An efficient approach to sulfate metabolites of polychlorinated biphenyls

Polychlorinated biphenyls (PCBs), a major class of persistent organic pollutants, are metabolized to hydroxylated PCBs. Several hydroxylated PCBs are substrates of cytosolic phase II enzymes, such as phenol and hydroxysteroid (alcohol) sulfotransferases; however, the corresponding sulfation products have not been isolated and characterized. Here we describe a straightforward synthesis of a series of ten PCB sulfate monoesters from the corresponding hydroxylated PCBs. The hydroxylated PCBs were synthesized by coupling chlorinated benzene boronic acids with appropriate brominated (chloro-)anisoles, followed by demethylation with boron tribromide. The hydroxylated PCBs were sulfated with 2,2,2-trichloroethyl chlorosulfate using DMAP as base. Deprotection with zinc powder/ammonium formate yielded the ammonium salts of the desired PCB sulfate monoesters in good yields when the sulfated phenyl ring contained no or one chlorine substituent. However, no PCB sulfate monoesters were isolated when two chlorines were present ortho to the sulfated hydroxyl group. To aid with future quantitative structure activity relationship studies, the structures of two 2,2,2-trichloroethyl-protected PCB sulfates were verified by X-ray diffraction.     

Delineating high-density areas in spatial Poisson fields from strip-transect sampling using indicator geostatistics: application to unexploded ordnance removal

An approach for delineating high anomaly density areas within a mixture of two or more spatial Poisson fields based on limited sample data collected along strip transects was developed. All sampled anomalies were transformed to anomaly count data and indicator kriging was used to estimate the probability of exceeding a threshold value derived from the cdf of the background homogeneous Poisson field. The threshold value was determined so that the delineation of high-density areas was optimized. Additionally, a low-pass filter was applied to the transect data to enhance such segmentation. Example calculations were completed using a controlled military model site, in which accurate delineation of clusters of unexploded ordnance (UXO) was required for site cleanup.     

Groundwater Denitrification Capacity of Riparian Zones in Suburban and Agricultural Watersheds1

Watson, Tara K., Dorothy Q. Kellogg, Kelly Addy, Arthur J. Gold, Mark H. Stolt, Sean W. Donohue, and Peter M. Groffman, 2010. Groundwater Denitrification Capacity of Riparian Zones in Suburban and Agricultural Watersheds. Journal of the American Water Resources Association (JAWRA) 46(2):237-245. DOI: 10.1111/j.1752-1688.2010.00418.x Abstract: We evaluated the relationship of dominant watershed land use to the structure and nitrogen (N) sink function of riparian zones. We focused on groundwater denitrification capacity, water table dynamics, and the presence and pattern of organically enriched deposits. We used the push-pull method (measurement of ¹⁵N-enriched denitrification gases derived from an introduced groundwater plume of ¹⁵N-enriched nitrate) to evaluate groundwater denitrification capacity on nine forested wetland riparian sites developed in alluvial or outwash parent materials in southern New England. Three replicate sites were located in each of the three watershed types, those with substantial (1) irrigated agriculture, (2) suburban development, and (3) forest. Soil morphology and water table dynamics were assessed at each site. We found significantly lower mean annual water tables at sites within watersheds with substantial irrigated agriculture or suburban development than forested watersheds. Water table dynamics were more variable at sites within suburban watersheds, especially during the summer. Groundwater denitrification capacity was significantly greater at sites within forested watersheds than in watersheds with substantial irrigated agriculture. Because of the high degree of variability observed in riparian sites within suburban watersheds, groundwater denitrification capacity was not significantly different from either forested or agricultural watersheds. The highly variable patterns of organically enriched deposits and water tables at sites within suburban watersheds suggests that depositional events are irregular, limiting the predictability of groundwater N dynamics in these riparian zones. The variability of riparian N removal in watersheds with extensive suburbia or irrigated agriculture argues for N management strategies emphasizing effective N source controls in these settings.     

THE NEED FOR HIGH RESOLUTION TIME SERIES DATA TO CHARACTERIZE HAWAIIAN STREAMS1

ABSTRACT: Streams in the Hawaiian Islands differ from many streams on the U.S. mainland presenting unique challenges to investigators attempting to characterize Hawaiian streams. Hawaiian streams are short; watersheds are small and steep; and rain events are usually short in duration but intense. As a result, most streams in Hawai'i are flashy. Time scales for storm hydrographs in Hawai'i are on the order of hours instead of days and flash flooding is a common hazard. To characterize the streams we were investigating, we found it necessary to obtain streamflow and water quality measurements at relatively short time intervals. While this resolution resulted in large sometimes onerous quantities of data, we would have otherwise missed certain phenomena, such as 60‐fold flow changes in 15 minutes or 30‐fold turbidity changes in five minutes. Even at five‐minute intervals, we found that attempts to predict TSS using a relationship obtained from in situ turbidity were not always satisfactory. Depending on the precision required, either higher resolution measurements or in vitro turbidity measurements of the TSS samples might be necessary. Finally, these high resolution measurements enabled us to observe other cyclical events that might have been missed if the measurement intervals were greater than one hour.     

The influence of pigmentation patterning on bumblebee foraging from flowers of Antirrhinum majus

Patterns of pigmentation overlying the petal vasculature are common in flowering plants and have been postulated to play a role in pollinator attraction. Previous studies report that such venation patterning is significantly more attractive to bee foragers in the field than ivory or white flowers without veins. To dissect the ways in which venation patterning of pigment can influence bumblebee behaviour, we investigated the response of flower-naïve individuals of Bombus terrestris to veined, ivory and red near-isogenic lines of Antirrhinum majus. We find that red venation shifts flower colour slightly, although the ivory background is the dominant colour. Bees were readily able to discriminate between ivory and veined flowers under differential conditioning but showed no innate preference when presented with a free choice of rewarding ivory and veined flowers. In contrast, both ivory and veined flowers were selected significantly more often than were red flowers. We conclude that advantages conferred by venation patterning might stem from bees learning of their use as nectar guides, rather than from any innate preference for striped flowers.     

The trophic ecology of two abundant mesopredators in south-east coastal waters of Tasmania, Australia

Investigating predator–prey relationships is an important component for identifying and understanding the factors that influence the structure and function of ecosystems. Mesopredators, defined as mid-level predators, have a profound effect on ecosystem structure by contributing an important link between apex predators and lower trophic levels. The diet of two elasmobranch mesopredators, Squalus acanthias and Mustelus antarcticus, was investigated in three locations in south-east Tasmania. Squalus acanthias consumed predominantly pelagic teleosts and cephalopods, while M. antarcticus predominantly consumed benthic crustaceans. As a result, there was low dietary and niche overlap between the two species. There was however evidence of intra-specific dietary variations between locations for both the species. This study has contributed to a better understanding of the top-down dynamics of the food web in coastal Tasmania, by providing important dietary information of two abundant mesopredators. In addition, the similar dietary patterns for S. acanthias and other Mustelus species over much of their global range suggest they may be consistent in their trophic roles across systems, with limited competition between these two sympatric mesopredators to be expected.     

The influence of host diversity and composition on epidemiological patterns at multiple spatial scales

Spatial patterns of pathogen prevalence are determined by ecological processes acting across multiple spatial scales. Host-pathogen interactions are influenced by community composition, landscape structure, and environmental factors. Explaining prevalence patterns requires an understanding of how local determinants of infection, such as community composition, are mediated by landscape characteristics and regional-scale environmental drivers. Here we investigate the role of local community interactions and the effects of landscape structure on the dynamics of barley and cereal yellow dwarf viruses (B/CYDV) in the open meadows of the Cascade Mountains of Oregon. B/CYDV is an aphid-transmitted, generalist pathogen of over 100 wild and cultivated grass species. We used variance components analysis and model selection techniques to partition the sources of variation in B/CYDV prevalence and to determine which abiotic and biotic factors influence host-pathogen interactions in a Cascades meadowsystem. B/CYDV prevalence in Cascades meadows varied by host species identity, with a significantly higher proportion of infected Festuca idahoensis individuals than Elymus glaucus or Bromus carinatus. Although there was significant variation in prevalence among host species and among meadows in the same meadow complex, there was no evidence of any significant variation in prevalence among different meadow complexes at a larger spatial scale. Variation in prevalence among meadows was primarily associated with the local community context (host identity, the relative abundance of different host species, and host species richness) and the physical landscape attributes of the meadow. These results highlight the importance of local host community composition, mediated by landscape characteristics such as meadow aspect, as a determinant of the spatial pattern of infection of a multi-host pathogen.