ML20008F616

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Process Control Program for Chem-Nuclear Sys,Inc Cement Solidification Units
ML20008F616
Person / Time
Site: Crystal River Duke Energy icon.png
Issue date: 03/19/1981
From:
CHEM-NUCLEAR SYSTEMS, INC.
To:
Shared Package
ML20008F609 List:
References
SD-OP-003-01, SD-OP-3-1, NUDOCS 8104210383
Download: ML20008F616 (19)


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PROCESS CONTROL. MiOGRAM FOR CNSI CDENT

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CONTRACT NO.

DOCUMENT NO.

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TA3LE OF CCNTENTS

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1.0 Scope 3

1.1 Purpose 3

1.2 Applicability 3

2.0 References 3

3.0 System Description

4 3.1 Process Description 4

3.2 Process Parameters 4

3.3 Mobile Unit Description 4

3.4 System Operations 5

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4.0 Requirements for Sample Verification 7

l 4.1 General Precautions 7

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4.2 Radiological Precautions 7

4.3 Prerequisites 8

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4.4 Sample Acceptance criteria 9

4.5 General Requirements 10 5.0 Sample Verification 11 C

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6.0 Administrative Procedures 19 j

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l.1 Purpose The purpose of the Process Control Program for CNSI Cement Solidi-fication Units is to establish a set of process parameters which provide reasonable assurance of complete solidification of low-level radioactive liquid waste.

1.2 Aeolicability This process Control Program shall be used by all personnel oper-ating the CNSI Cement Solidification Unit.

2.0 REFERENCES

2.1 QA-AD-001, CMSI Quality Assurance Program 2.2 CN-AD-019, CNSI ALARA Policy 2.3 EN-AD-002, CNSI Design Control i

2.4 SD-OP-004 CNSI Operating Procedure for Cement Solidification Unit Number 1.

2.5 NUREG 0472. Radiological Effluent Technical Specifications for PWR 2.6 NUREG 0473. Radiological Effluent Technical Specifications for BWR c,

2.7 Branch Technical Position-ESTB 11-3, Design Guidance for Solid g

Radioactive Waste Management Systems Installed in Light-Water-Cool-E ed Nuclear Power Reactor Plants 2.3 ANSI 199, Liquid Radioactive Waste Processing Systems for Pressur-g ized Water Reactor Plants 3

2.9 ANSI 197, Liquid Radioactive Waste' Processing Systems for Boiling A

Water Ractor Plants 3

2.10 NRC Regulatory Guide' l.143, Design Guides for Radioactive Waste Management Systems, Structures, and Components Installed in Light-Water Cooled Nuclear Power Plants.

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3.0 SYSTEM DESCRIPTION

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3.1 Process Descr6 tion The CNSI Cement Solidification Unit is specifically designed to optimize solidification of radioactive wastes, evaporator bottoms, ion exchange resin slurries and sludges.

The cement process makes use of the readily available Portland I cement to solidify liquid wastes.

The process is initiated by transferring liquid waste into the CNSI disposable liner.

The waste is then conditioned by dewatering or adding conditioning chemicals as required.

With continuous agitation provided by the installed mixer blades, cement is added to develop a thick paste like slurry which will solidify to a hard, water-free end product.

l 3.2 Process Parameters i

The basis for cement solidification is the chemical reaction be-(

tween cement and water called hydration, which permanently combines these two elements to form a stable solid product. Certain chemi-cals present in the waste such as sodium sulfate and boric acid will require pretreatment to insure the hydration reaction occurs in a controlled and acceptable manner.

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l The sample verification procedure will serve to determine the exact pretreatment required and the volume of cement and the additives necessary to achieve optimum solidification. The amount of chemi-h cals used to solidify the full scale liner is determined using the results from the sample verification procedure and using the form-3 ula provided by the sample verification form, Figure 2.

S 3.3 Mobile Unit Descriotion o

7 3.3.1 The CNSI Cement Solidification Unit is a portable system containing all

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equipment necessary to solidify radioactive liquid waste us-k ing the cement process.

3.3.2 The unit is composed of several processing subsystems, each controlling a specific function of the cement process. These subsystems include waste transfer, chemical addition, cement I

conveyor, vent and dewater systems.

Control functions for the unit are incorporated into the pneumatic and main control f

panels.

Service supplies are provided by the utility and distributed through the service air, water, and electrical distribution systems.

3.3.3 Most of the mobile unit components are arranged on portable frameworks (skids) to provide flexibility of operations for either indoor or outdoor use.

The cement conveyor, control panel, pump skid, hydraulic skid and fillhead contain most of the major elements of the mobile unit.

-3.3.4 A closed-circuit television' system is an integral part of the

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' mobile unit and allows the operator to monitor the solidifi-cation process.

3.4 Systen Operation o

b 3.4.1 Before beginning any waste processing with the Cement Solid-l ification Unit, the CNSI' operator shall complete a successful i

sample verific~ation in accordance with the Sample verifi-cation Procedure of Section 5.0.

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3.4.2 Parameters established during the sample verification are recorded on Figure 2A. These parameters will be transferred to Figure 2C and, using precise scaling factors, the required chemical volumes for full scale solidification will be 8

calculated.

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3.4.3 Actual full scale solidification shall then be conducted in

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accordance with the MSU Operating Procedure (Reference 2.4) using the parameters calculated on the batch solidification form.

3.4.4 Secuence of Ooeration The waste is added to the liner first. It can be interrupt-ed at any time and the mixer may be secured while waste is in the disposable liner.

NOTE: THE MIXER MAY HAVE INSUFFICIENT POWER TO START THE MIXER BLADES IN A RESIN BEAD OR POWDEX SOLUTION IF ALLOWED TO SETTLE FOR EXTENDED PERIODS OF TIME.

THE MIXER SHOULD BE RUN AT MINIMUM SPEED WHILE TRANSFERRING AND DEWATERING THESE WASTES.

The mixer must be in operation during the addition of conditioner to facilitate thorough mixing, however, this process may be interrupted. The mixer must be in operation

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prior to commencing cement addition.

Cement addition and mixer operation should not be interrupted until process is

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completed.

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o 3.4.5 Mixer Speed The mixer speed should be high enough to allow complete mixino of waste conditioner and cement.

Generally, the-speed will be set at 75 RPM while adding conditioner and 50 g

RPM when starting cement addition.

The speed will be in-y creased to 100 RPM after two-thirds of the cement has been h

added.

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3.4.6 Waste-to-Cement Ratio (by volume)

The normal waste-to-cement / conditioner ratio will be approx-g l

imately 1 to 1 for boric waste and 1.5 to 1 for resins. If 7

5i normal ratios,are exceeded, free standing water may appear at the top of the matrix, usually hours after mixing is se-O cured.

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Cure time will usually be 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> and the temperatures may 0

rise during this time to 200 F.

The liner should be ventilated until temperature starts decreasing indicating a completed reaction.

4.0 RJOUIREMENTS FOR SAMPLE VERIFICATION 4.1 General Precautions NOTE: IF DIFFICULTIES ARE ENCOUNTERED WITH ANY PART OF. THIS VERI-FICATION PROCEDURE OR UNEXPECTED RESULTS ARE OBTAINED, CON-TACT THE SOLIDIFICATION MANAGER OR PROJECT ENGINEER.

CAUTION:

SODIUM HYDROXIDE IS EXTREMELY CAUSTIC.

USE RUBBER GLOVES WHEN HANDLING SODIUM HYDROXIDE.

FOLLOW THE PRECAUTIONS INDICATED IN SECTION 3.3 0F THE MSU OPER-ATING INSTRUCTION (REFERENCE 2.4).

4.2 Radioloaical Precautions l

a.

The CNSI operator shall be subject to the applicable health i

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physics and safety precautions of the facility providing the 1

radioactive waste.

5 b.

Laboratory gloves, face shield and an apron shall be worn 3

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while handling, collecting and testing of all samples.

B c.

The CNSI operator shall establish radiologically clean and l

contaminated zones in the sample process area to prevent the possible spread of contamination.

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4.3.1 Wane Recirculation Due to importance of obtaining a representative sample for use in the verification procedure, the waste-generating facility personnel shall confirm that the contents of the waste storage tank have either been recirculated for a minimum of three volume turnovers or are adequately mixed to achieve a homogoneous mix-ture.

b.

Several mechanical operations of the waste storage tank may negate the effects of previous recircu-lation/ agitation period.

These operations would in-clude the following:

(a)

Introduction of additional waste into the star-age tank after recirculation has comenced.

(b)

Securing of recirculation while drawing the verification sample.

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(c)

Shifting from a recirculation mcde to a transfer mode.

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If any of the situations listed above occur, it will be necessary to repeat the recirculation process and sample verification procedure of Section 5.0 in order j

to re-establish the solidification process parameters.

4.3.2 Eouipment E

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Equipment required for use during the sample verification procedure is listed in Figure 1.

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minimum quantity required to begin the verification pro-cedure.

8 The CNSI operator shall insurt that all necessary equipment

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  • r FIGURE 1 EOUIPMENT REOUIRED FOR TESTING SAMPLES Magnetic Mixer with Hotplate (1) 600 M. containers with lids (2)

Stirring devices (5)

Five M. pipettes (2)

Pipettor (1) 0 0-212 F Thermometer (2) pH Measuring Paper (3 boxes) 1000 M. Plastic Beaker (2) 0-600 gm Triple balance beam (1) 100 ML of 50% NaOH Solution 50 ml Buret (2)

- Ring Stand (1)

Buret Clamp (2)

Marking Pen (1) pH Meter with additional probes (1) 4.4 Samole Acceptance Criteria In order to insure acceptable solidification has occurred, the CNSI operator shall confirm that all acceptance criteria are met as a

follows:

a 1.

Visual inspection of the mixture after cement addition will g

confinn that the mixture is homogeneous with no free water M

on the surface.

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2.

Visual inspection of the end product after hardening is a uniform, liquid free, free standing monolith, g

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The end product resists penetration when probed with a pen-cil sized probe.

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4.5 Recuirements for Samole Verification

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4.5.1 Verify that all material listed in Figure 1 (equipment re-quired for testing samples) is available and ready for use.

4.5.2 Refer to Figure 2 when conducting sample verification.

(a)

Figure 2A is used to record the quantities of material used for the successful sample verification pro-cedure.

The actual values determined on these foms are converted to full-scale solidification values.

(b)

Figure 2C is used to calculate waste, chemical conditioner and cement volumes used in the full scale solidification.

It is also used to calculate' liner

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depth settings for the level probes.

(c)

Figure 2D identifies volumes and dimensions of casks and liners necessary for calculations.

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4.5.3 Samole Recuiremen g (a)

Samples shall be taken prior to each batch solidifi-cation and verified using the steps outlined in Sect-ion 5 of this procedure.

If repeatability is cemon-E strated by verifying the same parameters for five (5) consecutive samples ai..! if there is no change in the g

chemical composition of the waste as verified by g

chemical analysis provided by the utility, test re-A suits will be conside-ed reproducible.

Complete 3

E sample verification shall then be required for every fifth batch solidification.

Samples will still be required for each batch solidification except that Oc chemical verification for each sample shall be con-1*

ducted as outlined in Section 5.1 through 5.6.

(Omit-ting Steps 5.7 through 5.10).

Verification of pH in O

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waste chemicals and the parameters established in ac-cordance with this Process Control Program.

(b)

Samsle Line Purce The CNSI operator shall insure that at least one sample line volume is purged prior to drawing the sample which will be used with the verification pro-cedure.

5.0 SAMPLE YERIFICATION 5.1 Record the known information on Figure 2A and 2C.

Complete the rest of Figure 2A thru 2C as the information is obtained.

5.2 Notify utility personnel that all preparations for verification testing have been completed and request that a sample be drawn from the waste source.

g 5.3 Place the predetermined volume of waste in a 600 ml container. For PWR wastes and wastes containing boric acids, place sample on the 0

heater provided and maintain temperature at 145 F

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g 5.4 Check the mixture pH and record this value in the space provided in Figure 2A.

Turn off the sample heater and slowly add the sodium g

hydroxide checking the pH frequently until a pH between 11 and 11.5 g

is reached.

Record the final temperature, pH and the actual A

quantity of sodium hydroxide (NaOH) added.

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NOTE: pH CHANGES WITH ADDITION OF NaOH WILL NOT BE ;.INEAR.

NaOH SHOULD BE ADDED SLOWLY AND IN 1 ML OR.2 K. AMOUNTS.

8 ADDITIONALLY, A PH OF LESS THAN 11 WILL CAUSE EXCESSIVE CURE g

TIME AND A PH OF GREATER THAN 12 MAY CAUSE EXCESSIVE HEAT GENERATED IN THE LINER WHICH COULD LEAD TO CRACKING OF THE E

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5.6 Add the cement gradually (over several minutes), mixing continually to insure that a homogeneous mixture is obtained.

If the mixture becomes so thick that the dry cement is not mixing, before all the.

cement is addedt 1.

Discontinue adding cement 2.

Record the actual cement weight added on Figure 2A.

3.

Continue with Ste.p 5.7 of Uris procedure.

5.7 Place the lid over the sample and store in a shielded area.

5.8 Observe the sample at the following intervals and record the re-sults in the space provided on the Sample Verification Form.

NOTE: SOME WATER MAY APPEAR ON THE SURFACE AND BE REABSORBED DURING SOLIDIFICATION.

a) 1 hour1.157407e-5 days <br />2.777778e-4 hours <br />1.653439e-6 weeks <br />3.805e-7 months <br /> -

Visual inspection for settling with free water on surface.

b) 4 hours4.62963e-5 days <br />0.00111 hours <br />6.613757e-6 weeks <br />1.522e-6 months <br /> -

Visual inspection for free water on surface.

c) 12 hours1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> - Visual inspection for free water on the sur-face.

Probe with stirrer to check for hard-ness.

Repeat this step at 12 hour1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br /> intervals e

until the probe will not penetrate the sample g

E billet. When hard, no free water is allowed on the surface.

2 5.9 Set the sample aside for future disposal in accordance with CNSI 3N Operating procedure SD-OP-004 3

5.10 Complete Figure 2B before proceeding with the full scale solidification.

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..F 5.11 Samole Verification Problems t

NOTE:

IF AT ANY TIME DURING SAMPLE VERIFICATION A CONDITION OR REACTION OCCl!RS WHICH IS NOT EXPLAINED OR IS UNFAMILI AR TO THE OPERATOR, THE SOLIDIFICATION MANAGER OR THE PROJECT ENGINEER SHALL BE CONTACTED IMMEDIATELY.

5.11.1 Excessive water appears on the surface of the cement.

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Water appearing on the surface is a normal condition during the first hour and is reabsorbed during the curing process.

a)

Cause Insufficient cement added to the waste allowed in-complete hydration.

b)

Corrective Action If water remains on surface four hours afte* mixing, return to Section 5.0 and repeat the sample verifi-cation increasing the amount of cement added by 5%.

s 5.11.2 Sample is hard, water free and cannot be probed by a stir-rer witHn one hour of mixing, a)

Cause The reaction is proceeding too rapidly due to high pH Ex or abnormal chemical properties of the waste.

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Corrective Action cn l

1.

Return to. Section, 5.0 and repeat the sample C

m verification. Ensure the pH is adjusted as low 3

as poss,1ble in the 11.0 to 11.5 range.

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If the reaction is, still proceeding too rapid-ly, repeat the verification by decreasing the g

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7 3.

Contact the Solidification Manager or Project I

l Engineer if this problem persists.

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3 5.11.3 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> have elapsed and the probe will still penetrate the sample.

a)

Cause Improper waste conditioning er insufficient cement

addition, b)

Corrective Action Repeat Section 5.0 ensuring proper pH range and in-creasing the amount of cement by 5%.

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.F SAMPLE YERIFICATION FORM

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Operator Date utility / Location Waste Type Temp:

NOTE: ATTACH UTILITY ANALYSI.S OF WASTE STREAM TO THIS FORM.

Samole Procortions Sample No.

Amount

$1 - Sample Waste Volume ml

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S2 - Sample Sodium Hydroxide Volume ml 53 - Sample Cement Weignt gm 54 - Final Sample Weight gm 55 - Final Sample Volume ml 56 - Final Sample Density (54/55) gm/ml (Waste pH

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(Waste Temp

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Material Ratios o

57 - Waste to Final Volume Ratio (51/55) 58 - Sodium hydroxide to Final Volume Ratio (S2/SS) 59 - Cement to Final Weight Ratio (53/54)

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51 VALUE FOR SAMPLE VERIFICATION SHOULD BE 100 ML OF WASTE.

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57 SHOULD NOT EXCEED.60.

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SAMPt.I VERIFICATION F00M 4

Sa:::ple No.

Describe sample appearance, water amount, etc.

Sample at completion of mixing:

Condition Sample at I hour:

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I Sample at 4 hour4.62963e-5 days <br />0.00111 hours <br />6.613757e-6 weeks <br />1.522e-6 months <br />s:

Condition l

l Sample at 12 hour1.388889e-4 days <br />0.00333 hours <br />1.984127e-5 weeks <br />4.566e-6 months <br />s:

o Condition E

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l NOTE:

IF SOLIDIFICATION IS NOT COMPLETE AFTER 12 HOURS, ATTACH SHEETS TO CONTIht'E OBSERVATIONS AT 12 HOUR INTERVALS (MORE FREQUENTLY IF RE-QUIRED).

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r SAMOLE VERIFICATION

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Operator Date Location Waste Type Sample No.

Liner Payload Calculations:

Pl - Liner Density (56 x 62.4) lb/cu ft P2 - Cask Payload Ibs P3 - Liner Weight lbs

  • P4 (A) - Waste Payload (P2-P3) lbs
  • P5 (A) - Liner Solidified Voluce (P4/P1) cu/ft
  • P4 (B) - Waste Payload (P1 x P5(B))

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'95 (B) - Liner Solidified Volen (Liner Capacity) cu/f t --

P6 - Volume of waste added to liner (57 x PS) cu/ft P7 - Volume of sodium hydroxide added to liner (53 x PS) x 7.48 gal P8 - Weignt of cement added to liner (59 x P4) lbs I

P9 - Volume of cement added to liner (P8/450) cycles L2-Waste Level in.

P6 X 2200 L3-Cement Level in. 'PS X 2200 2

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Due to the density of cement, some liners may be volume limited and some may be weight limited. Calculate P4(A) and (B) and P5(A) and (B) and use

.k the smaller of the two figures in further calculations.

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m (INSR AND CASK CALCULATIONS Liner Dieeter (01 Heicht (H)

Acc. Weicht (lbs1 L21-300 82" 104 1/2" 2400 L14-195 76" 75 1/2" 1850 LS-120 61" 71 1/2" 1250 L7-100 74 1/2" 37" 1400 L6-80 58" 54" 1100 CASK PAYLOADS:

6 7500 lbs 7-100 7000 lbs

~ 8-120 10000 lbs14-195 17700 lbs

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-.'r 6.0 ADMINISTRATIVE PRCOEDURES

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6.1 Maintenance of Recores 6.1.1 The CM51 operator shall forward a. copy of a.ll co pleted sample verification forms to the Solidification Manager for review following completion of liner solidification.

6.1.2 Figure 2A should be used as a cover sheet when forwarding records.

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