Combining target analysis with sum parameters—a comprehensive approach to determine sediment contamination with PFAS and further fluorinated substances

Recent studies aiming at a fluorine mass balance analysis in sediments combined the determination of extractable organic fluorine (EOF) with target analysis. They reported high fractions of unidentified organic fluorine (UOF) compounds, as the target analysis covers only a limited number of per- and polyfluoroalkyl substances (PFAS). For this reason, in this study, a comprehensive approach was used combining target analysis with an extended PFAS spectrum, the EOF and a modified total oxidisable precursor (TOP) assay, which includes trifluoroacetic acid, to determine the PFAS contamination in sediments (n=41) and suspended solids (n=1) from water bodies in Northern Germany (Lower Saxony). PFAS are ubiquitous in the sediments (detected in 83% of the samples). Perfluorinated carboxylic acids (PFCAs) were found in 64% of the samples; perfluorinated sulfonic acids (PFSAs) were detected less frequently (21%), with the highest concentration observed for perfluorooctanesulfonic acid (PFOS). Levels of precursors and substitutes were lower. Applying the TOP assay resulted in an increase in PFCAs in 43% of the samples analysed. In most cases, target analysis and the TOP assay could not account for the EOF concentrations measured. However, as the fraction of UOF decreased significantly, the application of the TOP assay in fluorine mass balance analysis proved to be an important tool in characterising the PFAS contamination of riverine sediments.

     

Monitoring tricyclazole residues in rice paddy watersheds

Pesticide application to rice paddies may affect the quality of environmental resources such as groundwater and surface water. The distribution of residues of tricyclazole, an environmentally persistent fungicide used widely in Italy, was monitored in the network of surface water bodies surrounding the main rice production area in Italy. The location of monitoring sites was based on the potential risk for contamination with tricyclazole. This was determined as a function of the area of rice grown, the geographical distribution of rice crops susceptible to the pest, and sales of tricyclazole. Monitoring sites were also located to represent different spatial scales (farm, catchment and basin). For water samples taken shortly after application in July and August, the highest concentrations of tricyclazole were measured at the farm sites. However, residues were also detected at the catchment and basin scale. The 95% of the measured residue levels was below 9.80, 1.20 and 1.15 microg l(-1), at the farm, catchment and basin scales, respectively. In sediment, tricyclazole residues were detected in 12 out 176 samples collected with the 95% of the measured residue levels below the concentration of 0.03 mg kg(-1). Residues were sporadically detected in samples taken after the crop was harvested in November and December. Variables such as the scale of sampling, the season and the year, were significant in determining pesticide residue distribution. The type of water body was less significant.     

The changing state of contamination in the Lagoon of Venice. Part 2: heavy metals

In order to verify whether pollution is increasing or decreasing, in 25 locations uniformly distributed in the central part of the Lagoon of Venice, a transitional environment suffering from man's urban and industrial activities, the same sampling scheme was repeated three times (in 1987, 1993 and 1998) over a 12-year period during which the lagoonal environment underwent substantial changes. Superficial sediments were sampled and analysed for heavy metals and total organic carbon contents, grain size and density. In general heavy metal contents were found to be correlated, with concentrations above the background level, e.g., for Hg, a concentration factor of 24 was observed in 1987. A temporal decrease in concentrations was observed for most of the metals. Detailed analysis on a smaller spatial scale showed that contamination significantly decreases from the inner border of the lagoon seawards, as highlighted in contour maps. The role of the Porto Marghera industrial zone as a source of pollutants at the border of the Lagoon was confirmed. The decrease in contamination could not be attributed only to a decrease in the intensity of sources, but also to erosion processes, worsened by intensive harvesting of clams with hydraulic dredges.     

Molecular phylogeography of two Italian sibling species of Calobius (Coleoptera, Hydraenidae, Ochthebiinae) inhabiting Mediterranean marine rock-pools

Marine rock-pools, commonly found along the Mediterranean coasts, are isolated patches of habitat characterised by large spatial and temporal variations. The phylogeography of Calobius quadricollis and C. urbanelliae, two sibling species of moss beetles (Coleoptera, Hydraenidae) inhabiting Italian temporary marine rock-pool ecosystems, were studied using mitochondrial cytochrome c oxidase subunit I (COI). Our data suggest a strong association between the scored genetic variability and the geographical distribution of populations sampled for both species. These analyses provided evidences of episodic species range expansion and fragmentation, recurrent “flush and crash” and bottleneck episodes probably occurring during the Glacial Cycles. The observed phylogeographical pattern is probably related to the historical and biogeographical processes of Mediterranean areas, as well as both to the ephemeral habitat tipology and limited dispersal ability of these beetles.     

The Structure of the Shear Layer in Flows over Rigid and Flexible Canopies

Flume experiments were conducted with rigid and flexible model vegetation to study the structure of coherent vortices (a manifestation of the Kelvin–Helmholtz instability) and vertical transport in shallow vegetated shear flows. The vortex street in a vegetated shear layer creates a pronounced oscillation in the velocity profile, with the velocity near the top of a model canopy varying by a factor of three during vortex passage. In turn, this velocity oscillation drives the coherent waving of flexible canopies. Relative to flows over rigid vegetation, the oscillation in canopy geometry has the effect of decreasing the amount of turbulent vertical momentum transport in the shear layer. Using a waving plant to determine phase in the vortex cycle, each vortex is shown to consist of a strong sweep at its front (during which the canopy is most deflected), followed by a weak ejection at its rear (when the canopy height is at a maximum). Whereas in unobstructed mixing layers the vortices span the entire layer, they encompass only 70% of the flexibly obstructed shear layer studied here.     

Reliability of groundwater vulnerability maps obtained through statistical methods

Statistical methods are widely used in environmental studies to evaluate natural hazards. Within groundwater vulnerability in particular, statistical methods are used to support decisions about environmental planning and management. The production of vulnerability maps obtained by statistical methods can greatly help decision making. One of the key points in all of these studies is the validation of the model outputs, which is performed through the application of various techniques to analyze the quality and reliability of the final results and to evaluate the model having the best performance. In this study, a groundwater vulnerability assessment to nitrate contamination was performed for the shallow aquifer located in the Province of Milan (Italy). The Weights of Evidence modeling technique was used to generate six model outputs, each one with a different number of input predictive factors. Considering that a vulnerability map is meaningful and useful only if it represents the study area through a limited number of classes with different degrees of vulnerability, the spatial agreement of different reclassified maps has been evaluated through the kappa statistics and a series of validation procedures has been proposed and applied to evaluate the reliability of the reclassified maps. Results show that performance is not directly related to the number of input predictor factors and that is possible to identify, among apparently similar maps, those best representing groundwater vulnerability in the study area. Thus, vulnerability maps generated using statistical modeling techniques have to be carefully handled before they are disseminated. Indeed, the results may appear to be excellent and final maps may perform quite well when, in fact, the depicted spatial distribution of vulnerability is greatly different from the actual one. For this reason, it is necessary to carefully evaluate the obtained results using multiple statistical techniques that are capable of providing quantitative insight into the analysis of the results. This evaluation should be done at least to reduce the questionability of the results and so to limit the number of potential choices.     

Coral cavity sponges depend on reef-derived food resources: stable isotope and fatty acid constraints

The diet of cavity sponges on the narrow fringing reefs of Curaçao, Caribbean was studied. The origin and resources of the bulk food of these sponges, i.e., dissolved organic matter (DOM), were identified using stable carbon and nitrogen isotopes and fatty acid biomarkers. We found that phytoplankton and its derived DOM from the adjacent open sea and from reef overlying water is not the main source of food for most of the sponges examined nor is bacterioplankton. Interestingly, dual stable isotope signatures (δ¹³C_org, δ¹⁵N_org) and fatty acid biomarkers appoint coral mucus and organic matter derived from crustose coralline algae (CCA) as probable food sources for encrusting sponges. Mucus-derived DOM may contribute up to 66% to the diet of examined sponges based on results of dual isotope mixing model analysis. The contribution of CCA (as purported representative for benthic algae) was smaller with values up to 31%. Together, mucus- and CCA-derived substrates contributed for 48–73% to the diet of sponges. The presence of the exogenous fatty acid 20:4ω6 in sponges, which is abundant in coral mucus of Madracis mirabilis and in CCA, highlights these reef-derived resources as sources of nutrition for DOM feeding cavity sponges. The relatively high concentrations of exogenous 20:4ω6 in all sponges examined supports our hypothesis that the bulk of the food of the cavity sponge community is reef-derived. Our results imply that cavity sponges play an important role in conserving food and energy produced within the reef.     

CORINE land cover and floristic variation in a Mediterranean wetland

The aims of the present study were to: (1) investigate whether CORINE land cover classes reflect significant differences in floristic composition, using a very detailed CORINE land cover map (scale 1:5000); (2) decompose the relationships between floristic assemblages and three groups of explanatory variables (CORINE land cover classes, environmental characteristics and spatial structure) into unique and interactive components. Stratified sampling was used to select a set of 100-m(2) plots in each land cover class identified in the semi-natural wetland surrounding a lake in central Italy. The following six classes were considered: stable meadows, deciduous oak dominated woods, hygrophilous broadleaf dominated woods, heaths and shrublands, inland swamps, canals or watercourses. The relationship between land cover classes and floristic composition was tested using several statistical techniques in order to determine whether the results remained consistent with different procedures. The variation partitioning approach was applied to identify the relative importance of three groups of explanatory variables in relation to floristic variation. The most important predictor was land cover, which explained 20.7% of the variation in plant distribution, although the hypothesis that each land cover class could be associated with a particular floristic pattern was not verified. Multi Response Permutation Analysis did not indicate a strong floristic separability between land cover classes and only 9.5% of species showed a significant indicator value for a specific land cover class. We suggest that land cover classes linked with hygrophilous and herbaceous communities in a wetland may have floristic patterns that vary with fine scale and are not compatible with a land cover map.