A Review of Organophosphate Esters in the Environment from Biological Effects to Distribution and Fate

  • Alana K. Greaves
  • Robert J. Letcher
Focused Review


Organophosphate esters (OPEs) are synthetic phosphoric acid derivatives used in a wide variety of applications including as flame retardants and plasticizers. Their production and usage has increased in recent years, due to the phase-out of other flame retardant formulations (e.g., polybrominated diphenyl ethers). As such, there has been a recent push to understand the global distribution of OPEs and their behaviour in biota. Multiple studies have been published over the last few years pertaining to OPE concentrations in biotic and abiotic environmental compartments, as well as the metabolism of OPEs in biota. This paper aims to provide a brief review of the occurrence and levels of OPEs in the environment, as well as recent developments concerning the elucidation of OPE metabolism in biota.


Organophosphate ester flame retardants Birds Fish Environmental distribution Metabolism Review 



This work is supported by Chemicals Management Plan (CMP; Environment and Climate Change Canada), as well as by the Natural Science and Engineering Research Council (NSERC) of Canada (to R.J.L.). Doctoral support for A. Greaves was in part from the Natural Science and Engineering Research Council (NSERC) of Canada (to R.J.L.) as well as an Ontario Graduate Scholarship (to A.K.G.).


  1. Bester K (2005) Comparison of TCPP concentrations in sludge and wastewater in a typical German sewage treatment plant–—comparison of sewage sludge from 20 plants. J Environ Monit 7:509–513CrossRefGoogle Scholar
  2. Brandsma SH, Leonards PEG, Leslie HA, de Boer J (2015) Tracing organophosphorus and brominated flame retardants and plasticizers in an estuarine food web. Sci Tot Environ 505:22–31CrossRefGoogle Scholar
  3. Chen D, Letcher RJ, Chu S (2012) Determination of non-halogenated, chlorinated and brominated organophosphate flame retardants in herring gull eggs based on liquid chromatography–tandem quadrupole mass spectrometry. J Chromatogr A 1220:169–174CrossRefGoogle Scholar
  4. Ciccioli P, Cecinato A, Brancaleoni E, Montagnoli M, Allegrini I (1994) Chemical composition of particulate organic matter (POM) collected at Terra Nova Bay in Antarctica. Int J Environ Anal Chem 55:47–59CrossRefGoogle Scholar
  5. Cristale J, García Vázquez A, Barata C, Lacorte S (2013) Priority and emerging flame retardants in rivers: occurrence in water, sediment, Daphnia magna toxicity and risk assessment. Environ Int 59:232–243CrossRefGoogle Scholar
  6. Crump D, Chiu S, Kennedy SW (2012) Effects of tris(1,3-dichloro-2-propyl) phosphate and tris(1-chloropropyl) phosphate on cytotoxicity and mRNA expression in primary cultures of avian hepatocytes and neuronal cells. Toxicol Sci 126:140–148CrossRefGoogle Scholar
  7. Eulaers I, Jaspers VLB, Halley DJ, Lepoint G, Nygård T, Pinxten R, Covaci A, Eens M (2014) Brominated and phosphorus flame retardants in white-tailed eagle Haliaeetus albicilla nestlings: bioaccumulation and associations with dietary proxies (δ13C, δ15N and δ34S). Sci Tot Environ 478:48–57CrossRefGoogle Scholar
  8. Evenset A, Leknes H, Christensen GN, Warner N, Remberger M, Gabrielsen GW (2009) Screening of new contaminants in samples from the Norwegian Arctic. NIVA report 4351-1, SPFO-report 1049/2009, TA-2510/2009Google Scholar
  9. Farhat A, Crump D, Chiu S, Williams KL, Letcher RJ, Gauthier LT, Kennedy SW (2013) In ovo effects of two organophosphate flame retardants TCPP and TDCPP on pipping success, development, mRNA expression, and thyroid hormone levels in chicken embryos. Toxicol Sci 134:92–102CrossRefGoogle Scholar
  10. Fernie KJ, Palace V, Peters LE, Basu N, Letcher RJ, Karouna-Renier NK, Schultz SL, Lazarus RS, Rattner BA (2015) Investigating endocrine and physiological parameters of captive American kestrels exposed by diet to selected organophosphate flame retardants. Environ Sci Technol 49:7448–7455CrossRefGoogle Scholar
  11. Fries E, Püttmann W (2003) Monitoring of the three organophosphate esters TBP, TCEP and TBEP in river water and ground water (Oder, Germany). J Environ Monit 5:346–352CrossRefGoogle Scholar
  12. Greaves AK, Letcher RJ (2014) Comparative body compartment composition and in ovo transfer of organophosphate flame retardants in North American Great Lakes herring gulls. Environ Sci Technol 48:7942–7950CrossRefGoogle Scholar
  13. Greaves AK, Letcher RJ, Chen D, McGoldrick DJ, Gauthier LT, Backus SM (2016a) Retrospective analysis of organophosphate flame retardants in herring gull eggs and relation to the aquatic food web in the Great Lakes. Environ Res 150:255–263CrossRefGoogle Scholar
  14. Greaves AK, Su G, Letcher RJ (2016b) Environmentally relevant organophosphate triester flame retardants in herring gulls: in vitro biotransformation and kinetics and diester metabolite formation using a hepatic microsomal assay. Toxicol Appl Pharmacol (accepted)Google Scholar
  15. Hallanger IG, Sagerup K, Evenset A, Kovacs KM, Leonards P, Fuglei E, Routti H, Aars J, Strøm H, Lydersen C, Gabrielsen GW (2015) Organophosphorous flame retardants in biota from Svalbard, Norway. Mar Pollut Bull 101:442–447CrossRefGoogle Scholar
  16. Kim J-W, Isobe T, Chang K-H, Amano A, Maneja RH, Zamora PB, Siringan FP, Tanabe S (2011) Levels and distribution of organophosphorus flame retardants and plasticizers in fishes from Manila Bay, the Philippines. Environ Pollut 159:3653–3659CrossRefGoogle Scholar
  17. Leonards P, Steindal EH, van der Veen I, Berg V, Ove Bustnes J, van Leeuwen S (2011) Screening of organophosphor flame retardants 2010. SPFO-report 1091/2011. TA-2786/2011Google Scholar
  18. Li H, Su G, Zou M, Yu L, Letcher RJ, Yu H, Giesy JP, Zhou B, Liu C (2015) Effects of tris(1,3-dichloro-2-propyl) phosphate on growth, reproduction, and gene transcription of Daphnia magna at environmentally relevant concentrations. Environ Sci Technol 49:12975–12983CrossRefGoogle Scholar
  19. Marklund A, Andersson B, Haglund P (2005) Organophosphorus flame retardants and plasticizers in Swedish sewage treatment plants. Environ Sci Technol 39:7423–7429CrossRefGoogle Scholar
  20. Martínez-Carballo E, González-Barreiro C, Sitka A, Scharf S, Gans O (2007) Determination of selected organophosphate esters in the aquatic environment of Austria. Sci Tot Environ 388:290–299CrossRefGoogle Scholar
  21. McGoldrick DJ, Letcher RJ, Barresi E, Keir MJ, Small J, Clark MG, Backus SM (2014) Organophosphate flame retardants and organosiloxanes in predatory freshwater fish from locations across Canada. Environ Pollut 193:254–261CrossRefGoogle Scholar
  22. O’Brien JW, Thai PK, Brandsma SH, Leonards PEG, Ort C, Mueller JF (2015) Wastewater analysis of census day samples to investigate per capita input of organophosphorus flame retardants and plasticizers into wastewater. Chemosphere 138:328–334CrossRefGoogle Scholar
  23. Papachilimitzou A, Barber JL, Losada S, Bersuder P, Deaville R, Brownlow A, Penrose R, Jepson PD, Law RJ (2015) Organophosphorus flame retardants (PFRs) and plasticisers in harbour porpoises (Phocoena phocoena) stranded or bycaught in the UK during 2012. Mar Pollut Bull 98:328–334CrossRefGoogle Scholar
  24. Porter E, Crump D, Egloff E, Chiu S, Kennedy SW (2014) Use of an avian hepatocyte assay and the avian ToxChip polymerase chain reaction assay for testing prioritization of 16 organic flame retardants. Environ Toxicol Chem 33:573–582CrossRefGoogle Scholar
  25. Salamova A, Ma Y, Venier M, Hites RA (2014) High levels of organophosphate flame retardants in the Great Lakes atmosphere. Environ Sci Technol Lett 1:8–14CrossRefGoogle Scholar
  26. Schreder ED, Uding N, La Guardia MJ (2016) Inhalation a significant exposure route for chlorinated organophosphate flame retardants. Chemosphere 150:499–504CrossRefGoogle Scholar
  27. Stackelberg PE, Furlong ET, Meyer MT, Zaugg SD, Henderson AK, Reissman DB (2004) Persistence of pharmaceutical compounds and other organic wastewater contaminants in a conventional drinking-water treatment plant. Sci Tot Environ 329:99–113CrossRefGoogle Scholar
  28. Su G, Crump D, Letcher RJ, Kennedy SW (2014) Rapid metabolism in vitro of triphenyl phosphate flame retardant and effects on cytotoxicity and mRNA expression in chicken embryonic hepatocytes. Environ Sci Technol 48:13511–13519CrossRefGoogle Scholar
  29. Su G, Letcher RJ, Moore JN, Williams LL, Martin PA, de Solla SR, Bowerman WW (2015) Spatial and temporal comparisons of legacy and emerging flame retardants in herring gull eggs from colonies spanning the Laurentian Great Lakes of Canada and United States. Environ Res 142:720–730CrossRefGoogle Scholar
  30. van den Eede N, Maho W, Erratico C, Neels H, Covaci A (2013) First insights in the metabolism of phosphate flame retardants and plasticizers using human liver fractions. Toxicol Lett 223:9–15CrossRefGoogle Scholar
  31. van den Eede N, Erratico C, Exarchou V, Maho W, Neels H, Covaci A (2015) In vitro biotransformation of tris(2-butoxyethyl) phosphate (TBOEP) in human liver and serum. Toxicol Appl Pharmacol 284:246–253CrossRefGoogle Scholar
  32. van den Eede N, Tomy G, Tao F, Halldorson T, Harrad S, Neels H, Covaci A (2016) Kinetics of tris(1-chloro-2 propyl) phosphate (TCIPP) metabolism in human liver microsomes and serum. Chemosphere 144:1299–1305CrossRefGoogle Scholar
  33. van der Veen I, de Boer J (2012) Phosphorus flame retardants: properties, production, environmental occurrence, toxicity and analysis. Chemosphere 88:1119–1153CrossRefGoogle Scholar
  34. Venier M, Dove A, Romanak K, Backus S, Hites RA (2014) Flame retardants and legacy chemicals in Great Lakes’ water. Environ Sci Technol 48:9563–9572CrossRefGoogle Scholar
  35. Wang Q, Liang K, Liu J, Yang L, Guo Y, Liu C, Zhou B (2013) Exposure of zebrafish embryos/larvae to TDCPP alters concentrations of thyroid hormones and transcriptions of genes involved in the hypothalamic–pituitary–thyroid axis. Aquat Toxicol 126:207–213CrossRefGoogle Scholar
  36. Zhu Y, Ma X, Su G, Yu L, Letcher RJ, Hou J, Yu H, Giesy JP, Liu C (2015) Environmentally relevant concentrations of the flame retardant tris(1,3-dichloro-2-propyl) phosphate inhibit growth of female zebrafish and decrease fecundity. Environ Sci Technol 49:14579–14587CrossRefGoogle Scholar

Copyright information

© Her Majesty the Queen in Right of Canada 2016

Authors and Affiliations

  1. 1.Wildlife and Landscape Directorate, Science and Technology Branch, Environment and Climate Change Canada, National Wildlife Research CentreCarleton UniversityOttawaCanada
  2. 2.Department of ChemistryCarleton UniversityOttawaCanada

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