IR 05000317/1986008

Insp Repts 50-317/86-08 & 50-318/86-08 on 860421-25.No Violation Noted.Major Areas Inspected:Nonradiological Chemistry Program,Including Measurement Control & Analytical Procedure Evaluation

ML20198S643
Person / Time
Site:	Calvert Cliffs
Issue date:	05/28/1986
From:	Pasciak W, Zibulsky H NRC OFFICE OF INSPECTION & ENFORCEMENT (IE REGION I)
To:
Shared Package
ML20198S618	List: IR 05000317/1986008 ML20198S616
References
50-317-86-08, 50-318-86-08, NUDOCS 8606100503
Download: ML20198S643 (6)

Text

--

. .

i U.S. NUCLEAR REGULATORY COMMISSION t REGION I 50-317/86-08 Report N /86-08 50-317 Docket N DPR-53 License No. DPR-69 Category C Licensee: Baltimore Gas & Electric C P. O. Box 1475 Baltimore, Maryland 21203 Facility Name: Calvert Cliffs Nuclear Power Plant, Units 1 and 2 Inspection At: Lusby, Maryland Inspection Conducted: April 21-25, 1986

'

Inspectors: 'b h' T-2 7- T fo H. Zibulskj C% mist date Approved by: -

)4A660 25 7 b W. J(@as'ciak, Chief, Ef fluents /d4te Radiat'fon Protection Sections, DRSS Inspection Summary.: Inspection on April 21-25, 1986 (Combined Inspection Report Nos. 50-317/86-08 and 50-318/86-08)

Areas Inspected: Routine, announced inspection of the nonradiological chemistry program. Areas reviewed included measurement control and analyti-cal procedure evaluation Results: No violations were identifie DR 860529 ADOCK 05000317 PDf,t

-

, .

OETAILS Individuals Contacted

• J. Lemons, Manager, Nuclear Operations Department

• P. Crinigan, General Supervisor, Chemistry Nuclear Operations Department

• Sprecher, Supervisor, Plant Chemistry, Nuclear Operations Department

• Putman, Senior Quality Assurance Auditor M. Bowman, General Supervisor, Technical Services -

Engineering S. Cowne, Licensing Engineer

• Denotes those present at the exit intervie The inspector also interviewed other licensee employees including members of the chemis'.ry staf . Action on Preiious Licensee Findings (Closed) 50-317/84-28-01 and 50-318/84-28-01 IFI - Control standards were

'not used or documented on control charts. The licensee has generated control charts with a 2 sigma alert parameter and a 13 sigma acceptance criteri (0 pen) 25-00-13 TI - The inspection covered part of this item. Of the two modules included in the TI, Module 79501 was complete . Measurement Control Evaluation The licensee's measurement control program will be verified through analysis of actual plant water samples. A simulated reactor coolant sample, with ammonia and lithium as matrices, was made and two feedwater samples were taken. Duplicate samples were sent to Brookhaven National Laboratory (BNL) for independent verification. Boron, chloride and fluoride analyses will be performed on the simulated reactor coolant sample, iron and copper analyses on one feedwater sample acidified with nitric acid, and silica, ammonia and hydrazine analyses on the other feedwater sample acidified with hydrochloric acid. On completion of the analyses by both laboratories, a statistical evaluation will be made (Inspector Followup Item 50-317/86-08-01 end 50-318/86-08-01).

The inspector reviewed the measurement control charts. The licensee generated the charts correctly and they reflected the performances of the measurement systems. For ammonia, the control standard, analyzed with the NRC standards, showed a positive bias and the results were not within the acceptance criteria range. The high bias was also shown with the NRC

_ _ . . _ _

__ _ - . . - . _-

. .

. 3

'

standards. For hydrazine, the control standard resulted in a negative

<

bias and was also out of the range of acceptance. The low bias was shown to be within the NRC standards. The results of the investigations of these biases will be discussed in paragraph '

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 solutions. The licensee agreed to maintain two standard stock solution .

The inspector reviewed the licensee's procedure for drawing the calibra-tion curves associated with the spectrophotometer. The licensee used a straight edge to draw a line through the data points. The inspector recommended that the calibration curves be statistically fit to the data points and not graphically approximated. This would result in a better interpolation of the area between the data points. The licensee said he will investigate the curve fittin . Analytical Procedures Evaluation During the inspection, standard chemical solutions were submitted by the

* inspector to the licensee for analysis. The standard solutions were i prepared by BNL for NRC Region I, 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 four out of twenty four comparisons were in disagreement under the criteria used for comparing results (see Attachment 1). The hydrazine disagreements were due to the loss of sensitivity to the

! spectrophotometric procedure when the laboratory eliminated a calibration curve that utilized a larger cell which had good sensitivity and detectability at lower concentrations. The licensee will construct a

calibration curve for the 40 mm cell and generate a control chart for that hydrazine concentration. The existing calibration curve and control

! chart was for a 20 mm cell. The ammonia disagreements were due to the deterioration of the standard stock solution. The control standard i identified the problem. This showed the need for the maintenance of two independent standard stock solutions to cross check one another. When

'

the licensee prepared a new standard stock solution and reran the Nessler's procedure, the comparisons were in agreemen ,

'

The inspector recommended some procedural changes. With the incorpora-tion of the changes, the licensee will have an effective measurement and

measurement control progra . . - - - - - _

l

!

'

_ _ _ - __ _ . _ _ _ . _ _ _ _ _ _ _ - . _ . . _ - _ _ _ . - ._ __ - , _ _ _ _ _

_._ , .

.

4 Exit Interview The inspector met with the licensee representatives (denoted in paragraph 1) at the conclusion of the inspection on April 25, 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 inspecto .

.~-e-.mn-- - - . - - - ~ - - - - - . - ,

. .

CAPABILITY TEST RESULTS Calvert Cliffs Nuclear Power Plant, Units I and 2 Parameter NRC Value Lic. Value (Lic./NRC) Comparison Results in parts per billion (ppb)

Chloride 20.6 i .8 1 .91 1 0.08 Agreement 6 .0 69.2 1 .0 Agreement 27.7 1 .7 i 2.1

1.11 1 0.14 Agreement Fluoride 19.2 1 .6 .02 0.06 Agreement 74.5 i .1 1 .91 0.07 Agreement 3 .0 36.5 i .11 0.08 Agreement Hydrazine 100 .7 1 .95 1 0.02 Disagreement 19.3 1 .7 i .87 1 0.10 Agreement 52.4 1 .0 1 .80 1 0.04 Disagreement Ammonia 1168 1 19 1293 1 15 1.11 1 0.02 Disagreement 120 1 3 147 t 12 1.23 1 0.09 Disagreement 356 i 11 '37010 1.04 i 0.03 Agreement iueenia 1168 1 19 1223 1 15 1.05 0.02 Agreement (Rer a) 120 1 3 113 1 .94 1 0.05 Agreement 356 1 11 377 i 15 1.06 1 0.05 Agreement Results in parts per million (ppm)

Boron 1014 1 15 1009 i 3 Agreement 3047 1 26 2977 i 7 0.98 i 0.01 Agreement 5040 i 130 4945 i 3 0.98 i 0.03 Agreement Iron 0.31 1 0.02 0.33 1 0.01 1.06 1 0.08 Agreement 0.57 1 0.02 0.63 1 0.02 1.11 1 0.05 Agreement 0.82 1 0.05 0.95 1 0.03 1.16 0.08 Agreement Copper 0.32 1 0 0.32 1 0 Agreement 0.62 1 0.01 0.62 1 0 Agreement 0.92 1 0.01 0.92 1 0 Agreement

. -~ - . . - - - - -- - -- . .

'

. ,

,

ATTACHMENT

,

j Criteria For Comparing Analytical Measurements i

This attachment provides criteria for comparing results of capability test In these criteria the judgment limits are based on the uncertainty of the ratio of the licensee's value to the NRC value. The following steps are j 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 propagate i If the absolute value of one minus the ratio is less than or equal twice the-l ratio uncertainty, the results are in agreemen ; (ll-ratio 11 s 2 uncertainty)

I Z=x, the, Sz2 = Sx2

.: i ~F x2 +k2

(From

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

I l

T i

I l

,

)

i

)

!

l

,

1,

.

,

t

- v v.- ---n - , . . . , , . - - ,e, .--,.,,,.c,, . . ,.-c,.-,,n--..--~,,.en,, -

-- ---.------,,..----rn.. --e--~ --

~~r-~.- - - -