Enrichment and Fractionation of Rare Earth Elements in an Estuarine Marsh Soil Receiving Acid Discharges from Legacy Sulfide Mine Wastes

This paper provides new insights into the geochemical cycling of rare earth elements (REEs) in acid sulfate soils developed on salt marsh sediments of the Huelva estuary (Spain) as a result of sulfide mineral oxidation in abandoned ore stockpiles. The study was aimed at determining the REE abundance, fractionation pattern and mineralogical control of the dispersal and retention of REEs in the soil system. Forty-one samples were collected at 13 core sampling sites along two transects extending across the degraded marshland, and they were subjected to XRD, ESEM-EDS and ICP-MS analyses. Measurements revealed that the soil receiving acid discharges has relatively high concentrations of ΣREEs (174.77 ± 19.77 mg kg−1) compared to local baseline concentrations. Shale-normalized REE patterns are generally flat, but a slight middle REE (MREE) enrichment is consistently apparent in all soil samples, involving relatively low LaN/GdN ratios (0.83 ± 0.08) and GdN/LuN ratios up to 1.42. The convex-upward REE pattern supports the possibility that iron oxy-hydroxide minerals play an important role in MREE retention through adsorption and co-precipitation mechanisms. Efflorescent sulfate salts left on the topsoil by the evaporation of acid waters show a strong depletion of light REEs (LaN/GdN = 0.16 ± 0.10) and act as a temporary reservoir of labile MREEs and heavy REEs during dry periods.

[1]  A. Ladeira,et al.  The role of iron in the rare earth elements and uranium scavenging by Fe-Al-precipitates in acid mine drainage. , 2021, Chemosphere.

[2]  C. R. Cánovas,et al.  Distribution and availability of rare earth elements and trace elements in the estuarine waters of the Ría of Huelva (SW Spain). , 2020, Environmental pollution.

[3]  A. Schippers,et al.  Biosorption of Rare Earth Elements by Different Microorganisms in Acidic Solutions , 2020, Metals.

[4]  C. Ayora,et al.  Sorption of rare earth elements on schwertmannite and their mobility in acid mine drainage treatments , 2020 .

[5]  A. Ojala,et al.  Extensive accumulation of rare earth elements in estuarine sediments affected by leaching of acid sulfate soils , 2020 .

[6]  J. C. Fortes,et al.  The UNESCO national biosphere reserve (Marismas del Odiel, SW Spain): an area of 18,875 ha affected by mining waste , 2019, Environmental Science and Pollution Research.

[7]  A. Bauriegel,et al.  Rare earth elements in soil profiles of various ecosystems across Germany , 2019, Applied Geochemistry.

[8]  Nianfang Xu,et al.  From source to sink: Rare-earth elements trace the legacy of sulfuric dredge spoils on estuarine sediments. , 2018, The Science of the total environment.

[9]  W. Gwenzi,et al.  Sources, behaviour, and environmental and human health risks of high-technology rare earth elements as emerging contaminants. , 2018, The Science of the total environment.

[10]  J. Grande,et al.  Mineralogical controls on mobility of rare earth elements in acid mine drainage environments. , 2018, Chemosphere.

[11]  M. Benzaazoua,et al.  Mobility of rare earth elements in mine drainage: Influence of iron oxides, carbonates, and phosphates. , 2018, Chemosphere.

[12]  K. Schmidt,et al.  The European Shale: An improved data set for normalisation of rare earth element and yttrium concentrations in environmental and biological samples from Europe , 2018 .

[13]  J. Nieto,et al.  Rare earth elements mobility processes in an AMD-affected estuary: Huelva Estuary (SW Spain). , 2017, Marine pollution bulletin.

[14]  C. Makowski,et al.  Coastal Wetlands: Alteration and Remediation , 2017 .

[15]  E. Burton,et al.  Acidic drainage drives anomalous rare earth element signatures in intertidal mangrove sediments. , 2016, The Science of the total environment.

[16]  J. Cable,et al.  Rare Earth Element Cycling in a Sandy Subterranean Estuary in Florida, USA , 2015 .

[17]  K. Hellwich,et al.  Brief guide to the nomenclature of inorganic chemistry , 2015 .

[18]  D. Dzombak,et al.  Rare earth element distributions and trends in natural waters with a focus on groundwater. , 2014, Environmental science & technology.

[19]  A. Grawunder,et al.  Origin of middle rare earth element enrichment in acid mine drainage-impacted areas , 2014, Environmental Science and Pollution Research.

[20]  F. Wall,et al.  Rare Earth Elements: Minerals, Mines, Magnets (and More) , 2012 .

[21]  L. Galván,et al.  Enrichment of rare earth elements as environmental tracers of contamination by acid mine drainage in salt marshes: a new perspective. , 2012, Marine pollution bulletin.

[22]  Jose Antonio Grande,et al.  Effect of acid mine drainage on dissolved rare earth elements geochemistry along a fluvial–estuarine system: the Tinto-Odiel Estuary (S.W. Spain) , 2012 .

[23]  A. Rate,et al.  Enrichment and fractionation of rare earth elements in FeS- and organic-rich estuarine sediments receiving acid sulfate soil drainage , 2012 .

[24]  J. Borrego,et al.  Rare-earth-element fractionation patterns in estuarine sediments as a consequence of acid mine drainage : a case study in SW Spain , 2012 .

[25]  J. C. Fernández-Caliani.  Risk-based assessment of multimetallic soil pollution in the industrialized peri-urban area of Huelva, Spain , 2012, Environmental Geochemistry and Health.

[26]  T. Hanebuth,et al.  Cycling of trace metals and rare earth elements (REE) in acid sulfate soils in the Plain of Reeds, Vietnam , 2011 .

[27]  J. Nieto,et al.  Rare earth element geochemistry of sulphide weathering in the São Domingos mine area (Iberian Pyrite Belt): A proxy for fluid–rock interaction and ancient mining pollution , 2010 .

[28]  J. Gustafsson,et al.  Lanthanoid behaviour in an acidic landscape. , 2010 .

[29]  C. Laveuf,et al.  A review on the potentiality of Rare Earth Elements to trace pedogenetic processes , 2009 .

[30]  J. C. Fernández-Caliani,et al.  Mobility and speciation of rare earth elements in acid minesoils and geochemical implications for river waters in the southwestern Iberian margin , 2009 .

[31]  A. Reis,et al.  Mineralogy and geochemistry of trace metals and REE in volcanic massive sulfide host rocks, stream sediments, stream waters and acid mine drainage from the Lousal mine area (Iberian Pyrite Belt, Portugal) , 2009 .

[32]  D. Kirste,et al.  Mineralogical control of rare earth elements in acid sulfate soils , 2009 .

[33]  D. Kirste,et al.  Jarosite dissolution I - trace cation flux in acid sulfate soils , 2007 .

[34]  S. R. Parker,et al.  The behavior of rare earth elements in naturally and anthropogenically acidified waters , 2006 .

[35]  M. Leybourne,et al.  Mobility and fractionation of rare earth elements during supergene weathering and gossan formation and chemical modification of massive sulfide gossan , 2006 .

[36]  E. Kothe,et al.  Rare earth element patterns: A tool for understanding processes in remediation of acid mine drainage , 2005 .

[37]  J. Borrego,et al.  Geochemistry of rare-earth elements in Holocene sediments of an acidic estuary: Environmental markers (Tinto River Estuary, South-Western Spain) , 2005 .

[38]  S. Wood,et al.  Diel behavior of rare earth elements in a mountain stream with acidic to neutral pH , 2005 .

[39]  J. Tarazona,et al.  Regulation of Contaminated Soils in Spain - A New Legal Instrument (4 pp) , 2005 .

[40]  D. Nordstrom,et al.  Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation , 2004 .

[41]  J. E. Dutrizac,et al.  The behaviour of the rare earths during the precipitation of sodium, potassium and lead jarosites , 2004 .

[42]  D. Nordstrom,et al.  Metal-sulfate Salts from Sulfide Mineral Oxidation , 2000 .

[43]  D. Nordstrom,et al.  Overview of Rare Earth Element Investigations in Acid Waters of U . S . Geological Survey Abandoned Mine Lands Watersheds , 1999 .

[44]  D. Brookins.  Chapter 8. AQUEOUS GEOCHEMISTRY OF RARE EARTH ELEMENTS , 1989 .