Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: I. Effect of hydraulic retention time

Sulfate-reducing passive bioreactors have proved to be an effective technology for the treatment of acid mine drainage (AMD) contaminated waters over relatively short periods of time (1–5 a). However, long-term efficiency can be limited by several factors including problems related to the hydraulic properties of the reactive mixture. In this study, the effect of two hydraulic retention times (HRTs) of 7.3 d and 10 d on the performance of passive bioreactors was evaluated over an 11-month period for the treatment of a highly contaminated AMD. Evolution of the porosity and hydraulic conductivity of the reactive mixture was also evaluated during the 15-month operation of two bioreactors. Results indicated that bioreactors were effective at both HRTs for increasing the pH and alkalinity of contaminated water and for SO₄ and metal removal (60–82% for Fe and up to 99.9% for Cd, Ni and Zn). Although the quality of treated effluent was significantly improved with the 10 d HRT compared to the 7.3 d HRT, results showed that the higher HRT reduced the porosity and the permeability of the reactive mixture which might lead to hydraulic related problems and, eventually, to limited efficiency in long-term operation compared to a shorter HRT. The choice of HRT for a passive bioreactor must therefore consider both the desired quality of treated effluent and the potential for deterioration of hydraulic properties in the reactive mixture.     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: II. Metal removal mechanisms and potential mobility

Column bioreactors were used for studying mechanisms of metal removal, assessment of long-term stability of spent reactive mixtures, as well as potential metal mobility after treating highly contaminated acid mine drainage (AMD; pH 2.9–5.7). Several physicochemical, microbiological, and mineralogical analyses were performed on spent reactive mixtures collected from 4 bioreactors, which were tested in duplicate for two hydraulic retention times (7.3d and 10d), with downward flow over an 11-month period. Consistent with the high metal concentrations in the AMD feed, and with low metal concentrations measured in the treated effluent, the physicochemical analyses indicated very high concentrations of metals (Fe, Mn, Cd, Ni, and Zn) in the top and bottom layers of the reactive mixtures from all columns. Moreover, the concentrations of Fe (50.8–57.8 g/kg) and Mn (0.53–0.70 g/kg) were up to twice as high in the bottom layers, whereas the concentrations of Cd (6.77–13.3 g/kg), Ni (1.80–5.19 g/kg) and Zn (2.53–13.2 g/kg) were up to 50-times higher in the top layers. Chemical extractions and elemental analysis gave consistent results, which indicated a low fraction of metals removed as sulfides (up to 15% of total metals recovered in spent reactive mixtures). Moreover, Fe and Mn were found in a more stable chemical form (residual fraction was 42–74% for Mn and 30–77% for Fe) relative to Cd, Ni or Zn, which seemed more weakly bound (oxidisable/reducible fractions) and showed higher potential mobility. Besides identifying (oxy)hydroxide and carbonate minerals, the mineralogical analyses identified metal sulfides containing Fe, Cd, Ni and Zn. Metal removal mechanisms were, therefore, mainly adsorption and other binding mechanisms with organic matter (for Cd, Ni and Zn), and the precipitation as (oxy)hydroxide minerals (for Fe and Mn). After 15 months, however, the column bioreactors did not lose their capacity for removing metals from the AMD. Although the metals were immobile during the bioreactor treatment, their mobility could increase from spent reactive mixtures, if stored inappropriately. Metal recovery by acidic leaching of spent substrates at the end of bioreactor operation could be an alternative.     

The presence of anomalous trace element levels in present day Jamaican soils and the geochemistry of Late-Miocene or Pliocene phosphorites

High levels of Cd and Zn in Jamaican soils observed in geochemical surveys are related to the presence of phosphorites of possible Late-Miocene or Pliocene age. The trace element and REE geochemistry of the phosphorites, together with SEM studies, indicate a guano origin for the phosphorites. No specific host minerals for Cd could be identified in the fossiliferous phosphorite which is characterized by uniquely high levels of Cd, Zn, Ag, Be, U and Y. However, in the soil Cd is present in lithiophorite and a complex history of pedological development is preserved in the aluminous–goethite present in the soil. The unique guano signature is preserved in the soil despite the fact that guanos themselves have either not been observed or have been destroyed by continuing karst and soil development. The phosphorite geochemical signature can be traced in the data of a 1988 island-wide soil geochemical survey, identifying areas where the Palaeo-environment that supported bird ‘rookeries’ existed in the Late-Miocene or Pliocene.     

Geochemical characterization of surface waters and groundwater resources in the Managua area (Nicaragua,Central America)

This paper reports new geochemical data on dissolved major and minor constituents in surface waters and ground waters collected in the Managua region (Nicaragua), and provides a preliminary characterization of the hydrogeochemical processes governing the natural water evolution in this area. The peculiar geological features of the study site, an active tectonic region (Nicaragua Depression) characterized by active volcanism and thermalism, combined with significant anthropogenic pressure, contribute to a complex evolution of water chemistry, which results from the simultaneous action of several geochemical processes such as evaporation, rock leaching, mixing with saline brines of natural or anthropogenic origin. The effect of active thermalism on both surface waters (e.g., saline volcanic lakes) and groundwaters, as a result of mixing with variable proportions of hyper-saline geothermal Na–Cl brines (e.g., Momotombo geothermal plant), accounts for the high salinities and high concentrations of many environmentally-relevant trace elements (As, B, Fe and Mn) in the waters. At the same time the active extensional tectonics of the Managua area favour the interaction with acidic, reduced thermal fluids, followed by extensive leaching of the host rock and the groundwater release of toxic metals (e.g., Ni, Cu). The significant pollution in the area, deriving principally from urban and industrial waste-water, probably also contributes to the aquatic cycling of many trace elements, which attain concentrations above the WHO recommended limits for the elements Ni (∼40 μg/l) and Cu (∼10 μg/l) limiting the potential utilisation of Lake Xolotlan for nearby Managua.     

The hydrochemistry of a semi-arid pan basin case study: Sua Pan,Makgadikgadi, Botswana

This study presents results on the fluid and salt chemistry for the Makgadikgadi, a substantial continental basin in the semi-arid Kalahari. The aims of the study are to improve understanding of the hydrology of such a system and to identify the sources of the solutes and the controls on their cycling within pans. Sampling took place against the backdrop of unusually severe flooding as well as significant anthropogenic extraction of subsurface brines. This paper examines in particular the relationship between the chemistry of soil leachates, fresh stream water, salty lake water, surface salts and subsurface brines at Sua Pan, Botswana with the aim of improving the understanding of the system’s hydrology. Occasionally during the short wet season (December–March) surface water enters the saline environment and precipitates mostly calcite and halite, as well as dolomite and traces of other salts associated with the desiccation of the lake. The hypersaline subsurface brine (up to TDS 190,000 mg/L) is homogenous with minor variations due to pumping by BotAsh mine (Botswana Ash (Pty) Ltd.), which extracts 2400 m³ of brine/h from a depth of 38 m. Notable is the decrease in TDS as the pumping rate increases which may be indicative of subsurface recharge by less saline water. Isotope chemistry for Sr (⁸⁷Sr/⁸⁶Sr average 0.722087) and S (δ³⁴S average 34.35) suggests subsurface brines have been subject to a lithological contribution of undetermined origin. Recharge of the subsurface brine from surface water including the Nata River appears to be negligible.     

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.