Passive air sampling theory for semivolatile organic compounds

The mathematical modelling underlying passive air sampling theory can be based on mass transfer coefficients or rate constants. Generally, these models have not been inter-related. Starting with basic models, the exchange of chemicals between the gaseous phase and the sampler is developed using mass transfer coefficients and rate constants. Importantly, the inter-relationships between the approaches are demonstrated by relating uptake rate constants and loss rate constants to mass transfer coefficients when either sampler-side or air-side resistance is dominating chemical exchange. The influence of sampler area and sampler volume on chemical exchange is discussed in general terms and as they relate to frequently used parameters such as sampling rates and time to equilibrium. Where air-side or sampler-side resistance dominates, an increase in the surface area of the sampler will increase sampling rates. Sampling rates are not related to the sampler/air partition coefficient (K(SV)) when air-side resistance dominates and increase with K(SV) when sampler-side resistance dominates.     

Screening of organic halogens and identification of chlorinated benzoic acids in carbonaceous meteorites

The occurrence of halogenated organic compounds measured as a sum parameter and the evidence of chlorinated benzoic acids in four carbonaceous meteorites (Cold Bokkeveld, Murray, Murchison and Orgueil) from four independent fall events is reported. After AOX (Adsorbable organic halogen) and EOX (Extractable organic halogen) screening to quantify organically bound halogens, chlorinated organic compounds were analyzed by gas chromatography. AOX concentrations varying from 124 to 209 microg Cl/g d.w. were observed in carbonaceous meteorites. Ion chromatographic analysis of the distribution of organically bound halogens performed on the Cold Bokkeveld meteorite revealed that chlorinated and brominated organic compounds were extractable, up to 70%, whereas only trace amounts of organofluorines could be extracted. Chlorinated benzoic acids have been identified in carbonaceous meteorite extracts. Their presence and concentrations raise the question concerning the origin of halogenated, especially chlorinated, organic compounds in primitive planetary matter.     

Genetic population structure of fishes: implications for coastal zone management

The pattern for distribution of genetic variation within and between populations is referred to as the genetic population structure of the species. To avoid depletion of genetic resources sustainable management should be based on knowledge of this structure. We discuss key aspects of genetic population structure in the context of identifying biological units for fisheries management, suggesting three basic types of structuring: distinct populations; continuous change; and no differentiation. The type of structure determines how units for genetically sustainable management are to be identified. We also review what is currently known regarding the genetic population structure of fishes exploited in the Swedish part of the Baltic Sea, and conclude that sufficient genetic information is lacking for most of the species. This is a serious problem, particularly considering that populations of several commercially exploited fishes are declining and some exhibit recruitment problems. For six species, Atlantic herring, Atlantic salmon, brown trout, European eel, turbot, and pike, sufficient genetic data are available to provide at least basic information on genetic structure and genetic units for biologically sustainable use. Current management practices do not sufficiently consider these data.     

Growth of Plants on TBT-contaminated Harbour Sludge and Effect on TBT Removal (10 pp)

Background Worldwide, large amounts of sediments have to be dredged annually from waterways and harbours. These sediments are sometimes polluted with a variety of toxic compounds. In some countries, including Belgium, the load with the biocide tributyltin (TBT) from ship coatings prohibits the dumping of harbour sludge into the sea. Land-based dumping is a commonly used alternative. Objective This research investigated the feasibility to use land-deposited harbour sludge for plant production. In a field trial, the growth of 38 more or less salt-tolerant plant species on low and high TBT-contaminated sediments was studied. The elimination of TBT from sludge with and without vegetation was compared. The uptake of TBT and its degradation products di- and monobutyltin (DBT and MBT) into harvest products under field conditions was determined. - Experimental Set-up. Sediments dredged in May 2003 from the brackish waters of the port of Antwerp were analysed in the laboratory for soil texture, pH, electroconductivity, sodium, magnesium, potassium, calcium, ammonium, nitrate, total nitrogen, chloride, sulphur and the organotins TBT, DBT and MBT. The sediments were lagooned for one year to dewater, desalinate and improve their structure. Salt-tolerant domestic and wild plants were selected and sown in May 2004. In August 2004, plants were harvested and the produced biomass was determined. Samples were taken from vegetated and non-vegetated top and bottom sediments and from plants growing above soil and analysed for TBT, DBT and MBT. Results The fresh sediments showed a good supply with nutrients and a neutral pH, but were rather saline (EC 14 mS cm-1 of the saturated paste extract). The salinity decreased to 3.7 mS cm-1 during lagoonation. The high and the low contaminated sediment had initially 43 and 1.6 mg TBT kg-1 dry weight, respectively. Besides TBT, several other contaminants were present in the sediments at critical levels. The biomass production of the plant species from the field trial ranged from 0.2 to 13 tons dry mass per hectare. Plants performing excellently were barley, sorghum, rape seed, a clover/grass mix and reed. If at all, a positive influence of TBT on plant growth was seen. TBT was degraded significantly faster (>40%) below barley. The uptake of TBT, DBT and MBT into stem and leaves of reed, grass and clover was very low, but measurable and not related to concentrations in soil. No uptake of TBT or its metabolites into corn of barley was found. Discussion This study confirmed former results: the toxicity of TBT to higher plants is low, and even high levels in soils would not be a hindrance for crop production. The removal of TBT seemed to be increased by both lagooning and plant growth, although the target values for sea dumping in use in certain European countries were not reached. A plausible explanation for the faster degradation of TBT under vegetation is that oxygen is a limiting factor, and plants dewater the soil, thus aerating it. The uptake of the organotins TBT, DBT and MBT into harvest products is probably due to attached soil particles. Conclusions To summarize, barley was the optimal species: it grew very well despite the salinity of the dredged sediments, it had a significantly positive effect on TBT removal; it showed no measurable uptake of TBT or the other butyltins into the harvested product; and it is a cash crop well established in European agriculture. Outlook The amounts of dredged sediments are high, and good soils are becoming increasingly rare. The feasibility of using dredged sediments for non-food production, such as energy crops, should be investigated by a critical risk assessment.     

Enhanced experimental flexibility and control in ecotoxicological mesocosm experiments--a new outdoor and indoor pond and stream system

Scope The German Federal Environmental Agency has put into operation a new modular mesocosm system consisting of eight outdoor and eight indoor ponds and streams in order to investigate fate and effects of chemicals and municipal wastewater in aquatic ecosystems. General design and special characteristics are given to demonstrate the wide range of possibilities for experimental research. - General design. Each of the 16 streams with riffle and pool sections can be varied in length up to 106 m. The streams can be run as circular or flow-through systems at a flow velocity of 0.02 to 0.6 m/s. Physico-chemical standard parameters are measured on-line. The 16 ponds, which can be connected to the stream systems, are equipped with drainage and pore water-sampling devices for simulating processes in the littoral zone including influent and effluent ground water flow. Perspectives Since the highly flexible and controllable construction also allows treating a wide range of hydrological and ecological experiments external institutions are invited to submit proposals.     

Endocrine disruption of water and sediment extracts in a non-radioactive dot blot/RNAse protection-assay using isolated hepatocytes of rainbow trout

Goal, Scope and Background In order to evaluate the estrogenic activity of sediments and XAD water extracts of selected sites of the catchment area of the River Neckar, a river system in Southern Germany, an integrative assessment approach was used to assess the ecological hazard potential of endocrine-disrupting compounds in sediment and water. Methods The approach is based on estrogen receptor-mediated vitellogenin synthesis induced in isolated hepatocytes of rainbow trout and quantified in a non-radioactive dot blot/RNAse protection-assay in parallel to comprehensive chemical analyses of estrogenic substances. Results and Discussion Numerous investigated extracts revealed an estrogen activity comparable to that of the positive control (1 nM 17?-estradiol corresponding to 270 ng/L in the test medium). Based on a concentration factor of 30 in the extracts and a recovery of XAD resins of approximately 80 %, 17?-estradiol equivalent concentrations between 20 and 26.7 ng/L could be calculated downstream of a sewage treatment plant (< 0.1 ng/L for a reference site). A comparison of the bioassay-derived Bio-TEQs (toxicity equivalents) and the Chem-TEQs revealed a high correlation with a Pearson coefficient of 0.85, indicating that the same ranking of the samples could be obtained with respect to the endocrine disrupting potential with both chemical and bioanalytical analysis. However, the TEQ concentrations computed from chemical analyses were significantly lower than the bioassay-derived TEQ concentrations. In fact, in none of the samples, more than 14 % of the vitellogenin-inducing potency could be attributed to the substances (steroids, alkylphenols, bisphenol A, diethylstilbestrol) analyzed. A comparison of the endocrine disrupting potential of sediments extracted by the solvents acetone and methanol revealed lower biological effects for acetone-extracted samples. Possible reasons may be a masking of endocrine effects in acetone extracts by cytotoxicity, a low extraction efficiency of the solvent acetone, or anti-estrogen potencies of some extracted sediment compounds. Using a mass balance approach, the contribution of the compounds analyzed chemically (Chem-TEQs) to the total endocrine activity (Bio-TEQs) was calculated. Based on the very low detection limits, particularly of the steroids with their high TEF factors, results revealed that a calculation of the Chem-TEQs is associated with considerable scale inaccuracy: Whereas only 7-15 % of the biological effectiveness (Bio-TEQs) could be explained by endocrine substances identified above the detection limits, the assumption of concentrations slightly below the given detection limits would result in a significant over estimation (137-197 %) of the Bio-TEQs. Even the interassay variation of the dot blot assay with different fish donors for primary hepatocyte (factor 2 - 2.5) is relatively low, when compared to the large range of the Chem-TEQ concentrations (factor 20) obtained when applying different modes of calculation. Conclusions and Outlook Overall, only a minor portion of the endocrine activity detected by bioassays could be linked to compounds identified by chemical analysis. In vitro assays for assessment of endocrine activities are useful as sensitive integrating methods that provide quantitative estimates of the total activity of particular receptor-mediated responses. Although discrepancies may also result from different bioanalytical approaches, it is overall likely that bioanalytical and not chemical analytical approaches give the correct estimate of endocrine disrupting potencies in environmental samples. As a conclusion, assessment of endocrine disruption based on chemical analysis alone does not appear sufficient and further research into the spectrum of substances with potential endocrine activity as well as into additive or even synergistic effects in complex environmental samples is urgently needed.     

Identifikation der kfz-bürtigen Schadstoffbelastung mit Hilfe der Verh?ltnisse der stabilen Isotope von Kohlenstoff und Schwefel

Zusammenfassung  Reifen-, Ru?-, Motoren?l-, Asphalt-, Plastik- und Lackproben aus dem Stra?enverkehr wurden auf ihre Kohlenstoff- und Schwefel-isotopenverh?ltnisse mit dem Ziel untersucht, die Frage zu beant-worten, ob diese Isotopenverh?ltnisse als Indikatoren für die Belastungssituation und die Schadstoffquellen bei der Untersuchung von stra?ennahen B?den eingesetzt werden k?nnen. Die δ¹¹C-Werte der technischen Substrate lagen zwischen-30‰ und-18‰ relativ zum PDB-Standard, Dabei zeigte sich aufgrund der unterschiedlichen Herstellungsverfahren eine deutliche Abgrenzung der Substrate untereinander. Asphalt hatte Werte zwischen-23 und-18‰, Ru? zwischen -27 und -22‰ Die Ru?proben unterschieden sich je nach Art des verwendeten Kraftstoffs. Plastik, Lack und Motor?le zeigten ?hnliche δ¹³C-Werte, die zwischen-30 und-27‰ lagen. Reifen haben relativ konstante δ¹³C-Werte um -26‰ Der Einflu? des Stra?enverkehrs auf die δ¹³C-Werte im Stra?ensediment und in stra?ennahen B?den konnte anhand verschiedener Kohlenstoffspezies an einem Transekt an einer Landstra?e aufgezeigt werden. Ein Vergleich mit verkehrstypischen Schwermetallemissionen ergab bei einzelnen Kohlenstoffspezies einen ?hnlichen Verlauf der Schwermetallkonzentrationen und der δ¹³C-Werte. Die δ³⁴S-Werte lagen zwischen -6 und +8‰ relativ zum CDT-Standard. Eine Abgrenzung der Substrate in ihren δ¹⁴S-Werten war hierbei nicht m?glich.      

Sensitivity of the terrestrial biosphere to climatic changes: impact on the carbon cycle

The biosphere is a major pool in the global carbon cycle; its response to climatic change is therefore of great importance. We developed a 5 degrees x 5 degrees longitude-latitude resolution model of the biosphere in which the global distributions of the major biospheric variables, i.e. the vegetation types and the main carbon pools and fluxes, are determined from climatic variables. We defined nine major broad vegetation types: perennial ice, desert and semi-desert, tundra, coniferous forest, temperate deciduous forest, grassland and shrubland, savannah, seasonal tropical forest and evergreen tropical forest. Their geographical repartition is parameterized using correlations between observed vegetation type, precipitation and biotemperature distributions. The model computes as a function of climate and vegetation type, the variables related to the continental biospheric carbon cycle, i.e. the carbon pools such as the phytomass, the litter and the soil organic carbon; and carbon fluxes such as net primary production, litter production and heterotrophic respiration. The modeled present-day biosphere is in good agreement with observation. The model is used to investigate the response of the terrestrial biosphere to climatic changes as predicted by different General Circulation Models (GCM). In particular, the impact on the biosphere of climatic conditions corresponding to the last glacial climate (LGM), 18 000 years ago, is investigated. Comparison with results from present-day climate simulations shows the high sensitivity of the geographical distribution of vegetation types and carbon content as well as biospheric trace gases emissions to climatic changes. The general trend for LGM compared to the present is an increase in low density vegetation types (tundra, desert, grassland) to the detriment of forested areas, in tropical as well as in other regions. Consequently, the biospheric activity (carbon fluxes and trace gases emissions) was reduced.     

Daytime resolved analysis of polycyclic aromatic hydrocarbons in urban aerosol samples - impact of sources and meteorological conditions

Urban aerosol was collected in a summer and a winter campaign for 7 and 3 days, respectively. Low volume samples were taken with a time resolution of 160 min using a filter/sorption cartridge system extended by an ozone scrubber. Concentrations of mainly particle associated polycyclic aromatic hydrocarbons (PAH) and oxidised PAH (O-PAH) were determined by gas chromatography/high resolution mass spectrometry. The sampling site was located in the city centre of Augsburg, Germany, near major roads with high traffic volume. The daily concentrations and profiles were mainly governed by local emissions from traffic and domestic heating, as well as by the meteorological conditions. During the winter campaign, concentrations were more than 10 fold higher than during the summer campaign. Highest concentrations were found concurrent with low boundary layer heights and low wind speeds. Significant diurnal variation of the PAH profiles was observed. Enhanced influences of traffic related PAH on the PAH profiles were evident during daytime in summer, whereas emissions from hot water generation and domestic heating were obvious during the night time of both seasons. A general idea about the global meteorological situation was acquired using back trajectory calculations (NOAA ARL HYSPLIT4). Due to high local emissions in combination with low air exchange during the two sampling campaigns, effects of mesoscale transport were not clearly observable.     

Transport of particulate matter in natural waters — modelling and in situ-measurements

The significant processes controlling the fate of particulates are convection an dispersion on one hand, and sedimentation on the other hand. Due to inteparticulated reactions, larger aggregates can be formed from smaller units thus changing the sedimentation characteristics. These phenomena are summarized in a mathematical model whereby hydrodynamic effects as well as the control mechanisms of the dissolved phase are included. A relationship was derived on the basis of energy considerations leading to the formulation of a critical sedimentation velocity of the suspensa, which determines the transport capacity of the flowing system. The sedimentation term is calculated from the above discussed transport capacity, hydro-dynamic parameters and suspending media properties. Aggregation effects are taken into account as an increase of sedimentation velocities of the particles. The equations are solved in a particular computational routine such that the horizontal distribution of suspended solids in a natural system can be describe as function of the above discussed phenomena. The model was tested with in situ-measurements. It was found that the observed processes are described satisfactorily by this model.