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  1. Abstract

    Two major barriers hinder the holistic understanding of subsurface critical zone (CZ) evolution and its impacts: (a) an inability to measure, define, and share information and (b) a societal structure that inhibits inclusivity and creativity. In contrast to the aboveground portion of the CZ, which is visible and measurable, the bottom boundary is difficult to access and quantify. In the context of these barriers, we aim to expand the spatial reach of the CZ by highlighting existing and effective tools for research as well as the “human reach” of CZ science by expanding who performs such science and who it benefits. We do so by exploring the diversity of vocabularies and techniques used in relevant disciplines, defining terminology, and prioritizing research questions that can be addressed. Specifically, we explore geochemical, geomorphological, geophysical, and ecological measurements and modeling tools to estimate CZ base and thickness. We also outline the importance of and approaches to developing a diverse CZ workforce that looks like and harnesses the creativity of the society it serves, addressing historical legacies of exclusion. Looking forward, we suggest that to grow CZ science, we must broaden the physical spaces studied and their relationships with inhabitants, measure the “deep” CZ and make data accessible, and address the bottlenecks of scaling and data‐model integration. What is needed—and what we have tried to outline—are common and fundamental structures that can be applied anywhere and used by the diversity of researchers involved in investigating and recording CZ processes from a myriad of perspectives.

     
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    Free, publicly-accessible full text available March 1, 2025
  2. The effects of fluoroethylene carbonate (FEC) electrolyte additive on charged sodium ion electrode/electrolyte reactivity at elevated temperatures were investigated using accelerating rate calorimetry (ARC). The beneficial effect of FEC on cell lifetime was demonstrated using Na0.97Ca0.03[Mn0.39Fe0.31Ni0.22Zn0.08]O2(NCMFNZO)/hard carbon (HC) pouch cells first prior to ARC measurements. Electrodes from these pouch cells were utilized as sample materials and 1.0 M NaPF6in propylene carbonate (PC):ethyl methyl carbonate (EMC) (1:1 by vol.) was chosen as control electrolyte. Adding 2 wt% and 5 wt% FEC to the electrolyte does not significantly affect the reactivity of de-sodiated NCMFNZO compared to the control electrolyte. However, the addition of FEC obviously changed the reactivity between sodiated HC and electrolytes, especially by showing a suppression on the exothermal behavior between 160 °C and 230 °C. These results give a head to head comparison of the reactivity of FEC additive containing electrolytes with charged sodium ion electrode materials at elevated temperatures and show that the use of FEC at additive levels should not compromise the cell safety when extending cell lifetime.

     
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  3. Despite extensive research efforts in developing aqueous rechargeable zinc metal batteries (RZMBs) as high-energy-density alternatives to both lithium ion and lithium metal batteries, the commercial prospects for RZMBs are still obfuscated by fundamental scientific questions. In particular, the electrode–electrolyte interphase properties and behaviors are still intensely debated topics in this field. In this review, we provide a comprehensive and thorough overview of the solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI) in aqueous RZMBs, with an emphasis on the formation mechanisms and characteristics of the SEI and CEI. We then summarize state-of-the-art techniques for characterizing the SEI/CEI to reveal the intrinsic correlation between the functionalities of the interphases and the electrochemical performances. Finally, future directions are proposed, including studies on aqueous SEI/CEI evolution as a function of pH and temperature, as well as SEI/CEI studies for high-energy-density and long-lifetime RZMBs. 
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  4. In the past decade, academia and industry have embraced machine learning (ML) for database management system (DBMS) automation. These efforts have focused on designing ML models that predict DBMS behavior to support picking actions (e.g., building indexes) that improve the system's performance. Recent developments in ML have created automated methods for finding good models. Such advances shift the bottleneck from DBMS model design to obtaining the training data necessary for building these models. But generating good training data is challenging and requires encoding subject matter expertise into DBMS instrumentation. Existing methods for training data collection are bespoke to individual DBMS components and do not account for (1) how workload trends affect the system and (2) the subtle interactions between internal system components. Consequently, the models created from this data do not support holistic tuning across subsystems and require frequent retraining to boost their accuracy. This paper presents the architecture of a database gym, an integrated environment that provides a unified API of pluggable components for obtaining high-quality training data. The goal of a database gym is to simplify ML model training and evaluation to accelerate autonomous DBMS research. But unlike gyms in other domains that rely on custom simulators, a database gym uses the DBMS itself to create simulation environments for ML training. Thus, we discuss and prescribe methods for overcoming challenges in DBMS simulation, which include demanding requirements for performance, simulation fidelity, and DBMS-generated hints for guiding training processes. 
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  5. Abstract

    Agricultural fields in drylands are challenged globally by limited freshwater resources for irrigation and also by elevated soil salinity and sodicity. It is well known that pedogenic carbonate is less soluble than evaporate salts and commonly forms in natural drylands. However, few studies have evaluated how irrigation loads dissolved calcium and bicarbonate to agricultural fields, accelerating formation rates of secondary calcite and simultaneously releasing abiotic CO2to the atmosphere. This study reports one of the first geochemical and isotopic studies of such “anthropogenic” pedogenic carbonates and CO2from irrigated drylands of southwestern United States. A pecan orchard and an alfalfa field, where flood-irrigation using the Rio Grande river is a common practice, were compared to a nearby natural dryland site. Strontium and carbon isotope ratios show that bulk pedogenic carbonates in irrigated soils at the pecan orchard primarily formed due to flood-irrigation, and that approximately 20–50% of soil CO2in these irrigated soils is calcite-derived abiotic CO2instead of soil-respired or atmospheric origins. Multiple variables that control the salt buildup in this region are identified and impact the crop production and soil sustainability regionally and globally. Irrigation intensity and water chemistry (irrigation water quantity and quality) dictate salt loading, and soil texture governs water infiltration and salt leaching. In the study area, agricultural soils have accumulated up to 10 wt% of calcite after just about 100 years of cultivation. These rates will likely increase in the future due to the combined effects of climate variability (reduced rainfall and more intense evaporation), use of more brackish groundwater for irrigation, and reduced porosity in soils. The enhanced accumulation rates of pedogenic carbonate are accompanied by release of large amounts of abiotic CO2from irrigated drylands to atmosphere. Extensive field studies and modelling approaches are needed to further quantify these effluxes at local, regional and global scales.

     
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  6. The Paradox Basin in the Colorado Plateau (USA) has some of the most iconic records of paleofluid flow, including sandstone bleaching and ore mineralization, and hydrocarbon, CO2, and He reservoirs, yet the sources of fluids responsible for these extensive fluid-rock reactions are highly debated. This study, for the first time, characterizes fluids within the basin to constrain the sources and emergent behavior of paleofluid flow resulting in the iconic rock records. Major ion and isotopic (δ18Owater; δDwater; δ18OSO4; δ34SSO4; δ34SH2S; 87Sr/86Sr) signatures of formation waters were used to evaluate the distribution and sources of fluids and water-rock interactions by comparison with the rock record. There are two sources of salinity in basinal fluids: (1) diagenetically altered highly evaporated paleo-seawater-derived brines associated with the Pennsylvanian Paradox Formation evaporites; and (2) dissolution of evaporites by topographically driven meteoric circulation. Fresh to brackish groundwater in the shallow Cretaceous Burro Canyon Formation contains low Cu and high SO4 concentrations and shows oxidation of sulfides by meteoric water, while U concentrations are higher than within other formation waters. Deeper brines in the Pennsylvanian Honaker Trail Formation were derived from evaporated paleo-seawater mixed with meteoric water that oxidized sulfides and dissolved gypsum and have high 87Sr/86Sr indicating interaction with radiogenic siliciclastic minerals. Upward migration of reduced (hydrocarbon- and H2S-bearing) saline fluids from the Pennsylvanian Paradox Formation along faults likely bleached sandstones in shallower sediments and provided a reduced trap for later Cu and U deposition. The distribution of existing fluids in the Paradox Basin provides important constraints to understand the rock record over geological time. 
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