Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Ontario, Canada.
Département de Chimie, Laboratory COVACHIMM2E, Université des Antilles, Pointe à Pitre Cedex, Guadeloupe (FWI), France.
PLoS One. 2020 Apr 13;15(4):e0231219. doi: 10.1371/journal.pone.0231219. eCollection 2020.
The historic use of chlordecone (C10Cl10O) as a pesticide to control banana weevil infestations has resulted in pollution of large land areas in the French West Indies. Although currently banned, chlordecone persists because it adsorbs strongly to soil and its complex bis-homocubane structure is stable, particularly under aerobic conditions. Abiotic chemical transformation catalyzed by reduced vitamin B12 has been shown to break down chlordecone by opening the cage structure to produce C9 polychloroindenes. More recently these C9 polychloroindenes were also observed as products of anaerobic microbiological transformation. To investigate the anaerobic biotransformation of chlordecone by microbes native to the French West Indies, microcosms were constructed anaerobically from chlordecone impacted Guadeloupe soil and sludge to mimic natural attenuation and eletron donor-stimulated reductive dechlorination. Original microcosms and transfers were incubated over a period of 8 years, during which they were repeatedly amended with chlordecone and electron donor (ethanol and acetone). Using LC-MS, chlordecone and degradation products were detected in all the biologically active microcosms. Observed products included monohydro-, dihydro- and trihydrochlordecone derivatives (C10Cl10-nO2Hn; n = 1,2,3), as well as "open cage" C9 polychloroindene compounds (C9Cl5-nH3+n n = 0,1,2) and C10 carboxylated polychloroindene derivatives (C10Cl4-nO2H4+n, n = 0-3). Products with as many as 9 chlorine atoms removed were detected. These products were not observed in sterile (poisoned) microcosms. Chlordecone concentrations decreased in active microcosms as concentrations of products increased, indicating that anaerobic dechlorination processes have occurred. The data enabled a crude estimation of partitioning coefficients between soil and water, showing that carboxylated intermediates sorb poorly and as a consequence may be flushed away, while polychlorinated indenes sorb strongly to soil. Microbial community analysis in microcosms revealed enrichment of anaerobic fermenting and acetogenic microbes possibly involved in anaerobic chlordecone biotransformation. It thus should be possible to stimuilate anaerobic dechlorination through donor amendment to contaminated soils, particularly as some metabolites (in particular pentachloroindene) were already detected in field samples as a result of intrinsic processes. Extensive dechlorination in the microcosms, with evidence for up to 9 Cl atoms removed from the parent molecule is game-changing, giving hope to the possibility of using bioremediation to reduce the impact of CLD contamination.
历史上曾使用十氯酮(C10Cl10O)作为杀虫剂来控制香蕉象鼻虫的侵害,导致法属西印度群岛的大片土地受到污染。尽管目前已被禁用,但十氯酮仍在持续存在,因为它强烈吸附在土壤上,其复杂的双立方烷结构在有氧条件下特别稳定。已证明,还原型维生素 B12 催化的非生物化学转化可以通过打开笼状结构来分解十氯酮,生成 C9 多氯茚。最近,这些 C9 多氯茚也被观察到是厌氧微生物转化的产物。为了研究法属西印度群岛本土微生物对十氯酮的厌氧生物转化,从受十氯酮污染的瓜德罗普岛土壤和污泥中构建了微宇宙,以模拟自然衰减和电子供体刺激的还原脱氯。原始微宇宙和转移物在 8 年的时间里进行了孵育,在此期间,它们反复添加十氯酮和电子供体(乙醇和丙酮)。使用 LC-MS 在所有具有生物活性的微宇宙中均检测到十氯酮和降解产物。观察到的产物包括单氢、二氢和三氢十氯酮衍生物(C10Cl10-nO2Hn;n=1,2,3),以及“开笼”C9 多氯茚化合物(C9Cl5-nH3+n n=0,1,2)和 C10 羧化多氯茚衍生物(C10Cl4-nO2H4+n,n=0-3)。检测到去除多达 9 个氯原子的产物。在无菌(中毒)微宇宙中未观察到这些产物。随着产物浓度的增加,活性微宇宙中的十氯酮浓度降低,表明发生了厌氧脱氯过程。数据允许对土壤与水之间的分配系数进行粗略估计,表明羧基化中间体吸附不良,因此可能被冲洗掉,而多氯茚则强烈吸附在土壤上。微宇宙中的微生物群落分析表明,可能参与厌氧十氯酮生物转化的厌氧发酵和产乙酸微生物得到了富集。因此,通过供体添加刺激受污染土壤中的厌氧脱氯是有可能的,特别是因为一些代谢物(特别是五氯茚)已经在现场样本中作为内在过程的结果被检测到。微宇宙中广泛的脱氯作用,证明母体分子上有多达 9 个氯原子被去除,这是一个改变游戏规则的发现,为使用生物修复来减少 CLD 污染的影响带来了希望。