Hemimorphite as a natural sink for arsenic in zinc deposits and related mine tailings: Evidence from single-crystal EPR spectroscopy and hydrothermal synthesis

Mao, Mao; Lin, Jinru; Pan, Yuanming

doi:10.1016/j.gca.2010.02.011

Cited by 16 publications

(23 citation statements)

References 69 publications

(100 reference statements)

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“…The calculated A( 75 As)/h constant of ~2240 MHz along the b axis ( Fig. 9) is significantly smaller than those for the [AsO 4 ] 4center (Dalal et al 1972, Mao et al 2010, but is within the range reported for the [AsO 3 ] 2radical (Lin & McDowell 1964, Serway & Marshall 1966, Dalal et al 1972, Xu 1992, Pöppl et al 1994. Unfortunately, this quartet is not detectable if the magnetic field is away from the b axis, presumably because of intensity reduction related to splitting arising from magnetically nonequivalent sites.…”

Section: Single-crystal Epr Spectramentioning

confidence: 77%

“…On the other hand, extensive substitutions of As 5+ for P 5+ , V 5+ and S 6+ are well known in minerals and synthetic compounds (Pan & Fleet 2002, Nagashima & Armbruster 2010. Similarly, evidence of As 5+ substitution for Si 4+ in tetrahedral sites has been reported in several silicates (Filatov et al 2004, Charnock et al 2007, Mao et al 2010, Nagashima & Armbruster 2010. …”

Section: Implications For Arsenic In Borates and Borate Depositsmentioning

confidence: 91%

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Arsenic Incorporation in Colemanite From Borate Deposits: Data From Icp-Ms, -Sxrf, Xafs and Epr Analyses

Lin

Pan

Chen

et al. 2011

The Canadian Mineralogist

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World-class borate deposits in Turkey and California contain elevated concentrations of arsenic, with adverse effects to not only local suppliers of water, but also the commercial exports of boron products. Most previous studies and remediation efforts of arsenic contamination in borate deposits have focused on sulfarsenides. Inductively coupled plasma -mass spectrometry (ICP-MS) analysis and synchrotron micro-X-ray fluorescence (m-SXRF) mapping reveal that colemanite, a major borate ore mineral, contains up to 125 ppm arsenic. Arsenic K-edge X-ray absorption near-edge structure (XANES) spectra suggest the presence of both As 3+ and As 5+ species in colemanite. The data on K-edge extended X-ray absorption fine structure (EXAFS) show preferential occupancies of As 5+ and As 3+ at the tetrahedral B2 site and the triangular B1 site, respectively. Single-crystal electron paramagnetic resonance (EPR) spectra of gamma-ray-irradiated colemanite measured at 40 K contain an [AsO 3 ] 2center, providing further support for the presence of As 5+ . Therefore, colemanite is a significant source of arsenic contamination, not only in commercial boron products, but also aquifers associated with borate deposits. sommairE Les gisements de borate de Turquie et de Californie, de classe internationale, ont des teneurs élevées en arsenic, ce qui a un effet néfaste non seulement pour les fournisseurs locaux d'eau, mais aussi en matière d'exportation de produits contenant du bore. La plupart des études antérieures et les efforts de remédiation pour contrer les effets de la contamination par l'arsenic ont ciblé les sulfarséniures. Les analyses par plasma inductivement couplé avec spectrométrie de masse (ICP-MS) et au moyen de cartes de répartition acquises par micro-fluorescence X (m-SXRF) avec synchrotron révèlent que la colemanite, composant majeur du minerai boraté, contient jusqu'à 125 ppm d'arsenic. D'après les spectres montrant l'absorption des rayons X au seuil K de l'arsenic (XANES), la colemanite contiendrait à la fois As 3+ et As 5+ . Les données sur la fine structure de l'absorption des rayons X au seuil K (EXAFS) montrent un taux d'occupation préférentiel de As 5+ et As 3+ aux sites tétraédrique B2 et triangulaire B1, respectivement. Les spectres de résonance paramagnétique des électrons (EPR) acquis sur monocristaux irradiés avec rayons gamma et mesurés à 40 K montrent un centre [AsO 3 ] 2-, et fournissent donc un appui additionnel à la présence de As 5+ . Il semble donc clair que la colemanite est une source importante de contamination due à l'arsenic, non seulement dans les produits commerciaux faits de bore mais aussi dans les aquifères associés aux gisements de borate.(Traduit par la Rédaction)

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Section: Single-crystal Epr Spectramentioning

confidence: 77%

Section: Implications For Arsenic In Borates and Borate Depositsmentioning

confidence: 91%

Arsenic Incorporation in Colemanite From Borate Deposits: Data From Icp-Ms, -Sxrf, Xafs and Epr Analyses

Lin

Pan

Chen

et al. 2011

The Canadian Mineralogist

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“…Secondary As-bearing minerals containing structural As include Fe arsenates such as scorodite [2] and kankite [14], Fe sulfoarsenates such as tooeleite [14,15], Ca-Fe arsenates such as yukonite ( Figure 1b) and amorphous forms [14,16,17], and Ca-Mg arsenates such as pharmacolite [18]. Arsenic can also be incorporated in trace amounts in a variety of minerals such as Fe, Mn or Al oxides (Figure 1c), hydroxides and sulfates, other hydrous and anhydrous sulfates, phosphates and hydrous silicates [4,5,13,14,[19][20][21][22][23]. In these cases, the As is taken up by sorption onto the mineral surface [24], or incorporated into the mineral structure by co-precipitation.…”

Section: Introductionmentioning

confidence: 99%

Arsenic-Microbe-Mineral Interactions in Mining-Affected Environments

Hudson‐Edwards

Santini

2013

Minerals

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Abstract:The toxic element arsenic (As) occurs widely in solid and liquid mine wastes. Aqueous forms of arsenic are taken up in As-bearing sulfides, arsenides, sulfosalts, oxides, oxyhydroxides, Fe-oxides, -hydroxides, -oxyhydroxides and -sulfates, and Fe-, Ca-Fe-and other arsenates. Although a considerable body of research has demonstrated that microbes play a significant role in the precipitation and dissolution of these As-bearing minerals, and in the alteration of the redox state of As, in natural and simulated mining environments, the molecular-scale mechanisms of these interactions are still not well understood. Further research is required using traditional and novel mineralogical, spectroscopic and microbiological techniques to further advance this field, and to help design remediation schemes.

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“…Hemimorphite has attracted a large number of studies for its catalytic applications (Breuer et al 1999, Yurieva et al 2001, Catillon-Mucherie et al 2007) and other interesting properties associated with its zeolite-like structure containing confined H 2 O molecules in the channels , Kolesov 2006, Frost et al 2007, Bissengaliyeva et al 2010, Seryotkin & Bakakin 2011. Another source of interest stems from the recognition of hemimorphite as a sink for As and heavy metals (Cd, Cu and Pb) in mine tailings and soils surrounding smelters (Walder & Chavez 1995, Day & Bowell 2005, Espiari et al 2006, Schaider et al 2007, Cabala et al 2009, Mao et al 2010. Mao et al (2010) reported that a suite of 10 samples of hemimorphite from Zn-Pb-Cu deposits contains 6 to 338 ppm As, <0.11 to 39 ppm Cd, 357 to 1200 ppm Cu and 1.9 to 1280 ppm Pb, whereas synthetic hemimorphite can contain up to 2.5 wt.% As 2 O 5 .…”

mentioning

confidence: 99%

“…Another source of interest stems from the recognition of hemimorphite as a sink for As and heavy metals (Cd, Cu and Pb) in mine tailings and soils surrounding smelters (Walder & Chavez 1995, Day & Bowell 2005, Espiari et al 2006, Schaider et al 2007, Cabala et al 2009, Mao et al 2010. Mao et al (2010) reported that a suite of 10 samples of hemimorphite from Zn-Pb-Cu deposits contains 6 to 338 ppm As, <0.11 to 39 ppm Cd, 357 to 1200 ppm Cu and 1.9 to 1280 ppm Pb, whereas synthetic hemimorphite can contain up to 2.5 wt.% As 2 O 5 . Single-crystal electron paramagnetic resonance (EPR) spectra of gamma-ray-irradiated hemimorphite revealed the presence of two arsenic-associated oxygen radicals, [AsO 4 ] 4and [AsO 4 ] 2-, derived from substitutional [AsO 4 ] 3groups at the Si site and provided unambiguous evidence for the sequestration of arsenate in its structure.…”

mentioning

confidence: 99%

Nature of Heavy Metals in Hemimorphite: A Cation-Exchange and Single-Crystal Epr Study

Mao

Pan

2012

The Canadian Mineralogist

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Hemimorphite, a zeolite-like mineral commonly present in supergene non-sulfide Zn deposits and Zn mine tailings, is known to contain elevated levels of As, Cd, Cu and Pb. Cation-exchange experiments of a natural hemimorphite (Mapimi, Durango, Mexico) with 0.1 M CaCl 2 solution at 110 ºC show that As and Cu are retained, whereas Cd and Pb are readily exchanged. The retention of As is consistent with previous single-crystal electron paramagnetic resonance (EPR) results that showed its occurrence as the substitutional As 5+ ion at the Si site. Single-crystal EPR spectra of hemimorphite from the M'Fouati Pb-Zn mine (Reneville, Congo), measured at 120 K and 295 K, show a Cu 2+ center. The best-fit spin Hamiltonian parameters g, A( 63 Cu), P ( 63 Cu) and A( 1 H) of this center at 120 K demonstrate that Cu 2+ resides at the tetrahedral Zn site, not in the channels as suggested by a previous powder EPR study. Cadmium and Pb in hemimorphite are probably present in the channels; this would account for their contrasting behavior from As and Cu during the cation-exchange experiments. However, single-crystal EPR spectra of ten samples of hemimorphite from various Pb-Zn deposits, including those taken after gamma-ray irradiation for doses up to 55 kGy, did not detect any paramagnetic Cd or Pb centers.

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Hemimorphite as a natural sink for arsenic in zinc deposits and related mine tailings: Evidence from single-crystal EPR spectroscopy and hydrothermal synthesis

Cited by 16 publications

References 69 publications

Arsenic Incorporation in Colemanite From Borate Deposits: Data From Icp-Ms, -Sxrf, Xafs and Epr Analyses

Arsenic Incorporation in Colemanite From Borate Deposits: Data From Icp-Ms, -Sxrf, Xafs and Epr Analyses

Arsenic-Microbe-Mineral Interactions in Mining-Affected Environments

Nature of Heavy Metals in Hemimorphite: A Cation-Exchange and Single-Crystal Epr Study

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