State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074, China; School of Environmental Studies, China University of Geosciences, Wuhan 430074, China; Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ, UK.
State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074, China.
Environ Pollut. 2018 Apr;235:560-570. doi: 10.1016/j.envpol.2017.12.071. Epub 2018 Jan 9.
Dicofol (2,2,2-trichloro-1,1-bis-(p-chlorophenyl)ethanol) found in the environment is not only a miticide originated from commercial use, but also a metabolite of dichlorodiphenyltrichloroethane (DDT), which is often overlooked. To verify the sources and transformation pathways of DDT and related metabolites in soils, we measured p,p'-(dicofol + DBP) (sum of p,p'-dicofol and 4,4'-dichlorobenzophenone), DDT and six metabolites in soils from Northwest Fujian, China. The ratios of 1,1,1-trichloro-2-(o-chlorophenyl)-2-(p-chlorophenyl)ethane (o,p'-DDT)/1,1,1-trichloro-2,2-bis-(p-chlorophenyl)ethane (p,p'-DDT) and the mass balance demonstrated that p,p'-(dicofol + DBP) predominantly originated from p,p'-DDT transformation rather than from actual dicofol application. p,p'-(dicofol + DBP) accounted for 45.0% as the primary metabolites of DDT in this study, more than 1,1-dichloro-2,2-bis-(p-chlorophenyl)ethylene (p,p'-DDE) and 1,1-dichloro-2,2-bis-(p-chlorophenyl)ethane (p,p'-DDD), which might lead to large overestimations of the fresh DDT input by using the traditional ratio of (∑DDD + ∑DDE)/∑DDT (with all o,p'- and p,p'- isomers included). In paddy fields where the conditions alternate between aerobic (dry period) and anaerobic (wet period), both p,p'-DDD and p,p'-DDE were likely to degrade to 1-chloro-2,2-bis-(p-chlorophenyl)ethylene (p,p'-DDMU), which further transformed to 2,2-bis(p-chlorophenyl)ethylene (p,p'-DDNU). Degradation of p,p'-DDMU to p,p'-DDNU mainly occurred in waterlogged paddy soils. However, p,p'-DDNU might not transform to other higher-order metabolites in aerobic surface soils. Overall, our study confirmed p,p'-(dicofol + DBP) as metabolites of p,p'-DDT, suggested DDE and DDD were parallel precursors of DDMU, and further verified the transformation pathways of DDT in surface soils.
环境中二氯苯醚菊酯(2,2,2-三氯-1,1-双-(对氯苯基)乙醇)不仅是一种源于商业用途的杀螨剂,还是常常被忽视的滴滴涕(DDT)的一种代谢物。为了验证土壤中滴滴涕和相关代谢物的来源和转化途径,我们测量了来自中国福建西北部土壤中的 p,p'-(二氯苯醚菊酯+DBP)(p,p' -二氯苯醚菊酯和 4,4'-二氯二苯甲酮的总和)、滴滴涕和六种代谢物。1,1,1-三氯-2-(邻氯苯基)-2-(对氯苯基)乙烷(o,p'-DDT)/1,1,1-三氯-2,2-双-(对氯苯基)乙烷(p,p'-DDT)的比值和质量平衡表明,p,p'-(二氯苯醚菊酯+DBP)主要来源于 p,p'-DDT 的转化,而不是实际的二氯苯醚菊酯的使用。在本研究中,p,p'-(二氯苯醚菊酯+DBP)作为滴滴涕的主要初级代谢物,占比 45.0%,超过了 1,1-二氯-2,2-双-(对氯苯基)乙烯(p,p'-DDE)和 1,1-二氯-2,2-双-(对氯苯基)乙烷(p,p'-DDD),这可能会导致传统的(∑DDD+∑DDE)/∑DDT 比值(包含所有 o,p'-和 p,p'-异构体)对新鲜滴滴涕输入的高估。在水稻田中,条件在有氧(干燥期)和无氧(湿期)之间交替,p,p'-DDD 和 p,p'-DDE 都有可能降解为 1-氯-2,2-双-(对氯苯基)乙烯(p,p'-DDMU),然后进一步转化为 2,2-双(对氯苯基)乙烯(p,p'-DDNU)。在水淹稻田土壤中,p,p'-DDMU 向 p,p'-DDNU 的降解主要发生。然而,p,p'-DDNU 可能不会在有氧表土中转化为其他更高阶的代谢物。总的来说,我们的研究证实了 p,p'-(二氯苯醚菊酯+DBP)是 p,p'-DDT 的代谢物,表明 DDE 和 DDD 是 DDMU 的平行前体,并进一步验证了滴滴涕在表土中的转化途径。