Toxic metal content of particulate matter (PM10), within the Greater Area of Athens

This study presents results from a yearlong particulate matter measurement campaign, conducted across the Greater Athens Area, at four locations, between 1st June 2001 and 31st May 2002. The collected PM(10) 24-h samples were analyzed for nine toxic metals and metalloids (Pb, As, Cd, Ni, Cr, Mn, V, Cu, Hg). Concerning the five elements regulated by the European Union, annual average concentrations of Pb were found below the limit values at all sites, Cd and Ni concentrations were lower than the prospective assessment thresholds at all sites, concentrations of As exceeded the assessment threshold at two sites, while concentrations of Hg were found below detection limits in all samples. Concentration levels of Mn and V were in compliance with the values proposed by the World Health Organization. The seasonal and spatial variability of metal concentrations was examined and site-specific correlation analysis was conducted for the identification of metals with similar origin. The association between trace metals and NO(x) concentrations was explored to account for the impact of automotive sources, at two traffic-impacted sites. Cu was the metal most closely linked with the road transport sector. The relation of concentration levels with the prevalence of winds from different sectors was studied in an effort to investigate the transport of metal particles from various zones of the city. Finally, factor analysis was carried out to extract the main components responsible for the variance of the dataset and to attribute them to specific source categories, with vehicle-related sources being important in all cases.     

Dry atmospheric inputs of trace metals at the Mediterranean coast of Israel (SE Mediterranean): sources and fluxes

This study presents the first detailed data on aerosol concentrations of trace metals (Cd, Pb, Cu, Zn, Cr, Mn, Fe and Al) at the SE Mediterranean coast of Israel, and assesses their sources and fluxes. Aerosol samples were collected at two sampling stations (Tel-Shikmona and Maagan Michael) along the coast between 1994 and 1997. Two broad categories of aerosol trace metal sources were defined; anthropogenic (Cd, Cu, Pb and Zn) and naturally derived elements (Al, Fe, Mn and Cr). The extent of the anthropogenic contribution was estimated by the degree of enrichment of these elements compared to the average crustal composition (EF_crust). High values (median >100) were calculated for Cd, Pb and Zn, minor values for Cu and relatively low values (<10) for Fe, Mn and Cr. The crustal-derived elements exhibited a statistically significant seasonal pattern of higher concentrations during spring and autumn (e.g. Al concentrations in some cases during these periods were observed to be in excess of 1500 ng m⁻³). In the eastern Mediterranean basin crustal-dominated elements are enriched by 2–3 times while others (Cd and Pb) are comparable to the northwestern Mediterranean. The Pb : Cd ratios of ∼150 are higher than in coastal European sites (60–116) or emission materials (∼50). It is speculated that these differences are attributed mainly to the mixing of crustal material with local and European emissions. At present, it is impossible to quantify the latter two fractions. Back trajectory analysis and the subsequent categorization of two main aerosol populations, ‘European’ and ‘North Africa–Arabian’, exhibited a significantly different geochemical imprint on the aerosol chemical composition. ‘European’-derived air masses indicated significantly higher EF_crust values for Cd and Pb due to the greater anthropogenic character of the aerosol population, with a dilution by crustal material of this population leading to comparatively lower EF_crust values associated with the North African–Arabian air masses.     

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.     

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.     

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.     

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.     

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.     

Concentrations of cadmium and other metals in Fucus vesiculosus L. and Fontinalis dalecarlica Br. Eur. from the northern Baltic Sea and the southern Bothnian Sea

Concentrations of Cd and ten other metals (Al, Co, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn) were determined in the brown seaweed Fucus vesiculosus L. and the aquatic moss, Fontinalis dalecarlica Br. Eur. from the northern Baltic Sea and the southern Bothnian Sea. Elevated concentrations of metals were found in samples taken close to densely populated areas, such as Stockholm and Nyn?shamn. Very high concentrations of especially Zn were found in both Fucus and Fontinalis samples taken from the area south of the Gulf of G?vle. The results indicate that mining and industrial activities along the river Dal?lven are the main sources of Zn and several other metals. Cd concentrations in Fucus plants reached maximum values (24.5 mg kg(-1)) at the northern site. The gradual increase of Cd concentrations in Fucus plants northward could not be totally explained by the salinity gradient in the Baltic Sea; reasons for this are discussed in this paper.     

Response of mosses to the heavy metal deposition in Poland--an overview

Concentrations of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) in Pleurozium schreberi (Brid.) Mitt., a common moss species, were used to indicate relative levels of atmospheric deposition in Poland in the years 1975-1998. Spatial and temporal differences in the heavy metal concentrations in mosses were found. The highest concentration of heavy metals was recorded in the moss samples from the southern, most industrialised part of the country, and the lowest from north-eastern Poland. A significant decrease of heavy metals over 20 years (1975-1998) was found.     

Study on PCBs,PCDD/Fs,organochlorine pesticides,heavy metals and arsenic content in freshwater fish species from the River Turia (Spain)

In this study samples of common trout, European eel and barbel have been analysed for the levels of heavy metals such as lead (Pb), cadmium (Cd), zinc (Zn), copper (Cu), and the metalloid arsenic (As). Polychlorinated biphenyls (PCBs), including three non-ortho substituted PCBs, 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and DDT and its two main metabolites were also analysed in some selected samples, in order to evaluate the extent of contamination of the River Turia basin. All samples presented detectable levels of the elements analysed, presenting zinc the highest concentrations. European eel was the species found to highly accumulate these contaminants. Regarding organochlorinated compounds, seven samples exhibited detectable levels of the most toxic PCDD/Fs congener, the 2,3,7,8-TCDD. Non-ortho PCBs were not detected or not quantified in almost all samples and the sum of the individual PCB congeners determined were low compared to other aquatic ecosystems with similar fish species.     

Moss (Bryum radiculosum) as a bioindicator of trace metal deposition around an industrialised area in Sardinia (Italy)

The moss Bryum radiculosum (Brid.), a species typical of dry and coastal environments, was used as a bioindicator for the estimation of atmospheric trace metal deposition around the industrial site of Portoscuso (Sardinia, Italy), which includes a lead-zinc smelter, two power plants, and aluminium production factories. For Cd, Pb, Zn, and V the results showed very similar patterns with extremely high values in the immediate surroundings of the industrial area. Copper and Cr showed somewhat different patterns, but still pointing to local pollution sources. The levels of metals at distance of about 13 km from the industrial site were still higher than in background samples. In order to evaluate the suitability of B. radiculosum for monitoring studies, trace metal concentrations in moss were compared with bulk deposition measurements in the same area. Correlation was significant only for Pb, Cd, and Zn. For Cr, Cu, and V the results showed high variability, mainly to be ascribed to soil factors.     

Concentrations of some heavy metals in water, sediment and fish species from the Atatürk Dam Lake (Euphrates), Turkey

Concentrations of heavy metals (Cd, Co, Cu, Fe, Hg, Mn, Mo, Ni, Pb and Zn) were measured in the water, sediment and fish species (Acanthobrama marmid, Chalcalburnus mossulensis, Chondrostoma regium, Carasobarbus luteus, Capoetta trutta and Cyprinus carpio) from the Atatürk Dam Lake, Turkey. Among the heavy metals studied Cd, Co, Hg, Mo and Pb were not detected in water, sediments and fish samples, while Ni was undetectable levels in fish samples. Levels of Cu, Fe, Mn and Zn varied depending on different tissues. The results of this study indicated that a general absence of serious pollution in the dam lake is due to heavy metals, where as the concentrations of elements found could mainly be attributed to geological sources.     

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.     

Distribution of metals and trace elements in adult and juvenile penguins from the Antarctic Peninsula area

The presence of metals in the Antarctic environment is principally a natural phenomenon caused by geochemical characteristics of the region, although some anthropogenic activities can increase these natural levels. Antarctic penguins present several of the characteristics of useful sentinels of pollution in Antarctica such as they are long-lived species situated at the top of food web. The concentrations of Al, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Cd, and Pb were determined by inductively coupled plasma–mass spectrometry in samples of liver, kidney, muscle, bone, feather, and stomach contents of gentoo, chinstrap, and Adélie penguin (12 adults, five juveniles) from carcasses of naturally dead individuals collected opportunistically in the Antarctic Peninsula area. The obtained results showed that accumulation and magnification of several elements can be occurring, so that Cd and Se reached levels potentially toxic in some specimens. The presence of human activities seems to be increasing the presence of toxic metals such as Mn, Cr, Ni, or Pb in penguins.     

Assessing heavy metal sources in agricultural soils of an European Mediterranean area by multivariate analysis

According to the European Thematic Strategy for Soil Protection, the characterization of the content and source of heavy metals in soils are necessary to establish quality standards on a regional level that allow the detection of sampling sites affected by pollution. In relation to this, the surface horizons of 54 agricultural soils under vegetable crops in the Alicante province (Spain), a representative area of the European Mediterranean region, were sampled to determine the content of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn. Analytical determinations were performed by atomic absorption spectroscopy after microwave sample digestion in acid solution. Results indicated that heavy metal levels were similar to those reported by authors working on agricultural soils from other parts of the Mediterranean region, with the exception of Cu and Pb in some samples. Multivariate analysis (principal component analysis and cluster analysis) was performed to identify a common source for heavy metals. Moreover, soil properties were determined in order to characterize agricultural soils and to analyze relationships between heavy metal contents and soil properties. The content of Co, Cr, Fe, Mn, Ni and Zn were associated with parent rocks and corresponded to the first principal component called the lithogenic component. A significant correlation was found between lithogenic metals and some soil properties such as soil organic matter, clay content, and carbonates, indicating an important interaction among them. On the other hand, elements such as Cd, Cu and Pb were related to anthropic activities and comprised the second (Cu and Pb) and third principal components (Cd), designated the anthropogenic components. Generally, Cd, Cu and Pb showed a lower correlation with soil properties due to the fact that they remain in available forms in these agricultural soils. Taking into account these results and other achieved in other parts of the European Mediterranean region, it can be concluded that soil quality standards are highly needed to declare soils affected by human induced pollution. This is particularly relevant for anthropogenic metals (Cd, Cu and Pb, and in some areas also Zn). Further research in other agricultural areas of the region would improve the basis for proposing such soil quality standards.     

Distribution and coassociations of trace elements in soft tissue and byssus of Mytilus galloprovincialis relative to the surrounding seawater and suspended matter of the southern part of the Korean Peninsula

The concentrations of Cd, Co, Cu, Cr, Fe, Hg, Mn, Ni, Pb, Sn, Ti and Zn were analyzed by AAS, ICP MS and AFS in soft tissues and byssal threads of Mytilus galloprovincialis from Masan Bay and Ulsan Bay, Korea. Spatial variations in metal concentrations were found. The levels of Cd, Pb, Hg, Cu, Zn, Co and Mn were very high in the mussels from Ulsan Bay (Sts. U1, U2) and comparable with elevated concentrations of these elements in Mytilus sp. reported to date for other geographical areas. Seasonal differences in some metal concentrations were also observed. These variations may be caused by factors such as: a large difference in seawater temperature, food supply for the mussel population and/or freshwater runoff of particulate metal to the coastal water and weight changes brought about by gonadal development and the release of sexual products. Pb, Cu, Zn, Co, Ni, Fe and Mn were more enriched in byssal threads than in the soft tissues, hence the byssus seems to be more sensitive in reflecting the availabilities of trace metals in the ambient waters. Concentrations of trace metals varied with respect to the size of mussels and season, depending on many factors like sexual development, and seawater temperature, etc. The levels of some trace metals in seawater, especially in suspended matter were correlated significantly with those in soft tissues and byssal threads. There were spatial variations in metal concentrations in the soft tissue and byssus attributed to different sources of trace elements located near the sampling sites. There were significant relationships between concentrations of some metals (Cd, Cu, Pb, and Zn) in mussel soft tissues and byssal threads and suspended matter. This suggests that M. galloprovincialis can be used as a sensitive biomonitor for the availabilities of trace elements in the coastal waters off Korea.     

Spatio-temporal distribution of metals in household dust from rural,semi-urban and urban environments in the Niger Delta,Nigeria

Concentrations of metals in household dust samples from rural, semi-urban and urban zones of the Niger Delta in Nigeria were measured during both 2009 and 2014 with the aim of providing information on changes in the concentrations, distribution patterns, sources and risks of metals in these zones. The concentrations of metals in the dust samples were quantified by using inductively coupled plasma atomic emission spectrophotometry (ICP-AES) after digestion with aqua regia. The measured concentrations (mg kg^?1) of metals in the three zones within the study periods were as follows: <LOQ–21.2; <LOQ–182; 7.90–265; <LOQ–117; <LOQ–471; 3.37–2310; 0.35–7.9; 4.25–365; 6.78–61,600; 219–37,700; and 1180–18,000 for Cd, Pb, Ba, Cr, Ni, Cu, Co, Mn, Zn, Fe and Al, respectively. The results from the two periods indicate significant changes in the concentrations, distribution patterns and risk factors which reflects a deterioration of the quality of the household environment over this time span. The hazard index (HI) values calculated for children were greater than 1 indicating significant non-cancer risks for these subjects in these areas. The HI values for adults were less than 1 and consequently do not pose a significant risk. The carcinogenic risk levels for exposure to metals for both adults and children in these zones were below the range specified as safe by the US EPA (×10^?6 and ×10^?4) thereby indicating a low cancer risk. The sources of metals in household dust from these zones include emissions from industries, traffic, artisanal workshops and releases from household furniture, metal-based fittings, metal roofing and pesticides.     

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.     

Evaluation of the anthropogenic influx of metal and metalloid contaminants into the Moulay Bousselham lagoon, Morocco, using chemometric methods coupled to geographical information systems

Superficial and cored sediment samples from the Moulay Bousselham lagoon and sub-watershed were analyzed for Al, Fe, Cu, Zn, Pb, Mn, Ni, Cr, As, Hg, and Cd. The temporal and spatial distributions of the main contamination sources of heavy metals were identified and described using chemometric and geographic information system (GIS) methods. Sediments from coastal lagoons near urban and agricultural areas are commonly contaminated with heavy metals, and the concentrations found in surface sediments are significantly higher than those from 50–100 years ago. The concentrations of these elements decrease sharply with depth in the sediment column, and the elements are preferentially enriched in the <2-μm-sized fraction of the sediment. The zones of enhanced risk of heavy metals were detected by means of GIS-based geostatistical modeling. According to sediment pollution indices and statistical analysis, heavy metals (Pb, Cu, Ni, Zn, Cr, and Hg) that pose a risk have become largely enriched in the lagoon sediments during the recent period of agricultural intensification.     

Heavy metals in soils from a typical industrial area in Sichuan,China: spatial distribution,source identification,and ecological risk assessment

Anthropogenic activities could result in increasing concentrations of heavy metals in soil and deteriorating in soil environmental quality. Topsoil samples from a typical industrial area, Shiting River Valley, Sichuan, Southwest China, were collected and determined for the concentrations of Cu, Zn, Cr, Cd, As, and Hg. The mean concentrations of these metals were lower than the national threshold values, but were slightly higher than their corresponding background values, indicating enrichment of these metals in soils in the valley, especially for Cu, Zn, and Hg. The topsoils in this area demonstrated moderate pollution and low potential ecological risk. Principal component analysis coupled with cluster analysis was applied to analyze the data and identified possible sources of these heavy metals; the results showed that soil Cd, Hg, As, Cu, and Zn were predominantly controlled by human activities, whereas Cr was mainly from the parent material. The spatial distribution of the heavy metals varied distinctly and was closely correlated to local anthropogenic activities. Furthermore, the concentrations of heavy metals in the industrial land demonstrated relatively higher levels than those of other land use patterns. Soil metal concentrations decreased with the distance increase from the traffic highway (0–1.0 km) and water system (0–2.0 km). Additionally, soil properties, especially pH and soil organic matter, were found to be important factors in the distribution and composition of metals.