Photocatalytic Generation of H2O2 Via a Hydrogen-Abstraction Pathway by Bi2.15WO6 under Visible Light.

Photocatalytic technology is a popular research area for converting solar energy into environmentally friendly chemicals and is considered the greenest approach for producing H2O2. However, the corresponding reactive oxygen species (ROS) and pathway involved in the photocatalytic generation of H2O2 by the Bi2.15WO6-glucose system are still not clear. Quenching experiments have established that neither •OH nor h+ contribute to the formation of H2O2, and show that the formed surface superoxo (≡Bi-OO•) and peroxo (≡Bi-OOH) species are the predominant ROS in H2O2 generation. In addition, various characterizations indicate the enhanced electron-transfer on the surface of Bi2.15WO6 with increasing contents of glucose via the ligand-to-metal charge transfer pathway, confirming H-transfer from glucose to ≡Bi-OO• or ≡Bi-OOH. The increased production of H2O2 with decreasing bond dissociation energy (BDEO-H) values of various phenolic compounds again supports the H-transfer mechanism from phenolic compounds to ≡Bi-OO• and then to ≡Bi-OOH. DFT calculations further reveal that on the Bi2.15WO6 surface, oxygen is sequentially reduced to ≡Bi-OO• and ≡Bi-OOH, while H-transfer from H2O or glucose to ≡Bi-OO• and ≡Bi-OOH, resulting in the production of H2O2. The lower energy barrier of H-transfer from adsorbed glucose (0.636 eV) than that from H2O (1.157 eV) indicates that H-transfer is more favorable from adsorbed glucose. This work gives new insight into the photocatalytic generation of H2O2 by Bi2.15WO6 in the presence of glucose/phenolic compounds via the H-abstraction pathway.

Satisfactory Tensile Strength and Strain of Recyclable Polyurethane with a Trimaleimide Structure for Thermal Self-Healing and Anticorrosive Coatings.

Bismaleimide (BMI) is often used as the cross-linking reagent in Diels-Alder (D-A)-type intrinsic self-healing materials (DISMs) to promote the connectivity of damaged surfaces based on reversible D-A bond formation on the molecular scale. Until now, although DISMs have exhibited great potential in the applications of various sensors, electronic skin, and artificial muscles, it is still difficult to prepare DISMs with satisfactory self-healing abilities and high tensile strengths and strains at the same time, thus largely limiting their applications in self-healing anticorrosive coatings. Herein, symmetrical trimaleimide (TMI) was successfully synthesized, and trimaleimide-structured D-A self-healing polyurethane (TMI-DA-PU) was prepared via the reversible D-A reaction (cycloaddition of furan and maleimide). As a DISM, TMI-DA-PU exhibits apparently higher self-healing efficiency (98.7%), tensile strength (25.4 MPa), and strain (1378%) compared to bismaleimide-structured D-A self-healing polyurethane (BMI-DA-PU) (self-healing efficiency, 90.2%; tensile strength, 19.3 MPa; strain, 1174%). In addition, TMI-DA-PU shows a high recycling efficiency (>95%) after 4 cycles of recycling. A series of characterizations indicate that TMI provides more monoene rings as the self-healing sites, forms denser cross-linked structures compared to BMI, and is, thus, more appropriate to be used for DISM applications. Moreover, the barrier abilities of coatings can be semi-quantitatively expressed by the impedance value at 0.01 Hz (|Z|0.01 Hz). The |Z|0.01 Hz value of the TMI-DA-PU coating is 3.93 × 109 Ω cm2 on day 0, which is significantly higher than that of the BMI-DA-PU coating (6.76 × 108 Ω cm2 on day 0), indicating that the denser rigid cross-linked structure of TMI results in the small porosity in the TMI-DA-PU coating, thus effectively improving the anticorrosion performance. The construction of DISMs with the structure of TMI demonstrates immense potential in self-healing anticorrosive coatings.

Contributions of Surface Oxidizing Species and Cu+ to the Antibacterial Activities of Cu2O with Different Crystalline Structures.

Although precise regulation of the crystalline structures of metal oxides is an effective method to improve their antibacterial activities, the corresponding mechanisms involved in this process are still unclear. In this study, three kinds of cuprous oxide (Cu2O) samples with different structures of cubes, octahedra, and rhombic dodecahedra (c-Cu2O, o-Cu2O, and r-Cu2O) have been successfully synthesized and their antibacterial activities are compared. The antibacterial activities follow the order of r-Cu2O > o-Cu2O > c-Cu2O, revealing the significant dependence of the antibacterial activities on the crystalline structures of Cu2O. Quenching experiments, as well as the NBT and DPD experiments indicate that ≡CuII─OO• superoxo and ≡CuII─OOH peroxo, instead of •OH, O2•-, and H2O2, are the primary oxidizing species in the oxidative damage to E. coli. Raman analysis further confirms the presence of both ≡CuII─OO• superoxo and ≡CuII─OOH peroxo on the surface of r-Cu2O. On the other hand, the NCP experiment reveals that Cu+, instead of Cu2+, also contributes to the antibacterial process. This study provides new insight into the antibacterial mechanisms of Cu2O.

Selective Oxidation of Cyclohexane to Cyclohexanol/Cyclohexanone by Surface Peroxo Species on Cu-Mesoporous TiO2.

Selective oxidation of cyclohexane to cyclohexanol/cyclohexanone (KA-oil) is an important chemical process, which is still constrained by low conversion and selectivity and high energy consumption. In this study, Cu-doped mesoporous TiO2 (Cu-MT) has been successfully synthesized via calcinating MIL-125(Ti) doped with copper acetylacetonate, which shows high reactivity in selective oxidation of cyclohexane to KA-oil by persulfate (PS) with the desirable cyclohexane conversion of 16.8% and a selectivity of 98.0% under mild conditions and the low ratio of PS/cyclohexane of 1:1. A series of characterizations and density functional theory calculations reveal that the doped Cu(I,II) on Cu-MT is the reactive site for non-radical activation of PS with the moderate elongation of the O-O bond in PS, which then abstracts 1H (1H+ + 1e-) from cyclohexane to form Cy• and eventually KA-oil. This study gives new insight on the importance of moderately activated PS in selective oxidation of C-H.

Mediation of water-soluble oligoaniline by phenol in the aniline-persulfate system under alkaline conditions.

Although synthesis of oligoaniline (OANI) by persulfate and aniline has been investigated in the recent years, the impact of phenol on the synthesized soluble OANI is still not clear. In this study, our results indicate that phenol and pH mediate the production of the blue water-soluble OANI (OANIblue) in the reaction between sodium persulfate (SPS) and aniline under alkaline conditions, and the yields of OANIblue increase with increasing concentrations of phenol and pH values. Quenching experiments rule out the contributions of SO4˙- and ˙OH to aniline oxidation and imply that the non-radical activation of SPS is an important pathway in the formation of OANIblue. MALDI-TOF-MS analysis indicates that phenol apparently inhibits the polymerization degree of aniline in that the molecular weights of OANIblue gradually decrease from 1586.4 to 684.6 when phenol is increased from 0 to 2.0 mM. FTIR and Raman analyses confirm the structure of aniline oligomers in OANIblue and indicate that phenol inhibits the phenazine-like structure in OANIblue and facilitates the transformation of benzenoid rings to quinoid rings in the oxidation products. However, simultaneous activation of SPS by phenol and aniline is likely to occur in the reaction system with the formation of PhNH˙, as indicated by DFT calculations. The high scavenging reactivity of phenol towards both PhNH2˙+ and PhNH˙ implies that PhNH2˙+ and PhNH˙ are not the intermediates in the formation of OANIblue. DFT calculations also reveal that apart from the one-electron transfer pathway between aniline and SPS, the two-electron transfer pathway is also likely to occur in the presence of phenol, resulting in the formation of PhNH+/PhN˙˙ without producing PhNH2˙+ and PhNH˙. The produced PhNH+/PhN˙˙ intermediates then couple with aniline, PhNH+, aminophenyl sulfate and its hydrolysate to form dimers, trimers, oligomers, and eventually OANIblue. This study not only describes a novel method to prepare water-soluble OANI, but also gives new insight on the importance of phenol in the production of OANIblue.

Formation and Oxidation Reactivity of MnO2+(HCO3-)n in the MnII(HCO3-)-H2O2 System.

The MnII(HCO3-)-H2O2 (MnII-BAP) system shows high reactivity toward oxidation of electron-rich organic substrates; however, the predominant oxidizing species and its formation pathways involved in the MnII-BAP system are still under debate. In this study, we used the MnII-BAP system to oxidize As(III) in that As(III), Mn2+, and HCO3- are common components in As(III)-contaminated groundwater. Kinetic results show that MnII(HCO3-)n [including MnII(HCO3)+ and MnII(HCO3)2] is a key factor in the MnII-BAP system to oxidize As(III). Quenching experiments rule out contributions of OH• and 1O2 to As(III) oxidation and reveal that O2•- and the oxidizing species generated from O2•- play predominant roles in the oxidation of As(III). We further reveal that the MnO2+(HCO3-)n intermediate generated in the reaction between MnII(HCO3-)n and O2•-, instead of O2•-, is the predominant oxidizing species. Although CO3•- also contributes to As(III) oxidation, the high reaction rate constant between CO3•- and O2•- indicates that CO3•- is not the predominant oxidizing species in the As(III)-MnII-BAP system. In addition, the presence of Mn(III) further indicates the important Mn(II)-Mn(III) cycling in the MnII-BAP system. We therefore suggest two important roles of MnII(HCO3-)n in the MnII-BAP system: (i) MnII(HCO3-)n reacts with H2O2 to form the MnIII(HCO3)3 intermediate, followed by a subsequent reaction between MnIII(HCO3)3 and H2O2 to produce O2•-; (ii) MnII(HCO3-)n can also stabilize O2•- with the formation of MnO2+(HCO3-)n. MnO2+(HCO3-)n is an electrophilic reagent and plays the predominant role in the oxidation of As(III) to As(V).

Formation of hydroperoxo (-OOH) species on the surface of self-doped Bi2.15WO6: reactivity towards As(iii) oxidation.

Bi2+xWO6 is a cost-effective and environmentally friendly photocatalyst that shows high reactivity in the oxidation of various contaminants under visible light. However, under alkaline conditions, the reactive oxidative species in the Bi2+xWO6 system are still not clear yet. In this study, it is observed that the oxidation rates of As(iii) increase with increasing pH values in the Bi2.15WO6 system. Photoluminescence and the Mott-Schottky analyses confirm that OH- promotes the separation and transfer of photogenerated electron-hole pairs over Bi2.15WO6, thus facilitating the oxidation of As(iii). Electron spin resonance spectra analysis and quenching experiments rule out contributions of •OH, O2˙-, 1O2 and superoxo species to As(iii) oxidation and indicate that surface -OOH and/or H2O2 are indeed the predominant species under alkaline conditions. The improved production of H2O2 by H-donors such as glucose and phenol, as well as the UV-vis diffuse reflectance and Raman analyses, further confirms the formation of surface -OOH on Bi2.15WO6 under alkaline conditions. In the dark, the significant higher oxidation rate of As(iii) by H2O2-Bi2.15WO6 than that by H2O2 alone reveals that surface -OOH, instead of H2O2, plays an important role in As(iii) oxidation. This study enriches our understanding of the diversity of reactive oxygen species (ROS) in the Bi2.15WO6 system and gives new insight into the mechanism involved in the oxidation of As(iii) under alkaline conditions.

The fast redox cycle of Cu(II)-Cu(I)-Cu(II) in the reduction of Cr(VI) by the Cu(II)-thiosulfate system.

Thiosulfate (S2O32-) is an important ligand to complex metal cations, however, the reactivity of metal-thiosulfate complexes has barely been mentioned. In this study, the reactivity of the Cu(II)-S2O32- system in the reduction of Cr(VI) was investigated. Kinetic results show that the reduction rates of Cr(VI) decrease with increasing pH values from 3.0 to 5.0, and 94.3% and 97.5% of 10 mg L-1 Cr(VI) was rapidly reduced within 1 min at pH 3.0 and within 30 min at pH 5.0, respectively at the molar ratio of Cu(II):S2O32- of 0.05. We rule out the contributions of S species of tetrathionate (S4O62-) and sulfite (SO32-) to Cr(VI) reduction and point out that the produced Cu(I) in the Cu(II)-S2O32- system is the key reductant that mediates the reduction of Cr(VI). We suggest that complexation between Cu(II) and S2O32- with the formation of CuII(S2O3)22- is the pre-requisite for the formation of CuI(S2O3)n1-2n, which plays an important role in Cr(VI) reduction, accompanied by the re-oxidation of Cu(I) to Cu(II) by Cr(VI), achieving the rapid redox cycling of Cu(II)-Cu(I)-Cu(II). Such a redox cycle also mediates the denitrification process of NO2- to NH3/NH4+ under weakly acidic conditions. This study enriches our understanding on the reducing reactivity of the Cu(II)-S2O32- system and the importance of the Cu(II)-Cu(I)-Cu(II) redox cycle towards environmental oxidizing contaminants.

Enhanced permeate flux by air micro-nano bubbles via reducing apparent viscosity during ultrafiltration process.

Micro-nano bubbles (MNBs) play important roles in the reduction of membrane fouling during membrane separation; however, such improvements are always attributed to the reduced concentration polarization on the surface of membranes and little attention has been paid on the variations of physicochemical properties of the feed caused by MNBs. In this study, the separation efficiencies of the feed containing humic acid (HA), bovine serum albumin (BSA), sodium alginate (SA) or dyes can be improved by MNBs during ultrafiltration, and the normalized fluxes can be maximally increased to 139% and 127% in the dead-end and cross-flow modes, respectively in the treatment of HA solution. We further reveal that the decreased apparent viscosity of the feed in the presence of MNBs is the key factor that enhances the normalized flux during ultrafiltration. This study gives new insight on the importance of MNBs in membrane separation and provides valuable clues for other chemical processes.

Selective oxidation of aniline contaminants via a hydrogen-abstraction pathway by Bi2·15WO6 under visible light and alkaline conditions.

Conversion of aniline wastes to value-added products is always a promising method to treat aniline wastewater. In this study, a selective oxidation of aniline contaminants by Bi2·15WO6 was carried out under visible light and alkaline conditions. Kinetic results show that the oxidation rates of aniline increase with increasing pH values under visible light. UV-vis absorption spectra and GC-MS analysis confirm that azobenzene is the primary oxidation product with aminophenol and N,N'-diphenylhydrazine as the secondary products. The analyses from Mott-Schottky, electrochemical impedance spectroscopy (EIS), transient photocurrent and photoluminescence (PL) further indicate that OH- promotes the separation and transfer of photogenerated electron-hole pairs on the surface of Bi2·15WO6, thus facilitating oxidation of aniline. Quenching experiments and electron spin resonance (ESR) analysis confirm that h+ is the predominant specie in the Bi2·15WO6 system and aniline radical cation (PhNH2•+) is an important intermediate. The Hammett and ΔBDEN-H plots further reveal that e- abstraction from aniline with the formation of PhNH2•+, followed by H+ abstraction from PhNH2•+ with the formation of anilino radicals (PhNH•), is the prerequisite for the formation of N,N'-diphenylhydrazine, which is then oxidized to azobenzene via the hydrogen-abstraction pathway. This work provides a cost-effective method to selectively oxidize aniline to azobenzene.

Photoreductive dissolution of schwertmannite induced by oxalate and the mobilization of adsorbed As(V).

Schwertmannite (Sch), a poorly crystalline iron mineral, shows high sorption capacity to As(V). In this study, the effects of UV irradiation and oxalate on the dissolution of pure Sch, Sch with adsorbed As(V) [Sch*-As(V)] and subsequent mobilization of As(V) were investigated at pH 3.0. Under UV irradiation, the dissolved Fe(II) took the majority of the total dissolved Fe during the dissolution of Sch and Sch*-As(V). In the presence of oxalate, Fe(III)-oxalate complexes formed on Sch [or Sch*-As(V)] could be converted into Fe(II)-oxalate by photo-generated electrons under UV illumination, and more total dissolved Fe produced compared to that without oxalate. In the dark, total dissolved Fe reached the maximum value (42.64 mg L-1 for Sch) rapidly and existed as Fe(III) predominately. In addition, UV irradiation has almost no effect on the mobilization of As(V) in Sch*-As(V) in the absence of oxalate. However, in the presence of oxalate, UV irradiation resulted in the mobilization of As(V) declined by 14-36.5 times compared to that in the dark. This study enhanced our understanding on the mobilization of As(V), and UV irradiation could contribute to the immobilization of As(V) on Sch in the aquatic environments containing oxalate.

As(III) removal and speciation of Fe (Oxyhydr)oxides during simultaneous oxidation of As(III) and Fe(II).

Abiotic oxidation of Fe(II) is an important pathway in the formation of Fe (oxyhydr)oxides. However, how can As(III) affect the oxidation rate of Fe(II) and the speciation of Fe (oxyhydr)oxides, and what's the extent of the newly formed Fe (oxyhydr)oxides on the removal of aqueous arsenic are still poorly understood. Oxidation of Fe(II) under neutral pH conditions was therefore investigated under different molar ratios of As:Fe. Our results suggest that co-existence of aqueous As(III) significantly slows down the oxidation rate of Fe(II). Speciation of Fe (oxyhydr)oxides is dependent on pH and As:Fe ratios. At pH 6.0, formation of lepidocrocite and goethite is apparently inhibited at low As:Fe ratios, and ferric arsenate is favored at high As:Fe ratios. At pH 7.0, lepidocrocite gradually degenerates with the increasing As:Fe ratios. At pH 8.0, arsenite significantly inhibits the development of magnetite and favors a formation of lepidocrocite. XPS analysis further reveals that more than half of As(III) is oxidized to As(V) at pH 6.0 and 7.0, whereas at pH 8.0, the rapid oxidation of Fe(II) as well as the rapid formation of Fe (oxyhydr)oxides facilitate a rapid removal of dissolved As(III) before its further oxidation to As(V).

Formation of iron (hydr)oxides during the abiotic oxidation of Fe(II) in the presence of arsenate.

Abiotic oxidation of Fe(II) is a common pathway in the formation of Fe (hydr)oxides under natural conditions, however, little is known regarding the presence of arsenate on this process. In hence, the effect of arsenate on the precipitation of Fe (hydr)oxides during the oxidation of Fe(II) is investigated. Formation of arsenic-containing Fe (hydr)oxides is constrained by pH and molar ratios of As:Fe during the oxidation Fe(II). At pH 6.0, arsenate inhibits the formation of lepidocrocite and goethite, while favors the formation of ferric arsenate with the increasing As:Fe ratio. At pH 7.0, arsenate promotes the formation of hollow-structured Fe (hydr)oxides containing arsenate, as the As:Fe ratio reaches 0.07. Arsenate effectively inhibits the formation of magnetite at pH 8.0 even at As:Fe ratio of 0.01, while favors the formation of lepidocrocite and green rust, which can be latterly degenerated and replaced by ferric arsenate with the increasing As:Fe ratio. This study indicates that arsenate and low pH value favor the slow growth of dense-structured Fe (hydr)oxides like spherical ferric arsenate. With the rapid oxidation rate of Fe(II) at high pH, ferric (hydr)oxides prefer to precipitate in the formation of loose-structured Fe (hydr)oxides like lepidocrocite and green rust.

Reductive dissolution of ferrihydrite with the release of As(V) in the presence of dissolved S(-II).

In this study, reductive dissolution of As(V)-ferrihydrite and the mobilization of As(V) in the presence of S(-II) were investigated under anoxic conditions. Mobilization of As(V) strongly depended on the S(-II):Fe ratio and the amount of As(V) loading on ferrihydrite. High S(-II):Fe ratio caused a more complete dissolution of ferrihydrite and a large fraction of As(V) could be released into solution. The percentages of the released As(V) were 2.5% and 7.5% at S(-II):Fe ratios of 0.240 and 24.0, respectively, at pH 6.1, while the released As(V) were 5.5%, 16.3% at pH 8.0 under similar conditions. As(V) loading showed a negative effect on the release of arsenate, with smaller fraction of arsenate released into solution when more As (V) adsorbed on ferrihydrite. After 43 h, 14.1%, 5.5%, 1.6% and 0.7% of As(V) were released as for 10, 20, 50 and 100 mg L(-1) of As(V) loading, respectively, at pH 8.0. During the dissolution, secondary minerals such as goethite, magnetite and FeS were detected and played different roles in the mobilization of As(V). The released As(V) was mainly repartitioned on the residual ferrihydrite, the newly-formed goethite and magnetite but not FeS.

Mobilization and re-adsorption of arsenate on ferrihydrite and hematite in the presence of oxalate.

In this study, mobilization and re-adsorption of arsenate on 2-line ferrihydrite and hematite in the presence of oxalate was investigated. Our results showed that arsenate could be mobilized during the dissolution of ferrihydrite and hematite. After reaching the maximum values, the released arsenate could re-adsorb on the residual ferrihydrite, whereas such an observation was not significant in hematite system. More reactive sites exposed during the dissolution of ferrihydrite could contribute to the re-adsorption of the released arsenate at pH 3.0, while the insignificant re-adsorption of arsenate on hematite could be explained by the inhibitory adsorption effect of oxalate on arsenate. Although dissolution rates of iron oxides decreased with the increase of arsenate on both ferrihydrite and hematite, dissolution rate was mainly determined by the reactivity of iron oxides, and ferrihydrite showed a higher reactivity than hematite in the presence of oxalate. Mathematic model proposed in our study further indicated that arsenate loading showed a more significant effect on arsenate mobilization in hematite system, while it was more effective in arsenate re-adsorption in ferrihydrite system.

Abiotic oxidation of Mn(II) induced oxidation and mobilization of As(III) in the presence of magnetite and hematite.

Manganese (hydr)oxides are powerful oxidants mediating the transformation of As(III) to As(V) under natural conditions, however, the presence of Mn(II) on the oxidation of As(III) in the pH range of 7.0-9.0 has not been reported so far. In this study, abiotic oxidation of Mn(II) to amorphous Mn(III, IV) (hydr)oxides (MnOx) on magnetite and hematite was confirmed, and the impact of newly formed MnOx on the fate of As(III) was investigated. With the addition of Mn(II) into As(III)-preloaded systems, the dissolved and the adsorbed As(III) was oxidized to As(V) at high pH, and Mn(II) mobilized the adsorbed As(III) and As(V) in hematite system. High production of dissolved As(V) and significant mobilization of As(III) were even more significant in hematite suspension (total As was 18.96 mgL(-1) after 60 h at pH 8.62) with simultaneous addition of Mn(II) and As(III), while magnetite showed a higher capacity for the retention of As(III) and As(V). It could therefore be deduced that the newly formed MnOx on iron oxides could oxidize the dissolved and the adsorbed As(III) to As(V). In addition, the MnOx formed at high pH would take up the sorption sites previously occupied by the adsorbed As(III), and then mobilized a fraction of the adsorbed As(III) into solution. The present study reveals that MnOx formed via abiotic oxidation on iron oxides plays an important role in the oxidation and mobilization of both dissolved and adsorbed As(III) in aquatic environment.

Adsorptive removal of dibenzothiophene from model fuels over one-pot synthesized PTA@MIL-101(Cr) hybrid material.

Hybrid nanomaterials comprising phosphotungstic acid (PTA) and MIL-101(Cr) were prepared through one-pot synthesis and post-modification methods and then were used as adsorbents of dibenzothiophene (DBT) from simulated diesel fuels. Samples obtained by different ways (encapsulation and impregnation) were characterized by nitrogen adsorption, transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR) and series of adsorption experiments. The equilibrium adsorption capacities of PTA@MIL-101(Cr) illustrated that the direct introduction of PTA into MIL-101(Cr) during synthesis resulted in a 10.7% increase compared with MIL-101(Cr). However, porous hybrid adsorbent PTA/MIL-101(Cr) prepared via post-modification method exhibited lower adsorption capacity than virgin MIL-101(Cr). The theoretical maximum adsorption capacity (Q0) of PTA@MIL-101(Cr) is 136.5mg S/g adsorbent, 4.2 times of MIL-101(Cr). Even in competitive adsorption between aromatic compounds, which possess strong affinity with MOFs, and DBT, PTA@MIL-101(Cr) and MIL-101(Cr) remained their effectiveness in removal of DBT in the system. Based on these results, it can be presumed that MIL-101(Cr), modified properly, can be used as a promising adsorbent for eliminating aromatics and S-compounds in commercial fuels simultaneously.

Effects of Mn(II) on the sorption and mobilization of As(V) in the presence of hematite.

In this study, the effects of Mn(II) on the sorption and mobilization of As(V) by synthetic hematite were investigated. Our results showed that As(V) removal by hematite was evidently dependent on pH, and simultaneous addition of Mn(II) and As(V) into hematite suspension resulted in more removal of As(V) via electrostatic attraction at pH 4.0, 7.0 and 8.3. However, in Mn(II) pre-loaded system, the removal percentages of As(V) at pH 8.3 decreased by 17.0%, 20.7% and 26.7% after 24h at the aging time of 2, 12 and 36 h, respectively. The concentrations of the released As(V) after the addition of 1mM Mn(II) were 23.6, 12.9 and 7.0 µM at pH 8.5 in 2, 3 and 4 g L(-1) hematite suspension, respectively. But Ca(2+) did not show such an effect under similar experimental conditions. Abiotic oxidation of Mn(II) on hematite played an important role in As(V) mobilization. The growing thin layer of Mn(III, IV) (hydr)oxides (MnO(x)) formed on hematite would take up the sorption sites pre-occupied by As(V) and resulted in the release of the adsorbed As(V) back into solution. This study enriched our understanding on As(V) fate in the coexistence of iron oxides and Mn(II).