Large-scale spatial pollution patterns around the North Sea indicated by coastal bird eggs within an EcoQO programme

To categorize the marine environmental health status, the Oslo and Paris commissions have recently formulated Ecological Quality Objectives (EcoQOs) for many ecological features including the contamination of coastal bird eggs with mercury and organochlorines. In this study, we describe spatial and temporal patterns of egg contamination around the North Sea and compared them to the EcoQOs. Concentrations of mercury, polychlorinated biphenyl (??PCB) congeners, dichlorodiphenyltrichloroethane (??DDT) and derivatives, hexachlorobenzene (HCB) and hexachlorocyclohexane (??HCH) isomers were analysed in two tern species (Sterna hirundo and Sterna paradisaea) and Oystercatcher (Haematopus ostralegus) eggs collected between 2008 and 2010 in a total of 21 sites in seven countries surrounding the North Sea. Hg, ??PCB and HCB were highest in the southern sites, while ??DDT and ??HCH concentrations were greatest in eggs from the western North Sea and the Elbe estuary. There were rarely any consistent decreases over time for any compounds. In the terns, Hg, HCB and ??HCH increased at most sites, ??PCB and ??DDT in Sweden and Norway. In the Oystercatcher, HCB and ??HCH increased at more than the half of the sites, ??PCB, ??DDT and Hg at several German sites. In the terns, Hg, ??PCB and ??DDT exceeded the EcoQO in all, HCB in most years and sites. At most sites, ??HCH fulfilled the EcoQO in some study years. In the Oystercatcher, Hg, ??PCB and ??DDT exceeded the EcoQO in all or most years and sites. HCB and ??HCH fulfilled the EcoQO in some or all years at most sites. The EcoQO was exceeded most frequently in estuaries. We conclude that EcoQOs are suitable for drawing contamination patterns of the coastal North Sea in an easily understandable manner, offering the opportunity to harmonize the EcoQOs with coordinated environmental monitoring programmes.     

Land-use legacies in the forest structure of silvopastoral oak woodlands in the Eastern Mediterranean

Eastern Mediterranean silvopastoral oak woodlands have been greatly damaged through forest conversion, illegal lumbering, overgrazing, and forest fires. The aim of this study was to assess land-use changes and the legacies that they have imprinted on the forest structure of Quercus macrolepis and accompanying Quercus pubescens and Quercus cerris woodlands on Lesvos Island, Greece. The size structures of adult oak populations were analyzed as indicators of long-term oak regeneration, while short-term recruitment was determined by counting oak seedlings and saplings. The size structure of the adult Q. macrolepis population was similar to the inverse J-shaped distribution typical for natural Mediterranean oak forests, indicating continuous recruitment with a constant mortality rate of mature individuals. Seedling and sapling densities were highly variable, but generally low in relation to adult oak densities. Recruitment of oak seedlings and saplings was positively related to determinants such as forest cover, adult oak density and basal area, woody plant richness, and litter cover. Both seedling and sapling occurrence were negatively associated with dung frequency, which suggests that sheep grazing imposes a barrier to oak recruitment. The study outlines a comprehensive land-use transition from the 1950 to 1970s, during which a complex and multifunctional agrosilvopastoral land-use system was simplified to an intensive grazing system. The discrepancy between the successful long-term regeneration and the less successful short-term recruitment of oaks illustrates that intensified livestock grazing has been a major driver of vegetation change. Grazing impact is likely to interact with increasing drought conditions, which may trigger a negative feedback cycle that undermines the capacity of woodlands to sustain ecosystem services.     

Perfluorooctane Sulfonate Increases the Genotoxicity of Cyclophosphamide in the Micronucleus Assay with V79 Cells: Further Proof of Alterations in Cell Membrane Properties Caused by PFOS (3 pp)

Background, Aim and Scope Perfluorooctane sulfonate (PFOS; C8F17SO3-) is a fully fluorinated organic compound which has been manufactured for decades and was used widely in industrial and commercial products. The recent toxicological knowledge of PFOS mainly concerns mono-substance exposures of PFOS to biological systems, leaving the potential interactive effects of PFOS with other compounds as an area where understanding is significantly lacking. However, a recent study, reported the potential of PFOS to enhance the toxicity of two compounds by increasing cell membrane permeability. This is of particular concern since PFOS has been reported to be widely distributed in the environment where contaminants are known to occur in complex mixtures. In this study, PFOS was evaluated alone and in combination with cyclophosphamide (CPP) to investigate whether a presence of PFOS leads to an increased genotoxic potential of CPP towards hamster lung V79 cells. Genotoxicity was investigated using the micronucleus (MN) assay according to the recent draft ISO/DIS 21427-2 method. PFOS alone demonstrated no genotoxicity up to a concentration of 12.5 mg/L. However, PFOS combined with two different concentrations of CPP, with metabolic activation, caused a significant increase in the number of micronucleated cells compared to treatments with CPP only. These results provide a first indication that PFOS has the potential to enhance the genotoxic action of CPP towards V79 cells, suggesting that together with the alterations in cell membrane properties shown previously, that genotoxicity of complex mixtures may be increased significantly by changes in chemical uptake. Together with an earlier study performed by the own working group it can be concluded that PFOS alone is not genotoxic in this bioassay using V79 cells up to 12.5 mg/L, but that further investigations are needed to assess the potential interaction between PFOS and other substances, in particular regarding the impact of membrane alterations on the uptake of toxic substances. Materials and Methods: - Results: - Discussion: - Conclusions: - Recommendations and Perspectives: -     

Messung und Quantifizierung von Mineralölkohlenwasserstoffen

Investigations concerning the measurement and evaluation of mineral oil hydrocarbons using Fourier-transform-infrared (FT/IR-)-spectroscopy,¹H-Nuclear magnetic resonance (¹H-NMR)-spectroscopy and Capillary gas chromatography — Flame ionisation detection (GC-FID) are presented. By means of various mineral oils and three certified reference materials (CRM) all tested methods were within a ±7%-range to the mineral oil nominal value and the 95% confidence intervals of the CRM’s, respectively. The GC-FID evaluation could be done without calibration using an relative response ratio of mineral oil to an internal standard (n-tetracontane). A¹H-NMR-method was developed for the quantitative determination of mineral oil hydrocarbons, successfully applied down to 0.2 mg/ml. Due to the determination limit achieved, the¹H-NMR-spectroscopy gain in importance as a reference method for the analysis of mineral oils.     

Analytical solutions for flow fields near continuous wall reactive barriers

Permeable reactive barriers (PRBs) are widely applied for in-situ remediation of contaminant plumes transported by groundwater. Besides the goal of a sufficient contaminant remediation inside the reactive cell (residence time) the width of plume intercepted by a PRB is of critical concern. A 2-dimensional analytical approach is applied to determine the flow fields towards rectangular PRBs of the continuous wall (CW) configuration with and without impermeable side walls (but yet no funnel). The approach is based on the conformal mapping technique and assumes a homogeneous aquifer with a uniform ambient flow field. The hydraulic conductivity of the reactive material is furthermore assumed to exceed the conductivity of the aquifer by at least one order of magnitude as to neglect the hydraulic gradient across the reactor. The flow fields are analyzed regarding the widths and shapes of the respective capture zones as functions of the dimensions (aspect ratio) of the reactive cell and the ambient groundwater flow direction. Presented are an improved characterization of the advantages of impermeable side walls, a convenient approach to improved hydraulic design (including basic cost-optimization) and new concepts for monitoring CW PRBs. Water level data from a CW PRB at the Seneca Army Depot site, NY, are used for field demonstration.     

Geochemical investigation of potentially harmful elements in household dust from a mercury-contaminated site,the town of Idrija (Slovenia)

A comprehensive geochemical investigation of potentially harmful elements (PHEs) in household dust from the town of Idrija (Slovenia), once a world-famous Hg mining town that is now seriously polluted, was performed for the first time. After aqua regia digestion, the content of mercury (Hg), arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), molybdenum (Mo), nickel (Ni), lead (Pb) and zinc (Zn) was measured. PHE-bearing particles were recognised and observed by scanning electron microscopy and energy-dispersive spectrometry before and after exposure to simulated stomach acid (SSA). Mercury binding forms were identified by Hg thermal desorption technique and gastric bioaccessible Hg was estimated after SSA extraction by ICP-MS. With regard to rural and urban background values for Slovenia, high Hg content (6–120 mg/kg) and slightly elevated As content (1–13 mg/kg) were found. Mercury pollution is a result of past mining and ore processing activities. Arsenic content is potentially associated with As enrichment in local soils. Four Hg binding forms were identified: all samples contained Hg bound to the dust matrix, 14 samples contained cinnabar, two samples contained metallic Hg (Hg⁰), and one sample assumingly contained mercury oxide. After exposure to SSA, Hg-bearing phases showed no signs of dissolution, while other PHE-bearing phases were significantly morphologically and/or chemically altered. Estimated gastric Hg bioaccessibility was low (<0.006–0.09 %), which is in accordance with identified Hg binding forms and high organic carbon content (15.9–31.5 %) in the dust samples.     

Effect of Gasoline Formulation on the Formation of Photosmog: A Box Model Study

Abstract

Based on exhaust gas analyses from the combustion of five different types of gasoline in a passenger car operated on a chassis dynamometer, box model simulations of the irradiation of exhaust/NO_x /air mixtures using an established chemical mechanism for a standardized photo-smog scenario were performed. The fuel matrix used covered wide fractional ranges for paraffinic, olefinic, and aromatic hydrocarbons. Two fuels also contained methyl tertiary butyl ether (MTBE). The different O₃ profiles calculated for each run were compared and interpreted. The O₃ levels obtained were strongly influenced by the exhaust gas concentrations of aromatic and olefinic hydro-carbons. The higher exhaust content of these compounds caused higher O₃ production in the smog system investigated. The conclusion of the present study is that the composition of gasoline cannot be taken directly for the estimation of the emissions’ O₃ creation potential from its combustion. Variation of the dilution in the different calculations showed evidence for an additional influence of transport effects. Accordingly, further detailed exhaust gas analyses followed by more complex modeling studies are necessary for a proper characterization of the relationship between fuel blend and gasoline combustion products.     

Spatially valid data of atmospheric deposition of heavy metals and nitrogen derived by moss surveys for pollution risk assessments of ecosystems

For analysing element input into ecosystems and associated risks due to atmospheric deposition, element concentrations in moss provide complementary and time-integrated data at high spatial resolution every 5 years since 1990. The paper reviews (1) minimum sample sizes needed for reliable, statistical estimation of mean values at four different spatial scales (European and national level as well as landscape-specific level covering Europe and single countries); (2) trends of heavy metal (HM) and nitrogen (N) concentrations in moss in Europe (1990–2010); (3) correlations between concentrations of HM in moss and soil specimens collected across Norway (1990–2010); and (4) canopy drip-induced site-specific variation of N concentration in moss sampled in seven European countries (1990–2013). While the minimum sample sizes on the European and national level were achieved without exception, for some ecological land classes and elements, the coverage with sampling sites should be improved. The decline in emission and subsequent atmospheric deposition of HM across Europe has resulted in decreasing HM concentrations in moss between 1990 and 2010. In contrast, hardly any changes were observed for N in moss between 2005, when N was included into the survey for the first time, and 2010. In Norway, both, the moss and the soil survey data sets, were correlated, indicating a decrease of HM concentrations in moss and soil. At the site level, the average N deposition inside of forests was almost three times higher than the average N deposition outside of forests.