ML20058E428
| ML20058E428 | |
| Person / Time | |
|---|---|
| Site: | South Texas  |
| Issue date: | 12/31/1989 |
| From: | Grover J, Henninger W, Rubin K WESTINGHOUSE ELECTRIC COMPANY, DIV OF CBS CORP. |
| To: | |
| Shared Package | |
| ML20058E414 | List: |
| References | |
| WCAP-12477, NUDOCS 9011070167 | |
| Download: ML20058E428 (61) | |
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HESTINGHOUSE CLASS 3 HCAP-12477 SPRAY ADDITIVE ELIMINATION ANALYSIS FOR THE SOUTH TEXAS PROJECT i
DECEMBER 1989 l
i APPROVED:
v H. li. Shannon, Manager Plant & Systems Evaluation Licensing Hork performed under Shop Order HHNP-4735 l
oHESTINGHOUSE ELECTRIC CORPORATION Nuclear Energy Systems P. 0.-Box 355' Pittsburgh, Pennsylvania 15230 l
l 0268D:lD/122789 o
-A
. ~. -
HESTINGHOUSE CLASS 3 CONTRIBUTORS K. Rubin J. L. Grover H. A. Henninger i
f
}
i 1
p.
l 0268D:10/122789 i
HESTINGHOUSE CLASS 3 TABLE OF CONTENTS SECTION IIILE PEI
1.0 INTRODUCTION
SUMMARY
AND CONCLUSIONS 1-1 1.1 Introduction 1-1 1.1.1
Background
1-1 5
1.1.2 Objectives 1-3 1.2 Conclusions 1-3 s
L-1.3 References - Section 1 1-4 l
2.0 BENEFITS 2-1 3.0 IODINE REMOVAL COEFFICIENTS AND DECONTAMINATION FACTORS 3-1 3.1 Elemental Iodine-Removal by Spray 3-1 l
3.2 Particulate Iodine Removal By Spray 3-4 3.3 Deposition. Removal of Elemental Iodine 3-6 3.3.1 Deposition Model Descr'.ption 3-6 3.3.2 Deposition Velocity.(Average Mass Transfer 3-7 q
Coefficient)
I 3.3.3 Deposition Surfaces 3-8 lt 3.3.4 Deposition Removal Rate 3-9 1
3.4 Iodine Retention In' Sump 3-9 3.5. Iodine Retention on Surfaces 3-10' I
3.6 References - Section 3 3-11 4.0 RADIOLOGICAL CONSEQUENCES 4-1
.4.1 LOCA Doses Hith Credit For Spray Additive 4-1 4.2 LOCA Doses Hith Spray Additive _ Removed.
4-2 4.3-Identification-of Conservatisms 4-3 4.4 References - Section 4 4-4 b
02680:10/122789 11
FiSTINGHOUSE CLASS 3 TAB'.E OF CONTENTS (Continued) 1 SECTION TITLE PEtE 5.0 EFFECTS ON HYDROGEN GENERATION AND EQUIPMENT QUALIFICATION 5-1 1
5.1. Hydrogen Production due to Aluminum 5-1 and Zinc Corrosion r
5.1.1 Aluminum Corrosion 5-1
-5.1.2 Zinc (Galvanized Steel) Corrosion 5-2 5.1.3 Zinc Enriched Paint Corrosion 5-3 5.1.4 Hydrogen Production - Conclusion 5-3 5.2 Equipment Protection 5-4 5.2.1 Protection of. Stainless Steel 5-4 5.2.2-Protection of Eler.trical Components 5-5 5.2.3 Protection of Containment Coatings 5-7 5.3 References - Section 5 5-8 6.0 -
ADJUSTHENT Of SUMP SOLUTION pH 6-1 6.1 Definition of Required Long Term pH 6-1 6.2 Caustic Addition 6-1 6.2.1 Sodium Hydroxide Spray Additive 6-1 6.2.2 Trisodium Phosphate 6-2 1
6.3 References - Section.6 6-4 7.0-TECHNICAL SPECIFICATIONS 7-1
'7.1 Description of Proposed Changes 7-1 7.2 Proposed Significant Hazards. Consideration 7-2 7.3 Basis for Proposed No Significant Hazards 7-3 Consideration Determination
7.4 Proposed
Technical Specification for Sump Additive 7-5.
0268D:lD/122889 iii
HESTINGHOUSE CLASS 3 LIST OF TABLES HUMBIB 111LE PKtE 3-1 Observed Deposition Velocities for Various Surface Coatings 3-14 3-2 Flooded or Other Surfaces 3-15 Assumed Not Available for Deposition 3-3 Summary of Spray and Deposition Surface Areas 3-16 6-1 Physical Data for Trisodium Phosphate 6-5
)
l i
026BD:lD/122789 iv l
l
HESTINGHOUSE CLASS 3 LIST OF FIGURES NUMBER IJJLI EAGE 1
3-1 Partition Coefficient vs. Iodine Concentration in Gas Phase 3-17 3-2 Equilibrium Iodine Partition Coefficient 3-18 3-3 The Effect of pH on the 1 Yield in an Irradiated 3-19 i
2 Solution 5-1 Relative Hydrogen Contribution From all Sources 5-9 I
5-2 Aluminum Corrosion Versus pH 5-10 5-3 Zine (Galvanized Steel) Corrosion Rate Constants 5-11 for Spray Injection 5-4 Zinc (Galvanized Steel) Corrosion Rate Constants 5-12 For Spray Recirculation I
i 5-5 Zinc Based Paint Corrosion Rate Constants 5-13 i
6-1 Titration Curves for TSP in Boric Acid Solution 6-6 j
4 i
0268D:10/122889 v
i HESTINGHOUSE CLASS 3
1.0 INTRODUCTION
SUMMARY
AND CONCLUSIONS l
1.1 Introduction 4
Containment sprays having a sodium hydroxide additive are currently assumed to provide the primary means of reducing the radioiodine concentrations in the containment atmosphere following a design basis large Loss of toolant Accident (LOCA). This post-LOCA iodine control function can be effectively performed by boric acid sprays and by deposition on containment surfaces. Thus, the j
soray additive tanks (SAT) which contain the sodium hydroxide, the additive delivery system, and the related testing and maintenance required by the Technical Specifications can be eliminated.
Performing the SAT related tests and maintenance required by the Technical Specifications is a resource drain L
%a handling of concentrated sodium hydroxide solution requires special L
precautions due to its hazardous nature.
There have been cases at power plants, including the South Texas Project, of contamination of primary grade water by sodium hydroxide leakage. Cleanup using demineralizers has led to ion exchange resin depletion which necessitated resin replacement.
In addition, at some other plants, SAT discharge valves that were inadvertently left closed following maintenance have resulted in Nuclear Regulatory l
Commission (NRC) enforcement actions and fines. Removal of the spray additive j
and related components can be justified by utilizing current radiological analysis techniques and current NRC evaluation criteria, This report describes the analyses and evaluations which were performed to demonstrate that elimination of the spray additive from the South Texas Project should result in relatively minor impact to the radiological consequences of a postulated LOCA, 1.1.1
Background
{
The Containment Spray System design for the South Texas Project currently utilizes caustic containment spray (pH 8.5 to 10,5) to assure the removal of radioactive iodine from the containment atmosphere following a postulated large break LOCA.
The removal of airborne iodine is necessary in order to 0268D:1D/122789 1-1
WESTINGHOUSE CLASS 3 minimize its release to the environment due to containment leakage and thus assure that the offsite dose guidelines of 10CFR100 are met.
The specification of the containment spray pH for fission product control was based on the following assumptions:
iodine removal capability of unadjusted boric acid spray is low, iodine removal capability of the spray is greatly enhanced at pH values greater than 8.5, and gaseous elemental iodine is the dominant species released from the reactor core (Reference 1).
Analyses performed by Westinghouse, combined with knowledge gained from many studies on the behavior of iodine in the post-LOCA environment, ht.ve demonstrated the relatively minor role cf the spray additive in meeting the dose guidelines of 10CFR100. The NRC methodology in Revision 2 to SRP 6.5.2 (Reference 2) goes even further in recognizing this relatively minor role of the spray additive by eliminating its consideration in determining the ability of sprays to remove airborne elemental iodine.
Also, while a considerable number of iodine-behavior studies indicate that the primary form of iodine will be non-volatile iodides, this SAT elimination analysis is based upon c.ontinued use of the assumption that elemental iodine is the predominant form.
The removal of the spray additive does not eliminate the need for adjusting the pH of the Emergency Core Cooling System (ECCS) recirculation solution.
To assure that the iodine removed by the sprays is retained in solution, to minimize chloride induced stress corrosion cracking of austenitic stainless steel components, and to minimize the hydrogen produced by the corrosion of galvanized surfaces and zinc-based paints, the long-term pH of the ECCS solution should be no less than 7.0.
Since the initial pH of the boric acid ECCS solution, without spray additive, will be approximately 4.5, a chemical additive must be utilized to raise the pH of the solution in the containment sump.
0268D:10/122789 1-2
HESTINGHOUSE CLASS 3 1.1.2 Objectives The prime objective of this analysis is to provide justification, and obtain NRC concurrence, that spray additive is not required.
Supporting objectives to meeting this primary objective are as follows:
1.
Evaluate the elemental iodine removal effectiveness of containment sprays and of surface deposition.
2.
Evaluate the particulate iodine removal effectiveness of the containment sprays.
3.
Evaluate the use of trisodium phosph" e for post-accident long-term pH control of the ECCS recirculation watar.
4.
Evaluate the potential for chloride induced stress corrosion cracking.
5.
Determine the impact of SAT elimination on hydrogen generation and equipment protection.
1.2 Conclusions The fundamental conclusion from the analysis is that the spray additive tank can be removed from the South Texas Units 1 and 2 without significantly l
affecting the radiological consequences of a postulated LOCA. Additional conclusions are:
1.
TSP is a good candidate for long term pH control in the'ECCS recirculation solution.
2.
Maintaining the sump solution pH greater than 7.0 satisfies the requirements of addressing the potential for chloride induced stress corrosion cracking and for assuring continued iodine retention in the sump solution.
0268D:1D/122789 1-3
WESTINGHOUSE CLASS 3 3.
Deletion of the spray additive will have little or no impact on hydrogen generation and equipment protection.
1.3 References - Section 1 1.
USNRC Regulatory Guide 1.4, " Assumptions Used for Evaluating the Potential Radiological Consequences of a loss-of-Coolant Accident for Pressurized Hater Reactors", Revision 2, June 1974.
2.
" Standard Review Plan for the Review of Safety Analysis Reports for Nuclear Power Plants", NUREG-0800 Section 6.5.2, Rev. 2, December 1988.
l 1
0268D:1D/122789 l-4
WESTINGHOUSE CLASS 3 2.0 BENEFITS Removal of the spray additive will provide significant benefits to plant operations.
The major benefits include simplification of plant design, elimination of hardware, elimination of Technical Specification requirements, and reduction in hazardous chemical exposure. Other benefits are summarized as follows:
1.
Elimination of Testing and Maintenance - Removal of the additive will eliminate testing and maintenance of the eductors, motor operated additive tank discharge valves and associated instrumentation.
Elimination of testing and maintenance reduces the operator exposure to sodium hydroxide.
The South Texas Project will keep the eductors and associated spray additive system loop piping as a mini-flow line for the containment spray pumps.
2.
Elimination of Additive Tank Discharge Valves - When the additive tanks are removed or decommissioned the discharge valves will be either removed or locked closed.
It should be noted that NRC enforcement actions and fines have resulted from these valves being inadvertently closed at a number of plants.
l 3.
Elimination of Refueling Hater Contamination - Spray additive system testing can result in sodium hydroxide contamination of the refueling water, which necessitates replacement of the. spent fuel pool cleanup l
system ion exchange resins used to remove the sodium contamination.
Eliminating the potential for this contamination eliminates the associated resin replacement, waste water processing costs, and radiation exposure.
I l
4.
Elimination of Caustic Cleanup - Inadvertent actuation of the containment spray system can result in time consuming containment cleanup and personnel radiation exposures.
Removal of the hydroxide from the spray will_ reduce the cleanup effort and personnel exposure to radiation and sodium hydroxide.
1' 0268D:lD/122789 2-1
HESTINGHOUSE CLASS 3 5.
Elimination of High pH environment - Elimination of the spray additive reduces the pH of the post-LOCA environment from 10.5 to a maximum of approximately 7.0.
Components qualified at the higher pH may have a longer post-accident service life when subjected to a less caustic spray environment.
6.
Elimination of Replacement Costs - Elimination of the additive subsystem will eliminate costs for replacement pumps, motors, valves and instrumentation.
7.
Flexible Spray Operation - Removal of the additive can add flexibility to the operation of the containment spray and emergency core cooling i
(ECC) systems. Hith the additive system, the spray injection phase is generally continued beyond the ECC injection phase in order that sufficient sodium hydroxide be added to the sump solution. Without spray additive, the duration of spray injection is not controlled by additive flow and pH restrictions.
8.
Flexible pH adjustment - Extended fuel cycles require increased boron concentrations (in the RCS, accumulators, and RHST) to accommodate higher core reactivity. Additional caustic may be required, due to the added boron, to raise the pH of the recirculated ECC solution into the required range.
The additional ccustic requirement may exceed the capacity of the current additive system.
A passive caustic delivery system, like the TSP basket system described in Section 6.0, can easily accommodate any future caustic requirement.
0268D:1D/122789 2-2
HEST 1NGHOUSE CLASS 3 3.0 IODINE REMOVAL COEFFICIENTS AND DECONTAMINATION FACTORS During a large break LOCA a major part of the calculated offsite thyroid dose is due to containment leakage of airborne radioactive iodine to the environment.
Based on TID-14844 (Reference 1), fifty percent of the core inventory of iodines is assumed to be instantaneously released to the containment atmosphere.
This airborne iodine activity is assumed to be primarily in the elemental form with smaller fractions appearing as organic compounds or as particulate.
The organic form of iodine is not easily removed from the atmosphere and is assumed to be removed only by radioactive decay.
The particulate iodine can be removed by containment sprays as well as through decay.
The elemental iodine is removed not only by decay but also by spreys and by deposition onto the surfaces inside the containment.
The methodology used to determine radiciodine removal is described in the following sections and the initial iodine removal coefficients are summarized as follows:
For elemental iodine removal by spray (3600 CPM flow rate)
A 20 hr-I s
for particulate iodine removal by spray (3600 GPM flow rate)
A 6.9 hr-I p
For elemental iodine removal by deposition A
4.5 hr-I d
3.1 Elemental Iodine Removal by Spray The current FSAR analysis takes credit for spray removal of elemental iodine assuming enhanced spray removal effectiveness due to the alkaline nature of 0268D:10/122789 3-1
l HESTINGHOUSE CLASS 3 the spray. With the deletion of spray additive, the spray will not be alkaline but will have a pH of about 4.5.
Although it has been generally held in the past (Reference 2) that the iodine removal capability of boric acid spray is very low, a number of spray experiments using either service water or standard grade boric acid solution (containing trace levels of impuritics) have shown elemental iodine removal rates comparable to those observed for sprays with either sodicin hydroxide or sodium thiosulphate added to bring the spray pH to approximately 9 (References 3,4,5,6).
The results of these experiments indicate that the iodine removal rate for sprays is sensitive to both iodine concentration and pH, and that concentration is the more influential parameter.
The Japanese investigated the effects of both pH and gas phase iodine concentration on the gas-liquid partition coefficient for iodine. The partition coefficient was found to be controlled by iodine concentration rather than by pH and, "the washout removal rate for iodine by city water spray is higher than those predicted from the partition rule due to some impurities in the water" (Reference 6). The results of the Japanese experiments are presented in Figure 3-1 which is taken directly from Reference 6.
The PSICO 10 experiments (Reference 5) indicate that, "The elemental iodine removal half-times obtained by spraying service water do not differ greatly from those found by spraying thiosulphate solution." Additionally, the results of the NSPP spray program (Reference 4) indicate that, " boric acid is much mc,re effective than expected".
A review of the CSE (Reference 3) and PSICO data by Brookhaven (Reference 7) indicates that,"... when the spray solution is fresh, all solutions appeared to effectively reduce the airborne iodine concentration, regardless of the presence or absence of an active spray additive".
The reports further indicate that, "when spray solution is fresh, the removal of iodine from the containment atmosphere is dominated by gas phase mass transport and is 026BD:1D/122789 3-2
HESTINGHOUSE CLASS 3 effectively independent of the equilibrium lodine partition coefficient of the solution, and primarily controlled by the amount of available surface to which iodine may be transported".
The current Gtandard Review plan (Reference 8) identifies a methodology for the determination of spray removal of elemental iodine independent of the use of spray additive.
The removal rate constant is determined by:
'*sE x-s VD Removal rate constant due to spray removal, hr-I where i-s Gas phase mass transfer coefficient, ft/ min K
g Time of fall of the spray drops, min T
3 Volume flow rate of sprays, ft /hr F
=
3 Containment volume, ft V
Mass-mean diameter of the spray drops, ft 0
Parameters for South Texas Project are:
9.84 ft/ min K
=
g 0.23 min T
3 28,879 ft /hr (3600 gpm)
F 3
3.56(6) ft V
4.4(-3) ft D
Hith these parameters the spray removal rate is calculated to be 25.4 hr-I which is reduced to 20 hr-I since this is the upper limit specified by this model.
l l
0268D:10/122789 3-3 J
HESTINGHOUSE CLASS 3 3.2 Particulate Iodine Removal by Spray Although unassociated with the removal of spray additive, particulate spray removal was reevaluated using the model described in Reference 8.
The first order spray removal rate constant for particulates may be written as follows:
3hf I
x p
2V d
Drop Fall Height where h
=
Spray Flow Rate F
=
Volume Sprayed V
=
Single Drop Collection Efficiency E
Drop Diameter d
Values for h, F, and V for the South Texas Project are:
143 ft h
=
3 28,879 ft /hr (3600 gpm)
F 6
3 2.74 x 10 ft V
The E/d term depends upon the particle size distribution and spray drop size.
The lower b und for particle washout by sprays is derived from the Containment Systems Experiment (CSE) cesium washout tests (References 3 and 9).
The following E/d values were estimated by Postma (Reference 10) from the CSE data.
[-0.1cm-I for C /C I 100 g t I
f - 0.01 cin for C /Ct > 100 g
l
'0208D: 10/122789 3-4
HESTINGHOUSE CLASS 3 Ratio of the initial aerosol concentration to the where C /C g t concentration at time t The model presented in Reference 8, conservatively uses h=0.1cm-I for C /C 1 50 g t f=0.01cm-I for C /Ct > 50 g
Using the Reference 8 model, the particulate removal constants are determined to be:
1 - 6.9 hr-I for C /C 1 50 p
g t A - 0.7 hr-I for C /Ct > 50 p
g It is noted that a lower bound estimate specifically for particulate iodine washout is also derived from the CSE tests.
The following E/d values are supported (Reference 10) f-0.3cm-I for C /C i 20 g t h=0.05cm-I for C /Ct > 20 g
The iodine collection efficiency is somewhat greater than the cesium efficiency owing to the larger iodine particle size.
If these iodine specific E/d values are used instead of the values from Reference 8, the particulate removal constants would be:
1 20.7 hr-I for C /C i 20 p
g t A
3.4 hr-I for C /Ct > 20 p
g The values for A calculated based on Reference 8 are thus seen to be p
highly conservative.
l
[
026BD:lD/122789 3-5 l
HESTINGHOUSE CLASS 3
- 3.3 Deposition Removal of Elemental Iodine In the current FSAR analysis, the deposition of iodine onto surfaces in the containment has been taken into account by assuming that half of the airborne iodine plates out instantaneously (References 1 and 11).
In this analysis for the deletion of sprey additive, a time dependent deposition model was used.
3.3.1 Deposition Model Description Of the models proposed to describe iodine removal due to surface deposition, the Knudsen-Hilliard model (described in Reference 12 and adopted by the NRC in Reference 8) provides the best agreement with available experimental data.
As discussed in Reference 10, this model was developed based on the Containment Systems Experiment (CSE) tests and it thus applies for thermal conditions which would exist after blowdown transients are over and where heat transport takes place with gas film temperature differences of one or two degrees Fahrenheit. This is conservative in comparison with the post-LOCA environment which would have higher temperature differentials, forced air circulation, and containment spray operation; all of which would enhance the rate of deposition of elemental iodine. Using the Knudsen-Hilliard model the equation for the deposition removal rate constant is written as:
'a^
xV d
Removal rate constant due to surface deposition (hr-I) where Ad-Average mass transfer coefficient (m/hr) k g
(deposition velocity) 2 Surface area for wall deposition (m )
A 3
Volume of contained gas (m )
V 0268D:1D/122789 3-6
HLSTINGHOUSE CLASS 3 3.3.2 Deposition Velocity (Average Mass Transfer Coefficient)
The determination of the deposition removal constant can take into account the various types of surfaces available for deposition as the value for the deposition velocity (k ) varies with the type of surface coating.
For g
conservatism, all galvanized and painted surfaces are assumed to have the same deposition velocity of 0.137 cm/ set (4.9 m/hr). As discussed in Reference 10, this value is based on the CSE tests and "its use assures that the predicted deposition rates remain within the range where the Knudsen-Hilliard model applies". Other surfaces such as stainless steel are not assumed to participate as deposition sites.
It should be noted that in the CSE tests the surfaces at the test facility were coated with phenolic paint and that tests of various coatings have shown that, while a deposition velocity of 0.137 cm/sec is appropriate for phenolic based coatings, significantly higher deposition velocities apply for epoxy based and zine coatings. Deposition velocities for a variety of coatings are presented in Table 3-1 (Reference 13).
A significant increase in iodine deposition is predicted to occur due to the operation of the containment sprays.
This phenomenon is attributed to the
-turbulence induced by the sprays in the bulk containment gas phase. An estimate of the spray enhancement effect on surface deposition can be made by comparing the kinetic energy dissipated by the sprays to the kinetic energy carried b; the exiting gas stream from the air cleaning system used in the CSE tests (References 10, 14).
For the South Texas Project, the kinetic energy dissipated by the sprays is 3
approximately 0.0201 ft-lb/see ft. This value is more than three times the highest value reported in the CSE tests.
Hence, the deposition enhancement reported by the CSE tests, 0.07 cm/sec, (2.5 m/hr) is a lower bound estimate for spray enhancement of surface deposition of the South Texas Project containments.
The 0.07 cm/sec value corresponds to a kinetic energy 3
dissipation of 0.006 ft-lb/sec ft,
0268D:lD/122789 3-7
WESTINGHOUSE CLASS 3 j
All containment surfaces will be subjected to spray induced turbulence, not just the surfaces wetted by the sprays.
The final value for the mass transfer coefficient (deposition velocity) should then be increased from 4.9 m/hr to 7.4 m/hr; however, in keeping with the approach described in Reference 8, no credit will be taken for the spray enhancement, 3.3.3 Deposition Surfaces Items considered to be in the post-LOCA flooded region were not used for surface deposition. Also, stainless steel surfaces were excluded as deposition sites because of its low mass transfer coefficient (deposition velocity).
The surface areas assumed unavailable for deposition are given in Table 3-2.
Included in Table 3-2 are baked enamel surface areas.
These were not used as a deposition surface because of the lack of deposition data for this material.
For components with outside and inside surfaces, only the outside surface was considered for deposition.
After the determination was made of which surfaces would be excluded as deposition sites, the remaining items were tabulated and are presented in Table 3-3.
In addition to the surface areas, the surface coating must also be considered.
As shown in Table 3-3, the areas selected for deposition surfaces are coated with either epoxy or zine base paint or are galvanized. These surfaces all have relatively higher mass transfer coefficients (deposition velocities). As discussed in Section 3.3.2, although a much higher rate of iodine deposition would exist for surfaces coated with epoxy or zine based paints, the lower deposition velocity associated with phenolic paints is used for all surfaces.
2 From Table 3-3, the area available for deposition is 1,172,447 ft. As an 6
2 additional conservatism, this area is reduced to 1.0 x 10 ft
~
2 (92,900 m ),
L 0268D:10/122789 3-8
HESTINGHOUSE CLASS 3 3.3.4 Deposition Removal Rate Using the model described in Section 3.3.1:
}
K - 4.9 m/hr g
6 2
2 A - 1 x 10 ft
- 92,900 m V - 3.56 x 10 ft - 1.01 x 105,3 6
3
)
The initial rate continues until the airborne concentration is reduced by a factor of 100 or more; the long term removal rate is typically less than ten percent of the initial rate (Reference 10).
For this analysis, the deposition removal rate is assumed to continue at its initial value until a decontamination factor (DF) of 100 is reached (i.e., the airborne concentration is one percent of its initial value). The removal rate is then assumed to continue at five percent of the initial value until a DF of 200 4 reached, after which point no additional credit is taken for iodine deposition.
3.4 Iodine Retention in Sump The decontamination factor (DF) to be used in the LOCA dose analysis is based on the combined iodine removal action of sprays and surface deposition. The DF described below is a measure of the elemental iodine loading capacity of only the sump solution. The DF can be expressed in terms of the containment liquid and gas volumes and the iodine partition coefficient.
DF-1+b(IPC)
V c
where DF - Ratio of the total iodine in the sump liquid and containment atmosphere to that in the containment atmosphere.
0268D:10/122789 3-9
WESTINGHOUSE CLASS 3 IPC - Equilibrium iodine partition coefficient (see Figure 3-2)
V, Volume of liquid in containment sump and sump overflow 4
3 (8.5 x 10 ft used for this analysis)
V - Containment net free volume less V e
s 6
3 (3.48 x 10 ft used for this analysis)
The iodine partition coefficient (IPC) presented in Figure 3-2 was provided in Reference 15.
To minimize the radiolytic production of volatile iodine, the short term IPC is based on a solution pH of 6.5.
Specifically, Lin (Reference
- 16) observed that the radiolytic 12 yield decreased substantially with pH above 4 and showed little additional decrease for pH greater than approximately 6.5 (see figure 3-3 taken from Lin).
Beahm (Reference 17) observed that the radiolytic conversion of I to I is more than a factor 2
of 100 greater at pH 3 than at pH 6.
Thus, radiolytic production of volatile iodine is minimized at pH 6.5.
Therefore, based on a pH of 6.5, a value of about 2500 for the short term (1000 seconds) IPC is seen to be appropriate from Figure 3-2.
As discussed in Section 5, an equilibrium sump solution p, of 1 7.0 is required to assure resistance to chloride induced stresi corrosion cracking of stainless steel.
The NRC has also specified a pH of 17.0 to assure continued retention of iodine in solution (Reference 8).
The longer term (say 1 hour1.157407e-5 days <br />2.777778e-4 hours <br />1.653439e-6 weeks <br />3.805e-7 months <br />)
IPC corresponding to a pH of 7.0 would be much greater; at least 10,000 (from Figure.3-2).
Utilizing the above values for the South Texas Project and an IPC of 2500 for conservatism, the DF is calculated to be approximately 60. With a DF of 60 the sump solution has the capacity to retain 98.3 percent of the iodine released to the containment.
3.5 Iodine Retention on Surfaces The adsorption surfaces within the South Texas Project containments have sufficient' capacity to retain all of the elemental iodine released from the Core.
0268D:1D/122789 3-10
I I
l HESTINGHOUSE CLASS 3 l
2 The specific surface loading for a single monolayer of 1 is 0.3 pg/cm,
2 4
Initial surface loadings greater than 10 monolayers have been observed on l
reacting surfaces (painted and galvanized) and up to 10 monolayers on inert surfaces such as glass (Reference 18).
For the South Texas Project containments, assuming all surfaces have the same affinity for iodine, the l
average surface loading (including I-127 and I-129) is approximately 2
10 pg/cm or 30 monolayers, the same order of magnitude as the inert 3
L surfaces capacity.
If, for example, a loading of only 10 monolayers was assumed for the reactive surfaces, the surfaces ce"1d accommodate approximately 30 times the iodine inventory releat to the containment.
l Hence, maximum surf ace loading is not a critical factor in the overall surface retention of iodine following a LOCA.
For paint, the amount of irreversibly absorbed iodine has been observed to vary between 40 and 100% of the initial loading.
Specifically, the long term retention for epoxy ranges from 40 to 60 percent, phenolic ranges from 70 to 90 percent and zinc is greater than 99 percent (Reference 13).
For the South Texas Project, the overall long term surface retention of iodine is expected to be at least 50 percent.
Considering that the potential for resuspension reducas the possible deposition loading by a factor of two, there is still sufficient capacity on the surfaces in containment to accommodate 17 times the iodine inventory released to containment.
3.6 References - Section 3 1.
" Calculation of Distance Factors for Power and Test Reactor Sites",
TID-14844, March 1962.
2.
" Standard Review Plan for the Review of Safety Analysis Reports for Nuclear Power Plants", NUREG-0800, Section 6.5.2, Rev. 1.
i 3.
Hilliard, R. K., et al., " Removal of Iodine and Particies from Containment Atmospheres by Sprays - Containment Systems Experiment Interim Report",
BNHL-1244, February 1970.
l l-0268D:1D/122789 3-11
HESTINGHOUSE CLASS 3 t
4.
Parsly, L. F., "Sor v Program at the Nuclear Safety Pilot Plant", Nuclear Technology, Vol. 10, April 1971.
5.
Barsali. L., et al., " Removal of Iodine by Sprays in the PSICO 10 Model Containment Vessel", Nuclear Technology, Vol 23, 1974.
6.
Nishizawa, Y., et al., " Removal of Iodine From A?mosphere by Sprays",
Nuclear Technology, Vol 10, April 1971.
7.
Davis, R. E., Nourbakhsh, H. P., and Khatib - Rahbar, M., " Fission Product Removal Effectiveness of Chemical Additives in PHR Containment Sprays",
Brookhaven National Laboratory. Technical Report A-3788, August 12, 1986, 8.
" Standard Review Plan for the Review of Safety Analysis Reports for Nuclear Power Plants", NUREG-0800 Section 6.5.2, Rev. 2, December 1988.
9.
Hilliard, R. K., and Postma, A. K., "The Effect of Spray Flow Rate on the Hashout of Gases and Particulates in the Containment Systems Experiment",
BNHL-1591, 1971.
- 10. Postma, A. K., et al, " Technological Bases for Models of Spray Washout of Airborne Contaminants in Containment Vessels", NUREG/CR-0009, October 1978,
- 11. " Assumptions Used.for. Evaluating the Potential Radiological Consequences of a Loss of Coolant Accident for Pressurized Hater Reactors", Regulatory Guide 1.4, Rev 2, June 1974.
- 12. Knudsen, J. G.,
and Hilliard, R. K., " Fission Product Transport by Natural Processes in Containment Vessels", BNHL-943, January 1969.
- 13. Rosenberg, H. S., et al, " Fission Product Deposition and its Enhancement Under Reactor Accident Conditions," Battelle Memorial Institute, BMI-1865, May 1969.
02l!"D:10/122789 3-12 d
1 WESTINHOUSE CLASS 3 14 McCormack, J. D.,
Hilliard, R. K., and Postma, A. K., " Removal of Airborne Fission Products by Recirculating Filter Systems in the Containment Systems Experiment", BNHL-1587, June 1971.
- 15. Bell, J. T., Lietzke, M. H., and Palmer, D.
A., " Predicted Rates of l
Formation of Iodine Hydrolysis Species at pH Levels, Concentrations, and Temperatures Anticipated in LHR Accidents", NUREG/CR-2900, November 1982.
- 16. Lin, C. C., " Chemical Effects of Gamma Radiation in Aqueous Solutions",
Journal of Inorganic Nuclear Chemistry 42, pp 1101-1107,1980.
1
- 17. Beahm, E. C., et al, " Chemistry and Transport of Iodine in Containment",
NUREG/CR-4697, October 1986.
- 18. Lemire, R.
J., et al., " Assessment of Iodine Behavior in Reactor Containment Buildings from a Chemical Perspect' 4"
Atomic Energy of Canada Limited, AECL-6812, June 1981.
j l
0268D:1D/122789 3-13
HESTINGHOUSE CLASS 3 TABLE 3-1 OBSERVED DEPOSITION VELOCITIES FOR VARIOUS SURFACE C0ATINGS (def. 13)
Coatina Name Coatina Tvoe Initial DeDoSition VelocitV. Cm/$et Phenoline 302 phenolic 0.148 Phenoline 368 phenolic 0.184 Amercoat epoxy 0.491 Corlar 588 epoxy 0.675 Dimetcote No. 3 inorganic zinc 0.707 Carbo-zine 11 inorganic zinc 0.678 0268D:10/122789 3-14
HESTINGHOUSE CLASS 3 TABLE 3-2 FLOODED OR OTHER SURFACES ASSUMED NOT AVAILABLE FOR DEPOSITION Surface 2
Item Material Area (Ft )
Containment Basement Paint (Epoxy 14,791 Mat Steel / Concrete Lined Halls (Partial)
Stainless Steel 9.318 Concrete 1
Stainless Steel Halls Stainless Steel 408 Stainless Steel Stainless Steel 1,666 Components 3",
4", 6" and 10" Stainless Steel 3,987 Dia. Pipes 3" and 4" Paint (Epoxy) 728 Dia. Pipes Carbon Steel Electrical Components Paint (Baked Enamel) 12,147 Painted Carbon Steel I&C and Electrical Galvanized 57,648 Cable Trays
- TOTAL AREA:
100,693
- l/2 of total area assumed not to be exposed to containment atmosphere.
0268D:lD/122789 3-15
I HESTINGHOUSE CLASS 3 TABLE 3-3 SUMHARY OF SPRAY AND DEPOSITION SURFACE AREAS (FOR CALCULATION OF IODINE DEPOSITION LAMBDA) i Surface 2
Item Material Area (ft )
A.
Containment Building Paint (Epoxy) 112.181 Steel Concrete B.
Internal Structures Paint (Epoxy) 449,643 (walls)
Concrete Steel / Concrete Carbon Steel C.
Mechanical Components Paint (Epoxy) 104,438 (Including Zine Painted Carbon Steel Mechanical Equipment)
Zinc Paint 1
D.
Electrical Component Galvanized 57,648 l
and Cable Trays
- E.
HVAC Galvanized 55,000 F.
Structural Steel Galvanized or 393,537 (Galvanized and Zinc Zinc Paint Painted Items)
TOTAL AREA:
1,172,447**
i
- 0nly 1/2 of total area was assumed to be exposed to containment atmosphere.
- To ensure that a conservative basis is used for the deposition area, the
{
total is reduced to 1,000,000 square feet, i
i 0268D:1D/122789 3-16
O t
HEST 8NGHOUSE CLASS 3 lif 80*
'tj-11NaOH M * ?D C" W N
- S3C** IMPCI A
=
h
,e M = W C"** 88PCI l1 x,~
.. m. _
o N% 15 90RIC ACID
+Q 8
r DilTILLED WATER E
, g (41% NaOH 8
g 90 a EPC, it DORIC ACID a
g JOISTILLED WATER
.\\1% NeOH l
+ SPC., it DORIC, ACID W'
lir*
lir*
IIT*
lir*
1 10 ICEltNE CONCENTR ATION IN CAS PilASE, C (mg/llter)
Figure 3-1.
Partition coefficient vs Iodine Concentration in Gas Phase (Ref 6) 0268D:1D/122789 3-17
e WESTINGHOUSE CLASS 3 1
onNL Dwo et-tN 9
I I
I I
I l /j/i/
I I
/
l l/,/
YCH01
/ 9,/
8 C/
A 40 f 4 8 t00 pH '9
/ /
)
/
C 7
C S00 A
//f E
Y
/ //
l ks
/ //
///
w
!/
/
pHe7
///
hs
///
g
/p/ /
,.~.....A.t.8. A.C,,,,_,,
7
//
L g4
// /
/,pH e 5 i
a.
g
///
/
///
/
.J 3
jf
/
I y a 10"8 T
- t00*C -
2
'.o.,,,**
1 min td
.1 4..t ~~'..' t h t
I i h
i i
1 i
-t 0
1 2
3 4
5 6
7 8
9 LOG TIME ( e )
1 i
figure 3-2.
Equilibrium Iodine Partition Coefficient (Ref 15) i 02680:10/122789 3-18
I HESTINGHOUSE CLASS 3 i
{
see a
6MtflAL t* CONCENTRATHM:
g 0
to-8m 80 --
a a
n m
Q Md M t
l 5
9 E.~. so 30
=
l O
i I
t I
O
_e 3
e
,e a
e
_e e
to la 9M l
Figure 3-3.
The Effect of pH on the 1 Yield 2
In an Irradiated Solution (Ref 16) 0268D:1D/122789-3-19
HESTINGHOUSE CLASS 3 4.0 RADIOLOGICAL CONSEQUENCES
'With the deletion of additive from the containment spray solution, the potential thyroid doses due to containment leakage during a postulated Loss-of-Coolant Accident (LOCA) need to be recalculated. The contribution to thyroid dose due to leakage of retirculated sump solution outside of containment does not need reevaluation since it is based on the conservative assumption that all iodine released to the containment is contained in the sump solution.
While airborne iodine is subject to removal by various processes, the noble gases, which are the primary contributors of gamma-body and beta-skin doses, are removed only by radioactive decay or by leakage to the-environment and thus are not impacted b,7 deletion of spray additive.
It is currently assumed by TID-14844 (Reference 1) that, as a result of a
[
the containment atmosphere and that (per Reference 2) the majority of the iodine appears in the elemental form and smaller fractions appear as organic compounds or as particulate (iodine absorbed on airborne particles). While the organic iodine can not readily be removed from the containment atmosphere, the particulate iodine can be removed by containment sprays and the elemental j
iodine can.be removed by sprays and by deposition onto surfaces in the l
containment.
'l c
t 4.1' LOCA Doses With Credit for Spray Additive The LOCA doses given in the South Texas Project FSAR (Amendment 56) were
-determined with spray soditive to enhance the spray removal of elemental iodine.. The reported thyroid doses due to' containment leakage following a LOCA are:
l t
i Site Boundary 125.5 rem i
LPZ Boundary 58.63 rem 02680:10/122789 4-1
HESTINGHOUSE CLASS 3 C
These doses are based on the following iodine removal parameters:
Elemental Iodine Spray removal constant (hr-I) 18.6 (DF1 12.3) and DF limit.
Deposition removal constant (hr-I) and DF limit:
unsprayed 7.06 (DFs 100) sprayed 0 534 (DF1 100) 1 Particulate Iodine Spray removal constant (hr-I) 6.13 (DFs 100) and DF limit Oraanic Iodine
-(No removal process assumed)-
'4.2 LOCA Doses with Spray Additive Removed Hith the spray additive' deleted, there is a significant change in the modelling of the spray removal of elemental iodine (see Section 3.1).
- Also,
.there are changes in the modelling of deposition removal of elemental iodine land in spray removal of particulate iodine. The new iodine removal parameters
=
-from Section 3 are summarized below:
' Elemental Iodine Spray removal constant (hr-I) 20 (DF1 60) and DF limit l
0268D:1D/122789 4-2
t i
HESTINGHOUSE CLASS 3 I
Deposition removal constant (hr'I) 4.5 (DFA 100) 7 and DF limit:
0.2 (100 < DFI 200) 0.0 (DF>200) i Particulate Iodine Spray removal constant (hr-I) 6.9 (DF1 50) i and DF limit:
0.7 (50 SDF1 1000) h
+
0.0 (DF>1000)
L Organic Iodine (No removal process assumed) i r
Since the current credit for spray removal-of elemental iodine is quite
-limited-(no removal beyond a DF of 12.3), the revised modelling will result in i
a significant increase in spray removal of iodine. Also, with the extension I
g of deposition removal to a DF of 200 instead of 100, there will be an
~ dditional reduction in the thyroid dose.
a
{
The revised modelling of the spray removal of' particulate iodine results in a minor increase in-the initial removal rate but the temoval rate is reduced to L10 percent of its original value at a DF of 50 instead of continuing unchanged
=
until a DF of 100 is reached. However, instead of stopping credit for iodine a
C removal at a'DF of 100, credit for spray removal of particulate iodine is continued at the reduced rate:until a DF of 1000 is reached.
Based on.the' review of the above changes in the iodine removal-parameters, it is. anticipated that the radiological consequence analysis:for the large break LOCA,_when performed for the spray additive elimination case, will show that the thyroid doses decrease from the values currently reported in the FSAR.
4.3-~ Identification of Conservatisms
'The.following conservatisms are related to the iodine removal parameters described in this section:
l 0268D:10/122789 4-3
i HESTINGHOUSE CLASS 3 l
1.-
Spray operation is expected to continue for at least two hours into the accident.
However, credit for elemental iodine removal by spray is stopped when-a DF of 60 is reached, which occurs well before 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br />.
2.
'At a decontamination factor (DF) of 60 for elemental iodine, spray removal is assumed to stop. This value is a conservative short-term value.
The long term DF will be greater than 100.
1 I
3.
The deposition removal rate is assumed to be reduced to 51, of the original value once a DF of 100 is reached and no additional credit is taken for deposition after a DF of 200 is reached.
4.
The eieraental' iodine deposition coefficient does not take into j
i account the different coating materials which would be expected to significantly increase the deposition rate.
j l
The source term that will be used in the offsite and control room dose analysis _-(not provided in this report) is assumed to be fifty percent of the i
core-iodines and is assumed to be released to the containment at the very i
~
beginning of the accident.
If a mechanistic determination of core fission product releases is assumed.the fraction of core iodines released would be a fraction.of the gap inventory.
Even if the total gap inventory were released j
to'the containment..this woul'd be approximately one percent of the core inventory of t dine.
Further there is evidence that the iodine released to i
th'e containmer
.ould primarily be.in the form of cesium iodide, which is
-highly soluble in water, rather than in the elemental form as is assumed.
This_would result in a smaller fraction of airboren iodine.
4.4, References - Section 4 1
1.
" Calculation of Distance Factors for Power and Test Reactor Sites,"
l TID-14844, March 1962.
0268D:lD/122789 4-4
HESTfNGHOUSE CLASS 3 2.
" Assumptions Used for Evaluating the Potential Radiological Consequences of a loss of Coolant Accident for Pressurized Hater Reactors," Regulatory Guide 1.4, Rev. 2, June 1974.
3.
" Standard Review Flan for the Review of Safety Analysis Reports for Nuclear Power Plants", NUREG-0800, Section 6.5.2, Revision 2. December 1988.
4.
Hilliard, R.
K., et al., " Removal of Iodine and Particles from Containment Atmospheres by Sprays - Containment Systems Experiment Interim Report",
8NHL-1244, February 1970.
I l
l
-02680:1D/122789 4-5 l
i HESTINGHOUSE CLASS 3 5.0 EFFECTS ON-HYDROGEN GENERATION AND EQUIPMENT QUALIFICATION 5.1:. Hydrogen Production due to Aluminum and Zinc Corrosion Following a large-break LOCA, hydrogen will be produced by the reaction of the zircaloy fuel clad and steam, by radiolytic decomposition of the core cooling solution and by the corrosion of aluminum and zine metals an'd zinc bearing primers.
Figurs 5-1 shows the relative hydrogen contribution due to the 4
various sources for the South Texas Project. Of these hydrogen sources, only
+
aluminum and zine corrosion will be affected by spray additive elimination.
~The corrosion rates of aluminum and zine are pH dependent.
Elimination of the spray additive decreases the pH of the injection sprays from a maximum of 11 to approximately 4.5.
The addition of caustic to raise the equilibrium pH to i
4 7.0 is necessary to. support retention of iodine in the water (see Section 3.4)-and to prevent chloride induced stress corrosion cracking of stainless steel (Section 5.2.1).
This pH of 7.0 is a decrease from the currently specified minimum equilibrium pH of 7.5 or greater for the recirculating
> solution. A discussion of aluminum and zine corrosion, relative to additive elimination, follows.
5.1.1 Aluminum Corrosion t
a The corrosion rate of aluminum decreases monotonically with decreasing pH.
!(Reference 1). Aluminum corrosion versus pH (taken from Reference 1) is
' presented in Figure 5-2.
Corrosion in solutions with pH in the range of;4 to
-5 appears -to be insignificant.
Thus, the reduction in injection spray pH and in equilibrium sump solution'pH would Mve the effect of reducing the rate of L
hydrogen production due to aluminum corrosion.
I t
L l
l 0268D:lD/122789 5-1 L..
HESTINGHOUSE CLASS 3
l5.1.2 Zinc (Galvanized Steel) Corrosion The corrosion of'zine is a function of pH and temperature, with temperature being the more influential parameter. The hydrogen production rate constant
_can be predicted with the following equation (Reference 2):
k - exp-(-8.07 - 2.84 X3 - 0.229 X) X3 - 0.177 Xj 2 3 X X) where:
I Xj --(pH-7)/3; for 4 1 pH I 10
'X2 - (ppm. Boron - 3000)/1000; for 2000 1 ppm B 1 4000 X3 = ((1/T) - 0.0027]/0.0004 T - Absolute l Temperature 2
and k - sem/m - hr
.The rate ~ constants for the spray injection period (approximately 250-300*F) were evaluated with spray additive (pH 10. 2100 ppm B) and without spray additive,(pH 5, 2100 ppm B).
The results of this evaluation are presented in FigureLS-3._ Although the graph shows a 10 percent rate decrease at 300'F and l
approximately an 8 percent increase at 150'F, only the high temperature portion. is applicable to the spray injection period.
The ' rate constants for the spray recirculation period (approximately 150-250*F) were also evaluated. The rate _ constants with spray additive.(pH L
7.5-to_9.5, 2100 ppm B) and without additive (assumes solution pH will be
. raised into the range'of 7-9.5) are. presented in Figure 5-4.
A maximum rate increase of 4 percent occurs at 150*F.
l L
p L
02680:10/122789 5-2
HESTINGHOUSE CLASS 3 C
5.1.3 Zinc Enriched Paint Corrosion
.The corrosion of zine based paints, like galvanized steel, is a strong function of temperature and exhibits little pH effect.
Hydrogen production
'l rates, for:zine paint corrosion, were obtained from a recent Sandia study q
(Reference 3).
Using a standard multiple regression. technique, the following equation was i
. developed to fit' the " vapor / spray" test data:
k - exp (-11.6738 + X) + X )
2 where:
X) = (4.1497 x 10-2) T; for 200 1 T'C 1 350 2 - (3.6345 x 10-3) pH; for 7 1 pH I 9 a
X LNote that,E ecause of data limitations, the pH range is restricted.
The b
results of this evaluation are presented in Figure 5-5.
4 The. maximum rate variation, over the specified pH range, is less than 1 il.
- percent, x
i In acidic solutions, zine based paint is expected to exhibit the same low temperature rate increase /high temperature rate decrease that was observed for
' galvanized steel..
1 L
Hydrogen Production - Conclusion ll 5.1.4
/ Elimination of the spray additive'will have little net effect on hydrogen generation due to the corrosion of aluminum and zine in the post-LOCA containment environment.
No changes are needed to the present hardware or to l
the current hydrogen generation analysis.
L l
l 0268D:1D/122789 5-3
l' i
HESTINGHOUSE CLASS 3 i
- 5.2 Equipment Protection 5.2.1 Protection of Stainless Steel To minimize the occurrence of chloride induced stress corrosion cracking (CISCC), Branch Technical. Position MTEB 6-1 (Reference 4) recommends that the minimum pH of the sump solution should be 7 and that tha b.i@er the pH, in the range of 7 to 9.5, the greater the assurance thtd no stress corrosi)n cracking
.will occur. This recommendaticr. ic hased primarily on the results )f Westinghouse tests (Reference 5) which showed that at pH.7, 100 ppm Cl,
- sensitized and nonsensitized samples of 304 stainless steel cracked in approximately 7.5 and 10 months, respectively.
Hestinghouse corrosion tests.(Reference 5) indicate that the minimum time to crack (1007 crack,-304 SS welded single U bend) in a pH 4.5, 100 ppm C1 solution is 3 days. No cracking of any of the test materials was observed before 8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br />.
Thus, crack initiation occurred between 8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> and three days.
l
'The'pH adjustment' must occur. prior to the initiation of cracking.
- Hence,
' based on the Westinghouse results, it is necessary that the pH of the sump solution be raised into the caustic range within 8-hours, l
L l^
R
.It'is.important to note that chlorides are not expected to instantaneously
- appear. in solution in' concentrations sufficient to initiate cracking.
The f
initial spray and' safety injection solution is drawn from the refueling water l
' storage' tank where the chloride concentration is limited to 0.15 ppm.
The L
injection phase lasts for approximately 40 minutes.
The Hestinghouse tests (Reference 5) -indicate that crack initiation in boric acid with 0.4 ppm chloride and pH of approximately 4 requires extended exposure times (12 months in one' example).
Hence, cracking.will not occur during spray and safety
' injection.
It is only during recirculation operation that potentially contaminated core cooling solution will contact vital equipment.
- 02680:1D/122789 5-4
X HESTINGHOUSE CLASS 3 l
" As-the solution washes over the containment structures and components,
' chlorides and other contaminants will be removed from the surfaces and dissolved in-solutibn. Concrete, which is a significant potential chloride
. source, is painted with a: nuclear qualified coating'which is expected to
. greatly impede chloride leaching.~
To provide perspective, approximately 600 pounds of salt (Nacl) would have to be leached for a 100 ppm Cl
= concentration...Thus, it appears that the time to reach a 100 ppm chloride concentration may be days rather than hours.
Despite the expectation that buildup of chloride concentration to a critical level would require an extended time period, it is recommended that the pH of the sump solution be adjusted to 1 7.0 within 8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> of the accident initiation.
Based on the above discussion, 8 hours9.259259e-5 days <br />0.00222 hours <br />1.322751e-5 weeks <br />3.044e-6 months <br /> is considered a conservatively short time period in wh6ch to make the adjustment.
'5.2.2 Protection.of Electrical Components Safety related electrical equipment is tested to confirm the ability of the seals.to exclude-the containnment eAvironment-from the interior of the
- component.- To maximize the challenge to seal materials, high pH sprays (pH 8-to 11) and temperature (250 to 300*F) and. extended time periods (approximately
'l year) have traditionally been used as the basis for testing to simulate the
' post-LOCA containment environment. As such, materials qualified forllong term exposure at high pH will not be. adversely affected by short term exposure to 110w pH solution. The ingress of chemical spray and/or steam (which will
~
L-
' condense), regardless of the chemical composition, will result in electrical
[
shofting and subsequent failure of the component to perform its safety related L
function.
Following a LOCA,' equipment and surfaces within the containment will initially be: covered with, boric acid spray solution of pH in the range of approximately i
7.5 to 10.5,' or spilled reactor coolant of pH in the range of approximately 6 to-9, depending on the concentration of boron and lithium hydroxide in the I
E coolant. Hith~ the elimination of the sodium hydroxide spray additive, the pH 0268D:lD/122789 5-5
=
f WESTINGHOUSE CLASS 3
-e s
of the~ containment spray solution (2500 2700 ppm boron solution from the RHST)-
i is reduced to approximately 4.5. Equipment in-containment will be exposed to
.this low pH. solution for less than one hour, during the spray injection I
phase.
During this time, trisodium phosphate (TSP), stored in baskets located
-in-containment, will begin to dissolve and raise the pH of the recirculating core: cooling solution into the range of 7.0 to 9.5 (see Section 6.2.2 for discussion of TSP dissolution time).
Spraying of recirculated fluid is anticipated to continue for approximately one hour following spray injection, providing a' total spray time of approximately 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br />.
Thus, all surfaces will eventually be resprayed with alkaline solution.
It is important to note l
that with the elimination of the spray additive only the pH of the short duration injection.spary is significantly different from that specified with spray additive.
The long term pH of the recirculation solution is essentially unchanged.
Fol' lowing a LOCA, the interactions between the containment spray and sump j
t solutions, and reactor coolant, can be categorized into physical effects and chemical effects that are dependent on the chemical composition of the sol ution_.1 In general, short term physical effects include polymer softening, due to elevated temperatures. and subsequent failure of the softened seal due to: elevated containment pressure.
Longer term chemical effects, due to the ionic strength of the solution rather than the pH, include osmotic swelling of-polymers and short circuiting.- To reiterate, elimination of the spray
~
. additive only-~affects the pH of the injection spray which'will' operate for alessithan~one hour.
To summarize, seal materials are. tested at high temperature and pH and for time periods simulating approximately one year of exposure.
Hence, exposures to low pH-solution for time periods less than 1 hour1.157407e-5 days <br />2.777778e-4 hours <br />1.653439e-6 weeks <br />3.805e-7 months <br /> will have no adverse effection the ability of the seal material to perform its intended function in the long term.
L 1
0268D:10/122889 5-6
l HESTINGHOUSE CLASS 3 5,'2.3-Protection of-Containment Coatings Coatings are used in-the containment to provide corrosion protection for metals and to aid in decontamination of surfaces during normal operation.
Coatings-that delaminate may clog the emergency sump screens, core, and heat
- exchanger flow paths and foul heat transfer surfaces.
?
-Like electrical equipment, coatings are also tested with a high pH solution i
for long time periods, to maximize the potential deterioration of the coating And, like seal materials coatings will not be adversely affected by short term exposure to low pH spray solution.
In general, coating failures tend to be i
. thermally related (Reference 3) rather than chemical.
In fact, one
.i
'Hestinghouse study (Reference 6) indicated that some coatings showed better resistance to mild acid solutions (pH 4 to 5) than to alkaline solutions.
i
/
i i
- ,I'..
r i
4
.0268D:1D/122789 5-7
HESTINGHOUSE CLASS 3 5.3 References - Section 5 1.
" Corrosion Study'for Determining Hydrogen Generation from Aluminum and Zinc During Post-Accident Conditions", HCAP-8776, (Non-Proprietary)
-April.1976.
2.
"The Relative Importance of Temperature, pH and Boric Acid Concentration on Rates of H Production From Galvanized Steel Corrosion",
i 2
NUREG/CR-2812, January 1984.
'3.
"The Effects of Post-LOCA Conditions on a Protective. Coating (Paint) for the Nuclear Power Industry", NUREG/CR-3803, March 1985.
4.:
NRC Branch Technical Position HTEB 6-1, "pH for Emergency Coolant Hater
-for PHR's"
)
l q
5.
" Behavior of Austenitic Stainless Steel in Post Hypothetical Loss of j
Coolant Environment", HCAP-7798-L.(Proprietary), November 1971, HCAP-7803
-(Non-Proprietary), December 1971.
6.
'" Evaluation of Protective Coatings for Use in Reactor Containment",
HCAP-7198-L (Proprietary), November 1971.
L l
l 0268D:1D/122889 5-8
1 I
NESTINGHOUSE CLASS 3 1
t l-
)
1 TOTAL H2 in RC8 j
gg 2.
200 RA010ALYSIS
~
1 220 f
no i
}
180 B in 1,n 3in i
g. in N
a 40 ZINC #AINT gWATER 20 C
^L *'* Y*
l i
0 0
2 4
6 8-
- 10. 12 14 16 10 20 22 24 26 28 30 32
- 34. 34-Title AFTER LOCA(DAY 8) l l
Figure 5-1 Relative. Hydrogen Contribution From All Sources (South Texas Project FSAR Figure 6.2.5-5) i t
l L
L 0268D:lD/122789 5-9
~.
WESTINGHOUSE CLASS.3 l100 soo*
1000 900 800 a
g.
~
700 E
Y 600
'E i
5 G
500 i
2 5
400 300 h
'l
-200 iso
- l 120'
.100
-l 0
6 7
8 9
10 il 12-pH
-l Figure 5-2 Aluminum Corrosion Versus pH (Ref 1) j L
1 l-1 1
I*
1 0268D:10/122789 5-10
1.
- 2 HESTINGHOUSE CLASS 3 IE-2
- pH 10 4
.x i lE-3
. ti '
ow a
g.
a EM D pH 5
'5o IE-4
-wg.
. Q...
cc lE-5 150 175 200 225 250' 275 300 TEMP - DEG-F
.e
' Figure 5-3 Zinc (Galvanized Steel) Corrosion Rate Constants for Spray Injection l
0268D:10/122769 5-11
HESTINGHOUSE CLASS 3-
- l' 1
~1E-2 o pH 7 d
i
- pH 9.5 A
I 3 IE-3 d
.o
.m
'l y- :
E D
3 gIE-4 u
w-p c:
6 i
IE-5.
150 175 200 225
'250 275 300 TEMP - DEG F l
is Figure 5-4 'Zine (Galvanized Steel) Corrosion Rate Constants for Spray Recirculation I
.0268D:10/122789 5-12 o
9.
1 s
HESTINGHOUSE CLASS 3
~' '
r IE-2 q
D pH 7
- pH 9
$g k
. g,
- m O
H IE-3 5
tE:
z.
o L)
O d
.g.
I IE-4 175 200 225
'250 275 300 l
150-TEMP - DEG F i
' Figure 5-5 Zine Based Paint Corrosion Rate Constants i
5-13 0268D:1D/122789'
l WESTINGHOUSE CLASS 3' 6.0 ADJUSTHENT OF SUMP SOLUTION pH 6.1 Definition of Required Long Term pH
'As discussed in Section 3.4, a sump solution pH of 1 7.0 is required to assure that the. iodine removed by the sprays is retained in solution.
From Section 5.1 it is seen that the long term corrosion rates for galvanized steel and l
zine based paint will be comparable to the FSAR rates at pH 7 to approximately
- 11. Also in Section 5.1 it.is seen that the long term aluminum corrosion rates at pH 7 will be significantly less than the FSAR rates.
In Section 5.2 it is stated that the minimum pH recommended to protect stainless steel from chloride cracking is 7.0.
A minimum pH of 7.0 satisfies all of the Section 3 and 5 requirements.
6.2 Caustic Addition iThis section describes the current spray additive system at the South Texas Project, which utilizes sodium-hydroxide solution, and the solid. trisodium
. phosphate system proposed to replace it.
~6.2.1-Sodium Hydroxide Spray Additive L he Containment Spray System currently in place at the South Texas Project is T
! designed to add sodium hydroxide to the containment spray solution to remove l
. iodine. from the containment atmosphere and ensure an equilibrium sump solution pH of 7.5 to 10.0 for the retention of elemental iodino.
Stainless steel tanks, located outside of the containment, contain sufficient 30-32 weight-percent.of' sodium hydroxide solution to bring the containment sump fluid to a minimum equilibrium pH of 7.5 upon mixing with the borated water from the RHST, the accumulators, and the reactor coolant.
Sodium tiydroxide is added to the spray liquid (drawn from the RHST) by a liquid jet eductor. On actuation, approximately 5 percent of each spray pump discharge flow is diverted through each spray additive eductor to draw sodium
-0268D:lD/122789 6-1
HESTINGHOUSE CLASS 3 a-
-hydroxide from the tanks.
The sodium hydroxide is added to the spray water until-the spray additive tank is empty or until the RHST. water reaches low-low level, whichever occurs.first.
6.2.2 Trisodium Phosphate The. proposed replacement for the liquid sodium hydroxide spray additive system
. consists of solid trisodium phosphate stored in baskets strategically located in the post-LOCA flooded region of the containment.
The initial-containment spray will be boric acid solution from the refueling water storage tank which has a pH of approximately 4.5.
As the initial spray solution and subsequently the recirculation solution comes in contact with the trisodium phosphate, the TSP dissolves raising tne pH of the sump solution to an equilibrium value of 2. 7.0.
Handling TSP requires an approved dust mask and the use of goggles and rubber gloves is recommended..
Titration curves for TSP in boric acid solution are provided in Figure 6-1, physical data is presented-in Table'6-1.
For the South Texas Project, the 4
12 H O)= required to provide an equilibrium mass of TSP (as Na 2
3 sump solution pH of 7.0 is 11,500 pounds.
TSP is a free flowing granular material that is highly soluble in water (112.8 Ht% - Reference.1).
However,' TSP will clump in a humid environment, e.g.
inside the reactor containment, and, in a worst case, will form a solid
. block.
~
L
.The time (T) required to dissolve the TSP can be estimated as follows-l T
- H / (R
- A) j.<
L g
p L
L l_
0268D:lD/122789 6-2
HESTINGHOUSE CLASS 3 Where M
- total mass of TSP in container 2
R
- dissolution rate constant - 0.7 lb/ft -min (derived from data in Reference 2, based on TSP in the form of a solid block, water at 160'F, and no agitation of the solution) i 2
A
- contact area - ft The TSP will be stored in six baskets, 4 ft by 7 ft, having a TSP bed depth of 1.5 feet.- The minimum bulk density of TSP, as loaded into the baskets is 54 3
lb/ft. A conservative contact surface area is assumed neglecting the side surfaces (assumes that the TSP is in contact with the sump solution only at the top'and bottom surfaces). With a required mass of TSP of 11,500 lb and a 2
surface area.of 336 ft, the dissolving time would be 49 minutes.
i LThe conservative total dissolution time is approximately 1.5 hours5.787037e-5 days <br />0.00139 hours <br />8.267196e-6 weeks <br />1.9025e-6 months <br /> assuming
. that the TSP is submerged in' approximately 40 minutes.
In an actual
, post-accident situation, all of the basket surfaces would be exposed to the l sump solution..Further, the initial water temperature would exceed 200*F and there would be significant agitation, All of these factors would reduce the
. time for' dissolution of the TSP.
U
' TSP will be stored in-containment at an elevation that will be flooded post-LOCA.. The TSP will be stored in six smail: baskets rather than in one
[L
'large basket.- Multiple baskets will minimize the TSP exposure to local steam 1
l:
or water leaks.
Distributing the baskets around the containment will assure a
- more uniform mixture in the sump solution.
L The TSP. baskets will be mesh sided to facilitate wetting post-accident and still retain the TSP. granules during normal operation.- The baskets have a low profile which will enhance submergence and dissolution.
U The baskets will be designed to hold the weight.of the TSP and, with the j
bolting, will withstand _ seismic loads.
i
'0268D:lD/122789 6-3
HESTINGHOUSE CLASS 3 6.3 References--- Seetion 6 5
- 1. - Occidental Chemical Corporation, Data Sheet No. 909A, April 1985.
2.
Letter from J. L. Hilkins, Assistant General Manager, Omaha Public Power District, to R. C. De Young, Assistant Director for PHRs, U.S. AEC, November 14, 1973.
L
=
-=
I
=
-0268D:lD/122789 6-4
^
?..
WESTINGHOUSE CLASS 3
.s TABLE 6-1 PHYSICAL DATA FOR TRIS 0DIUM PHOSPHATE (Ref. 1)
'1 Formula:
Na P04 - 12H 0 3
2 ha PO, minimum: 42.97%
3 4 3
Bulk density:
57 1 3 lbs/ft Screening (US Standard Sieve) on 20 mesh:
5%
on 65 mesh:. 85%
Thru 100 mesh:
5%
Solubility in water i
Temo
'F-81_%
104 43.9 140 73.3 t
176 94.0 212 112.8 r
t 6
s 1
'i L
1 '
I '
0268D:lD/122789 6-5
HESTINGHOUSE CLASS 3 I
8.0 2500 pm B 2000 ppm B 7.8 -
3000 ppm B Q 7.6 7.4 7.2 7.0 3
4 5
6 0
1 2
GRAMS-TSP / LITER OF SOLUTION i
I Figure 6-1.
Titration Curves for TSP in Boric Acid Solution 0268D:lD/122789 6-6
1 4
HESTINGHOUSE CLASS 3 q
7.0 TECHNICAL SPECIFICATIONS 7.1 - Description of Proposed Changes The proposed change would delete, in its entirety, Technical Specification 3/4.6.2.2 " Spray Additive System", and replace it with a new Technical Speci-fication requiring trisodium phosphate in the containment emergency sump area.
Technical Specification 3/4.6.2.2, " Spray Additive System" requires that three i
spray additive tanks, each containing a volume of between 1061 and 1342 gallons of between 30 and 32% by weight of Na0H solution, and three spray additive eductors each tip'able of adding Na0H solution from its associated
, spray-additive tank to its Containment Spray System pump flow be operable in'
[
Modes'1, 2, 3, and 4.
The original purpose of the spray additive system was to-ensure that sufficient NaOH would be added to the spray to raise the pH of
^ the injection spray solution to within the range of 7.5 to 10.5 and to maintain the equilibrium pH of the sump solution within the range of 7.5 to l
.10.0; -The effects of the increased pH levels are to increase the iodine l
removal capability of the spray and the iodine retention in the sump sol tion.
'An additional function of the NaOH in the Spray Additive Sys em, during the
?long term recirculation phase, is to maintain the pH level of sump solution at 2 7.0 to minimize the potential for chlorine induced stress-corrosion cracking of aust'enitic stainless steel.
l JJustification for the deletion of the Spray Additive Tanks and the Spray
- Additive System of Technical Specification 3/4.6.2.2 is provided in the an' lysis of this report. This analysis utilized current NRC methodology a
q (NUREG-0800, Section 6.5.2, Rev. 2), combined with knowledge gained from recent studies on the behavior of iodine in the post-LOCA environment, to I
demonstrate that the deletion of the Spray Additive Tank does not significantly change the. calculated offsite thyroid doses..Thus, low pH boric acid containment sprays (pH approximately 4.5) can effectively perform the iodine removal function that was previously performed by the sodium hydroxide sprays; 02680:10/122889 7-1
I HESTINGHOUSE CLASS 3 4
However, in the post-LOCA recirculation' phase, the Emergency Core Cooling (ECC) solution pH must be increased to 2. 7.0 to reduce the potential for
-chloride' induced-stress corrosion cracking of austenitic stainless steel components, assure the retention of iodine in the containment sump, and to
. limit the hydrogen produced by the t.orrosion of galvanized surfaces and zinc
. based paints. To accomplish this increase in the ECC solution pH, a new E
Technical Specification is proposed to replace Technical Specification 3.6.2.2.
This new Technical Specification requires the presence of a specified amount of trisodium phosphate in the containment area.
The analysis in this report has shown that this amount of trisodium phosphate will maintain
'long term pH control of the ECC recirculation solution, thereby reducing the potential for' chloride induced stress corrosion and assuring iodine retention in the sump solution.
7.2. Proposed Significant Hazards' Consideration The proposed changes discussed above shall be deemed to involve a significant hazards consideration if there is a positive finding in any of the following areas:
1.
Hill operation.of the facility. in accordance with this proposed change involve a significant increase in the probability or consequences of an accident previously evaluated?
Respons'e: No r
The plant systems, in which a change is proposed, are intended to respond to and mitigate the effects'of a LOCA.
The proposed changes have no i
effect on the probability of the occurrence of a LOCA.
As discussed in Section 4.2 of this report, with the deletion of the Spray Additive System'and its replacement with a sump pH control system, the radiological consequences'of a postulated LOCA are expected to be bounded by the values currently reported in the FSAR.
(Note: The actual determination of radiological consequences is the responsibility of l
l HL&P).
In addition, the use of TSP for a long term recirculation l-0268D:10/122889 7-2 t
l
a i
HESTINGHOUSE CLASS 3 phase pH control meets all the requirements for control of chloride induced stress corrosion and assures iodine retention in the sump solution.
Further, there will be'little net effect on hydrogen generation due to the corrosion of aluminum and zinc, and the hydrogen production analysis currently reported in the FSAR remains conservative and bounding.
2.
Hill operation of the facility in accordance with this proposed change create the possibility of a new or different kind of accident from any j
accident previously evaluated?
Response
No I
i The accident impacted by the substitution of a-passive TSP basket system i
for the containment spray additive system is the large-break LOCA.
This LOCA is currently described in the FSAR. The proposed change has no effect on the kind of accident.
3.
Hill operation of~the facility in accordance with the proposed change involve a significant reduction in a margin of safety.
Response
No
]
The radiological consequences of a postulated LOCA are anticipated to decrease from those reported in the FSAR. Also, the pH acceptance limit specified in MTEB 6-1 for assuring prevention of chloride induced stress corresion cracking of stainless steel will still be met.
There will be no adverse impact on electrical equipment, coatings, or hydrogen generation due to aluminum and zinc corrosion.
7.3 Basis for Proposed No Significant Hazards Consideratior. Determination Me Commission has provided guidance for determining whether a significant hazait consideration-exists by providing certain examples (48 FR 14870) of amendments that are considered not likely to involve significant hazards consideration.
Example (vi) relates to a change which either may result in some 0268D:1D/122889 7-3
1c!
HESTINGHOUSE CLASS 3-
. increase in the probability or consequences of a previously-analyzed accident l
-or.may in some way reduce a safety margin, but where the results of the change sare clearly within all acceptance criteria with respect to the system or
-component specified in the Standard Review Plan (SRP).
4 l
.SRP Sections-6.1.1, " Engineered Safety Features Materials," 6.5.2,_
" Containment Spray as a Fission Product Cleanup System," and 15.6.5, " Loss of
- Coolant Accidents Resulting From Spectrum of Postulated Piping Breaks Hithin the Reactor Coolant Pressure Boundary," define the pertinent acceptance t
-criteria.
SRP Section 6.1.1 requires that the composition of containment l
' spray and core cooling water be controlled to ensure a minimum pH of 7.0
-following a loss of coolant accident to inhibit initiation of stress corrosion cracking.
SRP Section 6.5.2 defines conditions under which the containment-o l
spray system can be credited for fission product removal.
SRP Section 15.6.5 l-defines, by reference to 10 CFR 100, the post accident dose limits.
l The only impact that the proposed Technical Specification change has on this system is the deletion of the.use of NaOH in the initial containment spray L
phase following a postulated LOCA, and the substitution of trisodium phosphate for NaOH in the sump' solution during the long term recirculation phase.
The current.FSAR Analysis (Amendment 56), taking credit-for NaOH addition, calculates a-0-2 hourgExclusion Zone Boundary (EZB) thyroid dose of 125.5_ REM and a 0-30-day. Low Population Zone (LPZ) thyroid dose of 58.63 REM.
In 10CFR100 an upper limit of 300 REM is specified for both categories.
For the I
new analysis, the corresponding EZB thyroid dose is (to be provided by HL&P)
REM and the LPZ thyroid dose is (to be provided by HL&P) REM.
It should be
.l noted that in all cases there is significant margin between the calculated thyroid doses and the-limits defined in 10CFR100. This margin is essentially independent of whether the Spray Additive Tank is operable or if the SAT is deleted and the Sump pH Control System is operable..Thus, the ' proposed change-i meets the dose acceptance criteria of SRP Section 15.6.5.
-t i
The proposed requirements will assure a post accident sump pH greater than or equal to 7.0 thereby meeting the SRP 6.1.1 requirements to minimize the potential-for chloride induced stress corrosion cracking of stainless steel
~0268D:1D/122889 7-4
The Light c o mp a ny *h l** P"'J"' U""I'"'""'""8 S'"""
- " " " *
- d '" "'"" I ' *
- flouston Lighting & Power October 30, 1990 ST HL AE-3378 File No.: G20.02.01 G2.06 10CFR50.90 U. S. Nuclear Regulatory Commission Attention: Document Control. Desk Washington, DC 20555 South Texas Project Electric Generating Station Units 1 and 2 Docket Nos. STN 50-498 and 50 499 Proposed Amendment to the Unit 1 and Unit 2 Technical Specifications to' Replace Sprav Additive with Recirculation Fluid oH Control Pursuant to 10CFR50.90, Houston Lighting & Power Company (HMP) hereby proposes to amend its Operating Licenses NPF 76 and NPF 80 for the South Texas Project Electric Generating Station (STPECS), Units 1 and 2, by incorporating the attached proposed change to the STPEGS Technical Specifications. The proposed change consists of replacing Technical Specification 3/4.6.2.2 " Spray Additive System" with a new specification entitled " Recirculation Fluid pH Control System" to be consistent with a planned plant modification which would eliminate the containment spray additive system. The proposed Technical Specification is included in Attachment 2.
HMP has reviewed the attached proposed amendment pursuant to 10CFR50.92 and determined that it involves no significant hazards considerations. The basis for this determination is provided in the attachments. In addition, based on the information contained in this submittal and the NRC Final Environmental Assessment for STPECS Units 1 and 2, H MP has concluded that, pursuant to 10CFR51, ther. a.e no significant radiological or nonradiological impacts associated with the t.oposed action and the proposed license amendment will not have a significant effect on the quality of the environment. The STPEGS UFSAR will be revised in accordance with this change subsequent to the NRC approval, e
The STPEGS Nuclear Safety Review Board has reviewed and approved the y
proposed changes.
m In accordance with 10CFR50.91(b), HMP is providing the State of Texas g'-
with a copy of this proposed amendment, i!
$6 Your approval is requested so that this change can be implemented for each unit during the respective 1991 refueling outages.
4 m o24.N12 A Subsidiary of flouston industries incorporated 7 0. c.
} i(
l g
HESTINGHOUSE CLASS 3 and the generation of hydrogen.
Therefore, because the proposed change meets the SRP acceptance criteria, it is similar to example (vi) of 48 FR 14870.
Based on the above Safety Analysis, it is concluded that:
(1) the proposed change does not constitute a significant hazards consideration as defined by r
10CFR50.92; (2) there is reasonable assur:uce that the health and safety of the public will not be endangered by the proposed change; and (3) this action will not result in a condition which significantly alters the impact of the station on the environment.
i 7.4 Proposed Technical Specification for Sump Additive Following are the proposed specifications for both Units 1 and 2:
s i
I l
1 02680:1D/122789 7-5 29
i WESTINGHOUSE CLASS 3 CONTAINMENT SYSI{M$
RECIRCULATION FLUID PH CONTROL SYSTEM LIMITING CONDITIONS FOR OPERATION 3.6.2.2 The recirculation fluid pH control system shall be operable with between 11,500 lbs. (213 cu. ft.) and 15,100 lbs. (252 cu ft.) of trisodium phosphate (w/12 hydrates), or equivalent, available in the storage baskets in the containment.
APPLICABILITY: Modes 1, 2, 3, and 4 AC110N:
With less than the required amount of trisodium phosphate available, restore the system to the correct amount within 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br /> or be in at least HOT STANDBY within the next 6 hours6.944444e-5 days <br />0.00167 hours <br />9.920635e-6 weeks <br />2.283e-6 months <br />; restore the system to the correct amount within the next 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> or be in COLD SHUTDOHN within the following 30 hours3.472222e-4 days <br />0.00833 hours <br />4.960317e-5 weeks <br />1.1415e-5 months <br />.
SURVEILLANCE REQUIREMENTS 4.6.2.2 During each refueling outage, as a minimum, the recirculation fluid i
pH control system shall be demonstrated operable by visually verifying that:
- 1) 6 trisodium phosphate storage baskets are in place, and
- 2) have maintained their integrity, and j
- 3) are filled with trisodium phosphate such that the level is above j
the indicated fill mark.
BASES m
3/4.6.2.2 RECIRCULATION FLUID PH CONTROL SYSTF#
j The operability of the recirculation fluid pH control system ensures that there is sufficient trisodium phosphate available in containment to guarantee a sump pH of 17.0 during the recirculation phase of a postulated LOCA.
This pH level is required to reduce the potential for chloride induced stress corrosion of austenitic stainless steel and assure the retention of iodine in the recirculating fluid.
The specified amounts of TSP will result in a recirculation fluid pH between 7.0 and 9.5.
02680:1D/122789 7-6 i
(
-r
'r L!
ATTACRMENT 1 SIGNIFICANT HAZARDS EVALUATION FOR THE REPLACEMENT OF Tile SPRAY ADDITIVE SYSTEM k'ITil Tile RECIRCULATIOh TLUID pil CONTROL SYSTEM Et A1/024.k12
Attschatnt 1 ST HL AE 3375 Pap 1 of 6 SIGNIFICANT HA2.ARDS EVALUATION FOR THE kl PIACEMEN'l of THE SPRAY ADDITIVE SYSTE/
VITH THE RECIRCULATION FLUID pH CONTROL SYSTEM Backe.round The Con t a i teen t Spray System design for STPECS currently utilizes caustic (sodium hydroxide. NaOH) containment spray (pH 7.5 to 10.5) to assure the removal of radioactive iodine f rom the contaitutent atmosphere following a larp break LOCA.
Airborne iodine must be removed to trininize the release to the environment due t o c ont aiturent leakage and thus assure that the offsite dore guidelines of 10CTR100 are met.
The Containment Spray System currently uses the Spray Additive Tanks (SAT) to provide the caustic containment spray. Techr.ical Specifications require performing SAT related tests and maintenance. This testing and maintenance is resource intensive and the handling of concentrated sodium hydroxide solution requit os special precaut ions due to its hazardous nature Additionally, contamination of the primary grade water by sodium hydroxide leakage into the Reactor Coolant System has occurred at STPECS. This contamination requires the use of the demineralizers to remove the contamination which depletes the resin.
Higher dose rates can result from this contamination due to personnel exposure to the depleted resin and transmuted sodium hydroxide in the Reactot Coolant System.
Revision 2 to Standard Review Plan (SRP) section 6.5.2,
" Co n t a i tutie n t Spray as a Fission Product Cleanup System" and industry precedence has made it possible for STPEGS to pursue design changes to isolate the Unit I and 2 spray additive systems. The methodology of SRP 6.5.2 (Rev. 2) identifies that post accident removal of elemental iodine (the predominant form) from the LOCA c ont aitunent atmosphere is essentially independent of spray pH.
Thus, H14P proposes to eliminat e Naoll addit ton t o contaitunent spray. This change has been approved for use at Millstone 2, Palo Verde. San Onofre, Calvert Cliffs, Davis Besse and St. Lucie 2.
The removal of the spray additive does not eliminate the need for adjusting the pH of the Emergency Core Cooling System,ECCS) tecirculation solutlon. To assure that the iodine removed by the sprays is retained in solution, to minimize chloride induced stress corrosion cracking of austenitic stainless steel components, and to minimize the hydrogen produced by the corrosion of galvanized surfaces and zine-based paints, the long-term pH of the ECCS solution should be no less than 7.0.
Since the initial pH of the boric acid ECCS solution, without spray additive, will be approximately 4.5, a chemical additive must be utilized to raise the pit of the solution in the containment sump.
Al/024 N12 P
i i
e ST.HL.AE.3378 s
Page 2 of 6 Backcround feont'd)
The proposed replacement for the liquid sodium hydroxide spray additive system consists of solid trisodium phosphate (TSP) stored in baskets strategically located in the post.LOCA flooded region of the containment (Figure 1.2 12). Additional detail is included in the attached WCAP 12477.
The initial containment spray will be boric acid solution from the refueling water storage tank which has a pH of approximately 4.5.
As the initial spray solution and subsequently the recirculation solution comes in contact with the trisodium phosphate, the TSP dissolves raising the pH of the
. sump solution to an equilibrium value of 2 7.0, WCAP 11611,_" Methodology for Elimination of the Containment Spray Additive", was prepared f or Westinghouse Owners Croup (WDC) participants to assist in the evaluation for elimination of spray additive systems. Choosing this course of action STPECS has performed a plant specific analysis entitled WCAP 12477, " Spray Additive Elimination Analysis for the South Texas Project" which is provided in Attachment 3.
It contains calculations of iodine removal coefficients and decontamination factors; also included are evaluations of the use of TSP for long term pH control, the potential for chloride induced stress corrosion cracking, hydrogen generation and equipment protection.
Offsite, Control Room, and Technical Support Center (TSC) dose calculations were revised for the design basis LOCA using the results of VCAP 12477, as well as the revised treatment of Control Room and FHB HVAC failures submitted in a STPECS License Amendment Request dated July 14, 1989 (ST.HL.AE.2940). The results of the calculations are reflected in the attached i
tables.
Procosed Chance L
The proposed change is to replace Technical Specification 3/4.6.2.2 l
" Spray Additive System" and its basis _with a specification entitled
" Recirculation Fluid pH Control System" and basis as shown in the attachments.
l Saferv Evaluntion Passive pH Control System l
The proposed Recirculation Fluid pH Control System will have the same i
function as the present Spray Additive System; i.e.,
to mitigate the effects of a loss-of coolant accident. The change to a passive pH control system will eliminate the possibility of an active spray additive component failure. The proposed pH control system cannot initiate any accident evaluated in the Updated I
FSAR (UFSAR), since it is an accident mitigation system designed to function only when in contact with a liquid.
A1/C24.N12 4
i, i
a S'l HL AE-3370 Page 3 of 6 Safetv Evalustion b>sive tsH Control System (cont'd!
The proposed change e liminates the potential for contartination of primary grade water by sodium hydroxide leakage into the Reactor Coolant System.
This leakage causes depletion of resin used to remove the contamination and can result in higher dose rates.
The Spray Additive Tank will be drained and the
(
associated valves will be closed upon implementation of the proposed change (Tigure 6.2.2-1).
LOCA Dos,t Proposed dose results are within 10CFR100 and Standard Review Plan (SRP limits. The offsite Exclusion Area Boundary (EAB) and Low Population Zone (LPZ) dose limits are 300 rem for thyroid and 25 rem for whole body (gamma). The results for offsite tbyroid and whole body (gamma) doses in Table 1 are within these limits.
The offsite skin (beta) dose at the EAB is 0.01 rett above the current UFSAP value. The whole body dose at the EAB is 0.01 rem below the current UFSAR value.
The control room operator dose limits are 30 rem for thyroid and skin (beta) and 5 rem for whole body (gamma).
The results in Table 1 for Control Room operator thyroid, skin, and whole body doses are within these limits. The Control Room operator thyroid dose is 3.41 rem above the current UTSAR value ren.aining well within the acceptance limit of 30 rem The TSC dose limits are 30 rem for thyroid and skin (beta) and 5 rem for whole body (gamma).
Again, the skin and thyroid doses are within the acceptance limit of 30 rem, with the larger of the two being the thyroid dose which is 4.99 rem above the current UFSAR value.
The whole body (gamma) dose is lower than the current UF5AR value.
The potential consequences of a LOCA are slightly above current UFSAR values, but remain below the limits set forth by 10CFR100 and the SRP.
Hydrogen Generation WCAP 12477 evaluates the impact of the proposed change to the amount of hydrogen generated af ter a LOCA due to the replacement of spray additivt. Of the possible hydrogen generation sources only aluminum and zinc corrosion are affected by this proposal. The proposed change will affect the pil by introducing an initial pH of 4.5 (borated water spray) followed by a pH range of 7.0 to 9.5, using TSP.
This is effectively a lower pH than the current range of 7.5 to 10.0, using NaOH.
The corrosion of aluminum decreases with decreasing pH, therefore, the hydrogen generation resulting from aluminum corrosion will decrease with the use of TSP The corrosion of zine and zine enriched paints, which is highly dependent on temperature, is shown to be sJallar for the pH ranges of NaOH and TSP sprays. As a result, the amount of hydrogen generated after a LOCA is not increased and the margin of safety is unaffected.
A1/024.N12 I
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ST HL-AE 337E Page 4 of 6 lafety Evaluation Eauipment Oualification
=.
The proposed change to a lower initial pH of 4.5 and lower equilibrium pH of 7.0 to 9.5 is expected to have no effect on equipment qualification or protective coatings, since both are currently analyzed for the more listiting condition of high pH for long time periods.
A review will be performed to identify any materials for equipment qualification adversely irtpacted by the new pH environment. Any items identified as unsatisfactory will be replaced with material suitable f or the new pH envirotunent.
Determination of No $1rnificant Hazards pursuant to 10CFR$0.91 this analysis provides a determination that the k
proposed change to Technical Specifications does not involve significant hazards consideration as defined in 10CFR$0 42.
(1)
The proposed change does not involve a significant increase in the probability or consequences of accidents previously evaluated.
The proposed change to a Recirculation fluid pH Control System does not increase the probability of accidents previously evaluated because the new system cannot initiate an accident because passive components would be used in place of active components and the system mitigates the consequences of an acc Lent.
The potential for failure of active components would be decreased by this proposal.
Therefore, the proposed change does not increase the probability of any accident previously evaluated. The consequences of previously evaluated accidents do not significantly increase since doses rertain within the I
acceptance criteria of 10CFR100 and SRp limits.
(2)
The proposed changen do not create the possibility of a new or different kind ot accident from any accident previously evaluated.
No new modes of operation are proposed and the proposed Recirculation Fluid pH Control System will provide the same function as the current spray additive system, to mitigate the e f f ec ts o f a IDCA. The proposed system would not be used during normal plant operations.
(3)
The proposed changes do not involve significant reductions in the margin of safety, The IEA doses do not significantly increase and remain within the m;
acceptance criteria of 10CFR100 and the SRP.
Additionally, hydrogen generation is not increased and equipment qualification will remain
=
within the acceptance criteria.
Al/026 N12 1
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,. 3 ST.HL.AE.3378 Page 5 of 6-
. Conclusion-The replacement of Technical Specification 3/4.6.2.2 " Spray Additive
- System" with
- Recirculation Fluid pH Control System" is acceptable because a passive post. accident mitigation system replaces an active system, the calculated dose results do not increase significantly, and the hydrogen generation analysis and equipment qualification remain valid. HLAP requests approval of the proposed changes.
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Table 1 Offsite, Control Room, and TSC Proposed Doses vs. UFSAR Doses Thyroid (rea)
Whole body Skin 1
h Gamma (res)-
&gla (rem) i Total Offsite Dose EAB 126.5 (143) 2.19'(2.2) 1.16 (1.15)
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(0 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br />) u-
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Tot.al Offsite Dose LPZ 58.42 (61.2)-
0.68 (0.68) 0.43-(0.43) p-
'(0 30 days)
Total Operator Dose, Control Room 18.21 (14.8)
'2.42 (2.43)
.18.'7 (18.7)
(0 30 days)-
. Total TSC Dose 24.85 (19.86) 4.74 (4.88) 21.64 (21.62) i t!l (0 30 days) i NOTE: Values in parenthesis are current UFSAR values.
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I ATTACitMENT 2 MARKUPS OF PROPOSED C} LANCE TO TECilNICAL SPECIFICATIONS
,201-1000023-901030 ~
PDR ADOCK 0b000490 P
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,5M AY ADP111rl SYSTIM 6
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3.6.2.2
'he Spray Additive Systen shall be OFIRABL[ with:
a.
Th e spray additive tanks each containing a volume of and 4? gallnns of between 30 and 32% by weight NaOH etween 1061 olution, and b.
Ihree sp y additive edveters each capable of addi frem its a sociated spray additive tank to its C NaOH solution System pumt low.
tainment Spray APPL IC A!1L 11Y: N00E5 1, 3, and 4.
AC110'h With the Strey Accitive System i neratle, restg e the system to CPIRAhl status within 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br /> or be in at restcre the Spray Additive System to 4(RAEtteast HDI 5 ANDBY within the next 6 hours6.944444e-5 days <br />0.00167 hours <br />9.920635e-6 weeks <br />2.283e-6 months <br />; or be in COLD SHUTCG'fi within the foil, in 00 hours0 days <br />0 hours <br />0 weeks <br />0 months <br />. status.ithin the next 4! hours
}2id31 lei 23h'HIMihU
- 4. 0. 2. 2 IM Strej At:itivt Syster
..all be cem strated OPERABLE:
At least once per 31 a.
c:.t ope rate d, or a* scretit) in t'.tys by verifying th *heach valve (ranuti, ficw t 'h that is not le:ied, s e a le c, c r e t *.e r. i' q
situ *t: i *. p : l i *, i c r., is its correct p:litic*;
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Vt ifyi'. tM ccntair.t: solution volu.e in eachN5 pray ac:itive
- tank, tc 2)
Ver fying the contenttation of the Na0i solution by c eri al
- lysis, c.
At east once per 18 fronths during shutdown, by verifying that Containment Pressure High 3 test signal; andon.atic valve a
- t SOUTH TEXA5 UN]T5 } & 2 3/4 6 15 f
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At least once per 5 3 ears by verifying:
d.
1) tech eductor suction flow rate is greater than
-r equal to 30 gem using the RW51 as the test source to the educ or inlet, and under the following conditions:
l a)
C5 pump suction pressure is > 15 p g,
b)
Valve C50019A, B, or C, as app 1' cable, is in the full open pcsition, and pu recirculation fle rate to the RWST is 800 gpm 2 2) lhe ines between the,$pr / additive tank and the eductors are not b,cled by verifyin-flee,
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RECIPCUIATION TLUID PH CONTROL SYSTEM LIMITING CONDITIONS FOR OPEPATION 3.6.2.2 The recirculation fluid pH control system shall be operabic with between 11,500 lbs. (213 cu. ft.) and 15,100 lbs. (252 cu. ft.) of trisodium phosphate (w/12 hydrates) available in the storage baskets in the containment.
APPLICAP.1LITY: Modes 1, 2, 3, and 4 ACTION:
Vith less than the required amount of trisodium phosphate availabic, restore the system to the correct amount within 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br /> or be in at least HOT STANDBY within the next 6 hours6.944444e-5 days <br />0.00167 hours <br />9.920635e-6 weeks <br />2.283e-6 months <br />; restore the system to the correct amount within the next 48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br /> or be in COLD SHUTDOWN within the fo110 wing.30 hours3.472222e-4 days <br />0.00833 hours <br />4.960317e-5 weeks <br />1.1415e-5 months <br />.
SURVEILIANCE REOUIREMENTS 4.6.2.2 During each refueling outage, as a minimum, the recirculation fluid pH control system shall be demonstrated operable by visually verifying that:
- 1) 6 trisodium phosphate storage baskets are in place, and
- 2) have maintained their integrity, and
- 3) are filled with trisodium phosphate such that the Icvol is above the indicated fill mark.
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(Otp AINui hl SiST[PS CM CONTAINMiNT V(NTllAT', 54 STEM (Continued) f ore, the SITE 60' NDARY dose guideline of 10 CFR Part 100 <oJ d not be exceeded in J
the event of an accident during containment PURGING operat on.
Leakage integrity tests with a maximum allowable le nge rate for containment purge supply and exhaust supply valves will provide early indication of resilient material seal degradation and will allow opportunity for repair before gross leak-age failures could develop. The 0.60 L leakage limit of Specification 3.6.1.2b.
shall not be Exceeded when the leakage fates determined by the leakage integrity tests of these valves are added to the previously determined total for all valves and penetrations su, ject to Type B and C tests.
3/4.6.2 DEPRE55URIZAllDN AND COOLING SYSTEMS 3/4 6 2.1 CONTAINMENT SPRA) SYSTEM The OPERABltITY of the Containment Spray System ensures that containment depressurization and cooling capability will be available in the event of a LOCA or steam ' int brea6.
The pressure reduction and resultant lower containment leakage rate are consistert with the assumptions used in the saf ety analyses.
The Containment Spre3 System and the Cont ainment Cooling System both pre-vide post-accident cooling of the containment atmosphere.
Eowever, the Con-tainment Spray System also provides a mechanism for removing lodine from the containment atmosphere and therefore the time requirements for restoring an inoperable Spray System to OPERABL[ status have been maintained consistent with that assigned other inoperable EST equipment.
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v 3/4 6.2 2 SPRAY ADDlllv[ SYSTEM The OPERABillT) of the Spray Additive System ensures that suf ficient NaOH is added to the containment spray and containment sump in the event of a LOCA.
t The limits on NaOH volume and concentration ensurt a pH value of between 7.5 and 10.0 f or the solution recirculated within.conth'inment af ter a LOCA. This pH band minimizes the evolution of iodine'and minimizes the effect of chloride and caustic stress corrosion on-mechanical systems and components. The con-i tained < lution volupe Jimit includes an allowance for solution not usable
! because of tank-ditcharge line location or other physical characteristics.
These asstrmplions are consistent with the iodine removal ef ficiency assumed in the--safety analyses.
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SOUTH TlAAS UNITS 1 & 2 B 3/4 6-3 f
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L px2 xT fi 3/4.6.2.2 RECIRCULATION FLUID PH COETROL SYSTEM The operability of the recirculation fluid pH control system ensures that there is sufficient trisodium phosphate available in containment to guarantee a sump pH of 1 7.0 during the recirculation phase of a postulated LOCA. This pH level is required to reduce the potential for chloride induced stress corrosion of austenitic stainless steel and assure the retention of iodine in the retirculating fluid. The specified amounts of iSP will result in a recirculation fluid pH between 7.0 and 9.5.
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ATTAC}lMENT 3 WCAP 12477, "SFRAY ADDITIVE ELIMINATION ANALYSIS FOR Tile SOUTil TEXAS PROJECT" A1/024.N12 I
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