Evaluation of uptake mechanisms of phosphate by Fe(III)(oxyhydr)oxides in Early Proterozoic oceanic conditions

Banded iron formations (BIF) are proxies of global dissolved inorganic phosphate (DIP) content in Precambrian marine waters. Estimates of Precambrian DIP rely on constraining the mechanisms by which Fe(III)(oxyhydr)oxides scavenge DIP in NaCl solutions mimicking elevated Precambrian marine Si and Fe(II) concentrations. The two DIP binding modes suggested for Early Proterozoic marine waters are 1) surface attachment on pre-formed Fe(III)(oxyhydr)oxides (adsorption), and 2) incorporation of P into actively growing Fe(III)(oxyhydr)oxides (coprecipitation) during the oxidation of Fe(II) to Fe(III)(oxyhydr)oxides in the presence of DIP. It has been suggested that elevated Si concentrations such as those suggested for Precambrian seawater, strongly inhibit adsorption of DIP in Fe(III)(oxyhydr)oxides, however recent coprecipitation experiments show that DIP is scavenged by Fe(III)(oxyhydr)oxides in the presence of Si, seawater cations and hydrothermal As. In this study we show that the DIP uptake onto Fe(III)(oxyhydr)oxides by adsorption is less than 5% of that by coprecipitation. Differences in surface attachment and the possibility of structural capture within the Fe(III)(oxyhydr)oxides are inferred from the robust influence Si has on DIP binding during adsorption, but inhibited for coprecipitation when As(III) and As(V) are present. The data imply that in the Early Proterozoic open oceans, Fe(III)(oxyhydr)oxides precipitated when deep anoxic Fe(II)-rich waters rose and mixed with the first permanently oxygenated ocean surface waters, caused DIP removal from surface waters through coprecipitation rather than adsorption. Local variations in DIP and perhaps even stratification of DIP in the oceans were likely created from the continuous removal of DIP from surface waters by Fe(III)(oxyhydr)oxides, and its partial release into the anoxic bottom waters and in buried sediments. In addition to a DIP famine, the selectivity for DIP over As(V) may have led to As enrichment in surface waters both of which would have most likely decreased the productivity of cyanobacteria and O2 production

Methane fluxes from coastal sediments are enhanced by macrofauna

Methane and nitrous oxide are potent greenhouse gases (GHGs) that contribute to climate change. Coastal sediments are important GHG producers, but the contribution of macrofauna (benthic invertebrates larger than 1 mm) inhabiting them is currently unknown. Through a combination of trace gas, isotope, and molecular analyses, we studied the direct and indirect contribution of two macrofaunal groups, polychaetes and bivalves, to methane and nitrous oxide fluxes from coastal sediments. Our results indicate that macrofauna increases benthic methane efflux by a factor of up to eight, potentially accounting for an estimated 9.5% of total emissions from the Baltic Sea. Polychaetes indirectly enhance methane efflux through bioturbation, while bivalves have a direct effect on methane release. Bivalves host archaeal methanogenic symbionts carrying out preferentially hydrogenotrophic methanogenesis, as suggested by analysis of methane isotopes. Low temperatures (8 °C) also stimulate production of nitrous oxide, which is consumed by benthic denitrifying bacteria before it reaches the water column. We show that macrofauna contributes to GHG production and that the extent is dependent on lineage. Thus, macrofauna may play an important, but overlooked role in regulating GHG production and exchange in coastal sediment ecosystems

Precipitation of Mn Oxides in Quaternary microbially induced sedimentary structures (MISS), Cape Vani Paleo-Hydrothermal Vent Field, Milos, Greece

Understanding microbial mediation in sediment-hosted Mn deposition has gained importance in low-temperature ore genesis research. Here we report Mn oxide ores dominated by todorokite, vernadite, hollandite, and manjiroite, which cement Quaternary microbially induced sedimentary structures (MISS) developed along bedding planes of shallow-marine to tidal-flat volcaniclastic sandstones/sandy tuffs, Cape Vani paleo-hydrothermal vent field, Milos, Greece. This work aims to decipher the link between biological Mn oxide formation, low-T hydrothermalism, and, growth and preservation of Mn-bearing MISS (MnMISS). Geobiological processes, identified by microtexture petrography, scanning and transmission electron microscopy, lipid biomarkers, bulk- and lipid-specific δ13Corganic composition, and field data, and, low-temperature hydrothermal venting of aqueous Mn2+ in sunlit shallow waters, cooperatively enabled microbially-mediated Mn (II) oxidation and biomineralization. The MnMISS biomarker content and δ13Corg signatures strongly resemble those of modern Mn-rich hydrothermal sediments, Milos coast. Biogenic and syngenetic Mn oxide precipitation established by electron paramagnetic resonance (EPR) spectroscopy and petrography, combined with hydrothermal fluid flow-induced pre-burial curing/diagenesis, may account for today’s crystalline Mn oxide resource. Our data suggests that MISS are not unique to cyanobacteria mats. Furthermore, microbial mats inhabited by aerobic methanotrophs may have contributed significantly to the formation of the MnMISS, thus widening the spectrum of environments responsible for marine Mn biometallogenesi

Mechanism of formation, mineralogy and geochemistry of the ooidal ironstone of Djebel Had, northeast Algeria

The Djebel Had Ironstone (DHIS), an 8 m thick stratiform sedimentary iron formation, forms part of the important mining district of south Tebessa, in northeastern Algeria. Stratigraphic, lithological, structural and metallogenic similarities, suggest the DHIS may extend further into southwestern Tunisia. We show that mineralization occurs as layers of ooidal ironstones and inter-laminated iron marl within mid-Eocene gypsiferous marls. The more or less rounded 0.1–2.0 mm brownish-blackish ooids, are composed of goethite, limonite, hematite, with traces of magnetite and piemontite. The grains display a smooth outer surface bound by an argilo-ferruginous layer embedded in siliceous-calcite cement. They are unusually friable, crumbling at the slightest shock. A high total iron (FeT) content of 50.12%, is dominated by up to 71.06% iron hydroxide (FeO(OH). Much of the iron is present as goethite, a common feature of iron-rich ooids of North African origin. However, the lack of prominent chlorite minerals suggest the DHIS is not of a detrital origin. Instead, a negligible Ti and Al oxide concentration suggest a chemical provenance for the DHIS. The data suggest that ferruginous conditions developed in a potentially restricted/semi-restricted continental shelf margin where seafloor redox was sensitive to the alternating cycles of sea level change. We propose a new mechanism for the formation of ooidal ironstones, associated with shelf surface water eutrophication, bottom water anoxia promoted by sea level rise and the weathering of iron phosphate-rich rocks. Phosphorus and cerium enrichment, coupled to reconstructed redox depositional conditions and sediment mineralogy, suggest that intense biomass production stimulated the deoxygenation of shelf bottom waters and the deposition of the DHIS beneath a ferruginous water column

Exceptional preservation of fungi as H2-bearing fluid inclusions in an Early Quaternary paleo-hydrothermal system at Cape Vani, Milos, Greece

The production of H2 in hydrothermal systems and subsurface settings is almost exclusively assumed a result of abiotic processes, particularly serpentinization of ultramafic rocks. The origin of H2 in environments not hosted in ultramafic rocks is, as a rule, unjustifiably linked to abiotic processes. Additionally, multiple microbiological processes among both prokaryotes and eukaryotes are known to involve H2-production, of which anaerobic fungi have been put forward as a potential source of H2 in subsurface environments, which is still unconfirmed. Here, we report fungal remains exceptionally preserved as fluid inclusions in hydrothermal quartz from feeder quartz-barite veins from the Cape Vani Fe-Ba-Mn ore on the Greek island of Milos. The inclusions possess filamentous or near-spheroidal morphologies interpreted as remains of fungal hyphae and spores, respectively. They were characterized by microthermometry, Raman spectroscopy, and staining of exposed inclusions with WGA-FITC under fluorescence microscopy. The spheroidal aqueous inclusions interpreted as fungal spores are unique by their coating of Mn-oxide birnessite, and gas phase H2. A biological origin of the H2 resulting from anaerobic fungal respiration is suggested. We propose that biologically produced H2 by micro-eukaryotes is an unrecognized source of H2 in hydrothermal systems that may support communities of H2-dependent prokaryote

Arsenic and high affinity phosphate uptake gene distribution in shallow submarine hydrothermal sediments

The toxicity of arsenic (As) towards life on Earth is apparent in the dense distribution of genes associated with As detoxification across the tree of life. The ability to defend against As is particularly vital for survival in As-rich shallow submarine hydrothermal ecosystems along the Hellenic Volcanic Arc (HVA), where life is exposed to hydrothermal fluids containing up to 3000 times more As than present in seawater. We propose that the removal of dissolved As and phosphorus (P) by sulfide and Fe(III)(oxyhydr)oxide minerals during sediment-seawater interaction, produces nutrient-deficient porewaters containing < 2.0 ppb P. The porewater arsenite-As(III) to arsenate-As(V) ratios, combined with sulfide concentration in the sediment and/or porewater, suggest a hydrothermally-induced seafloor redox gradient. This gradient overlaps with changing high affinity phosphate uptake gene abundance. High affinity phosphate uptake and As cycling genes are depleted in the sulfide-rich settings, relative to the more oxidizing habitats where mainly Fe(III)(oxyhydr)oxides are precipitated. In addition, a habitat-wide low As-respiring and As-oxidizing gene content relative to As resistance gene richness, suggests that As detoxification is prioritized over metabolic As cycling in the sediments. Collectively, the data point to redox control on Fe and S mineralization as a decisive factor in the regulation of high affinity phosphate uptake and As cycling gene content in shallow submarine hydrothermal ecosystems along the HVA

Antimicrobial Activity of Metals and Metalloids

Competition shapes evolution. Toxic metals and metalloids have exerted selective pressure on life since the rise of the first organisms on the Earth, which has led to the evolution and acquisition of resistance mechanisms against them, as well as mechanisms to weaponize them. Microorganisms exploit antimicrobial metals and metalloids to gain competitive advantage over other members of microbial communities. This exerts a strong selective pressure that drives evolution of resistance. This review describes, with a focus on arsenic and copper, how microorganisms exploit metals and metalloids for predation and how metal- and metalloid-dependent predation may have been a driving force for evolution of microbial resistance against metals and metalloids.BFU2016-75425-P (70% FEDER), PID2020-112634GB-I0