 0 1 0 1 12 0 1 0 0 1 0 -

0 0 0

! 13 0 0 0 1 0 0 0 1 0 14 0 1 0 0 0 1 1 1 1 j 15 1 1 0 1 0 1 0 1 1 18 0 0 0 1 1 0 0 0 1 j 17 1 1 1 0 1 0 0 0 1

! 18 1 0 0 0 1 1 0 0 1 19 0 0 1 0 0 1 0 1 1 20 1 0 0 0 0 1 0 1 0 i 21 1 1 1 1 1 1 1 1 1 3 U 1 1 0 1 0 0 0 0 0 23 1 1 1 0 0 0 0 1 0 24 1 1 0 0 0 1 1 1 0 25 0 0 0 0 0 1 1 0 0 26 0 0 1 0 1 1 0 0 0 27 0 0 1 0 1 0 0 1 1 1 28 0 1 0 0 0 0 0 1 1 29 0 1 0 0 1 1 0 1 1 4 30 0 0 0 1 1 1 0 1 0

31 0 0 0 0 1 0 1 0 0 32 1 0 0 1 1 1 1 0 0 l 33 0 1 0 1 0 0 1 1 0 l 34 0 1 1 0 0 0 1 0 0 l 35 1 0 1 0 0 0 1 1 0 l 36 .- 0 1 0 0 0 1 0 0 0

! 37 1 1 1 0 1 1 0 1 0 38 1 1 0 1 1 0 0 1 1 i 39 1 1 1 1 0 0 1 1 1 40 0 1 1 0 1 1 1 0 0 41 0 1 1 1 1 1 1 0 0-42 0 1 0 1 1 1 5 1 0 43 0 0 0 0 0 0 1 1 1

. 44 0 1 1 1 1 0 0 1 0 45 1 1 0 0 1 0 i 1 0 l 46 0 1 1 1 0 1 0 1 0

' -47 1 0 1 1 0 0 0 1 1

! 48 0 0 0 1 0 1 ') 0 1 49 1 0 1 1 0 1 0 0 0 50 0 0 1 1 1 1 1 0 1

51 0 0 1 1 0 1 1 1 0 4 52 1 0 0 1 0 0 1 0 0 53 1 0 1 0 1 1 1 1 0 54 0 0 1 1 0 0 1 0 1 55 0 1. 1 1 1 1 0 0 1 56 0 0 1 0 0 0 0 0 0 57 1 0 0 1 1 0 1 1 1 58 0 1 0 1 0 1 1 0 1 I

59 1 1 0 .1 1 1 0 0 0 60 1 1 0 0 0 0 1 0 1 61 0 0 1 1 1 0 1 1 0 62 1 1 0 0 1 1 1 0 1 63 1 0 1 1 1 1 0- 1 1 64 0 0 0 0 1 1 lk o, s 1 1 1 Key:1= VARIANT ADD AT MAX 1 MUM VALUE 0= VARIANT ADDED AT MINIMUM VALUE 6-

?

_ _ ._ _. _ . . . _ _ _ . . .- _ . . _ . _ . _. .~ . . _ _ _ _ _ - - _

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( , . WVNS-Ths 12h Rev. O I

\

TABLE 3: Salt Concentrations for the " Nominal" Simulant l! Recipe Based on 129.5" Heel i

f j Constituent Formula Weicht

]

Sodium Nitrate NANO 3 35.62 l 33.84 Sodium Nitrite NANO 2 i

l Sodium Sulfate Na2SO4 21.13 Sodium Bicarbonate NaHCO3

• l Potassium Nitrate KNO3 2.23

) Sodium Carbonate Na2CO3 6.02 Sodium Hydroxide NaOH 0.22 i Sodium Chromate Na2CrO4 0.308 Sodium Chloride Nacl O.234 Sodium Phoschate Na3PO4 0.190 i Sodium Molybdate Na2 moo 4 2H2C O.040 Sodium Borate Na2B407 0.024 Ci tric Acid C6H807. 0.032

Oxalic Acid C204H2 /s.032

/ Tartaric Acid C4H606 0.032 Water H2O 203.03 Total Weicht 302.982 Weicht of Solids 99.952 Weloht Percent Solids 33*/.

l

• Note: Sodium Bicarbonate does not acoear as i NaHCO3 at elevated pH 3

a

(

, 7

WNS-TRO-028 Rev. O TABLE 4: Lab-scale " Nominal" Eccipe Simulant 96 mL Cement / Calcium Nitrate Blend 140.5 g +/- 1.0 g Antifoam Emulsion 0.3 mL Sodium Silicate 11.0 g +/- 0.5 g i

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Doc. Number WV NS-TP -028

(^) West Valley Re ,1,1,n N m e, 0 Demonstration Project Revision Date 05/01/91 Engineering Release #2076 TEST PROCEDURE PROCEDURE FOR DEVELOPMENT OF PROCESS CONTROL P ARAMETERS FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS PREPARED BY .b L. E. Miennik Cogni::aggrdtier

-?

h APPROVED BY h --

D. C . Meess Cogni:: ant System Desi gn Manager APPROVED BY f/ I' Y/ - / - :a- - ' D. L. Shugars Quality Assurance Manager APPROVED BY &^I # cit MJ 9 5g-$V D. J. Harward Ra6iation and Safety Manager APPROVED BY '/#v 4- M [Cd. J. C . Cwynar Process ControlvEngineering West Valley Nuclear Services Co., Inc.

P.O. Box 191 KMJ0020: 3RM O West Valley, NY 14171-0191 WW1816, Rev.1

WNS TP-028 Rev. O RECORD OF REVISION PROCEDURE If there are changes to the procedure, the revision number increases by one.

These changes are indicated in the left margin of the body by an arrow (>) at the beginning of the paragraph that contains a change.

Example:

> The arrow in the margin indicates a change.

Revision On Rev. No. Description of Changes Page(s) Dated 0 Original Issue All 05/01/91 i

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WNS-TP 028 R4v. O RECORD OF REVISION (CONTINUATION. SHEET)

Re isi

-Rev. No. Description of Changes PagekS)on Dated L

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W-1807, Rev. 1 11 l KMJ0020:3RM i

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- . . ~ . _ ,. . . , . . _ . . , . , . . . _ . . . . _ . - _ . . _ _ . . . . . _ , , _ _ _ _ _ _ _ . . _ . _ _ . _ _ _ _ _ . . _ _ _ . _ . . _ _ . . _ . . - . . . . . _ , _ . - . ,

J TEST PROCEDURE FOR DEVELOPMENT OF PROCESS CONTROL PARAMETERS FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS i

VVNS-TP 028 l

. Rev, 0 1.0 SCOPE I

1.1 The objective of this overall testing criteria is to establish the

windows for full scale production of the sludge wash cement waste

form in which an acceptable product can be made. This is based upon i the require.nents stated in the NRC Technical position paper on Waste

{ Form Rev. 1 Section VI. These windows include variances in the l major chemical components of the simulated sludge wash liquid and d

the cement recipe enhancers. Laboratory specimens, two inch square 4 cubes, will be used to evaluated these windows, i 1.2 The work will include the formulation of a series of individual simulated sludge wash liquids with single component variationc and then a series of individual solutions with multi variances which will be evaluated by a statistical grid (see attachment A),

i 1.3 The single variances will include determination of an acceptable range for sulfate, nitrate / nitrite ratio, organics and aluminum, 1.4 An acceptable range for pH, total solids, phosphate and borate will i\ be evaluated with the use of a multi variance determination. The cement recipe enchancers to be evaluated will be water to cement

, ratio, calcium nitrate four hydrate, antifoam, sodium silicate and mix time and will also be determined by this multi variance j approach.

1.5 After an appropriate curing period, the laboratory specimens will be subjected to compressive strength testing. This testing will provide data on the influence of variations of the chemical composition of the sludge wash liquid and the recipe enhancers on j the compressive strength of the cement vaste form.

2.0 DEFINITIONS AND ABBREVIATIONS 2.1 Definitions

, Cement-Dry Portland Type I cement in accordance with ASTM Standard C-150-85.

Antifoam General Electric AF9020 emulsion of five percent Dimethylsilicone in water. This is used as a cement recipe enhancer to prevent air entrapment in the cement matrix during.high speed mixing.

t 4

KMJ0020:3RM 1

k'VHS -TP.02 8 Rev. O Sodium Silicate.is used as a recipe enhancer in the gelling of the cement vaste form and prevention of excess bleed water.

Calcium nitrate four hydrate-is used as a recipe enhancer in the setting of the cement waste form Cube ACM certified 2x2x2 inch mold used to make laboratory j specimens.

2.2 Abbreviations t

) ACM American Cube Mold i

ASTM American Standards of Testing Materials i

3.0 RESPONSIBILITIES 3.1 Analytical and Process Chemistry will be responsible for the 2

preparation and testing of the laboratory specimens in accordance to a

the applicable steps of the appropriate analytical chemistry methods.

.)

3.2 Quality Assurance will provide surveillance to ensure that the requirements of this testing are satisfied and verify the portions of the testing (where independent verification is required) are j perfo rmed.

4.0 TOOLS , EQUIPMENT, COMPO??ENTS AND REFERENCES

\

4.1 Tools and Equipment Lightnin Lab mixer with high shear impeller or equivalent j -

2x2x2 inch ACM plastic cube molds 1

100 milliliter plastic or glass Braduated cylinder with one milliliter divisions 4

l 500 milliliter polypropylene plastic bottles J

l -

20 milliliter plastic scintillation vials magnetic stirring plate and magnetic stir bar stopwatch or timer accurate to one second top loading balance readable to +/- 0.01 grams i

i

\-

% KMJ0020:3RM 2

WVNS TP 028 Rev 0 4.2 Reagents

( - Portland Type I cement Calcium Nitrate Four Hydrate, reagent grade 1

- Aluminum Nitrate, reagent grade

{

Citric Acid Monohydrate, reagent grade 1

Oxalic Acid Dihydrate, reagent grade d-Tartaric Acid, reagent grade i

j -

Sodium Silicate , technical grade

• 1 j -

Antiform General Electric AF9020*

Sodium Phosphate Mono hydrate, reagent grade 1

4 -

Sodium Tettsborate Decahydrate, reagent grade j -

Sodium Nitrite, reagent grado.

Sodium Nitrate, reagent grade 7

Sodium Carbonate, reagent grade Potassium Nitrate, reagent grade I VM Sodium Hydroxide, reagent grade Sodium Chromate four hydrate, reagent grade l -

Sodium Chloride, reagent grade v

Sodium Molybdate Dihydrate, reagent grade i

• Supplied by IRTS operations

4.3 References l

NRC Technical Position on Waste Form (Revision 1) Dec, 1990 i -

ASTM C 109-86 5.0 GENERAL INFORMATION 5.1 The testing of compressive strength on cement waste form specimens will be used to evaluate the process control parameters and is considered an acceptable criteria on the overall performance of the product as indicated in the NRC Technical Position Rev 1 section VI. The mean compressive strength indicated by any one process

(~

KMJ0020:3RM 3

i-1 -WVNS-TP 028 Rev. O j

! control parameter should yield at least five hundred psi after an i appropriate curing period. Although cement-products nominally 4 achieve seventy five percent of their_ strength in approximately twenty eight days, it has been.~ decided by convention that a curing L period of seven days for laboratory specimens will allow the specimens to gather sufficient strength in order to be evaluated.

! This curing process for process control ~ parameter cement specimens-l -involves the specimens-be placed in an oven or environmental chamber j and sealed individual or in a group-in plastic bags _for sixty one-j hours +/ eight hours at eighty eight degrees. celsius +/- two 4

degrees and then a pentameter test is performed on each specimen to see if the cement has set. The remain time period, for a total of seven days +/ eight hours, the specimens will cured at twenty-degrees celsius +/ five degrees. At this point the specimen will be tested for compressive strength by_ the applicable . steps of ACM.

l 4701.

l' a The results from this testing will provide a basis on the effects of l variances in the full scale process as indicated above and if these

! variances and at what extreme will still produce an acceptable j product defined by the NRC Technical Draft on Waste Form Rev 1.

j 6.0 PROCEDURQ l

6.1 Prerequisite Oven or environmental chamber should be set at proper temperature

- as defined in-section 5.0 Balances shall be calibrated according to ACP 7.1

- Safety procedures shoulo be reviewed in ACP 7.2 6.2 A nominal recipe simulant shall be prepared (see attachment B) and at least ten cubes shall be made according to-ACM-4801 within an eight hour period. This is considered to be cube set #1. After an appropriate curing period, the cubes will be subjected to compressive strength testing as described in ACM-4701.

6.3 A low sulfate and high sulfate sludge wash simulant shall be-prepared (see attachment B) and a least five cubes'from each of these simulants shall be made according to ACM-4801 within an eight hour period. This is considered cube set #2. After an appropriate curing period, the-cubes will be subjected to a. compressive strenSth test as-described in'ACM-4701.

6.4 A low organic and high organic. sludge, wash simulant.shall be prepared (see attachment B) and at least.five cubes from each of the-simulants shall be made according to_ACM-4801 within an eight hour period. This is considered to be cube set-#3. .After an' appropriate curing pericd the-cubes will_be subjected to a compressive-strength-test as described in ACM 4701.

D loiJ0020:3RM 4 l

_ .. _ .._._ _ a; _ _ _ . _ . _ . _ _ ,. . --

WNS TP 028 ,

Rev. O  !

6.5 A variance in nitrate to nitrite ratio simulants shall be prepared  ;

(see attachment B) and at least five cubes from the each of the two simulants shall be made according to ACM 4801 in an oi6h t hour period. This is considered cube set e4, After an appropriate ,

curing period the cubes will be subjected to a compressive strength l test as described in ACM.4701, t 6.6 A sludge wash simulant containing aluminum shall be prepared (see attachment B) and at least five cubes from this simulant shall be made according to ACM 4801 in an eight hour period. This is .

considered to be cube set e5. After an appropria'.a curing period,  !

the cubes will be subjected to a compressive strength test as described in ACM 4701.

6.7 The determination of nine additional factors including cement to water ratio, total solids, calcium nitrate four hydtate, pH, antifoam, sodium silicate, phosphate, borate and mix time will be investigated by multi variance statistical Grid. The grid will be made up of sixty four cubes with variation of the component from their extremes boundaries. This it considered cube set #6, The  ;

statistical grid will evaluate these comoonents influences on the compressive strength and to what degree. These cubes will be made (see attachment A) according to ACM.4801 in an eight hour period at -

four per day.

Fac to r,s Hip.h Q), Low (0) Nominal total Solids (t) 37 25 31 pH 12.5 11 12 Calcium Nitrate Four Hydrate (t) 12.0 3.0 5.7 l antifoam (mis) 0.6 0.1 0.3 Sodium silicate (grs) 22 5 11 mixtime (mins) 16 4 8 phosphate (gr/L) 1.6 0.4 0.8 borate (mg/L) 17,4 4.3 8.7*

(boron) water to cement (ratio) 0.80 0.30 0.61

• This will be added as Sodium Tetraborate Decahydrate to obtain a nominal concentration of 0.001 mg/ml boron, j After a appropriate curing period, these cubes will be subjected to a compressive strength test as described in ACM 4701.

O YMJ0020:3RM 5

~ r n -w , - --- -, , m,, , - = , --,,-e,.,,..n_ m - , - - . . . ..

,.--.pn w n, , ~, .,---,e.- ,- , -w r ,- - - - --r------

WNS TP.028 Rev. 0 7.0 DATA ACQUISITION ,

7.1 Two inch cube preparation and Compressive strength information will be presented on form W.2301 Rev 1, 7.2 Simulant preparation will be performed in accordance with ACP 7.1 l

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r3J0020:3Pd 6

MANS-ld-0:8

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• 0 Y11Y3liW3NI V iolp msoJ te appes pu wp soptne sotioa )enous niaJele Jp tsum seew ,gn 3eno dyosdyele soJene L L t t t 0 L 0 0 6 0 0 t 0 t i t t 0 L L t 0 0 0 0 t 0 6 6 0 t 0 L t t t 0 6 0 0 L L 0 L t 0 t L t 0 0 0 0 L 0 0 0 0 0 0 o L t 0 0 0 L 0 0 t 0 0 t 0 L t 0 L 0 0 t t i o o L 0 0 t t 0 L 0 L 0 L 0 L 0 t 0 0 L 0 0 0 0 0 0 0 t 0 0 0 L 0 0 6 0 0 0 t t t L 6 t 0 t 0 L 0 t t 0 0 0 6 t 0 0 c L t L L 0 L 0 0 0 L L 0 0 0 6 t 0 0 t - ,

0 0 4 0 0 6 0 t t t 0 0 0 0 L 0 L 0 L 4 L L L L t t t t t 0 6 0 0 0 0 0 t L L 0 0 0 0 t 0 t t 0 0 0 t L t 0 0 0 0 0 0 t t 0 0 0 0 L 0 t L 0 0 0 0 0 t 0 L 0 0 t t 0 L 0 0 0 0 0 t t 0 t O o L L 0 t t 0 0 0 L L L 0 6 0 0 0 0 0 L 0 L 0 0 L 0 0 L L L L 0 0 0 L 0 6 0 0 t t 0 0 L L 0 0 0 t 0 0 6 0 t 0 0 0 L 1 o o t 0 0 0 L 0 0 0 L L L 0 t t 0 t 0 t t o L L 0 0 t t t L t L 0 0 L L t ~

0 6 L 0 t L t 0 0 t t t L 0 t t 0 0 0 L 0 t t t t L 0 0 0 0 0 0 0 t t L 0 L L L L 0 0 6 0 t t 0 0 t 0 t t 0 0 t t t 0 t 0 L 0 t 0 t t 0 0 0 t t 0 0 0 t 0 L 0 0 L t 0 t t 0 L 0 0 0 0 0 t t t L t o L 0 0 t t 0 L L t 0 i

> t 0 0 t 0 0 4 0 0 l L 0 L 0 L L L L 0 0 0 t t 0 0 L 0 &

i t

0 L L L L t 0 0 i 0 0 L 0 0 0 0 0 0

' t 0 0 L L 0 t t t i 0 1 0 L 0 L L 0 t t t 0 t t t 0 0 0 t t 0 0 0 0 t 0 L 0 0 t L i 0 L L 0 t t 0 0 t t t 0 t t 0 t t t t 0 1 t 0 0 0 0 t t t L 6

) 4 l

l

WNS.TP 028 Rev. O Attachreent B Norninal Recipe High Sulfate Low Sulfate g/L g/L g/L 5

Sodium Nitrate 148.108 122.320 165.693

• Sodium Nitrite 140.707 116.208 157.413 Sodiwa Sulfate 87.859 145.123 49.145 Potassiwn Hydroxide 9.272 7.658 10.373 Sodium carbonate 25.031 20.673 'z8.003 ,

Sodium Hydroxide 0.915 0.756 1.024 Sodiwa Chromate 1.281 1.058 1.433 Sodiwa Chloride 0.973 0.804 1.089 Sodium Phosphate 0.790 0.652 0.884 Sodium Molybdate 0.166 0.137 0.186 Sodium Borate 0.100 0.083 0.112 Oxalic Acid 0.133 0.110 0.149 .

O Tartaric Acid Citric Acid 0.133 0.133 0.110 0.110 0.149 0.149 ,

HO2 843.796 844.200 844.200 Grass of Solids 415.601 415.800 415.800 Grams of Solution 1259.397 1260.000 1260.000 Wet Total Solids 33.00 33.00 33.00 i

l l

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High Nitrate / Low Nitrate / Alwninum i

i Nitrite Nitrite Addition i

g/L g/L g/L "

l 4

Sodiwn Nitrate 189.363 109.178 147.823-l Sodiwa Nitrite 102.040 177.376 140.436 Sodium Sulfate 86.203 89.564 87.690 t

l KMJ0020:3RM 8

~er--.,-~.we+.--,--,-7--, -m-,,,m--e-. ,,w w v...,,r.,.g-.y,,-.=w+-,m.w,w,,,.-wwww,-,,c,aw,....s,- , . . , ...4,,,-g-.g..-,e w,y,.w.,gww.=~,. --w--w ---,.r.,.+m---..-w--

WNS TP 028 Rev. O Attachment B Continued Nominal Recipe High Sulfate Low Sulfate VL VL VL Potassium Nitrate 9.097 9.452 9.254 Sodiwn Carbonate 25.559 25.517 24.983 Sodiwa Hydroxide 0.898 0.933 0.913 Sodium Chromate 1.257 1.306 1.279 Sodium Chloride 0.955 0.992 0.971 Sodium Phosphate 0.755 0.805 0.788 Sodium Molybdate 0.163 0.169 0.166 Sodium Borate 0.098 0.102 0.100 Aluminum o,998 Citric Acid 0.130 0.136 0.133 Tartaric Acid 0.130 0.136 0.133 0xalic Acid 0.130 0.136 0.133 HO 2 844.200 844.200 844.200 Crams of Solids 415.800 415,800 415.800 Grams of Solution 1260.000 1260.000 1260.000 Vtt of Total Solids 33.000 33.000 33.000

=

0 KMJ0020:3RM 9

i WNS TP 028 i Rev. 0 I

iO s Attachment B i

j Continued i l l

1 j High Low l l Organics Organics i

i vL ut l Sodium Nitrate 148.037 148.250 l Sodium Nitrite 140.639 140.841

} Sodium Sulfate 87.817 87.943 Potassium Nitrate 9.268 9.281

)

Sodium carbonate 25.019 25.055

]

j Sodium Hydroxido 0.915 0.916 i Sodium Chromate 1.280 1.282 j Sodium chloride 0.973 0.974 j Sodium Phosphate 0.790 0.791 l Sodium Molybdate 0.166 0.166 i

i Sodium Borate 0.100 0.100 i Oxalic Acid 0.266 0.067 j Tartarie Acid 0.266 0.067

. Citric Acid 0.266 0.067 i HO 2 864.200 844.200 f

i 1 Grams of Solids 415.800 415.800 i

j Grams of Solution 1260.000 1260,000 l We t of Total Solids 33.000 33.000 1

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!' KMJ0020:3RM 10 l

West VallevJ Doc. Number WNS TRQ 029 i i Demonstration Project . Revision sunber o Revision Date 04-04-91 Engineering Release #2053 TEST REQUEST PRODUCTION OF CEM.NT PRODUCT FROM ACTUAL SLUDCE WASH LIQUID PREPARED BY . / l!/4 [v re / fl % /< c. A, s3ith Cognizant Engin /

APPROVED BY /r - 3 27 41 D. C. Meess Cognizant System Design Manager 0 l f , l 1ftll APPROVED BY I N 'Of} / I/d D'C/ M N WD. hiL. Shugars l l Quality As4 6rance Manager AP BY ,o  ; 3d8/f//J). J. Harward Radiation 6"Sifety Managsr* I APPROVED BY k .0 O- 'N~ 3[1'/9 I J. C, Cwynar Pre. bess Control Engineering West Valley Nuclear Services Co., Inc.

P.O. Box 191 g

West Valley, NY 14171-0191 j 4

WV 1816, Rev.1

n '. b 5 + 1 hy

• V 4 V Rev. O RECORD OF REVISION PROCEDURE O If there are changes to the procedure, the revision number increases by one.

These changes are indicated in the left margin of the body by an arrow (>) at the beginning of the paragraph that contains a change.

Example:

> The arrow in the margin indicates a change.

Revision On Rev. No. Description of Changes Page(s) Dated 0 Original Issue All 04-04 91 i

O O VV-1807, Rev. 1 i BEL 0051:3RM

ava., m y vc y Rev. O RECORD OF REVISION (CONTINUATIO!1 SHEET)

Revision on O Rev. No. Description of Changes Page(s) Dated iO W-1807, Rev. 1 11 BEL 0051:3RM

I WNS TRQ 029 Rev. O PRODUCTION OF CEMENT PRODUCT FROM ACTUAL 5LUDCE k' ASH LIQUID

1.0 INTRODUCTION

1.1 This work is required to approximate the full scale sludge wash process that is being developed at the k'est Valley Demonstration Project (WDP) , on a lab scale. A confirmatory cube will be made using actual sludge wash solution produced in lab scale tests to determine accuracy or validity of similar tests to be used in the qualification program, per reference 7.1. This work is within the scope of WNS TPL 70 ll, section 4.6. All work contained in this document will be completed in the WNS Analytical & Process Chemistry (A&PC) Lab.

The results of solidification (e.g., gel time, free liquid, cement slurry density) will be compared with results of cube set al from WNS - TRQ. 02 8. Also, a decision will be made by the A & PC lab as to the accuracy of the simulant specified in WNS-TRQ 026 Composition of all four washes will be compared to that specified in reference 7.2 to assess the validity of simulant to be used in future qualification work, h

d 1.2 All work will be performed with an actual high-level waste tank (BD-2) sludge sample. (Reference 7.3) 1.3 Testing shall be conducted in accordance with a test procedure.

WNS TP 029, issued by the A & PC Lab.

2.0 OBJECTIVE NOTE: All weights are approximate. Actual weights should be 4,,0.1 grams of given weights, and be recorde.d per WNS TP 029, 2.1 The sludge sample (approximately 50 grams) shall be " washed" four times. The washes shall attempt to approximate actual sludge washing conditions. (Reference 7.4)

For the first wash, add:

The 44.8 grams sludge sample. (Sample contains interstitial liquid) 573 grams of 8D 2 Supernatant. Analyze supernatant for constituents given in section 2.4 70 grams of lab demin water and 5.8* grams of caustic soda (premixed before being added to mixing vessel)

O BEL 0051:3RM 1

w vwe age var--

j Rev. O i

For the second, third, and fourth wash, add:

I - 233 grams of lab demin water and 0.45* grams of caustic soda 4

j (premixed before being added to mixing vessel) i 1 2.1.1 Demin water should be analyzed for Na, Mg, Ca, SO4 , and K 1

j 2.2 Each vash will be 1 day in length and vessel agitation will 1 approximate actual washing procedure. After agitation, the liquid

! will be allowed to settle for 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />. Vessel temperature will be j j approximate 70 C for agitation. )

1 i

2.3 After each of the four washes are complete, the resulting wash j liquid shall be decanted off the top of the sludge according to j

WNS.TP.029 in the following approximate amounts. (Actual weights j

of decanted solutions shall be determined in WNS.TP.029, and e recorded for each vash.) '

l' Vash 1: 298 grams of solution Wash 2: 268 grams of solution l Wash 3: 262 grams of solution j Vash 4: 261 grams of solution

]

A & PC personnel to note:

1. Speed of solids settling

2. Approximate height of mixture and that.of settled solids

3. Approximate height after wash solution removed O 2.4 The liquid from all four washes will be analyzed for the following:

I NO 2 K PO4 Tl f

NO 3 Na Ca SO4

BO pH Cr0 4 i C1 Al U Tc-99 Cs.137 Sr.90 Alpha Pu Gross Alpha Gross Beta l

} Specific Gravity Total Dissolved Solids (TDS) t i Total Suspended Solids (TSS) i j 2.5 The wash liquid from washes 2, 3, and 4 will be stored in sealed I containers separately at the.A6PC lab for future testing. Label i *WNS TP.029 Wash a .

l

• Caustic Soda weights given are approximate. Actual weights will be i determined by Titrating and will be incorporated into WNS TP.029.

!v

! BEL 0051:3RM 2 r---rve--r-e ,..,wh-s

-- -ww-,-,.v-+,-~ .vy - .y w swwp.g.w w nw m w w

.,-mw,,.. y- 6,-ww- .-,,,my,wmemmem-,-,m.-3 g- w y,ww wr--..,rww r,

-w,-9i.,- -ttw-ry---'

www wu vu Rev. 0 2.6 The decant liquid from wash 1 shall be processed throu6h lab ion exchange columns containing zeolite at a rate of between .8 and 1.1 Column Volumes per Hour (CV/H). The configuration of these columns will be determined and is to be specified in WNS TP 029.

the ability to sample between columns is needed. These san.ples will j oe taken at the discretion of the cognizant A&PC scientist per i WNS TP 029. The samples will be analyzed for Cs 137 and Alpha

) Plutonium decontamination factor (DF). This information will also 1 be needed to calculate Cc 137 and Pu percent breakthrough.

l j 2.7 once a preset breakthrough point for Cs 137 is reached, the lead j column will be taken off line. All further column changing and j preparation will be specified in WNS TP 029, i

i 2.8 Step 2.7 will be repeated as often as necessary as determined by i Cs 137 breakthrough, to process total wash el volume.

I

2.9 Once all of the liquid has been processed through the columns, the j liquid will be analyzed for all constituents listed in step 2.4 a

1 2.10 The resultant " decontaminated" sludge wash solution will be slowly evaporated to a nominal 33 weight percent-Total Dissolved Solids 1 (TDS). (Per reference 7.4) The evaporati m will take place in- a

] glass container with a bottom heating unim At this point lab

] personnel should note any unusual oct w v..ces that may occur during boiling, e.g. precipitation, scaling on surfaces, etc.

1 2.11 The resultant " concentrates" will be analyzed per section 2.4 This 4

work can be done in parallel with steps 2.11 through 2.14.

f 2.12 A&PC will take 100 ml of the nominal 33 we percent decontaminated

} solution and make a cube using the recipe developed in WNS TP 025, j WNS TP 026, and applicable steps of ACM 4801.

i

. 2.13 The remaining solution will be stored in sealed containers for

{ possible future analysis. Label "WNE-TP 029 Wash a ,

j Concentrates",

i 2.14 A&PC will perform destructive tests on the cube per ACM.4701.

I l_ 2.15 All data vill'be reviewed and approved by a qualified A & PC j scientist or A & PC lab technician.

l 3.0 SAFETY i

I 3,1 Industrial hygiene practices will be as described in the WNS l Hygiene and Safety _ Manual WDP 011.

3.2 Radiological work will be performed in accordance with the WDP Radiological Controls Manual, WDP-010.

!O

! BEL 0051:3RM 3 I

, .c ~

3.3 Vork in the Analytical & Process Chemistry Lab will be performed in accordance with existing A6PC methods (ACM's).

4.0 EQUIPMENT CONFICURATION 4.1 All lab equipment will be set up as directed in WNS TP 029, 5.0 SAMPLING FREQUENCY 5.1 Additional samples will be obtained in the quantities and frequencies specified by the cognizant A6PC scientist and will be specified in WNS TP 029, 6.0 PERSONNEL QUALIFICATION 6.1 Testing will be performed by qualified Analytical 6 Process Chemistry Technicians usin6 Analytical 6 Chemistry Methods (ACM's) under the cognizance of an A&PC scientist.

6.2 Surveillance activity will be performed by qualifiec. Quality Assurance personnel.

7.0 REFERENCES

7.1 " Technical Position on Waste Form", Revision 1, dated December 1990.

7.2 " Preliminary Flowsheet Sludge Wash with Existing 8D 2 Heel",

EK:91:0047, J. L. Mahoney, dated 03/07/91.

7.3 Vork performed with S0P 8 20, "8D 2 Sludge Sampling" Composited in the A 6 PC Lab on January 10, 1990.

7.4 " Removal of Plutonium from West Valley High Level Liquid Vaste",

Bray, Hara, Kazmierczak, dated January 1991.

O BEL 0051:3RM 4

l West Valley .

Doo. numeer uVnS-TP-029x  ;

O Demonstration Project Reviaton number o Revision Date 04/18/91 Engineering Release #2065 TEST PROCEDURE PROCEDURE FOR CONFIRMATORY CUBE PREPARED BY M[

Cognizarf: Enginedr

,,/,,oh L.E. Michnik APPROVED BY [ & 'DiC. &#&f D.C. Meoss G Cognizant Sptom Design Manager

/ 'f1 , 'l l APPROVED BY ' (D/

/ ~ M e< W r, 7 V ' 11 '/// 7[#// D.L. Shugars Qualit/y Assurance Manager -

APPROVED BY *d NO3(L;3rLd d!N!T D.J. Harward IQQiation and Safety Manager APPROVED BY k ' b bw% hl7 /9 f J.C. Cwynar Pt> cess Cchntrol Ehgineering l

West Valley Nuclear Services Co., Inc.

l P.O. box 191 I p West Valley, NY 14171-0191 j PSK:TP-029 WV-1816 Rev.1 1

P WVHS-TP-029A Rev. O j () RECORD OF REVISION i PROCEDURE If there are any changes to the procedure, the revision number l increases by one. These changes are indicated in the left margin j of the body by an arrow (>) at the beginning of the paragraph

. that contains a change.

]

\

j Examolet

> The arrow in the margin indicates a change.

a i

i Revision On ,

l Rev. No. Description of Changes Page(s) Dated 0 Original Issuo All 04/18/91 i

I([)

i i

t 1

F i

()

. PSK TP-029A i m,_ - ,m- , . . , . _ , , , , . - . . , , _ _ , - -

.,~,.._,.,_,_,_,,,,,y .. . . , . . ~ , . _ ~ . _ . _ _ . - . - , . . , -m,. , - . , - . .-.,,,,,,,,y ,,1~-,-,

WV!lS-TP-029A Rev. O RECORD OF REVISIO!1 (CollTIliUATIoli SilEET)

Revision on Rov. Ilo. Description of Changen Page(s) Dated i

i O

4 O

PSK TP-029A

, 11

1 i

j WVilS-TP-029A

Rev. 0 1

j Test Procedure for Confirmatory Cuba 1

l 1.0 SCOPE

! 1.1 This procedure is for the preparation of a 2x2x2 inch i

coment cube made from actual sludge wash liquid generated i from WVlis #2: Sludge Wash #1 and Sludge Wash #2 using a nominal thirty-two inch supernatant heel. It provides j the procedure required to perform the tests stated in WVHS-TRQ-29 and WVHS-TE-029.1. The cube vill also j provide information on the reaction of the nominal recipe 4 for cement on actual sludge wash material and determine

if any unforeseen constituents are having an adverse j effect on the cement product.

I 1.2 The liquids will be combined and evaporated to j approximately one hundred milliliters (mis), which is the

minimal volume of liquid required to generate a cube.

1 The total dissolved solids in the concentrated material

will have a maximum value of thirty-three weight percent ,

! and a minimum value of twenty-nine.

O 1.2 The data eenerated from this cuee, comeressive sereneth, gel time, bleed water and penetration resistance will be 3 compared to the results obtained using data generated

! from simulated sludge wash liquid from the nominal thirty-three inch supernatant heel (see Attachment A) j produced under WV!1S-TRQ-025.

l 2.0 DEFINITIONS AND ABBREVIATIONS i

2.1 Definitions coment-Dry Portland Type I coment in accordance with ASTM l

Standard C-150-85.

! Antifoam-General Electric AF9020 emulsion of five percent i Dimethlysilicono in nanopure. This is used as a coment recipe enhancer to prevent air entrapment in the coment matrix during high speed mixing.

Sodium Silicate-is used as a recipe enhancer in the gelling of the cement waste form and prevention of excess bleed water.

PSK TP-029A b

_ . . -.. ._,_,,_ - , ., _-. s - . _ , - . , _ , , - _ ,-_.._,-__.._.m._ , . . , _ _ _ , , _.,..__._.__..c_. _ . . , . _ _ _ _ _ _ _ _ _ , . . - - _ _ _ _ . - , . .

_ _ - - - _ - _ _ - - - ~ _ - .- - - - - - . - . - _ - . - . . _ _ _ _

~ . - _ .

i ,

i WNS-TP-02 9 A Rev. 0 ,

j Calcium Nitrate tetra-hydrate is used as a recipe j enhancer in the setting of the cement waste form Cube-

2x2x2 inch plastic mold used to make laboratory

) specimens.

1 I

2.2 Abbreviations j ACM-Analytical Chemistry Method 1

ASTM-American Society for Testing and Materials

] 3.0 RESPONSIBILITIES i

! 3.1 Analytical and Process chemistry will be responsible for 2

the preparation and testing of the laboratory specimens

in accordance to the applicable steps of the appropriate analytical chemistry methods and WNS-TP-029A.

3.2 Quality Assurance will provide surveillance to ensure that the requirements of this test procedure and WNS-

. TRQ-029 and WNS-TE-029.1 are satisfied and verify the 1

final concentrate product, witnessing of the cube being made and also the crushing of the cube.

! 3.3 Radiation & Safety monitors radiation and contamination levels in the laboratory to insure work is conducted in accordance with the Rad Con Manual WDP-010 Rev 1.

l 3.4 Process Control Engineering will be responsible for issuing the test summary report , WNS-TSR-02 9, in

, accordance with EP-11-003.

! 4.0 TOOLS, EOUIPMENT. COMPONENTS AND REFERENCES l

l 4.1 Tools and Equipment i

Lightnin Lab mixer Model No. TS-1515 with high shear

impeller or equivalent

- 2x2x2 inch plastic cube molds l

100 milliliter (ml) plastic or glass graduated cylinder ,

with one ml divisions j 500 ml polypropylene plastic bottles 250 ml borosilicate beaker O PSK TP-029A 2 l

WVHS-TP-029A gS Rev. O V

Corning hotplate or equivalent 10 ml glass volumetric flask ,

20 ml plastic scintillation vials magnetic stirring plate and magnetic stir bar stopwatch or timer accurate to one second top loading balance readable to 0.01 ga (grams)

Blue M Oven Model No. C-2630-Q or Despatch Environmental Chamber Model No. 16307 Gilson Penetrometer, Model No. CT-421 4.2 Reagents Portland Type I cement Calcium Nitrate tetra-hydrate, reagent grade

() -

Nanopure water or ASTM Type I water Sodium Silicate, technical grade

• Antifoam General Electric AF9020*

• Supplied by IRTS operations 4.3 References NRC Technical Position on Waste Form (Revision 1) Dec, 1990 ACM-1701 " Destructive Test of 2 inch Cement Cubes" ACM-2401 " Density" Rev 3 ACM-2501 " Determination of Total Solids" Rev 2

" Removal of Plutonium from West Valley High-Level Liquid Waste", Dray, Hara, Kazmierczak, dated January, 1991 ASTM C 109-86 O PSK:TP-029A 3

WVHS-TP-029A .

Rev. O i

WVHS-TRQ-29 " Production of Cement Product for Actual Sludge Wash Liquid" .

l

- WVV. 4I-029.1  !

EP-11-003 5.0 GENERAL INFORMATION j This test will be used to evaluate the nominal cement

^

5.1 formulation recipe (see Attachment c) using actual sludge wash and supernatant from tank 8D-2 based upon a thirty-three inch supernatant heel. It will confirm the accuracy of data and observations generated by laboratory simulants (see Attachment D) and determine if any 1 unforseen constituent are having an undesirable effect on tne cement product. +

6.0 PROCEDURE i

6.1 Prerequisite ,

Oven or environmental chamber should be set at proper  :

O. temperature as defined in sec 6.3.17 and monitored by a calibrated thermocouple or thermometer per PRD 8.0 Rev.

1 Balances shall be calibrated according to ACP 7.1 Safety procedures should be reviewed in ACP 7.2 6.2.1 The liquids from WVNS 2, Sludge Wash #1 and i Sludge Wash #2 , pre and post concentrated i material,( see Attachment B) will be combined l in a two-hundred and fifty ml beaker and evaporated slowly, while stirring to reduce splattering. The liquid will be reduced to

• approximately three-quarters of its -initial j volume.-- At this point the total-solids will-

be determined by ACM-2401. If the total solid j content is between twenty-nine and thirty-F three-percent, the evaporation will stop and~

j the solution allowed to cool. If the solid

! content ~is lower than twenty-nine percent,

! evaporation will continue and the liquid tested f

iO

! PSK:TP-029A 4 I

I -;

L

WVlis-TP-029A Rev. O O

periodically by ACH-2401 until the speciflod range of the solids is achieved. At this point the total solid content will be confirmed by ACM-2501.

6.2.2 If the liquid is reduced to the point voro solids are falling out of solution, the ovaporation should stop and nanopuro water should be added in small increments and tho

' solution should be allowed to stir. Water and stirring shall be used to redissolvo the solids. A total solid determination should be mado and an appropriato amount of water added to achieve the total solido specified.

6.2.3 After the appropriate solid content has boon achieved ninety- six mis of the concentrate will be used to make the confirmatory cube as stated in sec 6.3 and the remaining will be used for the analysis stated in WV11S-TRQ-029 coc 2.4.

6.3.1 Make a fivo (5%) porcent antifoam solution.

Os Weigh 5.00 i 0.05 ga of well mixed AF9020 in a 100 ml volumotric flask and dilute to the manufacturer's mark with nanopure water. Mix well and transfer to a beaker with a magnetic stir bar and stir continuously on a stir plato.

6.3.2 Prepare 200 gs 5.7 percent calcium nitrate tetra-hydrate /coment mixture by adding 11.4 gs calcium nitrate tetra-hydrate to 200 gs Portland Type I coment in a 500 ml beaker and mix the dry ingredient thoroughly.

6.3.3 Use a five-hundred (500 ml) plastic bottle to make a mixing vossol by evenly cutting off the tip and producing an open onded cylinder, 6.3.4 Similarly cut tho, top off a two hundred and fifty (250 ml) plastic bottle. This container will be used to add the cement / calcium nitrate mixture to the liquid wasto.

6.3.5 Tare the cutoff two hundred-fifty (250 ml) bottle and add 140.5 19 coment/ calcium nitrato. Record weight on the appropriato Form p WV-2301.

PSKtTP-029A 5

, W!IS-TP-02 9 A Rev. 0 O

6.3.6 Place the cut empty five hundred (500 ml) mixing vessel prepared in stop 6.3.2 under j impoller and set mixer speed to one thousand rpm.

6.3.7 Monsuro 9612 ml of 29-33 Wtt sludge wash from stop 6. 2. 3 using a 100 ml graduated cylinder and record on Form W-2301.

6.3.8 Pour 96 ml of stimulant into the 500 ml mixing vennel prepared in 10.2. Rinse the graduated cylinder after each use with nanopure water.

6.3.9 To the sludge wash, use an Eppendorff pipet and transfer 0.3 1 0.006 ml of the 5% antifoam mixture from stop 6.3.1. Record on Form W-2301.

6.3.10 Tare a 10 ml disposable plastic cup and add to it approximately 11.00 1 0.5 gs sodium silicato. The exact amount transferred will be found by re-weighing the cup after the material is poured into the sludge wash. Record 5

the weight on Form W-2301 6.3.11 Support the mixer on a lab stand so that the impeller blado is one-quarter to one-oighth inch from the bottom of the 500 ml plastic bottle. Use a wide mouth clamp to support the 500 ml plastic bottle without crushing the side. Set a timer for eight minutos.

6.3.12 Begin the mixing at 1000 rpm and start the timor. Add the dry coment/ calcium nitrato mixture to the waste within the first thirty seconds. After forty-five seconds, slowly add the sodium silicate within an additional forty-five seconds. Continue to mix for a total mix time of eight minutes.

6.3.13 After the transfer of the sodium silicate re-weigh the cup and calculate the amount added by difference, record on Form W-2301. While mixing, mark a cube mold with a permanent marker with the dato, sample type, numerical identification sequence number and then weigh the cube mold, record the weight on Form W-2301.

O PSK TP-029A 6 l

i WNS-TP-02 9 A Rev. 0 6.3.14 After completion of the eight minute mix, stop the mixer and transfer the contents to a plastic 2" cube mold. Fill to the top and transfer the remaining to a 20 ml plastic scintillation vial and seal. Af ter weighing the cube tare the scale to zero and reweigh the cube with the cement in it. Record the weight on Form W-2 301. Determine the wet density of the material by the formula below.

Wet Density = Total weicht of cube (c) -Tare weicht of cube (a) 131 mis Record on Form W-2301. Af ter completing this step place the cube in a zip lock plastic bag.

6.3.15 Clean the impeller with water immediately after pouring.

6.3.16 Visually check for gelation of the cement in the 20 m1 scintillation vial. Check every five minutes and do not disturb between these time intervals. Record the time it take the cement O to gel.

determination, Gelation however is gelled a subjective cement is indicated when the 20 mi scintillation vial can be tipped slowly to a 90 degree position, parallel to the horizon. The cement should not deform, flow, and will retain a line of form perpendicular to the horizon. Bleedwater may be present, do not interpret as a sign of uncompleted gelation.

6.3.17 Transfer the cube to a drying oven with the temperature set at 88 2 celsius within two hour of preparation and allow to cure in the oven for 61 i eight hours. Record on Form WV-2301 time, date the cube was made and the time it was placed in the oven and also the start temperature.

6.3.18 Af ter 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />, determine in mis the bleedwater in the scintillation vial and also determine the pH by indicator paper; record it on Form WV-2301.

O PSK:TP-029A 7

I

}

i

{' WVHS-TP-029A Rev. 0

) 6.3.19 Calculate the water to cement ratio by weight

{ using formula below.

j ( A) (B) (1-C) j (D) ( 0. 94 3)

{ A= Volume in als of sample i B= Density value in gs/ml of sample i C= Total Solids value in decimal form I

D= Weight of cement used in gs 6.3.20 After sixty-one hours i 8 hour-take the cube 5 out of the oven and do the penetration I resistance analysis (see section 6.3.22) and I

record the time, date and temperature of the cube removal and also the penetration i resistance on Form WV-2301. '

4

{ 6.3.21 Caution: Do not remove the cube from the mold-for the-penetration test and only when ready 1 to crush.

i j 6.3.22 Using the concrete penetrometer model CT-421; perform the penetration resistance test by

,'O re ovins ene oude tro the des and visoine the

! penetrometer plunger in the center of the ,

i exposed side of the cube. Make cure the red

indicator ring has been set back to the zero i mark on the penetrometer. With a steady l Vertical force push the penetrometer against

! the cube until the red indicator ring is all

{ the way'down the scale when the penetrometer j shaft will. not penetrate the cement any

j. further.

1 6.3.23 On the handle of the penetrometer, read the j value on the red indicator ring and record the

number on Form WV-2301. If the red indicator i ring is all the way to the end of the scale, j a value of >700 psi shall be recorded.

4

6.3.24 When the sample cube is cured for a total of-l 7 days t 8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> Determine the d'.y density by i th e formula below

'

?

j O PSK:TP-029A 8

,,y-, ,cc-,m, .,  ;,,,e.ww,,-w,,-* ,..,a,y..e ,m.,.,y--+~e., ,..-,o.

,,m.m u.e4,, W.=~.. .e,.-,-.%-- ,,,w.w--.we. c w e. , -w.+,,,---&we

WVilS-TP-029A Rev. O Dry Density = Total welaht of dry cube foi-tare weicht of cube (a) 131 mis Record on form WV-2301 6.3.25 Crush the cube according to ACM-4701 using templates Model lio. ACM-140 7.0 DATA ACOUISITIOli 7.1 Two-inch cube preparation and Compressive strength information will be recorded on Form WV-2301, Rev 1.

7.2 Total solid content will be recorded on Form WV-2306 8.0 ATTACIIMEliTS

=

A) Composition of Simulant with 33 inch Supernatant Heel B) Analysis of Sludge Wash liquids C) Nominal Recipe for Sludge Wash Cement D) Nominal Cement Recipe Compressive Strength Data E) Density Workshoot, ACM-2401 Rev 2 F) Total Solids Worksheet, ACM-2501 Rev 2 PSK:TP-029A 9

l 1

1 i WVHS-TP-029A Rev. O Attachmont A l ION CONCENTRATIONS FOR CEMENT FORMULATION from TABLE 4-8 1 of Topical Report " CEMENT WASTE FORM QUALIFICATION REPORT - WVDP PUREX DECONTAMINATED SUPERNATANT"

) LD/20.9 gal **

! Salt Formula g/L g/L at 33 wt t Hol Wt i

iSodium Nitrate NANO 3 278.344 278.344 48.54' 85.010 iSodium Nitrite NANO 2 143.790 143.790 25.079 69.000 l 1 Sodium Sulfate Na2SO4 35.222 35.222 6.1432 142.060 iSodium Bicarbonate NaHCO3 19.656 19.656 3.4282 84.010 Pottonium Nitrate KNO3 16.753 16.753 2.9220 101.100 Sodium Carbonate Na2CO3 11.661 11.661 2.0339 106.000

, Sodium Hydroxide NaOH 8.100 8.100 1.4127 40.010 1 Sodium Chromate Na2Cr04 2.851 2.848 0.4967 161.970 iSodium Chloride Nacl 2.163 2.163 0.3773 58.450

! Sodium Phosphate Na3PO4 1.754 1.754 0.3060 163.940

! Sodium Molybdate Na2 moo 4.2H 0.374 0.374 0.0653 241.950 l Sodium Fluoride NaF 0.000 41.990

' Sodium Borate Na2B407 0.665 0.665 0.1159 201.270 iHO 2 800.682 1060.000 139.6500 4 0.000

! Citric acid 0.299 0.299 0.0521 192.120 i

or' ic acid 0.299 0.299 0.0521 126.070

!TL_~}aricacid 0.299 0.299 0.0521 150.090 1

Total Mole %

Wt %

lWt of Solids 522.230 522.227 91.084

'Wt of Solution 1322.912 1582.227 230.734 lWt% Solids 39.476 33.006 39.476 1255.74 ml I

t t

C:)

i PSK:TP-029A 10 4

,~ , - ~ . . - . . . . . . . , , . . . , . . , . , , , - , - - - , , . . , , , . ..,.,,.,,...,,,,,..~..+-..n,, - . . . , < , - ,

WVHS-TP-029A '

Rev. 0 Attachment B O DATA FOR THE LABORATORY SCALE SLUDGE WASTE AT pH 12.5 F. Hara 12/5/90 i

Sludge shows 29.3 wt % loss on drying at 104'C, 40.7 % loss during wash, and 30.1 wt % insoluble sludge.

Wt of Sludge 196 g Solid in Sludge 70.8 Dancity of Sludge (g/ml)

Raw Super from 8D-2 71.3 g Vol of Raw Super 60.2 Vol of Wash Water 500 ml Dcasity of Ray Super 1.184 Wt of Washed Dried Sludge 59.01 g or 30.1% of wet sludge CHEMICAL ANALYSIS OF LABORATORY SCALE SLUDGE WASHES REFORE DECONTAMINATION WITH TITANIUM COATED ZEOLITE Analysis of washed M asured Parameters or First Second Third Fourth dried Laboratory Analysis Wash Wash Wash Wash sludge Lab No (Sa ID) 9003305 Super (gram) 468 458 406 484 D nalty (g/ml) 1.109 1.032 1.009 1.002 Vol Super (ml) 422 444 402 483 Liq Vol in Sludge (til) 175 175 175 175 Total Liquid Vol (ml) 597 619 577 658 pH 11.87 11.58 11.63 11.59 Nitrite (ug/g soln) 21100 6080 2070 580 Nitrate (ug/g) 20600 5680 1830 399 SulfLie (ug/g) 25400 6620 2340 593 Chloride 'jg/g) 978 614 22 14 Phoaphate (ugff)

Sodium (ug/g) AA 44880 11510 4190 1710 47 Potacolum (ug/g) AA 1900 710 230 (.53)?

Urenium (ug/g) Fluorir.6ter 150 36 3.2 1.6 44100 Cr (ug/g) AA Tot 157 23 11 2.6 Ca (ug/g) AA 12.4 9.24 3.08 0.57 18370 Al (ug/g) 1000 180 100 60 18067 Ba (ug/g) 8900 q'v PSK:TP-029A 11

RVHS-TP-029A Rev. 0 h*

Attachment B hrs (cont'd)

CHEMICAL ANALYSIS OF LABORATORY SCALE SLUDGE WASHES BEFORE DECONTAMINATION WITH TITANIUM COATED ZEOLITE i

Analysis l of washed M;ccured Parameters or First Second Third Fourth dried Laboratory Analysis Wash Wash Wash Wash sludge

, Lab No (Sa ID)

Pu239 (uCi/g) 0.198 0.026 0.00732 0.0012 Totcl Pu (uci/g) 0.292 0.0382 0.0105 0.0016 101 Sr 90 (uCi/g) 0.282 0.0963 0.0.00203 0.00909 57000

-Ca 137 (uCi/g) 418 118 41.4 11.9 291 Co 60 (uCi/ml) ND HD <6.5E-3 <2.4E-4 Tc 99 Sb 125 <5.7E-1 <1.6E-1 <7.2E-2 <6.0E-3 Eu 154 <1.8E-1 <4.8E-2 <2.7E-2 <1.2E-3 F 155 <7.4E-1 <2.3E-1 <1.3E-1 <2.5E-3 Groce Alpha 1210 Gro D Beta 127000

[

TDS (Wt %) 10.7 4.19 0.76 <0.1 TDS from Decon Wash 13.93 5.48 1.13 0.53 Grams of TDS from WVHS-2 65.19212 25.64629 5.288377 2.480389 200,000 gal of super. 68.16050 20.27452 5.56 1.79 A

(_)

PSK:TP-029A 12

WVNS-TP-029A Rev. 0

(~3 Attachment B

\_/ (cont'd) 11/6/90 F. Hara t SLUDGE WASH OF WVNS-2 AT 70'C L DATA FOR 7FJ LABORATORY SCALE SLUDGE WASH AT pH 12.5 I

Wt of Sludge (gram) 196 grams Solid in Sludge Dansity of Sludge (g/ml)

Raw Super frm 8D-2 (ml) Solids in Raw Super Nol of Wash Water Density of Raw Super CHEMICAL ANALYSIS OF SLUDGE WASH - AFTER DECONTAMINATION WITH TITANIUM COATED ZEOLITE (8 wt% TiO2) COLUMNS M3ccured Parameters or First Second Third Fourth Laboratory Analysis Wash Wash Wash Wash fit Super (gram) lDsnsity (g/ml) 1.102 1.032 1.009 1.002

!Vol Super (ml) l Liq Vol in Sludge (ml) r~^31 Liquid Vol (ml) pi-) 11.6 11.67 11.9 11.81 Nitrite (ug/g soln) 21300 6600 1900 510 Ritrate (ug/g) 18700 6070 1700 370 Sulfate (ug/g) 21000 6400 1800 500 Chloride (ug/g)

Pho:phate (ug/g)

Sodium (ug/g) AA 44300 16400 4200 1700 Pota:sium (ug/g) AA 49 21 71 28 3rcnium (ug/g) Fluorimeter 52 30 17 1.2 Cr (ug/g) AA Tot 81 27 7.7 2.3 Ca (ug/g) AA 3.7 -1.2 20 0.7 S1 (ug/g) 820 250 120 77 ,

?u239 (uCi/g) 1.86E-06 1.65E-06 2.38E-06 6.94E-06 Cotal Pu (uci/g) 7.80E-06 2.90E-06 3.51E-06 1.06E-05 3r 90 (uci/g) 1.93E-05 1.48E-04 1.20E-05 3.24E-04 22 137 (uCi/g) 6.31E-02 1.99E-03 5.82E-05 3.77E-03 3c 60 (uCi/ml) <ND <1.5E-5 ND <1.5E-6 Oc 99 1.30E-01 2.94E-02 1.01E-02 2.80E-03

(~~)

RJ PSK:TP-029A 13 .

__ __..w-u----- --

WVHS-TP-029A Rev. O i .

Attachment B

() (cont'd)

CHEMICAL ANALYSIS OF SLUDGE WASH - AFTER DECONTAMINATION l WITH TITANIUM COATED ZEOLITE (8 wt% TiO2) COLUMNS i

i Macoured Parameters or First Second Third Fourth

Laboratory Analysis Wash- Wash Wash Wash 4

Sb 125 <1.5E-4 <9.5E-5 1.18E-03 1.70E-03 iEu 154 <5.2E-5 <5.1E-5 <7.4E-6 <7.9E-6 iEu 155 <3.4E-5 <5.7E-5 <1.4E-5 <2.7E-f Gross Alpha 5.12E-04 3.84E-04 <.00003 <.0000. -

Groco Beta 1.32E-01 2.84E-02 8.50E-03 7.32E 03

!TDS in wt% 13.93 5.48 1.13 0.aa jTSS Wt% 0.11 0.05 4

)

e i

l l

l l'

1 4

PSK:TP-029A 14

- _. . - ~ . . .. -.

WVNS-TP-029A Rev. 0

,f 3 Attachment B

(,) (cont'd)

CONCENTRATION OF DECONTAMINATED LAB WASH EXPERIMENTAL CHEMICAL ANALYSIS AFTER CONCENTRATION OF THE DECONTAMINATED WASH SOLUTION TO Wt% DETERMINED

'Concantrated SW # SW #1 SW #2 SW #3 SW #4 (2.92) (6.46)

Nitrite (ug/9 soln) 61800 48200 48500 25600 Nitrate (ug/g) 64600 50600 46400 34000

' Sulfate (ug/g) 44700 50400 51100 33800 l Chloride (ug/g) lPho2phate (ug/g)

Sodium (ug/g) AA 104400 101000 111000 95800

Poteccium (ug/g) AA 1600 1500 1600 1450 Uranium (ug/g) Fluorimeter Cr (ug/g) AA Tot 262 200 150 111 Co (ug/g) AA 8.2 9 14 4

'Al (ug/g) 2100 1470 <280 <70

P*9 (uCi/g) 1 Pu (uci/g) 1.64E-05 4.08E-0" 6.98E-06 2.30E-05 Sr 90 2.76E-06 2.88E-04 5.02E-05 6.04E-05

!Cs 137 (uCi/g) 1.22E-01 1.17E-02 1.43E-03 1.78E-01 Co 60 ND ND ND ND Tc 99 4.79E-01 3.03E-01 2.28E-01 1.16E-01 Sb 125 <3.05E-4 4.70E-03 1.74E-02 9.40E-02 Eu 154 <9.6E-5 <8.8E-5 <1.4E-4 <3.4E-4 Eu 155 <5.1E-4 <1.06E-4 <1.1E-4 <4.4E-4 Groso Alpha Grono Beta Dentity 1.297 1.265 1.26

• 1.25

• TDS 37.5 33.6 33 wt %* 33 wt %*

c Product diluted to remove from distillation apparatus.

O PSK:TP-029A 15

WVNS-TP-029A Rev. 0 7-) Attachment C L/

To: John Cvynar

. Lotter#: FH:91:0018 l From: Frank Hara and Larry E. Michnik

Subject:

Cement Recipe for Sludge Wash Simulant with 33 ins:h Supernatant heel Date: January 24, 1990

The recipe for the laboratory scale specimen cube (2x2x2) contain the

following amounts of ingredients

1) 140.0 grams of Portland Type I Cement with 5.7% Calcium Nitrate 4 Hydrate

2) 11.0 grams Sodium Silicate

3) 0.3 mls of 5.0 grams to 100 mis antifoam (AF-9020) i

4) 96 mls of 33.0 weight percent Sludge wash simulant This recipe will produce a product with a water /coment ratio of 0 il illiam F. MacKellar anager A&PCs -

i i

A V

PSK:TP-029A ..

16

WVNS-TP-029A Rev. O Attachment D O nomina 1 necive si=utant Template Method Seven Day curing Sample ID Comp Strength (psi) Date Prepared SWCF3 NR 5.7/4 1194 1/23/91 SWCF3 NR 5.7/4 1592 1/23/91 SWCF3 NR 5.7/4 1444 2/06/91 SWCF3 NR 5.7/4 1208 2/20/91 SWCF3 NR 5.7/4 1358 2/20/91 SWCF3 NR 5.7/4 1331 4/01/91 Average 1331 Std Dev 167 i

O -

=

0 PSK:TP-029A 17

WVHS-TP-029A Rev. O p Attachment E

'%)

DENSITY WORKSHEET Page of

SAMPLE NAME LOG NAME SPECIAL INSTRUCTIONS Instruments Used:

SAMPLE ID QC STANDARD

! SAMPLE VOL. (A) mL

. FLASK + oAMPLE (B) g.

FLASK (C) g.

O LABORATORY TEMP. *C TEMP. CORRECTION FACTOR (D)

SAMPLE DENSITY (B-Ci xD (g/mL)

A If % TDS Requested:

120.640177 (Sample Density) - 119.09553 = % TDS Sample has  % TDS ANALYST DATE t APPROVED DATE PSK:TP-029A 18

4 i

i i WVNS-TP-029A Rev. 0

{. Attachment F i

! TOTAL SOLIDS' WORK SHEET -

f- Page -- _of

!SAMPLENAME LOG NAME

!SPECIAL INSTRUCTIONS 1

1 (Balanco-(Model and S/N):

iSample Drying Method:

l

!Ovan (yes/no) S/N: . Hot Plate (yes/no) i 1

' SAMPLE ID

! DRY DISH (g)-= W,

+ SAMPLE (g) = W, D

2-

' DRIED SAMPLE + DISH j(g) = W, TOTAL SOLIDS (%)

lW- W,

o

W, - W, i

i i

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i I

i

ANALYST DATE a-j APPROVED DATE i

D'~ o

%LCULATIONS: Total Solids (%wt) = x-.100 PSK:TP-029A 19

O west Valley Demonstration Project Doc. N er mvNS.1Ro-030 Revision Number 0 Revision Date 05/01/91 Engineering Release //2075 TEST REQUEST FULL-SCALE CONFIRMATION OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS PREPARED BY TM # M. N. Baker Cognizant Engineer APPROVED BY _.

o D. C. Meess Cognizant System Design Manager APPROVED BY l 64d>t,/ 1,l +4. .*p. - C;We'.

'] '

D. L. Shugars

' Quality psui'ance APPROVED BY 6*/ [u,

_ ren ll35 T-b-f/D. J. Harward Ffadiation & Safety APPROVED BY 'b C%- i[37/91 J. C. Cwynar PVocess Corftrol Engineering West Valley Nuclear Services Co., Inc.

P.O. Box 191 West Valley, NY 14171-0191 WV-1816, Rev.1

l WNS-TRQ 030 Rev. 0 f RECORD OF REVISION PROCEDURE If there a ' changes to the procedure, the revision number increases by one.

These changes are indicated in the left margin of the body by an arrow (>) at the beginning of the paragraph that contains a change.

Exampic.

> The a a margin indicates a change.

Revision On Rev. No. Description of Changes Page(s) I'a t e d 0 Original Issue All 05/01/91 0

O W 1807 Rev.

DLSO431: 3P.M 1 1

WNS TRQ 030 j Rev. 0 l

l RECORD OF REVISION (CONTINUATION SHEET)

Rev. No. Description of Changes Pagefs Revisi n)on Dated i

l l

l W-1807, Rev. 1 11 DLSO431:3RM f

4 f

3 1

i TEST REQUEST WVNS-TRQ 030 REV 0 l

i i FULL SCALE CONFIRMATION OF THE NOMINAL RECIPE FOR CEMENT I SOLIDIFICATION OF SLUDGE WASH LIQUIDS l

1.0 INTRODUCTION

4 I

1,1 This work is required to demonstrate the stability of the " nominal"

{ vaste form recipe developed under Test Request VVNS-TRQ 026.

Characteristics which will be tested are required by 10 CFR 61, Code j of Federal Regulations. Title 10 " Licensing Requirements for Land i Disposal of Radioactive Waste," and the USNRC Branch Technical

i. Position on Waste Form, Revision 1, dated January, 1991.

1.2 Work will be performed using full scale square drums which were j processed using a simulant representing the actual waste liquid, and

the " nominal" recipe for cement addition and recipe enhancers. The

full scale drums will be processed under SIP 91-1.

1.3 This work is required by the Branch Technical Position, Appendix A.II.I.

1.4 Testing will be performed in accordance with' WVNS-TP-030, to be issued by Analytical and Process Chemistry, and WVNS-TPL 70-011.

1.5 Test results will be documented in a Test Summary Report (WVNS TRS-030), to be issued by the Cognizant Test Engineer in 4

accordance with EP-11-003.

, 2.0 OEJECTIVES

, 2.1 After curing for a time determined by WVNS-TP 026, but in no case less than 28 days, approximately five (5) drums will be core-drilled

to obtain 3" diameter X 6" long cylindrical samples. A total of twenty-two (22) samples will be obtained.

i l 2.2 Cores will be obtained from various locations in the drums ( top, middle, bottom locations) to demonstrate the homogenous-nature of the waste form. Locations will be recorded on SOP-70-44,

Attachment D.

2.3 Ten (10) of the samples will.be evaluated for compressive strength per ASTM Standard C 39 and QIP 27.

DLSO431:3RM 1 f

-- e,--w-,---ww

WVNS-TRQ 030 Rev. O

(g 2.4 Twelve (12) of the samples will be immersed in either deionized

. (,,/ water or synthetic sea water for a minimum of 90 days. After 90 i days' immersion, three (3) of the samples will be evaluated for compressive strength per ASTM Standard C-39 and QIP 27. Post-i immersion mean compressive strength shall be at least 75 percent of the pre-immersion mean compressive strength as determined by section l 2.3 above, and at least 500 PSI. If the post immersion mean

! compressive strength is less than 75 percent of phe pre immersion

mean compressive strength, but not less than 500 PSI, the immersion

testing interval shall be increased to a minimum of 180 days. The

remaining samples will then be evaluated for compressive strength at intervals of 120, 150, and 180 days of immersion to establish that j the compressive strengths level off and do not continue to decline l with time.

i l 2.4.1 The immersion liquid, either deionized water or synthetic sea i water, will be determined in advance of this test as part of the Leach Testing being conducted in accordance with 1

WVNS-TRQ-026, Section 2.4.

l

]

3.0 SAFETY l 3.1 Industrial Hygiene practices will be as described in the WVNS Hygiene & Safe ty Manual, VVDP-011.

3.2 Radiological work will be performed in accordance with the WVNS

()

Radiological Controls Manual, WVDP-010.

4 3.3 Work in the Analytical & Process Chemistry lab will be performed in accordance with existing A&PC methods (ACM's),

t 4.0 EQUIPMENT CONFICURATION 4.1 All equipment will be set up in accordance with WVNS-TP-030 and as j

directed by the cognizant A&PC scientist or qualified A&PC technician.

4.2 Core-Boring Equipment will be set up in accordance with SOP 70-44.

j 5.0 SAMPLINC FREQUENCY

, 3.1 Samples will be obtained in the quantities and frequencies specified l by section 2.1 of this Test Request.

5.2 Core-drilling will begin after a minimum cure time of 28 days. The actual cure time will be established in accordance with WVNS-TRQ-026, section 2.2.

j DLSO431:3RM 2 I \,)

WNS-TRQ 030-Rev. 0 4

6.0 PERSONNEL QUALIFICATION tq 6,1 Testing will be performed by qualified Analytical' & Process 4

Chemistry Technicians in accordance with WNS-TP 030 and Analytical Chemistry Methods (ACM's) under the cognizance of an A&PC Scientist, 6.2 Compressive Strength Testing shall be performed by qualified

, personnel in accordance with QIP-27, i

i I

1 4

9 4

1 O

1 l

5 A

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l WVNS-TRO-030 Rev. O I T -

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x ,

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0 5 \ h 71 D

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k S I il l E a s V :_ e

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Figure 1: Drum Sampling Locatioris i.

s-..

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

O west valley -c. " -der ="s-te-oso

"*"'"2"""""

Demonstration Project Revision Date 05/03/91 Engineering Release #2080 TEST PLAN TEST PLAN FOR FULL-SCALE CONFIRMATION OF NOMINAL RECIPE OF SLUDGE WASH LIQUIDS 4

i PREPARED BY Y[ u (/ L. E. Michnik Cognizantyt g APPROVED BY W;py D. C. Meess Cognizant System Design Manager APPROVED BY

/ ,4C.' / ; Win-hc!bC/'4 D. L. Shugars i

l Quality Apurance Manager APPROVED BY Dd M WRh D. J. Harward Ra(ajlon and Safety Manager

! APPROVED BY k . b O%m , J . C . C wyn ar Prc@ ss Contrd1 Engineering West Valley Nuclear Services Co., Inc.

P.O. Box 191 BELOO79 : 3RM O_ West Valley, NY 14171-0191 WV-1816, Rev.1

WNS TP 030 Rev. O RECORD OF REVISION PROCEDURE If there are changes to the procedure, the revision number increases by one.

These changes are indicated in the left margin of the body by an arrow (>) at the beginning of the paragraph that contains a change.

Example:

> The arrow in the margin indicates a change.

Revision on Rev. No. Description of Changes PaBe(s) Dated 0 Original Issue All 05/03/91 W-1807, Rev. 1 i BELOO79:3RM l

WNS TP 030 Rev. O RECORD OF REVISION (CONTINUATION SHEET)

Revision on Rev. No. Description of Changes Page(s) Dated 1

i O

W-1807, Rev. 1 11 BEL 0079:3RM O

- . . ~ - - . - . . . - - _ - . . - - .

a TEST PROCEDURE FOR FULL SCALI CONFIRMATION OF NOMINAL RECIPE OF SLUDCE WASH LIQUIDS VVNS TP 030 i REV. O 1.0 SCOPE i 1.1 This test procedure is being issued in response to k'VNS-TRQ 030- .

, The purpose of this test is to correlate the characteristics of l' full size products with those of laboratory size specimens in accordance with the requirements of appendix A of the NRC Technical-

Position on Waste Form, Rev. 1, dated January 1991.

1,2 The full scale waste form shall be fabricated in the CSS using simulated waste in accordance with SIP 91 01 (20 Drum Run).

1.3 Test specimens (3 inch diameter x 6-inch cylinders) shall be

]-

obtained from the full-scale waste form by coring in accordance with SOP 70 44 after a minimum of 28 days cure time.

l 1.4 Correlation of full-scale characteristics shall be accomplished by l performin8 compressive strength tests on specimens before and af ter 90 days immersion testing.

1.5 Compressive strength tests shall be conducted in accordance with QIP 027 and ASTM C 39.

1.6 The pre immersion compressive strength of the cores will be i determined on ten samples. The mean compressive strength of these samples should be at least five hundred psi.

. 2.0 DEFINITION AND ABBREVIATIONS i 2.1 Definitions f

Demineralized Water this water must have a conductivity of less

! than five micromho/cm at twency-five degrees celsius and a total organic carbon of less than three parts per million.

l- -

Simulated Sea Water-a combination of various inorganic j

compounds, The formulation is as follows:

23.497 grams Sodium Chloride 4.981 grams Magnesium Chloride 3.917 grams Sodium Sulfate i 1.102 grams Calcium chloride 0.664 grams Potassium Chloride 0.192 grams Sodium Carbonate j 0.096 grams Potassium Bromide 965.551 mL Demineralized Water N

BEL 0079:3RM 1-r 6

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r- e- . - - , , n . . . , . , - -

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- . - . _ - ~ - . . _- . . - - .- - - - . . - . - - - -_

WNVS-TP 030 Rev. 0 5

4 This formulation is from the Internationa Organization for

i. Standardization IOS 1691 1982(E).

k~.

2.2 Abbreviations f

! ACM Analytical Chemistry Method 1

ASTM American Society for Testing and Materials i ANSI /ANS-American Nuclear Standard-Institute /American Nuclear Society

QIP-Quality Inspection Procedure i SOP-Standard Operating Procedure s

J 3.0 RESPONSIBILITIES i

i 3.1 Analytical and Process Chemistry will be responsible for the testing of the laboratory specimens in accordance with the ACM 6400 and i ACM 6300.

j 3.2 Quality Assurance provides surveillance to ensure that the requirements of this test procedure are satisfied and will verify 2 those portions of the test where applicable. They also perform the compression testing of cylindrical specimens in accordance with QIP 027 and applicable steps of ASTM C 39.

,- 3.3 Waste Operations will be responsible for core boring the drums in accordance with SOP 70-44 j 3.4 IRTS Operations is responsible for mak'.ng the full scale drums in accordance with SIP 91 01.

1 3.5 Radiological work will be performed in accordance with WVNS

{ Radiological Control Manual, WVDP-010.

3.6 Industrial Hygiene practices are described in the WVNS Hygiene and i

Safety Manual, WVDP 011.

i 3.7 IRTS Process Control Engineering is responsible for providing

! technical support of the work outlined in TP-030. They will also

, issue TSR-030 in accordance with EP 11-003,

4.0 REFERENCES

I 4.1 NRC Technical Position on Waste Forms (Revision 1) , January, 1991.

l 4.2 ANSI /ANS 16.1 " Measurement of the Leachability of Solidified Low-level Radioactive Wastes by a Short-term Test Procedure".

I i

{

+

BEL 0079:3RM 2-4

~ ,- - , , . , . - - , , . , ,-nr .-, . . - . . , , ~ .v ,

. = - .. . . - - - - - __.. - - _. -- _- .-

1 WNVS TP 030 Rev. O I

l g 4.3 ACM 6400 " Immersion Testing of Cement Specimens" i

4.4 QIP 27 " Capping and Compressive Strength Testing of Cylindrical 4

Cement Specimens".

l 4.5 ASTMC-39 " Compressive Strength of Cylindrical Concrete Specimens".

4.6 EP-11-003 " Experimental and Developmental test Control for High-

Level Waste Form Qualification" .

i

! 4.7 WVNS TP 026 " Procedure for Qualification of the Nominal Recipe for l Cement Solidification of Sludge Wash Liquids" l 4.8 ACM 6300 " Leach Index of Cement Specimens".

1 5.0 GENERAL INFORMATION

5.1 This test will provide information on the correlation of the characteristics of full scale waste form produced from simulated waste with laboratory size specimens.

J i 6,0 PROCEDURE 6.1 Prerequisite A determination of the immersion liquid either de=ineralized l water or cimulaced saa water must be made before immersion

\ testing can be started. The most aggressive leaching liquid or 4

the one that produces the lowest Leaching Index number based upon j a twenty-four hour evaluation test, described in ANSI /ANS 16,1

! and performed according to ACM 6300, will be used for this test, i

IRTS Operations shall produce the drums in accordance with

SIP 91 01.

i The test specimens shall be cured for a -time determined by the Cognizant Engineer based on data for TP-026, but in no case less than twenty-eight days.

' - Waste Operations will obtain the cores from the drums in accordance with SOP-70-44 4

QA to be notified before start of work.-

6.2 Five drums will be cored in accordance with SOP-70-44 and twenty two samples will be obtained. See attachment-A, 6.3 Compressive strength will be determined on ten cores. See attachment A

. 6.4 The immersion testing on the cores shall be performed in~accordance p with ACM-6400. See attachment A.

BELOO79:3RM t 4

. . - .. . - - . . - . . _ . - . .~.

WNVS TP 030

Rev. 0 g 7.0 DATA ACQUISITION

! t,  ;

7.1 Compressive strength of the cores will be recorded on data sheets j in accordance with QIP 27.

7.2 Core position data will be recorded on data sheets in accordance with SOP 70 44.

I

j. 7.3 Run data will be recos .ed per SIP 91 01.

1 2

i i

1 1

i i

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!O 4

4 4

i i

i I

4 i

i 1

i i

'V BEL 0079:3RM -4

QWS.TP 030 Rev. O ATTACllMENT A DRUM TESTING MATRIX TOP MIDDLE BOTTOM DRUM #

1 1 I I I I I i 1 I c c 1 1 1 3 3 I I I I I I I I I I l I I I I I I 5 1 1 l c c I 2 I s l I I I I I I I I I I I k I l l I 10 l 2 l 3 I c c I I I I I I I I I I I I I I I I I 15 l 2 4 l C l 1 l I I I I l l I I I I i l 20 I c C l 4 4 [ C [

l I I I I I I l C - Compressive strength of samples to be determined.

1 - Sample Set al. compressive strength to be determined after 90 day immersion testing is complete.

2 - Sample set #2. Compressive strength to be determined, if necessary, after 120 day immersion testing is complete.

3 - Sample Set 23. Compressive strength to be determined, if necessary, after 160 day immersion testing is complete.

4 - Sample Set #4 Compressive strength to be determined, if necessary, after 180 day immersion testing is complete.

O v

BEL 0079:3RM A-1

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