Matrix-independent boron isotope analysis of silicate and carbonate reference materials by ultraviolet femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry with application to the cold-water coral Desmophyllum dianthus.

RATIONALE: Boron isotopes are a powerful tool for pH reconstruction in marine carbonates and as a tracer for fluid-mineral interaction in geochemistry. Microanalytical approaches based on laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) often suffer from effects induced by the sample matrix. In this study, we investigate matrix-independent analyses of B isotopic ratios and apply this technique to cold-water corals. METHODS: We employ a customized 193 nm femtosecond laser ablation system (Solstice, Spectra-Physics) coupled to a MC-ICP-MS system (Nu Plasma II, Nu Instruments) equipped with electron multipliers for in situ measurements of B isotopic ratios (11 B/10 B) at the micrometric scale. We analyzed various reference materials of silicate and carbonate matrices using non-matrix matched calibration without employing any correction. This approach was then applied to investigate defined increments in coral samples from a Chilean fjord. RESULTS: We obtained accurate B isotopic ratios with a reproducibility of ±0.9‰ (2 SD) for various reference materials including silicate glasses (GOR132-G, StHs6/80-G, ATHO-G and NIST SRM 612), clay (IAEA-B-8) and carbonate (JCp-1) using the silicate glass NIST SRM 610 as calibration standard, which shows that neither laser-induced nor ICP-related matrix effects are detectable. The application to cold-water corals (Desmophyllum dianthus) reveals minor intra-skeleton variations in δ11 B with average values between 23.01‰ and 25.86‰. CONCLUSIONS: Our instrumental set-up provides accurate and precise B isotopic ratios independently of the sample matrix at the micrometric scale. This approach opens a wide field of application in geochemistry, including pH reconstruction in biogenic carbonates and deciphering processes related to fluid-mineral interaction.

Influence of temperature on the δ13 C values and distribution of methanotroph-related hopanoids in Sphagnum-dominated peat bogs.

Methane emissions from peat bogs are mitigated by methanotrophs, which live in symbiosis with peat moss (e.g. Sphagnum). Here, we investigate the influence of temperature and resultant changes in methane fluxes on Sphagnum and methanotroph-related biomarkers, evaluating their potential as proxies in ancient bogs. A pulse-chase experiment using 13 C-labelled methane in the field clearly showed label uptake in diploptene, a biomarker for methanotrophs, demonstrating in situ methanotrophic activity in Sphagnum under natural conditions. Peat cores containing live Sphagnum were incubated at 5, 10, 15, 20 and 25°C for two months, causing differences in net methane fluxes. The natural δ13 C values of diploptene extracted from Sphagnum showed a strong correlation with temperature and methane production. The δ13 C values ranged from -34‰ at 5°C to -41‰ at 25°C. These results are best explained by enhanced expression of the methanotrophic enzymatic isotope effect at higher methane concentrations. Hence, δ13 C values of diploptene, or its diagenetic products, potentially provide a useful tool to assess methanotrophic activity in past environments. Increased methane fluxes towards Sphagnum did not affect δ13 C values of bulk Sphagnum and its specific marker, the C23 n-alkane. The concentration of methanotroph-specific bacteriohopanepolyols (BHPs), aminobacteriohopanetetrol (aminotetrol, characteristic for type II and to a lesser extent type I methanotrophs) and aminobacteriohopanepentol (aminopentol, a marker for type I methanotrophs) showed a non-linear response to increased methane fluxes, with relatively high abundances at 25°C compared to those at 20°C or below. Aminotetrol was more abundant than aminopentol, in contrast to similar abundances of aminotetrol and aminopentol in fresh Sphagnum. This probably indicates that type II methanotrophs became prevalent under the experimental conditions relative to type I methanotrophs. Even though BHP concentrations may not directly reflect bacterial activity, they may provide insight into the presence of different types of methanotrophs.

Temperature-induced increase in methane release from peat bogs: a mesocosm experiment.

Peat bogs are primarily situated at mid to high latitudes and future climatic change projections indicate that these areas may become increasingly wetter and warmer. Methane emissions from peat bogs are reduced by symbiotic methane oxidizing bacteria (methanotrophs). Higher temperatures and increasing water levels will enhance methane production, but also methane oxidation. To unravel the temperature effect on methane and carbon cycling, a set of mesocosm experiments were executed, where intact peat cores containing actively growing Sphagnum were incubated at 5, 10, 15, 20, and 25°C. After two months of incubation, methane flux measurements indicated that, at increasing temperatures, methanotrophs are not able to fully compensate for the increasing methane production by methanogens. Net methane fluxes showed a strong temperature-dependence, with higher methane fluxes at higher temperatures. After removal of Sphagnum, methane fluxes were higher, increasing with increasing temperature. This indicates that the methanotrophs associated with Sphagnum plants play an important role in limiting the net methane flux from peat. Methanotrophs appear to consume almost all methane transported through diffusion between 5 and 15°C. Still, even though methane consumption increased with increasing temperature, the higher fluxes from the methane producing microbes could not be balanced by methanotrophic activity. The efficiency of the Sphagnum-methanotroph consortium as a filter for methane escape thus decreases with increasing temperature. Whereas 98% of the produced methane is retained at 5°C, this drops to approximately 50% at 25°C. This implies that warming at the mid to high latitudes may be enhanced through increased methane release from peat bogs.