Transformation of Hexagonal Birnessite upon Reaction with Thallium(I): Effects of Birnessite Crystallinity, pH, and Thallium Concentration.

We examined the uptake of Tl(I) by two hexagonal birnessites and related phase transformations in laboratory experiments over 12 sequential additions of 0.01 M Tl(I)/Mn at pH 4.0, 6.0, and 8.0. The Tl-reacted Mn oxides were characterized for their structure, Tl binding, and morphology using X-ray diffraction, X-ray photoelectron and X-ray absorption spectroscopies, and transmission electron microscopy. Very limited Tl oxidation was observed in contrast to previous works, where equal Tl(I)/Mn was added in a single step. Instead, both birnessites transformed into a 2 × 2 tunneled phase with dehydrated Tl(I) in its tunnels at pH 4, but only partially at pH 6, and at pH 8.0 they remained layered. The first four to nine sequential Tl(I)/Mn additions resulted in lower residual dissolved Tl+ concentrations than when the same amounts of Tl(I)/Mn were added in single steps. This study thus shows that the repeated reaction of hexagonal birnessites with smaller Tl(I)/Mn at ambient temperature triggers a complete phase conversion with Tl(I) as the sole reacting cation. The novel pathway found may be more relevant for contaminated environments and may help explain the formation of minerals like thalliomelane [Tl+(Mn7.54+Cu0.52+)O16]; it also points to the possibility that other reducing species trigger similar Mn oxide transformation reactions.

Interplay of microbial communities with mineral environments in coralline algae.

Coralline algae are worldwide carbonate builders, considered to be foundational species and biodiversity hotspots. Coralline habitats face increasing pressure from human activities and effects related to Global Change, yet their ecological properties and adaptive responses remain poorly understood. The relationships of the algal microbiota with the mineral bioconstructions, as well as plasticity and resilience of coralline holobionts in a changing environment, are of particular interest. In the Gulf of California, Neogoniolithon trichotomum (Rhodophyta) is the main carbonate builder in tidal pools. We performed a multi-disciplinary assessment of the N. trichotomum microstructure using XRD, SEM microscopy and SR-FTIR spectromicroscopy. In the algal perithallus, magnesium-calcite and aragonite were spatially segregated and embedded in a polysaccharide matrix (rich in sulfated polysaccharides). Mg-calcites (18-19 mol% Mg) were the main mineral components of the thallus overall, followed by iron carbonates related to dolomite (ankerite) and siderite. Minerals of late evaporitic sequences (sylvite and bischofite) were also present, suggesting potential halophilic microenvironments within the algal thalli. The diverse set of abundant halophilic, halotolerant and oligotrophic taxa, whose abundance increase in the summer, further suggests this condition. We created an integrated model, based on environmental parameters and the microbiota distribution, that identified temperature and nutrient availability (particularly nitrate and silicate) as the main parameters related to specific taxa patterns. Among these, Hahella, Granulossicoccus, Ferrimonas, Spongiibacteraceae and cyanobacterial Xenococcaceae and Nostocaceae change significantly between seasons. These bacterial components might play relevant roles in algal plasticity and adaptive responses to a changing environment. This study contributes to the understanding of the interplay of the prokaryotic microbiota with the mineral microenvironments of coralline algae. Because of their carbonates with potential resistance to dissolution in a higher pCO2 world and their seasonally dynamic bacteria, coralline algae are relevant targets to study coastal resilience and carbonated systems responses to changing environments.

Production of nitrates and perchlorates by laser ablation of sodium chloride in simulated Martian atmospheres. Implications for their formation by electric discharges in dust devils.

Nitrates and perchlorates are present both on Earth and Mars. In the Martian environment perchlorates dominate over nitrates whereas on Earth is contrariwise. This implies that the mechanisms responsible for their formation are different for both planets. The chemical elements required for their formation are nitrogen and chlorine, which are present in the atmosphere and surface, respectively. Dust in the Martian atmosphere causes atmospheric perturbations that lead to the development of dust-devils and sandstorms. Dust devils contain both chemical elements simultaneously, and normally generate high electric fields that can trigger the formation of electric discharges. Here we present laboratory experiments of this phenomenon using laser ablation of a sodium chloride (NaCl) plate in two different simulated atmospheres: (1) 96% CO2, 2% N2 and 2% Ar; and (2) 66% CO2, 33% N2 and 1% Ar. The dust that condensed and accumulated on the walls of the reactor was analyzed by different analytical techniques that included Fourier transform infrared spectroscopy, visible spectroscopy using azo dyes, thermogravimetry/simultaneous thermal analyses coupled to mass spectrometry, powder X-ray diffraction, and ion chromatography. The main components of the ablated dust corresponded to NaCl ≥ 91.5%, sodium nitrate (NaNO3 = 1.6-6.0%), and sodium perchlorate (NaClO4 âˆ¼ 0.2-0.3%). It is interesting to note that these salts formed in a dry process that is relevant to Mars today. A thermochemical model was used to understand the chemical steps that led to the formation of these salts in the gas phase. The NaNO3NaClO4 (wt/wt) ratio of this process was estimated to vary from 5.0 to 30.0; this ratio is too high compared to that found on Mars (NO3-ClO4- (wt/wt)) from 0.004 to 0.13). This implies that gaseous NaCl was not efficiently oxidized to perchlorate by the electric discharge process. We propose instead that gaseous metal chlorides (e.g., MgCl2, NaCl, CaCl2, KCl) were supplied to the atmosphere by the volatilization of chloride minerals present in the dust by electric discharges generated in dust devils and were subsequently oxidized to perchlorate by photochemical processes. Further work is required to assess the relative contribution of this possible source.

Exploring Biogeochemistry and Microbial Diversity of Extant Microbialites in Mexico and Cuba.

Microbialites are modern analogs of ancient microbial consortia that date as far back as the Archaean Eon. Microbialites have contributed to the geochemical history of our planet through their diverse metabolic capacities that mediate mineral precipitation. These mineral-forming microbial assemblages accumulate major ions, trace elements and biomass from their ambient aquatic environments; their role in the resulting chemical structure of these lithifications needs clarification. We studied the biogeochemistry and microbial structure of microbialites collected from diverse locations in Mexico and in a previously undescribed microbialite in Cuba. We examined their structure, chemistry and mineralogy at different scales using an array of nested methods including 16S rRNA gene high-throughput sequencing, elemental analysis, X-Ray fluorescence (XRF), X-Ray diffraction (XRD), Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS), Fourier Transformed Infrared (FTIR) spectroscopy and Synchrotron Radiation-based Fourier Transformed Infrared (SR-FTIR) spectromicroscopy. The resulting data revealed high biological and chemical diversity among microbialites and specific microbe to chemical correlations. Regardless of the sampling site, Proteobacteria had the most significant correlations with biogeochemical parameters such as organic carbon (Corg), nitrogen and Corg:Ca ratio. Biogeochemically relevant bacterial groups (dominant phototrophs and heterotrophs) showed significant correlations with major ion composition, mineral type and transition element content, such as cadmium, cobalt, chromium, copper and nickel. Microbial-chemical relationships were discussed in reference to microbialite formation, microbial metabolic capacities and the role of transition elements as enzyme cofactors. This paper provides an analytical baseline to drive our understanding of the links between microbial diversity with the chemistry of their lithified precipitations.

Fractionation and mobility of thallium in areas impacted by mining-metallurgical activities: Identification of a water-soluble Tl(I) fraction.

Mining and metallurgy generate residues that may contain thallium (Tl), a highly toxic metal, for which it is currently not feasible to determine its geochemical speciation through X-ray absorption spectroscopy due to a combination of very low contents and the interference of accompanying high arsenic contents. Therefore, fractionation studies in residues and soils are required to analyze the mobility and bioavailability of this metal, which in turn provide information to infer its speciation. For this purpose, in this work a modification of the BCR procedure was applied to residues and contaminated soils from three mining zones of Mexico and two mining zones of Spain, spanning samples with acidic to alkaline pH values. The Tl extraction procedure consisted of the following fractions: (1) water-extractable, (2) easily exchangeable and associated to carbonates, associated to (3) poorly-crystalline and (4) crystalline Fe and Mn oxyhydroxides, and (5) associated to organic matter and sulfides; and finally a residual fraction as associated to refractory primary and other secondary minerals. The extracted contents were analyzed by Inductively-Coupled Plasma with Mass Spectrometry. Surprisingly, water-soluble, in Tl(I) oxidation state, was detected in most areas, regardless of the pH, a fact that has not been reported before in these environments, and alerts to potential health risks not previously identified. Most of the samples from a metallurgy area showed high levels of Tl in non-residual fractions and a strong correlation was obtained between extracted Mn and Tl in the third fraction, suggesting its association to poorly crystalline manganese oxides. In the majority of samples from purely mining environments, most of the Tl was found in the residual fraction, most probably bound to alumino-silicate minerals. The remaining Tl fractions were extracted mainly associated to the reducible mineral fractions, and in one case also in the oxidizable fraction (presumably associated to sulfides). Capsule: Soluble Tl(I) was found in all soil samples contaminated with either mining or metallurgical wastes. Additionally, in those affected by metallurgical wastes a very strong Tl-Mn correlation was found.

Salinity Effects on the Adsorption of Nucleic Acid Compounds on Na-Montmorillonite: a Prebiotic Chemistry Experiment.

Any proposed model of Earth's primitive environments requires a combination of geochemical variables. Many experiments are prepared in aqueous solutions and in the presence of minerals. However, most sorption experiments are performed in distilled water, and just a few in seawater analogues, mostly inconsistent with a representative primitive ocean model. Therefore, it is necessary to perform experiments that consider the composition and concentration of dissolved salts in the early ocean to understand how these variables could have affected the absorption of organic molecules into minerals. In this work, the adsorption of adenine, adenosine, and 5'AMP onto Na+montmorillonite was studied using a primitive ocean analog (4.0 Ga) from experimental and computational approaches. The order of sorption of the molecules was: 5'AMP > adenine > adenosine. Infrared spectra showed that the interaction between these molecules and montmorillonite occurs through the NH2 group. In addition, electrostatic interaction between negatively charged montmorillonite and positively charge N1 of these molecules could occur. Results indicate that dissolved salts affect the sorption in all cases; the size and structure of each organic molecule influence the amount sorbed. Specifically, the X-ray diffraction patterns show that dissolved salts occupy the interlayer space in Na-montmorillonite and compete with organic molecules for available sites. The adsorption capacity is clearly affected by dissolved salts in thermodynamic terms as deduced by isotherm models. Indeed, molecular dynamic models suggest that salts are absorbed in the interlamellar space and can interact with oxygen atoms exposed in the edges of clay or in its surface, reducing the sorption of the organic molecules. This research shows that the sorption process could be affected by high concentration of salts, since ions and organic molecules may compete for available sites on inorganic surfaces. Salt concentration in primitive oceans may have strongly affected the sorption, and hence the concentration processes of organic molecules on minerals.

Origin of clay minerals in Early Eocene volcanic paleosols on King George Island, Maritime Antarctica.

The paleoclimate during the Early Eocene in Maritime Antarctica is characterized by cool conditions without a pronounced dry season. Soils formed on volcanic material under such climate conditions in modern analogue environments are usually Andosols rich in nanocrystalline minerals without pedogenic smectite. The paleosols formed on volcanic material on King Georges Island are covered by basalts, dated by 6 new 40Ar/39Ar datings to 51-48 Ma, and are rich in smectite. A pedogenic origin of the smectites would suggest a semi-arid rather than a wet non-seasonal humid paleoclimate. To investigate the origin of the smectites in these paleosols we used X-ray diffraction and microscopic techniques. Minor mineralogical changes between the volcanic parent material and the paleosols and a homogenous distribution of smectites throughout the paleosol horizons indicate that these smectites were mainly inherited from the pyroclastic parent material, which was altered prior to surficial weathering. Nevertheless, the mineralogical properties, such as degree of crystallinity and octahedral site occupancy, of these smectites were modified during the ancient soil formation. Our findings highlight that trioctahedral smectites were a product of deuteric alteration of pyroclastic rocks and were progressively transformed to dioctahedral smectites during weathering in a soil environment on King George Island.