IR 05000245/1986004

Insp Repts 50-245/86-04 & 50-336/86-04 on 860317-21.No Violations Noted.Major Areas Inspected:Nonradiological Chemistry Program,Including Measurement Control & Analytical Procedure Evaluations

ML20202F800
Person / Time
Site:	Millstone
Issue date:	04/07/1986
From:	Pasciak W, Zibulsky H NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20202F789	List: IR 05000245/1986004 ML20202F784
References
50-245-86-04, 50-245-86-4, 50-336-86-04, 50-336-86-4, NUDOCS 8604140225
Download: ML20202F800 (5)

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U.S. NUCLEAR REGULATORY COMMISSION

REGION I

Report No /86-04 50-336/86-04 Docket No License Nos. DPR-21 DPR-65 . Priority --

Category C-Licensee: Northeast Nuclear Energy Company P.O. Box 270 Hartford, Connecticut 06101 Facility Name: Millstone Nuclear Power Plants, Units 1 and 2 Inspection At: Waterford, Connecticut Inspection Conducted: March 17-21, 1986 Inspector: b., we ~ N 7 3b bul y, Che st / h daje Approved by: f IJ, _ .i /m u t 9 '8 Ib W.~J. P ciak', Thief, EffTuents Radiation ilate Protec on Section, DRSS Inspection Summary: Inspection on March 17-21, 1986 (Combined Report No /86-04 and 50-336/86-04).

Areas Inspected: Routine, announced inspection of the nonradiological chemistry program. Areas reviewed included measurement control and analytical procedure evaluation Results: No violations were identifie f?D$ $

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DETAILS Individuals Contacted

• J.'Kelley, Station Services Superintendent

• J. Waters, Chemistry Supervisor

• G. D'Auria, U-2 Chemist J. Kangley, Radiological Services Supervisor J. Robertson, Senior Chemist T. Itteilag, U-2 Assistant Chemistry Supervisor D. Wilkens, U-1 Assistant Chemistry Supervisor

• Denotes those present at the exit intervie The inspector also interviewed other licensee employees including members of the chemistry staf . Action on Previous Licensee Findings (Closed) 50-245/84-06-01 and 50-336/84-08-01 IFI - Calibration standards i

were not documented or used over the range of interest. Control standards

.were not used or documented on control charts. The licensee has cali-brated the measurement systems over the range of interest and does not report any analyses below their lowest staadard or higher than their highest standard. The licensee has generated control charts with a 2 sigma alert parameter and a 3 sigma acceptance criteri (0 pen) 25-00-13 TI - Tne inspection covered part of this item. Of the two modules included in the TI, Module 79501 was completed.

L Measurement Control Evaluation I

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The licensee's measurement control program will be verified through

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analysis of actual plant water samples. Samples from the refueling water storage tank, steam generator and feedwater were taken and duplicate l samples were sent to Brookhaven National Laboratory (BNL) for independent verification. Boron analysis will be performed on the refueling water

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storage tank, ammonia and chloride analyses on the steam generator, and hydrazine analysis on the feedwater. On completion of the analyses by both laboratories, a statistical evaluation will be made (Inspector Follow-up Item 50-245/86-04-01 and 50-336/86-04-01).

The inspector reviewed the measurement control charts. The licensee

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generated the charts correctly and they reflected the performances of '

the measurement systems. For ammonia, the control chart showed a nega-tive systematic bias was present in the measurement. This was also shown

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with the NRC standard solution. The licensee polished the electrode and changed the standard reference electrode solution and the error was cor-rected. The inspector recommended that control charts be used for hydrazine, silica and some of the analytes measured with the ion chroma-l tograph. The licensee agreed to generate those charts.

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! The inspector observed that the' licensee used one standard stock solution for the calibration and control solutions. Maintenance of two standard stock solutions is required to provide an analytical cross check on.the continuing quality of the stock solution The licensee agreed to maintain

two standard stock solution , Analytical. Procedures Evaluation-During the inspection, standard chemical solutions were submitted by the inspector to the licensee for analysis. The. standard solutions were prepared by BNL for NRC Region 1, and were analyzed by the licensee using normal methods and equipment. The analysis of standards is used to verify the.various plant systems with respect to Technical Specification and other regulatory 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 measurements comparison indicated that six out of thirty-two comparisons were in disagreement under the criteria used for !

l comparing results (see Attachment 1). The fluoride, hydrazine, copper an nickel disagreements were due to sampling error. The two metals were on the conservative side and had a 7% bias. The ammonia disagreements were due to the deterioration of the standard solution in the reference elec-trode. This was identified by the licensee's measurement control stand-ard. The electrode was polished and new standard solution was introduce ,

The ammonia standards were rerun and the accuracy was acceptabl . Exit Interview The inspector met with the licensee representatives (denoted in para-graph 1) at the conclusion.of the inspection on March 21, 1986, 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.

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Capability Test Results l

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Millstone Nuclear Power Plants, Units 1 and 2 Chemical Ratio Parameter NRC Value Lic. Value (Lic./NRC) Comparison Results in parts per billion (ppb)

Chloride 10.3 .81 .95 0.07 Agreement (Ion Chromato- 69.713 72.4 .04 0.05 Agreement

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graph) 27.7 .7 .04 Agreement

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Fluoride 9.6 .31 .07 0.07 Agreement (Ion Chromato- 32.9 2 30.6 .93 0.06 Agreement graph)

Fluoride 38.4 .7 .0 Agreement (Specific 74.5 .7 .0 Agreement Ion Electrode)32.9 2 27.7 .84 0.07 Disagreement Ammonia 584 .5 0.94 0.03 Agreement 2401 .5 0.8910.05 Disagreement 356 1 .90 0.03 Disagreement Ammonia 584 .9- 1.02 0.03 Agreement (Rerun) 2401 .7 Agreement 35611 .5 0.96 0.04 Agreement Hydrazine 19.3 .0 0 1.0910.09 Agreement 52.41 .7 .0210.03 Agreement 100.0 2 108.0 .08 0.02 Disagreement Results in parts per million (ppm)

Boron 1014 15 1029 15 1.01 0.02 Agreement 3047 26 3002 31 0.98 0.01 Agreement 5040 130 4962 0 0.98 0.03 Agreement Iron 0.82 0.06 0.79 0.01 0.96 0.07 Agreement 1.53 0.06 1.64 0.01 1.07 0.04 Agreement 1.10 0.07 1.21 0.01 1.10 0.07 Agreement Copper 0.85 0.01 0.89 0.01 1.05 0.02 Agreement 1.66 0.03 1.73 0.01 1.04 0.02 Agreement 1.23 0.01 1.32 0.01 1.07 0.01 Disagreement Nickel 0.84 0.10 0.83 0.01 Agreement 1.65 0.08 1.68 0.01 1.02 0.05 Agreement 1.21 0.02 1.29 0.01 1.07 0.02 Disagreement -

Chromium 0.77 0.06 0.86 0.02 1.12 0.09 Agreement 1.72 0.03 1.67 0.02 0.9710.02 Agreement 1.20 0.09 1.27 0.02 1.06 0.08 Agreement

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AIIACllMENT Criteria for Comparing Analytical Measurements

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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 licensee's value to the NRC value. The following steps are performed:

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(1) the ratio of the licensee's value to the NRC value is computed Licensee Value (ratio = t'.9C Value );

(2) the uncertainty of the ratio is propagate 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-ratiol t 2 uncertainty)

Z , then Szz = Sx2 + Sy2 i.

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Z2 x2 y2 I

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

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