Types and Micromorphology of Authigenic Carbonates in the Kolyma Yedoma Ice Complex, Northeast Siberia

The study focuses on authigenic carbonates that are widespread in different deposition environments and are a component part of the terrestrial biogeochemical cycle of carbon. Samples from the Kolyma Yedoma Ice Complex that formed during the Sartan Cryochrone (MIS 2), the coldest period of the Late Pleistocene, in the northeastern Siberian lowlands, have been studied utilizing scanning electron microscopy and energy-dispersive spectroscopy with replica technique. The samples bear signatures of irreversible multistage cryogenic changes in structure and composition, with the formation of authigenic minerals. Authigenic carbonates as secondary phases in the Ice Complex deposits are remarkable by local changes in chemical, physical, and other properties, which induce gradual changes in the lattice and conversion of one mineral species to another. As a result, the sediments may contain stable and metastable minerals. Crystalline species like calcite or aragonite precipitate from aqueous solutions and their presence are restricted to free pore space in segregation ice. Metastable phases may be produced as an initial reaction product between the CO2 and the aqueous phase, while mineral surfaces and small pores act as possible nucleation sites. Organic matter is also an important agent in the cryometamorphism of sediments, including precipitation of authigenic phases due to the freezing of colloids and high-molecular compounds.

Deoxygenation dynamics on the western Nile deep-sea fan during sapropel S1 from seasonal to millennial timescales

Ocean deoxygenation is a rising threat to marine ecosystems and food resources under present climate warming conditions. Organic-rich sapropel layers deposited in the Mediterranean Sea provide a natural laboratory to study the processes that have controlled changes in seawater oxygen levels in the recent geological past. Our study is based on three sediment cores spanning the last 10 000 years and located on a bathymetric transect offshore from the western distributaries of the Nile delta. These cores are partly to continuously laminated in the sections recording sapropel S1, which is indicative of bottom-water anoxia above the western Nile deep-sea fan. We used a combination of microfacies analyses and inorganic and organic geochemical measurements to reconstruct changes in oxygenation conditions at seasonal to millennial timescales. Millimetre-thick laminations are composed of detrital, biogenic and chemogenic sublayers reflecting seasonal successions of sedimentation. Dark layers reflect the deposition of summer floods and two types of light layers correspond to autumn plankton blooms and authigenic carbonates formed in the water column during spring–early summer, respectively. The isotopic signature of the authigenic carbonates suggests permanent anoxic to euxinic bottom waters resulting in high levels of anaerobic remineralization of organic matter and highlights their potential to reconstruct seawater chemistry at times when benthic fauna was absent. Ratios of major elements combined with biomarkers of terrestrial and marine organic matter and redox-sensitive compounds allow changes in terrigenous input, primary productivity and past deoxygenation dynamics on millennial timescales to be tracked. Rapid fluctuations of oxygenation conditions in the upper 700 m water depth occurred above the Nile deep-sea fan between 10 and 6.5 ka BP, while deeper cores recorded more stable anoxic conditions. Synchronous changes in terrigenous input, primary productivity and past oxygenation dynamics after 6.5 ka BP show that runoff-driven eutrophication played a central role in rapid oxygenation changes in the south-eastern Levantine Basin. These findings are further supported by other regional records and reveal time-transgressive changes in oxygenation state driven by rapid changes in primary productivity during a period of long-term deep-water stagnation.

Laboratory Experimental Study on the Formation of Authigenic Carbonates Induced by Microbes in Marine Sediments

Authigenic carbonates are widely distributed in marine sediments, microbes, and anaerobic oxidation of methane (AOM) play a key role in their formation. The authigenic carbonates in marine sediments have been affected by weathering and diagenesis for a long time, it is difficult to understand their formation process by analyzing the samples collected in situ. A pore water environment with 10 °C, 6 MPa in the marine sediments was built in a bioreactor to study the stages and characteristics of authigenic carbonates formation induced by microbes. In experiments, FeCO3 is formed preferentially, and then FeCO3-MgCO3 complete isomorphous series and a small part of CaCO3 isomorphous mixture are formed. According to this, it is proposed that the formation of authigenic carbonates performed by AOM and related microbes needs to undergo three stages: the rise of alkalinity, the preferential formation of a carbonate mineral, and the formation of carbonate isomorphous series. This work provides experimental experience and reference basis for further understanding the formation mechanism of authigenic carbonates in marine sediments.

Anaerobic oxidation of methane by Mn oxides in sulfate-poor environments

Strongly 13C-depleted authigenic carbonates (e.g., δ13CVPDB <−30‰; VPDB—Vienna Peedee belemnite) in nature are generally believed to form by sulfate-dependent anaerobic oxidation of methane (AOM). However, we demonstrate using geochemical data and thermodynamic calculation that such calcites are most likely derived from biogenic oxidation of methane in sulfate-poor, nonmarine environments during early diagenesis, as observed in the Triassic sandy conglomerates from the Junggar Basin, northwestern China. This process operated through preferential oxidation of 13C-depleted methane by Mn oxides in closed conditions, producing calcites with higher Mn contents and δ13C values in association with more 13C-enriched residual methane as a result of kinetic isotope fractionation. Thus, the Mn-rich and 13C-depleted carbonates are proposed as tracers of Mn-dependent AOM, which should have served as an important sink of greenhouse methane in low-sulfate early Earth’s oceans.

Temperatures of Late Cretaceous (Campanian) methane-derived authigenic carbonates from the Western Interior Seaway, South Dakota, USA, using clumped isotopes

Methane seep deposits, comprising large, carbonate-rich mounds formed from hydrocarbon seepage, were widely distributed in the Late Cretaceous Western Interior Seaway (WIS) of North America. Well-preserved, methane-derived authigenic carbonates (MDACs) from these deposits have been shown to retain petrological, paleontological, and geochemical imprints of their ancient depositional setting, all of which are important for understanding the dynamics and evolution of the shallow, epeiric WIS. To better characterize the environmental conditions of WIS seeps, we applied clumped isotope paleothermometry to magnesium calcite MDAC samples from five seep localities in the upper Campanian Pierre Shale, South Dakota, USA. We measured 21 subsamples, including 18 micritic carbonates and demonstrated apparent clumped isotope equilibrium between MDACs and WIS bottom waters. Extreme 13C depletion in most samples (δ13C ranging to −45.44‰) indicates they were precipitated with oxidized methane as a major source of dissolved inorganic carbon, which itself implies a close association with ancient methanotrophic metabolism. The average clumped isotope paleotemperature from the micritic carbonates is 23 ± 7 °C (1σ standard deviation), which agrees with bottom water paleotemperatures inferred from δ18O measurements of MDACs and well-preserved mollusk shells at similar localities in the WIS. The calculated average δ18Ow value for these samples is −0.5 ± 1.7‰ (1σ SD), which is indistinguishable from previously reported calculation on Campanian seawater δ18Ow from fossil mollusk shells, but elevated above younger fossils collected from other locations in the WIS. Our conclusions are inconsistent with previously hypothesized disequilibrium for WIS MDAC clumped isotope and therefore we propose that fossil MDAC deposits may be used as paleotemperature archives.