Rostislav Červenka

Association of minor and trace elements with mineralogical constituents of urinary stones: A hard nut to crack in existing studies of urolithiasis

The role of metals in urinary stone formation has already been studied in several publications. Moreover, urinary calculi can also be used for assessing exposure of humans to minor and trace elements in addition to other biological matrices, for example, blood, urine, or hair. However, using urinary calculi for biomonitoring of trace elements is limited by the association of elements with certain types of minerals. In this work, 614 samples of urinary calculi were subjected to mineralogical and elemental analysis. Inductively coupled plasma mass spectrometry and thermo-oxidation cold vapor atomic absorption spectrometry were used for the determination of major, minor, and trace elements. Infrared spectroscopy was used for mineralogical analysis, and additionally, it was also employed in the calculation of mineralogical composition, based on quantification of major elements and stoichiometry. Results demonstrate the applicability of such an approach in investigating associations of minor and trace elements with mineralogical constituents of stones, especially in low concentrations, where traditional methods of mineralogical analysis are not capable of quantifying mineral content reliably. The main result of this study is the confirmation of association of several elements with struvite (K, Rb) and with calcium phosphate minerals, here calculated as hydroxylapatite (Na, Zn, Sr, Ba, Pb). Phosphates were proved as the most important metal-bearing minerals in urinary calculi. Moreover, a significantly different content was also observed for Fe, Zr, Mo, Cu, Cd, Se, Sn, and Hg in investigated groups of minerals. Examination of such associations is essential, and critical analysis of mineral constituents should precede any comparison of element content among various groups of samples.

The relationship between the mercury concentration in fish muscles and scales/fins and its significance

AbstractThe determination of mercury in fish typically involves analysis of muscles. For predicting the concentration of mercury in fish muscle on the basis of the analysis of fish scales or fins, the relationship between total mercury concentrations in fish muscles and in fish scales and fins was studied. Mercury content in fish muscles, scales and fins was determined by atomic absorption spectrometry with thermal decomposition of the sample in a flow of oxygen. A number of scale treatments were applied in order to remove impurities and to enhance the prediction quality. For scale treatment, 40 min of washing with DI water in an ultrasonic bath is recommended. A coefficient of determination r2= 0.93 for the relationship between Hg concentrations in muscles and scales was achieved for 40 fish among the different fish species tested (European bream, perch, roach) from the Hamry Reservoir, Czech Republic. With respect to fin sampling, the coefficient of determination r2 for these fish was 0.86. The analysis of fish scales and caudal fins is a useful screening tool for assessing the relative mercury contamination of monitored fish. The method of sampling scales is not suitable for fish species with small scales such as brown trout.

Urinary calculi — atypical source of information on mercury in human biomonitoring

AbstractChemical analysis of various biological matrices is routinely used for assessment of human exposure to various toxic metals. In this work, 489 samples of urinary calculi originating from almost the whole of The Czech Republic, were collected and subjected to mineralogical and elemental analysis. This study was aimed at mercury, the content of which was determined using thermo-oxidation — cold vapor — atomic absorption spectrometry. The effects of mineralogical composition, sex, age and region were recorded in order to verify the applicability of urinary calculi for biomonitoring. Relationships with other minor and trace elements were also investigated. Association of mercury with whewellite mineral was observed as well as a remarkable relationship with selenium, confirming the role of selenium in mercury excretion. No statistically significant effect was observed on the mercury content in stones with regard to the sex or region. Median values in age groups follow a trend with the maximum median value 0.365 mg kg−1 in the group of 41–50 year old donors, decreasing to 0.060 mg kg−1 for the oldest group (81–92 years). Our results confirm that urinary calculi can be helpful in providing complementary information on human exposure to mercury and its excretion.

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.

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.

Stabilizing Agents for Calibration in the Determination of Mercury Using Solid Sampling Electrothermal Atomic Absorption Spectrometry

Tetramethylene dithiocarbamate (TMDTC), diethyldithiocarbamate (DEDTC), and thiourea were investigated as stabilizing agents for calibration purposes in the determination of mercury using solid sampling electrothermal atomic absorption spectrometry (SS-ETAAS). These agents were used for complexation of mercury in calibration solutions and its thermal stabilization in a solid sampling platform. The calibration solutions had the form of methyl isobutyl ketone (MIBK) extracts or MIBK-methanol solutions with the TMDTC and DEDTC chelates and aqueous solutions with thiourea complexes. The best results were obtained for MIBK-methanol solutions in the presence of 2.5 g L−1 TMDTC. The surface of graphite platforms for solid sampling was modified with palladium or rhenium by using electrodeposition from a drop of solutions. The Re modifier is preferable due to a higher lifetime of platform coating. A new SS-ETAAS procedure using the direct sampling of solid samples into a platform with an Re modified graphite surface and the calibration against MIBK-methanol solutions in the presence of TMDTC is proposed for the determination of mercury content in solid environmental samples, such as soil and plants.