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.     

A simple procedure to harmonize class boundaries of assessment systems at the pan-European scale

A procedure for a large scale harmonization of assessment systems is delineated. The data collected for the two E.U. co-funded projects STAR and AQEM have been used as a benchmark dataset against which a test dataset derived from Italian standard monitoring programs was compared. A central step in the procedure adopted is the calculation of Intercalibration Common Metrics (STAR_ICMs). For both the benchmark and test datasets, six metrics were calculated, normalized and averaged to obtain an ICM index. The median values obtained for this index within each of the High and Good status classes, as defined within the STAR/AQEM dataset, were compared to the classes defined by the National method applied in Italy before WFD approval. The process of harmonization involved the re-positioning of the boundaries between Italian method quality classes until no more differences were found with the values observed in the STAR/AQEM samples. The re-setting of the Italian assessment boundaries by a step-by-step procedure lead to comparable STAR_ICM index values in the two datasets. Within this example, small refinements of the boundaries between high/good and good/moderate status were sufficient to harmonize the Italian assessment quality classes to the benchmark classification. Once a benchmark dataset is agreed among different countries, the procedure outlined can be easily applied to compare and harmonize assessment systems within and outside Europe. The main scientific and practical advantages of the procedure are listed and commented, especially facing the next steps of the Water Framework Directive Intercalibration process.     

A solvent-free method for spiking terrestrial algae (Desmococcus spp.) with pyrene for use in bioassays

Two methods for spiking terrestrial algae (Desmococcus spp., used as a foodstuff in bioassays with Collembola) with pyrene were tested; a "traditional" method that used a carrier solution of pyrene in acetone, and a solvent-free method developed using the principles of partition driven administration (PDA). The PDA method used a pre-spiked, highly-contaminated C18 disk as the source for pyrene, suspended and rotated in an aqueous algal suspension. The pyrene partitioned from the C18 disk into the aqueous phase, and a concentration of 18.4 +/- 0.7 microg pyrene g(-1)dwt. algae (mean +/- sd) was achieved after 18 h exposure by this method, with good reproducibility also observed for lower concentrations achieved over shorter exposure periods. The acetone-spiked algae lost much of its cell integrity and a significant amount of pigment, while cell integrity was maintained after 120 h spiking using the PDA method. Results from a short bioassay with Orchesella cincta (Collembola, Insecta) showed that animals fed acetone-spiked algae had slower growth rates and higher concentrations of pyrene metabolites than animals fed PDA-spiked algae. It is speculated that this was the result of the poor quality of the acetone-spiked food, and that the difference in food quality between treatments stimulated changes in body composition that may have affected the production of pyrene metabolites. The PDA spiking method is expected to be suitable for introducing a range of persistent organic pollutants into other types of sample matrix.     

Strength development of solidified/stabilized organic waste and optimum treatment design

Artificially contaminated (spiked) natural soils were solidified/stabilized using various combinations of commonly used additives, such as lime, cement, fly ash, activated carbon, and silica fume. The effectiveness of the solidification/stabilization (S/S) processes was evaluated based on experimental findings from compaction testing, unconfined compressive shear strength, and X-ray diffraction (XRD). Correlations of limited reliability between unconfined compressive strength and penetrometer and torvane measurements were derived. Results from XRD experiments indicated that certain organic contaminants (i.e., naphthalene and pyrene) might impact the S/S processes for a given combination of additives. The type and amount of organic contaminants also affected the pozzolanic reactions. Specifically, the absence or small peak intensity of pozzolanic product XRD patterns for a given combination of additives was a good indication that the type and the amount of organic contaminant present inhibited pozzolanic reactions. This phenomenon was tested and confirmed for actual field-contaminated samples.     

Past, current and future fire frequency in the Canadian boreal forest: implications for sustainable forest management

Over the past decades, there has been an increasing interest in the development of forest management approaches that are based on an understanding of historical natural disturbance dynamics. The rationale for such an approach is that management to favor landscape compositions and stand structures similar to those of natural ecosystems should also maintain biological diversity and essential ecological functions. In fire-dominated landscapes, this approach is possible only if current and future fire frequencies are sufficiently low, comparing to pre-industrial fire frequency, that we can substitute fire by forest management. We address this question by comparing current and future fire frequency to historical reconstruction of fire frequency from studies realized in the Canadian boreal forest. Current and simulated future fire frequencies using 2 and 3 x CO2 scenarios are lower than the historical fire frequency for many sites, suggesting that forest management could potentially be used to recreate the forest age structure of fire-controlled pre-industrial landscapes. There are however, important limitations to the current even-age management.     

A rule-based screening environmental risk assessment tool derived from EUSES

Within the context and scope of the forthcoming European Union chemical regulations (REACH), there is a need to be able to prioritise the chemicals for evaluation. Therefore, a simple, pragmatic and adequately conservative approach for the identification of substances of very low or no immediate concern at an early stage is presented. The fundamental principles and basic concepts are derived from the EU Technical Guidance Document and EUSES, and are translated into an easy-to-use rule-based system. For this development, the effect on risk characterisation ratios (RCRs) of the key environmental parameters in EUSES was quantified (taking into account several standardised chemical release scenarios). Using statistical analysis, ranges were identified for each key parameter, within which the end result of the assessment was not significantly affected. This information was then translated into a lookup table from which environmental risk characterisation ratios can be directly read as a function of a few parameters.     

The reproductive behavior and energetics of male gray seals (Halichoerus grypus) breeding on a land-fast ice substrate

The reproductive behavior of male gray seals (Halichoerus grypus) breeding on land-fast ice at Amet Island, Nova Scotia, was studied. Data on energy expenditure (rate of mass loss over time) were collected. The average time budget of males at Amet Island was comparable to that of land-breeding males. The behavior of males showed seasonal changes, with a decrease in the proportion of time spent in the water and an increase in agonistic behavior during the peak mating period. The estimated amount of body mass lost over the season ranged between 25.6 and 77.1 kg, and the estimated percent of initial body mass lost ranged between 7.7 and 26.5% (n=10). The maximum number of observed copulations for an individual male was nine. Only 15 out of 42 males observed during 1992 and 1993 were seen copulating. The number of observed copulations per male was strongly correlated with success in remaining close to, or attending, females (r=0.91, P<0.001, n=42). The mean duration of attendance was 4.5 ± 5.54 days (n=42). Large size was not an important factor in determining attendance success, but reproductive effort (the estimated proportion of body mass lost over the season) and success in agonistic interactions with other males were both correlated with male success.     

Heavy metals in soils and crops in Southeast Asia

In a reconnaisance soil geochemical and plant survey undertaken to study the heavy metal uptake by major food crops in Malaysia, 241 soils were analysed for cation exchange capacity (CEC), organic carbon (C), pH, electrical conductivity (EC) and available phosphorus (P) using appropriate procedures. These soils were also analysed for arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn) using aqua regia digestion, together with 180 plant samples using nitric acid digestion. Regression analysis between the edible plant part and aqua regia soluble soil As, Cd, Cr, Cu, Hg, Ni, Pb and Zn concentrations sampled throughout Peninsular Malaysia, indicated a positive relationship for Pb in all the plants sampled in the survey (R2 = 0.195, p < 0.001), for Ni in corn (R2 = 0.649, p < 0.005), for Cu in chili (R2 = 0.344, p < 0.010) and for Zn in chili (R2 = 0.501, p < 0.001). Principal component analysis of the soil data suggested that concentrations of Co, Ni, Pb and Zn were strongly correlated with concentrations of Al and Fe, which is suggestive of evidence of background variations due to changes in soil mineralogy. Thus the evidence for widespread contamination of soils by these elements through agricultural activities is not strong. Chromium was correlated with soil pH and EC, Na, S, and Ca while Hg was not correlated with any of these components, suggesting diffuse pollution by aerial deposition. However As, Cd, Cu were strongly associated with organic matter and available and aqua regia soluble soil P, which we attribute to inputs in agricultural fertilisers and soil organic amendments (e.g. manures, composts).