ML20095L605
| ML20095L605 | |
| Person / Time | |
|---|---|
| Site: | West Valley Demonstration Project |
| Issue date: | 05/01/1992 |
| From: | WEST VALLEY NUCLEAR SERVICES CO., INC. |
| To: | |
| Shared Package | |
| ML20095L603 | List: |
| References | |
| REF-PROJ-M-32 NUDOCS 9205070164 | |
| Download: ML20095L605 (298) | |
Text
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WASTE FORM QUALIFICATION PROGRAM FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUID l
WEST VALLEY DEMONSTRATION PROJECT VOL.1 OF 2
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}y- ISSUED 4/16/92 VOLUME I WASTE FORM QUALIFICATION. PROGRAM FOR CEMENT SOLIDIFICATION or SLUDGE WASH LIQUID l
TABLE OF CONTENTS l l
p_OCUMENT NO. TITLE REVISION STATUS WNS-TPL-70-011 TEST PLAN FOR THE WAFTE FORM 1 COMPLETE QUALIFICATION PROGRAM FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUID WVNS SIP 91-01 LWTS/ CSS INTEGRATED TEST 0 COMPLETE WVNS-TRQ-025 TEST REQUEST FOR DEVELOPMENT OF NOMINAL 0 COMPLETE RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS WNS-TP-02 5 PROCEDURE FOR DEVELOPMENT OF THE O COMPLETE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS WNS-TSR-2 5 DEVELOPMENT OF THE NOMINAL RECIPE FOR 0 COMPLETE CEMENT SOLIDIFICATION OF FLUDGE WASH LIQUIDS WVNS+TRQ-026 WASTE FORM QUALIFICATION WORK FOR THE O COMPLETE O)
s NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS WVNS-TP-026 TEST PLAN FOR QUALIFICATION OF NOMINAL 0 COMPLETE RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS WNS-TSR-02 6 TEST
SUMMARY
REPORT FOR QUALIFICATION O COMPLETE RECIPE FOR THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS WVNS-TRQ-028 TEST REQUEST FOR DEVELOPMENT OF THE 1 COMPLETE PROCESS PARAMETERS FOR CEMENT SOLIDIFICATION OF SLUDGF WASH LIQUID WVNS-TP-028A DEVELOPMENT OF PROCESS CONTROL 1 COMPI ETE PARAMETERS FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS WNS-TP-02 8 B WATER TO CEMENT RATIO VARIANCE IN O COMPLETE
-SIMULATED SLUDGE WASH SIUDGE WASH CEMFNT WASTE FORM O COMPLETE WNS-TSR-28 QUALIFICATION DEVELOPMENT OF PROCESS CONTROL PARAMETERS WVNS TRQ 029 PRODUCTION OF CEMENT PRODUCT FROM 1 COMPLETE ACTUAL SLUDGE WASH' LIQUID O
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DOCUMENT % TITLE REVISION g .]
WVHS-TP-029A~ TEST PROCEDURE FOR CONFIRMATORY CUBE O COMPLETE WVNS TSR-029 SLUDGE WASH CEMENT _ WASTE FORM I COMPLETE
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i QUALIFICATION WVNS-TRQ-030 TEST REQUEST FOR FULL-SCALE O COMPLETE CONFIRMATION OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUID WVNS-TP-030 FULL SCALE CONFIRMATION OF THE NOMINAL 0 COMPLETE RECIPE OF-SLUDGE WASH LIQUIDS WVNS-TSR-030- TEST
SUMMARY
REPORT ON FULL-SCALE FORECAST CONFIRMATION OF NOMINAL RECIPE FOR 4/30/92 SLUDGE WASH LIQUID 4 i
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Demonstration Project Rese1= N-eer i Revision Date 09-05-91 Engineering Release #2044 ECN #4534 TEST PLAN FOR THE WASTE FORM QUALIFICATION PROGRAM FOR CEMENT SOLIDIFIC ATION CF SLUDGE WASH LIQUID PREPARED BY ANN M. N. Baker Cognizant Engineer APPROVED BY 4 3.0 #@ D. C. Meees
[N (ognizant Systeq Design Manager
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APPROVED BY M' \)cL6. P. J. Valenti Faci'4jty Representative APPROVED BY ' ,*
';t) l_ d, /. ..-; W // / /k D. L. Shugars Quality Agourance Manager APPROVEDBYf/M6/ -
[ D. J. Harvard
' Radiation & pff'ety Manager /
APPROVED BY kil b w%v IR"l) Procesd Control Engineering J. C. Cwynar West Valley Nuclear Services Co., Inc.
P.O. Box 191 l (mj SAJ0062: 3RM West Valley, NY 14171-0191 WV-1816, Rev.1 l
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' WNS TPL-70 11 Rev. 1 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 'l the beginning of the paragraph that contains a change. l Example: ;
4 > The arrow in the margin indicates a change.
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Revision On Rev. No. Description of Changes- Page(s) Dated a
0 Original Issue All 03 25 91 1 Per ECN - 4534 2 thru 4 09-05-91 t
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WVNS TPL 70 11 TEST PLAN FOR THE WASTE FORM QUALIFICATION PROGRAM FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUID REV. 1 1.0 PURPOSE The purpose of this test plan is to describe the Waste Form Qualification Program for Cement Solidification of Sludge Wash Liquid. The plan specifies 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 Waste Form.
Revision 1, draft dated Decamber 1990.
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' GENERAL REQUIREMENTS-O 3.1 All procedures _for conducting tests and documenting and evaluating test results will be prepared, reviewed, and approved in accordance with the requirements of the WVNS Policy and Procedure Manual.
Engineering Procedures EP-ll-001, EP-11-003, and SCP 00-2, 3.2' Test requirements will be as specified'in Test Requests (TRQ) issued
, by the IRTS Process Control Engineering organization in accordance
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with EP-ll-003.
3.3 Testing in response to the lest Resquesta shall be performed in accordance with the Test Procedures (TP) issued by the Analytical &
Process Chemistry Laboratory in accordance with EP-11003.
3.4 Op. ration 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 pucformed in accordance with EP-ll-001 and EP 11 003 as applicable.
SAJ0062:3RM (
WVNS-TPL 70 11 Rev. 1 4.0 SCOPE 41 The scope of the qualification program will be as described in documents summarited in the flowchart (Figure 1).
l 4.2 Nominal Recipe Development (VVNS TRQ 025)
Devalopment 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, .
and Sodium Silicate.
4.3 Waste Form Qualification (WVNS-TRQ 026)
Qualification of the " nominal" recipe will include establishing a curve of compressive strength vs. time, determination of the maximum practical compressive . strength, verification of compressive strength af ter thermal cycling, determination of resistance of leaching of radionuclides, and verification of compressive strength af ter immersion.
4.4 Full-Scale Verification (WVNS TRQ-030)
Full-scale verification of the " nominal" recipe will take place aftir curing of the full-scale drums processed under SIP 91 1. The drums will be core drilled, and the cores will be evaluated for compressive strength, as well as compressive strength after immersion.
4, 5 Development of Process Control Parameters (VVNS-TRQ-028)
Recipe boundaries will be determined for the following parameters, as a minimum: Total Dissolved 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.
The effects of variations in the waste stream will be evaluated for the following parameters: Aluminum content, Sodium content, Organics, Sulfates, pH, Nitites, and Phosphates.
> Plackett-Burman Screrning Tests (WVNS-TP-028A)
> 28 cubes will be produced from 28 solutions representing variations .
in the liquid waste chemical compositions and recipe enhancers.
These cubes will be used to screen the degree of interaction between-13 individual components.
> The effects of vatiations will be evaluated for: bleedwater, gel time, and. penetration resistance.
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WNS TPL 70-11 .l Rev.-1'
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> Box Behnhen Tests (WNS TP 02898)
> Based on the. results of WNS-TP 028A above, additional tests of the key' variables (those with significant interactions) will be conducted to precisely define the recipe limits for each key i variab1'e. j
-4.6 Confirmatory Testing (WNS-TRQ-029)__ j For this test, a quantity of actual High Level Waste Tank Sludge will~ be decontaminated .in the laboratory, and the resulting liquid will be. solidified using the " nominal" recipe. The compressive strength of the solidified sample-will be determined.
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5.0 DESCRIPTION
i 5.1 Mixing of lab scale specimens shall be performed under conditions - ! which duplicate the full-scale mixing conditions mixer speed, mix . time, etc., to- the maximum extent practical, as discussed in the l 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 followtd 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 Compressive strength testing of cylinders (both cast and core-drilled) will be performed in accordance with the applicable steps of ASTM Standard C-39 and the Branch Technical Position, Appendix A.II.B. 5.5 Testing of thermal stability will be performed in accordance with the applicable sections of ASTM Standard B-553 as discussed in the Branch Technical Position, Appendix A.II.C. 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 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 hour test. 5.7 Development of process contrcl parameters will be performed in accordance with existing ACM's, and as discussed in the Branch Technical Position Appendix A.VI.A. 5.8 Immersion testing will be performed in accordance with the _ Test Procedures (TP's) for that work, and as discussed in the Branch Technical Position, Appendix A.II.G. The immersion testing will be performed using the most aggressive leachant (deionized 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 Branch Technical Position. 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 L Technical Position, Appendix A.II.H. Any free liquid encountered l .shall have a pH greater than or equal to 9. l SAJ0062:3RM= - . - -. - _- ..
4 - WNS TPL 7011 Rev. 1 5.10 Sufficient samples shall be-tested to provide enough data to j j establish a mean and a standard deviation, as discussed in the
- Branch Technical ~ Position,' Appendix A.IV
-5.11- Irradiation testing of the waste form will NOT be performed, because 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 schnical Position, Appendix A.II.E.
6.0 REFERENCES
l
6.1 10CFR61
Code-of Federal Regulations, Title 10, Part 61,
" Licensing Requirements for Land Disposal of Radioactive Wasto
i 6.2 ASTM C-39: Standard Test Method for Compressive Strength of Cylindrical Concrete Specimens 6.3 ASTM C-109: Standard test Method for Compressive Strength of
. Hydraulic Cement Mortars Usin6 2 inch or 50 mm Cube Specimens ,
6.4 -ASTM B-553: Test Method for Thermal Cycling of Electroplated 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
- Solic,1fied Low Level Radioactive Wastes by a Short-term Procedure
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"SUBKIT DATA S11E2T(S)'
O~ UNCONTROLLED CO)Y Applicable Field Changes -
.DO NOT USE FOR WORK SIP 91 01 LUTS/ CSS INTEGRATED TEST
' Rev. O Approved I)c__d3 Approved ' b . b- - s . - - -
IRTS(Dperations Manager Pti6 cess Condrol Engineering Manager Date 4- 6 o-S 1 Date '4!30 )9 l 8 _ Approved An ((.$* Approved & AI r!be Of h Radiation and Safety Quali$y Assurance Manager Date 5/~f/ Date l THIS PROCEDURE EXPIRES 07/31/91 . AFIER THIS DATE.-DISCARD EXCEPT FOR MASTER FILE AND COMPLETED WORK COPY System Quality Level C System Safety Class C The estimated accumulated dose for the work described in this document is less than 100 mrem. WEST VALLEY NUCLEAR SERVICES CO,, INC. May, 1991 i Prepared by: -@// M-M.'N. Baker BELOO19:8RM l 1 l l-l
SIP 91-01 Rev. O RECORD OF REVISION PROCEDUR_E If there are changes to the procedure, the revision number increases by one. l These changes are indicated in the left r.argin 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.
Procedure No. SIP 91 01, Rev. O Date: May 1991 Rev. No. Description of Changes No. of Page Dated 0 Initial' Document All 05/91 F) v
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SIP 91-01 ' O* Rev. O RECORD OF REVISION (CONTINUATION SHEET) Rev. No. Description of Changes No. of Page- Dated O
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Rev. O TABLE OF CONTENTS Step Description
.Pa.fle.
1.0 SC0PE...........................................................1 2.0 DEFINITIONS AND ABBREVIATIONS................................... 2 2.1 De f i ni t i o ns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2.2 Abbreviations................................ ............. 2 3.0 RESPONSIBILITIES. .............................................. 3 4.0 TOOLS, EQUIPMENT, COMPONENTS AND REFERENCES..................... 4 4.1 -Tools and Equipment......................................... 4 4.2 Components......................................... ....... 4 4.3 References......................................... ....... 4 5.0 C ENERAL INFORMATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
/,- 6.0 PROCEDURE....................................................... 8 v
, 6.1. Pr e r e quis i te s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 L 6.2 S bralant Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 6.3 CS S Op e ra t ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 6.4 Thermocouple-Equipped Drum.......... ...................... 10 6.5 S amp l in g . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -. . . . . . . . . . . . . . . . 11 6.6 Test Completion............................................ 12 7.0 ATTA CHMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 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 Locatior . . . . . . . . . . . . . . . . . . . . . . C-1 f BEL 0019:8RM 111 t
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-- SIP 91-01 ,
V Rev. O FULL-SCA1.E VERIFICATION TEST 1.0 SCOPE The objectives of the full-scale verification test of CSS are: 1.1 Verify that the full-scale vaste forms produced from simulated sludge wash solutions in the CSS meet the requizements of vaste stability per 10 CRF 61.56 by checking for free liquid, fill level, and penetration resistance per SOP 70-40, 1.2 Verify ths. the CSS consistently operates within the limits set by
.VVNS-TRQ 028, " Test Request for Developmant of the-Process Control Parameters for Cement Solidification of Sludge Wash Liquids."
tO 1.3 Verify the ability of the process instrumentation to measure and document process control parameters. 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, itVMS-TRQ-026. Correlation vill be accomplished by performing (1) compressive strength testing on as-cured material (cured a-mintmum of 28 days) 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 Rev. O sv 1.5 Verify that the full-acale vaste forms demonstrate the stab,ility k,,) . requirements of the USNRC Branch Technical Position on Waste Form, (reference 4.J.36) appendix A, and VVNS-TRQ-030. 1.6 Produce test specimens (40 cubes 2"x 2"x 2" and 50 cylinders 3" Diameter x 6" long)
'l.7 This-SIP will be conducted in accordance with VVNS-PCP-001, Rev. 4.
2.0 DEFINITIONS AND ABBREVIATIONS 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. 4 2,1,2 Data Acquisition System - Computer based system which . O' monitors and records the outputs of selected CSS instrumentation. 2.1.3 Total Dissolved Solids-- concentration of dissolved salts usually expressed as parts per million (ppm) or weight percent (w/o or we t). 2.2 Abbreviations A&PC - Analytical and Process Chemistry VDV. - Vaste Dispersing Vessel CSS - Sement Solidification System DAS Data Acquisition System EUP - Industrial Work-Permit IRTS - Liquid Waste Treatment System PCE - Process Control Engineer [. BEL 0019:8RM ,. -2
. SIP 91'+01 Rev. 0 REP - Radiation Work Permit R&S - Radiation and Safety SSS - Start-up Shift Supervisor l l
TDS. - Total Dissolved Solius. ; i 3.0 RESPONSIBILITIES 3.1 Inte5 rated Radwaste Treatment System (IRTS) Operations perfonu the testing required by this procedure and completes the data shoeu to document the procedure. 3.2 IRTS Support Engineering provides technical support as necessary. 3.3 Process Control Engineering (PCE) provides technical direction during testing and checkout, compares the test Benerated data to Test Plan VVNS-TPL-70-Oll, and issues Test Results Reports.
-. 3.4 QA provides surveillance to assure that the requirements of this ' procedure are satisfied, and signs to indicate verification of work performed and data collacted.
l 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 Manageraent operations performs filled drum movements to the
-drum cell and core-boring-per VVNS-TP-030.
3.8 A&PC analyze and verify satisfactory simulant chemical makeup. { BELOO19:8RM
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, SIP 91 01 I
, , Rov. 0 4,0 TOOLS, EQUIPMENT, COMPONENTS AND REFERENCES
(N- - L/ 4.1- Tools And Equipment Intercom System Solid Sample (s) Transport Container (s) Forney Compre'sive Strength Testing Equipment Lifting and rigging equipment D'Sposable Plastic 2" x 2" x 2" Cube Sample Molds Plastic 3" dia. X 6" high cylinder sample molds Controlled-Temperature Chamber j .
-/ 4.2 Components CSS - All Cement / Waste mixir.g equipment fully operational 4.3 References 4.3.1 SOP 70-1 Waste Transfer to the Cement Solidification System-4.3.2 SOP 70-3 Automatic Solidification Operation P
, 4.3.3 SCP 70-4 CSS Manual Solidification with the . Process Logic-Controller Operational 4.3.4 SCP 70-5 Gravimetrie. Feeder Operation i 4.3.5 SOP 70-6 Bulk Cement Transfer to Day Bin O BEL 001978RM ,.
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. SIP 91 01 Rev. 0
~_ 4.3.6 SOP 70 7 Cement Truck Unloading ,
G 4.3.7 SOP 70 8 Clean Drum Handling for Cement Solidification System 4.3.8 SOP'70-9 Automatic Drum Processing Operation 4.3.9 SOP 70-10 Full Drum Handling For CSS 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
-s 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 i
l 4.3.19 SOP 70-34 operation of the 01-14/ CSS Process Room 4-Ton Bridge Crane
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9 l 4.3.20 SOP 70-35 Operation of Kaintenance 2-Ton Bridge Crane-4.3.21 SOP 70-36 Drum Cell Crane Operation i
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r 4.3.22 SOP 70-37 Smear Robot Operation up)- BEL 0019:8RM ,.
, SIP 91 01 Rav. 0
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g 4.3.23 SOP 70 39 Draining and Flushing the UDV 4.3.24 SOP 70-40 CSS Drum Sampling Station Operatioa 4.3.25 SOP 70 41 CSS Preventive Maintenance Program 4.3.26 SOP 70 42 CSS Safe Shutdown Drring an Emergency Situation 4.3.27 SOP 70-43 Emergency Emptying of CSS Mixers 4.3.28 SOP 70-45 Waste Classification 4.3.29 SOP 70-46 Operation of the Sodium Silicate Delivery System 4.3.30 SOP 002 Guidelines for the Preparation of Facilities Work Ins':ruction Documents
\. 4.3.31 SOP 004 Lock and Tag Procedure 4.3.32 EP 11 ^01 Test Control 4.3.33 WV-222 Trouble Record.=
4.3.34 TPL 7011 Test Plan for the Vaste Foru Qualification , Program for Cement Solidification of Sludge Wash Liquid
- 4.3.35 WVNS PCP 001 1ss Control Plan for Cement Solidification of Decontami cernatant -
4.3.36. DOE ORDER 582- "a), Radioactive Waste Management l -- ,, n .* - .
- l. 4.3.37 US NRC Branch Technical Position on Waste Form, Rev. 1 dated January,1991 , ,
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, SIP 91-01
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4.3.38 WVNS-TP-026, Test Procedure for Waste Forn Qualification of
'v - the Nominal Recipe for Ce:nent Solidification of Sludge Wash i Liquid 1
4.3.39 WVNS-TP 030. Test Procedure for Full Scale Verification of the Nominal Recipe for Cement Solidification of Sludge Wash I Liquid
- 5. 0 CENE'lAL INTURMATION 5.1 Simulant mixed for this testin5 shall be transferred to the UDV in the CSS for solidification.
5.2 This Waste Stream shall be solidified in the CSS using recipes developed at Analytical and Process Chemistry, and listed in UVNS-PCP-001, Rev. 4. All operations chall be conducted per System 70 SOPS. V) 5.3 Cube samples and cast cylinders will be obtained from these drums and destructively tested. This testing will be performed in accordance with WVNS-TP-026. 5.4 Core samples obtained from these drums af ter curing a minimum of 28 days will be destructively tested in acce.rdance with WVHS-TP-030. 5.5 OPERATORS SHOULD PERFORM FREQUEKr CHECKS ON SYSTEMS THAT ARE TURNED ON OR SHDT DOWN TO ASSURE THAT THE SYSTEM DOES WHAT IS EXPECTED, I.E. , WATER FIDWS, PRESSURE RISES, LEVEL INDICATORS, ETC. IF THE REQUIRED ACTION THAT IS SUPPOSED TO HAPPEN DOES NOT HAPPEN, (1) STOP - DO NOT ATTEMPI TO PERFORM THE NEIT STEP, (2) SECURE
- c SYSTEM-IN A SAFE MODE, AND (3) NOTIFY SHIFT SUPERVISOR IMMEDIATELY. 4
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6.0 PROCEDURE (' h '
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ALL STEPS IN THIS PROCEDURE THAT REQUIRE AN INSPECTION, TIF. RECORDING OF DATA, OR A SIGN-OFF WIII BE DENOTED BY A [+] IN THE I2FT-HAND MARGIN. THE INSPECl' ION RESULTS, DATA, OR SIGN-OFF VIII AE RECORDED ON THE APPROPRIATE PRDCEDURE DATA SHEET (S). 6.1 Prerequisites [+] 6.1.1 Notify PCE and QA prior to performing any testing. Obtain i an RUP and IVP to perform drum testing. ' [+] 6.1.2 Shift Supervisor or Shift Engineer verify SOPS listed in Section 4.3 are current, i [+] 6.1.3 Record Serial Nua er and Calibration Data for Scales used in Section 6.2 on attachment A. 6.2 S,,jpulant Preparation 6.2.1 Mix cold test chemicals in accordance with the following simulant recipe: Chemical Symbol Weight Source Sodium Nitrate NANO 3 286.3# P.U. 49405 Sodium Nitrite NANO 272# P.O. 49408 Sodium Sulphate NaoS$ 4 169.9# P.O. 49871 Potassium Nitrate KNd 3 17.9 P.O. 49406 Sodium Carbonate Na2CO 3 48.4 _ P.O. 49406 _ Sodium Hydroxide NaOH 1.77 P.O.-49409 Sodium Bichromate Na2CrO4 2.48 P.O. 49871 < Sodium Chloride Nacl 1.88 From VIT , Sodium Phosphate NaPO 4 1.53 P.O. 49409 Sodium Molybdate Na2M04 0.33 P.O. 49871 Sodium Tetraborate Na3B0 3 0.19 P.O. 49871 Citric Acid - 0.26 .' P.O. 49920 - .- Oxalic Acid - 0.26 P.O. 49920 Tart mit Acid - 0.26 P.O.'49920 '~v . . p Demineralized Water M ,0 200 gallons
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. SIP 91 01 Rev. 0 I
6.2.2 Mix the chemicals and water in the tank and piping ' setup erected uncer separate work order (VO 9100084). [+] 6.2.3 Obtain a sample of the simulant. Record lab analysis number on attachment A. A&PC verify astisfactory. 6.3 CSS operation 6.3.1 Load the gravity feed conveyors with a minimum of 25 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 che mix tank pump to fill the Waste Dispensing vessel. 6.3.4 Repeat step as required to keep the UDV liquid level above the low level set point ( 35 gal . 6.3.5 Use SOP 70-3, to operate the CSS auto.aatically. 6.3.6 Uhen the last batch of vaste bains processed is in the mix cycle, switch the program selector to "A" to automatically stop the program when the batch is complete. 6.3.7 Use SOP 70-12 to flush the mixers. _, 6.3.8 Use 50P 70-39 to drain and flush the VDV if required. . 6.3.9 Hold the completed drums in the Drum Loadout Area,
~
Transportor, or Process Cell as required. BELOO19:8RM ,. _ _ _ _ _ - _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .
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4 SIP 91 01 Rav. O
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g [+] 6.3,10 Select ten (10) drums 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 run. Record drum numbers on attachment B. ,
[+] 6.3.11 For each drum sala:t:.d, determine through review of ; production data if cement /vaste mixture was produced within tolerances specified in recipe data sheets and record results on Data Sheet No. 2. 6.4 Thermocouple-Equipped Dnta 6.4.1 Equip the first drum processed with thermocouples and temperature recorder as follows: 6.4.2 Insert three (3) thermocouples 10", 20", 30" long through the vasta along the drum centerline. [(/ 6.4.3 Connect wires to a Molytek recorder
- a. Program the recorder to print the temperature at 10-minute intervals
- b. Plug the recorder into a ll5VAC receptacle in the Drum Loadout Area
- c. Locate the recorder near the drum c.;
.6.4.4 Equip one (1) of the cylinders cnst via step 6.5 with a 6" long K thermocoup% ,inconel 600) (no recorder). The' < -
instrument that th'is m rmocouple will be connected to must _, ,_ , be calibrated _co agaately display and/or record ,
.. temperature sensed by thermocoupie.
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- SIP 91 01 Rov. 0
- a. This cylinder will be used a9 a control cylinde,r during thermal. cycling testing per WNS TP 026 6.4.5 Hold the thermocouple equipped drum in the Drum Loadout Area until the drum centerline tempatature returns to ambient.
6.5 S_ampling 6.5.1 After the drum to be sampled is completed, enter the Process cell and obtain 2" x 2" x 2" cube samples:
- a. Vith the drum at Till f- ' ton M 15 RAISE the fill nozzle
- b. Move the drip tray IN
- c. Place the cube molds on a towel vipe
- d. Scoop the cement / waste product from the drum and fill the cube molds
- FILL THE HOLDS AS FULL AS POSSIBLE *
- e. Place the molds in a poly bag containing vipes
- f. Label the bag with the druin number, date, and time 2
6.5.2 Obtain 3* diameter x 6" 4.ug cylindrical samples as follove: 9
- a. Place the cyliador molds on a towel wipe ,
- b. Scoop the cement / waste product from the drum and fill r] the cylinder molds V
BELOO19:8RM . -11
SIP 91 9) Rev. 0
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- FII.L THE MOLDS AS FULL AS POSSIBLE * '
- c. Place the molds in a poly bag containing vipes
- d. Label the bag with the drum number, date, and time 6.5.3 Repeat for a total of forty (40) cubes from up to ten (10) drums.
- DO NOT OBTAIN MORE THAN TEN (10) CUBES FROM A DRUM
- 6.5.4 Repeat for a total of fifty (50) cylinders from up to ten (10) drums.
- DO NOT OBTAIN MORE TRAN TEN (10) CTLINDERS FROM A DRUM
- 5.5.5 Release the begged samples for transfer to the controlled temperature chamber for curing in accordance C with WNS TP 026.
- 6.6 Test completion 6.6.1 Flush the remaining simulant and chemicals f, a the mixing tank to the waste dispensing vessel.
6.6.2 When the last batch of simulant has been processed, flush the mixers per SOP 70 12, and shut down the CSS. [+] 6.6.3 Shift engineer verify all open items, TRs and TEs have been ' closed out. [+] 6.6.4 QA representative verify. ,, L) BELOO19:8PJi ,. . - - , - .. - -., .- - - - - - . - - , -.
., SIP 91 01 Rev. 0 4'
7.0 ArrACHMDITS , 7.1 Attachment A: Prerequisites and Test Completion Data Sheet No. 1 7.2 Attachment B: Data Sheet No. 2 7.3 Attachment C: Core Sampling Locations i O BEL 0019i8BM ,. _ .. .. . . . . - -- - - . . , - -. - - . - - . . - . - .. . -.
,' SIP 91 01 Rov. 0 ATTACHME!TT-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 Ices Serial No. Last Calibration 0 - M
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6.2.3 Simulant Sample Results: Sampled by Operator /Date Sample Results
, Lab Ana's.ysis No.
Results Acceptable , A&PC/Date . 6.6.2 Shift Engineer verify all test exceptions, trouble records, open < +.
..3 s4 j.,.--
items are closed out
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* ' SIP 91 01 Rev. O !
t e 7_ ATTACIUiENT B , Data Sheet No. 2 l l l l l l f 6.3.10 Drum Number l- l l l l l 1 1 I I I l Waste Type l l 1 l l l l l l l l 1 6.3.11 Drum Weight From M 15 (1bs) l l l l l l l i l I I l Drum Weight From Mixer j l l l l l 1.oad Cell (Iba) l -l l l 1 l l 1 I I I I
. Vasts Within Tolerance l l l l l l (Yes/No) l l l l l l l l l 1 l l O
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. Attcchtnant C: Drum Sampling Locations
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3, i C) West Valley ox " - " = "s-'ne ~ s Demonstration Project l Revision Date 04/30/91 Engineering Release #2074 I TEST REQUEST DEVELOP!1ENT OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS PREPARED BY 4/W W M. N. Baker Cognizant Engineer APPROVED BY 3/ D. C. Meess Cog 6Trant System Design Manager APPROVED BY _:/ :'r i cC6/f r [ . L. Shugars Quality Ap'irance Manager ARP[j^gBY 7 b. Aj / 0. J. H arw ar d I f V tsdiation apd 'Saf ety Manpfer APPROVED BY k. b b+ d,~~ Of i 9 l9 l J. C . Cwynar , Prodess ContrV1 Engineering ~ : . l-West Valley Nuclear Services Co., Inc. l P.O. Box 191 i BEL 0046 :3RM West Valley, NY 14171-0191 WV 1816, Flev.1
VVNS TRQ 025 Rev. 0 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 Laginning 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 04/30/91 O VV 1807, Rev. 1 BELOO46:3RM i
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WNS TRQ 025 Rev. 0 RECORD OF REVISION (CONTINUATION SilEET) 4 Rev. No. Description of Changes Revision on Page(s) Dated i
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___ _ _ _ _ _ _ --m..._- _ _ __ _ _ _ . -.. - -___ _ _ m _.m () VVNS TRQ 025 l Rev 0 DEVELOPMENT OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION 0F SLUDGE VASH LIQUIDS I 1,0 INTRODUCTION This work is required to develop a stable vaste form for cement solidification of Sludge Wash Liquids which meets the characteristics i required by 10 CFR 61, Code of Regulations, Title 10 " Licensing Requirements for Land Disposal of Radioactive Waste," and the USNRC
- Branch Technica' Position on Waste Form, Revision 1, dated January 1991. '
i 1.1 All work will be performed in accordance with VVNS-TPL 70 011, the Test Plan for the Vaste foru Qualification Program for Cement Solidification of Sludge Wash Liquid (reference 7.3) and related , test procedures. _ i 1.2 All work will be performed with a " nominal" simulant representing the actual waste liquid. The composition of;the " nominal"-simulant
-was identified by Analytical and Process Chemistry based on Sludgo Wash Experimentation (reference 7.1) and Mass Balance Modeling Calculation (reference 7.2). The composition of the "nominal" waste -
simulant is shown in table.l. 2.0 OBJ ECTIVE [
\-e') _
2.1 Using the simulant liquid, and the existing recipe for supernatant solidification,-develop.the " nominal" recipe as follows:
- a. Characterire the solids in the vasta liquids sulfates, nitrates / nitrites, aluminum, organics, etc.
- b. Determine the " nominal" percent solids (by weight) in the wasta liquid- *
- c. Determine the " nominal" range of Calcium Nitrate recipe enhancer to be blended with Portland Type I cement,
- d. Determine the ' nominal" water to cement ratio. Note that this ratio is to be calculated as follows:
V/C; (weight f waste) x (1 ;_ solids. fraction) fl - Calcium Nitrate fraction) x (weight of cement)
- e. Determine the " nominal" amount of Ant 1 foam (GE AF9020) recipe
- enhancer to be added to'each-batch. -
- f. l Determine the " nominal" amount of Sodium Silicate recipe-l- ' enhancer. -
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l WVNS TRQ.025 i
' Rev. 0 2.2 At a minimum, slurry density. Bel time, free liquid, penetration resiutance and compressive strength shall be determine for each s, specimen.
2.3 The compressive strength of the encapsulated waste shall achieve the maximum practical compressive strength, as required by the Branch Technical Position, appendix A.11.3. A mean compressive strength in excess of 500 psi is required. Lab scale specimens will be 2" x 2" x 2" cubes in accordance with the applicable steps of ASTM Standard C 109. 2.4 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.11.1. Correlation may be limited to compressive strength test results and immersion tests, as discussed in VVNS TRQ 026. 2,5 Lab.seale specimens shall be cured at 880 0 120 0, for 6118 hours, the same conditions as full scale products, as described in the Branch Technical Position, appendix A.111.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 test.ag, as discussed in the Branch Technical Position. appendix A.III.C. 3.0 SAFETY 3.1 Industrial hygiene practices will be an descr' bed in the VVNS Hygiene 6 Safety Manual, VVDP 011. 3.2 -Fadiological work will be performed in accordance with the VVDP " Radiological Controls Manuals, VVDP 010. 3.3 Work in the Analytical & Process = Chemistry lab will be performed in accordance with existing A61'C methods ~(ACM's). 4.0 EQUIPMENT CONFIGURATION 4.1 All lab equipment will be set up in accordance with WVNS TP 025, and as directed by the cognizant A&PC scientist or qualified A&PC technician. 5.0 SAMPLING FREQUENCY
, 5.1 A minimum of ten (10) cube specimens will be produced using the
" nominal" recipe as specified by the cognizant A&PC scientist.
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- Rev. 0 6.0 PERSONNEL QUALIFICATION I
6.1 Testing will be performed by qualified Analytical 6 Process Chemistry technicians in accordance with WVNS-TP 025 and using Analytical Chemistry Methods (ACM's) under the cognizance of an A&PC
. Scientist,
- a. Radiochemistry "B" Technicians qualified to WVNS-QS 014.
- b. Radiochemistry "A" Technicians qualified to WVNS-QS 016.
6.2 Surveillance activities will be performed by qualified Quality Assurance personnel.
7.0 REFERENCES
7.1 " White Paper on Extraction of Plutonium from 1kaline liigh Level Liquid Waste," L. A. Bray, F. T. Hara, and T, F. Karmierezak, Draft C, dated December 21, 1990. 7.2 "Proliminary Flowsheet: Sludge Wash with Existing 8D 2 Heel," letter EK:91:0047, dated March 7, 1991. 7.3 VVNS TPL 011, Test Plan for the Waste Form Qualification Program for Cement Solidification of Sludge Wash Liquids, M. N. Baker, dated March 25, 1991. 8,0 REPORTING 8.1 The test procedure (VVNS.TP-025) for conducting tests in accordance , with this test request shall be issued by the A6PC laboratory. 8.2 A Test Summary Report (TSR) will be issued by the Cognizant Engineer or Cognizant A&PC scientist documenting the results of- testing in accordance with EngineerinS Procedure EP-11 003. BEL 0046:3RM 3
,. _ ~ .. w , _ : . _ ..___..__,_.___.._..u_....- - . _ _ , . _ . _ _ . _ _ _ . _ _ , _ _ _ _ _ _ _ . _ _ _ .
WVNS-TRO-025 Rev. O TABLE 1: Salt Concentrations for the " Nominal" Recloe Based on 128.5" Heel Constituent Formula Weight Sodium Nitrate NANO 3 35.62 Sodium Nitrite NANO 2 33.84 l Sodlum Sulfate Na2SO4 21.13 Sodium Bicarbonate NaHCO3
- Potassium Nitrate KNO3 2.23 Sodium Carbonate Na2CO3 6.02 Sodium Hydroxide NaOH 0.22 Sodium Chromate Na2CrO4 0.308 Sodium Chloride Nacl 0.234 Sodium Phosphite Na3PO4 0.190 bodium Molybdate Na2 moo 4*2H2O O.040 Sodium Borate Na28407 0.024 Citric Acid C6H007 0.032 Oxalic Acid C2H204 0.032 l Tartaric Acid C4H606 0.032 Water H2O 203.03 Total Welont 302.982 Weight of Solids 99.952 Weight Percent Solids 33*/.
8 Notes Sodium Bicarbonate does not appear as NaHNO3 at elevated pH s 4
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West Valley- oec. "==ser ="s rr-o2s Demonstration Project """i""-"' Revision Date 05/24/,91 Engineering Release #2098 i TEST PROCEDURE PROCEDURE FOR DEVEL01 DENT OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS PREPARED BY 9/8 h M. N. Baker Cognizant Engineer APPROVED W D. C. Meess Cognt: ant System Desig,n Mana er O '/Af 9h[i A.PPROVED BY /t )>-L-ujR ..F gO. L. Shugars Quality AgJar'hnee Manager / APPROVED BY $) An $ N @D. J. Harvard kadiation ar.d Safety Manager APPROVED BY 4,6 k J. C. Cwynar PrVcess Conthol Engineering West Valley Nuclear Services Co., Inc. P.O. Box 191
/'s BELOO49:3RM
(/ . West Valley, NY 14171-0191 WV-1816, Rev.1 l 1 1
VVHS TP 025 4 Rev. 0 RECORD OF REVISION PROCEDURE
'%J 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 j Example:
> The arrow in the margin indicates a change.
l i Revision On ' Rev. No. Description of Changes Page(s) Dated i l 0 Original Issue All 05/24/91
-k) WV 1807 Rev. 1 BELOO49:3RM =
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l WVNS.TP.025
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RECORD OF REVIS10N'(CONTINUATION SHEET) ' fh , i V Rev, No.- Description of Changes Revisi n on Pageks) i Dated ; l
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_.. _. , __ _ = _ _ _ . _ _ . _ _ _ . . . . _ _ _ _ _ _ _ _ . _ _ _ . . . _ WVNS TP-025 O PROCEDURE FOR DEVELOPMENT OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE VASH LIQUIDS Rev. O f 1.0 SCOPE 1.1 This work is required to develop a stable waste form for cement solidification of Sludge Wash liquids which exhibits the characteristics required by 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. 1.2 The recipe for cement solidification of supernatant (DOE /NE/44139 49) will be used as a starting point for this tect procedure.
}
1.3 Work will be performed with a simulant representing the actual vasta liquid to develop the " nominal" recipe for solidification of sludge wash liquids. 1.4 A prerequisite for all work will be the decision by the IRTS Restart Task Force as to the actual level of supernatant liquid in High Level Vaste Tank 8D 2: 129 inches. 1.5 A prerequisite for all work will be the determination by the IRTS Restart Task Force of the expected amount of Sulfate in the Sludge Wash Liquid. The composition 'f the " nominal" recipe, based on letter No. EK:91:0047, is given in table 1. 1.6 ~ Vork will be performed using cubes 2" x 2" x 2" cast from a simulant / cement mixture produced in the Analytical Chemistry Lab.
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WVNS TP 025 Rev. 0 l
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() 1. 7- The " nominal" percent solids (by weight) in the wasta liquid will be determined. I 1.8 The " nominal" range of Calcium Nitrate recipe enhancer to be i blended with Portland Type I cement will be determined. 1.9 The " nominal" water-to cement ratio will be calculated as follows: i (Veight of waste) x (1 solids fraction) V/C - (1
- Calcium Nitrate fraction) x ( Weight of cement blend) ;
1.10 Determine the " nominal" amount of Antifoam recipe enhancer co be ; added to the liquid mixture. 1.11 Determine the " nominal" amount of Sodium Silicate recipe enhancer to be added to the vaste/ cement mixture. ; 1.12 .The maxinam practical compressive strength of the waste form will be determined. 1.13 The effects of variable recipe parameters on the " gel time" and free liquid of the waste mixture will be evaluated. > 1.14 The " nominal" recipe developed herein will be scaled up and qualified in accordance with VVNS TRQ 026. It will also serve as the " nominal" recipe for Process Control Plan parametric window tests being performed under UVNS-TRQ 028. 2.0 DEFINITIONS AND ABBREVIATIONS 2.1 Definitions I L Cement . Dry Portland Type I cement im accordance with A5'M i L Standard C 150 85. ' f-
-BEL 0049:3RM - 2-
4 VVNS TP 025 Rev. 0
,_ Cement Slend A homogenous mixture of Portland Type I cement with
) a percentage of technical grade flake or granular form calcium nitrate with NO ammonium nitrate.
Cast A specimen mixed in a poly bottle and then poured into a mold. Cube - A 2" x 2" x 2" cart specimen. 2.2 Abbreviations ACM Analytical Chemistry Method A&PC Analytical & Process Chemistry ACF Analytical Chemistry Procedure CSS Cement Solidifica:ron System IRTS Integraced Radwaste Treatment System IWP - Industrial Vork Permit PCR - Process Control Engineering
.(h QA - Quality Assurance R/S - Radiation & Safety TLS Total Dissolved Solide 3.0 RESPONSIBILITIES 3.1 Analytien'. & Process Chemistry performs all work in this Test Procedure. P -
3.2 Process Control Engineering (PCE) provides technical direction, and compares the test data to the Test Request. 3.3 Quality Assurance provides surveillance to ensure that the requirements of this test pro:edure are satisfied, and verifies that portions of the test (where independent verification is required) were performed.
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VVHS TP 025 Rev. O I 3.4 Radiation & Safety monitors radiation and contamination levels ! P ( ! 4.0 TOOLS, EQUIPMENT , COMPOND7TS, AND REFERENCES 4.1 Toole_and Equipment '
"LIGHTNIN" Model TS 1515 lab mixer with high shear impeller 2' x 2" x 2" plastic cube molds 500 mL poly bottles -
250 mL poly bottles 20 mL scintillation viel f magnetic stir plate and stirring bar () - timer top-loading analytical balance Forney Model PT+40 OR compressive strength testing machine with hydraulic power unit and capping see . 4.2 Reagents Portland Type I cement per ASTM C 150 85 General' Electric AF9020 antifoam emulsion-Sodium Silicate solution: Vater based solution witn 28.5 to 29 5 percent $102 Powdered calcium nitrate l +. ' p - bELOO49:3RM ' 4-l
VVHS TP 025 Rev. 0 () 4.3 Components Despatch Series 16000 Environmental Chamber fully operational 4.4 References _ 4.4.1 EP 11 001, Test Control 4 . 's . 2 EP 11 003, Development Test Control 4.4.3 UVMS 'fPL-70 Oll, Test Plan for Vaste Form for Cement Solidification o.' Sludee Vash Liquids 4.4.4 VVNS TRQ 025. Test Request for Development of the Nominal Recipe for Cement Solidification of Sludge Vash Liquids e 4.4.5 ACM CEMPREP 4801, Preparation of Coment Samples in the () Radiochemistry Lab written by C. V. McV2y, et. al. 4.4.6 ACP 7.2, Safety Practices for the Analytical & Process Chemistry Department 4.4.7 VVDP 010, WVNS Radiolo6 i cal Controls Manual 4.4.8 VVDP 011, WVNS Industrial Hygiene & Safety Manual ' 4.4.9 USNRC Branch Technical Position on Waste Form, revision 1, draft dated December 1990 4.4.10 ASTM Standard C 109, Standard Test Method for Compressive Strength of Hydraulic Cement Mortars (Using 2-inch or 50 mm cube specimens) O . BELOO49:3RM - 5-
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VVNS TP 025 Rev. 0 4.4.11 ASTM Standard C 617, Practice for Cappin6 Cylindrical () Concrete Specimens 4.4.12 ASTM Standard C 470, Specification for Molds for Forming Concrete Test Cylinders Vertically 4.4.13 ASTM Standard C 150, Specification for Portland Type I Cement J l 5.0 CENERAL INFORMATION l S.1 Performance of the " nominal" waste form developed under this pretedure will be qualified under Test Request VVNS TRQ 026, and Test Prccedure VVNS-TP 026. 5.2 Quality AssuranJe should'be notified prior to commencement of activities, in order to perform surveillance (s). 5.3 OVERATORS SHOULD PERFORM FREQUENT CHECKS ON SYSTEMS THAT ARE TURNED ON OR SHUT DOVN TO ASSURE THAT THE SYSTEM DOES WHAT IS
.EXP'.CTED, I.E., VATER FLOVS, PRESSURE RISES, ETC.
7F THE REQUIRED ACTION THAT IS SUPPOSED TO HAPPEN DOES NOT MAPPEN, (1) STOP DO NOT PERFORM YHE NEXT STEP, (2) SECURE THE SYSTEM IN A SAFE MODE. AND-(3) NOTIFY THE COGNIZANT.A&PC SCIENTIST OR COGNIZANT ENGINEER IMMEDIATELY. 6.0 EMEPCENC7 RESPON Q 6.1 For emergencies in the A&PC Lab, rec;onses will be as directed by ACP 7.2 and WVDP-Oll. 6.2 For emergencies elsewhere in the plant, responses will be as directed by VVDP 010 and VVDP 011. ts _- . BELOO49:3RM 6-
4 VVHS TP 025 Rev. 0 7.0 DETERMINATION OF THE "NOMiNg" PERCENT SOLIDS IN THE VASTE O This determination vill be made by the IRTS Startup Task Force prior to beginning this work, i i 8.0 DETERMINATION OF THE " NOMINAL
- RANCE OF CALCIUM NITRATE RECIPE DIHANCER j TO BE BLENDED WITH PORTLAND TYPE I CEMENT 8.1 starting with the original recipe for encapsulation of Decontaminated Supernatant, test the performance of the vaste form at varying percentages of Calcium Nitrate in the cement blend.
8.1.1 Prepare a cube using the " nominal" blend ratio of 5.7 percent Calcium Nitrate in accordance with ACM CEMPREP 4801. 8.1.2 Cure the cube at 88 + 5 degrees celsius for 48 hours. 8.1.3 After curing, remove the cube mold, 8.1.4 Sand rvo (2) opposite cube faces until flat 8.1.5 Placa the cube in the hydraulic press, and measure the pressure _ at the cube yield point. Record the pressure. and perform the compressive strength calculation per ASTM Stancard C-109. Record on form WV 2301, 8.2 Increase the Calcium Nitrate percentage to 6 percent, 7 percent, 8 percent, 9 percent, etc., up to 12 percent Calcium Nitrate in the cement blend. 8.2.1 Prepare cubes at each new cement blend ratio in accordance with ACM CEMPREP 4801. O BELOO49:3RM r
,m , _ - - c__,._ . . . _ _ . _ . . . _ _ . , - .
=
WHS.TP.025 Rov. 0 8.2.2 Cure the cubes, remove the molds, cap and perform compressive strength testing in accordance with section 8.1.2 through 8.1.5 above. 8.2.3 Record the 5e1 time, penetration resistance, and slurry density on form W.2301, 8.2.4 Record the presence or absence of bleed water on form W. 2301. If present, determine the pH. 8.3 Decrease the percentage of Calciws Nitrate in the cement to 4 percent. 8.3.1 Prepare the cubes at this cement blend ratto in accordance with ACM.CEMPREP 4801. 8.3.2 Cure the cubes, remove the molds, sand two opposite cube faces until flat and perform compressive strength testing in accordance with sections 8.1.2 through 8.1.5 above. 8.3.3 Record the gel time, penetration resistance. and slurry density on form W 2301, 8.3,4 Record the presence or absente of bleed water on form W.2301. If present, determine the pH. 9.0 CALCULATION OF THE NOMINA 1. VATER.TO. CEMENT PATIO 9.1 After the Calcium Nitrate fraction of the cement blend is determined (section 8.0 above), calculate the nominal water.co cement ratio as follows: c (weir.he of waste) x (1 . solids fraction) V/C - (1 Calcium Nitrate fraction) x (weight of cement blend) O BELOO49:3RM . 8
VVNS TP 025 ! Rev. 0 10.0 DETERMINATION OF THE NOMINAL AMOUNT OF ANTIFOAM 10.1 After the nominal Calcium Nitrate fraction in the cement blend and r nominal water to.coment ratio have been determined, the nominal amount of antifoss in the recipe is to be verified. ; 10.2 Vith all other recipe parameters remaining the same, or as previously determined in section 8.0 and 9.0 above, prepara a cube ! in accordance with ACM CEMPREP 4801. l 10.3 Cure the cube at 88 +5 degroes celsius for 48 hours.
'.0.4 After curing, remove the cube mold, 10.5 Sand two opposite faces of the cube until flat.
10.6 Place the capped cube in the hydraulic press, and measure the pressure at the cube yield point. Record the pressure, and ( perform the compressive strength calculation in accordance with ASTM Standard C 109. Record on fo 1 WV 2301. 11.0 DETERMINATION OF THE NOMINAL WEIntT OF SODIUM SILICATE RECIPE ENHANCER , TO BE ADDED 11.1 After the Calcium Nitrate fraction in the cement, water to-cement ratio, and amount of antifoam in the nominal recipe have been determined, the nominal amount of Sodium Silicate additive is to be verified. 11,2 Vith all other recipe parameters remaining the same, or as previously determined in sections 8.0, 9.0, and 10.0, prepare a cube in accordance with ACM CEMPREP 4801. 11.3 Cure the cube at 88 +5 degrees celsius for 48 hours, BEL 0049:3RM - . . - - - . - - . - . . .. . - - - , - . , . . -- - - . ,- .. - ., a.-.----,-.-- .-- .
.. WVNS TP 025 Rev. 0 l 11.4 After curing, remove the cube wold, l 11.5 Sand two opposite faces of the cube until flat. 11.6 Place the capped cube in the hydreulic press, and measure the pressure at the cube yield point. Record the pressure, and perform the comy,essive strength calculation per ASTM Standard C-109. Record on form VV 2301. , 12.0 DETERMINATION OF THE MAXIMUM COMPRESSIVE STRENCTH 12.1 After the Calcium Nitrate fraction in the cement blend, amount of Antifoam additive, amount of Sodium Silicate, water to cement ratio for the nominal recipe have been verified, deteraine the maximum practical compressive strength of the vaste fo rm . 12.2 A mean compressive strength in excess of 500 psi after 28 days curing is desired, as' discussed in the Branch Technical Position. appendix A.11.B. (G) 12.3 Sufficient samples shall be prepared to determine the mean compressive strength as well as the standard deviation. A minimum of 10 samples shall be evaluated. 12.4 the compressive strength vs. time will be determined as discussed in WVNS-TP-026, section 7.0. 11.0 CURINC 13.1 A curing temperature of 88 15 degrees celsius as required for Cement Solidification of Decontaminated Supernatant will be used for initial testing. 13.2 When processing full scale drums under Work Order 9100084, a drum was equipped 'with thermocouples and a temperature recorder. The BELOO49:3RM - 10 -
( WNS TP 025 Rev, 0 9 drum tempetature as a function of time was plotted. The effect of curing at this temperature profile will be evaluated as Aiscussed in the Branch Technical Position, appendix A.III.B. 13.3 For this procedure, the samples will be bagged and cured in an oven or temperature controlled chamber, 13.4 The chamber will be equipped with a calibrated thermometer and temperature readings will be continuously re:orded. 13.5 All samples will be kept in sealed containers and/or poly bags during curing and storage, as discussed its the Branch Technical Position,' appendix A.III.C. This is intended to simulate the environment in a sealed drum. 14.0 DETERMINATION OF "CEL TIMES
- 14.1 For all samples can in the A&PC Lab, the cube molds will be filled in accordance with AcM CEMPREP 4801, with a 20 mL i
scintillation vial filled fo6 each cube. 14.2 Visually check for gelation of the cement / waste product in the scintillation vial,
- a. Check for gelation every 5 minutes, and do not disturb the vial between these time intervals.
- b. Celation is a subjective determination; however, gelled product is indicated when the 20 mL scintillation vial can be tipped slowly to a 90 degree orientation, and the cement product will not deform or flow, and will retain a line perpendicular to the horizon.
- c. Bleedwater is NOT to be interpreted as a sign of incomplete gelation. Estimate the quantity and. determine the pH if not reabsorbed after 24 hours. ,
BEL 0049:3RM - 11 - I L
_ . . - _ _ - . - - ~ ~ - _. . 3' TABLE 1 WVHS TP 025 Rev. 0 REVISED SALT.lQfiCENTRATIONS FOR THE " NOMINAL' f' SlHULANT RECIPE BASED ON 128.5" HEEL CONSI1IDENT FORhsL' . Elgl1L Sodium Nitrate NANO 3 286 lbs. Sodium Nitrite nan 0 2 272 lbs. Sodium Sulfate 110 lbs. Na2SO4 Sodium Bicarbonate NaHCO
- 3
)
Potassium Nitrate KNO3 17.9 lbs. Sodium Carbonate 48.4 lbs. Na2CO3 Sodium Hydroxide Na0H **10.4 lbs. Sodium Dichromato, Dihydrate Na2Cr207 2H 2O 1590 g Sodium Chloride Nacl 1010 g Sodium Phosphate Dibasic 950 g Na2HPO4 Sodium Molybdate, D1 hydrate 226 g Na2Mo0 4 .IH 2O Sodium Tetraborate. Oecahydrate Na280 4 7 10H 2O 122 g Citric Acid, Anhydrv,-- CH0687 165 g IQ Oxalic Acid, Anhydrous CH0224 129 g Tartaric Acid, Anhydrous CH0466 180 g Water HO 1568.0 lbs._ 2 TOTAL WEIGifT 2483.1 lbs. Weight of Solids 815.1 lbs. Weight Percent Solids 32.83 perceed. Note that Sodium Bicarbonate does NOT appear as NaHCO3 at elevated pH's.
** The Sodium Hydroxide (NaOH) value is an approximation to arrive at a pH of 12.1. This value may vary.
SRC4094/)
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WVNS-TSR-02S TEST
SUMMARY
REPORT V' Rev. O TEST / TEST SERIES _ Waste Form.0ualification for Cement Solidification of Sludae Wash Liouids DESCRIPTION Development of the N3minal ReciDe for Cen,ent Solidification of Siudoe Wash Liouids TEST REQUEST !!0. WVNS-TR0-025 TEST PLAN NO. WVNS-TPL-70-Oll TEST COMMENCEM"NT DATE 5/1/91 TEST COMPLETION DATE 5/17/91 1.0 QBSERVATIONS/ COMMENTS: The purpose of this test procedure was to determine the nominal recipe for cement solidification of sludge wash liquids using the existing recipe for supernatant solidification as a first approximation. This test procedure verified that the existing supernatant recipe will be the nominal recipe used in future testing with the exception that the waste liquid will be 29 to 33% solHs instead of 37 to 41% used for supernatant.
2.0 EEFERENCES
O 1) Letter No. EK:91:0047, " Preliminary Flowsheet: Sludge Wash with Existing 8D-2 Heel", dated March 7,1991. L)
- 2) 00E/NE/44139-49, Topical Report on Development of the Recipe for Solidif tr.ation of Decontaminated Supernatant, McVay, et. al.
- 3) USNRC Branch Technical Position on Waste Form, Rev.1, dated January 1991.
- 4) Letter No. FH:91:0089, " Test Results on Nominal Recipe Qualification",
dated June 21, 1991. 3.0 OBJECTIVES MET: 3.1 Determine the acceptable range of percent solids (by weight) in the waste liquid. STATUS: Complete OBSERVATION: Increasing the percent solids in the waste liquid above the " nominal" range lowers the compressive strength of the waste form. DATA: Refer to Table 1 SRC4166:3RM WVNS-TSR-025 Rev. 0 3.2 Determine the acceptable range of calcium nitrate recipe enhancer to be blended with Portland Type I cement.- STATUS: Complete OBSERVATION: The waste form produced with no calcium nitrate in the cement blend exhibited lower compressive strength as well as slow gel times. Large amounts of calcium nitrate in the cement blend also resulted in lower compressive strength.. DATA: Refer to Table 2 3.3 Determine the acceptable range of water-to-cement ratio. STALES: Comp 1cte OBSERVATION: The waste form exhibits lower compressive strength at high water-to-cement ratios. LATA: Refer to Table 3 3.4. Determine the acceptable range of antifoam recipe enhancer to be added to the waste. STATUSI Complete O OBSERVATION: None O DATA: Refer to Table 4
-3.5 Deters .1e the acceptable range of sodium silicate recipe enhancer to be added to the waste / cement mixture.
-STATUS: Complete OBSERVATION: The waste form produced with no sodium silicate exhibited a slow gel time, and bleed water.
DATA: Refer to Table 5 3.6 Determine the maximum practical compressive strength of the waste form. STATUS: Complete OBSERVATION: The average compressive strength exhibited by the waste form at the " nominal" recipe was 1403 psi, with a 2 sigma (90% confidence-band) of 316 psi. DATA: Refer to Table 6 SRC.fl66:3RM . _ .
WVNS-TSR 025 Rev. O.
-i
'3.7 Evaluate the effects of the recipe parameters on ' gel time" and free p- liquid in the waste mixture. '
-J STATUS:. Complete OBSERVATION: See section 3.2 and 3.5 abbve.
DATA: Refer to -Table 7
4.0 CONCLUSION
S: 4.1 'The nominal recipe for supernatant processing will be used for sludge wash waste form qualificatior testing. This recipe is shown , in table 7. 4.2 There is a practical upper limit to the water-to-cement ratio, as well.as to the 3ercent solids in the waste stream and calcium nitrate cement alend. These are three variations of the same effect: cement must be
-hydrattid by water, and any parameter which changes the amount of water (solids in the waste liquid) or cement (calcium nitrate in the blend) will affect the hydration reaction.
S'. 0 ACCEPTABILITY OF RESULTS: : 5.1 -The results of this test are acceptable. It is. felt-that a reasonable number of test specimens were prepared and that the u'O) s results clearly _ demonstrate where an effect is encountered. 5.2 The results of tests where no effect is seen are sufficiently.close L in order of magnitude tr establish that no concern is justified. 6.0 ACTIONS OUTSTANDING: 6.1 The exact-limits for recipe parameters, as well as the possible
. interaction of all- variables will be evaluated during multi-variant
, testing as a scribed in WVNS-TP-028. 6.2- Characterization of th'e solids in the waste liquid, discussed in WVNS-TRQ-025,- was not performed, but the effect of sulfates. nitrates, nitrites, aluminum, ect., will be evaluated during WVNS- _TP-028/028A.
-.c . APPROVAL (S) M ADDITIONAL REVIEWERS: h NO (Test Requester) A.
$Nw,,wu ltV 'kfbfl % Mi si VWh ll
/J. C4 Cwyrdr Jl{ MahonlPy - .
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-SRC4166:3RM .
- +- , ,,
WVNS-TSR-025 1 Rev. 0 ' O kJ TABLE 1 COMP GEL TIME PENETRATION BLEED WATER STRENGTH SLURRY DENSITY EAMPLE ID. (mins) (DSi) (mis) (DSi) (C/ml) Total Solids Variations SWCF4 28.79% 10 >700 <1 2021 1.75 SWCF4 30.14% 10 >700 <1 1817 1.77 SWCF4 32.23% 5 >700 <1 1601 1.76 SWCF4 34.91% 7 >700 <1 1343 1.79 SWCF4 41.46% S8 >700 <1 859 1.81 () (/ SRC4166:3RM (~'T U
. . . .- . .. - . . - . - . - - . . - . .. .- -....... -... -- -- -. ~
WVNS-TSR-025
, Rev. 0 4 .V- - .
TABLE 2 COMP
= GEL TIME PENETRATIM BLEED WATER STRENGTH SLURRY DENSITY ~
' SAMPLE-ID. (mins) fosi) (mis) (osi) fo/ml)
Calcium Nitrate Variations *
- SWCF4 NR 0% 7 >700 <1 1054 .NA SWCF4 NR 0% -10 >700 <1 1334 -1.80 SWCF4 NR 0% 20 >700 <1 822 1.74 SWCF4-NR 3% 5-. >700 <1 1535 1.79-
-SWCF4 NR 3% 5 >700 <1 1359 l.74 SWCF4 NRL4% 5 >700- <1 1331 1.74
-SWCF4 NR 5.7%' 5 >700 <1 1581- 1.71 SWCF4 NR 9% -. 5 >700 - <1 1518- 1.a SWCF4 NR 11.4% 5 >700 <1 1274 1.67
. SWCF4 NR 17.'1%' 5- >700 <1 481 1.63 d
E f SRC4156:3RM O c
-WVNS-TSR-025-Rev. 0 .3 L
TABLE 3 i CORP-GEL TINE PENETRATION BLEED WATER -STRENGTH SLURRY DENSITY SANPLE ID. (mins) fosi) (mis) (osi) (a/ml) . Water to Cement Ratio
. SWCF4 0.50 5 >700 <1 2174- NA SWCF4 0.55- 5 >700 <1 1731 NA SWCF4 0.61-- 5 >700 <1 1434 1.77 SWCF4 0.70 5 >700- <1 1089 NA SWCF4 0.70 7 >700 <1 1216 1,71
- SWCF4 0.80 30 >700- <1 565 -NA SWCF4 0.80- 20 >700 <1 788 1.62 O
h 1
. SRC4166:3RM , O
WVNS-TSR-025
'Rev. O ! 'T ]
O TABLE 4 COMP GEL TIME PENETRATION- BLEED WATER STRENGTH -SLURRY DENSITY-SAMPLE ID. lains) (psi) (mis) (esi) (c/ml) Antifoam Variation-SHCF4 0 ml- 5. >700 <1 1777 1.69 , SWCF4 0.075 ml- 5 >700 <1 1695' 1.78 SWCF4 0.15 ml 5 >700 <1 947 1.76 SWCF4 0.30 ml 5- -- > 7 00 <1 1443 1.76 SWCF4 0.375 ml 5 >700 <1 1591 -1.75
-SWCF4 0.45 m1 ~5 _> 700 <1 1418 1.75-SWCF4 0.60 ml
- 5 >700 <1 1479 1.72
]
=
g
- n ll l
SRC4166:3RM O
. . . , . - . _ . - . -. . - . - - . - . . .. ~ . . , - . ..-..- -. - - . - . -_
l WVNS-TSR-025 Rev. 0 TABLE 15 COMP GEL TIME PENETRATION BLEED WATER STRENGTH SLURRY DENSITY
'$ AMPLE 10. (mins)- (psi) (als) (psi) (a/ml) !
Sodium Silicate Variations ' SWCF4 NR 0 g 10 >700 2 1926 1.80 SWCF4 NR 2.75 g 5 >700 <1 1400 NA
.SWCF4 NR 5.09 g 0' >700 <1 1367 1/66 -
SWCF4 NR 8.25 g. 5 >700 <1 1500 1/76 SWCF4 NR 10.04 g 5 >700 <1 1489- 1.74 SWCF4 NR 13.75 g 5 >700 <1 1321 1.77 , SWCF4 NR 15.38 g 7 >700 <1 1308 NA SWCF4 NR 16.88 g 20 >700 <1- 1281 1,71 l_ LO I 2 h-SRC4166:3RM O u l a _ ._. . _ _ __ _ __ _ --. --- .--
WVNS-TSR-025 Rev. 0 (_) TABLE 6 COMP GEL TIME PENETRATION BLEED WATER STRENGTH SLURRY DENSITY SAMPLE 10. -(mins) (Dsii . (mis) (Dsi) (a/ml) Nominal Recipe SWCF4 NR 5 >700 <1 1339 1.73 SWCF4 NR 5 >700 <1 1435 1.71 SWCF4 NR 5 >700 <1 1203 1,74 SWCF4 NR 5 >700 <1 1253 1.75 SWCF4 NR 5 >700 <1 1438 1.70 SWCF4 NR 5 >700 <1 1263 1.75 SWCF4 NR 5 >700 <1 1694 NA SWCF4 NR 5 >700 <1 1296 NA SWCF4 NR 5 >700 <1 1303 NA SWCF4 NR 5 >700 <1 1722 1.75 SWCF4 NR 5 >700 <1 1432 1,77 SWCF4 NR 5 >700 <1 1401 1.76 SWCF4 NR 5 >700 <1 1464 1.77 [)! N. SRC4166:3RM J
i'
. WVHS-TSR-025 Rev. 0 TABLE'7-
=
" NOMINAL" RECIPE SATISFACTORY RANGE ;
FOR SUPERNATANT FROM THIS PARAMETER PROCESSING TEST PROCEDURE
-%. Solids in Waste 37 to 41% 28.79 to 34.91% ,
Calcium Nitrate 4.7 to 7.4% 3.0-to 11.4% W/C Ratio 0.54 to 0.70 0.50 to 0.70 Antifoam 0.30 mL 0 mL to 0.60 mL a . Sodium Silicate 10.5 to-11.5 grams 2.75 to 15.3 grams Compressive Strength >500 PSI 1403 PSI Average Gel Time o to 90 minutes 5 to 10 minutes i
.F .i W
SRC4166:3RM ?
,..L - _,
O west Valley ooe "#=eer wvus-rao-o26 Demonstration Project """""*"" - Revision Dato 05/01/91 Engineering Release #2077 TCST REQUEST WASTE FORM QUALIFICATION WORK FOR THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS PREPARED BY 9/M M . M. N. Baker Cognizant Engineer APPROVED BY & D. C. Meess Cognizant System Design Manager [ N L. Shugars If ,_ech+17 8^ n ef44{D. (s APPROVED BY / ca/ ' ' Quality Aspurancs Mana ger AP BY- [ , D. J. Harward fadialionapSafetyManab[ APPROVED BY k .b be 4fl9 k( Prodss ContrcQ Engineering J. C. Cwynar West Valley Nuclear Senrices Co., Inc. P.O. Box 191 BEL 004723RM West Valley, NY 14171-0191 W W1816,Rev.1
~
WNS.TRQ 026
. Rev. 0 RECORD OF REVISION ' g]. PROCEDURE kf 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:
> ~he arrow in the margin indicates a change.
Revision On Rev..No. Description of Changes Page(s) Dated 0 Original Issue Al1 05/01/91
-(
[i W-1807. Rev. 1 i ( BELOO47:3RM
WNS-TRQ-026
, Rev. 0
. RECORD OF REVISION (CONTINUATION SHEET)
Rev, No, Re isi Description of Changes PagekE)on Dated O W-1807, Rev. 1 11 BELOO47:3RM O
4 VVNS TRQ 026
- - Rev. 0 VASTE FORM QUALIFICATION WORK FOR THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE VASH LIQUIDS
1.0 INTRODUCTION
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 the 10 CFR 61, Code of Federal Regulations, 11t.e 10, " Licensing Requirements for Land Disposal of Radioactive Waste," and the USNRC Branch Technical Position on Waste Form, revision 1, dated January,1991. 1.2 This work is performed as a part of WVNS-TPL-70-011. 1.3 Work will be performed with a simulant representing the actual waste liquid. The simulant is shown in Table 1 and will be verified under WVNS TRQ-025, 1.4 Work will be performed using both 2" x 2" x 2" cubes and 3" diameter x 6" long cylinders cast from full scale drums processed in the 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. Leach testing specimens will be 1" diameter x 3" high cylinders prepared in the A&PC laboratory using the lab-scale mixer. Leach specimens will be " spiked" with x ,) appropriate radionuclides. 1.5 Test Procedure WVNS TP 026, providing instructions for testing in accordance with this Test Request shall be issued by Analytical and Process Chemistry per EP-11 003. 1.6 Test Summary Report, WVNS TSR-026, documenting the results of this testing, will be issued by the Cognizant Engineer per EP 11-003, 2.0 ORJECTIVES 2.1 A curve of compressive strength vs. cure time will be established for both cubes and cylinders. The cure time which produces a compressive strength within 75 percent of maximum shall be determined. 2.2 The compressive strength of the vaste form as required by the Branch Technical Position, appendix A.II.B will be verified at cure times of 7, 14, 21, 28, 35, and 42 days. A mean compressive strength in excess of 500 psi after 28 days is required. 2.3 Thermal cycling stability of the waste form will be tested in accordance with ASTM Standard B-553, and the Branch Technical Position, appendix A.II.C. -("~) \ BEL 0047: 3RM 1 1 1 l l
4 UVHS TRQ 026 Rsv. 0
~
2.4 Resistance to leaching of radionuclides will be performed using a
,e S simulant liquid " spiked" with Cesium 137 Strontium 90, and
('~~) Plutonium 241. - Leaching will be performed in accordance with the Branch Technical Position, appendix A.II.F, and ANS/ ANSI procedure 16.1. Preliminery testing vill be performed to identify the leachant as deioni:ed water or synthette sea water. A Leachability Index, calculated in accordanca with ANS/ ANSI 16.1, greater than 6.0 is required. 2.5 Immersion testing shall be performed in accordance with the Branch Technical Position, appendix A.II.G. After curing for a minimum of 26 days or the cure time as indicated by the compressive strength vs. time testing in paragraph 2.? above, at least three (3) cylinders will be imaersed for a period of 90 days. Following 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 maan post-immersion compressive strength is less than 75% of the pre-immersion mean compressive strength, the immersion testing interval shall be extended (using different specimens) to 120, 150, and 180 dcys. 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) spe.imen, the leachability of the following " heavy
metal" shall be evaluated in accordance with the Toxicity Characteristics Leaching Procedure (TCLP): Chromium.
3.0 SAFETY 3.1 Industrial hygiene practices will be as described in the WVNS j Hygiene & Safety Manual, WVDP 011. 3,2 Radiological work will be performed in accordance with the WVDP Radiological Controls Manual, WVDP 010. 3.3 Work in the Analytical & Process Chemistry lab will be performed in accordance with existing A&PC methods (ACM's). 4.0 EQUIPMENT CONFICURATION 4.1 All lab equipment will be set up in accordance with WVNS-TP 026 and 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, etc., as discussed in the Branch Technical Position, appendix A.III.A.
~s BEL 0047:3RM 2
a WNS-TRQ 026 Rev. 0 n 4.3 Curing of the samples will be performed in a manner which duplicates, to the extent practical, the curing temperature profile
.(' ~) 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 WNS-QlP-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. 6.0 PERSONNEL QUALIFICATION '~ 6.1 Laboratory testing will be performed by qualified Analytical & Process Chemistry Technicians in accordance with WNS-TP 026 and Analytical Chemistry Methods (ACM's) under the co5nizance of an A&PC Scientist. a) Radiochemistry "B" Technicians qualified to WNS-QS 014 b) Radiochemistry "A" Technicians qualified to WNS-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 REPORTING 7.1 A Test Summary Report (WNS-TSR-026) documenti.ng the results of testing performed per this test request shall be issued by the Cognizant. Test Engineer. l I i (' BELOO47:3RM 3
- _ _. . . - . . . _ . . _ . _ - _ _ ~ . _ _ _ . _ _ . _ .
.;4 '
-.t'-
< (_,/;
WVNS-TRO-o26 Rev. O TABLE in- Salt Concentrations for the-" Nominal'*-Recios Based on-128.5" Heel Constituent ~ -Formula Weight Sodium: Nitrate- NANO 3 - 35.62-Sodium Nitrite NANO 2 33.04. Sodium--Sulfate Na2SO4 21.13 Sovium Bicarbonate NaHCO3
- Potassium Nitrate
~
KNO3 -2.23 Sodium Carbonate -Na2CO3 6.02
-Sodium Hydroxide NaOH- 0.22 Sodium-Chromate- 'Na2CrO4 0.308
. Sodium -- Ch l oride - Nacl 0.234 Sodium Phosphate. Na3PO4 0.190 bodium Molybdate Na2 moo 4*2H2O- 0.040
- Sodium: Borate' -Na28407- 0.024 Citric Acid-- C6H007 0.032 Oxalic' Acid C2H204 0.032
-Tartaric Acid C4H606- 0.032 Water H20 203.03
-Total Weignt 302.982 Weight-of Solids 99.952
_ Weight-Percent Solids 33% 8 Note: Sodium Bicarbonate does'not ADDear as NaHNO3 at elevated pH's l, t-t f-O BELOO47:3RM 4
g j l (m 'l g Doc. Number WVNS-TP.026-Revision Number 0
-Demonstrat=on i Proj=ect Revision Date 05/02/91 Engineering Release #2079 TEST PROCEDURE PROCEDURE FOR QUALIFICATION OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS PREPARED BY M , A). b a8L v [Qc c_ M. N. Baker Cognizant Engine'ef
#44 * #
APPROVED BY D. C. Meess Cognizant System Design Manager APPROVED BY__ o,e /m D. L. Shugars Qu.vtftf Assurance' Managys " " APPROVED BY dbh\ D. J. Harvard Rad @ ion and Safety Manage 7 ~ APPROVED BY S b. d%- J, C. Gwynar ProVess Conc 61 Engineering West Valley Nuclear Services Co., Inc.
~x F.O. Box 191
) BELOO48:3RM
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4 West Valley, NY 14171-0191 WW1816, Flev.1 i t
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, . 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.
Example: l
> The arrow in the margin indicates a changc.
Revision On Rev. No. Description of Changes P. age ( s ) Dated O. Original Issue All 05/02/91 O O - W 1807, Rev. 1 i BTLOO48i3RM
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, WNS TP 026
--Rev,-0 RECORD OF REVISION (CONTINUATION SHEET)
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-Rev.:No',- Descriptibn of Changes Revisir.n)on Pagets Dated
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(\ _ ~ W-1807, Rev. 1 11 t- BELOO48:3RM i u
[v[ VVNS-TP 026 PROCEDURE FOR QUALIFICATION OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDCE WASH LIQUIDS "ev.
. 0 1.0 SCODE 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 CFR 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 VVNS TPL-70-11, " Test Plan for the Waste Fora Qualification Program for Cement Solidification of Slud Se Wash Liquid."
1.2 Work will be performed with a simulant representing the actual vaste liquid. After all tests have been performed, a small sample of the actual sludge wash product will be solidified using the qualified recipe, This sample will be subjected to compressive strength testing. This work will be perf snned under VVNS TRQ 029. 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 tests is 'to establish a cortslation between the full-scale cylinders, full-scale cubes, and lab-scale cubes. 1.4. A curve of compressive strength vs. cure time will be established for both cubes and cylinders, 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. 1.6 Thermal cycling stability of the vaste form will be tested in accordance with ASTM Standard 3-553, aection 3.1. 1.7 - Resistance to leaching of radionuclides will _be performed using a simulant liquid " spiked"'vich Cesium-137, Strontium 90, and Plutonium-241, in cccordance 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 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 90 days. Following immersion, the specimens shall be subjected [h
\_,)
to compressive attength testing. A mean post-immersion compressive strer.Sth not less than 75 percent of the mean BELOO48:3RM
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- WNS TP-026
, .s Rev; O f..g -compressive strength (paragraph 1.4 abov.e) is required. _-If the-V mean-post-Lamersion-compressive' strength is_less than 75 percent-
? of the mean pre.inamersion compressive strength,. the immersion
. interval shall be_ extended (using different specimens)-co-120, 150, and 180 days. This testing is required to establish that the "x~
compressive strengths level off and do not continue to-decrease with time. 1.9 For:one (1) specimen, the leachability of the chromium shall be evaluated in accordance.with the Toxicity Characteristic Leaching-Procedure (TCLP). 2.0- DEFINITIONS AND ABBREVIATIONS-2.1 Definitions Canent - Dry Portland Type I cement.in accordance with ASTM Standard C-150 C4 ment Bland - 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.
Casti A' cube'or-cylinder-specimen produced in the mixer, then scooped into the mold
, ; ' Cub'e - A 2*x2"x2"; cast- speci:nen produced either in a lab mixer or
-U the full-scale mixer-Cylinder - A cast specimen 3" diameter x 6" long produced in the '
-full-scale mixer.
. Demineralized Water l- water having 'a conductivity less than 5
_niicromho/cm at 25' degrees Celsius and a total organic carbon content less.than 3 parts /million. SyntheticLSeavater - a combination of various inorganic compounds as follows: Sodium Chloride 23.497 grams
; Magnesium Chloride 4.981 grams Sodium Sulfate 3.917 grams.
Calcium Chloride l'.102 grams Sodium carbonate 0.192 grams , Potasium Brpaide 0.096 grams
- Demineralized Vater 965.551 milliliters
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UVNS-TP 026 Rov 0
,e~S 2.2 Abbreviations Q- ~
ACM - Analytical Chemistry Method A&PC Analytical & Process Chemistry ACP - Analytical Chemistry Procedure CSS Cement Solidification System DAS - Data Acquisition System IWP - Industrial Work Permit IRTS - Integrated Radvaste Treatment System LWTS-.- Liquid Waste Treatment System PCE - Process Control Engineering QA - Quality Assurance R&S - Radiation and Safety SIP Special Instructions Procedu-o SOP Standard Operating Procedure TDS Total Dissolved Solids 3.0 RESPONSIBILITIES 3.1 Integrated Radwaste Treatment System (IRTS) Operations personnel operate the Cement Solidification. System (CSS) in accordance with SIP 91-01 and WVNS PCP 001 to produce the full-scale drums of solidified simulant liquid required for this test procedure. 3.2 IRTS Support Engineerin5 Provides technical support as necessary. 3.3 Process Control Engineering (PCE) provides rechnical <1rection, (~')N i, s and compares the test data to the Test Request requirmeents. 3.4 Quality Services provides surveillance to ensure that the requirements of this test procedure are satisfied, and verifies that portions of the test (where independent verification is required) were performed. 3.5 Quality Services performs compressive strength testing of cylinders in accordance with QIP 027. 3.6 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 thermal 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~ t A.- BELOO48:3RM
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' WVNS TP 026
.Rev. 0
., 4.0 TOOLS, EQUIPMENT, COMPONENTS, AND REFERENCES-
-A 4.1 Tools and Equipment '
2"-x 2" x 2" poly cube molds 3": diameter x 6"'long cylinder solds per ASTM Standard C 470 d- Poly bags q solid sample (s) transport container (s) 5 gallon high ' density polysthlene pails with lids 20 Liters Domineralized Water 20.-Liters Synthetic Seawater- , recording-thermometer readable to +/ 0.5 degree Celsius 4.2 Components. CSS equipment fully operational , Despatch Series 16000 Environmental Chamber fully operational Forney Model FT-40-DR Compressive Strength Testing Unit fully " u operational- . 4,3 Re ferences -- 4.3.1L CSS (System 70) Standard Operating Procedures 4.3.2 EP-11,001, Test Control 4.3.3' EP-11 003, Development. Test Control 4.3.4 WVNS TPL-70iO11,-Test-Plan-for Waste Form for Cement , < Solidification of Sludge Washi Liquid 4.3.5 WVNS-TRQ-026 Test Request:for Wasta Form Qualification Work for the Nominal Recipe -for- Cement Solidification of
-Sludge Wash Liquid
.4.3.6 WVDP-010', WVNS Radiation-Controls Manual 4.3.7. WVDP 011, WVNS Industrial Hygiene & Safety Manual 14.3.8. USNRC Branch Technical Position on Waste Form, Revision 1, dated January. 1991 L
BELOO48:3RM - -
, WVNS-TP 026 Rev. 0
('g 4.3.9 AFIM C-109 Standard Test method for_ Compressive Strength of a
) Hydraulic Cement Mortars (Using 2 in, or 50 mm Cube Specimens) 4.3.10 ASTM C-39 Standard Test Method for Compressive Strength of Cylindrical Concrete Specimens
.3.11 ASTM B-553 Standard Test Method for Thermal Cyclin $ of Electroplaced Plastics 4.3.12 ANSI /ANS 16.1 American National Standard Messurement of the Leachability of Solidified Low Level Radioactiv<a 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 VVNS TRQ-025, Test Request for Development of the Nominal Recipe for Cement Solidification of Sludge Wash Liquids 4.3.17 VVNS TP-025 Test Procedure for Development of the Nominal
( Recipe for Cement Solidification of Sludge 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 Method 4.3.21 ACM 5901, Analytical Chemistry Method for Toxicity Characteristics Leaching Procedure (TCLP) 4.3.22 ACM 6200, Analytical Chemistry Method for Operation of Despatch Envirornental 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
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V. T BELOO48:3RM WNS-TP 026 l Rsv. 0 'l
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p- t 5.0 CENERAL INFORMATION
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5.1 The nominal recipe being qualified by this test procedure will be developed under Test Request WNS-TRQ 025, and Test Procedure WNS-TP 025. 5.2 Results of this testing will be compared to the results obtained under WNS-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., VATER 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 MOP', AND (3) - NOTIFY THE COGNIZANT A&PC SCIENTIST OR COGNIZANT ENGINEER IMMEDIATELY. 6.0 EMERGENCY RESPONSE 6.1 For emergencies in the A&PC Lab, responses will be as directed by ACP 7.2 and WDP-010.
-6.2 For emergencies elsewhere in the plant, responses will be as
[_} U directed by WDP-010. 7.0 COMPRESSIVE STRENGTH V5. TIME 7.1 After curing 7 days in the controlled-temperature chamber and at roca 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. 7.2 After curing 14 days in the controlled-temoerature chamber and at room temperature as discussed in section 13. below, a total of three (3) cubes.will be subjected to compresalve strength testing per applicable steps of ASTM Standard C-109 and the applicable 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 thrr:e (3) cubes will be subjected to compressive strength testing per applicable steps of ASTM Standard C 109 and the applicable steps of ACM-4801. p'_ BELOO48:3RM
.. $ VVNS TP 026 Rev. 0 7.4 After curing _28. days in the controlled temperature chamber-and at O, toon 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.
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 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 Af ter curing 42 days in the controlled-temperature chamber and at room temperattre 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 THERKAL CYCLING 8.1 -The-heating /coolin5 chamber shall' conform to the description given in ASTM Standard B-553. The ther .1 cyc11pg test shall be performed in accordance with ACM u200. 8.2 E=cause ASTM Standard B-553 addresses thermal cycling- of electroplaced plastics, some- modifications to the test method are required. Testing vill be performed on " bare" (i.e., not in a container) cylinders. 8.3 After a cure time of at least 28_ days, or-longer, as identified in section_7 above,.unbagged-cylinders chould 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 (a40 degrees C) temperature limits. Thermal equilibrium should be confirmed by measurements of the centerline temperature of at least one (1) specimer 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 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 P BELOO48:3RM l . l
. UVNS TP 026 !
Rov. O i 7s \ cylinder condition without assessing vt..cher the defects are ( significant. Visible evidence of significant degradation wo"ld be indicative of a failure of.the test. 8.6 If there are NO significant .efects, the test cylinders shall be subjected to compressive strength testing per QIP-27 or ACM-4701 and applicable stetions of ASTM Standard C 39. A mean compressive strength g: eater 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 simulant " spiked" with Cesium 137, Strontium-90, and Plutor. Lum 241.
's . 2 After curing, the cylinder will be immersed in either deionized water or synthetic sea watar 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 watar) 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 race) will be used for the remaining tests. tO (s,) l 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 incarvals of 2, 7, 24, 48, 72, 90, and 120 hours. Upon removal of the cylinder (in accordance with ANSI /ANS 16.1, section 2.3) the leachant will be analyzed for Casium-137, Strontium-90, and Plutonium 241 concentration. Each concentration is expressed as an "L" value for that leaching interval. The "L" value is the logarithm of the inverse of the effective diffusivity for each isotope. The "Leachability Index" is the arithmetic mean of the "L" valuer. The Leachability Index, as calculated in accordance with ANS/ ANSI 16.1, should be greater than 6.0. 10.0 IMMERSION TESTING 10.1 No " Standard Method of Test" for immersion testing has been adopted for low-level radioactive waste. The test, however, is discussed in the Branch Technical Position, appendix A.II.G. and l-shall be performed in accordance with ACM-6400. l 10.2 After a cure time of 28 days, or as indicated by the compressive strength vs. cure time testin6 Performed in section 7.0 above, at least three (3) cylindars will be immersed for a period of l 90 days, t i
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BELOO48:3RM l
WNS TP 026 Rev. 0 10.3 The inersion liquid shall be either deionized water or synthetic ' O sea water. The immersion liquid will be selected during the leach testinB described in section 9.3 above. 10.4 Tollowing imersion, 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 time, a E 10.5 If there is no evidence of significant degradation, the specimens shall be subjected to compressive strength testin5 per QIP 27 or -
. ACM 4701 and Applicable sections of ASTM Standard C 39. Post-imersion mean compressive strengths should be greater than or {
equal en 500 psi, and not less than 75 percent of the pre. k imersion (as cured) mean compressive acrength. 10.6 If the post-imnersion mean coorpressive stranSth is less than 75 m I percent of the as-cured specimens' pre imersion mean compressive g strength, but not less than 500 psi, the imersion testing interval should be extended (using additional specimens) to a l g, ininimum of 180 dayn. For these cases, compressive strength i testing should be conducted after 120, 150, and 180 days of innersion to establish that the compressive strengths level off and do not continue to decreaes teith time. 10.7 Quality Assurance may perform surveillance of the imersion, post- - immersion inspection, and compresalve etten5th testing processes, 11.0 }J'.ACH, TESTING TOR HEAW METALS r 11.1 One (,'.) cursd sample specimen will be used for Toxicity y Chartmeteristic Leaching Procedure (TCLP) testing for Chrc.atuc:. o 11,s A total of 100 grams of the sample material will be er hd Jr.d extracted in accordance with ACM-5901. 11.3 The resulting extract liquid will be analyzed for the presence of chroutum. 11.6 A Chromium concentration less than the regulatory limit of 5.0 ag/L is required, p 12.0 j,AJpLING h 12.1 Lab scale (cube) camples will be produced ir accordance with E ACM 4701. E 7 12.2 Full scale cube and cylinder samples will be produced in [l decordance with SIP 91 01. 1 i O n BELOO48:3RM 1
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j l l VVNS.TP.026 i Rev. 0 l 12.3 A total of forty (40) cubes and fifty (50) cylinders will be O required in accordance with Table 1. 13.0 CURING 13.1 Lab. scale cube specimens, full scale cube specimens, and full. seals cylindrical specimens will be cured, to the extent prac;:ical, at the same conditions as full scale drums, as 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 with thermocouples and a temperature recorder. The drum I centerline temperature will be plotted as a function of time. l This temperatur.* profile will be duplicated, to the extent practical, for all samples cured outside of the drum. i l 13.3 tor this procedure, the samples will be bagged and curef in a controlled. temperature chamber for a period of time equivalent to the peak hydration period. This period is taken to be that
. required for the t. rum centerline temperature to decrease to 30 degrees celsium.
13.4 The chamber will be equipped with a calibrated thermometer, and continuous terparature 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 O. Position, appendix A.III.C. This is inter.ded to simulate the environment in a sealed drum. '
-14.0 COMPRESSIVE STRINGTH TESTINC OF CYLINDERS 14.1. The maximum practical compressive strength of the waste form will be avalu. sed 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, 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. r O BELOO48:3RM 10 -
__- _ _ ___ . . - . . _m . _ . _ _ _ _ . _ _ _ _ _ _ . _ . _ . _ _. - VVNS TP 026 Rev. 0 TABLE 1 Sample Schedule for Qualification of the Nominal Recipe for Cement Solidification of Sludge Wash Liquids Elapsed Event Cubes Cylinders Dsys 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) (BE1DW) 28 thermal cycling - 4 28 TCLP - 1 35 35 day compressive 3 3 strength 42 42 day compressive ; ? - strength 118 Post immersion 3 3 lompressive Strength - 148 Post issnersion 3 3 Compressive Strength 178 Pome inumersion 3 3 Compressive Stren5th 208 Post immerston 3 3 Compressiva Strength TOTAL 37 42 BEI4048:3RM 11
, WVNS TP.026 , Rev. 0 TABLE 2 Salt Concentrations for the " Nominal" Simulant Recipe Based on 128.5" Heel Constituent Formula Weight Sodium Nitrate NANO 3 35.62 Sodium Nitrite NANO 2 33'00 Sodium Sulfate Na2SO 4 21.13 Sodium Bicarbonate NaliCO 3
- Potassium Nitrate KNO 3 2.23 Sodium Carbonate Na2CO 3 6.02 Sodium Hydroxide NaOH 0.22 Sodium Chromate Na2C rog 0.308 Sodium Chloride Nact i 0.234 Sodium Phosphate 0.190 Na3PO 4 Sodium Molybdste -
0.040 Na2Mo04 Sodium Borate Na2B0 47 0.024 Citric Acid CH0 687 0.032 Oxalic Acid C0H 242 0.032 Tartaric Acid CH0 466 0.032 Water HO 203.03 2 Total Weight 302.982 j Weight of Solids 99.952 Weight Percent Solids 33% r - l 0 V l
- Note: Sodium Bicarbonate does not appear as NaHCO3 at elevated pH BELOO48:3RM __ _
WYMS-TP-026 e 'Rev. O I O : Figure 1: Despctch Series 16000 Environmental Chamber with MRC 7000 Controller Oven Chamber y (Oven Pan 0 rear) located t 1 hermocouple Port ,--- *-
/ .atch L
Oven - O . Recording Chart emperature-- _ T I, l % l *
% N gg MRC Series 7000 Contro11e Power Switch *- - -
l- - - [.see. .s Casling. Unit Swit :h
, )
Cooling Unit Compressor p ' p (located 9 rear)
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r O m m _ l
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. i O VEST VALLEY NUCLEAR SERVICES COMPANY M NT RELEASE FOP 3 Document No.: VVNS TSR 026 ,__
Title:
Test 5'ummary Results Report For Outlification Vork For The Nominal , Reelee For Cement Solidification of Sludre Unsh Liouids Revision: 0 Date: 02/06/92 Special Instructions: O
\ l V Distribution: .
Controlled Cooies Egginient Eg. gip.Lgng Uncontrolled Cooies Recipient Recioient MRC MS-508 J . L. MA30NEY MS M L. E. MICHNIK MS 56 Quality Services, MS L A, J . Il0VELL MS W D. C. MEESS MS 81F R. J. LEUANDOWSKI MS-B H. N. BAKER MS W P. J. VAI,ElrTI MS W R. A. PAIMER MS 56 W. J. DALTON MS B1F WV-1008, Rev. 2 l KMJ0040.WP3. L; . . _ . . _- _ _ _ _ . - - . _-
4 . WNS TS:( 026 ! TEST
SUMMARY
REPORT ( O Rev. O TEST / TEST SERIES Studre Vash Cement Vaste Form Oualification DESCRIPTION 7ualification Vork with Cubes & Cylinders TEST REQUEST No. WNS TRO 026 TEST PIAN NO, WNS TP 026 ! TEST COMMENCEMENT DATE 05/02/91 TEST COMPLETION DATE 08/27/91 Engineering Release #2272 Date 02/06/92 1.0 OBSERVATIONS / COMMENTS l The purpose of this test procedure was to perform qualification work on ! cenerit waste forms simulating the cement waste to be generated following sludge washing, The test procedure is partially complete and a future revision to this Test Summary Report will_be issued to incorporate the , results of immersion and TCLP Cr tests. The individual objectives defined in the Test Request are reviewed in section 3.0.
2.0 REFERENCES
- 1) TE W7NS TRQ 026 001 Test Exception change of nominal recipe listed in TRQ 026, 5 28 91, M. N. Baker
?. ) TE WNS TRQ 026 002 Test Exception change of spike simulant for leachant selection testing, 5 29 91, J. L. Mahoney
- 3) TE WNS-TP 026 001 Test Exception change of curing time and temperature for cubes & :ylinders, 5 13 91, M. N. Baker
- 4) TE WNS TP 026 002 Test Exception change of nominal recipe listed in-
' TP 026, 5 28 91, M. N, Baker 5)' TE WNS TP 026 003 Test. Exception change of spike simulant for leachant selection testirg, 5 29 91, J. L. Mahoney
- 6) TE WNS-TP-026 004 Tesc Exception substitution of an undersized cube for compressive strength measurement with another cube, 6 6 91, M. N. Baker KMJ0040.WP3 1-
' VVHS.TSR.026 Rev. 0
- 7) Letter TH:91:0107 L. E. Michnik to J. L. Mahoney, "15 day Summary of Vork Performe1 for WVNS.TRQ.026", dated May 8,1991
- 8) WVNSiSIP 91 01, "LWTS/ CSS Incegrated Test", May 2, 1991 including Test Exceptions TE.VVNS.51P.91 01 001 through TE.WVNS. SIP.91 01 009.
- 9) United States Nuclear Regulatory Commission " Technical Position on -
Waste Form' Revision 1. January, 1991. }
3.0 CONCLUSION
S / ACCEPTABILITY OF RESULTS/0BJECTIVES MET The' acceptability of results of the six objectives from WVNS.TRQ*026 are ' presented below, 3.1 Comnressive Strength vs Curo Time (obiective 2.1) Activity Determine the compressive strength of both cubes and cylinders as a function of cure time, Identify a cure time that achieves a strength of 75% of the peak compressive strength. lask Accomolished This' task was completed. During the LVTS/ CSS Integrated Test Run, twenty batches of cement waste were sampled (SIP-91 01). During the sampling, cube forms and cylinder forms were filled with cement product. The i filled forms were inserted into a controlled temperatur<a chamber for l curing at 79 1 2'C for a total of 90 .0/+8 hours (TP.026). Following ' this high temperature cure, the cubes and cylinders vern allowed to finish their cu'ing at room temperature. At pre-defined days, a minimum of three cubes and cylinders were crushed. After a minimum of four weeks, core samples were taken from several full-scale drums (TP.030) for c rushing. Compressive strength data for cubes, cylinders, and corea are presented in Table 1. Figures 1, 2, and 3 indicate the time. dependent nature of the compressive strength measurements. 3 Statistical comparisons indicate the cube compressive strength measurements up through 21' days of curing can be proven to be from a different population than the strengths from 27 days and beyond 1 (Appendix A). Cured strength values need to be differentiated from those samples that are not fully cured. This statistical comparison indicates that any sample cured for at least 27 days can be considered fully cured. O The pre. cured average compressive strength for cubes is 844 pai. The average cured strength is 1046 i 80 psi (at 95% confidence of the mean). A. Chi. Square test of the distribution of compressive strength values for KMJ0040 WP3 2-
VVNS TSR 026 Rev. 0 (N all data f ror. 27 days and beyond show the measurements to be no rmally
\_- distributed (Appandix B) . For cubes, the 75% of peak compressive strength value is 784 pai vnich is achieved within the first 7 days of curin6-For cylinder data, statistical comparisons indicate the compressive strength measurements up through only 8 days of curing can be proven to be from a different populatiot. than the strengths from 15 days and beyond (Appendix A). The pre curec. average compressive strength for cylinders is 1118 psi. The average cured strength is 1284 1 62 psi (at 95%
confide.nce of the mean). A Chi Square test of the distribution of ccmpressive strength values for all data from 15 days and beyond show the - measurements to be normally distributed (Appendix B). For cylinders, the 75% of peak compressive strength value is 963 pai which is also achieved within the first 7 days of curing. A cross plot of compressive strength measurements of cylinders versus those for cubes (both made from the same cement batch in CSS) is shown in Fir,ure 4. The scatter (correlation coefficient - 0.01) shows no - correlation betwestt the measurements. This indicates that the uncertainties in both compressive strength measurements dominate the range of data. G 3.2 ,?ompressive Strennth After 28 Days (obiective 2.2) Activity Verify _the compressive strength of the cement product is greater than - 500 psi after a minimum of 28 days of curing. Task Accomolishcd As noted above, the mean compressive strength for both cubes and cylinders was greater chan 500 pai as early as 7 days of curing. After 2P days of curing the strengths remained above 500 pai. 3.3 Ther:nal Cycline Stability (obiective 2.3) 6stivity Complete a thermal cycling stability test per the US NRC " Technical Po11tien on Waste form" and the ASTM standard B 553. Confirm that the mean compressive strength is greater than 500 psi and that no
/ (,,
f'")s significant cracking, spalling, or disintegration of the specimens occ'rred. KMJ0040.VP3 .. _ _ . - - - _ _ - _ . - - - - - - - _ . - - - _ _ _ _ - - - - - _ _ _ _ _ . _ _ . - _ ------ --__--_- .~
k'VHS TSR 026 ! Rev. O Ingh,,&rgqnwnli shed After curing for 49 days, three cylinders and one instrunented cylinder were placed into a controlled temperature chamber. The temperature was cycled from 60'c to 20'c to 40'c and back with one hour soak periods at each temperature. Thirty of these teaperature cycles were completed on , the cylinders. Compressive strength data is presented in Table 2. Statistically, the compressive strength of the cylinders that were i tbstmally cycled cannot bn di.stinguished from cured cylinders. The average for the cycled cylinders is 1229 psi versus the cured cylinder mean of 1284 i 62 psi. No crackin6, spalling, or disintegration-of the test specimens were detected. 3.4 Leachant Selection (obiective 2:41 Activity , Complete measurements of the resistanJe to both deionized water and l synthetic sea water per the US NRC " Technical Position on Waste Form" and the ANS/ ANSI procedure 16.1. Identify the more aggressive teachant for immersion tests. Confirm the vaste form has a leachability index , (per ANS/ANS1 procedure 16.1) greater than 6.0. Task Accomnlished Cement. waste mini cylinders (l' diameter x 3" height) we:e fabricated from spiked decontaminated supernate. Samples of decontaminated , supernate were collected in the laboratory. These combined solutions were spiked with additional sodium sulfate and pH adjusted to 11.8 to i simulate sludge wash solutions. By using chemically adjusted supernate, i the levels and chemical states of the key radionuclides of interest were l prese rvedi l Table 3 lists the calculated leach indices (per ANS/ ANSI procedure 16.1) ' i at intervals from 2 to 120 hours for Tc 99, Sr-90, Cs 137, and alpha Pu j in both demineralited water and synthetic sea water. All indices are over- 6.0 showing the vaste form meets -its leaching criteria. The data are also plotted in Figures 5 and 6. Technetium was the species leached most rapidly (lowest leach index). The nominal more aggressive leachant varied with time and radionuclide. L O Although Table 3 lists the nominal more aggressive leachant, a statistical comparison of the two for Tc-99 shows almost no discernable difference. KKJ0040.WP3 _ . - _ .
_. . . . . - _ .. _ - . _ _ _ - _ _ , .-~ _ ._ . . . _ . --_ .. _ _ _.. ... VVNS TSR.026 Rev. 0 () Table 4 lists the triplicate measurements that are the source of the averages listed in Table 3. The second portion of Table 4 performs the comparison of differences between demineralized water and synthetic sea water. A significance level (see Appendix A for the equation to determine the significance level) is calculateu based on the comparison of the two sets of measurements. For the time marks of 2, 24, 72, and 96 hours, domineralized water and synthetic sea water were equally aggressive on the cement waste form. At 7 hours, domineralized water was more aggressive. Synthetic sea water was more aggressive at the 48 and 120 hour mark. Overall the two leachants were deemed to be equally aggressive thus domineralized water would be used for the immersion tests. 3.5 Imraersion Testine (obiective 2.5) Activity Following leachant selection tests, perform immersion testing o' the cement waste form for a minimum of 90 days or up to 180 days. Compressive strengths of the immersed waste forms shall be compared to the cured average prior to immersion.per the US NRC Branch Technical O- Position petar. Confirm that the tert specimens show compressive strengths greater than 75% of the average cured pre immersion strength after 90 days of immersion. If strength values are below 751, confirm that the immersed strength levels off above 500 psi after 180 days of immersion. In either case, also confirm that the test specimens show no significant cracking spalling, or bulk disintegration. Task Accomolished This cask remains open. The immersion tests are underway in demineralized water. Compressive strength measurements will be collected and compared to the cured average per the US NRC paper. 3.6 TCLP Cr Testine (obiective 2.6) Activity Complete a standard Toxicity Characteristics Leaching Procedure (TCLP) test for chromium on a vaste form produced during the LVTS/ CSS Integrated Test Run. Confirm the test specimens yield < 5 ppm Cr in the (. u
.leachant, KMJ0040.VP3 - 5 ec- m x-w. -.r,4 p- g .e , 4, , - c -e-- e- w-ee-+, - , e=.msr-w,a e--== -
's we m-m 1- wsw .r. *
- r- er- - --
- .=- .
. i
, VVNS TSR 026 Rev. 0 Task Accomolished
( This task remains open. A cube produced from cement waste collected during the LVTS/ CSS Integrated Test Run was extracted for chromium on 1 July 23, 1991. Per the test procedure, the extract must be analyzed for j Cr within 180 days. Pollowing analysis, the data vill be presented in a revision to this test summary. 4.0 ACTIONS OUTSTANDING Desired activities and analyses that remain as of this writing are outlined below: 4.1 Immersion Testine (obiective 2.5) l t Complete compressive strength measurements of the immersed waste forme for up to 180 days from start- of immersion. Compare the waste form compressive strengths to those of the unimmersed cured waste. Action: Analytical & Process Chemistry Timing: January 15, 1992 4.2 TCLP Cr Testine (obiective 2.6,1 Per the TCLP procedure, complace the chromium measurement of the esment waste form extract. Action: Analytical & Process Chemistry Timing: January 24, 1992 4.3 Revise the Test Summary Report Update the TSR to reflect results from both the immersion tents and TCLP-Cr tests, i Action: IRTS Engineering Timing: March 1. 1992 P KMJ0040.VP3 , _ - - _ . . _ , _ - _ _ - . . _ _ . _ _ _ ~ . . _ . _ - . _ _ ,. _ , _...~_. _ - _ . _ . . , _ _ ._ _ , . -
WHS TSR.026 Rev. 0 O /
')! d.u, APPROVAL (S) . , . .
ADDITIONAL REVIEVERS: YES NO [L. Mahoria nun i7;' L.e(l' M. N. Baker A.f J. Howell
+M d Tilk ;
?D. C. Meess
/
j // i ll tv2 )} [ ft:,,,seh.i;, <j':; Quali(y^ Assurance (d 1 O, a TN 0040.VP3 ,- - - . . _ _ . - ., . - . . . - . . , . - . . . - - . _ . _ . . . . - . . .. . - . - .
_ . _ _ . . _ . - _ _ _ . _ _ . _ _ _ _ . . . _ _ _ . _ _ . .____.__...m____ UVNS TSR.026 Rev. 0
/^
. (]
' Table 1 Compressive Strength of Cubes, Cylinders, & Cores Cubes -Cubes Cy1 Cy1 Core Core DAX1 E11 DDEL. Ell Dl32 _. Ell DB2 DAY.1 7 785 81438 1111 81438 7 862 81632 1188 81632 7 789 81653 1026 81653 8 749 81299 934 81299 8 802 81408 1082 81408 8 795 81420 1365 81420 15 823 81300 1493 81301 15 851 81438 1408 81438 15 519 81439 1514 81439 21 767 81265- 1231 81265
-21 839 81298' 1203 81298 21 1025 81406 1125 81406 21 1108 81416 1394 81416 21 813 81439 1344 81439 21 IQ22_ 81632 1323 81440 28 1119 81293 1500 81298 1120 81632 28 28- 1177 81433 1358 81433 28 996 81439- 1464 81439 35 750 81294 1252 81294 1204 81632 35 35 1084 81296 1337 81296
(T 35 35
.995 1189 81300 1096 81300 \s / 81301 1337 81301 35 735- 81408 828 81408 1389 81632 42 35 1071 81632 1211 81o32 1431 81632 42 42 1005 81263 1698 81263 1305 81632 42 42 1210 81440 1239 81440 1215 81300 43 42 946 81653 1004 81653 1199 81300 43 43 752 81418 1549 81418 909 81300 '43 43 810 81433 1436 81433 1296 81300 43 43 1149 81438 1075 81438 1279 81439 45 45 1.'17 81263 1210 81263 1086 81439 45 45 1274 81418 1337 -81418 883 81439 45 45 881 81418 1252 81418 1389 81414 47 45 776 81433 1181 81433 1431 81414 47 4/ 1011 81296 1153 81296 1215 81420 48 47 1291 81299 1287 81299 1360 81420 48 47 1008 81414 1153' 81414 1191 81439 49 47 1271 81416 1217 81416 1328 81439 49 47 1279 81420 1125 81420 1441 81439 49 O
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.CompressivelStrength Analysis TP-026
- Cylinder Strength vs Curing Time
- Compressive Strength [ PSI]
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l . . . . . . . . . 0 5 10 15 20 25 30 35 40 45 50 Cure Time [ Days] i . Avg cured: 1284 62 psi . n gure 2 -
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Compressive Strength Analysis TP-026 Cylinder Strength vs Cube Strength Cylinder Strength [ PSI] 1800 . . 1600 - - - - - :- - - - - :- - - - - -:.
.o 1400 - - - - - - - - - -
=
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800 1200 1300 1400 1500 500 600 700 800 900 1000 1100 Cube Strength [ PSI] Figure 4 4e
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+
l . VVNS.TSR 026 Rev. O J'\ Table 2 ' Compressive Strength of Thermal Cycled Cylinders Compressive ' Drum Strength [ PSI) 81294 1079 81296 1324 i 81414 1283 Table 3 Leachant Selection Testing Results '
-In Domineralized Water Average Leachability Indax ;
hrs Tc.99 Sr-90 Cs+137 a Pu 2 7.725 10.026 7.813 14.047 7 7.831 9.974 8.051 14.219 24 7.692 10.08 7.976 14.224 48 8.112 10.3$5 8.457 12.962
- 72. 8.555 10.695 8.91 13.083 f 96 8.936 10.985 9.324 13.186 120 9.299 11.313 9.681 13.269 l
) In Synthetic Sea Water Average Leachability Index hrs Tc.99 Sr.90 Cs 137 a Pu 2 7.885 10.424 7.977 11.751 7 8.010 10.726 8.289 11.924 24 7,797 11.392 8.060 13.235-48 8.026 10.85 8.393 11.153 '
72 8.459 10.637 8.847 11.682 96 8.879 11.509 9.225 11.783 120 9.138 11.783 9.598 12.106 More Aggressive Leachant hrs Tc 99' Sr 90 Cs.137 a Pu 2 Demin Demin Demin Sea 7 Demin Demin Demin Sea 24 Demin bemin Demin. Sea 48 Sea- Demin Se a -- Sea 72 Sea Sea Sea Sea 96 Sea Demin Sea Sea 120 Sea Demin Sea Sea KMJ0040.VP3 13 -
. _ . . - .. __ . _ _ . _ _ _ . . , _ _ . _ - _ . . _ _ _ . - . . - _ - - _ . _ . _ . - . . ~ _ _ _ _ . . . . . . -
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. W h ,TTSR-026 , ,
""~
Leachability Indicies TP-026 . Demineralized Water. -
. Leach Index 16 . . . . . . . . . . .
m me.......k........................................... 14 . . . . . . . . . . . 3 .' u
. . -a .
Radionuclide 12 - - - :.- - - - :- :- -- - - :: - - :: - - - :: - - - :. - - -::- -:.- -::-- - - :- - - -
--- Tc-99
.: .r n. ---
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- Figure 5 [
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W h l-VSR-OZ6 Leachability Indicies TP-026 Syntheti~c Sea Water i
. Leach Index i 19 . . . . . . . . . . .
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Y- . 30 ... .......... 3c_99 , , . . . . . . . . . s % i Sr-90 8
...............~......... ........ ^
'*' Cs-137 i
4 a lpha Pu 6 --- .--- . 4 4 ! 0 10 20 30 40 50 60 70 80 90 100 110 120
,I,est ,I nne Hours. :
1 Figure 6 i
- f. 1
(' a i
, VVNS TSR 026 i Rev. 0
( Table 4 Statistical Comparison of Leach Indices for Tc-99 leach Indices Triplicate Measurements for Tc.99 I hrs Demineralized Vater Synthetic Sea Water l 2 7.716- 7.744 7.718 8.091 7.781 7.785 7 7.894 7 782 7.816 8.016 7.991 8.024 24 7.765 7.640 7.672 7.815 7.781 7.794 ! 48 8.074- 8.122 8.141 7-985 8.053 8.040 72 6.588 8.490 8.587 8.430 8.508 8.439 96 8.919 8.954 -- 8.892 8.866 -- 120 9.246 9.280 9.370 9.170 9.131 9.114
-Statistical Comparison of Leach Indices for Tc 99 4
/'~ Demin Water Synth Sea Water Signif
(- hrs Avg Var Avg Var Delta Level Diff7 ! 2 7.73 0.00015 7.89 0.02108 0.16 0.29 No 7 7.83 'O.00220 8.01 -0.00020 0.18 0.10 Yes 24 7.69 'O.00281 7.80- 0.00020- 0.10 0.11 No r 48 8.11 0.00079 8.03 0.00087 0.09- 0.08 Yes 72 8.56 0.00211 8.46 0.00121 0.10 0.11 No
- 96. 8.94 .0.00051 8.88 0.00017 0.06 -0.07 No 120. 9.30 0,00274 9.14 0.00055 0.16 0.11-- Yes t t
s 1 KMJ0040.VP3' ,. , -, . . , .,, ,-- . . , . . . - - - - . - . - - . - - ~ - - - ~ - - . - - - - .
E ,
]
, VVNS TSR.026 Rev. 0
)- Appendix A Statistical comparison of Compressive Strengths Pre-Cured Versus Cured Strengths for Cubes Days PSI Days PSI 7 785 844 aversge 28 1119 7 862 14266 variance 28 1177 7 789 15 no points 28 996 8 749 35 750 8- 802 35 1084 8 795 35 995 15 823 35- 1189 15- 851 35 735.
15 619 35 1071 21 767 42 1005 21 839 42 1210 21- 1025- 42 946 21- 1108 43 752 21- 813 43 810 21 1027 43 1149 1046 average 45 1317 34122 variance 45 1274 24 no. points 45 881 O- 45 776 47 1011 < 47 1291 47 1008 47 1271 47 1279 Delta between group averages - 202 ' Significant delta - (var,*n,+ var,*n,)/(n,+n,-2)* . (n,+n )/n,/n,) ^0.5*t statistic ' var , var, : variance of the two groups
- n. , A : - number of data points in each group t-statistic: from standard tables for 951 confidence with n,+n. 2 degrees of freedom Significant delta - 111
' Delta between_ group averages > significant delta -therefore, the two groups are significantly different.
KMJ0040.WP3 17 .
~ . _ - _ , , _ _ . - . . _ , - . - _ . _
VV!1S TSR 026 Rev. O Appendix A (Cont.) Statistical Comparison of Compressive Strengths Pre Cured Versus Cured Strengths for Cylinders Days PSI Days PSI 7 1111 1118 average 15 1493 7 1188 18262 variance 15 1408 7 1026 6 no. points 15 1514 8 934 21 1231 8 1082 21 1203 8 1365 ?1 1125 21 1394 21 1344 21 1323 28 1500 28 1358 28 1464 35 1252 35 1337 35 1096 1284 average 35 1337 29522 variance O 33 no. points 35 35 42 828 1217 1698 42 1259 42 1004 43 1549 43 1436 43 1075 45 1210 45 1337 45 1252 Delta between groups - 166 Significant delta - 154 Delta between groups > significant delta, therefore, the two groups are significantly different. O KMJ0040.WP3 _
^
- WNS TSR 026 Rev. O Appendix B Chi-Square Test of compressive Strength Data for cubes i
Sorted Z value Area Qty Actual Error i S trer.gths Expected Qty in group ' infin 0 735 750 752 group 1 3.5 5 0.67 . 776 810 avt break 845.5 1.06 0.1446 881 1 946 . l 995 group 2 6.5 5 0.36 ' 996 1005 , avg break 1006.5 0.21 0.4168 1008 1011 1071 group 3 6.3 5 0.28 1084 :
. 1119 ,
avg break 1134 0.47 0.6808 1149 1177-1189 1210 1271 1274 , oup
; 4 7.7 9 0.23 1279 1291 1317
+infin 1 Total group errors 1,55 90% significance Chi Square Value 3.84
Conclusion:
Normal Gaussian Distribution I 4 KMJ0040.WP3 19 -
-. . - . . . _ _. - - . . _ . _ . . . . . . _ . ~ _ _ . _ . . .. ., _ _ __,
4-VVNS TSR 026 Rev. O I (
.i Appendix B (Cont)
Chi Square Test of Compressive Strength Data for Cylinders Sorted Z value Area Qty Actual Error Strengths Expected Qty in group
-infin 0 828 1004 1075 1096 group 1 6.7 6 0.07 1125 1125 I avg break 1139 -0.83 0.2033 1153 i 1153 1181 group 2 4.7 5 0.02 1203 1210 avg break 1213.5 0.40 0.3446 1217 1217 1231 group 3 3.0 5 1.28 1252 L252 av5 break 1255.5 +0.16 0.4364 T 1259
[d-1287 1 1323 1337 group 4 6.4 6 0.02 1337 1337 avg break 1340.5 0.33 0.6293 1344 ' 1358 1394 Sroup 5 6.6 5 0.38 1408 1436 avg break 1450 0.95 0.8289 1464~ 1493 1500 1514 group 6 5.6 6 0.02 1549 1698
+infin 1 Total group errors 1.81 >
95% significance Chi Square Value 7.84 *
Conclusion:
Normal Caussian Distribution l l O L KMJ0040.VP3 20 -
- 1. , , .. , . . . . - , - - - - - -. . . - - . . . - - - - - - . . - - . -- - -
4 o West Valley Doo. u.se, m S.Tn,.0,s V Demonstration Project Revi ion N - oer i Revision Date 07/01/91 Engineering Release #2055 Per ECN H388 TEST REQUEST DEVELOPMENT OF THE PROCESS CONTROL PARAMETERS FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUIDS PREPARED BY f -
.n 6/25[9/ J. L. Mahoney Cogn ngineeK APPROVED BY / 74.-9 (
, D. C. Meess Cogn7zant Systse Design ManaEer APPROVED BY d!// 4mf# 9 $ 0 D. L. Shugars Quality Arg6rance Manager A BY ,
Radiation /id Safety Manfger I D. J. hasward APPROVED BY h*b bi w 6[27[9# J. C . Cwynar IRTV Process C6ntrol "ngineering West Valley Nuclear Services Co,, Inc. P.O. Box 191 Ba0050 :3RM West Valley, NY 14171-0191 O - WV 1818. Rev.1 e---y e y --4e -..---m.- --p- -.- w -. - . ewag-
4
- WNS.TRQ.028 Rev. 1 RECORD OF REVISION PROCEDURE
( If there are changes te 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 Example:
> The arrow in the margin indicates a change.
Revision On Rev. No. Description of Changet Page(s) Dated 0 Original Issue All 04/91 1 Per ECN =4388 All 07/01/91 O W.1807, Rev.1 i O BELOO50:3RM
4 WNS TRQ.028
,- Rev, 1 RECORD OF REVISION (CONTINUATION SHEET)
O Rev. No, Description of Changes Revisi{non Page s) Dated i O
)
e W 1807, Rev. 1 11 BELOO50:3RM O
,. m m . . . - . .2.2.. _. . m m,..,_.m .m. . . - - . . - # -.... ..2 ., ..
4 RNVS TRQ-028 Rev. 1 DEVELOPMENT OF THE PROCESS CONTROL PARAMETERS FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUID 3
1.0 INTRODUCTION
1.1 This work is required to demonstrate the stability of the waste form at vatisble cement recipe and waste parameters. The characteristics which will be tested are required by 10 CFR 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, draft dated December 1990.
1.2 Work will be performed with a simulant representing the actual waste 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 with the cement blend and other additives. The effect of variations in additives will also be evaluated, as discussed in the Branch ( A . Snical Positioa, Appendices A.V. and A. VI.
> ' A u reening +est set as well as a multi-variant test set will be pertcrmed. Tae test matrices'are shown in Tables 1 and 2.
- 1. s Test Procedure VVNS-TP 028, providing instructions for testing in 2neardance with this Test Request shall be issued by Analytical &
.txocess Chemistry per EP 11 003, 1.7 A Test Summary Report documenting the results of this testing shall be issued by the Cognizant Test-Engineer per EP-11 003, 2.0 OBJECTIVES
>~ 2.1 Screening Tests Thirteen variables will be varied from low (indicated by " " in Table 1) to high (indicated by "+" in Table 2) as part of a Plackett-Burman type 28 run screening experiment. The thirteen variables are listed below with applicable low and high values
-(ratios, i.e. 0.5x, are relative to the nominal LWTS concentrates recipe in Table 3, or cement recipe in Table 4):
./ fdLOO50:3RM 1
, . . ~ = .
WVNS-TRQ 028 Rsv. 1
> variable- number low high
('~N (_,) sulfate 1 0.5x 2x nitrate: nitrite ratio 2 0.5 2.8 organics _ 3 0.5x 4x aluminum (gm Al/gm C1) 4 0 2.5 cotal solids (TDS) 5 25 37 water: cement ratio 6 0.3 0.8 calcium nitrate 7 0.5x 2x pH 8 11 13 mix time (mins) 9 4 16 anti foam 10 0.3x 2x sodium silicate 11 0.5x 2x
- phosphate (gm P04/gm Cl) 12 0.01 7.0 boron (gm B/gm C1) 13 0.001 0.15 Followirq compressive strength crushing of the cement cubes, data reduction will be mandatory by the Cognizant Test Engineer and Cognizant A&PC Scientist. The data reduction will identify key process variables (variances statistically significant compared to pooled varia.nce) which will be varied in the multi variant testing in the next section.
> 2.2 Mulri variant Testing The multi variant response of cement compressive strergth will be evaluated via a Box Behnken test. A two-set, five-variable Box.
(} Behnken design is presented in Table 2. This type of experiment
\,,/ will provide response surface coefficisnes which cover all single variable and quadratic terms.
Before proceeding with this section of the test, an agreement will be reached betvein the Cognir. ant Test Engineer and Cognizant Scientist. This agreemant will be documented in the form of a Test Exception -(TE) to Test Procedurt (VVNS-TP 028) per EP-ll-003. The TE will define the number of variables in the study and the ranges to be evaluated in the test (in Trble 2 high amounts are noted as
"+1", low amounta are noted as ".1", and nominal values are noted as "0").
3.0 SAFETY
'3.1 Industrial safety practices shall be as described in the VVNS Hygiene & Safety Manual, WVDP 011.
3.2 Radiological work will be performed in accordance with the WVDP-Radiological Controls Manual, WVDP-010. 3.3 . Safety practices specific to the A&PC Laboratory will be as described in ACP 7.2, Safety Practices for the Analytical & Process Chemistry Department.
~
[ t BELOO50:3RM 2
UVNS TPQ 028 dov. 1 4.0 EQUIPMENT CONFIGURATION ( j' _, 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. 4.2 Balances and other weighing equipment accurate to 0.01 gram will be calibrated prior to use in accordance with ACP 7.1, 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, etc., as discussed in the 3 ranch Technical Position, appenoix A.III.A. 4.4 Curing of the samples will be performed in a manner which duplicates, to the extent practical, the curing temperature profile encountered in the full-scale drum, as discussed in the Branch Technical Position, appendix A.III.B. A temperature-:ontrolled chamber will be utiliand. 4.5 Calibration of compressive strength testing equipment will be in accordance with ASTM Method C-39 and C 109, 5.0 SAMPLING 5.1 Samples will be produced in the quantities and frequencies specified ('] in UVNS-TP 028. V
> 5.2 The test matricles are shown in Tables 1 and 2. Each test will be conducted with the variables adjusted to the maximum (shown by a "+"
or "&l"), the nominal value (shown by a "0"), or the minimum value (shown by a " " or " 1"). Independent as well as dependent variables will be evaluated. 6.0 PERSONNEL QUALIFICATION 6.1 Testing will be performed by qualified Analytical & Process Chemistry Technicians using WVNS TP-028 and approved Analytical Chemistry Methods (ACM's) under the cognizance of an A&PC scientist.
- a. Radiochemistry "B" Technicians qualified to WVNS-QS 014
- b. Radiochemistry "A" Technicians o,ualified to WVNS-QS 016 r~s,
( I BELOO50:3RM 3
f ~.. /~X j,~ .} kv ) ' WNS-TRQ-028 Rev. 1
.)
Table 1 WENTY-EICHT-RUN FIACKETT-BURMAN SCREENING DESIGN Note: Before running tests, the order shall be randomized Variable Number Trial 1 2 3 4 5 6 7 8 9 10 11 12 13 1 + -
+ + + + - - - - + - -
2 + + - + + + - - - - -
+ +'
3 -
+ + + + + - - -
+ - - -
4 - - -
+ + + +
+ - -
+ -
5 - - -
+ + + +
+ + - - -
6 - - - -
+ + + + + -
+ -
+
7 + + + - - -
+ -
+ - -
+ -
8 + + + - -
+ +
+ - -
+
9 + + + -
+
+ -
+ - -
10 -
+ - - -
+ +
+ + -
+
11 - -
+ + - -
+ - - -
+ + +
12 + - - -
+ +
+ -
+ -
13 - -
+ -
+ - - -
+ + -
+ +
14 + - - - -
+ + - -
+ + - -
15 -
+ -
+ - - -
+ - -
+ + + -
16 - -
+ -
+
+ -
+ -
+ +
17 + - -
+ - - - -
+ + + -
+
18 -
+ - -
+ -
+
19
+ + -
+ + -
+ -
+ + +
+ -
+ +
20 -
+ + + + + +
+ + +
21 + -
+ -
+ +
+ + -
+ +
22 + + +
+ + -
+ -
+
23 + +
+
+ + + + - .
'24 -
+ + +
+
+ -
+ + - -
25 + -
+ + -
+ +
+ -
+ + +
26 + + -
+ +
+ + + + +
27 -
+ + + +
+ -
+ + + +
28 - - - - - - - - BELOO50:3RM 4
./ \
{J u . Y ~ WNS-TRQ-028 :
> Rev. 1 Table 2 TUO-SET, FIVE VARIABl.E BOX-BEllNKEN TEST DESIGN Note: Before running' tests, the order in each set shall be randomized, but the sets shal1 not' be mixed.
~
Variable Number Variable Number Trial 'l 2 3 4 5 Trial 1 2 3 4 5 1 +1 +1 0 0 0 24 0 +1 +1 0 0 2 +1 -1 0 0 0 25 0 +1 -1 0 0 3 -1 +1 0 0 0 26 0 -1 4
-1 0 0
-1 -1 0 0 0 27 0 0
-1 -1 0 0 5 0 +1 +1 0 28 +1 0 0 +1 0 6 0 0 +1 -1 0 29 +1 0 0 -1 0 7 0 0 -1 +1 0 30 -1 0 0 +1 0 8 0 0 -1 -1 0 31 -1 0 0 -1 0 9 0 .+1 0 0 +1 32 0 +1 0 0 +1 10 0 +1 0 0 -1 33 0 +1 0 0 -1 11 0 -1 0 0 +1 34 0 -1 0 0 +1 12 0 -1 0 0 -1 35 0 -1 0 0 -1 13 +1 0 0 0 0 36 +1 0 0 0 +1 14 +1 0 0 0 0 37 +1 0 0 0 -1 15 -1 0 0 0 0 38 -1 0 0 0- +1 16 -1 0 0 0 0 17 39 -1 0 0 0 -1 0 0 0 0 0 40 0 +1 0 +1 0 18 0 0 0 0 0 41 0 +1 0 -1 0 19 0 0 0 0 0 42 0 -1 0 +1 0 20 0 0 0 0 0 43 0 -1 0 -1 0 21 0 0 0 0 0 44 0 0 0 0 0 22 0 0 0 0 0 45 0 0 0 0 0 23 0 0 0 0 0 46 0 0 0 0 0 t
BELOO50:3RM 5
_ _ _ _ ._. ~ . . _ - . _ - - _ - - - - . ,. . _ . . . _ . . . - _ .. .. _ .m. _ - e. i WNS TRQ 028 -
,+. Rav, 1.
>- 'TAbl.E 3: REVIShlD SALT 00NCElrmATIONS FUE THE "NOKIMAL" .
- f - V SIMUIAirr RECIPE BASED ON 129" HEEL ;
, CMSTITURNT FORMULA WEIGHT
-t Sodium Nitrate- NANO 3 286 lbs.
Sodium Nitrito nan 0 2- 272 lbs. Sodium Sulfate 170 lbs. Na2SO4 t Sodium Bicarbonate NaHCO *- 3 Potusiun Nitrate- KNO 3 17.9 lbs, Sodium Carbonate 48,4 Ibs, Na2CO 3 . Sodium Hydroxide. NaOH **10.4 lbs. Sodium Dichromate, Dihydrate Na2Cr207 2H 2O -1590 g Sodium Chloride Nacl 1310 g Sodius' Phosphate Dibasic Na2HPO 4 950 g ;
. Sodium Molybdate, Dihydrate .Na2Mo04.2H 226 g 2O Sodium Tetraborate, Decahydrate B0 Na2 4 7 10H 2O 122 g
- Citric Acid,s Anhydrous- CH0;-
687 160 g Oxalic Acid, Anhydrous CH0 224 129 g
- Tartaric Acid, ' Anhydrous CH0466 180 g Water HO 1668.0 lbs.
2 TOTAL VEICHT 2483.1 lbs. [
- l. Veight of Solids 815,1 Ib's.
Veight Percest Solids 32.83 percent Note that--Sodium Bicarbonate does NOT appear as NaHCO3 at elevated pH's.
** The Sodium Hydroxide (Na0!!) value is an approximation to arrive at a- pH of 12.1. This'value may vary..
BELOO50:3RM- 6 p. L
-+ WNS.TRQ,028
- Ray. 1 e >-
TABLE 4: Lab scale " Nominal" Recipe
/
I A Simulant 96 mL Cement / Calcium Nitrate Blend 140.5 g +/ 1.0 g Antifoam Eaulsion 0.3 mL Sodiun Silicate 11.0 g +/- 0.5 g
. . _ __ __ _ _ __ . _ _ _ _ _ _ _ _ m , s4 Doc. Number WVNS-TP-028 A O(/ - West Vallev# Revision Number 1 Demonstration Project Re,1eien Date 0,,16a1 Engineering Release #2076 l Per ECN #4429 l
l TEST PROCEDURE PROCEDURE FOR DEVELOPMENT OF DROCESS CONTROL P ARAMETERS FOR CEMENT SOLIDIFICATION OF SLUDOE WASH LIQUIDS i PREPARED BY .b h _ L. E. Michni k l CognirapWer n O b APPROVED BY Cognizant System Design Manager D. C . Mees s
/ 1 APPROVED BY , _ f / N / d'/w/M
+
o -' 7 D. L. Shugars Quality Assurance M& nager APPROVED BY 6M u Fc/t[4J'fdgfD.J. Harw ard Radiation and Stret.y Manager APPROVED BY G1#he M ICC. Process Control /Engifteering J. C . Cwynar West Valley lluclear Services Co., Inc. P.O. Box 191 (O (j West Valley, NY 14171-0191 MIB0900: 3PJi WV-1816, Rev.1
i i
, , , WVNS TP 028A Rev, 1 l 9
RECORD OF REVISION : l PROCEDURE u If there are changes to the procedure, the revision number increases by one. These changes are-indicated it. the left margin of the body by an arrow (>) at the beginning of the paragraph that contains a change. Example;
>- The arros in the margin indicates a change.
Revision On Rev, No. Description of Changes Page(s) Dated 0- Original Issue as VVNS TP 028 All 05/01/91 1 Per ECN #4429 A1) 07/16/91 (Issusd as VVNS-TP-028A) I'~ v) () WV-1807, Rev. 1
- MIB0900 3RM 1
.. . . . - . - _.- . _ . . - - - . . ~ . - ~ . . . . - ---- --... - -.- -... -. - . . . . . . . . .
. o- WNS-TP 028A Rev. l' RECORD OF REVISION-(CONTINUATION SHEET) .
, Rev.-No. Description of Changes Revision)on Page(s Dated t J t 'l i W-1807, Rev. 1 11
-MIB0900:3RM l
+- '* y'y-y
,, ,, . VVHS-TP 028A Rev. 1, TABLE OF CONTENTS
- (
Section . Description. Page 1.0 SC0PE,.........................,....,, . . . . . . . . . . . , , , , , , , , 1 2,0: DEFINITIONS.AND ABBREVIATIONS................ . . . . . . . , , . . . 2
~3.0 QUALITY ASSURANCE,.... .......... ......................., 3 4.0- TOOLS, EQUIPMENT, COMPONENTS, AND REFERENCES . , , , . . . . , , , . 4 5.0 CENERAL'INFORMATION,,,,..... ............................. 6 6.0- PROCEDURE,..............................., . . . . . , , , , , , , , , 7_
7.0 DATA ACQUISITION.................. . . . , , , , . . . . . . . . . . . 14 TABLE 1: BAS E ' S OLUTI ON . . . . . . . . . ............... . . . . . . . . . . . . . . . . . 15 TABLE 2: TWENTY-EIGHT RUN PIACKETT BURMAN SCREENING DESIGN. . . . . . . 16 TABLE 3: ' VARIABLE CUBE PARAMETERS,.... ,, ...,,.,,,,,,,.... . . . . . . 17
.p ATTACHMENT A. . MULTI VARIANT CUBE WORKSHEET,,.,,,.,, ,, .,,.. , , A1 v-
'MIB0900:3RM i11
(- i-g i, i-
..m ._ - _ _ _ . . . _ -
~ ~ . - - - .
,_. ,, WNS-TP 028A Rev-. ' l y WNS-TP-028A
- PROCEDURE FOR- DEVELOPMENT OF PROCESS CONTROL PARAMETERS FOR CEMENT SOLIDIFICATION.0F SLUDGE VASH LIQUIDS Rev. 1
~
1,0 SCOPE, 1.1. This Test Procedure is being written in partial fulfillment of WNS-TRQ-028 and WNS-TPL 70-11. The completion of WNS TRQ 028 vill be fulfilled under WNS-TP 028B. The objective of this overall testing criteria is to establish windows for full scale production of the sludge wash cement waste form within which an acceptable-product _can be made. This is, based upon the requirements stated in appendix A, section VI,rf the NRC Technical Position on Wasta Forn., Revi-1, dated January 1991. These windows include variances In the major chemical- components of the simulated sludge wash liquid, the cement recipe enhancers as well as physical parameters. Laboratory specimens, 2-inch squaro cubes, will be used in evaluate these h
%J
~
-windows.
1.2 The- work will include the formation of a series of 28 solutions representing variations in the liquid waste chemical components and cement cecipe enhancer which will produce 28 individual 2-inch by 2-inch cubes. 1.3 These-28. cubes' vill be used to screen the degree of interactions between 13 individual components and will be based upon the cube's
~
compressive strength _via a Plackett Burman Screening Design test, 1.4 The 13 individual components will include variation in the chemical constituents of sulfate, nitrate: nitrite ratio, organics, aluminum, pH,; phosphate -and borate. Also to be varied will be the physical parameters of_ total solids, mixtime, water: cement ratio, and the cement recipe enhancers of calcium, antifoam, and sodium silicate. MIB0900:3RM 1
, VVNS TP 028A Rev. 1 4 1
1.5 ' Af ter an' appropriat s curing period, per section 5.1, the laboratory specimens vill-be subjected to compressive strength testing-as per section 6.3. This testin8 will Provide data on the influence of-variations of the chemical composition of the sludge sasn liquid and the recipe. enhancers on the cenpressive strength or' the cement waste form. 1.6_ The gel time, free liquid volume, pH of the free liquid end penetration resistance will be measured and recorded for each cube as part of ACM 4801. 2.0 DEFINITIONS AND ABBREVIATIONS 2.1 Definitions 2.1.1 - Cement-Dry Portland Type I cement in accordance with ASTM Standard C-150-85.
\.
2.1.2 Antifoam-General Electric AF9020 emulsion of 5 percent dimethlysilicone in nanopure water. This is used as a cement recipe enhancer to prevent air entrapment in the cement matrix during.high speed mixing. 2.1.3 Sodium silicate - is used as a-recipe enhancer in the gelling of the cement waste form and prevention of excess bleed water. 2.1.4 Calcium nitrate tetra-hydrate - is used as a recipe enhancer in the setting of the cement vaste form.
-2.1.5' Cube - 2x2x2-inch mold -used to make laboratory specimens.
MIB0900:3RM. 2 s
- . ..... .. ~ - - . - - - . ~ . - . . . . -. - __
WVNS TP 028A Rev. 1 1 2.2 Abbreviations
.. (
ACM - Analytical Chemistry Method ASTM - American Society for Testing and Materials NRC - Nuclear Regulatory Commission = 3.0 QUALITY ASSURANCE 3.1 - Analytical and Process Cheraistry (A&PC) will be responsible for the , preparation and testing of the laboratory specimens in accordance with this test procedure and the applicable steps in the appropriate Analytical Chemistry Methods (ACM). A&PC shall. verbally notify cognizant Quality Engineer and Quality Service Manager 24 hours prior to commencement of work.
-3.2- Quality Assurance Responsibilities 3.2.1. Quality Assurance shall verify all chemical used in testing
() having the correct chemical formula on container as is required for this test procedure. 3.2.2 Quality Assurance shall provide independent verification of all chemical processing, measuring, mixing, and other processes required to produce-the first five cubes. Quality Assurance may parform the above activities on remaining 23 cubes. 3.3 All WVNS personnel are responsible for documenting nonconformances con cube recipes and/or cube preparation. Nonconformances shall be documented.using Nonconformance Report Form, WV 9202. Any cube rejected shall be reported and rejected cube documented with data
.from other cubes.
>~ MIB0900:3RM. 3 k
.y.7, 9e >9 y g- w- 'm
, o WNS TP 028A Rev. 1 3,4 .A&PC shall maintain-material control by labeling all containers used ~
in testing. A bond laboratory notebook will be used to record solution contents and testing observation along with attachment A. 4',0 TOOLS,' EQUIPMENT, COMPONENTS, AND REFERENCES 4.1 Tools and Equipment. Ligntnin Lab Mixer, Model No. TS-1515 with hiS h-shear impeller er equivalent 2x2x2-inch plastic American Cube Molds
'100 milliliter (mL) plastic or glass graduated cylinder with 1 mL divisions 500 mL polypropylene plastic bottles
- Corning'het-plate or equivalent
- 10 mL glass volumetric flask 20 mL plastic scintillation vials G' -L magnetic stirring plate and magnetic stir bar stopwatch or timer accurate to 1 second top loading balance readable'to + 0,01 grams (g) I Blue M' Oven Model No. C 2630-Q or Despatch Environmental-Chamber Model No, 16301_
< -Gilson' Penetrometer Model'No. CT-421~
fine sand or' emery paper
.4,2- Reagents Portland Type 1 cement Calcium Nitrate tetra-hydrate, reagent grade
-- Aluminum Nitrate, reagent grade
' Citric Acid Monohydrate, reagent grade MIB0900:3RM 4 e
o
WVNS TP 028A
.* Rev. 1
-- Oxalic Acid Dihydrate, reagent grade
- d Tartarie Acid,. reagent grade Sodiut Silicate, 38 vcight percent in a water base, technical grade-
- Antifoam Ceneral Electric AF9020*
- Aluminum Nitrate
- 9 H 20, resgent grade Sodium Phosphate Mono hydrate, reagent grade
-Sodium Tetraborate Decahydrate, reagent grade Sodium Nitrate, reagent grade Sodium Nitrate, reagent grade Sodium Carbonate, reagent grade Potassium Nitrate, reagenc grade
' Sodium Hydroxide, reagent grade Sodium Chromate tetra-hydrate, reagent grade
. -' Sodium Chloride, reagent grade
--- Sodium Molybdate Dihydrate, reagent grade nanopure or-ASTM Type I water
*-supplied by IRTS operations 4.3 References
- NRC Technical Position on Waste Form (Revision 1), January 1991
- ASTM C-150-85 " Specifications for Portland Cement"-
ASTM C-109-86 " Compressive Strength of Hydraulic Cement and Mortars (Using 2 in or 50-mm Cube Specimens)" WVNS-TPL 70-ll " Test Plan of the Waste Form Qualification Program for Cement Solidification of Sludge Wrsh Liquid" WVNS-TRQ-028 " Test Request for Development of the Process Control Parameters for Gement Solidification of Sludge Wash Liquids" MIB0900:3RM' 5
, .3 WVNS TP 028A-Rsv. 1 V[~'j _
ACM 4701 " Destructive Test of 2-inch Cement Cubes" ACM 4801 " Cement Test Cube Preparation Method" ACM-2401 " Density" ACM 2502 " Total Solids" (Microwave) ACM 2601 "pH" (Electrode) 5.0 CENFRAL INFORMATION 5.1 The' compressive- strength tests on cement vaste form specimens will be used to evaluate the process control parameters and is considered an acceptable critsria for the overall performance of the product as indicated in appendix A, section VI of the NRC Technical Position on Vaste Form, Rev.1, January 1991. Although cement products nominally achieve _75 percent of their strength in approximately i28 days, it has been decided by convention that a curing period of 7 days for laboratory specimens will allow the specimenn to gathet
.(s sufficient strength in order to be evaluated, This_ curing process \s- for process control parameter cement specimens requires they be ,
placed in an oven or environmental chamber and sealed individually or in a group in plastic bags for 9018 hours at 79 + 2 C and then a penetrometer test is performed on each specimen to see if _ the cement has set and must-be greater than 700 psi. During the remaining time period, for a total of 7 days 1 8 hours, the specimens;will be cure at 20 1 5 C. At this point the specimen will be testing for compressive strength by the applicable steps of ACM-4701. The results from this testing will provide a basis for the effects of variances which could be experienced in the full-scale process.
,-~s MIB0900:3RM 6 O)
l WNS TP-028A l Rev. 1 6.0 PROCEDURE Oven or environmental chamber should be set at proper teruperature as defined =in section 5.1. Temperature sensing and recording instrumentation shall be calibrated according to ACP 7.1, Rev. 2. Balances shall be calibrated according to ACP 7.1. Safety procedures should be reviewed in ACP 7.2. 6.1 -Prepare 4 liter of a base solution from the recipe presented in table 1. This will be a base solution for the preparatien of four 1 liter stock solutions. 6.2 The f4u,t stock solution will contain high sulfate and high nitrate: nitrite ratio. Add 208.8 g sodium sulfate, 420.2 g sodium nitrate, and 163.1 g sodium nitrite to.1000 mL of a base solution. The amount of sodina sulfate, sodium nitrate, and sodium nitrite
.( will be added to the stock solution slowly; one component at a time while mixing on a stir plate. The individual component shall be allowed to go into solution before the next component is -added-and -
low heating may be applied to accelerate ene dissolution process.
'After this stock is made_it vill be used to produce cubes 2, 7, 8, 9, 19, 23, and 26 as presented in table 2. T' additional component variations for each cube.will be added on an individual basis. The variation amounts are presented in table 3. and the variable combination sequence for each cube is-presented in table 2.
6.3 The addition of-the chemical components of organics, aluminum,
. phosphate, ard boron will be added to each cube solution based upon 100 mL being generated. These chemicals will be added one at a time while mixing on a stir plate, and each will be allowed to go into solution before the next one is added. At this point, the pH of
_ MIB0900:3RM 7 < l
m _. . __ _ _ __ . - _ _ _. _ _ . _ . - . - _ ..__ _ --_. _
, ., WVNS TP.028A Rev, 1 each cube solution will be measured and adjusted according to 3 -ACM.2601 with 10N sodium hydroxide and the amount recorded on attachment A. The total solid content for each solution will be measured according to ACM-2502. At!this point, adjustments to the total solid cont,ent can_be made if necessary by the addition of demineralized water to the solution or evaporation of water from the solution by heating. The final density measurement will be performed according to ACM 2401, the total solids measurement according to ACM-2502 and recorded on attachment A.
6,4 Once the cube solution has been generated; it should be labeled with the cube number. All the cube solutions in each stock set will be prepared and then'those solutions wil' be made into cement cubes, The water to cement ratio will be calculated based on the equation presented in section 6.26. .The proper amount of simulant will be added to the appropriate amount of cement blend, sodium silicate, and antifoam based upon that cube's variable combination presented in table 2 and the amounted presented in table 3. The cube will-be made according to the procedure started with section 6.8 and the gel time, free volume liquid, pH of liquid, penetration resistance, and compressive strength will be recorded on WV 2301 from ACM-4801.
-6.5 The second stock solution will contain low sulfate.and low nit ste: nitrite ratio, Add 51,0.g sodium sulfate, 74.4 g sodium nitrate, and 163.1 g sodium' nitrite to 1 liter of the base solution. Allow the chemicals to go into the solution as stated in section 6.2. This stock will be used to make cubes 4, 5, 6, 11, 13, 16, and 28 as presented in table 2. The additional component variations for each cube will be added on a individual basis. The variation amounts are presented in table 3 and the variable combination sequence for each cube is presented in table 2. The solutions will be made according the sections 6.2 through 6.3 and the simulate vaste cement prepared according to section 6.4.
MIB0900:3RM 8
\
l
' ' WNS-TP 028A Rev. 1-6,6 The third stock solution will contain low sulfate and high
. p. e G-nitrate: nitrite ratio. Add $1,0 g sodium sulfate, 420.2 g sodium-- nitrate, and 163.1 g sodium nitrite to 1 liter of the base solution.- Allow the chemicals to go into solution as stated in section 6,2,2. This stock will be used to make cubes 3, 10.-15, 18.- 20, 24, and 27 as presented in table 2. The additional component variations for each cube will be added on an individual bv.is. The variation amounts are presented in table 3 and the variabic < combination' sequence for each cube is prer,ented in-table 2. The solutions will be made according to sections 6.2 through 6,3 and simulate vaste cement prepared according to section 6.4. 6.7 The fourth stock solution will contain high sulfate and low nitrateinitrite-ratio, Add 203.8 g sodium sulfate, 74.4 g sodium nitrate, and 163.1 g sodium nicrite to 1 liter of the base solution.' Allow the chemicals to go into solution es stated in section 6.2.2. This stock will be used to make cubes 1, 12, 14, 17, 21,-22, and 25 as presented in table 2. The additional component variations for each cube will be added on an individual basis. The variation amounts are present.ed in table 3 and the variable combination sequence for each cube is presented in table 2. The solutions will be made according to sections 6.2 through 6.3 and simulant waste cement prepared according'to section 6.4. 6.8 Make a 5 percent antifoam solution, Weight 5,00 1 0.05_ g of well ! mixed AF9020 in a 100-mL volumetric 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 plate. 6.9: Prepare 2000 g 2.85 percent calcium nitrate tetra hydrate / cement
-mixture by added in 57.0 g calcium nitrate tatra-hydrate to 1943 g Portland Type I cement in a 5000 mL beaker and mix the dry MIB0900:3RM 9
. , . .- _ . - . - . - . - . _ . - - ~ - .- . . . . . . ._. . - . . . -
7, . VVNS TP 028A
-Rev, 1 z
7 ingredient thoroughly. Also prepare 2000 g-11.4 percent calcium ()_ nitrate tetra. hydrate / cement mixture by' adding 228 g calcium r.itrate tetra-hydrate to 1772 g Portland Type I cement in a 5000 mL beaker and mix the dry ingredient-thoroughly. r 6,10 Use a 500 mL plastic bottle to make a mixing vessel by evenly cutting off the tip and producing an open ended cylinder. 6;11 Similarly cut the top off a 250 mL plastic bottle. This container '
.will be used to add the cement / calcium nitrate mixture to the liquid waste.
6.12 Tare the cutoff 250-mL bottle and add the appropriate amount. cement / calcium nitrcte blend based upon the cuu. sequence variation. Record weight on the appropriate form WV-2301 and attachment A, 6.13 Place the cut empty 500 mL mixing vessel prepared in step 6.3.2 () under impeller and set mixer speed to 1000 rpm. 6.14. Calculate. the amount of simulant necessary to produce the water to cement ratio desired based on the density and total solids information in section 6.3 and the calculation in section 6.26. Dispense.the amount by the use of a grtduated cylinder,
-6.15 Pour the~ appropriate amount of simulant into the 500 mL mixing vessel. Rinse the graduated cylinder af ter each use with nanopure water.
6,16 To-the simulant, use an Eppendorff pipet and transfer 0,09 1 0.006 mL of the 5 percent antifoam mixture from step 6.3.1 for low antifoam variation and 0.6 1 0.003 mL from step 6.3.1 for high antifoam variation work. Record on. form WV-2301 and attachment A. MIB0900:3RM. 10= O
, . - .. .-. - - - . _ . . - .- - - . . - . - . _ - - . . - . . . . - . . . ~ .-
WNS Tp 028A
.- !K Rev. 1-i q( 6.17 Tare a 10'mL disposable plastic cup and add to it approximately
~
.5.5 1 0.5 g sodium silicate for low sodium silicate variation and 22.0 1 0.5 g sodium silicate for hi Sh sodiuin silicate variation.
The exact amount transferred will be found to reweighing the cup after'the material is poured into the sludge wash. Record the weight on_ form W-2301 and attachment /.. 6.18 Support the mixer on a lab stand so that the impeller blade is 1/4 to-1/8 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 4 minutes if doing low mixtime variation and 16 minutes for high mixtime variation. Record on attachment A. 6i19 Begin-the mixing at 1000 rpm and start the timer. Add the dry cement / calcium nitrate mixture to the waste appropriate for your cube preparation presented in table 2 within the first 30 seconds, 6 After 45 seconds, slowly add the sodium silicate within an additional 45 seconds. Continue to mix fer tne appropriate time.
'6.20~ After the transfer ot the sodium silicate, reweigh the cup and calculate- the amount added by differenco. record on form W-2301 and .
attachment A. While mixing, mark a cube mold with a permanent marker with the date,-sample type, numerical identification sequence number, and then weigh the cube mold, record the weight on form W 2301. 6.21 After completion of the mix, stop the mixer and transfer the contents to a plastic 2-inch cube. mold. Fill to the top and transfer the remaining to a.20 mL plastic scintillation vial and seal. After weighing the cube, tare the' scale to zero and reweigh the cube with the cement in it. Record the weight on MIB0900:3RM 11
, , VVNS TP-028A l Rev. 1 j~ Aform WV;2301 - Determine the wet, density of the material by the -l >( formula below.-
Vet Density - Total weight of cube (g)'- tare weight (g) 131 mL Record on form WV-2301. After completing this step, place the cube-in a zip lock plastic bag. t
-6,22. Clean-the impeller with water immediately after pouring.
6.23 Visually check for gulation of the cement in the 20 mL scintillation vial. Check every 5 minutes and do not disturb hetween these time intervals. Record the time it takes the cement to gel. Celacion is-a subjective determination, however gelled cement is indicated when the -20 mL 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.
(' y Bleedwater may be ' present; do not interpret as a sign of unccmpleted
-V' gelation.
6.24 Transfer eb, cube to a drying oven with the temperature set at 79_ i 2 celsius within 2: hours of preparation and allow to cure in the oven for 90 1 8 hours, Record on-formLWV 9301 time, date the cube was made and the1 time it was placed in the oven and also the
-start temperature.
6.25' After 24 hours, determine in milliliters the bleedwater in the scintillation vial and also determine the pH by indicator paper; record it en form WV-2301,
~
_MIB0900:3RM 12 [ %- 1-l i
. . WVNS TP 028A=
Rev. 1
.,_ q 6.26 Calculate the water to cement ratio by weight using formula below, i i L)
R - (A) (B) (1 Cl (D) (1 E) R - Cement to water ratio A - Volume in milliliters of sample B - Density vales in grams / milliliters of sample C - Total Solids value in decimal form D - Weight of cement used in grams E - Percent calcium nitrate in the cement blend in decimal form 6.27 After 90 hours + 8 hours, take the cube out of the oven and do the penetration resistance analysis (sse section 6.3.22) and record the time, date, and temperatute of the cube removal and also the penetration resistance on form WV 2001. 6.28 CAITTION: DO NOT REMOVE Tile CUBE FROM TIIE MOLD IVR Tite PENETRATION [7 TEST AND ONLY Wi!EN READY TO CRUSil.
-6.29 Using the concrete penetrometer mooel CT 421; perform the penetration resistance test by removing the cube from the bag and placing the penetrometer plunger in the center of the exposed side of the cube. Make sure the red indicator ring has been set back to the zero mark on the penetrometer. With a steady vertical force push the penetrometer against the cube until the red indicator ring is all the way down the scale when the penetrometer shaft will not
. penetrate the cement any further, 6.30 On the hendle of the penetrometer,-read the value on the red indicator ring and record the number on form WV-2301. If the red indicator ring is all the way to the end of the scale, a value of
>700 psi shall be recorded.
-~
MIB0900:3RM 13
\.)
., . WVHS TP 028A Rev. 1
,-,- 6,31 When the sample cube is cured for a total of 7 days + 8 hours, ! ) determine the dry density by the formula below.
Dry Density - Total weight of dry cube (g) - tare weight (R) 131 mL Record on form WV-.2301, 6.32 Crush the cube according to ACM 4701.
*/ . O DATA ACQUISITION 7.1 Two-inch cube preparation and compressive strength information wil.
be recorded on form WV-2301, Rev. 1. 7,2 The cube sequence variations presented in table 2 will be recorded on attachment A. 7.3 Simulant preparation will be performed in accordance with ACP 7.1.
! L
-N . 7.4 A brief test summary and records transfer to the MRC, documenting results of the testing shall be issued by the co6nizant A&PC scientist per EP 11-003. g-~ MIB0900:3RM 14 6
- g. .- . _ . __ _ . . _ _ _ _ _ . _ . . _
, ., WNS TP 028A Rev. 1
-TABLE 1: BASE SOLUTION
, Corstituent Formula ~ Grams / Liter Potassium Nitrate KNO3- 10.73~
-Sodium Carbonate Na200 3 29.03 ,
Sodium Chromate -Tetra hydrate s Na2C rof*4H 2O 2.610 Sodium Chloride Nacl 1.730 7 Sodium Tetraborate, Decahydrate Na2 4B 0 10H 2O 0,161 Water HO 2 1000,00 Srams fi
'\J a .-
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1 + - - ' - - + - - + + + - - + + - + + - + + - - - + + + - 1 N G I S 0 1 - - + - + - - + - + - + + + - + r - + + - - - - + + + - E D G N I N E E 9 - - - + + + + - + + - - + - - - + - + - + + - + - + + - R C S N A M 8 - - - + + + - + + - - + - - + + - - - + + - + + + + - - R U B r
- e T b T m E u K N 7 - - - + + + + + - - + - - + - - - + + + - + + - + - + -
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i i r R m a o 6 + + + + - + - - - + - - - + - + - - + - + - + + + - + - d V T n H a G r I E e Y b T l 5 + + + - + + - - - - - + - - - - - + - + + + + - - + + - N l E a W h T s r 2 e 4+++++ - - - - . + - - - + - + - + + - + - + + + - - d E' r L o B e A h T t
, 3 + - + - - - + + + - + - + - - + - - - + + + - + + - + -
s t s e t g 2 - + + - - - + + + + - - - - + - - + + + - - + + - + + - i n n n u r e 1 + + - - - - + + + - - + - + - - + - + - + + + - + + - - r o M f R e 3 B : 0 0
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t o i a123456789012345678901 2345678 r 1 11 11 11 11 1 222222222 B I N T M
1 W N$ TP 028A Rev. 1 TABLE 3: VARIABLE CUBE PARA'tETERS Pactors lity.h (4) Low ( . ) Nominal Chemical j{irlable Cv.mponents per 100 mL - Phosphate (g PO 4 /g Cl*) 1.09 g 0.0015 g 0.08 g (Sodium Phosphate, Dibasic) Boron (g B/g Cl*) 0.134 g 0.0009 g 0.0018 g (Sodium Tetraborate. Decahydrate) Aluninwa (g A1/g C1,) 4.05 g 0.00 g 0.00 g (Aluminwa Nitrate *9H 2O) Organics Citric Acid, Menohydrate 0.096 g 0.012 g 0.024 g Oxalic Acid, Dihydrate 0.095 g 0.012 g 0.024 g D* Tartaric Acid 0.095 g 0.012 g 0.024 g pH . 13.0 11.9 12.0 (10N Sodium Hydroxide) Physical Variable 1omponents Total Solida (t) 37 25 33 Water to Cement Ratio 0.8 0.3 0.61 Hixtime (mins) 16.0 4.0 8.0 Cement kecipe Enhancers Coiponent_a Percent Calciwn Nitrate 11.4 2.85 5.7 Antifoam (mL) 0.6 0.09 0.3 Sodiwa Silicate (,;) - 22.0 5.5 11.0 a MIB0900:3RM 17 O/ 1
i i ,
, WNS.TP 028A l Rev. 1 !
i I q ATTACHMENT A MULTI VARIENT CUBE WORKSHEET I Date: Laboratory ID: Cube No.: Stock Solution: _ Component Variance (+/-) Amount chemicg Compoyent Variables
- 1. Phosphate ( ) x l (Sodiurn Phosphate. Honobasic)
- 2. Boron ( ) x (Sodium Tetraborate Dwahydrate)
- 3. Aluminum ( ) _
r, I (Aluminum Nitrate *9 H 2O) i
- 4. Citric Acid, Monohydrate ( ) K
- 5. Oxalic Acto, Dihydrate ( ) g !
t 64 D Tartaric Acid ( ) r. ;
- 7. pH. ( ) S.U. !
Amount- of 10 N Sodiurs Hydroxide Added mL Physica1Jeroponent Variables
- 8. Total Solids. (- ) t
=9. Water to Cement ratio ( )
10, Mixtime . ( ) , mins Cement Recipe Enhancers 11, Calcium Nitrate ( ) _t
- 12. 5 Percent Antifoam Solution ( ) mL
- 13. -Sodium Silicate ( ) , n Analyst: __ Date: ,
Approved: Date: l .- MIB0900:3RM A-1
-., ,a.. . . . - . . . . . , - .. . . . - , . . - . _
, -=. .- . .
e Doc. Numter WVNS-TP-028B West Valley
~~
,,,, ,, ,, s i, ,
U Demonstration Project nevi ion Date 09"w 91 Engineering Release #2,91 TEST PROCEDURE WATER TO CEMENT RATIO VARI ANCE IN SIMULATED SLUDGE WASH
! I PREPARED BY cs . L - / tdti) L. E. Mi chni k Cogni zant En(taw #~ _ , _
APPh0VED BY D. C. Meess Cognizant System Design Manager APPROVED BY b' 1/,,1 J . C . Cw yn ar/ Cognizant System t,anager P. J. Valenti ( APPROVED BY [ D. J. Fauth Latr 4I ories Maaager , y -1
,1 l'; #'
APPROVED BY '/ ~0;3 / T[^< - [D. L. Shugars Quality A{strance Manager APPROVED BY ,, /
~
o P.abIhtion VfaTety Ranagerf D. J. Harward j West Valley Nuclear Services Co., Inc. P.O. Box 191 RL A0510 :3RM V est Valley, NY 14171-0191 i r~T l l h WV.1816. Rev 1
I i WNS TP 028B Rev. O RECORD OF REVISION {ROCEDl'RE If there are chan6es 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 ch4nge. l l
l l Revision On Rev. No. Description of Changes Page(s) Dated 0 Original Issue All 09/20/91 : b a W 1807,~ Rev 1 t-RiA0510; 3RM
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WNS.TP 0288 l 4 Rev. O I RECORD OF REVISION (CONTINUATION SHEE. Rev, No. Description of Changes 'ffg,{s)0" Dated ; t k 4 t 1 5 W.1807, Rev 1 gg RIA0510 : 3RM - i t
VVNS.TP 028B f~) VATER TO CEMENT RATIO VARIANCE IN SIMUIATED SLUDGE VASH 1 l REV. 0 1.0 SCOPE 1.1 This test procedure is being written to complete the request l initiated under WNS TRQ 0P '" VVNS TPL 70 011. The objective of this overall is tic', - ri, i s to better defire the effects of watet e erop ' h an the simulated sludge wash cement's gel time, uts. water, penstration restSr.ance and compressive stren5th i According to results obtained from VVNS TP 028A and the e~ Plackett Burman screening matrix used in this test procedure (,,j) f the only observed effect on the cement waste form was deterait ni to be water to cement ratio variance. 1.2 The work will include 18 2 inch square cubes with water to cement ratios from 0.45 to 0.80 at 0.05 increments however at 0.65, 4 cubes will be made at this increment. After an appropriate curing period, per section 5.0, the 2 inch square cubes will E subjected to compressive strength testing per section 6.2.1. 1.3 The compressive strength, bleedwater, pH of the bleed water, and pet,etration resistance will be measured and recorded for each cube as part of ACM 4801.
'[h
%Y RLA0510:3RM 1-i
. . . _ . _ . . _ . _ . . ~ . _ . _ - , _ ~_ . - _ . . _ . . .
- WVNS.TP 0288 Rev. 0 2.0 DEFINITIONS AND ABBREVIATIONS r
( 2.1 Definjitons l l 2.1.1 Cement . Dry Portland Type I cement in accordance l l with ASIM Standard C 150 85, 2.1.2- Antifoam . General Electric AF90290 emulsion of 5 percent dimethlysilicone in nanopure water. This. is used as a cement recipe enhancer to prevent air entrapment in the cement matrix during high speed mixing. 2.1.3 Sodium Silicate is used as a recipe enhancer in the gelling of the cement waste form and prevention of excess bleed water. 2.1.4 Calcium nitrate tetra. hydrate is used as a recipe g-'s enhancer in the setting of the cemene waste form. 2.1.5 Cube . 2x2x2 inch mold used to make laboratory specimens. 2.2 Abbreviations ACM Analytical Chemistry Method ASTM American Society for Testing and Materials l' 3.0 QUALITY ASSURANCE 3.1 Analytical and Process Chemistry (A&PC) will be responsible for the preparation and testing of the laboratory specimens in secordance with this test procedure and the applicable RIA0510: 3RM O
- WNS TP+0288 l Rov. 0 '
steps in the appropriate Analytical and Chemistry Methods (ACM). A&PC shall verbally notify the cognizant Quality Engineer and Quality Manager 24 hours prior to commencement l of work. 3.2 Quality Assurance will perform surveillance as required. 3.3 A&PC shall maintain control by labeling all containers used ; in testing. A bound laboratory notebook will be used to record solution contents and testing observation. 4.0 TOOLS. EQUIPMENT _ COMPONENTS, AND__ REFERENCES 4.1 Tools and Equipment Ligntnin Lab Mix 3r, Model No TS 1515 with high shear impeller or equivalent 2x2x2 inch plastic American Cube Molds ' 100 milliliter (mL) plastic or glass graduated cylinder with 1 mL divisions
'500 mL polypropylene plastic bottles Corning hot plate or wquivalent 100 mL glass volumetric flask 20 mL plastic scintillation viala magnetic stirring plate with ma5netic stir bar stopwatch or timer accurate to 1 second top loading balance readable to +/ 0.01 grams (g)
+ Blue M Oven Model No. C 2630-Q Gilson Penetrometer Model No. CT 421
- fine sand or emery paper t
RIA0510: 3RM , _
WNS TP.0288 Rev. 0 4.2 Reagents ( A Portland Type I cement
. Calcium Nitrate tetra. hydrate, reagent grade
. Citric Acid Honohydrate, reagent grade
. Oxalic Acid Dihydrate, reagent grade !
- d. Tartaric Acid, reagent grade
. Socium Silicate, 38 weight percent in water basi, technical grade '
. Antifoam General Electric AF9020*
. Sodium Phosphate Monohydrate, reagent grade '
. Sodium tetraborate Decahydrate, reagent grade
. Sedium Nitrate, reagent grade
. Sodium Nitrite, reagent grade
. Soditun Carbonate, reagent grade '
Potassium Nitrate, reagent grade
. Sodium Hydroxide, reagent grade
. Soditus Chromate, tetra. hydrate, reagent grade
. Sodiuni Chloride, reagent grade
. Sodium Molybdate Dihydrate, reagent grade nanopure or ASTM Type I water supplied by IRTS operations 4.3 References
. NRC Technical Position on Vaste Form (Revision 1),
January, 1991 ASTM C 150 8%." Specification for Portland Cement" i
. ASTM C.109 86 " Compressive Strength of Hydraulic Cement and Mortors (Using 2*in or 50 mm Cube-Specimens)"
. WNS.TPL 7011 " Test Plan of the Waste form Qaalification Program for Cencnt Solidification of the Sludge Wash liquid" h
u RIA0510: 3RM 4
z
- i l
' WNS TP 0288 I Rev. O !
. WNS.TRQ 028 " Test Request for Devolopment of the Process Control Parameters for Cement Solidification of Sludge
-( Vash Liqalds" v-WNS TP 025 " Procedure for Development of the Nominal Recipe for Cement Solidification of Sludge Wash Liquids" WNS TP 028A " Procedure for Development of Process control Parameters for Cement Solidification of Sludge Wash Liquids"
" Cement Vaste Form Process Control Parameters Screening Test Results" Letter NO. CJ:91:0078 To P.J. Valenti, from ;
~
John Mahoney, August 12, 1991. ACH 4701 " Destructive Test of 2 inch Cement Cubes" l ACM 4801 " Cement Test Cube Preparation Method" ACM 2401 " Density" ACM 2502 " Total Solids" (Microwave) ACM 2601 "pH" (Electrode) 5.0 CENERAL INFORMATION Test Procedure WNS TP 02iA Revision 1 was used to evaluate the effects of 13 variables in the cement waste form production throug,h the use of the Plackett Burman Screening test. The one variable that showed any significant effect on the compressive strength of the cement and secondary effects of excessive bleedwater and get time was water to cement ratio. This effect was clearly shown to have an almost linear correlation between water / cement and compressive strength and was also demonstrated in WNS-TP 025 in the total solids variance and water to cement ratio. This effect will be more clearly defined in this test procedure by the use of a single variance analysis of water to cement ratio over a smaller defined window with the evaluation of a large set of data points. The water to cement ratio will be evaluated from 0.45 to 0.8 at increments of 0.05 and a total of RIA0510: 3RM 5
l VVHS.TP 0288 Rov. 0 18 cubes will be made based on duplicate cubes being produced at each increment level. The cubes will be cured at 79' +/ 2"C for () 90 +/. 8 hours and the remaining time period for a total of 7 days of curing will be a ambient temperature. At this point in time the compressive strength value for each cube will be evaluated according to ACH 4101. 6.0 PROCEDtfRE 6.1 Prerequisite
. Oven shall be set at a proper t.mperature as defined in section 5.0.' Temperature sensing and recording instrumentation shall be calibrated according to ACP 7.1, Rev. 2.
l Balances shall be calibrated according to ACP 7.1 Safety procedures shall be reviewed in ACP 7.2 6.2 A nominal recipe simulant shall be prepared (see attachment A) and 2 cubes shall be made starting with a water to cement ratio of 0.45 and continuing to 0.80 in incremor.t of 0.05. The first nine cubes-should be made according to section 6.3 thru 6.3.25 within an 8 hour period and the cubes shall be placed in the oven within 1 hours of preparation. The last nine cubes should be made according to section 6.3 thru 6.3.25 within a 8 hour period and the cubes placed in the oven within 1 hours of preparstion. 6.2.1 After curing, per section 5.0, the cubes will be subjected to compressive strength testing according to ACM 4701 with the exception that in section 10.1.3, two opposite facos shall be ground with fine emery paper to the tolerances stated in section 9.6.2 of ASTM C 109. f d RIA0510: 3RM ,
..- - = -- . -- . - - - , . --. .. -
WNS.TP 0288 Rov. 0 O 6.2.2 All compressive strength results, gel time, ! penetration resistance and bleedwater will be recorded on W.2301 6.3 Make a five (54) percent antifoam solution. Weigh 5.00
+/ 0.05 g of well mixed AF9020 in a 100 mL volumetric 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 plate. 6.3.1 Prepare 3000 g 5.7 percent calcium nitrate tetra. hydrate / cement mixture by adding 171 g calcium nitrate tetrahydrate to 2829.5 g Portland Type I cement in a 5000 mL beaker and mix the dry ingredient thoroughly. 6.3.2 Use a five.hundred (500 mL) plastic bottle to make a p mixing vessel by evenly cutting off the tip and b producing an open ended cylinder. 6.3.3 Similarly cut the 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 waste. 6.3.4 Tare the cutoff two hundred fifty (250 mL) bottle and add 140.5 +/ 1 cement / calcium nitrate. Record weight on the appropriate Form W.2301, 6.3.5 Place the cut empty five hundred (500 mt.) mixing vessel prepared in step 6.3.1 under impeller and set mixer speed to one thousand rpm. RIA0510:3RM -
VVNS TP 0288 Rov. 0 6.3.6 Measure appropriate amounc of 29 33 weight percent (T
*,/ simulant based on the water to cement ratio and using equation in section 6.3.18 using a 100 mL graduated cylinder and record this amount on Form VV 2301.
6.3.7 pour the simulant into the 500 mL mixing vessel prepared according to attachment A. Rinse the graduated cylinder after each use with nanopure water. 6.3.8 To the sludge wash, use an Eppendorff pipet and transfer 0.3 +/ 0.006 mL of the 5 percent antifoam mixture from step 6.3.1. Record the volume on Form VV 2301. 6.3.9 Tare a 10 mL disposable plastic cup and add to it approximately 11.00 +/ 0.5 g sodium silicate. The exact amount transferred will ba found by re weighing es g the cup after the material is poured into the sludge (__,/ wash. Record the weight on Form VV 2301 6.3.10 Support the mixer on a lab stand so that the impeller blade is one quarter to one eighth. 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 timer for 8 minutes. 6.3.11 Begin the mixing at 1000 rpm and start the timer. Add the dry cement / calcium nitrate mixture to the waste within the first 30 seconds. After 45 seconds, slowly add the sodium silicate within an additional 45 seconds . Continue to mix for a total mix time of 8 minutes, f RLA0510:3RM 8-
, . - . -- , ,, , , _ , n -
-. .-- . - _- - -. . __. ~ - .-_ .
- WNS TP 0288 Rev. 0 6.3.12 After the transfer of the sodium silicate re weigh the cup and calculate the amount added by difference, k
record the weight on Form W 2301. While mixing, mark on a cube sold with a permanent marker with the date, sample type, numerical identification sequence number and then weigh the cube mold, record this weight on Form W 2301, 6.Y.13 Af ter completion of the 8 minute mix, stop the mixer and transfer the contents to e plastic 2 inch cube mold. Fill to the top and transfer the remaining to a 20 mL plastic scintillation vial and seal. After weighing the cube, tare the scale to zero and re-weigh the cube with the cement in it. Record the weight on Form W 2301. Determine the wet density of the material by the formula below. Vet Density - Total weight of cube (g) - Tare weight of cube (a) 131 mLs V Record the wet density on Form W 2301. After completing this step, place the cube in a zip lock plastic bag. 6.3.14 Clean the impeller with water immediately after pouring. 6.3.15 Visually check for gelation of the cement in the 20 mL scintillation vial. Check every 5 minutes and do not disturb between these time intervals. Record the time it take the cement to gel. Celation is a subjective determination, however gelled cement can be determined when the 20 mL scintillation vial can ( RIA0510: 3RM 9-
4 WNS TP 028B Ray. 0 be tipped slowly to a 90 degree position, parallel to r~s the horizon. The cement should not deform, flow, and V) will retain a line of form perpendicular to the horizon. Bleedwater may be present, do not interpret this as a sign of uncompleted gelation. 6.3.16 Transfer the cube to a drying oven with the temperature set at 79 +/ 2 celsius within 2 hours of preparation and allow to cure in the oven for 90 +/ 8 hours. Record on Form W 2301 the time, date the cube was made and the time it was placed in the oven and also the start tem: rature. , 6.3.17 After 24 hours, determine in mLs the bleedwater in the scintillation vial and also determine the pH by indicator paper (if bleedwater is present); record both on Form W 2301. 6.3.18 Calculate the water to cement ratio by weight usirg b Q formula below. Vater to cement - (A)(B)(1 C) (D)(0.943) A - Volume in mLs of sample B = Density value in g/mL of sample C - Total Solids value in decimal form D - Weight of cement used in gretss 6.3.19 After 90 +/ 8 hours, take the cube out of the oven and do the penetration resistance analysis (see section 6.3.22) and record the time, date and temperature of the cube removal and also the penetration resistance on Form W-2301.
'RLA0510:3RM - . - . - .
UVNS*TP.0288 Rov. 0 6.3.20 CAUTION: Do not remove the cube from the sold for tT the penetration test. Remove it only when ready to kl crush. 6.3.21 Using the concrete penetrometer model CT 421, perform the penetration resistance test by removing the cube from the bag and placing the penetrometer plunger in the center of the exposed side of the cube. Make sure the red indicator ring has been set back to the zero mark on the penetrometer. With a steady vertical force push the penetrometer against the cube until the red indicator ring is all the way dovn the scale when the penetrometer shaft will not penetrate the cement any further, 6.3.22 On the handle of the penetrometer, read the value on the red indicator ring and record the number on Form VV 2301. If the red indicator ring is all the way to the end of the scale, a value of >700 psi (,) 7- s shall be recorded. 6.3.23 When the sample cube is cured for a total of 7 days
+/ 8 hours Determine the dry density by the formula below Dry Density - Total weight of Dry cube (R) tare weir.ht (R) 131 mLs Record on the dry density form WV 2301 6.3.24 Crush the cube according to ACM 4701.
,n
{ RLAC310:3RM 11 - 'G
4 VVNS TP 028B Rsv. 0 7.0 DATA ACQUISITION O' 7.1 Two inch cube preparation and compressive strength information vill be recorded on Form VV 2301, Rev 1. 7.2 Simulant preparation vill be nerformed in accordance with ACP 8.1 and recorded in Laboratory Notebook 7.3 A test summary report VVNS TSR 028, documenting the results of this test procedure vill be issued by the cognizant engineer and reviewed by the cognizant A6PC scientist. ! r (;;') RLA0510:3RM - 12 - l -; l
.- - , . . . . . . - . ~ , . . . , , . . . . . . . . , _ .c _~ . , m _. .. . . ,,. _ , . . . ... . . . _- -. .,..-_._ ,_ . . - -
8 VVHS.TP.028B Rov. 0 ATTACHMENT A
;v r
SIMUIANT RECIPE BASED ON 128.5. INCH HEEL Const}tuent Formula d Sodium Nitrate NANO 3 171.5 Sodium Nitrite NANO 2 103*1 Sodium Sulfate 101.9 Na2504 Sodium Nitrate KNO 3 10.73 Sodium Carbonate 29.02 Na2CO 3 Sodium Hydroxide NaOH 6.24* Sodium Chromate Tetrahydrate Na2C r04 4HO 2.60 2 Sodium Phosphate Monobasic 1.25 NaH2 PO4 1HO 2 Sodium Chloride Nacl 1.73 Sodtum Molybdate Dihydrate Na2M04 2HO 0.300 2 Sodiurs Borate Decahydrste B Na2f07 10 H 2O 0.161
- q. Citric Acid Monohydrate CH0 624 1HO 2 0.240 Oxalic Acid Dihydrate CH0 224 2HO 0.238 2
D Tartaric Acid CH0 466 0.238 Vater- HO 1000g 2 Veight of Solids 474.8g Weir,ht Percent of Solids 32.834
*The Sodium Hydroxide (NaOH) value is approximate, this chemical should be edded last and only 'in the amount to adjust the pH of the solution to 12 +/ 0.2 SU. . V l RiA0510:3RM 13 -
L ,
_ _ . .- - -... - -.-. - . -.-.. _. - _.... .-- - .- .~ - - . - - _ 9 e l kEST VALLEY NUCLEA?. SEAVICES COMPANY DOCUMENT RELEASE FORM Docwnent No.: kV S TSR 028
Title:
SLUDC(VASH CEMENT VASTE FORM OUAL _ MELOP. OF PROCESS CONTROL PARAMETESQ ) Revision: 0
-Date: 02/06/92 Special Instructions:
Distribution: Controlled Cooles Rectoient Egeleient O Uncontrolled Cooies Reeioient;- Eqsiniggg MRC MS 50B J . L. MAHONEY MS M L. E. MICHNIX MS $6 , A.-J. HOWEL MS-W R. J. LNANDOWSKI MS-B D. C. MEESS MS-W P J. VALENTI MS W R. A. PAIMER MS 56 W. J. DALTON MS B1F
- QUALITY SERVICES MS-L M. N. BAKER MS W '
.MAKE ANY ADDITIONS OR DELETIONS TO THE DISTRIBUTION LIST AND RETURN COMPLETE PACKA'IE TO DOCUMENT CONTROL - DIANA SMITHMEYER FOR DISTRIBUTION, I
I.
\
WV 1008, Rev. 2 DLSO491.R3
UVNS.TSR.M8 ' e TEST
SUMMARY
REPORT Rev. O TEST / TEST SERIES Sludre Wash Cement Vaste Form Oualification DESCRIPTION Development of Process Control Parameters TEST REQUEST NO. VVNS.TRO 026 TEST PLAN NO VVNS.TP.026 TEST COMMENCEMENT DATE 2/,lsl.o, L TEST COMPLETION DATE 7/31/91 Engineering Release f2271, Date 02/06/92 1.0 OBSERVATIONS / COMMENTS 9 n e purpose of this test procedure was to perform qualification work on cement vaste forms simulating the cement waste to be generated following sludge washing. The test procedure was divided into parts A and B. Part A, which has been completed, served as a screening test of variables that could effect gel time, bleed water, and /. day cured compressive strength of 2" x 2" x 2" cubes prepared in the laboratory. Procedure part B would have tested the variables identified in part A under a closer multi variant lay out. Due to the immersion .tength ' failure of the nominal cement recipe, part B of this test series was canceled.
2.0 REFERENCES
1)- UVNS.TRQ.028 Revision 1 " Test Request for Development of the O
-V Process Control Parameters for Cement Solidification of Sludge Vash Liquids", 7 1 91, J . L. Mahoney
- 2) WVNS.TP 028A Revision 1. " Procedure for Development of Process Control Parameters.for Cement Solidification of Sludge Wash Liquids", 7 16 91, L. E. Michnik
- 3) Letter _FH;91:0104, L. E. Michnik to J. L. Mahoney, " Compressive Strength Results from Multi dariant Simulated Sludge Wash Coment",
dated August 2, 1991 *
- 4) Letter nl:91:0105, L. E. Michnik to J. L. Mahoney, "Results from Multi. Variant Simulated Sludge Wash Cement", dated August 5, 1991
- 5) Letter FH:91:0120, L, E. Michnik to J. L. Mahoney, " Initial Test Summary Report on UVNS.TRQ.028 Rev. 1" dated October 8, 1991 .
- 6) Letter CJ:91:0078, J. L. Mahoney to P. J. Valenti. ." Cement Waste Forr Process Control Parameters Screening Test Results", dated Octt..er 8, 1991
- 7) United States Nuclear Regulatory Commission " Technical Position on Waste Form" Revision 1, January, 1991.
l
3.0 CONCLUSION
S / ACCEPTABILITY OF RESULTS/0BJECTIVES MET The acceptability of the objectives from VVNS.TRQ.028 are presented below, h
-DLSO491.R3' 1 u _ ._ _ _-_-.__ _ . _ _ _ _ _
. . - . - . . . _ , ~ . - - . . - - _ - - . - - . - - _ _ . - - . - - - _ _ _ . - -
e e VVHS.TSR 028 Rev. 0 3.1 igy,ggnjg,,,,Itsts of 13 Variables (obiective ?.1) ; 6111111% Perform a Plackett Burm. screening test of 13 possible variables that may affect the cure time, presence of bleed water, penetration resistance, and 7 day cured compressive strength of 2" x 2" x 2' cubes prepared with simulants in the laboratory. Task Accomolished This task was completed. Twenty eight 2" cubes were prepared por TP.028A, yieldin6 compressive strengths, gel times, penetration resistances, and bleed water volumes. A full vrite up of the , results of the screening test can be found in reference 6 listed under Section 2. The hoy statistical conclusion is that only the water to coment ratio was foe.nd to be important in affecting both the gel time and the cured compressive strength. No variation was seen in penetration resistance for the range of variables tested. Bleed water was present on only 3 cubes which were all at both high water.co.coment ratios and high phosphate levela. 3.2 Multi Variant Testine of Mey Variables (obiective 2.2) Activity Key variables identified under the screenin5 test will be retested under a. Box Behnken multi variant test program. The tests will evaluate full interaction of the identified key variables. Task Accomolished-As noted in Section 1, this portion of the test request will not be performed. Results from other test requests on the nc.rinal cement recipe, have shown a failure in immersion strength. 4.0 ACTIONS OUTSTANDING No activities remain to be completed as part of this test request series. APPROVAL (3) wA ADDITIONAL REVIEVERS NO
/J! L.- M'ahcmp(Y WS SW N L. E. Ktetntik 00$dY A .' . Howe 11 o 'b)$cb.,De d /
ea11 , ss _ . .. c. ...s. DLSO491.R3 , _ , . _ _ _ _ _ . _ , _ . . , , _ . . . _ _ _ , - . . _ , _ _ . _ _ . _ . _ _ _ . _ _ _ _
. i n(/ West Valley Doc Nuaber WNS TRQ.029 Demonstration Project Revision unuser i Revision Date 09-05-91 Engineering Rele.se #2053 ECN 2 522 7EST REQUEST PRODUCTION OF CEMENT PRODUCT FROM ACTUAL SLUDCE WASH LIQUID PREPARED BY ilf [t <> M h ~' C. A. Smith Cognizant Englefeye /
/
APPROVED BY " 3 27-91 D. C. Meess Cognizant System Design Manager 1 i p ] ll APPROVED BY s' 4172 /' WMfIt'd - L. Shugars QualityAspranceManager AP Y 4. > Nf[f/1D. J. Harvard Radiation &".HIfety Managf r ' F APPROVED BY k .b - 3 [18/ 9 i J. C. Cvynar Prikess Control Engineering West Valley Nuclear Services Co., Inc. P.O. Box 191
/' j West Valley, NY 14171-0191 (d B 005 W /
WV 1818, Rev.1
l WNS TRQ.029 1 Rev 1 i RECORD 05' 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 tlin 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 1 Per ECN 4522 All 09 05 91 O
,- W 1807, Rev. 1 i BELOO51:3RM
')
WNS TRQ 029
, Rev. 1 RECORD OF REVISION (CONTINUATION SHEET)
Rev. No'- Description of Changes Rep j j n on O 1
- W-1807, Rev. 1 11 BELOO51:3RM ;
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- '**'-8 we~v-r*.--,-.,- ,_y,,, , ,, , **8 "*a-ews,.,s_,, g_ ,
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t r% VVNS-TRQ.029 _s Rev. 1 l PRODUCTION OF CEMENT PRODUCT FROM ACTUAL SLUDGE VASH LIQUID
1.0 INTRODUCTION
> -1.1 This work is required to approximate the full scale sludge wash process that is being developed at the West Valley Demonstration Proj ect (VVDP), on a lab scale. Confirmatory cubes will be made using actual sludge wash solution produced in lab scale tests to determins a :.aracy or validity of similar tests to be used in the qualificacith program, per reference 7.1. This work is within the scope of VVNS TPL 70 11, section 4.6. All work contained in this document will be completed in the VVNS 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 I VVNS TRQ 028. Also, a decision will be made by the A & PC lab as to the accuracy of the simulant specified in VVNS-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. 1.2 All work will be performed with an actual high level waste tank (SD.2) sludge sample. (Reference 7.'j)
> 1.3 Testing shall be conducted in accordance with a test procedure.
VVNS TP 029A, issued by the A & PC Lab. 2.0 OBJECTIVE
> NOTE: All weights are approximate. Actual weights should be 101 grams of given weights, and be recorded per VVNS TP 029A.
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. Arplyze supernatant 1 t , constituents given in section 2.4 70 grams of lab demin water and 5.8* gramc of caustic soda (premixed before being added to mining se=rol) s BELOO51:3RM 1
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1 VVNS TRQ.029 Rev. 1 4 For the second, third, and fourth wash, add: 233 grams o!! lab domin eater and 0.45* grams of caustic soda (premixed before being added to mixing vessel) 2.1.1 Demin v. iter should be analyzed for Na, Ng, Ca, S04 , and K 2.2 Each wash will be 1 day in length and vessel agitation will approximate actual washing procedure. After agitation, the liquid will be allowed to settle for 24 hours. Vessel temperature will be , approximate 70*C for agitation. , 2.3 After each of the four washes are complete, the resulting wash liquid shall be decanted off the top of the sludge accordind to VVNS.TP 029 in the following approximate amounts. (Actual weights of decanted solutions shall be determined in VVNS TP 029, and
.ecorded for each wash.)
Wash 1: 298 grams of solution Wash 2: 268 grams of solution Wash 3: 262 grans-of solution Wash 4: 261 grams of solution A & PC personnel to note:
- 1. Speed of solids settling O 2. Approximate height of mixture and that of settled solids
- 3. Approximate height after wash solution removed 2.4 The liquid from all four washes will be analyzed for the following:
NO 2 K PO 4 Ti NO 3 Na SO 4 Ca i BO pH Cr0 4 C1 Al U Tc-99 Cs-137 Sr-90 Alpha Pu Gross Alpha Gross Beta Specific Gravity Total Dissolved Solids (TDS) Total Suspended Solids (TSS)
> 2.5 The wash-liquid from washes 2, 3, and 4 will be . stored in sealed containers separately at the A&PC lab for future testing. Label "VVNSatP 029A Vash * .
- Caustic Soda weights given are approximate. Actual weights will be determined by Titrating and will be incorporated into VVNS TP 029.
BELOO51:3RM 2
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4 WNS TRQ 029 , Rev. 1 O > 2.6 The decant liquid frors wash 1 shall be processed through lab ion exchange columns containing zeolite at a rate of between .8 and 1.1 Column Volumes pet Hour (CV/H). The configuration of these columns will be deterrined and is to be specified in WNS TP 029A. The ability to sample between columns is needed. These samples will be taken at the discretion of the cognizant A&PC scientist per WNS TP 029. The samples will be analyzed for Cs.13) and Alpha Plutonium decontamination factor (DF). This informaticn will also be needed to calculate Cs-137 ano Pu percent breakthrough,
> 2.7 Once a preset breakthrough point for Cs 137 is reached, the lead column will'be taken off line. All further column changing and preparation will be specified in WNS TP 029A.
2.8 Step 2.7 vill be repeated as often as necessary an determined by Cs-137 breakthrough, to process total wash al volume. 2.9 Once all of ths liquid has been processed through the columns, the liquid will be analyzed for all constituents listed in step 2.4 2.10 The resultant " decontaminated" sludge wash solution will be slowly evaporatedtoanominal33jweightpercentTotalDissolvedSolids (TDS). (Per reference 7.4) The evaporation will take place in a glass container with a bottom heating unit. At this point lab O personnel should note any unusual occurrences that may occur during boiling. e.g. precipitation, scaling on surfaces, etc. 2.11 The resultant " concentrates" will be analyzed per section 2.4. This work can be done in parallel with steps 2.11 through 2.14 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, WNS TP 026, and applicable steps of AGM-4801.
> 2.13 The remaining solution will be stored in sealed containers for possible future analysis, l.abel "WNS TP 029A, Wash # ,
Concentrates". , 2.14 A&PC will perform destructive tests on the cube per ACM 4701. 2.15 All data will be reviewed and approved by a qualified A & PC scientist or A & PC lab technician, 3.0 SAFETY 3.1 Industrial hygiene practices will be as oescribed in the WNS Hygiene and Safety Manual, WDP 011. 3.2 Radiological work will be performed in accordance with the WDP Radiological Controls Manual, WDP-010. BELOO51:3RM 3
1
)
- VVNS.TRQ.079 Rev. 1 '
1 3.3 Vork in the Analytical & Process Chemistry Lab will be performed in iO accordance with existing A&PC methods (ACM's). 4.0 EQUIPMENT CONFIGURATION !
.> 4,1 All lab equipment will be set up as directed in WNS TP 029A.
5.0 SAMPLING FREQUENCY
> 5.1 Additional samples will be obtained in the quantities and frequencies specified by the cognizant A&PC scientist and will be specified in VVNS TP 029A.
6.0 PERSONNEL QUALIFICATION 6.1 Testing will be performed by qualified Analytical & Procesa Chemistry Technicians using Analytical & Chemistry Methods (ACM's) under the cognizance of an A6PC scientist. 6.2 Surveillance activity will be performed by qualified Quality Assurance personnel. ,
7.0 REFERENCES
7.1 " Technical Position on Waste Form", Revision 1, dated December 1990. ( 7.2 "Prelimir.ary Flowsheet Sludge Wash with Existing 80 2 lleel", EK:91:0047, J. L. Mahoney, dated 03/07/91. 7.3 Work performed with SOP 8-20, "8D-2 Sludge Sampling". Composited in the A & PC Lab on January 10, 1990. 7.4 " Removal of Plutonium from West Valley High Level Liquid Wasre", Bray, Hara -Kazmierezak, dated January 199L BELOO51:3RM 4
West Valley Doc. nueer wvns-TP-o29 A-O Demonstration Project Revision nue er o Revision Date 04/18/91 Engineering Releare #2065 S TEST PROCEDURE PROCEDURE FOR CONFIRMATORY CUBE -d G PREPARED BY M. k. , /, o h L.E. Michnik Cognizant Engineer APPROVED BY f_f M &cg.f D.C. Meess
. G Cognizant Sp tes Design Manager 9 _
APFROVED BY
~
/w/w 177 '
/ D.L. Shugars Quality Assurance Manager'
,. APPROVED BY 'dbed M l D.J. Harward Q ation and satety hanager APPROVED P3 k ' b ' b-%, h17 /9l J.C. Cwynar Ptpcess Control Eagineering West Valley Nuclear Services CO., Inc.
P.O. Box 191 West Valley, NY 14171-0191 wv.4Sbi.V;2,
..--,..y.. , . . . _ - . . .
c' WVNS-TP-029A Rev. 0 RECORD OF REVISION 4 PROCEDURE If there are any changes to the procedure,-the rie ision num' w increases by one. These changes are indicated in the left na r pn. of the body by an arrow (>) at the beginning of the paragrape , that contains a change. Example:
> The arrow in the margin indicates a change.
Revision On Rev. No. Description of Changes Page(s) Dated 0 Criginal Issue- All 04/18/91 O F PSK:TP-029A i ,
WVHS-TP-029A
-Rev. O O \_)
RECORD OF REVISION (CONTINUATION SHEET) Revision on Rev. No. Description-of Changes Page(s) -Dated-O rO.
- ()
PSK:TP-029A
.. 11
4 em WVNS-TP-029A
) Rev. O Test Procedure kor Confirmatory Cube 1.0 SCOPE 1.1 This procedure is for the preparation of a 2x2x2 inch ceJaant cube made from actual sludge wash liquid generated from.WVNS #2: Sludge Wash #1 and Sludge Wash #2 using a nominal thirty-two inch supernatant heel. It provides the procedure required to perform the tests stated in WVNS-TRQ-29 and WVNS-TE-029.1. The cube. Will also provide information on the reaction of the nominal recipe for cement on actual sludge wash material and determine
'if any unforeseen constituents are having an adverse effect on the cement product.
1.2 The liquids will be combined and evaporated to approximately one hundred milliliters (mls), which is the minimal volume of liquid required to generate a cube. The total dissolved solids in the concentrated material ' will have a maximum value of thirty-three weight percent
,o and a minimum value of twenty-nine. '~] 1.3 The data generated from this cube, compressive strength, gel time, bleed water and penetration resistance will be compared to the results obtained using data generated from simulated sludge wash liquid from the nominal thirty-three inch supernatant heel (see Attachment A) produced'under WVNS-TRQ-025, 2.0 REEINITIONS AND APBREVTATIONS 2.1 Definitions Cement-Dry Portland Type I cement in accordance with ASTM Standard C-150-85.
Antifcam-General Electric AF9020 emulsion of five percent Dimethlysilicone in nanopure. This is used as a cement recipe enhancer to prevent air entrapment in the cement 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. (D ()
~
PSK:TP-029A
/(,)} WVNS-TP-029A Rev. O Calcium Nitrate tetra-hydrate is used as a recipe enhancer in the setting of the cement waste form Cube-2x2x2 inch plastic mold used to make laboratory specimens.
2.2 Abbreviations ACM-Analytical Chemistry Method ASTM-American Society for Testing and Materials 3.0 RESPONSIBILITIES 3.1 Analytical and Process Chemistry will be responsible for the preparation and testing of the laboratory specimens in accordance to the applicable steps of the appropriate analytical chemistry methods and WVNS-TP-029A. 3.2 Quality Assurance will provide surveillance to ensure that the requirements of this test procedure and WVNS-TRQ-029 and WVNS-TE-029.1 a c satisfied and verify the
,-) final concentrate product, U caessing of the cube being
( j 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 WVDP-010 Rev 1. 3.4 Process Control Engineering will be responsible for issuing the test summary report,WVNS-TSR-029, in accordance with EP-11-003. 4.0 TOOLS. EOUTPMENT. COMPONENTS AND REFERENCES 4.1 Tools and Equipment Lightnin Lab mixer Model No. TS-1515 with high shear impeller or equivalent 2x2x2 inch plastic cube molds 100 milliliter (ml) plastic or glass graduated cylinder with one al divisions 500 ml polypropylene plastic bottles () 250 ml borosilicate beaker PSK:TP-029A 2
- .- - - ~ - . ~ - . - - i I
J 1 WVNS-TP-029A.
. Rev. 0 Corning hotplate or equivalent lo al-glass volumetric flhsk 20 al plastic scintillation vials magnetic stirring plate and magnetic stir bar '
stopwatch or timer accurate to one second top loading balance readable to 0.01 gs (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, csagent grade
.I Nanopure teater or ASTM Type-I water Sodium Silicate, technical grade *
-Antifcan General Electric AF9020*
- Supplied by IRTS operations 4.3. References NRC Technical Position on Waste Form (Revision 1)1 Dec,-
1990. ACM-4701 " Destructive Test of 2 inch Cement Cubes" ACM-2401 " Density" Rev 3 ACM-2501-" Determination of Total' Solids" Rev 2
" Removal of Plutonium from WestLValley High-Level Liquid
- Wasta", Bray,'Hara, Kazmierczak, dated January, 1991 ASTM C 109-86 PSK:TP-029A 3
9 n) ( V WVNS-TP-029A Rev. O WVNS-TPQ-29 " Production of Cement Product for Actual Sludge Wash Liquid" WVNS-TE-029.1 EP-11-003 5.O GENERAL INFORMATION 5.1 This test will be used to evaluate the nominal cement formulation recipe (see Attachment C) using actual sludge wash and supernatant from tank BD-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 unforseen constituent are having an undesirable effect on the cement product. 6.0 PROCEDURE 6.1 Prerequisite
/%
l )
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Oven or environmental chamber should be set at proper 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 reviewod in ACP 7.2 6.2.1 The liquids from WVNS 2, Sludge Wash #1 and sludge Wash #2 , pre and post concentrated material,( see Attachment B) will be combined in a two-hund.ed and fifty m1 beaker and evaporated slowly, while stirring to reduce splattering. The liquid will be reduced to approximately three quarters of its initial volume. At this point the total solids will be determined by ACM-2401. If the total solid content is between twenty-nine and thirty-three percent, the evaporation will stop and the solution allowed to cool. If the solid content is lower than twenty-nine percent, evaporation will continue and the liquid tested D)
. \._
PSK:TP-029A 4
WVNS-TP-029A ( ]) (,, Rev. O periodically by ACM-2401 until the specified 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 were solids are falling out of solution, the evaporation should stop and nanopure water should be added in small increments and the solution should be allowed to stir. Water and stirring shall be used to redissolve the solids. A total solid determination should be made and an appropriate amount of water added to achieve the total solids specified. 6.2.3 After the appropriate solid content has been 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 WVNS-TRQ-029 sec 2.4. fh. 6.3.1 Make a five (5%) percent antifoam solution. ('~) Weigh 5.00 t 0.05 gs of well mixed AF9020 in a 100 mi volumetric 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 plate., 6.3.2 Prepara 200 gs 5.7 percent calcium nitrate tetra-hydrat--/ cement mixture by adding 11.4 gs calcium nitrate tetra-hydrate to 200 gs Portland Type I cement 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 esssel by evenly cutting off the tip and producing an open ended cylinder. 6.3.4 Similarly cut thef 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 waste. 6.3.5 Tare the cutoff two hundred-fifty (250 ml) bottle and add 140.'5 t lg cement / calcium nitrate. Record weight on the appropriate Form (3 7 v j WV-2301. PSK:TP-029A 5
g , WVNS-TP-029A (v) Rev. O
'6.3.6 Place the cut empty five hundred (500 ml) mixing vessel prepared in step 6.3.2 under impeller and set mixer speed to one thousand rpm.
6.3.7 Measure 96 i 2 al of 29-33 Wtt sludge wash from step 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 vessel 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 step 6.3.1. Record on Form W-2301. 6.3.10 Tara a 10 ml disposable plastic cup and add to it approximately 11.00 0.5 gs sodium silicate. The exact amount transferred will be found by re-weighing the cup after the ( )
'v' material is poured into the sludge wash. Record the weight on Form WV-2301 6.3.11 Support the mixer on a' lab stand so that the impeller blade is one-quarter to one-eighth 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 minutes.
6.3.12 Begin the mixing at 1000 rpm and start the timer. Add the dry cement / calcium nitrate mixture to the waste within the first thirty seconds. Af ter 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 WV-2301. While mixing, mark a cube mold with a permanent marker with the date, sample type, numerical identification sequence nymber and then weigh the cube mold, record the weight on Form WV- _ [st 2301. v PSK:TP-029A 6
m WVHS-TP-029A (v) Rev. O 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 WV-2301. Determine the wat density of the material by the formula below. Wet Density 4otal weicht of cube (a) -Tare weicht of cube (a) 131 mis Record on Form WV-2301. After 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 m . minutes and do not disturb between these time [\J intervals. Record the time it take the cement to gel. Galation is a subjective determination, however galled cement is indicated when the 20 m1 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 t2 celsius within two hour of preparation and allow to cure in the oven for 61 -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 .1., After 24 hours, determine in als the bleedwe.ter in the scintillation vial and also determine the pH by indicator paper; record it on Form WV-2301.
'" N, Q) l PSK:TP-029A 7
,, WVNS-TP-029A
[ ') Rev. O V 6.3.19 Calculate the water to cement ratio by weight using formula below. ( A) (B) (1-C) (D) (0. 94 3 ) A= Volume in als of sample B= Density value in gs/ml of sample C= Total Solids value in decimal form D= Weight of cement used in gs 6.3.20 After sixty-one hours t 8 hour take the cube out of the oven and do the penetration resistance analysis (see section 6.3.22) and record the time, date and temperature of the cube removal and also the penetration resistance on Form WV-2301. 6.3.21 Caution: Do not remove the cube from the mold for the penetration test and only when ready to crush. 6.3.22 Using the concrete penetror.eter model CT-421; l7_') perform the penetration resistance test by
'J~
removing the cube from the bag and placing the penetrometer plunger in the center of the exposed side of the cube. Make sure the red indicator-ring has been set back to the zero mark on the penetrometer. With a steady vertical force push the penetrometer against the cube until the red indicator ring is all the way down the scale when the penetrometer shaft will not penetrate the cement any further. 6.3.23 On the handle of the penetrometer, read the value on the red indicator ring and record the number on Form WV-2301. If the red indicator ring is all the way to the end of the scale, a value of >700 psi shall be recorded. 6.3.24 When the sample cube is cured for a total of 7 days t 8 hours Determine the dry density by the formula below: i ( A_)/ PSK:TP-029A '8
1 . WVNS-TP-029A
- !'-~) Rev. O Dry Density = Total weicht of dry cube (ci-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 No. ACM-140 7.0 DATA ACOUISITION 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 ATTACHMENTS A) Composition of Simulant with 33 inch Supernatant Heel B) Analysis of Sludge Wash liquids f C) Nominal Recipe for Sludge Wash Cement (' D) Nominal Cement Recipe Compressive Strength Data E) Density Worksheet, ACM-2401 Rev 2 F) Total Solids Worksheet, ACM-2501 Rev 2 k' _./ PSK:TP-029A 9
WVNS-TP-029A Pev. 0 Attachment A (v) ION CONCENTRATIONS FOR CEMENT FORMULATION from TABLE 4-8 of Topical Report " CEMENT WASTE FORM QUALIFICATION REPORT - WVDP PUREX DECONTAMINATED SUPERNATANT" LB/20.9 gal ** 30lt Formula g/L g/L at 33 wt % Mol Wt 3 odium Nitrate NANO 3 278.344 278.344 48.547 85.010 3 odium Nitrite NANO 2 143.790 143.790 25.079 69.000 3 odium Sulfate Na2SO4 35.222 35.222 6.3432 142.060 3 odium Bicarbonate NaHCO3 19.656 19.656 3.42P2 84.010
?otacsium Nitrate KNO3 16.753 16.753 2.9220 101.100 3 odium Carbonate Na2CO3 11.661 11.661 2.03:a 106.000 3 odium Hydroxide NaOH 8.100 8.100 1.4127 40.010 3 odium Chromate Na2CrO4 2.851 2.848 0.4967 101.970 iodium Chloride Nacl 2.163 2.163 0.3773 58.450 3 odium Phosphate Na3PO4 1.754 1.754 0.3060 163.940 3 odium Molybdate Na2 moo 4.2H 0.374 0.374 0.0653 241.950 3 odium Fluoride NaF 0.000 41.990 iodium Borate Na2B407 0.665 0.665 0.1159 201.270 102 800.682 1060.000 139.6500 0.000 24 ic acid 0.299 0.299 0.0521 192.120 tc acid 0.299 0.299 0.0521 126.070 . aric acid 0.299 0.299 0.0521 150.000 Total Mole %
It % it of Solids 522.230 522.227 91.084 it of Solution 1322.912 1582.227 230.734 it % Solids 39.476 33.006 39.476 1255.74 ml (- 4 i_) PSK:TP-029A 10
' WVNS-TP-029A Rev. 0 ( ) Attachment B DATA FOR THE LABORATORY SCALE SLUDGE WASTE AT pH 12.5 F. Hara 12/5/90 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 Denaity of Sludge (g/ml) Raw Super from 8D-2 71.3 g Vol of Raw Super 60.2 Vol of Wash Water 500 ml Density 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 BEFORE DECONTAMINATION WITH TITANIUM COATED ZEOLITE Analysi. of wasbet M2ncured Parameters or First Second Third Fourth dried Labsratory Analysis Wash Wash Wash Wash slur:ge No (Sa ID) 900330 900331 Wt Super (gram) 468 458 406 484 Denalty (g/ml) 1.109 1.032 1.009 1.002 Vol Super (ml) 422 444 402 483 Liq Vol in Sludge (ml) 175 175 175 175 Total Liquid Vol (ml) 597 619 577 658 pH 11.8"i 11.58 11.63 11.59 Nitrite (ug/g soln) 21100 6080 2070 580 Nitrate (ug/g) 20600 5680 1830 399 SulfCte (ug/g) 25400 6620 2340 593 Chlcride (ug/g) 978 614 22 14 Pho phate (ug/g) Sodium (ug/g) AA 44880 11510 4190 1710 47 Pota2sium (ug/g) AA 1900 710 230 (.53)? Urznium (ug/g) Fluorimeter 150 36 3.2 1.6 44100 Cr (ug/g) AA Tot 157 23 11 2.6 C3 (ug/g) AA 12.4 9.24 3.08 0.57 18370 Al (ug/g) 1000 180 100 60 18067 Ba (ug/g) a900
,m I }
v PSK:TP-029A il
4
- WVNS-TP-029A Rev. 0
T Attachment B
(.) (cont'd) CHEMICAL ANALYSIS OF LABORATORY SCALE SLUDGE WASEES BEFORE DECONTAMINATION WITH TITAh2UM COATED ZEOLITE Analysis of washed M cured Parameters or First Second Third Fourth dried Labsratory Analysis Wash Wash Wash Wash sludge Lab No (Sa ID) Pu239 (uCi/g) 0.198 0.026 0.00732 0.0012 Tot 21 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 CD 137 (uci/g) 418 118 41.4 11.9 291 Co 60 (uCi/ml) ND ND <6.5E-3 <2.4E-4 Tc 99 Sb 125 <5.7E-1 <1.6E-1 <7.2E-2 <6.0E-3 E 154 <1.8E-1 <4.8E-2 <2.7E-2 <1.2E-3
'55 <7.4E-1 <2.3E-1 <1.3E-1 <2.5E-3 Groca Alpha 1210 Groza Beta 127000 TDS (Wt %) 10.7 4.19 0.76 <0.1 TDS from Decon Wash 13.93 5.48 1.13 0.53 Grcms of TDS from WVNS-2 65.19212 25.64629 5.288377 2.480389 200,000 gal of super. 68.16050 20.27452 5.56 1.79 f
m. PGK:TP-029A 12
WVNS-TP-029A Rev. 0
') Attachment B x ,) (cont'd) 11/6/90 F. Hara SLUDGE WASH OF WVNS-2 AT 70*C DATA FOR THE LABORATORY SCALE SLUDGE WASH AT pH 12.5 4t cf Sludge (gram) 196 grams Solid in Sludge Jenalty of Sludge (g/ml)
R:w Super fra SD-2 (ml) Solids in Raw Super 701 of Wash Water Density of Raw Super CHEMICAL APALYSIS OF SLUDGE WASH - AFTER DECONTAMINATION WITH TITANIUM COATED ZEOLITE (8 wt% TiO2) COLUMNS inncured Parameters er First Second Third Fourth Laboratory Analysis Wash Wash Wash Wash Vt Super (gram) Jenaity (g/ml) 1.102 1.032 1.009 1.002 701 Super (ml) Li Vol in Sludge (ml) Liquid Vol (ml)
? 11.6 11.67 11.9 11.81 Mitrite (ug/g soln) 21300 6600 1900 510 litrate (ug/g) 18700 6070 1700 170 3ulfate (ug/g) 21000 6400 1800 d 'O 2hloride (ug/g)
Phocphate (ug/g) Sodium (ug/g) AA 44300 16400 4200 1700 Pottraium (ug/g) AA 49 21 71 28 Uranium (ug/g) Fluorimatar 52 30 17 1.2 Cr (ug/g) AA Tot 81 27 7.7 2.3 C2 (ug/g) AA 3.7 1.2 20 0.7 Al (ug/g) 820 250 120 77 Pu239 (uCi/g) 1.86E-06 1.65E,-06 2.38E-06 6.94E-06 T;tal Pu (uCi/g) 7.80E-06 2.90E-06 3.51E-06 1.06E-05 Sr 90 (uci/g) 1.93E-05 1.48E-04 1.20E-05 3.24E-04 CJ 137 (uCi/g) 6.31E-02 1.99E-03 5.82E-05 3.77E-03 Co 60 (uCi/ml) <ND <1.5E-5 ND <1.5E-6 Tc 99 1.30E-01 2.94E-02 1.01E-02 2.80E-03 j PSK:TP-029A , 10 , l
}
WVNS-TP-029A Rev. O
~ Attachment B- <
(cont'd) CHEMICAL-ANALYSIS OF SLUDGE WASH - AFTER DECONTAMINATION
- WITH TITANIUM COATED ZEOLITE (8 vt% TiO2) COLUMNS M00 cured Parameters or First Second Third _ Fourth Laboratory Analysis Wash Wash Wash Wash Sb-125 <1.5E-4 <9.5E-5 1.18E 1.70E-03 Eu 154 <5.2E-5 <5.1E-5 <7.4E-6 <7.9E-6
- Eu 155 <3.4E-5 <5.7E-5 <1.4E-5 <2.7E-5 Gro30 Alpha 5.12E-04 3.84E-04 <.00003 <.00003 ]
- Gro20 Beta 1.32E-01 2.84E-02 8.50E-03 7.32E-03 TDS in wt% 13.93 5.48 1.13 0.53
- TSS Wt% 0.11 0.05 P
O
.PSK:TP-029A 14 l
WVNS-TP-029A Rev. 0
/~T Attachment B
(_ (cont'd) CONCENTRATION OF DECONTAMINATED LAB WASH EXPERIMENTAL CHEMICAL ANALYSIS AFTER CONCENTRATION OF THE DECONTAMINATED WASH SOLUTION TO Wt% DETERMINED 2cnc ntrated SW # SW #1 SW #2 SW #3 SW #4 fitrite (ug/g soln) (2.92) (6.46) 61800 48200 48500 25600 litrate (ug/g) 64600 50600 46400 34000 3ulfate (ug/g) 44700 50400 51100 33800 Chloride (ug/g)
?hosphate (ug/g) 3 odium (ug/g) AA 104400 101000 111000 95800 ?otocsium (ug/g) AA 1600 1500 1600 1450 Jranium (ug/g) Fluorimeter 3r (ug/g) AA Tot 262 200 150 111
- n (ug/g) AA 8.2 9 14 4 11 (ug/g) 2100 1470 <280 <70 i* 9 (uCi/g)
$_-). Pu (uCi/g) 1.64E-05 4.08E-05 6.98E-06 2.30E-05 3r 90 2.76E-06 2.88E-04 5.02E-05 6.04E-05
- D 137 (uCi/g) 1.22E-01 1.17E-02 1.43E-03 1.78E-01
- o 60 ND ND ND ND fc 99 4.79E-01 3.03E-01 2.28E-01 1.16E-01 3b 125 <3.05E-4 4.70E-03 1.74E-02 9.40E-02 Su 154 <9.6E-5 <8.8E-5 <1.4E-4 <3.4E-4 Su 155 <5.1E-4 <1.06E-4 <1.1E-4 <4.4E-4 3 rocs Alpha-3 rosa Beta Den 3ity 1.297 1.265 1.26
- 1.26
- FDS 37.5 33.6 33 wt %* 33 wt %*
- Product diluted to remove from distillation apparatus.
D k) . PSK:TP-029A 15
\
.- WVNS-TP-029A Rev. O
; Attachment-C TO: John Cwynar Letteri FH:91:0018 From: Frank Hara--and Larry E. Michnik
Subject:
Cement Recipe for Sludge Wash Simulant with 33 inch Supernatant heel
-Date: ; January 24, 1990 The recipe for the laboratory scale specimen cube _(2x2x2) contain the following amounts of ingredients:
1)=140.O grams of. Portland Type I' Cement with 5.7% Calcium Nitrate 4~ Hydrate
- 2) 11.O grams Sodium Silicate
- 3) 0.3 als of 5.0 grams to 100-mis antifoam (AF-9020) 4)'96 mis of 33.0 weight percent Sludge wash simulant This recipe will produce a product with a water / cement ratio of 0.61
^* 4
' b .lliam
. nagerF. MacKellar A&PCs i
1 O PSK:TP-029A , 16
_ _ _ . _ . - . . . .. .. - ~ . . . . - _ ~ - - . .4 J'-
^WVNS-TP-029A Rev. O.
J ~'
. Attachment D
.s Nominal Recipe Simulant
? Template Method-Seven Day Curing Sample ID Comp Strength (psi)- Date Vrepared 1SWCF31NR'5.7/4 1194 1/23/91 SWCF3 NR.5.7/4 1592- 1/23/91 SWCF3 ' ER 5. 7/4 1444- "/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 O
.PSK:TP-029A 17
- WVNS-TP-029A Rev. O
~~'; Attachment E l
DENSITY WORKSHEET Page of SAMPLE NAME LOG NAME SPECIAL INSTRUCTIONS Instruments Used: 3 AMPLE ID QC STANDARD 3 AMPLE VOL. (A) mL FLASK + SAMPLE (B) 9 1 7LASK (C) g. j 9 2BORATORY TEMP. *C i CEMP. CORRECTION FACTOR (D) 3 AMPLE DENSITY (B-C) x D (g/mL) A If % TDS Requested: 120.640177 (Sample Density) - 119.09553 = % TDS Sample has % TDS
, ANALYST DATE i
_.) APPROVED DATE l PSK:TP-029A 18
.i l
- t. "
WVNS-TP-029A Rev. 0 ( Attachment F' TOTAL SOLIDS WORK SHEET Page of AMPLE NAME LOG NAME PECIAL-INSTRUCTIONS- -
~clcnce--(Model and S/N):- __
ample Drying' Method:' . vcn - (yes/no) S/N:- Hot Plate (yes/no) AMPLE.ID I RY DISH-(g)== W,_ l
' '- + SAMPLE (g). = Wi RIED SAMPLE.+ DISH s
= g) = Wo_:
I
. OTAL = SOLIDS ' - ( % )
- _'o W, .
- ', - WJ ANALYST DATE APPROVED DATE I
k/ W, - W, 2ALCULATIONS: Total Solids-(%wt) =- x-100 PSK:TP-029A 19
. - . . . . .. ~ - -
.s. g't VVNS TSR 029 Enngineering Release m2149 rsy Per ECN v4618 ( l
%) TEST
SUMMARY
REPORT REV. 1 TEST / TEST SERIES Sludge Wash Cement Vaste Form Qualification DESCRIPTION Cement Product from Actual __ Sludge Wash Liquid TEST REQUEST NO. WVNS TRQ 029 TEST PLAN NO. VVNS TP 029A TEST COMMENCEMENT DATE 4/18/91 TEST COMPLETION DATE 8/20/91 1.0 OBSERVATIONS / COMMENTS /
REFERENCES:
After release of WVNS-TRQ 029, it was realized that the tests could not be completed as requested. Test Plan WVNS TP 029A, in fact was written and authorized as a substitute for a portion of the work specified in UVNS TRQ 029. Specifically, objectives 2.11, 2.12, and 2.10 of the test request were completed per test procedure VVNS-TP 029A. Test procedure VVNS TP-029A combined the remaining portions of laboratory decontaminated sludge wash solutions from previous experiments into one collective sample. The sample was sampled for analyser and then concentrated prior to creation of a cement cube. The combined wash i solution was yellow and slightly cloudy with no observable solids collecting at the bottom of the lab vessel. The original laboratory solutions were filtered before being concentrated. Following completion of the tests, a test exception was written against the original test request (TE-WVNS TRQ-029 1) cancelling all other portions of the objectives. The work, as originally defined, is scheduled to be completed under different test requests: WVNS-TRQ-032, WVNS-TRQ 033, and UVNS-TRQ-034
2.0 REFERENCES
- 1) Letter FH:91:0073, L. E' Michnik and D. J. Fauch to J. C. Cwynar, "32-inch ' Heel Sludge Wash Confirmatory Cube ," dated May 8,1991.
> 2) Letter FL:91:0089, L. E. Michnib and R. A. Palmer and R. J. Lewandowski, to J. . L. Mahoney, " Initial Test Summary of WVNS TRQ-029A" dated September 9, 1991.
3.0 CONCLUSION
S / ACCEPTABILITY OF RESULTS/ OBJECTIVES MET: The acceptability of the three objectives retained from UNVS-TRQ 029 are presented below, p V WPC1047:3RM i
. VVHS TSR 029 Rev, 1 3.1 Analyze concentrates (objective 2.11) hw/
Activity
> ' Analyze the concentrates used in the preparation of a cement cube.
Task Accomplished
> Following concentration end filtration through a 0.45p filter, the liquid was sampled and analyzed. The results are presented in Table
- 1. Physical data lor the concentrates are a density of 1.23 gm/ml with a weight percent Total Dissolved Solids (TDS) of 29.7. This meets the defined acceptance window of 31 + 2 weieht percent TDS (section 1.2 of VVNS-TP 029A)
Tuo requested analyses could not be completed. There was an insufficient amount of undissolved solids in the concentrates such that the percent Total Suspended Solids (TSS) could not be measured. This result was expected and confirmed via this measurement. The other analysis not completed was for phosphate. With this matrix, the Ion Chromatograph was not capable of detecting phosphate. A new method would be needed for phosphate measurement. In future tests, total phosphorous (P) will be measured with the ICP AES and the equivalent phosphate (PO 4~3) calculated. 3.2 Prepara a Reference 2 inch Cement Cube (objective 2.12) r~ Activity k Use the concentrates to prepare a reference 2 inch cement cube per the standard Analytical Chemistry Method (ACM). Task Accomplished The cube was pr3 pared. a cement slurry density of 1.76 gm/ml was measured. A gel time of 35.5 minutes in the A&PC lab matches very well to general guides ' maintained by L. E. Michnik, A&PC Cognizant Scientist. The results prior to curing are very acceptable for a
- ement w6i e form enat meets the 10 CFR 61 criteria and general guides for CSS operation per VVNS-PCP 01.
3.3 Perform Tests on the Cement Cube (objective 2.14) Activity Check for bleedwater at the end of a 24 hour period following pouring of the cement cube. Perform a penetration test on the cube after a 61-hour cure at elevated temperature: also complete a destructive compressive strength measurement of the cube following a 7 day curing period.
\s./
VPC1047:3RM
. . ~ -
' WVNS TSR 029 Rev. 1 Task Accomplished
[ No bicedyater was detected for this cement recipe at the 24 hour
. k)/ ma r!. . An initial curing cycle of 61 hours at 88 + 2 C was ccepleted. O netration testing following the 61 hour period yielded a value of >7C1 psi (beycnd range of penetrometer) which is typical and very acceptable for laboratory cubes.
Following completion of a seven day curing period (total time), destructive compression testing on the cube was performed. The cube was compressed using templates (not recognized yet in ASTM C 109). The result (694 psi) exceeds the minimum mean strength (500 psi) specified in the NRC Technical Position on Waste Form, Revision 1. For comparison three cubes were prepared in the A&PC lab using reagent grade chemicals to simu" te the concentrates used in this experiment. The three cubes ute1 a simulant recipe as shown in Table 2. Trace levels of organics in the recipe are about 30 percent higher than the level defined for sludge wash solution with a 129 inch heel. The results of compressive strength crushing (sising templates) for the three cubes were 841, 1079, and 1138 psi. Combined with a t-statistic of 2.92, the range of strengths that should cover 95 percent of a gausian distribution go from 560 psi up to 1478 psi. This implies that the simulant cubes are exhibiting the same compressive strengths as the laboratory concentrates cube. I The conclusion of this work is that the nominal recipe developed for sludge washing is acceptable although the cube was representative of
-sludge washing with a 32 inch heel. Additional experiments are defined in WNS-TRQ 032, WVNS TRQ 033, and WVNS TRQ-034 to confirm the cement recipe for sludge washing with a 129 inch heel.
4.0 ACTIONS OUTSTANDING:
> No actions remain outstanding for closure of this test series.
APPROVAL (3) _ _ ADDITIONAL REVIEWERS. YES NO L. Mahoney -
/
- 0. &w f I t
'U. A. Sm W 4) C. Cwyr&{
L. E.~ - W 'l c_ i f k 44 , & D. C. Meess QualitpAssurance G I WPC1047:3RM f-
- WNS TSR 029 Rev. l' TABLE 1 f, Analyses of Laboratory Produced LVTS Coteentrates
(
%) ' .-
unitsfare pgm/gm- units are pga/gm Al- 1210 NO2 ' 52,300 B 58.4 NO3 ' 42,600
.Ca <15 PO4 ' N t Measured C1' 3100 Sos 2 41,200 Cr 161 Ti <4.7 K 882 U 169 Na -. 94,700 pH _
12,36 Total Dissolved Solids (TDS) 29.7% density [gm/ml] . _ 1.23 Total Suspended Solids.(TSS) Insufficient Sample Units are pCi/gm . units are pCi/gm alpha.Pu _ <5.8E 4 CS-137 0.058
-gross alpha <1.4E-3 Sr 90 2.31E-5 -( h) .- gross beta -0.224 Tc 99 -%) 0.227
- /'N
\_)
WPC1047:3RM flJ; WNS TSR 029. e o Rev. 1- {
.s
- TABL8 2 h Composition of Simulated Sludge Wash h
Dry Weight Percent NANO 3 25.0 NANO 2 30.2 Na2SO 4 35.8 NaHCO 2.69 3 KNO 3 2.29 Na2CO 3 1.59 Nacl 0.30 Na3PO 4 0.24 Na2M o04,2H 2O 0.051 Na2B0 4 7,10H 2O 0,091 Citric Acid (.1H 2O) 0.082
'f M (f Oxalic Acid (,2H O) 2 0.082 Tartaric Acid (anhydr) 0,082 Na2C r04 0.39 NaOH 1.11 y~
\
WPC1047:3RM 5-
o y'- West Valley Demonstration Project Doc. N . Der wvNS 1Rc 030 Revision Ntaber 0 Revision Date 05/01/91 Engineering Release #2075 TEST REQUEST FULL-SCALE CONFIRMATION OF THS NOMINAL RECIPE FOR CEMINT SOLIDIFICATION OF SLUDGE W ASH LIQUIDS PREPARED BY @/// M. N. Baker Cognizant Engineer APPROVED BY km Cognizant System Design Manager D. C . M e es s APPROVED BY _ /4444/g._ slh/)f 4 e # (h ., D. L. Shugars _Wuality pstfrance APPROVED BY GM , An MT 13-f/D. J. Harward ffadiatio'n & Safety APPROVED BY k 'b - - d30/9; J. C. Cwynar PVocess Co:jtrol Engineering West Valley Nuclear Services Co., Inc. P.O. Box 191 West Valley, NY 14171-0191 WV-1816, Rev.1
. WNS.TRQ.030 Rev. 0 AECORD OF _ REVISION,
- . }'ROCEDURE 2i % re are changes to the procedurt 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 tnat contains a change.
i l Examph:
> The arrow in the margin indicates a change.
Revis.a On Rev. No. Description of Changes Page(s) Dated 0 Original Issue All 05/01/91 i O . v t 4 t W.1807, Rev.1 i DLS0431:3RM
- _ - .- . . -- - .. .-.. . - - - - - - - . - ~ . - . . . ~ . . . - . - ~ . . - . .
e ; WNS.TRQ.030 , Rev. 0 RECORD OF EEVISION (CONTINUATION SHEET) I Rev. No. Description of Changes fagefS)" Dated t i i t 1 t i O 1 W.1807, Rev. 1 - 11 D1.SO431:3RM
l.. TEST REQUEST O, WNS TRQ 030 REV. O FULL SCALE CONFIRMATION OF THE NOMINAL RECIPE FOR CEMENT SOLIDIFICATION OF SLUDCE VASH LIQUIDS
1.0 INTRODUCTION
1.1 This work is required to demonsttste the stability of the "ncminal" vaste fora recipe developed und e Test Requert WNS-TRQ 026. Characteristics which vill be tested are required by 10 CFR 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. 1.2 Vork will be performed using full scale square drums vSich were processed using a siraulant rep w.enting the actual vaste liquid, and the " nominal" recipe for cement addition and recipe enhancers. 'the full scale drums vill be processed under SIP 91-1, 1.3 This work is required by the Branch Technical Position. Appendix A.II.I. 1.4 Testing vill be performed in accordance with WNS TP 030, to be issued by Analytical and Process Chemistry, and WNS TPL 70 011. 1.$ Test resulta vill be documented in a Test Summary Report (WNS TRS 030), to be issued by the Cognizant Test Engineer in accordance with EP 11 003 2.0 OIVECTIVES 2.1 Af ter curing for a time determined by WNS-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. 2.2 Cores :.ill be obtained from various locations in the drums ( top, middle, bottom locations) te demonstrate the homogenous nature of the waste form. Iocations will be recorded on SOP 70 44 Attachment D. c.3 Ten (10) of the samples will be evaluated for compressive strength per ASTK Standard C 39 and QIP 27. DLSO431: 3RM 1
WVHS.TRQ.030 Rev. 0 7-- 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 days' immersion, three (3) of the s&mples will be evaluated for compressive strength per ASTM Standard C.39 and Q1P 27. Post. immersion p*?n compressive strength shall be at least 75 percent of the pre.!w w ebm mean compressive strength as determined by section 2.3 above c?s t least 500 PSI. If the post immersion mean compressin cysngth is less than 75 percent of the pre. immersion mean compressive strength, but not less than 500 PS1, the immersion testing interval shc11 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 the compressive strengths level off and do not concinue to decline with time. 2.4.1 The immersion liquid, either deionized water or synthetic sea " veter, will 'ce determined in advance of this test as part if the Leach Testing being conductec in accordance with VVN7. TRQ.026, Section 2.4. 3.0 SAFETY 3.1 Industrial Hygiene practices will be as described in the VVNS Hygiene 6 Safety Manual, VVDP.011. 3.2 Radiological work will be performed in accordance with the VVNS Radiological controls Manual, VVDP.010, O- 3.3 Work in the Analytical & Process Chemistry lab will be performed in accordunce with existing A6PC methods (ACM's). 4.0 EQUIPMENT CONflGURATION 4.1 All equipment will be set up in accordance with VVNS.TP.030 and as directed by the c)gnizant A&PC scientist or qualified A6PC technician. 4.2 Core Boring Equipment will be set up in accordance with SOP 70 44. 5.0 SAMPLING FREQUENCY 5.1 Samples will be obtained in the quantities and frequencies specified by section 2.1 of this Test Request. 5.2 Core drilling vill begin after a minimum cure time of 23 days. The actual cure time will be established in accordance with VVNS.TRQ. 026, section 2.2. I DLSO431:3RM 2 n v 1 l l l
- . . . , _ , , - - , _ . . - - . - . . , , , . - - . . . ~ - - , . . -, . , . - , .. . . - - . , - - . . .-
4 WNS.TRQ.030 Rev. O o, 6.0 PERSONNEL QUALIFICATION 6.1 Testing vill be performed by qualified Analytical & Process cheinistry Technicians in accordance with WNS.TP.033 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. O DLSO431:3RM 3 O
4 WVNS- Tit 0-030
's Rey, o
.j - :
Lc3ej c 8 4 3 .
/ T uJ u
A
,a * . 4 0; g \q \ ) _
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LO Figure la Drum Sampling Location's l l-
West Valley ooe. ""meer = "s-te-oso 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 PREPARED BY c< [ )(, L. E. Michnik Cognizangn ri c7 APPROVED BY '4pv D. C. Meess Cognizant System Design Manager Q , ,71/ j . APPROVED BY klulu . ~.' ;G'Wv-/c d4WFit
. O. L. Shugars Quality Apurance Manager APPROVED BY D 1. b M Da D. J. Harward Ra(ajion and Safety Manager APPROVED BY k . b . 0%.m . J. C. Cwynar PrdG hss Contrsl Engineering West Valley Nuclear Services Co., Inc.
- P.O. Box 191 Q, 3 BELOO79:3RM West Valley, NY 141714191 WW1816,81ev.1 .
- , - - , . - , , . - - - - - . n- -
WNS TP 030 Rev. 0 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 05/03/91 O O W 1807, Rev. BELOO79:1RM 1 i
1 WNS TP 030 Rev. O i RECORD OF REVISION (CONTI! NATION SHEET) i Rev. No. Description of Changes Revision)on Page(s Dated 1 1 t t 4
\
t r W-1807, Rev. 1 11
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- TEST PROCEDURF FOR PULL SCALE CONFIRMATION OF NOMINAL RECIPE OF SLUDCE WASH LIQUIDS VVNS TP.030 REV. 0 1.0 SCOPE '
1.1 This test procedure is being issued in response to VVNS TRQ 030. The purpose of this test is to correlate the characteristics of 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. 1.4 Correlation of full scale characteristics shall be accomplished by performing compressive strength tests on specimens before and aftsr 90 days immersion testing. []/ s_ 1.5 Compressive strength cents shall be conducted in accordance with QIP 027 and ASTM C 39, 1.6 The pre-immersion compressive strength of the cores will be docernined on ten samples. The mean compressive strength of these samples should be at least five hundred psi. 7.0 DEFINITION AND ABBREVIATIONS 2.1 Definitions Domineralized Water this water must have a conductivity of lees than five micromho/cm at twenty five degrees celsius and a total organic carbon of less than three parts per million. Simulated Sea Water a combination of various inorganic compounds. The fctmulation is as follows: 23.497 grams Sodium Chloride 4.981 grams Magnesium Chloride 3.917 grams Sodium Sulfate 1.102 grams Calcium Chloride 0.664 grams Potassium Chloride 0.192 grams Sodium carbonate 0.096 grams Potassium Bromide
, 965.551- mL Dcmineralized Water BELOO79:3RM 1-
WNVS TP 030 Rov. 0 This formulation is from the International Organization for y ) Standardization IOS 1691 1982(E). 2.2 Abbreviations ! i ACM. Analytical Chemistry Method ASTM.American Society for Testing and Materials ANSI /ANS.American Nuclear Standard Institute /American Nuclear Society QIP. Quality Inspection Procedure
-SOP. Standard Operating Procedure 3.0 RESPONSIBILITIES 3.1 Analytical and Process Chemistry will be responsible for the testing of the laboratory specimens in accordance with the ACM 6400 and ACM.6300.
3.2 Quality Assurance provides surveillance to ensure that the requirements of this test procedure are satisfied and will verify those portions of the test where applicable. They also perform the compression testing of cylindrical specimens in accordance with t' QIP.027 and applicable steps of ASTM C 39.
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3.3 Vaste Operations will be responsible for core boring the drums in accordance with SOP 70 44, 3.4 IRTS Operations is .esponsible for making the full scale drums in accordance with SIP 9101. 3.5 Radiological work will be performed in accordance with WVNS ' hadiological Control Manual, WVDP 010. 3.6 Industrial Hygiene practices are described in the WVNS Hygiene and Safety Manual, WVDP-011. 3.7 IRTS Process Control En6 1 neering-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
4.1 NRC Technical Position on Vaste Forms (Revision 1), January,1991. 4.2 ANSI /ANS -16.1 "Messurement of the Leachability of Solidified Low level Radioactive Wastes by a Short-tern Test Procedure". BELOO79:3RM 2-e .r , w w - - , -t- ,a +-7-- .p .-
WNVS TP 030 Rev. 0 {} (s / 4.3 ACM 6400 " Immersion Testing of Cement Specimens" 4.4 QIP 27 " Capping and Compressive Strength Testing of Cylindrical Cement Specimens". 4.$ ASTMC 39 " Compressive Strength of Cylindrical Concrete Specimens". 4.6 EP 11 003 " Experimental and Developmental Test Control for High-Level Vasta Form Qualification". - 4.7 WVNS TP 026 " Procedure for Qualification of the Nominal Recipe for Cement Solidification of Sludge Wash Liquids" 4.8 ACM 6300 " Leach Index of Cement Specimens",
$.0 CENERAL 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.
6.0 PROCEDURE 6.1 Prerequisite O' - A determination of the immersion liquid either de=ineralized water-or simulated sea water must be made before irmae rsion testing can be started. The most aggressive leaching liquid or the one that produces the lowest Leaching Index number based upon a twenty-four hour evaluation test, described in ANSI /ANS 16.1 and performed according to ACM-6300, will be used for this test. IRTS Operations shall produce the drums in accordance with SIP 91 01. 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 drues in accordance with SOP 70 44 QA to bs 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
.(,,(~') . with ACM 6400. See attachment A.
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WVS TP 030 Rev. 0 7.0 DATA ACQUISITION 7.1 Compressive strength of the cores will be recorded on data sheets { in accordance with QIP 27 ' 7.2 Core position data will be recorded on data sheets in accordance with SOP 70 44. 7.3 Run data will be recorded per SIP 91 01. 1 I l l
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i-VNVS TP 030 Rev. 0 ATTACliMENT A ( DRUM TESTINC MATRIX TOP MIDDL.E BOTTOM DRUM # 1 I I I I I l l 1 l C C I 1 l 3 3 I I I I I l _._ - 1 I I I I I I I I l l
$ 1 1 l C C l 2 I I I I l i I I I I I I I I I I i 10 l 2 l 3 l C C l l l l l l 1 1 I i l I I I i l i 15 l 2 4 ! C l 1 l
.I I l l l 1 1 I I I I 20 l C C l 4 4 l C l l 1 1 I I I -1 l C Compressive strength of samples to be determined.
1 Sample set si, compressive strength to be determined after 90 day immersion testing is complete. Sample set 82. Compressive strength to be determined, if necessary, after 120 day inmersion testing is complete. 3 - Sample Set #3, Compressive strength to be determined, if necessary, after 160 day itunersion testing is complete, 4 - Sample Set #4 Compressive strength to be determined, if necessary, after 180 day immersion testing is complete. O . BELOO79:3RM A-1
l WASTE FORM QUALIFICATION PROGRAM FOR CEMENT SOLIDIFICATION OF SLUDGE WASH LIQUID DEMONSTRATION PROJECT
. 6 VOL. 2 OF 2
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s IS.9UED 4/16/92 , b
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VOLUME II WASTE FORN QUALIFICATION PROCl'.AH ! FOR CEMENT SOLIDIFICATION I OF SLUDGE WASH LIQUID TABLE OF CONTENTS DOCUMENT NO. TITLE ((Ryl)10]f JIA M I WVNS-TPL-70-012 CEMENT WASTE FORM QUALIFICATION OF 1 COMPLETE SLUDGE WASH LIQUIDS WVNS-TRQ-034 TEST REQUEST PRODUCTtON OF CEMENT 0 COMPLETE PRODUCT FORM ACTUAL LAB. SLUDGE WAlill LIQUIDS WVNS-TP-034 TEST PROCEDURE FOR CONFIRMATORY CUllE O COMPLETE WVNS-TRQ-044 WASTE FORM QUALIFICATION WORK FOR COMPLETE SLUDGE WASH LIQUIDS WVNS-TP-044 PROCEDURE FOR WASTE FORM 0 COMPLETE QUALIFICATION WORK FOR SLUDGE WASit LIQUIDS WVHS-TRQ-045 PROCEDURE FOR HULTIVARIANT TESTING 0 COMPLETE OF CEMENT WASTE FORMS USING SIMULATED WASH SOLUTIONS
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V 1
4 o'~ West Valley *t. s-ser -N S . PC P . w 2 Demonstration Project """"""-6= o Revision Date Engineering Release *
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4-PROCESS CONTROL PLAN PROCESS CONTROL PLAN FOR CEMENT SOLIDIFICATION OF SLUDGE VASH LIQUID
,A.
k PREPARED BY - M. N. Baker Cognizant Engineer APPROVED BY D. C. Meess Cognizant Systern Design Manager APPROVED BY D. J . Harvard Radiation and Safety Manager APPROVED BY D. L. Shugars Quality Assurance Manager
- West Valley Nuclear Services Co., Inc.
P.O. Box 191 SAJ0057:3RM - West Valley, NY 14171-0191 WW1816, Rev.1
4
- VVNS PCP 002 Rev, 0 RECORD OF REVISION PROCEDURE If there are changes to the procedure, tha 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 Chat.ges Page(s) Dated 0 Original Issue All O VV 1807, Rev. 1 i S AJ0057 : 3RM O nu pu d
t l LYNS PCP 002
,' Rev. O RECORD OF REVISION (CONTI! NATION SHEET)
O Revision on Rev. No. Description of Changes Page(s) Dated E W 1807 Rev.1 it SAJ0057:3RM . O
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< WVNS.PCP.002
. Rev. O. Draft B PROCESS CONTROL PLAN FOR CEMENT !
Os SOLIDIFICATION OF SLUDGE VASH LIQUID { Table of content,s Page 1.0 SC0PE............................................................. 1
2.0 REFERENCES
........................................................ 1 3.0 S YS T EM D E S C R I PT I ON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 3.1 Process Description......................................... 1 3.1.1 Waste Storage and Dispensin6 Subsystem............... 2 3.1.2 Mixer Flush Subsystem................................ 3 3.1.3 Chemical Additive Systems............ ............... 3 3.1.4 Cement Transfer and Storage Subsyster ..... ........, 4 3.1.5 The Cement Metering Subsystem...............
........ 5 3.1.6 The High Shear Mixing Subsystem...................... 5 3.1.7 Drum Feed, Positioning and Transfer Subsystem. . . . . . . . i 3.2 Process Chemistry Formulation for De c o n t am i na t e d S up e rna t a n t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 3.3 Handling Flush Drums and Drums Suspected to be in Noncompliance.................................... 6 3.4 . Drum F111................................................... 7
('~' 3.5 System Operation.......... ................................ 8
-3.6 Process Control System......................................
17 3.7 CSS Data Acquisition System................................. 18 4.0 REQUIREMENTS FOR SAMPLE VERIFICATION.............................. 22 4.1 Laboratory Safety........................................... 22 42 Prerequisites.......................... .................... 22 4.3 Sample Acceptance Criteria...... .... .........,........... 24 4.4 Requirements for Sample Verification........................ 24
$.0 S AMPLE VERIFICATION PROCEDURE . . . . . . . . . . . . . . . . . . . . . . . . . . ......... 25 6.0 FU LL. S CALE S O LI D I FI CAT I ON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 6.1 Calculation of Full Scale Formulation. ..................... 35 6.2 Full Scale Focmu1ation...................................... 35 6.3 Full Scale Fo rmula tion Contro1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 7.O RECORDS. DOCUMENT CONTROL, AND QUALITY ASSURANCE..,..,............ 36 8.0 FULL. SCALE DRUM. TESTING........................................... 37 i
L i Attachment A - Cement Solidification System Run Plan. ............ A1 l lr i SAJ0057:3RM 111
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L WVHS PCP 002 s Rev. O. Draft 8 PROCESS CONTROL PIAN FOR CEMEffT
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SOLIDIFICATION OF SLUDGE VASH LIQUID 1.0 SCOPE This Process Control Plan describes the Cement Solidification Process, its controls, and product quality requirements which will be used during solidification of the slud 6e wash liquid. The solidification recipe used was developed and demonstrated to comply with the requirements of 10 CFR 61 Section 61.55 and 61.56 for low level waste stabilization. The recipe was further tested at Vest Valley to demonstrate process performance and the capability to contr91 the recipe constituents at full scale. This Process Control Plan describes the means of controlling the process to assure that the waste form produced is in conformance with the qualified recipe. t To provide assurance that the vaste/ cement will perform to its qualified recipe, test cubes will be made, as a minimum for each 5000 gallons of waste to be processed. This will involve one (1) cube for tank 5 D 15A2 (gtess capacity 5000 gallons) and two (2) cubes for tank 5 D.15Al (gross capacity 10,000 gallons). In order to confirm the uniform nonhazardous nature of the waste form, one (1) sample of the concentrated decontaminated sludge wash will be analyzed for chromium concentration during each Integrated Radwaste Treatment System (IRTS) campaign. O O
2.0 REFERENCES
Standard Operating Procedures pertinent to this Process Control Plan are listed in actcchment A. 3.0 SYSTEM DESCRIPTION 3.1 Process Descriptier. The Cement Solidification System (CSS) includes all piping, valves, instruments, controls, tanks, and equipment required to solidify waste in cement, place it into drums, and remotely move the drums onto a' shielded truck for transport to the storage facility. Attachment A (the Run Plan) contains a graphic flow diagram describing the solidification system and its functions, controls and procedures. The CSS utilizou a high shear mixer to blend waste, cement and additives into a homogeneous slurry. The impeller located at the bottom of the mixer causes the contents to be drawn to the center of the mixer housing and forces the fluid between the impeller and i the casin5 This method of mixing ensures thorough and homogeneous l blending of all ' components. l l; . i t I v SAJ0057:3RM 1- { l
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VVHS PCP 002
, Rev. O, Draft B The CSS performs the following functions:
o Vaste Solidification mixing decontaminated sludge wash vaste with Portland Type I cement and chemical additives, and packaging the resulting mixture into 269 L square drums. o Process Control monitoring and controlling recipe constituent addition, equipment functions and safety interlocks. o Cement Storage and Transfer - bulk storage of dry Forciand Type I cement powder blended with nominally 5.711.7 (minimum of 4.0, maximum of 7.4) w/o Ca(NO 3 )2 and transfer of batch quantities to the mixers, o Materials Handling remote handling of empty and f t11ed drums within the facility and loading filled drums onto vehicles for transport to the RTS Drum Cell. The CSS is composed of the following subsystems: ' 3.1.1 Vaste Storage and Dispensing Subsystem The Vaste Storage and Dispensing Subsystem is the beginning of the treatment process and is composed of the Waste Dispensing Vessel and the Vaste Dispensing Pump. The waste liquid is collected and stored here before being mixed with , cement; recirculation through the Vaste Dispensing Pump maintains bomogeneity of the waste while it is stored within O. the Vaste Dispensing Vessel. Feeds to the Waste Dispensing Vessel are sampled at the final tank feeding the vessel (typically 5 D 15A1 and 15A2 for decontaminated sludge wash solution). Other waste streams will not be added to the Waste Dispensing Vessel during sludge wa..h processing. The waste feed solids concentration is controlled by the LVTS evaporator at 20 w/o total solids. The allowable range is 19 to 21 w/o. (Product Requirement) The effect of tbts range is a variance in water to cement ratio within ene allowable range of 0.64 to 0.68. If necessary, the feed can be diluted to nominally 20 w/o. The method of analysis and tests performed on the samples are discussed in Section 4.0, " Requirements for Sample Verification". 3.1.2 Mixer Flush subsystem Whenever the CSS is shutdown for maintenance, or at least at the end of each operating day, the High Shear Mixers will be flushed to prevent residual cement / waste mixture from hardening inside the mixing vessel. O SAJ0057:3RM 2-
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.- WNS.PCP.002 Rov. O, Draft B This process is controlled by the operator at the HS. CSS O Panel. Vhen flushing is required,-utility water is transferred to each mixer through a spray nozzle with the mixers shut down; the amount transferred is controlled by weight. The mixers are then started on high speed (2000 RPM) creating a highly turbulent transient . rave which provides good flushing action. After two or three minutes of agitation at high speed, the flush solutions are dumped into a specially designed decent drum at the fill station.
The arocedure is repeated with rinse water. The Flush Drum at the Fill Station is transferred to the Flush Drum Storage Station where the residue is allowed to settle out, the remaining liquid is decanted to an underground storage tank (7 D 13) and will be processed through the existing plant radwasta system. The drum is reused until it is half tull of residue ( 102 litres); the drtue is then filled with a water / cement mix, and is transported to a storage area. It is expected that each mixer will be flushed prior to system shut down or as ' required based.on mixer build up. Each flush drum holds i multiple flushes. . If the waste is greater than Class A (see Section 3.3). it will have. to be overpacked in a high
. integrity container prior to disposal.
3.1.3 Chemical. Additive Systems (Producc Requirement) i Systems are provided to add chemicals'to the mixers to accelerate the gelation rate of the waste and contral the rate at which the cement sets to minimize i.tildup of solidified cement in the mixers minimizing the number of f1pshes required. Calcium nitrate at nominally 5.7 w/o is blended with dry Portland Type i cement by the cement supplier as-a gel-accelerating component. Testing performed ; to data indicates that the recipe performance is insensitive ' to variations in calcium nitrate, and sodium silicate.
= additive over the approved range indicated in the recipe sheets. The acceptance range in calcium nitrate in Portland Type I is 5.7 +1.7 percent. The blending operation is conducted by a vendor using approved procedures under the WNS quality assurance program. Samples are analyzed by the '
analytical laboratory for nitrate concentration to verify acceptable blending by- the vendor. Experience has shown that-the calcium nitrate does not separate during transport or transfer because it adheres to the cement particles. The dry coment/ calcium nitrate blend is stored in the cement
.sao and is-added to the mixers by the coment metering subsystem. Antifoan (CE AF.9020) is added to the mixers with the waste. solution to reduce air entrainment in the L waste product. Sodium silicato is added to the mixers as the second component of the set enhancer. The amount of-
. antifoam added is shown on the recipe sheets. It is added l
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WNS.PCP.002 Rev. O, Draft B by injection directly to the mixers from a lab scale O positive displacement pump. Only the sodium silicate addition is varied depending on the particular sludge wash waste batch being processed, the rer= Ndar of the i constituents are held constant. The amount of sodium silicate added to each batch is expected to vary only i
)
slightly, if at all, because of the decontaminated sludge , wash solutions homogeneity. The amount of sodium silicate j to be added is nominally 18 pounds per batch. The i homogeneity of the sludge wash being processed is such that i valid solidification results can be gained on a sample of the full batch. Full scale racipes for TBD to TBD gallons ' of vaste are contained in Section 3.5. ' Homo 6eneity of the calcium nitrate cement blend is assured through-the use of an approved blending procedure submitted by the supplier, periodic quality assurance of the
-supplier's blending operation and chemical analysis of the blend to assure homogeneity. >
3.1.4 Cement Transfer and Storage Subsystem : The Careent Storage and Tgansfer System provides a bulk storage capacity of 70 m (about 100 tons) for the dry coment/ calcium nitrate blend -and transfers ! c :?o the Cement i Metering Subsystem. The blend is delivere from off site by O truck and transferred pnewsatically to tL, Bulk Storage Silo. The transfer air exits the silo through a dust filter at the top. A blower is used to pneumatically transfer the ' blend to the Acrison day bin in the Cement Metering Subsystem on demand. The transport air is vented back to the Bulk Storage Silo where'it vents through a dust filter. 3.1.5 The Cement Metering' Subsystem-(Product Requirement) This subsystem uses a gravimetric (loss in. weight) feeder to accurately dispense the Portland Type 1 dry cement / calcium ' nitrate blend from the Acrison day bin into the mixers. A bulk dry cement storage silo is located near the CSS to facilitate the filling of the day bin and minimize dust ,
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inside the facility. 3.1.6 The High Shear Mixing Subsystem Batch control for the High Shear Mixer is automatic, che
. operator sets the panel controls for the recipe to bs processed and initiates the process. The process parameters are controlled automatically by che HS. CSS programmable
, logic controller (see Section 3.6). The waste feed, cement / calcium nitrate. blend, and additives are metered into l- the mixer, which runs. continuously during operation. ** l- batch is mixed to. assure homogeneity and is dischargo D to l SAJ0057:3RM 4 i n . . , - - . - - - - - - . - - - - - - - - - -
WNS PCP 002 Rev. O. Dreft B the vaste drum (typically 269L square drums). The process (c) v is controlled to assure the recipe is followed and the container is fillea to greater than 85 percent capacity. 3.1.7 Drum Teed, Positioning and Transfer Subsystem A remotely operable conveyor system is installed at CSS to: o Move empty drums into the Process Cell, o Place drums in position for filling, o Read drum dose rates and bar code labels for drum identification, o Manipulate filled drums to the smear station for surface contamination measurements and to the overpack station if required, o Install and crimp lids on filled drums, o Provide for storage of drums prior to load out from the facility, o To transfer filled drums onto the shielded truck for transport to the drum cell, and (V o Periodically test drums for fill, free water and penetration resistance. 3.2 Process Chemistry Formulation for Decontaminated Sludge Vash Portland Type I cement and waste alone do not produce an acceptable product because of the delay in gelation and ultimately the set time. It is necessary to utilize admixtures of constituents normally present in both the waste stream and the Portland cement to accelerate gelation assuring proper dispersal of waste in the matrix by preventing cement particle settling and s.: ting of the final product in a reasonable time period following production. Early gelation is required to permit timely transport of drums to the stora6e area. Prior to transferring waste from IVIS to the Vaste Dispensing Vessel, the concentraces collection tank (either 5 D 15A1 or 5 D 15A2) is sampled. Sufficient sample volume is collected for radiochemical analysis and preparation of a verification sample for solidification. Due to its larger operating volume, tank $D 15A1 is sampled prior to solidification and also at 50 percent t10 percent level as an in process check. The second sample vill be for presolidification testing only. The purpose of these samples is to assure that the batch of waste to be transferred can be properly solidified using the reference qualified recipe and to b G SM0057 : 3eH 5-l
1 1 WNS PCP.002 Rov. O, Draft B o provide isotopic analysis for waste classification. The results of I the isotopic analysis can be correlated with the vaste solution i composition. The requirements for sample verification are contained in Section 4.0. The process control systems and logic used to asrare that the product is produced in accordance with the qualified formulation is described in Section 3.6, Process Control System. 3.3 Handling Flush Drums _and Drums Suspected to be in Noncompliance As described in Section 3.1, mixers may be periodically flushed to maintain them free of excessive et. ment buil p. The residual flush water will be decanted from the drums leaving behind a relatively dry cement product. 'Ihe residual cement following decanting will be capped with a cement and water mix specified in a flush recipe to provide a means of solidifying any small amount of free water that may remain on the surface of the decanted cement. Since the cement remaining after decanting consists of residuals from several batches, its qualification and classification are uncertain. These drums will not be processed for immediate disposal, but will be transferred to a stora6e area where the cement will be allowed to set. The drums will be classified and transferred .into a high integrity containst (if neesssary) prior to ultimate disposal. Those flush drums which qualify as Class A waste will be stored for later disposal in,tha Class A disposal facility. (~ Even though the process is well controlled to produce a product Q} meeting the qualified product characteristics, it may be possible through process upsets to produce material which is outside the qualified region. These containers are referred to as " suspect drums" and could be "out of specification" as a result of variations in PRODUCT REQUIREMENTS or PROCESS REQUIREMENTS. PRODUCT REQUIREMENTS will be those necessary to produce an acceptable vaste form per 10CFR61. PROCESS REQUIREMENTS will be those necessary for smooth operation fa the Cement Solidification System. TRODUCT REQUIREMENTS include: Vater to cement ratio, percent solids in the waste, sulfate percent of total solids, drum percent full, free water in the drum, verification (cube) compressive strength, and addition of recipe admixtures. PROCESS REQUIREMENTS include: mix time, gel time of presolidification verification (cube) sample and data base corrections. All " suspect drums" resulting from process upsets will be evaluated on a case by. case basis, and documented on a Nonconformance Report. Upsets in PRODUCT REQUIREMENTS will be set aside for further evaluation, including compressive strength and leachability ( testing. A critique will be held to investigate the cause of the upset, and prevent recurrance. Upsets in PROCESS REQUIREMENTS p ' 4~ SM0057 : 3RM 6 l l l
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' WNS PCP 002 , Rev. O. Draft B j O will be set aside until a technical evaluation can be completed to determine product acceptability.
Drums originally considered " suspect" that are found to be l acceptable after technical evaluation or testing will be placed in l the D.am Cell stack. For upsets in PRODUCT REQUIREMENTS, the ) Nonconformance Report will be referenced on the drum data base, documenting the upset condition, evaluatior or test results, and corrective actions (s). Those containers which are unacceptable for disposal will be removed from storage and will uw placed in high integrity containers prior to disposal. 3.4 Drum Fill (Product Requirement) , Drums produced for disposal must be at least 85 percent full of qualified cement product or other suitable inert backfill which meets the 10CFR61 requirements. The drum fill is controlled through the volume of waste, admixtures, and cement prepared for addition to the druen by onch mixer and may be verifiwd by load cell wei6 ht indication. A representative sample of . a k 5D 15A1 or 5D-15A2 is analyzed for cesium, strontium, plutonium, and sulfate and total solids. Once this data is known, the data in table I en pages TBD through TBD is used to detertaine both vaste and ce e me addition criteria. Table usage is based on determinatian o. total O solids concentration in the wasta combined with reca,.a bat;h size (e.g., 20 gallon batches) to achieve the desired drum fill. Vaste and cement (with calciu:s nitrate) additions are pteprogrammed into the HSCSS and acrison control panels such that feed to the mixers is controlled and monitored. One drum per each process Tank 5D 15A1 or 5D 15A2 is physically inspected for freeboard determination, free liquid presence and per-crometer resistance. The sludge wash solution to be processed i <ery homogeneous so it is unlikely that modification of the recipe will be required during the processing period for either tank (usually 2 4 days). The drum that is physically inspected is considered to be representative ot' tk entire batch of drums from either 3D-15Al or 5D 15A2. Tables TBD thru TBD show the calcuaated range of drurs fills produced, acceptable recipe variations, the amount of each constituent to be added, and the water to cement ratio. Percent fill is verified by the ~uata Acquisition System based on the weight of constituents added to the mixer within the acceptable fill range. O SAJ0057:3RM 7 _. -,_ ___ . _ _ - , ,_ _ _ _ _ _ _.-- _ _ __ _.m.
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- WNS PCP.002 Rev. O. Draft B i
3.5 System Operation oefore beginning any processing of decontaminated waste from the LVTS storage tanks, a successful sample verification must be completed in accordance with the Sample Verification Procedure of Section 5.0. The successful sample solidification parameters are l recorded on the Solidification Data Sheet. Thess parameter are i used to verify that the reference recipe is either acceptabte as specified or to specify minor changes to the recipe within the qualified region. ' i O SAJ0057:3RM 8
c VVNS PCP 002 4 Rev, 0, Draft B 1 !] ,. t v)
' Table 1 - Summary of CSS Warte Stream Formulations 10A -
;2.' Gallons /M.xer Batch 10B -
16.5 Cs11ons/ Mixer Batch 10C - 19.0 Callons/ Mixer Batch 100 - 19.5 Gallons / Mixer Batch 10E - 20.0 callons/ Mixer Batch 10F - 20.5 Gallons / Mixer Batch Notes for Table 10A - 10F I (v) 1. Drum volume accounts for plastic liner.
- 2. Calcf.um addition briad on 5,7 w/o nominal of cement, l_ 3.
Sodium silicate addition based on 12.4 w/o of water in sludge wash solution 4 Antifoam emulsion added at 0.57 to 0.76 ml/ gallon of sludge wash solution i
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WNS PCP.002 P Rev, 0, Draft B
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. m -. n CSS W.STE . STREAM RECIPE TABLES 10A THRO'H 10F
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,o 1 WVNS PCP 002-
,-o Rev. O Draft B TABLE 10A f-m _
{] CSS WASTE STREAM REC 7PE WASTE STREAM FORMULATION - 18 CALIDNS SUPERNATAtlT PER MIXER BATCH SP.GR (SOL'N) SOLIDS (SOL'N) GALLOPS (50L'N) NOM RATIO CaNO3 (1b)- NaSi (1b) MIN ANTIFOAM (ml) MAX ANTIFOAM (ml)
VASTE (SOL'N)-
(sec) (ENT(+CaNo3) ASTE
.A WASTE MIN CEMENT (+CaNo3) ,
MAX CEMENT (+CaNo3) MIN RATIO MAX RATIO (+Na&C4) hIN DRUM WT +Na&Ca MAX DRUM'WT +Na&ca I LB BATC!!/ MIXER DRUM %. Full SLURRY DENSITY l l: 1 ( l SAJ0057:3RM -11 1
WVNS-PCP-002 Rev. O, Draft B TABLE 10B CSS WASTE STREAM RECIPE WASTE STREAM FORMUIATION 18.5 CALLONS SUPERNATANT PER MIXER BATCH SP.CR (SOL'N) SOLIDS (SOL'N) CALIANS (SOL'N) NOM PATIO CaNO3 (lb) NaSi (Ib) MIN ANTIFOAM (ml) MAX ANTIFOAM (ml) LB VASTE (SOL'N) TIMER (sec) LB CEMENT (+CaNo3) MIN WASTE MAX WASTE MIN CEMENT (+CaNo3)
!%X CEMENT (+CaNo3)
MIN RATIO MAX RATIO (+Na&Ca) MIN DRUM VT+Na&Ca MAX DRUM WT+Na&Ca LB BATCH / MIXER DRUM % FULL SLURRY DF.NSITY O SAJ0057:3RM .I2
WNS PCP 002
..- .' Rev -0, Draft B TABLE 10C CSS VASTE STREAM RECIPE WASTE STREAM FORMULATION - 19.0 CALIDNS SUPERNATANT PER MIXEK EATCH SP,CR (SOL'N)
SOLIDS (SOL *N) GALLONS (SOL'N) NOM RATIO. CaNO3 (Ib) NaSi (lb)
-MIN ANTIFOAM (ml)
MAX' ANTIFOAM (ml) LB VASTE (SOL'N) n TIMER (sec) LB CEMENT (+CaNo3)
-MIN WASTE MAX: WASTE MIN CEMENT (+CaNo3)
A CEMENT (+CaNo3)
' MIN RATIO MAX RATIO (+Na&Ca)
MIN. DRUM V.'+Na&Ca MAX DRUM VT+Na&Ca-LB BATCH /hlXER DRbd % ULL SLURRY DENSITY SAJ0057:3RM WNS PCP 002 Rov, 0, Draft B s TABLE 10D
'v - CSS WASTE STREAM RECIPE WASTE STRFAM FORMUIATION 19.5 GALLONS PER MIXER BATCH
-SP.CR (SOL'N)
SOLIDS (SOL'N) CALLONS (SOL'N) DM RATIO CaNO3 (lb) NaS1 (lb)- MIN ANTIFOAM (ml) MAX ANTITOAM (M1)- LB WASTE-(SOL'N) TIMER-(sec)
~
LB CEMENT (+CaNo3) MIN VASTE MAX WASTE
-MIN CEMENT (+CaNo3) ;( y -, MAX CEMENT (+CaNo3)
V. : MIN RATIO MAX RATIO (+Na&Ca)
. MIN DRUM WT+Na&Ca MAX D2UM WT+Na&Ca LB BATCH / MIXER DRUM % FULL SLURRY DENSITY
'v SAJ0057:3RM le-
WVNS ?CP 002 Rev. O. Draft B a g TABLE 10E CSS VASTE STREAM RECIPE WASTE STREAM FORMU1ATION 20,0 CALLONS SUPERNATANT PER MIXER BATCH SP.CR (SOL'N) SOLIDS (SOL'N) CALLONS (SOL'N) NOM RATIO CaNO3 (1b) NaSi (Ib) MIN ANTIFOAM (M1) MAX ANTIFCAM (ini) LB WASTE (SOL'N) TIMER (see) LB CEMENT (+CaNo3) MIN WASTE MAX WASTE MIN CEMENT (+CaNo3) MAX CEMENTf+CaNo3)
-(
\-
MIN' RATIO MAX RATIO (+Na&Ca) < MIN DRUM WT+Na&Ca MAX DRUM WT+Na&Ca LB BATCH / MIXER DRUM % FULL SLURRY DENSITY l SAJ0057:3RM 15-l
WNS PCP 002 Rev. O, Draft B TABLE 10F CSS WASTE STREAM RECIPE WASTE STREAM FORMULATION - 20.5 CALLONS SUPERNATAltT PER MIXER BATCH SP.CR (SOL'N) SOLIDS (SOL'N) CALLONS (SOL'N) NOM RAITO Ca NO3 (1b) Na Si (lb) MIN ANTIFOAM (M1) MAX ANTIFOAM (M1) LE WASTE (SOL'N) TIMER (SEC)
# CEMENT + CaNO 3 MIN, WASTE KAX WACTE MIN CEMENT & CaNO 3 MAX CEMENT & sCs110 3 MIN RATIO MAX RATIO (Na&Ca)
MIN DRUM WT Na&Ca MAX DRUM WT Na&Ca
# BATCH / MIXER DRUM t DJLL SLURRY DENSIrs O SAJ0057:3RM __ - _ _ _ _ _ _ _ _ _ _ _ _ _ - _ _ _ _ _ - - _ _ _ - _ _ _ - _ _ - _ _ _ - - - - - - - - - - - - - - - - - _
F
~ ,
VVHS PCP 002 Rev. O, Isreft B
. (~') Actual full-eeale solidification is then conducted in accordance with ik_/ the Ceaent Solidification System Run Plan (attachment A).
The sequence of operations is as follows: o Decontaminacea vaste is added batchwise to the mixers from the recirculation line of the Waste Dispensing Vessel using the Waste Dispensing Pump, o The recipe quantity of Antifoam (OE AF 9020) is added to the mixer and the solution mixed at 2,000 rpm for 10 seconds, o The mixer speed is reduced to 1,000 rpm and cement / calcium nitrate addition is initiated. Metering of the proper amount of dry mixture into the mixer requires between 2 and 4 minutes, o At the end of the cement feed step, sodium silicate is added in a water based solution. The feed is accomplished with the mixer continuing to run at 1,000 rpm. Mixer speed is monitored. The addition requires less than 30 seconds. A mixing time of 60 seconds is counted from the end of the sodium feed to the opening of the dump valve, which is held open for 40 seconds to
-discharge the batch into the drum,
~3.6 Process Control System W _
('s ') _ Dae HS CSS PLC-(Programmable Logic Controller) controls the f- automatic solidification process. Three indepen,~nt subprograms L exist within the main program, one controlling mixer No. 1. one controlling mixer No. 2, the third controlling the fill nozzle and lid handler / turner with checks for proper drum positioning. This allows single or 2 mixer operation with no reduction in processing rate. The programs are arranged to permit only the correct operating sequences to occur. Events called for must take place in step or programs 'are inhibited and addition of any ingredient prevented. The PLC controls the additions of waste, Antifoam, and sodium silicate and mix time as specified by operator-controlled settings on the control panel. The DAS (Data Acquisition System) records weights at the direction
- of the PLC at appropriate program steps. The mixer programs allow repetition of waste and cement feeds in iner'. mental amounts should
' the weight of the charge transferred be low, as checked by DAS for recipe correlation during the process. l l n SAJ0057:3RM -17 l l
.= ,
WVNS PCP 002 Rev. O, Draft B
\
Valve V 2 which discharges liquid vaste into the mixers in the [l
\s- automatic mode has been tested and shown to give a 99 percent contidence factor by a regression analysis. The HS CSS controller provides checks to maintain this accuracy. Among these checks are:
o BefoIe any V 2 operation is allowed, its position indications of "open" and "closeu" are checked for nonsimultanaous location, o To allow V 2 operation, recirculation loop flow must be equal to or greater than 97 percent of expected nominal flow, o When called upon to open or close, valve response time is monitored and if not proper, the Waste Dispensing Pump is stopped and program is - terminated, o If valve V-14 is not directed to mixer 1 and 2 as called for, the program is inhibited, preventing double batching of one mixer, o Timing of-valve opening is controlled to within 0.1 second. Typical time settings are in ran es of 12 to 14 seconds.
-o The cement mix time sequence is not a variable. It is sat and not changed during processing.
The addition of the sodium-silicate additive is controlled by an air operated piston pump; tl.a total volume charged to a mixer is y controlled by_ counts of pump strokes by the PLC. Settings are made
-(' by the operators on the control panel based on the recipe requirements. The pumps have been calibrated for a specific discharge per stroke. Out-of-range-charging vill be alarmed by the DAS,-based on mixer weight increase measured by load cells.
1( control logic diagram for the HS CSS control system is shown in Figure 1.
- 3. 7- CSS Data Acquisition System The CSS Data Acquisition System (DAS) is used to document the processing of aach vaste drum and of each mixer batch that went into the vaste drums. The DAS accepts signals from the mixer load cells,
- the dry cement metering system, drum dose race monitor, and bar code reader. The DAS also accepts digital signals from the HSCSS control system to record weight readings for waste and cement at the proper time in the process. Note that back up-data is manually taken as part of the UVNS Standard Operating Procedures.
l' SAJ0057:3RM 18-l
, ._ _ . . . _ . . _...__.m-. ._.. ._..__ ... _ _ _ _ _ . _ _ . _ _ . . . . .___m_..____. . _ _ .
WNS.PCP 002
.-,- Rev. O. Draft B Insert Figure 1
)
e l' l l (. i SAJ0057:3RM O l- j l' l
VVNS PCP-002 Rev. O, Draft B The Data Acquisition System also is ured to insure that each mixer O batch is within acceptable limits, as detereined by the qualified recipe parameters for min / max waste weight and min / max water to czment. ratio. If any one of these parameters is outside the acceptable limits for the mixer batch, che DAS will alarm and alert the operator. At this point, mid stream manual corrections for such conditions as low waste weight or high water to cement ratio may be made, while maintaining automatic control, thus assuring that each mixer batch and each vaste drum conforms with the qualified recipe. Final drum weight is calculated and recorded by the DAS as the sum of the recipe constituents. A real time display and printout of all major process steps and alarm conditions is generated using the DAS (an IBM Industrial AT microcomputer system). In addition, the DAS maintains files for all drums made during the course of production. An online display exists to allow instant display of drum / mixer weights, water to-cement ratios, overpacks and dose rates of any drum monitored by the DAS. A weekly activity file is maintained on disk in order to identify drums made during an operational period. These ASCII formatted drum records may be copied to diskette during nonoperational periods and placed in spreadsheet form for further off-line analysis. The following is a brief summary of the DAS accuracy in calculating drum weight.- () 1. The-DAS retains the empty
- mixer weight reading from the previously weighed batch.
VARIANCE: Accuracy of mixer load cell (+/ 3 pounds).
- 2. The DAS first calculates the weight of the added waste. It.
takes the alxer reading after the wasts has been added, and subtracts the empty mixer weight (from step No. 1.). VARIANCE: Accuracy of mixer load cell (+/- 3 pounds). 3, The DAS then obtains the weight of the added cement / calcium nitrate from the Acrison System (direct loss-in weight reading from the cement day bin). i VARIANCE: Accuracy of Acrison (+/- 2 pounds).
- 4. The Antifoam agent is ther added. The weight for_this additive is not computed, as only 10 to 15 millilitres per batch is used.
VARIANCE: Minor i Empty mixer weight plus any remaining mix. SAJ0057:3RR l l l l
WVNS PCP.002-Rev. O Draft B [ 5. The weight of sodium sili.: ate added is- calculated from its density and the volume added as determined by HS. CSS pump stroke data. VARIANCE: Accuracy of pump stroke times the number of strokes +1/2of a stroke (t 1 pounds) NOTE: 0.15 litre / stroke and 5 litres required per batch. Periodic calibration of these pumps is performed as well as trending analysis.
- 6. After mixing is complete and the batch is dumped from the mixer to a drum, the empty
- mixer weight is read.
VAR;UTCE: Accuracy of mixer load cell (+/- 3 pounds).
- 7. DAS calculates the batch weight as follows:
BEGINNING EMPTY MIXER WEIGHT (step 1) + TOTAL WASTE WEIGHT (step
- 2) + TOTAL CEMENT WEIGHT (step 3) + ADMIXTURE (step 5) (-)
ENDING EMPTY MIXER VEIGHT (step 6).
- 8. After both batches have b n added to the drum, the DAS ip\
calculates the total drum weight as follows: BATCH *1 UEIGHT + BATCH #2 WEIGHT + TARE DRUM WEIGHT (CONSTANT) A potential variance of 9 pounds per batch is possible: Load cell reading two times 2x3- 6 Acrison reading one time 1x2- 2 Admixture one time 1x1= 1 A potential variance:of pounds per total drum weight is possible: Two batch readings per drum 2x9- 18 Variance in empty drum weight - 5 Based on 20. gallons of waste / batch, average net mix would be about 900 pounds. Using highest drum weight variance (23 pounds), percentage of error is 2.6 percent. Empty mixer weight plus any remaining mix. m SAJ0057:3RM f 21-
! )-
_ . . ._ _ _ _ _ _ .._ ._ m >_mm . ~ . u .
-, x
, ~
fWVHS 1:P 002 3 Rev. O Draft B 1 NOTES: 1, Mixer being' rerd ha.s no movement variance of scale is 4()s~gzi
? :+/ 3 pounds.
;N-<jL
- 2. Effect of mixer 1 (mixing) on reading of mixer 2 (no
- movement of mixer 2) is +/ 3 pounds.
- 3. Variance if reading scale while mixer is mixing is +/-
4 pounds. 4 . Accuracy and reliability of the dry cement metering system (Acrison feeder) and Waste Metering Valve (V 2) was experimentally determined to be > 99 peteunt.
- 5. Empty drum weight has-a potential variance of +/-
- 5 pounds.
4.0 REQUIREMENTS FOR SAMPLE VERIFICATION The tanks which-fecd'the waste dispensing vessel'are sampled using an s installed sampling system designed to provide a representative sample of the tanks. The samples are delivered to the Analytical Laboratory where they are analyzed for: o Total dissolve'd solid content, o1 Specific-radionuclide' analysis _for waste classification,
'o- pH , _
o -Sulfate
.i
' '~ o Density, and-o Presolidification compressive strength.
These measurements'are used to ensure that the waste to be processed at
~ _the CSS lis - compatible with the. reference ' formulation. In addition to
- these: analyses. a sample of the waste is solidified using.the reference recipe to assure that a dry, solid final waste form can be produced in theffull-scale system. The sample solidification verification f requirement's and procedures used are discussed in sections 4.0 a-d 5.0,-
respectively. 4.1 1.aboratory Safety
~
4.1.1 All' safety precautions outlined in Analytical Chemistry Procedure (ACP) 7.2 " Laboratory Safety" must be followed. 4.1.2 While working with radioactive material, ACP 7.4 " Handling
-Radioactive Materials" must be followed.
'4 . 2 Prerequisites
-4.2.1 ' Representative samples of the decontaminated sludge wash, one-sample per nominal 5,000 gallons of waste to be processed is
, required. (A batch consists of the combined contents of Tank
) SAJ0057:3RM d I /
L VVNS.PCP 002 l Rev. O. Dreft B
,- s. SD 15Al and 50-15A2.) Two samples are obtained from SD 15A1,
; )' one when the tank is full and one at half capacity, and one
'/
sample is obtained from 3D lSA2 when it is full, af ter the tanks have been sufficient 1 mixed
/ to ensure a homogeneous mixture.
4.2.2 Chemical and radischutical analyses are performed te include the following: A. Gross alpha and beta B. Gamma scan C. Total solids (TS) D. Density (p) E. pH F. Radiochemical analyses for ra411 des listed in .0CFR61 C. Sulfate The analyses will be checked for mutual self-consistency. 4.2.3 Equipvent required for test specimen preparartons. A. Sample curing oven, thermostatically controllable in the range of 70 C t 5 C equipped with a calibrated temperature sensing device (Thermocouple) . B. Metler top loading balance sensitive to the nearest 0,01 fs gram with a loading capacity of at least 1,200 grams.
'~
C. " Lighting Lab Mixer" equipped with variable speed control, watt loading, automatic timer, and high sheer mixing blade. D. ASTM certified 2 inch cube cement molds. E. Various containers and glassware ae required. F. Calibrated compressive strength testing instrument. G. Chemicals
- 1. Portland Type 1 cement / calcium nitrate mixture obtained from operations.
- 2. Antifoam agent CE AF 9020,
- 3. Sodium silicate solution Silica to soda ratio 3.23 t .05 Water 62 t 34 Na20 9.0 t 0.1%
SiO 2 29.0 t 0.2%
,~ s SAJ0057 : 3Eut t
' 23-Q,ls 6
- e. .
WVNS PCP 002 Rev. O, Draft B (p) 4,3 Sample Acceptance Criteria To ensure that an acceptable solidified waste for= has been produced, the technician shall verify that all acceptance criteria are met as follows: 4.3.1 Visaal inspection of the sample after pauring into the mold to look for any separation of liquid on the surface. If separation occurs, estimate how much and when the liquid separated. Observe the liquid and check for readsorption. If readsorbed, record when. (Product Requirement) 4.3.2 Visual inspection of the 2-inch cube after the cure period shows that a firm dry monolith has formed, and that no degredation (cracking or spalling) has occured. 4.3.3 Compressive strength (ASTM C 109) of the 2. inch cube exceeds TBD psi. (Product Requirement) 4.3.4 Pourability of the mixer is such that retention of product in the mixing :ontainer is minimal (<5 percent of constituents). 4.3.5 Celation is centrolled to occur not more than 90 minutes following the pour. (Product Requirement) This range of gel times allows a sufficient amount of gelation prior to (} s,,- transporting the drums of encapsulated waste to the drum cell. l l I In the event that presolidification cannot be achieved within the qualified recipe range, the_ process will be stopped. At this point, further qualification testing would be required prior to proceeding. 4.4 Requirements for Sample Verification 4.4.1 Verify that all materials and equipment listed in Section 4.2.3 are ready and available to use in the Radiochemistry Laboratory. 4.4.2 Refer to Section 5.0 as applicable when conducting sample verification. Use the Solidification Data Sheet, Figure 1, for all sample solidifications. 4.4.3 Sample Requirements l A. A sample shall be solidified prior to full-scale solidification of waste. j .. l SAJ0057:3RM 24-(('"' l-
VVNS-PCP 002 Rov. 0,-Draft B B. If no additional material has been added to the hold tank (-~)
_(5-D 15Al or 15A2) after the sample was taken, aolidified test specimen is considered representative of tank contents. Note: An additional sample will be removed from 5 D 15Al at 50 +10 percent level and used as an in process check for an additional cube sample verification.
C. Test specimen sample solidification will be performed, thereafter, on each new hold-tank batch of waste to be processed. D. The technician shall verify that the semples used for the three 2 inch cube specimens are representative of the homogeneous waste samples obtained from the sparged 5-D-15Al or 5 D 15A2 hold tanks. 5.0 SAMPLE VERIFICATION PROCEDURE 5.1 - Operations group will provide the laboratory with 150 mL representativo sample of decontaminated sludge wash from either of the feed tanks SD15A1 or 3D15A2, 52 Upon receipt of sample, visually inspect sample for precipitates, insoluble phases or nondissolved suspensions, and record observations on worksheet (figure 3). In the event that undissolved
~ ,f{} solids are found, the process will be stopped. Mix the sample i ,/ thoroughly and remove sample for Chemical and Radiochamical analysis using the following Analytical Chemistry Methods (ACM):
NOTE:
' THIS METHOD 01DCY WILL BE USED UNTIL SUFFICIENT EXPERIENCE AND DATA ARE AVAILABLE TO ESTABLISH WASTE CLASSIFICATION BY KEY ISOTOPE RATIONS. THE DECISION TO UTILIZE RATIONS VERSUS SPECIFIC ISOTOPIC ANALYSIS WILL BE MADE BY THE MANAGER, ANALYTICAL AND PROCESS CHEMISTRY.
5.2.1 Measure gross alpha and beta by ACM Cross 1201 5.2.2 Measure Sb-125, Cs-137, Am-241 and Co-60 by ACM-Gamma-3101 5.2.3 Measure Tc-99 by ACM-Tc.99-4001 5.2.4 Measure H-3 by ACM H 3-4301 and EM-13 5.2'5. Measure total Plutonium by ACM Pu-2701 5.2 6 Measure Sr 90 by ACM-Sr-3001 ( SAJ0057;3RM k-
l WNS PC*-002 j Rev. O Draft B 5.2.7 Measure TS by ACM TS/TDS 2502 5.2.8 Measure density by ACM Den 2401 5.2.9 Measure pH by ACM pH 2601 5.2.10 Measure hulfate by TBD 5.2.11 Total Carbon by TBD 5.3 Ratio the following radionuclide accordin6 to the best data available for rationing (Ratios originally established by Rykken, DOE /NE/44139 14 (DE87005887] "High Level Vaste Characterization of West Valley", dated June 2,1986. ) (and TBD) 5.3.1 I 129 ratio to Sb 125 5.3.2 Ni-59 and 63 ratio to Co-60 5.3.3 cm-242 ratio Am 241 5.3.4 C-14 to total carbon 5.4 Prepara a lab scale sample of sufficient size to make a two inch cube using the cement / calcium nitrats mixture, antifoam emulsion and sodium silicate used in the plant. The lab scale recipe must be rigorously scaled down from the plant recipe for producing the waste form. 5.5 The cement is to be prepared per ACM Cem Prep -4801, preparation of 2-inch square cubes for compressive strenBeh testing. 5.6 Place 2-inch cube mold and sample into cure oven; record oven temperature and time on solidification data sheet. 5.7 Cure sample for a minimum of 24 hours. 5.8 Visually inspect the sample after the cure period in the oven. The sample must be a firm solid cube with no physical degredation and with a compressive strength of greater than TBD psi. SAJ0057:3RM 26-1 l l
WNS PCP 002 Rev. O. Draf t B INSERT FIGURE 2- page 1 of 4 Analytical Request SD15Als O SAJ0057:3RM O 27
.g.. . , .
WNS PCP 002 Rev. 0. Draft B INSERT F' JRE 2 page 2 of 4 Analytical Request SD15Al# O f l l SAJ0057:3RM !~O l t- [- i __
. . - . . .~ .... . . . .. .- . - . . -... - . - .-. .., - - ._. .. .. - ~. - - - ..- - - . . . . _ . .
WNS.PCP 002 Rev. O, Draft B INSERT FIGURE 2 page-3 of 4 Analytical Raquest SD15Al# 1 s r S 4
. SAJ0057:3RM 29
. . . . . . . - . . , - . . . - . . . _ . . . . ~ - . . . . - . ~ . . . - . . - . - - - . - . . . . - ~ . - - . . . . . -
- . = -
'e' WNS PCP 002 <
l Rev. O, Draft B : I INSERT FIGURE'2- page 4 of 4 Analytical Request
- SD15Als ,
i I A l l. l t l '. l SM0057:3RM , _ - _ , _ _ , . . - . . . . . , . . . - .
i , WVNS.PCP.002-Rev. O. Draft B i. [l FICURE 3
- (f Solidification Data Sheet Sample Log No. Time and Date Sample Taken:
Tank Sampled Cross alpha uCi/g TS 4 Cross beta uCi/g Density g/mL Cs-137 uCi/g pH SU SO 4 ug/g Decontaminated Supernatant Voluee mL Weight of Cement / Calcium Nitrace mixture grams Antifoam Volume mL Sodium Silicate- mL Water to Cement Ratio
/ Time Sample Produced b' Cure Oven Temperature C Cure Time , hours Solidification Results:
Free Liquid Volume mL Physical defects present: Yes No- psi
-Compressive Strength - 24 hour cure psi Obse rvations : ' (Including pourability, gel time, visual inspection and others as detected.)
Sample prepared by: Date:
+Results Approved: , Manager Analytical Laboratory Date: /"%
(s,) SAJ0057:3RM 31
=r ,
- WNS PCP 002 Rev. O. Drafe B
.O INSERT FICURE 4 PRESOLIDIFICATION VERIFICATION FLOWCHART O SAJ0057:3RM .
=m- - +-- c -- ' - - g+ w
.. ? .-.
. VVNS PCP 002
( -, Rev. O. Draft B f.
!., _,/ . ATTACHMENT A TO SOP 70 33 Copies to: QA upon completion of campaign.
CEMENT SOLIDIFICATION RECIPE INPUT DATA OSR/TR-IRTS-2 Concentrates Tank (5D15A1 or 5D15A2) Lab Analysis Log Number (attached) Batch Size (Gallons) Minimum Mixer Liquid Weignt (1bs) Maximum Mixer Liquid Weight (lbs) Minimum Sodium Silicate Wei6 ht (1bs) Nominal Sodium-Silicate Weight (1bs) Maximum Sodium Silicate Weight (lbs) Percent Water In Waste Slurry Specific Cravity - Minimum Mix Time (secs.) Minimum Water /Coment Ratio Nominal Water / Cement Ratio V-2 Timer Setting *. k Acrison Set-Point Antifoam Pump Timer Setting NaSi Pump Setting (strokes) PROCESS CONTROL ENGINEER /DATE VERIFIED BY , SS/PCE
* - If V 2 setting is changed to accomodate processing, denote new setting and initial-drum affected.
/Nc SAJ0057:3RM N,
y
.- VVNS-PCP 002 Rov, O. Draft B gs 5.9 The CSS Shift Supervisor will be given a copy of the analytical
'- request fonn showing the performance of the waste form to this point, which will allow processing of the batch of waste.
5.9.1 Shift Engineer reviews all data including gel time, and the following Technical Requirements:
- a. TR IRTS TBD: Cs-137 concentration T.BD
- b. TR IRTS-TBD: -
Completion of presolidification testing to ensure compressive strength greater than TBD psi.
- c. TR-I.TS TBD CSS Cement Recipe
- d. Total Pu: TBD
- e. Sulfate Sog: TBD
- f. TDS: TBD 5.9.2 If satisfactory, the Shift Engineer completes the Recipe Input Data Sheet-(SOP 70-33).
NOTE: IF THE COMPRESSIVE STRENGTH OF A CUBE SAMPLE IS BELOW TBD PSI, THEN A VIOLATION OF WVNS TECHNICAL REQUIREMENT OSR/TR IRTS 8 OCCURS. PROCESSING WILL NOT PROCEED. A CRITIQUE WILL BE HELD TO INVESTIGATE THE CAUSE OF THE LOW COMPRESSIVE STRENGTH, AND ALL WASTE FROM THAT BATCH WILL BE CONSIDERED SUSPECT. A NONCONFORMANCE REPORT WILL
' [) AGAIN BE ISSUED, \_ /
ALL DRUMS FOUND 10 BE OUT-OF SPECIFICATION WILL BE HANDLED IN ACCORDANCE WITH SECTION 3.3 0F THIS PROCEDURE. 5.13 The gel time of the first full scale drum from each lot will be verified by visual inspection. If the get time of the full-scale product is less chan 90 minutes, processing may proceed. If the gel time of a full-scale drum is greater than 90 minutes, the process will be stopped, and an Occurrence-Report will be completed per WV-987. Processing may or may not be resumed, based on a technical evaluation of processing variables, including, but not limited to: water to cement ratio, source of cement /CaNO 3 blend, CaNO3 content in the blend, NaSi addition, etc. 6.0 FULL-SCALE SOLIDIFICATION 6.1 Calculation of Full-Scale Formulation The constituents for the full scale recipe on a unit basis are identified in Section 6.2 for decontaminated sludge wash. The recipe is verified for each batch of waste collected following evaporation in-5-D-15Al or -15A2 as described in Section 4.0 and
,A SAJ0057:3RM ~L k
- WVNS PCP 002 Rev. 0, Draft B r- 5.0. The decontaminated sludge wash solution has been demonstrated
(' to be homogeneous during preoperational testing and the need for recipe changes is considered unlikely. Note that the CSS Vaste Dispensing Vessel (400 gallon nominal capacity) is recirculated at 80 CPM. Homogeneity is, however, verified by chemical and radiochemical analyses in conducting routine verification of solidification. Following verification in the laboratory, the Shif t Engineer selects a full-scale recipe depending on the batch size to be processed from Tables TBD. These recipes are all based on the standard recipe varying in percent of drum fill only. The recipe utilized is documented in the shift log and during processing; process limits are controlled to within the permitted variance stated in the recipe. In the event that the sample cannot be solidified using constituents within the allowed recipe variance, full-scale proceusing is secured and the Operations Manager is notified, Full scale solidification is not permitted until the recipe is resolved. 6.2 Full Scale Fo rmula tion The following full scale reference formula vill produce a dry solid monolith capable of p.rformin6 in accordance with the 10 CFR 61 requirement for stablized LLW. The data are provided for one gallon of waste:
'~N ./ o Decontaminated supernatant gallon ' \,,) (at 20 w/o nominal total dissolved solids) o Portland #1 cement with nominally 5.8 w/o pounds Ca (NO3 )2 preblended o Silicon Based Antifoam to mL additive GE AF-9020 o Liquid Sodium Silicate pounds 6.3 Full Scale Formulation Control Laboratory verification of the full-scale formulat!"a is described for each batch of waste to be processed in Section 4,0. Calculation of the recipe based on the laboratory verification is discussed in Section 6.1 and the run plan, attachment A. Process control and full-scale recipe data recording are discussed in Section 3.6.
Vaste classification is based on the isotopic content of the decontaminated sludge wash as determined by the analytical methods described in Section 5.0 and the total drum weight as recorded in the Data Acquisition System (Section 3.6). O SAJ0057: 3RM m ,e4 __ n, u,. A_. WNS PCP 002
, Rev. O, Draft B
- t 7.0 RECORDS, DOCUMENT CONTROL, AND QUALITY ASSURANCE T_ V( Sample verification is performed in the Analytical Laboratory using approved Analytical Procer'ures and Analytical Methods. Decontaminated sludge wash concentrate samples are withdrawn from either tank 5-D 15Al or 5-D 15A2 and are delivered to the laboratory for analysis (specific analyses are described in Section 4.0 and 5.0). The sample identification number is assigned by the Analytical Laboratory and is logged in according to sample receiving procedures. The required analyses are performed (see Sections 4.0 and 5.0) and the data recorded on analytical data sheets for radiochemical anal sis and on the Solidification Data Sheet for sample solidification verif! cation. All data sheets are reviewed in accordance with Analytical Chomistry Procedure, ACP-5.1. All analyses are performed in accordance with approved procedures and under the Analytical Quality Assurance Program. Copies of the Analytical Data Sheets are delivered to the CSS Shift Supervisor. The Shift Engineer reviews all data and calculates the recipe to be used for the decontaminated waste batch to be processed. The Shif t Engineer and CSS Shif t Supervisor sign the Recipe Input Data Sheet (SOP 70 33) and attach the corresponding Analytical Request Forms, prior to processing the batch. The Analytical Sample Log number is recorded in the shift log. The recipe is calculated by the shift engineer using the calculation she.et contained in the shift log. The recipe talculation for a single tank's volume of waste will remain
. unchanged for a nonnal processing week because of the capacity of the g sampled tank (about 5 10,000 gallons) and its homogeneity. Since the L waste is homogeneous, recipe changes during any processing week are not e.nticipated, although, slight variation in the recipe within the limits provided in approved recipes (Tables TBD through TBD) is permitted. The recipe calculation is reviewed and approved by the Shift Supervisor if the full-scale recipe is determined to be within the recipe variances allowed. If the recipe is calculated to be outside the allowed variance, full scale solidification is not permitted to proceed and the Operations ManaSer is contacted for resolutior Periodic quality assurance survei) .a ce of the log book sheets, solid' fication operations and ana -ical work is performed to assure that the calculations are performed cortectly and in accordance with approved procedwees.
The Analytical Data Sheets are controlled in accordance with the Analytical Laboratory Document Control Procedures. The operating log book contains uniquely numbered pages for each day of operation. These logs are retained in the shift office during use and are retained by the Plant System Operations Document Control group when completed. All records are available for retrieval if necessary. Data Acquisition System (DAS) output contains a processing record for each drum produced at CSS. Records are also maintained through the WDP Master Records Center. Each drum produced is classified by the W ste SAJ0057:3RM VVNS.PCP.002 Rev. O. Draft B l Disposal Operations group using radiochemical analysis data as described ('~ in Section 5,0 and the drum weight as calculateo by the DAS. The waste classification methodology is controlled by Standard operating Procedure 9 8, Vaste Classification. Classifica. tion records are retained for each drum by the Vaste Disposal Operations group. The DAS output is retiined by Operations Document Control in accordance with Standard Operating Procedure 001, " Control of Work Instruction Documents". Individual drum data sheets are transmitted to Vaste Disposal Operations in accordance with Standard Operating Procedure 9 2. "Felid Radioactive Umste Disposal *. A complete data rackage for each drum will be , maintained in accordance wit.h SOP 70.TBD. 8.0 tut.1..SCAlf DRUM TESTING In addition to the sample verification described in Section 4.0 and 5.0, full scale verification of solidification is also planned. One drum per process tank (based on the observed consistency of the process) will be sampled at randos to verify predicted fill as calculated from recipe canstituarsts (see Tables TBD.TBD) absence of any free liquid and penetratl)n resistance following a 3 day cure. The objective of these tests is to confirm successful solidification in the full scale waste
' form, confirming the sample solidification results. Deficiencies observed in the full scale vaste will prompt further investigation of drums produced from a given waste batch.
During production of the full scale waste fore, one drum per production process tank is placed into a test fixture located in the Process Cell. O The drum is allowed co cure and is inspected foi fill height, free liquid cnd pene" ration resistance. An Inspection Data Sheet is prepared in
.accordance with SOP 70 40 inspection procedura rui forward?d to Operations in accordance with SOP 00 1, attachm,st B 1. The testing'will be done in accordance with the run plan. \
SAJ0057:3RM 37
VVHS PCP 002 Rev. O Draft B ATTACHMENT A CEMDT SOLIDII'ICATION SYSTEM RUN PLAN IUR S1 EDGE WASH LIQUID TABLE OF CONTENTS Pa r.e 1.C INTRODUCTION............................................. .......A 1 2.0 OBJ ECTIVES . . . . . . . . . . . ...... .................... .... ..........A 1 3.0 SAFETY..... .......... ..... ......... ........ ...... .. .......A 1 3.1 Industrial Safety.......... ......... .. .. . .. ..... ...A-1 3.2 Radiation Safety............................... ............A 1 3.3 0SR's......................... .......... .. ........ . ....A 1 4.0 EQUIPMENT.... ........ .............................. ...........A 2 50 REFERENCES. ............................ ............. ..........A 2 6.0 VASTE TRANSFERS......................................... . .....A 4 7.0 CSS OPERATIONS............................................. .....A 4 7.1 General System Operations............ .............. ...A 4 7.2 Waste Recipe........................ ........ ........A 6 7.3 Mixcr Flushing and Flush Processint- ..................A 6 7.4 Sys ters Flushing. . . . . . . . . . . . . . . . . . . ..................A 6 7.5 Conduct of Operations . . . . . . . . . .. ... ............. ...A 7 8.0 alESPONSE TO EMERGENCIES.,.................................... ...A 7 8.1 Waste Transfer...................... ............... ......A 7 8.2 Vaste Processing in Automatic............... ...............A 7 8.3 Vaste Prer ting in Manual.... .. ......... . .. . .. ......A 8 8.4 Flushire >
'.ush Processing....... ... ..... ............A 8 8.5 D ru's S v n ..;, and Lo a dou t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A 8 8.6 Loss al Ventilation............... .. .........., .. .. ...A 8 8.7 Loss of Electric Power. .. .......... .......... ....... ...A 8 9.0 QUAI,ITY ASSURANCE AND RECORDS MANAGEMENT............ ,....... ...A 9 9.1 Sample Verification Data Sheets....... .....................A 9 9.2 Log Book Records...... ....................... .............A 9 9.3 DAS 0utput..................................................A 9 9.4 Full Scale Drum Testing........... ....... ... ......... ..A 10 SAJ0057:3RM A-1
' WNS PCP 002 Rev. O. Draft B ATTACIMENT A TAB 12 0F CONTDCS (continued)
Page
- 10. 0 PREVDU1VE MAINTENANCE AND CALIBRATIONS . . . . . . . . . . . . . . . . .. .....A 11 10.1 Preventive Maintenance....................................A 11 10.2 Calibration.................. .. ..... ..................A 11 ATTACIMENT Al Reference Recipes for Sludge War.h Liquid... . ....A1 1 _.
4 ATTACIMENT A2 Run Plan Graphic..... ............. ...... .. ... . ..A2 1 .a SAJ0057:3RM A.it
WNS PCP.002 Rev. O. Draft B ATTACHMDIT A CJMDir SOLIDIFICATION SYSTEy RUN PIAN 1.0 InnODUCTION This Run Plan addresses the procedures, equipment, and controls necessary for proper operation of the Cement Solidification System. 2.0 OILIEcrIVES The objective of the CSS is to solidify decontaminated sludge wash solution processed by the LVTS with cement to produce a vaste form meeting the requiretuents of 10Cilt61. 3.0 SAFETY 3.1 Industrial Safety O Safe operation of this system is the responsibility of the CSS operating personnel. Control will be effected through the use of approved SOP's. 3.2 Radiation Safety All operations will be performed in accordance with the latest revision of the WNS Radiological Controls Manual, WDP 010 and operating proceduras, 3.3 OSR8 a Operation will also be conducted within limits and conditions set by the Operational Safety Requirements. OSR requirements are indicated O S AJ0057 : 3s.M A1 1
VVNS.PCP.002 Rev. O. Draft B ATTACllHENT A (continued) in the SOP's, shift log data sheets and the Run Plan Graphic (attachment A2) which is posted in the control room. 4.0 175TilHIN_T The following equipment shall be available in the area dering CSS operatious: A. Tool box with assorted hand tools B. Drwn pallets C. Anti C clothing D. Respirators 5.0 RfffGt13CFS O A. Process Control Plan, WNS PCP 002 B. Cement Solidification System Safety Analysis Report, SAR Volume IV C. Design Criteria D. Standard Operating Procedures indicated in the following listing: SOP 70 1 Vaste Transfer to CSS SOP 70 3 Automatic Solidification Operation SOP 70 4 CSS Manual Solidification with the Process Logic Controller Operational SOP 70 5 t,ravimetric Feeder Operation SOP 70 6 Bulk Cement Transfer to Dry Bin SAJ0057:3RM A2
____ . . _ _ _ . _ __ _- -_ _ _ _ - _ - - _ - - . _ . - _ _ - _ _ _ _ _ ~ VVHS.PCP.002 Rev. O. Draft 8 ATTACHMFJTT A (continued) 5.0 REFERENCF.S (continued) l O1 SOP 70 7 Cement Truck Unloading l S0P 70 8 Clean Drum Handling for CSS SOP 70 9 Automatic Drum Operations for Cement Solidification System SOP 70 10 CSS Drum /Overpack Handling SOP 70 11 CSS Manual Operation with Process Logic Controller Nonoperational SOP 70 12 CSS Mixer System Flush Operation SOP 70 14 01 14 Building Ventilation System SOP 70 7) 01 14 Building H&V filter Change SOP 70 16 Filter Change Rc.om Filter Change SOP 70 17 Manual Drum Operations for CSS SOP 0 18 Alarm Procedure for CSS SOP 70 19 CSS r.mergency Procedure Power Failure 50P 70 25 Calibration Procedure for CSS Cravimetric Teeder
,-. SOP 70 31 CSS Drum conveyor Alarm Responses SOP 70 32 Operation of the CSS Silo Air bryer 50P 70 33 Data Acquisition System Operation SOP 70 34 Operation of the 01 14/ CSS Process Room 4. Ton Bridge Crane SOP 70 35 Operation of the Maintenance 2 Ton Bridge Crane SOP 70 37 Smear Robot Operation SOP 70 39 Draining and Flushing the Vaste Dispensing Vessel SOP 70 40 Full Size Testing of Solidified Product SOP 70 41 CSS Preventive Maintenance Program SOP 70.TBD Vaste Certification Run Plan Craphic Drawings 9000.TBD. Sheets 1 and 2 O S AJ0057: 3RM A3
T
- VVNS PCP 002 Rev. O, Draft B ATTACHMENT A (continued)
U 6.0 UASTE TRANSFERS Vaste transfers to the CSS will be made as required using SOP 70 1. The batch siae transferred to the Waste Dispensing Vessel will be approximately 400 gallons, which is enough to produce about ten (10) drums of solidified waste. The waste will be sampled prior to the first transfer at 5 D 15A1 or 5 D-15A2 in accordance with the Process Control Plan. The sample will be assigned a sample log number when it is received at the Analytical Laboratory and will be analyzed for it's chemical and radiochemical composition i'.. accordance with the Process control Plan. A portion of the sample will be solidified to verify that use of the reference recipe will result in solid dry menolith with appropriate compressive strength. The analysis results and Solidification Data Sheet will be sent to the CSS shift office; using the solidification sample verification data sheet, the shift engineer will selec: an approved full scale recipe from attachment Al and document the
~~ calculation in the shift log book. Full scale solidification will not be
, initiated without acceptable verification of solidification in the laborato ry .
Due to its larger operating volume, tank 5D15A1 is sampled prior to solidification and at 50 parcent + 10 percent level as at. in process check. 7.0 CSS OPERATIONS 7.1 ceneral System operations Prior to initiating transfers to the Vaste Dispersing Vessel, verification of solidification for a sample of waste to be transferred and recipe calculation for the full scale pre.'at must be completed. O C l l SAJ0057:3RM A4
I. .
,' VVNS PCP 002 Rev. O. Draft B ATTACHMENT A (continued)
O d 7.1.1 Vaste may be transfer-ed to the Waste D!spensing Vessel frois either Concentrates Storage Tanks 5 D 15A1 or 5 D 15A2 while the solidification process is ongoing provided that solidification verification was performed on a sample of the waste being transferred prior to initiating the transfer. Transfers are made just prior to reaching the low level alarm pofat in the Waste Dispensing Vessel. At that point, sufLeient volume remains in the Waste Dispensing Vessel to continue processing for 40 minutes. Three (3) or four (4) transfers will be required per shift. Vasta transfers are performed in accordance with SOP 70 1 7.1.2 Drums will be tested for surface contaminat an prior to release to the Drum 1.oadout Area. Drums released to the Drum Loadout Area must have smearable surface contamination levels less than 50 dpa/100 cm2Alpha and less than 500 dpm/100 cm2 Beta contamination. All drums with greater amovats of reinovable contamination will be decontaminared. Contamination testing of packages is performed 1n accordano with SOP 7') 37. The top, sides, and bottom will bs tested. 7.1.3 Two (2) mixers will normally be used for waste processing using SOP 70 3. 7.1.4 Prior to any extended shutdown of the process, the mixers will be flushed to a decant drum using S0P 70 12. 7,1.5 As oight (6) drums are staged in the Drum Loadout Area, the drums will be loaded out by Waste Operations and transported to the RTS Drum CeM. All drums will be labeled with an individual bar code serial number. All drum data: production recipe, date filled, weight, dose rate, surface contamination l SAJ0057: 3RM A5 1
WNS PCP 002 Rev. O, Draft. 8 ATTACHMDIT A (continued) level, etc., will be cross referenced to this bar code serial number and recorded by the Data Acquisition System (DA$). Drum production records as recorded by the DAS will be retained by Operations Document Control in accordance with SOP 00 1. Individual drum data sheets are transmitted to Vaste Operations in accordance with SOP 9 2. 7.1.6 All drum records including processing data, waste classification data sheets, and DAS data will be compiled into a vaste certification package in accordance with SOP 70 TBD. 7.2 Vasta Recipe The decontarainated sludge wash solution will be solidified in the CSS in accordance with CSS SOP's. The approved recipes are shown in Table 1. Recipe verification is discussed in Section 6.0. As an operator aid, a graphic is included in attachment A2 showing the process flow, process procedures, operational safety requirements, product quality requirements and process requirements. 7.3 N!.xer nushing and Flush Processing Flush operations will be conducted using SOP 70 12. 7.4 System M ushing If necessary for maintenance, the system may be flushed. 7.4.1 The Vaste Dispensing Vessel is flushed and drained in accordance with SOP 70 39. . 7.4.2 The mixers are flushed in accordance with SOP 70 12. a i SAJ0057:3P3 A6
- - -. - -_ - _ _ _ . .. - -._-. - . _ ~ . . _ . . _ _ _-. . - . . _ - _ _
WNS PCP 002 Rev. O Draft 8 i ATTACHMENT A (coatinued) 7.5 conduct of Operations A Shift Engineer and a CSS Shif t Supervi.sor will be on each shif t to l assure safe and technically correct operation of the cepent Solidification System. Technical direction of the work is the responsibility of the Shift Engineer, all direction provided to the operators or Maintenance personnel will be made through the CSS Shift Supervisor. In the event of any casualty or emergency situation, the CSS Shift Supervisor, by virtue of training and experience, is solely responsible to direct any actions necessary to stop and recover from such situations. Full recovery from any casusity or emergency situation will performed in accordance with established emergency procedures. 8.0 RESPONSE T ENERCENCIES l Should a fire, or other emergency requiring evacuation occur during processing operations, the operating personnel should take the following steps: 8.1 Vaste Transfer ! Immediately stop the operation in accordance with SOP 70 1 and follow planc emergency procedures. 8.2 Vasta Processing in Automarie Allow the batch to continue in accordance with SOP 70 3. The system will finich the batch and stop when an empty drum is not transferred to the Fill Station. Follow plant emergency procedures. SAJ0057:3RM A-7
e
'w'VHS PCP 002 Rev. O. Draft 8 ATTACKHLYT A (continued)
("~~\ l 4 _,/ 8.3 Easto Processing in Kanual l Discharge mixers to drum in accordance with SOP 70 11, follow plant ' emergency procedures, i 8.4 Flushing or Flush Processing
)
l Immediately stop the operation in accordance with SOP 70 12 and ' follow plant emergency procedures. 8.5 Drum Senearinr. and Loadout Immediately stop the operation in accordance with SOP 70 37 and follow plant emergency procedures. Note that if the Drum Loadout Shield Door is OPEN, any drums should be indexed clear of the shield door, the truck drawbridge should be raised, and the shield door should be CLOSED. 8.6 IDSS OF VFKrILATION Allow the batch to complete per SOP 70 3 (Automatic) or 50P 70 11 (Manual). Do not resume operation t ' !1 ventilation has been restored in accordance with SOP 70 14 Evacuation of the CSS Control Room is not required. 8.7 IMSS OF ELECTRIC POWER Complete the batch and initiate flush in accordance with SOP 70-
- 19. Evacuation of the CSS Control Room is not required.
r-(v SAJ0057:3RM A8 i l
4 5 e
VNS
. PCP 002 Rev. O. Draft B ATTACHMENT A (continued) 9.0 QUALITY ASSURANCE AND RECORDS MANAGEMENT 9.1 Sample Verification Data Sheets Sample verification is performed for each tank volume 5 D 15Al or
$ D-15A2 feeding to the CSS Waste Dispensing Vessel to assure proper solidification of the waste us'ng the reference recips. Copies of the solidification sample data sheets are sent to Process Control Engineering. Data sheets are approved in accordance with Analytical Jhemistry Procedure ACP 5.1.
9,2 tor Book Records A daily log book, one set of unique y numbered entry pages per day, is maintained at the CSS shift office. The log book is used for data 79ording required by procedure and for documentation of the C recipe used. The log book contains the sample solidification (j\ verification log number assigned for each feed tank of waste to be processed 5 D 15Al or 5 D 15A2 by the Analytical Laboratory as a reference. Log book entries are reviewed and approved by the CSS shift supervisor and when completed for an operating year, are submitted to the Master Record Center for retention 9.3 Uaste Certification DAS output contains production d;ta for each drum processed.at CSS, The DAS weekly activity file is maintained on disk. Drum records may be copied to diskette during nonoperational periods. Manual data recorded on SOP 70 '+, attachment B, and DAS Real Time Printout are reviewed by Process Control Engineering and forwarded f to Quality Assurance with transmie.tal sheet. S0P 70 33, attachment B. SAJ0057:3RM A-9
l
- VVNS PCP 002 9 Rev. O. Draft B ATTACFMENT A (continued)
A copy of Presolidification Test Data, Analytical Request Form WV 1113, is forwarded from Analytical & Process Chemistry to Quality Assurance and Disposal Operations. Missing data or data requiring clarification is corrected by Process Control Engineerin6 and Quality Assurance. Revisions to the Drum Data Base are recorded and authorized on attachment C to SOP 70-33. Final drum classification, based on drum data and radiochemical analysis is completed by Analytical and Process Chemistry in accordance with SOP 9 8, " Waste Classification" and verified by Waste Engineering. All drum data, includin6 drum classification ar.d processing data, are compiled by Process Control Engineering per SOP 70 TBD. 9.4 Full Scale Drum Testinr. ( i i x/ From each Processing Tank 5 D 15Al or A2, a drum is pulled at random from the production line and la placed into the drum test fixture located in the process room. The drum is tested to assure proper fill, proper penetration resistance and dryness with respect to free liquids as required in SOP 70-40. X \ (' t SAJ0057:3RM A 10 p
s *
/
VVNS PCP.002 s Rev. O. Draft B ATTACHMENT A (continued) 10.0 PREVDrrIVE MADfrENANCE AND cal.IBRATIONS 10.1 Proventive Maintenartee l I i Periodic preventive maintenance required for the CSS is described i l in S0P 70 41, periodic preventive maints.tance items are scheduled in the maintenance recall system. 10.2 Calibrationa Instruments requiring periodic calibration are identified in the appropriate maintenance recall lists. l t l () S AJ0057 : 3RM A 11 l t l .
1 *' WNS PCP 002 Rev. O. Draft B O 9 ATTACitMENT Al REFERENCE RECIPES FOR . SLUCCE VASil LIQUID O . O S-S 7 : - .t.1
0
- e'
- WNS PCP 002 Rev. O, Draft 8 ATTACHMENT A2 RUN PIAN GRAPHIC SAJ0057:3RM A2 1
s 1 Waste Form Interim Qualification Report () WVDP Stabilized Sludge Wash Cement-Waste Table of Contents 1.0 INTRODUCTIOh
2.0 BACKGROUND
3.O WASTE CllARACTERIZATION 4.0 MINIMUM REQUIREMENTS OF 10 CFR 61.56 (a) 4.1 Packaging 4.2 Liquid Waste 4.3 Free Liquid 4.4 Reactivity of Produce 4.5 Gas Generation 4.6 Pyrophoricity 4.7 Gaseous Waste 4.8 Ha:ardous Wasto 5.0 STABILITY RPQUIREMENTS OF 10 CFR 61.56 (b) 6.0 REQUIEEMENTS OF 1991 TECHNICAL POSITION PAPER O 6.1 6.2 6.3 Comprettive Strength Radiatio.: Resistance Biodegradation Resistance 6.4 Leachability 6.5 Immersion Resistance 6.6 Thermal Cycling 6,7 Free Liquids 6.8 Full-Scale Specimen Test Results 6.9 Qualification Test Specimen Preparation 6.10 Process Control Program 6.10.1 Process Parameters 6.10.2 Verification and Surveillance Specimens
7.0 CONCLUSION
S 7.1 Key Qualification Tests 7.2 Additional Waste Characterization Information 7.3 Additional Qualification Testing 7.4 PCP Information
8.0 REFERENCES
O
1.0 Il[TAODUCTION f~'} V This document is presented by West Valley Nuclear Services Co., Inc. (WVNS) to provide technical information on a stabilized (Class A, B, or C) cement-Waste form te be produced at the West Valley Demonstration Pcoject (WVDP) . The information is intended to show compliance to the requirements for radioactive low-level waste (LLW) as set forth in 10 CFR 61, supplemented by the 1991 US NRC Technical Position paper (TP). l 2.0 DACKGROUND The West Valley Demonstration Project Act of October 1, 1980 (Public Law 96-368) directs the Department of Energy (DOE) to carry out a radioactive high-level waste (HLW) management demonstration project at the West Valley, New York site. The West Valley site was the location of the only operating commercial nuclear fuel reprocessing plant in the United States. West Valley Nuclear Services Co. , Inc., a subsidiary of Westinghouse Electric Corporation, has been the prime contractor to DOE for site operations since 1982. The demonstration project will remove HLW from underground storage tanks and solidify it into a borosilicate glass for s long-term storage at a future federal repository. The major T portion of the HLW amounted to about 2 million liters of J fluid stored in an underground storage tank, designated Tanh 8D-2. The tank also contained a sludge layer on the floor of the tank that had insoluble oxides, hydroxides, and carbonates of many species (principally iron). Also in the sludge layer was undissolved sodium sulfate crystals that precipitated from the supernatant liquid. Prior to HLW stabilization in borosilicate glass, several pretreatment operations were defined that would minimize the final volume of HLk glass. Beginning in 1988, WVNS processed the liquid supernatant solution from Tank 8D-2 through an ion-exchange process to yield a LLW solution (Figure 1). The LLW stream was concentrated and made into a cementicious waste form. The Class C cement-waste is described in a previous topical report "Coment Waste Form Qualification Report - WVDP PUREX Decontaminated Supernatant". Cement-waste drums were made up through November, 1990. A new pretreatment step is being implemented at the WVDP. The HLW in Tank 8D-2 is being mobilized by five pumps, wnich allows the sodium sulfate crystals to dissolve into the sludge wash water. By adding caustic during the sludge washing operation, uranium, strontium, and plutonium will be maintained at trace levels in the sludge wash solution. ("')i 1
O O O . R d Uguid Remove I Radioactive Material gr -. j Mk;- M [Il q_listuddsQ qpp G2
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\/ The resulting sludge wash solution will be treated in the ion exchange process as was done with the p;evious supernatant solution. A .cne ion exchange eolite will be used to retain cesium, strontium, and plutonium from the sludge wash solution. The resulting LLW stream will be concentrated and made into a cementicious wacte form similar to previous supernatant cement-waste in the Cement solidification System (CSS).
Depending on the level of plutonium, strontium, and cesium after ion-exchange, the coment-Waste may be classified as A, B or C waste forms. Class A can be achieved because of the trace levels of strontium and plutonium from the sludge wash process, the new lon exchange eolite to retain strontium and plutonium, and the lower weight percent salt content in the final'LLW stream (compared to the supernatant process). By chooning to qualify the waste form as stabilized, any class cament-waste may be produced. In doing so, WVHS acquires an option on the final disposal of this new waste form. If deemed appropriate, these new cement-waste forms may be disposed in conjunction with the previous supernatant Class C cement-waste material.
) 3.0 WASTE CHARACTERIZATION The LLW stream for which data are presented to demonstrate qualification is sludge wash solution with 20 wt% dissolved salts. The candidate waste has the following characteristics:
Major Constituentst Nominal 20 wt% salt solution composed primarily of sodium, nitrate, nitrite, and sulfate salts (about 95% of the total salts)
'Densityt. Nominal 1.15 - 1.16 g/ml Temperature Ambient - 90*F Secondary Species: Laboratory-generated sludge wash solution and nreliminary Tank 8D-2 actual sludge wash compositione are depicted in Table 1.
Non-radioactive surrogate solutions for qualification testing are shown in Table 2. l 3 l l l i
Table 1 chemical Composition of Laboratory-Generated Sludge Wash Solution
& Preliminary Actual Sludge Wash solution Laboratory Tank 8D-2 Dry Wtt g/l Dry Wtt g/l Majort Na 31 75 31 69 NO 3 27 66 28 63 NO 2 23 56 25 56 SO 4 10 25 10 23 Minor K 1.2 3.0 Al 0.52 1.3 0,13 0.30 Cl 0.20 0.49 0.21 0.49 Ca* 0.20 0.48 B 0.16 0.39 P 0.15 0.37 Cr- 0.11 0.26 Fe* 0.053 0.13 U* 0.0071 0.017 0.0020 0.0048 O pH 12.2 12.5
- not used in surrogate solution O 4
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r Table 2
\
Chemical Composition of Surrogate Sludge Wash Solutions For Coment-Waste Qualification Tests Original Surrogate Future Surrogate l Dry g/l Dry g/l Wtt 020% TDS Wt% 020% TDS Majort Na 31 73 30 71 NO 3 27 62 26 62 NO 2 22 51 24 56 SO 4 14 33 9.6 23 CO 3 2.6 5.9 2.8 6.6 Minor K 0.85 2.0 1.1 2.7 Cl 0.21 0.49 0.21 0.49 Cr 0.15 0.35 0.16 0.38 P 0.057 0.13 0.20 0.48 TOC 0.042 0.097 0.045 0.11 , Mo 0.024 0.056 0.026 0.062 B 0.0037 0.0087 0.17 0.39 Al --- --- 0.13 0.30 TOC = Total Organic Carbon Table 3 Trace Chemicals Expected in Sludge Wash Solution Dry ppm g/l F 187- 0.044 Sn_ 60 0.014 Rb 53 0.012 Te 34 0.0980 Si 18 0.0042 Se 5 0.001 Cu 2 0.0004 Sr- 1 0.0003 Li 1 0.0003 Mg <1 Calculated from previous characterization work of supernatant solution (Reference 3] 5
O Other trace species that are expected in the sludge wash solution based on previous HLW supernatEnt characterization are shown in Table 3. Analyses of the actual decontaminated sludge wash solution will be provided at a later date. Radioisotopes: Key radionuclides for laboratory-generated decontaminated sludge wash solution are shown in Table 4. Other trace radionuclides that are expected in the sludge wash solution based on previous HLW supernatant characterization are shown in Table 5. Analyses of the actual decontaminated sludge wash solution will be provided at a later date. 4.0 MINIMUM REQUIREMENTS OF 10 CFR 61.56(al Section 61.56(a) of 10 CFR Part 61 contains the minimum requirements for all classes of waste. The following sections summarize the different criteria and how the proposed waste form will meet those criteria. 4.1 Eag.kaqinq - Criteria The waste form must not be packaged for disposal in cardboard or fiberboard ' boxes. Waste Form: The waste form will be poured into plastic-lined 268 liter square 16 gage steel containers as shown in Figure 2. 4.2 Liguid Waste Criteria: The liquid waste must be solidified or packaged in sufficient absorbent material to absorb twice the volume of the liquid. Waste Form: The 20% salt solution will be made into a cementicious material with no free ( liquid. 6
~
Tablo 4
.( ~
Key P*dionUC11 des in Decontaminas ",1udge Wash Solution Calculated .' Measured For Cement-Wasto Value. with20%TDSpLW 4Ci/g solution Ci/m Tc-99* 0.284 0.19 Sr-90** 0.00048 0.00032 Cs-137** 0.27 0.18 alpha Pu** 0.012 0.90 nci/gm
- Measured in actual Tank 8D-2 sludge wash solution
**Moasured near a column change in laboratory sludge wash experimenti corrected to 20% total solids (TDS).
i O 7 2__ __ . _ _ . . _ . _ . _ . - _ . - _ _ . _ . , __
( Trole 5 Trace Radionuclides Expected in Decontaminated Sludge Wash Solution As of 4/1/92 Ci Ratio Cement-Waste Relative Relative 920% TDS to Tc-99 to Cs-137 mci /m3 H-3 0.047 --- 8.9 C-14 0.086 --- 16 Ni-63 0.54 --- 102 Se-79 0.023 --- 4.4 Zr-93 0.00014 --- 0.027 Nb-93m 0.000065 --- 0.012 Ru-106 0.000034 --- 0.0064 Rh-106 0.000034 --- 0.0064 Pd-107 7.5E-06 --- 0.0014 Cd-113m 0.010 --- 1.9 Sn-121m 8.7E-07 --- 0.00016 Sb-125 0.011 --- 2.0 Te-125m 0.0024 --- 0.46 Sn-126 0.00025 --- 0.048 Sb-126m 0.00025 --- 0.048 O Sb-126 I-129 Cs-134 0.00010 0.00013 0.00043 0.019 0.025 0.077 Cs-135 --- 0.000024 0.0043 Ce-144 2.7E-10 ---
<0.0000001 Pr-144 2.7E-10 ---
<0.0000001 Pm-147 0.030 ---
5.6 Sm-151 0.00066 --- 0.13 Eu-152 0.000021 --- 0.0039 Eu-154 0.0057 --- 1.1 Eu-155 0.00074 - - 0.14 Tc-99 calculated to be 0.19 Ci/m3 Cs-137 assigned to be 0.18 Ci/m3 Calculated from previous characterization work of supernatant solution (Reference 3) O 8
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('~ 4.3 Free Licuid (m- ' Criteria: Free standing liquid in the solid waste shall not exceed 1% of the solid volume. ; Waste Form: Cement-waste product made ith surrogato sludge wash solution has demonstrated no free liquid within one hour after creation of the comenticious material. 4.4 R_eactivity of Product critoria: The waste must not be readily capable of detonation or of cxplosive decomposition or reaction at normal pressure and temperatures, or of explosive reaction with water. Waste Form: After solidification, the wanto form will not contain any substances capable of such reactions.
- 4. 5 Gas Generation Criteria: The waste must not contain or be capable of generating toxic ( 1ses, vapors, or 7- fumes harmful to persons transporting, handling or disposing of the wasto form.
Waste Form: After solidification, the wanto form will not contain any substancos capable of such gas releases. 4.6 Pyrophoricity Criteria: The waste must not be pyrophoric or contain material thich are pyrophoric as defined in 20 CFR 61.4. Waste Form: The waste form does not contain any pyrophoric materials. 4.7 Gaseous Waste This provision is not applicable to a solidified waste form. O 10 y y ., -
, , . - , uo,_ .- _ .-
4 (~ ( 4.8 Hagardogg Waste C'riteria : Waste containing hazardous, biological, pathogenic, or infectious material must bv treated to reduce the potential hazard. Waste Forms Chromium in the LLW salt solution is at a level to be considered hazardous por applicable EPA guidelines. After solidification, the chromium will be readily retained in the cement matrix. Results.of TCLP testing of actual radioactive sludge wash cement-waste will be provided at a later date. 5.0 DTABILITY REQUIREMENTS CF 10 CPR 61.5fjh1 Section 61.56(b) of 10 CPR Part 61 contains the stability requirements for stabilized waste forms. Two of the critoria, structural stability and free liquids, are specifically addressed in the Technical Position paper (TP) . [ Section 6 covers the recommendations of the TP and the data supporting the stabilized cement-waste form. The other criteria in this section of the regulations cover the void spaces within the waste and between the waste and its package. The steel drums that will contain the processed cement waste will be filled while the waste form is still fluid. As a result, the void space between the waste and the containers are minimized to the maximum extent possible. Also, specific directions are provided in the Process Control Plan to ensure at least an 85% fill of a drum. 6.0 BRQMIEEMENTS OF 1991 TECHNIQhL POSITION PAPER The Technical Position paper (TP) contains recommendations on the st.bility requirements for all classes of stabilized waste. The following sections summarize key criteria trom the TP, including Appendix A. Results of testing are presented to show that the waste form meets the criteria. Two different sets of results are cited in this section. Where available, test results for the proposed waste form (cement-waste made with 20 wt%'TDS surrogate sludge wash i solution) are presented. Some results are not available for 11 i
the waste form made from 20% TDS sludge wash solution. For these cases, results from an alternate waste form, cement waste made with sludge wash solution concentrated to 33 wt% dissolved salts, are presented. Additional testing for ] these cases is also identified and summarized in section 7.3. 6.1 99poressive Strenoth Criteria: Sufficient specimens (at least 10) shall be compression tested after a minimum cure time of 28 days. Average compression strength gIl eater than 500 psi is required. Testing shall also be - performed to determine. the compressive strength increase with time to ensure that the specimens have attained near-maximum compressive ntrength. Waste Form: Cores (2 5/8" diameter x 5 1/4" length) were removed from coment-waste drums 1; prepared with non-radioactive surrogate
- 9 sludge wash solutien over the period of several weeks. Results are shown in Figure 3. .
Lines representing the 95% confidence interval of the regression line through all the data are provided. The waste-form does not show any statistically significant strength increase beyond 28 days nC curing. The average of all the cores is 1247 psi, well in excess of the 300 p.1 minimum. { ? 6.1 Radiation Resistance Waste forms containing ien-excaange resins or other organic materials shall be tested for radiation stability. The proposed WVNS waste form does not centain any ion-exchange resin and only trace gnantities of organic materials, thus this test is not required. 6.3 Biodegradation Resistance Waste forms containing carbonac4ous materials shall be teated for blocegradation resistance. The proposed WVNS waste form does not contain appreciable carbonaceous materials, thus this test is not required. O 12
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7s 6.4 Leachability i\ J) Criteria: Leach testing in accordance with
-ANSI /ANS-16.1 shall be performed on the waste form. Five day tests in both i demineralized water and synthetic sea water shall be completed on the cement-stabilized waste form. Leach indices, as calculated per the ANSI /ANS method, shall be greater than 6.0.
Waste Form: The proposed waste form is a stabilized cement-waste made with sludge wash solution at 20% total dissolved salts (TDS). Prior research wit 1. the same wash solut' 1, but concentrated to 33% TDS was pet.ormed. Radioactive solution from the HLW tank was collected prior to washing of the HLW sludge. The sample was p!! adjusted and supplemented with sodium sulfate to simulate the anticipated sludge wash solution. Mini-cylinders 1" diameter x 3" length were prepared in the laboratory. (D i ,/ The results of the leachability testing are shown in Tables 6 and 7 as well as Figures 4 and 5. The lowest leach index for any of the key radionuclides was 7.69 for Tc-99 in demineralized water leachant. These positive results at the higher salt loading are suggestive of similar success at the lower salt loading. WVNS will perform leachability testing of cement-waste made with cctual sludge wash solution at the lower TDS loading. Results will be reported at a later date, 6.5 ImJtersion Resistance Criteria: Waste specimens shall be immersed for 90 days in the more aggressive leachant identified in the leachability test. Visual examination of the immersed samples shall be performed to verify no significant degradation (e.g. cracking
,-ss
- or spalling). The average compression 14
.s:
((~ Table 6 Leachability Testing Results Lab-Prepared 33% TDS Mini-cylinders In Demineralized Water Average Leachability Index hrs Tc-99 Sr-90 Cs-137 a Pu 2 7.725 10.026 -7.813 14.047 7 7.831 9.974 8.051 14.219
; 24 7.692 10.080 7.976 14.224-48 -8.112' 10.355 8.457 12.96L 72- 8.555 10.895 8.910 13.083 96 8.936 10.985 9.324 13.186 120 9.299 11.313 9.681 13.269 In Synthetic Sea Water Average Leachability Inde.
hrs Tc-99 Sr-90 Cs-137 a Pu [-sT- 2 '7.855 10.424 7.977 11.751 A/ 7 '8.010 10.726 8.289 11.924 24 7.797 11.392 8.060 13.235 48 8.026 10,~150 8.393 11.153 72 8.459 10.637 8.847 11.682 96 8.879 11.509 9.225 11.783 120 9.138- -11.783 9.598 12.106 More Aggressive Leachant hrs Tc-99 Sr-90 Cs-137 a Pu 2 Demin Demin- Demin Sea 7~ Demin- Camin Demin Sea 24- 'Demin Deuin Demin- Sea 48 Sea Demin Sea Sea 72 Sea- Sea Sea Sea
+
96 Sea. Demin Sea Sea
- 120 Sea Demin Sea Sea r"
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Table 7 Leachability Testing Results for Tc-99 Lao-Prepared 33% TDS Mini-cylinders Leach Indices Triplicate Measurements for Tc-99 hrs _ Demineralized Water Synthetic Sea Water 2 7.716 7.743 7.718 8.091 7.781 7.785 7- 7.894 7.782 7.816 8.016 7.991 8.024 24 7.765 7.640 7.672 7.815 7.781 7.794 48 8.074 8.122 8.141 7.985 8.053 8.040
'72 8.588 8.490 8.587 8.430 8.508 8.439 96 8.919 8.954 ---
8.892 8.866 --- 120 9.246 9.280 9.370 9.170 9.131 9.114 Statistical Comparison of Leach Indices for Tc-99 Difference Between Demineralized and Synthetic Sea Water? Demin Water Sea Water Signif hrs Avg Var. Avg Var Delta Level Diff? I--}s
-'- ' 2 7.73 0.00015 7.89 0.02108 0.16 0.29 No 7 7.83 0.00220 8.01 0.00020 0.18 0.10 Yes 24- 7.69 0.00281- 7.80 0.00020 0.10 0.11 No 48 8~.11 0,00079 8.03 0.00087- 0.09 0.08. Yes 72 8.56.-0.00211 8.46- 0.00121 0.10 0.11 No 96 8.94 .0.00031 8.88 0.00017 0.06 0.07 No 120 9'.30 0.00274 9.14 0.00055 0.16 0.11 Yes
_ Var = variance _of replicate measurements-Delta = difference between averages-Signif Level = 95% confidence value for differences between
'the two averages Diff = Is delta more than the significance level?
conclusion: During 5-day test, only subtle differences can be detected for the Tc-99 leach indices in de.nineralized water and synthetic sea water.
. J{ 16
! Leachability Indicies Demineralized Water i Leach Index 16 . . . .
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4' 110 120 O 10 20 30 40 50 60 70 80 90 100 Test Time [Hoursj Simulated Cement-Waste from 33% TDS solution J L bt Jf M/9?
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l (~3 value after immersion shall be greater J- than 500 psi and more than 75% of the un-immersed baseline average. ! For those waste forms that lose more than 25% of the compressive strength compared to the un-immersed average, additional immersion testing through 180 days shall be completed. Sufficier.t samples she.11 be testad to show a stabilization of the compression strength by 180 days of immersion. Visual examination of the immersed samples chall be performed to verify no significant degradation (e.g. cracking or spalling). Tne average compression value after immersion shall be greater than aca psi. Waste Form: Cores (2 5/8" diameter x 5 1/4" length) were removed from full-scale cement-waste drums prepared with non-radioactive surrogate sludge wash solution. Three cores were placed into j demineralized water and three into _ synthetic sea water.
-- After 90 days of immersion, the specimens showed only minor cracking.
Average compression strength after immersion was 1722 psi for demineralized water and 1189 psi for synthetic sea water. Compared to tha un-immersed ~ baseline average of 1247 psi these represent an increase of over 30% and a decrease of under 5%. Based on these results, the proposed waste form made with 20 wt% TDS sludge wash so?ution meets this criteria. As noted in 6.4, prior research with the same LLW stream, but concentrated to 33% TDS was performed. Cores of cement-waste drums made with surrogate solution were immersed in demineralized water. Sulfate attack of the waste form was significant. After 90 days immersion, compressive strength was less than 75% of the un-immersed average. By 120 days of immersion, the strength had fallen below 500 psi. Significant spalling and (~]
'j cracking of the waste form was noted.
19 l
1 . f f (g~,) Failure of the cement-waste form in this test loud to the investigation of reduced salt loading in the waste form. A reduction of the waste loading by using sludge wash solution concentrated to 20% TDS yields excellent immersion resistance perfonaance. WVNS will perform additional immersion resistance testing to evaluate the significance of wt% TDS, water-to-cement ratio, and sulfate level in the LLW. Results from these tests will be reported at a later date. 6.6. Thermal cyclina Criteria: Waste specimens shall be subjected to thirty thermal cycles between -40*C and 60*C in accord with ASTM BS53. Visual examination of the cycled samples shall be performed to verify no significant degradation (e.g. cracking or spalling). The average compression value after fg cycling shall be greater than 500 psi, t i
'l Waste Form: As noted in 6.4, prior research with the same LLW stream, but concentrated to 33%
TCS was performed. Non-radioactive simulated sludge wash solution was used in the full-scale equipment to fill drums with the cement-waste. Cylindrical molds (3" diameter x 6" length) were filled with the cement-waste by scooping material directly from the waste drum. One special mold was equipped with a tnermocouple along the centerline. The molds were capped and placed into an environmer.tal chamber. The specimens were cured at 79 2*C for a total of 90 -0/+8 hours. The temperature corresponds to a measured peak for a 33% TDS cement-waste drum fitted with a thermocouple along the centerline. Total' time includes the time needed for the drum centerline to cool to 30"C. Following the high-temperature cure, the cylinders were cured for a total time of 49 days. {%/'} 20 l 1
b f x__ (_) After removal from the molds, the specimens along with the special instrumented specimen were inserted into the environmental chamber. Thirty temperature cycles were-completed from 60*C to 20*C to -40'C and back with one hour soak periods at each' temperature. After removal from the chamber, the specimens were viewed. No spalling or cracking was noted. Average compression strength values of the cycled specimens was 1229 psi versus 1284 psi for specimens that did not undergo thermal cycling. These positive results at the higher salt loading _(33% TDS sludge wash solution) are suggestive of similar success at the lower salt loading (20% TDS sludge wash solution). WVNS will perform thermal cycle testing of cores taken from cement-waste drums made with sludge wash solution at the lower TDS loading. Results will be reported at a later date. (/) x_ 6.7 Free Licuids Criteria: Waste specimens shall have less than
-0.5% (by volume) of the waste as free liquids as measured by the method in Appendix 2 of ANS 55.1.
Waste Form: WVNS proposes alternate testing to meet this criteria. A three step approach is presented to show equivalence. As noted in section 6.4, prior research was conducted with surrogate sludge wash , solutions at 33% TDS. Step one was to. prepare small-scale specimens (2" x 2" x 2" cubes) in the laboratory from non-radioactive sludge wash surrogate
-solution. Twenty-eight different cubes were prepared in a statistically-designed screening test (Plackett-Burman structure). Thirteen pcssible variables were used in the screening test as noted in Table 8.
o( 21
.e .
~
j m. Table 8 Twenty-Eight-Run Plackett-Burman Screening Test (
) . Index of Variables Varicklg Number Low Hiqh Sulfate 1 0.5x 2x Nitrate: Nitrite Ratio 2 0.5 2.8 Organics 3 0.5x 4x Aluminum (gm Al/gm Cl) 4 0 2.5 Total Solids (TDS) 5 25 37 Water: Cement Ratio 6 0.3 0.8 Calcium Nitrate 7 0.5x 2x pH 8 11 13 Mix Time (rins) 9 4 16 Anti-foam 10 0.3x 2x Sodium Silicate 11 0.5x 2x
' Phosphate (gm PO4 /gm Cl) 12 0.01 7.0 Boron.(gm B/gm Cl) 13 0.001 0.15 Note: Above. values, when listed with an accompanying."x" are rtultipliers'to the nominal 33% TDS-sludge wash-cement-waste formula presented in WVMS-TP-028A m ,,
, ,, . . - .- - . . - . . . ~ . _ - -. .- - ._- -. . -
'f,.. 'a
.n
.itI f(~'t Over the range-of wt% TDS from 25 to 37, (j only-the water-to-cement-ratio was found
.to be statistically important in .
. 'affecting' gel time and 7-day cured
-compressive-strength. -Free water was present after l' hour on only.three-cubes, which allEhad-high water-to- ,
cement ratios (0.80) and high trace phosphate levels l(200% increase over lab-generated sludge wash solution). No free water was present after.24 hours. Step two of the' approach was to fabricate full-size drums using the 20% TDS surrogate sludge wash recipe. After-curing, the' drums were extensively cored.- Almost-5% of the drum contents was-sampled from side-to-side and top-to-bottom' . No free. liquids were detected. The cores provided material for baseline compressive' strength tests, homogeneity verification, and immersion tests.- < The-final step to show equivalency is to perform.a limited variability' test.on full-rnale' drums using actual N- radioactive sludge wash solution.- WVNS will vary-the water-to-cement ratio-and TDS.of the sludge wash solution. After curing, the drums will be cored : ana the absence'of any free' liquids established. Results:of this test will be reported at a later date. 6.81 Full-Scale Specimen Test Results criteria: If small, simulated laboratory-size specimens are used to support the above tests, test data from cores of- the full-scale. products-also-should be obtained. Correlations between the-performance of
-the lab-sizeLspecimens and the core data shall bs. prepared. >
Samples shall'be taken from'throughout the entire full-scale waste form to ensure that product is homogeneous and Lall regions offthe product will have i compressive strengths of at'least 500 F psi._ uD 23 l?
jw -
- 4
(( b; -Waste Form: For every keyfsupporting test, cores
^-s/ from cement-waste Edrums have been the specimens of choice. Tests identified for future' reporting shall be completed
- on core soecimens. -Verification
~
specimens using cubes are discussed in section 6.10.2. A cement-waste. drum prepared with 20% TDS surrogate sludge wash solution had 18 cores.(2 5/8" diameter x 5 1/4" length) removed. The cores were taken from different-heights and distances to the centerline. -The twelve cures tested to be statistically all f_om the same
-nopulation-and visibly showed no inhomogeneities. Six-additional cores that underwent immersion testing also showed no inhomogeneities-(see section 6.5). The proposed waste form is homogeneous and meets the'~500 psi strength value for all regions.
-6.9: Oualification Test Specimen Preparation 7']; -Criteriai Appendix A of the TP recommends certain J(p/; '
precautions be.taken during the mixing, curing, and storage of_ qualification test specimens. . The goal is-to produce
; specimens in the. laboratory that are representative of the actual waste form product.
Waste Form: Two preliminary tests used laboratory specimensEwith a 33%'TDS surrogate-recipe to dimulate the proposed waste form: thermal cycling and leachability. WVNS followed.the: recommendations in the TP~to simulate'the degree of mixing, methodLof curing,:and-storage of specimens before testing. As noted in section 6.8, these~ tests will be repeated ontcores_taken from drums f'11.ed with1 actual radioactive sludge-- w .,n solution. - LO .. f _.. ~ ~ ~ , - ,
+ g n 9 m"+
e t. 6.10 Process Control-Procram A Process Control Program shall be instituted to control the variables that influence the process and affect the final waste-form product. Previously for the WVDP supernatant cement-waste, a Process Control Plan (WVNS-PCP-001) was issued. A new version of the Process Control Plan (WVNS-PCP-002) is attached in the Appendix. This section discusses the key criteria cited in the TP and the features of the WVNS PCP that meet those needs. 6.10.1 Process Parameters Criteria: The PCP shall identify and restrict within acceptable bounds variables that influence the process and affect the product. Waste Form: As noted in section 6.7, screening tests were performed on a wide range of process variables. The only key variable for gel time and compressive strength was the water-to-cement ratio. Only at excessive water-to-coment L O ratios (0.80) and excessive phosphate levels (200% increase over lab-generated sludge wash solution) was any free water I detectable beyond 1 hour. After 24 , hours no free water was detecable. In addition, a variability test will be performed by WVNS to determine the key variables for success in the immersion test (see section 6.5). Samples with 33%_TDS surrogate sludge wash solution failed the immersion test whereas those with RO% TDS surrogate sludge Wash solution passed the test. In the latter case, the sulfate in the surrogate-sludge wash solution was 40% higher than the actual ' sludge wash solution. WVNS_ proposes three controls be set up to regulate the process:
- water-to-cement ratio
- TDS of sludge wash soluticn
- - SO4 level 25
6.10 Process Control Program A Process Control Program shall be instituted to control the variables that influence the process and affect the final waste-form product. Previously for the WVDP supernatant cement-waste, a Process Control Plan (WVNS-PCP-001) was issued. A new version of the Process Control Plan (WVNS-PCP-002) is attached in the Appendix. This section discusses the key criteria cited in the TP and the features of the WVNS PCP that meet those needs. 6.10.1 Rocess Parameters Criteria: The PCP shall identify and restrict within acceptable bounds variables __.. that influence the process and affect the product. Waste Form: As noted in section 6.7, screening tests were performed on a biue range of process variables. The only key variab]e for gel tima and compressive strength was the water-to-cement ratio. Only at excessive water-to-cement ratios (0.80) and excessive O phosphate levels (200% increase over lab-generated sludge wash solution) was any free water detectable beyond 1 hour. After 24 hours no free water was detectable. In addition, a variability test - will be performed by ?!VNS to , determine the key variable for success in the immersion test (see section 6.5). Samples with 33% TDS surrogate sludge wash solution failed the immersion test whereas those with 20% TDS surrogate sludge wash solution passed the test. In the latter case, the sulfate in the surrogate sludge wash solution was 40% higher than the actual sludge wash solution. WVMS proposes three controls be set up to regulate the process:
- water-to-cement ratio
- TDS of sludge wash solution
- SO4 level 26
Erst WVNS proposes to produce the cement
.?\ '[ waste form at a water-to-cement ratic of 0.66-i 0.02. Combined with this, the salt content of the LLW stream shall be controlled to 20 1 wt% total solids. Along with a check on the level of sulfate, these ec7trols regulate the relative proportion of sulfate-to-cement in the product (immersion performance).
These controls ars the main variables that influence the process and tne cement-waste product. All other variables fall within the wide operating ranges evaluated in the screening tests. The order of addition is:
- 1) LLW-solution
- 2) Antifoam
- 3) Cement blend
- 4) Sodium silicate solution More specific information can be
/'T found in the Process Control Plan.
)
A wider range of water-to-cement catios will be identified in the feture variability tests noted above._ When completed, the results of these tests will be-reperted along with tne.new control range for the CSS process. 6.10.2 Verification and Surveillance SDecimens Criteria: Prior to solidifying full-scale wacte forms, verification specimens should be prepared for examination and compressive strength testing. The specimens should be free of significant visible defects (e.g. cracking or spalling) and should exhibit less than 0.5% by volume free liquid. ! Compressive strengths should be L measured within 24 hours after preparation. The values should be ("\ ij s within two standard deviations of 27 i
. . . . . - . . . . -- . -- . . ~ . -. - ~ . . _ __-
yl Sfy
-w_
~
0.14 gram'SO4 per_ gram-total _calts.-
~i This limit corresponds to-the level Q p 3-/ - in.the surrogate solution'that
- passed immersion testing.- ,
When the results of the immersion variability tests are in, new operating. ranges will be defined for the full-scale CSS process. Results from these-tests and an
~
updated Process Contro Plan will be provided at a later date.. Preparation'of additional-specimens for long-term performance testing is not required of the WVNS waste-form. The waste stream that is being solidified does not belong to , the cited special class of waste - streams (bead resins, chelates, filter sludges, and floor drair-wastes) that require this-effos.,
'7 . 0 - CONCLUW1'ONS if-p '.This section. summarizes the key qualification test results, and consolidates future. testing commitments by WVNS for the
-(' ,
proposed waste' form. 7.1 : Kev Oualification Tests' , Compressivefstrength oficores taken from cured full-Escale product drums lmade with-20% TDS surrogate sludge wash:Aolution~ yielded.1247. psi for an average of 12 is --samples.. Immersion testing in'both demineralized water 1and synthetic-seatwaterishowed. excellent long-term-physical-stability. In demineralized watar-the average of=three cores was 1722-psi; forl sea water it was 1189-psi. An1 alternate' testing methodology is-proposed to meet' - thelspecified free liquids limit. Laboratory tests with surrogate solutions _between:25% and 37% TDS showed' that only1the water-to-cement ratio.was key to compressive c strength and gel time.- The test also indicated only high water-to-cement ratis 1 (0.80)' and
-highi phosphate 1(200% increase:above-lab-generated-
, sludge wash' solution). yielded'any free water after 1 - hourron small specimens. No free water was detected after-24 hours. Extensive coring of a full-scale drum filledLwith the 20%-TDS surrogate-sludge wash cement-l1 i 28 L [: s e r , , ,-- , ,
L . c g s- waste has shown no free water. A final series of full-
)
~
scale waste forms made with actual radioactive sludge wash solution with varying water-to-cement ratios and TDS levels will be produced and cored. Tests with the same surrogate sludge wash solution at a higher salt content (33% TDS versus 20% for the proposed waste form) have shown success for leachability and therma] cycling. Radiation resistance and biodegradation tests of the waste form are not required. f.2 Additional Waste Characterization Information WVNS has produced nearly complete characterization information on the sludge wash solution that will be stabilized. Final updates to the characterization information will be provided. 7.3 Additional Oualification Testing The proposed waste form meets and exceeds the various criteria set forth in the Technical Position paper. A few follow-up tests have been noted. These include:
- 1) Cores taken from actual radioactive 20% TDS sludge wash cement-waste drums will undergo thermal f~Ns-) cycling and compressive strength testing.
- 2) Cores taken from actual radioactive 20% TDS slud9 J wash cement-waste drums will undergo leachability testing.
- 3) Cores taken from actual radioactive 20% TDS sludge wash cement-waste drums will undergo TCLP testing.
- 4) Free liquid determinations will be made on a series of actual radioactive 20% TDS sludge wash cement-waste drums produced at varying water-to-cement ratios and wt% TDS levels.
7.4 PCP Information Tests in the laboratory have shown that very few controls are needed to produce a qualified waste-form. Key control variables for production of full-scale drums are:
- water-to-cement ratio: 0.66 0.02
- salt in LLW stream: 20 1 1 wt%
- sulfate in LLW stream: < 14% of total salt, ,
n 29
~
4 S Pending results of the imme.sion variability tests, O WVHS will resubmit this report with the wider operating ranges. ) During actual radioactive processing, verification samples will be taken from the tank feeding the full-scale solidification system. After preparation of a cube in the labcrutary, visual confirmation of no free water and no physical degradation will be performed. A compressive strength measurement of the cube will be - made and compared to a minimum value. WVNS will prepare a series of cement cubes in the I$- laboratcry using actual radioactive sludge wash solution. The cubes will be made to the same
-3 specification as the full-scale process. A minimum 24-T ,
hour compressive strength value sill be established using these specimens.
8.0 REFERENCES
1 " Technical Position on Waste Form", Revision 1, Technical Branch of the Low Level Waste Management and Decommissioning Division of the US Nuclear Regulatory Commission, dated January,-1991, 2 McVay, C. W, Stimmel, J. R, and Marchetti S., "Coment Waste Form Qualification Report - WVDP PUREX Decontaminated Supernatant", DOE /NE/44139-49 (DE89009019), Augast, 1988. 3 Rykken, Larry E., "High-Level Waste Characterization at West Valley: Report of Work Performed 1982 - 1985", DOE /NE/44139-14 (DE87005887), June 2, 1986. 4 Mahoney, John L., " Sludge Wash Cement Waste Form Qualification Development of Process Control Parameters:, WVNS-TSR-028, Revision 0, dated February 6, 1992. 5 Mahoney, John L., " Test Summary Results Report-for Qualification Work for the Nominal Recipe for Cement Solidification of Sludge Wash Liquids", WVNS-TSR-026, Revision 0, dated February 6, 1992. O 30 m
o f. AP_PENDIX WVNS-PCP-002 Process Control Plan for Cement-Waste with Sludge Wash Liquids J O J 4
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