Environmental Science and Pollution Research

, Volume 25, Issue 20, pp 19546–19554 | Cite as

Simultaneous accelerated solvent extraction and purification for the determination of 13 organophosphate esters in soils by gas chromatography-tandem mass spectrometry

  • Qing LuoEmail author
  • Shiyu Wang
  • Li-na Sun
  • Hui Wang
Research Article


Through the optimization of extraction, purification, and determination parameters, a reliable and convenient analytical method for the simultaneous determination of 13 organophosphate esters in soils was developed. The method is based on one-step extraction and purification by accelerated solvent extraction and analysis by gas chromatography-ion trap tandem mass spectrometry. Under the optimal conditions, the method detection limits and method quantitation limits ranged from 0.10 to 0.22 ng/g and from 0.33 to 0.72 ng/g, respectively. The recoveries obtained were in the range of 81.7–107%, and the relative standard deviations were less than 12%. As compared to other methods, this proposed method was simple and time and solvent saving. The developed method was successfully applied to analyze organophosphate esters in soil samples collected from Liaohe estuarine wetland, China. Thirteen organophosphate esters were detected in all of the soil samples which indicated that Liaohe estuarine wetland has polluted by organophosphate esters.


Organophosphate esters Gas chromatography-tandem mass spectrometry Ion trap mass analyzer Accelerated solvent extraction Soils 


Funding information

We are grateful to the financial support from the Natural Science Foundation of Liaoning Province (No. 20170520384) and the National Program on Key Basic Research Project of China (973 Program) (No. 2014CB441100). The funder had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.

Supplementary material

11356_2018_2047_MOESM1_ESM.doc (249 kb)
ESM 1 (DOC 249 kb)


  1. Aragón M, Marcé RM, Borrull F (2012) Determination of phthalates and organophosphate esters in particulated material from harbour air samples by pressurised liquid extraction and gas chromatography-mass spectrometry. Talanta 101(1):473–478CrossRefGoogle Scholar
  2. Brommer S, Harrad S, Van den Eede N, Covaci A (2012) Concentrations of organophosphate esters and brominated flame retardants in German indoor dust samples. J Environ Monit 14(9):2482–2487CrossRefGoogle Scholar
  3. Cao S, Zeng X, Song H, Li H, Yu Z, Sheng G, Fu J (2012) Levels and distributions of organophosphate flame retardants and plasticizers in sediment from Taihu Lake, China. Environ Toxicol Chem 31:1478–1484CrossRefGoogle Scholar
  4. Castro-Jiménez J, Berrojalbiz N, Pizarro M, Dachs J (2014) Organophosphate ester (OPE) flame retardants and plasticizers in the open Mediterranean and black seas atmosphere. Environ Sci Technol 48:3203−3209CrossRefGoogle Scholar
  5. Castro-Jiménez J, González-Gaya B, Pizarro M, Casal P, Pizarro-Álvarez C, Dachs J (2016) Organophosphate ester flame retardants and plasticizers in the global oceanic atmosphere. Environ Sci Technol. 50:12831–12839CrossRefGoogle Scholar
  6. Chu SG, Letcher RJ (2015) Determination of organophosphate flame retardants and plasticizers in lipid-rich matrices using dispersive solid-phase extraction as a sample cleanup step and ultra-high performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry. Anal Chim Acta 885:183–190CrossRefGoogle Scholar
  7. Cristale J, Lacorte S (2013) Development and validation of a multiresidue method for the analysis of polybrominated diphenyl ethers, new brominated and organophosphorus flame retardants in sediment, sludge and dust. J Chromatogr A 1305:267–275CrossRefGoogle Scholar
  8. Cristale J, Katsoyiannis A, Sweetman AJ, Jones KC, Lacorte S (2013) Occurrence and risk assessment of organophosphorus and brominated flame retardants in the River Aire (UK). Environ Pollut 179:194–200CrossRefGoogle Scholar
  9. Cui KY, Wen JX, Zeng F, Zhou X, Lia SC, Zeng ZX (2017) Determination of organophosphate ester flame retardants and plasticizers in soil samples by microwave-assisted extraction coupled with silica gel/alumina multilayer solid-phase extraction and gas chromatography-mass spectrometry. Anal Methods 9:986–993CrossRefGoogle Scholar
  10. Fan X, Kubwabo C, Rasmussen PE, Wu F (2014) Simultaneous determination of thirteen organophosphate esters in settled indoor house dust and a comparison between two sampling techniques. Sci Total Environ 491-492:80–86CrossRefGoogle Scholar
  11. 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(1):92–102CrossRefGoogle Scholar
  12. Fries E, Mihajlovic I (2011) Pollution of soils with organophosphorus flame retardants and plasticizers. J Environ Monit 13(10):2692–2694CrossRefGoogle Scholar
  13. García-López M, Rodríguez I, Cela R (2007) Microwave-assisted extraction of organophosphate flame retardants and plasticizers from indoor dust samples. J Chromatogr A 1152:280–286CrossRefGoogle Scholar
  14. García-López M, Rodríguez I, Cela R (2009) Pressurized liquid extraction of organophosphate triesters from sediment samples using aqueous solutions. J Chromatogr A 1216(42):6986–6993CrossRefGoogle Scholar
  15. Guo X, Mu T, Xian Y, Luo D, Wang C (2016) Ultra-performance liquid chromatography tandem mass spectrometry for the rapid simultaneous analysis of nine organophosphate esters in milk powder. Food Chem 196:673–681CrossRefGoogle Scholar
  16. He CT, Zheng J, Qiao L, Chen SJ, Yang JZ, Yuan JG, Yang ZY, Mai BX (2015) Occurrence of organophosphorus name retardants in indoor dust in multiple microenvironments of southern China and implications for human exposure. Chemosphere 133:47–52CrossRefGoogle Scholar
  17. Kim JW, Isobe T, Chang KH, 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(12):3653–3659CrossRefGoogle Scholar
  18. Liu X, Ji K, Choi K (2012) Endocrine disruption potentials of organophosphate flame retardants and related mechanisms in H295R and MVLN cell lines and in zebrafish. Aquat Toxicol 114:173–181CrossRefGoogle Scholar
  19. Liu SL, Zhang H, Hu XH, Qiu YL, Zhu ZL, Zhao JF (2016) Analysis of organophosphate esters in sediment samples using gas chromatography-tandem mass spectrometry. Chin J Anal Chem 44(2):192–197CrossRefGoogle Scholar
  20. Long P, Yang P, Ge L, Du J, Zhang H (2017) Accelerated solvent extraction combined with solid phase extraction for the determination of organophosphate esters from sewage sludge compost by UHPLC–MS/MS. Anal Bioanal Chem 409(5):1435–1440CrossRefGoogle Scholar
  21. Losada S, Parera J, Abalos M, Abad E, Santos FJ, Galceran MT (2010) Suitability of selective pressurized liquid extraction combined with gas chromatography-ion-trap tandem mass spectrometry for the analysis of polybrominated diphenyl ethers. Anal Chim Acta 678(1):73–81CrossRefGoogle Scholar
  22. Lu JX, Ji W, Ma ST, Yu ZQ, Wang Z, Li H, Ren GF, Fu JM (2014) Analysis of organophosphate esters in dust, soil and sediment samples using gas chromatography coupled with mass spectrometry. Chin J Anal Chem 42(6):859–865CrossRefGoogle Scholar
  23. Luo YM, Teng Y, Guo Y (2005) Soil remediation—a new branch discipline of soil science. Soils 37(3):230–235Google Scholar
  24. Ma Y, Cui K, Feng Z, Wen J, Liu H, Zhu F, Ouyang G, Luan T, Zeng Z (2013) Microwave-assisted extraction combined with gel permeation chromatography and silica gel cleanup followed by gas chromatography–mass spectrometry for the determination of organophosphorus flame retardants and plasticizers in biological samples. Anal Chim Acta 786(13):47–53CrossRefGoogle Scholar
  25. Makinen MS, Makinen MR, Koistinen JT, Pasanen AL, Pasanen PO, Kalliokoski PJ, Korpi AM (2009) Respiratory and dermal exposure to organophosphoras flame retardants and tetrabromobkphenol A at five work environments. Environ Sci Technol 43(3):941–947CrossRefGoogle Scholar
  26. Malavia J, Santos FJ, Galceran MT (2011) Simultaneous pressurized liquid extraction and clean-up for the analysis of polybrominated biphenyls by gas chromatography-tandem mass spectrometry. Talanta 84(4):1155–1162CrossRefGoogle Scholar
  27. Matuszewski BK, Constanzer ML, Chavezeng CM (2003) Strategies for the assessment of matrix effect in quantitative bioanalytical methods based on HPLC-MS/MS. Anal Chem 75(13):3019–3030CrossRefGoogle Scholar
  28. Meeker JD, Stapleton HM (2010) House dust concentrations of organophosphate flame retardants in relation to hormone levels and semen quality parameters. Environ Health Perspect 118:318CrossRefGoogle Scholar
  29. Mihajlovic I, Fries E (2012) Atmospheric deposition of chlorinated organophosphate flame retardants (OFR) onto soils. Atmos Environ 56:177–183CrossRefGoogle Scholar
  30. O’Brien JW, Thai PK, Brandsma SH, Leonards PE, Ort C, Mueller JF (2015) Wastewater analysis of census day samples to investigate per capita input of organophosphoms flame retardants and plasticizes into wastewater. Chemosphere 138:328–334CrossRefGoogle Scholar
  31. Peverly AA, O’Sullivan C, Liu LY, Venier M, Martinez A, Hornbuckle KC, Hites RA (2015) Chicago’s sanitary and ship canal sediment: polycyclic aromatic hydrocarbons, polychlorinated biphenyls, brominated flame retardants, and organophosphate esters. Chemosphere 134:380–386CrossRefGoogle Scholar
  32. Quintana JB, Rodil R, Lopez-Mahia R, Muniategui-Lorenzo S, Prada-Rodríguez D (2007) Optimisation of a selective method for the determination of organophosphorous trimesters in outdoor particulate samples by pressurized liquid extraction and large-volume injection gas chromatography-positive chemical ionisation-tandem mass spectrometry. Anal Bioanal Chem 388(5–6):1283–1293CrossRefGoogle Scholar
  33. Regnery J, Puttmann W (2010) Occurrence and fate of organophosphorus flame retardants and plasticize in urban and remote surface waters in Germany. Water Res 44(14):4097–4104CrossRefGoogle Scholar
  34. Saini A, Thaysen C, Jantunen L, McQueen RH, Diamond ML (2016) From clothing to laundry water: investigating the fate of phthalates, brominated flame retardants, and organophosphate esters. Environ Sci Technol 50:9289–9297CrossRefGoogle Scholar
  35. Salamova A, Ma Y, Venier M, Hites RA (2014a) High levels of organophosphate flame retardants in the Great Lakes atmosphere. Environ Sci Technol Lett 1(1):8–14CrossRefGoogle Scholar
  36. Salamova A, Hermanson MH, Hites RA (2014b) Organophosphate and halogenated flame retardants in atmospheric particles from a European Arctic site. Environ Sci Technol 48(11):6133–6140CrossRefGoogle Scholar
  37. Tan XX, Luo XJ, Zheng XB, Li ZR, Sun RX, Mai BX (2016) Distribution of organophosphorus flame retardants in sediments from the Pearl River Delta in South China. Sci Total Environ 544:77–84CrossRefGoogle Scholar
  38. USEPA (1986) EPA Regulation 40 CFR Part 136 (Appendix B) Appendix B to Part 136—Definition and Procedure for the Determination of the Method Detection Limit—Revision 1.11. US Environmental Protection Agency (EPA), Available at [Accessed 05 Mar 2013]
  39. Wan WN, Zhang SZ, Huang HL, Wu T (2016) Occurrence and distribution of organophosphorus esters in soils and wheat plants in a plastic waste treatment area in China. Environ Pollut 214:349–353CrossRefGoogle Scholar
  40. Wang RM, Tang JH, Xie ZY, Mi W, Chen Y, Wolschke H, Tian C, Pan X, Luo Y, Ebinghaus R (2015) Occurrence and spatial distribution of organophosphate ester flame retardants and plasticizers in 40 rivers draining into the Bohai Sea, North China. Environ Pollut 198:172–178CrossRefGoogle Scholar
  41. Yang R, Ding J, Huang W, Xie W, Liu W (2014) Particle size-specific distributions and preliminary exposure assessments of organophosphate flame retardants in office air particulate matter. Environ Sci Technol 48(1):63–70CrossRefGoogle Scholar
  42. Zeng XY, Liu Y, He LX, Cao S, Song H, Yu Z, Sheng G, Fu J (2015) The occurrence and removal of organophosphate ester flame retardants/plasticizers in a municipal wastewater treatment plant in the Pearl River Delta, China. J Environ Sci Health A Tox Hazard Subst Environ Eng 50(12):1291–1297CrossRefGoogle Scholar
  43. Zheng J, Gao Z, Yuan W, He H, Yang S, Sun C (2014) Development of pressurized liquid extraction and solid-phase microextraction combined with gas chromatography and flame photometric detection for the determination of organophosphate esters in sediments. J Sep Sci 37(17):2424–2430CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Key Laboratory of Regional Environment and Eco-Remediation of Ministry of Education, College of EnvironmentShenyang UniversityShenyangChina

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