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With increasing battery demand comes a need for diversified Li sources beyond brines. Among all Li-bearing minerals, spodumene is most often used for its high Li content and natural abundance. However, the traditional approach to process spodumene is costly and energy-intensive, requiring the mineral be transformed from its natural α to β phase at >1000 °C. Acid leaching is then applied, followed by neutralization to precipitate Li2CO3. In this work, we report an alternative method to extract Li directly from α-spodumene, which is performed at lower temperatures and avoids the use of acids. It is shown that Li2CO3 is formed with >90% yield at 750 °C by reacting α-spodumene with Na2CO3 and Al2O3. The addition of Al2O3 is critical to reduce the amount of Li2SiO3 that forms when only Na2CO3 is used, instead providing increased thermodynamic driving force to form NaAlSiO4 and Li2CO3 as the sole products. We find that this reaction is most effective at 4 h, after which volatility limits the yield. Following its extraction, Li2CO3 can be isolated by washing the sample using deionized water. This energy-saving and acid-free route to obtain Li2CO3 directly from spodumene can help meet the growing demand for Li.

Terrestrial production and export of dissolved organic and inorganic carbon (DOC and DIC) to streams depends on water flow and biogeochemical processes in and beneath soils. Yet, understanding of these processes in a rapidly changing climate is limited. Using the watershed-scale reactive-transport model BioRT-HBV and stream data from a snow-dominated catchment in the Rockies, we show deeper groundwater flow averaged about 20% of annual discharge, rising to ∼35% in drier years. DOC and DIC production and export peaked during snowmelt and wet years, driven more by hydrology than temperature. DOC was primarily produced in shallow soils (1.94 ± 1.45 gC/m2/year), stored via sorption, and flushed out during snowmelt. Some DOC was recharged to and further consumed in the deeper subsurface via respiration (−0.27 ± 0.02 gC/m2/year), therefore reducing concentrations in deeper groundwater and stream DOC concentrations at low discharge. Consequently, DOC was primarily exported from the shallow zone (1.62 ± 0.96 gC/m2/year, compared to 0.12 ± 0.02 gC/m2/year from the deeper zone). DIC was produced in both zones but at higher rates in shallow soils (1.34 ± 1.00 gC/m2/year) than in the deep subsurface (0.36 ± 0.02 gC/m2/year). Deep respiration elevated DIC concentrations in the deep zone and stream DIC concentrations at low discharge. In other words, deep respiration is responsible for the commonly-observed increasing DOC concentrations (flushing) and decreasing DIC concentrations (dilution) with increasing discharge. DIC export from the shallow zone was ~66% of annual export but can drop to ∼53% in drier years. Numerical experiments suggest lower carbon production and export in a warmer, drier future, and a higher proportion from deeper flow and respiration processes. These results underscore the often-overlooked but growing importance of deeper processes in a warming climate.

The presence of toxic metals in tobacco smoke is well documented. However, few studies have quantified trace metals in secondhand smoke (SHS) and thirdhand smoke (THS). Their presence in indoor air can contribute to nonsmokers’ exposures and health effects. In this study, emission and deposition rates of toxic trace metals were determined, and their airborne concentration in typical indoor scenarios was predicted. PM2.5 was collected on Teflon-coated filters at various times following a smoking event in a room-sized chamber over a 43 h period. The concentration of 28 trace metals was determined by extraction and analysis using inductively coupled plasma-triple quadrupole-mass spectrometry (ICP-QQQ-MS). Emission and indoor deposition rates of cadmium, arsenic, chromium, manganese, beryllium and selenium were determined, and used to predict concentrations expected in a smokers’ home and a smoking bar. In most of the considered scenarios, average indoor concentrations of Cd, As, and Cr exceeded their corresponding cancer risk thresholds and, in some cases, also noncancer reference exposure levels, more than 3 h after smoking ended. The fraction of cadmium that remained airborne was significantly higher than those of other metal traces and that of PM2.5, suggesting an association of Cd traces with small particles.

Summer streamflow predictions are critical for managing water resources; however, warming-induced shifts from snow to rain regimes impact low-flow predictive models. Additionally, reductions in snowpack drive earlier peak flows and lower summer flows across the western United States increasing reliance on groundwater for maintaining summer streamflow. However, it remains poorly understood how groundwater contributions vary interannually. We quantify recession limb groundwater (RLGW), defined as the proportional groundwater contribution to the stream during the period between peak stream flow and low flow, to predict summer low flows across three diverse western US watersheds. We ask (a) how do snow and rain dynamics influence interannual variations of RLGW contributions and summer low flows?; (b) which watershed attributes impact the effectiveness of RLGW as a predictor of summer low flows? Linear models reveal that RLGW is a strong predictor of low flows across all sites and drastically improves low-flow prediction compared to snow metrics at a rain-dominated site. Results suggest that strength of RLGW control on summer low flows may be mediated by subsurface storage. Subsurface storage can be divided into dynamic (i.e., variability saturated) and deep (i.e., permanently saturated) components, and we hypothesize that interannual variability in dynamic storage contribution to streamflow drives RLGW variability. In systems with a higher proportion of dynamic storage, RLGW is a better predictor of summer low flow because the stream is more responsive to dynamic storage contributions compared to deep-storage-dominated systems. Overall, including RLGW improved low-flow prediction across diverse watersheds.

Lithium-aluminum layered double hydroxides (LDHs) selectively sorb lithium from brines, concentrating and purifying this critical element for subsequent conversion to active battery components. Lithium ion partitioning into lattice vacancies within the LDH structure is selectively enhanced with iron doping. However, this process leads to a highly coupled set of intercalation interactions whose mechanisms are challenging to assess in situ. Here, we show that iron modulates the size- and shape-dependent composition of LDHs and imposes a powerful control on lithium sorption processes in complex fluids. We observe fundamental units of LDH layers and aluminum ferrihydrite nanoclusters that (dis)assemble to form at least five distinct particle types that influence LDH lithium capacity and cyclability. Importantly, lithium sorption is controlled by feedbacks arising from the dynamic interconversion of planar stacks and scrolls of LDH layers, which exchange lithium, water, and other species in the process of (un)rolling due to similar energy scales of hydration, sorption, and deformation. Under appropriate iron redox conditions, the cycling efficiency and stability of lithium sorption can be optimized for the range of lithium concentrations found in many natural brines.

The authors regret that in the original article, the kinetic fractionation factors (KFFs) related to the CO2 hydroxylation reaction (CO2(aq) + OH– → HCO3–) were calculated using atmospheric δ18OCO2 values of 0.0 ± 0.5 ‰ (VPDB) while the correct values are 10.25 ± 0.5 ‰ (VPDB). We erroneously employed the atmospheric δ18OCO2 values from the NOAA CO2 global network (Trolier et al., 1996) by not converting atmospheric δ18OCO2 from the VPDB-CO2 scale to the VPDB scale through the following expression (e.g. Srivastava and Verkouteren, 2018): [Formula presented] This correction affects the reported oxygen isotope KFFs for CO2 hydroxylation to form HCO3– prior to CaCO3 precipitation. We have corrected Table 7 and Fig. 13 accordingly (see below). The composition of atmospheric CO2 was also incorrectly plotted on the VPDB scale in Figs. 1, 8 and 15 of our original manuscript based on previous works (Fig. 8 in Clark and Fontes, 1990; Fig. 2 in Clark et al., 1992). Importantly, the modelling outputs and main conclusions of the original article are not affected by these corrections. Nevertheless, the updated KFFs resolve an apparent discrepancy between the laboratory and field studies in our original article. Moreover, the oxygen isotope KFF for CO2 hydroxylation now displays a positive temperature dependence over the 4–28 °C range, which was not statistically significant in the original article (Fig. 13c, r2 = 0.86, n = 10, p-value

Fractures are integral to the hydrology and geochemistry of watersheds, but our understanding of fracture dynamics is very limited because of the challenge of monitoring the subsurface. Here we provide evidence that long-term, high-frequency measurements of the river concentration of the ultra-trace element thorium (Th) can provide a signature of bedrock fracture processes spanning neighboring watersheds in Colorado. River Th concentrations show abrupt (subdaily) excursions and biexponential decay with approximately 1-day and 1-week time constants, concentration patterns that are distinct from all other solutes except beryllium and arsenic. The patterns are uncorrelated with daily precipitation records or seasonal trends in atmospheric deposition. Groundwater Th analyses are consistent with bedrock release and dilution upon mixing with river water. Most Th excursions have no seismic signatures that are detectable 50 km from the site, suggesting the Th concentrations can reveal aseismic fracture or fault events. We find, however, a weak statistical correlation between Th and seismic motion caused by distant earthquakes, possibly the first chemical signature of dynamic earthquake triggering, a phenomenon previously identified only through geophysical methods.

Quantifying flow and transport from hillslopes is vital for understanding water quantity and quality in rivers, but remains obscure because of limited subsurface measurements. Using measured hydraulic conductivity K profiles and water balance over a single year to calibrate a transmissivity feedback model for a hillslope in the East River watershed (Colorado) proved unsatisfactory for predicting flow over the subsequent years. Well-constrained field-scale K were obtained by optimizing subsurface flux predictions over years having large differences in recharge, and by including estimates of interannual transfer of excess snowmelt recharge. Water and solute exports during high snowmelt recharge occur predominantly via shallow groundwater flow through weathered rock and soil because of their enlarged transmissivities under saturated conditions. Conversely, these shallow pathways are less active in snow drought years when the water table remains deeper within the weathering zone. Hillslope soil water monitoring showed that rainfall does not infiltrate deeply during summer and fall months, and revealed water losses consistent with model ET predictions. By combining water table-dependent fluxes with pore water chemistry in different zones, time-dependent rates of solute exports become predictable. As an example, calibrated K were combined with dissolved nitrogen concentrations in pore waters to show the snowmelt-dependence of reactive nitrogen exported from the hillslope, further supporting the recent finding that the weathering zone is the dominant source of reactive nitrogen at this site. Subsurface export predictions can now be obtained for wide ranges of recharge based on measurements of water table elevation and profiles of pore water chemistry.

Mental State Language (MSL) is language that refers to individuals' inner states, including terms relating to "emotion," "desire-&-preference," "perception" and "cognition." This study explores the nature of eight Chinese educators' MSL in their interactions with infants during structured and free play. In total, 3169 language messages (one message includes a subject and a verb) were analyzed and it was revealed that MSL messages make up 7.7% of the educators' language. In conversational interactions, educators' MSL appeared more frequently in structured than in free play. The "desire-&-preference" terms were used most frequently and tended to trigger short conversational interactions (3-4 turns). Combining the analysis of communicative functions ("question," "statement," "command," "offer"), MSL of "cognition" and "perception" presented in "question" facilitated long conversational interactions (5 turns or above). These findings inform educators about how to use MSL effectively. It raises the consideration of balancing structured and free play in nursery routines that could vary in different cultures.

【Objective】 Soil salinization is one of many factors faced by cotton production in Xinjiang. Improving irrigation is one way to mitigate their detrimental impact. In this paper, we present an innovative drip irrigation system to ameliorate the effect of soil salinization and conserve water resources. 【Method】 The proposed method was based on that under drip irrigation, salt accumulates in the periphery of the wetted zone around the drip emitters. We reconfigured the conventional drip irrigation system into a system consisting of three-capillary tubes with staggered emitters. Parameters, including spacing between the capillary tubes, drip layout patterns, irrigation amount, and salt leaching were determined experimentally to elucidate its efficacy on salt migration in the wetted zones. 【Result】 Keeping soil properties and water quality consistent, we implemented the staggered delivery of water through the system in a cotton field. After six rounds of irrigation, soil samples were collected from the wetted zone to assess salt content in it. The vertical salt content distribution at a location 40 cm from the wetted zone decreased from 105.21 g/kg to 49.015 g/kg. This means that the proposed system effectively increased the desalination of the root zone and resulted in a reduction in annual saltwater usage by three times per year, compared with conventional drip irrigation. 【Conclusion】 The expansion of the desalination zone in the root zone is contingent on factors such as soil bulk density, irrigation method, frequency, drip patterns, soil salinity, irrigation water salinity, and irrigation cycles. As irrigation rounds increase, the desalination range grows. The method hence offers a promising strategy for managing saline-alkali lands while in the meantime optimizing water use efficiency.

BackgroundBiogeochemical exports from watersheds are modulated by the activity of microorganisms that function over micron scales. Here, we tested the hypothesis that meander-bound regions share a core microbiome and exhibit patterns of metabolic potential that broadly predict biogeochemical processes in floodplain soils along a river corridor.ResultsWe intensively sampled the microbiomes of floodplain soils located in the upper, middle, and lower reaches of the East River, Colorado. Despite the very high microbial diversity and complexity of the soils, we reconstructed 248 quality draft genomes representative of subspecies. Approximately one third of these bacterial subspecies was detected across all three locations at similar abundance levels, and ~ 15% of species were detected in two consecutive years. Within the meander-bound floodplains, we did not detect systematic patterns of gene abundance based on sampling position relative to the river. However, across meanders, we identified a core floodplain microbiome that is enriched in capacities for aerobic respiration, aerobic CO oxidation, and thiosulfate oxidation with the formation of elemental sulfur. Given this, we conducted a transcriptomic analysis of the middle floodplain. In contrast to predictions made based on the prominence of gene inventories, the most highly transcribed genes were relatively rare amoCAB and nxrAB (for nitrification) genes, followed by genes involved in methanol and formate oxidation, and nitrogen and CO2 fixation. Within all three meanders, low soil organic carbon correlated with high activity of genes involved in methanol, formate, sulfide, hydrogen, and ammonia oxidation, nitrite oxidoreduction, and nitrate and nitrite reduction. Overall, the results emphasize the importance of sulfur, one-carbon and nitrogen compound metabolism in soils of the riparian corridor.ConclusionsThe disparity between the scale of a microbial cell and the scale of a watershed currently limits the development of genomically informed predictive models describing watershed biogeochemical function. Meander-bound floodplains appear to serve as scaling motifs that predict aggregate capacities for biogeochemical transformations, providing a foundation for incorporating riparian soil microbiomes in watershed models. Widely represented genetic capacities did not predict in situ activity at one time point, but rather they define a reservoir of biogeochemical potential available as conditions change. Video abstract.

The U.S. Department of Energy's (DOE) Colorado East River Community Observatory (ER) in the Upper Colorado River Basin was established in 2015 as a representative mountainous, snow-dominated watershed to study hydrobiogeochemical responses to hydrological perturbations in headwater systems. The ER is characterized by steep elevation, geologic, hydrologic and vegetation gradients along floodplain, montane, subalpine, and alpine life zones, which makes it an ideal location for researchers to understand how different mountain subsystems contribute to overall watershed behaviour. The ER has both long-term and spatially-extensive observations and experimental campaigns carried out by the Watershed Function Scientific Focus Area (SFA), led by Lawrence Berkeley National Laboratory, and researchers from over 30 organizations who conduct cross-disciplinary process-based investigations and modelling of watershed behaviour. The heterogeneous data generated at the ER include hydrological, genomic, biogeochemical, climate, vegetation, geological, and remote sensing data, which combined with model inputs and outputs comprise a collection of datasets and value-added products within a mountainous watershed that span multiple spatiotemporal scales, compartments, and life zones. Within 5 years of collection, these datasets have revealed insights into numerous aspects of watershed function such as factors influencing snow accumulation and melt timing, water balance partitioning, and impacts of floodplain biogeochemistry and hillslope ecohydrology on riverine geochemical exports. Data generated by the SFA are managed and curated through its Data Management Framework. The SFA has an open data policy, and over 70 ER datasets are publicly available through relevant data repositories. A public interactive map of data collection sites run by the SFA is available to inform the broader community about SFA field activities. Here, we describe the ER and the SFA measurement network, present the public data collection generated by the SFA and partner institutions, and highlight the value of collecting multidisciplinary multiscale measurements in representative catchment observatories.

The Cedars ultramafic block hosts alkaline springs (pH > 11) in which calcium carbonate forms upon uptake of atmospheric CO2 and at times via mixing with surface water. These processes lead to distinct carbonate morphologies with “floes” forming at the atmosphere-water interface, “snow” of fine particles accumulating at the bottom of pools and terraced constructions of travertine. Floe material is mainly composed of aragonite needles despite CaCO3 precipitation occurring in waters with low Mg/Ca (

Atmospheric nitrous oxide contributes directly to global warming, yet models of the nitrogen cycle do not account for bedrock, the largest pool of terrestrial nitrogen, as a source of nitrous oxide. Although it is known that release rates of nitrogen from bedrock are large, there is an incomplete understanding of the connection between bedrock-hosted nitrogen and atmospheric nitrous oxide. Here, we quantify nitrogen fluxes and mass balances at a hillslope underlain by marine shale. We found that, at this site, bedrock weathering contributes 78% of the subsurface reactive nitrogen, while atmospheric sources (commonly regarded as the sole sources of reactive nitrogen in pristine environments) account for only the remaining 22%. About 56% of the total subsurface reactive nitrogen denitrifies, including 14% emitted as nitrous oxide. The remaining reactive nitrogen discharges in porewaters to a floodplain where additional denitrification probably occurs. We also found that the release of bedrock nitrogen occurs primarily within the zone of the seasonally fluctuating water table and suggest that the accumulation of nitrate in the vadose zone, often attributed to fertilization and soil leaching, may also include contributions from weathered nitrogen-rich bedrock. Our hillslope study suggests that, under oxygenated and moisture-rich conditions, weathering of deep, nitrogen-rich bedrock makes an important contribution to the nitrogen cycle.

There is a growing understanding of the role that bedrock weathering can play as a source of nitrogen (N) to soils, groundwater and river systems. The significance is particularly apparent in mountainous environments where weathering fluxes can be large. However, our understanding of the relative contributions of rock-derived, or geogenic, N to the total N supply of mountainous watersheds remains poorly understood. In this study, we develop the High-Altitude Nitrogen Suite of Models (HAN-SoMo), a watershed-scale ensemble of process-based models to quantify the relative sources, transformations, and sinks of geogenic and atmospheric N through a mountain watershed. Our study is based in the East River Watershed (ERW) in the Upper Colorado River Basin. The East River is a near-pristine headwater watershed underlain primarily by an N-rich Mancos Shale bedrock, enabling the timing and magnitude of geogenic and atmospheric contributions to watershed scale dissolved N-exports to be quantified. Several calibration scenarios were developed to explore equifinality using >1600 N concentration measurements from streams, groundwater, and vadose zone samples collected over the course of four years across the watershed. When accounting for recycling of N through plant litter turnover, rock weathering accounts for approximately 12% of the annual dissolved N sources to the watershed in the most probable calibration scenario (0-31% in other scenarios), and 21% (0-44% in other scenarios) when considering only "new" N sources (i.e. geogenic and atmospheric). On an annual scale, instream dissolved N elimination, plant turnover (including cattle grazing) and atmospheric deposition are the most important controls on N cycling.

This study examined the distribution of language expansion in parent-child (preschool aged) mealtime conversations in 30 Chinese middle-class families. The conversations were categorised into four types: "contextualised & conflicted," "contextualised & non-conflicted," "decontextualised & conflicted," and "decontextualised & non-conflicted." The language expansions were analysed using the systemic functional linguistic theory related to cohesive patterns in language expansion: "elaborations," "extensions," and "enhancements." While the parents dominated the conversations generally, the children were active contributors, initiating over one-quarter of the conversations. Initiation had an impact on the distribution of the conversational types: the proportions of "contextualised & non-conflicted" conversations was significantly higher in child-initiated conversations. The "contextualised & conflicted" conversations accounted for a higher proportion in parent-initiated conversations. It was the conversational type rather than initiation, which had an effect on the distribution of language expansion patterns. The least occurring "decontextualised & conflicted conversations" generated the most extensions. The frequently appeared "contextualised & non-conflicted" conversations, however, produced the fewest expanded messages. The implications from the findings for promoting high-quality mealtime conversations conducive to children's language learning are discussed.

Although bedrock weathering strongly influences water quality and global carbon and nitrogen budgets, the weathering depths and rates within subsurface are not well understood nor predictable. Determination of both porewater chemistry and subsurface water flow are needed in order to develop more complete understanding and obtain weathering rates. In a long-term field study, we applied a multiphase approach along a mountainous watershed hillslope transect underlain by marine shale. Here we report three findings. First, the deepest extent of the water table determines the weathering front, and the range of annually water table oscillations determines the thickness of the weathering zone. Below the lowest water table, permanently water-saturated bedrock remains reducing, preventing deeper pyrite oxidation. Secondly, carbonate minerals and potentially rock organic matter share the same weathering front depth with pyrite, contrary to models where weathering fronts are stratified. Thirdly, the measurements-based weathering rates from subsurface shale are high, amounting to base cation exports of about 70 kmolc ha-1 y-1, yet consistent with weathering of marine shale. Finally, by integrating geochemical and hydrological data we present a new conceptual model that can be applied in other settings to predict weathering and water quality responses to climate change.

Major components of hydrologic and elemental cycles reside underground, where their complex dynamics and linkages to surface waters are obscure. We delineated seasonal subsurface flow and transport dynamics along a hillslope in the Rocky Mountains (USA), where precipitation occurs primarily as winter snow and drainage discharges into the East River, a tributary of the Gunnison River. Hydraulic and geochemical measurements down to 10 m below ground surface supported application of transmissivity feedback of snowmelt to describe subsurface flow and transport through three zones: soil, weathering shale, and saturated fractured shale. Groundwater flow is predicted to depths of at least 176 m, although a shallower limit exists if hillslope-scale hydraulic conductivities are higher than our local measurements. Snowmelt during the high snowpack water year 2017 sustained flow along the weathering zone and downslope within the soil, while negligible downslope flow occurred along the soil during the low snowpack water year 2018. We introduce subsurface concentration-discharge (C-Q) relations for explaining hillslope contributions to C-Q observed in rivers and demonstrate their calculations based on transmissivity fluxes and measured pore water specific conductance and dissolved organic carbon. The specific conductance data show that major ions in the hillslope pore waters, primarily from the weathering and fractured shale, are about six times more concentrated than in the river, indicating hillslope solute loads are disproportionately high, while flow from this site and similar regions are relatively smaller. This methodology is applicable in different representative environments within snow-dominated watersheds for linking their subsurface exports to surface waters.

River to floodplain hydrologic connectivity is strongly enhanced by beaver- (Castor canadensis) engineered channel water diversions. The hydroecological impacts are wide ranging and generally positive, however, the hydrogeochemical characteristics of beaver-induced flowpaths have not been thoroughly examined. Using a suite of complementary ground- and drone-based heat tracing and remote sensing methodology we characterized the physical template of beaver-induced floodplain exchange for two alluvial mountain streams near Crested Butte, Colorado, USA. A flowpath-oriented perspective to water quality sampling allowed characterization of the chemical evolution of channel water diverted through floodplain beaver ponds and ultimately back to the channel in 'beaver pond return flows'. Subsurface return flow seepages were universally suboxic, while ponds and surface return flows showed a range of oxygen concentration due to in-situ photosynthesis and atmospheric mixing. Median concentrations of reduced metals: manganese (Mn), iron (Fe), aluminum (Al), and arsenic (As) were substantially higher along beaver-induced flowpaths than in geologically controlled seepages and upstream main channel locations. The areal footprint of reduced return seepage flowpaths were imaged with surface electromagnetic methods, indicating extensive zones of high-conductivity shallow groundwater flowing back toward the main channels and emerging at relatively warm bank seepage zones observed with infrared. Multiple-depth redox dynamics within one focused seepage zone showed coupled variation over time, likely driven by observed changes in seepage rate that may be controlled by pond stage. High-resolution times series of dissolved Mn and Fe collected downstream of the beaver-impacted reaches demonstrated seasonal dynamics in mixed river metal concentrations. Al time series concentrations showed proportional change to Fe at the smaller stream location, indicating chemically reduced flowpaths were sourcing Al to the channel. Overall our results indicated beaver-induced floodplain exchanges create important, and perhaps dominant, transport pathways for floodplain metals by expanding chemically-reduced zones paired with strong advective exchange.

Watersheds are important suppliers of freshwater for human societies. Within mountainous watersheds, microbial communities impact water chemistry and element fluxes as water from precipitation events discharge through soils and underlying weathered rock, yet there is limited information regarding the structure and function of these communities. Within the East River, CO watershed, we conducted a depth-resolved, hillslope to riparian zone transect study to identify factors that control how microorganisms are distributed and their functions. Metagenomic and geochemical analyses indicate that distance from the East River and proximity to groundwater and underlying weathered shale strongly impact microbial community structure and metabolic potential. Riparian zone microbial communities are compositionally distinct, from the phylum down to the species level, from all hillslope communities. Bacteria from phyla lacking isolated representatives consistently increase in abundance with increasing depth, but only in the riparian zone saturated sediments we found Candidate Phyla Radiation bacteria. Riparian zone microbial communities are functionally differentiated from hillslope communities based on their capacities for carbon and nitrogen fixation and sulfate reduction. Selenium reduction is prominent at depth in weathered shale and saturated riparian zone sediments and could impact water quality. We anticipate that the drivers of community composition and metabolic potential identified throughout the studied transect will predict patterns across the larger watershed hillslope system.

Understanding concentration-discharge (C-Q) relationships are essential for predicting chemical weathering and biogeochemical cycling under changing climate and anthropogenic conditions. Contrasting C-Q relationships have been observed widely, yet a mechanistic framework that can interpret diverse patterns remains elusive. This work hypothesizes that seemingly disparate C-Q patterns are driven by switching dominance of end-member source waters and their chemical contrasts arising from subsurface biogeochemical heterogeneity. We use data from Coal Creek, a high-elevation mountainous catchment in Colorado, and a recently developed watershed reactive transport model (BioRT-Flux-PIHM). Sensitivity analysis and Monte-Carlo simulations (500 cases) show that reaction kinetics and thermodynamics and distribution of source materials across depths govern the chemistry gradients of shallow soil water and deeper groundwater entering the stream. The alternating dominance of organic-poor yet geo-solute-rich groundwater under dry conditions and organic-rich yet geo-solute-poor soil water during spring melt leads to the flushing pattern of dissolved organic carbon and the dilution pattern of geogenic solutes (e.g., Na, Ca, and Mg). In addition, the extent of concentration contrasts regulates the power law slopes (b) of C-Q patterns via a general equation (Formula presented.). At low ratios of soil water versus groundwater concentrations (Cratio = Csw/Cgw  1.8), flushing arises; chemostasis occurs in between. This equation quantitatively interprets b values of 11 solutes (dissolved organic carbon, dissolved P, NO3−, K, Si, Ca, Mg, Na, Al, Mn, and Fe) from three catchments (Coal Creek, Shale Hills, and Plynlimon) of differing climate, geologic, and land cover conditions. This indicates potentially broad regulation of subsurface biogeochemical heterogeneity in determining C-Q patterns and wide applications of this equation in quantifying b values, which can have broad implications for predicting chemical weathering and biogeochemical transformation at the watershed scale.

Recharge of alluvial aquifers is a key component in understanding the interaction between floodplain vadose zone biogeochemistry and groundwater quality. The Rifle Site (a former U-mill tailings site) adjacent to the Colorado River is a well-established field laboratory that has been used for over a decade for the study of biogeochemical processes in the vadose zone and aquifer. This site is considered an exemplar of both a riparian floodplain in a semiarid region and a post-remediation U-tailings site. In this paper we present Sr isotopic data for groundwater and vadose zone porewater samples collected in May and July 2013 to build a mixing model for the fractional contribution of vadose zone porewater (i.e. recharge) to the aquifer and its variation across the site. The vadose zone porewater contribution to the aquifer ranged systematically from 0% to 38% and appears to be controlled largely by the microtopography of the site. The area-weighted average contribution across the site was 8% corresponding to a net recharge of 7.5 cm. Given a groundwater transport time across the site of ~1.5 to 3 years, this translates to a recharge rate between 5 and 2.5 cm/yr, and with the average precipitation to the site implies a loss from the vadose zone due to evapotranspiration of 83% to 92%, both ranges are in good agreement with previously published results by independent methods. A uranium isotopic (234U/238U activity ratios) mixing model for groundwater and surface water samples indicates that a ditch across the site is hydraulically connected to the aquifer and locally significantly affects groundwater. Groundwater samples with high U concentrations attributed to natural bio-reduced zones have 234U/238U activity ratios near 1, suggesting that the U currently being released to the aquifer originated from the former U-mill tailings.

Understanding terrestrial carbon cycling has relied primarily on studies of topsoils that are typically characterized to depths shallower than 0.5 m. At a semiarid site instrumented down to 7 m, we measured seasonal- and depth-resolved carbon inventories and fluxes and groundwater and unsaturated zone flow rates. Measurements showed that ~30% of the CO2 efflux to the atmosphere (60% in winter) originates from below 1 m, contrary to predictions of less than 1% by Earth System Model land modules. Respiration from deeper roots and deeper microbial communities is supported by favorable subsurface temperatures, moisture, and oxygen availability. Below 1 m, dissolved organic carbon fluxes from the overlying soil and C from deep roots and exudates are expected to be important in sustaining microbial respiration. Because these conditions are characteristic of semiarid climate regions, we contend that Earth System Model land modules should incorporate such deeper soil processes to improve CO2 flux predictions.

A non-electrostatic generalized composite surface complexation model (SCM) was developed for U(VI) sorption on contaminated F-Area sediments from the U.S. Department of Energy Savannah River Site, South Carolina. The objective of this study was to test if a simpler, semi-empirical, non-electrostatic U(VI) sorption model (NEM) could achieve the same predictive performance as a SCM with electrostatic correction terms in describing U(VI) plume evolution and long-term mobility. One-dimensional reactive transport simulations considering key hydrodynamic processes, Al and Fe minerals, as well as H+ and U surface complexation, with and without electrostatic correction terms, were conducted. The NEM was first calibrated with laboratory batch H+ and U(VI) sorption data on F-Area sediments, and then the surface area of the NEM was adjusted to match field observations of dissolved U(VI). Modeling results indicate that the calibrated NEM was able to perform as well as the previously developed electrostatic model in predicting the long-term evolution of H+ and U(VI) at the site, given the variability of field-site data. The electrostatic and NEM models yield somewhat different results for the time period when basin discharge was active; however, it is not clear which modeling approach may be better to model this early time period because groundwater quality data during this period were not available. A key finding of this study is that the applicability of NEM (and thus robustness of its predictions) to the field system evolves with time and is strongly dependent on the pH range that was used to develop the model.

Transport from the soil surface to groundwater is commonly mediated through deeper portions of the vadose zone and capillary fringe, where variations in temperature and water saturation strongly influence biogeochemical processes. This technical note describes a sediment column design that allows laboratory simulation of thermal and hydrologic conditions found in many field settings. Temperature control is particularly important because room temperature is not representative of most subsurface environments. A 2.0-m-tall column was capable of simulating profiles with temperatures ranging from 3 to 22°C, encompassing the full range of seasonal temperature variation observed in the deep vadose zone and capillary fringe of a semiarid floodplain in western Colorado. The water table was varied within the lower 0.8-m section of the column, and profiles of water content and matric potential were measured. Vadose zone CO2 collected from depth-distributed gas samplers under representative seasonal conditions reflected the influences of temperature and water table depth on microbial respiration. Thus, realistic subsurface biogeochemical dynamics can be simulated in the laboratory through establishing column profiles that represent seasonal thermal and hydrologic conditions.

Environmentally benign, economical, and effective surfactants and additives are needed in engineering subsurface energy recovery processes. Biosurfactants have some advantages over chemically synthesized surfactants, but the high costs of microbial-biosynthesis limit their applications in subsurface engineering. Here we propose to use naturally occurring biosurfactants contained within Earth's readily available and inexpensive humus deposits for subsurface engineering applications. We collected humus samples of different types from four different regions, and developed a simple method for extracting natural biosurfactant (NBS) using only four common chemicals. The average NBS extraction yields are 16 ± 3% of the raw humus. No significant differences in elemental composition and functional group chemistry were found among the NBS extracted from humus of different origins, suggesting that any humus deposit can be used for NBS extraction. Measurements of interfacial tensions between air-water and supercritical (sc) CO2-water interfaces indicate that the NBS is a highly effective surfactant. NBS has good foaming ability. Preliminary tests with only 0.5 mass % NBS in the aqueous phase (no other additives) yielded scCO2-in-water foams of 83% foam quality. The apparent viscosity of 13 cP measured at a shear rate of 2320 s-1 indicates that much higher viscosities are achievable at lower shear rates. These results suggest that NBS merits further research and development for potential applications in subsurface energy production.

In order to understand the transport and humification processes of dissolved organic matter (DOM) within sediments of a semi-arid floodplain at Rifle, Colorado, fluorescence excitation-emission matrix (EEM) spectroscopy, humification index (HIX) and specific UV absorbance (SUVA) at 254nm were applied for characterizing depth and seasonal variations of DOM composition. Results revealed that late spring snowmelt leached relatively fresh DOM from plant residue and soil organic matter down into the deeper vadose zone (VZ). More humified DOM is preferentially adsorbed by upper VZ sediments, while non- or less-humified DOM was transported into the deeper VZ. Interestingly, DOM at all depths undergoes rapid biological humification process evidenced by the products of microbial by-product-like (i.e., tyrosine-like and tryptophan-like) matter in late spring and early summer, particularly in the deeper VZ, resulting in more humified DOM (e.g., fulvic-acid-like and humic-acid-like substances) at the end of year. This indicates that DOM transport is dominated by spring snowmelt, and DOM humification is controlled by microbial degradation, with seasonal variations. It is expected that these relatively simple spectroscopic measurements (e.g., EEM spectroscopy, HIX and SUVA) applied to depth- and temporally-distributed pore-water samples can provide useful insights into transport and humification of DOM in other subsurface environments as well.

Although important for riverine solute and nutrient fluxes, the connections between biogeochemical processes and subsurface hydrology remain poorly characterized. We investigate these couplings in the East River, CO, a high-elevation shale-dominated catchment in the Rocky Mountains, using concentration-discharge (C-Q) relationships for major cations, anions, and organic carbon. Dissolved organic carbon (DOC) displays a positive C-Q relationship with clockwise hysteresis, indicating mobilization and depletion of DOC in the upper soil horizons and emphasizing the importance of shallow flow paths during snowmelt. Cation and anion concentrations demonstrate that carbonate weathering, which dominates solute fluxes, is promoted by both sulfuric acid derived from pyrite oxidation in the shale bedrock and carbonic acid derived from subsurface respiration. Sulfuric acid weathering dominates during base flow conditions when waters infiltrate below the inferred pyrite oxidation front, whereas carbonic acid weathering plays a dominant role during snowmelt as a result of shallow flow paths. Differential C-Q relationships between solutes suggest that infiltrating waters approach calcite saturation before reaching the pyrite oxidation front, after which sulfuric acid reduces carbonate alkalinity. This reduction in alkalinity results in CO2 outgassing when waters equilibrate to surface conditions, and reduces the riverine export of carbon and alkalinity by roughly 33% annually. Future changes in snowmelt dynamics that control the balance of carbonic and sulfuric acid weathering may substantially alter carbon cycling in the East River. Ultimately, we demonstrate that differential C-Q relationships between major solutes can provide unique insights into the complex subsurface flow and biogeochemical dynamics that operate at catchment scales.

Capillary pressure (Pc)-saturation (Sw) relations are essential for predicting equilibrium and flow of immiscible fluid pairs in soils and deeper geologic formations. In systems that are difficult to measure, behavior is often estimated based on capillary scaling of easily measured Pc–Sw relations (e.g., air-water, and oil-water), yet the reliability of such approximations needs to be examined. In this study, 17 sets of brine drainage and imbibition curves were measured with air-brine, decane-brine, and supercritical (sc) CO2-brine in homogeneous quartz and carbonate sands, using porous plate systems under ambient (0.1 MPa, 23°C) and reservoir (12.0 MPa, 45°C) conditions. Comparisons between these measurements showed significant differences in residual nonwetting phase saturation, Snw,r. Through applying capillary scaling, changes in interfacial properties were indicated, particularly wettability. With respect to the residual trapping of the nonwetting phases, Snwr, CO2 > Snwr, decane > Snwr, air. Decane-brine and scCO2-brine Pc–Sw curves deviated significantly from predictions assuming hydrophilic interactions. Moreover, neither the scaled capillary behavior nor Snw,r for scCO2-brine were well represented by decane-brine, apparently because of differences in wettability and viscosities, indicating limitations for using decane (and other organic liquids) as a surrogate fluid in studies intended to apply to geological carbon sequestration. Thus, challenges remain in applying scaling for predicting capillary trapping and multiphase displacement processes across such diverse fields as vadose zone hydrology, enhanced oil recovery, and geologic carbon sequestration.

Although CO2 fluxes from soils are often assumed to originate within shallow soil horizons (

Flood plains play a potentially important role in the global carbon cycle. The accumulation of organic matter in flood plains often induces the formation of chemically reduced groundwater and sediments along riverbanks. In this study, our objective is to evaluate the cumulative impact of such reduced zones, water table fluctuations, and temperature gradients on subsurface carbon fluxes in a flood plain at Rifle, Colorado located along the Colorado River. 2-D coupled variably-saturated, non-isothermal flow and biogeochemical reactive transport modeling was applied to improve our understanding of the abiotic and microbially mediated reactions controlling carbon dynamics at the Rifle site. Model simulations considering only abiotic reactions (thus ignoring microbial reactions) underestimated CO₂ partial pressures observed in the unsaturated zone and severely underestimated inorganic (and overestimated organic) carbon fluxes to the river compared to simulations with biotic pathways. Both model simulations and field observations highlighted the need to include microbial contributions from chemolithoautotrophic processes (e.g., Fe⁺² and S⁻² oxidation) to match locally-observed high CO₂ concentrations above reduced zones. Observed seasonal variations in CO₂ concentrations in the unsaturated zone could not be reproduced without incorporating temperature gradients in the simulations. Incorporating temperature fluctuations resulted in an increase in the annual groundwater carbon fluxes to the river by 170 % to 3.3 g m⁻² d⁻¹, while including water table variations resulted in an overall decrease in the simulated fluxes. We conclude that spatial microbial and redox zonation as well as temporal fluctuations of temperature and water table depth contribute significantly to subsurface carbon fluxes in flood plains and need to be represented appropriately in model simulations.