Enantiomeric separation of metolachlor and its metabolites using LC-MS and CZE

The stereoisomers of metolachlor and its two polar metabolites [ethane sulfonic acid (ESA) and oxanilic acid (OXA)] were separated using liquid chromatography-mass spectrometry (LC-MS) and capillary zone electrophoresis (CZE), respectively. The separation of metolachlor enantiomers was achieved using a LC-MS equipped with a chiral stationary phase based on cellulose tris(3,5-dimethylphenyl carbamate) and an atmospheric pressure chemical ionization source operated under positive ion mode. The enantiomers of ESA and OXA were separated using CZE with gamma-cyclodextrin (gamma-CD) as chiral selector. Various CZE conditions were investigated to achieve the best resolution of the ESA and OXA enantiomers. The optimum background CZE electrolyte was found to consist of borate buffer (pH=9) containing 20% methanol (v/v) and 2.5% gamma-CD (w/v). Maximum resolution of ESA and OXA enantiomers was achieved using a capillary temperature of 15 degrees C and applied voltage of 30 kV. The applicability of the LC-MS and CZE methods was demonstrated successfully on the enantiomeric analysis of metolachlor and its metabolites in samples from a soil and water degradation study that was set up to probe the stereoselectivity of metolachlor biodegradation. These techniques allow the enantiomeric ratios of the target analytes to be followed over time during the degradation process and thus will prove useful in determining the role of chirality in pesticide degradation and metabolite formation.     

Learning from local knowledge: modeling the pastoral-nomadic range management of the Himba, Namibia.

It is widely accepted that successful grazing management strategies in semiarid ecosystems need to be adapted to the highly temporal and spatially heterogeneous forage production. Nevertheless, a full understanding of the key factors and processes for sustainable adaptive management has yet to be reached. The investigation of existing, successful range management systems by simulation models may help to derive general understanding and basic principles. The semi-nomadic Himba in northern Namibia applied a sophisticated management system until the mid-1990s which combined season-dependent pasture use (resulting in rainy-season pastures and dry-season pastures), preservation of reserves for drought and sanctions for rule breaking. A stochastic ecological simulation model has been developed here which represents the main aspects of this management system. With this model we analyze (1) which components of the traditional Himba strategy are essential for sustainability and (2) what happens to the state of the rangeland system under socioeconomic changes. This study shows that temporally and spatially heterogeneous pasture use yields higher productivity and quality of a pasture area than the pressure of homogeneous permanent grazing. Two aspects are of importance: (1) intra-annual heterogeneous use (resting of the dry-season pastures during the rainy season) and (2) interannual heterogeneous use (spatial extension of grazing in years of drought). This management system leads to an effective build-up and use of a buffer in the system: the reserve biomass (the non-photosynthetic reserve organs of the plants), an indicator for grazing and management history. Analyzing purchase as one form of socioeconomic change, we demonstrate that easier market access to purchase livestock may lead to a decline in vegetation quality. However, cattle production increases as long as rest periods on parts of the pasture during the rainy season are granted. Methodologically, we emphasize that simulation models offer an excellent framework for analyzing and depicting basic principles in sustainable range management derived from local knowledge. They provide the opportunity of testing whether these basic principles are also valid under different ecological and socioeconomic settings.     

Aristolochic acid content of South-East Asian troidine swallowtails (Lepidoptera: Papilionidae) and of Aristolochia plant species (Aristolochiaceae)

Summary. Analysis of South-East Asian troidine swallowtails revealed high variability in the content of aristolochic acids among individuals. The presence or absence of these compounds depends on the Aristolochia species available as food plant for the larvae. Only one plant species (Aristolochia philippinensis) contained a high concentration of aristolochic acids, while other species from various localities contained none or only marginal amounts. Whether aristolochic acids have a distinct function in chemical defense of these swallowtails is still an open question. Received 11 December 2000; accepted 4 August 2001.     

Individual differences in the mechanisms underlying the onset and maintenance of paternal behavior and the inhibition of infanticide in the monogamous biparental California mouse,Peromyscus californicus

Virgin male Peromyscus californicus tend to behave infanticidally or nonparentally towards pups, whereas virtually all males exhibit parental behavior following birth of their own young. Most males (65–75%) living with their pregnant partner attacked or ignored unfamiliar pups and did not become parental (behave parentally) prior to birth of their young. However, a significant minority of males (34%) living with their partner became parental after just 24 h of postcopulatory cohabitation with the female and remained parental throughout their mate's pregnancy. Males that were infanticidal before the birth of their young became parental only after their young were born. The presence of the mother was necessary for the postpartum maintenance of paternal behavior and the inhibition of infanticide in males that were infanticidal prepartum. In contrast, males that were paternal prior to birth of their young continued to be paternal after birth, even in the absence of postpartum contact with the mother. Thus, different mechanisms are involved in the inhibition of infanticide and the onset and maintenance of paternal behavior. Correspondence to: D.J. Gubernick     

Predicting change in fish mercury concentrations following reservoir impoundment

Fish mercury concentrations frequently increase after impoundment of a reservoir. Soil flooding releases organic matter and nutrients, providing food to bacterial communities that methylate inorganic mercury. Methylation and bioaccumulation are the primary pathways for mercury accumulation in fish. We investigated if changes in fish mercury concentrations could be predicted from the change in reservoir size. Data for three fish species, northern pike (Esox lucius), walleye (Stizostedion vitreum), and lake whitefish (Coregonus clupeaformis) from reservoirs in northern Manitoba and northern Quebec were used to evaluate four simple models of change in mercury with change in flooded area. For three additional fish species, all primary carnivores, the preferred model consisted of a single exponential enrichment term. This model successfully predicted two cases not used in model development-one with a large change in area and one with a small change in area. Models with good predictive skill can be developed when the underlying dynamics are known.     

Elevated alpha-fetoprotein and human chorionic gonadotropin as a marker for placental trisomy 16 in the second trimester?

In a series of 2961 consecutive cases with second-trimester biochemical triple screening for Down's syndrome and neural tube defect (NTD), ten (0.3 per cent) showed an apparent increased risk for both conditions. Three cases had chromosomal abnormalities, namely trisomy 16 confined to the placenta. Since placental trisomy 16 as well as cases with increased alpha-fetoprotein (AFP) and human chorionic gonadotropin (hCG) are associated with (intrauterine growth retardation (IUGR), oligohydramnios, and fetal demise, at least some cases with this atypical biochemical profile could be explained by this chromosomal abnormality. From our results we recommend that in cases with increased risk for both Down's syndrome and NTD, fetal karyotyping should preferably be done on a placental biopsy, especially when ultrasound in the absence of anomalies demonstrates early IUGR.     

Cycads: their evolution,toxins, herbivores and insect pollinators

Palaeobiological evidence indicates that gymnosperms were wind-pollinated and that insect pollination began in angiosperms in the Lower Cretaceous (ca. 135 mya) leading to close associations between higher plants and their pollinators. Cycads, which were widespread and pervasive throughout the Mesozoic (250-65 mya) are among the most primitive living seed-plants found today. Because pollination by beetles and by thrips has now been detected in several modern cycads, it is attractive to speculate that some insects and cycads had already developed similar mutualistic interactions in the Triassic (250-205 mya), long before the advent of angiosperms. We also draw attention to another key factor in this insect-plant relationship, namely secondary, defensive plant substances which must always have controlled interspecific interactions. Cycads mainly produce toxic azoglucosides and neurotoxic non-protein amino acids (e.g. BMAA), which apparently are crucial elements in the development and maintenance of mutualism (pollination) and parasitism (herbivory) by cycad-linked herbivores. We now add new results on the uptake and storage of the main toxin, cycasin, of the Mexican cycad Zamia furfuracea by its pollinator, the weevil Rhopalotria mollis, and by a specialist herbivore of Zamia integrifolia, the aposematic Atala butterfly Eumaeus atala.     

Adaptation to environmental stress in Daphnia magna simultaneously exposed to a xenobiotic

In standardized ecotoxicological testing chemicals are investigated under optimal conditions for the test organisms despite the fact that environmental factors such as predation pressure and food availability are important parameters regulating natural populations. Food limitation and predator presence can induce shifts in life-history traits in various Daphnia species, especially trade-offs in reproductive biomass allocation. These adaptive responses are thought to ensure survival of the population in a highly variable environment. A xenobiotic dispersant (used in textile dyeing processes) also shifted the biomass allocation of Daphnia magna. To assess whether the dispersant could hinder D. magna adaptation to varying environmental conditions, we conducted experiments with food level and presence of Chaoborus larvae as environmental factors and simultaneous exposure to the dispersant. At low food level and in presence of the predator, D. magna produced fewer but larger sized neonates, regardless of dispersant exposure. The dispersant shifted biomass allocation towards more but smaller sized offspring in all experiments. However, the adaptive response to the environmental factors and the dispersant effect cancelled each other out in that they induced independently from each other opposite shifts in biomass allocation. In summary, the dispersant exposure resulted not in an inhibition of the adaptive response but in a reduction of the value of the response. Our study with this model substance demonstrates that xenobiotics can affect the adaptation of organisms to environmental stress which can result in effects likely to be overlooked in standardized testing.