Persistente organische Schadstoffe in Böden, Gewässern und in Firn der Region nördliches Piringebirge (Bulgarien)

Systematic environmental screenings are still the exception in South-Eastern Europe. Especially, there is a decisive lack of information concerning the occurrence and behaviour of xenobiotic and toxic compounds like volatile-and non volatile halogenated organics, suppressed by the surrogate AOX, synthetic chelating agents, pesticides, like DDT as well as chlorate in the biosphere. The analysis of soils, waters and firns of a representative area in Bulgaria, the Pirin mountains, indicate a relatively low back ground pollution. The accumulation of the xenobiotics in this high mountain region is recognised to be low. Nevertheless, traces of pesticides and chelating agents like EDTA and NTA in ice (firns) and soils were found. The surrogate AOX should be a parameter, suitable for routine environmental screenings of such areas.     

饮用水水源中半挥发性有机污染物监测方法的探讨

江苏省饮用水水源地水质中富含有机物质,这类化合物种类多、浓度高,在色谱分析中,容易与痕量半挥发性有机毒物形成共流物,干扰分析。根据四极杆质谱检测器和离子阱质谱检测器的工作原理,建立了54种半挥发性有机物的选择性离子监测和2级质谱法监测方法,确定了选择性离子监测方法所选的离子范围,2级质谱法监测所选的母离子、CID电压,对比了选择性离子监测和2级质谱法监测的检测限。在此基础上初步建立了将两种质谱监测相结合的方法,该方法在实际样品分析中简便准确,可有效减少前处理工作。     

DDT und Metaboliten in Sedimenten Berliner Gewässer

Sediment samples from rivers and lakes of Berlin (Germany) were analysed for their contamination with organic compounds by means of qualitative and quantitative GC/MS analysis. The principal compounds detected were PAH, organotin derivates, several classes of chlorinated, brominated and mixed halogenated compounds and some of their related metabolites. The DDT metabolites DDD, DDE, DDCN, DDMU and DDMS were the most abundant compounds of halogenated pesticides in a wide range of samples. The main metabolite determined was p,p′-DDD, with concentrations up to 1230 μg/kg dw. The parent DDT compound was detected in only a few samples. The acute cytotoxicity of selected DDT-metabolites was determined with the permanent cell line RTG-2 from the gonads of the rainbow trout (Oncorhynchus mykiss). The results indicate a high cytotoxic potential of these metabolites. The oestrogenic potential was determined by the Dot-Blot/RNase-Protection-Assay an the order from o,p′-DDT>p,p′-DDMS>p,p′-DDMU≥p,p′-DDCN. Risk assessments based on chemical analysis of DDT, DDD and DDE alone is not able to estimate the real toxic potential of DDT and its metabolites. The development of a method for bioassay directed assessment seems to be an effective strategy to solve this problem. Especially scarce or not available data of combinatory effects, differences between different trophic levels and their availability to biota and low knowledge about the metabolism in situ as well as the enantioselective characteristics of most chiral DDT metabolites warrant future analyses.     

Rapid incorporation and short-term distribution of a nonylphenol isomer and the herbicide MCPA in soil-derived organo-clay complexes

Organo-clay complexes in soil are a major sink for xenobiotics and, thus, often enhance their persistence dramatically. However, the knowledge on environmental processes of non-extractable residue formation on a short time scale is very restricted. Therefore, this study examined the distribution of 4-(3,5-dimethylhept-3-yl)phenol (NP) and 4-chloro-2-methylphenoxyacetic acid (MCPA) in soil over a short time period of 48 h and in different soil sub-fractions. The overall proportion of organo-clay-associated bound residues was not only abundant but also in the same range for both substances (MCPA: 8%; NP: 11% of applied ¹⁴C-radioactivity). However, a more detailed view revealed two different distribution patterns: a higher proportion of clay-associated NP was accompanied by a lower content of bound residues, whereas a smaller fraction of clay-associated MCPA was characterized by a higher proportion of non-extractable residues. Further on, a selective accumulation of bound residues among clay-associated humic fractions was observed. NP residues were linked predominantly to humic acids, whereas MCPA residues tended to be incorporated more into fulvic acids. It was evident that the overall distribution was influenced primarily by the physico-chemical properties of the contaminants. This study demonstrates in detail a rapid initial incorporation accompanied by a specific distribution into soil sub-fractions for selected xenobiotics in soil and points to a complex interaction of clay-associated organic matter with low molecular weight compounds.     

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.     

可离子化有机污染物对大型溞的毒性及QSAR研究

取代苯酚、苯胺和苯甲酸类化合物是在环境水体中具有较强生物毒性的芳香族可离子化有机化合物,它们在水体中对水生生物和水生生态系统都有较大危害。测定此类化合物在p H值为6、7.8和9的条件下对大型溞的24 h急性毒性,计算化合物在不同p H值条件下的中性态分子所占比例F0。研究毒性与F0的相关性,结果表明F0对取代苯酚和苯甲酸类化合物的毒性的影响较大而对取代苯胺毒性的影响很小。对于卤代苯甲酸类化合物,毒性与疏水性的相关性较好,但是羟基苯甲酸类化合物的毒性与疏水性参数的相关性很差,引入量子化学参数EHOMO和取代羟基个数NOH,可以改进苯甲酸类化合物的模型的质量。     

Retrospektives Monitoring von Organozinnverbindungen in biologischen Proben aus Nord- und Ostsee – sind die Anwendungsbeschränkungen erfolgreich?

Background, aim, and scope Organotin compounds are used as biocides, plastic additives and catalysts. With respect to environmental effects, tributyltin (TBT) and triphenyltin (TPT) compounds are the most relevant, because of their high aquatic toxicity and endocrine effects on mussels and snails. TBT was mainly used as antifouling agents in coatings of ships and boats. In 1989, Germany banned the application to ships <?25?m length. Finally, in 2003, the use of organotin-based antifoulants within the European Union was completely banned. To verify the effectiveness of the restrictions a retrospective monitoring study was initiated. Material and methods A set of appropriate archived samples was retrieved from the German environmental specimen bank (ESB) comprising standardized pooled samples of eelpout (Zoarces viviparus) muscle tissue and of soft bodies of common mussels (Mytilus edulis) sampled at two locations in the North Sea and one in the Baltic Sea. Analysis of organotin compounds included n-hexane extraction, derivatisation with sodium tetraethyl borate, capillary gas-chromatographic separation and atomic emission detection. Results and Discussion Altogether, time series cover the period 1985 to 2006, including data of an earlier study (Rüdel et al. 2003). Until the late 1990s, TBT remained more or less constant in all samples (e.?g. 17?±?3?ng/g wet weight, ww, in mussels from Jadebay/North Sea). The German ban of TBT-based antifoulings for small ships had no effects on environmental concentrations because large ships dominate in the investigated North Sea regions. After the EU-wide ban of TBT in 2003, however, significant decreases in mussel and fish contamination could be observed. In mussels from Jadebay, TBT concentrations were 14 and 6?ng/g ww in 2004 and 2005, respectively. TBT contamination in eelpout of the same region decreased to about 30 percent of the initial concentrations in 2006. Corresponding decreases were detected for TPT. Declining trends were also found in fish and mussels sampled from a Baltic Sea offshore site. Conclusions The results demonstrate the effectiveness of the legal measures undertaken to control organotin inputs into the aquatic environment. Nevertheless, organotin compounds are still relevant pollutants. Water concentrations calculated from the measured tissue concentrations by using the respective bioconcentration factors are still above the Environmental Quality Standards derived in the context of the Water Framework Directive (0.2?ng/l) and the OSPAR mussel EAC (Environmental Assessment Criteria; 2.4?ng/g ww). Thus adverse effects to marine organisms cannot be excluded. Recommendations and perspectives Further studies should be performed to verify the declining trends. More sensitive analytical methods, e.?g. species-specific isotope dilution analysis, are recommended in order to detect lower environmental concentrations.     

Abschätzung der Einträge von polyzyklischen aromatischen Kohlenwasserstoffen in deutsche Gewässer

Background, aim, and scope Polycyclic aromatic hydrocarbons (PAH) result from incomplete combustion of almost every organic materials, e.?g. due to forest fires, residential heating, combustion engines, grilling, or smoking. PAH are predominantly distributed over the air-path. Their usage in products (e.?g. moth-balls) has been limited strictly or completely forbidden in the past. In the context of the EU Water Framework Directive (WFD), the single substances anthracene, fluoranthene and naphthalene, as well as PAHs as group of substances, are listed as “priority” substances. Background of this work is a first compilation of sources of PAH emissions, and in this context, the collection of all relevant data and information to calculate the total emissions into surface waters in Germany. Materials and methods Within the scope of diverse research projects, funded by the German Environmental Agency, the available data material concerning PAH input in surface waters has been analyzed by the Fraunhofer Institute for Systems and Innovation Research. On the basis of the collected data, a first evaluation of relevance of the different sources has been conducted using the model MONERIS. Results As a result of the atmospheric deposition, PAHs enter, to a large extent, surface waters directly or indirectly through surface runoff (e.?g. urban areas, wastewater treatment plants, erosion). Discussion Although there is still additional research need for some of the covered PAH sources, a noticeable distribution pattern of relevance emerges. Conclusions The scenarios, based on the currently known sources, show that the implementation or the neglect of emission reduction measures in the field of diffuse air-borne PAHs are crucial for the further development of the deposition of PAHs in surface waters. More far-reaching studies are necessary, e.?g. concerning emissions from inland navigation/motor boats, the inhomogeneous source “products”, or the path “erosion”. Recommendations and perspectives According to the EU-WFD, all depositions, emissions and losses of “priority hazardous” classified substances, such as the group of PAHs, have to be stopped or gradually finished in the long term. Until the year 2015, environmental quality standards (EQS) have to be met for all “priority substances”. Presently, the EQS often are not completely fulfilled for many substances of the PAH group, including benzo(a)pyrene. Reduction measures are necessary within diverse areas, especially concerning diffuse atmospheric emissions (e.?g. “residential heating”).     

Veränderung von Biokonzentration und Wirkung vom PSM in Anwesenheit von Huminstoffen

Humic substances, in aqueous bodies primarily fulvic acids, may demonstrate an inhibitory as well as an activating influence on organisms. We present evidence with bacteria-containing algal cultures and with cultures of the nematodeCaenorhabditis elegans. Structural elements of the fulvic acids which may be responsible for such effects are not yet known. Furthermore, the presence of fulvic acids may lead to increases in bioconcentration of xenobiotics. Increase in the toxicity of xenobiotics in the presence of humic substances have also been described. We present studies applying lethal as well as sublethal toxicity endpoints.     

Bioakkumulation von Metallen und Stickstoff zwischen 1990 und 2005 in Niedersachsen

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 Lower Saxony, 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 and nitrogen 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 Lower Saxony 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 and nitrogen bioaccumulation, site specific characteristics as well as information on land use and emissions was analysed by bivariate nonparametric correlation analysis, contingency tables and Classification and Regression Trees (CART). Results The results of the quality controlled chemical analyses shows a significant decrease of the metal bioaccumulation in Germany from 1990 to 2000 for all elements but Zn. From 2000 to 2005 a further significant decrease can be stated for Cd, Hg and Pb, to most parts non significant increases can be observed for Cr, Cu, Fe, Sb and Zn. Cr thereby exhibits the highest accumulation in 2005 when compared to the results of 1990, 1995 and 2000. The MMI illustrates the temporal trend of the metal bioaccumulation as a whole: From 1990 to 2000 a continuous significant decrease can be observed. From 2000 to 2005 the median of the MMI increases, again significantly, from 3.4 to 4. The N concentration in mosses in Lower Saxony reaches from 1.1 to 1.9?% in dry mass. High N concentrations were detected in agriculturally intensively used areas. Highly significant bivariate correlations between the metal bioaccumulation and land use in the surroundings of the sampling sites were found reaching from 0.3 to 0.5. Other location criteria with similar correlation coefficients/Cramér’s V are moss species, altitude, distance to the North and Baltic Sea and the distance of the sampling site to the nearest tree crown. N only shows negative correlations to urban land use and the distance to the nearest tree. Exemplified for Sb multivariate correlations were furthermore detected by CART. It could be shown that the Sb bioaccumulation interacts with the moss species and the ratio of agriculture, forests and urban areas around the sampling site. Discussion The decrease of the continuously decrease of heavy metals reflects the improving air quality in the past 15 years. Compared to other environmental monitoring and modelling programmes the moss surveys registered increasing concentrations of toxic metal elements between 1990 and 2005, e.?g. Cr. High Cr loads in mosses were also registered in other European countries like in Switzerland. Further investigations are therefore necessary to investigate whether this is due to different emission conditions or biogenic effects (e.?g. as a result of increasing nitrogen depositions). Contrary to deposition measurements that exhibit a higher temporal resolution the moss surveys provide measurement data on a wide range of elements. Some of these elements are important with regard to human-toxicological aspects (e.?g. As, Al, Hg, Sb, V). Due to its ecotoxicological relevance nitrogen was monitored in the European moss survey 2005 for the first time. Compared to the metals regionally high emissions of nitrogen compounds into the atmosphere can be detected in Lower Saxony. The standardised biomonitoring of atmospheric pollution with mosses is an important link between the technical acquisition of depositions and the accumulation in biological material. To claim that the element concentrations in mosses should correlate to a high degree with measured or modelled depositions is not appropriate since these approaches are considering different biological or physical receptors. Nevertheless, the accumulation of air pollutants in terricolous mosses reflects the degree of air pollution which is permanently deposited and affects the system of plants and soils. The degree of correlation thereby depends on the boundary conditions of the physical processes, like regional and site-specific meteorological conditions within the accumulation period, the vertical and horizontal vegetation structure or land use conditions. Conclusions 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 incl. arable crops. If environmental monitoring is seen as a continuous task and the applied methodology works well as an early warning system then environmental policy is enabled to act in preventative sense and to pursue unexpected developments. No other environmental monitoring programme provides such a wide range of ecotoxicologically relevant elements measured as spatially dense as the case for the moss surveys. The spatial distribution of environmental information is an essential criterion for their usability in terms of political measures for the federal states and the federation. Recommendations and perspectives 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.     

Whole pictures of halogenated disinfection byproducts in tap water from China’s cities

When bromide/iodide is present in source water, hypobromous acid/hypoiodous acid will be formed with addition of chlorine, chloramine, or other disinfectants. Hypobromous acid/hypoiodous acid undergoes reactions with natural organic matter in source water to form numerous brominated/iodinated disinfection byproducts (DBPs). In this study, tap water samples were collected from eight cities in China. With the aid of electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 35, m/z 81, and m/z 126.9, whole pictures of polar chlorinated, brominated, and iodinated DBPs in the tap water samples were revealed for the first time. Numerous polar halogenated DBPs were detected, including haloacetic acids, newly identified halogenated phenols, and many new/unknown halogenated compounds. Total organic chlorine, total organic bromine, and total organic iodine were also measured to indicate the total levels of all chlorinated, brominated, and iodinated DBPs in the tap water samples. The total organic chlorine concentrations ranged from 26.8 to 194.0 μg·L^–1 as Cl, with an average of 109.2 μg·L^–1 as Cl; the total organic bromine concentrations ranged from below detection limit to 113.3 μg·L^–1 as Br, with an average of 34.7 μg·L^–1 as Br; the total organic iodine concentrations ranged from below detection limit to 16.4 μg·L^–1 as I, with an average of 9.1 μg·L^–1 as I; the total organic halogen concentrations ranged from 31.3 to 220.4 μg·L^–1 as Cl, with an average of 127.2 μg·L^–1 as Cl.     

Behavioral and electroantennographic responsiveness of adult butterflies of six nymphalid species to food-derived volatiles

While adults of most species of butterflies visit flowers for food (nectar), those of certain species can feed on rotting food (e.g., exuded tree sap and rotting fruits). These food sources considerably differ in odor; flowers emit species-specific scents and rotting-food odors are characterized by fermentation products. To determine whether adult butterflies have different olfactory performances adaptive to their food selections, we examined the following responses of naïve adults of six nymphalid species, namely, Nymphalis xanthomelas, Kaniska canace, Vanessa indica, Cynthia cardui, Hypolimnas bolina, and Argyreus hyperbius: the proboscis extension reflex (PER) was evaluated as the behavioral criterion of preference for scent compounds, and the electroantennographic (EAG) response was assessed as the sensory criterion of antennal perception. All of these species are nectarivorous, but N. xanthomelas, K. canace, and V. indica also forage rotting food. The PERs to 52 tested compounds were in good agreement with the food habits of these butterflies. The six species showed high PERs to several aromatic compounds widely found in flower scents. Fermentation products such as ethanol and acetic acid elicited intermediate to high responses from the three species feeding on rotting foods. The other three species showed low PERs to these compounds, and acetic acid strongly inhibited the PER-eliciting activities of the other compounds. These results demonstrate that the olfactory preference for fermentation products is a characteristic of the rotting-food feeders. The spectrum of EAG responses to 37 tested compounds was relatively similar among the six species. Particular acyclic aliphatic compounds, including green leaf volatiles, elicited high EAG responses from all the species. Despite a high PER-eliciting activity, most aromatic compounds induced intermediate EAG responses; however, ethanol and acetic acid evoked very weak responses. The results suggest that in food selection, adult butterflies use a specific olfactory system to perceive these major food-derived volatiles.     

n-Octyl esters of long-chain fatty acids are not anthropogenic pollution markers

n-Octyl esters of higher fatty acids have been reported as markers of urban wastewater in sediments, polychaeta, fish, crabs and oysters (Chaler et al. in J Chromatogr A 1046:203–210, 2004)). However, up to date, there were no subsequent studies to confirm this claim. Likewise, Chaler and co-workers did not consider that the mentioned compounds might occur naturally in the environment. Here we found seven n-octyl straight-chain alkanoates, from C-20 to C-26, in the wild-growing plant Heracleum sphondylium L., Apiaceae, from 14 locations. Those plant metabolites were unambiguously identified by gas chromatographic co-injection of the synthesized esters with the inflorescence washings. All identified octyl esters represent new natural compounds, except for octyl docosanoate. Since we have demonstrated that n-octyl esters occur naturally, and in abundance, they cannot be recognized any longer as wastewater markers. Additionally, here we provide evidences that the compounds identified by Chaler et al. (2004) are in fact 2-ethylhexyl esters, mistakenly identified as n-octyl esters.     

Halogenated metabolites in two marine polychaetes and their planktotrophic and lecithotrophic larvae

This study investigated the occurrence and ontogenetic changes of halogenated secondary metabolites in planktotrophic and lecithotrophic larvae and adults of two common, infaunal polychaetes, Streblospio benedicti (Spionidae) and Capitella sp. I (Capitellidae), with different life-history traits. S. benedicti contains at least 11 chlorinated and brominated hydrocarbons (alkyl halides) while Capitella sp. I contains 3 brominated aromatic compounds. These halogenated metabolites are potential defense compounds benefiting both larvae and adults. We hypothesized that: (1) planktotrophic larvae contain halogenated metabolites because they are not protected by adult defenses, (2) quantitative and qualitative variation of planktotrophic larval halogenated metabolites parallels that of adults, and (3) brooded lecithotrophic larvae initiate the production of halogenated metabolites only after metamorphosis. To address these hypotheses, volatile halogenated compounds from polychaete extracts were separated using capillary gas chromatography and identified and quantified using mass spectrometry with selected ion monitoring. All four life stages (pre- and post-release larvae, new recruits, adults) of both S. benedicti and Capitella sp. I contained the halogenated metabolites previously identified from adults. This is the first report of halocompounds identified and quantified in polychaete larvae. Allocation of potential defense compounds to offspring varied as a function of species, feeding type and developmental stage. Pre-release larvae of S. benedicti with planktotrophic development contained the lowest concentration of total halogenated metabolites (1.75 ± 0.65 ng mm⁻³), post-release and new recruits contained intermediate concentrations (8.29 ± 1.72 and 4.73 ± 2.63 ng mm⁻³, respectively), and planktotrophic adults contained significantly greater amounts (28.9 ± 9.7 ng mm⁻³). This pattern of increasing concentrations with increasing stage of development suggests synthesis of metabolites during development. Lecithotrophic S. benedicti post-release larvae contained the greatest concentrations of halometabolites (71.1 ± 10.6 ng mm⁻³) of all S. benedicti life stages and developmental types examined, while the amount was significantly lower in new recruits (34.0 ± 15.4 ng mm⁻³). This pattern is consistent with a previously proposed hypothesis suggesting a strategy of reducing potential autotoxicity during developmental transitions. Pre-release lecithotrophic larvae of Capitella sp. I contained the highest concentration of total halogenated metabolites (1150 ± 681 ng mm⁻³), whereas the adults contained significantly lower total amounts (126 ± 68 ng mm⁻³). All concentrations of these haloaromatics are above those known to deter predation in previously conducted laboratory and field trials. As a means of conferring higher larval survivorship, lecithotrophic females of both species examined may be expending more energy on chemical defenses than their planktotrophic counterparts by supplying their lecithotrophic embryos with more of these compounds, their precursors, or with energy for their synthesis. This strategy appears common among marine lecithotrophic larval forms. Received: 14 July 1999 / Accepted: 20 January 2000     

Huminstoffe in Sedimentporenwässern ausgewählter Bundeswasserstraßen

Humic substances are an important component of organic carbon in natural waters. Their character and properties are determined by the sources and the processes of their origin. Humic substances are not exclusively refractory compounds, but they are involved in several transformation processes in the water. It is not possible to directly analyze humic substances, therefore several methods were applied for their characterization. The presented LC-OCD-technique is a size-exclusion-chromatography with online UV- and carbon detection. Carbon fractions, e.?g. humic substances were differentiated by their molecular size. The portion of humic substances in sediment porewaters of the rivers Elbe, Rhine, Danube, Oder, Müritz-Elde-Waterway was determined. With only a few exceptions it ranges from 50 to 67?% of the dissolved organic carbon. The high molecular weight fraction accounts for 10 to 34?%, and the fraction of the low molecular weight substances was from 7 to 37?%. The ratio between the spectral absorption coefficient (254?nm) and the organic carbon is called SUVA (L/mg × m) and is an inidicator of the proportion of unsaturated bonds in the humic substances. Both high molecular herbal components (e.?g. cellulose, lignin) and biological degradiation products (e.?g. amino acids, sugar) are involved in sediment porewater transformation and degradiation processes. This demonstrates the distribution of the dissolved organic carbon between the fractions.     

离子色谱在砷化物形态分析中的应用

砷的分析方法最初有光度法、原子吸收光谱法和极谱法等，但这些方法仅能用于总砷，不能用于砷的形态分析．因而又发展了电感耦合等离子体质谱法(ICP-MS)、离子色谱法(IC)、气相色谱法、气相色谱-原子吸收光谱联用、液相色谱-质谱联用、离子色谱-电感耦合等离子体质谱、离子色谱-原子吸收／发射光谱联用技术等．由于砷化物在水中多以离子形式存在，采用离子色谱法能同时分析不同形态的砷离子．同时，采用电感耦合等离子体质谱及原子吸收光谱测定砷化物具有较高的灵敏度，因此，离子色谱及离子色谱与电感耦合等离子体质谱、原子吸收／发射光谱的联用技术在砷化物的形态分析中得到了较多的应用^[1-8]。     

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.     

Stoffflussanalyse von quartären Ammoniumverbindungen für die Schweiz

Background, aim, and scope Compared to other micropollutants such as pesticides or pharmaceuticals, less attention has been paid to biocides so far. A prioritisation of the biocides currently used in Switzerland in terms of pollution of waters revealed that quaternary ammonium compounds (QAC), the isothiazolinones chloromethylisothiazolinone and benzisothiazolinone as well as Irgarol exhibit the highest risk potential. The QAC benzalkoniumchloride (BAC) and didecyldimethylammoniumchloride (DDAC-C10) are used in considerable amounts and have a high biological activity. Materials and methods The emissions of selected QAC in waters and soil and the predicted environmental concentrations (PECs) were estimated by means of a substance flow analysis (SFA). The study was based on data from the Swiss products register, on literature, contacts to producers and users as well as on own assumptions. Results and discussion The consumption of BAC (four homologues) and DDAC-C10 in biocidal applications in Switzerland amounts to 90 and 30 tons annually. The most important applications are disinfectants for public health areas, food and feed areas as well as wood preservatives. The total emissions to the environment of all five substances account for approximately 11?t/a. The PECs in surface waters and sediments vary from values slightly lower than the predicted no-effect concentration (PNEC) to roughly three orders of magnitude below the PNEC. However, concentrations above the PNEC are possible at certain locations, particularly downstream of wastewater treatment plants (WWTP) effluents and sewer overflows. Effects on aquatic organisms can therefore not be excluded. Three BAC homologues could not be assessed, as there were no PNEC values available. Conclusions The contribution of emissions from WWTP (punctual emissions) to the environment is only about one tenth and relatively low compared to diffuse emissions. This means that measures for the emission reduction focussing only on end-of-pipe solutions in WWTP will not reduce the emissions significantly. Moreover, for the evaluation of measures, attention has to be paid to the fact that biocides such as the selected QAC are often also applied in non-biocidal applications (e.?g. three times higher volumes in the case of BAC). Recommendations and perspectives SFA serves as a useful tool for early recognition of environmental problems caused by chemicals. This allows recommending appropriate risk reduction measures in the production, the use and the end-of-life phase. It is advisable to use the SFA already in the development stage of chemicals and later on as a quality control tool. The relevant sources of chemicals and sinks in the environment can thus be determined in complex systems, even in absence of extensive measurements or product registers with consumption figures by means of estimations and scenarios.     

Effects of three years’ increase in density of the geometrid Epirrita autumnata on the change in metabolome of mountain birch trees (Betula pubescens ssp. czerepanovii)

The principal objective of the study was to characterize effects of increasing density of the autumnal moth, Epirrita autumnata (Lepidoptera, Geometridae), for 3 successive years on the change in metabolome of mountain birch trees (Betula pubescens ssp. czerepanovii). During the three study years (2000–2002), the larval density varied from low to very high (outbreak) density. Samples of leaves were collected from the same 12 trees at the same phenological stage of the trees each year. The leaves were collected from undamaged trees in the first year, from trees slightly damaged by larvae in the second year, and from trees heavily damaged by larvae in the third year. Metabolome analysis showed that the increase in density of E. autumnata larvae and degree of damage of birch trees caused multiple biochemical changes in the leaves, including increased concentrations of phenolic compounds (proanthocyanidins and hydrolysable tannins) and reduced concentrations of nutritive metabolites (monosaccharides, amino acids and some organic acids). These changes reduced the quality of leaves as food for larvae and, probably, were associated with induced chemical resistance of the birches to herbivorous insects. Additionally, the concentration of α-tocopherol was significantly higher in both slightly and heavily damaged trees. Mechanisms of changes in the metabolism of phenolic compounds and carbohydrates, and the role of α-tocopherol in their regulation are discussed.