Determination of baseline element composition of lichens using samples from high elevations

The results of a survey aimed at providing baseline element composition of lichens from unpolluted or very low polluted areas are reported. Lichen samples collected at high elevation areas in Himalayas (Nepal), Mt. Kenya (Kenya) and the Alps (Italy) were analyzed for their trace element content, mostly by INAA, allowing for a multi-element analysis. The elemental composition of lichen samples was essentially influenced by natural occurrence, mainly airborne soil dust. However, also anthropogenic input determined by long-distance atmospheric transport of pollutants was involved for some highly volatile elements such as Br, Cd and Sb. To avoid the influence of soil contamination and air pollution, and obtain baseline concentrations to be used as reference (the "natural" elemental composition of lichens), the average of the lowest concentrations is suggested.     

Comparison between the accumulation capacity of four lichen species transplanted to a urban site

The capacity to accumulate trace elements from the atmosphere of the lichens Hypogymnia physodes, Parmelia sulcata, Pseudevernia furfuracea and Usnea gr. hirta transplanted to an urban site of N Italy was compared. Twenty-nine elements (Al, As, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Fe, Hg, I, K, La, Mg, Mn, Ni, Pb, Rb, Sb, Sc, Se, Sm, Th, Ti, V, Zn) were analyzed by Instrumental Neutron Activation Analysis (INAA) and Electro-Thermal Atomic Absorption Spectroscopy (ET-AAS). The ratio between the concentrations of each element in exposed samples to that of control samples (exposed-to-control ratio and EC ratio) was used to investigate the accumulation rates of lichen thalli. The results showed that in general elements did not exhibit well defined trends, but rather showed fluctuations, and indicated that H. physodes, P. furfuracea and U. gr. hirta have a similar accumulation capacity, while that of P. sulcata is lower.     

Metal homeostasis in Hypogymnia physodes is controlled by lichen substances

The hypothesis was tested that the lichen substances produced by the epiphytic lichen Hypogymnia physodes control the intracellular uptake of divalent transition metals. Incubating lichen thalli with and without their natural content of lichen substances with metal solutions showed that the lichen substances of H. physodes selectively inhibit the uptake of Cu(2+) and Mn(2+), but not of Fe(2+) and Zn(2+). Such behavior is ecologically beneficial, as ambient concentrations of Cu(2+) and Mn(2+) in precipitation and bark are known to limit the abundance of H. physodes, whereas limiting effects of Fe(2+) or Zn(2+) have never been found. This suggests that increasing the Cu(2+) and Mn(2+) tolerance stimulated the evolution of lichen substances in H. physodes. The depsidone physodalic acid is apparently most effective at reducing Cu(2+) and Mn(2+) uptake among the seven lichen substances produced by H. physodes. Probably lichen substances play a general role in the metal homeostasis of lichens.     

Baseline concentrations of elements in the Antarctic macrolichen Umbilicaria decussata

Total concentrations of major and trace elements were determined in samples of the epilithic lichen Umbilicaria decussata from 24 ice-free areas in coastal Victoria Land (Antarctica). Overall average concentrations of trace elements except Cd were the lowest ever reported for lichens of the genus Umbilicaria. Specifically, the mean level of Pb in lichens from granitic rocks (0.46 +/- 0.18 microg g(-1) dry wt) was more than four times lower than the lowest record in Arctic lichens. No impact of local human activities was detected, but the elemental composition of U. decussata was affected by entrapment of soil or rock dust particles and probably by uptake of soluble elements from substrate. Relationships between elements and their distribution patterns in the study area indicated that the marine environment is the main source of major ions and perhaps of Cd in lichens. Accumulation of P was detected in samples from coastal sites frequented by seabirds. Although the present results can be taken as baseline levels of major and trace elements in Antarctic U. decussata from substrates with very different geochemical features, further research is necessary to evaluate the relative element contribution from each substrate with respect to those from snow, marine aerosol, salt encrustations and guano.     

Bioaccumulation behaviour of transplants of the lichen Flavoparmelia caperata in relation to total deposition at a polluted location in Portugal

This experiment compares the short and long time element accumulation behaviour of transplants of Flavoparmelia caperata lichen thalli and total deposition in an atmospheric polluted area. It was found that lichens exposed for a short time behaved differently from lichens in cumulative exposition suggesting the presence of acclimatization behaviour. The lichen transplant elemental content does not unequivocally represent the average or cumulative environmental availability of the exposure period. Reflection characteristics depend on the element and the lichen physiological conditions. Good correlations between lichen elemental contents and total deposition were obtained when a physiological lichen parameter was introduced in a mathematical model, suggesting that metabolically mediated accumulation is important.     

Relationship between epiphytic lichens, trace elements and gaseous atmospheric pollutants

A study was conducted to determine the joint effect of gaseous atmospheric pollutants and trace elements on epiphytic lichens. We used our data to test the hypothesis that lichens are generally insensitive to toxic effects of trace elements, and can therefore be used as accumulator organisms to estimate concentrations of these elements in the environment. In a field study in The Netherlands the abundance of epiphytic lichen species was estimated, and their supporting bark was collected. Concentrations of a range of trace elements were determined in the bark, and concentrations of atmospheric trace gases were estimated at the sites of collection. Multivariate statistics were used to determine the relation between the abundance of the species and pollutant concentrations. Atmospheric SO2 and NO2 appeared to be the most important factors determining lichen biodiversity. Nearly all species were sensitive to these compounds. The effect of the other trace elements was very slight; only Sb had a significantly negative effect on the abundance of a few species. It is concluded that lichens can safely be used as accumulator organisms in pollution studies, provided that concentration in lichen thalli reflect atmospheric concentrations.     

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.     

Monitoring air quality with lichens: a comparison between mapping in forest sites and in open areas

Four different methods of epiphytic lichen mapping were used for the assessment of air quality in the region under the influence of the Sostanj Thermal Power Plant (Salek Valley, Slovenia). Three methods were based on the presence of different lichen species (VDI, EU and ICP-Forest), the fourth on a frequency and coverage assessment of different growth forms of epiphytic lichens, e.g. crustose, foliose and fruticose (SI). A comparison of the results from the assessment of air quality between forest sites (ICP-Forest, SI) and open areas (VDI, EU and SI), obtained by the different methods of epiphytic lichen mapping, is presented in the contribution. Data showed that lichen species richness is worse in forest sites in comparison with open areas. From the data obtained it can be concluded that epiphytic lichen mapping in open areas is a better method for the assessment of air pollution in a given area than mapping in forest sites. The species-based methods in open areas are more powerful and useful for air quality assessment in polluted research areas than the SI and ICP-Forest methods.     

Iron content and its relations to the sulphur and titanium contents of epiphytic and terricolous lichens and pine bark in Finland

The iron content was studied in the epiphytic lichens Hypogymnia physodes (L.) Nyl. and Pseudevernia furfuracea (L.) Zopf, in the terricolous lichens Cladina sp. and Peltigera aphthosa (L.) Willd., and in pine bark collected from 31 sites in Finland. There appeared to be differences between lichen species, epiphytes having generally higher concentrations. The iron content of H. physodes was highly significantly correlated (p<0.001) with its sulphur content, reflecting the relations of these elements in precipitation. The highly significant correlations between the iron and titanium contents indicated differences of the phorophytes. The iron/sulphur ratio of H. physodes on pine was 1.3 and on birch 1.4 and iron/titanium ratios were 10.4 and 11.3 respectively. The iron content of Cladina sp. showed highly significant parallel correlations (p<0.001) with its sulphur and titanium contents. The iron/titanium ratio decreased from 9.6 to 8.2 when the iron content increased by 95%, the sulphur content being equal. The iron/titanium ratio of Cladina sp. was nearly identical to that of P. furfuracea. The relation between iron and sulphur, and the fraction of soluble and insoluble iron in precipitation versus lichens and pine bark were considered. Special attention was paid in the discussion to differences in substrate: pine and birch bark for H. physodes, and soil for Cladina sp.     

Influence of angular exposure and proximity to vehicular traffic on the diversity of epiphytic lichens and the bioaccumulation of traffic-related elements

This study investigated the influence of angular exposure and distance from vehicular traffic on the diversity of epiphytic lichens and the bioaccumulation of traffic-related elements in a town of central Italy. An Index of Lichen Diversity (ILD) was calculated on the street-facing and the opposite side of road-lining trees and in a urban park 250 m away, and the content of selected trace elements (Al, Ba, Ce, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V, and Zn) was determined in samples of the lichen Punctelia borreri (Sm.) Krog growing on tree bark, both on the exposed and opposite sides. ILD increases with distance from traffic emissions. However, at the site with vehicle traffic, non-nitrophilous lichens decreased while nitrophilous ones increased. The concentration of the traffic-related elements Ba, Cr, Cu, Mn, Sb, and Zn accumulated in thalli of P. borreri was higher on roadside trees than in trees from the urban park. ILD was not affected by the angular exposure to the road and the bioaccumulation of traffic-related elements was similar in lichens from the side of the bole exposed to traffic emissions and particulate resuspension and from the opposite side. The angular exposure in respect to the traffic source does not influence trace element accumulation. These results are important when using lichens for biomonitoring purposes, both for planning future studies and for the reliability of the interpretation of past surveys that do not report information about the angular exposure of the collected lichen material.     

Sulphur isotope composition of epiphytic and terricolous lichens and pine bark in Finland

The sulphur isotope composition of the epiphytic lichens, Hypogymnia physodes (L.) Nyl and Pseudevernia furfuracea (L.) Zopf, of the terricolous lichens, Cladina sp. and Peltigera aphthosa (L.) Willd., and of pine bark, at 31 sites in Finland, appeared to be dependent on lichen and tree species. The negative correlation of sulphur isotope composition with sulphur content was highly significant (P<0.001) in H. physodes and significant (P<0.01) in Pseudevernia furfuracea and Peltigera aphthosa. No correlation between the sulphur isotope composition and sulphur content was found for Cladina sp. and pine bark. The sulphur isotope compositions displayed statistically significant regional variation from south to north. Microenvironmental factors were considered, including phorophyte species and the chemical form of sulphur.     

Historical and current atmospheric deposition to the epilithic lichen Xanthoparmelia in Maricopa County,Arizona

Spatial patterns of atmospheric deposition of trace elements to an epilithic lichen were assessed using a spatial grid of 28 field sites in 1998 throughout Maricopa County, Arizona, USA. In addition, samples of Xanthoparmelia spp. from Arizona State University lichen herbarium material (1975-1976) was utilized for a limited number of sites in order to explore temporal trends. The lichen material was cleaned, wet digested and analyzed by ICP-MS for a suite of elemental concentrations [antimony (Sb), cadmium (Cd), cerium (Ce), chromium (Cr), cobalt (Co), copper (Cu), dysprosium (Dy), europium (Eu), gadolinium (Gd), gold (Au), holmium (Ho), lead (Pb), lutetium (Lu), neodymium (Nd), nickel (Ni), palladium (Pd), platinum (Pt), praseodymium (Pr), samarium (Sm), scandium (Sc), silver (Ag), terbium (Tb), thulium (Tm), tin (Sn), uranium (U), ytterbium (Yb), yttrium (Y), and zinc (Zn)]. Cluster analysis and principal component analysis suggest three major factors, which, depending on regional aerosol fractionation, explain most of the variation in elemental signatures: (1) a group of widely distributed rare earth elements (2) a highly homogenous Co, Cr, Ni, and Sc component representing the influence of mafic rocks, and (3) anthropogenic emissions. Elemental concentrations in Maricopa County lichens were generally comparable to those reported for relatively unpolluted areas. Only highly urbanized regions, such as the greater Phoenix Metropolitan Area and the NW corner of the county, exhibited elevated concentrations for Zn, Cu, Pb, and Cd. Lead levels in lichens have fallen over the last 30 years by 71%, while Zn concentrations for some regions have increased by as much as 245%. From the spatial pattern of elemental deposition for Cd, Cu, Ni, Pr, Pb, and Cu, we infer that agriculture, mining, industrial activities, and traffic probably are the major air pollutant sources in Maricopa County.     

Atmospheric dispersion of pollutants in Sado estuary (Portugal) using biomonitors

Epiphytic lichen transplants and aerosol samplers were put together in the Setubal area, Portugal. They were analysed by Instrumental Neutron Activation Analysis (INAA) and Proton Induced X-ray Emission (PIXE). The lichen dataset pointed out nine factors. No relevant differentiation was found towards different positioning of the lichens. T-transplants were delayed towards F-transplants, and for both after 3 and 6 months the accumulation was as much as at 9th month. Direct rainfall protection favoured accumulation for a few elements only. The elemental accumulation in lichens depended more on temperature and humidity conditions. Aerosol data towards lichen database showed an excellent correlation.     

Determination of trace elements and evaluation of their enrichment factors in Himalayan lichens

Within the framework of the Ev-K2-CNR research program of the Italian National Research Council a specific task project has been initiated for the identification of trace elements in lichens in remote high altitude areas. This is to evaluate the possibility of using lichens as biomonitors of trace elements of atmospheric pollution. In this preliminary study, more than 20 elements have been determined in some species of lichens collected at different altitudes (from 1300 to 5000 m) in the region of the Sagarmatha National Park (Nepal). Samples of superficial soils were also collected and analyzed to calculate the trace element enrichment factors (EF) using scandium as a normalizing element. Most of the trace elements were determined by instrumental neutron activation analysis (INAA), while lead and cadmium measurements were carried out with electrothermal atomic absorption spectroscopy (ET-AAS). The EF values as well as the elemental concentrations are reported and discussed.     

The use of the barbell cluster ANOVA design for the assessment of environmental pollution: a case study, Wigierski National Park, NE Poland

This report presents an assessment of chemical variability in natural ecosystems of Wigierski National Park (NE Poland) derived from the calculation of geochemical baselines using a barbell cluster ANOVA design. This method enabled us to obtain statistically valid information with a minimum number of samples collected. Results of summary statistics are presented for elemental concentrations in the soil horizons-O (Ol + Ofh), -A and -B, 1- and 2-year old Pinus sylvestris L. (Scots pine) needles, pine bark and Hypogymnia physodes (L.) Nyl. (lichen) thalli, as well as pH and TOC. The scope of this study also encompassed S and C stable isotope determinations and SEM examinations on Scots pine needles. The variability for S and trace metals in soils and plant bioindicators is primarily governed by parent material lithology and to a lesser extent by anthropogenic factors. This fact enabled us to study concentrations that are close to regional background levels.     

Air pollution and climate gradients in western Oregon and Washington indicated by epiphytic macrolichens

Human activity is changing air quality and climate in the US Pacific Northwest. In a first application of non-metric multidimensional scaling to a large-scale, framework dataset, we modeled lichen community response to air quality and climate gradients at 1416 forested 0.4 ha plots. Model development balanced polluted plots across elevation, forest type and precipitation ranges to isolate pollution response. Air and climate scores were fitted for remaining plots, classed by lichen bioeffects, and mapped. Projected 2040 temperatures would create climate zones with no current analogue. Worst air scores occurred in urban-industrial and agricultural valleys and represented 24% of the landscape. They were correlated with: absence of sensitive lichens, enhancement of nitrophilous lichens, mean wet deposition of ammonium >0.06 mg l(-1), lichen nitrogen and sulfur concentrations >0.6% and 0.07%, and SO(2) levels harmful to sensitive lichens. The model can detect changes in air quality and climate by scoring re-measurements.     

Calibration of lichen transplants considering faint memory effects

Biomonitoring, among other purposes, can be used as a tool to study the dispersion of trace elements through the atmosphere and back to the earth's surface again. In this sense it has been used for more than 20 years now. Yet, the calibration of biomonitors elemental contents against other atmospheric element dispersion variables like deposition or airborne concentration is still an open subject. The knowledge of a calibration nevertheless represents a qualitative improvement upon the use of biomonitors. Biomonitors elemental contents are usually assumed to depend in a linear way on the average values of atmospheric element dispersion variables, thus a linear regression is assumed to provide a good calibration. In this work: the element dispersion variables like deposition or airborne concentration will be referred in general as availability variables due to reasons that will be clarified; an uptake experiment using transplants of lichen Parmelia sulcata carried out in Portugal during a 2-year period (1994/1996) is described; and new concepts and calibration methods are presented. Lichen and aerosol samples were analysed by nuclear analytical techniques PIXE and INAA, and total deposition dry residue samples were analysed by ICP-MS. A database of roughly 70,000 values was thus created and biomonitor calibration carried out considering that biomonitors are not mechanical instruments but that they rather describe their exposure with a non-perfect memory. Data shows that surveying lichens four times within 1 year, with a period of 3 months in between sampling campaigns, allows the recovery of availability mean, maxima and standard deviation for many elements.     

Lichens as sentinels for air pollution at remote alpine areas (Italy)

The present study was undertaken with the aim of using epiphytic lichens as sentinels for air pollution at two remote alpine sites (1,400 and 1,800 m above sea level (asl)) of NW Italy. The results indicated that the site at 1,800 m prompted for early warning indications of biological changes. Although levels of the many elements assayed in samples of the lichen Pseudevernia furfuracea (L.) Zopf, ranging from minor elements (e.g., Al) to ultra-trace (e.g., Pt), were at normal levels, indications of a slowly worsening environment were given by the lichen biodiversity and by damage to cell membranes. The analysis of Pb isotopic ratios suggested that the origin of Pb accumulated in lichens is not local, but linked to the long-range transport by air masses. It was concluded that the origin of pollutants is from air mass coming from the Po plain of Italy and from densely populated areas of Switzerland and France.     

The use of autecological and environmental parameters for establishing the status of lichen vegetation in a baseline study for a long-term monitoring survey

In 1997 the ecological characteristics of the epiphytic species (83 lichens and two algae) of an urban area (Grenoble, France) were determined. Seven autecological indices were used to characterize the lichen ecology: illumination index, humidity index, pH of bark, nutrient status of substratum, ecological index of IAP and frequency. Six clusters (A1-A6) were defined using cluster analysis and principal component analysis. Seven environmental parameters characterizing the stations and the lichen releves were also used: elevation, parameters of artificiality (urbanization, traffic and local land use), IAP, and the percentage of nitrophytic and acidophytic species. Six clusters (B1-B6) were defined using cluster analysis and canonical correspondence analysis. Four clusters (C1-C4) were finally defined using an empirical integrated method combining the autecological and environmental parameters. This final clustering which established the status of the lichen vegetation in 1997 can be reliably used as a baseline study to effectively monitor environmental changes in this urban area.     

Uptake and biotransformation of arsenate in the lichen Hypogymnia physodes (L.) Nyl

The uptake and metabolism of arsenate, As(V), as a function of time and concentration were examined in the lichen Hypogymnia physodes (L.) Nyl. Lichen thalli were exposed to As(V) in the form of a solution. Exponential uptake of As(V) from 4 microg mL(-1) As(V) solution was accompanied by constant arsenite, As(III), excretion back into the solution. Arsenate taken up into the lichens from 0, 0.1, 1, 10 microg mL(-1) As(V) solutions was partially transformed into As(III), dimethylarsinic acid (DMA) and (mono)methylarsonic acid (MA). 48 h after exposure, the main arsenic compound in the lichens was DMA in 0.1, As(III) in 1 and As(V) in 10 microg mL(-1) treatment. The proportion of methylated arsenic compounds decreased with increasing arsenate concentration in the exposure solution. These results suggest that at least two types of As(V) detoxification exist in lichens; arsenite excretion and methylation.