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Abstract This paper is focused on the hydrogeochemical characterization of the Negro River along its course, as well as in the proposal of a functioning model for the contamination processes in order to establish potential cause-effect relationships between water quality, geology (ARD), mining activities (AMD) and the tectonic framework as transmission vector of acidity, metals and sulphates. The scenario shows a heavily-contaminated river compared to the unaffected regional background. By graphical and statistical treatments of physico-chemical data of Negro River and the unaffected values of regional background and other AMD/ARD representative rivers' it is possible to conclude that Antamina Mine, is not the cause of the Negro River contamination, without the need of isotopic tracers, but just through the inexistent concentrations of Cu, Bi and Mo found in the waters. In the proposed contamination model, climatic factors (glacial retreat) activate geological (ARD) processes. The tectonic scenario (faults) intervenes as a transport medium of the contamination flux from the sulphide oxidation surface in upper altitudes until the spring in lower altitudes. At the end, it is concluded that this contamination comes from the recent glacial retreat in areas near the Cordillera Blanca that has left massive amounts of sulphide materials exposed to weathering conditions, oxidizing naturally (ARD processes) and finally contributing to the contamination of the Negro River through faults. In this case, we would face an ARD process in the strict sense, which is the direct oxidation of sulphides outcropping in the upper part of the mountain with the generation of sulphates, the release of hydrogen ions and the consequent generation of acid and the dissolution of the metals. This ARD process would come from the glacial retreat, which, through the faults, transports contaminated water until the spring. Graphical abstract Unlabelled Image Highlights • Copper, Bismuth and Molybdenum as indicators of AMD affected rivers • Application of Cluster Analysis to discriminate ARD/AMD processes in the Negro River • Glacial retreat and ARD generating processes [ABSTRACT FROM AUTHOR]

Abstract Aljustrel mining area (South Portugal) belongs to the Iberian Pyrite Belt (IPB). It is classified of high environmental risk due to its large tailings and to the Acid Mine Drainage (AMD) affected waters, generated by sulphides' oxidation. Integrating biological parameters (for the first time) in the input data matrix of the software PreFuRGe, allowed a better discrimination of the diatoms' responses to the stimuli caused by the hydrochemical changes imposed by the processes affecting water quality. Each hydrochemical scenario, was modeled by imposing maximum and minimum limits for each antecedent, according to the conditions imposed by the consequent, which in this case were the number of diatom species and pH. Thus, PreFuRGe evidenced some qualitative aspects that could not be achieved by classic statistics. pH appeared as the main discriminator of diversity and diatom species composition, nevertheless and due to the complex environment under study other chemical interactions must be considered: (a) AMD waters, with extremely low pH values, but also with extremely high hydrogeochemical complexity, represented by a mixture of metals, do not allow to associate, unequivocally, the reduction in diatom diversity to pH, but also to high metal (loid)s concentrations; (b) in the most alkaline waters, with higher abundance of diatom species, average to high concentrations of Na and Cl (due to Cenozoic sediments) do not seem to affect diatom diversity. This methodology proved to be an efficient tool to establish, for the first time, cause-effect relationships, improving the comprehension between biological (diatoms) and hydrochemical parameters. Highlights • IPB is considered of high contamination hazard due especially to AMD draining to the streams. • Fuzzy Logic was for the first time applied to biological parameters. • pH was the main modeler of the communities' diversity. • Fuzzy Logic allowed a better understanding of AMD contamination process. • Fuzzy Logic allowed a better understanding of natural salinisation process. [ABSTRACT FROM AUTHOR]

The Iberian Pyrite Belt (IPB), in the southwest of Europe, is characterized by high levels of contamination by acid mine drainage (AMD) in a large extent of its river network. In this scenario, it is necessary to characterize the degree of pollution of the mining leachates in the AMD-generating sources as well as of the main receiving watercourses. A map of impact of each basin was developed, based on the model proposed by Grande (2011) and the European Directive 98/83/EC that defines the quality standards for drinking water. The results indicate that practically all the mining leachates exceeded the maximum concentrations established by Directive 98/83/CE for Fe and Cd, almost 90% exceeded the limit for Mn and 82% for Al. Likewise, Fe, Cd, and Mn caused ‘extremely high’ degradation in most sampled leachates. Similarly, these metals, in addition to Pb, produced more pollution in watercourses located downstream of exploitations. [ABSTRACT FROM AUTHOR]

Highlights: [•] This paper describes solid phases associated to AMD in a massive sulfide deposit. [•] The study was performed in Tharsis mines, in the Iberian Pyrite Belt. [•] The AMD-precipitates are dominated by efflorescent sulfate minerals. [•] There are two mineralogical environments differentiated by composition and variety. [•] The open pits reflect a proximal paragenesis; the Meca River reflects a distal one. [Copyright &y& Elsevier]

Abstract: This study describes the spatial evolution of the hydrogeochemical parameters which characterise a strongly affected estuary by Acid Mine Drainage (AMD). The studied estuarine system receives AMD from the Iberian Pyrite Belt (SW Spain) and, simultaneously, is affected by the presence of an industrial chemical complex. Water sampling was performed in the year of 2008, comprising four sampling campaigns, in order to represent seasonality. The results show how the estuary can be divided into three areas of different behaviour in response to hydrogeochemical variables concentrations that define each sampling stations: on one hand, an area dominated by tidal influence; in the opposite end there is a second area including the points located in the two rivers headwaters that are not influenced by seawater; finally there is the area that can be defined as mixing zone. These areas are moved along the hydrological year due to seasonal chemical variations. [Copyright &y& Elsevier]

The Ria of Huelva estuary, in SW Spain, is known to be one of the most heavy metal contaminated estuaries in the world. River contribution to the estuary of dissolved Cu, Zn, Mn, Cr, Ni, Cd, and As were analysed for the period 1988–2001. The obtained mean values show that this contribution, both because of the magnitude of total metals (895.1 kg/h), composition, toxicity (8.7 kg/h of As+Cd+Pb) and persistence, is an incomparable case in heavy metal contamination of estuaries. The amount and typology of heavy metal discharge to the Ria of Huelva are related to freshwater flow (and, consequently, to rainfall); as a result, two different types of heavy metal discharge can be distinguished in the estuary: during low water (50% of the days), with only 19.3 kg/h of heavy metals, and during high water or flood (17% of the days), where daily maximum discharge of 72,475 kg of heavy metals were recorded, from which 1481 kg were of As, 470 kg of Pb, and 170 kg of Cd. In the most frequent situation (77% of the days), the Odiel River discharges from 90% to 100% of the freshwater received by the estuary. Despite this, the high concentration of heavy metals in the Tinto River water causes this river to discharge into the Ria of Huelva 12.5% of fluvial total dissolved metal load received by the estuary. [Copyright &y& Elsevier]

Water pollution caused by sulfide oxidation responds to two geochemical processes: a natural one of temporal patterns, and the ‘acid mine drainage’, an accelerated process derived from the extractive activity. The Odiel River is located in Southwestern Spain; it flows to the south and into the Atlantic Ocean after joining the Tinto River near its mouth, forming a common estuary. There are three kinds of metallic mining in the Odiel River Basin: manganese, gold and silver, and pyrite mining, the latter being the most important in this basin, which is the object of this study.The main objective of the present study is centred in the characterisation of the sources responsible for the ‘acid mine drainage’ processes in the Odiel River Basin, through the sampling and subsequent chemical and statistical analyses of water samples collected in three types of sources: mine dumps, active mines and abandoned mines. The main conclusion is that mean pH values in the target area are remarkably lower than those in other active and abandoned mines outside of the study zone. On the contrary, mean values for heavy metal sulfates are much higher. Regarding mine dumps, mean values for pH, sulfates and heavy metals are within a similar range to those data known for areas outside the study zone. [Copyright &y& Elsevier]

In the last few decades, the study of space–time distribution and variations of heavy metals in estuaries has been extensively studied as an environmental indicator. In the case described here, the combination of acid water from mines, industrial effluents and sea water plays a determining role in the evolutionary process of the chemical makeup of the water in the estuary of the Tinto and Odiel Rivers, located in the southwest of the Iberian Peninsula.Based on the statistical treatment of the data from the analysis of the water samples from this system, which has been affected by processes of industrial and mining pollution, the 16 variables analyzed can be grouped into two large families. Each family presents high, positive Pearson r values that suggest common origins (fluvial or sea) for the pollutants present in the water analyzed and allow their subsequent contrast through cluster analysis. [Copyright &y& Elsevier]

Rare earth elements (REE) were analyzed in river waters, acid mine waters, and extracts of secondary precipitates collected in the Iberian Pyrite Belt. The obtained concentrations of the REE in river water and mine waters (acid mine drainage - AMD) were in the range of 0.57 μg/L (Lu) and 2579 μg/L (Ce), which is higher than previously reported in surface waters from the Iberian Pyrite Belt, but are comparable with previous findings from AMD worldwide. Total REE concentrations in river waters were ranged between 297 μg/L (Cobica River) and 7032 μg/L (Trimpancho River) with an average of 2468 μg/L. NASC (North American Shale Composite) normalized REE patterns for river and acid mine waters show clear convex curvatures in middle−REE (MREE) with respect to light- and heavy−REE. During the dissolution experiments of AMD-precipitates, heavy−REE and middle−REE generate the most enriched patterns in the solution. A small number of precipitates did not display MREE enrichment (an index Gd n /Lu n  < 1.0) in NASC normalized pattern and produced relatively lower REE concentrations in extracts. Additionally, very few samples, which mainly contained aluminum sulfates, e.g., pickeringite and alunogen, displayed light−REE enrichment relative to heavy−REE (HREE). In general, the highest retention of REE occurs in samples enriched in magnesium (epsomite or hexahydrite) and aluminum sulfates, mainly pickeringite. [ABSTRACT FROM AUTHOR]

The province of Huelva is one of the areas most affected by acid mine drainage (AMD) in the world, which can produce big enhancements and fractionations in the waters affected by AMD. There are very few studies on this issue, and none on polonium-210. Twenty-two water reservoirs were sampled, and the 210 Po was measured in both dissolution and particulate phases. The 210 Po concentrations in the waters were in the same order of magnitude to those ones for unperturbed systems, although the data published to particulate matter are very scarce. A mean value and standard uncertainty for 210 Po of 0.25 ± 0.03 mBq L −1 in the dissolved matter, and 62 ± 9 mBq g −1 in the particulate matter can be established as base line for the reservoirs of the Huelva area. The distribution coefficients (k d ) range from 10 4 to 10 6 L kg −1 , in agreement to the found ones by other authors for the case of neutral waters, but being the lowest values for the more acidic reservoirs. It has been also found that 210 Po has a high tendency to be associated to the particulate matter for neutral-alkaline waters, however, under extreme acid conditions (pH < 3), increases the Po tendency to be associated to the dissolved phase. Therefore, the main conclusion obtained in this work is that AMD has no a significant influence on the total activity concentration of 210 Po in the waters of reservoirs, but the acidity has a clear influence on its distribution between both dissolved and the particulate phases. [ABSTRACT FROM AUTHOR]