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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. 

Abstract More above‐ground biomass (kg m⁻²) grows in the northern Appalachian Mountains (USA) in forests on shale than on sandstone at all landscape positions other than ridgetops. This has been tentatively attributed to physical (rather than chemical) attributes of the substrates, such as elevation, particle size, and water capacity. However, shales have generally similar phosphorus (P) concentrations to sandstones and, in the Valley and Ridge province, they erode more quickly. This led us to hypothesize that faster replenishment of the lithogenic nutrient P in shale soils through erosion + soil production could instead control the differences in biomass. To test this, soils and foliage from 10 sites on shales and sandstones in the northern Appalachians from roughly the same elevation and aspect were analysed. We discovered that, when controlling for location, concentrations of bioavailable P in soils and P in foliage were higher and P resorbed from senescing red oak leaves was lower on slower‐eroding sandstone than on faster‐eroding shale. Lower resorption generally can be attributed to lower P limitation for trees. Further investigation of weathering and erosion on one of the sandstone–shale pairs within a larger, paired watershed study revealed that the differences in P concentrations in biomass and foliage between lithologies likely developed because sandstones act as ‘collectors’ that trap nutrients from residual and exogenous sources, while shales erode quickly and thus promote production of soil from bedrock that releases P to ecosystems. We concluded that the combined effects of differential rates of dust collection and erosion results in roughly equal biomass growing on sandstone and shale ridgetops. This work emphasizes the balance between a landscape's capacity to collect dust versus produce soil in controlling bioavailability of nutrients.