Enantiomeric separation of imidazolinone herbicides using chiral high-performance liquid chromatography

Chiral high-performance liquid chromatography (HPLC) is one of the most powerful tools to prepare enantiopure standards of chiral compounds. In this study, the enantiomeric separation of imidazolinone herbicides, i.e., imazethapyr, imazapyr, and imazaquin, was investigated using chiral HPLC. The enantioselectivity of Chiralpak AS, Chiralpak AD, Chiralcel OD, and Chiralcel OJ columns for the three analytes was compared under similar chromatographic conditions. Chiralcel OJ column showed the best chiral resolving capacity among the test columns. The resolved enantiomers were distinguished by their signs of circular dichroism detected at 275 nm and their structures confirmed with LC-mass spectrometric analysis. Factors affecting the chiral separation of imidazolinones on Chiralcel OJ column were characterized. Ethanol acted as a better polar modifier than the other alcohols including 2-propanol, 1-butanol, and 1-pentanol. Although the acidic modifier in the mobile phase did not influence chiral recognition, it was necessary for reducing the retention time of enantiomers and suppressing their peak tailing. Thermodynamic evaluation suggests that enantiomeric separation of imidazolinones on Chiralcel OJ column is an enthalpy-driven process from 10 to 40 degrees C. This study also shows that small amounts of pure enantiomers of imidazolinones may be obtained by using the analytical chiral HPLC approach.     

Agricultural sustainability: concepts, principles and evidence

Concerns about sustainability in agricultural systems centre on the need to develop technologies and practices that do not have adverse effects on environmental goods and services, are accessible to and effective for farmers, and lead to improvements in food productivity. Despite great progress in agricultural productivity in the past half-century, with crop and livestock productivity strongly driven by increased use of fertilizers, irrigation water, agricultural machinery, pesticides and land, it would be over-optimistic to assume that these relationships will remain linear in the future. New approaches are needed that will integrate biological and ecological processes into food production, minimize the use of those non-renewable inputs that cause harm to the environment or to the health of farmers and consumers, make productive use of the knowledge and skills of farmers, so substituting human capital for costly external inputs, and make productive use of people's collective capacities to work together to solve common agricultural and natural resource problems, such as for pest, watershed, irrigation, forest and credit management. These principles help to build important capital assets for agricultural systems: natural; social; human; physical; and financial capital. Improving natural capital is a central aim, and dividends can come from making the best use of the genotypes of crops and animals and the ecological conditions under which they are grown or raised. Agricultural sustainability suggests a focus on both genotype improvements through the full range of modern biological approaches and improved understanding of the benefits of ecological and agronomic management, manipulation and redesign. The ecological management of agroecosystems that addresses energy flows, nutrient cycling, population-regulating mechanisms and system resilience can lead to the redesign of agriculture at a landscape scale. Sustainable agriculture outcomes can be positive for food productivity, reduced pesticide use and carbon balances. Significant challenges, however, remain to develop national and international policies to support the wider emergence of more sustainable forms of agricultural production across both industrialized and developing countries.     

Avian disease at the Salton Sea

A review of existing records and the scientific literature was conducted for occurrences of avian diseases affecting free-ranging avifauna within the Salton Sea ecosystem. The period for evaluation was 1907 through 1999. Records of the U.S. Department of Agriculture, Bureau of Biological Survey and the scientific literature were the data sources for the period of 1907–1939. The narrative reports of the U.S. Fish and Wildlife Service's Sonny Bono National Wildlife Refuge Complex and the epizootic database of the U.S. Geological Survey's National Wildlife Health Center were the primary data sources for the remainder of the evaluation. The pattern of avian disease at the Salton Sea has changed greatly over time. Relative to past decades, there was a greater frequency of major outbreaks of avian disease at the Salton Sea during the 1990s than in previous decades, a greater variety of disease agents causing epizootics, and apparent chronic increases in the attrition of birds from disease. Avian mortality was high for about a decade beginning during the mid-1920s, diminished substantially by the 1940s and was at low to moderate levels until the 1990s when it reached the highest levels reported. Avian botulism (Clostridium botulinum type C) was the only major cause of avian disease until 1979 when the first major epizootic of avian cholera (Pasteurella multocidia) was documented. Waterfowl and shorebirds were the primary species affected by avian botulism. A broader spectrum of species have been killed by avian cholera but waterfowl have suffered the greatest losses. Avian cholera reappeared in 1983 and has joined avian botulism as a recurring cause of avian mortality. In 1989, avian salmonellosis (Salmonella typhimurium) was first diagnosed as a major cause of avian disease within the Salton Sea ecosystem and has since reappeared several times, primarily among cattle egrets (Bubulcus ibis). The largest loss from a single epizootic occurred in 1992, when an estimated 155000 birds, primarily eared grebes (Podiceps nigricollis), died from an undiagnosed cause. Reoccurrences of that unknown malady have continued to kill substantial numbers of eared grebes throughout the 1990s. The first major epizootic of type C avian botulism in fish-eating birds occurred in 1996 and killed large numbers of pelicans (Pelecanus occidentalis & P. erythrorhynchos). Avian botulism has remained as a major annual cause of disease in pelicans. In contrast, the chronic on-Sea occurrence of avian botulism in waterfowl and shorebirds of previous decades was seldom seen during the 1990s. Newcastle disease became the first viral disease to cause major bird losses at the Salton Sea when it appeared in the Mullet Island cormorant (Phalacrocorax auritus) breeding colony during 1997 and again during 1998.     

Stability of bacterial populations in tropical soil upon exposure to Lindane

The effect of the pesticide Lindane on microbial populations was analyzed in soil with a history of contamination with various chemicals, including this pesticide. Soil microcosms were amended with 100 mg Lindane/kg soil and microbial populations were monitored for 70 days. Bacterial cell concentrations, metabolic versatility (whole community Biolog), and genetic diversity (16S rDNA/denaturing gradient gel electrophoresis) were used to monitor microbial communities. Results show the persistence of Lindane in the soil environment; at the end of the experiment, 70% of the added Lindane remained undegraded. A reduction of 50% in bacterial cell concentration was observed in Lindane-amended microcosms during the 2nd week of the experiment. This reduction was correlated with a reduction in the rate of substrate utilization as observed by Biolog. Overall, no effect of Lindane was observed on the metabolic versatility and genetic diversity in these soils, demonstrating the ability of these bacterial populations to tolerate the pressure caused by the addition of pesticides.     

Effects of Melia azedarach, (Meliaceae) fruit extracts on the leafminer Liriomyza huidobrensis, (Diptera, Agromyzidae): Assessment in laboratory and field experiments

Control of the widely distributed pest Liriomyza huidobrensis, is complicated due to the protected habit of the leafmining larvae, and their resistance to insecticides. The effects of Melia azedarach, (Meliaceae) fruit extracts against adults and larvae of L. huidobrensis, were investigated. In the laboratory, leaves of Cucurbita, sp. infested with first and third instar larvae were treated with different extract solutions. Larval and pupal survival, as well as wing‐spread of adults, were ssessed. Female adult behaviour towards the extract was also analysed in terms of number of feeding punctures and number of offspring left on treated/untreated leaves. In the field, an infested Vicia faba, crop was sprayed four times at weekly intervals with plant extract, water, and a blank solution. The number of adult leafminers and parasitoids emerging from sampled leaves from each treatment were compared. The laboratory tests showed translaminar action of the extracts, which negatively affected leafminer pupal survival, while body size was not affected. The extracts also deterred feeding by adult females and may also have caused reduction in oviposition rates. All solutions and concentrations tested had similar effects. In the field, extract effects were consistent with those from laboratory trials, number of pupae and pupal survival being lower on treated plants. Percentage parasitism was not affected by plant extract treatment, suggesting a selective activity.     

Persistent organochlorine pesticides detected in blood and tissue samples of vultures from different localities in South Africa

Gaschromatography was used to establish the presence of quantifiable residues of 14 persistent chlorinated hydrocarbon pollutants in whole blood, clotted blood, heart, kidney, liver and muscle samples obtained from individual African whitebacked (Pseudogyps africanus), Cape griffon (Gyps coprotheres) and Lappetfaced (Torgos tracheliotos) vultures from different localities in South Africa. The levels of pesticides measured in whole blood samples of live specimens were compared between nestlings from two natural breeding colonies, adults from a wildlife area and birds held in captivity. Statistically significant (P<0.05) differences between populations were detected in geometric means calculated for γ-BHC (lindane), α(cis)-chlordane and α-endosulfan. Five of the organochlorine contaminants displayed significant variations between concentrations detected in the clotted blood, organs and muscles excised from vulture carcasses. This includes residues of γ-BHC, α-chlordane, dieldrin, β-endosulfan and heptachlor epoxide. Values of the respective biocides measured in vulture samples were generally low in comparison to results documented for a number of avian species. Although no threat is posed by any of the organochloride pesticides, continual monitoring of especially breeding colonies is recommended. Furthermore, the suitability of African whitebacked vulture nestlings as basic bioindicators is highly advocated.     

Review on the sublethal effects of pure and formulated glyphosate on bees: Emphasis on social bees

Bees are declining worldwide, and the use of pesticides has been linked to this problem. Studies show that even herbicides can negatively impact bees, causing death or compromising health. As a result, concern about the use of glyphosate (GLY) has increased, as it is the most sold pesticide. Studies have shown that exposure of bees to GLY can trigger sublethal effects. Considering the speed with which information is published, reviews become important for the integration of knowledge, aiding understanding of the topic. Therefore, the present study aimed to review the literature on the sublethal effects of GLY and the different commercial formulations on bees. After the literary review, it was observed that the exposition, acute and chronic, of larvae and adults of social and solitary bees, to GLY and its formulations, can trigger alterations in gene expression, enzyme functioning, oxidative metabolism, cell/tissue structure, intestinal microbiota diversity, learning, food consumption, flight and vertical displacement capacity, circadian cycle and body development of these insects. The most used species in the studies was Apis mellifera L. Studies are still necessary to understand the sublethal effects of GLY on bees, in the medium and long term, on colony homeostasis, especially about the information on the toxicity of some surfactants present in the different commercial formulations.     

Effect of Some Pesticides on Reproduction of Rotifer <Emphasis Type="Italic">Brachionus plicatilis</Emphasis> Müller

Pesticides have been major contributors to environmental pollution and they are now widely distributed in aquatic environments. Zooplankters are frequently used as test animals to detect aquatic contaminants because of their sensitivity and ecological importance. We investigated the effect of a 7-day exposure to four commonly used pesticides (diazinon, fenitrothion, methoprene and isoprothiolane) on reproduction of the rotifer Brachionus plicatilis. Pesticide concentrations of 3–7 times lower than the 24-h 50% lethal concentration (24-h LC₅₀) were tested to determine the ‚no observed effect’ concentration (NOEC), ‚lowest observed effect’ concentration (LOEC), and the ‚50% effective’ concentration (EC₅₀) on specific growth rate (r), sexual reproduction, fertilization, resting egg production, and hatchability of resting eggs. Results showed that the lowest EC₅₀ value of r, mixis, fertilization, and resting egg production of 1.4 μM for diazinon was 63 times lower than its 24-h LC₅₀ of 88.4 μM, while for fenitrothion it was 66 times (3.5 and 229.8 μM, respectively). For isoprothiolane, the lowest EC₅₀ value of r, mixis, fertilization, and resting egg production of 8.9 μM was 25 times lower than its 24-h LC₅₀ of 220.7 μM, while for methoprene was 37 times (2.7 and 100.8 μM, respectively). In all pesticides, hatching rate of resting eggs consistently gave the lowest EC₅₀ values which is about 2–40 times lower than the lowest EC₅₀ of r, mixis, fertilization, and resting egg production. Hatchability of resting eggs therefore is the most sensitive parameter in detecting effects of pesticides exposure in rotifer B. plicatilis.     

From Metchnikoff to Monsanto and beyond: the path of microbial control

In 125 years since Metchnikoff proposed the use of Metarhizium anisopliae to control the wheat cockchafer and brought about the first field trials, microbial control has progressed from the application of naturalists' observations to biotechnology and precision delivery. This review highlights major milestones in its evolution and presents a perspective on its current direction. Fungal pathogens, the most eye-catching agents, dominated the early period, but major mycological control efforts for chinch bugs and citrus pests in the US had questionable success, and interest waned. The discoveries of Bacillus popilliae and Bacillus thuringiensis began the era of practical and commercially viable microbial control. A program to control the Japanese beetle in the US led to the discovery of both B. popilliae and Steinernema glaseri, the first nematode used as a microbial control agent. Viral insect control became practical in the latter half of the 20th century, and the first registration was obtained with the Heliothis nuclear polyhedrosis virus in 1975. Now strategies are shifting for microbial control. While Bt transgenic crops are now planted on millions of hectares, the successes of more narrowly defined microbial control are mainly in small niches. Commercial enthusiasm for traditional microbial control agents has been unsteady in recent years. The prospects of microbial insecticide use on vast areas of major crops are now viewed more realistically. Regulatory constraints, activist resistance, benign and efficacious chemicals, and limited research funding all drive changes in focus. Emphasis is shifting to monitoring, conservation, integration with chemical pesticides, and selection of favorable venues such as organic agriculture and countries that have low costs, mild regulatory climates, modest chemical inputs, and small scale farming.     

Pollutant effects on Pacific oyster, Crassostrea gigas (Thunberg), hemocytes: Screening of 23 molecules using flow cytometry

The shellfish industry is an important economic activity in France, occurring mostly in estuarine zones subject to pollution due to anthropogenic activities. The harmful effects of pollutants on species inhabiting these estuarine zones are not well known. Among marine species, bivalve mollusks---particularly Pacific oyster, Crassostrea gigas---may serve a model of interest. The species is sedentary and filter-feeding, which favors bioaccumulation of pollutants in their tissues. Oysters may be suitable for studies on disturbance by pollutants of physiological activities, among which defense mechanisms are poorly documented in bivalves. In this study, effects of pollutants on hemocyte functions were monitored in Pacific oyster, C. gigas. Hemocytes were exposed in vitro to selected pollutants. The strategy for investigating the effects of pollutants on hemocyte functions is based on several biomarkers, which is more relevant than that of published papers based on single-endpoint experiments. Pollutants belonging to the most important groups of xenobiotics (PAHs, PCBs, and pesticides) were selected and their effect on hemocyte activities was analyzed using flow cytometry. Twenty-three pollutants were tested and eight of them showed significant modulation of hemocyte activities. PAHs and PCB 77 induced a decrease of hemocyte activity after an incubation periods of 4 and 24 h at 200 μmol/L. Three pesticides (2,4D, paraoxon, and chlorothalonil) modulated hemocyte activities. A mixture of eight pesticides also decreased phagocytotic activity. This study is one of the first to investigate the effects of so many pollutants on hemocyte functions at the same time and therefore allows a real comparison of different pollutant effects