Photochemical behaviour of the systemic fungicide carboxin

Irradiation of carboxin (1) with a 500 W UV lamp (filter Pyrex) in CH3CN leads to the products 3, 5-8, 12-14 depending upon the reaction conditions. All photo-products were isolated and characterized. Photooxidation occurred even if unsensitized, while photoalteration was very slow in the absence of oxygen. The main oxygenated-products 3 and 13 were also recovered under biomimetic conditions by exposure of an aqueous solution of 1 to sunlight.     

Natural formation and degradation of chloroacetic acids and volatile organochlorines in forest soil--challenges to understanding

- DOI: http:/dx.doi.org/10.1065/espr2005.06.262 Goal, Scope and Background The anthropogenic environmental emissions of chloroacetic acids and volatile organochlorines have been under scrutiny in recent years because the two compound groups are suspected to contribute to forest dieback and stratospheric ozone destruction, respectively. The two organochlorine groups are linked because the atmospheric photochemical oxidation of some volatile organochlorine compounds is one source of phytotoxic chloroacetic acids in the environment. Moreover, both groups are produced in higher amounts by natural chlorination of organic matter, e.g. by soil microorganisms, marine macroalgae and salt lake bacteria, and show similar metabolism pathways. Elucidating the origin and fate of these organohalogens is necessary to implement actions to counteract environmental problems caused by these compounds. Main Features While the anthropogenic sources of chloroacetic acids and volatile organochlorines are relatively well-known and within human control, knowledge of relevant natural processes is scarce and fragmented. This article reviews current knowledge on natural formation and degradation processes of chloroacetic acids and volatile organochlorines in forest soils, with particular emphasis on processes in the rhizosphere, and discusses future studies necessary to understand the role of forest soils in the formation and degradation of these compounds. Results and Discussion Reviewing the present knowledge of the natural formation and degradation processes of chloroacetic acids and volatile organochlorines in forest soil has revealed gaps in knowledge regarding the actual mechanisms behind these processes. In particular, there remains insufficient quantification of reliable budgets and rates of formation and degradation of chloroacetic acids and volatile organochlorines in forest soil (both biotic and abiotic processes) to evaluate the strength of forest ecosystems regarding the emission and uptake of chloroacetic acids and volatile organochlorines, both on a regional scale and on a global scale. Conclusion It is concluded that the overall role of forest soil as a source and/or sink for chloroacetic acids and volatile organochlorines is still unclear; the available laboratory and field data reveal only bits of the puzzle. Detailed knowledge of the natural degradation and formation processes in forest soil is important to evaluate the strength of forest ecosystems for the emission and uptake of chloroacetic acids and volatile organochlorines, both on a regional scale and on a global scale. Recommendation and Perspective As the natural formation and degradation processes of chloroacetic acids and volatile organochlorines in forest soil can be influenced by human activities, evaluation of the extent of this influence will help to identify what future actions are needed to reduce human influences and thus prevent further damage to the environment and to human health caused by these compounds.     

Factors influencing the total mercury and methyl mercury in the hair of the fishermen of Kuwait

Total and methyl mercury (MeHg) levels in the hair of fishermen are described anticipating that they represent the critical group for dietary exposure. One-hundred human hair samples were collected from fishermen (Egyptians: age range 25-60), living in Doha Fishing Village, Kuwait. Thirty-five additional samples were taken from a control group working in a local construction company (age range 26-35). Overall mean concentrations in the hair of the population of fishermen are 4.181+/-3.220 and 4.025+/-3.130 microg g(-1) for total and MeHg, respectively. The equivalent values for the control are 2.617+/-1.404 and 2.556+/-1.391 microg g(-1) for total and MeHg, respectively. MeHg concentrations are strongly correlated to those of total Hg ( [Formula: see text], [Formula: see text] ) and MeHg concentrations in human hair are unrelated to age and duration of residence in Kuwait but show a positive correlation with the quantity of fish consumed. Levels of Hg in hair also show a tendency to increase in those who prefer to eat the entire fish, including the heads. In general, the concentrations of total and MeHg in fishermens' hair are twice the WHO 'normal' level (2.0 microg g(-1)) but are still less than the WHO threshold level (10.0 microg g(-1)). The results also show that grey hair contains undetectable amounts of Hg and therefore does not reflect individual exposure to this contaminant.     

The effects of air pollution and meteorological parameters on respiratory morbidity during the summer in São Paulo City

Effects of meteorological variables and air pollutants on child respiratory morbidity are investigated during two consecutive summers (December-March 1992/1993 and 1993/1994) at the Metropolitan Area of S?o Paulo (MASP), Brazil. The MASP, with almost 17 million inhabitants, is considered the most populous region in South America. Due to warmer temperatures, increased rainfall and consequent low levels of air pollutants during the summer compared to winter, less attention has been paid to epidemiological studies during this season, especially in tropical urban areas such as S?o Paulo. In the present work, principal component analysis (PCA) is applied to medical end environmental data to identify patterns relating child morbidity, meteorological variables and air pollutants during the summer. The following pollutant concentrations are examined: SO2, inhalable particulate matter (PM10), and O3. The meteorological variables investigated are air temperature, water vapor (water vapor density) and solar radiation. Although low correlation between respiratory morbidity and environmental variables are, in general, observed for the entire dataset, the PCA method indicates that child morbidity is positively associated with O3 for the 1992/1993 summer. This pattern is identified in the third principal component (PC3), which explains about 19% of the total variance of all data in this summer. However, the 1993/1994 summer shows a more complex association between both groups, suggesting stronger ties with meteorological variables. Marked changes in synoptic conditions from the end of January to end of March of the 1993/1994 summer seem to have played an important role in modulating respiratory morbidity. A detailed examination of meteorological conditions in that period indicates that prefrontal (postfrontal), hot (cold) and dry (wet) days favored the observed decrease (increase) of respiratory morbidity.     

Spider webs as environmental indicators

Analysis of spider webs from limestone arches in New South Wales, Australia showed levels of lead and zinc to be several times higher at Jenolan Caves than reference sites at Abercrombie and Wombeyan Caves. The high concentrations at Jenolan were attributed to emissions from motor vehicles that travel through the arch. Analysis of water-soluble ions in webs from Jenolan and Abercrombie Caves showed large differences between the sites, which could be explained by differences in the geology and biology of the cave environments. Spider webs proved useful indicators of environmental chemistry and undoubtedly have applications beyond the cave environments studied here.     

Multi-bioassay approach for assessing the potency of complex mixtures of polycyclic aromatic hydrocarbons

The chick embryotoxicity screening test (CHEST) and the Salmonella/microsome bioassay were used to evaluate embryotoxic and mutagenic endpoints from crude coal tar (CT) and its fractionated polycyclic aromatic hydrocarbon (PAH) mixtures (designated as A, B, C, D and E). In the CHEST assay, CT and PAH mixtures were injected into the egg yolk. A dose-dependent increase in embryo mortality was observed for all fractions. The E fraction resulted in 47% embryo mortality at a dose of 0.125 mg/kg and was more toxic than CT. At a dose of 1 mg/kg, 85-100% embryonic deaths occurred in fractions C and D and these two fractions were more potent than fractions A and B. The main visual toxic manifestations were liver lesions, discoloration of the liver, and edema. Both CT and fractionated PAH mixtures were also tested in the Salmonella/microsome plate incorporation assay with Salmonella typhimurium strain TA98 and were evaluated with and without metabolic activation at five dose levels. In the presence of S9, the CT and fractions C, D and E induced a dose-dependent positive response. Results from the Salmonella/microsome assay were in good agreement with findings from the CHEST assay suggesting that these two bioassays in combination may facilitate the rapid detection and ranking of complex PAH mixtures.     

Prediction of pressure drop in an orifice scrubber based on a Lagrangian approach

A mathematical model has been developed to predict pressure drop in an orifice scrubber. This model is based on a Lagrangian approach for droplet movement and a particle-source-in-cell (PSI-CELL) model for calculating droplet concentration distribution. The k-epsilon turbulent model including body force due to the drag force between fluid and droplets was used to evaluate the fluid velocity distribution. The effect of orifice size on pressure drop and the correlations for mean droplet diameter have been studied. The results from the model have been compared with experimental data. This comparison shows excellent agreement between the calculated results and the experimental data.     

Shade and flow effects on ammonia retention in macrophyte-rich streams: implications for water quality

Controlled releases of NH4-N and conservative tracers (Br- and Cl-) to five reaches of four streams with contrasting macrophyte communities have shown differing retentions, largely as a result of the way plants interact with stream flow and velocity. First-order constants (k) were 1.0-4.8 d(-1) and retention of NH4-N was 6-71% of amounts added to each reach. Distance travelled before a 50% reduction in concentration was achieved were 40-450 m in three streams under low-flow conditions, and 2400-3800 m at higher flows. Retention (%) of NH4-N can be approximated by a simple function of travel time and k, highlighting the importance of the relationship between macrophytes and stream velocity on nutrient processing. This finding has significant management implications, particularly with respect to restoration of riparian shade. Small streams with predominantly marginal emergent plants are likely to have improved retention of NH4-N as a result of shading or other means of reducing plant biomass. Streams dominated by submerged macrophytes will have impaired NH4-N retention if plant biomass is reduced because of reduced contact times between NH4-N molecules and reactive sites. In these conditions water resource managers should utilise riparian shading in concert with unshaded vegetated reaches to achieve a balance between enhanced in-stream habitat and nutrient processing capacity.     

Evaluation of method of preparation of passive diffusion tubes for measurement of ambient nitrogen dioxide

This study was carried out in response to suggestions that the measurement of NO(2) by Palmes-type passive diffusion tubes (PDT) is affected by the method of preparation of the triethanolamine (TEA) absorbent coating on the grids. The following combinations of factors were investigated: TEA solvent (acetone or water), volume composition of TEA in solvent (50% or 20%), and grid coating method (dipping in solution prior to assembly or pipetting solution on after assembly). Duplicate PDTs prepared by each of the 8 methods were exposed in parallel, in urban air, for a total of 80 separate 1 week exposures. NO(2) concentrations derived from PDTs prepared by pipetting methods were significantly less precise than concentrations from dipping methods, with mean RSDs for duplicate measurements of 13.8% and 8.5%, respectively (n= 316 each category). Pipetting methods using solutions of 50% TEA composition were particularly imprecise (mean RSD 17.2%). Data from PDTs prepared by pipetting methods were systematically more poorly correlated with each other and with data from co-located chemiluminescence analysers, than corresponding data from PDTs prepared by dipping methods, indicating that more consistent accuracy was also obtained by the latter PDTs. The statistical evidence suggested that PDTs prepared by pipetting 50% TEA in water generally gave lower NO(2) concentrations. Although this is in agreement with a previous study, it is also possible that such an observation here may be a statistical artefact given the demonstrably poorer precision of this method. The general tendency of PDTs to show positive bias in NO(2) measurement in urban air in 1 week exposures was again evident in this study (mean biases at roadside and urban centre locations of +35% (n= 475) and +18% (n= 112), respectively) consistent with augmentation of within-tube NO(2) flux by chemical reaction between co-diffusing NO and O(3). Overall, it is recommended that the pipetting method of PDT grid preparation is avoided, or at least investigated further, because of the apparent degradation in precision and accuracy of NO(2) measurement. Potential reasons for the effect are discussed.     

MODELING NITROGEN UPTAKE AND POTENTIAL NITRATE LEACHING UNDER DIFFERENT IRRIGATION PROGRAMS IN NITROGEN-FERTILIZED TOMATO USING THE COMPUTER PROGRAM NLEAP

Readily available nitrogen (N) sources such as ammonium nitrate with excessive irrigation present a potential hazard for the environment. The computer program Nitrate Leaching and Economic Analysis Package (NLEAP) is a mechanistic model developed for rapid site-specific estimates of nitrate-nitrogen (NO₃-N) moving below the root zone in agricultural crops and potantial impacts of NO₃-N leaching into groundwater. In this study, the value of NLEAP was tested to simulate N uptake by crops and NO₃-N leaching parameters in large lysimeters under the tomato crop. Three seedlings of tomato variety of H-2274 (Lycopersicum esculentum L.) were transplanted into each lysimeter. N fertilizer at the rate of 140 kg N ha^–1 was sidedressed in two split applications, the first half as ammonium sulphate and the second half as ammonium nitrate. The lysimeters were irrigated based on programs of C 0.75, 1.00, 1.25 and 1.50, C referring to class A-Pan evaporation coefficients. Parameters such as leaching index (LI), annual leaching risk potential (ALRP), N available for leaching (NAL), amount of NO₃-N leached (NL) and amount of N taken up by the crops (NU) were estimated using the NLEAP computer model. To test the ability of model to simulate N uptake and NL, measured values were compared with simulated values. Significant correlations, R² = 0.92 and P < 0.03 for the first year and R² = 0.86 and P < 0.06 for the second year, were found between measured and simulated values for crop N consumption, indicating that the NLEAP model adequately described crop N uptake under the varied irrigation programs using an optimal N fertilization program for the experimental site. Significant correlations, R² = 0.96 and P < 0.01 for the first year and R² = 0.97 and P < 0.01 for the second year, were also found between measured and simulated values of NL, indicating that the NLEAP model also adequately predicted NL under the varied irrigation programs. Therefore, this computer model can be useful to estimate the NO₃-N moving beyond the root zone under conditions in which the present experiment was carried out. Also, the NLEAP-estimated NAL values and other parameters can also be used to improve N management practices and N fertilizer recommendations that will help to decrease the adverse effect of N fertilizer on groundwater quality and farm profitability.