A Raman spectral study of stream waters and efflorescent salts in Rio Tinto, Spain.

Acidic waters and sulfate-rich precipitates are found in mine tailings such as Rio Tinto (Huelva, SW, Spain). In this work we have characterized the chemical constituents of stream water and have identified some efflorescent salts and precipitates by means of Raman spectroscopy. Variable amounts of sulfate and bisulfate are found in the aqueous samples, suggesting changes in the acidity of the solutions. An estimation of the sulfate/water relative abundance is also given. Solid samples are readily identified as gypsum and as mixtures of hydrated hydroxysulfates belonging to the copiapite group. These results are consistent with previous works reporting the mineralogy and water composition of acid mine drainage-related sites, and proves the importance of Raman spectroscopy as a tool for accurate and noninvasive analyses of acid waters and associated geochemistry.

Microbiology and Nitrogen Cycle in the Benthic Sediments of a Glacial Oligotrophic Deep Andean Lake as Analog of Ancient Martian Lake-Beds.

Potential benthic habitats of early Mars lakes, probably oligotrophic, could range from hydrothermal to cold sediments. Dynamic processes in the water column (such as turbidity or UV penetration) as well as in the benthic bed (temperature gradients, turbation, or sedimentation rate) contribute to supply nutrients to a potential microbial ecosystem. High altitude, oligotrophic, and deep Andean lakes with active deglaciation processes and recent or past volcanic activity are natural models to assess the feasibility of life in other planetary lake/ocean environments and to develop technology for their exploration. We sampled the benthic sediments (down to 269 m depth) of the oligotrophic lake Laguna Negra (Central Andes, Chile) to investigate its ecosystem through geochemical, biomarker profiling, and molecular ecology studies. The chemistry of the benthic water was similar to the rest of the water column, except for variable amounts of ammonium (up to 2.8 ppm) and nitrate (up to 0.13 ppm). A life detector chip with a 300-antibody microarray revealed the presence of biomass in the form of exopolysaccharides and other microbial markers associated to several phylogenetic groups and potential microaerobic and anaerobic metabolisms such as nitrate reduction. DNA analyses showed that 27% of the Archaea sequences corresponded to a group of ammonia-oxidizing archaea (AOA) similar (97%) to Nitrosopumilus spp. and Nitrosoarchaeum spp. (Thaumarchaeota), and 4% of Bacteria sequences to nitrite-oxidizing bacteria from the Nitrospira genus, suggesting a coupling between ammonia and nitrite oxidation. Mesocosm experiments with the specific AOA inhibitor 2-Phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO) demonstrated an AOA-associated ammonia oxidation activity with the simultaneous accumulation of nitrate and sulfate. The results showed a rich benthic microbial community dominated by microaerobic and anaerobic metabolisms thriving under aphotic, low temperature (4°C), and relatively high pressure, that might be a suitable terrestrial analog of other planetary settings.

Raman signal processing software for automated identification of mineral phases and biosignatures on Mars.

Data from the ESA ExoMars Rover Mission will provide invaluable input for further studies in astro/exobiology. The search for mineral products as indicators of present and/or past biogenetic activities in Mars' surface and subsurface samples is the main objective of the compact Raman-laser-induced breakdown spectroscopy (LIBS) instrument. The inherent features of Raman spectroscopy and LIBS make the combined instrument a unique and very powerful tool in the search for biomarkers and hence it is regarded as the highest priority instrument for mineral analysis within the mission. We have developed a software package for the on-board processing of the instrument's data outputs, including spectral conditioning and search-match characterization of mineral phases and biomarkers. In this paper we show the mathematical and physical basis of the software package.

Dalangtan Saline Playa in a Hyperarid Region of Tibet Plateau: III. Correlated Multiscale Surface Mineralogy and Geochemistry Survey.

We report the first multiscale, systematic field-based testing of correlations between orbital scale advanced spaceborne thermal emission and reflection radiometer visible near-infrared (VNIR)/shortwave infrared (SWIR) reflectance and thermal infrared relative emissivity and outcrop scale Raman spectroscopy, VNIR reflectance, X-ray diffraction (XRD), and laser-induced breakdown spectroscopy (LIBS) mineralogy and chemistry in a saline dry lakebed. This article is one of three reports describing the evolution of salt deposits, meteorological record, and surface and subsurface salt mineralogy in Dalangtan, Qaidam Basin, a hyperarid region of the Tibet Plateau, China, as potential environmental, mineralogical, and biogeochemical analogs to Mars. We have successfully bridged remote sensing data to fine scale mineralogy and chemistry data. We have defined spectral end-members in the northwestern Qaidam Basin and classified areas within the study area on the basis of their spectral similarity to the spectral end-members. Results of VNIR/SWIR classification reveal zonation of spectral units within three large anticlinal domes in the study area that can be correlated between the three structures. Laboratory Raman, VNIR reflectance, XRD, and LIBS data of surface mineral samples collected along a traverse over Xiaoliangshan (XLS) indicate that the surface is dominated by gypsum, Mg sulfates, Na sulfates, halite, and carbonates, with minor concentrations of illite present in most samples as well. Our results can be used as a first step toward better characterizing the potential of orbital reflectance spectroscopy as a method for mineral detection and quantification in salt-rich planetary environments, with the benefit that this technique can be validated on the ground using instruments onboard rovers.

Dalangtan Saline Playa in a Hyperarid Region on Tibet Plateau: II. Preservation of Salts with High Hydration Degrees in Subsurface.

Based on a field expedition to the Dalangtan (DLT) saline playa located in a hyperarid region (Qaidam Basin) on the Tibet Plateau and follow-up investigations, we report the mineralogy and geochemistry of the salt layers in two vertical stratigraphic cross sections in the DLT playa. Na-, Ca-, Mg-, KCaMg-sulfates; Na-, K-, KMg-chlorides; mixed (K, Mg)-chloride-sulfate; and chlorate and perchlorate were identified in the collected samples. This mineral assemblage represents the last-stage precipitation products from Na-K-Mg-Ca-Cl-SO4 brine and the oxychlorine formation from photochemistry reaction similar to other hyperarid regions on Earth. The spatial distributions of these salts in both stratigraphic cross sections suggest very limited brine volumes during the precipitation episodes in the Holocene era. More importantly, sulfates and chlorides with a high degree of hydrations were found preserved within the subsurface salt-rich layers of DLT saline playa, where the environmental conditions at the surface are controlled by the hyperaridity in the Qaidam Basin on the Tibet Plateau. Our findings suggest a very different temperature and relative humidity environment maintained by the hydrous salts in a subsurface salty layer, where the climatic conditions at surface have very little or no influence. This observation bears some similarities with four observations on Mars, which implies not only a large humidity reservoir in midlatitude and equatorial regions on Mars but also habitability potential that warrants further investigation.

Geoelectrodes and Fuel Cells for Simulating Hydrothermal Vent Environments.

Gradients generated in hydrothermal systems provide a significant source of free energy for chemosynthetic life and may play a role in present-day habitability on ocean worlds. Electron/proton/ion gradients, particularly in the context of hydrothermal chimney structures, may also be relevant to the origins of life on Earth. Hydrothermal vents are similar in some ways to typical fuel cell devices: redox/pH gradients between seawater and hydrothermal fluid are analogous to the fuel cell oxidant and fuel reservoirs; the porous chimney wall is analogous to a separator or ion-exchange membrane and is also a conductive path for electrons; and the hydrothermal minerals are analogous to electrode catalysts. The modular and scalable characteristics of fuel cell systems make for a convenient planetary geology test bed in which geologically relevant components may be assembled and investigated in a controlled simulation environment. We have performed fuel cell experiments and electrochemical studies to better understand the catalytic potential of seafloor minerals and vent chimneys, using samples from a black smoker vent chimney as an initial demonstration. In a fuel cell with Na+-conducting Nafion® membranes and liquid fuel/oxidant reservoirs (simulating the vent environment), the black smoker mineral catalyst in the membrane electrode assembly was effective in reducing O2 and oxidizing sulfide. In a H2/O2 polymer electrolyte membrane (PEM) fuel cell with H+-conducting Nafion membranes, the black smoker catalyst was effective in reducing O2 but not in oxidizing H2. These fuel cell experiments accurately simulated the redox reactions that could occur in a geological setting with this particular catalyst, and also tested whether the minerals are sufficiently active to replace a commercial fuel cell catalyst. Similar experiments with other geocatalysts could be utilized to test which redox reactions could be driven in other hydrothermal systems, including hypothesized vent systems on other worlds.

Dalangtan Saline Playa in a Hyperarid Region on Tibet Plateau: I. Evolution and Environments.

Since 2008, we have been studying a saline lake, Dalangtan (DLT) Playa, and its surroundings in a hyperarid region of the Qaidam Basin on the Tibetan Plateau as a potential Mars analog site. We describe the evolution of saline deposits in the Qaidam Basin (including DLT), based on investigative findings accumulated over the course of 60 years of geological surveys. In addition, we report regional meteorological patterns recorded for the past 32 years along with meteorological station recorded data at DLT since 2012. Overall, the DLT area on the Tibetan Plateau has low atmospheric pressure, high ultraviolet radiation, low annual mean temperatures (T) but large seasonal and diurnal T cycles, and extremely low relative humidity, all of which bear some similarities with the equatorial region on Mars. In addition, salt types similar to those found on Mars, such as magnesium-sulfates, chlorides, and perchlorates, are found at the surface and subsurface in the DLT area (and the other two playas in the Qaidam Basin), thus supporting DLT as a Mars analog in terms of mineralogy and geochemistry.

Self-assembling iron oxyhydroxide/oxide tubular structures: laboratory-grown and field examples from Rio Tinto.

Rio Tinto in southern Spain has become of increasing astrobiological significance, in particular for its similarity to environments on early Mars. We present evidence of tubular structures from sampled terraces in the stream bed at the source of the river, as well as ancient, now dry, terraces. This is the first reported finding of tubular structures in this particular environment. We propose that some of these structures could be formed through self-assembly via an abiotic mechanism involving templated precipitation around a fluid jet, a similar mechanism to that commonly found in so-called chemical gardens. Laboratory experiments simulating the formation of self-assembling iron oxyhydroxide tubes via chemical garden/chemobrionic processes form similar structures. Fluid-mechanical scaling analysis demonstrates that the proposed mechanism is plausible. Although the formation of tube structures is not itself a biosignature, the iron mineral oxidation gradients across the tube walls in laboratory and field examples may yield information about energy gradients and potentially habitable environments.

Raman spectroscopy of efflorescent sulfate salts from Iron Mountain Mine Superfund Site, California.

The Iron Mountain Mine Superfund Site near Redding, California, is a massive sulfide ore deposit that was mined for iron, silver, gold, copper, zinc, and pyrite intermittently for nearly 100 years. As a result, both water and air reached the sulfide deposits deep within the mountain, producing acid mine drainage consisting of sulfuric acid and heavy metals from the ore. Particularly, the drainage water from the Richmond Mine at Iron Mountain is among the most acidic waters naturally found on Earth. The mineralogy at Iron Mountain can serve as a proxy for understanding sulfate formation on Mars. Selected sulfate efflorescent salts from Iron Mountain, formed from extremely acidic waters via drainage from sulfide mining, have been characterized by means of Raman spectroscopy. Gypsum, ferricopiapite, copiapite, melanterite, coquimbite, and voltaite are found within the samples. This work has implications for Mars mineralogical and geochemical investigations as well as for terrestrial environmental investigations related to acid mine drainage contamination.

Analysis of Arctic ices by remote Raman spectroscopy.

A portable remote Raman instrument for field analysis has been developed. This instrument has been tested in the Arctic conditions during AMASE (Arctic Mars Analog Svalbard Expedition) campaigns 2007, 2008 and 2009. Besides its capability for mineral detection the remote system proved to be a very useful tool for ice structural analysis of icebergs and ice-wall in glaciers. For the first time at our knowledge Arctic ice has been analyzed in situ in different conditions and at distances ranging from 10 to 120m. The spectra obtained have enough quality to be used for quantitative spectral analysis.

Model-based measurements of diffusion of sulfuric acid into water using Raman spectroscopy.

The diffusion of molecular species within a sulfuric acid-water system has been monitored by Raman spectroscopy, a thermodynamic-chemical model of the mass transport properties of the species has been established, and its parameters optimized. It has been shown that the non-ideality of this multicomponent system plays a crucial role in its mass transport properties, which have been explained in terms of a diffusion model for the molecular species. The individual effective diffusion coefficients are not constant (characteristic of ideal systems) but are a function of the concentration of the species in solution. The model has been conceived in such a way that it can be adapted to any multicomponent mixture when the equilibriums among the ions are known. Raman spectroscopy provides the means to derive the speciation and concentration of species in multicomponent systems, and we have shown that the model-based measurement of the diffusion properties using Raman is a robust and accurate technique that allows for measuring the individual diffusion coefficients of the species in the mentioned system.