Department of Environmental Science and Engineering , Huaqiao University , Xiamen 361021 , Fujian , China.
Department of Cellular Biology and Pharmacology, Herbert Wertheim College of Medicine , Florida International University , Miami 33199 , Florida , United States.
Environ Sci Technol. 2019 Dec 3;53(23):13648-13656. doi: 10.1021/acs.est.9b04026. Epub 2019 Nov 14.
Massive amounts of methyl [e.g., methylarsenate, MAs(V)] and aromatic arsenicals [e.g., roxarsone (4-hydroxy-3-nitrophenylarsonate, Rox(V)] have been utilized as herbicides for weed control and growth promotors for poultry and swine, respectively. The majority of these organoarsenicals degrade into more toxic inorganic species. Here, we demonstrate that the legume symbiont both reduces MAs(V) to MAs(III) and catalyzes sequential two-step reduction of nitro and arsenate groups in Rox(V), producing the highly toxic trivalent amino aromatic derivative 4-hydroxy-3-aminophenylarsenite (HAPA(III)). The existence of this process suggests that possesses the ability to transform pentavalent methyl and aromatic arsenicals into antibiotics to provide a competitive advantage over other microbes, which would be a critical process for the synthetic aromatic arsenicals to function as antimicrobial growth promoters. The activated trivalent aromatic arsenicals are degraded into less-toxic inorganic species by an MAs(III)-demethylating aerobe, suggesting that environmental aromatic arsenicals also undergo a multiple-step degradation pathway, in analogy with the previously reported demethylation pathway of the methylarsenate herbicide. We further show that an FAD-NADPH-dependent nitroreductase encoded by gene catalyzes nitroreduction of roxarsone both in vivo and in vitro. Our results demonstrate that environmental organoarsenicals trigger competition between members of microbial communities, resulting in gradual degradation of organoarsenicals and contamination by inorganic arsenic.
大量的甲基[例如,甲基砷酸盐,MAs(V)]和芳香族砷化物[例如,洛克沙胂(4-羟基-3-硝基苯砷酸,Rox(V)]分别被用作除草剂来控制杂草和作为家禽和猪的生长促进剂。这些有机砷化物中的大多数会降解为毒性更高的无机物种。在这里,我们证明豆科植物共生体 既能将 MAs(V)还原为 MAs(III),又能催化 Rox(V)中硝和砷酸盐基团的连续两步还原,生成高度毒性的三价氨基芳香衍生物 4-羟基-3-氨基苯砷酸(HAPA(III))。这个过程的存在表明 具有将五价甲基和芳香族砷化物转化为抗生素的能力,从而为其提供相对于其他微生物的竞争优势,这对于作为抗菌生长促进剂的合成芳香族砷化物来说是一个关键过程。激活的三价芳香族砷化物被一种 MAs(III)-去甲基化需氧菌降解为毒性较低的无机物种,这表明环境芳香族砷化物也经历了一个多步降解途径,与之前报道的甲基砷酸盐除草剂的去甲基化途径类似。我们进一步表明,由 基因编码的 FAD-NADPH 依赖性硝基还原酶在体内和体外都能催化洛克沙胂的硝基还原。我们的结果表明,环境有机砷化物引发微生物群落成员之间的竞争,导致有机砷化物逐渐降解和无机砷污染。