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.     

Reconstructing temporal trends in heavy metal deposition: assessing the value of herbarium moss samples

The use of the herbarium moss archive for investigating past atmospheric deposition of Ni, Cu, Zn, As, Cd and Pb was evaluated. Moss samples from five UK regions collected over 150 years were analysed for 26 elements using ICP-MS. Principal components analysis identified soil as a significant source of Ni and As and atmospheric deposition as the main source of Pb and Cu. Sources of Zn and Cd concentrations were identified to be at least partly atmospheric, but require further investigation. Temporal and spatial trends in metal concentrations in herbarium mosses showed that the highest Pb and Cu levels are found in Northern England in the late 19th century. Metal concentrations in herbarium moss samples were consistently higher than those in mosses collected from the field in 2000. Herbarium moss samples are concluded to be a useful resource to contribute to reconstructing trends in Pb and Cu deposition, but not, without further analysis, for Cd, Zn, As and Ni.     

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.     

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.     

Air quality for metals and sulfur in Shanghai, China, determined with moss bags

In order to better understand the spatial and temporal distribution pattern of metals and sulfur present in Shanghai, moss bags with Haplocladium microphyllum (Hedw.) Broth. were suspended at 14 local monitoring stations from April through June 2006 in Shanghai, the largest city in China. The results showed that the concentrations of S, Cu, Pb, and Zn in the moss bags after exposure were higher at the sites in the industrial district and most urban districts and lower at the sites in suburban areas, and well correlated with SO₂ API and PM10 API in the air both in terms of space and time. The present study provided evidence that the moss H. microphyllum is suitable for bio-monitoring air pollution with moss bags and further confirmed that the moss-bag method is a simple, inexpensive and useful technique.     

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.     

Atmospheric trace element deposition: principal component analysis of ICP-MS data from moss samples

Data from a Norwegian survey on atmospheric deposition, including 33 elements in 495 moss samples collected in 1990, are presented. The biomonitor moss used was Hylocomium splendens, and the analyses were carried out by ICP-MS. Principal component analysis is used to identify possible sources of the elements determined in the mosses. Dominant factors represent long-range atmospheric transported elements (Bi, Pb, Sb, Mo, Cd, V, As, Zn, Tl, Hg, Ga), windblown mineral particles (Y, La, Al, Li, U, Th, Ga, Fe, V, Cr), local emission sources (Ni, Cu, Co, and As; Zn, Cd, and Hg; Fe, Cr, and Al), transport from the marine environment (Mg, B, Na, Sr, Ca), and contribution from higher plants (Cs, Rb, Ba, Mn). Comparison of the results with similar surveys from 1977 and 1985 show a decreasing contribution of most long-range transported elements to southern Norway.     

Distribution of trace metals in moss biomonitors and assessment of contamination sources in Portugal

A biomonitoring survey using the moss species [Hypnum cupressiforme Hedw. and Scelopodium touretii (Brid.) L. Kock] was performed in the whole territory of Portugal, in order to evaluate the atmospheric deposition of the following elements: Cd. Cr, Cu, Fe, Mn, Ni, Pb and Zn. The concentrations of the same elements were also obtained in two types of soil samples, collected under the moss and in nearby plots without any plant coverage, and relationships between moss and soil concentrations was investigated using the multivariate statistical method of Co-inertia Analysis. Also, relationships between concentrations in moss and several anthropogenic, geologic, pedologic and environmental parameters were screened using the same method of Co-inertia Analysis. Higher concentrations of Cu, Pb and Zn were found in areas of higher population density, with higher gasoline consumption, while higher values of Fe and Cr occur in the driest region, with lower plant coverage, indicating strong contamination by resuspended soil particles. Results also show good agreement between moss and soil contents, even for elements with high contribution of anthropogenic sources. The spatial pattern in Portugal of element contents in mosses were also detected and discussed in relation to local contamination sources.     

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.     

Estimation of metal uptake efficiencies from precipitation in mosses in Lithuania

The main sources contributing to heavy metal content in mosses in Lithuania were examined by a comparison of heavy metal concentrations in moss and corresponding deposition levels calculated from bulk deposition analysis. Bulk deposition was collected in open areas as well as under the canopy of trees. Uptake efficiencies in moss were calculated for Cd, Cr, Cu, Fe, Mn, Ni, V and Zn. All elements in moss except Pb and Cd appeared to be more or less influenced by sources other than air pollution. The general order of this influence on the heavy metal content in moss was observed as follows: Ni < V < Cr < Zn < Fe < Mn. The contents of Mn and Zn in moss were greatly influenced by leaching from the canopy while Pb was the only element which showed a net metal retention by the canopy. Concentrations of Fe and Cr in moss were dominating due to contribution from soil dust.     

Characteristics and impacts of trace elements in atmospheric deposition at a high-elevation site,southern China

To investigate the regional background trace element (TE) level in atmospheric deposition (dry and wet), TEs (Fe, Al, V, Cr, Mn, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, and Pb) in 52 rainwater samples and 73 total suspended particles (TSP) samples collected in Mt. Lushan, Southern China, were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS). The results showed that TEs in wet and dry deposition of the target area were significantly elevated compared within and outside China and the volume weight mean pH of rainwater was 4.43. The relative contributions of wet and dry depositions of TEs vary significantly among elements. The wet deposition fluxes of V, As, Cr, Se, Zn, and Cd exceeded considerably their dry deposition fluxes while dry deposition dominated the removal of pollution elements such as Mo, Cu, Ni, Mn, and Al. The summed dry deposition flux was four times higher than the summed wet deposition flux. Prediction results based on a simple accumulation model found that the content of seven toxic elements (Cr, Ni, Cu, Zn, As, Cd, and Pb) in soils could increase rapidly due to the impact of annual atmospheric deposition, and the increasing amounts of them reached 0.063, 0.012, 0.026, 0.459, 0.076, 0.004, and 0.145 mg kg^?1, respectively. In addition, the annual increasing rates ranged from 0.05% (Cr and Ni) to 2.08% (Cd). It was also predicted that atmospheric deposition induced the accumulation of Cr and Cd in surface soils. Cd was the critical element with the greatest potential ecological risk among all the elements in atmospheric deposition.     

Air dispersion of heavy metals in the vicinity of the As-Sb-Tl abounded mine and responsiveness of moss as a biomonitoring media in small-scale investigations

A systematic study was carried out to investigate air deposition and to explore the natural distribution and enrichment (contamination) with trace elements in the small area (cca. 13 km²) of an antimony-arsenic-thallium mineralization outcrop at an abandoned mine “Allchar.” The mine is located on the northwestern part of Ko?uf Mount, Republic of Macedonia. The locality of Allchar is unique in its mineral composition; besides a very intriguing mineral, lorandite, there are 45 other minerals, some of which are rare. The distribution of 53 elements (with special attention to As, Sb, and Tl) were detected in 69 moss samples from eight various species collected from this area. Moss samples were analyzed following microwave digestion by inductively coupled plasma–mass spectrometry and inductively coupled plasma–atomic emission spectrometry. It was found that the atmospheric deposition for As in the moss samples on or around the Allchar mine is >6.5 times higher and for Tl is 19 times higher compared to values for the samples from the rest of the Allchar area. By the application of multivariate cluster and R-mode factor analyses (FA), five geochemical associations were determined. Cluster and R-mode FA were used to identify and characterize element associations, and five associations of elements were determined by the method of multivariate statistics. F1 (Co, Cr, Fe, Sc, Li, V, Ga, Y, Ni, Mn, Al, La-Lu, Cu, Ge, Be, Bi, and Hf); F2 (As, Tl, Sb, and Mg); F3 (Rb, Cs, and Mo); F4 (Sr, Ba, Hf, Zr, La-Lu, and Bi), and F5 (Cd, Zn, Ag, and Cu).     

Atmospheric trace metal pollution in the Naples urban area based on results from moss and lichen bags

The results of trace element content analysed in Sphagnum capillifolium and Pseudevernia furfuracea exposed in bags in 1999 are reconsidered to evaluate the reliability of moss and lichen transplants to detect urban trace element atmospheric pollution, using Naples as a case example. After 4 months' exposure, trace element concentrations were at least twice as high as the pre-exposure values and in general higher in Sphagnum than in Pseudevernia. Moss samples were enriched in the following order: As=Cu>Mo>Pb>V>Co>Cr>Zn; lichen samples in the order: Mo>Cu>As=Co=Ni>V>Pb. Based on the calculation of a cumulative load factor, all sites located along the coast had higher trace element loads compared to sites in the hilly inland area. Complementary SEM, TEM and EDS observations showed, despite significant damage to tissue and cell integrity, the recurrent presence of particulate matter in moss and lichen, indicating the considerable presence of dust in the urban atmosphere which, according to chemical composition, may be due both to anthropogenic and natural sources such as volcanic rock and soil and sea salts.     

Element concentrations in the forest moss Hylocomium splendens: variation associated with altitude, net primary production and soil chemistry.

Net primary production (NPP) of the forest moss Hylocomium splendens increased significantly along an elevational gradient in the southern Alps of Italy. Extracellularly bound metals (Al, Ca, Co, Cr, Fe, Ni, Mo, Ni, Pb) showed declining concentrations in moss tissue with increasing altitude, presumably because the amount of exchange sites on the cell wall increases less than total biomass. Concentrations of intracellular elements did not vary (Cd, Cu, Mg, Na, Zn), or even increased (K) with altitude. The observed patterns were always independent of precipitation amount and soil concentrations of exchangeable elements. A higher soil nutrient status only enhanced K uptake by the moss. We concluded that variations in moss NPP, associated with elevational gradients, may significantly affect estimates of atmospheric deposition based on moss analysis in mountainous regions.     

Airborne trace element pollution in 11 European cities assessed by exposure of standardised ryegrass cultures

Within a European biomonitoring programme, Italian ryegrass (Lolium multiflorum Lam.) was employed as accumulative bioindicator of airborne trace elements (As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, V, Zn) in urban agglomerations. Applying a highly standardised method, grass cultures were exposed for consecutive periods of four weeks each to ambient air at up to 100 sites in 11 cities during 2000–2002. Results of the 2001 exposure experiments revealed a clear differentiation of trace element pollution within and among local monitoring networks. Pollution was influenced particularly by traffic emissions. Especially Sb, Pb, Cr, Fe, and Cu exhibited a very uneven distribution within the municipal areas with strong accumulation in plants from traffic-exposed sites in the city centres and close to major roads, and moderate to low levels in plants exposed at suburban or rural sites. Accumulation of Ni and V was influenced by other emission sources. The biomonitoring sites located in Spanish city centres featured a much higher pollution load by trace elements than those in other cities of the network, confirming previously reported findings obtained by chemical analyses of dust deposition and aerosols. At some heavily-trafficked sites, legal thresholds for Cu, Pb, and V contents in foodstuff and animal feed were reached or even surpassed. The study confirmed that the standardised grass exposure is a useful and reliable tool to monitor and to assess environmental levels of potentially toxic compounds of particulate matter.     

Current multi-element distribution in forest epigeic moss in the Czech Republic--a survey of the Czech national biomonitoring programme 2000

The content of 35 elements was determined in moss samples collected at 250 sites in the Czech Republic (CZ) in 2000. Four main areas of increased element contents in moss were revealed in the CZ (southern Moravia, Czech part of the former Black Triangle I territory, industrial northeastern Moravia, and the surroundings of a smelting town in southwestern Bohemia). The bioindicated high levels of Al, Ce, Co, Ga, La, Li, Pr, S, Th, U, V and Y atmospheric deposition loads in southern Moravia have never been reported in any paper before. Correlations were found in element content in moss vs. altitude, precipitation sums and bedrock types of the moss sampling plots. The current variability of element content in the CZ moss samples can be explained by the operation of not more than six factors.     

Monitoring of heavy metal deposition in Northern Italy by moss analysis

A survey of heavy metal deposition in the mountainous territories of Northern Italy was carried out in 1995-96. Moss samples (mainly Hylocomium splendens) were collected in a dense network of sites (about 3.2 sites/1000 km(2)) and the data of metal concentrations in moss tissues were statistically correlated with environmental and climatic factors, as well as with bulk deposition of elements and elemental concentrations in the soil. Three main geographic patterns of metal concentration in mosses could be defined: (1) Fe, Ni, and Cr, all derived both by soil particulates and anthropogenic emissions connected with ferrous metal manufacturing, were mostly concentrated in Northwestern Italy; (2) Cu and Zn, as typical multi-source elements, showed rather high concentrations with little ranges of variation over the whole area and small peaks reflecting local source points; (3) Cd and Pb reflected long-distance transport and showed highest concentrations in the regions with highest precipitation, especially in the Eastern Alps.     

Mosses and lichens as biomonitors of trace metals. A comparison study on Hypnum cupressiforme and Parmelia caperata in a former mining district in Italy.

Samples of the moss Hypnum cupressiforme and the epiphytic lichen Parmelia, caperata were collected during the summer of 1999 in an area (Colline Metallifere, central Italy) intensively exploited in the past for metals (Cu, Fe, Pb, Zn) and currently for geothermal resources. Lichens were more sensitive than mosses to emissions of S compounds near geothermal fields and abandoned sulphide ore smelting plants. Comparison of elemental compositions of the two cryptogamic species from the same sampling sites showed significantly higher concentrations of lithophile elements (Al, Cr, Fe, Mn, Ni, Ti) in the moss and atmophile elements (Hg, Cd. Pb, Cu, V, Zn) in the lichen. Patterns of bioaccumulation of elements throughout the study area were quite similar for widespread pollutants such as S, B, As, Zn, Cr and Ni, but the lichen and the moss showed different distribution patterns of Hg, Cd and other elements subject to long-range atmospheric transport. These results are due to differences in the morphology and ecophysiology of mosses and lichens and indicate that these organisms cannot be used interchangeably as biomonitors of metals in areas with mineral deposits.     

Multi-elements atmospheric deposition study in Albania

For the first time, the moss biomonitoring technique and inductively coupled plasma–atomic emission spectrometric (ICP-AES) analytical technique were applied to study multi-element atmospheric deposition in Albania. Moss samples (Hypnum cupressiforme) were collected during the summer of 2011 and September–October 2010 from 62 sites, evenly distributed over the country. Sampling was performed in accordance with the LRTAP Convention–ICP Vegetation protocol and sampling strategy of the European Programme on Biomonitoring of Heavy Metal Atmospheric Deposition. ICP-AES analysis made it possible to determine concentrations of 19 elements including key toxic metals such as Pb, Cd, As, and Cu. Cluster and factor analysis with varimax rotation was applied to distinguish elements mainly of anthropogenic origin from those predominantly originating from natural sources. Geographical distribution maps of the elements over the sampled territory were constructed using GIS technology. The median values of the elements in moss samples of Albania were high for Al, Cr, Ni, Fe, and V and low for Cd, Cu, and Zn compared to other European countries, but generally were of a similar level as some of the neighboring countries such as Bulgaria, Croatia, Kosovo, Macedonia, and Romania. This study was conducted in the framework of ICP Vegetation in order to provide a reliable assessment of air quality throughout Albania and to produce information needed for better identification of contamination sources and improving the potential for assessing environmental and health risks in Albania, associated with toxic metals.     

Assessment of intermittent trace element pollution by moss bags

Moss bags of the aquatic bryophyte Rhynchostegium riparioides (Hedw.) C. Jens. were transplanted into an irrigation ditch in the Province of Vicenza (NE Italy), affected by intermittent trace element contamination due to galvanics. The study aimed at: (a) testing the ability of mosses to detect different patterns of pollution, (b) providing information about intensity and temporal extension of pollution events, and (c) localising the main sources. Moss bags were collected after 20, 34, 48 and 62 days of exposure. The concentrations of As, Cd, Cr, Cu, Hg, Mn, Ni, Pb and Zn in the desiccated apical shoots of mosses were determined by atomic absorption spectrophotometry. The mean concentrations measured in non-contaminated stations of a previous work were adopted as background values, to calculate the contamination factor (CF). Transplants were able to: (a) detect spatial patterns of bioaccumulation, (b) reveal chronic contamination by Pb and Cu, intermittent contamination by Cr, Zn, and Ni, and a release of Cd by moss bags, and (c) localise the main emission sources.