Heavy Metal–Mineral Associations in Coeur d’Alene River Sediments: A Synchrotron-Based Analysis

Nearly a century of mining activities upstream have contaminated Lake Coeur d’Alene and its tributaries with Pb, Zn, and other heavy metals. Heavy metal concentrations in sediments of the Coeur d’Alene watershed have been shown to be inversely proportional to the sediment size fraction; thus, analysis on a very small scale is essential to determine the mobility and stability of heavy metals in this environment. Micron-scale synchrotron-based methods were used to determine the association of heavy metals with solid phases in sediments of the Coeur d’Alene River. Bulk X-ray diffraction (XRD), extended X-ray absorption fine structure spectroscopy, and synchrotron-based microfocused XRD combined with microfocused X-ray fluorescence mapping indicate the presence of crystalline Pb- and Zn-bearing mineral phases of dundasite [Pb2Al4(CO3)4(OH)8·3H2O], coronadite [PbMn8O16], stolzite [PbWO4], mattheddleite [Pb10(SiO4)3.5(SO4)2Cl2], bindheimite [Pb2Sb2O7], and smithsonite [ZnCO3]. Likely phases for Zn and Pb adsorption were ferrihydrite, diaspore [AlO(OH)], manganite [Mn(III)O(OH)], muscovite [KAl2(Si3Al)O10(OH,F)2], biotite [K(Fe,Mg)3AlSi3O10(F,OH)2], and montmorillonite [Na0.3(Al,Mg)2Si4O10(OH)2·8H2O]. The large predominance of Fe and Mn (hydr)oxides over other sorbent minerals suggests that the metal sorption behavior is dominated by these (hydr)oxide phases.

[1]  Robert B. Cook,et al.  Effect of mining and related activities on the sediment trace element geochemistry of lake coeur D'Alene, idaho, USA. Part I: Surface sediments , 1993 .

[2]  J. Lloyd,et al.  Microbial detoxification of metals and radionuclides. , 2001, Current opinion in biotechnology.

[3]  R. Kukkadapu,et al.  Biotransformation of Ni-substituted hydrous ferric oxide by an Fe(III)-reducing bacterium. , 2001, Environmental science & technology.

[4]  Scott Fendorf,et al.  Metal(loid) diagenesis in mine-impacted sediments of Lake Coeur d'Alene, Idaho. , 2006, Environmental science & technology.

[5]  J. Mahoney,et al.  Analysis of arsenic speciation in mine contaminated lacustrine sediment using selective sequential extraction, HR-ICPMS and TEM , 2008 .

[6]  Samuel M. Webb,et al.  SIXpack: a graphical user interface for XAS analysis using IFEFFIT , 2005 .

[7]  G. Geesey,et al.  Resolving biogeochemical phenomena at high spatial resolution through electron microscopy , 2008, Geobiology.

[8]  P. Weidler,et al.  Far-Infrared Spectroscopy of Interlayer Vibrations of Cu(II), Mg(II), Zn(II), and Al(III) Intercalated Muscovite , 2006, Applied spectroscopy.

[9]  M. Schlegel,et al.  Zn incorporation in hydroxy-Al- and keggin Al13-intercalated montmorillonite: a powder and polarized EXAFS study. , 2007, Environmental science & technology.

[10]  James G. Moberly,et al.  Reactive diffusive transport of heavy metals in Lake Coeur d'Alene sediments , 2006 .

[11]  R. Rosenzweig,et al.  Redistribution of trace elements from contaminated sediments of Lake Coeur d'Alene during oxygenation , 1999 .

[12]  J. Post,et al.  Manganese oxide minerals: crystal structures and economic and environmental significance. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[13]  A. Horowitz,et al.  The effect of mining and related activities on the sediment–trace element geochemistry of Lake Coeur d'Alene, Idaho, USA. Part III. Downstream effects: the Spokane River Basin , 2001 .

[14]  P. E. Rosenberg,et al.  Isotope Geochemistry of Ankerite-Bearing Veins Associated with the Coeur d’Alene Mining District, Idaho , 2000 .

[15]  V. Salters,et al.  PROVENANCE OF ORE METALS IN BASE AND PRECIOUS METAL DEPOSITS OF CENTRAL IDAHO AS INFERRED FROM LEAD ISOTOPES , 2006 .

[16]  A. Paulson.  The transport and fate of Fe, Mn, Cu, Zn, Cd, Pb and SO4 in a groundwater plume and in downstream surface waters in the Coeur d'Alene Mining District, Idaho, U.S.A. , 1997 .

[17]  David J. Vaughan,et al.  Experimental studies of the interaction of aqueous metal cations with mineral substrates: Lead, cadmium, and copper with perthitic feldspar, muscovite, and biotite , 1997 .

[18]  J. Bowles.  Iron Oxides in the Laboratory , 1992, Mineralogical Magazine.

[19]  J. Mauk,et al.  Stratigraphy of the Proterozoic Revett Formation and Its Control on Ag-Pb-Zn Vein Mineralization in the Coeur d’Alene District, Idaho , 2004 .

[20]  B. Bostick,et al.  Seasonal fluctuations in zinc speciation within a contaminated wetland. , 2001, Environmental science & technology.

[21]  R. Signell,et al.  Role of sediment resuspension in the remobilization of particulate-phase metals from coastal sediments. , 2007, Environmental science & technology.

[22]  D. Sparks,et al.  Kinetic controls on Cu and Pb sorption by ferrihydrite. , 2001, Environmental science & technology.

[23]  D. Leach,et al.  Metamorphic origin of the Coeur d'Alene base- and precious-metal veins in the Belt basin, Idaho and Montana , 1988 .

[24]  H. A. Gebbie,et al.  Far-infrared spectroscopy , 1971 .

[25]  M. Siegert,et al.  Developments in Earth and Environmental Sciences , 2008 .

[26]  M. Mergeay,et al.  Characterization of the bacterial community of a zinc-polluted soil. , 1999, Canadian journal of microbiology.

[27]  A. Konopka,et al.  Microbial Biomass and Activity in Lead-Contaminated Soil , 1999, Applied and Environmental Microbiology.

[28]  G. F. Eaton,et al.  Age and Origin of Base and Precious Metal Veins of the Coeur D’Alene Mining District, Idaho , 2000 .

[29]  A. Greene,et al.  Microbial Formation of Manganese Oxides , 1991, Applied and environmental microbiology.

[30]  A. Paulson.  Biogeochemical removal of Zn and Cd in the Coeur D'Alene River (Idaho, USA), downstream of a mining district. , 2001, The Science of the total environment.

[31]  A. Bookstrom,et al.  Lead-rich sediments, Coeur d'Alene River Valley, Idaho: area, volume, tonnage, and lead content , 2001 .

[32]  C. Wai,et al.  Heavy metal content in the sediments of the southern part of the coeur d'Alene Lake , 1974 .

[33]  T. Borch,et al.  Chromate reduction and retention processes within arid subsurface environments. , 2005, Environmental science & technology.

[34]  John W. Anthony,et al.  Handbook of mineralogy , 1990 .

[35]  R. Cook,et al.  The Effect of mining and related activities on the sediment-trace element geochemistry of Lake Coeur d'Alene, Idaho, U.S.A.; Part II, Subsurface sediments , 1993 .

[36]  L. Balistrieri,et al.  Modeling precipitation and sorption of elements during mixing of river water and porewater in the Coeur d'Alene River basin. , 2003, Environmental science & technology.

[37]  L. Fanfani,et al.  The crystal structure of dundasite , 1972, Mineralogical Magazine.

[38]  S. Spring,et al.  Evidence for Microbial Fe(III) Reduction in Anoxic, Mining-Impacted Lake Sediments (Lake Coeur d'Alene, Idaho) , 2000, Applied and Environmental Microbiology.

[39]  P. Brookes.  Microbial biomass and activity measurements in soil , 1985 .

[40]  L. Balistrieri,et al.  Modeling metal removal onto natural particles formed during mixing of acid rock drainage with ambient surface water. , 2002, Environmental science & technology.

[41]  D. Bish,et al.  Rietveld refinement of the coronadite structure , 1989 .

[42]  L. Balistrieri,et al.  Modeling Removal of Cd, Cu, Pb, and Zn in Acidic Groundwater during Neutralization by Ambient Surface Waters and Groundwaters , 1999 .

[43]  Akademii︠a︡ medit︠s︡inskikh nauk Sssr.  Journal of physics , 1939 .

[44]  J. Vincent,et al.  Chemical speciation of lead dust associated with primary lead smelting. , 1998, Environmental health perspectives.

[45]  R. Rosenzweig,et al.  Biotic Generation of Arsenic(III) in Metal(loid)-Contaminated Freshwater Lake Sediments , 1998 .

[46]  R. Kukkadapu,et al.  Secondary Mineralization Pathways Induced by Dissimilatory Iron Reduction of Ferrihydrite Under Advective Flow , 2003 .

[47]  T. Borch,et al.  Chapter 12 Phosphate Interactions with Iron (Hydr)oxides: Mineralization Pathways and Phosphorus Retention upon Bioreduction , 2009 .

[48]  S. Simpson,et al.  Effect of overlying water pH, dissolved oxygen, salinity and sediment disturbances on metal release and sequestration from metal contaminated marine sediments. , 2007, Chemosphere.

[49]  Yu Liu,et al.  Kinetic Responses of Activated Sludge Microorganisms to Individual and Joint Copper and Zinc , 2003, Journal of environmental science and health. Part A, Toxic/hazardous substances & environmental engineering.

[50]  L. Incoccia,et al.  Glitches compensation in EXAFS data collection , 1983 .

[51]  A. Farag,et al.  Concentrations of Metals Associated with Mining Waste in Sediments, Biofilm, Benthic Macroinvertebrates, and Fish from the Coeur d'Alene River Basin, Idaho , 1998, Archives of environmental contamination and toxicology.

[52]  James S. Kuwabara,et al.  Importance of Sediment–Water Interactions in Coeur d’Alene Lake, Idaho, USA: Management Implications , 2003, Environmental management.

[53]  Barbara Lothenbach,et al.  Immobilization of Heavy Metals by Polynuclear Aluminium and Montmorillonite Compounds , 1997 .

[54]  U. Schwertmann,et al.  Iron Oxides in the Laboratary , 2000 .

[55]  T. Borch,et al.  Phosphate imposed limitations on biological reduction and alteration of ferrihydrite. , 2007, Environmental science & technology.

[56]  G. Oberdörster,et al.  Nanotoxicology: An Emerging Discipline Evolving from Studies of Ultrafine Particles , 2005, Environmental health perspectives.

[57]  P. Woods,et al.  Nutrient and trace-element enrichment of Coeur d'Alene Lake, Idaho , 1996 .

[58]  R. Rosenzweig,et al.  Phase Associations and Mobilization of Iron and Trace Elements in Coeur d'Alene Lake, Idaho , 1998 .

[59]  C. Wai,et al.  Heavy metal pollution in the sediments of the Coeur d'Alene River, Idaho , 1978 .

[60]  W. Farrand.  Mapping the distribution of mine tailings in the Coeur d'Alene River Valley, Idaho, through the use of a constrained energy minimization technique , 1997 .

[61]  Peter A. Williams,et al.  A low temperature oxygen isotope thermometer for cerussite, with applications at Broken Hill, New South Wales, Australia , 2001 .

[62]  Anne K. Camper,et al.  Evaluation of Characterization Techniques for Iron Pipe Corrosion Products and Iron Oxide Thin Films , 2008 .

[63]  Brent M. Peyton,et al.  Copper-Induced Inhibition of Growth of Desulfovibrio desulfuricans G20: Assessment of Its Toxicity and Correlation with Those of Zinc and Lead , 2001, Applied and Environmental Microbiology.

[64]  Nicolas Geoffroy,et al.  Natural speciation of Zn at the micrometer scale in a clayey soil using X-ray fluorescence, absorption, and diffraction , 2004 .

[65]  Joseph S. Meyer,et al.  Distribution of metals during digestion by cutthroat trout fed benthic invertebrates contaminated in the Clark Fork River, Montana and the Coeur d'Alene River, Idaho, U.S.A., and fed artificially contaminated Artemia , 2000 .

[66]  R. Rosenzweig,et al.  A Laboratory Evaluation of Trace Element Mobility from Flooding and Nutrient Loading of Coeur d'Alene River Sediments , 1998 .

[67]  S. Bender,et al.  Toxic metal contamination in the lateral lakes of the Coeur d'Alene River valley, Idaho , 2000 .

[68]  C. Wai,et al.  Heavy metal pollution in the sediments of the Coeur d'Alene river delta , 1974 .