Simultaneous combustion preparation for mercury isotope analysis and detection of total mercury using a direct mercury analyzer.

Mercury (Hg) stable isotope signatures are widely used to understand Hg cycling in the environment. Sample preparation methods for determining Hg isotope ratios by CV-MC-ICP-MS vary widely among laboratory facilities and sample types. Here, we present a novel and rapid method for preparing solid samples prior to determining Hg isotope composition. We use a direct Hg analyzer (that measures total Hg) for sample combustion, amalgamation and analysis. During the thermal release of Hg from the amalgamator and following detection, the analyte gas enters a trapping solution consisting of 10% HCl/BrCl (5:1, vol/vol). We find Hg blank values are less than 1% of the Hg introduced during sample analysis, Hg detection is not altered by modifying the system, and more than 90% of the introduced Hg is recovered in the trapping solution. Hg isotope results are statistically indistinguishable from accepted values for previously published certified reference materials and uncertainty of 2σ (0.05-0.12‰) is similar to the solution standard RM8610 (2σ = 0.09‰). This new method allows for solid sample preparation for Hg isotope analysis in under 15 min. It has the additional advantage of minimizing use of sample mass during simultaneous detection and preparation.

Updates to instrumentation and protocols for isotopic analysis of nitrate by the denitrifier method.

RATIONALE: The denitrifier method allows for highly sensitive measurement of the (15) N/(14) N (δ(15) N value) and (18) O/(16) O (δ(18) O value) of nitrate dissolved in natural waters and for highly sensitive δ(15) N measurement of other N forms (e.g., organic N) that can be converted into nitrate. Here, updates to instrumentation and protocols are described, and improvements in data quality are demonstrated. METHODS: A 'heart cut' of the N2 O was implemented in the extraction system to (1) minimize introduction of contaminants into the mass spectrometer, reducing isotopic drift and (2) decrease the fraction of sample lost at the open split to improve sensitivity. Referencing protocols were updated, including a correction scheme for a weak dependence of nitrate δ(18) O values on nitrate concentration. Analyses of samples from the US GEOTRACES North Atlantic Program and of reference solutions from the same analysis batches were used to characterize performance. RESULTS: The drift is typically <0.1‰ for both δ(15) N and δ(18) O values. Within-batch and inter-batch replication yields 1 standard deviation (SD) of ≤0.06‰ for δ(15) N values and ≤0.14‰ for δ(18) O values down to 5 µM nitrate and ≤0.08‰ and ≤0.23‰ at 2 and 1 µM. The blank is typically 0.06 nmol N, 0.3% of the N in a 20 nmol N sample. Differences between reference materials in seawater are indistinguishable from reported differences for δ(15) N values, with a contraction for δ(18) O values of ≤5%. CONCLUSIONS: The new instrumentation and protocols yield nitrate isotopic data with external precision of ≤0.1‰ for large sample sets such as those derived from oceanographic sections. Further study should investigate the causes of (1) the weak dependence of nitrate δ(18) O values on nitrate concentration and (2) the inter-batch variation in the δ(18) O contraction (due mostly to oxygen atom exchange with water). Nevertheless, comprehensive correction schemes are in place for the measurement of both the δ(15) N and δ(18) O values of nitrate. Copyright © 2016 John Wiley & Sons, Ltd.

Bacterial diversity in hydrothermal sediment and epsilonproteobacterial dominance in experimental microcolonizers at the Mid-Atlantic Ridge.

We report here a molecular survey based on 16S rRNA genes of the bacterial diversity found in two deep-sea vent niches at the Mid-Atlantic Ridge: hydrothermal sediment (Rainbow site), and microcolonizers made of three different substrates (organic-rich, iron-rich and pumice) that were exposed for 15 days to a vent emission. Bacterial diversity in sediment samples was scattered through many bacterial divisions. The most abundant and diverse environmental sequences (phylotypes) in our libraries corresponded to the Gammaproteobacteria, followed by the Acidobacteria. We detected members of all the subdivisions within the Proteobacteria. Myxobacterial lineages were the most represented within the delta subdivision. Phylotypes ascribing to the Cytophaga-Flavobacterium-Bacteroides, Planctomycetales, high and low G + C Gram-positives, Nitrospirae, and the candidate division TM7 were also identified. Compared to this broad taxonomic coverage, microcolonizers were almost exclusively colonized by epsilonproteobacteria, although these exhibited considerable morphological and phylogenetic in-group diversity. No specificity for any of the substrates tested was seen. This observation further supports the idea of the ecological dominance of epsilonproteobacteria in the fluid-seawater interface environment. Because oxidation of reduced S species and/or sulphur-reduction is thought to be essential for their energetic metabolism in these areas, we mapped different oxidation states of S in individual bacterial filaments from the iron-rich microcolonizer. For this, we used high-resolution, non-destructive synchrotron micro-X-ray Absorption Near-Edge Spectroscopy (micro-XANES), which revealed the co-existence of different S oxidation states, from sulphide to sulphate, at the level of individual cells. This suggests that these cells were metabolizing sulphur in situ.