Natural subsurface environment is a complex heterogeneous system. To investigate the effect of ionic strength (IS) and heterogeneity on the transport and remobilization of graphene oxide (GO)-facilitated uranium (U(VI)) in saturated porous media, column experiments were performed by the injection of U(VI) alone and U(VI)+GO mixtures into homogeneous and heterogeneous porous media under low and high ionic strength (1 and 50 mM) conditions, and then the columns were successively flushed with background solution and DI water. Results showed that when U(VI) only was introduced into the columns, IS had little effect on the migration of U(VI) alone in both media and the presence of preferential flow in heterogeneous media slightly enhanced the mobility of U(VI). As U(VI)+GO mixtures were injected into the columns, GO showed strong mobility at low IS and high released peak at high IS. The appearance of GO significantly enhanced U(VI) transport in both media. Under low IS condition, the mobility of U(VI) was significantly enhanced at the injection phase, and the medium heterogeneity further promoted the amount of GO-sorbed U(VI) transport. At high IS, less GO-sorbed U(VI) was observed during injection phase, and a large amount of retained GO-sorbed U(VI) were released with GO remobilization during water flushing phase, and the release showed the longer-tailing phenomenon and the release amount was more pronounced in heterogeneous media. The findings in this study showed that the coupled effect of solution chemistry and media heterogeneity played important roles on GO-facilitated U(VI) transport and release in soil and groundwater system.

Huelva is a highly industrialized city in SW Spain hosting, among others, a Cu smelter, a phosphate fertilizer plant, a power plant, and oil refineries. This study aims to evaluate metal concentrations in lichens as bioindicators of atmospheric pollution in the impacted urban areas. Xanthoria parietina species from Huelva and nearby villages, as well as reference samples from remote, non-contaminated urban areas, were analyzed for trace elements (V, Cr, Mn, Co, Ni, Cu, Zn, Sr, As, Cd, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Er, Tm, Yb, Lu, Pb, Th, U) using Inductively Coupled Plasma-Mass Spectrometry; and for major elements (Ca, K, Mg, P, and S) by Inductively Coupled Plasma-Optical Emission Spectrometry after acid digestion.The metal composition of X. parietina exhibits spatial distribution patterns with extremely elevated concentrations (Co, Ni, Cu, Zn, As, Cd, Sb, Ba, Pb, U, and S) in the surroundings of the industrial estates to <1 km distance. Mean concentrations were significantly lower in the urban areas >1 km from the pollution sources. However, air pollution persists in the urban areas up to 4 km away, as the mean concentrations of Cu, Zn, As, Cd, Sb and S remained considerably elevated in comparison to the reference samples. Though rigorous source apportionment analysis was not the aim of this study, a good positive correlation of our results with metal abundances in ambient particulate matter and in pollution sources points to the Cu smelter as the main source of pollution. Hence, the severe air pollution affecting Huelva and nearby urban areas may be considered a serious health risk to local residents.

Abiotic reduction represents an attractive technology to control U(VI) contamination. In this work, an abiotic route of U(VI) reduction with humic acid at mineral surfaces is proposed and reaction mechanisms are addressed by periodic density functional theory calculations. Different influencing factors such as ligand effect, content of CO₃²⁻ ligands and substituent effect are inspected. The coordination chemistry of uranyl(VI) surface complexes relies strongly on substrates and ligands, and the calculated results are in good agreements with experimental observations available. For the OH⁻ ligand, two competitive mechanisms co-exist that respectively produce the U(IV) and U(V) species, and the former is significantly preferred because of lower energy barriers. Instead, the NO₃⁻ ligand leads to the formation of U(V) while for the Cl⁻ ligand, the U(VI) surface complex remains very stable and is not likely to be reduced because of very high energy barriers. The U(V) and U(IV) complexes are the predominant products for low and high CO₃²⁻ contents, respectively. Accordingly, the abiotic reduction processes with humic acid are efficient to manage U(VI) contamination and become preferred under basic conditions or at higher CO₃²⁻ contents. The U(VI) reduction is further promoted by introduction of electron-donating rather than electron-withdrawing substituents to humic acid. Electronic structure analyses and vibrational frequency assignments are calculated for the various uranium surface complexes of the reduction processes, serving as a guide for future experimental and engineered studies. The molecular-level understanding given in this work offers an abiotic route for efficient reduction of U(VI) and remediation of U(VI)-contaminated sites at ambient conditions.

The decontamination of U(VI) on graphene oxide/nano-alumina (GO/Al₂O₃) composites were investigated by batch, XRD, FT-IR and XPS techniques. The characterization results showed that GO/Al₂O₃ composites presented a variety of oxygen-containing functional groups, which provided the more surface reactive sites. The batch experiments indicated that sorption equilibrium of U(VI) on GO/Al₂O₃ composites was achieved within 30 min, and the maximum sorption capacity derived from Langmuir model was 142.8 mg/g at pH 6.5. In addition, the slight decrease of sorption capacity was observed even after fifth recycling times. These results indicated that GO/Al₂O₃ composites displayed the fast sorption rate, high sorption capacity and good regeneration performance. No effect of ionic strength revealed the inner-sphere surface complexation of U(VI) on GO/Al₂O₃ composites. FT-IR and XPS analysis demonstrated that the high adsorption of U(VI) on GO/Al₂O₃ was attributed to the various oxygen-bearing functional groups. In addition, the nano Al₂O₃ was transferred to amorphous AlO(OH) mineral phase by XRD pattern, which provided the additional reactive sorption sites. These observations indicated that GO-based composites can be regarded as a promising adsorbent for immobilization and pre-concentration of U(VI) from aqueous solutions in the environmental remediation.

There is a need to develop highly efficient materials for capturing uranium from nuclear wastewater. Here, 5-methylbenzotriazole modified graphene oxide (MBTA-GO) was used to adsorb U(VI) from aqueous solution. By the trials of different conditions, we found that the removal of U(VI) from acidic solution was strongly dependent on pH but independent of ionic strength. The U(VI) adsorption was perfectly conformed to the pseudo-second-order kinetics and the adsorption isotherms were simulated by the Langmuir model well. A high removal capacity (qₘₐₓ = 264 mg/g) for U(VI) at pH 3.5 was obtained. XPS, EXAFS analyses and DFT calculations revealed that the mechanism of uranium capture was ascribed to (i) the surface complexation by benzotriazole and carboxyl groups (providing lone pair electrons) on MBTA-GO and (ii) enhanced synergistic coordination ability of delocalized π-bond of triazole group toward U due to the transfer of electrons from graphene sheet to benzotriazole. DFT calculations further demonstrated that benzotriazole displayed stronger binding with U(VI) compared to carboxyl group due to higher binding energy of [Side/Surface-U-MBTA-GO] (79.745, 54.986 kcal/mol) than [MBTA-GO–COOH–U] (27.131 kcal/mol). This work will provide valuable insight into designing novel nitrogen-containing adsorbents for practical application in wastewater treatment.

In this study, graphene aerogel (GA) was successfully prepared through a simple hydrothermal method. The resulting GA exhibited a porous network structure with a large specific surface area (350.8 m²/g), ultra-light mass and easy separation from water. The pHIEP value of the GA was estimated to be 3.5. The adsorption process and the factors that affect adsorption capacity were studied. The adsorption could be conducted in a wide pH range from 2.0 to 7.0. The maximum adsorption capacity of GA towards U(VI) at pH 4.0 and T = 298 K was 238.67 mg/g calculated from the Langmuir model. The GA had greatly rapid adsorption property for the removal of U(VI) at pH 4.0. Kinetic data showed good correlation with pseudo-second-order equation. Fourier transform infrared spectroscopy and X-ray photoelectron spectrometry characterizations showed that GA adsorbed U(VI) through chemical interaction by oxygen-containing and nitrogen-containing groups functional groups. The results show that GA has excellent application potential as an adsorbent material for removing U(VI) from aqueous solution.

Efficient containment and capture of uranium (U(VI)) from aqueous solution is an essential component to ensure socially and environmentally sustainable development. Herein, the three-dimensional graphene/titanium dioxide composite (3D GA/TiO₂) was synthesized and applied as an effective adsorbent to remove U(VI) from wastewater as a function of contact time, temperature, pH and ion strength. The 3D GA/TiO₂ material was characterized by X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The batch experiments results indicated that the adsorption of U(VI) on materials were fitted with the pseudo-second order kinetics and Langmuir models. More specifically, 3D GA/TiO₂ (441.3 mg/g) was observed to outperform the GO (280.0 mg/g), rGO (140.9 mg/g) and TiO₂ (98.5 mg/g) at pH 5.0, which was attributable to the excellent cooperative effects. Furthermore, XPS analyses and DFT calculations confirmed the formation of surface complexes between oxygen-containing group and U(VI) with the U–O bonds length of 2.348 Å (U–O1) and 2.638 Å (U–O2). Meanwhile, the adsorption energy was calculated to be 1.60 eV, which showed a very strong chemisorption during the interaction process. It is believed that the 3D GA/TiO₂ revealed good removal performance for uranyl ions, which showed a great potential application to control the nuclear industrial pollution.

The effluents from nuclear mining processes contain relatively high content of radionuclides (such as uranium), which may seriously threaten the environment and human health. Herein, a novel adsorbent, porous hydroxyapatite, was prepared and proven highly efficient for removal of uranyl ions (U(VI)) given its high U(VI) uptake capacity of 111.4 mg/g, fast adsorption kinetics, and the potential stabilization of adsorbed U(VI). A nearly complete removal of U(VI) was achieved by porous HAP under optimized conditions. Langmuir model could well describe the adsorption equilibrium. The data fit well with pseudo-second-order kinetic model, suggesting that U(VI) adsorption is primarily attributed to chemisorption with porous HAP. Intraparticle diffusion analysis showed that the intraparticle diffusion is the rate-limiting step for U(VI) adsorption by porous HAP. After removal by porous HAP, the adsorbed U(VI) ions were incorporated into tetragonal autunite, which has a low solubility (log Ksp: −48.36). Our findings demonstrate that the porous HAP can effectively remediate uranium contamination and holds great promise for environmental applications.

This work reports the architecture of a novel class of membrane-supported 1D MOF hollow superstructures, by using the bio-inspired polydopamine (PDA) mediated contra-diffusion synthetic strategy, for facile and efficient separation of uranium in a flow-through mode. PDA chemistry was firstly employed to modify the inner surfaces of the cylindrical pore channels of polycarbonate track-etched membrane (PCTM), thereby regulating the heterogeneous nucleation and interfacial growth of ZIF-8 crystals. ZIF-8 hollow superstructures embedded in membrane matrix with well-defined 1D channels were obtained. These membrane-supported MOF hollow superstructures then, for the first time, served as integrated chromatographic micro-column arrays for effective entrapment of uranium from aqueous solutions. It is highlighted that the PCTM supported ZIF-8 superstructures exhibited outstanding uranium entrapment ability in both traditional batch mode (capacity 62.3 mg/g) and fast flow-through mode (removal rate over 90% for 3 level). Moreover, new insights into the interaction between ZIF-8 and uranyl ions were obtained, suggesting that an ion-exchange mechanism involved synergistic effect was responsible for uranium binding, especially in a long-term exposure. The membrane-supported 1D MOF hollow superstructures developed in this work represent a new category of organic-inorganic composite membrane. And, it is envisioned that the methodology established in this work would be versatile for preparing more MOF superstructures with deployable form for separation applications.In summary, a novel class of membrane-supported ZIF-8 hollow superstructure was fabricated for effective separation of uranyl ions.

Determinations of the mobility of metals from tailings is a critical part of any assessment of the environmental impacts of mining activities. The leaching of thorium and uranium from the tailings of different processing stages of a niobium mine was investigated for several pH, ionic strengths and concentrations of natural organic matter (NOM). The pH of the leaching solution did not have a noticeable impact on the extraction of Th, however, for pH values below 4, increased U mobilization was observed. Similarly, only a small fraction of Th (0.05%, ≤15 μg kg⁻¹) and U (1.22%, ≤6 μg kg⁻¹) were mobilized from the tailings in the presence of environmentally relevant concentrations of Ca, Mg or Na. However, in the presence of 10 mg L⁻¹ of fulvic acid, much higher concentrations of ca. 700 μg kg⁻¹ of Th and 35 μg kg⁻¹ of U could be extracted from the tailings. Generally, colloidal forms of Th and dissolved forms of U were mobilized from the tailings, however, in the presence of the fulvic acid, both dissolved and colloidal forms of the two actinides were observed. Single Particle ICP-MS was used to confirm the presence of Th (and U) containing colloids where significant numbers (up to 10⁷ mL⁻¹) of Th and U containing colloids were found, even in 0.2 μm filtered extracts. Although mass equivalent diameters in the range of 6–13 nm Th and 6–9 nm for U could be estimated (based upon the presence of an oxyhydroxide), most of the colloidal mass was attributed to larger (>200 nm) heterocomposite particles.