Resembling a “natural formation pattern” of chlorinated dibenzo-p-dioxins by varying the experimental conditions of hydrothermal carbonization

Until several years ago dioxins were considered as just an unwanted by product of anthropogenic activities and stigmatized as the symbol of man-made environmental pollution. Natural processes, such as forest fires, can emit dioxins, but compared to industrial processes, usually very low quantities are emitted. However after a case of food contamination occurred in the United States of America in 1996 caused by kaolinitic clay a discussion on the provenience started. Besides the relatively high concentration also an unusual PCDD/F distribution pattern was found in these ball clay samples. This specific pattern related to none of the known anthropogenic sources for these contaminants and, in relation to a supposed natural formation, later it was named “natural formation pattern”. Hydrothermal carbonization (HTC) can transform biomass within hours into a brown coal-like product which resembles naturally occurring coal formation. HTC can also transform an already present PCDD/F contamination in a way to obtain a “natural formation pattern” characterized by an unusual high ratio between 1,2,3,7,8,9-HxCDD and 1,2,3,6,7,8-HxCDD and the absence of almost all chlorinated dibenzofurans. By varying the experimental conditions of the HTC process applied to sewage sludge samples contaminated with PCDD/Fs from anthropogenic sources, beside the “natural formation pattern” at a temperatures of 255 °C, a remarkable increase of the toxicity based on WHO–TEQ was observed.     

Molecular effects and bioaccumulation of levonorgestrel in the non-target organism Dreissena polymorpha

Bioaccumulation and effects of the contraceptive hormone levonorgestrel were examined in the non-target organism Dreissena polymorpha. Molecular biomarkers of biotransformation, elimination, antioxidant defence and protein damage were analyzed after exposure to increasing concentrations of levonorgestrel in a flow-through system. The lowest concentration (0.312 μg L⁻¹) was 100-fold bioconcentrated within four days. A decrease of the bioconcentration factor was observed within one week for the highest test concentrations (3.12 and 6.24 μg L⁻¹) suggesting enhanced excretory processes. The immediate mRNA up-regulation of pi class glutathione S-transferase proved that phase II biotransformation processes were induced. Disturbance of fundamental cell functions was assumed since the aryl hydrocarbon receptor has been permanently down-regulated. mRNA up-regulation of P-glycoprotein, superoxide dismutase and metallothioneine suggested enhanced elimination processes and ongoing oxidative stress. mRNA up-regulation of heat shock protein 70 in mussels exposed to the two highest concentrations clearly indicated impacts on protein damage.     

Water quality indices across Europe--a comparison of the good ecological status of five river basins

The European Water Framework Directive (WFD) requires the definition of near-natural reference conditions to determine the extent of water bodies' deviation from "good ecological status" caused by stress gradients. However, the classification of ecological quality depends on the assessment method applied and the stressor concerned. While assessment methods that are generally applicable would be favourable, many European countries employ the locally developed water quality metrics that assess the impact of organic pollution (including eutrophication) and the associated decrease in dissolved oxygen. These indices do not specifically address stress from organic toxicants, such as pesticides. The aim of this study was to examine the performance of presently used assessment methods to identify reference conditions of non-contaminated streams in five selected European river basins, covering the geographical region from Spain to Finland, as a crucial prerequisite to indicate toxic gradients. The analysis comprised the Belgium biotic index (BBI), the biological monitoring working party (BMWP) scoring system and the revised German saprobic index. For comparison, we included an adaptation of the recently developed SPEAR index. In two previous field studies, this metric highly correlated with measured pesticide gradients. In this study, SPEAR was the only indicator that was generally applicable to all monitoring data and capable of determining "high ecological status" of reference conditions in all basins. Thus, based upon previous and own results, the authors suggest the species at risk (SPEAR) index to be potentially useful as a European-wide index to address deviations from "good ecological status" due to organic toxicants and recommend it for consideration in integrated water-resource evaluations under the WFD.     

Post-combustion syntheses of PCDD/F and PBDD/F from halogen-rich fuel is suppressed by a pebble heater technology

GOAL, SCOPE AND BACKGROUND: Changes in German and European legislation shifted processing of polymer-rich shredding residues (SR) from landfill to thermal treatment. However, when waste of electric and electronic equipment (WEEE) is the source of SR, thermal treatment is complicated by halogens as well as the presence of polybrominated dioxins and furans (PBDD/F) and brominated flame retardants (BFR). Hence, WEEE requires high temperature incineration with sufficient residence times. Post-combustion synthesis of polyhalogenated dioxins and furans (PXDD/F) is dominant in the temperature range between 250-450 degrees C. Thus, a very rapid gas cooling from 450 degrees to 250 degrees C is important for proper raw gas treatment. The pebble heater technology developed by ATZ Entwicklungszentrum (Sulzbach-Rosenberg, Germany) might serve as an alternative to the state-of-the-art quench cooling. It is based on the application of a pebble bed of natural bulk material, which the exhaust gases flows through radially. It provides an excellent heat transfer and a temperature gradient in the range of 1,500-2,000 K/m. The paper presents data of a pilot application of the pebble heater technology for the treatment of raw gas derived from the incineration of polymeric materials from WEEE. METHODS: A liquid fuel was chosen in order to minimise technical modifications of the plant. It was analysed for halogens by x-ray fluorescence, for brominated flame retardants by HPLC-UV/MS and for PXDD/F by GC-HRMS. Combustion gases were rapidly cooled down to temperatures below 200 degrees C and emissions of PBDD/F and PCDD/ F were estimated without further off-gas treatment. PBDD/F emissions were computed as PCDD/F toxicity equivalents applying two different calculation approaches. RESULTS AND DISCUSSION: PCDD/F emissions accounted for 0.04 ng I-TEQ/Nm3 and are in compliance with European emission limits. Calculated PBDD/F toxicity equivalents exceeded the emission limit of 0.1 ng I-TEQ/Nm3 by factors of 75 and 208 depending on the calculation approach. A mass balance of PBDD/F and PCDD/F congeners revealed an efficient elimination of more than 95% in most cases. Lower reduction rates (76% for 2,3,7,8-TeBDF and 82% for 1,2,3,7,8-PeBDF) were attributed to incomplete combustion. An intended recovery of halogens by one-stage scrubbing downstream of the pebble heater was ineffective, recovering 28% of the applied chlorine and 9% of the bromine, only. CONCLUSIONS: Our pilot incineration test indicates that the pebble heater technology can effectively suppress a post-combustion synthesis of PCDD/F and PBDD/F, resulting in low PCDD/F emission levels without further off-gas treatment. The presented data state that WEEE is sensible to incomplete combustion, which will lead to increased PBDD/F emissions without increasing PCDD/F emission limits. This finding is especially relevant for small and low-technical incineration appliances, which have been reported to treat WEEE in developing countries and are considered to serve as a significant source of PXDD/F these days. RECOMMENDATIONS AND PERSPECTIVES: Monitoring of PCDD/F emissions only might considerably underestimate the total emission of dioxins and dioxin-like compounds. It is therefore an ineffective means for assessing resulting health risks, at least for those waste treatment plants which are considered to handle the increasing amounts of PBDD/ F-containing polymers from WEEE in future. Consequently, it is recommended to initiate a screening programme for PXDD/F emissions in large scale incineration facilities which are capable of treating WEEE shredder residues.     

Langfristigkeit ökosystemarer Forschung

Time in environmental science continues to be almost neglected. In connection with rising ecological problems long-term research, as is necessary for the evaluation and prediction of environmental conditions, seems to be an exception. Complex ecosystems, e.g. terrestrial and marine systems, however, are characterized by long lasting natural time-scales which must be taken into account by analyzing them. In this context the role of time in ecosystems research becomes important. Therefore, a data base was conceptualized that could take up the main characteristics of ecosystematic analyses. Annual research reports of ecosystem research centers were revised for taking them up into the data base. In this way it is possible to evaluate the pool of data on special aspects, especially on the time parameters of the analyses. One result — besides a partial unequality of the time scales in experiment and reality — is that long-term research in terrestrial ecosystems is very rare. The reasons for this are various, but cannot divert from the need for a greater consideration of longterm observation of the ecosystems. Otherwise the ecosystematic research will not be able to meet their tasks of evaluation and prediction.     

德国环境保护与空间规划

本文对德国的环境保护发展状况作了简要介绍。对德国空间环境规划作了详细说明和分析。     

In situ evaluation of the genotoxic potential of the river Nile: I. Micronucleus and nuclear lesion tests of erythrocytes of Oreochromis niloticus niloticus (Linnaeus, 1758) and Clarias gariepinus (Burchell, 1822)

This study aimed to investigate the genotoxic potential of chemicals present along the course of the river Nile using frequencies of micronuclei (MN) and nuclear lesions (NL) in erythrocytes of Nile tilapia Oreochromis niloticus niloticus and African catfish Clarias gariepinus, as biomarkers. Results showed that most of the physicochemical parameters detected and heavy metal concentrations were significantly higher in the water collected from the estuaries of the river Nile compared to other sites of the upper Nile. The frequencies of MN and NL in peripheral blood erythrocytes of Nile tilapia and African catfish were significantly higher in estuary sites in Damietta and Rosetta compared to upper sites. The lowest level of genotoxicity was observed at two sites (Aswan and Kena), considered to be less contaminated. Our results suggested that higher frequencies of MN and NL determined at Damietta and Rosetta sites may be indicative of damage produced by pollutants in these areas. The most remarkable result was that MN and NL frequencies appear to be strongly related to water quality at different sites examined, indicating that MN frequencies may serve as a reliable biomarker for testing genotoxicity in situ. The positive correlation between MN and NL induction suggested that NL may be a useful complementary assay for genotoxicity analyses when fish are used as experimental animals. It was also found that seasonal variations in MN and NL frequencies might contribute to a better understanding of genotoxic responses in the field. The use of fish as indicator organisms for monitoring the presence of genotoxic-inducing contaminants in the environment seemed justified because the effects of exposure to a “complex mixture” such as river water were obtained. Nile tilapia appears to be a more suitable bioindicator species than African catfish in studying genotoxic chemical pollution in the river Nile attributed to a higher sensitivity.     

Source and Distribution of Heavy Metals in Food†

Diet is the major route of exposure to contaminants, therefore food monitoring programs are essential to estimate the degree of human risk. We present a study undertaken in Austria dealing with the total uptake of mercury, cadmium, arsenic and lead. The dates were calculated from diet as well as from commercial food. Higher contaminated foodstuffs are registered and a comparison was made between body burden of babies and adults on the basis of bodyweight. It was pointed out, that cooked or washed food ready to eat has a lower burden of lead and cadmium than non prepared food due to household processing, which may decontaminate food to some extent’ Arsenic content was not reduced, because it is bound chemically and not primarily deposited on the surface of food such as in the case of lead. It was mentioned that the type of compound plays an important role in the assessment of action of those elements on humans.

Their biological activity is not necessarily related to their concentration in food. As in the case of selenium and chromium one has to take into consideration that there is a narrow range between benefit and harm, toxicity, and minor supply.

Therefore we conclude, that due to interactions of elements, their different biological activity and due to the difference of compounds present in food, we have to relativate the terms toxicity and essentiality. Then we can get a more profound insight into the problems of trace elements in food.     

Null model analysis of species associations using abundance data

The influence of negative species interactions has dominated much of the literature on community assembly rules. Patterns of negative covariation among species are typically documented through null model analyses of binary presence/absence matrices in which rows designate species, columns designate sites, and the matrix entries indicate the presence (1) or absence (0) of a particular species in a particular site. However, the outcome of species interactions ultimately depends on population-level processes. Therefore, patterns of species segregation and aggregation might be more clearly expressed in abundance matrices, in which the matrix entries indicate the abundance or density of a species in a particular site. We conducted a series of benchmark tests to evaluate the performance of 14 candidate null model algorithms and six covariation metrics that can be used with abundance matrices. We first created a series of random test matrices by sampling a metacommunity from a lognormal species abundance distribution. We also created a series of structured matrices by altering the random matrices to incorporate patterns of pairwise species segregation and aggregation. We next screened each algorithm-index combination with the random and structured matrices to determine which tests had low Type I error rates and good power for detecting segregated and aggregated species distributions. In our benchmark tests, the best-performing null model does not constrain species richness, but assigns individuals to matrix cells proportional to the observed row and column marginal distributions until, for each row and column, total abundances are reached. Using this null model algorithm with a set of four covariance metrics, we tested for patterns of species segregation and aggregation in a collection of 149 empirical abundance matrices and 36 interaction matrices collated from published papers and posted data sets. More than 80% of the matrices were significantly segregated, which reinforces a previous meta-analysis of presence/absence matrices. However, using two of the metrics we detected a significant pattern of aggregation for plants and for the interaction matrices (which include plant-pollinator data sets). These results suggest that abundance matrices, analyzed with an appropriate null model, may be a powerful tool for quantifying patterns of species segregation and aggregation.