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铁和电子穿梭介导的(生物)降解 2,4-二硝基苯甲醚(DNAN)。

Iron and Electron Shuttle Mediated (Bio)degradation of 2,4-Dinitroanisole (DNAN).

机构信息

Environmental Engineering and Earth Sciences, Clemson University , 168 Rich Laboratory, Anderson, South Carolina 29625, United States.

Geosyntec Consultants, Ewing, New Jersey 08628, United States.

出版信息

Environ Sci Technol. 2017 Sep 19;51(18):10729-10735. doi: 10.1021/acs.est.7b02433. Epub 2017 Sep 8.

DOI:10.1021/acs.est.7b02433
PMID:28849653
Abstract

The Department of Defense has developed explosives with the insensitive munition 2,4-dinitroanisole (DNAN), to prevent accidental detonations during training and operations. Understanding the fate and transport of DNAN is necessary to assess the risk it may represent to groundwater once the new ordnance is routinely produced and used. Experiments with ferrous iron or anthrahydroquinone-2,6-disulfonate (AHQDS) were conducted from pH 6.0 to 9.0 with initial DNAN concentrations of 100 μM. DNAN was degraded by 1.2 mM Fe(II) at pH 7, 8, and 9, and rates increased with increasing pH. Greater than 90% of the initial 100 μM DNAN was reduced within 10 min at pH 9, and all DNAN was reduced within 1 h. AHQDS reduced DNAN at all pH values tested. Cells of Geobacter metallireducens were added in the presence and absence of Fe(III) and/or anthraquinone-2,6-disulfonate (AQDS), and DNAN was also reduced in all cell suspensions. Cells reduced the compound directly, but both AQDS and Fe(III) increased the reaction rate, via the production of AHQDS and/or Fe(II). DNAN was degraded via two intermediates: 2-methoxy-5-nitroaniline and 4-methoxy-3-nitroaniline, to the amine product 2,4-diaminoanisole. These data suggest that an effective strategy can be developed for DNAN attenuation based on combined biological-abiotic reactions mediated by Fe(III)-reducing microorganisms.

摘要

美国国防部已经开发出了一种名为 2,4-二硝基苯甲醚(DNAN)的钝感炸药,以防止在训练和行动过程中发生意外爆炸。为了评估新型弹药常规生产和使用后对地下水可能造成的风险,有必要了解 DNAN 的归宿和迁移情况。实验在初始 DNAN 浓度为 100 μM、pH 值为 6.0 到 9.0 的条件下,用二价铁或蒽氢醌-2,6-二磺酸盐(AQDS)进行。在 pH 值为 7、8 和 9 时,1.2 mM 的二价铁可以使 DNAN 降解,且随着 pH 值的升高,降解速率也随之增加。在 pH 值为 9 时,初始 100 μM 的 DNAN 在 10 分钟内被还原超过 90%,而在 1 小时内所有的 DNAN 都被还原。在所有测试的 pH 值下,AQDS 都能还原 DNAN。在有或没有三价铁和/或蒽醌-2,6-二磺酸盐(AQDS)存在的情况下,添加 Geobacter metallireducens 细胞,DNAN 也在所有细胞悬浮液中被还原。细胞直接还原该化合物,但 AQDS 和三价铁都通过产生 AHQDS 和/或二价铁来提高反应速率。DNAN 通过两种中间产物(2-甲氧基-5-硝基苯胺和 4-甲氧基-3-硝基苯胺)降解为胺产物 2,4-二氨基苯甲醚。这些数据表明,基于三价铁还原微生物介导的生物-非生物联合反应,可以开发出一种有效的 DNAN 衰减策略。

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