Origin,characteristics and morphology of weathering crusts on Istria stone in Venice

To evaluate the effects of the environment on weathering of monuments of Istria stone in Venice, systematic mineralogical, petrographical and elemental analyses of depth profiles were performed on samples of surficial crusts (dendritic black, compact black, grey and white). Decay products of deposition and interactions between gases and stone, including wind blown dust, marine salts, anthropic aerosol, gypsum and nitrates, are incorporated into the mineral matrix down to a depth of 10 mm. In areas sheltered from rain, where black and grey crusts are observed, the high general humidity, carbonaceous particles and deposition of aerosols lead to the development of gypsum and other salts. In compact and grey crusts decay products decrease; in grey crusts carbonaceous particles are reduced, but in compact black crust products of previous treatments are found. In white crusts, formed in areas experiencing effective wash-out, chemical and mechanical attack cause surface recession.     

Black layers on historical architecture

Background, aim and scope

The external surface of any building in urban polluted environment is unavoidably destined to be covered with layers that assume a grey to black colour and are generally called ‘black crusts’. These, according to standard protocols and glossary, are deteriorated surface layers of stone material; they can have variable thickness, are hard and fragile and can detach spontaneously from the substrate, which, in general, is quite decayed. Plain visual examination may lead to consider ‘black crusts’ all similar, whilst only a careful diagnostic investigation can distinguish ‘black crusts’ and the consequences of their formation on stone substrates. In this paper, various black layers on marble are studied and compared and the morphological and compositional characteristics discussed according to the related mechanisms of formation. Differences between old (hundred years) and recent crusts (30 years) are investigated and pointed out.

Materials and methods

Samples of black crusts collected from the Milan Cathedral façade (Candoglia Marble) have been studied and compared with the careful and synergic employ of traditional techniques: optical (transmission and reflected VIS light) and electron microscopy, X-ray spectrometry and micro-Fourier transform infrared spectroscopy.

Results

Visual examination of loose fragments does not allow to point out outstanding differences amongst the various samples; black layers have similar main mineral components, gypsum and airborne particles, with different spatial distribution. The microscopic studies allowed to point out the porosity differences, the gypsum crystallisation habit, different amount of embedded particles, level and progress of marble decay.

Discussion

The observations lead to define three main types of black crusts: black crust deriving from marble sulphation, compact deposit and encrustation due to exogenic materials deposition. Black crusts show evidence of sulphation in progress, without a clear continuity solution between crust and marble; the lack of separation is particularly evident in ‘recent’ crust, where the sulphation process is more active. Black compact deposits show a higher porosity than black crusts because gypsum is not coming from the chemical corrosion of the substrate but from outside; actually, in the former case, the substrate is sound. Encrustations show a highly regular crystal organisation of gypsum (close packed tabular crystals) that cannot be traced back to casual atmospheric deposit or to corrosion of the substrate but rather to the crystallisation of a solution coming from an external source. Also in this case, the marble is sound; evidence of the effect of some protection treatment is pointed out.

Conclusions

In spite of the apparent similarity of the examined samples, analytical results have evidenced three main types of black crusts: black crust with decayed substrate, compact deposit and black encrustation showing a sound substrate underneath. Experimental evidence of calcite grains sulphation in progress, taking place according to a model recently proposed, has been observed. Sulphation process is prevented where particular conservation treatments had been applied in the past.

Recommendations and perspectives

New experimental studies can be focussed to understand the specific conditions (measurements of micro-climatic and thermodynamic parameters) and mechanisms for black crusts formation in situ. The problem of the kinetic of the sulphation process of marble, the assessment of black layers formation in the case of different carbonate stone materials and the study of acid attack in presence of surface protecting layers deserve further investigation.     

The characterisation of carbonaceous fly-ash particles from major European fossil-fuel types and applications to environmental samples

This paper describes the development of a technique to characterise carbonaceous fly-ash particles produced from five major European fuel-types (coal, oil, brown coal, peat and oil shale) using individual particle chemistries derived from energy dispersive spectroscopy as part of the EU COPERNICUS funded FLAME project. The final classification employed an hierarchy of quadratic discriminant functions such that 80% of the particles could be allocated to the correct fuel-type. The technique was then applied to particles extracted from the surface sediments of 196 lakes across four countries (UK, Estonia, Czech Republic and Ireland) so that the spatial distribution of impacts from these fuel sources could be determined. Spatial trends in fuel-type showed good agreement with known emission sources but absolute percentages were low in all countries due to high allocations to the “coal” fuel-type. It is thought that these high coal values are due to mineral particles surviving the acid pre-treatment. However, the results can still be used to determine sources of pollutant deposition. The technique is applicable to particles extracted from any depositional sink including, atmospheric collectors, building stone crusts, leaves and soils.     

Air pollution records on selenite in the urban environment

Black crusts (BC) on selenite, i.e. gypsum stone used in buildings and monuments in the city of Bologna (northern Italy) have been studied.The crusts have been compared with genetically identical ones encountered on gypsum outcrops in the area surrounding the same city, in a relatively clean rural environment.Because of gypsum's high solubility, also in the past, BC began to form and embed particles of atmospheric aerosol as soon as the stone was used in construction, even though the SO₂ levels in the air were probably much lower than today. Unlike other types of stone (sandstone, limestone, marbles), selenite is currently undergoing a deceleration of dissolution processes, following the acidification of the environment caused by industrialisation. For this reason the BC on selenite are older (up to 580±45 yr), thicker (up to 4 cm) and far more stable than those encountered on other types of building stones used in the same area.The BC are stratified: at the base, in contact with the stone, the crust contains numerous prismatic black particles originating from wood combustion; immediately above the base layer these particles progressively increase; finally, in the outer part of the crust one encounters the characteristic black, spongy spherical fly-ash originating from the combustion of mineral oils.From the chemical point of view, a comparison between urban and rural crusts shows that elements such as C, Si, K, Fe, V, Cr, Ni, Zn, Ga, As and Pb are due to present-day and/or past pollutant sources within the city itself.Moreover, the chemical data from the stratigraphy of the BC show that, while C and K were more abundant in the past than now, elements such as Fe, V, Cr, (Mn, Ni), Cu, (Zn), (Ga), As, Pb characterise recent and current urban atmospheres.     

Embryonic sulphated black crusts on carbonate rocks in atmospheric simulation chamber and in the field: role of carbonaceous fly-ash

Experimental conditions characteristic of the urban pollution in many European cities over the last decades were reproduced in a simulation chamber in which samples of limestone were exposed for a period of 12 months, both naked or sprinkled with carbonaceous fly-ash. In agreement with the findings reported in the literature the fly-ash emitted by heavy fuel combustion are highly reactive, undergoing chemical and morphological transformations which give rise to crystals growth, especially gypsum. The development of gypsum crystals was observed overall in close proximity of fly-ash anchoring them to the limestone surface. Samples of the same limestone exposed in the field in a polluted environment for the same period of time led to similar results. The preliminary mechanisms leading to the genesis of sulphated black crusts in polluted environments were thus highlighted. Because of their roughness the embryonic black crusts increase the development of the crust by trapping new particles. This trapping is also facilitated by the wetness of the stone surface leading to the development of hydrated mineral (gypsum) in the water meniscus between fly-ash and stone surface.     

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.     

Assessment of airborne heavy metal pollution by aboveground plant parts

Italian stone pine (Pinus pinea L.) and oleander (Nerium oleander L.) leaves, bark and wood samples were collected at different sites around an industrial area (Huelva, SW Spain) and compared with samples of the same species from a background site. Samples were analysed with respect to the following pollutants: Al, Ba, Cr, Cu, Fe and Pb by ICP-AES. The suitability of different plant parts as biomonitors of pollution was investigated. In pine samples from the polluted sites the ratio of concentrations between bark and wood was high for Al, Ba, Cu and Fe, whereas no differences were found in samples from the unpolluted area. No differences were detected in oleander for the same ratio. In the oleander species, the ratio between leaves and wood concentration allowed to distinguish between control and polluted sites. The ratio of the concentration between leaves and wood was elevated for Al, Ba and Fe in pine samples from the polluted sites. The ratio of the concentration in bark or leaves to their concentration in wood might be useful to detect inorganic atmospheric pollutants.     

Composition of weathering crusts on sandstones from natural outcrops and architectonic elements in an urban environment

This work presents mineralogical and chemical characteristics of weathering crusts developed on sandstones exposed to various air pollution conditions. The samples have been collected from sandstone tors in the Carpathian Foothill and from buildings in Kraków. It has been stated that these crusts differ in both fabric and composition. The sandstone black crust from tors is rich in organic matter and composed of amorphous silica. Sulphate incrustations accompanied by dust particles have been only sometimes observed. Beneath the black crust, a zone coloured by iron (oxyhydr)oxides occurs. The enrichment of the surface crust in silica and iron compounds protects the rock interior from atmospheric impact. The sandstones from architectonic details are also covered by a thin carbon-rich black crust, but they are visibly loosened. Numerous salts, mainly gypsum and halite, crystallise here, thus enhancing deterioration of the rock. Moreover, spherical particles originated from industrial emissions are much more common. Gypsum in natural outcrops, forms isolated and well-developed crystals, whilst these found on the architectonic details are finer and densely cover the surface. Such diversity reflects various concentrations of acid air pollutants in solutions.     

Differentiation of the contribution of local resuspension from that of regional and remote sources on trace elements content in the atmospheric aerosol in the Mediterranean area

For the determination of effects of contaminated crude soil on the content of trace elements in the atmospheric aerosol, trace elements in crude soil samples from within the area of influence of local resuspension were analysed. The obtained results were used for determining the contribution of local resuspension on contents of trace elements in the atmospheric aerosol using the enrichment factors (EF) method. The content of trace elements in a crude soil could arise from the geochemical background of the soil or from anthropogenic contributions. Analysis of the quantile showed that Cd, Se and Ni originate from local emission sources. PCA showed that four groups of sources contributed to the content of trace elements in PM in part of the receptor. Using EF, it was ascertained that local resuspension of crude soil particles had a dominant influence on the content of Fe, Mn and Ti in the atmospheric aerosol, and that local resuspension had no influence on the content of Se in the atmospheric aerosol. Dust originating from deserts of North Africa and Middle East, through long-range transport and through resuspension of settled dust particles, significantly contributes to the content of Fe, Mn and Ti in the atmospheric aerosol. Cd originated from contaminated crude soil. The other investigated elements originated partly from crude soil but also from some other emission sources in the region.     

Exposure to trace elements of flamingos living in a biosphere reserve, the Camargue (France)

Recent research has shown that some adult flamingos Phoenicopterus roseus collected from the Camargue Biosphere Reserve had tissue metal concentrations considerably higher than the average for this species. As the range of these birds is large, the origin of the contamination was unknown. Blood and feather samples from nestling flamingos were therefore analysed for trace metals to determine the presence and origin of local contamination. A comparison of elemental concentration in the feathers of nestling and adult flamingos revealed higher concentrations of Cd, Cu, Pb and Se in adults, and higher concentrations of Zn in juveniles. This was attributed to increased exposure to atmospheric pollutants of adults, and either differences in Zn requirements and metabolism between adults and juveniles, or a local contamination of the juveniles' food supply by Zn. Concentrations of Zn in serum were also very elevated compared with human standards. Cd, Cu, Zn and Se concentrations were analysed in outer (O) and inner (I) barbs (i.e. barbs that are, respectively, exposed or not exposed to external deposits) of greater coverts of nestling flamingos. A comparison of elemental concentrations in these two feather components indicates a local atmospheric contamination by Cd, Cu and Pb.     

A new approach for the fractionation of water-soluble organic carbon in atmospheric aerosols and cloud drops

A novel approach is described for the fractionation of water-soluble organic carbon (WSOC) in atmospheric aerosols and cloud drops. The method is based on the preliminary adsorption of the sample, acidified at pH 2, on a polymeric styrene-divinylbenzene resin (XAD-2) and subsequent elution with a series of solvents, which leads to the fractionation of the sample into three classes of compounds. The method was set up using synthetic mixtures of organic compounds and then applied to selected samples of atmospheric aerosols and cloud drops. All samples and collected fractions were analysed using size exclusion chromatography (SEC). This method proved particularly useful both in providing information on the organic content of the samples and for the characterisation of the macromolecular compounds (MMCs) in the samples. Synthetic samples were prepared using humic, fulvic and tannic acid to simulate naturally occurring MMCs. In the first fraction, eluted with HCl, only the most soluble organic compounds (oxalic acid, formic acid and acetic acid) were collected. In the second fraction, eluted with methanol, the major part of the organic material was collected together with the more hydrophilic constituents of the humic substances. In the third fraction, it was possible to separately recover the more hydrophobic component of the humic substances. A large number of atmospheric samples (fog, aerosol, cloud) were then analysed using SEC. Most of these samples evidenced a noteworthy chromatogram at 254 nm. Moreover, the chromatographic area evidenced a clear linear correlation with the total organic carbon (TOC) values. The fractionation method on XAD-2 was finally applied to selected atmospheric samples, yielding three classes of organic compounds. In each sample, a non-negligible amount of compounds with dimensional and chemical properties similar to humic substances were collected in the third fraction. The carbon content in this latter fraction was estimated both by TOC and by means of the correlation between TOC and SEC area.     

Determination of aliphatic and polycyclic aromatic hydrocarbons in atmospheric particulate samples of a coruña city (Spain)

The hydrocarbon composition of atmospheric particulate matter from A Coruña city (Northwest Spain) has been studied. TSP (total suspended particulate) and PM₁₀ (particulate matter with aerodynamic diameter <10 µm) samples were taken over 7 and 4 months at two stations located in residential and industrial sectors of A Coruña city, respectively. The levels of hydrocarbons found in atmospheric particulate samples of A Coruña city are higher than the ones found in other cities over the world. Ratios between the analysed compounds and their sources were established. Both anthropogenic and biogenic origins were found.     

Airborne particulate matter around the Cathedral of Burgos (Castilla y León,Spain)

A methodology to collect and analyse atmospheric particulate matter has been developed at the Cathedral of Burgos (Spain). Particles were collected in a portable particle sampler on carbon layers and stone surfaces. The analyses were undertaken under SEM-EDX by means X-ray mapping and Featurescan (a program for the automated characterisation of particles). To determine their possible sources, particles collected in the sampler and on carbon layers were classified according to their composition, mainly by cluster analysis. Then, they were compared with those deposited on stone surfaces. This classification is useful when a plan of preventive conservation for monuments is to be undertaken. In general, no important differences are observed between the chemical composition of particles directly collected from the atmosphere and those deposited on different substrates. Fine particles present the highest sulphur contents (almost 100%), while calcium is the major element in the medium and coarse particles. Other abundant elements are silicon, chlorine and phosphorus. The number of iron-rich particles is small. The study of the material deposited on carbon layers and stone substrates has confirmed the presence of gypsum in all cases.     

POPs in the Lagoon of Venice: budgets and pathways

Dioxins and furans (PCDD/Fs), polychlorobiphenyls (PCBs) and hexachlorobenzene (HCB) in the ecosystem of the Lagoon of Venice were studied, in order to provide a general picture of conditions in the lagoon in terms of contamination by persistent organic pollutants (POPs). We present here novel data on atmospheric deposition, water, sediment and clam samples collected in the lagoon during the period January 2001-December 2004. Atmospheric deposition was sampled monthly at six sites located both close and far from large industrial and urban sources. Water samples were collected monthly from fifteen stations, and twenty-five samples of sediments and clams (Tapes philippinarum) were collected in four areas where clams are farmed and harvested inside the lagoon. All samples were analysed for PCDD/Fs, PCBs and HCB by HRGC/HRMS in the same laboratory. All samples examined (atmospheric deposition and water) substantially confirmed the spatial pattern reported in previously published data on sediments and atmospheric deposition: the zone surrounding the Porto Marghera petrochemical plant always had the highest levels of POPs (i.e., PCDD/Fs: atmosphere approximately 6 pg of 2,3,7,8-TCDD equivalents (I-TE) m(-2)d(-1); water 0.37 pg I-TEl(-1); sediment: 300 ng kg(-1); clam 2.8 pg I-TE g(-1)), and the minima were found at points on the margins of the lagoon (PCDD/Fs: atmosphere approximately 1 pg I-TEm(-2)d(-1); water 0.05 pg I-TEl(-1); sediment: approximately 5 ng kg(-1); clam approximately 0.2 pg I-TE g(-1)). Intermediate values were often encountered in the historical city centre of Venice and in the central part of the lagoon. To confirm this, new data on correlation between levels of PCDD/F in sediments and clams are reported, both for absolute values and for the PCDD/F "fingerprint". There is always a clear fingerprinting signature (PCDF/PCDD>1) for samples collected near Porto Marghera, and the opposite (PCDF/PCDD<1) in the rest of the lagoon.     

Fluorocarbons in the Los Angeles Basin

Ambient air concentrations of fluorocarbon 11 (fluorotrichloromethane) and fluoro-carbon 12 (dichlorodifluoromethane) have been measured using a gas chro-matograph equipped with a pulsed, electron capture detector. Air samples taken on a moderately smoggy day in July 1970, at several locations near Los Angeles gave average readings of fluorocarbon 12, 0.7 ppb and fluorocarbon 11, 0.56 ppb. These readings were contrasted with those taken in early February 1973 when the air was clear and marked with turbulence due to several seasonal rain storms. The readings of both fluorocarbon 1 1 and 12 averaged about 25% less during clear weather than those taken during moderate smog. The effects of weather conditions on the concentration were also dramatically pointed out by the February samples, in that as much as a tenfold change in concentrations of both fluorocarbons from location to location and from day to day at the same location was observed. A concentration versus altitude study clearly revealed that fluorocarbons are trapped by an inversion layer. Examination of air samples taken in the vicinity of factories known to be users of fairly large quantities of fluorocarbons revealed in part how large users contribute to the atmospheric concentrations of fluorocarbons. A comparison of fluorocarbon levels in homes and public buildings with ambient outside air levels revealed that the concentrations in some homes and buildings may be as much as several thousand times as high as levels in outside air. Inside the homes and public buildings, levels were as high as one-half of a part per million. Long term photolysis studies in simulated sunlight of both fluorocarbons 11 and 12 in ambient air samples and in air samples with 1 ppm of hydrocarbon and 1 ppm of nitrogen oxides revealed that the two fluorocarbons are photochemically stable even when photolyzed for several weeks.     

Calibration of lichen transplants considering faint memory effects

Biomonitoring, among other purposes, can be used as a tool to study the dispersion of trace elements through the atmosphere and back to the earth's surface again. In this sense it has been used for more than 20 years now. Yet, the calibration of biomonitors elemental contents against other atmospheric element dispersion variables like deposition or airborne concentration is still an open subject. The knowledge of a calibration nevertheless represents a qualitative improvement upon the use of biomonitors. Biomonitors elemental contents are usually assumed to depend in a linear way on the average values of atmospheric element dispersion variables, thus a linear regression is assumed to provide a good calibration. In this work: the element dispersion variables like deposition or airborne concentration will be referred in general as availability variables due to reasons that will be clarified; an uptake experiment using transplants of lichen Parmelia sulcata carried out in Portugal during a 2-year period (1994/1996) is described; and new concepts and calibration methods are presented. Lichen and aerosol samples were analysed by nuclear analytical techniques PIXE and INAA, and total deposition dry residue samples were analysed by ICP-MS. A database of roughly 70,000 values was thus created and biomonitor calibration carried out considering that biomonitors are not mechanical instruments but that they rather describe their exposure with a non-perfect memory. Data shows that surveying lichens four times within 1 year, with a period of 3 months in between sampling campaigns, allows the recovery of availability mean, maxima and standard deviation for many elements.     

Temporal trends of persistent organochlorine residues in human adipose tissue from Japan, 1928-1985

The presence of pesticide residues in rain, throughfall, stemflow and in ambient air in two Italian forests affected by the forest damage phenomenon were investigated. Pesticides measured were: alachlor, atrazine, carbaryl, 2,4-D, diazinon, dichlobenil, fluazifop-butyl, MCPA, parathion, phorate and trifluralin. Rainwater samples were collected from May to October 1988 at Vallombrosa and Renon, air and atmospheric particulates were sampled during April-June 1989, only at Vallombrosa. A total of 146 samples of rainfall and 20 samples of ambient air were analysed and 49 out of 166 samples contained at least one active ingredient. Herbicides were more frequent than insecticides, and their concentrations were also higher (max 3.44 microg litre(-1)).     

Instrumental neutron activation analysis of ambient air dust particulates from metropolitan cities in India

Ambient air dust samples were collected from industrial, commercial and residential areas of four metropolitan cities (Delhi, Calcutta, Madras and Cochin) in India, and were analysed for 27 elements (As, Ba, Br, Ce, Co, Cr, Cs, Cu, Eu, Hf, Hg, Fe, Ga, La, Lu, Na, P, Sb, Sc, Se, Sr, Ta, Tb, Th, Rb, Yb and Zn) by Instrumental Neutron Activation Analysis (INAA). Samples were irradiated with thermal neutrons in a nuclear reactor for 1 day and counted by high resolution gamma spectrometry at different intervals. Several environmental standards such as Coal (SRM 1932b); Urban Particulate Matter (SRM 1648) from NIST, USA; Vehicle Exhaust from NIES, Japan; and Soil-5 from IAEA, Vienna were also analysed for quality assurance. The results reveal that the concentrations of several pollutant elements in dust samples from the four cities are highly variable. Wide differences were observed for elemental concentrations of As, Ba, Br, Cu, Cr, Hg, Fe, Sb, Se and Zn and these variations are explained in terms of their possible sources of origin.     

Order-of-magnitude increase of Hg in Norwegian peat profiles since the outset of industrial activity in Europe

Peat cores from six ombrotrophic bogs at different latitudes in Norway (58 degrees N-69 degrees N) were analysed for Hg by atomic fluorescence spectrometry. In all cases a smooth decrease of Hg with depth was observed down to 15-20 cm. At greater depths Hg showed a relatively constant level of the order of 10% of that in the peat surface layer. In the surface peat Hg concentrations exhibit moderate variation with latitude. The pre-industrial levels of Hg in the peat correspond to a net annual Hg accumulation of 0.3-0.9 microgm(-2). The Hg accumulation over the last 100 years is about 15 times higher on average than the pre-industrial level. The present work supports the view that a major part of the present atmospheric Hg in the Northern Hemisphere is of anthropogenic origin. It is speculated that the comparatively high Hg contemporary accumulation rates observed at the And?ya bog on 69 degrees N may be related to the Arctic springtime depletion of Hg.     

Temporal trends of elements in Turin (Italy) atmospheric particulate matter from 1976 to 2001

The temporal trends of major, minor and trace elements in the total atmospheric particulate sampled in the urban area of Turin (Italy) were determined for the following years: 1976, 1986, 1996 and 2001. The wavelength dispersive X-ray fluorescence (WD-XRF) technique was adopted to determine the concentrations of Ba, Br, Ca, Cl, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, S, Ti and Zn. A smaller number of samples was also analysed by ICP atomic emission spectroscopy (ICP-AES) and the results were compared with those obtained by WD-XRF to confirm their validity. A clear seasonal pattern with higher concentrations of the aforementioned elements in the cold periods was observed. Moreover, a change in the chemical composition of atmospheric particulate matter was evidenced, particularly between the first (1976 and 1986) and the last (1996 and 2001) years. This change can be attributed both to the greater contribution of Pb and Br to atmospheric pollution in the past and, in recent years, to the higher level of pollutants associated with increased vehicular traffic and industrial activities. The application of chemometric techniques (Principal Component Analysis and Cluster Analysis) allowed us to speculate about the main emitting sources influencing the total atmospheric particulate in these years.