The Source of Organic Matter and Its Role in Producing Reduced Sulfur for the Giant Sediment-Hosted Jinding Zinc-Lead Deposit, Lanping Basin, Yunnan, Southwest China

The Jinding deposit, located in the northern part of Lanping basin in southwest China, is the second largest Zn-Pb deposit in China and the third largest Mississippi Valley-type deposit identified globally. The deposit consists of several large tabular orebodies within the Jinding dome. Two stages of sulfide mineralization (sphalerite, galena, and pyrite) are identified, which are mainly hosted in the siliciclastic strata of Early Cretaceous and Paleocene age. The early sulfide minerals are mostly fine grained (<100 μm) and disseminated in the host rocks, whereas the late minerals are ty pically coarse grained (up to 1 mm in diameter) and colloform. It is estimated that about 3.17 × 106 m3 of reduced sulfur (H2S) was involved in the sulfide mineralization of the Jinding deposit, although its origin remains equivocal. Here, we investigate the biomarker signatures of organic matter and the mechanism of generation of the H2S. The organic matter in the Jinding deposit occurs mainly as petroleum filling fractures and cavities in the wall rocks and solid bitumen intergrown with sulfides or calcite. Abundant solid bitumen is also found on the surfaces of the carbonate rocks in the Sanhedong Formation as well as in the rock fractures associated with framboidal pyrite. The petrographic characteristics and maturity-related biomarker parameters show that the solid bitumen in the ores has higher thermal maturity than that in the Sanhedong Formation, suggesting that it was generated at different temperatures in the two settings. The source-related parameters suggest that the solid bitumen in the ores and Sanhedong Formation probably both originated in a mixed marine shale and carbonate environment and that the source rocks for the bitumen precursor were late Triassic marine strata. The δ34S values, ranging from –30 to –10‰ for the fine-grained and disseminated sulfide minerals and from –24.50 to –16.27‰ for the solid bitumen in the early (main) mineralization stage, suggest that H2S was generated by microbial sulfate reduction. We propose that this occurred in the Triassic strata prior to or during migration of hydrocarbons to the Jinding dome to form a H2S-enriched paleo-oil reservoir. This hypothesis is supported by the similarity of the δ34S values (–27.62 to –17.38‰) of solid bitumen in the Sanhedong Formation (the source rocks) to that of bitumen in the ores. The late-ore sulfide, however, displays significantly higher δ34S values, ranging from –8 to 0‰. We propose that the H2S of this stage was mainly generated by thermochemical sulfate reduction as a result of the interaction between hydrocarbons, sulfate, and hydrothermal fluid. The hydrocarbons were oxidized into bitumen that has δ34S values from –7.38 to –4.61‰.

“Candidatus Chlorobium masyuteum,” a Novel Photoferrotrophic Green Sulfur Bacterium Enriched From a Ferruginous Meromictic Lake

Anoxygenic phototrophic bacteria can be important primary producers in some meromictic lakes. Green sulfur bacteria (GSB) have been detected in ferruginous lakes, with some evidence that they are photosynthesizing using Fe(II) as an electron donor (i.e., photoferrotrophy). However, some photoferrotrophic GSB can also utilize reduced sulfur compounds, complicating the interpretation of Fe-dependent photosynthetic primary productivity. An enrichment (BLA1) from meromictic ferruginous Brownie Lake, Minnesota, United States, contains an Fe(II)-oxidizing GSB and a metabolically flexible putative Fe(III)-reducing anaerobe. “Candidatus Chlorobium masyuteum” grows photoautotrophically with Fe(II) and possesses the putative Fe(II) oxidase-encoding cyc2 gene also known from oxygen-dependent Fe(II)-oxidizing bacteria. It lacks genes for oxidation of reduced sulfur compounds. Its genome encodes for hydrogenases and a reverse TCA cycle that may allow it to utilize H2 and acetate as electron donors, an inference supported by the abundance of this organism when the enrichment was supplied by these substrates and light. The anaerobe “Candidatus Pseudopelobacter ferreus” is in low abundance (∼1%) in BLA1 and is a putative Fe(III)-reducing bacterium from the Geobacterales ord. nov. While “Ca. C. masyuteum” is closely related to the photoferrotrophs C. ferroooxidans strain KoFox and C. phaeoferrooxidans strain KB01, it is unique at the genomic level. The main light-harvesting molecule was identified as bacteriochlorophyll c with accessory carotenoids of the chlorobactene series. BLA1 optimally oxidizes Fe(II) at a pH of 6.8, and the rate of Fe(II) oxidation was 0.63 ± 0.069 mmol day–1, comparable to other photoferrotrophic GSB cultures or enrichments. Investigation of BLA1 expands the genetic basis for phototrophic Fe(II) oxidation by GSB and highlights the role these organisms may play in Fe(II) oxidation and carbon cycling in ferruginous lakes.

Sulfurization of dissolved organic matter in the anoxic water column of the Black Sea

Today’s oceans store as much dissolved organic carbon (DOC) in the water column as there is CO2 in the atmosphere, and as such dissolved organic matter (DOM) is an important component of the global carbon cycle. It was shown that in anoxic marine sediments, reduced sulfur species (e.g., H2S) abiotically react with organic matter, contributing to carbon preservation. It is not known whether such processes also contribute to preserving DOM in ocean waters. Here, we show DOM sulfurization within the sulfidic waters of the Black Sea, by combining elemental, isotopic, and molecular analyses. Dissolved organic sulfur (DOS) is formed largely in the water column and not derived from sediments or allochthonous nonmarine sources. Our findings suggest that during large-scale anoxic events, DOM may accumulate through abiotic reactions with reduced sulfur species, having long-lasting effects on global climate by enhancing organic carbon sequestration.

Metagenomic insights into mixotrophic denitrification facilitated nitrogen removal in a full-scale A2/O wastewater treatment plant

Wastewater treatment plants (WWTPs) are important for pollutant removal from wastewater, elimination of point discharges of nutrients into the environment and water resource protection. The anaerobic/anoxic/oxic (A2/O) process is widely used in WWTPs for nitrogen removal, but the requirement for additional organics to ensure a suitable nitrogen removal efficiency makes this process costly and energy consuming. In this study, we report mixotrophic denitrification at a low COD (chemical oxygen demand)/TN (total nitrogen) ratio in a full-scale A2/O WWTP with relatively high sulfate in the inlet. Nitrogen and sulfur species analysis in different units of this A2/O WWTP showed that the internal sulfur cycle of sulfate reduction and reoxidation occurred and that the reduced sulfur species might contribute to denitrification. Microbial community analysis revealed that Thiobacillus, an autotrophic sulfur-oxidizing denitrifier, dominated the activated sludge bacterial community. Metagenomics data also supported the potential of sulfur-based denitrification when high levels of denitrification occurred, and sulfur oxidation and sulfate reduction genes coexisted in the activated sludge. Although most of the denitrification genes were affiliated with heterotrophic denitrifiers with high abundance, the narG and napA genes were mainly associated with autotrophic sulfur-oxidizing denitrifiers. The functional genes related to nitrogen removal were actively expressed even in the unit containing relatively highly reduced sulfur species, indicating that the mixotrophic denitrification process in A2/O could overcome not only a shortage of carbon sources but also the inhibition by reduced sulfur of nitrification and denitrification. Our results indicate that a mixotrophic denitrification process could be developed in full-scale WWTPs and reduce the requirement for additional carbon sources, which could endow WWTPs with more flexible and adaptable nitrogen removal.