Mapping Lichen Diversity as a First Step for Air Quality Assessment

The evaluation of air quality is an important topic. It is well known that lichens have a set of characteristics that make them well suited for biomonitoring purposes. Sampling lichen diversity is not as expensive as chemical analysis, allowing a dense sampling grid and reducing the costs. Lichen diversity can be used to identify more disturbed areas, resulting from pollution, land use or ecological variables. In recent years, in order to enable extended use of lichens and to reduce ambiguities, i.e., variations due to unwanted environmental variables, efforts have been made to develop a feasible protocol for lichen sampling for biomonitoring purposes. This work aims at providing the information needed a priori for an air quality assessment study, in the form of a map showing areas where lichen diversity and abundance is lower. This study was done by sampling foliose and fruticulose lichen diversity and frequency, in a region in southwest Portugal (Sines) with large industrial facilities. A long-term study has been underway in the same area since the 1970s using lichens as bioindicators to evaluate air quality. In this work, we used a standard protocol to determine a lichen diversity value (LDV), to be used as an indicator of environmental quality. In order to reduce uncertainty concerning the type of disturbance affecting lichens, sampling sites were restricted using well-defined criteria. Whenever possible, sampling site variables were quantified. This method allowed us to reduce the many sources of variability affecting lichen diversity.     

Calibration of Four Species of Tillandsia as Air Pollution Biomonitors

Many organisms have been used as bioindicators of atmospheric contamination, with moss and lichen species being the most common. However, studies using epiphytic vascular species of Tillandsia have shown a good correlation between the presence of pollutants and the bioindicator's response. Therefore, the aim of our investigation was to calibrate and compare the response of four Tillandsia species of Argentina to ascertain whether they could be used as atmospheric contamination biomonitors. For this, we analysed the correlation between the levels of heavy metals in total atmospheric deposition samples and: a) their rate of enrichment; b) the physiological response of the plant samples. Tillandsia samples collected from a non contaminated area in the province of Córdoba were transplanted to four areas in the capital city with different sources of pollution (industrial or traffic emissions). They were exposed for a period of 3 to 6 months after which the concentrations of Pb, Ni, Fe, Zn, Cu and S as well as the physiological parameters of foliar damage were determined. Simultaneously samples of total atmospheric deposition were also taken.The highest level of metal enrichment was found in T. capillaris followed by T. tricholepis, T. permutata and T. retorta. Also, the use of a foliar damage index proved to be effective and could be a useful tool to evaluate different levels of atmospheric quality in these species. The rate of heavy metal deposition was higher in the industrial area for all metals except for Zn whose values were higher in areas with high levels of traffic.     

Lichens as Biomonitors of Depleted Uranium in Kosovo

This paper reports the results of a study using lichens as biomonitors to investigate the environmental distribution of depleted uranium (DU) at selected Kosovo sites as a consequence of the use of DU ordnance during the conflict of 1999. The results suggested that the use of DU ammunitions did not cause a diffuse environmental contamination in such a way to have caused a detectable U enrichment in lichens. Also isotopic ²³⁵U/²³⁸U measurements did not indicate the presence of DU particles in lichens, except for some samples at a heavily shelled site, which resulted contaminated by DU.     

Diversity of Epiphytic Lichens and Hg Contents of Xanthoria parietina Thalli as Monitors of Geothermal Air Pollution in the Mt. Amiata Area (Central Italy)

The diversity of epiphytic lichens and mercury concentrations in lichen samples were measured to monitor the release of airborne pollutants from the industrial exploitation of geothermal resources in the Mt. Amiata area (Italy). The lichen biodiversity showed a general condition of moderate environmental alteration around the geothermal power plants, contrasting with the low environmental alteration of the remaining sites investigated. According to the accumulated Hg in lichen thalli, it was possible to estimate mean Hg and H₂S concentrations in the air, which resulted in very good agreement with values measured instrumentally. Based on these data and the correlation between lichen diversity values and Hg concentrations in lichens, it was possible to calculate the threshold of 8 μg/m³ H₂S as responsible for the worsening from low to moderate environmental alteration according to the biodiversity of epiphytic lichens, and to infer that around geothermal power plants, although not toxic to humans, H₂S concentrations are such to alter the nasal quality of the air. Based on the growth rate of X. parietina, it was possible to convert Hg concentrations into estimates of average Hg deposition rates, which showed fluxes of the order of 65–100 mg/ha/y, indicating a dispersions factor of about 10⁴ for the Hg emitted from the geothermal power plants.     

Biomonitoring of heavy metals by <Emphasis Type="Italic">Pseudevernia furfuracea</Emphasis> (L.) Zopf in Ankara (Turkey)

The objective of this study was to determine the air pollution level of Ankara and to generate the air pollution map of this city by using Pseudevernia furfuracea (L.) Zopf as a biomonitor. Lichen samples were collected from unpolluted area at Yaprakli Mountains, Cankiri in November 2002 and transplanted to 27 localities in Ankara. Lichen samples were retrieved following an exposure of 3 and 6 months. Heavy metal, Cu, Mn, Ni, Pb and Zn, contents were determined by using inductively coupled plasma spectrometry (ICP). The chlorophyll a and b contents were determined by using DMSO method. The increase in Ni, Pb, Zn and chlorophyll a content of the specimens were statistically important. All the increases and decreases in the variables could be explained by the environmental stress like pollution, but it is hard to say that this is the only reason of these changes, also climatic conditions, seasons, strength of the light and the physiological status of the plant itself effective on these changes. According to the results of heavy metal analysis Pseudevernia furfuracea continued to accumulate heavy metals and worked well as a biomonitor. The air pollution level of Ankara shows great variations because of the great area of the city.     

Metabolised Tritium and Radiocarbon in Lichens and Their Use as Biomonitors

Lichens are now well known for their potential as bio-indicators of environmental pollution, but less is known about their suitability as quantitative biomonitors for atmospheric emissions of tritium (mainly as tritiated water, HTO) and radiocarbon (as ¹⁴CO₂) from nuclear facilities, although both radionuclides could result in non-trivial individual or collective radiation doses due to their high environmental mobility and their long half-lives. ³H and ¹⁴C are fixed in lichens mainly by the photosynthesis of the algal partner and then stored in the organic molecules of both alga and fungus. They have the advantage of allowing the monitoring of atmospheric water vapour without interference of soil water or soil organic substances as long as soil-inhabiting species are avoided. Lichens were collected in the surroundings of (military and civil) nuclear facilities, in areas away from any direct source of contamination and some were transplanted from a contaminated area to a non-contaminated one. The influence of the nuclear facilities can be clearly traced, sometimes in a spectacular way and the first results of analyses after transplants give a base for estimating the effective half-life of ³H in lichens.     

Biomonitoring of Trace Metals by Different species of Lichens (Parmelia) in North-West Italy

The concentrations of Cd, Cu, Mn, Ni, Pb, V, and Zn were measured in four different species of lichens (Parmelia caperata, P. pastillifera, P. saxatilis, P. sulcata) sampled in North-West Italy, in order to obtain maps showing metal distribution and the degree of deviation from background (natural) conditions. Significant differences among the species were found for Zn, Mn, Pb and V, suggesting that the combined use of mixed species in biomonitoring surveys can affect the interpretation of results. Results obtained for Parmelia caperata samples have been compared with background (natural) levels, and maps showing the distribution of each metal expressed as deviation from background levels have been obtained. Overall such maps show a medium to high alteration degree in the study area.     

Polyamine Production in Lichens Under Metal Pollution Stress

In the present study, thalli of the lichen species Pseudevernia furfuracea Zopf. and Evernia prunastri (L.) Ach. transplanted around an oil-fired power station. Following an exposure of 4 months, trace element concentrations (Al, Cd, Cr, Cu, Fe, Ni, Pb, V and Zn) and polyamine (PA) content [putrescine (Put), spermidine (Spd) and spermine (Spm)] of thalli were measured to study the polyamines production in lichens under metal pollution stress. The polyamine production was not significantly different for the two species but two types of statistically significant relationships were revealed between polyamines production and metals concentration in lichen thalli: a positive linear relationship for the pairs total PAs–Cd (P. furfuracea), total PAs–Cu (E. prunastri), Put–Pb (E. prunastri), Spm–Pb (E. prunastri) and a second-order polynomial relationship for the pairs Put–Cd (P. furfuracea), Spm–Cr (E. prunastri) and total PAs–V (E. prunastri). A possible involvement of polyamines in metal pollution stress response of lichens is discussed.     

Interactive Effects of UV-B Radiation and Chemical Contamination on Physiological Parameters in the Lichen Ramalina lacera

To assess the impact of ultraviolet B (UV-B) radiation under laboratory conditions on lichens from different biomonitoring sites, thalli of the lichen Ramalina lacera were transplanted from a clean air site to nine different polluted sites in Israel. Our objective was to determine the probability of synergistic/antagonistic effects on physiological parameters by considering two stressors: chemical contamination and UV-B. Exposure to both airborne pollutants in the field and subsequent UV-B radiation in the laboratory which led to a severe disintegration of cell membranes, followed by electrolyte leakage, indicate the probability of a synergistic effect. The impairment of the potential quantum yield of electron transfer through photosystem II (PSII) of photosynthesis indicated by a significant decrease of the ratio F_v/F_m, further demonstrated the synergistic effect of both chemical contamination and UV-B radiation. Besides enlarged amounts of stress-ethylene in lichens at contaminated sites, the reduced levels of ethylene production upon UV-B radiation in the present study suggest the likelihood of an antagonistic effect of xenobiotic elements and UV-B radiation as a result of an impaired ethylene-producing system.     

Temperature changes the dynamics of trace element accumulation in Solanum tuberosum L.

A simulated warming manipulation was conducted to evaluate the effects of temperature increase on cadmium (Cd), lead (Pb), copper (Cu), iron (Fe) and zinc (Zn) accumulation in Solanum tuberosum L. at Dingxi, Gansu, in the semiarid northwest of China. The objective of this study was to determine if temperature increases significantly changed trace element concentrations and contents in the different ecosystem compartments by affecting soil content, soil solubility and plant capture. The results reveal that an increase in temperature will lead to a significant change in trace element concentrations and contents in Solanum tuberosum L. The strongest effects of a 3°C temperature increase are increased Cu, Zn and Fe leaf concentrations of 25, 27 and 24%, respectively; but decreases in Cd, Pb, Fe, Zn and Cu tuber concentrations of 27, 55, 41, 29 and 23%, respectively. The increasing concentrations of some trace elements in Solanum tuberosum L. leaves are related to greater retranslocation, photosynthetic capacity and growth. Warming decreases the concentrations of some trace elements in tubers, implying that tuber growth rate exceeds its metal uptake rate at higher temperatures. Indeed, it is expected that by the year 2050 the increased temperature will have induced a decrease of concentrations of Cd, Pb, Cu, Fe and Zn of 9.1, 11.5, 18.5, 16.8 and 15.8%, respectively, in tubers in the study area. In addition, the results indicate that a 1–3°C increase in temperature will improve the availability of selected trace elements and transfer potential of these elements from soil to Solanum tuberosum L.     

Lichen as quantitative biomonitors of atmospheric heavy metals deposition in Central India

Three different growth forms of lichens belonging to six species; Phaeophyscia hispidula, Parmotrema praesorediosum (foliose); Caloplaca subsoluta, Diploschistes candidissmus (crustose) and Peltula euploca, Phylliscum indicum (squamulose) were studied comparatively for the biomonitoring of Al, Cd, Cr, Cu, Fe, Ni and Zn in Mandav city in central India. Based on the anthropogenic activities three sites were selected for lichen collection. To identify the sources of heavy metal pollution, their concentration was analyzed in thallus as well as in their respective substrates. The thallus of studied lichens showed higher concentration of metals such as Cd, Cr, Ni and Zn, while most of the metals were absent or present in negligible amount in substrates (Fe, Al, Cu), which proves that the accumulated metals were air borne. The foliose lichens (P. hispidula and P. praesorediosum) found highly significant in metal accumulation at each sites followed by crustose and squamulose forms. Lichen samples collected from site 2, adjacent to road side accumulated maximum quantities of Zn, Ni, Cd and Cr whereas the city centre (Site 1) had maximum concentrations of Fe, Cu and Al. The site 3 situated away from the city had lowest amount of all the metals. The analysis of variance and LSD indicated that the metal concentrations among lichen species as well as between substratum is significant at p < 0.05% and P < 0.01% level respectively.     

Sources of Biological Aerosols in Winter Precipitation in the South of Western Siberia

The results of studying biological aerosols (pollen spectra) in precipitation registered in the south of Western Siberia in the winter of 2014/15 are presented. Pollen grains of birch (Betula sp.), willow (Salix sp.), pine (Pinus sp.), and poplar (Populus sp.) were identified in the three of 28 analyzed precipitation samples. The comprehensive analysis of synoptic conditions during precipitation, back trajectories of air masses calculated with the HYSPLIT model as well as the analysis of the Northern Hemisphere snow cover dynamics and the area of distribution of the identified taxa were carried out. The results allowed determining the Euro-Scandinavian region as the main source of pollen grains inflow with precipitation to the south of Western Siberia in March 2015.     

Uranium Isotopes, Metals and Other Elements in Lichens and Tree Barks Collected in Bosnia–Herzegovina

The United Nations Environment Programme (UNEP) performed field surveys at 15 sites in Bosnia–Herzegovina where depleted uranium (DU) ammunition was used by the North Atlantic Treaty Organization (NATO) during the Balkans conflict (1994–1995). During the field missions, the Italian Environmental Protection Agency (APAT) evaluated airborne contamination due to DU dusts or aerosol particles, generated at the time of the conflict by the impact of DU ammunition on hard targets, using lichens and tree barks as biomonitors. Each sample was analyzed by alpha-spectrometry for DU determination. The ²³⁴U/²³⁸U activity concentration ratios were used to distinguish natural from anthropogenic uranium. This paper reports the data obtained by the UNEP investigation, including (non-radioactive) metal and other element concentrations in lichen and tree bark samples measured by instrumental neutron activation analysis (INAA). The results indicated: (i) lichens and tree barks are sensitive bio-accumulators of past airborne contamination by depleted uranium dusts; (ii) 8 years after the conflict, environmental DU contamination is still present at some of the target sites; and (iii) the highest concentrations of most non-radioactive elements were found at sites used for ammunition destruction.     

Vertical Distribution Patterns of Trace Elements in an Urban Environment as Reflected by their Accumulation in Lichen Transplants

The results of an investigation about the vertical distribution patterns of selected trace elements in an urban environment, as reflected by their accumulation in lichen transplants, are reported. Thalli of the lichen Pseudevernia furfuracea were transplanted in 2 sites in the urban area of Thessaloniki (N Greece), subjected to very different traffic loads: 1) Tsimiski, downtown of Thessaloniki, at one of the busiest streets of the city, a street canyon 2) Toumba, far from the city centre, at the edge of the city, at an open street. In each site, thalli were suspended along a vertical transect at 3, 6, 9 and 12 m, and retrieved after one year. The results showed that while at Toumba the elemental composition of lichen samples was essentially influenced by natural occurrence, mainly airborne soil dust, at Tsimiski also anthropogenic input of pollutants determined by vehicle traffic was involved for some elements such as Cd, Cu, Ni, Pb and Zn. The vertical distribution patterns of heavy metals accumulated in lichens showed that in general elevation has no statistically significant influence on the concentration of most metals, but this was not true for Pb, whose concentrations increased with increasing elevation from ground. Residents may thus be more exposed to high concentrations of Pb than pedestrians.     

Spatial trends in heavy metals and nitrogen deposition in Navarra (Northern Spain) based on moss analysis

A biomonitoring survey using the moss species Hypnum cupressiforme Hedw. was performed in the North of Navarra (Spain) in 2006. The levels of V, Cr, Mn, Ni, Cu, Zn, As, Zr, Cd, Hg and Pb, and the total nitrogen content were determined in the samples by means of ICP-MS, CV-AA, and the Kjeldahl method. PCA analysis showed a differentiation between lithogenic (V, Cr, Mn, Ni, As and Zr) and anthropogenic elements (Mn, Cu, Zn, Cd, Hg and Pb). Spatial distribution maps were drawn using the kriging method, in order to identify the most affected areas and the main pollution sources. A similar spatial distribution was observed for the elements belonging to each group separated by the PCA, showing an important contribution from metal industries located in the Basque Country, as well as influence of long-range transboundary pollution processes. Background levels were also determined for the study area, along with the contamination factor for the different elements analysed. Mosses seemed to be good biomonitors of N deposition in areas of accumulation.     

Halogenation processes linked to red wood ant nests (<Emphasis Type="Italic">Formica</Emphasis> spp.) and tectonics

We investigated and evaluated the occurrence of fault zone tracer gases (CO₂, He, Rn), volatile organohalogens (CH₃Cl, CHCl₃, CHBr₃), alkanes and limonene in soil and nest gases of red wood ants (RWA) in comparison to ambient air, in a seismically active area. In this new approach, we compared RWA-free areas to RWA-areas by combining different investigation and analytical methods. In soil gas, the fault zone tracer gas Rn was surprisingly highly correlated to limonene, suggesting a combination of biotic production of limonene and abiotic degassing of Rn in a seismically active area; moderate correlations were found with trihalomethanes and other halocarbons. In RWA nests a variety of elevated concentrations of haloforms were found, while remaining below the atmospheric background values in RWA-free areas. The evidence of CHCl₃ in RWA nests is the first record. Its average concentrations in nests of F. rufa and F. polyctena were up to 3 fold higher than atmospheric background and up to 28–70 fold higher compared to e.g. volcanic emissions being considered as one of its main geogenic sources. Thus, RWA nests could possibly be an additional source for CHCl₃ liberation. Consequently, apart from RWA being bioindicators for seismically active degassing faults, they might also be used as bioindicators for CHCl₃ formation in forest soils. Although we cannot yet differentiate between a geogenic/abiotic and a biotic formation. RWA nests will have to be reconsidered for halocarbon formation in future quantifications of geochemical cycles at global scale, since they impact organic soil chemistry through biotic and/or abiotic pathways. Therefore, further larger-scale research in different tectonic settings but also in well-known CHCl₃ “hot spot” study areas such as the Klosterhede area (Denmark) should focus directly on gas sampling from confirmed active fault systems. Nests of other ant species should be addressed to compare seasonal, diurnal and nocturnal variations of degassing procedures in relation to earth tides, different geologic settings, and tectonic events such as earthquakes and on quantifying the fluxes to the atmosphere.     

Continental origin and industrial sources of trace metals in the Northwest Atlantic troposphere

Trace metals (Mn, Fe, Ni, Cu, Zn, Cd, Pb and stable lead isotopes) have been analyzed in precipitation and total aerosols collected in the northwest Atlantic troposphere in April and November 1989. According to stable lead isotope signatures we encountered two main air mass sources, Mediterranean easterlies (206Pb/207Pb=1.131) and US westerlies (206Pb/207Pb=1.195–1.205). The phasing out of leaded gasoline has been invoked to explain the decrease of the 206Pb/207Pb ratios from 1.22 to 1.20 for the past 10 years in North America. Based on trajectory analyses, intermediate 206Pb/207Pb ratios are explained by a mixing of pure US westerlies with Canadian air masses (206Pb/207Pb=1.190–1.195) or Mediterranean air masses (206Pb/207Pb=1.18–1.19). Isentropic trajectories are very useful in explaining the variability of trace metal concentrations, a result of the fluctuating transport range of anthropogenic aerosols to remote marine areas of the North Atlantic. Lead concentrations appear to be closely correlated to the air mass transport patterns as defined from the meteorological analyses. For instance oceanic air masses transported over remote marine areas for more than three days were characterized by lead concentrations 2 to 10 times lower (Pb=0.5 to 2 ng/scm) than coastal air masses (Pb=3 to 10 ng/scm).Anthropogenic trace metal concentrations are generally in good agreement with the air mass signatures which display Pb and Cu, Ni, Zn concentrations higher than 2 and 10 ng/scm respectively in aerosol samples for the US source. Trace metal elemental ratios and soil enrichment factors were used to define industrial sources. Aerosol originating from the US exhibits the distinct industrial signature of Cu/Ni production and coal-oil combustion, while steel metallurgy could account for more than 50% of the overall Mn input into the Northwest Atlantic ocean.     

A summer and winter apportionment of particulate matter at urban and rural areas in northern France

The apportionment of atmospheric aerosols undertaken in Northern France during two sampling campaigns allowed to determine the influence of the atmospheric contribution of a heavy industrialized urban center on the particulate matter composition at a nearby rural site. The concentrations of major components and trace elements sampled by bulk filtration have been determined on June–July 2000 and January–February 2001, and the comparison of these two campaigns shows very well the importance of wind directions. The sources of 10 trace elements (Al, Ba, Cu, Fe, K, Mn, Pb, Sr, Ti and Zn) and 7 major components (Cl⁻, NO₃⁻, SO₄²⁻, NH₄⁺, Na, Mg and Ca) are better identified by studying their elemental contribution at each sampling site according to wind sectors. This kind of study shows that the concentrations recorded at the urban sampling site are always higher than those observed at the rural site as well during the summer campaign (about + 35%) as during the winter campaign (+ 90%), because of the predominance of the W–NW wind sector, corresponding to the influence of the urban and industrialized areas.     

Trace gases and PM2.5-bound metal abundance over a tropical urban environment,South India

Pre and Post-Monsoon levels of ambient SO₂, NO₂, PM_2.5 and the trace metals Fe, Cu, etc. were measured at industrial and residential regions of the Kochi urban area in South India for a period of two years. The mean PM_2.5, SO₂ and NO₂ concentrations across all sites were 38.98?±?1.38 µg/m³, 2.78?±?0.85 µg/m³ and 11.90?±?4.68 µg/m³ respectively, which is lower than many other Indian cities. There was little difference in any on the measured species between the seasons. A few sites exceeded the NAAQS (define acronym and state standard) and most of the sites exceeded WHO (define acronym and state standard) standard for PM_2.5. The average trace metal concentrations (ng/m³) were found to be Fe (32.58)?>?Zn (31.93)?>?Ni (10.13)?>?Cr (5.48)?>?Pb (5.37)?>?Cu (3.24). The maximum concentration of trace metals except Pb were reported in industrial areas. The enrichment factor, of metals relative to crustal material, indicated anthropogenic dominance over natural sources for the trace metal concentration in Kochi’s atmosphere. This work demonstrates the importance of air quality monitoring in this area.

     

Arsenic Speciation in Transplanted Lichens and Tree Bark in the Framework of a Biomonitoring Scenario

Arsenic and its chemical species were determined in transplanted lichens (Parmelia caperata) and tree bark (Platanus hybrida), in order to get a better understanding of their atmospheric cycling and the suitability of these materials for biomonitoring purposes. Various strategies were used (discontinuous and cumulative exposure of transplants) to biomonitor two locations in Portugal, viz. the northern Lisbon area and Sines, both highly industrialised areas.Analytical techniques comprised instrumental nuclear activation analysis (INAA), inductively coupled plasma-mass spectrometry (ICP-MS) and high performance liquid chromatography-hydride generation atomic fluorescence spectrometry (HPLC-HGAFS) for determination of total arsenic in solid materials, total arsenic in extracts of solid materials and arsenic species in extracts of solid materials, respectively.Only a fraction (up to 50%) of the extracted arsenic species could be identified and quantified in the transplanted lichens, being mainly inorganic arsenic and some methylated arsenic species. Since in a previous study these methylated arsenic species were not found in aerosols collected in the same area, it is probable that the lichen transplants studied (Parmelia caperata) do not behave as genuine passive biomonitors but are able to actively methylate inorganic arsenic to methylated arsenic species. Furthermore, this lichen-induced methylation occurs with some delay, possibly as a reaction to the transplantation of the lichen itself, and therefore transplanted lichens are only suitable for long-term biomonitoring studies. For tree bark only total arsenic concentration data could be generated since speciation analysis failed due to too low an initial total arsenic concentrations.