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Abstract: The power conversion efficiency of organic solar cells (OSCs) is exceeding 20%, an advance in which morphology optimization has played a significant role. It is generally accepted that the processing solvent (or solvent mixture) can help optimize morphology, impacting the OSC efficiency. Here we develop OSCs that show strong tolerance to a range of processing solvents, with all devices delivering high power conversion efficiencies around 19%. By investigating the solution states, the film formation dynamics and the characteristics of the processed films both experimentally and computationally, we identify the key factors that control morphology, that is, the interactions between the side chains of the acceptor materials and the solvent as well as the interactions between the donor and acceptor materials. Our work provides new understanding on the long-standing question of morphology control and effective guides to design OSC materials towards practical applications, where green solvents are required for large-scale processing.

The cathode–electrolyte interphase plays a pivotal role in determining the usable capacity and cycling stability of electrochemical cells, yet it is overshadowed by its counterpart, the solid–electrolyte interphase. This is primarily due to the prevalence of side reactions, particularly at low potentials on the negative electrode, especially in state-of-the-art Li-ion batteries where the charge cutoff voltage is limited. However, as the quest for high-energy battery technologies intensifies, there is a pressing need to advance the study of cathode–electrolyte interphase properties. Here, we present a comprehensive approach to analyse the cathode–electrolyte interphase in battery systems. We underscore the importance of employing model cathode materials and coin cell protocols to establish baseline performance. Additionally, we delve into the factors behind the inconsistent and occasionally controversial findings related to the cathode–electrolyte interphase. We also address the challenges and opportunities in characterizing and simulating the cathode–electrolyte interphase, offering potential solutions to enhance its relevance to real-world applications.

Co- and Ni-free disordered rocksalt cathodes utilize oxygen redox to increase the energy density of lithium-ion batteries, but it is challenging to achieve good cycle life at high voltages >4.5 V (versus Li/Li+). Here we report a family of Li-excess Mn-rich cathodes that integrates rocksalt- and polyanion-type structures. Following design rules for cation filling and ordering, we demonstrate the bulk incorporation of polyanion groups into the rocksalt lattice. This integration bridges the two primary families of lithium-ion battery cathodes—layered/spinel and phosphate oxides—dramatically enhancing the cycling stability of disordered rocksalt cathodes with 4.8 V upper cut-off voltage. The cathode exhibits high gravimetric energy densities above 1,100 Wh kg−1 and >70% retention over 100 cycles. This study opens up a broad compositional space for developing battery cathodes using earth-abundant elements such as Mn and Fe.

Water is an increasingly precious resource in California as years of drought, climate change, pollution, as well as an expanding population have all stressed the state's drinking water supplies. Currently, there are increasing concerns about whether regulated and unregulated contaminants in drinking water are linked to a variety of human-health outcomes particularly in socially disadvantaged communities with a history of health risks. To begin to address this data gap by broadly assessing contaminant mixture exposures, the current study was designed to collect tapwater samples from communities in Gold Country, the San Francisco Bay Area, two regions of the Central Valley (Merced/Fresno and Kern counties), and southeast Los Angeles for 251 organic chemicals and 32 inorganic constituents. Sampling prioritized low-income areas with suspected water quality challenges and elevated breast cancer rates. Results indicated that mixtures of regulated and unregulated contaminants were observed frequently in tapwater throughout the areas studied and the types and concentrations of detected contaminants varied by region, drinking-water source, and size of the public water system. Multiple exceedances of enforceable maximum contaminant level(s) (MCL), non-enforceable MCL goal(s) (MCLG), and other health advisories combined with frequent exceedances of benchmark-based hazard indices were also observed in samples collected in all five of the study regions. Given the current focus on improving water quality in socially disadvantaged communities, our study highlights the importance of assessing mixed-contaminant exposures in drinking water at the point of consumption to adequately address human-health concerns (e.g., breast cancer risk). Data from this pilot study provide a foundation for future studies across a greater number of communities in California to assess potential linkages between breast cancer rates and tapwater contaminants.

Groundwater aquifers worldwide experience unsustainable depletion, compounded by population growth, economic development, and climate forcing. Managed aquifer recharge provides one tool to alleviate flood risk and replenish groundwater. However, concerns grow that intentional flooding of farmland for groundwater recharge, a practice known as Ag-MAR, may increase the leaching of pesticides and other chemicals into groundwater. This study employs a physically based unsaturated flow model to determine the fate and transport of residues of four pesticide in three vadose zone profiles characterized by differing fractions of sand (41 %, 61 %, and 84 %) in California's Central Valley. Here, we show that the complex heterogeneity of alternating coarse and fine-grain hydrogeologic units controls the transit times of pesticides and their adsorption and degradation rates. Unsaturated zones that contain a higher fraction of sand are more prone to support preferential flow, higher recharge rates (+8 %), and faster (42 %) water flow and pesticide transport, more flooding-induced pesticide leaching (about 22 %), as well as more salt leaching correlating with increased risks of groundwater contamination. Interestingly, considering preferential flow predicted higher degradation and retention rates despite shorter travel times, attributed to the trapping of pesticides in immobile zones where they degrade more effectively. The findings underscore the importance of considering soil texture and structure in Ag-MAR practices to minimize environmental risks while enhancing groundwater recharge. The study also highlights that selecting less mobile pesticides can reduce leaching risks in sandy areas.

Abstract. The hydrological cycle of sub-arctic areas is dominated by the snowmelt event. An understanding of the mechanisms that control water fluxes during high-volume infiltration events in sub-arctic till soils is needed to assess how future changes in the timing and magnitude of snowmelt can affect soil water storage dynamics. We conducted a tracer experiment in which deuterated water was used to irrigate a plot on a forested hilltop in Lapland, tracked water fluxes of different mobility and monitored how the later snowmelt modifies the labelled soil water storage. We used lysimeters and destructive soil coring for soil water sampling and monitored and sampled the groundwater. Large spatiotemporal variability between the waters of different mobility was observed in the subsurface, while surface water flow during the tracer experiment was largely controlled by a fill-and-spill mechanism. Extensive soil saturation induced the flow of labelled water into the roots of nearby trees. We found that labelled water remained in deeper soil layers over the winter, but the snowmelt event gradually displaced all deuterated water and fully homogenized all water fluxes at the soil–vegetation interface. The conditions required for the full displacement of the old soil water occur only during a snowmelt with a persistently high groundwater table. We propose a conceptual model where infiltration into the soil and eventual soil water replenishment occur in three stages. First, unsaturated macropore flow is initiated via the surface microtopography and is directed towards the groundwater storage. The second stage is characterized by groundwater rise through the macropore network, subsequent pore water saturation and increased horizontal connectivity of macropores. Shallow subsurface lateral fluxes develop in more permeable shallow soil layers. In the third stage, which materializes during a long period with a high groundwater table and high hydrological connectivity within the soil, the soil water is replenished via enhanced matrix flow and pore water exchange with the macropore network.

Abstract: Huang and Merwade (2023), https://doi.org/10.1029/2023wr034947, hereafter conveniently referred to as HM23, wrongly claim improvement of their method for postprocessing multi‐model water stage predictions using Bayesian Model Averaging (BMA). Their results show all signs of a flawed implementation of the Metropolis algorithm. In this comment I will point out the many mistakes and shortcomings of the BMA methodology of HM23. Their method is deficient, inefficient and ineffective and wrongly quantifies BMA model parameter and predictive uncertainty. Furthermore, HM23 misrepresent BMA literature, articulate a poor understanding of Markov chain Monte Carlo methods and misuse the autocorrelation function for monitoring convergence of the sampled Markov chains. A proper implementation of the random walk Metropolis algorithm would have led HM23 to substantially different results and findings about their ensemble of water stage predictions. The MODELAVG toolbox of Vrugt (2018) https://www.researchgate.net/publication/299458373_MODELAVG_A_MATLAB_Toolbox_for_Postprocessing_of_Model_Ensembles satisfies all requirements of HM23 and provides robust estimates of BMA model parameter and prediction uncertainty for symmetric, skewed and truncated conditional forecast distributions of the ensemble members.

Urban landscapes homogenize our world at global scales, contributing to “extinction of experience”, a progressive decline in human interactions with native greenspace that can disconnect people from the services it provides. College age adults report feeling disconnected from nature more than other demographics, making universities a logical place to explore interventions intended to restore a connection with nature. This study surveyed 1088 students and staff across four university campus communities in Southern California, USA and used multicriteria decision analysis to explore their landscape preferences and the implications of those preferences for combatting extinction of experience. Our results suggest that perspectives of, and preferences for, different greenspace forms vary significantly (i.e., they are not perceived as substitutable). Support for native ecosystems, particularly coastal sage scrub (top ranked landscape) was generally high, suggesting that disaffection with wild nature is not particularly widespread. Programs for replacing turf grass lawns (lowest ranked landscape) with native plants were also well supported, but support for stormwater bioswales was more moderate (and variable). This may reflect their relative newness, both on university campuses and in urban spaces more generally. Not all members of campus communities preferred the same landscapes; preferences differed with degree of pro-environmentalism and university status (undergraduate student, graduate student, staff). Even so, all respondents exhibited landscape preferences consistent with at least one approach for combatting extinction of experience, suggesting that ecologists, engineers and urban planners have a viable set of generalizable tools for reconnecting people with nature.

The capture and separation of carbon dioxide (CO2) has been the focus of a plethora of research in order to mitigate its emissions and contribute to global development. Given that CO2 is commonly found in natural gas streams, there have been efforts to seek more efficient materials to separate gaseous mixtures such as CO2/CH4. However, there are only a few reports regarding adsorption processes within pressurized systems. In the offshore scenario, natural gas streams still exhibit high moisture content, necessitating a greater understanding of processes in moist systems. In this article, a metal-organic framework synthesis based on zirconium (MOF-808) was carried out through a conventional solvothermal method and autoclave for the adsorption of CO2 and CH4 under different temperatures (45–65 °C) and pressures up to 100 bar. Furthermore, the adsorption of humid CO2 was evaluated using thermal analyses. The MOF-808 synthesized in autoclave showed a high surface area (1502 m2/g), a high capacity for CO2 adsorption at 50 bar and 45 °C and had a low selectivity to capture CH4 molecules. It also exhibited a fine stability after five cycles of CO2 adsorption and desorption at 50 bar and 45 °C − as confirmed by structural post-adsorption analyses while maintaining its adsorption capacity and crystallinity. Furthermore, it can be observed that the adsorption capacity increased in a humid environment, and that the adsorbent remained stable after adsorption cycles in the presence of moisture. Finally, it was possible to confirm the occurrence of physisorption processes through nuclear magnetic resonance (NMR) analyses, thus validating the choice of mild temperatures for regeneration and contributing to the reduction of energy consumption in processing plants.

Terrestrial evapotranspiration is the second-largest component of the land water cycle, linking the water, energy, and carbon cycles and influencing the productivity and health of ecosystems. The dynamics of ET across a spectrum of spatiotemporal scales and their controls remain an active focus of research across different science disciplines. Here, we provide an overview of the current state of ET science across in situ measurements, partitioning of ET, and remote sensing, and discuss how different approaches complement one another based on their advantages and shortcomings. We aim to facilitate collaboration among a cross-disciplinary group of ET scientists to overcome the challenges identified in this paper and ultimately advance our integrated understanding of ET.

Results of previous research on chemigated imazamox for control of branched broomrape (Phelipanche ramosa) in processing tomatoes suggested potential soil-type differences in imazamox availability. Over two years, there were differences in crop-injury between two sites less than 30-km apart: imazamox-treated tomatoes in the Davis location had relatively minor early season injury while tomatoes at the Woodland location were severely injured or killed. The following study was conducted to investigate imazamox sorption in four California soils to determine if differences in herbicide adsorption played a role in variable crop-injury observed in the field trials. To determine the sorption capacity of imazamox of each soil, a batch-equilibrium study was conducted. There were significant differences in sorbed imazamox: the clay soil had the highest adsorption (Robert's Island: 742.5 pg µL-1 sorbed), followed by the sandy loam soil (Ripon: 723.9 pg µL-1 sorbed), while the loam soils from both trial sites (Davis: 704.2 pg µL-1 sorbed; Woodland: 699.9 pg µL-1 sorbed) had the lowest adsorption and were not significantly different from one another. Results from this study illustrate only minor differences in imazamox adsorption among the soils tested which suggests that soil type was likely not a major factor contributing to differences in crop-injury.

Anode-free batteries possess the optimal cell architecture due to their reduced weight, volume and cost. However, their implementation has been limited by unstable anode morphological changes and anode–liquid electrolyte interface reactions. Here we show that an electrochemically stable solid electrolyte and the application of stack pressure can solve these issues by enabling the deposition of dense sodium metal. Furthermore, an aluminium current collector is found to achieve intimate solid–solid contact with the solid electrolyte, which allows highly reversible sodium plating and stripping at both high areal capacities and current densities, previously unobtainable with conventional aluminium foil. A sodium anode-free all-solid-state battery full cell is demonstrated with stable cycling for several hundred cycles. This cell architecture serves as a future direction for other battery chemistries to enable low-cost, high-energy-density and fast-charging batteries.

Non-fused ring electron acceptors (NFREAs) potentially have lower synthetic costs than their fused counterparts. However, the low backbone planarity and the presence of bulky substituents adversely affect the crystallinity of NFREAs, impeding charge transport and the formation of bicontinuous morphology in organic solar cells. Here we show that a binary solvent system can individually control the crystallization and phase separation of the donor polymer (for example, D18) and the NFREA (for example, 2BTh-2F-C2). We select solvents such as chloroform and o-xylene that evaporate at different temperatures and rates and have different solubility for D18. Upon evaporation of chloroform, D18 starts to assemble into fibrils. Then, the evaporation of o-xylene induces the rapid formation of a fibril network that phase segregates 2BTh-2F-C2 into pure domains and leads to a bicontinuous morphology. The well-defined interpenetrating network morphology affords an efficiency of 19.02% on small-area cells and 17.28% on 1 cm2 devices.

Community solar, a business model where multiple customers buy output from shared solar systems, has expanded solar access among multifamily housing occupants, renters, and low-income households. Policies to enable community solar could be expanded and benefits of access augmented through targeted measures to support community solar adoption in underserved communities.

Correction to: Nature Energyhttps://doi.org/10.1038/s41560-024-01546-2, published online 3 June 2024 In the version of the article initially published, data in Fig. 5b–d were displayed incorrectly and have now been amended in the HTML and PDF versions of the article. The original and corrected figures can be seen below in Fig. 1. (Figure presented.)

The long-lived radiotoxicity of the high-level radioactive waste generated by nuclear power plants requires safe isolation from the biosphere for many hundreds of thousands of years. An international consensus has emerged that such isolation can best be provided by disposal in mined geologic repositories, a strategy that today is pursued by most countries dealing with radioactive waste. However, the need to predict the performance of such repositories over very long time periods generates large uncertainties that have to be accounted for in safety assessments. The findings from such safety assessments need to be conveyed to all stakeholders in a clear way, such that public confidence in geologic disposal solutions can be achieved. It is suggested here that close international collaboration on the technical aspects of geologic waste disposal has helped, and will continue to help, building trust and increasing confidence. This paper discusses a particular international collaboration initiative referred to as DECOVALEX, which brings together multiple teams and disciplines to collectively tackle complex experimental and modeling challenges related to geologic disposal. By describing how DECOVALEX works and by providing joint research examples, a case is made that such international collaboration contributes to knowledge transfer and confidence building in radioactive waste disposal science.

Rooftop and community solar are alternative product classes for residential solar in the United States. Community solar, where multiple households buy solar from shared systems, could make solar more accessible by reducing initial costs and removing adoption barriers for renters and multifamily building occupants. Here we test whether community solar has expanded solar access in the United States. On the basis of a sample of 11 states, we find that community solar adopters are about 6.1 times more likely to live in multifamily buildings than rooftop solar adopters, 4.4 times more likely to rent and earn 23% less annual income. We do not find that community solar expands access in terms of race. These differences are driven, roughly evenly, by inherent differences between the two solar products and by policies to promote low-income community solar adoption. The results suggest that alternative solar products can expand solar access and that policy could augment such benefits.

Complete representation of rainfall–runoff responses in complex, large watersheds using a single-objective parameterization approach in watershed models is often unachievable. In this study we present a calibration approach for the SWAT+ model that independently fits model parameters for different flow segments of the hydrograph. The approach is demonstrated for the Feather River, California, USA, using daily streamflow from the Lake Oroville Reservoir outlet gage. Results show that when model parameters were independently fitted for different flow segments the KGE, NSE, PBIAS, and RSR values improved to 0.96, 0.99, −3.3, and 0.10, respectively, compared to 0.72, 0.66, −9.30, and 0.53, respectively, achieved under a multiobjective and full hydrograph (average hydrograph) calibration. The results highlight that when considering the average hydrograph and flow duration curves, a more balanced representation of both poorly and well-performing segments is achieved, emphasizing the importance of segment-specific parameterization and multi-objective evaluation for accurately representing different flow conditions.

The constitutive relations of the Richardson-Richards equation encode the macroscopic properties of soil water retention and conductivity. These soil hydraulic functions are commonly represented by models with a handful of parameters. The limited degrees of freedom of such soil hydraulic models constrain our ability to extract soil hydraulic properties from soil moisture data via inverse modeling. We present a new free-form approach to learning the constitutive relations using physically constrained neural networks. We implemented the inverse modeling framework in a differentiable modeling framework, JAX, to ensure scalability and extensibility. For efficient gradient computations, we implemented implicit differentiation through a nonlinear solver for the Richardson-Richards equation. We tested the framework against synthetic noisy data and demonstrated its robustness against varying magnitudes of noise and degrees of freedom of the neural networks. We applied the framework to soil moisture data from an upward infiltration experiment and demonstrated that the neural network-based approach was better fitted to the experimental data than a parametric model and that the framework can learn the constitutive relations.

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.

Distribution forecasts P over future quantities or events are routinely made in hydrology but usually traded for a (likelihood-weighted) mean or median prediction to accommodate error measures or scoring functions such as the mean absolute error or mean squared error. Case in point is the so-called KG efficiency (KGE) of Gupta et al. (2009, https://doi.org/10.1016/j.jhydrol.2009.08.003) and improvements thereof (Lamontagne et al., 2020, https://doi.org/10.1029/2020wr027101), which have rapidly gained popularity among hydrologists as alternative scoring functions to the commonly used Nash and Sutcliffe (1970, https://doi.org/10.1016/0022-1694(70)90255-6) efficiency, but are equally exclusive in how they quantify model performance using only single-valued output of the quantities of interest. This point-valued mapping necessarily implies a loss of information about model performance. This paper advocates the use of probabilistic watershed model training, evaluation and diagnostics. Distribution evaluation opens a mature literature on scoring rules whose strong statistical underpinning provides, as we will demonstrate, the theory, context and guidelines necessary for the development of robust information-theoretically principled metrics for watershed signatures. These so-called hydrograph functionals are scalar-valued mappings of major behavioral watershed functions embodied in a strictly proper scoring rule. We discuss past developments that led to the current state-of-the-art of distribution evaluation in hydrology and review scoring rules for dichotomous and categorical events, quantiles (intervals) and density forecasts. We are particularly concerned with elicitable functionals and scoring rule propriety, discuss the decomposition of scoring rules into a sharpness, reliability and entropy term and present diagnostically appealing strictly proper divergence scores of hydrograph functionals for flood frequency analysis, flow duration and recession curves. The usefulness and power of distribution-based model evaluation and diagnostics by means of scoring rules is demonstrated on simple illustrative problems and discharge distributions simulated with watershed models using random sampling and Bayesian model averaging. The presented theory (a) enables a more complete evaluation of distribution forecasts, (b) offers a statistically principled means for watershed model training, evaluation, diagnostics and selection using hydrograph functionals and/or extreme events and (c) provides a universal framework for metric development of watershed signatures, promoting metric standardization and reproducibility.

Geochemically driven alterations of fractures in multi-mineral media can create altered layers (ALs) at the fracture-matrix interface. Spatial variations in the AL significantly influence mass transfer across the interface, and the hydraulic and mechanical properties of the fractured medium. A real-rock based microfluidic experiment reported spatial variations in AL thickness despite the initially smooth fracture surface, suggesting potential effects of matrix heterogeneity on AL development. However, the respective contribution of structural and mineralogical characteristics is still poorly understood. Using the microfluidic experimental data and a micro-continuum reactive transport model, we systematically evaluated how micro-porosity and initial mineral texture impact AL development and thus the overall reactive transport behaviors. Our simulation results confirmed that the extent of AL spatial variations, mainly controlled by mineralogical texture, influences the evolution of reaction and permeability in different ways. Accounting for spatial heterogeneity in mineral distribution produces “channeling” structures in ALs and lower overall reaction (by up to 35.6%), but larger permeability increase (by up to 9.8%). The characteristic length of the reactive mineral cluster was observed to dominate the internal texture of ALs. Whereas the presence of micro-porosity can enhance mineral accessibility via improving connectivity for flow and transport, and lead to both higher bulk reaction, that is, thicker ALs, and permeability enhancement. Considerations of surface roughness with characteristic length on the same order of magnitude as mineral texture did not change the overall development of AL, which further highlights the importance of accounting for rock matrix properties in predicting long-term evolution of fractured media. The resulting spatial variations of ALs and their impacts on bulk properties, however, are expected to be further complicated by the coupling of chemical and mechanical processes, and may trigger matrix disaggregation, erosion and other mechanisms of fractured media alteration.

We present a new pore-scale model for multicomponent advective-diffusive transport with coupled mineral dissolution and precipitation. Both dissolution and precipitation are captured simultaneously by introducing a phase transformation vector field representing the direction and magnitude of the overall phase change. An effective viscosity model is adopted in simulating fluid flow during mineral dissolution-precipitation that can accurately capture the velocity field without introducing any empirical parameters. The proposed approach is validated against analytical solutions and interface tracking simulations in simplified structures. After validation, the proposed approach is employed in modeling realistic rocks where mineral dissolution and precipitation are dominant at different locations. We have identified three regimes for mineral dissolution-precipitation coupling: (a) compact dissolution-precipitation where dissolution is dominant near the inlet and precipitation is dominant near the outlet, (b) wormhole dissolution with clustered precipitation where dissolution generates wormholes in the main flow paths and precipitation clogs the secondary flow paths, and (c) dissolution dominant where all solid grains are gradually dissolved. In the three regimes, the proposed approach provides reliable porosity-permeability relationships that cannot be described well by traditional macroscale models. We find that the permeability can increase while the overall porosity decreases when the main flow paths are expanded by dissolution and adjacent pore spaces are clogged by precipitation.

Knowledge of the recurrence intervals of precipitation extremes is vital for infrastructure design, risk assessment, and insurance planning. However, trends and shifts in rainfall patterns globally pose challenges to the application of extreme value analysis (EVA) which relies critically on the assumption of stationarity. In this paper, we explore: (1) the suitability of nonstationary (NS) models in the presence of statistically significant trends, and (2) their potential in modeling out-of-sample data to improve frequency analysis of extreme precipitation. We analyze the benefits of using a nonstationary Generalized Extreme Value (GEV) model for annual extreme precipitation records from Southern Brazil. The location of the GEV distribution is allowed to change with time. The unknown GEV model parameters are estimated using Bayesian techniques coupled with Markov chain Monte Carlo simulation. Next, we use GAME sampling to compute the evidence (and their ratios, the so-called Bayes factors) for stationary and nonstationary models of annual maximum precipitation. Our results show that the presence of a statistically significant trend in annual maximum precipitation alone does not justify the use of a NS model. The location parameter of the GEV distribution must also be well defined, otherwise, stationary models of annual maximum precipitation receive more support by the data. These findings reiterate the importance of accounting for GEV model parameters and predictive uncertainty in frequency analysis and hypothesis testing of annual maximum precipitation data records. Furthermore, a meaningful EVA demands detailed knowledge about the origin and persistence of observed changes.

The intensity of global groundwater use rose from 124 m3 per capita in 1950 to 152 m3 in 2021, for a 22.6% rise in the annual per capita use. This rise in global per capita water use reflects rising consumption patterns. The global use of groundwater, which provides between 21% and 30% of the total freshwater annual consumption, will continue to expand due to the sustained population growth projected through most of the 21st century and the important role that groundwater plays in the water-food-energy nexus. The rise in groundwater use, on the other hand, has inflicted adverse impacts in many aquifers, such as land subsidence, sea water intrusion, stream depletion, and deterioration of groundwater-dependent ecosystems, groundwater-quality degradation, and aridification. This paper projects global groundwater use between 2025 and 2050. The projected global annual groundwater withdrawal in 2050 is 1535 km3 (1 km3 = 109 m3 = 810,713 acre-feet). The projected global groundwater depletion, that is, the excess of withdrawal over recharge, in 2050 equals 887 km3, which is about 61% larger than in 2021. This projection signals probable exacerbation of adverse groundwater-withdrawal impacts, which are worsened by climatic trends and the environmental requirement of groundwater flow unless concerted national and international efforts achieve groundwater sustainability.

Most of the available data on diffusion in natural clayey rocks consider tracer diffusion in the absence of a salinity gradient despite the fact that such gradients are frequently found in natural and engineered subsurface environments. To assess the role of such gradients on the diffusion properties of clayey materials, through-diffusion experiments were carried out in the presence and absence of a salinity gradient using salt-diffusion and radioisotope tracer techniques. The experiments were carried out with vermiculite samples that contained equal proportions of interparticle and interlayer porosities so as to assess also the role played by the two types of porosities on the diffusion of water and ions. Data were interpreted using both a classical Fickian diffusion model and with a reactive transport code, CrunchClay that can handle multi-porosity diffusion processes in the presence of charged surfaces. By combining experimental and simulated data, we demonstrated that (i) the flux of water diffusing through vermiculite interlayer porosity was minor compared to that diffusing through the interparticle porosity, and (ii) a model considering at least three types of porous volumes (interlayer, interparticle diffuse layer, and bulk interparticle) was necessary to reproduce consistently the variations of neutral and charged species diffusion as a function of salinity gradient conditions.

Geologic features (e.g., fractures and alluvial fans) can play an important role in the locations and volumes of groundwater discharge and degree of groundwater-surface water (GW-SW) interactions. However, the role of these features in controlling GW-SW dynamics and streamflow generation processes are not well constrained. GW-SW interactions and streamflow generation processes are further complicated by variability in precipitation inputs from summer and fall monsoon rains, as well as declines in snowpack and changing melt dynamics driven by warming temperatures. Using high spatial and temporal resolution radon and water stable isotope sampling and a 1D groundwater flux model, we evaluated how groundwater contributions and GW-SW interactions varied along a stream reach impacted by fractures (fractured-zone) and downstream of the fractured hillslope (non-fractured zone) in Coal Creek, a Colorado River headwater stream affected by summer monsoons. During early summer, groundwater contributions from the fractured zone were high, but declined throughout the summer. Groundwater contributions from the non-fractured zone were constant throughout the summer and became proportionally more important later in the summer. We hypothesize that groundwater in the non-fractured zone is dominantly sourced from a high-storage alluvial fan at the base of a tributary that is connected to Coal Creek throughout the summer and provides consistent groundwater influx. Water isotope data revealed that Coal Creek responds quickly to incoming precipitation early in the summer, and summer precipitation becomes more important for streamflow generation later in the summer. We quantified the change in catchment dynamic storage and found it negatively related to stream water isotope values, and positively related to modeled groundwater discharge and the ratio of fractured zone to non-fractured zone groundwater. We interpret these relationships as declining hydrologic connectivity throughout the summer leading to late summer streamflow supported predominantly by shallow flow paths, with variable response to drying from geologic features based on their storage. As groundwater becomes more important for sustaining summer flows, quantifying local geologic controls on groundwater inputs and their response to variable moisture conditions may become critical for accurate predictions of streamflow.

Understanding connectivity between the soil and deeper bedrock groundwater is needed to accurately predict a watershed's response to perturbation, such as drought. Yet, the bedrock groundwater dynamics in mountainous environments are typically under-constrained and excluded from watershed hydrologic models. Here, we investigate the role of groundwater characterized with decadal and longer water ages on the hydrologic and mass-transport processes within a steep snow-dominated mountain hillslope in the Central Rocky Mountains (USA). We quantify subsurface and surface water mass-balance, groundwater flowpaths, and age distributions using the ParFlow-CLM integrated hydrologic and EcoSLIM particle tracking models, which are compared to hydrometric and environmental tracer observations. An ensemble of models with varied soil and hydrogeologic parameters reproduces observed groundwater levels and century-scale mean ages inferred from environmental tracers. The numerical models suggest soil water near the toe of the hillslope contains considerable (>60 % of the mass-flux) contributions from bedrock flowpaths characterized with water ages >10 years. Flowpath connectivity between the deeper bedrock and soil systems is present throughout the year, highlighting the potentially critical role of groundwater with old ages on processes such as evapotranspiration and streamflow generation. The coupled numerical model and groundwater age observations show the bedrock groundwater system influences the hillslope hydrodynamics and should be considered in mountain watershed conceptual and numerical models.