Akkumulation von Metallen und Stickstoff in Moosen in Nordrhein-Westfalen 1990–2005 (Accumulation of metals and nitrogen in mosses in North Rhine-Westfalia 1990-2005)

Every five years since 1990, the European moss surveys provide data on concentrations of heavy metals and since 2005 on nitrogen (N) in mosses. Germany participated in the monitoring campaigns 1990 – 2005. As part of a series reporting the trends for Germany and single federal states, this article is on North Rhine-Westphalia showing that the metal concentrations decreased from 1990 to 2000 for all elements but Zn. From 2000 to 2005 an increase can be stated for As, Cr, Cu, Ni, Sb, Zn and the Multi Metal Index MMI1990-2005. The N concentration reaches from 1.08 to 2,29% in dry mass showing significant correlations to the agriculture density (+), the height of the surrounding trees (+), the forests density (−), the distance to trees (−), altitude (−) and the precipitation sum for the accumulation period (−). The according correlation coefficients (Spearman) reach from rs 0.32 to 0.49 (p <0.01). The correlation of the metal loads in the mosses and land use characteristics in the vicinity of the sampling sites lie between rs = 0.21 and rs = 0.54 (0.01 <p <0.05). The type of moss species and the moss growth patterns are associated to a similar degree (Cramér´s V-values between 0.27 and 0.56). Of all investigated site specific information on forest density (Cd, Cu, Pb, Zn, N), urban density precipitation (Cd, Ni, Pb, V, N), altitude (As, Cd, Cr, Cu, Fe, Ni, Ti, Zn, N) and the distance of the sampling site to roads (Cr, Fe, Ni, Ti), trees or bushes (As, Cd, Cr, Cu, Fe, Ni, Zn) are those showing significant correlations to the elements enumerated in brackets before. The urban land use density in a radius of 5 km around the sampling site as well as altitude and the distance of the sampling site to nearby trees are the statistically most significant factors for the Cu concentrations in mosses sampled in 2005. The total deposition of Cd (EMEP) and Cd concentrations in mosses are correlated significantly (0.57 ≤ rs ≥0.71, p <0.01)

Mapping background values of atmospheric nitrogen total depositions in Germany based on EMEP deposition modelling and the European Moss Survey 2005

Background: In order to map exceedances of critical atmospheric deposition loads for nitrogen (N) surface data on the atmospheric deposition of N compounds to terrestrial ecosystems are needed. Across Europe such information is provided by the international European Monitoring and Evaluation Programme (EMEP) in a resolution of 50 km by 50 km, relying on both emission data and measurement data on atmospheric depositions. The objective of the article at hand is on the improvement of the spatial resolution of the EMEP maps by combining them with data on the N concentration in mosses provided by the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops (ICP Vegetation) of the United Nations Economic Commission for Europe (UNECE) Long-range Transboundary Air Pollution (LTRAP) Convention. Methods: The map on atmospheric depositions of total N as modelled by EMEP was intersected with geostatistical surface estimations on the N concentration in mosses at a resolution of 5 km by 5 km. The medians of the N estimations in mosses were then calculated for each 50 km by 50 km grid cell. Both medians of moss estimations and corresponding modelled deposition values were ln-transformed and their relationship investigated and modelled by linear regression analysis. The regression equations were applied on the moss kriging estimates of the N concentration in mosses. The respective residuals were projected onto the centres of the EMEP grid cells and were mapped using variogram analysis and kriging procedures. Finally, the residual and the regression map were summed up to the map of total N deposition in terrestrial ecosystems throughout Europe. Results and discussion: The regression analysis of the estimated N concentrations in mosses and the modelled EMEP depositions resulted in clear linear regression patterns with coefficients of determination of r2 = 0.62 and Pearson correlations of rp = 0.79 and Spearman correlations of rs = 0.70, respectively. Regarding the German territory a nationwide mean of 18.1 kg/ha/a (standard deviation: 3.49 kg/ha/a) could be derived from the resulting map on total N deposition in a resolution of 5 km by 5 km. Recent updates of the modelled atmospheric deposition of N provided a similar estimate for Germany. Conclusions: The linking of modelled EMEP data on the atmospheric depositions of total N and the accumulation of N in mosses allows to map the deposition of total N in a high resolution of 5 km by 5 km using empirical moss data. The mapping relies on the strong statistical relationship between both processes that are physically and chemically related to each other. The mapping approach thereby relies on available data that are both based on European wide harmonized methodologies. From an ecotoxicological point of view the linking of data on N depositions and those on N bioaccumulation can be considered a substantial progress

Mapping atmospheric depositions of cadmium and lead in Germany based on EMEP deposition data and the European Moss Survey 2005

Background: Every five years since 1990, the European Heavy Metals in Mosses Survey provided data on atmospheric heavy metal bioaccumulations in mosses throughout Europe at a high spatial resolution. The moss data show the effectiveness of air quality control policies: for Germany the metal bioaccumulations decreased between 1990 and 2000, whilst they increased from 2000 to 2005. This investigation is intended to show how the moss data could be used to map atmospheric depositions of Cd and Pb, which later on might serve for the calculation of Critical Loads Exceedances. In addition, we compared how much heavy metal concentrations in mosses in Germany deviate from background data observed in Greenland. Methods: Mapping heavy metals with a high spatial resolution for the German territory was conducted according to the following methodology: EMEP deposition maps (50 km by 50 km spatial resolution) were intersected within a GIS with Kriging maps on Cd and Pb accumulations in mosses (EMEP (European Monitoring and Evaluation Programme) is a scientifically based and politically driven programme under the Convention on Long-range Transboundary Air Pollution for international co-operation to solve transboundary air pollution problems). Subsequently, the statistical relations between the EMEP modelled depositions and the bioaccumulations in mosses were quantified by using regression analysis. The regression functions were used to transform the moss concentration maps into deposition maps. The resulting maps on Cd and Pb depositions have a spatial resolution of 5 km by 5 km and were added to the respective map on the residuals of the regression functions (Regression Kriging). Finally, the territory of Germany was extracted from the European maps on Cd and Pb depositions and the legends were adjusted accordingly in terms of n standard deviations from the German mean value. The concentrations of Al, As, Cd, Cr, Cu, Mo, Pb, Sb, Sn, and Zn in the mosses sampled in 1990, 1995, 2000 and 2005 in Germany were compared with background values derived from mosses sampled in north-eastern Greenland (Zackenberg Background Values). The differences between heavy metal concentrations in mosses in Germany and Greenland were calculated for the 16 federal states of Germany and mapped for Pb. Results and discussion: The regression models corroborate that the Cd concentration in mosses is correlated with the EMEP modelled total Cd deposition across Europe (regression coefficient according to Pearson, rp = 0.67; regression coefficient according to Spearman, rs = 0.69). The coefficient of determination is r2 = 0.44. The same is true for Pb with rp = 0.76 and rs = 0.77 and r2 = 0.58. Based on the regression models and the respective residuals, maps on the total deposition of Cd and Pb were calculated for the year 2005. The German mean value of total Cd and Pb deposition was 0.342 g/ha/a (standard deviation 0.08 g/ha/a and 8.6 g/ha/a (standard deviation 2.1 g/ha/a) respectively. The maps depict the spatial patterns of the total Cd and Pb deposition in terms of n standard deviations from the respective German wide mean value. The spatial resolution of the maps is 5 km × 5 km and reflects the mesh size of the moss monitoring net. Even today, the bioaccumulation of several metals in Germany still exceeds the background values observed in Greenland. This is true especially for Cd, Cr, Cu, Mo, Pb, Sb, Sn and Zn. Comparing the results of this investigation with those from other methods it can be concluded that the mean values calculated for the total Cd and Pb deposition for Germany differ from such assessed by deposition measurements and models. The latter are used to calculate Critical Loads Exceedances, which complement the ecotoxicological endpoint 'accumulation'. The deposition measurements in Germany are mainly based on monitoring systems conducted by the federal states. When trying to use deposition measurements from the ICP Forests level II programme for the validation of the EMEP deposition modelling, problems arose due to a lack of methodical harmonization and the quality of the depositions measurements. That is why in this investigation the quality controlled and spatially high resolved moss data were used to empirically validate EMEP modelled deposition maps. Conclusions: In Germany, the moss measurement data provide a valuable tool at a high spatial resolution for the validation of modelling and mapping of atmospheric heavy metal deposition and should as such be used for this purpose. The comparison of the metal concentrations in mosses in Germany with the values found in Greenland indicate that atmospheric deposition of heavy metals in Germany is still considerably higher than the natural background deposition

First Europe-wide correlation analysis identifying factors best explaining the total nitrogen concentration in mosses

In this study, the indicative value of mosses as biomonitors of atmospheric nitrogen (N) depositions and air concentrations on the one hand and site-specific and regional factors which explain best the total N concentration in mosses on the other hand were investigated for the first time at a European scale using correlation analyses. The analyses included data from mosses collected from 2781 sites across Europe within the framework of the European moss survey 2005/6, which was coordinated by the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops (ICP Vegetation). Modelled atmospheric N deposition and air concentration data were calculated using the Unified EMEP Model of the European Monitoring and Evaluation Programme (EMEP) of the Convention on Long-range Transboundary Air Pollution (CLRTAP). The modelled deposition and concentration data encompass various N compounds. In order to assess the correlations between moss tissue total N concentrations and the chosen predictors, Spearman rank correlation analysis and Classification and Regression Trees (CART) were applied. The Spearman rank correlation analysis showed that the total N concentration in mosses and modelled N depositions and air concentrations are significantly correlated (0.53 ≤ rs ≤ 0.68, p < 0.001). Correlations with other predictors were lower than 0.55. The CART analysis indicated that the variation in the total N concentration in mosses was best explained by the variation in NH4+ concentrations in air, followed by NO2 concentrations in air, sampled moss species and total dry N deposition. The total N concentrations in mosses mirror land use-related atmospheric concentrations and depositions of N across Europe. In addition to already proven associations to measured N deposition on a local scale the study at hand gives a scientific prove on the association of N concentration in mosses and modelled deposition at the European scale

First thorough identification of factors associated with Cd, Hg and Pb concentrations in mosses sampled in the European Surveys 1990, 1995, 2000 and 2005

The aim of this study was, for the first time ever, to thoroughly identify the factors influencing Cd, Hg and Pb concentrations in mosses sampled within the framework of the European Heavy Metals in Mosses Surveys 1990–2005. These investigations can be seen as a follow up of a previous study where only the moss data recorded in the survey 2005 was included in the analysis (Schröder et al. 2010). The analyses of this investigation give a complete overview on the statistical association of Cd, Hg and Pb concentrations in mosses and sampling site-specific and regional characteristics, encompassing data from 4661 (1990), 7301 (1995), 6764 (2000) and 5600 (2005) sampling sites across Europe. From the many metals monitored in the European moss surveys, Cd, Hg and Pb were used as examples, since only for these three metals deposition measurements are being recorded in the framework of the European Monitoring and Evaluation Programme (EMEP). As exemplary case studies revealed that other factors besides atmospheric deposition of metals influence the element concentrations in mosses, the moss datasets of the above mentioned surveys were analysed by means of bivariate statistics and decision tree analysis in order to identify factors influencing metal bioaccumulation. In the analyses we used the metadata recorded during the sampling as well as additional geodata on, e.g., depositions, emissions and land use. Bivariate Spearman correlation analyses showed the highest correlations between Cd and Pb concentrations in mosses and EMEP modelled total deposition data (0.62 ≤ rs ≤ 0.73). For Hg the correlations with all the tested factors were considerably lower (e.g. total deposition r s  ≤ 0.24). Decision tree analyses by means of Classification and Regression Trees (CART) identified the total deposition as the statistically most significant factor for the Cd and Pb concentrations in the mosses in all four monitoring campaigns. For Hg, the most significant factor in 1990 as identified by CART was the distance to the nearest Hg source recorded in the European Pollutant Emission Register, in 1995 and 2000 it was the analytical method, and in 2005 it was the sampled moss species. The strong correlations between the Cd and Pb concentrations in the mosses and the total deposition can be used to calculate deposition maps with a regression kriging approach on the basis of surface maps on the element concentrations in the mosse

Secretome analysis of Phanerochaete chrysosporium strains CIRM-BRFM41 grown on softwood

 Abstract Proteomic analysis was performed to determine and differentiate the composition of the secretomes of Phanerochaete chrysosporium CIRM-BRFM41, a peroxidase hypersecretory strain grown under ligninolytic conditions and on softwood chips under biopulping conditions. Extracellular proteins from both cultures were analyzed by bidimensional gel electrophoresis and matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry. A total of 37 spots were identified. The secretome in liquid synthetic medium comprised mainly peroxidases, while several wood-degrading enzymes and enzymes involved in fungal metabolism were detected in biopulping cultures on softwood. This prompted an analysis of the impact of secretome modulation in the presence of softwood chips. Biotreated wood was submitted to kraft cooking and chemical bleaching using chlorine dioxide. The fungal pre-treatment led to a significant increase in pulp yield and a better bleachability of the pulp. This bleachability improvement could be explained by the production of specific lignocellulose-degrading enzymes