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.     

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.     

The impact of nitrogen deposition on acid grasslands in the Atlantic region of Europe

A survey of 153 acid grasslands from the Atlantic biogeographic region of Europe indicates that chronic nitrogen deposition is changing plant species composition and soil and plant-tissue chemistry. Across the deposition gradient (2-44 kg N ha⁻¹ yr⁻¹) grass richness as a proportion of total species richness increased whereas forb richness decreased. Soil C:N ratio increased, but soil extractable nitrate and ammonium concentrations did not show any relationship with nitrogen deposition. The above-ground tissue nitrogen contents of three plant species were examined: Agrostis capillaris (grass), Galium saxatile (forb) and Rhytidiadelphus squarrosus (bryophyte). The tissue nitrogen content of neither vascular plant species showed any relationship with nitrogen deposition, but there was a weak positive relationship between R. squarrosus nitrogen content and nitrogen deposition. None of the species showed strong relationships between above-ground tissue N:P or C:N and nitrogen deposition, indicating that they are not good indicators of deposition rate.     

Assessing spatial patterns of metal bioaccumulation in French mosses by means of an exposure index

Background, aim and scope  

The European Heavy Metals in Mosses Surveys (UNECE-ICP Vegetation) is a programme performed every 5 years since 1990 in at least 21 European countries. The moss surveys aim at uncovering the spatiotemporal patterns of metal and nitrogen bioaccumulation in mosses. In France, the moss survey was conducted for the third time in 2006. Five hundred thirty-six monitoring sites were sampled across the whole French territory. The aim of the presented study is to give an integrative picture of the metal bioaccumulation for the entire French territory without geographical gaps. Furthermore, confounding factors of the metal bioaccumulation in mosses should be investigated.     

Compositional fractionation of polycyclic aromatic hydrocarbons (PAHs) in mosses (Hypnum plumaeformae WILS.) from the northern slope of Nanling Mountains,South China

High mountains may serve both as condenser for vapor phase persistent organic pollutants (POPs) and as barrier/sink for particulate associated less volatile POPs. The fractionation of POPs along altitudinal profiles is of interest in understanding the role of high mountains in the atmospheric transport of POPs. In the present study, polycyclic aromatic hydrocarbons (PAHs) in a selected moss species, Hypnum plumaeformae WILS, from two altitudinal profiles on the northern slope of Nanling mountains in Southern China were analyzed and compared with those in air samples. The total PAH concentration in the mosses was 310–1340 ng g⁻¹ dry weight, with phenanthrene being the most abundant. The distribution patterns of PAHs in the moss samples matched well with those in bulk atmosphere deposition in the adjacent source areas. The PAH distribution pattern in the mosses was a composite of both particle-associated and vapor phase PAHs, with heavy PAHs are susceptible to uptake/retention by mosses than light PAHs. A plot of log (C_moss/C_air) against log K_oa gave a good linear relationship in the log K_ao range of 6.7–10.2. It is suggested that the widely spread moss, H. plumaeformae WILS, can be used as an effective tool in the biomonitoring of atmospheric PAHs pollution in East Asia. The concentrations of most PAHs in the mosses generally declined with increasing altitude. In addition, there was a shift in compound pattern with an increase in the proportion of light PAHs (2–3 rings), a decrease in heavy PAHs (5–6 rings) and a relatively stable content of 4-ring PAHs. A combination of particulate scavenging and cold condensation are proposed as the major mechanisms for the compositional fractionation of PAHs along the altitudinal profile.     

Assessing the Impacts of Long-Range Sulfur and Nitrogen Deposition on Arctic and Sub-Arctic Ecosystems

For more than a decade, anthropogenic sulfur (S) and nitrogen (N) deposition has been identified as a key pollutant in the Arctic. In this study new critical loads of acidity (S and N) were estimated for terrestrial ecosystems north of 60° latitude by applying the Simple Mass Balance (SMB) model using two critical chemical criteria (Al/Bc = 1 and ANC_le = 0). Critical loads were exceeded in large areas of northern Europe and the Norilsk region in western Siberia during the 1990s, with the more stringent criterion (ANC_le = 0) showing the larger area of exceedance. However, modeled deposition estimates indicate that mean concentrations of sulfur oxides and total S deposition within the Arctic almost halved between 1990 and 2000. The modeled exceeded area is much reduced when currently agreed emission reductions are applied, and almost disappears under the implementation of maximum technically feasible reductions by 2020. In northern North America there was no exceedance under any of the deposition scenarios applied. Modeled N deposition was less than 5 kg ha⁻¹ y⁻¹ almost across the entire study area for all scenarios; and therefore empirical critical loads for the eutrophying impact of nitrogen are unlikely to be exceeded. The reduction in critical load exceedances is supported by observed improvements in surface water quality, whereas the observed extensive damage of terrestrial vegetation around the mining and smelter complexes in the area is mainly caused by direct impacts of air pollution and metals.     

Long-term changes in nitrogen deposition in Finland (1990–2006) monitored using the moss Hylocomium splendens

Nitrogen deposition in Finland was investigated on the basis of the nitrogen concentration in the forest moss, Hylocomium splendens, collected during heavy metal moss surveys carried out in 1990, 1995, 2000, and 2005/06. Significant regional differences were found in the nitrogen concentrations in mosses. The concentrations were the highest in the southern part of the country in all the surveys, with a decreasing trend on moving northwards. The mean concentrations in the surveys were 1.07%, 1.00%, 0.89% and 0.92%. In general, the concentrations in mosses reflected nitrogen deposition at the level of the whole country. However, they did not correlate very well with the modelled nitrogen deposition because of the high local variation in the nitrogen concentration in H. splendens. One reason for the high variation was the effect of the structure of the tree stand on nitrogen concentrations in H. splendens.     

Historical nitrogen content of bryophyte tissue as an indicator of increased nitrogen deposition in the Cape Metropolitan Area, South Africa

Information on changes in precipitation chemistry in the rapidly expanding Cape Metropolitan Area (CMA) of South Africa is scarce. To obtain a long-term record of N deposition we investigated changes in moss foliar N, C:N ratios and nitrogen isotope values that might reflect precipitation chemistry. Tissue from 9 species was obtained from herbarium specimens collected between 1875 and 2000 while field samples were collected in 2001/2002. There is a strong trend of increasing foliar N content in all mosses collected over the past century (1.32-1.69 %N). Differences exist between ectohydric mosses which have higher foliar N than the mixohydric group. C:N ratios declined while foliar δ¹⁵N values showed no distinct pattern. From relationships between moss tissue N and N deposition rates we estimated an increase of 6-13 kg N ha⁻¹ a⁻¹ since 1950. Enhanced N deposition rates of this magnitude could lead to biodiversity losses in native ecosystems.     

Spatially valid data of atmospheric deposition of heavy metals and nitrogen derived by moss surveys for pollution risk assessments of ecosystems

For analysing element input into ecosystems and associated risks due to atmospheric deposition, element concentrations in moss provide complementary and time-integrated data at high spatial resolution every 5 years since 1990. The paper reviews (1) minimum sample sizes needed for reliable, statistical estimation of mean values at four different spatial scales (European and national level as well as landscape-specific level covering Europe and single countries); (2) trends of heavy metal (HM) and nitrogen (N) concentrations in moss in Europe (1990–2010); (3) correlations between concentrations of HM in moss and soil specimens collected across Norway (1990–2010); and (4) canopy drip-induced site-specific variation of N concentration in moss sampled in seven European countries (1990–2013). While the minimum sample sizes on the European and national level were achieved without exception, for some ecological land classes and elements, the coverage with sampling sites should be improved. The decline in emission and subsequent atmospheric deposition of HM across Europe has resulted in decreasing HM concentrations in moss between 1990 and 2010. In contrast, hardly any changes were observed for N in moss between 2005, when N was included into the survey for the first time, and 2010. In Norway, both, the moss and the soil survey data sets, were correlated, indicating a decrease of HM concentrations in moss and soil. At the site level, the average N deposition inside of forests was almost three times higher than the average N deposition outside of forests.     

Response of stable carbon isotope in epilithic mosses to atmospheric nitrogen deposition

Epilithic mosses are characterized by insulation from substratum N and hence meet their N demand only by deposited N. This study investigated tissue C, total Chl and δ¹³C of epilithic mosses along 2 transects across Guiyang urban (SW China), aiming at testing their responses to N deposition. Tissue C and total Chl decreased from the urban to rural, but δ¹³C_moss became less negative. With measurements of atmospheric CO₂ and δ¹³CO₂, elevated N deposition was inferred as a primary factor for changes in moss C and isotopic signatures. Correlations between total Chl, tissue C and N signals indicated a nutritional effect on C fixation of epilithic mosses, but the response of δ¹³C_moss to N deposition could not be clearly differentiated from effects of other factors. Collective evidences suggest that C signals of epilithic mosses are useful proxies for N deposition but further works on physiological mechanisms are still needed.     

Assessing the recovery potential of alpine moss-sedge heath: reciprocal transplants along a nitrogen deposition gradient

The potential of alpine moss-sedge heath to recover from elevated nitrogen (N) deposition was assessed by transplanting Racomitrium lanuginosum shoots and vegetation turfs between 10 elevated N deposition sites (8.2-32.9 kg ha⁻¹ yr⁻¹) and a low N deposition site, Ben Wyvis (7.2 kg ha⁻¹ yr⁻¹). After two years, tissue N of Racomitrium shoots transplanted from higher N sites to Ben Wyvis only partially equilibrated to reduced N deposition whereas reciprocal transplants almost matched the tissue N of indigenous moss. Unexpectedly, moss shoot growth was stimulated at higher N deposition sites. However, moss depth and biomass increased in turfs transplanted to Ben Wyvis, apparently due to slower shoot turnover (suggested to result partly from decreased tissue C:N slowing decomposition), whilst abundance of vascular species declined. Racomitrium heath has the potential to recover from the impacts of N deposition; however, this is constrained by the persistence of enhanced moss tissue N contents.     

Stable sulphur and nitrogen isotopes of the moss Haplocladium microphyllum at urban,rural and forested sites

Elemental (S and N) and isotopic (δ³⁴S and δ¹⁵N) contents in the moss Haplocladium microphyllum at urban, rural and forested sites in acid rain area of South China have been analyzed for comparisons to show whether they are different and can be effectively used to identify S and N sources of atmospheric deposition. Average moss S content at rural sites (0.29 ± 0.06%) was found to be in between those at urban (0.35 ± 0.05%) and forested (0.25 ± 0.04%) sites, which are significantly different. Average N contents of urban (2.60 ± 0.56%) and rural mosses (2.84 ± 0.77%) are not significantly different, while both are significantly different to that of forested mosses at most areas, indicating that the atmosphere over rural sites has been polluted by N as seriously as that over urban sites. Nitrogen supply, relative to S supply, was in excess of the requirement for protein synthesis, especially at rural and forested sites. Moss stable isotope signatures have been proven to be effective tools for deciphering atmospheric S and N sources at these sites. Through moss δ³⁴S signatures, we found that atmospheric S at urban and forested sites was mainly from local coal combustion and domestic biomass burning, respectively, whereas northerly air masses contributed more S to forested sites. The relatively negative moss δ¹⁵N values (?7.5 ± 3.0, ?3.4 ± 2.1 and ?0.8 ± 2.1‰) demonstrated that the main form in the N deposition was NH_x in these sites. More negative δ¹⁵N signatures in urban mosses (?7.5 ± 3.0‰) indicated the contribution of NH₃ released from untreated city sewage and wastes, while relatively less negative δ¹⁵N for rural and forested mosses (3.4 ± 2.1 and ?0.8 ± 2.1‰) was largely derived from agricultural NH₃.     

δ13C and δ15N of moss Haplocladium microphyllum (Hedw.) Broth. for indicating growing environment variation and canopy retention on atmospheric nitrogen deposition

Mosses have been recognized as a useful tool for biomonitoring atmospheric deposition and assessing regional environment. This study was carried on whether the same moss growing in areas with identical regional atmospheric deposition while under different growing environments would have the same indicating signals.Similar variations in mean δ¹³C and δ¹⁵N signatures were found between mosses collected from five habitats, with an increasing sequence from mosses under canopies to epilithic mosses, indicating that habitats were potentially regulating δ¹³C and δ¹⁵N values of mosses. Dryer habitats (lower water availability) and input of more aerosol N were the main reasons for higher δ¹³C and δ¹⁵N values of mosses at open sites (especially for epilithic species), while more negative values of mosses under canopies were attributed to their wetter habitats and less uptake of aerosol N. Additionally, δ¹⁵N values not δ¹³C varied linearly with canopy thickness from −7.84‰ (1 m) to −4.71±0.7‰ (4 m), suggesting δ¹⁵N was more sensitive for indicating canopy retention.Consequently, isotopic data of mosses under different environments could not be compared for atmospheric deposition research with each other even collected at the same site. Moss δ¹³C and δ¹⁵N were affected not only by regional atmospheric N sources but also by their growing environments. δ¹⁵N of epilithic Haplocladium microphyllum at open sites can be taken as confident bio-indicator of atmospheric N deposition, which would deepen the application of stable nitrogen isotope of bryophytes in atmosphere–plant system study.     

Analyses of platinum group elements in mosses as indicators of road traffic emissions in Austria

The concentrations of platinum group elements (PGE; platinum, palladium, rhodium) and 17 other elements in mosses growing at 32 sampling sites along 12 roads in Austria were analysed. The study included passive monitoring of naturally growing mosses with an experimental design using mosses samples exposed in a tunnel experiment. PGEs (Pt, Pd, Rh) were analysed by ICP-MS (ELAN DRC II, Perkin Elmer SCIEX) according to EN ISO 17294-2 Tl.29. Mean concentrations of PGEs in five moss species were: Pt 7.07±9.97, Pd 2.8±5.2 und Rh 0.6±0.8 ng g⁻¹ dry weight. This is comparable to data derived from measurements of gasoline autocatalyst emissions or airborne particles (<10 μm). Compared to soils and road dust along highways, concentrations in mosses were lower by a factor of ten, compared to grasses they were comparable or somewhat higher. The ratios between the various PGEs were calculated as follows (mean values): Pt/Pd 7.9±10.2, Pt/Rh 12.6±8.3 and Pd/Rh 3.7±2.2. The number of light duty vehicles (<3.5 t) and the distance from the road were the main influential factors for PGE concentrations. Especially strong correlations could be found between Pt and Sb, Cu, Zn, and Cd (in decreasing order), which are all elements derived mainly from road traffic emissions. Cluster analysis (Partioning Around Medoids Method) separated elements derived mainly from soil dust (Ca, Al). An analysis of spatial deposition patterns of PGEs showed a reciprocal decrease of concentrations with increasing distance from the road, reaching background values at distances between 10 and 200 m, sometimes even more, but outside the spatial range of our investigation.     

Base cation deposition in europe-part I. Model description, results and uncertainties

Deposition of base cations (Na⁺, Mg²⁺, Ca²⁺, K⁺) in Europe was mapped for 1989 with a spatial resolution of 10 x 20 km using the so-called inferential modeling technique. Deposition fields resembled the geographic variability of sources, land-use and climate. Dry deposition constituted on average 45% of the total base cation deposition in Europe. Modeled deposition estimates compared reasonably well with deposition estimates derived from throughfall and bulk-precipitation measurements made at 174 sites scattered over Europe. Using error propagation, the random and systematic error in total deposition for an average grid cell of 10 x 20 km was estimated to equal 35–50% and 25–40%, respectively. Within individual grids a relatively large variability in deposition is expected.     

Interspecies and interregional comparisons of the chemistry of PAHs and trace elements in mosses Hylocomium splendens (Hedw.) B.S.G. and Pleurozium schreberi (Brid.) Mitt. from Poland and Alaska

Comparative biogeochemical studies performed on the same plant species in remote areas enable pinpointing interspecies and interregional differences of chemical composition. This report presents baseline concentrations of PAHs and trace elements in moss species Hylocomium splendens and Pleurozium schreberi from the Holy Cross Mountains (south-central Poland) (HCM) and Wrangell–Saint Elias National Park and Preserve (Alaska) and Denali National Park and Preserve (Alaska). Total PAH concentrations in the mosses of HCM were in the range of 473–2970 μg kg^?1 (dry weight basis; DW), whereas those in the same species of Alaska were 80–3390 μg kg^?1 DW. Nearly all the moss samples displayed the similar ring sequence: 3 > 4 > 5 > 6 for the PAHs. The 3 + 4 ring/total PAH ratios show statistically significant differences between HCM (0.73) and Alaska (0.91). The elevated concentrations of PAHs observed in some sampling locations of the Alaskan parks were linked to local combustion of wood, with a component of vehicle particle- and vapor-phase emissions. In HCM, the principal source of PAH emissions has been linked to residential and industrial combustion of coal and vehicle traffic. In contrast to HCM, the Alaskan mosses were distinctly elevated in most of the trace elements, bearing a signature of the underlying geology. H. splendens and P. schreberi showed diverse bioaccumulative capabilities of PAHs in all three study areas.     

Temporal trends (1990-2000) in the concentration of cadmium, lead and mercury in mosses across Europe

The European heavy metals in mosses survey provides data on the concentration of 10 heavy metals in naturally growing mosses. The survey has been repeated at five-yearly intervals and in this paper we report on the temporal trends in the concentration of cadmium, lead and mercury between 1990 and 2000. Metal- and country-specific temporal trends were observed. In general, the concentration of lead and cadmium in mosses decreased between 1990 and 2000; the decline was higher for lead than cadmium. For mercury not enough data were available to establish temporal trends between 1990 and 1995, but between 1995 and 2000 the mercury concentration in mosses did not change across Europe. The observed temporal trends for the concentrations in mosses were similar to the trends reported for the modelled total deposition of cadmium, lead and mercury in Europe.     

Use of mosses to study atmospheric deposition of trace elements: contributions from investigations in Norway

This paper presents essential features of biomonitoring work carried out in the author's laboratory during more than 25 years using various analytical techniques for the determination of over 50 elements. A substantial part of this work concerns large-scale deposition surveys in Norway using the moss Hylocomium splendens, where five nationwide surveys have been carried out since 1977. Considerable efforts have also been spent on intercalibration of different species of mosses and transformation of concentrations in moss to absolute deposition rates. Other significant activities include establishment of recommended values for moss reference samples, source apportionment of lead in mosses by stable isotope ratios and monitoring of local metal deposition around factories. Experience from this work has facilitated a critical evaluation of the contribution from sources other than atmospheric deposition to the elemental composition of the moss, as well as factors leading to depletion of elements in the moss. Recent work indicates that mosses may also be suitable for the monitoring of persistent halogenated organic pollutants and ¹³⁷Cs deposition.     

Modelling atmospheric mercury transport and deposition across Europe and the UK

There are inadequate measurements of surface ambient concentrations of mercury species and their deposition rates for the UK deposition budget to be characterized. In order to estimate the overall mercury flux budget for the UK, a simple long-term 1D Lagrangian trajectory model was constructed that treats emissions (1998), atmospheric transformation and deposition across Europe. The model was used to simulate surface concentrations of mercury and deposition across Europe at a resolution of 50 km×50 km and across the UK at 20 km×20 km. The model appeared to perform adequately when compared with the few available measurements, reproducing mean concentrations of elemental gaseous mercury at particular locations and the magnitude of regional gradients. The model showed that 68% of the UK's mercury emissions are exported and 32% deposited within the UK. Of deposition to the UK, 25% originates from the Northern Hemisphere/global background, 41% from UK sources and 33% from other European countries. The total mercury deposition to the UK is in good agreement with other modelling, 9.9 tonne yr⁻¹ cf. 9.0 tonne yr⁻¹, for 1998. However, the attribution differs greatly from the results of other coarser-scale modelling, which allocates 55% of the deposition to the UK from UK sources, 4% from other European countries and 60% from the global background atmosphere. The model was found to be sensitive to the speciation of emissions and the dry deposition velocity of elemental gaseous mercury. The uncertainties and deficiencies are discussed in terms of model parameterization and input data, and measurement data with which models can be validated. There is an urgent requirement for measurements of removal terms, concentrations, and deposition with which models can be parameterized and validated.