Artificial Neural Network and Full Factorial Design Assisted AT-MRAM on Fe Oxides, Organic Materials, and Fe/Mn Oxides in Surficial Sediments

Artificial neural network（ANN） and full factorial design assisted atrazine（AT） multiple regression adsorption model（AT-MRAM） were developed to analyze the adsorption capability of the main components in the surficial sediments（SSs）. Artificial neural network was used to build a model（the determination coefficient square r2 is 0.9977） to describe the process of atrazine adsorption onto SSs, and then to predict responses of the full factorial design. Based on the results of the full factorial design, the interactions of the main components in SSs on AT adsorption were investigated through the analysis of variance（ANOVA）, F-test and t-test. The adsorption capability of the main components in SSs for AT was calculated via a multiple regression adsorption model（MRAM）. The results show that the greatest contribution to the adsorption of AT on a molar basis was attributed to Fe/Mn（–1.993 μmol/mol）. Organic materials（OMs） and Fe oxides in SSs are the important adsorption sites for AT, and the adsorption capabilities are 1.944 and 0.418 μmol/mol, respectively. The interaction among the non-residual components（Fe, Mn oxides and OMs） in SSs interferes in the adsorption of AT that shouldn’t be neglected, revealing the significant contribution of the interaction among non-residual components to controlling the behavior of AT in aquatic environments.

Antimony oxidation and adsorption by in-situ formed biogenic Mn oxide and Fe–Mn oxides

Antimony（Sb）, which can be toxic at relatively low concentrations, may co-exist with Mn（Ⅱ）and/or Fe（Ⅱ） in some groundwater and surface water bodies. Here we investigated the potential oxidation and adsorption pathways of Sb（Ⅲ and V） species in the presence of Mn（Ⅱ） and Mn-oxidizing bacteria, with or without Fe（Ⅱ）. Batch experiments were conducted to determine the oxidation and adsorption characteristics of Sb species in the presence of biogenic Mn oxides（BMOs）, which were formed in-situ via the oxidation of Mn（Ⅱ） by a Mn-oxidizing bacterium（Pseudomonas sp. QJX-1）. Results indicated that Sb（Ⅲ） ions could be oxidized to Sb（V） ions by BMO, but only Sb（V） originating from Sb（Ⅲ） oxidation was adsorbed effectively by BMO. Introduced Fe（Ⅱ） was chemically oxidized to Fe OOH, the precipitates of which mixed with BMO to form a new compound, biogenic Fe–Mn oxides（BFMO）. The BMO part of the BFMO mainly oxidized and the Fe OOH of the BFMO mainly adsorbed the Sb species. In aquatic solutions containing both As（Ⅲ） and Sb（Ⅲ）, the BFMO that formed in-situ preferentially oxidized Sb over As but adsorbed As more efficiently. Chemical analysis and reverse transcription real-time polymerase chain reaction revealed that the presence of Fe（Ⅱ）, As（Ⅲ） and Sb（Ⅲ） accelerated the oxidation of Mn（Ⅱ） but inhibited the activity of Mn-oxidizing bacteria. These results provide significant insights into the biogeochemical pathways of Sb, Mn（Ⅱ） in aquatic ecosystems, with or without Fe（Ⅱ）.

Removal of tungsten from molybdate solution by Fe-Mn binary oxide adsorbent

Considering the different geochemical enrichment behaviors of W and Mo,Fe?Mn binary oxide(FMBO),ferric hydroxide(Fe(OH)3)and manganese dioxide(MnO2)were studied to separate W from molybdate solution,respectively.The experimental results demonstrated that Fe?Mn binary oxide(FMBO)was the most suitable adsorbent for the separation.Under a wide pH(6.9?11.3)region,more than80%W removal efficiency and less than3%Mo loss could be obtained.In addition,the Fe?Mn binary oxide adsorbent can be regenerated by treating with3mol/L NaOH,and the W adsorption efficiency was retained after five adsorption?desorption?regeneration cycles.All these indicate that the Fe?Mn binary oxides have the potential for the separation of W from molybdate solution.

Recent progress in Li and Mn rich layered oxide cathodes for Li-ion batteries

Li and Mn rich(LMR)layered oxides,written as xLi_(2) MnO_(3)·(1-x)LiMO_(2)(M=Mn,Ni,Co,Fe,etc.),have been widely reported in recent years due to their high capacity and high energy density.The stable structure and superior performance of LMR oxides make them one of the most promising candidates for the next-generation cathode materials.However,the commercialization of these materials is hindered by several drawbacks,such as low initial Coulombic efficiency,the degradation of voltage and capacity during cycling,and poor rate performance.This review summarizes research progress in solving these concerns of LMR cathodes over the past decade by following three classes of strategies:morphology design,bulk design,and surface modification.We elaborate on the processing procedures,electrochemical performance,mechanisms,and limitations of each approach,and finally put forward the concerns left and the possible solutions for the commercialization of LMR cathodes.

Arsenite oxidation by three types of manganese oxides

Oxidation of As（Ⅲ） by three types of manganese oxides and the effects ofpH, ion strength and tartaric acid on the oxidation were investigated by means of chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Three synthesized Mn oxide minerals, bimessite, cryptomelane, and hausmannite, which widely occur in soil and sediments, could actively oxidize As（Ⅲ） to As（Ⅴ）. However, their ability in As（Ⅲ）-oxidation varied greatly depending on their structure, composition and surface properties. Tunnel structured cryptomelane exhibited the highest ability of As （Ⅲ） oxidation, followed by the layer structured birnessite and the lower oxide hausmannite. The maximum amount of As （Ⅴ） produced by the oxidation was in the order （mmol/kg） of cryptomelane （824.2） 〉 bimessite （480.4） 〉 hausmannite （117.9）, As pH increased from the very low value（pH 2.5）, the amount of As（Ⅲ） oxidized by the tested Mn oxides was firstly decreased, then negatively peaked in pH 3.0 6.5, and eventually increased remarkably. Oxidation of As（Ⅲ） by the Mn oxides had a buffering effects on the pH variation in the solution. It is proposed that the oxidative reaction processes between As （Ⅲ） and biruessite（or cryptomelane） are as follows： （1） at lower pH condition： （MnO2）x＋ H3AsO3 ＋ 0.5H^＋=0.5H2AsO4^- ＋ 0.5HAsO4^2- ＋Mn〉^2＋ （MnO2）x-1 ＋ H2O; （2） at higher pH condition： （MnO2）x ＋ H3AsO3 = 0.5H2AsO4^- ＋ 0.5HAsO4^2- ＋ 1.5H^＋ ＋ （MnO2）x-1. MnO. With increase of ion strength, the As（Ⅲ） oxidized by bimessite and cryptomelane decreased and was negatively correlated with ion strength. However, ion strength had little influence on As （Ⅲ） oxidation by the hausmarmite. The presence of tartaric acid promoted oxidation of As（Ⅲ） by birnessite. As for cryptomelane and hansmannite, the same effect was observed when the concentration of tartaric acid was below 4 mmol/L, otherwise the oxidized As（Ⅲ） decreased. These findings are of great significance in improving our understanding of As geochemical cycling and controlling As contamination.

Measurement of Atrazine Adsorption onto Surficial Sediments(Natural Surface Coatings)——New Evidence for the Importance of Fe Oxides

To reveal the relative contribution of the components, Fe, Mn oxides or organic materials（OMs） in the surficial sediments（SSs）, and the natural surface coating samples（NSCSs） to adsorbing atrazine（AT）, a selective chemical extraction technique was employed, to remove the different components, and the adsorption characteristics of AT on the SSs and the NSCSs were investigated. The observed adsorptions of AT on the original and extracted SSs and NSCSs were analyzed by nonlinear least squares fitting（NLSF） to estimate the relative contribution of the components. The results showed that the maximum adsorption of AT on the NSCSs was greater than that in the SSs, before and after extraction treatments, implying that the NSCSs were more dominant than the SSs for organic pollutant adsorption. It was also found that the Fe oxides, OMs, and residues in SSs（NSCSs） facilitated the adsorption of AT, but Mn oxides directly or indirectly restrained the interaction of AT with SSs（NSCSs） particles. The contribution of the Fe oxides to AT adsorption was more than that of OMs; the greatest contribution to AT adsorption on a molar basis was from the Fe oxides in the nonresidual fractions, indicating that the Fe oxides played an important role in controlling the environmental behavior of AT in an aquatic environment.

Mineralogy of Manganese Oxide Minerals in Iron Manganese Nodules of Several Main Soils in China

X-ray diffraction and selective chemical dissolution methods were used to investigate the composition of Mn oxide minerals in Fe-Mn nodules of several main types of soils in China. The changes of relative intensity of X-ray diffraction patterns were studied both before and after chemically selective dissolution. It was found that lithiophorite was a common Mn oxide in all examined Fe-Mn nodules. Todorokite, however, was a predominant Mn oxide in Fe-Mn nodules in caf-aquic Vertisols of Linyi, Shandong Province. The Fe-Mn nodules of arp-udic Luvisols in Wuhan and Zaoyang, Hubei Province, contained birnessite and vernadite. Hollandite was found in Fe-Mn nodules of alt-udic Ferrisols of Yizhang, Hunan Province; arp-udic Luvisols of Zaoyang, Hubei Province; and cal-aquic Vertisols of Linyi, Shandong Province. The Fe-Mn nodules in alt-udic Ferrisols of Guiyang, Hunan Province, had a few coronadites. Mineralogy of Mn oxide minerals in soil Fe-Mn nodules was related to soil environment, soil types and quantities of relevant cations.

Oxidation of As^Ⅲ by Several Manganese Oxide Minerals in Absence and Presence of Goethite

Oxidation of As^Ⅲ by three types of manganese oxide minerals affected by goethite was investigated by chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Three synthesized Mn oxide minerals of different types, birnessite, todorokite, and hausmannite, could actively oxidize As^Ⅲ to Asv, and greatly varied in their oxidation ability. Layer structured birnessite exhibited the highest capacity of As^Ⅲ oxidation, followed by the tunnel structured todorokite. Lower oxide hansmannite possessed much low capacity of As^Ⅲ oxidation, and released more Mn^2＋ than birnessite and todorokite during the oxidation. The maximum amount of Asv produced during the oxidation of As^Ⅲ by Mn oxide minerals was in the order： birnessite （480.4 mmol/kg） 〉 todorokite （279.6 mmol/kg） 〉 hansmannite （117.9 mmol/kg）. The oxidation capacity of the Mn oxide minerals was found to be relative to the composition, crystallinity, and surface properties. In the presence of goethite oxidation of As^Ⅲ by Mn oxide minerals increased, with maximum amounts of Asv being 651.0 mmol/kg for birnessite, 332.3 mmol/kg for todorokite and 159.4 mmol/kg for hansmannite. Goethite promoted As^Ⅲ oxidation on the surface of Mn oxide minerals through adsorption of the Asv produced, incurring the decrease of Asv concentration in solutions. Thus, the combined effects of the oxidation （by Mn oxide minerals）-adsorption （by goethite） lead to rapid oxidation and immobilization of As in soils and sediments and alleviation of the As^Ⅲ toxicity in the environments.

Enhanced catalytic performance of Cu-and/or Mn-loaded Fe-Sep catalysts for the oxidation of CO and ethyl acetate

The Fe-modi fied sepiolite-supported Mn–Cu mixed oxide(Cux Mny/Fe-Sep) catalysts were prepared using the co-precipitation method.These materials were characterized by means of the XRD,N_2 adsorption–desorption,XPS,H_2-TPR,and O_2-TPD techniques,and their catalytic activities for CO and ethyl acetate oxidation were evaluated.The results show that catalytic activities of the Cux Mny/Fe-Sep samples were higher than those of the Cu1/Fe-Sep and Mn2/Fe-Sep samples,and the Mn/Cu molar ratio had a distinct in fluence on catalytic activity of the sample.Among the Cux Mny/Fe-Sep and Cu1Mn2/Sep samples,Cu1Mn2/Fe-Sep performed the best for CO and ethyl acetate oxidation,showing the highest reaction rate and the lowest T50 and T90 of 4.4×10^(-6) mmol·g-1·s-1,110,and 140 °C for CO oxidation,and 1.9×10^(-6) mmol·g-1·s-1,170,and210 °C for ethyl acetate oxidation,respectively.Moreover,the Cu1Mn2/Fe-Sep sample possessed the best lowtemperature reducibility and the lowest temperature of oxygen desorption as well as the highest surface Mn^(4+)/Mn^(3+) and Cu^(2+)/CuO atomic ratios.It is concluded that factors,such as the strong interaction between the Cu or Mn and the Fe-Sep support,good low-temperature reducibility,and good mobility of chemisorbed oxygen species,might account for the excellent catalytic activity of Cu1Mn2/Fe-Sep.

Heterogeneously-catalyzed aerobic oxidation of furfural to furancarboxylic acid with CuO-Promoted MnO_(2)

A cost-effective and sustainable noble-metal free catalyst system based on ubiquitously available Mn-Cu bimetallic oxides was served as efficient catalysts for furfural selective oxidation to furancarboxylic acid(FA). Interestingly, Mn_(2)Cu_(1)O_(x)exhibited an excellent furfural conversion of 99% with quantitative selectivity toward FA. Especially, we demonstrate the significant weakening of the Mn-O bonds with the incorporation of CuO into the Mn-Cu oxides, resulting in an improved OLreactivity of Mn_(2)Cu_(1)O_(x), which brings about a higher catalytic activity for furfural oxidation. More importantly, Mn_(2)Cu_(1)O_(x)could exhibit YFA>90% over 5 cycles of reusability test. Through this study, the relationship between the morphology, surface chemistry, and catalytic activity of Mn-Cu bimetallic oxides are elucidated, providing a simple and environmentally friendly catalytic strategy and scientific basis for the development of Mn-Cu bimetallic oxides bioderived molecular aerobic oxidation materials.

STUDIES OF OXYGEN ADSORPTION AND INITIAL OXIDATION ON SINGLE CRYSTAL Mn_5Si_3(111) SURFACE

Kinetics of oxygen adsorption on single crystal Mn5Si3 （111） surface and initial surface oxidation were investigated. Oxygen chemisorbs dissociatively at room temperature on Mn and Si atoms. A fast oxidation of Si atoms occurs followed by oxidation of Mn atoms at RT. The MnO2 was reduced by Si atoms and the SiO was oxidized further to SiO2 during the sample heating.

Combined Chemical and Mineralogical Evidence for Heavy Metal Binding in Mining- and Smelting-Affected Alluvial Soils

The binding of metallic contaminants （Pb, Cd, and Zn） and As on soil constituents was studied on four highly contaxninated alluvial soil profiles from the mining/smelting district of Pribram （Czech Republic） using a combination of mineralogical and chemical methods. Sequential extraction analysis （SEA） was supplemented by mineralogical investigation of both bulk samples and heavy mineral fractions using X-ray diffraction analysis （XRD） and scanning electron microscopy with an energy dispersive X-ray spectrometer （SEM/EDS）. The mineralogy of Fe and Mn oxides was studied by voltammetry of microparticles （VMP） and diffuse reflectance spectrometry （DRS）. Zinc and Pb were predominantly bound in the reducible fraction attributed to Fe oxides and Mn oxides （mainly birnessite, Na4Mn14O27.9H2O）, which were detected in soils by XRD and SEM/EDS. In contrast, Cd was the most mobile contaminant and was predominantly present in the exchangeable fraction. Arsenic was bound to the residual and reducible fractions （corresponding to Fe oxides or to unidentified Fe-Pb arsenates）. SEM/EDS observations indicate the predominant affinity of Pb for Mn oxides, and to a lesser extent, for Fe oxides. Thus, a more suitable SEA procedure should be used for these mining-affected soils to distinguish between the contaminant fraction bound to Mn oxides and Fe oxides.

Effect of Interaction of Non-residual Fractions on Adsorption of Atrazine onto Surficial Sediments and Natural Surface Coating Samples

To quantify the effect of the interaction of non-residual fractions[Fe oxides（Fe）, Mn oxide（Mn）, organic materials（OMs）] in the surficial sediments and the natural surface coating samples on the adsorption of atrazine（AT）, an AT multiple regression adsorption model（AT-MRAM） was developed. The AT-MRAM improves upon the previous AT additional adsorption model（AT-AAM） with superior goodness-of-fit test（adjusted R2=ca.1.000）, F-test and t-test（P〈0.01）, and reveals the effect of the interaction among the components in the surficial sediments（SSs） and na- tural surface coatings samples（NSCSs） on the adsorption of AT, which was neglected by the AT-AAM. Meanwhile, the AT-MRAM was also verified through adsorption experiments of AT and the relative deviation between predicted maximum adsorption of AT and the experimental one is less than 15%. The resulted information shows that Mn is prone to interact with other non-residual components, the total maximum adsorption of AT is inversly proportional to the level of Mn, and Fe and OMs facilitate the adsorption of AT. The results also indicate that the adsorption of AT is not only dominated by Fe, OMs, Fe/OMs, but also restrained by Fe/Mn, Fe/Mn/OMs, with lesser roles attributed to Mn, and the estimated AT distributions among the components do not agree with that previously predicted by the AT-AAM, especially with the relative contribution of Mn to the adsorption of AT, revealing significant contribution of the interactions among non-residual components in controlling the behavior of AT in aquatic environments.

Quantifying aluminosilicate manganese release and dissolution rates across organic ligand treatments for rocks, minerals,and soils

Manganese is ubiquitous in terrestrial environments and most studies have focused on dissolution of Mn oxides,but aluminosilicates also release Mn.Here,we evaluated oxic Mn dissolution from six rocks and minerals(amphibolite,anorthosite,kaolinite,kyanite,muscovite,orthoclase feldspar) and soils from four Critical Zone Observatories(CZOs) under four LMWOLs treatments(catechol,citric acid,oxalic acid,control).Overall rock and mineral Mn mass-normalized release was 1.4 ± 0.5 nM μM^(-1) 14 d^(-1) and dissolution rate was 2403 ± 935 nM m^(-2) d^(-1) x 10^(3).Overall CZO soil Mn release was 16.7±5.1 nM μM^(-1) 14 d^(-1) and dissolution rate was 7010 ± 2570 nM m^(-2) d^(-1) × 10^(3).Anorthosite and kyanite had the highest Mn dissolution rates but kaolinite and kyanite had the highest Mn mass-normalized release rates.We hypothesize the structural location of Mn,surface area,and potential inclusions of highly-weatherable-phases control Mn dissolution for rocks and minerals.CZO soils with the highest solid phase Mn had the highest Mn release and dissolution rates.Citric acid and catechol had higher Mn release and dissolution rates than the control while oxalic acid did not.For rocks and minerals,we found pH 4 had higher Mn release and dissolution rates than pH6,but not for control treatments without LMWOL.Our study highlights that the abundance of Mn drove Mn release in soils but not rocks and minerals.Moreover,LMWOLs are important for Mn dissolution,even under acidic pH conditions.

Remediation performance and mechanisms of Cu and Cd contaminated water and soil using Mn/Al-layered double oxide-loaded biochar

The combined pollution of heavy metals is ubiquitous worldwide.Mn/Al-layered double oxide-loaded crab shells biochar (LDO/BC) was prepared,so as to remediate the combined pollution of Cd and Cu in soil and water.The pristine and used LDO/BC were characterized and the results revealed that the layered double oxide was successfully loaded on crab shells biochar (BC) and metal element Ca in crab shells was beneficial to the formation of more regular layered and flake structure.The maximal adsorption capacity (Qm) of LDO/BC for aqueous Cu^(2+)and Cd^(2+)was 66.23 and 73.47 mg/g,respectively.LDO/BC and BC were used to remediate e-waste-contaminated soil for the first time and exhibited highly efficient performance.The extraction amount of Cu and Cd in the contaminated soil by diethylene triamine penta-acetic acid (DTPA) after treating with 5% LDO/BC was significantly reduced from 819.84 to 205.95 mg/kg (with passivation rate 74.8%) and 8.46 to 4.16 mg/kg(with passivation rate 50.8%),respectively,inferring that the bioavailability of heavy metals declined remarkably.The experimental result also suggested that after remediation by LDO/BC the exchangeable and weak acid soluble Cu and Cd in soil translated to reducible,residual and oxidizable fraction which are more stable state.Precipitation,complexation and ion exchange were proposed as the possible mechanisms for Cd and Cu removal.In general,these experiment results indicate that LDO/BC can be a potentially effective reagent for remediation of heavy metal contaminated water and soil.

Induced transformation of antimony trioxide by Mn(II) oxidation and their co-transformed mechanism

Antimony(Sb)is a toxic and carcinogenic element that often enters soil in the form of antimony trioxide(Sb_(2)O_(3))and coexists with manganese(Mn)in weakly alkaline conditions.Mn oxides such as birnessite have been found to promote the oxidative dissolution of Sb_(2)O_(3),but few researches concerned the co-transformations of Sb_(2)O_(3) and Mn(II)in environment.This study investigated themutual effect of abiotic oxidation of Mn(II)and the coupled oxidative dissolution of Sb_(2)O_(3).The influencing factors,such as Mn(II)concentrations,pH and oxygen were also discussed.Furthermore,their co-transformed mechanism was also explored based on the analysis of Mn(II)oxidation products with or without Sb_(2)O_(3) using XRD,SEM and XPS.The results showed that the oxidative dissolution of Sb_(2)O_(3) was enhanced under higher pH and higher Mn(II)loadings.With a lower Mn(II)concentration such as 0.01 mmol/L Mn(II)at pH 9.0,the improved dissolution of Sb_(2)O_(3) was attributed to the generation of dissolved intermediate Mn(III)species with strong oxidation capacity.However,under higher Mn(II)concentrations,both amorphous Mn(III)oxides and intermediate Mn(III)species were responsible for promoting the oxidative dissolution of Sb_(2)O_(3).Most released Sb(∼72%)was immobilized by Mn oxides and Sb(V)was dominant in the adsorbed and dissolved total Sb.Meanwhile,the presence of Sb_(2)O_(3) not only inhibited the removal of Mn(II)by reducing Mn(III)to Mn(II)but also affected the final products of Mn oxides.For example,amorphous Mn oxides were formed instead of crystalline Mn(III)oxides,such as MnOOH.Furthermore,rhodochrosite(MnCO_(3))was formed with the high Mn(II)/Sb_(2)O_(3) ratio,but without being observed in the low Mn(II)/Sb_(2)O_(3) ratio.The results of study could help provide more understanding about the fate of Sb in the environment and the redox transformation of Mn.

Effect of Cobalt-Doped Framework on Formation of Todorokite from Layered Manganese Oxides with Mg^(2+)/Co^(2+) Ions as Template

Cobalt （Co） exists in significant quantities in naturally occurring manganese （Mn） oxides and alters the growth of Mn oxide crystals. Four-layered Mn oxides, Na-buserite （Na-bus） and three Co-doped Na-buserite samples prepared from oxidation of Mn（OH）2 with 5%, 10%, and 20% Co/（Mn ＋ Co） molar ratios （5Co-Na-bus, 10Co-Na-bus, and 20Co-Na-bus）, were used to prepare todorokite, a common Mn oxide on the Earth＇s surface, using Mg2＋/Co2＋ ions as a template. The results showed that todorokites could be obtained by reflux treatment of Mg2＋-exchanged non-doped Na-buserite and three Co-doped Na-buserites at atmospheric pressure. However, the formation of todorokites was prohibited by reflux treatment of Co2＋-exchanged Na-bus, 5Co-Na-bus, and 10Co-Na-bus samples. Instead, todorokite was obtained by the reflux treatment of Co2＋-exchanged 20Co-Na-bus samples under atmospheric pressure. X-ray photoelectron spectroscopy analysis showed that doped Co existed as Co3＋ in the MnOs layers of doped Na-buserites. The amount of substituted Co3＋ in the MnO6 layers may play a key role in the conversion of buserite to todorokite using Co2＋ ions as a template.

Characterization and reactivity of biogenic manganese oxides for ciprofloxacin oxidation

Biogenic manganese oxides （BioMnOx） were synthesized by the oxidation of Mn（II） with Mn- oxidizing bacteria Pseudomonas sp. G7 under different initial pH values and Mn（II） dosages, and were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and UV-Vis absorption spectroscopy. The crystal structure and Mn oxidation states of BioMnOx depended on the initial pH and Mn（lI） dosages of the medium. The superoxide radical （O2） was observed in Mn-containing （III/IV） BioMnOx suspensions by electron spin resonance measurements. BioMnOx（0.4）-7, with mixed valence of Mn（II/III/IV） and the strongest O^- signals, was prepared in the initial pH 7 and Mn（II） dosage of 0.4 mmol/L condition, and exhibited the highest activity for ciproftoxacin degradation and no Mn（II） release. During the degradation of ciprofloxacin, the oxidation of the Mn（II） formed came from biotic and abiotic reactions in BioMnOx suspensions on the basis of the Mn（II） release and O2- formation from different BioMnOx. The degradation process of ciprofloxacin was shown to involve the cleavage of the hexatomic ring having a secondary amine and carbon-carbon double bond connected to a carboxyl group, producing several compounds containing amine groups as well as small organic acids.

Arsenic and cadmium removal from water by a calcium-modified and starch-stabilized ferromanganese binary oxide

A new calcium-modified and starch-stabilized ferromanganese binary oxide (Ca-SFMBO)sorbent was fabricated with different Ca concentrations for the adsorption of arsenic (As)and cadmium (Cd) in water.The maximum As(Ⅲ) and Cd(Ⅱ) adsorption capacities of 1%CaSFMBO were 156.25 mg/g and 107.53 mg/g respectively in single-adsorption systems.The adsorption of As and Cd by the Ca-SFMBO sorbent was pH-dependent at values from 1 to 7,with an optimal adsorption pH of 6.In the dual-adsorbate system,the presence of Cd(Ⅱ) at low concentrations enhanced As(Ⅲ) adsorption by 33.3%,while the adsorption of As(Ⅲ) was inhibited with the increase of Cd(Ⅱ) concentration.Moreover,the addition of As(Ⅲ) increased the adsorption capacity for Cd(Ⅱ) up to two-fold.Through analysis by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR),it was inferred that the mechanism for the co-adsorption of Cd(Ⅱ) and As(Ⅲ) included both competitive and synergistic effects,which resulted from the formation of ternary complexes.The results indicate that the Ca-SFMBO material developed here could be used for the simultaneous removal of As(Ⅲ) and Cd(Ⅱ) from contaminated water.

Phase transformation of Cr(Ⅵ)-adsorbed ferr ihydr ite in the presence of Mn(Ⅱ): Fate of Mn(Ⅱ)and Cr(Ⅵ)

Ferrihydrite is an important sink for the toxic heavy metal ions, such as Cr(Ⅵ). As ferrihydrite is thermodynamically unstable and gradually transforms into hematite and goethite, the stability of Cr(Ⅵ)-adsorbed ferrihydrite is environmentally significant. This study investigated the phase transformation of Cr(Ⅵ)-adsorbed ferrihydrite at different pH in the presence of aqueous Mn(Ⅱ), as well as the fate of Mn(Ⅱ) and Cr(Ⅵ) in the transformation process of ferrihydrite. Among the ferrihydrite transformation products, hematite was dominant, and goethite was minor. The pre-adsorbed Cr(Ⅵ) inhibited the conversion of ferrihydrite to goethite at initial pH 3.0, whereas little amount of adsorbed Mn(Ⅱ) favored the formation of goethite at initial pH 7.0. After the aging process, Cr species in solid phase existed primarily as Cr(Ⅲ) in the presence of Mn(Ⅱ) at initial pH 7.0 and 11.0. The aqueous Mn concentration was predominantly unchanged at initial pH 3.0, whereas the aqueous Mn(Ⅱ) was adsorbed onto ferrihydrite or form Mn(OH)_(2) precipitates at initial pH 7.0 and 11.0, promoting the immobilization of Cr(Ⅵ). Moreover, the oxidation of Mn(Ⅱ) occurred at initial pH 7.0 and 11.0, forming Mn(Ⅲ/Ⅳ)(hydr)oxides.