Study of TiO2 anatase nano and microstructures with dominant {001} facets for NO oxidation

Introduction

TiO₂ anatase nanoplates and hollow microspheres were fabricated by a solvothermal?Chydrothermal method using titanium isopropoxide as a titanium precursor and hydrofluoric acid as a capping agent in order to enhance the formation of the {001} crystal facets of the anatase nanocrystals.

Methods

These different morphological structures of TiO₂ anatase can be achieved by only changing the solvent, keeping the amount of the precursor and of the capping agent identical during the solvothermal?Chydrothermal process.

Results and discussion

After calcination of the samples, the adsorbed fluoride atoms on the {001} crystal facets of the TiO₂ anatase nanocrystals were completely removed from their surface according to XPS analysis. The calcined TiO₂ anatase structures were higher crystallized and the specific surface area of the catalysts increased, enhancing their photocatalytic activity in comparison to the non-calcined TiO₂ anatase structures. All TiO₂ anatase samples with adsorbed as well as non-adsorbed fluoride atoms on their {001} crystal facets, exhibited a higher photonic efficiency than Degussa P25, which was used as a reference.

Conclusion

The fluoride free TiO₂ anatase nanoplates exhibited the best photocatalytic activity in oxidizing the NO gas to NO₂ and NO₃ ^?.     

A Novel Affinity Chromatographic Material for the Purification of Extracellular Polyhydroxybutyrate Depolymerases

A novel affinity chromatographic material, which is composed of silica matrix, coated with polyhydroxybutyrate (PHB) powder, suitable for the purification of PHB depolymerases, was developed. The surface morphology of the PHB-silica coated particles (silica-PHB composite particles) was examined by scanning electron microscopy and revealed a successful uniform coating of silica particles with PHB. Moreover, the complex of these materials retained its homogeneity even after incubation at 80 °C for 6 h, whereas the strong binding of PHB on silica surface was further verified by thermal gravimetric analysis and by PHB extraction- from silica surface- experiments. This novel material was demonstrated to be suitable for both, the one-step on-batch and on-column purification of Thermus thermophilus extracellular PHB depolymerase. The enzyme exhibited higher affinity against the composite of silica-PHB particles than PHB powder, since the one-step purification-fold and the overall recovery of the enzyme were 2.8 and 4 times higher respectively, in the first case. Reusability of the silica-PHB composites particles was examined by determining the recoveries of PHB depolymerase. The enzyme recoveries were ranged from 30 to 35% for the first five uses, whereas for further uses recoveries gradually dropped to 15–18% indicating that the particles could be used repeatedly for five times. This material could be also a suitable support for lipases or other proteins that exhibit strong affinity to hydrophobic materials.     

Influence of a 1,800 MHz electromagnetic field on the EEG energy

The present study investigated the influence of electromagnetic fields (EMF), similar to that emitted by mobile phones, on brain activity. Ten women and ten men, matched for age and educational level, performed a short memory task (Wechsler test), with simultaneous Electroencephalogram (EEG) recordings at 15 scalp electrodes, both without (baseline) and with exposure to an 1,800 MHz signal. The EEG energy was found concentrated at the four basic EEG bands [α (8–13 Hz), β (14–30 Hz), δ (0–4 Hz), and θ (5–7 Hz)]. The analysis revealed that in the presence of EMF, the energy of the β band was significantly greater for females than for males at the majority of the electrodes. Since beta oscillation is associated with the shift of attention during the perception, these findings may indicate that the particular EMF (1,800 MHz signal) exerts an influence on this brain activity, which appears to be gender-related.     

PTR-MS measurements and analysis of models for the calculation of Henry's law constants of monosulfides and disulfides

Sulfides are known for their strong odor impact even at very low concentrations. Here, we report Henry’s law constants (HLCs) measured at the nanomolar concentration range in water for monosulfides (dimethylsulfide, ethylmethylsulfide, diethylsulfide, allylmethylsulfide) and disulfides (dimethyldisulfide, diethylsulfide, dipropylsulfide) using a dynamic stripping technique coupled to Proton Transfer Reaction-Mass Spectrometry (PTR-MS). The experimental data were compared with literature values and to vapor/solubility calculations and their consistency was confirmed employing the extra-thermodynamic enthalpy-entropy compensation effect. Our experimental data are compatible with reported literature values, and they are typically lower than averaged experimental literature values by about 10%. Critical comparison with other freely available models (modeled vapor/solubility; group and bond additivity methods; Linear Solvation Energy Relationship; SPARC) was performed to validate their applicability to monosulfides and disulfides. Evaluation of theoretical models reveals a large deviation from our measured values by up to four times (in units of M atm⁻¹). Two group contribution models were adjusted in view of the new data, and HLCs for a list of sulfur compounds were calculated. Based on our findings we recommend the evaluation and adaption of theoretical models for monosulfides and disulfides to lower values of solubility and higher values of fugacity.     

Characterization and dispersion modeling of odors from a piggery facility

Piggeries are known for their nuisance odors, creating problems for workers and nearby residents. Chemical substances that contribute to these odors include sulfurous organic compounds, hydrogen sulfide, phenols and indoles, ammonia, volatile amines, and volatile fatty acids. In this work, daily mean concentrations of ammonia (NH3) and hydrogen sulfide (H2S) were measured by hand-held devices. Measurements were taken in several places within the facility (farrowing to finishing rooms). Hydrogen sulfide concentration was found to be 40 to 50 times higher than the human odor threshold value in the nursery and fattening room, resulting in strong nuisance odors. Ammonia concentrations ranged from 2 to 18 mL m(-3) and also contributed to the total odor nuisance. Emission data from various chambers of the pig farm were used with the dispersion model AERMOD to determine the odor nuisance caused due to the presence of H2S and NH3 to receptors at various distances from the facility. Because just a few seconds of exposure can cause an odor nuisance, a "peak-to-mean" ratio was used to predict the maximum odor concentrations. Several scenarios were examined using the modified AERMOD program, taking into account the complex terrain around the pig farm.     

Characterization of Rain and Roof Drainage Water Quality in Xanthi, Greece

Thirteen field campaigns were undertaken in the period from December 2, 2002 until September 1, 2004 to collect water samples in order to characterize the quality of rainfall and roof drainage in the city of Xanthi, a typical provincial city in Greece. In each campaign, water samples were collected from 10 representative sites in the city (in total 130 samples), representing areas of distinct land use and human activities (i.e., traffic volume, residence density and industrial activity). The water samples were analyzed according to drinking water criteria for total coliform (not detected), temperature (range: 0.9–20°C), pH (range: 3.6–11.4), alkalinity (range: 0–21.5 mg CaCO₃/L), nitrate (range: 0–2456 μg/L), ammonium (range: 0–2628 μg/L), sulfate (range: 0–0.5 mg/L), calcium (range: 259.1–3064 μeq/L), magnesium (range: 0.8–488.8 μeq/L), potassium (range: 0.0–110.6 μeq/L) and dissolved heavy metals (Fe, range: 0.01–0.18 mg/L; Mn, range: 0.01–0.09 mg/L; Zn, range: 0.01–0.54 mg/L; Cu, Cr and Ni, not detected). Pollutant concentrations were generally higher in roof drainage than in rainwater, but both were lower than drinking water standards. Dissolved heavy metal concentrations were generally higher in the areas of intensive human activities, such as roads with high traffic volume and densely populated residential areas. The satisfactory quality of rainwater, which results from this analysis, makes its use as grey water possible.     

Monometal and competitive adsorption of heavy metals by sewage sludge-amended soil

Sewage sludge-amended soils may alter their ability to adsorb heavy metals over time, due to the decomposition of sludge-borne organic matter. Thus, we studied Cd, Ni, and Zn adsorption by a sewage sludge-amended soil (Typic Xerofluvent) before and after one-year incubation in both monometal and competitive systems. In the monometal system, the order of decreasing sorption was Zn>Cd>Ni. Competition significantly reduced metal K(d), especially that of Cd which decreased by nearly 50%. Over the course of the incubation there was a 31% reduction of soil organic matter content. At the same time, in competitive systems Cd K(d) significantly decreased, while Zn K(d) significantly increased, and Ni K(d) remained unaffected. This study shows that sewage sludge-amended soils may change in their ability to sorb heavy metals over time at high metal concentrations. The data suggest that Cd is likely to be of most environmental significance in such soils, since it exhibited decreased sorption under competitive conditions and as the organic matter content of the soil was reduced. The potential for long-term release of metals should be considered in the risk assessment associated with sewage sludge addition to soils, particularly in climates where degradation of organic matter is likely to be enhanced.     

Groundwater hydrogeochemistry of Trikala municipality, central Greece

Sixty-four samples from the groundwater resources of Trikala municipality, central Greece, were collected during two periods (2006 and 2007) and analyzed for physico-chemical parameters (temperature, pH, specific electrical conductivity, and total dissolved solids), major ions (Ca²⁺, Cl^?, HCO ₃ ^? , K⁺, Mg²⁺, Na⁺, NO ₃ ^? , SO ₄ ^2? ), and several potentially toxic elements (Al, B, Ba, Br, Ca, Ce, Cl, Cr, Cu, Fe, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, P, Pb, Rb, S, Sc, Si, Sn, Sr, U, V, Y, Zn). European Council directives and USEPA guidelines were used to assess the water quality. The results indicate that all samples are fresh water, suitable for human consumption. All basic ions and physico-chemical parameters have average concentrations below their recommended optimum limits with the exception of electrical conductivity, for January 2007, and nitrate for October 2006 and January 2007 sampling periods. This exceedance is the result of dissolution of minerals such as calcite and dolomite that are present in the surrounding rocks and the application of fertilizers, respectively. Lead is the only element with an average value that exceeds the recommended EC guideline, while special attention should be paid to one borehole (T9) which has elevated NO ₃ ^? values which may pose a risk to human health.     

Simultaneous determination of chlorothalonil and its metabolite 4-hydroxychlorothalonil in greenhouse air: dissipation process of chlorothalonil

An analytical method was developed and tested for the simultaneous determination of chlorothalonil and its main metabolite 4-hydroxychlorothalonil, in airborne samples. High performance liquid chromatography equipped with Ultra-violet detector was used to separate and quantify the analytes. Glass microfibre filters for the collection of the analytes' particles were tested. Solid sorbents, such as Tenax, Florisil, XAD-2 and silica gel, were studied to find out the most suitable material for the collection of the analytes in the gas phase. The results have shown that only chlorothalonil was trapped in the vapor phase with highest results obtained when silica gel was the sorbent of choice. Linearity was demonstrated in a wide concentration range 0.01-10.00 mg L(-1). Recoveries from spiked glass microfibre filters and silica gel cartridges for chlorothalonil and 4-hydroxychlorothalonil were almost quantitative. The quantification limits were calculated to be 8.4 and 19.6 ng m(-3) in air for chlorothalonil and 4-hydroxychlorothalonil, respectively. The two analytes spiked on the GF/A filters and silica gel cartridges were proven to be stable for more than 15 days, at 4degrees C and ambient temperature. The applicability of the present method was demonstrated by the analysis of the chlorothalonil and its metabolite in greenhouse air.     

Soil column experiments used as a means to assess transport, sorption, and biodegradation of pesticides in groundwater

Soil column experiments are used to investigate the fate of three pesticides of high, intermediate, and low solubility in groundwater: N- phosphonomethyl glycine (glyphosate); O,O-diethyl-S-[(ethylthio)methyl]phosphorodithioate (phorate); (2,4-dichlorophenoxy)acetic acid (2,4-D). Feed solutions are prepared by adding each pesticide (100 mg/L glyphosate, 50 micro g/L phorate, 50 mg/L 2,4-D) along with conservative tracer, KBr, in synthetic groundwater. The concentration of the pesticides in effluents is detected by ion chromatography (glyphosate, 2,4-D) and GC-FID (phorate). The Br(-) breakthrough curves are employed to estimate the dispersion coefficient and mean pore velocity in each column. Solute transport and reactive models accounting for equilibrium/non-equilibrium sorption and biodegradation are coupled with inverse modeling numerical codes to estimate the kinetic parameters for all pesticides.