Surface engineering of multifunctional nanostructured adsorbents for enhanced wastewater treatment: A review.

Rapid urbanization and industrialization have significantly contributed to the contamination of the environment through the discharge of wastewater containing various pollutants. The development of high-performance surface functional nanostructured adsorbents is of wide interest for researchers. Therefore, we explore the significant advancements in this field, focusing on the efficiency of nanostructured materials, as well as their nanocomposites, for wastewater treatment applications. The crucial role of surface modification in enhancing the affinity of these nanostructured adsorbents towards targeted pollutants, addressing a key bottleneck in the utilization of nanomaterials for wastewater treatment, was specifically emphasized. In addition to highlighting the advantages of surface engineering in enhancing the efficiency of nanostructured adsorbents, this review also provides a comprehensive overview of the limitations and challenges associated with surface-modified nanostructured adsorbents, including high cost, low stability, poor scalability, and potential nanotoxicity. Addressing these limitations is essential for realizing the commercial viability of these state-of-the-art materials for large-scale wastewater treatment applications. This review also thoroughly discusses the potential scalability and environmental safety aspects of surface-modified nanostructured adsorbents, offering insights into their future prospects for wastewater treatment. It is believed that this review will contribute significantly to the existing body of knowledge in the field and provide valuable information for researchers and practitioners working in the area of environmental remediation and nanomaterials.

Ammonia removal and simultaneous immobilization of manganese and magnesium from electrolytic manganese residue by a low-temperature CaO roasting process.

A large amount of open-dumped electrolytic manganese residue (EMR) has posed a severe threat to the ecosystem and public health due to the leaching of ammonia (NH4+) and manganese (Mn). In this study, CaO addition coupled with low-temperature roasting was applied for the treatment of EMR. The effects of roasting temperature, roasting time, CaO-EMR mass ratio and solid-liquid ratio were investigated. The most cost-effective and practically viable condition was explored through response surface methodology. At a CaO: EMR ratio of 1:16.7, after roasting at 187 °C for 60 min, the leaching concentrations of NH4+ and Mn dropped to 10.18 mg/L and 1.05 mg/L, respectively, below their discharge standards. In addition, the magnesium hazard (MH) of EMR, which was often neglected, was studied. After treatment, the MH of the EMR leachate was reduced from 60 to 37. Mechanism analysis reveals that roasting can promote NH4+ to escape as NH3 and convert dihydrate gypsum to hemihydrate gypsum. Mn2+ and Mg2+ were mainly solidified as MnO2 and Mg(OH)2, respectively. This study proposes an efficient and low-cost approach for the treatment of EMR and provides valuable information for its practical application.

Ferrihydrite transformation impacted by coprecipitation of lignin: Inhibition or facilitation?

Lignin is a common soil organic matter that is present in soils, but its effect on the transformation of ferrihydrite (Fh) remains unclear. Organic matter is generally assumed to inhibit Fh transformation. However, lignin can reduce Fh to Fe(II), in which Fe(II)-catalyzed Fh transformation occurs. Herein, the effects of lignin on Fh transformation were investigated at 75°C as a function of the lignin/Fh mass ratio (0-0.2), pH (4-8) and aging time (0-96 hr). The results of Fh-lignin samples (mass ratios = 0.1) aged at different pH values showed that for Fh-lignin the time of Fh transformation into secondary crystalline minerals was significantly shortened at pH 6 when compared with pure Fh, and the Fe(II)-accelerated transformation of Fh was strongly dependent on pH. Under pH 6, at low lignin/Fh mass ratios (0.05-0.1), the time of secondary mineral formation decreased with increasing lignin content. For high lignosulfonate-content material (lignin:Fh = 0.2), Fh did not transform into secondary minerals, indicating that lignin content plays a major role in Fh transformation. In addition, lignin affected the pathway of Fh transformation by inhibiting goethite formation and facilitating hematite formation. The effect of coprecipitation of lignin on Fh transformation should be useful in understanding the complex iron and carbon cycles in a soil environment.

Migration of spent grain-modified colloidal ferrihydrite: Implications for the in situ stabilization of arsenic, lead, and cadmium in co-contaminated soil.

The increase of metal mining, processing, and smelting activities has precipitated a substantial escalation in the contamination of soil by heavy metals. Ferrihydrite (FH) has been commonly used as an amendment for the immobilization of heavy metals in contaminated soil. However, FH suffers from drawbacks such as agglomeration and nonmigratory characteristics, which limit its practical application in soil remediation. Herein, a novel spent grain-modified ferrihydrite (FH-SG) colloidal system was developed, and the FH-SG transport mechanisms in the soil medium were fully studied, focusing in particular on the simultaneous in situ stabilization of arsenic (As), lead (Pb), and cadmium (Cd) in co-contaminated soil. The results showed that the stabilization rates of the FH-SG material reached 94.66%, 96.12%, and 95.52% for water-soluble As, Pb, and Cd, respectively, and 72.22%, 49.39%, and 25.30% for bioavailable As, Pb, and Cd, respectively. The FH-SG material demonstrates notable migration properties in porous media. Theoretical calculation results of a single collector show that the migration deposition of FH-SG material in media is primarily governed by its inherent diffusion characteristics with minimal influence by gravitational forces and media interception. It is noteworthy that the maximum migration distance in quartz sand and soil media with different particle sizes can reach 2.07-2.92 m and 0.78-1.08 m, respectively. Altogether, our findings clearly demonstrate that FH-SG exhibits better stabilization and migration than those of FH alone and most proposed FH colloidal systems. The FH-SG colloidal system holds significant promise for the remediation of various kinds of complex polluted soil.

Molecular level insight of thiocyanate degradation by Pseudomonas putida TDB-1 under a high arsenic and alkaline condition.

It is a big challenge to bioremediate thiocyanate pollution in the gold extraction heap leaching tailings and surrounding soils with high contents of arsenic and alkali. Here, a novel thiocyanate-degrading bacterium Pseudomonas putida TDB-1 was successfully applied to completely degrade 1000 mg/L thiocyanate under a high arsenic (400 mg/L) and alkaline condition (pH = 10). It also leached the contents of thiocyanate from 1302.16 to 269.72 mg/kg in the gold extraction heap leaching tailings after 50 h. The maximum transformation rates of S and N in thiocyanate to the two finial products of SO42- and NO3- were 88.98 % and 92.71 %, respectively. Moreover, the genome sequencing confirmed that the biomarker gene of thiocyanate-degrading bacterium, CynS was identified in the strain TDB-1. The bacterial transcriptome revealed that critical genes, such as CynS, CcoNOQP, SoxY, tst, gltBD, arsRBCH and NhaC, etc. in the thiocyanate degradation, S and N metabolisms, and As and alkali resistance were significantly up-regulated in the groups with 300 mg/L SCN- (T300) and with 300 mg/L SCN- and 200 mg/L As (TA300). In addition, the protein-protein interaction network showed that the glutamate synthase encoding by gltB and gltD served as central node to integrate the S and N metabolism pathways with thiocyanate as substrate. The results of our study provide a novel molecular level insight for the dynamic gene expression regulation of thiocyanate degradation by the strain TDB-1 with a severe arsenic and alkaline stress.

Synchronous stabilization of As, Cd, and Pb in soil by sustained-release of iron-phosphate.

Anionic arsenic (As) exhibits geochemical behavior opposite to those of cationic cadmium (Cd), and lead (Pb), which makes the synchronous remediation of As, Cd, and Pb challenging. The synchronous stabilization of As, Cd, and Pb to form Cd/Pb-phosphate and iron­arsenic precipitates is a promising strategy. However, the effectiveness of soluble phosphate or iron-based materials is limited by the activation of Cd, Pb, or As, while low mobility hinders insoluble particles. In this study, we developed an amorphous structure that releases iron and phosphate at a sustained rate. Thus, the stabilization efficiencies of NaHCO3-extractable As, DTPA-extractable Cd and Pb reached 44.6 %, 40.8 %, and 48.1 %, respectively. The proportion of residual fraction of As, Cd, and Pb increased by 12.1 %, 14.5 %, and 36.4 %, respectively, after 28 d. Ferrihydrite was chosen as the soil component to monitor the chemical behavior and speciation transformation of As, Cd, and Pb in the reaction. During the process, the released iron directly reacted with dissolved As to form iron­arsenic precipitation and phosphate directly reacted with Cd/Pb to form Cd/Pb-phosphate precipitation. Simultaneously, phosphate replaced the adsorbed As and transformed into a dissolved state, which could be re-precipitated with the released iron ions. Thus, this study provides a reliable strategy for the remediation of As, Cd, and Pb combined pollution in soil.

Organic acid, phosphate, sulfate and ammonium co-metabolism releasing insoluble phosphate by Klebsiella aerogenes to simultaneously stabilize lead and cadmium.

Here, a novel phosphate-solubilizing bacterium (PSB), Klebsiella aerogenes Wn was applied to develop an environmental-friendly method to simultaneously stabilize Pb and Cd. The maximum dissolved phosphate was up to 701.36 mg/L by the strain Wn. The high performance liquid chromatography (HPLC) and Pearson correlation analyses showed that the acetic acid produced by the strain Wn was significantly positively associated with the released phosphate. Moreover, 100% of 500 mg/L of Pb and 100 mg/L of Cd were simultaneously stabilized in the classical NBRIP medium and the major products were Pb5(PO4)3Cl, Ca7.7Cd0.8(PO4)8(H2O)2.4 and CdS, respectively. In addition, the bacterial genome and transcriptome analyses showed that the pentose phosphate pathway (PPP), pyruvate metabolism pathway, thiamine metabolic pathway, sulfate reduction and ammonium bio-transformation were coupled to promote releasing insoluble phosphate and stabilizing Pb and Cd. In the metabolism networks, the critical genes of gcd, aceE, thiE, thiS and cysH, etc. were significantly up-regulated. Our results are beneficial to deeper understand the molecular mechanisms of releasing insoluble inorganic phosphate by PSBs and develop a technology prototype to simultaneously stabilize Pb and Cd using the PSBs.

Ferrate modified carbon felt as excellent heterogeneous electro-Fenton cathode for chloramphenicol degradation.

In this study, a novel and efficient heterogeneous electro-Fenton (EF) process with a potassium ferrate (K2FeO4) modified carbon felt (Fe-CF) cathode was developed for chloramphenicol (CAP) removal. The catalytic activity was assessed by the comparison of different systems and the effects of multiple operating parameters (K2FeO4 dosage, initial solution pH, applied current) and co-existing constituents. Results indicated that the Fe-CF cathode exhibited excellent performance for CAP degradation (almost 100% removal efficiency within 60 min) over a wide range of pH (pH 3-9) during heterogeneous EF ascribed to the synergistic effect of embedded iron species and porous graphitic carbon structure and effective utilization of the in-situ generated H2O2. Moreover, the Fe-CF cathode possessed good recyclability with low metal leaching (98.2% CAP removal efficiency after reused for 5 times) and outstanding real water application performance. The ∙OH and O2∙- were responsible for CAP degradation, while ∙OH played a main role. Moreover, the toxicity evaluation by E. coli growth experiments demonstrated an efficient toxicity reduction in this system. Overall, a novel heterogeneous EF functional cathode with superior performance was fabricated via a green, low-cost one-step method, which shows promising application potential for actual wastewater treatment.

Dual functional sites strategies toward enhanced heavy metal remediation: Interlayer expanded Mg-Al layered double hydroxide by intercalation with L-cysteine.

The discharge of toxic heavy metals poses a serious threat to human health and environment. The existing water purification systems are lack of promising materials for rapid, efficient, and cost-efficient remediation of numerous toxic heavy metals. Herein, we report on the development of L-cysteine (Cys) intercalated Mg-Al layered double hydroxide (MgAl-LDH/Cys) with a loose lamellar porous architecture as an efficient and economically viable adsorbent for Pb(II) and Cd(II) removal. The intercalation with Cys creates dual functionality, i.e., the interlayer expansion accelerates the diffusion of heavy metals, while Cys acts as additional capture sites for heavy metals. Therefore, remarkable high maximum sorption capacities of 279.58 and 135.68 mg g-1 for Pb(II) and Cd(II) were obtained for MgAl-LDH/Cys compared to those for pristine MgAl-LDH (30.15 and 36.77 mg g-1). MgAl-LDH/Cys exhibits also much faster sorption kinetics in comparison with MgAl-LDH. Such enhancements are attributed to the intercalation of the chelating agent Cys in the MgAl-LDH interlayer channels. Moreover, it is proposed that the adsorption mechanisms involve the isomorphous replacement of Mg sites by Cd(II) forming CdAl-LDH, the precipitation of PbS and CdS, and the chelation of sulfhydryl, carboxyl and amine groups toward Cd(II). Altogether, its facile and environmentally friendly fabrication, ultrahigh sorption efficiencies, and rapid kinetics demonstrate that MgAl-LDH/Cys has potential for practical applications in heavy metal remediation.

Iron-doped hydroxyapatite for the simultaneous remediation of lead-, cadmium- and arsenic-co-contaminated soil.

Since lead, cadmium and arsenic have completely opposite chemical behaviors, it is very difficult to stabilize all these three heavy metals simultaneously. Herein, a novel iron-doped hydroxyapatite composite (Fe-HAP) was developed via an ultrasonic-assisted microwave hydrothermal method for the simultaneous remediation of lead-, cadmium-, and arsenic-co-contaminated soil in Hunan Province, South China. Using DTPA/sodium bicarbonate extractant to extract bioavailable Pb, Cd and As in soil after Fe-HAP remediation for 60 days, the immobilization efficiencies were 79.77%, 51.3% and 37.5% for Pb, Cd and As, respectively. The soil extractable and exchangeable fractions of Pb, Cd and As decreased significantly. In batch experiments, the adsorption kinetics of Pb, Cd and As on Fe-HAP were well described by pseudo-second-order models, indicating that the adsorption is controlled by chemisorption. In the Langmuir adsorption isotherm, the maximum adsorption capacities of Cd2+ and As(V) were 476.2 mg g-1 and 195.69 mg g-1, respectively, while Pb2+ fit the Freundlich model better. The XRD, SEM and XPS analyses indicated that Fe-HAP formed stable minerals of Pb5(PO4)3OH, Cd3(PO4)2·4H2O, Cd(OH)2 and Fe3(AsO4)2·6H2O with Pb, Cd and As. Overall, its facile and efficient immobilization performance indicate that Fe-HAP has potential for practical applications in integrative remediation of Pb-, Cd-, and As- co-contaminated soil.

Enhancing the anti-oxidation stability of vapor-crystallized arsenic crystals via introducing iodine.

The oxidation of arsenic restricts its application in high-performance electronic devices and functional materials. Herein, a removable iodine-regulation method was proposed for the first time to enhance the anti-oxidation behavior of arsenic. In a gradient of 500-650 â„ƒ, the introduction of 0.6-5.0 at% iodine into arsenic vapor could regulate an arsenic crystal. The oxygen content on the regulated arsenic crystal surface was lowered below 2.5 at% after exposure to ambient conditions for 96 h, reducing over 90% compared with the control group. The residual iodine barrier, which was mainly in the As-I2 state, suppressed the long-term oxidation of arsenic. First-principles calculation suggested that the adsorbed I2 weakened the delocalization of lone-pair electrons and inhibited charge transfer from the arsenic surface. Iodine regulation stabilized arsenic surface, which preferred (003) or (012) facets. Their surface energies were 22.4 meV and 47.6 meV, respectively. The synergistic effect of surface stabilization and I2 passivation lowered the surface energy and continuously slowed the oxidation of arsenic. Therefore, iodine regulation comprehensively enhanced the anti-oxidation properties of arsenic. Moreover, heating at 200 â„ƒ left the arsenic surface iodine content below 0.1 at% with little variation in structure. The improved anti-oxidation property of arsenic preserves resources for further advanced applications.

Selenium-sulfur functionalized biochar as amendment for mercury-contaminated soil: High effective immobilization and inhibition of mercury re-activation.

The contamination of soils by mercury (Hg) seriously threatens the local ecological environment and public health. S-functionalized amendments are common remediation technology, yet, Hg re-activation often occurs in the commonly used immobilization remediation by S-functionalized amendments, resulting in an unsatisfactory remediation effect. In this study, a novel FeS-Se functionalized biochar composite (FeS-Se-BC) amendment was prepared and applied for the efficient remediation of Hg-polluted soil. An immobilization efficiency of 99.62% and 99.22% for H2O-extractable Hg and TCLP solution-extractable Hg was achieved with the application of FeS-Se-BC(0.05) after 180 d. The analyses of XPS, Hg-TPD, SEM-EDS demonstrated that excellent remediation performance by FeS-Se-BC resulted from the synergistic effect of FeS and Se to form HgS and HgSe concurrently. In comparison to the treatments of biochar and FeS-functionalized biochar (FeS-BC), FeS-Se-BC promoted the transformation of exchangeable, carbonate-bound, and Fe-Mn oxides-bound Hg fractions into organic material-bound, and residual fractions, effectively reducing the risk of Hg-contaminated soil from a highly dangerous level to a low risk. Furthermore, the introduction of Se clearly inhibited the re-activation of Hg and reduced the release of Hg by 81.12% compared to FeS-BC when the ratio of S2- to Hg was 5: 1 due to the formation of extremely stable HgSe. These results suggest that FeS-Se-BC has good potential for remediation of Hg-polluted soils which provides a new inhibitory idea for Hg re-activation after immobilization.

Highly efficient removal of arsenic (III/V) from groundwater using nZVI functionalized cellulose nanocrystals fabricated via a bioinspired strategy.

Utilizing nanoscale zero valent iron (nZVI) to purify groundwater contaminated by arsenic species [As(III/V)] is an efficient technology, but the fast and severe aggregation of nZVI limits its practical applications. Herein, nZVI was anchored onto the mussel-inspired polydopamine-coated cellulose nanocrystals (CNCs-PDA-nZVI) as an efficient material for As groundwater remediation. In this set, the introduction of nZVI was expected to significantly enhance the arsenic removal property, while cellulose nanocrystals (CNCs) endowed nZVI with ultrahigh dispersibility. The batch results showed that the maximum As adsorption capacities of CNCs-PDA-nZVI (i.e., 333.3 mg g-1 and 250.0 mg g-1 for As(III) and As(V), respectively) were ten times higher compared with those of pristine CNCs. The kinetics results revealed that chemical adsorption was dominant for As adsorption. The isotherms indicated that a homogeneous adsorption for As(III) and heterogenous adsorption for As(V) on the surface of CNCs-PDA-nZVI. The removal mechanisms for As by CNCs-PDA-nZVI included adsorption-oxidation, coprecipitation and inner-sphere complexation. Overall, the excellent arsenic removal efficiency makes CNCs-PDA-nZVI a promising material for the remediation of As polluted groundwater, and this in-situ anchoring strategy can be extended to overcome the aggregation bottleneck of other nanoparticles for various applications.

Co-Co3O4 encapsulated in nitrogen-doped carbon nanotubes for capacitive desalination: Effects of nano-confinement and cobalt speciation.

Capacitive deionization (CDI) has gained increasing attention as an environmentally friendly and energy-efficient technology for brackish water desalination. However, traditional CDI electrodes still suffer from low salt adsorption capacity and unsatisfactory reusability, which inhibit its application for long-term operations. Herein, we present a facile and effective approach to prepare Co and Co3O4 nanoparticles co-incorporating nitrogen-doped (N-doped) carbon nanotubes (Co-Co3O4/N-CNTs) via a pyrolysis route. The Co-Co3O4 nanoparticles were homogeneously in-situ encapsulated in the inner channels of the conductive CNTs to form a novel and efficient CDI electrode for the first time. The encapsulation of Co-Co3O4 nanoparticles in CNTs not only inhibits the Co leaching but also significantly enhances the desalination capacity. The morphology, structure, and capacitive desalination properties of the Co-Co3O4/N-CNTs were thoroughly characterized to illuminate the nano-confinement effects and the key roles of the interaction between cobalt species in the CDI performance. The co-existing metallic cobalt and cobalt oxides act as the roles of effective active sites in the CDI performance. As a consequence, the optimum Co-Co3O4/N-CNTs electrode displays an outstanding desalination capacity of 66.91 mg NaCl g-1 at 1.4 V. This work provides insights for understanding the nano-confinement effects and the key roles of the interaction between cobalt species on the CDI performance.

Performance and mechanisms of microwave-assisted zerovalent iron/pyrite for advance remediation of strongly alkaline high Cr(VI) contaminated soil.

Strongly alkaline high Cr(VI) contaminated (SAHCR) soil poses a high risk to the environment and public health, yet lacks rapid and efficient remediation technology. In this study, a novel approach combining microwave irradiation with zerovalent iron/pyrite (FeS2/ZVI) was developed for the remediation of SAHCR soil. The results indicated that fast and efficient remediation of the SAHCR soil was achieved by microwave irradiation-assisted FeS2/ZVI, with 99.9% of removal rate of Cr(VI) within 10 min, and Cr(VI) concentration from 3900.8 plummeted to 2.38 mg kg-1. The data of Cr(VI) reduction kinetics at different temperatures indicated that the activation energies (Ea) for microwave-FeS2/ZVI system was 27.4 kJ mol-1, 28.5% lower than that without microwave irradiation, suggesting that in addition to the heating effect of microwave, the accelerated Cr(VI) reduction also comes from the catalytic effect of "hot spots" on FeS2/ZVI under microwave irradiation. Furthermore, it was demonstrated that microwave irradiation promoted the transformation of reduced Cr(III) into the stable FeCr2O4 mineral and the excellent long-term stability of the remediated SAHCR soil. These findings can provide a perspective for advanced remediation of the difficult-to-treat SAHCR soil by the synergism of microwave irradiation with the iron-sulfur based reducing materials.

Application of biochars in the remediation of chromium contamination: Fabrication, mechanisms, and interfering species.

Chromium (Cr) is one of the most toxic pollutants that has accumulated in terrestrial and aqueous systems, posing serious risks towards living beings on a worldwide scale. The immobilization, removal, and detoxification of active Cr from natural environment can be accomplished using multiple advanced materials. Biochar, a carbonaceous pyrolytic product made from biomass waste, is considered as a promising material for the elimination of Cr contamination. The preparation and properties of biochar as well as its remediation process for Cr ions have been well investigated. However, the distinct correlation of the manufacturing, characteristics, and mechanisms involved in the remediation of Cr contamination by various designed biochars is not summarized. Herein, this review provides information about the production, modification, and characteristics of biochars along with their corresponding effects on Cr stabilization. Biochar could be modified via physical, hybrid, chemical, and biological methods. The remediating mechanisms of Cr contamination using biochars involve adsorption, reduction, electron shuttle, and photocatalysis. Moreover, the coexisting ions and organic pollutants change the pattern of the remediating process of biochar in actual Cr contaminated water and soil. Finally, the present limitations and future perspectives are proposed.

Oxidation of 2,4-dichlorophenol in saline water by unactivated peroxymonosulfate: Mechanism, kinetics and implication for in situ chemical oxidation.

Inorganic and organic pollutants present a hazard to surface and groundwater resources. Peroxymonosulfate (PMS, HSO5-) has received increasing attention for in situ chemical oxidation (ISCO) capable of remediating contaminated sites. Considering that saline waters occur widely in natural environments, it is desirable to evaluate the effect of Cl- on the PMS oxidation of organic compounds. In this study, 2,4-dichlorophenol (2,4-DCP) was used as a model pollutant. At a PMS concentration of 2.0 mM, Cl- concentration of 50 mM, and solution pH of 7.0, 2,4-DCP was completely degraded by PMS in the presence of Cl- (PMS/Cl- system), while PMS alone exhibited almost no reactivity with 2,4-DCP. The degradation of 2,4-DCP was optimized at a solution pH of 8.4 and high concentrations of PMS and Cl-. Quenching experiments and degradation pathway analyses indicated that HClO was responsible for 2,4-DCP oxidation, and HClO was mainly generated by the interaction of Cl- with HSO5-, rather than SO52-. Consequently, the transformation from HSO5- to HClO appeared under a solution pH of 10.0 and was favored in an acidic solution. Given the ambient pH and Cl- concentrations of saline waters, a considerable amount of HClO may be produced by the interaction of PMS with Cl- in the oxidant delivery stage of ISCO processes. Interestingly, H2O2 and peroxydisulfate did not exhibit reactions similar to those of PMS. This research indicated that caution must be exercised when choosing an oxidant for ISCO processes in saline waters.

Enhanced adsorption of antimonate by ball-milled microscale zero valent iron/pyrite composite: adsorption properties and mechanism insight.

Ball-milling is considered as an economical and simple technology to produce novel engineered materials. The ball-milled microscale zero valent iron/pyrite composite (BM-ZVI/FeS2) had been synthesized through ball-milling technology and applied for highly efficient sequestration of antimonate (Sb(V)) in aqueous solution. BM-ZVI/FeS2 exhibited good Sb(V) removal efficiency (≥ 99.18%) at initial concentration less than 100 mg Sb(V)/L. Compared to ball-milled zero valent iron (ZVI) and pyrite (FeS2), BM-ZVI/FeS2 exhibited extremely higher removal efficiency due to the good synergistic adsorption effect. BM-ZVI/FeS2 showed efficient removal performance at broad pH (2.6-10.6). Moreover, the coexisting anions had negligible inhibition influence on the Sb(V) removal. The antimony mine wastewater can be efficiently remediated by BM-ZVI/FeS2, and the residual Sb(V) concentrations (< 0.96 µg/L) can meet the mandatory discharge limit in drinking water (5 µg Sb/L). Experimental and model results demonstrated that endothermic reaction and chemisorption were involved in Sb(V) removal by BM-ZVI/FeS2. The XRD and XPS analyses confirmed that the complete corrosion of ZVI occurred on BM-ZVI/FeS2 after Sb(V) adsorption, resulting in the enhanced Sb(V) sequestration. Mechanism analyses showed that the excellent removal performance of BM-ZVI/FeS2 was ascribed to the high coverage of iron (hydr)oxide oxidized from ZVI. Because of the advantages of economical cost, high Sb(V) removal capacity and easy availability, BM-ZVI/FeS2 offers a promising adsorbent for Sb(V) remediation.

An experimental and theoretical study on the degradation of clonidine by hydroxyl and sulfate radicals.

Emerging contaminants such as pharmaceuticals that cannot be completely removed by traditional biological treatments are ubiquitously present in water bodies with detected concentrations ranging from ng L-1 to mg L-1. Advanced oxidation technologies (AOTs) are promising, efficient, and environmentally friendly for the removal of these pharmaceuticals. In this study, we investigated the degradation kinetics of a model pharmaceutical, clonidine (CLD), via hydroxyl radical (OH) in UV/H2O2 and sulfate radical (SO4•-) in UV/peroxydisulfate (PS) systems for the first time. The second-order rate constants (k) of protonated cationic CLD with OH and SO4•- were measured to be (2.15 ±â€¯0.07) × 109 M-1 s-1 and (1.12 ±â€¯0.03) × 109 M-1 s-1, respectively. We also calculated the pKa value of CLD and thermodynamic behaviors for reactions of CLD/HCLD+ with OH and SO4•- at M05-2X/6-311++G**//M05-2X/6-31+G** level with SMD solvation model. The pKa value was calculated to be 8.14, confirming the literature value. H atom abstraction pathway was the most favorable pathway for both OH and SO4•-, while single electron transfer pathway was thermodynamically feasible only for SO4•- for CLD but not for HCLD+. In addition, the reactivities of both tautomeric forms of CLD (i.e., amino and imino CLD) with both radicals were also investigated. This study contributed to a better understanding on the degradation mechanisms of CLD and proposed the possibilities of the elimination of pharmaceuticals by applying AOTs during wastewater treatment processes.

Compressible cellulose nanofibril (CNF) based aerogels produced via a bio-inspired strategy for heavy metal ion and dye removal.

A sustainable nanomaterial, cellulose nanofibril (CNF) was used to prepare aerogel sorbents to remove various contaminants in wastewater. A mussel-inspired coating strategy was used to introduce polydopamine onto the surface of CNFs, which were cross-linked with polyethylenimine (PEI) to form the aerogels. The synthetic procedure was optimized to achieve a minimal consumption of raw materials to produce a robust porous structure. The aerogels possessed a low density (25.0 mg/cm3), high porosity (98.5%) and shape recovery in air and water. Adsorption studies were conducted on two representative contaminants, Cu (II) and methyl orange (MO). The kinetic data obeyed the pseudo 2nd order kinetic model and the mechanism of adsorption could be described by the intra-particle diffusion model. The Langmuir model fitting yielded a maximum adsorption capacity of 103.5 mg/g and 265.9 mg/g for Cu (II) and MO, respectively. The effects of pH on the adsorption performance were evaluated, confirming that the aerogels can maintain a high adsorption capacity over a wide pH range.