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.     

Active moss biomonitoring of trace elements with Sphagnum girgensohnii moss bags in relation to atmospheric bulk deposition in Belgrade, Serbia

Active biomonitoring with wet and dry moss bags was used to examine trace element atmospheric deposition in the urban area of Belgrade. The element accumulation capability of Sphagnum girgensohnii Russow was tested in relation to atmospheric bulk deposition. Moss bags were mounted for five 3-month periods (July 2005-October 2006) at three representative urban sites. For the same period monthly bulk atmospheric deposition samples were collected. The concentrations of Al, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, and Pb were determined by instrumental neutron activation analyses and atomic absorption spectrometry. Significant accumulation of most elements occurred in the exposed moss bags compared with the initial moss content. High correlations between the elements in moss and bulk deposits were found for V, Cu, As, and Ni. The enrichment factors of the elements for both types of monitor followed the same pattern at the corresponding sites.     

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.     

Natural and pre-treatments induced variability in the chemical composition and morphology of lichens and mosses selected for active monitoring of airborne elements

To enhance the reliability of the moss and lichen transplant technique for active biomonitoring of trace metals in urban environments, we evaluated the natural variability in the chemical composition of the (epilithic and epiphytic) moss Hypnum cupressiforme and the epiphytic lichen Pseudevernia furfuracea from two reference areas in NE Italy. Green shoots of epilithic mosses and lobes of epiphytic lichens from larch branches showed rather homogenous composition and were selected for the exposure in nylon bags. As different physico-chemical pre-treatments are usually applied to selected cryptogamic material before its exposure, we also evaluated the effects of oven-drying at 120 degrees C for 24h, washing in 1N HNO3 solution, and in 0.5% NH4 oxalate solution at 85 degrees C for 15 h on the chemical composition and morphology of water-washed moss shoots and lichen lobes. Pre-treatments remarkably changed the chemical composition of selected materials but not their surface morphology.     

Bags with oven-dried moss for the active monitoring of airborne trace elements in urban areas

To define a harmonized methodology for the use of moss and lichen bags as active monitoring devices of airborne trace elements in urban areas, we evaluated the element accumulation in bags exposed in Naples in different spring weather conditions for 6- and 12-weeks. Three different pre-exposure treatments were applied to moss and lichen materials: water-washing, acid-washing and oven-drying. During the different exposure periods in the Naples urban environment the moss accumulated always higher amounts of elements (except Hg) than lichens and the element accumulation increased during wetter weather and higher PM₁₀ conditions. The oven pre-treatment did not substantially modify the morphology and element composition of moss and the exposure in bags of this material for 6-weeks was sufficient to detect the pattern of airborne trace elements.     

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.     

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.     

Elemental composition of Hoh Rainforest Olympic National Park Washington, USA

The concentration, enrichment factor and storage of 27 elements was examined for growing in Olympic National Park, Washington. Most element concentrations changed significantly as the moss aged. Concentrations of copper, zinc, and lead were among the lowest found to date. Crustal enrichment factors indicated many elements were initially derived from atmospheric sources. These data indicate concentrations of heavy metals in remote, unpolluted sites may be considerably lower than initially thought.Mosses have been used to monitor air pollution because they accumulate trace elements and their growth is sensitive to pollutants. and were used to monitor trace element contamination in Europe (Yale and Lloyd 1984, Goodman and Roberts 1971, Lotschert and Wardtner 1982). The older portions of tended to have higher concentrations of copper and zinc than the newer portions. Sweiboda and Kalemba (1981) used and other mosses to monitor the presence of sulfur and flourine. An ecological index of contamination was developed by Le Blanc, et al. (1974) based heavily on the presence and absence of lichen and moss species around a copper mill area in Quebec, Canada. These studies demonstrate that the chemical composition of moss tissues and changes in species abundance are sensitive to atmospheric chemical composition.     

Active moss biomonitoring of small-scale spatial distribution of airborne major and trace elements in the Belgrade urban area

In urban environments, human exposure to air pollutants is expected to be significantly increased, especially near busy traffic streets, street canyons, tunnels, etc. where urban topography and microclimate may additionally cause poor air conditions giving rise to pollution hotspots. As a practical and cost-effective approach, active moss biomonitoring survey of some major and trace element air pollution was performed in the Belgrade street canyons and city tunnel in 2011 with the aim to evaluate possibility of using Sphagnum girgensohnii moss bags for investigation of the small-scale vertical and horizontal distribution patterns of the elements. In five street canyons, the moss bags were hung at heights of about 4, 8 and 16 m, during 10 weeks, and also, for the same time, the moss bags were exposed in the tunnel, in front of and out of it. After the exposure period, the concentrations of Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, V and Zn in the moss were determined by inductively coupled plasma optical emission spectrometry. According to the results, in all street canyons, the vertical distribution patterns of the moss elements concentration (Al, Ba, Co, Cr, Cu, Ni, Pb, Sr, V and Zn) showed statistically significant decrease from the first to the third heights of bags exposure. In the tunnel experiment, from inner to out of the tunnel, for Al, Ba, Cd, Co, Cr, Cu, Fe, K and Zn, decreasing trend of concentrations was obtained. Significantly higher concentration of the elements was pronounced for the tunnel in comparison with the street canyons. The results indicate that the use of S. girgensohnii moss bags is a simple, sensitive and inexpensive way to monitor the small-scale inner city spatial distribution of airborne major and trace element content.     

Implementation of airborne trace element monitoring with devitalised transplants of Hypnum cupressiforme Hedw.: assessment of temporal trends and element contribution by vehicular traffic in Naples city

A biomonitoring of airborne trace elements was performed in 2006 in Naples urban area through the exposure of devitalised Hypnum cupressiforme for 10 weeks at 4 m height. In one street, the moss was exposed at different heights to assess vertical gradients of element concentrations. Results were compared with those of a 1999 biosurvey. Correlations among Al, Fe and Ti suggested a soil particles contribution to element uptake. Cu, Mo and Fe were related with traffic flows. Long-range transport contributed to Cd, Cu and Mo accumulation in moss at higher heights. As in 1999, the airborne element load was higher in coastal sites, more affected by marine aerosols and traffic. In all sites, contents of Cd, Fe, Pb, Ni and V in moss were remarkably lower than in 1999, indicating a positive effect of actions set up in recent years to reduce the traffic and to improve the city air quality.     

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.     

Effects of Sphagnum moss and urban runoff on bioavailability of lead and zinc from acidic wetlands of the New Jersey pinelands

The effects of Sphagnum and urban runoff on the bioavailability of metals were tested by adding PbCl2 and ZnCl2 to laboratory microcosms constructed of peat substrate with or without live Sphagnum spp. and planted with Acer rubrum L. seedlings or Vaccinium macrocarpon Ait. shoots. We hypothesized that Sphagnum would increase bioavailability through its acidifying action, while urban runoff would decrease availability through increases in alkalinity. Metals were more available to the test plants treated with acidic swampwater than with alkaline runoff. Sphagnum moss caused increases in tissue concentrations in V. macrocarpon, but not in A. rubrum. The latter species took up more metals when grown on substrate from sites receiving runoff, whereas the former took up more metals from substrate from undisturbed sites, despite the lower substrate metal concentrations. Differences in uptake by the two species may reflect differences in their ability to root in the Sphagnum mat. The results demonstrate that Sphagnum spp. exerts strong species-specific effects on the uptake of metals by vascular plants, and that plant species native to acidic wetlands vary widely in their response to metals in the substrate.     

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.     

Sphagnum fuscum moss as an indicator of atmospheric cadmium deposition across Canada

The concentration of cadmium was determined in samples of Sphagnum fuscum moss collected from 37 sites across Canada from the Pacific Ocean to the Atlantic Ocean and Labrador Sea. At 22 of the sites, Cd was less than 0.2 mg kg(-1), the detection limit. Elevated Cd levels were only found in mosses collected in the vicinity of the smelters at Flin Flon, Manitoba, and Rouyn-Noranda, Quebec, where a maximum concentration of 12 mg kg(-1) was measured.     

The fate of some components of acidic deposition in ombrotrophic mires

The ability of ombrotrophic Sphagnum species to immobilise inorganic nitrogen deposited from the atmosphere was investigated in a series of simple lysimeter experiments. In an unpolluted mire, Sphagnum fuscum mats retained all the nitrogen deposited to them in natural precipitation events. Sphagnum capillifolium mats, transplanted from an unpolluted site to the polluted southern Pennines in England, also initially retained a large proportion of deposited nitrate and ammonium. However, a laboratory experiment demonstrated that high rates of nitrogen supply cause a loss of the ability of the moss to retain nitrate, which suggests that this may occur as a result of increased nitrogen deposition in polluted regions, resulting in increased nitrate availability in the peat. Investigation of the volume of precipitation and amounts of sulphate and chloride passing through the Sphagnum mats in the southern Pennines, as compared to that collected in adjacent bulk deposition gauges, showed that conventional deposition monitoring grossly underestimates rates of deposition to vegetation. Efficient trapping of occult and dry deposition by the moss led to much greater volumes of precipitation and amounts of sulphate and chloride being measured in throughflow than in bulk precipitation samples. Physiological response of S. fuscum to occult precipitation and heavy rainfall was investigated by measuring nitrate reductase activity induced in the moss by nitrate supplied in 'fine mist' and 'large droplet' applications of solutions to moss in the field. Greater response was shown to occult deposition, suggesting that this form of precipitation may be important in vegetation damage in polluted regions.     

Leaf accumulation of trace elements and polycyclic aromatic hydrocarbons (PAHs) in Quercus ilex L

Quercus ilex L. leaves were collected four times in one year at six urban sites and one remote area in order to determine trace element and PAH accumulation through concomitant analyses of unwashed and water-washed leaves. Both unwashed and washed leaves showed the highest amounts of trace elements and PAHs in the urban area. Unwashed leaves showed greater differences between urban and remote areas and among the urban sites than washed leaves for trace element and PAH concentrations. Water-washing resulted in a significant (P<0.001) decrease in leaf concentrations of Cr, Cu, Fe, Pb, V and Zn. By contrast, Cd and total PAH concentrations showed no differences between unwashed and washed leaves.     

Epilithic Lichen—Atmospheric Deposition Monitors of Trace Elements and Organohalogens?

ABSTRACT

Epilithic lichen (Xanthoria elegans in Canada, Lecanora muralis in Germany) were gathered from 17 locations in Ontario, Canada (from Lake Ontario to James Bay) and 43 locations in Germany (from the Alps to the North Sea and from the Baltic Sea to the Erzgebirge). Sample aliquots were digested in nitric acid and trace elements were analyzed by inductively coupled plasma-mass spectrom-etry techniques. The organohalogens were determined as absorbable organic halogens (AOXs) by coulometry. Concentration ranges from Germany for trace element samples and AOXs were determined. The lichen showed high spatial resolution in their element enrichment patterns. This allowed for differentiation between natural and anthropogenic dominance in ambient air concentrations. This biomonitoring method has proven to be very sensitive, fast, and reliable. No clear relationship could be found between trace element and AOX concentrations. The AOX values may reflect individual metabolic rates of the fungal partner in lichen symbionts.     

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.     

Trace elements biomonitoring in a historical mining district (les Malines, France)

The aim of this study is to investigate the trace elements (TE) contents of potential biomonitors in a historical Zn–Pb mining district: apiary products (honey, royal-jelly and beeswax) lichen and moss were sampled and analysed. In spite of high TE concentrations in mining waste and soil, apiary products are free of TE contamination originating from historical mining. Lichen/moss show high TE levels, which suggest atmospheric input of local dust. Pb isotopes analysis proved the origin of TE found in lichen/moss to be mainly mining waste. These results help discuss the choice of relevant organisms for monitoring TE in the environment and bring additional data on the potential impacts of brownfields left after mining, especially on food products from apiaries.     

PCA and multidimensional visualization techniques united to aid in the bioindication of elements from transplanted <Emphasis Type="Italic">Sphagnum palustre</Emphasis> moss exposed in the Gdańsk City Area

GOAL, SCOPE AND BACKGROUND: During the last decades, a technique for assessing atmospheric deposition of heavy elements was developed based on the principle that samples of moss are able to accumulate elements and airborne particles from rain, melting snow and dry deposition. Despite a broad interest in bioindication there are still ongoing works aimed at the preparation of a standard procedure allowing for a comparison of research carried out in various areas. This is why the comparison of living and dry moss of the same species and growth site seems to be interesting, logical and promising. A most reliable approach seems to be the application of bioindication connected with multivariate statistics and efficient visualization techniques in the interpretation of monitoring data. The aim of this study was: (i) to present cumulative properties of transplanted Sphagnum palustre moss with differentiation into dry and living biomaterial; (ii) to determine and geographically locate types of pollution sources responsible for a structure of the monitoring data set; (iii) to visualize geographical distribution of analytes in the Gdańsk metropolitan area and to identify the high-risk areas which can be targeted for environmental hazards and public health. MATERIALS AND METHODS: A six month air pollution study based on Sphagnum palustre bioindication is presented and a simplified procedure of the experiment is given. The study area was located at the mouth of the Vistula River on the Baltic Sea, in Gdańsk City (Poland). Sphagnum palustre was selected for research because of its extraordinary morphological properties and its ease in being raised. The capability of dry and living moss to accumulate elements characteristic for anthropogenic and natural sources was shown by application of Principal Component Analysis. The high-risk areas and pollution profiles are detected and visualized using surface maps based on Kriging algorithm. RESULTS: The original selection of elements included all those that could be reliably determined by Neutron Activation Analysis in moss samples. Elimination of variables covered the elements whose concentrations in moss were lower than the reported detection limits for INAA for most observations or in cases where particular elements did not show any variation. Eighteen elements: a, Ca, Sc, Fe, Co, Zn, As, Br, Mo, Sb, Ba, La, Ce, Sm, Yb, Lu, Hf, Th, were selected for the research presented. DISCUSSION: Two runs of PCA were performed since, in the first-run a heavy polluted location (Stogi - 'Sto') understood as outlier in the term of PCA approach was detected and results in the form of block diagrams and surface maps were presented. As ensues from the first-run PCA analysis, the factor layout for both indicators is similar but not identical due to the differences in the elements accumulation mechanism. Three latent factors ('phosphatic fertilizer plant impact', 'urban impact' and 'marine impact') explain over 89% and 82% of the total variance for dry and living moss respectively. In the second-run PCA three latent factors are responsible for the data structure in both moss materials. However, in the case of dry moss analysis these factors explain 85% of the total variance but they are rather hard to interpret. On the other hand living moss shows the same pattern as in first-run PCA. Three latent factors explain over 84% of the total variance in this case. The pollution profiles extracted in PCA of dry moss data differ tremendously between both runs, while no deterioration was found after removal of Stogi from data set in case of living moss. Performance of the second-run PCA with exception of Stogi as a heavy polluted location has led to the conclusion that living moss shows better indication properties than dry one. CONCLUSIONS: While using moss as wet and dry deposition sampier it is not possible to calculate deposition values since the real volume of collected water and dust is hard to estimate due to a splash effect and irregular surface. Therefore, accumulation values seam to be reasonable for moss-based air pollution surveys. Both biomaterials: dry and living Sphagnum palustre show cumulative properties relative to elements under interest. Dry moss has a very loose collection of the atmospheric particles, which can also easily get lost upon rinsing with rainwater running through exposed dry moss material. The living moss may, on the contrary, incorporate the elements in its tissue, thus being less susceptible to rinsing and thus better reflecting the atmospheric conditions. Despite the differences in element uptake and uphold capabilities dry and living moss reflect characteristic anthropogenic and natural profiles. Visible differences in impacts' map coverage exist mostly due to the accumulation mechanisms differentiating dry from living moss. However, in case of each indicator 'phosphatic fertilizer plant impact' is recognized as the strongest pollution source present in examined region. RECOMMENDATIONS AND PERSPECTIVES: General types of pollution sources responsible for a structure of monitoring data set were determined as high-risk/low-risk areas and visualized in form of geographic distribution maps. These locations can be targeted for environmental hazards and public health. Chemometric results in the form of easy defined surface maps can became a powerful instrument in hands of decision-makers working in the field of sustainable development implementation.