SOME WELL-PUBLICIZED INCIDENTS FROM THE PAST FEW DECADES… The Cuyahoga River in Ohio became so polluted with chemicals it caught fire. There were many things being dumped in the river such as: gasoline, oil, paint, and metals. The river was called "a rainbow of many different colors". Fires erupted on the river several times before June 22, 1969, when a river fire captured national attention when Time Magazine reported it. Some river! Chocolate-brown, oily, bubbling with subsurface gases, it oozes rather than flows. "Anyone who falls into the Cuyahoga does not drown," Cleveland's citizens joke grimly. "He decays." Time Magazine, August 1969

SOME WELL-PUBLICIZED INCIDENTS FROM THE PAST FEW DECADES… A plant accident in Bhopal, India, released methyl isocyanate. Nearly 20 000 people died, 150 000 sick. Canadian company responsible: Union Carbide 40 000 kg released in 1984…loss of eyesight, respiratory failure, cancer, death

SOME WELL-PUBLICIZED INCIDENTS FROM THE PAST FEW DECADES… An accidental release of chemicals, including dioxin, in Seveso, Italy, in 1976 resulted in death of farm animals and long-term health problems for many local residents.

ENVIRONMENTAL DISASTERS DDT CFCs Love Canal

Environmental disasters Love Canal in Niagara Falls, NY a chemical and plastics company had used an old canal bed as a chemical dump from 1930s to 1950s. The land was then used for a new school and housing track. The chemicals leaked through a clay cap that sealed the dump. It was contaminated with at least 82 chemicals (benzene, chlorinated hydrocarbons, dioxin). Health effects of the people living there included: high birth defect incidence (like limb abnormalities) and seizure-inducing nervous disease among the children.

ENVIRONMENTAL DISASTERS Became rallying points for environmental laws Cuyahoga River- 1972 Clean Water Act Love Canal- 1980 Comprehensive Environmental Response, Compensation & Liability Act, better known as Superfund. Emergency Planning & Community Right-to-Know Act, requires that industries report toxic releases. Pollution Prevention Act 1990

MANY COUNTRIES HAVE ALREADY ENACTED LAWS AND SIGNED INTERNATIONAL TREATIES TO REDUCE POLLUTION LEVELS, INCLUDING: Montreal Protocol to Protect the Ozone Layer…ban on CFC’s Global Treaty on Persistent Organic Pollutants Rio Declaration on Environment and Development

Risk Due to a Hazardous Substance Risk=f(Hazard, Exposure) environmental laws attempt to control exposure Controlling Exposure = “end of the pipe solution”

Cost to Industry Industries in the US spend over $100 billion/year on waste treatment, control, and disposal. 1996 Dupont spent $ 1 billion for environmental compliance (research budget $ 1 billion; chemical sales of $18 billion)

THE POLLUTION PREVENTION ACT OF 1990 Risk=f(HAZARD, Exposure) Eliminate the hazard, no need to worry about the exposure!

IN A SUSTAINABLE CIVILIZATION… Technologies used for production of needed goods are not harmful to the environment or to human health. Renewable resources (such as plant-based substances or solar energy) are used rather than those, like fossil fuels, that will eventually run out.

IN A SUSTAINABLE CIVILIZATION… At the end of their use, materials are recycled if they are not biodegradable (easily broken down into harmless substances in the environment).

IN A SUSTAINABLE CIVILIZATION… Manufacturing processes are either designed so as not to produce waste products, – OR – Waste products are recycled or biodegradable.

WHILE WE HAVE MADE SOME PROGRESS IN ACHIEVING THESE GOALS, WE STILL HAVE A LONG WAY TO GO… Mountains of solid waste are piling up—particularly in non- industrialized nations (eg. poor countries take in container ships of garbage for a fee) Air and water pollution continue to be problems in many places. (Eg. Beijing- Olympic games

GREEN CHEMISTRY WORKS TOWARD SUSTAINABILITY BY: Making chemical products that do not harm either our health or the environment, Using industrial processes that reduce or eliminate hazardous chemicals Designing more efficient processes that minimize the production of waste materials Saving companies money by using less energy and fewer/safer chemicals, thus reducing the costs of pollution control and waste disposal

Examples of Green Chemistry Presidential Green Chemistry Challenge Award Winners For more informational on Presidential Green Chemistry Challenge Award Winners: http://www.epa.gov/greenchemistry/presgcc.html New syntheses of Ibuprofen and Zoloft- atom economy Integrated circuit production. Removing Arsenic and Chromate from pressure treated wood. Many new pesticides are biodegradable. New oxidants for bleaching paper and disinfecting water. Getting the lead out of automobile paints. Recyclable carpeting. Replacing VOCs and chlorinated solvents. Biodegradable polymers from renewable resources.

EXAMPLES OF GREEN CHEMISTRY Safer dry cleaning Initially gasoline and kerosene were used Chlorinated solvents are now used, such as perc Supercritical/liquid carbon dioxide (CO2) an even better choice

A SAFER METHOD OF DRY CLEANING Liquid CO2 can be used as a safer solvent if a wetting agent is used with it to dissolve grease. This method is now being used commercially by some dry cleaners. Dry cleaners using this method put a sign on their windows that say “perc free”

LEAD POLLUTION HAS BEEN DECREASED BY… Replacing lead in paint with safe alternatives, and Replacing tetraethyl lead with less toxic additives (e.g., “lead-free” gasoline).

PUTTING OUT FIRES THE GREEN WAY A new foam called Pyrocool FEF has now been invented to put out fires effectively without producing the toxic substances found in other fire-fighting materials.

Recycling is one way to head towards sustainability Polar fleece made from plastic bottles Company: Patagonia Torontonians use 100-125 million plastic bottles a year Only 50% is recycled The percent that is recycled…some is used to make polar fleece clothing. It takes on average 25 bottles to make 1 item Bird feeders…an example of upcycling Company: TerraCycle “ outsmart waste” Example Problems: Currently there isn’t an easy way to recycle car tires. There are on average 126 million car tires discarded a year in the world. About 50% are burned and 48% are stockpiled…this is one area that needs work

Design for degradation…design the product as biodegradable PLA and PHA plastics made with corn decomposes in 50 days in appropriate conditions - awarded Presidential Green Chemistry Award in 2002 Consider making PLA with other non-food crops such as miscanthus, kenaf, mustard plant…

Other idea: Raw Materials from Renewable Resources-The BioFine Process Paper mill sludge Levulinic acid Green Chemistry Challenge Award 1999 Small Business Award Agricultural residues, Waste wood Municipal solid waste and waste paper Levulinic acid used to make paints, flavours, biodegradeable herbicides, containers, cosmetics… example of end of use made useful

Use less energy to make the product Design the synthesis of the product so that it can be made at room temperature and pressure. Minimize use of ovens, stoves, refrigeration…use less energy and save the environment If energy is needed, consider alternate renewable sources…like Sally’s cereal sold at Walmart uses wind energy

Use safer solvents…antifoulants Antifoulants…marine pesticide…used to use TBTO… TBTO works by gradually leaching from the hull killing the fouling organisms in the surrounding area These compounds are chronically toxic to marine life and can enter food chain. They are bio-accumulative Now we use Sea-Nine® 211 DCOI Which won Presidential Green Chemistry Award Only organisms attached to hull of ship are exposed to toxic levels of DCOI. Readily biodegrades once leached from ship (half-life is less than one hour in sea water).  

Design for atom economy and higher yields Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product Similar to a synthesis reaction where the product you want is the only product formed… A + B → AB no other side product like single displacement or double displacement AB + C → AC + B AB + CD → AD + CB Eg: ibuprophen from 40% to 77 % mm of product/mm of all the reactants x100

GREEN CHEMISTRY DEFINITION GREEN CHEMISTRY IS ABOUT Green Chemistry is the utilization of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products *. GREEN CHEMISTRY IS ABOUT Waste Minimisation at Source Use of Catalysts in place of Reagents Using Non-Toxic Reagents Use of Renewable Resources Improved Atom Efficiency Use of Solvent Free or Recyclable Environmentally Benign Solvent systems

5 goals of green chemistry 1- Sustainability Use Renewable Materials…like garbage and biomass Example: 2- Safety Prevention, Less Hazardous Chemicals, Reduced Toxicity, Safer Solvents, Minimize Accidents 3- Process efficiency Atom Economy, Reduce Derivatives, Use Catalysis, Real-time Analysis 4- Energy efficiency Design for Energy Efficiency…use less energy 5- End of life degradation Design for Degradation…breaks down naturally-biodegradable

Green Chemistry Is About... W__________ M___________ H__________ Reducing R______ E__________ E__________ I______ C______ Everybody wins!..even the companies!

Green Chemistry Is About... Waste Materials Hazard Reducing Risk Energy Environmental Impact COST Everybody wins!..even the companies!