Polyethylene terephthalate (PET) microplastics as radionuclide (U-232) carriers: Surface alteration matters the most.

Polyethylene terephthalate (PET) plastics find widespread use in various aspects of our daily lives but often end up in the environment as (micro)plastic waste. In this study, the adsorption efficiency of PET microplastics for U-232 has been investigated prior and after surface alteration (e.g. oxidation (PET-ox), MnO2-coating (PET/MnO2) and biofilm-formation (PET/Biofilm)) in the laboratory (at pH 4, 7 and 9) and seawater samples under ambient conditions and as a function of temperature. The results revealed a significant increase in the adsorption efficiency upon surface alteration, particularly after biofilm development on the MP's surface. Specifically, the Kd values evaluated for the adsorption of U-232 by PET, PET-ox, PET/MnO2 and PET/Biofilm are 12, 27, 73 and 363, respectively, at pH 7 and under ambient conditions. The significantly higher adsorption efficiency of the altered and particularly biofilm-coated PET, emphasizes the significance of surface alteration, which may occur under environmental conditions. In addition, according to the thermodynamic investigations the adsorption of U-232 by PET-MPs (both non-treated and modified), the adsorption is an endothermic and entropy-driven reaction. A similar behavior has been also observed using seawater solutions and assumes that surface alteration is expected to enhance the radionuclide, stability, mobility and bioavailability in environmental water systems.

Kinetic and competitive effects of sorption on multi-element migration through crushed granite and biotite gneiss in Ca-HCO3-SO4 type groundwater.

Crystalline rock is used as the host rock for the disposal of high-level radioactive waste. Two cationic elements (Cs(I) and Ni(II)) and three anionic elements (Se(IV/VI), Mo(VI), and U(VI)) were selected to comprehensively evaluate the sorption behaviors of these radionuclides on crystalline granite and biotite gneiss. The anionic elements showed weak sorption (log Kd (L·kg-1) < 1) and little competition effect, while the cationic elements (log Kd (L·kg-1) = 2-3) showed clear competition (18-98% in Kd values) even at low concentrations. Analysis by pseudo-second-order kinetics showed that Cs(I) sorbed at similar rates on both rocks (20% faster on biotite gneiss), but Ni(II) sorbed 190% faster on biotite gneiss than on granite. That is why the retardation factors for Cs(I) and Ni(II) were reversed in the biotite gneiss column compared to their distribution coefficients. Therefore, the sorption kinetics cannot be neglected in groundwater systems with high flow rates. In the desorption column test, the retardation followed the order of the distribution coefficient. The desorption column test revealed that the distribution coefficient determines the strength of sorption on crystalline rocks.

Application of Natural Antibacterial Plants in the Extraction of Uranium from Seawater.

Marine biofouling directly affects the performance and efficiency of uranium (U(VI)) extraction from seawater. Compared to traditional chemical methods, natural plant extracts are generally biodegradable and nontoxic, making them an environmentally friendly alternative to synthetic chemicals in solving the marine biofouling problem. The effectiveness of natural antibacterial plants (i.e., pine needle, peppermint, Acorus gramineus Soland, Cacumen platycladi, and wormwood) in solving the marine biofouling problem was evaluated in this work. Experimental results showed that natural antibacterial plants could kill Vibrio alginolyticus in solution and effectively solve the marine biofouling problem of U(VI) extraction. To improve the adsorption capacity of natural plants for U(VI) in seawater, poly(vinylphosphonic acid) (PVPA) was modified on natural antibacterial plant surfaces by irradiation grafting technology. PVPA and natural antibacterial plants work as active sites and base materials for the U(VI) extraction material, respectively. The recovery performance of PVPA/pine needle for U(VI) was preliminarily studied. Results show that the adsorption of U(VI) on PVPA/pine needle follows pseudo-second-order and Langmuir models, and the maximum adsorption capacity is 111 mg/g at 298 K and pH 8.2.

U(VI) mitigation via forward osmosis: Elucidation of retention mechanisms and co-ion effects.

Uranium (U) is a chemical and radioactive toxic contaminant affecting many groundwater systems. The focus of this study was to evaluate the suitability of forward osmosis (FO) for uranium rejection from contaminated groundwater under field-relevant conditions. Laboratory experiments with aqueous solution containing uranium were performed with FO membrane to understand the uranium rejection mechanism under varied pH, draw solution concentration, and presence of co-ions. Further, experiments were performed with U-contaminated field groundwater. Results of the hydrogeochemcial modelling using PHREEQC indicated that the rejection mechanism of uranium was highly dependent on aqueous speciation. Uranium rejection was maximum at alkaline pH with ca. 99% rejection due to charge-based interactions between membrane and dominant uranyl complexes. The results of the co-ion study indicated that nitrate and phosphate ions decrease uranium rejection. Whereas, bicarbonates, calcium, and magnesium ions concentrated uranium in feed solution. Further, the uranium adsorption onto the membrane surface primarily depended on pH of the aqueous solution with maximum adsorption at pH 5.5. Our results show that the World Health Organization's drinking water guideline value of 30 µgL-1 for U could be achieved via FO process in field groundwater containing low dissolved solids.

The permeability evolution mechanism of ore-bearing strata during acid in-situ leaching of uranium: A case study of Bayanwula uranium mine in Inner Mongolia of China.

Uranium mainly comes from ISL of sandstone-type uranium deposits in China. The change of porosity and permeability caused by blockage of ore-bearing strata is one of the most serious problems in acid ISL of uranium. In this paper, the groundwater tracer test was carried out before and 1 year after ISL to explore the pore and permeability evolution characteristics of the ore-bearing layer during ISL. The test results showed that the leaching solution migrated along two seepage channels and the water-bearing medium was isotropic. After 1 year of ISL, the flow rate of the leaching solution decreased obviously. However, the flow rate of the leaching solution in slower channel decreased more than that in the faster channel in all directions, which was caused by the more adequate chemical reactions between the leaching solution and the minerals of the ore-bearing layer and the more corresponding precipitation in the slower channel. In addition, the flow rate along the direction of groundwater flow decreased less than that in the direction of vertical groundwater flow. This was closely related to the transformation of aquifer medium by hydrodynamic field. Initial stage of ISL, the occurrence of plugging is closely related to the precipitation-dissolution process of iron and aluminum minerals under the change of pH, which is accompanied by the continuous precipitation of gypsum.

Variation of groundwater and mineral composition of in situ leaching uranium in Bayanwula mining area, China.

The reaction between the lixiviant and the minerals in the aquifer of In-situ uranium leaching (ISL) will result mineral dissolution and precipitation. ISL will cause changes in the chemical composition of groundwater and the porosity and permeability of aquifer, as well as groundwater pollution. Previous studies lack three-dimension numerical simulation that includes a variety of minerals and considers changes in porosity and permeability properties simultaneously. To solve these problems, a three-dimensional reactive transport model (RTM) which considered minerals, main water components and changes in porosity and permeability properties in Bayanwula mine has been established. The results revealed that: (1) Uranium elements were mainly distributed inside the mining area and had a weak trend of migration to the outside. The strong acidity liquid is mainly in the mining area, and the acidity liquid dissolved the minerals during migrating to the outside of the mining area. The concentration front of major metal cations such as K+, Na+, Ca2+ and Mg2+ is about 150m away from the boundary. (2) The main dissolved minerals include feldspar, pyrite, calcite, sodium montmorillonite and calcium montmorillonite. Calcite is the most soluble mineral and one of the sources of gypsum precipitation. Other minerals will dissolve significantly after calcite is dissolved. (3) ISL will cause changes in porosity and permeability of the mining area. Mineral dissolution raises porosity and permeability near the injection well. Mineral precipitation reduced porosity and permeability near the pumping well, which can plugging the pore throat and affect recovery efficiency negatively.

Chemical implication of the partition coefficient of 137Cs between the suspended and dissolved phases in natural water.

After the Fukushima Daiichi nuclear power plant accident, the terrestrial environment became severely contaminated with radiocesium. Consequently, the river and lake water in the Fukushima area exhibited high radiocesium levels, which declined subsequently. The partition coefficient of 137Cs between the suspended sediment (SS) and dissolved phases, Kd, was introduced to better understand the dynamic behavior of 137Cs in different systems. However, the Kd values in river water, ranging from 2 × 104 to 7 × 106 L kg-1, showed large spatiotemporal variability. Therefore, the factors controlling the 137Cs partition coefficient in natural water systems should be identified. Herein, we introduce a chemical model to explain the variability in 137Cs Kd in natural water systems. The chemical model includes the complexation of Cs+ with mineral and organic binding sites in SS, metal exchange reactions, and the presence of colloidal species. The application of the chemical model to natural water systems revealed that Cs+ is strongly associated with binding sites in SS, and a major chemical interaction between 137Cs and the binding sites in SS is the isotope exchange reaction between stable Cs and 137Cs, rather than metal exchange reactions with other metal ions such as potassium ions. To explain the effect of the SS concentration on Kd, the presence of colloidal 137Cs passing through a filter is significant as the dominant dissolved species of 137Cs in river water. These results suggest that a better understanding of stable Cs dissolved in natural water is important for discerning the geochemical and ecological behaviors of 137Cs in natural water.

Effect of grain size variation on strontium sorption to heterogeneous aquifer sediments.

Strontium-90 (90Sr) is a major contaminant at nuclear legacy sites. The mobility of 90Sr is primarily governed by sorption reactions with sediments controlled by high surface area phases such as clay and iron oxides. Sr2+ adsorption was investigated in heterogeneous unconsolidated aquifer sediments, analogous to those underlying the UK Sellafield nuclear site, with grainsizes ranging from gravels to clays. Batch sorption tests showed that a linear Kd adsorption model was applicable to all grainsize fractions up to equilibrium [Sr] of 0.28 mmol L-1. Sr2+ sorption values (Kd; Langmuir qmax) correlated well with bulk sediment properties such as cation exchange capacity and surface area. Electron microscopy showed that heterogeneous sediments contained porous sandstone clasts with clay minerals (i.e. chlorite) providing an additional adsorption capacity. Therefore, gravel corrections that assumed that the > 2 mm fractions are inert were not appropriate and underestimated Kd(bulk) adsorption coefficients. However, Kd (<2 mm) values measured from sieved sediment fractions, were effectively adjusted to within error of Kd (bulk) using a surface area dependant gravel correction based on particle size distribution data. Amphoteric pH dependent Sr2+ sorption behaviour observed in batch experiments was consistent with cation exchange modelling between pH 2-7 derived from the measured cation exchange capacities. Above pH 7 model fits were improved by invoking a coupled cation exchange/surface complexation which allowed for addition sorption to iron oxide phases. The overall trends in Sr2+ sorption (at pH 6.5-7) produced by increasing solution ionic strength was also reproduced in cation exchange models. Overall, the results showed that Sr2+ sorption to heterogeneous sediment units could be estimated from Kd (<2 mm) data using appropriate gravel corrections, and effectively modelled using coupled cation exchange and surface complexation processes.

Electrochemistry-assisted in-situ regeneration of oxygen vacancies and Ti(III) active sites for persistent uranium recovery at a low potential.

Electrochemical uranium extraction (EUE) from seawater is a very promising strategy, but its practical application is hindered by the high potential for electrochemical system, as well as the low selectivity, efficiency, and poor stability of electrode. Herein, we developed creatively a low potential strategy for persistent uranium recovery by electrochemistry-assisted in-situ regeneration of oxygen vacancies and Ti(III) active sites coupled with indirect reduction of uranium, finally achieving high selectivity, efficient and persistent uranium recovery. As-designed titanium dioxide rich in oxygen vacancies (TiO2-VO) electrode displayed an EUE efficiency of ∼99.9 % within 180 min at a low potential of 0.09 V in simulated seawater with uranium of 5∼20 ppm. Moreover, the TiO2-VO electrode also showed high selectivity (89.9 %) to uranium, long-term cycling stability and antifouling activity in natural seawater. The excellent EUE property was attributed to the fact that electrochemistry-assisted in-situ regeneration of oxygen vacancies and Ti(III) active sites enhanced EUE cycling process and achieved persistent uranium recovery. The continuous regeneration of oxygen vacancies not only reduced the adsorption energy of U(VI)O22+ but also serve as a storage and transportation channel for electrons, accelerating electron transfer from Ti(III) to U(VI) at solid-liquid interface and promoting EUE kinetic rate.

Open-Framework Vanadate as Efficient Ion Exchanger for Uranyl Removal.

The elimination of uranium from radioactive wastewater is crucial for the safe management and operation of environmental remediation. Here, we present a layered vanadate with high acid/base stability, [Me2NH2]V3O7, as an excellent ion exchanger capturing uranyl from highly complex aqueous solutions. The material possesses an indirect band gap, ferromagnetic characteristic and a flower-like morphology comprising parallel nanosheets. The layered structure of [Me2NH2]V3O7 is predominantly upheld by the H-bond interaction between anionic framework [V3O7]nn- and intercalated [Me2NH2]+. The [Me2NH2]+ within [Me2NH2]V3O7 can be readily exchanged with UO22+. [Me2NH2]V3O7 exhibits high exchange capacity (qm = 176.19 mg/g), fast kinetics (within 15 min), high removal efficiencies (>99%), and good selectivity against an excess of interfering ions. It also displays activity for UO22+ ion exchange over a wide pH range (2.00-7.12). More importantly, [Me2NH2]V3O7 has the capability to effectively remove low-concentration uranium, yielding a residual U concentration of 13 ppb, which falls below the EPA-defined acceptable limit of 30 ppb in typical drinking water. [Me2NH2]V3O7 can also efficiently separate UO22+ from Cs+ or Sr2+ achieving the highest separation factors (SFU/Cs of 589 and SFU/Sr of 227) to date. The BOMD and DFT calculations reveal that the driving force of ion exchange is dominated by the interaction between UO22+ and [V3O7]nn-, whereas the ion exchange rate is influenced by the mobility of UO22+ and [Me2NH2]+. Our experimental findings indicate that [Me2NH2]V3O7 can be considered as a promising uranium scavenger for environmental remediation. Additionally, the simulation results provide valuable mechanistic interpretations for ion exchange and serve as a reference for designing novel ion exchangers.

Leaching behaviour of 226Ra from uranium tailings and adsorption behaviour in geotechnical medias.

The leaching process of uranium tailings is a typical water-rock interaction. The release of 226Ra from uranium tailings depends on the nuclides outside the intrinsic properties of uranium tailings on the one hand, and is influenced by the water medium on the other. In this paper, a uranium tailings repository in southern China was used as a research object, and uranium tailings at different depths were collected by drilling samples and mixed to analyze the 226Ra occurrence states. Static dissolution leaching experiments of 226Ra under different pH conditions, solid-liquid ratio conditions, and ionic strength conditions were carried out, and the adsorption and desorption behaviours of 226Ra in five representative stratigraphic media were investigated. The results show that 226Ra has a strong adsorption capacity in representative strata, with adsorption distribution coefficient Kd values ranging from 1.07E+02 to 1.29E+03 (mL/g) and desorption distribution coefficients ranging from 4.97E+02 to 2.71E+03 (mL/g), but the adsorption is reversible. The 226Ra in uranium tailings exists mainly in the residual and water-soluble states, and the release of 226Ra from uranium tailings under different conditions is mainly from the water-soluble and exchangeable state fractions. Low pH conditions, low solid-liquid ratio conditions and high ionic strength conditions are favourable to the release of 226Ra from uranium tailings, so the release of 226Ra from uranium tailings can be reduced by means of adjusting the pH in the tailings and setting up a water barrier. The results of this research have important guiding significance for the management of existing uranium tailings ponds and the control of 226Ra migration in groundwater, which is conducive to guaranteeing the long-term safety, stability and sustainability of uranium mining sites.

Adsorption-desorption of 241Am(â ¢) on montmorillonite colloids and quartz sand: Effects of pH, ionic strength, colloid concentration and grain size.

Clay colloids in the subsurface environment have a strong adsorption capacity for radionuclides, and the mobile colloids will carry the nuclides for migration, which would promote the movability of radionuclides in the groundwater environment and pose a threat to the ecosphere. The investigations of the adsorption/desorption behaviors of radionuclides in colloids and porous media are significant for the evaluation of the geological disposal of radioactive wastes. To illustrate the adsorption/desorption behaviors of 241Am(Ⅲ) in Na-montmorillonite colloid and/or quartz sand systems at different pH (5, 7 and 9), ionic strengths (0, 0.1 and 5 mM), colloid concentrations (300 and 900 mg/L), nuclide concentrations (500, 800, 1100 and 1400 Bq/mL) and grain sizes (40 and 60 mesh), a series of batch sorption-desorption experiments were conducted. Combining the analysis of the physical and chemical properties of Na-montmorillonite with the Freundlich model, the influencing mechanism of different controlling factors is discussed. The experimental results show that the adsorption/desorption behaviors of 241Am(Ⅲ) in Na-montmorillonite colloid and/or quartz sand strongly are influenced by the pH value and ionic strength of a solution, the colloid concentration as well as quartz sand grain size. The adsorption and desorption isotherms within all the experimental conditions could be well-fitted by the Freundlich model and the correlation coefficients (R2) are bigger than 0.9. With the increase in pH, the adsorption partition coefficient (Kd) at 241Am(Ⅲ)-Na-montmorillonite colloid two-phase system and 241Am(Ⅲ)-Na-montmorillonite colloid-quartz sand three-phase system presents a trend which increases firstly followed by decreasing, due to the changes in the morphology of Am with pH. The Kd of 241Am(Ⅲ) adsorption on montmorillonite colloid and quartz sand decreases with increasing in ionic strength, which is mainly attributed to the competitive adsorption, surface complexation and the reduction of surface zeta potential. Additionally, the Kd increases with increasing colloid concentrations because of the increase in adsorption sites. When the mean grain diameter changes from 0.45 to 0.3 mm, the adsorption variation trends of 241Am(Ⅲ) remain basically unchanged. The research results obtained in this work are meaningful and helpful in understanding the migration behaviors of radionuclides in the underground environment.

Carboxymethyl cellulose and metal-organic frameworks immobilized into polyacrylamide hydrogel for ultrahigh efficient and selective adsorption U(VI) from seawater.

Metal-organic frameworks (MOF)-polymer hybrid hydrogel solves the processable forming of MOF powder and energy consumption of uranium extraction. However, the hybrid hydrogel by conventional synthesis methods inevitably lead to MOF agglomeration, poor filler-polymer interfacial compatibility and slowly adsorption. Herein, we designed that ZIF-67 was implanted into the carboxymethyl cellulose/polyacrylamide (CMC/PAM) by network-repairing strategy. The carboxyl and amino groups on the surface of CMC/PAM drive the uniform growth of ZIF-67 inside the CMC/PAM, which form an array of oriented and penetrating microchannels through coordination bonds. Our strategy eliminate the ZIF-67 agglomeration, increase the interfacial compatibility between MOF and polymer. The method also improve the free and fast diffusion of uranium in CMC/PAM/ZIF-67 hydrogel. According to the experimental, these enhancements synergistically enabled the CMC/PAM/ZIF-67 have a maximum adsorption capacity of 952 mg g-1. The adsorption process of CMC/PAM/ZIF-67 fits well with pseudo-second-order model and Langmuir isotherm. Meanwhile, the CMC/PAM/ZIF-67 maintain a high removal rate (87.3 %) and chemical stability even during ten adsorption-desorption cycles. It is worth noting that the adsorption amount of CMC/PAM/ZIF-67 in real seawater is 9.95 mg g-1 after 20 days, which is an ideal candidate adsorbent for uranium extraction from seawater.

Unraveling the mechanism of iodate adsorption by anthocyanin-rich fruit waste as green adsorbents for Applications of radioactive iodine remediation in water environment.

In aquatic settings, radioactive iodine from nuclear waste can exist as iodate (IO3-). This study explored the efficiency and mechanism of IO3- adsorption by minimally modified anthocyanin-based adsorbents. Pomegranate peels and mangosteen pericarps were selected from an initial screening test and could remove over 70% of 10 mg/L IO3-. The adsorbents yielded adsorption capacity (q) of 9.59 mg/g and 2.31 mg/g, respectively, at room temperature. At 5 °C, q values increased to 14.5 and 5.13 mg/g, respectively. Pomegranate peels showed superior performance, with approximately 4 times the anthocyanin content of mangosteen pericarps. Both adsorbents took 120 min to reach adsorption equilibrium, and no desorption was observed after 8 days (I-131 half-time). Confirmation of physisorption was indicated by the fit of the pseudo-first-order reaction model, negative entropy (exothermic), and negative activation energy (Arrhenius equation). IO3- inclusion was confirmed through adsorbent surface modifications in scanning electron microscope images, the increased iodine content post-adsorption in energy-dispersive X-ray spectroscopy analysis, and alterations in peaks corresponding to anthocyanin-related functional groups in Fourier transform infrared spectroscopy analysis. X-ray absorption near-edge spectroscopy at 4564.54 eV showed that iodine was retained in the form of IO3-. Through the computational analysis, electrostatic forces, hydrogen bonds, and π-halogen interactions were deduced as mechanisms of IO3- adsorption by anthocyanin-based adsorbents. Anthocyanin-rich fruit wastes emerged as sustainable materials for eliminating IO3- from water.

Molten salt mediated single-step synthesis of reusable nanostructured CaTiO3 for the removal and recovery of Sr2+: A potential adsorbent for the contaminated water bodies.

The facile synthesis approach for the adsorbent preparation and recyclability during decontamination of radioactive pollutants is a significant concern in water treatment. The objective of this study is to, synthesis via solid-state reaction of the nanostructured CaTiO3 for the removal and recovery of strontium (Sr2+) from the various water sources. The influence of the adsorption-dependent parameters including, initial concentration, adsorbent dose, pH, contact time and co-existing ions interference were investigated. The prepared adsorbent was characterized by different analytical techniques like FT-IR, SEM with EDAX, TEM, TGA-DTG, Powder XRD and BET surface analysis. The kinetic models were also used, and according to the kinetic models, a pseudo-second-order kinetic model (R2 = 0.999) was better fitted to the adsorption of Sr2+ ions onto CaTiO3 rather than pseudo-first-order kinetics, which could properly represent the observed adsorption of Sr2+. For the isotherm study, the results are best fitted to the Langmuir isotherm model (R2 = 0.98) with a maximum adsorption capacity of 102.04 mg/g. The common ions (Na+, Mg2+, Ca2+, and K+) and Sr2+ having a concentration of 1:2, 1:3, and 1:4, where 82.8, 79.5, and 68.2 % removal was achieved of Sr2+ in each respective matrix. In addition, the adsorption and corresponding recovery and removal for the different Sr2+spiked matrices in deionized water, tap water, well water, lake water, and seawater were investigated with 97, 65.6, 76.5, 73.9 and 17.8 % removal respectively. Also, the CaTiO3 showed excellent recyclability with minimal loss even after 5 consecutive recyclability cycles and >90% removal of strontium achieved. Hence, prepared nanostructured CaTiO3 could be considered a promising adsorbent for the removal and recovery of Sr2+ions from contaminated water bodies.

Weak electro-stimulation promotes microbial uranium removal: Efficacy and mechanisms.

Removal and recovery of uranium from uranium-mine wastewater is beneficial to environmental protection and resource preservation. Reduction of soluble hexavalent U (U(VI)) to insoluble tetravalent uranium (U(IV)) by microbes is a plausible approach for this purpose, but its practical implementation has long been restricted by its intrinsic drawbacks. The electro-stimulated microbial process offers promise in overcoming these drawbacks. However, its applicability in real wastewater has not been evaluated yet, and its U(VI) removal mechanisms remain poorly understood. Herein, we report that introducing a weak electro-stimulation considerably boosted microbial U(VI) removal activities in both synthetic and real wastewater. The U(VI) removal has proceeded via U(VI)-to-U(IV) reduction in the biocathode, and the electrochemical characterization demonstrates the crucial role of the electroactive biofilm. Microbial community analysis shows that the broad biodiversity of the cathode biofilm is capable of U(VI) reduction, and the molecular ecological network indicates that synthetic metabolisms among electroactive and metal-reducing bacteria play major roles in electro-microbial-mediated uranium removal. Metagenomic sequencing elucidates that the electro-stimulated U(VI) bioreduction may proceed via e-pili, extracellular electron shuttles, periplasmic and outer membrane cytochrome, and thioredoxin pathways. These findings reveal the potential and mechanism of the electro-stimulated U(VI) bioreduction system for the treatment of U-bearing wastewater.

Retention of immobile Se(0) in flow-through aquifer column systems during bioreduction and oxic-remobilization.

Selenium (Se) is a toxic contaminant with multiple anthropogenic sources, including 79Se from nuclear fission. Se mobility in the geosphere is generally governed by its oxidation state, therefore understanding Se speciation under variable redox conditions is important for the safe management of Se contaminated sites. Here, we investigate Se behavior in sediment groundwater column systems. Experiments were conducted with environmentally relevant Se concentrations, using a range of groundwater compositions, and the impact of electron-donor (i.e., biostimulation) and groundwater sulfate addition was examined over a period of 170 days. X-Ray Absorption Spectroscopy and standard geochemical techniques were used to track changes in sediment associated Se concentration and speciation. Electron-donor amended systems with and without added sulfate retained up to 90% of added Se(VI)(aq), with sediment associated Se speciation dominated by trigonal Se(0) and possibly trace Se(-II); no Se colloid formation was observed. The remobilization potential of the sediment associated Se species was then tested in reoxidation and seawater intrusion perturbation experiments. In all treatments, sediment associated Se (i.e., trigonal Se(0)) was largely resistant to remobilization over the timescale of the experiments (170 days). However, in the perturbation experiments, less Se was remobilized from sulfidic sediments, suggesting that previous sulfate-reducing conditions may buffer Se against remobilization and migration.

Facile modification of graphene oxide and its application for the aqueous uranyl ion sequestration: Insights on the mechanism.

Graphene oxide (GO) has been proved with favorable affinity to U(VI), while some drawbacks such as poor dispersity and low adsorption performance limit its application. Herein, cetyltrimethylammonium bromide (CTAB) modified graphene oxide (MGO) composites were successfully fabricated, characterized and compared with graphene oxide (GO) in the sequestration of U(VI) in aqueous solutions. The results showed that maximum adsorption rate of MGO (99.21%) was obviously higher than that of GO (66.51%) under the same initial condition. Simultaneous introduction of C-H and NO coupled with the enhanced dispersity of GO after modification were mainly responsible for the updated performance verified with multiple characterization techniques. Based on the results of kinetics and isotherms investigations, the experimental data were best described by Pseudo-first-order kinetic model and Redlich-Peterson isotherm model. The results of ΔH, ΔS and ΔG show that adsorptive behaviors of uranyl ion on MGO are endothermic and spontaneous. The study provides a feasible alternative to the chemical modification of GO and enhancing the performance towards uranyl ion removal from solution.

Factors influencing the reduction of U(VI) by magnetite.

Under suboxic and anoxic environments, magnetite is one corrosion product of iron being used in nuclear waste canisters. Previous studies have reported a complete reduction of U(VI) on the surfaces of biogenic and natural magnetite crystals, while incomplete reductions to U(V)/U(IV)-containing species have been observed on chemosynthetic magnetite. To date, the reasons behind such disparities remain poorly studied. This study shows that uranyl nitrate or uranyl acetate is mainly reduced to UO2+x oxides (e.g., U4O9, U3O8, etc.) by chemosynthetic magnetite under acidic conditions. When extra zero valent-iron was added, the reaction rate was significantly increased, and an improved but still incomplete U(VI) reduction was observed. Nitrate and ferric ions are ubiquitous in natural environment. Results demonstrate that the nitrate ion associated with uranyl and the ferric ion contained in magnetite or generated from U(VI) reduction have a non-negligible oxidative effect on the final products, which could mainly account for the incomplete reduction of U(VI) by chemosynthetic magnetite in the absence or presence of extra zero valent-iron observed in this study. Furthermore, the surface loading of uranium in U-Fe systems can, in part, unravel the discrepancies in various observations. An enhanced understanding of the U-Fe reaction mechanism can facilitate predictions of the extent of uranium mobility with respect to nuclear waste disposal and radioactive decontamination.

Characterization of subsurface media from locations up- and down-gradient of a uranium-contaminated aquifer.

The processing of sediment to accurately characterize the spatially-resolved depth profiles of geophysical and geochemical properties along with signatures of microbial density and activity remains a challenge especially in complex contaminated areas. This study processed cores from two sediment boreholes from background and contaminated core sediments and surrounding groundwater. Fresh core sediments were compared by depth to capture the changes in sediment structure, sediment minerals, biomass, and pore water geochemistry in terms of major and trace elements including pollutants, cations, anions, and organic acids. Soil porewater samples were matched to groundwater level, flow rate, and preferential flows and compared to homogenized groundwater-only samples from neighboring monitoring wells. Groundwater analysis of nearby wells only revealed high sulfate and nitrate concentrations while the same analysis using sediment pore water samples with depth was able to suggest areas high in sulfate- and nitrate-reducing bacteria based on their decreased concentration and production of reduced by-products that could not be seen in the groundwater samples. Positive correlations among porewater content, total organic carbon, trace metals and clay minerals revealed a more complicated relationship among contaminant, sediment texture, groundwater table, and biomass. The fluctuating capillary interface had high concentrations of Fe and Mn-oxides combined with trace elements including U, Th, Sr, Ba, Cu, and Co. This suggests the mobility of potentially hazardous elements, sediment structure, and biogeochemical factors are all linked together to impact microbial communities, emphasizing that solid interfaces play an important role in determining the abundance of bacteria in the sediments.