Handling Hazardous Material Shipboard

OSHA (Federal Occupational Health and Safety Administration) regulations require that all chemicals brought on board are properly labeled and that Material Safety Data Sheets (MSDS) are available and readily accessible.

The scientist responsible for the Hazardous Materials is required to attach the MSDS to the online shipping form. This allows the MSTs to review the MSDS prior to the chemicals arriving so they can plan storage. Healy has a chemical storage locker in the main lab.

Shipboard handling and offload of Hazardous waste is the responsibility of the scientist. Please make arrangements prior to the cruise and inform the MSO of the plan.

Hazmat background taken from http://arctic.cbl.umces.edu/sbi/web-content/Cruise%20Link%20Information/...

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. 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 is removed from the ship while in port and disposed of by the scientist responsible for the waste generation. 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. Notify ships force when the containers are near full and/or upon completion of your experiments and inform them of the plan for removal from the ship.

  • 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

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2. INORGANIC CHEMICALS

  • This list comprises water-soluble compounds of low toxicity hazard cations and anions. Compounds of any of these ions that are strongly acidic or basic should be neutralized before disposal down the drain.

    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

    • dioxins- 2,3,7,8 tetrachloro-dibenzo-p-dioxin
      (TCDD)

and others
asbestos
3. EPA PRIORITY POLLUTANTS (continued)

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