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.     

Biodegradation of aliphatic and aromatic hydrocarbons by natural soil microflora and pure cultures of imperfect and lignolitic fungi

The biodegradation of aliphatic and aromatic hydrocarbons by natural soil microflora and seven fungi species, including imperfect strains and higher level lignolitic species, is compared in a 90-day laboratory experiment using a natural, not-fertilized soil contaminated with 10% crude oil. The natural microbial soil assemblage isolated from an urban forest area was unable to significantly degrade crude oil, whereas pure fungi cultures effectively reduced the residues by 26-35% in 90 days. Normal alkanes were almost completely degraded in the first 15 days, whereas aromatic compounds (phenanthrene and methylphenanthrenes) exhibited slower kinetics. Aspergillus terreus and Fusarium solani, isolated from oil-polluted areas, produced the more efficient attack of aliphatic and aromatic hydrocarbons, respectively. Overall, imperfect fungi isolated from polluted soils showed a somewhat higher efficiency, but the performance of unadapted, indigenous, lignolitic fungi was comparable, and all three species, Pleurotus ostreatus, Trametes villosus and Coriolopsis rigida, effectively degraded aliphatic and aromatic components. The simultaneous, multivariate analysis of 22 parameters allowed the elucidation of a clear reactivity trend of the oil components during biodegradation: lower molecular weight n-alkanes > phenanthrene > 3-2-methylphenanthrenes > intermediate chain length n-alkanes > longer chain length n-alkanes > isoprenoids approximately 9-1-methylphenanthrenes. Irrespective of the individual degrading capacities, all fungi species tested seem to follow this decomposition sequence.     

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.     

The effect of papermill wastewater and organic amendments of sodium accumulation by potted cottonwoods

In this experiment, the impacts of pulp mill effluent irrigation, Fraser cottonwood (Populus deltoides 'Fraser') seedlings, and pulp sludge and manure soil amendments on sodium accumulation and distribution in the soil profile were evaluated during a 6 month greenhouse study. Sludge soil amendments and wastewater irrigation did not reduce stem biomass production of the cottonwood. Increased stem biomass production associated with manure soil amendments resulted in greater total uptake of sodium into stem material. This uptake was 0.002% of wastewater sodium inputs. In containers with seedlings, sodium concentrations were less in the surface horizon and more in the lower horizons than in containers with no seedlings. Infiltration rates and total sodium accumulation in the soil profile were not affected by the presence of Fraser cottonwood or the application of sludge or manure amendments to soil.     

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.     

Influence of reduced dietary calcium on the accumulation and effects of lead, cadmium, and aluminum in birds

The influence of low dietary calcium on the accumulation and effects of dietary lead, cadmium and aluminum was examined in zebra finches and ring doves. In zebra finches fed a diet containing 0.3% Ca, the hepatic and renal accumulation of lead was enhanced approximately 400% and of cadmium about 150-200%, compared to birds fed a 3.0% Ca diet. Low dietary Ca also caused bones of female finches to lose an average of about 60% of their normal Ca content. Loss of bone-Ca was also observed in male finches, but was less than in females. In reproductively active ring doves, low (0.4%) dietary Ca enhanced the accumulation of lead and cadmium, but not of aluminum, compared with accumulation in doves consuming a 2.0% Ca diet. Enhanced accumulation of lead and cadmium was accompanied by increased synthesis of the metal-binding protein metallothionein and by greater inhibition of delta-aminolevulinic acid dehydratase activity. These results indicate that, under conditions of reduced dietary Ca availability, such as can occur in acid-impacted environments, wild birds risk increased uptake of certain toxic metals and may accumulate toxic concentrations of these metals more rapidly. Researchers should take account of dietary Ca levels when interpreting results of dosing studies in which metals such as lead and cadmium are administered to birds.     

Effects of mercury exposure on ionic regulation in the crayfish Orconectes propinquus

Hemolymph sodium, potassium and calcium concentrations were determined in crayfish (Orconectes propinquus) exposed to (203)HgCl(2) mixed with food to a concentration of 1 microg Hg g(-1). Dummy-fed animals were exposed to Hg-dosed food wrapped in dialysis tubing to control for mercury reaching the animals via leaching from food to water. Hemolymph analyses were made following 14-day Hg exposures and again after a further 21-day 'depuration' period during which all animals were fed Hg-free food. After 14 days, the mercury reached a concentration of 0.175 microg g(-1) in the hepatopancreas and approximately half this level in the gills of Hg-fed animals. No depuration occurred from the hepatopancreas although the gills lost approximately two-thirds of their labelled mercury during the depuration period. Hemolymph sodium concentrations in Hg-exposed crayfish, both fed and dummy-fed, after 14 days were significantly lower than in Hg-free controls and remained low following the 21-day depuration period. Hemolymph calcium concentrations were lower in Hg-fed animals than in dummy-fed and control animals after 14 days although calcium levels rose in all treatments after 35 days. This may have been due to the incidence of pre-molt animals in all experimental groups, although the relationship between this and mercury exposure was not established unequivocally. Hemolymph potassium levels showed no differences between treatments.     

A “source” for asteroid larvae?: recruitment of Pisaster ochraceus,Pycnopodia helianthoides and Dermasterias imbricata in Nootka Sound,British Columbia

A major recruitment of the forcipulate asteroid Pisaster ochraceus was observed in September 1987 in the channel leading into Boca del Infierno, a semi-enclosed bay on the southeastern shore of Nootka Island, on the west coast of Vancouver Island, British Columbia, Canada. Newly settled recruits were observed at high densities subtidally in the channel (mean maximal density=1.23x10⁴m^-2) and at nearby sites. Subsequent surveys in 1988 to 1991 and size-frequency distributions of adults indicated strong yearly recruitment of P. ochraceus. Recruits of P. ochraceus were found on all available substrata, including hard and soft bottoms and on benthic algae. The initial food of the recruits included newly settled mussels (Mytilus sp.), snails and barnacles. Recruitment of the forcipulate Pycnopodia helianthoides was observed in 1987 to 1989 and in 1991, while recruitment of the spinulosan Dermasterias imbricata occurred only in 1988. High densities of planktonic bipinnaria larvae were found in the bay of Boca del Infierno in late May. We hypothesise that the high density population of adult P. ochraceus found in the channel of Boca del Infierno spawns synchronously and most of the resulting embryos and larvae are retained within the bay. This area may act as a source of larvae that then disperse locally. Post-recruitment mortality was estimated by comparing the density of recruits of P. ochraceus in 1987 with the numbers of juveniles presumed to be 1 yr old in 1988. Post-recruitment mortality was in excess of 97% with few individuals surviving to 1 yr. Moreover, even after the first year, mortality or emigration of the juveniles resulted in the almost complete loss of the 1-yr cohort at North Saavedra between 1988 and 1989. This study provides evidence that the P. ochraceus population in this area of Nootka Island may not be open, but may be regularly supplied from a source of larvae in the bay of Boca del Infierno. Post-settlement processes may, however, have significant effects on the local population, resulting in a poor correlation between the rate of recruitment and the incorporation of yr-1 + individuals into the adult population.     

Relation between heavy metal concentrations in salt marsh plants and soil

The aim of the research reported here was to investigate the relation between heavy metal concentrations in salt marsh plants, extractability of the metals from soil and some soil characteristics. In April 1987, Spartina anglica and Aster tripolium plants and soil were collected from four salt marshes along the Dutch coast. The redox potential of the soil between the roots of the plants and at bare sites was measured. Soil samples were oven-dried and analyzed for chloride concentration, pH, fraction of soil particles smaller than 63 microm (f < 63 microm), loss on ignition (LOI) and ammonium acetate and hydrochloric acid extractable Cd, Cu and Zn concentrations. The roots and shoots of the plants were analyzed for Cd, Cu and Zn. Because drying of the soil prior to chemical analysis might have changed the chemical speciation of the metals, and therefore the outcome of the ammonium acetate extraction, a second survey was performed in October 1990. In this survey A. tripolium plants and soil were collected from two salt marshes. Fresh and matched oven-dried soil samples were analyzed for water, ammonium acetate and diethylene triaminepentaacetic acid (DTPA) extractable Cd, Cu and Zn concentrations. The soil samples were also analyzed for f < 63 microm, LOI and total (HNO(3)/HCl digestion) metal concentrations. Soil metal concentrations were correlated with LOI. Drying prior to analysis of the soil had a significant effect on the extractability of the metals with water, ammonium acetate or DTPA. Plant metal concentrations significantly correlated only with some extractable metal concentrations determined in dried soil samples. However, these correlations were not consistently better than with total metal concentrations in the soil. It was concluded that extractions of metals from soil with water, ammonium acetate or DTPA are not better predictors for metal concentrations in salt marsh plants than total metal concentrations, and that a major part of the variation in metal concentrations in the plants cannot be explained by variation in soil composition.     

Dry deposition of nitrogen and sulfur to Ponderosa and Jeffrey pine in the San Bernardino national forest in Southern California

Little is known about the concentrations, deposition rates, and effects of nitrogenous and sulfurous compounds in photochemical smog in the San Bernardino National Forest (SBNF) in southern California. Dry deposition of NO(3)(-) and NH(4)(+) to foliage of ponderosa pine (Pinus ponderosa Laws.) and Jeffrey pine (Pinus jeffreyi Grev. & Balf.) was correlated (R = 0.83-0.88) with historical average hourly O(3) concentations at 10 sites across an O(3) gradient in the SBNF. Mean deposition fluxes of NO(3)(-) to ponderosa and Jeffrey pine branches were 0.82 nmol M(-2)s(-1) at Camp Paivika (CP), a high-pollution site, and 0.19 nmol m(-2) s(-1) at Camp Osceola (CAO), a low-pollution site. Deposition fluxes of NH(4)(+) were 0.32 nmol m(-2) s(-1) at CP and 0.17 nmol m(-2) s(-1) at CAO, while mean values for SO(4)(2-) were 0.03 at CP and 0.02 nmol m(-2) s(-1) at CAO. Deposition fluxes to paper and nylon filters were higher in most cases than fluxes to pine branches at the same site. The results of this study suggest that an atmospheric concentration and deposition gradient of N and S compounds occurs along with the west-east O(3) gradient in the SBNF. Annual stand-level dry deposition rates for S and N at CP and CAO were estimated. Further studies are needed to determine if high N deposition loads in the SBNF significantly affect plant/soil nutrient relations, tree health, and the response of ponderosa pine to ozone.