IR 05000334/1987009

Insp Rept 50-334/87-09 on 870519-22.No Violations Noted. Major Areas Inspected:Nonradiological Chemistry Program, Including Analytical Procedure Evaluations & Measurement Control

ML20216G040
Person / Time
Site:	Beaver Valley
Issue date:	06/18/1987
From:	Pasciak W, Zibulsky H NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20216G010	List: IR 05000334/1987009 ML20216G006
References
50-334-87-09, 50-334-87-9, NUDOCS 8706301005
Download: ML20216G040 (5)

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U.S. NUCLEAR REGULATORY COMMISSION

REGION I

Report N /87-09 Docket N License N OPR-66 Priority --

Category- C Licensee: Ouquesne Light Company  :

435 Sixth Avenue Pittsburgh, Pennsylvania 15219 Facility Name: Beaver Valley Power Station, Unit 1 Inspection At: Shippingport, Pennsylvania Inspection Conducted: May 19 - 22, 1987 In spector.: @ d2-IF-T 7 H. Zibulsk), enemist '

date Approved by: M M Syt le-lT-T 7 l W. J. PascihkFJChief \ U date Effluents Radiation Protection Sec. , DRSS Inspection Summary: Inspection on May 19-22, 1987, (Report.No. 50-334/87-09)

Areas Inspected: Routine, announced inspection of the nonradiological chemi stry program. Areas reviewed included analytical procedure evaluations and measurement contro Results: No violations were identifie ,

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8706301005 870619 PDR ADDCK 05000334 G PDR

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DETAILS

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1 Individuals Contacted

• D. Hunkele, Director, QA Operations

• V.' Linnenbom,. Director, Plant Chemistry

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~ *D; Evans, Chemistry, Trend and Analysis Coordination

• F. Lipchick', Senior Licensing Supervisor

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• Vincinie, Senior QA Specialist 1 O. Orndorf, Senior. Chemist I

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Sepelak, Licensing Engineer i J. Bost, Licensing Engineer Ai Dulik, Chemistry Supervisor

The inspector also interviewed other licensee employees including-members of the. cumistry .staf * denotes those present at the. exit intervie d

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Analytical procedure-Evaluation During the. inspection, standard chemical solutio $ were submitted to the y licensee:for analysi The standard solutions were prepared by the-

• Brookhaven National Laboratory for the NRC, and the standards were -

analyzed by.the licensee using normal methods'.and equipment. The analysis of' standards is used to ' verify the licensee's capability to monitor chemical parameters in various plant systems with respect to Technical q-Specification requirements and other regulatory requirements. In addition, the analysis of standards is used to evaluate the licensee's analytical

. procedures with1 respect to accuracy and precisio The results of the standard measurements comparison indicated that two.out of thirty comparisons' were in disagreement under the criteria used for comparing results ('ees attachment 1). The results of the comparisons are listed in Table 1. ~

The hydrazine and silica'results reported in Table 1 are reruns. The NRC'

,? l standards identified that the 1 cm cell used in the spectrophotometric analysis for~hydrazine and silica was too small for good resolution and accuracy.at~ the lower concentrations. of the two analytes. - The licensee-re an the hydrazine analysis using a 5 cm cell in a new instrument. The results improved, but were still biased low. The silicas were rerun using a'2 cm cell. The results were good and the bias'was eliminate ';

a The boron standards were rerun. ..The original licensee values had positive biases which wer'e identified by the inspector to be the result of l

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inadequate temperature control. The NRC standards were made up and- !

analyzed in a temperature of about 25 C and the licensee's room i temperature was.about 21 When the temperature difference was j compensated for,-the boron result on the boron standard that was in I I

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, 3 disagreement was. reduced by 2%. The inspector recommended better temperature control for both the hot and cold laboratorie The fluoride, chloride and sulfate standards were rerun. The licensee's control standards identified a problem with the ion chromatograph. The licensee replaced the columns in the instrument and the results were well within the acceptance criteri . Measurement Control Verification of the licensee's measurement capabilities on actual plant- ;

water samples is done by splitting samples with the licensee and BNL. The l condensate sample was taken for anion analysis, .the feedwater sample was I taken for iron and copper analyses, the hot well sample was taken for hydrazine analysis and the holding tank was taken for boron analysis. The condensate sample was spiked with a standard solution of fluoride,-

chloride and sulfate and the feedwater sample was spiked with a standard solution of iron and copper. 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 (Inspection Follow-up Item 50-344/87-09-01).

Two independent standard. stock solutions for calibration and measurement l contral'were being used. The licensee was able to identify a degenerated standard solution and verify the quality of the standard The licensee has generated calibration curves that were statistically fit to the data points. The linear regression program was computerized. The i licensee generated control charts with acceptance criteria of 2 sigma and an unacceptable parameter of 3 sigma. In some charts, the licensee was using control standards with twice the concentration as the samples they I were analyzing. The error in the measurement system was not reflected for the concentration of the analyte being determined. The licensee will correct this by generating control charts with standards in approximate i concentrations of the analytes being analyze ~

4. Exit Interview q The inspector met with the licensee representatives (denoted in paragraph 1) at the conclusion of the inspection on May 22, 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 inspector, j l

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TABLE 1

Cap' ability Test Results Beaver Valley Power Station, Unit 1  !

Results in parts per billion (ppb) I Fluoride Ion Chromatograph 9.2 .8 .95 0.08 Agreement 8.7 {

8.41 .97 0.08 Agreement 16.7 .21 .97 0.04 Agreement-Chloride Ion Chromatograph 9.61 .0 0 5

. 0.94 0.06 Agreement 7.5 .1 .95 0.05 Agreement

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16.1 .6 .97 0.03 Agreement j

Sulfate Ion Chromatograph 12.01 .71 .98 0.05 Agreement 12.3 .8 .96 0.08 Agreement ;

32.3 .11 .93 0.05 Agreement Iron Graphite Furnace 4.9 .8 .98 0.10 Agreement ;

9.6 .0 .1510.08 Agreement 14.7 .2 .1010.09 Agreement Copper Graphite Furnace 4.71 .51 .96 0.22 Agreement 9.7 .71 .90 0.05 Agreement l 14.5 .6 .94 0.045 Agreement Sodium Flame Emission 4.61 .0 .09 0.12 Agreement 9.2 .2 .1010.10 Agreement :

14.4 .9 .0310.06 Agreement I Ammonia Spectrophotometry 87.6 .0 18.3 1.04 0.22 Agreement 314 26 286-13 0.91 0.09 Agreement s

938185 1006 12 1.07 0.10 Agreement Hydrazine Spectrophotometry 22.3 .3 .87 0.08 Agreement 56.9 .3 .92 0.02 Disagreement 104 .3 0.6 Agreement Silica Spectrophotometry 21.7 .0 0 1.01 0.10 Agreement 43.6 .0 1 1.01 0.07 Agreement 64.0 .0 1 0.97 0.03 Agreement Results in parts per million (ppm)

Boron Mannitol Titration 985 10 1008 .02 0.01 Agreement i 2980 50 1.01 0.02

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299716 Agreement 4870 60 5005 9 1.03 0.01 Disagreement

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.1 ATTACHMENT 1 CRITERIA FOR COMPARING ANALYTICAL MEASOREMENTS This. attadhment provides-criteria for comparing.results 5f capability test In:these criteria.the. Judgement limits are based on:the uncertainty of,the

., ' ratio lof;the licensee's value'to the NRC value. The.following. steps.are-i'~> ' performed: -

,c M  :(1)':the ^ ratio' of the licensee'sf value to the.NRC value is computed .

Jr , LicenseeTValue! I

. ratio =.NRC Value );

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

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If the absolute value of1 one minus the ratio is less than or equal:to:

1twice thel ratio ' uncertainty, Lthe results are'in agreemen ratiol 5 2 uncertainty)L

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1Z=' x, then 52- 32 32- g-j *f + f ,

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1(From: Bevington,-P. R., Data. Reduction and Error Analysis for the

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Physical' Sciences, McGraw-Hill, New York, 1969)

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