Miloš Miler

Assessment of Metal Pollution Sources by SEM/EDS Analysis of Solid Particles in Snow: A Case Study of Žerjav, Slovenia

Solid particles in snow deposits, sampled in mining and Pb-processing area of Žerjav, Slovenia, have been investigated using scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDS). Identified particles were classified as geogenic-anthropogenic, anthropogenic, and secondary weathering products. Geogenic-anthropogenic particles were represented by scarce Zn- and Pb-bearing ore minerals, originating from mine waste deposit. The most important anthropogenic metal-bearing particles in snow were Pb-, Sb- and Sn-bearing oxides and sulphides. The morphology of these particles showed that they formed at temperatures above their melting points. They were most abundant in snow sampled closest to the Pb-processing plant and least abundant in snow taken farthest from the plant, thus indicating that Pb processing was their predominant source between the last snowfall and the time of sampling. SEM/EDS analysis showed that Sb and Sn contents in these anthropogenic phases were higher and more variable than in natural Pb-bearing ore minerals. The most important secondary weathering products were Pb- and Zn-containing Fe-oxy-hydroxides whose elemental composition and morphology indicated that they mostly resulted from oxidation of metal-bearing sulphides emitted from the Pb-processing plant. This study demonstrated the importance of single particle analysis using SEM/EDS for differentiation between various sources of metals in the environment.

Chemical and morphological characteristics of solid metal-bearing phases deposited in snow and stream sediment as indicators of their origin.

Detailed scanning electron microscopy/energy dispersive spectroscopy of metal-bearing particles in snow deposits and stream sediment from a steelworks area was performed. Identified metal-bearing phases were apportioned according to their chemical and morphological characteristics to anthropogenic phases and secondary weathering products. Anthropogenic metal-bearing phases are the most abundant in both media and are represented by various irregular ferrous oxides, ferrous alloys, spherical ferrous oxides, and ferrous silicates with variable contents of Cr, Mn, Ni, V, W, and Mo. Secondary weathering products are Al silicates, Fe oxy-hydroxides, and Fe oxy-hydroxy sulfates with minor contents of transition metals, resulting from weathering of anthropogenic phases and Pb–Zn ore minerals from a closed Pb–Zn mine located upstream from the study area. Comparison of anthropogenic metal-bearing phases in both media showed agreement in their compositions and morphologies and indicated their sources are high-temperature processes in steel production. It also showed that spherical metal-bearing phases were transported by the same transport medium, which is the atmosphere, while other phases were transported into stream sediment mostly by other pathways, such as precipitation runoff over contaminated surfaces.

Characterization of black deposits in karst caves, examples from Slovenia

Karst caves are important tourism and natural heritage destinations. Within dry cave passages otherwise notable for their rich flowstone decoration, areas with a characteristic black color can sometimes be observed on cave walls and floors and on speleothems. To determine the origin of these black deposits, mineralogical and chemical analyses were carried out in two caves (Postojna Cave and Črna Jama (Kočevje), Slovenia). Qualitative chemical composition was obtained by scanning electron microscopy in conjunction with energy dispersive X-ray spectrometry (SEM/EDS). Organic matter in black deposits was confirmed by the Walkley–Black (wet burning) and loss-on-ignition (LOI, dry burning) methods. Results showed that black deposits from the caves studied could be attributed to natural and anthropogenic causes. Natural causes are related to Mn–Fe oxide precipitation and are probably dependent on microorganism activity. Anthropogenic sources are related to historic (or/and prehistoric) human activities such as cave visitors using torches and fires, events outside the caves such as forest and settlement fires, and recent air pollution. Black deposits show the effect of long-term environmental impact on karst caves and could be included in guided tours of show caves along with a scientific explanation of their causes and origin.

Application of Scanning Electron Microscopy/Energy-Dispersive X-Ray Spectroscopy for Characterization of Detrital Minerals in Karst Cave Speleothems

Micro-scale observations in karst caves help to identify different processes that shaped local morphology. Scanning electron microscopy/energy-dispersive X-ray spectroscopy inspection of speleothems from two karst caves in Slovenia, Predjama and Črna Jama, confirmed the presence of sub-angular to sub-rounded detrital fragments of clay minerals, feldspars, quartz, Fe-oxides/hydroxides, rutile and Nb-rutile, xenotime, kassite, allanite, fluorapatite, epidote, ilmenite, monazite, sphene, and zircon, between 2 and 50 μm across. These occur in porous layers separating calcite laminae in the clayey coating on the layer below the surface of the speleothems, and are also incorporated within actual crystals. It is likely that they are derived from the weathered rocks of the Eocene flysch. Probably they were first transported into the caves by floodwaters forming cave sediments. Later, depending upon the climate conditions, they were moved by air currents or by water to the surface of active speleothems. They might also be redeposited from overlying soils enriched with wind-transported minerals from the flysch, or from higher passages filled with weathered flysch sediment, by drip water percolating through the fissured limestone. As some of the identified minerals are carriers of rare earth elements, Ti and Zr, their presence could affect any palaeoclimatic interpretations that are based upon the geochemical composition of the speleothems.

Calcite precipitates in Slovenian bottled waters

Storage of bottled waters in varying ambient conditions affects its characteristics. Different storage conditions cause changes in the initial chemical composition of bottled water which lead to the occurrence of precipitates with various morphologies. In order to assess the relationship between water composition, storage conditions and precipitate morphology, a study of four brands of Slovenian bottled water stored in PET bottles was carried out. Chemical analyses of the main ions and measurements of the physical properties of water samples were performed before and after storage of water samples at different ambient conditions. SEM/EDS analysis of precipitates was performed after elapsed storage time. The results show that the presence of Mg2+, SO42−, SiO2, Al, Mn and other impurities such as K+, Na+, Ba and Sr in the water controlled precipitate morphology by inhibiting crystal growth and leading to elongated rhombohedral calcite crystal forms which exhibit furrowed surfaces and calcite rosettes. Different storage conditions, however, affected the number of crystallization nuclei and size of calcite crystals. Hollow calcite spheres composed of cleavage rhombohedrons formed in the water with variable storage conditions by a combination of evaporation and precipitation of water droplets during high temperatures or by the bubble templating method.

Characterisation of secondary metal-bearing phases in used dental amalgam and assessment of gastric solubility

Detailed SEM/EDS investigation of used dental amalgams was carried out in order to characterise morphology and chemical composition of secondary metal-bearing phases resulting from long-term exposure of dental amalgam to oral environment, and assess their solubility in gastric environment. The investigation revealed numerous secondary phases, represented by compositionally and morphologically complex Hg-, Cu-, Sn-, Ag-, Zn-bearing sulphides and oxides/hydroxides, while sulphates and phosphates are scarce. Secondary metal-bearing phases mostly occur at the amalgam/tooth interface; however, some phases were found only on the occlusal surfaces of amalgam. Secondary phases mostly form porous aggregates of minute crystallites and micro- or nanocrystalline crusts. In oral environment, these phases are mostly stable and represent trapping media for dissolved potentially toxic metals released during amalgam corrosion. Simplified PHREEQC calculations of solubility of secondary metal-bearing phases in aqueous environment under conditions similar to those in gastric environment showed that secondary phases are more soluble in gastric environment than in oral solutions, which is mostly due to their forms of occurrence. Secondary phases in gastric environment thus act as secondary sources of potentially toxic metals, particularly Sn, Zn and also Cu, which are released both under reducing and oxidising conditions especially in acidic environment. Only very small amounts of Hg are potentially released and should not represent serious threat. Secondary phases that contribute the most to bioaccessibility of these metals are Sn hydroxychlorides, Sn oxides/hydroxides, Sn sulphates/hydroxysulphates, Sn oxides, Zn sulphides and Cu sulphides (Cu2S).