E X T O X N E T: Chlorpyrifos
E X T O X N E T: Chlorpyrifos
PMEP Home Page Pesticide Active Ingredient Information EXTOXNET: The Extension Toxicology Network Carbaryl to Dicrotophos Chlorpyrifos
                                                 E  X  T  O  X  N  E  T
                                                           Extension Toxicology Network
          A Pesticide Information Project of Cooperative Extension Offices of Cornell University, Michigan State University, Oregon
           State University, and University of California at Davis. Major support and funding was provided by the USDA/Extension
                                     Service/National Agricultural Pesticide Impact Assessment Program.
                Pesticide                                                            Chlorpyrifos
                Information
                Profile                                                                Publication Date: 9/93
          REGULATORY STATUS
          The EPA has established a 24-hour reentry interval for entering crop areas treated with emulsifiable
          concentrate or wettable powder formualtions of chlorpyrifos without protective clothing (40).
          Products containing chlorpyrifos must bear the signal word "Warning" or "Caution," depending on
          the toxicity of the formulation (46). Check specific state regulations for local restrictions which may
          apply.
          INTRODUCTION
          Chlorpyrifos is a broad spectrum insecticide, a chemical used to kill a wide variety of insects. It was
          introduced in 1965 (45). While originally used primarily to kill mosquitoes in the immature, larval
          stage of development, chlorpyrifos is no longer registered for this use. Chlorpyrifos is effective in
          controlling a variety of insects, including cutworms, corn rootworms, cockroaches, grubs, flea
          beetles, flies, termites, fire ants, and lice (38). It is used as an insecticide on grain, cotton, field, fruit,
          nut and vegetable crops, and well as on lawns and ornamental plants (40, 2). It is also registered for
          direct use on sheep, turkey, for horse site treatment, for treatment of dog kennels, and for domestic
          dwellings, farm buildings, storage bins, and commercial establishments (40). Chlorpyrifos is
          available in emulsifiable concentrate, dust, flowable, pellet, spray, granular and wettable powder
          formulations (46).
          Chlorpyrifos acts on pests primarily as a contact poison, with some action as a stomach poison. It is a
          nonsystemic contact chemical, meaning that it is acts only where it comes into direct contact with
          plant tissues, and is not transported to other plant parts.
TOXICOLOGICAL EFFECTS
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          ACUTE TOXICITY
          Chlorpyrifos is moderately toxic to humans (50). Poisoning from chlorpyrifos may affect the central
          nervous system, the cardiovascular system, and the respiratory system (31). It is also a skin and eye
          irritant (49). While some organophosphates are readily absorbed through the skin, studies in humans
          suggest that skin absorption of chlorpyrifos is more limited (45). Skin which has come in contact
          with this material should be washed immediately with soap and water and all contaminated clothing
          should be removed. The acute dermal LD50 for chlorpyrifos in male and female rats is greater than
          2,000 mg/kg (53).
          Three hundred and nineteen human exposure incidents were reported by the Pesticide Incident
          Monitoring System (PIMS) from 1970 through 1981, most resulting from inhalation and dermal
          exposure. Three human deaths were caused by chlorpyrifos and/or chlorpyrifos combined with other
          active ingredients (41). Persons with respiratory ailments, recent exposure to cholinesterase
          inhibitors, cholinesterase impairment, or liver malfunction are at increased risk from exposure to
          chlorpyrifos.
          The organophosphate insecticides are cholinesterase inhibitors which may be absorbed through all
          routes of exposure. When toxic amounts are inhaled, the first effects are usually respiratory and may
          include bloody or runny nose, coughing, chest discomfort, difficult or short breath, and wheezing due
          to constriction or excess fluid in the bronchial tubes. Skin contact with organophosphates may cause
          localized sweating and involuntary muscle contractions. Eye contact may cause pain, bleeding, tears,
          pupil constriction, and blurred vision. Following exposure by any route, other systemic effects may
          begin within a few minutes or be delayed for up to 12 hours. These may include pallor, nausea,
          vomiting, diarrhea, abdominal cramps, headache, dizziness, eye pain, blurred vision, constriction or
          dilation of the eye pupils, tears, salivation, sweating, and confusion. Severe poisoning will affect the
          central nervous system, producing incoordination, slurred speech, loss of reflexes, weakness, fatigue,
          involuntary muscle contractions, twitching, tremors of the tongue or eyelids, and eventually paralysis
          of the body extremities and the respiratory muscles. In severe cases there may also be involuntary
          defecation or urination, psychosis, irregular heart beats, unconsciousness, convulsions and coma.
          Death may be caused by respiratory failure or cardiac arrest (39).
          Some organophosphates may cause delayed symptoms beginning 1 to 4 weeks after an acute
          exposure which may or may not have produced immediate symptoms. In such cases, numbness,
          tingling, weakness and cramping may appear in the lower limbs and progress to incoordination and
          paralysis. Improvement may occur over months or years, and in some cases residual impairment will
          remain (39).
          Since chlorpyrifos is absorbed through the skin, especially through cuts and scratches, dermal
          contact should be avoided (40). In addition to causing inhibition of cholinesterase, acute exposure to
          chlorpyrifos may cause skin irritation. Absorption through the skin may result in systemic
          intoxication, or general poisoning in a bodily system. The severity of poisoning will determine the
          amount and range of symptoms which are experienced (31).
          Inhalation of chlorpyrifos may cause absorption of the insecticide through the mucous membranes,
          resulting in systemic intoxication (31). Plasma cholinesterase levels activity has been shown to be
          inhibited when chlorpyrifos particles are inhaled (1).
          The amount (dose) of a material that causes death in one-half (50%) of the test population, when it is
          given on a short-term basis by mouth is referred to as its oral lethal dose (LD50). The oral LD50 for
          chlorpyrifos in rats is 82 to 270 milligrams per kilogram (mg/kg) (21, 41, 2). This indicates that it
          takes 82 to 270 mg of chlorpyrifos for each kg of body weight to kill 50 percent of the experimental
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          animals tested (14, 49). The LD50 for chlorpyrifos in mice is 60 mg/kg, 1000 mg/kg in rabbits, 32
          mg/kg in chickens, 500 to 504 mg/kg in guinea pigs, and 800 mg/kg in sheep (2, 14, 17, 49). The
          dermal LD50 in rats is greater than 2000 mg/kg (53), and 1000 to 2000 mg/kg in rabbits (2, 17).
          The lethal concentration fifty, or LC50, is that concentration of a chemical in air or water that kills
          half of the experimental animals exposed to it for a set time period. The 4-hour inhalation LC50 for
          chlorpyrifos in rats is greater than 200 mg/m3 (54).
          CHRONIC TOXICITY
          Repeated or prolonged exposure to organophosphates may result in the same effects as acute
          exposure including the delayed symptoms. Other effects reported in workers repeatedly exposed
          include impaired memory and concentration, disorientation, severe depressions, irritability,
          confusion, headache, speech difficulties, delayed reaction times, nightmares, sleepwalking and
          drowsiness or insomnia. An influenza-like condition with headache, nausea, weakness, loss of
          appetite, and malaise has also been reported (49).
          When technical chlorpyrifos was fed to dogs at doses of 0.01, 0.03, 0.1, 1 and 3 mg/kg/day for 2
          years, increased liver weight occurred at 3.0 mg/kg. Signs of cholinesterase inhibition occurred at 1
          mg/kg. Rats and mice given technical chlorpyrifos in the diet for 104 weeks showed no adverse
          effects other than cholinesterase inhibition (50). An occupational study on 22 pest control operators
          exposed to an 8 hour level of 27.6 microgram per cubic meter (ug/m3) of Dursban showed inhibition
          of plasma cholinesterase when compared to a control group of the same age and sex (37). A
          measurable change in plasma and red blood cell cholinesterase levels was seen in spray workers
          exposed to 0.5% chlorpyrifos emulsion in field trials for malaria control. Human volunteers who
          ingested 0.1 mg/kg of chlorpyrifos daily for four weeks showed significant plasma cholinesterase
          inhibition (1). A low blood cholinesterase level can sometimes persist from two to six weeks with
          long-term exposure to chlorpyrifos (31).
          Two-year feeding studies of 1 and 3 mg/kg/day of chlorpyrifos to rats produced moderate depression
          of plasma and red blood cell cholinesterase. Brain cholinesterase was decreased with the larger dose.
          Cholinesterase levels recovered when the experimental feeding was discontinued (18). Identical
          results occurred in a 2-year feeding study with dogs. No long-term health effects were seen in either
          the dog or rat study (1, 45). In some animal species, chlorpyrifos may produce neurotoxicity, or harm
          to nerve tissue (14).
Reproductive Effects
          EPA has determined that chlorpyrifos does not adversely affect reproduction (40, 50). In two studies
          reviewed by the EPA, no effects were seen in the animals tested at dose levels up to 1.2 mg/kg/day
          (40). No effects on reproduction occurred in a 3-generation study with rats fed dietary doses as high
          as 1 mg/kg/day (1, 50). In another study in which rats were fed 1.0 mg/kg/day for two generations,
          the only effect observed was a slight increase in the number of deaths of newborn offspring (18).
          Once in the bloodstream, chlorpyrifos may cross the placenta (49).
Teratogenic Effects
          EPA has determined that chlorpyrifos is not teratogenic. No teratogenic or other adverse effects to
          offspring were found when pregnant rats were fed doses as high as 15 mg/kg/day for 10 days. When
          pregnant mice were given doses of 1, 10 or 25 mg/kg/day for 10 days, minor skeletal variations and a
          decrease in fetal length occurred at the highest dose tested. The developmental NOEL was 10
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          mg/kg/day (35, 40, 50). No birth defects were seen in the offspring of male and female rats fed 1.0
          mg/kg per day during a three-generation reproduction and fertility study (18, 1).
Mutagenic Effects
          EPA has determined that chlorpyrifos is not mutagenic. No evidence of mutagenicity was found in
          any of 4 tests reviewed by EPA (50). Mutagenic effects were observed in fruit flies given oral
          concentrations of 50 parts per billion (ppb) of chlorpyrifos for 3 days (27).
Carcinogenic Effects
          EPA has determined that chlorpyrifos is not carcinogenic. There was no increase in the incidence of
          tumors when rats were fed 10 mg/kg/day for 104 weeks nor when mice were fed 2.25 mg/kg for 105
          weeks (50).
Organ Toxicity
          Chlorpyrifos primarily affects the nervous system through inhibition of cholinesterase, an enzyme
          required for proper nerve functioning.
          In humans, chlorpyrifos and its principal metabolites are eliminated relatively rapidly following a
          single dose (30). It is readily absorbed into the bloodstream through the gastrointestinal tract if it is
          ingested, through the lungs if it is inhaled, or through the skin if there is dermal exposure (40).
          After a single oral dose, its half-life in the blood appears to be about one day (29). Chlorpyrifos was
          found in its original form in the blood, brain and liver of a 61-year old man who lived only one day
          after accidentally eating this material (18).
          Chlorpyrifos is eliminated primarily through the kidneys in urine (38). Following oral intake of
          chlorpyrifos by rats, 90% was removed in the urine and 10% was excreted in the feces (17). It is
          detoxified quickly in rats, dogs and other animals (44). The major metabolite found in rat urine after
          administration of a single oral dose of 0.5 or 25 mg/kg was TCP. TCP does not inhibit cholinesterase
          and it is not mutagenic (50). Following intake, some chlorpyrifos becomes stored in fat tissues. It is
          eventually moved out of the fat tissue and eliminated from the body, with a half-life of about 62
          hours (18, 45).
          Research indicates that chlorpyrifos does not build up or persist in body tissues. It does not have a
          significant bioaccumulation potential (29). When formulated chlorpyrifos (Dursban) was fed to
          cows, unchanged pesticide was found in the feces, but not in the urine or milk (37). Chlorpyrifos was
          detected in the milk of cows for 4 days following spray dipping with a 0.15% emulsion. The
          maximum concentration in the milk was 0.304 ppm. This concentration was decreased by 26 to 47%
          by pasteurization (45). In a rat study, chlorpyrifos did not accumulate in any tissue except fat (26).
          Residues of granular formulations of chlorpyrifos were found in salt marsh snails immediately after
          they were treated with the material and for up to five weeks after treatment. When an emulsion
          formulation was used, residues were found immediately following treatment, and for up to 3 weeks
          afterwards (23).
ECOLOGICAL EFFECTS
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          The US EPA requires precautionary language on chlorpyrifos product labels, warning of the hazard
          that this insecticide poses to birds, wildlife and aquatic organisms. It should not be applied directly to
          water. Drift and runoff from treated areas may be hazardous to aquatic organisms in adjacent aquatic
          sites (2, 40).
Effects on Birds
          Chlorpyrifos is moderately to very highly toxic to birds (50). Its oral LD50 in pheasants is 8.41
          mg/kg, 112 mg/kg in mallard ducks, 21.0 mg/kg in house sparrows, and 32 mg/kg in chickens (17,
          37, 50). The LD50 for a granular product (15G) in bobwhite quail is 108 mg/kg (50).
          Two one-generation reproductive studies resulted in NOELs of 125 ppm (the highest dose tested) for
          bobwhite quail and 25 ppm for mallard ducks. At 125 ppm, mallards laid significantly fewer eggs
          (50).
          There was no evidence of changes in weight gain, or in the number, weight and quality of eggs
          produced by hens fed dietary levels of 50 parts per million (ppm), or about 5.12 mg/kg, of
          chlorpyrifos (18). Bird deaths have not been observed in repeated mosquito control efforts (17).
          Chlorpyrifos is very highly toxic to freshwater fish, aquatic invertebrates and estuarine and marine
          organisms (50). Cholinesterase inhibition was observed in acute toxicity tests of fish exposed to very
          low concentrations of this insecticide (29). Precautions and restrictions are being imposed by EPA to
          decrease potential hazards (40). Application of concentrations as low as 0.01 pounds of active
          ingredient per acre may cause fish and aquatic invertebrate deaths (50).
          Chlorpyrifos accumulates in the tissues of aquatic organisms. Studies involving continuous exposure
          of fish during the embryomic through fry stages have shown BCF values of 58 to 5100 (52).
          Chlorpyrifos toxicity to fish may be related to water temperature. Its 96-hour LC50 varied in rainbow
          trout from 7.1 micrograms per liter (ug/l) to 51 ug/l at three different temperatures (34). The 24-hour
          LC50 for chlorpyrifos in goldfish is 180 ug/l, and less than 1,000 ug/l in mosquito fish (46). The 96-
          hour LC50 for chlorpyrifos in mature rainbow trout is 9 ug/l, 98 ug/l in lake trout, 806 ug/l in
          goldfish, 10 ug/l in bluegill, and 331.7 ug/l in fathead minnow (38).
          Due to its high acute toxicity and its persistence in sediments, chlorpyrifos may represent a hazard to
          sea bottom dwellers (34). Smaller organisms appear to be more sensitive than larger ones (38).
          When fathead minnows were exposed to Dursban for a 200-day period during which they
          reproduced, the first generation of offspring had decreased survival and growth, as well as a
          significant number of deformities. This occurred at approximately 2.68 microgram per liter (ug/l)
          exposure for a 30 day-period (37).
          Aquatic and general agricultural uses of chlorpyrifos may be extremely poisonous to wildlife and
          honeybees (40, 17). Treated areas should not be used for grazing, nor should the chemical be used
          when bees are actively collecting pollen or nectar (2, 25, 36). Studies indicate that with continuous
          exposure over time, chlorpyrifos may accumulate to toxic levels in test animals (36).
While one study did not detect any negative effect to nontarget insects when chlorpyrifos was
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          applied to rice fields at 0.01 to 0.02 kilogram per hectare (kg/ha), another study reported that
          practically all nontarget insects died after a similar application (15).
          ENVIRONMENTAL FATE
          Chlorpyrifos is moderately persistent, but relatively immobile in the environment (50). Chlorpyrifos
          may bioconcentrate at very low levels in ecological systems (BCF = 2.50 to 3.54) (48).
          Chlorpyrifos adsorbs strongly to soil particles and it is not readily soluble in water (47, 52). It is
          therefore immobile in soils and unlikely to leach or to contaminate groundwater (32, 50, 52). It is not
          mobile in sandy loam and loamy sand soils (41). TCP, the principle metabolite of chlorpyrifos,
          adsorbs weakly to soil particles and appears to be moderately mobile and persistent in soils. EPA has
          required additional testing to determine the environmental fate of TCP (50).
          In aerobic soils, the soil half-life of chlorpyrifos was from 11 to 141 days in seven soils ranging in
          texture from loamy sand to clay and with soil pHs from 5.4 to 7.4. Chlorpyrifos was less persistent in
          the soils with a higher pH. Soil half-life was not affected by soil texture or organic matter content. In
          anaerobic soils, the half-life was 15 days in loam and 58 days in clay soil (50). Adsorbed
          chlorpyrifos is subject to degradation by UV light, chemical hydrolysis and by soil microbes. When
          treated on moist soils, the volatility half-life of chlorpyrifos was 45-163 hours, with 62-89% of the
          applied chlorpyrifos remaining on the soil after 36 hours. In another study, 2.6 and 9.3% of the
          chlorpyrifos applied to sand or silt loom soil remained after 30 days (52). The half-life of
          chlorpyrifos in soil, or the time that it takes for half of the insecticide to be broken down, is usually
          between 60 and 120 days, but can range from 2 weeks to over 1 year, depending on the soil type,
          climate and other conditions (17, 40, 48).
          The current label for this material states that it is not to be applied directly to bodies of water. In open
          waters, the concentration and persistence of chlorpyrifos will vary depending on the type of
          formulation. For example, immediately after entering open waters, emulsifiable concentrates and
          wettable powders tend to produce a large increase in chlorpyrifos concentrates in water. As the
          pesticide adheres, or (adsorbs) to sediments and suspended organic matter, however, concentrations
          rapidly decline. Granules and controlled- release formulations do not produce as rapid an increase in
          the concentration of insecticide in the water, but the resulting concentration persists longer (38).
          Slow desorption from sediments can also maintain low (ppb) residual concentrations of chlorpyrifos
          in open waters for long periods of time (48).
          Chlorpyrifos enters freshwater and saltwater ecosystems primarily as spray drift. It is also carried on
          eroded soil particles from treated areas (38). If soil with adsorbed chlorpyrifos is carried by runoff,
          surface water may be contaminated (32).
          In water, chlorpyrifos readily adsorbs to suspended sediment and bottom materials. Volatilization is
          probably the primary route of loss of chlorpyrifos from water. Volatility half-lives of 3.5 and 20 days
          have been estimated for pond water (52). The photolysis half-life of chlorpyrifos is 3 to 4 weeks
          during midsummer in the U.S., but photodegradation of chlorpyrifos is not expected to be significant
          in deep waters, during winter, or in waters which sunlight can not penetrate (48). Its change into
          other natural forms (biotransformation) is slow (34). Research suggests that this insecticide is
          unstable in water, and the rate at which it is hydrolyzed increases with temperature, decreasing by 2.5
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          to 3-fold with each 10 degrees C drop in temperature. The rate of hydrolysis is constant in acidic to
          neutral waters, but increases in alkaline waters. In water at pH 7.0 and 25 degrees C, it had a half-life
          of 35 to 78 days (48). The half-life of chlorpyrifos in water of an unknown pH was about 80-100
          days (37).
          Chlorpyrifos may be toxic to some plants, such as head lettuce (23). Residues remain on plant
          surfaces for approximately 10-14 days (36, 16). Data indicate that this insecticide and/or its soil
          metabolites, can accumulate in certain crops (41).
          Information is limited on chlorpyrifos toxicity to freshwater plants, although algal blooms frequently
          follow its field application (38).
          Chlorpyrifos is corrosive to copper and brass (17). It is compatible with most fungus-killing
          chemicals (fungicides) and other insecticides (16). Chlorpyrifos is stable in neutral or acidic aqueous
          solutions. Non-aqueous solutions of chlorpyrifos can be stored indefinitely under appropriate storage
          conditions. It is, however, unstable under alkaline conditions (18, 41).
          Technical-grade chlorpyrifos has generally been found to be more toxic than an equal amount of
          active ingredient in a formulated product. The effects of inert ingredients can not, therefore, be
          ignored (38). Avoid eye and skin contact with chlorpyrifos as well as inhalation of its vapors, dusts,
          or sprays (17). A pesticide face mask (respirator) is recommended (2). Chlorpyrifos should not be
          used near water (17).
          Persons who work with organophosphate materials for long periods of time should have frequent
          blood tests of their cholinesterase levels. If the cholinesterase level falls below a critical point, no
          further exposure should be allowed until it returns to normal (51).
          Protective clothing must be worn when handling chlorpyrifos. Before removing gloves, wash them
          with soap and water. Always wash hands, face and arms with soap and water before smoking, eating
          or drinking.
          After work, remove all work clothes and shoes. Shower with soap and water. Wear only clean clothes
          when leaving the job. Wash contaminated clothing and equipment with soap and water after each
          use. Keep contaminated work clothes separate from regular laundry.
Exposure Guidelines:
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Chlorpyrifos                                                    http://pmep.cce.cornell.edu/profiles/extoxnet/carbaryl-dicrotopho...
Physical Properties:
          CAS #:          2921-88-2
          Specific gravity:
                          1.398 at 43 degrees C (49)
          H2O solubility: low; 2 ppm at 35 degrees C (29, 18, 23); 2 ppm water at 2 degrees C (44)
          Solubility in   In benzene 790, acetone 650, chloroform 630, carbon disulfide 590, diethyl ether
          other solvents: 510, xylene 645, methylene chloride 714, isooctane 79, methanol 45 (all in g/100
                          g at 25 degrees C) (17)
          Melting Point: 41.5 to 44 degrees C (106 to 108 degrees F) (52)
          Flash point:    greater than 200 degrees F (54).
          Vapor pressure: 1.87 x 10 to the minus 5 power mm Hg at 25 degrees C (35b)
          Kow:            66,000 at 23 degrees C (29)
          BASIC MANUFACTURER
          DowElanco
          9002 Purdue Rd.
          Indianapolis, IN 46268-1189
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