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Scientific opportunities in the National Landscape Conservation System

The National Landscape Conservation System consists of unique and beautiful places across America’s landscapes where identified resources and values are protected and science is highlighted. The mission of the National Landscape Conservation System (NLCS), which is managed by the Bureau of Land Management and is often referred to as the agency’s National Conservation Lands, is to conserve, protect, and restore nationally significant landscapes for their cultural, ecological, and scientific values. This clear inclusion of science in the NLCS mission sets the stage for individual units to serve as places of learning, teaching, discovery, and innovation. Science is an integral part of managing the National Conservation Lands, and science conducted within and across the more than 900 units that make up the NLCS can inform and influence conservation and public land management well beyond its boundaries. Here, we highlight seven core aspects of National Conservation Lands that present valuable science opportunities: (1) the scientific values for which individual units are designated; (2) the many other resources, objects, and values within units; (3) the value of units as “control” sites for understanding the effects of activities such as mineral extraction that commonly occur elsewhere on multiple-use public lands but are often prohibited within National Conservation Lands; (4) the value of units for studying the effects of activities such as recreation that regularly occur and may be intensified on National Conservation Lands; (5) the high visibility of units, which draws strong interest and engagement from scientists, partners, and the public; (6) the functioning of the units as a network managed for a common purpose, which provides an opportunity to explore cross-cutting science questions across widely varying contexts and geographies; and (7) the opportunities units provide to promote and apply Indigenous Knowledge to scientific research to manage natural and cultural resources. Because of all of these characteristics, National Conservation Lands can serve as hubs for basic and applied science that can inform management of all public lands and resources into the future. We highlight these science opportunities through examples from existing units and suggest two actions that could help further science activities and impact on National Conservation Lands.

Parks Stewardship Forum

Rare earth element potential in coal and coal ash in the U.S. Gulf Coast

United States heavy reliance on imports of critical minerals (CMs), including rare earth elements (REEs), underscores the importance of development of domestic sources. The study objective was to quantify CM and REE concentrations in coal and coal ash in the US Gulf Coast region. CM and REE concentrations were measured for 118 samples from outcrops and 14 mines in the Gulf Coast. Results show that total REE + Yttrium (REY) concentrations (dry coal basis) are comparable to those of the upper continental crust (UCC) with localized hot spots, such as the Texas Gibbons Creek mine (REY ≤ ~ 2860 ppm). When normalized to UCC REY concentration (169 ppm, dry coal basis), REY to UCC ratios for Gulf Coast coal samples range from 0.1 to 17 (median ratio 0.6). REE extractability from lignites is high (median: 63%–93%) using environmentally benign weak acid. In addition to raw coal, coal ash from power plants could also serve as an REE source with a median ratio of REY in ash relative to coal of 4; however, extractability from coal ash is generally much lower (≤ 5% using the same weak acid as in coal). The median basket price for extracted REY as oxides from coal, assuming 70% extractability, is $3.2 per tonne of coal and $186 billion based on 58 billion metric tonnes of dry coal in the Gulf Coast. REEs important for magnets (Pr + Nd + Tb + Dy) account for ~ 80% of the total value. The corresponding median basket price for extracted REY as oxides from coal ash, assuming ~ 30% extractability, is ~$4.4 per tonne of ash and $1.2 billion based on 258 million tonnes of ash. REE production from coal would likely require co-products, such as activated carbon or humic acids, to attain economic viability. Production of REEs from coal ash could offset remediation costs related to potential water contamination. This reconnaissance study shows the potential for REE production from coal and coal ash in the Gulf Coast; however, carbon coproducts and/or societal benefits would likely be required for socioeconomic viability.

Alabama, Florida, Louisiana, Mississippi, Texas

Linking distribution and return-on-investment models to optimize woody management for prairie grouse in Nebraska

Grasslands in Nebraska, USA, face threats from agricultural conversion, urban development, and woody encroachment, all of which negatively affect prairie grouse ( Tympanuchus spp.) populations. To optimize conservation planning, Nebraska wildlife agencies developed probabilistic area-based surveys for greater prairie-chicken ( T. cupido ) and sharp-tailed grouse ( T. phasianellus ) to sample landscapes across a range of environmental conditions. This design improves historical surveys and enables the development of distribution models that quantitatively define habitat associations and support scenario-based conservation planning. Using survey data collected during 2020–2022, we modeled prairie grouse occurrence and abundance as functions of land cover, topography, and climate using Bayesian logistic and zero-inflated negative binomial models with regularized horseshoe priors. We then conducted a maximum potential return-on-investment analysis of woody cover treatments, assuming sustained treatment success, relative to projected impacts of woody encroachment on prairie grouse populations by 2050. Among modeled associations were a positive association with grasslands having low woody cover and a negative association with grasslands having high woody cover. Across the 3-year period, median estimated annual populations were 142,380 for greater prairie-chicken (range of 95% CIs across years = 68,821–277,615) and 64,154 for sharp-tailed grouse (range of 95% CIs across years = 27,550–146,559). Under projected woody encroachment, mean predicted population declines were 10% for greater prairie-chicken (range of 95% CIs = 7–14%) and 6% for sharp-tailed grouse (range of 95% CIs = 5–7%). Areas with high prairie grouse density and low treatment costs in 2021, and high projected woody encroachment and population loss by 2050, offered the greatest return on investment for woody management. Return on investment was greatest in the northwestern Shortgrass Prairie ecoregion (northwestern Nebraska) for sharp-tailed grouse and the eastern Sandhills ecoregion (central Nebraska) for both species. These models underscore the value of evidence-based, quantitative approaches for prioritizing conservation actions on working lands. Scenario-based modeling could be extended to guide other treatments, such as optimizing restoration (e.g., Conservation Reserve Program) or incentivizing grassland persistence in areas with predicted climate resilience.

Nebraska

Tapwater exposures, residential risk, and mitigation in a PFAS-impacted-groundwater community

Tapwater (TW) safety and sustainability are priorities in the United States. Per/polyfluoroalkyl substance(s) (PFAS) contamination is a growing public-health concern due to prolific use, widespread TW exposures, and mounting human-health concerns. Historically-rural, actively-urbanizing communities that rely on surficial-aquifer private wells incur elevated risks of unrecognized TW exposures, including PFAS, due to limited private-well monitoring and contaminant-source proliferation in urbanizing landscapes. Here, a broad-analytical-scope TW-assessment was conducted in a hydrologically-vulnerable, Mississippi River alluvial-island community, where PFAS contamination of the shallow-alluvial drinking-water aquifer has been documented, but more comprehensive contaminant characterization to inform decision-making is currently lacking. In 2021, we analyzed 510 organics, 34 inorganics, and 3 microbial groups in 11 residential and community locations to assess (1) TW risks beyond recognized PFAS issues, (2) day-to-day and year-to-year risk variability, and (3) suitability of the underlying sandstone aquifer as an alternative source to mitigate TW-PFAS exposures. Seventy-six organics and 25 inorganics were detected. Potential human-health risks of detected TW exposures were explored based on cumulative benchmark-based toxicity quotients ( ∑ TQ ). Elevated risks ( ∑ TQ ≥ 1) from organic and inorganic contaminants were observed in all alluvial-aquifer-sourced synoptic samples but not in sandstone-aquifer-sourced samples. Repeated sampling at 3 sites over 52–55 h indicated limited variability in risk over the short-term. Comparable PFAS-specific ∑ TQ for spatial-synoptic, short-term (3 days) temporal, and long-term (3 years quarterly) temporal samples indicated that synoptic results provided useful insight into the risks of TW-PFAS exposures at French Island over the long-term. No PFAS detections in sandstone-aquifer-sourced samples over a 3 year period indicated no PFAS-associated risk and supported the sandstone aquifer as an alternative drinking-water source to mitigate community TW-PFAS exposures. This study illustrated the importance of expanded contaminant monitoring of private-well TW, beyond known concerns (in this case, PFAS), to reduce the risks of a range of unrecognized contaminant exposures.

Wisconsin

Properties of solid bitumen formed during hydrous, anhydrous, and brine pyrolysis of oil shale: Implications for solid bitumen reflectance in source-rock reservoirs

Solid bitumen reflectance (BR o in %) is widely used as a thermal maturity proxy in source-rock reservoirs, yet solid bitumen texture and physical attributes may be affected by varying environmental constraints during its formation, e.g., water saturation, mineral catalysis, or salinity. Herein we investigated the development of solid bitumen properties during artificial maturation using three diverse (lacustrine to marine) oil shale samples containing abundant amorphous H-rich sedimentary organic matter (bituminite). The oil shales were treated via pyrolysis (320 °C, 72 h) using hydrous, anhydrous, and brine conditions, causing the development of a newly formed solid bitumen in the experiment residues from the thermal conversion of bituminite. The properties of the newly formed solid bitumen then were evaluated via geochemical screening tests, optical and electron microscopy, and infrared spectroscopy. Experimental residues also were treated via solvent extraction, allowing characterization of the effects of extraction on solid bitumen. Results showed that bituminite with higher resin and asphaltene components evolved to a solid bitumen with higher reflectance (as a percentage of the original value) when exposed to the same heat treatment, relative to bituminite with higher saturate and aromatic components. Aromatization of solid bitumen also was generally more pronounced in the presence of deionized water relative to anhydrous conditions, supporting prior observations. These results suggest the compositions of primary sedimentary organic matter, and the local concentration of water, affect the development of solid bitumen during thermal advance, potentially explaining the origin of multiple solid bitumen populations with varying reflectance in source-rock reservoir samples or in a single microscope field. Experiments using brine were inconclusive regarding enhanced/decreased aromatization, which could be attributed to the salinities of the brines used in the tests. Extraction of residues caused a consistent increase in BR o values, suggesting that migrating or expelled oils could cause an increase in BR o via natural solvation and absent an increase in temperature. This work provides insights into the development and evolution of BR o in source-rock reservoirs as a function of the composition of the original bituminite and changing environmental conditions, with potentially broad application for petroleum prospecting and resource estimation.

Colorado

Fluid inclusion constraints on the geometry of the magmatic plumbing system beneath Mauna Loa – Part 2: Xenoliths

Mauna Loa volcano erupts crystal-poor material at its summit and more crystal-rich material on its rift zones. Some of the more olivine-rich lava flows contain xenoliths with diverse mineralogy, including cumulate harzburgites with high-Mg# orthopyroxenes and high-Fo olivines (both > 84). Previous experimental work and thermodynamic modelling has proposed that high-Mg# orthopyroxenes only crystallize from Mauna Loa melts at high pressures (> 6 kbar, > 20 km), leading to suggestions that there is a region of sub-Moho magma storage at Mauna Loa in addition to the geophysically imaged magma reservoir at 2–5 km depth below the summit. We use melt and fluid inclusion barometry combined with thermodynamic models to further investigate this suggestion. Fluid inclusion data from harzburgites and dunitic xenoliths yield storage depths remarkably similar to those found in non-xenolithic crystals from lavas and tephras, with a clear peak at ~ 2–3 km (below the summit). Depths from melt inclusions in these xenoliths overlap with fluid inclusion pressures, ruling out the possibility of fluid inclusion re-equilibration during a period of stalling in a shallower reservoir. We examine five different thermodynamic models and find that the minimum pressure of olivine-orthopyroxene co-saturation varies by ~ 4 kbar (~ 12 km). These models also fail to predict that orthopyroxene is stable in ~ 15–80% of compositionally relevant experimental charges which grew orthopyroxene. Overall, this shows that phase stability modelling is an unreliable method of determining magma storage depth at Mauna Loa. We suggest that model discrepancies reflect a lack of experimental constraints on orthopyroxene stability at > 1200 ℃ and 0.01–5 kbar. Based on the presence of large oikocrystic orthopyroxenes completely enclosing rounded olivine chadacrysts, we suggest that these harzburgitic xenoliths formed through the reaction of intruding melts with olivine mush piles within the Mauna Loa edifice at ~ 3 km depth below the summit, with no need for a deeper storage reservoir. The predominance of pre-eruptive shallow storage means that there is more chance of detecting reservoir destabilization with geophysical monitoring techniques compared to a scenario where melts are supplied from sub-Moho reservoirs.

Hawaii

Inference of pattern-based geological CO2 sequestration and oil recovery potential in a commingled main pay and residual oil zone CO2-EOR flood

Several detailed studies have shown that residual oil zones (ROZs) can present significant resources for additional hydrocarbon recovery as well as subsurface carbon dioxide (CO 2 ) sequestration via enhanced oil recovery by injecting CO 2 (CO 2 -EOR). Field development strategies included new wells drilled dedicated to main pay zones (MPZ) and ROZs, or existing wells in MPZs deepened to ROZs for commingled injection-production using different well patterns. The latter presented a challenge when discerning the injection and production from each of the zones, and for subsequent quantification of CO 2 sequestration and EOR potential from different patterns and from the field. In this paper, an innovative method for analyzing commingled injections and productions from MPZs and ROZs, with application to pattern-based data from four staggered line drive patterns in Wasson Field's Denver Unit, Texas, USA, was developed. Decline curve and ratio-trend methods were used as means of history-matching and forecasting. Cumulative production-time and cumulative production-rate data for oil, gas, and water, as well as water-oil ratio (WOR) and gas-oil ratio (GOR), were analyzed along with injection data for time intervals covering major injection events in MPZ, or MPZ and ROZ combined. A combined analysis enabled inference of allocation of fluids into different zones during WAG (water alternating gas) injection and thereby estimation of CO 2 storage, utilization, and retention in different zones as a function of total injection. Results show that ROZs generally present higher CO 2 sequestration potential compared to MPZs, and a comparable incremental oil recovery factor of ∼20%, on average. Results based on ratio analysis further show that while the WOR trend of the pattern production is mostly dominated and controlled by ROZ, GOR is controlled by both intervals. Although the method relying on decline curves and the approach used in zonal fluid allocations are subject to their limitations, this study presents a practical and innovative well-pattern-based method to infer and forecast CO 2 sequestration and oil recovery quantities and fluid ratios from MPZs and ROZs in commingled operations and highlight the added potential offered by ROZs.

Texas

Influence of inherited structure on flexural extension in foreland basin systems: Evidence from the northern Arkoma basin and southern Ozark dome, USA

Extensional faults are key components of foreland basin systems. They form within the upper crust in response to flexure of the lithosphere and accommodate subsidence within the foredeep and forebulge depozones. Such faults are excellent proxies for orogenic system evolution and control the distribution of natural resources and hazards. However, the spatiotemporal evolution of flexural extension has not been documented previously at a regional scale, thereby limiting our understanding of underlying geodynamic controls. Here, we resolve late Paleozoic flexural extension in the northern Arkoma basin and southern Ozark dome, USA. We synthesize a large database of previous mapping, existing research, subsurface data, and geophysical data into 3D geologic and 2D kinematic models. Mesh surfaces representing several key horizons from the Carboniferous Period (ca. 335-306 Ma) were constructed. These surfaces were built from oil and gas well tops (n = ∼10,000) and surface geologic map contacts using an advanced kriging method. The mesh surfaces are offset by a complex 3D fault network, allowing detailed analysis of along-strike and down-dip variations in fault displacement. Analysis of the 3D model reveals a regular and repeated fault segmentation pattern wherein E -W striking, left- and foreland-stepping en échelon normal faults are segmented by inherited NE striking basement faults. Maximum vertical separation along the E -W normal faults is generally focused between the inherited NE-trending faults. This suggests that the inherited basement faults delocalized extensional strain during late Paleozoic normal faulting. Maximum vertical separation and fault localization may correlate to areas with high-amplitude positive magnetic anomalies interpreted as Mesoproterozoic granitic rocks. Speculative covariance of magnetic anomalies and fault displacements implies that the relatively strong basement granite concentrated stress, leading to localized faulting within the relatively thin sedimentary cover. Lastly, we show that flexural extension migrated southeast to northwest from the Chesterian-Morrowan (ca. 335-319 Ma) to the Desmoinesian (ca. 306 Ma). The migratory flexural extension may be explained by diachronous loading during Pangean assembly, or by synchronous loading but variable load compensation due to inherent factors.

Arkansas, Oklahoma

Solution-collapse breccia pipe uranium deposits of the southern Colorado Plateau, northwestern Arizona, USA

Some of the highest-grade uranium deposits in the United States occur in breccia pipes that formed by solution and collapse of sedimentary strata, which occur in the southern portion of the Colorado Plateau in northwestern Arizona. The host breccia pipes are up to 1200 m in vertical extent, average about 90 m in diameter, and can cross-cut strata from their base in the Mississippian Redwall Limestone to as stratigraphically high on some plateaus as the Triassic Chinle Formation. These uranium-base metal deposits are up to 600 m thick and formed within the breccia pipes where they transect the Permian Coconino Sandstone, Hermit Formation, and the Esplanade Sandstone. Of the hundreds of breccia pipes identified across this region, only a small percentage are known to contain mineralization. The main uranium ore mineral is uraninite that is intergrown with at least 20 base-metal sulfide minerals, which contribute Fe, Cu, Co, As, Pb, Zn, Ni, and Ag to the deposits. This study considered regional stratigraphy, sulfur isotope systematics, mineralogy, in situ dating, and compilation and analysis of previous work on the deposits. A comprehensive deposit model has not been published for these deposits. This analysis identified new additions to update the deposit model for these unusual, possibly unique deposits. Proposed modifications to the model include: (1) the source, mechanisms, timing of the base-metal sulfide mineral assemblages, and (2) the source, mechanism, and timing of the uranium mineralization. Sulfide and uranium deposition are shown to be separate mineralization events. The study proposes the possible role of gypsum as a source of sulfur for the sulfide minerals in the deposits. Groundwaters carrying uranium encountered the preexisting sulfides in breccia pipes, reducing the uranyl ions, and precipitating U oxide (as uraninite). Analysis of the regional stratigraphy recognized that numerous beds of gypsum are in the strata that lie only tens of meters above the breccia pipe deposits. In the breccia pipe region, if these stratigraphic units (Toroweap and Kaibab Formations) do not contain gypsum layers then the underlying pipes are not mineralized; where these Permian gypsum layers do occur, breccia pipes can host mineralization. This new understanding should be useful in identifying the prospective region for mineralized pipes.

Arizona

Groundwater structures fish growth and production across a riverscape

Landscapes are composed of habitat patches and conditions that vary across space and time. While habitat variability and complexity can support important ecological processes and ecosystem services, the dynamic nature of habitats can also constrain organismal growth and production as optimal conditions are fleeting. In riverine ecosystems, groundwater discharge to streams stabilises water temperature and flow regimes, thus mediating how habitat complexity is expressed. Yet, how stable habitats structure growth and production within the broader landscape matrix is not well understood. In this study, we explored the effects of groundwater on spatiotemporal variation in growth and production for juvenile Yellowstone cutthroat trout ( Oncorhynchus virginalis bouvieri ) across the upper Snake River catchment, Wyoming, USA. We combined machine learning techniques and remotely sensed landscape data to estimate groundwater availability across the river network, which we linked to stream temperature regimes and conspecific density. We then used Bayesian hierarchical models to quantify the effects of temperature, density and groundwater on spatiotemporal variation in fish growth and production in 52 focal reaches. Finally, we predicted body size trajectories and trends in total production continuously over both space and time to understand the effect of groundwater at the riverscape scale. Groundwater discharged to streams where topography changes abruptly in valley-bottom areas underlain by coarse glacial deposits. Groundwater stabilised temperature regimes and was associated with high trout densities. Temperature and density, in turn, interacted to influence growth rates: growth increased strongly with temperature, but this effect was reduced when density was high. Accordingly, variation in groundwater availability among stream reaches diversified growth and production regimes. In reaches with low groundwater availability, growth and production declined over time from summer maxima. In contrast, in reaches with high groundwater availability, temporal trends in growth and production were hump-shaped—peaking in autumn—and mean production was greater. At the riverscape scale, temporal asynchrony in growth rates generated convergent spatial variation in growth capacity, but—when combined with density—led to the formation of distinct hotspots of production. Our results demonstrate how groundwater, an important driver of aquatic ecosystem heterogeneity, structures trout growth and production across space and time. Importantly, rare, but stable habitats may disproportionately affect ecological processes and serve as key sources of population diversity at larger spatial scales.

Wyoming

Isotopic evaluation of the National Water Model reveals missing agricultural irrigation contributions to streamflow across the western United States

The National Water Model (NWM) provides critical analyses and projections of streamflow that support water management decisions. However, the NWM performs poorly in lower-elevation rivers of the western United States (US). The accuracy of the NWM depends on the fidelity of the model inputs and the representation and calibration of model processes and water sources. To evaluate the NWM performance in the western US, we compared observations of river water isotope ratios ( 18 O / "> 16 O and 2 H / "> 1 H expressed in δ notation) to NWM-flux-estimated (model) river reach isotope ratios. The modeled estimates were calculated from long-term (2000–2019) mean summer (June, July, and August) NWM hydrologic fluxes and gridded isotope ratios using a mass balance approach. The observational dataset comprised 4503 in-stream water isotope observations in 877 reaches across 5 basins. A simple regression between observed and modeled isotope ratios explained 57.9 % ( δ 18 O) and 67.1 % ( δ 2 H) of variance, although observations were 0.5 ‰ ( δ 18 O) and 4.8 ‰ ( δ 2 H) higher, on average, than mass balance estimates. The unexplained variance suggest that the NWM does not include all relevant water fluxes to rivers. To infer possible missing water fluxes, we evaluated patterns in observation–model differences using δ 18 O diff ( δ 18 O obs − δ 18 O mod ) and d diff ( δ 2 H diff - 8 ⋅ δ 18 O diff "> ). We detected evidence of evaporation in observations but not model estimates (negative d diff and positive δ 18 O diff ) at lower-elevation, higher-stream-order, arid sites. The catchment actual-evaporation-to-precipitation ratio, the fraction of streamflow estimated to be derived from agricultural irrigation, and whether a site was reservoir-affected were all significant predictors of d diff in a linear mixed-effects model, with up to 15.2 % of variance explained by fixed effects. This finding is supported by seasonal patterns, groundwater levels, and isotope ratios, and it suggests the importance of including irrigation return flows to rivers, especially in lower-elevation, higher-stream-order, arid rivers of the western US.

Hydrology and Earth Systems Science

Geological context and significance of the clay-sulfate transition region in Mount Sharp, Gale crater, Mars: An integrated assessment based on orbiter and rover data

On Mars, phyllosilicate (“clay”) minerals are often associated with older terrains, and sulfate minerals are associated with younger terrains, and this dichotomy is taken as evidence that Mars’ surface dried up over time. Therefore, in situ investigation of the Mount Sharp strata in Gale crater, which record a shift from dominantly clay-bearing to sulfate-bearing minerals, as seen in visible−near-infrared orbital reflectance spectra, is a key science objective for the Mars Science Laboratory (MSL) Curiosity rover mission. Here, we present regional (orbiter-based) and in situ (rover-based) evidence for a low-angle erosional unconformity that separates the lacustrine and marginal lacustrine deposits of the Carolyn Shoemaker formation from the dominantly eolian deposits of the lower Mirador formation within the orbitally defined clay-sulfate transition region. The up-section record of wetter (Carolyn Shoemaker formation) to drier (lower Mirador formation) depositional conditions is accompanied by distinct changes in diagenesis. Clay minerals occur preferentially within the Carolyn Shoemaker formation and are absent within the lower members of the Mirador formation. At and above the proposed unconformity, strata are characterized by an increase in diagenetic nodules enriched in X-ray amorphous Mg-sulfate. Early clay formation in the Carolyn Shoemaker formation may have created a hydraulic barrier such that later migrating magnesium- and sulfur-rich fluids accumulated preferentially within the lower members of the Mirador formation. The proposed unconformity may have also acted as a fluid conduit to further promote Mg-sulfate nodule formation at the Carolyn Shoemaker−Mirador formation boundary. These results confirm an association of the clay-sulfate transition with the drying of depositional environments, but they also suggest that at least some orbital sulfate signatures within the region are not time-congruent with the environmental signals extracted from primary sedimentology. Our findings highlight that complex interactions among primary depositional environment, erosion, and diagenesis contribute to the transition in clay-sulfate orbital signatures observed in the stratigraphy of Mount Sharp.

GSA Bulletin

James Buttle review: The characteristics of baseflow resilience across diverse ecohydrological terrains

The dynamic storage of aquifers is the portion of groundwater that can potentially drain to any given point along a stream to create baseflow. Baseflow typically occurs year-round in perennial streams, though the characteristics and stability of dynamic storage are often most important to instream processes during extended dry periods (without precipitation and snowmelt) when runoff and quickflows are minimised. The term ‘baseflow resilience’ is defined for this review as the tendency of baseflow in streams to maintain a consistent volume and water quality year to year while under stress from climate variability and extremes, along with anthropogenic stressors such as water withdrawals, land use change, and water quality degradation. ‘Baseflow resilience’ has, in part, a user-defined meaning spanning water supply and water quality variables of primary interest. Watershed characteristics that directly impact resilience can often produce non-intuitive feedbacks that enhance some attributes of baseflow while simultaneously impairing others. For example, permeable stream corridor geology creates strong stream-groundwater hydrologic connectivity, yet fast groundwater drainage via preferential high-permeability flowpaths can lead to streamflow not being sustained during extended dry periods. Also, shallow groundwater sources are generally more immediately vulnerable to extreme events, warming, salinization, transpiration, and precipitation drought, compared to deeper groundwater. Yet baseflow drought in streams influenced by deeper groundwater can lag precipitation drought by years, and contaminant legacies may propagate through deep groundwater flowpaths to receiving waters for decades to centuries. Finally, irrigation withdrawals can intercept groundwater that would have drained to streams, and the application of irrigation may leach contaminants from the soil zone by unnaturally raising water tables, yet irrigation return flows can sustain baseflow and groundwater-dependent habitats in semiarid areas. This review covers the concept of hydrologic resilience in the context of stream baseflow processes and summarises the common hydrogeological controls on, and multiscale stressors of, dynamic groundwater storage. Further, we present several quantitative metrics to assess a range of water supply to water quality baseflow characteristics using both broadly available and boutique data types, a subset of which are demonstrated using data from the Delaware River Basin, USA.

Delaware River Basin

Metal fingerprints of Eocene rhyolite magmas coincident with Carlin-type gold deposition in Nevada USA

Eocene magmatic systems contemporaneous with world-class Carlin-type Au deposits in Nevada (USA) have been proposed by some researchers as a key ingredient for Au mineralization, though evidence conclusively demonstrating their genetic relationship remains tenuous. This study provides the first direct evidence of the pre-eruptive metal budget of volatile- and metal-charged silicic magmas coincident in time (~41 to 34 Ma) and space (within 5 km) with Carlin-type Au deposits. We characterize the pre-eruptive metal fingerprints of these diverse magmatic systems to assess their potential as sources of metals for Carlin-type Au mineralization. Metal abundances from quartz-hosted melt inclusions (Au, Te, Ag, Sb, Tl, Mo, W, Sn, As, Pb, Co, Cu, Ni, and Zn) characterized in situ by SHRIMP-RG and LA-ICP-MS represent our best (and only) estimates for the pre-eruptive metal budget in these systems. Median metal concentrations are generally within one order of magnitude of average upper crust and average continental rhyolite values. But there are two notable exceptions, with median Au contents extending >1 order of magnitude higher than average upper crust and median Cu contents ranging >1 order of magnitude lower than upper crust. Despite this, melts contain lower Au/Cu (<0.1), Au/Ag (<5), and Au/Tl (<0.3) than most ore-grade Carlin-type rock samples and quartz-hosted fluid inclusions, regardless of their age and timing relative to nearby Carlin-type Au mineralization. The metal fingerprints of these magmatic systems, de-fined both by traditional and multivariate compositional data analysis techniques, are distinct from one another. Yet none are particularly specialized, e.g., high Au/Cu, in terms of being ideal ingredients as postulated by magmatic models for Carlin-type Au mineralization. Magmatic Au contents do not appear to be correlated with rhyolite “flavors” in the way that Cu, Sn, and Nb contents are. Fluid/melt partitioning modeling and magma volume estimates support the idea that a diverse array of non-specialized silicic magmas could feasibly contribute some or potentially all of the Au, Ag, and Cu in Carlin-type systems. The compositional diversity among contemporaneous magmatic systems could possibly contribute to some of the diversity observed across Carlin-type Au districts in Nevada.

Nevada

The addition of 144Nd atomic mass to routine ICP-MS analysis as a Quick Screening Tool for Approximating Rare Earth Elements (Q-STAR) in natural waters

Rare earth elements (REEs) are a class of critical minerals, all of which can have supply chain vulnerability that impacts economic security. These elements are widely measured in environmental matrices via inductively coupled plasma mass spectrometry (ICP-MS); however, successful quantification can require time-consuming, sample-specific optimization. While a sample-by-sample approach is appropriate for targeted quantification studies, this approach is not suitable for mineral exploration efforts where rapidly screening thousands of samples for the presence of REEs is desired. Here, we demonstrated the use of a Quick Screening Tool for Approximating REEs (Q-STAR) to detect REEs in surface water and groundwater matrices, collected as part of existing environmental studies. A mass-to-charge ratio of 144 ( m / z = 144) was added to an ICP-MS method to screen for REEs in filtered water samples submitted for metals analyses to the U.S. Geological Survey (USGS) National Water Quality Laboratory. We detected the presence of REEs above a reference threshold of 1200 counts per second in 18 % of pre-selected 6626 samples. Using this screened dataset, we mapped estimated dissolved REE concentrations across the United States in relation to ecoregions and underlying geology. Data are constrained to where sample collection took place but nevertheless show estimated aqueous dissolved REE concentrations on a geographic scale that has not yet been studied. To validate Q-STAR, REEs were measured in a USGS standard reference sample, a subset of 88 archived filtered water samples, and in fresh filtered surface water samples. Our targeted analyses demonstrated a strong linear relationship between Q-STAR predicted and measured values in all archived samples for Nd (r 2 = 0.94), and light REEs (LREEs) such as lanthanum (La) (r 2 = 0.93), praseodymium (Pr) (r 2 = 0.94) and samarium (Sm) (r 2 = 0.94). Using Q-STAR screen values, nine field sites were identified and surface water samples recollected to confirm the continued presence of Nd and LREEs. Q-STAR can be used to screen an unlimited number of water samples for the presence of REEs prior to time-intensive and costly quantitative analyses and to generate large REE datasets for further investigation.

Journal of Geochemical Exploration

A geospatial analysis of water-quality threats from orphan wells in principal and secondary aquifers of the United States

Throughout the history of oil and gas production in the United States, millions of wells have been drilled for exploration and energy production. Hundreds of thousands of unplugged wells are no longer actively producing and are currently under orphan status, with no responsible party obligated for plugging. Orphan wells can pose threats to water resources by providing pathways for contaminants such as hydrocarbons and brines to migrate into water-supply aquifers. In this study, we investigate the potential threats to groundwater resources posed by orphan wells at the national scale. Water-quality data is extremely sparse in relation to orphan wells nationally and may not be suitable for identifying contamination from oil and gas development. We used geospatial and statistical methods to evaluate which principal and secondary aquifer systems may be most susceptible to contamination from orphan wells. Analysis involved three sets of susceptibility factors including: 1) factors related to the number and density of orphan wells; 2) factors that can threaten well integrity and contribute to transport of contaminants; and 3) factors related to groundwater withdrawal rates and the affected populations/communities in the event of water quality disturbances. From a dataset of 117,672 documented orphan wells, 64,203 fall within a principal aquifer system, while the remainder fall within a secondary aquifer system. By assessing the combination of well integrity and hydrogeologic factors within these aquifer systems, five groupings of principal aquifers were identified, where groups ranged from aquifer systems with high numbers of orphan wells, multiple well integrity threats and high withdrawals, to aquifers with a relatively low number of orphan wells, limited well integrity threats and minimal water use. Three regions of the country emerge containing aquifers with higher susceptibility to contamination from orphan oil and gas wells. These regions include 1) The Appalachian Basin (including the Pennsylvanian Aquifer System), 2) The Gulf Coast Aquifers (including the Coastal Lowlands Aquifer system) and 3) The California Aquifers (including the California Coastal Basin Aquifer system). This work is the first multivariate geospatial investigation of orphan wells and groundwater resources on a national scale, and sheds light on which aquifers are most susceptible to groundwater contamination from orphan wells.

Science of the Total Environment

Evaluation of solid bitumen created from marine oil shale bituminite under hydrous and anhydrous pyrolysis conditions

To test the influence of environmental conditions on aromaticity of solid bitumen generated during petroleum generation, four organic-rich (26–36 wt% total organic carbon) oil shale samples collected from the Neoproterozoic–Lower Cambrian restricted marine Salt Range Formation in the upper Indus Basin, Pakistan, were pyrolyzed under hydrous and anhydrous conditions. Experiments used closed system batch reactors at subcritical water temperatures between 300 and 370°C for 72 h. Thermal conversion of bituminite in the Salt Range oil shales created a newly formed solid bitumen, similar to previous observations from experiments on the Eocene lacustrine Green River Formation Mahogany zone oil shale. Newly formed solid bitumen in the Salt Range Formation oil shales generally has higher reflectance (R o ) in hydrous residues compared to anhydrous experiments subjected to the same time-temperature conditions, also similar to prior observations. This finding supports the hypothesis that radical disproportionation is favored in the presence of hydrogen contributed by water, promoting aromatization in the solid bitumen residue with concomitant increased expulsion of saturated hydrocarbons. Indigenous solid bitumen (and vitrinite in a comparison sample) also shows higher reflectance values in hydrous versus anhydrous residues, indicating that additional aromatization in the presence of exogenous hydrogen occurs both in newly formed organic matter and in organic matter that is present throughout the experiment. Despite similarities in their bulk rock geochemical screening parameters, R o evolution shows different trajectories amongst the four Salt Range oil shales, suggesting as-yet undetermined differences in kinetic properties which are probably related to differences in a priori chemical composition. These results have implications for the use of solid bitumen reflectance (BR o ) as a thermal proxy, suggesting BR o values and appearance could vary as a function of the concentration of water. Variation in water concentration may be present at the reservoir or formation scale, but may also be present at a much finer scale in tight oil shales where permeability is several orders of magnitude lower than conventional reservoirs. Therefore, local variations in the presence of water potentially could explain substantial variation in BR o values and appearance in closely spaced source rock samples and even within an individual microscope field.

Journal of Analytical and Applied Pyrolysis

Using stable oxygen isotope dual-inlet isotope-ratio mass spectrometry to elucidate uranium transport and mixed 230Th/U calcite formation ages at the seminal Devils Hole, Nevada, natural laboratory

Rationale Vein calcite in Devils Hole has been precipitating continuously in oxygen-isotope equilibrium at a constant temperature for over 500 000 years, providing an unmatched δ 18 O paleoclimate time series. A substantial issue is that coeval calcite (based on matching δ 18 O values) has uranium-series ages differing by 12 000 years. Methods An unparalleled high-accuracy δ 18 O chronology series from continuously submerged calcite was used to correct the published uranium-series ages of non-continuously formed calcite in two cores, cyclically exposed by water-table decline during glacial–interglacial transitions. This method relies on the premise that the δ 18 O values of coevally precipitated calcite are identical, allowing matching calcite δ 18 O values to establish formation ages. Results Exposed calcite can have apparent ages that are 12 000 years too young due to unrecognized uranium mobility and resulting mixed ages identified in over 50 mixed uranium-series ages from previous studies. Secondary uranium in fluids, sourced from the formation or dissolution of porous carbonate deposits (folia) with high uranium-238 ( 238 U) concentrations, has migrated up to 10 mm into vein calcite. Conclusions The continuously submerged Devils Hole δ 18 O chronology is not explained by orbital forcing. Rather, this chronology represents a regional climate record in the southern Great Basin of sea-surface-temperature (SST) variations off California, variations that preceded the last and penultimate deglaciations by 5000 to approximately 10 000 years. Temporal discrepancies between the continuously submerged Devils Hole chronology and other regional δ 18 O records (e.g., the Leviathan chronology) can be explained by unrecognized cryptic, pernicious uranium mobility, leading to model estimations that may be thousands of years younger than actual ages. Consequently, paleo-moisture availability, water-table, and groundwater recharge models based on these mixed uranium-series ages are too young by as much as 12 000 years. The potential for post-formation uranium addition in subaerial cores and speleothems underscores the need for caution in uranium-series dating, highlighting δ 18 O time-series comparisons as a method for identifying mixed ages.

Nevada