Enhanced removal of Cr(Ⅵ) by biochar with Fe as electron shuttles

Biochar is extensively used as an effective soil amendment for environmental remediation.In addition to its strong contaminant sorption capability, biochar also plays an important role in chemical transformation of contaminant due to its inherent redox-active moieties.However, the transformation efficiency of inorganic contaminants is generally very limited when the direct adsorption of contaminants on biochar is inefficient. The present study demonstrates the role of Fe ion as an electron shuttle to enhance Cr(Ⅵ) reduction by biochars. Batch experiments were conducted to examine the effects of Fe(Ⅲ) levels,pyrolysis temperature of biochar, initial solution pH, and biochar dosage on the efficiency of Cr(Ⅵ) removal. Results showed a significant enhancement in Cr(Ⅵ) reduction with an increase in Fe(Ⅲ) concentration and a decrease of initial pH. Biochar produced at higher pyrolysis temperatures(e.g., 700°C) favored Cr(Ⅵ) removal, especially in the presence of Fe(Ⅲ), while a higher biochar dosage proved unfavorable likely due to the agglomeration or precipitation of biochar. Speciation analysis of Fe and Cr elements on the surface of biochar and in the solution further confirmed the role of Fe ion as an electron shuttle between biochar and Cr(Ⅵ). The present findings provide a potential strategy for the advanced treatment of Cr(Ⅵ) at low concentrations as well as an insight into the environmental fate of Cr(Ⅵ) and other micro-pollutants in soil or aqueous compartments containing Fe and natural or engineered carbonaceous materials.     

A collaborative strategy for enhanced reduction of Cr(Ⅵ) by Fe(0) in the presence of oxalate under sunlight:Performance and mechanism

Nanometer-size zero-valent iron(NZVI) is an efficient reducing agent,but its surface is easily passivated with an oxide layer,leading to reaction inefficiency.In our study,oxalate(OA) was introduced into this heterogeneous system of NZVI,which could form ferrioxalate complexes with the NZVI surface-bound Fe~(3+) and dissolved Fe~(3+) in the solution.Photolysis of ferrioxalate complexes can facilitate the generation of Fe~(2+) from Fe~(3+)and CO_2~(·-) radical,both species have strong reduction capacity.Hence,a "photo-oxalate-Fe(0)"system through sunlight induction was established,which not only prohibited the formation of a surface passivation layer,but also displayed a synergetic mechanism of ferrioxalate photolysis to enhance reduction,exhibiting remarkably higher degradation activity(several times faster) toward the model pollutant Cr(Ⅵ) than the mechanism with NZVI alone.Factor tests suggested that both NZVI dosage and OA content markedly affected the reduction rate.Low pH was beneficial to the reduction efficiency.Moreover,recyclability experiment showed that the reduction rate decreased from 0.21706 to 0.03977 min~(-1) after three cycles of reuse due to the NZVI losing reaction activity generally,but the system still maintained considerable reduction capacity.Finally,a mechanism was revealed whereby NZVI would transform to Fe oxides after the exhaustion of its reductive power,and the photolysis of ferrioxalate to promote the cycling of iron species played the predominant role in providing extra reduction ability.These features confirm that introduction of OA into Cr(Ⅵ) reduction by NZVI through sunlight induction is advantageous and promising.     

Investigation of adsorption/desorption behavior of Cr(Ⅵ) at the presence of inorganic and organic substance in membrane capacitive deionization(MCDI)

The adsorption and desorption behavior of Cr(Ⅵ) in membrane capacitive deionization(MCDI) was investigated systematically in the presence of bovine serum albumin(BSA) and KCl with different concentrations, respectively. Results revealed that Cr(Ⅵ) absorption was enhanced and the adsorption amount for Cr(Ⅵ) increased from 155.7 to 190.8 mg/g when KCl concentration increased from 100 to 200 mg/L in the adsorption process, which was attributed to the stronger driving force. However, the adsorption amount sharply decreased to 90.2 mg/g when KCl concentration reached up to 1000 mg/L suggesting the negative effect for Cr(Ⅵ) removal that high KCl concentration had. As for the effect of BSA on ion adsorption, the amount for Cr(Ⅵ) significantly declined to 78.3 mg/g and p H was found to be an important factor contributing to this significant reduction. Then, the desorption performance was also conducted and it was obtained that the presence of KCl had negligible effect on Cr(Ⅵ) desorption, while promoted by the addition of BSA. The incomplete desorption was obtained and the residual chromium ions onto the electrode after desorption was detected via energy-dispersive X-ray spectroscopy(EDS). Based on above analysis, the enhanced removal mechanism for Cr(Ⅵ) in MCDI was found to be consisted of ion adsorption onto electrode surface, the redox reaction of Cr(Ⅵ) into Cr(III)and precipitation, which was demonstrated by X-ray photoelectron spectroscopy(XPS) and scanning electron microscope(SEM).     

Experimental study on Cr(Ⅵ) reduction by Pseudomonas aeruginosa

Investigation on Cr( Ⅵ ) reduction was conducted using Pseudomonas aeruginosa. The study demonstrated that the Cr(Ⅵ) canbe effectively reduced to Cr( Ⅲ ) by Pseudomonas aeruginosa. The effects of the factors affecting Cr( Ⅵ ) reduction rate including carbon source type, pH, initial Cr(Ⅵ) concentration and amount of calls inoculum were thoroughly studied. Malate was found to yield maximum biotransformation, followed by succinate and glucose, with the reduction rate of 60.86%, 43. 76% and 28.86% respectively. The optimum pH for Cr( Ⅵ ) reduction was ?.0, with reduction efficiency of 61.71 % being achieved. With the increase of initial Cr(Ⅵ) concentration,the rate of Cr(Ⅵ) reduction decreased. The reduction was inhibited strongly when the initial Cr(Ⅵ) concentration increased to 157 mg/L. As the amount of cells inoculum increased, the rate of Cr( Ⅵ ) reduction also increased. The mechanism of Cr( Ⅵ ) reduction and final products were also analysed. The results suggested that the soluble enzymes appear to be responsible for Cr (Ⅵ) reduction by Pseudomonas aeruginosa, and the reduced Cr( Ⅲ ) was not precipitated in the form of Cr(OH)3.     

Performance and mechanism of Cr(Ⅵ) removal by zero-valent iron loaded onto expanded graphite

Zero-valent iron(ZⅥ) was loaded on expanded graphite(EG) to produce a composite material(EG-ZⅥ) for efficient removal of hexavalent chromium(Cr(Ⅵ)). EG and EG-ZⅥ were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM),Fourier-transform infrared(FTIR) spectroscopy and Brunauer–Emmett–Teller(BET) analysis. EG-ZⅥ had a high specific surface area and contained sub-micron sized particles of zero-valent iron. Batch experiments were employed to evaluate the Cr(Ⅵ) removal performance. The results showed that the Cr(Ⅵ) removal rate was 98.80% for EG-ZⅥ,which was higher than that for both EG(10.00%) and ZⅥ(29.80%). Furthermore, the removal rate of Cr(Ⅵ) by EG-ZⅥ showed little dependence on solution p H within a p H range of 1–9.Even at pH 11, a Cr(Ⅵ) removal rate of 62.44% was obtained after reaction for 1 hr. EG-ZⅥ could enhance the removal of Cr(Ⅵ) via chemical reduction and physical adsorption,respectively. X-ray photoelectron spectroscopy(XPS) was used to analyze the mechanisms of Cr(Ⅵ) removal, which indicated that the ZⅥ loaded on the surface was oxidized, and the removed Cr(Ⅵ) was immobilized via the formation of Cr(III) hydroxide and Cr(III)–Fe(III)hydroxide/oxyhydroxide on the surface of EG-ZⅥ.     

A novel strategy of tannery sludge disposal –converting into biochar and reusing for Cr(Ⅵ)removal from tannery wastewater

Tannery sludge with high chromium content has been identified as hazardous solid waste due to its potential toxic effects.The safety disposal and valorization of the tannery sludge remains a challenge.In this study,the chromium stabilization mechanism was systematically investigated during chromium-rich tannery sludge was converted to biochar and the removal performance of the sludge biochar (SBC) for Cr(Ⅵ) from tannery wastewater was also investigated.The results showed that increase in pyrolys...     

Synthesis of a novel illite@carbon nanocomposite adsorbent for removal of Cr(Ⅵ) from wastewater

A novel illite@carbon(I@C) nanocomposite adsorbent has been synthesized via a facile hydrothermal carbonization process(HTC) using glucose as carbonaceous source and illite as the carrier.The morphology,microstructure and surface properties of the prepared nanocomposite adsorbent were analyzed by FESEM,TGA,XRD,FT-IR and Zeta potential measurements.Batch experiments were carried out on the adsorption of Cr(Ⅵ) to determine the adsorption properties of the composite.The adsorption of Cr(Ⅵ) onto the I@C nanocomposite was well described by the pseudo-second-order kinetic model and Langmuir isotherm.Compared with the illite and carbon material(SC) separately,the prepared I@C nanocomposite adsorbent exhibited enhanced adsorption performance for Cr(Ⅵ) with a maximum adsorption capacity of 149.25 mg/g,which was higher than that of most reported adsorbents.In addition,the adsorption process was spontaneous and endothermic based on the adsorption thermodynamics study.The adsorption of Cr(Ⅵ) by I@C was highly p H-dependent and the optimum adsorption occurred at p H 2.0.The Zeta potential analysis results indicated that the electrostatic interactions between anionic Cr(Ⅵ) and the positively charged surface of the adsorbent might be critical to the adsorption mechanism.This study demonstrated that the I@C nanocomposite should be a promising candidate for a low-cost,environmental friendly and highly efficient adsorbent for the removal of toxic Cr(Ⅵ) from wastewater.     

Intensification of adsorption process by using the pyrolytic char from waste tires to remove chromium(Ⅵ) from wastewater

Pyrolysis has the potential of transforming waste into valuable recyclable products. Pyrolytic char (PC) is one of the most important products from the pyrolysis of used tires. One of the most significant applications for pyrolytic char recovered is used for the removal of Cr( Ⅵ ) in the wastewater effluent to control waste by waste. The surface chemistry properties of surface element distribution/concentration and chemical structure were examined for the pyrolytic char and the commercial activated carbon(CAC) respectively. The results showed that surfaces of PC possesses a large amount of ester and hydrocarbon graft, whereas there are mainly carbon functional components of C-OH, C=O and COOH on the surface of CAC. Therefore the surface electronegativity of PC is lower than that of CAC in the water. The repulsive interactions between the surfaces of PC and the negatively charged Cr（Ⅵ ) ion are weaker than that of CAC,which results in an intensification of the adsorption process by the utilization of PC. The adsorption isotherms of Cr( Ⅵ ) ion on the two kinds of carbons were determined experimentally. The larger adsorption amount on the PC in the case of Cr( Ⅵ ) may be attributed mainly to its special surface micro-chemical environment. The mechanism of the removal Cr( Ⅵ ) from aqueous solution was assumed to be the integration of adsorption and redox reaction. The adsorption was the rate-controlled step for Cr( Ⅵ ) removal. The adsorption of Cr( Ⅵ )was identified as pseudo-second-order kinetics. The rate constants of adsorption were evaluated.     

Removal of Cr(Ⅵ) by glutaraldehyde-crosslinked chitosan encapsulating microscale zero-valent iron: Synthesis,mechanism, and longevity

Microscale zero-valent iron(mZVI) has shown great potential for groundwater Cr(Ⅵ) remediation. However, low Cr(Ⅵ) removal capacity caused by passivation restricted the wide use of mZVI. We prepared mZVI/GCS by encapsulating mZVI in a porous glutaraldehydecrosslinked chitosan matrix, and the formation of the passivation layer was alleviated by reducing the contact between zero-valent iron particles. The average pore diameter of mZVI/GCS was 8.775 nm, which confirmed the mesoporous characteristic ...     

Sodium citrate and biochar synergistic improvement of nanoscale zero-valent iron composite for the removal of chromium (Ⅵ) in aqueous solutions

Sodium citrate (SC) is a widely-used food and industrial additive with the properties of complexation and microbial degradation. In the present study, nano-zero-valent iron reaction system ([email protected]) was successfully established by modifying nanoscale zero-valent iron (nZVI) with SC and biochar (BC), and was employed to remove Cr(Ⅵ) from aqueous solutions. The nZVI, SC-nZVI and [email protected] were characterized and compared using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analyses (TGA), vibrating sample magnetometer (VSM), scanning electron microscope (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results showed that nZVI was successfully loaded on the biochar, and both the agglomeration and surface passivation problems of nanoparticles were well resolved. The dosage of SC, C:Fe, initial pH and Cr(Ⅵ) concentration demonstrated direct effects on the removal efficiency. The maximum Cr(Ⅵ) removal rate and the removal capacity within 60 min were 99.7% and 199.46 mg/g, respectively (C:Fe was 1:1, SC dosage was 1.12 mol.%, temperature was 25°C, pH = 7, and the original concentration of Cr(Ⅵ) was 20 mg/L). The reaction confirmed to follow the pseudo-second-order reaction kinetics, and the order of the reaction rate constant k was as follows: [email protected] > [email protected] > SC-nZVI > nZVI. In addition, the mechanism of Cr(Ⅵ) removal by [email protected] mainly involved adsorption, reduction and co-precipitation, and the reduction of Cr(Ⅵ) to Cr(Ⅲ) by nano Fe⁰ played a vital role. Findings from the present study demonstrated that the [email protected] exhibited excellent removal efficiency toward Cr(Ⅵ) with an improved synergistic characteristic by SC and BC.     

Oxidation of Cr(Ⅲ) on birnessite surfaces: The effect of goethite and kaolinite

Oxidation of Cr(Ⅲ) by manganese oxides may pose a potential threat to environments due to the formation of toxic Cr(Ⅵ) species. At present, it was still unclear whether the extent of Cr(Ⅲ) oxidation and fate of Cr(Ⅵ) would be changed when manganese oxides co-exist with other minerals, the case commonly occurring in soils. This study investigated the influence of goethite and kaolinite on Cr(Ⅲ) oxidation by birnessite under acidic p H condition(p H 3.5)and background electrolyte of 0.01 mol/L Na Cl. Goethite was found not to affect Cr(Ⅲ)oxidation, which was interpreted as the result of overwhelming adsorption of cationic Cr(Ⅲ) onto the negatively-charged birnessite(point of zero charge(PZC) 3.0) rather than the positively-charged goethite(PZC = 8.8). However, more Cr(Ⅵ) would be retained by the surface with the increase in addition of goethite because of its strong ability on adsorption of Cr(Ⅵ) at low p H. Moreover, either Cr(Ⅲ) oxidation or distribution of the generated Cr(Ⅵ)between the solid and solution phases was not affected by kaolinite(PZC 3.0), indicating its low affinity for Cr species. Reactions occurring in the present mixed systems were suggested, which could be partly representative of those in the soils and further indicates that the mobility and risk of Cr(Ⅵ) would be decreased if goethite was present.     

Bacterial reduction and release of adsorbed arsenate on Fe(Ⅲ)-, Al- and coprecipitated Fe(Ⅲ)/Al-hydroxides

Mobilization of arsenic under anaerobic conditions is of great concern in arsenic contaminated soils and sediments. Bacterial reduction of As(V) and Fe(Ⅲ) influences the cycling and partitioning of arsenic between solid and aqueous phase. We investigated the impact of bacterially mediated reductions of Fe(Ⅲ)/Al hydroxides-bound arsenic(V) and iron(Ⅲ) oxides on arsenic release. Our results suggested that As(V) reduction occurred prior to Fe(Ⅲ) reduction, and Fe(Ⅲ) reduction did not enhance the release of arsenic. Instead, Fe(Ⅲ) hydroxides retained their dissolved concentrations during the experimental process, even though the new iron mineral-magnetite formed. In contrast, the release of reduced As(Ⅲ) was promoted greatly when aluminum hydroxides was incorporated. Thus, the substitution of aluminum hydroxides may be responsible for the release of arsenic in the contaminated soils and sediments, since aluminum substitution of Fe(Ⅲ) hydroxides universally occurs under natural conditions.     

Radiation-induced reduction of chromium(Ⅵ) in aqueous solution by γ-irradiation in a laboratory-scale

Radiation-induced reduction of chromium（Ⅵ）（Cr（Ⅵ） by ,γ-irradiation was studied with an initial concentration of 42 mg/L in aqueous solutions. Several factors which might affect the reduction of Cr（Ⅵ） to Cr（Ⅲ） were examined, pH of aqueous solution affects the reduction efficiency significantly. Acidic condition of aqueous solution accelerates the process. At pH 2, a reduction of 86.2% was achieved with the absorbed dose of 15 kGy, while, with the same dose, at pH 5 and 7, the reduction ofCr （Ⅵ） were only 36.3% and 22.2%, respectively. Ethanol （0.1% in V：V） and sodium carbonate （1 mmol/L） were added into the solution respectively as relatively non-toxic hydroxyl radical scavengers. Reduction rate increased greatly in the presence of ethanol at each pH. Reduction efficiency of Cr（Ⅵ） was enhanced in neutral condition with the addition of sodium carbonate, however, no enhancement was found in acidic condition. The reduction of Cr（Ⅵ） was restrained when the solution was saturated with oxygen; however, the restraint was not significant.     

Enhanced U(Ⅵ) bioreduction by alginate-immobilized uranium-reducing bacteria in the presence of carbon nanotubes and anthraquinone-2,6-disulfonate

Uranium-reducing bacteria were immobilized with sodium alginate, anthraquinone-2,6-disulfonate(AQDS), and carbon nanotubes(CNTs). The effects of different AQDS-CNTs contents, U(Ⅳ) concentrations, and metal ions on U(Ⅳ) reduction by immobilized beads were examined. Over 97.5% U(Ⅵ)(20 mg/L) was removed in 8 hr when the beads were added to 0.7% AQDS-CNTs, which was higher than that without AQDS-CNTs. This result may be attributed to the enhanced electron transfer by AQDS and CNTs. The reduction of U(Ⅵ) occurred at initial U(Ⅵ) concentrations of 10 to 100 mg/L and increased with increasing AQDS-CNT content from 0.1% to 1%. The presence of Fe(Ⅲ), Cu(Ⅱ) and Mn(Ⅱ)slightly increased U(Ⅵ) reduction, whereas Cr(Ⅵ), Ni(Ⅱ), Pb(Ⅱ), and Zn(Ⅱ) significantly inhibited U(Ⅵ) reduction. After eight successive incubation-washing cycles or 8 hr of retention time(HRT) for 48 hr of continuous operation, the removal efficiency of uranium was above 90% and 92%, respectively. The results indicate that the AQDS-CNT/AL/cell beads are suitable for the treatment of uranium-containing wastewaters.     

Synthesis,characterization and application of Lagerstroemia speciosa embedded magnetic nanoparticle for Cr(Ⅵ)adsorption from aqueous solution

Lagerstroemia speciosa bark(LB) embedded magnetic nanoparticles were prepared by co-precipitation of Fe~(2+) and Fe~(3+) salt solution with ammonia and LB for Cr(Ⅵ) removal from aqueous solution.The native LB,magnetic nanoparticle(MNP),L.spedosa embedded magnetic nanoparticle(MNPLB) and Cr(Ⅵ) adsorbed MNPLB particles were characterized by SEM-EDX,TEM,BET-surface area,FT-IR,XRD and TGA methods.TEM analysis confirmed nearly spherical shape of MNP with an average diameter of 8.76 nm and the surface modification did not result in the phase change of MNP as established by XRD analysis,while led to the formation of secondary particles of MNPLB with diameter of 18.54 nm.Characterization results revealed covalent binding between the hydroxyl group of MNP and carboxyl group of LB particles and further confirmed its physico-chemical nature favorable for Cr(Ⅵ) adsorption.The Cr(Ⅵ) adsorption on to MNPLB particle as an adsorbent was tested under different contact time,initial Cr(Ⅵ) concentration,adsorbent dose,initial pH,temperature and agitation speed.The results of the equilibrium and kinetics of adsorption were well described by Langmuir isotherm and pseudo-second-order model,respectively.The thermodynamic parameters suggest spontaneous and endothermic nature of Cr(Ⅵ)adsorption onto MNPLB.The maximum adsorption capacity for MNPLB was calculated to be 434.78 mg/g and these particles even after Cr(Ⅵ) adsorption were collected effortlessly from the aqueous solution by a magnet.The desorption of Cr(Ⅵ)-adsorbed MNPLB was found to be more than 93.72%with spent MNPLB depicting eleven successive adsorption-desorption cycles.     

Simultaneous adsorption of As(Ⅲ) and Pb(Ⅱ) by the iron-sulfur codoped biochar composite:Competitive and synergistic effects

Simultaneous elimination of As(Ⅲ) and Pb(Ⅱ) from wastewater is still a great challenge.In this work,an iron-sulfur codoped biochar (Fe/S-BC) was successfully fabricated in a simplified way and was applied to the remediate the co-pollution of As(Ⅲ) and Pb(Ⅱ).The positive enthalpy indicated that the adsorption in As-Pb co-pollution was an endothermic reaction.The mechanism of As(Ⅲ) removal could be illustrated by surface complexation,oxidation and precipitation.In addition to precipitation and com...     

Preparation of metal-doped Cu–Mn/HTS-1 catalysts and their mechanisms in efficient degradation of toluene

In order to study their synergistic catalytic effects in toluene degradation, CuMn_2O_4/HTS-1(HTS-1 was a titanium silicon molecular sieve), Cu_(0.7)Mn_2Y_(0.3)O_x/HTS-1 and Cu_(0.7)Mn_2Ce_(0.3)O_x/HTS-1 catalysts were prepared by the impregnation method.The textural properties, redox properties and acidity of the catalysts were characterized by X-ray diffractometer(XRD),transmission electron microscopy(TEM), scanning electron microscopy(SEM), H_2 temperature-programmed reduction(H_2-TPR), X-ray photoelectron spectroscopy(XPS),frustrated total internal reflection(FT-IR), ammonium temperature-programmed desorption(NH_3-TPD) and pyridine adsorption internal reflection(Py-IR) measurements.The potential roles of Lewis acid sites(activating dioxygen) were discussed, and the experimental results indicated that the most efficient route for toluene degradation over Cu_(0.7)Mn_2Ce_(0.3)O_x/HTS-1(toluene conversion rate of 90%(T99) = 295℃) was ascribed to regulation of the synergistic effects of redox properties(activating molecular toluene) and Lewis acid sites(activating dioxygen).The Mars–Van–Krevelen(MVK) model was adopted to describe the reaction process of toluene oxidation, which gave an in-depth view into the toluene degradation over CuMn_2O_4/HTS-1, Cu_(0.7)Mn_2Y_(0.3)O_x/HTS-1 and Cu_(0.7)Mn_2Ce_(0.3)O_x/HTS-1.In addition, the synergistic effects between redox properties and Lewis acid sites were studied in detail.     

Preliminary study on the electrocatalytic performance of an iron biochar catalyst prepared from iron-enriched plants

Eichhornia crassipes is a hyperaccumulator of metals and has been widely used to remove metal pollutants from water, but disposal of contaminated plants is problematic.Biochar prepared from plants is commonly used to remediate soils and sequester carbon.Here, the catalytic activity of biochar prepared from plants enriched with iron was investigated as a potentially beneficial use of metal-contaminated plants.In a 30-day hydroponic experiment, E.crassipes was exposed to different concentrations of Fe(Ⅲ)(0, 4, 8, 16, 32 and 64 mg/L), and Fe-biochar(Fe-BC) was prepared by pyrolysis of the plant roots.The biochar was characterized using X-ray diffraction(XRD), scanning electron microscopy(SEM), energy dispersive X-ray spectrometry(EDS), Brunauer–Emmett–Teller(BET) analysis, X-ray photoelectron spectroscopy(XPS) and atomic absorption spectrometry(AAS).The original root morphology was visible and iron was present as γ-Fe_2O_3 and Fe_3O_4.The biochar enriched with Fe(Ⅲ) at 8 mg/L(8-Fe-BC) had the smallest specific surface area(SSA, 13.54 m~2/g) and the highest Fe content(27.9 mg/g).Fe-BC catalytic activity was tested in the electrocatalytic reduction of H_2O_2 using cyclic voltammetry(CV).The largest reduction current(1.82 mA/cm~2) was displayed by 8-Fe-BC, indicating the highest potential catalytic activity.We report here, for the first time, on the catalytic activity of biochar made from iron-enriched plants and demonstrate the potential for reusing metalcontaminated plants to produce a biochar catalyst.     

A collaborative strategy for enhanced reduction of Cr(VI) by Fe(0) in the presence of oxalate under sunlight: Performance and mechanism

Nanometer-size zero-valent iron (NZVI) is an efficient reducing agent, but its surface is easily passivated with an oxide layer, leading to reaction inefficiency. In our study, oxalate (OA) was introduced into this heterogeneous system of NZVI, which could form ferrioxalate complexes with the NZVI surface-bound Fe³⁺ and dissolved Fe³⁺ in the solution. Photolysis of ferrioxalate complexes can facilitate the generation of Fe²⁺ from Fe³⁺ and CO₂^?- radical, both species have strong reduction capacity. Hence, a “photo-oxalate-Fe(0)” system through sunlight induction was established, which not only prohibited the formation of a surface passivation layer, but also displayed a synergetic mechanism of ferrioxalate photolysis to enhance reduction, exhibiting remarkably higher degradation activity (several times faster) toward the model pollutant Cr(VI) than the mechanism with NZVI alone. Factor tests suggested that both NZVI dosage and OA content markedly affected the reduction rate. Low pH was beneficial to the reduction efficiency. Moreover, recyclability experiment showed that the reduction rate decreased from 0.21706 to 0.03977 min^?1 after three cycles of reuse due to the NZVI losing reaction activity generally, but the system still maintained considerable reduction capacity. Finally, a mechanism was revealed whereby NZVI would transform to Fe oxides after the exhaustion of its reductive power, and the photolysis of ferrioxalate to promote the cycling of iron species played the predominant role in providing extra reduction ability. These features confirm that introduction of OA into Cr(VI) reduction by NZVI through sunlight induction is advantageous and promising.     

Mechanism of Cu(Ⅱ) adsorption inhibition on biochar by its aging process

Biochar exposed in the environment may experience a series of surface changes, which is called biochar aging. In order to study the effects of biochar aging on Cu（Ⅱ） adsorption, we analyzed the surface properties before and after biochar aging with scanning electron microscopy（SEM） coupled to an energy-dispersive X-ray spectrometer（EDX） and diffuse reflectance infrared Fourier transform spectroscopy（DRIFTS）, and then explored the influence of the aging process on Cu（Ⅱ） adsorption by batch experiments. After the aging process, the oxygen concentration, phenolic hydroxyl groups, aromatic ethers and other oxygen-containing functional groups on the biochar surface increased, while carboxyl groups slightly decreased. Thus, over a range of pH, the cation exchange capacity（CEC） and adsorption capacity of Cu（Ⅱ） on the aged biochar were smaller than those of new biochar,indicating that when biochar is incubated at constant temperature and water holding capacity in the dark, the aging process may inhibit Cu（Ⅱ） adsorption. Meanwhile, the dissociation characteristics of oxygen-containing functional groups changed through the aging process, which may be the mechanism by which the biochar aging process inhibits the Cu（Ⅱ） adsorption. Carboxyl groups became more easily dissociated at low pH（3.3–5.0）,and the variation of maximum adsorption capability（qm） of Cu（Ⅱ） on the old biochar was enlarged. Phenolic hydroxyl groups increased after the aging, making them and carboxyl groups more difficult to dissociate at high pH（5.0–6.8）, and the variation of qmof Cu（Ⅱ） on the aged biochar was reduced.