IR 05000354/1985059

Preoperational Insp Rept 50-354/85-59 on 851118-22.No Violations Noted.Major Areas Inspected:Chemical & Radiochemical Measurements Programs Using Lab Assistance Provided by DOE & BNL Including Lab QA & Procedures

ML20136E611
Person / Time
Site:	Hope Creek
Issue date:	12/27/1985
From:	Kottan J, Pasciak W, Rabatin K NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20136E605	List: IR 05000354/1985059 ML20136E601
References
50-354-85-59, NUDOCS 8601070074
Download: ML20136E611 (12)

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U.S. NUCLEAR REGULATORY COMMISSION

REGION I

Report N /85-59 Docket N License N CPPR-120 Category C Licensee: Public Service Electric and Gas Company 80 Park Plaza - 17C Newark, New Jersey 07101 Facility Name: . Hope Creek Generating Station Inspection At: Hancock's Bridge, New Jersey Inspection Conducted: November 18-22, 1985 Inspectors: M.G- 4+6 /2 /2.6/85" J. J. Kotta'n, Radiation Laboratory / date Specialist Y. ' kNsJ () 3%

K. L. Rabatin, Radiation Specialist date'

Approyed oy: . d'es' c4, ik %"I 1*C W. J{ljasciak, Chief, BWR Radiological $ ate, ProtTction Section Inspection Summary:

Inspection on November 18-22, 1985 (Report No. 50-354/85-59)

Areas Inspected: Routine, announced, pre-operational inspection of the licensee's chemical and radiochemical measurements programs using laboratory assistance provided by DOE: Brookhaven National Laboratory, and Idaho National Engineering Laboratory. Areas reviewed included: chemical capability test standards, radiological capability test standards, laboratory QA, and procedures. The inspection involved 72 inspector hours by two NRC regionally l based inspectors.

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Results: Of the areas inspected, no violations were identifie l V

8601070074'B51230 4 PDR ADOCK 050

. DETAILS Individuals Contacted E. Yockheim, Chemistry Engineer

• T. Vanoy, Senior Chemistry Supervisor G. Suey, Chemistry Supervisor, Laboratory M. Adzima, Senior Chemistry Technician J. Fortenberry, Senior Chemistry Technician P. Quick,-Assistant Chemistry Technician D. Golden, Assistant Chemistry Technician

' T. Rekart, Licensee Contractor

• R. Lovell, Radiation Protection / Chemistry Manager G. Morrill, Radiation Protection Supervisor C. Nolin, Senior Health Physics Technician R. Agvilera, Assistant Health Physics Technician R. Matthews, Assistant Health Physics Technician

• A. Giardino, Manager - Station QA

• A. Barnabet, Prinicpal QAE

• R. Griffith, Principal QAE

• Metcalf, Principal QAE

• R. Donges, Lead QAE

• denotes'those present at the exit meeting on November 22, 1985.

The inspector -also interviewed other licensee chemistry and health physics personne . Licensee Action on Previous Inspection Findings L (0 pen) Follow-up Item (354/85-44-06): Chemistry procedure All chemistry procedures have not yet been finalized and issued, including laboratory QA procedures. See Paragraph (0 pen) Follow-up Item (354/85-52-05): Training of health physics tech-nicians in operation of the gamma spectroscopy syste The technicians have yet to be trained. See Paragraph (0 pen) Follow-up Item (354/85-52-27): Health physics gamma spectroscopy system procedures. Procedures have yet to be issued in this are See Paragraph . Chemical Capability Test Standards During the inspection, standard chemical solutions were submitted to the licensee for analysis. The standard solutions were prepared by the Brookhaven National Laboratory (BNL), Safety and Environmental Protection Division, for the NRC Region I. The standards were analyzed by the licensee using routine methods and equipment. The analysis of standards is used to verify the licensee's capability to monitor chemical parameters

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in various plant systems with respect to proposed Technical Specification requirements, 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 measurements comparison indicated that 11 of the results were in disagreement, 12 of the results were in agreement, and 2 results could not be compared under the criteria for comparing result (See Attachment 1). The results of the comparisons are listed in Table All. standards were analyzed in triplicate. Metals (Cu, Cr, Ni, Fe) were submitted to the licensee at 5, 10, and 15 ppb concentrations. The analyses were perfoi. ad using an atomic absorption spectrophotometer (AA)

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with a graphite furnace. The first attempt at 10 ppb levels resulted in the Cu, Cr, and Ni values being in disagreement with the licensee unable to obtain an iron value. A second attempt at 10 ppb resulted in two of the four results (Ni and Fe) being in agreement. At.the 15 ppb concen-tration levels two values were in agreement, one was in disagreement, and the iron value resulted in negative numbers for the results. The in-spector then submitted a metals standard at the 100 ppb level in order to determine if problems encountered at the 10 and 15 ppb levels would also be encountered at a concentration approximately 10 times higher. Three-of.the four results at 100 ppb (Cu, Ni, Fe) were in agreement. The licensee calibrates the AA at one concentration and uses the oriain (obtained with blank water) as a second point for constructing a curve of concentration versus absorbance which is stored in the instrument. The inspector noted that the licensee is still gaining experience in the operation of the / A in that, for example, the licensee could not construct

.a multi point calioration curv All of the boron results were in disagreement under the criteria used for comparing results. Again this method, manitol titration, was recently implemented by the licensee, and the licensee is still gaining experience with i Two of the three fluoride results and all of the chloride results were in agreement. The fluorides were determined using a specific ion electrode, and the chloride was determined using an ion chromatograph (IC). Ini-tially the 30 and 70 ppb chloride concentrations caused the IC integrator to go offscale without the licensee being aware of this problem. The licensee recalibrated the IC using three points at higher concentrations (100, 50, and 10 ppb), as opposed to the initial calibration at one point-10 ppb, and obtained chloride values which were in agreement with the NRC value The inspector noted that the licensee had not intercompared standards with any other laboratory prior to analysis of the NRC standards. The licensee stated that the problems with the instrumentation and methods noted during this inspection would be reviewed and appropriate corrective action would be taken. The inspector had no further questions in this area. No violations were identifie .

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4 Radiological Capability Test Standards

.During the inspection, radioactivity standards were submitted to the licensee in order to evaluate the licensee's capability to measure

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radioactivity in effluents as required by the proposed Technical Specifications. The test standards were prepared by the NRC reference laboratory, DOE Radiological and Environmental Sciences Laboratory (RESL),

and duplicated the types of samples and nuclides that the licensee would encounter during operation. The standards were analyzed by the licensee's chemistry and health physics personnel using their routine methods and equipmen ~The results of the standards measurements comparison indicated that all of the measurements were in agreement under the criteria used for com-paring results. (See Attachment 2) The results are listed in Table Although all results were in agreement, the initial comparison of charcoal cartridge results indicated that the licensee had calibrated the charcoal cartridge with the " cold" or outlet side facing the detector rather than the inlet or " hot" side facing the detecto The licensue recalibrated the detectors during this inspection. Also, standards were submitted requiring wet chemistry: tritium, Sr-89, Sr-90, and Fe-55. These results will be compared in a subsequent report after the analyses are complete The inspector had no further questions in this are No violations were identifie . Laboratory Quality Assurance (QA)

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The inspector reviewed the licensee's program for the qt.ality assurance of both chemical and radiological analytical measurements. Procedure CH-AP.22-017(Q), " Chemistry Quality Control Program" details the licensee's program. To date, however, the approved version of this proce-dure contains no provisions for radiological instrumentation and measure-ments. In addition, the procedure as issued is not being implemented with regard to chemical measurements. The procedure requires standard curves to consist of three points not including zero, but the AA and IC are calibrated using zero and one data point. The procedure requires that the data for calibration curves be fit to a curve, yet the fluoride specific ion electrode calibration curve was hand drawn. Also no control charts were maintained for the laboratory instrumentation or procedures even though data was being accumulated which could be plotted on control charts. The inspector stated that implementation of a laboratory QA pro-gram both in the chemical and radiological measurements areas would be an inspector follow-up item (354/85-59-01). The inspector further noted that had the QA program been implemented, some of the problems encountered during the analysis of NRC standards would have been encountered sooner and solved. This would have resulted in a greater percentage of the chemical measurements being in agreement. No violations were identifie .

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5 Procedures The inspector reviewed the appropriate procedures for operation and calibration of the instrumentation used for analysis of the NRC stan-dards. The inspector noted that the procedures for the AA and IC were in the process of being tested or validated and significant changes would have to be made to those procedures: for example, so that three point versus one point calibrations could be performed, and that instruments, such as integrators, going offscale could be identified and corrective action taken. The inspector stated that revision and issue of the revised AA and IC procedures would be an inspector follow-up item (354/85-59-02).

Also, the inspector noted that the licensee's health physics technicians did not have a procedure for use in operating the health physics gamma spectroscopy system. The health physics technicians could not indepen-dently analyze the radiological standards submitted to them by the NR Furthermore, a QA program for the health physics gamma spectroscopy system has not been implemented. The licensee stated that the chemistry counting and QA procedures would be used for operation and QA of the health physics gamma spectroscopy system. Both the health physics gamma spectroscopy system procedures and training of health physics technicians in operating the gamma spectroscopy system were previously identified as inspector follow-up items (354/85-52-27 and 354/85-52-05 respectively). The inspec-tor stated that these items will continue to remain ope The inspector noted that the licensee used a laboratory computer for fitting a curve to the IC recalibration data. After fitting the curve, the licensee attempted to input a peak height value and have the computer calculate the resultant concentration. The result, however, was in error. The inspector inquired as to the software written for the labo-ratory computer and the procedures used for software documentation and verification. The licensee stated that at the present time nothing had been implemented for documentation and verification of laboratory com-puter software, but that action would be taken in this area. The inspec-tor stated that this would be an inspector follow-up item (354/85-59-03),

and would be reviewed during a subsequent inspection. The inspector had no further questions in this area. No violations were identifie . Exit Interview The inspector met with the licensee representatives denoted in Paragraph 1 at the conclusion of the inspection on November 22, 1985. The inspector summarized the purpose, scope, and findings of the inspection. The licensee stated that analyses requiring wet chemistry listed in Paragraph 4 would be completed in a timely manner and the results provided to the NRC.

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

(1) the ratio of the licensee's value to the NRC value is computed Licensee Value (ratio = NRC-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 uncertainly, the results are in agreement. '(l1-ratio l s 2 uncertainty)

Z = X, then Sz2 = Sx2 + sy2 V 27~ X2 y2 (From: Bevington, P.R., Data Reduction and Error Analysis for the Physical Sciences, McGraw-Hill, New York, 1969)

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, ATTACHMENT 2

Criteria for Comparing Analytical Measurements

'This attachment provides criteria for comparing results of capability tests and verification measurements. The criteria are based on an empirical relation-ship which combines prior experience and the accuracy needs of this progra In these criteria, the judgement limits are variable in relation to the com-

-parison of the NRC Reference Laboratory's value to its associated uncertaint As that ratio, referred to in this program as " Resolution", increases the acceptability of a licensee's measurement should be more selective. Conversely, poorer agreement must be considered acceptable as the resolution decrease \

Resolution = NRC REFERENCE VALUE RATIO = LICENSEE VALUE REFERENCE VALUE UNCERTAINTY NRC REFERENCE VALUE i

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Resolution Agreement

<3 0.4 - .5 - '

0.6 - 1,66-16 - 50 O.75 - 1.33 51 - 200 0.80 - 1.25

>200 0.85 - 1.18

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TABLE 1 * CHEMICAL CAPABILITY TEST RESULTS ,

f CHEMICAL PARAMETER NRC VALUE LICENSFE VALUE RATIO fLIC-NRC1 COMPARIEAR RESULTS IN PARTS PER BILLION foob1 Cappe r 10.4 i .89 i 0.09 0.95: 1 0.02 - Di sag reement '

'9.56 1 0.12 '

O.92 1 0.02 D i sa g reement 15.36 1 0.16 16.52 1 0.10 1.976 i O.013 Di sag reement 104 1 2 104.1 1 .00 1 0.02 Ag reement Chromium 10.8 1 .79 1 0.12 0.91 1 0.02 Di sag reement

'9.67 i O.10 0.90 1 0.02 D i sag reement 15.0 1 .1 1 .01 1 0.08 Ag reement 108 2 2 ' 98.9 1 .92 1 0.02 D i sag reement Cickel 10.3 i .83 1 0.10 1.15 1 0.06 Di sag reement

• 10.4 1 .01 1 0.06 Ag reement 15.2 1 .1 1 .93 1 0.05 Ag reement .

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103 1 5 100 1 2 0.97 1 0.05 Ag reement Iron 9.6 1 No-Result No Comparison '

1. 11 1 2 , 1.2 1 Ag reement

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13.7 1 No Results --- No Comparison 9614 102.6 i .07 1 0.05 Ag reement Chloride 10.3 1 .C i .87 1 0.10 Ag reement 28 i 3 27.1 1 .97 1 0.11 Ag reement 70 1 3 . 7014 1.00 1 0.07 Ag reement

• Second attempt at 10 ppb leve t u

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CHEMICAL PARAMETER NRC VAtiJE~ LICENSEE VALUE -

RATIO fLIC-NRC1 1 ..tc COMP /.R I SON

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, RESULTS IN PARTS PER MILLION foom).  ;

Boron 1014 1 15 961 i 6 -0.95 1 0.02 Di sag reement -

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3050 i 30 '2832 1 13 0.928.1 0.010 Di sag reement 5040 i 130 4690 1 40 0.93 1 0.03 Di sag reement Fluoride 9.6 1 .8 1 .13 1 0.06 Di sag reement .

3312 29.5 1 . 0.89 1.0.06 Ag reement

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75 1 4 71.3 i .95 2 0.05 Ag reement

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A TABLE 2 RADIOLOGICAL CAPABILITY TEST RESULTS SAMPLE E ikeV) NRC VALUE LICENSEE VALUE COMPARISON RESULTS IN CAMMAS PER SECOND Simulated off-gas vial 186 160 1 9 209 i 5% Ag reement Chemistry detector 1 242 344 1 16 402 1 3.3% Ag reement 989 1 1.9%

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Shelf 3 295 851 2 42 Ag reement 351 1639 i 82 1749 i 1.3% Ag reement .

609 2062 1 101 2128 1 1.4% Ag reement 1120 682 i 34 743 i 3.9% Ag reement 1238 . 271 1 14 292 1 6.4%- Agreement 1765 703 1 35 711 1 4.3% Agreement Simulated off-gas vial 186 160 i 9 203 i 5.1% - Ag reement Chemistry detector 1 242 344 i 16 408 1 3.2% Ag reement Shelf 2 295 851 1 42 1034 1 1.8% Ag reement 351 1639 i 82 1877 1 1.3% Ag reement 609 2062 1 103 2215 i 1.4% Ag reement 1120 682 1 34 808 1 3.4% Ag reement 1238 271 1 14 319 i 8.2% Ag reement 1765 703 1 35 760 i 4.1% Ag reement .

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Tp TABLE 2 A '1 RADIOLOGICAL" CAPABILITY TEST RESULTS SAMPg ISOTOPE NRC VALUE jdgENSEE VALUE i COMPARISON '

- RESULTS IN TOTAL MICROCURIES

' ij Sp i ked Cha rc'ca l Cs-137 (9 74 1 0.05]E-3 (9.2 1 0.4)E-3 Ag reeme Ca rt ridge Co-60 (9.84 1 0.05)E-3 (1.06 1 0.05)E-3 Ag reement

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Chemistry detector 2 Shelf 3 Spiked Charcoal Cs-137 (9.74 1 0.05)E-3 ( 9. 7 i 0. 2- ) E-3 Ag reement Co-60- (9.85 1 0.05)E-3 (1.05 1 0.03)E-2 Ag reement

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Spiked Cha rcoa l Cs-137 (9.74 1 0.05)E-3 (9.36 1 0.10)E-3 '

Ag reement Cartridge Co-60 (9.04 i 0.05)E-3

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(1.008 1 0.014)E-2 ' Ag reement Chemistry detector 2 *

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Spiked Cha rcoa l Cs-137 (9.74 1 0,05)E-3 (9.4 1 0.4)E-3 i Ag reement '

C2rtridge , Co-60 (9.84 1 0.05)E-3 (1.07 1 0.06)E-2 ' Ag reemen t T Chemistry detector 3 -

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Spiked Filter Ce-144 (3.46 1 0.02)E-2 (4.02 1 0.13)E32 Ag reement Chemistry dete. .or 2 Cs-137 - (1.50 1 0.02)E-2 (1.686 1 0.015)E-2 Ag reement Shelf 1 Mn-54 (1.47 1 0.02)E-2 ., (1.80 1 0.04)E-2 Ag reement Co-60 (2.68 1 0.02)E-2 (3.14 1 0.03)E-2 Ag reement Spiked Filter Ce-144 (3.46 1 0.02)E-2, (3.9 1 0.3)E-2 Ag reement chemistry detector 3 Cs-137 (1.50 1 0.02)E-2 (1.33 i O.04)E-2 Ag reement Shelf 2 Mn-54 (1.47 i 0.02)E-2 (1.34 i 0.10]E-2 Ag reement Co-60 (2.68 i 0.02)E-2 (2.46 1 0.06)E-2 Ag reement Spiked Filter Ce-144 (3.46 1 0.02)E-2 (3.8 1 0.6)E-2 Ag reement Chemistry detector 3 Cs-137 (1.50 1 0.02)E-2 (1.54 1 0.07)E-2 Ag reement Shelf 3 Mn-54 (1.47 1 0.02)E-2 (1.8 1 0.2)E-2 Ag reement Co-60 (2.68 1 0.02)E-2 (2.77 1 0.12)E-2 Ag reement

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RADIOLOCICAL CAPABILITY TEST RESULTS  !

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SAMPLE ISOTOPE NRC VALUE LICENSEE VALUE COMPARISON ,

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RESULTS IN TOTAL MICROCURIES Sp i ked Cha rcoa l Cs-137 (9.74 1 0.05)E-3 (9.3 1 0.2)E-3 ' Ag reement / E> '

Ca rt ridge Co-60 (9.84 1 0.05)E-3 (9.0 1 0.3)E-3 Ag reement ' -

Health Physics d3tector 4

. Shelf 2 Spiked Cha rcoa l Cs-137 (9.74 1 0.05)E-3 (1.066 1 0.013)E-2 Ag reement Ca rt ridge Co-60 (9.84 1 0.05)E-3 (1.14 i 0.02)E-2 Ag reement H:alth Physics dstector 4 Shelf 1 Spiked Cha rcoa l Cs-137 (9.74 1 0.05)E-3 (1.01 1 0.05)E-2 Ag reement Cartridge Co-60 -(9.84 1 0.05)E-3 (9.4 1 0.7)E-3 Ag reement Health Physics detector 4 -

Sheir 3 Spiked Filter Ce-144 (3.46 1 0.02)E-2 (3.2 1 0.6)E-2 Ag reemen t Hsalth Physics Cs-137 (1.50 1 0.02)E-2 (1.31 1 0.06)E-2 Ag reement dstector 5 Mn-54 (1.47 i 0.02)E-2 (1.5 1 0.2)E-2 Ag reement Shelf 3 Co-60 (2.68 1 0.02)E-2 (2.65 1 0.12)E-2 Ag reement Spiked Filter Ce-144 (3.46 1 0.02)E-2 (3.2 1 0.3)E-2 Ag reement Health Physics Cs-137 (1.50 1 0.02)E-2 (1.34 1 0.03)E-2 Agreement datector 5 Mn-54 (1.47 i 0.02)E-2 (1.46 1 0.12)E-2 Ag reement Shelf 2 Co-60 (2.68 1 0.02)E-2 (2.50 1 0.06)E-2 Ag reement RESULTS IN MICROCURIES PER MILLILITER Spiked water sample Co-60 (1.58 i 0.04)E-5 (1.78 1 0.06)E-5 Ag reement Chemistry detector 3 Cs-137 (1.94 1 0.04)E-5 (1.93 1 0.06)E-5 Ag reement Spiked water sample Co-60 (1.58 i 0.04)E-5 (1.85 1 0.04)E-5 Ag reement Chemistry detector 2 Cs-137 (1.94 1 0.04)E-5 (2.17 1 0.04)E-5 Ag reement

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