New type of filaments for improved accuracy of multiple sulfur isotope analyses by electron-impact gas-source mass spectrometry.

RATIONALE: The analysis of the three sulfur stable isotope ratios (33S/32S, 34S/32S, 36S/32S) is routinely performed by gas-source isotope ratio mass spectrometry (IRMS) on the SF6 gaseous molecule, collecting SF5 + ions at m/z ~ 127, 128, 129 and 131. High precision and accuracy are commonly achieved owing to a lack of correction because fluorine has only one isotope and the inert nature of the SF6 molecule. The analysis of the 36S/32S ratio is, however, complicated by the low abundance of 36S (~0.015%) and the possible occurrence of trace amounts of fluorocarbon compounds leading to 12C3F5 + ions at m/z ~ 131, i.e. where 36SF5 + ions are collected. METHODS: We used gas-source high-resolution IRMS to better characterize the nature of possible interferences, and we tested novel types of filaments in order to investigate their influence on possible interferences. RESULTS: We confirm that the 12C3F5 + ion represents the main isobaric interference at m/z ~ 131. We also demonstrate that tungsten fluoride adducts are formed from the reaction of fluorine ions derived during fragmentation of the SF6 molecule with the hot tungsten filament. These reactions lead to the formation of e.g. WF5 +, WF4 +, WF3 + ions, including doubly charged ions. WF4 ++, in particular, leads to isobaric interference on m/z ~ 128, 129 and 131 from 180WF4 ++, 182WF4 ++ and 186 WF4 ++ ions, respectively. Because 180W (0.12%) is at low abundance, its influence on δ33S measurements would remain negligible, but 182W (26.5%) and 186W (28.4%) lead to scale contraction for both δ34S and δ36S. CONCLUSIONS: Rather than correcting for these interferences, or working at high mass resolution, we suggest avoiding W isobaric interferences by using other types of filaments, with initial reports on both pure Re filaments and Y2O3-coated W filaments.

Rapid pyritization in the presence of a sulfur/sulfate-reducing bacterial consortium.

Sedimentary pyrite (FeS2) is commonly thought to be a product of microbial sulfate reduction and hence may preserve biosignatures. However, proof that microorganisms are involved in pyrite formation is still lacking as only metastable iron sulfides are usually obtained in laboratory cultures. Here we show the rapid formation of large pyrite spherules through the sulfidation of Fe(III)-phosphate (FP) in the presence of a consortium of sulfur- and sulfate-reducing bacteria (SRB), Desulfovibrio and Sulfurospirillum, enriched from ferruginous and phosphate-rich Lake Pavin water. In biomineralization experiments inoculated with this consortium, pyrite formation occurred within only 3 weeks, likely enhanced by the local enrichment of polysulfides around SRB cells. During this same time frame, abiotic reaction of FP with sulfide led to the formation of vivianite (Fe3(PO4)2·8H2O) and mackinawite (FeS) only. Our results suggest that rates of pyritization vs. vivianite formation are regulated by SRB activity at the cellular scale, which enhances phosphate release into the aqueous phase by increased efficiency of iron sulfide precipitation, and thus that these microorganisms strongly influence biological productivity and Fe, S and P cycles in the environment.

Microbial diversity involved in iron and cryptic sulfur cycling in the ferruginous, low-sulfate waters of Lake Pavin.

Both iron- and sulfur- reducing bacteria strongly impact the mineralogy of iron, but their activity has long been thought to be spatially and temporally segregated based on the higher thermodynamic yields of iron over sulfate reduction. However, recent evidence suggests that sulfur cycling can predominate even under ferruginous conditions. In this study, we investigated the potential for bacterial iron and sulfur metabolisms in the iron-rich (1.2 mM dissolved Fe2+), sulfate-poor (< 20 µM) Lake Pavin which is expected to host large populations of iron-reducing and iron-oxidizing microorganisms influencing the mineralogy of iron precipitates in its permanently anoxic bottom waters and sediments. 16S rRNA gene amplicon libraries from at and below the oxycline revealed that highly diverse populations of sulfur/sulfate-reducing (SRB) and sulfur/sulfide-oxidizing bacteria represented up to 10% and 5% of the total recovered sequences in situ, respectively, which together was roughly equivalent to the fraction of putative iron cycling bacteria. In enrichment cultures amended with key iron phases identified in situ (ferric iron phosphate, ferrihydrite) or with soluble iron (Fe2+), SRB were the most competitive microorganisms, both in the presence and absence of added sulfate. The large fraction of Sulfurospirillum, which are known to reduce thiosulfate and sulfur but not sulfate, present in all cultures was likely supported by Fe(III)-driven sulfide oxidation. These results support the hypothesis that an active cryptic sulfur cycle interacts with iron cycling in the lake. Analyses of mineral phases showed that ferric phosphate in cultures dominated by SRB was transformed to vivianite with concomitant precipitation of iron sulfides. As colloidal FeS and vivianite have been reported in the monimolimnion, we suggest that SRB along with iron-reducing bacteria strongly influence iron mineralogy in the water column and sediments of Lake Pavin.