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 pH condition (pH 3.5) and background electrolyte of 0.01 mol/L NaCl. 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 pH. 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.     

Phase transformation of Cr(VI)-adsorbed ferrihydrite 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.     

Chromium transformation driven by iron redox cycling in basalt-derived paddy soil with high geological background values

The flooding and drainage of paddy fields has great effects on the transformation of heavy metals, however, the transformation of Cr in basalt-derived paddy soil with high geological background values was less recognized. The typical basalt-derived paddy soil was incubated under alternating redox conditions. The Cr fractions and the dynamics of Fe/N/S/C were examined. The HCl-extractable Cr increased under anaerobic condition and then decreased during aerobic stage. The UV-vis spectra of the supernatant showed that amounts of colloids were released under anaerobic condition, and then re-aggregated during aerobic phase. The scanning transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) revealed that Fe oxides were reduced and became dispersed during anaerobic stage, whereas Fe(II) was oxidized and recrystallized under aerobic condition. Based on these results, a kinetic model was established to further distinguish the relationship between the transformation of Cr and Fe. During anaerobic phase, the reduction of Fe(III) oxides not only directly released the structurally bound Cr, but also enhanced the breakdown of soil aggregation and dissolution of organic matter causing indirect mobilization of Cr. During aerobic phase, the oxidation of Fe(II) and further recrystallization of newly formed Fe(III) oxides might induce the re-aggregation of soil colloids and further incorporation of Cr. In addition, the kinetic model of Cr and Fe transformation was further verified in the pot experiment. The model-based findings demonstrated that the Cr transformation in the basalt-derived paddy soil with high geological background values was highly driven by redox sensitive iron cycling.     

The role of copper and oxalate in the redox cycling of iron in atmospheric waters

During daytime, the redox cycling of dissolved iron compounds in atmospheric waters, and the related in-cloud transformations of photooxidants, are affected by reactions of Fe and Cu with hydroperoxy (HO₂) and superoxide (O₂⁻) radicals and the photoreduction of Fe(III)-oxalato complexes. We have investigated several of the important chemical reactions in this redox cycle, through laboratory simulation of the system, using γ-radiation to produce HO₂/O₂⁻. At concentrations comparable to those measured in atmospheric waters, the redox cycling of Fe was dramatically affected by the presence of oxalate and trace concentrations of Cu. At concentrations more than a hundred times lower than Fe, Cu consumed most of the HO₂/O₂⁻, and cycled between the Cu(II) and Cu(I) forms. Cu⁺ reacted with FeOH²⁺ to produce Fe(II) and Cu(II), with a second order rate constant of approximately 3 × 10⁷ M⁻¹s⁻¹. The presence of oxalate resulted in the formation of Fe(III)-oxalato complexes that were essentially unreactive with HO₂/O₂⁻. Only at high oxalate concentrations was the Fe(II)C₂O₄ complex also formed, and it reacted relatively rapidly with hydrogen peroxide (k = (3.1 ± 0.6) × 10⁴ M⁻¹s⁻¹). Simulations incorporating measurements for other redox mechanisms, including oxidation by ozone, indicate that, during daytime, Fe should be found mostly in the ferrous oxidation state, and that reactions of FeOH²⁺ with Cu(I) and HO₂/O₂⁻, and to a lesser degree, the photolysis of Fe(III)-oxalato complexes, are important mechanisms of Fe reduction in atmospheric waters. The catalytic effect of Cu(II)/Cu(I) and Fe(III)/Fe(II) should also significantly increase the sink function of the atmospheric liquid phase for HO₂ present in a cloud. A simple kinetic model for the reactions of Fe, Cu and HO₂/O₂⁻, accurately predicted the changes in Fe oxidation states that occurred when authentic fogwater samples were exposed to HO₂/O₂⁻.     

Aqueous S(IV) oxidation—I. Catalytic effects of some metal ions

Catalytic effect of metal ions [Fe(III), Mn(II), Cu(II), Pb(II) and Zn(II)] on the oxidation of S(IV) in aqueous solution at concentrations of metal ions and S(IV) as found in an urban atmosphere were studied under controlled experimental conditions (T, pH air flow rate, mixing, concentration of reactant, etc.). The following rate expressions were obtained: −r_S(IV) = k [Fe(III)] [S(IV)], −r_S(IV) = k [Mn(II)] [S(IV)]^0.65, −r_S(IV) = k [Cu(II)] [S(IV)]². The activation energy equals 104 kJ mol⁻¹ for Fe(III), 63.3 kJ mol⁻¹ for Mn(II), and 116.8 kJ mol⁻¹ for Cu(II) catalysed S(IV) oxidation.     

Kinetics and mechanism of the sulfite-induced autoxidation of Fe(II) in acidic aqueous solution

A spectrophotometric study employing stopped-flow techniques was performed of the sulfite-induced autoxidation of Fe(II) in acidic aqueous solution (pH < 3.9). In the presence of an excess Fe(II), simultaneous autoxidation of Fe(II) and sulfite occurs, and completes the catalytic cycle for the Fe(III) catalyzed autoxidation of sulfite. In the presence of an excess sulfite, the rapid formation of Fe(III) is followed by a slower redox process during which Fe(II) and sulfate are produced. The sulfite-induced autoxidation of Fe(II) is independent of the Fe(II) concentration. The suggested mechanism involves the rate-determining formation of SO₃⁻, followed by the formation of SO₅⁻and the subsequent oxidation of Fe(II).     

Roles of manganese oxides in degradation of phenol under UV-Vis irradiation: Adsorption, oxidation, and photocatalysis

The effect of crystal structure on photocatalytic activities of manganese oxides and underlying reaction mechanism were investigated.     

Ligand effects on arsenite removal by zero-valent iron/O2: Dissolution, corrosion, oxidation and coprecipitation

Ligands may increase the yields of reactive oxygen species (ROS) in zero-valent iron (ZVI)/O₂ systems. To clarify the relationship between the properties of ligands and their effects on the oxidative removal of contaminants, five common ligands (formate, acetate, oxalate, ethylenediaminetetraacetic acid (EDTA), and phosphate) as well as acetylacetone (AA) were investigated with arsenite (As(III)) as the target contaminant at three initial pH values (3.0, 5.0, and 7.0). The addition of these ligands to the ZVI/O₂ system resulted in quite different effects on As(III) removal. EDTA enhanced the oxidation of As(III) to arsenate (As(V)) but inhibited the removal of As(V). Oxalate was the only ligand in this work that accelerated both the removal of As(III) and As(V). By analyzing the ligand effects from the four aspects: dissolution of surface iron (hydr)oxides, corrosion of ZVI, reaction with ROS, and interference with precipitation, the following properties of ligands were believed to be important: ability to provide dissociable protons, complexation ability with iron, and reactivity with ROS. The complexation ability is a double-edged sword. It could enhance the generation of ROS by reducing the reduction potential of the Fe(III)/Fe(II) redox couple, but also could inhibit the removal of arsenic by coprecipitation. The elucidated relationship between the key property parameters of ligands and their effects on the ZVI/O₂ system is helpful for the rational design of effective ZVI/ligand/O₂ systems.     

模拟环境条件下δ-MnO2氧化As(III)的搅拌流动动力学特征

采用搅拌流动法研究了酸性水钠锰矿及水羟锰矿2种δ-MnO2矿物氧化As(Ⅲ)的动力学过程,构建了可用于多相体系的搅拌-流动氧化还原反应动力学模型.经过As吸附量的校正后,该模型对酸性水钠锰矿及水羟锰矿氧化As(III)动力学数据拟合度分别为0.980和0.951,模型拟合得到pH 7时2种矿物单位比表面上氧化As(III)的初始反应速率常数k分别为0.131,0.014min-1×m-2.相比而言,该速率常数明显高于批量法得到的表观速率常数kobs,0.021,0.001min-1×m-2更接近真实的化学动力学参数.搅拌流动法与批量法得到的不同矿物的速率常数大小趋势一致,即尽管酸性水钠锰矿对As(III)的氧化率低于水羟锰矿,单位比表面上酸性水钠锰矿氧化As(III)初始反应速率却远高于水羟锰矿.反应过程分析表明,反应初始阶段,As(III)的吸附为主要限速步骤;而随着反应的进行,矿物表面反应位点逐渐钝化或减少,反应位点数量成为限速步骤.     

掺钴水钠锰矿对铅的吸附及对砷的氧化

为了研究过渡金属离子掺杂对锰氧化物作为环境友好材料物理化学性质的影响,在浓盐酸还原高锰酸钾制备水钠锰矿过程中添加氯化钴,在常压回流条件下一步合成了三维纳米微球状水钠锰矿,考察了其铅吸附和砷氧化能力.应用粉晶X射线衍射、化学分析、N2物理吸附、场发射扫描电镜（FE-SEM）、X射线光电子能谱（XPS）等手段表征产物晶体结...     

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...     

碱性水钠锰矿氧化Cr(Ⅲ)的影响因素研究

采用氧化还原法合成3个不同氧化度的碱性水钠锰矿,并表征其晶体结构、比表面积和表面化学性质,探讨其对Cr(Ⅲ)的氧化及影响因素。研究表明:随着合成反应的n(Mn7+)/n(Mn2+)逐渐减小,合成碱性水钠锰矿的氧化度和比表面积逐渐减小,其PZC逐渐升高。反应时间和反应条件(p H、Cr(Ⅲ)浓度和矿物用量)均影响碱性水钠锰矿对Cr(Ⅲ)的氧化。在低p H值范围内Cr(Ⅲ)氧化率随着p H的增加逐渐增加,但在高p H值范围内氧化率随着p H的升高而减小。此外,Cr(Ⅲ)的氧化率随着Cr(Ⅲ)浓度的升高逐渐降低,但随着氧化度的提高显著增加。     

Metal affinities in single and multiple ion adsorption reaction at sulfide mineral surfaces

Sulfide minerals are found in porous media in both aerobic and anaerobic environments, they should have a high affinities for certain metals. The relative binding affinities and reaction processes for 10 metal/metalloid ions reacting with four sulfide mineral surfaces has been defined.The order of reactivity is chalcocite > pyrite > galena >> sphalerite. For any particular metal and mineral, the greater reactivity occurs in the single-ion metal system except Ag(I) on pyrite and Cu(II) on galena.Both precipitation and adsorption reaction can decrease metal ion mobility on porous media, the order of metal mobility in the presence of the four sulfide minerals is predicted to be: Zn(II), Cd(II) and Ni(II) - mobile; Cu(II), Pb(II), Fe(III), As(III) and Cr(III) - variable mobility and Ag(I) - immobile.MINTEQA1 predictions on metal phase distribution / partitioning compared quite well with those observed experimentally. Solubility product considerations, intrinsic acidity constant of the mineral, EH, pH and th     

Anaerobic oxidation of arsenite by bioreduced nontronite

The redox state of arsenic controls its toxicity and mobility in the subsurface environment. Understanding the redox reactions of arsenic is particularly important for addressing its environmental behavior. Clay minerals are commonly found in soils and sediments, which are an important host for arsenic. However, limited information is known about the redox reactions between arsenic and structural Fe in clay minerals. In this study, the redox reactions between As(III)/As(V) and structural Fe in nontronite NAu-2 were investigated in anaerobic batch experiments. No oxidation of As(III) was observed by the native Fe(III)-NAu-2. Interestingly, anaerobic oxidation of As(III) to As(V) occurred after Fe(III)-NAu-2 was bioreduced. Furthermore, anaerobic oxidization of As(III) by bioreduced NAu-2 was significantly promoted by increasing Fe(III)-NAu-2 reduction extent and initial As(III) concentrations. Bioreduction of Fe(III)-NAu-2 generated reactive Fe(III)-O-Fe(II) moieties at clay mineral edge sites. Anaerobic oxidation of As(III) was attributed to the strong oxidation activity of the structural Fe(III) within the Fe(III)-O-Fe(II) moieties. Our results provide a potential explanation for the presence of As(V) in the anaerobic subsurface environment. Our findings also highlight that clay minerals can play an important role in controlling the redox state of arsenic in the natural environment.     

氧化亚铁硫杆菌密度与营养供给对硫铁矿生物氧化的影响

探究硫铁矿生物氧化过程的影响因素有利于揭示酸性矿山废水形成规律.本研究采用摇瓶试验,探究了氧化亚铁硫杆菌Acidithiobacillus ferrooxidans LX5(A.ferrooxidans LX5)密度对硫铁矿生物氧化的影响.同时,在菌密度为1.40×107cells·m L-1的环境中,研究了微生物营养(无铁改进型9K液体培养基)供给对硫铁矿生物氧化的影响.结果表明,A.ferrooxidans LX5及其营养成分的引入显著加速了硫铁矿生物氧化体系H+的释放,0.70×107~2.10×107cells·m L-1A.ferrooxidans LX5的引入,可使得H+释放量较无菌对照提高1.51~3.31倍.半量浓度和全量浓度无铁改进型9K液体培养基的加入,可使菌密度为1.40×107cells·m L-1硫铁矿氧化体系的H+释放量提高3.24与2.75倍.相对于A.ferrooxidans LX5密度为0.70×107cells·m L-1的体系,1.40×107cells·m L-1或2.10×107cells·m L-1A.ferrooxidans LX5的引入明显提高硫铁矿氧化体系总Fe离子与SO2-4的释放效率,且71.9%~88.3%的总Fe离子主要以Fe2+存在.微生物营养供给使得总Fe离子与SO2-4的释放效率加速显著,而总Fe离子几乎全部以Fe3+存在.当菌密度大于1.40×107cells·m L-1时,体系生物氧化后所得硫铁矿表面存在明显的侵蚀坑.相对于半量浓度改进型9K培养基养分供给,全量改进型9K液体培养基的引入由于体系次生铁矿物覆盖硫铁矿明显而抑制了总Fe离子与SO2-4的释放.硫铁矿氧化所得酸性废水经Ca O中和至pH约为7.00,总Fe近乎全部去除,而SO2-4去除率相对较低(26.7%~73.9%).本研究所得结果对明晰酸性矿山废水形成规律具有一定的指导意义.     

Simultaneous Fe(III) reduction and ammonia oxidation process in Anammox sludge

In recent years, there have been a number of reports on the phenomenon in which ferric iron (Fe(III)) is reduced to ferrous iron [Fe(II)] in anaerobic environments, accompanied by simultaneous oxidation of ammonia to NO₂^-, NO₃^-, or N₂. However, studies on the relevant reaction characteristics and mechanisms are rare. Recently, in research on the effect of Fe(III) on the activity of Anammox sludge, excess ammonia oxidization has also been found. Hence, in the present study, Fe(III) was used to serve as the electron acceptor instead of NO₂^-, and the feasibility and characteristics of Anammox coupled to Fe(III) reduction (termed Feammox) were investigated. After 160days of cultivation, the conversion rate of ammonia in the reactor was above 80%, accompanied by the production of a large amount of NO₃^- and a small amount of NO₂^-. The total nitrogen removal rate was up to 71.8%. Furthermore, quantities of Fe(II) were detected in the sludge fluorescence in situ hybridization (FISH) and denaturated gradient gel electrophoresis (DGGE) analyses further revealed that in the sludge, some Anammox bacteria were retained, and some microbes were enriched during the acclimatization process. We thus deduced that in Anammox sludge, Fe(III) reduction takes place together with ammonia oxidation to NO₂^- and NO₃^- along with the Anammox process.     

Mn(Ⅲ)在水钠锰矿氧化Cr(Ⅲ)反应中的作用

环境中的氧化锰矿物是可氧化Cr(Ⅲ)的唯一天然无机氧化剂,氧化锰矿物与Cr(Ⅲ)相互作用的反应速率与机制备受关注.本研究以水钠锰矿为对象,采用批量动力学方法研究了其结构中Mn(Ⅲ)在氧化Cr(Ⅲ)反应中的作用及动力学特点.结果表明,水钠锰矿氧化Cr(Ⅲ)符合准一级动力学方程,表观速率常数Kobs为0.0313 min-1,以Na4P2O7预处理水钠锰矿可络合出结构中的部分Mn(Ⅲ),使其Mn的平均氧化度升高.当处理Na4P2O7浓度为10、20、50 mmol/L时,其Mn氧化度由3.50升高至3.63、3.73和3.78,处理后的水钠锰矿对Cr(Ⅲ)的平衡氧化率增加,但初始氧化速率变化并不明显,其相应表观速率常数分别为0.0351、0.0325和0.0309 min-1.水钠锰矿氧化Cr(Ⅲ)的反应历程中,Mn(Ⅳ)→Mn(Ⅲ)的电子转移过程生成的Mn(Ⅲ)显著影响水钠锰矿氧化Cr(Ⅲ)的速率.当新生成Mn(Ⅲ)被Na4P2O7络合后,反应速率降低45%~88%,且水钠锰矿的氧化度较低时,结构中Mn(Ⅲ)含量高,反应中被络合的新生态Mn(Ⅲ)多,反应速率降低幅度相对较大.因此,反应新生成的Mn(Ⅲ)具有较高的反应活性和较快的电子转移速率,而Mn(Ⅳ)→Mn(Ⅲ)的电子转移速率较慢,可能为水钠锰矿氧化Cr(Ⅲ)的反应速率控制步骤.     

The effect of light on the Mn(II) or Fet(lll)-catalyzed oxidation of aqueous S(IV)

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稀土钙钛矿型催化剂对CO催化氧化活性及表面氧种的研究

研究了CO在不同催化剂La1 -xSrxMn1 -xBxO3(B =Fe、Ni、Cr)上的氧化反应活性 ,并利用程序升温热脱附(TPD)的方法对不同x值催化剂表面氧种及其含量的变化规律进行了考察 ,结合反应活性及表面吸附氧种随x值的变化规律 ,研究了催化剂对CO氧化反应的活性与表面活性氧种的关系。