IR 05000213/1987029

Insp Rept 50-213/87-29 on 871130-1204.No Violations Noted. Major Areas Inspected:Nonradiological Chemistry Program. Areas Reviewed Included Measurement Control & Analytical Procedure Evaluations

ML20148R673
Person / Time
Site:	Haddam Neck File:Connecticut Yankee Atomic Power Co icon.png
Issue date:	01/14/1988
From:	Jang J, Pasciak W, Zibulsky H NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20148R584	List: IR 05000213/1987029
References
50-213-87-29, NUDOCS 8802020259
Download: ML20148R673 (6)

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V. S. NUCLEAR REGULATORY COMMISSION

REGION I

Report No. 50-213/87-29 Docket N License N DPR-61 Priority --

Category C Licensee: Connecticut Yankee Aton:ic Power Company P. O. Box 270 Hartford, Connecticut 06101 Facility Name: Haddam Neck Nuclear Power Station Inspection At: Haddam Neck, Connecticut Inspection Conducted: November 30-December 4, 1987 Inspectors: 9 ibulsky, QMemist \

/ -Y-U date C- e i- 4 - sr date Jang,SeniorpdiationSpecialist An Approved by:/ /fi /m41 / - f8

/ -date G Msc~iak, Chief ETTluents

' diation Protection Section Inspection Summary: Inspection on November 30-December 4, 1987 (Report N /87-29)

Arecs Inspected: Routine, annoenced inspection of the nonradiological chemistry program. Areas reviewed included measurement control and analytical l procedure evaluations.

i Results: No violations were identified.

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! 8802020259 880119 i PDR ADOCK 05000213 i

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DETAILS Individual Contacted G. Bouchard, Station Service Superintendent

• P. Heffernan, Assistant Chemistry Supervisor

• G. Goncarovs, Chemist S. Matthess, Chemist

• D. Miller, Jr.. Station Superintendent M. Quinn, Chemistry Supervisor

• Denotes those present at the exit intervie The inspector also interviewed other licensee employees including members of the chemistry staf . Measurement Control Evaluation Verification of the licensee's measurement capabilities on actual plant water samples is done by splitting samples with the licensee and Brookhaven National Laboratory (BNL). The steam generator sample was taken for anion and metal analyses and the mix tank sample was taken for boron analysis. One steam generator sample was spiked with a standard solution of fluoride, chloride, and sulfate and another steam generator sample was spiked with a standard solution of iron, copper, nickel, and chromium. These 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 50-213/87-29-01). Analytical Procedures Evaluation Standard cheinical solutions were submitted to the licensee for analysis during this inspectio The standard solutions were prepared by BNL for the NRC, and were analyzed by the licensee using normal methods and equipmen The anelysis of standards is used to verify the licensee's capability to monitor chemical parameters in various plant systems with respect to Technical Specification, 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 one out of thirty six measurements was in disagreement under the criteria used for comparing results (see attachment 1). The results of the comparisons are listed in Table The nickel, chromium, and iron results in Table 1 are rerun analyse The licensee's standard solutions for the three analytes, were degrade The licensee, therefore, prepared new standard solutions to calibrate equipment. In addition, the micro-pipet which was used to aliquot the NRC standard solutions was also calibrate _ _ _ _ _ _ _ - _ - _ _ _ - _ - _ __ _ ___ _ __ ___-___ _ _ _ _ _ _ _ _ _ . _ - _ _ _ _ - _ _ _ __ - . _ _ _ _ _ _ _ _ ______

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The inspectors observed that two point calibrations were being performed for the atomic absorption analyses of the netals. Nonlinearity of the calibration curves were difficult to identify. A minimum of three data points, excluding zero, for calibrations will be incorporated into the licensee's measurement progra The fluoride disagreement at low concentration (around 5 ppb) using the ion chromatograph was due to the equipment rather than the analytical procedure. The licensee used an ion chromatograph (Waters ILC-1 Model)

to measure fluoride concentration. The "air" peak was immediately followed by the fluoride peak (the air peak partially overlapped the fluoride peak), making it difficult to separate the two peaks. Two methods, area integration and peak-height determination, can be used to measure the fluoride concentration. The licensee used the area integration method and the results were not in agreement. During the inspection, the licensee used the peak-height determination method to determine the fluoride value and the results are listed in Table 1. The licensee is going to investigate the possibility of using a different eluant concentration to separate the air peak and the fluoride peak in the near futur One fluoride disagreement was due to calculated statistical differenc The actual difference was 7% of BNL's value which is not considered significan . Exit Interview The inspectors met with the licensee representatives (denoted in paragraph 1) at the conclusion of the inspection on December 4,1987, and summarized the scope and findings of the inspection. At no time during this inspection was written material provided to the licensee by the inspectors.

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Table 1 Capability Test Results Haddam Neck Nuclear Power Station Chemical Analytical Parameter Procedure NRC Value Lic. Value Ratio (Lic./NRC) Comparison Results in Part Per Million (ppm)

• Boron Aut Titration 1000 10 1000 1 Agreement 3024 46 2998 2 0.99 0.02 Agreement 4947 61 4978 3 1.01 0.01 Agreement Ammonia Spectrophotometry 1.7510.11 1.94 0.001 1.11 0.07 Agreement 3.14 0.26 2.97 0.006 0.94 0.08 Agreement 1.88 0.17 1.9820.009 1.05 0.10 Agreement

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Results in parts per billion (ppb)

Sodium AA-Flame 10.2t .7 .8510.08 Agreement 18.8 .3 .13 0.12 Agreement 28.8 .3 .91 0.05 Agreement

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Copper AA-Flame 46.8 .0 .15 0.11 Agreement 96.6 .3 .01 0.05 Agreement 145.0 .7 .01 0.07 Agreement

• Iron AA-Flame 48.9 .7 .1010.10 Agreement (Rerun) 95.5 .0! .97 0.05 Agreement 147.0 .7 .98 0.04 Agreement

• Nickel Graphite 50.9 .0t .0810.06 Agreement (Rerun) Furnace 102.0 .7 .06 0.03 Agreement 153.0 .0 .06 0.03 Agreement

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• Chromium Graphite 50.9 .0 .04 0.06 Agreement (Rerun) Furnace 94.1 .0tl.7 1.0820.04 Agreement 143.0 .7 2.1 1.06 0.06 Agreement Hydrazine Spectrophotometry 89.2 .0 .91 0.06 Agreement 28.5! .8 0 0,98 0.02 Agreement 52.0 .0 0 0.98 0.01 Agreement

• Silica Spectrophotometry 108.6 1 .7 1.2 0.95 0.10 Agreement 218.0 1 .0 1.0 0.97 0.06 Agreement 320.0!1 .0 2.0 0.97 0.03 Agreement

• Fluoride Ion 5.8 .9 .84i0.04 Disagreement (Rerun) Chromatograph 10.9 .6 .9720.05 Agreement 20.9 .3 .07 0.03 Statistical Disagreement

• Chloride Ion 6.0 .4 .90 0.12 Agreement Chromatograph 9.4 .4 0.06 1.11 0.09 Agreement 20.1 .2 .0520.04 Agreement

• Sulfate Ion 10.0 .11 .01 0.10 Agreement Chromatograph 20.5 .7 .9610.06 Agreement 40.4 .0 .97 0.05 Agreement

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ATTACHMENT 1 CRITERIA FOR COMPARING ANALYTICAL MEASUREMENTS This attachment provides criteria for comparing results of capability test In these criteria the judgement limits are based on the uncertainty of the ratio of the li ensee'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 );

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

If the absolute value of one minus the ratio is less than or eaual to twice the ratio uncertainty, the results are in agreemen (l1-ratic( 5 2 uncertainty)

2 2

Z= x, then 5 2 , 3 3 x .

Y 2 2 Z x y2

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

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