Airborne particulate matter (PM) has a major impact on the biogeochemical cycles of chemical elements in the urban environment. Anthropogenic-derived PM emissions are the cause of some of the most severe environmental and health problems. The presented study aims to improve our knowledge of PM dynamics by introducing a multi-media, multi-analytical and multi-elemental holistic approach to geochemical studies of inorganic PM in the urban environment. The importance of the holistic approach is highlighted and its application in a case study of Maribor (Slovenia) is presented. The chemical composition and individual particulate characteristics of street, attic and household dust were determined and compared with the characteristics of airborne PM, and PM deposited in snow, together with the chemical composition of the soil. We found that the mineralogical and chemical composition and the individual solid particle characteristics of the studied media differ considerably. Nevertheless, minerals of geogenic origin are present in all media. The highest levels of potentially toxic elements (PTEs) in all media, except household dust, are typical for industrial areas. Street dust primarily reflects the influence of winter road maintenance and industrial activities, while characteristics of household dust are predominantly influenced by indoor activities and properties of dwellings. The comparison of the chemical composition of attic and street dust indicates that emissions of As, Cd, Pb, S and Zn were higher in the past. The characterisation of airborne PM and PM deposited in snow is essential for the identification of the most recent sources of PTE-bearing particles. Several industrial sources and the fate of some particle types in the environment have been determined based on the findings of the SEM/EDS analyses. This study confirms that various environmental media are carriers of diverse geochemical information and highlights the importance of a holistic approach in geochemistry of PM in urban areas.

Sulfur-impregnated zeolite has been obtained from the natural zeolite clinoptilolite by chemical modification with Na₂S at 150 °C. The purpose of zeolite impregnation was to enhance the sorption of Hg(II) from aqueous solutions. Chemical analysis, acid and basic properties determined by Bohem’s method, chemical behavior at different pH_o values, zeta potential, cation-exchange capacity (CEC), specific surface area, X-ray powder diffraction (XRPD), scanning electron microscopy with energy-dispersive X-ray analysis (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), as well as thermogravimetry with derivative thermogravimetry (TG-DTG) were used for detailed comparative mineralogical and physico-chemical characterization of natural and sulfur-impregnated zeolites. Results revealed that the surface of the natural zeolite was successfully impregnated with sulfur species in the form of FeS and CaS. Chemical modification caused an increase in basicity and the net negative surface charge due to an increase in oxygen-containing functional groups as well as a decrease in specific surface area and crystallinity due to the formation of sulfur-containing clusters at the zeolite surface. The sorption of Hg(II) species onto the sulfur-impregnated zeolite was affected by the pH, solid/liquid ratio, initial Hg(II) concentration, and contact time. The optimal sorption conditions were determined as pH 2, a solid/liquid ratio of 10 g/L, and a contact time of 800 min. The maximum obtained sorption capacity of the sulfur-impregnated zeolite toward Hg(II) was 1.02 mmol/g. The sorption mechanism of Hg(II) onto the sulfur-impregnated zeolite involves electrostatic attraction, ion exchange, and surface complexation, accompanied by co-precipitation of Hg(II) in the form of HgS. It was found that sulfur-impregnation enhanced the sorption of Hg(II) by 3.6 times compared to the natural zeolite. The leaching test indicated the retention of Hg(II) in the zeolite structure over a wide pH range, making this sulfur-impregnated sorbent a promising material for the remediation of a mercury-polluted environment.

A comprehensive study of attic dust in an urban area is presented. Its entire life cycle, from determining historical emission sources to recognising the processes that take place in attic dust and its potential to impact human health is discussed. Its chemical composition and morphological characteristics of individual solid particles reflect past anthropogenic activities. High levels of Be-Cd-Cu-Sb-Sn-Pb-Te-Zn and occurrence of Cu-Zn shavings are typical for an industrial zone characterised by a foundry and a battery factory. High levels of Co-Fe-Mo-Ni-W-Ba-Cr-Mg-Mn-Nb-Ti and occurrence of various solid Fe-oxides, particularly spherical particles, were identified in another industrial zone, which was dominated by the automotive and metal-processing industries. Emissions from coal combustion affected the distribution of S-Se-Hg-Tl-As-Ag-U. The predominant mineral in attic dust is gypsum, which was presumably formed in situ by the reaction of carbonate dust particles and atmospheric SO₂ gas. The high oral bioaccessibility of As-Cd-Cu-Pb-Zn in the gastric phase and high bioaccessibility of As-Cu-Cd-Ni in the gastrointestinal phase were identified. Determined characteristics of attic dust and identified possibilities of prolonged human exposure to it indicate that attic dust should be treated as an excellent proxy for historical air contamination as well as a potentially hazardous material for human health.

An important aspect of geochemical studies is determining health hazard of potentially toxic elements (PTEs). Key information on PTEs behaviour in the human body in case of their ingestion is provided with the use of in vitro bioaccessibility tests. We analysed and compared oral bioaccessibility of a wide range of PTEs (As, Cd, Ce, Cr, Cu, Hg, La, Li, Ni, Pb, Sb, Sn, Zn), including some that are not often studied but might pose a human health hazard, in soil, attic dust, street dust, and household dust, using Unified BARGE Method (UBM). Additionally, feasibility of usage of scanning electron microscope techniques in analyses of solid residuals of UBM phases was tested. Results show that bioaccessible fractions (BAFs) of PTEs vary significantly between individual samples of the same medium, between different media and between the gastric and gastro-intestinal phases. In soil, attic dust and street dust, bioaccessibility of individual PTE is mostly higher in gastric than in gastro-intestinal phase. The opposite is true for PTEs in household dust. In all four media, with the exception of Pb in household dust, among the most bioaccessible PTEs in gastric phase are Cd, Cu, Pb, and Zn. During the transition from the stomach to small intestine, the mean BAFs of most elements in soil, attic dust, and street dust decreases. The most bioaccessible PTEs in gastro-intestinal phase are Cu, Cd, Ni, and As. Micromorphological and chemical characterisation at individual particle level before and after bioaccessibility test contribute significantly to the understanding of oral bioaccessibility.

Ombrotrophic peatlands contain a very small percentage of mineral matter that they receive exclusively from atmospheric deposition. Mineral matter deposited on the Šijec bog was characterized using scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS). We collected solid atmospheric deposition from snow, rainwater, and using passive samplers. Samples were collected at average atmospheric conditions and after two dust events. Size, morphology, and chemical composition of individual particles were determined. We distinguished four main particle groups: silicates, carbonates, organic particles, and Fe-oxyhydroxides. Silicate particles are further divided into quartz and aluminosilicates. Proportions of these groups vary between samples and between sample types. In all samples, silicate particles predominate. Samples affected by dust events are richer in solid particles. This is well observed in passive deposition samples. Carbonates and organic particles represent smaller fractions and are probably of local origin. Iron-oxyhydroxides make up a smaller, but significant part of particles and are, according to their shape and chemical composition, of both geogenic and anthropogenic origin. Estimated quantity and percentage of main groups vary throughout the year and are highly dependent on weather conditions. Dust events represent periods of increased deposition and contribute significantly to mineral matter input to peatlands.