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.     

Aerosols in a Mediterranean Forest: Sulfates,Particle Size Distribution,and Growth Rates

ABSTRACT

Particle size distribution measurements in 16 nonlinear intervals covering the 0.1–7.5 μm range and concurrent sulfate concentrations were continuously recorded in September 1996 over the period of two weeks in a Mediterranean forest. Sulfate size distribution was derived from a linear correlation fit between the concentrations and the number of particles recorded at each particle size interval. The results revealed two modal diameters for sulfates, with typical diameters at 0.3 and 0.675 μm. These results were associated with two different dominant chemical mechanisms governing sulfate formation.

In order to describe the dominant chemical mechanism, the growth law approach was applied. Growth rates were determined using the parameter estimates of the fitted particle size distribution function. By matching these data with sulfate concentrations, the dominant chemical reactions were identified. The results have shown that sulfate formation is governed by both homogeneous and heterogeneous reactions and that the latter process was dominant. Condensation reactions prevailed in the early morning and late afternoon, and volume reactions at night, particularly in high-moisture conditions. From the observational data, the gas-to-particle conversion rate for sulfur dioxide (SO₂) at nighttime was also derived, yielding a 2.18%/hr^-1.     

Long-Term Efficiency of Catalytic Converters Operating in Mexico City

ABSTRACT

A 1999 ordinance by the Government of Mexico City bans 1993 model-year vehicles from on-road operation if their catalytic converters are not replaced with new ones. To validate the benefits of this action, we examined three issues related to exhaust emissions of vehicles equipped with catalytic converters. After selecting representative fleets of in-use vehicles, a comparison between emissions and catalyst efficiency in cars with two categories of exhaust emission limits was carried out. For that purpose, two fleets were selected, each made up of 10 vehicles run under similar conditions. A third, larger fleet with emissions control systems was used to evaluate and simulate real-world conditions of vehicles in a controlled laboratory. Finally, the aging effect on the catalytic converter was studied on vehicles run for 100,000 km, replacing their old emission control devices for new ones.

The 1991-1992 model-year vehicles showed a high percentage of compliance with the corresponding emissions standard (90%) in comparison with 1993 model-year and later vehicles (Tier 0). However, NO_x emissions were higher for the newer vehicles. Fifty percent of the 1991-1992 model-year vehicles evaluated under the official inspection/maintenance (I/M) procedure did not meet the regulated emissions standard when the results were compared with those of the U.S. Federal Test Procedure     

The transboundariness approach and prioritization of transboundary aquifers between Mexico and Texas

“Transboundariness” refers to a new approach that identifies and prioritizes transboundary aquifers using socio-economic and political criteria, improving their characterization by using other variables in addition to their mere physical boundaries. This approach is applied to the hydrogeological units/aquifers shared by Mexico and Texas, with the following results. First, the rankings agree with the current level of attention to transboundary aquifers in the region by both countries, providing a quantifiable system that could be tested in other transboundary aquifers. Second, this approach provides a holistic and integrative perspective for transboundary aquifer assessment and prioritization. Third, this prioritization exercise expands the criteria currently used into a more integrative regime of groundwater links to the community as a whole. Finally, the results reflect not only how the transboundary aquifers are being used (or neglected) but also the socio-political context of the populations that depend on these resources for current and future development.     

Energy efficiency during conventional and novel sintering processes: the case of Ti–Al2O3–TiC composites

The conventional (hot pressing or HP) and the novel (spark plasma sintering or SPS) consolidation techniques were compared when processing Ti–Al₂O₃–TiC powders obtained by self-propagating high-temperature synthesis (SHS). It was found that the two different methods are able to produce similar materials, in some cases (Vickers hardness and wear rate) slightly better for SPSed samples. However, SPS does not need sintering temperatures as high as HP to obtain fully dense products. Most significantly, processing times were strongly reduced when adopting the SPS technique instead of HP, i.e. 4–7 min and about 5 h, respectively. Finally, when the total energies required during each SPS or HP experiment were compared, it was found that the use of the SPS technology allowed for an energy saving in the order of 90–95%. This fact makes SPS significantly advantageous from environmental and economical points of view compared to HP.     

A new FTIR method to monitor transesterification in biodiesel production by ultrasonication

New renewable fuels are urgently needed due to increasing fossil fuel pollution. Biodiesel, which contains alkyl esters produced by transesterification of oils, is an alternative fuel. Nevertheless, the main problem of biodiesel is its high price. Costs can be reduced by replacement of the current homogeneous catalysts by heterogeneous catalysts; however, research for new catalysts is actually slowed by lengthy analytical techniques. Here, we set up a simple and rapid analytical method using Fourier transform infrared (FTIR) to monitor transesterification. Conversion of sunflower and recycled cooking oils to their corresponding methyl esters was easily measured using a linear correlation between the intensity of an infrared peak at 1,437 cm^?1 and the percent conversion. The results obtained by infrared were validated by gas chromatography. We also studied the effect of 20 kHz ultrasonic irradiation on biodiesel synthesis. Using our FTIR method, we found that replacing mechanical stirring with an ultrasonic probe leads to quality biodiesel in 10 min for sunflower oil and 20 min for recycled cooking oil.     

Influence of task demands on occupational stress: Gender differences

IntroductionOccupational stress is a common phenomenon in our society, and generates problems for both workers' health and the functioning of organizations. Over past decades numerous studies have examined occupational stress from the perspective of gender, offering somewhat contradictory results. Some of them found no differences and others indicated that either men or women suffer from greater amounts of occupational stress.MethodThe purpose of this study was to analyze gender differences in stress in situations that involve certain occupational demands. The data used were taken from a random sample population of 11,054 (5,917 men and 5,137 women) from the VI National Survey on Working Conditions (NSWC) which was conducted in Spain in 2007. To carry out this study, a probabilistic model was constructed using Bayesian networks, with the following variables related to task demands: working with tight deadlines, quick work, intellectually demanding work, complicated tasks, repetitive tasks, excessive work, and work demanding high attention levels.ResultsThe results of this study reveal that: the indicators studied significantly increased stress levels; women initially had higher stress levels than men; and when exposed to determined task demands, stress differences between genders tended to increase.Impact on IndustryCompanies need to consider the gender of their workers when assigning tasks in high demand/stress jobs.     

Feasibility of using salivary biomarkers to assess human exposure to chlorpyrifos

The objective of this study was to determine the feasibility of using salivary biomarkers to assess chlorpyrifos exposure using data collected from laboratory controlled animal study, as well as from farmers in Thailand and Nicaragua who applied chlorpyrifos in the field. Time-matched saliva and arterial blood samples were collected from rats and adult agricultural workers, while spot saliva samples were collected from children. Specimen samples were analyzed for chlorpyrifos using a commercially available enzyme-linked immunosorbent assay. The results from both animal and farmer studies show that chlorpyrifos is excreted into saliva. Nevertheless, salivary excretion of chlorpyrifos seems to differ from other pesticides, as evidenced by the lack of correspondence of chlorpyrifos levels between saliva and plasma samples. The lower chlorpyrifos concentrations in saliva collected from rats, and from farmers and their children, may have resulted from the rapid hydrolysis of chlorpyrifos during the intracellular passive diffusion in the salivary gland. In conclusion, chlorpyrifos is excreted into saliva; however, the majority of chlorpyrifos that is excreted in saliva may have been metabolized due to base-dependent hydrolysis. Because of this finding, it was hypothesized that it would be ideal to measure its metabolite, 3,5,6-trichloropyridinol, in saliva as the biomarker for chlorpyrifos exposure.     

Removal of an airborne low volatility metal under fuel-rich and fuel lean conditions through condensation onto soot and/or sorbent particles.

The removal by a sorbent of a low volatility heavy metal, barium, from a combustor exhaust stream was investigated experimentally. The barium was introduced into the gas phase through a combustion process simulating incineration of waste materials. Sorbent- and metal-feed-rate, temperature and air intake were varied to study the impact on the gas-to-particle conversion and the metal condensation process. Peak temperature and subsequent temperature drop were found to be the dominant factors affecting the condensation process. Fuel-rich and fuel-lean conditions result in lower peak temperatures and a more rapid temperature drop relative to stoichiometric conditions. Since the metal vapor saturation pressure falls exponentially with temperature a larger condensation rate was observed, as long as nucleation was suppressed. Fuel-rich conditions promote the formation of soot particles. These particles function as sites for subsequent metal-species condensation. Chlorine was injected into the flow, to study the effect on metal vaporization. Chlorine promoted the volatilization of barium and therefore the subsequent condensation capture was made more effective.     

Air quality monitoring system using lichens as bioindicators in Central Argentina

Air quality studies with bioindicators have not been well developed in South America. In the city of Córdoba, there are not permanent air pollutant measurements by equipment. In order to develop an air quality biomonitoring system using lichens, we applied a systematic sampling in the city of Córdoba, Argentina. A total of 341 plots were sampled in the area of the city which is a square of 24 × 24 km. In each sample plot we selected three phorophytes and estimated the frequency and cover of lichen species growing at 1.5 m on trunks. We also calculated the Index of Atmospheric Purity (IAP) using lichen frequencies. Maps with number of lichen species, cover values, and IAP were performed. The lichen community was described with nine species where Physcia undulata and Physcia endochryscea were the most frequent. Moreover, these two species were dominant in the community with the highest cover index. The central area of the city is considered a lichen desert with poor air quality. The southeast and northwest areas of the city showed the highest IAP values and number of species. In general, the city shows fair air quality and few areas with good and very good air quality.