A review of microbial-environmental interactions recorded in Proterozoic carbonate-hosted chert.

The record of life during the Proterozoic is preserved by several different lithologies, but two in particular are linked both spatially and temporally: chert and carbonate. These lithologies capture a snapshot of dominantly peritidal environments during the Proterozoic. Early diagenetic chert preserves some of the most exceptional Proterozoic biosignatures in the form of microbial body fossils and mat textures. This fossiliferous and kerogenous chert formed in shallow marine environments, where chert nodules, layers, and lenses are often surrounded by and encased within carbonate deposits that themselves often contain kerogen and evidence of former microbial mats. Here, we review the record of biosignatures preserved in peritidal Proterozoic chert and chert-hosting carbonate and discuss this record in the context of experimental and environmental studies that have begun to shed light on the roles that microbes and organic compounds may have played in the formation of these deposits. Insights gained from these studies suggest temporal trends in microbial-environmental interactions and place new constraints on past environmental conditions, such as the concentration of silica in Proterozoic seawater, interactions among organic compounds and cations in seawater, and the influence of microbial physiology and biochemistry on selective preservation by silicification.

Formation of Zerovalent Iron in Iron-Reducing Cultures of Methanosarcina barkeri.

Methanogenic archaea have been shown to reduce iron from ferric [Fe(III)] to ferrous [Fe(II)] state, but minerals that form during iron reduction by different methanogens remain to be characterized. Here, we show that zerovalent iron (ZVI) minerals, ferrite [α-Fe(0)] and austenite [γ-Fe(0)], appear in the X-ray diffraction spectra minutes after the addition of ferrihydrite to the cultures of a methanogenic archaeon, Methanosarcina barkeri (M. barkeri). M. barkeri cells and redox-active, nonenzymatic soluble organic compounds in organic-rich spent culture supernatants can promote the formation of ZVI; the latter compounds also likely stabilize ZVI. Methanogenic microbes that inhabit organic- and Fe(III)-rich anaerobic environments may similarly reduce Fe(III) to Fe(II) and ZVI, with implications for the preservation of paleomagnetic signals during sediment diagenesis and potential applications in the protection of iron metals against corrosion and in the green synthesis of ZVI.

Light-driven anaerobic microbial oxidation of manganese.

Oxygenic photosynthesis supplies organic carbon to the modern biosphere, but it is uncertain when this metabolism originated. It has previously been proposed1,2 that photosynthetic reaction centres capable of splitting water arose by about 3 billion years ago on the basis of the inferred presence of manganese oxides in Archaean sedimentary rocks. However, this assumes that manganese oxides can be produced only in the presence of molecular oxygen3, reactive oxygen species4,5 or by high-potential photosynthetic reaction centres6,7. Here we show that communities of anoxygenic photosynthetic microorganisms biomineralize manganese oxides in the absence of molecular oxygen and high-potential photosynthetic reaction centres. Microbial oxidation of Mn(II) under strictly anaerobic conditions during the Archaean eon would have produced geochemical signals identical to those used to date the evolution of oxygenic photosynthesis before the Great Oxidation Event1,2. This light-dependent process may also produce manganese oxides in the photic zones of modern anoxic water bodies and sediments.

System-Wide Adaptations of Desulfovibrio alaskensis G20 to Phosphate-Limited Conditions.

The prevalence of lipids devoid of phosphorus suggests that the availability of phosphorus limits microbial growth and activity in many anoxic, stratified environments. To better understand the response of anaerobic bacteria to phosphate limitation and starvation, this study combines microscopic and lipid analyses with the measurements of fitness of pooled barcoded transposon mutants of the model sulfate reducing bacterium Desulfovibrio alaskensis G20. Phosphate-limited G20 has lower growth rates and replaces more than 90% of its membrane phospholipids by a mixture of monoglycosyl diacylglycerol (MGDG), glycuronic acid diacylglycerol (GADG) and ornithine lipids, lacks polyphosphate granules, and synthesizes other cellular inclusions. Analyses of pooled and individual mutants reveal the importance of the high-affinity phosphate transport system (the Pst system), PhoR, and glycolipid and ornithine lipid synthases during phosphate limitation. The phosphate-dependent synthesis of MGDG in G20 and the widespread occurrence of the MGDG/GADG synthase among sulfate reducing ∂-Proteobacteria implicate these microbes in the production of abundant MGDG in anaerobic environments where the concentrations of phosphate are lower than 10 µM. Numerous predicted changes in the composition of the cell envelope and systems involved in transport, maintenance of cytoplasmic redox potential, central metabolism and regulatory pathways also suggest an impact of phosphate limitation on the susceptibility of sulfate reducing bacteria to other anthropogenic or environmental stresses.

Mercury methylation and demethylation in highly contaminated sediments from the Deûle River in Northern France using species-specific enriched stable isotopes.

The methylation-demethylation processes in sediments of the Deûle River were determined using well-established isotope experiments. For this purpose, species-specific isotopically enriched tracers in the form of inorganic mercury IHg ((199)Hg) and methylmercury MeHg (Me(201)Hg) were used to determine Hg dynamics in the Deûle River. Sediment cores were collected at two sampling locations chosen in the most polluted zone of the Deûle River (Northern France) in proximity of a Zn, Pb, Cu, and Ni smelter called "Metaleurop" that had closed in 2003. Site I was chosen in the vicinity of the historic smelter site and site II upstream of the Deûle River. The incubation was realized directly in the sediment cores during the 24 hour experiment under environmental conditions close to the real natural systems (the same temperature, pH, humidity, light/dark conditions, oxygen levels…). The enriched isotopes were injected by needle into different sections of the core. After incubation, the core was sliced and the concentration of Hg species was determined in each section. The highest methylation potentials were found at sediment depths away from the sediment-water-interface. At site I, the methylation potential varied between 0.02-0.9% and at site II between 0.001-0.2%. The demethylation potentials fluctuated between 0.001-60% at site I and between 4-53% at site II. In both sites, negative net methylation potentials were obtained in several sediment depths, representing a net sink for MeHg. The average net methylation potential in site I demonstrated a negative value of 1919 ng g(-1) day(-1). It seems that in site I the demethylation process predominates methylation. Whereas, in site II, the average net methylation potential was a positive value of 138 ng g(-1) day(-1), demonstrating the dominance of methylation over demethylation.

Biogeochemical factors affecting the distribution, speciation, and transport of Hg species in the Deûle and Lys Rivers (Northern France).

The Deûle River is a highly polluted River by heavy metals caused by the historical discharges of ore minerals from the former ore smelter "Metaleurop." The potential mercury (Hg) pollution in the Deûle River implicates the importance of Hg distribution study in the river. As well as to configure the different biogeochemical factors that control the distribution and the potential transport of Hg to distant places. Four different sites were studied as follows: D-A (Deûle River, a site located upstream the river), D-B (Deûle River, a site located near a Zn, Pb, Cu, and Ni smelter that closed in 2003), L-C (Lys River, a site located upstream the confluence of the Deûle River with Lys River), and L-D (downstream the rivers confluence). Different Hg analyses were performed including total mercury in sediment (HgTS), methylmercury (MeHg) in sediment, total mercury in pore water (HgTPW), total mercury in surface water (HgTD), and total suspended particulate Hg in water (HgTP). HgTS decreases downstream from the Deûle River sites with a mean value of 11 ± 0.34 mg/kg to Lys River site (L-D) with a mean value of 0.53 ± 0.02 mg/kg at the confluence. The unaffected side of the Lys River, localized before the confluence (L-C), is characterized by low HgTS of an average value of 0.042 ± 0.003 mg/kg and high % MeHg reaching 4.2 %. Whereas, the highly contaminated Deûle sites are designated by low % MeHg with an average value of 0.053 %. Low pristine environments like that found in L-C site with more favorable biogeochemical conditions of lower concentrations of HgTS, sulfides, and Corg host more active biotic methylation than that of the highly polluted Deûle sites with high concentrations of HgTS and sulfides concentrations. Methylation in D-B (the closet site to Metaleurop smelter) is an old and recent methylation activity that has contributed to MeHg accumulation in the sediments as opposed to the exclusive recent events of methylation in Lys sites. MeHg in all sites is produced in situ rather than exported from other potential sources confirmed by significant relations of % MeHg with %Corg and AVS. Hg pollution is transported from the Deûle River to the Lys River (L-C and L-D) through suspended particles leached or remobilized from the River catchment. The dominance of reducing conditions in the Deûle River attributed to higher sulfide concentration has contributed to higher HgTPW than the Lys sites. Diffusive fluxes of HgT from sediment to water column for the Deûle and Lys River sites (L-C and L-D) were estimated to be 224, 53, and 2 ng/cm(2) year, respectively.

Profile of trace metals accumulation in core sediment from Seine river estuary (docks basin).

The Seine is one of the most polluted rivers in Europe with respect to potentially harmful elements. It receives effluents from the upstream Paris urban and industrial area, and also local inputs from the heavily industrialized Rouen and Le Havre regions. The present study deals with this environmental topic and the concentrations of Cd, Ni, Pb, Hg, Zn and Cu were determined in sediment cores collected in the docks basin of Rouen harbour in 2008. The intensity of metal pollution during recent decades was evaluated using an enrichment factor (EF) and a geoaccumulation index (Igeo). The results of vertical distribution showed that the metal pollution in the past is much higher than in the surface sediment. Mercury was found to be the heaviest pollutant (with Igeo and EF exceeding 4 and 20, respectively), and Cd and Pb were the second most important pollutants. A slight contamination in Ni was observed with very low Igeo values. To estimate the sediment toxicity, simultaneously extracted metals/acid volatile sulfides ratio (SEM/AVS) was calculated. Low values of the toxicity index SEM/AVS were observed in the core sediments indicating the inexistence of metal potential toxicity. Also the concentrations of these trace metals were lower than the probable effect concentration values reported as consensus-based sediment quality guidelines for fresh water ecosystems.

Preconcentration of total mercury from river water by anion exchange mechanism.

A simple and cheap analytical technique was developed for the measurement of total mercury in river water samples using inductively coupled plasma-mass spectrometry (ICP-MS). It is based on the direct complexation of mercury ions using iodide and a cationic surfactant in water for its subsequent solid-phase extraction. Mercury ions are retained on the silica phase as ion pairs in the presence of iodide ions and dodecyltrimethylammonium bromide. Parameters having influential influence on the retention of Hg(II) were investigated: sample flowrate, eluent type, sample volume, iodide and surfactant concentrations. The retained mercury ions are stripped off from silica phase using 10 mL of 8 mol L(-1) HNO3 and quantified by ICP-MS. An enrichment factor of 50 was achieved with a maximum adsorption capacity of 718 µg Hg(II) g(-1). The limit of detection of Hg(II) was 8 pg mL(-1). The developed method was applied for the determination of total mercury in river and tap-water samples.

Solid phase extraction of inorganic mercury using 5-phenylazo-8-hydroxyquinoline and determination by cold vapor atomic fluorescence spectroscopy in natural water samples.

8-Hydroxyquinoline (8-HQ) was chosen as a powerful ligand for Hg solid phase extraction. Among several chelating resins based on 8-HQ, 5-phenylazo-8-hydroxyquinoline (5Ph8HQ) is used for mercury extraction in which the adsorption dynamics were fully studied. It has been shown that Hg(II) is totally absorbed by 5Ph8HQ within the first 30 minutes of contact time with t 1/2 5 minutes, following Langmuir adsorption model. At pH 4, the affinity of mercury is unchallenged by other metals except, for Cu(II), which have shown higher Kd value. With these latter characteristics, 5Ph8HQ was examined for the preconcentration of trace levels of Hg(II). The developed method showed quantitative recoveries of Hg(II) with LOD = 0.21 pg mL(-1) and RSD = 3-6% using cold vapor atomic fluorescence spectroscopy (CV-AFS) with a preconcentration factor greater than 250.