ML18003B288

Rev 0 to Procedure CRC-826, Post-Accident Sample Chloride Analysis.

ML18003B288
Person / Time
Site:	Harris
Issue date:	07/09/1985
From:	Sipp J CAROLINA POWER & LIGHT CO.
To:
Shared Package
ML18003B287	List: ML18003B286 ML18003B288 ML18003B289
References
CRC-826, NUDOCS 8605270110
Download: ML18003B288 (18)

Text

SFR073 CAROLINA POWER & LIGHT COMPANY SHEARON HARRIS NUCLEAR POWER PLANT PLANT OPERATING MANUAL VOLUME 5 PART 3 PROCEDURE TYPE: Chemistry and Radiochemistry NUMBER: CRC-826 PROCEDURE TITLE: Post-Accident Sample Chloride Analysis REVISION 0 APPROVED:

S re Date TITLE: lIllB-E a g Bb05270110 Sb0519 PDR ADOGK 05000400 PDR'age 1 of 12

SPR073

~ ~ ~

List of Effeotive Pa es

~Pa e Revision 1" 12 0 CRC-826 Rev.0 Page 2 of 12

p ~

SPR073 1.0 PURPOSE This procedure is to be used for determining the chloride ion concentration in ppm in diluted post-accident reactor coolant or residual heat removal pump discharge samples'his procedure is used to satisfy the initial scoping analyses for chloride to verify that the chloride concentration is detectable at a minimum of 10.0 ppm provided that the dissolved oxygen concentration can be verified to be less than 0.10 ppm. Chloride analysis on post-accident samples is necessary for evaluating the extent and type of core damage following an accident and in developing plant recovery operations. This procedure should be used subsequent to obtaining an RCS/RHR liquid sample in accordance with CRC-821. The expected accuracy of this procedure is 2 105.

2.0 REFERENCES

1. SHNPP Final Safety Analysis Report, " Post Accident Sampling System", Vol. 16, Section 9.3.2.2.3, Amendment 14.

2. Nuclear Regulatory Commission, Nuclear Regulatory Guide (NUREG) 0737,Section II B.3.

3. SHNPP, Plant Operating Manual Vol.5, Part 3, Chemistry and Radiochemistry procedure CRC'-001, "SHNPP Chemistry Program".

SHNPP, Plant Operating Manual, Vol.5, Part 3, Chemistry and- Radiochemistry Procedure, CRC-821, "PASS RCS/RHR Pump Discharge Diluted Liquid Sampling During Accident Conditions".

5. SHNPP, Plant Operating Manual,. Vol. 5, Part 3, Chemistry and Radiochemistry Procedure, CRC-501, "Operation of the Ion Chromatograph".

3.0 RESPONSIBILITIES

1. The Site Emergency Coordinator or Radiological Control Director will be responsible for providing the decision to utilize the PASS during post-accident conditions.

2. The Personnel Protection & Decontamination Team Leader will advise the Plant Monitoring Team Leader on the expected radiological conditions at the PASS and in the laboratory during sample analysis.

CRC-826 Rev.0 Page 3 of 12

0

SPR073 3.0 RESPONSIBILITIES (continued)

3. The Plant Monitoring Team Leader will brief the Plant Monitoring Team Members on the sampling, analysis requirements, and expected radiological conditions after first conferring with the Personnel Protection and Decontamination Team Leader. The Plant Monitoring Team Leader will brief the members of the plant monitoring team either in person or by phone from the operational support room in the Technical Support Center.

4. The Plant Monitoring Team will report all sample data to the Plant Monitoring Team Leader as soon as possible.

5. Members of the Plant Monitoring Team are responsible for analyzing PASS samples for chloride ion concentration using the ion chromatograph.

4.0 DEFINITIONS AND ABBREVIATIONS F 1. Definitions Not Applicable 4.2 Abbreviations .

1. PASS Post Accident Sampling System

2. RCS Reactor Coo'lant System

3. 'HR Residual Heat Removal RAB Reactor Auxiliary Building

5. RCB Reactor Containment Building

6. DI De-ionized

7. IC Ion Chromatograph

8. ALARA As Low As Reasonably Achievable

9. N Normal

10. M Molar CRC-826 Rev.0 Page 4 of 12

SPR073

~

4 ~

5.0 GENERAL Ion chromatography is a powerful tool for the quantitative analysis of low ionic concentration solutions. The method,'pplicable to both anions and cations, is based on the elution selectivity of ion exchange media for different ionic species. Sample size, physical size of the ion exchange column, ionic capacity of the resin, eluent concentration, and sample flowrate can all be held constant. The time after sample injection that a conductivity peak appears can be assigned to a specific ionic species. The Dionex ion chromatograph when upgraded with a fiber suppressor column is continuously regen-erated with 0.025 N sulfuric acid solution thus eliminating downtime for suppressor column regeneration. In addition, this procedure incorporates ion chromatograph flushing with deionized water and a sodium carbonate-sodium hydroxide eluent to flush radioactive anions from the separator column.

The range for ion chromatographic chloride analysis is 0.10 ppm-20.0 ppm with an expected accuracy of approximately 2 10K,.

.1. This procedure shall be used to determine chloride ion concentrations in diluted post-accident liquid samples taken in accordance with procedure CRC-821, " PASS RCS/RHR Pump Discharge Diluted Liquid Sampling During Accident Conditions",.

2. Auxiliary system flushing fluids such as deionized water, nitrogen, and service air must be available to the ion chromatograph.

NOTE: The decision to place the ion chromatograph in an operating fume hood will be made when necessary by the Personnel Protection and Decontamination Team Leader.

3. The fume hood containing the ion chromatograph must be operating and equipped with a drain for accepting radioac-tive liquids prior to sample analysis.

Plant Monitoring Team Members performing this procedure shall be thoroughly familiar with procedure CRC-501, "Operation of the Ion Chromatograph".

5. An emergency radiation work permit has been prepared for analyzing post-accident samples inthe laboratory.

6. The Site Emergency Coordinator has declared that a chloride ion analysis on diluted RCS/RHR samples taken from the PASS is required.

CRC-826 Rev.0 Page 5 of 12

SPR073 7.0 PRECAUTIONS AND LIMITATIONS This procedure involves the processing of water that will be highly radioactive. Follow proper radiation practices and employ ALARA considerations throughout the entire procedure.

I l

2. Chloride analysis must be completed within 96 hours0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br /> after decision is made to obtain PASS sample and analyze for

"'he chloride.

3. The Plant Monitoring Team leader or other designated member of the Plant Monitoring Team will identify the appropriate PASS start-up requirements.

4.. The Plant Monitoring Team Leader will brief the Plant Monitoring Team Members on sampling and analysis requirements prior to the team's entry.to the Reactor Auxiliary Building.

5. If any steps of this procedure cannot be performed or if an abnormal condition exists, contact the Plant Monitoring Team Leader immediately.

6. The ion chromatograph, shall. be flushed after each set of samples to prevent, the buildup of radioactivity in the sample lines.

7'. Ion chromatographic. chloride analysis should only be performed on diluted post-accident. samples.

8.0 REAGENTS AND APPARATUS NOTE: Eluent and regenerant strengths may be adjusted as necessary to provide acceptable chromatograms.

8.1 ~Rea ents

1. 0.025 N Sulfuric (H2SO<) Acid (Anion Fiber Suppressor Regenerant)

& Fill a four-liter beaker approximately half full with deionized water.

b. Carefully pipet 2.8 ml of concentrated sulfuric acid (H2SO<) into the beaker and mix the solution.

c Add two liters of deionized water and completely mix the solution.

d. Pour the solution into a container having a volume of four liters.

CRC-826 Rev.0 Page 6 of 12

I.

SPR073 8.1 ~Rea ants (continued)

e. Label the solution with the concentration, date of preparation, technician's initials and the expiration date of the acid solution. This acid has a chemical shelf life of three (3) months.

2 ~ 0.0024 M Sodium Carbonate (Na2C03)/ 0.0016 M Sodium Hydroxide (NaOH) Anion Eluent Solution.

a. Pill a four (4) liter beaker with two liters of deionized water.'.

Add 1.018 grams of sodium carbonate (Na2C03) and 64 ml of 0.1 N sodium hydroxide (NaOH) to the beaker and mix well.

Ce Add an additional two liters of deionized water and continue to mix the beaker's contents until the

'solution is thoroughly mixed.

d. Transfer the solution to a four-liter container and label the container with the solution's name, concen-tration, date of preparation, technician's initials and the expiration date.. This solution has a shelf-life of three (3) months.

8.2 a~status

1. Ion Chromatograph Columns

a. 'ionex AS4 Anion Separator Column

b. Dionex AG4 Anion Guard Column

c. Dionex AFS Anion Fiber Suppressor Column

2. Shielded Sample Transport Container

3. Milton-Roy Sample Loading Pump or equivalent

4. Dionex Model 2120i Ion Chromatograph or equivalent

5. Spectrophysics Model 4270A Recording Integrator or equivalent.

9.0 ACCEPTANCE CRITERIA Not Applicable CRC-826 Rev.0 Page 7 of 12

SPR073 10.0 PROCEDURE 10.1 Ion Chromato ra h Setu NOTE: The Personnel Protection and Decontamination Team Leader will make the decision for setting up the ion chromatograph under a fume hood for analysis of post-accident samples, if necessary.

1. Install sample loop with a minimum volume of 100 microliters on the System 1 LOAD/INJECT valve.

2. Remove the Luer syringe fitting fxom the System 1 in-jection port and install the fitting from the outlet of the sample loading pump.,

3. Check that the following columns are installed in System 1 of the ion"chxomatograph.

a. Guard Column  : AG 4

b. Separator Column  : AS 4

c. Suppressor Column : Anion Fiber Suppressor

4. Prepare four (4) liters of anion eluent in accordance with section 8.2.

5. Connect the eluent line to the No.l bulkhead fitting on the System 1 pump, module.

NOTE: As an alternate method to setting individual instrument controls, the analysis sequence can be programmed into the Auto-Ion Controller. If this method is used, program the controller fox three sample injections.

6. Set the flow note of the System 1 pump at 2.0 ml/min.

~ 7 ~ Place the System 1 "A" valve in the "OFF" position.

8. Place the System 1 "A" LOAD/INJECT valve in the "LOAD" position.

9. Establish regenerant flow (0.025 N H2S04) through the anion fiber suppressor.

10. Set the System 1 conductivity detector at 3 pS full scale.

NOTE: A stable baseline i~ usually achieved, in 15-30 minutes.

CRC-826 Rev.0 Page 8 of 12

I SPR073 10.1 Ion Chromato ra h Setu (continued)

11. Start the System 1 pump and monitor the system conductivity until a stable baseline is obtained.

12. Isolate the waste line and route it to a suitable drain for accepting radioactive waste.

13. Set the sample loading pump at 50K, flow on the vernier dial.

10.2 Ion Chromato ra h Standardization

1. Prepare a 0 '0 ppm chloride standard by appropriately diluting a chloride stock solution. P

2. Place the sample inlet tube from the sample loading pump into a container of deionized water.

3. Turn on, the sample loading pump and pump the deionized water through the injection loop for two (2) minutes then stop the sample loading pump.

4. Simultaneously place the System 1 LOAD/INJECT A or B switch on the integrator.

NOTE: The chloride ion peak will, appeaq at approximately two (2) minutes following the injection.

5. Vait at least ten (10) minutes from the time of injection to allow all peaks to elute from the ion chromatograph's columns.

6. Place the LOAD/INJECT valve in the "LOAD" position then stop the integrator.

7. Repeat steps 2, 3, and 4 of this section of the procedure until no measurable chloride peak is observed.

8. Place the inlet tube from the sample loading pump into the 0.10 ppm chloride standard.

9. Turn on the sample loading pump and pump standard chloride solution through the injection loop for two (2) minutes then stop the sample loading pump.

10. Simultaneously plac~the System 1 LOAD/INJECT valve in the "INJECT" position and press the INJECT A or B switch on the integrator.

11. Vait at least ten (10) minutes from the time of injection to allow all peaks to elute from the ion chromatograph's columns.

CRC-826 Rev.0 Page 9 of 12

SPR073 10.2 Ion Chromato ra h Standardization (continued)

12. Place the LOAD/INJECT valve in the "LOAD" position then stop the integrator.

13. Calibrate the integrator based on the 0.10 ppm chloride

,standard and record the data on Form CRC-826-1.

li

14. Repeat steps 8 through 12 of this section of the procedure with a second 0.10 ppm chloride standard.

15. The integrator printout for the second standard must be within the acceptance criteria for standardization checks stated in CRC-501.

10.3 Diluted Reactor Coolant Sam le Anal sis

1. Place the shielded cask containing the diluted reactor coolant sample under the ventilated hood area.

2. Quickly place the sample loading pump inlet tube into the sample by forcing the inlet tube through the septum of the sample vial.

3. Turn on the sample loading pump and pump sample through the injection loop for two (2) minutes then stop the loading pump.

Simultaneously place the LOAD/INJECT valve in the "INJECT" position and press the INJECT' or B switch on the inte-grator.

NOTE: If chloride'ons. are present in the sample, a chloride peak wi.ll appear at approximately two (2) minutes.

5. Wait at least ten (10) minutes from the time of in]ection to allow all-peaks to elute from the ion chromatograph's columns.

6. Place the LOAD/INJECT valve in the "LOAD" position then stop the integrator.

NOTE: If the integrator printout indicates greater than 0.1 ppm, report-the result for the chloride ion concentration as hlOppm, then contact the plant monitoring Team Leader to determine if further sample dilution is required. If additional sample dilution is requested, dilute the sample appropriately then perform Step 10.3 of this procedure.

7. Calculate the sample chloride concentration according to step 11.3 of this procedure and record the result on form CRC-826"1-0.

CRC-826 Rev.O Page 10 of 12

~

~ SPR073

~ ~

10.4 Ion Chromato ra h Flushin

1. Cycle the System 1 LOAD/INJECT valve ten (10) times before leaving the valve in the "LOAD" position.

2 Place the sample loading pump inlet tube into a container of deionized water.

3. Turn on the sample loading pump and pump deionized water through the injection loop'or a minimum of thirty (30) minutes to flush the loop.

4. Maintain eluent flow through the ion chromatograph's columns for a minimum of thirty (30) minutes after com-pletion of sample analysis to flush the columns.

5. After flushing the ion chromatograph for a minimum of thirty (30) minutes turn off the sample loading pump and the analytical pump..

11. DIAGRAMS ATI'ACHMENTS CALCULATIONS 11.1 ~Dfa zams Not Applicable 11.2 Attachments:

Attachment. 1: CRC-826-1-0,, Data Sheet'or Post-Accident Sample Chloride Analysis.

11.3 Calculations Calculate the chloride ion concentration of the sample in ppm by using the following equation.

C ci~WmxDF where: C cE

= chloride ion concentration of the sample, ppm.

C = measured chloride ion concentration in the m

sample taken from the chromatograph's integrator, ppm.

DF = sample dilution factor.

CRC-826 Rev.O Page 11 of 12

1 I II SPR073 FORM : CRC-826-1-0, Rev.0 Data Sheet for Post-Accident Sam le Chloride Anal sis Sample Date Sample Time Sample Origin Sampled by Analysis Date Analysis Time Dilution Factor Analyzed by EBC Technician Chloride ion concentration as measured in the analyzed sample (from integra-tor)

Injection No. l ~pm Injection No. 2 ~pm Injection No. 3 ~pm Average ~pm Chloride ion concentration of undiluted PASS sample (calculated) ~pm Review by  : / /

Plant Monitoring Team Leader Date CRC-826 Rev.O Page 12 of 12