Hydrogeochemical characteristics of the Tinto and Odiel Rivers (SW Spain). Factors controlling metal contents.

The Tinto and Odiel Rivers are strongly affected by acid mine drainage (AMD) due to the intense sulphide mining developed in their basins over the past 5000 years. In this study the results obtained from a weekly sampling in both rivers, before their mouth in the Ría of Huelva, over three and a half years of control are analysed. In the Tinto River, the concentrations of sulphates, Al, Cd, Co, Li and Zn are double to those of the Odiel as a consequence of lower dilution. However, the concentration of Fe in the Odiel River is 20 times lower, since the precipitation of Fe oxyhydroxysulphates caused by neutralisation processes is more intense. Lower As, Cr, Cu and Pb concentrations are also found in the Odiel River as, to a greater or lesser extent, they are sorbed and/or coprecipitated with Fe. Other elements such as Be, Mn, Ni and Mg show similar values in both systems, which is ascribed to lithological factors. The seasonal evolution of contaminants is typical of rivers affected by AMD, reaching a maximum in autumn due to the dissolution of evaporitic salts precipitated during the summer. Nevertheless, in the Tinto River, Ca, Na and Sr show a strong increase during the summer, probably due to a greater water interaction with marly materials, through which the last reach of the river flows. Barium has a different behaviour from the rest of the metals and its concentration seems to be controlled by the solubility of barite. Iron, As and Pb show different behaviours in both rivers, those for Fe and As possibly linked to the prevalence of different dissolved species of Fe. The different Pb pattern is probably due to the control of Pb solubility by anglesite or other minerals rich in Pb in the Tinto River.

[1]  J. Borrego,et al.  Geochemical characteristics of heavy metal pollution in surface sediments of the Tinto and Odiel river estuary (southwestern Spain) , 2002 .

[2]  D. Nordstrom,et al.  Geochemistry of acid mine waters , 1999 .

[3]  M. Sogin,et al.  Microbiology: Eukaryotic diversity in Spain's River of Fire , 2002, Nature.

[4]  F. Morel,et al.  Surface Complexation Modeling: Hydrous Ferric Oxide , 1990 .

[5]  D. Nordstrom The effect of sulfate on aluminum concentrations in natural waters: some stability relations in the system Al2O3-SO3-H2O at 298 K , 1982 .

[6]  J. C. Fernández-Caliani,et al.  Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt , 2003 .

[7]  E. Achterberg,et al.  Metal geochemistry in a mine-polluted estuarine system in Spain , 2003 .

[8]  M. Kawano,et al.  Geochemical modeling of bacterially induced mineralization of schwertmannite and jarosite in sulfuric acid spring water , 2001 .

[9]  E. Boyle,et al.  A 120-yr record of widespread contamination from mining of the Iberian pyrite belt , 1997 .

[10]  E. Achterberg,et al.  Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter. , 2003, Environmental pollution.

[11]  M. Olı́asa,et al.  Seasonal water quality variations in a river affected by acid mine drainage : the Odiel River ( South West Spain ) , 2004 .

[12]  M. Hodson,et al.  Fe-sulphate-rich evaporative mineral precipitates from the Río Tinto, southwest Spain , 2003, Mineralogical Magazine.

[13]  N. Yanase,et al.  A natural attenuation of arsenic in drainage from an abandoned arsenic mine dump , 2003 .

[14]  J. Rubí,et al.  The Impact of Acid Mine Drainage on the Water Quality of the Odiel River (Huelva, Spain): Evolution of Precipitate Mineralogy and Aqueous Geochemistry Along the Concepción-Tintillo Segment , 2006 .

[15]  D. Nordstrom,et al.  Seasonal variations of Zn/Cu ratios in acid mine water from Iron Mountain, California , 1993 .

[16]  J. Grande,et al.  Characterisation of heavy metal discharge into the Ria of Huelva. , 2004, Environment international.

[17]  R. Sáez,et al.  The Iberian type of volcano-sedimentary massive sulphide deposits , 1999 .

[18]  C. Palmer,et al.  Solubility of jarosite at 4-35°C , 1996 .

[19]  C. Ayora,et al.  The behavior of trace elements during schwertmannite precipitation and subsequent transformation into goethite and jarosite , 2006 .

[20]  J. Nieto,et al.  An archaeological approach to regional environmental pollution in the south-western Iberian Peninsula related to Third millennium BC mining and metallurgy , 2005 .

[21]  Richard V. Morris,et al.  The Río Tinto Basin, Spain: Mineralogy, sedimentary geobiology, and implications for interpretation of outcrop rocks at Meridiani Planum, Mars , 2005 .

[22]  P. Rojík,et al.  Iron-rich precipitates in a mine drainage environment: Influence of pH on mineralogy , 2003 .

[23]  K. Hudson-Edwards,et al.  Mineralogy and geochemistry of alluvium contaminated by metal mining in the Rio Tinto area, southwest Spain , 1999 .

[24]  H. Chang,et al.  Apparent solubilities of schwertmannite and ferrihydrite in natural stream waters polluted by mine drainage , 1999 .

[25]  J. W. Ball,et al.  The Geochemical Behavior of Aluminum in Acidified Surface Waters , 1986, Science.

[26]  Marc Leblanc,et al.  4,500-YEAR-OLD MINING POLLUTION IN SOUTHWESTERN SPAIN: LONG-TERM IMPLICATIONS FOR MODERN MINING POLLUTION , 2000 .

[27]  Jean-Marie Beckers,et al.  Metal biogeochemistry in the Tinto-Odiel rivers (Southern Spain) and in the Gulf of Cadiz: A synthesis of the results of TOROS project , 2001 .

[28]  D. Nordstrom,et al.  Iron and Aluminum Hydroxysulfates from Acid Sulfate Waters , 2000 .

[29]  J. Nieto,et al.  Beudantite: a natural sink for As and Pb in sulphide oxidation processes , 2003 .

[30]  Nicholas F. Gray,et al.  Acid mine drainage composition and the implications for its impact on lotic systems , 1998 .

[31]  W. Perkins,et al.  Acid Mine Drainage in Wales and Influence of Ochre Precipitation on Water Chemistry , 1993 .

[32]  J. Drever,et al.  Geochemistry of suspended particles in a mine-affected mountain stream , 2001 .

[33]  Roger C. Viadero,et al.  The Geochemistry of Acid Mine Drainage , 2005, Encyclopedia of Water.

[34]  C. Bethke,et al.  A process model of natural attenuation in drainage from a historic mining district , 2000 .

[35]  J. Morales,et al.  Stratigraphic sequence, elemental concentrations and heavy metal pollution in Holocene sediments from the Tinto-Odiel Estuary, southwestern Spain , 1998 .

[36]  M. Leblanc,et al.  Bacterial immobilization and oxidation of arsenic in acid mine drainage (Carnoulès creek, France). , 2003, Water research.

[37]  R. Amils,et al.  A Comparative Ecological Study of Two Acidic Rivers in Southwestern Spain , 1999, Microbial Ecology.

[38]  Udo Schwertmann,et al.  Thermodynamics of iron oxides: Part III. Enthalpies of formation and stability of ferrihydrite (~Fe( , 2004 .

[39]  J. Torres,et al.  The Tinto River, an extreme acidic environment under control of iron, as an analog of the Terra Meridiani hematite site of Mars , 2002 .

[40]  M. Olías,et al.  Evaluation of the dissolved contaminant load transported by the Tinto and Odiel rivers (South West Spain) , 2006 .

[41]  Martin Williams Arsenic in mine waters: an international study , 2001 .

[42]  Jerry M. Bigham,et al.  SCHWERTMANNITE AND THE CHEMICAL MODELING OF IRON IN ACID SULFATE WATERS , 1996 .

[43]  D. Langmuir Aqueous Environmental Geochemistry , 1997 .

[44]  Robert R. Seal,et al.  Secondary sulfate minerals associated with acid drainage in the eastern US: Recycling of metals and acidity in surficial environments , 2005 .

[45]  J. Verstraten,et al.  Acid neutralization mechanisms in three acid sandy soils , 1994 .

[46]  A. Sáinz,et al.  Influence of the very polluted inputs of the Tinto-Odiel system on the adjacent littoral sediments of southwestern Spain: a statistical approach. , 2006, Chemosphere.

[47]  J. Rubí,et al.  The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt , 2006 .

[48]  E. L. Mosier,et al.  Geologic controls on the composition of natural waters and mine waters draining diverse mineral-deposit types , 1999 .

[49]  D. L. Parkhurst,et al.  User's guide to PHREEQC (Version 2)-a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations , 1999 .

[50]  B. Lottermoser Evaporative mineral precipitates from a historical smelting slag dump, Río Tinto, Spain , 2005 .

[51]  D. Blowes,et al.  Environmental geochemistry of sulfide oxidation , 1993 .

[52]  I. Gibson Statistics and Data Analysis in Geology , 1976, Mineralogical Magazine.

[53]  Lotta Hallbeck,et al.  Geochemistry of acidic Rio Tinto headwaters and role of bacteria in solid phase metal partitioning , 2004 .

[54]  E. Santofimia,et al.  Acid mine drainage in the Iberian Pyrite Belt (Odiel river watershed, Huelva, SW Spain): Geochemistry, mineralogy and environmental implications , 2005 .

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