Description: During Earth’s history, precipitation of calcium carbonate by heterotrophic microbes has substantially contributed to the genesis of copious amounts of carbonate sediment and its subsequent lithification. Previous work identified the microbial sulfur and nitrogen cycle as principal pathways involved in the formation of marine calcium carbonate deposits. While substantial knowledge exists for the importance of the sulfur cycle, specifically sulfate reduction, with regard to carbonate formation, information about carbonate genesis connected to the microbial nitrogen cycle is dissatisfactory. In addition to the established pathways for carbonate mineral formation, also the potential of microbial carbonic anhydrase, a carbonate-relevant, zinc-containing enzyme, is receiving currently increased attention. However, also in this field knowledge is scarce and fragmentary. Here we demonstrate microbial carbonate precipitation as a direct result of the interplay between the microbial nitrogen cycle and a microbially produced enzyme. Using Alcanivorax borkumensis as a model organism, our experiments depict precipitation of a peloidal carbonate matrix within days to weeks, induced by simultaneous ammonification and extracellular carbonic anhydrase activity. The precipitates show similar morphology, mineralogy, δ44/40Ca, and δ88/86Sr to analogs of modern carbonate peloids. The obtained Sr/Ca partition coefficient DSr showed no clear deviation from inorganic carbonate phases, indicating that microbially mediated carbonate precipitation, indeed, follows the principles of physico-chemical precipitation. The observed relative enrichment of the precipitates in zinc might help to constrain zinc variations in natural carbonate archives. Our study demonstrates that ammonification, due to intense microbial organic matter degradation, and carbonic anhydrase may play a substantial role for calcium carbonate precipitation in paleo- and recent shallow marine environments.

Description: Highlights • In cold seeps of Guaymas Basin, aragonite, barite and pyrite precipitated from modified seawater. • Aragonite is highly depleted in 13C suggesting formation via anaerobic oxidation of methane. • Barite formed through mixing of reducing, Ba-rich seep fluids with a 34S-rich sulfate pool. • Pyrite framboids formed under anoxic-sulfidic water via microbial sulfate reduction. Abstract Authigenic carbonate crusts, surface muds and bivalve shell fragments have been recovered from inactive and active recently discovered cold seep sites in central Guaymas Basin. In this study, for first time, redox conditions and fluid sources involved in mineral precipitation were investigated by analyzing the mineralogy and textures of surface samples, along with skeletal contents, and C, O and S isotopes variations. The δ13C values of aragonitic bivalve shells and non-skeletal carbonate from some surface muds (1‰ to −3.7‰ V-PDB) suggest that carbonate precipitated from ambient dissolved inorganic carbon, whereas fibrous aragonite cement and non-skeletal carbonate from other sites are highly depleted in 13C (down to −47.6‰ V-PDB), suggesting formation via anaerobic oxidation of methane, characteristic of methane seepage environments. δ18O in most of the carbonates varies from +1.4‰ to +3.2‰ V-PDB, indicating that they formed from slightly modified seawater. Some non-skeletal carbonate grains from surface muds have lower δ18O values (−12.5‰ to −8.2‰ V-PDB) reflecting the influence of 18O-depleted pore water. Size distribution of pyrite framboids (mean value: 3.1 μm) scattered within diatomaceous sinter suggests formation from anoxic-sulfidic bottom waters. δ34S in pyrite is of −0.3‰ V-CDT compared to +46.6‰ V-CDT in barite, thus implying a fluid sulfate−sulfide fractionation of 21.3‰ that argues in favor of microbial sulfate reduction as the processes that mediated pyrite framboid formation, in a semi-closed system. Barite formation occurred through the mixing of reducing and Ba-rich seep fluids with a 34S-enriched sulfate pool that resulted from microbial sulfate reduction in a semi-closed system. The chemical composition of aragonite cement, barite and pyrite suggest mineral precipitation from modified seawater. Taken together, our data suggest that mineralization at the studied seep sites is controlled by the mixing of seawater with minor amounts of hydrothermal fluids, and oxygen-depleted conditions favoring anaerobic microbial processes.

Description: The formation of mud volcanoes in the Gulf of Cadiz is closely linked to diapirism in the deep subsurface. The Mercator mud volcano (MMV) is a rare example where diapiric emplacement, in addition to being key for upward fluid migration, is also an important zone for fluid and mineral diagenesis. The most intriguing findings in the near-surface muds of the MMV are extremely high salinities of up to 5.2 M of NaCl from diapiric and evaporitic halite dissolution and the occurrence of authigenic gypsum and anhydrite crystals, both of which have not been observed to date in the Gulf of Cadiz. Employing a thermodynamic model we elucidate how the interplay of temperature pulses, strong salinity gradients, and fluid flow dynamically drive mineral dissolution and re-formation. The strong increase in salinity in the pore fluids has important implications for thermodynamic equilibria by significantly lowering the activity of water, thereby raising the gypsum–anhydrite transition zone from 〉1 km to about 400 m sediment depth at the MMV. This transition is further shifted to immediately below the seafloor during intervals of active mud and fluid expulsion when the MV surface temperature is heated up to at least 30 °C. As a consequence, precipitation of authigenic gypsum near the sediment surface (1–2 mbsf) has been linked to the dissolution of evaporites below the MMV. More precisely, the mechanisms generating supersaturation in the ascending gypsum-saturated MMV fluids are (1) the slow and constant cooling of these fluids along the geothermal gradient during their ascent leading to formation of ubiquitous micro-crystals and (2) the more rapid cooling after a heat pulse or transport from greater and warmer depth during an active mud volcano phase leading to the precipitation of cm-scale gypsum crystals or even fist-size concretions. The MMV fluids approaching the salt diapir from farther below have experienced a genesis similar to those of other mud volcanoes in the Gulf of Cadiz located above deep-rooted faults. These processes include clay mineral dewatering, thermogenic degradation of organic matter and deep high-temperature leaching of terrigenous sediments or continental crust.

Description: Highlights • High abundance of active anaerobic methanotrophs in sediments of the blowout crater suggests adaptation to methane seepage within at most two decades. • Fast exchange processes in permeable surface sediments prevent sulfate depletion and probably methane-derived carbonate precipitation. • Methane seepage impacts isotopic and assemblage composition of benthic foraminifera. Abstract Methane emissions from marine sediments are partly controlled by microbial anaerobic oxidation of methane (AOM). AOM provides a long-term sink for carbon through precipitation of methane-derived authigenic carbonates (MDAC). Estimates on the adaptation time of this benthic methane filter as well as on the establishment of related processes and communities after an onset of methane seepage are rare. In the North Sea, considerable amounts of methane have been released since 20 years from a man-made gas blowout offering an ideal natural laboratory to study the effects of methane seepage on initially “pristine” sediment. Sediment cores were taken from the blowout crater and a reference site (50 m distance) in 2011 and 2012, respectively, to investigate porewater chemistry, the AOM community and activity, the presence of authigenic carbonates, and benthic foraminiferal assemblages. Potential AOM activity (up to 3060 nmol cm−3 sediment d−1 or 375 mmol m−2 d−1) was detected only in the blowout crater up to the maximum sampling depth of 18 cm. CARD-FISH analyzes suggest that monospecific ANME-2 aggregates were the only type of AOM organisms present, showing densities (up to 2.2*107 aggregates cm−3) similar to established methane seeps. No evidence for recent MDAC formation was found using stable isotope analyzes (δ13C and δ18O). In contrast, the carbon isotopic signature of methane was recorded by the epibenthic foraminifer Cibicides lobatulus (δ13C −0.66‰). Surprisingly, the foraminiferal assemblage in the blowout crater was dominated by Cibicides and other species commonly found in the Norwegian Channel and fjords, indicating that these organisms have responded sensitively to the specific environmental conditions at the blowout. The high activity and abundance of AOM organisms only at the blowout site suggests adaptation to a strong increase in methane flux in the order of at most two decades. High gas discharge dynamics in permeable surface sediments facilitate fast sulfate replenishing and stimulation of AOM. The accompanied prevention of total alkalinity build-up in the porewater thereby appears to inhibit the formation of substantial methane-derived authigenic carbonate at least within the given time window.

Description: Highlights: • The Giant Gjallar Vent is still active in terms of fluid migration and faulting. • The Base Pleistocene Unconformity acts as a seal to upward fluid migration. • Seal bypass in at least one location leads to a new phase of fluid venting. The Giant Gjallar Vent (GGV), located in the Vøring Basin off mid-Norway, is one of the largest (~ 5 × 3 km) vent systems in the North Atlantic. The vent represents a reactivated former hydrothermal system that formed at about 56 Ma. It is fed by two pipes of 440 m and 480 m diameter that extend from the Lower Eocene section up to the Base Pleistocene Unconformity (BPU). Previous studies based on 3D seismic data differ in their interpretations of the present activity of the GGV, describing the system as buried and as reactivated in the Upper Pliocene. We present a new interpretation of the GGV’s reactivation, using high-resolution 2D seismic and Parasound data. Despite the absence of geochemical and hydroacoustic indications for fluid escape into the water column, the GGV appears to be active because of various seismic anomalies which we interpret to indicate the presence of free gas in the subsurface. The anomalies are confined to the Kai Formation beneath the BPU and the overlying Naust Formation, which are interpreted to act as a seal to upward fluid migration. The seal is breached by focused fluid migration at one location where an up to 100 m wide chimney-like anomaly extends from the BPU up to the seafloor. We propose that further overpressure build-up in response to sediment loading and continued gas ascent beneath the BPU will eventually lead to large-scale seal bypass, starting a new phase of venting at the GGV.

Description: Carbonate chimney-like deposits up to 60 m high are scattered or arranged in rows at the shores of a desiccating hypersaline and alkaline lake from a continental rift setting (Lake Abhé, Afar Rift, Djibouti). The chimneys formed sub-aqueously in the lake water body at a higher water level than observed today. Alternating calcite and low-Mg calcite + silica concentric layers compose the chimney structures. Mineralogical and geochemical investigations of the chimneys, lake water, and hot spring (hydrothermal) fluids suggest that the chimneys are a result of rapid carbonate precipitation during the mixing of hydrothermal fluids with lake water. In contrast to the hot spring fluid, lake water is enriched in HREE and possesses a pronounced positive Ce anomaly, features that are preserved in the carbonate chimney layers. Mixing calculations based on Sr-isotope and concentration data indicate a hydrothermal fluid contribution of ~ 45% in the chimney interior, which decreases to ~ 4% in the external chimney layer. Sr in the hydrothermal fluids is predominantly leached from the underlying volcanic rocks, whereas the lake's Sr budget is dominated by riverine input. Considering the fluid mixing ratios calculated by Sr-data, the measured C and O isotope compositions indicate that chimney carbonates precipitated at temperatures between 14 °C (internal part) and 22 °C (external part) with δ13C-carbonate mainly controlled by isotope equilibrium exchange of lake water with atmospheric CO2. The low-Mg calcite layers, including the outermost layer, have enhanced signals of lake water inheritance based on elevated concentrations of immobile elements, ΣREE, and Sr and Ca isotope compositions. Ca-isotope data reveal that internal chimney layers formed by non-equilibrium calcite precipitation with a predominantly hydrothermal Ca source. The external low-Mg calcite layer received Ca contributions from both hydrothermal fluid and lake water, with the latter being the dominant Ca source. Highly positive δ44/40Ca of lake water likely reflects non-equilibrium Ca-carbonate precipitation during lake water evaporation with resulting 44Ca enrichment of residual lake water. The strong degree of 44Ca enrichment may point towards multiple lake drying and Ca-reservoir depletion events. Coupled C–O–Ca-isotope data of the sampled carbonate chimney suggest late-stage (low-temperature) hydrothermal carbonate chimney formation during strongly evaporative lake conditions at the time of low-Mg calcite precipitation. U–Th age dating suggests that the chimneys formed no earlier than 0.82 kyr BP (0.28 ± 0.54).

Description: The dating of polymetamorphic rocks with the U-Pb zircon method often results in discordant data. Thus a new technique combining cathodoluminescence imaging (CL) and thermal ion mass spectrometry (TIMS) measurements was developed. Cathodoluntinescence-controlled UPb dating (CLC-method) works with bisected zircons and was successfully applied to the multistage S-type granitoids of the Swiss Silvretta nappe. CLC-method enables the resolution of the different anatectic events and later major overprints (Cambrian, Ordovician, Silurian) and gives information about the protolith (Archaean) of the investigated gneisses. This is achieved by conventional UPb dating of selected grains, recovered from the SEM (scanning electron microscope) mounts after cathodoluminescence (CL) imaging. Applying this new combination of two established techniques yields geologically meaningful UPb zircon ages even for complex polymetamorphic rocks.

Description: Lithium concentration and isotope data (δ7Li) are reported for pore fluids from 18 cold seep locations together with reference fluids from shallow marine environments, a sediment-hosted hydrothermal system and two Mediterranean brine basins. The new reference data and literature data of hydrothermal fluids and pore fluids from the Ocean Drilling Program follow an empirical relationship between Li concentration and δ7Li (δ7Li = −6.0(±0.3) · ln[Li] + 51(±1.2)) reflecting Li release from sediment or rocks and/or uptake of Li during mineral authigenesis. Cold seep fluids display δ7Li values between +7.5‰ and +45.7‰, mostly in agreement with this general relationship. Ubiquitous diagenetic signals of clay dehydration in all cold seep fluids indicate that authigenic smectite–illite is the major sink for light pore water Li in deeply buried continental margin sediments. Deviations from the general relationship are attributed to the varying provenance and composition of sediments or to transport-related fractionation trends. Pore fluids on passive margins receive disproportionally high amounts of Li from intensely weathered and transported terrigenous matter. By contrast, on convergent margins and in other settings with strong volcanogenic input, Li concentrations in pore water are lower because of intense Li uptake by alteration minerals and, most notably, adsorption of Li onto smectite. The latter process is not accompanied by isotope fractionation, as revealed from a separate study on shallow sediments. A numerical transport-reaction model was applied to simulate Li isotope fractionation during upwelling of pore fluids. It is demonstrated that slow pore water advection (order of mm a−1) suffices to convey much of the deep-seated diagenetic Li signal into shallow sediments. If carefully applied, Li isotope systematics may, thus, provide a valuable record of fluid/mineral interaction that has been inherited several hundreds or thousands of meters below the actual seafloor fluid escape structure.

Description: Oceanic oxygen decline due to anthropogenic climate change is a matter of growing concern. Tropical oxygen minimum zones (OMZs) are the most important areas of oxygen depletion in the modern oceans. A quantitative oxygen proxy in OMZs is highly desirable in order to identify and monitor recent dynamics as well as to reconstruct pre-Anthropocene changes in amplitude and extension of oxygen depletion. A previous study revealed that there are significant correlations between I/Ca ratios of foraminiferal bulk samples for different benthic foraminiferal species from the Peruvian OMZ. Nevertheless, species for which less specimens were available showed a higher variability between I/Ca ratios in different badges. To test if this might be related to intra- or inter-shell heterogeneity we focused on microanalyses of I/Ca ratios within these species in our present study. We developed a method for measuring benthic foraminiferal I/Ca ratios, a potential proxy for the reconstruction of marine oxygen concentrations. We applied 92 spot analyses in individual foraminiferal specimens from the Peruvian OMZ using secondary ion mass-spectrometry (SIMS). The I/Ca ratios on 8 of 11 cleaned Uvigerina striata and Planulina limbata specimens determined with SIMS showed no significant difference to previous ICP-MS measurements on bulk samples from the same species. This indicates that both techniques are suited to the analysis and that the applied cleaning protocols efficiently removed the strong iodine contaminations. Nevertheless, despite the highly significant correlation between bulk ICP-MS I/Ca ratios and bottom water oxygen concentrations for U. striata, no significant correlation was observed for the SIMS derived individual I/Ca ratios. This indicates that ICP-MS bulk analyses on pooled bulk samples might be more suitable for reliable oxygen reconstructions using I/Ca ratios. On the contrary, the strong intra-test (e.g. -shell) variations could be induced by the oxygen variability in the habitats of foraminifera. Therefore, the high resolution findings provide the perspective for tracking relative short term oxygen fluctuations by measuring ontogenetic changes in I/Ca ratios within individual foraminiferal tests. Measurements on cross-sections of uncleaned U. striata specimens revealed a strong contaminant iodine phase within the massive centre of the foraminiferal test walls which usually would be considered to be free of contamination. The contaminant iodine is probably associated to organic matter and located inside a microporous framework within the foraminiferal calcite. This might be related to microtubular structures which have been revealed in previous studies during early dissolution states of foraminiferal test walls.

Description: Highlights • Vertical marsh growth in the RdlP is well above present and future SLR rates. • Drivers for vertical marsh growth show high spatial variability within the estuary. • Deposition rates on the RdlP marshes tend to be higher since the early 1970s. • Extreme storm surges positively affect the growth of the outer RdlP marshes. • Temporal variations in river discharge are more important for the inner RdlP marshes. Abstract The vertical growth of coastal wetlands is known to primarily be controlled by local tidal range and sediment availability as well as the occurrence of storm events. In estuaries, sediment availability additionally depends on riverine sediment input, the effect of which may be more pronounced in some parts of the estuary, thereby introducing a distinct spatial pattern that depends on the estuary's shape as well as the riverine sediment input and the hydro-meteorological regime. In the present study, we investigate how estuarine marshes along the whole Río de la Plata (RdlP) are affected by decadal and long-term variations in river discharge and storm activity. The El Niño Southern Oscillation (ENSO), in this context, appears to introduce a pronounced decadal variability on sediment loads brought into the RdlP. Based on 15 sediment cores, recovered along the RdlP and adjacent Atlantic coast, vertical marsh growth rates were studied using radionuclide dating (210Pb and 137Cs) and grain size distributions. By comparing these sedimentological records with historic river discharge and storm surge data, we spatially interpret the relative importance of temporal variations in river discharge and storm activity on estuarine marsh growth. By delivering the first estimates for vertical growth rates of the RdlP marshes, we conclude that with average vertical marsh growth rates between 0.4 and 2.6 cm year− 1, the RdlP marshes are highly resilient against drowning under present and future sea-level rise (SLR) conditions. Furthermore, our results confirm a large spatial variability of the drivers for vertical marsh growth; extreme storm surges appear to play a role in the development of the outer RdlP marshes whereas the temporal variations in river discharge seem to be hierarchically more important for the marshes in the inner estuary.