Estimation of the atmospheric emissions of trace elements from anthropogenic sources in Europe

The total emissions of 15 elements from various anthropogenic sources in Europe are presented here. The data were obtained on the basis of trace element emission factors and statistical information on the consumption of ores, rocks and fuels and the production of various types of industrial goods. Available information on types of fuels, ores and rocks and differences in manufacturing techniques used in the European countries have been taken into account. Different types of dust removal installations and their effectiveness have also been considered, as well as import-export relations of fuels and ores between particular countries. The author assessed the spatial distributions of trace element emissions based on information on location of industrial areas in Europe and plant capacities.     

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

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

Use of atmospheric elemental size distributions in estimating aerosol sources in the Helsinki area

In June 1996–June 1997 Berner impactors were used in the Helsinki area to measure size distributions of atmospheric aerosols simultaneously at an urban and at a rural site. Ten sample pairs were collected in the size range of 0.03–15.7 μm of equivalent aerodynamic diameter (EAD). Average size distributions at the two sites were calculated for 29 elements, particulate mass, and sulphate. At both sites especially sulphate, As, B, Bi, Cd, Ni, Tl, and V were enriched in fine particles (EAD<2.3 μm). In order to estimate local fine-particle sources of the various chemical components, the similarities and dissimilarities in the accumulation-mode parameters were studied separately for both sites. It was observed that often in different samples, different components had similar accumulation modes. At both sites, particulate mass, As, and Pb had similar accumulation modes to sulphate which suggests that long-range transport (LRT) is important for these components. V, Ni, Mo, and Co formed another group of similar accumulation modes at both sites suggesting that these elements largely originated from local and regional oil combustion. In addition, other groups of similar accumulation modes were observed but these groups were different between the sites. The meteorological parameters indicated that seven sample pairs formed a subset of the data in which the local emissions of the Helsinki area were transported to the urban site but not to the rural site. For this subset the rural fine-particle concentrations were considered to represent an upper limit estimate for the LRT. These upper limit LRT estimations were further improved by utilising the quantitative relative size distributions (QRSD) method at the rural site. The QRSD method supposes that in the fine-particle size range the LRT fractions of all chemical components have a similar shape in their size distributions. Fine-particle sulphate is typically long-range transported, and was therefore selected as the model component that represents the shape of LRT material. Sulphate size distribution was then scaled to give an estimation of the LRT contribution of each component at the rural site. These rural “sulphate scaled” LRT estimates were subtracted from the corresponding urban concentrations to give the local contributions (ng/m³) downwind of the Helsinki area. In particles with EAD below 2.3 μm, the highest absolute and relative downwind local contributions were observed for several common sea-salt and road-dust components. Also the combustion-related elements Ni and V showed fairly high downwind local contributions. Because of the limited number of samples, the local and LRT contributions were not estimated for different wind directions.     

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.     

Investigation of sources of atmospheric aerosol at a hot spot area in Dhaka, Bangladesh

Samples of fine and coarse fractions of airborne particulate matter were collected at the Farm Gate area in Dhaka from July 2001 to March 2002. Dhaka is a hot spot area with very high pollutant concentrations because of the proximity of major roadways. The samples were collected using a "Gent" stacked filter unit in two fractions of 0- to 2.2-microm and 2.2- to 10-microm sizes. The samples were analyzed for elemental concentrations by particle-induced X-ray excitation (PIXE) and for black carbon by reflectivity methods, respectively. The data were analyzed by positive matrix factorization (PMF) to identify the possible sources of atmospheric aerosols in this area. Six sources were found for both the coarse and fine PM fractions. The data sets were also analyzed by an expanded model to explore additional sources. Seven and six factors were obtained for coarse and fine PM fractions, respectively, in these analyses. The identified sources are motor vehicle, soil dust, emissions from construction activities, sea salt, biomass burning/brick kiln, resuspended/fugitive Pb, and two-stroke engines. From the expanded modeling, approximately 50% of the total PM2.2 mass can be attributed to motor vehicles, including two-stroke engine vehicle in this hot spot in Dhaka, whereas the PMF modeling indicates that 45% of the total PM2.2 mass is from motor vehicles. The PMF2 and expanded models could resolve approximately 4% and 3% of the total PM2.2 mass as resuspended/fugitive Pb, respectively. Although, Pb has been eliminated from gasoline in Bangladesh since July 1999, there still may be substantial amounts of accumulated lead in the dust near roadways as well as fugitive Pb emissions from battery reclaimation and other industries. Soil dust is the largest component of the coarse particle fraction (PM2.2-10) accounting for approximately 71% of the total PM2.2-10 mass in the expanded model, whereas from the PMF modeling, the dust (undifferentiated) contribution is approximately 49%.     

Sources and trends of trace elements and polycyclic aromatic hydrocarbons in a shallow lake in the Mediterranean area from sediment archives of the Anthropocene

Environmental Science and Pollution Research - In this study, the anthropogenic contamination in Trasimeno lake (Central Italy) was investigated using three sediment cores spanning over the last...     

Determination of sources of atmospheric aerosol in Copenhagen based on receptor models

A statistical analysis is presented of atmospheric aerosol element composition data collected at five monitoring stations in Copenhagen in 1983. The objective is to identify sources of air pollution, to estimate the variation of total suspended particles (TSP) for the different sources and to calculate the annual average source contribution to TSP. The basis for analysis is the chemical mass balance equations. Factor analysis methods are used to identify major sources of pollution and the contribution from each of the sources to the variation in TSP is estimated by an additional multiple regression. Finally, the influence of serial correlations between daily element contributions is discussed and it is stressed that the result of the analysis is not seriously affected by these correlations.     

Distribution and seasonal variability of trace elements in atmospheric particulate in the Venice Lagoon

Size distribution and selected element concentrations of atmospheric particulate matter (PM) were investigated in the Venice Lagoon, at three sites characterised by different anthropogenic influence. The PM₁₀ samples were collected in six size fractions (10-7.2, 7.2-3.0, 3.0-1.5, 1.5-0.95; 0.95-0.49 and <0.49 μm) with high volume cascade impactors, and the concentration of 17 elements (Al, As, Ca, Cd, Co, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb, Sr, V, Zn) was determined by inductively coupled plasma quadrupole mass spectroscopy. More than 1 year of sampling activities allowed the examination of seasonal variability in size distribution of atmospheric particulates and element contents for each site.At all the stations, particles with an aerodynamic diameter <3 μm were predominant, thus accounting for more than 78% of the total aerosol mass concentration. The highest PM₁₀ concentrations for almost all elements were found at the site which is more influenced by industrial and urban emissions. Similarity in size distribution of elements at all sites allowed the identification of three main behavioural types: (a) elements found mainly within coarse particles (Ca, Mg, Na, Sr); (b) elements found mainly within fine particles (As, Cd, Ni, Pb, V) and (c) elements with several modes spread throughout the entire size range (Co, Cu, Fe, K, Zn, Mn).Factor Analysis was performed on aerosol data separately identified as fine and coarse types in order to examine the relationships between the inorganic elements and to identify their origin. Multivariate statistical analysis and assessment of similarity in the size distribution led to similar conclusions on the sources.     

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.     

Characterization of the Atlanta area aerosol,elemental composition and possible sources

This paper presents a study or the elemental characterization of the Atlanta area aerosol at one rural and several urban sites. It includes a determination of the concentrations of major elemental components of the aerosol and a statistical analysis of the relationships between these components as a means of investigating possible sources. This research has emphasized the study of the graphitic carbon, C_e, and elemental sulfur, S, components of the aerosol (these two components are important in visibility reduction studies). The measurements show that C_e and S represent, respectively 3.1–9.9% and 1.9–4.4% of the total suspended paniculate, TSP, mass. The concentrations of C_e, S and TSP exhibit strong seasonal variations with C_e decreasing from winter to summer and S and TSP increasing over this period. All elemental components exhibit less concentration at the rural site than at the urban sites. Analysis results show that C_e appears to be statistically separate from S, which is assumed to be present as sulfate, indicating that the sources for C_e and particulate sulfate are distinct. S and TSP, however, appear to be linked through common regional scale meteorological processes.     

Size distribution and sources of trace metals and n-alkanes in the Athens urban aerosol during summer

Size-resolved, 24-h aerosol samples were collected from June–July 2001 by means of an Andersen high-volume cascade impactor. Sampling was conducted in a central avenue (Patission) characterised by heavy traffic, 21 m above street level, in the Athens city centre. Samples were analysed by atomic absorption spectrometry and gas chromatography to determine the size distribution of nine metallic elements (Cd, Pb, V, Ni, Mn, Cr, Cu, Fe, Al) and n-alkanes (with carbon numbers in the range 18–35). The aerosol mass median diameter (MMD) was calculated by means of probit analysis on the cumulative mass concentration size distribution for each metals and n-alkane. The total n-alkane mass concentration (TNA) in total suspended particles (TSP) ranged from 72 to 1506 ng m⁻³ while the total metal concentration ranged from 5.6 to 28.6 μg m⁻³. The results showed that metals such as Cd, V and Ni are characterised by a MMD <1 μm, while the MMD for Pb and Mn are ∼1 μm. Such metals are generally considered to have anthropogenic emission sources. Other metals such as Al, Fe, Cu and Cr were found to have MMD=2–6 μm, which generally originate from soil dust or mechanical abrasion processes. The Carbon number profile of n-alkane compounds showed a strong anthropogenic source with only a minor biogenic influence. The concentration of most n-alkanes was characterised by high variability during the sampling period, in contrast to the concentration of most trace metals. Most n-alkanes had a unimodal size distribution with MMD=1–2 μm similar to those of some trace metals (Pb, Mn), which originate mostly from vehicle emissions. This is a strong indication that these species have a common source. Finally, gas–particle partitioning of n-alkanes was also examined for different particle sizes by means of the relationship between the partition constant K_p and saturation vapour pressure (p_L⁰) as proposed by current sorption models.     

Evaluating the size distribution characteristics and sources of atmospheric trace elements at two mountain sites: comparison of the clean and polluted regions in China

Size-resolved trace metal concentrations at two background sites were assessed during a 1-year observation campaign, with the measurements performed in parallel at two mountain sites, where Mt. Dinghu (DHS) located in the rural region of Pearl River Delta (PRD) and Mt. Gongga (GGS) located in the Tibetan Plateau region. In total, 15 selected trace elements (Mg, Al, K, V, Mn, Fe, Cu, Zn, As, Mo, Ag, Cd, Ba, Tl, and Pb) in aerosol samples were determined using inductively coupled plasma mass spectrometry (ICPMS). The major metals in these two mountain sites were Fe, K, Mg, and Ca with concentrations ranging between 241 and 1452 ng/m³, 428 and 1351 ng/m³, 334 and 875 ng/m³, and 376 and 870 ng/m³, respectively, while the trace metals with the lowest concentrations were Mo, Ag, Cd, and Tl with concentrations lower than 4 ng/m³ in DHS and 2 ng/m³ in GGS. The pronounced seasonal variability in the trace elements was observed in DHS, with lower concentrations in spring and summer and relatively high in winter and autumn, whereas seasonal variance of trace elements is hardly observed in Mt. Gongga. The size distribution pattern of crustal elements of Al, Mg, K, Ba, and Fe was quite similar in DHS and GGS, which were mainly found in coarse particles peaked at 4.7–5.8 μm. In addition, V, Mo, Ag, and Tl were also concentrated in coarse particles, although the high enrichment factor (EF?>?100) of which suggested anthropogenic origin, whereas trace metals of Cd, Mn, Zn, As, Cu, and Pb concentrated in fine mode particles. Specifically, these trace metals peak at approximately 1.5 μm in DHS, while those in GGS peaked at diameter smaller than 0.3 μm, indicating the responsible for long-range transport from the far urban and industrialized areas. Multivariate receptor model combined with the enrichment factor results demonstrated that the trace elemental components at these two background sites were largely contributed from the fossil fuel combustion (55.4% in DHS and 44.0% in GGS) and industrial emissions factors (20.1% vs. 26.5%), which are associated with long distance transport from the coastal area of Southeast China and the Northwestern India, respectively, as suggested by the backward air mass trajectory analysis. Local sources from soil dust contributed a minor variance for trace elements in DHS (9.7%) and GGS (13.8%), respectively.

     

Use of mosses to study atmospheric deposition of trace elements: contributions from investigations in Norway

This paper presents essential features of biomonitoring work carried out in the author's laboratory during more than 25 years using various analytical techniques for the determination of over 50 elements. A substantial part of this work concerns large-scale deposition surveys in Norway using the moss Hylocomium splendens, where five nationwide surveys have been carried out since 1977. Considerable efforts have also been spent on intercalibration of different species of mosses and transformation of concentrations in moss to absolute deposition rates. Other significant activities include establishment of recommended values for moss reference samples, source apportionment of lead in mosses by stable isotope ratios and monitoring of local metal deposition around factories. Experience from this work has facilitated a critical evaluation of the contribution from sources other than atmospheric deposition to the elemental composition of the moss, as well as factors leading to depletion of elements in the moss. Recent work indicates that mosses may also be suitable for the monitoring of persistent halogenated organic pollutants and ¹³⁷Cs deposition.     

Monitoring of sources and atmospheric processes controlling air quality in an urban Mediterranean environment

Different monitoring parameters (PM mass concentrations, number–size distribution, black carbon, gaseous pollutants, and chemical composition, among others) are currently used in air quality studies. Urban aerosols are the result of several sources and atmospheric processes, which suggests that a single monitoring technique is insufficient to quantitatively evaluate all of them.This study assesses the suitability of a number of monitoring techniques (PM mass concentrations, number and size distribution of ultra-fine particles, levels of gaseous pollutants, and a complete chemical characterization of PM₁₀ and PM_2.5) by examining the response of those techniques to the different emission sources and/or atmospheric processes affecting an urban Mediterranean area (Barcelona, NE Spain).The results of this work reveal that the PM mass, the number concentration and the chemical composition give different, but complementary, information. Whereas the mineral matter, a key atmospheric aerosol component across the Mediterranean, is not properly quantitatively assessed by measuring sub-micrometric particles, the monitoring of the number concentration is indispensable to interpret the origin of specific aerosol episodes. Furthermore, the chemical composition yields very relevant information to deduce the causes of specific pollution episodes.The number concentration of ultra-fine particles in urban areas is strongly dependent upon vehicle exhaust emissions, which may cause adverse health impacts. Moreover, urban Mediterranean environments are favourable to produce nucleation-mode particles (<20 nm) with photochemical origin. In those cases, these particles are expected to be of high solubility and consequently their toxicity may differ from that of traffic-generated ultra-fine particles. Thus, the use of a single monitoring parameter to evaluate the health effects seems to be not enough.     

Source origin of trace elements in PM from regional background,urban and industrial sites of Spain

Despite their significant role in source apportionment analysis, studies dedicated to the identification of tracer elements of emission sources of atmospheric particulate matter based on air quality data are relatively scarce. The studies describing tracer elements of specific sources currently available in the literature mostly focus on emissions from traffic or large-scale combustion processes (e.g. power plants), but not on specific industrial processes. Furthermore, marker elements are not usually determined at receptor sites, but during emission. In our study, trace element concentrations in PM₁₀ and PM_2.5 were determined at 33 monitoring stations in Spain throughout the period 1995–2006. Industrial emissions from different forms of metallurgy (steel, stainless steel, copper, zinc), ceramic and petrochemical industries were evaluated. Results obtained at sites with no significant industrial development allowed us to define usual concentration ranges for a number of trace elements in rural and urban background environments. At industrial and traffic hotspots, average trace metal concentrations were highest, exceeding rural background levels by even one order of magnitude in the cases of Cr, Mn, Cu, Zn, As, Sn, W, V, Ni, Cs and Pb. Steel production emissions were linked to high levels of Cr, Mn, Ni, Zn, Mo, Cd, Se and Sn (and probably Pb). Copper metallurgy areas showed high levels of As, Bi, Ga and Cu. Zinc metallurgy was characterised by high levels of Zn and Cd. Glazed ceramic production areas were linked to high levels of Zn, As, Se, Zr, Cs, Tl, Li, Co and Pb. High levels of Ni and V (in association) were tracers of petrochemical plants and/or fuel-oil combustion. At one site under the influence of heavy vessel traffic these elements could be considered tracers (although not exclusively) of shipping emissions. Levels of Zn–Ba and Cu–Sb were relatively high in urban areas when compared with industrialised regions due to tyre and brake abrasion, respectively.     

Spatial and temporal variations of aerosol sulfate and trace elements in a sourcedominated urban environment

Time-resolved measurements of SO₂, sulfate, particulate carbon and trace metal (Pb, As, K, Mn, Fe and V) concentrations were performed simultaneously at four locations in Ljubljana, Yugoslavia, during February and April of 1985. During the winter three different SO₄²⁻ formation regimes are identified: A—morning period coinciding with maximum emissions and high humidity resulting in maximum SO₄²⁻ concentrations, with the sulfate formation during this period attributed to fast heterogeneous, aqueous oxidation of local SO₂ involving combustion products; B—late evening period with low humidity and high emissions when most SO₄²⁻ is primary; C—the remainder of the day when SO₄²⁻ appears to be of a regional origin and formed by a combination of heterogeneous and homogeneous processes. During the non-heating season, the SO₄²⁻ appears to be of regional origin.     

Physical features of the atmospheric aerosol determined with an aureolemeter and a FSSP probe in the Mediterranean Lampedusa island

In order to investigate the influence of the atmospheric aerosol on the ultraviolet radiation on earth, the measurement campaign Photochemical Activity and Ultraviolet Radiation (PAUR II) Modulation was carried out in the central Mediterranean Sea during the period May–June 1999. Two sites were chosen for measurements: the island of Crete (Greece), and the island of Lampedusa (Italy). The aerosol features over the Lampedusa island, as well as the dust coming from Sahara desert, were investigated by measurements of direct and diffuse solar irradiance carried out with an aureolemeter. The columnar volume size distributions of the aerosol showed a four-modal shape in a less turbid atmosphere when the aerosol optical depth was less than 0.2 at λ=500 nm, and a tri-modal shape in a turbid atmosphere when the aerosol optical depth at the same wavelength was greater than 0.5; the background aerosol turned out to be mainly composed of sea salt. The increase of the aerosol optical depth and of the particles density with radius about 1 μm has been found to be strictly related to the passage of Saharan dust in the time periods 14–22 May and 1–3 June, 1999. The columnar volume of particles obtained by the aureolemeter has been compared with the columnar volume of particles retrieved by in situ measurements carried out with a forward scattering spectrometer probe (FSSP) aboard a light aircraft flying over the island. Although the above two techniques refer to aerosol columns of different height and operate with different resolutions, their relevant results are in good agreement, especially during days with lower aerosol content. The two volume radius distributions have been also compared and their behaviours show a satisfactory agreement, mainly for particles with radius greater than 1 μm.     

The use of multivariate analysis to identify sources of selected elements in the Boston urban aerosol

The concentrations of eighteen elements were determined by instrumental neutron activation analysis for samples of air particulates collected over a five month period in the Boston metropolitan area. This set of data is analyzed for underlying structure by the methods of common factor analysis and hierarchial aggregative cluster analysis. The data can be interpreted on the basis of six common factors accounting for 77.5% of the total variance in the system. These factors are attributed to various sources of particulate material by noting the dependence of the factors on the elements. The cluster analysis assists in the interpretation of the factors.     

Quantifying the sources of hazardous elements of suspended particulate matter aerosol collected in Yokohama,Japan

We analyzed metals (Mg, Al, Ca, V, Cr, Mn, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Ag, Cd, Cs, Ba, Pb and Bi), water-soluble ions (Na⁺, NH₄⁺, K⁺, Ca²⁺, Cl^?, NO₃^? and SO₄^2?) and carbonaceous mass (EC and OC) in SPM aerosol samples using an ICP-MS, ion chromatograph and CHN corder, respectively. The SPM samples were collected from 1999 to 2005 at two locations (urban site A and industrial site B) of Yokohama, Japan with concentrations in mean and ranges of 34.2 and 19.7–50.3 μg m^?3 and 22.9 and 12.7–35.1 μg m^?3 for the respective location. Source apportionment of SPM aerosol was conducted appropriately for the first time to these locations employing PCA-APCS technique. Major sources of SPM at site A were a) crustal source, b) urban origin, c) undefined, and d) mineral rock. At site B, the sources were predicted as a) urban origin, b) undefined, c) crustal source, and d) secondarily formed aerosol. The tracers and nature of the source related to urban origin at both sites were similar but retaining different source strength. Secondarily formed aerosol was quite unique at site B. However, mineral rock was remarkable at site A.