Anthropogenic forcings on the surficial osmium cycle.

Osmium is among the least abundant elements in the Earth's continental crust. Recent anthropogenic Os contamination of the environment from mining and smelting activities, automotive catalytic converter use, and hospital discharges has been documented. Here we present evidence for anthropogenic overprinting of the natural Os cycle using a ca. 7000-year record of atmospheric Os deposition and isotopic composition from an ombrotrophic peat bog in NW Spain. Preanthropogenic Os accumulation in this area is 0.10 +/- 0.04 ng m(-2) y(-1). The oldest strata showing human influence correspond to early metal mining and processing on the Iberian Peninsula (ca. 4700-2500 cal. BP). Elevated Os accumulation rates are found thereafter with a local maximum of 1.1 ng m(-2) y(-1) during the Roman occupation of the Iberian Peninsula (ca. 1930 cal. BP) and a further increase starting in 1750 AD with Os accumulation reaching 30 ng m(-2) y(-1) in the most recent samples. Osmium isotopic composition ((187)Os/(188)Os) indicates that recent elevated Os accumulation results from increased input of unradiogenic Os from industrial and automotive sources as well as from enhanced deposition of radiogenic Os through increased fossil fuel combustion and soil erosion. We posit that the rapid increase in catalyst-equipped vehicles, increased fossil fuel combustion, and changes in land-use make the changes observed in NW Spain globally relevant.

[1]  P. Sedwick,et al.  Anthropogenic osmium in rain and snow reveals global-scale atmospheric contamination , 2009, Proceedings of the National Academy of Sciences.

[2]  I. Rodushkin,et al.  Osmium in environmental samples from Northeast Sweden. Part II. Identification of anthropogenic sources. , 2007, The Science of the total environment.

[3]  R. Creaser,et al.  Re–Os elemental and isotopic systematics in crude oils , 2007 .

[4]  M. Molina,et al.  Platinum group elements in airborne particles in Mexico City. , 2006, Environmental science & technology.

[5]  F. Nocete The first specialised copper industry in the Iberian peninsula: Cabezo Juré (2900-2200 BC) , 2006, Antiquity.

[6]  M. Kylander,et al.  Refining the pre-industrial atmospheric Pb isotope evolution curve in Europe using an 8000 year old peat core from NW Spain [rapid communication] , 2005 .

[7]  Kristine H. Ek,et al.  Platinum group element concentrations and osmium isotopic composition in urban airborne particles from Boston, Massachusetts. , 2005, Environmental science & technology.

[8]  F. Grousset,et al.  Tracing dust sources and transport patterns using Sr, Nd and Pb isotopes , 2005 .

[9]  X. P. Pombal,et al.  Linking changes in atmospheric dust deposition, vegetation change and human activities in northwest Spain during the last 5300 years , 2005 .

[10]  A. Poirier,et al.  Isotopic signature and impact of car catalysts on the anthropogenic osmium budget. , 2005, Environmental science & technology.

[11]  David Selby,et al.  Direct Radiometric Dating of Hydrocarbon Deposits Using Rhenium-Osmium Isotopes , 2005, Science.

[12]  T. Meisel,et al.  Determination of anthropogenic input of Ru, Rh, Pd, Re, Os, Ir and Pt in soils along Austrian motorways by isotope dilution ICP-MS. , 2004, The Science of the total environment.

[13]  B. Peucker‐Ehrenbrink,et al.  Source characterisation of atmospheric platinum group element deposition into an ombrotrophic peat bog. , 2004, Journal of environmental monitoring : JEM.

[14]  B. Peucker‐Ehrenbrink,et al.  Recent changes in platinum group element concentrations and osmium isotopic composition in sediments from an urban lake. , 2004, Environmental science & technology.

[15]  B. Peucker‐Ehrenbrink,et al.  Rhenium‐osmium isotope systematics and platinum group element concentrations in oceanic crust from DSDP/ODP Sites 504 and 417/418 , 2003 .

[16]  H. Emons,et al.  Two thousand years of atmospheric rare earth element (REE) deposition as revealed by an ombrotrophic peat bog profile, Jura Mountains, Switzerland. , 2003, Journal of environmental monitoring : JEM.

[17]  K. Turekian,et al.  Atmospheric supply of osmium to the oceans , 2002 .

[18]  B. Peucker‐Ehrenbrink,et al.  Rhenium‐osmium isotope systematics and platinum group element concentrations: Loess and the upper continental crust , 2001 .

[19]  H. Prichard,et al.  Platiniferous chromitite and the tectonic setting of ultramafic rocks in Cabo Ortegal, NW Spain , 2001, Journal of the Geological Society.

[20]  J. Blusztajn,et al.  An osmium isotope excursion associated with the Late Paleocene thermal maximum: Evidence of intensified chemical weathering , 2001 .

[21]  B. Peucker‐Ehrenbrink,et al.  The marine osmium isotope record , 2000 .

[22]  J. Morales,et al.  Rio Tinto estuary (Spain): 5000 years of pollution , 2000 .

[23]  B. Peucker‐Ehrenbrink,et al.  The effects of sampling artifacts on cosmic dust flux estimates: a reevaluation of nonvolatile tracers (Os, Ir) , 2000 .

[24]  B. Peucker‐Ehrenbrink,et al.  Rapid determination of Os isotopic composition by sparging OsO4 into a magnetic-sector ICP-MS , 2000 .

[25]  R. Mathur,et al.  Age and sources of the ore at Tharsis and Rio Tinto, Iberian Pyrite Belt, from Re-Os isotopes , 1999 .

[26]  J. Nóvoa-Muñoz,et al.  Mercury in a spanish peat bog: archive of climate change and atmospheric metal deposition , 1999, Science.

[27]  P. Schiano,et al.  Rhenium–osmium isotopic investigation of Java subduction zone lavas , 1999 .

[28]  Gloor,et al.  History of atmospheric lead deposition since 12,370 (14)C yr BP from a peat bog, jura mountains, switzerland , 1998, Science.

[29]  S. Hart,et al.  Re–Os isotope evidence for the composition, formation and age of the lower continental crust , 1998, Nature.

[30]  R. Walker,et al.  THE Re-Os ISOTOPE SYSTEM IN COSMOCHEMISTRY AND HIGH-TEMPERATURE GEOCHEMISTRY , 1998 .

[31]  E. García-Rodeja,et al.  Four Thousand Years of Atmospheric Pb, Cd and Zn Deposition Recorded by the Ombrotrophic Peat Bog of Penido Vello (Northwestern Spain) , 1997 .

[32]  D. Pyle,et al.  PGE and Os isotopic analyses of single sample aliquots with NiS fire assay preconcentration , 1997 .

[33]  J. Morgan,et al.  Re-Os systematics of early proterozoic ferropicrites, Pechenga Complex, northwestern Russia: Evidence for ancient 187Os-enriched plumes , 1997 .

[34]  Sungmin Hong,et al.  A reconstruction of changes in copper production and copper emissions to the atmosphere during the past 7000 years , 1996 .

[35]  J. Morgan,et al.  The osmium isotopic composition of the Earth's primitive upper mantle , 1996, Nature.

[36]  M. Bothner,et al.  Osmium isotopes and silver as tracers of anthropogenic metals in sediments from Massachusetts and Cape Cod bays , 1996 .

[37]  K. Turekian,et al.  Anthropogenic osmium in coastal deposits , 1993 .

[38]  D. L. Finnegan,et al.  Osmium isotopes in the aerosols of the mantle volcano Mauna Loa , 1992 .

[39]  J. Ruíz,et al.  Osmium isotopes and crustal sources for platinum-group mineralization in the Bushveld Complex, South Africa , 1991 .

[40]  J. Southon,et al.  Vesuvius/Avellino, one possible source of seventeenth century BC climatic disturbances , 1990, Nature.

[41]  J. Luck,et al.  Osmium isotopes as petrogenetic and geological tracers , 1980 .

[42]  I. C. Smith,et al.  Osmium: An Appraisal of Environmental Exposure , 1974, Environmental health perspectives.

[43]  R. Bindler Estimating the natural background atmospheric deposition rate of mercury utilizing ombrotrophic bogs in southern Sweden. , 2003, Environmental science & technology.

[44]  G. Mckay,et al.  Geochemistry and mineralogy of rare earth elements , 1989 .

[45]  R. H. Silsbee,et al.  Energy transitions. , 1980, Science.