New biodegradable polyester-copolymers from commodity chemicals with favorable use properties

Copolyesters composed of aliphatic and aromatic compounds were synthesized by the polycondensation of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, sebacic acid, adipic acid, and terephthalic acid. By applying an appropriate ratio of aliphatic to aromatic acids, the synthesized materials proved to be biodegradable, as was verified by several degradation test methods such as aqueous polymer suspension inoculated by a soil eluate (Sturm test), a soil burial test (at ambient temperature), and a composting simulation test at 60°C. The degradability of the polyester-copolymers (measured as weight loss) was investigated with respect to the aliphatic monomer components and the fraction of terephthalic acid. Excellent biodegradability was observed even for copolymers with a content of terephthalic acid up to 56 mol% (of the acid fraction) and melting points in the range up to 140°C. Degradation by chemical hydrolysis of the polyesters was determined independently and was found to facilitate microbial attack significantly only at higher temperatures. The findings demonstrate that biodegradable polymers with advantageous usage properties can easily be manufactured by conventional techniques from commodity chemicals (adipic acid, terephthalic acid, and ethylene glycol or 1,4-butanediol).Dedicated to Prof. J. Klein's 60th birthday.     

Enantiomer ratios,patterns and levels of toxaphene congeners in human milk from Germany

High resolution gas chromatography (HRGC) coupled to quadrupole negative ion chemical ionization (NICI) mass spectrometry (MS) was used to investigate congener patterns, levels and enantiomer distribution of selected toxaphene congeners (#26, #41, #44, #50, #63, B7-1453) in human milk from Germany. #50 and #26 were the most abundant congeners. Furthermore, the identification of B7-1453, B8-1412, #41, #42, #44 and #63 was possible. Levels for the sum of #26, #41, #44 and #50 ranged from 7 to 24 microg kg(-1) milk fat and contributed between 2 and 9% to the total burden of investigated organochlorines such as selected compounds of the chlordane group, HCH, DDT and polychlorinated biphenyls (PCB). Capillaries coated with heptakis-(2,3,6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (TBDMS-CD) or octakis-(2,3,6-tri-O-ethyl)-gamma-cyclodextrin (TEG-CD) were used for the enantioselective separations. Enantiomer ratios (ER) and enantiomer fractions (EF) of the abundant toxaphene congeners #26 and #50 as well as of B7-1453, #41 and #63 were determined. Greatest deviations from a racemic composition in individual human milk samples were found for #41 (1.54-2.37), #50 (1.37-1.72) and #63 (0.53-0.71) whereas ERs for #26 were close to 1. Compared to wildlife biota such as fish and raptors ER changes were more pronounced in human milk but comparable to human adipose tissue.     

PCDD/F levels in the neighbourhood of a municipal solid waste incinerator after introduction of technical improvements in the facility

In 1998 and 1999, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in soil and herbage samples collected in the vicinity of an old municipal solid waste incinerator (MSWI) (S. Adrià del Besòs, Barcelona, Spain). Just after the 1999 collection, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in this facility. The purpose of the present study was to determine the current concentrations of PCDD/Fs in soil and herbage samples collected in the neighbourhood of the MSWI and to compare these concentrations with those obtained in the 1998 and 1999 surveys. During the period 1998-1999, an increase of 31% (P>.05) was found in the median PCDD/F levels in soils, while a reduction of 40% (P>.05) was observed in the period 1999-2000. Similarly, in the period 1998-1999 an increase of 41% (P>.05) was found in the levels of PCDD/Fs in vegetation, while a 30% decrease (P<.05) was seen in the period 1999-2000. Although after introduction of the technical improvements in the MSWI a notable reduction in the levels of PCDD/Fs in soil and vegetation has been noted, the median decreases have not been as great as it could be expected according to the very pronounced reductions in PCDD/F emissions from the stack. It indicates that other emission sources of PCDD/Fs also have a notable impact on the area under direct influence of the MSWI.     

Chemical Changes in Sediment Pore-Waters of an Acidic Mining Lake After Addition of Organic Substrate and Lime for Stimulating Lake Remediation

In the past five years, enclosures have beeninstalled in an acidic mining lake in Lusatia to investigate insitu remediation processes. They were treated with straw, withstraw and Carbokalk, or with Carbokalk alone, where Carbokalkis a by-product of the sugar industry (solid precipitate ofnon-sugars after lime clarification of extracted sugar beetjuice). Sediment samples were taken as cores to get informationabout the behaviour of organic and inorganic components insediment pore-water with depth. Vertical distributions of pH,soluble reactive phosphate, nitrate, ammonium, silica,aluminium, iron, manganese, calcium, magnesium, sodium,potassium, sulphate, and DOC were measured. The resultingprofiles, each consisting of 15 data points at differentdepths, were compared by cluster analysis. The similarities ofsediment cores from different treated enclosures relating toprofiles of chemical components were discussed. Increasedconcentrations of potassium and sulphate were found in pore-water after substrate treatment. The data imply dissolution ofpotassium iron sulphate hydroxide minerals (jarosite) after anincrease of pH caused by dissolution of lime and by sulphatereducing processes which were stimulated by organic substrateaddition.     

Industrial Tailings in Traunsee (Austria) Revisited: The Status of 1999

Alkaline tailings from a salt work and a soda plant have been pumped into the southernmost part of Traunsee at Ebensee for many decades. A survey in 1981 showed an accumulation of more than 3 × 10⁶ m³ alkaline mud in the Bay of Ebensee and the existence of slumping structures and turbidites in the profundal zone of the lake. A new survey of the industrial tailings has been performed in 1999. Compared to the earlier survey, the accumulation in the Bay of Ebensee has grown to >4 × 10⁶ m³, which suggests an average yearly input of 90 000 m³. Slumping structures and turbidites document the unstable situation of the tailings near the waste inlet. The lake area occasionally affected by the turbidity currents in the profundal zone has increased to 19%. Within the central profundal area these tailings reach <1 m in thickness.     

A method for evaluating areas for national park status

A procedure for evaluating different areas as national parks based on a scoring system is proposed. A National Park Evaluation Form (NPEF) evaluating natural, cultural, and recreational resources in accordance with international criteria for national parks is presented. The evaluation points given to an area indicate the possibility of the area becoming a national park. In this method, subjectivity and bias have been minimized by a special application of the Delphi technique. The method outlined here could help in the efforts of selecting and establishing national parks in many countries.     

Formation of polyester blends by a recombinant strain ofPseudomonas oleovorans: Different poly(3-hydroxyalkanoates) are stored in separate granules

WhenPseudomonas oleovorans (GPo1) is grown on sodium octanoate under ammonium limiting conditions, it is able to accumulate a copolyester consisting of medium chain length 3-hydroxyalkanoic acids (PHA_m). 3-Hydroxybutyrate is only incorporated in trace amounts. WhenP. oleovorans is equipped with the PHB biosynthetic genes ofAlcaligenes eutrophus (GPo1[pVK101::PP1]), it forms a polyester containing major amounts of 3-hydroxybutyrate. The resulting polymer however is a blend of PHA_m and PHB, rather than a copolymer of 3-hydroxybutyrate and medium chain length 3-hydroxyalkanoic acids [11]. To establish whether PHA_m and PHB molecules are stored in the same or separate granules by this recombinantP. oleovorans strain, we studied polymer forming cells by freeze-fracture electron microscopy. This approach is possible because previous freeze-fracture electron microscopy studies on PHA_m and PHB accumulating strains have shown that PHA_m and PHB granules can be distinguished from each other: PHA_m granules from mushroom-like structures, whereas PHB granules from needle structures during freeze-fracturing. In this paper we show that stationary phase cells of GPo1[pVK101::PP1] contained both mushroom and needle-like structures, indicating that PHA_m and PHB chains were stored in separate granules. To be able to determine whether the separation of PHA_m and PHB is complete, the respective granules were separated on sucrose gradients. A total cell extract of GPo1[pVK101::PP1] which was subjected to sucrose gradient centrifugation revealed two white bands of different densities: the upper band with a density of 1.05 g/mL consisted exclusively of PHA_m granules, while the lower band with a density of 1.19 g/mL consisted of PHB granules only. Thus, when bacteria synthesize both PHA_m and PHB, the resulting polymer chains are segregated completely and stored in separate granules.