ML023220214

Emergency Plan Implementing Procedures Manual Volume B, Revision 2002-10

ML023220214
Person / Time
Site:	Oconee
Issue date:	11/11/2002
From:	Rosalyn Jones Duke Power Co
To:	Document Control Desk, Office of Nuclear Security and Incident Response
References
Download: ML023220214 (34)

Text

I Duke Power A Duke Energy Company November 11, 2002 U. S. Nuclear Regulatory Commission Document Control Desk Washington, D.

C.

20555

Subject:

Oconee Nuclear Station Docket Nos. 50-269, -270,

-287 Emergency Plan Implementing Procedures Manual Volume B, Revision 2002-10 Please find attached for your use and review copies of Oconee Nuclear Station Emergency Plan:

Volume B Revision 2002-10 the revision to the November 2002 This revision is being submitted in accordance with 10 CFR 50-54(q) and does not decrease the effectiveness of the Emergency Plan or the Emergency Plan Implementing Procedures.

Any questions or concerns pertaining to this Emergency Planning Manager at 864-885-3301.

By copy of this letter, two copies of this NRC, Region II, Atlanta, Georgia.

revision please call Rodney Brown, revision are being provided to the vey

yours, R.

.'nes VP, Oconee Nuclear Site xc:

(w/2 copies of attachments)

Mr. Luis Reyes, Regional Administrator, Region II U.

S. Nuclear Regulatory Commission 61 Forsyth St.,

SW, Suite 24T23 Atlanta, Georgia 30303 w/copy of attachments Mr. Steven Baggett Rockville, Maryland (w/o Attachments, Oconee Nuclear Station)

NRC Resident Inspector M. D. Thorne, Manager, Emergency Planning www duke-energy com R. A. JONES Vice President Duke Power 29672 / Oconee Nuclear Site 7800 Rochester Highway Seneca, SC 29672 864 885 3158 864 885 3564 fax

November 11, 2002 OCONEE NUCLEAR SITE

SUBJECT:

Emergency Plan Implementing Procedures Volume B, Revision 2002-10 Please make the following changes to the Emergency Plan, Volume B by following these instructions.

REMOVE Cover Sheet Rev. 2002-09 Table of Contents page 1 Chemistry Lab -

LM/O/P003C (11/18/96)

Chemistry Lab -

LM-O-P919 (07/18/02)

ADD Cover Sheet Rev. 2002-10 Table of Contents page 1 Chemistry Lab -

LM/O/PO03C (11/06/02)

Chemistry Lab -

LM 0 P919 (10/28/02)

DUKE POWER EMERGENCY PLAN IMPLEMENTING PROCEDURES VOLUME B APPROVED:

W. W. Foster, Manager Safety Assurance 11/11/2002 Date Approved 11/11/2002 Effective Date VOLUME B REVISION 2002-10 NOVEMBER 2002

Chemistry Lab LM-O-PO03C Chemistry Lab LM-O-P919 CP/1/A/2002/004C CP/1 &2/A/2002/005 CP/2/A/2002/004C CP/3/A/2002/004C CP/3/A/2002/005 HP0/B/1 009/009 HP0/1B/1009/012 I1P/0/B11009/015 HP/O/B/1009/016 HIP/l/A/10091017 IIP/2/A/1009/017 IP/3/A/1009/017 RP/OJB/10001011 RP/OB/B11000/025 RP/O/B/1000/027 VOLUME B TABLE OF CONTENTS Determination Of Boron By Manual Colorimetric Titration Boron Analysis by Mettler DL 58 Boron Titration Operating Procedure For The Post Accident Liquid Sampling System (PALSS)

Post Accident Caustic Injection Into The Low Pressure Injection System Operating Procedure For The Post Accident Liquid Sampling System (PALSS)

Operation Procedure For The Post-Accident Liquid Sampling System (PALSS)

Post Accident Caustic Injection Into The Low Pressure Injection System Procedure For Determining The Inplant Airborne Radioiodine Concentration During Accident Conditions Distribution Of Potassium Iodide Tablets In The Event Of A Radioiodine Release Procedure For Sampling And Quantifying High Level Gaseous Radioiodine And Particulate Radioactivity Procedure For Emergency Decontamination Of Personnel And Vehicles On-Site And From Off-Site Remote Assembly Area Operating Procedure For Post-Accident Containment Air Sampling System Operating Procedure For Post-Accident Containment Air Sampling System Operating Procedure For Post-Accident Containment Air Sampling System Planned Emergency Exposure Operational Support Center Manager Procedure Re-Entry Recovery Procedure 1

11/06/02 10/28/02 01/08/02 07/24/02 01/08/02 01/08/02 07/24/02 12/03/97 01/09/01 07/23/01 12/29/97 09/13/00 09/13/00 09/13/00 02/01/94 03/20/02 05/30/00 Revision 2002-10 November 2002

ia.

Duke Power Company Nuclear Generation Department LABORATORY METHOD PROCESS RECORD Reference Use INFORMATON ONLY Station:

Oconee LMO 0 /P0 0 3 C Rev. #: 2 Change:

(A, B, or C, etc.)

Title:

Determination of Boron by Manual Colorimetric Titration (check applicable boxes)

El This Method is based on General Lab Method LM/G/

Rev, _

without substantive changes.

o This Method is based on General Lab Method LMG/.

Rev, _

with substantive changes.

This Method is not based on a General Lab Method.

El This revision does not invalidate criteria for use of a laboratory method (reference SCM-6, Section 5.1.1)

(if any of these criteria are no longer valid, then a Technical Procedure must be used for this activity)

El These changes affect the associated method development package.

El Field testing performed.

Date:

Initials:

Description of Change: (Attach additional pages if necessary)

Basis for Change: (Attach additional pages if necessary)

3.

,Oo

,,~

Field Testing Comments: (Attach additional pages if necessary)

Prepared by 4

1 e

Date./5/

0./,

Technical Review by Date

//

Additional Review bh (optional)

Date Approved by

/

.00 Date

//A,/a7.

LMIOoPoO3 C Page 2 of 6 Determination of Boron by Manual Colorimetric Titration Using Phenolphthaline Indicator

1. Discussion NOTE:

A control copy of this procedure shall be routed to the Emergency Preparedness Team within three working days after any approved changes.

1.1 Scope This procedure describes the determination of boron by a manual colorimetric titration in samples containing multiple forms of boron.

The intent of this procedure is to provide a mechanism to analyze borated samples during an Appendix "R", which has resulted in the loss of our normal analytical instrumentation and when a high degree of accuracy is not required.

1.2 Principle Boric acid is a very weak, monobasic acid with an ionization constant (KA) of 6.4 X 10-1O. Because it is a very weak acid, the concentration of boric acid in aqueous solutions cannot be potentiometrically determined directly with a strong base. However, boric acid in the presence of mannitol acts as a much stronger acid with a KA = IX 10-4, and can be directly determined by titration with a strong base. The dramatic increase in the ionization constant of boric acid is due to the formation of a mannitol - borate complex. In this determination, an excess of mannitol is added to the sample to be analyzed, then standard sodium hydroxidle is added to the sample until a faint pink color is observed and remains consistent.

1.3 Limits and Ranges This procedure is applicable to samples containing between 100 and 2500 ppm boron. It is recommended for conservation of time and dose that samples > 1000 ppm should be diluted.

1.4 Precision and Accuracy The precision should be +/- 10 ppm and the accuracy should be +/- 5.0 %.

I

uWO/P003 C Page 3 of 6 1.5

- Interferences 1.5.1 Lithium hydroxide is an interfering factor in low boron concentrations (< 100 ppm B). 1.56 ppm B per ppm Li should be added to the calculated boron concentration. Also, phosphate, (over 10 ppm), germanium, and tetravalent vanadium react with mannitol like boron and should be absent.

1.5.2 Any error from atmospheric carbon dioxide can be minimized by utilizing a drying column attached tothe sodium hydroxide titrant bottle.

1.6 Precautions CAUTION:

Chemical hazards shall be known prior to use. For additional information and first aid requirements, refer to the MSDS Sheets.

1.6.1 Results obtained by this lab method may affect Reactivity Management.

1.6.2 If failed fuel exceeds 1%, follow instructions given by Radiation Protection and perform analysis according to CSM 5.2.

1.6.3 The following PPE shall be worn for:

1.6.3.1 8% mannitol

• safety glasses

• rubber or vinyl gloves

• lab coat A

1.6.3.2 0.1005 - 0.0995 N NaOH

• safety glasses

• rubber or vinyl gloves

• lab coat 1.6.3.3 Boron standard

• safety glasses

• rubber or vinyl gloves

• lab coat 1.6.3.4 Phenolphthalein indicator

• safety glasses rubber or vinyl gloves

• lab coat

uvuOf 003 C Page 4 of 6 1.6.3.5 Methanol

• chemical splash goggles Srubber gloves

• lab coat

2. Apparatus 2.1 200 mL Tall Form Beaker or a 250 mL Erlenmeyer flask

2.2 Burette

with sufficient volume to dispense up to 25 mL NaOH titrant

2.3 Pipettes

10 mL glass class "A" for sample and standard transfer 2.4 Graduated Cylinder: 100 mL for mannitol measurement

3. Reagents NOTE:

It is imperative that certified 0. 1 N NaOH and 1000 PPM boron standard be used in this analysis.

3.1 Mannitol Solution, 8% WIV Dissolve 320 grams _+/- 1 gm of d - mannitol per 4 liters of demineralized water and adjust the pH to 8.5 + 0.1 with dilute NaOH or HCI Stable for two (2) weeks.

3.2 0.1005 - 0.0995 N (Certified) Sodium Hydroxide:

Use Fisher SS-276 or equivalent. Expiration date as noted on manufacturer's bottle.

3.3 Boron Standard:

Use Fisher SB-155, certified 1000 ppm =/- 1% or equivalent. Expiration date as noted on manufacturer's bottle.

3.4 Phenolphthalein Indicator:

Add 0.1 grams of disodium salt of phenolphthaline to 200 mL of methanol. Shelf life is indefinite.

IMO/Po03 C Page 5 of 6

4. Procedure NOTE:

When performing this analysis, two aliquots of the 1000 ppm boron standard must be analyzed with each set of samples or once per day whichever is less frequent.

• Calculations Boron Equivalency Factor (BEF)

(0.17485mgB) 61.83mgH3BO3 lOOOppm 1081 SmgH3BO3 meqH3BO3 mgBImL) 10 m-L sample vol.

where:

0.17485 =fraction B in H 3B0 3 61.83 = equivalent weight of H 3BO3 1000 = conversion mg B/mL to ppm Vol. of Titrant X Normality of Titrant X BEF = ppm Boron 4.1 Fill the titration burette with 0.1 N NaOH and record the initial reading of the meniscus.

4.2 Using a volumetric pipet, transfer 10.00 +/- 0.01 mL of the 1000 ppm standard or sample to an appropriate beaker.

4.3 Add 100 mLs +/- 1.0 mL of 8% mannitollsolution to the sample or standard and mix thoroughly by swirling the beaker.

4.4 Add 3 to 7 drops of phenolphthaline to the sample/standard to be analyzed and mix by slowly swirling the beaker.

4.5 Using the titration buret, slowly open the stopcock until NaOH begins to flow in a uniform "droplet" pattern. Continue to titrate the solution, swirling the beaker slowly, with the Certified Standard Sodium Hydroxide (0.1 N) until one drop produces a faint, constant pink color.

4.6 Carefully record the final burette reading and determine the amount of sodium hydroxide used by subtracting the initial burette reading from the final burette reading.

4.7 Perform a duplicate analysis by repeating Steps 4.1 through 4.5. Samples and standards must agree within +/- 0.2 mLs.

IMiOIPo3 C Page 6 of 6 4.8 Calculate sample and standard concentration by:

(Titrant Buret Vol.) x (0.1 N NaOH) x (1081) = ppm Boron 4.9 Log standard results in Enclosure 6.1.

5. References 5.1 B&W Water Chemistry Manual (1385), Rev. 5 5.2 McGuire Nuclear Station, LM/M/P903, Rev. 1, "Manual Boron Analysis"

6. Enclosures 6.1 Boron Manual Titration Performance Check

.1 L/O/P003 C Boron Manual Titration Performance Check Page 1 of 1 DAILY, IF USED 1000 + 50 ppm DATE TIME STD. CONC.

ANALYST COMMENTS

Station:

Ocon Duke Power Company Nuclear Generation Department LABORATORY METHOD PROCESS RECORD Referec INFORMATION ee LMIO/P919 Rev. #: 7 Change:

(A, B, or C, etc.)

Boron Analysis by Mettler DL-58 Boron Titrator (check applicable boxes)

El This Method is based on General Lab Method LM/G/__

Rev, without substantive changes.

0 This Method is based on General Lab Method LMIGI___

Rev, with substantive changes.

0 This Method is not based on a General Lab Method.

This revision does not invalidate criteria for use of a laboratory method (reference SCM-6, Section 5. 1. 1)

(if any of these criteria are no longer valid, then a Technical Procedure must be used for this activity)

El These changes affect the associated method development package.

O3 Field testing performed.

Date:

Initials:

Description of Change: (Attach additional pages if necessary)

• ee

,47-7&a-c-.ke Basis for Change: (Attach additional pages if necessary) rSee,4711'cLe,0 Field Testing Comments: (Attach additional pages if necessary)

Prepared by 7-Ze' Date A911.7160 Technical Review by Date o0/t z Additional Review by ptional)

Approved by

_ IA Lo4ll Date

Title:

Changes to LM/O/P919 Boron Analysis By Mettler DL-58 Boron Titrator Added statement in "Precautions" to bracket samples with appropriate QC, (10 ppm samples <100, and 1000 ppm >100 ppm).

Added requirement to obtain Fisher Certificate of Analysis (COA) for each 1000 ppm standard lot number.

Added instructions to prepare 10 ppm Boron standard.

Added notes where applicable:

(6'O','O/,7a.)

• 2 level teaspoons equates to approximately 5 grams of mannitol

• mannitol may be added anytime between placing it in the sample changer and starting analysis Clarified during standardization when to choose "Save Entry" or "Modify Entry" 4.4.13 Corrected reference to steps PIP 4841.2 Section 4 - Rewrote section to allow for adding any programmed method as an additional sample series to an existing one.

IT

LM/O/P919 Page 2 of 2 Boron Analysis by Mettler DL58 Boron Titration

1. Purpose NOTE:

Seven Control Copies and one Information Only copy of this Lab Method shall be routed to the Emergency Preparedness Team within three (3) working days following any approved changes/modifications.

1.1 Scope CAUTION:

This laboratory method describes the automatic titrimetric method for determining boron in aqueous solutions. This laboratory method is applicable for Primary Systems.

I 1.2 Principle Boric acid is a weak acid and cannot be titrated directly with a strong base to an accurate endpoint. Mannitol is added to stabilize the anion of boric acid and increase the strength of the acid.

The mannitol-borate complex can then be titrated with a strong base. The concentration of boron is proportional to the amount of standard sodium hydroxide required to titrate the boron to a pH endpoint of 8.3.

The titration is performed by a Mettler DL58 automated titration system. Samples are loaded onto a Mettler ST20A Sample Transport Unit. A digital buret assembly dispenses titrant into the sample. The rate of titrant delivery is slowed near the equivalence point.

This allows ample time for thorough mixing and reaction of titrant with the sample until the pH equivalence point is obtained.

1.3 Interferences 1.3.1 Carbon Dioxide is an interferent; however, the interference should be negligible if the following conditions are met:

• Water used for preparing sodium hydroxide is boiled or deaerated.

• Sodium hydroxide reservoir is air tight or equipped with a CO2 absorption tube filled with drying agent.

• Sample is not over-stirred.

• Sample exposure to air is minimized.

1.3.2 Lithium Hydroxide and Ammonium Hydroxide are potential interferences; however, these interferences have been determined to be negligible as the change in boron concentration that they cause is less than the required accuracy needed.

1.4 Limits This method is applicable for samples containing between 0.2 - 10,000 ppm boron as boric acid.

LM/O/P919 Page 3 of 3 1.5 Precautions 1.5.1 The pH electrode should be stored in a conditioning agent as recommended by the electrode manufacturer when not in use.

1.5.2 The sodium hydroxide reservoir should be emptied and refilled rather than "topped off" when the supply is low.

1.5.3 Typically, when the titrator has been idle, the first standard/sample will show a high bias result. Therefore, when the titrator has been idle, the first standard/sample of a titration series should be run in duplicate and the first result discarded.

1.5.4 If the titrator does not initiate analysis after pressing the [Run] key twice, then the

[Run] key may need to be pressed again or the [Start] key may be pressed.

1.5.5 If the titrator goes into the Hold mode when adding samples to a series, the [Hold]

key may need to be pressed to resume analysis.

1.5.6 This laboratory method is related to plant Reactivity Management. Reactor coolant boron directly impacts Reactivity Management. Reactor coolant and support system boron concentrations are determined by this method.

1.5.7 When determining the concentration of PALSS boron, results obtained must be multiplied by the PALSS dilution factor found in the appropriate PALS S procedure(s).

1.5.8 Wear the following minimum proper personal protective equipment (PPE) when performing this analysis.

• Labcoat Safety glasses

• Gloves

• Apron and faceshield or hood sash when handling 50% W/W Sodium Hydroxide or Hydrochloric Acid 1.5.9 When boric acid is heated at 1000 to 160'C, it gradually decomposes and loses water to form metaboric acid (HBO 2) then pyroboric acid (H2B40 7 ), and finally boric anhydride (B20 3). Hence, in preparing a boron standard, boric acid is neither dried nor desiccated prior to weighing.

1.5.10 For error messages and/or malfunctions, refer to Enclosure 6.3.

1.5.11 Sample concentration must not exceed a burette delivery volume of 40 ml. See Section 4.4.2 for selecting appropriate sample size.

1.5.12 Sodium Hydroxide lines and delivery tip must be kept free of air bubbles at all times. Air bubbles will result in unreliable sample results.

1.5.13 Samples should be bracketed with an appropriate QC. For samples < 100 ppm expected use a 10 ppm QC, for > 100 ppm expected a 1000 ppm QC.

LMIO/P919 Page 4 of 4

2. Apparatus 2.1 Mettler DL58 Compact Titrator System 2.1.1 DL58 Titrator 2.1.2 20 ml Buret or 10 mL Buret 2.1.3 ST20A Sample Transport 2.1.4 Printer 2.1.5 Electronic Balance with Data Output Module 2.1.6 Combination pH electrode, pH 0-14 2.2 Sample cups, 100 mL 2.3 Volumetric flasks 2.4 Volumetric pipets

3. Reagents CAUTION:

Chemical hazards shall be known prior to use. For additional information and first aid "requirements, refer to MSDS Sheets.

3.1 pH Buffers, 7, 9, 10 3.1.1 Fisher buffers or equivalent may be purchased or prepared and used per package instructions.

3.1.2 Use manufacturer stated shelf life OR record shelf life as 3 months.

3.2:-

Electrode Filling Solution 3.2.1 Use solution specified by the manufacturer of the electrode in use.

3.2.2 Use manufacturer stated shelf life.

NOTE:

Reagents may be prepared in varying quantities as long as the ratios remain unchanged.

3.3 Sodium Hydroxide (NaOH), 0.10 N 3.3.1 Purchased NaOH (Fisher SS278-1 or equivalent) 3.3.1.1 Use manufacturer stated shelf life.

3.3.1.2 Store in an air tight container OR a container fitted with a carbon dioxide (CO2) absorption tube.

3.3.1.3 Standardize solution once per week or prior to use, whichever is less frequent, per Section 4.3 (NaOH Standardization).

LM/OJP919 Page 5 of 5 3.3.2 Prepared NaOH, 0.10N WARNING: Sodium Hydroxide is corrosive. Level III PPE (labcoat, safety glasses, gloves, and faceshield or hood sash) is required when handling 50% W/W Sodium Hydroxide.

I 3.3.2.1 Add 32.0 grams (31.5 - 32.5) of liquid 50% W/W NaOH to 3850 (3845 - 3855) mLs of boiled or dearated reagent grade water AND mix.

3.3.2.2 Store in an air tight container OR a container fitted with a carbon dioxide (CO 2) absorption tube.

3.3.2.3 Record shelf life as 1 year.

3.3.2.4 Standardize solution once per week or prior to use, whichever is less frequent, per section 4.3 (NaOH Standardization).

3.4 Electrode Storage Solution (0.5 mol/L KCL) 3.4.1 Weigh out 37.275g +/- 0.1g anhydrous KCI. Add to a 1 L volumetric flask and bring to volume with deionized water.

3.4.2 Record shelf life as 3 months.

3.5 Standard Boric Acid Solution (NaOH Standardization), 1000 mg/L 3.5.1 Dissolve 5.7194 grams (5.7189 - 5.7199) of Boric Acid (H 3B0 3) with reagent grade water in a 1000 mL volumetric flask AND dilute to volume.

3.5.2 Record shelf life as 1 year.

3.5.3 Verify solution concentration per section 4.4 (QC Check/Sample Analysis).

3.6 QC Boric Acid Solution, 1000 mg/L 3.6.1 Use purchased 1000 mg/L Boric Acid Standard 3.6.2 Use manufacturer stated shelf life.

3.6.3 Obtain certificate of analysis (COA) from Fisher for each lot number.

3.7 QC Boric Acid Solution, 10 mg/L 3.7.1 Using a volumetric pipet and a volumetric flask, dilute 10 mL of the purchased Fisher standard to 1000 mL with deionized water.

3.7.2 Record shelf life as 1 month.

3.8 Mannitol

LM/O/P919 Page 6 of 6 3.9 Hydrochloric Acid (HCI), 0.0025N WARNING: Hydrochloric acid is corrosive. Level IiI PPE (labcoat, apron, safety glasses, gloves, faceshield or hood sash) is required when handling concentrated Hydrochloric Acid.

3.9.1 Add 250 p.L of concentrated HC1 to a 1000 mL volumetric flask partially filled with reagent grade water.

3.9.2 Dilute to volume with reagent grade water AND mix.

3.9.3 Record shelf life as 1 month.

NOTE:

1. It is NOT the intent of this procedure to perform the sections sequentially but to perform only those section(s) necessary to meet the need at the time.

2. During troubleshooting specific keystroke functions can deviate from this method in order to identify and correct instrument problems.

The programmed methods in the instrument are:

1. Probe Cal. (pH probe calibration)

2. Measure pH (pH 9 buffer check)

3. Blank (mannitol)

4. Boron NaOH Standardization (titer factor)

5. Boron (density corrected) (QC/Sample analysis)

4. Procedure 4.1 Initial Setup 4.1.1 Ensure power to titrator, balance, sample changer, and printer is on.

4.1.2 Ensure sufficient volume of sodium hydroxide and reagent grade water in reservoirs.

4.1.3 If needed, refer to Enclosure 6.1 (Sample Changer Manual Operation) to operate the sample changer in the manual mode at any time during the performance of this procedure 4.1.4 If needed, refer to Enclosure 6.2 (Sample Series Manipulations) to perform any of the following at any time during the performance of this procedure:

• Delete a sample from a sample series

• Add additional samples to end of sample series

• Insert an urgent sample into a sample series

• Add additional sample series to existing series.

K>

LM/O/P919 Page 7 of 7 4.2 Daily pH Electrode Standardization 4.2.1 Ensure electrode is clean.

4.2.2 Check filling solution level AND fill as necessary.

4.2.3 Ensure cap is not covering vent hole.

4.2.4 Using approximately 50 mL of each buffer, place cup of pH 7 buffer in 1st sample changer position, pH 10 buffer in 2nd position, and pH 9 buffer in 3 rd position.

4.2.5 Press or select the following in the order listed:

4.2.5.1

[Sample]

4.2.5.2

[F5] (Add) 4.2.5.3 Select "New Sample Series" 4.2.5.4

[F5] (OK) 4.2.5.5 Select "Number of Samples" 4.2.5.6

[2]

4.2.5.7 Scroll down and select "Method ID" 4.2.5.8

[1]

4.2.5.9

[F5] (OK) 4.2.5.10

[F5] (OK) 4.2.5.11

[F5] (OK) 4.2.5.12

[F5] (Add) 4.2.5.13 Select "New Sample Series" 4.2.5.14

[F5] (OK) 4.2.5.15 Select "Number of'Samples" 4.2.5.16

[1]

4.2.5.17 Scroll down and select "Method ID" 4.2.5.18

[2]

4.2.5.19

[F5] (OK) 4.2.5.20

[751 (OK) 4.2.5.21

[Run]

LMIO/P919 Page 8 of 8 4.2.5.22

[F5] (OK) 4.2.5.23

[F5] (START) 4.2.5.24

[F5] (OK)

NOTE:

Measurements will be made and calculations carried out automatically for the first two buffers.

4.2.6 After first sample series has completed and calibration results have printed, press

[Run] to continue to 2ud sample series (pH 9 buffer).

4.2.7 IF pH 9 buffer result is outside 9 +/- 0.1 pH units, THEN repeat Steps 4.2.4 - 4.2.7.

4.2.8 On a daily basis, record slope value in appropriate database or logsheet for instrument performance trending.

4.3 NaOH Burret Rinse:

4.3.1 Perform this section:

• When NaOH reservoir is refilled.

4.3.2 Stir NaOI-reservoir to thoroughly mix AND perform the following:

4.3.2.1 Place empty sample cup in 1st position of sample changer and refer to.1 (Sample Changer Manual Operation) to position electrode assembly in sample cup.

4.3.2.2 Perform the following to rinse buret:

A. Press [Burette]

B. Select "Dispense" C. Press [F5](OK)

D. Ensure the following are selected:

1. Burette drive 2

2.

Burette volume per volume of dispenser being used.

3.

Volume (mL) 100 for 20 mL dispenser or 50 (ml) for 10 mL dispenser E. Press [F5] (Start)

LM/O/P919 Page 9 of 9 1

<2 I NOTE:

The buret will rinse 5 times the volume of the dispenser.

4.3.2.3 Verify there are no air bubbles in the NaOH delivery line or tip.

4.3.2.4 IF air bubbles are present, repeat Steps 4.3.2.1 to 4.3.2.3.

4.4 NaOH Standardization 4.4.1 Perform this section:

"* Once per week OR prior to use, whichever is less frequent.

"* WHEN NaOH reservoir has been refilled and buret rinsed per Step 4.3.

4.4.2 Analyze a Blank as follows:

I NOTE:

= 5 grams of mannitol equates to 2 level teaspoons.

4.4.2.1 Place cup in Ist position of sample changer AND add 5 grams (4 - 6) of Mannitol to empty sample cup.

4.4.2.2 Press or select the following in the order listed:

A. [Sample]

B.

[F5] (Add)

C. Select "NewSample Series" D. [F5] (OK)

E. Select "Number of Samples" F.

[1]

G. Scroll down and select "Method ID" H. [3]

I.

[F5] (OK)

J.

[F5](OK)

K. [Run]

L.

[F5] (OK)

M. [F5] (START)

N. [F5] (OK) rf

<2'-

I I

I

LM/O/P919 Page 10 of 10 NOTE:

• The blank will run, results will be entered and printed out automatically.

0 A high blank value > 0.0300 mL will skew the results and should be verified by additional blank analysis by repeating Step 4.4.

4.4.3 Determination of titer factor with standard boric acid solution (1000 ppm) 4.4.3.1 Press or select the following-in the order listed:

A. [Sample]

B.

[F5] (Add)

C. Select "New Sample Series" D. [F5] (OK)

E. Select "Number of Samples" F.

[2]

G. Scroll down and select "Method ID" H. [4]

I.

[F51 (OK) 4.4.4 Place a sample cup on balance pan AND tare.

4.4.5 Transfer 20 g (18.0 - 22.0) of Standard Boric Acid Solution (NaOH Standardization) into sample cup.

4.4.6 When balance reading stabilizes, press [F4] (Balance).

4.4.7 Press [F5] (OK) twice 4.4.8 IF weight is accepted, select "Save Entry".

4.4.9 IF you choose to reweigh the sample select "Modify Entry" and repeat Steps 4.4.4 to 4.4.9.

4.4.10 Press [F5] (OK) 4.4.11 Place sample cup containing Standard Boric Acid Solution in sample changer.

LM/O/P919 Page 11 of 11 NOTE:

1. = 5 grams of mannitol equates to 2 level teaspoons.

2. Mannitol may be added at anytime once the sample has been placed in the sample changer prior to starting the analysis (Step 4.4.14).

4.4.12 Add = 5 grams (4 - 6) Mannitol to each sample cup.

4.4.13 Repeat Steps 4.4.4 to 4.4.12 once.

4.4.14 Press [Run]

4.4.15 Press [F5] (OK) 4.4.16 Press [F5] (START) 4.4.17 Press [F5] (OK)

NOTE:

Boric Acid Standard Solution will run, results will be entered and printed out automatically.

-4.4.18 Analyze a QC check per Step 4.5 (QC Check/Sample Analysis) to verify that the standardization is acceptable.

4.5 QC Check/Sample Analysis 4.5.1 IF analyzing samples containing borax with pH >6.4 (following post accident conditions), THEN adjust sample pH to 6.2 (6.0 - 6.4) using 0.0025N HC.

4.5.2 Select appropriate sample size:

Approximate Boron Concentration Approximate Sample Size (ppm)

(grams) 4.5.3 Press or select the following in 'the order listed:

4.5.3.1

[Sample]

4.5.3.2

[F5] (Add) 4.5.3.3 Select "New Sample Series" 4.5.3.4

[F5] (OK) 4.5.3.5 Select "Number of Samples" 0-500 25 500-2000 10 2000- 10,000 5

LM/O/P919 Page 12 of 12 4.5.3.6

[Enter number of samples in sample set, i.e. 6]

4.5.3.7 Scroll down and select "Method ID" 4.5.3.8

[5]

4.5.3.9

[F5] (OK) 4.5.4 IF entering sample ID is desired, press [A] to select "Sample ID" AND using the keyboard enter sample name, THEN press [v] to select "weight [g]".

4.5.5 Place sample cup on balance pan AND tare.

4.5.6 Transfer appropriate amount of sample into the sample cup AND weigh.

4.5.7 When balance reading stabilizes, press [F4] (Balance).

4.5.8 Press [F5] (OK) twice.

4.5.9 Place sample cup in sample changer.

NOTE:

1. = 5 grams of mannitol equates to 2 level teaspoons.

2.- Mannitol may be added at anytime once the sample has been placed in the sample changer prior to starting the analysis (Step 4.5.12).

4.5.10 Add = 5 grams (4 - 6) Mannitol to each sample cup.

4.5.11 IF analyzing more than one sample, THEN repeat Steps 4.5.4 - 4.5.10 for each additional sample.

4.5.12 Press [Run]

4.5.13 Press [F5] (OK) 4.5.14 Press [F5] (Start) 4.5.15 Press [15] (OK) 4.6 Instrument Standby 4.6.1 Place sample cup of conditionirg agent in last available position in sample changer.

4.6.2 Place red marker in hole next to sample cup of conditioning agent.

LM/O/P919 Page 13 of 13 NOTE:

The sample changer will recognize the marked sample cup as the last in the sample set and place the electrodes in it automatically.

4.7 Calculations NOTE:

These calculations are performed automatically by the instrument.

4.7.1 Boron Result 1

ppm Boron = Const x eight x V x Conc 10.811 g Boron Where:

Const -

mol -LBO3 leq / mol Weight = Sample weight in grams I

.V=mlx1 total buret vol (ml)

V = titrant consumption at the equivalence point in buret units.

Conc=

1 Weight Const Reag V

Conc = titrant concentration in milli-equivalents per buret volume 61.83 g I-IB30/

eq Const Reag -

00 1000 4.7.2 Density Correction

[B] mg/L = [B]

,glkg* (0.99707 + (1.96082E-6, [B] mgft))

Where:

1.96082E76 = factor based on linear regression of boric acid solution densities.

0.99707

= density of water at 25*C.

5. References 5.1 Mettler Toledo DL58 Titrator Reference Handbook.

5.2 Nuclear Generation Department Analytical Quality Control Program.

LM/O/P919 Page 14 of 14

6. Enclosures 6.1 Sample Changer Manual Operation 6.2 Sample Series Manipulations 6.3 Error Messages,Malfunctions, and Troubleshooting 6.4 Routine Maintenance for the DL-58

.1 Sample Changer Manual Operation

1. Change Lift Position LMIO/P919 Page 1 of 1 Press or select the following in the order listed:

1.1.1

[Changer] or [F1] (Esc) to return to/bring up sample changer menu.

1.1.2 Select "Change lift position" 1.1.3

[F5] (OK) 1.1.4

[F4] (Modify) to select "Top", "Bottom", or "Middle" 1.1.5

[F5] (Start) 1.1.6

[F1] (Esc) to return to menu.

2. Rotate Turntable 2.1 Press or select the following in the order listed:

2.1.1

[Changer] or [Fl] (Esc) to return to/bring up sample changer menu.

"~2. 1.2 Select "Rotate turntable" 2.1.3 2.1.4 2.1.5 2.1.6 2.1.7 2.1.8 2.1.9

[F5] (OK)

Select "Direction"

[F4] (Modify) to select "Forward" or "Backward" Select "Number of Positions

Enter the number of positions to move from the numeric keypad

[F51 (Start)

[F1] (Esc) to return to menu.

1.1 0

.1 LM/O/P919 Sample Changer Manual Operation Page 2 of 2

3. Rinse Electrodes with Demineralized Water 3.1 Press or select the following in the order listed:

3.1.1

[Changer] or [F1] (Esc) to return to/bring up sample changer menu.

3.1.2 Select "Dispense/rinse" 3.1.3

[F5] (OK) 3.1.4

[F4] (Modify) to select "Rinse" NOTE:

The "Dose" and "Dispense" options are not used.

3.1.5

[F5] (Start)

NOTE:

Water will rinse electrodes until [F5] is pressed again.

3.1.6 3.1.7

[F51 (Stop)

[F1] (Esc) to return to menu.

.2 LMIO/P919 Sample Series Manipulations Page 1 of 1

1. Delete a Sample from a Sample Series 1.1 Press or select the following in the order listed:

1.1.1

[Sample]

1.1.2 Select sample to be deleted 1.1.3

[F2] (Delete) 1.1.4

[OK].

1.2 Remove deleted sample from sample changer AND move any remaining samples forward one position.

1.3 Press [Run] to return to measured values screen.

2. Add Additional Samples to Sample Series 2.1 Press or select the following in the order listed:

2.1.1

[Sample]

-2.1.2 Select last sample in series 2.1.3

[15] (Add) 2.1.4 Select "Sample to Series" 2.1.5

[75] (OK).

2.2 Perform Steps 4.5.4 - 4.5.10 of the procedure.

2.3 Repeat Steps 2.1 - 2.2 for each additional sample.

2.4 Press [Runi

3. Insert an Urgent Sample into Sample Series NOTE:

Active sample will continue to run while adding urgent sample.

3.1 Press or select the following in the order listed:

3.1.1

[Sample]

3.1.2 Select active sample 3.1.3

[F5] (Add) 3.1.4 Select "Urgent sample"

.2 Sample Series Manipulations LM/O/P919 Page 2 of 2 3.1.5

[F5] (OK) 3.1.6 Select "Method ID" 3.1.7

[5]

3.1.8

[F5] (OK) 3.2 Repeat Steps 4.5.4 - 4.5.8 of the procedure.

3.3 Place sample cup in appropriate position in sample changer AND move remaining samples as needed.

3.4 Add = 5 grams (4 - 6) Mannitol to sample cup (equivalent to 2 level teaspoons).

3.5 When active sample completes and results print, press "Run" to start urgent sample.

3.6 When urgent sample completes and results print, press [F5] (OK) to continue with original sample series.

4. Add Additional Sample Series to Existing Series NOTE:

The last sample in the current series must be selected prior to adding the new series (1F5(Add)).

4.1 At anytime up to 2 additional sample series/methods may be loaded into the titrator program along with the current method being run. This can be accomplished as follows:

4.1.1 Refer to the section associated for the preferred method and perform as written:

"* Method 1 / Method 2 pH calibration / 9 Buffer check Section 4.2

"* Method 3 Blank Analysis Section 4.4.2

"* Method 4 Titer Factor Section 4.4.3

"* Method 5 QC/sample analysis Section 4.5 4.1.2 After each sample series is complete, press [Run] to start the next programmed series.

4.1.3 Repeat at 4.1.1 as desired as long as no more than 3 sample series are programmed to run at one time.

.3 Error Messages, Malfunctions and Troubleshooting

1. Malfunctions not reported by the DL-58 Titrator LM/O/P919 Page 1 of 1 Malfunction Potential Cause Action No display on titrator Titrator not connected to power supply Connect to power supply, if fault persists contact METTLER TOLEDO Service Several points of the display Contact METTLER TOLEDO missing Service Display does not match the Contact METTLER TOLEDO pressed key Service Stirrer does not rotate Stirrer not properly assembled or sensors Check stirrer and seating of the block it at the titration stand sensors Transfer error to attached Peripheral faulty or switched off Check attached device is peripheral functioning properly Device (printer, balance, Device not switched on Switch on device terminal) at Centronics or RC interface do not react Wrong settings Settings and configuration must Configuration (switch settings) wrong match (see Section 2.7)

Burette does not move to zero Burette drive faulty Contact METTLER TOLEDO position when switched on Senice Wrong potential or pH values Electrode faulty Check electrode (see electrode data sheet)

Calibration data wrong Check defined data "Use new electrode Faulty cable Replace cable No dispensing, the titrant is Burette tip clogged Clean burette tip discharged from stopcook or piston Follower cam on burette mounted Insert follower cam correctly wrongly (see Section 10.2.3)

.3 Error Messages, Malfunctions and Troubleshooting

2. Error Messages generated by the DL-58 Titrator LMIO/P919 Page 2 of 2 3.

Message Potential Problem Action EPROM or RAM Test Failed Memory is faulty Contact Staff or METTLER TOLEDO Support Internal Error Potential Hardware Failure has occurred Contact Staff or METTLER TOLEDO Support Memory Faulty Parts of User Memory is faulty Contact Staff or METTLER TOLEDO Support Faulty Data Deleted Stored Methods have been partially or Reload Methods manually or from totally deleted memory card Storage Not Possible Memory capability of processor has Notify Staff been exceeded Common Problems and Troubleshooting 3.1 Message Potential Problem Action pH 9 Buffer Out of Control Bad pH probe (more likely problem)

Replace probe Faulty cable Replace cable Observe jumpy pH readings Faulty cable (more likely problem)

Replace cable with NaOH additions Faulty probe Replace probe Insufficient stirring of mannitol Broke propeller blades on stirrer Replace stirrer Insufficient water dispensed Worn pump tubing Replace small tubing inside pump cover OOC QC and/or samples not

- any of above

- 3ee related action trending

- poor standardization

- recalibrate and/or restandardize

- air bubbles in NaOH dispensing line

- clear line of air bubbles

- clogged dispensing line

- check line & change if needed

- worn buret and/or piston (visible

- inspect, clean or rep'lace as needed leakage)

- noticeable temperature shift in lab

- write R005 for air handling problems and recalibrate &

standardize Sample Changer skips sample Sensor is dirty Clean Sample Changer and Sensor Reset Electronics by switching Electronics confused DL58 and Sample Changer OFF then back ON r

.3 LM/O/P919 Error Messages, Malfunctions Page 3 of 3 and Troubleshooting 32 IF normal troubleshooting within the shift fails to correct the problem, the instrument should be declared out-of-service and documented per the QC Program.

3.3 IF both titrators are declared out-of-service at the same point of time, actions shall be taken (i.e. reagent preparation) to be ready to perform a Manual Boron Analysis per LMIO/PO03C.

4

.4 LMIO/P919 Routine Maintenance for the DL-58 Page 1 of 1 K2 NOTE:

All daily, weekly, and monthly routine maintenance will be logged in the comments section of the Chemdesk QC Chart. Major maintenance activities will be logged in the Maintenance Log.

1. Weekly Maintenance 1.1 Check probe.

1.2 Change probe fill solution.

1.3 Empty NaOH dispensing line and refill (during buret flush).

1.4 Empty, rinse, and refill water container.

"2. Monthly Maintenance 2.1 Change drying tube.

2.2 Clean Titrator table.

2.3 Inspect stirrer arm.

2.4 Clean buret and piston.

3. Bi-Annual Maintenance 3.1 Change small tubing inside cover of water pump.