Crystallization behavior of predominantly syndiotactic poly(β-hydroxybutyrate)

Predominantly syndiotactic poly(-hydroxybutyrate), syn-PHB, of variable syndioregularity (syndyad fractions 0.59, 0.62, 0.64, and 0.71) and molecular weight was prepared by the dibutyltin dimethoxide catalyzed ring opening of racemic-butyrolactone (BL). The crystallization behavior of the syn-PHB polymers was investigated by DSC and X-ray diffraction analyses. DSC of films after melting and annealing showed at least one, and often two distinct melting transitions occuring over a broad (often 40°C) temperature range. These results indicate that syn-PHB chain segments of variable syndioregularity form crystalline regions with very different thermodynamic stabilities. Maximum degrees of crystallinity for melt annealed 0.64- and 0.71-syn-PHB was observed at an annealing temperature (T _c ) of 30°C. AtT _c values at 45°C and higher, crystallization of relatively lower syndioregular chain segments was apparently excluded to variable degrees dependent onT _c and sample syndiotactic dyad content. After crystallization of syn-PHB samples at elevated temperatures, ambient temperature annealing resulted in an observed lower temperature melting transition at 50°C. This result showed little to no dependence on syn-PHB syndio-regularity andT _c . Both solution precipitated 0.62-syn-PHB and 0.71-syn-PHB have WAXS patterns with poorly resolved crystalline reflections superimposed on amorphous haloes indicating low levels of crystallinity (17% and 25%, respectively) and poorly formed crystals. Isothermal crystallization monitored by DSC showed that the syn- and natural origin PHB showed fastest crystallization rates at temperatures between 50°C and 70°C and 60°C and 90°C, respectively. From the dependence of the higher melting transition onT _c it was determined that the equilibrium melting temperatures for 0.62-syn-PHB (M _n =83,700 g/mol) and a 0.64-syn-PHB (M _n =11,900 g/mol) were 157 and 154°C, respectively. An Avrami analysis of syn-PHB yielded results similar to that found for natural origin PHB indicating that crystal growth occurs by a two-dimensional mechanism.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Prediction of particulate air pollution from a landfill site using CFD and LIDAR techniques

Landfill sites have been the most common way of eliminating solid urban waste, as well as that of public and mining wastes. Landfill sites are a constant source of environmental pollution and wind is the most important contributing factor to air pollution, due to the erosion which it produces over the landfill site surfaces, transporting dust away from the source point. This causes serious risks for human health and general dirt in the surrounding areas of the landfill site. The result of dust air pollution produced in a landfill site is analysed through CFD3D (Computational Fluid Dynamics) by joining the LIDAR (Light Detection and Ranging) technique and Ansys CFX 10.0 software. The CFD simulations determine the wind velocity distribution on the landfill site surface and the different particle threshold friction velocities which determine the dust emission in multiphase simulations (air-particles). These simulations are validated from field data obtained in three measurement programmes for each type of landfill site surface treatment which has been studied. It was determined that the superficial landfill site treatment with the lowest air pollution is tall grass and bushes. The methodology used can be applied to the dust emission calculation in the design or evaluation of other landfill sites.     

Transcervical chorionic villus biopsy with a brush

A brush delivered to the biopsy site by a metal introducer and cannula set was tested as an alternative implement for transcervical collection of chorionic villi. This implement was easy to use and readily identified by ultrasound. With only one attempt at sampling, the overall collection rate for 83 patients was 65 per cent. With practice 84 per cent successful collection was achieved. Gestations between 8 and 11 weeks was the best time for collection of chorionic villi. A single sampling can produce adequate material (15 mg wet weight) suitable for diagnostic purposes. No gestation sac was perforated but some slight bleeding followed the procedure. Appreciable success following a single sampling attempt coupled with the low complication rate suggests that this technique may have clinical application and deserves further investigation.     

Multi-decadal changes in tundra environments and ecosystems: synthesis of the International Polar Year-Back to the Future project (IPY-BTF)

Understanding the responses of tundra systems to global change has global implications. Most tundra regions lack sustained environmental monitoring and one of the only ways to document multi-decadal change is to resample historic research sites. The International Polar Year (IPY) provided a unique opportunity for such research through the Back to the Future (BTF) project (IPY project #512). This article synthesizes the results from 13 papers within this Ambio Special Issue. Abiotic changes include glacial recession in the Altai Mountains, Russia; increased snow depth and hardness, permafrost warming, and increased growing season length in sub-arctic Sweden; drying of ponds in Greenland; increased nutrient availability in Alaskan tundra ponds, and warming at most locations studied. Biotic changes ranged from relatively minor plant community change at two sites in Greenland to moderate change in the Yukon, and to dramatic increases in shrub and tree density on Herschel Island, and in subarctic Sweden. The population of geese tripled at one site in northeast Greenland where biomass in non-grazed plots doubled. A model parameterized using results from a BTF study forecasts substantial declines in all snowbeds and increases in shrub tundra on Niwot Ridge, Colorado over the next century. In general, results support and provide improved capacities for validating experimental manipulation, remote sensing, and modeling studies.     

Temporal and spatial trends of PCB congeners in UK gannet eggs

Gannet (Sula bassana) eggs collected from Ailsa Craig, Western Scotland between 1977-1998 have been analyzed retrospectively for several PCB congeners. Concentrations of a range of congeners were determined in 8-10 eggs analyzed separately for several individual years. All congeners declined in concentrations throughout the time period, but the rates of decline differed for different congeners. Declines were first order and half-lives varied between 5.4 years for PCB-101 to 10.1 years for PCB-180. Egg concentrations reflect the maternal body burden, which itself is controlled by the birds rate of intake (principally via the diet) and losses (via metabolism and other clearance mechanisms). The declining concentrations in eggs, therefore, broadly reflect reductions in prey concentrations (principally herring and mackerel) and--in turn--water column concentrations. Rates of change in PCB concentrations from this study were similar to those noted in fish-eating birds from the Baltic Sea and North American Great Lakes, and ambient air in the UK. This provides indirect evidence that gannet eggs are broadly reflecting regional/global scale clearance/removal mechanisms which are controlling ambient PCB concentrations.     

Predicting Gran alkalinity and calcium concentrations in river waters over a national scale using a novel modification to the G-BASH model

Monthly stream water calcium and Gran alkalinity concentration data from 11 sub-catchments of the Nether Beck in the English Lake District have been used to appraise the transferability of the Scottish, River Dee-based G-BASH model. Readily available riparian zone geochemistry and flow paths were used initially to predict minimum and mean stream water concentrations at the Nether Beck, based on calibration equations from the River Dee catchment data. Predicted values significantly exceeded observed values. Differences in runoff between the two areas, leading to a dilution effect in the Nether Beck, explained most of the difference between observed and predicted values. Greater acid deposition in the Lake District also reduced stream water Gran alkalinity concentrations in that area. If regional differences in precipitation, evapotranspiration and pollutant deposition are incorporated into the model, it may then be used reliably to predict catchment susceptibility to acidification over a wide regional (national) scale.