Losantos Diana, Fernández-Arribas Julio, Pérez-Trujillo Míriam, Eljarrat Ethel, Sarrà Montserrat, Caminal Glòria
Department of Chemical, Biological and Environmental Engineering, Universitat Autònoma de Barcelona, Escola d'Enginyeria, Campus Bellaterra, 08193 Cerdanyola del Vallès, Spain.
Environmental and Water Chemistry for Human Health (ONHEALTH), Institute of Environmental Assessment and Water Research (IDAEA), Spanish Council for Scientific Research (CSIC), Jordi Girona 18-26, 08034 Barcelona, Spain.
Sci Total Environ. 2025 Jan 10;959:178260. doi: 10.1016/j.scitotenv.2024.178260. Epub 2025 Jan 2.
The environmental persistence of organophosphate flame retardants (OPFRs) in water is becoming and environmental concern. White Rot Fungi (WRF) have proven its capability to degrade certain OPFRs such as tributyl phosphate (TBP), tris(2-butoxyethyl) phosphate (TBEP), tris(2-chloroethyl) phosphate (TCEP) and tris(2-chloroisopropyl) phosphate (TCPP). Despite this capability, there is limited knowledge about the specific pathways involved in the degradation. In this study, three different WRF were paired with individual OPFRs, and potential transformation products (TPs) were identified by UHPLC-HRMS. Some compounds structures were further validated by NMR. From these data degradation pathways were proposed. TBP was degraded by successive hydroxylation and hydrolysis reactions, with a novel dehydrogenation step suggested. Both TCEP and TCPP underwent oxidative dechlorination, with TCEP experiencing subsequent hydrolysis. Uncommon reductive dehalogenation was also observed. TCPP further underwent hydroxylation and environmentally relevant methylation. TBEP generated numerous TPs, mainly by successive dealkylations, along with hydroxylation. Notably, demethylation in TBEP degradation was proposed for the first time. Additional secondary products were formed through hydroxylation and oxidation of the initial metabolites. Finally, in vivo and in silico toxicity assessments were conducted, identifying certain TPs as potentially toxic.
有机磷酸酯阻燃剂（OPFRs）在水中的环境持久性正成为一个环境问题。白腐真菌（WRF）已被证明有能力降解某些OPFRs，如磷酸三丁酯（TBP）、磷酸三（2-丁氧基乙基）酯（TBEP）、磷酸三（2-氯乙基）酯（TCEP）和磷酸三（2-氯异丙基）酯（TCPP）。尽管有这种能力，但关于其降解所涉及的具体途径的了解仍然有限。在本研究中，将三种不同的白腐真菌与单独的OPFRs配对，并通过超高效液相色谱-高分辨质谱（UHPLC-HRMS）鉴定潜在的转化产物（TPs）。一些化合物结构通过核磁共振（NMR）进一步验证。根据这些数据提出了降解途径。TBP通过连续的羟基化和水解反应降解，并提出了一个新的脱氢步骤。TCEP和TCPP都经历了氧化脱氯反应，TCEP随后发生水解。还观察到罕见的还原脱卤反应。TCPP进一步经历了羟基化和与环境相关的甲基化。TBEP产生了大量的TPs，主要是通过连续的脱烷基反应以及羟基化反应。值得注意的是，首次提出了TBEP降解过程中的脱甲基反应。通过初始代谢产物的羟基化和氧化形成了额外的二级产物。最后，进行了体内和计算机模拟毒性评估，确定某些TPs具有潜在毒性。
