『Abstract
Denitrification driven by pyrite oxidation can play a major role
in the removal of nitrate from groundwater systems. As yet, limited
information is available on the interactions between the micro-organisms
and aqueous and mineral phases in aquifers where pyrite oxidation
is occurring. In this study, we examine the groundwater and sediment
composition along a well-characterized redox gradient in a heavily
nitrate-polluted pyritic sandy aquifer in Oostrum (the Netherlands)
to identify the sequence of steps involved in denitrification
coupled to pyrite oxidation. Multi-isotope analyses (δ15N-NO3-, δ18O-NO3-,
δ34S-SO42-, δ18O-SO42- and δ34Spyrite)
confirm that pyrite is the main electron donor for denitrification
at this location. Enrichment factors derived from the observed
changes in nitrate isotopic composition range from -2.0 to -10.9‰
for ε15N and from -2.0 to -9.1‰ for ε18O.
The isotopic data indicate that pyrite oxidation accounts for
approximately 70% of the sulfate present in the zone of denitrification.
Solid-phase analyses confirm the presence of pyrite- and organic
matter-rich clay lenses in the subsurface at Oostrum. In addition,
sulfur XANES and iron XAS results suggest the presence of a series
of intermediate sulfur species (elemental sulfur and SO32-)
that may be produced during denitrification. Consistent with geochemical
analysis, 16S rRNA gene sequencing revealed the presence of bacteria
capable of sulfide oxidation coupled to nitrate reduction and
that are tolerant to high aqueous metal concentrations.
Keywords: Denitrification; Pyrite; Groundwater; Isotopes; Microbiology;
Sediment』
1. Introduction
2. Materials and methods
2.1. Study site and sampling
2.2. Analytical methods
2.2.1. Isotope analysis
2.2.2. Solid sulfur XANES analysis
2.2.3. Solid iron XAS analysis
2.2.4. Microbial community analysis
3. Results and discussion
3.1. Pore water profiles of aqueous components
3.1.1. Isotopic analysis of coupled denitrification-pyrite oxidation
3.1.2. Isotopic evidence for microbial sulfate reduction
3.1.3. Time scales
3.2. Solid-phase analysis
3.3. Linking geochemistry to microbial community composition
4. Conclusions
Acknowledgments
Appendix A. Supplementary data
References