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.     

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.     

Trace element accumulation by moss and lichen exposed in bags in the city of Naples (Italy)

This paper presents the results of a bioaccumulation study of trace elements in the Naples urban area based on the use of the moss Sphagnum capillifolium (Ehrh.) Hedw. and the lichen Pseudevernia furfuracea (L.) Zopf exposed in bags in 23 sites. Moss and lichen bags were exposed for 4 months starting from the beginning of July 1999. Bags gathering was carried out after 10 weeks of exposure, at the end of the dry season, and after 17 weeks, during the wet season. The elements Al, As, Ca, Cd, Cr, Co, Cu, Fe, K, Mg, Mn, Mo, Ni, Pb, Ti, V and Zn were analysed by inductively coupled plasma-mass spectrometry ICP-MS in both biomonitors. For the majority of the elements the total amounts found in S. capillifolium were higher than in P. furfuracea whether considering the whole period of exposure or the weekly uptake. It was observed that there was a much greater difference in metal accumulation by P. furfuracea between the dry and wet seasons compared with S. capillifolium. In the wet period, the lichen seems to accumulate a larger quantity of metals. With the exception of Mn, trace element concentrations did not appear to be significantly affected by the washing away of rainfall. K loss during exposure suggested cell membrane damage in both organisms. For P. furfuracea the K leakage was limited to the dry period of exposure. A clear distinction between "lithophilic" and "anthropogenic" elements was achieved by cluster analysis. Significant correlations were found among Fe-Cu-Cr-Ni, Pb-Cd-Co, V-Cr-Ni, Zn-Ni-Pb, suggesting a common source for each group of elements.     

Lichen and moss bags as monitoring devices in urban areas. Part II: trace element content in living and dead biomonitors and comparison with synthetic materials

Lobes of the lichen Pseudevernia furfuracea (L.) Zopf and shoots of the moss Hypnum cupressiforme Hedw. were subjected to different treatments (water washing, oven drying, HNO3 washing, NH4-oxalate extraction) to assess the influence of vitality on accumulation efficiency, during a 6-week exposure in bags in two Italian cities, Trieste and Naples. No trend emerged between treatments, in terms of accumulation ability, for major and trace elements. Only water-washed lichens showed an increased C and N content after exposure in both cities. Element concentrations generally reached higher values in mosses than in lichens, especially for Al, Fe, and Zn (both cities), and for Cu, Mg and Na (Naples). Surface development strongly influenced accumulation capacity of the biomonitors. Quartzose and cation exchange filters revealed, on a weight basis, a poor performance. In urban environments, surface interception of atmospheric particulate seems to play a major role in accumulation, irrespective of organism vitality.     

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.     

Sulphur, nitrogen and carbon content of Sphagnum capillifolium and Pseudevernia furfuracea exposed in bags in the Naples urban area

The accumulation ability of the major elements sulphur, nitrogen and carbon by the moss Sphagnum capillifolium (Ehrh.) Hedw. and the lichen Pseudevernia furfuracea (L.) Zopf exposed in bags in Naples urban area,was investigated. Bags were exposed at the beginning of July 1999 and gathered in two subsequent moments: at the end of the dry season (after 10 weeks of exposure) and during the wet season (after 17 weeks of exposure), to include the effects of rainy conditions. Sulphur and N content of the lichen increased all over the exposure period, while the level of C did not change significantly either after 10 or 17 weeks of exposition. For the moss the S accumulation was limited to the dry period of exposure, whereas N and C content decreased with exposure. Results, in contrast with those obtained in a previous study on trace elements bioaccumulation [Adamo et al., Environmental Pollution, (2003) 122, 91-103], suggest that accumulation of gaseous pollutants is strongly influenced by biomonitor vitality and that lichen bags are a more reliable and effective tool for monitoring S, N and C atmospheric depositions in urban areas compared to moss bags, because of greater lichen resistance to dry and stressing conditions of urban environment.     

Correlation between the nitrogen concentration of two epiphytic lichens and the traffic density in an urban area

A field experiment was carried out in the urban environment of the Grenoble area using two epiphytic lichens: the nitrophytic Physcia adscendens and the acidiphytic Hypogymnia physodes. Two complementary studies characterized this experiment. Firstly, a sampling of the two lichens in 48 sites randomly located throughout the Grenoble area indicated that roads (size and proximity to sampling sites) influenced the nitrogen concentrations of P. adscendens, but not those of H. physodes. Secondly, to study more accurately the influence of roads, a traffic index was calculated and applied along two transects located perpendicularly to urban motorways. Significant positive correlations were found between this traffic index and the total nitrogen concentration of P. adscendens.     

Comparison of the heavy metal bioaccumulation capacity of an epiphytic moss and an epiphytic lichen

This study compared the heavy metal bioaccumulation capacity in the epiphytic moss Scorpiurum circinatum and the epiphytic lichen Pseudevernia furfuracea, exposed in bags for 3 months in the urban area of Acerra (S Italy). The content of Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V, and Zn was measured by ICP-MS. The results showed that both species accumulated all the heavy metals assayed. The moss had the highest bioaccumulation capacity for all metals and showed a more constant and linear accumulation trend than the lichen. Intra-tissue heavy metal bioaccumulation was assessed by X-ray microanalysis applied to ESEM operated in high and low vacuum and ESEM modes.     

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.     

The accumulation of alkylphenols in submersed plants in spring in urban lake, China

The concentrations of alkylphenols (APs) were investigated in water, sediments and submersed macrophytes from the Moon Lake, Wuhan city, China. The water samples contained APs, ranging up to 26.4 microg l-1 for nonylphenol (NP) and 0.68 microg l-1 for octylphenol (OP). APs were found in the sediment samples with concentrations ranging from 4.08 to 14.8 for NP and from 0.22 to 1.25 microg g-1 dry weight for OP. The samples from the site near former sewage inlet showed the highest concentrations of APs in both water and sediments. The results of distribution pattern and dynamics of NP and OP in submersed macrophytes of the Moon Lake showed that the two pollutants were all found in Myriophyllum verticillatum, Elodea nuttallii, Ceratophyllum oryzetorum, and Potamageton crispus collected from the Moon Lake. For NP, M. verticillatum had the highest capacity of accumulation, followed by E. nuttallii, C. oryzetorum and P. crispus. However the distribution pattern of OP differed from that of NP, and the highest amount of accumulation was observed in E. nuttallii, followed by M. verticillatum, P. crispus, and C. oryzetorum. The temporal pattern of APs was also observed in submersed macrophytes from March to May, and the highest accumulation period was in May.     

The potential of lichens as long-term biomonitors of natural and artificial radionuclides

Lichens were used as biomonitors of Chernobyl fallout 137Cs, of cosmogenic 7Be and of radioactive members of the natural uranium and thorium decay chains. Samples were taken from two locations in France, including lichens sampled at different distances of a coal fired power plant and close to a uranium ore processing waste disposal site. All samples were analyzed gamma-spectrometrically after equilibrium concentrations of short-lived isotopes had been attained. Activity concentrations of the members of the uranium and thorium decay chains in Parmelia sulcata sampled 1994 decrease with distance from the plant, whereas in lichens taken at the waste disposal site a decrease with time was observed. Comparison of 7Be activity concentrations measured in lichens with atmospheric deposition rates confirms that P. sulcata can be used as a quantitative biomonitor of radioactive trace substances. Retention half-lives calculated with a simple one-compartment model are 2.6 +/- 1.2 years for cesium, which was detected in all samples even more than a decade after the Chernobyl accident, and of 0.7 (+/- 0.1) to 3.3 (+/- 0.7) years for lead. Consequences of our results for model identifiability and parameter estimation of a two-compartment model are discussed.     

Accumulation of nutrients in soils affected by perennial colonies of piscivorous birds with reference to biogeochemical cycles of elements

The accumulation of selected N, K, and P forms in soils within three perennial colonies of black cormorant (Phalacrocorax carbo sinensis) and grey heron (Ardea cinerea) located in northern and eastern Poland were investigated. Soil samples were collected beneath the nests from the most representative for each colony plots. Control samples were taken outside the colonies within sites adjacent to the nesting areas but not affected by bird excrement. From each genetic horizon (20 horizons) in soil profiles, a cumulative sample of about 25-30 kg of soil was taken for analysis. Nitrogen by Kjeldahl, ammonium ions (N(NH(4))), nitrates (N(NO(3))), exchangeable potassium (K(ex)), available potassium (K(av)), and available phosphorus (P(av)) were determined. The soils affected by birds demonstrated a very strong enrichment with N, K, and P in comparison to the control sites, especially in the topsoil horizons. The content of N(NH(4)) in individual soil horizons from the colonies was from 1.7 to 10.1 times higher than the respective control, N(NO(3)) from 2.9 to 215.7, K(ex) from 2.0 to 35.1, K(av) from 1.1 to 48.1, and P(av) in the range from 2.4 to 53.0 times. The highest increment of chemical elements was noticeable in the soils of territories inhabited by cormorants and the least in forest occupied by herons. Some relationships between soil texture and accumulation of biogenic nutrients were determined. Clay loam soil showed the greatest enrichment with analysed forms of elements with the exception of N(NH(4)).     

Initial studies for the phytostabilization of a mine tailing from the Cartagena-La Union Mining District (SE Spain)

Mine tailings are one of the main environmental problems in post-mining landscapes and their removal is often complicated due to their high heavy metal content and dimensions. In this sense, using plant species for in situ stabilization may be an interesting and low cost option. Moreover, there are some plant species that have adapted to these conditions and are usually present at these contaminated sites. In this study, a mine tailing located in South-East Spain was investigated in order to establish lines for further phytostabilization research. A plot sampling design was carried out in order to characterize the soil properties. In addition, two plant species that have naturally colonized some parts of the tailing, Hyparrhenia hirta and Zygophyllum fabago, were sampled, including the analyses of their respective rhizospheric soils. The results of plot soil samples showed pH values from ultra acid to slightly alkaline. The electrical conductivity values were around 4dSm(-1) in plots with vegetation and 8dS m(-1) in the plot without vegetation. Total metal concentrations were high (4000 mg kg(-1) for Pb, 9000-15000 mg kg(-1) for Zn). DTPA- and water-extractable Zn were 5% and 3% of the total, respectively. H. hirta accumulated around 150 mg kg(-1) Pb in both shoots and roots. Zn concentration was 750 mg kg(-1) in Z. fabago shoots. DTPA-extractable Zn and Cu were positively correlated to plant uptake.     

Morphology, chemistry and distribution of neoformed spherulites in agricultural land affected by metallurgical point-source pollution

Metal distribution patterns in superficial soil horizons of agricultural land affected by metallurgical point-source pollution were studied using optical and electron microscopy, synchrotron radiation and spectroscopy analyses. The site is located in northern France, at the center of a former entry lane to a bunker of World War II, temporarily paved with coarse industrial waste fragments and removed at the end of the war. Thin sections made from undisturbed soil samples from A and B horizons were studied. Optical microscopy revealed the occurrence of yellow micrometer-sized (Ap horizon) and red decamicrometer-sized spherulites (AB, B(1)g horizons) as well as distinct distribution patterns. The chemical composition of the spherulites was dominated by Fe, Mn, Zn, Pb, Ca, and P. Comparison of calculated Zn stocks, both in the groundmass and in spherulites, showed a quasi-exclusive Zn accumulation in these neoformed features. Their formation was related to several factors: (i) liberation of metal elements due to weathering of waste products, (ii) Ca and P supply from fertilizing practices, (iii) co-precipitation of metal elements and Ca and P in a porous soil environment, after slow exudation of a supersaturated soil solution in more confined mineral media.     

Lichens and mosses as biomonitors of trace elements in areas with thermal springs and fumarole activity (Mt. Amiata, central Italy)

The contribution of thermal springs and fumaroles to environmental levels of Al, As, B, Cd, Cu, Fe, Hg, Mo, Pb, S, Sb and Zn was evaluated by means of lichens (Parmelia sulcata) and mosses (Hypnum cupressiforme) used as bioaccumulators. Compared to the data reported for unpolluted areas, accumulation of Hg, S and Al was found, with values of Hg and S in the same range as in the vicinity of geothermal power plants. Furthermore, fumaroles turned out to be a significant source of atmospheric arsenic.     

Impact of soil quality on elemental uptake by, and distribution in, Colocasia esculenta (Amadumbe), an edible root

In this study the elemental distribution of selected essential (Ca, Mg, Al, Mn, Cu, Fe, Co, Cr, Zn, Ni and Se) and the non-essential (Pb, Hg and As) elements were determined in the bulb and peel of Amadumbe (Colocasia esculenta) samples from eight different sites in KwaZulu-Natal, South Africa. The concentration of Se and As in the soil and in the Amadumbe bulbs were below the detection limit of 0.09 μg g?1. The total and bioavailable concentrations of the elements in conjunction with pH, soil organic matter (SOM) and cation exchange capacity (CEC) were determined in the soil samples from the eight sites. Statistical analysis was done to evaluate the impact of soil quality parameters on the chemical composition of the Amadumbe root. The results show accumulation or exclusion of certain elements by the bulb as evidenced by the noticeable increase or decrease of the concentrations of elements, respectively. Ca and Mg were found to be major elements in the range (2000-12000 μg g?1), whilst Mn, Zn, Fe and Al were found to be minor elements in the range (20-400 μg g?1). A general trend observed was that the plant favours the absorption of Zn over Cu. A positive correlation between Mg & Ca, Cu & Fe and Co & Ni was also observed. Statistical analysis revealed that the plant tended to accumulate Mg, Ca, Co, Cr and Pb whilst it excluded Hg and Fe, to a lesser extent.     

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.     

Lichen and moss bags as monitoring devices in urban areas. Part I: influence of exposure on sample vitality

Samples of the lichen Pseudevernia furfuracea (L.) Zopf and the moss Hypnum cupressiforme Hedw. were exposed for 6 weeks in nylon bags in two air pollution monitoring stations in Trieste and Naples (Italy) with different climates and pollution loads to evaluate influence of environmental conditions on sample vitality. This was assessed before and after exposure by transmission electron microscopy observations, K cellular location, and measurements of C, N, S and photosynthetic pigments content, CO2 gas exchange, and chlorophyll fluorescence. Almost all data sets indicate that exposures caused some damage to the species, considerably heavier in the moss, especially in Naples. The two cryptogams differed significantly in accumulation and retention of C, N, and S, the lichen clearly reflecting NO2 availability. The difference in vitality loss was related to the different ecophysiology of the species, because concentrations of phytotoxic pollutants were low during exposure. Critical notes on the analytical techniques are also given.     

Effects of soil properties on heavy metal accumulation in flowering Chinese cabbage (Brassica campestris L. ssp. chinensis var. utilis Tsen et Lee) in Pearl River Delta,China

This study was conducted to investigate the effects of soil properties on the heavy metal accumulation in flowering Chinese cabbage (Brassica campestris L. ssp. chinensis var. utilis Tsen et Lee) at the field scale. The concentrations of cadmium (Cd), mercury (Hg), and chromium (Cr) in topsoil and vegetable samples from Nanhai district of Foshan city in the Pearl River Delta (PRD) were analyzed. The results showed that 56.5% of the soil samples exceeded the grade II of the Chinese Soil Environmental Quality Standard (GB 15618-1995) for Hg concentrations, while 8.70% and 17.4% of the vegetable samples exceeded the criteria of the Chinese Safety Qualification of Agricultural Products (GB 18406.1-2001) for Cd and Hg concentrations, respectively. The calculated bio-concentration factor (BCF; i.e., the ratio of the metal concentration in the edible parts of flowering Chinese cabbage to that in soil) values were ranked as: Cd (0.1415) > Cr (0.0061) > Hg (0.0012) (p < 0.01), which demonstrated that Cd was easier to be accumulated in the edible parts of flowering Chinese cabbage than Hg and Cr. Furthermore, the following relationships between (bio-concentration factor) BCF values (BCFs) and soil physicochemical properties were concluded from our results: i) the mean BCFs of coarse-textured soils were higher than those of fine-textured soils; ii) the BCFs decreased with increasing soil pH; iii) the soils with high organic matter(OM) and Cation exchange capacity (CEC) have low BCFs, resulting from their high sorption capacities for Cd, Hg, and Cr. The stepwise linear multiple regression analyses showed that total metal concentrations and available calcium in soils were two main factors controlling the accumulation of Cd, Hg, and Cr in the flowering Chinese cabbage.     

Effects of soil properties on heavy metal accumulation in flowering Chinese cabbage (Brassica campestris L. ssp. chinensis var. utilis Tsen et Lee) in Pearl River Delta, China

This study was conducted to investigate the effects of soil properties on the heavy metal accumulation in flowering Chinese cabbage (Brassica campestris L. ssp. chinensis var. utilis Tsen et Lee) at the field scale. The concentrations of cadmium (Cd), mercury (Hg), and chromium (Cr) in topsoil and vegetable samples from Nanhai district of Foshan city in the Pearl River Delta (PRD) were analyzed. The results showed that 56.5% of the soil samples exceeded the grade II of the Chinese Soil Environmental Quality Standard (GB 15618-1995) for Hg concentrations, while 8.70% and 17.4% of the vegetable samples exceeded the criteria of the Chinese Safety Qualification of Agricultural Products (GB 18406.1-2001) for Cd and Hg concentrations, respectively. The calculated bio-concentration factor (BCF; i.e., the ratio of the metal concentration in the edible parts of flowering Chinese cabbage to that in soil) values were ranked as: Cd (0.1415) > Cr (0.0061) > Hg (0.0012) (p < 0.01), which demonstrated that Cd was easier to be accumulated in the edible parts of flowering Chinese cabbage than Hg and Cr. Furthermore, the following relationships between (bio-concentration factor) BCF values (BCFs) and soil physicochemical properties were concluded from our results: i) the mean BCFs of coarse-textured soils were higher than those of fine-textured soils; ii) the BCFs decreased with increasing soil pH; iii) the soils with high organic matter(OM) and Cation exchange capacity (CEC) have low BCFs, resulting from their high sorption capacities for Cd, Hg, and Cr. The stepwise linear multiple regression analyses showed that total metal concentrations and available calcium in soils were two main factors controlling the accumulation of Cd, Hg, and Cr in the flowering Chinese cabbage.