On-line coupling flow injection microcolumn separation and preconcentration to electrothermal atomic absorption spectrometry for determination of (ultra)trace selenite and selenate in water

A flow injection manifold with an air-segmented and air-transported operational sequence for on-line coupling of microcolumn separation and preconcentration to electro-thermal atomic absorption spectrometry (ETAAS) was developed for the determination of (ultra)trace selenite and selenate in water. The determination of selenite was achieved by selective reaction with pyrrolidine dithiocarbamate (PDC), sorption of the resultant Se-PDC compound onto a conical microcolumn (10.2 microL) packed with RP C18 sorbent, elution with ethanol, and detection by ETAAS. The concentration of selenate was obtained as the difference between the concentrations of selenite after and before prereduction of selenate to selenite. With the developed manifold and operation sequence,the dispersion during elution and eluate transport and the eluent volume required for complete elution of the sorbed analyte were minimized. As a result, the sorbed analyte was quantitatively eluted from the column with only 26 microL of ethanol, and all the eluate was automatically introduced into the graphite tube by an air flow without the need of preheating the graphite tube or precise timing. Pretreatment of the graphite tube with iridium as a long-term "permanent" modifier effectively prevented analyte loss arising from the high volatility of the Se-PDC compound and greatly improved the precision, sensitivity, and detection limit. One thermal pretreatment of the graphite tube with injection of 150 microgram of iridium made possible at least 200 repetitive atomization cycles. With a preconcentration time of 180 s and a sample flow rate of 1.4 mL min(-1), an enhancement factor of 112 was achieved in comparison with direct injection of 30 microL of aqueous solution. The detection limit (3s) was 4.5 ng L(-1)Se. The RSD (n = 7) was 3.8% at 20 ng L(-1)Se. The concentrations of selenite and selenate determined in synthetic aqueous mixtures were in good agreement with the expected values. The recoveries for selenite from spiked seawater samples ranged from 98 to 102%. The concentrations of selenite in several seawater reference materials obtained with simple aqueous standard solutions for calibration agreed well with the certified and information values, respectively. In addition, the developed method was successfully applied to the certification of selenite and selenate in water.     

Sorption of arsenite and arsenate on ferrihydrite: effect of organic and inorganic ligands

We studied the sorption of As(III) and As(V) onto ferrihydrite as affected by pH, nature and concentration of organic [oxalic (OX), malic (MAL), tartaric (TAR), and citric (CIT) acid] and inorganic [phosphate (PO(4)), sulphate (SO(4)), selenate (SeO(4)) and selenite (SeO(3))] ligands, and the sequence of anion addition. The sorption capacity of As(III) was greater than that of As(V) in the range of pH 4.0-11.0. The capability of organic and inorganic ligands in preventing As sorption follows the sequence: SeO(4) ≈ SO(4) < OX < MAL ≈ TAR < CIT < SeO(3) ? PO(4). The efficiency of most of the competing ligands in preventing As(III) and As(V) sorption increased by decreasing pH, but PO(4) whose efficiency increased by increasing pH. In acidic systems all the competing ligands inhibited the sorption of As(III) more than As(V), but in alkaline environments As(III) and As(V) seem to be retained with the same strength on the Fe-oxide. Finally, the competing anions prevented As(III) and As(V) sorption more when added before than together or after As(III) or As(V).     

Determination of dissolved selenium species in environmental water samples using isotope dilution mass spectrometry.

In order to clarify the species composition of selenium in environmental water samples, analytical methods have been developed for the selective determination of different chemical forms of this element (selenite, selenate, and organic species including trimethylselenonium) using isotope dilution mass spectrometry (IDMS). The species analysis was made possible by means of chromatographic separation procedures and an 82Se-enriched selenate, selenite, and trimethylselenonium spike for the isotope dilution process. The total selenium concentration was determined after decomposition of organic compounds with a HNO3/HCIO4 mixture. Selenium was measured in the mass spectrometer by producing negative Se- thermal ions for detection. Precise determination at the parts-per-trillion level was achieved. This new methodology was applied to different types of natural water samples (groundwater, pond water, river water, moorland lake water) with total selenium concentrations in the range of 200 pg/g to 15 ng/g. Selenite and selenate have been the only detected species in most of the investigated samples, with selenate dominating all except one. In samples with high contents of dissolved organic carbon, however, different organoselenium compounds including trimethylselenonium ions were additionally quantified in the range of 10-95 pg/g. In these cases, the sum of all selenium species agreed well with the independently determined total element concentration.     

稻草生物炭对铕的吸附行为及机理研究

以农业残留物为原料制备的生物炭被广泛应用于去除重金属, 这对于环境保护具有双重意义。本研究以稻草为原料制备了生物炭, 通过系列静态实验和光谱技术研究其对重金属铕(Eu)的吸附行为及机理。研究发现溶液pH显著影响生物炭对Eu(III)的吸附量, 但不改变吸附反应时间; 腐殖酸/富里酸(HA/FA)在pH<7.0的溶液中能促进生物炭对Eu(III)的吸附, 而在pH>7.0的溶液中则抑制Eu(III)的吸附; 吸附过程主要涉及共沉淀或内表面络合机制; 该吸附属于化学吸附, 且吸附速率受内颗粒扩散过程的限制。此外, Freundlich模型对该吸附拟合最好, Langmuir模型显示稻草生物炭对Eu(III)的最大吸附量为40.717 mg/kg, 这可能与生物炭的层状结构和丰富的官能团有关; 热力学分析表明该吸附是自发的吸热过程。这些发现有利于评估稻草生物炭在去除水中重金属方面潜在的应用价值。     

Low temperature stabilized rutile phase TiO2 films grown by sputtering

The deposition of rutile phase TiO₂ films on unheated substrates by radio frequency magnetron sputtering is elaborated. The effect of total pressure and O₂/Ar flow ratio on the growth of rutile film on different substrates has been studied thoroughly. The development of crystalline phase along with film deposition rate, surface morphology, optical transmission and band gap were also investigated for various growth conditions. It was found that the rutile phase crystallinity increased with decrease in total pressure and increase in O₂ flow. In addition, the grown rutile films have interesting optical characteristics such as high transmittance (~ 85%) and high refractive index (~ 2.7) with a band gap about 3.2 eV.     

Enhanced sorption of radiocobalt from water by Bi(III) modified montmorillonite: a novel adsorbent

In this study, Ca-montmorillonite (Ca-Mt) modified with Bi³⁺ was used as a novel adsorbent for the sorption of Co(II) from aqueous solutions. The sorption of Co(II) on Bi-montmorillonite (Bi-Mt) was investigated as a function of contact time, pH, ionic strength, adsorbent content, Co(II) concentrations, fulvic acid (FA) and temperature. Compared to Ca-Mt, Bi-Mt showed a higher affinity to bind Co(II) ions. The sorption percentage of Co(II) on Bi-Mt increased with increasing pH at pH 3.0-8.5, and then maintained the high level at pH 8.5-12. The sorption of Co(II) on Bi-Mt was dependent on ionic strength at low pH, and independent of ionic strength at high pH. The presence of FA enhanced Co(II) sorption at low pH, but suppressed Co(II) sorption at high pH. The thermodynamic data derived from temperature dependent sorption isotherms suggested that the sorption of Co(II) on Bi-Mt was spontaneous and endothermic process. Outer-sphere surface complexation and/or ion exchange were the main mechanisms of Co(II) sorption on Bi-Mt at low pH, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. From the experimental results, it is possible to conclude that Bi-Mt is suitable for application of Co(II) removal from aqueous solutions.     

Synthesis of nanostructure rutile TiO2 in a carboxyl-containing ionic liquid

Nanostructure rutile TiO₂ was prepared in a carboxyl-containing ionic liquid, 1-methylimidazolium-3-acetate chlorine ([AcMIm]Cl), by using TiOCl₂ solution as a precursor at low temperature. The obtained nanostructure TiO₂ was analyzed with fourier transform infrared (FTIR), X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The as-prepared TiO₂ present only rutile crystal phase and a novel flower-like morphology. The as-prepared rutile TiO₂ shows better photocatalytic performance in the degradation of methyl orange. The template-directing performance of ionic liquid is due to the bidentate chelating complexation between the carboxylic functional group of ionic liquid and titania.     

Controllable synthesis and photocatalytic activities of water-soluble TiO2 nanoparticles

Water-soluble anatase, mixed-phase (anatase and rutile) and rutile TiO₂ nanoparticles (NPs) or nanorods were synthesized under mild solution conditions using polyethylene glycol 400 (PEG 400) as a stabilizer and HCl as a phase controlling reagent. The photocatalytic properties of these NPs with different crystal phases were evaluated by photocatalytic degradation experiments of methyl orange (MO). As-prepared pure anatase TiO₂ NPs show a higher photocatalytic activity than other samples and commercial P25, which may be related to the high crystallinity, the pure anatase phase, small size and the enhanced absorbability associated with the existence of PEG 400 on the NP surface.     

Bioprocessing of seleno-oxyanions and tellurite in a novel Bacillus sp. strain STG-83: a solution to removal of toxic oxyanions in presence of nitrate

Bioremediation of toxic nonmetal and metalloid oxyanions is of great interest. In this study, among 148 bacterial isolates from two types of polluted water, strain STG-83 showed maximum oxyanion reduction and resistance ability. Sequencing of the 16S rDNA gene of STG-83 showed that the strain is closely related to Bacillus pumilus and morphological and biochemical tests confirmed the result. The strain was nitrate negative, but it could reduce half of tellurite in solution containing 1-mM concentration and completely reduced selenite and selenate in solutions containing 1-mM concentrations. Both reduction to elemental form and volatilization occurred in case of all oxyanions tested, according to hydride generation atomic absorption spectroscopy and proton induced X-ray emission analytical methods. The strain was able to tolerate remarkably high concentrations of selenite (640 mM), selenate (320 mM), and tellurite (1250 microM); and tolerance to tellurite increased in presence of selenite and selenate. Biochemical tests and zymogram of extracted culture solutions on gel electrophoresis showed that the strain was nitrate negative and therefore nitrate did not interfere with reduction of other oxyanions. Thus, the strain opens up good opportunities for the bioremediation of polluted waters in natural environment, since nitrate usually inhibits or decelerates reduction of the mentioned toxic oxyanions.     

Synthesis of highly-active single-crystalline TiO2 nanorods and its application in environmental photocatalysis

Highly-active anatase TiO₂ nanorods have been successfully synthesized via a simple two-step method, hydrothermal treatment of anatase/rutile titanium dioxide nanoparticle powder in a composite-hydroxide eutectic system of 1:1 M KOH/NaOH, followed by acid post-treatment. The morphology and crystalline structure of the obtained nanorods were characterized using XRD, TEM, SEM/EDX and BET surface area analyzer. The obtained TiO₂ nanorods have a good crystallinity and a size distribution (about 4-16 nm); with the dimensions of 200-300 nm length and of 30-50 nm diameter. Compared with its precursor anatase/rutile TiO₂ nanoparticles and the titanate nanotubes, the pure anatase TiO₂ nanorods have a large specific surface area with a mesoporous structure. The photocatalytic performance of the prepared nanorods was tested in the degradation of the commercial Cibacrown Red (FN-R) textile dye, under UV irradiation. Single-crystalline anatase TiO₂ nanorods are more efficient for the dye removal.     

New high capacity getter for vacuum insulated mobile LH2 storage tank systems

Current “Non-evaporable getters” (NEGs) are important for the improvement of vacuum by the help of metallic surface sorption of residual gas molecules. High porosity alloys or powder mixtures of Zr, Ti, Al, V, Fe and other metals are the base material for this kind of gas sorbents. The development of vacuum technologies creates new challenges for the field of getter materials. The main sorption parameters of the current NEGs, namely, pumping speed and sorption capacity, have reached certain level limits. Chemically active metals are the basis of NEGs of a new generation. The appearance of new materials with high sorption capacity at room temperature is a long-felt need. It is obvious, that chemically active metals and alloys with reactivity higher, than that of transition metals, can become this kind of materials. The potential of active metals as the strongest gas sorbents is very high. The improved getter materials allow faster pumping speed. The sticking rate on the chemically active surface is significantly higher, and sorption capacity can be increased by up to 104 times (during the life-time of a device the entire getter material reacts with residual gases). The main structural form of the new getter concepts are spherical powders, granules and porous multi-layers. The full pumping performance takes already place at room temperature and the activation temperature can be adjusted between room temperature and 660 °C. The successful insertion of this new chemical getter pump in a mobile double-walled LH₂ tank system shows the very high sorption capacity of all relevant residual gases including H₂. This new invention opens the possibility for significant vacuum improvements especially in the field of H₂ pumping, which is an important challenge in many different vacuum devices and processes.     

Sorption behaviors of aromatic anions on loess soil modified with cationic surfactant

Modification of soils with hydrophobic cationic surfactants is an effective approach for enhancing the sorptive capabilities of soil in the vadose zone for the purpose of retaining organic contaminants prior to cleanup. The objective of this study was to examine the sorptive behavior of the cationic surfactant-modified loess soil for aromatic anions in the aqueous phase in an attempt to define the sorptive mechanisms. Some dominant factors governing the sorption, such as ionic strength and divalent heavy metal cation, were investigated. The sorption isotherms of 2,4-dinitrophenol (DNP) and benzoic acid (BA) in the modified soil samples were obtained using the batch equilibration method. Under the laboratory conditions, the modified loess soil utilized in this study was prepared by replacing the cations of loess soil with a cationic surfactant—hexadecyltrimethylammonium (HDTMA) bromide. The acidic aromatic compounds, DNP and BA existing as aromatic anions in the natural mixture of loess soil and aqueous phase, were selected as indicator compounds to measured the sorption behaviors of aromatic anions on the HDTMA-modified loess soil. The results confirmed that the sorptive capabilities of aromatic anions in loess soil were greatly enhanced by modification with HDTMA. The increase of ionic strength and the addition of divalent heavy metal cation Zn²⁺ significantly increased the sorption of aromatic anions on the HDTMA-modified loess soil. In binary solute systems, the sorbed amounts either of DNP or BA on the HDTMA-modified loess soil were reduced if two compounds existed simultaneously in the soil. This results indicated that competitive adsorption between the two aromatic anions occurred in soil matrix.     

TiO2 nanorod films grown on Si wafers by a nanodot-assisted hydrothermal growth

We report the controlled hydrothermal growth of rutile TiO₂ nanorods on Si wafers by using an anatase TiO₂ nanodot film as an assisted growth layer. The anatase nanodot film was prepared on the wafer by phase-separation-induced self-assembly and subsequent heat-treatment at 500 °C. The nanodots on the wafer were then subjected to hydrothermal treatment to induce the growth of rutile TiO₂ nanorod films. The size and dispersion density of the resulting TiO₂ nanorods could be varied by adjusting the Ti ion concentration in the growth solution. The TiO₂ nanorods were of the rutile phase and grew in the [001] direction. The growth mechanism reveals that the growth of the rutile nanorods was wholly dependent on the existence of rutile TiO₂ seeds, which could be formed by the dissolution-reprecipitation of the anatase nanodots during hydrothermal treatment or under the high-temperature conditions of the subsequent heat-treatment of the as-prepared nanodots. In controlling the rutile nanorod growth, the anatase nanodots show more efficiency than a dense anatase film. Preliminary evaluations of the rutile nanorod films have demonstrated that the wettability changed from highly hydrophobic to superhydrophilic and that the photocatalytic activity was enhanced with increasing nanorod dispersion density.     

Preparation of pure rutile and anatase TiO2 nanopowders using RF thermal plasma

We synthesized pure rutile and anatase nanopowders using in-flight oxidation of titanium nitride powder in an r.f. thermal plasma reactor. The mechanism of the in-flight oxidation of TiN powder was elucidated, and the effects of oxygen and hydrogen input concentrations on phase composition and morphology were investigated. The characteristics of the synthesized powder were evaluated using X-ray diffraction, optical microscopy, scanning electron microscopy and Raman scattering spectroscopy. The phase composition depended mainly on the ambient oxygen concentration. At high oxygen concentrations, the anatase content increased to over 93%. Introducing hydrogen promoted the formation of oxygen-deficient rutile nanopowder, and pure rutile nanopowder averaging 50 nm in diameter was produced with excess hydrogen. The synthesized powder had good photocatalytic activity in the decomposition of aqueous methylene blue under visible light.     

Surface Modification of Sericite Using TiO2 Powders Prepared by Alkoxide Hydrolysis: Whiteness and SPF Indices of TiO2-Adsorbed Sericite

Titania (TiO₂) powders have been prepared from the 0.025-M titanium isopropoxide/ethanol solution and the 0.5-M distilled water/ethanol solution. The prepared TiO₂ powders showed an anatase phase and a rutile phase after heat treatment at 500°C for 2 h and 1000°C for 2 h, respectively. The heterocoagulation adsorption between TiO₂ powder and sericite surface in water was achieved in the range of pH 3.63.7 (where this pH range shows a maximum Zeta-potential difference for two powders). On the other hand, an anomalous transformation behavior appeared in the TiO₂-adsorbed sericite after heat treatment at 1000°C. The surface modification of sericite through the TiO₂-adsorption improved the whiteness as well as the SPF (Sun Protection Factor) indices.     

Processing and photocatalytic properties of Cu-grafted TiO2 powder from acid treated BaTiO3

The respective influences of calcination, drying methods, and washing conditions on the morphologies, surface properties, and photocatalytic activities of TiO₂ powders prepared from acid treatments of BaTiO₃ were investigated. Rutile powder was obtained using the treatment under strong acid conditions. It possesses a bundle-like shape and comprises rutile nanorods. After calcination, characteristic voids were observed in the particles. Anatase powder was obtained by adjusting pH values of a BaTiO₃ suspension to 2.5-3. Drying at 110 °C engendered the formation of spheroidal anatase, although freeze-dried anatase particles assembled into a flake-like shape. The freeze-dried samples show lower crystallinity. With grafting Cu ions, rutile exhibited better photocatalytic performance for the decomposition of gaseous 2-propanol (IPA) under visible light, although it did not work effectively for anatase.     

Sorption of Cd(II) and Se(IV) from aqueous solution using modified rice husk

A carbonaceous sorbent was prepared from rice husk via sulfuric acid treatment. Removal of Cd(II) and Se(IV) from aqueous solution was studied varying time, pH, metal concentration, temperature and sorbent status (wet and dry). Cd(II) sorption was found fast reaching equilibrium within approximately 2 h while Se(IV) sorption was slow reaching equilibrium within approximately 200 h with better performance for the wet sorbent than for the dry. Kinetics data for both metals were found to follow pseudo-second order model. Cd(II) sorption was low at low pH values and increased with pH increase, however, Se(IV) sorption was high at low pH values, and decreased with the rise in initial pH until pH 7. A fall in the final pH was noticed with Cd(II) sorption due to the release of protons indicating an ion exchange mechanism. However, for Se(IV) sorption, a rise in the final pH was observed due to protons consumption in the process. For both metals, sorption fit well the Langmuir equation with higher uptake by rising the temperature. Analysis by scanning electron microscope and X-ray powder diffraction for the sorbent after the reaction with acidified Se(IV) confirmed the availability of elemental selenium, Se(0), as particles on the sorbent surface. The reduction process of acidified Se(IV) to Se(0) is accompanied by surface oxidation. Physicochemical tests showed an increase in sorbent acidity, cation exchange capacity and surface functionality after the reaction with acidified Se(IV) indicating that oxidation processes took place on the sorbent surface. On the other hand, no changes in physicochemical tests were found after Cd(II) sorption indicating the absence of redox processes between Cd(II) and the sorbent.     

Reactive mechanical grinding of magnesium in hydrogen and the effects of additives

The use of reactive mechanical grinding (MG under H₂) of magnesium powder improves the hydrogen sorption properties. The hydrogenation of Mg starts in situ during the milling process, thus circumventing the activation procedure that is generally required for Mg. The effects of the addition of various elements or compounds have been studied. The hydriding is determined to be a two-step process: nucleation and diffusion. A direct relationship exists between the nucleation duration and the specific surface area of the magnesium powder. A critical milling time exists up to which the diffusion process is improved and above which no more improvement is observed (the maximum internal stress in the powder is also reached at this critical time). The diffusion is controlled by the number of crystallites per particle that can be reduced by increasing the milling time up to 10 hr. The addition of Co (catalyst), YNi (hydrogen pump), or oxides (abrasive elements and nucleation centers) leads to an improvement of the hydrogen sorption properties (but a strong dependence upon the milling time is reported). Finally, the sorption properties of these mixtures are comparable with those reported for MgH₂-metal mixtures.     

Geochemical modelling of arsenic and selenium leaching in alkaline water treatment sludge from the production of non-ferrous metals

Geochemical modelling of leaching of oxyanion forming elements such as arsenic (As) and selenium (Se) is frequently not successful. A consistent thermodynamic dataset of As and Se was therefore composed, not only including precipitation, but also adsorption and solid solution, and was applied to the pH-dependent leaching behaviour of As and Se in an alkaline residue with a pH 11.1 from the lime treatment of sulphuric acid wastewaters from the production of non-ferrous metals. The As and Se content ranged up to 6.7 wt% and 0.29 wt%, respectively and speciation analysis showed that 96.3% of As occured as arsenate whereas Se speciation comprised 79% selenate and 21.0% selenite. XRD and SEM/EDX analysis showed that arsenate occurred as rauenthalite (Ca(3)(AsO(4))(2).10H(2)O), associated with gypsum, the most important mineral. Arsenate and arsenite concentrations were only slightly below equilibrium with rauenthalite and calciumarsenite (CaHAsO(3)), respectively and consideration of adsorption and solid solution only marginally improved model predictions. Selenate (Se(VI)) and selenite (Se(IV)), on the other hand, were far from equilibrium with their corresponding calcium metalate. The application of solid solutions and adsorption of Se(VI) and Se(IV) oxyanions with gypsum, calcite and ettringite significantly improved model predictions but missing thermodynamic data and especially the lack of a comprehensive model for solid solution and surface exchange with calcite and ettringite still hampered efficient modelling.