Heavy metal and nitrogen concentrations in mosses are declining across Europe whilst some "hotspots" remain in 2010.

In recent decades, naturally growing mosses have been used successfully as biomonitors of atmospheric deposition of heavy metals and nitrogen. Since 1990, the European moss survey has been repeated at five-yearly intervals. In 2010, the lowest concentrations of metals and nitrogen in mosses were generally found in northern Europe, whereas the highest concentrations were observed in (south-)eastern Europe for metals and the central belt for nitrogen. Averaged across Europe, since 1990, the median concentration in mosses has declined the most for lead (77%), followed by vanadium (55%), cadmium (51%), chromium (43%), zinc (34%), nickel (33%), iron (27%), arsenic (21%, since 1995), mercury (14%, since 1995) and copper (11%). Between 2005 and 2010, the decline ranged from 6% for copper to 36% for lead; for nitrogen the decline was 5%. Despite the Europe-wide decline, no changes or increases have been observed between 2005 and 2010 in some (regions of) countries.

Comparison of metal concentrations in three species of mosses and metal freights in bulk precipitations.

Concentration of 25 trace metals in mosses ( Hylocomium splendens, Pleurozium schreberi and Hypnum cupressiforme) are compared with bulk deposition freights (Bergerhoff method) at 3 sites in Switzerland, one on the plateau, a second in the northern prealps and a third in the southern alps. The three moss species are interchangeable and the atmospheric background deposition can be estimated with sufficient accuracy for Ag, Al, As, Cd, Ce, Co, Cr, Cu, Fe, Ga, Ge, La, Li, Mo, Nb, Ni, Pb, Th, Ti, U, V, W, Y, Zn. For Hg this study does not give definite results. No seasonal differences in moss concentrations from spring to autumn can be shown.

Spatial distribution of PAH concentrations and stable isotope signatures (δ13C, δ15N) in mosses from three European areas--characterization by multivariate analysis.

Polycyclic aromatic hydrocarbon (PAH) concentrations and N, C stable isotope signatures were determined in mosses Hypnum cupressiforme Hedw. from 61 sites of 3 European regions: Île-de-France (France); Navarra (Spain); the Swiss Plateau and Basel area (Switzerland). Total PAH concentrations of 100-700 ng g(-1), as well as δ(13)C values of -32 to -29‰ and δ(15)N values of -11 to -3‰ were measured. Pearson correlation tests revealed opposite trends between high molecular weight PAH (4-6 aromatic rings) content and δ(13)C values. Partial Least Square regressions explained the very significant correlations (r > 0.91, p < 0.001) between high molecular weight PAH concentrations by local urban land use (<10 km) and environmental factors such as elevation and pluviometry. Finally, specific correlations between heavy metal and PAH concentrations were attributed to industrial emissions in Switzerland and road traffic emissions in Spain.

Country-specific correlations across Europe between modelled atmospheric cadmium and lead deposition and concentrations in mosses.

Previous analyses at the European scale have shown that cadmium and lead concentrations in mosses are primarily determined by the total deposition of these metals. Further analyses in the current study show that Spearman rank correlations between the concentration in mosses and the deposition modelled by the European Monitoring and Evaluation Programme (EMEP) are country and metal-specific. Significant positive correlations were found for about two thirds or more of the participating countries in 1990, 1995, 2000 and 2005 (except for Cd in 1990). Correlations were often not significant and sometimes negative in countries where mosses were only sampled in a relatively small number of EMEP grids. Correlations frequently improved when only data for EMEP grids with at least three moss sampling sites per grid were included. It was concluded that spatial patterns and temporal trends agree reasonably well between lead and cadmium concentrations in mosses and modelled atmospheric deposition.

Nitrogen concentrations in mosses indicate the spatial distribution of atmospheric nitrogen deposition in Europe.

In 2005/6, nearly 3000 moss samples from (semi-)natural location across 16 European countries were collected for nitrogen analysis. The lowest total nitrogen concentrations in mosses (<0.8%) were observed in northern Finland and northern UK. The highest concentrations (≥ 1.6%) were found in parts of Belgium, France, Germany, Slovakia, Slovenia and Bulgaria. The asymptotic relationship between the nitrogen concentrations in mosses and EMEP modelled nitrogen deposition (averaged per 50 km × 50 km grid) across Europe showed less scatter when there were at least five moss sampling sites per grid. Factors potentially contributing to the scatter are discussed. In Switzerland, a strong (r(2) = 0.91) linear relationship was found between the total nitrogen concentration in mosses and measured site-specific bulk nitrogen deposition rates. The total nitrogen concentrations in mosses complement deposition measurements, helping to identify areas in Europe at risk from high nitrogen deposition at a high spatial resolution.

Mosses as biomonitors of atmospheric heavy metal deposition: spatial patterns and temporal trends in Europe.

In recent decades, mosses have been used successfully as biomonitors of atmospheric deposition of heavy metals. Since 1990, the European moss survey has been repeated at five-yearly intervals. Although spatial patterns were metal-specific, in 2005 the lowest concentrations of metals in mosses were generally found in Scandinavia, the Baltic States and northern parts of the UK; the highest concentrations were generally found in Belgium and south-eastern Europe. The recent decline in emission and subsequent deposition of heavy metals across Europe has resulted in a decrease in the heavy metal concentration in mosses for the majority of metals. Since 1990, the concentration in mosses has declined the most for arsenic, cadmium, iron, lead and vanadium (52-72%), followed by copper, nickel and zinc (20-30%), with no significant reduction being observed for mercury (12% since 1995) and chromium (2%). However, temporal trends were country-specific with sometimes increases being found.

Moss interspecies comparisons in trace element concentrations.

Within the framework of a European-scaled moss survey, various moss species were sampled throughout The Netherlands [NL], Germany [D], and Switserland [CH], and used in moss interspecies comparisons of elemental concentrations. Moss species considered were Pleurozium schreberi [NL,D,CH], Brachythecium rutabulum [NL], Hypnum cupressiforme [D,CH], Hylocomium splendens [D,CH], and Scleropodium purum [D]. Element analysis was carried out directly (The Netherlands, Instrumental Neutron Activation Analysis: As, Br, Ce, Cr, Cs, Fe, La, Mn, Na, Rb, Sc, Se, Sm, Th, Ti, V and Zn), or after sample digestion (The Netherlands, ICP-MS: Pb, Germany, AAS/ICP-AES: Cd, Cr, Cu, Fe, Ni, Pb, Ti, V, and Zn; Switzerland, ICP-AES/ICP-MS: Co, V, and Zn).Local variations (=within sampling sites) in element concentrations were estimated, based upon in-site multiple sampling and analysis of Pleurozium schreberi species in The Netherlands. Element concentrations in moss species were compared in linear correlations, both in unweighted and weighted fits, with weighing factors based on the local variation data. Weighted fits were shown to generally improve the calibration characteristics, as tracked by X (2) calculations.The calibration data suggest the presence of previously unnoticed outliers in element concentrations. The absence of further information, however, may prescribe the use of all data in comparison procedures. These results indicate that interlaboratory analysis of replicate samples and the use of dedicated certified reference materials may help solving problems in the analysis of the sample series.For several of the considered interspecies comparisons, weighted calibrations could be based on significant correlations (P=0.05). Actual use, however, will remain arbitrarily decided upon, and may be based on decisions as to what to accept with respect to the levels of uncertainty in the calibration parameters. Furthermore, the use of calibrations in extrapolation modes is greatly restricted by the necessary reservations in geographically larger-scaled applications.

Field intercomparison of diffusive samplers for measuring ammonia.

Agricultural production systems are recognised as a major source of atmospheric ammonia. Deposition of ammonia and ammonium may contribute to undesired changes in oligotrophic ecosystems. The continuous measurement of atmospheric ammonia requires expensive and sophisticated techniques and is performed only in a very restrict number of ambient air stations in Europe. Therefore, the application of passive samplers, which have the advantage of being easy to handle and cost-efficient, is useful. In the past the comparability of different passive samplers must be considered as rather scarce. In a joint European project under the leadership of the GSF-Forschungszentrum für Umwelt und Gesundheit, Neuherberg, in 1997 a comparison of different passive ammonia monitoring methods was carried out in a prealpine rural site near Garmisch-Partenkirchen. It was considered valuable to include not only well established systems but also methods still being developed. For the comparative test ten working groups with different methods took part. A wet annular denuder system, which has been developed by the Netherlands Energy Research Foundation for on-line measurement of atmospheric ammonia, served as reference of passive methods. The experiment, which started in June and finished in December, showed that most of the passive samplers fulfil the requirements and can be recommended for further measurements. Additional measurements of meteorological parameters were performed to check the influences of different weather conditions on passive sampling.