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Soil food webs are traditionally considered to have distinct energy channels through which resources flow belowground. Resources enter the soil food web either from roots or from detrital inputs. Compared to this traditional view we are now much more aware of the flow of carbon, nitrogen and other resources through the microbes in the soil food web. Currently, the function of some groups of bacteria and fungi is known. The lowering of the costs of high throughput sequencing methods enables us to acquire more data on who is around, when and where in the soil food web. For soil fauna, gut content analyses in combination with sequencing can reveal feeding preferences, which enables establishing real trophic links based on observations, which can then be visualised as networks of feeding interactions. The fate of carbon flow through the soil food web can be traced by using stable isotopes combined with sequence based techniques. This provides insight into trophic connections and interaction strength. As the sequencing costs decrease rapidly, the level of detail in soil food web knowledge will similarly increase rapidly and enhance the feasibility of combined techniques. Using these techniques to broaden our insight into soil subsystems and their soil food webs will lead to more targeted decisions on management practices.

The Uddelermeer is a unique lake for The Netherlands, containing a sediment record that continuously registered environmental and climatic change from the late Pleistocene on to the present. A 15.6-m-long sediment record was retrieved from the deepest part of the sedimentary basin and an age–depth model was developed using radiocarbon dating, 210Pb dating, and Bayesian modeling. Lake-level change was reconstructed using a novel combination of high-resolution palaeoecological proxies (e.g. pollen, non-pollen palynomorphs, chironomids), quantitative determinations of lake-level change (ground-penetrating radar), and estimates of changes in precipitation (lipid biomarker stable isotopes). We conclude that lake levels were at least as high as present-day water levels from the late glacial to 3150 cal. yr BP, with the exception of at least one lake-level lowstand during the Preboreal period. Lake levels were ca. 2.5 m lower than at present between 3150 and 2800 cal. yr BP, which might have been the result of a change in moisture source region prior to the so-called 2.8-kyr event. Increasing precipitation amounts around 2800 cal. yr BP resulted in a lake-level rise of about 3.5–4 m to levels that were 1–1.5 m higher than at present, in line with increased precipitation levels as inferred for the 2.8-kyr event from nearby raised bog areas as well as with reconstructions of higher lake levels in the French Alps, all of which have been previously attributed to a phase of decreased solar activity. Lake levels decreased to their present level only during recent times, although the exact timing of the drop in lake levels is unclear.

Plaggic Anthrosols are the result of historical forms of land management in cultural landscapes on chemically poor sandy substrates. Application of plaggic manure was responsible for the development of the plaggic horizons of these agricultural soils. Pollen diagrams reflect aspects of the environmental development but the interpretation of the pollen spectra is complicated due to the mix of the aeolian pollen influx of crop species and species in the surroundings, and of pollen occurring in the used stable fillings. Pollen diagrams and radiocarbon dates of plaggic Anthrosols suggested a development period of more than a millennium. Calluna is present in almost all the pollen spectra, indicating the presence of heath in the landscape during the whole period of soil development. Optically stimulated luminescence dating of the plaggic horizon made clear that the deposition of plaggic covers started in the 16th century and accelerated in the 18th century. The stable fillings, used for the production of plaggic manure and responsible for the rise of the soil surface, cannot be identified with pollen diagrams alone. Biomarker analyses provide more evidence about the sources of stable fillings. The oldest biomarker spectra of the plaggic horizons of three typical plaggic Anthrosols examined in this study were dominated by biomarkers of forest species such as Quercus and Betula while the spectra of middle part of the plaggic horizons were dominated by biomarkers of stem tissue of crop species such as Secale and Avena. Only the youngest spectra of the plaggic horizons were dominated by biomarkers of Calluna. This indicates that the use of heath sods as stable filling was most likely introduced very late in the development of the Anthrosols. Before the 19th century the mineral component in plaggic manure cannot be explained by the use of heath sods. We conclude that other sources of materials, containing mineral grains must have been responsible for the raise of the plaggic horizon.

Invasive exotic plant species often have fewer natural enemies and suffer less damage from herbivores in their new range than genetically or functionally related species that are native to that area. Although we might expect that having fewer enemies would promote the invasiveness of the introduced exotic plant species due to reduced enemy exposure, few studies have actually analyzed the ecological consequences of this situation in the field. Here, we examined how exposure to aboveground herbivores influences shifts in dominance among exotic and phylogenetically related native plant species in a riparian ecosystem during early establishment of invaded communities. We planted ten plant communities each consisting of three individuals of each of six exotic plant species as well as six phylogenetically related natives. Exotic plant species were selected based on a rapid recent increase in regional abundance, the presence of a congeneric native species, and their co-occurrence in the riparian ecosystem. All plant communities were covered by tents with insect mesh. Five tents were open on the leeward side to allow herbivory. The other five tents were completely closed in order to exclude insects and vertebrates. Herbivory reduced aboveground biomass by half and influenced which of the plant species dominated the establishing communities. Exposure to herbivory did not reduce the total biomass of natives more than that of exotics, so aboveground herbivory did not selectively enhance exotics during this early stage of plant community development. Effects of herbivores on plant biomass depended on plant species or genus but not on plant status (i.e., exotic vs native). Thus, aboveground herbivory did not promote the dominance of exotic plant species during early establishment of the phylogenetically balanced plant communities. Electronic supplementary material The online version of this article (doi:10.1007/s00442-015-3472-6) contains supplementary material, which is available to authorized users.

Bacteria and fungi are important micro-organisms in the soil, but may differ in their impact on net N-mineralization. The hypothesis was tested that fungi are characterized by low microbial activity, but also low immobilization, and bacteria by high activity and high immobilization. A one-month laboratory incubation experiment with selective inhibition of fungi (cycloheximide) or bacteria (streptomycin) was conducted with samples of organic layer and mineral topsoil (0-10. cm) from neutral, bacteria-dominated and acidic, fungi-dominated Luxembourg beech forests. In the control treatment, respiration was higher in neutral than in acidic soil, but net N-mineralization was lower, due to higher immobilization. In the antibiotic treatments, differences in nitrification suggest that selective inhibition indeed occurred; in all soils and horizons, nitrification was especially limited by bactericide. Besides as inhibitor of the target group, antibiotics may also serve as source of C and N for the non-target group. For both bactericide and fungicide, acidic soils showed higher net recovery of C and N from antibiotics than neutral soil, which suggests that uptake or sorption of antibiotics is higher in the latter. Clear differences between neutral and acidic soils arose when the main micro-organisms were stimulated. In bacteria-dominated neutral soil, application of fungicide led to increased microbial respiration. In fungi-dominated acidic soil, however, application of bactericide did not lead to higher respiration, but to increased net N-mineralization per unit respiration, which supports a lower immobilization. Differences between antibiotics were consistent for organic layer and mineral topsoil, with increase in activity with fungicide, and lower immobilization with bactericide. The results provide correlative and experimental evidence that reduced immobilization by fungi compensates for their lower rates of activity with respect to N-availability to the vegetation.

Microorganisms capable of degrading herbicides are essential to minimize the amount of chemical compounds that may leach into other environments. This work aimed to study the potential of sandy-loam soil fungi to tolerate the herbicide Herburon (50% diuron) and to degrade the active ingredient diuron. Verticillium sp. F04, Trichoderma virens F28, and Cunninghamella elegans B06 showed the highest growth in the presence of the herbicide. The evaluation of biotransformation showed that Aspergillus brasiliensis G08, Aspergillus sp. G25, and Cunninghamella elegans B06 had the greatest potential to degrade diuron. Statistical analysis demonstrated that glucose positively influences the potential of the microorganism to degrade diuron, indicating a cometabolic process. Due to metabolites founded by diuron biotransformation, it is indicated that the fungi are relevant in reducing the herbicide concentration in runoff, minimizing the environmental impact on surrounding ecosystems.

Many wetlands are heavily modified and identifying the environmental drivers of indicator groups like aquatic insects is complicated by multiple stressors and co-varying environmental factors. Yet, incorporating data from other biological groups, such as microbial communities, potentially reveals which environmental factors are underpinning insect community composition. In the present study we investigated the application of benthic microbial community composition, as determined by phospholipid fatty acid (PLFA) analysis, alongside aquatic insect data in 25 peatland ditches in the province of North Holland, The Netherlands. We applied clustering and principal component analysis to a matrix of 26 PLFAs to group ditches by the microbial community. Generalized linear models were used to examine correlations between microbial PLFAs, insects, vegetation (emergent and submerged) and abiotic factors. The ratio of heterotrophic (e.g. sulphate reducing bacteria) to autotrophic (e.g. algae and cyanobacteria) derived PLFAs could be estimated as the ratio between saturated and branched to monounsaturated and polyunsaturated fatty acids (SB/MP). SB/MP was correlated with insect community composition, differences in water chemistry (in particular bicarbonate, sulphate and nutrients) and vegetation cover in the ditches. Moreover, ditches distinguished by their microbial communities differed in the number of insects they supported with differences most pronounced for Odonata, Trichoptera and Chironomus larvae. This study demonstrates that integrating microbial and aquatic insect community data provides insight into key environmental drivers in modified aquatic ecosystems and may facilitate the development of remediation strategies for degraded wetlands.

Because of large-scale production and use of an increasing diversity of chemicals in modern society, estuarine and coastal waters may be contaminated with numerous substances. Some of these compounds have the potential to affect microalgae at the base of the pelagic food chain. Therefore, we identified the main chemical stressors that negatively affect the effective photosystem II efficiency (øPSII) in marine microalgae of the Dutch estuarine and coastal waters. An enhanced effect-directed analysis (EDA) was carried out by combining reversed-phase ultra performance liquid chromatography fractionation of extracts from passive samplers, followed by effect assessment using the pulse amplitude modulation fluorometry assay and chemical analysis of biologically active fractions using high-resolution mass spectrometry. This study focuses on a novel microfractionation technique using 96-well plates to enhance throughput in EDA, structure elucidation, and the analytical and effect confirmation of the compounds that are identified. Although there are numerous unknown compounds present in estuarine and coastal waters, our EDA study shows that atrazine, diuron, irgarol, isoproturon, terbutryn, and terbutylazine are the main contributors to the observed effect on the øPSII of marine microalgae. © 2014 American Chemical Society.

Relatively hazardous brominated flame retardants (BFRs) are currently substituted with halogen-free flame retardants (HFFRs). Consequently, information on their persistence, bioaccumulation and toxicity (PBT) is urgently needed. Therefore, we investigated the chronic toxicity to the water flea Daphnia magna of two HFFRs, aluminum diethylphosphinate (ALPI) and 9,10-dihyro-9-oxa-10-phosphaphenanthrene-oxide (DOPO). The toxicity of ALPI increased from a 48 h LC50 of 18 mg L(-1) to a 21 day LC50 value of 3.2 mg L(-1), resulting in an acute-to-chronic ratio of 5.6. This may imply a change in classification from low to moderate toxicity. ALPI also affected sublethal life cycle parameters, with an EC50 of 2.8 mg L(-1) for cumulative reproductive output and of 3.4 mg L(-1) for population growth rate, revealing a nonspecific mode of action. DOPO showed only sublethal effects with an EC50 value of 48 mg L(-1) for cumulative reproductive output and an EC50 value of 73 mg L(-1) for population growth rate. The toxicity of DOPO to D. magna was classified as low and likely occurred above environmentally relevant concentrations, but we identified specific effects on reproduction. Given the low chronic toxicity of DOPO and the moderate toxicity of ALPI, based on this study only, DOPO seems to be more suitable than ALPI for BFR replacement in polymers.

There is a tendency to substitute frequently used, but relatively hazardous brominated flame retardants (BFRs) with halogen-free flame retardants (HFFRs). Consequently, information on the persistence, bioaccumulation and toxicity (PBT) of these HFFRs is urgently needed, but large data gaps and inconsistencies exist. Therefore, in the present study the toxicity of a wide range of HFFRs to the water flea Daphnia magna was investigated. Our results revealed that four HFFRs were showing no effect at their Sw (saturated water concentration) and three had a low toxicity (EC50 > 10 mg L− 1), suggesting that these compounds are not hazardous. Antimony trioxide had a moderate toxicity (EC50 = 3.01 mg L− 1, 95% CL: 2.76-3.25) and triphenyl phosphate and the brominated reference compound tetra bromobisphenol A were highly toxic to D. magna (EC50 = 0.55 mg L− 1, 95% CL: 0.53-0.55 and EC50 = 0.60 mg L− 1, 95% CL: 0.24-0.97 respectively). Aluminum trihydroxide and bisphenol A bis(diphenyl phosphate) caused limited mortality at Sw (26 and 25% respectively) and have a low solubility (< 10 mg L− 1). Hence, increased toxicity of these compounds may be observed when for instance decreasing pH could increase solubility. By testing all compounds under identical conditions we provided missing insights in the environmental hazards of new generation flame retardants and propose as best candidates for BFR replacements: APP, ALPI, DOPO, MHO, MPP, ZHS and ZS.

Studies of biological responses in the terrestrial environment to rapid changes in climate have mostly been concerned with aboveground biota, whereas less is known of belowground organisms. The present study focuses on mites and springtails of heathland ecosystems and how the microarthropod community has responded to simulated climate change in a long-term field experiment. Increased temperature and repeated drought was applied for 13 years to field plots located in Wales, The Netherlands and Denmark representing sites of contrasting climatic conditions with respect to precipitation and temperature. This approach provided an opportunity to study biological responses on a local (within sites) and regional scale. Warming treatments increasing night time temperature (0.3-1 °C higher than ambient at 5 cm soil depth) had no detectable effects on the microarthropod communities. Increased intensity and frequency of drought had only weak persistent effects on springtail species composition, but practically no effect on major mite groups (Oribatida, Prostigmata or Mesostigmata) suggesting that ecosystem functions of microarthropods may only be transiently impacted by repeated spring or summer drought.

The aim of this revision was to build an updated collection of information focused on the mechanisms and elements involved in metabolic pathways of aromatic hydrocarbons by bacteria. Enzymes as an expression of the genetic load and the type of electron acceptor available, as an environmental factor, were highlighted. In general, the review showed that both aerobic routes and anaerobic routes for the degradation of aromatic hydrocarbons are divided into two pathways. The first, named the upper pathways, from the original compound to central intermediate compounds still containing the aromatic ring but with the benzene nucleus chemically destabilized. The second, named the lower pathway, begins with ring de-aromatização and subsequent cleavage, resulting in metabolites that can be used by bacteria in the production of biomass. Under anaerobic conditions the five mechanisms of activation of the benzene ring described show the diversity of chemical reactions that take place. Obtaining carbon and energy from an aromatic hydrocarbon molecule is a process that exhibits the high complexity level of the metabolic apparatus of anaerobic microorganisms. The ability of these bacteria to express enzymes that catalyze reactions, known only in non-biological conditions, using final electron acceptors with a low redox potential, is a most interesting topic. The discovery of phylogenetic and functional characteristics of cultivable and non-cultivable hydrocarbon degrading bacteria has been made possible by improvements in molecular research techniques such as SIP (stable isotope probing) making trace of 13C, 15N and 18O into nucleic acids and proteins.

Acid atmospheric emissions within Europe and North America have decreased strongly since 1985 and most recent acidification studies have focused on the changes occurring within ecosystems as a result of this decreased deposition. This current study documents a soil acidification trend under ambient N deposition conditions over a 13 year period, suggesting that acidification continues to be a process of concern at this Calluna vulgaris dominated heathland with an acidic sandy soil. The annual manipulation of climatic conditions on this heathland simulated the predicted summer rainfall reduction (drought) and resulted in a long term retardation of the soil acidification trend. The pH of the soil solution significantly decreased over the course of the trial for both treatments, however, in the final two years the decline continued only in the Control treatment. This retardation is primarily associated with the reduction in rainfall leading to lower drainage rates, reduced loss of cations and therefore reduced lowering of the soil acid neutralizing capacity (ANC). However, a change in the underlying mechanisms also indicated that N transformations became less important in the Drought treatment. This change corresponded to an increase in groundcover of an air-pollution tolerant moss species and it is hypothesized that this increasing moss cover filtered an increasing quantity of deposited N, thus reducing the N available for transformation. A soil acidification lag time is expected to increase between the two treatments due to the cumulative disparity in cation retention and rates of proton formation. To the authors knowledge, this is the first study in which such acidification trends have been demonstrated in a field-scale climate manipulation experiment.

During the last decade, compound-specific hydrogen isotope analysis of plant leaf-wax and sedimentary n -alkyl lipids has become a promising tool for paleohydrological reconstructions. However, with the exception of several previous studies, there is a lack of knowledge regarding possible effects of early diagenesis on the δD values of n -alkanes. We therefore investigated the n -alkane patterns and δD values of long-chain n -alkanes from three different C3 higher plant species ( Acer pseudoplatanus L., Fagus sylvatica L. and Sorbus aucuparia L.) that have been degraded in a field leaf litterbag experiment for 27 months. We found that after an initial increase of long-chain n -alkane masses (up to ∼50%), decomposition took place with mean turnover times of 11.7 months. Intermittently, the masses of mid-chain n -alkanes increased significantly during periods of highest total mass losses. Furthermore, initially high odd-over-even predominances (OEP) declined and long-chain n -alkane ratios like n -C 31 /C 27 and n -C 31 /C 29 started to converge to the value of 1. While bulk leaf litter became systematically D-enriched especially during summer seasons (by ∼8‰ on average over 27 months), the δD values of long-chain n -alkanes reveal no systematic overall shifts, but seasonal variations of up to 25‰ ( Fagus , n -C 27 , average ∼13‰). Although a partly contribution by leaf-wax n -alkanes by throughfall cannot be excluded, these findings suggest that a microbial n- alkane pool sensitive to seasonal variations of soil water δD rapidly builds up. We propose a conceptual model based on an isotope mass balance calculation that accounts for the decomposition of plant-derived n -alkanes and the build-up of microbial n -alkanes. Model results are in good agreement with measured n -alkane δD results. Since microbial ‘contamination’ is not necessarily discernible from n -alkane concentration patterns alone, care may have to be taken not to over-interpret δD values of sedimentary n -alkanes. Furthermore, since leaf-water is generally D-enriched compared to soil and lake waters, soil and water microbial n -alkane pools may help explain why soil and sediment n -alkanes are D-depleted compared to leaves.

Lignin is a main component of plant litter. Its degradation is thought to be critical for litter decomposition rates and the build-up of soil organic matter. We studied the relationships between lignin degradation and the production of dissolved organic carbon (DOC) and of CO2 during litter decomposition. Needle or leaf litter of five species (Norway spruce, Scots pine, mountain ash, European beech, sycamore maple) and of different decomposition stage (freshly fallen and up to 27 months of field exposure) was incubated in the laboratory for two years. Lignin degradation was followed with the CuO method. Strong lignin degradation occurred during the first 200 incubation days, as revealed by decreasing yields of lignin-derived phenols. Thereafter lignin degradation leveled off. This pattern was similar for fresh and decomposed litter, and it stands in contrast to the common view of limited lignin degradation in fresh litter. Dissolved organic carbon and CO2 also peaked in thefirst period of the incubation but were not interrelated. In the later phase of incubation, CO2 production was positively correlated with DOC amounts, suggesting that bioavailable, soluble compounds became a limiting factor for CO2 production. Lignin degradation occurred only when CO2 production was high, and not limited by bioavailable carbon. Thus carbon availability was the most important control on lignin degradation. In turn, lignin degradation could not explain differences in DOC and CO2 production over the study period. Our results challenge the traditional view regarding the fate and role of lignin during litter decomposition. Lignin degradation is controlled by the availability of easily decomposable carbon sources. Consequently, it occurs particularly in the initial phase of litter decomposition and is hampered at later stages if easily decomposable resources decline.

Dung from a mammoth was preserved under frozen conditions in Alaska. The mammoth lived during the early part of the Late Glacial interstadial (ca 12,300 BP). Microfossils, macroremains and ancient DNA from the dung were studied and the chemical composition was determined to reconstruct both the paleoenvironment and paleobiology of this mammoth. Pollen spectra are dominated by Poaceae, Artemisia and other light-demanding taxa, indicating an open, treeless landscape (‘mammoth steppe’). Fruits and seeds support this conclusion. The dung consists mainly of cyperaceous stems and leaves, with a minor component of vegetative remains of Poaceae. Analyses of fragments of the plastid rbcL gene and trnL intron and nrITS1 region, amplified from DNA extracted from the dung, supplemented the microscopic identifications. Many fruit bodies with ascospores of the coprophilous fungus Podospora conica were found inside the dung ball, indicating that the mammoth had eaten dung. The absence of bile acids points to mammoth dung. This is the second time that evidence for coprophagy of mammoths has been derived from the presence of fruit bodies of coprophilous fungi in frozen dung. Coprophagy might well have been a common habit of mammoths. Therefore, we strongly recommend that particular attention should be given to fungal remains in future fossil dung studies.

article i nfo Shelf sediments of the southern North Sea, were studied with a microanalytical (electron probe X-ray microanalysis (EPXMA)) and two bulk (X-ray diffraction (XRD) and X-ray fluorescence (XRF)) techniques. The investigation proved that the promptness of the microanalytical method is combined with a reasonable analytical reliability. XRD studies of such a type of sediments with monotonous mineral composition are not able to provide mineralogical information beyond the main well-crystalline minerals and the mineralogical quantitative characteristic of the sediment based on XRD estimations are incorrect. The EPXMA mineralogical interpretations are based on the statistical evaluation of a huge data set (thousands of mineral particles) and provide a rather correct quantitative determination of the main minerals. The comparative EPXMA-XRF study revealed that the Al, Si, K, Ca, Fe and to some extent Ti contents estimated by EPXMA are fairly reliable. In this respect the accuracy of the EPXMA-based mineral identification of the pure silicates, pure aluminosilicates, and Al-, Ca-, Fe- and Ti-containing minerals with simple composition is very high. Mg- calcite, augite and apatite determinations are assessed to be correct. The supposed accuracy of the clay mineral determinations is slightly lower (70-80%) than that of the other main minerals due to the complex and varying composition of the clays. The identification of XRD-invisible accessory minerals and quantification of their presence in the sediments is an essential advantage of the EPXMA, which makes it a useful approach in tracing the origin of the sediments, the pathways of their transport and the geochemical processes they have undergone. However, the EPXMA has several flaws, which need to be solved in the future sediment investigations: (1) calibration with natural standards is needed in order to provide a higher accuracy of the mineral determinations; (2) any EPXMA study of sediments needs to be secured with XRF examinations of selected samples since EPXMA gives only semi-quantitative information about the abundance of the elements; (3) ultra-thin window EPXMA of low-Z elements has to be used since some of them (O, C) are always present in the main sediment components: silicates, aluminosilicates, carbonates and metal oxyhydr- oxides; (4) the interpretations of the clay fraction have to be supported with detailed XRD investigations of selected samples, while the mineralogy of the silt and sand fractions needs to be backed up with optical microscopy studies. The information from different analytical techniques (EPXMA with XRF-XRD-optical microscopy of selected samples) combined with the knowledge about the most possible minerals in a given environment, would give the most reliable results in studying mineralogical composition of shelf sediments.

As part of a longitudinal cohort study, now in its second decade, we determined PCDDs/Fs dl-PCBs and PBDEs in serum of adolescents with known perinatal PCDD/F exposure. Of the original cohort, 33 adolescents aged 14-19 years, who had been studied previously during their neonatal (n=60), toddler and pre-pubertal period (n=41) agreed to participate in the current follow-up. PCDD/F-, dl-PCB- and PBDE congeners were measured using GC/MS. Current serum levels of PCDD/Fs determined in our cohort were relatively low (mean of 2.2 pg/g) compared to the perinatal exposure. No correlation between perinatal exposure and current serum PCDD/F was found. Planar PCB TEQ levels were 2.2 pg/g. Current summation operatorPBDE levels were 8.7 ng/g lipid. There was one outlier with a summation operatorPBDE of 74 ng/g lipid. The presence of this high value indicates that the exposure pathway is different from PCDD/F and PCB, most likely by dust and food contaminated with dust. Concluding we can say that current PCDD/F levels are quite low compared to the perinatal PCDD/F exposure of the cohort. PBDE levels however are relatively high compared to other European countries, more research on possible health effects of these levels, especially for subjects with outlier concentrations, should be performed.

The environmentally persistent perfluorooctane sulfonate (PFOS) is a perfluoroalkylated acid (PFA), which has been found to accumulate and biomagnify through food webs all over the world. In the present investigation, the accumulation kinetics of PFOS was explored using the bioaccumulation model OMEGA. As accumulation behavior of PFOS may show similarities to fatty acids as well as to neutral organic compounds, different modeling approaches were used. Accumulation kinetics of PFOS was modeled similar to (1) moderately and (2) highly hydrophobic compounds, (3) metals and (4) as a combination of hydrophobic compounds and metals. Modeled elimination and uptake rate constants were compared to empirical rate constants from literature. Subsequently, model predictions were compared to field-based biota-suspended solids accumulation ratios (BSAF) in the estuarine food chain of the Western Scheldt. The Netherlands. Results show that uptake of PFOS is comparable to moderately hydrophobic compounds and elimination is best described by elimination kinetics of metals. These observations indicate that the accumulation behavior of PFOS is comparable to that of short and medium chained fatty acids. (C) 2007 Elsevier Ltd. All rights reserved.

The Rio Santiago in the Cordillera Negra of Peru is severely contaminated by acid mine drainage in its headwaters. In a strongly acid stream, at about 3800 m above sea level (masl), microterraces were found with terrace walls built up of dead moss, with encrustations and interstitial fine, creamy sediment. The stream water was turbid due to the presence of similar suspended sediment, which also occurred as a thin basal layer in inter-rim basins. The moss was identified as the rare bryophyte Anomobryum prostratum (Müll. Hal.) Besch. Chemical and mineralogical analyses show that green, living parts of the moss are gradually coated by Al/Fe (hydr)oxides, inducing their senescence and death. The necromass is covered by creamy crusts through precipitation of schwertmannite-type material from the stream water and simultaneous ‘capture’ of fine sediment. The latter consists of a mixture of precipitate and fine detrital primary minerals. These processes are held responsible for the formation of the microterraces, which regarding their composition and environment seem to be unique. Remarkable is the high As content of the creamy crusts and sediment, attributed to strong sorption of As, whereas its solute concentration is relatively low. This calls for more attention to suspended fine sediment in the assessment of environmental risks of stream water use. Lastly, the results raise serious doubts about the use of aquatic bryophytes as bioindicator for chemical pollution in acid mine drainage-polluted streams. Electronic supplementary material The online version of this article (doi:10.1007/s11270-015-2390-x) contains supplementary material, which is available to authorized users.

Traditionally, bioassays are used to assess the toxicity of chemicals. Bioassays often focus on one specific mode of action or end point and their responses offer a limited understanding of the health status and underlying pathways of the species under consideration. Metabolomics can be used to detect hundreds of metabolites in which each metabolite, or set of metabolites, represents short term and long term changes, indicating the status of the organism. The effects of the herbicide diuron, one of the compounds of concern for European water bodies, on the marine microalgae Dunaliella tertiolecta were investigated through non-target metabolomic profiling and bioassay testing. The pulse amplitude modulation (PAM) fluorometry bioassay was employed to measure the effective photosystem II efficiency (ϕPSII), while non-target metabolomic profiling using complementary analytical techniques characterized the metabolomic response in the algae during diuron exposure. The use of complementary analytical techniques was necessary to identify a broad range of metabolites. Twenty-eight compounds were identified as metabolites affected by diuron exposure, including several amino acids, adenosine, lactic acid, and citric acid. Collectively, these metabolites indicated that diuron negatively affects energy processes in the algae both at the citric acid cycle pathway as well as on the amino acid metabolism at realistic environmental concentrations. In addition, dose-response relationships were found between a number of affected metabolites and the inhibition of the ΦPSII of D. tertiolecta. Non-target metabolomic profiling using complementary analytical techniques proved to have additional and complementary benefits to traditional toxicology tests.

The mechanics of root reinforcement have been described satisfactorily for a single root or several roots passing a potential slip plane and verified by field experiments. Yet, precious little attempts have been made to apply these models to the hillslope scale pertinent to landsliding at which variations in soil and vegetation become important. On natural slopes positive pore pressures occur often at the weathering depth of the soil profile. At this critical depth root reinforcement is crucial to avert slope instability. This is particularly relevant for the abandoned slopes in the European part of the Mediterranean basin where root development has to balance the increasing infiltration capacity during re-vegetation. Detailed investigations related to root reinforcement were made at two abandoned slopes susceptible to landsliding located in the Alcoy basin (SE Spain). On these slopes semi-natural vegetation, consisting of a patchy herbaceous cover and dispersed Aleppo pine trees, has established itself. Soil and vegetation conditions were mapped in detail and large-scale, in-situ direct shear tests on the topsoil and pull-out tests performed in order to quantify root reinforcement under different vegetation conditions. These tests showed that root reinforcement was present but limited. Under herbaceous cover, the typical reinforcement was in the order of 0.6 kPa while values up to 18 kPa were observed under dense pine cover. The tests indicate that fine root content and vegetation conditions are important factors that explain the root reinforcement of the topsoil. These findings were confirmed by the simulation of the direct shear tests by means of an advanced root reinforcement model developed in FLAC 2D. Inclusion of the root distribution for the observed vegetation cover mimics root failure realistically but returns over-optimistic estimates of the root reinforcement. When the root reinforcement is applied with this information at the hillslope scale under fully saturated and critical hydrological conditions, root pull-out becomes the dominant root failure mechanism and the slip plane is located at the weathering depth of the soil profile where root reinforcement is negligible. The safety factors increase only slightly when roots are present but the changes in the surface velocity at failure are more substantial. Root reinforcement on these natural slopes therefore appears to be limited to a small range of critical hydrological conditions and its mitigating effect occurs mainly after failure.

Vetiver grass (Vetiveria zizanioides), also known as Chrysopogon zizanioides, is a graminaceous plant native to tropical and subtropical India. The southern cultivar is sterile; it flowers but sets no seeds. It is a densely tufted, perennial grass that is considered sterile outside its natural habitat. It grows 0.5–1.5 m high, stiff stems in large clumps from a much branched root stock. The roots of vetiver grass are fibrous and reported to reach depths up to 3 m thus being able to stabilize the soil and its use for this purpose is promoted by the World Bank. Uprooting tests were carried out on vetiver grass in Spain in order to ascertain the resistance the root system can provide when torrential runoffs and sediments are trying to uproot the plant. Uprooting resistance of each plant was correlated to the shoot and root morphological characteristics. In order to investigate any differences between root morphology of vetiver grass in its native habitat reported in the literature, and the one planted in a sub-humid environment in Spain, excavation techniques were used to show root distribution in the soil. Results show that vetiver grass possesses the root strength to withstand torrential runoff. Planted in rows along the contours, it may act as a barrier to the movement of both water and soil. However, the establishment of the vetiver lags behind the reported rates in its native tropical environment due to adverse climatic conditions in the Mediterranean. This arrested development is the main limitation to the use of vetiver in these environments although its root strength is more than sufficient.

An extensive study was carried out in the Netherlands on the occurrence of a number of estrogenic compounds in surface water, sediment, biota, wastewater, rainwater and on the associated effects in fish. Compounds investigated included natural and synthetic hormones, phthalates, alkylphenol(ethoxylate)s and bisphenol-A. The results showed that almost all selected (xeno-)estrogens were present at low concentrations in the aquatic environment. Locally, they were found at higher levels. Hormones and nonylphenol(ethoxylate)s were present in concentrations that are reportedly high enough to cause estrogenic effects in fish. Field surveys did not disclose significant estrogenic effects in male flounder (Platichthys flesus) in the open sea and in Dutch estuaries. Minor to moderate estrogenic effects were observed in bream (Abramis brama) in major inland surface waters such as lowland rivers and a harbor area. The prevalence of feminizing effects in male fish is largest in small regional surface waters that are strongly influenced by sources of potential hormone-disrupting compounds. High concentrations of plasma vitellogenin and an increased prevalence of ovotestes occurred in wild male bream in a small river receiving a considerable load of effluent from a large sewage treatment plant. After employing in vitro and in vivo bioassays, both in situ and in the laboratory, we conclude that in this case hormones (especially 17α-ethynylestradiol) and possibly also nonylphenol(ethoxylate)s are primarily responsible for these effects. © 2005 Elsevier Ltd. All rights reserved.

The use of the molecular mechanics AMBER force field (FF) to predict product profiles for the hydroxylation of the monoterpenes 1R-camphor, 1S-camphor, 1R-norcamphor, 1S-norcamphor and camphane by the enzyme cytochrome P450cam from the soil bacterium Pseudomonas putida was investigated. Predictions were carried out by applying multiple substrate (starting) orientations in the enzyme pocket in two procedures: a procedure based on molecular dynamics (MD) and a procedure based on short MD simulations followed by geometry optimisations. The latter (GO) procedure is faster and enabled the use of more monoterpene starting orientations. Monoterpene orientations were transformed into product profiles by applying both energetic and geometrical criteria appropriate for the (monoterpene) hydrogen abstraction reaction. Good predictions compared to experimental data were obtained for most compounds in both the MD and GO procedures. Prior to the product profile calculations, the FF was calibrated by reproducing the exp...

Commercial hexabromocyclododecane (HBCD) is a high-production-volume flame-retardant applied in polystyrene foams. It contains three stereoisomers, of which gamma-HBCD always dominates. Here we report on the levels of HBCD in blubber of harbor porpoise and common dolphin from different European seas. The highest total (sigma)-HBCD levels were measured in harbor porpoises stranded on the Irish and Scottish coasts of the Irish Sea (median concentration 2.9 microg (g of lipid)(-1)) and the northwest coast of Scotland (median concentration 5.1 microg (g of lipid)(-1)). The median levels in other areas were, for the harbor porpoise south coast of Ireland, 1.2 microg (g of lipid)(-1), for the coasts of The Netherlands, Belgium, and France north of Calais (southern North Sea), 1.1 microg (g of lipid)(-1), for the east coast of Scotland (northern North Sea), 0.77 microg (g of lipid)(-1), and, for Galicia (Spain), 0.1 microg (g of lipid)(-1). The median levels for the common dolphin were, for west coast of Ireland, 0.9 microg (g of lipid)(-1), for the French coast of the English Channel between Normandy and Brest, 0.4 microg (g of lipid)(-1), and, for Galicia, 0.2 microg (g of lipid)(-1). A subset of 10 harbor porpoise and 9 common dolphin blubber samples representing all areas were analyzed by LC/MS to determine the diastereomeric composition of their HBCD residues. All samples showed exclusively the peak of alpha-HBCD. To test if biotransformation by the cytochrome P450 system could explain the observed compositional difference with technical HBCD mixtures, a number of in vitro assays with microsomal preparations of liver were carried out. We had to revert to material stored at -80 degrees C from laboratory rats and a fresh harbor seal found dead in the Dutch Wadden Sea, since such liver samples of cetaceans were not in our possession. The in vitro assays showed that beta- and gamma-HBCDs were indeed significantly metabolized when incubated in the presence of NADPH as electron donor, compared to a set of reference samples which were identical except for the addition of NADPH. In contrast, the peak of alpha-HBCD did not decrease significantly in the presence of NADPH. In separate microsomal assays with beta- and gamma-HBCDs, new peaks of brominated compounds (signal at m/z = 79 or 81) with masses of [M + 0] were formed only when NADPH was added. This confirms the process of cytochrome P450 mediated biotransformation. Although rat and harbor seal belong to different families of the mammalia than the cetaceans, we propose that biotransformation by the cytochrome P450 system is also the most likely process to explain the exclusive accumulation of alpha-HBCD in harbor porpoise and common dolphin.

The vine weevil Otiorhynchus sulcatus is a parthenogenetic reproducing species which forages for suitable host plants at night, but is found congregated in dark places during the day. Frass of this weevil species is suspected to contain attractive compounds that are host‐plant related. Using a still‐air olfactometer, we tested adult vine weevils at night for their behavioural response to odours from conspecifics, feeding on a mixture of spindle tree (Euonymus fortunei) and yew (Taxus baccata), and to a sexually reproducing related species (Otiorhynchus salicicola), feeding on a mixture of ivy (Hedera helix) and cherry laurel (Prunus laurocerasus). Their attraction to conspecifics and O. salicicola appeared to be related to frass production. Freshly collected frass from O. sulcatus and from O. salicicola males and females was attractive. Prunus laurocerasus and H. helix have not been observed to be hosts of the vine weevil in the field. However, our tests showed that the vine weevil was attracted to mechanically damaged leaves of both plant species, whereas undamaged leaves were not attractive. Only undamaged young unfolding leaves of H. helix were also attractive. The attraction to odours from mechanically damaged host and non‐host plants suggested the involvement of compounds that are commonly found in many plant species. The involvement of plant compounds and/or aggregation pheromones in attraction to frass of the vine weevil and frass of the related weevil species O. salicicola is discussed.

Plant ecophysiological changes in response to climatic change may be different in northern and southern European countries because different abiotic factors constrain plant physiological activity. We studied the effects of experimental warming and drought on the photosynthetic performance of two ericaceous shrubs (Erica multiflora and Calluna vulgaris) along a European gradient of temperature and precipitation (UK, Denmark, The Netherlands, and Spain). At each site, a passive warming treatment was applied during the night throughout the whole year, whereas the drought treatment excluded rain events over 6–10 weeks during the growing season. We measured leaf gas exchange, chlorophyll a fluorescence, and leaf carbon isotope ratio (δ13C) during the growing seasons of 1999 and 2000. Leaf net photosynthetic rates clearly followed a gradient from northern to southern countries in agreement with the geographical gradient in water availability. Accordingly, there was a strong correlation between net photosynthetic rates and the accumulated rainfall over the growing season. Droughted plants showed lower leaf gas exchange rates than control plants in the four sites. Interestingly, although leaf photosynthetic rates decreased along the precipitation gradient and in response to drought treatment, droughted plants were able to maintain higher leaf photosynthetic rates than control plants in relation to the accumulated rainfall over the months previous to the measurements. Droughted plants also showed higher values of potential photochemical efficiency (Fv/Fm) in relation to controls, mainly at midday. The warming treatment did not affect significantly any of the studied instantaneous ecophysiological variables.

Horizons of humus profiles contain pollen and spores. The palynological information of pollen spectra of terrestrial humus forms must be validated by micropedological knowledge of the processes of infiltration, incorporation, conservation, transport and decay of pollen grains in the soil system. This study presents the results of combined palynological and micromorphological analyses of two mormoder humus forms, sampled in the Forestry Gieten, The Netherlands. The aim of this study was to establish the distribution pattern and life cycle of pollen grains in mormoders. The first step of this cycle of pollen grains in the humus profile is eolian deposition on the soil surface. The second step is incorporation of the grains in organic aggregates in the upper part of the F horizon. In ‘acid’ mormoders, grains are embedded by ageing small excrements of micro-arthropods and incorporated in the resulting organic aggregates. In ‘mild’ mormoders, the same process is observable, but additional pollen grains are also directly incorporated (and slightly transported) in medium excrements of small earthworm. The third step in the cycle is release by microbial attack of the aggregates in the lower part of the F horizon and the H and Ah horizons. The fourth step is re-incorporation of the released grains in organic aggregates of ageing small sized excrements of micro-arthropods, which consume decaying root tissue. Not re-incorporated grains will finally mineralise by microbial consumption. Mineralising of released pollen grains is the main process in the mineral AE horizon. Based on knowledge of the distribution pattern and life cycle of pollen grains in mormoders, pollen diagrams can be used for the reconstruction of the forest development.

Subsurface horizons contain considerable amounts of soil organic matter (SOM), which has generally a relatively recalcitrant nature and may be an important key in the examination of the role of soils in the sequestration of carbon. Nonetheless, this part of SOM is hardly studied. This paper focuses on the effects of soil acidification on the formation of SOM in sandy subsurface horizons under Corsican pine ( Pinus nigra var. maritime ) and common oak ( Quercus robur L.) forests in coastal dunes (The Netherlands) as characterized by pyrolysis and thermally assisted hydrolysis and methylation. In the pine forests of 50–70 y old SOM appeared to be only slightly affected by soil pH, whereas SOM from oak forests (100–200 years) showed pronounced changes upon soil acidification. With decreasing soil pH in the oak forests, lignin was more degraded (decrease in syringyl/guaiacyl ratio, reduction of the relative concentration) and the contribution of suberin-derived aliphatic moieties increased. The latter compounds may therefore play an important role in the formation of SOM in the studied subsoils.

The present study seeks quantitative measures for photoenhanced toxicity under natural light regimes by comparing the effects of an aromatic compound under natural and laboratory light. To this purpose, the influence of light irradiance and spectral composition on the extent of photoenhanced toxicity of acridine, a three-ringed azaarene, to the marine diatom Phaeodactylum tricornutum was analyzed. Under laboratory light containing ultraviolet radiation (UV), the 72-h EC50 growth value for acridine was 1.55 microM. Under natural light, a 72-h EC50 value for acridine below the lowest test concentration (0.44 microM) was observed. Under both laboratory and natural light, the toxicity of acridine was equally enhanced by total UV (UV-A and UV-B) and UV-A radiation, while in the absence of UV no enhancement of toxicity was observed. Hence, the UV-A region of light was dominant in the photoenhanced toxicity of acridine to P. tricornutum, in accordance with its absorption spectrum in the UV-A region. Therefore, the total amount of UV radiation absorbed by aqueous acridine was calculated for each separate treatment. The amount of UV absorbed by acridine effectively described the effect of acridine on the growth of P. tricornutum in a dose-response-dependent manner. It is concluded that photoenhanced toxicity of aromatic compounds expressed as a function of the actually absorbed UV may circumvent some of the variability between studies using different concentrations of the phototoxic compounds and light sources. The UV quantity absorbed by these compounds allows a comparison with the absorption characteristics of natural waters and, thus, is a key parameter to determine the role of photoenhanced toxicity in water.

Aims To perform wastewater analyses to assess spatial differences and temporal changes of illicit drug use in a large European population. Design Analyses of raw wastewater over a 1-week period in 2012 and 2013. Setting and Participants Catchment areas of wastewater treatment plants (WWTPs) across Europe, as follows: 2012: 25 WWTPs in 11 countries (23 cities, total population 11.50 million); 2013: 47 WWTPs in 21 countries (42 cities, total population 24.74 million). Measurements Excretion products of five illicit drugs (cocaine, amphetamine, ecstasy, methamphetamine, cannabis) were quantified in wastewater samples using methods based on liquid chromatography coupled to mass spectrometry. Findings Spatial differences were assessed and confirmed to vary greatly across European metropolitan areas. In general, results were in agreement with traditional surveillance data, where available. While temporal changes were substantial in individual cities and years (P ranging from insignificant to −3), overall means were relatively stable. The overall mean of methamphetamine was an exception (apparent decline in 2012), as it was influenced mainly by four cities. Conclusions Wastewater analysis performed across Europe provides complementary evidence on illicit drug consumption and generally concurs with traditional surveillance data. Wastewater analysis can measure total illicit drug use more quickly and regularly than is the current norm for national surveys, and creates estimates where such data does not exist.

Over the last two decades much has been written about the consequences of perinatal dioxin and PCB exposure in humans. In this paper we strive to elucidate the data on puberty in relation to these endocrine disruptive compounds in human populations. Effects in PCB/dioxin-exposed human populations on puberty are seen, not only in highly exposed cohorts, but also in average populations with background exposures. Study showed effects like increased weight, a delay in pubic hair growth and male genital development in boys, sex-hormone homeostasis, reduced penile length, and delayed age at first ejaculation after PCB exposure. Effects seen after dioxin exposure include retarded initiation and stage of breast development in girls, earlier menarche, disruption of sex hormone homeostasis, reduced testicular volume and reduced penile length in boys. The data published by different studies were inconclusive as a result of different methodological setup as well as because of multiple exposure settings. Populations were exposed to different mixtures of dioxin/PCB congeners or mixtures with other endocrine disrupters, and therefore synergistic and antagonistic effects with PCBs and dioxins are possible. Dioxinlike compounds disturb the hormonal balance mainly through interaction with the Ah receptor, which may influence the synthesis of hormones or their transport proteins. However, we have to keep in mind that hormonal balance during puberty could also be altered by disruption of the thyroid homeostasis. Another important possible mechanism is the induction of epigenetic changes or effects on genetic polymorphism. The fact that exposure to background concentrations of dioxin-like compounds and PCBs also has effects on the reproductive development is disconcerting and warrants further research and long term follow-up studies.

The origin and chemical nature of soil organic matter (SOM) in the ectorganic (L, F and H) horizons from four profiles from different stages of a primary vegetation succession on drift sand was studied to evaluate the impact of the vegetation on organic matter formation. In addition, the main sources of SOM, i.e. needles, leaves and (fine) roots of the covering species were analysed. Using conventional pyrolysis, virtually no differences were found between profiles in the same pine forest but with (chemically) different undergrowths ( Deschampsia flexuosa vs. Empetrum nigrum ) that clearly delivered leaf and root litter to SOM. Thermally assisted hydrolysis and methylation (THM) of the same samples released compounds that were not detected by conventional pyrolysis without methylation. These compounds included methyl ethers and methyl esters of ((poly)hydroxy)alkanoic acids and were identified as building blocks of cutin and suberin. Both biopolymers appeared to be better tracers of the various inputs of plant material than lignin, particularly in case of the most humified SOM. Although there was evidence of alteration of cutin and suberin compositions in the course of the succession in the beech forest, an inventory was still possible of above- and below ground litter as sources of SOM.

Root water uptake patterns are often studied with simulation models of the unsaturated soil water flow, as they are difficult to measure directly. Calibration of these models is not straightforward and causes uncertainties in simulated uptake distributions. In this paper we study how uncertainties in the calibration of the SWIF model affect uncertainty intervals in simulated uptake patterns of an Austrian pine stand (Pinus nigra var. nigra) on a sandy soil. After calibrating and validating SWIF with a large data set of more than 125 000 measured soil water contents over a three year period, uncertainty ranges in simulated soil water dynamics and root water uptake distributions were estimated with a Monte Carlo analysis. In general, uncertainties in root uptake patterns were small (typically

This study summarises the results of the levels of 21 perfluoroalkyl substances (PFASs) in 50 selected pooled samples representing 15 food commodities with the special focus on those of animal origin, as meat, seafood, fish, milk, dairy products and hen eggs, which are commonly consumed in various European markets, e.g. Czech, Italian, Belgian and Norwegian. A new, rapid sample preparation approach based on the QuEChERS extraction procedure was applied. Ultra-performance liquid chromatography (UHPLC) coupled to tandem mass spectrometry (MS/MS) employing electrospray ionisation (ESI) in negative mode was used for the quantification of target analytes. Method quantification limits (MQLs) were in the range of 1–10 ng kg−1 (ng l−1) for fish, meat, hen eggs, cheese and milk, and in the range of 2.5–125 ng kg−1 for butter. Only 16 of the group of 21 PFASs were found in at least one analysed sample. From 16 PFASs, perfluorooctane sulfonate (PFOS) was the most frequently detected analyte present in approximately 50% of samples (in the range of 0.98–2600 ng kg−1). PFCAs with C8–C14 carbon chain were presented in approximately 20% of samples. The concentration ranges of individual compounds in the respective groups of PFASs were: 2.33–76.3 ng kg−1 for PFSAs (without PFOS), 4.99–961 ng kg−1 for PFCAs, 10.6–95.4 ng kg−1 for PFPAs, and 1.61–519 ng kg−1 for FOSA. The contamination level in the analysed food commodities decreased in the following order: seafood > pig/bovine liver >> freshwater/marine fish > hen egg > meat >> butter. When comparing the total contamination and profiles of PFASs in food commodities that originated from various sampling countries, differences were identified, and the contents decreased as follows: Belgium >> Norway, Italy > Czech Republic.

A screening campaign of drugs of abuse (DOA) and their relevant metabolites in the aqueous environment was performed in the Netherlands. The presence of DOA, together with the potential risks for the environment and the possible human exposure to these compounds through consumption of drinking water was investigated. Sewage water (influent and effluent), surface water of the rivers Rhine and Meuse, and drinking water (raw and finished) were analysed by four different laboratories using fully in-house validated methods for a total number of 34 DOA and metabolites. In this way, data reported for several compounds could also be confirmed by other laboratories, giving extra confidence to the results obtained in this study. In total 17 and 22 DOA were detected and quantified in influent and effluent sewage samples, respectively. The tranquilizers oxazepam and temazepam, and cocaine and its metabolite benzoylecgonine were found in high concentrations in sewage water. Nine compounds were possibly not efficiently removed during treatment and were detected in surface waters. The results indicated that substantial fractions of the total load of DOA and metabolites in the rivers Rhine and Meuse enter the Netherlands from abroad. For some compounds, loads appear to increase going downstream, which is caused by a contribution from Dutch sewage water effluents. As far as data are available, no environmental effects are expected of the measured DOA in surface waters. In raw water, three DOA were detected, whereas in only one finished drinking water out of the 17 tested, benzoylecgonine was identified, albeit at a concentration below the limit of quantification (

The aim of this study was to integrally address the uncertainty associated with all the steps used to estimate community drug consumption through the chemical analysis of sewage biomarkers of illicit drugs. Uncertainty has been evaluated for sampling, chemical analysis, stability of drug biomarkers in sewage, back-calculation of drug use (specific case of cocaine), and estimation of population size in a catchment using data collected from a recent Europe-wide investigation and from the available literature. The quality of sampling protocols and analytical measurements has been evaluated by analyzing standardized questionnaires collected from 19 sewage treatments plants (STPs) and the results of an interlaboratory study (ILS), respectively. Extensive reviews of the available literature have been used to evaluate stability of drug biomarkers in sewage and the uncertainty related to back-calculation of cocaine use. Different methods for estimating population size in a catchment have been compared and the variability among the collected data was very high (7-55%). A reasonable strategy to reduce uncertainty was therefore to choose the most reliable estimation case by case. In the other cases, the highest uncertainties are related to the analysis of sewage drug biomarkers (uncertainty as relative standard deviation; RSD: 6-26% from ILS) and to the back-calculation of cocaine use (uncertainty; RSD: 26%). Uncertainty can be kept below 10% in the remaining steps, if specific requirements outlined in this work are considered. For each step, a best practice protocol has been suggested and discussed to reduce and keep to a minimum the uncertainty of the entire procedure and to improve the reliability of the estimates of drug use.

Background Polychlorinated dioxins and –furans (PCDD/Fs) and polychlorinated-biphenyls (PCBs) are environmental toxicants that have been proven to influence thyroid metabolism both in animal studies and in human beings. In recent years polybrominated diphenyl ethers (PBDEs) also have been found to have a negative influence on thyroid hormone metabolism. The lower brominated flame retardants are now banned in the EU, however higher brominated decabromo-diphenyl ether (DBDE) and the brominated flame retardant hexabromocyclododecane (HBCD) are not yet banned. They too can negatively influence thyroid hormone metabolism. An additional brominated flame retardant that is still in use is tetrabromobisphenol-A (TBBPA), which has also been shown to influence thyroid hormone metabolism. Influences of brominated flame retardants, PCDD/F’s and dioxin like-PCBs (dl-PCB’s) on thyroid hormone metabolism in adolescence in the Netherlands will be presented in this study and determined if there are reasons for concern to human health for these toxins. In the period 1987-1991, a cohort of mother-baby pairs was formed in order to detect abnormalities in relation to dioxin levels in the perinatal period. The study demonstrated that PCDD/Fs were found around the time of birth, suggesting a modulation of the setpoint of thyroid hormone metabolism with a higher 3,3’, 5,5’tetrathyroxine (T4) levels and an increased thyroid stimulating hormone (TSH). While the same serum thyroid hormone tests (- TSH and T4) were again normal by 2 years of age and were still normal at 8-12 years, adolescence is a period with extra stress on thyroid hormone metabolism. Therefore we measured serum levels of TSH, T4, 3,3’,5- triiodothyronine (T3), free T4 (FT4), antibodies and thyroxine-binding globulin (TBG) in our adolescent cohort. Methods Vena puncture was performed to obtain samples for the measurement of thyroid hormone metabolism related parameters and the current serum dioxin (PCDD/Fs), PCB and PBDE levels. Results The current levels of T3 were positively correlated to BDE-99. A positive trend with FT4 and BDE-99 was also seen, while a positive correlation with T3 and dl-PCB was also seen. No correlation with TBG was seen for any of the contaminants. Neither the prenatal nor the current PCDD/F levels showed a relationship with the thyroid parameters in this relatively small group. Conclusion Once again the thyroid hormone metabolism (an increase in T3) seems to have been influenced by current background levels of common environmental contaminants: dl-PCBs and BDE-99. T3 is a product of target organs and abnormalities might indicate effects on hormone transporters and could cause pathology. While the influence on T3 levels may have been compensated, because the adolescents functioned normal at the time of the study period, it is questionable if this compensation is enough for all organs depending on thyroid hormones.

An uptake study was carried out to assess the potential human exposure to perfluorinated alkyl acids (PFAAs) through the ingestion of vegetables. Lettuce (Lactuca sativa) was grown in PFAA-spiked nutrient solutions at four different concentrations, ranging from 10 ng/L to 10 μg/L. Eleven perfluorinated carboxylic acids (PFCAs) and three perfluorinated sulfonic acids (PFSAs) were analyzed by HPLC-MS/MS. At the end of the experiment, the major part of the total mass of each of the PFAAs (except the short-chain, C4-C7, PFCAs) taken up by plants appeared to be retained in the nonedible part, viz. the roots. Root concentration factors (RCF), foliage/root concentration factors (FRCF), and transpiration stream concentration factors (TSCF) were calculated. For the long chained PFAAs, RCF values were highest, whereas FRCF were lowest. This indicates that uptake by roots is likely governed by sorption of PFAAs to lipid-rich root solids. Translocation from roots to shoots is restricted and highly depending on the hydrophobicity of the compounds. Although the TSCF show that longer-chain PFCAs (e.g., perfluorododecanoic acid) get better transferred from the nutrient solution to the foliage than shorter-chain PFCAs (e.g., perfluoroheptanoic acid), the major fraction of longer-chain PFCAs is found in roots due to additional adsorption from the spiked solution. Due to the strong electron-withdrawing effect of the fluorine atoms the role of the negative charge of the dissociated PFAAs is likely insignificant.

In order to meet environmental quality criteria, grey water was treated in four different ways: 1) aerobic 2) anaerobic + aerobic 3) aerobic + activated carbon 4) aerobic + ozone. Since each treatment has its own specific advantages and disadvantages, the aim of this study was to compare the ecotoxicity of differently treated grey water using Chironomus riparius (96 h test) and Daphnia magna (48 h and 21d test) as test organisms. Grey water exhibited acute toxicity to both test organisms. The aerobic and combined anaerobic + aerobic treatment eliminated mortality in the acute tests, but growth of C. riparius was still affected by these two effluents. Post-treatment by ozone and activated carbon completely removed the acute toxicity from grey water. In the chronic toxicity test the combined anaerobic + aerobic treatment strongly affected D. magna population growth rate (47%), while the aerobic treatment had a small (9%) but significant effect. Hence, aerobic treatment is the best option for biological treatment of grey water, removing most of the toxic effects of grey water. If advanced treatment is required, the treatment with either ozone or GAC were shown to be very effective in complete removal of toxicity from grey water.

The analysis of sewage for urinary biomarkers of illicit drugs is a promising and complementary approach for estimating the use of these substances in the general population. For the first time, this approach was simultaneously applied in 19 European cities, making it possible to directly compare illicit drug loads in Europe over a 1-week period. An inter-laboratory comparison study was performed to evaluate the analytical performance of the participating laboratories. Raw 24-hour composite sewage samples were collected from 19 European cities during a single week in March 2011 and analyzed for the urinary biomarkers of cocaine, amphetamine, ecstasy, methamphetamine and cannabis using in-house optimized and validated analytical methods. The load of each substance used in each city was back-calculated from the measured concentrations. The data show distinct temporal and spatial patterns in drug use across Europe. Cocaine use was higher in Western and Central Europe and lower in Northern and Eastern Europe. The extrapolated total daily use of cocaine in Europe during the study period was equivalent to 356 kg/day. High per capita ecstasy loads were observed in Dutch cities, as well as in Antwerp and London. In general, cocaine and ecstasy loads were significantly elevated during the weekend compared to weekdays. Per-capita loads of methamphetamine were highest in Helsinki and Turku, Oslo and Budweis, while the per capita loads of cannabis were similar throughout Europe. This study shows that a standardized analysis for illicit drug urinary biomarkers in sewage can be applied to estimate and compare the use of these substances at local and international scales. This approach has the potential to deliver important information on drug markets (supply indicator). (C) 2012 Elsevier B.V. All rights reserved.

11 páginas, 7 figuras, 3 tablas., The heating effect on the soil organic matter (SOM) of a Mediterranean soil was studied in two fractions (macro- and microaggregates) and in two environments (soil under canopy of Quercus coccifera and bare soil between plants). Samples were heated under laboratory conditions at different temperatures (220, 380 and 500 degrees C) to establish their effects on the SOM quality and quantity by comparison with unheated control samples (25 degrees C). The SOM content in the soil under canopy was higher than in the bare one and in the microaggregate fractions than in the macroaggregate ones. Increasing temperatures caused, in general. the decrease of SOM content in both soils as well as in both aggregate classes. The quality of SOM was determined after extraction with 0.1 M NaOH and analysed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Obtained pyrolysates were characterized by the presence of polyphenols and other aromatic pyrolysis products (lipids, polysaccharides, proteins and lignin derivatives). Some of the products in these control samples, and furthermore the presence of black carbon (BC) markers (e.g. benzene, pyridine and toluene), confirmed the occurrence of past wildfires in the study zone. The composition of the SOM extracted from the soils heated at 220 degrees C, was quite similar to that obtained from unheated soils. The products derived from polysaccharides and lignin, and some coming from polyphenols, were not detected in the pyrolysates of the soil heated at 380 and 500 degrees C., This study was supported by the Conselleria d’Educació de la Generalitat Valenciana and its program “Beca para estancias de becarios y contratados predoctorales en centros de investigación fuera de la Comunidad Valenciana” (BEFPI/2008/018)and the Agreement Generalitat Valenciana – CSIC (2005020112)“Impacto de los incendios forestales repetidos sobre los procesos de erosión hídrica del suelo y la recuperación de la cubierta vegetal. Seguimiento y evaluación en una estación permanente de campo”. We also thank Leo Hoitinga and Joke Westerveld in the University of Amsterdam for helping in the SOM extraction and Py-GC/MS use, and Elizabeth Barrachina and Dolores Rius in the CIDE laboratory for SOM content determinations and Eugenia Gimeno-García for statistics assistance. Comments from two anonymous reviewers prompted significant improvements in the presentation of results.

The increasing time spent indoors combined with the abundant usage of diverse indoor chemicals led to concerns involving the impact of these compounds on human health. The current study focused on two groups of important indoor contaminants i.e. Brominated flame retardants (BFRs) and Perfluorinated compounds (PFCs). Concentrations of both compound classes have been measured in Flemish indoor dust samples from homes and offices. Sigma Polybrominated diphenyl ethers (PBDEs) (BDE 47, 99, 100, 154, 153, 197, 196 and 203) and BDE 209 in homes ranged between 4-1214 ng g(-1) dw (median 35) and

Since bacteria degrading polycyclic aromatic hydrocarbon compounds (PAHs) in polluted soils are generally exposed to mixtures of PAHs, we examined the influence of simple PAH mixtures on the degradation activity of Sphingomonas sp. strain LB126. Fluorene serves as sole carbon and energy source for the strain LB126 and phenanthrene and fluoranthene are cometabolically degraded by this species. Chemostat cultures of the strain LB126 were used to study a potential inhibiting effect of phenanthrene and fluoranthene on the degradation of fluorene that was previously observed in batch cultures. We also looked at the effect of phenanthrene on the degradation of glucose in a chemostat culture to see if this effect was specific for the PAH-metabolic pathway or for the total metabolism of the strain. The co-substrates were supplied in a 5% to 30% fraction of fluorene. Phenanthrene and fluoranthene had no significant influence on growth. However, fluorene degradation was inhibited by both phenanthrene and fluoranthene. The effect of phenanthrene was about 10 times stronger than the effect of fluoranthene. Nevertheless, more than 95% removal of fluorene took place together with more than 95% removal of either phenanthrene or fluoranthene. The effect of phenanthrene on the strain LB126 could be ascribed to both toxicity and competitive inhibition, but the effect observed at steady state was due to competitive inhibition only. It appeared that the strain LB126 adapts to the toxicity of phenanthrene within five generations. The inhibitory effects observed previously in batch cultures of the strain LB126 should mainly be ascribed to the toxic effect of phenanthrene.

article i nfo The aim of the present study was to elucidate consistent patterns in chronic polycyclic aromatic compound (PAC) toxicity to soil and sediment inhabiting invertebrates. Therefore we examined our experimental dataset, consisting of twenty-one chronic effect concentrations for two soil invertebrates (Folsomia candida and Enchytraeus cripticus) and two sediment invertebrates (Lumbriculus variegatus and Chironomus riparius) exposed to six PACs (two homocyclic isomers, anthracene and phenanthrene; two azaarene isomers: acridine and phenanthridine; and two azaarene transformation products, acridone and phenanthridone). In order to determine if effect concentrations were accurately predicted by existing toxicity-Kow relationships describing narcosis, chronic pore water effect concentrations were plotted jointly against logKow. Fifteen of the twenty- one effect concentrations (71%) were above the lower limit for narcosis, showing that narcosis was the main mode of action for the majority of the tested homo- and heterocyclic PACs during chronic exposure. Toxicity of all tested compounds to soil organisms was accurately described by the toxicity-Kow relationship. However, for the sediment invertebrates exposed to some of the tested heterocyclic PACs deviations from narcosis were identified, related to specific physicochemical properties of the test compounds and/or species specific sensitivities. It is concluded that existing toxicity-Kow relationships describing narcosis in some cases underestimate chronic PAC toxicity to sediment inhabiting invertebrates.

Azaarones (oxidized derivatives of azaarenes) is a group of newly emerging chemical compounds. Little is known about their occurrence in the aquatic environment. Azaarenes are polycyclic aromatic heterocyclic compounds containing one nitrogen atom in one of the aromatic rings. The (photo) oxidized metabolites of the azaarenes are often more toxic than the parent compound.For the first time the concentration of seven azaarenes and seven primary metabolites have been measured in the surface sediments (fraction < 63 μm) of the Dutch coastal zone of the North Sea. Samples collected in 2000 and 2001 were analyzed using a newly developed method to determine the contents of azaarenes and azaarones simultaneously in a single GC-MS run.The concentrations of acridine, benz[a]acridine, benz[c]acridine and 5,6-benzoquinoline varied between 10-63, 3.9-25, 3.3-11 and 3.98-10.84 ng g−1, respectively. Concentrations of 7,8-benzoquinoline and phenanthridine were below the limit of detection. 2-Hydroxyquinoline and 5-hydroxyquinoline, probably metabolites of quinoline, were present in relatively high concentrations: 7.4-949 and 11-188 ng g−1.A gradient was observed with highest concentrations of the sum of azaarenes and the sum of the concentration of their metabolites close to the coast and lower concentrations further offshore. The concentrations of azaarenes and their metabolites are in the same order of magnitude as those found to induce phototoxicity to algae.The concentrations of mineral oil and PAHs in the surface sediments of the Dutch coastal zone of the North Sea were, at most locations, above the Dutch chemical targets for environmental protection. Spatial distribution of PAHs and mineral oil were slightly different from those of azaarenes and transformation products.Simultaneous GC-MS for azaarenes and their degradation products is possible but extraction/clean up can be further improved. Azaarenes as well as their primary metabolic products are present in the marine environment. In sediments the cumulative concentrations of transformation products amount to about four times the cumulative concentrations of the azaarenes. In conclusion, azaarenes and their metabolites constitute a new group of emerging polycyclic aromatic compounds which need more attention in the future.

12 páginas, 7 figuras, 2 tablas., Aim To test whether the onset of spring growth in European shrublands is advanced in response to the warmer conditions projected for the next two decades by climate models, and, if there is a change, whether it differs across Europe. Location The studied sites spanned a broad north–south European gradient with average annual temperatures (8.2–15.6 °C) and precipitation (511–1427 mm). Methods ‘Bud break’ was monitored in eight shrub and grass species in six European sites under control and experimentally warmer conditions generated by automatic roofs covering vegetation during the night. Results Species responsive to increased temperatures were Vaccinium myrtillus and Empetrum nigrum in Wales, Deschampsia flexuosa in Denmark, Calluna vulgaris in Netherlands, Populus alba in Hungary and Erica multiflora in Spain. Although the acceleration of spring growth was the commonest response to warming treatments, the responses at each site were species specific and year dependent. Under experimental warming 25% of cases exhibited a significantly earlier onset of the growing season and 10% had a significantly delayed onset of vegetative growth. No geographical gradient was detected in the experimental warming effects. However, there was a trend towards a greater dominance of phenological advances with more intense the warming treatments. Above 0.8 °C warming, only advancements were recorded. Main conclusions Our results show that warmer temperatures projected for the next decades have substantial potential effects on the phenology of the spring growth of dominant species in different European shrublands, with a dominant trend towards advancements the more intense the warming is. However, our study also demonstrates the overall difficulties of applying simple predictive relationships to extrapolate the effects of global change on phenology. Various combinations of environmental factors occur concurrently at different European sites and the interactions between different drivers (e.g. water and chilling) can alter phenology significantly., The work was supported financially by the EU (contracts ENV4-CT97-0694 and EVK2- CT-2000-00094) and the participating research institutes. The CREAF group also received financial help from the Spanish Government (grant CGL2006-04025/BOS and grant Consolider Montes CSD2008-00040) and the Catalan Government (SGR2005-00312). The Hungarian team received financial help from the Hungarian Government (grants NKFP 3B-0008/2002) and the Hungarian Scientific Research Fund OTKA (T34790).