Evaluation of the biodegradability of copolyesters containing aromatic compounds by investigations of model oligomers

Model oligo esters of terephthalic acid with 1,2-ethanediol, 1,3-propanediol, and 1,4-butanediol have been investigated with regard to their biodegradability in different biological environments. Well-characterized oligomers with weight-average molar masses of from 600 to 2600 g/mol exhibit biodegradation in aqueous systems, soil, and compost at 60°C. SEC investigations showed a fast biological degradation of the oligomer fraction consisting of 1 or 2 repeating units, independent of the diol component used for polycondensation, while polyester oligomers with degrees of polymerization higher than 2 were stable against microbial attack at room temperature in a time frame of 2 months. At 60°C in a compost environment chemical hydrolysis also degrades chains longer than two repeating units, resulting in enhanced degradability of the oligomers. Metabolization of the monomers and the dimers as well by the microorganisms could be confirmed by comparing SEC measurements and carbon balances in a Sturm test experiment. Based on these results degradation characteristics of potential oligomer intermediates resulting from a primary chain scission from copolyesters consisting of aromatic and aliphatic dicarbonic acids can be predicted depending on their composition. These results will have an evident influence on the evaluation of the biodegradability of commercially interesting copolyesters and lead to new ways of tailor-made designing of new biodegradable materials as well.     

Vertical gradients of ozone and carbon dioxide within a deciduous forest in Central Pennsylvania

Ambient concentrations of ozone (O(3)) and carbon dioxide (CO(2)) were measured at locations from the forest floor to the top of the canopy in a deciduous forest at the Moshannon State Forest in northcentral Pennsylvania. O(3) concentrations were measured from May-September for three years (1993-1995) while CO(2) concentrations were measured only during July and August of 1994. O(3) concentrations increased steadily during the day at all locations, peaking during the middle to late afternoon hours. O(3) concentrations then steadily declined to their lowest point, just before dawn. Vertical O(3) concentration gradients varied seasonally and among years. However, O(3) concentrations were highest within the forest canopy and lowest at the forest floor, with an average difference of approximately 13%. Differences in O(3) concentrations between the canopy and forest floor were greatest at night. O(3) concentrations were slightly higher at locations within the canopy than above the canopy. CO(2) concentrations were consistenly higher near the forest floor and were higher above the canopy than within the canopy. CO(2) concentrations were higher at night than during the day at all locations, especially near the forest floor.     

Long-term trends and sources of organochlorine contamination in Canadian tundra Peregrine Falcons, Falco peregrinus tundrius

Levels of eggshell thinning, and organochlorine residues in egg contents, blood plasma of adults and juveniles, tissue samples, and prey species were determined for a population of migratory Peregrine Falcons (Falco peregrinus tundrius) breeding in the Canadian Arctic. Temporal trends were assessed by comparing data collected during 1991-1994, with data from 1982-1986, for the same population. Shells (n=54) from 1991-1994 averaged 15% thinner than eggs produced prior to the introduction of DDT. No improvement in shell thickness was detected between decades. Mean DDE residue levels in eggs showed a decline from 7.6 mg kg (1982-1986) to 4.5 mg kg (1991-1994), but there was no significant change in SigmaPCB residues. Moreover, the proportion of clutches with eggs exceeding critical SigmaPCB, DDE, and dieldrin residue levels (10%) did not change between decades. Relative to Greenland and Alaskan populations, F. p. tundrius at Rankin Inlet show high levels of organochlorine contamination and little reduction in residues over the last decade. These Tundra Peregrines continue to be exposed to organochlorines in Latin America; however, results also link relatively high levels in the study population with waterfowl species that do not leave Canada in winter.     

Biomass and production of amphipods in low alkalinity lakes affected by acid precipitation

Population biomass and production of the amphipod Hyalella azteca (Saussure) were found to be related to alkalinity (ranging from 0.2 to 58.1 mg liter(-1)) in 10 Canadian Shield lakes in south-central Ontario. Biomass and production of amphipods in the two lakes characterized by spring depressions of pH below 5.0 were found to be lower than those for populations inhabiting lakes that did not experience such acid pulses. The proportional biomass of amphipods in relation to the total littoral zoobenthos community was lower in lakes of low alkalinity than in circumneutral or hardwater lakes. Because production in these amphipod populations is known to depend closely on population abundance, the labour-intensive derivation of production rates yields relatively little information for biomonitoring that cannot be obtained from abundance data alone.     

Congestion at Recreation Areas: Empirical Evidence on Perceptions, Mitigating Behaviour and Management Preferences

Economists have tried to estimate the demand for recreation under conditions of congestion, struggling especially with a model that uses observed rather than stated behaviour to obtain results. This paper reports statistical analyses of data on perceptions, mitigating behaviour and management preferences in order to highlight the difficulties related to empirical analysis of congestion. We offer evidence that may be of assistance to those wishing to construct measures of congestion for use in an observed behaviour model. The results may also be useful to recreation area managers who can implement a quota or permit system or change site entry or access fees to control access to the site they manage.     

Selectivity in the complexation of actinides by humic substances

The interactions of a range of actinide elements (Th, U, Np, Pu, Am) with humic substances from the Needle's Eye natural analogue site were studied by gel permeation chromatography. Bulk humic substances were isolated by ammonia extraction, followed by dialysis against distilled water and freeze-drying. The gel permeation results suggest that Needle's Eye humic substances can be fractionated into three incompletely resolved fractions with average molecular weights determined by analytical ultracentrifugation around 49 000 for Fraction 1, around 14 700 for Fraction 2 and around 8000 for Fraction 3. Although there are significant differences between the organic matter elution patterns in individual gel permeation experiments, presumably due to differences in column packing, these are much smaller than the differences between metal ions. The uranium that is naturally present in these humic substances is largely bound in the late-eluting fraction. Spikes of the early actinides, including Np and Pu in controlled valency states, have been added to the humic substances, and gel permeation of the spiked humic substances shows that the three humic fractions vary greatly in their effectiveness and selectivity as ligands for early actinides.     

Patterns of soil copper contamination and temporal changes in vegetation in the vicinity of a copper rod rolling factory

Patterns of soil copper contamination have been examined in the vicinity of a copper rod rolling plant in Prescot, Merseyside, UK. The site, established in 1975, was found to possess clear patterns of soil copper contamination, with the highest levels of HNO3 and water-extractable fractions encountered in the factory grounds adjacent to the location of the furnace chimney. The majority of the copper had accumulated in the upper soil horizons. The site is surrounded by planted lawns, established at different times after the commissioning of the plant. The species composition of the extant grassland communities, found at sites with differing soil copper levels, was compared to the composition of the original seed mixtures sown at each of ten sites. These surveys clearly showed that different levels of soil copper contamination had produced significant changes in grassland composition with time. At the most polluted site, copper tolerant Agrostis capillaris clones were the main grasses present only two years after the area was sown with a four-species mixture of non-tolerant grass seed. Lolium perenne possessed extreme sensitivity to copper. A number of dicotyledonous species, normally considered sensitive to elevated copper levels, were found to be unaffected where such conditions had arisen after plants had established from seed.     

Distribution of Organochlorine Pesticides in the Chao Phraya River, Thailand

Water samples from the Chao Phraya River, the main river in Thailand were collected and analyzed during 1988–1994. Organochlorine pesticides such as HCHs, DDTs, aldrin, dieldrin and chlordanes were determined. Aldrin and dieldrin had high frequencies of occurrence in water samples. The concentration median of the pesticides was approximately one order of magnitude higher than those of total HCHs and DDTs. Levels of aldrin were relatively high in the upstream while levels of DDTs were high in the urban area of Bangkok during 1989–1990. p,p-DDE levels were relatively higher in 1992. No clear trends in the levels of pesticides were observed.     

Enzymatic degradation of poly([R,S] β-hydroxybutyrate)

The synthetic analogue of a bacterially produced polyester, poly(-hydroxybutyrate) (PHB) was synthesized from racemic -butyrolactone using anin situ trimethyl aluminum-water catalyst. The polymer was fractionated into samples differing in molecular weight and isotactic diad content. The latter was closely related to degree of crystallinity. The biodegradation of these fractions were examined by monitoring mass loss over time in the presence of anAlcaligenes faecalis T1 extracellular bacterial poly(-hydroxybutyrate) depolymerase. The fraction with high isotactic diad tacticity content showed little or no degradation over a 50 hour incubation period, whereas the fraction of intermediate isotactic diad content degraded in a continuous steady fashion at a rate that was less than that for bacterial PHB. The low isotactic diad fraction underwent a rapid initial degradation, followed by no further mass loss. The presence of stereoblocks in the polymer structure of the various fractions was an influence on the degree of susceptibility towards degradation and is related to sample crystallinity.