ML20151G682

Forwards Addl Info in Response to NRC Request Re Premature Solidification of Radioactive Decontamination Solution Waste

ML20151G682
Person / Time
Site:	Quad Cities
Issue date:	07/15/1988
From:	Johnson I COMMONWEALTH EDISON CO.
To:	Murley T Office of Nuclear Reactor Regulation
References
NUDOCS 8807290103
Download: ML20151G682 (42)

Text

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Commonwealth Edison s

/ One First Natonai Plaza. Chicago, Ilknois g

7 Address Revy to. Post Offce Box 7C

,/ CNcago, Ithnois 60690 0767 July 15, 1988 Mr. Thomas E. Murley, Director Of fice of Nudear Reactor Regulation U. S. N uc.' s 2.; Regulatory Commission Washington, DC 20555

Subject:

Quad Cities Station Units 1 and 2 "Response to NRC Request for Information Pertaining to the Premature Solidification of Radioactive Decontamination Solution Waste at Quad Cities Station" URC_ Docket Nog. 50-254 and 50-26 Reference (a): Meeting Minutes Generated by T. Ross (NRC) f rora May 24, 1988 Heeting with Comonwealth Edison, Chem Nuclear and NRC Personnel Regarding above Referenced Topic

Dear Mr. Murley:

The purpose of this letter is to provide additional information to members of your staff regarding the premature solidification of a decontami-aation solution radioactive waste liner which occurred at Quad Cities Station on April 20, 1988.

The details of this event are documented in Quad Cities Licensee Event Report (LER)88-014, Rev. 00, dated June 22, 1989 Additionally, there have been numerous telephone conference calls between representatives of Commonwealth Edison (I.M. Johnson, D.L. Farrar, S. Davis, i

G. Spedl, et.al.) and members of your staff, in particular, Mr. T. Ross, (NRR Quad Cities Licensing Project Manager) and Mr. J. Lee (NRR, Plant Systems Branch). These discussions culminated in a May 24, 1988 meeting between NRC, l

CECO and Chem Nuclear personnel. Reference (a) documents the scope of the l

discussion, as well as those items for which additional information was being l

requested. Commonwealth Edison initially agreed to respond to these items within forty-five days of the meeting. This commitment date was extended to July 15, 1988 in subsequent discusalons between I.M. Johnson and T. Ross.

Attached, please find Commonwealth Edison's response.

The response consists of several sections which are described as follows:

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ADOCK 05000254 PDC

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T.E. Murley July 15, 1988

1) Attachment A Information Perteining to the Quad Cities Unit 2 Decontamination and Resultant Waste Solidification This includes a discussion of event and factors that may have caused premature acceleration of the solidification process. This includes information on the decontamination as well as other information which had been requested by the staff during the meeting, but not detailed in the meeting minutes (specifically the order in which the resins had been sluiced into the liner).

2) Attachment B:

Corresponding Between Commonwealth Edison and Chem-Nuclear Regarding the Affected Liner.

3) Attachment C:

Past Practices of Surrogate Waste Samples in the Solidification of Decontamination Solutions at Quad Cities Station.

This includes a letter from P. Denault to S. Davis, (CECO), dated July 14, 1988 which describes in more detail the process by which the surrogate sample is prepared.

4) Attachment D Plans for Disposal of Waste Liner and Implementation Schedule.

5) Attachment Et Proposed Long Term Corrective Actions.

Reference (a) also indicated that Commonwealth Edison would receive, under separate cover, a request to transmit solidified resin material samples to the NRC, or its contractor.

These samples were collected at Quad Cities by the Idaho National Engineering Laboratory (INEL), personnel who were partici-pating in a project under the direction of Dr. P. Reed, NRC, Research. The request for sample transmittal is to also explain the intended disposition of said samples. The samples which were collected represent both unsolidified resin which had been sluiced into the liner, prior to the addition of cement, as well as samples that were "grabbed" f rom the top of the liner af ter the mixer shaft selsed.

It is our preliminary judgement that these samples may not accurately depict the actual Quad Cities liner.

At this time, it is uncertain that the unsolidified mixed resin samples are truly representative of the liner since the samples were taken f rom the top portion of the cask, af ter it had been agitated, but not during the actual period of agitation.

In the case of the samples taken f rom the liner following the addition of concrete, their representativeness to the liner is also in question. These dip samples were taken from the top of the liner and may have collected an unrepresentatively

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T.E. Murley

- July 15, 1988 large percontage of f aam in the event foam was formed during mixing.

Commonwealth Edison is doiny further reviews of these samples in order to confirm thar h+ 11e f s. The results of our review will be provided to your staf f at ti e that the samples are transmitted to your contractor for off-sita tonwealth Edison's current plan to encapsulate the affected liner ant aor disposal to Barnwell, South Carolina by early September, 1988.

Please direct any questions that you may have regarding this matter to this office.

Yours very truly,

. y1 I. M. Johns n /

Huclear Licensing A istrator Im Attachments A Information Pertaining to the Quad Cities Unit 2 Decontamination and Resultant Waste Solidification f

B:

Correspondence Between Commonwealth Edison and Chem-Nuclear Regarding the Affected Liner C

Past Practices of Surrogate Waste Sample Usage D

Plans for Disposal of Waste Liner and Implementation Schedule Et

?roposed Long Term Corrective Actions cc:

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Ross-NRR QC Resident Inspector 4910K

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j AD ACBW M _A "INFORMATION PERTAINING TO THE OUAD CITIES UNIT 2 DECONTAMINATION AND RESULTANT WASTE SOLIDIFICATION" Narrative Summary of the Decontamination and Sol.idification Process Cause of Premature Hardening Order in which Resin Wastes Were Sluiced into Solidification Liner l'

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NABRATIVE SUMARY OF THE DECONTAMINATION AND SOLIDIFICATION PROCESS In late April 1988, Unit 2 of Commonwealth Edison's Quad Cities Station was chemically cleaned using the LOMI process. This method employs a solution of vanadous formate with picolinic acid'as a sequestrant for iron, partially neutralized with sodium hydroside. Make up water is usually treated with hydrazine to remove dissolved oxygen.

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The decontaminstion was perfcrmed first on the recirc pump discharge piping, followed by recirculation of the spent solvent through cleanup resin columns containing Weak Base Anion (WBA) resin and Strong Acid Cation (SAC).

Due to station concerns relating to high reactor vessel water level, excess water was drained through resin columns consisting of mixed bed Strong Base Anion (SBA) resin and SAC.

All resin used at that point was sluiced tot he solidification liner. New resin was then loaded into the resin columns, followed by decon of the suction piping. Upon completion, solvent was cleaned up using WBA and SAC resin. Once the majority _of solvent was removed from the suction piping, the expended resin was sluiced to the liner and fresh resin reloaded. A final clean-up or polishing of the water-from the entire system was performed.

Finally, the remaining re11n was sluiced, from the resin columns into the solidification liner. These operations were performed by the decontaminstion vendor, LN Technologies.

A sample of simulated spent resin waste was also prepared by LN Technologies and used by the solidification vendor for purposes of performing test solidifications. The rationale.for use and preparation of the simulated waste sample will be discussed in more detail later.

The waste solidification process was performed by Chem-Nuclear.

Excess water was drawn out of the liner to the extent prescribed by the solidification formula to be used. The liner mixing motor was then started, and after some period of mixing resin samples were drawn by a representative af EG&G Idaho.

The solidification formula called for the addition of 7500 pounds of cement to the liner.

Per normal operations of the cement additional was stopped for a period of approximately 15 minutes after the first 2400 pounds

. had been added to permit Chem-Nuclear personnel time to refill the cement addition hopper.

During this 15 minute delay, however, the entire cement mixture increased in viscosity to the point that no further addition was

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possible. At that point, the EG&G samples were drawn from the surface o' the cement mixture.

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CAUSE OF PREMATURE HARDENING During the extensive investigation into this event performed by CECO and its representatives, it was determined that the only parameter that underwent significant change in this case involved the formula used by Chem-Nu: lear to solidify the spent resin waste. This change involved the total deletion of time.

Through considerable research, no evidence appears to exist that calcium undergoes significant chelation reaction with picolinic acid (unlike other cLelates such as EDTA). Thus, it appears that lime reaction with excess chelant is not a consideration.

However, it has been well documented and demonstrated both in the nuclear industry and elsewhere that the introduction of limo to a cement mixture serves to retard or slow the hydration reaction.

Furthermore, lime will ect to neutralize the relatively low pH waste, thus introducing a very significant heat of neutralization to the liquid waste in the liner.

Some small quantity of heat will also be given off through the ion exchange of calcium with the unexpended sites on cation resin (CECO estimates that only 50% of the theoretical capacity for the mixed bed resin used for polishing was expended).

-Previous Chem-Nuclear solidification practices involved the introduc-tion and thorough mixing of the entire quantity of lime to the 11guld waste prior to commencing with cement addition. The lime addition step normally took % to I hour to complete. The introduction of cement to the liner was alto performed at a slow enough rate that the heat contributions of neutraliza-tion and resin depletion would normally have on the order of two hours to diselpate prior to the time significant cement hydration could occur. With the deletion of lime from the formula used in the subject case, the cement itself had to provide neutralizing and ion exchange capacity. The simultaneous use of the cement to neutralize and solidify the waste brought about a circumstance whereby the heat of neutralization raised the temperature of the cement mixture (calculation shows by approximately 45*F), which acted to greatly accelerate the hydration, the heat from which would have acted to cause further acceleration of the process.

In summary, CECO concludes that the heat of chelation is not of significance. The heat of neutralization, the heat of hydration, and to a lesser exteat, the heat of lon exchange acted together to cause a significant temperature increase in the cement. The fact that this heat could not dissipate quickly enough, together with the E3sence of a retardant from the solidification formula resulted in the premature hardening of the cemented waste.

Thus, CECO concludes that the deletion of lime, together with no requirement in the Chem-Nuclear PCP to require monitoring of the hydration rate of the test solid!.fication are the causes of premature hardening.

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._m ORDE1 LIE _1f}{ICH RESIN WASIIS WERE SLUICED INTO THE SOLIDIFICATION LINER 1.

First, 3 columns of SAC clean-up resin were sluiced, 21 ft3 total 2.

Then 3 columns of WBA clean-up resin, 21 ft3 total 3.

3 columns mixed bed SAC /SBA 21 ft3 total (14 ft3 SBA, 7 ft3 SAC) 4.

2 columns SAC, 14 ft3 total 5.

2 columns WBA, 14 ft3 total 6.

2 columns mixed bed SAC /SBA 14 ft3 total (9 ft3 CBA, 5 ft3 SAC) 7.

1 column 5 ft3 WBA, 2 ft3 SAC 1 column 3 f t3 SAC, 4 ft3 SBA 40 ft3 WBA 27 ft3 SBA 52 ft3 SAC 119 ft3 total 4910K

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,4 ATTACMENT B "CORRESPONDENCE BE*lHEEN COMMONWEALTH EDISON AND CHEM-NUCLEAR REGARDING AFFECTED LINER" June 15,-1988 letter from J. Jeffrey (Chem-Nuclear) to S. Davis (CECO)

June 17, 1988 letter from J. Jeffrey (Chem-Nuclear) to R. Petri (CECO) 4910K

r CHEM-NUCLEAR SYSTEMS,INC.

Stoneridge Drive

• Columbia, South Carohna 29210 June 15, 1988 Hr. Steve Davis Commonwealth Edison Company Technical Center, Room 306 1319 South First Avenue Haywood, IL 60153

Dear Mr. Davis:

I enjoyed our meeting in Channahon on June 10th and feel it was very productive.

The following is a list of questions that you desired to be answered and Chem-Nuclear's (CNSI) response to those questions.

1.

Question:

What is CNSI's current theory on the cause of the Problem?

Response

Testing was conducted at our Barnwell Testing Facility uttlizing LOHI and Bead Resin Solution with a pH of 3.0 based on the surrogate sample provided by Quad Cities prior to the solidification.

It was found that the addition of P-20 Binder initially increased the temperature 200F due'to the heat of neutralization of the solution.

It was also found that addition of lime caused the same temperature increase.

Temperature increase for a more typical Bead /LOHI with a pH of 5 to 6 was only 3-40F.

This increased temperature doubled the rate of hydration, which increased the viscosity and effectively reduced mixing time by half. Although addition of lime initially would have given the same temperature increase, no thickening would have occurred and the mix could be allowed to cool to ambient prior to the cement addition.

2.

Question:

Why has CNSI changed its opinion of why the problem occurred?

Response

At the time of our original assesspent of the situation, it appeared that premature thickening of the waste hindered l

addition of all the requirecfbinder.

This premature thickening was thought to be 'due to' chemical reactions involving the decon solution and the lime formed during the l

initial hydration of cement.

This opinion was based on CNSI's kncwledge of chelate material in general and was not l

based on actual testing. Once surrogate sample testing was initiated, it was evident that the Quad Cities waste was more susceptible to thickening due to higher temperatures as explained in the Response to Question #1.

3.

Question:

Do you have a Certificate of Compliance on the P-20 used?

Response

Certificate of Compliance on the P-20 is enclosed as Addendum I.

(803) 256-o450

• Telex: 216947

s Steve. Davis June 15, 1988 Page 2 4.

Question:

What do you intend to do to prevent reoccurrence of the problem?

Response

All future solidification will be accomplished utilizing an approved PCP formula.

This includes the use of lime when prescribed.

In addition, solidification procedures will be changed to alert the operator to low pH situations.

Steps will be added to monitor for temperature rise caused by waste neutralization following lime addition.

If this temperature rise is observed, the solidification process will be interrupted to allow the temperature to decay to ambient.

It will then not add to the temperature rise from cement hydration causing faster hydration and the attendant higher viscosity.

5.

Question:

Do you have the procedure available for encapsulation of the problem liner?

Response

CNSI Procedure SD-0P-084-445 for encapsulation of the Quad Cities liner is enclosed as Addendum II.

It has also been officially sent to both the plant and the CNSI operator.

6.

Question:

Has the encapsulation process been accepted by the' State of South Carolina for burial at Barnwell?

Response

Encapsulation is an accepted practice for disposal of certain waste forms at the Barnwell site.

Recent convershtions with the State (DHEC) have confirmed that encapsulation is a viable method of providing stability for this liner.

7.

Question:

In what time frame did the samples, which were run to determine minimum binder needs, go hard?

Response

As stated in our letter of June 6 to Mr. Ray Petrie, the samples, which were run to determine the minimum amount of binder which could be stirred into the mixture to assure there was no free liquid, were hard and water free within 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />. Although no hour-by-hour check was made of the progress of solidification, it was noted that both samples tested were firm and definitely not mixable six hours after mixing.

If I can be of further assistance in this area or if there are additional questions, please do not hesitate to call me.

Sincerely, ffrey General Manager Nuclear Services c:

Irene Johnson Ray Petrie Mike Ryan

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June 10, 1988-CERTIFICATION This is to certify that Portland Pozzalon Cement manufactured by Santee Cement Company, Holly Hill, S. C. and packaged by Concrete Bag Products Co.,

Inc., Gilbert, S. C.

for Chem-Nuclear Systems, Inc., Barnwell, S. C. under the label of P-20 contains 81% + or - 1% Type I Portland Cement and 19%

+ or - 1% Fly Ash, meeting the ASTM specifications C595 for Portland Pozzalon Cement, purchased under these #N-447375,

1. N-448077, #N-450083.

CONCRETE BAG PRODUCTS C0 INC.

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M. R. Greenthal'er President i

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.r.M coment Company P.O. Box 0024 A Subsidiary of eveses ColumtWa. South CaroNna 20200 (803) 7364702 Mr. Dan Lackey Chem Nuclear Systems, Inc.

P O Box 726

Barnwell, S.C.

29812 AIIID 3y1T W is is to certify that TYPE IP Portland-Pozzoland Cementj s manufac-a tured by SANTEE CDENT CCMPANY at our facilities at Holly Hill, South Carolina, is warranted to ccnform at time of shipnent to present A.S.T.M.

Specificatico C-595; A.A.S.H.T.O. Specification M-240 and Federal Specification SS-C-1960/4 for TYPE IP Portland-Pozzolan Canent. De Pozzolan used ccnfonns to A.S.T.M. C0618, Class F and amount used does not exceed 20% by weight of canent. h e total alkali expressed as sodiun; equivalent (Na20+K20 (0.685))is less than 0.60%

No other warranty is zhade or to be inplied.

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NCffAPY PUBLIC OF'SOUIH CAROLLNA My comtissico expires: 6-30-1990 l

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DESCRIPTION DATE APP. OVED C

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DATE REVISION $TATUS SHEET 1

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RED DATE jg 5-t- 86 CHEM - NUCLEAR SYSTEMS, INC.

OPERATING PROCEDURE FOR IN-SITU SOLIDIFICATION USING ENGINEER MOBILEIN-SITUUNIT(HIV-1)ATQUADCITIES.

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TABLE OF CONTENTS k.

PAGE NO.

1.0 SCOPE..............................

3 1.1 Purpose 3

1.2 Applicability 3

2.0 REFERENCES

3 3.0 REQUIREMENTS..........................

3 3.1 Prerequisites 3

3.2 Equipment 3

4.0 ASSEMBLY.............................

4 5.0 PRE-0PERATIONAL TESTING....................

5 6.0 SYSTEH OPERATION 6

7.0 SYSTEH SHUTDOWN / DISASSEMBLY,..,..............

7 8.0 ACCEPTANCE CRITERIA.......................

8 9.0 R ECORDS AND R E PORTS......................

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9.1 Process Memo......................

8 9.2 Solidification Records.................

8 APPENDIX A - SAF E TY DATA SH E ETS...................

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1.0 SC0ff i

1.1 Puroote This is a procedure for In-Situ Encapsulation Of 14-195 and Smaller Liners.

It provides instructions for batch mixing cement in a mixing liner and transfer of the cement mixture to a 21-300 encapsulation liner.

1.2 AeolicabilitV The instructions contained in this document apply to use of the In-Situ Solidification equipment.

2.0 REFERENCES

2.1 CNSI Procedure, SD-OP-003, "Process Control Program For CNSI Cement Solidification Units" 2.2 CNSI Procedure QA-TP-009, "Hydrostatic Test Requirements" 2.3 CNSI Procedure, FO-AD-007, "Nuclear Services Equipment Shipping Procedure."

3.0 RE0VIREMENTS 3.1 Prerecuisites 3.1.1 Acquire a Radiation Work Permit (or equivalent) from the utility's Health Physics Department.

3.1.2 Inspect and use, as appropriate, protective clothing, safety glasses, chemical splash goggles, face shield, hard hat, safety shoes, gloves and respirator.

Know where the closest eye wash and safety shower are and' how to use them.

CAUTION:

HOSES AND OTHER PRESSURE RETAINING COMPONENTS HAY BE PRESSURIZED.

FACE SHIELDS AND APPROPRIATE PROTECTIVE CLOTHING SHALL BE HORN DURING DISASSEMBLY OF THIS EQUIPHENT.

3.1.3 All straight ladders must be tied at the top or held at the bottom by a co-worker.

3.2 f_ qui oment The equipment required consists of a mixing liner, hydraulic power unit, pumps, hoses, and a 21-300 encapsulation liner which will contain the liner to be encapsulated with cement.

3.2.1 Hixina Liner The mixing liner is a steel liner with the addition of an outlet in the bottom with isolation valves and connection to a cement transfer system.

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I, 3.2.2 Transfer System i

The transfer system is a 1-1/2" or 2" diaphragm pump, suction and discharge hose with a disposable tail i

piece, and manually operated valves used to transfer the cement mixture from the mixing liner to the encapsulation liner.

3.2.3 Air Hanifold The air manifold consists of the necessary valves, air dryer, hoses, piping and fittings necessary to connect an air supply from the utility and operate'the cement transfer system pump (s).

3.2.4 Encapsulation Liner This process uses a 21-300 encapsulation liner with.

. pre-poured cement base and top motion limiters to center the liner to be encapsulated and prevent it from floating.

3.2.5 Level Indication Level indication is monitored by either a TV camera or mirror and a' clearly marked indicator to ensure proper cement level in the encapsulation liner, hj 3.2.6 Service Water Hanifold The service water manifold consists of the necessary valves, piping and fittings to connect a service water supply from the utility to the mix liner.

4.0 ASSEMBLY 4.1 Set mix liner off the trailer to a level surface capable of supporting its weight in area adjacent to process area.

4.2 Install mixer head on mix liner.

4.3 Locate hydraulic unit next to mix liner.

4.3.1 Connect hydraulic hoses between mixhead and hydraulic unit.

4.3.2 Connect hydraulic power lead to 3 phase 60 cycle 480 VAC, 60 AMP source.

4.4 Locate air distribution manifold adjacent to hydraulic unit.

4.4.1 Connect plant service air to manifold inlet.

4.4.2 Check oil level of oiler.

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4.4.3 Check all outlet valves shut.

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4.5 Locate cement transfer pump adjacent to mix liner (a location midway between mix and disposable liner may better suit the situation).

4.5.1 Connect the air supply hose from the air manifold to the transfer pump supply.

Fully open the throttle valve on the pump inlet block.

4.5.2 Connect section(s) of 1-1/2" non-collapsable suction hose between cement transfer pump suction and mix tank outlet.

4.5.3 Connect 1-1/2" discharge hose from cement transfer pump to the encapsulation liner.

4.6 Locate service water manifold adjacent to hydraulic unit.

4.6.1 Connect service water supply from the plant source to inlet of the manifold. -

4.6.2 Connect the 1/2" hose from the service water manifold and secure end to mix tank.

5.0 P_R_E-0PERATIONAL TESTING -

The trahsfer system is connected between the mixing liner and a service water discharge.

_r 5.1 Perform a pre-operational check of the transfer system using

service water.

5.1.1 Test the transfer system for proper operation and leakage by adding service water to the mixing liner and pump with the transfer pump with discharge hose plugged. -Precautions shall be taken to vent hose prior to removal of plug (test to be performed and documented IAH Reference 2.2).

NOTE:

00 NOT DISCHARGE SERVICE HATER INTO THE ENCAPSULATION LINER.

5.2 Perform pre-operational check of Hydraulic Unit.

5.2.1 Ensure hydraulic reservoir is at proper level. Add oil as necessary as determined by sight glass.

5.2.2 Jog hydraulic unit to ensure proper direction of rotation.

5.2.3 Operate hydraulic unit to ensure proper operation mixing motor and check all hydraulic hose connect

.n for leakage.

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I 6.0 SYSTEM OPERATION

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6.1 Verify the following conditions exist:

1 6.1.1 The liner to be encapsulated is ready for transfer.

6.1.2 A PCP sarrple has been completed satisfactorily in accordance with Reference 2.1.

6.1.3 Pre-operational checks have been completed satisfactorily in accordance with Steps 5.1 through 5.2.

6.1.4 <

The mixer head is ready for operation on the mixing liner.

6.2 Prepare the encapsulation liner to receive the liner to be encapsulated and the cement mixture.

6.2.1

' Open and inspect the encapsulation liner for foreign materials, damage, and ensure that the pre-poured bottom is intact.

Record liner condition and serial number in the Daily Operations Log.

6.2.2 Install the temperature prob,e.

6.2.3 Install a clearly marked indicator such that the cement level in the encapsulation liner after filling will be

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at least 5 inches above the encapsulation liner top.

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Ensura level indicator is visible.

-. 6.2.4 Firmly attach a disposable cement hose tailpiece to the encapsulation liner and connect to cement transfer pump.

6.2.5 Transfer tne liner to be encapsulated'into the encapsulation liner and ensure thpt it is properly positioned to provide required encapsulation thickness.

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6.2.6 Install the rebar grid work on top of the liner.

The grid should rest on the barrel-top and be approximately centered above the liner being encapsulated.

6.2.7 Install the nrotion limiter in the encapsulation liner.

l 6.3 Add and mix the required arnounts of chemicals and cement to the mixing liner and prepare for transfer per the following steps:

NOTE:

REFER TO THE PROCESS CONTROL PROGRAM (REFERENCE 2.1 FOR THE PROPER AMOUNT OF HATER AND CHEMICALS.

6.3.1 Add the required amount of water to the rnixing liner.

6.3.2 Start the mixer and adjust the speed to approximately 10 rpm.

(Speed may be varied at operators discretion to ensure proper mixing.)

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6.3.3 Add the required amount of cement in accordance with j

the Process Control Program.

6.3.4 Add the rpquired amount of lime in accordance with the Process Cvntrol Program.

6.3.5 Increase mixer speed to approximately 20 rpm.

(Speed may be varied at operators discretion to ensure proper mixing.)

6.5.6 Confirm the flow characteristics of the mixture and that it has a smooth, fluid consistency.

Continue to mix for 15 minutes.

NOTE:

BORIC ACID AND/0R S00IUH SULFATE MAY BE ADDED TO THE LINER TO ASSIST IN CONTROL OF THE EXOTHERH BASED ON THE TEMPERATURE AT THE START OF THE PROCESS. REFER TO REFERENCE 2.1 FOR REQUIRED AHOUNTS.

NOTE:

ALL DRY CHEMICAL ADDITIONS HILL BE 1101. OF CALCULATED AHOUNTS.

6.3.7 Ensure the transfer hos6 is attached to the encapsulation liner, level indicator is visible and the temperature indicator is installed to monitor the exotherm.

6.3.8 Transfer the cement mixture into the encapsulation liner until the proper level is achieved (level indicator is covered). Secure the transfer system.

6.3.9 Disconnect the transfer hose at the disposable tailpiece.

Flush any remaining cement mixture into a suitable container.

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6.3.10 Disconnect tailpiece from encapsulation liner.

6.3.11 The TV camera can be de-energized and removed (if used).

6.3.12 After cement begins to set (approximately I hour),

remove the motion limiter and fill holes, if necessary.

7.0 SYSTEM SHUTDOWN / DISASSEMBLY 7.1 Secure the hydraulic unit and disconnect hoses and electrical power.

7.2 Flush the fillhead, reixing liner, and transfer system.to ensure removal of all cement mixture.

NOTE:

IF IT IS NECESSARY TO ADD ADDITIONAL CEMENT HIXTURE TO LINER DUE TO SLUMPING, EIPEA' STEPS 6.4 THRU 7.2.

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7.3 After Section 8.0 (Acceptance Criteria) has been completed, seal the encapsulation liner.

7.4 After final process is complete drain the mix tank completely.

7.5 Olsassembly may be in any order; ensure all systems disconnected from plant supplies.

(Any contaminated hoses may be disposed of in process liner or in accordance with plant directions.)

7.6 Package for shipment in accordance Reference 2.3.

8.0 ACCEPTANCE CRITERIA 8.1 A solidified cement encapsulatien liner shall be considered acceptable if the following conditions are met:

8.1.1 Visual inspection of the end product, normally 24-72 hours af ter process completion, shows a uniform product

• with no free-standing water.

8.1.2 The end product, after satisfactory visual inspection, resists penetration when probed with a wooden rod or dowel approximately 1" in diameter.

CAUTION:' THE SOLIDIFIED MATRIX HUST BE LESS THAN 175'F AND BE STEADILY DECREASING IN TEMPERATURE PRIOR TO SEALING. ADD A SHALL (u

AHOUNT OF DRY CEMENT TO SOLIDIFY ANY LIQUID L

ON THE BILLET SURFACE THAT HAS NOT ABSORBED HITH THE DECREASING TEMPERATURE. THE LINER SHALL NOT BE SEALED S0ONER THAN 30 HOURS AFTER COMPLETION OF HIXING.

9.0 RECORDS AND REPORTS 9.1 Process Memo The Process Memo shall accompany the shipment with appropriate copies mailed to the Supervisor, Haste Processing Services.

9.2 Solidification Records The technician shall maintain a copy of the CNSI Solidification Horksheets. A copy of the CNSI Solidification Worksheets and the temperature recording of each solidification shall be mailed to the Supervisor, Haste Processing Services upon completion of the solidification.

DOCUMENT R E Y.

gMEET SD-0P-084-445 8

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APPENDIX A l

HATERIAL SAFETY DATA SHEETS (6 PAGES) l e

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l I

REV.

SHEET SD-OP-084-445 9

L J

Material Safety Data Sheet

$R1C ACd 4

From Genium's Reference Collection (Revision C)

Genium Publishin Corporation 1145 Catal Street Issue.d: March 1983 Schenectady, NY l 3031836 USA t

f51D 377 8855 coauw mes cow.

Revised: January 1987

SECTION 1. MATERI AL IDENTIFICATION

' ~

22 MATERIAL NAME: BORIC ACID DESCRIF' TION /USES: Natural state is the mineral sassollte. lUsed for heat resistant glass; glass O

fibers; porcelain enamels; bo O O in fengus control on citrus fr(on chemicals; metallurgy; as a flame retardant in teatile products; uits; ointment; electroplating baths.

OTHER DESIGNATIONS: Orthoboric Acid, Boracie Acid, fydrogen Borate.

HMIS H_3BO ; CAS s10043 35 3 3

H 0

MANUFACTURER /SUPPflER: Available from several suppliers, including:

Ashland Chemical Co, Industrial Chemicals & Solvents Div, PO Box 2219, F 0 R 1 Columbus, OH 43216; Telephone: (614) 889 3333 R

0 I

US Borax and Chemical Cck,3075 Willshire Blvd., les Angeles, CA 90010; PPE*

S 2 Telephone:(213) 3815311

• See Sect. 8 K0 SECTION 2. INGREDIENTS AND HAZARDS"

%W-HAZARD DATA-Boric Acid, CAS s10043 35 3 ca 100 No TLV Established.'

Rat, Oral, LE50 26N) mg/kg Human, Sidn,15 mg/3 Days, Intermittent: Mild Irritation

• Control as a nuisance particulate.

ACGill1LV is 30 mppcf or 10 mg/m total dust, or 5 mg/m3 espirable Y8 3

r du st.

. SECTION 3. PilYSICAL DATA '

Boiling Point Not Found Melting Point 339 to 356'F (170 to 1$0'C) e Vapor Pressure,21*C, rnm Hg 15 (due to H O)

% Volatile by Volume Not Found 2

Water Solubility, g/100g @ 20*C -. 4.9 Molecular Weight 61.84 Vapor Density,(Air - 1) Not Found pli @ 20'C,1% Aqueous Soln. ca 5.2 Evaporation Rate Not Found 4% Aqueous Soln.ca 3.9 Specific Gravity (110 1). 1.435 2

Appearaoce and odcr:

Fine or granular white powder or color! css crystals. Odorless.,

SECTION 4. FIRE AND EXPLOSION DATA' LOWER UPPER Flash Point and Method Autoignition Temperature Flammability Limits in Air Not Not Noncombustible Not Found Not Found Found Found EXTINGUISHING MEDIA: Use whatever agent is most appropriate to extinguish surrounding fire. Boric acid does not support combustion and is noncernbustible.

There are no unusual fire or explosion hanrds associated with this material.

'There are no special fui fighting procedures when extinguishing a boric acid fee.

Fire fighters should ute self contained breathing apparatus and wear fully protectim clothing when fighting fires of borie acid.

SECTION S. REACTIVITY DATA Boric acid is stable. Haurdous pol)rneriution cannot occur.

Boric acid is a weak acid. It loses chemically combined water upon heating, forming metaboric acid (11002 at 212 to 221*F (100 to 105'C), then pyroboric acid (118.g0 ) at 285 ta 320*F (140 to 160*C), are boric anhydride (D 2

7 23 temperaturcs.

It reacts with basic materials such as alkali carbonates and hydroxides to form borate salts. A misture of potassium and toric acid may caplode on impact. When it is mixed with acetic anhydride, it can text violently when heated to 136140'F (58 60*C).

If moisture is present, boric acid can be conosive to iron.

/

No products of haurdous decomposition should be espected.:

5$?JT E"' % N-C"4w.w r- - a ""

SD-0P-084-445, APPENDIX A PAGE 1 l

• ~

NA4 1/87 BORIC ACID SECTION 6. IIEALTH liAZARD INFORMATION lTLV Boric acid is not listed as a carcinogen by the FUP, IARC, or OSilA.

SUMMARY

OF RISKS: Excessive inhalation of boric acid dust can cause initation to the mucous membranes of the i

respiratory tract. This material is not significantly absorbed through imaG1 skin. It is reMuy absorbed through damaged, abrMed, and bumed skin, or open wou)ds and areas of active dermautis when they are exposed to dry materials or aqueous.

solutions. Ingesdon or absorpoon of boric acid may cause nausea, somiting, anuna (absence of or detective excretion of prine), crythematous (abnormally red) lesions on the skin and mucous membranes, abdominal cramps CNS effects after 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />, circulatory failure, and coma. Poisoning can be acute or chronic. The acute fatal dose to adults is reported at 5 to

>30g (moderate to slightly toxic). Studies of dogs and ' rats have showri that infertility and damage to testes can result from acute or chronic ingestion of boric, acid. Evidence of toxic effects on the human reproductive systern is inadegunte. TARGET ORGANS: Skin and central nervous systern. The primary route of entry is by way of damaged or abraded skan, ingesdon, or Inhaladoo. AClfrE EFFECTS: Eye irritation, skin irritation, and gastnc disturbances from ingesGon. CHRONIC EFFECTS:

Excessive amovots of this materiajiabsorbed into the blood stream may result in erythema, a macular (blotchy) rash, dizziness, gastric disturbances, and depression. FIRST AID EYE CONTACD Flush eyes thoroughly, locluding under cyclids, with running water for 15 minutes. Get medical help.' SKIN CONTACT: Rernove gross! conuminated clothing under a safety shower. Flush affected area with water; wash with soap and water. Get med; cal he.' INHALATION: Remove i

victim to fresh air. Restore arWor support his breathing as required. Get medical help ' INGEST

Rinse victim's rnouth with water. Give him 2 to 3 glasses of water to drink to dilute the material. Induce vorniting. Never give anything by rnouth to someone who is unconscious or convulsing. Get rnedical help.'

' GET MEDICAL ASSISTANCE = In plar( paramedic, community. Get rnedical help for further treatment, observa6on, and sugert after first aH SECTION 7. SPILL, LEAK, AND DISPOSAL PROCEDURES Before using boric acid it is essends! that proper ernergency procedures be established and mMe known to all personnel involved with it.

Notify safety personnel of boric acid spills. Provide adequate ventilation. Cleanup personnel need protection against inhalation of dust Sweep up or vacuum the spill, avo'id dusting condidons, and place waste material in an appropriate container for reclamation or disposal. Absorb liquid spills on vermiculite or dry sand. Flush the residue with a lot of water.

Reclaim dry toric acid for salvage or reuse. Unsalvageable waste may be buried in an approved landfill. Follow Federal, state, and local regulations.

SECTION 8. SPECIAL PROTECTION INFORMATION When dusty conditions prevail, use a NIOSH approved dust respirator. Provide gexral ddudon and local exhaust ventilation in sufficient volurne and pattern to keep concentr:Gon of hazardous ingredients listed in section 2 at a minimurrt Wear body. protective clothing appropriate to the work situation to minimite skin contact Prevent eye contact by wearing chemical safety geg'gles where dusty conditions occur or splashing is possible. Use rubber gloves e prevent repeated or prolonged skin contact. Soikd clothing must be laundered before it is worn again.

Eyewash stations, w ashing facilides, and safety showers should be available to areas of use and hsndling.

Contact lenses pose a special hazard; soft lenses may absorb irriunts and all lenses concentfate thern. Particles may adhere'to contact lenses and cause corneal damage.

SECTION 9. SPECIAL PRECAUTIONS AND COMMENTS 54 orc boric acid in closed containers in a cool, dry area. Storage bins should have a 60. degree sloping. cone bottom with a provision to prevent the entry of water. Carbon steel or aluminum containers are suitable for this dIy storage. Stainless steel is raded for moist conditions.

Practice good housekeeping to prevent the accumulation and generation of dust Avoid breathing boric acid dust. Minimize skin contxt by using proper gloves and suitable work clothing appropriate to the work situxion. Practice good personal hygiene. hh thoniughly after handling this material and tefore eatirig, drinking, or smoking. Do not take this material out of your work area or to your horm on your clothing or equipment Do not eat boric acid. Avoid contact with this material, especially when skin is cut or abraded or if active dermatitis is present DOT Classification Not listed.

Data Source (s) Code: 1, 4 11,14, 25, 26, 34. 42. 43, 4 8. 40, 55,.8. g l. g4. CK w w eeem o i m yv.nram,w.we,.ra e xa m o:=

Apprmals ['Na-4 ~

s r

M sere N

8 rn,

. sadly lwthscfs n,.sewitmJ,u.1hottom. ahgb tchenJNc cmrwu o-rmss "'. i.

a i t.w.. me p,ce,,o..r.

c Indusl. li.gg'iene/Safel7

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w4.o.m a r,rei

t. he acovac y.c su aMy or such aformt.o. li. ajyhcJt e. Lo (Wheeft e wmaarwo-w= cad==

s, Medical Reslew

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r l y' LT.T *JL'~,,,1.T.C.37tp COP >right o January 1,1987 S D- 0P- 084 - 4 4 5, APPENDIX A PAGE 2

~

w MATERIAL SAFETY DATA SHEET

(

GENIUM PUBUS.ilNG CORPORATION CALCIUM HYDROXIDE s

1145 CATALYN ST., SCHENECTAET(, NY 12303 USA Revision A

• * " ~ * * *

(518)377-8854 OAtt October 1984 SECTION 1. MATERIAL IDENTIFICATION l

CALCIUM HYDROX1DE i

IONS: Hydrat ime Hig IcM etc. CE Materi 1 D4, CAS,i 5 620 i

Hydrated Lime, ust Lime c

Hydrate, S kedLine,CakH 2, ASTM 2 MANUFACTURER: Material available from man,sourc,es, including:

Ash Grove nt Co.

hav emi al Co.

Wa er Colel8Ind. Mineral Div.

Ov.O. Box 2 P

E.

7th P. iefonte, PA Box 66255 C eveland, OH tNet106 (913)381KS erland Park Be 16823 8901 Tel: (216) 721-8300 (Tel: (717) 355-4761 Tel:

SECTION !!. INGREDIENTS AND HAZARDS HAZARO OATA Typical Composition

• 3 Calcium hydroxide, Ca(OH)2

>90 8-hr TVA 5mg/m,

Calcium carbonate, CACO 4

3 Magnesium oxide, Mgo

<3 Other oxides (Al 0

'Fe O, SiO ' '"* *)

<3 y3 23 2

• Coenercial material prepared by hydration of lime.

Rat, Oral LD 7.3 Em/kg 50

• • ACCIH (1984) TLV; no specific OSHA PEL established (minimum control vould be as a nuisance particulate),

SECTION lil. PHYSICAL DATA 580 Specific gravity (H 0=1) --------

2.3-2.4 Decomposition point (-H O),

2 Witer solubili'ty, g/100 sat. solution:

y_H of saturated sol tion at 25 C - 12.5

)

at 0 C 74*l 0.185~

Molecular weight ca(OH)2

~~~~~~~~

0.159 at 25 C 0.017 at 100 C Appearance & Odor: Crystals or soft, white powder or granules. Odorless.

SECTION IV. FIRE AND EXPLOSION DATA tower Upper flesh Pe.at ea4 Me Aed Aviegnese Temp.

Flemmebl@ Lamses ip Air N/A N/A N/A Extinguishing media: This material is not combustible. Use extinguishing media which is appropriate for the surrounding fire.

When heated above 580 C, material can decompose to produce Cao. When this material is involved in a fire situation, firefighters should wear full protective clothing, and use eye protection and self-contained breathing apparatus.

SECTION V. REACTIVITY DATA This is a stable rolid in a sea:ed container at room temperature. When exposed to the air it will slowly absorb carbon dioxide to torm cdicium carbonate. When heated at tempera-tures above 580 C, it loses water to form calcium oxide or lime.

Calcium hydroxide is a strongly alkaline material which is incompatible with acidic matecials. It forms salts with nitroparaffins in the presence of water whigh are explosive when dried. It gan cause the explosive decomposition of maleic anhydride.

Boiling elemental phosphorus in a calcium hydroxide solution can liberate spontaneously flamuble phosphines. It liberates NH) from ammonium salts.

I

!Y UY.*1N,*,7,..

wu.a SD-0P-084-445, ADPENDIX A PAGE 3

g-"

(

NCL 39 SECTION VI. HEALTH HAZARD INFORMATION TLv 3

5 mg/m This material in the presence of moisture, is a moderately caustic irritant and can be damaging to human tissue. Excessive skin contact will irritate the skin and produce dermatitis. Eye contact gives a burning sensation with severe irritation and possible damage. Inhalation in particulate form is irritating and can be damaging to the mucous membranes of the upper respira2ory tract. Do not ingest.

FIRST AID:

Eye contact: Promptly flush with plenty of running water, including under eyelids, for at least 15 minutes; then, get prompt medical attention.

Skin

Contact:

Wash exposed skin with plenty of water. Remove contaminated clothing promptly. Cet medical help if exposed area is large or if irritation persists.

Inhalation: Remove to fresh air. Contact physician immediately.

Intestion: Dilute by giving 2 glasses of water or milk to drink, followed by fruit juice or diluted vinegar to neutralize the alkali; then consult physician.

SECTION Vll. SPILL. LEAX, AND DISPOSAL PROCEDURES Ihose involved in clean up of spills should use protective equipment (See Sect. VIII).

Pick up spill.a powder avoiding dustint conditions and place in a clean steel enntainer for recls.is or disposal. sarety personneA snoulci be involved when large spills occur.

Traces of residue can be flushed to the sever with much water dilution.

DISPOSAL: Consider the following methods of disposing of scrap material Use to neutralire

. vaste acid; spread on surface or ground in an isolatet prcrtected area to react with CO from the air to form CACO 3 (limestone); or disperse in

• vater, neutralize with hydro-2 chloric acid, precipitate with soda ash and flush to sever with much water to keep below 250 mg NaC1/11ter. Follow Federal, State, and Local regulations.

SECTION Vill. SPECIAL PROTECTION INFORMATION Provide general ventilation and local exhaust ventilation for dust control (or mist con-trol if used as a water dispersion) to meet TLV requirements. Vent dust to appropriate collector. fr' ovide approved dust or mist repirators or self-contained respirators for non-routine or emergency use above the TLV.

Wear rubber gloves, protective clothing, long sleeve shirt with buttone,d coller, apron, safety git.sses or goggles, f ace shield, etc. to prevent skin or eye contact with this,

materialasrequiredfortheconditionsunderwhichitisused,yseofprotectivecreams or areas of skin exposed to dust has been recorraended.

An eyetash station and safety shower siust be readily available where this material, or its water dispersions, are used.

Remove severely contaminated clothing promptly and launder before reuse.

SECTION IX. SPECIAL PRECAUTIONS AND COMMENTS Store in a cool, dry area in tightly closed containers. Protect containers from physical damage. Keep away from acidic caterials and other incompatibles (See Sect. V).

Prevent contact with clothing or with the body, or inhalation of dust or solution mist.

Use due caution in mixing with water and handling the alkaline water dispersions of this material (milk of line). Follow good personal hygiene practices. Wash thoroughly, af ter handling.

DATA SOURCE (5) CODE:1,2,4-9,11,14,20,4 7 j R. (W u,

., m e d w m w A99ROVALS: Mts/CR0

[h O-INDUST. HYGIENE /5AFE TVV Jd/.N.W MEDICAL REVIEW: 27 September 1984 GENIUM PUBilSHING SD-0P-084-445, APPENDIX A PAGE 4

f v.s. a :

i.e SAFETY DATA SHEET k.

Chem-Nucl. ear Systems, Inc.

SECTION I - INDENTIFICATION Product Name or Code No.

S-4 Physical Description White eranular substance General Chemical Compositon

salts

, e SECTION IT - PHYSICAL DATA Boiling Point ( F.)

Specific Gravity (H O = 1).

N/A N/A True Density (Solids) 2.7 Solubility In Water Particle Size (Typical)

High N/A SECTION III - FIRE AND EXPLOSION HAZARDS Flash Point (Liquids)-

pyg Fire Extinguishing Hethods

~

water fog to keep containers cool Flammability (Solids)

N/A Explosive Limits Lower Upper In Air N/A s

SECTION IV - HEALTH HAZARDS, HANDLING, AND STORAGE Toxicity Avoitd ingestion and prolonged skin contact R'scommended Handling avoid excessive dusting Rscommended Storage store in dry area S D- 0P- 084 - 4 45, APPENDIX A PAGE 5

4,

,,' i. i SAFETY DATA SHEET

?!(

Chem-Nuclear Systems, Inc.

SECTION V - REACTIVITY Stability Conditions To Avoid Unstable Stable XX Incompatability (Materials to avoid) strong alkalies, mineral acids Hazardous Decomposition Products Conditions To Avoid Hazardous May Occur Polymerization Will Not Occur XX

.n ;

SECTION VI - SPILL PROCEDURES AND WASTE DISPOSAL Steps To Be Taken In. Case Material Is Released Or Spilled flusli With excess Water Waste Disposa). Method

,(.

Cf soil or sanitary landfill SECTION VII - SPECIAL PRECAUTIONS none EMERGENCY CONTACT:

CNSI BARNWELL, SOUTH CAROLINA (803) 259-1782 SD-0P-084-445, APPENDIX A

~

PAGE 6

3 CHEM-NUCLEAR SYSTEMS,INC.

2o Stonerloge Drive

• Columtsa, Soutn Carolina 29210 June 17, 1988 3145A Hr. Ray Petrie Commonwealth Edison Company Quad Cities Station 22710 206th Avenue North Cordova, IL 61242

Dear Mr. Petrie:

Hix testing performed subsequent to the problems encountered with the Quad Cities liner indicata that the amount of P-20 added to the waste was sufficient to absorb all free water in the liner, even if only 75% of the reduced amount was mixed into the billet.

Lab tests were performed to estimate the physical condition of the solidified product at Quad Cities, where only one-third of the planned amount of P-20 binder had been added to a liner containing radioactive resin beads saturated with LOHI chelating chemicals.

The waste material was simulated by soaking 231 gm. of virgin MR-3 resin beads in 100 gm. of LOMI liquid overnight, and then adjusting the pH to 3.0 with about 7 gm. of 50% sodium hydroxide.

From this mixture, two 100 ml.

portions were transferred to small polyethylene cylinders to represent the geometry of the actual liner.

Standard P-20 binder was then added in each case to a total of 33 gm. instead of the 100 gm. normally required.

The following table shows that after oven curing for 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> no frec liquid was generated if 75% of the binder had been dispersed in the waste.

Mix 1 Mix 2 _

Simulated Haste 100 ml.

100 ml.

P-20 Added and Hixed 33 gm.

25 gm.

P-20 Spread on Top None 8 gm.

Total P-20 Added 33 gm.

33 gm.

Condition of Product After Curing @ 1450F Hard - No Firm - No And Then Cooling To Liquid On Liquid On Room Temp. Before Bottom Bottom Opening Bottom Of Container Based on processing logs and reports from the operator, which indicate proper mixing throughout the majority of the processing period, it can be theorized thit a minimum of 75% of the binder was mixed properly and that there is no free water in the container.

If I can be of any further assistance, please contact me.

Sincerely, General anager Nuclear Services JDJ:gp (803) 2!6 0450

• Te eu. 218947

,J REVIEW OF CHEM-NUCLEAR LETTER DATED JUNE 15, 1988 The premature hardening is more likely the cause of both thermal and chemical (lack of retardant) factors, rather than just thermal considerations as described in the Chem-Nuclear letter.

Solidification vendors should ideally perform PCP solidifications in an adiabatic, or at least, well insulated condition to avoid the situation whereby excessive heat dissipation from a small sample could yield a non-conservatively high indication of the hydration rate of the sample.

The Chem-Nuclear letter also implies in the response to Question il that the subject waste batch did not have a pH typical of LOMI/ Resin waste.

CECO later learned that the basis for this stems solely from Chem-Nuclear's pH measurement of several simulated waste samples rather than actual waste s ample s. CECO's current position is that the pH of the waste batch was very typical given the fact the pH of the spent solutions deposited on the resin was quite typical of other decons performed at CECO stations which involved the use of LOHI.

4910K

, af-l.

REVIEW OF CHE*4-NUCLEAR LETTER DATED JUNE 17, 1988 This let*.er provides a basis for Chem-Nuclear's position that the liner is currently free of standing 11guld.'

Although CECO was not on hand to observe the lab scale solidifications described in this letter, CECO agrees with the test methodology'and the conclusions drawn therein.

4910K

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&TIACIBGNT C 1

r Past Practices of Us.8.ng Surre, gate Waste Samples in the Solidification of Decontamination Solutions at Quad Cities Station Discussion'of Past CECO BWR Decontaminations

' 1tter f rom P. DeNault (LN Technology) to S. Davis (CECO Dated July 14, 1988 Regarding LONI Surrogate Sample Preparation a

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EAST PRACTICES OF USING SURROGATE WASTE SAMPLES IN THE SOLIDIFICATIONS DECQtLTAMINATION SOLUTIONS AT OUAD CITIES STATION l

l The practice of using simulated waste samples for the Process. Control Program -(PCP) began in 1983 with the first decontamination of the Unit 2 Recirculation System Piping. Quad Cities was recognized as having one of the highest source terms in the country with dose rates on the risers of-1500 mrem /hr, on the suction and discharge piping of 500 mrem /hr and on the ring i

header 800 mrcm/hr. Dose rates on the ion exchange columns and liner were estimated to be as high as 300 R/hr. Measured dose rates on ion exchange columns (remote reading) yellow results greater than 70 R/hr (detector next to a single column).

These elevated dose rates caused great concern for how much dose would be obtained in pulling an actual sample of waste. These ALARA concerns gave way to discussions on the use of simulated waste samples for the PCP.

A simulated waste sample was able to be made that was believed to be equivalent

-to the real waste. The PCP was run without any difficulty and the formula t

scaled up for the full liner. The full liner of real waste behaved as expected with no problems arising.

The practice of using simulated waste in the PCP was continued in future decontaminations for the same ALARA concerns.

CECO and its representatives have investigated whether the use of a simulated resin waste sample (rather than en actual waste sample) could have been a contributing cause of premature hardening. Although CECO recognizes that the use of the simulated sample was a violation of the vendor PCP and thus was a violation of Station Technical Specifications, CECO does not consider the use of a simulated sample to have been a contributing cause of the premature hardening for the following reasons.

The Chem-Nuclear PCP in use at the time the test solidification was performed did not call for the vendor to monitor either the temperature of the test mixture during hydration or the time required for the test mixture to harden. This established circumstences wt by it would be h3ghly unlikely that premature hardening of the te't solid. cation would have been detected prior to the performance of the full scale solidification. Thus, premature hardening of the contents of the liner would have likely occurred even had an actual waste sample been used.

4910K

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P.AST.JICQtS._EfJtFORMED. AT OUAD' CITIES AND OTHER Ceco STATIONS The subject' chemical decontamination was the sixth such performed at r-

-Quad Cities, and the eleventh performed at a CECO BWR.

Enclosure l'provides a summary of these decons..This chart had been provided to the'NRC during the May 24, 1988 meeting.

Each of the prior decon waste batches described therein had been successfully solidified in cement, all but one having been solidified by Chem-Nuclear.

During some decons it has become necessary to perform multiple decon solvent applications to the recirc discharge piping in order to obtain~the desired reduction in radiation levels, or Dr.

In two cases, a subsequent decon involved the use of a decon agent different than that used in-the initial decon. Yet another decon involved the use of a different decon agent to decon the Fuel. Pool heat exchangers as was used on the recirc and reactor water cleanup p! ping.

Yet, the solidification vendor had not encountered I

difficulty in performing the solidification prior to the subject case.

Each of the previous' waste batches were properly solidified with no free standing 11guld.

The chemical characteristics of the subject batch.of decon waste were evaluated in an effort to identify possible causes for the premature har6ening of the contr3ts of the liner.

It can be seen from the enclosure that the pH of the spent solvent prior to deposition on resin, resin quantity and chelate concentration were not atypical in the subject batch. A review of the quantitles of chemicals used in the formation of previous decon solvent batches also substantiates the conclusion that the subject batch was not atypical. These analyses show that if chemical characteristics of this batch of waste could have caused premature hardening of the cement, premature hardening would have likewise occurred during the solidification of one or more previous waste batches.

From this, CECO concludes that the waste characteristics did not cause premature hardening of the cement.

4910K'

&N-gjctage J

A Commonwealth Edison 8WR Chemical Decontaminations Decontamination Solidtfication Date Station-Decon Decon System Metals Restn Percent Solution Solidification Solidification Mo/vr Unit Vendor Agent Deconned Content

_fty Chetates pH Vendor Finder 10/83 Quad London Can-Recirc 11.7 Kg 50 ft Chem-Nuclear Coment Cities-2 Nuclear Decon 3/84 Quad London Can-Recirc/

6.0 Kg 55 ft Chem-Nuclear Coment Cities-1 Nuclear Decon RWCU 1/86 Ouad London LOMI Recirc/

8.4 Mg 168 ft 3.8 D5.5.54.7 Chem-Nuclear Coment Cities-1 Nuclear (NP/LOMI) RWCU (D2.7).04.3 R4.1 eur86 Quad LN Tech LOMI Rectrc/

15.3 Kg 156 ft 3.9 D4.5. (OX6.0 Chem-Nuclear Coment Cities-2 (NP)

RWCU DE2.0).54.7 R4.7 9/87 Quad LN Tech LOMI Recirc/

9.2 Mg 94 ft 6.6 D4.1.54.3 Chem-Nuclear Coment Cities-1 RWCU/

R4.1 Can-Derem FC HX 13.2 Mg 22 ft 4/88 Ouad LN Tech LOMI Rectre 5.4 Mg 119 ft 5.9 04.4.54.74 Chem-Nuclear Cement Cities-2 3/88 LaSalle-1 LN Tech LOMI Recirc 4.0 Kg I20 ft 5.4 D4.2.54.3 LN Tech Coment 11/83 Dresden-3 London Can-Rectrc/

10.6 Kg 60 ft Chem-Nuclear Cement Nuclear Decon RWCU 11/84 Dresden-2 IT/PNSS 10%

Recirc/

18.5 Kg 400 ft Chem-Nuclear Coment NS-1 RWCU 4

11/85 Dresden-3 London LOMI/

Rectrc/

10.4 Kg 163 ft 4.6 05.1.53.9 Chem-Nuclear Coment Nuclear LOMI RWCU D4.6.55.1 R4.0 12/06 Dresden-2 LN Tech LOMI/

Rectrc/

13.9 Mg 160 ft 5.8 04.4.54.5.

Chem-Nuclear Coment LOMI RWCU D4.5 R4.3 R4.7 i --

I

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5 Commonwealth Edtson SWR Chemical Decontaminations recontamtnation Sol 9dif1 cat 4on Date Station-Decon De.?on System Metals Restn Percent Solution Solldtftcation Solidification Mo/vr Untt Vancor Aps.',

Deconneo Content Qty Chetstes pH Vendor Sinder 10/83 Quad London Can-Rectre 11.7 Mg 50 ft Chem-Nucle 9e Coment Cities-2 Nuclear Decon 11/83 Dresden-3 London Can-Rectrc/

10.5 Mg 60 ft Chem-NucleP-Coment Nuclear Decon RWCU 3/84 Quad London Can-Rectrc/

6.0 kg 55 ft Chem-Nuclear Coment Cities-1 Nuclear DeCon RWCU 11/84 Dresden-2 IT/PNSS 10 %

Rectrc/

18.5 Kg 400 ft Chem-Nuclear Coment NS-1 RwCU 11/85 Dresden-3 London LOMI/

Recirc/

10.4 Kg 163 ft 4."

D5.1.53.9 Chem-Nuclear Cement Nuclear LOMI RwCU D4.6.55.1 R4.0 1/86 Quad London LOMI Rectrc/

8.4 Mg 168 ft 3.8 05.5.54.7 Chem-Nuclear Cement Cities-1 Nuclear NP/LOMI RWCU

( D2. 7 ). D.1. 3 R4.1 10/86 Quad LN Tech LOMI Rectrc/

15.3 Kg 156 ft 3.9 D4.5.(Ox6.0, Chem-Nuclear Cement Cities-2 NP RwCU DE2.0) S4.7 R4.7 12/86 Dresden-2 LN Tech LOMI/

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13.9 Mg 160 ft 5.8 D4.4.S4.5 Chem-Nuclear Cement LOMI RwCU D4.5.R4.3 R4.7 9/87 Quad LN Tech LOMI Recirc/

9.2 Kg 94 ft 6.6 D4.1.54.3 Chem-Nuclear Cement Cities-1 Can-RwCU/

R4.1 Decem FC HX 13.2 Kg 22 ft 3/88 LaSalle-1 LN Tech LOMI Rectre 4.0 Kg 120 ft 5.4 D4.2.54.3 LN Tech Coment 4/88 Quad LN Tech LOMI Rectre 5.4 Kg 119 ft 5.9 D4.4.54.74 Chem-Nuclear Coment Ctttes-2

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TWCHNOLOGWS C O APO A ATION 1501 KEY ACAD, COLUMBIA. G.C. 29201 (803)258 4355 July 14, 1988 LN-88-00397/PW Mr. Steve Davis Commonwealth Edison 1319 South First Ave.

Maywood, IL 60153 Dear Steves To help you in your investigation of the recent Quad Cities

.decontamination resin solidification problem, I have prepared the following answers to questions which you communicated by telephone.

1.

Lack of strong base anion resin in the resin sample given Chem Nuclear for the PCP.

The volume of LOMI loaded resin generated during a decon normally comprises 80-90% of the total waste resin expected.

The other 10-20% is polishing resin used to remove traces of chemi-cals from the water prior to sending it to radwaste.

The polish-ing resin is an equivalent mixture of strong acid cation (EBR) and strong base anion (SBA) resin, with 2/3 of the volume being SBR.

Therefore, the percentage of SBR normally found in the liner is between 7-144.

The mixed resin contains very little chemicals.

If we as-cume a ctraight line relationship betwcon concentration and con-ductivity, the weak base resins removed 97.5% of the chemicals used on the discharge side and greater than 93% of the chemicals used on the suction side at Quad Cities.

We know that the strong base resins are only slightly depleted.

This is by design since the column outlet water must be of a high purity.

Since the SBR contains very little of the chemical and since the anticipated SBR volume was small, our chemistry staff on site at the time a resin sample was requested decided to leave it out of the sample.

It was assumed that the small amount of SSR resin would not affect the cement setting in the liner.

Data our waste group has generated during resin stabi-lization testing supports the above assumption.

Our data show that LONI resins and SBR resins can be stabilized with similar formulations.

From this we can conclude that the SBR resins do not affect the PCP results.

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Mr. Steve Davis July 14, 1988 Page 2 My personal recollection of previous decontaminations at Quad Cities is that no set procedure for preparing the resins for a PCP has been followed.

The mix of SAC and WBA resins and the chemical loading used to simulate the LOMI chemical removal step is standardized.

However, whether SBA resin is added is not documented and I know it has not been added in all cases, if at

all, our decon procedures, approved by the plant and CBCo staff, do not address waste processing operations.

On jobs where LN has performed both the decontamination and waste handling, the PCP

. sample preparation is covered under separate waste procedures which are submitted for plant review with the decon procedures.

2.

CECO and plant staff did not know that strong base anion was not added to the PCP resin sample.

LN has not received clear instructions nor have procedures been written on how to prepare a resin sample to support the Chem Nuclear waste processing operations.

LN was asked to provide a resin sample, typical of that generated during a LOMI decon-tamination.

CECO and plant staff may have assumed that SEA resins were added.

LN staff, because of reasons given in item (1) have not added SBA resins.

3.

The chemical loading on the PCP resins varied 10-20% with that calculated for the actual waste.

Our pre-decon calculations indicated that approximately 100 cubic feet of resin would be generated during the QC-1 recircula-tion system decontamination.

In fact, an additional 21 cubic feet were generated due to unexpected operational problems during the decon.

I refer to the high water level in the reactor vessel prior to the suction side decontamination.

LH was re-quested to drain the excess water through their ion exchange columns to the plant radwaste system.

Thia procedure produced the extra waste resin.

Since no extra chemical

• were used during this process, the extra resins effectively diluted the volume of LOMI resins and hence reduced the concentration of chemicale on the total resin volume.

The higher depletion factor for the actual resins is due to the dissolved iron, nickel, manganese from the oxide film which were removed by cation resin.

The PCP resins were not depleted with simulated oxide cations.

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4.

How was surrogate PCP sample prepared?

LN uses manufacturer's capacity factors adjusted to reflect actual field application experience to determine the chemical loading on the resins and hence the total resin waste volume to be generated.

The same factors are used for the PCP resin sample.

The required amount of vanadous formate, picolinic acid and sodium hydroxide is added to water to form a homogeneous mixture.

The necessary amount of SAC and WBA resins are added to the beaker to absorb the ions.

The mixture is stirred until the ex-

. change process is complete.

This occurs when the characteristic black color of the decon solution disappears and a water-white solution remains.

LN has performed tests in its laboratories to show that greater than 90% of the chemicals are absorbed using this procedure.

The PCP resins are essentially loaded to the Same extent as the process resins.

The resins are then washed witu demin water and stored until required for the PCP.

5.

Why were cations not added to the PCP resins to simulate metals from the oxide film?

The exact amount of oxide film to 'be dissolved is not known prior to the decon.

Because of this, it is very difficult to simulate the cation resin loading.

As mentioned in section 1, virgin or undepicted resins are more difficult to stabillae with cement based processes.

LN does not add metals to the PCP resin sample to create a worst case during PCP testing.

If the PCP resins set and solidify when not fully depleted, the actual liner resins will behave accordingly.

I trust this information is satisfactory to your needs.

Please feel free to contact me if further data is required.

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'A Paul Donault Director Chemical Decontamination Services PDapw cc:

Regan E. Voit uennis rarrar Joe Sirovy A Member of The SNc Group

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REVIEW OF LN TECHNOLOGIES LETTER DATED JULY 14, 1988 The use of WBA and SAC resin only in the preparation of the simulated waste sample as compared to the use of WBA, SBA and SAC in the full scale process is of very minor consequence. Again, even the use of an actual waste sample would not have prevented the event. The ratio of anion to cation resin in the simulated sample was very close to that in the actual waste.

It seems likely that the influence on solidification chemistry of SBA and WBA would not be significantly different than that of just NBA.

The vendor's fleid experience should be adequate to judge what constitutes an average metal oxide removal quantity to use toward producing a more representative simulated sample than by not factoring this into sample preparation at all.

All of this is, of course, obviated by the use of an actual rather than a simulated PCP sample.

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.o ATIACEME2iT_D PLANS FOR DISEQSAL OF WASTE LINER AND 111PLEMENTATION SCHEDULE 4910K

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PLANS FOR DISPOSAL OF WASTE LINER AtiD IMPLEMENTATION SCHEDULE Based on discussion and correspondence (specifically, the June 17, 1988 letter from J. Jeffrey to R. Petri), Commonwealth Edison has confidence that the contents of the liner are solid.

In order to assure that long-term stability of the liner, Commonwealth will encapsulate the liner using an approved procedure which represents a change to the Station PCP.

This change to the Station PCP will be reviewed at both the Station and Corporate Level.

It is our intent.*.o have Chem-Nuclear arrive at Quad Cities Station with the 6ncapsulation equipment in mid-August following the complete on-site review of Chem-Nuclear documents in support of this effort. We anticipate that the encapsulated liner will be ready for shipment and ultimate burial in early September.

The revision to the PCP (which addresses the encapsulation procedure) will be submitted to the NRC in accordance with Section 6.9 of the Quad Cities Station Unit 2 Technical Specifications (DPR-30) via the Radioactive Effluent

-Release Report for the period during which the change was made.

This report will be submitted to the NRC in February, 1989.

However,.an advance copy will be provided to your staff for information by August 15, 1988.

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q 11 j' ATIACINEMI_E PROPOSED LQiG TERM CORRECTIVE ACTIONS 4910K

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PROPOSED LeiG TERM CORRECTIVE ACTICHS Commonwealth Edison believes that the problems experienced in the solidification of the LOM1 liner were due to a number of factors.

Chem-Nuclear provided a revised attachment to the station prior to the.

solidification attempt.

This revised attachment addressed the deletion of lime from the recipe. This revision was predicated on both lab scale testing and the technical judgements of vendor personnel who are cement solidification chemistry experts. CECO does not have such expertise and therefore, would not have been able to anticipate that deletion of lime would have had such a severe adverse affect on the. hydration rate as we now believe it did.

Nonetheless, CECO investigation into this matter brought to light some fairly. broader weaknesses, i.e., the inadequate management / technical oversight of vendor's activities.

Consequently, Commonwealth Edison has committed to the following activities (a) CECO will ensure that actual waste samples are used in the preparation of the test solidification of all waste batches at each of the CECO Stations.

(b) CECO will perform and document reviews of all revisions to solidification vendors PCPs. CECO will Initiate this review process prior to September 30, 1988.

(c) CECO will ensure that the pH of all decon waste batches processed at each of the CECO stations will be properly adjusted per requirements of the vendor PCP.

Finally, as a result of this event, Quad Cities Station has developed a set of procedures to be used each time a waste batch of any type is solidified or dewatered. These procedures provide a mechanism by which the Station can ensure that adequate overview is maintained. These have been On-Site reviewed and approved.

It is Commonwealth Edison's position that these programmatic changes give us assurance that such an event should not recur.