ML20246D034
| ML20246D034 | |
| Person / Time | |
|---|---|
| Site: | Seabrook  |
| Issue date: | 12/31/1988 |
| From: | Snooks J PUBLIC SERVICE CO. OF NEW HAMPSHIRE |
| To: | |
| Shared Package | |
| ML20246D025 | List: |
| References | |
| YAEC-1660, NUDOCS 8905100095 | |
| Download: ML20246D034 (51) | |
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Seabrook Station Off-Site Hazardous Chemical Analysis Update Major Contributor: J. H. Snooks December 1988 6888R 8905100095 890428 PDR ADOCK 05000443 P PDC
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' J plsciolt1ER OF RESP 014SIBILITY This document was prepared by Yankee Atomic Electric Company
(" Yankee").
The use of inf ormation contained in this document by anyone other than Yankee, or the Organization for which this document was prepared under contract, is not authorized and, with respect to any unauthorized use, neither Yankee nor its officers, directors, agents, or employees assume any obligation, responsibility, or liability or make any warranty or representation as to the accuracy or completeness of the material contained in this document.
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ABSTRACT A study was undertaken to update and' evaluate the.effect of any-changes in the amount or type of hazardous chemicals transported past.or stored by j
industries near Seabrook Station. A field survey out to five miles of I j
Seabrook Station and interviews with area emergency management personnel, 1 coupled with Federal Regulatory Guides, were used to assess potential effects to Control. Room habitability in the event of a chemical release. The results l
indicate that the previous evaluation, contained in the Seabrook Station Final Safety Analysis Report, remains valid - i.e., the Seabrook Station Control Room is appropriately protected from hazardous chemical releases. l In addition, an analysis was conducted to assess the effects of a nearby chemical warehouse fire on the Seabrook Control Room if meteorological conditions had been unfavorable. An air quality dispersion model was used to demonstrate that the concentrations from fire combustion products would not have had any adverse effects on the Control Room operators even under worst f case conditions.
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TABLE OF C0FTENTS Pace DISCLAIMER.................................................. 11 ABSTRACT.................................................... iii TABLE OF C0NTENTS........................................... iv 1.0 I N TRO D U CT I ON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 2.0 CH EM I CA L WAR EH OUS E FI R E . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2.1 Approach............................................... 2 2.2 Results................................................ 2 3.0 INDUSTRIAL HAZARDOUS CHEMICALS.............................. 4 3.1 Approach............................................... 4 3.2 Results................................................ 4 4.0 TRANSPORTED HAZARDOUS CHEMICALS............................. 18 4.1 Approach............................................... 18 4.2 Results...................... ......................... 18 5.0 EVALUATION.................................................. 20 5.1 Chemical Warehouse Fire................................ 20 5.2 Industrial Hazardous Chemicals......................... 20 5.3 Transported Hazardous Chemicals........................ 21 5.4 Conclusion............................................. 22
6.0 REFERENCES
.................................................. 23 APPENDIX Modeling of Combustion Product Concentrations Resulting l
from the Johnson Matthey Chemical Warehouse Fire.
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1.0 INTRODUCTION
As discussed in Regulatory Guide 1.78, "The Control Room of a nuclear power plant should be appropriately protected from hazardous chemicals that may be discharged as a result of ... events or conditions outside the control l l
of the nuclear power plant."[1] ~
The occurrence of such situations and their possible effect on control room habitability has been reviewed in the Seabrook Station Final Safety Analysis Report (FSAR), Section 2.2, " Nearby Industrial, Transportation, and ,
1 Military Facilities." That review, last revised in 1982, showed that there I were no toxic chemicals stored or used in nearby facilities in any significant amount or transported past the Seabrook Station at a frequency that posed an unacceptable risk.
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l The demography of the Seabrook Station surrounding industries, however, has changed since 1982. In addition, a recent chemical warehouse fire in the j Town of Seabrook drew significant area-wide attention. Accordingly, the results for the FSAR analysis were reviewed with regard to the warehouse fire, and a study was undertaken to update and evaluate the effect of any changes in the amount or type of hazardous chemicals either transported past or stored by industries near Seabrook Station. The purpose of this report is to present the results of these efforts.
Section 2.0 briefly summarizes the methodology and results of the chemical fire analysis, which was conducted by a consultant. A copy of the consultant's report is included as an appendix to this report. Section 3.0 describes the approach and results of the nearby industries update, which is followed by a description of the transportation update in Section 4.0. An evaluation of the Seabrook Station Control Room habitability is contained in Section 5.0. References are presented in Section 6.0.
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2.0 CHEMICAL WAREHOUSE FIRE On March 12, 1988, a fire occurred at the Johnson Matthey Company ]
chemical storage warehouse in the Town of Seabrook, located at-a distance of 4,800 feet from the nearest Control Room intake for Seabrook Station.
Approximately 1,200 chemicals, most in small quantities, were stored in the warehouse.
During the course of the fire, the wind was not directly blowing toward Seabrook Station. As . result, no effects were noted in the Control Room.
However, a etudy was commissioned to determine whether dangerous concentrations of chemicals would have arrived at the Control Room intakes if 4 the wind had been blowing.toward the station with a worst case speed and atmospheric stability. ERT of Concord, Massachusetts, conducted the study.
Their complete report is presented as an appendix to this report.
2.1 Approach Tu make their determination, ERT employed an air quality dispersion model. The model was modified to include a maximum concentration-duration event and to account for initial dilution, including. building wake effects, plume growth due to dispersion, and plume rise due to both momentum and buoyancy effects. ERT also used th'e extremely conservative assumption that the entire inventory of warehouse chemicals became airborne during the course of the fire. j l
2.2 Ren 11s 1
The model was run for various stability classes to determine the variation of emission concentration with distance and then define a worst case j peak concentration. The peak concentration was then modeled for different wind speeds and a normalized value used to determine the maximum concentration of chemicals at the nearest Control Room intake. The resulting concentrations .I 6888R
l were compared with worst case Immediately Dangerous to Life and Health (IDLH)* l levels (see Table 3 in the appendix) to evaluate possible effects to the Control Room operators.
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The calculated concentrations in all cases were below the IDLH level.
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- The IDLil level is "a maximum concentration from which... one could escape within 30 minutes without expyrigncing any escape-impairing or irreversible health effects."L19J l
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3.0. INDUSTRIAL HAZARDOUS CHEMICALS 3.1 Approach Whether an off-site storage area constitutes a hazard to'. Control Room habitability is determined on the basis of chemicals stored, the distance from
'the plant, the design of the Control Room, and the applicable toxicity limits. These parameters-are detailed in Regulatory Guide 1.78, and are the principal factors followed in this update, as they were in the initial FSAR evaluation. In particular, the location of facilities reviewed extended out to five miles of Seabrook Station.
The approach used to identify such industries was twofold. First, a survey was-performed of the most recent directories of manufacturers.
Emphasis was placed upon Standard Industrial Classification (SIC) codes of facilities that handle, store, use, or produce potentially hazardous chemicals as defined in Regulatory Guide 1.78.
Second, use was made of public information submitted to local and state authorities as required by the Community Right-to-Know Act passed by Congress.
in 1986. Commonly referred to as SARA, Title III, the Act' mandates the -
establishment of state and local planning authorities with responsibility'to develop emergency plans to be followed in-the event of an emergency chemical release. The Act also imposes new requirements on a broad range of facilities to report information regarding the presence and release of specific chemicals to these authorities.
3.2 Results A total of 51 industries that store or use hazardous chemicals were identified within five miles of the Seabrook site. They are listed in Table 3.1.
Based upon a review of each facility's SIC code, product line, employment level, a physical survey of.Its location, and interviews with local-officials [5-8] fifteen were selected as requiring further investigation for 6888R '
potential impact. Each facility was then contacted to determine the type, use, and amount of hazardcus chemicals at its plant site. The information is summarized in Table 3.2.
From Table 3.2, it can be seen that nine of the facilities reported l limited use, storage, or production of hazardous chemicals. Typically, materials are stored in drums of 55 gal. or less. The six other facilities provide, or may provide, sufficient quantities (usually through bulk storage) of hazardous chemicals to produce a potential' hazard to the Seabrook Station Control Room habitability. Figure 3.1 shows the location of these six facilities, and their description is as follows:
- 1. The Bailev Corporation is located in the Town of Seabrook, one mile west-southwest of the site. Bailey stores Linuid Propane (LP) gas on-site for use in their operations, which include a large paint shop. There are two LP gas storage tanks, each with a capacity of 30,000 gals. In addition, the plant may store approximately 10,000 gals. of paint at one time.
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- 2. The Rockingham Fireworks Companv/NH Pvro Products. Inc., is located
- in the Town of Seabrook, 1-1/4 miles west of the site. The l
facility uses 1cw energy explosives, primarily black powder, to produce fireworks. The companies maintain nine storage magazines.
One magazine (capacity 5,000 lbs.) is utilized for the storage of black powder, but is limited by regulation to 1,000 R s., according to the owner. 0]
The remaining eight magazines are used for storage of the finished product, and have a combined capacity of the finished product is 20,000 lbs.
- 3. The K. J. Ouinn & Company. Inc., is located in the Town of Seabrook, two miles southwest of Seabrook Station, just north of the Massachusetts border. The plant uses several chemicals and solvents in its manufacturing process. Bulk storage is provided for liquified nitrogen (6,400 lbs.), xylene, methyl ethyl ketone, '
and ethyl acetate, each at 11,900 gals., and 8,500 gals. of toluene 1
di-isocyanate. Drum storage is provided for ethanol (750 gals.),
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isopropanol- (1,000 gals. ), and dimethane di-isocyanate (550 gals.). In addition, up to 10,000 gals. of flammable finished.
product may be stored.
- 4. The Sag.amore Industrial-Finish Company is located in'Amesbury, Massachusetts, approximately 4-3/4 miles southwest of the Seabrook site center. The plant has 17,000 gals. of bulk storage for its paints, thinners, varnishes, and industrial solvents. In addition, the plant may have approximately two hun 6 red 55-gal. drums for storage or for shipping out their product.
- 5. The NANCO facility is a storage depot for industrial gases located in Amesbury, Massachusetts, 4-3/4 miles southwest of Seabrook Station.. The facility maintains bulk ctorage of nitrous oxide r (28,000 lbs. ), carbon dioxide (62,000 lbr.), oxygen (3,000 gals. ),
nitrogen (9,000 gals.), argon (1,600 gals.), and propane l
(2,000 gals.). 'Ihere is also cylinder storage of helium (34,100 cu. ft.) and acetylene (32,750 cu. ft.), as well as nitrous t oxide (2,280 lbs. ) and carbon dioxide (8,750 lbs.).
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- 6. The Hysol Aerospace Industries plant is located in the Town of Seabrook, two miles west-southwest of the site. Hysol produces hot melt adhesives and stores bulk quantities of liquified nitrogen and freon of about 100,000 lbs. total. Other chemicals include anhydrous ammonia, corrosives, flammables, and organic solvents, none of which is in bulk quantities. The storage of these materials is either in limited quantity drums or cylinderr.
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- 6 N A A
1 IABLE 3.2 ,
Eummary of Hazardous Materials Usage Location Easility Direction - M11gg . Hazardous Materials Statua Bailey Corporation ** WSW 1-2 Storage for 60,000 gals.
liquid propane and 10,000 gals. of paint. q Rockingham Fireworks ** W 1-2 Storage capacity for-20,000 lbs. of low energy .
explosives.-
SW 1-2 Storage for-44,000 gals, of j K. J. Quinn & Company **
chemicals and solvents.
Sagamore Industrial SW 4-5 Storage for 17,000 gals. of Finishes ** paints, thinners, and. )
' finishes. j Hysol Aerospace Industries ** WSW 2-3 Bulk quantities (100,000 lbs.) of nitrogen-and freon; unspecified l solvents, corrosives, and flammables.
Amesbury Metal Products SW 4-5 Limited quantities of solvents, oils, and paints used or stored.
)
Advanced Absorber SW 4-5 Limited quantity of solvents Products used or stored.
NANCO** SW 4-5 Storage for 90,000 lbs, of 1' industrial gases.
Craig System Division SW 4-5 Limited quantities of
) flammables, corrosives, and compressed gases used or-l stored.
Eastern Manufacturing Corp. SW 4-5 Limited quantities of solvents, corrosives, and J
I ammonia used or stored.
Tech Ceram SW 4-5 Limited quantities of solvents,~ ammonia, and acid used or stored.
6888R I
- 1.5 _
IhD.Lia_3 J (Continued)
Location Easility Direction - dij_es Hazardous Materials Status Aqua Laboratories SW 4-5 Limited quantities of flammables and corrosives used or stored.
Vaughn Manufacturing Corp. SW 4-5 Tank storage (18,000 -
24,000 lbs.) of urethane.
Foss Manufacturing N 3-4 Drum storage of flammables, corrosives, aad oxidizers
'1.200 eations).
Morton Thiokol, Inc. SW 1-2 Limited quantities of solvents and propane used or stored; bulk storage of 55,000 gals. of polymers.
- Bulk storage of potentially hazardous materials.
6888R
FIGURE 3.1 Facilities With Bulk Hazardous Materials
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-l 4.0- TRANSPORTED HAZARDOUS CHEMICALS 1 4.1 Approach As in Section 3.0, Regulatory Guide 1.'78 details the parameters needed-to evaluate whether the transportation of hazardous chemicals past Seabrook j I
poses a hazard'to Control Room habitability. The principal factors to ..
'I consider are chemical' type, quantity, distance, and frequency of. transport.
1 J
The approach used to identify transported hazardous chemicals was to review and update two earlier studies. The first concerned railroad !
transportation, and is part of FSAR Section 2.2. The se.cond' concerned.
highway transportation, and was performed in 1982. The results were then. compared with Regulatory Guide 1.78 criteria, especially frequency of shipments to determine if further consideration was necessary in the evaluation of Control Room habitability.
4.2 Results Itailroad There is only one rail line that serves the areas within five miles of the Seabrook site, the Boston and Maine (ELM), Salisbury Branch. The branch provides service to areas generally north of Seabrook, as described in the FSAR. Tracks south of the site, however, are present but are not -l utilized.
l 1
There are no hazardous: chemicals (vinyl chloride, chlorine, etc.) i transported by the BLM on the Salisbury Branch, mostly lumber and plastics. The Newington Branch, north of Seabrook, does transport hazardous materials, but it is located greater than five miles from the site.
I 1
i i
i 6888R i 18 l
l
Illshway Previous studies '
assessed the transportation of hazardous chemicals by the highway passing Seabrook Station. There were two important results. First, chlorine is the only large-volume hazardous chemical frequently transported past the site - i.e., 16-ton shipments of at least ten per year - that meet Regulatory Guide 1.78. Second, a 16-ton chlorine cargo tank truck accident could result in a buildup to toxic levels of chlorine vapors in the Control Room. A probabilistic hazard model, accordingly, was developed to determine how likely this type of accident is. 20 The result was a distribution of probabilities with the mean probability being 6]
2.8 x 10~ per year.
Recent data showing an increase in the number of chlorine shipments past the site changes the probability. The hazard model previously developed, therefore, was updated to include this new information as well as refinements to other model parameters.
~7 The updated model results now show the probability to be 3.2 x 10 per year.
6]
6888R
M M
5.0 EVALUATION To evaluate the effect on Control Room habitability, the assumptions 5 made in Regulatory Guide 1.78 were followed. Of particular importance are the quantity of stored chemicals and the distance to the Control Room. As distances increase, a larger quantity must be releaced to cause a potentially deleterious effect. Otherwise, atmospheric dispersion will dilute and disperse the released plurie to such a degree that the concentration will be of no consequence, er there would be sufficient time for Control Room operators to take appropriate t.ction. In addition, a different methodology recently 3 developed by the U.S. Environmental Protection Agency, et al.,[16] to assess the hazards related to potential airborne releases of hazardous substances, was used to check the results.
Lastly, if the above guidelines were exceeded, the hazardous chemical was viewed with regard to the accident events that may cause its release, and thereby affect Control Room habitability. Such events may be considered acceptable if their probability of occurrence is sufficiently low.
5.1 Chemical Warehouse Fire Even under the most unfavorable meteorological conditions, ERT concluded that "the concentrations of combustion products from the fire would h not have adversely affected the ability of the Seabrook Power Plant Control Room operators to perform their duties."I23 The point is moot, however, because Johnson Matthey does not plan to e reopen the warehouse. In addition, the company has removed all hazardous 1-materials from a nearby facility.[20]
5.2 Indus111aLilarar_dans_Chemicala B
iiiiii Section 3.2, lists those facilities which contain hazardous materials in large enough quantities ta be a potential hazard to Seabrook Station. Each 0 was reviewed with regard to the analysis performed in the FSAR, Section 2.2, and new data obtained during this update.
~
6888R The Bailey Corporation kventory of hazardous chemicals has not changed since last reviewed. Consequently, the analysis of potential accidents in the FSAR (explosion and flammable vapor cloud releases) still applies. This is also the case for the Sagamore Industrial Finish Company.
The Rockingham Fireworks Company and the K. J. Quinn & Company have slightly different inventories than previously reported. The maximum amount of storage for finished product at the fireworks company, for example, has increased. However, applying Regulatory Guide 1.91, the nearest station unit to the company is well beyond the required safe distance for the amount of low energy explosives that can be stored.
Similarly, bulk storage ha:: increased at K. J. Quinn & Company. The additional quantities and the distance from the station, however, are well within the guideline established for Control Room evaluations and emergency planning. '
This also is the case for the NANCO and Hysol facilities, where distance and quantities are within the guidelines. '
5.3 Transported liazardous Chemicals As indicated in Section 4.2, potential hazards to the Control Room depend on the mode of transportation. The railways, on the one hand, are not a concern because no hazardous chemicals are transported within five miles of the Seabrook site.
l The highways, on the other hand, pose a potential hazard. In particular, a chlorine cargo tank truck accident could produce toxic vapors within the Control Room under certain conditions. The probability of such an event, however, is very low. Although recent data has increased the
-7 likelihood of such an event to 3.2 x 10 per year, the value still meets the regulatory objective of approximately 10- per year.[25]
Regardless, the probability of this event will decrease in 1990. At that time, the transporter's principal customer for the chlorine is scheduled to discontinue chlorine use. The frequency of transport past Seabrook, 6888R
accordingly, will decrease significantly. The result will be a decrease in the probability of accident occurrence to when little or no chlorine was transported past the site.
5.4 Cnaclusion All the facilities reviewed that store or use hazardous chemicals have either limited quantities of those chemicals, or are at distances far enough away from Seabrook's air intakes not to affect Control Room habitability. In addition, hazardous chemicals transported past the site do not present an undue risk. The FSAR evaluation of hazards, accordingly, remains valid; i.e.,
" hazards in the vicinity of the site, due to potential accidents from nearby industrial, transportation ... installations indicate that such accidents cannot affect the safe operation of the plant, and that the probability of those accidents which may affect safe operation is acceptably low, of the order of 10- per year or less. Accordingly, it is not necessary to define any design basis events relating to these hazards."
E 6888R
.~ .
m:..t. . . .
6.0 REFERENCES
- 1. Regulatory Guide 1.78, " Assumptions for Evaluating the Habitability of a Nuclear Power Plant Control Room During a Postulated Hazardous Chemical Release," U.S. Nuclear Regulatory Commission, June 1974.
- 2. "Modeling of Combustion Product Concentrations Resulting from the Johnson Matthey Chemical Warehouse Fire," Document No. 7442-001, ERT, Concord, Massachusetts, 1988.
- 3. Dir_entory of Mas _Eachuset.ts_Manularturers, 1988-1989 Edition, Geo. D. Hall Company, Boston, Massachusetts.
- 4. Made inlaw_Jiampf. hire.1987. NH Office of Industrial Development, Concord, New Hampshire.
- 5. Office of Emergency Management, Town of Seabrook, New Hampshire, personal communication, September 16, 1988.
- 6. Civil Defense, Town of Amesbury, Massachusetts, personal communication, September 16, 1988.
- 7. Fire Department, Town of Hampton, New Hampshire, personnel communications, October 18, 1988.
- 8. Fire Department, Town of Salisbury, Massachusetts, personal communication, October 12, 1988.
- 9. The Bailey Corporation, Seabrook, New Hampshire, personal communication, September 22, 1988.
- 10. The Rockingham Firework Company /NH Pyro Products Inc., Seabrook New Hampshire, personal communication, September 22, 1988.
- 11. K. J. Quinn & Company, Inc., Seabrook, New Hampshire, personal communication, September 22, 1988.
- 12. Sagamore Industries Finish Company, Amesbury, Massachusetts, personal communication, September 22, 1988.
- 13. NANCO, Amesbury, Massachusetts, personal communication, September 21, 1988.
- 14. Final Safety Analysis Report, Seabrook Station, Docket Nos. 50-443 and 50-444, Public Service Company of New Hampshire.
- 15. Regulatory Guide 1.91, " Evaluation of Explosives Postulated to Occur on Transportation Routes Near Nuclear Power Plants," U.S. Nuclear Regulatory Commission, February 1978.
- 16. " Technical Guidance for Hazards Analysis, Emergency Planning for l Extremely Hazardous Substances," U.S. Environmental Protection Agency, Federal Emergency Management Agency, U.S. Department of Transportation, December 1987.
6888R mu_... . . - __.
- - - ----- - - ~ - -
e
- 17. Hysol Aerospace Industries, Seabrook, New Hampshire, telephone communication, October 11, 1988.
- 18. Mills, M. T., "Modeling the Release and Dispersion af Toxic Combustion Products From Chemical Fires," International Confere2.ce on Vapor Cloud Modeling, November 2-4, 1987, Cambridge, Massachusetts.
- 19. " Pocket Guide to Chemical Hazards," National Institute for Occupational Safety and Health, U.S. Department of Health and Human Services, September 1985.
- 20. Johnson Matthey Company, Aesar Division, Philadelphia, Pennsylvania, telephone communication, October 14 1988.
- 21. " Assessment of Hazardous Materials Transportation, Seabrook Station, Seabrook New Hampshire," 1982, Engineering Calculation SBC-35, Yankee Atomic Electric Company, Framingham, Massachusetts.
- 22. Guilford Industries Corporation, Boston and Maine Railroad, No.
Billerica, Massachusetts, telephone communication, November 8, 1988.
- 23. "Effect of a Chlorine Tank Truck Accident on Route I-95 on Seabrook Control Room Habitability," 1982, Engineering Calculation SBC-30, Yankee Atomic Electric Company, Framingham, Massachusetts.
- 24. Jones Chemical, Manchester, New Hampshire, telephone communication, November 8, 1988.
- 25. U.S. Nuclear Regulatory Commission, " Standard Review Plan," NUREG-0800, Washington, DC.
- 26. " Hazardous Materials Transportation Update, Seabrook Station," 1988, Engineering Calculation SBC-296, Yankee Atomic Electric Company, Bolton, Massachusetts.
6888R
0 0 ed 4
APPENDIX 5
E
y n.. . - . . .. ... .... . _ _ _ _ . _. _ _
I
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L "
- t Y .
- h\. o, *** 'e' ' ' r Document No. 7442-001 odeling of Combustion Product concentrations Resulting from rie. Johnson Matthey Chemical arehouse Fire inal Report 5
Prepared for:
Yankee Atomic Electric Company
-raminglam, V A July 1988 )
An ENSR Company
- - - ~ . - - _ _____ ._
L L and-n ENSR Company 26 VIRGINI A ROAD. CONCOAD MA 01742. (617) 369-8910 environntental and engineering excellence ERT REF: 7442-001 19 July 1988 Mr. John Snooks Yankee Atomic Electric Company 1671 Worceste' cad Framingham, MA J1701
Dear Mr. Snooks:
Enclosed you will find ERT's final report covering the impact of the chemical warehouse fire which occurred in Seabrook, New Hampshire on March 12, 1988. This report confirms our findings communicated you by telephone on Friday, May 27, 1988.
Even under the most unfavorable meteorological conditions, the concentrations of combustion products from the fire would not have adversely affected the ability of Seabrook Power Plant control room operators to perform their duties. This conclusion is based upon conservative assumptions regarding the amounts of chemicals released during the course of the fire.
Yours,truly, 21 & & [. h' Mi~chael T. Mills, Ph.D.
Principal Scientist
N.irDRFMA : COLORADO ELLit;Cle, 0.u SSACHUSETTS MINNESOT A DoEW JERSEY PENNSYLVANIA A TIE %AS WASwaG10N
I Document No. 7442-001 Vlodeling of Com bustion Proc uct Concentrations Resulting from he. Johnson Matthey Chemical
'arehouse Fire Final Report Prepared for:
Yankee Atomic Electric Company
-raming lam, V A July 1988 An ENSR Company
J. .
MODELIIIG OF CCMBUSTIOli PRODUCT C011CE11TRATIONS RESULTING FROM THE JOHNSON MATTHEY CHEMICAL WAREHOUSE FIRE 1.0 Introduction On Saturday March 12th at approximately 7 pm, a fire started in the Johnson Matthey chemical storage warehouse in Seabrook, New Hampshire, located at a distance of 4800 feet from the nearest control room intake vent for the Seabrook Nuclear Power Plant. The fire in the one-story concrete block building was fueled primarily by wooden shelving, partitions and packaging materials. Approximately 1200 distinct chemicals, most in small quantities, were stored in the warehouse. During the course of the fire, the wind was not directly blowing toward the power plant. The purpose of this study was to determine whether dangerous concentrations of chemicals would have arrived at the control room inlets if the wind had been blowing toward the plant with a worst case speed and atmospheric stability. In making this determination, the extremely conservative assumption is made that the entire inventory of warehouse chemicals becomes airborne during the course of the fire. Section 2 of this report will discuss the method for estimating the quantities of chemicals involved in the fire. This will be followed in Section 3 by a E description of air quality modeling assumptions and results.
References are presented in Section 4.
5 1
3 1
n ,,_u. : s __. .u-m.._....
2.0 Estimation of Chemical Quantities Involved in the Fire ERT reviewed the inventory of chemicals in the warehouse at the time of the fire. The inventory includes all materials present in the building, without knowledge of which materials or sections of the building were directly involved in the fire. For the emissions calculations, it was assumed that all of the listed materials were subject to the fire, although communications with the New Hampshire Department of Environmental Services (DES) staff and the Johnson Matthe'y environmental staff indicated that a significant quantity of material was unaffected by the fire ( many enemical containers have reportedly been found intact).
The inventory is 139 pages long, listing 25 items per page.
Considering that many items had multiple listings ( e.g. 2 pages list various forms of copper metal), approximately 1200 distinct chemicals were stored in the building in various quantities.
Quantities of individual substancee range from grams ( e.g. 6 grams of gold sulfide) to over 1000 kilograms ( e.g. 1600 kilograms of copper metal) . Essentially all of the chemicals were inorganic, with the inventory consisting primarily of pure metals, metal salts and oxides, acids, bases and organometallic complexes. Inorganic compounds based on 73 elements were listed.
The chemistry of fires is complex, and the potential involvement of over 1000 inorganic chenicals compounds the complexity. Fires require a fuel source, usually an organic liquid or gas (such as oil or propane) or an organic solid ( such as wood or plastics). The flammability of many chemicals in the inventory was determined using two chemical reference handbooks (References 1 and 2). This review indicated that most of the chemicals are not especially flammable, however several are explosive or would react violently upon contact with air or water. The Seabrook Fire Chief indicated that the fire was primarily fueled by wooden shelving and partitions in the building, which corroborates the supposition that the chemicals were not the primary fuel for the fire.
2
i Toxic chemicals could potentially have been released to the atmosphere during the fire via three mechanisms: combustion, volatilization, and chemical reaction. Combustion generally involves the reaction of a substance with oxygen to produce heat.
Combustible substances, such as magnesium and zinc powder, were present in the warehouse. These would form their respective oxides upon combustion. Some of the metal nitrates and perchlorate that were prLsent would also be combustible. The many halogen salts (chlorides, bromides, fluorides and iodides) ,
phosphates and borates present are not generally combustible. In fact, these compounds are used as fire retardants or chemical extinguishers (Reference 3).
The heat of the fire could vaporize some of the solid and liquid chemicals stored in the warehouse. The fire temperature would not be expected to exceed 10000 C during the cource of the I
two hour fire (Reference 3). Although some of the materials present would volatilize at this temperature, most of the pure metal and metal salts have boiling points greater than 1000 0C.
Of the metals present, only sodium, potassium, rubidium, cesium, cadmium and mercury boil at temperatures lower than 10000 C(Reference 4). Of these, cadmium and mercury are of the greatest concern due to their toxicity.
Chemical reactions between inorganic chemicals in the warehouse could release volatile products to the atmosphere.
Based upon the available information, it is impossible to estimate the type or quantity of reaction products formed during the fire. Since any given chemical reaction requires, at a minimum, the direct contact of two or more specific starting materials, it is unlikely that any one metallic reaction product was formed in large quantity during the fire. Some of the likely reaction products of concern are halogens (chlorine, bromine, fluorine or iodine) or halogen acids ( hydrochloric, hydrobromic or hydrofluoric acids), formed by the decomposition of chemicals in the fire.
l The quantities of the acutely toxic chemicals potentially 3
~
~~
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l released during the fire were estimated in a conservative fashion. Acute toxicity, as it is applied here, refers to chemicals which might pose an immediate debilitating human health hazard upon exposure. Carcinogens are not acutely toxic, although they may be potent at low exposure levels.
Acutely toxic compounds were selected by.two methods. The National Institute of Occupational Health and Safety (NIOSH) evaluates the toxicity of various industrial chemicals for protection of workers. Table 1 displays the NIOSH IDLH(Immediately Dangerous to Life or Health) limits (Reference 5) for chemicals which could possibly have been released during the fire. Many of the metals in the fire (such as copper, iron oxide, magnesium oxide, etc.) are not acutely toxic and therefore do not have IDLH values. In addition to a review of the NIOSH documentation, a senior ERT toxicologist independently reviewed the list of metal substances in the warehouse to identify acutely toxic materials. Based upon this review, the final list of acutely toxic chemicals potentially released from the fire is shown in Table 2.
Precise calculation of the emitted quantities of each of the substances listed in Table 2 is not possible. For each substance it was assumed that all compounds containing the element or anion (cyanide and carbonyl) cf interest were released to the atmosphere during the fire. The chemical inventory was reviewed and the masses of all relevant compounds were totaled to yield a worst-case estimate of the release quantity of each material.
These release quantities, given in Table 2, were the basis for the emission rate and dispersion modeling calculations discussed in Section 3.
It is important to recognize that the release quantities calculated are overestimates of the actual quantities released.
First, it was assumed that all relevant materials were released to the air. This is unlikely, since not all material would volatilize, combust or react and since parts of the inventory were reportedly unaffected by the fire. Secondly, stoichiometry 4
?
~
y o , .,e . a s :.aw. . , , . .
was not accounted for in the calculations. For example, the entire mass of chlorine compound was included in the sum, even though only a fraction of the compound was the. element chlorine.
Therefore, the effective mass of chlorine, or any of the other substances is overestimated.
Some items on the inventory could not be readily quantified and, therefore, were not included in the total quantity estimates. Typical examples were metal rods and wire, whose quantities were expressed in units of length or standard solutions of dissolved materials, whose quantities were expressed by volume of a solution of a given concentration. Although metal rods and wire represent a potentially large mass of material, their form makes them less susceptible to combustion. The standard solutions are minor, since they contain a relatively small quantity of toxic material.
i I
5
3.0 Air Quality Dispersion Modeling To estimate the chemical concentrations associated with the conservative release estimates given in Section 2, an air quality dispersion model was used which accounted for initial dilution (including building wake effects), plume growth due to dispersion, and plume rise due to both momentum and buoyancy effects. The model used was a modified version of the model described in Reference 6. For the purpose of these modeling calculations, it was assumed, based upon conversations with the Seabrook Fire Chief, that the major portion of the fire lasted i for 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> and that the fire was primarily feed by wooden shelving and partitions. Although no estimate of the amount of wood burned was available, it seems reasonable to assume that at least 1000 kg of wood were consumed during the two hour period.
By assuming an average heat of combustion for wood of 19.4 kJ/g, the buoyancy flux for the fire could be computed. According the fire chief, the flames exited the warehouse through a 4 foot by 4 foot hole in the roof, which was opened by the firemen shortly after their arrival on the scene. The dimensions of this opening were used to calculate the momentum rise of the fire plume.
Although a flame temperature as high as 10000 C could occur in the fire, a conservative value of 6000 C was used for the modeling.
For the building wake effects calculation a building height of 20 feet and an area of 8000 square feet were used. The height of the air intake vent above the ground is 8 feet.
During the actual fire the average wind speed was 1.7 m/s, the average ambient temperature was 33 0 F, and the stability class was "F". For scaling purposes it was assumed that 1 kilogram of emissions were released during the 2 hour2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> duration of the fire. The variation of concentration with distance and stability class is given in Figure 1. The worst case stability class ("F") turns out to be the stability class which actually occurred. At the distance corresponding to the nearest intake vent (1456 meters), the concentration is estimated to be 0.003 6
n u Ju,a... : ... . . . . .
Je mg/m3 The variation of this peak vent concentration with wind speed is shown in Figures 2 through 6. For each wind speed, the concentration remains at roughly 0.003 mg/m 3 due the compensating effects of increased plume dilution and decreased plume rise.
This normalized concentration was then used to determine the maximum concentration of chemicals at the nearest intake vent using the kilogram quantities given in Table 2. The resulting concentrations and a comparison with worst case IDLH values are given in Table 3. Even with the extremely conservative assumptions regarding the amounts of chemicals involved in 'the fire, the calculated concentrations are be-low the IDLH values.
I 7
Tabic 1. IDLH Values for Chemicals Which Could Have Been Released During the Fire Chemical IDLH Value.
L f (mg/m3 )
Antimony and compounds 80 Barium soluble compounds 250 Bromine 71 Cadmium dust 40 Chlorine -
79 Chlorine dioxide 25 Chromic acid and chromates 30 soluble chromic and chromous salts 250 Cobalt metal fume.and dust 20 Cyanides 50 Fluorine 45 I Hafnium and halnium compounds 250 Hydrogen bromide 181 Hydrogen chloride 163 Hydrogen cyanide 60 Hydrogen fluoride 19 Hydrogen selenide 7
," Hydrogen sulfide 455 Iodihe 113
- Lead arsenate 300 m
Manganese 24,500
- Mercury 28
- Nickel carbonyl 0.0076 Nitrogen dioxide 103 Osmium tetroxide 1 Phosgene 9 Selenium compounds 100
~
Sulfur dioxide 286 l Soluble thallium compounds 20 8
___________.-_______________-_____m_.___
-- - . . . - , . . . ~ . . - . . . . - - . - . - . - - . . - - . . . - - - . . . . - . - - _ - - - - - - - - - - - - - - - _ _ - - - - - - -
1 4
I a .
1 Table 1. IDLH Values for Chemicals Which could Have Been 1
) Released During the Fire (continued) 1 i
Chemical IDLH Value (mg/m 3)
I
\
i Inorganic tin compounds 400 q Uranium and insoluble compounds 30 I I
Soluble uranium compounds 20 i I
Vanadium pentoxide fume 70 i Zirconium compounds 500 l
l 9
Table 2. Final List of Toxic Chemicals Potentially Released During the Fire l
Chemical Type Total Mass Worst Case IDLH (kg) (mg/m 3) i Arsenic compounds 72 300 I J
Cadmium compounds 257 40 1 Chromium compounds 2002 30 Lead compounds 771 300 Mercury compounds 165 28 Osmium compounds 0.23 1 Selenium compounds 94 100 Bromine compounds 191 71 Chlorine compounds 1811 25 Fluorine compounds 622 45 Iodine compounds 72 113 Carbonyls 1 0.0076 Cyanidos 303 50 1
l 1
10 !
Table 3. Worst Case Calcula'ed Vent Concentrations Compared with IDUI Values Chemical Concentration IDLH Type (mg/m 3) (mg/m3 )
Arsenic compounds 0.22 300 Cadmium compounds 0.77 40 Chromium compcunds 6.0 30 Lead compounds 2.3 300 Mercury compounds 0.5 28 Osmium compounds 0.0007 1
__ Selenium 0.28 100 S Bromine compounds 0.57 71 Chlorine compounds 5.4 25 4 Fluorine compounds 1.9 45
. Iodine compounds 0.22 113 Carbonyls 0.003 0.0076 Cyanides 0.91 50 8
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4.0 References
- 1. Hawley, G.G.(1981), The Condensed Chemical Dictionary - loth l Edition, Van Nostrand Reinhold Company, New York.
l
- 2. The Merck Index - Encyclopedia of Chemical Drugs and Biologicals - 10th Edition, Merck and Company, Inc., Rahway, New York.
- 3. Drysdale, D.(1985). An Introduction to Fire Dynamics, John Wiley and Sons, Ltd., Chichester.
- 4. Douglas, B., D.H. McDaniel and J.J. Alexander (1983), Concepts and Models of Inorganic Chemistry, John Wiley and Sons, Inc.,
- 5. NIOSH Pocket Guide to Chemical Hazards, September 1985, U.S.
Department of Health and Human Services.
- 6. Mills, M.T., "Modeling the Release and Dispersion of Toxic Combustion Products from Chemical Fires," paper presented at the International Conference on Vapor Cloud Modeling, November 2-4, 1987, Cambridge, Massachusetts, sponsored by the Center for Chemical Process Safety of the American Institute of Chemical Engineers.
18
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