Ondřej Zvěřina

Determination of mercury species using thermal desorption analysis in AAS

Analytical aspects of the determination of inorganic mercury (Hg) species by thermal desorption followed by atomic absorption spectrometry (AAS) detection were investigated in this work. Characteristic Hg release curves of the following species were observed: Hg0, HgCl2, HgO, HgSO4, HgS, and the Hg bound to humic acids. Particular attention was dedicated to the thermal stability and change of bond of Hg0 in the following matrices: sand, kaolinite, granite, peat, power plant ash, and soil. The bond of elemental Hg in environmental materials was described on basis of this experiment. Contaminated soil samples from two locations in the Czech Republic were investigated by thermal desorption analysis. Afterwards, the contents of volatile and plant-available Hg in the studied samples were determined. The determination of Hg0 using the thermal method was related to the results of liquid sequential extraction. The development of Hg speciation and the stability of Hg were assessed on basis of the data obtained. Thus, the analytical procedure used is a suitable tool for the study of inorganic Hg species in contaminated soils.

Ultra-trace analysis of Hg in alkaline lavas and regolith from James Ross Island

Abstract Polar regions represent a unique environment for the study of mercury cycling in the global ecosystem. Our research was focused on the assessment of the origin and mobility of mercury in the geochemical cycle in Maritime Antarctic (James Ross Island) by means of atomic absorption spectrometry. Mercury content in a set of extrusive (subaerial, subaqueous) and intrusive (dyke) alkaline basalts ranged between 1.6 µg kg-1 (for samples without xenoliths) and 8 µg kg-1 (for samples containing crustal xenoliths). The mercury content in alkaline basalts indicates a very low concentration of mercury in peridotitic mantle sources. Samples of regolith from James Ross Island were subjected to a comprehensive analytical procedure proposed for ultra-trace mercury concentrations involving fractionation and thermal analysis. Total mercury contents in regolith (2.7–11.3 µg kg-1) did not deviate from the natural background in this part of Antarctica. Additionally, the obtained results are about two orders of magnitude smaller than values formerly assumed for primary mercury contents in basaltic lavas. Our results from Antarctica were compared with mercury contents in basaltic rocks from Greenland and the findings were confirmed. It seems that the input of mercury of geological origin into the polar ecosystem is apparently lower than expected.

Effects of the soil microbial community on mobile proportions and speciation of mercury (Hg) in contaminated soil

ABSTRACT The precise characterization of the behavior of individual microorganisms in the presence of increased mercury contents in soil is necessary for better elucidation of the fate of mercury in the soil environment. In our investigation, resistant bacterial strains isolated from two mercury contaminated soils, represented by Paenibacillus alginolyticus, Burkholderia glathei, Burkholderia sp., and Pseudomonas sp., were used. Two differently contaminated soils (0.5 and 7 mg kg−1 total mercury) were chosen. Preliminary soil analysis showed the presence of methylmercury and phenylmercury with the higher soil mercury level. Modified rhizobox experiments were performed to assess the ability of mercury accumulating strains to deplete the mobile and mobilizable mercury portions in the soil by modification; microbial agar cultures were used rather than the plant root zone. A sequential extraction procedure was performed to release the following mercury fractions: water soluble, extracted in acidic conditions, bound to humic substances, elemental, and bound to complexes, HgS and residual. Inductively coupled plasma mass spectrometry (ICP-MS) and a single-purpose atomic absorption spectrometer (AMA-254) were applied for mercury determination in the samples and extracts. Gas chromatography coupled to atomic fluorescence spectrometry (GC-AFS) was used for the determination of organomercury compounds. The analysis of the microbial community at the end of the experiment showed a 42% abundance of Paenibacillus sp. followed by Acetivibrio sp., Brevibacillus sp., Cohnella sp., Lysinibacillus sp., and Clostridium sp. not exceeding 2% abundance. The results suggest importance of Paenibacillus sp. in Hg transformation processes. This genus should be tested for potential bioremediation use in further research.

Mercury characterisation in urban particulate matter

A five-step sequential extraction procedure was proposed in order to assess the distribution of mercury (Hg) forms in urban particulate matter (PM): exchangeable, HCl-soluble, organic-bound, elemental and other slightly soluble Hg species, mercury(II) sulphide (HgS), and residual Hg. This process was applied to the analysis of urban dust samples collected at locations in Prague (Czech Republic) with high traffic density. In addition to sequential extractions, thermal desorption analysis was performed. The differences in Hg concentrations between untreated and thermally treated samples were indicated as the thermally releasable amount of Hg. For the study of PM-adsorbing capacity, Hg vapours were passed through the samples as long as the enrichment of materials was observed. The retained elemental Hg was readily released by thermal desorption. All Hg analyses were based on the highly sensitive pyrolysis technique of atomic absorption spectrometry using the mercury analyser AMA-254.

Macro- and microelements in soil profile of the moss-covered area in James Ross Island, Antarctica.

The study of Antarctic ecosystem provides a valuable insight into the nature development on the Earth. Biocenosis formation and colonization of land by organisms are noticeable especially in newly-deglaciated areas. In this research, soil profile development in the coastal zone of James Ross Island was investigated. The main objective was the characterisation of soil horizons. The contents of As, Ca, Cd, Co, Cr,Cu, Fe, K, Mg, Mn, Ni, P, Se and Zn were measured using ICP-MS technique. Soil parameters like organic carbon content, pH and content of sub-63 micro_m fraction were also determined. Based on the results obtained, the mineral-depleted and mineral-enriched layers in the soil profile were distinguished. With increasing depth, the shallow soil profile consisted mainly of weathered regolith. Apparently, the basic processes which are prerequisite for the development of soil ecosystem in the studied area were confirmed.

Mercury species in formerly contaminated soils and released soil gases

Total mercury (T-Hg), elemental mercury (Hg0), methylmercury (MeHg+), phenylmercury (PhHg+), and gaseous elemental mercury (GEM) species were determined in soils formerly contaminated by different processes from two sites in the Czech Republic. Analytical methods involved atomic absorption spectrometry (AAS) using a single-purpose Advanced Mercury Analyser AMA-254 and radiochemical neutron activation analysis (RNAA) for T-Hg determination, a thermal desorption method was used for Hg0 determination, gas chromatography coupled with atomic fluorescence spectrometry (GC-AFS) was employed for assay of MeHg+ and PhHg+, while GEM measurement was carried out using a portable Zeeman-AAS device Lumex RA-915+. The first sampling site was in the surroundings of a former PhHgCl-based fungicide processing plant next to Příbram (central Bohemia). Although the use of Hg-based fungicides as seed mordant have been banned, and their production stopped at the end of 1980s, highly elevated Hg contents in soil are still observed in the vicinity of the former plant, reaching T-Hg values >13mgkg-1. The second sampling site was an abandoned mining area named Jedová hora Hill near Hořovice (central Bohemia), where cinnabar (HgS) was occasionally mined as by-product of Fe ores hematite and siderite. Mining activities have been stopped here in 1857. Very high contents of T-Hg are still found at this site, up to 144mgkg-1. In most cases we found a statistically significant correlation between T-Hg and Hg0 values regardless of the pollution source. On the contrary, insignificant correlation was observed neither between T-Hg and GEM values, nor between GEM and Hg0. Concentrations of the investigated organomercury species were above a limit of detection (LOD) only in the most contaminated samples, where their levels were about two to three orders of magnitude lower compared to those of T-Hg.

Mercury associated with size-fractionated urban particulate matter: three years of sampling in Prague, Czech Republic

An analysis of suspended particulate matter, with an emphasis on the Hg chemical forms, is presented. Dust samples originating from an area highly affected by traffic pollution in the city of Prague (Czech Republic) were sampled over a period of three years from air-conditioner filters and fractioned by size. The samples were morphologically characterised by scanning electron microscopy. The main method used for the analysis of constituent mercury compounds was sequential extraction by leaching solutions in combination with thermal desorption. The total mercury content ranged from 0.37 mg kg−1 to 0.82 mg kg−1. It emerged that the mercury was distributed in a wide spectrum of forms, and various trends in the distribution of these forms among the different size classes were observed. The fraction leached by nitric acid (consisting of elemental and complex-bound mercury) was the main constituent of total mercury. The highest content of this fraction was observed in the finest particle size class. The heterogeneity of morphology of the material increased with the size fraction.

Nitrate and ammonium ions contents in field minibioreactors with Antarctic freshwater autotrophs

The content of nitrate and ammonium ions in aquatic environment is an important factor in the development of microorganisms colonies especially in low-nutrient environment. In this study, field experiments using small-volume minibioreactors were performed directly on the James Ross Island in Antarctica in order to describe changes in nitrate and ammonium ions contents in the Antarctic environment The ion concentrations in minibioreactors with local freshwater autotrophs was monitored for increased eutro- phication conditions. The content of nitrogen forms was determined in water samples taken from the minibioreactors regularly. Samples were taken to the laboratory of the Johann Gregor Mendel station where nitrogen content was evaluated using ion-selective electrodes. Furthermore, the freshwater autotrophs was subjected to basic taxonomic study. Closed system of the minibioreactors allowed the monitoring of nitrogen speciation changes which take place in the environment. These changes can be attributed to both the biological activity of microorganisms and external conditions. Increased eutrophication of water did not induce a rapid development of the freshwater autotrophs.