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.

Human health risks associated with urban soils in mining areas.

We studied the chemical composition of As and Pb in total (<2 mm) and fine fractions (<50 µm) of 52 urban soil samples from Minas de Riotinto (mining area) and Aracena (non-exposed area) in SW Spain. In addition to a soil phytotoxicity bioassay using Lactuca Sativa L., we modelled and performed carcinogenic and non-carcinogenic human health risk assessment, later comparing our data with relative cancer mortality rates reported at the municipal level. This study demonstrates that mineralized bedrock and natural soil-forming processes affect the geochemistry of natural (in-situ) urban soils, which in many cases surpass the regulatory levels for As (36 mg/kg) and Pb (275 mg/kg). Fine fractions of in-situ and mixed urban soils -susceptible of inhalation- are significantly enriched in As and Pb with respect to fine fractions of aggregate materials (ex-situ soils of chalky sands and gravel) in Minas de Riotinto. The soils in Minas de Riotinto are significantly enriched in As (total and fine fractions) and Pb (total fraction) with respect to Aracena. Despite elevated bulk concentrations of As and Pb, only one in-situ sample exhibits phytotoxic effects of the soil-water extracts on Lactuca Sativa L. seeds. Health risk assessment of these towns as exposure areas indicates that the soils of Minas de Riotinto are indeed a health risk to the residents, whereas there is no potential risk in Aracena. The reported relative mortality rates in Minas de Riotinto show a greater mortality of carcinogenic tumors potentially related to As and Pb exposure, including lung cancer. Both soil type and use must be considered when administrators or policy-makers evaluate health risks involved in urbanistic decision-making. To minimize exposure risk and adverse health outcomes, we recommend that in-situ soils surpassing regulatory levels for As and Pb in public playgrounds and passing areas should be covered with aggregate materials.

Socio-Demographic Health Determinants Are Associated with Poor Prognosis in Spanish Patients Hospitalized with COVID-19.

INTRODUCTION: Social vulnerability is a known determinant of health in respiratory diseases. Our aim was to identify whether there are socio-demographic factors among COVID-19 patients hospitalized in Spain and their potential impact on health outcomes during the hospitalization. METHODS: A multicentric retrospective case series study based on administrative databases that included all COVID-19 cases admitted in 19 Spanish hospitals from 1 March to 15 April 2020. Socio-demographic data were collected. Outcomes were critical care admission and in-hospital mortality. RESULTS: We included 10,110 COVID-19 patients admitted to 18 Spanish hospitals (median age 68 (IQR 54-80) years old; 44.5% female; 14.8% were not born in Spain). Among these, 779 (7.7%) cases were admitted to critical care units and 1678 (16.6%) patients died during the hospitalization. Age, male gender, being immigrant, and low hospital saturation were independently associated with being admitted to an intensive care unit. Age, male gender, being immigrant, percentile of average per capita income, and hospital experience were independently associated with in-hospital mortality. CONCLUSIONS: Social determinants such as residence in low-income areas and being born in Latin American countries were associated with increased odds of being admitted to an intensive care unit and of in-hospital mortality. There was considerable variation in outcomes between different Spanish centers.

Antimony as a tracer of non-exhaust traffic emissions in air pollution in Granada (S Spain) using lichen bioindicators.

We have studied the metal air pollution trends in a medium-sized Spanish city suffering from traffic emission using in-situ lichen Xanthoria parietina as a bioindicator. The large scale sampling included 97 samples from urban, metropolitan and remote control areas of Granada that were analyzed by Inductively Coupled Plasma-Mass Spectrometry. Enrichment factor of Sb exhibited severe anthropogenic enrichment, whereas Cu and Sb showed significantly higher median values in the urban areas with respect to metropolitan areas. Additionally, bioaccumulation ratios of V, Cr, Ni, Cu, Zn, Cd, Sb, and Pb -associated to exhaust and non-exhaust traffic emissions- enabled us to delineate hot spots of metal(loid) accumulation in the main accesses to the city, characterized by dense traffic and copious traffic jams. To distinguish non-exhaust emissions, we studied the spatial distribution of the Cu:Sb ratio -a tracer of brake wear- highlighting the surroundings of the highway and the main traffic accesses to the city likely due to sudden hard braking and acceleration during frequent traffic jams. Our study shows that the metal(loid) contents in lichens are excellent proxies for non-exhaust traffic emissions and that their contribution to the metal(loid) air pollution in Granada is more significant than previously thought.

Effects of redox oscillations on the phosphogypsum waste in an estuarine salt-marsh system.

Salt marshes are natural deposits of heavy metals in estuarine systems, where sulphide precipitation associated with redox changes often results in a natural attenuation of contamination. In the present study, we focus on the effects of variable redox conditions imposed to a highly-polluted phosphogypsum stack that is directly piled over the salt marsh soil in the Tinto River estuary (Huelva, Spain). The behaviour of contaminants is evaluated in the phosphogypsum waste and in the marsh basement, separately, in controlled, experimentally-induced oscillating redox conditions. The results revealed that Fe, and to a lesser extent S, control most precipitation/dissolution processes. Ferric iron precipitates in the form of phosphates and oxyhydroxides, while metal sulphide precipitation is insignificant and appears to be prevented by the abundant formation of Fe phosphates. An antagonistic evolution with changing redox conditions was observed for the remaining contaminants such as Zn, As, Cd and U, which remained mobile in solution during most of experimental run. Therefore, these findings revealed that high concentrations of phosphates inhibit the typical processes of immobilisation of pollutants in salt-marshes which highlights the elevated contaminant potential of phosphogypsum wastes on coastal environments.

Lichens as a spatial record of metal air pollution in the industrialized city of Huelva (SW Spain).

Huelva is a highly industrialized city in SW Spain hosting, among others, a Cu smelter, a phosphate fertilizer plant, a power plant, and oil refineries. This study aims to evaluate metal concentrations in lichens as bioindicators of atmospheric pollution in the impacted urban areas. Xanthoria parietina species from Huelva and nearby villages, as well as reference samples from remote, non-contaminated urban areas, were analyzed for trace elements (V, Cr, Mn, Co, Ni, Cu, Zn, Sr, As, Cd, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Er, Tm, Yb, Lu, Pb, Th, U) using Inductively Coupled Plasma-Mass Spectrometry; and for major elements (Ca, K, Mg, P, and S) by Inductively Coupled Plasma-Optical Emission Spectrometry after acid digestion. The metal composition of X. parietina exhibits spatial distribution patterns with extremely elevated concentrations (Co, Ni, Cu, Zn, As, Cd, Sb, Ba, Pb, U, and S) in the surroundings of the industrial estates to <1 km distance. Mean concentrations were significantly lower in the urban areas >1 km from the pollution sources. However, air pollution persists in the urban areas up to 4 km away, as the mean concentrations of Cu, Zn, As, Cd, Sb and S remained considerably elevated in comparison to the reference samples. Though rigorous source apportionment analysis was not the aim of this study, a good positive correlation of our results with metal abundances in ambient particulate matter and in pollution sources points to the Cu smelter as the main source of pollution. Hence, the severe air pollution affecting Huelva and nearby urban areas may be considered a serious health risk to local residents.

Unraveling the impact of chronic exposure to metal pollution through human gallstones.

This study aims to explore the impact of chronic metal exposure derived from persistent pollution from mining activity using human gallstones as proxies. The samples were obtained from patients residing in geologically and environmentally contrasting areas in the Province of Huelva, SW Spain, allowing for the evaluation of the regional effect of metal pollution. The study group resides in the Iberian Pyrite Belt characterized by natural and anthropogenic metal pollution from mining activities, whereas the control group resides in the Ossa Morena Zone famous for its natural parks. A total of 68 gallstones were first classified based on their phase composition and structure and subsequently their chemical composition was studied using solution Inductively Coupled Plasma-Mass Spectrometry. The metal concentrations increased in the cholesterol-rich gallstones from pure, to mixed and composite cholesterol stones along with the increasing amount of minor phases, such as bilirubinate, carbonate, and phosphate. These cholesterol stones did not show an evident enrichment tendency. On the contrary, pigment stones, composed of bilirubinate, carbonate, and phosphate phases, were rich in a variety of elements and the regional comparison showed that the pigment stones from the study area were enriched in sulfide-associated metal(loid)s, Mn, Fe, Cu, Zn, Sr, As, Ag, Sb, and Pb with respect to the control group. Inhalation of polluted airborne particulate matter is considered as one of the main exposure routes among the residents of the study area. Additionally, consumption of local water and locally produced food products such as fruit and vegetables and dermal contact may be possible sources of exposure, but no direct connection was observed.

Stable isotope insights into the weathering processes of a phosphogypsum disposal area.

Highly acidic phosphogypsum wastes with elevated potential for contaminant leaching are stack-piled near coastal areas worldwide, threatening the adjacent environment. Huge phosphogypsum stacks were disposed directly on the marshes of the Estuary of Huelva (SW Spain) without any impermeable barrier to prevent leaching and thus, contributing to the total contamination of the estuarine environment. According to the previous weathering model, the process water ponded on the surface of the stack, initially used to carry the waste, was thought to be the main washing agent through its infiltration and subsequently the main component of the leachates emerging as the edge outflows. Preliminary restorations have been applied to the site and similar ones are planned for the future considering process water as the only pollution agent. Further investigation to validate the pollution pathway was necessary, thus an evaluation of the relationship between leachates and weathering agents of the stack was carried out using stable isotopes (δ18O, δ2H, and δ34S) as geochemical tracers. Quantification of the contribution of all possible end-members to the phosphogypsum leachates was also conducted using ternary mixing via the stable isotopic tracers. The results ruled out ponded process water as main vector of edge outflow pollution and unveiled a continuous infiltration of estuarine waters to the stack implying that is subjected to an open weathering system. The isotopic tracers revealed a progressive contribution downstream from fluvial to marine signatures in the composition of the edge outflows, depending on the location of each disposal zone within the different estuarine morphodynamic domains. Thus, the current study suggests that the access of intertidal water inside the phosphogypsum stack, for instance through secondary tidal channels, is the main responsible for the weathering of the waste in depth, underlying the necessity for new, more effective restorations plans.

Effects of seawater mixing on the mobility of trace elements in acid phosphogypsum leachates.

This research reports the effects of pH increase on contaminant mobility in phosphogypsum leachates by seawater mixing, as occurs with dumpings on marine environments. Acid leachates from a phosphogypsum stack located in the Estuary of Huelva (Spain) were mixed with seawater to achieve gradually pH7. Concentrations of Al, Fe, Cr, Pb and U in mixed solutions significantly decreased with increasing pH by sorption and/or precipitation processes. Nevertheless, this study provides insight into the high contribution of the phosphogypsum stack to the release of other toxic elements (Co, Ni, Cu, Zn, As, Cd and Sb) to the coastal areas, as 80-100% of their initial concentrations behaved conservatively in mixing solutions with no participation in sorption processes. Stable isotopes ruled out connexion between different phosphogypsum-related wastewaters and unveiled possible weathering inputs of estuarine waters to the stack. The urgency of adopting effective restoration measures in the study area is also stressed.

New insights into the metal partitioning in different microphases of human gallstones.

Chronic metal exposure, e.g. from metal mining, may cause accumulation of metals in soft and hard tissues, and in developing biomineralizations in the human body. Gallstones are biomineralizations formed in the gallbladder which are able to trap trace elements from the bile. Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) was used to analyze gallstone cross-sections to trace the elemental abundances and correlate them with the principal phases constituting gallstones, namely cholesterol, Ca bilirubinate salts, Ca carbonate, and Ca phosphate. Five different types of gallstones (pure, mixed, and composite cholesterol stones, pigment stone, and carbonate stone) were chosen according to a previous classification based on phase characterization by different spectroscopic and microscopic techniques. These data were combined with bulk solution ICP-MS/OES analyses for total elemental concentrations. The results indicated that cholesterol has a zero capacity to retain elements except for Ca. Hence, pure cholesterol stones contained the lowest bulk metal concentrations, and the metals were found in the scarce carbonate and phosphate phases in these calculi. Calcium and trace element concentrations increased in other types of gallstones along with increasing amount of bilirubinate, carbonates and phosphates; pigment stones being the most enriched in metals. Phosphates were the principal carriers of Ca, P, Na, Mg, Mn, Fe, Pb, and Cd, whereas carbonate phases were enriched in Ca, Mg, Na, and Mn in order of decreasing abundance. Bilirubinate on the other hand was enriched in Ca, Cu, Ag, and Ni. The higher trace metal affinities of bilirubinate and phosphate explain the elevated metal concentrations observed in the pigment stones. These results give new insight to the trace metal behavior in the gallstone formation and the metal accumulation in the human body, validating the possible use of these biomineralizations as a proxy for exposure to metal pollution.

Combined microstructural and mineralogical phase characterization of gallstones in a patient-based study in SW Spain - Implications for environmental contamination in their formation.

This study explores the environmental impact of metal exposure on humans through detailed phase and structural characterization of gallstones from two environmentally contrasting populations in Huelva Province (SW Spain). A total of 42 gallstone samples, obtained after surgical intervention at the Riotinto Hospital, were studied by powder X-ray diffraction (XRD), Fourier Transformed Infra-Red spectroscopy (FTIR), FTIR-µ-ATR (Attenuated Total Reflection) coupled with an optical microscope, and by Environmental Scanning Electron Microscope with Energy Dispersive X-ray Spectroscopy (ESEM-EDS), and subsequently classified according to their phase composition and structure. Additionally, the patients were enquired for their living habits in order to analyze the source of possible exposure to metal contamination. The gallstones were classified into pure, mixed and composite cholesterol stones, black and brown pigment stones, and carbonate stones. The patients from the study group residing in a region with acknowledged metal contamination of both natural and anthropogenic origin have a higher risk of metal exposure through contaminated soil, particle matter in the air, and consumption of local water and food products. According to our findings, the metal exposure is related to a higher tendency of forming black pigment stones in the study group in comparison to the control group residing in a natural park with nearly pristine environmental conditions. Moreover, the gallstones from the study group showed to contain more abundant metal components, such as Cu, Fe, Ni, and Zn, than those from the control group. To our knowledge this is the first study to examine the regional environmental impact of metal exposure on human gallstones.

Spectral induced polarization (SIP) response of mine tailings.

Mine tailings impoundments are a source of leachates known as acid mine drainage (AMD) which can pose a contamination risk for surrounding surface and groundwater. Methodologies which can help management of this environmental issue are needed. We carried out a laboratory study of the spectral induced polarization (SIP) response of tailings from the Haveri Au-Cu mine, SW Finland. The primary objectives were, (1) to determine possible correlations between SIP parameters and textural properties associated with oxidative-weathering mechanisms, mineralogical composition and metallic content, and (2) to evaluate the effects of the pore water chemistry on SIP parameters associated with redox-inactive and redox-active electrolytes varying in molar concentration, conductivity and pH. The Haveri tailings exhibit well defined relaxation spectra between 100 and 10,000Hz. The relaxation magnitudes are governed by the in-situ oxidative-weathering conditions on sulphide mineral surfaces contained in the tailings, and decrease with the oxidation degree. The oxidation-driven textural variation in the tailings results in changes to the frequency peak of the phase angle, the imaginary conductivity and chargeability, when plotted versus the pore water conductivity. In contrast, the real and the formation electrical conductivity components show a single linear dependence on the pore water conductivity. The increase of the pore water conductivity (dominated by the increase of ions concentration in solution) along with a transition to acidic conditions shifts the polarization peak towards higher frequencies. These findings show the unique sensitivity of the SIP method to potentially discriminate AMD discharges from reactive oxidation zones in tailings, suggesting a significant advantage for monitoring threatened aquifers.