共存的磷酸盐控制铁(II)催化水合铁转化过程中砷酸盐的形态和分配。

IF 2.9 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
ACS Earth and Space Chemistry Pub Date : 2025-06-10 eCollection Date: 2025-06-19 DOI:10.1021/acsearthspacechem.5c00061
Jeffrey Paulo H Perez, A Li Han Chan, J Frederick W Mosselmans, Liane G Benning
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引用次数: 0

摘要

砷在土壤和沉积物中的固定化主要是通过其吸附或掺入活性土壤矿物质(如氧化铁)来控制的。然而,共存的离子(如溶解的碳酸氢盐、磷酸盐、二氧化硅和有机物)会对有毒的砷酸盐与铁(氧)-氢氧化物的相互作用产生负面影响。特别值得注意的是无机磷酸盐,由于其化学和结构性质与无机砷酸盐相似,它是吸附位点的有力竞争者。我们对磷酸盐和砷酸盐之间这种竞争性质的理解主要集中在对矿物吸附能力和动力学的影响上。然而,我们对共存的磷酸盐如何改变含砷铁(氧)氧化物的稳定性和转化途径知之甚少。特别是,在缺氧条件下,砷酸盐固定的长期命运和行为是未知的。在这里,我们通过矿物转化反应记录了磷酸盐(P)和砷酸盐[As-(V)]在次生矿物产品中的固定化,并表征了它们在转化过程中变化的成分。我们在控制初始P/As-(V)比率的情况下做到了这一点。我们的研究结果表明,在没有P/As-(V)比或P/As-(V)比较低的情况下,初始的水合铁迅速转化为绿锈硫酸盐(GRSO4),并在180天后进一步转化为磁铁矿。同时,较高的P/As-(V)比导致GRSO4与活铁矿混合,磁铁矿占一小部分。P/As-(V)比值对As-(V)的形成和分配也有一定的影响。较高的P/As-(V)比值也导致矿物结合的As-(V)更快地部分还原为As-(III)。最重要的发现是,最初的铁水合体结合的As-(V)在结构上被结合到磁铁矿[低P/As-(V)比]或橄榄石[高P/As-(V)比]中,因此被固定而不稳定。总的来说,我们的研究结果强调了共存的磷酸盐在控制缺氧、富Fe2+地下环境(如受污染的含水层)的毒性和流动性方面的影响。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Coexisting Phosphate Controls Arsenate Speciation and Partitioning during Fe(II)-Catalyzed Ferrihydrite Transformation.

Arsenic immobilization in soils and sediments is primarily controlled by its sorption onto or incorporation into reactive soil minerals, such as iron (oxyhydr)-oxides. However, coexisting ions (e.g., dissolved bicarbonate, phosphate, silica, and organic matter) can negatively impact the interaction of the toxic arsenate species with iron (oxy)-hydroxides. Of special note is inorganic phosphate, which is a strong competitor for sorption sites due to its analogous chemical and structural nature to inorganic arsenate. Much of our understanding of this competing nature between phosphate and arsenate focuses on the impact on mineral sorption capacities and kinetics. However, we know very little about how coexisting phosphate will alter the stability and transformation pathways of arsenate-bearing Fe (oxyhydr)-oxides. In particular, the long-term fate and behavior regarding arsenate immobilization are unknown under anoxic conditions. Here, we document, through mineral transformation reactions, the immobilization of both phosphate (P) and arsenate [As-(V)] in secondary mineral products and characterize their changing compositions during the transformations. We did this while controlling the initial P/As-(V) ratios. Our results document that, in the absence or at low P/As-(V) ratios, the initial ferrihydrite rapidly transforms to green rust sulfate (GRSO4 ), which further transforms into magnetite after 180 days. Meanwhile, high P/As-(V) ratios resulted in a mixture of GRSO4 and vivianite, with magnetite as a minor fraction. Invariably, the speciation and partitioning of As-(V) were also affected by the P/As-(V) ratio. A higher P/As-(V) ratio also led to a faster partial reduction of mineral-bound As-(V) to As-(III). The most important finding is that the initial ferrihydrite-bound As-(V) became structurally incorporated into magnetite [low P/As-(V) ratio] or vivianite [high P/As-(V) ratio] and was thus immobilized and not labile. Overall, our results highlight the influence of coexisting phosphate in controlling the toxicity and mobility in anoxic, Fe2+-rich subsurface settings, such as contaminated aquifers.

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来源期刊
ACS Earth and Space Chemistry
ACS Earth and Space Chemistry Earth and Planetary Sciences-Geochemistry and Petrology
CiteScore
5.30
自引率
11.80%
发文量
249
期刊介绍: The scope of ACS Earth and Space Chemistry includes the application of analytical, experimental and theoretical chemistry to investigate research questions relevant to the Earth and Space. The journal encompasses the highly interdisciplinary nature of research in this area, while emphasizing chemistry and chemical research tools as the unifying theme. The journal publishes broadly in the domains of high- and low-temperature geochemistry, atmospheric chemistry, marine chemistry, planetary chemistry, astrochemistry, and analytical geochemistry. ACS Earth and Space Chemistry publishes Articles, Letters, Reviews, and Features to provide flexible formats to readily communicate all aspects of research in these fields.
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