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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

High performance earth-abundant electrocatalysts for hydrogen evolution reaction and other reactions

Electrodes for catalyzing electrochemical reactions (e.g., the hydrogen evolution reaction) are provided. The electrode may comprise a ternary pyrite-phase transition metal phosphochalcogenide (e.g., CoPS) disposed on a substrate, wherein the ternary pyrite-phase transition metal phosphochalcogenide is a solid material of a ternary compound of a transition metal, phosphorous (P), and a chalcogen, the solid material characterized by a substantially single, ternary alloy phase having a pyrite crystal structure. Methods of using and making the electrodes are also provided.

Jin, Song↗
DOE OSTI2017

Chemical evolution of groundwater in the Wilcox aquifer of the northern Gulf Coastal Plain, USA

The Wilcox aquifer is a major groundwater resource in the northern Gulf Coastal Plain (lower Mississippi Valley) of the USA, yet the processes controlling water chemistry in this clastic aquifer have received relatively little attention. The current study combines analyses of solutes and stable isotopes in groundwater, petrography of core samples, and geochemical modeling to identify plausible reactions along a regional flow path ∼300 km long. The hydrochemical facies evolves from Ca-HCO{sub 3} upgradient to Na-HCO{sub 3} downgradient, with a sequential zonation of terminal electron-accepting processes from Fe(III) reduction through SO{sub 4}{sup 2−} reduction to methanogenesis. In particular, decreasing SO{sub 4}{sup 2−} and increasing δ{sup 34}S of SO{sub 4}{sup 2−} along the flow path, as well as observations of authigenic pyrite in core samples, provide evidence of SO{sub 4}{sup 2−} reduction. Values of δ{sup 13}C in groundwater suggest that dissolved inorganic carbon is contributed both by oxidation of sedimentary organic matter and calcite dissolution. Inverse modeling identified multiple plausible sets of reactions between sampled wells, which typically involved cation exchange, pyrite precipitation, CH{sub 2}O oxidation, and dissolution of amorphous Fe(OH){sub 3}, calcite, or siderite. These reactions are consistent with processes identified in previous studies of Atlantic Coastal Plain aquifers. Contrasts in groundwater chemistry between the Wilcox and the underlying McNairy and overlying Claiborne aquifers indicate that confining units are relatively effective in limiting cross-formational flow, but localized cross-formational mixing could occur via fault zones. Consequently, increased pumping in the vicinity of fault zones could facilitate upward movement of saline water into the Wilcox.

58 GEOSCIENCES↗
DOE OSTI2021

Organic sulfur fluxes and geomorphic control of sulfur isotope ratios in rivers

Pyrite oxidation plays a critical role in the relationship between weathering and climate, and its impact on the global carbon cycle has previously been constrained through inversion models utilizing observations of river sulfate ($SO^{2–}_{4}$) and its 34 S/ 32 S isotope ratio (δ 34 S SO4 ). However, measurements from some rivers have suggested that SSO4 can be substantially impacted by processes such as microbial sulfate reduction and/or sulfur assimilation and cycling, rather than simply reflecting a weighted mixture of lithologic sulfur sources. To study the prevalence and controls on $SO^{2–}_{4}$ transformations, in this study we measured dissolved major element concentrations and δ 34 S SO4 in river water samples from throughout western Iceland. Our analyses focused on samples from a small catchment hosting the Efri Haukadalsá river, a system with relatively uniform and isotopically constrained basaltic bedrock. We also measured sediment δ 34 S and sulfur speciation using sulfur K-edge X-ray absorption spectroscopy on sediment and vegetation samples from this catchment. Values of dissolved δ 34 S SO4 in the Efri Haukadalsá ranged from 2.5‰ to 23.7‰ and had a linear relationship with Cl – /$SO^{2–}_{4}$ ratios, indicating that $SO^{2–}_{4}$ predominantly derived from basalt weathering and meteoric precipitation. The lower δ 34 S SO4 values were found in fluvial valleys with V-shaped cross sections, while higher values of δ 34 S SO4 occurred in U-shaped, glacially eroded valleys with thick alluvial fills blanketing the valley floor. Spectroscopic observations identified organic sulfur phases in suspended river sediment, floodplain deposits, and vegetation. Mass balance calculations quantified the organic sulfur flux as less than 10% of $SO^{2–}_{4}$ export, and sediment δ 34 S values were comparable to river δ 34 S SO4 . We interpreted these isotopic and chemical patterns as reflecting differences in the availability of unweathered bedrock across the Efri Haukadalsá catchment, with V-shaped valleys having greater access to fresh sulfide-bearing minerals than alluviated U-shaped valleys; this interpretation is in contrast to one in which the elevated δ 34 S SO4 values reflect fractionation during sulfur transformations along alluvial reaches. These results validated the application of river inversion models for constraining weathering fluxes and affirmed that pyrite oxidation globally, even in the presence of river sulfur cycling, modulates the abundance of atmospheric carbon dioxide.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Mineral dissolution and precipitation during CO 2 injection at the Frio-I Brine Pilot: Geochemical modeling and uncertainty analysis

During the Frio-I Brine Pilot CO 2 injection experiment in 2004, distinct geochemical changes in response to the injection of 1600 tons of CO 2 were recorded in samples collected from the monitoring well. Previous geochemical modeling studies have considered dissolution of calcite and iron oxyhydroxides, or release of adsorbed iron, as the most likely sources of the increased ion concentrations. We explore in this modeling study possible alternative sources of the increasing calcium and iron, based on the data from the detailed petrographic characterization of the Upper Frio Formation “C”. Particularly, we evaluate whether dissolution of pyrite and oligoclase (anorthite component) can account for the observed geochemical changes. Due to kinetic limitations, dissolution of pyrite and anorthite cannot account for the increased iron and calcium concentrations on the time scale of the field test (10 days). However, dissolution of these minerals is contributing to carbonate and clay mineral precipitation on the longer time scales (1000 years). The one-dimensional reactive transport model predicts carbonate minerals, dolomite and ankerite, as well as clay minerals kaolinite, nontronite and montmorillonite, will precipitate in the Frio Formation “C” sandstone as the system progresses towards chemical equilibrium during a 1000-year period. Cumulative uncertainties associated with using different thermodynamic databases, activity correction models (Pitzer vs. B-dot), and extrapolating to reservoir temperature, are manifested in the difference in the predicted mineral phases. Furthermore, these models are consistent with regards to the total volume of mineral precipitation and porosity values which are predicted to within 0.002%.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Comparative study of microfacies variation in two samples from the Chittenango member, Marcellus shale subgroup, western New York state, USA

This study demonstrates the significant lithologic variations that occur within the two shale samples from the Chittenango member of the Marcellus shale formation from western New York State in terms of mineralogical composition, type of lamination, pyrite occurrences and fossil content using thin section detailed description and field emission Scanning electron microscope (FESEM) with energy dispersive X-Ray Spectrum (EDX). This study is classified samples as laminated clayshale and fossiliferous carbonaceous shale. The most important detrital constituents of these shales are the clay mineral illite and chlorite, quartz, organic matter, carbonate mineral, and pyrite. The laminated clayshale has a lower amount of quartz and carbonate minerals than fossiliferous carbonaceous shale while it has a higher amount of clay minerals (chlorite and illite) and organic matter. FESEM analysis confirms the presence of chlorite and illite. The fossil content in the laminated clayshale is much lower than the fossiliferous carbonaceous shale. This can provide greater insights about variations in the depositional and environmental factors that influenced its deposition. This result can be compiled with the sufficient data to be helpful for designing the horizontal wells and placement of hydraulic fracturing in shale gas exploration and production.

58 GEOSCIENCES↗
DOE OSTI2017

Finely Dispersed Micro- and Nano-Gold Recovery Using Thermomorphic Polymer with Diphenylphosphine

The article reports test data on adsorption and flotation characteristics of thermomorphic polymer joined with diphenylphosphine—TMPD. The test materials are natural pyrite and arsenopyrite, and models of gold-bearing sulfide minerals. Electron microscopy and X-ray structure analysis prove that reductive adsorption of gold at the surface of sulfide minerals from HAuCl{sub 4} solution allows modeling natural aggregates of sulfides and finely dispersed gold. UV spectrophotometry proves selective adsorption of TMPD at gold. Laser scanning microscopy shows connection of TMPD with micro- and nano-size gold on polished sections of pyrite and arsenopyrite. During monomineral flotation, joint use of TMPD and butyl xanthate at a ratio of 1:1 doubles the yield of gold-bearing sulfides and enables maximum recovery of gold minerals at the total consumption of reagents reduced by 30–50%. It is found that TMPD is selective relative to gold-bearing minerals and its combination with xanthate ensures a considerable increment in gold-bearing mineral recovery by flotation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Reactivity of Iron Bearing Minerals and CO 2 Sequestration: A Multi-­Disciplinary and Experimental Approach

The reactivity of sandstones was studied under conditions relevant to the injection of supercritical carbon dioxide in the context of carbon geosequestration. The emphasis of the study was on the reactivity of iron-­bearing minerals when exposed to supercritical CO 2 (scCO 2 ) and scCO 2 with commingled aqueous solutions containing H 2 S and/or SO 2 . Flow through and batch experiments were conducted. Results indicate that sandstones, irrespective of their mineralogy, are not reactive when exposed to pure scCO2 or scCO 2 with commingled aqueous solutions containing H 2 S and/or SO 2 under conditions simulating the environment near the injection point (flow through experiments). However, sandstones are reactive under conditions simulating the edge of the injected CO 2 plume or ahead of the plume (batch experiments). Sandstones containing hematite (red sandstone) are particularly reactive. The composition of the reaction products is strongly dependent on the composition of the aqueous phase. The presence of dissolved sulfide leads to the conversion of hematite into pyrite and siderite. The relative amount of the pyrite and siderite is influenced by the ionic strength of the solution. Little reactivity is observed when sulfite is present in the aqueous phase. Sandstones without hematite (grey sandstones) show little reactivity regardless of the solution composition.

58 GEOSCIENCES↗
DOE OSTI2016

Experimental Studies of Engineered Barrier Systems Conducted at Los Alamos National Laboratory (FY16)

Over the past five years the Used Fuel Campaign has investigated Engineered Barrier Systems (EBS) at higher heat loads (up to 300°C) and pressure (150 bar). This past year experimental work was hindered due to a revamping of the hydrothermal lab. Regardless, two experiments were run this past year, EBS-18 and EBS-19. EBS-18 was run using Low Carbon Steel (LCS) and opalinus clay in addition to the bentonite and opalinus brine. Many of the past results were confirmed in EBS-18, such as the restriction of illite formation due to the bulk chemistry, pyrite degradation, and zeolite formation dependent on the bentonite and opalinus clay. The LCS show vast amounts of pit corrosion (over 100μm of corrosion in six weeks), leading a corrosion rate of 1083 μm/year. In addition, a mineral goethite, an iron-bearing hydroxide, formed in the pits of the LCS. Preliminary results from EBS-19 water chemistry are included but SEM imaging, micro probe and XRD are still needed for further results. Copper corrosion was investigated further and over 850 measurements were taken. It was concluded that pitting and pyrite degradation drastically increase the corrosion rate from 0.12 to 0.39 μm/day. However, the growth of a layer of the mineral chalcocite is thought to subdue the corrosion rate to 0.024 μm/day as observed in the EBS-13, a sixth month experiment. This document presents the findings of this past year.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Monitoring of U(VI) Bioreduction after ARCADIS demonstration at Savannah River Site F-Area - 15699

The F/H Area Seepage Basins located in the center of Savannah River Site (SRS) received approximately 1.8 billion gallons of acidic waste solutions. The acidic nature of the basin waste solutions triggered the mobilization of metals and radionuclides including soluble uranium (VI). SRS F-Area sediments are acidic and composed predominantly of quartz sand with varying amounts of fine-grained minerals and iron-oxides. In 2010, ARCADIS implemented in-situ injections of a carbohydrate substrate to establish anaerobic reactive zones for metal and radionuclide remediation via the Enhanced Anaerobic Reductive Precipitation (EARP) process at the SRS F-Area (Figure 2). The addition of the molasses substrate solution to groundwater produces anaerobic conditions with redox values in the methanogenic or sulfate-reducing range conducive to the reductive precipitation of uranium. Objectives: Determine the mineral composition of SRS fine clay fractions and identify all iron-oxide phases. Establish if ferrous carbonate and ferrous sulfide compounds will be present in the sediment after the bioreduction process has occurred. The presence of these compounds will indicate that anaerobic reductive conditions were established. Determine the types of reactions that might occur in the anaerobic aquifer. Determine if conditions will return to the initial state once samples are returned to aerobic conditions. Microcosm studies were prepared with SRS sediments treated using a basal medium solution augmented with sulfate and molasses as well as a trace metal solution. To create anaerobic conditions necessary for the experiment, a vinyl anaerobic airlock chamber from COY Lab Products was used to ensure that no oxygen reached the samples. Half of the samples were augmented with sulfate in an attempt to create iron sulfide and stabilize reduced uranium. A pH evolution study was conducted to find the type of pH changes that occurred in the samples. Samples were sieved to 180 mm before X-ray Diffraction (XRD) analysis was conducted to identify any mineralogical changes in the samples. The experimental patterns were compared against known XRD patterns for siderite and pyrite. Liquid samples were filtered through 0.45 mm filters and were diluted by a factor of 200 in nitric acid (1%) for ICP-OES analysis to determine the ferrous iron concentration. XRD analysis indicated that the sediments contained quartz, kaolinite, montmorillonite, and goethite. All of the samples have followed a similar trend, with a decline in the pH values. It was noted that samples amended with sulfates had slightly higher pH than sulfate-free samples. The pH drop can be attributed to the fermentation process of molasses and the natural acidity of SRS soil used for the microcosm study. The low pH conditions are believed to have hindered the formation of bicarbonate/carbonate ions used to form the iron precipitates. XRD results confirmed the assumption that with low pH values no iron compounds would precipitate in the samples. The experimental patterns for each sample was compared with the patterns for siderite and pyrite; the results for these analyses were negative. ICP-OES analysis confirmed that there is ferrous iron present in the samples. The highest iron concentration being 13312.8 ppb for Batch 1, Sample 1-2, the lowest were in Batch 2 Samples 2,3, and 4 which may be below the calibration curve. This may also be an indication that the iron has precipitated in these samples. Future work: Conduct ICP analysis on the Batch 2 samples using a lower dilution factor. Determine the types of reactions that might occur in the anaerobic aquifer. Verify the continued sequestration of U(VI) in relation to the possible re-oxidation of minerals from the bioreduction zone. Sulfate concentrations will be examined using an ion analysis technique. Determine pH levels, sulfate concentrations, and iron concentrations after re-oxygenation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Organic sulfur from source to sink in low‐sulfate Lake Superior

Abstract Organic sulfur plays a crucial role in the biogeochemistry of aquatic sediments, especially in low sulfate (< 500 μ M) environments like freshwater lakes and the Earth's early oceans. To better understand organic sulfur cycling in these systems, we followed organic sulfur in the sulfate‐poor (< 40 μ M) iron‐rich (30–80 μ M) sediments of Lake Superior from source to sink. We identified microbial populations with shotgun metagenomic sequencing and characterized geochemical species in porewater and solid phases. In anoxic sediments, we found an active sulfur cycle fueled primarily by oxidized organic sulfur. Sediment incubations indicated a microbial capacity to hydrolyze sulfonates, sulfate esters, and sulfonic acids to sulfate. Gene abundances for dissimilatory sulfate reduction ( dsrAB ) increased with depth and coincided with sulfide maxima. Despite these indicators of sulfide formation, sulfide concentrations remain low (< 40 nM) due to both pyritization and organic matter sulfurization. Immediately below the oxycline, pyrite accounted for 13% of total sedimentary sulfur. Both free and intact lipids in this same interval accumulated disulfides, indicating rapid sulfurization even at low concentrations of sulfide. Our investigation revealed a new model of sulfur cycling in a low‐sulfate environment that likely extends to other modern lakes and possibly the ancient ocean, with organic sulfur both fueling sulfate reduction and consuming the resultant sulfide.

Phillips, Alexandra A.↗
DOE OSTI2024

Mineral and fluid transformation of hydraulically fractured shale: case study of Caney Shale in Southern Oklahoma

This study explores the geochemical reactions that can cause permeability loss in hydraulically fractured reservoirs. The experiments involved the reaction of powdered-rock samples with produced brines in batch reactor system at temperature of 95 °C and atmospheric pressure for 7-days and 30-days respectively. Results show changes in mineralogy and chemistry of rock and fluid samples respectively, therefore confirming chemical reactions between the two during the experiments. The mineralogical changes of the rock included decreases of pyrite and feldspar content, whilst carbonate and illite content showed an initial stability and increase respectively before decreasing. Results from analyses of post-reaction fluids generally corroborate the results obtained from mineralogical analyses. Integrating the results obtained from both rocks and fluids reveal a complex trend of reactions between rock and fluid samples which is summarized as follows. Dissolution of pyrite by oxygenated fluid causes transient and localized acidity which triggers the dissolution of feldspar, carbonates, and other minerals susceptible to dissolution under acidic conditions. The dissolution of minerals releases high concentrations of ions, some of which subsequently precipitate secondary minerals. On the field scale, the formation of secondary minerals in the pores and flow paths of hydrocarbons can cause significant reduction in the permeability of the reservoir, which will culminate in rapid productivity decline. This study provides an understanding of the geochemical rock–fluid reactions that impact long term permeability of shale reservoirs.

58 GEOSCIENCES↗
DOE OSTI2013

Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County, Pennsylvania, USA

Stable isotopes were used to determine the sources and fate of dissolved inorganic C (DIC) in the circumneutral pH drainage from an abandoned bituminous coal mine in western Pennsylvania. The C isotope signatures of DIC (δ{sup 13}C{sub DIC}) were intermediate between local carbonate and organic C sources, but were higher than those of contemporaneous Pennsylvanian age groundwaters in the region. This suggests a significant contribution of C enriched in {sup 13}C due to enhanced carbonate dissolution associated with the release of H{sub 2}SO{sub 4} from pyrite oxidation. The Sr isotopic signature of the drainage was similar to other regional mine waters associated with the same coal seam and reflected contributions from limestone dissolution and cation exchange with clay minerals. The relatively high δ{sup 34}S{sub SO4} and δ{sup 18}O{sub SO4} isotopic signatures of the mine drainage and the presence of presumptive SO{sub 4}-reducing bacteria suggest that SO{sub 4} reduction activity also contributes C depleted in {sup 13}C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased, accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H{sub 2}SO{sub 4} dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO{sub 2} outgassing.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

Multimodal study of the impact of stimulation pH on shale pore structure, with an emphasis on organics behavior in alkaline environments

The tight nature of shale formations calls for hydraulic fracturing techniques able of altering the pore architecture to facilitate the production of hydrocarbon resources. The composition, pH, salinity, density and chemistry of Hydraulic Fracturing Fluids (HFF) vary substantially depending on reservoir characteristics. pH is among the most important stimulation fluid properties, ranging from very acidic, for carbonate reservoirs, to basic, in the case of clay-rich formations. pH regulates what geochemical reactions take place between the stimulation fluid and shale, as well as pore architecture alteration. The dissolution of carbonates and pyrite, and the precipitation of common minerals such as barite, gypsum and iron oxides in acidic environments have been extensively documented. In contrast, alkali stimulation environments and the role of organic components have received less attention. This research provides insight into the role of both minerals and organic components during alkaline stimulation, and the resulting pore architecture alterations. Here, a set of reactive experiments are performed using three different shales, with varying organic matter (OM) content, at different pH (3, 6, 8, 10, 12). The analysis of pore architecture alteration induced by the reaction was performed via nitrogen (N2) gas adsorption and Time-Domain Nuclear Magnetic Resonance (TD-NMR). Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES) was used to measure the composition of the stimulation fluid post-reaction. The system with a larger impact on the pore architecture (pH 12) underwent a more extensive analysis through the application of Focused Ion Beam Scanning Electron Microscopy (FIB-SEM) and x-ray Diffraction (XRD). Results show that mineral dissolution contributed to the creation of secondary porosity, mainly through dissolution of clays and silicates. We show that the abundance and distribution of organic matter both play a significant role in changes in pore architecture. Most samples showed an increase in inter-organic porosity, likely due to the organic acids within kerogen reacting with the stimulation fluid. Samples with a larger amount and more widespread distribution of organic matter show the most significant alterations. Finally, we also highlight the dissolution process of iron-rich minerals, including framboidal pyrite, as another important source of secondary porosity.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2014

Mobilization of Metals from Eau Claire Siltstone and the Impact of Oxygen under Geological Carbon Dioxide Sequestration Conditions

Geologic CO2 sequestration (GCS) has been proposed as a viable strategy to reduce anthropogenic CO2 emission; however, the increased cost that will be incurred by fossil energy production facilities is a deterrent to implementation of this technology. Allowing impurities in the effluent CO2 stream could result in significant financial and energy savings for CO2 capture and separation. However, impurities such as O2 have the potential to influence the redox state and alter the geochemical interactions that occur within GCS reservoirs, which increases the concern for CO2 and brine leakage from the storage reservoir as well as the overlying groundwater contamination. In this work, to investigate the impact of O2 co-injected with CO2 on the geochemical interactions, especially the trace metal mobilization from a GCS reservoir rock, batch studies were conducted with Eau Claire siltstone collected from CO2 sequestration sites. The rock was reacted with synthetic brines in contact with either 100% CO2 or a mixture of 95 mole% CO2-5 mole% O2 at 10.1 MPa and 75 °C. Both microscopic and spectroscopic measurements, including 57Fe-Mössbauer spectroscopy, Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry, powder X-ray diffraction, scanning electron microscopy-energy dispersive x-ray spectroscopy, and chemical extraction were combined in this study to investigate reaction mechanisms. The Eau Claire siltstone contains quartz (52 wt%), fluorapatite (40%), and aluminosilicate (5%) as major components, and dolomite (2%), pyrite (1%), and small-particle-/poorly-crystalline Fe-oxides as minor components. With the introduction of CO2 into the reaction vessel containing rock and brine, the leaching of small amounts of fluorapatite, aluminosilicate, and dolomite occurred. Trace metals of environmental concern, including Pb, As, Cd, and Cu were detected in the leachate with concentrations up to 400 ppb in the CO2-brine-rock reaction system within 30 days. In the presence of O2, the mobilization of Pb, Cd, and Cu was significantly enhanced, whereas As concentrations decreased, compared with the reaction system without oxygen. The presence of oxygen resulted in the formation of secondary Fe-oxides which appear to be Fe(II)-substituted P-containing ferrihydrite. Although the rock contained only 1.04 wt% total Fe, oxidative dissolution of pyrite, leaching and oxidation of structural Fe(II) in fluorapatite, and precipitation of Fe-oxides significantly decreased the pH in brine with oxygen(pH 3.3-3.7), compared with the reaction system without oxygen (pH 4.2-4.4). In the CO2-rock-brine system without O2, the majority of As remained in the rock, with about 1.1% of the total As being released from intrinsic Fe-oxides to the aqueous phase. The release behavior of As to solution was consistent with competitive adsorption between phosphate/fluoride and As on Fe-oxide surfaces. In the presence of O2 the mobility of As was reduced due to enhanced adsorption onto both intrinsic and secondary Fe-oxide surfaces.When O2 was present, the dominant species in solution was the less toxic As(V). This work will advance our understanding of the geochemical reaction mechanisms that occur under GCS conditions and help to evaluate the risks associated with geological CO2 sequestration.

CO2 sequestration, metal release, ground↗
DOE OSTI2019

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 in our research by examining 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, ERCZO); 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 &laquo 0.2–0.4 mm yr ₋1 in ERCZO &laquo 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 conditions. Thus, microfracturing is a process that can couple physical erosion and chemical weathering in shales.

58 GEOSCIENCES↗
DOE OSTI2021

Mineralogy-dependent sulfide oxidation via polysulfide and thiosulfate pathways during weathering of mixed-sulfide bearing mine waste rock

Tracking the S oxidation pathway in sulfide-bearing mine waste-rock piles is complicated by variations in water content, O 2 and Fe 3+ concentrations, microbial diversity, mineralogy, the occurrence of a variety of S species associated with incomplete oxidation, and nonlinear coupling between physicochemical processes. Synchrotron-based S K-edge X-ray absorption near edge structure (XANES) spectroscopy facilitates the identification and quantification of S species (i.e., S 2– , $S_{2}O_{2}^{2–}$, S 8 , $S_{2}O_{3}^{2–}$, and $S_{2}O_{4}^{2–}$) in a weathered mine waste-rock pile containing pyrite, sphalerite, galena, pyrrhotite, and chalcopyrite. Mineralogy-dependent polysulfide and thiosulfate pathways both affect the S oxidation within the waste-rock pile. Currently, the polysulfide pathway, with S 8 as the intermediate S species, generates high concentrations of dissolved metals (from the rapid oxidation of monosulfides including sphalerite, galena, pyrrhotite, and chalcopyrite). As these monosulfides are depleted, the thiosulfate pathway of pyrite oxidation, including intermediate oxidation products (i.e., S 8 and $S_{2}O_{3}^{2–}$), will become the dominant oxidation pathway, resulting in the potential for generation of additional acidic drainage. This information highlights the importance of identifying the sulfide-mineral oxidation reaction pathways when attempting to estimate acid generation potential, and when developing remediation strategies for the storage and management of sulfide-bearing waste rock.

58 GEOSCIENCES↗
DOE OSTI2022

Mineralogical, magnetic and geochemical data constrain the pathways and extent of weathering of mineralized sedimentary rocks

The oxidative weathering of sulfidic rock can profoundly impact watersheds through the resulting export of acidity and metals. Weathering leaves a record of mineral transformation, particularly involving minor redox-sensitive phases, that can inform the development of conceptual and quantitative models. In sulfidic sedimentary rocks, however, variations in depositional history, diagenesis and mineralization can change or overprint the distributions of these trace minerals, complicating the interpretation of weathering signatures. Here we show that a combination of bulk mineralogical and geochemical techniques, micrometer-resolution X-ray fluorescence microprobe analysis and rock magnetic measurements, applied to drill core samples and single weathered fractures, can provide data that enable the development of a geochemically consistent weathering model. This work focused on one watershed in the Upper Colorado River Basin sitting within the Mesaverde Formation, a sedimentary sandstone bedrock with disseminated sulfide minerals, including pyrite and sphalerite, that were introduced during diagenesis and subsequent magmatic-hydrothermal mineralization. Combined analytical methods revealed the pathways of iron (Fe), carbonate and silicate mineral weathering and showed how pH controls element retention or release from the actively weathering fractured sandstone. Drill core logging, whole rock X-ray diffraction, and geochemical measurements document the progression from unweathered rock at depth to weathered rock at the surface. X-ray microprobe analyses of a 1-cm size weathering profile along a fracture surface are consistent with the mobilization of Fe(II) and Fe(III) into acidic pore water from the dissolution of primary pyrite, Fe-sphalerite, chlorite, and minor siderite and pyrrhotite. These reactions are followed by the precipitation of secondary minerals such as of goethite and jarosite, a Fe-(oxyhydr)oxide and hydrous Fe(III) sulfate, respectively. Microscale analyses also helped explain the weathering reactions responsible for the mineralogical transformations observed in the top and most weathered section of the drill core. For example, dissolution of feldspar and chlorite neutralizes the acidity generated by Fe and sulfide mineral oxidation, oversaturating the solution in both Fe-oxides. The combination of X-ray spectromicroscopy and magnetic measurements show that the Fe(III) product is goethite, mainly present either as a coating on fracture surfaces in the actively weathering region of the core or more homogeneously contained within the unconsolidated regolith at the top of the core. Low-temperature magnetic data reveal the presence of ferromagnetic Fe-sulfide pyrrhotite that, although it occurs at trace concentrations, could provide a qualitative proxy for unweathered sulfide minerals because the loss of pyrrhotite is associated with the onset of oxidative weathering. Pyrrhotite loss and goethite formation are detectable through room-temperature magnetic coercivity changes, suggesting that rock magnetic measurements can determine weathering intensity in rock samples at many scales. In conclusion, this work contributes evidence that the weathering of sulfidic sedimentary rocks follows a geochemical pattern in which the abundance of sulfide minerals controls the generation of acidity and dissolved elements, and the pH-dependent mobility of these elements controls their export to the ground- and surface-water.

58 GEOSCIENCES↗