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Western Arctic Shelf-Basin Interactions (SBI) Project
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Handling Hazardous Waste
Shipboard I. Introduction Vessels are required by Annex (I-V) of the International Convention for the Prevention of Pollution from Ships (MARine POLution 73/78) and United States laws and regulations to comply with vessel-generated waste discharge requirements. MARPOL 73/78 is a Convention of the International Maritime Organization (IMO), a specialized agency of the United Nations. It consists of five annexes designed to reduce marine pollution by controlling or prohibiting discharges of harmful substances from vessels into the sea. A harmful substance, as defined by the Convention, "means any substance which, if introduced into the sea, is liable to create hazards to human health, to harm living resources and marine life, to damage amenities or to interfere with other legitimate uses of the sea, and includes any substances subject to control by the present Convention." The five annexes set discharge limits for the following harmful substances: · Annex I: Oil · Annex II: Noxious liquid substances in bulk · Annex III: Harmful substances carried in packaged form · Annex IV: Sewage · Annex V: Garbage and all other ordinary vessel generated solid and liquid waste not covered by Annexes I, II, III and IV. In the United States, MARPOL 73/78 is implemented through the Act to Prevent Pollution from Ships, as amended and in 33 CFR 151. II. Waste Management The guiding principles for proper hazardous waste management shipboard are three fold: · Source reduction · Waste generation minimization · Proper disposal The first two principles are commonly referred to as pollution prevention initiatives and are practiced by the Coast Guard. It is hoped consideration is given to the following when formulating and conducting your experiments: 1. Maintain good housekeeping · Clearly mark the contents of all containers of hazardous materials and waste · Keep up-to-date inventory of all hazardous materials 2. Analyze all waste generated and ask if it is necessary and how it could be minimized. 3. Substitute less hazardous chemicals for hazardous ones. 4. Ship all unused chemicals to your institution or organization for further use upon departure from the vessel. 5. Reduce the scale of processes so that less waste is generated. Encl.(1) To facilitate proper waste disposal all scientists shall provide the following to the ship's Hazardous Material Control Officer two weeks prior to getting underway: 1) Material Safety Data Sheets (MSDS) of all chemical materials to be used shipboard, 2) a list of all laboratory-generated waste streams, and 3) a workspace management plan for handling hazardous materials/waste. Science laboratory waste generated shipboard is segregated into categories, turned over to ships force and disposed of by the Coast Guard. There are two types of waste generated underway: solid waste and hazardous waste. Solid waste is nonhazardous and is collected and handled as ships garbage. Hazardous waste (as defined by 40 CFR 261) is containerized labeled and turned over to ships force for disposal ashore. Chemical laboratory liquid waste is disposed of in one of two ways: first is normal drain disposal and the second is to request a drain disconnect for container collection. III. Rules For Laboratory Chemical Waste Drain Disposal Hazardous wastes are prohibited from discharge. Chemical wastes are hazardous if they are corrosive, reactive, ignitable, and/or moderately or highly toxic as defined by 40 CFR 261. The general rules for drain disposal are: 1. Laboratory disposal of chemicals is limited to the occasional disposal of small amounts of chemicals that are part of the experiment process. 2. Only water-soluble substances shall be disposed of in the laboratory sink. Solutions containing flammable solvents must be sufficiently dilute that they do not pose a fire hazard. All solutions should be flushed down the drain with an appropriate amount of water. (A compound is considered water soluble if it dissolves to the extent of at least 3%.) 3. Strong acids and bases should be neutralized or diluted to the pH 5-10 range before they are poured down the drain. 4. Use the chemical classification guidelines outlined below to determine if your chemicals can be drain disposed or must be container collected. We have assembled a list of chemicals (Appendix I, II and III) commonly found in research laboratories and have divided them into three groups with regard to drain disposal. If your chemicals are not on the list use the list as a guide to determine the proper drain disposal option. The drain disposal options regarding chemicals are: · Class A: Chemicals of little or no hazard in dilute aqueous solution. These solutions are suitable for disposal down the drain in quantities of up to about 100 grams of solute per laboratory per day. (These chemicals include many simple organic and inorganic compounds, as well as common inorganic chemicals. This includes most normal biological metabolites and nontoxic cellular constituents such as proteins, nucleic acids, carbohydrates, soluble fats and their precursors and catabolites.) · Class B: Chemicals of moderate hazard in dilute aqueous solution. These solutions are suitable for disposal down the drain with excess water in quantities no greater than 1 gram of solute per laboratory per day. (These chemicals include all the chemicals listed as toxic in the California Code of Regulations Section 22-66261.30 et. seq. that are water soluble and are not listed in the other appendices. Chemicals that are commonly considered "high hazard" inorganic salts are also listed.) · Class C: Chemicals that may not be drain disposed in any amount. (These chemicals include all chemicals that are not soluble as defined above, chemicals that are toxic or reactive at concentrations below 1 ppm in aqueous solution. Also included are the Federal Clean Water Act priority pollutants listed in 40 CFR 122 Appendix D, Tables II and III.) Chemicals that cannot be drain disposed shall be collected, via drain disconnect or other suitable means, in plastic chemical resistant bottles. The bottles shall be provided by the Coast Guard and labeled as to contents by the scientist. Turn over waste to ships force when the containers are near full and/or upon completion of your experiments. Appendix I - Class A Class A chemicals. Chemicals of little or no hazard in dilute aqueous solution. These are suitable for disposal down the drain with in quantities of up to about 100 grams of solute per laboratory per day. Class A chemicals include many simple organic and inorganic compounds, as well as common inorganic chemicals. This includes most normal biological metabolites and nontoxic cellular constituents (proteins, nucleic acids, carbobydrates, soluble fats, and their precursors and catabolites). 1. ORGANIC CHEMICALS Normal biological metabolites and nontoxic cellular constituents (proteins, nucleic acids, carbohydrates, soluble fats, and their precursors and catabolites). Alcohols Alkanols with fewer than 5 atoms Alkanediols with fewer than 8 atoms Sugars and sugar alcohols Alkoxyalkanols with fewer than 7 carbon atoms butanol, 1-(n-butyl alcohol) butanol, 2-(sec-butyl alcohol) ethanol ethanol,2-(2-butoxyethoxy) ethylene glycol glycerol methanol methyl 1-propanol, 2-(isobutyl alcohol) methyl 2- butanol, 2-(t-amyl alcohol) methyl 2-propanol, 2-(tert-butyl alcohol) propanol, 1-(n-propyl alcohol) propanol, 2-(isopropyl alcohol) Aldehydes: Aliphatic aldehydes with fewer than 5 carbon atoms acetaldehyde butyraldehyde formaldehyde gluteraldehyde propionaldebyde Amides RCONH2 and RCONHR with fewer than 5 carbon atoms RCONR2 with fewer than 11 carbon atoms formamide propionamide methyl propionamide N--butanamide Appendix I - Class A continued Amines** Aliphatic amines with fewer than 7 carbon atoms Aliphatic diamines with fewer than 7 carbon atoms benzyl amine butylamine n--dimethylamine dipropylamine propylamine pyridine Carboxylic Acids** Alkanoic acids with fewer than 6 carbon atoms Alkanedioic acids with fewer than 6 carbon atoms Hydroxyalkanoic acids with fewer than 6 carbon atoms Aminoalkanoic acids with fewer than 7 carbon atoms Ammonium, Sodium, and Potassium salts of the above acid classes with fewer than 21 carbon atoms acetic acid citric acid oxalic acid potassium binoxalate propanoic acid formic acid sodium acetate sodium citrate ** N.B. those organic compounds with a disagreeable odor, such as dimethylamine, 1,4 butanediamine, butyric acids and valeric acids, should be neutralized, and the resulting salt solutions flushed down the drain, diluted with at least 1000 volumes of water. Esters: Esters with fewer than 5 carbon atoms: ethyl acetate, isopropyl acetate, methyl acetate, methyl formate, methyl propionate, propyl formate, n-- Ethers dioxane, 1,4-dioxolane tetrahydrofuran Ketones: Ketones with fewer than 6 carbon atoms: acetone (2-propanone), cyclohexanone, methyl ethyl ketone (2-butanone), methyl isobutyl ketone, pentanone, 2- Appendix I - Class A continued Nitriles: acetonitrile propionitrile Sulfonic Acids: Sodium or potassium salts of most are acceptable
Cations: Aluminum Al3+ Ammonium NH4+ Calcium Ca2+ Cesium Cs+ Hydrogen H+ Lithium Li+ Magnesium Mg2+ Potassium K+ Sodium Na+ Strontium Sr2+ Tin Sn2+ Titanium Ti3+, Ti4+ Zirconium Zr2+ Anions: Borate (BO3 3-, B4O7 2-) Bromide (Br-) Carbonate (CO3 2-) Chloride (Cl-) Bisulfite (HSO3-) Hydroxide (OH-) Oxide (02-) Iodide (I-) Nitrate (NO3-) Phosphate (PO4 3-) Sulfate (SO4 2-) 3. PROPRIETARY PRODUCTS A generic class of chemicals sold under brand name and not in a concentrated form. Bleach (sodium hypochlorite solution) Detergents (alkanesulfonates) Photographic solutions- black and white developers and developer replenishers (No Fixers!): None approved at this time Biodegradable Liquid Scintillation Cocktails: None approved at this time Household ammonia Appendix I - Class A cont. Alphabetical Lists of Commonly Used Class A Chemicals CLASS A Organic acetaldehyde acetic acid acetone (2-propanone) acetonitrile benzyl amine butanamide butanol, 1-(n-butyl alcohol) butanol, 2-(sec-butyl alcohol) butylamine n--butyraldehyde citric acid cyclohexanone dimethylamine dioxane 1,4 -dioxolane dipropylamine ethanol ethanol 2-(2-butoxyethoxy) ethyl acetate ethylene glycol formaldehyde formamide formic acid gluteraldehyde glycerol isopropyl acetate methanol methyl 1-propanol, 2-(isobutyl alcohol) methyl 2- butanol, 2-(t-amyl alcohol) methyl 2-propanol, 2-(tert-butyl alcohol) methyl acetate methyl ethyl ketone (2-butanone) methyl formate methyl isobutyl ketone methylpropionamide, N -methyl propionate oxalic acid pentanone, 2 -potassium binoxalate propanoic acid propanol, 1-(n-propyl alcohol) propanol, 2-(isopropyl alcohol) propionaldehyde propionamide propionitrile propyl formate, n -propylamine pyridine sodium acetate sodium citrate tetrahydrofuran CLASS A Inorganic ammonium chloride ammonium nitrate ammonium sulfate ammonium thiosulfate boric acid calcium carbonate calcium chloride calcium hydroxide calcium nitrate calcium sulfate cesium chloride hydrochloric acid (neutralized) lithium bromide lithium chloride magnesium chloride magnesium oxide magnesium sulfate nitric acid (neutralized) perchloric acid (neutralized) phosphoric acid (neutralized) Plaster of Paris (calcium sulfate) potassium bicarbonate potassium bromide potassium carbonate potassium chloride potassium iodide potassium nitrate potassium phosphate potassium sulfate sodium bicarbonate sodium borate sodium carbonate sodium chloride sodium hydroxide (neutralized) sodium iodide sodium molybdate sodium nitrate sodium phosphate sodium sulfate sodium sulfite sodium thiosulfate sulfuric acid (neutralized) Appendix II - Class B Class B Chemicals: Chemicals of moderate hazard. These are suitable for disposal down the drain with excess water in quantities no greater than 1 gram of solute per laboratory per day. The final concentration in wastewater must not exceed 1 ppm after flushing with an appropriate amount of water. 1. ORGANIC CHEMICALS Commonly used Class B organic chemicals: acrylamide trypan blue 2. INORGANIC CHEMICALS Cations of the following metals: Barium Cobalt Gallium Germanium Hafnium Indium Iridium Iron Manganese Molybdenum Osmium Platinum Rhenium Rhodium Ruthenium Tellurium Tungsten Vanadium Anions and neutral compounds: Aluminum hydride (AIH4) Amide (NH2-) Azide (N3-) Borohydride (BH4-) Bromate (BrO3-) Chlorate (CIO3-) Fluoride (F-) Hydride (H-) Hydroperoxide (O2 Hydrosulfide (SH-) Hypochlorite (OCI-) Iodate (1O3-) Nitrite (NO2-) Perchlorate (CIO4-) Permanganate (MnO4-) Peroxide (O2 2-) Persulfate (S208 2-) Sulfide (S2-) Appendix III - Class C Class C Chemicals: Chemicals that may not be drain disposed in any amount. 1 . ORGANIC CHEMICALS All alkanes and water-insoluble hydrocarbons. All chlorinated and brominated hydrocarbons. EPA Priority Pollutants (see list below). Specific commonly used Class C organic chemicals: benzene cyclohexane ethyl ether ethidium bromide hexane phenol and phenolic compounds toluene xylene chlorinated hydrocarbons chloroform carbon tetrachloride methylene chloride (dichloromethane) PCBs tetrachloroethylene trichloroethane trichloroethylene chlorofluorocarbons (freons, halons) 2. INORGANIC CHEMICALS Chemicals containing the following metals and compounds Antimony Arsenic (including arsenate [AsO3-, AsO43-] and Arsenite [AsO2-]) Beryllium Cadmium Chromium (including chromate and dichromate) Copper Cyanides, Cyanates (OCN-), Thiocyanates (SCN-) Lead Mercury Nickel Selenium Silver, including photographic fixer Thallium Zinc Specific commonly used Class C inorganic chemicals: sodium azide, sodium cyanide, Chromium glassware cleaners: Chromerge, chromium trioxide/sulfuric acid solutions 3. EPA PRIORITY POLLUTANTS (40 CFR Part 122 Appendix D, Tables 11 and 111) TABLE II-ORGANIC TOXIC POLLUTANTS IN EACH OF FOUR FRACTIONS IN ANALYSIS BY GAS CHROMATOGRAPHY/ MASS SPECTROSCOPY (GS/MS) Volatiles 1V acrolein 2V acrylonitrile 3V benzene 5V bromoforrn 6V carbon tetrachloride 7V chlorobenzene 8V chlorodibromomethane 9V chloroethane 10V 2 chloroethylvinyl ether 11V chloroform 12V dichlorobromomethane 14V 1,1-dichloroethane 15V 1,2-dichloroethane 16V 1,1-dichloroethylene 17V 1,2-dichloropropane 18V 1,3 dichloropropylene 19V ethylbenzene 20V methyl bromide 21V methyl chloride 22V methylene chloride 23V 1,1,2,2-tetrachloroethane 24V tetrachloroethylene 25V toluene 26V 1,2-trans-dichloroethylene 27V 1,1,1-trichloroethane 28V 1,1,2-trichloroethane 29V trichloroethylene 31V vinyl chloride Acid Compounds 1A 2-chlorophenol 2A 2,4-dichlorophenol 3A 2,4-dimethylphenol 4A 4,6-dinitro-o-cresol 5A 2,4-dinitrophenol 6A 2-nitrophenol 7A 4-nitrophenol 8A p-chloro-m-cresol 9A pentachlorophenol 10A phenol 11A 2,4,6-trichlorophenol Base/Neutral 1B acenaphthene 2B acenaphthylene 3B anthracene 4B benzidine 5B benzo(a)anthracene 6B benzo(a)pyrene 7B 3,4-benzofluoranthene 8B benzo(ghi)perylene 9B benzo(k)Quoranthene 10B bis(2-chloroethoxy)methane 11B bis(2 chloroethyl)ether 12B bis(2 chloroisopropyl)ether 13B bis(2-ethylhexyl)phthalate 14B 4-bromophenyl phenyl ether 15B butylbenzyl phthalate 16B 2-chloronaphthalene 17B 4 chlorophenyl phenyl ether 18B chrysene 19B dibenzo(a, h)anthracene 20B 1,2-dichlorobenzene 21B 1,3-dichlorobenzene 22B 1,4-dichlorobenzene 23B 3,3'-dichlorobenzidine 24B diethyl phthalate 25B dimethyl phthalate 26B di-n-butyl phthalate 27B 2,4-dinitrotoluene 28B 2,6-dinitrotoluene 29B di-n-octyl phthalate 30B 1,2-diphenylhydrazine (as azobenzene) 31B fluroranthene 32B fluorene 33B hexachlorobenzene 34B hexachlorobutadiene 35B hexachlorocyclopentadiene 36B hexachloroethane 37B indeno(1,2,3-cd)pyrene 38B Isophorone 39B 39B naphthalene 40B nitrobenzene 41B N-nitrosodimethylamine 42B N-nitrosodi-n-propylamine 43B N-nitrosodiphenylamine 44B phenanthrene 45B pyrene 46B 1,2,4-trichlorobenzene Pesticides 1P aldrin 2P alpha-BHC 3P beta-BHC 4P gamma-8HC 5P delta-BHC 6P chlordane 7P 4,4'-DDT 8P 4,4'-DDE 9P 4,4'-DDD 10P dieldrin 11P alpha-endosulfan 12P beta-endosulfan 13P endosulfan sulfate 14P endrin 15P endrin aldehyde 16P heptachlor 17P heptachlor epoxide 18P PCB-1242 19P PCB-1254 20P PCB-1221 21P PCB-1232 22P PCB-1248 23P PCB-1260 24P PCB-1016 25P toxaphene 3. EPA PRIORITY POLLUTANTS (cont) TABLE II-ORGANIC TOXIC POLLUTANTS…. Other
(TCDD) asbestos
TABLE III - OTHER TOXIC POLLUTANTS (METALS AND CYANIDE) AND TOTAL PHENOLS Antimony, Total Arsenic, Total Beryllium, Total Cadmium, Total Chromium, Total Copper, Total Cyanide, Total Lead, Total Mercury, Total Nickel, Total Phenols, Total Selenium, Total Silver, Total Thallium, Total Zinc, Total |