Innovative strategy for the effective utilization of coal waste slag in the Fenton-like process for the degradation of trichloroethylene.

In response to environmental concerns at the global level, there is considerable momentum in the exploration of materials derived from waste that are both sustainable and eco-friendly. In this study, CS-Fe (carbon, silica, and iron) composite was synthesized from coal gasification slag (CGS) and innovatively applied as a catalyst to activate PS (persulfate) for the degradation of trichloroethylene (TCE) in water. Scanning electron microscope (SEM), fourier transmission infrared spectroscopy (FTIR), energy dispersive x-ray spectroscopy (EDS), brunauer, emmet, and teller (BET) technique, and x-ray diffractometer (XRD) spectra were employed to investigate the surface morphology and physicochemical composition of the CS-Fe composite. CS-Fe catalyst showed a dual nature by adsorption and degradation of TCE simultaneously, displaying 86.1% TCE removal in 3 h. The synthesized CS-Fe had better adsorption (62.1%) than base material CGS (36.4%) due to a larger BET surface area (770.8 m2 g-1), while 24.0% TCE degradation was recorded upon the activation of PS by CS-Fe. FTIR spectra confirmed the adsorption and degradation of TCE by investigating the used and fresh samples of CS-Fe catalyst. Scavengers and Electron paramagnetic resonance (EPR) analysis confirmed the availability of surface radicals and free radicals facilitated the degradation process. The acidic nature of the solution favored the degradation while the presence of bicarbonate ion (HCO3-) hindered this process. In conclusion, these results for real groundwater, surfactant-added solution, and degradation of other TCE-like pollutants propose that the CS-Fe composite offers an economically viable and favorable catalyst in the remediation of organic contaminants within aqueous solutions. Further investigation into the catalytic potential of coal gasification slag-based carbon materials and their application in Fenton reactions is warranted to effectively address a range of environmental challenges.

Nanobubbles improve peroxymonosulfate-based advanced oxidation: High efficiency, low toxicity/cost, and novel collaborative mechanism.

Cl- activated peroxymonosulfate (PMS) oxidation technology can effectively degrade pollutants, but the generation of chlorinated disinfection byproducts (DBPs) limits the application of this technology in water treatment. In this study, a method of nanobubbles (NBs) synergistic Cl-/PMS system was designed to try to improve this technology. The results showed the synergistic effects of NBs/Cl-/PMS were significant and universal while its upgrade rate was from 12.89% to 34.97%. Moreover, the synergistic effects can be further improved by increasing the concentration and Zeta potential of NBs. The main synergistic effects of NBs/Cl-/PMS system were due to the electrostatic attraction of negatively charged NBs to Na+ from NaCl, K+ from PMS, and H+ from phenol, which acted as a "bridge" between Cl- and HSO5- as well as phenol and Cl-/HSO5-, increasing active substance concentration. In addition, the addition of NBs completely changed the oxidation system of Cl-/PMS from one that increases environmental toxicity to one that reduces it. The reason was that the electrostatic attraction of NBs changed the active sites and degradation pathway of phenol, greatly reducing the production of highly toxic DBPs. This study developed a novel environmentally friendly oxidation technology, which provides an effective strategy to reduce the generation of DBPs in the Cl-/PMS system.

Unlocking the power of activated carbon-mediated peracetic acid activation for efficient antibiotics abatement in groundwater: Coupling the processes of electron transfer, radical production, and adsorption.

The activation of peracetic acid (PAA) by activated carbon (AC) is a promising approach for reducing micropollutants in groundwater. However, to harness the PAA/AC system's potential and achieve sustainable and low-impact groundwater remediation, it is crucial to quantify the individual contributions of active species. In this study, we developed a combined degradation kinetic and adsorption mass transfer model to elucidate the roles of free radicals, electron transfer processes (ETP), and adsorption on the degradation of antibiotics by PAA in groundwater. Our findings reveal that ETP predominantly facilitated the activation of PAA by modified activated carbon (AC600), contributing to ∼61% of the overall degradation of sulfamethoxazole (SMX). The carbonyl group (CO) on the surface of AC600 was identified as a probable site for the ETP. Free radicals contributed to ∼39% of the degradation, while adsorption was negligible. Thermodynamic and activation energy analyses indicate that the degradation of SMX within the PAA/AC600 system requires a relatively low energy input (27.66 kJ/mol), which is within the lower range of various heterogeneous Fenton-like reactions, thus making it easily achievable. These novel insights enhance our understanding of the AC600-mediated PAA activation mechanism and lay the groundwork for developing efficient and sustainable technologies for mitigating groundwater pollution. ENVIRONMENTAL IMPLICATION: The antibiotics in groundwater raises alarming environmental concerns. As groundwater serves as a primary source of drinking water for nearly half the global population, the development of eco-friendly technologies for antibiotic-contaminated groundwater remediation becomes imperative. The innovative PAA/AC600 system demonstrates significant efficacy in degrading micropollutants, particularly sulfonamide antibiotics. By integrating degradation kinetics and adsorption mass transfer models, this study sheds light on the intricate mechanisms involved, emphasizing the potential of carbon materials as sustainable tools in the ongoing battle for clean and safe groundwater.

The longevity evaluation of multi-metal stabilization by MgO in Pb/Zn smelter-contaminated soils.

The re-mobilization risks of potentially toxic elements (PTEs) during stabilization deserve to be considered. In this study, artificial simulation evaluation methods based on the environmental stress of freeze-thaw (F-T), acidification and variable pH were conducted to assess the long-term effectiveness of PTEs stabilized by MgO in Pb/Zn smelter contaminated soils. Among common stabilizing materials, MgO was considered as the best remediation material, since PTEs bioavailability reduced by 55.48% for As, 19.58% for Cd, 10.57% for Cu, and 26.33% for Mn, respectively. The stabilization effects of PTEs by MgO were best at the dosage of 5 wt%, but these studied PTEs would re-mobilize after 30 times F-T cycles. Acid and base buffering capacity results indicated that the basicity of contaminated soils with MgO treatment reduced under F-T action, and the leached PTEs concentrations would exceed the safety limits of surface water quality standard in China (GB3838-2002) after acidification of 2325 years. No significant changes were found in the pH-dependent patterns of PTEs before and after F-T cycles. However, after F-T cycles, the leaching concentrations of PTEs increased due to the destruction of soil microstructure and the functionality of hydration products formed by MgO, as indicated by scanning electron microscopy (SEM) coupled with energydispersive Xray spectroscopy (EDS) results. Hence, these findings would provide beneficial references for soil remediation assessments of contaminated soils under multi-environmental stress.

A novel mycelial pellet applied to remove polycyclic aromatic hydrocarbons: High adsorption performance & its mechanisms.

Mycelial pellets formed by Penicillium thomii ZJJ were applied as efficient biosorbents for the removal of polycyclic aromatic hydrocarbons (PAHs), which are a type of ubiquitous harmful hydrophobic pollutants. The live mycelial pellets were able to remove 93.48 % of pyrene at a concentration of 100 mg/L within 48 h, demonstrating a maximum adsorption capacity of 285.63 mg/g. Meanwhile, the heat-killed one also achieved a removal rate of 65.01 %. Among the six typical PAHs (pyrene, phenanthrene, fluorene, anthracene, fluoranthene, benzo[a]pyrene), the mycelial pellets preferentially adsorbed the high molecular weight PAHs, which also have higher toxicity, resulting in higher removal efficiency. The experimental results showed that the biosorption of mycelial pellets was mainly a spontaneous physical adsorption process that occurred as a monolayer on a homogeneous surface, with mass transfer being the key rate-limiting step. The main adsorption sites on the surface of mycelia were carboxyl and N-containing groups. Extracellular polymeric substances (EPS) produced by mycelial pellets could enhance adsorption, and its coupling with dead mycelia could achieve basically the same removal effect to that of living one. It can be concluded that biosorption by mycelial pellets occurred due to the influence of electrostatic and hydrophobic interactions, consisting of five steps. Furthermore, the potential applicability of mycelial pellets has been investigated considering diverse factors. The mycelia showed high environmental tolerance, which could effectively remove pyrene across a wide range of pH and salt concentration. And pellets diameters and humic acid concentration had a significant effect on microbial adsorption effect. Based on a cost-effectiveness analysis, mycelium pellets were found to be a low-cost adsorbent. The research outcomes facilitate a thorough comprehension of the adsorption process of pyrene by mycelial pellets and their relevant applications, proposing a cost-effective method without potential environmental issues (heat-killed mycelial pellets plus EPS) to removal PAHs.

Surfactant enhanced persulfate system for the synergistic oxidation and reduction of mixed chlorinated hydrocarbons.

Surfactant-enhanced in-situ chemical oxidation (S-ISCO) is widely applied in soil and groundwater remediation. However, the role of surfactants in the reactive species (RSs) transformation remains inadequately explored. This work introduced nonionic surfactant Tween-80 (TW-80) into a nano zero-valent iron (nZVI) activated persulfate (PS) system. The findings indicate that PS/nZVI/TW-80 system can realize the concurrent removal of trichloroethylene (TCE), tetrachloroethene (PCE), and carbon tetrachloride (CT), whereas CT cannot be eliminated without TW-80 presence. Further analysis unveiled that hydroxyl (HO•) and sulfate radicals (SO4－•) were the primary species for TCE and PCE degradation, while CT was reductively eliminated by surfactant radicals generated from TW-80. Moreover, the surfactant radicals were found to accelerate Fe(III)/Fe(II) cycle, reduce the production of iron sludge, and increase PS decomposition. The possible degradation routes of mixed chlorinated hydrocarbons (CHCs) and the decomposition pathways of TW-80 were proposed through the density function theory (DFT) calculation and intermediates analysis. Additionally, the effects of other nonionic surfactants on the simultaneous removal of TCE, PCE, and CT, and the practical applications using the actual contaminated groundwater were also evaluated. This study provides theoretical support for the simultaneous removal of CHCs, particularly those containing perchlorinated contaminants, using the S-ISCO techniques.

Targeted degradation of naphthalene by peroxymonosulfate activation using molecularly imprinted biochar.

Polycyclic aromatic hydrocarbons (PAHs) in aquatic environments are threatening ecosystems and human health. In this work, an effective and environmentally friendly catalyst based on biochar and molecular imprinting technology (MIT) was developed for the targeted degradation of PAHs by activating peroxymonosulfate. The results show that the adsorption amount of naphthalene (NAP) by molecularly imprinted biochar (MIP@BC) can reach 82% of the equilibrium adsorption capacity within 5 min, and it had well targeted adsorption for NAP in the solution mixture of NAP, QL and SMX. According to the comparison between the removal rates of NAP and QL by MIP@BC/PMS or BC/PMS system in respective pure solutions or mixed solutions, the MIP@BC/PMS system can better resist the interference of competing pollutants (i.e., QL) compared to the BC/PMS system; that is, MIP@BC had a good ability to selectively degrade NAP. Besides, the removal rate of NAP by MIP@BC/PMS gradually decreased as pH increased. The addition of Cl- greatly promoted the targeted removal of NAP in the MIP@BC/PMS system, while HCO3- and CO32- both had an inhibitory effect. Furthermore, SO4•-, O2•- and 1O2 produced by BC activating PMS dominated the NAP degradation, and it was inferred that the vacated imprinted cavities after NAP degradation can continue to selectively adsorb NAP and this could facilitate the reusability of the material. This study can promote the research on the targeted degradation of PAHs through the synergism of biochar/PMS advanced oxidation processes and MIT.

Resource utilization of rice straw to prepare biochar as peroxymonosulfate activator for naphthalene removal: Performances, mechanisms, environmental impact and applicability in groundwater.

Herein, biochar was prepared using rice straw, and it served as the peroxymonosulfate (PMS) activator to degrade naphthalene (NAP). The results showed that pyrolysis temperature has played an important role in regulating biochar structure and properties. The biochar prepared at 900°C (BC900) had the best activation capacity and could remove NAP in a wide range of initial pH (5-11). In the system of BC900/PMS, multi-reactive species were produced, in which 1O2 and electron transfer mainly contributed to NAP degradation. In addition, the interference of complex groundwater components on the NAP removal rate must get attention. Cl- had a significant promotional effect but risked the formation of chlorinated disinfection by-products. HCO3-, CO32-, and humic acid (HA) had an inhibitory effect; surfactants had compatibility problems with the BC900/PMS system, which could lead to unproductive consumption of PMS. Significantly, the BC900/PMS system showed satisfactory remediation performance in spiked natural groundwater and soil, and it could solve the problem of persistent groundwater contamination caused by NAP desorption from the soil. Besides, the degradation pathway of NAP was proposed, and the BC900/PMS system could degrade NAP into low or nontoxic products. These suggest that the BC900/PMS system has promising applications in in-situ groundwater remediation.

Efficient Fenton-like degradation of tetracycline by stalactite-like CuCo-LDO/CN catalysts: The overlooked contribution of dissolved oxygen.

In the Fenton-like processes, the resources that exist in the system itself (e.g., dissolved oxygen, electron-rich pollutants) are often overlooked. Herein, a novel CuCo-LDO/CN composite catalyst with a strong "metal-π" effect was fabricated by in situ calcination which could activate dissolved oxygen to generate active oxygen species and degrade the electron-rich pollutants directly. The CuCo-LDO/CN (1:10) with the largest specific surface aera, most C-O-M bonds and least oxygen vacancies exhibited the best catalytic performance for tetracycline (TC)degradation (TC removal efficiency 93.2% and mineralization efficiency 40%, respectively, after 40 min at neutral pH) compared to CuCo-LDO and other CuCo-LDO/CN composite catalysts. In the absence of H2O2, dissolved oxygen could be activated by the catalyst to generate O2·-and ·OH, which contributed to approximately 20.7% of TC degradation, providing a faster and cost-effective way for TC removal from wastewater. While in the presence of H2O2, it was activated by CuCo-LDO/CN to generate·OH as the dominant reactive oxygen species and meanwhile TC transferred electrons to H2O2 through C-O-M bonds, accelerating the Cu+/Cu2+ and Co2+/Co3+ redox cycles. The possible degradation pathways of TC were proposed, and the environmental hazard of TC is greatly mitigated according to toxicity prediction.

The occurrence of "yellowing" phenomenon and its main driving factors after the remediation of chromium (Cr)-contaminated soils: A literature review.

Chromium (Cr) is a highly toxic element, which is widely present in environment due to industrial activities. One of most applicable technique to clean up Cr pollution is chemical reduction. However, the Cr(VI) concentration in soil increases again after remediation, and meanwhile the yellow soil would appear, which is commonly called as "yellowing" phenomenon. To date, the reason behind the phenomenon has been disputed for decades. This study aimed to introduce the possible "yellowing" mechanism and the influencing factors based on the extensive literature review. In this work, the concept of "yellowing" phenomenon was explained, and the most potential reasons include the reoxidation of manganese (Mn) oxides and mass transfer were summarized. Based on the reported finding and results, the large area of "yellowing" is likely to be caused by the re-migration of Cr(VI), since it could not sufficiently contact with the reductant under the effects of the mass transfer. In addition, other driving factors also control the occurrence of "yellowing" phenomenon. This review provides valuable reference for the academic peers participating in the Cr-contaminated sites remediation.

Electrokinetically-delivered persulfate and pulsed direct current electric field induced transport, mixing and thermally activated in situ for remediation of PAHs contaminated soil.

Herein, we proposed and proved a novel strategy that enhanced the delivery of persulfate (PS) to soil by electrokinetics (EK), and then applying a pulsed direct current (DC) electric field thermally activated the PS in situ, and synchronously promoted PS plume mixing, contaminants-free radicals reaction and continued to replenish PS to the soil, to achieve efficient degradation of contaminants in low permeability zones. Results showed that transport rate of PS in tested soil by EK was approximately 12.3 times than diffusion. Applying an irregular pulsed DC field maintained the targeted temperature (30-50 â„ƒ) during activation phase, and generated two oxidative radicals (SO4∙-/∙OH). Concurrently, in the case, electromigration and electroosmosis have promoted the PS transport and the reactive mixing of PS/free radicals with polycyclic aromatic hydrocarbons (PAHs) contaminated soil and enhance the PAHs degradation. PS concentrations in pore fluid was characterized by an increase accompanied by continuous fluctuations. Eventually, in case of the long-term low-temperature activation (i.e., 30-40 ℃), a significant decreases (nearly 60%) in average concentration of PAHs in the whole soil cell was observed over 10 days. These results demonstrates that the novel strategy has great potentiality in the remediation of low permeability contaminated soil.

Defect-rich MoS2/NiS2 nanosheets loaded on SiNWs for efficient and stable photoelectrochemical hydrogen production.

Photoelectrochemical (PEC) reaction with efficient, stable, and cost-effective photocathodes using non-precious metals will be one of the most environmentally friendly technologies for hydrogen (H2) generation under the worldwide pressure for carbon neutrality. Herein, a new 3-dimentional (3D) SiNWs@MoS2/NiS2 photocathode was designed and synthesized. Defect-rich MoS2/NiS2 nanosheets on silicon nanowires (SiNWs) provide more active sites to promote charge transfer and photo-generated electron-hole separation. Meanwhile, the 3D structure of the photocathode provides an effective charge transfer mode and an open channel for rapid H2 release. The SiNWs@MoS2/NiS2 photocathode exhibits the maximum photocurrent density (21.4 mA·cm-2 at 0.9 V vs. RHE), highest H2 production rate (183 µmol·h-1), smallest diffusion resistance (34.7 Ω), and excellent catalytic stability for more than 10 h at pH = 7. Based on density function theory calculation, the MoS2/NiS2 nanosheets are conducive to chemical adsorption of H2 intermediates, which are crucial for the maintenance of the composite photocathode in PEC H2 production.

The mechanistic insights into the leaching behaviors of potentially toxic elements from the indigenous zinc smelting slags under the slag dumping site scenario.

Since lager quantities of the zinc (Zn) smelting slags were traditionally dumped at the indigenous Zn smelting sites, the release characterization of potentially toxic elements (PTEs) from the Zn smelting slags under various environmental conditions were of great significance for an environmental risk analysis. The acidification of the Zn smelting slags to pH= 4 and 6 would result in the leaching concentrations of Cd and Mn exceeding the fourth-class standard of surface water quality standard in China (GB3838-2002). Notably, most metals exhibited an amphoteric leaching pattern, where the highest leached concentrations of As, Cd, Cu, Mn, Pb, and Zn were 4.15, 4.21, 140.0, 78.1, 156.9 and 477.0 mg/L, respectively. In addition, the highest release of toxic metals within 96 h reached 0.17 % of As, 3.50 % of Cd, 2.77 % of Cu, 6.92 % of Mn, 0.13 % of Pb, and 2.57 % of Zn, respectively. The combined results of various characterization techniques suggested that the PTEs remobilization effected by rhizosphere-like organic acids were mainly controlled by the precipitation of newly formed Fe, Mn and Al (hydr) oxides and the complexation of organic ligands. The present study results could provide valuable insights into the long-term leaching behaviors of PTEs from the Zn smelting slags to reduce ecological hazard.

Therapeutic Effect of Renifolin F on Airway Allergy in an Ovalbumin-Induced Asthma Mouse Model In Vivo.

Renifolin F is a prenylated chalcone isolated from Shuteria involucrata, a traditional minority ethnic medicine used to treat the respiratory diseases and asthma. Based on the effects of the original medicine plant, we established an in vivo mouse model of allergic asthma using ovalbumin (OVA) as an inducer to evaluate the therapeutic effects of Renifolin F. In the research, mice were sensitized and challenged with OVA to establish an allergic asthma model to evaluate the effects of Renifolin F on allergic asthma. The airway hyper-reactivity (AHR) to methacholine, cytokine levels, ILC2s quantity and mircoRNA-155 expression were assessed. We discovered that Renifolin F attenuated AHR and airway inflammation in the OVA-induced asthmatic mouse model by inhibiting the regulation of ILC2s in the lung, thereby, reducing the upstream inflammatory cytokines IL-25, IL-33 and TSLP; the downstream inflammatory cytokines IL-4, IL-5, IL-9 and IL-13 of ILC2s; and the co-stimulatory factors IL-2 and IL-7; as well as the expression of microRNA-155 in the lung. The findings suggest a therapeutic potential of Renifolin F on OVA-induced airway inflammation.

Is biochar a reliable catalyst for activating peroxydisulfate? Damage of biochar during catalytic process.

The unsatisfactory reuse performance of biochar in the catalytic system has become an important factor limiting its application. Damage of biochar in the catalytic systems has been reported, but the mechanism of damage is still unclear. In this study, cotton stalk and walnut shell biochar were used to activate peroxydisulfate (PDS) for sulfamethazine degradation, and multiple characterization methods were used to determine the damage of biochar. The comparative experiments of biochar, recycled biochar, and the biochar treated by PDS in catalytic reaction showed that the performance of biochars decreased by 37.5%-65.3%. After the catalytic reaction, the unstable carbon in biochar was lost, and the biochar surface was oxidized, which reduced its affinity to organic matter. CO2 physisorption showed that the pore structure of biochars barely changed. However, for walnut shell biochar, its adsorption capacity of nitrogen decreased obviously. Moreover, the electrochemical tests showed that the conductivity of walnut shell biochar decreased, which would lead to the reduction of its catalytic performance through the electron transfer path. Overall, the effects of catalytic process on the performance of biochar cannot be ignored. Therefore, more efforts are needed to improve the stability and homogeneity of biochar as an efficient and sustainable PDS activator.

Insight into the Adsorption Behaviors of Antimony onto Soils Using Multidisciplinary Characterization.

Antimony (Sb) pollution in soils is an important environmental problem, and it is imperative to investigate the migration and transformation behavior of Sb in soils. The adsorption behaviors and interaction mechanisms of Sb in soils were studied using integrated characterization techniques and the batch equilibrium method. The results indicated that the adsorption kinetics and isotherms of Sb onto soils were well fitted by the first-order kinetic, Langmuir, and Freundlich models, respectively, while the maximum adsorbed amounts of Sb (III) in soil 1 and soil 2 were 1314.46 mg/kg and 1359.25 mg/kg, respectively, and those of Sb (V) in soil 1 and soil 2 were 415.65 mg/kg and 535.97 mg/kg, respectively. In addition, pH ranging from 4 to 10 had little effect on the adsorption behavior of Sb. Moreover, it was found that Sb was mainly present in the residue fractions, indicating that Sb had high geochemical stability in soils. SEM analysis indicated that the distribution positions of Sb were highly coincident with Ca, which was mainly due to the existence of calcium oxides, such as calcium carbonate and calcium hydroxide, that affected Sb adsorption, and further resulted in Sb and Ca bearing co-precipitation. XPS analysis revealed the valence state transformation of Sb (III) and Sb (V), suggesting that Fe/Mn oxides and reactive oxygen species (ROS) served as oxidant or reductant to promote the occurrence of the Sb redox reaction. Sb was mobile and leachable in soils and posed a significant threat to surface soils, organisms, and groundwater. This work provides a fundamental understanding of Sb adsorption onto soils, as well as a theoretical guide for studies on the adsorption and migration behavior of Sb in soils.

Elucidating the effect of different desorbents on naphthalene desorption and degradation: Performance and kinetics investigation.

In this work, the effect of different desorbents (low molecular weight organic acids (LMWOAs), surfactants, and inorganic salts) on naphthalene (NAP) desorption in soil was investigated, and the results showed that NAP desorption pattern fitted the pseudo-second-order kinetics. The addition of LMWOAs, especially citric acid (CA), could stimulate the reactive oxygen species (ROS) generation and NAP degradation in Fe(II) activated persulfate (PS) system, while the presence of surfactants and CaCl2 could inhibit the NAP removal due to the competitive consumption of ROS. The maximum removal of NAP was 97.5% within 120 min at the PS/Fe(II)/CA/NAP molar ratio of 15/5/1/1, and the pseudo-first-order kinetic constant of NAP removal increased from 0.0110 min-1 to 0.0783 min-1 with the addition of CA. Compared with surfactants and inorganic salts, LMWOAs, especially CA, were more suitable as desorbent in soil washing coupled with in situ chemical oxidation technique. Moreover, 1.86 mg L-1 desorbed amount and 36.1% removal of NAP from soil could be obtained with the presence of 1 mM CA. Finally, the significant removal of NAP and other contaminants (phenanthrene, fluoranthene, and benzene series) in actual groundwater could provide theoretical basis and technical support for the remediation of organic contaminated sites with desorbents.

A Novel In Situ Method for Simultaneously and Selectively Measuring AsIII, SbIII, and SeIV in Freshwater and Soils.

Anthropogenic and climatic perturbations redistribute arsenic (As), antimony (Sb), and selenium (Se) within the environment. The speciation characteristics of these elements determine their behavior and biogeochemical cycling, but these redox-sensitive species are challenging to capture, with few methods able to harmonize measurements across the whole plant-soil-ecosystem continuum. In this study, we developed a novel diffusive gradient in thin films (DGT) method based on aminopropyl and mercaptopropyl bi-functionalized mesoporous silica spheres (AMBS) to achieve in-situ, simultaneous, and selective quantification of AsIII, SbIII, and SeIV, three typical/toxic but difficult to measure inorganic species. When used for environmental monitoring within a river catchment, AMBS-DGT exhibited stable/accurate predictions of these species despite varying water chemistries (ionic strength 0.01-200 mmol L-1 NO3-, pH 5-9 for AsIII and SbIII, and pH 5-7.5 for SeIV). Furthermore, river deployments also showed that time-averaged species concentrations by AMBS-DGT were reproducible compared with high-frequency sampling and measurement by high performance liquid chromatography coupled with inductively coupled plasma mass spectroscopy. When AMBS-DGT was used for sub-mm scale chemical imaging of soil solute fluxes, the method resolved concomitant redox-constrained spatial patterns of AsIII, SbIII, and SeIV associated with root O2 penetration within anaerobic soil. Improved capabilities for measurement of compartment interfaces and microniche features are critical alongside the measurement of larger-scale hydrological processes that dictate the fine-scale effects, with the AMBS-DGT achieving this for AsIII, SbIII, and SeIV.

A typical case study from smelter-contaminated soil: new insights into the environmental availability of heavy metals using an integrated mineralogy characterization.

Mineralogy was an important driver for the environmental release of heavy metals. Therefore, the present work was conducted by coupling mineral liberation analyzer (MLA) with complementary geochemical tests to evaluate the geochemical behaviors and their potential environmental risks of heavy metals in the smelter contaminated soil. MLA analysis showed that the soil contained 34.0% of quartz, 17.15% of biotite, 1.36% of metal sulfides, 19.48% of metal oxides, and 0.04% of gypsum. Moreover, As, Pb, and Zn were primarily hosted by arsenopyrite (29.29%), galena (88.41%), and limonite (24.15%), respectively. The integrated geochemical results indicated that among the studied metals, Cd, Cu, Mn, Pb, and Zn were found to be more bioavailable, bioaccessible, and mobile. Based on the combined mineralogical and geochemical results, the environmental release of smelter-driven elements such as Cd, Cu, Mn, Pb, and Zn were mainly controlled by the acidic dissolution of minerals with neutralizing potential, the reductive dissolution of Fe/Mn oxides, and the partial oxidation of metal sulfide minerals. The present study results have confirmed the great importance of mineralogy analysis and geochemical approaches to explain the contribution of smelting activities to soil pollution risks.

Multi-component removal of Pb(II), Cd(II), and As(V) over core-shell structured nanoscale zero-valent iron@mesoporous hydrated silica.

The application of nanomaterials for the removal of heavy metals has received a great deal of attention because of their high efficiencies in the environment. But it is difficult to remove multiple heavy metals simultaneously with high efficiency and stability. Herein, the core-shell structured nanoscale zero-valent iron (nZVI) encapsulated with mesoporous hydrated silica (nZVI@mSiO2) were prepared for efficient removal of heavy metals including Pb(II), Cd(II), and metalloid As(V). The material prepared uniformly with a high surface area (147.7 m2 g-1) has a nZVI core with the particle size of 20-60 nm and a modified dendritic mesoporous shell of 19 nm. 0.15 g L-1 of the optimal material exhibited an extraordinary performance on removing Cd(II) and the maximum adsorption capacity for Pb(II), Cd(II), and As(V) reached 372.2 mg g-1, 105.2 mg g-1, and 115.2 mg g-1 with a pH value at 5.0, respectively. The dissolved iron during the reaction showed that the mesoporous silica (mSiO2) played an important role in enhancing the stability of nZVI. In addition, the competitive relationship between the coexistence of two heavy metals was discussed and it was found that the removal efficiency of the material for both was improved when Cd(II) and As(V) were removed synergistically.