IR 05000267/1988009

Insp Rept 50-267/88-09 on 880411-15.No Violations or Deviations Noted.Major Areas Inspected:Licensee Chemistry/ Radiochemistry Program & Water Chemistry & Radiochemistry Confirmatory Measurements

ML20154L202
Person / Time
Site:	Fort Saint Vrain
Issue date:	05/13/1988
From:	Baer R, Nicholas J, Wise R NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION IV)
To:
Shared Package
ML20154L193	List: IR 05000267/1988009 ML20154L190 ML20154L199
References
50-267-88-09, 50-267-88-9, NUDOCS 8805310203
Download: ML20154L202 (22)

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. APPENDIX B U.S. NUCLEAR REGULATORY COMMISSION

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REGION IV

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NRC Inspection Report: 50-267/88-09 Operating License: DPR-34 Docket: .50-267 Licensee:-~Public Service Company of Colorado (PSC)

2420 W. 26th Avenue, Suite 15c-Denver, Colorado 80211

Facility Name: Fort'St. Vrain Nuclear Generating Station (FSV)

Inspection At: FSV Site, Weld County, Platteville, Colorado Inspection Conducted: April-11-15, 1988

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Inspectors: JM J 6. Nicholas, Senior Radiation Specialist

.r/ahr Date l' acilities Radiological Protection Section mh.abr

R./ Wise, Radiation Specialist, Facilities Date-

/ Radi ol ogical - Protecti'on. Secti on

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Approved: #d /

R.'E. Baer, Acting Chief, Facilities M3/88 Date Radiological-Protection Section Inspection Summary

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Inspection Conducted April 11-15, 1988 (Report 50-267/88-09)

i Areas Inspected: Routine, unannounced inspection of the licensee's

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chemistry / radiochemistry program and water chemistry and radiochemistry confirmatory measurements.

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Results: Within the areas inspected, one violation was identified (failure to

use quality control charts to evaluate water chemistry laboratory instrument performance, paragraph 7). No deviations were identified. One previously identified open item was close PDR ADOCK 05000267 Q DCD L

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f 2-DETAILS Persons' Contacted PSC

• O. Williams', Jr., Vice President, Nuclear Operations H.-E. Adamski, Senior Chemist W. L. Alderman, Radiochemist F. J. Borst, Manager, Nuclear Training J. C. Brungardt, Senior Chemist S. L. Chambers, Radiochemist L. Olug, Chemist

• M. J. Ferris,~ Manager, Operations Quality Assurance D. L. Fetteroff, Senior Chemist V.' H. Frahm, Senior Radiochemist

• M. H. Holmes, Manager,-Nuclear Licensing

• R. O. Hooper, Nuclear. Training Administration Supervisor L. C. Hutchins, Nuclear Training Specialist

• V. A. Lucero, Chemistry-Superv,isor G. S. Madison, Radiochemist-

• D. Miller, Radiochemistry. Supervisor

• F. J. Novachek,- Manager, Technical / Administrative Services

• T. E. Schleiger, Health Physi.cs Supervisor

• L.~ D.~ Scott, Manager, Quality-Assurance Services,

.*L. R. Sutton, Quality. Assurance Auditing Supervisor

• P. F. Tomlinson, Manager, Quality. Assurance

• D. O. Warembourg, Manager, Nuclear Engineering J. E. Worley, Chemist-NRC R. E. Farrell, Senior Resident Inspector, FSV

• P. W. Michaud, Resident Inspector, FSV

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• Denotes those individuals present during the exit interview on April 15, 198 . Followup on Previously Identified Inspection Findings (92701)

-(Closed) Open Item 267/8421-03: Quality Assurance (QA) Program - This item was identified in NRC Inspection Report 50-267/84-21 and involved the lack of a comprehensive QA audit program for water chemistry and radiochemistry activities, which included the use of a technical specialist with expertise in water chemistry and radiochemistry as an audit team membe The licensee had performed a comprehensive audit of the water chemistry and radiochemistry programs in June 1987. The audit

. team. included a technical specialist knowledgeable in water chemistry and radiochemistry activities at nuclear power facilitie '

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l 3. Open Items Ident'ifie'd During This Inspection An'open item is a matter.that requires further review and evaluation by the NRC inspectors. Open. items are used to document, track, and ensure-

adequate-followup on matters of concern to the NRC inspectors. The u following .open item was identified:

Open Item Title Paragraph 267/8809-02 Water Chemistry Confirmatory-Measurements 7 4. NRC Inspectors Observation The following'are observations the NRC inspectors discussed with the licensee during the exit interview on April 15, 1988. These observations are not violations,_ deviations, unresolved items, or open items. These observations were identified for licensee consideration for program improvement, but the observations have no specific regulatory requirements. The licensee stated that these ' observations would be evaluate Water Chemistry and Radiochemistry Personnel Training - The licensee had-not completed the-1987 continuing training program for water chemistry and radiochemistry personnel as proposed.in interoffice memos (see paragraph 6). Water Chemistry Calibration Standards Verification - The licensee was

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not using two independent standard stock solutions for instrument calibration and measurement quality control (see paragraph 7).

l Water Chemistry Instrument Calibration - The licensee was not I

generating multiple point calibration curves for the atomic l absorption system, ultraviolet / visible (UV/VIS) spectrometer, and ion chromatograph (see paragraph 7).

5. Organization and Management Controls (83722/83522)

The NRC inspectors reviewed the licensee's organization, staffing, identification and correction of program weaknesses, audits and appraisals, communication to employees, and documentation and implementation of the water chemistry section (WCS) and radiochemistry section (RCS) programs to determine adherence to commitments in Chapter 12 of the Updated Safety Analysis Report (USAR) and the requirements in Section 7.1 of the Technical Specifications (TS).

The NRC inspectors verified that the organizational structure of the WCS and RCS were as defined in the USAR and T The NRC inspectors reviewed the FSV management control procedures and position descriptions for the assignment of responsibilities for the management and implementation of i

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the FSV water chemistry and radiochemistry program The NRC inspectors verified that the administrative control responsibilities specified by the

.FSV procedures were being implemente The NRC inspectors reviewed the staffing of the WCS and RCS and noted that, since the previous NRC water chemistry / radiochemistry inspection in June 1986, the WCS had experienced no personnel changes and the RCS had lost the radiochemistry supervisor and three radiochemistry technician The radiochemistry supervisor's position had been filled with the former senior radiochemist and the three vacant radiochemistry technician positions had been filled with qualified personnel. The RCS staff turnover rate during the past 22 months had been approximately 60 percen The WCS and RCS staffing were determined to be in accordance with licensee commitment No violations or deviations were identifie . Training and Qualifications (83723/83523)

The NRC inspectors reviewed the licensee's training and qualification program for WCS and RCS personnel including education and experience, adequacy and quality of training, employee knowledge, qualification requirements, new employees, Institute of Nuclear Power Operations (INP0)

. accreditation, and audits and appraisals to determine' adherence to commitments in Chapter 12'of the USAR and the requirements in Section of the T The NRC inspectors reviewed the education and experience backgrounds of the present water chemistry and radiochemistry staffs and determined that all personnel met the qualifications specified in the USAR, TS, and ANSI N18.1-197 The NRC inspectors determined that the licensee had an adequate staff to meet staffing requirement The NRC inspectors reviewed the licensee's training program for training-and qualification of FSV WCS and RCS personnel including a review of the chemistry training instructor's qualifications, training facilities, water chemistry and radiochemistry technician training procedures, water chemistry and radiochemistry training schedules for 1987 and 1988, continuing training schedules and topics for 1987 and 1988, selected course lesson plans and job performance measures, and WCS and RCS personnel training records and qualification cards. It was determined that the chemistry and radiochemistry training programs were in the final stages of INP0 accreditatio The NRC inspectors reviewed the WCS and RCS individual staff training records and determined that the two recently hired radiochemistry technicians were in the process of completing the required qualification training. It was observed that the proposed 1987 continuing training programs for water chemistry and radiochemistry as outlined in interoffice memos PPC-87-1608 and PPC-87-1609 dated May 5, 1987, had not been completed as scheduled. It was determined that the WCS and RCS staffs had I

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difficulty.in allocating scheduled time for training activitie Therefore, training had been conducted on a convenience basis. This observation was discussed with the licensee during the exit interview and more effort may need to be devoted to ensure that WCS and RCS personnel attend scheduled training. The licensee indicated that they would evaluate the NRC inspectors' concern and take corrective action as necessar No violations or deviations were identifie . Light Water Reactor Chemistry Control and Chemical Analysis (79701/79501)

The NRC inspectors reviewed the licensee's water chemistry program including establishment and; implementation of.a water chemistry control program, sampling, facilities and equipment, establishment and implementation of a quality control program for chemical measurements, and water chemistry confirmatory measurements to determine adherence to commitments in Chapter 10'of the USAR and'the requirements in Sections and 7.4 of the T The NRC inspectors' review of the water chemistry program found that the licensee had revised and approved administrative procedures, surveillance procedures, chemical control procedures, instrument calibration and quality control procedures, and analytical procedures. A-review of selected procedures revised and written since the previous NRC inspection in June 1986 indicated that the WCS and RCS had established sufficient programmatic procedures to meet the requirements of the USAR and T The NRC inspectors inspected the facilities and equipment used by the WCS and RCS staff. The following facilities were inspected: water chemistry laboratory, radiochemistry laboratory, and radiochemistry counting roo The laboratories were equipped with the necessary chemicals, reagents, labware, and analytical instrumentation to perform the required analytical procedure The water chemistry and radiochemistry facilities and analytical instrumentation appeared to be adequate to perform routine chemistry and radiochemistry requirements to support plant operation.

i The NRC inspectors reviewed selected water chemistry procedures for operation, calibration, and quality control of the laboratory instrumentation used for analysis of the NRC water chemistry standards to l determine the adequacy and effectiveness of the licensee's chemistry l

measurement quality control program. It was observed that the licensee was not using two independent standards for calibration and measurement of quality control of chemistry analytical instrumentation. The licensee could not verify the integrity of the standard solutions. The licensee had not initiated a program of two independent standard stock solutions prepared from independent sources, i.e., different vendors or different stock lots. This program would include one standard stock solution dedicated for instrument calibration and a second independent standard-stock solution dedicated for quality contro The use of independent standards affords a crosscheck on the stability of the standards and

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. . i identifies a degenerated standard solution. The licensee was using only single point calibrations for instruments such as atomic absorption, spectrometry, and ion chromatography., The single point calibrations implied.that the instrument results were linear with the standard concentration for all concentrations measured. The licensee was not able to identify slope changes in the-calib' ration curves which would cause erroneous results. .The licensee had not generated instrument calibration curves using a minimum of three data po_ints, excluding zero, bracketing the concentration range for the expected analytical results. The calibration curves should be statistically fit to the data point These observations were discussed with the licensee at the exit interview. The licensee agreed to evaluate the observations and consider actions for program improvement .

The licensee had implemented an instrument quality control program for water chemistry laboratory instruments in response to an INP0 finding in 1986. The licensee's Water Chemistry Procedure (WCP) -356, "Analytical Control Charts," Issue 1, dated October 21, 1987, controls the development and implementation of water chemistry laboratory instrument quality control charts for the Dionex 2120i Ion Chromatograph, Perkin-Elmer

! Model 306 Atomic Absorption System, Perkin-Elmer Model 460 with HGA 500 Graphite Furnace, and.UV/VIS Spectrometers. The above referenced procedure establishes criteria to identify and evaluate data biases of out-of-control i situations identified in daily or periodic quality control analyses of l chemical parameter Paragraph 5.8.2 of WCP-356 establishes the criteria

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that when evaluating instrument contrc,1 chart data either of the following three conditions would indicate an out-of-control situation: Any point beyond the control limits (three standard deviations), Seven successive points on the same side of the value x (arithmetic mean),or .Seven successive points falling between two standard deviations and three standard deviations.

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instrument, standards, or procedural malfunctions is to be started, i Paragraphs 5.8.3, 5.8.4, and 5.8.5 define corrective actions to be taken l-when out-of-control situations are identified. These include the following: , Analysis must be stopped'until the nroblem has been identified and resolved after which the frequency should be increased for the next few quality control checks and the problem anc solutions must be documented;

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-.' ... If after corrective action.has been taken and the instrument is stil'1 out-of-control but determined to be functioning _ correctly, new-control charts will be made utilizing new standards, duplicates, and-spikes; and All analyses since the last in-control point must be evaluated and appropriate actions, such as a memo to plant management, will be initiate The NRC inspectors reviewed. instrument quality control charts for the water chemistry laboratory instruments for the time period November 11, 1987, through April 13, 1988. Contrary to the above procedural criteria for identifying and evaluating data biases or out-of-control situations in instrument quality control data, the NRC inspectors determined that out-of-control situations existed for chloride by ion chromatography, silica by spectroscopy, and iron and copper by graphite furnace atomic absorption without documented evaluation or corrective actions taken, such as analyses stopped, new control charts made, or memos to plant management written for notification of laboratory instrument problem Examples of out-of-control situations which existed and were not evaluated and corrective actions taken included the following: The chloride 20 ppb standard had seven successive points above the arithmetic mean value between January 21 and 27, 1988, and eight successive points above the. arithmetic mean value between March 24 and 31, 198 The chloride 5 ppb standard had 17 successive points below the arithmetic mean value with 1 of those. points below three standara deviations- between January 16 and February 7,1988, and 10 successive points below the arithmetic mean value with 2 of those points below three standard deviations between April 5, and 13, 198 The silica 100 ppb standard had 8 successive points below the arithmetic mean value between' January 19 and 26, 1988, and 11 successive points below the arithmetic mean value between March 15 and 25, 1988. On February 1, 1988, the 100 ppb standard result was below three standard deviation The silica 5 ppb standard had eight successive points above the arithmetic mean value between March 16 and 23, 198 The iron 50 ppb standard had eight successive points above the arithmetic mean value between February 10 and 18, 198 The iron 10 pbb standard had seven successive points below the arithmetic mean value between February 4 and 10, 198 '

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8 The copper 25 ppb standard had seven successive points below the arithmetic mean value with one of those points below three standard deviations between January 31 and February 5,1988, and seven successive points below the arithmetic mean value between April 4 and 12, 1988. On April 13,1988, the 25 pbb standard result was above three standard deviation The copper 5 ppb standard had seven successive points below the arithmetic mean value between February 5 and 11, 1988, and ten successive points below the arithmetic mean value between April 2 and 12, 1988. On April 13, 1988, the 5 ppb standard result was above-three standard deviation The failure to properly identify and evaluate water chemistry instrument quality control data out-of-control situations, take appropriate corrective. actions, and document these conditions and solutions during the period November 11, 1987, through April 13, 1988, is an apparent violation of TS AC 7.4 and licensee's implementing quality control chart procedur (267/8809-01)

During the inspection, standard chemical solutions were provided to the licensee for confirmatory measurements analyses. The standards were analyzed by the licensee using routine methods and equipment. The results of the measurements comparisons are summarized in Attachments 1, 2, and 3 to this repor The licensee's original analytical results indicated that 17 of the 36 results were in agreement giving a 47 percent agreement overall. After several attempts to resolve analytical problems including standard preparation and instrument calibration and quality control, the licensee's final analysis results showed 64 percent agreement with the Brookhaven National Laboratory (BNL) results based on 23 agreement results out of 36 total results compared. The NRC inspectors were concerned with the high percentage of disagreements in the confirmatory measurements analyses of the water chemistry standards. This is considered to indicate significant analytical problems in the water chemistry laboratory. This item is considered open (267/8809-02) pending the licensee being able to achieve a satisfactory performance of 90 percent or higher agreement on the water chemistry confirmatory measurements standard No deviations were identified.

i 8. Quality Assurance and Confirmatory Measurements for In-Plant Radiochemical Analysis (84725/84525)

The NRC inspectors reviewed the licensee's radiochemical analysis program including procedures, facilities and equipment, implementation of a qu'ality control program, postaccident sampling system (PASS), and radioanalytical confirmatory measurements to determine adherence to commitments in Chapter 4 of the USAR and the requirements in Sections and 7.4 of the T _ _ _ - _ _ _ _ - -

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The NRC inspectors reviewed selected procedures revised and approved since the previous NRC inspection in June 1986 and determined that the licensee 1 had established and implemented sufficient programmatic procedures to meet the USAR and TS requirement The NRC inspectors reviewed the licensee's records for the period January 1987 through March 1988 involving instrument calibration and quality control. It was verified that the radiochemistry counting room instruments had been calibrated according to procedures and an instrument quality control program had been implemente The NRC inspectors verified that the PASS equipment and associated procedures satisfied the requirements of NURN-0737, Item II.B.3, for representative rampling and analysis of reacu r coolant and containment atmosphere following a reactor incident. The NRC inspectors verified that the normal sampling points for reactor coolant and containment atmosphere are to be used and present analytical laboratory instrumentation would be used to determine required chemical and radiochemical isotopic concentrations of the reactor coolant and containment atmosphere. The RCS staff had received annual training and were qualified in operating the PASS equipment and calculating mitigating core damage from chemical and radiochemical analytical results. The licensee's procedures and analytical sensitivities of chemistry and radiochemistry parameters were consistent with PASS requirement During the inspection, radiological confirmatory measurements were performed on standards and split samples by the licensee and the NRC inspectors in the Region IV mobile laboratory. The standards and samples were analyzed by the licensee using routine methods and equipment. The

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results of the measurements comparisons are summarized in Attachments 1, 4, and No violations or deviations were identifie . Quality Assurance Program (79701/79501; 84725/84525)

The NRC inspectors reviewed the licensee's QA monitoring and audit programs regarding water chemistry and radiochemistry activities to determine adherence with commitments in Chapter 12 of the USAR and requirements in Section 7.1 of the T The NRC inspectors reviewed the audit schedules for 1987 and 1988, QA audit plans and checklists, and the quai'fications of monitoring inspectors and auditors. Monitoring reports and audit reports of QA activities performed during 1987 in the areas of water chemistry and radiochemistry were reviewed for scope to ensure thoroughness of program evaluation. The NRC inspectors noted that the QA audit was designed to determine compliance with the USAR, TS, and FSV procedures. The NRC inspectors verified that the audit findings had beer reviewed by licensee's management and that responses and correct:ye actions to

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findings had been completed and documented in accordance with QA

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a procedures. . It was noted that the audit team included a technical

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specialist trained and. knowledgeable _ in water chemistry and radiochemistry activities 4t. nuclear power facilitie No violations or deviations were identifie . . Contractor Activities (84725/84525)

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The NRC inspectors determined that the licensee was not using contractor personnel or laboratories to perform chemical or radiochemical analyse . . Exit Interview The NRC inspectors met with the NRC resident inspector and the licensee representatives identified in paragraph 1 of this report at the conclusion of the inspection on April 15, 1988. The NRC inspectors summarized the scope of the inspection and discussed the inspection findings, inspectors observations, open items, item of noncompliance, and the results of the

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water _ chemistry and radiocl emistry confirmatory measurements as presented in this repor .

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AJTACHHFNT 1 A_n_alyM cA 1 Mea sur_ejnent e Waler _Chemistty_Confirmatorv Measurements During the inspection, standard chemical solutions were provided to the licensee for analysi The standard solutions were prepared by the Brookhaven National Laborator) (BNL), Safety and Environmental Protection Division, for the NR The standards were analyzed by the licensee using routine methods and equipmen The analysis of I chemical standards is used to verify the licensee's capability to monitor chemical parameters in various plant. systems with respect to l

Technical Specification (TS) requirements and other industry

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standard In addition, the analyses of standards are used to l

evaluate the licensee's analytical procedures with respect to accuracy and precisio The results of the measurements comparison are listed.in Attachment 2.

l Attachment 3 contains the criteria used to compare result All i standards were analyzed in triplicate. The licensee's origina analytical results indicated that 17 of the 36 results-were in agreemen The chloride midrange concentration result analyzed by ion chromatography was found in disagreement and biased high. The licensee's chloride quality control standards did not indicate a data bia The chloride results analyzed by selective ion electrode were statistically in agreement according to the NRC acceptance criteria; however, the precision and accuracy of the results were totally unacceptabl The selective ion electrode method of analysis for chloride should not be used routinely without proper electrode conditioning and satisfactory calibratio The analysis result for the low concentration of sulfate was in disagreement due to the instrument calibration based on a 20.0 ppb standard and the instrument calibration not linear at low concentration The sulfate S.O ppb quality control standard showed a data bias of approximately 60 percent high which was also reflected in the sample analysis. The copper results analyzed by graphite furnace atomic absorption'were all biased low over the entire concentration rang The copper low and midrange concentration results were in disagreement. This was possibly due to the licensee using only a one point calibration at a concentration of 50.0 ppb which had not been independently verified to be 50.0 ppb and the instrument calibration not linear at low concentrations. The licensee's results for all concentrations of iron analyzed by flame atomic absorption were in disagreement and approximately 23 percent lo This indicated an instrument systematic bias or calibration proble The licensee prepared new dilutions of the BNL standards and reran the iron analyse The rerun results for iron showed no changes from the original result The licensee's original low and high concentration results for copper analyzed by flame atomic absorption were in disagreement and biased low as were the copper quality control standard The licensee prepared new copper calibration and quality control standards and recalibrated the flame atomic absorption system for coppe After recalibration the licensee reran the copper BNL standards and all results were in

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ATTACHMENT-1 2 agreemen The chromium r e%:l ts for the low and midrange concentrations analyzed.by flame atomic absorption were in disagreement and biased high as were the chromium quality control standards. The licensee prepared new chromium calibration and quality-control standards and recalibrated the flame atomic absorption system for chromiu After recalibration the licensee reran the chromium BNL standards and the chromium low concentration' result was in agreement but the midrange concentration result remained in disagreemen The licensee's original sodium results were all in disagreement, biased high, and showed very poor precision and accurac The results indicated poor sample preparation and possible sample contaminatio The licensee prepared new dilutions of the BNL standards and reran the sodium analyse The rerun results for sodium showed very little improvement from the original results and were still in disagreemen A third series of dilutions was prepared from the BNL standards and the sodium analyses reru The second rerun results for sodium were in agreemen The licensee's original silica results for the low and midrange concentrations were in disagreement and biased low. The licensee prepared new silica calibration and quality control standards and recalibrated the spectroscopy syste After retalibration the licensee reran the silica BNL standards and the silica results were all in disagreement approximately 12 percent lo This indicated an instrument systematic bias or calibration problem resulting from a one point calibration performed with a standard which had not been independently verifie The licensee *s final analytical results after retests showed 64 percent agreement with the BNL results based on 23 agreement results out of 36 total results compare The high percentage of disagreements in the confirmatory measurements comparisons of the water chemistry standards is considered to indicate significant analytical problems in the water chemistry laborator . Radiological Confirmatorv Measurements Confirmatory measurements were performed on the following standards and samples in the Region IV mobile laboratory at Fort St. Vrain Nuclear Station during the inspection:

(1) Primary Coolant Gas Sample (125 cc Serum Gas Vial)

(2) Waste Gas Sample (125 cc Serum Gas Vial)

(3) Particulate Filter Standard (24838-109)

(4) Cesco Charcoal Cartridge Standard (24840-109)

(S) Simulated Gas Standard, 125 cc Serum Gas Vial (25714-109)

(6) Simulated Gas Standard, 1 liter Gas Marinelli (2S716-109)

(7) Tritiam Sample (20 ml Scintillation Vial)

(8) 1987 Radiological Environmental Sciences Laboratory (RESL)

Quality Control Sample

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.ATTCHMENT 1 3 The confirmatory measurements tests consisted of comparing

measurements made by the licensee and the NRC mobile laborator The

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NRC's mobile laboratory measurements are referenced to the. National l Bureau of Standards by laboratory intercomparisons. Confirmatory measurements-are made only for those nuclides identified by the NRC as being present in concentrations greater than 10 percent of the respective isotopic values for liquid and gas concentrations as stated- in 10 CFR Part 20, Appendix B. Table I Attachment 5 contains the l

criteria used to compare result *

l At the time of the inspection, the licensee had three detectors in the-radiochemistry counting roo One of the radiochemistry counting room detectors was recently placed into service and was not currently calibrated for all geometrie All three detettors are used for routine isotopic analysis of radioactive samples to demonstrate compliance with TS and regulatory requirements. The detectors labeled (1), (2) and (4) are located and maintained in the radiochemistry counting room and are primarily used for isotopic analysis-of primary system sample The licensee performed the tritium analysis on their liquid scintillation counting syste The individual sample analyses and comparison of analytical results of the confirmatory measurements are tabulated in Attachment The licensee's ridiochemistry section gamma isotopic results from the listed samples in Attachment 4 showed 100 percent agreement with the NRC's analyses results. The licensee's tritium result was in agreement with the NRC's analysis resul Confirmatory measurements were performed by the licensee on a liquid radiochemistry sample prepared by RESL in Idaho Falls, Idaho. The sample was provided to the licensee in July 198 The analytical results were compared to the known sample activities and the results of the comparisons are presented in Attachment 4, sample The licensee's results were in 86 percent agreement with the certified activitie _ _ - _ _ - _ _ _ _ _ _ _ _ _ _ _ - _ _ - _ _ _ _ -

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ATTACHMENT 2 ;

Water' Chemistry Confirmatory Measurements Results Fort Saint Vrain Nuclear Station-NRC. Inspection Report: 50-267/88-09

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' Chloride Analysis _(2-20 ppb) Ion Chromatograph FSV Results NRC Results FSV/NRC Comparison Sample (oob) (ppb) Ratio- Decision 87A 4.8510.33 4.6010.02 1.0510.07- Ag re emen t, 878- 11.4310.69 9.3210.08 1.2310.07 Disagreement '

87C- 19.7111.33 19.1310.30 1.0310.03, Agreement

- ' Chloride Analysis (5-20 ppb) Selective Ion Electrode FSV Results NRC Results FSV/NRC Comparison Samole (pob) (oob) Ratio Decision 87A 9.6016.40 4.6010.02 2 . 0 9 1 1 '. 3 9 Agreement

~87B 5.6014.90 9.3210.08 0.6010.53 Agreement 87C 21.8019.90 19.1310.30 1.1410.52 Agreement

1- . Sulfate Analysis (5-20 ppb) Ion Chromatograph i FSV Results NRC Results FSV/NRC Comparison Sample (ppb) (oob) Ratio Decision

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! 87A 7.9810.16 4.8810.35 1.6410.12 Disagreement 87B 12.2412.40 9.5810.68 1.2810.27 Agreement 87C 20.0711.33 19.5010.58 1.0310.07 Agreement i

4 Iron' Analysis (10-50 ppb) Graphite Furnace Atomic Absorption FSV Results NRC Results FSV/NRC Comparison

! Sample Loob) (pob) Ratio Decision i

87G 12.71 .41 .02 0.25 Agreement 87H 22.01 .5! .8310.04 Disagreement 871 35.31 .01 .9110.05 Agreement ,

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' ATTACHMENT 2 2 C_ggper Analysis (10-50 ppb) Graphite Furnace Atomic Absorption FSV Results NRC Results FSV/NRC Comparison Samp_Le (pob) (ppb) Ratio Decision

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87G 11.31 .31 .8510.05 Disagreement 87H 23.31 .91 .8710.04 Disagreement 87I 36.71 .01 .9210.04 Agreement i Iron Analysis (100-1000 ppb) Flame Atomic Absorption l

l FSV Results NRC Results FSV/NRC Comparison l Sample (opb) ( o p b_L Ratio Decision 87G 141.711 .Oi .7610.08 Disagreement 87H 313.01 .01 .7810.02 Disagreement

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871 454.311 .011 .77 0.03 Disagreement ( ~

Retest - on 4/13/88 on same BNL standard dilutions.

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FSV Results NRC Results FSV/NRC Comparison Sample (pob) (opb) Ratio Decision 87G 141.71 .01 .7610.08 Disagreement 87H 310.012 .01 .7810.02 Disagreement 871 451.31 .011 .7710.03 Disagreement Cgager Analysis (100-1000 ppb) Flame Atomic Absorption FSV Results NRC Results FSV/NRC Comparison Samole Lp_p_b l (opb) Ratio Decision 87G 187.31 .01 .9410.02 Disagreement 87H 3'3.71 / 403.011 .9310.04 Agreement 871 572.01 . Oil .9510.02 Disagreement Retest - on 4/13/88 on same BNL standard dilution FSV Results NRC Results FSV/NRC Comparison Samgle ,pob)

( (pob) Ratio Decision 87G 194.01 .01 .9710.02 Agreement 87H 392.71 .011 .9710.04 Agreement 871 596.71 .G11 .9910.03 Agreement

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jATTACHMENT 2 3 Chromium Analysis _ (100-1000 ppb) Flame' Atomic Absorption

'FSV Results NRC Results FSV/NR Comparison

' Sampl Latkl (opb) Ratio Decision 87G 275.01 .01 .3810.00' Disagreement-87H 435.31 .Ot .1310.02 Disagreement 871 592.311 .011 .0210.03 Agreement Retest - on 4/13/S8 on same BNL standard dilution FSV Results NRC Results FSV/NRC Comparison Sample (ppbl (ppb) Ratio Decision 87G 204.71 .01 .0310.03 Agreement j 87H 403. Oi .385.01 .05 0.01 Disagreement 871 569.7 .011 .9810.02 Agreement'

l Sodium Analysis (10-100 ppm) Flame Atomic Absorptio FSV Results NRC Results FSV/NRC Comparison Sample (ppb) (opb) Ratio Decision

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87J 54.712 .21 .71 Disagreement

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87K 102.7 3 .01 .93 Disagreement 87L 120.311 .01 .52 .Disag reemen t -

Retest - New standard dilutions were made from new BNL standard FSV Results NRC Results FSV/NRC Comparison Sample (ppb) (opb) Ratio Decision'

B7J 25.3 1 .21 .2510.10 Disagreement 87K 76.71 .01 .4510.10 Disagreement 87L 104.71 .01 .33tO.08 Disagreement

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Retest - New standard dilutions were prepared from 86 series BNL l standard FSV Results NRC Results FSV/NRC Comparison Sample (oob) (ppb) Ratio Decision 86J 32.Ot1 .21 .1110.78 Agreement 86K 44.Ot .21 .95 0.09 Agreement 86L 64.71 .0 .9010.07 Agreement

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' ATTACHMENT 2 4

.1 Ammonia' Analysis-(C.5-10 ppm) Selective Ion Electrode FSV Results NRC.Results FSV/NRC -Comparison Sarp_1e 1ppml (com) Ratio Decision-boM O.6210.33 0.52ir.0 .19 0.64 Agreement 86N 1.W,'io.67 1.51:0.02 1.30tO.44 Agreement 860 4.3510.18 4.9210.23 0.8810.05 Disagreement-1 Hydrazine Analysis (10-100 ppb) Spectroscop FSV Results NRC Results FSV/NRC Comparison 1 Samole (oob) (ppb) ' Ratio . Decisio P 19.3 .91 .9710.03 Agreement 870 45.71 .91 .9210.02 Disagreement 87R 93.01 .100.01 .93iO.05 Agreement

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1 Silica Analysis (5-100 ppb) Spectroscupy FSV Results NRC Results FSV/NRC Comparison Samole (ppb) (pob) Ratio Decision 875 12.31 .61 .7010.05 Disagreement 87T 30.01 .71 .8610.04 Disegreement-87T 80.31 .71 .9310.04 Agreement Retest - on 4/13/88 on same BNL standard dilution FSV Results NRC Results FSV/NRC Comparison Sample (pob) (oob) Ratio Decision 875 14.01 .61 .8010.07 Disagreement 87T 30.71 .71 .8810.05 Disagreement 87T 76.01 .71 .8810.04 Disagreement

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eIIBEODEUI_3 CBIIEBle_EQB_CDDEeB100_sueLYIlceL_tgeSUBEdEUIL

.iis attachment provides criteria f or comoaring 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 valu The following steps are performed (1) The ratio of the licensee's value to the NRC value i s coinputed

= L i C '"'" ' ' v*l"'

(ratio ); and NRC VALUE (2) the uncertainty of the ratio is propagate If the absoluto value of one minus the ratio is less than or equal to twice the ratio uncertainty, the results are in agreemen (l1-ratio l 5 2x uncertainty)

x si si s; Z= , then = + .-

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

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ATTACHMENT'4

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'Radiolooical Confirmatory Measurements'Results

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Fort St. Vrain Naclear Station NRC Inspection Report 50-267/89-09 1. - 'Drimary Coolant-(125cc Gas Serum Vial)

(Sampled 13:00, MST, April 13, 1986)

Sample' analyzed on. detector (1).

. FSV Results NRC Results FSV/NRC Comparison

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Nyc_lide ( uCi /c c ). (uCi/cc)' Ratio Decision-Xe-131m 5.24tO.92E-5 7.22211.589E-5 10.73 Agreement Xe-133m 2.60iO.31E-5 3.07610.376E-5 0.85 Agreemen 'Xe-133 1.0510.10E-3 9.389tO.059E-4 1.12 ' Agreement Waste Gas. Sample (125cc Serum Gas Vial)

(Sampled: 10:04, MST, April 12, 1988)

. Sample' analyzed on detector (1).

FSV Results NRC Results FSV/NRC Comparison Nuclide (uCi/cc) (uCi/cc) R3tio Decision Xe-133 1.1810.12E-4 1.142tO.013E-4 1.03 Agreement

. _ Particulate Filter Standard (24838-100,1 No comparison was made on this standar The licensee's particulate filter geometry was different from the NRC standard geumetry provide ,

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i 4 Cesco Charcoal Cartridae Standard (24840-309)

No comparison mede on this standar The licensee's cartridge media was different from the NRC charcoal cartridge provide I i

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A_T_T ACHME N T 4 2 Simulated Gas Standard, 125cc Gas Vial (25714-109)

(Standardized: 08:00, MST, April 12, 1988)

Standar '

analyzed on detectors (1), (2) and (4).

FSV Results NRC Results FSV/NRC Comparison Nuc1ide (uCi/samole) Lu_C i / s a m p_l el Ratio Decision Cd-109 1.3910.12E+0 1.47710.OO8E+0 0.94 Agreement 1.4110.11E+0 0.95 Agreement 1.33tO.10E+0 0.90 Agreement Co-57 2.5610.18E-2 2.73210.028E-2 0.94 Agreement 2.6110.19E-2 0.96 Agreement 2.4210.17E-2 0.88 Agreement Ce-139 2.12iO.21E-2 2.19010.027E-2 0.97 Agreement 2.1210.21E-2 0.97 Agreement 2.1410.21E-2 0.98 Agreement Hg-203 2.26 0.20E-2 2.31310.036E-2 0.98 Agrenment 2.2710.21E-2 0.98 Agreement 2.2010.20E-2 0.95 Agreement Sn-113 3.9810.2SE-2 4.14910.063E-2 0.96 Agreement 4.0610.27E-2 0.98 Agreement 4.0710.2SE-2 0.98 Agreement Sr-85 2.67 0.17E-2 2.84SiO.049E-2 0.94 Agreement 2.7610.22E-2 0.97 Agreement 2.7810.18E-2 0.98 Agreement

! Cs-137 4.8110.31E-2 S.17910.049E-2 0.93 Ag r eemr.u t

! 4.9110.40E-2 0.95 Ag r e e'aen t 4.8110.32E-2 0.93 Agreement Y-88 , 6.6910.38E-2 7.01210.092E-2 0.95 Agreement 6.5910.44E-2 0.94 Agreement 6.4610.39E-2 0.92 Agreement ,

Co-60 S.3810.35E-2 S.28010.087E-2 1.02 Agreement j S.13? ME-2 0.97 Agreement S.191v .36E-2 0.98 Agreement l

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ATTACHMENT 4 3 Simulated Gas _ Standard u_1 Liter Gas Marinelli (25716-109)

(Standardized: 08:00, MST, April 12, 1988)

Standard analyzed on detectors (1), (2) and (4).

FSV Results NRC Results FSV/NRC Comparison Nuclide [uCi/samplel (uCi/ sample) Ratio Decision Cd-109 1.8810.16E+O 1.77410.010E+c 1.06 Agreement 1.7710.11E+0 1.00 Agreement 1.8310.14E+0 1.03 Agreement Co-57 3.3710.33E-2 3.33910.026E-2 1.01 Agreement 3.2910.22E-2 0.99 Agreement 3.25!O.23E-2 0.97 Agreement Ce-139 2.6710.26E-2 2.66810.023E-2 1.00 Agreement 2.5810.17E-2 0.97 Agreement 2.7010.27E-2 1.01 Agreement Hg-203 2.7410.24E-2 2.72710.032E-2 1.00 Agreement 2.6110.26E-2 0.96 Agreement 2.6510.24E-2 0.97 Agreement Sn-113 5.12iO.31E-2 5.048!O.054E-2 1.01 Agreement 4. 92to. 45E- 2 0.97 Agreement 5.1510.34E-2 1.02 Agreement Sr-85 3.52!O.22E-2 3.49810.043E-2 1.01 Agreement 3.40tO.23E-2 0.97 Agreement 3.52iO.25E-2 1.01 Agreement Cs-137 6.41 0.40E-2 6.29210.068E-2 1.02 Agreement 6.1410.46E-2 0.98 Agreement 6.3210.44E-2 1.00 Agreement Y-88 8.36 0.82E-2 8.443to.083E-2 0.99 Agreement 8.2010.57E-2 0.97 Agreement l

8.1510.52E-2 0.97 Agreement Co-60 6.5810.44E-2 6.589 0.078E-2 1.00 Agreement 6.5110.46E-2 0.99 Agreement 6.35tO.48E-2 0.96 Agreement Tritium lample (20 ml Scintillatton Vial)

(Sampled: 14:00, MST. April 14, 1988)

FSV Results NRC Results FS\'.'NRC Comparison Nuc1ide (uCi/ml) Lit C

_i /_m_Q R a t.4 s Decision h-3 1.57tO.OOSE-3 1.6410.05F-3 0.96 Agreement

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A_TTACHMENT 4 4 RESL Unknown Liould Sample (Standardized: 12:00, MST, January 11, 1987)

FSV *asults NRC Results FSV/NRC Comparison tju.g l i d e (uCi/ml) LuCi/ml) Ratio Decision Mn-54 2.94!O.54E-5 2.86tO.06E-5 1.03 Agreement Co-60 2.8110.53E-S 2.7510.05E-5 1.02 Agreement Cs -137 4.0910.87E-5 4.0310.12E-5 1.01 Agreement Fe-SS .t.OO O.42E-4 1.0310.02E-4 0.97 Ag r ee.nen t Sr-89 2.11 0.10E-4 2.3010.07E-4 0.92 Agreement Sr-90 3.0810.07E-5 2.0910.08E-5 1.47 Disagreement H-3 1.5610.02E-4 1.6810.03E-4 0.93 Agreement NRC results were taken from the standard certification supplied to the NRC Region IV office au prepared by RESL and traceable to the National Bureau of Standards, l

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GIIOCbdEUI_D CBIIEB10_EQB_COdB08100_000LYIICOL_DEOSUBEDEUIS The f ollowing are the criteria used in comparing the results of capability tests and verification measurement The criteria are based on an empirical relationship established through prior experience and this program's analytical requirement In these criteria, the judgement limits vary in relation to the comparison of the resoluti o =

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Resolution MRC UNCERTAINTY LICENSEE VALUE Ratio =

NRC VALUE Comparisons are made by first determining the resolution and then reading across the same line to the corresponding ratio. The f ollowing table shows the acceptance value RESOLUTION AGREEMENT RATIO (4 0.40 - 2.50 4 -7 0.50 - 2.00 8- 15 0.60 - 1.66 16 - 50 0.75 - 1.33 51 - 200 0.80 - 1.25

>200 0.85 - 1.18 The above criteria are applied to the f ollowing analyseus (1) Gamma Spectrometry ,

(2) Tritium in li quid samples (3) lodine on adsorbers (4) Sr and Sr determinations .

(5) Gross Beta where samples are counted on the same date using the same reference nuclid f

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