Aguasanta M. Sarmiento

Toxicity and potential risk assessment of a river polluted by acid mine drainage in the Iberian Pyrite Belt (SW Spain).

Metal contamination from acid mine drainage (AMD) is a serious problem in the southwest of the Iberian Peninsula, where the Iberian Pyrite Belt is located. This zone contains original sulfide reserves of about 1700Mt distributed among more than 50 massive sulfide deposits. Weathering of these minerals releases to the waters significant quantities of toxic elements, which severely affect the sediments and surface waters of the region. The main goal of this paper is to evaluate the toxicity and the potential risk associated with the mining areas using Microtox test and different factors which assess the degree of contamination of the sediments and waters. For this, a natural stream polluted by AMD-discharge from an abandoned mine has been studied. The results show that elevated concentrations of Cu, As and Zn involve an important potential risk on the aquatic environment, associated both with sediments and waters. Microtox test informs that the sediments are extremely or very toxic, mainly related to concentrations of Fe, As, Cr, Al, Cd, Cu and Zn. Pollution is mainly transferred to the sediments increasing their potential toxicity. A natural creek affected by AMD can store a huge amount of pollution in its sediments while exhibiting a not very low water pH and low water metal concentration.

Inorganic arsenic speciation at river basin scales : The Tinto and Odiel Rivers in the Iberian Pyrite Belt, SW Spain

The Tinto and Odiel rivers are heavily affected by acid mine drainage from mining areas in the Iberian Pyrite Belt. In this work we have conducted a study along these rivers where surface water samples have been collected. Field measurements, total dissolved metals and Fe and inorganic As speciation analysis were performed. The average total concentration of As in the Tinto river (1975 microg L(-1)) is larger than in the Odiel river (441 microg L(-1)); however, the mean concentration of As(III) is almost four times higher in the Odiel. In wet seasons the mean pH levels of both rivers (2.4 and 3.2 for the Tinto and Odiel, respectively) increase slightly and the amount of dissolved total arsenic tend to decrease, while the As(III)/(V) ratio strongly increase. Besides, the concentration of the reduced As species increase along the water course. As a result, As(III)/(V) ratio can be up to 100 times higher in the lower part of the basins. An estimation of the As(III) load transported by both rivers into the Atlantic Ocean has been performed, resulting in about 60 kg yr(-1) and 2.7t yr(-1) by the Tinto and Odiel rivers, respectively.

Natural attenuation processes in two water reservoirs receiving acid mine drainage

Characteristics of water profiles and sulphide formation processes in sediments were studied in two water reservoirs affected by acid mine drainage in order to investigate the mechanisms controlling the physical and chemical processes that, under favourable conditions, act to reduce the toxicity, mobility and concentration of metals and metalloids in the water column. Water columns and pore-waters from sediments were analysed for Fe species, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn, Cr), sulphide, sulphate and bicarbonate. Inorganic reduced sulphur compounds (acid volatile sulphur, pyrite sulphur and elemental sulphur) and reactive Fe were determined in the sediments. A sequential extraction was also performed. Both reservoirs behave like holomictic and monomictic lakes, with a summer thermal stratification that disappears during winter. pH values between 4 and 7 can be observed along the water columns. Pore-water concentrations of up to 25 mg/l of Fe, 4 mg/l of Al, 1.3 mg/l of Zn, 170 microg/l of Pb, 11 microg/l of As, etc. have been found. The results suggest that toxic elements such as Cu, Zn, Co, Pb, Cr, As, etc. are mainly found in the bioavailable fraction which is the most hazardous for the environment. The calculated degree of sulphidization (DOS) and degree of pyritization (DOP) values indicates that removal of trace elements from anoxic pore-waters occurs by coprecipitation and/or adsorption on newly formed Fe sulphides (framboidal pyrite), attenuating the contamination. However oxidation of the sediments during turnover periods also occurs, which releases toxic elements back into the water column.

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.

Metal mobility and toxicity to microalgae associated with acidification of sediments: CO2 and acid comparison

The injection and storage of CO2 into marine geological formations has been suggested as a mitigation measure to prevent global warming. However, storage leaks are possible resulting in several effects in the ecosystem. Laboratory-scale experiments were performed to evaluate the effects of CO2 leakage on the fate of metals and on the growth of the microalgae Phaeodactylum tricornutum. Metal contaminated sediments were collected and submitted to acidification by means of CO2 injection or by adding HCl. Sediments elutriate were prepared to perform toxicity tests. The results showed that sediment acidification enhanced the release of metals to elutriates. Iron and zinc were the metals most influenced by this process and their concentration increased greatly with pH decreases. Diatom growth was inhibited by both processes: acidification and the presence of metals. Data obtained is this study is useful to calculate the potential risk of CCS activities to the marine environment.

New preservation method for inorganic arsenic speciation in acid mine drainage samples

A new preservation method has been proposed for the speciation of As(III) and As(V) in acid mine drainage (AMD) samples, characterised by low pH and high metallic content. Samples were taken from a polymetallic sulphides mining area in the province of Huelva (SW Spain), under exploitation until the 1960s for its Cu, Pb and Zn sulphides. The abandoned mine works and the numerous waste rocks heaps produce AMD with high As content, an aqueous pollution source for the nearby streams. Short-term (from few hours to 1 week) preservation of the two inorganic arsenic species was studied, trying different containers (polyethylene, glass), presence or absence of light, temperatures (ambient, refrigerated, frozen), preserving agents and procedures (EDTA, HCl or AcH acids, cation-exchange resin). The speciation results obtained by liquid chromatography-hydride generation-atomic fluorescence spectrometry (HPLC-HG-AFS) indicated a rapid conversion of the samples with most of the preservation procedures reported in the literature after 3h after sample collection. A promising method for arsenic preservation has been developed in this work, which maintains the arsenic species distribution in the original samples for a longer time. It consists in the use of opaque glass containers, acidification of the samples with HCl and in situ cleanup with cationic exchange resin, which allowed to preserve the samples for As speciation for at least 48 h.

Metal cycling during sediment early diagenesis in a water reservoir affected by acid mine drainage

The discharge of acid mine drainage (AMD) into a reservoir may seriously affect the water quality. To investigate the metal transfer between the water and the sediment, three cores were collected from the Sancho Reservoir (Iberian Pyrite Belt, SW Spain) during different seasons: turnover event; oxic, stratified period; anoxic and under shallow perennially oxic conditions. The cores were sliced in an oxygen-free atmosphere, after which pore water was extracted by centrifugation and analyzed. A sequential extraction was then applied to the sediments to extract the water-soluble, monosulfide, low crystallinity Fe(III)-oxyhydroxide, crystalline Fe(III)-oxide, organic, pyrite and residual phases. The results showed that, despite the acidic chemistry of the water column (pH<4), the reservoir accumulated a high amount of autochthonous organic matter (up to 12 wt.%). Oxygen was consumed in 1mm of sediment due to organic matter and sulfide oxidation. Below the oxic layer, Fe(III) and sulfate reduction peaks developed concomitantly and the resulting Fe(II) and S(II) were removed as sulfides and probably as S linked to organic matter. During the oxic season, schwertmannite precipitated in the water column and was redissolved in the organic-rich sediment, after which iron and arsenic diffused upwards again to the water column. The flux of precipitates was found to be two orders of magnitude higher than the aqueous one, and therefore the sediment acted as a sink for As and Fe. Trace metals (Cu, Zn, Cd, Pb, Ni, Co) and Al always diffused from the reservoir water and were incorporated into the sediments as sulfides and oxyhydroxides, respectively. In spite of the fact that the benthic fluxes estimated for trace metal and Al were much higher than those reported for lake and marine sediments, they only accounted for less than 10% of their total inventory dissolved in the column water.

Evaluation of heavy metals and arsenic speciation discharged by the industrial activity on the Tinto-Odiel estuary, SW Spain.

This study reports the annual amount of heavy metals discharged by industrial activity into the estuary of the Ría of Huelva (SW Spain). The findings showed that the discharged metals found in highest amounts were Fe (11 t y⁻¹), Zn (3.4 t y⁻¹) and Mo (0.88 t y⁻¹). There were other metals with high pollutant charge, such as Ti (232 kg y⁻¹), As (228 kg y⁻¹), Ni (195 kg y⁻¹), Pb (100 kg y⁻¹), Cr (39 kg y⁻¹) and Cd (33 kg y⁻¹). These results were compared with pollutants transported via the Tinto and Odiel rivers from abandoned mining activities in the Iberian Pyrite Belt (IPB), and it was deduced that the amounts spilled exclusively by industries were less than 1% in relation to the total discharge. Hence, the treatment of residues from the IPB should be the priority goal to improve water quality in the estuary.

Pollutant flows from a phosphogypsum disposal area to an estuarine environment: An insight from geochemical signatures.

Phosphogypsum wastes from phosphate fertilizer industries are stockpiled in stacks with high contamination potential. An assessment of the environmental impact, including the use of geochemical tracers such as rare earth elements (REE) and Cl/Br ratios, was carried out in the phosphogypsum stack located at the Estuary of Huelva (SW Spain). Inside the pile, highly polluted acid pore-waters flows up to the edge of the stack, emerging as small fluvial courses, known as edge outflows, which discharge directly into the estuary. The disposal area is divided into four zones; two unrestored zones with surface ponds of industrial process water and two a priori already-restored zones. However, an extensive sampling of edge outflows conducted in the perimeter of the four zones demonstrates the high potential of contamination of the whole stack, including those zones that were supposedly restored. These solutions are characterized by a pH of 1.9 and concentrations of 6100 mg/L for P, 1970 mg/L for S, 600 mg/L for F, 200mg/L for NH4(+), 100mg/L for Fe, 10-30 mg/L for Zn, As and U, and 1-10mg/L for Cr, Cu and Cd. Preliminary restoration actions and those planned for the future prioritize removal of ponded process water and cover of the phosphogypsum with artificial topsoil. These actions presuppose that the ponded process water percolates through the porous medium towards the edge up to reach the estuary. However, geochemical tracers rule out this connection and point to an estuarine origin for these leachates, suggesting a possible tidal-induced leaching of the waste pile in depth. These findings would explain the ineffectiveness of preliminary restoration measures and should be considered for the development of new action plans.

Assessment of metal contamination, bioavailability, toxicity and bioaccumulation in extreme metallic environments (Iberian Pyrite Belt) using Corbicula fluminea.

The Iberian Pyrite Belt (SW Iberian Peninsula) has intense mining activity. Currently, its fluvial networks receive extremely acid lixiviate residue discharges that are rich in sulphates and metals in solution (acid mine drainage, AMD) from abandoned mines. In the current study, the sediment and water quality were analysed in three different areas of the Odiel River to assess the risk associated with the metal content and its speciation and bioavailability. Furthermore, sediment contact bioassays were performed using the freshwater clam Corbicula fluminea to determine its adequacy as a biomonitoring tool in relation to theoretical risk indexes and regulatory thresholds. Reburial activity and mortality were used as the toxic responses of clams when exposed to contaminated sediment. The results showed coherence between the water and sediment chemical contamination for most of the metals. The reburial activity was correlated with the metal toxicity, but no clam mortality was registered. The bioaccumulation of the studied metals in the clam did not have a significant correlation with the bioavailable fraction of the metal content in the environment, which could be related to a potential different speciation in this singular environment. The bioaccumulation responses were negative for As, Cd and Zn in highly contaminated environments and were characterized as severe, considerable and low potential environmental risks, respectively. The results show that C. fluminea is a good biomonitor of Cu and Pb.