skip to main content


Title: Chemical reactions, porosity, and microfracturing in shale during weathering: The effect of erosion rate
The rate of chemical weathering has been observed to increase with the rate of physical erosion in published comparisons of many catchments, but the mechanisms that couple these processes are not well understood. We investigated this question by exam- ining the chemical weathering and porosity profiles from catchments developed on marine shale located in Pennsylvania, USA (Susquehanna Shale Hills Critical Zone Observatory, SSHCZO); California, USA (Eel River Critical Zone Observatory, ERC- ZO); and Taiwan (Fushan Experimental Forest). The protolith compositions, protolith porosities, and the depths of regolith at these sites are roughly similar while the catchments are characterized by large differences in erosion rate (1–3 mm yr􏱝1 in Fushan 􏱞 0.2–0.4 mm yr􏱝1 in ERCZO 􏱞 0.01–0.025 mm yr􏱝1 in SSHCZO). The natural experiment did not totally isolate erosion as a variable: mean annual precipitation varied along the erosion gradient (4.2 m yr􏱝1 in Fushan > 1.9 m yr􏱝1 in ERCZO > 1.1 m yr􏱝1 in SSHCZO), so the fastest eroding site experiences nearly twice the mean annual temperature of the other two. Even though erosion rates varied by about 100􏱟, the depth of pyrite and carbonate depletion (defined here as regolith thickness) is roughly the same, consistent with chemical weathering of those minerals keeping up with erosion at the three sites. These minerals were always observed to be the deepest to react, and they reacted until 100% depletion. In two of three of the catchments where borehole observations were available for ridges, these minerals weathered across narrow reaction fronts. On the other hand, for the rock-forming clay mineral chlorite, the depth interval of weathering was wide and the extent of depletion observed at the land surface decreased with increasing erosion/precipitation. Thus, chemical weathering of the clay did not keep pace with erosion rate. But perhaps the biggest difference among the shales is that in the fast-eroding sites, microfractures account for 30–60% of the total porosity while in the slow-eroding shale, dissolution could be directly related to secondary porosity. We argue that the microfractures increase the influx of oxygen at depth and decrease the size of diffusion-limited internal domains of matrix, accelerating weathering of pyrite and carbonate under high erosion-rate condi- tions. Thus, microfracturing is a process that can couple physical erosion and chemical weathering in shales.  more » « less
Award ID(s):
1830732
NSF-PAR ID:
10251604
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Geochimica
ISSN:
0096-3089
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. In weathered bedrock aquifers, groundwater is stored in pores and fractures that open as rocks are exhumed and minerals interact with meteoric fluids. Little is known about this storage because geochemical and geophysical observations are limited to pits, boreholes, or outcrops or to inferences based on indirect measurements between these sites. We trained a rock physics model to borehole observations in a well-constrained ridge and valley landscape and then interpreted spatial variations in seismic refraction velocities. We discovered that P-wave velocities track where a porosity-generating reaction initiates in shale in three boreholes across the landscape. Specifically, velocities of 2.7 ± 0.2 km/s correspond with growth of porosity from dissolution of chlorite, the most reactive of the abundant minerals in the shale. In addition, sonic velocities are consistent with the presence of gas bubbles beneath the water table under valley and ridge. We attribute this gas largely to CO2produced by 1) microbial respiration in soils as meteoric waters recharge into the subsurface and 2) the coupled carbonate dissolution and pyrite oxidation at depth in the rock. Bubbles may nucleate below the water table because waters depressurize as they flow from ridge to valley and because pores have dilated as the deep rock has been exhumed by erosion. Many of these observations are likely to also describe the weathering and flow path patterns in other headwater landscapes. Such combined geophysical and geochemical observations will help constrain models predicting flow, storage, and reaction of groundwater in bedrock systems.

     
    more » « less
  2. 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.

     
    more » « less
  3. Abstract

    Knowing little about how porosity and permeability are distributed at depth, we commonly develop models of groundwater by treating the subsurface as a homogeneous black box even though porosity and permeability vary with depth. One reason for this depth variation is that infiltrating meteoric water reacts with minerals to affect porosity in localized zones called reaction fronts. We are beginning to learn to map and model these fronts beneath headwater catchments and show how they are distributed. The subsurface landscapes defined by these fronts lie subparallel to the soil‐air interface but with lower relief. They can be situated above, below, or at the water table. These subsurface landscapes of reaction are important because porosity developed from weathering can control subsurface water storage. In addition, porosity often changes at the weathering fronts, and when this affects permeability significantly, the front can act like a valve that re‐orients water flowing through the subsurface. We explore controls on the positions of reaction fronts under headwater landscapes by accounting for the timescales of erosion, chemical equilibration, and solute transport. One strong control on the landscape of subsurface reaction is the land surface geometry, which is in turn a function of the erosion rate. In addition, the reaction fronts, like the water table, are strongly affected by the lithology and water infiltration rate. We hypothesize that relationships among the land surface, reaction fronts, and the water table are controlled by feedbacks that can push landscapes towards an ‘ideal hill’. In this steady state, reaction‐front valves partition water volumes into shallow and deep flowpaths. These flows dissolve low‐ and high‐solubility minerals, respectively, allowing their reaction fronts to advance at the erosion rate. This conceptualization could inform better models of subsurface porosity and permeability, replacing the black box.

     
    more » « less
  4. Abstract

    Lithium isotopes are used to trace weathering intensity, but little is known about the processes that fractionate them in highly weathered settings, where secondary minerals play a dominant role in weathering reactions. To help fill this gap in our knowledge of Li isotope systematics, we investigated Li isotope fractionation at an andesitic catchment in Puerto Rico, where the highest rates of silicate weathering on Earth have been documented. We found the lowest δ7Li values published to date for porewater (−27‰) and bulk regolith (−38‰), representing apparent fractionations relative to parent rock of −31‰ and −42‰, respectively. We also found δ7Li values that are lower in the exchangeable fraction than in the bulk regolith or porewater, the opposite than expected from secondary mineral precipitation. We interpret these large isotopic offsets and the unusual relationships between Li pools as resulting from two distinct weathering processes at different depths in the regolith. At the bedrock‐regolith transition (9.3–8.5 m depth), secondary mineral precipitation preferentially retains the lighter6Li isotope. These minerals then dissolve further up the profile, leaching6Li from the bulk solid, with a total variation of about +50‰withinthe profile, attributable primarily to clay dissolution. Importantly, streamwater δ7Li (about +35‰) is divorced entirely from these regolith weathering processes, instead reflecting deeper weathering reactions (>9.3 m). Our work thus shows that the δ7Li of waters draining highly weathered catchments may reflect bedrock mineralogy and hydrology, rather than weathering intensity in the regolith covering the catchment.

     
    more » « less
  5. 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. 
    more » « less