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.     

Environmental impacts of coastal aquaculture in eastern mediterranean bays the case of astakos gulf,Greece

GOAL, SCOPE AND BACKGROUND: Over the last decade Greece has become a leading country in the EU as concerns the cage farming of seabream and seabass. A strong debate has risen, however, about the environmental impacts of aquacultures in the coastal areas. The present paper deals with this problem and it is based on measurements of physico-chemical parameters in the water column, particulate matter and sediments in the area of Astakos Gulf, a coastal embayment in western Greece where three big fish farms are currently operating. METHODS: Water samples were collected by using Hydro-Bios sampling bottles, whereas a prototype sediment trap was installed under a fish cage for the collection of particulate matter. Temperature, dissolved oxygen, pH and salinity were measured in situ using portable equipment. Nutrients were determined by standard spectrophotometric methods. Trace metals were determined by Atomic Absorption Spectrometry. Dissolved organic carbon was determined by a Shimadzu 5000A carbon analyzer, whereas organic carbon in sediments was determined titrimetrically. RESULTS AND DISCUSSION: No clear eutrophication incidents have been identified, although the water column near the fish farms was enriched in nutrients and organic carbon. A sludge 'blanket' covers considerable parts of the seabed and is enriched in colloidal organic carbon and trace metals (Cd, Cu, Fe and Zn) that come from unused fish food. The biodegradation of this sludge leads to the development of anoxic conditions followed by the formation of undesirable gases, precipitation or remobilization of metals and the extinction of benthic fauna. CONCLUSION: The operation of fish farms at the coastal area of Astakos Gulf, and probably in similar Mediterranean gulfs, affects the marine environment, particularly in the vicinity of the cages. The most significant influence concerns the near-bottom water layer. The environmental impacts depend on the amount of food given to fishes, the mode of feeding, the fish density in cages, the annual production and the years of unit operation. The hydrology and the geomorphology of the area are also critical factors for its environmental quality. RECOMMENDATION AND OUTLOOK: The success of the fish-farming sector in the Mediterranean is accompanied by environmental and, in some extents, by social and marketing problems. These problems, derived from the rapid development of fish farming, can be solved only through an integrated management, using methods such as environmental impact assessment, risk assessment, economic evaluation, vulnerability assessments, resource accounting, cost-benefit analysis and outcome-based monitoring.     

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.     

Real-time indoor and outdoor measurements of black carbon in an occupied house: an examination of sources

Black carbon (BC) was measured every 5 min for two years (May 1998-May 2000) inside and immediately outside a northern Virginia house (suburban Washington, DC) occupied by two nonsmokers. Two aethalometers, which measure BC by optical transmission through a quartz fiber tape, were employed indoors and outdoors. Meteorological parameters were obtained on an hourly basis from nearby Dulles airport. Indoor activities were recorded to identify indoor sources such as combustion activities, which occurred 9% of the time during the first year and 4% of the time during the second year. At times without indoor sources, indoor/outdoor BC ratios averaged 0.53 in the first year and 0.35 in the second year. The main outdoor source of BC was the general regional background, contributing 83-84% of the total during each of the two years. Morning rush hour traffic contributed 8-9% of the total BC. An evening peak in the fall and winter, thought to include contributions from wood burning, was responsible for approximately 8% of the annual average BC concentration. The main indoor sources of BC were cooking and candle burning, contributing 16 and 31%, respectively, of the annual average indoor concentrations in the two years. Relative humidity (RH) affected the outdoor aethalometer in both years. An artifact associated with the tape advance was noted for the aethalometer, but a correction factor was developed that reduced the associated error by a factor of 2.