A review on photocatalytic attribution and process of pyrolytic biochar in environment.

Biochar has attracted significant attention due to its excellent environmental benefits and extensive applications. Recently, a consensus has been accepted that biochar can act as a photocatalyst and trigger effective photocatalytic reactions in the environment, which is important to energy conversion and the cycle of elements. However, its photocatalytic processes and the corresponding environmental impacts need to receive more and due attention. In this review, we provide a comprehensive summary of the underlying correlations among the pyrolytic evolution of biomass, the structure characteristic of biochar, and the resultant photocatalytic performance. Moreover, the photocatalytic processes and the influence of environmental factors were elaborately investigated on biochar. Finally, future tendencies and challenges in the photocatalysis of biochar have been prospected in the environmental field. This review has offered innovative insights into the photocatalytic essential of biochar and highly enhanced the understanding of its environmental impact.

Different photoreduction processes of Cr(VI) on cellulose-rich and lignin-rich biochar.

In this study, a series of biochar were prepared via pyrolyzing cellulose-rich pakchoi (PBC) and lignin-rich corncob (CBC) to explore the photoreduction process of Cr(VI). X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy confirmed higher oxygenated functional groups in PBC (48.9%-57.1%), whereas CBC exhibited more aromatization properties due to the stable aromatic network in lignin. For PBC, the valence bands decreased from 1.42 eV to 1.20 eV with the increase of pyrolysis temperature from 300 °C to 500 °C; however, an opposite trend was observed for CBC. The photoreduction of Cr(VI) clearly showed that both PBC and CBC had the best performance at the carbonization temperature of 300 °C (named PBC300 and CBC300). It is noted that PBC300 exhibited the most effective photoreduction of Cr(VI), which was about 1.3 times higher than that of CBC300. The maximum reduction capacities of Cr(VI) were 68.2 mg g-1 on PBC300 and 66.1 mg g-1 on CBC300 at pH∼2.0. Compared with the insoluble char substances, dissolved black carbons made more contributions for Cr(VI) photoreduction, ∼70% in PBC and almost 100% in CBC, which suggested that in the case of PBC, the insoluble char and the corresponding dissolved black carbons play an important role in the photoreduction of Cr(VI). However, only dissolved black carbons contributed to Cr(VI) photoreduction on CBC. As the key reaction pathway, the interfacial electron transport dominated Cr(VI) reduction on PBC and CBC. Moreover, the radical of •O2- had some contribution to the reduction of Cr(VI) only in the PBC system. Interestingly, •OH could promote the photoreduction of Cr(VI) in both PBC and CBC systems, which might be due to the fact that •OH facilitated the formation of small molecule fragments. These findings provide an essential basis for evaluating the environmental impact of photocatalytic behaviors of biochar.

Visual tracking of label-free microplastics in wheat seedlings and their effects on crop growth and physiology.

The effects of microplastics on crop plants have attracted growing attention. However, little is known about the effects of microplastics and their extracts on the growth and physiology of wheat seedlings. In this study, hyperspectral-enhanced dark field microscopy and scanning electron microscopy were used to accurately track the accumulation of 200 nm label-free polystyrene microplastics (PS) in wheat seedlings. The PS accumulated along the root xylem cell wall and in the xylem vessel member and then moved toward to the shoots. In addition, lower concentration (≤ 5 mg·L-1) of microplastics increased root hydraulic conductivity by 80.6 %- 117.0 %. While higher PS treatment (200 mg·L-1) considerably decreased plant pigments content (chlorophyll a, b, and total chlorophyll) by 14.8 %, 19.9 %, and 17.2 %, respectively, and decreased root hydraulic conductivity by 50.7 %. Similarly, catalase activity was reduced by 17.7 % in root and 36.8 % in shoot. However, extracts from the PS solution showed no physiological effect on wheat. The result confirmed that it was the plastic particle, rather than the chemical reagents added in the microplastics, contributed to the physiological variation. These data will benefit to better understanding on the behavior of microplastics in soil plants, and to providing of convincing evidence for the effects of terrestrial microplastics.

Remediating petroleum hydrocarbons in highly saline-alkali soils using three native plant species.

Phytoremediation of total petroleum hydrocarbons (TPHs) contamination is a process that uses the synergistic action of plants and rhizosphere microorganisms to degrade, absorb and stabilize pollutants in the soil, and has received increasing attention in recent years. However, this technology still has some challenges under certain conditions (e.g., highly alkaline and saline environments). The present study was selected three native plant species (alfalfa, tall fescue, and ryegrass) to remediate petroleum pollutants in greenhouse pot experiments. The results indicate that TPH contamination not only inhibited plant growth, soil chemical properties and soil fertility (i.e. lower plant biomass, chlorophyll, pH, and electrical conductivity), but also increased the malondialdehyde, glutathione, and antioxidant enzyme activities (catalase and polyphenol oxidase). Further, correlation analysis results illustrated that TPH removal was strongly positively correlated with chlorophyll, soil fertility, and total organic carbon, but was negatively correlated with dehydrogenase, polyphenol oxidase, pH, and electrical conductivity. The highest TPHs removal rate (74.13%) was exhibited by alfalfa, followed by tall fescue (61.79%) and ryegrass (57.28%). The degradation rates of short-chain alkanes and low rings polycyclic aromatic hydrocarbons (PAHs) were substantially higher than those of long-chain alkanes and high rings PAHs. The findings of this study provide valuable insights into petroleum decontamination strategies in the highly saline - alkali environments.

Speciation of Zn and Cd in sierozem soil, northwest China: bulk EXAFS and micro synchrotron X-ray fluorescence.

Previous research studies have confirmed that Zn and Cd are the most predominant heavy metals in the Baiyin district, Gansu province, China. Furthermore, the speciation of Zn and Cd is a key factor in controlling the mobility, bioavailability, and toxicity of metals in Zn/Cd co-contaminated soil. In this study, the speciation of Zn and Cd in different types of agricultural soils including the Yellow River irrigated soil (s3) and sewage irrigated soil (s1 and s2) was investigated and compared by a combination of sequential extraction, bulk X-ray absorption fine structure (XAFS), and micro-X-ray fluorescence (µ-XRF) techniques. The results of the speciation quantified by XAFS were in general agreement with those obtained by sequential extraction, and the combination of both approaches allowed a reliable description of Zn/Cd speciation in soil. The speciation of Zn in the s1 soil exposed around the smelter was similar to speciation of Zn in the sewage irrigated s2 soil. In both soils, Zn was predominantly present as Zn-Al LDH (31-36%), Zn adsorbed on calcite (37-47%), and primary minerals (14-18% sphalerite and 9% franklinite). In contrast, the proportions of organic Zn (23%) and Zn-Al LDH (53%) were significantly higher in the Yellow River irrigated s3 soil, while that of Zn-calcite (24%) was lower. This indicated that Zn in s3 was less mobile and bioavailable than that in s1 and s2 soils. The content of bioavailable Zn in s3 was much lower than the background value and Zn did not pose a threat to the Yellow River irrigated soil. In addition, Cd was strongly correlated with Zn content and exhibited a simpler speciation. Cd adsorbed on illite and calcite was found as the major species in both soil types, posing higher migration and toxicity to the environment. Our study reported the speciation and correlation of Zn/Cd in sierozem soil for the first time and provided a significant theoretical basis for remediation actions to minimize Zn/Cd risks.

Interactions between micaceous minerals weathering and cesium adsorption.

The environmental behavior of radioactive cesium (RCs) in contaminated areas is generally governed by soil and sediment components and natural weathering conditions. In this study, desorption tests and spectroscopic approaches were used to explore the interaction between the weathering of micaceous minerals (i.e., biotite and phlogopite) and the adsorption of Cs+ and the critical role of weathering in the environmental behavior of RCs. Results showed that the reaction sequence between weathering and Cs+ adsorption significantly affected the surface species of Cs+ and the structure of biotite and phlogopite. Regardless of whether it occurred before, after, or during Cs+ adsorption, weathering generated more high-affinity adsorption sites, namely, interlayer sites (ITs) and frayed edge sites (FESs), to different extents, and then facilitated the uptake of Cs+ at FESs and ITs on micaceous minerals in a poorly exchangeable state. Cs+ stabilized the micaceous mineral structure once it was absorbed within collapsed interlayers by hindering cation exchange and preventing further destruction during weathering. As important weathering factors, high temperature and Ca2+ content promoted the binding of Cs+ in the interlayers of biotite and phlogopite by enhancing interlayer cation exchange. These findings are beneficial for a better understanding of the environmental behaviors of RCs in the hydrosphere and pedosphere.

High Durability of Fe-N-C Single-Atom Catalysts with Carbon Vacancies toward the Oxygen Reduction Reaction in Alkaline Media.

Single-atom catalysts (SACs) have attracted extensive interest to catalyze the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. However, the development of SACs with high selectivity and long-term stability is a great challenge. In this work, carbon vacancy modified Fe-N-C SACs (FeH -N-C) are practically designed and synthesized through microenvironment modulation, achieving high-efficient utilization of active sites and optimization of electronic structures. The FeH -N-C catalyst exhibits a half-wave potential (E1/2 ) of 0.91 V and sufficient durability of 100 000 voltage cycles with 29 mV E1/2 loss. Density functional theory (DFT) calculations confirm that the vacancies around metal-N4 sites can reduce the adsorption free energy of OH*, and hinder the dissolution of metal center, significantly enhancing the ORR kinetics and stability. Accordingly, FeH -N-C SACs presented a high-power density and long-term stability over 1200 h in rechargeable zinc-air batteries (ZABs). This work will not only guide for developing highly active and stable SACs through rational modulation of metal-N4 sites, but also provide an insight into the optimization of the electronic structure to boost electrocatalytical performances.

Influence mechanism of organic matter and low-molecular-weight organic acids on the interaction between minerals and PAHs.

Investigate the effect of soil organic matter (SOM) and low molecular weight organic acids (LMWOAs) on minerals adsorption of PAHs. Batch adsorption experiments have been carried out to study the adsorption of PAHs (Naphthalene (NaP), Phenanthrene (Phe) and Pyrene (Pyr)) by minerals (Montmorillonite (Mnt), kaolinite (Kln) and calcite (Cal)). This research found that compared with Kln and Cal, Mnt showed the maximum adsorption capability for PAHs. And the order of PAHs adsorption by Mnt was: Pyr > Phe > Nap, which corresponds to the octanol-water partition coefficient (Kow) of different PAHs. The adsorption kinetic and isotherm were well fitted by Pseudo-second-order kinetic model, Freundlich and Linear isotherm model. Furthermore, inorganic ions (Ca2+) impacted PAHs adsorption by competitive adsorption and cation-π interactive. Cal has the maximum desorption of PAHs among three minerals, and there was desorption hysteresis phenomenon. Field emission-scanning electron microscope (Fe-SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) analysis indicated that SOM enhanced the sorption of PAHs by van der Waals, hydrogen bonding, π-π interactions, and chemical bonding. LMWOAs significantly inhibited PAHs adsorption and promote PAHs desorption from the minerals. As a result, LMWOAs increased of PAHs bioavailability, which provide a new strategy to improve PAHs cleanup efficiency.

New Strategy for the Persistent Photocatalytic Reduction of U(VI): Utilization and Storage of Solar Energy in K+ and Cyano Co-Decorated Poly(Heptazine Imide).

The photocatalytic conversion of soluble U(VI) into insoluble U(IV) is a robust strategy to harvest aqueous uranium, but remains challenging owing to the intermittent availability of solar influx and reoxidation of U(IV) without illumination. Herein, a dual platform based on K+ and cyano group co-decorated poly(heptazine imide) (K-CN-PHI) is reported that can drive persistent U(VI) extraction upon/beyond light. K-CN-PHI achieves the photocatalytic reduction of U(VI) with a reaction rate of 0.89 min-1 , being 47 times greater than that over pristine carbon nitride (PCN). This system can further be triggered by light to form long-living radicals, driving the reduction of U(VI) in the dark for over 3 d. The flexible structural K+ as counterions stabilize the electrons trapped by cyanamide groups, enabling the long lifetime of the generated radicals. The results collectively prove K-CN-PHI to be a novel and efficient photocatalyst enabling persistent U(VI) extraction around the clock, and broadening the practical applications of the photocatalytic extraction of U(VI).

Photoreduction behavior of Cr(VI) on oxidized carbon nanoparticles: From photocatalytic efficiency to oxygenated groups.

Clarifying the reaction process and specific mechanism between variable-valence elements and oxidized carbon nanoparticles is essential to evaluate the environmental impact of carbon nanomaterials. In this study, the photocatalytic reduction of Cr(VI) on oxidized carbon nanotubes (OCNTs), oxidized graphene ribbons (OGRs), and graphene oxide sheets (GOs) was explored by batch experiments and spectroscopic analyses. The reaction efficiencies strongly depended on the number of oxygenated groups in the oxidized carbon nanoparticles. The abundant oxygenated groups enabled the GOs to exhibit the highest photocatalytic activity, followed by the OGRs and OCNTs. As a result, the photoreduction efficiency of Cr(VI) reached 96% for GOs, whereas those of OGRs and OCNTs were only 40% and 13%, respectively. In addition, different types of oxygenated groups exhibited various activities based on molecular model tests, following the sequence carboxylic > hydroxyl > carbonyl > ether > aldehyde > edge. Based on the underlying relationship between the oxygenated groups, topological structures, and mechanical strain in the carbon nanoparticles, we speculate that mechanical strain plays a critical role in the formation of oxygenated groups, thereby regulating their photocatalytic activities. The findings in this work provide novel insights into the roles of oxygenated groups and the mechanical strain of carbon nanoparticles in their environmental behavior.

New Insights into the Cellular Toxicity of Carbon Quantum Dots to Escherichia coli.

In this study, the cytotoxicity and toxic mechanism of carbon quantum dots (CQDs) to E. coli were evaluated in vitro. The synthetic CQDs were extremely small in size (~2.08 nm) and displayed strong fluorescence. The results demonstrated that CQDs showed good biocompatibility with E. coli within a short culture time. However, when the exposure time exceeded 24 h, the toxicity of CQDs became apparent, and the contents of reactive oxygen species, lactate dehydrogenase, and the crystal violet absorption rate increased significantly. To further explore the cytotoxic mechanism, approaches including confocal laser scanning microscopy, scanning electron microscopy, and biological transmission electron microscopy combined with zeta potential tests, osmotic pressure measurement, and comet assays were performed. On the one hand, the CQDs altered the surface charges of cells and induced lipid peroxidation by adhesion on the surface of E. coli, leading to an increase in the permeability of the cell wall. On the other hand, when the concentration of CQDs reached 200 µg/mL, the osmotic pressure of the extracellular environment was significantly reduced. These are the main factors that lead to cell edema and death. Finally, the comet assays confirmed that CQDs could induce DNA damage, which could inhibit the proliferation of E. coli.

Spatial distribution, composition, and source analysis of petroleum pollutants in soil from the Changqing Oilfield, Northwest China.

Petroleum contamination surrounding oilfields has attracted more concerns. However, the levels, distribution and source of petroleum of Changqing Oilfield soil still remain lots of knowns, which is important for local environmental protection. Given soil contamination issues in Changqiong Oilfield were investigated. The maximum concentrations of total petroleum hydrocarbons (TPHs), N-alkanes (TNAs) and polycyclic aromatic hydrocarbons (PAHs) were determined to be 1960.29, 96.13 and 0.82 mg/kg, respectively. TPHs were higher in the north than the south of the study area. TPHs decreased in the horizontal and vertical distribution as soil depth and distance from oil wells increased. Source analysis showed that TNAs mainly originated from petroleum, PAHs were controlled by petroleum spills, combustion and traffic. Correlation analysis implied that TPHs residues had an effect on soil environmental quality. This study have important implications for understanding the environmental behavior of petroleum and can provide support for petroleum remediation and risk control.

Sequestration of heavy metals in soil aggregates induced by glomalin-related soil protein: A five-year phytoremediation field study.

Glomalin-related soil protein (GRSP) is an essential bioactive component that may respond to heavy metal stress; however, its exact influence on metal bioavailability and the associated mechanism remains poorly understood. This study investigated the speciation and distribution of heavy metals in soil aggregates associated with GRSP through macroscopic and microscopic approaches. A field study showed that the metal ions were distributed to the macro-aggregate fraction by partitioning the particle size classes during phytoremediation. Partial least squares path modeling (PLS-PM) demonstrated that the heavy metal bioavailability was negatively affected by aggregate stability (61.5%) and GRSP content (52.8%), suggesting that the soil aggregate properties regarding GRSP were vital drivers in mitigating environmental risk closely associated with toxic metal migration in soil-plant systems. The nonideal competitive adsorption (NICA)-Donnan model fitting suggested that GRSP were rich in acid site density, and the complexation with deprotonated groups dominated the speciation of heavy metals in soil. Further, the microfocus X-ray absorption/fluorescence spectroscopy analysis indicated that GRSP might promote the formation of stable metal species by binding with sulfur-containing sites. This study highlights the role of GRSP in heavy metal sequestration in contaminated soils, providing new guidance on the GRSP intervention for phytoremediation strategies.

Seasonal variations of geofluids from mud volcano systems in the Southern Junggar Basin, NW China.

Variations in the chemical composition of geofluids and of gas fluxes are significant parameters for understanding mud volcanism and correctly estimate their emissions in carbon species, particularly greenhouse gas, methane. In this study, muddy water and gas samples were collected from the Anjihai, Dushanzi, Aiqigou, and Baiyanggou mud volcanoes in the southern Junggar Basin during the four seasons, around a year. This region hosts the most active mud volcanism throughout China. Gas and water were analyzed for major molecular compositions, carbon and hydrogen isotopes of the gas phase, as well as cations and anions, hydrogen and oxygen isotopes of water. The emitted gases are dominated by CH4 with some C2H6, CO2, and N2. The seasonal changes in the chemical composition and carbon isotopes of emitted gases are not significant, whereas clear variations in the amounts of cations and anions dissolved in the water are reported. These are higher in spring and summer than autumn and winter. The CH4, CO2, and C2H6 fluxes are 157.3-1108 kg/a, 1.8-390.1 kg/a, and 10.2-118.7 kg/a, respectively, and a clear seasonal trend of the gas seepage flux has been observed. In January, the macro-seepage flux of open vents is ≥65 % higher than in April, whereas the micro-seepage flux significantly decreased, probably due to the frozen shallow ground and blockage of soil fractures around the vents by heavy snow and ice during January. This probably causes an extra gas pressure transferred to the major vents, resulting in higher flux of the macro-seepage in the cold season. However, the total flux of the whole mud volcano system is generally consistent around a year.

Oxygen-containing groups in cellulose and lignin biochar: their roles in U(VI) adsorption.

The adsorption behaviors of cellulose and lignin biochar depend on the evolution of their oxygen-containing groups to some extent. In this study, cellulose-rich pakchoi and lignin-rich corncob were selected to prepare the pyrolytic biochar at variable temperatures, named PBC and CBC, respectively. Their structure-function relationships were in-depth studied via the combination of the adsorption experiments of U(VI) and comprehensive spectral analyses. The maximal adsorption capacity of PBC 300, obtained at 300 °C, was measured as 46.62 mg g-1 for U(VI), which was ⁓1.3 times higher than 35.60 mg g-1 of CBC 300. U(VI) adsorption on PBC and CBC were predominantly ascribed to the coordination interaction between oxygen-containing groups and U(VI). Interestingly, the main complexation groups were distinct in both biochars due to the different inherent evolutions of cellulose and lignin. Volatile d-glucose chains in cellulose were apt to degrade rapidly, and the formed carboxyls acted as the most important sites in PBC. However, the stable aromatic network in lignin led to a slow degradation, and more hydroxyls thus remained in CBC, which controlled U(VI) adsorption. In this study, we obtained greatly cost-effective adsorbents of U(VI) and provided some essential insights into understanding the structural evolution-function relationship of cellulose and lignin biochar.

Light Promotes the Immobilization of U(VI) by Ferrihydrite.

The environmental behaviors of uranium closely depend on its interaction with natural minerals. Ferrihydrite widely distributed in nature is considered as one main natural media that is able to change the geochemical behaviors of various elements. However, the semiconductor properties of ferrihydrite and its impacts on the environmental fate of elements are sometimes ignored. The present study systematically clarified the photocatalysis of U(VI) on ferrihydrite under anaerobic and aerobic conditions, respectively. Ferrihydrite showed excellent photoelectric response. Under anaerobic conditions, U(VI) was converted to U(IV) by light-irradiated ferrihydrite, in the form of UO2+x (x < 0.25), where •O2− was the dominant reactive reductive species. At pH 5.0, ~50% of U(VI) was removed after light irradiation for 2 h, while 100% U(VI) was eliminated at pH 6.0. The presence of methanol accelerated the reduction of U(VI). Under aerobic conditions, the light illumination on ferrihydrite also led to an obvious but slower removal of U(VI). The removal of U(VI) increased from ~25% to 70% as the pH increased from 5.0 to 6.0. The generation of H2O2 under aerobic conditions led to the formation of UO4•xH2O precipitates on ferrihydrite. Therefore, it is proved that light irradiation on ferrihydrite significantly changed the species of U(VI) and promoted the removal of uranium both under anaerobic and aerobic conditions.

Mechanistic study for mutual interactions of Pb2+ and Trichoderma viride.

Fungi play significant roles in the geochemical processes of heavy metals in the environment. However, the interaction between heavy metals and fungi, especially at the cellular level, is quite complicated and remains unknown. This study explored the mutual interaction mechanism between Pb2+ and Trichoderma viride by combining batch experiments, spectroscopy, and in vitro approaches. Batch experiments revealed that Pb2+ had toxic effect on T. viride, originally causing the biomass of T. viride decreased from 1.3 g in the control group to 0 g in the presence of 200 mg/L Pb2+. The difference in biomass further led to varied pH, even decreasing from 5.7 at the outset to 3.4 due to the acid-production properties of T. viride. Moreover, structural deformation and damage of T. viride mycelium appeared when exposed to Pb2+, and were more evident at a higher dose of Pb2+ exposure. The growth curve exhibited that T. viride gradually adapted to Pb2+ exposure, which related to Pb2+ exposure concentration. Further, intracellular and extracellular secretions of T. viride changed with varying exposure concentrations of Pb2+, indicating that T. viride adapted differently to different concentrations of Pb2+, and MT participated in the detoxification of T. viride. SEM-EDX showed that T. viride could bio-adsorb and bioaccumulate more Pb2+ when exposed to more Pb2+, which was closely related to the content of P. And carbonyl, phosphate, and amino groups of T. viride participated in the Pb2+ biosorption onto T. viride, as evidenced by FT-IR and XPS. Meanwhile, the biomineralization and reduction of Pb2+ by T. viride were observed by XRD and XPS, which might be a possible factor for Pb2+ biosorption and bioaccumulation. CLSM showed that the bio-adsorbed and bioaccumulated Pb2+ were mainly distributed in the membrane of T. viride mycelium.

Microbial metabolic limitation of rhizosphere under heavy metal stress: Evidence from soil ecoenzymatic stoichiometry.

Slow nutrient turnover and destructed soil function were the main factors causing low efficiency in phytoremediation of heavy metal (HM)-contaminated soil. Soil ecoenzymatic stoichiometry can reflect the ability of soil microorganisms to acquire energy and nutrients, and drive nutrient cycling and carbon (C) decomposition in HM-contaminated soil. Therefore, for the first time, we used the enzymatic stoichiometry modeling to examine the microbial nutrient limitation in rhizospheric and bulk soil of different plants (Medicago sativa, Halogeton arachnoideus and Agropyron cristatum) near the Baiyin Copper Mine. Results showed that the main pollutants in this area were Cu, Zn, Cd, and Pb, while Cd and Zn have the greatest contribution according to the analysis of pollution load index (PLI). The activities of soil C-, nitrogen (N)-, and phosphorus (P)-acquiring enzymes in the rhizosphere of plants were significantly greater than that in bulk soil. Moreover, microbial C and P limitations were observed in all plant treatments, while the lower limitation was generally in the rhizosphere compared to bulk soil. The HM stress significantly increased microbial C limitation and decreased microbial P limitation, especially in the rhizospheric soil. The partial least squares path modeling (PLS-PM) further indicated that HM concentration has the greatest effects on microbial P limitation (-0.64). In addition, the highest enzyme activities and the lowest P limitation were observed in the rhizospheric and bulk soil of M. sativa, thereby implying that soil microbial communities under the remediation of M. sativa were steadier and more efficient in terms of their metabolism. These findings are important for the elucidation of the nutrient cycling and microbial metabolism of rhizosphere under phytoremediation, and provide guidance for the restoration of HM-contaminated soil.

Interaction behaviors of Cr(VI) at biotite-water interface in the presence of HA: Batch, XRD and XPS investigations.

The interaction behaviors of heavy metals and micaceous minerals are extremely important to understand the environmental behaviors of heavy metals. In this work, the interaction behaviors of Cr(VI) and biotite in the presence and absence of HA were studied combining batch and spectroscopic approaches. Batch experiments showed that biotite had the ability to remove Cr(VI) from the water and the removal markedly increased with decreasing pH. However, sorption of total Cr onto biotite increased with increasing pH (2.0-4.0), whilst quickly decreased above pH âˆ¼ 4.0. It was worth noting that redox process of Cr(VI) to Cr(III), caused by structural Fe(II) on biotite, was another important factor for the high removal of Cr(VI) in a pH range of 2.0-4.0. Ionic strength also influenced Cr(VI) removal that Cr(VI) removal became higher with increasing ion strength. The presence of HA did not show obvious macroscopic effect on Cr(VI) removal, however, HA could cover biotite surface, and promote the sorption of total Cr onto biotite and attenuate the reduction effect caused by Fe(II) on biotite. Spectroscopic approaches, like FT-IR, XRD and XPS further confirmed the existence of Cr(III) on biotite interacting with Cr(VI) and the reduction of Cr(VI) to Cr(III) was drove by the Fe(II) dissolving from biotite to Fe(III). Further, sorption effect and reduction effect competitively contributed to the Cr(VI) removal by biotite, and reduction effect played a more important role at lower pH.

Insights into sorption speciation of uranium on phlogopite: Evidence from TRLFS and DFT calculation.

Knowledge of the sorption speciation of uranium at mineral/water interface is essential to construct reliable retention and migration models. In this work, the sorption speciation of U(VI) at the phlogopite/water interface was studied at trace concentrations by combining batch sorption, time-resolved luminescence spectroscopy, and theoretical calculation. Batch experiments showed that the sorption of U(VI) on phlogopite was strongly dependent on pH but weakly affected by ionic strength, implying that the inner-sphere surface complexation was mainly responsible for U(VI) sorption on phlogopite. The diverse luminescence spectral characteristics indicated the formation of multiple inner-sphere surface species at the phlogopite/water interface, whose abundances varied as a function of pH. A portion of U(VI) precipitated as uranyl oxyhydroxides such as metaschoepite and becquerelite at high pH. Density functional theory calculation revealed that the bidentate complex at the edge of phlogopite (≡AlO-MgO-UO2(H2O)3) was the most favorable sorption configuration for U(VI) at acidic condition. The increasing temperature enhanced the sorption of U(VI) on phlogopite without altering the sorption species, and such enhancement in U(VI) sorption was withdrawn once the temperature decreased. These findings are essential for understanding the immobilization mechanism of U(VI) in mica-rich granitic terrains at a molecular scale and building a reliable retention model.