Are cadmium, lead and mercury concentrations in mosses across Europe primarily determined by atmospheric deposition of these metals?

Purpose

This study aimed at investigating correlations between heavy metal concentrations in mosses and modelled deposition values as well as other site-specific and regional characteristics to determine which factors primarily affect cadmium, lead and mercury concentrations in mosses. The resulting relationships could potentially be used to enhance the spatial resolution of heavy metal deposition maps across Europe.

Materials and methods

Modelled heavy metal deposition data and data on the concentration of heavy metals in naturally growing mosses were integrated into a geographic information system and analysed by means of bivariate rank correlation analysis and multivariate decision trees. Modelled deposition data were validated annually with deposition measurements at up to 63 EMEP measurement stations within the European Monitoring and Evaluation Programme (EMEP), and mosses were collected at up to 7,000 sites at 5-year intervals between 1990 and 2005.

Results and discussion

Moderate to high correlations were found between cadmium and lead concentrations in mosses and modelled atmospheric deposition of these metals: Spearman rank correlation coefficients were between 0.62 and 0.67, and 0.67 and 0.73 for cadmium and lead, respectively (p?<?0.001). Multivariate decision tree analyses showed that cadmium and lead concentrations in mosses were primarily determined by the atmospheric deposition of these metals, followed by emissions of the metals. Low to very low correlations were observed between mercury concentrations in mosses and modelled atmospheric deposition of mercury. According to the multivariate analyses, spatial variations of the mercury concentration in mosses was primarily associated with the sampled moss species and not with the modelled deposition, but regional differences in the atmospheric chemistry of mercury and corresponding interactions with the moss may also be involved.

Conclusions

At least for cadmium and lead, concentrations in mosses are a valuable tool in determining and mapping the spatial variation in atmospheric deposition across Europe at a high spatial resolution. For mercury, more studies are needed to elucidate interactions of different chemical species with the moss.     

Comparison of biological collectors of airborne heavy metals near ferrochrome and steel works

The value of several biological monitors of the distribution of airborne Cr and Ni dust was studied in the vicinity of ferrochrome and stainless steel works. The following indigenous biomonitors were compared: the forest mosses Pleurozium schreberi and Hylocomium splendens, the epiphytic lichen Hypogymnia physodes, bark of Scots pine (Pinus silvestris), needle litter, earthworms (Dendrobaena octaedra) and moths (mainly Xylena vetusta). Results were compared and related to the heavy metal deposition estimated by the vertical snow sampling method. The representative sampling size at different pollution levels was investigated. In Cr it varied from 1 to 300 mg m^?2 a^?1. Of the biomonitors studied, the mosses showed most effective accumulation of heavy metals, their results having a clear relationship to the deposition and good replicability. The lichen gave almost as good results as the mosses. Both mosses and lichens collected heavy metals more effectively at low to moderate pollution loads than near the pollution source. The accumulation of heavy metals in bark was lower than in the mosses or lichen. The heavy metal content of earthworms indicated the degree of pollution well, but the replicability of the method was poor. The accumulation of heavy metals in moths was low.     

The Geochemistry of Ombrotrophic Sphagnum Species Growing in Different Microhabitats Of Eight German and Belgian Peat Bogs and the Regional Atmospheric Deposition

Comparing today’s atmospheric deposition records with the elemental concentration and the net-uptake rates of ombrotrophic Sphagnum mosses from eight German and Belgian peat bogs revealed that most of all the quality and number of regularly obtained deposition monitoring data is not satisfactory. Moreover, it seems likely that the deposition rate, determined by Sphagnum mosses, does not reliably reflect the record of the total open field deposition indicated by the deposition monitoring data. The moss data, too, show a distinct spatial variability possibly because the geochemistry of peat mosses differs according to the annual growth in height, the total surface area and the surface roughness of the receptor ‘peat moss’ (special interception deposition). Increased Ti concentration values, for example, combined with a high annual growth rate in height at the hollow moss S. cuspidatum resulted in generally high Ti net-uptake rates and a high Ti inventory (total Ti in sample). We, therefore, suggest that productive Sphagnum species might be able to fix more Ti particles on their larger surface area than less productive species do. Moreover, the results demonstrate that for reliably calculating Sphagnum elemental net-uptake rates, as well as for all quantification of Sphagnum or peat geochemistry on a time and area basis, an accurate knowledge of the period the collected samples were exposed to atmospheric deposition is required. In particular, to do reliable reconstructions of past atmospheric deposition rates using peat deposits, further studies are needed to precisely specify the spatial variability in the geochemistry of living Sphagnum mosses.     

The Spatial Distribution of Characterised Fly-Ash Particles and Trace Metals in Lake Sediments and Catchment Mosses: Ireland

Spheroidal carbonaceous particles (SCPs) from the sediments of 48 Irish lakes were enumerated and characterised according to fuel type. The concentration of metals was determined in the surface sediments and in selected mosses from the catchments of these lakes. Generally the metal concentrations in both the surface sediments and mosses were consistent with background levels found in the remote parts of Europe. Where higher metal concentrations occurred these could often be accounted for by local geochemical sources. SCP levels in the sediments of the selected lakes along the east coast were of sufficient magnitude to suggest a transboundary influence notwithstanding local sources. SCP characterisation also suggests the influence of emissions in Northern Ireland on deposition, particularly in the north-west of Ireland. There was reasonable correlation between the concentration of oil particles in the surface sediments and vanadium, but not with nickel, in mosses. SCP concentrations were not correlated with measured physical characteristics of the lakes. The level of deposition indicated is not likely to have a significant impact on human health over and above the damaging effects of urban dwelling but the adverse impact of this deposition on acid-sensitive surface waters in Ireland has been recorded.     

Estimation method of residual alkylating agents in water treated with chloring-containing oxidant

Concentrations of trace metals in mosses Hylocomium splendens (Hs) and Pleurozium schreberi (Ps) are compared along with wet deposition at 8 sites in Sweden. Cd, Mn, Zn and Cr concentrations were similar in both mosses, while Cu, Fe, Pb, Ni and V levels were 14 to 24% higher in Hs than in Ps. The comparison to wet deposition estimates indicates that concentrations in mosses are also influenced by other factors than the adsorption of precipitation. No correlation was observed between the wet deposition of Mn, Cr and Ni and moss concentrations.     

The use of moss,lichen and pine bark in the nationwide monitoring of atmospheric heavy metal deposition in Finland

Mosses, lichens and pine bark were compared as indicators of atmospheric heavy metal deposition in Finland. The samples were collected from the nationwide sampling network systematically covering the country as a whole. All three bioindicators showed a fairly similar result concerning heavy metal deposition. The major emission sources and the areas affected were reflected in the metal concentrations in the samples. However, there were differences between the accumulation of metals. The correlation between concentrations in mosses and lichens was generally higher than that between mosses and bark or lichens and bark. Concentrations in lichens were the highest and lichens reflected the regional differences in background areas as well as the local emission sources. The concentrations in the mosses were slightly lower than those in lichens and also the mosses pinpointed the emission sources and the extend of the areas polluted. Bark had the lowest concentrations and bark did not generally reveal regional differences as well as mosses and lichens. In spite of the differences, all three bioindicators proved to be suitable for monitoring atmospheric heavy metal deposition.     

Metals in small Norwegian lakes: Relation to atmospheric deposition of pollutants

Water chemistry data from 165 lakes in Norway are discussed in relation to contribution from long-range transported air pollutants. Concentrations of lead and antimony in terrestrial mosses are used to express the relative contribution from long range transport to each lake. The contents of Al and Zn in lake water and of ‘excess’ SO₄ in low Ca lakes show high correlations with the relative heavy metal deposition values from moss analysis. The ‘excess’ SO₄ in low Ca lakes correlates strongly with Al and too a lesser extent with Mn and Fe. It is suggested that the lake water levels of Al and Mn, and even to some extent Fe, are significantly affected by acidic precipitation enhancing the leaching of these metals from mineral matter in soils and sediments. In the case of Zn, airborne supply to the lakes and their catchments appears to strongly affect the water content.     

Statistical models for the accumulation of PAH,chlorinated hydrocarbons and trace metals in epiphytic Hypnum cupressiforme

Concentrations of PAH (1.12-benzoperylene, 3.4-benzopyrene, fluoranthene), chlorinated hydrocarbons (α-BHC, lindane, PCB) and trace metals (Zn, Pb, Cu) in bulk precipitation, as well as PAH and trace metal concentrations in atmospheric dust samples from 14 sites in Bavaria, F.R.G. are presented for two vegetation periods (1979 and 1980). The same substances were also analyzed in epiphytic moss (Hypnum cupressiforme var. filiforme) sampled from tree trunks in October 1979 and 1980. Using mean immission values and the amount of precipitation as predictors and concentrations of pollutants in moss samples as criteria, a number of multiple regression models were computed in order to quantify the relationships between absolute air pollution data and accumulated trace substance values. Beta values of all variables help to determine whether bulk precipitation or atmospheric particulate matter has dominant influence on the uptake of trace substances by mosses. The study shows that epiphytic mosses can be used to monitor both heavy-metal, PAH and chlorinated hydrocarbons.     

A Comparison of Temporal Patterns in Trace Metal Concentration in Tree Rings of Four Common European Tree Species Adjacent to a Cu-Cd Refinery

Metal processing at a Cu-Cd refinery at Prescot in N.W. England has led to severe contamination of the surrounding soils and vegetation, although Cu and Cd in bulk deposition declined dramatically between 1975 and 1990. Despite high spatial and temporal variability in metal deposition, mean Cd concentrations in annual tree rings of sycamore (Acer pseudoplatanus L.), lime (Tilia europaea L.) and beech (Fagus sylvatica L.) at Prescot were correlated with annual bulk Cd deposition. In contrast, mean Cd concentrations in ash (Fraxinus excelsior L.) were unrelated to Cd deposition and there was no significant relationship between mean Cu concentrations in tree rings and Cu deposition in any species. Mean Pb concentrations in sycamore, lime and beech at Prescot and the reference site also decreased over time. At Prescot however, Cd concentrations in tree rings formed in the mid 1990s were up to 10-fold higher than the reference site despite Cd deposition values during this period that were typical of levels expected for urban areas in the UK. The high Cd concentrations in wood during this period indicate that the majority of Cd in tree rings at Prescot is derived from soil, limiting the usefulness of dendrochemistry for monitoring temporal changes in metal deposition. It appears that trees are not simply passive recorders of metal deposition and other possibilities, in addition to decreasing atmospheric deposition, may explain the patterns of Cd and Pb found in sycamore, lime and beech. More research on the physiology of metal cycling in trees is required before dendrochemical techniques can be applied with confidence in environmental monitoring programs.     

Mechanisms for Translocation of Heavy Metals from Soil to Epigeal Mosses

The mechanisms for translocation of heavy metals from soil to epigeal mosses were investigated. The first mechanism was demonstrated for ¹³⁷Cs and involved the uplifting of the pollutant-containing dust from the soil, followed by the local secondary deposition on surfaces of epigeal mosses and epiphytic lichens. The second mechanism involved the diffusion of metal cations from the soil through water wetting the moss into the gametophyte. The mechanism was demonstrated by measuring the electric conductance of wetted gametophytes with single ends immersed in solutions of Cu and Na salts. In addition, the concentrations of Cu and Cd were compared in moss samples exposed to the natural soil and to the soil contaminated with the metals. The exposition to the contaminated soil resulted in the statistically significant increase of metal concentrations in the gametophytes.     

An index of atmospheric pollution survey in Armadale,Central Scotland

A modified ‘Index of Atmospheric Pollution’ (I.A.P.) survey was carried out in December 1980/January 1981, in Armadale, Central Scotland. The purpose of this survey was to obtain a general picture of the pollution pattern within Armadale and an information base necessary for future detailed metal pollution surveys. The results revealed four different pollution zones in Armadale, with the most polluted zone being in the vicinity of the steel foundry; all zones were slightly elongated in the direction of the main wind axis. These zones probably reflected a combination of the foundry pollution and, to a lesser extent, of the SO₂ pollution from domestic coal combustion. Following on from the I.A.P. survey, several metal pollution studies were carried out within Armadale, one of which has been briefly introduced in this article purely for comparison with the I.A.P. survey. The averages of site metal values inHypnum cupressiforme in each I.A.P. zone were calculated. Both the lichens and mosses in the I.A.P. survey and the indigenousHypnum in the subsequent metal pollution study had been exposed to Armadale's air pollution for several years. Hence, it was thought logical to compare the spatial relationship of the metal zone values to the I.A.P. values in order to determine whether or not metal pollution was playing a role in the formation of the four zones of the I.A.P. survey in Armadale; nevertheless it was considered that further comparisons with subsequent metal pollution studies in Armadale would be necessary before definitive conclusions could be drawn.     

The Spatial Distribution of Characterised Fly-Ash Particles and Trace Metals in Lake Sediments and Catchment Mosses in the United Kingdom

Spheroidal carbonaceous particles (SCP) and trace metals (Cd, Cu, Pb, Ni, V and Zn) were analysed from 75 lake surface sediments across the UK. Trace metals were additionally analysed from catchment mosses (Hylocomium splendens and Pleurozium schreberi) from 43 of the sites but were absent from the remainder. Spatial distribution of SCP concentration and trace metal concentrations in sediments and mosses showed good agreement with each other and with known emission sources. Particles were allocated to their fuel-type and spatial trends in these data showed good agreement with potential sources. High areas of oil particle deposition were identified in the south-east of England, Merseyside, Galloway / Northern Ireland, the Firth of Forth and eastern Scotland. Oil SCP concentrations showed good agreement with Ni and V concentrations in mosses suggesting an atmospheric source for these metals from the combustion of this fuel. Characterised SCP trends also showed good agreement with predictions from models such as HARM and EMEP. Most high deposition areas of metals and particles were found to coincide with population centres suggesting a possible impact on human health.     

The Spatial Distribution of Characterised Fly-Ash Particles and Trace Metals in Lake Sediments and Catchment Mosses: Estonia

The concentrations of fly-ash particles were studied in the surface sediments of 42 lakes in Estonia. Concentrations of both spheroidal carbonaceous particles (SCPs) and inorganic ash spheres (IASs) were determined and the particles chemically characterised to different fuel types. This was accompanied by trace metal analyses from lake surface sediments and catchment mosses in order to determine the distribution of atmospheric pollutants. The obtained spatial distribution data for fly-ash particles varied to a great extent, partly due to differences in sedimentation rates but mainly due to higher deposition in industrial areas. The distribution patterns of the different particle types in lake sediments, as well as the trace metals in mosses, show that the deposition of airborne particulates is of local origin around pollution sources and that the share of long-range transported atmospheric impurities is high along the main cyclonic routes in Estonia.     

Accumulation of Cadmium,Chromium, and Zinc by the Moss Sphagnum Papillosum Lindle

In a series of laboratory experiments employing radiotracer methodology, the uptake of Cd,Cr, and Zn by Sphagnum papillosum Lindle moss from solutions of deionized water and bogwater was investigated. Bioaccumulation of the metals was a passive process, since living anddead moss accumulated metal equally. No significant differences were found in metal uptake ratesfrom single metal solutions and mixed metal solutions, suggesting insignificant competitionbetween the metals occurred at the low concentration range used (10-10 to 10-7 M). Metaluptake conformed with Freundlich adsorption isotherms. Concentration factors of metals inSphagnum papillosum in bog water (103 for Cd and Zn, 102 for Cr) were lower than in deionizedwater (104 for Cd and Zn, 103 for Cr), possibly due to metal complexation by dissolved organicmatter, competition by other major cations present in the bog water (Na+, K+, Mg2+, Ca2+) orcomplexation by chlorides in the bog water. While earlier studies have demonstrated the potentialof using sphagnum mosses for monitoring environmental metal contamination, these experimentsare the first to assess metal uptake in moss using low, environmentally realistic metalconcentrations. The results confirm that mosses would be very effective bioindicators ofenvironmental metal concentrations because the concentration of metal in the moss rapidly anddirectly reflects the metal concentrations in the ambient water.     

Aquatic mosses for the detection and follow-up of accidental discharges in surface waters

Aquatic mosses have been used to study four accidental discharges of the heavy metals Cd, Zn and Hg or the chlorinated hydrocarbons pentachlorophenol (PCP) and lindane in highly contrasting river types. Hg, PCP and lindane moss concentrations reached 880, 4500 and 350 ng g^?1, respectively. In the case of Cd and Zn, water samples and transferred bioindicators were taken simultaneously throughout an accidental discharge. The very high dissolved metal concentrations reached during this accident (9 mg L^?1 Zn, 90 μg L^?1 Cd) induced accumulation by the mosses of up to 28 mg g^?1 for Zn and 225 μg g^?1 for Cd. The increase in concentrations in the mosses was as rapid and substantial as in the water, the time lag due to accumulation kinetics being almost zero. On the other hand, the memory effect enabled mosses to retain marked evidence of Cd, Zn, Hg, PCP and lindane up to 13 days after the accident when difference from background levels can hardly be detected in the water. The four case studies, which killed fish, but not the mosses, show that the previously established scales of quality based on the analysis of aquatic mosses are well suited to estimating the potential damage to the aquatic ecosystem as a whole.     

The Flame Research Project: Introduction and Methods

The FLAME (FLy-Ash and Metals in Europe: Implications for human and environmental health) research project funded by the EU COPERNICUS programme ran from 1994 to 1996. The main aims of the programme were to further develop an automated chemical characterisation to discriminate between fly-ash particles from the major fossil-fuels used throughout Europe (coal, oil, peat, brown coal and oil shale) and apply this to particles extracted from lake sediments taken from the four participating countries (Estonia, Czech Republic, Ireland and U.K.) in order to determine spatial distributions of deposited particulates from large combustion sources. In combination with trace metal analyses from lake surface sediments and catchment mosses, the fly-ash particle data were able to identify areas of elevated pollutant deposition and suggest potential sources for them. Given the transboundary nature of the pollutants, the techniques and results of FLAME are of relevance throughout Europe. Other papers in this volume describe results and interpretation. This paper describes the background and aims of the FLAME project, outlines the methods employed for sampling sediments and mosses and the analytical techniques for particle enumeration and trace metal analysis for sediments and mosses. Finally brief details of the particle characterisation are given showing how a hierarchical discriminant function was developed, based on energy dispersive spectroscopy (EDS) derived particle chemistry which correctly allocated particles from the five fuel-types with 80% accuracy.     

Occurrence and infectivity of arbuscular mycorrhizal fungi in some norwegian soils influenced by heavy metals and soil properties

Mycorrhizae are ubiquitous symbiosis which can mediate uptake of some plant nutrients. In polluted soils they could be of great importance in heavy metal availability and toxicity to plants. Mycorrhizae have also been reported to protect plants against toxic metals. We investigated the occurrence and infectivity of arbuscular mycorrhizal (AM) spores as affected by heavy metal levels and other soil properties in Norwegian soils collected from heavy metal polluted, high natural background and non-polluted areas. Spore numbers, mycorrhizal infectivity and spore germination of indigenous mycorrhizal fungi and of a reference strain (Glomus mosseae) in soils showed lower values in two soils with high metal concentrations and in one soil with a low pH. Mycorrhizal infectivity was negatively correlated with extractable metals. Spore number and mycorrhizal infectivity in a soil with naturally high heavy metal content were not different to in non-polluted soils, and indigenous AM fungi appeared more tolerant to metals than those in non-polluted soils. Mycorrhizal infectivity, expressed as MSI₅₀ values, was significantly correlated (r′=0.89, P< 0.05) with the percentage of germinating G. mosseae spores in the soils. However, the number of spores per volume of soil was not significantly correlated with infectivity or spore germination of the reference strain. The spore germination method is discussed as a bioassay of heavy metal toxicity in soil.     

Growth and Metal Accumulation of Geyer and Mountain Willow Grown in Topsoil versus Amended Mine Tailings

Willows (Salix spp.) are an integral component in the restoration of wetland plant communities that have been impacted by the fluvial deposition of mine tailings. A greenhouse study was conducted to compare growth and metal uptake of Geyer (S. geyeriana) and mountain (S. monticola) willow grown in topsoil versus lime and biosolids amended mine tailings. Biomass, leader length, and tissue metal contents were measured after four months growth. Above and belowground biomass and leader length of Geyer willow were greater for plants grown in topsoil compared to amended mine tailings. However, soil type did not affect mountain willow growth. Analysis for five metals yielded complex results for the two willow species and soil types. As compared to mountain willow, Geyer had greater concentrations of Mn and Pb in aboveground tissues, and Cu in senesced leaves and bark-less leaders when grown in tailings; mountain willow leaves contained greater levels of Cd than Geyer when grown in tailings. Both willow species had foliar Cd levels which were above livestock toxicity tolerance values. Based on growth characteristics, mountain willow appeared better suited for restoration of mine tailings compared to Geyer willow. However, because of the high Cd uptake by both willow species, care should be taken in restoration efforts where wildlife and domestic livestock are likely to browse on the willows.     

Specifics and Temporal Changes in Air Pollution in Areas Affected by Emissions from Oil Shale Industry, Estonia

Atmospheric air pollution levels and long-term effects on the environment caused by simultaneous presence of SO₂ and oil shale alkaline fly ash during the last five decades (since 1950) were investigated. The annual critical value of SO₂ for forest (20 µg m^?3) was surpassed in 1% (～35 km²) of the study area where the load was 30–40 µg m^?3. No effect of long-term SO₂ concentrations of up to 10–11 µg m^?3 (0.5-h max up to 270 µg m^?3) and simultaneous fly ash loads of up to 95 µg m^?3 (1000 µg m^?3) on the growth and needle longevity of Pinus sylvestris was established. The yearly deposition (average load up to 20–100 kg S ha^?1) was alkaline rather than acidic due to an elevated base cation deposition in 1960–1989. Since 1990, the proportion of SO₂ in the balance of components increased: about 70–85% of the total area was affected while the ratio of annual average concentrations of SO₂ to fly ash was over 1. The limit values of fly ash for Sphagnum mosses and conifers in the presence of SO₂ are recommended.     

Trace Metals in Forest Soils at Four Sites in Southern China

Industrial development has increased fast in China the last decades. This has led to a range of environmental problems. Deposition of heavy metals to forest ecosystems via the atmosphere is one potential problem. In this paper we report results from a pilot study where the heavy metal levels in forest soils at four different sites have been measured. Three of the sites are located relatively close to the large cities Chongqing, Guiyang and Guangzhou; one site is located in a remote, mountainous area in Guizhou province. Total metal contents as well as fractions according to Tessier's scheme were determined. With a few exceptions, the metal concentrations can be characterized as low; i.e. in most cases within the range of what has been reported as typical background values in the literature. High content of arsenic (up to 100 ppm) was found in the samples from the site outside Guangzhou, most likely due to naturally high arsenic levels in the soil. Metals bound to organic matter and to iron- and manganese oxides were the dominant fractions. No clear differences in metal levels were found between topsoil and subsoil samples, indicating that the atmospheric deposition of heavy metals has been low.