Estimation of uncertainty arising from different soil sampling devices: the use of variogram parameters

In the frame of the international SOILSAMP project, funded and coordinated by the National Environmental Protection Agency of Italy (APAT), uncertainties due to field soil sampling were assessed. Three different sampling devices were applied in an agricultural area using the same sampling protocol. Cr, Sc and Zn mass fractions in the collected soil samples were measured by k(0)-instrumental neutron activation analysis (k(0)-INAA). For each element-device combination the experimental variograms were calculated using geostatistical tools. The variogram parameters were used to estimate the standard uncertainty arising from sampling. The sampling component represents the dominant contribution of the measurement uncertainty with a sampling uncertainty to measurement uncertainty ratio ranging between 0.6 and 0.9. The approach based on the use of variogram parameters leads to uncertainty values of the sampling component in agreement with those estimated by replicate sampling approach.     

Epiphytic lichens as biomonitors of atmospheric pollution in Slovenian forests

Two country-wide surveys using epiphytic lichens as biomonitors of atmospheric pollution carried out during 2000 and 2001 in Slovenia were compared with surveys in 1991 and 1992. In the first survey, epiphytic lichen cover was studied in more than 500 plots of the 4 x 4 km national grid carried out within the framework of forest decline inventories. In the second survey, the epiphytic lichen Hypogymnia physodes (L.) Nyl., was collected on a 16 x 16 km bioindication grid and analysed for S, N, As, Br, Ce, Cd, Cr, K, La, Mo, Rb, Sb, Th, U and Zn contents. Only 'forested area' sampling points were included in the present study. Lichen cover was low, with about 70% of plots with less than 10% foliose lichen cover. No relationship was found between Hypogymnia trace element, N and S concentrations and foliose epiphytic lichen cover.     

Metallakkumulation in Moosen: Standörtliche und regionale Randbedingungen des Biomonitoring von Luftverunreinigungen

Goal and Scope

Several studies show that the concentration of metals in mosses depends not only on metal deposition but also on factors such as moss species, canopy drip, precipitation, altitude, distance to the sea and the analytical technique used. However, contrasting results have been reported and the interpretation of the spatial variability of the metal accumulation in mosses remains difficult. In the presented study existing monitoring data from the European Heavy Metals in Mosses Surveys together with surface data on precipitation, elevation and land use are statistically analysed to assess factors other than emissions that have an influence on the metal accumulation in the mosses.

Main Features

Inference statistics and Spearman correlation analysis were applied to examine the association of the metal accumulation and the distance of the monitoring sites to the sea as well as the altitude. Whether or not significant differences of the metal loads in the mosses exist at national borders was examined with help of the U-test after Mann and Whitney. In order to identify and rank the factors that are assumed to have an influence on the metal uptake of the mosses Classification and Regression Trees (CART) were applied.

Results

No clear tendency could be derived from the results of the inference statistical calculations and the correlation analyses with regard to the distance of the monitoring site to the sea and the altitude. According to the results of the CART-analyses mainly the moss species, potential emission sources around the monitoring sites, canopy drip and precipitation have an effect on the metal bioaccumulation. Assuming that each participating country followed strictly the manual for sampling and sample preparation the results of the inference statistical calculations furthermore suggest that in most cases different techniques for digestion and analysis bias the measurements significantly.

Discussion

For the first time a national monitoring data base consisting of measurement data and metadata as well as surface information on precipitation, land use and elevation was applied to examine influence factors on the metal bioaccumulation in mosses. The respective results mirror existing knowledge from other national studies to a large extend, although further analyses are necessary to affirm the findings. These analyses should include data from other national monitoring programmes and should additionally be carried out with other decision tree algorithms than CART.

Conclusions

The local variability in the metal concentration in mosses can be uncovered in terms of predictors or underlying hidden causes by using CART. Ideally, such an approach should be applied across the whole of Europe. This will only be feasible if all participating countries provide additional information about site characteristics as currently is done in for example the German moss surveys.

Recommendations

The UNECE Metals in Mosses Survey experimental protocol should be improved in order to reduce the observed influences, to enhance standardisation, and to strengthen the quality control. This implies the integration of sampling site describing metadata into the assessment. Furthermore, basis research is needed to test the hypothesis concerning moss species-specific accumulation of depositions.

Perspectives

Provided that the presented results hold true in further analyses correction factors should be applied on the moss data in order to get the depicted spatial patterns and temporal trends of metal bioaccumulation unbiased. Such factors should be calculated for natural landscape units or ecoregions that are homogeneous with regard to climate, vegetation and altitude.     

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 (r² = 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.     

Suspended particle adhesion on aquatic plant surfaces: implications for 137Cs and 133Cs uptake rates and water-to-plant concentration ratios

Suspended particle adhesion on aquatic biota can significantly increase the apparent concentration of radionuclides above their endogenous value, leading to an overestimation of the uptake rate and concentration ratios. This study is an attempt to assess quantitatively the importance of suspended particle adhesion on periphyton samples (biological material coating submerged surfaces). The concentrations of 137Cs and stable Cs (133Cs) in periphyton, suspended particles and filtered water were measured to determine the net water-to-periphyton concentration ratios for 137Cs and stable Cs. The net amount of 133Cs (or 137Cs) taken up by periphyton was calculated by subtracting from the total amount of 133Cs (or 137Cs) on the collected material (periphyton + inorganic particles), the 133Cs (or 137Cs) due to the inorganic particles adhering to periphyton. The mass of suspended particles adhering to the periphyton surface was calculated using scandium as an indicator of the mineral fraction of the suspended particles. The relationship between the concentration ratios for 137Cs and stable Cs and suspended particle adhesion on periphyton external surfaces is discussed.     

Lichens as integrating air pollution monitors

In this work an attempt to combine the results of lichen mapping with the quantitative levels of certain trace elements in Hypogymnia physodes (L.) Nyl. collected on a national scale is presented. An Index of Atmospheric Purity (IAP) was calculated using a simple method of mapping lichens based on the assessment of the cover and frequency of crustose, foliose and fruticose lichens on different tree species. For determination of trace elements in lichens k0-instrumental neutron activation analysis was used. From the IAP results it can be concluded that the epiphytic lichen flora look quite poor with more than 70% of the territory in the fourth and third classes, which represent highly polluted and moderately polluted air. By comparing IAP results with elemental levels in H. physodes using multivariate statistical methods it was found that the elemental levels do not have a direct negative effect on the diversity of lichens but can help in identification of the type of possible pollution sources and their origin.     

Modelling spatial patterns of correlations between concentrations of heavy metals in mosses and atmospheric deposition in 2010 across Europe

Background

This paper aims to investigate the correlations between the concentrations of nine heavy metals in moss and atmospheric deposition within ecological land classes covering Europe. Additionally, it is examined to what extent the statistical relations are affected by the land use around the moss sampling sites. Based on moss data collected in 2010/2011 throughout Europe and data on total atmospheric deposition modelled by two chemical transport models (EMEP MSC-E, LOTOS-EUROS), correlation coefficients between concentrations of heavy metals in moss and in modelled atmospheric deposition were specified for spatial subsamples defined by ecological land classes of Europe (ELCE) as a spatial reference system. Linear discriminant analysis (LDA) and logistic regression (LR) were then used to separate moss sampling sites regarding their contribution to the strength of correlation considering the areal percentage of urban, agricultural and forestry land use around the sampling location. After verification LDA models by LR, LDA models were used to transform spatial information on the land use to maps of potential correlation levels, applicable for future network planning in the European Moss Survey.

Results

Correlations between concentrations of heavy metals in moss and in modelled atmospheric deposition were found to be specific for elements and ELCE units. Land use around the sampling sites mainly influences the correlation level. Small radiuses around the sampling sites examined (5 km) are more relevant for Cd, Cu, Ni, and Zn, while the areal percentage of urban and agricultural land use within large radiuses (75–100 km) is more relevant for As, Cr, Hg, Pb, and V. Most valid LDA models pattern with error rates of <?40% were found for As, Cr, Cu, Hg, Pb, and V. Land use-dependent predictions of spatial patterns split up Europe into investigation areas revealing potentially high (=?above-average) or low (=?below-average) correlation coefficients.

Conclusions

LDA is an eligible method identifying and ranking boundary conditions of correlations between atmospheric deposition and respective concentrations of heavy metals in moss and related mapping considering the influence of the land use around moss sampling sites.

     

Biomonitoring with epiphytic lichens as a complementary method for the study of mercury contamination near a cement plant

The study was focused on understanding the mercury contamination caused by a cement plant. Active and passive biomonitoring with epiphytic lichens was combined with other instrumental measurements of mercury emissions, mercury concentrations in raw materials, elemental mercury concentrations in air, quantities of dust deposits, temperatures, precipitation and other measurements from the cement plant's regular monitoring programme. Active biomonitoring with transplanted lichens Pseudevernia furfuracea (L.) Zopf was performed at seven of the most representative sites around the cement plant and one distant reference site for periods of 3, 6 and 12 months. In situ lichens of different species were collected at the beginning of the monitoring period at the same sites. Mercury speciation of the plant exhaust gas showed that the main form of emitted mercury is reactive gaseous mercury Hg2?, which is specific for cement plants. Elemental mercury in air was measured in different meteorological conditions using a portable mercury detector. Concentrations in air were relatively low (on average below 10 ng m?3). In situ lichens showed Hg concentrations comparable to lichens taken from the background area for transplantation, indicating that the local pollution is not severe. Transplanted lichens showed an increase of mercury, especially at one site near the cement plant. A correlation between precipitation and Hg uptake was not found probably due to a rather uniform rainfall in individual periods. Dust deposits did not influence Hg uptake significantly. Lichens vitality was affected over longer biomonitoring periods, probably due to some elements in dust particles, their alkalinity and the influence of other emissions. Mercury uptake measured in vital transplanted lichens was in a good correlation with the working hours (i.e. emitted Hg quantity) of the kiln. The study showed that selected lichens could be used to detect low to moderate Hg emissions from a cement plant and that the biomonitoring procedure could be further standardized and used as part of an environmental monitoring programme.     

Metal accumulation in mosses across national boundaries: uncovering and ranking causes of spatial variation

This study aimed at cross-border mapping metal loads in mosses in eight European countries in 1990, 1995, and 2000 and at investigating confounding factors. Geostatistics was used for mapping, indicating high local variances but clear spatial autocorrelations. Inference statistics identified differences of metal concentrations in mosses on both sides of the national borders. However, geostatistical analyses did not ascertain discontinuities of metal concentrations in mosses at national borders due to sample analysis in different laboratories applying a range of analytical techniques. Applying Classification and Regression Trees (CART) to the German moss data as an example, the local variation in metal concentrations in mosses were proved to depend mostly on different moss species, potential local emission sources, canopy drip and precipitation.     

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 ≤ r_s ≤ 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.