The Structure of manganese oxide formed by the fungus Acremonium sp. strain KR21-2

Manganese oxides are observed to form by the oxidation of aqueous solutions of Mn(II) catalyzed by the action of microorganisms. In contrast to the widely studied material produced by bacteria, manganese oxide phases produced by the action of fungi have received only limited attention.A detailed study of the MnO_x material produced by the action of the fungus Acremonium KR21-2, utilizing X-ray diffraction, XANES, EXAFS and transmission electron microscopy is reported. The MnO_x material is produced as small crystalline particles which adopt a todorokite-like tunnel structure, in striking contrast to previously reported microbial MnO_x materials which adopt layered birnessite-type structures. ICPMS measurements reveal there are no templating metal ions present in the fungally mediated MnO_x material, in contrast to analogous bacterially mediated material, suggesting these cations play a critical role in determining the structure of the material precipitated. A phylogenetic analysis places KR21-2 with other Acremonium species in the Hypocreales.     

Photocatalytic performance of TiO<Subscript>2</Subscript> and WO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanoparticles coated on urban green infrastructure materials in removing nitrogen oxide

This study investigated the performance of UV light active TiO₂ and UV–visible light active WO₃/TiO₂ nanoparticles as air purifying materials that can be potentially applied to urban green infrastructures such as rain gardens and pervious pavements. Using a laboratory-scale continuous gas flow photoreactor, the removal efficiency of gaseous nitrogen oxide (NO _x ) by two different photocatalytic nanoparticles coated on natural zeolites and pervious concrete blocks was evaluated. The results showed that the TiO₂- and WO₃/TiO₂-coated zeolites are excellent photoactive materials providing enhanced air purification function (~95% removal efficiency of NO _x ) under UV and UV–visible light irradiation, respectively. In contrast, both of the TiO₂- and WO₃/TiO₂-coated pervious concrete blocks showed a measurable NO _x removal (~60%) only under UV irradiation, whereas the visible light activity of the WO₃/TiO₂-coated concrete block was significantly reduced (~20%) mainly due to the decrease in the photocatalytic reaction sites for visible light. This study revealed the potential utility of photocatalytic nanoparticles in improving urban air quality, in the form of the surface component of various urban infrastructures.     

Ferromanganese oxide deposits from the Central Pacific Ocean,I. Encrustations from the Line Islands Archipelago

Chemical and mineralogical analyses of a well-controlled suite of ferromanganese encrustations from the Line Islands Archipelago (Central Pacific) suggest that they represent purely hydrogenous deposits—i.e. they have formed through the slow accumulation of trace metal-enriched oxides directly from the water-column. Mineralogically they consist predominantly of δMnO₂ and amorphous FeOOHxH₂O. Compositionally, they are similar to δMnO₂ nodules from adjoining basinal areas but are enriched in both Mn (mean = 20.4%, max = 29.3%) and Co (mean = 0.55%, max = 1.57%). δMnO₂ is the most important trace metal bearing phase; strong associations are noted between it and Co, Mo, Ni, Zn, and Cd, whilst only Be is associated specifically with FeOOH. V, Sr and Pb are partitioned between the authigenic oxide phases, whilst Ti most probably occurs as TiO₂xH₂O. Cu is contained in both aluminosilicate contaminant phases and Fe oxide phases. These relations are considered to reflect the differing scavenging behaviour of Mn and Fe oxides in the water column.Crusts from ~1–2 km are enriched in Mn and the Mn-related elements and exhibit higher $\text{Mn}\text{Fe}$ ratios than deeper crusts, which are compositionally constant. The higher $\text{Mn}\text{Fe}$ ratios may result from a supply of Mn from continental borderland sediments at these depths, which is transported horizontally by advective-diffusive processes. Since manganophile elements are enriched relative to Mn in the 1–2 km crusts, it is considered that the supply of Mn is scavenged by existing oxides, is oxidised and effectively occludes them. A higher proportion of oxide particles thus exhibit Mn oxide scavenging properties in the 1–2 km depth zone. The increased vertical flux of Mn resulting from the supply at ~1–2 km is not reflected by higher $\text{Mn}\text{Fe}$ ratios in deeper crusts, so that the vertical flux of oxides is not simply related to the standing crop. The $\text{Mn}\text{Fe}$ ratios of the crusts thus reflect the composition of suspended oxides at similar depths.     

Influence of energy efficiency on VOCs decomposition in non-thermal plasma reactor

In order to promote the plasma technology for commercial application and improve the energy efficiency of non-thermal plasma, a series of experiments on energy efficiency of plasma reactor were carried out for volatile organic compounds removal. This research adopts a pipe-line reaction device with plasma generated by dielectric barrier discharge technology to examine the effects of different experimental parameters, including medium packing, electric field strength, the pollutant initial concentration, and gas velocity, on the energy efficiency. In the study, four kinds of packed materials were packed into the plasma reactor: a complex catalyst, Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃, MnO₂/γ-Al₂O₃, and γ-Al₂O₃. Through optimizing the experimental parameters, the best decomposition efficiency of toluene and the best energy efficiency were achieved. The experimental results show that the energy efficiency has a trend from increasing to decreasing with increasing pollutant gas velocity, and the energy efficiency changes from increasing to decreasing with the increasing of initial concentration of pollutants, and the decomposition efficiency and the energy efficiency have the same order from high to low with different packed materials in the plasma reactors, in turn, packed with complex catalyst, Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃, MnO₂/γ-Al₂O₃, γ-Al₂O₃ and no padding. The optimized parameters for toluene decomposition are: the gas flow rate of 2 mL/min, the initial concentration range of 1500–2000 mg/m³, the field strength intensity of 9.6 kV/cm, and the plasma reactor packed with a complex catalyst, which results in the best energy efficiency of 10 g/kWh. This research provides not only a new way to develop the plasma technology, but also a reference for the commercial application.     

Decomposition of benzene by non-thermal plasma processing: Photocatalyst and ozone effect

Plasma technology has some shortcomings, such as higher energy consumption and byproducts produced in the reaction process. However non-thermal plasma associated with catalyst can resolve these problems. Therefore this kind of technology was paied more and more attention to treat waste gas. A hybrid system comprising a non-thermal plasma reactor and nanometer titanium dioxide catalyst was used for benzene removal in the air. The paper described the synergistic effect of ozone and photocatalyst in the plasma reactor. Except of electric field strength, humidity and flow velocity, the synergistic behavior of ozone and photocatalyst was tested. The removal efficiency of benzene reaches nearly 99% when benzene concentration is 600 mg/m³, and the removal efficiency of benzene also reaches above 90% when benzene concentration is 1500 mg/m³. The plasma reactor packed with photocatalyst shows a better selectivity of carbon dioxide than that without photocatalyst. The final products is mostly carbon dioxide, water and a small quantity of carbon monoxide.     

A new particulate Mn-Fe-P-shuttle at the redoxcline of anoxic basins

Pelagic redoxclines of anoxic basins and deeps form the suboxic transition between oxygenated surface and anoxic or even sulfidic bottom waters. Intense element cycling, favoured by elevated microbial activity, causes steep gradients of physico-chemical parameters, nutrients and redox-sensitive trace metals. This study presents a conceptual model for authigenic particle formation at pelagic redoxclines, which is based on the tight coupling of Mn, Fe, and P cycles. Besides the well-known occurrence of Mn-oxides, textural (SEM-EDX) and geochemical (ICP-OES, ICP-MS) analyses of particles from the redoxclines of the Black Sea and the Baltic Sea (Gotland Basin, Landsort Deep) evidence the existence of earlier postulated Fe-oxyhydroxo-phosphates and emphasize mixed phases consisting of Mn-oxides and Fe-oxyhydroxo-phosphates as a new solid species. Most of the analyzed particles are star-shaped, of about 5 μm in size, and occur as single particles or aggregates without any morphological differences between Mn-oxides, Fe-oxyhydroxo-phosphates, and mixed phases. Throughout the redoxcline, these minerals show a general succession with maximum abundance of Mn-oxides above the redoxcline followed by mixed phases and almost pure Fe-phosphates within and below the redoxcline, respectively. Molar Fe/P ratios of single particles argue against the formation of known pure Fe-phosphates like vivianite or strengite at the lower end of the redox transition zone, but are consistent with recent experimental findings for colloidal P-bearing hydrous ferric oxides. Moreover, morphological similarities suggest the formation of irregular Fe-oxyhydroxo coatings due to oxidation of upward diffusing Fe²⁺ by oxygen and stepwise replacement of Mn(IV) by Fe(III) on sinking MnO_x particles followed by immediate adsorption or even co-precipitation of phosphate. Batch-type experiments using biogenic MnO_x particles demonstrate the efficient potential of Fe²⁺ oxidation by sinking MnO_x particles. When entering sulfidic waters MnO_x particles are progressively reduced leading to an increasing relative abundance of Fe- and P-rich particles. In deeper parts of the water column these particles are also reductively dissolved, thereby releasing Fe²⁺ and phosphate to the water column. This Mn-Fe-P-shuttle likely affects phosphate transport throughout the water column and thus impacts primary production at least over longer time scales. Furthermore, the particulate Mn-Fe-P-shuttle must have played an important role for the cycling of P and certain trace metals in ancient ocean basins, e.g., during certain periods of Cretaceous black shale formation and should be considered in future mass balances and modeling approaches dealing with oxic/anoxic interfaces of aquatic ecosystems.     

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.     

Defining manganese(II) removal processes in passive coal mine drainage treatment systems through laboratory incubation experiments

Oxic limestone beds are commonly used for the passive removal of Mn(II) from coal mine drainage (CMD). Aqueous Mn(II) is removed via oxidative precipitation of Mn(III/IV) oxides catalyzed by Mn(II)-oxidizing microbes and Mn oxide (MnO_x) surfaces. The relative importance of these two processes for Mn removal was examined in laboratory experiments conducted with sediments and CMD collected from eight Mn(II)-removal beds in Pennsylvania and Tennessee, USA. Sterile and non-sterile sediments were incubated in the presence/absence of air and presence/absence of fungicides to operationally define the relative contributions of Mn removal processes. Relatively fast rates of Mn removal were measured in four of the eight sediments where 63–99% of Mn removal was due to biological oxidation. In contrast, in the four sediments with slow rates of Mn(II) removal, 25–63% was due to biological oxidation. Laboratory rates of Mn(II) removal were correlated (R² = 0.62) to bacterial biomass concentration (measured by phospholipid fatty acids (PLFA)). Furthermore, laboratory rates of Mn(II) removal were correlated (R² = 0.87) to field-scale performance of the Mn(II)-removal beds. A practical recommendation from this study is to include MnO_x-coated limestone (and associated biomass) from an operating bed as “seed” material when constructing new Mn(II)-removal beds.     

Volatile organic compounds decomposition using nonthermal plasma coupled with a combination of catalysts

A series of experiments were performed for toluene decomposition from a gaseous influent at normal temperature and atmospheric pressure by nonthermal plasma coupled with a combination of catalysts technology. Nonthermal plasma was generated by dielectric barrier discharge. γ-Al₂O₃ was used to be a sorbent and a catalyst carrier. Nanocatalysts were MnO₂/γ-Al₂O₃ coupled with modified ferroelectric of nano-Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃. γ-Al₂O₃ played an important role in prolonging reaction time of nonthermal plasma with volatile organic compounds molecules. MnO₂/γ-Al₂O₃ has an advantage for ozone removal, while nano-Ba_0.8Sr_0.2Zr_0.1Ti_0.9O₃ is a kind of good ferroelectric material for improving energy efficiency. Thus these packed materials were incorporated together to strengthen nonthermal plasma power for volatile organic compounds decomposition. The results showed the synergistic technology resulted in greater enhancement of toluene removal and energy efficiencies and a better inhibition for ozone formation in the gas exhaust. Based on the data analysis of the Fourier transforms infrared spectrum, the reaction process of toluene decomposition and the mechanism of synergistic effect are discussed. The results showed in a complex oxidation mechanism of toluene via several pathways, producing either ringretaining or ringopening products. The final products were carbon dioxide and water.     

Characterization of manganese oxide precipitates from Appalachian coal mine drainage treatment systems

The removal of Mn(II) from coal mine drainage (CMD) by chemical addition/active treatment can significantly increase treatment costs. Passive treatment for Mn removal involves promotion of biological oxidative precipitation of manganese oxides (MnO_x). Manganese(II) removal was studied in three passive treatment systems in western Pennsylvania that differed based on their influent Mn(II) concentrations (20–150 mg/L), system construction (±inoculation with patented Mn(II)-oxidizing bacteria), and bed materials (limestone vs. sandstone). Manganese(II) removal occurred at pH values as low as 5.0 and temperatures as low as 2 °C, but was enhanced at circumneutral pH and warmer temperatures. Trace metals such as Zn, Ni and Co were removed effectively, in most cases preferentially, into the MnO_x precipitates. Based on synchrotron radiation X-ray diffraction and Mn K-edge extended X-ray absorption fine structure spectroscopy, the predominant Mn oxides at all sites were poorly crystalline hexagonal birnessite, triclinic birnessite and todorokite. The surface morphology of the MnO_x precipitates from all sites was coarse and “sponge-like” composed of nm-sized lathes and thin sheets. Based on scanning electron microscopy (SEM), MnO_x precipitates were found in close proximity to both prokaryotic and eukaryotic organisms. The greatest removal efficiency of Mn(II) occurred at the one site with a higher pH in the bed and a higher influent total organic C (TOC) concentration (provided by an upstream wetland). Biological oxidation of Mn(II) driven by heterotrophic activity was most likely the predominant Mn removal mechanism in these systems. Influent water chemistry and Mn(II) oxidation kinetics affected the relative distribution of MnO_x mineral assemblages in CMD treatment systems.     

The adsorption of aqueous heavy metals on inorganic minerals

Two models have been used to explain the in-situ control of heavy metals: (1) solubility controls, where precipitation of a solid phase occurs under varying metal and ligand concentrations, and (2) surface chemical controls, where adsorption or exchange occurs at the solid/solution interface. Based on experiments presented in this paper, surface chemical controls can account for the removal of heavy metals, particularly Zn(II), from metal solutions which are undersaturated with respect to the hydroxide, oxide, or other controlling solid phases. Adsorption isotherms are presented for varying solution pHs, total metal ion concentrations, ionic strengths, and mineral substrates. The minerals chosen for illustration are SiO₂, TiO₂, FeOOH, Al₂O₃, MnO_x and HgS which range widely in surface acidity, electrical double layer properties, specific surface areas, and surface functional groups.     

Oxide solution mechanisms in silicate melts: Systematic variations in the activity coefficient of SiO2

Phase equilibria and spectroscopic data are used to develop a simple model for the interaction of various oxide components and molten SiO₂. Network modifying oxides, M_xO_y produce nonbridging oxygens thereby depolymerizing the SiO₂ network. The energetics of nonbridging oxygen formation are least favorable when the field strength of the metal cation is high. This produces relatively strong M-O and Si-O-Si bridging bonds at the expense of weaker Si-O-M bonds (De Jonget al., 1980). This relationship is manifested by an increase in positive deviations from ideality with increasing cation field strength in M_xO_y-SiO₂ systems; the activity coefficient of SiO₂ is inversely correlated with Si-O-M bond strength. Network forming oxides (aluminates, phosphates, titanates. zirconates, etc.) may copolymerize with the SiO₂ network. Mixing on the same quasi-lattice produces solutions which approach ideality. Deviations from ideality in such solutions can be linked to distortions in the SiO₂ network. Discrete anion formers (phosphates, titanates, chromates, zirconates) complex with metal oxides other than SiO₂ to form discrete structural units which do not copolymerize with SiO₂. The SiO₂ network is essentially shielded from the high charge density cations in such systems and unmixing is common. As a result, the relative deviations from ideality in such melts are high. It is important to recognize that oxides such as P₂O₅, TiO₂ and ZrO₂ may act as either network-formers or discrete anion formers depending upon melt composition, and are probably distributed between these two “sites” in most geologically important liquids. The latter structural role is favored in more basic compositions.     

Oxidation of manganese by spores of a marine bacillus: Kinetic and thermodynamic considerations

The catalytic properties of spores of a marine Bacillus known to oxidize divalent manganese were used to perform laboratory Mn(II) oxidation experiments at environmental conditions of pH and Mn(II) concentration. We found that at pH 7.8 the initial kinetics of Mn(II) oxidation facilitated by the spores was four orders of magnitude greater than that which would be expected for abiotic autocatalysis on a colloidal MnO₂ surface. The rate progressively decreased as the spores became coated with manganese oxide, eventually becoming very near that predicted for abiotic surface catalysis. Transmission electron microscopic observations and oxidation state measurements of solids precipitated at pH 7.5 and [Mn(II)] < 50 nM indicated that the initial oxidation product was hausmannite (Mn₃O₄ or MnO_x where x = 1.33) which aged to more highly oxidized MnO₂ (x = 1.9) in the time scale of weeks. By utilizing spores to catalyze the oxidation rate, we were able to maintain our experimental system within the seawater range of pH and Mn(II) where highly oxidized manganese oxide precipitates are thermodynamically stable. In doing so we obtained, for the first time, laboratory precipitates with oxidation states similar to that found in marine particulate material. These results suggest that the concentration of manganese in seawater and the oxidation state of marine manganese oxides are controlled by the rapid precipitation of Mn₃O₄, which can be microbially mediated, followed by the disproportionation to MnO₂.     

Rapid photo-oxidation of Mn(II) mediated by humic substances

The oxidation of Mn(II) by O₂ to Mn(III) or Mn(IV) is thermodynamically favored under the pH and pO₂ conditions present in most near surface waters, but the kinetics of this reaction are extremely slow. This work investigated whether reactive oxygen species, produced through illumination of humic substances, could oxidize Mn at an environmentally relavent rate. The simulated sunlight illumination of a solution containing 200 μM Mn(II) and 5 mg/L Aldrich humic acid buffered at pH 8.1 produced ∼19 μM of oxidized Mn (MnO_x where x is between one and two) after 45 minutes. The major oxidants reponsible for this reaction appear to be photoproduced superoxide radical anion, O₂⁻, and singlet molecular oxygen, ¹O₂. The dependencies of MnO_x formation on Mn(II), humic acid, and H⁺ concentration were characterized. A kinetic model based largely on published rate constants was established and fit to the experimental data. As expected, analysis of the model indicates that the key reaction rate controlling MnO_x production is the rate of decomposition of a MnO₂⁺ complex formed from the reaction of Mn(II) with O₂⁻. This rate is strongly dependent on the Mn(II) complexing ligands in solution. The MnO_x production in the seawater sample taken from Bodega Bay, USA and spiked with 200 μM Mn(II) was well reproduced by the model. Extrapolations from the model imply that Mn photo-oxidation should be a significant reaction in typical surface seawaters. Calculated rates, 5.8 to 55 pM h⁻¹, are comparable to reported rates of biological Mn oxidation, 0.07 to 89 pM h⁻¹. Four fresh water samples that were spiked with 200 μM Mn(II) also showed significant MnO_x production. Based on these results, it appears that Mn photo-oxidation could constitute a significant, and apparently unrecognized geochemical pathway in natural waters.     

Gaseous phase benzene decomposition by non-thermal plasma coupled with nano titania catalyst

Synergistic effect of atmospheric non-thermal plasma generated by dielectric barrier discharge and nano titania photocatalyst for benzene decomposition was tested. The paper indicated the effect of photocatalyst on removal efficiency of benzene, the compare of photocatalyst characteristic in different high temperatures by heat treatment, analysis of by-products. The results showed that the effect of degradation was visible by added photocatalyst in the plasma reactor. When concentration of benzene was 600 mg/m3 and electric field strength was 10 kV/cm, the removal efficiency of benzene was increased up to 81 % without photocatalyst. At the same condition, the removal efficiency was increased to 15 % higher with photocatalyst. Nano titania crystal was anatase crystal in 450 °C heat treatment which is best for benzene removal. The plasma reactor packed with photocatalyst shows a better selectivity of carbon dioxide than that without photocatalyst. By-products are mostly carbon dioxide, water and a small quantity of carbon monoxide.     

Vacancy and defect structures in metal oxides

The self-consistent local density (LD) theory is used to model vacancy and defect structures in metal oxides by use of the embedded cluster scheme. LCAO-MO expansions of cluster orbitals are obtained by the DV-Xα discrete variational method, and used to characterize energy levels, charge distributions, X-ray absorption and cohesive energies. Examples are drawn from recent work on transition metal monoxides such as Fe_1?x O, ceramic materials such as yttrium-stabilized zirconia, and the alumina/ruby system. It is shown that in addition to predicting spectroscopic properties, LD theory has now reached a stage of implementation where lattice stability and local site geometry can be usefully explored.     

High temperature calorimetric studies of heat of solution of NiO, CuO, La2O3, TiO2, HfO2 in sodium silicate liquids

The enthalpies of solution of La₂O₃, TiO₂, HfO₂, NiO and CuO were measured in sodium silicate melts at high temperature. When the heat of fusion was available, we derived the corresponding liquid-liquid enthalpies of mixing. These data, combined with previously published work, provide insight into the speciation reactions in sodium silicate melts. The heat of solution of La₂O₃ in these silicate solvents is strongly exothermic and varies little with La₂O₃ concentration. The variation of heat of solution with composition of the liquid reflects the ability of La(III) to perturb the transient silicate framework and compete with other cations for oxygen. The enthalpy of solution of TiO₂ is temperature-dependent and indicates that the formation of Na-O-Si species is favored over Na-O-Ti at low temperature. The speciation reactions can be interpreted in terms of recent spectroscopic studies of titanium-bearing melts which identify a dual role of Ti⁴⁺ as both a network-former end network-modifier. The heats of solution of oxides of transition elements (Ni and Cu) are endothermic, concentration-dependent and reach a maximum with concentration. These indicate a charge balanced substitution which diminishes the network modifying role of Na⁺ by addition of Ni²⁺ or Cu²⁺. The transition metal is believed to be in tetrahedral coordination, charge balanced by the sodium cation in the melts.     

Reduction of Manganese Oxides: Thermodynamic,Kinetic and Mechanistic Considerations for One- Versus Two-Electron Transfer Steps

Manganese oxides, typically similar to δ-MnO₂, form in the aquatic environment at near neutral pH via bacterially promoted oxidation of Mn(II) species by O₂, as the reaction of [Mn(H₂O)₆]²⁺ with O₂ alone is not thermodynamically favorable below pH of ~?9. As manganese oxide species are reduced by the triphenylmethane compound leucoberbelein blue (LBB) to form the colored oxidized form of LBB (λ_max?=?623 nm), their concentration in the aquatic environment can be determined in aqueous environmental samples (e.g., across the oxic–anoxic interface of the Chesapeake Bay, the hemipelagic St. Lawrence Estuary and the Broadkill River estuary surrounded by salt marsh wetlands), and their reaction progress can be followed in kinetic studies. The LBB reaction with oxidized Mn solids can occur via a hydrogen atom transfer (HAT) reaction, which is a one-electron transfer process, but is unfavorable with oxidized Fe solids. HAT thermodynamics are also favorable for nitrite with LBB and MnO₂ with ammonia (NH₃). Reactions are unfavorable for NH₄⁺ and sulfide with oxidized Fe and Mn solids, and NH₃ with oxidized Fe solids. In laboratory studies and aquatic environments, the reduction of manganese oxides leads to the formation of Mn(III)-ligand complexes [Mn(III)L] at significant concentrations even when two-electron reductants react with MnO₂. Key reductants are hydrogen sulfide, Fe(II) and organic ligands, including the siderophore desferioxamine-B. We present laboratory data on the reaction of colloidal MnO₂ solutions (λ_max?~?370 nm) with these reductants. In marine waters, colloidal forms of Mn oxides (<?0.2 µm) have not been detected as Mn oxides are quantitatively trapped on 0.2-µm filters. Thus, the reactivity of Mn oxides with reductants depends on surface reactions and possible surface defects. In the case of MnO₂, Mn(IV) is an inert cation in octahedral coordination; thus, an inner-sphere process is likely for electrons to go into the empty e _g ^* conduction band of its orbitals. Using frontier molecular orbital theory and band theory, we discuss aspects of these surface reactions and possible surface defects that may promote MnO₂ reduction using laboratory and field data for the reaction of MnO₂ with hydrogen sulfide and other reductants.     

Photocatalytic ozonation of 2, 4-dichlorophenoxyacetic acid in water with a new TiO2 fiber

More effective techniques are required to mineralize the increasing number of recalcitrant organic contaminants at low concentrations in the water environment using advanced oxidation process. Though relatively new, photocatalytic ozonation (O₃/UV/TiO₂) is considered superior to ozonation (O₃) and photocatalysis (UV/TiO₂), due to synergistic effects and use of immobilized TiO₂ photocatalysts is a milestone in advance oxidation process. This article aimed to elucidate 2, 4-dichlorophenoxyacetic acid (2, 4-D) mineralization characteristics in low aqueous solutions by O₃/UV/TiO₂ using the world’s first high-strength TiO₂ fiber catalyst in laboratory experiments. 2, 4-D degradation and TOC removal in O₃, UV/TiO₂ and O₃/UV/TiO₂ followed pseudo-first order reaction kinetic. The removal rates for 2, 4-D and TOC in O₃/UV/TiO₂ were respectively about 1.5 and 2.4-fold larger than the summation of the corresponding values in O₃ and UV/TiO₂. The O₃/UV/TiO₂ process was characterized by short-lived few aromatic intermediates, faster degradations of aliphatic intermediates and dechlorination as a major step in 2, 4-D mineralization. The significantly enhanced 2, 4-D mineralization in the process was attributed to increased ozone decomposition and reduced electron-hole recombination on TiO₂ surface resulting to a large number of OH generation. The O₃/UV/TiO₂ process with the TiO₂ fiber catalyst was very promising with respect to the major challenges being faced in AOP involving TiO₂, namely separation of powder catalyst in suspension and reduced efficiency of immobilized catalysts (e.g. TiO₂ film/fiber).     

Development of a reactive zone technology for simultaneous in situ immobilisation of radium and uranium

Simultaneous in situ immobilisation of uranium (U) and radium (²²⁶Ra) by injectible amounts of grey cast iron (gcFe), nano-scale iron (naFe) and a gcFe/MnO₂ mixture (1:1) was studied in batch and column tests. Both 0.5 g/L naFe and gcFe are effective in ²²⁶Ra and U removal from mine water, whereas MnO₂ addition clearly increased the efficiency of gcFe for ²²⁶Ra and U immobilisation. In a column test with 0.6 wt% gcFe/MnO₂ mixture (1:1), neither ²²⁶Ra nor U was detected in the effluent after replacement of 45 pore volumes. A sequential extraction under flow condition revealed ²²⁶Ra to be mostly occluded in manganese oxides. Uranium was mostly sorbed onto poorly crystalline iron hydroxides, but a significant part was found to be occluded in manganese oxides also. The results of this study suggest that MnO₂ promotes iron hydroxide formation under slightly reducing environmental conditions resulting in an increased pollutant retention capacity.