Metal mobility and bioaccessibility from cyanide leaching heaps in a historical mine site.

Unlike acidic sulfide mine wastes, where metal/loid mobility and bioaccessibility has been widely studied, less attention has been paid to alkaline cyanide heap leaching wastes. Thus, the main goal of this study is to evaluate the mobility and bioaccessibility of metal/loids in Fe-rich (up to 55%) mine wastes resulting from historical cyanide leaching activities. Wastes are mainly composed of oxides/oxyhydroxides (i.e. goethite and hematite), oxyhydroxisulfates (i.e. jarosite), sulfates (i.e., gypsum, evaporitic sulfate salts), carbonates (i.e., calcite, siderite) and quartz, with noticeable concentrations of metal/loids (e.g., 1453-6943 mg/kg of As, 5216-15,672 mg/kg; of Pb, 308-1094 mg/kg of Sb, 181-1174 mg/kg of Cu, or 97-1517 mg/kg of Zn). The wastes displayed a high reactivity upon rainfall contact associated to the dissolution of secondary minerals such as carbonates, gypsum, and other sulfates, exceeding the threshold values for hazardous wastes in some heap levels for Se, Cu, Zn, As, and sulfate leading to potential significant risks for aquatic life. High concentrations of Fe, Pb, and Al were released during the simulation of digestive ingestion of waste particles, with average values of 4825 mg/kg of Fe, 1672 mg/kg of Pb, and 807 mg/kg of Al. Mineralogy may control the mobility and bioaccessibility of metal/loids under rainfall events. However, in the case of the bioaccessible fractions different associations may be observed: i) the dissolution of gypsum, jarosite and hematite would mainly release Fe, As, Pb, Cu, Se, Sb and Tl; ii) the dissolution of an un-identified mineral (e.g., aluminosilicate or Mn oxide) would lead to the release of Ni, Co, Al and Mn and iii) the acid attack of silicate materials and goethite would enhance the bioaccessibility of V and Cr. This study highlights the hazardousness of wastes from cyanide heap leaching, and the need to adopt restoration measures in historical mine sites.

Effects of estuarine water mixing on the mobility of trace elements in acid mine drainage leachates.

This research reports the effects of pH increase on contaminant mobility in acid mine drainage from the Iberian Pyrite Belt by seawater mixing in the laboratory, simulating the processes occurring in the Estuary of Huelva (SW Iberian Peninsula). Concentrations of Al, Fe, As, Cu and REY in mixing solutions significantly decreased with increasing pH. Schwertmannite precipitation at pH 2.5-4.0 led to the total removal of Fe(III) and As. Subsequently, iron-depleted solutions began to be controlled by precipitation of basaluminite at pH 4.5-6.0, which acted as a sink for Al, Cu and REY. Nevertheless, as the pH rises, schwertmannite becomes unstable and releases back to solution the previously retained As. Moreover, other elements (S, Zn, Cd, Ni and Co) behaved conservatively in mixing solutions with no participation in precipitation processes. Some toxic elements finally end up to the Atlantic Ocean contributing to the total pollutant loads and environmentally threatening the coastal areas.

Thallium distribution in an estuary affected by acid mine drainage (AMD): The Ría de Huelva estuary (SW Spain).

This study investigates the behavior of Tl in the Ría de Huelva (SW Spain), one of the most metal polluted estuaries in the world. Dissolved Tl concentration displayed a general decrease across the estuary during the dry season (DS); from 5.0 to 0.34 µg/L in the Tinto and Odiel estuaries, respectively, to 0.02 µg/L in the channel where the rivers join. A slighter decrease was observed during the wet season (WS) (from 0.72 to 0.14 µg/L to 0.02 µg/L) due to the dilution effect of rainfalls in the watersheds. These values are 3 orders of magnitude higher than those reported in other estuaries worldwide. Different increases in Tl concentrations with salinity were observed in the upper reaches of the Tinto and Odiel estuaries, attributed to desorption processes from particulate matter. Chemical and mineralogical evidences of particulate matter, point at Fe minerals (i.e., jarosite) as main drivers of Tl particulate transport in the estuary. Unlike other estuaries worldwide, where a fast sorption process onto particulate matter commonly takes place, Tl is mainly desorbed from particulate matter in the Tinto and Odiel estuaries. Thus, Tl may be released back from jarositic particulate matter across the salinity gradient due to the increasing proportion of unreactive TlCl0 and K+ ions, which compete for adsorption sites with Tl+ at increasing salinities. A mixing model based on conservative elements revealed a 6-fold increase in Tl concentrations related to desorption processes. However, mining spills like that occurred in May 2017 may contribute to enhance dissolved and particulate Tl concentrations in the estuary as well as to magnify these desorption processes (up to around 1100% of Tl release), highlighting the impact of the mine spill on the remobilization of Tl from the suspended matter to the water column.

Stream-pit lake interactions in an abandoned mining area affected by acid drainage (Iberian Pyrite Belt).

Opencast mining of sulfide ore deposits may lead to the formation of anthropogenic acidic lakes with highly polluted waters. In these systems, it is crucial to understand the hydrological connections between surface and groundwater and their contribution to the pollutant load delivered to the downgradient streams. This study characterizes the interactions between surface and groundwater in an acidic pit lake using different geochemical tracers (i.e., REE and other trace metals). The San Telmo pit lake, located in one of the most pollutant sources of the Iberian Pyrite Belt (IPB), can be considered as a flow-through pit lake except during dry periods, when it behaves as a terminal lake due to lower inputs by surface waters and higher outputs by evaporation. Results based on geochemical tracers indicate that the main inputs to the pit lake come from surface waters, with minor groundwater inputs rich in As, Cr, Cu, Fe and Pb. The contaminant load released from the mining area is very high (e.g., median values of 520 kg/day of Fe and 38 kg/day of Zn), causing the degradation of the fluvial network downstream. Most of released pollutants come from waste dumps located at the W of the mining zone (~50-70% of Al, Cd, Mg, Mn, Ni, SO4 and Zn and > 70% for Cu, Cr, Fe and, V), while the contribution of the water coming out the pit lake and other dumps is much lower. Thus, remediation efforts to improve the area and fluvial courses downstream must focus on the W waste dumps.

Geochemical behaviour and transport of technology critical metals (TCMs) by the Tinto River (SW Spain) to the Atlantic Ocean.

This paper addresses the behaviour of several technology critical metals (TCMs), i.e., rare earth elements (REEs), Y, Sc, Ga and Tl, in the Tinto River (SW Spain), quantifying their fluxes to the Atlantic Ocean and unravelling the governing geochemical processes controlling their solubility. To accomplish this goal, a high-resolution (2-24 h) sampling was performed during the hydrological year 2017/18. Mean dissolved concentrations of 380 µg/L of REE, 99 µg/L of Y, 15 µg/L of Sc, 9.2 µg/L of Ga and 4.8 µg/L of Tl were found. Most TCMs followed a behaviour similar to that of sulphate and base metals throughout the year, exhibiting a quasi-conservative behaviour due to acidic conditions. However, dissolved Tl concentrations seem to be strongly controlled by Tl incorporation onto secondary minerals and diatoms deposited on the riverbed, especially during the dry season. The remobilization of riverbed sediments led to the transport of significant amounts of TCMs associated with particulate matter, especially Al oxy-hydroxy-sulphates or Al-silicates rather than Fe precipitates (except for Tl and Ga). Around 5.8 t of REE, 1.3 t of Y, 248 kg of Sc, 139 kg of Ga and 138 kg of Tl were delivered annually in their dissolved forms by the Tinto River to the Atlantic Ocean, which constitutes around 0.09% of the dissolved global flux into the oceans of Y, 0.02% of the REE flux, 0.01% of the Ga flux and 0.001% of the Sc flux.

Distribution and availability of rare earth elements and trace elements in the estuarine waters of the Ría of Huelva (SW Spain).

Metal pollution in estuaries represents a serious environmental challenge, especially in areas affected by industrial and mining activities. This study investigates the metal partitioning and availability of rare earth elements (REE), Y and other trace metals (Ag, Tl, U and Cs) in the Ria of Huelva estuary (SW Spain), strongly affected by mining and industrial activities. A 30 h monitoring campaign was performed collecting periodic water samples and deploying diffusive gradient in thin films (DGTs) devices to determine the main factors controlling metal availability. The dissolved concentrations of U (3118-3952 ng/L) and Cs (284-392 ng/L) were in the same order of magnitude than those reported in other estuaries and coastal waters worldwide, however, REE (26-380 ng/L), Y (15-109 ng/L), Ag (14-307 ng/L) and Tl (29-631 ng/L) concentrations exceeded these values for the same salinities. Unlike most metals (i.e. Ag, Tl, U, Cs), which were mainly found in the dissolved form (87-100% of total), REE and Y were found in the particulate phase (22-36% of total). Metal lability was mainly related to the concentration in the water column following this order: U>REE>Y>Ag>Tl. A similar binding mechanism was observed for Tl and Cd, due to its chemical affinity. This relationship between chemical properties and absorption by DGT-resin was also observed for REE (and Y), Rb and Sr, which may cause bioaccumulation upon persistent exposure, considering the ability of these metals to cross the biological membranes. The lability of metals predicted by geochemical codes did not coincide with absorption of labile metals by DGTs due probably to the instability of complexes in contact with the DGT membranes, the inability of metals to form thermodynamically stable complexes or the absorption of colloids. From this work it can be concluded that DGT passive sampling should complement traditional sampling to monitor metal availability in aquatic environments.

Metal partitioning and speciation in a mining-impacted estuary by traditional and passive sampling methods.

This study deals with the metal partitioning and bioavailability of metal/loids in the estuary Ria of Huelva (SW Spain) which is strongly affected by historical mining and industrial activities. To address this issue, traditional (i.e., grab samples) and passive sampling (i.e., diffusive gradient in thin films, DGTs) was carried out in the outer part of the estuary during different tidal cycles in order to determine the dissolved and particulate metal/loid concentrations. The dissolved concentrations exceeded, by several orders of magnitude, those reported in other estuaries worldwide that are affected by anthropogenic activities. A spatial pattern was observed in the metal distribution; a decrease seaward was recorded for some of the elements associated with mining (e.g., Cu, Zn, and Cd), the opposite tendency is observed for others associated with harbor emissions (e.g., Sn, Ni, or Pb). A different metal/loid partitioning pattern was also observed; Fe, and to a lesser extent Pb and Sn, were chiefly found in the particulate matter, while the rest of the elements were mainly found in the dissolved form. The bioavailability of the metal/loids was studied by speciation using both geochemical modeling and DGTs; while concentrations in DGTs supported metal/loid speciation for Zn, Cd, Mn, Co, As, and Sb according to their affinity to form strong or weak complexes, some discrepancies were observed for other elements such as Cu, V, Fe, and Pb, which are prone to forming strong complexes. The main reason behind the unexpectedly high Fe and Pb DGTs concentrations may be associated with their presence in the colloidal particles passing through the DGT. There was a strong positive correlation between dissolved and DGT concentrations for Cd and Mn, and to a lesser extent for Fe and Cu, highlighting the direct relationship between the concentrations in water and availability to living organisms in the estuary.

Effects on the mobility of metals from acidification caused by possible CO2 leakage from sub-seabed geological formations.

Carbon dioxide capture and storage (CCS) in submarine geological formations has been proposed as a mitigation measure for the prevention of global warming. However, leakage of CO2 to overlying sediments may occur over time, leading to various effects on ecosystems. Laboratory-scale experiments were performed, involving direct release of carbon dioxide into sediment, inside non-pressurized chambers, in order to provide data on the possible effects of CO2 leakage from geological storage sites on the fate of several metals. Marine sediments from three sites with different levels of contamination were sampled and submitted to acidification by means of CO2 injection. The experiment lasted 10 days and sediment samples were collected at the beginning and end of the experiment and pore water was extracted for metal analysis. The results revealed that mobility of metals from sediment to pore water depends on the site, metal and length of time exposed. Mobilization of the metals Al, Fe, Zn, Co, Pb and Cu increases with acidification, and this response generally increases with time of exposure to CO2 injection. The geochemical model applied suggests that acidification also influences the speciation of metals, transforming metals and metalloids, like As, into species much more toxic to biota. The data obtained from this study will be useful for calculating the potential risk of CCS activities to the marine environment.