Evaluation of a multiresidue method for pesticides in cereals using supercritical fluid extraction and gas chromatographic detection

Supercritical fluid extraction (SFE) was evaluated to be applied for residue analysis of 22 gas chromatography/electron capture detector-nitrogen phosphorus detector (GC/ECD-NPD) amenable pesticides in rice, wild rice and wheat. Samples were extracted with supercritical carbon dioxide at 200 atm pressure and 50°C temperature, using methanol as a static modifier. Mean recoveries obtained with the proposed SFE method at two spiking levels with four replicates per level are compared with those obtained with an ethyl acetate-based solvent extraction/gel permeation chromatography (GPC) clean up method. Both methods gave consistent high recoveries for almost all the pesticides from all the commodities with overall mean recoveries higher than 70% with relative standard deviations lower than 20%. Remarkable exceptions were captafol and dimethoate, for which low and/or non-reproducible recoveries were obtained with the SFE method. Residue levels determined with both methods in nine different incurred samples of wheat, containing some of the studied pesticides, were very similar, but, in all cases, slightly higher levels were determined with the SFE method.     

Effectiveness evaluation of glyphosate oxidation employing the H2O2/UVC process: Toxicity assays with Vibrio fischeri and Rhinella arenarum tadpoles

The H₂O₂/UVC process was applied to the photodegradation of a commercial formulation of glyphosate in water. Two organisms (Vibrio fischeri bacteria and Rhinella arenarum tadpoles) were used to investigate the toxicity of glyphosate in samples M_1, M₂, and M₃ following different photodegradation reaction times (120, 240 and 360 min, respectively) that had differing amounts of residual H₂O₂. Subsamples of M₁, M₂, and M₃ were then used to create samples M_1,E, M_2,E and M_3,E in which the H₂O₂ had been removed. Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were measured in tadpoles to determine possible sub-lethal effects. In V. fischeri, M_1,E, which was collected early in the photodegradation process, caused 52% inhibition, while M_3,E, which was collected at the end of the photodegradation process, caused only 17% inhibition. Survival of tadpoles was 100% in samples M₂, M₃, and in M_1,E, M_2,E and M_3,E. The lowest percentages of enzymatic inhibition were observed in samples without removal of H₂O₂: 13.96% (AChE) and 16% (BChE) for M₂, and 24.12% (AChE) and 13.83% (BChE) for M₃. These results show the efficiency of the H₂O₂/UVC process in reducing the toxicity of water or wastewater polluted by commercial formulations of glyphosate. According to the ecotoxicity assays, the conditions corresponding to M₂ (11 ± 1 mg a.e. L^?1 glyphosate and 11 ± 1 mg L^?1 H₂O₂) could be used as a final point for glyphosate treatment with the H₂O₂/UV process.     

Sorption and desorption of sulfentrazone in Brazilian soils

This study was undertaken to obtain information about the behavior of sulfentrazone in soil by evaluating the sorption and desorption of the herbicide in different Brazilian soils. Batch equilibrium method was used and the samples were analyzed by high performance liquid chromatography. Based on the results obtained from the values of Freundlich constants (Kf), we determined the order of sorption (Haplic Planosol < Red-Yellow Latosol < Red Argisol < Humic Cambisol < Regolitic Neosol) and desorption (Regolitic Neosol < Red Argisol < Humic Cambisol < Haplic Planosol < Red-Yellow Latosol) of sulfentrazone in the soils. The process of pesticide sorption in soils was dependent on the levels of organic matter and clay, while desorption was influenced by the organic matter content and soil pH. Thus, the use of sulfentrazone in soils with low clay content and organic matter (low sorption) increases the probability of contaminating future crops.     

PCBs in wild mussels (Mytilus galloprovincialis) from the N-NW Spanish coast: current levels and long-term trends during the period 1991-2009

Concentrations of polychlorinated biphenyls (PCBs) were determined in wild mussels (Mytilus galloprovincialis) from seven areas of the N-NW Spanish coast, during the period 1991-2009. The studied area is comprised of highly productive ecosystems which support important commercial fishing and shellfishing activities. The seven PCBs indicator congeners recommended by ICES (IUPAC nos. 28, 52, 101, 118, 138, 153 and 180), were analysed by gas chromatography with an electron capture detector (GC-ECD). Lowest average concentrations of PCBs were recorded in Arousa (1.04 μg kg(-1) wet weight), a low populated area with no industry; while the highest levels were found in areas near cities and/or showing a high industrial activity such as: Bilbao Ziérbena (139 μg kg(-1) ww) or A Coru?a (55 μg kg(-1) ww). The hexachlorinated congeners CB153 and CB138 dominated the profiles in all wild mussel populations, although a geographical pattern was found in which the relative contributions of the lower chlorinated congeners were higher in the west coast (Rías of Vigo, Pontevedra and Arousa), which may reflect the occurrence of recent inputs of those compounds in the area. Finally, the application of the Mann-Kendall's test demonstrate the existence of a significant decrease in PCBs levels since 1991 up to 1996 in the studied area, whereas either a slow decrease or stable concentrations were registered over the past decade.     

Modeling short-term variability of semivolatile organic chemicals in air at a local scale: an integrated modeling approach

Monitoring campaigns from different locations have recently shown how air concentrations of persistent semivolatile contaminants such as polychlorinated biphenyls (PCBs) often exhibit short-term (less than 24 h) variations. The observed patterns have been ascribed to different factors, such as temperature-mediated air-surface exchange and variability of planetary boundary layer (PBL) height and dynamics. Here, we present a new modeling approach developed in order to investigate the short-term variability in air concentrations of organic pollutants at a local scale. A new dynamic multimedia box model is supplied by a meteorological preprocessor (AERMET) with hourly values of air compartment height and wind speed. The resulting model is tested against an existing dataset of PCB air concentrations measured in Zurich, Switzerland. Results show the importance of such modeling approach in elucidating the short- and long-term behavior of semivolatile contaminants in the air/soil system.     

Composition changes in the cuticular surface lipids of the helophytes <Emphasis Type="Italic">Phragmites australis</Emphasis> and <Emphasis Type="Italic">Juncus effusus</Emphasis> as result of pollutant exposure

Aim of the study  

Helophytes like rush and reed are increasingly used for phytoremediation of contaminated water. This study characterises the response of rush and reed plants to chemical stressors such as chlorobenzene, benzene and methyl-tert-butyl ether. The extractable wax layer of the cuticle was chosen for detailed investigations due to its multiple, particularly, protective functions for plants and its easy availability for analysis.     

Phenol degradation using combined effects of hydrodynamic cavitation and oxidant: Doehlert matrix

Hydrodynamic cavitation (HC)-based treatments have been proposed for the degradation of phenol as a toxic pollutant. The present work aimed to optimize the degradation of phenol using HC by means of Doehlert experimental design, which has not been previously addressed. Initially, operational parameters of hydraulic characteristics of the pump, inlet pressure, solution pH, and initial concentration were optimized; later, the effects of pH solution and H₂O₂ loading or initial pollutant concentration on phenol degradation were explored using the Doehlert experimental design. It was observed that phenol degradation is strongly dependent on the pH of the solution. Also, the acidic condition favors the formation of hydroxyl radicals and thus, the degradation of phenol. Based on the Doehlert matrix, the 94.1% phenol degradation and 68.60% total organic carbon (TOC) were obtained in 180 min at 304.5 mg/L of hydrogen peroxide at an initial concentration of 20 mg/L, 2.0 pH, and 90 psi inlet pressure, providing a cavitational yield of 6.33 × 10⁻⁶ mg/J and minimum treatment cost of US$/L 0.13. Overall, it has been observed that HC can be a promising route for the removal of pollutants (phenol) effectively using hydrogen peroxide as an additive.     

Improving Water Resistance of Soy-Based Adhesive by Vegetable Tannin

In this research tannic acid was used to prepare soy-based adhesives for making plywood and fiber board. The different resin formulations were analyzed by Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and its derivative as a function of temperature (DTG) and Fourier Transform Infra-red (FTIR) spectroscopy. The results showed that the addition of tannic acid to soy-based adhesive decreased soy-based adhesive viscosity and its pH. The DSC analysis showed that the denaturation temperature of soy-based adhesives decrease by adding tannic acid. The TGA and DTG curves showed that the thermal degradation of soy flour starts above 146 °C. The FTIR spectroscopy results also showed that the soy flour amino acids appeared to react well with tannic acid. Furthermore, delamination and shear strength test results showed the good water resistance of plywood bonded with soy-based tannic acid-modified adhesive. The mechanical and physical properties such as MOR, MOE, IB, and water resistance of fiberboard were improved, by adding tannic acid to the soy-based adhesive.     

Assessing heavy metal pollution by biomonitoring honeybee nectar in Córdoba (Spain)

Environmental Science and Pollution Research - Nectar of honeybee colonies has been used in order to identify heavy metals and establish the benefit of this type of studies as a tool for...