IR 05000412/1987025

Insp Rept 50-412/87-25 on 870407.No Violations Noted.Major Areas Inspected:Nonradiological Chemistry Program,Including Measurement Control & Analytical Procedures Evaluation

ML20214S324
Person / Time
Site:	Beaver Valley
Issue date:	05/22/1987
From:	Pasciak W, Zibulsky H NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20214R705	List: IR 05000412/1987025 ML20214R701
References
50-412-87-25, NUDOCS 8706090229
Download: ML20214S324 (6)

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U.S. NUCLEAR REGULATORY COMMISSION

REGION I

Report N /87-25 Docket N License N CPPR-105 Priority -

Category B Licensee: Duquesne Light Company 435 Sixth Avenue Pittsburgh, Pennsylvania 15219 Facility Name: Beaver Valley Power Station, Unit 2 Inspection At: Shippingport, Pennsylvania Inspection Conducted: April 7-10, 1987 Inspector: Od Um M% Lh W P)

H. Zibulsky, ChemisQ date Y Approved by: 4L/ >\ ,f, c-t < <m 2/.' ([$7 F N. J rfascnk, Chief, eft 1uents Radiation date'

PrdjbetionSection,DRSS

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Inspection Summary: Inspection on April 7-10. 1987 (Report No. 50-412/87-25)

Areas Inspected: Rout;ae, announced inspection of the nonradiological chemistry program. Areas reviewed included measurement control and analytical procedures evaluatio Results: No violations were identifie PDR ADOCK 05000412 G PDR .

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DETAILS

, Individuals Contacted

• T. Noonan, Assistant Plant Manager

• V. Linnenbom, Director, Plant Chemistry

• N. Daugherty, Director, Systems Testing

• D. Hunkele, Director, QA Operations

• T. Zyra, Director, Site T and PP

• J. Kosmal, Manager, Radiological Control

• D. Girdwood, Director, Radiological Operations

• K. Winter, Senior H.P. Specialist

• R. Martin, Manager, Regulatory Affairs i *G. Wargo, Assistant Director, Quality Control

• J. Johns, Supervisor, QA Surveillance

• D. Evans, Chemistry, Trend and Analysis Coordinator

• S. Palian, Senior Chemist U-2

• L. Rabenau, Lead Compliance Engineer-

• J. Godleski, Senior Test Engineer '

• A. Lonnett, Health Physicist Specialist

• D. Claridge, Compliance Engineer J. Kalinyak, Senior Chemist U-2

• Denotes those present at the exit intervie The inspector 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 the standards were 1 analyzed by the licensee using normal methods and equipment. The anal-

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l ysis of standards is used to verify the licensee's capability to monitor !

chemical parameters in various plant systems with respect to Technical Specification requirements and other regulatory requirements. In addition, the analysis of standards is used to evaluate the licensee's i analytical procedures with respect to accuracy and precisio The results of the standard measurement comparisons indicated that four out of twenty-one measurements were.in disagreement under the criteria used far comparing results (see Attachment 1). The results of the compartsons are listed in Table 1.

3 The four disagreements were due to sampling error. Those disagreements were not viewed as significant.

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The laboratory personnel were in the process of revising analytical procedures and installing gas and water lines in the hot lab. The ton chromatograph and the graphite furnace could not be. evaluated with the

NRC standards because those instruments were not yet operational. When

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these instruments become functional, NRC standards will be submitted to the licensee for analysis; iron, copper, nickel and chromium for the graphite furnace and fluoride, chloride and sulfate for the ion chromatograp The hydrazine, silica, chloride and fluoride results reported in Table 1 are reruns. The NRC standards identified that the 1 cm cell used in the spectrophotometric analysis for hydrazine and silica is too small for good resolution and accuracy at the lower concentrations of the two analyte The licensee reran the. analysis using a 4 cm cell. The results were good and eliminated a systematic bias identified in the lower concentrations using the I cm cell. A 2 cm cell would be ideal for the interested parameters of hydrazine and silica. The licensee had crdered 2 cm cells

., which had not been received at the time of the inspectio The NRC standards identified that the specific ion electrodes for chloride and fluoride may have to be polished and the reference solutions changed '

more than once per week as stated in the' procedures. These procedures are being revised to eliminate a set time for maintaining the electrodes.

l The frequency of the maintenance depends on the reiterative use of the

electrodes.

The inspector had some concern that experienced chemists have transferred from the laboratory to other departments. If this continues, it will pose a problem when the plant starts up. The experienced chemists will be needed to interpret chemical analytical data. The licensee management should look into this situatio '

' Laboratory Measurement Control Verification of the licensee's measurement capabilities on actual plant water samples is done by splitting samples with the licensee and BNL. No split samples were taken because the fuel had not been loaded. When the plant starts up, samples will be taken and an evaluation of the data will be made by the NRC inspector.

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The inspector reviewed the licensee's measurement control program which was found to be good. The licensee generated and maintains control charts with parameters of 2 sigma and 3. sigma. The licensee expressed a desire in identifying the accuracy of the analysis to the made-up standard value. The inspector recommended another control chart that is used by other . laboratories in the region showing such data. The control chart is generated by plotting the difference of the analyzed value of the standard to the made-up value of the standard, using a parameter of 2 sigma. The licensee is already recording this difference but not plotting the dat This chart will trend the standard solution values.

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The licensee is using two independent standard stock solutions for cali-bration and measurement control. This allowed for an analytical cross check on the continuing quality of the standard solutions. The use of the two independent stock solutions was being practiced by the licensee but was not written into any analytical or measurement control procedure. The new analytical procedure revisions will include this usag . The calibration curves for the various measurement systems were generated

with a minimum of three data points. The curves were statistically fit j using a Least-Squared computer program print-ou . Exit Interview

, The inspector met with the licensee representatives (denoted in para-graph 1) at the conclusion of the inspection on April 10, 1987,'and summarized the scope and findings of the inspectio No written material was provided to the licensee, i

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TABLE 1 CAPABILITY TEST RESULTS BEAVER VALLEY POWER STATION. UNIT 2 Chemical Analytical NRC Li Ratio Pa ramete r Procedu re Value Value (Lic./NRC Compa ri son Results in parts per billion (ppb)

Sp. lon Chloride Electrode 48.21 .31 .1110.06 Ag reement 37.41 .71 .9010.04 D i sag reemen t 80.51 .01 .0 Ag reement Sp. lon Fluoride El ect rode 46.21 .11 .9810.02 Ag reement

, 43.51 .31 .0610.05 Ag reement

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83.51 .11 .0410.03 Ag reement Sodium AA 4.61 .11 .1110.13 Ag reement 9.21 .41 .1310.10 Ag reement 14.41 .01 .0410.06 Ag reement Ammonia Spectrophotometry 262.811 .31 .0 Ag reement 314.012 .01 .8810.08 Ag reement 938.018 .0110.0 Ag reement Hyd razine Spec t ropho tomet ry 66.91 .31 .9610.06 Ag reement 1141 .0 0.9210.01 Di sag reement 1561 .2 1.0310.02 Ag reement Silica Spect rophotomet ry 27.21 .31 .8910.10 Ag reement 54.51 .71 .9710.09 Ag reement 80.01 .71 .9310.03 Di sag reement Results in parts per million (ppm)

Boron Mannitol Titration 985110 100613 1.0210.01 Ag reement 2980150 3032141 1.0210.02 Ag reement 4870160 5041111 1.0410.01 D i sag reement

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ATTACHMENT 1 CRITERIA FOR COMPARING ANALYTICAL MEASUREMENTS

_ This attachment provides criteria for comparing results of capability tests.

i In these criteria the judgement limits are based on the uncertainty of the

, ratio of the licensee's value to the NRC value. The following steps are l performed:

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

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

, If the absolute value of one minus the ratio is less than or equal to twice the ratio uncertainty, the results are in agreemen (ll-ratio l s 2 uncertainty)

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Z = x, then Sz2 + Sx2 + sy2 y Z2 x2 y2

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

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