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DOI | 10.1016/j.chemgeo.2017.04.023 |
Uptake of nickel by synthetic mackinawite | |
Wilkin, Richard T.; Beak, Douglas G. | |
发表日期 | 2017-06-25 |
ISSN | 0009-2541 |
卷号 | 462页码:15-29 |
英文摘要 | The uptake of aqueous Ni(II) by synthetic mackinawite (FeS) was examined in anaerobic batch experiments at near-neutral pH (5.2 to 8.4). Initial molar ratios of Ni(II) to FeS ranged from 0.008 to 0.83 and maximum Ni concentrations in mackinawite, expressed as the cation mol fraction, were as high as X-Ni= 0.56 (Fe1-xNixS; 0 <= x <= 1). Greater than 99% Ni removal from solution occurred when Ni loading remained below 0.13 +/- 0.03 (1 sigma) mol Ni per mol FeS due to sorption of Ni at the mackinawite surface. Characterization of experimental solids using X-ray diffraction and Raman spectroscopy showed patterns characteristic of nanocrystalline mackinawite; no evidence of nickel monosulfide (alpha-NiS or millerite), polydymite (Ni3S4), or godlevskite [(Ni,Fe)(9)S-8] formation was indicated regardless of the amount of Ni loading. Slight expansion of the c-axis correlated with increasing Ni content in synthetic mackinawite, from c = 5.07 +/- 0.01 angstrom at X-Ni = 0.02 to c = 5.10 +/- 0.01 angstrom at X-Ni= 0.38. Ni K-edge extended X-ray absorption fine structure (EXAFS) spectra of synthetic Ni-bearing mackinawite are similar in phase and amplitude to the Fe K-edge EXAFS spectrum of Ni-free mackinawite, indicating that the molecular environment of Ni2+ in Ni-bearing mackinawite is similar to that of Fe2+ in Ni-free mackinawite. EXAFS data fitting of Ni-bearing mackinawite with X-Ni = 0.42 indicated a coordination number of 4.04 +/- 0.30 and an average Ni-S bond distance of 2.28 angstrom, in good agreement with the Fe-S bond distance of 2.26 angstrom in mackinawite, tetrahedral Fe coordination, and slight lattice expansion along the c-axis. At lower Ni loadings (X-Ni = 0.05-0.11), EXAFS analysis showed a decrease in Ni-S coordination towards CN = 3, which reflects the influence of sorbed Ni. Continued Ni uptake, past the maximum amount of sorption, was accompanied by proportional molar release of Fe to solution. Interstitial occupancy of Ni within the mackinawite interlayer may be transitional to structural substitution of Fe. The Ni-mackinawite solid-solution is described by a one-site binary mixing model: lnK(d) = ln K-e-W/RT(1-2X(M)) where Kd is the distribution coefficient, Ke is the ratio of equilibrium constants for Ni-mackinawite and mackinawite (14.4 +/- 1.3), W is an ion interaction parameter, and Xisli is the mole fraction of end-member NiS in the solid solution. The experimentally determined value of W is 17.74 +/- 1.15 kJ/mol and indicates significant non-ideality of the solid solution. Transformation processes were evaluated by aging Ni-mackinawite with polysulfides and solutions saturated with air. Reaction of Ni-mackinawite with polysulfides led to the formation of pyrite (FeS2) and Ni retention in the solid phase. When Ni-mackinawite was aged in the presence of dissolved oxygen, transformation to goethite (FeOOH) and violarite (FeNi2S4) was observed. |
英文关键词 | Nickel;FeS;Mackinawite;Iron sulfide;Groundwater;Adsorption;Solid solution |
语种 | 英语 |
WOS记录号 | WOS:000403517900002 |
来源期刊 | CHEMICAL GEOLOGY
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来源机构 | 美国环保署 |
文献类型 | 期刊论文 |
条目标识符 | http://gcip.llas.ac.cn/handle/2XKMVOVA/56634 |
作者单位 | US EPA, Natl Risk Management Res Lab, Ground Water & Ecosyst Restorat Div, 919 Kerr Res Dr, Ada, OK 74820 USA |
推荐引用方式 GB/T 7714 | Wilkin, Richard T.,Beak, Douglas G.. Uptake of nickel by synthetic mackinawite[J]. 美国环保署,2017,462:15-29. |
APA | Wilkin, Richard T.,&Beak, Douglas G..(2017).Uptake of nickel by synthetic mackinawite.CHEMICAL GEOLOGY,462,15-29. |
MLA | Wilkin, Richard T.,et al."Uptake of nickel by synthetic mackinawite".CHEMICAL GEOLOGY 462(2017):15-29. |
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