Corkhill,C.L., Wincott,P.L., Lloyd,J.R. and Vaughan,D.J.(2008): The oxidative dissolution of arsenopyrite (FeAsS) and enargite (Cu3AsS4) by Leptospirillum ferrooxidans. Geochimica et Cosmochimica Acta, 72, 5616-5633.

『鉄酸化細菌Leptospirillum ferrooxidansによる硫砒鉄鉱(FeAsS)と硫砒銅鉱(Cu3AsS4)の酸化溶解』


Abstract
 Arsenopyrite (FeAsS) and enargite (Cu3AsS4) fractured in a nitrogen atmosphere were characterised after acidic (pH 1.8), oxidative dissolution in both the presence and absence of the acidophilic microorganism Leptospirillum ferrooxidans. Dissolution was monitored through analysis of the coexisting aqueous solution using inductively coupled plasma atomic emission spectroscopy and coupled ion chromatography-inductively coupled plasma mass spectrometry, and chemical changes at the mineral surface observed using X-ray photoelectron spectroscopy and environmental scanning electron microscopy (ESEM). Biologically mediated oxidation of arsenopyrite and enargite (2.5 g in 25 ml) was seen to proceed to a greater extent than abiotic oxidation, although arsenopyrite oxidation was significantly greater than enargite oxidation. These dissolution reactions were associated with the release of 〜917 and 〜180 ppm of arsenic into solution. The formation of Fe(III)-oxyhydroxides, ferric sulphate and arsenate was observed for arsenopyrite, thiosulphate and an unknown arsenic oxide for enargite. ESEM revealed an extensive coating of an extracellular polymeric substance associated with the L.ferrooxidans cells on the arsenopyrite surface and bacterial leach pits suggest a direct biological oxidation mechanism, although a combination of indirect and direct bioleaching cannot be ruled out. Although the relative oxidation rates of enargite were greater in the presence of L.ferrooxidans, cells were not in contact with the surface suggesting an indirect biological oxidation mechanism. Cells of L.ferrooxidans appear able to withstand several hundreds of ppm of As(III) and As(V).』

1. Introduction
2. Experimental methods
 2.1. Sample preparation and procedure
 2.2. Analytical instrumentation
3. Results
 3.1. XPS analysis of arsenopyrite and enargite surfaces
  3.1.1. Freshly cleaved arsenopyrite
   3.1.1.1. Fe 2p(3/2) spectrum
   3.1.1.2. As 3d(5/2) spectrum
   3.1.1.3. S 2p(3/2) spectrum
  3.1.2. Freshly cleaved enargite
   3.1.2.1. Cu 2p(3/2) spectrum
   3.1.2.2. As 3d(5/2) spectrum
   3.1.2.3. S 2p(3/2) spectrum
  3.1.3. Surface treatment of arsenopyrite with L.ferrooxidans vs abiotic control surfaces
   3.1.3.1. Fe 2p(3/2) spectrum
   3.1.3.2. As 3d(5/2) spectrum
   3.1.3.3. S 2p(3/2) spectrum
  3.1.4. Surface treatment of enargite with L.ferrooxidans vs abiotic control surfaces
   3.1.4.1. Cu 2p(3/2) spectrum
   3.1.4.2. As 3d(5/2) spectrum
   3.1.4.3. S 2p(3/2) spectrum
 3.2. Auger parameter analysis
 3.3. Arsenopyrite and enargite surface morphology and attachment of L.ferrooxidans (ESEM)
  3.3.1. Fresh and abiotically reacted surfaces
  3.3.2. Leptspirillum ferrooxidans reacted surfaces
 3.4. Aqueous phase chemistry
  3.4.1. Major element analysis
   3.4.1.1. Arsenopyrite
   3.4.1.2. Enargite
  3.4.2. Arsenic speciation analysis
4. Discussion
 4.1. Influence of bacteria on the oxidative dissolution of arsenopyrite
  4.1.1. Abiotic vs bacterially mediated oxidative dissolution
  4.1.2. Arsenopyrite geochemistry and biological response to arsenic
 4.2. Cell attachment and biofilm formation - implications for direct vs indirect bioleaching
 4.3. Influence of bacteria on the oxidative dissolution of enargite
5. Conclusions
Acknowledgments
References



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