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At least 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

The role of dissolved pyrogenic carbon from biochar in the sorption of As(V) in biogenic iron (oxyhydr)oxides

Water contamination by arsenic (As) affects millions of people around the world, making techniques to immobilize or remove this contaminant a pressing societal need. Biochar and iron (oxyhydr)oxides [in particular, biogenic iron (oxyhydr)oxides (BIOS)] offer the possibility of stabilizing As in remediation systems. However, little is known about the potential antagonism in As sorption generated by the dissolved organic carbon (DOC) from biochar, or whether DOC affects how As(V) interacts with BIOS. For this reason, our objectives were to evaluate the i) As(V) sorption potential in BIOS when there is presence of DOC from pyrolyzed biochars at different temperatures; and ii) identify whether the presence of DOC alters the surface complexes formed by As(V) sorbed in the BIOS. We conducted As(V) sorption experiments with BIOS at circumneutral pH conditions and in the presence of DOC from sugarcane (Saccharum officinarum) straw biochar at pyrolyzed 350 (BC350) and 750 °C (BC750). The As(V) content was quantified by inductively coupled plasma mass spectrometry, and the BIOS structure and As(V) sorption mechanisms were investigated by X-ray absorption spectroscopy. In addition, the organic moieties comprising the DOC from biochars were investigated by attenuated total reflectance Fourier transform infrared spectroscopy. The addition of DOC did not change the biomineral structure or As(V) oxidation state. The presence of DOC, however, reduced by 25 % the sorption of As(V), with BC350 being responsible for the greatest reduction in As(V) sorption capacity. Structural modeling revealed As(V) predominantly formed binuclear bidentate surface complexes on BIOS. The presence of DOC did not change the binding mechanism of As(V) in BIOS, suggesting that the reduction of As(V) sorption to BIOS was due to site blocking. In conclusion, our results bring insights into the fate of As(V) in surface waters and provide a basis for understanding the competitive sorption of As(V) in environments with biochar application.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Highly efficient removal and sequestration of Cr(VI) in confined MoS 2 interlayer Nanochannels: Performance and mechanism

Environmental contamination by Cr(VI) is of particular concern because of its severe toxicity and high mobility. In this study, we employed two-dimensional MoS 2 nanosheets in the removal of Cr(VI), with an emphasis on revealing the removal mechanisms, and how the compositional and structural uniqueness of 2D MoS 2 nanomaterials intrinsically impact the Cr removal efficiency. Through batch experiments with dispersed nanosheets, we found that MoS 2 nanosheets exhibited a high Cr(VI) removal capacity at ~1100 mg/g via a phase-dependent mechanism. Particularly, the 1T polymorph in the MoS 2 nanosheets removed Cr(VI) through a redox-reaction mechanism, which was different from the adsorptive removal of Cr(VI) by MoS 2 reported previously, highlighting the compositional effects on the removal mechanism and performance. More importantly, the reduced product Cr(III) was concurrently removed via precipitation and adsorption onto the MoS 2 nanosheets, which could avoid the additional pH-elevation step that is typically needed in the conventional treatment. The unique 2D flake-like structure of MoS 2 nanosheets enabled the formation of aligned and ion-accessible nanochannels, where Cr(VI) species were accommodated, reduced and sequestered. The irreversible shrinking of the nanochannels under drying modified the interior of the layer-stacked structure into confined compartments preventing the release and re-oxidation of the immobilized Cr(III). In conclusion, the compiled results highlight the effects of MoS 2 composition and structure on the Cr removal efficiency and mechanism, which has substantial implications on future studies tailoring these unique features of 2D nanomaterials for various remediation scenarios.

42 ENGINEERING↗
DOE OSTI2021

Resampling and data augmentation for short-term PV output prediction based on an imbalanced sky images dataset using convolutional neural networks

Integrating photovoltaics (PV) into electricity grids is challenged by potentially large fluctuations in power generation. In recent years, sky image-based PV output prediction using convolutional neural networks (CNNs) has emerged as a promising approach to forecasting fluctuations. A key challenge is imbalanced sky image datasets: because of the geography of solar PV system installations, sky image datasets are often rich in sunny condition data but deficient in cloudy condition data. This imbalance contrasts with the fact that model errors are dominated by cloudy condition performance. In this study, we attempt to remedy this by exploring the enrichment and augmentation of an imbalanced sky images dataset for two PV output prediction tasks: nowcasting (predicting concurrent PV output) and forecasting (predicting 15-minute-ahead future PV output). We empirically examine the efficacy of using different resampling and data augmentation approaches to create a rebalanced dataset for model development. A three-stage greedy search is used to determine the optimal resampling approach, data augmentation techniques and over-sampling rate. The results show that for the nowcast problem, resampling and data augmentation can effectively enhance the model performance, reducing overall root mean squared error (RMSE) by an average of 4%, or a 15 std. (standard deviation) of improvement compared to the variability of the baseline model. In contrast, the treatment RMSE for the forecast problem nearly always overlaps the baseline performance at the ± 2 std. level. The optimal resampling approach expands on the original dataset by over-sampling the minority cloudy data, with the best results from large over-sampling rate (e.g., 4 ~ 6 times over-sampling of cloudy images).

14 SOLAR ENERGY↗
DOE OSTI2020

The role of peer review and science for advancing public understanding

We live in a time of rapid change. The Covid-19 pandemic has united the world to understand and develop solutions to protect the health and wellbeing of society. At the same time, access to information on the internet and social media has exploded. People are exposed to information with many claims. Some of the information is relevant and accurate. A significant fraction may be inaccurate, biased, and potentially dangerous. With Covid-19, the information might point to cures that are toxic or risks that are not relevant. The scientific community has developed a process to develop and convey knowledge. The validation of results and their interpretation is critical to advancing knowledge. The core of the scientific process is based on developing a hypothesis-driven concept, designing and executing an experimental approach to prove or disprove the hypothesis, conducting a statistical analysis of the results to confirm their validity, and interpreting their meaning and impact. When their work is completed the scientist prepares to publish the work. Publication requires peer review. Hypotheses, experimental approaches, results, and interpretation of results are independently and anonymously reviewed by a scientific peer. The reviewers are selected based on their expertise in the field. The peer review process is essential for the integrity of the scientific process. Without a robust scientific process, society cannot discriminate between validated results and interpretations and biased, inaccurate, and potentially dangerous conjecture. With inaccurate science society and policy makers may make poor decisions that could hurt people and the world around them. While scientists should not censor information available to the public, scientists have a responsibility to inform the public. We must articulate what the scientific process is and why it is essential when considering the validity of information. Scientist are responsible for pointing out when public information has not been vetted through a scientific process and therefore cannot be considered conclusive. Scientists are responsible for highlighting information that has been generated and vetted with the scientific process. Over time, our goal is for the public to value the scientific process based on peer review. The public could become enlightened to the necessity for peer review to support decisions and action. Scientists need to contribute to advancing public knowledge. When invited to serve as a peer reviewer, scientists have a responsibility to contribute to the process. We all are extremely busy making peer review a distraction. While peer review does not directly benefit our own work and career, it benefits our chosen field of science. This is very important for the research area that our journal, Water-Energy Nexus, is focusing on. We cover the convergence of science and technology integrating across large spatial ranges (micro to global) in environmental pollution and the balance of remediation issues with energy use. Water-Energy Nexus wants to provide scientists with a platform for scientific debate and discussion on this rich and complicated topic. With the manuscripts submitted to WEN cover integrated research topics across a broad range of subjects from environment sciences through energy engineering, the role of peer review is essential. Peer review on a new submission to WEN should not be biased towards a specific science field. It should be done considering the complex nature of issues in the water-energy nexus. Scientists need to contribute to the public dialog. To accomplish these goals, we need to be honest, accurate, articulate, and use understandable language. The impact of WEN is very diverse affecting society in many ways. The scientific audience for WEN is diverse and readers may not fully understand the content of the papers outside their research expertise. Therefore, scientists, especially those who want to contribute to WEN, should work with communications specialists to convey message to benefit society. The audience includes the general public and researchers outside the author’s core specialty. While the peer-reviewed journal article is the cornerstone of our careers and critical for advancing scientific knowledge, a general interest story could benefit society even more. The author cannot lose sight that our work has two audiences, the science community, and more importantly, our family, friends, neighbors, and policy makers.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

In Situ Wood Delignification toward Sustainable Applications

As one of the most abundant and versatile natural materials on Earth, recently wood has attracted tremendous attention from scientists and engineers due to its outstanding advantages, including hierarchically porous microstructure, high mechanical strength, environmental friendliness, renewability, and biodegradability. Wood’s hierarchically porous structure and chemical components (e.g., cellulose, hemicelluloses, and lignin) enable its mechanical, ionic, optical, and thermal properties to be tuned via physical, chemical, and/or thermal modifications. Among these various approaches, the chemical delignification of bulk wood is the most fascinating, in which the majority of lignin and hemicelluloses is removed while leaving the cellulose intact, maintaining wood’s physical integrity and hierarchical structure. This delignified structure is unique, composed of hollow, aligned channels made up of cellulose microfibrils, and particularly attractive given its origin from a sustainable and renewable resource. As a result, delignified wood has attracted increasing attention for applications that go far beyond traditional wood utilization, such as lightweight yet strong structural materials, energy storage and conversion, environmental remediation, flexible electronics, and bioengineering. Here, we review recent developments in bulk wood delignification strategies toward the achievement of such advanced wood technologies for sustainable applications, with a focus on the research in our group. Similar to chemical pulping and bleaching, wood delignification involves a series of nucleophilic reactions based on alkaline Na 2 SO 3 or Na 2 S systems (i.e., chemical pulping) or electrophilic, radical, and oxidation reactions based on H 2 O 2 , ClO 2 , or NaClO systems (i.e., chemical bleaching) to deconstruct, fragment, and promote the hydrophilicity of lignin macromolecules, which finally make lignin easier to be removed. We discuss the structure and properties of partially and near-completely delignified wood, with a focus on process-structure–property relationships. The resulting delignified wood materials, with tunable structure and properties, demonstrate various advanced functions, in a wide range of advanced applications, such as building and construction, green energy, and electronics. Finally, the potential challenges and appealing perspectives of in situ wood delignification are discussed. In situ wood delignification, as a powerful modification strategy, has speeded up the development of advanced wood technologies and wood-based functional materials and products.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Recent Advances in Nonclassical Crystallization: Fundamentals, Applications, and Challenges

We report crystals are ubiquitous and play an important role in our daily life. Recent studies on properties and formation of crystals have proven the attachment of particle ranging from ion pairs to well-crystallized nanocrystal is one of the most important ways for crystallization. Compared with the monomer-by-monomer (i.e., atoms, ions, or molecules) addition described in longstanding classical theories, so-called nonclassical crystallization pathways are more complex as the non-specific interaction of variation in system free energy and reaction kinetics. In view of the detailed insights into nonclassical crystallization pathways has broadened the scope of research across various disciplines such as geological events, biomineralization mechanisms, environmental remediation, and the development of functional materials, this paper reviews the current state of the art in nonclassical nucleation (the prenucleation clusters pathway, aggregation pathway, etc.) and growth pathways (oriented attachment and random attachment) based on several spotlights. In addition, the observed specific phenomena on crystallization in the last 10 years as well as recent advancements and achievements made on the synthesis of mesocrystals are also elucidated. With implications and perspectives of nonclassical crystallization researches proposed in this paper, this review aims to summarize research advancement regarding crystallizing systems. Emphasis will be placed on novel insights into nonclassical crystallization of materials, which are expected to provide completely new perspectives on the underlying crystallization mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Thermally Driven Interfacial Degradation between Li 7 La 3 Zr 2 O 12 Electrolyte and LiNi 0.6 Mn 0.2 Co 0.2 O 2 Cathode

Solid-state batteries offer higher energy density and enhanced safety compared to the present lithium-ion batteries using liquid electrolytes. A challenge to implement them is the high resistances, especially at the solid electrolyte interface with the cathode. Sintering at elevated temperature is needed in order to get good contact between the ceramic solid electrolyte and oxide cathodes and thus to reduce contact resistances. Many solid electrolyte and cathode materials react to form secondary phases. It is necessary to find out which phases arise as a result of interface sintering and evaluate their effect on electrochemical properties. Herein, we assessed the interfacial reactions between LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and Li 7 La 3 Zr 2 O 12 (LLZO) as a function of temperature in air. We prepared model systems by depositing thin-film NMC622 cathode layers on LLZO pellets. The thin-film cathode approach enabled us to use interface-sensitive techniques such as X-ray absorption spectroscopy in the near-edge as well as the extended regimes and identify the onset of detrimental reactions. We found that the Ni and Co chemical environments change already at moderate temperatures, on-setting from 500 °C and becoming especially prominent at 700 °C. By analyzing spectroscopy results along with X-ray diffraction, we identified Li 2 CO 3 , La 2 Zr 2 O 7 , and La(Ni,Co)O 3 as the secondary phases that formed at 700 °C. The interfacial resistance for Li transfer, measured by electrochemical impedance spectroscopy, increases significantly upon the onset and evolution of the detected interface chemistry. Our findings suggest that limiting the bonding temperature and avoiding CO 2 in the sintering environment can help to remedy the interfacial degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Site-Selective Atomic Layer Deposition at Thermally Generated Surface Oxygen Vacancies on Rutile TiO 2

Unique atomic arrangements (i.e., defects) on material surfaces may exhibit distinctive reactivity that affords opportunities for selective surface chemistry exclusively at those sites. While theoretically appealing, site-selective atomic layer deposition (ALD) processes remain largely unrealized experimentally. Here we provide evidence for site-selective ALD that exclusively targets oxygen vacancies thermally generated at the surface of TiO 2 single crystals. High-resolution in situ ellipsometry reveals the nucleation behavior of dimethylaluminum isopropoxide (DMAI) and water at process conditions precisely tuned for selective hydroxylation of surface defects. An island growth model for nucleation and atomic force microscopy (AFM) imaging are consistent with a site-selective growth mechanism that depends on the surface oxygen vacancy density. This approach to direct ALD reactions at defective surface sites may provide future opportunities for targeted remediation of electronically imperfect interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Expanding the Design Space of Polymer–Metal Organic Framework (MOF) Gels by Understanding Polymer–MOF Interactions

The fabrication of polymer-MOF composite gels holds great potential to provide emergent properties for drug delivery, environmental remediation, and catalysis. To leverage the full potential of these composites, we investigated how the presence and chemistry of polymers impact MOF formation within the composites and, in turn, how MOFs impact polymer gelation. We show that polymers with a high density of strongly metal-binding carboxylic acids inhibit MOF formation; however, reducing the density of carboxylic acids or substituting them with weaker metal-binding hydroxyl groups permits both MOF formation and gelation within composites. Preparing composites with poly(ethylene glycol) (PEG), which does not bind MOF zirconium (Zr)-oxo clusters, and observing gelation suggests that MOFs can entrap polymer chains to create cross-links in addition to cross-linking them through polymer-Zr-oxo interactions. Both simulations and experiments show composite hydrogels formed with poly(vinyl alcohol) (PVA) to be more stable than those made with PEG, which can reptate through MOF pores upon heating. We demonstrate the generalizability of this composite formation process across different Zr-based MOFs (UiO-66, NU-901, UiO-67, and MOF-525) and by spin-coating gels into conformable films. PVA-UiO-66 composite hydrogels demonstrated high sorption and sustained release of methylene blue relative to the polymer alone (3× loading, 28× slower release), and PVA-MOF-525 composite hydrogels capably sorb the therapeutic peptide Angiotensin 1–7. By understanding the influence of polymer-MOF interactions on the structure and properties of composite gels, this work informs and expands the design space of this emerging class of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

NiAl–MoO 2 S 2 Nanoparticles: Structural Evolution and Mechanistic Insights into High-Performance Selenium Oxyanion Removal across Diverse pH Conditions

Advancing sorbent materials for the selective removal of toxic oxyanions from water requires synthetic control, tunable chemistry, and an atomic-level understanding of structure–function relationships. Here, we report the synthesis and detailed characterization of NiAl–MoO 2 S 2 , a novel layered double hydroxide (LDH) nanomaterial designed for the efficient sequestration of selenium oxoanions (SeO 3 2– and SeO 4 2– ) from complex aqueous environments. The material is synthesized through a room-temperature ion-exchange process, wherein interlayer NO 3 – anions in NiAl–LDH are replaced with MoO 2 S 2 2– clusters, forming high-surface-area, flower-like nanoparticles. Comprehensive structural analysis using the synchrotron X-ray pair distribution function, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy reveals a distinct chemical transformation of intercalated [MoO 2 S 2 ] 2– into [Mo 2 O 2 S 6 ] 2– -like clusters, generating redox-active interlayers that drive selenium capture. This tailored interfacial chemistry underpins the material’s exceptional sorption performance, achieving distribution coefficients (K d ) ≥ 10 6 mL/g and maximum capacities of 343 mg/g for SeO 4 2– and 514 mg/g for SeO 3 2– , outperforming state-of-the-art inorganic sorbents. Importantly, NiAl–MoO 2 S 2 maintains high selectivity and capacity across acidic, neutral, and alkaline pH, efficiently removing selenium from ppm to sub-10 ppb trace levels, even in the presence of competing ions typical of natural and industrial waters. The selenium uptake proceeds via reductive precipitation coupled with the oxidation of molybdenum and sulfide within the LDH framework. This study highlights the power of strategic synthetic modification and interlayer functionalization in LDHs to unlock new structural motifs and redox chemistries, offering a scalable route to advanced materials for environmental remediation.

Adsorption↗
DOE OSTI2022

Review of Multifunctional Separators: Stabilizing the Cathode and the Anode for Alkali (Li, Na, and K) Metal–Sulfur and Selenium Batteries

Alkali metal batteries based on lithium, sodium, and potassium anodes and sulfur-based cathodes are regarded as key for next-generation energy storage due to their high theoretical energy and potential cost effectiveness. However, metal–sulfur batteries remain challenged by several factors, including polysulfides’ (PSs) dissolution, sluggish sulfur redox kinetics at the cathode, and metallic dendrite growth at the anode. Functional separators and interlayers are an innovative approach to remedying these drawbacks. Here we critically review the state-of-the-art in separators/interlayers for cathode and anode protection, covering the Li–S and the emerging Na–S and K–S systems. The approaches for improving electrochemical performance may be categorized as one or a combination of the following: Immobilization of polysulfides (cathode); catalyzing sulfur redox kinetics (cathode); introduction of protective layers to serve as an artificial solid electrolyte interphase (SEI) (anode); and combined improvement in electrolyte wetting and homogenization of ion flux (anode and cathode). It is demonstrated that while the advances in Li–S are relatively mature, less progress has been made with Na–S and K–S due to the more challenging redox chemistry at the cathode and increased electrochemical instability at the anode. Throughout these sections there is a complementary discussion of functional separators for emerging alkali metal systems based on metal–selenium and the metal–selenium sulfide. The focus then shifts to interlayers and artificial SEI/cathode electrolyte interphase (CEI) layers employed to stabilize solid-state electrolytes (SSEs) in metal–sulfur solid-state batteries (SSBs). The discussion of SSEs focuses on inorganic electrolytes based on Li- and Na-based oxides and sulfides but also touches on some hybrid systems with an inorganic matrix and a minority polymer phase. The review then moves to practical considerations for functional separators, including scaleup issues and Li–S technoeconomics. The review concludes with an outlook section, where we discuss emerging mechanics, spectroscopy, and advanced electron microscopy (e.g. cryo-transmission electron microscopy (cryo-TEM) and cryo-focused ion beam (cryo-FIB))-based approaches for analysis of functional separator structure–battery electrochemical performance interrelations. Finally, throughout the review we identify the outstanding open scientific and technological questions while providing recommendations for future research topics.

25 ENERGY STORAGE↗
DOE OSTI2023

Oxide– and Silicate–Water Interfaces and Their Roles in Technology and the Environment

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by “anomalies” or “non-idealities” such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide– and silicate–water interfaces. This critical review discusses how science progresses from understanding ideal solid–water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. Further, we anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Synthetic Biology of Plants and Microbes for Agriculture, Environment, and Future Applications

Agriculture is under pressure to provide food for a growing population and the feedstock required to drive the bioeconomy. Methods to breed and genetically modify plants are inadequate to keep pace. When engineering crops, traits are painstakingly introduced into plants one-at-a-time, combine unpredictably, and are continuously expressed. Synthetic biology is changing these paradigms with new genome construction tools, computer aided design (CAD), and artificial intelligence (AI). “Smart plants” contain circuits that respond to environmental change, alter morphology, or respond to threats. Further, the plant and associated microbes (fungi, bacteria, archaea) are now being viewed by genetic engineers as a holistic system. Historically, plant health has been enhanced by many natural and laboratory-evolved soil microbes marketed to enhance growth, provide nutrients, or confer pest/stress resistance. Synthetic biology has expanded the number of species that can be engineered, increased the complexity of engineered functions, controlled environmental release, and assembled stable consortia. New CAD tools will manage genetic engineering projects spanning multiple plant genomes (nucleus, chloroplast, mitochondrion) and the thousands of genomes of associated bacteria/fungi. Here, this review covers advanced genetic engineering techniques to drive the next agricultural revolution, as well as push plant engineering into new realms for manufacturing, infrastructure, sensing, and remediation.

Clauer, Phillip [Massachusetts Inst. of Technology↗
DOE OSTI2026

Breakthrough Zn(II) Catalyst for Direct Air Capture Employing CO 2 Hydration

Direct air capture (DAC) represents a vital technology for atmospheric CO₂ remediation, but few studies have tested catalysts at dilute atmospheric CO₂ concentrations. Inspired by the carbonic anhydrase metalloenzyme, we report a catalytic DAC strategy employing robust zinc(II) enzyme mimics that enable efficient CO₂ sequestration pathways. A catalyst-mediated CO₂ hydration cycle in aqueous sorbents facilitates accelerated capture from dilute atmospheric air, thereby addressing the kinetic limitations observed in carbonate-based systems. Our developed complexes [ZnC1] and [ZnC2] enhance capture rates up to two-fold at millimolar concentrations and improve CO₂ mass transfer by 40-60% in 1 M K₂CO₃ sorbent under ambient conditions. These bench-stable, earth-abundant zinc catalysts operate effectively under dilute CO₂ concentrations, overcoming the kinetic limitations of conventional carbonate-based sorbents. As a result, mechanistic studies support a biomimetic catalytic cycle that facilitates rapid CO₂ conversion, demonstrating that catalyst-assisted DAC can enable energy-efficient, scalable carbon capture technologies.

Atmospheric chemistry↗
DOE OSTI2020

Insights into the Biogeochemical Cycling of Cobalt: Precipitation and Transformation of Cobalt Sulfide Nanoparticles under Low-Temperature Aqueous Conditions

Cobalt sulfide precipitates, key phases in the natural biogeochemical cycling of cobalt and in relevant remediation and resource recovery processes, remain poorly defined under low-temperature aqueous conditions. Here, we systematically studied the Co-(Fe) sulfides precipitated and aged in environmentally relevant solutions, defined by different combinations of pH, initial cobalt-to-iron ratios ([Co] aq /[Fe] aq ), with/without S 0 , and the presence/absence of sulfate-reducing bacteria. The initial abiogenic precipitates without Fe aq were composed exclusively of amorphous Co-sulfide hydrates (CoS· x H 2 O), whose estimated log K* was three orders of magnitude higher than that previously reported for crystalline Co-sulfides. The addition of S 0 , in combination with acidic pH and elevated temperature (60°C), resulted in the recrystallization of the amorphous precipitates into nanocrystalline jaipurite (hexagonal CoS) within one month (which otherwise remained stable for up to two months). In the presence of Fe(II) aq , the abiogenic precipitates were composed of more crystalline Co-sulfide hydrates and/or Co-rich mackinawite, the exact phase being dependent on the specific [Co] aq /[Fe(II)] aq . The biogenic precipitates displayed higher crystallinity for Co sulfides (up to the formation of nanocrystalline cobalt pentlandite, Co 9 S 8 ) and lower crystallinity for Co-rich mackinawite, suggestive of mineral-specific bacterial interaction. The revealed precipitation and transformation pathways of Co-(Fe-)sulfides in this study allows for predicting the prevalent Co-bearing phases in various natural and engineered environments.

58 GEOSCIENCES↗
DOE OSTI2021

Effect of Groundwater Age and Recharge Source on Nitrate Concentrations in Domestic Wells in the San Joaquin Valley

Nitrate is one of the most abundant contaminants in groundwater globally, in the United States, and in California (CA). We studied well construction information, water chemistry, stable isotopes, and noble gases to understand how groundwater travel time and recharge source and mechanism control nitrate concentrations in domestic wells in the San Joaquin Valley (SJV), CA, a large semiarid, irrigated agricultural region. Using nonparametric statistics, we find a decreasing trend in nitrates with groundwater travel time and well depth. Samples collected from wells that are closer to rivers and that show indications of river water recharge, either low recharge temperature or low δ 18 O signature, have lower concentrations of nitrates than samples with isotopic signatures indicating mixed source or local precipitation recharge. The curbing effect of river water recharge on nitrate concentrations in domestic wells is similar for direct river recharge and water applied as irrigation. This suggests that irrigation with river water also has a diluting effect that reduces the concentration of nitrate found in groundwater. This conclusion supports the idea that flood-managed aquifer recharge may be considered for remediation of groundwater nitrate when designing replenishment of aquifers.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Coprecipitation of Fe/Cr Hydroxides with Organics: Roles of Organic Properties in Composition and Stability of the Coprecipitates

Iron hydroxides are important scavengers for dissolved chromium (Cr) via coprecipitation processes; however, the influences of organic matter (OM) on Cr sequestration in Fe/ Cr-OM ternary systems and the stability of the coprecipitates are not well understood. Here, Fe/Cr-OM coprecipitation was conducted at pH 3, and Cr hydroxide was undersaturated. Acetic acid (HAc), poly(acrylic acid) (PAA), and Suwannee River natural organic matter (SRNOM) were selected as model OMs, which showed different complexation capabilities with Fe/Cr ions and Fe/Cr hydroxide particles. HAc had no significant effect on the coprecipitation, as the monodentate carboxyl ligand in HAc did not favor complexation with dissolved Fe/Cr ions or Fe/Cr hydroxide nanoparticles. Contrarily, PAA and SRNOM with polydentate carboxyl ligand had strong complexation with Fe/Cr ions and Fe/Cr hydroxide nanoparticles, leading to significant amounts of PAA/SRNOM sequestered in the coprecipitates, which caused the structural disorder and fast aggregation of the coprecipitates. In comparison with that of PAA, preferential complexation of Cr ions with SRNOM resulted in higher Cr/Fe ratios in the coprecipitates. This study advances the fundamental understanding of Fe/Cr-OM coprecipitation and mechanisms controlling the composition and stability of the coprecipitates, which is essential for successful Cr remediation and removal in both natural and engineered settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Facet-Dependent Photodegradation of Methylene Blue by Hematite Nanoplates in Visible Light

The expression of specific crystal facets in different nanostructures is known to play a vital role in determining the sensitivity toward photodegradation of organics, which can generally be ascribed to differences in surface structure and energy. Herein, we report the synthesis of hematite nanoplates with controlled relative exposure of basal (001) and edge (012) facets, enabling us to establish direct correlation between surface structure and the photocatalytic degradation efficiency of methylene blue (MB) in the presence of hydrogen peroxide. MB adsorption experiments showed that the capacity on (001) is about three times larger than on (012), and this is supported by density functional theory calculations suggesting adsorption energies about 1.5 times higher. However, this alone cannot explain the observed MB photodegradation rate, which is around 14.5 times faster on (001) than (012). The enhancement we attribute to a higher availability of photoelectron accepting surface Fe3+ sites on the (001) facet. This facilitates more efficient iron valence cycling and the heterogeneous photo-Fenton reaction yielding MB-oxidizing hydroxyl radicals at the surface. Our findings help establish a rational basis for design and optimization of hematite nanostructures as photocatalysts for environmental remediation.

Zong, Meirong↗