Changes in toxicity and Ah receptor agonist activity of suspended particulate matter during flood events at the rivers Neckar and Rhine — a mass balance approach using in vitro methods and chemical analysis

Background, aim, and scope  

As a consequence of flood events, runoff and remobilized sediments may cause an increase of ecotoxicologically relevant effects from contaminant reservoirs. Aquatic and terrestrial organisms as well as cattle and areas of settlement are exposed to dislocated contaminants during and after flood events. In this study, the impacts of two flood events triggered by intense rain at the rivers Neckar and Rhine (Southern Germany) were studied. Effects in correlation to flood flow were assessed at the river Neckar using samples collected at frequent intervals. River Rhine suspended particulate matter (SPM) was sampled over a longer period at normal flow and during a flood event. Three cell lines (H4L1.1c4, GPC.2D.Luc, RTL-W1) were used to compare Ah receptor agonist activity in different biotest systems. Multilayer fractionation was performed to identify causative compounds, focusing on persistent organic contaminants.     

Long Term Effects of Acid Irrigation at the Höglwald on Seepage Water Chemistry and Nutrient Cycling

In order to test the hypothesis of aluminium toxicity induced by acid deposition, an experimental acid irrigation was carried out in a mature Norway spruce stand in Southern Germany (Höglwald). The experiment comprised three plots: no irrigation, irrigation (170 mm a^?1), and acid irrigation with diluted sulphuric acid (pH of 2.6–2.8). During the seven years of acid irrigation (1984–1990) water containing 0.43 mol_c m^?2 a^?1 of protons and sulphate was added with a mean pH of 3.2 (throughfall?+?acid irrigation water) compared to 4.9 (throughfall) on both control plots. Most of the additional proton input was consumed in the organic layer and the upper mineral soil. Acid irrigation resulted in a long lasting elevation of sulphate concentrations in the seepage water. Together with sulphate both aluminium and appreciable amounts of base cations were leached from the main rooting zone. The ratio between base cations (Ca?+?Mg?+?K) and aluminium was 0.79 during acid irrigation and 0.92 on the control. Neither tree growth and nutrition nor the pool of exchangeable cations were affected significantly. We conclude that at this site protection mechanisms against aluminium toxicity exist and that additional base cation runoff can still be compensated without further reduction of the supply of exchangeable base cations in the upper mineral soil.     

Plant-specific responses to zinc contamination in a semi-field lysimeter and on hydroponics

The species Agrostis stolonifera, Brassica napus and Trifolium repens representing different ecological strategies, were selected to study the effect of Zn contamination on Zn tolerance, uptake and accumulation patterns. Parallel tests were carried out with increasing concentrations of Zn in a semi-field lysimeter and hydroponics in the climate chamber. A significant reduction in biomass production or root length and an increase in shoot Zn concentration was observed for all species at increasing external Zn concentrations. However, shoot biomass production, Zn tolerance and Zn accumulation differed significantly among the tested species. The results in both experimental set-ups were quite similar concerning Zn tolerance and accumulation and improved the validity of the findings. The rather specific responses of the different plant species to Zn contamination interfere with the more generic approach used in risk assessment studies. Maximum amounts of Zn in shoot are not likely to cause a risk to herbivores.     

Verbleib von spurenschadstoffen bei der methylesterherstellung aus altspeisefett im technikumsmaßstab

Aims and Scope

In Germany, 120,000 tons per year of waste edible fats are collected from the catering and the food industry Until recently, these fats have widely been used as a nutritional additive for poultry and other animals fodder. Due to the BSE crisis and some affairs based on dioxins in feeding stuff, waste fats are now barely used as fodder. Currently, these fats substitute fresh vegetable oils in the chemical industry and are used as raw material for the production of biodiesel. Therefore, alternative fields of application are required. In this context, the Deutsche Bundesstiftung Umwelt (DBU) is sponsoring a joint research project which deals with the production and testing of cooling lubricants based on monoesters made from waste edible fats.

Methods

In a first step, characteristics and quality of wasteedible fats of different origins were chemically analysed and monitored. The investigations covered the following fat specific parameters: total contamination, sulphate ash, water content, peroxide number, iodine value, kinematical viscosity, neutralisation number (free fatty acids) and fatty acid spectra. In the next step, a process development/optimisation was carried out for the production of methylesters based on the raw material waste fat, leading to the construction of a pilot plant. To investigate the fate of trace pollutants during the production process of waste-fat methylester, samples were systematically contaminated with polycyclic aromatic hydrocarbons, polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and the elements Al, Cd, Cr, Cu, Ni, P, Pb, Sn, and Zn. These contaminated fat samples were transesterified in laboratory scale. The primary and by-products were analysed subsequently.

Results

Valuable hints on the design of the technical process of fatty adid methylester production based on waste edible fats were gained by regarding the fat specific parameters. For example, filtration and dewatering of the waste fats proved necessary. The saturated fatty acids, most wanted for the production of cooling lubricants due to their high oxidation stability, were present in the range of 11,3% to 31,6%. Due to the low content of free fatty acids, a base catalysed process occurred more suitable for the transesterification of the waste edible fats. Trace analytical investigations concerning inorganic and organic pollutants proved a low basic contamination of the waste edible fats. Experiments with systematic contamination of the fats indicated an accumulation of the heavy metals in the glycerol phase during the transesterification process, whereas the organic pollutants were detected in the methylester fraction by amounts of 80% to 95%.

Outlook

In a next step, the further processing of the methylesters to monoesters with alcohols of the chain length C2 to C8 will be presented. Associated results of chemical-analytical investigations on the process and the application of the cooling lubricants will also be given.     

Determination of pentachlorophenol (PCP) in waste wood--method comparison by a collaborative trial

Two independently developed and validated procedures for the determination of pentachlorophenol (PCP) in waste wood were compared by means of a collaborative trial. Both methods foresee quantification of PCP by gas chromatography (GC-ECD) after acetylation and differ with regard to the use of methanol or toluene/sulphuric acid, respectively, as solvent in the sonication extraction step. Test samples with established analyte homogeneity were prepared from a ground "real life" starting material. A total of 23 participating laboratories with experience in wood preservative analysis were instructed to apply both methods to three levels of content in the range of 0.5-20 mg PCP/kg. In case of the toluene/sulphuric acid extraction, lower recoveries and higher interlaboratory dispersion of results at the higher PCP contents were observed. Seen against the background of the Horwitz equation a reproducibility standard deviation of approximately 19% for the methanol extraction at the 4.5 mg/kg level meets the requirement for a sound analytical method. Thus, the sonication extraction procedure with methanol has been annexed as a reference method to the German waste wood regulation.     

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.