Quantification of Polymerisation Processes During The Oxidative Degradation of 14C-Labelled Chlorophenols

In experiments employing the lignocellulose-decaying basidiomycetes Trametes versicolor and Stropharia rugosoannulata degrading uniformly¹⁴C-labelled 2,4-dichlorophenol and pentachlorophenol, acombination of size exclusion chromatography (SEC),fractionation, and -scintillation counting wasapplied to quantify polymerisation products formed duringchlorophenol degradation. Time-dependent mass balances weregenerated by analysis of ¹⁴C in polymerisation products,CO₂, as well as monomer non-polar and polar metabolites.Approximately 30% of the chlorophenols were found to bepolymerised. A major fraction of the polymerised productscorresponded to a molecular weight range from 0.24 – 40 kDa.Only a minor fraction could be attributed to a molecularweight >40 kDa. This method proved to be useful inquantification of polymerisation products and kinetics of thepolymerisation processes, whereas UV/Vis detection ofpolymerisation products separated by SEC led to false positiveresults. The SEC-¹⁴C method could also be applied forother complex processes where polymerisation ordepolymerisation occurs (humification, degradation oflignocellulose, formation of bound residues from xenobioticssuch as polycyclic aromatic hydrocarbons or 2,4,6-trinitrotoluene) and where spectrophotometric determinationsare difficult or impossible.     

Landscape ecology of eastern coyotes based on large-scale estimates of abundance.

Since their range expansion into eastern North America in the mid-1900s, coyotes (Canis latrans) have become the region's top predator. Although widespread across the region, coyote adaptation to eastern forests and use of the broader landscape are not well understood. We studied the distribution and abundance of coyotes by collecting coyote feces from 54 sites across a diversity of landscapes in and around the Adirondacks of northern New York. We then genotyped feces with microsatellites and found a close correlation between the number of detected individuals and the total number of scats at a site. We created habitat models predicting coyote abundance using multi-scale vegetation and landscape data and ranked them with an information-theoretic model selection approach. These models allow us to reject the hypothesis that eastern forests are unsuitable habitat for coyotes as their abundance was positively correlated with forest cover and negatively correlated with measures of rural non-forest landscapes. However, measures of vegetation structure turned out to be better predictors of coyote abundance than generalized "forest vs. open" classification. The best supported models included those measures indicative of disturbed forest, especially more open canopies found in logged forests, and included natural edge habitats along water courses. These forest types are more productive than mature forests and presumably host more prey for coyotes. A second model with only variables that could be mapped across the region highlighted the lower density of coyotes in areas with high human settlement, as well as positive relationships with variables such as snowfall and lakes that may relate to increased numbers and vulnerability of deer. The resulting map predicts coyote density to be highest along the southwestern edge of the Adirondack State Park, including Tug Hill, and lowest in the mature forests and more rural areas of the central and eastern Adirondacks. Together, these results support the need for a nuanced view of how eastern coyotes use forested habitats.     

Determination of volatile organic sulfur compounds in contaminated groundwater

A practical method for the quantification of total purgeable organic sulfur (POS) in highly contaminated groundwater is described. Volatile organic sulfur compounds (VOSC) are purged from the water samples by a stream of oxygen and combusted. The emerging sulfur dioxide is absorbed in H₂O₂ and converted to sulfate which is quantified by ion chromatography and reported as mass sulfur equivalent. The overall limit of quantification is 0.03 mg l⁻¹. The content of POS is balanced with the total VOSC determined by GC-AED after liquid–liquid extraction. Separate determination of the non-volatile organic sulfur compounds by direct combustion of the water sample and adsorption to charcoal yielded a mass balance of the total sulfur content. Semi-quantitative GC-MS after purge & trap accumulation revealed that the VOSC mixture is composed of C₁–C₄ alkyl sulfides. The implementation of the developed methodology for the quantification of VOSC as potential catalyst poison in a cleaning plant for groundwater contaminated with volatile haloorganics (VOX) is presented.     

Moosmonitoring als Spiegel der Landnutzung?

Goal, Scope and Background

The study was conducted to test the hypothesis that the regional variability of nitrogen (N) and metal accumulations in terrestrial ecosystems are due to historical and recent ways of land use. To this end, in two regions of Central Europe the metal and N accumulations in both regions should be examined by comparative moss analysis. The regions should be of quantitatively specified representativity for selected ecological characteristics of Europe. Within both regions these characteristics should be covered by the sites where the moss samples were collected. The number of samples should allow for geostatistical estimation of the measured nitrogen and metal loads.

Methods

The two regions of investigation were selected according to an ecological land classification of Europe which was computed by classification trees. Within each of both research areas the sampling points were localized according to the areas occupied by the ecologically defined land classes. The sampling and chemical analysis of mosses was conducted in accordance with an appropriate UNECE guideline by means of ICP-MS (metals) and combustion analysis (N). The quality of measurements was assured using certified reference materials. The differences of deposition loads were tested for statistical significance with regard to time and space. Variogram analysis was used to examine and model the spatial autocorrelation function of the measurements. Ordinary kriging was then applied for surface estimations.

Results

By use of the ecological regionalisation of Europe the Weser-Ems Region (WER) and the Euro Region Nissa (ERN) were selected for investigation. The sampling sites represent quite well the natural landscapes and the land use categories of both regions. The measurement values corroborate the decline of metal accumulation observed since the beginning of the European Mosses Monitoring Survey in 1990. The metal loads of the mosses in the ERN exceed those in the WER significantly. The opposite holds true for the N concentrations: those in the WER are significantly higher than those in the ERN.

Discussion

The decrease of heavy metal emissions is correlated with lowered deposition and accumulation rates in terrestrial ecosystems. The accumulation of nitrogen in the biosphere is not following this trend.

Conclusions

The technique of moss analysis is adequate for spatially valid biomonitoring of spatial and temporal trends of metals and nitrogen in terrestrial ecosystems. By this, it enables to prove the efficiency of environmental policies.

Recommendations and Perspectives

The accumulation of N in ecosystems is still a serious environmental problem. Related ecological impacts are the eutrophication of aquatic ecosystems like ground waters, lakes, rivers and oceans as well as the biocoenotic changes in terrestrial ecosystems. Thus, a statistically valid exposure analysis must encompass both, accumulation of metals and N bioaccumulation. Further, the bioaccumulation of persistent organic pollutants should be monitored. Finally, environmental biomonitoring should be conducted in much closer contact with human health aspects.     

Metallakkumulation in Moosen: Standörtliche und regionale Randbedingungen des Biomonitoring von Luftverunreinigungen

Goal and Scope

Several studies show that the concentration of metals in mosses depends not only on metal deposition but also on factors such as moss species, canopy drip, precipitation, altitude, distance to the sea and the analytical technique used. However, contrasting results have been reported and the interpretation of the spatial variability of the metal accumulation in mosses remains difficult. In the presented study existing monitoring data from the European Heavy Metals in Mosses Surveys together with surface data on precipitation, elevation and land use are statistically analysed to assess factors other than emissions that have an influence on the metal accumulation in the mosses.

Main Features

Inference statistics and Spearman correlation analysis were applied to examine the association of the metal accumulation and the distance of the monitoring sites to the sea as well as the altitude. Whether or not significant differences of the metal loads in the mosses exist at national borders was examined with help of the U-test after Mann and Whitney. In order to identify and rank the factors that are assumed to have an influence on the metal uptake of the mosses Classification and Regression Trees (CART) were applied.

Results

No clear tendency could be derived from the results of the inference statistical calculations and the correlation analyses with regard to the distance of the monitoring site to the sea and the altitude. According to the results of the CART-analyses mainly the moss species, potential emission sources around the monitoring sites, canopy drip and precipitation have an effect on the metal bioaccumulation. Assuming that each participating country followed strictly the manual for sampling and sample preparation the results of the inference statistical calculations furthermore suggest that in most cases different techniques for digestion and analysis bias the measurements significantly.

Discussion

For the first time a national monitoring data base consisting of measurement data and metadata as well as surface information on precipitation, land use and elevation was applied to examine influence factors on the metal bioaccumulation in mosses. The respective results mirror existing knowledge from other national studies to a large extend, although further analyses are necessary to affirm the findings. These analyses should include data from other national monitoring programmes and should additionally be carried out with other decision tree algorithms than CART.

Conclusions

The local variability in the metal concentration in mosses can be uncovered in terms of predictors or underlying hidden causes by using CART. Ideally, such an approach should be applied across the whole of Europe. This will only be feasible if all participating countries provide additional information about site characteristics as currently is done in for example the German moss surveys.

Recommendations

The UNECE Metals in Mosses Survey experimental protocol should be improved in order to reduce the observed influences, to enhance standardisation, and to strengthen the quality control. This implies the integration of sampling site describing metadata into the assessment. Furthermore, basis research is needed to test the hypothesis concerning moss species-specific accumulation of depositions.

Perspectives

Provided that the presented results hold true in further analyses correction factors should be applied on the moss data in order to get the depicted spatial patterns and temporal trends of metal bioaccumulation unbiased. Such factors should be calculated for natural landscape units or ecoregions that are homogeneous with regard to climate, vegetation and altitude.     

Antagonistic interactions between plant competition and insect herbivory

Interspecific competition between plants and herbivory by specialized insects can have synergistic effects on the growth and performance of the attacked host plant. We tested the hypothesis that competition between plants may also negatively affect the performance of herbivores as well as their top-down effect on the host plant. In such a case, the combined effects of competition and herbivory may be less than expected from a simple multiplicative response. In other words, competition and herbivory may interact antagonistically. In a greenhouse experiment, Poa annua was grown in the presence or absence of a competitor (either Plantago lanceolata or Trifolium repens), as well as with or without a Poa-specialist aphid herbivore. Both competition and herbivory negatively affected Poa growth. Competition also reduced aphid density on Poa. This effect could in part be explained by changes in the biomass and the nitrogen content of Poa shoots. In treatments with competitors, reduced aphid densities alleviated the negative effect of herbivory on above- and belowground Poa biomass. Hence, we were able to demonstrate an antagonistic interaction between plant-plant interspecific competition and herbivory. However, response indices suggested that antagonistic interactions between competition and herbivory were contingent on the identity of the competitor. We found the antagonistic effect only in treatments with T. repens as the competitor. We conclude that both competitor identity and the herbivore's ability to respond with changes in its density or activity to plant competition affect the magnitude and direction (synergistic vs. antagonistic) of the interaction between competition and herbivory on plant growth.     

Mapping atmospheric depositions of cadmium and lead in Germany based on EMEP deposition data and the European Moss Survey 2005

Background

The vertical migration of phytoplankton was investigated in natural waters using in situ fluorescence profiling, chlorophyll a concentrations and life counts at two study sites differing in coloured dissolved organic matter (cDOM) concentrations. The data from the corresponding water depths (50-cm intervals down to 10 m) and times (hourly, before dawn to sunset, several days) were related to the highly resolved (2 nm) underwater ultraviolet radiation (UVR)/photosynthetic active radiation (PAR) transparency (290 to 700 nm).

Results

Chlorophyll a maxima of mainly motile dinoflagellates were observed in situ at all days and at both study sites (open marine, brackish waters), independent on prevailing weather conditions or cDOM concentrations. Phytoplankton migration was triggered solely by irradiance in the 400- to 700-nm wavelength range (PAR) at the particular water depth, irrespective of PAR/UVR ratios and surface UVR (290 to 400 nm), after an illumination period of about 40 min. Interestingly, the PAR tolerance levels of the phytoplankton, which have been lower in cDOM-rich waters, matched their light acclimation values determined by parallel PAM measurements.

Conclusions

The response of the phytoplankton to PAR is not a sufficient protection strategy versus increasing UVR levels, which might have wide ecological implications beyond the level of primary producers to impact important ecosystem functions such as the delicate trophic interactions.     

Egg-mimicry as a mating strategy in the fantail darter,Etheostoma flabellare: females prefer males with eggs

Summary In some species of fishes with paternal care, females prefer to spawn with males already defending eggs. Such female preference appears to have resulted in adoption of unrelated eggs as a male mating strategy in several species. Page and Swofford (1984) proposed that such female preference may have also resulted in the evolution of male egg-mimics in several species of darters (Percidae); however, their hypothesis has not been tested. We examined female preference in the fantail darter (Etheostoma flabellare) and found that females preferred males with eggs over males without eggs, and males with egg-mimics over males without egg-mimics. Thus it appears that female preference for males already guarding eggs may have led to the evolution of specialized egg-mimicking morphology in males.