Geological and anthropogenic factors influencing mercury speciation in mine wastes: an EXAFS spectroscopy study

Mercury (Hg) speciation influences mobility, reactivity, and bioavailability in areas impacted by Hg mining. Physical, geological, and human influences also affect Hg behavior and fate. The degree of influence of these variables on Hg speciation was studied using extended X-ray absorption fine struc...

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Published in:	Applied geochemistry Vol. 19; no. 3; pp. 379 - 393
Main Authors:	Kim, Christopher S., Rytuba, James J., Brown, Gordon E.
Format:	Journal Article
Language:	English
Published:	Oxford Elsevier 01.03.2004
Subjects:	Earth sciences Earth, ocean, space Engineering and environment geology. Geothermics Exact sciences and technology Pollution, environment geology United States California Nevada USA, Nevada USA, California X-ray data mobility mining waste mercury silica fine-grained materials cinnabar pollution North America human activity spectroscopy particles sulfides chlorides absorption concentration mining impacts halides carbonates speciation mines phase transformation metacinnabar complexes
ISSN:	0883-2927
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Abstract	Mercury (Hg) speciation influences mobility, reactivity, and bioavailability in areas impacted by Hg mining. Physical, geological, and human influences also affect Hg behavior and fate. The degree of influence of these variables on Hg speciation was studied using extended X-ray absorption fine structure spectroscopy on Hg-bearing wastes from mine-impacted regions of California and Nevada. Samples from hot spring Hg deposits contained soluble Hg-chloride phases, which were mainly absent in samples from silica-carbonate Hg deposits. Both deposits, however, had Hg-sulfides dominating as cinnabar and metacinnabar. Calcining appears to promote transformation of cinnabar to metacinnabar, through heating. Total Hg levels in calcines is strongly correlated with particle size, suggesting that insoluble but soft Hg-sulfides weather (mechanically) preferentially and eventually become enriched in the fine-grained fraction, while soluble Hg phases leach out more readily as particle size decreases. Mine waste Hg speciation resembles that in sediments downstream from the tailing piles; i.e., transport does not alter speciation much.
AbstractList	The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X- ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg- sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600 degree C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345 degree C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500-2000 mu m and <45 mu m size fractions (e.g. from 97-810 mg/kg Hg in calcines from the Sulphur Bank Mine, CA). The proportion of Hg-sulfides present also increased by 8-18% as particle size decreased over the same size range. This finding suggests that insoluble yet soft Hg-sulfides are subject to preferential mechanical weathering and become enriched in the fine-grained fraction, while soluble Hg phases are leached out more readily as particle size decreases. The speciation of Hg in mine wastes is similar to that in distributed sediments located downstream from the same waste piles, indicating that the transport of Hg from mine waste piles does not significantly impact Hg speciation. Hg L sub(III)-EXAFS analysis of samples from Au mining regions, where elemental Hg(0) was introduced to aid in the Au recovery process, identified the presence of Hg-sulfides and schuetteite (Hg sub(3)O sub(2)SO sub(4)), which may have formed as a result of long-term Hg(0) burial in reducing high-sulfide sediments. Mercury (Hg) speciation influences mobility, reactivity, and bioavailability in areas impacted by Hg mining. Physical, geological, and human influences also affect Hg behavior and fate. The degree of influence of these variables on Hg speciation was studied using extended X-ray absorption fine structure spectroscopy on Hg-bearing wastes from mine-impacted regions of California and Nevada. Samples from hot spring Hg deposits contained soluble Hg-chloride phases, which were mainly absent in samples from silica-carbonate Hg deposits. Both deposits, however, had Hg-sulfides dominating as cinnabar and metacinnabar. Calcining appears to promote transformation of cinnabar to metacinnabar, through heating. Total Hg levels in calcines is strongly correlated with particle size, suggesting that insoluble but soft Hg-sulfides weather (mechanically) preferentially and eventually become enriched in the fine-grained fraction, while soluble Hg phases leach out more readily as particle size decreases. Mine waste Hg speciation resembles that in sediments downstream from the tailing piles; i.e., transport does not alter speciation much.
Author	Kim, Christopher S. Brown, Gordon E. Rytuba, James J.
Author_xml	– sequence: 1 givenname: Christopher S. surname: Kim fullname: Kim, Christopher S. – sequence: 2 givenname: James J. surname: Rytuba fullname: Rytuba, James J. – sequence: 3 givenname: Gordon E. surname: Brown fullname: Brown, Gordon E.
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Keywords	X-ray data mobility mining waste mercury silica fine-grained materials cinnabar pollution North America human activity spectroscopy particles sulfides chlorides absorption concentration mining impacts halides carbonates speciation mines phase transformation metacinnabar complexes
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Snippet	Mercury (Hg) speciation influences mobility, reactivity, and bioavailability in areas impacted by Hg mining. Physical, geological, and human influences also... The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation...
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SubjectTerms	Earth sciences Earth, ocean, space Engineering and environment geology. Geothermics Exact sciences and technology Pollution, environment geology
Title	Geological and anthropogenic factors influencing mercury speciation in mine wastes: an EXAFS spectroscopy study
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