Temporal variability of PM10 concentrations
The studied daily concentrations of PM10 ranged from 10.90 to 167.70 µg/m3 (Fig. 2), with an average mass concentration of 46.31 μg/m3. The mean PM10 mass concentration was higher during the cold period (67.24 µg/m3, October–March) than during the warm period (25.38 µg/m3, April-September). During winter, the higher PM10 concentrations are correlated with fossil fuel and biomass burning emissions, and enhanced by the meteorological conditions, such as thermal inversions, which favors the accumulation of PM10 and other pollutants (Szép and Mátyás 2014; He et al. 2017). The annual mean concentration (46.31 μg/m3) was higher than the WHO air quality guideline (20 μg/m3), and the European Union's limit value for PM10 (40 μg/m3).
Elemental composition
Table 1 summarizes the elemental arithmetic means, maximum, minimum, and median of PM10 mass. The most abundant PM10 elements are O, C and Si, accounting to the 85% of the total PM10 mass. During the analyzed days from the cold period (January, February, October, November, December) the O and Si weight percent were lower than in the warm period (March-September). Si has major contributions from sources, such as vegetation, decomposed volcanic rocks, diesel engines, gasoline engines and smoking, while aluminum comes mainly from terrestrial sources, soils and the breakdown of silicates (Cao et al. 2008).
Table 1 Elemental weight percent in Ciuc basin for the studied daily of 2015 The concentration of C varied during the study period from 13.46 wt% to 56.91 wt% (mean 27.83 wt%). The next higher elemental weight percent’s are for Na, Ca, Ti and Al, with 1.20 wt%, 1.18 wt%, 1.07 wt% and 1.00 wt%, respectively, suggesting the common mineralogical sources, derived from soil, resuspension or other anthropogenic activities (Genga et al. 2012). The presence of Na can be due to sea spray and numerous anthropogenic activities, such as wood/biomass combustion (Cao et al. 2008; NIPHE 2012; Keresztesi et al. 2020).
Source identification
Elemental ratios
Normally PM10 Ca weight percent may indicate the terrestrial sources, but the 0.69 mean Ca/Mg ratio much lower than the Ca/Mg ratios in dolomite (1.65) and in crust (1.78) (Taylor 1964) indicate the significant independent sources of Ca, which can be attributed to secondary pollution, such as resuspension. Ti (rangeing between 0.10 and 5.73; mean 1.07) has been identified as markers for vehicles emission and resuspension dust (Cheng et al. 2018). The Si/Al ratios were examined and found to range between 4.81 and 82.61 (mean 36.76). In the Earth’s crust Si/Al ratios were 3.42 (Taylor 1964). The significant differences between ratios may be due to the variation of periods of drought and rainy seasons. During the dry periods of the year, the concentration of silica is much higher than that of aluminum, mainly due to differences in soil concentration. The differences are also seasonal. In winter, the differences are significantly smaller between the two pollutants, indicating their common source. Most road surfaces (95–99%) are composed of rock material (Samiksha and Sunder Raman 2017). The contents of S, Zn, Mn, Mg, Fe, K and P had values varying from 0.54 to 0.88 wt%. Low Cl, Cu, W, Sr, Ba and N elemental weight percent (0.004–0.34 wt%) were also observed. The emission sources of Sr, Zn and Ba can be vehicle brake wearing and tearing (Cheng et al. 2018; Kalaiarasan et al. 2018), while Mn and Cu may come from industry (Xue et al. 2019). The mean ratios of Cl/Na (0.31) are significantly lower in the samples than that in seawater (1.8) (Chesselet et al. 1972; Xu et al. 2013). This fact is mainly due to continental air mass circulations, without a significant marine influence or to air masses that lost their sea spray content by travelling to the interior of the continent, being loaded with pollutants from anthropogenic sources or components from terrestrial ones. These aspects can also be observed from the Hysplit analysis (Fig. 7). The mean S/Ca ratio was 2.80, also much higher than the 0.80 S/Ca ratio in calcareous rocks (gypsum). The results show that the sources of S can be attributed to fossil fuel combustion and rubber tire wearing and other anthropic activities (Xue et al. 2019).
Enrichment factor, pollution load index and geo-accumulation index
According to Espitia-Pérez et al. (2018), to identify the impact of emission sources, the crustal EFs of the trace elements can be compared to the Earth's crust. The results regarding the EF values are following the downward order S > N > Cl > Si > Zn > Sr > K > Ca > P > W > Ba > Mg > Al > Cu > Na > Ti > Mn, suggesting an origin dominated by anthropogenic sources (Table 2). The results of EFs showed that S, N, Cl and Si were enriched in PM10. S had the highest EF values among the studied elements, having a remarkably high enrichment (average value 203.99), indicating the substantial contribution from anthropogenic emissions, such as fossil fuel combustion or rubber tire wearing. The EFs of Na, Ti, Cu, Mn (< 1), Al, Mg, Ba (1–2) and Ca, K, P, W (2–5) showed lower values than 10, indicating the elements mainly had terrestrial origins (Li et al. 2018). Sr and Zn (ranging between 5 and 20) were medially enriched and were probably under the impact of motor vehicle and brake wearing emissions (Xue et al. 2019).
Table 2 EF average crustal and PM10 compositions The EF values suggest that Al, Ca, and Si have an anthropogenic component from the total mass composition, K originates from biomass burning and agriculture, while Mn and Cu can be attributed to industrial activities. Fossil fuel burning and industry is the main generator for S, while Zn can be originated from motor vehicle emissions and also industry (Yan et al. 2017; Yu et al. 2018; Xue et al. 2019). In Table 3 the Si, S, Cl and Zn show PLI values greater than 1, which may be due to the influence of anthropogenic sources, such as industrial processes, abrasion of metallic materials and traffic-related sources and construction works (Cheng et al. 2018; Casares et al. 2019).
Table 3 PLI and Igeo values The calculated Igeo values (Table 3) indicate that only Si, S and Cl have high positive values (Igeo = 0.18, 0.48 and 0.35) which are ranked in class 1. Other elements (Na, Mg, Al, P, K, Ca, Ti, Mn, Fe, Cu, Ba, Sr, W and Zn) have negative Igeo values. The contents of S, Si and Cl increase as a result of some anthropogenic activities in the Ciuc basin, indicating the presence of mixed sources, such as household wood combustion, traffic, industrial activities, and construction works (Wang 2015). S can be attributed to vehicle fuel combustion, biomass burning and industrial activities, while Cl can be originated from biomass burning and marine sources. Si can be emitted from biomass burning, coal combustion and soil resuspension (Xie et al. 2009; Casares et al. 2019).
Particle mass reconstruction
Based on the determination of the amount of resuspended soil particles in particulate matter (Eq. 7), they are present in 72.10% of the average composition of the analyzed samples. The elements used in the formula are Al, Si, Ca, Fe and Ti, of which Si is present in significant amounts. We also used Eq. 8 in order to verify the percentage of resuspended soil particles. This resulted in 68.79% which supports the correctness of Eq. 7. During winter, in the Ciuc basin the main heating sources are biomass combustion and natural gas, which are major contributors to air pollution in the studied area (Szép et al. 2019).
The RCM elementary analysis estimates that the average PM10 composition is 72.10% soil, 20.92% smoke K, 13.84% salt, 1.53% sulfate and 1.02% organic matter. The average RCM calculated for the dataset was about 95.71% as compared to the PM10 concentration. The missing 4.29% of mass could be water vapor, which was not measured in this study. The comparison of RCM and gravimetric mass is presented in Fig. 3. The significant correlation coefficient (0.88) between the RCM and gravimetric mass suggests a good agreement between the methods.
Correlation analysis
Several different techniques have been used in our study to define the various emission sources and the observed pollutant concentrations: first from the correlation coefficients of each of these pollutants with each other, and then applying PCA. In Fig. 4 the correlation matrix coefficients can be observed.
A positive correlation between Ca/Fe (0.611) would be indicative of the presence of ferromagnesian silicates and other common terrestrial sources. The significant correlation between Ca and Mg (0.810) suggests the same source origin (Valdés et al. 2005), such as dolomite, calcite and limestone, showing that Ca and Mg mainly comes from the weathering of calcareous, dolomitic rocks (Keresztesi et al. 2017). Silicate minerals are presumed to be present in this fraction as evidenced by the high Mg/Fe (0.903) elemental ratio. The origin of silicates are volcanic, metamorphic rocks, common in the Ciuc basin, containing Mg, Fe and Al. This also explains the presence of the significant positive correlations between Mg/Al (0.573) and Fe/Al (0.903). On the other hand, the presence of the mineral fractions in the PM10 can also support the significant correlations between Ca/Na (0.439). Si/Mg (0.483), Ti/Mn (0.725), Al/K (0.903), Na/P (0.479) and S/Mg (0.435), confirming again the crustal origin of these elements in PM10 (Avino et al. 2014). Another part of the PM10 fraction, as mentioned in the determinations of pollution indices, derives from emission sources and resuspension. The major components of coarse PM10 could be aluminosilicates and other oxides from crust (Pfeiffer 2005). This explains the presence of the correlations between Na/O (0.643), Ca/O (0.557), Al/O (0.569), Si/O (0.819), Si/Ca (0.532), O/S (0.457) and O/P (0.692). The positive correlation values between Si/Cl (0.508), Si/Na (0.608), Si/S (0.489), Ca/K (0.611) and S/Fe (0.435) indicates the common sources, such as biomass burning. S and Fe take part in the neutralization of the PM10 layers as synergistic elements and they have high geochemical affinities, if they meet each other in any medium they start to react to the other element (Roy et al. 2015). The correlation coefficients between Si/Cl, Si/Na, Si/S and Ca/Al (0.563) can also be an indicator for industrial activities. Na/Cl correlation (0.485) indicates the possible presence of sea-spray contribution to PM10 and other common sources.
Principal component analysis
According to Malandrino et al. (2013) the chemometric treatment of the experimental data was carried out through the application of principal component analysis (PCA). Table 4 presents the Varimax rotated factor loadings with eigenvalues > 1, explaining 91.99% of the total variance. The first factor (F1) explaining most of the total variance (35.87%) has high loadings of O, C, Si, K, S and Cl. The association of these elements can suggest post volcanic activity, but high loadings of Cl and S are also a tracer of anthropogenic emissions, such as biomass burning or fuel combustion (Johansen et al. 2011).
Table 4 Analysis Source apportionment using Principal Component Analysis Representing 22.72% of the total variance with high loadings of Al, K, Fe, Na and P the second factor is considered to have mixed sources. The correlation between Al, K, Fe and Na can be related to the resuspension of these elements, in the form of crustal material and soil dust (Koçak et al. 2011; Ramírez et al. 2018). According to Malandrino et al. (2013) the correlation of Fe and P is more difficult to explain, but P in the aqueous form in correlation with sodium can form Na3PO4, which in the industry is used as a cleaning agent, lubricant, food additive, stain remover and degreaser. The association of K and P can be found in N type chemical fertilizers. The third factor (F3) is related to terrestrial sources, accounting for 14.44% of the total variance with high loadings of Ca and Mg. These two elements are a common tracer of crustal material and can be associated with the dissolution of calcareous and dolomite rocks, or resuspended or long-range transported road dust (Keresztesi et al. 2017). Factor 4 (F4) explained 11.93% of the total variance, showing high loadings of Ti and Mn, which are usually associated with mineral aerosols or industry (Allen et al. 2001). The fifth factor represented only 7.03% of the total variance with a significant proportion of Zn, which is a representative for vehicle sources. Zn is associated with tire wear and brake abrasion (Ramírez et al. 2018), being a vulcanizing agent in tire manufacturing (Tanner et al. 2008).
Overall, it can be said that at the studied area the major source of aerosol components is represented by post volcanic activity and crustal origin, caused by the resuspension of crustal material and soil dust.
Geochemical analysis
The Ciuc basin consists of partly volcanic, metamorphic, and partly sedimentary rocks: andesites, dolomites and crystalline slates. Analyzing Fig. 5, one can observe mixed sources: high Si concentrations, higher than those of andesites, suggesting that most of them originate from secondary, anthropogenic sources, such as resuspension of the abandoned materials. In the particulate matter samples, the Si concentration does not follow the original rock composition, suggesting that particulate matter tends to accumulate based on element affinity and charge neutralization.
The major oxides of the studied samples have a large variation in SiO2 (85.74–97.91 wt %), K2O (0.17–5.96 wt %), Al2O3 (0.26–3.62 wt %), MgO (0.17–3.19 wt%), CaO (0.56–3.06 wt%), Fe2O3 (0.09–2.15 wt%), Na2O (0.02–1.61 wt%), P2O5 (0.01–0.53 wt%), TiO2 (0.001–0.37 wt%). The above-mentioned oxides are the common oxides of the soil, in addition to water and carbonates (Malm et al. 1994; Motallebi et al. 2003), they appear in the atmosphere through resuspension (Gietl et al. 2010). Moreover, the De La Roche diagram shows that the concentrations of Ca, Mg and Al do not reach the composition of the rocks, showing the accumulation of Si.
Back–trajectory analysis
Long-range simulations were carried out with HYSPLIT Lagrangian model to analyze the possible pollution sources in the Ciuc basin. The main aim of the HYSPLIT simulation was to determine the origin of PM10 arriving from different regions during the selected period. The optimum number of clusters were selected based on the TSV change against the number of iteration graph (Fig. 6) for 400 m and y for 1500 m, respectively (Su et al. 2015). As a result, the numbers of selected clusters are 5 and 4, where sharp decreases were observed. In order to decipher the air mass movements during the 1-year period the clusters (average trajectories) for both altitudes were analyzed and are presented in Fig. 7.
More than 70% of the simulated wind flow pattern shows south westerly circulation origin, which is indicating a high-pressure system. On the other hand, the model-simulated wind flow shows strong north, north-east flow. The significant difference between 400 and 1500 m altitude is that the origins of air parcels are higher in case of 1500 m (higher with at least 500 m for each cluster). As stated earlier the optimal number of clusters for 1500 m was 4. Comparing the 4 and 5 cluster solutions (1500 m) the main difference was that the air masses paths originated over Croatia, Hungary and western part of Romania in 4-cluster solution were separated into sub-systems (clusters), however in 5 cluster solutions the contribution percentages were the same. The air systems obtained for 400 m and the contribution percentage of each cluster (5-cluster solution) was as follows: cluster 5 originated from the north-eastern part and passed through Ukraine, Moldova and then reached the Ciuc basin. The followed trajectory is a few hundred kilometers long and represents 11% of all the trajectories obtained for the one-year period. On the other hand, two clusters of westerly and south-easterly inflow, (clusters 1 and 4), have mainly local or regional characteristics, with shortest travel distance and represent more than 60% of all the clusters. Clusters 2 and 3 seem to have the longest trajectories, which can transport pollutants from long distances from countries like Hungary and Ukraine. Both clusters have a contribution of ~ 10% and are characterized by fast movements. Analyzing and comparing the results obtained for 1500 m, it is obvious that important similarities are between the two solutions. The dominating clusters were as follows: 1, 3 and 4, with a contribution of 22%, 37% and 35%, respectively. The remaining 5% (cluster 2) -distinctive system- was characterized by the fastest transport pattern (longest in length) among all the clusters (400 and 1500 m). Originated from Netherlands and transported over Western and Central Europe (Germany, Czech Republic, Slovakia, eastern part of Hungary) has the potential to be loaded with pollutants generated by anthropogenic activities. This can be attributed to the highly industrialized countries; however, this system has the minimum contribution, only 5%.
On the other hand, we must mention that the impact of natural sources may also be significant under certain meteorological conditions. The study demonstrated that PM concentrations in Ciuc basin may be influenced by winds arriving in the region from and outside Romania. The results show that significant amount of PM10 may arriving to the studied area, while the most frequent air masses entering Ciuc basin and hence influencing PM10 concentrations come from the West and South, specifically the SW directions. In case of 400 m solutions 77% of the trajectories were originated from these directions and similar tendency was observed at 1500 m with 72%. The proposed methodology used through the study e.g. long-range trajectory and cluster analysis were satisfactory to identify the source regions of the trajectories arriving to the study area and carrying anthropogenic and natural sources pollutants. As a conclusion we can say that the source regions were identified using long-range simulations and it is a reliable tool to understand the contribution of pollutants transported from the source regions to the studied area.
Health risks of metals in PM10
The cumulative risk (HQ and HI) values of non-carcinogenic substances of Al, Ba, Cl, Cu, Fe, Mn, P, Sr, Ti, W and Zn for both children and adult are shown in Table 5. These values are for the three exposure pathways of ingestion, inhalation, and dermal contact (Sah et al. 2019). Although estimated HIs for all the studied chemical compounds/elements were below the safe level (i.e. < 1) for both adults and children, several HIs were found to be higher than others, indicating the necessity to carefully monitor their concentration. The HQ values of Cu (2.90E-03 and 1.24E-03), Mn (2.20E-02 and 6.74E-03) for both children and adults via inhalation, P (1.41E-03 and 1.51E-04), Fe (2.39E-03 and 2.57E-04) via ingestion and Al (1.60E-02 and 8.80E-02), Cl (9.42E-03 and 5.18E-02), Fe (1.51E-02 and 8.30E-02), Mn (6.61E-03 and 3.63E-02), Ti (5.49E-03 and 3.02E-02), Zn (2.29E-04 and 1.26E-03) for children and adults via dermal contact were almost reaching the safe level, while in the case of other elements the HQ values were lower than the safe level. In the case of HI results the elements almost reached the level of safety, except the values of Ba (7.88E-07 and 8.88E-08) Sr (6.52E-08 and 7.25E-09), W (5.28E-08 and 5.50E-09). Some of the aforesaid metals are key components of human homeostasis, but in increased concentration they become toxic causing pathologic states and diseases. For example, the vital role of Fe is widely acknowledged, Fe being involved in fundamental biological activities such as oxygen transportation, cellular metabolism, mitochondrial respiration, DNA synthesis, cellular growth and differentiation (Ganz 2013; Paul et al. 2017).
Table 5 HQ and HI for metals in PM10 Excessive Fe accumulation may result in augmented oxidative stress and successive dysfunction of various organs and systems such as liver, spleen, heart, bone marrow, pancreas and central nervous system (Gujja et al. 2010). According to Chen et al. (2018), Mn is known as a cofactor for several enzymes implicated in antioxidant protection, energy production, immune response, and regulation of neuronal activities. The brain is the critical target of Mn intoxication, which has been associated with cognitive, motor, and behavior deficits through amplified oxidative stress and apoptosis, mitochondrial dysfunction, protein misfolding, autophagy dysregulation, and impairment of other metal homeostasis (Holley et al. 2011; Chen et al. 2018). Mn exposure is a public health concern especially in young age when the brain is still developing (Bjørklund et al. 2017). The summary regarding the relationship between health effects and measured contaminants in the studied area via the inhalation exposure pathway is shown in Table 6 (IEC 2009). The elements which were studied and analyzed during the present study are not carcinogens, but they can cause several other diseases.
Table 6 Hazard identification summery table according to (IEC 2009) Being the third most abundant element on Earth, Al is easily distributed and frequently present in the environment, being toxic for the human organism, especially to bones, bone narrow and the nervous system (Saiyed and Yokel 2005). According to Oskarsson (2015) acute or chronic exposure to barium salts can cause several disorders, such as renal intoxication, hypertension, cardiac malfunction, and hearing loss at experimental animals.