Science Officer`s Workbook
Transcription
Science Officer`s Workbook
2011 Science Officers POCKET FULL OF KNOWLEDGE This is a guide for Science Officers to use. It is intended to be used as a RULE OF THUMB. There are no absolutes in Hazmat. Clint Greenwood, Ryan Marlar, Robbie Bay, Matt Tennell, John Carpenter, Mike Mahoney and Scott Lance 1/1/2011 CHEMICAL FORMULAS Key Points If a product’s formula has a C&H in it the product formula will most likely burn. o o o Organophosphates are some of o o the most toxic chemicals; in o their chemical formulas you should be able to spell “CHOP”. o Examples Toluene C5H6CH3 this product burns. Propylene Oxide C3H5O this product burns. Malathion C10H19O6PS2 Trimethyl Phosphite (CH 30)3P Sarin C3H7FO2P+ VX CH3CH2O-P(O)(CH3)SCH2CH2N(C3H7)2 Tabun C5H11N2O 2P Explanation An easy way to remember this is think C&H = “CHar”. Note: The “CHOP” can be in any order in the formula as long as all the letters of chop are present. These can be nerve agents too. VAPOR PRESSURES Key Points Examples o Chlorine has a vapor pressure of 6.8atm, so it is a gas. o Dipropyl Ketone has a vapor pressure of 5mm/Hg, so it is a liquid. Explanation Rule of thumb vapor pressure of gases are typically given in atmospheres (atm). 760mm/Hg = 14.7psi = 1atm, is the Rule of thumb – vapor liquid/gas hinge point pressure of liquids are typically given in millimeters of mercury (mmHg). At about 40mm/Hg chemicals o Water has a vapor pressure begin to evaporate and of 21 mm/Hg. escape their container o Nitric Acid has a vapor A good rule of thumb to consider: Liquids with a vapor pressure pressure of 48 mm/Hg. of 100mm/Hg and above o Acetone has a vapor should be considered a high pressure of 180 mm/Hg. vapor pressure (volatile). Gases – V.P. in ATM multiply it by 14.7 psi. Liquids – V.P. in mmHg multiply by 0.02 psi. Vapor pressures listed in the NIOSH o Chlorine has a vapor pocket guide are based on a 68° day pressure of 6.8 atm at 70°. unless otherwise noted. o So the pressure in a Chlorine containers have container carrying chlorine about 100 psi on a 70° degree For every degree +/-temperature can be figured by day. change a +/-change of 2 psi in a multiplying 14.7psi x 6.8 closed container. atm = 99.96 psi. We use 70°, it easier to do the math. o Chlorine has a vapor Vapor pressures listed in the NIOSH pressure of 100 psi on 70° 80° - 70° = 10° x 2 = 20 psi. pocket guide are based on a 68° day degree day. 100 + 20 = 120 psi in unless otherwise noted. o Today’s temperature is 80 container today. We use 70°, it easier to do the math. degrees. 2 8/25/2011 MOLECULAR WEIGHT Key Points Atmospheric air has a molecular weight of 29. A molecular weight greater than 29, the vapors will sink. A molecular weight less than 29, the vapors will rise. Vapor Density = M.W. ÷ 29 Flammable and corrosive liquid vapors sink. Examples/Explanation Atmospheric air is the means of comparison for other gases and vapors. Cyclohexane has a molecular weight of 84.2, so the vapors sink. Ammonia has a molecular weight of 17.0, so the vapors rise. Propane has a molecular weight of 44.1. 44.1 ÷ 29 = Vapor Density of 1.5 Gasoline has a molecular weight of 110, so the vapors sink. Sulfuric Acid has a molecular weight of 98.1, so the vapors will sink. Products that rise: 4h Hydrogen Medic Methane Anna Anhydrous Ammonia Helium Ethylene Neon Hydrogen Cyanide Diborane Nitrogen Hydrogen Fluoride Illuminating gas Acetylene Carbon Monoxide SOLUBILITY Key Points Examples The human body is comprised primarily of water. Miscible and highly soluble products pose a potential higher hazard to the human body Explanation Hydrazine – miscible Sulfuric acid – miscible Sodium hydroxide – soluble 111% Potassium hydroxide – soluble 107% If products have a solubility of less than 10% o Chlorine 0.7% solubility, you should air ventilate. air ventilate. Water will not be effective o Vinyl Chloride 0.1% solubility, air ventilate. on these products. o Triethylamine 2% Decon will typically require solubility, air ventilate. soap to remove the product. o Hydrogen Chloride 67%, If products have a solubility of more than water ventilate. 10%, water ventilate. o Trimethylamine 48%, water ventilate. Decon may be o Propylene Oxide 41%, accomplishable by water water ventilate. alone. 3 Less than 10% solubility means the product will not grab an appreciable amount of product to make a difference. It won’t take knock down vapors. Note water will be effective in decon with products that have greater than 10% solubility. If water is added, consult the “Chemical Reactivity Worksheet” in CAMEO to determine outcome. 8/25/2011 SPECIFIC GRAVITY Key Points Products that float: If a product floats on water it generally has a higher vapor pressure. o o o o o o Examples Hydrocarbons (alkanes, alkenes) Aromatics (benzene, toluene, xylene) Polar organics with generally more than 4 carbons (ester, aldehydes, amines) Long chain alcohols & organic acids. Cyclopentadiene sp.gr. 0.80 & V.P. 400mmHg. Gasoline sp.gr. 0.72-0.76 & V.P. 30300mmHg. Products that sink: o Halogenated Hydrocarbons (tetrachloroethylene). o Nitro Compounds (nitromethane). o Organic Peroxides (methyl ethyl ketone peroxide, benzoyl peroxide). If a product sinks in water it generally has a very low vapor pressure. o Malathion sp.gr 1.21 & V.P. 0.00004mmHg. o Phorate sp.gr 1.16 & V.P. 0.0008mmHg. Products that mix: o Inorganic corrosives (sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide) o Organic compounds, dependent upon their molecular weight. o Carbonyl & hydrogen bonds. Explanation Likely LEL present. Anytime a hydrogen is taken away and replaced with any other element, is automatically becomes heavier than what it was originally. If a product sinks you should consider it toxic until you can prove otherwise. Likely no LEL present. Products that are convinced to mix: Products that emulsify: Products that chill Figuring the weight of products using specific gravity. o Organic compounds that contain a carbonyl bond. o o o o o Organophosphates (malathion) Organochlorine (DDT) Thiophosphate (demeton) Some herbicides (2,4,5-T Cold pack (inorganics: nitrates, ammonium salt, thiosulfates) o Specific gravity is compared to water at 1 o Water weighs 8.33 lbs. per gallon. 4 Organic Acids: formic acid, acetic acid Alcohol: methanol, ethanol, propanol Ketones: acetone Ketones: methyl ethyl ketone Aldehydes: acrolein Amine: dimethylamine Esters: methyl acetate Tend to emulsify & turn a creamy white color in solution. Subtle and easily missed. Sulfuric acid sp.gr is 1.84 8.33 (water) x 1.84 (sulfuric acid) = 15.33 lbs. per gallon. 8/25/2011 MELTING POINT Key Points Products with a four digit melting point are inorganic and most likely will not burn. Products with a three digit melting point are organic and will most likely burn. Use the spoon test on solids to determine melting point. Examples o Calcium Cyanamide 2444:F Explanation HazMat I.D., PID, 4-gas, HazMat inorganic. CAD, won’t see inorganic products. o Camphor 345:F organic. o Sugar (sucrose) 320-367:F organic. HazMat I.D., PID, 4-Gas, HazMat CAD will see organic products. Use table sugar (sucrose) to establish a baseline temperature. CORRELATION Key Points Products that have a low boiling point and flashpoint have a high vapor pressure, ignition temperature, and produce more vapors. Products that have a high boiling point and flashpoint have a low vapor pressure, ignition temperature. Examples o Ethyl Mercaptan - 442mmHg. ↓B.P. 95: ↓FL.P-55: & ↑V.P. o Acetaldehyde - 740mmHg. ↓B.P. 69: ↓FL.P-36: & ↑V.P. Explanation Vapor Pressure Vapor Production Boiling Point Boiling Point o Propyl Acetate - 25mmHg. ↑B.P. 215: ↑FL.P 55: ↓V.P. 5 Vapor Pressure Vapor Production 8/25/2011 ALKANES EXHIBIT: Low Boiling Points and Flash Points which increase with carbon count. High Vapor Pressures that decrease with carbon length. Solubility Insoluble to <1% to slight. All are floaters WET CHEMISTRY: pH slightly acidic (4-7) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – very low GENERAL DESCRIPTION: Also known as the “parafins” of the aliphatic family. Chemical name ends in “ane”. Are considered stable hydrocarbons. Flammable to combustible; 1% - 8%. Formula contains: “C” & “H” only. Formula contains: CnH2n+2 OBSERVATIONS FOR FLAME: COMMON USES: C1 – C4: Petroleum gases C5 – C9: Light naphthas, (pentane, hexane, heptane) gasoline (octane) C10 – C16: Fuel oils, mineral spirits, kerosene (fuel oil #1), solvents C17 – C25: Heavy fuel oils; diesel fuel (fuel oil #2) & residual bunker fuels (fuel oil #4,5 & 6) ELECTRONICS: C26 & up: Lubricating oils, asphalt, tar EXAMPLES: Gases: Methane, ethane, propane, butane Liquids: Pentane, hexane, heptane, octane, nonane, decane Luminous, tall orange flame; invisible or blue base. Clear smoke would indicate simple, single-bonded organic with low carbon number (methane, propane). Some sooty black smoke would indicate single-bonded organic with higher carbon number (gasoline, kerosene, diesel). 4gas – good LEL response PID: C1 – C4 all I.P. over 10.6eV C5 and up all I.P. below 10.6eV HazMatID variable sharp peaks from: Variable, sharp peaks from 3000-2800 Specific gravity – floater Alka-seltzer – should not fiz Q-tip – flammable to combustible Ketone test – does not melt styrofoam ALKENES EXHIBIT: Relatively low Boiling Points and Flash Points which increase with carbon count. Relatively high Vapor Pressures that decrease with carbon length. Solubility Insoluble to <1% to slight. All are floaters WET CHEMISTRY: pH slightly acidic (4-7) Spylfiter test #4 – most common are flammable gases M8/M9 – most common are flammable gases KI paper – no change Solubility – most common are flammable gases, very low Specific gravity – floater GENERAL DESCRIPTION: Also known as the “olefins” of the aliphatic family. Chemical name ends in “ene”. Contains double bond. Are considered less stable (polymerize) unsaturated hydrocarbons. Flammable to combustible. Formula contains: “C” & “H” only. Formula contains: CnH2n & “=” OBSERVATIONS FOR FLAME: Black smoke with a few spiderwebs would indicate an unsaturated hydrocarbon (double bonds) or a mixture. COMMON USES: Short-chain alkenes are valued for their ability to polymerize and such are the backbone of the rubber and plastics industry. EXAMPLES: Gases: Ethylene/ethene, propylene/propene, butylene/butene ELECTRONICS: 4gas – good LEL response PID – all I.P. below 10.6eV HazMatID: Liquid from pentene onward, but not commonly encountered. Liquids: Pentene, onward 7 8/25/2011 ALKENES EXHIBIT: Low Boiling Points and Flash Points which increase with carbon count. Very high Vapor Pressures that decrease with carbon length. Solubility Insoluble to <1% to slight. WET CHEMISTRY: pH slightly acidic (4-7) Spylfiter test #4 – most common are flammable gases M8/M9 – most common are flammable gases KI paper – no change Solubility – most common are flammable gases, very low Specific gravity – floater GENERAL DESCRIPTION: Chemical name ends in “yne” of the aliphatic family Contains a triple bond. Are considered a highly unstable , highly reactive (polymerize to explosive) unsaturated hydrocarbons. Generally have very wide flammble ranges. Formula contains: “C” & “H” only. Formula contains: CnH2n-2 & “≡” COMMON USES: The only alkynes that are commercially important are used for cutting & welding of metals. EXAMPLES: Gases: Ethyne/acetylene, propyne/methacetylene OBSERVATIONS FOR FLAME: Black smoke with a few spiderwebs would indicate an unsaturated hydrocarbon (double bonds) or a mixture. ELECTRONICS: 4gas – good LEL response PID – some I.P. over 10.6eV HazMatID: Liquid from pentene onward, but not commonly encountered. Liquids: Butyne/dimethylacetylene, onward 8 8/25/2011 AROMATICS EXHIBIT: High Boiling Points and Flash Points which increase with carbon count. Low Vapor Pressures that decrease with carbon length. Solubility <1%. All are floaters GENERAL DESCRIPTION: Also referred to as “BTEX”. Chemical name ends in “ene”. Are considered very stable hydrocarbons due to the resonant bonding. Flammble to combustible; 1% - 7% Formula contains: “C” & “H” only. CnHn (minimum of 6 carbons) WET CHEMISTRY: Used mainly as solvents and as feedstock chemicals for chemical processes that produce other valuable chemicals. EXAMPLES: Liquids: Benzene, Toluene, Ethyl benzene, Xylene Solubility – very low Specific gravity – floater Alka-seltzer – should not fiz Q-tip – flammable to combustible Ketone test – does not melt styrofoam OBSERVATIONS FOR FLAME: Orange flame, no blue base: BTEX (benzene, toluene, ethyl benzene, xylene) COMMON USES: pH slightly acidic (4-7) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Look for black spider-webs in the smoke. Considerable black soot remains on watch glass. So stable they burn with a high degree of incomplete combustion. ELECTRONICS: 4gas – good LEL response PID – all I.P. below 10.6eV HazMatID: Weak, sharp peaks from 3100-3000 Strong sharp peaks below 850 9 8/25/2011 ETHERS EXHIBIT: Low Boiling Points and Flash Points which increase with carbon count. High Vapor Pressures that decrease with carbon length. Solubility <10%. All are floaters WET CHEMISTRY: pH slightly acidic (5-7) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – very low Specific gravity – floater Alka-seltzer – should not fiz Q-tip – generally very flammable Ketone test – does not melt styrofoam GENERAL DESCRIPTION: As a class of flammable liquids, ethers are generally more dangerous than the other classes of flammable liquids because their flash points are usually lower, and the hazard of the anesthetic properties poses an additional danger. May become unstable (oxidize into a peroxide) if not used within 6 months after opening. Generally very flammable 2% -48% Formula contains: “C” & “H” along with a single “O” COMMON USES: In the ether family, there is a wide range of solvents, refrigerants, and pharmaceutical application. EXAMPLES: Liquids: Ethyl ether (starter fluid), Isopropyl ether OBSERVATIONS FOR FLAME: Low flash point. Yellowish orange tall flame, blue base, clean smoke, or only very little black in the smoke. Ethers have about twice the amount of yellow flame, giving them an almost banana look. ELECTRONICS: 4gas – good LEL response PID – all I.P. below 10.6eV HazMatID: One or more strong, sharp peaks nearby 1000. Hydrocarbon peaks near 3000. 10 8/25/2011 ORGANOPHOSPHATES EXHIBIT: High Boiling Points and Flash Points which increase with carbon count. Very low Vapor Pressures that decrease with carbon length. Solubility <1% to insoluble Most emulsify, most all are sinkers WET CHEMISTRY: pH – slightly acidic (3-7) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – look for a clear unknown that turns an opaque, milky white when poured into the water, emulsifies. Alka-seltzer – should not fiz Q-tip – generally a difficult combustible Ketone test – does not melt styrofoam GENERAL DESCRIPTION: Organophosphate is a commonly used name for pesticides, which actually encompasses many chemicals. The family of pesticides is a large group of very diverse compounds from rat bait to snail poison. Formula contains: “CHOP” OBSERVATIONS FOR FLAME: White on or in flame would indicate organo-sulfur or organo-phosphorous compounds and herbicides COMMON USES: Insecticides target insects, herbicides target plants, rodenticides kill rats, however, all of these pesticides are toxic to humans in some degree. ELECTRONICS: EXAMPLES: Liquids: Malathion, diazinon, demeton 4gas – weak to no LEL response; may get CO or H2S false positives. PID – many I.P. are undetermined. HazMatID: One or more strong, sharp peaks nearby 1000. Hydrocarbon peaks near 3000. 11 8/25/2011 ALKYL HALIDES EXHIBIT: High Boiling Points and Flash Points which increase with carbon count. Very low Vapor Pressures that decrease with carbon length. Solubility <1% to insoluble. All are sinkers. GENERAL DESCRIPTION: Also known as halogenated hydrocarbons. The simplest hydrocarbon derivative involves the addition of a halogen onto the hydrocarbon backbone, resulting in the Halogenated Hydrocarbons: Fluorine, Chlorine, Bromine, Iodine Formula contains: “C” & “H” along with a “Fl”, or “Cl”, or “Br”, or “I” COMMON USES: Have commonly been used as: Refrigerant (Freon 10, carbon tetrachloride) Fire extinguishing agent (halon 1211, 1301) Cleaning solvents (perchloroethylene) Pesticides (chlordane) WET CHEMISTRY: pH slightly acidic (3-7) some are very corrosive Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – <1% Specific gravity - sinker Alka-seltzer – should not fiz Q-tip – Combustible to noncombustible Ketone test – may melt styrofoam OBSERVATIONS FOR FLAME: Self-extinguishing, turquoise band at base of flame indicates a chlorinated organic. The higher the ratio of chlorine to hydrocarbon, the more turquoise will be seen. Copper wire test – blue/green flame. ELECTRONICS: 4gas – weak to no LEL response Some are corrosive PID – many I.P. are over 10.6eV. HazMatID: Strong, sharp peak(s) below 800 12 8/25/2011 NITROS EXHIBIT: High Boiling Points and Flash Points which increase with carbon count. Low Vapor Pressures that decrease with carbon length. Solubility 10% or less. All are sinkers. WET CHEMISTRY: pH slightly acidic (4-7) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – <1% Specific gravity - sinker Alka-seltzer – should not fiz Q-tip – Combustible to noncombustible Ketone test – should not melt styrofoam GENERAL DESCRIPTION: Contains at least one nitrogen with two single bonded oxygen. Oxygen-to-oxygen single bonds are very unstable and reactive. Formula contains: “C” & “H” along with “NO2” OBSERVATIONS FOR FLAME: Gray or pink/purple flame that may be almost white indicates a nitro compound. COMMON USES: Commonly found as explosives. Powerful fuels. Used as racing fuel & for RC cars. EXAMPLES: Liquids: Nitromethane, nitroethane, nitroglycerine, etc. ELECTRONICS: 4gas – weak to no LEL response PID – many I.P. are over 10.6eV. HazMatID: Strong, sharp peak near 1550. Strong, sharp peak, similar intensity near 1350. 13 8/25/2011 ORGANIC PEROXIDES EXHIBIT: High Boiling Points and Flash Points which increase with carbon count. Low Vapor Pressures that decrease with carbon length. Solubility <1% to soluble. All are sinkers. WET CHEMISTRY: pH slightly acidic (4-7) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – change; black, purple, blue Solubility – <1% Specific gravity - sinker Alka-seltzer – should not fiz Q-tip – Flammable to combustible Ketone test – may melt styrofoam GENERAL DESCRIPTION: The organic peroxides are a group of hazardous materials into which man packed as many hazards as he possibly could. Designed to be a “fire waiting to happen”. They all contain two legs of the fire triangle: They are organic and all organic materials burn. The presence of the peroxide radical is an intimate source of oxygen. Will have a “MSST” & “SADT” temperature. Formula contains: “C” & “H” along with a “O2” or “OO”. OBSERVATIONS FOR FLAME: ELECTRONICS: COMMON USES: Most commonly used as initiators or catalysts in polymerization reactions. EXAMPLES: Liquids: Methyl ethyl ketone peroxide, benzoyl peroxide Varying results from just flammable, to intense flammability, to explosive 4gas – LEL response varies, generally weak. PID – many I.P. are undetermined. HazMatID: Not able to see peroxide radicals. 14 8/25/2011 ORGANIC ACIDS EXHIBIT: High Boiling Points and Flash Points which increase with carbon count. Low Vapor Pressures that decrease with carbon length. Solubility Super-duper miscible. WET CHEMISTRY: pH acidic (2-3) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – Super-duper miscible Specific gravity – super-duper miscible Alka-seltzer – will fiz “acidic” Q-tip – combustible Ketone test – does not melt styrofoam GENERAL DESCRIPTION: Also commonly referred to as carboxylic acid. The most polar of the hydrocarbon derivatives, considered “super-duper” polar. An acid containing carbon making them “organic” acids. Formula contains: “C” & “H” along with “COOH” OBSERVATIONS FOR FLAME: Nothing specific COMMON USES: Organic acids are much less reactive with metals than are strong mineral acids, and are used for oil and gas well stimulation treatments when long contact times between acid and pipe are needed. ELECTRONICS: EXAMPLES: Liquids: Formic acid, acetic acid, propionic acid, ethanoic acid, butyric acid **Caution CORROSIVE** 4gas – weak LEL response PID – few with I.P. above 10.6eV HazMatID: Strong, sharp peak from 1720-1680. Broad, bumpy peak around 3000 15 8/25/2011 ALCOHOLS EXHIBIT: High Boiling Points and Flash Points which increase with carbon count. Low Vapor Pressures that decrease with carbon length. Solubility Super miscible. WET CHEMISTRY: pH slightly acidic (5-7) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – super miscible Specific gravity – super miscible Alka-seltzer – may fiz (70% isopropyl) Q-tip – flammable Ketone test – does not melt styrofoam GENERAL DESCRIPTION: Very miscible, second most polar functional group to organic acid. The alcohol series has no gases, they are all liquids. As compared to other compound, alcohols have relatively high B.P. & moderate Fl.P. due to their polarity. Very very flammable 1% -36% Alcohols react with the same compounds that water reacts with. Formula contains: “C” & “H” along with “OH”. COMMON USES: Nature produces a tremendous amount of methyl alcohol, simply by the fermentation of wood, grass, etc. Ethanol, also known as grain alcohol, is consumable alcohol. EXAMPLES: OBSERVATIONS FOR FLAME: Ghost to blue flame, generally colored, invisible in direct light, indicates an alcohol. Some orange at the top, ethanol or isopropyl alcohol. ELECTRONICS: 4gas – strong LEL response PID – most with I.P. below 10.6eV HazMatID: Broad, bell-shaped peak nearby 3400. Strong peak near 1000 Liquids: Methanol, ethanol, propanol, butanol 16 8/25/2011 KETONES EXHIBIT: Relatively low Boiling Points and Flash Points which increase with carbon count. Relatively high Vapor Pressures that decrease with carbon length. Solubility miscible to >10% solubility. WET CHEMISTRY: pH slightly acidic (5-7) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – convincible mixer Specific gravity – super miscible Alka-seltzer – should not fiz Q-tip – flammable Ketone test – will melt styrofoam GENERAL DESCRIPTION: Miscible in water and require polarsolvent foam to extinguish fires. Short chain ketones are soluble in water. Less polar than organic acids & alcohols. Generally have higher flash points than ethers. Generally flammable 2% to 12% Formula contains: “C” & “H” along with “CO”. COMMON USES: Most widely used solvent. Found in the home as a solvent for many adhesives. Nail polish remover, PVC primer. EXAMPLES: OBSERVATIONS FOR FLAME: Yellow flame, blue base, clean smoke, or only some black on the smoke. Ketones have more blue in the base. ELECTRONICS: 4gas – strong LEL response PID – most with I.P. below 10.6eV HazMatID: Strong, sharp peak from 1720 – 1705. Liquids: Acetone, methyl ethyl ketone 17 8/25/2011 ALDEHYDES EXHIBIT: Relatively low Boiling Points and Flash Points which increase with carbon count. Relatively high Vapor Pressures that decrease with carbon length. Solubility miscible to >10% solubility. WET CHEMISTRY: pH slightly acidic (3-5) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – convincible mixer Specific gravity – miscible to floater Alka-seltzer – should not fiz Q-tip – flammable Ketone test – will not melt styrofoam GENERAL DESCRIPTION: All aldehydes are irritants. From a medical standpoint, aldehydes account for a majority of the irritants and sensitivities such as chemical bronchitis, pneumonitis, pulmonary edema, etc. Aldehydes are very chemically reactive. Very small carbon number autopolymerize. Generally very flammable 3% -55% Formula contains: “C” & “H” along with “CHO”. OBSERVATIONS FOR FLAME: ELECTRONICS: COMMON USES: Acrolein is the major irritant in smoke given off by burning of wood and wood products, along with other Class A combustibles. EXAMPLES: Liquids: Acrolein, acetaldehyde, crotonaldehyde, formaldehyde Nothing specific 4gas – strong LEL response PID – most I.P. below 10.6eV HazMatID: Strong, sharp peak from 1740-1720 Weak, sharp peak near 2750 18 8/25/2011 ESTERS EXHIBIT: WET CHEMISTRY: Moderate Boiling Points and Flash Points which increase with carbon count. Moderate Vapor Pressures that decrease with carbon length. Solubility generally >10% solubility. pH slightly acidic (3-6) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – convincible mixer Specific gravity – miscible to floater Alka-seltzer – should not fiz Q-tip – flammable Ketone test – will not melt styrofoam GENERAL DESCRIPTION: All the fragrances and tastes of nature are due to the esters. Esters have distinctive odors. Some are very disagreeable, while others are familiar and quite pleasant (banana, fruity, etc.). Many Esters are toxic at relatively low levels. Generally flammable 1%-16% End in “ate” or “oate”. Formula contains: “C” & “H” along with “COO”. OBSERVATIONS FOR FLAME: Nothing specific ELECTRONICS: COMMON USES: Some esters are commonly used as artificial flavoring. Neurotoxin chemical warfare agents are esters, in particular those that are sulfur or phosphorous based. EXAMPLES: Liquids: Methyl acetate, methyl formate, ethyl acetate 4gas – strong LEL response PID – most I.P. below 10.6eV HazMatID: Strong, sharp peak from17501725 Strong peak near 1150 19 8/25/2011 AMINES EXHIBIT: High Boiling Points and Flash Points which increase with carbon count. Low Vapor Pressures that decrease with carbon length. Solubility generally >10% solubility to miscible. WET CHEMISTRY: pH slightly basic (10-12) Spylfiter test #4 – positive for hydrocarbon M8/M9 – absorbs into paper/tape KI paper – no change Solubility – convincible mixer Specific gravity – miscible to floater Alka-seltzer – may fiz (basic) Q-tip – flammable Ketone test – will not melt styrofoam GENERAL DESCRIPTION: Commonly referred to as ammonia derivatives, they are derivatives of the base ammonia. Corrosive, are the organic BASES. Any increase in pH in an organic compound indicates the presence of nitrogen. Have unpleasant odor similar to bowel or rotten flesh or fish. Rapid absorption can occur through all routes that can become systemic. Generally flammable 2% - 20%. Formula contains: “C” & “H” along with either “NH2” or “NH” or “N”. COMMON USES: Corrosion inhibitors. Stabilizer in cellulose nitrate explosives. For solubilizing herbicides. Nitrogen Mustard Agents fall into the general category of amines. EXAMPLES: Liquids: Diethylamine, triethylamine OBSERVATIONS FOR FLAME: Pink or purple stripe in the flame ELECTRONICS: 4gas – good LEL response PID – most I.P. below 10.6eV HazMatID: Broad, pointed peak(s) nearby 3400 Variable peak near 1200 20 8/25/2011 # of Carbon Hydrocarbon Name Formula Derivative name 1 2 3 4 5 6 7 8 9 10 Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Decane CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 Methyl, Form Ethyl, Acet, Vinyl Propyl, Allyl, Acryl Butyl Pentyl, Amyl Hexyl, Ben, Phen Heptyl Octyl Nonyl Decyl Typical Flammable Ranges Of Flammable Liquid Families Alkane Fuel Family Aromatic Hydrocarbons Ketones Esters Amines Alcohols Ethers Aldehydes 1 to 8% 1 to 7% 2 to 12% 1 to 9% 2 to 14% 1 to 36% 2 to 48% 3 to 55% Specific Gravity/Solubility Test Sinkers ▪ LEL at chemical ▪ Solubility well below 10% ▪ Generally higher B.P. & Fl.P. ▪ Generally lower V.P. Organic liquids: ▪ Halogenated hydrocarbons (Fl, Cl, Br, Io) ▪ Nitro compound (NO2) ▪ Organic Peroxides (R-OO-R) ▪ Amine (aniline) ▪ Dimethyl esters (dimethylphthalate) ▪ Carbon disulfide Organic Solids: ▪ Halogenated ▪ Naphthalene Emulsifies ▪ Solubility well below 10% ▪ Generally lower B.P. & Fl.P. ▪ Generally higher V.P. Liquids: ▪ Likely LEL present ▪ Hydrocarbons: ▪ Alkanes ▪ Alkenes ▪ Aromatics: ▪ Benzene, Toluene, Xylene, etc. ▪ Polar organics with generally more than 4 carbons: ▪ Ester, Aldehydes, Amines ▪ Long chain alcohols & organic acids. ▪ Mineral oils. Solids: ▪ Plastics, flour, cellulose, wood, pumice, lava rock, etc. Organics: ▪ Likely LEL present ▪ Solubility miscible ▪ Generally higher B.P. & Fl.P. ▪ Generally lower V.P. ▪ Require AR-AFFF or ATC. ▪ Polar organics with generally less than 4 carbons: ▪ Alcohol (pH 5-7) (3400 hump & peak 1000) ▪ Organic acid (pH 2-3) (peak 1720-1680) ▪ Acetone (pH 5-7) (peak 1720-1705) Inorganics: ▪ Most all mix in water ▪ Inorganic acids (pH 0-1) sulfuric, hydrochloric, nitric ▪ Ammonia, solids, powders (pH blue) hydroxides ▪ Likely LEL present ▪ Solubility over 10% ▪ Require AR-AFFF or ATC. ▪ Polar organics with generally less than 4 carbons: ▪ Ketones (pH 5-7) (peak 1720-1705) Example: MEK ▪ Ester (pH 5-7) (peak 1750-1725) ▪ Aldehyde (pH 4-5) (peak 1740-1720) ▪ Amines (pH 11-12) ▪ Natural oils ▪ Uniform, milky white solutions that do not settle except perhaps after a long time. ▪ Solubility well below 10%, requiring suspension agent. ▪ Generally higher B.P. & Fl.P. ▪ Generally lower V.P. Organics ▪ Pesticide/Insecticides: ▪ Organophosphate ▪ Organochlorine ▪ Thiophosphate ▪ Some herbicides ▪ Water-soluble cutting oils Opalescence Convincible Mixers Mixers Floaters Unknown liquid separates from water a strong indicator that the liquid is organic. ▪ An appearance of a dense milky iridescent medium, or like a prism. ▪ Solubility over 10% ▪ What would normally be an oily liquid that can dissolve in water ▪ Example: brake fluid Chillers ▪ Subtle and easily missed ▪ Inorganics: nitrates, ammonium salt, thiosulfates ▪ Example: cold pack Q-Tip Test Q-tip does not burn & turns black Q-tip has to be stuck in the flame and ignites once heated Flame jumps or leaps into Q-tip Product is nonflammable Product is combustible Product is flammable Combustibility Test Ignites before lighter reaches the edge of the watch glass Ignites either when the lighter is at the edge of the dish or when the lighter touches the liquid Large flame that cannot be sustained without the lighter Small flame that cannot be sustained without the lighter Flashes and burns but self-extinguishes, leaving a substantial amount of liquid Flashes, but then goes out immediately; no way to sustain flame Extremely flammable Fl.P. below 73°F Inhalation hazard Flammable Fl.P. of 100°F or lower Fl.P. near 100°F Fl.P. above 141°F and below 200°F Indicates a mixture, probably alcohol or acetone and less than 40% water. Water remains after more volatile solvent burns off. Indicates a mixture of a soluble, or miscible, organic compound and water. At about 40% water or less the flame can be sustained. Smoke Color Test Clear smoke Indicates simple, single-bonded organic with low carbon number Some black Indicates a longer carbon skeleton, or smoke; no a mixture of materials spider-webs Many black spider-webs, Benzene, Toluene, considerable black soot Ethyl benzene, Xylene remains on the watch glass Watch Glass Flame Test Orange flame; no blue base; dirty smoke; spiderwebs Luminous, tall orange flame; invisible or blue base Blue flame (invisible in bright light) Green flame Turquoise, selfextinguishing flame (test tube char ignition) Gray or pink/purple flame may be almost white Pink stripe near the top of the flame Orange flame with faint blue white edges Benzene, Toluene, Ethyl Benzene, Xylene May be saturated hydrocarbons, ketones, or ethers Alcohol, if unknown sank in water, may be carbon disulfide Ketones and other polar solvents may give a green tinge to a ketone-type flame Chlorinated, alkyl halide Nitro or alcohol containing a nitro group. Likely engine fuel May indicate amines or other nitrogenated compounds including nitriles Indicates phosphides. Noxious odor may be noted. Pesticide likely Other Combustibility Reactions Liquid creeps away, leaving a clear area around the burning lighter; solid material remains after the flame goes out The flame burns at the edge of the puddle initially, then moves across the entire puddle, or goes out Indicates a solid dissolved in a liquid This usually indicates a mixture of flammable and nonflammable Melting Point Test Below 1000°F ▪ Typically indicates an organic ▪ Combustible; generally pH 7 or lower Above 1000°F ▪ Typically indicates an inorganic ▪ Non-flammable; generally pH blue pH 5-7 pH 11-12 Possible oxidizer: ▪ Spylfiter test #4, M8, M9 beads up. ▪ Potassium Iodide strip black, purple, blue ▪ Q-tip test nonflammable ▪ Alka-seltzer fizzer Possible organo-pesticide: ▪ Spylfiter test #4, M8, M9 absorbs in. ▪ Emulsifier Possible aldehyde: ▪ Spylfiter test #4, M8, M9 absorbs in. ▪ Miscible to highly soluble Possible amine: (the organic bases) ▪ Spylfiter test #4, M8, M9 absorbs in. ▪ Q-tip test flammable to combustible ▪ Alka-seltzer non-fizzer ▪ Short chain mixer; long chain floater ↑ pH 1-3 Possible organic acid: (non-fumer) ▪ Formic, acetic, propionic, butyric acid ▪ Spylfiter test #4, M8, M9 absorbs in. ▪ Q-tip test mostly combustible, few flammable ▪ Miscible to highly soluble Possible water: ▪ Spylfiter test #4, M8, M9 beads up. ▪ Q-tip test nonflammable ▪ Alka-seltzer fizzer Possible organic peroxide: ▪ Spylfiter test #4, M8, M9 absorbs in ▪ Potassium Iodide strip black, purple, blue ▪ Q-tip test combustible to energetic flammable ▪ Alka-seltzer non-fizzer ▪ Sinker Possible hydrocarbon: ▪ Alkane, alkene, aromatic, alcohol, ketone, ether, ester, halogenated, organic peroxide, etc. ▪ Commonly “halo” pH paper. ▪ Spylfiter test #4, M8, M9 absorbs in. ▪ Q-tip test flammable to combustible ▪ Alka-seltzer non-fizzer ▪ Floater, mixer, or sinker pH 12 & pH 0-1 Likely inorganic or mineral acid: (fumers) ▪ Hydrochloric/muriatic acid (foil test) ▪ Nitric acid (penny test) ▪ Sulfuric acid (sugar test) ▪ Phosphoric, boric, hydrofluoric, hydrobromic ▪ Spylfiter test #4, M8, M9 beads up, may destroy test papers. ▪ Q-tip test non-flammable ▪ Miscible to highly soluble; likely to produce heat when placed into water pH 4-6 pH Test Likely inorganic base: (some liquids, mostly solids) ▪ Possibly ammonia ▪ May contain “hydroxide” in chemical name ▪ Q-Tip test non-flammable ▪ Miscible to highly soluble M8 Paper Test Potassium Iodide Paper (KI) Test Beads up: ▪ Typically non-flammable, inorganic Absorbs in: ▪ Red color change, generally indicates hydrocarbon ▪ Orange color change, common for some corrosives to do. ▪ It is recommended to put 1 to 2 drops of HCL (muriatic acid) on the KI paper before applying product to increase sensitivity. ▪ No color change, no oxidizer present M9 Tape Test Beads up: ▪ Typically non-flammable, inorganic Absorbs in: ▪ Typically flammable/combustible, organic Black then to white Black to purple Blue to dark purple ▪ If strip turns black immediately, then quickly returns to white, this is a very strong oxidizer. Possibilities: ▪ Hypochlorites, hypobromites, concentrated nitric. ▪ If strip turns black or dark purple immediately this indicates a strong oxidizer. ▪ If strip turns blue or dark purple in a few seconds, continue testing but be aware you may be dealing with a very hazardous chemical. ▪ If strip turns blue or purple after time, weak oxidizer. Test #2 Oxidizer Risk: Test #3 Fluoride Test: Test #4 Petroleum Product: Test #5 Iodine/ Bromine/ Chlorine: ▪ Pink = Not Present ▪ Yellow = Present ▪ Possible hydrofluoric acid present ▪ Light Blue = Not Present ▪ If product beads up on the strip it is typically not flammable. ▪ Dark Blue = Present ▪ If product absorbs in, it indicates carbon is present. ▪ Peach = Not Present ▪ Violent = Present Hydrochloric Acid Test Sulfuric Acid Test Test #1 Acid/Base Risk: ▪ Red = Strong Acid ▪ Typically non-flammable ▪ Inorganic or mineral acid ▪ Orange = Moderately Acidic ▪ Possible flammable/combustible ▪ Yellow = Weak Acid ▪ Possible flammable/combustible ▪ Green = Neutral ▪ Dark Green = Moderately Basic ▪ Dark Blue = Strong Basic ▪ Typically non-flammable ▪ Likely inorganic (ammonia, hydroxide) ▪ Light or Dark Blue = Present Note: KI paper is a much more sensitive test ▪ White = Not Present Inorganic Acid Test Nitric Acid Test Spylfiter Test Strip Add 6 to 7 drops of unknown to aluminum foil. Give it a couple of minutes. If it fizzes it moderate to high concentration of HCL or muriatic acid. Add 2 to 3 drops of unknown to a pre1982 copper penny. If it turns green, nitric acid is present. Add 5 to 6 drops of unknown to granulated sugar. A high concentration of sulfuric will turn sugar black. A moderate concentration of sulfuric will turn sugar yellowish to dark brown. A lower concentration of sulfuric may only wet the sugar cube. Alka-Seltzer Test NonFizzer ▪ Likely a hydrocarbon/flammable Fizzer ▪ Likely: ▪ Water or water based (example: 70% isopropyl alcohol) ▪ Acidic or basic solution Ketone Test Styrofoam doesn’t melt Styrofoam melts Probably: ▪ Not a ketone or halogenated hydrocarbon Likely: ▪ Ketone ▪ Halogenated hydrocarbon RAPID RISK ASSESSMENT SOLIDS Suffix -ide -oxide -peroxide -ate or –ite -hydroxide -hydrate -cyandide Element Naming Metal + NonMetal Metal + Oxygen Metal + O2 Metal + Oxy ion Metal + hydroxide (OH) Salt • H20 Metal + CN Common Name Basic Hazards Some are H2O Rx (‡ see gas) Mild corrosive with H2O H2O Rx Oxidation Oxidizer H2O Rx Alkali Affinity for H2O Toxic and Rx with acids H2O Rx Family Name Binary Salt Metal Oxides Inorganic Peroxides Oxy Salts Metal Hydroxide Hydrate Cyanide Salt First two columns LIQUIDS Suffix -ic -ic or –ous -ane -ene -yne, acetylene -ide, -ane, -ene -amine -ether -O Peroxides -cyanide, nitrile -ol, Alcohol -thiol -al, aldehyde -one, ketone -ate, ester -ic acid Naming H + halogen or H + ion H + halogen or H + ion Carbon chain >5 C. single bond Carbon chain > 4 C. double bond, Rx Carbon chain > 4 C. triple bond Very Rx Benz, Phenyl Halogen + carbon chain > 4 C. N+ Carbon chain > 3 C. Carbon chain Carbon chain Carbon chain Carbon chain Carbon chain Carbon chain > 3 C. Carbon chain Carbon chain Carbon chain Basic Hazards Toxic/Corrosive Acids Flammable Flammable Family Name Halogens Mineral Acids Alkanes Alkenes Flammable Alkynes Flammable/Toxic Asphyxiant/Toxic Flammable/Toxic/Corrosive Flammable/Toxic Flammable/Polymerize Flammable/Toxic/Polymerize Aromatics Alkyl Halides Amines Ether Peroxides O. Cyanides Flammable/Toxic Flammable/Toxic Flammable/Toxic/Polymerize Flammable/Toxic Flammable/Toxic/Polymerize Corrosive/Flammable/Toxic Alcohols (Polar) Mercaptins (Polar) Aldehydes (Polar) Ketones (Polar) Esters (Polar) Organic Acids (Polar) GASES Suffix -ide -ane -ene -yne -ide, -ane, -ene -amine -al, -alde-, hydes Naming F, Cl C chain C chain C chain C chain N + C chain C chain Gas (§=Cryogenic, ‡ = Pressure) ‡Acetylene ‡Ammonia §Argon Carbon Monoxide Chlorine Fluorine §Helium §‡Hydrogen ‡Hydrogen Sulfide Krypton Liquefied Natural Gas Methane §Neon §Nitrogen §Oxygen Phosgene ‡Phosphine Propane §Xenon Basic Hazards Toxic/Corrosive Flammable Flammable Flammable Flammable Corrosive/Flammable Flammable/Toxic/Polymerize Hazard Flammable Corrosive/Toxic Asphyxiant Corrosive/Toxic/Flammable Corrosive/Toxic/Oxidizer Corrosive/Oxidizer Asphyxiant Flammable Flammable/Toxic Asphyxiant Flammable Flammable Asphyxiant Asphyxiant Oxidizer Toxic Flammable/Toxic Flammable Asphyxiant Family Name Halogens Alkanes Alkenes Alkynes Alkyl Halides Amines Aldehydes Expansion Ration 865 to 1 855 to 1 842 to 1 680 to 1 458 to 1 981 to 1 745 to 1 850 to 1 700 to 1 693 to 1 635 to 1 693 to 1 1445 to 1 696 to 1 860 to 1 400 to 1 700 to 1 270 to 1 559 to 1 Basic Chemical Recognition and Identification SOLID LIQUID GAS Tend not to burn, some Tends to burn or emit vapors, some Tend to burn or displace act as oxidizers. act as oxidizers. oxygen. Some may sublime (move Potential acid or base. Some are soluble in water. from a solid to a vapor). May not mix in water. All are toxic or asphyxiating. Potential acid or base Can be toxic. Some act as oxidizers. when in contact with Representative Containers Representative Containers water. Corrosive Liquid Cargo Tank Pressure Cargo Tank MC331 Soluble in water or water MC312/DOT412 Cryogenic Liquid Tank MC338 reactive. Nonpressure Cargo Tank High Pressure Tube Trailer Can be toxic if ingested MC306/DOT406 One Ton Containers or when contacting Low Pressure Cargo Tank Pressure Tank Containers DOT unprotected skin. MC307/DOT407 Spec51/Spec 51L Representative Containers Nonpressure Tank Containers Cryogenic IMO Type 7 Dry bulk commodity IM101/IM102 Tube Modules-trailers carriers. Portable bins (totes) Pressure Tank Car Super sacks or bulk bags. Nonpressure (general service) Tank Cryogenic Liquid Tank Car Covered hopper cars. Cars. Cylinders Drums and boxes. Corrosive Liquid Tank Car Bottles, Multicell packages, carboys. pH - 1- 3 Red pH - 4-9 pH - 4-9 pH - 4-9 pH - 4-9 pH - 10-14 Blue Possibilities Conditions O2 - 20.9 ↓ O2 - 20.9 ↑ O2 - 20.9 O2 - 20.9 ↓ O2 - 20.9 ↓ O2 - 20.9 ↑↓ LEL - 0.0 Acid gases Fluorine Chlorine Bromine Iodine LEL - 0.0 Oxygen Oxygen Production LEL % Alkanes Alkenes Alkynes Cyclos Aromatics Ether Alkyl Halides LEL % Methane Ethane Propane Butane Ethene Ethylene Hydrogen LEL 0.0 Nitrogen Noble Gases Helium Neon Argon Krypton Xeon Radon LEL % Low Ammonia NH4, Derivatives Amines Amides Azides Inorganic Acids Organic Acids Fluorine – move to RED Chlorine – move to RED Ammonia – move to BLUE Alcohols Aldehydes Ketones Esters Solid Product Cyanide Sulfides Hydroxides Liquid Product Hydroxides Ammonia NH4, Derivatives The state of matter identifies the container in which they are held. Many materials once out of their containers revert back to its natural state of matter. SOLIDS LIQUIDS GASES Solids can be placed in liquids, once heated they revert back to the solid form. Solids may be in particulate form and may act similar to vapors. Liquids moving out of containment systems may produce static electricity, have high vapor pressures and move to low areas. Gases out of their container will expand and occupy a larger area. During release static electricity may be produced. Chemical and Physical Properties to consider based upon state of matter. Appearance (Color) Melting Point Density Solubility Sublimation (Solid to Vapor) Freezing Point pH (Acids and Bases) Appearance (Color) Density Specific Gravity (Liquids) Vapor Density (Vapors) Solubility Flash Point (vapors, no gases) Melting Point pH (Acids and Bases) Ignition Point Flammable Ranges – LEL/UEL Tend not to burn. Some may sublime (Moves from a solid to a gas.) Potential Acid or Base when in contact with water. Soluble in water. Can be toxic if ingested or skin contact. Tend to burn or flammable vapors. Potential Acid or Base. May not mix in water. Can be toxic. Appearance (Color) Density Vapor Density Solubility (Greater or Less Than 10%) Flash Point Boiling Point pH (Acids) Ignition Point Flammable Ranges – LEL/UEL Expansion Ratios Tend to burn or displace oxygen. Some are soluble in water. All are toxic or asphyxiating. Representative Containers Representative Containers Pressure Cargo Tank MC331 Corrosive Liquid Cargo Tank MC312/DOT412 Cryogenic Liquid Tank MC338 Nonpressure Cargo Tank High Pressure Tube Trailer MC306/DOT406 One Ton Containers Low Pressure Cargo Tank Pressure Tank Containers Representative Containers MC307/DOT407 DOT Spec 51/Spec 51L Dry Bulk Commodity Nonpressure Tank Containers Cryogenic IMO Type 7 Carriers IM101/IM102 Tube Modules – Trailers Super Sacks or Bulk Bags Portable bins (Totes) Pressure Tank Car Covered Hopper Cars Nonpressure Tank Car Cryogenic Liquid Tank Car Drums and Boxes Corrosive Liquid Tank Car Cylinders Bottles, Multicell packages, carboys. Melting point→→→→→→→→ Vaporization→→→→→→→→→→→ Solid ←←←←←←←←Freezing Point Liquid ←←←←←←←←←←←Condensation Gas Step 1: Look at your observations. 7 Hazmat Clues Occupancy And Location Container Shapes Markings And Colors Placards And Labels Shipping Papers And Facility Documents Monitoring And Detection Equipment Senses Chemical Observations (Smoke, Fumes, Solid, Liquid and Gas.) Step 2: Gather initial critical readings. Check for radiation. Check for acids/bases/oxidizers/peroxides. Check for flammables. Utilize multiple technologies that are available. (Electronics/Colormetrics). Step 3: Develop a hypothesis: Does the data from Steps 1 and 2 point to a chemical characterization or family? What are the polar qualities? What other methods can be used to test the hypothesis? (Wet chemistry/IR-Raman/Colormetrics Step 4: Execute Response Plan: Take steps to mitigate hazards. Perform continuous air monitoring based upon what you have discovered. UNKNOWN SOLIDS Radiation 2x Background Turns White Perchlorate Test SOLIDS pH Test Base Hydroxides Cyanides Sulfides Azides Chlorinated Product Cl2 Oxy Salts Caution Crystalized solids on or around container openings should be considered as an explosive. Acid Cyanide Test Sulfide Test Cyanide Salts Oxidizer Test Sulfide Salts Peroxide Test Peroxides Hydroperoxides Organic Peroxides Perchlorates = Violet Chromates = Red/ Brown Cyanides = Green Covalent Bonds Nitrate/ Nitrate Test Biological Peaks InfaRed Nitrates Nitrites Nitrogen Based Explosives 3300, 1650, 1550 Inorganic Salts = Oxi Salts Cyanides Solid Organics Positive Protein Assessment of Peptide Bonds DNA Markers Or Create 10-6 dilutions to control hook effect. Handheld Assays Antigen/Antibody Reaction Bioluminescence DNA Comparisons PCR Transport To LRN UNKNOWN LIQUIDS Heavy Molecules – High boiling point, low vapor pressure greater than 64 ◦F (18◦C). Light Molecules – Low boiling point, high vapor pressure less than 64 ◦F (18◦C). Polar Molecules – Changes state of matter to liquids vapor pressure changes. CH4 Gas Fuels Liquefied Petroleum Gas Liquefied Natural Gas C4H10 C5H12 Liquid Fuels Gasoline C13H28 Hydrocarbon Derivatives C14H30 Liquid Fuels Fuel Oils C17H35 Diesel Fuel Jet Fuel C18H38 Heating Oils Heavy Fuel C20H42 Oils C22H46 Heavy Oils Lubrication Oils LIQUIDS Turns White Observations: Fuming in high humidity. Formic Acid Colormetric Test. IR Peaks (See region chart.) Chlorinated Product Cl2 Oxi Salts in Water. Mineral Acids Formic Acid = Red Hydroflouric Acid Hydrochloric Acid Hydrobromic Acid Hydrosulfuric Acid Hydrossulfurous Acid Hydrophosphoric Acid Hydronitric Acid Hydronitrous Acid Radiation pH Test Organic Acids Formic Acid = Yellow Formic Acid Acetic Acid Propionic Acid Butyric Acid Baleric Acid Caproic Acid Caprylic Acid Capric Acid 2x Background Acid Base Ammonia Ammonia derivatives Amines Azides Hydroxides Smoke colors due to fire or reaction: White/Clear – Single bonds, alcohols, halogens. Black – Single bonds, ling carbon chains. Heavy Black – Double, triple bonds, aromatic groups. Red/Orange – Nitrogen based products, Nitric Acid, Bromine. Purple – Iodinated compound. Sharp White – Phosphoric compounds. Basic Wet Chemistry Observations: Polarity Test (Solubility) Floats – Small CH chain – LEL Present Sinks – Large CH chain – LEL at chemical Mixes – LEL present – low weighted alcohols, aldehydes, ketones, esters, amines. Polar Observations: Weak LEL Reaction Weak PID Reaction Weak Fid Reaction Miscible when polar. IR peaks (See regional chart) Colormetrics for family ID. Solubility Observations: Strong LEL Reaction Strong PID Reaction Strong FID Reaction IR peaks (see region chart) Colormetrics for family ID. Polar Fuels: Alcohols Aldehydes Esters Ketones Basic Wet Chemistry Observations: Flame Test Combustible – Sample burns next to or in test flame. Flammable – Sample burns away from test flame. Flammable PID Flame Test Fuels with varying Vapor Pressure O2 = 20.9 Combustible Gas Inidicator Oberservations: LEL = % High Numbers VP high, Flammable Low Numbers VP low, Combustible O2 =20.9 =/- 0.2 (sensor drift) Fuels with varying Vapor Pressures. Observations: Strong LEL Reaction Strong PID Reaction Polar and Non-Polar fuels with significant Strong FID Reaction Vapor Pressure. Carbons greater than 5. IR peaks (See region chart) Colormetrics for family ID. InfraRed Non-Polar Fuels >5 Carbon – chained HC Halogenated Hydrocarbons Aromatics Ethers Epoxides Paint thinners. Combustible Multi-Gas Monitor FID Fuels with varying Vapor Pressure below 10.6 eV. Non-Polar Analogous Familes Functional Groups (see IR Card) Mixtures that are Combustible: Motor Oils Diesel Fuels Mineral Oils Vegetable Oils Kerosenses Transmission Fluids Sythetic Oils Paint Thinners Observations: Very weak LEL Reaction. Very weak PID Reaction. Very weak FID Reaction. IR peaks (See region chart) Colormetrics for family ID. UNKNOWN GASES Chlorinated products. GASES Turns White Radiation 2X Background Halogenated Acids Fumes from liquid acids. Ammonia Amines Acids pH Test Bases Multi-Gas Monitor Fuels with strong Vapor Pressure O2 = varies Flammables that displace Oxygen. Low weighted (<5 Carbons) chained hydrocarbons. Methane Hydrogen Ethane Ethene Propane Propene Butane Acetylene Observations: Strong LEL Reaction Strong Oxygen displacement IR peaks (See regions) Colormetrics for ID Multi-Gas Monitor Observations: LEL = % O2 = 20.0 =/- .2 PID = Will miss the first 4 HC of alkanes, ethyne, first cyclos, and first alkyl halides. Non Flammable that displaces Oxygen. Noble gases Nitrogen Low weighted Halogenated Hydrocarbons Carbon Monoxide Carbon Dioxide Observations: Strong LEL Reaction Strong Oxygen Displacement IR peaks (See regions) Colormetrics for ID. Multi-Gas Monitor Observations: LEL = 0% O2 = Below 20.9 =/- .2 PID – 0 or # Infrared Analogous Families Functional groups (see IR Card) PID Fuels with strong Vapor Pressure below 10.6 eV. FID Fuels with varying Vapor Pressure. LABWARE Laboratory ware or labware (including glassware and plasticware) is used for three main purposes: 1. 2. 3. Storage Measurement Confinement of fluid transfer, chemical reactions, and the like. Note: Except for bottles, storage items are also used for confining reactions. Other purposes include connections for storage or containment and stirring or spreading. Storage Beaker An unrestricted or simple restricted vessel with high a height-toorifice diameter ratio. Usually has no handle. The most common form is a Griffin low form beaker. Bottle and Jar A rigid or semi-rigid container that is typically made of glass or plastic. Usually no handle. Bottle: Neck or mouth is comparatively narrow. Jar: Neck or mouth almost as wide as the rest. Erlenmeyer Flask A flat-bottomed, conical laboratory flask. Usually with a short cylindrical neck. Fernbach Flask An Erlenmeyer flask with a very broad base and a short cylindrical neck. Typically holds 2.4 liters (L). Used to culture microbes on shaker-incubators. Florentine Flask A flat-bottomed laboratory flask with a round bottom and cylindrical neck. Uncommon in biology. Stopper A plug or cap used to plug openings in labware. Test Tube A plain or lipped tube that is usually made of thin glass and closed at one end. The closed end can be round or flat. May have a threaded lip for a screw cap. Used in chemistry and biology. Centrifuge Tube A test tube made of either glass or plastic, with a conical bottom. Often has a threaded lip for a screw cap. Used both for centrifugation and simply as a test tube. Measurement Burette A graduated glass tube with a small aperture and stopcock. Used to deliver measured quantities of liquid. Also used to measure a liquid or gas received or discharged. More common in chemistry than in biology. Graduated Cylinder A tall narrow container with a volume scale. Used to measure and transfer liquids. Pipette (Pipet) A tube, usually open at both ends. A transfer pipet often includes a bulb at the top. Used to transfer and measure liquids from one container to another. Pipet Filler A device for non-transfer pipets to avoid mouth pipetting. Volumetric Flask Used to prepare a solution of fixed volume with great accuracy. Has only one mark for volume etched or printed on it. Volumetric Pipette A pipet with great accuracy. Has only one mark for volume etched on it. Containment Boiling Flask Used to distill liquids. A Claisen flask is an example. Rarely used in biology. Column A tube or cylinder with a bottom cap to hold resin beads. The bottom cap has a tube for collecting drops of solution, controlled by a stopcock or a tube with a clamp. Used for chromatographic separation. Condenser A device in which a gas or vapor is condensed to liquid. Water is run through the jacket to cool the inner tube. Rarely used in biology. Staining Dish and Jar A dish or jar with a cover and internal ridges on the sides to support microscopic slides. Staining Dish: A small, square or rectangular dish with high sides. Coplin jar: A jar with a square cross-section. Used in biology to stain specimens fixed to slides. Cuvette A small sample container with good optical properties. Used for spectroscopic measurements of samples. Funnel A utensil which usually consists of a hollow cone with a tube extending from the small end. Designed to catch and direct a downward flow. Bϋchner funnels have an internal support for filtration. Petri Dish (Agar Plate) A small, shallow dish with a loose cover made of thin glass or plastic. When filled with agar, used for bacterial and fungal cultures. Reaction Vessel A vessel used to contain a chemical transformation. Separatory Funnel A funnel with a narrow top opening and a bottom opening controlled by a stopcock. Used to separate media, e.g., oil and water mixtures. Watch Glass A shallow curved glass. Includes concave “dishes” that are used as beaker lids. Also used for a variety of other purposes: To hold protists and other invertebrates for viewing under a microscope; To dissolve materials such as crystals and powders; etc. Adapter Used to join parts with different diameters. Joint Used to join two pieces of tubing. Stirring Rod A piece of hollow or solid glass tubing. Spreader A bent stirring rod or a T-shaped rod. Used to spread media on a Petri dish. RESPONSE TO SUSPECTED BIOLOGICAL INCIDENTS 1. Plan for wind speed and direction. a. Set up and enter scene accordingly. 2. Determine credibility of incident. 3. Interrogate affected persons. 4. Examine container for clues of origin. Contain suspected substance in plastic bag. 5. Establish sufficient decon for situation. (Seek out a private area for decon.) 6. Establish sufficient PPE. Level “B” or “C” is adequate for “white powder” calls. 7. Acquire samples with Hepa Vac or other means that will enable a sample to be screened, tested and sent to State Health Department. 8. Screen samples inside or in a private area. Screen for the following: a. Corrosives – pH, Spilfyters b. Radioactive – Ludlum 14c c. Toxic – PID, FID, Spilfyters d. Flammable – Multi-gas, Spilfyters e. Hit on any of the above is “negative” for biological. f. Hazmat ID – Look for protein alert. g. If there is a positive for protein on the Hazmat ID sample needs to be sent to State Health Department. Sample will need to be screened with a biological sample kit. (BTA or Ramp System) h. Responder IR All samples are “double bagged” before they are sent to the State Health Department. 9. Acquire all affected persons contact information. Chain of Custody form will need to be filled out on all samples taken to the State Health Department. BIOLOGICAL WEAPONS SIGNATURES 1. These media indicate bacteriologic or, less likely, mycologic (fungal) work. The type of medium used can tell own which bacteria or fungi to exclude. The difference between broth and agar is that the latter has 12 to 20 g of agar added to the broth. This 1.2 – 2.0% agar, weight to volume (w/v). By the way; “agar” is pronounced “AH-grr”. a. Most transparent media are not rich, a so they do not support growth of many agents. Examples include tryptic soy broth or agar (abbreviated TSB, TSA), nutrient broth or agar, and plate count agar. b. However, if the medium is an infusion broth or agar, more organisms grow on it. Examples include heart infusion broth or agar and brain heart infusion broth or agar (BHIB, BHIA). i. Bacillus anthracis, Yersinia pestis, and a few strains of Francisella tularensis grow well on these. c. Sheep’s blood agar, or simply blood agar (SBA or BA) is prepared by adding 5% sheep’s blood (v/v) to autoclaved TSA after it cools but before it starts to solidify. i. Blood agar plates are often abbreviated BAP. ii. Both B. anthracis and Y. pestis grow well on BA. d. Chocolate agar (Choc) is made by adding the sheep’s blood when the autoclaved TSA is hotter. The heat lyses (breaks open) the red blood cells so that the nutrients are released into the medium. This is very rich agar. i. Bacillus anthracis, Yersinia pestis, and Francisella tularensis all grow well on Chocolate agar. 2. Anaerobes require removal of oxygen, so look for candle jars, anaerobic jars or chambers with gas generators, and nitrogen tanks on fermenters. a. Clostridium botulinum is a strict anaerobe; the vegetative cells do not survive long in the presence of oxygen. It grows well on BA, but also grows well on egg yolk agar, CDC anaerobic blood agar, and Schaedler’s agar. b. Oxyrase agar plates are designed to grow anaerobes without using candle jars or anaerobic chambers. 3. Growth on a Petri dish may look bacterial, but could be yeast; Fungi may grow as yeast (rough or smooth, but not fuzzy or furry) or as mold (fuzzy or furry). 4. The lot numbers on the media can be traced to a supplier, who can give a list of those who paid to purchase media in those lots. If the purchase may be traced to a clinical laboratory, the media may not be stolen. Hospital and clinical laboratories keep records of disposition of out-dated media. They regularly give such media to training programs within hospitals and to nearby educational institutions. 5. A flask with growth separate from fermenters may contain a starter culture for the fermenters. Haziness, cloudiness, or turbidity of the broth almost always indicates growth. “Homemade” Fermenters 6. Corn steep liquor is used in place of D-glucose (dextrose) as a carbon source, but almost exclusively in fermenters. 7. Antifoam is used in microbiology exclusively to suppress foaming in fermenters. Other Microbiology 8. Stains: a. Gram stains are used to check the purity and production of the material in the starter culture, scale-up cultures(s), and fermenter. b. Malachite Green is used in microbiology only to stain spores. 9. The Bacti-Cinerator® (Sherwood Medical Industries Inc., St. Louis, MO) is a device found in clinical microbiology laboratories, which have banned open flame (Bunsen burners) since at least the late 1980’s. Other brands are now available. Many microbiologists may never see one in their careers, so this device suggests strongly that whoever set up this clandestine laboratory has some knowledge of infectious disease microbiology. 10. A glove box (Class III Biological Safety Cabinet) may be large enough to contain a setup for the full process of fermentation, concentration, drying and grinding. A glove box usually is not the best source for a sample; to enter it would add energy to the system and may compromise evidence. However, one could take a sample from the glove box if need be. First, grab the sample with a glove, then pull the glove out of the box without detaching it to invert it. Next, tie off the glove at two near positions, then cut the glove between the ties (“umbilical-cord cut”). Finally bleach and put epoxy on the exposed ends of the cut. The sample will be in the sealed, inverted glove. Note: This method may not be accepted in all jurisdictions. 11. A funnel with a filter sitting on an aspiration (side-arm) flask serves to remove most of the broth from the microbes. a. A side-arm (Bernoulli) addition to a water spigot or an air pump can aspirate air out the side arm. b. Note: If bacteria or fungi are being collected, then one saves the paste in the filter. If toxins are collected, then one saves the liquid filtrate. Drying, Milling, and Dissemination 12. If heat is used to dry product, focus on Bacillus anthracis spores and a very few toxins. a. A toaster oven can serve to dry paste collected in filter paper. b. Note: Remember that different preparations, using different media, can give different colors to a product. 13. To grind the dried product, one can use a coffee-bean mill initially, then a mortar and pestle. 14. One can use a rock tumbler in which a ceramic bead mill could be placed for the final milling step for spores, some toxins, and some viruses. a. If the laboratory appears to be for bacterial production, the mill strongly indicates production of bacterial spores, i.e., those of Bacillus anthracis. The tumbler and mill are available at hobby stores. This final step is when one can add silica powder (Cab-O-Sil®, Aerosil®, or another brand) as “fluidizer”. b. Ceramic bead mills and similar devices usually should not be opened, to avoid spreading material. Also, they are excellent evidentiary samples intact. However, enough powder should have leaked along the seal for detection of agent with a HHA. The powder is end product, or is very close to it. 15. Reversing electrical polarity on a medical aspirator makes it a dissemination device. It should not be opened to minimize energy. Also, it is an excellent evidentiary sample intact. However, it should have sufficient amount of powder on the outside and in the clamped-off tubing for a sample and for detection of agent with a HHA. Proteins, Including Many Toxins 16. The presence of large amounts of salts such as ammonium sulfate, sodium sulfate, calcium chloride, or polyethylene glycol (PEG) of various chain lengths, relative to other compounds present in a biology laboratory typically indicate that the worker is purifying proteins by salting in or salting out. Some proteins fall out of the solution (in the precipitate), while some stay in the liquid (the supernatant). a. Ammonium sulfate is perhaps the most popular salt to try first. b. Laboratory workers usually use ammonium sulfate or sodium sulfate to purify ricin, but can use other salts. c. Laboratory workers use calcium chloride to purify botulinum toxin. Viruses and Certain Bacteria 17. T-flasks are used for animal cell culture. Animal cell culture is necessary to support the growth of viruses and such bacterial pathogens as Rickettsia species, Orientia tsutsugamushi, and Coxiella burnetii. Because of the thickness of the flask, one cannot use a typical light microscope to focus on the cells growing on the inside bottom of the flask. To look at the monolayer of cells, one uses an inverted microscope. The light source is on top, pointed down; the objective lenses are underneath. MEDIA AND ORGANISMS IF THIS MEDIUM IS PRESENT IT LOOKS LIKE Tryptic soy or agar (TSB, TSA) COLOR Light to straw. CLARITY Transparent Nutrient broth or agar. Plate count agar. Light amber to straw. Light amber to straw. Transparent Transparent Heart infusion broth or agar. Light to medium amber. Transparent Brain heart infusion or agar (BHIB, BHIA) Most other infusion broths or agars. Light to medium amber, yellow, or tan. Transparent to slightly hazy. CONSIDER THESE ORGANISMS Bacillus anthracis Bacillus cereus and other Bacillus spp. Bacillus anthracis Other Bacillus spp. Yersinia pestis and other Yersinia spp. (Sheep’s) blood agar (BA, BHIA) Note: May be; -tryptic soy agar, - heart infusion agar, - Or other base. Chocolate agar (Choc) Bright red. Opaque Bacillus spp. Yersinia spp. Clostridium spp. Chocolate brown. Opaque Almost anything. Cysteine rabbit heart agar w/antibiotics. Bright red. Opaque Francisella tularensis. CIN agar base (Yersinia selective agar base). Reddish-orange. Translucent to opaque. Yersinia spp. CDC anaerobic blood agar (Ana BA) Egg yolk agar (EYA). Schaedler’s agar with blood. Medium red. Whitish-yellow. Dark Red. Opaque Translucent Opaque Clostridium botulium Clostridium perfringens and other. Clostridium spp.