Influence of the structure and composition of Fe–Mn binary oxides on rGO on As(III) removal from aquifers

Fe–Mn binary oxide (FMBO) possesses high efficiency for As(III) abatement based on the good adsorption affinity of iron oxide and the oxidizing capacity of Mn(IV), and the composition and structure of FMBO play important roles in this process. To compare the removal performance and determine the optimum formula for FMBO, magnetic graphene oxide (MRGO)–FMBO and MRGO–MnO₂ were synthesized with MRGO as a carrier to improve the dispersity of the adsorbents in aquifers and achieve magnetic recycling. Results indicated that MRGO–FMBO had higher As(III) removal than that of MRGO–MnO₂, although the ratios of Fe and Mn were similar, because the binary oxide of Fe and Mn facilitated electron transfer from Mn(IV) to As(III), while the separation of Mn and Fe on MRGO–MnO₂ restricted the process. The optimal stoichiometry x for MRGO–FMBO (Mn_xFe_3-xO₄) was 0.46, and an extraordinary adsorption capacity of 24.38 mg/g for As(III) was achieved. MRGO–FMBO showed stable dispersive properties in aquifers, and exhibited excellent practicability and reusability, with a saturation magnetization of 7.6 emu/g and high conservation of magnetic properties after 5 cycles of regeneration and reuse. In addition, the presence of coexisting ions would not restrict the practical application of MRGO–FMBO in groundwater remediation. The redox reactions of As(III) and Mn(IV) on MRGO–FMBO were also described. The deprotonated aqueous As(III) on the surface of MRGO–FMBO transferred electrons to Mn(IV), and the formed As(V) oxyanions were bound to ferric oxide as inner-sphere complexes by coordinating their “–OH” groups with Mn(IV) oxides at the surface of MRGO–FMBO. This work could provide new insights into high-performance removal of As(III) in aquifers.     

Rates and processes affecting As speciation and mobility in lake sediments during aging

Sediments from an arsenic(As) contaminated groundwater vent site were used to investigate As( Ⅲ) binding, transformation and redistribution in native and iron oxide amended lake sediments using aging spiked batch reactions and a sequential extraction procedure that maintains As(V) and As( Ⅲ) speciation. In the native sediments, fractionation analysis revealed that 10% of the spiked As( Ⅲ) remained intact after a 32-day aging experiment and was predominantly adsorbed to the strongly sorbed(NH_4H_2PO_4 extractable) and amorphous Fe oxide bound(H_3PO_4 extractable) fractions. Kinetic modelling of the experimental results allowed identifying the dominant reaction path for depletion of dissolved As( Ⅲ) to As( Ⅲ)absorbed on to the solid phase, followed by oxidation in the solid phase. Arsenite was initially adsorbed primarily to the easily exchangeable fraction((NH_4)_2SO_4 extractable), then rapidly transformed into As(V) and redistributed to the strongly sorbed and amorphous Fe oxide bound fractions. Oxidation of As( Ⅲ) in recalcitrant fractions was less efficient. The iron oxide amendments illustrated the controls that iron oxides can have on As( Ⅲ) binding and transformation rates. In goethite amended samples As( Ⅲ) oxidation was faster and primarily occurred in the strongly sorbed and amorphous Fe oxide bound fractions. In these samples,19.3 μg Mn was redistributed(compared to the native sediment) from the easily exchangeable and crystalline Fe oxide bound fractions to the strongly sorbed and amorphous Fe oxide bound fractions, indicating that goethite may act as a catalyst for Mn(Ⅱ) oxidation, thereby producing sorbed Mn( Ⅲ/Ⅳ ), which then appears to be involved in rapidly oxidizing As( Ⅲ).     

Co-adsorption of gaseous benzene, toluene, ethylbenzene, m-xylene (BTEX) and SO2 on recyclable Fe3O4 nanoparticles at 0-101% relative humidities

We herein used Fe3O4 nanoparticles(NPs) as an adsorption interface for the concurrent removal of gaseous benzene, toluene, ethylbenzene and m-xylene(BTEX) and sulfur dioxide(SO2), at different relative humidities(RH). X-ray diffraction, Brunauer–Emmett–Teller, and transmission electron microscopy were deployed for nanoparticle surface characterization.Mono-dispersed Fe3O4(Fe2O3·Fe O) NPs synthesized with oleic acid(OA) as surfactant, and uncoated poly-dispersed Fe3O4 NPs demonstrated comparable removal efficiencies.Adsorption experiments of BTEX on NPs were measured using gas chromatography equipped with flame ionization detection, which indicated high removal efficiencies(up to(95 ± 2)%) under dry conditions. The humidity effect and competitive adsorption were investigated using toluene as a model compound. It was observed that the removal efficiencies decreased as a function of the increase in RH, yet, under our experimental conditions, we observed(40 ± 4)% toluene removal at supersaturation for Fe3O4 NPs, and toluene removal of(83 ± 4)% to(59 ± 6)%, for OA-Fe3O4 NPs. In the presence of SO2, the toluene uptake was reduced under dry conditions to(89 ± 2)% and(75 ± 1)% for the uncoated and coated NPs, respectively, depicting competitive adsorption. At RH 100%,competitive adsorption reduced the removal efficiency to(27 ± 1)% for uncoated NPs whereas OA-Fe3O4 NPs exhibited moderate efficiency loss of(55 ± 2)% at supersaturation.Results point to heterogeneous water coverage on the NP surface. The magnetic property of magnetite facilitated the recovery of both types of NPs, without the loss in efficiency when recycled and reused.     

Influence of moderate pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing activated carbon

A novel adsorbent based on iron oxide dispersed over activated carbon(AC) were prepared, and used for phosphate removal from aqueous solutions. The influence of pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing AC were determined. Two series of ACs, non-oxidized and oxidized carbon modified by iron(denoted as AC-Fe and AC/OFe), resulted in a maximum impregnated iron of 4.03% and 7.56%, respectively. AC/O-Fe showed 34.0%–46.6% higher phosphate removal efficiency than the AC-Fe did. This was first attributed to the moderate pre-oxidation of raw AC by nitric acid, achieved by dosing Fe(II) after a pre-oxidation, to obtain higher iron loading, which is favorable for phosphate adsorption. Additionally, the in-situ formed active site on the surface of carbon, which was derived from the oxidation of Fe(II) by nitric acid dominated the remarkably high efficiency with respect to the removal of phosphate. The activation energy for adsorption was calculated to be 10.53 and 18.88 kJ/mol for AC-Fe and AC/OFe, respectively. The results showed that the surface mass transfer and intra-particle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism.     

Simultaneous removal and oxidation of arsenic from water by δ-MnO2 modified activated carbon

The ubiquitous arsenic in groundwater poses a great risk to human health due to its environmental toxicity and carcinogenicity. In the present work, a new adsorbent, δ-MnO₂ modified activated carbon, was prepared, and its performance for the uptake of arsenate and arsenite species from aqueous solutions was investigated by batch experiments. Various techniques, including FESEM-EDX, p-XRD, XPS and BET surface area analysis, were employed to characterize the properties of the adsorbent and the arsenic adsorption mechanisms. The results showed that δ-MnO₂ covered on the surface and padded in the pores of the activated carbon. Adsorption kinetic studies revealed that approximately 90.1% and 76.8% of As(III) and As(V), respectively, were removed by the adsorbent in the first 9 hr, and adsorption achieved equilibrium within 48 hr. The maximum adsorption capacities of As(V) and As(III) at pH 4.0 calculated from Langmuir adsorption isotherms were 13.30 and 12.56 mg/g, respectively. The effect of pH on As(V) and As(III) removal was similar, and the removal efficiency significantly reduced with the increase of solution pH. Arsenite oxidation and adsorption kinetics showed that the As(V) concentration in solution due to As(III) oxidation and reductive dissolution of MnO₂ increased rapidly during the first 12 min, and then gradually decreased. Based on the XPS analysis, nearly 93.3% of As(III) had been oxidized to As(V) on the adsorbent surface and around 38.9% of Mn(IV) had been reduced to Mn(II) after As(III) adsorption. This approach provides a possible method for the purification of arsenic-contaminated groundwater.     

Integrated removal of NO and mercury from coal combustion flue gas using manganese oxides supported on TiO2

A catalyst composed of manganese oxides supported on titania(MnO_x/TiO_2) synthesized by a sol–gel method was selected to remove nitric oxide and mercury jointly at a relatively low temperature in simulated flue gas from coal-fired power plants. The physico-chemical characteristics of catalysts were investigated by X-ray fluorescence(XRF), X-ray diffraction(XRD), and X-ray photoelectron spectroscopy(XPS) analyses, etc. The effects of Mn loading,reaction temperature and individual flue gas components on denitration and Hg~0 removal were examined. The results indicated that the optimal Mn/Ti molar ratio was 0.8 and the best working temperature was 240°C for NO conversion. O_2 and a proper ratio of [NH_3]/[NO]are essential for the denitration reaction. Both NO conversion and Hg~0 removal efficiency could reach more than 80% when NO and Hg~0 were removed simultaneously using Mn0.8 Tiat 240°C.Hg~0 removal efficiency slightly declined as the Mn content increased in the catalysts. The reaction temperature had no significant effect on Hg~0 removal efficiency. O_2 and HCl had a promotional effect on Hg~0 removal. SO2 and NH_3were observed to weaken Hg~0 removal because of competitive adsorption. NO first facilitated Hg~0 removal and then had an inhibiting effect as NO concentration increased without O_2, and it exhibited weak inhibition of Hg~0 removal efficiency in the presence of O_2. The oxidation of Hg~0 on Mn O x/TiO_2 follows the Mars–Maessen and Langmuir–Hinshelwood mechanisms.     

Ethanol mediated As(Ⅲ) adsorption onto Zn-loaded pinecone biochar:Experimental investigation,modeling,and optimization using hybrid artificial neural network-genetic algorithm approach

Organic matters(OMs) and their oxidization products often influence the fate and transport of heavy metals in the subsurface aqueous systems through interaction with the mineral surfaces. This study investigates the ethanol(EtO H)-mediated As(Ⅲ) adsorption onto Zn-loaded pinecone(PC) biochar through batch experiments conducted under Box–Behnken design. The effect of EtO H on As(Ⅲ) adsorption mechanism was quantitatively elucidated by fitting the experimental data using artificial neural network and quadratic modeling approaches. The quadratic model could describe the limiting nature of EtO H and pH on As(Ⅲ) adsorption,whereas neural network revealed the stronger influence of Et OH(64.5%) followed by pH(20.75%)and As(Ⅲ) concentration(14.75%) on the adsorption phenomena. Besides, the interaction among process variables indicated that Et OH enhances As(Ⅲ) adsorption over a pH range of2 to 7, possibly due to facilitation of ligand–metal(Zn) binding complexation mechanism.Eventually, hybrid response surface model–genetic algorithm(RSM–GA) approach predicted a better optimal solution than RSM, i.e., the adsorptive removal of As(Ⅲ)(10.47 μg/g) is facilitated at 30.22 mg C/L of Et OH with initial As(Ⅲ) concentration of 196.77 μg/L at pH 5.8. The implication of this investigation might help in understanding the application of biochar for removal of various As(Ⅲ) species in the presence of OM.     

Effect of competing solutes on arsenic（Ⅴ） adsorption using iron and aluminum oxides

The study focused on the effect of several typical competing solutes on removal of arsenic with Fe_2O_3 and AL_2O_3.The test results indicate that chloride,nitrate and sulfate did not have detectable effects,and that selenium(Ⅳ)(Se(Ⅳ))and vanadium(Ⅴ)(V(Ⅴ)) showed slight effects on the adsorption of As(Ⅴ)with Fe_2O_3.The results also showed that adsorption of As(Ⅴ)on AL_2O_3 was not affected by chloride and nitrate anions,but slightly by Se(Ⅳ)and V(Ⅴ)ions.Unlike the adsorption of As(Ⅴ)with Fe_2O_3,that with Fe_2O_3 was affected by the presence of sulfate in water solutions.Both phosphate and silica have significant adverse effects on the adsorption of As(Ⅴ)adsorption with Fe_2O_3 and Al_2O_3.Compared to the other tested anions,phosphate anion was found to be the most prominent solute affecting the As(Ⅴ)adsorption with Fe_2O_3 and Al_2O_3.In general,Fe_2O_3 has a better performance than Al_2O_3 in removal of As(Ⅴ)within a water environment where multi competing solutes are present.     

Adsorptive removal of As(Ⅲ) ions from water using spent grain modified by polyacrylamide

In order to enhance the removal efficiency of As(III), a pre-oxidation process is generally applied first to convert As(III) to As(V), which may cause unwanted new contaminants. To overcome this problem, efforts were made to develop an effective way to remove As(III)directly without an oxidation step. The effect of polyacrylamide polymers(PAMs) such as anionic PAM, cationic PAM and nonionic PAM, on As(III) ion adsorption by spent grain(SG)was investigated. The physico-chemical properties of the three PAM-polymerized SGs(APSG(anionic PAM-polymerized modified spent grain), CPSG(cationic PAM-polymerized spent grain) and NPSG(nonionic PAM-polymerized spent grain)) were analyzed using Fourier transform infrared(FT-IR), scanning electron microscope(SEM) and zeta potential.Batch experimental data showed that the sequence of preferential adsorption for As(III) was APSG CPSG NPSG. Active functional groups such as amino group(NH2), carbonyl group(C_O), C–N bond of the amide group(CONH2), and hydroxyl group(O–H) were responsible for As(III) adsorption. Many tubular structures occurring on the surface of APSG possibly increase the specific surface areas and favor the adsorption of As(III) ions. A fixed-bed study was carried out by using APSG as an adsorbent for As(III) from water. Three factors such as bed height, initial concentration and flow rate were studied, and breakthrough curves of As(III) were obtained. The Adams–Bohart model was used to analyze the experimental data and the model parameters were evaluated.     

Practical performance and its efficiency of arsenic removal from groundwater using Fe-Mn binary oxide

A treatment unit packed by granular adsorbent of Fe-Mn binary oxide incorporated into diatomite (FMBO(1:1)-diatomite) was studied to remove arsenic from anaerobic groundwater without any pre-treatment or post-treatment. The raw anaerobic groundwater containing 35-45 μg/L of arsenic was collected from suburb of Beijing. Arsenic(III) constituted roughly 60%-80% of the total arsenic content. Approximately 7,000 bed volumes (ratio of efluent volume to adsorbent volume) treated water with arsenic concentration below 10 μg/L were produced in the operation period of four months. The regeneration of FMBO(1:1)-diatomite had been operated for 15 times. In the first stage, the regeneration process significantly improved the adsorption capacity of FMBO(1:1)-diatomite. With increased loading amount of Fe-Mn binary oxide, the adsorption capacity for arsenic decreased 20%-40%. Iron and manganese in anaerobic groundwater were oxidized and adsorptive filtrated by FMBO(1:1)-diatomite efficiently. The final concentrations of iron and manganese in efluents were nearly zero. The continued safe performance of the treatment units proved that adsorbent FMBO(1:1)-diatomite had high oxidation ability and exhibited strong adsorptive filtration.     

Simultaneous removal of Congo red and cadmium(II) from aqueous solutions using graphene oxide–silica composite as a multifunctional adsorbent

Graphene oxide is a very high capacity adsorbent due to its functional groups and π?π interactions with other compounds. Adsorption capacity of graphene oxide, however, can be further enhanced by having synergistic effects through the use of mixed-matrix composite. In this study, silica-decorated graphene oxide (SGO) was used as a high-efficiency adsorbent to remove Congo red (CR) and Cadmium (II) from aqueous solutions. The effects of solution initial concentration (20 to 120 mg/l), solution pH (pH 2 to 7), adsorption duration (0 to 140 min) and temperature (298 to 323 K) were measured in order to optimize the adsorption conditions using the SGO adsorbent. Morphological analysis indicated that the silica nanoparticles could be dispersed uniformly on the graphene oxide surfaces. The maximum capacities of adsorbent for effective removal of Cd (II) and CR were 43.45 and 333.33 mg/g based on Freundlich and Langmuir isotherms, respectively. Langmuir and Freundlich isotherms displayed the highest values of Q_max for CR and Cd (II) adsorption in this study, which indicated monolayer adsorption of CR and multilayer adsorption of Cd (II) onto the SGO, respectively. Thermodynamic study showed that the enthalpy (ΔH) and Gibbs free energy(ΔG) values of the adsorption process for both pollutants were negative, suggesting that the process was spontaneous and exothermic in nature. This study showed active sites of SGO (π-π, hydroxyl, carboxyl, ketone, silane-based functional groups) contributed to an enormous enhancement in simultaneous removal of CR and Cd (II) from an aqueous solution, Therefore, SGO can be considered as a promising adsorbent for future water pollution control and removal of hazardous materials from aqueous solutions.     

Removal of heavy metals and arsenic from a co-contaminated soil by sieving combined with washing process

Batch experiments were conducted with a heavy metals and arsenic co-contaminated soil from an abandoned mine to evaluate the feasibility of a remediation technology that combines sieving with soil washing.Leaching of the arsenic and heavy metals from the different particle size fractions was found to decrease in the order: 0.1,2–0.1,and 2 mm.With increased contact time,the concentration of heavy metals in the leachate was significantly decreased for small particles,probably because of adsorption by the clay soil component.For the different particle sizes,the removal efficiencies for Pb and Cd were75%–87%,and 61%–77% for Zn and Cu,although the extent of removal was decreased for As and Cr at 45%.The highest efficiency by washing for Pb,Cd,Zn,and As was from the soil particles 2 mm,although good metal removal efficiencies were also achieved in the small particle size fractions.Through SEM-EDS observations and correlation analysis,the leaching regularity of the heavy metals and arsenic was found to be closely related to Fe,Mn,and Ca contents of the soil fractions.The remediation of heavy metal-contaminated soil by sieving combined with soil washing was proven to be efficient,and practical remediation parameters were also recommended.     

On the effect of Fe(Ⅲ) on proliferation of Microcystis aeruginosa at high nitrate and low chlorophyll condition

The impact of Fe concentrations on the growth of Microcystis aeruginosa in aquatic systems under high nitrate and low chlorophyll conditions was studied. The responses of cell density,total and cell chlorophyll-a intracellular Fe content and organic elemental composition of M.aeruginosa to different concentration gradients of Fe(Ⅲ) in the solutions were analysed. The results showed that the proliferation speeds of M. aeruginosa were:(1) decelerated when the Fe(Ⅲ) concentration was lower than 50 μg/L in the solutions,(2) promoted and positively related to the increase of Fe(Ⅲ) concentration from 100 to 500 μg/L in the solutions over the experimental period, and(3) promoted in the early stage but decelerated in later stages by excess adsorption of Fe by cells when the Fe(Ⅲ) concentration was higher than 500 μg/L in the solutions. The maximum cell density, total and cell chlorophyll-a were all observed at 500 μg Fe(Ⅲ)/L concentration. The organic elemental composition of M. aeruginosa was also affected by the concentration of Fe(Ⅲ) in the solutions, and the molecular formula of M. aeruginosa should be expressed as C_(7–7.5)H_(14)O_(0.8–1.3)N_(3.5–5)according to the functions for different Fe(Ⅲ)concentrations. Cell carbon and oxygen content appeared to increase slightly, while cell nitrogen content appeared to decrease as Fe(Ⅲ) concentrations increased from 100 to 500 μg/L in the solutions. This was attributed to the competition of photosynthesis and nitrogen adsorption under varying cell Fe content.     

Preparation and evaluation of Zr-β-FeOOH for efficient arsenic removal

A Zr-β-FeOOH adsorbent for both As(V) and As(III) removal was prepared by a chemical co-precipitation method.Compared with β-FeOOH,the addition of Zr enhanced the adsorption capacities for As(V) and As(III),especially As(III).The maximum adsorption capacities for As(III) and As(V) were 120 and 60mg/g respectively at pH 7.0,much higher than for many reported adsorbents.The adsorption data accorded with Freundlich isotherms.At neutral pH,for As(V),adsorption equilibrium was approached after 3 hr,while for As(III),adsorption equilibrium was approached after 5 hr.Kinetic data fitted well to the pseudo second-order reaction model.As(V) elimination was favored at acidic pH,whereas the adsorption of As(III) by Zr-β-FeOOH was found to be effective over a wide pH range of 4-10.Competitive anions hindered the adsorption according to the sequence:phosphate > silicate > bicarbonate > sulfate > nitrate,while Ca2+ and Mg2+ increased the removal of As(III) and As(V) slightly.The high adsorption capability and good performance in other aspects make Zr-β-FeOOH a potentially attractive adsorbent for the removal of both As(III) and As(V) from water.     

Preparation of Fe–Co based MOF-74 and its effective adsorption of arsenic from aqueous solution

To obtain a cost-effective adsorbent for the removal of arsenic in water,a novel nanostructured Fe–Co based metal organic framework(MOF-74)adsorbent was successfully prepared via a simple solvothermal method.The adsorption experiments showed that the optimal molar ratio of Fe/Co in the adsorbent was 2:1.The Fe_2Co_1MOF-74 was characterized by various techniques and the results showed that the nanoparticle diameter ranged from60 to 80 nm and the specific surface area was 147.82 m~2/g.The isotherm and kinetic parameters of arsenic removal on Fe_2Co_1MOF-74 were well-fitted by the Langmuir and pseudo-second-order models.The maximum adsorption capacities toward As(III)and As(V)were 266.52 and 292.29 mg/g,respectively.The presence of sulfate,carbonate and humic acid had no obvious effect on arsenic adsorption.However,coexisting phosphate significantly hindered the removal of arsenic,especially at high concentrations(10 mmol/L).Electrostatic interaction and hydroxyl and metal–oxygen groups played important roles in the adsorption of arsenic.Furthermore,the prepared adsorbent had stable adsorption ability after regeneration and when used in a real-water matrix.The excellent adsorption performance of Fe_2Co_1MOF-74 material makes it a potentially promising adsorbent for the removal of arsenic.     

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.     

Hg0 removal from flue gas over different zeolites modified by FeCl3

The elemental mercury removal abilities of three different zeolites(Na A, Na X, HZSM-5)impregnated with iron(Ⅲ) chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy, and temperature programmed desorption(TPD) analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg0, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury(Hg0)into oxidized mercury(Hg2+). The crystallization of Na Cl due to the ion exchange effect during the impregnation of Na A and Na X reduced the number of active Cl species on the surface, and restricted the physisorption of Hg0. Therefore, the Hg0 removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of Fe Cl3–HZSM-5 was mainly in the form of mercuric chloride(Hg Cl2), while on Fe Cl3–Na X and Fe Cl3–Na A it was mainly mercuric oxide(Hg O).     

Effects of cobalt doping on the reactivity of hausmannite for As(III) oxidation and As(V) adsorption

Hausmannite is a common low valence Mn oxide mineral, with a distorted spinel structure, in surficial sediments. Although natural Mn oxides often contain various impurities of transitional metals (TMs), few studies have addressed the effect and related mechanism of TM doping on the reactivity of hausmannite with metal pollutants. Here, the reactivity of cobalt (Co) doped hausmannite with aqueous As(III) and As(V) was studied. Co doping decreased the point of zero charge of hausmannite and its adsorption capacity for As(V). Despite a reduction of the initial As(III) oxidation rate, Co-doped hausmannite could effectively oxidize As(III) to As(V), followed by the adsorption and fixation of a large amount of As(V) on the mineral surface. Arsenic K-edge EXAFS analysis of the samples after As(V) adsorption and As(III) oxidation revealed that only As(V) was adsorbed on the mineral surface, with an average As-Mn distance of 3.25–3.30 Å, indicating the formation of bidentate binuclear complexes. These results provide new insights into the interaction mechanism between TMs and low valence Mn oxides and their effect on the geochemical behaviors of metal pollutants.     

Evaluation of heavy metal contamination hazards in nuisance dust particles, in Kurdistan Province, western Iran

The effects of natural andgeochemical factors depending on heavy metal contamination in nuisance dust particles were evaluated. The nuisance dust particles were sampled using passive deposit gauge method for one year from April2010 to March2011 and the obtained samples were measured for the total contents and the contamination levels of Fe, Mn, Cu and As usinggeo-accumulation index (Igeo ), enrichment factor (EF) and the integrated pollution index (IPI). The results showed that, the contamination levels of Fe and Mn based on Igeo values, were uncontaminated (Igeo < 0) (variations of the Igeo index was from -3.11 to -1.751 for Fe, from -0.630 to -1.925 for Mn), while the values of Cu and As were demonstrated to have moderate contamination based on Igeo values (variations of Igeo index was from -1.125 to 0.848 for Cu, and from -2.002 to 1.249 for As). The analysis of EF also revealed minor to moderate enrichment for Mn (1.215-4.214), minor to moderately severe enrichment for Cu (2.791-6.484), and As (1.370-8.462), respectively. The variation of the IPI index also showed low to moderate level of heavy metal pollution in nuisance dust particulates (0.511-1.829). The analysis of the results also approved that the natural processes andgeochemical variables (the changing meteorological parameters) can significantly affect the availability of heavy metals in nuisance dust particles in Western Iran.