Beschreibung: Methods for measuring aerobic methane oxidation (MOx) rates in aquatic environments are often based on the incubation of water samples, during which the consumption of methane (CH4) is monitored. Typically, incubation vessels are sealed with butyl rubber because these elastomers are essentially impermeable for gases. We report on the potential toxicity of five different commercially available, lab-grade butyl stoppers on MOx activity in samples from marine and lacustrine environments. MOx rates in incubations sealed with non-halogenated butyl were 〉 50% lower compared to parallel incubations with halogenated butyl rubber stoppers, suggesting toxic effects associated with the use of the non-halogenated butyl type. Aqueous extracts of non-halogenated butyl rubber were contaminated with high amounts of various organic compounds including potential bactericides such as benzyltoluenes and phenylalkanes. Comparably small amounts of organic contaminants were liberated from the halogenated butyl rubber stoppers but only two halogenated stopper types were found that did not seem to leach any organics into the incubation medium. Furthermore, the non-halogenated and two types of the halogenated butyl elastomers additionally leached comparably high amounts of zinc. While the source of the apparent toxicity with the use of the non-halogenated rubber stoppers remains elusive, our results indicate that leaching of contaminants from some butyl rubber stoppers can severely interfere with the activity of MOx communities, highlighting the importance of testing rubber stoppers for their respective contamination potential. The impact of leachates from butyl rubber on the assessment of biogeochemical reaction rates other than MOx seems likely but needs to be verified.

Beschreibung: © The Author(s), 2015. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 12 (2015): 7483-7502, doi:10.5194/bg-12-7483-2015.

Beschreibung: Nitrogen (N) is a key component of fundamental biomolecules. Hence, its cycling and availability are central factors governing the extent of ecosystems across the Earth. In the organic-lean sediment porewaters underlying the oligotrophic ocean, where low levels of microbial activity persist despite limited organic matter delivery from overlying water, the extent and modes of nitrogen transformations have not been widely investigated. Here we use the N and oxygen (O) isotopic composition of porewater nitrate (NO3−) from a site in the oligotrophic North Atlantic (Integrated Ocean Drilling Program – IODP) to determine the extent and magnitude of microbial nitrate production (via nitrification) and consumption (via denitrification). We find that NO3- accumulates far above bottom seawater concentrations (~ 21 μM) throughout the sediment column (up to ~ 50 μM) down to the oceanic basement as deep as 90 m b.s.f. (below sea floor), reflecting the predominance of aerobic nitrification/remineralization within the deep marine sediments. Large changes in the δ15N and δ18O of nitrate, however, reveal variable influence of nitrate respiration across the three sites. We use an inverse porewater diffusion–reaction model, constrained by the N and O isotope systematics of nitrification and denitrification and the porewater NO3- isotopic composition, to estimate rates of nitrification and denitrification throughout the sediment column. Results indicate variability of reaction rates across and within the three boreholes that are generally consistent with the differential distribution of dissolved oxygen at this site, though not necessarily with the canonical view of how redox thresholds separate nitrate regeneration from dissimilative consumption spatially. That is, we provide stable isotopic evidence for expanded zones of co-occurring nitrification and denitrification. The isotope biogeochemical modeling also yielded estimates for the δ15N and δ18O of newly produced nitrate (δ15NNTR (NTR, referring to nitrification) and δ18ONTR), as well as the isotope effect for denitrification (15ϵDNF) (DNF, referring to denitrification), parameters with high relevance to global ocean models of N cycling. Estimated values of δ15NNTR were generally lower than previously reported δ15N values for sinking particulate organic nitrogen in this region. We suggest that these values may be, in part, related to sedimentary N2 fixation and remineralization of the newly fixed organic N. Values of δ18ONTR generally ranged between −2.8 and 0.0 ‰, consistent with recent estimates based on lab cultures of nitrifying bacteria. Notably, some δ18ONTR values were elevated, suggesting incorporation of 18O-enriched dissolved oxygen during nitrification, and possibly indicating a tight coupling of NH4+ and NO2− oxidation in this metabolically sluggish environment. Our findings indicate that the production of organic matter by in situ autotrophy (e.g., nitrification, nitrogen fixation) supplies a large fraction of the biomass and organic substrate for heterotrophy in these sediments, supplementing the small organic-matter pool derived from the overlying euphotic zone. This work sheds new light on an active nitrogen cycle operating, despite exceedingly low carbon inputs, in the deep sedimentary biosphere.

Beschreibung: Funding for this work was provided in part by the International Ocean Drilling Program, Woods Hole Oceanographic Institution and a grant from the Center for Dark Energy Biosphere Investigations (C-DEBI) to SW and WZ and a postdoc fellowship to CB from C-DEBI. WZ was supported in part by NSF grant OCE-1131671.