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.     

Stable sulphur and nitrogen isotopes of the moss Haplocladium microphyllum at urban,rural and forested sites

Elemental (S and N) and isotopic (δ³⁴S and δ¹⁵N) contents in the moss Haplocladium microphyllum at urban, rural and forested sites in acid rain area of South China have been analyzed for comparisons to show whether they are different and can be effectively used to identify S and N sources of atmospheric deposition. Average moss S content at rural sites (0.29 ± 0.06%) was found to be in between those at urban (0.35 ± 0.05%) and forested (0.25 ± 0.04%) sites, which are significantly different. Average N contents of urban (2.60 ± 0.56%) and rural mosses (2.84 ± 0.77%) are not significantly different, while both are significantly different to that of forested mosses at most areas, indicating that the atmosphere over rural sites has been polluted by N as seriously as that over urban sites. Nitrogen supply, relative to S supply, was in excess of the requirement for protein synthesis, especially at rural and forested sites. Moss stable isotope signatures have been proven to be effective tools for deciphering atmospheric S and N sources at these sites. Through moss δ³⁴S signatures, we found that atmospheric S at urban and forested sites was mainly from local coal combustion and domestic biomass burning, respectively, whereas northerly air masses contributed more S to forested sites. The relatively negative moss δ¹⁵N values (?7.5 ± 3.0, ?3.4 ± 2.1 and ?0.8 ± 2.1‰) demonstrated that the main form in the N deposition was NH_x in these sites. More negative δ¹⁵N signatures in urban mosses (?7.5 ± 3.0‰) indicated the contribution of NH₃ released from untreated city sewage and wastes, while relatively less negative δ¹⁵N for rural and forested mosses (3.4 ± 2.1 and ?0.8 ± 2.1‰) was largely derived from agricultural NH₃.     

Long-term (1992-2004) record of lead, cadmium, and zinc air contamination in Warsaw, Poland: Determination by chemical analysis of moss bags and leaves of Crimean linden

Between 1992 and 2004, air contamination with lead (Pb), cadmium (Cd), and zinc (Zn) in Warsaw, Poland, was monitored annually with moss (Sphagnum fallax) bags on a network of 230 sites covering the entire city. During the study the highest contamination was near the Warszawa Steel Mill, northwestern Warsaw. Lead concentrations in moss bags decreased in time, while those of Cd and Zn did not show clear trends. Between 1994 and 2004, Pb, Cd, and Zn were also monitored in the Crimean linden (Tilia Euchlora) foliage along the main city avenue and in a northwestern warsaw park. Lead concentrations decreased more near the avenue than in the park, indicating that the phasing-out of leaded gasoline had a major effect on reduced Pb contamination in Warsaw. At the same time, foliar concentrations of Cd and Zn in both areas decreased much less.     

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.     

Atmospheric transport of urban-derived NH(x): Evidence from nitrogen concentration and delta(15)N in epilithic mosses at Guiyang, SW China

Nitrogen concentration and δ¹⁵N in 175 epilithic moss samples were investigated along four directions from urban to rural sites in Guiyang, SW China. The spatial variations of moss N concentration and δ¹⁵N revealed that atmospheric N deposition is dominated by NH_x-N from two major sources (urban sewage NH₃ and agricultural NH₃), the deposition of urban-derived NH_x followed a point source pattern characterized by an exponential decline with distance from the urban center, while the agricultural-derived NH_x was shown to be a non-point source. The relationship between moss N concentration and distance (y = 1.5e^−0.13x + 1.26) indicated that the maximum transporting distance of urban-derived NH_x averaged 41 km from the urban center, and it could be determined from the relationship between moss δ¹⁵N and distance [y = 2.54 ln(x) − 12.227] that urban-derived NH_x was proportionally lower than agricultural-derived NH_x in N deposition at sites beyond 17.2 km from the urban center. Consequently, the variation of urban-derived NH_x with distance from the urban center could be modeled as y = 56.272e^−0.116x − 0.481 in the Guiyang area.     

Tissue S/N ratios and stable isotopes (δS and δN) of epilithic mosses (Haplocladium microphyllum) for showing air pollution in urban cities in Southern China

In urban cities in Southern China, the tissue S/N ratios of epilithic mosses (Haplocladium microphyllum), varied widely from 0.11 to 0.19, are strongly related to some atmospheric chemical parameters (e.g. rainwater SO₄²⁻/NH₄⁺ ratios, each people SO₂ emission). If tissue S/N ratios in the healthy moss species tend to maintain a constant ratio of 0.15 in unpolluted area, our study cities can be divided into two classes: class I (S/N > 0.15, S excess) and class II (S/N < 0.15, N excess), possibly indicative of stronger industrial activity and higher density of population, respectively. Mosses in all these cities obtained S and N from rainwater at a similar ratio. Sulphur and N isotope ratios in mosses are found significantly linearly correlated with local coal δ³⁴S and NH₄⁺-N wet deposition, respectively, indicating that local coal and animal NH₃ are the major atmospheric S and N sources.     

Progress in developing an ANN model for air pollution index forecast

An air pollution index (API) reporting system is introduced to selected cities of China for public communication on air quality data. Shanghai is the first city in China providing daily average API reports and forecasts. This paper describes the development of an artificial neural network (ANN) model for the API forecasting in Shanghai. It is a multiple layer perceptron (MLP) network, with meteorological forecasting data as the main input, to output the next day average API values. However, the initial version of the MLP model did not work well. To improve the model, a series of tests were conducted with respect to the training method and structure optimization. Based on the test results, the training algorithm was modified and a new model was built. The new model is now being used in Shanghai for API forecasting. Its performance is shown reasonably well in comparison with observation. The application of the old model was only weakly correlated with observation. In 1-year application, the correlation coefficients were 0.2314, 0.1022 and 0.1710 for TSP, SO₂ and NO_x, respectively. But for the new model, for over 8 months application, the correlation coefficients are raised to 0.6056, 0.6993 and 0.6300 for PM₁₀, SO₂, and NO₂. Further, the new algorithm does not rely on manpower intervention so that it is now being applied in several other Chinese cities with quite different meteorological conditions. The structure of the model and the application results are presented in this paper and also the problems to be further studied.     

First Europe-wide correlation analysis identifying factors best explaining the total nitrogen concentration in mosses

In this study, the indicative value of mosses as biomonitors of atmospheric nitrogen (N) depositions and air concentrations on the one hand and site-specific and regional factors which explain best the total N concentration in mosses on the other hand were investigated for the first time at a European scale using correlation analyses. The analyses included data from mosses collected from 2781 sites across Europe within the framework of the European moss survey 2005/6, which was coordinated by the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops (ICP Vegetation). Modelled atmospheric N deposition and air concentration data were calculated using the Unified EMEP Model of the European Monitoring and Evaluation Programme (EMEP) of the Convention on Long-range Transboundary Air Pollution (CLRTAP). The modelled deposition and concentration data encompass various N compounds. In order to assess the correlations between moss tissue total N concentrations and the chosen predictors, Spearman rank correlation analysis and Classification and Regression Trees (CART) were applied. The Spearman rank correlation analysis showed that the total N concentration in mosses and modelled N depositions and air concentrations are significantly correlated (0.53 ≤ r_s ≤ 0.68, p < 0.001). Correlations with other predictors were lower than 0.55. The CART analysis indicated that the variation in the total N concentration in mosses was best explained by the variation in NH₄⁺ concentrations in air, followed by NO₂ concentrations in air, sampled moss species and total dry N deposition. The total N concentrations in mosses mirror land use-related atmospheric concentrations and depositions of N across Europe. In addition to already proven associations to measured N deposition on a local scale the study at hand gives a scientific prove on the association of N concentration in mosses and modelled deposition at the European scale.     

Assessing the recovery potential of alpine moss-sedge heath: reciprocal transplants along a nitrogen deposition gradient

The potential of alpine moss-sedge heath to recover from elevated nitrogen (N) deposition was assessed by transplanting Racomitrium lanuginosum shoots and vegetation turfs between 10 elevated N deposition sites (8.2-32.9 kg ha⁻¹ yr⁻¹) and a low N deposition site, Ben Wyvis (7.2 kg ha⁻¹ yr⁻¹). After two years, tissue N of Racomitrium shoots transplanted from higher N sites to Ben Wyvis only partially equilibrated to reduced N deposition whereas reciprocal transplants almost matched the tissue N of indigenous moss. Unexpectedly, moss shoot growth was stimulated at higher N deposition sites. However, moss depth and biomass increased in turfs transplanted to Ben Wyvis, apparently due to slower shoot turnover (suggested to result partly from decreased tissue C:N slowing decomposition), whilst abundance of vascular species declined. Racomitrium heath has the potential to recover from the impacts of N deposition; however, this is constrained by the persistence of enhanced moss tissue N contents.     

Monitoring of heavy metal concentrations in home outdoor air using moss bags

One monitoring station is insufficient to characterize the high spatial variation of traffic-related heavy metals within cities. We tested moss bags (Hylocomium splendens), deployed in a dense network, for the monitoring of metals in outdoor air and characterized metals’ long-term spatial distribution and its determinants in Girona, Spain. Mosses were exposed outside 23 homes for two months; NO₂ was monitored for comparison. Metals were not highly correlated with NO₂ and showed higher spatial variation than NO₂. Regression models explained 61-85% of Cu, Cr, Mo, Pb, Sb, Sn, and Zn and 72% of NO₂ variability. Metals were strongly associated with the number of bus lines in the nearest street. Heavy metals are an alternative traffic-marker to NO₂ given their toxicological relevance, stronger association with local traffic and higher spatial variability. Monitoring heavy metals with mosses is appealing, particularly for long-term exposure assessment, as mosses can remain on site many months without maintenance.     

A multi-approach monitoring of particulate matter, metals and PAHs in an urban street canyon

For the first time until now, the results from a prediction model (Atmospheric Dispersion Modelling System (ADMS)-Road) of pollutant dispersion in a street canyon were compared to the results obtained from biomonitors. In particular, the instrumental monitoring of particulate matter (PM10) and the biomonitoring of 14 polycyclic aromatic hydrocarbons (PAHs) and 11 metals by Quercus ilex leaves and Hypnum cupressiforme moss bags, acting as long- and short-term accumulators, respectively, were carried out. For both PAHs and metals, similar bioaccumulation trends were observed, with higher concentrations in biomonitors exposed at the leeward canyon side, affected by primary air vortex. The major pollutant accumulation at the leeward side was also predicted by the ADMS-Road model, on the basis of the prevailing wind direction that determines different exposure of the street canyon sides to pollutants emitted by vehicular traffic. A clear vertical (3, 6 and 9 m) distribution gradient of pollutants was not observed, so that both the model and biomonitoring results suggested that local air turbulences in the street canyon could contribute to uniform pollutant distribution at different heights.     

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.     

Active biomonitoring of polycyclic aromatic hydrocarbons by means of mosses

Spherical bags, packed with 20 g of peat moss (Sphagnum spp.), were exposed to ambient air at a distance of 1 km from a plant manufacturing electrodes for the production of aluminium, near Rotterdam, The Netherlands. In these bags, the concentrations of six polycyclic aromatic hydrocarbons were determined, and compared with the concentrations in moss bags that had been exposed in relatively clean areas. From the results it can be concluded that, in addition to their useful application for biomonitoring of heavy metals, mosses can be applied in active biomonitoring of polycyclic aromatic hydrocarbons in ambient air.     

Compositional fractionation of polycyclic aromatic hydrocarbons (PAHs) in mosses (Hypnum plumaeformae WILS.) from the northern slope of Nanling Mountains,South China

High mountains may serve both as condenser for vapor phase persistent organic pollutants (POPs) and as barrier/sink for particulate associated less volatile POPs. The fractionation of POPs along altitudinal profiles is of interest in understanding the role of high mountains in the atmospheric transport of POPs. In the present study, polycyclic aromatic hydrocarbons (PAHs) in a selected moss species, Hypnum plumaeformae WILS, from two altitudinal profiles on the northern slope of Nanling mountains in Southern China were analyzed and compared with those in air samples. The total PAH concentration in the mosses was 310–1340 ng g⁻¹ dry weight, with phenanthrene being the most abundant. The distribution patterns of PAHs in the moss samples matched well with those in bulk atmosphere deposition in the adjacent source areas. The PAH distribution pattern in the mosses was a composite of both particle-associated and vapor phase PAHs, with heavy PAHs are susceptible to uptake/retention by mosses than light PAHs. A plot of log (C_moss/C_air) against log K_oa gave a good linear relationship in the log K_ao range of 6.7–10.2. It is suggested that the widely spread moss, H. plumaeformae WILS, can be used as an effective tool in the biomonitoring of atmospheric PAHs pollution in East Asia. The concentrations of most PAHs in the mosses generally declined with increasing altitude. In addition, there was a shift in compound pattern with an increase in the proportion of light PAHs (2–3 rings), a decrease in heavy PAHs (5–6 rings) and a relatively stable content of 4-ring PAHs. A combination of particulate scavenging and cold condensation are proposed as the major mechanisms for the compositional fractionation of PAHs along the altitudinal profile.     

Assessment of atmospheric sulfur with the epilithic moss Haplocladium microphyllum: Evidences from tissue sulfur and δS analysis

The application of geochemical signals in mosses is more and more popular to investigate the deposition of atmospheric pollutants, but it is unclear whether records of atmospheric sulfur in mosses differ between their diverse habitats. This study aimed to investigate the influence of growing condition on tissue sulfur and δ³⁴S of Haplocladium microphyllum. Epilithic and terricolous mosses in open fields, mosses under different canopy conditions were considered. We found that tissue sulfur and δ³⁴S of mosses under different habitats were not consistent and could not be compared for atmospheric sulfur research with each other even collected at the same site, moss sulfur and δ³⁴S records would be distorted by subsoil and upper canopies in different degrees, which possibly mislead the interpretation of atmospheric sulfur level and sources. Consequently, mosses on open rocks can be used reliably to assess atmospheric-derived sulfur in view of their identical sulfur and δ³⁴S evidences.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

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.     

Tree bark as a passive air sampler to indicate atmospheric polybrominated diphenyl ethers (PBDEs) in southeastern China

The different barks were sampled to discuss the influence of the tree species, trunk circumference, and bark thickness on the accumulation processes of polybrominated diphenyl ethers (PBDEs) from air into the bark. The results of different PBDE concentrations indicated that barks with a thickness of 0–3 mm collected from weeping willow, Camphor tree, and Masson pine, the trunk circumferences of which were 100 to 150 cm, were better PBDEs passive samplers. Furthermore, tree bark and the corresponding air samples were collected at Anji (AJ), Hangzhou (HZ), Shanghai (SH), and Wenling (WL) to investigate the relationship between the PBDE concentrations in bark and those in air. In addition, the significant correlation (r ²?=?0.906; P?<?0.05) indicated that atmospheric PBDEs were the principle source for the accumulation of PBDEs in the barks. In this study, the log K _BA (bark–air partition coefficient) of individual PBDE congeners at the four sites were in the range from 5.69 to 6.79. Finally, the total PBDE concentration in WL was 5 to 20 times higher than in the other three cities. The result indicated that crude household workshops contributed a heavy amount of PBDEs pollution to the environment, which had been verified by the spatial distribution of PBDEs levels in barks collected at Wenling (range, 26.53–1317.68 ng/g dw). The good correlation between the PBDE concentrations in the barks and the air samples and the variations of the PBDE concentrations in tree barks collected from different sites reflected that the bark could be used as a passive sampler to indicate the atmospheric PBDEs.     

Visibility Regulations

Experiments were conducted to investigate the appearance of contaminants in fluorocarbon-film bags which have been widely used as photochemical reactors and storage containers in air pollution research. Clean air stored in such bags was gradually contaminated by a wide range of heavy hydrocarbons (≥ C₅ ) as well as by nitrogen oxides. Warming a bag dramatically increased the contamination rate for hydrocarbons. The substances observed in the bags appear to have originated in the air outside the bags and appeared in the bags due to the permeability of the film. When a bag was stored in a controlled clean environment, the rate of contamination by hydrocarbons was dramatically reduced. Experiments in which high concentration mixtures of hydrocarbons and nitrogen oxides were stored in the bags likewise showed that some high molecular weight hydrocarbons as well as NO and NO₂ permeate through the bag walls. Decontamination of the bags can be accomplished by storing them in a clean environment.