Predicting logP of pesticides using different software

We compared experimental and calculated logP values using a data set of 235 pesticides and experimental values from four different sources: The Pesticide Manual, Hansch Manual, ANPA and KowWin databases. LogP were calculated with four softwares: HyperChem, Pallas, KowWin and TOPKAT. Crossed comparison of the experimental and calculated values proved useful, especially for pesticides. These are harder to study than simpler organic compounds. Structurally they are complex, heterogeneous and similar to drugs from a chemical point of view. They offer an interesting way to verify the goodness of the different methods. Other studies compared several logP predictors using a single set of experimental values taken as a reference. Here we discuss the utility of the different logP predictors, with reference to experimental data found in different databases. This offers three advantages: (1) it avoids bias due to the assumption that one single data set is correct; (2) a given predictor can be developed on the same data set used for evaluation; (3) it takes account of experimental variability and can compare it with the predictor's variability. In our study Pallas and KowWin gave the best results for prediction, followed by TOPKAT.     

Trimethylbenzoic acids as metabolite signatures in the biogeochemical evolution of an aquifer contaminated with jet fuel hydrocarbons

Evolution of trimethylbenzoic acids in the KC-135 aquifer at the former Wurtsmith Air Force Base (WAFB), Oscoda, MI was examined to determine the functionality of trimethylbenzoic acids as key metabolite signatures in the biogeochemical evolution of an aquifer contaminated with JP-4 fuel hydrocarbons. Changes in the composition of trimethylbenzoic acids and the distribution and concentration profiles exhibited by 2,4,6- and 2,3,5-trimethylbenzoic acids temporally and between multilevel wells reflect processes indicative of an actively evolving contaminant plume. The concentration levels of trimethylbenzoic acids were 3-10 orders higher than their tetramethylbenzene precursors, a condition attributed to slow metabolite turnover under sulfidogenic conditions. The observed degradation of tetramethylbenzenes into trimethylbenzoic acids obviates the use of these alkylbenzenes as non-labile tracers for other degradable aromatic hydrocarbons, but provides rare field evidence on the range of high molecular weight alkylbenzenes and isomeric assemblages amenable to anaerobic degradation in situ. The coupling of actual tetramethylbenzene loss with trimethylbenzoic acid production and the general decline in the concentrations of these compounds demonstrate the role of microbially mediated processes in the natural attenuation of hydrocarbons and may be a key indicator in the overall rate of hydrocarbon degradation and the biogeochemical evolution of the KC-135 aquifer.     

Emission and fate assessment of methyl tertiary butyl ether in the Boston area airshed using a simple multimedia box model: comparison with urban air measurements

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 microg/m3 MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 microg/m3 and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (*OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

A study on emission of phthalate esters from plastic materials using a passive flux sampler

Phthalate esters are used as plasticizer in many plastics, and several studies have shown their toxicity. Phthalate esters are gradually emitted over time, and so it is conceivable that they pose a significant health risk. This study aims to investigate the temperature dependence of the emissions of various phthalate esters and to estimate the health risks of these emissions at various temperatures. A passive-type sampler was developed to measure the flux of phthalate esters from the surface of plastic materials. With this sampler, we examined three widely used plastic materials: synthetic leather, wallpaper and vinyl flooring. The observed maximum emissions of diethyl phthalate, dibutyl phthalate, and diethylhexyl phthalate (DEHP) from these materials at 20°C were 0.89, 0.77, and 14 μg m⁻² h⁻¹, respectively. Emissions at 80°C were 2.8, 4.5×10², and 1.5×10³ μg m⁻² h⁻¹, respectively. The results showed this temperature dependence is determined primarily by the type of phthalate ester and less so by the type of material. The estimation from the results of temperature dependence indicated the concentration of DEHP in a vehicle left out in the sunshine during the day can exceed the recommended levels of Japan Ministry of Health, Labour and Welfare.     

Flooding patterns of the Okavango Wetland in Botswana between 1972 and 2000

The inundated area of the Okavango Delta changes annually and interannually. The variability relates to regional precipitation over the catchment area in the Angolan highlands, and to local rainfall. The patterns of the wetland were captured using more than 3000 satellite images for the period 1972 to 2000, near daily NOAA AVHRR data for 1985-2000, and less frequent images of the Landsat sensors from 1972 onwards. One AVHRR image for every 10-day period was classified into land and water using an unsupervised classification method. Evaluation against Landsat TM and ERS2-ATSR data indicate an agreement of 89% for the size of estimated inundation area. Results show that the wetland area has varied between approximately 2450 km2 and 11400 km2 during the last 30 years.     

Deforestation control in Mato Grosso: a new model for slowing the loss of Brazil's Amazon forest

Controlling deforestation in Brazil's Amazon region has long been illusive despite repeated efforts of government authorities to slow the process. From 1997 to 2000, deforestation rates in Brazil's 9-state "Legal Amazon" region continually crept upward. Now, a licensing and enforcement program for clearing by large farmers and ranchers in the state of Mato Grosso appears to be having an effect. The deforestation rate in Mato Grosso was already beginning to slacken before initiation of the program in 1999, but examination of county-level data suggests that deforestation in already heavily cleared areas was falling due to lack of suitable uncleared land, while little-cleared areas were experiencing rapid deforestation. Following initiation of the program, the clearing rates declined in the recent frontiers. Areas with greater enforcement effort also appear to have experienced greater declines. Demonstration of government ability to enforce regulations and influence trends is important to domestic and international debates regarding use of avoided deforestation to mitigate global warming.     

An interpersonal perspective of perceived stress: Examining the prosocial coping response patterns of stressed managers

We adopt an interpersonal perspective and examine the adaptive effects of managers' perceived stress on their behavior towards subordinates. Drawing from the transactional model of stress (Lazarus & Folkman, 1984), we advance a model that highlights the propensity for stressed managers to engage in prosocial coping behaviors towards their employees, which in turn are related to lower levels of turnover and higher levels of job performance. We tested our predictions in a sample of 281 employees and their 53 managers working in a clothing retailer in Turkey. Consistent with predictions, we found positive effects of managers' perceived stress on their prosocial coping behaviors and employee outcomes. Managers' perceived stress was positively related to sharing credit with employees for managers who held positive implicit prototypes about employees. Results also indicated that managers' perceived stress was positively related to sharing knowledge with their subordinates regardless of implicit follower prototypes. Both sharing credit and sharing knowledge, in turn, were related to turnover intentions and actual turnover, and sharing credit was related to job performance. This study extends past work by adopting an interpersonal perspective of stress and demonstrating that managerial stress can have positive effects on employee outcomes via prosocial coping behaviors.     

Emission factors of fine particulate matter,organic and elemental carbon,carbon monoxide,and carbon dioxide for four solid fuels commonly used in residential heating by the U.S. Navajo Nation

Most homes in the Navajo Nation use wood as their primary heating fuel, often in combination with locally mined coal. Previous studies observed health effects linked to this solid-fuel use in several Navajo communities. Emission factors (EFs) for common fuels used by the Navajo have not been reported using a relevant stove type. In this study, two softwoods (ponderosa pine and Utah juniper) and two high-volatile bituminous coals (Black Mesa and Fruitland) were tested with an in-use residential conventional wood stove (homestove) using a modified American Society for Testing and Materials/U.S. Environmental Protection Agency (ASTM/EPA) protocol. Filter sampling quantified PM_2.5 (particulate matter with an aerodynamic diameter ≤2.5 μm) and organic (OC) and elemental (EC) carbon in the emissions. Real-time monitoring quantified carbon monoxide (CO), carbon dioxide (CO₂), and total suspended particles (TSP). EFs for these air pollutants were developed and normalized to both fuel mass and energy consumed. In general, coal had significantly higher mass EFs than wood for all pollutants studied. In particular, coal emitted, on average, 10 times more PM_2.5 than wood on a mass basis, and 2.4 times more on an energy basis. The EFs developed here were based on fuel types, stove design, and operating protocols relevant to the Navajo Nation, but they could be useful to other Native Nations with similar practices, such as the nearby Hopi Nation.

Implications: Indoor wood and coal combustion is an important contributor to public health burdens in the Navajo Nation. Currently, there exist no emission factors representative of Navajo homestoves, fuels, and practices. This study developed emission factors for PM_2.5, OC, EC, CO, and CO₂ using a representative Navajo homestove. These emission factors may be utilized in regional-, national-, and global-scale health and environmental models. Additionally, the protocols developed and results presented here may inform on-going stove design of the first EPA-certified wood and coal combination stove.     

Comparison of episodic acidification in Canada, Europe and the United States

Episodic acidification is practically a ubiquitous process in streams and drainage lakes in Canada, Europe and the United States. Depressions of pH are often smaller in systems with low pre-episode pH levels. Studies on European surface waters have reported episodes most frequently with minimum pH levels below 4.5. In Canada and the United States, studies have also reported a number of systems that have had minimum pH levels below 4.5. In all areas, change in water flowpath during hydrological events is a major determinant of episode characteristics. Episodic acidification is also controlled by a combination of other natural and anthropogenic factors. Base cation decreases are an important contributor to episodes in circumneutral streams and lakes. Sulphate pulses are generally important contributors to episodic acidification in Europe and Canada. Nitrate pulses are generally more important to episodic acidification in the Northeast United States. Increases in organic acids contribute to episodes in some streams in all areas. The sea-salt effect is important in near-coastal streams and lakes. In Canada, Europe and the United States, acidic deposition has increased the severity (minimum pH reached) of episodes in some streams and lakes.     

Fractionation of atmospheric acid and base components within storm events by precipitation scavenging processes

Concentrations of ions in storm rainwater in Texas have been monitored for each 0.254 mm increment of precipitation. The changes in concentrations have been analyzed to investigate the role of differential rates of scavenging of particulate matter of differing particle size, and especially the major acid and base components. The empirical trend at the onset of rainfall is a chemical fractionation of acids and bases with correspondingly wide pH variations. These results are confirmed by model calculations, which show a significant preferential scavenging of calcium relative to sulfate in the first 10 mm of rainfall, resulting in fractionation of bases and acids from their atmospheric concentrations. Previous studies, using Target Transformation Factor Analysis of ion concentrations in storm precipitation and regional ambient aerosol data, statistically determined the average source for acidic secondary species and alkaline particulate matter. Two types of crustal sources were identified as western and eastern soil dust. In this study, an alternate physical explanation for these two soil dust factors is offered. As a storm progresses, the elements in the local soil dust are fractionated as a result of their differential rates of precipitation scavenging, enriching species predominantly in the fine particle size and depleting elements predominantly in the coarse particle size. This fractionation process results in a single source having different elemental ratios at the beginning and at the end of a rain event. For Austin, Dallas, and Tyler, Texas, the soil dust previously identified as being from eastern sources could, instead, be a fractionated form of the western soil source.