Sulfur-containing amino acid methionine as the precursor of volatile organic sulfur compounds in algea-induced black bloom

After the application of methionine, a progressive and significant increase occurred in five volatile organic sulfur compounds （VOSCs）： methanethiol （MESH）, dimethyl sulfide （DMS）, dime^yl disulfide （DMDS）, dimethyl trisulfide （DMTS） and dimethyl tetrasulfide （DMTeS）. Even in the untreated control without a methionine addition, methionine and its catabolites （VOSCs, mainly DMDS） were found in considerable amounts that were high enough to account for the water＇s offensive odor. However, blackening only occurred in two methionine-amended treatments. The VOSCs production was observed to precede black color development, and the reaching of a peak value for total VOSCs was often followed by water blackening. The presence of glucose stimulated the degradation of methionine while postponing the occurrence of the black color and inhibiting the production of VOSCs. In addition, DMDS was found to be the most abundant species produced after the addition of methionine alone, and DMTeS appeared to be the most important compound produced after the addition of methionine＋glucose. These results suggest that methionine acted as an important precursor of the VOSCs in lakes suffering from algea-induced black bloom. The existence of glucose may change the transformation pathway of methionine into VOSCs to form larger molecular weight compounds, such as DMTS and DMTeS.

Chemical, carbon and sulfur isotopic compositions constrain the origin of Upper Carboniferous-Lower Triassic gases in eastern Sichuan Basin, SW China

Methane dominated gas is one of the cleanest energy resources;however, there is no direct method to determine its source rock. Natural gases produced from the eastern Sichuan Basin together with seismic data were studied for their sources and secondary alteration by thermochemical sulfate reduction(TSR). Our results demonstrate that Upper Permian to Lower Triassic(P_(3)ch-T_(1)f) gases in the surrounding of the Kaijiang-Liangping area show volatile organic sulfur compounds(VOSCs) δ^(34)S values close to those of the associated H_(2)S, and may have been altered by methane-dominated TSR, resulting in positive shift in methane δ^(13)C_(1)values with increasing TSR extents. Other(or group 2) gases produced from the P_(3)ch-T_(1)f reservoirs from the southern area and the Upper Carboniferous to Middle Permian(C_(2)h-P_(2)q) from the eastern Sichuan Basin are not significantly changed by TSR, show similar δ^(34)S values between the kerogens and some VOSCs, and may have been derived from the Lower Silurian and Middle Permian source rocks. This study demonstrates a case for the first time showing the δ^(34)S values of VOSCs can be used as a tool for direct correlation between non-TSR altered gas and source rocks. Methane-dominated gas pools can be found using gas and source rock geochemistry combined with seismic data.

Marine Carbon-Sulfur Biogeochemical Cycles during the Steptoean Positive Carbon Isotope Excursion(SPICE) in the Jiangnan Basin, South China

Global occurrences of Steptoean Positive Carbon Isotope Excursion（SPICE） during Late Cambrian recorded a significant perturbation in marine carbon cycle, and might have had profound impacts on the biological evolution. In previous studies, SPICE has been reported from the Jiangnan slope belt in South China. To evaluate the bathymetric extent of SPICE, we investigate the limestone samples from the upper Qingxi Formation in the Shaijiang Section in the Jiangnan Basin. Our results show the positive excursions for both carbonate carbon（δ^（13）C） and organic carbon（δ^（13）C_（org）） isotopes, as well as the concurrent positive shifts in sulfur isotopes of carbonate associated sulfate（CAS, δ^（34）S_（CAS）） and pyrite（δ^（34）S_（pyrite））, unequivocally indicating the presence of SPICE in the Jiangnan Basin. A 4‰ increase in δ^（13）C_（carb） of the Qingxi limestone implies the increase of the relative flux of organic carbon burial by a factor of two. Concurrent positive excursions in δ^（34）S_（CAS） and δ^（34）S_（pyrite） have been attributed to the enhanced pyrite burial in oceans with extremely low concentration and spatially heterogeneous isotopic composition of seawater sulfate. Here, we propose that the seawater sulfur isotopic heterogeneity can be generated by volatile organic sulfur compound（VOSC, such as methanethiol and dimethyl sulfide） formation in sulfidic continental margins that were widespread during SPICE. Emission of 32S-enriched VOSC in atmosphere, followed by lateral transportation and aerobic oxidation in atmosphere, and precipitation in open oceans result in a net flux of ^（32）S from continental margins to open oceans, elevating δ^（34）S of seawater sulfate in continental margins. A simple box model indicates that about 35% to 75% of seawater sulfate in continental margins needs to be transported to open oceans via VOSC formation.

Beyond hypoxia: Occurrence and characteristics of black blooms due to the decomposition of the submerged plant Potamogeton crispus in a shallow lake

Organic matter-induced black blooms （hypoxia and an offensive odor） are a serious ecosystem disasters that have occurred in some large eutrophic shallow lakes in China. In this study, we investigated two separate black blooms that were induced by Potamogeton crispus in Lake Taihu, China. The main physical and chemical characteristics, including color- and odor-related substances, of the black blooms were analyzed. The black blooms were characterized by low dissolved oxygen concentration （close to 0 mg/L）, low oxidation-reduction potential, and relatively low pH of overlying water. Notably higher Fe^2＋ and ∑S2- were found in the black-bloom waters than in waters not affected by black blooms. The black color of the water may be attributable to the high concentration of these elements, as black FeS was considered to be the main substance causing the black color of blooms in freshwater lakes. Volatile organic sulfur compounds, including dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide, were very abundant in the black-bloom waters. The massive anoxic degradation of dead Potamogeton crispus plants released dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide, which were the main odor-causing compounds in the black blooms. The black blooms also induced an increase in ammonium nitrogen and soluble reactive phosphorus levels in the overlying waters. This extreme phenomenon not only heavily influenced the original lake ecosystem but also greatly changed the cycling of Fe, S, and nutrients in the water column.

Isolation and Characterization of Methanethiol-Producing Bacteria from Agricultural Soils

Methanethiol(MT) produced from terrestrial soils can have important effects on atmospheric chemistry and ecosystem-level processes, and it originates mainly from the metabolism of sulfur-containing amino acids by microorganisms.Methanethiol producing bacteria(MPB) were enriched and isolated from agricultural soils in a modified basal medium containing methionine(Met) as the sole carbon source.The isolates were identified as Bacillus sp.WH-R1, WH-R2, and WH-R3; Arthrobacter sp.SZLB-W3; and Delftia sp.CHZG-R4 based on cell morphology, physiological and biochemical characteristics, and 16 S r RNA sequence analysis.Delftia sp.CHZG-R4 was identified as a novel strain producing MT using Met as a precursor, and it had the most active MT-producing potential, with the production of MT being 21.8 μg at 30℃ and pH 7.0.Optimal MT production was observed at 35℃ and pH6.0, with 51.3% of sulfur content in Met being converted into MT.Under these conditions, MT production changed according to the supply of both carbon and nitrogen sources.The addition of 2 g L^(-1) each of starch, sucrose, urea, and potassium nitrate promoted MT production by more than 10%, whereas addition of 2 g L^(-1) each of ammonia sulfate and peptone decreased MT production by16% and 87%, respectively.This is the first study to report MT production by Delftia sp.CHZG-R4, providing useful information for the microbial mechanism of MT production from agricultural soils.Our findings also contribute to improving our knowledge of the function of Delftia sp.CHZG-R4.