permit revision (minor) fpl-turkey point power plant ...0 jul 11 2001 fp ptn-lic-0 1-012 mr. allen...

0 JUL 11 2001 FP

PTN-LIC-0 1-012

Mr. Allen Hubbard Industrial Wastewater Section Florida Department of Environmental Protection 2600 Blair Stone Road Tallahassee, Florida 32399-2400

RE: Permit Revision (Minor) FPL-Turkey Point Power Plant Wastewater Permit FLO0O 1562 Request for use of Alternate Amines- Dimethylamine

Mr. Hubbard,

Part E, Section 8, of Wastewater Permit Number FL001562 for the Turkey Point Plant requires that Florida Power and Light Company (FPL) notify the Florida Department of Environmental Protection (FDEP), in writing, at least six months prior to the planned use and discharge of any chemical or other product(s) which may be toxic to aquatic life.

The purpose of this letter is to request a revision to Wastewater Facility Permit Number FLO0O 1562 to incorporate the test and use of Alternate Amines, Dimethylamine, in the Turkey Point Units 3 and 4 steam generators. The request for use and discharge of Dimethylamine is submitted as a Minor Revision to the Wastewater Permit. Attachment 1 provides the Dimethylamine Material Safety Data Sheet. Attachment 2 is the FPL-Turkey Point NuclearDimethylamine Fact Sheet. The notification information required by Part E, Section 8, of the Wastewater Permit is listed below and in the attachments to this letter as referenced. Attachment 4 is the FDEP Application to a Wastewater Facility or Activity Permit. Attachment 5 is the check for the associated application fee.

1. Name and general composition of the chemicals:

See attachment 1

2. Frequency of use:

DIMETHYLAMINE will be used on a continual basis at or below the dosing rates referenced on the FPL Fact Sheet. See attached FPL Fact Sheet- Attachment 2 and Engineering Evaluation- Attachment 3.

3. Quantities to be used:

DIMETHYLAMINE will be fed at a concentration of 10 - 25 parts per million for all affected systems.

4. Proposed discharge concentration:

Discharge of Dimethylamine from the Steam Generators should be authorized without limitation or monitoring requirements.

an FPL Group company

PTN-LIC-O1-012

5. Any acute and chronic toxicity data:

Reference MSDS sheets provided in attachment 1

6. Product data sheet:

See attachment 1

7. Product label:

See attachment 1

If you have any questions on this matter, or need any additional information, please contact Ms. Cindy Connelly at (305) 246-6841.

Sincerely,

R. J. Hovey Vice President Turkey Point Plant

SF

Attachments Attachment 1- MSDS for Dimethylamine Attachment 2- FPL Fact Sheet Attachment 3- FPL Engineering Evaluation Attachment 4- Application for a Minor Revision to a Wastewater Facility Permit Attachment 5- Check for a Minor Revision to a Wastewater Facility Permit

Bcc: Sean Fletcher P/S/ PTN James Berg CHEM/PTN Gabe Mendoza CHEM/ PTN Cindy Connelly CHEM/ PTN Al Gould JES/ JB Chuck Zyne PTN/ ENG PTN NPDES File

Attacflmeft 1* * - .. - -~ I L9S1 I U

MATERIAL SAFETY DATAViAqebtf4SM76 P. 04

SHEIET

PTN-LIC-01 -012 AN C W*"C 0 a P c a A Tr s c e

24 Howr Emergency Tejephone-(412)77780

P.O. Box 2346 Rftsixrgh PA 15230-1346

Section L. PRODUCr MDENTMFCA71ON

nROnUCr NAMIFh Pk*-Tect 9002HP

CHEMICAL DUESCRU'fON.- Aqueous amine solution PRQDUCr CLASS: Boiler water treatmwiet MW COME 0M6

Section 2. INFORMATION ON INGRDNS

CAS % by Gieniical Name Nubr Wei&b OSHA PEL ACC* TnV

DimtyI~uin (DMAj 124-4"- Z 7WA 10 ppm. IS IWA 5 ppm. 9.2 m~m3 gkn2 STEL 15

ppes, 27.6 mgfM3

Section 3. HAZARDS DEN-iIMCA77ON

***************** EMRG-ENCY OVERVIEW *~*******

DANGER May cause severe eye and skin damage. May be hannfiz! if swaflowed. M4ay cause aller&i sldn reaction. May cause respiratory tract unitation. Com~bustible liquid arnd vaporMay form suspected cancer-causing Witiosaminin if ma-zed with nitrites.

PRIMARY ROUIES OF ENTRY: Eye and skinx cmtact, inhalation, skidn absorption, ingestion

TARGET ORGANS: Eye, sidn, Iunn& mucous membranes, liver

MEENCAL Q2N=fIONS AGGrAVATED BY EXPOSURE:

*Skin disorders and affergies *(3uronic respiratory diseas. e.g., bronchitis, emphysema *Eye disease

MSDS Code: 0P64 Issue lDate- 0516-9%

Page I Continued on Page 2

L... a ib-1Vt- M1a44J 41 -mmI UliLmI VWLKA Lid"i Fi- T 1879386 P8

MATERIAL SAFETY DATA SHEET

POTENTLAL HEALTHI mEPICr:

EYE CONTACT: This priduct may Cure ireveruble eye damage upon contact depending ca the length of expsa'e, solution concentration and flist aid measures. Product vapor in low concentafloms can cause tearing, connctvi and ccruta edema when absorbed into the tisu o the eye fom the atmosphere. Cameal edema may give rise to a perception of "blue haze- o. ,,ogr around lights. The condition is transient and has no known residual effect.

SN CONTACr: This product may produce burns upon contact with the skin. The severity of the burn is generally deiermined by the concentration of the solution and the duration of the exposure. The vapow may also be inating to the skin. DMA may cause an allergic skin reaction and may be absorbed through the skin causing nausea, headache, and genezal discomfort.

INGESION: Ingestion of this product may cause severe irritation or brum of the mucous mnebganes of the mouth, thuvat, esophagu and stomach.

INHALATlON: DMA vapors am irritating to the respiratory tract, Inhalation of vapors may produce chemical pAeumna, pulmonary edema, and delayed scarring of the arway, and other affected Organs. pepeated and/or prolonged exposwe to vapors may cause dcronic iritation of the respiratory tract, trinchopneuuinia, and other adverse respiratory effects such as cough, tightsm= of chcast, or shostmss Of breadIL

SVBCHRONMC, C-RONIM: DMA added to the diet of rats at 1M) mg/kg for 3.5 months increased liver demethylase activity even in the presence of the enzyme inducer casein. In a subchronic study, 15 rats, 15 guinea pigs, 3 rabbits, 2 dogs, and 3 monkeys were exposed continuously by halation at approximately 5 ppm of DMA for 90 days. There were no deaths or signs of toodcity and all hematologic values were normal. On listopathologic examination, inte stitWal inflamnatory Changes were noted in the kMps of each Speces. Further, the 3 rabts and 2 monkeys showed diataion of the bronchi

In a 2-year inhalation study, groups of 95 male and 95 female rats and mice were exposed 6 hoIrsday, 5 days/week at 20, 5D, or 175 ppm of DMA. Concentration-dependent toxicity was Iharatetrized by decased body weight (175 ppm only) and progressive tory, degenerative, and hyperplastic lesions of the nasal passages. Nasal toxicity was similar in both rats and mice (no sex differences) affecting respiratory and olfactory epidulia. Lesions were severe at 175 ppm, moderate at 50 ppm, and focal and mild at 10 ppm.

CARCINOGENCrY: N TP:

"No ingredients Usted in this section"

"No ingredients listed in this sectionOSHAM

"No ingredients listed in this Section"

Section 4. FIRST AID MEASURES

EYE CONTACT: In case of cotact, immediately flush eyes with plenty of water for at least 15 minutes. Seek medical aid immediately.

NEDS Code: WF64 Page 2 issue Date: 05-16-95 Continued on Page 3

TO 914076943706 P. 05

7-> WV t-t ERn IA-L.Xf MUMM LtYU- DATA JU 914076943706 MATERIAL SAFETY DATA SH{EET.

P.06

SKIN CONTACT: In case of conact, immediately flush skin with plenty of water for at least IS minutes while removing contaminated dothing ard shoes. Seek medical aid immediately. Wash dohuing before reuse. Destroy contaminated leather apparel. Victims with major skin contact should be maintained under medical obseration fir at least 24 hours due to the possibility of delayed reaction.

iNGES"ION: If swallowed, do NOT induce vomiting. Give large quantities of water. Seek mau-."a .d ty. Never give anything by mouth to an uncoascious perso.

Note to Fhysidan This Ixrduct is hk , inju s to aU tissues, similar to that of ammonia or ammonia gas. Ceical pneumonifis. pulmonary edema, lryngeal edema and delayed scarring of the airway at ottw affected tissues =ay occur following e .osure There is no specs& treatuen Cinical management is based on spportive treatment, which is similar to that for theral bua s.

INHA•AITON: If inhaled, remove to fiesh air. If not breathLng, give artificial respiratior. If breathing is diffcoilt. give oxy=g. Seek medical aidL Ptevent aspiatmin of vawni Turn victim's head to the side. Assure mucous does not obstruct airway.

Section 5. FERE-FIGHTING MEASURES

HFASH FOINfl: 27-F (COc) This product is a combustible liquid.

LOWER FLAMM"AMBL IT: Not ava-lable UPFER FLAMMABLE LIMIT. Not avaijabe

AUTO-IGNIMION ITEERAUMRE Not available

E)CINGUISHING MED[A. Use CO2, dry chmical, alcoW foam.

FIR-FIGHTING INSTRUCU1ONS:

FIRE & EXPLOSION HAZARDS:

Exercise caution when fghting any dcemical fie. A self-contained breathing apparatus and protective dothng are essential. Use water to keep fire-egpsed containew cooL

Product emits toxic gases under fire conditions. Product vapors ame heavier than air and may travel a considerable distance to a source of ignition and flash back. Vapors may collect in dosed spaes such as sewers, caves or dosed strctures.

DECOPOSITION PRODUCMh: Upon d pcomPtion, ammonmia vapO are liberated. Upon combustion in the presence of sufficient oxyge product generates harmfu carbon monoxide, carbon dioxide, and nitrogen oxide gases. Niftoge oxide can read with water vapor to yield nitric add. Combwsti of product under oxygen-starved coanditioas can be ea•pected to produce numerous toxic products induding nitriles, cyanic acid. isocyanates, cyanogens, nitosamines, amides, carbamates.

NFPA RATMNGS: Health = 3 Fammality - 2 Reactivity = 0 Special Hazard = None

Hazard rating scale 0-- flnmal 1- Sight 2- Modeute 3= Seriogs 4= Severe

MUMSu Date: 0-6Issue Date: 05-16-95

Page 3 Continued on Page 4

= k d4e 1rtd_.l -• LJj21J rUA •tI ' I U 48 9 7 P 7


Section 6. ACCIDENTAL RELEASE MEASURES

STEPS TO BE TAKEN IF MAMMIAL IS RELEASED OR SP.LED: Ventilate area of spill. Eliminate all gition soue. Appmach release fix= upwind. Use water spray to coal and disperse vapow, prutw

pezronrel, and dilute spills to fom nonflammable mixtures. Five percent sulfiuc add may be used to meutmlike diluted pocir. Weain appoprWe personal protective equipment, contain piM. 3aiect onto

csVAlMbuStWe absorbent ilk sand or earth and place into suitable coanu-er. Vapoms tend to zremain doae to the gpound and collect in out-of-the-way place. Use =xi-sparklng blowers ar venwation faclies to rmove potential expladve or toodc aamimulations.

Section 7. HANDLING AND STORAGE

HANTEMQ

SroRAME

Do not get in eyes an 46 or clothing. Avoid breathing vapor or mdsL Keep away ftam heat and fame. Use with adequate ventilaton. Wash thaotrogy after hanclng. Keep containmer dosed when not in use. Remove all equipment .dc hi may be a source of ignition from viciity whlle handling. Empty cantainers may contain erplosive vapors. Flush empty antainers with water to remove residual flamunable liquid and vapors.

Keep away from oxidizes, heat or flames. Store away from ignition souce. Ground all containers during transfer. Store in steel containers preferably located outdoors, above round, and surrounded by dike to contain spils or leaks. Electrical installafion should be

in accordance with Article 50 of the Natina Electrical Code for Class I Diviiou 2 locations.

Section L EXPOSURE CONTROLS I PERSONAL PROTECTION

PERSONAL PROTECIE EQU2MMqr.

EY•/FACE PROTEClONM Chemical splash goggles and face shield SK • O'E-ION: ChemiW resistant gloves and protective clothing RESPMATORY PROTECTION: If airborne concentrations exceed published eacmne limits, use a NIOSH

approved respirtor in accordance with OSHA respiratory protection requirements (29 CFR 1910.134).

MMN N CONTROLM. Loeal ehaust ventilatkm may be required in addition to general room ventation to maintain airbone concentrations below exposure limits.

WORK MRAC=l•. Eye wash station and safety shower should be accessible in the immediate area of use.

UNSA WISFACTORY MATERIALS OF CONSIXUCTION: DMA corrodes copper, aluminum, zin, and galvanized surace.

MSDS Codc OF" Issue Date. 0S-16-95

Page 4 Continued oan Page 5

914076943786 P. 07

LA 1i.. 0i6-1995 09: 42 FROJM CAU30N POWaER GROLP P6-I TO 91407643706 P.0


Section 9. PHYSICAL AND CHEMICAL PRORTS

BOILNG POINT: Not available SOLUBILITY IN WATER: Complete

VAPOR PRESSURE: 2 twr 0 10'C (for DMA) SPEOFC GRAMY:- N~ot available

VAPOR DENSIIY (air- IN IM5 (far DMA) pmH Basic

%VOIATIRE BY WEIGHT:- 200 FREEZING POINT: Not avaflable

APPE~ARANCE AND ODO1R Clear, colorless liquid with ammon-iacalm*shy odor~.

Section 10. STABILrTY AND REAC11VITY

CHENvUCAL STAEI1flY:- Stable HAZARDOUS POLYMEPIULATION: WMl zmt oaz

CONtDMON TO AVOII)h. Keep away hrow heat and flame.

IKOMPAU~ul]MM: Strong oxidizers, add~s, copper, aluminumt, zinc and galvanized surfaces.

DECOWOSU1ON PRODUCrS: Upon decomposition, ammonia. vapors are liberated. upon conbustiaa in the presence of suffident axygez product gemetates harmfU carbon mmoloide, carbon dioxide, and nitrogen oxide gases. Nitragen oxide can, react with wrater vapor to yield nrdic acdd. Con-bustion of product under oxygen-starved cocuditions can be expected to produce inumrznco toxic products induding niftiles, cyanic add, isocyanates, cyanogens, nitrosamines, arnids carbamates.

Section 11. TOXICOLOGICAL INFORM7TION

ON PRODUCr: See the following infoxiration on avctv ingredient.

ON INGREDIENTS:

CeiaNaeOral 11)50 Dermul LD~o inhalaton WA~ CeiaNae(rat) (rabbit) (rt Dimethylamine (DMA) as8 rngI)g Not awilable 454 pn26

Section 22- ECOLOGICAL INFORMATION

ON FRODUCr:Aqualic taxidty dafta on a 10% asduton of DMA: 48 liw LC~ (Daphntia masna)-: 675 ppm 961hr LC4 (fathead ainnow): > 1000 ppm 96 hr LJC~o (bluegill sunfish): > 1000 ppma

Aqua&i toxicity data an a 2% sollutia of DMA: 7-day NOEC (Ceziodaphnia dulia): 1000 ppm (for survval and reproduction)

MSDS Code: OF64 Issue Date. 05-16-95 Page 5

Confirmed an Page 6

l.A. a-~-i TJ;4. t-*411 CRLji-"' I-IJAR= Ui4.V P M- 1479376 P

MATERIAL. SAFETY DATA SHEET

Section 13. DISPOSAL CONSIDERATIONS

RCRA STATUS: The EPA Hazardous Waste Number is U092.

DISPOSAL: Dispose Of in, aamdance with local, state and federal regulations. lnmatian is acceptue and the prefered method of ispMaL However, nitrogen o-r. i edssion controls may be required to meet Stons. Ch andw bological dkerAdation is feasible. A sitable industra o munidpal waste treameint system cn be used depending on the quality and quantity of waste to be treated, the treatment plant capabMt, and d5scbArge water quality standards. Ininerate in an open ntainer. Do not dump into mundpal sewen o encoed drains tUt prcsent a fire cc exposion hazard.

Section 14. TRANSPORT INFORMATION

DOT CLASSIFICAMTON: aassiD Msiu 3 Proper Shipping Name: FLmmable liquid, coarsive. ums. (Dimethylauine) Label: Flammable iquid C ve Packng Group: m ED Number. UN 2924

Section 15. REGULATORY NFORMATION

OSHiA Hazard Conumsn1cati Status: HFazardous . CA: The ingredients of this product are risted on the Toxic Substances Contrl Act CTSCA) Oemical

"* Substanm -. CERQA reportable quantity of EPA hazardous substamces in product:

Chende Name Methylamine (DMA) 100D lb

Product RQ: 50,000 lb (Notify EPA of product spill exeedin t0s amounL)

SARA MfMLE IU

Seaie. 302 Exremely Hazardous Substance=

aremicad Name CAS 9 TPO "N ingredens listed in this section"

Seddo 311 and 312 Health and FhyxiLaW Hazardsm Immediate, Delayed Fire Pressure Reactivity

(yes] [yes] [yes] (nol [no)

Section 313 Toe~ Chemicals:

C ical Nme CAS# % by Weight Dimthylamine (DMA) .24.40-3 2

MSDS Code:. F64 Page 6 Issue Date: 05-16-95 Continued on Page 7

9140'76943706 P. 09

OCT-06-1995 09:43 FI~11 CRLGN POWaER GROLP PG-I TO 914876943766 P. 10 LkL JLJMItEUAL bA1rkl1Y IJATJLA SHELU±

Secton 16. 0O7-UR INFOMATION

HLOS RA11CSc Health. 3- fiamnmability -2 Rteactmviy ý-0 Piwn Fotectiv Equipment - X (to be specified by user depending an use concaitons)

Mwhee we pokcutiai duwnic health effects to cnider.

Hazad rating SWCa 0- Ifinim~al I - SNigh 2w Moderate 3 - Serious 4 =Sowjm

MSDS REVMOPI SUMMARY: Superses MSDS issued an 9-21-n4 The LM S has been changed in Section

ibit ths i f~gIon -am set forlb hwe'en are bet jevu CO he lc~w at as of thle date hereof, CAOL CQPOSATI9 FAKES NO UARRANTT VIT1 RESPECT NEREO AM0 DISCLAIMS ALL LIABILITT FRW RELIANC THEN=.

PREARED BY: P.3. Maloney

m5TUj LOGC U Issue Date: 05-16-%S Page 7"

Last Page

TO3TAt P. 10

Attachment 2 PTN-LIC-01-012

FPL -Turkey Point Nuclear Plant- Dimethylamine Fact sheet

1. Dimethylamine (DMA) in an aqueous solution of a modified amino compound.

2. The expected dosing rates of DMA during wet lay-up are 15 to 25 PPM. During normal operation the expected dosing rates of DMA will be 10 to 15 PPM.

3. At the end of a refueling outage the steam generators, or a portion thereof, that contain 25 PPM DMA will be drained to the Turkey Point Cooling canals (these canals are not classified as waters of the United States). Each of the three steam generators contains approximately 26,000 gallons of water that is released at a rate of approximately 225 gpm. This blowdown is mixed with the effluent from the circulating water pump (156,000 gpm).

225gpm (Blowdown Flow) x 25ppm (DMA Concentration) /156,000 gpm = 0.03 6 PPM of DMA.

Please note that this calculation is conservative as there are actually four (4) circulating water pumps providing dilution and there should be little or no DMA present in the discharge.

4. Comparison of Aquatic Toxicity (from MSDS sheets)

Organism DMA LC50

Daphnia magna 675 PPM

Fathead minnow >1000 PPM

Bluegill sunfish >1000 PPM

5. A major decomposition product of DMA is ammonia. Ammonia is already in the steam generator blowdown stream.

A-uacrimeni %j PTN-LIC-01 -012

Nuclear Safety Evaluation Review And Approval

SE Number: PTN-ENG-SEMS-01-0025 REV.0

SE Title: ADDITION OF ALTERNATE AMINES TO THE

SECONDARY SIDE SYSTEM.

The following plant departments/groups have reviewed the Safety Evaluation:

Department Name Comments Lic Yes, [ NoD 1 , Ops Yes No Maint Yes E No 0 QA Yes [ No [I

CHEMISTRY Yes I No 0 Yes NolQ Yes 0 No Yes 0 NoO

Note: A yes to Comments requires that the comments be attached

~4/4 I t(

Potential corrective actions identified in review: -a 44 41

PNSC Review:

Vice--C-imrn= Signature PNSC Number

r •Jlvx rlJpiuvaA, / I/Sigatiure 'Date

Compensatory/Corrective actions transmitted to PMAI Coordinator:

Signature Date

O riinp tr n m te 9 e D c mnt Control:

Signature Date

- a-r, ý, .

S-k/l/V l5ate'

a Inter-Office Correspondence

IPL PTN-ENG-01-0126

To: R. J. Earl Date: May 10, 2001

From: D. J. Tomaszewski Department: PTN Engineering

Subject: Turkey Point Units 3 & 4 Safety Evaluation PTN-ENG-SEMS-01-0025, Rev. 0 TITLE Addition of Alternate Amines to the Secondary Side System

Reference: P.O. 00048457 (PR 130815)

Attached please find:

Draft package for {) Minimum Quorum OR { } IR-OR review

[X ] Final package (Safety Evaluation)

This Safety Evaluation is categorized as follows:

Top 20 '98 Unit 3 Refueling Outage List

[1 ] Top 20 '99 Unit 4 Refueling Outage List

[ ] Top 30 Modifications List

Minor Scope REA (0-ADM-510)

[X] Emergent work

[ ] Drawing Change

This Safety Evaluation provides for additional alternate amines to be used within the secondary system to

further minimize corrosive environments.

Should you have any questions or comments, please contact Chuck Zyne at extension 6174

PTN Engineering Manager

DJT/WAS~t~msd:

Attachment: PTN-ENG-SEMS-01-0025, Revision 0 Westinghouse SECL 00-174, Rev. 1

cc: S. Boling J. Manso

FLORIDA POWER & LIGHT CO.

TURKEY POINT UNITS 3 & 4

SAFETY EVALUATION

FOR

ADDITION OF ALTERNATE SECONDARY SIDE

AMINES TO THE SYSTEM

PTN-ENG-SEMS-O1-0025

REVISION 0

SAFETY RELATED

PTN-ENG-SEMS-01-0025 Revision 0 Page 2 of 7

REVIEW AND APPROVAL RECORD

PLANT Turkey Point UNIT 3 & 4

TITLE Safety Evaluation for Addition of Alternate Amines to the Secondary Side System

LEAD DISCIPLINE Mechanical Engineerin2

ENGINEERING ORGANIZATION Turkey Point Site Engineering

REVIEW/APPROVAL:

INTERFACE TYPE GROUP PREPARED VERIFIED APPROVED FPL APPROVED*

INPUT REVIEW N/A

MECH X 9

ELECT X /I / N/A

I&C X N/A N/A N/A N/A

CIVIL X N/A N/A N/A N/A

DSN BASIS- X N/A N/A NIA

CSI X N/A N/A N/A N/A

NUC FUEL X N/A N/A N/A N/A

SYS ENG X N/A N/A N/A N/A

* For Contractor Evals As Determined By Projects "Review Interface As A Min On All 10CFR50.59 Evals and PLAs

FPL PROJECTS APPROVAL- ý , ýA/'DATE:5//OIO/

OTHER INTERFACES

Westinghouse, Siemens Corporation and PTN Chemistry Dept.

G: \JPN


Table of Contents

A bstract ..................................................................................................... 4

1.0 Description and Purpose ........................................................................ 4

2.0 License Requirements ........................................................................... 4

3.0 Analysis of Effects on Safety ................................................................ 5

4.0 Failure Mode and Effects Analysis .......................................................... 5

5.0 Plant Restrictions ................................................................................... 5

6.0 Effect on Technical Specifications .......................................................... 6

7.0 Unreviewed Safety Question Determination .............................................. 6

8.0 Actions Required ................................................................................. 6

9.0 Verification Statement ......................................................................... 6

10.0 References .......................................................................................... 7

11.0 Affected Documents ............................................................................ 7

ATTACHMENTS

1) Westinghouse Safety Evaluation, SECL 00-174, Rev. 1, 14 Pages

2) E-Mail Correspondence from Siemens Corp. (Frank Baldino) to PTN Engineering

(C. Zyne), dated 4/30/01, 2 Pages

PTN-ENG-SEMS-01-0025 Revision 0

Page 4 of 7

Abstract

The purpose of this safety evaluation is to assess the addition of a combination of

alternate amines into the secondary water system at Turkey Point Units 3 and 4.

The use of alternate amines, including ethanolamine (ETA), dimethylamine (DMA),

methoxypropylamine (MPA), and morpholine, has been proposed for use in the

secondary systems and has been reviewed with respect to the other existing

secondary side chemical control agents, specifically hydrazine, carbohydrazide, and

ammonium hydroxide. This evaluation supports the conclusion that the addition of a

combination of alternate amines, with or without boric acid addition does not

represent an unreviewed safety question as defined in 10 CFR 50.59(a)(2).

No FSAR Change Package has been provided within this evaluation since the

affected FSAR section has already been revised via Revision 17 (see Section 2.0

below).

1.0 DESCRIPTION AND PURPOSE

The purpose of this evaluation is to assess the addition of (DMA), (MPA), or

morpholine in the secondary systems of the Turkey Point Units 3 and 4. This

evaluation covers the addition of the alternate amines either alone or in combination

with each other with respect to the balance of secondary side chemical control

agents, specifically ETA, hydrazine, carbohydrazide, and ammonium hydroxide.

The proposed addition of alternate amines to the secondary side systems is evaluated

against the 10 CFR 50.59 criteria to determine if these changes constitute an

unreviewed safety question.

This evaluation is classified as Safety Related since it impacts the safety related

steam generators.

2.0 LICENSE REQUIREMENTS

UFSAR and Technical Specifications applicable excerpts:

UFSAR:

Section 10.2.4.1 discusses chemical addition as part of a corrosion protection

program. Therefore, no changes are required.

Technical Specifications:

There is no impact to the Technical Specification.

PTN-ENG-SEMS-01 -0025 Revision 0

Page 5 of 7

3.0 Analysis of Effects on Safety

In summary, the proposed use of additional alternate amines to the secondary side

systems will not adversely impact the existing secondary side chemistry regime at

Turkey Point Units 3 and 4. Therefore, there is no likely adverse impact to safety systems.

4.0 Failure Mode and Effects Analysis

As per review of the attached Westinghouse evaluation (see Attachment #1), the

introduction of additional alternate amines will not create any new failure modes

within the power plant. As a result of Siemens Corporation's recent acquisition of

Westinghouse's turbine division, Siemens technical and chemistry representatives

were contacted to determine if the use of the alternate amines described in this

evaluation would increase turbine metal corrosion. They had confirmed that no likely

turbine corrosion would occur as a result of the use of these chemicals in its

prescribed concentrations and while combined with other approved chemicals (see

Attachment #2). The Siemens Chemistry Rep. did have concerns with potential rising

cation conductivity levels, which occurs when alternate amines decompose to

organic acids. The Rep. indicated that PTN may be required to operate the

condensate polishers continuously to maintain our secondary system cation

conductivity within the recommended limits. PTN Chemistry Staff will not use

concentrations of DMA that would raise the cation conductivity above current limits.

Therefore, the current operation of the condensate polishers only during startup may

be maintained.

Section 3.0 of the Westinghouse Evaluation discusses the PTN chemistry control

program utilizing 150-200 ppb hydrazine, however, the Chemistry Dept. has

indicated that this concentration has been reduced to a current value of 100-120 ppb

hydrazine. This reduced hydrazine concentration, combined with identified amines,

does not minimize the capability of reducing iron transport on the secondary side.

Hydrazine concentrations at PTN will continue to be reduced as other previously

approved amines, including the amines discussed within this evaluation are

introduced in the secondary system.

5.0 Plant Restrictions

There are no plant design or operating mode restrictions associated with the

introduction of additional alternate amines for secondary side system chemistry

control.


6.0 Effect on Technical Specifications

The proposed introduction of additional alternate amines for secondary side system

chemistry control changes does not affect the Technical Specification. Additionally,

a review of the impacts of use of the noted alternate amines has determined that

no change to the Technical Specification is required. This evaluation has no effect

on the Fire Protection Program (FPP) and is not associated with any action defined

by the ODCM. The use of the noted alternate amines could impact the

Environmental Protection Program (EPP), therefore an assessment of that impact

would be addressed by a separate document (see Section 8.0, Action Items).

7.0 Unreviewed Safety Question Determination

As per the attached Westinghouse safety evaluation, the "Assessment of

Unreviewed Safety Question" section concluded that the use of the noted alternate

amines do not involve an unreviewed safety question and may be implemented

without prior approval of the NRC.

Conclusion

The use of alternate amines as noted in the attached safety evaluation within the

secondary systems for Turkey Point Nuclear Plant Units 3 and 4 does not impact safe

operation of the plant, constitute an unreviewed safety question or require a change

to the Turkey Point Technical Specifications. Therefore, this activity does not require

prior NRC approval.

8.0 Action Items

1. Chemistry shall revise the Nuclear Chemistry Parameters Manual to incorporate

the use of the noted chemicals (and respective limits), as required, within the

secondary system. Chemistry shall also revise current chemistry procedures to

include the use and application of the approved alternate amines.

2. Site Environmental Group shall revise the site Environmental Permit for the use

of noted alternate amines.

3. Site Environmental Group shall provide the NRC a copy of the revised site

Environmental Permit.

9.0 Verification Statement

The design bases were reviewed against the Technical Specifications, DBD, UFSAR,

10 CFR 50, Engineering Ql's, TQAR and Nuclear Industry Reference Guides to ensure

that the evaluation considers all applicable codes, standards and regulatory

requirements, and that design interfaces were properly assigned. The codes,

standards, design bases and regulatory requirements are properly identified. The

PTN-ENG-SEMS-01 -0025 Revision 0 Page 7 of 7

assumptions and inputs used to perform this evaluation are adequately described,

reasonable and appropriately identified for subsequent reverification.

The analysis was independently verified by review of the inputs utilized. Methodology

is appropriate and applied correctly. The output provided by this evaluation is

reasonable when compared to the inputs. The acceptance criteria are adequately

documented to allow verification that the regulatory requirements have been

satisfactorily accomplished. The rationale provided in assigning the Safety

Classification was verified against the requirements of Engineering QI 2.6, Safety

Classifications. It was correctly concluded that this evaluation shall be classified as

Safety Related.

10.0 References

1. Updated Final Safety Analysis Report, electronic version (Lotus Notes) updated through 5/8/01

2. Turkey Point Technical Specifications, Amendment 211/205, dated 1/31/01

3. ENG-QI 2.6, Safety Classifications, Rev. 1, dated 8/31/97

4. Westinghouse SECL 00-174, Revision 1

11.0 Affected Documents

Nuclear Chemistry Parameters Manual

Attachments

1) Westinghouse Safety Evaluation, SECL 00-174, Rev. 1, 14 Pages

2) E-Mail Correspondence from Siemens Corp. (Frank Baldino) to PTN Engineering

(C. Zyne), dated 4/30/01, 2 Pages

Attachment to FPL-01-1 15 SECL 00-174, Revision I Page 1 of 14

Attachment I to ýPTJ-E! 6ý - S .i -01-00-2) 2",o. o Customer Reference No(s)

Page. of Hq Westinghouse Reference No(s).

WESTINGHOUSE

SAFETY EVALUATION CHECK LIST

1) NUCLEAR PLANT(S): Turkey Point Units 3 and 4

2) CHECK LIST APPLICABLE TO: Addition of Alternate Amines to the Secondary Side System

3) The written safety evaluation of the revised procedure, design change or modification required by 10

CFR 50.59 has been prepared to the extent required and is attached. If a safety evaluation is not

required or is incomplete for any reason, explain on Page 2. Parts A and B of this Safety Evaluation

Check List are to be completed only on the basis of the safety evaluation performed.

CHECK LIST - PART A

Yes X Yes Yes Yes

No___ No X No X NoX

"A change to the plant as described in the FSAR? "A change to procedures as described in the FSAR? "A test or experiment not described in the FSAR? "A change to the plant technical specifications (Appendix A to the Operating License)?

4) CHECK LIST - PART B (Justification for Part B answers must be included on page 2.)

4.1) Yes_ No X

4.2) Yes_ NoX

4.3) Yes NoX

4.4) Yes_ No X

4.5) Yes_ No X

4.6) Yes_ NoX

4.7) Yes_ No X

Will the probability of an accident previously evaluated in the FSAR be increased?Will the consequences of an accident previously evaluated in the FSAR be increased? May the possibility of an accident which is different than any already evaluated in the FSAR be created? Will the probability of a malfunction of equipment important to safety

previously evaluated in the FSAR be increased?

Will the consequences of a malfunction of equipment important to safety previously evaluated in the FSAR be increased? May the possibility of a malfunction of equipment important to safety

different than any already evaluated in the FSAR be created?

Will the margin of safety as defined in the bases to any technical specification be reduced?

3.1) 3.2) 3.3) 3.4)

AttachdW i to - -P-0 - - •. SECL 00-174, Revision 1

Page 2.- ofjjj. Page 2 of 14

If the answer to any of the above questions is unknown, indicate under 5.) REMARKS and explain below.

If the answer to question 3.4 (Part A) or any of the questions in Part B cannot be answered in the negative, based on written safety evaluation, the change review would require an application for license amendment as required by 10 CFR 50.59(c) and submitted to the NRC pursuant to 10CFR50.90.

5) REMARKS:

The answers given in Section 3, Part A, and Section 4, Part B, of the Safety Evaluation Checklist, are based on the attached Safety Evaluation.

FOR FSAR UPDATE

Section: 10.2.4.1 Pages: 10.2.8 Tables: N/A Figures: N/A

Reason for / Description of Change:

Revise Subsection 10.2.4.1 as follows:

Ammonium Hydroxide or an alternate amine is added to the condensate at the pump discharge to control pH. Hydrazine is also added to control oxygen.

SAFETY EVALUATION APPROVAL LADDER

Prepared by: _ _ _ _ _ _ _

Regulatory and Licensing Engineering D. A. Lindgren

Reviewed by: Regulatory and Licensing Engineering/

Date: 2Z-/. •

77C-ý--

Reviewed by: , tv 'r-L '? r c.,

Chemistry Diagnostics & Materials Engineering Thomas B. Wright

Reviewed by: Z7-1- D ePA )Dae

Date:F)J-

Reviewed by: Date:

SAi chment 'to

c- _o•-SECL 00-174, Revision I

Page 3 of j 0 Page 3of4

TURKEY POINT UNITS 3 AND 4 ADDITION OF ALTERNATE AMINES TO THE SECONDARY SIDE SYSTEM

SAFETY EVALUATION

1.0 INTRODUCTION

Site-specific chemistry programs are established to provide a chemical approach for minimizing corrosion damage and performance losses in the secondary water system. The use of alternate amines, including ethanolamine (ETA), dimethylamine (DMA), methoxypropylamine (MPA), and morpholine, has been proposed for use in the secondary systems at Turkey Point Nuclear Plant Units 3 and 4. These combinations will be reviewed with respect to the other existing secondary side chemical control agents, specifically hydrazine, carbohydrazide, and ammonium hydroxide. The alternate amines may be used with and without the addition of boric acid to the Westinghouse Model 44F steam generators.

The purpose of this evaluation (Reference 7) is to assess the addition of a combination of alternate amines, demonstrating that plant operation following the change will not be adversely affected. This evaluation will demonstrate that operation of the steam generators with alternate amines, will not have an adverse effect on the pressure boundary integrity or function of the steam generator and the secondary systems (feedwater, steam and condensate systems). This evaluation supports the conclusion that the addition of a combination of alternate amines, with or without boric acid addition does not represent an unreviewed safety question as defined in 10 CFR 50.59(a)(2). This secondary chemistry change will not involve a change to plant Technical Specifications. Therefore, this change may be implemented without prior NR-C approval.

2.0 LICENSING BASIS AND SCOPE

Title 10 of the Code of Federal Regulations, Part 50, Section 59 (10 CFR 50.59) allows the holder of a license, authorizing operation of a nuclear power facility, the capacity to investigate and disposition a change to the normal plant configuration. The proposed chemistry represents a change to the normal plant configuration. Prior Nuclear Regulatory Commission (NRC) approval is not required to implement a change provided that the proposed change does not involve an unreviewed safety question or result in a change to the plant technical specifications. However, it is the obligation of the licensee to maintain a record of the changes or modifications to the facility, to the extent that such changes impact the Updated Final Safety Analysis Report (UFSAR). The code further stipulates that these records shall include a written safety evaluation that provides the basis for the determination that the change does not involve an unreviewed safety question.

The addition of ETA and/or MPA, with or without boric acid addition to the secondary system does require a change to Section 10.2.4.1 ("Chemical Addition") of the UFSAR, but does not impact the plant Technical Specifications or constitute an unreviewed safety question. As a minimum the UFSAR must to revised to refer to more than one alternate amine and must include the use of boric acid if such is determined to be necessary. This evaluation documents the bases for the determination that the addition of an alternate amine with or without boric acid addition to the secondary system at Turkey Point Units 3 and 4 does not represent an unreviewed safety question.

Attachment to -'N• - E-N C--C m -o I -0- L• 0. SECL 00-174, Revision 1

Page jq of H Page 4 of 14

3.0 EVALUATION

This safety evaluation is written to allow Turkey Point Units 3 and 4 to execute the "Secondary Chemistry Optimization Plan" (Reference 1). This plan was established as a site specific chemistry program that

represents the best chemical approach for minimizing corrosion damage and performance losses in the secondary water system. The program is based on a secondary chemistry effectiveness assessment that is preformed at the end of each refueling outage. The assessment integrates in-service inspection (ISI) and

nondestrictive examination (NDE) data into the chemistry program. This data along with chemistry operational trends, hideout return evaluations, corrosion product transport, and sludge loading and analysis provide an overall assessment of the condition of the steam generators and secondary systems.

In turn, the result of each unit's assessment determines if there are any necessary changes to the chemistry program and if additional measures may need to be taken to ensure the integrity and reliability of the systems throughout the plant lifetime. These measures may include but are not limited to, changes to the combination of alternate amines, addition of boric acid to the steam generators, the use of scale conditioning agents, modification to sludge lancing techniques, or chemical cleaning.

Currently the units are using ethanolamine (ETA) as a pH and erosion-corrosion control agent at Turkey Point Units 3 and 4. A recently completed two-phase study of the effects of ETA and MPA chemistry

regimens supports the permanent use of ETA and/or MPA as a secondary system pH control additive at Turkey Point Units 3 and 4 (References 2 and 3).

With the current chemistry control program of 150-200 ppb hydrazine, the feedwater iron concentrations at Turkey Point Units 3 and 4 are routinely being maintained at - 1-3 ppb. Combined amine usage, coupled with a hydrazine during normal operation, may offer additional benefits relative to reducing iron transport on the secondary side.

The purpose of this evaluation is to assess the addition of (DMA), (MPA), or morpholine in the secondary

systems of the Turkey Point Units 3 and 4. This evaluation covers the addition of the additional amines: either alone or in combination with each other with respect to the balance of secondary side chemical control agents, specifically ETA, hydrazine, carbohydrazide, and ammonium hydroxide.

General

The use of ETA or MPA in the secondary system at Turkey Point has been evaluated in References 1 and

2. References I and 2 address the compatibility of ETA or MPA with the Turkey Point steam generators I and balance of plant materials of construction.

The justification for the use of the proposed alternate amines, either alone or in combination with each

other, are discussed in EPRI reports, specifically References 4 and 5. These EPRI reports discuss the

impact of these amines on typical plant system materials, plant operations and water chemistry are

discussed in the EPRI reports, PWR Advanced Amine Application Guidelines and PWR Secondary Water Chemistry Guidelines (References 4 and 5).

Attachment i • -- N.JkJ(.- S \ - O i-D7zs- SECL 00-174, Revision 1

Page ofs ., . Page 5 of 14

Most US PWRs initially utilized ammonia for secondary system pH control, either directly via ammonium hydroxide addition or indirectly through hydrazine injection and decomposition. In later years studies were conducted using morpholine as an alternate to ammonia for secondary system pH control (Reference 8). Based on the favorable morpholine experience EPRI began an extensive program to evaluate candidate amines for use as pH control agents.

The proposed alternate amines have a higher ionization constant, Kb, or lower pKb which means that they have higher base strength than morpholine. At the same concentrations, the alternate amines would provide higher pH than morpholine..

The proposed alternate amines are much less volatile than morpholine alone with the exception of MPA. Relative volatility is the ratio of the amine concentration in the steam phase to the amine concentration in the liquid phase. This property is very beneficial in minimizing corrosion in the moisture separator reheater (MSR) drain piping. A higher concentration of the amine carries over into the MSR water where it condenses and is pumped forward with the feedwater. This path results in higher pH in the components and at the same time reduces amine concentration in the condensate that will be processed by the condensate polishing system. At Turkey Point Units 3 and 4 this is not of significant concern as the condensate polishers are only placed into operation during startup. During power operation the condensate polishers are not operated.

According to EPRI, the selection of the best amine(s) for a particular plant requires careful study and evaluation (Reference 4). A careful evaluation must consider existing plant materials, historical secondary side chemistry, corrosion product transport data, condensate polisher operation and cost. Furthermore, EPRI states that the use of a combination of amines may be of particular benefit in attempting to achieve minimum corrosion rates of all secondary system components. The effectiveness of an amine depends on both base strength and volatility. An amine with very low volatility would provide excellent protection of wet steam areas, important in controlling flow-assisted corrosion (FAC), but would provide less relative protection against general corrosion of the condensate system. An additional concern is the low temperature feed train, between the condensate pump discharge and the entry point of the heater drain pumps. Since the advanced amines with low volatility will tend to cycle through the heater drains, the addition rate required to maintain the desired amine concentration can be quite low. This limits the amount of protection in the low temperature feedwater section of the plant.

Field Experience

Numerous US utilities have converted to advanced amine treatment, specifically ETA. Virtually all of these utilities have reported substantial decreases in iron transport. Overall, the reductions in iron concentrations observed with ETA pH control are very significant compared to typical ammonia and low morpholine chemistry control. To date, there have been no significant problems reported by utilities that have converted to ETA pH control.

A number of US plants are using MPA for secondary chemistry pH control. In addition, a number of utilities are using MPA in combination with ETA. Operation of the blowdown demineralizers with MPA is greatly improved with MPA as compared to ETA. Blowdown performance has been shown to be enhanced by the higher selectivity of the resin for sodium relative to MPA.

Attachment I to T -• - oo-.s- , Z.oSECL 00-174, Revision I

Page j Otif I q Page 6of4

DMA is also currently in use in a number of US PWRs. It has been used successfully in combination with morpholine (5 ppm) and with ETA (2.5 ppm). In some utilities, full-flow condensate filter

demineralizers are operated in the morpholine form using pre-morpholated ion exchange resins. DMA was chosen for use in some plants because of its good base strength at low concentrations, and its apparent effects of reducing fouling on heat transfer surfaces.

Most US utilities are using advanced amine(s) without the addition of boric acid to the steam generators. However, a few PWRs are presently adding boric acid to the steam generators via the feedwater chemical

feed system. The rationale is to provide additional protection against caustic induced corrosion of the

steam generator tubes; specifically the crevice regions. There is a potential of corrosion of carbon

steelwhen exposed to boric acid at high concentrations. However, field experience shows that at the low

concentrations of 0.5 to 1.0 ppm in the feedwater and 5-10 ppm in the steam generator blowdown that

corrosion of feedtrain and steam generator carbon steel material does not occur with proper secondary side pH control.

Water Chemistry

The justification for the use of the proposed amines and their impact on typical plant system materials,

plant operations and water chemistry are discussed in the EPRI reports, PWR Advanced Amine

Application Guidelines and PWR Secondary Water Chemistry Guidelines (References 4 and 5). These

documents will be used as the initial basis for the implementation of advanced amines at Turkey Point

Units 3 and 4.

As noted in Table 1, the proposed alternate amines have a higher ionization constant which means that

they have higher base strength than morpholine. As previously mentioned, at the same concentrations, the alternate amines would provide higher pH than morpholine.

The proposed alternate amines are more thermally stable than morpholine as shown in Table 1. Organic

amnines decompose and react with trace oxygen forming short chain organic acids; primarily acetic,

formic and glycolic acids. Though these acids do not pose any major problem, they do complicate

chemistry monitoring. Production of excessive organic acids puts additional load on the condensate

polishers (anion resins), reduces the usefulness of the cation conductivity as a measure of aggressive

anionic contaminants and results in a small decrease in the alkalinity (pH) provided by the amine. At

Turkey Point Units 3 and 4 the condensate polishers are in operation only during start-up. Furthermore,

initial data from eight (8) PWR plants testing ETA in combination with an additional alternate amine

(MPA)indicate that the organic acid production rates are lower than that with morpholine (Reference 6).

Turkey Point Plant has an ion chromatograph which is capable of measuring concentrations of organic

acids and strong acid anions separately, therefore, the impact of organic acids on cation conductivity is

not a problem.

The use of the aforementioned alternate amines were reviewed with respect to the other existing

secondary side chemical control agents, specifically hydrazine, carbohydrazide, and ammonium

hydroxide. References 4 and 5 reports discuss the impact of the alternate amines and the combinations of

these amines on present water chemistry control in PWRs. A review of these references indicates that

the use of any single amine or combination of amines will not adverse impact the existing secondary side

chemistry regime at Turkey Point Units 3 and 4.

Attachment to - - -- --- SECL 00-174, Revision I

Page 7 of 14

Effects on Steam Generator Materials

The use of the aforementioned alternate amines were reviewed with respect to the other existing

secondary side chemical control agents, specifically hydrazine, carbohydrazide, and ammonium

hydroxide. In addition, the use of combinations of the alternate amines were reviewed both with and

without the addition of boric acid to Westinghouse model 44F steam generators.

The implementation of the Turkey Point Plant's alternate amine optimization program for Units 3 and 4

should be consistent with the program outlined in Section 14 of the PWR Advanced Amine Applications

Guidelines (Reference 4). The secondary system materials of construction, which include the steam generator tubing material, will not be adversely impacted by either the use of ETA, DMA, MPA, morpholine or a combination of these amines for secondary system pH control.

Increased deposit removal may be observed by the increased pH afforded by alternate amines over

conventional ammonia or morpholine treatment. However, this is likely to stabilize as the system

equilibrates. If this occurs, it will be temporary and no chemistry or corrosion concerns are expected. The lower volatility of the amines will increase the at-temperature pH in liquid areas of the steam

generator, and lower the corrosion rates of large-area carbon-steel structural components within the steam

generator. Corrosion rates of these components are already low due to the formation of passive oxide films, so this impact is likely to be negligible.

Constant extension rate tests (CERT) and heat flux crevice tests were performed to evaluate the behavi6o

of typical steam generator materials with alternate amines. The CERT tests were performed to evaluate

the possibility that a particular chemical would cause enhancement of stress corrosion cracking. Three

microstructures of Alloy 600 were tested: mill annealed, sensitized, and thermally treated. Specimens

were heated to 315'C and strained at 5 x 10- in/sec to specimen failure. Stress corrosion cracking did not

occur in these tests (Reference 9).

Heat flux crevice tests were performed to evaluate the effect of alternate amines on intergranular attack

(IGA). These tests were performed on mill-annealed and sensitized Alloy 600, and thermally treated Alloy 690 tubing. IGA was induced in some of the sensitized Alloy 600 specimens prior to the test.

Crevice areas were packed with magnetite. The test solution consisted of ETA, DAE (1, 2

diaminoethane), and AMP (2 amino, 2 methyl propanol). The test solution was pumped through an

autoclave at 0.5 gallons/hr. for 2014 hours (temperatures of 288°C at autoclave inlet to 315 0C at autoclave

outlet). The test results demonstrated that the amines did not initiate or promote IGA in crevice areas.

Even though MPA was not used in the heated crevice tests, the chemical composition of ETA and MPA

are very similar. Additionally, the thermal stability, decomposition products, and base strength for MPA

do not give reason to expect differing behavior for MPA, in comparison to ETA or AMP in these tests (Reference 9).

Plants that have converted from ammonia to alternate amines have observed increases in steam generator

blowdown cation conductivity, due to increased concentration of short-chained organic acids (acetic and

formic acids). The increase in organic acids is due to a slight breakdown of the amine at operating

temperature, and dissolution of organic impurities in the secondary system, caused by the introduction of

the amine. The actual amount of the increase will depend primarily on the quantity of impurities in the

secondary system. Potential sources could include secondary side organic lubricants or sealants, which

Attachment ( to PTN - E&-P S c-ge s - o\ -op •- SECL 00-174, Revision I

page ',5 of -a I P 2. C Page 8ofl14

may be dissolved by any of the amines. Consequently, it is not possible to accurately predict the magnitude of any temporary cation conductivity increase that may occur. Any increase in cation conductivity due to organic acids is not considered detrimental to steam generator structural materials.

Effects on Balance of Plant Materials

There is no evidence to suggest that the use of ETA, MPA, DMA or morpholine will have any impact on the corrosion rates of other alloys in the balance of plant, such as stainless steel. Both the general corrosion rates and flow assisted corrosion rates of high alloy materials such as stainless steel are much lower than that of carbon steel.

The PWR Secondary Water Chemistry Guidelines also indicate that the "use of natural rubber products such as Buna-N rubber, Butyl rubber, Neoprene, and Viton A should be avoided in the amine feed system when organic amines are being fed." Testing has been conducted on elastomers used throughout secondary systems in various seals and packing. The advanced amines were shown to attack natural rubber products such as Buna-N, Butyl rubber, Neoprene, Red rubber, and Viton A at chemical feed concentrations of greater than 10,000 ppm. Dixosteam, EPDM, Kalrez, and Teflon PTFE were found to be acceptable for use with MPA at high concentrations in chemical feed systems. These materials are also acceptable for use with other alternate amines. Under typical condensate/feedwater conditions (2007F), Buna-N rubber, Butyl rubber, Dixosteam, EPDM, Kalrez, Teflon PTFE, and Polypropylene were found to be acceptable for use with MPA and other amines.

Turbine Considerations

The use of ETA, MPA, DMA or morpholine in nuclear plant secondary systems has not resulted in any reported corrosion to turbine materials. In implementing the use of alternate amines, Westinghouse has stressed the importance of steam purity in reference to specific contaminant concentrations. There is no reason to anticipate that the use of ETA, MPA, DMA or morpholine will have any impact on steam purity. Steam generator bulk contaminant concentrations, and therefore the steam specific contaminant concentrations are not directly affected by the secondary side pH control scheme. Control of impurities in the steam will be assured by appropriate chemistry monitoring.

Concern has been expressed regarding the potential of organic acids to produce acidic conditions at the point of first condensation in the low pressure turbines (Wilson Line). This is because the organic acids produced in highest concentration - acetic, formic, and glycolic - have low volatility and may seek the water phase as the steam quality decreases.

The general characteristics of all the amines considered for secondary side pH control are similar. As a result, the behavior of these compounds with respect to decomposition products does not vary significantly with the choice of amine. The current operating history which has been obtained with ETA, MPA, DMA and morpholine is extensive, and turbine corrosion at the Wilson Line has not been identified as an ongoing corrosion issue at the plant utilizing these alternate amines.

The turbine has no safety-related design function therefore, turbine corrosion would be an economic issue not a safety-related issue. This discussion does not imply that Westinghouse endorses the use of ETA,

Attachment to SN - C-NZ -- EC MS - \ -_ -0 1 -5- SECL 00-174, Revision I

Page 9 of 14 PageeOfj

MPA, DMA or morpholine with respect to the Turkey Point turbines. It is recommended that separate approval be obtained from the turbine manufacturer prior to the implementation of alternate amines at the Turkey Point units.

Operational Considerations

Initial Addition

Potential impacts on operation include (1) increased organic acid concentrations and cation conductivity due to organic residuals (such as linseed oil used to seal turbine casings) and (2) increased blowdown of

suspended solids due to sludge mobilization within the steam generators. These potential chemistry perturbations should be addressed by following the action level guidance given in the current revision of the PWR Guidelines for Secondary Water Chemistry (Reference 4).

It has been reported that the Turkey Point units share common systems in the secondary system. This may result in amine transfer to the unit not using alternate amines when initially applied. The small quantity of amine transferred to the other unit is not likely to impact secondary system chemistry significantly, however, plant chemistry personnel should be prepared for possible increases in organic acid concentrations and cation conductivity due to amine oxidation and decomposition as well as possible dissolution of organic material residuals. This effect is likely to be small on the unit not implementing amine chemistry at the time, and should be able to be addressed by routine responses to off normal chemistry control (e.g., increased blowdown, increased monitoring).

Wet Lay-up and Plant Startup

Due to the potential for oxygen ingress during makeup water addition in wet lay-up, it is recommended that a pH control agent be used during wet lay-up to achieve the pH in accordance PWR Secondary Water Chemistry Guidelines (Reference 5). Several US PWRs are using alternate amines to achieve the pH in the aforementioned guidelines. However, in the presence of oxygen, alternate amine decomposition can be enhanced as much as five times at elevated temperatures. While this may not be an immediate concern during wet lay-up, it can result in amine decomposition during plant heat-up. Decomposition during plant heat-up could lead to elevated concentrations of organic acids. This would not present a corrosion concern for the steam generator, but would provide useful function for system corrosion control at that time.

Plant Trips

Following a plant trip with loss of condenser vacuum, the presence of elevated dissolved oxygen concentrations at high temperature can result in increased alternate amine decomposition. Alternate amine addition should be terminated at this time to prevent excessive decomposition of the residuals. Alternate amine addition may be reestablished for feedwater chemistry control during the subsequent

startup.

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Page 1O of _1a Page10of14

Plant Shutdowns

In order to achieve plant shutdown conditions with minimal impact on secondary system impurity

concentrations, alternate amine addition may be suspended prior to a planned plant shutdown.

Suspension of amine addition prior to plant shutdown can limit the extent of amine decomposition due to

elevated dissolved oxygen concentration at high temperatures. As indicated in the previous sections, this

is not a necessary constraint based on steam generator corrosion concerns, but rather a suggested measure

to limit the extent of amine decomposition and elimination following loss of condenser vacuum.

Secondary Chemistry Changes

Cation conductivity measurements are used as a diagnostic tool to assess the cumulative concentration of

anionic species in the secondary system. This parameter does not give chemical information about any

specific anionic species. The information regarding a particular anionic species is determined through

laboratory analyses and/or through various on-line instrumentation. In order to effectively assess the

cation conductivity data to evaluate the system chemistry, analysis of specific anionic contaminants is

required. It is recognized by EPRI that the organic ion decomposition products from the use of alternate

amines present no deleterious effect to secondary system corrosion mechanisms. However, continued

monitoring of cation conductivity due to the presence of chloride and sulfate is necessary to monitor

contaminant ingress to the secondary side. At Turkey Point Units 3 and 4, secondary side chloride and

sulfate concentrations are monitored on a regular basis to facilitate the determination of possible

contaminant ingression.

Conclusions/Exclusions

After review of the preceding information with consideration of Turkey Point Units 3 and 4 specific

design, Westinghouse concurs with the use of the discussed alternate amines or combinations of these

amines, specifically ethanolamine (ETA), dimethylamine (DMA), methoxypropylamine (MPA), and/or

morpholine, within the Turkey Point Units 3 and 4 secondary side. It is recommended that separate

approval be obtained from the turbine manufacturer prior to the implementation of alternate amines at the

Turkey Point units.It is concluded that these amines may be used in the secondary side with respect to the

other existing secondary side chemical control agents, specifically hydrazine, carbohydrazide, and

ammonium hydroxide. In addition, Westinghouse concurs with the use of combinations of the

aforementioned alternate amines both with or without the addition of boric acid to the existing

Westinghouse model 44F steam generators.

No corrosion is expected to occur in the steam generators or balance of the secondary plant at Turkey

Point due directly to the implementation of the combination of alternate amine secondary side chemistry

control. Increased protection for balance of plant carbon steel materials against erosion-corrosion should

actually reduce feedwater iron concentration and result in a reduced state of steam generator deposit

accumulation, in comparison to just ETA/hydrazine chemistry control.

Attachment I to QTMJ -•b--•- se'&•-oqg' - L-5 QSECL 00-174, Revision I

Page . of Page 11 of 14

Table 1 Comparison of Amines

NOTES: 1. pKb = -loglo, K; KI, = ionization constant 2. RV = relative volatility

4.0 ASSESSMENT OF UNREVIEWED SAFETY QUESTION

The addition of alternate amines to the secondary side system at Turkey Point Units 3 and 4 has been evaluated based on the criteria of 10 CFR 50.59(a)(2). Its use does not involve an unreviewed safety question on the basis of the following justification and may be implemented without prior approval of the NRC.

1. Will the probability of an accident previously evaluated in the UFSAR be increased?

No. The addition of alternate amines to the secondary side system will not adversely affect the steam generator tubes, tube support plates, secondary shell, piping, or secondary side component relative to their structural integrity and their safety functions. Moreover, the addition of alternate amines to the secondary side system will not act as an initiator for any accidents previously evaluated in the FSAR. Therefore, the probability of an accident previously evaluated in the FSAR has not been increased.

2. Will the consequences of an accident previously evaluated in the UFSAR be increased?

No. The addition of alternate amines to the secondary side system will not impact the accident analyses or plant accident scenarios. The response of the plant safety systems, when subjected to accident conditions, will not be affected such that their function in the control of radiological consequences is affected. The addition of alternate amines to the secondary side system does not

pKb (°C) 10 ppm RV (°C) Plant Resin

25 150 300 25 150 300 Use Testing Comments Ethanolamine 4.5 4.8 6.3 0.01 0.26 0.66 Yes Yes Has excellent distribution ratio, (ETA) good pKb, low decomposition,

readily available, low dosage required. Decomposition product of morpholine.

3-methoxypro- 3.9 4.2 5.6 0.13 0.81 0.72 Yes Yes Best pKb but less favorable pylamine dist. Ratio than others. (MPwA) Dimethyla- 3.22 3.63 5.44 - - - Yes Yes Has excellent distribution ratio, mine (DMA) good pKB, also used for SG hot

soaks Morpholine 5.5 5.3 6.5 0.12 0.78 1.28 Yes Yes For comparison. Although an

improvement over NH3, high dosage & less favorable distribution ratio than others.

Attachment I to f• •-•C- - • E • - - 0 0 7o SECL 00-174, Revision 1

Page I -L of-L-i Page 12 of 14

alter any assumption previously made in the radiological consequence evaluations nor affect the mitigation of the radiological consequences of an accident described in the FSAR. The addition of alternate amines to the secondary side system will not affect safety system performance and, therefore, will not increase the consequences of an accident previously evaluated in the FSAR.

3. May the possibility of an accident which is different than any already evaluated in the UFSAR be increased?

No. There is no residual effect on the pressure boundary material of the steam generator and secondary system. Hypothetical damage due to the misapplication of the addition of alternate amines to the secondary side system would be bounded by the analysis of a steam line break

accident. The configuration and operation of the steam generator and secondary system are not altered such that a different type of accident could be created.

4. Will the probability of a malfunction of equipment important to safety previously evaluated in the UFSAR be increased?

No. The primary side components are not affected by the addition of alternate amines to the secondary side system. The design and operation of the steam generator and secondary system are not altered by the addition of alternate amines to the secondary side system. The probability of a malfunction is not increased by addition of alternate amines to the secondary side system.

5. Will the consequences of a malfimction of equipment important to safety previously evaluated in the UFSAR be increased?

No. The performance and integrity of the steam generator and secondary system are not affected

such that their control of radiological consequences is altered. The addition of alternate amines to the secondary side system does not result in a different response of safety-related systems and components to accident scenarios than that postulated in the UFSAR. No new equipment malfunctions have been introduced that will affect fission product barrier integrity. The addition of alternate amines to the secondary side system does not result in original design specifications, such as seismic requirements, electrical separation requirements, and environmental qualification,

being altered. In addition, the addition of alternate amines to the secondary side system does not result in equipment used in accident mitigation to be exposed to an adverse environment. The

installed systems assumed operable to mitigate the radiological consequences of an accident per

plant Technical Specifications and analysis assumptions are not adversely affected by addition of

alternate amines to the secondary side system. Therefore, the addition of alternate amines to the secondary side system will not increase the consequences of a malfunction of equipment

important to safety previously evaluated in the UFSAR.

6. May the possibility of a malfunction of equipment important to safety different than any already evaluated in the UFSAR be created?

No. The addition of alternate amines to the secondary side system does not have any affect on

the ability of the steam generator and secondary system to perform their intended safety function.

The addition of alternate amines to the secondary side system does not alter the loads,

- Attachment \ to f]5 -• • S t- -O\ - 0OL5- SECL 00-174, Revision 1

Pag 19Ld .I. 0) Page 13 of 14 Page ! ofe~ol

configuration, or function of the steam generator and secondary system. The addition of alternate amines to the secondary side system does not create failure modes that could adversely impact safety-related equipment. The addition of alternate amines to the secondary side system does not create any new failure modes that could adversely impact safety-related equipment. Therefore, it will not create the possibility of a malfunction of equipment important to safety different than previously evaluated in the UFSAR.

7. Will the margin of safety as defined in the bases to any technical specification be reduced?

No. The margin of safety is provided, in part, by the safety factors included in the ASME Code and by the conservatisms inherent in the accident analysis acceptance criteria. The addition of alternate amines to the secondary side system will have no adverse affect on the availability, operability, or performance of the steam generator. Operation of Turkey point Units 3 and 4 following the addition of alternate ainies to the secondary side system will not require a change to the Technical Specifications nor will it prevent inspections required by the Technical Specifications. Therefore, the margin of safety defined in any basis of the Technical Specifications is not expected to be reduced.

5.0 CONCLUSIONS

Based on the above, it is concluded that the use of alternate amines, including ethanolamine (ETA), dimethylamine (DMA), methoxypropylamine (MPA), and morpholine, within the secondary systems for Turkey Point Nuclear Plant Units 3 and 4 does not represent an unreviewed safety question. The amines and their possible combinations were reviewed with respect to the other existing secondary side chemical control agents, specifically hydrazine, carbohydrazide, and ammonium hydroxide. The addition of alternate amines to the secondary side system will not require a change to the Technical Specifications. Per the criteria in 10CFR50.59 the addition of alternate amines to the secondary side system may be implemented without prior approval of the NRC.

6.0 REFERENCES

1. 'Turkey Point Nuclear Plant Secondary Chemistry Optimization Plan", Revision 0, May 26,

1998.

2. NSD-E-CD&ME-99-276, "FPL Phase I Alternate Amine Survey", December 16, 1999

3. NSD-E-CD&ME-99-277, "FPL Alternate Amine Study - Phase 2", December 16, 1999

4. EPRI TR-102052-R2, "PWR Advanced Amine Application Guidelines", Revision 2, October 1997.

5. EPRI TR-102134-R5, "PWR Secondary Water Chemistry Guidelines", Revision 5, March 2000.

6. EPRI TR-102952, "PWR Advanced Amine Applications Guidelines, Revision 0, September, 1993.

-- N D'0t -p, -SECL 00-174, Revision 1I

Page iA -of',j4 Page 14 of 14

7. LTR-CDME-00-2 11, "Turkey Point Unit 3 and 4: Alternate Amine Optimization Safety Evaluation", December 15, 2000.

8. EPRI TR-100756, "Loop Testing of Alternative Amines for All-Volatile Treatment Control in PWRs", Revision 0, June 1992.

9. Battaglia, P.J., "The Implementation of Methoxypropylamine (MPA) for Secondary Side pH and Erosion-Corrosion Control of Vogtle Units 1 and 2", NSD-E-CDM&E-98-045, SG-98-03-005, April 1998.

SAttachment to

Page , .of 2 "Baldino Frank" To: 'chuck [email protected] <chuck [email protected]> <Frank.BaIdino@swp cc:

c.siemens.com> Subject: FW: Introduction of Alternate Amines/Impact with "Former" Westing house Turbines

04/30/2001 11:30 AM

----Original Message ----From: Bellows James

Sent: Friday, April 27, 2001 10:54 AM

To: Baldino Frank

Cc: Johnson Ray; Martin Harry

Subject: RE: Introduction of Alternate Amines/Impact with "Former"

Westinghouse Turbines

I looked through the evaluation from Westinghouse. They are planning to use

one of several alternate amines. As Westinghouse, I always said that if

they met the steam purity recommendations, I had no issue with alternate

amines. The problem tends to be that the alternate amines decompose to

organic acids that raise the cation conductivity. I have never given relief

on the cation conductivity recommendation. To achieve the cation

conductivity, they might need to run the condensate polishers continuously.

If they run outside the cation conductivity recommendation, they do so at

their own risk.

More than this is a FAR

JIM

----Original Message ----

From: Baldino Frank

Sent: Wednesday, April 25, 2001 1:46 PM

To: Bellows James

Subject: FW: Introduction of Alternate Amines/Impact with "Former"


Jim,

Can you help/comment on this request from FPL?

Thank you,

FX Baldino

----Original Message----

From: [email protected] [mailto:[email protected]]

Sent: Wednesday, April 25, 2001 1:33 PM

To: Baldino Frank

Subject: Introduction of Alternate Amines/Impact with "Former"


Frank:

Per our conversation earlier today, I am seeking assistance from Siemens on

Airchment 2 to

Page .Z of the allowance of use of the below noted alternate amines in our secondary

side systems (feedwater, etc) . Westinghouse was contracted to provide us a

safety evaluation approving the use of ethanolamine (ETA), dimetylamine

(DMA), methoxypropylamine (MPA), and morpholine (these alternate amines may

be used with or without the addition of boric acid to the Westinghouse

Model 44F steam generators). Since Westinghouse sold off their turbine

units to your group, they are not able (legally) to endorse the use of

these chemicals with respect to the Turkey Point turbines. They were quoted

in the safety eval. as saying "It is recommended that separate approval be

obtained from the turbine manufacturer prior to the implementation of

alternate amines at the Turkey Point units". I would like to fax you their

final evaluation for you to read their particulars and to discuss any open

issues with our Chemistry rep. at Turkey Point. What we are looking for

from Siemens is a concurrence that will be no likely adverse effects on the

turbine equipment as a result of the introduction of these alt. amines.

We'll ultimately add your statement to our internal evaluation.

Please provide me a fax # to transmit the eval (in the meantime trying to

get Westinghouse to give me an e-file).

Thanks,

Chuck Zyne at 305-246-6174

Attachment 4 to PTN-LIC-01-012

Application for a Minor Revision To a Wastewater Facility or Activity Permit

S rAPPLICATION FOR A MINOR REVISION TO

A WASTEWATER FACILITY OR ACTIVITY __Fo____ PERMIT

1. Instructions

a. In accordance with Rule 62-620.325, F.A.C., this form must be submitted to the appropriate Department district office or approved local program when requests for minor revisions to a permit or minor modifications to a facility are made by a permittee, except for transfer of a permit to a new permittee and addition of a major user of reclaimed water to a Part III reuse system. Application for transfer of a permit to a new permittee shall be made on DEP Form 62-620.910(11). Application for addition of a major user of reclaimed water shall be made on DEP Form 62-610.300(4)(a)1.

b. Each applicable item must be completed in full in order to avoid delay in processing of this form. Where attached sheets or other technical documentation are provided, indicate appropriate cross-references.

c. Three (3) copies of this application with supporting documentation shall be submitted with this form. d. All information is to be typed or printed in ink. Dates are to be entered in MM/DD/YR format. e. This application and attachments shall be signed in accordance with Rule 62-620.305, F.A.C. Also, as

applicable, this application and all attachments shall be signed and sealed by a professional engineer registered in Florida in accordance with Rule 62-620.310, F.A.C.

2. Facility Information

a. Permit Number: FL 0001562 b. Facility Identification Number: FLD000733683 c. Project/Facility Name: Use of Dimethylamine/ FPL Co. Turkey Point Plant d. Contact Name: Cindy Connelly

Number and Street: 9760 SW 344th Street City/State/Zip Code: Homestead,Florida 33035 Telephone 305-246-6841

3. Type of Revision

EL Correct Typographical Errors1 - Submit one copy of each page of the permit showing revisions being requested.

"LI Change Improvement Schedule1 - Provide a description of the improvement, a list of the dates to be revised, and a reason for the proposed change in each date.

"LI Change Expiration Date of Permit' - Provide the current and proposed expiration dates for the permit and the reasons for the proposed change.

El Change Staffing Requirements2 - Describe the proposed change and submit justification for the change in accordance with Chapter 62-699, F.A.C.

'A processing fee is not required. DEP Form 62-620.910(9)

'A processing fee is required with the application Effective October 23, 2000 in accordanee with Rule 624.050, F.A.C.

ED Change Monitoring and Reporting Requirements2 - Describe the proposed change and submit justification for the change in accordance with Chapter 62-60 1, F.A.C.

El Modify Approved Pretreatment Program1 - Describe the proposed modification and provide the information required by Rule 62-625.540, F.A.C.

F] Delete Point Source Outfall1 - Identify the outfall and explain why the outfall is being eliminated.

RI Modify or Expand Approved Residuals Land Application Sites2 - Attach a new or updated Agricultural Use or Dedicated Site Plan as required by Chapter 62-640, F.A.C.

0 Minor Modification to the Facility2 - Provide a description of the proposed modification. If applicable, attach any reports, plans, and specifications which have been developed to implement this modification.

RI Other2 - Provide appropriate documentation. Describe.

4. Certifications

a. Applicant or Authorized Representative

I certify under penalty of law that I have personally examined and am familiar with the information submitted in this application and all attachments and that, based on my inquiry of persons immediately responsible for obtaining the information contained in the application, I believe that the information is true, accurate and complete. I am aware that there are significant penalties for submitting false information, including the possibility of fine and imprisonment.

(Signa e ofpplicant or Authorized Representative3 ) (Date)

Name (please type) R. J. Hovey Title Vice President Phone: 305-246-1300

Company Name Florida Power & Light Co. Company Address: 9760 SW 344th Street

City/State/Zip Code: Florida City, Florida 33034

b. Professional Engineer Registered in Florida

I certify that the engineering features of this project have been (designed) (examined) by me and found to conform to engineering principles applicable to such projects. In my professional judgement, this facility, when properly constructed, operated, and maintained, will comply with all applicable statutes of the State of Florida and rules of the Department.

Name (please type): Sergio P. Chaviano Florida Registration Number: 41855 Company Name: Florida Power & Light Co. Company Address: 9760 SW 344th Street City/State/Zip Code: Florida City, Florida 33034 Phone Number: 305-246-6927

'if signed by the authorized rpresentative,

attach a letter of authorization in accordance Rule 62-620.305, F.A.C.

(Seal, Signature, Date, and Registration Number)

2 DEP Form 62-620.910(9)

Effective October 23, 2000

Attachment 4 to PTN-LIC-01-12 Page 3 Inter-Office Correspondence

FPL

To: Mgrs/Dept Heads/Supervisors Date: March 01, 2001

From: R. J. Hovey/Signature on File Department:: VP-PTN

Subject: PTN Vice President Designee 2001

In the event that I am unavailable, my designee in order will be the following:

1. Plant General Manager 2. Maintenance Manager 3. Operations Manager 4. The On Duty NPS

RJH:cas

Copies:

T. F. Plunkett J. A. Stall R. J. Acosta R. S. Kundalkar

Attachment 5 to PTN-LIC-01-012

WARNING: Original document has a reflective watermark on reverse side. Hold at an angle to view. For Inquiries call (3051485-67000

FPLCheck Date: 07/1112001 Check No. 0192547

TWO HUNDRED FIFTY DOLLARS

PAY TO THE ORDER OF

STATE OF FLORIDA

DEPT OF ENVIRONMENTAL PROTECTION

2600 BLAIR STONE ROAD

TALLAHASSEE FL 32399

nu019325417`1 1 :0F.112788i:

Florida Power & Light Co. Vendor Name: STATE OF FLORIDA

FLORIDA POWER & LIGHT CO.

3 2999??777 1In

Check Date : 07/11/2001 Check Number: 0192547

WASTEWATERPERMIT 07/10/2001 1900081357 FLQ001562 PTN

Check Total .............................

250.00 0.00 250.00

$ 250.00

______________________ ± ____________ J .1. .1- ________________

SAP Disbursement Account Bank of America Atlanta, Dekalb County, Georgia

64-1278 611

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