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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. 

Predicting the partitioning between aqueous and gaseous C across landscapes is difficult because many factors interact to control carbon dioxide (CO₂) concentrations and removal as dissolved inorganic carbon (DIC). For example, carbonate minerals buffer soil pH and allow CO₂dissolution in porewaters, but nitrification of fertilizers may decrease pH so that carbonate weathering results in a gaseous CO₂efflux. Here, we investigate CO₂partitioning in an agricultural, first‐order, mixed‐lithology humid, temperate watershed. We quantified soil mineralogy and measured porewater chemistry, soil moisture, and soil pCO₂and pO₂as a function of depth at three hillslope positions. Variation of soil moisture along the hillslope was the dominant control on the concentration of soil CO₂, but mineralogy acted as a secondary control on the partitioning of CO₂between gaseous and aqueous phases. Regression slopes of pCO₂versus pO₂in the carbonate‐bearing soils indicate a deficit of aerobically respired CO₂relative to O₂(p < 0.05). Additionally, nitrification of upslope fertilizers did not lower soil pH and therefore did not cause a gaseous CO₂flux from carbonate weathering. We concluded that in the calcareous soils, up to 43% of respired C potentially dissolves and drains from the soil rather than diffusing out to the atmosphere. To explore the possible implications of the reactions we evaluated, we used databases of carbonate minerals and land uses to map types of soil degassing behaviors. Based on our maps, the partitioning of respired soil CO₂to the aqueous phase could be important in estimating ecosystem C budgets and models.

 

To investigate how bedrock transforms to soil, we mapped the topography of the interface demarcating onset of weathering under an east‐west trending shale watershed in the Valley and Ridge province in the USA Using wave equation travel‐time tomography from a seismic array of >4,000 geophones, we obtained a 3D P‐wave velocity (Vp) model that resolves structures ∼20 m below land surface (mbls). The depth of mobile soil and the onset of dissolution of chlorite roughly match Vp = 600 m/s and Vp = 2,700 m/s, respectively. Chlorite dissolution initiates porosity growth in the shale matrix. Depth to the 2,700 m/s contour is greater under the N‐ as compared to S‐facing hillslopes and under sub‐planar as compared to concave‐up land surfaces. Broadly, the geometries of the ‘soil’ and ‘chlorite’ Vp contours are consistent with the calculated potential for shear fracture opening under weak regional compression. However, this calculated fracture potential does not consistently explain observations related to N‐ versus S‐facing aspect nor fracture density observed by borehole televiewer. Apparently, regional compression is only a secondary influence on Vp: the primary driver of P‐wave slowing in the upper layers of this catchment is topographic control of reactive water flowpaths and their integrated effects on weathering. The Vp result is best explained as the long‐term integrated effect of groundwater flow‐induced geochemical weathering of shale in response to climate‐driven patterns of micro‐ and macro‐topography.

 

The critical zone sustains terrestrial life, but we have few tools to explore it efficiently beyond the first few meters of the subsurface. Using analyses of high‐frequency ambient seismic noise from densely spaced seismometers deployed in the forested Shale Hills subcatchment of the Susquehanna Shale Hills Critical Zone Observatory (SSHCZO), we show that temporal changes in seismic velocities at depths from ∼1 m to tens of m can be detected. These changes are driven by variations at the land surface. The Moving‐Window Cross‐Spectral (MWCS) method was employed to measure seismic‐velocity changes in coda waves at hourly resolution in 10 different frequency bands. We observed a diurnal signal, a seasonal signal, and a meteorological‐event‐based signal. These signals were compared to time‐series measurements of precipitation, well water levels, soil moisture, soil temperature, air temperature, latent heat flux, and air pressure in the heavily instrumented catchment. Most of the velocity changes can be explained by variations in temperature that result in thermoelastic strains that propagate to depth. But some double minima in seismic velocity time‐series observed after large rain events were attributed in part to the effects of water infiltration. These results show that high‐frequency ambient noise data may in some locations be used to detect changes in the critical zone from ∼1 to ∼100 m or greater depth with hourly resolution. But interpretation of such data requires multiple environmental data sets to deconvolve the complex interrelationships among thermoelastic and hydrological effects in the subsurface critical zone.

 

We used seismic refraction to image the P‐wave velocity structure of a shale watershed experiencing regional compression in the Valley and Ridge Province (USA). From estimates showing strong compressional stress, we expected the depth to unweathered bedrock to mirror the hill‐valley‐hill topography (“bowtie pattern”) by analogy to seismic velocity patterns in crystalline bedrock in the North American Piedmont that also experience compression. Previous researchers used failure potentials calculated for strong compression in the Piedmont to suggest fractures are open deeper under hills than valleys to explain the “bowtie” pattern. Seismic images of the shale watershed, however, show little evidence of such a “bowtie.” Instead, they are consistent with weak (not strong) compression. This contradiction could be explained by the greater importance of infiltration‐driven weathering than fracturing in determining seismic velocities in shale compared to crystalline bedrock, or to local perturbations of the regional stress field due to lithology or structures.