Chlorpyrifos in freshwater and marine water

​​Toxicant default guideline values for protecting aquatic ecosystems

October 2000

Description of chemical

Organophosphorus pesticides are derivatives of phosphoric, phosphonic, phosphorothioic, or phosphonothioic acids, comprising many chemicals with a wide range of uses (WHO 1986). They exert their acute effects in insects, fish, birds and mammals by inhibiting the acetylcholinesterase (AChE) enzyme, but may also have a direct toxic effect (WHO 1986).

Chlorpyrifos (CAS 2921-88-2) is a phosphorothioate organophosphorus (OP) pesticide, developed by DowElanco, with a non-systemic mode of action through contact ingestion or breathing vapour (Tomlin 1994). Its IUPAC name is O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate, formula is C₉H₁₁Cl₃NO₃PS and molecular weight is 350.6. Chlorpyrifos is only slightly soluble in water to 1.4 mg/L at 25°C (Tomlin 1994) and its log K_ow is 4.7 (Tomlin 1994). The current analytical practical quantitation limit (PQL) for chlorpyrifos in water is 0.1 µg/L (NSW EPA 2000).

Uses and environmental fate

Chlorpyrifos has a wide range of insecticidal uses against Diptera (two-winged flies and mosquitoes), Homoptera, Coleoptera (beetles), Lepidoptera (moths), Isoptera, Blattelidae (cockroaches), Muscidae, in a wide variety of locations. In Australia, chlorpyrifos has over 1200 registered uses, on around 100 crops (NRA 1997a), including cotton, wheat, vegetables and fruit, as well as an insecticide in pasture, machinery, stored grain and hides, turf plus home, garden and pet uses. An important use of chlorpyrifos is against subterranean termites (NRA 1997a), where it replaced the persistent organochlorine pesticides, and it is one of the most widely used insecticides in Australia.

Chlorpyrifos degrades more rapidly in alkaline pH and the DT₅₀ varies from 1.5 d at pH 8 (25°C) to 100 days at pH 7 (15°C) (Tomlin 1994). Racke (1993) has reviewed the environmental fate of chlorpyrifos, including a number of field studies. Chlorpyrifos at overspray levels dissipated completely within 21-30d in ponds and estuaries. Sediments contributed to most of the persistence, as it was removed rapidly from the water column. It degrades in the presence of copper and other chelating metals. Bioconcentration factors for fish continuously exposed to chlorpyrifos from embryonic to juvenile stages varied from 58 to 5100 (Racke 1993). NRA (2000) reviewed the environmental risk of chlorpyrifos and reported BCF figures to fish up to 1400. However, it was reported that depuration was rapid (≤ 2 days) in clean water.

Environmental toxicology

As an OP pesticide, chlorpyrifos inhibits the acetylcholinesterase (AChE) enzyme in organisms. The oxon metabolite (from initial oxidation of the P=S bond) is more toxic. Chlorpyrifos had very high toxicity to most groups except marine molluscs and algae. Barron and Woodburn (1995) have reviewed the ecotoxicology of chlorpyrifos. Invertebrates are most sensitive to chlorpyrifos.

Freshwater fish: 16 species, 48 to 96-hour LC50 of 1.3 (Cyprinus carpio) to 542 µg/L, although outlying figures were reported for Ictalurus (806 to 810 µg/L) and Gambusia (1018 µg/L) (lower figures for both species were included in the 16 species). Chronic NOEC for Pimephales promelas: 32 to 216-day mortality (0.63 to 3.2 µg/L); 30-day development (1.3 µg/L); 7 to 136-day growth (0.012 to 3.900 µg/L; geometric mean = 0.63 µg/L: the 0.012 µg/L figure may be anomalous, as several other figures for the same species and test duration of 1.2 µg/L were reported); 200 to 216-day reproduction (0.27-1.2 µg/L; geometric mean = 0.57 µg/L).

Freshwater crustaceans: 14 species, 48 to 96-hour LC50 or EC50 immobilisation, 0.06 to 6.00 µg/L, although outlying figures were reported for crayfish Procambarus clarki of 21-23 µg/L and the crab, Oziotelphusa senex senex, of 300 to 700 µg/L. Geometric means for the sensitive species were 0.08 µg/L (Gammarus pulex), 0.12 µg/L (Ceriodaphnia dubia), 0.13 µg/L (Hyalella azteca), 0.14 µg/L (G. lacustris), 0.21 µg/L (G. pseudolimnaeus), 0.3 µg/L (Daphnia longispina). Cladocerans (water fleas) were most sensitive. Chronic NOEC figures for two species; D. magna, 21-day reproduction, 0.056 µg/L and mortality of 0.06 to 1.00 µg/L, giving an ACR of 10; D. pulex, 25-day reproduction 0.065 µg/L. A 10-day mortality NOEC for H. azteca (amphipod) was 0.09 µg/L.

Freshwater insects: 13 species, 48 to 96-hour LC50 of 0.2 to 10.0 µg/L. 11 species had LC50 values below 1 µg/L. A 9-day LC50 of 0.97 µg/L was reported for Neopleas striola (backswimmer).

Freshwater molluscs: one species; 96-hour LC50 of 2.7 µg/L.

Freshwater rotifer: one species, 48-hour LC50 of 360 µg/L [outlying figure of 12,000 µg/L, AQUIRE (1994). Branchionus calyciflorus had a 72-hour NOEC reproduction of 200 µg/L.

Freshwater ciliate: NOEC, growth, 72 hours for Tetrahymena, 330 µg/L.

Freshwater algae: six species, 7-day NOEC (growth) of 10-100 µg/L.

Marine fish: 10 species, 48 to 96-hour LC50 of 0.25-7 µg/L. [Outlying figures for three additional species: Cyprinodon variegatus (140 to 270 µg/L); Fundulus sp. (470 µg/L); and Opsanus beta (68 to 520 µg/L).]

Marine crustaceans: seven species, 48 to 96-hour LC50 of 0.035 to 5.400 µg/L. NRA (2000) reported a NOEC for growth impairment of 0.0046 µg/L for a mysid.

Marine molluscs: one species, Crassostrea gigas, 48 hours, growth and development of 34 to 2000 µg/L.

Marine algae: three species, 48 to 96-hour EC50 (growth) of 140 to 300 µg/L, although 48-day NOEC (growth) on six species was 1200 to 10,000 µg/L.

Mesocosm studies: Up to 27 mesocosm studies have been reported on chlorpyrifos. Unfortunately, most of these did not satisfy the criteria for acceptance of mesocosm data, and only eight could be considered for an initial investigation. The problem with many of these eight was insufficient number of treatments and/or insufficient replication, as well as insufficient breadth of taxa. For some, the lowest concentration produced an effect, giving a LOEC but not a NOEC figure. LOEC figures reported for zooplankton were 5 µg/L (Mani & Konar 1988); 1.7 µg/L (Lucassen & Leeuwangh 1994); 1.5 µg/L (Roberts et al. 1973); 0.5 µg/L (Brazner et al. 1989) and 0.37 µg/L (Nelson & Evans 1973). Other studies produced LOEC values: phytoplankton (1.2 µg/L; Brown et al. 1976); for insect colonisation, caddis abundance and fish mortality (1.15 µg/L; Macek et al. 1972); for transient reduction in bug abundance (0.03 µg/L; Giddings 1993, Biever et al. 1994); and for elevated community respiration (0.004 µg/L; Butcher et al. 1977).

Three studies produced NOEC figures: 0.06 µg/L (after pulse exposure to stream macroinvertebrates) (Pusey et al. 1994); 0.065 µg/L for D. pulex in ponds (van Wijngaarden & Leeuwangh 1989); and 0.1 µg/L for overall community effects for zooplankton and macroinvertebrates in ditches (van den Brink et al. 1996). These are similar to the chronic NOECs for invertebrates. At this stage, it was not considered appropriate to use these data to derive a guideline figure, although the figure derived from the laboratory data is 6 to 10-fold lower than the lowest of those mesocosm NOECs.

Australian and New Zealand data

The only Australian dose-response data was for the waterflea C. dubia, with a 48-hour LC50 of 0.25 µg/L, which is similar to data for other cladocerans. Abdullah et al. (1993) found that a concentration of 1 µg/L was lethal to the shrimp Paratya australiensis in 24 hours but 0.1 µg/L reduced AChE levels by 28%. Exposure to 0.05 µg/L for 28 days resulted in moribund shrimp with acetyl cholinesterase (AChE) depression over 85%. Repeat exposures to 0.1 µg/L at 7-day intervals gave increased AChE depression.

Factors that effect toxicity

Toxicity of chlorpyrifos to Oncorhynchus mykiss and P. promelas increased 2 to 15 times with a 16°C increase in temperature (Johnson & Finley 1980). Toxicity of chlorpyrifos to cutthroat trout, Salmo clarki, increased by 3 times when the pH was increased from 7.5 to 9.0 (Johnson & Finley 1980). Patra et al. (1995a) found almost a four-fold increase in the 96-hour LC50 to the silver perch, Bidyanus bidyanus, over the range of 15 to 35 ⁰C. LT50 values for three species of Australian fish exposed to 1.5 µg/L chlorpyrifos decreased at 35°C. Critical thermal maximum temperatures for three Australian fish species (Patra et al. 1995b) decreased significantly for fish exposed to sublethal levels (3.5 to 5.0 µg/L) of chlorpyrifos.

Naddy et al. (2000) reported that chlorpyrifos toxicity to D. magna varied with exposure duration and intervals between pulses. Daphnids exposed to two 12-hour pulses of chlorpyrifos at 0.5 µg/L showed around 85% mortality regardless of the pulse interval (3 to 14 days). However, they were able to survive if exposed to two 6-h pulses if separated by at least 3 days.

Guideline

There was a comprehensive dataset for chlorpyrifos. Rotifers and ciliate 72-hour figures were included in the chronic data.

References

Abdullah AP, Lim RP & Chapman JC 1993. Inhibition and recovery of acetylcholinesterase in Paratya australiensis exposed to the organophosphate insecticide chlorpyrifos. Fresenius Environmental Bulletin 2, 752–757.

ANZECC & ARMCANZ 2000. Australian and New Zealand Guidelines for Fresh and Marine Water Quality, Australian and New Zealand Environment and Conservation Council and Agriculture and Resource Management Council of Australia and New Zealand, Canberra.AQUIRE (Aquatic Toxicity Information Retrieval Database) 1994. AQUIRE standard operating procedures. USEPA, Washington, DC.

Barron MG & Woodburn KB 1995. Ecotoxicology of chlorpyrifos. Reviews of Environmental Contamination and Toxicology 144, 1-146.

Biever RC, Giddings JM, Kiamos M, Annunziato MF, Meyerhoff R & Racke K 1994. Effects of chlorpyrifos on aquatic mesocosms over a range of off-target spray drift exposure levels. In Brighton crop protection conference: Pests and diseases, British Crop Protection Council, UK, 1367-1372. (Cited in Barron & Woodburn 1995)

Brazner JC, Heinis LJ & Jensen DA 1989. A littoral enclosure for replicated field experiments. Environmental Toxicology and Chemistry 8, 1209-1216.

Brown JR, Chow LY & Deng CB 1976. The effects of Dursban upon fresh water phytoplankton. Bulletin of Environmental Contamination and Toxicology 15, 437-441.

Butcher JE, Boyer MG & Fowle CD 1977. Some changes in pond chemistry and photosynthetic activity following treatment with increasing concentrations of chlorpyrifos. Bulletin of Environmental Contamination and Toxicology 17, 752-758.

Giddings JM 1993. Chlorpyrifos (Lorsban® 4E): Outdoor aquatic microcosm test for environmental fate and ecological effects. Rep 92-9-4288. Springborn Laboratories, Wareham. (Cited in Barron & Woodburn 1995)

Johnson WW & Finley MT 1980. Handbook of acute toxicity of chemicals to fish and aquatic invertebrates. US Department of the Interior, Fish and Wildlife Service, No 137, Washington DC.

Lucassen WGH & Leeuwangh P 1994. Responses of zooplankton to Dursban® 4E insecticide in a pond experiment. In Aquatic mesocosm studies in ecological risk assessment, eds RL Graney, JH Rodgers & JH Kennedy, Lewis Publishers, MI, 517-534.

Mani VGT & Konar SK 1988. Pollutional hazards of the pesticide chlorpyrifos on aquatic ecosystems. Environmental Ecology 6, 460-462.

Macek KJ, Walsh DF, Hogan JW & Holz DD 1972. Toxicity of the insecticide Dursban to fish and aquatic invertebrates in ponds. Transactions of the American Fisheries Society 101, 420-427.

Naddy RB, Johnson KA & Klaine SJ 2000. Response of Daphnia magna to pulsed exposures of chlorpyrifos. Environmental Toxicology and Chemistry 19, 425–431.

Nelson JH & Evans ES 1973. Field evaluations of the larvicidal effectiveness. Effects on non-target species and environmental residues of a slow-release formulation of chlorpyrifos. Rep 44-022-73/75. US Army. (Cited in Barron & Woodburn 1975)

NRA 1997a. Database extraction of selected pesticides: Registered uses in Australia, National Registration Authority, July 1997, Canberra.

NRA 2000. Technical report on the NRA review of Chlorpyrifos. Draft for public comment, January 2000, National Registration Authority, Canberra.NRCC 1982. Chlorinated phenols: Criteria for environmental quality. Associate Committee on Scientific Criteria for Environmental Quality, National Research Council of Canada, Ottawa. NRCC No 18578.

NSW EPA 2000. Analytical Chemistry Section, Table of Trigger Values 20 March 2000, LD33/11, Lidcombe, NSW.

Patra R, Chapman JC, Gehrke PC & Lim RP 1995b. Effects of sub-lethal concentrations of endosulfan on the critical thermal maxima of freshwater fish. Poster abstract PW113. In Proceedings Second SETAC World Congress (16th Annual Meeting) Vancouver BC, 5-9 November 1995.

Patra R, Chapman JC, Lim RP & Gehrke PC 1995a. Effects of temperature on the acute toxicity of endosulfan to silver perch, Bidyanus bidyanus. Poster abstract PW 129. In Proceedings Second SETAC World Congress (16th Annual Meeting), Vancouver BC, 5-9 November 1995, 252.

Pusey BJ, Arthington AH & McLean J 1994. The effects of a pulsed application of chlorpyrifos on macroinvertebrate communities in an outdoor artificial stream system. Ecotoxicology and Environmental Safety 27, 221-250.

Racke K 1993. Environmental fate of chlorpyrifos. Reviews of Environmental Contamination and Toxicology 131, 1-150.

Roberts DR, Roberts LW, Miller TA, Nelson LL & Young WW 1973. Polymer formulations of mosquito larvicides II. Effects of a polyethylene formulation of chlorpyrifos on non-target populations naturally infesting artificial field pools. Mosquito News 33, 165-172.

Tomlin C 1994. The pesticide manual: A world compendium. 10th edn, British Crop Protection Council & Royal Society of Chemistry, Bath, UK.

van den Brink PJ, Van Wijngaarden RPA, Lucassen WGH, Brock TCM & Leeuwangh P 1996. Effects of the insecticide Dursban® in outdoor experimental ditches: II invertebrate community responses and recovery. Environmental Toxicology and Chemistry 15, 1143-1153.

van Wijngaarden R & Leeuwangh P 1989. Relationship between toxicity in laboratory and pond: An ecotoxicological study with chlorpyrifos. (Cited in Barron & Woodburn 1995)

WHO 1986. Environmental health criteria 63. Organophosphorus insecticides: A general introduction. World Health Organization, Geneva.