Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems

The rates of chemical reactions between aqueous sulfates and sulfides are essentially identical to sulfur isotopic exchange rates between them, because both the chemical and isotopic reactions involve simultaneous oxidation of sulfide-sulfur atoms and reduction of sulfate-sulfur. The rate of reaction can be expressed as a second order rate law: R = k·[∑SO₄^2?]·[∑S^2?], where R is the overall rate, k is the rate constant and [∑SO₄^2?] and [∑S^2?] are molal concentrations. We have computed the rate constants from the available experimental data on the partial exchange of sulfur isotopes between aqueous sulfates and sulfides using the rate law established by us: $\text{ln(}\text{α}{}^{\mathrm{e}}\text{? α}\text{α}{}^{\mathrm{e}}\text{? α}{}^0\text{) = ? kt([∑SO}{}_4{}^{\mathrm{2?}}\text{] + [∑S}{}^{\mathrm{2?}}\text{])}$, where t is time and α⁰, α, and α^e are, respectively, the fractionation factors at t = 0 (the initial condition), at the end of experiment, and at equilibrium. The equilibrium fractionation factor can be expressed as: $\text{1000 ln α}{}^{\mathrm{e}}\text{=}\text{6.463 × 10}{}^6\text{T}{}^2\text{+ 0.56 (±.5)}$ (T in Kelvin).The rate constants are strongly dependent on T and pH, but not in as simple a manner as suggested by Igumnov (1976). Our rate constants in Na-bearing hydrothermal solutions decrease by 1 order of magnitude with an increase in pH by 1 unit at pH's less than ~3, remain constant in the pH range of ~4 to ~7, and again decrease at pH >7. The activation energy for the reaction also depends on pH: 18.4 ± 1 kcal/mole at pH = 2, 29.6 ± 1 kcal/mole at pH = 4 to 7, and between 40 and 47 kcal/mole at pH around 9. The observed pH dependence of the rate constant and of the activation energy can be best explained by a model involving thiosulfate molecules as reaction intermediates, in which the intramolecular exchange of sulfur atoms in thiosulfates becomes the rate determining step.The rate constants obtained in this study were used to compute the changes in the isotopic fractionation factors between aqueous sulfates and sulfides during cooling of fluids. Comparisons with data of coexisting sulfate-sulfide minerals in hydrothermal deposits, suggest that simple cooling was not a likely mechanism for coprecipitation of sulfate and sulfide minerals at temperatures below 350°C. Mixing of sulfide-rich solutions with sulfate-rich solutions at or near the depositional sites is a more reasonable process for explaining the observed fractionation.The degree of attainment of chemical equilibrium between aqueous sulfates and sulfides in a hydrothermal system, and the applicability of a_O2-pH type diagrams to mineral deposits, depends on the ∑S content and the thermal history of the fluid, which in turn is controlled by the flow rate and the thermal gradient in the system.The rates of sulfate reduction by non-bacterial processes involving a variety of reductants are also dependent on T, pH, [∑SO₄^2?], and [∑S^2?], and appear to be fast enough to become geochemically important at temperatures above about 200°C.     

Validation of Landslide Susceptibility Maps; Examples and Applications from a Case Study in Northern Spain

A procedure for validating landslide susceptibility maps wasapplied in a study area in northern Spain and the results obtained compared. Validationwas used to carry out sensitivity analysis for individual variables and combinationsof variables. The validity of different map-making methods was tested, as well as theutility of different types of Favourability Functions. The results obtained show thatvalidation is essential to determine the predictive value of susceptibility maps. Italso helps to better select the most suitable function and significant variables, thus improving the efficiency of the mapping process. Validation based on a temporal strategy makes it possible to derive hazard maps from susceptibility maps.     

Crystallization conditions of Los Angeles, a basaltic Martian meteorite

The texture of Los Angeles (stone 1) is dominated by relatively large (0.5−2.0 mm) anhedral to subhedral grains of pyroxene, and generally subhedral to euhedral shocked plagioclase feldspar (maskelynite). Minor phases include subhedral titanomagnetite and ilmenite, Fe-rich olivine, olivine+augite-dominated symplectites [some of which include a Si-rich phase and some which do not], pyrrhotite, phosphate(s), and an impact shock-related alkali- and silica-rich glass closely associated with anhedral to euhedral silica grains. Observations and model calculations indicate that the initial crystallization of Mg-rich pigeonitic pyroxenes at ≤1150 °C, probably concomitantly with plagioclase, was followed by pigeonitic and augitic compositions between 1100 and 1050 °C whereas between 1050 and 920 to 905 °C pyroxene of single composition crystallized. Below 920 to 905 °C, single composition Fe-rich clinopyroxene exsolved to augite and pigeonite. Initial appearance of titanomagnetite probably occurred near 990 °C and FMQ-1.5 whereas at and below 990 °C and ≥FMQ-1.5 titanomagnetite and single composition Fe-rich clinopyroxene may have started to react, producing ilmenite and olivine. However, judging from the most common titanomagnetite compositions, we infer that most of this reaction likely occurred between 950 and 900 °C at FMQ-1.0±0.2 and nearly simultaneously with pyroxene exsolution, thus producing assemblages of pigeonite, titanomagnetite, olivine, ilmenite, and augite. We deem this reaction as the most plausible explanation for the formation of the olivine+augite-dominated symplectites in Los Angeles. But we cannot preclude possible contributions to the symplectites from the shock-related alkali- and silica-rich glass or shocked plagioclase, and the breakdown of Fe-rich pigeonite compositions to olivine+augite+silica below 900 °C. Reactions between Fe-Ti oxides and silicate minerals in Los Angeles and other similar basaltic Martian meteorites can control the T-fO₂ equilibration path during cooling, which may better explain the relative differences in fO₂ among the basaltic Martian meteorites.     

Gravimetric and magnetic fabric study of the Sintra Igneous complex: laccolith-plug emplacement in the Western Iberian passive margin

International Journal of Earth Sciences - The geometry and emplacement of the ~ 96 km2, Late Cretaceous Sintra Igneous complex (SIC, ca. 80 Ma) into the West Iberian passive...     

Hydrogeological research on intensively exploited deep aquifers in the ‘Loma de Úbeda’ area (Jaén, southern Spain)

The intensive use of groundwater for irrigation in the area of Úbeda (‘Loma de Úbeda’, Jaén, southern Spain) has transformed an area of traditionally rain-fed dry farmland into fields with some of the highest olive oil productivity in the world. Early hydrogeological research studies, initiated just after the beginning of the groundwater exploitation, revealed that the water was collected from three different overlapping aquifers occupying an area of over 1,100 km², with the lower aquifers located at depths from 300 to over 700 m in an area of 440 km². Multidisciplinary research, based on geological characterization, and piezometric, hydrochemical and isotopic data, has led to a conceptual model of functioning in this complex hydrogeological system. The proposed model allows for the identification of the recharge areas, and the discharge, which is at present mainly associated with the groundwater pumping. Areas of mixing of waters from the different aquifers and the main hydrogeochemical processes affecting groundwater quality are described.     

Pre‐Alpine discordant granitic dikes in the metamorphic core of the Betic Cordillera: tectonic implications

Pegmatite dikes bearing andalusite crosscut foliation S₂ in Alpujarride gneisses and schists. Post‐S₂ andalusite is transposed by a foliation S₃, defined by fibrolite, which affects the dikes. The dikes represent highly differentiated granitic magmas with low REE and Zr contents and a positive Eu anomaly. U‐Pb SHRIMP dating of magmatic zircons provided Pan‐African ages (cores) and late Variscan ages (rims). However, U‐rich rims also provided metamorphic Alpine ages, supporting a polyorogenic tectonometamorphic history for pre‐Mesozoic Alpujarride rocks.     

Episodic Biogeochemical Variability in a Low-Flow Mediterranean Estuary

To investigate to what extent episodic physical processes regulate nutrient availability and phytoplankton assemblages of the Mahon estuary (Minorca Island), we carried out an intensive field study during 2010–2011. During the study period, environmental conditions spanned from intense stratification to a continuous mixing and from lack of riverine inflow to intense runoff. Our data reveals a sequence of biogeochemical states of the estuary that result from the interplay between runoff, other non-periodic forcings (winds, sea level oscillations), and variations in water renewal. Seasonal runoff was revealed as a major driver of winter circulation and of the influx of inorganic nutrients, in particular nitrate. However, because of the combination between runoff and flushing time, the effects of floodwater events on phytoplankton are short-lived (days). Conversely, during summer, when freshwater influx declines, water renewal relies on pulsed atmospheric forcing that may be of local or remote origin. As depicted from the low nitrate concentrations (<1 μM) and enhanced ammonium (>1 μM), this change in circulation and external loads carries nutrient assimilation within the estuary head and forces the use of remnant nutrients through regenerating pathways to sustain an enhanced phytoplankton biomass at the lower estuary. Episodic variability represented between 52 and 65% of the annual chlorophyll variance. Despite the fact that episodic pulses represented intense departures from base biogeochemical state of the estuary, at time scale larger than weeks, the phytoplankton community composition and dynamics was largely regulated by the integrated effect of these episodes and other environmental drivers associated with seasonality rather than by individual storm events only. Our results suggest that even though the system presents good recovery capacity to individual storm episodes, it may be more vulnerable to increased nutrient fluxes during summer, as well as to changes in episode timing and frequency.     

Spatial and temporal variation of the nekton and hyperbenthos from a temperate European estuary with regulated freshwater inflow

The aquatic macrofauna of the Guadalquivir estuary were sampled (1 mm mesh persiana net) at 5 sampling sites located along the entire (except the tidal freshwater region) estuarine gradient of salinity (outer 50 km). A total of 134 fish and macroinvertebrate species was collected but only 62 were considered common or regularly present in the estuary. Univariate measures of the community structure showed statistically significant differences among sampling sites: species richness, abundance, and biomass decreased in the upstream direction, being positively correlated with the salinity. Temporal differences of these three variables were also statistically significant. While a clear seasonal pattern (minimum densities in winter and maximum in spring-summer) was observed for abundance and biomass, no such pattern existed for the number of species. Mysids was the most dominant group throughout the estuary (96% to 99% of abundance; 49% to 85% of biomass), although fish biomass was also important at the outer estuary (36% to 38%). Multivariate analyses indicated highly significant spatial variation in the macrofaunal communities observed along the salinity gradient. These analyses suggest that the underlying structure was a continuum with more or less overlapping distributions of the species dependent on their ability to tolerate different physicochemical conditions. There were also significant temporal (intermonthly + interannual) variation of the estuarine community; the relative multivariate dispersion indicated that monthly variation was more considerable (relative multivariate dispersion >1) at the outer part of the estuary during the wet year (last 20 km) and was higher in the inner stations during the dry year (32 to 50 km from the river mouth). Since a clear negative exponential relationship was observed between the freshwater input (from a dam located 110 km upstream) and water salinity at all sampling stations, it is concluded that the human freshwater management is probably affecting the studied estuarine communities. While the higher seasonal (long-term) stability of the salinity gradient, due to the human control of the freshwater input, may facilitate the recruitment of marine species juveniles during the meteorologically unstable early-spring, the additional (short-term) salinity fluctuations during the warm period may negatively affect species that complete their lifecycle within the estuary.