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.     

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.     

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.     

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.     

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 ^?.     

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.     

Hazardous waste incinerators under waste uncertainty: Balancing and throughput maximization via heat recuperation

Hazardous waste incinerators (HWIs) differ substantially from thermal power facilities, since instead of maximizing energy production with the minimum amount of fuel, they aim at maximizing throughput. Variations in quantity or composition of received waste loads may significantly diminish HWI throughput (the decisive profit factor), from its nominal design value. A novel formulation of combustion balance is presented, based on linear operators, which isolates the wastefeed vector from the invariant combustion stoichiometry kernel. Explicit expressions for the throughput are obtained, in terms of incinerator temperature, fluegas heat recuperation ratio and design parameters, for an arbitrary number of wastes, based on fundamental principles (mass and enthalpy balances). The impact of waste variations, of recuperation ratio and of furnace temperature is explicitly determined. It is shown that in the presence of waste uncertainty, the throughput may be a decreasing or increasing function of incinerator temperature and recuperation ratio, depending on the sign of a dimensionless parameter related only to the uncertain wastes. The dimensionless parameter is proposed as a sharp a’ priori waste ‘fingerprint’, determining the necessary increase or decrease of manipulated variables (recuperation ratio, excess air, auxiliary fuel feed rate, auxiliary air flow) in order to balance the HWI and maximize throughput under uncertainty in received wastes. A 10-step procedure is proposed for direct application subject to process capacity constraints. The results may be useful for efficient HWI operation and for preparing hazardous waste blends.     

Dynamic stock and end-of-life flow identification based on the internal cycle model and mean-age monitoring

Planning of end-of-life (EoL) product take-back systems and sizing of dismantling and recycling centers, entails the EoL flow (EoLF) that originates from the product dynamic stock (DS). Several uncertain factors (economic, technological, health, social and environmental) render both the EoLF and the remaining stock uncertain. Early losses of products during use due to biodegradation, wear and uncertain factors such as withdrawals and exports of used, may diminish the stock and the EoLF. Life expectancy prediction methods are static, ignoring early losses and inapt under dynamic conditions. Existing dynamic methods, either consider a single uncertain factor (e.g. GDP) approximately or heuristically modelled and ignore other factors that may become dominant, or assume cognizance of DS and of the center axis of the EoL exit distribution that are unknown for most products. As a result, reliable dynamic EoLF prediction for both durables and consumer end-products is still challenging. The present work develops an identification method for estimating the early loss and DS and predicting the dynamic EoLF, based on available input data (production + net imports) and on sampled measurements of the stock mean-age and the EoLF mean-age. The mean ages are scaled quantities, slowly varying, even under dynamic conditions and can be reliably determined, even from small size and/or frequent samples. The method identifies the early loss sequence, as well as the center axis and spread of the EoL exit distribution, which are subsequently used to determine the DS and EoLF profiles, enabling consistent and reliable predictions.     

Combining steam injection with hydraulic fracturing for the in situ remediation of the unsaturated zone of a fractured soil polluted by jet fuel

A steam injection pilot-scale experiment was performed on the unsaturated zone of a strongly heterogeneous fractured soil contaminated by jet fuel. Before the treatment, the soil was stimulated by creating sub-horizontal sand-filled hydraulic fractures at three depths. The steam was injected through one hydraulic fracture and gas/water/non-aqueous phase liquid (NAPL) was extracted from the remaining fractures by applying a vacuum to extraction wells. The injection strategy was designed to maximize the heat delivery over the entire cell (10 m × 10 m × 5 m). The soil temperature profile, the recovered NAPL, the extracted water, and the concentrations of volatile organic compounds (VOCs) in the gas phase were monitored during the field test. GC-MS chemical analyses of pre- and post-treatment soil samples allowed for the quantitative assessment of the remediation efficiency. The growth of the heat front followed the configuration of hydraulic fractures. The average concentration of total hydrocarbons (g/kg of soil) was reduced by ～ 43% in the upper target zone (depth = 1.5-3.9 m) and by ～ 72% over the entire zone (depth = 1.5-5.5 m). The total NAPL mass removal based on gas and liquid stream measurements and the free-NAPL product were almost 30% and 2%, respectively, of those estimated from chemical analyses of pre- and post-treatment soil samples. The dominant mechanisms of soil remediation was the vaporization of jet fuel compounds at temperatures lower than their normal boiling points (steam distillation) enhanced by the ventilation of porous matrix due to the forced convective flow of air. In addition, the significant reduction of the NAPL mass in the less-heated deeper zone may be attributed to the counter-current imbibition of condensed water from natural fractures into the porous matrix and the gravity drainage associated with seasonal fluctuations of the water table.