Fate of pesticides in the arid subtropics, Botswana, Southern Africa.

Despite a history of pesticide usage, few data exist on their concentrations in air and soil of Southern Africa. To add to the understanding of the processes controlling the fate of organic contaminants in arid regions, the levels, spatial trends, and seasonal variability of pesticides were studied in air and soil from Botswana. XAD resin-based passive air samplers (PAS) were deployed at 15 sites across the country from May 2006 to May 2007. Soil samples were collected from the vicinity of nine of the PAS sampling sites. In addition, 27 24-h high-volume air samples were collected in Maun, at the southeastern edge of the Okavango Delta, every two weeks for one year. Levels of pesticides in PAS were low, with α-endosulfan and lindane being most abundant. Concentrations in soils were extremely low and only soils with high organic carbon contained notable amounts of dieldrin and traces of other pesticides. In particular, air and soil from the Okavango Delta had very low levels even though the area had repeatedly been sprayed with DDT and endosulfan in the past. Air samples from Eastern Botswana, where the majority of the population lives, contained higher levels. Higher air concentrations of α-endosulfan occurred during summer and higher HCB levels occurred in winter. This seasonality was related with neither minor seasonal changes in temperature nor hydrological seasonal events such as the rainy season or the flooding of the Okavango Delta. Thus, the observed spatial and seasonal patterns are more likely related to pesticide usage pattern than to environmental factors or historical use. High temperature and low organic matter content limit the uptake capacity of most subtropical soils for pesticides. No evidence was found that sorption to dry mineral matter plays a major role. Arid soils in subtropical regions are therefore neither a major reservoir of organic contaminants nor do they constitute a significant long-term source of pesticides to the atmosphere.

Spatial and temporal pattern of pesticides in the global atmosphere.

As part of the Global Atmospheric Passive Sampling (GAPS) study, XAD-resin based passive samplers are being deployed for consecutive one-year periods at numerous sites on all seven continents to determine annually averaged concentrations of persistent organic pollutants. Concentrations of banned organochlorine pesticides as well as a number of current-use pesticides in samples from the first four years, roughly coinciding with 2005, 2006, 2007 and 2008, show distinct spatial and temporal patterns. Whereas organochlorine pesticides such as alpha- and gamma-hexachlorocyclohexane, endosulfans, DDT and its metabolites, and chlordane-related compounds tend to be more prevalent in developing countries, especially in Asia, concentrations of current use pesticides such as trifluralin and chlorothalonil are often higher in Europe and North America. Based on 15 stations with four years of data, levels of hexachlorobenzene, hexachlorocyclohexanes and chlordanes decline in most world regions, which may reflect decreased usage in response to global restrictions. Levels of organochlorine pesticides in India, however, remain exceptionally high. Concentrations of alpha-endosulfan, chlorothalonil and trifluralin decrease in the European atmosphere during the sampling periods, indicating reduced usage. Consistently high alpha/gamma-HCH ratios in air samples from high Northern latitudes confirm that re-volatilization from the Arctic Ocean is a significant source of alpha-HCH. The highest levels of alpha-HCH, however, occur in conjunction with high gamma-HCH levels, suggesting that lindane use is now the major source of alpha-HCH to the global atmosphere. Although a wide variety of sampling site types aids in characterizing the entire global concentration variability of a pesticide, it also increases greatly the number of sites required for a robust regional differentiation.

Novel fluoropeptidomimetics: synthesis, stability studies and protease inhibition.

Designer fluoropeptidomimetics as protease inhibitors are revealed. The key peptidomimetic region in the inhibitors contains a '-CHF-S-' moiety and is designed to mimic the tetrahedral oxyanion species during the hydrolysis of a peptide bond. Designed fluoropeptidomimetics in aqueous methanol slowly (in several hours to days) yielded the corresponding methyl ether and/or the oxazole derivatives after cyclization. Alkyl substitutions at the C-2 position exhibited enhanced aqueous stability. Nature of '-CHF-S-' moiety and the stabilities of various fluoropeptidomimetics in aqueous solution are disclosed in detail. Fluoropeptidomimetics containing bulky substitutions at P1 such as compounds 15 and 16 exhibited time-dependent loss of activities against chymotrypsin, upto [corrected] 67% and 79% with a Ki of 63 and 120 microM, respectively. Fluoropeptidomimetics are a novel class of protease inhibitors and the next generation of fluoropeptidomimetics should incorporate enhanced stability.