IR 05000245/1987028

Insp Repts 50-245/87-28 & 50-336/87-24 on 871102-06.No Violations Noted.Major Areas Inspected:Nonradiological Chemistry Program,Including Measurement Control & Analytical Procedure Evaluations

ML20149E392
Person / Time
Site:	Millstone
Issue date:	12/22/1987
From:	Jang J, Pasciak W, Zibulsky H NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20149E386	List: IR 05000245/1987028 ML20149E381
References
50-245-87-28, 50-336-87-24, NUDOCS 8801130328
Download: ML20149E392 (6)

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i U. S. NUCLEAR REGULATORY COMMISSION

REGION I

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Report No. 50-245/87-28 50-336/87-24

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License Nc. DPR-21 Priority -- Category C DPR-65 Licensee: Northeast Nuclear Energy Company P. O. Box 270 Hartford, Connecticut 06101 Facility Name: Millstone Nuclear Power Plants, Units 1 and 2 Inspec. tion At: Waterforo, Connecticut Inspection Conducted: November 2-6, 1987 Inspectors: Wk ,

ibulskyl, CMmist '

12 -7- F7 date 44 4 % 0- V64V - f- S 9 d Ja g. Senior Rauiatiog Specialist date Approved by: -

  , dVrA  /rRfM Me W .V d .

Radi iak, Chief. Effluents on Protection Section, DRSS f- fate Inspection Sunna,y: Inspection on November 2-6, 1987 (Combined Report No /87-28 and 50-336/87-24).

Areas Inspected: Routine, announced inspection of the nonradiological chemistry Fogram. Areas reviewed included measurement control and analytical procedure ' evaluations.

, Results: No violations were identified.

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'8801130328 DR 871230 ADOCK 05000245 DCD
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Details 1. Individuals Contacted H. Haynes, Station Services Superintendent J. Waters, Chemistry Supervisor T. Iteillag, Unit 2 Assistant Supervisor T. Burns, Unit 3 Assistant Supervisor G. D'Auria, Analytical Chemist S. C.andall, Unit 2 Chemist F. Mueller, Unit 3 Chemist J. Glaub, Unit 1 Chemistry Specialist All were present at the exit intervie The inspectors also interviewed other licensee employees including members of the chemistry staf . Analytical Procedures Evaluation During the inspection, standard chemical solutions were submitted to the licensee for analysis. The standard solutions were prepared by the Brookhaven National Laboratory (BNL) for the NRC, and were analyzed by the licensee using normal methods and equipment. The analysis of stand-ards is used to verify the licensee's capability to monitor chemical parameters in various plant syster.3 with respect to Technical Specifica-tion, vendor and fuel warranty requirements. In addition, the analysis of standards is used to evaluate the licensee's analytical procedures with respect to accuracy and precisio The results of the standard measurement comparisons indicated that six out of thirty-eight measurements were in disagreement under the criteria used for comparing results (see Attachment 1). The results of the comparisons are listed in Table The fluoride disagreements were probably caused by the eluent the licensee was us ng. Approximately 15% of the fluoride was not being eluted. The licensee will investigate this proble The hydrazine disagreement was due to the licensee not statistically fitting the calibration curve. The licensee did generate a new calibration data using absorbance versus concentration. A least square . fit curve was generated by the computer from the data. The concentration that was 19% biased fell to 1% and was in agreement from the data. The boron and copper disagreements were due to sampling errors. The ammonia disagreement was due to the licensee using a single point calibration for the specific ion electrode. The licensee will use three data points, excluding zero, to generate calibration curves for any specific ion electrode procedure that will be used for analysis. With a single point calibration, the licensee was unable to identify a slope change or nonlinearity in the calibration curv . . ..

2 Measurement Control Evaluation Verification of the licensee's measurement capabilities on actual plant water samples is done by splitting samples with the licensee and BN The standby liquid control tank sample was taken for boron analysis, the steam generator sample was taken for anion, ammonia and hydrazine analyses and the feedwater system sample was taken for metal analyse The steam generator sample was spiked with a standard solution of fluoride, chloride and sulfate, and the feedwater sample was spiked with a standard solution of iron, copper, nickel and chromium. The standard spike solutions were prepared by BNL for the NRC. On completion of the analyses by BNL and the licensee, an evaluation will be made (Inspector Follow-up Item 50-245/87-28-01 and 50-336/87-24-01).

The inspectors observed that the licensee was using two independent standard stock solutions for calibration and control. The maintenance of two standard stock nlutions provided the licensee with an analytical cross check on the contuiuing quality of the stock solution The licensee is initiating a new measurement control procedure with new forms for data documentation and control. With this new procedure and the resolution of the measurement problems identified with the NRC standards, the licensee will have a good measurement program. The program and resolutions should be in effect by mid December 198 . Exit Interview The inspectors met with the licensee representatives (denoted in paragraph 1) at the conclusion of the inspection on November 6, 1987, and summarized the scope and findings of the inspection. At no time during this inspec-tion was written material provided to the licensee by the inspector . . .-

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Capability Test Results " Millstone Nuclear Power Plants, Units 1 and 2 Chemical Analytical NRC Li Ratio Parameter Procedure Yalue Value (Lic./NRC) Comparison _ Resultsinpartsperbillion(ppb) Chloride Ion Chromatograph (anion) 6.0 0.8 4.9 .8210.11 Agreement 9.4 0.3 9.6* .0210.05 Agreement , 20.1 0.6 20.81 .0320.05 Agreement Chloride Ion Chromatograph 6.0i0.8 4.8 0.02 0.8010.12 Agreement (org.) 9.410.3 10.2 0.1 1.09 0.04 Agreement 20.110.8 20.81 .0310.04 Agreement " Fluoride Iun Chromatograph 5.81 .02 .8610.03 Disagreement 10.9 .li .83i0.04 Disagreement - i Sulfate Ion Chromatograph 5.0 0.2 5.5 0.03 1.0910.05 Agreement

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10.310.6 10.4 0.3 1.0110.07 Agreement 20.2i0.8 20.410.2 1.0110.04 Agreement Sodium Graphite Furnace 4.6 .010.02 1.09 0.12 Agreement 9.2 0.8 10.1 0.1 1.10 0.09 Agreement 14.410.8 15.52 .0820.06 Agreement Hydrazine Spectrophometry 11.2 0.7 10.8 .96t0.22 Agreement 28.5 0.4 23.2 .81 0.02 Disagreement 52.0 0.5 48.9 .9410.03 Agreement Ammonia Specific lon 87.6 5.3 90.7 .0410.08 Agreement j Electrode 314 26 26813 0.85 0.07 Disagreement :

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235221 22518 0.9610.09 Agreement

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Sil.;a Spectro-photometry 27.2 2.8 24.7 .91 0.11 Agreement 54.Si2.8 50.3 .9210.06 Agreenient 80.022.5 75.7 .95 0.05 Agreement Resultsinpartspermillion(ppm) Boron Titration 1000110 1030 10 1.0310.01 Disagreement 3024 46 2992114 0.9910.02 Agreement 4947 61 5110149 1.0320.02 Agreement Copper AA-Flame 0.75 0.04 0.85i0.01 1.1310.06 Disagreement 1.5510.08 1.64t0.01 1.0610.06 Agreement 2.3210.10 2.41 0.01 1.04 0.05 Agreement Iron AA-Flame 0.78 0.06 0.81 0.01 1.0420.08 Agreement 1.5310.05 1.5320.03 Agreement 2.3510.07 2.31 0.03 0.98 0.03 Agreement Nickel AA-Flame 0.8110.04 0.8110.02 Agreement 1.63 0.05 1.5620.01 0.96 0.03 Agreement 2.45 0.06 2.35 0.02 0.96 0.02 Agreement Chromium AA-Flame 0.8210.05 0.8410.02 1.02 0.07 Agreement 1.5110.05 1.5210.05 1.01 0.05 Agreement 2.29 0.13 2.27 0.02 0.99t0.06 Agreement l l

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.' .,. . . ATTACHMENT 1 l

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CRITERIA FOR COMPARING ANALYTICAL MEASUREMENTS I l

This attachment provides criteria for comparing results of capability tests. In these criteria the judgement limits are based on the uncertainty of the ratio of the licensee's value to the NRC valu The following steps are performed:

(1) the ratio of the licensee's value to the NRC value is computed
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Licensee Value (ratio = NRC Value ); .

(2) the uncertainty of the ratio is propagated.'

If the absolute value of one minus the ratio is less than or ecual to twice the ratto uncertainty, the results are in agree en (l1-ratio 4 s 2 uncertainty) 2 2 2

 * Z= x, then 5 , 5 , 3 Y 2 2 2_

Z x y 8(From: Bevington, P. R., Data Reduction and Error Analysis for the Physical Sciences, McGraw-Hill, New York, 1969)

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