Spectroscopic behavior of oxygenated combustion by-products

The oxygenated species, massively produced in the energy production plants based on combustion processes, constitute one of the most numerous categories of hazardous air pollutants. Therefore, development of real time diagnostic tools are needed in order to study their formation during combustion processes and to reveal their presence both in the exhaust and in the atmosphere. In this work, oxygenated compounds were identified inside fuel-rich premixed ethylene/air flames by means of ultraviolet fluorescence spectroscopy with the support of qualitative chemical analysis of the sampled combustion gases.

Strong band progression, typical of aldehydic functionality, were recognized in fluorescence spectra (λ_exc=355 nm) measured in the early oxidation region of premixed flames varying the equivalence ratio from 3.0 up 21.6. Downstream of the oxidation region, spectroscopic signatures of pyrolytic species were found to prevail on those peculiar of oxygenated compound. The position and the extension of the two main flame zones were found to depend on the flame conditions (C/O ratio) due to the effect of the C/O ratio on the temperature history along the flame axis. This correlation was interpreted on the basis of the measured axial temperature profiles.     

Evaluation of soil temperature effect on herbicide leaching potential into groundwater in the Brazilian Cerrado

The effect of annual variations in the daily average soil temperatures, at different depths, on the calculation of pesticide leaching potential indices is presented. This index can be applied to assess the risk of groundwater contamination by a pesticide. It considers the effects of water table depth, daily recharge net rate, pesticide sorption coefficient, and degradation rate of the pesticide in the soil. The leaching potential index is frequently used as a screening indicator in pesticide groundwater contamination studies, and the temperature effect involved in its calculation is usually not considered. It is well known that soil temperature affects pesticide degradation rates, air-water partition coefficient, and water-soil partition coefficient. These three parameters are components of the attenuation and retardation factors, as well as the leaching potential index, and contribute to determine pesticide behavior in the environment. The Arrhenius, van't Hoff, and Clausius-Clapeyron equations were used in this work to estimate the soil temperature effect on pesticide degradation rate, air-water partition coefficient, and water-soil partition coefficient, respectively. The relationship between leaching potential index and soil temperature at different depths is presented and aids in the understanding of how potential pesticide groundwater contamination varies on different climatic conditions. Numerical results will be presented for 31 herbicides known to be used in corn and soybean crops grown on the municipality of S?o Gabriel do Oeste, Mato Grosso do Sul State, Brazil.     

Organochlorine and butyltin residues in walleye pollock (Theragra chalcogramma) from Bering Sea, Gulf of Alaska and Japan Sea

Persistent organochlorine (OC) and toxic butyltin compounds (BTs) were determined in walleye pollock (Theragra chalcogramma) collected from Gulf of Alaska, Bering Sea and Japan Sea, during 1991 and 1992. Polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDTs) and its metabolites were the most abundant compounds ranging up to 3200 and 2500 ng/g on lipid weight, respectively, followed by chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs) and hexachlorobenzene (HCB) in the liver of walleye pollock. Concentrations of HCHs and HCB in walleye pollock from these remote areas were higher than those in fishes from the western North Pacific and Japanese coastal waters, indicating atmospheric transport of these compounds to higher latitude regions such as Bering Sea and Gulf of Alaska and/or local input around northern Japan Sea. The concentrations of other OCs were generally comparable to those in fishes from North Pacific Ocean and Japanese waters but significantly lower than in cod-like fishes from North Atlantic and European countries. Among sampling locations, walleye pollock from Japan Sea showed higher concentrations of DDTs and HCHs compared to fishes from Bering Sea and Gulf of Alaska, suggesting greater input of these compounds around Japan Sea. Slower declining trend of DDTs and CHLs and an increasing pattern of PCBs concentrations were found in walleye pollock from Bering Sea during 1982-1992. This may imply a continuous input of these compounds by long-range transport and/or long-term persistency in these cold regions. Compared to the fishes from Japan Sea, walleye pollock from Bering Sea and Gulf of Alaska showed higher proportions of alpha-HCH and p,p'-DDE in the composition of HCH isomers and DDT compounds, respectively. This suggests selective transportability of these compounds during long-range transport to higher latitude remote areas. Concentrations of tributyltin (TBT) in the muscle of walleye pollock ranged from 1.1 to 5.5 ng/g on wet weight. Concentrations of TBT in deep-sea walleye pollock from Gulf of Alaska and Bering Sea were lower than those in Japan Sea.     

Solventless sample preparation for pesticides analysis in environmental water samples using solid-phase microextraction-high resolution gas chromatography/mass spectrometry (SPME-HRGC/MS)

Solid-phase micro-extraction (SPME) coupled on line with high resolution gas chromatography and mass spectrometric detection is described for the analysis of pesticides in environmental water samples. Experiments were performed in order to optimize the SPME extraction conditions for selected pesticides including tiomethon, trichorfon, dimethoate, diazinon, malathion, dicofol, methidathion, ethion, bromopropylate and pyrazophos from spiked water solutions. To enhance the SPME efficiency, experimental conditions including the fiber composition, stirring rate, temperature, adsorption time, desorption time and salt concentration were optimized. After validation, the SPME-GC/MS methodology was applied to real-world environmental water samples.     

Sustainable watershed management: an international multi-watershed case study

Global freshwater resources are being increasingly polluted and depleted, threatening sustainable development and human and ecosystem health. Utilizing case studies from 4 different watersheds in the United States, Japan, Switzerland, and Brazil, this paper identifies the most relevant sustainability deficits and derives general vectors for more sustainable water management. As a consequence of the demographic and economic developments experienced in the last few decades, each watershed has suffered declines in water quality, streamflow and biotic resources. However, the extent and the cultural perception of these water-related problems vary substantially in the different watersheds, leading to specific water-management strategies. In industrialized countries, exemplified by the US, Switzerland, and Japan, these strategies have primarily consisted of finance- and energy-intensive technologies, allowing these countries to meet water requirements while minimizing human health risks. But, from a sustainability point of view, such strategies, relying on limited natural resources, are not long-term solutions. For newly industrialized countries such as Brazil, expensive technologies for water management are often not economically feasible, thus limiting the extent to which newly industrialized and developing countries can utilize the expertise offered by the industrialized world. Sustainable water management has to be achieved by a common learning process involving industrialized, newly industrialized, and developing countries, following general sustainability guidelines as exemplified in this paper.     

A voltammetric screening method to determine ronidazole in bovine meat

Abstract

An original voltammetric screening method, employing glassy carbon electrode (GCE) with the differential-pulse voltammetry technique (DPV), has been developed to determine residues of the anti-parasitic agent Ronidazole (RNZ) in bovine meat. By using cyclic voltammetry (CV), it has been demonstrated that an irreversible cathodic process occurs at approximately ?0.740?V (vs. Ag|AgCl, KCl 3?mol L^?1) in a 0.100?mol L^?1 phosphate buffer at pH 6.5 as supporting electrolyte. Furthermore, the behavior of RNZ in CV indicates the occurrence of a diffusion mass transfer process to the working electrode surface. The RNZ reduction mechanism was proposed as a 6-electron transfer, similar to Metronidazole under the same pH range. Quantification of RNZ and method validation were then carried out by DPV. The relative standard deviation (RSD) were 3.21% for intraday precision of 10 consecutive repetitions and 6.78% for interday precision after five analysis. Limits of detection and quantification were also obtained, and the values were 0.107 and 0.358?mg kg^?1, respectively. The recovery percentage for three different concentrations of RNZ in the bovine meat matrix ranged between 98.1% and 100.3%. The method proved to be efficient for screening RNZ in bovine meat.     

Solvent and surfactant enhanced solubilization, stabilization, and degradation of amitraz

In an effort to help with the development of effective dip vat management and waste disposal strategies this study determined how solution properties such as pH, buffer composition, ionic strength, temperature, solubility in organic solvents and the addition of commonly used solubilizing agents influenced the hydrolysis of amitraz. Amitraz degrade by means of hydrolysis described by a pseudo-first order rate process and a type ABCD pH rate profile. Hydrolysis increased with temperature and was fastest at low pH, slowest at neutral to slightly alkaline pH, and slightly increased above pH 10. However, buffer concentration and ionic strength influenced the hydrolysis rate and had to be accounted for before constructing a pH rate profile. Hydrolysis seems to depend on the dielectric constant of solvent mixtures and was fastest in water, slower in propylene glycol and ethanol solutions, and slowest in DMSO mixtures. In surfactant solutions, anionic micelles enhanced and cationic micelles retarded the hydrolysis rate. The magnitude of micellar effects decreased with increasing concentrations of the surfactants. The increased solubility and faster hydrolysis of amitraz in the sodium lauryl sulfate solutions showed that anionic surfactants potentially could be used for cleaning up amitraz spills, because it both solubilized the drug and catalyzed hydrolysis.     

Enhanced solubilization of arsenic and 2,3,4,6 tetrachlorophenol from soils by a cyclodextrin derivative

The application of extracting aqueous solutions with cyclodextrins in several soil remediation technologies has been increasingly studied but little is known about their removal capacities toward the inorganic species. Herein, the effectiveness of cyclodextrins (CDs) in extracting arsenic, copper, and iron from a mining soil is presented. In a preliminary test of four types of CD aqueous solutions, only the addition of carboxylmethyl-beta-cyclodextrin CMCD (a cyclodextrin derivative) led to a significant enhancement in arsenic removal. An increase in the concentration of copper and iron in the leachates was also observed with CMCD. Kinetic study of arsenic release was carried out at two temperatures (20 and 35 degrees C). The arsenic concentration in the leachates increases with increasing cyclodextrin concentration. At an 80 mM CMCD concentration, arsenic, copper, and iron released in filtrates were about 20-, 1,000-, and 4,000-fold greater, respectively, than that obtained using deionized water. In the soil system, the CMCD capacity removal was found to be higher for cations than for arsenic. Because the tetrachlorophenol can co-occur with arsenic and copper in several contaminated sites, its solubilization by CMCD was also investigated. Extraction experiments were performed to extract 2,3,4,6 tetrachlorophenol (TeCP) in spiked soil with CMCD. The results of batch experiments have shown that CMCD could significantly increase the TeCP extraction from soil. CD sorption on soils as quantified by a fluorescence technique was low, indicating no significant loss of CD during the leaching experiments. The use of CMCD as a flushing agent to enhance the removal of both inorganic and organic pollutants from mixed-contaminated soils appears as a promising remediation method.