Photolytic dehalogenation of the marine halogenated natural product Q1

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) has been detected in high-trophic level biota throughout the world. In this study we UV-irradiated Q1 in order to produce hexahalogenated 1'-methylbipyrroles (Cl(6)-MBPs). Q1 was transformed with half-lives of <5 min. Already after 5 min, all of the five existing Cl(6)-MBPs (H1-H5) were detected in the irradiated sample. Only one Cl(6)-MBP (2,3,3',4',5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-77, H2) has been previously described in the literature. H5 was identified as 2,3,3',4,4',5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-75) by a specific fragment ion detected by GC/ECNI-MS. Fractionations of the irradiation mixture by reversed-phase HPLC followed by (1)H NMR analysis led to the structure of H4, i.e. 2,3,3',4,4',5-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-74). H1 and H3 showed virtually identical (1)H NMR data. Therefore, it could not determined which of either isomers is 2,3,3',4,5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-76) and which is 2,3,4,4',5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-78). In addition, two pentachloro-MBPs (P1 and P3) could be traced back to MBP-62 and MBP-69. Cl(6)-MBPs were analyzed in whale blubber from Australia and skua adipose tissue from Antarctica. The marine mammals contained all Cl(6)-MBPs except for the most abundant in the irradiation experiment. The concentrations of the Cl(6)-MBPs amounted to 0.04-1.76% of the concentration of Q1. The highest concentrations of Cl(6)-MBP isomers in the biota samples were found for MBP-76, MBP-77, and MBP-78. These congeners appeared to be the most lipophilic ones owing to the highest retention time in RP-HPLC. Nevertheless, it remained unclear whether the Cl(6)-MBPs were actual halogenated natural products or environmental metabolites of Q1.     

Fugacity modelling to predict the distribution of organic contaminants in the soil:oil matrix of constructed biopiles

Level I and II fugacity approaches were used to model the environmental distribution of benzene, anthracene, phenanthrene, 1-methylphenanthrene and benzo[a]pyrene in a four phase biopile system, accounting for air, water, mineral soil and non-aqueous phase liquid (oil) phase. The non-aqueous phase liquid (NAPL) and soil phases were the dominant partition media for the contaminants in each biopile and the contaminants differed markedly in their individual fugacities. Comparison of three soils with different percentage of organic carbon (% org C) showed that the % org C influenced contaminant partitioning behaviour. While benzene showed an aqueous concentration worthy of note for leachate control during biopiling, other organic chemicals showed that insignificant amount of chemicals leached into the water, greatly reducing the potential extent of groundwater contamination. Level II fugacity model showed that degradation was the dominant removal process except for benzene. In all three biopile systems, the rate of degradation of benzo(a)pyrene was low, requiring more than 12 years for soil concentrations from a spill of about 25 kg (100 mol) to be reduced to a concentration of 0.001 microgg(-1). The removal time of 1-methylphenanthrene and either anthracene or phenanthrene was about 1 and 3 years, respectively. In contrast, benzene showed the highest degradation rate and was removed after 136 days in all biopile systems. Overall, this study confirms the association of risk critical contaminants with the residual saturation in treated soils and reinforces the importance of accounting for the partitioning behaviour of both NAPL and soil phases during the risk assessment of oil-contaminated sites.     

Microcosm investigations of stormwater pond sediment toxicity to embryonic and larval amphibians: variation in sensitivity among species

Stormwater ponds have become common features of modern development and often represent significant amounts of open space in urbanized areas. Although stormwater ponds may provide habitat for wildlife, factors responsible for producing variation in wildlife use of ponds have received limited attention. To investigate the role of variation in species tolerances of pollutants in structuring pond-breeding amphibian assemblages, we exposed species tolerant (Bufo americanus) and not tolerant (Rana sylvatica) of urbanization to pond sediments in laboratory microcosms. Pond microcosms had elevated sediment metal levels and chloride water concentrations. Among R. sylvatica embryos, exposure to pond sediments resulted in 100% mortality. In contrast, B. americanus embryos and larvae experienced only sublethal effects (i.e., reduced size at metamorphosis) due to pond sediment exposure. Our results suggest variation in pollutant tolerance among early developmental stages of amphibians may act in concert with terrestrial habitat availability to structure amphibian assemblages associated with stormwater ponds.     

Kin conflict over caste determination in social Hymenoptera

We argue that caste determination, the process whereby females in the social Hymenoptera develop into either queens or workers, is subject to kin-selected conflict. Potential conflict arises because developing females are more closely related to their would-be offspring than to those of other females. Therefore, they may favour becoming queens contrary to the interests of other developing females and of existing queens and workers. We suggest two contexts leading to potential caste conflict. The first occurs when queens are reared in a reproductive phase following an ergonomic phase of worker production, while the second occurs when queens and workers are reared simultaneously. The first context assumes that workers' per capita contribution to colony survival and productivity falls with rising colony size. A critical feature influencing whether potential conflict is realized is the extent to which developing females can determine their own caste (“self-determination”). Self-determination is facilitated when female larvae control their own food intake and when queen-worker size dimorphism is low. We know of no strong evidence for actual conflict over caste fate arising in the first context. However, stingless bees and polygynous ants with excess queen-potential larvae that are either forced to develop as workers or are culled as adults demonstrate actual caste conflict in the second context. Caste conflict does not preclude caste regulation for “the good of the colony”, but such regulation is contingent on either the absence of potential conflict or on developing females losing control of their caste fate. Received: 22 March 1999 / Received in revised form: 15 June 1999 / Accepted: 19 June 1999     

Associations between sleep,risk and safety climate: A study of offshore personnel on the Norwegian continental shelf

The demands and constraints of the offshore working environment can have adverse effects on health, particularly the quality of sleep. Perceived risk and safety are significant psychological stress factors which may interfere with and deteriorate the sleep quality of offshore personnel. The present study explores the relationship between risk perception, safety climate and sleep quality. Data were collected under the auspices of the Petroleum Safety Authorities in Norway using a cross-sectional design. A total of 9601 offshore workers from 52 offshore installations on the Norwegian continental shelf participated in the study. Our findings indicate that both risk perception and safety climate are significantly related to sleep quality. The results of the present study suggest that risk perception and safety climate not only are important aspects of safety performance in the offshore industry, but also have an impact on sleep quality.     

The Ecotoxicological Recovery of Ely Creek and Tributaries (Lee County, Va) After Remediation of Acid Mine Drainage

The Ely Creek watershed (Lee County, VA) was determined in 1995 to be the most negatively affected by acid mine drainage (AMD) within the Virginia coalfield. This determination led the US Army Corps of Engineers to design and build passive wetland remediation systems at two major AMD seeps affecting Ely Creek. This study was undertaken to determine if ecological recovery had occurred in Ely Creek. The results indicate that remediation had a positive effect on all monitoring sites downstream of the remediated AMD seeps. At the site most impacted by AMD, mean pH was 2.93 prior to remediation and improved to 7.14 in 2004. Benthic macroinvertebrate surveys revealed that one AMD influenced site had increased taxa richness from zero taxa in 1997 to 24 in 2004. While in situ testing of Asian clams resulted in zero survival at five of seven AMD influenced sites prior to remediation, some clams survived at all sites after. Clam survival was found to be significantly less than upstream references at only two sites, both downstream of un-mitigated AMD seeps in 2004. An ecotoxicological rating (ETR) system that combined ten biotic and abiotic parameters was developed as an indicator of the ecological status for each study site. A comparison of ETRs from before and after remediation demonstrated that all sites downstream of the remediation had experienced some level of recovery. Although the remediation has improved the ecological health of Ely Creek, un-mitigated AMD discharges are still negatively impacting the watershed.     

The Role of Mineral Weathering Rate Determinations in Generating Uncertainties in the Calculation of Critical Loads of Acidity and their Exceedance

Current legislation within Europe aimed at limitingecosystem damage resulting from inputs of atmosphericpollution is based on the critical load concept. Mineralweathering rates are central to the calculation ofcritical loads (acceptable levels) of acid deposition.The authors have undertaken a number of studies whichillustrate the complications and limitations inherent inpredicting mineral weathering rates and the implicationswhich these have for critical loads calculations andmapping. Calculated weathering rates and critical loadsfor two acid-sensitive parent materials (greywackes andgranites) are presented and are used to illustrate theimpact that uncertainty can have on critical loadexceedances. The results have obvious implications forportraying the uncertainties of critical loads to policy makers.