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

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

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.     

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.     

The use of mosses as environmental metal pollution indicators

The possibility of using mosses as environmental indicators of metal pollution has been investigated. Mosses of the species Bryum argenteum were collected from different parts of Piedmont (Italy), ranging from highly polluted areas to nearly uncontaminated mountain areas. Periodical samplings were planned in every site on a monthly base, in order to check variations of metal uptake throughout one year; correlations with pluviometric and thermal patterns were investigated for all sampling stations. On every moss sample 20 elements, ranging from major (K, P, Al, Ca, Fe and Mg) to minor (Mn, Na, Ti and Zn) and trace (As, Ba, Cd, Co, Cr, Cu, Li, Ni, Pb and Sr), were quantitatively determined by inductively coupled plasma-atomic emission spectrometry or graphite furnace-atomic absorption spectrometry, depending on the needed sensitivity. Statistical analyses, carried out with principal component analysis and cluster analysis methods, revealed that a good correlation exists between metal content in mosses and pollution degree in the areas sampled.     

Chromium speciation in river sediment pore water contaminated by tannery effluent

Cr(VI) is far more soluble and toxic than Cr(III). Sediment pore water was investigated in a river adjacent to the property of a large former tannery, into which Cr-contaminated effluent was discharged over a 55-year period, and where extremely high Cr concentrations have been found in the sediments. Dialysis cells, or peepers, were used to generate depth profiles of Cr concentration in sediment pore water. Samples were analyzed for total Cr using inductively coupled plasma-mass spectrometry (ICP-MS) and for Cr species using high performance liquid chromatography (HPLC)-ICP-MS. The results show an absence of Cr(VI) in all samples. Furthermore, incomplete recovery of Cr(VI) added to the samples collected at the locations with highest sediment Cr concentrations indicate strong reducing conditions at those locations, which are not conducive to the presence of Cr(VI).     

Trace element accumulation by moss and lichen exposed in bags in the city of Naples (Italy)

This paper presents the results of a bioaccumulation study of trace elements in the Naples urban area based on the use of the moss Sphagnum capillifolium (Ehrh.) Hedw. and the lichen Pseudevernia furfuracea (L.) Zopf exposed in bags in 23 sites. Moss and lichen bags were exposed for 4 months starting from the beginning of July 1999. Bags gathering was carried out after 10 weeks of exposure, at the end of the dry season, and after 17 weeks, during the wet season. The elements Al, As, Ca, Cd, Cr, Co, Cu, Fe, K, Mg, Mn, Mo, Ni, Pb, Ti, V and Zn were analysed by inductively coupled plasma-mass spectrometry ICP-MS in both biomonitors. For the majority of the elements the total amounts found in S. capillifolium were higher than in P. furfuracea whether considering the whole period of exposure or the weekly uptake. It was observed that there was a much greater difference in metal accumulation by P. furfuracea between the dry and wet seasons compared with S. capillifolium. In the wet period, the lichen seems to accumulate a larger quantity of metals. With the exception of Mn, trace element concentrations did not appear to be significantly affected by the washing away of rainfall. K loss during exposure suggested cell membrane damage in both organisms. For P. furfuracea the K leakage was limited to the dry period of exposure. A clear distinction between "lithophilic" and "anthropogenic" elements was achieved by cluster analysis. Significant correlations were found among Fe-Cu-Cr-Ni, Pb-Cd-Co, V-Cr-Ni, Zn-Ni-Pb, suggesting a common source for each group of elements.     

Hair element concentrations in females in one acid and one alkaline area in southern Sweden

Concentrations of 34 trace elements in hair have been determined in 47 females from an acid region in southern Sweden, who were compared with 43 females from an alkaline area. The concentrations of these elements in hair and drinking water were determined by inductively coupled plasma optical emission spectroscopy and inductively coupled plasma mass spectrometry. The hair concentrations of boron and barium were significantly higher (p < 0.001) in hair samples from the acid region, the hair levels of calcium, strontium, molybdenum, iron, and selenium were significantly higher (p < 0.001) in the alkaline region. For some metals, e.g. calcium, lead, molybdenum, and strontium, there were positive correlations between the concentrations in hair and water (rs = 0.34-0.57; p < or = 0.001), indicating the importance of intake from minerals in water. The increased ratio of selenium/mercury concentrations in hair samples obtained in the alkaline district (p < 0.001) indicates that these subjects may have better protection against the toxic effects of mercury.     

Assessing the suitability of Norway spruce wood as an environmental archive for sulphur

The aim of this study was to assess the suitability of Norway spruces (Picea abies L. Karst.) as an environmental archive for sulphur. For this purpose spruce trees were sampled in two distinct regions of Switzerland: the Alps and the Swiss Plateau, which differ significantly with respect to S immission. Wood samples were measured using two methods: LASER Ablation high resolution inductively coupled plasma mass spectrometry (LA-HR-ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP-OES) after acid digestion. Independently corroborated by previous measurements of sulphur in peat bogs, the rise and fall of sulphur dioxide pollution in Switzerland appears to be reflected in spruce wood sulphur content. While the wood sulphur content profile of trees sampled in the Alps is relatively flat, the profiles of trees located on the Swiss Plateau display a characteristic sulphur peak. This corresponds to air pollution data in the different regions and indicates that the trees reacted on the changing S supply and recorded a pollution signal in the wood.     

Heavy metal extractable forms in sludge from wastewater treatment plants

The analysis of heavy metals is a very important task to assess the potential environmental and health risk associated with the sludge coming from wastewater treatment plants (WWTPs). However, it is widely accepted that the determination of total elements does not give an accurate estimation of the potential environmental impact. So, it is necessary to apply sequential extraction techniques to obtain a suitable information about their bioavailability or toxicity. In this paper, a sequential extraction scheme according to the BCR's guidelines was applied to sludge samples collected from each sludge treatment step of five municipal activated sludge plants. Al. Cd, Co, Cu, Cr, Fe, Mn, Hg, Mo, Ni, Pb, Ti and Zn were determined in the sludge extracts by inductively coupled plasma atomic emission spectrometry. In relation to current international legislation for the use of sludge for agricultural purposes none of metal concentrations exceeded maximum permitted levels. In most of the metal elements under considerations, results showed a clear rise along the sludge treatment in the proportion of two less-available fractions (oxidizable metal and residual metal).     

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.     

Chemometric approach to evaluate element distribution in muscle,liver and fish bone of roach (Rutilus rutilus), silver bream (Blicca bjoerkna) and crucian carp (Carassius carassius) from Swarzędzkie Lake (Poland) using ICP-MS and FIAS-CVAAS techniques

The content of elements in fish tissues and organs from Swarz?dzkie Lake was investigated in order to evaluate the possible risk associated with their consumption by animals as well as humans. Samples of muscle, liver and fish bone of three fish species; roach (Rutilus rutilus), silver bream (Blicca bjoerkna) and crucian carp (Carassius carassius) were collected from seine catches undertaken as part of the biomanipulation of Swarz?dzkie Lake. Element concentration (Al, As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Zn) was determined by inductively coupled plasma mass spectrometry (ICP-MS), with the exception of Hg where the flow injection analysis system cold vapour atomic absorption spectrometry (FIAS-CVAAS) was applied. The study indicated a large variation in the occurrence of the investigated elements in different parts of the fish body. The highest content of Al and Zn was stated in all fish organs for each fish species. The majority of the applied statistical and chemometric methods (e.g., PCA, CA) refer to roach since we had a large number of data for this species. The obtained results were assessed in terms of their accuracy and precision using certified reference material of Fish Muscle ERM BB422.     

Estimation of plant sampling uncertainty: an example based on chemical analysis of moss samples

In order to estimate the level of uncertainty arising from sampling, 54 samples (primary and duplicate) of the moss species Pleurozium schreberi (Brid.) Mitt. were collected within three forested areas (Wierna Rzeka, Piaski, Posłowice Range) in the Holy Cross Mountains (south-central Poland). During the fieldwork, each primary sample composed of 8 to 10 increments (subsamples) was taken over an area of 10 m² whereas duplicate samples were collected in the same way at a distance of 1–2 m. Subsequently, all samples were triple rinsed with deionized water, dried, milled, and digested (8 mL HNO₃ (1:1) + 1 mL 30 % H₂O₂) in a closed microwave system Multiwave 3000. The prepared solutions were analyzed twice for Cu, Fe, Mn, and Zn using FAAS and GFAAS techniques. All datasets were checked for normality and for normally distributed elements (Cu from Piaski, Zn from Posłowice, Fe, Zn from Wierna Rzeka). The sampling uncertainty was computed with (i) classical ANOVA, (ii) classical RANOVA, (iii) modified RANOVA, and (iv) range statistics. For the remaining elements, the sampling uncertainty was calculated with traditional and/or modified RANOVA (if the amount of outliers did not exceed 10 %) or classical ANOVA after Box-Cox transformation (if the amount of outliers exceeded 10 %). The highest concentrations of all elements were found in moss samples from Piaski, whereas the sampling uncertainty calculated with different statistical methods ranged from 4.1 to 22 %.

     

PCA and multidimensional visualization techniques united to aid in the bioindication of elements from transplanted <Emphasis Type="Italic">Sphagnum palustre</Emphasis> moss exposed in the Gdańsk City Area

GOAL, SCOPE AND BACKGROUND: During the last decades, a technique for assessing atmospheric deposition of heavy elements was developed based on the principle that samples of moss are able to accumulate elements and airborne particles from rain, melting snow and dry deposition. Despite a broad interest in bioindication there are still ongoing works aimed at the preparation of a standard procedure allowing for a comparison of research carried out in various areas. This is why the comparison of living and dry moss of the same species and growth site seems to be interesting, logical and promising. A most reliable approach seems to be the application of bioindication connected with multivariate statistics and efficient visualization techniques in the interpretation of monitoring data. The aim of this study was: (i) to present cumulative properties of transplanted Sphagnum palustre moss with differentiation into dry and living biomaterial; (ii) to determine and geographically locate types of pollution sources responsible for a structure of the monitoring data set; (iii) to visualize geographical distribution of analytes in the Gdańsk metropolitan area and to identify the high-risk areas which can be targeted for environmental hazards and public health. MATERIALS AND METHODS: A six month air pollution study based on Sphagnum palustre bioindication is presented and a simplified procedure of the experiment is given. The study area was located at the mouth of the Vistula River on the Baltic Sea, in Gdańsk City (Poland). Sphagnum palustre was selected for research because of its extraordinary morphological properties and its ease in being raised. The capability of dry and living moss to accumulate elements characteristic for anthropogenic and natural sources was shown by application of Principal Component Analysis. The high-risk areas and pollution profiles are detected and visualized using surface maps based on Kriging algorithm. RESULTS: The original selection of elements included all those that could be reliably determined by Neutron Activation Analysis in moss samples. Elimination of variables covered the elements whose concentrations in moss were lower than the reported detection limits for INAA for most observations or in cases where particular elements did not show any variation. Eighteen elements: a, Ca, Sc, Fe, Co, Zn, As, Br, Mo, Sb, Ba, La, Ce, Sm, Yb, Lu, Hf, Th, were selected for the research presented. DISCUSSION: Two runs of PCA were performed since, in the first-run a heavy polluted location (Stogi - 'Sto') understood as outlier in the term of PCA approach was detected and results in the form of block diagrams and surface maps were presented. As ensues from the first-run PCA analysis, the factor layout for both indicators is similar but not identical due to the differences in the elements accumulation mechanism. Three latent factors ('phosphatic fertilizer plant impact', 'urban impact' and 'marine impact') explain over 89% and 82% of the total variance for dry and living moss respectively. In the second-run PCA three latent factors are responsible for the data structure in both moss materials. However, in the case of dry moss analysis these factors explain 85% of the total variance but they are rather hard to interpret. On the other hand living moss shows the same pattern as in first-run PCA. Three latent factors explain over 84% of the total variance in this case. The pollution profiles extracted in PCA of dry moss data differ tremendously between both runs, while no deterioration was found after removal of Stogi from data set in case of living moss. Performance of the second-run PCA with exception of Stogi as a heavy polluted location has led to the conclusion that living moss shows better indication properties than dry one. CONCLUSIONS: While using moss as wet and dry deposition sampier it is not possible to calculate deposition values since the real volume of collected water and dust is hard to estimate due to a splash effect and irregular surface. Therefore, accumulation values seam to be reasonable for moss-based air pollution surveys. Both biomaterials: dry and living Sphagnum palustre show cumulative properties relative to elements under interest. Dry moss has a very loose collection of the atmospheric particles, which can also easily get lost upon rinsing with rainwater running through exposed dry moss material. The living moss may, on the contrary, incorporate the elements in its tissue, thus being less susceptible to rinsing and thus better reflecting the atmospheric conditions. Despite the differences in element uptake and uphold capabilities dry and living moss reflect characteristic anthropogenic and natural profiles. Visible differences in impacts' map coverage exist mostly due to the accumulation mechanisms differentiating dry from living moss. However, in case of each indicator 'phosphatic fertilizer plant impact' is recognized as the strongest pollution source present in examined region. RECOMMENDATIONS AND PERSPECTIVES: General types of pollution sources responsible for a structure of monitoring data set were determined as high-risk/low-risk areas and visualized in form of geographic distribution maps. These locations can be targeted for environmental hazards and public health. Chemometric results in the form of easy defined surface maps can became a powerful instrument in hands of decision-makers working in the field of sustainable development implementation.     

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.     

Application of spectrometric analysis to the identification of pollution sources causing cultural heritage damage

Black crusts are recognized to have been, up to now, one of the major deterioration forms affecting the built heritage in urban areas. Their formation is demonstrated to occur mainly on carbonate building materials, whose interaction with an SO₂-loaded atmosphere leads to the transformation of calcium carbonate (calcite) into calcium sulfate dihydrate (gypsum) which, together with embedded carbonaceous particles, consequently forms the black crusts on the stone surface. An analytical study was carried out on black crust samples collected from limestone monumental buildings and churches belonging to the European built Heritage, i.e., the Corner Palace in Venice (Italy), the Cathedral of St. Rombouts in Mechelen (Belgium), and the Church of St. Eustache in Paris (France). For a complete characterization of the black crusts, an approach integrating different and complementary techniques was used, including laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Fourier transform infrared spectroscopy, optical and scanning electron microscopy. In particular, the application of LA-ICP-MS permitted to obtain a complete geochemical characterization in terms of trace elements of the black crusts from the inner parts to the external layers contributing to the identification of the major combustion sources responsible for the deterioration over time of the monuments under study. In addition, the obtained results revealed a relation between the height of sampling and the concentration of heavy metals and proved that the crust composition can be a marker to evaluate the variation of the fuels used over time.     

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.     

Environmental impact of a coal combustion-desulphurisation plant: abatement capacity of desulphurisation process and environmental characterisation of combustion by-products

The fate of trace elements in a combustion power plant equipped with a wet limestone flue gas desulphurisation (FGD) installation was studied in order to evaluate its emission abatement capacity. With this aim representative samples of feed coal, boiler slag, fly ash, limestone, FGD gypsum and FGD process water and wastewater were analysed for major and trace elements using the following techniques: inductively coupled plasma-mass spectrometry (ICP-MS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), ion chromatography (IC), ion selective electrode (ISE) and atomic absorption spectroscopy (AAS). Mass balances were established allowing to determine the element partitioning behaviour. It was found that, together with S, Hg, Cl, F, Se and As were those elements entering in the FGD plant primarily as gaseous species. The abatement capacity of the FGD plant for such elements offered values ranged from 96% to 100% for As, Cl, F, S and Se, and about 60% for Hg. The environmental characterisation of combustion by-products (boiler slag, fly ash and FGD gypsum) were also established according to the Council Decision 2003/33/EC on waste disposal. To this end, water leaching tests (EN-12457-4) were performed, analysing the elements with environmental concern by means of the aforementioned techniques. According to the leaching behaviour of combustion by-products studied, these could be disposed of in landfills for non-hazardous wastes.     

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.     

Traffic and catalytic converter - related atmospheric contamination in the metropolitan region of the city of Rio de Janeiro, Brazil

In this work, 24-h PM10 samples were collected in Rio de Janeiro, Brazil, and analysed for trace elements (Cd, Ce, Cu, La, Mo, Ni, Pb, Pd, Rh, Sb and Sn). The sampling was carried out at five locations (Bonsucesso; Centro, downtown city; Copacabana; Nova Igua?u and Sumaré) with different traffic densities and anthropogenic activities. An analytical method based on the EPA method for the determination of trace elements in airborne particulate matter (PM), using ultrasonic-assisted extraction and inductively coupled plasma mass spectrometry (ICP-MS) was applied. Our results suggest that vehicular traffic is the most important source of environmental pollution at the studied sites. The presence of Mo, Pd and Rh in the analysed filters reflects an additional source of pollution caused by the erosion and deterioration of automotive catalytic converters.     

Radionuclides and heavy metals in Borovac,Southern Serbia

BACKGROUND, AIM, AND SCOPE: The paper presents the complex approach to the assessment of the state of the environment in Southern Serbia, surroundings of Bujanovac, the region which is of great concern as being exposed to contamination by depleted uranium (DU) ammunition during the North Atlantic Treaty Organization (NATO) attacks in 1999. It includes studies on concentrations of radionuclides and heavy metals in different environmental samples 5 years after the military actions. MATERIALS AND METHODS: In October 2004, samples of soil, grass, lichen, moss, honey, and water were collected at two sites, in the immediate vicinity of the targeted area and 5 km away from it. Radionuclide ((7)Be, (40)K, (137)Cs, (210)Pb, (226)Ra, (232)Th, (235)U, (238)U) activities in solid samples were determined by standard gamma spectrometry and total alpha and beta activity in water was determined by proportional alpha-beta counting. Concentrations of 35 elements were determined in the samples of soil, moss, grass, and lichen by instrumental neutron activation analysis (INAA). RESULTS: The results are discussed in the context of a possible contamination by DU that reached the environment during the attacks as well as in the context of an environmental pollution by radionuclides and heavy metals in Southern Serbia. The results are compared to the state of environment in the region and other parts of the country both prior to and following the attacks. DISCUSSION: This is the first comprehensive study of the contents of radionuclides and heavy metals in Southern Serbia and consequently highly important for the assessment of the state of environment in this part of the country concerning possible effects of DU ammunition on the environment, as well as anthropogenic source of pollution by radionuclides and heavy metals and other elements. Also, the highly sensitive method of INAA was used for the first time to analyze the environmental samples from this area. CONCLUSIONS: The results of the study of radionuclides in the samples of soils, leaves, grass, moss, lichen, honey, and water in Southern Serbia (Bujanovac) gave no evidence of the DU contamination of the environment 5 years after the military actions in 1999. Activities of radionuclides in soils were within the range of the values obtained in the other parts of the country and within the global average. The ratio of uranium isotopes confirmed the natural origin of uranium. In general, concentrations of heavy metals in the samples of soils, plant leaves, mosses, and lichen are found to be less or in the lower range of values found in other parts of the country, in spite of the differences in plant and moss species or soil characteristics. Possible sources of heavy metal contamination were identified as a power coal plant in the vicinity of the sampling sites and wood and waste burning processes. RECOMMENDATIONS AND PERSPECTIVES: The collected data should provide a base for the health risk assessments on animals and humans in the near future. It should be emphasized that the sampling was carried out 5 years after the military action and that the number of samples was limited; therefore, the conclusions should be accepted only as observed tendencies and a detailed study should be recommended in the future.