Synthesis of Metal-Nitrogen-Carbon Electrocatalysts with Atomically Regulated Nitrogen-Doped Polycyclic Aromatic Hydrocarbons.

Tuning the active site structure of metal-nitrogen-carbon electrocatalysts has recently attracted increasing interest. Herein, we report a bottom-up synthesis strategy in which atomically regulated N-doped polycyclic aromatic hydrocarbons (N-PAHs) of NxC42-x (x = 1, 2, 3, 4) were used as ligands to allow tuning of the active site's structures of M-Nx and establish correlations between the structures and electrocatalytic properties. Based on the synthesis process, detailed characterization, and DFT calculation results, active structures of Nx-Fe1-Nx in Fe1-Nx/RGO catalysts were constructed. The results demonstrated that the extra uncoordinated N atoms around the Fe1-N4 moieties disrupted the π-conjugated NxC42-x ligands, which led to more localized electronic state in the Fe1-N4 moieties and superior catalytic performance. Especially, the Fe1-N4/RGO exhibited optimized performance for ORR with E1/2 increasing by 80 mV and Jk at 0.85 V improved 18 times (compared with Fe1-N1/RGO). This synthesis strategy utilizing N-PAHs holds significant promise for enhancing the controllability of metal-nitrogen-carbon electrocatalyst preparation.

Facile low-temperature supercritical carbonization method to prepare high-loading nickel single atom catalysts for efficient photodegradation of tetracycline.

Environmental photocatalysis is a promising technology for treating antibiotics in wastewater. In this study, a supercritical carbonization method was developed to synthesize a single-atom photocatalyst with a high loading of Ni (above 5 wt.%) anchored on a carbon-nitrogen-silicate substrate for the efficient photodegradation of a ubiquitous environmental contaminant of tetracycline (TC). The photocatalyst was prepared from an easily obtained metal-biopolymer-inorganic supramolecular hydrogel, followed by supercritical drying and carbonization treatment. The low-temperature (300°C) supercritical ethanol treatment prevents the excessive structural degradation of hydrogel and greatly reduces the metal clustering and aggregation, which contributed to the high Ni loading. Atomic characterizations confirmed that Ni was present at isolated sites and stabilized by Ni-N and Ni-O bonds in a Ni-(N/O)6C/SiC configuration. A 5% Ni-C-Si catalyst, which performed the best among the studied catalysts, exhibited a wide visible light response with a narrow bandgap of 1.45 eV that could efficiently and repeatedly catalyze the oxidation of TC with a conversion rate of almost 100% within 40 min. The reactive species trapping experiments and electron spin resonance (ESR) tests demonstrated that the h+, and ·O2- were mainly responsible for TC degradation. The TC degradation mechanism and possible reaction pathways were provided also. Overall, this study proposed a novel strategy to synthesize a high metal loading single-atom photocatalyst that can efficiently remove TC with high concentrations, and this strategy might be extended for synthesis of other carbon-based single-atom catalysts with valuable properties.

Reductive Sequestration of Cr(VI) and Immobilization of C during the Microbially Mediated Transformation of Ferrihydrite-Cr(VI)-Fulvic Acid Coprecipitates.

Cr(VI) detoxification and organic matter (OM) stabilization are usually influenced by the biological transformation of iron (Fe) minerals; however, the underlying mechanisms of metal-reducing bacteria on the coupled kinetics of Fe minerals, Cr, and OM remain unclear. Here, the reductive sequestration of Cr(VI) and immobilization of fulvic acid (FA) during the microbially mediated phase transformation of ferrihydrite with varying Cr/Fe ratios were investigated. No phase transformation occurred until Cr(VI) was completely reduced, and the ferrihydrite transformation rate decreased as the Cr/Fe ratio increased. Microscopic analysis was uncovered, which revealed that the resulting Cr(III) was incorporated into the lattice structure of magnetite and goethite, whereas OM was mainly adsorbed on goethite and magnetite surfaces and located within pore spaces. Fine line scan profiles showed that OM adsorbed on the Fe mineral surface had a lower oxidation state than that within nanopores, and C adsorbed on the magnetite surface had the highest oxidation state. During reductive transformation, the immobilization of FA by Fe minerals was predominantly via surface complexation, and OM with highly aromatic and unsaturated structures and low H/C ratios was easily adsorbed by Fe minerals or decomposed by bacteria, whereas Cr/Fe ratios had little effect on the binding of Fe minerals and OM and the variations in OM components. Owing to the inhibition of crystalline Fe minerals and nanopore formation in the presence of Cr, Cr sequestration and C immobilization can be synchronously favored at low Cr/Fe ratios. These findings provide a profound theoretical basis for Cr detoxification and synchronous sequestration of Cr and C in anoxic soils and sediments.

Iterative Approach of Experiment-Machine Learning for Efficient Optimization of Environmental Catalysts: An Example of NOx Selective Reduction Catalysts.

An iterative approach between machine learning (ML) and laboratory experiments was developed to accelerate the design and synthesis of environmental catalysts (ECs) using selective catalytic reduction (SCR) of nitrogen oxides (NOx) as an example. The main steps in the approach include training a ML model using the relevant data collected from the literature, screening candidate catalysts from the trained model, experimentally synthesizing and characterizing the candidates, updating the ML model by incorporating the new experimental results, and screening promising catalysts again with the updated model. This process is iterated with a goal to obtain an optimized catalyst. Using the iterative approach in this study, a novel SCR NOx catalyst with low cost, high activity, and a wide range of application temperatures was found and successfully synthesized after four iterations. The approach is general enough that it can be readily extended for screening and optimizing the design of other environmental catalysts and has strong implications for the discovery of other environmental materials.

Microscopic insights into the variations of antibiotics sorption to clay minerals.

Understanding the adsorption behavior of antibiotic molecules on minerals is crucial for determining the environmental fate and transport of antibiotics in soils and waters. However, the microscopic mechanisms that govern the adsorption of common antibiotics, such as the molecular orientation during the adsorption process and the conformation of sorbate species, are not well understood. To address this gap, we conducted a series of molecular dynamics (MD) simulations and thermodynamics analyses to investigate the adsorption of two typical antibiotics, tetracycline (TET) and sulfathiazole (ST), on the surface of montmorillonite. The simulation results indicated that the adsorption free energy ranged from - 23 to - 32 kJ·mol-1, and - 9 to - 18 kJ·mol-1 for TET and ST, respectively, which was consistent with the measured difference of sorption coefficient (Kd) for TET-montmorillonite of 11.7 L·g-1 and ST-montmorillonite of 0.014 L·g-1. The simulations also found that TET was adsorbed through dimethylamino groups (85% in probability) with a molecular conformation vertical to the montmorillonite's surface, while ST was adsorbed through sulfonyl amide group (95% in probability) with vertical, tilted and parallel conformations on the surface. The results confirmed that molecular spatial orientations could affect the adsorption capacity between antibiotics and minerals. Overall, the microscopic adsorption mechanisms revealed in this study provide critical insights into the complexities of antibiotics adsorption to soil and facilitate the prediction of adsorption capacity of antibiotics on minerals and their environmental transport and fate. This study contributes to our understanding of the environmental impacts of antibiotic usage and highlights the importance of considering molecular-level processes when assessing the fate and transport of antibiotics in the environment.

An integrated supervision framework to safeguard the urban river water quality supported by ICT and models.

Models and information and communication technology (ICT) can assist in the effective supervision of urban receiving water bodies and drainage systems. Single model-based decision tools, e.g., water quality models and the pollution source identification (PSI) method, have been widely reported in this field. However, a systematic pathway for environmental decision support system (EDSS) construction by integrating advanced single techniques has rarely been reported, impeding engineering applications. This paper presents an integrated supervision framework (UrbanWQEWIS) involving monitoring-early warning-source identification-emergency disposal to safeguard the urban water quality, where the data, model, equipment and knowledge are smoothly and logically linked. The generic architecture, all-in-one equipment and three key model components are introduced. A pilot EDSS is developed and deployed in the Maozhou River, China, with the assistance of environmental Internet of Things (IoT) technology. These key model components are successfully validated via in situ monitoring data and dye tracing experiments. In particular, fluorescence fingerprint-based qualitative PSI and Bayesian-based quantitative PSI methods are effectively coupled, which can largely reduce system costs and enhance flexibility. The presented supervision framework delivers a state-of-the-art management tool in the digital water era. The proposed technical pathway of EDSS development provides a valuable reference for other regions.

Dynamic Changes in Biofilm Structures under Dynamic Flow Conditions.

Quantitative assessment of the responses of biofilm structure to external hydrodynamics is critical for understanding biofilm detachment mechanisms. This study used multidimensional imaging and numerical simulation approaches to elucidate the complex relationships between biofilm detachment and hydrodynamics with Shewanella oneidensis MR-1. By integrating real-time confocal laser scanning microscopy (CLSM) images with image analysis tools, the three-dimensional structural changes occurring in thin MR-1 biofilms (<10 µm) under hydrodynamic treatment at a flow velocity of 0.42 × 10-3 to 3.3 × 10-3 m/s in the laminar flow regime were visualized in situ and quantified with single-cell resolution. Analyses of the imaging results revealed high spatial heterogeneity in the degree and intensity of biofilm detachment. Spots with thick and rough biofilm surfaces or high flow rates had high detachment rates, indicating that local biofilm morphology, including thickness and roughness, and hydrodynamic flow conditions collectively controlled the detachment rate. Numerical simulations revealed a significant correlation between local detachment events and the shear stress induced by hydraulic flow at the three-dimensional level. Compared to the even or thin biofilm, a thick or rough structure might induce a 2-fold increase in shear stress over local biofilm surfaces at a microscale dimension. The results provide quantitative and microscopic insights into biofilm detachment processes in subsurface environments, especially in domains under dynamic flow conditions, such as those in hyporheic zones. The relationship between biofilm detachment and hydrodynamics and biofilm structural factors can be integrated into reactive transport models used to describe microbial growth and transport in porous media. IMPORTANCE Detachment is an important process determining the structure and function of bacterial biofilm, which has significant implications for biogeochemical cycling of elements, biofilm application, and infection control in clinical settings. Quantifying the responses of biofilm structure to hydrodynamics is crucial for understanding biofilm detachment mechanisms in aquatic environments. In this work, the spatial and temporal changes occurring in biofilm structures in response to different hydrodynamic conditions were studied by using flow cell reactors. We established the quantitative relationships among detachment, biofilm morphology, and shear stress induced by changes in hydrodynamic conditions. This work provides a quantitative understanding of the complex relationship between biofilm detachment and hydrodynamics in natural environments.

Legacy Effects of Sorption Determine the Formation Efficiency of Mineral-Associated Soil Organic Matter.

Sorption of dissolved organic matter (DOM) is one major pathway in the formation of mineral-associated organic matter (MOM), but there is little information on how previous sorption events feedback to later ones by leaving their imprint on mineral surfaces and solutions ("legacy effect"). In order to conceptualize the role of legacy effects in MOM formation, we conducted sequential sorption experiments with kaolinite and gibbsite as minerals and DOM derived from forest floor materials. The MOM formation efficiency leveled off upon repeated addition of identical DOM solutions to minerals due to the retention of highly sorptive organic molecules (primarily aromatic, nitrogen-poor, hydrogen-poor, and oxygen-rich molecules), which decreased the sorption site availability and simultaneously modified the mineral surface charge. Organic-organic interactions as postulated in multilayer models played a negligible role in MOM formation. Continued exchange between DOM and MOM molecules upon repeated sorption altered the DOM composition but not the MOM formation efficiencies. Sorption-induced depletion of high-affinity compounds from solutions further decreased the MOM formation efficiencies to pristine minerals. Overall, the interplay between the differential sorptivities of DOM components and the mineral surface chemistry explains the legacy effects that contribute to the regulation of fluxes and the distribution of organic matter in the soil.

Chemodiversity of Soil Dissolved Organic Matter.

Dissolved organic matter (DOM) plays a key role in many biogeochemical processes, but the drivers controlling the diversity of chemical composition and properties of DOM molecules (chemodiversity) in soils are poorly understood. It has also been debated whether environmental conditions or intrinsic molecular properties control the accumulation and persistence of DOM due to the complexity of both molecular composition of DOM and interactions between DOM and surrounding environments. In this study, soil DOM samples were extracted from 33 soils collected from different regions of China, and we investigated the effects of climate and soil properties on the chemodiversity of DOM across different regions of China, employing a combination of Fourier transform ion cyclotron resonance mass spectrometry, optical spectroscopy, and statistical analyses. Our results indicated that, despite the heterogeneity of soil samples and complex influencing factors, aridity and clay can account for the majority of the variations of DOM chemical composition. The finding implied that DOM chemodiversity is an ecosystem property closely related to the environment, and can be used in developing large-scale soil biogeochemistry models for predicting C cycling in soils.

Impact of Physico-Chemical Heterogeneity on Arsenic Sorption and Reactive Transport under Water Extraction.

Heterogeneity in physical and chemical properties is a common characteristic in a subsurface environment. This study investigated the effect of physico-chemical heterogeneity on arsenic (As) sorption and reactive transport under water extraction in a layered system with preferential flow paths. A flume experiment was performed to derive the spatio-temporal data of As reactive transport. The results indicated that the heterogeneous system significantly accelerated downward (vertical direction) As migration as a coupled effect of physical and chemical heterogeneity that led to fast As transport with low As sorption along the preferential flow paths. The results also indicated that such a heterogeneity effect was driven by water extraction that enhanced the downward groundwater flow along the preferential flow paths. Numerical simulations were performed by matching the experimental results to provide insights into the dominant processes controlling the As migration in the heterogeneous systems. The simulation results highlighted the importance of the kinetic oxidation of mineral-bonded Fe(II) to Fe(III) in the clay matrix that dynamically increased As sorption affinity and retarded As reactive transport. A coupled model of reactive transport along the preferential flow paths, sorption-retarded diffusion from the preferential flow paths into the clay matrixes, and reactions that change sorption affinity in the matrix was required to describe the As reactive transport systems with physico-chemical heterogeneities. The results have strong implications for understanding and modeling As downward migration from shallow to deep aquifers under groundwater pumping conditions in field systems with inherent heterogeneity.

Conduction Band of Hematite Can Mediate Cytochrome Reduction by Fe(II) under Dark and Anoxic Conditions.

While it was recently reported that the conduction band of iron minerals can mediate electron transfer between Fe(II) and different Fe(III) lattice sites during Fe(II)-catalyzed mineral transformation, it is unclear whether such a conduction band mediation pathway occurs in the microbial Fe(II) oxidation system under dark and anoxic subsurface conditions. Here, using cytochrome c (c-Cyts) as a model protein of microbial Fe(II) oxidation, the in vitro kinetics and thermodynamics of c-Cyts reduction by Fe(II) were studied. The results showed that the rates of c-Cyts reduction were greatly enhanced in the presence of the semiconducting mineral hematite (Hem, α-Fe2O3). The electrochemical experiments separating Fe(II) and c-Cyts demonstrated that electrons from Fe(II) to the electrode or from the electrode to c-Cyts could directly penetrate hematite, resulting in enhanced current. Independent photochemical and photoluminescence experiments indicated that c-Cyts could be directly reduced by the conduction band electrons of hematite which were generated under light illumination. In c-Cyts+Fe(II)+Hem, the redox potential of Fe(II)-Hem was shifted from -0.15 to -0.18 V and that of c-Cyts+Hem changed slightly from -0.05 to -0.04 V. For the bulk hematite, Mott-Schottky plots illustrated that the flat band was shifted negatively and positively in the presence of Fe(II) and oxidized c-Cyts, respectively, and the surface electron/charge density was higher in the presence of Fe(II)/c-Cyts. As a consequence, the redox gradients from adsorbed Fe(II) to adsorbed c-Cyts allow electron transfer across the conduction band of hematite and facilitate c-Cyts reduction. This mechanistic study on conduction band-mediating electron transfer could help interpret the role of semiconducting minerals in the microbial Fe(II) oxidation process under dark anoxic conditions.

Elucidating the Role of Sulfide on the Stability of Ferrihydrite Colloids under Anoxic Conditions.

While the reaction mechanisms between ferrihydrite and sulfide are well-documented, the role of redox reactions on the particle-particle stability of ferrihydrite colloids is largely overlooked. Such reactions are critical for a number of (bio)geochemical processes governing ferrihydrite-based colloid processing and their associated role in nutrient and contaminant subsurface dynamics. Taking a fundamental colloid chemistry approach, along with a complementary suite of characterization techniques, here, we explore the stability mechanisms of ferrihydrite colloids over a wide range of environmentally relevant sulfide concentrations at pH 6.0. Results show that sulfide lowered the stability of both ferrihydrite colloids in a concentration-dependent fashion. At lower sulfide concentrations (15.6-62.5 µM), ferrihydrite colloids are apparently stable, but their critical coagulation concentration (CCC) in NaCl linearly decreases with increasing sulfide concentration. This is attributed to the formation of negatively charged elemental sulfur (S(0)) nanoparticles on the surfaces of positively charged ferrihydrite, intensifying the electrostatic attractions between oppositely charged regions on adjacent ferrihydrite surfaces. Further increasing sulfide concentration generates more S(0) attaching to the ferrihydrite surface. This results in effective surface charge neutralization and then subsequent charge reversal, leading to extensive aggregation of ferrihydrite (core) colloids. Interestingly, for the ferrihydrite colloids with higher hydrodynamic diameter, aggregation rates linearly decreases with increasing sulfide concentration from 156.3 to 312.5 µM, which is likely due to the formation of substantial amounts of negatively charged S(0) and FeS. Findings highlight the significance of sulfidation products in controlling the stability of ferrihydrite colloids in sulfidic environments.

Coupled Kinetics Model for Microbially Mediated Arsenic Reduction and Adsorption/Desorption on Iron Oxides: Role of Arsenic Desorption Induced by Microbes.

The dynamic behavior of arsenic (As) species is closely associated with iron mineral dissolution/transformation in the environment. Bacterially induced As(V) desorption from iron oxides may be another important process that facilitates As(V) release from iron oxides without significant reductive dissolution of iron oxides. Under the impact of bacterially induced desorption, As kinetic behavior is controlled by both the microbial reduction of As(V) and the As(III)&As(V) reactions on iron oxide surfaces. However, there is still a lack of quantitative understanding on the coupled kinetics of these processes in complex systems. We developed a quantitative model that integrated the time-dependent microbial reduction of As(V) with nonlinear As(III)&As(V) adsorption/desorption kinetics on iron oxides under the impact of bacterially induced As(V) desorption. We collected and modeled literature data from 11 representative studies, in which microbial reduction reactions occurred with minimal iron oxide dissolution/transformation. Our model highlighted the significance of microbially induced As(V) desorption and time-dependent changes of microbial reduction rates. The model can quantitatively assess the roles and the coupling of individual reactions in controlling the overall reaction rates. It provided a basis for developing comprehensive models for As cycling in the environment by coupling with other chemical, physical, and microbial processes.

A Generalized-Rate Model for Describing and Scaling Redox Kinetics in Sediments Containing Variable Redox-Reactive Materials.

This study developed a generalized modeling approach for describing and scaling redox reactions from reactive components to the sediments and their assemblages, using Cr(VI) reduction as an example. Batch experiments were performed to characterize the rates of Cr(VI) reduction in four Fe(II)-containing sediments and their assemblages. The experimental data were first used to calibrate a generalized-rate model of Cr(VI) reduction with generic rate parameters. The generalized-rate model was then used to describe the kinetics of Cr(VI) reduction in the sediment assemblages by linearly scaling the rate parameters from the individual sediments. Via comparison with the experimental results, this study found that the generalized-rate model with generic rate parameters can describe Cr(VI) reduction in individual sediments and their assemblages with different redox reactivity toward Cr(VI) reduction. The sediment-associated Fe(II) and its reactivity were found to be the key variables in the generalized model for describing the Cr(VI) reduction in the studied sediments. A three-step extraction method was subsequently developed to estimate the rate-specific Fe(II) pools that can facilitate the application of the scaling approach in field systems.

Coupled Hydro-Biogeochemical Processes Controlling Cr Reductive Immobilization in Columbia River Hyporheic Zone.

An experiment and modeling study was conducted to investigate coupled hydro-biogeochemical processes controlling reductive immobilization of groundwater Cr in the hyporheic zone (HZ) at the U.S. Department of Energy's Hanford Site, where dynamic surface water-groundwater exchange occurs on a daily basis. Experiments were performed to calibrate kinetic models, and the calibrated models were incorporated into a multicomponent reactive transport model to simulate Cr redox transformation and immobilization under field hydrological conditions. The results revealed that the rates of Cr(VI) reduction, Cr(III) accumulation, and Cr(VI) release to the river are mostly affected by dynamic sediment redox conditions represented by Fe(II) reactivity, which is controlled by its cyclic interaction with O2 carried by river water, microbial activities, and the supply and bioavailability of organic carbon (OC) that is present in the HZ and/or carried by transport. In addition, the HZ geophysical properties including hydraulic conductivity and the thickness of the top alluvial layer have a significant influence on Cr reactive transport and immobilization by controlling residence times for reactions and the supply rates of O2, Cr, and OC into the HZ. The results provide important insights into the dynamic redox environments in the HZ that can reductively immobilize contaminants.

Functional Enzyme-Based Approach for Linking Microbial Community Functions with Biogeochemical Process Kinetics.

The kinetics of biogeochemical processes in natural and engineered environmental systems is typically described using Monod-type or modified Monod-type models. These models rely on biomass as surrogates for functional enzymes in microbial communities that catalyze biogeochemical reactions. A major challenge of applying such models is the difficulty of quantitatively measuring functional biomass for the constraining and validation of the models. However, omics-based approaches have been increasingly used to characterize microbial community structure, functions, and metabolites. Here, we propose an enzyme-based model that can incorporate omics data to link microbial community functions with biogeochemical process kinetics. The model treats enzymes as time-variable catalysts for biogeochemical reactions and applies a biogeochemical reaction network to incorporate intermediate metabolites. The sequences of genes and proteins from metagenomes, as well as those from the UniProt database, were used for targeted enzyme quantification and to provide insights into the dynamic linkage among functional genes, enzymes, and metabolites that are required in the model. The application of the model was demonstrated using denitrification, as an example, by comparing model simulations with measured functional enzymes, genes, denitrification substrates, and intermediates.

Effect of Water Chemistry and Hydrodynamics on Nitrogen Transformation Activity and Microbial Community Functional Potential in Hyporheic Zone Sediment Columns.

Hyporheic zones (HZ) are active biogeochemical regions where groundwater and surface water mix. N transformations in HZ sediments were investigated in columns with a focus on understanding how the dynamic changes in groundwater and surface water mixing affect microbial community and its biogeochemical function with respect to N transformations. The results indicated that denitrification, DNRA, and nitrification rates and products changed quickly in response to changes in water and sediment chemistry, fluid residence time, and groundwater-surface water exchange. These changes were accompanied by the zonation of denitrification functional genes along a 30 cm advective flow path after a total of 6 days' elution of synthetic groundwater with fluid residence time >9.8 h. The shift of microbial functional potential toward denitrification was correlated with rapid NO3- reduction collectively affected by NO3- concentration and fluid residence time, and was resistant to short-term groundwater-surface water exchange on a daily basis. The results implied that variations in microbial functional potential and associated biogeochemical reactions in the HZ may occur at space scales where steep concentration gradients present along the flow path and the variations would respond to dynamic HZ water exchange over different time periods common to natural and managed riverine systems.

Internal Domains of Natural Porous Media Revealed: Critical Locations for Transport, Storage, and Chemical Reaction.

Internal pore domains exist within rocks, lithic fragments, subsurface sediments, and soil aggregates. These domains, termed internal domains in porous media (IDPM), represent a subset of a material's porosity, contain a significant fraction of their porosity as nanopores, dominate the reactive surface area of diverse media types, and are important locations for chemical reactivity and fluid storage. IDPM are key features controlling hydrocarbon release from shales in hydraulic fracture systems, organic matter decomposition in soil, weathering and soil formation, and contaminant behavior in the vadose zone and groundwater. Traditionally difficult to interrogate, advances in instrumentation and imaging methods are providing new insights on the physical structures and chemical attributes of IDPM, and their contributions to system behaviors. Here we discuss analytical methods to characterize IDPM, evaluate information on their size distributions, connectivity, and extended structures; determine whether they exhibit unique chemical reactivity; and assess the potential for their inclusion in reactive transport models. Ongoing developments in measurement technologies and sensitivity, and computer-assisted interpretation will improve understanding of these critical features in the future. Impactful research opportunities exist to advance understanding of IDPM, and to incorporate their effects in reactive transport models for improved environmental simulation and prediction.

(99)Tc(VII) Retardation, Reduction, and Redox Rate Scaling in Naturally Reduced Sediments.

An experimental and modeling study was conducted to investigate pertechnetate (Tc(VII)O4(-)) retardation, reduction, and rate scaling in three sediments from Ringold formation at U.S. Department of Energy's Hanford site, where (99)Tc is a major contaminant in groundwater. Tc(VII) was reduced in all the sediments in both batch reactors and diffusion columns, with a faster rate in a sediment containing a higher concentration of HCl-extractable Fe(II). Tc(VII) migration in the diffusion columns was reductively retarded with retardation degrees correlated with Tc(VII) reduction rates. The reduction rates were faster in the diffusion columns than those in the batch reactors, apparently influenced by the spatial distribution of redox-reactive minerals along transport paths that supplied Tc(VII). X-ray computed tomography and autoradiography were performed to identify the spatial locations of Tc(VII) reduction and transport paths in the sediments, and results generally confirmed the newly found behavior of reaction rate changes from batch to column. The results from this study implied that Tc(VII) migration can be reductively retarded at Hanford site with a retardation degree dependent on reactive Fe(II) content and its distribution in sediments. This study also demonstrated that an effective reaction rate may be faster in transport systems than that in well-mixed reactors.

Molecular dynamics simulations of uranyl and uranyl carbonate adsorption at aluminosilicate surfaces.

Adsorption at mineral surfaces is a critical factor controlling the mobility of uranium(VI) in aqueous environments. Therefore, molecular dynamics (MD) simulations were performed to investigate uranyl(VI) adsorption onto two neutral aluminosilicate surfaces, namely, the orthoclase (001) surface and the octahedral aluminum sheet of the kaolinite (001) surface. Although uranyl preferentially adsorbs as a bidentate inner-sphere complex on both surfaces, the free energy of adsorption on the orthoclase surface (-15 kcal mol(-1)) is significantly more favorable than that at the kaolinite surface (-3 kcal mol(-1)), which is attributed to differences in surface functional groups and the ability of the orthoclase surface to release a surface potassium ion upon uranyl adsorption. The structures of the adsorbed complexes compare favorably with X-ray absorption spectroscopy results. Simulations of the adsorption of uranyl complexes with up to three carbonate ligands revealed that uranyl complexes coordinated to up to two carbonate ions are stable on the orthoclase surface whereas uranyl carbonate surface complexes are unfavored at the kaolinite surface. Combining the MD-derived equilibrium adsorption constants for orthoclase with aqueous equilibrium constants for uranyl carbonate species indicates the presence of adsorbed uranium complexes with one or two carbonates under alkaline conditions, in support of current uranium(VI) surface complexation models.