Lectures 19 and 20

April 7 and 12, 2011

Pesticides and Herbicides

Organochlorine Insecticides Toxic Effects Dose-response relationship The Distribution of Environmental Pollutants Organophosphate and Carbamate Insecticides Herbicide triazines, 2,4-D, Agent Orange

Learn more from the major producers of Pesticides and the pollution they have left behind http://www.epa.gov/pesticides/ http://www.dowagro.com/usag/ http://www.monsanto.com/default.asp

Pesticides
- Insecticides - Herbicides - Fungicides Nearly half of the use of Pesticides in North America involves Agriculture 80-90% of households in the US have at least one synthetic pesticides Insecticides mainly in growing cotton Herbicides mainly in growing corn and soybeans Pesticide regulation to date has not paid enough attention to the protection of health

Organochlorine Insecticides
Stability against decomposition or degradation in the environment Very low solubility in water High solubility in hydrocarbon-like environments (fatty materials) Relatively high toxicity to insects but low toxicity to humans HCB used as a fungicide for cereal crops, now being phased out 99% of Americans have detectable levels of HCB

Environmental Contamination at Production Facility .. A case study

http://www.epa.gov/superfund/sites/npl/nar1425.htm National Priorities List (NPL) Site Narrative for Chevron Chemical Co. CHEVRON CHEMICAL CO. (ORTHO DIVISION) Orlando, Florida
Federal Register Notice: May 31, 1994 The Chevron Chemical Co. Inc. (Ortho Division) site is located in Orlando, Orange County, Florida. The site covers approximately 4.39 acres in an industrial area at 3100 Orange Blossom Trail. The Chevron Chemical Co. operated a chemical blending facility for pesticides and other crop sprays between 1950 and 1976. The facility formulated a variety of liquid and powdered pesticides, citric sprays, and nutritional sprays. Chemicals used in pesticide formulation included xylene, kerosene, mineral oil, and aromatic naphtha. A few of the pesticides formulated in large volumes consisted of chlordane, lindane, dieldrin, and aldrin.

Prior to 1970, two unlined rinsate ponds onsite were used for the collection and disposal of pesticide formulating rinse water, barrel rinse water, and storm water. After 1970, the pesticide formulating rinsate was collected and disposed of offsite at an unknown location.

http://www.thenewatlantis.com/publications/the-bhopal-injustice

Pesticides that kill Lions _CBS 60 minutes http://www.youtube.com/watch?v=U8wC-7MYHaw&feature=related

The Story of Silent Spring

http://www.nrdc.org/health/pesticides/hcarson.asp

How a courageous woman took on the chemical industry and raised important questions about humankind's impact on nature.

Rachel Carson's Silent Spring, which in 1962 exposed the hazards of the pesticide DDT, eloquently questioned humanity's faith in technological progress and helped set the stage for the environmental movement.
http://www.rachelcarson.org/

DDT, the most powerful pesticide the world had ever known, exposed nature's vulnerability. Unlike most pesticides, whose effectiveness is limited to destroying one or two types of insects, DDT was capable of killing hundreds of different kinds at once. Developed in 1939, it first distinguished itself during World War II, clearing South Pacific islands of malaria-causing insects for U.S. troops, while in Europe being used as an effective de-lousing powder. Muller, DDT's inventor, was awarded the Nobel Prize in 1948.

Silent Spring: It meticulously described how DDT entered the food chain and
accumulated in the fatty tissues of animals, including human beings, and caused cancer and genetic damage. A single application on a crop, she wrote, killed insects for weeks and months, and not only the targeted insects but countless more, and remained toxic in the environment even after it was diluted by rainwater. Carson concluded that DDT and other pesticides had irrevocably harmed birds and animals and had contaminated the entire world food supply. The book's most haunting and famous chapter, "A Fable for Tomorrow," depicted a nameless American town where all life -- from fish to birds to apple blossoms to human children -- had been "silenced" by the insidious effects of DDT. First serialized in The New Yorker in June 1962, the book alarmed readers across America and, not surprisingly, brought a howl of indignation from the chemical industry. "If man were to faithfully follow the teachings of Miss Carson," complained an executive of the American Cyanamid Company, "we would return to the Dark Ages, and the insects and diseases and vermin would once again inherit the earth." Monsanto published and distributed 5,000 copies of a brochure parodying Silent Spring entitled "The Desolate Year," relating the devastation and inconvenience of a world where famine, disease, and insects ran amuck because chemical pesticides had been banned. Some of the attacks were more personal, questioning Carson's integrity and even her sanity. http://www.nrdc.org/health/pesticides/hcarson.asp

Did Your Shopping List Kill a Songbird?

March 30, 2008

By BRIDGET STUTCHBURY, a professor of biology at York University in Toronto, and the author of Silence of the Songbirds.
Migratory birds, modern-day canaries in the coal mine, reveal an environmental problem hidden to consumers. Testing by the United States Food and Drug Administration shows that fruits and vegetables imported from Latin America are three times as likely to violate Environmental Protection Agency standards for pesticide residues as the same foods grown in the United States. Some but not all pesticide residues can be removed by washing or peeling produce, but tests by the Centers for Disease Control show that most Americans carry traces of pesticides in their blood. American consumers can discourage this poisoning by avoiding foods that are bad for the environment, bad for farmers in Latin America and, in the worst cases, bad for their own families.

Now that spring is here, we take it for granted that the birds cheerful songs will fill the air when our apple trees blossom. But each year, as we continue to demand out-of-season fruits and vegetables, we ensure that fewer and fewer songbirds will return.

Reflecting Pool at Notre Dame

How do they keep the reflecting pool clean? Have you noticed the color of the water? What do they do when they empty the water before a major event or before winter?

DDT
Hailed as miraculous during its use in WWII Found to be effective against the mosquitoes that carry malaria, body lice that can transmit typhus and against plague-carrying fleas Low vapor pressure and low solubility in water gave protection for weeks to months Saved lives of millions of people Its effectiveness led to overuse in agriculture

http://www.youtube.com /watch?v=LQ64sV0nSV U&feature=related

Dichlorodiphenyldichloroethene, DDE
DDE is a metabolite of DDT. Also produced slowly during the degradation in the environment Greatly affected bird population DDE interferes with the enzyme that regulates the distribution of calcium.leads to thin eggshells

-HCl

DDT

DDE in Body Fat

Solubility in fat and animal tissue has caused accumulation of DDT and DDE in birds, fish and humans DDT is now banned in most industrialized countries

Concentration of DDT and DDE in Salmon

Concentration of DDT and DDE in breast milk

Accumulation of Organochlorines in Biological Systems Bioconcentration factor, BCF

Partition Coefficient Kow = [S]octanol/[S]water For DDT log Kw = 6 or Kw= 1000000 BCF for DDT lies 20000 400000 Hence Kw gives aprox measure of BCF Higher theKw more likely chemical is bound to organic matter in soil and fatty materials

Biomagnification A chemical whose concentration increases along a food chain is said to be biomagnified.
Variation with age of DDT concentration in Lake Ontario Trout

Biomagnification results from a sequence of bioaccumulation steps

http://video.on.nytimes.com

Biomagnification
25 ppm of fat in the fat of the Cormorants 2 ppm of DDT in Needlefish 0.5 ppm of DDT in the fat of minnows

0.04 ppm of DDT in Plankton

0.003 ppb of DDT in Long Island seawater

Analogs of DDT

The para-chlorines of DDT are replaced in methoxychlor by methoxy groups. The degradation products are water soluble and degrade in the environment. Also the products are excreted rather than accumulated by organisms

Other Organochlorine Insecticides

Toxaphene, a mixture of hundreds of similar substances (partially chlorinated camphene- pine tree product) was widely used as insecticide during 1966-1976 in the US Toxaphene is extremely toxic to fish Restrictions were placed in 1982 and a total ban in 1990

Spread of Toxaphene in Northern America

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Chlorinated Cyclohexane and Cyclopentadiene

Triclosan is a chlorinated aromatic compound which has functional groups representative of both ethers and phenols. Triclosan is slightly soluble in water, but soluble in ethanol, diethyl ether, and stronger basic solutions such as 1 M sodium hydroxide, like many other phenols. The EPA registers it as a pesticide, giving it high scores as a risk to both human health and the environment.
http://www.cnn.com/video /#/video/health/2005/10/2 0/cohen.soap.bacteria.cnn ?iref=videosearch http://www.epa.gov/oppsrrd1/REDs/factsheets/triclosan_fs.htm

5-chloro-2-(2,4-dichlorophenoxy)-phenol

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Toxic Effects Dose-Response Relationships

The dose of the substance administered in toxicity tests is usually expressed as the mass of the chemical usually in milligrams per unit of test animals body weight (usually kg) The dose that proves to be lethal to 50% of the population of test animals is called LD50 value The smaller the LD50 value, the more potent the chemical LOD50 refers to Lethal Oral Dose

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Risk Assessment To perform risk assessment, it is important to know Hazard evaluation information (accute, cancer ???) Quantitative dose-response information An estimate of the potential human exposure to the chemical The highest dose at which no observable effects level is called NOEL (expressed in terms of mg/kg body weight/day) To determine the threshold level for the most sensitive members of the human population, EPA uses Toxicity reference dose or RfD. (RfD is also referred as Acceptable Daily Intake or ADI) RfD (or ADI) = NOEL/100

If NOEL for a chemical is 0.01 mg/kg/day, the ADI or RfD for a 80 kg man would be (0.01 mg/kg/day /100) x 80 kg = 0.008 mg

http://www.epa.gov/opp00001/regulating/laws/fqpa/index.htm FQPA dramatically changed the safety standards EPA uses in evaluating potential pesticide risks, especially to infants and children. Since FQPA was enacted, effective protection of children, already a priority, received additional emphasis through the addition of an extra tenfold Children's Safety Factor. This additional factor is now standard in dietary risk assessments, unless reliable data support a different factor.

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The Distribution of Environmental Pollutants

Fugacity of a substance is proportional to concentration in a given phase

f = C/Z
Z is a fugacity capacity constant for the substance and the phase. Generally higher the Z value, the greater the tendency to accumulate in that phase ..analogous to equilibrium constant For a given phase (x)

fx = Cx/Zx

Or Cx= fx .Zx

If total number of moles preset is is ntotal, and in phase x is nx Cx = nx/Vx or nx =Cx.Vx

nx=f.Zx.Vx

ntotal = f.ZxVx

Or

f = ntotal /ZxVx

..Follow the fugacity example on page 462/335

Organophosphate and Carbamate Insecticides

Organophosphate and carbamate insecticides are commonly used for small animals as flea and tick powders, sprays, foggers, shampoos and dips, flea collars, and formerly, as systemic insecticides. They are also frequently used as household, garden, and farm insecticides. Chlorpyrifos, parathion, diazinon, famphur, phorate, terbufos, and malathion are examples of organophosphates while carbofuran, aldicarb, and carbaryl, are carbamates. They are all marketed under a wide variety of trade names.
All OP/Carbamate insecticides are fat soluble and therefore are easily absorbed through the skin and then transported throughout the body. These chemicals kill insects and cause poisoning in animals by inhibiting the enzyme, acetylcholinesterase (AChE) which normally functions to degrade acetylcholine in nerve synapses. Inhibition of AChE in the nerves results in a buildup of acetylcholine (ACh) and overstimulation of ACh receptors.
http://www.addl.purdue.edu/newsletters/1998/summer/organos.html

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Organophosphate Insecticides

Unlike organochlorins, organophosphates donot bioaccumulate Decompose within days-weeks after the accumulation.

Consumption of organophosphate pesticides by various crops in the US

Structurally all organophosphate pesticides contain a central pentavalent P atom and R- groups are connected through oxygen or sulfur atom

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The organophosphates, e.g., parathion, are related to the nerve gases developed during World War II. They react irreversibly with the enzyme acetylcholinesterase, which is responsible for inactivating acetylcholine (ACh) at neuromuscular junctions and at certain synapses in the central and peripheral nervous systems. Some other examples: malathion diazinon phosmet (Imidan) chlorpyrifos (Lorsban) Some of the organophosphates are very toxic. Parathion, for example, is 30 times more toxic than DDT. Each year organophosphates poison thousands of humans throughout the world, causing hundreds of deaths.

Carbamate Insecticides

Carbamate insecticides are inhibitors of acetylcholinesterase, but their action is reversible. Some examples: carbaryl (Sevin) aldicarb (Temik) methomyl (Lannate) Features: These compounds are rapidly detoxified and excreted so their risk to warmblooded animals is less than the other agents we have looked at. They are degraded rapidly in the environment so persistence is not a problem. They are, however, a danger to many useful insects, especially honeybees.

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Pesticides from Natural Sources

-Obtained from flowers, chrysanthemum -Paralyze insects but do not strong enough to kill them -Synthetic pyretrins are called pyrethroids -Common ingredients in domestic insecticides

Herbicides

Selective herbicide, effective in killing many broadleaf plants. Marketed under many different names: Weed-BGon (Chevron), Fernoxone (ICI), and Weedone (Union Carbide), to name a few. Over 30,000 tons of 2,4-D are utilized in the US each year. Natural degradation in water is slow (6-170 days).

Cl O CH 2 CO 2 H Cl

2,4-Dichlorophenoxyacetic acid

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Pesticides in the Hydrologic System

About 1 billion pounds of pesticides are used each year in the United States to control weeds, insects, and other organisms. About 80 percent of this quantity is used in agriculture. Although the use of pesticides has resulted in increased crop production and other benefits, it has raised concerns about potential adverse effects on the environment and human health. In many respects, the greatest potential for unintended adverse effects of pesticides is through contamination of the hydrologic system, which supports aquatic life and related food chains and is used for recreation, drinking water, irrigation, and many other purposes. Water is one of the primary pathways by which pesticides are transported from their application areas to other parts of the environment

Pesticide movement in the hydrologic cycle

http://ca.water.usgs.gov/pnsp/rep/fs09200/

TRIAZINES

Atrazine is a selective triazine herbicide used to control broadleaf and grassy weeds in corn, sorghum, sugarcane, pineapple, christmas trees, and other crops, and in conifer reforestation plantings. Over 64 million acres of cropland were treated with atrazine in the U.S. in 1990. Trade or generic names: Aatrex, Aktikon, Alazine, Atred, Atranex, Atrataf, Atratol, Azinotox, Crisazina, Farmco Atrazine, G-30027, Gesaprim, Giffex 4L, Malermais, Primatol, Simazat, and Zeapos Use: Selective triazine - herbicide used to control broadleaf and grassy weeds Toxicity: Atrazine is slightly to moderately toxic to humans and other animals. It can be absorbed orally, dermally, and by inhalation. Symptoms of poisoning include abdominal pain, diarrhea and vomiting, eye irritation, irritation of mucous membranes, and skin reactions

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Largest producer of Atrazine based herbicides Sales in 2008 were approximately $9.2 billion.

http://www.syngenta.com/en/index.aspx

Video

http://www.syngenta.com/en/media/multimedia-downloads.html#

http://www.berkeley.edu/news/media/releases/2006/02/02_pesticides.shtml

Pesticide combinations imperil frogs

By Robert Sanders, Media Relations | 02 February 2006 UC BERKELEY The pesticide brew in many ponds bordering Midwestern cornfields is not only affecting the sexual development of frogs, but is making them more prone to deadly bacterial meningitis, according to a new study by University of California, Berkeley, scientists. These physiological effects combine with environmental disruptions to make the life of a frog seem like something out of a horror movie and are likely among the factors causing a decline in amphibian populations worldwide, the researchers said.

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Atrazine Health Effects Atrazine is moderately soluble (30 ppm) in water Low BCF (Kow~10) LOD50 2g/kg Usually cannot be removed by water treatment Only carbon filtration is effective Excessive exposures to people (e.g. farm workers) have shown disturbing links to cancer - EPA has listed it as a possible human carcinogen (evaluations are underway)

EPA Won't Restrict Toxic Herbicide Atrazine, The EPA has decided not to limit one of the nation's most widely used weedkillers, a chemical that, according to several recent studies, threatens human health and the environment. The October 2003 decision -- which the EPA was required to make under a court-approved consent decree reached with NRDC in 2001 -- will allow Syngenta, the main manufacturer of atrazine, and other companies to continue to sell the chemical in the United States with no significant restrictions. Get to know the views of both sides http://www.nrdc.org/health/pesticides/natrazine.asp http://www.epa.gov/oppsrrd1/reregistration/atrazine/

WASHINGTON, DC, February 21, 2005 (ENS) The U.S. Environmental Protection Agency (EPA) is illegally negotiating and brokering regulatory agreements with pesticide manufacturers that are friendly to the industry, according a lawsuit filed by the Natural Resources Defense Council (NRDC).

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Chloroacetamides

Herbicides Alachlor, metachlor and acetochlor represent variation in R1 & R2 Alachlor is carcinogen in animals Chloracetamide undergo hydrolysis in water producing amine and chloroacetic acid O R1R2N-C-CH2Cl +H-OH O R1R2N-H + HO-C-CH2Cl

Both pesticides and degradation products are detected in ground water near corn fields

Phosphonate-based herbicides

Monsanto remains the primary global producer of glyphosate, the active ingredient in Roundup agricultural herbicides. Monsanto's herbicide products include more than 90 glyphosatebased herbicides globally, including Roundup agricultural herbicides and Roundup branded turf and ornamental products. These products can be used to control weeds on the farm, the golf course and in home gardens, create sustainable agricultural systems that preserve top soil, help retain soil moisture, and provide a valuable tool for integrated pest management programs.

http://www.monsanto.com/

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Glyphosate Facts

Structurally similar to organophosphates one of four oxygen is replaced by methylene group, attached to glycine (amino acid) Glyphosate operates by inhibiting synthesis of amino acids containg aromatic ring. This in turn prevents protein synthesis Greater tendency to remain in soil means less chance of runoff Dermal and oral absorption is expected to be small high LD50 values

Phenoxides

Phenoxide ion is reactive towards R-Cl C6H5ONa+ + Cl-R C6H5-O-R + NaCl By employing R-Cl as Cl-CH2-COOH we can obtain phenoxy acetic acid ,,,,,commercial route to large scale production of herbicide

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February 5, 2008

Indiana among top Gulf polluters Study: Midwest farms are responsible for much of the runoff that creates coastal 'dead zone Gannett News Service
WASHINGTON -- Farms in Indiana and eight other states cause most of the pollution that creates a "dead zone" in the Gulf of Mexico, a new government study says. The study by the U.S. Geological Survey also says that manure runoff from pasture, rangeland and feedlots is a bigger contributor to the problem than previously thought. The dead zone, which lies along the coast of Louisiana and Texas, is created in the summer when phosphorus and nitrogen flow out of the Mississippi River and encourage the growth of algae in the Gulf. The algae growth robs the water of oxygen, forcing fish, shrimp, crabs and other sea life from the region. Fertilizer runoff from corn and soybean farms in the Midwest and South is the largest source of nitrogen that reaches the Gulf and a leading source of phosphorus. Scientists worry that production of biofuels will make the problem worse, as farmers increase corn acreage and nitrogen fertilizer to keep up with the demand for ethanol. . "More corn means more fertilizer." Indiana farmers planted 6.5 million acres of corn last year, an 18 percent increase from 2006. In addition to increased production, he said, there are fewer wetlands, which would slow the fertilizer-laden runoff and filter out some of the nutrients before they reach the Gulf.
http://www.indystar.com/apps/pbcs.dll/article?AID=/20080205/LOCAL/802050420

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Agent Orange
Agent Orange is the code name for a powerful herbicide and defoliant used by the U.S. military in its Herbicidal Warfare program during the Vietnam War. Agent Orange is a roughly 1:1 mixture of two phenoxy herbicides in ester form, 2,4dichlorophenoxyacetic acid (2,4-D) and 2,4,5trichlorophenoxyacetic acid (2,4,5-T). Approximately 20 million gallons of herbicides were used in Vietnam between 1962 and 1971 to remove unwanted plant life and leaves which otherwise provided cover for enemy forces during the Vietnam Conflict. Shortly following their military service in Vietnam, some veterans reported a variety of health problems and concerns which some of them attributed to exposure to Agent Orange or other herbicides. (http://www1.va.gov/agentorange/ )

Before

After spraying Agent Orange

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Get to know more about your exposure to pesticides

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