Stratification of Metal and Sulphate Loads in Acid Mine Drainage Receiving Water Dams - Variables Regionalization by Cluster Analysis.

The Sancho Reservoir (Iberian Pyrite Belt, SW Spain) is nourished by the waters of the river Meca, which is affected by acid mine drainage (AMD) processes from the abandoned Tharsis mine. The aim of the present work is to study the hydrochemical variations in this reservoir, in order to define potential stratification processes in metal load and sulphates. A stratified sampling from the surface, with one meter deep intervals to the bottom of the dam, was performed. The results show a clear stratification of temperature, pH, electric conductivity, dissolved oxygen, metal and sulphate loads associated with depth. There is an increase of metal loads at the bottom of the reservoir, though previous studies only detect iron. The proximity between pH and aluminium suggests that water chemistry is strongly influenced by aluminium precipitation processes. This indicates the buffer effect that aluminium exercises, which precipitates as amorphous or low crystalline phases, introducing hydrogen ions to the system, while alkalinity input tends to raise pH.

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.

Water quality of the Guadiamar River after the Aznalcóllar spill (SW Spain).

In April 1998, a spill of 6 hm3 of pyritic mud and acidic water was released into the Guadiamar River due to the rupture of the Aznalcóllar tailings dam. Before the spill, the river was already strongly affected by acid mine drainage (AMD). In this study, the water quality of the Guadiamar River is analysed from a periodic sampling started after the spill. Previous data of the water quality have also been obtained. A recovery of the water quality is observed from 2002 on. The distribution of arsenic is opposed to that of the rest of metals, with the lowest concentrations to the north, due to the adsorption and/or coprecipitation on ferric oxyhydroxides. In the southern area, when pH values are close to 8, arsenic desorption occurs. There is a seasonal pattern of the trace metal content evolution, different in the northern and southern zones of the river. In the northern area the highest polluting levels occur in summer, due to a lower dilution of the mining leachates. In the southern area, the highest metal levels occur during the winter, since during the summer metals remain held by surface sorption processes in the hyporheic zone of the river.

Distribution of rare earth elements in an alluvial aquifer affected by acid mine drainage: the Guadiamar aquifer (SW Spain).

This work analyses the spatial distribution, the origin, and the shale-normalised fractionation patterns of the rare earth elements (REE) in the alluvial aquifer of the Guadiamar River (south-western Spain). This river received notoriety in April 1998 for a spill that spread a great amount of slurry (mainly pyrites) and acid waters in a narrow strip along the river course. Groundwaters and surface waters were sampled to analyse, among other elements, the REEs. Their spatial distribution shows a peak close to the mining region, in an area with low values of pH and high concentrations of sulphates and other metals such as Zn, Cu, Co, Ni, Pb, and Cd. The patterns of shale-normalised fractionation at the most-contaminated points show an enrichment in the middle rare earth elements (MREE) with respect to the light (LREE) and heavy (HREE) ones, typical of acid waters. The Ce-anomaly becomes more negative as pH increases, due to the preferential fractionation of Ce in oxyhydroxides of Fe.

Seasonal water quality variations in a river affected by acid mine drainage: the Odiel River (South West Spain).

This paper intends to analyse seasonal variations of the quality of the water of the Odiel River. This river, together with the Tinto River, drains the Iberian Pyrite Belt (IPB), a region containing an abundance of massive sulphide deposits. Because of mining activity dating back to prehistoric times, these two rivers are heavily contaminated. The Odiel and Tinto Rivers drain into a shared estuary known as the Ría of Huelva. This work studies dissolved contaminant data in water of the Odiel River collected by various organisations, between October 1980 and October 2002, close to the rivers entry into the estuary. Flow data for this location were also obtained. The most abundant metals in the water, in order of abundance, are zinc (Zn), iron (Fe), manganese (Mn) and copper (Cu). Arsenic (As), cadmium (Cd) and lead (Pb) are also present but in much lower quantities. The quality of the river water is linked to precipitation; the maximum sulphate, Fe, Zn, Mn, Cd and Pb concentrations occur during the autumn rains, which dissolve the Fe hydroxysulphates that were precipitated during the summer months. In winter, the intense rains cause an increase in the river flow, producing a dilution of the contaminants and a slight increase in the pH. During spring and summer, the sulphate and metal concentration (except Fe) recover and once again increase. The Fe concentration pattern displays a low value during summer due to increased precipitation of ferric oxyhydroxides. The arsenic concentration displays a different evolution, with maximum values in winter, and minimum in spring and summer as they are strongly adsorbed and/or coprecipitated by the ferric oxyhydroxides. Mn and sulphates are the most conservative species in the water. Relative to sulphate, Mn, Zn and Cd, copper displays greater values in winter and lower ones in summer, probably due to its coprecipitation with hydroxysulphates during the spring and summer months. Cd and Zn also appear to be affected by the same process, although to a lower degree than Cu, experiencing a slight reduction in summer with respect to Mn and sulphates.

Assessment of the dissolved pollutant flux of the Odiel River (SW Spain) during a wet period.

The abandoned mining districts of the Iberian Pyrite Belt (IPB, SW Spain) are an extreme source of pollution by acid mine drainage (AMD) to the Tinto and Odiel rivers. The pollutant flux transported by the Odiel River during a high stage period was assessed using concentration-discharge relationships and concentration-conductivity relationships, for the hydrological year 2009/10 (which was especially wet). Both correlations were high (R(2)>0.80) for most of the elements studied. The two methods for flux calculation gave similar results with differences generally lower than 10%. The dissolved contaminant flux transported by the Odiel River just before its mouth mainly includes sulphate (257,534±13,464 t/yr), Al (13,259±1071 t/yr), Zn (4265±242 t/yr), Mn (2532±146 t/yr) and Cu (1738±136 t/yr), and minor amounts of other elements. These findings confirm that, up to our knowledge, the Odiel River can be considered to be the largest contributor of mining-related pollutants to the world's oceans.