Synthesis of halogenated diphenyl ethers and dibenzofurans - A discussion of specific isomers available

Synthetic routes for the preparation of halogenated diphenyl ethers and dibenzofurans are reviewed, and isomers reported in the literature are listed. In addition, the routes preferred for the synthesis of specific chlorinated isomers - especially from the point of view of an unambiguous structural assignment - are discussed in detail. The route recommended for chlorinated diphenyl ethers is the coupling of biaryliodonium salts with phenols, and for chlorinated dibenzofurans the palladium acetate-promoted cyclization of diphenyl ethers. Chlorinated isomers of diphenyl ethers and dibenzofurans which are available via these routes are listed. Furthermore, the synthesis of a new octachlorodiphenyliodonium salt and its coupling with three different chlorophenols are described, and the cyclization of an octachlorodiphenyl ether to octachlorodibenzofuran is shown.     

雄性波罗的海灰海豹(Halichoerus grypus)骨组织的矿物密度

本文利用非侵入计算层析X射线摄影法(pQCT)研究了雄性波罗的海灰海豹(4～23岁龄)骨组织的矿物密度(mg/cm3).资料按照收集的年份分组.A组1850～1955年,有机氯(OCs)大量引入之前的时期;B组1965～1985年,OC污染十分严重的时期;C组1986～1997年,OCs浓度逐渐减小的时期.测量结果的复现性良好,变异系数(CV)为0.1%～2.1%.1986～1997年收集的标本中桡骨小梁的矿物密度比1965～1985年收集的标本的明显要高(p＜0.05).1986～1997年收集的标本中,下颌骨的皮层骨矿物密度明显地低于1850～1955年收集的标本(p＜0.05).这些结果表明小梁和皮层骨在一段时间内的不同响应.在OC污染非常严重的时期(1965～1985年),小梁骨矿物密度最低,而在1985～1997年收集的标本中,皮层骨密度最低,该时段是一个OC污染程度相当低的时期.有关这些效应背后的机制目前尚不知道.但是,可以假定这里涉及到OCs.由于目前缺乏有关研究个体中OCs残留水平的资料,因此不可能评估OCs在这方面的影响.     

Determining gestational age using genome methylation profile: A novel approach for fetal medicine

Gestational age determination by traditional tools (last menstrual period, ultrasonography measurements and Ballard Maturational Assessment in newborns) has major limitations and therefore there is a need to find different approaches. In this study, we looked for a molecular marker that can be used to determine the accurate gestational age of the newborn. To this end, we performed reduced representation bisulfite sequencing (RRBS) on 41 cord blood and matching placenta samples from women between 25 and 40 weeks of gestation and generated an epigenetic clock based on the methylation level at different loci in the genome. We identified a set of 332 differentially methylated regions (DMRs) that undergo demethylation in late gestational age in cord blood cells and can predict the gestational age (r = −.7, P = 2E-05). Once the set of 411 DMRs that undergo de novo methylation in late gestational age was used in combination with the first set, it generated a more accurate clock (R = .77, P = 1.87E-05). We have compared gestational age determined by Ballard score assessment with our epigenetic clock and found high concordance. Taken together, this study demonstrates that DNA methylation can accurately predict gestational age and thus may serve as a good clinical predictor.     

1,2,3,5,6,7-Hexachloronaphthalene and 1,2,3,4,6,7-hexachloronaphthalene - selective retention in rat liver and appearance in wildlife

The two isomers 1,2,3,5,6,7- and 1,2,3,4,6,7-hexachloronaphthalene are shown to be selectively retained in the liver of rats orally dosed with the commercial PCN product Halowax 1014. The retention was further studied by dosing rats orally with a mixture of the two compounds. The rats were sacrificed after 1, 10, 35 and 120 days, respectively. The two hexachloronaphthalenes were found to be strongly retained in the liver and the concentration ratios liver/adipose tissue were remarkably high. 1,2,3,5,6,7- And 1,2,3,4,6,7-hexachloronaphthalene were also found to be present in two environmental samples from the Swedish east coast, cod liver and guillemot egg.     

Application of a Life Cycle Simulation Model to Evaluate Impacts of Water Management and Conservation Actions on an Endangered Population of Chinook Salmon

Fisheries and water resource managers are challenged to maintain stable or increasing populations of Chinook salmon in the face of increasing demand on the water resources and habitats that salmon depend on to complete their life cycle. Alternative management plans are often selected using professional opinion or piecemeal observations in place of integrated quantitative information that could reduce uncertainty in the effects of management plans on population dynamics. We developed a stochastic life cycle simulation model for an endangered population of winter-run Chinook salmon in the Sacramento River, California, USA with the goal of providing managers a tool for more effective decision making and demonstrating the utility of life cycle models for resource management. Sensitivity analysis revealed that the input parameters that influenced variation in salmon escapement were dependent on which age class was examined and their interactions with other inputs (egg mortality, Delta survival, ocean survival). Certain parameters (river migration survival, harvest) that were hypothesized to be important drivers of population dynamics were not identified in sensitivity analysis; however, there was a large amount of uncertainty in the value of these inputs and their error distributions. Thus, the model also was useful in identifying future research directions. Simulation of variation in environmental inputs indicated that escapement was significantly influenced by a 10% change in temperature whereas larger changes in other inputs would be required to influence escapement. The model presented provides an effective demonstration of the utility of life cycle simulation models for decision making and provides fisheries and water managers in the Sacramento system with a quantitative tool to compare the impact of different resource use scenarios.     

Brominated phenols,anisoles, and dioxins present in blue mussels from the Swedish coastline

Introduction  

Naturally occurring hydroxylated polybrominated diphenyl ethers (OH-PBDEs), their methoxylated counterparts (MeO-PBDEs), and polybrominated dibenzo-p-dioxins (PBDDs), together with their potential precursors polybrominated phenols (PBPs) and polybrominated anisoles (PBAs), were analyzed in blue mussels (Mytilus edulis) gathered along the east coast (bordering the Baltic Sea) and west coast of Sweden (bordering the North Sea). Brown algae (Dictyosiphon foenicolaceus) and cyanobacteria (Nodularia spumigena) from the Baltic Sea, considered to be among the primary producers of these compounds, were also analyzed for comparison.     

Long-term dynamic of forest vegetation after reduction of copper smelter emissions

The state of tree and ground vegetation layers in spruce-fir forests around the Middle Ural Copper Smelter (Revda, Sverdlovsk oblast) has been repeatedly evaluated in 25 permanent sampling plots at 5- to 10-year intervals (1989–2013). The results have been used to characterize the dynamics of plant communities in the period of reduction of emissions from the smelter. Although the annual amount of emissions has decreased from 150–225 × 10³ t in the 1980s to less than 5 × 10³ t after 2010, the vegetation in the impact zone (1 and 2 km from the smelter) remains severely suppressed: the trees continue to die off, and the diversity of ground vegetation layer is very low. In zones with low and moderate levels of industrial pollution (30 and 4–7 km from the smelter), natural factors associated with windfall disturbance after the 1995 windstorm with snow have played a more important role in the dynamics of forest communities than the reduction of emissions itself.     

Evidence-Based Knowledge Versus Negotiated Indicators for Assessment of Ecological Sustainability: The Swedish Forest Stewardship Council Standard as a Case Study

Assessing ecological sustainability involves monitoring of indicators and comparison of their states with performance targets that are deemed sustainable. First, a normative model was developed centered on evidence-based knowledge about (a) forest composition, structure, and function at multiple scales, and (b) performance targets derived by quantifying the habitat amount in naturally dynamic forests, and as required for presence of populations of specialized focal species. Second, we compared the Forest Stewardship Council (FSC) certification standards’ ecological indicators from 1998 and 2010 in Sweden to the normative model using a Specific, Measurable, Accurate, Realistic, and Timebound (SMART) indicator approach. Indicator variables and targets for riparian and aquatic ecosystems were clearly under-represented compared to terrestrial ones. FSC’s ecological indicators expanded over time from composition and structure towards function, and from finer to coarser spatial scales. However, SMART indicators were few. Moreover, they poorly reflected quantitative evidence-based knowledge, a consequence of the fact that forest certification mirrors the outcome of a complex social negotiation process.     

Placental transfer of polychlorinated biphenyls, their hydroxylated metabolites and pentachlorophenol in pregnant women from eastern Slovakia

The aim of the present study was to understand the placental transfer of polychlorinated biphenyls (PCBs), specific hydroxylated PCB metabolites (OH-PCBs), and pentachlorophenol (PCP) in blood serum, in a birth cohort from eastern Slovakia. During the period 2002-2004, cord blood specimens were collected in parallel with maternal specimens from women delivering in the two eastern Slovak districts of Michalovce and Svidnik/Stropkov. A total of 92 pairs of mother-cord specimens at delivery were selected for this study. 4-OH-CB107, 3-OH-CB153, 4-OH-CB146, 3'-OH-CB138, 4-OH-CB187, and 4'-OH-CB172 were quantified. The median concentrations of Sigma(17)PCBs, Sigma(6)OH-PCBs, and PCP in cord serum were 0.92, 0.33, and 0.69 ng/g wet wt., respectively and highly correlated with the corresponding maternal serum levels (correlations were R(2)=0.61, 0.78, and 0.82, respectively). The median cord to mother ratios of the Sigma(17)PCBs, Sigma(6)OH-PCBs, and PCP were 0.18, 0.75, and 1.10, respectively. The median ratio of the Sigma(6)OH-PCBs to the Sigma(17) PCBs in the cord serum was 0.38 from wet weight based concentrations, which was about four times higher than the ratio of these compounds in maternal serum (0.09). PCP was more abundant than any PCB or OH-PCB congener measured in cord serum. The higher cord to maternal ratios of OH-PCB metabolites as compared with the parent compounds suggests either a higher placental transfer rate or greater metabolism in the fetus as compared with the maternal compartment. These findings are consistent with their preferential binding to TTR that can cross the placenta. The cord to maternal ratio varies by congener (e.g., 4-OH-CB107=0.58, 4-OH-CB146=0.74, 3'-OH-CB138=1.01).