ABSTRACT
Although metal redox reactions in soils can strongly affect carbon mineralization and other important soil processes, little is known about temporal variations in this redox cycling. Recently, potentiostatically poised electrodes (fixed-potential electrodes) have shown promise for measuring the rate of oxidation and reduction at a specific reduction potential in situ in riparian soils. Here for the first time, we used these electrodes in unsaturated soils to explore the fine-scale temporal redox fluctuations of both iron and manganese in response to environmental conditions. We used three-electrode systems with working electrodes fixed at 100 mV (vs. SHE) and 400 mV at 50 cm and 70 cm in the valley floor soil of a headwater watershed. Electrodes fixed at 100 mV to mimic iron oxides and at 400 mV to mimic manganese oxides allowed real-time reduction and oxidation rates to be calculated from temporal variations in the electric current. Electrode measurements were compared to soil porewater chemistry, pCO2, pO2, groundwater level, resistivity measurements, and precipitation. The fixed-potential electrodes recorded fluctuations over timescales from minutes to weeks. A consistently negative current was observed at 100 mV (interpreted as oxidation of Fe), while the 400-mV electrode fluctuated between negative and positive currents (Mn oxidation and reduction). When the water table rose above the electrodes, reduction was promoted, but above the water table, rainfall only stimulated oxidation. Precipitation frequency thus drove the multi-day reduction or oxidation events (return interval of 5-10 days). These measurements represent the first direct detections of frequency, period, and amplitude of oxidation and reduction events in unsaturated soils. Fixed-potential electrodes hold promise for accurately exploring the fast-changing biogeochemical impacts of metal redox cycling in soils and represent a significant advance for reactions that have been difficult to quantify.
ABSTRACT
Oxidative weathering of pyrite plays an important role in the biogeochemical cycling of Fe and S in terrestrial environments. While the mechanism and occurrence of biologically accelerated pyrite oxidation under acidic conditions are well established, much less is known about microbially mediated pyrite oxidation at circumneutral pH. Recent work (Percak-Dennett et al., 2017, Geobiology, 15, 690) has demonstrated the ability of aerobic chemolithotrophic microorganisms to accelerate pyrite oxidation at circumneutral pH and proposed two mechanistic models by which this phenomenon might occur. Here, we assess the potential relevance of aerobic microbially catalyzed circumneutral pH pyrite oxidation in relation to subsurface shale weathering at Susquehanna Shale Hills Critical Zone Observatory (SSHCZO) in Pennsylvania, USA. Specimen pyrite mixed with native shale was incubated in groundwater for 3 months at the inferred depth of in situ pyrite oxidation. The colonized materials were used as an inoculum for pyrite-oxidizing enrichment cultures. Microbial activity accelerated the release of sulfate across all conditions. 16S rRNA gene sequencing and metagenomic analysis revealed the dominance of a putative chemolithoautotrophic sulfur-oxidizing bacterium from the genus Thiobacillus in the enrichment cultures. Previously proposed models for aerobic microbial pyrite oxidation were assessed in terms of physical constraints, enrichment culture geochemistry, and metagenomic analysis. Although we conclude that subsurface pyrite oxidation at SSCHZO is largely abiotic, this work nonetheless yields new insight into the potential pathways by which aerobic microorganisms may accelerate pyrite oxidation at circumneutral pH. We propose a new "direct sulfur oxidation" pathway, whereby sulfhydryl-bearing outer membrane proteins mediate oxidation of pyrite surfaces through a persulfide intermediate, analogous to previously proposed mechanisms for direct microbial oxidation of elemental sulfur. The action of this and other direct microbial pyrite oxidation pathways have major implications for controls on pyrite weathering rates in circumneutral pH sedimentary environments where pore throat sizes permit widespread access of microorganisms to pyrite surfaces.
