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在 pH 值为 4 和 7 条件下 Fe-As 共沉淀的长期稳定性:控制砷行为的机制。

The long-term stability of Fe-As coprecipitates at pH 4 and 7: Mechanisms controlling the arsenic behavior.

机构信息

Key Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang, 110016, China.

Key Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang, 110016, China.

出版信息

J Hazard Mater. 2019 Jul 15;374:276-286. doi: 10.1016/j.jhazmat.2019.04.054. Epub 2019 Apr 15.

Abstract

Hydrometallurgical Fe-As coprecipitates, which are amorphous in nature, could re-crystallize gradually and pose risks of contamination to the environment. However, the mechanisms controlling the As behavior when the Fe-As coprecipitates stored at different pHs is still not fully understood. This work systematically investigated the fate of As and the transformation process of the coprecipitates (Fe/As = ˜4) at different pHs and temperatures. XRD, EXAFS, HRTEM, and chemical extraction methods were employed to characterize the crystallinity degrees and the transformation products of the coprecipitates. The results showed that the coprecipitates are more stable at acidic pH than at neutral pH. For those samples aged at pH 4, the arsenic speciation includes poorly crystalline ferric arsenate (PCFA) and As adsorbed on 2-line ferrihydrite (Fh). Due to the presence of PCFA, the Fe/As molar ratio for the latter phase is much higher than the bulk Fe/As molar ratio (˜4 in this work) of the coprecipitates and controls As release. However, for those samples aged at pH 7, due to the fact that 2-line Fh is the major As-bearing phase, slight changes of the crystallinity degrees of 2-line Fh will trigger As release.

摘要

水冶法铁砷共沉淀物本质上是无定形的,可能会逐渐重结晶,并对环境造成污染的风险。然而,当铁砷共沉淀物在不同 pH 值下储存时,控制砷行为的机制仍未完全理解。本工作系统地研究了不同 pH 值和温度下砷的归宿和共沉淀物(Fe/As≈4)的转化过程。采用 XRD、EXAFS、HRTEM 和化学提取方法来表征共沉淀物的结晶度和转化产物。结果表明,共沉淀物在酸性 pH 值下比在中性 pH 值下更稳定。对于在 pH 4 下老化的样品,砷的形态包括非晶态铁砷酸盐(PCFA)和吸附在 2 线水铁矿(Fh)上的砷。由于 PCFA 的存在,后一相中 Fe/As 的摩尔比远高于共沉淀物的本体 Fe/As 摩尔比(本工作中约为 4),控制砷的释放。然而,对于在 pH 7 下老化的样品,由于 2 线 Fh 是主要的含砷相,2 线 Fh 的结晶度稍有变化就会引发砷的释放。

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