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In the salth-marshes of the Tinto River (Huelva estuary, SW Spain), are stored in stacks around 100 Mt of PG, covering a surface of 1000 ha without any type of isolation, which produce an important impact in the surrounding environment. On the other hand, this ecosystem it is affected by acid mine drainage (AMD) from sulphide mines located upstream the Tinto River. The aim of this study is to evaluate the deep pollution of the underlain salt-marsh sediments due to leachates from the PG stacks. For that purpose, 7 cores were collected from zones 2 and 3 of the stacks, and PG and salt-marsh sediments samples from different depths were analyzed. The physicochemical parameters, mineralogy, granulometry and the concentration of the main elements of interest were determined in the samples. Most analysed salt-marsh sediments are not affected by PG stacks pollution, because sediments act as a “barrier” for the leachates from the PG, concentrating the contaminants in the first decimetres (0.5 m) under PG-sediments contact, and the deep infiltration is very limited. The obtained results suggest that the perimeter channel which is projected to build in the restauration project, should has a depth of 1 m below the level of the PG stacks for assuring the complete collection of leachates from the stacks, and avoid their liberation into the Tinto River estuary.

This paper investigates the paleoenvironmental evolution of a core extracted in the middle sector of the Tinto River estuary, SW Spain, one of the most polluted areas in the world due to mining over thousands of years (>4 kyr BP) and recent industrial discharges. This evolution includes alluvial sands (>6.4 cal kyr BP), bioclastic sands and silts deposited in subtidal and intertidal channels during and after the Holocene transgression maximum (6.4-4.3 cal kyr BP), the sedimentation of clayey-sandy silts in low and high marshes during the last 2.4 kyr BP and a final anthropic filling. Three sharp peaks of pollution have been detected, representing a) a natural origin during the Holocene transgression; b) the impact of the first mining activities (~4.5 cal kyr BP); and c) the effect of industrial discharge and a new period of mining activity throughout the 19th and 20th centuries. Foraminifera, ostracods and molluscs disappeared during these last two peaks., Este trabajo investiga la evolución paleoambiental inferida a partir del estudio de un testigo extraído en el sector medio del estuario del río Tinto (SO de España), una de las zonas más contaminadas del mundo por actividades mineras milenarias (>4 kyr BP) y descargas industriales recientes. Esta evolución incluye arenas aluviales (>6.4 cal kyr BP), arenas bioclásticas y limos depositados en canales submareales e intermareales durante y después del máximo transgresivo holoceno (6.4-4.3 cal kyr BP), la sedimentación de limos arcillosos-arenosos marismeños durante los últimos 2.4 kyr BP y un relleno antrópico final. Se han detectado tres picos de contaminación, que proceden de: a) un origen natural durante el máximo transgresivo holoceno; b) el impacto de las primeras actividades mineras (~ 4.5 kyr BP); y c) el efecto conjunto de los vertidos industriales y un nuevo período de actividad minera durante los siglos XIX y XX. Los foraminíferos, ostrácodos y moluscos desaparecieron durante estos dos últimos picos.

The Odiel and Tinto rivers show singular characteristics due to the significant acid mine drainage (AMD) generated in the first section of their basins and the phosphogypsum (PG) stacks located on their common estuary. AMD leads to low pH and high redox potential, which keep high amounts of toxic elements and radionuclides in dissolution. The objective of this work was to analyse the seasonal evolution of U-Th isotopes and 210Po in these rivers and the estuarine mixing zone. Four sampling points were selected (a fluvial point and an estuarine one for each river) and water samples were collected monthly throughout a year. The concentrations of natural radionuclides in the dissolved and particulate phases were determined by alpha spectrometry. The Odiel and Tinto rivers show concentrations of U-Th isotopes and 210Po from one to three orders of magnitude higher than background continental waters due to the strong effect of AMD, and 234U/238U activity ratios up to 2. The studied radionuclides show a clear seasonal behaviour in these rivers, with three different stages during the year: (1) concentration peaks observed during November and December due to the “washing effect” produced by the first rainfalls of the hydrological year, (2) a “dilution effect” by runoff in the rainy winter, and (3) a progressive “concentration effect” during the spring and summer. A non-conservative behaviour of the analysed radionuclides in the estuaries was demonstrated due to precipitation processes produced by the increase of pH. The polluted outflows from the PG stacks located in the Tinto estuary produce a significant radioactive impact, mainly during the rainiest months, increasing the concentration of U-isotopes and 210Po in the particulate phase.

The Olivargas River drains materials from the Iberian Pyrite Belt with a large number of abandoned sulphide mining complexes that produce highly contaminated acid mine drainages (AMD). The Olivargas River is regulated by a reservoir that receives these acid leachates through its three main tributaries. In this study, the chemical composition of the waters from the reservoir and the water courses in its watershed are investigated based on samples taken throughout a hydrological year. We calculated the contaminant load for Al, Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn, SO4 and other elements entering the reservoir by two methods, establishing the relations of the dissolved element concentrations with 1) the water flow and 2) the specific conductance. The most extreme conditions were found in the tributary Los Peces Creek, with a mean pH value of 2.8 and concentrations of up to 736 mg/L of Zn and 291 mg/L of Al, making it the main source of metals in the reservoir (up to 65 t/year of Zn). Given that the volume of acid mine water pouring into the reservoir is relatively low, the water pH in the reservoir remains neutral. Under these conditions, most of the mine-derived metals (especially Al and Fe) form precipitates that accumulate in the bottom sediments, while dissolved concentrations are low (0.2 mg/L of Al and

The failure of the tailing dam at the Aznalcóllar mine (SW Spain) in 1998 released ≈ 6 million m3 of pyrite sludge and acidic waters, and caused an enormous environmental disaster in the Agrio and Guadiamar rivers. A small aquifer formed by recent alluvial materials deposited by both rivers was also affected. The mine closed as a result of the spill but a new project for its reopening is currently being developed. The area covered by the spill (≈ 60 km long) was later transformed into a protected green corridor, which connects two important natural reserves. This work describes the effectiveness of the remediation measures taken and analyzes the evolution of water quality in the area since 1980 (almost 20 years before the accident occurred). The contaminant levels in both surface and groundwater showed a sharp decrease the first years after the spill, followed by a subsequent stabilization of pollution levels. Nowadays, pollutant concentrations in surface waters are even lower than those recorded before the spill, due to the cessation of mining and the effectiveness of the remediation. Despite this fast and outstanding improvement, the alluvial aquifer close to the mining zone is still polluted, with acidic pH values in some areas, probably due to the slow movement of groundwater together with the existence of some areas with polluted soils. As this aquifer feeds the streams, some pollutants (e.g. Al, Cd, and Zn) reach the surface waters. Remediation of the polluted soils as well as the alluvial aquifer in this sector is strongly recommended to achieve the complete rehabilitation of the affected area.

The Tharsis mine is presently abandoned, but the past intense exploitation has left large dumps and other sulphide-rich mining wastes in the area generating acid mine drainages (AMD). The main goal of this work is to study the effect of hydrogeochemical processes, hydrological regime and the waste typology on the physicochemical parameters and dissolved concentrations of pollutants in a deeply AMD-affected zone. Extreme leachates are produced in the area, reaching even negative pH and concentrations of up to 2.2 g/L of As and 194 g/L of Fe. The results of the comparison of ore grades of sulphide deposits with dissolved concentrations in waters shows that Pb is the least mobile element in dissolution probably due to the precipitation of Pb secondary minerals and/or its coprecipitation on Fe oxyhydroxysulphates. Arsenic, Cr, and V are also coprecipitated with Fe minerals. Seasonal patterns in metal contents were identified: elements coming from the host rocks, such as Al, Mn and Ni, show their maximum values in the dry period, when dilution with freshwater is lower and the interaction of water-rock processes and evaporation is higher. On the other hand, As, Cr, Fe, Pb and V show minimum concentrations in the dry period due to intense Fe oxyhydroxysulphate precipitation. In this sense, large sulphide rich waste heaps would be a temporal sink of these elements (i.e. Pb, As, Cr and V) in the dry period, and a significant source upon intense rainfalls., This work was supported by the Spanish Ministry of Economic and Competitiveness through the projects CGL2016-78783-C2-1-R (SCYRE) and by H2020 European Institute of Innovation and Technology (EIT RawMaterials) through the projects Modular recovery process services for hydrometallurgy and water treatment (MORECOVERY). The authors thank to Prof. Yong Sik Ok (Associate Editor) and five different reviewers for their helpful comments that notably improved the quality of the manuscript.

This study characterizes the hydrogeochemical behavior of one of the most pollutant sources in the Iberian Pyrite Belt, namely, the Poderosa adit outflow. This artificial spring arises from an anthropogenic mine aquifer with a similar hydrogeological behavior to karstic systems, where the infiltration area is an endorheic zone and the aquifer shows allogenic recharge. Recent mining has markedly increased the contaminant levels. The pollutant load released from the adit to the receiving water body is very high, with average loads of 280 kg/day of Fe, 47 kg/day of Al, 17 kg/day of Cu and so on. However, a high variability is observed related to hydrological and geochemical factors, especially during intense rainy episodes. Thus, the pollutant load during these events suffers a dramatic increase, i.e., from ~100–200 kg/day of Fe during base flow to almost 2200 kg/day during the flow peak. These data highlight the importance of short but intense rainy events on metal fluxes from mining areas, which has been previously reported in surface waters but scarcely reported in mine adits, with expected lower response times to rainfall. The pollutant load released by non-point sources, i.e., spoil heaps, is lower than that released from the adit most of the year, although it increased noticeably during intense rainy events. Some remediation measures were adopted during the 1990s without a suitable hydrogeological characterization and were shown to be ineffective. On the basis of the obtained results, potential restoration measures are discussed.

Fluxes of acidity and contaminants from acid mine drainage (AMD) sources to the receiving surface water bodies were studied in a mining-impacted watershed (Meca River, SW Spain) using a novel methodology based on the joint application of EMMA and MIX codes. The application of EMMA and elemental ratios allowed delimiting the end-members responsible for water quality variations at a catchment scale. The further application of MIX quantified the significant impact of AMD on the river quality; less than 10% of AMD relative contribution is enough to maintain acidic conditions during most of the year. The mixing model also provided information about the element mobility, distinguishing those elements with a quasi-conservative behavior (e.g., Cu, Zn, Al, Co or Ni) from those affected by mineral precipitation/dissolution (e.g., K, Si, Na, Sr, Ca, Fe, Pb, or As). Floods are the main driver of dissolved and, mainly particulate, contaminants in the catchment. Thus, the first rainfall events in November only accounted for 19% of the annual Meca flow but yielded between 26 and 43% of the net acidity and dissolved metal loads (mainly, Fe, As and Pb). Concerning particulate transport, around 332 tons of particulate Fe, 49 tons of Al, 0.79 tons of As and 0.37 tons of Pb were recorded during these first floods. The particulate As concentration can be up to 34 times higher than the dissolved one during floods and between 2 and 4 times higher for Fe, Pb and Cr. This integrated modeling approach could be a promising and useful tool to face future restoration plans in derelict mines worldwide. This approach would allow prioritizing remedial measures, achieving an environmental and cost-effective restoration of degraded areas.

Next to the city of Huelva (SW of Spain), around 100 Mt of phosphogypsum (PG) are stored in stacks on the salt-marshes of the Tinto River estuary covering a surface of about 1000 ha. Due to the high content of 238U series natural radionuclides of the PG, its acidic nature (pH about 3), and the fact that PG stacks were disposed without any kind of isolation from the substrate, they could produce a potential radioactive impact into the underlying sediments. The aim of this work is to assess the pollution of the underlying sediments by natural radionuclides coming from the PG stacks. To this end, seven cores were taken, and PG and sediments samples collected at different depths were analysed. The activity concentrations of the main long half-live natural radionuclides of interest were determined by applying both gamma-ray and alpha-particle spectrometry radiometric techniques. The results of this study showed that the first decimeters of salt-marsh sediment act as a “barrier” for the radionuclides coming from the PG stacks decreasing rapidly its activity concentration in depth, affecting mainly sediments located in the first 20 cm below the contact due to mixing processes. While 230Th, 226Ra and 210Pb pollution is mainly restricted to the first 20 cm of sediments, U-isotopes can reach higher depths (up to around 50 cm) by leaching processes due to their lower reactivity and higher concentration in the polluted leachates. The obtained results have high relevance for the design of the perimeter channel which is projected to build in the restoration project, suggesting that should has around 1 m deep under the base of the PG stacks, to ensure the full collection of polluting leachates, and to prevent their release into the estuary of the Tinto River.

On August 3, 1492, Christopher Columbus departed from the port of Palos de la Frontera, located in a small cove in southwestern Spain, and returned to this same port on March 15, 1493. On the basis of sedimentology, geochemistry, paleontology and dating of a long core (18 m) collected in this cove, thirteen facies are distinguished in the Neogene-Holocene evolution of its sedimentary infilling, with a transition from Miocene marine environments to Late Holocene marshes, going through an intermediate period that includes fluvial gravels, alluvial sediments and shallow coastal deposits that characterize the maximum of the Fladrian transgression in this area (~6.5 cal kyr BP). These data and others contributed by historical sources allow an approximate reconstruction of this cove at the end of the 15th century.

In May 2017, a spill from La Zarza pit lake (SW Spain) resulted in the release of approximately 270,000 m3 of extremely acidic waters to the Odiel River. Around 780 × 103 kg of Fe, 170 × 103 kg of Al, 2.15 × 103 kg of As and high amounts of other trace metals and metalloids were spilled. The purpose of this study is to explain the causes, consequences and impacts of the mine spill on the receiving water bodies. To this end, an extensive sampling along the mine site, river and estuary as well as a hydrological model of the pit lake was performed. Around 53 km of the Odiel River's main course, which was already contaminated by acid mine drainage (AMD), were affected. The mine spill resulted in an incremental impact on the Odiel River water quality. Thus, dissolved concentrations of some elements increased in the river up to 450 times; e.g. 435 mg/L of Fe and 0.41 mg/L of As. Due to low pH values (around 2.5), most metals (e.g., Cu, Zn, Mn, Cd) were transported in the dissolved phase to the estuary, exhibiting a conservative behavior and decreasing their concentration only due to dilution. However, dissolved concentrations of Fe, Cr, Pb, Se, Sb, Ti, V and especially As decreased significantly along the river due to Fe precipitation and sorption/coprecipitation processes. At the upper zone of the estuary, a noticeable increment of metal concentrations (up to 77 times) was also recorded. The water balance illustrates the existence of groundwater inputs (at least 16% of total) to the pit lake, due probably to local infiltration of rainwater at the mining zone. The probable existence of an ancient adit connected to the pit lake indicates that potential releases could occur again if adequate prevention measures are not adopted.

Estuaries are very sensitive ecosystems to human activities and the natural evolution of their drainage basins located upstream. Pollution derived from human activities, such as historical mining or recent industrial wastes, can significantly affect their environmental quality. This paper analyzes the silver and copper contents of four cores extracted in two estuaries of SW Spain. Its chronology and vertical evolution allow to differentiate the effects of several pollution episodes (natural, Roman, 19th-20th centuries) on its different sedimentary environments in the last 6 million years. Possible future applications are included in the fields of environmental management or even education.

Summary The input of water from precipitation is one of the most important aspects of a hydrologic model because it controls the basin’s water budget. The model should reproduce the amount and distribution of rainfall in the basin, spatially and temporally. SWAT (Soil and Water Assessment Tool) is one of the most widely used hydrologic models. In this paper the rainfall estimation in SWAT is revised, focusing on the treatment of orographic precipitation. SWAT was applied to the Odiel river basin (SW Spain), with a surface of 2300 km 2 . Results show that SWAT does not reflect reallisticaly the spatial distribution of rainfall in the basin. In relation to orographic precipitation, SWAT estimates the daily precipitation in elevation bands by adding a constant amount to the recorded precipitation in the rain gauge, which depends on the increase in precipitation with altitude and the difference between the mean elevation of each band and the elevation of the recording gauge. This does not reflect rainfall in the subbasin because the increase in precipitation with altitude actually it is not constant, but depends on the amount of rainfall. An alternative methodology to represent the temporal distribution of orographic precipitation is proposed. After simulation, the deviation of runoff volume using the SWAT elevation bands was appreciably higher than that obtained with the proposed methodology.

The Tinto and Odiel rivers in southwest Spain drain the world's largest sulfide mineral formation: the Iberian Pyrite Belt which has been worked since 2,500 BC. The Tinto and Odiel estuarine zones include both an extensive area of salt marsh and an intensively industrialized urban area. As a consequence of pyrite oxidation, the Tinto and Odiel rivers are strongly acidic (pH 3) with unusually high and quite variable metal concentrations. In this study, seasonally varying concentrations of dissolved major and trace elements were determined in the acid mine drainage affected estuary of the Ría de Huelva. During estuarine mixing, ore-derived metal concentrations exhibit excellent correlations with pH as the main controlling parameter. As pH increases, concentrations of dissolved ore-associated elements are attenuated, and this process is enhanced during the summer months. The decrease in Fe and Al concentrations ranged from 80 to 100 % as these elements are converted from dissolved to sediment-associated forms in the estuary. Coprecipitation/adsorption processes also removed between 60 and 90 % of the originally dissolved Co, Cu, Mn, Pb, Zn, and Th; however, Cd and Ni exhibited a greater propensity to remain in solution, with an average removal of approximately 60 %. On the other hand, As and U exhibited a different behavior; it is likely that these elements remain in dissolved forms because of the formation of U carbonates and soluble As species. Concentrations of As remain at elevated levels in the outer estuary (average = 48 μg L(-1)) which exceeds concentrations present in the Tinto River. Nevertheless, the estuary has recently witnessed improvements in water quality, as compared to results of several previous studies reported in the 1990s.

The Tinto River estuary is one of the most contaminated coastal systems in the world due to the high amounts of pollutants this acidic river transports. The tidal influence and the fluvial discharges control the water mixing, which include a salt-induced process (that is typical of all estuaries) and an acid neutralization process (pH-induced mixing). These processes affect the geochemical behavior of uranium, which has a non-conservative pattern. Despite the high concentrations of dissolved uranium in the Tinto River, 234U/238U shows that uranium stems mostly from seawater (between 80 and 100%). Riverine uranium is adsorbed onto both Fe and Al precipitates when the acidic river water is mixed with seawater. Distribution coefficients (Kd) show that dissolved and particulate uranium are controlled by adsorption–desorption processes and the formation of carbonate complexes, both depending on pH. At low pH, uranium tends to be dissolved, and the adsorption by suspended particles is low. As the pH increases, the adsorption processes onto Fe and Al particles are more intense, increasing particulate uranium which reaches a maximum at pH 5.5, where the uranium solubility minimum occurs. At higher pH values, dissolved uranium increases by carbonate complexation.

The Odiel River Basin (SW Spain) drains the central part of the Iberian Pyrite Belt (IPB), a world-class example of sulfide mining district and concomitantly of acid mine drainage (AMD) pollution. The severe AMD pollution and the incipient state of remediation strategies implemented in this region, coupled with the proximity of the deadline for compliance with the European Water Framework Directive (WFD), urge to develop a restoration and water resources management strategy. Furthermore, despite the presence of some reservoirs with acid waters in the Odiel basin, the construction of the Alcolea water reservoir has already started. On the basis of the positive results obtained after more than 10 years of developing a specific passive remediation technology (dispersed alkaline substrate (DAS)) for the highly polluted AMD of this region, a restoration strategy is proposed. The implementation of 13 DAS treatment plants in selected acid discharges along the Odiel and Oraque sub-basins and other restoration measurements of two acidic creeks is proposed as essential to obtain a good water quality in the future Alcolea reservoir. This restoration strategy is also suggested as an economically and environmentally sustainable approach to the extreme metal pollution affecting the waters of the region and could be considered the starting point for the future compliance with the WFD in the Odiel River Basin. © 2016, Springer-Verlag Berlin Heidelberg., This work was supported by the Spanish Ministry of Economic and Competitiveness through the projects EMPATIA (CGL2013-48460-C2-1-R) and SCYRE (CGL2016-78783-C2-1-R) and LIFE-ETAD project (LIFE12 ENV/ES/000250) and partially financed by Program U-INICIA VID 2014, grant 193, University of Chile, and by CONICYT, Program Fondecyt Iniciacion, Project Nº 111500002. R. Pérez-López also thanks the Spanish Ministry of Science and Innovation and the “Ramón y Cajal Subprogramme” (MICINN-RYC 2011). M.A. Caraballo gratefully acknowledges the support from the Advanced Mining Technology Center of the University of Chile. C.R. Cánovas was funded by the European Union’s Seventh Framework Program, Marie Skłodowska-Curie actions, and the Ministry of Economy, Innovation, Science and Employment of the Junta de Andalucía by the program Talent Hub (COFUND-Grant Agreement 291780). We would also like to thank Dr. Philippe Garrigues (editor in chief) and an anonymous reviewer for the support and comments that significantly improved the quality of the original manuscript.

The Tinto River shows very high concentrations of toxic elements and acidity from its source in the mining area to its mouth. In this paper, we studied the evolution of the levels of toxic elements during part of the Quaternary from the analysis of fluvial deposits that, forming terraces, were originated by the dynamics of the Tinto River. Using a detailed geomorphological cartography, up to nine terrace levels were differentiated in the lower sector of the basin, whose ages range from the Pleistocene to the Holocene. Sampling and geochemical analyses (major elements and trace) were carried out in six of these levels, in addition to sediments of the current flood plain. The results of these analyses do not show any bias from the mid Pleistocene (T8 - Terrace 8) to the early Holocene (T1). Moreover, these geochemical contents are similar to the average values obtained by other authors for the entire South-Portuguese Zone of the Iberian Massif. However, the current sediments of the Tinto River (T0) show a sharp increase in the levels of As, Cu, Pb and Zn compared to the rest, which indicates a serious increment of contamination by toxic elements. Although there are evidences on the existence of a natural process of oxidation of sulfides since the Miocene, the amounts of toxic elements released should be very small compared to those generated since the beginning of the mining activities in the Iberian Pyrite Belt., This research was funded by two Spanish-FEDER projects (AMB99-0226-C03, CGL2010-15810/BTE) and one Research Group of the Andalusia Board RNM-293.

The accurate estimation of metal loads transported by streams is necessary to calculate reliable mass transfers of metals between compartments, both at local and global scales. This estimation is particularly relevant in the case of the Tinto and Odiel Rivers (SW Spain) due to their significant contribution to the total metal transfer from continents to the ocean. At a local scale, the metal load transported by streams plays a key role in predicting the biogeochemical evolution of water reservoirs affected by Acid Mine Drainage (AMD). This work uses the relationships between specific conductivity (SC) and dissolved elements to calculate the metal load of the River Meca, a tributary of the Odiel. The SC and the water level were continuously monitored from April 2009 to June 2010. Water samples were also collected and measurements of the discharge were carried out manually once a month. The relationships between the SC and the concentration of dissolved elements are, in general, very good (R2 > 0.90). However, some key elements such as Fe show a very poor correlation. A simple methodology based on the MIX code (a maximum likelihood method to estimate mixing ratios) was used to elucidate their different behaviours. During the dry period (April–December, 2009) the Fe concentration was lower than that deduced from the SC recorded value due to the precipitation of Fe-oxihydroxides, which also reduced the concentrations of As, Cr, Pb and, to a lesser extent, Cu. At the same time Na, Sr, Ca and Li were enriched because of the higher interaction with the riverbed materials. Correlations between the SC and the metal concentration improved significantly when each period was considered separately. A second dry period (April–June 2010) shows high SC values, although no dissolution/precipitation of solid phases is evidenced. This indicates that SC alone is not enough to predict the dissolved metal loads in Mediterranean AMD streams. The metal load transported by the River Meca was determined for the hydrological year 2009/10 as 1933 ± 129 tonnes of Fe, 990 ± 155 of Al and 378 ± 41 of Zn.

In 1998, the Agrio and Guadiamar rivers underwent an enormous environmental disaster caused by the rupture of the Aznalcóllar tailings dam and the release of 6 hm(3) of pyrite sludge and acidic water. Both rivers run over recent alluvial materials which form a small-sized aquifer which is however important because underground water feeds the flow of the rivers. This work analyzes the state of groundwater 10 years after the spill. Before the dam failure, this aquifer was already contaminated in the zone nearest to the mine, to which the impact of the spill was added. Contamination levels in the alluvial aquifer of the Agrio River have decreased remarkably. However, they are still important, with acidic pH values and high concentrations of toxic elements (maximum values of 16 mg/L of Zn and 15 mg/L of Al). There are also important levels of contamination in the Guadiamar alluvial area closest to the mine, as well as in specific zones located further south. The concentration of toxic elements is mainly controlled by pH. The evolution of contaminant levels show a sharp decrease after the first years following the spill, followed by a subsequent stabilization. It is necessary to take measures for the recovery of the aquifer because, otherwise, groundwater will continue contributing contaminants into the Agrio and Guadiamar rivers.

The multidisciplinary analysis of core sediments from Donana National Park, south Spain, permits to delimitate both the paleoenvironmental changes and the geochemical evolution of this area during the Holocene. In a first phase (10–6.5 kyr cal), this area was occupied by freshwater/brackish marshes with periodical alternation of dry periods and humid intervals. In a second phase, these marshes were inundated during the Flandrian transgression (~6.5 kyr cal), with the deposition of bioclastic sands. The third phase (6.5–3.6 kyr cal) is characterized by the transition to an old lagoon, with unpolluted, bottom sediments. The geochemical concentrations of these clayey sediments can be used as a geochemical background for present-day and future environmental evaluations of this area. In the following 600 years approximately, two tsunamis caused the partial infilling of this area with bioclastic, marine sediments. In the interval comprised between these two tsunamis, this lagoon was polluted with heavy metals derived from historical mining activities. This environmental contamination represents one of the oldest evidences of mining pollution in the world (>3 kyr cal BP).

The Odiel River is located in southwestern Spain; the greater portion of its basin is composed of materials from the Iberian Pyrite Belt (IBP), an area with numerous massive sulfide deposits that have been highly exploited since the third millennium BC. As sulfides come into contact with the atmosphere due to mining activity, oxidation occurs, generating a highly toxic acidic leachate with large concentrations of sulfates and metals, a process which is known as acid mine drainage (AMD). As a result, the Odiel River and most of its tributaries are severely contaminated. The construction of two large dams in the Odiel River basin is planned. The most advanced project is that of the Alcolea reservoir, with a storage capacity of 274 hm3, whose construction has already begun, with a total budget of around €164 million. There are reasonable doubts about the final quality of the reservoir water, as this dam will regulate a river with a mean pH close to 3.5 and large concentrations of toxic elements. This paper analyzes the data of water quality in the Alcolea reservoir. The results show that the reservoir water will be acidic and not useful at all, although more specific studies are necessary to obtain the exact estimation of its hydrochemical characteristics. It seems unwise to start building the dam, which requires a large economic investment and will have a vast environmental impact, without first conducting these studies. This proves that water management in Spain is still based on political motivation rather than on technical criteria and good management of natural and economic resources.

Summary The Meca River is highly contaminated by acid mine drainage coming from the Tharsis mining district, belonging to the Iberian Pyrite Belt. This river is regulated by the Sancho reservoir (58 hm3), with a pH close to 4.2. In this work, the load transported by the Meca River to the Sancho reservoir has been assessed. Due to the lack of streamflow data, the hydrological behaviour of the Meca River basin has been simulated using the SWAT model. The model has been calibrated against registered daily inflows of the Sancho reservoir (1982–2000), excluding the hydrological years 2000/2001 and 2001/2002 that were kept for the validation. The results were satisfactory; the evaluation coefficients for monthly calibration were: r = 0.85 (Pearson’s correlation coefficient), NSE = 0.83 (Nash–Sutcliffe coefficient) and DV = 1.08 (runoff volume deviation). The main uncertainty was the calibration during low water because of the poor accuracy in the measurement of the inputs to the reservoir in these conditions. Discharge and dissolved concentration relationships for different elements were obtained from hydrochemical samplings, which allowed us to estimate the element pollutant load transported to the reservoir: 418 ton/year of Al, 8024 ton/year of SO4, 121 ton/year of Zn, etc. Based on these loads, concentrations in the reservoir were calculated for some elements. Apart from Mn and Sr, good adjustment between calculated and measured values was observed (±20% for Ca, Co, Li, Mg, Na, Ni, Zn and SO4). Capsule: Hydrological model combined with water quality data show how pollution by AMD can generate huge loads of contaminants acidifying streams and reservoirs.

Regulatory actions taken in the Adra River basin (746 km2), located south of the Sierra Nevada Mountains (SE Spain), are analyzed. The Beninar Reservoir (60 hm3), which entered into service in 1983, has suffered from severe leakage from the outset, preventing it from performing the water management functions originally foreseen for it; however, it has also made it possible to determine the response of the underlying carbonate aquifer into which the reservoir water is draining. This response has been studied based on historical data as well as the occurrence of an extraordinary recharge produced by a period of exceptionally heavy rainfall. A conceptual model of the system’s functioning has been established by analyzing leakage rates, piezometric variations, the discharge through the only spring in the area (the Fuentes de Marbella spring) and the physical-chemical characteristics of the aquifer water. Geological and structural aspects of the carbonate formation were also included. An alternative solution for water regulation in the river basin is proposed: the construction of a smaller dam downstream from the spring. This dam would induce recharge through the permeable base of the reservoir, raise the piezometric level and thus increase its storage capacity, as well as control and regulate the water discharged from the spring.

The Odiel river Basin is heavily affected by acid mine drainage (AMD) from the sulphide mining areas in the Iberian Pyrite Belt (IPB). A thorough study has been conducted along this fluvial system, monitoring the seasonal influence on the pollution level and its hydrochemical characteristics. From 2002 to 2006, surface water samples were collected at 91 different points throughout the Odiel river Basin and analyzed by field and laboratory methods for dissolved metals and metalloids. Acid mine drainage affects 37% of the length of the drainage network, which shows a great diversity of geochemical conditions as well as significant variations through the hydrological year. Unaffected streams show different water types depending on the lithological substrate and the marine aerosol influence. Mean concentrations in the contaminated streams are very high: 231 mg/L of Fe, 135 mg/L of Al, 56 mg/L of Zn, 16 mg/L of Cu, etc. Four types of contaminated streams were recognized based on hydrochemical and physicochemical characteristics. There are important seasonal variations depending on the precipitation regimen, level of pollution and proximity to the AMD sources. In the more contaminated samples the M/Fe ratio (M = metals other than Fe) decreases during the summer season. Slightly contaminated samples show an inverse evolution as this ratio increases in spring and summer due to substantial Fe precipitation. A recomparison of contaminant loads suggests that the Odiel river Basin (including the Tinto river) accounts for 15% of the global gross flux of dissolved Zn and 3% of the global gross flux of dissolved Cu transported by rivers into the ocean.

Summary Sierra de Segura (Betic Cordillera), with a total area of over 3000 km 2 , is the source of the two principal rivers in southern Spain, the Guadalquivir and the Segura. Due to the orographic effect of these mountains, precipitations are considerably more abundant than in nearby lowland areas, where the climate is semi-arid. Sierra de Segura is constituted of Mesozoic and Cenozoic sedimentary rocks, among which there are thick limestone–dolomitic formations which have given rise to extensive outcrops of permeable materials. In geomorphological terms, there is a large plateau intensively karstified that constitutes the main recharge area. Discharge takes place via a large number of springs, of which the 50 most important add up to a mean spring flow of about 13,500 l/s. The active geochemical processes in aquifers of Sierra de Segura, with their corresponding time sequence, are: dissolution of CO 2 , dissolution of calcite, incongruent dissolution of dolomite, dedolomitization, exsolution of CO 2 , and precipitation of calcite. More evolved water has higher temperature, magnesium content and Mg/Ca ratio; therefore, these parameters can be utilised as indicators of the degree of hydrochemical evolution. In addition, a good correlation between water temperature and magnesium concentration (or Mg/Ca ratio) indicates that an increase in temperature accelerates the kinetics of the dissolution of dolomite. Finally, the distribution of the temperatures in the vadose zone, determined by atmospheric thermal gradient, implies an apparent stratification of the predominant hydrochemical processes and of the groundwater physical and chemical characteristics.

The aim of this work is to study the hydrochemical variations during flood events in the Rio Tinto, SW Spain. Three separate rainfall/flood events were monitored in October 2004 following the dry season. In general, concentrations markedly increased following the first event (Fe from 99 to 1130 mg/L; Q(max) = 0.78 m(3)/s) while dissolved loads peaked in the second event (Fe = 7.5 kg/s, Cu = 0.83 kg/s, Zn = 0.82 kg/s; Q(max) = 77 m(3)/s) and discharge in the third event (Q(max) = 127 m(3)/s). This pattern reflects a progressive depletion of metals and sulphate stored in the dry summer as soluble evaporitic salt minerals and concentrated pore fluids, with dilution by freshwater becoming increasingly dominant as the month progressed. Variations in relative concentrations were attributed to oxyhydroxysulphate Fe precipitation, to relative changes in the sources of acid mine drainage (e.g. salt minerals, mine tunnels, spoil heaps etc.) and to differences in the rainfall distributions along the catchment. The contaminant load carried by the river during October 2004 was enormous, totalling some 770 t of Fe, 420 t of Al, 100 t of Cu, 100 t of Zn and 71 t of Mn. This represents the largest recorded example of this flush-out process in an acid mine drainage setting. Approximately 1000 times more water and 1408 200 times more dissolved elements were carried by the river during October 2004 than during the dry, low-flow conditions of September 2004, highlighting the key role of flood Events in the annual pollutant transport budget of semi-arid and and systems and the need to monitor these events in detail in order to accurately quantify pollutant transport. (c) 2007 Elsevier B.V. All rights reserved.

The variations of groundwater quality in the unconfined zone of the Almonte-Marismas aquifer, upon which Donana National Park is located, are analysed. Most sampled points are multiple piezometers, allowing for the vertical distribution study of the hydrogeochemical characteristics in the aquifer. Temperature, pH, electrical conductivity, dissolved oxygen and redox potential were determined in the field. A large number of parameters, including major ions and a large amount of minor and trace elements, were analysed. In the southern zone, where aeolian sands crop out, water composition in the shallower part of the aquifer is of the sodium chloride type, with low pH (5.5–6) and mineralization (

Scarcity of waters is the main limiting factor of economic development in most arid and semi-arid regions worldwide. The construction of reservoirs may be an optimal solution to assure water availability if the drainage area shows low disturbances. This is the quandary of mining areas where economic development relies on water accessibility. Water acidification trends were investigated in the Sancho Reservoir (SW Spain) in the last 20 years. The acidity (pH3-5) and high dissolved metal concentrations (e.g., 4.4 mg/L of Al, 2.1mg/L of Mn, 1.9 mg/L of Zn) observed in the Sancho, together with the large volume stored (between 37 and 55 Mm(3)), makes this reservoir an extreme case of surface water pollution worldwide. A progressive acidification has been observed since 2003, as evidenced by decreasing pH values and increasing dissolved metal concentrations, especially noticeable after 2007. The increase in the net acidity in the reservoir originates from the higher input of metals and acidity due to the rebound effect after the mining closure in 2001. This trend was not detected in the river feeding the reservoir due to its great hydrological and hydrochemical variability, typical of the Mediterranean climate. Chemical analysis and absolute dating of sediments identified a progressive enrichment in S and metals (i.e., Fe, Zn Cu, Ni, Co and Cd) in the upper 20 cm, which reinforce the year 2002/03 as the onset of the acidification of the reservoir. The decrease of pH values from 4-5 to 3-4 occurred later than the increase in sulfate and metals due to pH-buffering by Al. The acid mine drainage (AMD) pressure has caused an increment of dissolved Fe and other metals, as well as a change in the pH buffering role, exerted now by Fe. These processes were simulated by PHREEQC, which confirms that the acidification trend will continue, causing pH values to reach 2.5 if AMD pressure persists.

The Tinto and Odiel rivers are heavily affected by acid mine drainage (AMD). However, the exact quantities of contaminants transported into the Huelva estuary and the Gulf of Cadiz are unknown. The existing previous investigations are, in general, based on studies with few data or incorrect methodology, and are therefore unreliable. This study aims to present a reliable estimation of the dissolved contaminant load transported by both rivers for the periods 1995/96 to 2002/03. The methodology used is based principally on the correlation between contaminant concentration and flow rate. The results show that both rivers transport enormous quantities of dissolved contaminants: 7900 t a −1 of Fe, 5800 t a −1 Al, 3500 t a −1 Zn, 1700 t a −1 Cu, 1600 t yr −1 Mn and minor quantities of other metals. These values represent 60% of the global gross flux of dissolved Zn transported by rivers in to the ocean, and 17% of the global gross flux of dissolved Cu.

A multidisciplinary study of El Melah Lagoon (NE Tunisia) permits the analysis of the present scenario of this coastal environment. Salinity and pH values indicate a main marine origin for the permanent waters, which present locally high nutrient contents owing to the continuous flows coming from both the Slimene’s treatment station (STS) and the agricultural activities surrounding the southeastern margins of the lagoon. The heavy metal concentrations of the clayey-silty bottom sediments may be moderate to high near the STS’s effluent and close to a parapharmaceutical plant. Seven zones were distinguished in this limited area (200 ha), according to the physical–chemical parameters and nutrient contents of waters, the grain size and heavy metal contents of the bottom sediments and the distribution of ostracode assemblages (marine, high brackish and freshwater to low brackish). This analysis, together with the information provided by aerial photos (1948–1996), is the basis to hypothesize a future evolution of the system.

A multivariate analysis of the foraminifera collected in three estuaries of southwestern Spain (Guadiana, Piedras, Tinto-Odiel) permits recognition of three main assemblages, with spatial distribution depending on sedimentary environments, grain size classes and salinity variations. Assemblage 1 (Trochammina inflata, Jadammina macrescens) is typical of salt marsh deposits with high salinity variations and percentages of important silt. Assemblage 2 (Ammonia beccarii, Ammonia tepida, Astrononion stelligerum, Elphidium williamsoni) includes the most abundant estuarine species, with increasing densities from the channel margin to the subtidal channel. Assemblage 3 (Quinqueloculina seminulum, Elphidium crispum) is mainly found in the sandy sediments of the subtidal channels located near the mouth, with normal marine conditions. These results and the sedimentological interpretation of seven drill cores collected in the Domingo Rubio Channel (Tinto River) allow reconstruction of the palaeogeographic changes of this small estuary in the last ca. 6500 14 C years BP. Seven phases were distinguished, with an evolution from an open marine bay to

Four phases are distinguished in the Mid-Holocene evolution of the southwestern Donana National Park (SW Spain), based on the multidisciplinary study of sediments in drill cores. In the oldest phase (> 5500–5400 cal. years BP), a coastal, brackish lagoon occupied the central part of the study area, partly enclosed by the Donana spit and limited by fluvial levees. An evolution from subtidal to intertidal conditions characterized the areas located close to the inner side of the Donana spit during the same phase. The following phase (∼5400–5200 cal. years BP) is characterized by a high-energy event (tsunami?), which caused the breakthrough of the Donana spit and the creation of new littoral strands in the inner areas. In the first period of the third phase (∼5200–4200 cal. years BP), estuarine infilling was probably the dominant process, with the accumulation of phyllosilicate-rich clays in the lagoon bed. This was followed by a renewed phase of instability (∼4200–4100 cal. years BP) indicated by the presence of fine storm-lain deposits and thicker, probably tsunami-induced shelly deposits. The last phase (∼4100–3700 cal. years BP) comprises: a) an infilling period, with a diminution of the marine influence; and b) two new high-energy events, which caused the erosion of the Donana spit and the creation of new cheniers. In the last 7000 years, the comparison of these results with a revision of both geological and historical records has revealed the occurrence of twenty tsunamis (at least) during this period in Portugal and southern Spain. Evidences of these high-energy events are washover fans, bioclastic coarse-sized layers within salt marsh deposits or the presence of giant boulders and pebbles. The determination of the recurrence period is very difficult owing to the very scarce data, although our data and other authors do not discard a possible periodicity of 2000 years for a cycle of two events separated by 300–400 years.

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.

On 25 April 1998 the tailings dam of the Aznalcollar mine burst, a great quantity of pyrite waste sludge and acid water was spilled reaching the vicinity of the Donana National Park. In surface and ground water samples taken a week after dam breaking, metals, trace elements and Pb isotopic ratios (206Pb/207Pb and 208Pb/206Pb) were analysed. In September 1998 a second sampling survey was carried out. The surface waters have a similar isotopic composition as the lead contained in the pyrite from the Aznalcollar mine. The polluted groundwater of the Guadiamar aquifer also shows the influence of the mining origin of the lead. Lead isotope ratios (206Pb/207Pb and 208Pb/206Pb) in the groundwater of the Almonte-Marismas are very low and they differ clearly from the rest of groundwater samples. A further group of wells has a lead isotope composition intermediate between the Aznalcollar mine and the atmospheric aerosols of the Iberian Peninsula.

The Tinto River estuary is highly polluted with the acid lixiviates from old sulphide mines. In this work the behaviour of dissolved and particulate trace metals under strong chemical gradients during a tidal cycle is studied. The pH values range from 4.4 with low tide to 6.9 with high tide. Precipitation of Fe and Al is intense during rising tides and As and Pb are almost exclusively found in the particulate matter (PM). Sorption processes are very important in controlling the mobility (and hence bioavailability) of some metals and particularly affect Cu below pH 6. Above pH ~ 6 Cu is desorbed, probably by the formation of Cu(I)–chloride complexes. Although less pronounced than Cu, also Zn desorption above pH 6.5 seems to occur. Mn and Co are affected by sorption processes at pH higher than ca. 6. Cd behaves conservatively and Ni is slightly affected by sorption processes.

This paper describes a comprehensive study of the behaviour of U in the Ria of Huelva estuary, formed by the Tinto and Odiel rivers. This ecosystem is conditioned by two hydrochemical facts: one connected with the acid mining drainage (AMD) generated in the first section of the river basins, and another one related to the fertilizer industry located at the estuary. AMD gives a singular character to these rivers; low pH and high redox potential that keep high amounts of toxic elements and radionuclides in dissolution. Most of the data for dissolved U in estuaries indicate conservative mixing, but there are examples of non-conservative behaviour attributed to oxidation/reduction processes or solubility variations. In the Ria of Huelva estuary the U shows a non-conservative behaviour due to solubility changes produced by variations in the pH. A complete removal of riverine dissolved U is observed in a pH range of 4–6. At higher pH values, U release from suspended matter, and probably also from sediments into the dissolved phase is found.

An accidental spillage of gasoline in a sector of the ‘Vega de Granada’ alluvial aquifer (Spain) affected a number of wells in the area. Hydrocarbon concentrations in ground water were monitored over a period of two years and five months. Monitoring indicated that the contamination levels tended to decrease, although sharp fluctuations were observed. Correlation and spectral analysis were used, among other methods, to construct a model of the hydrocarbon concentrations' evolution. We established the existence of maximum values of cross-correlation between the time series for hydrocarbon content and rainfall, with different lags for each well. Cross correlation is most clear in several wells located along a paleochannel in which the contamination tended to flow. Quantification was therefore possible of both the contaminant propagation rate and the permeability of the aquifer in that area. Although more detailed analysis showed that the high correlation values were due to a single data set (corresponding to the maximum concentrations observed in each well after a period of exceptionally heavy rainfall), the above conclusions may still be considered valid for periods of intense recharge of the aquifer, as demonstrated by an artificial recharge test.

Acid mine drainage in the Iberian Pyrite Belt is probably the worst case in the world of surface water pollution associated with mining of sulphide mineral deposits. The Iberian Pyrite Belt is located in SW Iberian Peninsula, and it has been mined during the last 4,500 years. The central and eastern part of the Iberian Pyrite Belt is drained by the Tinto and Odiel rivers, which receive most of the acidic leachates from the mining areas. As a result, the main channels of the Tinto and Odiel rivers are very rich in metals and highly acidic until reaching the Atlantic Ocean. A significant amount of the pollutant load transported by these two rivers is delivered during the rainy season, as is usual in rivers of Mediterranean climate regions. Therefore, in order to have an accurate estimation of the pollutant loads transported by the Tinto and Odiel rivers, a systematic sampling on a weekly basis and a high temporal resolution sampling of floods events were both performed. Results obtained show that metal fluxes are strongly dependent on the study period, highlighting the importance of inter-annual studies involving dry and wet years.

The Tinto and Odiel rivers are seriously affected by acid mine drainage (AMD) from the long-term mining activities in Iberian Pyrite Belt (IPB). As a consequence, the Huelva estuary is heavily contaminated by metals and metalloids. This study presents an estimation of the seasonal variation, and the dissolved contaminant load transported by both rivers from February 2002 to September 2004. Besides, toxicity and bioaccumulation tests with the sediments of the estuary have been conducted in order to measure the mobility of the toxic metals. Results show that the Tinto and Odiel rivers transport enormous quantities of dissolved metals to the estuary: 7900 t yr−1 of Iron (Fe), 5800 t yr−1 Aluminium (Al), 3500 t yr−1 Zinc (Zn), 1700 t yr−1 Copper (Cu), 1600 t yr−1 Manganese (Mn) and minor quantities of other metals and metalloids. These values represent 37% of the global gross flux of dissolved Zn transported by rivers in to the ocean, and 15% of the global gross flux of dissolved Cu. These metals and metalloids usually sink in the estuarine sediments due to pH and salinity changes. The increase of salinity in the estuary favours the adsorption and trapping of metals. For this reason, the mobility and bioavailability of metals such as Zn, Cd and Cu is higher in sediments located in the area of fresh water influence that in sediments located in the marine influenced area of the estuary, showing a higher percentage of fractionation and bioaccumulation of these metals in the station influenced by the fresh water environment. Keywords: Tinto and Odiel rivers, Acid mine drainage, Water and sediment pollution, Huelva estuary, Iberian Pyrite Belt

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 Ria 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.

The Iberian Pyrite Belt (IPB) is one of the most famous sulfide mining regions in the world. Mining activity in the IPB dates back to prehistoric times, and though today there is no active mining, the pollution continues to generate. The result is acidic drainage containing elevated concentration of sulfate and heavy metals. This is responsible for the pollution and degradation of the Odiel River basin in south-western Spain. In this work we have conducted a study along the entire Odiel basin. During the years 2002 and 2003 we have collected water samples at 69 points in order to characterize and quantify the pollutants that the Odiel River receives as a consequence of the AMD inputs within its watershed. The contaminant load transported by the Odiel River into the Huelva Estuary has also been calculated. Due to the great quantity of samples and analyses, the use of statistical multivariate techniques (Principal Component Analysis) was used to interpret the results. PCA of the samples showed strong interrelationships between the generation of acid by sulfide mineral weathering and metal loads. In downstream reaches, the rock forming elements (K, Ca, Na, Mg, etc.) dominate as the acidic waters dissolve the rocks in the stream bed. The contaminant load transported by the Odiel River to the Huelva Stuary is dominated by SO4 2- , Al and Fe, with lesser quantities of Zn, Cu, Cd, etc.