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.     

Scots pine needle surfaces on radial transects across the north boreal area of Finnish Lapland and the Kola Peninsula of Russia

To gain an understanding of the characteristics of the needle surfaces of naturally regenerated Scots pine (Pinus sylvestris L.) and their geographical distribution, eight physicochemical variables were investigated within the north boreal forest area. The visibly undamaged needles were collected in autumn 1990 from 114 plots (3-5 pines per plot) along radial transects from the Monchegorsk and Nikel smelters, emitting SO2 and heavy metals, on the Kola Peninsula, Russia, to Finnish Lapland. The needles were examined by scanning electron microscopy (SEM) and measured for surface wettability using the droplet contact angle (DCA) method. Significant geographical south-north and west-east patterns could be observed in needle surface characteristics, correlating with emissions from the smelters and to climate. Despite the slightly higher initial DCAs (61.4-87.6 degrees) towards the north, the pine needle surfaces of the northernmost transects exhibited higher annual needle wettability change (ANWC) and wax erosion rate (AWER), expressed as the reduction in DCAs and epistomatal wax tube distribution (WTD) during one year, respectively, but a lower occurrence of particles and fungal hyphae than those of more southern transects. The higher ANWC was related to higher atmospheric SO2 concentration, and to the lower long-term temperature sum, but not clearly to annual precipitation. In the Monchegorsk smelter area, the current needles exhibited, on average, a 15% higher WTD and seven degree larger DCA, resulting in more hydrophobic needle surfaces than in Finnish Lapland, but during their first year, both the AWER and ANWC, were greatly increased. In Finnish Lapland, 30%, of all the epistomatal wax tubes disappeared from the needle surface during the first year, the value being 70% for the pines located 8 km from the smelter. The mineral composition of the particles deposited on the needle surfaces mirrored that of the minerals being produced by the smelters (e.g. FexSx, CuFeS2, NixSx, FexOx). Stomatal densities were in the range of 71.1-141.7 stomata mm(-2). The lower densities of stomata on needles close to the smelters correlated with reduced number of needle age classes of the pines, higher dry weights, higher pollutant accumulation and lower Mn and Zn concentrations in the needles. The AWER and ANWC were able to indicate the most seriously deteriorated needle surfaces on a regional scale, e.g. including the surroundings of both smelters, although the plot-specific relationships between 'needle surface variables' and 'pollution variables' were generally weak. The present study showed that the exposure of pine needles to the combined effects of ambient pollutants and harsh climate led to a deterioration in the physicochemical characteristics of the epicuticular wax, which may have serious ecophysiological consequences in the long term.     

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.     

The uptake of particulates by an urban woodland: site description and particulate composition

Woodlands may improve local air quality by increasing the uptake rates of gaseous, particulate and aerosol pollutants from the atmosphere and can also act as relatively permanent sinks for some pollutants. Rough Wood, Walsall was selected for a study of the material which accumulates on tree foliage because of its location in a densely populated urban area, and its proximity to a motorway with high traffic flow (the M6) and to other pollutant sources. Methods were developed for leaf washing to allow determination of the quantity of dust and the identification of the dust particles present on oak leaves. Elemental analysis of particles was also undertaken using scanning electron microscopy coupled with electron probe microanalysis. A large proportion of particles were organic in origin. Of the inorganic particles, the majority contained silicon and aluminium in varying proportions suggesting that they were soil derived. Some particles were clearly identified as the products of combustion, and sea or road salt was present on leaf surfaces. Some particles contained copper, tin and titanium which may reflect the proximity of Rough Wood to local metal workings. The number of particles counted on leaf surfaces decreased as distance from the motorway increased.     

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.