Surface complexation of Pb(II) by hexagonal birnessite nanoparticles

Natural hexagonal birnessite is a poorly crystalline layer type Mn(IV) oxide precipitated by bacteria and fungi which has a particularly high adsorption affinity for Pb(II). X-ray spectroscopic studies have shown that Pb(II) forms strong inner-sphere surface complexes mainly at two sites on hexagonal birnessite nanoparticles: triple corner-sharing (TCS) complexes on Mn(IV) vacancies in the interlayers and double edge-sharing (DES) complexes on lateral edge surfaces. Although the TCS surface complex has been well characterized by spectroscopy, some important questions remain about the structure and stability of the complexes occurring on the edge surfaces. First-principles simulation techniques such as density functional theory (DFT) offer a useful way to address these questions by providing complementary information that is difficult to obtain by spectroscopy. Following this computational approach, we used spin-polarized DFT to perform total-energy-minimization geometry optimizations of several possible Pb(II) surface complexes on model birnessite nanoparticles similar to those that have been studied experimentally. We first validated our DFT calculations by geometry optimizations of (1) the Pb-Mn oxyhydroxide mineral, quenselite (PbMnO₂OH), and (2) the TCS surface complex, finding good agreement with experimental structural data while uncovering new information about bonding and stability. Our geometry optimizations of several protonated variants of the DES surface complex led us to conclude that the observed edge-surface species is very likely to be this complex if the singly coordinated terminal O that binds to Pb(II) is protonated. Our geometry optimizations also revealed that an unhydrated double corner-sharing (DCS) species that has been proposed as an alternative to the DES complex is intrinsically unstable on nanoparticle edge surfaces, but could become stabilized if the local coordination environment is well-hydrated. A significant similarity exists in the structural parameters for the TCS complex and those for a DCS edge-surface complex that is protonated in the same manner as the optimal DES complex, which could complicate detecting the DCS complex in X-ray absorption spectra.     

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

The kinetics of iodide (I⁻) and molecular iodine (I₂) oxidation by the manganese oxide mineral birnessite (δ-MnO₂) was investigated over the pH range 4.5-6.25. I⁻ oxidation to iodate proceeded as a two-step reaction through an I₂ intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I⁻ from solution was first order with respect to I⁻ concentration, pH, and birnessite concentration, such that −d[I⁻]/dt = k[I⁻][H⁺][MnO₂], where k, the third order rate constant, is equal to 1.08 ± 0.06 × 10⁷ M⁻² h⁻¹. The data are consistent with the formation of an inner sphere I⁻ surface complex as the first step of the reaction, and the adsorption of I⁻ exhibited significant pH dependence. Both I₂, and to a lesser extent, sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I₂ and , as well as the biophilic nature of I₂, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.     

Mechanisms of siderophore sorption to smectite and siderophore-enhanced release of structural Fe

Sorption of the trihydroxamate siderophores desferrioxamine-B and -D (DFOB and DFOD, respectively) and of the monohydroxamate ligand acetohydroxamic acid (aHA) to smectite were examined in batch sorption studies (pH 5.5, 0.1 M ionic strength) coupled with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Both DFOB and DFOD, which have similar molecular structures but different charge properties (cationic versus neutral, respectively) showed a high affinity for smectite. In contrast, the smaller aHA molecule did not sorb appreciably. XRD analysis indicated that DFOB and DFOD each absorbed in the interlamellar region of the clay to give d-spacings of 13.4-13.7 Å at equilibrium solution concentrations <250 μM. FTIR spectra of sorbed DFOB and DFOD indicated that the conformation of each species was distinct from its conformation in the crystalline or dissolved states. At elevated initial solution concentrations of 500-1500 μM, DFOB formed a bilayer in the clay interlayer. Changes in the FTIR spectra of the DFOB-loaded clay samples at these higher surface loadings were consistent with the presence of a metal-siderophore complex in the interlayer. DFOB and DFOD both enhanced Fe and Al release from smectite, but aHA did not. Possible dissolution mechanisms are discussed in light of the FTIR and batch dissolution results.     

水钠锰矿氧化硫化物的过程与动力学研究

水钠锰矿是表生环境中常见的氧化锰矿物之一,影响土壤溶液中硫化物的迁移、转化和归趋。本文考察了酸性水钠锰矿氧化硫化钠溶液的反应过程,采用分光光度法、离子色谱法分析S2-及其氧化产物的浓度和变化趋势,用XRD、SEM表征酸性水钠锰矿粉末反应前后的晶体结构和微观形貌,探讨了温度、pH值、矿物用量对S2-氧化速率的影响。结果表明,S2-的氧化产物主要为单质S,其氧化速率符合准一级动力学规律,且氧化速率随着温度升高、pH值降低和矿物用量增加而增大;酸性水钠锰矿首先被还原生成Mn(OH)2,Mn(OH)2在空气中与O2作用转化成Mn3O4,Mn3O4可进一步转化生成MnOOH。     

Nitrate sorption by organosmectites

The use of organoclays as adsorbents in the remediation of polluted water has been the subject of many recent studies. In this present work, a Tunisian smectite modified by two cationic surfactants was used as a sorbent for the investigation of the adsorption kinetics, isotherms and thermodynamic parameters of nitrate ions at various contact time, initial concentrations and temperatures. Two simplified kinetic models, first-order and second-order, were used to predict the adsorption constants. It was found that the adsorption kinetics of nitrate was best described by the second-order model. Adsorption isotherms and equilibrium adsorption capacities were determined by the fittings of the experimental data to two well-known isotherm models including Langmuir and Freundlich. The results showed that Langmuir model appears to fit the adsorption better than Freundlich model. The equilibrium constants were used to calculate thermodynamic parameters, such as the change of free energy, enthalpy and entropy.     

Selective nickel and cobalt uptake from pressure sulfuric acid leach solutions using column resin sorption

Selective removal of Ni and Co, from a high pressure acid leach (HPAL) solution of a Brazilian laterite nickel ore that contains relatively high concentration of impurities, was carried out with an ion exchange chelating resin possessing iminodiacetic acid group (Amberlite IRC 748®). The resin was tested in column experiments. The experimental results showed that higher pH values improved the ion exchanger performance and higher nickel load capacities were achieved. Besides, increasing nickel concentration in solution, nickel uptake and selectivity were substantially improved. The breakthrough experimental curves also showed that many metals were immediately brokenthrough just after the initiation of the feed, while the breakthrough of Ni began later. These results suggested that it is feasible to purify HPAL solution recovering nickel selectively using the chelating resin Amberlite IRC748® if some specific conditions related to pH, flow rate and nickel concentration are applied. Removal of metals from the resin was successfully performed with HCl and H₂SO₄ solutions. Nickel was eluted concentrated more than 20 times its initial concentration in the feed solution, while only a trace amount of impurities was eluted.     

碱性介质中合成水钠锰矿的几个影响因素

水钠锰矿是土壤和沉积物中常见的氧化锰矿物。较系统地研究了碱性介质中合成水钠锰矿几个影响因素的作用规律。结果表明,在实验条件下,反应液的流动速率和氧气流量是合成水钠锰矿的主要影响因素,在反应中使用机械搅拌,可以使水钠锰矿的合成简单易行;而反应前通氮气处理和反应温度对水钠锰矿的合成没有影响;实验合成单相水钠锰矿的条件为:OH-/Mn摩尔比为13.7,O2的流量2L/min,在常温和机械搅拌下氧化5h;其平均化学组成为Na0.25MnO2.07·0.66H2O。     

Processes and kinetics of Cd2+ sorption by a calcareous aquifer sand

The rate of Cd²⁺ sorption by a calcareous aquifer sand was characterized by two reaction steps, with the first step reaching completion in 24 hours. The second step proceeded at a slow and nearly constant rate for at least seven days. The first step includes a fast adsorption reaction which is followed by diffusive transport into either a disordered surface film of hydrated calcium carbonate or into pore spaces. After 24 hours the rate of Cd²⁺ sorption was constant and controlled by the rate of surface coprecipitation, as a solid solution of CdCO₃ in CaCO₃ formed in recrystallizing material. Desorption of Cd²⁺ from the sand was slow. Clean grains of primary minerals, e.g. quartz and aluminosilicates. sorbed much less Cd²⁺ than grains which had surface patches of secondary minerals, e.g. carbonates, iron and manganese oxides. Calcite grains sorbed the greatest amount of Cd²⁺ on a weight-normalized basis despite the greater abundance of quartz. A method is illustrated for determining empirical binding constants for trace metals at in situ pH values without introducing the experimental problem of supersaturation. The binding constants are useful for solute transport models which include a computation of aqueous speciation.     

Oxidation of arsenite to arsenate on birnessite in the presence of light

The effect of simulated solar radiation on the oxidation of arsenite [As(III)] to arsenate [As(V)] on the layered manganese oxide, birnessite, was investigated. Experiments were conducted where birnessite suspensions, under both anoxic and oxic conditions, were irradiated with simulated solar radiation in the presence of As(III) at pH 5, 7, and 9. X-ray absorption spectroscopy (XAS) was used to determine the nature of the adsorbed product on the surface of the birnessite. The oxidation of As(III) in the presence of birnessite under simulated solar light irradiation occurred at a rate that was faster than in the absence of light at pH 5. At pH 7 and 9, As(V) production was significantly less than at pH 5 and the amount of As(V) production for a given reaction time was the same under dark and light conditions. The first order rate constant (k_obs) for As(III) oxidation in the presence of light and in the dark at pH 5 were determined to be 0.07 and 0.04 h^?1, respectively. The As(V) product was released into solution along with Mn(II), with the latter product resulting from the reduction of Mn(IV) and/or Mn(III) during the As(III) oxidation process. Post-reaction XAS analysis of As(III) exposed birnessite showed that arsenic was present on the surface as As(V). Experimental results also showed no evidence that reactive oxygen species played a role in the As(III) oxidation process.     

The molecular mechanism of Mo isotope fractionation during adsorption to birnessite

Fractionation of Mo isotopes during adsorption to manganese oxides is a primary control on the global ocean Mo isotope budget. Previous attempts to explain what drives the surprisingly large isotope effect δ^97/95Mo_dissolved-δ^97/95Mo_adsorbed=1.8‰ have not successfully resolved the fractionation mechanism. New evidence from extended X-ray absorption fine structure analysis and density functional theory suggests that Mo forms a polymolybdate complex on the surfaces of experimental and natural samples. Mo in this polynuclear structure is in distorted octahedral coordination, while Mo remaining in solution is predominantly in tetrahedral coordination as . Our results indicate that the difference in coordination environment between dissolved Mo and adsorbed Mo is the cause of isotope fractionation. The molecular mechanism of metal isotope fractionation in this system should enable us to explain and possibly predict metal isotope effects in other systems where transition metals adsorb to mineral surfaces.     

The mechanisms of Co(II) oxidation on synthetic birnessite

Studies of the adsorption of Co(II) on synthetic birnessite have been carried out at pH 4, 6, 7, 8 and 10. At pH values of 4, 6 and 7 cobalt(II) is oxidized to Co(III) while at pH 8 and 10 surface cobalt corresponds to Co(II). The Co(II) produced at pH 8 and 10 appears to be Co(OH)₂ produced via precipitation on the MnO₂ surface. The oxidizing agent is identified as surface Mn(IV) from a comparison of x-ray photoelectron spectroscopic results for samples prepared at pH 6.5 under anaerobic and aerobic conditions. The identification of Mn(III) is accomplished by comparing the Mn 2p core electron binding energies and the Mn 3s multiplet splitting values with the results for a variety of manganese oxides.     

Kinetic analysis of cation exchange in birnessite using time-resolved synchrotron X-ray diffraction

In this study, we applied time-resolved synchrotron X-ray diffraction (TRXRD) to develop kinetic models that test a proposed two-stage reaction pathway for cation exchange in birnessite. These represent the first rate equations calculated for cation exchange in layered manganates. Our previous work has shown that the substitution of K, Cs, and Ba for interlayer Na in synthetic triclinic birnessite induces measurable changes in unit-cell parameters. New kinetic modeling of this crystallographic data supports our previously postulated two-stage reaction pathway for cation exchange, and we can correlate the kinetic steps with changes in crystal structure. In addition, the initial rates of cation exchange, R (ų min⁻¹), were determined from changes in unit-cell volume to follow these rate laws: R = 1.75[]^0.56, R = 41.1[]^1.10, R = 1.15[]^0.50. Thus, the exchange rates for Na in triclinic birnessite decreased in the order: Cs ? K > Ba. These results are likely a function of hydration energy differences of the cations and the preference of the solution phase for the more readily hydrated cation.     

The sorption of silver by poorly crystallized manganese oxides

The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized γ-MnO₂. All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnO_x at pH 7) while the γ-MnO₂ showed the least (0.3 moles silver/ mole MnO_x at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values.Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium.     

Arsenic sequestration by sorption processes in high-iron sediments

High-iron sediments in North Haiwee Reservoir (Olancha, CA), resulting from water treatment for removal of elevated dissolved arsenic in the Los Angeles Aqueduct system, were studied to examine arsenic partitioning between solid phases and porewaters undergoing shallow burial. To reduce arsenic in drinking water supplies, ferric chloride and a cationic polymer coagulant are added to the aqueduct upstream of Haiwee Reservoir, forming an iron-rich floc that scavenges arsenic from the water. Analysis by synchrotron X-ray absorption spectroscopy (XAS) showed that the aqueduct precipitate is an amorphous hydrous ferric oxide (HFO) similar to ferrihydrite, and that arsenic is associated with the floc as adsorbed and/or coprecipitated As(V). Arsenic-rich floc and sediments are deposited along the inlet channel as aqueduct waters enter the reservoir. Sediment core samples were collected in two consecutive years from the edge of the reservoir along the inlet channel using 30- or 90-cm push cores. Cores were analyzed for total and extractable arsenic and iron concentrations. Arsenic and iron speciation and mineralogy in sediments were examined at selected depths by synchrotron XAS and X-ray diffraction (XRD). Sediment-porewater measurements were made adjacent to the core sample sites using polyacrylamide gel probe samplers. Results showed that sediment As(V) is reduced to As(III) in all cores at or near the sediment-water interface (0-4 cm), and only As(III) was observed in deeper sediments. Analyses of EXAFS spectra indicated that arsenic is present in the sediments mostly as a bidentate-binuclear, inner-sphere sorption complex with local atomic geometries similar to those found in laboratory studies. Below about 10 cm depth, XAS indicated that the HFO floc had been reduced to a mixed Fe(II, III) solid with a local structure similar to that of synthetic green rust (GR) but with a slightly contracted average interatomic Fe-Fe distance in the hydroxide layer. There was no evidence from XRD for the formation of a crystalline GR phase. The release of dissolved iron (presumably Fe²⁺) and arsenic to solution, as monitored by in situ gel probes, was variable but, in general, occurred at greater depths than arsenic reduction in the sediments by spectroscopic observations and appears to be near or below the depth at which sediment GR was identified. These data point to reductive dissolution of the sorbent iron phase as the primary mechanism of release of sorbed arsenic to solution.     

The formation of todorokite and birnessite in sea water pumped from under ground

Manganese oxides precipitated from aerated well sea water at the Marine Science Museum, Tokai University, have been analyzed chemically and mineralogically. The $\text{O}\text{Mn}$ ratios are lower in todorokite than in birnessite but these minerals have similar contents of minor transition metals, which can be taken up additionally from sea water after the precipitation of Mn oxides. On the basis of these results, the genesis of Mn minerals is discussed in relation to marine Mn nodules.     

Diffusion and sorption experiments using a DKS permeameter

The analysis of contaminant transport through clay liner is a relevant aspect in the design of industrial, urban and mining waste disposal systems, since these areas must be designed and operated to prevent contaminating substances from reaching underground water systems in unacceptable concentrations. The design requires an estimate of the potential contaminant transport rate. However, before any attempt at quantification can be made, values for transport mechanism control parameters must be established. Clayey materials are frequently used as contaminant barriers. In these materials, which have low hydraulic conductivity, the main contaminant transport mechanism is molecular diffusion. Parameters controlling transport for these conditions are the diffusion coefficient and sorption parameters. These parameters depend on soil constituents and characteristics as well as on the chemical constitution of the contaminant. The great complexity of the factors involved makes it necessary to determine the parameters of each type of soil. This paper discusses an equipment called DKS permeameter (diffusion, convection, sorption), for the study of soil-contaminant transport mechanisms, designed at the Institute for Soil Mechanics of the Ruhr-University Bochum, and some results obtained from its use at COPPE/Federal University of Rio de Janeiro (UFRJ), Brazil. This equipment determines the effective diffusion coefficient and sorption parameter with a better reflection of field conditions. The soil under study is a mix of sodium–bentonite that has low hydraulic conductivity (k=10⁻⁹ cm/s) with adequate liner characteristics. The result indicated the relevance of determining sorption parameters for structured soils, since the sorption perceived from batch test results using pulverised soil represents maximum soil capacity. Designs based on this parameter would overestimate the attenuation capacity of the liner.     

太阳能电池协同强化水钠锰矿光电催化染料降解研究

电催化、光催化、光电催化等电化学技术以其高效、廉价、环保等特点被认为是一种极具前途的环境污染深度净化技术,在有机废水处理等方面得以广泛应用。本文借助电化学电量控制法制备了水钠锰矿电极,通过X射线衍射(XRD)、扫描电镜(SEM)表征其物相形貌,UV-Vis漫反射吸收谱结果表明水钠锰矿对300~600 nm波长范围可见光表现出良好吸收能力,计算其直接带隙约为2.14 e V,Mott-Schottky曲线计算其平带电位约1.15 V,0.1 mol/L Na2SO4介质中载流子浓度约为3.3×1019cm-3,是良好的可见光激发n型半导体材料。同时,本文以廉价高效的太阳能电池板取代了传统电化学工作站等外加电场设备,成功实现了协同强化水钠锰矿光电催化降解作用。协同作用下甲基橙60 min降解率为90.2%,效率远高于水钠锰矿光催化(2.2%)与电极电催化(33.6%)作用,强化了水钠锰矿光电催化降解反应,节省能耗的同时显著提高了降解效率。批次循环降解实验表明第4轮降解率(86.8%)较之第1轮(90.3%)降低程度5%,表明其具有良好长时间运行稳定性。