Anreicherung atmosphärischer Depositionen von Metallen und Stickstoff in Moosen Mecklenburg-Vorpommerns von 1990 bis 2005

Background, aim and scope Since 1990 the UN ECE Heavy Metals in Mosses Surveys provide data inventories of the atmospheric heavy metal bioaccumulation across Europe. In the survey 2005 the nitrogen accumulation was measured for the first time in most of the participating countries. In Germany, the surveys were conducted in close cooperation of the relevant authorities of both the Federal Republic and the sixteen states. Therefore, statistical evaluations of the moss survey data with regard to the whole German territory and single federal states are of interest. This article concentrates on Mecklenburg-Western Pomerania, dealing with the mapping of the spatiotemporal trends of metal accumulation from 1990 to 2005, the spatial patterns of nitrogen accumulation in 2005, and the spatial variability of bioaccumulation due to characteristics of the sampling sites and their surroundings. Materials and methods The bioaccumulation of up to 40 trace elements in mosses was determined according to a Europe-wide harmonised methodology. The according experimental protocol regulates the selection of sampling sites and moss species, the chemical analysis and quality control and the classification of the measured values for mapping spatial patterns. In Mecklenburg-Western Pomerania all sampling sites were described with regard to topographical and ecological characteristics and several criteria to be fulfilled according to the guideline. Together with the measurements this metadata was combined with other information regarding land use in the surroundings of the sampling sites in the WebGIS MossMet. The spatial structure of the metal bioaccumulation was analysed and modelled by variogram analyses and then mapped by applying different kriging techniques. Furthermore, multi metal indices (MMI) were derived for both the sampling sites and raster maps with help of percentile statistics: The MMI_1990–2005 was calculated for As, Cd, Cr, Cu, Fe, Ni, Pb, Ti, V and Zn. The statistical association of the metal bioaccumulation, site specific characteristics as well as information on land use and emissions was analysed by bivariate nonparametric correlation analysis, contingency tables and Chi-square Automatic Interaction Detection (CHAID). Results The results of the quality controlled chemical analyses show a significant decrease of the metal bioaccumulation in Germany from 1990 to 2000 for all elements. However, in Mecklenburg-Western Pomerania the concentrations of Cr and Zn are even significantly higher than those found in 1990. From 2000 to 2005?a further non-significant increase can be stated for As, Cu, Ni and Ti. The concentrations of Cd and Pb decreased significantly throughout all four surveys. The MMI illustrates the temporal trend of the metal bioaccumulation as a whole: After a significant decrease from 1990 to 2000 it increased significantly till 2005. The N concentration in mosses in Mecklenburg-Western Pomerania reaches from 1.3 to 2.3?% in dry mass and is negatively correlated with the forest ratio in the surroundings of the moss sampling sites and to the same degree positively correlated with the area ratio of agricultural land uses. Except for Cd, Pb and Sb all metal concentrations in the mosses are negatively correlated with the forest ratio around the sampling sites. With the exception of Cr all metal concentrations are further negatively correlated with the precipitation sums of the accumulation periods. Only the Cu and Zn concentrations show no or rather a negative correlation with the tree height whereas all other elements exhibit positive correlations. Furthermore, all elements except Cr are significantly associated to the sampled moss species, the growth pattern and the frequency of occurrence of the mosses at the respective sampling sites. Exemplified for Cu multivariate correlations were furthermore detected by CHAID. It could be shown that the frequency of the mosses, the sampled moss species, the distance to motorways and the distance to the Baltic Sea are the statistically most significant boundary conditions of the Cu concentrations in the mosses sampled in Mecklenburg-Western Pomerania in 2005. No correlations were found between the modelled total depositions and the concentrations of Cd, Hg and Pb in the mosses at p < 0.1. For Pb in 1995?r is 0.52 at p = 0.012, for the other surveys no correlations at p < 0.05 could be found. Discussion The increase of the Cr bioaccumulation from 2000 till 2005 is particularly pronounced in Mecklenburg-Western Pomerania. This trend is confirmed with regional differences in the national average as well as in other participating countries like in Switzerland. Deposition measurements did not register this trend. In contrast to the UNECE area, the federal territory and several federal states no correlations were found between the modelled total depositions and the metal concentrations in the mosses. Conclusions The fact that no correlations were found between the modelled total depositions and the element concentrations in the mosses may be caused by the low spatial resolution (50?×?50?km) of the EMEP data. The moss surveys contribute to the heavy metal and the multi-component-model of CLRTAP because they prove on different spatial scales how air pollution control influences the accumulation of emitted substances in environmental subjects of protection like vegetation. In contrast to deposition measurement networks the moss monitoring identified a trend reversal in Mecklenburg-Western Pomerania: The continuous decrease of the metal bioaccumulation in mosses from 1990 till 2000 has changed to an increase of several metals between 2000 and 2005. This increase is significant for Cr and Zn. Recommendations and perspectives The spatial resolution of the EMEP deposition data should be enhanced based on the Europe-wide regression relationship between the element concentrations in the deposition and in the mosses. For regional studies the existing but so far not useable deposition measurement data of the federal states should be made available. It should further be investigated what caused the increase of the Cr concentrations above the level of 1990 – perhaps emissions or biogenic effects as a consequence of simultaneously increased nitrogen loads? The Heavy Metals in Mosses Surveys are a positive example for environmental monitoring activities reaching across three spatial and administrative levels: regional (e.?g. federal state or natural landscape), nation wide (e.?g. Germany) and continental (e.?g. Europe). In Germany the harmonised and quality controlled moss data are made available via a WebGIS portal. Therefore the moss data may easily be accessed for environmental monitoring purposes and the control of environmental political actions. Hence, the continuous task of environmental monitoring can be met and carried on in the future. It should further be considered to expand the moss monitoring on the survey of persistent organic pollutants and apply it in human-biomonitoring. This would facilitate the acquisition of indoor and outdoor pollution with the same receptor.     

Konzentrationen von Schwermetallen in Bodenlösungen aus bayerischen Wäldern

Goal and Methods

During two years, soil solution samples were collected at 18 forest sites with low anthropogenic heavy metal loads in Bavaria using ceramic suction cups. The collected samples were analysed for pH, conductivity, dissolved organic compounds, and the trace elements Al, Cr, Fe, Mn, Ni, Cu, Zn, Cd, Ba, and Pb.

Results

In addition to initial interference effects caused by the installation of suctions cups, time series were characterised by seasonal variations. The results obtained for the replicated suction cups were comparable for every individual area with standard deviations of 20 to 25 percent. With increasing soil depth, the pH of the soil solution increases specifically at those sites (up to 2.5 pH units) where the topsoils have been acidified. On the other hand, concentrations of all trace elements investigated — excepted of Al and Mn — are not influenced by the soil depth. The forest stand has no significant additional effect on trace element concentrations. Contents of Al, Mn, and Zn are correlated with low pH-values in the soil solution, whereas the mobilisation of Ba is mainly caused by ion exchange. Complexes of trace elements and dissolved organic matter were only detected for Cu at one site. Element concentrations in the soil solution are not significantly influenced by the contents of aqua regia soluble portions in the soil matter. Only very high qua soluble portions increase the concentrations in the soil solution. The overall heavy metal concentrations determined in soil solutions are low compared with different limiting and threshold values, respectively.

Conclusions

Trace element concentrations in soil solutions are mainly influenced by the soil properties themselves. The contribution of the forest stand is negligible. Therefore, from the ecotoxicologic point of view, the risk of leaching heavy metals contaminating the groundwater is not significant for the investigated forest sites and without any respect to silviculture practices.     

Verteilung und Abnahme von bodennahem Ozon in städtischen und ländlichen Regionen

The compilation of ozone data for the federal states of Hesse and Northrhine-Westphalia (NRW) in Germany indicated that the concentration of ozone level slightly decreased during the years 1990–1998. The average concentration of ozone over forest areas is significantly higher than over cities. Only the maximum figures in the years approached one another. However, values passing the legal thresholds (180 μg ozone/m³) were two to three-fold higher over forests than over cities. The ozone concentration in air is inversely proportional to the traffic density. It is suggested that the lower NOx concentration over the forest than over cities is involved in the maintenance of the higher ozone-concentration over forest areas. In the cities, the ozone is reduced by NO to almost zero at night, whereas it is reduced by only about 50% over forests with lower NO concentrations. This reduction is only partially compensated in connection with the photolysis of NO₂ and the subsequent oxidation of O₂ to O₃ during the day. The ozone situation is principally the same in the federal states of Hesse and Northrhine-Westphalia.     

Verhalten von Nanosilber in Kläranlagen und dessen Einfluss auf die Nitrifikationsleistung in Belebtschlamm

Background, aim and scope The application of nanosilver is increasing. Knowledge on the fate and behavior of nanosilver in wastewater and wastewater treatment plants is scarce. Studies under real world conditions are completely lacking. We studied (1) the impact of nanosilver on the nitrification of sewage sludge, (2) quantified the mass flow of nanosilver in a pilot-plant, and (3) verified the mass balance in a full-scale municipal wastewater treatment plant where nanosilver is introduced to the municipal plant by an indirect discharger. Materials and Methods The addition of four different nanosilver additives on ammonia oxidation in activated sludge has been studied in batch-reactors at two concentrations (1, 100?mg/L Ag) with two exposure times (2?h, 6?days). The pilot-plant treating 70 population equivalents of domestic wastewater is operated with a 12?day sludge age. Nanosilver was applied to the activated sludge tank within two sludge ages. The silver concentrations were measured in sludge and effluent samples during dosing and the following two sludge ages. The adsorption and speciation of silver particles has been analyzed using scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX). Influent, effluent and sludge were sampled on a full-scale plant (60?000 equivalent inhabitants) and analyzed for silver. Results Silver nitrate, metallic nanosilver, nano-scaled silver chloride and microcomposite silver did not show any effect on ammonia oxidation after the addition of 1?mg/L Ag to the activated sludge (corresponding to 250?mg Ag per kg solids). In contrast, 100?mg/L Ag inhibited the nitrification process by 100?% after the addition of silver nitrate and 20–30?% after addition of colloidal polymer-coated nanosilver. A complete mass balance of the pilot-plant, a steady-state system with known fluxes, demonstrates significant enrichment of silver in the sewage sludge (96?%) after the addition of silver chloride to the plant and small losses of silver into the secondary effluent (4?%). The mass fluxes are similar to metallic colloidal nanosilver investigated under the same conditions. The mass balance has been consistently confirmed by the full-scale study in a municipal wastewater treatment plant. The silver fluxes correspond to the fluxes of the suspended solids in sludge and effluent. Overall, it is estimated that from public wastewater treatment plants about 4–40?mg/a Ag per inhabitant equivalent are discharged annually to the receiving water. The analysis by SEM-EDX demonstrates adsorption and incorporation of nanosilver on biological flocs. This method yields first insight into complex building and transformation of silver associated with sulfide after adding metallic nanosilver and silver chloride to wastewater. Discussion Silver ions released from nanosilver react immediately with large amounts of chloride present in wastewater to form silver chloride. Silver ions may react with organic ligands or sulfide groups additionally. Consequently, even silver nitrate added with 1?mg/L Ag (250?mg Ag/kg TS) to activated sludge did not inhibit nitrification activity. Very high amounts of nanosilver, i.?e. 100?mg/L Ag, overburdened the system and equilibrium condition between silver ion release and ligands was not reached. The mass balance reflects the excellent attachment of nanosilver to activated sludge and biological flocs. Therefore, the main elimination process of nanosilver is attachment to the activated sludge. The elimination of nanosilver is high compared to organic and inorganic micro pollutants omnipresent in wastewater. Any further reduction of suspended solids in the effluent water will reduce the silver load. Conclusions Generally, in wastewater nanosilver occurs bonded to activated sludge flocs and therefore the elimination of nanosilver is efficient under operation conditions typical for wastewater treatment plants. The major fraction of nanosilver is removed from the system by the excess sludge withdrawal. Nonetheless, the efficiency may be further improved by a tertiary filtration step. All analyses of influent, effluent and sludge confirmed that silver exists as silver sulfide. Due to a negligible water solubility of this silver species, silver ions are not subsequently released. Recommendations and perspectives Nanosilver research should be driven to the identification of transformation processes in real environmental matrices and the influence of coatings on the adsorption behavior. There is no need for action to take special measures for nanosilver removal in the area of municipal wastewater treatment plants compared to ubiquitous hazardous organic pollutants may present in wastewater. Nevertheless, source control measures following the precautionary principle should be performed.     

Bestimmung von Phthalsäureestern in Lebensmitteln, Frauenmilch, Hausstaub und Textilien

25 food samples, 5 mother’s milk specimens, 4 dust samples, and 16 textiles were analysed for phthalic acid esters. Phthalic acid esters were detected in all samples, with di (2-ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DBP) being the most abundant phthalates. Raw milk samples revealed average concentrations of total phthalate of 0.1 mg/kg. Retail milk did not contain higher loads than raw milk, even storing samples until their “best-before” date did not result in elevated levels. Skimmed milk was less contaminated than whole milk. The higher concentrations of DEHP and total phthalates in cream samples are due to their higher fat content. With concentrations up to 1.54 mg/kg, ground hazelnuts, almonds, and nutmeg in plastic packagings showed relatively high levels. In infant food, only traces of DEHP and DBP could be found while other phthalic acid esters were not detectable. The mother’s milk samples also exhibited only low amounts of approx. 0.1 mg/kg, thus indicating that there is no accumulation of phthalate esters in the human body. Extraordinarily high concentrations were found in dust samples; with the levels ranging from 300 to 5370 mg/kg and DEHP being the major compound. This leads to the conclusion that the air path must play a considerable role in the transfer of phthalic acid esters. As dust contains considerable amounts of textile fibres, textiles were also included in the investigation. The phthalic ester levels in the textile samples ranged from 3.42 to 34.44 mg/kg. Therefore, the high phthalate contaminations of dust cannot be explained by textile fibres.     

Berücksichtigung von Variabilität und Unsicherheit in quantitativen Risikoabschätzungen (QRA)

Using the example of residential living on a contaminated site, a probabilistic exposure assessment is performed with variability and uncertainty being modelled separately. Probability distributions are used in the exposure model in order to characterize person-related variables (e.g. body weight) only; chemical-specific parameters are being held constant. In addition, uncertainty concerning one selected variable (soil ingestion rate) was modelled. Comparing these results to conventional “worst case” estimates, we find those estimates located in the uppermost range of the probabilistic estimates. The worst case estimates tend to be highly conservative and possibly unrealistic.     

Toxizitätsänderungen in Photoreaktionen von Azaarenen

The azaarenes and the structurally analogous PAH accompany each other and occur ubiquitously in nature. Photochemical conversions like direct photolysis or the photoreaction with nitrate are important natural degradation reactions of azaarenes. Furthermore, photoreactions with chlorine and bromine radicals can be expected in nature. The reactions generate a large number of oxidized, nitrated and halogenated products with unknown toxicity. In this paper, a first screening of changes is reported in acute toxicity during the course of the photochemical reactions. As test system luminescent bacteria are used. For quinoline, isoquinoline and phthalazine the investigations show different changes of the toxicity of the reaction mixtures in dependence on the respective reaction type. The toxicity of the reaction mixtures of quinazoline and quinoxaline increases in all reactions investigated. Furthermore the reactions of bromine radicals with azaarenes also show an increase of the toxicity in all cases. Compared with the azaarenes in all reactions products with significantly higher toxicity are formed.     

Bioassay zur Bestimmung von TCDD-Toxizitätsäquivalenten (TEQ) von Umweltproben und Reststoffen

Polychlorinated aromatic hydrocarbons (HAH) like 2,3,7,8-tetrachloro-p-dioxin (TCDD) elicit a multitude of toxic and biological effects. A common trait of these substances is their affinity for a cytosolic receptor protein and the subsequent induction of the synthesis of several gene products, including cytochrome P450 1A1 (CYP 1A1). In this publication we present a bioassay to determine the induction of CYP 1A1 as a sum parameter for the total toxic potential of critical halogenated compounds in complex environmental matrices. In order to eliminate compounds like polycyclic aromatic hydrocarbons (PAH) and naturally occurring substances which might interfere with the bioassay we developed a simple cleanup procedure. TEQ values derived from bioassay are in good agreement with those obtained from chemical analysis. This bioassay in combination with the simplified “single column” clean up represents a cost and time effective alternative to chemical analysis for the screening of large numbers of environmental matrices.     

Die Rolle der Globalisierung und Klimaveränderung auf die Entwicklung von Stechmücken und von ihnen übertragenen Krankheiten in Zentral-Europa

Mosquitoes and mosquito-borne diseases know no borders, and their spread is a consequence of globalization related to high mobility of humans and international trade as well as on climate change. Higher temperatures and precipitation favour the development of mosquitoes as well as the pathogens and parasites which are transmitted by mosquitoes. An increase of about 2?°C would shorten the time for the development of larvae and pupae of Anopheles messeae (vector of malaria) by almost three days resulting in an increase of gonotrophic cycles and number of generations. The higher numbers of breeding sites for Anopheles species such as An. plumbeus in cess pools due to the change of agricultural practises increase the contact with potential vectors of malaria as well. However, at least in Germany, malaria will not play an important role anymore. The invasion of new species such as Stegomyia albopicta (formerly Aedes albopictus) is enhanced by human migration and international trade. St. albopicta was first discovered in Germany in 2007. Nowadays, this species, originally from Southeast Asia, occurs in 13 European states. Thus, the risk for outbreaks of arboviroses is increased.     

Abschätzung des umweltchemischen und ökotoxikologischen Verhaltens von Stoffen durch computergestützte Analyse von Struktur und Verhalten sowie von Struktur und Wirkung

Risk assessment of chemicals requires comprehensive data material, which often is not available. To provide substitutes for the lacking experimental ecotoxicological and physico-chemical data, a software-system (SAR-System) has been developed comprising more than 90 estimation models for relevant endpoints. The approach is based on quantitative structure-activity relationships (QSAR). Two major aspects characterize the SAR-System:

1. The implemented models were tested for their validity and application range.
2. The QSARs are accessible by a menu-driven programme package.

The following endpoints are included: Thysico-Chemical Data: 1-Octanol/water-partition-coefficient log P_ow, vapour pressure, water solubility, pK_a-value, boiling point Biological Data: Toxicity towards fish, daphnia, tetrahymenae, algae, bacteria and mammals, mutagenicity. Distribution: soil sorption, bioconcentration, Henry-Constant, Mackay (Level I). Degradation: photodegradation, biodegradability.     

Stabilitätsverhalten von ausgewählten anorganischen Spurenstoffen in Niederschlagsproben

The stability of H⁺, NH ₄ ⁺ , and PO ₄ ^3? ions in rainwater samples was in vestigated under different conditions cf storage and transport. Microbiological and physicochemical processes account for changes. Suppression of microbiological activities in deposition networks using conventional analyses may be achieved by adding AgCl-powder and by cooling to +4 °C.     

Bestimmung von leicht freisetzbarem Cyanid in Böden und Wässern mit der Mikrodestillation

Easy-liberatable cyanide has to be analysed if soils and waters are contaminated by cyanide. The aim of this study was to determine easy-liberatable cyanide in these environmental samples using a micro-distillation apparatus by means of a modified digestion vessel. Pure aqueous solutions of different cyanide species, five contaminated and uncontaminated soil samples and two water samples were analysed by micro-distillation according to the German standards. Recovery was determined by analysis of spiked samples. When using the modified digestion vessels, the pH of 4 which is demanded by the standard method can be adjusted. The recovery of potassium cyanide and weakly-complexed zinc-cyanide ranged from 93–101% for standards, and from 87–98% for spiked samples. In contrast, the recovery of strong iron-cyanide complexes was below 4% both for pure solutions and spiked samples. The precision of the method expressed as a relative standard deviation was 25% in cases of very low easy-liberatable cyanide contents (< 1 mg CN kg^?1) and below 12% in case of high easy-liberatable cyanide contents (> 1 mg CN kg^?1) for contaminated soils. The determination of easily-liberatable cyanide in soils and waters using micro-distillation combined with the modified digestion sample is an alternative to other distillation methods.     

Existierende dioxininventare weltweit und neue methodik zur erstellung von vergleichbaren und vollständigen emissionsinventaren

Presently, there are less than 20 inventories to estimate releases of dioxins and furans. According to a recent survey, 12,900 g TEQ of these unwanted byproducts are emitted into the atmosphere by 16 countries. Highest emissions are from the densely populated industrialized countries of the Northern hemisphere — Japan and the United States of America. Whereas the metal producing and recycling industry is the sector with the highest dioxin emissions in Europe, waste incineration is considered to be the major source in many other countries. Measures to reduce dioxin emissions have resulted in strong downward trends, as shown e.g. in Germany and Japan; however, potentials for further reduction have been identified. So far, countries have utilized own methods to calculate their dioxin emissions and the majority has addressed releases to air only. The future Stockholm Convention on POPs will require to continuously reduce dioxin emissions. In order to assist countries in inventory making, UNEP has produced the Toolkit, a methodology to establish comparable dioxin inventories that address releases to air, water and land, with products and in residues.     

Untersuchungen zum ökotoxikologischen Schädigungspotenzial und Erosionsrisiko von kontaminierten Sedimenten in staugeregelten Flüssen

Particle-bound pollutants accumulate in river-bottom sediments, a process which results in a significant decrease in the ecotoxicological availability of toxicants for the majority of aquatic organisms. Under normal hydrologic conditions, the release of contaminants from bottom sediments is usually of minor importance. In contrast, flood events may remobilize highly contaminated sediments via in-stream erosion. The objective of this study was to develop a combined ecotoxicological and hydraulic approach to elucidate the ecotoxicological implications associated with the risk of erosion of contaminated sediments. This integrated strategy was applied to the lock-regulated Neckar river in Southern Germany. Both the bottom-sediment cores and suspended matter from two intensive flood events were investigated. Sediment samples below an erosional unconformity showed a sharp increase in the ecotoxicological load. Moreover, it was found that major flood events (HQ₅ and higher) could possibly erode even very old, well-consolidated and highlycontaminated sediments. The suspended matter of the high discharge events investigated (return periods of 15 to 20 years) exerted significantly higher cytotoxicity and mutagenicity than a moderate flood with a 1-year return period. These findings support the conclusion that the observed ecotoxicological effects during major floods may at least in part be due to the in-stream erosion of highly contaminated bottom sediments.     

Raumbezug und Repräsentativität in der Ökologischen Flächenstichprobe

The quality of regionalizations can only be evaluated with regard to its specific purposes. In environmental monitoring, regionalizations, besides being an analysis tool, has a great importance on the selection of monitoring sites. The article describes the relationship between regionalization, selection procedure and representativeness using the example of Ecological Area Sampling (EAS) and presents the regionalization which was tested in an EAS pilot study.     

Identifizierung toxischer Verbindungen in Sedimenten: Ansätze zur Integration von Wirkung und Bioverfügbarkeit

Sediments play an important role for aquatic ecosystem functions. However, they also act as sink, storage and source of lipophilic toxicants and metals. Effect-directed analysis (EDA) is a powerful tool to identify compounds causing adverse effects. In order to avoid misinterpretations and biased prioritization bioavailability needs to be considered together with effects. Bioavailability is a complex process finally resulting in the transfer of a so far particle bound molecule to the target location within the organism where it causes an effect. In order to operationalize this concept for EDA it can be divided into several partial processes. These include desorption from sediments and thus bioaccessibility, equilibrium partitioning of desorbable compounds between sediment, water and organisms driven by activity, and toxicological bioavailability as a result of toxicokinetics including resorption, transport, metabolization and excretion. Bioaccessibility is based on desorption kinetics and can be simulated with mild extraction methods e.?g. using TENAX. Equilibrium partitioning can be simulated with partition-based dosing techniques. First results with these approaches indicate that consideration of bioavailability increases the significance of polar sediment-associated toxicants relative to classical non-polar contaminants such as polycyclic aromatic hydrocarbons.     

Auftreten von PCDD/PCDF in Brandfällen

Over the last years, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDF) have been identified in the soot of various accidental fires at concentrations which have made an extensive reconstruction of the buildings necessary. In these cases, dioxin precursors like polychlorinated biphenyls (PCB) or large amounts of other halogenated organic compounds like PCV cable coatings were involved. Dependent on the circumstances of the fire and the materials burnt, the levels of contamination and the congener pattern of the PCDD/PCDF in the soot were different. The analytical results from various accidental fires were evaluated and compared with laboratory data. A hierarchical cluster analysis supports the interpretation of the data and shows that the contamination of the soot from the fire in the Düsseldorf Airport in April 1996 was a mixed contamination primarily caused by PCB and PVC.