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Alternative approaches to dryland reclamation enhance vegetation cover and soil stability at a former uranium mine

Introduction Conventional reclamation methods to recover dryland ecosystems after mineral extraction often have low success. Alternative reclamation techniques may help overcome the many challenges to establishing persistent native vegetation and stable soils. Objectives Compare conventional reclamation approaches that focus primarily on soil stabilization to alternative approaches that may improve native ecosystem restoration at the Kanab North Mine in northern Arizona. Methods In a fully crossed experiment, conventional seed mix (native and non-native species) and seeding methods (drill-seeding) were compared to alternative practices, including a native-only seed mix, connectivity modifiers (ConMods) with hand seeding, and a biocrust inoculation. Restoration metrics like plant establishment, species composition, soil surface cover and stability, biocrust establishment, and near-surface wind-driven sediment were monitored over the first 5 years post-reclamation. Results While all restoration metrics improved with time, compared to traditional methods, ConMods increased total, graminoid, and native plant species cover, and the native-only seed mix increased woody, native, and perennial species cover. Biocrust inoculation increased late-successional biocrust development, but biocrusts only persisted over 5 years in combination with ConMods. Soil stability increased in all treatments, but both ConMods and biocrust inoculation increased stability compared to traditional practices. Conclusion Overall, alternative approaches to reclamation tested here (ConMods, native seed, and biocrust inoculation) were more effective than traditional practices at increasing total plant cover, facilitating biocrust establishment, and promoting soil stability after uranium mine reclamation.

Arizona

Dynamic drainage reorganization in Eastern Tibet: Insights from the Yangtze River first bend

The modern drainage network of eastern Tibet is widely believed to have developed through a series of river capture and flow reversal events; however, the timing and mechanisms driving this reorganization remain contentious. Among these events, the river capture that formed the First Bend of the Yangtze River (YFB) stands out as both iconic and particularly debated. Here we present sedimentary provenance data from the Late Miocene–Quaternary Dali Basin, located south of the YFB, which indicate that a southward-flowing Jinsha River (i.e., the present-day upper Yangtze River) sourced sediment to the Dali basin at ∼7.4–6.4 Ma in a drainage configuration different from that of today. Because this interval postdates the initial establishment of a near-modern Jinsha River system prior to the Miocene, our results imply at least two discrete fluvial reorganizations occurred at the YFB—one preceding ∼7.4 Ma and another following ∼6.4 Ma. By integrating these findings with landscape evolution modeling, we infer that the initiation of rapid uplift of the Yulong-Haba Mountains and the Diancang Shan may have been responsible for these drainage reorganizations. These results underscore that Cenozoic drainage systems on the eastern Tibetan Plateau have evolved dynamically on a short timescale of ∼10 5 –10 6 -year, rather than remaining in a long-term stationary configuration on ∼10 7 -year timescales.

eastern Tibetan Plateau, first bend of the Yangtze

Case study of deep learning image segmentation for the purposes of rapid 2D petrographic analysis in volcanic rocks

Automation using deep learning methods is a useful alternative to manual methods of petrographic segmentation, but often requires user familiarity with coding and/or algorithms. We examine the Dragonfly TM program's deep learning tools for application by users with a variety of skill levels as a method for petrographic image segmentation. An image processing methodology, bimodal image stacking, was created for low-input-data, high-efficacy training of models which can then be applied to varied samples. Using backscatter electron images we show that the resulting model segmentations agree with manual segmentation total and modal crystallinity values within 5%, and calculated plagioclase crystal size distribution (CSD) values within 2σ, despite limitations in discriminating mafic phases. Model creation and training takes <24 hours, 1–3 hours of which are supervised, and the resultant model can then be applied to new uncharacterized samples in <15 minutes per image. This allows for non-experts to create and utilize deep learning models to segment images of variable brightness and texture, at low user-time cost and resulting in size and shape data which are within uncertainty of manual segmentation. While some limitations are noted (for example, sieve-textured phases may need manual correction, and different minerals with similar BSE intensity may not be resolved as separate phases), this methodology can be utilized for general application of models to wide ranges of volcanic crystalline and bubble textures, and to create a library of models for rapid petrological analysis during volcanic eruptions.

Alaska

False positives in the identification of dynamic earthquake triggering

Dynamic earthquake triggering is commonly identified through the temporal correlation between increased seismicity rates and global earthquakes that are possible triggering events. However, correlation does not imply causation. False positives may occur when unrelated seismicity rate changes coincidently occur at around the time of candidate triggers. We investigate the expected false positive rate in Southern California with global M ≥ 6 earthquakes as candidate triggers. We compute the false positive rate by applying the statistical tests used by DeSalvio and Fan (2023), https://doi.org/10.1029/2023jb026487 to synthetic earthquake catalogs with no real dynamic triggering. We find a false positive rate of ∼3.5%–8.5% when realistic earthquake clustering is present, consistent with the 95% confidence typically used in seismology. However, when this false positive rate is applied to the tens of thousands of spatial-temporal windows in Southern California tested in DeSalvio and Fan (2023), https://doi.org/10.1029/2023jb026487 , thousands of false positives are expected. The expected false positive occurrence is large enough to explain the observed apparent triggering following 70% of large global earthquakes (DeSalvio & Fan, 2023, https://doi.org/10.1029/2023jb026487 ), without requiring any true dynamic triggering. Aside from the known triggering from the nearby El Mayor-Cucapah, Mexico, earthquake, the spatial and temporal characteristics of the reported triggering are indistinguishable from random false positives. This implies that best practice for dynamic triggering studies that depend on temporal correlation is to estimate the false positive rate and investigate whether the observed apparent triggering is distinguishable from the correlations that may occur by chance.

JGR Solid Earth

Substrate Enhancement Pilot Project—Monitoring summary and evaluation, Kootenai River, Idaho, 2012–22

To assess changes in substrate conditions and the efficacy of artificially placed substrates at select sites on the Kootenai River near Bonners Ferry, Idaho, the U.S. Geological Survey, in cooperation with the Kootenai Tribe of Idaho, completed repeat bathymetric, velocimetric, and underwater videography surveys. Collectively, three project sites throughout the Kootenai River make up the Substrate Enhancement Pilot Project (SEPP), an effort intended to improve spawning and egg incubation viability at locations identified to be aquatic habitat limited for the endangered Kootenai River white sturgeon (Acipenser transmontanus). Following the placement of coarse substrates at each site, bathymetric, velocimetric, and underwater videography data were collected from 2012 to 2022 to assess the role of deposition and erosion on maintaining suitable white sturgeon spawning and incubation substrates. Minimal erosion and deposition occurred at all Substrate Enhancement Pilot Project sites, according to interannual and intra-annual net volumetric changes between bathymetric surveys. Depending on the timing of bathymetric surveys relative to the annual peak streamflow conditions, isolated locations of deposition or erosion were observed at each site and the potential for deposition or erosion was supported by measured mean depth-averaged velocities. This study concluded that variability of deposition and scour were common at each site throughout the monitoring period and may be attributed to fluctuations in streamflow. Repeat bathymetric, underwater videography, and velocity mapping surveys were used to verify the interstitial spaces and surfaces of substrates at each SEPP site remained free of fine sediments for intervals longer than a year but were susceptible to deposition between high streamflow events.

Idaho

Regional variations in sea ice and primary productivity in the Bering Sea during Marine Isotope Stage 11

Marine Isotope Stage (MIS) 11 (424-374 ka) has long been an analog for Holocene climate, because it is the most recent interglacial period with similar orbital conditions. However, there is significant global and regional variability in the climate response to MIS 11 warmth. Here, we review sediment core records from across the Bering Sea to investigate changes in paleoceanographic conditions during Marine Isotope Stages 12-10. Sea ice was present over much of the Bering Sea during MIS 11, but today, none of the sites investigated are ever ice-covered. This suggests that sea ice regimes in the Bering Sea during MIS 11 were different to those of the Holocene. There are also regional differences in the response of sea ice to MIS 11 warming. At the Umnak Plateau, Southeastern Bering Sea, sea ice concentrations decline during deglaciation, but they remain high at the slope sites until Peak MIS 11. Sea ice re-advances over the Umnak Plateau during peak interglacial warmth, at the same time that it declines over the slope sites. Late MIS 11 is characterized by high concentrations of seasonal sea ice at the Umnak Plateau, whilst sea ice at the slope sites fluctuates between consolidated and unconsolidated ice cover. This east-west dichotomy may be explained by changes in the behavior of the Aleutian Low. Productivity increases dramatically during deglaciation due to increased upwelling and sea level rise bringing fresh nutrients into the oceans. This is characterized by increased diatom productivity, increased terrestrial carbon deposition, and laminations at all sites.

Alaska

Hazard potential of compound flooding from rainfall, storm surge, and groundwater in coastal New York and Connecticut

Compound flood events, the co-occurrence of multiple flood drivers, can result in flood hazard potential exceeding that of any single driver alone. To evaluate compound flooding in a semi-urbanized coastal area, historical records dating back to 1970 are used to study the co-occurrences of high precipitation, storm surge, and shallow groundwater conditions along the coastlines of New York and Connecticut. Joint return periods for coincident precipitation-surge events were computed using statistical dependence models and compared to the assumption of independence as a ratio, referred to here as a return period adjustment. Results indicate distinct seasonality where compound events in the area disproportionately occur in the cold season between October and April. Return period adjustments range from a factor of 1 to almost 9, demonstrating the range in precipitation-storm surge dependence across the study area. Across all 24 station triad locations, groundwater levels were elevated during times of precipitation- surge co-occurrence, reflecting the tendency for coastal storms and shallow groundwater conditions to co-occur seasonally. The result is a pseudo-trivariate compound flood hazard score and corresponding hazard map that integrates dependence between daily precipitation-surge events and overall monthly groundwater levels (as a precondition) into a relative compound hazard score. The location with the highest compound flood hazard score is on the south shore of Long Island, as well as locations across coastal Connecticut where groundwater levels compound the co-occurrence of heavy precipitation and storm surge.

Connecticut, New York

From exploration to production: Understanding the development dynamics of lithium mining projects

Recently, there has been considerable recent controversy whether current and new lithium mines will be able to supply the rapidly growing needs of the electromobility transition. Mineral exploration projects are typically active for many years, and only some become operational mines. From exploration to production, the projects go through several stages of characterisation and evaluation. At each stage, decisions are made by companies and stakeholders to advance, continue or stop the project. This is a complex process, and even projects with very similar geological and technical characteristics may take very different trajectories, depending on external factors such as global market conditions and local regulatory environments. The present study investigates the dynamics of this process for lithium exploration projects. A global database of 397 lithium projects was compiled, covering their progression through major development stages between 2004 and 2022. Ordinal logistic regression was used for the statistical analysis of this data. Different explanatory variables were tested, including economic, geological, technical, and geographic factors, to identify the best predictors for project progress at each development stage. The results suggest an essential role for lithium carbonate prices, and a variable role for other factors at each stage. Critically, the already elapsed lead time and project economics, which are traditionally considered important for the prediction of the start-up of individual mines, do not appear to be relevant in all cases. The results provide important insights into the dynamics of lithium supply and may eventually allow more realistic forecasts to be made for future lithium market dynamics.

Resources Policy

The geologic history of the Chehalis Forearc Basin, Washington State, USA

The Chehalis basin is located between the Cascade arc and the Coast Range in southwest Washington State. It consists of sedimentary and volcanic rocks deposited throughout the Cenozoic and is underlain by the Siletzia terrane, a thick, large igneous province accreted in the Eocene. Here, we constrain evolution of the Chehalis basin depocenter using isochore maps derived from isostatic gravity anomalies, borehole data, and stratigraphy for several time periods: the Eocene (47.6–36.8 Ma), the Oligocene (36.8–20 Ma), and the Neogene (20–0 Ma). Our results suggest that local subsidence is driven by deformation on faults that bound and intersect the basin. We see northward depocenter migration, interpreted as a shift in deformation from the northwest striking Cedar Creek fault to the west striking Doty fault. We interpret these data in terms of the long-term north-south shortening and clockwise rotation of the Cascadia forearc. During the Eocene, the Cedar Creek fault was preferentially aligned with north-south shortening, but became less active when clockwise rotation brought the Doty fault into east-west alignment with the stress field. Sediment accumulation rates decreased from 196 m/Myr in the Paleogene (∼40–20 Ma) to 27 m/Myr in the Neogene (∼20–0 Ma) as Miocene uplift of the Coast Range limited accommodation space and shifted the depositional environment from marine to fluvial. Our results are consistent with the geologic evolution of the Portland and Tualatin basins to the south and reveal a depositional and structural history uniquely shaped by clockwise rotation of the Cascadia forearc.

Washington

High resolution identification and quantification of diffuse deep groundwater discharge in mountain rivers using continuous boat-mounted helium measurements

Discharge of deeply sourced groundwater to streams is difficult to locate and quantify, particularly where both discrete and diffuse discharge points exist, but diffuse discharge is one of the primary controls on solute budgets in mountainous watersheds. The noble gas helium is a unique identifier of deep groundwater discharge because groundwater with long residence times is commonly enriched in helium. In this study, a portable mass spectrometer was used to measure longitudinal variation in dissolved helium concentrations in two mountainous rivers at high spatial resolution not feasible with traditional sampling techniques. Helium profiles were then simulated using a mass-balance model to quantify longitudinal variation in groundwater discharge to the receiving rivers. Results indicate helium concentrations were enriched by multiple orders of magnitude above atmospheric equilibrium in both rivers and that this persisted for up to 18 km below observed pulse inputs in the Colorado River. Helium mass-balance models match observed longitudinal patterns with the exception of sharp initial increases in helium observed in the rivers. Increased longitudinal groundwater discharge rates correspond to mapped geologic structures in both watersheds that likely transport deep geothermal water. Models show variable sensitivity to spatial assignment of input variables representing the groundwater source, illustrating the importance of collecting data from discrete groundwater discharges where possible. The methodology shows promise for field experiments designed to assess air–water exchange rates and to quantify total groundwater discharge from a combination of discrete and diffuse sources.

Colorado, Utah

Laboratory assessment for recovery of porcine circovirus 2 and porcine reproductive and respiratory syndrome virus using two types of commercially available hollow-fiber ultrafilters

Groundwater near swine farms is an uninvestigated reservoir for porcine reproductive and respiratory syndrome virus (PRRSV) and porcine circoviruses (PCVs). Enteric microorganisms are often collected from groundwater via dead-end ultrafiltration, but recovery of PRRSV and PCV with this method has not been assessed. We recovered PRRSV2 and PCV2 by dead-end ultrafiltration followed by polyethylene glycol (PEG) precipitation, nucleic acid extraction, and reverse-transcription quantitative real-time PCR. We also compared 2 commercial hemodialysis ultrafilters (Asahi Kasei Rexeed-25A, Nipro Elisio-25H) and compared PRRSV2 recovery in these filters to other waterborne microorganisms. On average, 8 ± 1% of PRRSV2 was recovered by dead-end ultrafiltration and PEG precipitation, compared to 25 ± 6% for adenovirus 41. Full-process recovery of bacteria in the same filters was 5–15%; Cryptosporidium parvum recovery was 42 ± 12%. PCV2 was detected in 4 of 12 replicate filters, but low stock concentrations precluded quantitative recovery estimates. Elisio-25H ultrafilters performed similarly to Rexeed-25A filters for all organisms tested and is an effective replacement for the Rexeed-25A, which is no longer available in the United States. Our recovery of PRRSV2 and PCV2 by dead-end ultrafiltration in the laboratory suggests that PRRSV2 detection limits are as low as 3–50 genomic copies/L in sample volumes of 100–1,500 L. Based on quantitative microbial risk assessment, these concentrations are relevant to PRRSV2 infection rates in the U.S. swine herd.

Journal of Veterinary Diagnostic Investigation

PFAS mixture composition and internal exposure profiles shape biological responses under field-realistic exposure

Per- and polyfluoroalkyl substances (PFAS) occur as complex mixtures, yet mixture-dependent biological effects under environmentally realistic exposure conditions remain poorly understood. We conducted multiyear (2018, 2019, 2021) continuous-flow, field-based exposures of male fathead minnows ( Pimephales promelas ) using a low-PFAS reference well (REF; sum of measured PFAS (∑PFAS) 0.1–0.2 μg L –1 ) and PFAS-contaminated groundwater from a fire-training area (FTA) at Joint Base Cape Cod, Massachusetts. Dilution treatments enabled separation of concentration and mixture effects. Groundwater from well FTA1 was perfluorooctanesulfonate (PFOS) dominated (∑PFAS 10–31 μg L –1 ), whereas groundwater from well FTA2 had higher concentrations and was enriched in perfluorooctanoate (PFOA) and diverse precursors (∑PFAS ∼ 80 μg L –1 ). Despite comparable plasma ∑PFAS and PFOS in FTA1–100% and FTA2–50% on day-7, cumulative mortality reached approximately 35% in FTA2–50% and 17% in FTA2–100%, and secondary sex trait expression was reduced by approximately 65–80% relative to REF, whereas sperm motility effects were mixture- and time-dependent. Plasma PFAS profiles were dominated by perfluorohexanesulfonate (PFHxS), PFOS, and sulfonamide precursors. Liver transcriptomics from REF-acclimated fish revealed robust disruption of metabolic, mitochondrial, and endocrine pathways that link PFAS mixture chemistry and internal exposure profiles to organismal outcomes, and testis transcriptomics provided complementary insight into reproductive impairment. These results indicate that PFAS mixture composition and internal exposure profiles, including precursor-associated differences, are important determinants of ecotoxicological outcomes under field-realistic conditions.

Massachusetts

Dendroseismological investigation of redwood trees along the North Coast section of the San Andreas Fault

Sequoia sempervirens (coast redwood) tree rings have the potential to annually resolve late-Holocene earthquakes on the northern San Andreas Fault based on direct (e.g., physical damage) and indirect (e.g., co-seismic environmental change) impacts, but scarcity of suitable samples and challenges crossdating this long-lived species have limited progress. More precise dating of the pre-1906 (penultimate) earthquake can improve hazard assessment and understanding of rupture segmentation. We target old trees (maximum >815 yr) along the North Coast section of the fault (increment cores via rope-climbing, 11 living trees; plunge cuts, 23 stumps) and employ complementary disturbance detection methods including radial-growth averaging (tree- and series-level), cataloging anatomical indicators (e.g., traumatic resin ducts, TRD), and dating structural components (e.g., reiterated trunks, leans). Multi-centennial ring-width chronologies at Fort Ross (1569−2023) and Gualala (1397−2023) promote continued study with incomplete crossdating limiting utilization of some series. Growth pulses (reductions, releases) and TRD dispersed across the record reflect dynamic environments that obfuscate detection of earthquake signals. The 1906 earthquake did not leave strong signatures on most trees, and when it did, within-tree response varied from normal presentation to discoloration, TRD, and missing rings. Synchrony of indicators at both locations identified 1678−1680 (6 of 15 trees) and 1698−1700 (8 of 16 trees) as the strongest disturbances among dated rings in the time range of the penultimate earthquake, peaking at 1698 (15.7 % of possible growth and anatomical indicators), but the triggering mechanisms for these events are unknown.

California

“Leaky weirs” capture alluvial deposition and enhance seasonal mountain-front recharge in dryland streams

“Leaky weirs” are rock structures installed in dryland streams, which are anchored into exposed bedrock, loosely cemented, and designed to allow water to slowly pass through. They are being tested at a ranch in southeastern Arizona, USA, to restore and conserve the historic range and desert wetlands. Data are collected to assess how leaky weirs impact surface water, subsurface water, and groundwater recharge—including stream discharge, timing, and depth of infiltration, and groundwater elevations. Three adjacent watersheds, two with outlets just below leaky weirs and one with leaky weirs farther upstream, were instrumented with water-level loggers, wildlife cameras, and crest stage instruments with temperature sensors in the soil. As most groundwater recharge is assumed to be focused along the mountain fronts in this region, mountain-block recharge is also evaluated to differentiate between the two using isotope analyses. Finally, a single, late-season flood event is scrutinized to consider the leaky weir effect on all monitored components in the water budget. Results indicated groundwater flow is primarily from the mountains to the east via older, regional mountain-block recharge. However, the development of shallow alluvial aquifers is supported by the leaky weirs, that slow flows, capture permeable sediments, and allow infiltration, thus enhancing mountain-front recharge. In turn, these new pockets of water help support the restoration of historic wetlands. Sediment accumulates where leaky weirs are installed, reducing flashy peak flows, and resulting in a series of infiltration ponds along the channel that support vegetation during growing seasons and recharge the shallow aquifer during non-growing seasons.

Arizona

Concentration-discharge relations and transient metal loads reveal spatiotemporal variability in solute-generation mechanisms in a mine-affected watershed

Concentration-discharge (CQ) relations are commonly used to understand geochemical and hydrologic controls on the generation of solutes in watersheds. Despite the widespread application of CQ relations, this technique has been infrequently applied to acid mine drainage (AMD) sites, but the CQ framework may allow mechanistic understanding of remedial outcomes such as impoundment of water within underground mines. Results of CQ analyses and changes in metal loads in an AMD affected watershed in Colorado, USA indicate that dissolved loads increased at many individual locations following water impoundment within mine workings. Although increased loads were observed at most individual locations, these increases were offset by a large decrease in loading from the largest mine. A loading analysis that included data from an instream monitoring location showed a statistically significant decrease in Fe and Zn after bulkhead emplacement, indicating a net positive effect of bulkheads. Streams generally displayed dilution CQ patterns whereas mines and springs showed either flushing or chemostatic patterns prior to bulkheading, which transitioned to chemostatic patterns following bulkheading, indicating a transition from dynamic to equilibrium geochemical processes. Saturation indices for sulfide and secondary minerals indicated that mines and springs were near equilibrium for phases including schwertmannite, fluorite, and gypsum. Saturation indices vary through time for mines suggesting progressive leaching of sulfide minerals as the mass of available minerals in the mine workings decreases. Together, these diverse analyses provide an integrated understanding of the variability in solute generating processes in this watershed and may inform remediation plans for similarly affected sites by indicating the nature of mineralogic controls on water quality.

Colorado

Land application of drill waste: A scope analysis

Drilling fluid waste land application, a process where drilling wastes are spread and tilled into the land surface, has become common in some petroleum-producing states, however, the potential benefits and risks of this practice are not well studied. Drilling fluids can be water- or oil-based and can have high concentrations of total soluble salts and total petroleum hydrocarbons. Comprehensive chemical characterization of these fluids is not well documented in the literature, and the extent of land application is largely unknown. We hypothesized that the land application of drill waste would fluctuate over time due to economic factors. To begin to understand the extent of historical and potential future land application, we analyzed data from over 5,800 drilling fluid land application permits collected by the Oklahoma Corporation Commission for years 2000, 2005, 2010, and 2015–2020. During the years studied, drilling fluid wastes were applied to more than 250,000 acres in Oklahoma, with over 54,000 thousand barrels (Mbbl) of liquids and nearly 21,000 Mbbl of solids applied. Land application is widespread (occurring in 59/77 counties), however recent drilling activity, land availability, and the economics of transportation have created conditions favorable for land application specifically in the Anadarko Basin. Land application can co-occur with sensitive areas, such as important groundwater and surface-water drinking sources and agricultural fields used for subsistence or feed crop production. Our approach for quantifying the extent of land application, along with further chemical characterization studies, can aid operators and land managers who are considering this practice in assessing the associated benefits and risks.

Oklahoma

The influence of postfire root strength decay on shallow landslide susceptibility in western Oregon

Severe wildfires can increase the potential for postfire landslides, partly due to the loss of vegetation and root reinforcement. This study investigates the multi-year dynamics of root strength following wildfire in coniferous forests of western Oregon and evaluates implications for postfire slope stability. Root tensile strength was measured through laboratory testing of 969 roots collected from 26 test pits over four postfire timeframes: unburned conditions, 4–12 months postfire (Cedar Creek, 2022), 24–35 months postfire (Holiday Farm, 2020), and 59–67 months postfire (Eagle Creek, 2017). Variables analyzed include root diameter, tensile thread strength, stiffness, progressive tensile strength with displacement, time-dependent strength and ductility, root area ratio, and cohesion. Results indicate a 50% reduction in root strength after wildfire, with the lowest values occurring around 4 years postfire. Projections indicate it could take 10–22 years following fire for root strength to recover to 70% and 90% of the prefire original root strength, respectively. This timeline indicates a multi-year window of vulnerability for shallow landslides that reaches a maximum approximately 4 years following fire. Brittle failure behavior was observed in burned root systems compared to unburned root systems, signaling a more abrupt loss of strength at yield. Simple slope stability analyses show that reduced root strength can lead to instability on more gentle slopes and under less saturation in comparison to unburned conditions. These findings highlight the critical role of root reinforcement in postfire slope stability and the long-term implications of wildfire disturbance on landslide susceptibility.

Oregon

Diverging mineral chemistry of iron and nickel throughout Earth’s changing redox conditions reveals foundation for their evolution as protein cofactors

Iron (Fe) and nickel (Ni) were both foundational to early metabolism, yet their biological trajectories diverged as Earth’s surface redox state changed. Here, we integrate mineral chemistry network analysis, protein metal-site coordination-sphere analysis, and curated redox comparisons to test how geochemistry and metalloprotein architecture co-evolved. Mineral network analyses show broader electronegativity variation and network diversity for Fe-bearing minerals through time relative to Ni-bearing minerals. In structural analyses of protein metal centers in a combined Fe/Ni protein structure set, it is shown that Fe- and Ni-associated environments differ in amino-acid composition, hydropathy structure, and cysteine representation. The greater chemical diversity and electronegativity variation in Fe minerals mirror the higher redox and structural versatility of Fe-binding proteins. The presence of Fe in a broader range of mineral and protein environments demonstrates the chemical adaptability of the metal, from the anoxic Archean to oxidative Earth surface conditions following the Great Oxidation Event. Iron, with its broad redox potential range in Fe-oxidoreductases, has a central role in both anaerobic and aerobic metabolisms. Nickel, by contrast, is less widespread in biology. Today, Ni is predominantly employed in deeply branching anaerobic pathways and by proteins with narrower redox potential ranges. Our results show that evolutionary processes, constrained by metal chemistry, habitually utilize Fe as a redox generalist while retaining Ni in specialized roles. The divergent paths of Ni and Fe, from rocks to proteins, demonstrate the intimate relationship between planetary geochemistry and metabolic origins on Earth and suggest that Fe/Ni geochemistry may inform habitability assessments in extraterrestrial environments when interpreted within specific planetary environmental contexts.

Life