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Subject: Determination of Downsind Hazardous Area Chemical Transport Spills Reference: Illinois Environmental Protection Agency Engineers Incident/Episode Manual The following procedure is excerpted from page 3-18 of the reference engineer's manual. o - A When Dispatched to Incident Scene: -1. Before departing for the scene of an incident, make sure that you have your response equipment. This equipment should include: a. Wlndmeter b. Thermometer c. Compass d. Flashlight e. Protective clothing (hardhat, smock (coveralls)) f. Air sampling equipment (if necessary) g. Sliderule h. MCA Chem-card Manual i. Engineers' Manual j. Identification 2. Upon arrival at the scene of an air pollution Incident, report to the individual in charge. This person will usually be the highest ranking law enforcement official or civil defense official or the fire marshal. If it is not known who is in charge, then make the assumption that the senior law enforcement official will be ultimately in charge. Inform him of your presence, responsibilities, and capabilities. Tell him that you are responsible for pro viding information as to the toxicity, flarrmabil ity, ex plosiveness, and concentration of hazardous air contaminants. Let him know the monitoring equipment you have on hand and of your ability to obtain outside assistance. Determine if he has specific relevant duties for you to perform. Obtain his name and record on Response Sheet (Figure 4) and Checklist (Figure 5). RSV 0012934 4 3. Visually examine the incident scene. Determine the location of the release or spillage of hazardous material. 4. Determine identity of hazardous naterial(s) from personnel at scene. If this is not possible, determine material(s) in accordance with the following instructions: a. Fixed Sites: Situations where released material is unidentified seldom occur at fixed sites, since persons at industrial plants usually know what hazardous substances are handled there. b. Mobile Sites: In many cases material escaping from mobile sources is not immediately identifiable since the tank truck driver, barge captain, or railroad engineer may have fled the scene or may himself be overcome by the materials. The following actions should be taken to help Identify the material: If tne source can be approached with safety from upwind, look for identifying labels of all kinds that might give the name of the carrier or shipper, vehicle registration number, or warnings or cargo characteristics and handling. Look for placards displayed on the trucks in accordance with the Department of Transportation regulations. If the cab of the vehicle Is accessible, look for a Chem-card that is required to be In every vehicle carrying hazardous materials. If you are unable to identify the cargo, determine as much information as you possibly can and inform the DAPC Emergency Action Center. You should obtain and report the following information, if available: the name of the factory or carrier, the physical characteristies, of the hazardous material, its color and smell, its physical affects upon people or foliage, and whether it is readily rising into the air. If you are unable to contact Emergency Action Center personnel, then contact the Chemical Trans portation Emergency Center (CHEMTREC) at the toll-free number, (800) 424-9300, Provide them with the information you have gathered concerning the nature of the material. CHEMTREC is available 24-hours a day to provide immediate guidance on what to do in case of spills or leaks, fire, or exposure to hazardous naterials. c. Actions if materials cannot be identified: Materials that cannot be identified from labels or other readily available sources should be assumed to be dangerous until proven otherwise. The responsibility of our Division in this case is not altered. We are the experts who must determine the nature of the chemical or gas involved in the incident. A first attempt to determine the material will be made by the Emergency Action Center. If the material cannot be identified in this manner, then you should attempt to determine the material by using the chemical detection tubes RSV 0012935 Estimate the quantity of material being Released and enter on the response checklist. If the source strength (Q) is not known and cannot be estimated, assume a source strength of 1 kg/sec (1000 gm/sec). This emission rate is typical of what has been observed or calculated for rocket fuel spills and no other estimates are available at this time. Hazardous substances that are transported as liquids ray have been either liquid or gaseous at normal pressure and temperature. In the latter case, the gases are liquefied and pressurized to several atmospheres within their container. When vented to the atmosphere, pressurized liquid rapidly returns to the gaseous state, carrying along aerosolized liquid particles that vaporize in a few seconds. In such cases, the source strength may be assumed to be 100% of the material emitted. You will have to estimate the amount of liquid being released per second and use the conversion factor of 1 gal/sec 3 kg/sec (3000 gm/sec). However, other hazardous substances that are liquid though volatile at normal pressure and temperature may spill from their container to the ground, and enter the atmosphere only through vaporization. In such cases the source strength for the same quantity of spill as a liquefied gas will be somewhat less than that of the gas by a factor that depends on its rate of evaporation. The rate of evaporation is not constant; It depends upon the temperature, pressure, and wind speed of interfacing arrbient air, and In the case of hydroscopic material like anhydrous ammonia, on the relative humidity as well. It also depends upon its vapor pressure curve. In the event of a volatile liquid spillage, vapor source strength, Q, may be determined by the following procedure: a'. Estimate the rate of liquid spillage, expressed in gm/sec. b. From Table 1, read the percentage of source strength. c. Determine vapor source strength, Q, by multiplying the liquid source strength by the percentage of source strength for the material involved. RSV 001Z936 6 Hazardous Material TABLE 1 Percentaae of Liauid Spill Rate Acetaldehyde 100 Acetic anhydride Negligible Acetone 60 Acetone cyanohydrin Negligible Acrylonitrile 25 Ammonia 100 Aniline Neolioible Benzene 15 Butadiene (inhibited) 100 Butane 100 Butenes 100 Butyl alcohol Neolioible Carbon disulfide 8b Carbon tetrachloride 25 Chlorine Chlorosulfonic acid 100 Negligible Cumene (isopropyl benzene) Neolioible Dichloro difluoromethane 100 Dodecvl benzene 100 Ethyl alcohol (ethanol) Negligible Ethyl benzene Negligible * Ethyl chloride 100 Ethylene dichloride 60 Ethylene oxide Fluorine ________________ IfiQ___________________ Negligible Formaldehyde 100 Hexamethy1enediamine Negligible Hydrogen chloride 100 Hydrogen cyanide 100 Hydrogen fluoride 100 Hydrooen sulfide 100 Insecticides (parathion), etc. Negligible Isopropyl alcohol Negligible LPG (see propane) ------------------------- TOO' ----------------------- Methyl alcohol 2b - Methyl ethyl ketone 5 Methyl methacrylate Negligible Nitric acid (fumes) Perchloric acid Negligible Perchloroethylene Negligible Phenol Negligible Phthalic anhydride Propane Negligible 100 Sul fur dioxide 100 Sulfuric acid (fumes) Negligible Styrene Nealiaible Tetraethyl lead * Negligible Toluene Negligible Trichloro-ethane Negligible Trichloroethylene Negligible Vinyl acetate 25 Vinyl chloride 100 Xylenes (xylols) Negligible Cyclohexane 15 RSV 0012937 7 "CAUTION" Ensure that all persons at the scene, including yourself, follow these instructions: "DO NOT ENTER OR HOVE ABOUT INSIDE A POTENTIALLY HAZARDOUS CLOUD WITHOUT PROPER PROTECTIVE GEAR. KEEP SPARKS, OPEN FLAMES, AND LIT TOBACCO OUT OF THE HAZARDOUS AREA." Each Regional Office has a multiple purpose detection kit that will be used to detect unknown gases. The detector kit contains a hand pump and sample tubes. A prescribed amount of gas is drawn into the pump and then forced back through a hollow needle into the detector tube. If the proper gas is in the air, a chemical reaction will take place in the detector tube. Con centration of the gas is estimated by comparing the color change or length of stain of the reagent in the tube with a reference calibration chart included with the tubes. When sampling for an unknown gas, it would be senseless to start searching at random or in alphabetical order. For this reason, a list of the 15 most common gases has been prepared. Measures to identify the material should be started with the first chemical on the list and then continued until all tubes are used up or until a deter mination of the chemical Is obtained. 15 MOST COMMON GASES INVOLVED IN AIR POLLUTION INCIDENTS Hydrogen sulfide Vinyl chloride (chloroethylene) Ethylene oxide Chlorine Anhydrous ammonia Acetaldehyde Hydrogen cyanide (hydrocyanic acid) Acrylonitrile (vinyl cyanide) Methanol (methyl alcohol) Benzerre (benzol) Formaldehyde Acetone Butane(s) Propane Ethyl chloride (chloroethane) Once the substance has been identified, further informa tion will be furnished to the engineer at the scene by the Emergency Action Center regarding the characteristics of the hazardous materials including its toxicity, flam mability, explosibility, and reactivity. MSL 0032833 If unable to determine the chemical or gas after these actions, then collect, If possible, samples of the material and call the Emergency Action Center for instructions. The Emergency Action Center will make arrangements for the samples to be analyzed at the nearest chemical analysis laboratory. If, after these actions, the material is still unidentified, the Episode Unit will take action to procure experts from the academic community to analyze the situation. RSV 0012938 8 6. Estimate windspeed and direction. Take windmeter in one hand and compass in the other. Hold winditieter in vertical position in front of you with your arm extended. Do not . block holes in bottom of meter. If wind is stronger than 10 mph, hold your finger over the red cover hole and read wind speed on high scale. Rotate yourself slowly until highest windspeed is obtained; record this windspeed on checklist in meters per second (Figure 1 ). Examine compass to determine wind direction. Remeirber, you are facing the direction from which the wind is blowing. Hold compass hori zontally and wait-a short period of time to insure that the compass needle has stabilized. Record direction from which wind is blowing by degrees on checklist. Place in terms of compass points by rounding direction to the nearest 10 degrees and using Table 2. TABLE 2 Direction in Degrees 350*-10* 20*-30* 40*-50* 60*-70* 80*-100* 110*-120* 130*-140* 150*-160* 170*-190* 200*-210* 220*-230* 240*-250* 260*-280* 290*-300* 310*-320* 330*-340* Compass Direction N NNE NE ENE E ESE SE SSE S ssw sw wsw w WNW NW NNW 7. Record temperatures on checklist. 8. Identify stability class (in general the following will apply): Unstable - Category B - Fair to partly cloudy day with 1ight wind Neutral - Category D - Cloudy day or night or anytime wind over 10 mph Stable - Category F - Fair night with light wind 0012939 Observe the cloud cover and determine which cloud cover classification in Table 3 is appropriate. From Table 3 determine the Net Radiation class. Enter this category on the checklist. 9 FIGURE 1 RSV 0012940 10 TR5EE 3----------------- , NET RADIATION CLASSES Cloud Cover Night <3/8 3/8 or 4/8 at any hgt or broken abv 16000 ft (incl. -) abv 16000 ft or CD between 7000 ft and 16000 ft CD below 7000 ft below 7000 ft -2 -1 -1 0 0 Elevation of Sun All days > lb" but 35* *Feb. 10- Apr. 16Nov. 2 Auo. 26 >35* but > 6(r *60* -1 +1 +2 +3 0 +1 +2 +3 0 0 +1 +1 0 0 +1 +1 00 00 TABLE 4 STABILITY CATEGORY BASED ON WIND SPEED AND NET RADIATION Surface Wind Speed Net Radiation Class (see Table3 ) m/sec knots +3 +2 i +1 0 -1 -2 <2 <4 2-3 4-6 3-5 6-10 5-6 10-12 >6 >12 B B BD F F B B BD F F B B DD D D D D DD D D D D DD D 0 rNote Dates indicate days on which the maximum elevation of the sun will be in the angular range during some period of the day. RSV OOI2941 -u - 9. Obtain excursion threshold value (ETLV). from Table 5 and enter on checklist. 10. Determine downwind hazardous area by following method; Enter (ETLV), windspeed, and source strength in following expression: source strength (Q)(gm/sec) x 10^ K s - -- - windspeed (m/sec) x ETLV (mg/m3) Enter K in Figure ? and obtain downwind distance in desired units. Enter downwind distance given in meters into Figure 3 and obtain crosswind distance. Construct downwind hazardous area. i 0cO1 I I * - wind direction downwind distance crosswind distance ^*3 crosswind distance 11. Adjustments for terrain: Predicted hazard areas may require adjustment for variations In terrain. This task can only be approached subjectively, guided by the engineer's familiarity with the terrain in the threatened area. The following generalities may be of help. a. Winds under 5 m/sec (11-12 mph) tend to follow paths of least resistence: river channels, valleys, city streets, etc. b. Winds are diverted by obstacles such as prominent hills, and in cities by large buildings. With stronger winds that are forced upward, around, and over these obstacles, reverse eddies tend to appear on the lee side in which there are zones of increased and decreased concentrations of airborne contaminants. Hence, the lee side of a hill or building may not offer temporary safety from a toxic cloud. RSV 00X2942 T'FLE 5 .JSTANCE CODE Acetaldehyde 0006 Acetic Acid (glacial) 0037 Acetic Anhydride 0038 Acetone 0057 Acetone Cyanohydrin 0058 Acetonitrile (raethylcyanide) 0066 Acetyl Chloride 0082 Acetylene 0131 Acetylene Dichloride (1, 2 Dichloro Ethylene)0136 Acrolein 0153 Acrylonitrile Allyl Alcohol Ammonia (anhydrous) Amyl Acetate Amyl Alcohol Aniline Antimony Trichloride Arsenic Trioxide Barium Chlorate Barium Nitrate 0158 - 0205 0451 0542 0550 0657 0714 0779 0870 0904 Barium Peroxide Benzene zoyl Peroxide benzyl Chloride Bromine Butadiene utane(L.F.G.) Butyl Acetate Butyl Alcohol Butyraldehydes 0914 0976 1086 1117 1269 1420 1422 1430 1435 1564 Calcium Calcium Cyanide Calcium Hypochlorite Carbon Disulfide Carbon Monoxide Carbon Tetrachloride Chlorine Chlorobenzene Chloroisocyanuric Acid Chloroform 1643 1665 1675 1778 1780 1792 1924 1963 1998 2023 Chlorosulfonic Acid Chromic Acid Cresol Cyanoacetlc Acid Cyanogen ' lohexane Lopropane * .aborane Diborane Dichlorobenzene 2105 2159 2357 2465 2471 2485 2506 2517 2685 2845 Excursion TLV (Max. cone. permitted for short time) o*2/m3 125 15 5 1000 15 60 7.5 Asphyxiant 250 0.3 225 38 21 2400 52 105 24 988 0.75 30 4 38 125 125 7.5 - - - _ 25 2 0.3 1000 500 188 125 250 _ 10 1 30 75 15 2 94 60 31 68 10 27 656 450 28 2.8 4.0 0.5 0.5 0.5 80 10 10 2.1 2200 1200 888 378 738 5 o (bleaching povde 5(anhydrous) 90 82 98 6 438 402 150 5 _ 7.5 60 20 300 500 0.15 0. 3 50 23 0.3 33 209 43 1050 662 0.9 0.3 300 m o o o cfi QC SUBSTANCE Diesel Fuel Oil Diethyl Amine Dicthylene Triamine Dimethyl Formamide 1,1-DimethyIhydrazine Dimethyl Sulfate Dinitro Aniline Dinitro Benzene Dinitro Toluene Dioxane (Diethylene Dioxide) Epichlorohydrin Echanolamine (moneochanolamine) Ethyl Acetate Ethyl Acrylate Ethyl Alcohol (Ethanol) Ethyl Benzene Ethyl Chloride Ethyl Ether Ethylene Ethylene Dichloride (1,2 Dichloroethane) Ethylene Oxide Fluorine Formaldehyde para-Formaldehyde Formic Acid Hydrazine Hydrochloric Acid (Hydrogen Chloride) Hydrocyanic Acid (Hydrogen Cyanide) Hydrofluoric Acid (Hydrogen Fluroide) Hydrogen Peroxide Hydrogen Sulfide Kerosene Lead Nitrate Lead Oxides Malathion Maleic Anhydride Mercaptans Mesityl Oxide Methyl Acetate Methyl Acrylate Methyl Alcohol (Methanol) Methyl Amine9 Methyl Bromide Methyl isoButyl Ketone Methyl Chloride Methyl Chloroform Methyl Ethyl Ketone (2-Butanone) Methyl Formate Methyl Hydrazine CODE 2981 3000 3130 3383 3391 3456 3487 3500 3565 3584 3794 3831 3859 3866 3870 3897 3939 3970 4116 4126 4135 4247 4283 4285 4296 4753 4788 4803 4806 4814 4817 5116 5194 5197 5460 5462 5499 5581 5615 5623 5628 5633 5675 5692 5711 5715 5760 5770 5797 --T13 - Excursion TLV (Max. cone. permitted for short time) ppm mg/rn^ 625 38 2 15 1.5 2 1 - 125 7.5 6 400 38 1000 125 1000 400 Asphyxiant 62 4700 112 8 45 3 10 7 3 3 450 28 12 1400 150 1900 544 2600 1212 250 75 135 24 23 10 12 10 18 2 2.6 57 15 16 64 2 2.8 15 500 - - - .75 15 38 250 22 3200 0.3 0.2 20 3 15-30 150 762 15 250 15 22 100 125 350 250 125 0.2 52 328 18 90 411 260 1900 738 312 0.35 RSV 0012944 SUBSTANCE CODE Methylene Chloride (Dichloromethane) Napthalene Nitric Acid Nitroaniline Nitro Benzol (Micro Benzene) Nitrochlorobenzene Nicroethane Nitrotoluene Nitrogen Tetroxide Parachlon 5957 6022 6236 6271 6299 6350 6386 6498 6534 6757 Pentaborane Perchloroethylene Phenol (Carbolic Acid) Phosgene (Carbonyl Chloride) Phosphoric Acid Phosphoric Anhydride (Phosphorus Pencoxide) Phosphorus, Red Phosphorus, White (Yellow) Phosphorus Oxychloride Phosphorus PentaSulflde 6771 6814 68S0 7003 7017 7019 7023 7024 7049 * 7053 Phosphorus Trichloride Phthalic Anhydride Potassium Cyanide Propane Propionaldehyde isoPropyl Alcohol isoPropyl Amine Propylene Propylene Oxide Pyridine 7067 7079 7219 7360 7371 7391 7394 7481 7490 7516 Silver Nitrate Sodium Chlorite Sodium Dichromate , Sodium Hydroxide Sodium Potassium Alloys Styrene (Monomer) (Phenylethylene) Sulfur Chlorides Sulfur Dioxide Sulfuric Acid, Fuming (oleum) Sulfuric Acid 7858 7925 7934 7950 8005 8157 8199 8025 8213 8214 ' Tetraethyl Lead Tetra Hydrofuran Toluene (Toluol) Toluene DiisoCyanate Toluidine Trichloroethylene Turpentine (oil) Vinyl Acetate Vinyl Chloride (Chloroethylene) Xylene Zinc Chlorate 8335 8344 8629 8631 8664 8824 9068 9197 9206 9231 9323 Excursion TLV (max. cone. permitted for short time) sm ag/m-i 500 15 4 2 2 0.5 1740 75 10 12 10 3 125 7.5 388 42 5 18(Liquid) 9( .025 0.3 0.015 125 7.5 0.3 0.75 1 Non toxic 0.5 0.03 838 26 1.2 3 5.8 0.3 3 3 1 3 - Asphyxiant 200 500 7.5 4000 125 7.5 6 18 5 476 1225 18 6900 300 22 _ 0.01 - 0.74 - 0.3 -4 -2 125 525 2(Monochloriddl2 7.5 19 0.75 3 0.75 3 0.03 250 125 0.02 7.5 125 125 15 250 125 - 0.45 738 469 0.14 33 669 695 45 962 544 1 RSV 0012945 FIGURE 2 15 .06 .12 .19 .31 .62 1.2 1.9 3.1 DOWNWIND rTwTANCE 6.2 (raecers) 12 19 31 62 (miles) RSV 0012946 FIGURE 3 16 - CROSSVJIND DISTANCE DOWNWIND DISTANCE RSV 0012947 - 17 - c. If the wind travels upslope, gases that are significantly heavier than air may not be transported.as far as the calculated downwind distance. The pattern of concentra tion would be foreshortened, and contamination in the valley would be heavier than expected. d. This correction may be required for all the 15 gases on the priority list with the exception of airmonia and hydrogen cyanide. If the wind travels downslope, gases that are significantly lighter than air, chiefly ammonia and to a lesser extent hydrogen cyanide, would appear in lower concentrations downwind"than expected. 12. Adjustments for fire: The fire hazard has not been considered in construction of the hazardous area. Many of these chemicals are highly flanmable. In some cases ignition caused by a spark or open flame some distance downwind may flash back to the source, resulting In an initial explosion or fire of wide di mensions. Once In progress the fire tends to be concentrated at the source only, and the emanating cloud consists of combustion products that may or may not be toxic but are at least suffocating or highly irritating. Atmospheric dispersion models that treat this phenomenon generally consider the "stack effect" of the fire and the local atmospheric instability condition that rapidly develops near the source. However evacuation of people from an area farther than about 1 km from the fire is seldom required. The Emergency Action Center personnel can provide assistance In determining the hazardous area under such conditions. 13. Determine if additional support is required. Since your specific responsibilities are concerned with the contamination of the atmosphere, additional support required should be limited to such items as the need for more engineers or technicians, outside experts to determine the nature of the gas or chemicals involved, or meteorological support. You should appraise the overall situa tion. Determine if the general population is in danger, and if the local law enforcement of civil defense officials are performing their duties properly. If they are not, notify the Episode Unit of this fact. 14. If members of the press are present at the scene and ask to inter view you, you should request that they speak to the individual in charge of controlling the incident. You should refrain from making comments to the press other than to inform them of the nature of the gas or chemical involved. RSV 0012948 AJK POLLUIIUN INUUbNI FIGURE 4 1A - . .RESPONSE-SHEET BATES ; TIKE KOTIFIED : ANS. SERVICE Q CALLER'S NAME: ORGANIZATION;____________________________________________________________________ CALL BACK NUMBER: LOCATION: ` CHFHI CAL /MATERIAL INVOLVED: QUANTITY:CONTAINER TYPE: NUMBER OP CONTAINERSS PROBLEM (include type of accident, time of accident* Injuries* details): LOCATION (give distance 6 location from nearest eltp* highway Ambers* road n*nes, populated or open area): VLATLLR (list significant weather such as rain, drisxle, snow, fog, etc. after contents) STY CONDITION: TEMPERATURE: WIND SPEED AND DIRECTION: COMMENTS: i TJT.SONNEL AT SCENE; CIVIL DEFENSE POUCE n ntire WATER FOLLUTION PI PUBLIC WATER SUPPLIES PI AIR POLLUTION PI ... OTHER ' - CARRIER NAME AND TYPE; RAIL CAR NUMBER: ORIGIN: __ ____EUGINEER/EAC PERSONNEL FILINS REPORTr TKUCE/TRAILER NUMBER: DESTINATION: IU.W*S _Z?A KERD*CT 24-ER. TELEPHONE NUMBER: (217) 525-3637 RSV 0012949 CHECKLIST Date __. Engineer ________________ Report to individual in charge (Name Material(s) involved: _____ _________________ , ). , Quantity of material involved: ______________ Quantity of material being released. (source strength in gm/sec) _______________________ If volatile liquid, vapor pressure from Table 1: Source strength (gm/sec) x X of spill rate * source strength Windspeed Wind direction x * (gm/sec). (m/s). _(degrees) compass point Temperature F. Net radiation class (Table 3): Stability category (Table 4): Excursion threshold value Downwind hazardous area: Q (gm/sec) x 103 (ugm*3) windspeed (m/sec) x ETLV (mg/m3) ,,( ) x 103 ( ) x( ) Downwind distance: Crosswind distance: mi (Figure 2). mi (Figure 3). RSV 0012950