This paper provides strong evidence for the contribution of the phylum Firmicutes in mediating the primary precipitation of Mg-rich carbonates (hydromagnesite, dolomite, magnesite, and nesquehonite) in recent microbialites from a highly alkaline and ephemeral inland lake (Las Eras, Central Spain). The carbonate mineral precipitation occurs sequentially as the microbial mats decay. Scanning electron microscopy (SEM) provided solid proof that hydromagnesite nucleation is initiated on the exopolymeric substances (EPS) and the microbial cells associated to the microbial mat degradation areas. The progressive mineralization of the EPS and bacterial cells by hydromagnesite plate-like crystals on their surface, results in the entombment of the bacteria and formation of radiating aggregates of hydromagnesite crystals. The hydrous phases, mostly hydromagnesite, were produced at a high percentage in the first stages of the microbial degradation of organic matter. When the availability of organic substrates declines, the heterotrophs tend to reduce their number and metabolic activity, remain dormant. At this stage, the anhydrous phases, dolomite and magnesite, nucleate on bacterial nanoglobules and/or collapsed cells. Evidence for the sequential formation of the Mg-rich carbonates trough the decay of organic matter by a fermentative EPS-forming bacterium isolated from the microbialites, Desemzia incerta, is drawn through a comparative analysis of carbonate formation in both natural and experimental settings. This study will help to constrain potential mechanisms of carbonate formation in natural systems, which are of fundamental importance not only for understanding modern environments but also as a window into the geologic past of Earth and potentially Mars.
A Tandem Approach to Functionalized Carbazoles from Indoles via Two Successive Regioselective Oxidative Heck Reactions Followed by Thermal Electrocyclization. -The synthesis of functionalized carbazoles is achieved via two successive oxidative Heck-reactions, subsequent 6-electrocyclization, and oxidative aromatization. The synthesis of unsymmetrically and trisubstituted carbazoles (XI) and (XIII) is also presented. -(LAHA*, J. K.; DAYAL, N.; Org. Lett. 17 (2015) 19, 4742-4745,
Salar de Pajonales, a Ca-sulfate salt flat in the Chilean High Andes, showcases the type of polyextreme environment recognized as one of the best terrestrial analogs for early Mars because of its aridity, high solar irradiance, salinity, and oxidation. The surface of the salar represents a natural climate-transition experiment where contemporary lagoons transition into infrequently inundated areas, salt crusts, and lastly dry exposed paleoterraces. These surface features represent different evolutionary stages in the transition from previously wetter climatic conditions to much drier conditions today. These same stages closely mirror the climate transition on Mars from a wetter early Noachian to the Noachian/Hesperian. Salar de Pajonales thus provides a unique window into what the last near-surface oases for microbial life on Mars could have been like in hypersaline environments as the climate changed and water disappeared from the surface. Here we open that climatological window by evaluating the narrative recorded in the salar surface morphology and microenvironments and extrapolating to similar paleosettings on Mars. Our observations suggest a strong inter-dependence between small and large scale features that we interpret to be controlled by extrabasinal changes in environmental conditions, such as precipitation-evaporation-balance changes and thermal cycles, and most importantly, by internal processes, such as hydration/dehydration, efflorescence/deliquescence, and recrystallization brought about by physical and chemical processes related to changes in groundwater recharge and volcanic processes. Surface structures and textures record a history of hydrological changes that impact the mineralogy and volume of Ca-sulfate layers comprising most of the salar surface. Similar surface features on Mars, interpreted as products of freeze-thaw cycles, could, instead, be products of water-driven, volume changes in salt deposits. On Mars, surface manifestations of such salt-related processes would point to potential water sources. Because hygroscopic salts have been invoked as sources of localized, transient water sufficient to support terrestrial life, such structures might be good targets for biosignature exploration on Mars.
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