Mechanisms shaping the gypsum stromatolite-like structures in the Salar de Llamara (Atacama Desert, Chile).

The explanation of the origin of microbialites and specifically stromatolitic structures is a problem of high relevance for decoding past sedimentary environments and deciphering the biogenicity of the oldest plausible remnants of life. We have investigated the morphogenesis of gypsum stromatolite-like structures currently growing in shallow ponds (puquíos) in the Salar de Llamara (Atacama Desert, Northern Chile). The crystal size, aspect ratio, and orientation distributions of gypsum crystals within the structures have been quantified and show indications for episodic nucleation and competitive growth of millimetric to centimetric selenite crystals into a radial, branched, and loosely cemented aggregate. The morphogenetical process is explained by the existence of a stable vertical salinity gradient in the ponds. Due to the non-linear dependency of gypsum solubility as a function of sodium chloride concentration, the salinity gradient produces undersaturated solutions, which dissolve gypsum crystals. This dissolution happens at a certain depth, narrowing the lower part of the structures, and producing their stromatolite-like morphology. We have tested this novel mechanism experimentally, simulating the effective dissolution of gypsum crystals in stratified ponds, thus providing a purely abiotic mechanism for these stromatolite-like structures.

101 contact twins in gypsum experimentally obtained from calcium carbonate enriched solutions: mineralogical implications for natural gypsum deposits.

Gypsum twins are frequently observed in nature, triggered by a wide array of impurities that are present in their depositional environments and that may exert a critical role in the selection of different twin laws. Identifying the impurities able to promote the selection of specific twin laws has relevance for geological studies aimed at interpreting the gypsum depositional environments in ancient and modern deposits. Here, the effect of calcium carbonate (CaCO3) on gypsum (CaSO4·2H2O) growth morphology has been investigated by performing temperature-controlled laboratory experiments with and without the addition of carbonate ions. The precipitation of twinned gypsum crystals has been achieved experimentally (101 contact twin law) by adding carbonate to the solution, and the involvement of rapidcreekite (Ca2SO4CO3·4H2O) in selecting the 101 gypsum contact twin law was supported, suggesting an epitaxial mechanism. Moreover, the occurrence of 101 gypsum contact twins in nature has been suggested by comparing the natural gypsum twin morphologies observed in evaporitic environments with those obtained in experiments. Finally, both orientations of the primary fluid inclusions (of the negative crystal shape) with respect to the twin plane and the main elongation of sub-crystals that form the twin are proposed as a fast and useful method (especially in geological samples) to distinguish between the 100 and 101 twin laws. The results of this study provide new insights into the mineralogical implications of twinned gypsum crystals and their potential as a tool to better understand natural gypsum deposits.

Multi-isotope (carbon and chlorine) analysis for fingerprinting and site characterization at a fractured bedrock aquifer contaminated by chlorinated ethenes.

The use of compound specific multi-isotope approach (C and Cl) in the characterization of a chlorinated ethenes contaminated fractured aquifer allows the identification of several sources and contaminant plumes, as well as the occurrence of biodegradation and mixing processes. The study site is located in Spain with contamination resulting in groundwater concentrations of up to 50mg/L of trichloroethene (TCE), the most abundant chlorinated ethene, and 7 mg/L of tetrachloroethene (PCE). The potential sources of contamination including abandoned barrels, an underground tank, and a disposal lagoon, showed a wide range in δ(13)C values from -15.6 to -40.5‰ for TCE and from -18.5 to -32.4‰ for PCE, allowing the use of isotope fingerprinting for tracing of the origin and migration of these contaminants in the aquifer. In contrast, there is no difference between the δ(37)Cl values for TCE in the contaminant sources, ranging from +0.53 to +0.66‰. Variations of δ(37)Cl and δ(13)C in the different contaminant plumes were used to investigate the role of biodegradation in groundwater. Moreover, the isotopic data were incorporated into a reactive transport model for determination of whether the isotope pattern observed downstream from the tank's source could be explained by the simultaneous effect of mixing and biodegradation. The results demonstrate that a multi-isotope approach is a valuable tool for characterization of complex sites such as fractured bedrock aquifer contaminated by multiple sources, providing important information which can be used by consultants and site managers to prioritize and design more successful remediation strategies.

Processes releasing arsenic to groundwater in the Caldes de Malavella geothermal area, NE Spain.

Arsenic concentrations exceeding the World Health Organization drinking water guideline (10 µg/L) have been measured in thermal and non-thermal groundwaters from the Caldes de Malavella geothermal area (La Selva graben, NE Spain). The CO(2)-rich Na-HCO(3) thermal waters (up to 60 °C at the spring) have elevated arsenic concentrations ([As(T)] from 50 to 80 µg/L). The non-thermal waters are of Ca-Na-HCO(3)-Cl type and have [As(T)] between <1 and 200 µg/L, defining a hot-spot distribution. The present-day contribution of As from CO(2)-rich thermal waters to non-thermal aquifers is very limited, as shown by the concentration of geothermal tracers such as Li and B. Redox-controlling processes appear to govern the mobility of As in the non-thermal waters. Arsenate is clearly predominant in most oxidizing groundwaters (>85% of As(V) over total As), whereas reducing, high-As groundwater reaches up to 100% in arsenite. The reductive dissolution of Fe(III) oxyhydroxides and the coupled release and reduction of adsorbed As explain the elevated dissolved arsenite (up to 190 µg/L) and Fe (up to 14 mg/L) content in the more reducing non-thermal groundwater. Conversely, the high levels of nitrate (up to 136 mg/L) ensure an oxidizing environment in most non-thermal groundwaters ([As(T)] between <1 and 60 µg/L). Under these conditions, Fe(III) oxyhydroxides are stable and As release to groundwater is not related to their dissolution. Instead, dissolved arsenate concentrations up to 60 µg/L are explained by a competition for sorption sites with other species, mainly bicarbonate and silicic acid, while arsenate desorption due to pH increase is not considered a major process.

Fertilizer characterization: isotopic data (N, S, O, C, and Sr).

A detailed isotopic characterization (delta15N(Ntotal), delta15N(NO3), delta18O(NO3), delta34S(SO4), delta18O(SO4), (delta13C(Ctotal), and 87Sr/86Sr) of 27 commercial fertilizers used in Spain is presented in this paper. Results together with a compilation of fertilizer isotopic published data are used for two purposes: (i) to identify the origin of the primary constituents and raw materials used in fertilizer manufacture and relate these data with their heavy metals and rare earth elements (REE) contents; (ii) to compare the fertilizer isotopic signatures with natural values and other anthropogenic pollutants and evaluate the usefulness of multi-isotopic analyses to trace fertilizer contaminations in future study cases. Isotope data permit us to know, in most cases, the origin of the primary constituents of fertilizers, and the 87Sr/86Sr ratio distinguishes the origin of the phosphate content--phosphorites or carbonatites--which in turn implies a qualitatively defined and potentially contaminant presence of REE and heavy metals in fertilizers. Delta15N, delta34S, and 87Sr/86Sr have already been used to trace fertilizer contaminations. Their utility can be improved by the coupled use of delta15N(NO3)-delta18O(NO3) and delta34S(SO4)-delta18O(SO4) to evaluate the fractionation processes that can affect contaminants. Moreover, multi-isotopic analyses, using heavy isotopes, allow us to see beyond the fractionation effects to the fertilizer stable isotope signatures and a better distinction from other anthropogenic contaminants.