In this paper, the authors investigated changes in mass concentrations of particulate matter (PM) during the Coronavirus Disease of 2019 (COVID-19) lockdown. Daily samples of PM1, PM2.5 and PM10 fractions were measured at an urban background sampling site in Zagreb, Croatia from 2009 to late 2020. For the purpose of meteorological normalization, the mass concentrations were fed alongside meteorological and temporal data to Random Forest (RF) and LightGBM (LGB) models tuned by Bayesian optimization. The models’ predictions were subsequently de-weathered by meteorological normalization using repeated random resampling of all predictive variables except the trend variable. Three pollution periods in 2020 were examined in detail: January and February, as pre-lockdown, the month of April as the lockdown period, as well as June and July as the “new normal”. An evaluation using normalized mass concentrations of particulate matter and Analysis of variance (ANOVA) was conducted. The results showed that no significant differences were observed for PM1, PM2.5 and PM10 in April 2020—compared to the same period in 2018 and 2019. No significant changes were observed for the “new normal” as well. The results thus indicate that a reduction in mobility during COVID-19 lockdown in Zagreb, Croatia, did not significantly affect particulate matter concentration in the long-term..
This paper present seasonal variation in the equivalent concentration (BaPeq) of PAHs in order to assess the potential cancer risk for two different groups of residents via ingestion, dermal contact and inhalation pathways. The possible ecological risk caused by PAH atmospheric deposition based on risk quotient was also estimated. A bulk (total, wet and dry) deposition and PM10 particle fraction (particles with an equivalent aerodynamic diameter < 10 µm) were collected from June 2020 to May 2021 at an urban residential location in the northern part of Zagreb, Croatia. The monthly average of total equivalent BaPeq mass concentrations of PM10 varied from 0.057 ng m−3 in July to 3.656 ng m−3 in December; the annul ∑BaPeq average was 1.348 ng m−3. In bulk deposition, ∑BaPeq mass concentrations varied from 1.94 to 57.60 ng L−1. In both investigated media, BaP had the highest contribution in carcinogenic activity. For PM10 media, dermal absorption implied the greatest potential cancer risk, followed by ingestion and inhalation. For bulk media, a moderate ecological risk for BaA, BbF and BaP was observed according to the risk quotient approach.
Tomato waste was studied as a low-cost biosorbent for the removal of five pharmaceuticals (dexamethasone, febantel, procaine, praziquantel, and tylosin) from water. Tomato waste was characterized chemically and microstructurally before and after simulated sorption. Sorption performance was interpreted as a function of the initial pharmaceuticals concentration, temperature, and physicochemical properties of the tomato waste. The linear, Freundlich, and Dubinin–Radushkevich (D-R) isotherms were used to describe the experimental results at different temperatures (298, 303, and 308 K). Thermodynamic parameters such as standard free energy (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) were determined. Negative values of ΔG° in the temperature range of 298–308 K strongly indicate the spontaneous nature of the biosorption process. In addition, the values of ΔH° for the biosorption of dexamethasone, procaine, praziquantel, and tylosin on tomato waste were negative, indicating exothermic processes, while the positive value for febantel indicated an endothermic process. The kinetic data were analyzed using (i) kinetic models to determine the kinetic parameters (Lagergren’s pseudo-first order and Ho’s pseudo-second order) and (ii) adsorption–diffusion models to the describe transport mechanisms of pharmaceuticals from aqueous solution onto tomato waste as adsorbent (Weber–Morris intraparticle diffusion and Boyd film diffusion models).
Atmospheric bulk and wet deposition samples were collected simultaneously at the background coastal site in the Eastern Middle Adriatic region in order to assess the impact of major ions (Cl−, NO3−, SO42−, Na+, K+, NH4+, Mg2+, Ca2+) on deposition acidity and distinguish the main sources. Higher ion levels were observed during the cold period, especially for Cl−, Na+, Mg2+ and K+. Dust intrusion caused significant increases in levels of Ca2+, Mg2+ and K+, while open-fire events increased the levels of K+. Deposition acidity showed seasonal differences as well as the influence of dust intrusion. Low ionic balance ratios indicated acidic deposition properties and the presence of organic anions. The highest neutralization ability was found for Ca2+, Na+ and NH4+. Several natural (marine, crustal) and anthropogenic sources were determined, as well as the formation of secondary aerosols. Wet deposition was characterized by higher contribution of sea salt fraction compared to bulk deposition and lower contribution of crustal fraction.
Understanding how atmospheric pollutants interact with soil pollution is essential for assessing long-term environmental and human health risks. This study compares concentrations of polycyclic aromatic hydrocarbons (PAHs) and potentially toxic elements (PTEs) in PM10 and surface soil near air quality monitoring stations in Zagreb, Croatia. While previous work identified primary emission sources affecting PM10 composition in the area, this study extends the analysis to investigate potential pollutant transfer and accumulation in soils. Multivariate statistical tools, including correlation analysis and principal component analysis (PCA), were employed to gain a deeper understanding of the sources and behavior of pollutants. Results reveal significant correlations between air and soil concentrations for several PTEs and PAHs, particularly when air pollutant data are averaged over extended periods (up to 6 months), indicating cumulative deposition effects. Σ11PAH concentrations in soils ranged from 1.2 to 524 µg/g, while mean BaP in PM10 was 2.2 ng/m3 at traffic-affected stations. Strong positive air–soil correlations were found for Pb and Cu, whereas PAH associations strengthened at longer averaging windows (3–6 months), especially at 10 cm depth. Seasonal variations were observed, with stronger associations in autumn, reflecting intensified emissions and atmospheric conditions that facilitate pollutant transfer. PCA identified similar pollutant groupings in both air and soil matrices, suggesting familiar sources such as traffic emissions, industrial activities, and residential heating. The integrated PCA approach, which jointly analyzed air and soil pollutants, showed coherent behaviour for heavier PAHs and several PTEs (e.g., Pb, Cu), as well as divergence in more volatile or mobile species (e.g., Flu, Zn). Spatial differences among monitoring sites show localized influences on pollutant accumulation. Furthermore, this work demonstrates the value of coordinated air–soil monitoring in urban environments and provides an understanding of pollutant distributions across different components of the environment.