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Fe(Ⅲ) Nucleation in the Presence of Bivalent Cations and Oxyanions Leads to Subnanoscale 7 A Polymers

机译:Fe(Ⅲ)在二价阳离子和高氧阴离子存在下的成核作用导致亚纳米级7 A聚合物

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摘要

Highly disordered Fe(Ⅲ) phases formed in the presence of bivalent cations and oxyanions represent important components of the global Fe cycle due to their potential for rapid turnover and their critical roles in controlling the speciation of major and trace elements. However, a poor understanding of the formation pathway and structure of these Fe phases has prevented assessments of their thermodynamic properties and biogeochenucal reactivity. In this work, we derive structural models for the Fe(Ⅲ)-As(Ⅴ)-Ca and Fe(Ⅲ)-P-Ca polymers formed from Fe(Ⅱ) oxidation and Fe(Ⅲ) polymerization in the presence of As(Ⅴ)/P and Ca. The polymer phase consists of a less than 7 A coherent network of As(Ⅴ)/P coordinated to Fe(Ⅲ) polyhedra, with varying amounts of Ca bound directly and indirectly to the oxyanion. This phase forms at the onset of Fe(Ⅱ) oxidation and, because of its large oxyanion:Fe solids ratio, depletes the oxyanion concentration with only small amounts of Fe. Our results demonstrate that when a steady supply of Fe(Ⅲ) is provided from an Fe(Ⅱ) source, these Fe(Ⅲ) polymers, which dominate oxyanion uptake, form with little dependence on the initial oxyanion concentration. The formation mechanisms and structures of the oxyanion-rich Fe(Ⅲ) polymers determined in this study enable future thermodynamic investigations of these phases, which are required to model the interrelated biogeochemical cycles of Fe, As(Ⅴ)/P, and Ca.
机译:在存在二价阳离子和氧阴离子的情况下形成的高度无序的Fe(Ⅲ)相代表了全球Fe循环的重要组成部分,因为它们具有快速更新的潜力以及在控制主要和微量元素的形成中的关键作用。但是,对这些Fe相的形成途径和结构的了解不足,无法评估其热力学性质和生物地球化学反应性。在这项工作中,我们推导了在Fe(Ⅱ)氧化和Fe(Ⅲ)聚合存在下,由Fe(Ⅱ)氧化和Fe(Ⅲ)聚合形成的Fe(Ⅲ)-As(Ⅴ)-Ca和Fe(Ⅲ)-P-Ca聚合物的结构模型。 Ⅴ)/ P和Ca。聚合物相由少于7 A的As(Ⅴ)/ P相干网络组成,与Fe(Ⅲ)多面体配位,并且有不同数量的Ca直接或间接与氧阴离子键合。该相在Fe(Ⅱ)氧化开始时形成,由于其高的氧阴离子:Fe固形比,仅少量的Fe就消耗了氧阴离子浓度。我们的结果表明,当从Fe(Ⅱ)来源提供稳定的Fe(Ⅲ)供给时,这些主要控制氧阴离子吸收的Fe(Ⅲ)聚合物的形成对初始氧阴离子浓度的依赖性很小。在这项研究中确定的富氧阴离子Fe(Ⅲ)聚合物的形成机理和结构使这些相的未来热力学研究成为可能,以模拟相关的Fe,As(Ⅴ)/ P和Ca的生物地球化学循环。

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  • 来源
    《Environmental Science & Technology》 |2014年第20期|11828-11836|共9页
  • 作者单位

    Department of Civil and Environmental Engineering, University of California, Berkeley, Berkeley, California 94720, United States ,Institut de Dynamiques de la Surface Terrestre, University of Lausanne, Lausanne, Switzerland;

    Department of Civil and Environmental Engineering, University of California, Berkeley, Berkeley, California 94720, United States ,Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States;

    Institut de Dynamiques de la Surface Terrestre, University of Lausanne, Lausanne 1015, Switzerland;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
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