Provenance and sedimentary environment of the Ek2 shale in the Cangdong Sag, the central Bohai Bay Basin, China

The second member of the Kongdian Formation (usually abbreviated as the E k2 shale) is one of the most significant exploring targets for shale oil at the Cangdong Sag of the central Bohai Bay Basin. It consists of siliceous shale, mixed shale, and calcareous shale. To better understand why organic matter accumulated in the E k2 shale, we have analyzed major and trace elemental compositions to reconstruct the provenance and sedimentary environment. Tectonic discriminatory diagrams suggest that the tectonic setting of the parental rocks for the E k2 shale belonged to the Continental Island Arc. The distribution patterns of trace elements and rare earth elements + yttrium (REEs + Y) are close to the intermediate igneous rock. The ratios of Al2O3/TiO2 ranging from 21.41 to 27.59 with a mean value of 23.93 also demonstrate a parental rock of the intermediate igneous rock. Siliceous and mixed shales indicate K2O/Al2O3 of 0.17–0.29, chemical index of weathering of 28.79–97.79, plagioclase index of alteration of 38.24–95.57, and chemical index of alteration of 40.29–80.23. These weathering proxies denote that the E k2 shale underwent a low weathering degree in an arid climate and a high weathering degree in a semiarid climate. The V/(V + Ni) ratios and pyrite framboids indicate an anoxic sedimentary condition. The δ18O values of carbonate minerals in the E k2 shale range from −9.8‰ to 0.7‰, and they are positively correlated to the δ13C values. The Sr/Ba ratios, δ18O, and chemical mineral associations indicate that siliceous and mixed shales were deposited in a fresh to brackish anoxic water column under a semiarid climate. Whereas calcareous shale was deposited in a saline to hypersaline anoxic water column under an arid climate.

Anoxic depositional overprinting of 238U/235U in calcite: When do carbonates tell black shale tales?

The fidelity of uranium isotopes (δ238U) in marine carbonates as a paleoredox proxy relies on whether carbonates can record and preserve seawater δ238U. Although modern carbonate sediments deposited under oxic conditions have been shown to track seawater δ238U, it remains unknown whether this is true for carbonates deposited under anoxic conditions. This is a crucial question because many ancient carbonates were likely deposited or reworked under anoxic bottom waters. To better understand the behavior of uranium isotopes under this scenario, we investigated U isotope geochemistry in the meromictic Fayetteville Green Lake (FGL; New York, USA), where primary calcite is precipitated from oxic surface waters, sinks past the chemocline, and is deposited under anoxic bottom waters. We observed significant depletions of dissolved U concentration (from 2.7 to 0.9 ppb) and δ238U (from –0.55‰ to –0.96‰) below the chemocline in FGL. Parallel with these depletions, δ238U of sediment traps increased progressively from –0.51‰ to –0.16‰, suggesting that U(VI) reduction was occurring in the anoxic water column. Carbonate sediments deposited under anoxic bottom waters were enriched in U by 6–18× compared to primary calcite. Our data suggest that such significant authigenic U enrichments resulted from U(VI) reduction in the anoxic water column and below the sediment-water interface. The δ238U value in the top 0.25 cm of sediments was –0.29‰ ± 0.10‰, overprinting original δ238U in primary calcite (–0.51‰ ± 0.02‰). Future applications of carbonate δ238U as a paleoredox proxy should consider depositional environments (oxic vs. anoxic) of carbonates.

Methane oxidation in the waters of a humic-rich boreal lake stimulated by photosynthesis, nitrite, Fe(III) and humics

Small boreal lakes are known to contribute significantly to global CH4 emissions. Lake Lovojärvi is a eutrophic lake in southern Finland with bottom water CH4 concentrations up to 2 mM. However, the surface water concentration, and thus the diffusive emission potential, was low (< 0.5 µM). We studied the biogeochemical processes involved in CH4 removal by chemical profiling and through incubation experiments. δ13C-CH4 profiling of the water column revealed a methane-oxidation hotspot just below the oxycline and zones of CH4 oxidation within the anoxic water column. In incubation experiments involving the addition of light and/or oxygen, CH4 oxidation rates in the anoxic hypolimnion were enhanced 3-fold, suggesting a major role for photosynthetically fueled aerobic CH4 oxidation. We observed a distinct peak in CH4 concentration at the chlorophyll-a maximum, caused by either in situ CH4 production or other CH4 inputs such as lateral transport from the littoral zone. In the dark anoxic water column at 7 m depth, nitrite seemed to be the key electron acceptor involved in CH4 oxidation, yet additions of Fe(III), anthraquinone-2,6-disulfonate and humic substances also stimulated anoxic CH4 oxidation. Surprisingly, nitrite seemed to inhibit CH4 oxidation at all other depths. Overall, this study shows that photosynthetically fueled CH4 oxidation can be a key process in CH4 removal in the water column of humic, turbid lakes, thereby limiting diffusive CH4 emissions from boreal lakes. Yet, it also highlights the potential importance of a whole suite of alternative electron acceptors, including humics, in these freshwater environments in the absence of light and oxygen.

Marine snow as a habitat for microbial mercury methylators in the Baltic Sea

Methylmercury (MeHg), a neurotoxic compound biomagnifying in aquatic food webs, can be a threat to human health via fish consumption. However, the composition and distribution of the microbial communities mediating the methylation of mercury (Hg) to MeHg in marine systems remain largely unknown. In order to fill this gap of knowledge, we used the Baltic Sea Reference Metagenome (BARM) dataset to study the distribution of the genes involved in Hg methylation (the hgcAB gene cluster). We determined the relative abundance of the hgcAB genes and their taxonomic identity in 81 brackish metagenomes that cover spatial, seasonal and redox variability in the Baltic Sea water. The hgcAB genes were predominantly detected in anoxic water, but some hgcAB genes were also detected in hypoxic and normoxic waters. Higher relative quantities of hgcAB genes were found in metagenomes from marine snow compared to free-living communities in anoxic water, suggesting that marine snow are hotspot habitats for Hg methylators in oxygen-depleted seawater. Phylogenetic analysis identified well-characterized Hg methylators such as Deltaproteobacteria in oxygen-depleted water, but also uncovered Hg methylators within the Spirochaetes and Lentisphaerae phyla. Altogether, our work unveils the diversity of the microorganisms mediating MeHg production in the Baltic Sea and pinpoint the ecological niches of these microorganisms within the marine water column.