The multi-element content of the lichen Parmelia sulcata, soil, and oak bark in relation to acidification and climate.

Understanding how biodiversity is influenced by changing atmospheric conditions is important for conservation, public policy and environmental health. In a recent study, an impact on two of the most abundant lichens in Europe (Parmelia sulcata and Hypogymnia physodes) was recorded at Burnham Beeches lying 40 km west of London (UK) during unusual atmospheric conditions whilst other species remained unaffected. Bark and soil chemistry also influence lichen vitality and community composition. Correlations between element concentrations and element ratios in different samples help understand element cycling. To study this further, the multi-element content of the lichen P. sulcata and bark sampled in 2000 from 16 oak (Quercus robur) trees at Burnham Beeches was compared with the same elements determined in 24 surface soils sampled in 2005 from beneath the same trees. Soil pH ranged from 4.1 to 6.7. Highly significant correlations (p<0.001) for Mn/Ca ratios in lichen versus bark, soil versus bark and soil versus lichen samples confirmed cycling via the soil-tree-lichen system. Similar Mn/Ca ratios were reported in coniferous forests where high Mn concentrations were shown to limit epiphytic lichen abundance. Soil acidification influences element bioavailability and bark chemistry in Burnham Beeches with implications for lichen diversity and health. Recovery was recorded in P. sulcata, including regeneration within monitoring quadrats. Biological systems are well known to be influenced by pollution episodes.

The lichen transplant methodology in the source apportionment of metal deposition around a copper smelter in the former mining town of Karabash, Russia.

The lichen transplant monitoring methodology has been tested for source apportionment of metal deposition around the Cu smelter and former mining town of Karabash. Transplants of the lichen Hypogymnia physodes (L.) Nyl., collected from a 'control' site in July 2001, were set up at 10 stations along a 60 km NE-SW transect centred on Karabash. Samples were collected after 2 and 3 month monitoring periods and analysed using established wet-chemical techniques. The sources of particulate investigated were the smelter blast furnace and converter, floatation tailings, metallurgical slags, local road dusts, top soils and ambient airborne total suspended particulate. From multi-element least-squares modelling the blast furnace was the main source of particulate in transplants close to the smelter (<10 km). Particulate from the converter, with relatively high Pb and Zn, was found to be more widely dispersed, being finer-grained and so having a longer atmospheric residence time. Ambient airborne particulate, sampled in Karabash town using air-pump apparatus, was almost entirely derived from the converter, very different to the lichen transplants from the same area which mainly contained blast furnace particulate. It is proposed that lichens close to the smelter mainly trapped larger blast furnace-derived particulate as they have a low capture efficiency for smaller (converter) particles. The study demonstrates the utility of lichen transplants for monitoring atmospheric deposition and highlights the caution required in their use to assess ambient air quality in human health studies.

Diversity and sensitivity of epiphytes to oxides of nitrogen in London.

This study investigated the distribution and diversity of epiphytes in London in relation to NO(x) using fine-scale atmospheric dispersion modelling. The survey recorded over 3000 epiphytes from 334 trees (Fraxinus excelsior) representing 74 lichen, 14 moss, 7 fungal and 3 algal species. There was a significant inverse relationship between diversity and NO(x). Diversity declined where NO(x) exceeded 70 microg m(-3) and NO2 exceeded 40 microg m(-3), suggesting a phytotoxic effect. However, there was a significant positive relationship between NO(x) and lichen abundance due to the ubiquitous distribution of pollution tolerant species, mainly associated with eutrophication. A scale of lichen sensitivity to NO(x) has been derived.

Lichen and bryophyte distribution on oak in London in relation to air pollution and bark acidity.

Epiphytic lichen and bryophyte distribution and frequency were investigated on the trunks of 145 young oak trees throughout London and surrounding counties, and compared with pollution levels and bark pH. Sixty-four lichen and four bryophyte species were recorded. Three major zones were identified: (i) two central regions with a few lichens, bryophytes absent; (ii) a surrounding region with a more diverse flora including a high cover of nitrophyte lichens; and (iii) an outer region, characterised by species absent from central London, including acidophytes. Nineteen species were correlated with nitrogen oxides and 16 with bark pH, suggesting that transport-related pollution and bark acidity influence lichen and bryophyte distribution in London today. Lichens and bryophytes are responding to factors that influence human and environmental health in London. Biomonitoring therefore has a practical role to assess the effects of measures to improve London's air quality.

Biogeochemical signatures in the lichen Hypogymnia physodes in the mid Urals.

Multi-element content and uranium (U) isotopes were investigated in the lichen Hypogymnia physodes (native and transplants) sampled across a 60-km transect, centred on Karabash smelter town, from Turgoyak Lake (SW) to Kyshtym (NE) to investigate the origin of U. Kyshtym was the site of a major nuclear accident in 1957. (234)U/(238)U activity ratios in native thalli sampled during July 2001 were within the natural isotopic ratio in minerals. Uranium/thorium (U/Th) ratios were higher in native thalli towards the NE (average 0.73) than those in the SW (average 0.57). Element signatures in native thalli and transplants suggest U was derived from fossil fuel combustion from Karabash and sources lying further to the east. Systematic and significant U enrichment indicative of a nuclear fuel cycle source was not detected in any sample. Element signatures in epiphytic lichen transplants and native thalli provide a powerful method to evaluate U deposition.

Biomonitoring using the lichen Hypogymnia physodes and bark samples near Zlatna, Romania immediately following closure of a copper ore-processing plant.

Lichen transplants were established along a 40km transect centred on a large mine waste dump close to Zlatna town centre, two weeks after closure of a major industrial source, to compare spatial patterns of element concentrations in lichen and bark samples. After 3 months of exposure, spatial patterns of 4 element concentrations (Pb, Cu, Zn and Fe) in transplants confirmed deposition due to a point source 'Zlatna influence'. Cu and Pb reached concentrations 8 and 4 times, respectively, higher than samples transplanted in the 'background' site, and over 200 (Cu) and 2000 (Pb) times higher relative to 'background' bark. Ten out of 15 elements analysed reached highest concentrations in bark. Spatial patterns confirmed long-term pollution for 6 elements (Pb, S, Fe, Cu, Zn and Ba). The study provides a model baseline to monitor recovery following closure of major industrial sources and highlights the importance of considering biogeochemical processes when interpreting metal concentrations.

Characterisation of airborne particulate pollution in the Cu smelter and former mining town of Karabash, South Ural Mountains of Russia.

Airborne total suspended particulates (TSP), dusts from smelter blast furnace and converter stacks, and filtrates of snow melt waters have been characterised in the Cu smelter and former mining town of Karabash, Russia. TSP was collected at sites up- and downwind of the smelter and large waste and tailings dumps (Oct. 2000 and July 2001). Methods for particle size, mineralogical and elemental determinations have been tested and described, and a new PSD-MicroSOURCE XRD technique developed for the mineralogical analysis of microsamples on filter substrates. TSP in downwind samples has a mean equivalent spherical diameter of 0.5 microm (s.d. = 0.2) and was found to be 100% respirable. The main element of human health/environmental concern, above Russian maximum permitted levels (1 microg m(-3), average over any time period), was Pb which was measured at 16-30 microg m(-3) in downwind samples. Individual particulates mainly consisted of complex mixtures of anglesite (PbSO4), Zn2SnO4 and poorly ordered Zn sulphates. From experimental and theoretical considerations, a high proportion of contained Pb, Zn, Cd and As in this material is considered to be in a readily bioavailable form. Chemical and mineralogical differences between the TSP, stack dusts and snow samples are discussed, as well as the implications for human and regional environmental health.

SEM-EDX analysis in the source apportionment of particulate matter on Hypogymnia physodes lichen transplants around the Cu smelter and former mining town of Karabash, South Urals, Russia.

Scanning electron microscopy with energy-dispersive X-ray analysis (SEM-EDX) of particulate matter on lichen transplant thalli (Hypogymnia physodes) was assessed as a complementary technique to wet chemical analysis for source apportionment of airborne contaminants. Transplants (2 month exposure) stationed in the Cu smelter and former mining town of Karabash were compared with those from a control site 30 km south. Particulate matter in Karabash samples (715 analyses) showed higher levels of S, Pb, Cu, Sn and Zn compared with the control (598 analyses). Complex element associations among the particles confounded detailed mineralogical identifications, and therefore a simplified particle classification scheme was devised for source apportionment. Karabash samples contained high levels of particles classified as mining-related (MRP), and these were also identified in control samples, indicating wide spatial dispersion from the smelter and highlighting the sensitivity of the method. It was noted that MRP <2.5-microm diameter were poorly represented on lichen surfaces suggesting this may limit the usefulness of Hypogymnia transplants as proxies when assessing human health impacts from airborne particulates. Analyses of the lichen thallus surface (away from surface particulates) revealed high levels of Cu, Zn, Fe and Pb associated with organics in the Karabash samples compared with the control, with a proportionate loss of K, interpreted as being due to a stress-related increase in cell membrane permeability. This type of analysis may provide a novel SEM-EDX-based method for assessing lichen vitality. The techniques developed are presented and further implications of the study are discussed.

Lead isotopes in lichen transplants around a Cu smelter in Russia determined by MC-ICP-MS reveal transient records of multiple sources.

Transplants of the lichen Hypogymnia physodes, which is relatively tolerant to SO2 and heavy metals, were deployed for 3 months over a 60 km long SW-NE transect centered on a highly polluting Cu smelter and its adjoining town of Karabash, southern Urals, Russia. The abundance of 206Pb, 207Pb, 208Pb, and 204Pb were determined by MC-ICP-MS. The measurement of 204Pb revealed critical features, which would otherwise remain concealed: (i) The precise isotope ratios referenced to 204Pb allowed several different sources to be resolved even within the small area covered: (a) the obvious pollutant source of the Karabash Cu smelter; (b) two dispersed sources, likely to include soil with lower and different contributions of thorogenic and uranogenic lead; and (c) one anthropogenic source with higher contribution of 235U derived Pb. (ii) In part of the transect, the Pb isotope composition changed while the Pb concentrations remained the same. This indicates that the Pb content of the transplantation material from the background site was largely replaced and that the transplants provide a transient record reflecting a continuous accumulation and loss of environmental Pb, probably mainly in the form of extracellular particles. Overall, the method of lichen transplantation coupled with Pb isotope ratio determinations proved effective in assessing the usefulness of lichens in biomonitoring and in resolving different sources of atmospheric deposition.

Which factors are responsible for the changing lichen floras of London?

SO(2) is no longer the principal factor influencing the vitality and composition of lichen assemblages in London. We provide direct evidence for an impact on lichen growth during episodic high exhaust emissions coupled with unusual climatic conditions. This suggests a combination of particles and nitrogen plays a major role in influencing lichen growth. Nitrogen from traffic emissions may be at least as important as agriculture in influencing the composition of lichen assemblages.

Bioaccumulation of lead by the lichen Acarospora smaragdula from smelter emissions.

Accumulation of lead in the crustose lichen Acarospora smaragdula sensu lato is reported in the vicinity of an ore- processing plant where it is subjected to acidification and metal particulate fallout. A combination of light microscopy, X-ray element mapping, field emission scanning electron microscopy (FESEM) and other analytical techniques identifies Pb accumulation within specific fungal tissues derived from smelter particles (PM10s). No Pb was detected within the photobiont layer. Our studies suggest that Pb is highly mobile under the prevailing acidic conditions, and is fixed within the lichen cortex and melanized apothecia. Lead is also accumulated within the medulla and at the rock-lichen interface where it may precipitate as amorphous botryoidal encrustations on medullary hyphae and iron-rich particles. Modern FESEMs and microprobes enable analysis of minute quantities of material, and are important tools in understanding the fate of metals within lichens necessary to develop their use as predictive and sensitive bioindicators of aerial particulate contaminants. We suggest that crustose lichens, hitherto largely ignored in metal pollution studies, may be useful bioindicators of aerial particulate contaminants in polluted areas where macrolichens are absent.