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A study was conducted to investigate the air deposition and explore the distribution of potentially toxic elements in the Mariovo region, North Macedonia, using moss samples as biomonitors of air pollution. The distribution of 44 chemical elements was detected in 20 moss samples collected in the area. The moss samples were analyzed after microwave digestion using inductively coupled plasma - atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS). It was found that atmospheric deposition for some potentially toxic elements in the moss samples in the study area was influenced only by lithogenic origin. R-mode factor analysis was used to identify and characterize elemental associations. Three factors were separated from the group of macroelements determined by ICP-AES: Factor 1 (Cr, Fe, Ni, V, Al, Zn, Pb, and Li), F2 (Li, Sr, and Ba), and F3 (P, and K); and two associations were separated from the group of trace elements determined by ICP-MS: Factor 1 (Ga, Sc, Ti, Co, Zr, Rb, As, Cs, Ge, Y, Sn, Mo, and rare earth elements - REEs) and Factor 2 (Br, B, Cd, I, and Sb).

This study addresses the atmospheric deposition of trace elements investigated in Albania, Croatia and Macedonia in 2010 as part of the European Moss Study. This study provides data on the concentration of ten metals (Cd, Cr, Cu, Ni, Pb, V, Zn, Fe, Al, and Li) in naturally growing mosses. In general, all concentration data follow a lognormal distribution. Cd, Cr, Ni, and Zn show strong fluctuations in the moss samples from Albania and Macedonia, and Pb, Fe, and Al in the mosses from Croatia. The concentrations of Cd, Cu, and Zn were higher in the samples from Croatia than in those from Albania and Macedonia; the concentrations of Cr, Ni, V, Fe, Al, and Li were higher in the samples from Albania than in those from Croatia and Macedonia; and a higher concentration of Pb was found in the samples from Macedonia. The observed relationship between the concentration of lithogenic elements (Al, Fe, and V) and the air quality index (AQI) confirms that moss species have a high capacity to retain atmospheric deposition particles. The anthropogenic emission sources of these elements from local and long-range transport were considered to be the most important factors affecting air quality in the studied areas.

A study was carried out to investigate air deposition and to explore the natural distribution and contamination with potentially toxic elements (PTEs) in the Kumanovo Region, North Macedonia, by using moss samples as biomonitors for air pollution. The distribution of 51 elements was detected in 42 moss samples collected from this area. Moss samples were analyzed following microwave digestion by inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS). It was found that the atmospheric deposition for some PTEs in the moss samples in specific parts of the study area is influenced by anthropogenic and urban activities. R-mode factor analysis was used to identify and characterize element associations, and six associations of elements were determined. Four factors were separated from the group of macroelements determined by ICP-AES: Factor 1 (Al, Cr, Fe, Li, Ni, V, and Zn), F2 (K, Mg, and P), F3 (Ba and Sr), and F4 (Cd, Pb, and Zn); and two associations were separated from the group of trace elements determined by ICP-MS: Factor 1 (As, Co, Cs, Ga, Ge, Sc, Ti, Y, Zr, and rare earth elements-REEs) and Factor 2 (Bi, Br, Hg, I, Sb, Sn, and W).

In the summer of 2005 and 2010, moss samples were collected from 72 sampling sites evenly distributed all over the territory of Republic of North Macedonia. Kjeldahl method was used to determine the nitrogen content in the samples. Descriptive statistics and distribution maps were prepared. Data obtained from these two surveys were compared, and additional comparison was done with data obtained from similar studies in the South-Eastern European countries and Finland as a clean area. The median value of N content in the samples collected in 2005 is 1.21%, varies from 0.70% to 1.54%, while the content of N in samples collected in 2010 ranges between 0.68% and 1.75% with the median value of 1.06%. High contents of N were found in the Northern and Central parts of the country mainly as a result of agricultural activities, industry and traffic.

The air quality of Albania is evaluated by trace metals atmospheric deposition using moss biomonitoring method. Bryophyte moss (Hypnum cupressiforme Hedw.) samples were collected during August and September 2015 from 55 sampling points distributed over the entire territory of Albania. The concentrations of Cr, Cu, Fe, Ni, Pb, V, and Zn in moss samples was determined by ICP-AES, ETAAS (As and Cd), and CVAAS (Hg) analysis. Spatial distribution and temporal trend of the moss elements is discussed in this study. Different variability was found in moss metal concentrations that may reflect their spatial distribution patterns and may identify the location of the areas with high contamination of each element. Compared with the measurements of moss collected in 2010, significant differences were found in the concentrations of As, Cr, Cu, Hg, Ni, Pb, and Zn. The differences between two moss surveys may reflect changes in the bioavailability of the elements resulting from wet and dry deposition respectively during 2015 and 2010 moss biomonitoring survey. The pollution loading index that was applied to judge the content of metal contamination indicated moderate pollution throughout Albania. Examination of the potential ecological risk found that As, Cd, Cr, Hg, Ni, and Pb pose the highest potential ecological risks particularly in the areas with high metal contents. Factor analysis applied to investigate the probable sources of metals in the environment suggested that Al and Fe likely originated from natural sources. As, Cd, Hg, Pb, Cu, Zn, Ni, and Cr likely originated from anthropogenic sources associated with long-range transport, transboundary pollution and local emission sources.

In this work attic dust was examined as historical archive of anthropogenic emissions, with the aim of elucidating the pathways of enrichments associated with exploitation of Cu, Pb, and Zn minerals in the Bregalnica river basin region. Attic dust samples were collected from 84 settlements. At each location for attic dust sampling, topsoil samples from the house yards were also collected. Mass spectrometry with inductively coupled plasma (ICP-MS) was applied as analytical technique for determination of Ag, Bi, Cd, Cu, In, Mn, Pb, Sb, Te, W, and Zn. The Universal Kriging method with linear variogram interpolation was applied for the construction of spatial distribution maps. Thеsе elements are normally associated with air pollution (Cd-Pb-Zn), and usually are not influenced by lithological background. This investigation fortifies an extended anthropogenic association (Ag, Bi, In, and Mn) that implement some other anthropogenic activities such as agricultural activities (use of urban sludge, manure and fertilizers) or their occurrence can be a secondary affection from mine poly-metallic pollution. Spatial patterns showed intensive deposition in the areas of Pb-Zn mining activities ("Sasa" and "Zletovo" mines) and copper mine "Bučim". Long-distance distributions of higher contents of these elements from the mines were not detected.

This study presents the spatial distribution of 37 elements in 48 moss samples collected over the whole territory of Albania and provides information on sources and factors controlling the concentrations of elements in the moss. High variations of trace metals indicate that the concentrations of elements are affected by different factors. Relations between the elements in moss, geochemical interpretation of the data, and secondary effects such as redox conditions generated from local soil and/or long distance atmospheric transport of the pollutants are discussed. Zr normalized data, and the ratios of different elements are calculated to assess the origin of elements present in the current moss samples with respect to different geogenic and anthropogenic inputs. Factor analysis (FA) is used to identify the most probable sources of the elements. Four dominant factors are identified, i.e. natural contamination; dust emission from local mining operations; atmospheric transport of contaminants from local and long distance sources; and contributions from air borne marine salts. Mineral particle dust from local emission sources is classified as the most important factor affecting the atmospheric deposition of elements accumulated in the current moss samples. The open slag dumps of mining operation in Albania is probably the main factor contributing to high contents of Cr, Ni, Fe, Ti and Al in the moss. Enrichment factors (EF) were calculated to clarify whether the elements in the present moss samples mainly originate from atmospheric deposition and/or local substrate materials., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Distributions of a total of 21 elements were monitored in significantly lead-zinc polluted area using moss species (Hypnum cupressiforme and Camptothecium lutescens) used interchangeably, covering a denser sampling network. Interspecies comparison was conducted using Box-Cox transformed values, due to their skewed distribution. The median concentrations of trace elements in the both mosses examined decreased in the following order: Fe>Mn>Zn>Pb>Cu>Ni∼Cr∼As>Co>Cd>Hg. For almost all analyzed elements, H. cupressiforme revealed higher bio-accumulative abilities. For arsenic contents was obtained ER-value in favor of C. lutescens. The ER for the element contents according to the distance from the pollution source in selected areas was significantly enriched for the anthropogenic introduced elements As, Cd, Cu, Pb and Zn. After Box-Cox transformation of the content values, T B was significantly different for As (4.82), Cd (3.84), Cu (2.95), Pb (4.38), and Zn (4.23). Multivariate factor analysis singled out four elemental associations: F1 (Al-Co-Cr-Fe-Li-Ni-V), F2 (Cd-Pb-Zn), F3 (Ca-Mg-Na-P) and F4 (Cu) with a total variance of 89%. Spatial distribution visualized the hazardously higher contents of "hot spots" of Cd > 1.30 mg/kg, Cu > 22 mg/kg, Pb > 130 mg/kg and Zn > 160 mg/kg. Therefore, main approach in moss biomonitoring should be based on data management of the element distribution by reducing the effect of extreme values (considering Box-Cox data transformation); the interspecies variation in sampling media does not deviate in relation to H. cupressiforme vs. C. lutescens.

Attic dusts were examined as historical archives of anthropogenic emissions, with the goal of elucidating the enrichment pathways associated with hydrothermal exploitation of Cu, Pb, and Zn minerals in the Bregalnica River basin in the eastern part of the Republic of Macedonia. Dust samples were collected from 84 settlements. Atomic emission spectrometry and mass spectrometry with inductively coupled plasma were applied as analytical techniques for the determination of 69 element contents. Multivariate analysis was applied for the extraction of dominant geochemical markers. The lithogenic distribution was simplified to six dominant geochemical markers: F1: Ga-Nb-Ta-Y-(La-Gd)-(Eu-Lu); F2: Be-Cr-Li-Mg-Ni; F3: Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn; F4: Ba-Cs-Hf-Pd-Rb-Sr-Tl-Zr; F5: As-Co-Ge-V; and F6: К-Na-Sc-Ti. The anthropogenic effects on the air pollution were marked by a dominance of F3 and secondary dominance of F5. The fifth factor also was determined as a lithogenic marker for the occurrence of the very old Rifeous shales. The first factor also presents a very unique association that despite the heterogeneity relays on natural phenomena of tracking the deposition in areas of Proterosoic gneisses; related to the distribution of fine particles was associated with carbonate-silicate volcanic rocks. Intensive poly-metallic dust depositions were recorded only in the surroundings of localities where the hydrothermal extractions are implemented. Long-term deposition can be considered as pollution indexes for these hot spots. This mainly affects the Cd, Pb, and Zn deposition that is as high as 25, 3900, and 3200 mg/kg, respectively.

Atmospheric deposition was investigated using the terrestrial moss species Hypnum cupressiforme (Hedw.) and Homolothecium lutescens (Hedw.) in the Bregalnica River basin, Republic of Macedonia. Long-term emission occurs in this area due to the hydrothermal exploitation of Pb-Zn deposits (Sasa and Zletovo mines) and copper ore exploitation and floatation (Bučim mine). Determination of the chemical elements was conducted using atomic emission spectrometry with inductively coupled plasma (ICP-AES) and mass spectrometry with inductively coupled plasma (ICP-MS). A combination of multivariate techniques (PCA, FA and CA) was applied for data processing and identification of element association with lithogenic/anthropogenic origin. Seven dominant factors were extracted from the total of 69 analysed elements. Spatial distribution maps were constructed for the determination and localisation of smaller areas with higher contents of certain anthropogenic elements. In this way, the influences of selected human activities on local air pollution can be determined. The summarised data show quantification of the element distributions. This not only allows the determination of the distribution of hazardous elements but also presents complete characterisation of element deposition in the environs of mines.

For analysing element input into ecosystems and associated risks due to atmospheric deposition, element concentrations in moss provide complementary and time-integrated data at high spatial resolution every 5 years since 1990. The paper reviews (1) minimum sample sizes needed for reliable, statistical estimation of mean values at four different spatial scales (European and national level as well as landscape-specific level covering Europe and single countries); (2) trends of heavy metal (HM) and nitrogen (N) concentrations in moss in Europe (1990-2010); (3) correlations between concentrations of HM in moss and soil specimens collected across Norway (1990-2010); and (4) canopy drip-induced site-specific variation of N concentration in moss sampled in seven European countries (1990-2013). While the minimum sample sizes on the European and national level were achieved without exception, for some ecological land classes and elements, the coverage with sampling sites should be improved. The decline in emission and subsequent atmospheric deposition of HM across Europe has resulted in decreasing HM concentrations in moss between 1990 and 2010. In contrast, hardly any changes were observed for N in moss between 2005, when N was included into the survey for the first time, and 2010. In Norway, both, the moss and the soil survey data sets, were correlated, indicating a decrease of HM concentrations in moss and soil. At the site level, the average N deposition inside of forests was almost three times higher than the average N deposition outside of forests.

Moss species (Homalothecium lutescens, Hypnum cupressiforme, Brachythecium glareosum, and Campthotecium lutescens) were used as suitable sampling media for biomonitoring the origin of heavy-metal pollution in the lead-zinc (Pb-Zn) mine "Toranica" near the Kriva Palanka town, Eastern Macedonia. The contents of 20 elements-silver (Ag), aluminum (Al), arsenic (As), barium (Ba), calcium (Ca), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), potassium (K), lithium (Li), magnesium (Mg), manganese (Mn), sodium (Na), nickel (Ni), Pb, strontium (Sr), vanadium (V), and (Zn) were determined by atomic emission spectrometry with inductively coupled plasma. Data processing was applied with combinations of multivariate statistical methods: factor analysis, principal component analysis, and cluster analysis. Moss' responsiveness to the atmospheric distribution of the selected elements was investigated in correlation to the specific geology of the region (soil dusting). Lithogenic distribution was characterized with the distribution of three dominant geochemical associations: F1: Al-Li-V-Cr-Ni-Co, F2: Ba-Ca-Sr, and F3: Cd-Zn-Pb-Cu. Spatial distribution was constructed for visualization of the factor deposition. Furthermore, air distribution (passive biomonitoring) versus soil geochemistry of the analyzed elements was examined. Significant correlations were singled out for Pb, Zn, and Cd and for Mg(moss)/Na(soil). Characteristic lithological anomaly characterized the presence of the oldest geological volcanic rocks. Zone 1 (Pb-Zn mine surrounding) presents a unique area with hydrothermal action of Pb-Zn mineralization leading to polymetallic enrichments in soil. This phenomenon strongly affects the environment, which is a natural geochemical imprint in this unique area (described with the strong dominance of the geochemical association Cd-Zn-Pb-Cu).

Moss biomonitoring technique using moss species Homolothecium lutescens (Hedw.) Robins and Hypnum cupressiforme (Hedw.) was applied to air pollution studies in the Republic of Macedonia. The study was performed in the framework of the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops under the auspices of the United Nations Economic Commission for Europe (UNECE) Convention on Long-Range Transboundary Air Pollution (LRTAP). The presence of 47 elements was determined by instrumental epithermal neutron activation analysis, atomic absorption spectrometry and atomic emission spectrometry with inductively coupled plasma. Normality of the datasets of elements was investigated, and Box-Cox transformation was used in order to achieve normal distributions of the data. Different pollution sources were identified and characterized using principal component analysis (PCA). Distribution maps were prepared to point out the regions most affected by pollution and to relate this to the known sources of contamination. The cities of Veles, Skopje, Tetovo, Radoviš and Kavadarci were determined to experience particular environmental stress. Moreover, three reactivated lead-zinc mines were also shown to contribute to a high content of lead and zinc in the eastern part of the country. However, a comparison with the previous moss survey conducted in 2005 showed a decreasing trend of pollution elements that are usually associated with emission from industrial activities.

In recent decades, naturally growing mosses have been used successfully as biomonitors of atmospheric deposition of heavy metals and nitrogen. Since 1990, the European moss survey has been repeated at five-yearly intervals. In 2010, the lowest concentrations of metals and nitrogen in mosses were generally found in northern Europe, whereas the highest concentrations were observed in (south-)eastern Europe for metals and the central belt for nitrogen. Averaged across Europe, since 1990, the median concentration in mosses has declined the most for lead (77%), followed by vanadium (55%), cadmium (51%), chromium (43%), zinc (34%), nickel (33%), iron (27%), arsenic (21%, since 1995), mercury (14%, since 1995) and copper (11%). Between 2005 and 2010, the decline ranged from 6% for copper to 36% for lead; for nitrogen the decline was 5%. Despite the Europe-wide decline, no changes or increases have been observed between 2005 and 2010 in some (regions of) countries., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The atmospheric deposition of heavy metals in Albania was investigated by using a carpet-forming moss species (Hypnum cupressiforme) as bioindicator. Sampling was done in the dry seasons of autumn 2010 and summer 2011. Two different sampling schemes are discussed in this paper: a random sampling scheme with 62 sampling sites distributed over the whole territory of Albania and systematic sampling scheme with 44 sampling sites distributed over the same territory. Unwashed, dried samples were totally digested by using microwave digestion, and the concentrations of metal elements were determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and AAS (Cd and As). Twelve elements, such as conservative and trace elements (Al and Fe and As, Cd, Cr, Cu, Ni, Mn, Pb, V, Zn, and Li), were measured in moss samples. Li as typical lithogenic element is also included. The results reflect local emission points. The median concentrations and statistical parameters of elements were discussed by comparing two sampling schemes. The results of both sampling schemes are compared with the results of other European countries. Different levels of the contamination valuated by the respective contamination factor (CF) of each element are obtained for both sampling schemes, while the local emitters identified like iron-chromium metallurgy and cement industry, oil refinery, mining industry, and transport have been the same for both sampling schemes. In addition, the natural sources, from the accumulation of these metals in mosses caused by metal-enriched soil, associated with wind blowing soils were pointed as another possibility of local emitting factors.

Moss samples from four dominant species (Hypnum cupressiforme, Pleurozium schreberi, Homalothecium sericeum and Brachythecium rutabulum) were collected during the summer and autumn of 2010 from 121 sampling sites evenly distributed over the territory of Croatia. Samples were totally digested by using microwave digestion system, whilst mercury was analysed by using cold vapour atomic absorption spectrometry (CV-AAS). Descriptive statistics were done from analyses of mercury in all moss samples. The content of mercury ranged from 0.010 to 0.145 mg kg(-1) with a median value of 0.043 mg kg(-1). Hg distribution map shows the sites of the country with higher levels of this element. High contents of Hg were found in moss samples collected from the regions of Podravina and Istria as a result of anthropogenic pollution. Comparison of median values and ranges with those found in moss samples in 2006 shows slight reduction of mercury air pollution. When compared to the results obtained from recent studies conducted in Slovenia, Macedonia and especially in Norway-which serves as a reference considering the fact that it is a pristine area-mercury air pollution in Croatia is insignificant.

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.

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 km(2)) of an antimony-arsenic-thallium mineralization outcrop at an abandoned mine "Allchar." The mine is located on the northwestern part of Kožuf 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).

Moss samples were collected from 121 sampling sites all over Croatia during the summer and autumn of 2010. They were totally digested by using microwave digestion system and analysed by using atomic emission spectrometry with inductively coupled plasma (ICP-AES). Descriptive statistics and maps of distribution were made. The data obtained in this study were compared with those from the study in 2006 and additionally with the data obtained in the similar studies in neighbouring countries and Norway as pristine area. The median value of nickel is 3.16 mg kg(-1) and the content varies from 1.04 to 14.66 mg kg(-1). The content of vanadium ranges between 0.23 and 37.26 mg kg(-1) with the median value of 2.55 mg kg(-1). High contents of these elements are found in the vicinity of Rijeka, Zagreb and Sisak as a result of their emission from oil refinery, thermal power plant and industrial processes.

Moss biomonitoring technique was applied in a heavy-metal pollution study of Croatia in 2006 when this country participated in the European moss survey for the first time. This survey was repeated in 2010, and the results are presented in this study. For this purpose, 121 moss samples were collected during summer and autumn 2010. The content of 21 elements was determined by inductively coupled plasma-atomic emission spectrometry and atomic absorption spectrometry. Principal component analyses was applied to show the association between the elements. Six factors (F1-F6) were determined, of which two are anthropogenic (F3 and F6), two are mixed geogenic-anthropogenic (F1 and F5), and two are geogenic factors (F2 and F4). Geographical distribution maps of the elements over the sampled territory were constructed using geographic information systems technology. Comparison of the median values of some of the anthropogenic elements-such as arsenic, cadmium, chromium, copper, mercury, nickel, lead, vanadium, and zinc-with those from the 2006 study shows that anthropogenic pollution has changed insignificantly during the last 5 years. The data obtained in the investigation in Norway are taken for comparison with pristine area, which indicates that Croatia is somewhat polluted but still, shows a more favourable picture when compared with two neighbouring countries.

Mineral phases and their content were determined in attic dust samples collected from 27 houses in the Tikveš Valley, Republic of Macedonia. By using quantitative X-ray diffraction, the principal mineral phases were determined to be the serpentinite group (chrysotile, lizardite) and amphibole group of minerals (ribecite, tremolite, actinolite) present in the attic dust samples from this region which are not common constituents of urban dust. Strong correlations existed between these mineral phases in the dust and those in ores processed at a ferronickel smelter plant situated in this region. Spatial distributions of specific mineral phases were made and were consistent with wind directions and predicted deposition (60-70 %) of dust emitted from the metallurgical plant.

The purpose of this study was to determine the atmospheric deposition of chromium in Croatia by using moss biomonitoring technique and atomic emission spectrometry with inductively coupled plasma (ICP-AES). Moss samples (Hylocomium splendens, Hypnum cupressiforme, Brachythecium rutabulum and Homalothecium Sericeum) were collected from 121 sampling sites evenly distributed over the country, during the summer and autumn of 2010. Collected samples were air dried, then cleaned and digested by using microwave digestion system. The median value obtained in this study (1.94 mg kg⁻¹) compared with the median value of previous investigation performed in 2006 (2.75 mg kg⁻¹) shows that the content of chromium decreased. Higher contents of chromium were found in moss samples collected in the regions of Central Croatia, in/near the cities of Zagreb, Sisak and Kutina, which, in the most of the cases, are result of anthropogenic activities. In Costal Croatia, higher values have a natural origin due to the significantly higher content of Cr in soil from this region. The results were compared with those from similar studies in neighboring and other Balkan countries. It was established that the content of chromium in Croatia is lower than in the most of these countries.

Previous analyses at the European scale have shown that cadmium and lead concentrations in mosses are primarily determined by the total deposition of these metals. Further analyses in the current study show that Spearman rank correlations between the concentration in mosses and the deposition modelled by the European Monitoring and Evaluation Programme (EMEP) are country and metal-specific. Significant positive correlations were found for about two thirds or more of the participating countries in 1990, 1995, 2000 and 2005 (except for Cd in 1990). Correlations were often not significant and sometimes negative in countries where mosses were only sampled in a relatively small number of EMEP grids. Correlations frequently improved when only data for EMEP grids with at least three moss sampling sites per grid were included. It was concluded that spatial patterns and temporal trends agree reasonably well between lead and cadmium concentrations in mosses and modelled atmospheric deposition., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The purpose of this study was to establish the atmospheric deposition of various elements in the Kavadarci region, Republic of Macedonia (known for its ferronickel mining and metallurgical activities) using moss biomonitoring, and to determine whether the deposition is anthropogenic or from geogenic influences. The sampling network includes 31 moss samples evenly distributed over a territory of about 600 km(2). A total of 46 elements (Ag, Al, As, Au, Ba, Be, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hg, Ho, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Rb, Sb, Sm, Sr, Tb, Th, Ti, U, V, Yb, Zn, Zr) were determined by mass spectrometry with inductively coupled plasma (ICP-MS). Based on a distribution pattern of elements determined in moss, two anthropogenic geochemical associations (Co-Cr-Cu-Fe-Mg-Ni and As-Cd-Cu-Hg-Pb-Zn), were detected. The distribution of these elements shows an increased content (especially Ni, Co and Cr) in the moss samples from the surroundings of the smelter plant compared to the rest of the samples. Thus, the median value of Ni in moss samples from the whole region (40 mg kg(-1)) is much higher than the median for Macedonia (5.82 mg kg(-1)). Moreover, the median content of Ni in the moss samples from the polluted area (around the smelter) is 178 mg kg(-1) with an enrichment ratio in the moss samples of almost 5.5 times higher than the unpolluted areas (32 mg kg(-1)). This fact confirms the influence of the dust from the ferronickel plant to the air pollution in this region.

In 2002 and 2005 the moss biomonitoring technique was applied to air pollution studies in the Republic of Macedonia in the framework of the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops under the auspices of the United Nations Economic Commission for Europe (UNECE-ICP Vegetation) Convention on Long-Range Transboundary Air Pollution (LRTAP). In August 2005 samples of the terrestrial mosses Homolothecium lutescens and Hypnum cupressiforme were collected at 72 sites evenly distributed over the territory of the country, in accordance with the sampling strategy of the European moss survey programme. A total of 41 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Zr, Mo, Cd, Sb, I, Cs, Ba, La, Ce, Sm, Eu, Tb, Dy Hf, Ta, W, Hg, Pb, Th, and U) were determined by instrumental epithermal neutron activation analysis and atomic absorption spectrometry. Principal component analysis was used to identify and characterize different pollution sources. Distributional maps were prepared to point out the regions most affected by pollution and to relate this to known sources of contamination. A few areas, as in 2002, are experiencing particular environmental stress: Veles, Skopje, Tetovo, Radoviš and Kavadarci-Negotino, whereas the agricultural regions in the south, south-west, and south-east show median European values for most elements of mainly pollution origin. A significant increase in the content of Ni is noticed in the 2005 moss survey compared with 2002, due to the increased production of the ferro-nickel smelter in Kavadarci. A higher content of Cd, Hg, and Pb in 2005 relative to 2002 can be explained by pollution from the lead-zinc smelter in Veles, as well as the pollution that comes from the open slag waste dump of this smelter. Protection activities on the dump of slag from the former ferrochromium smelter located near Tetovo resulted in a lower content of Cr in the 2005 moss survey.

The main aim of this article was to assess the atmospheric pollution with heavy metals due to copper mining Bučim near Radoviš, the Republic of Macedonia. The open pit and mine waste and flotation tailings are continually exposed to open air, which leads to winds carrying the fine particles into the atmosphere. Samples of attic dust were examined as historical archives of mine emissions, with the aim of elucidating the pathways of pollution. Dust was collected from the attics of 29 houses, built between 1920 and 1970. Nineteen elements (Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Li, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn) were analyzed by atomic emission spectrometry with inductively coupled plasma. The obtained values of the investigated elements in attic dust samples were statistically processed using nonparametric and parametric analysis. Factor analysis revealed three factors governing the source of individual chemical elements. Two of them grouping Ca, Li, Mg, Mn, and Sr (Factor 1) and Co, Cr, and Ni (Factor 2) can be characterized as geogenic. The third factor grouping As, Cu, and Pb is anthropogenic and mirrors dust fallout from mining operation and from flotation tailings. Maps of areal deposition were prepared for this group of elements, from which correlation of these anthropogenic born elements was confirmed.

This investigation was undertaken to determine the atmospheric pollution with heavy metals due to copper mining Bucim near Radovis, the Republic of Macedonia. Moss samples (Hyloconium splendens and Pleurozium schrebery) were used for biomonitoring the possible atmospheric pollution with heavy metals in mine vicinity. Sixteen elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mn, Na, Ni, Pb, Sr, and Zn) were analysed by application of flame and electrothermal atomic absorption spectrometry (FAAS and ETAAS) and atomic emission spectrometry with inductively coupled plasma (ICP-AES). The obtained values were statistically processed using nonparametric and parametric analysis. The median value for copper obtained from moss samples (10 mg kg(-1)) was much lower compared with the same values for the whole territory of the Republic of Macedonia (22 mg kg(-1)). The range of values (2.1-198 mg kg(-1)) shows much higher content of this element in the samples taken from the study area compared to the appropriate values for the whole territory of Macedonia. The association of elements As, Cd, Cu, Fe, Pb, and Zn was singled out by factor analysis as a characteristic anthropogenic group of elements. Maps of area deposition were made for this group of elements, wherefrom correlation of these anthropogenic born elements was confirmed.