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DEVELOPMENT AND OPTIMIZATION OF AN LC-MS/MS METHOD FOR THE SIMULTANEOUS DETERMINATION OF ORGANOPHOSPHATE FLAME RETARDANTS IN SEAWATER SAMPLES
Abstract
Organophosphate flame retardants (OPFRs) have emerged as replacements for banned brominated flame retardants, raising growing environmental concern due to their persistence, bioaccumulation potential, and toxicity. Despite their global detection, limited data exist for marine environments such as the Black Sea, where monitoring is hindered by the lack of sensitive analytical methods. This study reports the development and validation of a reliable LC-MS/MS method for the simultaneous determination of eight OPFRs and three degradation products in seawater. Method optimization included testing different chromatographic columns and mobile phases, with the best separation achieved using a Zorbax Eclipse Plus C18 column and a methanol-water gradient containing formic acid. Detection was performed in both positive and negative ESI modes under multiple reaction monitoring. Sample preparation was optimized through solid-phase extraction, where Strata-X polymeric cartridges with acetonitrile elution achieved recoveries above 90%. The method exhibited excellent linearity (R- > 0.99), high precision (RSD less than 10%), and low detection limits in the nanogram-per-liter range. Application to Black Sea seawater samples confirmed the presence of several OPFRs, with TCEP, TCPP, and TPP being the dominant compounds. The proposed method provides a robust and sensitive tool for environmental monitoring of OPFRs in marine ecosystems, supporting future pollution control and risk assessment efforts.
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Greaves A.K., Letcher R.J., A review of organophosphate esters in the environment from biological effects to distribution and fate, Bulletin of Environmental Contamination and Toxicology, USA, 2017, pp. 2�7, ISSN 0007-4861, DOI: � DOI: 10.1007/s00128-016-1898-0
Gao X.Z., Xu Y.P., Wang Z.J., Progress in environmental exposure, transport and transformation of organophosphorus flame retardants, Asian Journal of Ecotoxicology, China, 2015, Vol. 10 (2), pp. 56�68, ISSN �
Miyake Y., Tokumura M., Wang Q., Amagai T., Takegawa Y., Yamagishi Y., Ogo S., Kume K., Kobayashi T., Takasu S., Ogawa K., Kannan K., Identification of novel phosphorus-based flame retardants in curtains purchased in Japan using Orbitrap mass spectrometry, Environmental Science & Technology Letters, Japan, 2018, Vol. 5 (7), pp. 448�455, ISSN 2328-8930, DOI: � DOI: 10.1021/acs.estlett.8b00263
Stockholm Convention, Stockholm Convention on Persistent Organic Pollutants, Switzerland, 2008, Available at: http://chm.pops.int/
Wagner S., Schlummer M., Legacy additives in a circular economy of plastics: current dilemma, policy analysis, and emerging countermeasures, Resources, Conservation and Recycling, Netherlands, 2020, Article 104800, ISSN 0921-3449, DOI: 10.1016/j.resconrec.2020.104800
European Commission, Commission Regulation (EU) 2017/227 of 9 February 2017, Official Journal of the European Union, Belgium, 2017, L35/6, ISSN 1977-0677
Pang L., Yang H.Q., Yang P.J., Zhang H.Z., Zhao J.H., Trace determination of organophosphate esters in white wine, red wine, and beer using dispersive liquid�liquid microextraction and UHPLC�MS/MS, Food Chemistry, China, 2017, Vol. 229, pp. 445�451, ISSN 0308-8146 DOI: 10.1016/j.foodchem.2017.02.103
Lee S., Jeong W., Kannan K., Moon H., Occurrence and exposure assessment of organophosphate flame retardants through the consumption of drinking water in Korea, Water Research, Korea, 2016, Vol. 102, pp. 182�188, ISSN 0043-1354 DOI: 10.1016/j.watres.2016.07.034
Kim U.J., Wang Y., Li W.H., Kannan K., Occurrence of and human exposure to organophosphate flame retardants/plasticizers in indoor air and dust from various microenvironments in the United States, Environment International, USA, 2019, Vol. 125, pp. 342�349, ISSN 0160-4120 DOI: 10.1016/j.envint.2019.01.065
Ding J., Deng T., Xu M., Wang S., Yang F., Residuals of organophosphate esters in foodstuffs and implications for human exposure, Environmental Pollution, China, 2018, Vol. 233, pp. 986�991, ISSN 0269-7491 DOI: 10.1016/j.envpol.2017.09.092
He C., Wang X.Y., Tang S.Y., Thai P., Li Z.R., Baduel C., Mueller J.F., Concentrations of organophosphate esters and metabolites in food from Southeast Queensland, Australia, Environmental Science & Technology, Australia, 2018, Vol. 52, pp. 12765�12773, ISSN 0013-936X DOI: 10.1021/acs.est.8b03043
Ni Y., Kumagai K., Yanagisawa Y., Measuring emissions of organophosphate flame retardants using a passive flux sampler, Atmospheric Environment, Japan, 2007, Vol. 41, pp. 3235�3240, ISSN 1352-2310 DOI: 10.1016/j.atmosenv.2006.10.080
Yu X.L., Yin H., Peng H., Lu G.N., Liu Z.H., Dang Z., OPFRs and BFRs induce A549 cell apoptosis via caspase-dependent mitochondrial pathway, Chemosphere, China, 2019, Vol. 221, pp. 693�702, ISSN 0045-6535 DOI: 10.1016/j.chemosphere.2019.01.074
Wang Q.Z., Zhao H.X., Xu L., Wang Y., Uptake and translocation of organophosphate flame retardants by hydroponically grown wheat (Triticum aestivum L.), Ecotoxicology and Environmental Safety, China, 2019, Vol. 174, pp. 683�689, ISSN 0147-6513 DOI: 10.1016/j.ecoenv.2019.03.029
Ali N., Eqani S.A.M.A.S., Ismail I.M.I., Malarvannan G., Kadi M.W., Albar H.M.S., Rehan M., Covaci A., Brominated and organophosphate flame retardants in indoor dust of Jeddah, Kingdom of Saudi Arabia: implications for human exposure, Science of the Total Environment, Saudi Arabia, 2016, Vol. 569�570, pp. 269�277, ISSN 0048-9697 DOI: 10.1016/j.scitotenv.2016.06.093
European Commission, Commission Directive 2014/79/EU of 20 June 2014 amending Appendix C of Annex II to Directive 2009/48/EC on toy safety regarding TCEP, TCPP, and TDCP, Official Journal of the European Union, Belgium, 2014, L182, pp. 49�51, http://data.europa.eu/eli/dir/2014/79/oj
Teo T.L.L., McDonald J.A., Coleman H.M., Khan S.J., Analysis of organophosphate flame retardants and plasticisers in water by isotope dilution GC�EI�MS/MS, Talanta, Australia, 2015, Vol. 143, pp. 114�120, ISSN 0039-9140 DOI: 10.1016/j.talanta.2015.04.091
Guo X., Mu T., Xian Y., Luo D., Wang C., Rapid simultaneous analysis of nine organophosphate esters in milk powder using UPLC�MS/MS, Food Chemistry, China, 2016, Vol. 196, pp. 673�681, ISSN 0308-8146 DOI: 10.1016/j.foodchem.2015.09.100
Wu Z.J., Liu J.P., Peng Y., Determination of trace organophosphate esters in dairy products using QuEChERS and isotope dilution UHPLC�MS/MS, Analytical Methods, China, 2017, Vol. 9 (15), pp. 2290�2298, ISSN 1759-9660 DOI: 10.1039/c6ay03162e
Kersnakova Z., Lemak I., Bajtos P., Vabcova J., Hrouzkova S., Occurrence and consequences of matrix effects in simultaneous multi-class LC�MS/MS determination of pesticides, pharmaceuticals, and perfluoroalkyl substances in groundwater, Water, Air, & Soil Pollution, Slovakia, 2024, Vol. 235, Article 396, DOI: 10.1007/s11270-024-07221-2
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