Stable Carbon Isotope Signature of Methane Released From Phytoplankton

Unidad de excelencia María de Maeztu CEX2019-000940-MAquatic ecosystems play an important role in global methane cycling and many field studies have reported methane supersaturation in the oxic surface mixed layer (SML) of the ocean and in the epilimnion of lakes. The origin of methane formed under oxic condition is hotly debated and several pathways have recently been offered to explain the "methane paradox." In this context, stable isotope measurements have been applied to constrain methane sources in supersaturated oxygenated waters. Here we present stable carbon isotope signatures for six widespread marine phytoplankton species, three haptophyte algae and three cyanobacteria, incubated under laboratory conditions. The observed isotopic patterns implicate that methane formed by phytoplankton might be clearly distinguished from methane produced by methanogenic archaea. Comparing results from phytoplankton experiments with isotopic data from field measurements, suggests that algal and cyanobacterial populations may contribute substantially to methane formationobserved in the SML of oceans and lakes

A fast and sensitive method for the continuous in situ determination of dissolved methane and its d13C-isotope ratio in surface waters

A fast and sensitive method for the continuous determination of methane (CH4) and its stable carbon isotopic values (d13C-CH4) in surface waters was developed by applying a vacuum to a gas/liquid exchange membrane and measuring the extracted gases by a portable cavity ring-down spectroscopy analyser (M-CRDS). The M-CRDS was calibrated and characterized for CH4 concentration and d13C-CH4 with synthetic water standards. The detection limit of the M-CRDS for the simultaneous determination of CH4 and d13CCH4 is 3.6 nmol L21 CH4. A measurement precision of CH4 concentrations and d13C-CH4 in the range of 1.1%, respectively, 1.7& (1r) and accuracy (1.3%, respectively, 0.8& [1r]) was achieved for single measurements and averaging times of 10 min. The response time s of 5765 s allow determination of d13C-CH4 values more than twice as fast than other methods. The demonstrated M-CRDS method was applied and tested for Lake Stechlin (Germany) and compared with the headspace-gas chromatography and fast membrane CH4 concentration methods. Maximum CH4 concentrations (577 nmol L21) and lightest d13C-CH4 (235.2&) were found around the thermocline in depth profile measurements. The M-CRDS-method was in good agreement with other methods. Temporal variations in CH4 concentration and d13C-CH4 obtained in 24 h measurements indicate either local methane production/oxidation or physical variations in the thermocline. Therefore, these results illustrate the need of fast and sensitive analyses to achieve a better understanding of different mechanisms and pathways of CH4 formation in aquatic environments

Hydrogen and carbon isotope fractionation during degradation of chloromethane by methylotrophic bacteria

Chloromethane (CH3Cl) is a widely studied volatile halocarbon involved in the destruction of ozone in the stratosphere. Nevertheless, its global budget still remains debated. Stable isotope analysis is a powerful tool to constrain fluxes of chloromethane between various environmental compartments which involve a multiplicity of sources and sinks, and both biotic and abiotic processes. In this study, we measured hydrogen and carbon isotope fractionation of the remaining untransformed chloromethane following its degradation by methylotrophic bacterial strains Methylobacterium extorquens CM4 and Hyphomicrobium sp. MC1, which belong to different genera but both use the cmu pathway, the only pathway for bacterial degradation of chloromethane characterized so far. Hydrogen isotope fractionation for degradation of chloromethane was determined for the first time, and yielded enrichment factors (epsilon) of -29 parts per thousand and -27 parts per thousand for strains CM4 and MC1, respectively. In agreement with previous studies, enrichment in C-13 of untransformed CH3Cl was also observed, and similar isotope enrichment factors (e) of -41 parts per thousand and -38 parts per thousand were obtained for degradation of chloromethane by strains CM4 and MC1, respectively. These combined hydrogen and carbon isotopic data for bacterial degradation of chloromethane will contribute to refine models of the global atmospheric budget of chloromethane

Minimum Information about a Biosynthetic Gene cluster

A wide variety of enzymatic pathways that produce specialized metabolites in bacteria, fungi and plants are known to be encoded in biosynthetic gene clusters. Information about these clusters, pathways and metabolites is currently dispersed throughout the literature, making it difficult to exploit. To facilitate consistent and systematic deposition and retrieval of data on biosynthetic gene clusters, we propose the Minimum Information about a Biosynthetic Gene cluster (MIBiG) data standard.Chemistry and Chemical Biolog

Triple‐Element Stable Isotope Analysis of Chloromethane Emitted by Royal Fern and Degraded by Club Moss

AbstractChloromethane (CH3Cl) is the most abundant natural chlorinated organic compound in the atmosphere playing an important role in catalyzing stratospheric ozone loss. Vegetation emits the largest amounts of CH3Cl to the atmosphere but its source strength is highly uncertain leading also to large uncertainties in the global budget of CH3Cl. Triple‐element stable isotope analysis may help to reduce uncertainties because it provides additional process‐level information compared to conventional quantification methods. In this study we performed experiments to obtain a first triple‐elemental isotopic fingerprint (2H, 13C, 37Cl) of CH3Cl emitted by a relevant plant species (royal fern, Osmunda regalis). Isotopic values of all three elements showed considerable differences compared to isotopic values of industrially manufactured CH3Cl which bodes well for future applications to distinguish individual sources. Isotopic analysis of potential precursors (rain, methoxy groups) of CH3Cl in plants revealed no measurable change of hydrogen and chlorine isotopic ratios during formation which may provide a simpler route to estimate the isotopic composition of CH3Cl emissions. Plant degradation experiments of CH3Cl were carried out with club moss (Selaginella kraussiana) revealing significant isotopic fractionation for all three elements. The fractionation pattern characterized by epsilon and lambda is inconsistent with known biotic dechlorination reactions indicating a yet unreported biotic degradation mechanism for CH3Cl. Overall, this study provides first insights into the triple‐elemental isotopic fingerprint of plant emissions and degradation. The results may represent important input data for future isotope‐based models to improve global budget estimates of CH3Cl and to explore the yet unknown degradation pathways.Plain Language Summary: Chloromethane is the most abundant chlorinated organic compound in the atmosphere. It contributes to the destruction of the ozone layer that protects us from skin cancer and genetic damage. Currently, we do not have a good understanding of the sources and removal processes of chloromethane in the atmosphere. In this paper, we use a technique that takes advantage of the different varieties of a chemical element. These so‐called isotopes behave differently during chemical reactions that lead to individual isotopic fingerprints depending on the source or removal process. We used isotopic fingerprints of all three chemical elements in chloromethane and showed that chloromethane produced by a plant (royal fern) differs substantially from chloromethane manufactured by industry. Other plant species such as club moss are able to remove chloromethane from the atmosphere but it is often not clear how this occurs. Isotopic analysis revealed that the studied club moss uses a unique, thus far unknown, way to break down chloromethane. This study demonstrates how information extracted from isotopic fingerprints will help to improve our understanding of sources and removal processes of chloromethane in the atmosphere. It can help to better predict how ozone destruction in the stratosphere affects us in the future.Key Points: First triple‐element isotopic characterization of plant CH3Cl emission and degradation. Plant degradation experiments suggest another yet unknown transformation pathway. Important input data for future isotope based models to improve understanding of global CH3Cl budget.Helmholtz Association http://dx.doi.org/10.13039/501100009318Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659https://doi.org/10.48758/ufz.1338

Triple-element stable isotope analysis of chloromethane emitted and degraded by royal fern and club moss

In this study we explored the potential benefits of triple element isotope analysis (2H, 13C, 37Cl) of CH3Cl emitted by royal fern (Osmunda regalis) and degradation by a club moss (Selaginella kraussiania). CH3Cl emitted by royal fern showed depleted isotopic values for all elements compared to anthropogenically produced CH3Cl which bodes well for the distinction of different sources. Degradation by club moss showed relatively large stable chlorine isotope effects consistent with other dechlorination reactions. Stable hydrogen and stable chlorine isotope fractionation were larger for hydrogen and smaller for carbon which may indicate a yet unreported degradation mechanism for CH3C