ML18003B289

Rev 1 to Procedure CRC-827, Post-Accident Sample Boron Analysis by Fluoroborate Specific Ion Electrode.

ML18003B289
Person / Time
Site:	Harris
Issue date:	11/20/1985
From:	Sipp J CAROLINA POWER & LIGHT CO.
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ML18003B287	List: ML18003B286 ML18003B288 ML18003B289
References
CRC-827, NUDOCS 8605270114
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Text

A'RC004

~ k ' OS2 ,0 CAROLINA POVER & LIGHT COMPA%'HEARON HARRIS NUCLEAR POWER PLANT PLANT OPERATING MANUAL VOLUME 5 PART 3 PROCEDURE TYPE: CHEMISTRY AND RADIOCHEMISTRY NUMBER: CRC-827 TITLE 'OST-ACCIDENT SAMPLE BORON ANALYSIS BY FLUOROBORATE SPECIFIC ION ELECTRODE REVISION 1 APPROVED:

Signature Date TITLE:

F(ECElVFO SbOM70114 ADOCK 05000400 Sb0519'DR NOV 26 885 PDR Page 1 of 14

CRC004

.OS2 List of Effective Pa es

~pa e Revision 1-14 CRC-827 Rev. 1 Page 2 of 14

CRC004

'S2 1.0 PURPOSE This procedure is to be used for measuring boron concentration in diluted post-accident reactor coolant or residual heat removal pump discharge samples. The boron concentration in the diluted sample should be greater than 0.05 ppm and less than 10ppm. The analysis time excluding the required time for sampling, reagent preparation, and calibration curve preparation is forty (40) minutes.

2.0 REFERENCES

1. Nuclear Regulatory Commission, Nuclear Regulatory Guide (NUREG) 0737, Section'I.B.3.

2. NUS Report, "Final Report - Analyses for Dissolved Hydrogen, Dissolved Oxygen, Boron, Chloride, pH and Conductivity Under Normal and Post-Accident Conditions",

R-.27-10-0-2, dated October 22, 1980.

I 3.0 RESPONSIBILITIES The Plant Monitoring Team member responsible for performing the boron analysis on post-accident samples shall report the results to the Plant Monitoring Team Leader as soon as practicable following the analysis.

4.0 DEFINITIONS AND ABBREVIATIONS 4.1 Definitions Not Applicable 4.2 Abbreviations

1. PASS - Post-Accident Sampling System

2. RCS - Reactor Coolant System

3. RHR - Residual Heat Removal

4. AAT >> Accident Assessment Team

5. RAB - Reactor Auxiliary Building

6. 'SIE - Specific Ion Electrode

7. ALARA - As Low As Reasonably Achievable

8. ml - Milliliter

9. mV - Millivolt CRC-827 Rev. 1 Page 3 of 14

CRC004 OS2

4. 2 Abbreviations (continued)

10. STDBY - Standby

11. DI - Deionized

12. N - Normal

13. ppm - Parts Per Million 5.0 GENERAL Boron measurements on post-accident samples are required to verify the proper shutdown margin has been achieved. This procedure is qualified for 1:1000 diluted samples containing 0.5 to 6.0 ppm boron. This range can be extended by calibration in the region of interest. The mean absolute bias determined by NUS Operating Services Corporation during testing i

(refer to reference 2.2),of the procedure was 3.0 percent at boron levels of 2.0 ppm, and 2 10 percent at boron levels of 0.5 ppm. Assuming a. 1:1000 dilution, the range of the procedure is 500-6000 ppm boron in reactor coolant samples.

Thus, the fluoroborate method meets the accuracy and range requirements identified in the Nuclear Regulatory Commission's post implementation evalugtion criteria guidelines.

1 ~ Prior to analyzing the sample or preparing a calibration curve, ensure that all reagents have not expired their stated chemical shelf-life.

2. Prior to analyzing a sample, ensure that the calibration curve has been prepared. within the previous three months.

3. A working boron standard must be analyzed in conjunction with each sample.

. 4. Samples and boron standards shall be analyzed in duplicate.

5. A normal or emergency radiation work permit has been prepared for analyzing the PASS sample.

6. The Site Emergency Coordinator has determined a boron "analysis of the sample obtained from the PASS is necessary.

CRC-827 Rev. 1 Page 4 of 14

CRC004

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OS2 7.0 PRECAUTIONS AND LIMITATIONS Very high dose rates and high levels of airborne radioactivity may be present in unexpected locations of the Reactor Auxiliary Building (RAB); therefore, strict compliance to radiation control requirements shall be followed.

2. All reactor coolant and residual heat removal pump discharge samples shall be assumed to be extremely radioactive unless otherwise determined by a radiological survey. All liquid volumes collected during post-accident sampling and analysis including dilutions shall be handled with extreme care to prevent unnecessary personnel exposures

3. All operations shall be carried out in an operating hood with lead bricks stacked as a shield between the sample and the technician performing the analysis.

4. Temperature variance between 'standards and samples must, be controlled to within a 5 C range. The maximum temperature at which samples can be analyzed is 40 C.

5. Sample stirring action should be controlled at a rate which precludes the formation of a vortex or bubbles.

6. Fluoride solutions aze poisonous. Acidic fluoride solutions are very corrosive. Do not allow acidic fluoride solutions to contact skin. Vash with water and apply a dispute calcium chloride solution if acidic solution contacts skin. Do not dispose of a concentrated fluoride-containing solutions in the radwaste system if processed water will be reused in the plant. Instead, transfer the fluoride-containing waste solutions to a plastic bottle containing an absorbent material such as Drierite or Sozb-All and dispose of it later as solid waste ~

7. The pH meter must be placed in the STDBY mode before removing the electrodes from solution. Failure to do so will cause the electrode's response to drift.

8. Normally, the electrodes used in this procedure are only good for six months following their initial use, although their life is sometimes longer. A calibration curve check should be used to decide if the electrodes need replacing.

If reproducible readings for calibrations cannot be obtained electrode replacement is necessary.

The stirring rate used for sample and standard analysis must be kept constant.

CRC-827 Rev. 1 Page 5 of 14

CRC004 OS2 ~

7.0 PRECAVi'IONS AND LIMITATIONS (continued)

10. Ensure that no bubbles are adhering to the electrode bottom near the membrane when making a measurement.

ll. All millivolt readings taken will be as relative millivolts.

12. Electrodes should be stored when not in use by soaking them in a beaker of distilled water.

8.0 REAGENTS AND APPARATUS 8.1 R~ea eats NOTE: Commercially prepared reagents are available.

1. Saturated Sodium Fluoride

a. Add 30 grams of reagent grade sodium fluoride to 100ml of demineralized water.

b. Mix well.

c. Store the solution in a properly labeled plastic bottle.

d. The chemical shelf-life of this solution is one year.

NOTE: If the solution forms two layers, decant the upper layer and discard the bottom layer.

2. Sulfuric Acid " 10 N

a. Slowly and cautiously add 28ml of concentrated sulfuric acid to approximately 50ml of demineralized water contained in a 100ml volumetric flask.

b. Carefully mix the solution and allow it to cool to Moom temperature.

c. Dilute the solution to the mark, then mix well.

d. Store the solution in a properly labeled plastic bottle.

e. The chemical shelf-life of this solution is one year.

CRC-827 Rev. 1 Page 6 of 14

P CRC004 OS2 8.1 ~Rea ants (cnntdnned)

3. . Boron Standard - 1000 ppm'.

Use Fisher Cat. No. SO-B-155 or equivalent.

b. The chemical shelf-life for this solution is six months following the opening of the bottle or as recommended by the vendor. When opening new bottle, the date opened and technician's initials should be noted on the label.

4. Boron Stock Solution - 100 ppm

a. Dilute 10.0ml of 1000 ppm boron solution to 100ml of demineralized water and mix well.

h. Store the solution in a properly labeled plastic bottle.

c. The chemical shelf-life of this solution is three months.

5. Boron Working Solutions

a. Prepare boron working solutions from the 100 ppm

. boron stock solution as follows:

ml of 100 ppm Boron ppm Boron of Solution Diluted to 100ml Workin Boron Solutions 0.50 0.5 1.00 1.0 2.00 2.0 3.00 3.0 5.00 5.0

b. Store each working boron solution in a properly labeled plastic bottle.

c. The chemical shelf-life for each working boron solution is thirty days.

6. 3 m KCL Reference electrode fill solution.

8.2 8~states

1. pH Meter - Capable of measuring in the relative millivolt mode

2. Fluoroborate Specific Ion Electrode - Orion Model 93-05 or equivalent CRC-827 Rev. 1 Page 7 of 14

~

2

CRC004

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OS2

8. 2 ~Aazatus (continued)

3. Plastic Single Junction Reference Electrode - Orion Model 90-01 or equivalent

4. Magnetic Stirrer

5. Micro Stirring Bar

6. Plastic Beakers - 30ml

7. Pipettes - 0.5, 1.0, 2.0, 3.0, 5.0 and 10.0ml

8. Volumetric Flasks - 100ml

9. Two Cycle Semi-Logarithmic Graph Paper

10. Timer

11. Plastic Bottle. - 4 oz,

12. Top-Loading Balance

13. Drierite or Sorb-All 9.0 ACCEPTANCE CRITERIA The difference between the millivolt response between duplicate samples should not be greater than 2 millivolts.

10.0 PROCEDURE 10.1 Pre aration of a Calibration Curve NOTE: The electrodes should be stored in deionized water at all times. When using new electrodes, soak them in deionized water for at least 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br />, or as long as possible prior to use ~

NOTE: Place micro stirring bar into the sample prior to placing electrodes into the sample.

1. Pipette 5.0ml of deionized water (blank), and 5.0ml of the following boron standards into separate plastic beakers.

~ .Boron Concentration Volume 0.5 ppm 5.0 ml 1.0 ppm 5.0 ml 2.0 ppm 5.0 ml 3 ~ 0 ppm 5.0 ml 5.0 ppm 5.0 ml CRC-827 Rev. 1 Page 8 of 14

CRC004 OS2 10.1 Pre aration of a Calibration Curve (continued)

2. Pipette 1.0ml of saturated sodium fluoride solution into each of the blank and standard boron solutions.

3. Pipette 0.5 ml of 10 N sulfuric acid into each of the blank and standard boron solutions at exactly 5 minute intervals.

4. Record the time of each acid addition on Form CRC-827-1-0.

E NOTE: Rinse the electrodes with demineralized water and blot the tips dry prior to testing the next solution.

5. Place the electrodes into each solution 15 f 1 minute after each acid addition.

NOTE: Stir the solutions at a constant rate while measuring the millivolt response. Ensure that no bubbles are adhering to electrode bottom near the membrane when measuring. The reaction is time dependent and the millivolt response should  !

be read as close to 20.0 minutes as practicable.

6. Measure and record the relative millivolt response at 20 minutes (i 15 seconds) after the acid addition to each blank and standard. Use Form CRC-827-1"0 to record the millivolt readings.

7. Plot the boron solutions concentrations in ppm on the logarithmic axis versus the relative millivolt response for the boron standards on the linear axis of two-cycle semi-logarithmic graph paper.

8. Draw the best fit curve through the obtained data points.

10.2 Sam le Anal sis NOTE: Soak the electrodes in deionized water for at least

.twenty-four (24) hours or as long as possible prior to use.

NOTE: The boron standard used should be approximately the same boron level as the sample.

NOTE: If necessary, the sample must be diluted to contain a boron concentration of 0.50 to 5.0 ppm.

CRC-827 Rev. 1 Page 9 of 14

CRC004 OS2 10.2 Sam le Anal sis(continued)

1. Pipette 5.0ml of reactor coolant or residual heat removal pump discharge sample containing between 0.5 and 5.0 ppm boron and 5.0ml of a boron working standard into separate plastic beakers.

2. Pipette 1.0ml of saturated sodium fluoride and 0,5ml of 10 N sulfuric acid into the working boron solution. Record the time of acid addition on Form CRC-827-1-0.

3. Wait 5 minutes, then pipette 1.0ml of saturated sodium fluoride and 0.5ml of 10 N sulfuric acid into the diluted reactor coolant (residual heat removal pump discharge) sample. Record the time of acid addition on Form CRC-827-1-0.

4. At 15 2 1 minutes after the acid addition to the standard boron solution, rinse the electrodes with deionized water and insert them into the beaker containing the boron standard.

NOTE: Use the relative millivolt mode on the meter and stir the solution at a constant rate while measuring the millivolt response.

NOTE" If 'the millivolt reading for the boron standard does not correspond with the calibration curve, adjust the meter's calibration control knob to read the correct value for the standard.

5. Measure and record the millivolt response at 20 minutes (+

15 seconds following acid addition). Use Form CRC-827-1-0 to record the millivolt response.

6. At 15 k 1 minutes after the acid addition to the diluted reactor coolant (residual heat removal pump discharge) sample, rinse the electrodes with deionized water and insert them into the beaker containing the sample.

NOTE: Stir the solution at a constant rate while avoiding the bubbles and measuring the millivolt response and record the millivolt reading as close to 20.0 minutes following acid addition as practicable.

7. Measure and record the sample's relative millivolt response at 20 minutes (2 15 seconds) following the acid addition. Use Form CRC"827-1<<0 to record the millivolt response.

CRC-827 Rev. 1 Page 10 of 14

CRC004 OS2

8. Determine the sample's boron concentration in ppm from the calibration curve. V

11. 0 DIAGRAMS ATI'ACHMENTS CALCULATIONS 11.1 ~Dia rams Not Applicable 11.2 ATl'ACHMENTS NOTE: Use the controlled copy of the current calibration curve to determine the boron concentration of the sample.

l. ATTACHMENT .1: Example Calibration Curve NOTE: Attachment 1 is for informational purposes and is not to be used as a substitute for a current calibration curve.

2. ATTACHMENT 2: Form CRC-827-1-0, Data Sheet for Fluoroborate-Boron Analysis 11.3 Calculations

1. Multiply the sample's boron concentration determined from the calibration curve by the dilution factor to determine the final boron concentration in the sample.

Bf~DFf xBc Where:

B f= the final boron concentration of the sample in ppm B = the boron concentration of the diluted sample as read from the c

calibration curve in ppm DF = Final Dilution factor f

2. The final dilution factor (DFf) of samples is calculated as follovs:

Vf DFf => xDFi s

CZC-827'ev. 1 Page 11 of 14

CRC004 OS2 11.3 Calculations (continued)

Where:

DF = the final dilution factor of the sample V = the. final volume to which the sample is diluted in ml f

V = the volume of sample that is diluted in ml s

DF = the initial dilution factor of the sample that is obtained by diluting the sample at the PASS.

3. To calculate the .diluted liquid grab sample's dilution factor (DFi),

apply the following equation.

DF =W W 1 n(0. 10)

Where:

W 2

= the final weight of the sample bottle following collection of sample and dilution, grams.

W 1

= the initial weight of the sample bottle prior to sample collection, grams.

n = the number of aliquots taken DF = diluted liquid sample dilution factor CRC-827 Rev. 1 Page 12 of 14

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) m CRC004 OS2 Form CRC-827-1, Rev. 0 Fluoroborate - Boron Anal sis Data Sheet I. Calibration Curve Data Boron Standard Time of Acid Time of Millivolt Relative Millivolt Concentration Addition Measurement . Measurement 0.0 ppm (Blank) mV 1.0 ppm mV 2.0 ppm mV 3.0 ppm mV 5.0 ppm mV Date of Calibration: / /

Prepared By:

s (Name of E&C Technician)

II. Post-Accident Sam le Collection and Dilution Data Final Volume of Sample Smsple Time: has. After Dilution ml Sample Ordain: Volume of Sample Diluted ml Boron Std. Used: ppm Dilution Factor III. PASS Sam le Anal sis Date Analyzed: / /

Time analyzed: hrs.

Time of Time of Relative Expected Acid Millivolt Millivolt Millivolt Addition Measurement Measurement Measurement Boron Std.

Sample (1) mV Sample (2) mV Boron Concentration Dilution Final Boron From Graph x Factor Concentration Sample (1) ppm x ppm Sample.(2) ppm x ppm Analyzed Ey:

(Name of E&C Technician)

Reviewed:

(Plant Monitoring Team Leader) Date CRC"827 Rev. 1 Page 14 of 14