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

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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

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now being phased out • 99% of Americans have detectable levels of HCB 3 .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.

dieldrin. Prior to 1970. Florida. After 1970. lindane.com/watch?v=U8wC-7MYHaw&feature=related 4 .Environmental Contamination at Production Facility …. Orange County. The site covers approximately 4.gov/superfund/sites/npl/nar1425. Florida Federal Register Notice: May 31. (Ortho Division) site is located in Orlando. and storm water. 1994 The Chevron Chemical Co. and aromatic naphtha. A case study http://www. The Chevron Chemical Co.. CHEVRON CHEMICAL CO. and aldrin.39 acres in an industrial area at 3100 Orange Blossom Trail.htm National Priorities List (NPL) Site Narrative for Chevron Chemical Co. mineral oil.youtube.com/publications/the-bhopal-injustice Pesticides that kill Lions _CBS 60 minutes http://www. operated a chemical blending facility for pesticides and other crop sprays between 1950 and 1976. Chemicals used in pesticide formulation included xylene. citric sprays. kerosene. two unlined rinsate ponds onsite were used for the collection and disposal of pesticide formulating rinse water. the pesticide formulating rinsate was collected and disposed of offsite at an unknown location. http://www. barrel rinse water.thenewatlantis. (ORTHO DIVISION) Orlando. A few of the pesticides formulated in large volumes consisted of chlordane. Inc. The facility formulated a variety of liquid and powdered pesticides. and nutritional sprays.epa.

Rachel Carson's Silent Spring.org/health/pesticides/hcarson. and insects ran amuck because chemical pesticides had been banned.org/ DDT. A single application on a crop. killed insects for weeks and months. clearing South Pacific islands of malaria-causing insects for U. exposed nature's vulnerability.had been "silenced" by the insidious effects of DDT. http://www. "If man were to faithfully follow the teachings of Miss Carson. The book's most haunting and famous chapter." complained an executive of the American Cyanamid Company. http://www. and not only the targeted insects but countless more. it first distinguished itself during World War II. the book alarmed readers across America and. the most powerful pesticide the world had ever known. First serialized in The New Yorker in June 1962.The Story of Silent Spring http://www. Developed in 1939. and caused cancer and genetic damage. which in 1962 exposed the hazards of the pesticide DDT. "A Fable for Tomorrow. whose effectiveness is limited to destroying one or two types of insects. questioning Carson's integrity and even her sanity. not surprisingly.from fish to birds to apple blossoms to human children -. DDT was capable of killing hundreds of different kinds at once. Some of the attacks were more personal. eloquently questioned humanity's faith in technological progress and helped set the stage for the environmental movement. DDT's inventor." Monsanto published and distributed 5.nrdc. and the insects and diseases and vermin would once again inherit the earth. while in Europe being used as an effective de-lousing powder.asp 5 . brought a howl of indignation from the chemical industry. Silent Spring: It meticulously described how DDT entered the food chain and accumulated in the fatty tissues of animals. disease.S. Muller.org/health/pesticides/hcarson. Unlike most pesticides. and remained toxic in the environment even after it was diluted by rainwater. troops.asp How a courageous woman took on the chemical industry and raised important questions about humankind's impact on nature.rachelcarson." relating the devastation and inconvenience of a world where famine. was awarded the Nobel Prize in 1948. she wrote." depicted a nameless American town where all life -. Carson concluded that DDT and other pesticides had irrevocably harmed birds and animals and had contaminated the entire world food supply.000 copies of a brochure parodying Silent Spring entitled "The Desolate Year. including human beings.nrdc. "we would return to the Dark Ages.

bad for their own families. 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. in the worst cases. bad for farmers in Latin America and. reveal an environmental problem hidden to consumers. we ensure that fewer and fewer songbirds will return. and the author of “Silence of the Songbirds. Some but not all pesticide residues can be removed by washing or peeling produce. But each year. we take it for granted that the birds’ cheerful songs will fill the air when our apple trees blossom. modern-day canaries in the coal mine. a professor of biology at York University in Toronto.” Migratory birds. 2008 By BRIDGET STUTCHBURY. …… Now that spring is here.Did Your Shopping List Kill a Songbird? March 30. American consumers can discourage this poisoning by avoiding foods that are bad for the environment. as we continue to demand out-of-season fruits and vegetables. but tests by the Centers for Disease Control show that most Americans carry traces of pesticides in their blood. 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? 6 .

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. 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….com /watch?v=LQ64sV0nSV U&feature=related Dichlorodiphenyldichloroethene.leads to thin eggshells -HCl DDT 7 .DDT • Hailed as miraculous during its use in WWII • Found to be effective against the mosquitoes that carry malaria.

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 8 . 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.DDE in Body Fat Solubility in fat and animal tissue has caused accumulation of DDT and DDE in birds.

nytimes.com Biomagnification 25 ppm of fat in the fat of the Cormorants 2 ppm of DDT in Needlefish 0. Variation with age of DDT concentration in Lake Ontario Trout Biomagnification results from a sequence of bioaccumulation steps http://video.5 ppm of DDT in the fat of minnows 0.Biomagnification A chemical whose concentration increases along a food chain is said to be biomagnified.003 ppb of DDT in Long Island seawater 9 .on.04 ppm of DDT in Plankton 0.

The degradation products are water soluble and degrade in the environment.Analogs of DDT The para-chlorines of DDT are replaced in methoxychlor by methoxy groups.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 10 . a mixture of hundreds of similar substances (partially chlorinated camphene. Also the products are excreted rather than accumulated by organisms Other Organochlorine Insecticides • Toxaphene.

bacteria.com/video /#/video/health/2005/10/2 0/cohen.epa. http://www.gov/oppsrrd1/REDs/factsheets/triclosan_fs. diethyl ether.Chlorinated Cyclohexane and Cyclopentadiene Triclosan is a chlorinated aromatic compound which has functional groups representative of both ethers and phenols. and stronger basic solutions such as 1 M sodium hydroxide. but soluble in ethanol. Triclosan is slightly soluble in water. giving it high scores as a risk to both human health and the environment.4-dichlorophenoxy)-phenol 11 .soap. The EPA registers it as a pesticide.cnn ?iref=videosearch http://www.cnn.htm 5-chloro-2-(2. like many other phenols.

the more potent the chemical LOD50 refers to Lethal Oral Dose 12 .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 animal’s 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.

effective protection of children. it is important to know Hazard evaluation information (accute.008 mg http://www.01 mg/kg/day /100) x 80 kg = 0. Since FQPA was enacted.gov/opp00001/regulating/laws/fqpa/index. This additional factor is now standard in dietary risk assessments.epa. the ADI or RfD for a 80 kg man would be (0.01 mg/kg/day. 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.Risk Assessment To perform risk assessment. EPA uses Toxicity reference dose or RfD. already a priority. 13 .htm FQPA dramatically changed the safety standards EPA uses in evaluating potential pesticide risks. received additional emphasis through the addition of an extra tenfold Children's Safety Factor. (RfD is also referred as Acceptable Daily Intake or ADI) RfD (or ADI) = NOEL/100 If NOEL for a chemical is 0. especially to infants and children. unless reliable data support a different factor.

sprays. the greater the tendency to accumulate in that phase …. and in phase x is nx Cx = nx/Vx or nx =Cx. Generally higher the Z value. They are also frequently used as household. are carbamates. These chemicals kill insects and cause poisoning in animals by inhibiting the enzyme. acetylcholinesterase (AChE) which normally functions to degrade acetylcholine in nerve synapses. Chlorpyrifos.ΣZxVx Or f = ntotal /ΣZxVx ….html 14 .purdue.. shampoos and dips. Inhibition of AChE in the nerves results in a buildup of acetylcholine (ACh) and overstimulation of ACh receptors.analogous to equilibrium constant For a given phase (x) fx = Cx/Zx Or Cx= fx .Vx  nx=f. garden. terbufos. diazinon. phorate. foggers. famphur.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.edu/newsletters/1998/summer/organos.Zx. aldicarb.Vx ntotal = f.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. They are all marketed under a wide variety of trade names. parathion. All OP/Carbamate insecticides are fat soluble and therefore are easily absorbed through the skin and then transported throughout the body. and formerly.Zx If total number of moles preset is is ntotal. and malathion are examples of organophosphates while carbofuran. http://www.addl.. and farm insecticides. flea collars. as systemic insecticides. and carbaryl.

Organophosphate Insecticides Unlike organochlorins. organophosphates donot bioaccumulate Decompose within days-weeks after the accumulation.groups are connected through oxygen or sulfur atom 15 . Consumption of organophosphate pesticides by various crops in the US Structurally all organophosphate pesticides contain a central pentavalent P atom and R.

They are degraded rapidly in the environment so persistence is not a problem. for example.The organophosphates. Carbamate Insecticides Carbamate insecticides are inhibitors of acetylcholinesterase. but their action is reversible. especially honeybees.g. are related to the nerve gases developed during World War II. 16 . e. a danger to many useful insects. however. is 30 times more toxic than DDT. They are. Parathion. which is responsible for inactivating acetylcholine (ACh) at neuromuscular junctions and at certain synapses in the central and peripheral nervous systems. 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. Some other examples: malathion diazinon phosmet (Imidan®) chlorpyrifos (Lorsban®) Some of the organophosphates are very toxic.. causing hundreds of deaths. parathion. Each year organophosphates poison thousands of humans throughout the world. They react irreversibly with the enzyme acetylcholinesterase.

Natural degradation in water is slow (6-170 days). to name a few. and Weedone (Union Carbide). chrysanthemum -Paralyze insects but do not strong enough to kill them -Synthetic pyretrins are called pyrethroids -Common ingredients in domestic insecticides Herbicides • • Selective herbicide.000 tons of 2.4-D are utilized in the US each year. effective in killing many broadleaf plants. • Cl O CH 2 CO 2 H Cl • 2. Fernoxone (ICI). Over 30.Pesticides from Natural Sources -Obtained from flowers. Marketed under many different names: Weed-BGon (Chevron).4-Dichlorophenoxyacetic acid 17 .

About 80 percent of this quantity is used in agriculture. Giffex 4L. Farmco Atrazine. Simazat. Atranex. and many other purposes. In many respects. G-30027. the greatest potential for unintended adverse effects of pesticides is through contamination of the hydrologic system. 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. insects. Atrataf. Trade or generic names: Aatrex. diarrhea and vomiting. Aktikon. irrigation. Malermais. and other organisms. Atred. Azinotox. and by inhalation.water.usgs. and other crops. sugarcane.herbicide used to control broadleaf and grassy weeds Toxicity: Atrazine is slightly to moderately toxic to humans and other animals. and Zeapos Use: Selective triazine .Pesticides in the Hydrologic System About 1 billion pounds of pesticides are used each year in the United States to control weeds. Crisazina. christmas trees. Atratol.S. Gesaprim. sorghum. dermally. Alazine. Symptoms of poisoning include abdominal pain. Primatol. and skin reactions 18 . pineapple. and in conifer reforestation plantings. which supports aquatic life and related food chains and is used for recreation. Although the use of pesticides has resulted in increased crop production and other benefits. Over 64 million acres of cropland were treated with atrazine in the U.gov/pnsp/rep/fs09200/ TRIAZINES Atrazine is a selective triazine herbicide used to control broadleaf and grassy weeds in corn. drinking water. irritation of mucous membranes. in 1990. It can be absorbed orally. it has raised concerns about potential adverse effects on the environment and human health. eye irritation.

but is making them more prone to deadly bacterial meningitis.com/en/media/multimedia-downloads.2 billion. Berkeley. according to a new study by University of California.syngenta.Largest producer of Atrazine based herbicides Sales in 2008 were approximately $9.edu/news/media/releases/2006/02/02_pesticides. the researchers said. http://www.com/en/index. 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.aspx Video http://www.syngenta.shtml Pesticide combinations imperil frogs By Robert Sanders.berkeley. 19 .html# http://www. 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.

and other companies to continue to sell the chemical in the United States with no significant restrictions. 20 .nrdc. according a lawsuit filed by the Natural Resources Defense Council (NRDC).g.EPA has listed it as a possible human carcinogen (evaluations are underway) EPA Won't Restrict Toxic Herbicide Atrazine. a chemical that.S. The October 2003 decision -. Get to know the views of both sides http://www.gov/oppsrrd1/reregistration/atrazine/ WASHINGTON.asp http://www. threatens human health and the environment.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. according to several recent studies. 2005 (ENS) The U. The EPA has decided not to limit one of the nation's most widely used weedkillers.which the EPA was required to make under a court-approved consent decree reached with NRDC in 2001 -.epa. DC. the main manufacturer of atrazine. farm workers) have shown disturbing links to cancer . February 21.will allow Syngenta.org/health/pesticides/natrazine. Environmental Protection Agency (EPA) is illegally negotiating and brokering regulatory agreements with pesticide manufacturers that are friendly to the industry.

and provide a valuable tool for integrated pest management programs. including Roundup agricultural herbicides and Roundup branded turf and ornamental products. These products can be used to control weeds on the farm. the active ingredient in Roundup® agricultural herbicides.monsanto. help retain soil moisture. create sustainable agricultural systems that preserve top soil.com/ 21 . 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. http://www. Monsanto's herbicide products include more than 90 glyphosatebased herbicides globally.Chloroacetamides Herbicides Alachlor. the golf course and in home gardens.

. attached to glycine (amino acid) • Glyphosate operates by inhibiting synthesis of amino acids containg aromatic ring..Glyphosate Facts • Structurally similar to organophosphates –one of four oxygen is replaced by methylene group.. 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 C6H5ONa+ + 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 22 .

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In addition to increased production.dll/article?AID=/20080205/LOCAL/802050420 24 .indystar. as farmers increase corn acreage and nitrogen fertilizer to keep up with the demand for ethanol. a new government study says. there are fewer wetlands. forcing fish. 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." Indiana farmers planted 6.5 million acres of corn last year.Farms in Indiana and eight other states cause most of the pollution that creates a "dead zone" in the Gulf of Mexico. The dead zone.February 5. "More corn means more fertilizer. an 18 percent increase from 2006. Scientists worry that production of biofuels will make the problem worse. which would slow the fertilizer-laden runoff and filter out some of the nutrients before they reach the Gulf.com/apps/pbcs. rangeland and feedlots is a bigger contributor to the problem than previously thought. The study by the U.“ http://www. 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. shrimp. Geological Survey also says that manure runoff from pasture. crabs and other sea life from the region. The algae growth robs the water of oxygen. 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 -. he said.S. ….

5trichlorophenoxyacetic acid (2. 2.4. 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.S.4-D) and 2. (http://www1.4.Agent Orange Agent Orange is the code name for a powerful herbicide and defoliant used by the U. Shortly following their military service in Vietnam.4dichlorophenoxyacetic acid (2. some veterans reported a variety of health problems and concerns which some of them attributed to exposure to Agent Orange or other herbicides.5-T). military in its Herbicidal Warfare program during the Vietnam War.va.gov/agentorange/ ) Before…… After spraying Agent Orange…… 25 . Agent Orange is a roughly 1:1 mixture of two phenoxy herbicides in ester form.

Get to know more about your exposure to pesticides 26 .

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