Green Chemistry in Labs: Waste Management
Green Chemistry in Labs: Waste Management
Planning
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  •isolating nonhazardous waste from hazardous waste;                                               Microscale Work and Wet Chemistry Elimination
  •using a column purification system for recycling of used solvent
                                                                                                    Microscale chemistry-amounts of materials used are
                                                            Recovery rate : 97% and more.           reduced to 25-100 mg for solids and 100-200 μL for
                                                            Recycle time : 4 to 6 hours.            liquids, compared with the usual 10-50 g for solids or
                                                            Easy to use : processor controlled,     100-500 mL for liquids.
                                                            easy residue removal and positive-
                                                            seal cover.                             • Smaller scale synthetic methods save money because
                                                            Recycles most popular solvents,           they require less reagent and result in less waste.
                                                            including mineral spirit, Acetone,      • Not all laboratory procedures can be scaled down.
                                                            IPA, MEK, Xylene, Hexane,                 Multigram laboratory preparation is often required
                          SR 180 and SR 180V (48 gallons)
 Applications:                                              Diacetone Alcohol, Ethyl, Methyl,         to provide sufficient material for further work.
 •Solvent Recovery                                          Chlorinated solvents, flexo press
 •VOC Steam Stripping                                                                               • Exercise precaution appropriate to the scale, as well
 •Alcohol Recovery
                                                            wash, flexo plate wash & litho
 •Vacuum Distillation                                       solvents and more.                        as the inherent hazards, of the procedure.
• When purchasing equipment to automate                                                             Solution: The lab purchased more glassware, better
  lab processes, choose equipment that is                                                           brushes, and an ultrasonicator that uses a mild detergent.
  efficacious, but uses the least amount of                                                          The lab installed bench lab dishwashers, which resulted in
  reagents or solvents, or least hazardous                                                          further reductions in solvent use for cleaning.
  materials.
                                                                                                    The savings in solvent purchase and disposal paid back the
                                                                                                    price of the new purchases in 3 months.
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2. ATOM ECONOMY
Better yield implies lower cost.                 Can this material be replaced by one that will expose the staff,
                                               and others who handle it, to less potential hazard?
Material substitution can be an                   Can this material be replaced by one that will reduce or
important consideration in                     eliminate the hazardous waste and the resulting cost of waste
manufacturing process design                   disposal?
because of the large quantity, and               Can these steps be taken in conjunction with yield maximization
potential cost of chemicals used.              and minimization of overall waste and cost?
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Labs are safer when they substitute nonhazardous, or less               • Consider carefully the use of reagents containing
                                                                          toxic heavy metals.
hazardous, chemicals by considering alternative synthetic routes
and alternative procedures for working up reaction mixtures.            Example:
 • To reduce the amount of copper released to the sewer,                Detergents for glassware are a safer substitute for
   use iron complexes rather than copper when studying                  chromic acid cleaning solutions. Various chromium(VI)
                                                                        and other metal oxidants are used in synthetic organic
   spectrophotometry.                                                   chemistry, but other oxidants are possible substitutes.
 • In liquid scintillation counting of low-level radioactive
                                                                        When planning a reaction, consider the cost of disposal
   samples, use nonflammable, lower toxicity, water-                    of heavy metal waste in addition to its utility.
   miscible solvents rather than xylene, toluene, or dioxane,
   so as to eliminate fire hazard and toxic wastes.
Example:
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                                            Keep it cool
                                               Upgrading a freezer could be even more
                                               efficient than expected.
                                               “Several models have been designed with
                                               energy efficiency in mind . . . often consuming
                                               60 percent less energy than freezers using older
                                               technology.”
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     Keep it organized
        Building a spreadsheet that includes all of the
        lab’s equipment. That lets you keep track of
        what you have in the lab, as well as when it was
        purchased and serviced.
9. Use Catalysts
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   Design Experimental Products for Degradation   11. Analyze in Real Time to Prevent Pollution
   After Use
  Green chemistry practitioners plan
  synthesis and other processes so that
  the products and byproducts are
  rendered safe or less hazardous.
  -include experimental plan reaction
  workup steps that deactivate hazardous
  materials or reduce their toxicity.
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                                                                     Flowchart for
                                                                     categorizing unknown
  An institution should minimize the amount of chemical              chemicals for waste
  accepted as a gift or as part of a research contract. The          disposal.
 • Elementary neutralization; the mixing of acidic and alkaline         Treatment of Acids and Bases
   waste to form a salt solution, has long been encouraged as
   long as safety considerations are addressed. In particular,
   dilute solutions should be used to avoid rapid heat generation.       • Neutralization of acids and bases (corrosives) is exempt from a
                                                                           treatment permit. Because the products of the reaction are
 • Treat before it becomes a waste.                                        often disposed of in the sanitary sewer, it is important to ensure
                                                                           that hazardous waste such as toxic metal ions is not a part of the
 • Treatment of by products assumes the material has not been              effluent.
   declared a waste or handled in a waste-like manner. Such
   treatment cannot be performed anywhere other than the                 • If both waste acids and waste bases are generated. It is
   location where the byproduct was generated.                             economical to collect them separately and neutralize. If
                                                                           additional acid or base is required, sulfuric or HCl and sodium or
                                                                           Mg(OH)2, can be used.
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                                                                 ACQUISITION OF CHEMICALS
                                                                   • Ordering Chemicals
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                                                                Storage Limits for Flammable and Combustible Liquids for Labs with Sprinkler System
                                                                                                                       Excluding Quantities in Rated   Including Quantities in Rated
                                                                                                                       Storage Cabinets/Safety Cans    Storage Cabinets/Safety Cans
                                                                                                                                      2
                                                                                                                       (max per 100 ft )               (max per 100 ft2)
                                                                Laboratory Unit Fire
                                                                Hazard Class              Class of Liquid              gal          L                  gal                   L
                                                                A(high fire hazard)       Class I flammable            10          38                  20                   76
                                                                                          (flash point <100 °F)
                                                                                          Combined Class I, II, IIIA   20          76                  40                  150
                                                                                          (fash point <200 °F)
                                                                B(moderate fire hazard)   Class I flammable             5          20                  10                   38
                                                                                          (flash point <100 °F)
                                                                                          Combined Class I, II, IIIA   10          38                  20                   76
                                                                                          (flash point <200 °F)
                                                                C(low fire hazard)        Class I flammable             2          7.5                  4                   15
                                                                                          (flash point <100 °F)
                                                                                          Combined Class I, II, IIIA    4          15                   8                   30
                                                                                          (flash point <200 °F)
                                                                D(minimal fire hazard)    Class I flammable             1           4                   2                  7.5
                                                                                          (flash point <100 °F)
                                                                                          Combined Class I, II, IIIA    1           4                   2
                                                                                          (flash point <200 °F)
 •Keep incompatible classes of gases stored separately. Keep      Can the chemical be managed safely
                                                                  when it arrives? Does it require special
 flammables away from reactives, which include oxidizers          storage, such as in a drybox, refrigerator,
 and corrosives.                                                  or freezer?
 •Segregate empty cylinders from full cylinders.                  Do receiving personnel need to be
 •Keep in mind the physical state—compressed, cryogenic, or       notified of the order and given special
                                                                  instructions for receipt? Will any special
 liquefied—of the gases.                                          equipment necessary to use the
 •Do not abandon cylinders in the dock storage areas.             chemical be ready when it arrives?
 •Return cylinders to the supplier when you are finished with
 them.                                                                     An effort should be made to order chemicals for just-in-time
                                                                           delivery by purchasing all unstable or extremely reactive materials
                                                                           from the same supplier with a request for one delivery at the best
                                                                           time for performing an experiment.
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Laboratory waste
   -generated from laboratories in industry and in educational
   centers such as secondary schools and universities.
   • Hazardous
   • Clinical
   • Biological
   • Electrical
   • Chemical Laboratory
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    • By-product, side products, process residues, spent reaction                • Long term environmental hazards including chronic
      media, contaminated plant or equipment or other substances
      from manufacturing operations and as consumer discard of
                                                                                   toxicity upon repeated exposure, carcinogenicity,
      manufactured products which present unreasonable risk
                                                                                   resistance to detoxification process such as
      and/or injury to health and safety and to the environment.                   biodegradation, the potential to pollute underground
                                                                                   or surface waters, or aesthetically objectionable
                                                                                   properties such as offensive odors.
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   Hazardous wastes exhibit any one of the following                         Ignitable wastes are capable of causing or
   characteristics, and here is a little TRIC(K) to                          intensifying a fire during routine handling. A waste
   remember them:                                                            is characteristic for ignitability if it has any one of
                                                                             the following properties:
     T    Toxicity                Wastes that causes health or
                                  environmental effects                       • a liquid with a flash point less than 140 o F (60o C)
                                                                              • a solid, capable under standard temperature and pressure, of
                                                                                causing fire through friction, absorption of moisture, or
    R     Reactivity              Wastes that readily explodes of               spontaneous chemical changes, and when ignited, burns
                                  undergo violent reaction.                     vigorously and persistently.
                                                                              • an ignitable compressed gas
                                  Wastes that easily catch on fire            • an oxidizer.
     I   Ignitability
                                  and sustain combustion
                                                                                                         Acetone       Ethyl ether     Pentane
                                                                             most organic
                                  Wastes that are acidic or alkaline                                     Benzene       Heptane         Petroleum Ether
     C Corrosivity                                                           solvents                    Ethanol       Hexane          Toluene
                                  that readily corrode or dissolve
                                                                                                         Ethyl acetate Methanol Xylene
                                  materials they are in contact with.
     Corrosive wastes: A waste has the characteristic of corrosivity         • cyanide or sulfide bearing waste which, when exposed to pH
     if it has one of the following properties:                              conditions between 2 and 12.5, can generate toxic gases,
                                                                             vapors or fumes in a quantity sufficient to present a danger to
     • an aqueous waste with pH 2 or less, OR pH 12.5 or greater;            human health or the environment;
     • a liquid that corrodes steel at a rate greater than 6.35mm            • is capable of detonation or explosive reaction if subjected to
     (0.25 inches) per year.                                                 a strong initiating source or heated under confinement;
     A waste has the characteristic of reactivity if it:                     • is readily capable of detonation or explosive;
     • is normally unstable and readily undergoes violent change             • is a forbidden explosive or a Class A or Class B explosive.
     without detonating;
     • reacts violently with water;
                                                                              Toxic wastes are harmful or fatal when ingested or absorbed.
     • forms potentially explosive mixtures with water;
                                                                              When they are disposed of on land, contaminated liquid may
     • mixes with water to generates toxic gases, vapors or fumes
                                                                              drain (leach) from the waste and pollute groundwater.
     in a quantity sufficient to present a danger to human health or
     the environment;
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   • Any water or waste containing readily releasable cyanide             • Any gasoline, benzene, naphtha, fuel oil, or other flammable or
     (cyanide released at a temperate of 150oF (65o C) and pH –             explosive liquids, solids or gases.
     1.5) in excess of 2 mg/L; any water or waste containing total
     cyanide in excess of 5 mg/L.                                         • Any water or waste containing fats, wax, grease or oils whether
                                                                            emulsified or not, in excess of 100 mg/L r containing
   • Any liquids or wastes containing toxic or poisonous substances         substances which may solidify or become viscous at
     in sufficient quantities or rate of flow as to injure or interfere     temperatures between 33 o Fahrenheit and 105 o Fahrenheit (1
     with any of the sewage                                                 and 65° Centigrade)
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                                                                                    ETHER DISPOSAL
  Each section in the lab will collect hazardous wastes in a one
  gallon bottle, and each container is properly labeled as                          Ethyl ether should be disposed when ANY ONE of the
  follows:                                                                          following criteria are met:
  a) The date collection begin in this container                                          a. Ether has reached the expiration date stamped
                                                                                    on the original container.
  b) Where generation took place, room number                                             b. 1 year has expired since the production of
                                                                                    ether. The date is stamped on the original container.
   c) If the contents are primarily of one material, ex. Acetone,
  identify the contents with the name of the material, If the                            c. 30 days has elapsed since the container was
  contents are a mixture of materials, give the percentage of                       opened for the first time.
  each.
                                                                                    TO DISPOSE OF ETHER:
  d) Give the total number of containers.
                                                                                    Ether should be “Lab. Packed”
  e) Check all of the appropriate hazards.
Collect Hg salts into a 4 liter unbreakable container and                   DATE:           GENERATOR ID:         LOCATION OF
label with complete waste material I.D. form.                               GENERATION:
                                                                            NAME OF MATERIAL:        FORM:        NUMBER OF
HAZARDOUS WASTE DISPOSAL FORM                                               CONTAINERS:
                                                                            Describe contents giving HAZARD INFORMATION:
Laboratory Name
Label – “CAUTION - WASTE MATERIAL”                                          Components, concentrations, Check all that you think apply and
Attached to a compatible, non-leaking container with a non-leaking          information reference
sealable closure, the following label when properly completed meets
                                                                                                   ___ ACIDIC            ___ FLAMMABLE
these requirements:
A. Identifies and qualifies the chemical components in the containers                             ___ BASIC              ___ NEUTRAL
B. Establishes the date when the filling process began.                                           ___ BIOHAZARD           ___ OXIDIZER
C. Identifies the hazard(s) associated with the contents of the container                         ___ BURNS READILY       ___ REACTIVE
D. Identifies the person who served as generator and the location where                           ___ CARCINOGEN          ___ REDUCER
generation too place.                                                                             ___ EXPLOSIVE
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GUIDELINES FOR DISPOSAL OF LABORATORY HAZARDOUS WASTES GUIDELINES FOR DISPOSAL OF LABORATORY HAZARDOUS WASTES
                                                                                                                  Incineration
                                                                 Ethers                                           Dilution with higher boiling point
                                    PREFERRED METHOD OF
 COMPOUND CLASS                                                                                                   alcohols may be necessary
                                    DISPOSAL                     Mercaptans                                       Incineration
 Hydrocarbons                       Incineration                 Organosulfer compounds                           Incineration or disposal site
                                                                 Carbocyclic acids                                Incineration
 Halogenated HC             Recycling                            Other organic acids                              Incineration
 Recoverable halogenated HC Landfill                             Acid halides and anhydrides
                                                                                                                  Incineration or hydrolysis in sewer
                                                                                                                  disposal
                                                                 Other acids derivatives, ester, anides
                                    Incineration or some prior                                                    Incineration
 Other halogenated                                               and nitriles
                                    hydrolysis with Ethynolic    Aldehydes and ketones                 Incineration
 compounds
                                    Potassium Hydroxide          Amines                                Incineration
                                                                                                       Incineration or landfill except those
 Alcohols and Phenols               Incineration                 Nitro compounds
                                                                                                       know to be explosive
                                                                 Organic peroxides and hydro peroxides Incineration or decomposition
                                                                 Dyes and pigments                     Incineration
Chemicals in which neither cation nor anion presents               Chemicals in which neither cation nor anion presents
significant hazard.                                                significant hazard.
                                  PREFERRED METHOD OF                                                              PREFERRED METHOD OF
   COMPOUND CLASS                                                  COMPOUND CLASS
                                  DISPOSAL                                                                         DISPOSAL
   Soluble compounds              Decant into sewer                                                                Chemical decomposition and
                                                                   Metal fluorides
                                                                                                                   sewer disposal
   Insoluble compounds            Sanitary landfill
                                                                                                                   Chemical decomposition and
   Chemical with toxic cationic                                    Inorganic cyanides
                                  Secure landfill                                                                  sewer disposal
   element
                                                                                                                   Chemical decomposition and
   Chemical with toxic anionic    Incineration or chemical         Metal azides
                                                                                                                   sewer disposal
   component                      decomposition
                                                                   Metal anides                                    Dispose of as explosives
   Oxidizing agents               Reduction and sewer disposal
                                                                                                                   Incineration of chemical
   Metal hydrides                 Chemical decomposition           Alkaline metals
                                                                                                                   decomposition and sewer disposal
   Metal sulfides                 Chemical decomposition           Organometallic chemical                         Incineration or secure landfill
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  a. How can stubborn residues be avoided?                                       Collection containers for disposal must be appropriate to the intended
                                                                                 content. The disposal vessels must never be closed tight during us to
  -removing coarse residue manually before cleaning.                             prevent pressure build-up.
  When there are very stubborn types of contamination it is                      Solvent waste is cost effective as many chemicals can be disposed of
  recommended that the items to be cleaned are put in an immersion               relatively cheaply in this way. The mixture of different reagents does
  bath with cleaning agents.                                                     however present a risk of chemical reactions which cannot be
                                                                                 predicted. Reactive chemicals may therefore only be added to the
  Autoclaving should be carried out if the biological material requires it.      disposal vessel in small quantities.
c. Which wastes/residues are separated on disposal and on what basis? What requirements must a cleaning agent meet?
Solvent waste is disposed of separately in two categories: halogen-free            The selection of the correct cleaning agent is linked to the type of
and halogen-containing solvents.                                                   soiling to be removed and the framework conditions such as time,
                                                                                   material properties and mechanical system which can be used.
Filtration and absorption masses such as e.g. chromatography films are             There are also a few fundamental requirements of a cleaning agent
collected in the plastic buckets provided for this purpose and passed              e.g.:
on for disposal.
                                                                                      good ability to remove dirt               not hazardous to health
Contaminated used oil from vacuum pumps is disposed of as special                     high dirt carrying capacity               ideally non-scenting
waste.                                                                                suitable on most surfaces                 very cost effective
                                                                                      good rinsing properties                   environmentally friendly
Broken glass is collected separate to other waste in the containers                   easy handling
provided.
                                                                              Degree of Purity
 In which work areas does disinfection play a role?
                                                                               a. What does “clean glass” actually mean?
 Disinfection plays a role in the following areas among others:
 microbiology, pathology, diagnostics, histology, immunology and               This means that the surface of the laboratory glass can be described as optically clean
                                                                               and surfaces of the lab glass must also be free of residues which could affect the
 production of cosmetics, medicines and foodstuffs..                           analytical results.
When is disinfection absolutely necessary? b. How residue-free does the glass have to be?
 In all areas in which personal protection against infectious                  With automated cleaning ,the program sequence will determine how many cleaning
 material or the prevention of a transfer of germs (e.g. cosmetic              stages occur. It can be assumed that the items cleaned have only minimal residues of
                                                                               process chemicals on them. Trace element detection is important, or critical
 agents, medicines etc.) are necessary.                                        applications such as pharmaceutical production.
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• Rule LVI “Penalties for other Violations and other provisions under the ACT”        R.A 9275
   • Section 1 to 12                                                                  “The Philippine Clean Water Act of 2004”
        • Burning of waste 2 years and 1 day to 4 years imprisonment.                 Salient Features
                                                                                                                   Signed March 22, 2004
        • Burning of hazardous substances and waste - 4 years and one day to 6
          years imprisonment.                                                                 • Facts:
        • Burning of biomedical waste - 4 years and 1 day to 6 years imprisonment.
        • Smoking in public places- 6 months and 1 day to 1 year imprisonment or              • Only 51% of the country’s classified rivers still met the standard.
          fine of Php10,000                                                                   • Domestic wastewater is the principal cause of organic pollution.
        • Manufacture, Sales, introduction to commerce, conveyance,                           • Only 3% of investment in water supply and sanitation were
                                                                                                going on to sanitation and sewerage treatment.
          transportation of fuel - 3 years and 1 day to 5 years imprisonment.
                                                                                              • Metro Manila is second to the lowest in sewer connection
        • Manufacture of fuels and fuels additives - 2 years and 1 day to 4 years               among major cities in Asia and less than 7% compared to 20%
        • misfuelling - 1 year and 1 day to 3 years imprisonment or a fine of Php               for Katmandu and 30% for Dhaka, Bangladesh.
          20,000.                                                                             • 30% of all illnesses are attributed to polluted waters.
        • DENR shall prepare the schedule of fines and the ranges shall be not less
          than Php10,000 and not more than Php100,00.
  It aims to protect the country’s water bodies from pollution from all                           • Effluent trading per management area.
  sources (industries, commercial establishment, agriculture and
  community/household activities).                                                                • Rewards for discharger whose discharge is better than the
                                                                                                    quality of the receiving body of water.
  It provides for a comprehensive and integrated strategy to prevent and
  minimize pollution through a multi-sectoral and participatory approach                          • Fiscal and Non-fiscal incentives for LGU’s Water District,
                                                                                                    enterprise, private entities and individuals who develop and
  involving all stakeholders.                                                                       undertake outstanding and innovative projects in water
                                                                                                    quality management
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                                                                                          E.coli
                     COD          - measure of the amount of                                  - Statistical indication of the presence of
                                  oxidizable compounds; for both                              recent human pathogen contamination in
                                  biodegradable and recalcitrant                              terms of MPN/100 mL.
                                  organic carbon.
                                                                                              - Escherichia coli is not a pathogen.
                                                                                    UPD-NEC
Solids Color
pH Temperature
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                                                                     Priority Pollutants
Fats, Oils, and Grease (FOG)
                                                                               Name                           USE                CONCERN
                                                                          Non-Metals
                                                                                              Alloying additive for metals:    Carcinogen and
   Fats and oils usually originate from the food industry in the             Arsenic          semicon, boiler tubes, cable     mutagen
   form of butter, lard, margarine, and vegetable oils, and from                              Electronics, computer cores,     Depression,
                                                                             Selenium         rectifiers, colorant for glass   Weakness
   meat processing.                                                       Metals
                                                                                              Deoxidizer for copper, spark-    Nerve block,
   Kerosene, lubricating, and road oils are derived from petroleum
                                                                             Barium           plug alloys, X-ray tubes         Powder-flamm.
   and coal tar.                                                                              Metal an ceramic application,    Carcinogen,
                                                                             Cadmium          Ni-Cd batteries, Vapor lamps     Powder-flamm.
   FOGs interfere with biological action, cause maintenance
                                                                                              Alloying and plating element,    Hexa Cr is
   problems, and create unsightly floating matter and films on               Chromium         Protective coating, Pigments     carcinogenic
   surface waters..                                                                           Storage batteries, gasoline      Brain and
                                                                             Lead             additive, piping, ammunition     kidney damage
                                                                                              Electrical apparatus,            Central nervous
                                                                             Mercury          instruments, lamps               system damg.
                                                                                              Photo chemicals, linings,        Toxic metal,
                                                                             Silver           mirror, laboratory, medicine     eyes, skin prb.
Priority Pollutants
     Ethylbenzene
                    Intermediate in styrene
                    production, solvent
                                                      Toxic and
                                                      irritant
                                                                                                 IS YOUR
                    Aviation gasoline, solvents for   Toxic,
     Xylene         paints, dyes, adhesives
                    Plastics, paint removers,
  Halogenated Cpds. solvents, degreasers
                                                      flammable
                                                      Carcinogen,
                                                      narcotic
                                                                                                  ROLE?
                    Insecticides, fumigants,          Toxic,
  Pesticides        pesticides, herbicides            persistent
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