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.     

Trace element contamination of Norwegian Lake sediments

Concentrations of Sb, Hg, Bi, Cd, Mo, As, Co, Ni, Cr, Cu, V, Pb and Zn in surface and preindustrial sediments from 210 lakes in Norway were used for studying modern atmospheric depositions of these elements. Surface sediments had considerably higher concentrations of Sb, Hg, Bi, Cd, As, Pb than preindustrial sediments. The differences decreased with latitude and altitude. A multivariate analysis including the trace elements and the major constituents (organic matter, Si, Al, Fe and Mn) of surface sediments suggested the following relationships: Sb, Hg, Bi, As, and Pb formed a group with strong associations to organic matter. Ni, Cr and Cu formed a second group, weakly associated to the inorganic sediment fraction (Si and Al). Zn and Cd formed a third group with weak associations to organic matter. Co was associated to Mn, whereas Mo and V showed no important covariations with any other trace elements or major components.     

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.     

Trace elements in size-segregated urban aerosol in relation to the anthropogenic emission sources and the resuspension

Size segregated particulate samples of atmospheric aerosols in urban site of continental part of Balkans were collected during 6 months in 2008. Six stages impactor in the size ranges: Dp?≤?0.49 μm, 0.49?2?≈?30 %) followed by traffic (PC2, σ²?≈?20 %) that are together contributing around 50 % of elements in the investigated urban aerosol. The EF model shows that major origin of Cd, K, V, Ni, Cu, Pb, Zn, and As in the fine mode is from the anthropogenic sources while increase of their contents in the coarse particles indicates their deposition from the atmosphere and soil contamination. This approach is useful for the assessment of the local resuspension influence on element’s contents in the aerosol and also for the evaluation of the historical pollution of soil caused by deposition of metals from the atmosphere.     

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.     

Annual input fluxes and source identification of trace elements in atmospheric deposition in Shanxi Basin: the largest coal base in China

Industrialization and urbanization have led to a great deterioration of air quality and provoked some serious environmental concerns. One hundred and five samples of atmospheric deposition were analyzed for their concentrations of 13 trace elements (As, Cd, Cu, Fe, Al, Co, Cr, Hg, Mn, Mo, Pb, Se, and Zn) in Shanxi Basin, which includes six isolate basins. The input fluxes of the trace elements in atmospheric deposition were observed and evaluated. Geostatistical analysis (EF, PCA, and CA ) were conducted to determine the spatial distribution, possible sources, and enrichment degrees of trace elements in atmospheric deposition. Fe/Al and K/Al also contribute to identify the sources of atmospheric deposition. The distribution of trace elements in atmospheric deposition was proved to be geographically restricted. The results show that As, Cd, Pb, Zn, and Se mainly come from coal combustion. Fe, Cu, Mn, Hg, and Co originate mainly from interactions between local polluted soils and blowing dust from other places, while the main source of Al, Cr, and Mo are the soil parent materials without pollution. This work provides baseline information to develop policies to control and reduce trace elements, especially toxic elements, from atmospheric deposition. Some exploratory analytical methods applied in this work are also worth considering in similar researches.     

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.     

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.     

Correlation patterns of metals in the epiphytic moss Hypnum cupressiforme in Bavaria

Since 1981, the Bavarian State Office for Environmental Protection (LfU) has been operating a bioindication network of epiphytic mosses Hypnum cupressiforme located on a regular grid with distances 16 km, in order to observe immission-derived metal accumulation in plant material. About 300 specimens are collected yearly (since 1991 every second year) at the end of the growth period, and the concentration of trace metals is determined. In order to gain insight into predominant sources of metal pollution in Bavaria, correlation patterns between Al, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, Sb, Hg, and Pb are analyzed by Principal Component Analysis. Detailed results are presented for the 1984 and 1995 data. At least 80% of the variance can be explained by five components. The following factors are extracted from both data sets by varimax rotation: factor 1 with similar loadings of Al, Ti, V, Cr, Fe, and As; factor 2 representing Cd and Zn; factor 3 with loadings of Sb, Pb, and Cu; factor 4 representing Mn; factor 5 being nearly identical with the Hg variable. For comparison, published region-specific correlation matrices from the 1991 moss survey performed by the German Federal Environmental Agency (UBA) – observing epigeic mosses Pleurozium schreberi – were submitted to Principal Component Analysis. With respect to the first factor, our 1991 results from Bavaria are similar to those from the Southern former GDR, but different from those from Western Germany (including Bavaria). Possible common and specific sources are discussed.     

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.     

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.     

西湖沉积物中元素分布特征研究

分析测定了西湖沉积物（２０ｍ钻探样品）不同层次中Ｆｅ、Ａｌ、Ｃａ、Ｍｇ、Ｔｉ、Ｍｎ、Ｃｕ、Ｚｎ、Ｃｄ、Ｎｉ、Ｈｇ、Ｃｒ、Ａｓ、Ｃｏ、Ｖ等１５种元素的含量，并根据元素的分布特征探讨了西湖沉积物的形成发展及重金属污染状况。     

Use of mosses (Hylocomium splendens and Pleurozium schreberi) as biomonitors of heavy metal deposition: from relative to absolute deposition values

Concentrations of 48 elements in the ground growing mosses Hylocomium splendens and Pleurozium schreberi have been compared with wet deposition data for the same elements at 13 Norwegian sites. Significant positive correlations were found for V, Fe, Co, As, Y, Mo, Cd, Sb, Ce, Sm, Er, Tl and Pb in Hylocomium splendens, and for Mg, V, Fe, Co, As, Se, Y, Mo, Cd, Sb, Tl and Pb in Pleurozium schreberi. Regression equations for transforming moss concentration data to absolute deposition rates have been calculated for those of the above elements which are of interest from a pollution point of view. The concentration levels of Li, Be, Mg, Ca, Zn, Ge, As, Se, Sr, Y, Zr, Sn, Cs, Ba, La, Ce, Pr, Nd, Sm, Ho, Yb, Hf, Ta and U were similar in the two moss species. Hylocomium splendens had highest concentrations of Cr, Fe, Co, Ni, Cu, Ga, Nb, Mo, Sb, Eu, Gd, Tb, Dy, Er, Tm, Lu, W, Tl, Pb and Th, whereas V, Mn, Rb and Cd were highest in Pleurozium schreberi. No variations were observed in the concentrations of the studied elements during the sampling season.     

Seasonal variability and source apportionment of metals in the atmospheric deposition in Belgrade

The primary objective of this study is to assess anthropogenic impacts on the environment by determination of element atmospheric depositions. Bulk depositions were collected monthly, from June 2002 to December 2006, at three urban locations in Belgrade. Concentrations of Al, V, Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb were analyzed by atomic absorption spectrometry and the current deposition fluxes of atmospheric metals were established. Fourier analysis was applied in order to investigate seasonal variation of the monthly data set. Nickel, V, Fe and Al showed pronounced seasonal dependence, while seasonal variation of the other elements was not evident. The enrichment factors of Pb, Zn, Cd and Cu were obviously above those who could have been caused by natural processes, indicating a mainly anthropogenic origin. Nickel was intermediately enriched suggesting participation of both natural and anthropogenic sources. The multivariate receptor model, Unmix, was used to analyze a 5-yr element atmospheric depositions data set. Three main source profiles (mixed road dust, oil combustion and metal processing) were identified and the overall average percentage source contributions determined.     

Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

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.     

Identification of trace element sources and associated risk assessment in vegetable soils of the urban-rural transitional area of Hangzhou, China

In the urban-rural transitional area of Hangzhou, China, 74 topsoil samples were collected from vegetable fields to measure the contents of arsenic (As), copper (Cu), cobalt (Co), cadmium (Cd), chromium (Cr), mercury (Hg), manganese (Mn), nickel (Ni), lead (Pb) and zinc (Zn). The combination of multivariate statistical and geostatistical methods successfully separated the contaminating elements (As, Cd, Cu, Hg, Pb and Zn) from uncontaminated elements (Co, Cr, Ni and Mn). A significant correlation was found between these uncontaminated elements and total Al2O3, Fe2O3, and SiO2 of the soils, indicating that the source of these elements was mainly controlled by soil-forming factors. On the other hand, these contaminating elements showed relatively weaker correlation and higher spatial variability, indicating that their enrichment and spatial heterogeneity were mostly affected by anthropic inputs. Through the pollution evaluation, it was found that only 30.8% of the study area did not suffer from moderate or severe pollution.     

应用地质累积指数评价抚顺市PM10中元素的污染

2006-2007年采暖季、风沙季和非采暖季分别在抚顺市的6个采样点采集PM10样品,用等离子体原子发射光谱(ICP-AES)法测定样品中Ti、Al、Mn、Mg、Ca、Na、K、Cu、Zn、As、Pb、Cr、Ni、Co、Cd、Fe、V等17种元素的含量,并用地质累积指数对其污染状况进行初步评价。结果表明:(1)从PM10中元素在不同采样点的含量看,抚顺市PM10中Ti、Mn、Mg、Cu、Zn、Pb、Cr、Ni、Co这9种元素在各采样点间的差别较大;Al、Ca、Na、K、As、Cd、Fe、V这8种元素差别较小。(2)从PM10中元素在不同采样季的含量看,抚顺市PM10中Mn、Mg含量的季间差别较大,其余15种元素季间差别较小。(3)Zn、Cd污染较重;Ti、Al、Mg、Ca、Na、K、As、Fe和V污染较轻;其他6种元素在6个采样点和3个采样季污染程度差别较大。(4)水库采样点各元素污染级别均不是最高;新华采样点PM10中Cu、Zn、Pb、Cr、Ni、Co、Cd污染级别均较高。(5)3个采样季PM10中Cd、Zn污染均较重,属于重度或严重污染;在采暖季PM10中Cu、Pb、Cr的地质累积指数较风沙季、非采暖季大;在非采暖季PM10中Mn、Co受到的污染比采暖季和风沙季稍严重。     

Lichens and mosses as biomonitors of trace elements in areas with thermal springs and fumarole activity (Mt. Amiata, central Italy)

The contribution of thermal springs and fumaroles to environmental levels of Al, As, B, Cd, Cu, Fe, Hg, Mo, Pb, S, Sb and Zn was evaluated by means of lichens (Parmelia sulcata) and mosses (Hypnum cupressiforme) used as bioaccumulators. Compared to the data reported for unpolluted areas, accumulation of Hg, S and Al was found, with values of Hg and S in the same range as in the vicinity of geothermal power plants. Furthermore, fumaroles turned out to be a significant source of atmospheric arsenic.