Toxic metals in cyanobacterial mat of Big Lachman Lake, James Ross Island, Antarctica.

The northern part of James Ross Island is the largest deglaciated area in the Antarctic Peninsula region with a unique ecosystem created during the Late Glacial. This research aims to evaluate the degree of contamination of the locality with toxic metals (As, Hg, Cd, and Pb) through bioindicators in the aquatic environment-colonies of cyanobacteria and algae. For this purpose, bottom lake sediments of Big Lachman Lake were studied for contents of Fe, As, Hg, Cd, Pb, Cr, Co, Ni, Cu, and Zn, as well as samples of cyanobacterial mat, in which Fe, As, Hg, Cd, and Pb were determined. Metal contents were determined by means of inductively coupled plasma optical emission spectrometry and atomic absorption spectrometry. The contents of metals in sediments did not differ from the usual values in the area of the Antarctic Peninsula. The bioaccumulation of metals in cyanobacterial mat was evaluated by calculating enrichment factors (the calculation to Fe as a reference element). According to this method, moderate pollution of Big Lachman Lake was confirmed for Hg and Cd.

Current Strategies for Selenium and Iodine Biofortification in Crop Plants.

Selenium and iodine are essential trace elements for both humans and animals. Among other things, they have an essential role in thyroid function and the production of important hormones by the thyroid gland. Unfortunately, in many areas, soils are deficient in selenium and iodine, and their amount is insufficient to produce crops with adequate contents to cover the recommended daily intake; thus, deficiencies have an endemic character. With the introduction of iodized table salt in the food industry, the thyroid status of the population has improved, but several areas remain iodine deficient. Furthermore, due to the strong relationship between iodine and selenium in metabolic processes, selenium deficiency often compromises the desired positive impact of salt iodization efforts. Therefore, a considerable number of studies have looked for alternative methods for the simultaneous supplementation of selenium and iodine in foodstuff. In most cases, the subject of these studies is crops; recently, meat has also been a subject of interest. This paper reviews the most recent strategies in agriculture to fortify selenium and iodine in crop plants, their effect on the quality of the plant species used, and the potential impact of food processing on their stability in fortified crops.

Preconcentration and Separation of Gold Nanoparticles from Environmental Waters Using Extraction Techniques Followed by Spectrometric Quantification.

The quantification of gold nanoparticles (AuNP) in environmental samples at ultratrace concentrations can be accurately performed by sophisticated and pricey analytical methods. This paper aims to challenge the analytical potential and advantages of cheaper and equally reliable alternatives that couple the well-established extraction procedures with common spectrometric methods. We discuss several combinations of techniques that are suitable for separation/preconcentration and quantification of AuNP in complex and challenging aqueous matrices, such as tap, river, lake, brook, mineral, and sea waters, as well as wastewaters. Cloud point extraction (CPE) has been successfully combined with electrothermal atomic absorption spectrometry (ETAAS), inductively coupled plasma mass spectrometry (ICP-MS), chemiluminescence (CL), and total reflection X-ray fluorescence spectrometry (TXRF). The major advantage of this approach is the ability to quantify AuNP of different sizes and coatings in a sample with a volume in the order of milliliters. Small volumes of sample (5 mL), dispersive solvent (50 µL), and extraction agent (70 µL) were reported also for surfactant-assisted dispersive liquid-liquid microextraction (SA-DLLME) coupled with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS). The limits of detection (LOD) achieved using different combinations of methods as well as enrichment factors (EF) varied greatly, being 0.004-200 ng L-1 and 8-250, respectively.

Bioleaching of Manganese Oxides at Different Oxidation States by Filamentous Fungus Aspergillus niger.

This work aimed to examine the bioleaching of manganese oxides at various oxidation states (MnO, MnO·Mn2O3, Mn2O3 and MnO2) by a strain of the filamentous fungus Aspergillus niger, a frequent soil representative. Our results showed that the fungus effectively disintegrated the crystal structure of selected mineral manganese phases. Thereby, during a 31-day static incubation of oxides in the presence of fungus, manganese was bioextracted into the culture medium and, in some cases, transformed into a new biogenic mineral. The latter resulted from the precipitation of extracted manganese with biogenic oxalate. The Mn(II,III)-oxide was the most susceptible to fungal biodeterioration, and up to 26% of the manganese content in oxide was extracted by the fungus into the medium. The detected variabilities in biogenic oxalate and gluconate accumulation in the medium are also discussed regarding the fungal sensitivity to manganese. These suggest an alternative pathway of manganese oxides' biodeterioration via a reductive dissolution. There, the oxalate metabolites are consumed as the reductive agents. Our results highlight the significance of fungal activity in manganese mobilization and transformation. The soil fungi should be considered an important geoactive agent that affects the stability of natural geochemical barriers.

A simple dilute-and-shoot procedure for the determination of platinum in human pleural effusions using HR-CS GF-AAS.

BACKGROUND: High-resolution continuum source AAS is an emerging technique for the determination of trace elements in clinical analysis. We aimed to develop a method for the direct determination of platinum (Pt) in pleural effusions that could deepen the understanding of the dynamics of intrapleural Pt concentration during cytostatic therapy. MATERIALS AND METHODS: Samples were collected by thoracic drainage from five patients with lung cancer undergoing platinum based chemotherapy. A simple dilute-and-shoot method for Pt determination in the pleural effusions was developed. Ashing of the sample in an oxygen flow in a graphite tube allowed for direct analysis without prior mineralization. The trueness of the method was verified using an independent technique (ICP-MS). As platinum derivatives are only active in its free form (not bound to proteins), Pt in samples was further divided into free and protein-bound forms by means of ultrafiltration. RESULTS: Using the proposed method, Pt contents (free and total) were determined in samples collected at different times after the intravenous application of the Pt derivative. The concentration of total Pt reached values of up to 5,000 µg/L and different patterns of its dynamics in intrapleural fluid were observed. CONCLUSIONS: The developed method enables the fast and simple determination of Pt in biological fluids. It may be applied on a large scale to improve the understanding of Pt dynamics during cytostatic therapy, and also to determine the optimal timing of both thoracic drainage and administration of systemic chemotherapy.

Production of Methyl-Iodide in the Environment.

Iodine is an essential micronutrient for most of the living beings, including humans. Besides its indispensable role in animals, it also plays an important role in the environment. It undergoes several chemical and biological transformations resulting in the production of volatile methylated iodides, which play a key role in the iodine's global geochemical cycle. Since it can also mitigate the process of climate change, it is reasonable to study its biogeochemistry. Therefore, the aim of this review is to provide information on its origin, global fluxes and mechanisms of production in the environment.

Different trends of Cr, Fe and Zn contents in hair between obese, overweight and normal-weight men.

OBJECTIVES: Overweight and obesity are risk factors for many diseases, nutrition leading to these phenomena is not only a question of disbalance between energy intake and expenditure, but also the presence of micronutrients. In our study, we focused on measuring residues of chromium, zinc and iron in the hair of men with different BMI. METHODS: Hair samples and anthropometric questionnaires were collected from 45 males. Numbers of subjects and age structure were comparable between the three BMI groups. The determination of metal levels was performed by inductively coupled plasma mass spectrometry after mineralization of the hair. RESULTS: The hair of obese men contained significantly higher chromium (0.096 µg/g vs. 0.045 µg/g, p = 0.0039) and iron (9.42 µg/g vs. 5.84 µg/g, p = 0.0009) concentrations than that of overweight men, but no significant difference between the normal-weight group and the obese group were found. The concentration of zinc was lower in obese subjects compared to overweight subjects (183.5 µg/g vs. 206.2 µg/g, p = 0.038). Also, statistically significant correlations between chromium and iron concentrations in hair and BMI were found (r = 0.307, p = 0.040, r = 0.360, p = 0.015, respectively). According to our results, age did not significantly affect chromium, iron and zinc concentrations in hair. CONCLUSION: Consistent with some published studies, we have found that obese men have higher chromium and iron concentrations and lower zinc concentrations in hair.

Inorganic pollutants in the indoor environment of the Moravian Library: assessment of Cd, Pb, Cu, and Zn in total suspended particles and dust using HR-CS GF-AAS.

In this study, the occurrence of lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) in the environment of the Moravian Library in Brno, the second largest library in Czechia, was in focus. The materials of interest were airborne particles, dust originating from books, and also book pages. Total suspended particles (TSP) were sampled in different areas of the library, including the reading room, the book depository, and an external book warehouse. Samples of dusts were obtained from the book-cleaning system, and, moreover, some pages taken from old books were also analyzed. Samples were microwave-digested and analyzed using graphite furnace high-resolution continuum source AAS (HR-CS GF-AAS). During the analysis, possibilities of the signal intensity modulation of the HR-CS technique were demonstrated and employed in order to determine Zn, an element which is rarely determined by GF-AAS. The median TSP concentrations (in ng/m3) were as follows: Pb, 4.4; Cd, 0.07; Cu, 2.6; and Zn, 20.9. Such concentrations are safely below allowed limits. Contents of Pb determined in dust samples and book pages were slightly higher (up to 707 and 38 mg/kg, respectively) than the usually reported values. However, none of these results indicate a potential risk to library staff or readers.

Determination of cadmium in lichens by solid sampling graphite furnace atomic absorption spectrometry (SS-GF-AAS).

The determination of trace metal contents directly from a solid sample is a trend in modern atomic spectrometry. The aim of this study was to develop an analytical method for the routine determination of Cd in lichens using solid sampling graphite furnace atomic absorption spectrometry (SS-GF-AAS). For the determination of Cd, the temperature program of the graphite furnace was optimized using a mixed matrix modifier (Pd + Mg (NO3)2 + Triton X-100). The limit of detection and the limit of quantification were 0.9 µg/kg and 3 µg/kg, respectively. The analytical method for Cd determination in the plant matrix was verified by the analysis of certified reference materials of lichens, seaweed, and rye grass. The developed procedure was applied to the study of Cd distribution in thalli of Usnea antarctica lichen from James Ross Island, Antarctica. The SS-GF-AAS analytical method is particularly suited for use in environmental studies and plant physiology (the microanalysis of anatomical structures).

The impact of tourism on extremely visited volcanic island: Link between environmental pollution and transportation modes.

The enormous tourism boom raises concern about possible negative environmental impacts worldwide. One of the risks posed by tourism may be heavy metal pollution. On the example of the volcanic island of Santorini, a popular tourist destination, pollution of soils categorized according to the tourism load was monitored. Significant anthropogenic contamination by heavy metals, especially Cu, Cr and Pb, was found out. This contamination may constitute a moderate ecological risk to the island ecosystems. Tourism has been shown to be a significant pollution factor as evidenced by the contaminated soils near the airport. Simultaneously, airport traffic has been proved to be an important emitter of Co, Cr and especially Zn. The comparison with other volcanic islands has shown that on Santorini the content of heavy metals in soils is significantly lower, despite frequently higher tourism intensity. On this basis, it can be concluded that in case of volcanic islands the dominant factor determining the content of heavy metals in the soil is the parent rock. Given high and ever-increasing intensity of tourism on the island, it can be assumed that soil contamination will continue to rise rapidly. Therefore, without proper steps reducing tourism, increase in soil degradation, growing negative impacts on local ecosystems as well as on the quality of produced wine can be expected on Santorini.

Estimation of cadmium load from soybeans and soy-based foods for vegetarians.

Soybeans, as legumes, belong among food items that contribute most to the dietary intake of the heavy metal cadmium (Cd). The consumption of soy-based foods may contribute significantly to Cd intake in vegetarians as probably the most frequent consumers of these foods. In this research, the weekly dietary intake of Cd from soy-based foods was investigated in 119 participants (including vegetarians, vegans, and non-vegetarians) in the Czech Republic by means of a semi-quantitative food frequency questionnaire (SFFQ) with personal assistance and the measurement of body weight. Cd content in soy-based foods available on the market was determined by means of atomic absorption spectrometry after microwave digestion. Tofu, as the most frequently consumed food item in the vegetarian/vegan group, contributed most to the total dietary Cd intake. It contained 7.6 ± 0.1 µg Cd/kg, while the highest Cd content was observed in tempeh (18.1 ± 0.4 µg/kg). The highest mean dietary Cd intake per week from soy-based foods was 0.4 µg/kg b.w. and was found in the vegan group. The consumption of soy-based foods was the lowest in the non-vegetarian group as was the dietary intake of Cd, which was 0.04 µg/kg b.w. per week.

Simultaneous determination of cadmium and iron in different kinds of cereal flakes using high-resolution continuum source atomic absorption spectrometry.

A method for simultaneous determination of cadmium and iron in cereal flakes using high-resolution continuum source graphite furnace atomic absorption spectrometry is presented. Sample digest is introduced into the graphite furnace together with Pd/Mg(NO3)2 modifier. The primary absorption line of cadmium and adjacent secondary line of iron are used for the determination. Atomization is performed as a two-step process in order to meet ideal conditions for both elements. Interference produced by molecular absorption of PO molecular bands is suppressed by correction model using least squares background correction. Using the proposed method, levels of cadmium and iron were determined in different kinds of cereal flakes, where both elements are of great interest. Working range (0.01-2 µg L-1 for Cd and 10-500 µg L-1 for Fe) was suitable for the determination of analytes in samples. The method is fast, robust, and may be routinely used routinely in the analysis of foodstuffs.

Correction to: Model of Mercury Flux Associated with Volcanic Activity.

The original version of this article contained a mistake in Fig. 2. The country names have been missed in the figure legend along with the X-axis. The corrected figure is given below.

Model of Mercury Flux Associated with Volcanic Activity.

Volcanic activity is one of the primary sources of mercury in the earth's ecosystem. In this work, volcanic rocks from four geotectonically distinct localities (the Czech Republic - intraplate, rift-related alkaline basaltic rocks; Iceland - hotspot/rift-related tholeiitic basaltic rocks; Japan - island arc calc-alkaline andesites; and Alaska - continental arc calc-alkaline dacites) were studied. Ultra-trace Hg contents in all samples ranged from 0.3 up to 6 µg/kg. The highest Hg content was determined for volcanic ash from Mount Redoubt (Alaska, USA). In the case of basaltic volcanic rocks, the obtained results are about two orders of magnitude smaller than values formerly assumed for primary mercury contents in basaltic lavas. They are close to predicted Hg contents in the mantle source, i.e. below 0.5 µg/kg. Hg degassing is probably a key process for the resulting Hg contents in material ejected during volcanic eruption, which is previously enriched by Hg in the shallow-crust.

The contents and distributions of cadmium, mercury, and lead in Usnea antarctica lichens from Solorina Valley, James Ross Island (Antarctica).

Lichens are efficient and cost-effective biomonitors of the environment. Their geographic distribution together with their slow growth rate enable investigation of the deposition patterns of various elements and substances. In this research, levels of cadmium, lead, and mercury in Usnea antarctica lichens in the area of James Ross Island, Antarctica, were investigated. The lichens were microwave-digested, and the metals were determined by means of atomic absorption spectrometry with graphite furnace and a direct mercury analyzer. Median total contents of Cd, Hg, and Pb were 0.04, 0.47, and 1.6 mg/kg in whole lichens, respectively. The bottom-up distributions of these metals in the fruticose lichen thalli were investigated, and it was revealed that the accumulation patterns for mercury and lead were opposite to that for cadmium. The probable reason for this phenomenon may lie in the inner structure of thalli. The total contents of metals were comparable with those published for other unpolluted areas of maritime Antarctica. However, this finding was not expected for mercury, since the sampling locality was close to an area with some of the highest mercury contents published for Antarctic lichens. In short, lichens proved their usability as biological monitors, even in harsh conditions. However, the findings emphasize the need to take into account the distributions of elements both in the environment and in the lichen itself.

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 Príbram (central Bohemia). Although the use of Hg-based fungicides as seed mordant have been banned, and their production stopped at the end of 1980's, 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 Horovice (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.

Leaching of mercury from seal carcasses into Antarctic soils.

More than 400 seal mummies and skeletons are now mapped in the northern part of James Ross Island, Antarctica. Decomposing carcasses represent a rare source of both organic matter and associated elements for the soil. Owing to their high trophic position, seals are known to carry a significant mercury body burden. This work focuses on the extent of the mercury input from seal carcasses and shows that such carcasses represent locally significant sources of mercury and methylmercury for the environment. Mercury contents in soil samples from the surrounding areas were determined using a single-purpose AAS mercury analyzer. For the determination of methylmercury, an ultra-sensitive isotopic dilution HPLC-ICP-MS technique was used. In the soils lying directly under seal carcasses, mercury contents were higher, with levels reaching almost 40 µg/kg dry weight of which methylmercury formed up to 2.8 % of the total. The spatial distribution implies rather slow vertical transport to the lower soil layers instead of a horizontal spread. For comparison, the background level of mercury in soils of the investigated area was found to be 8 µg/kg dry weight, with methylmercury accounting for less than 0.1 %. Apart from the direct mercury input, an enhanced level of nutrients in the vicinity of carcasses enables the growth of lichens and mosses with accumulative ability with respect to metals. The enhanced capacity of soil to retain mercury is also anticipated due to the high content of total organic carbon (from 1.6 to 7.5 %). According to the results, seal remains represent a clear source of mercury in the observed area.

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

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.

[Medicine at a polar station in Antarctica]. / Medicína na polární stanici v Antarktide.

The paper describes specific aspects of work of a scientific expedition doctor and the stay and life at a polar research station in Antarctica. Apart from the outline of everyday problems, the first named author also learns about the history of medical practitioners working in Antarctica, writes about the results of the biomedical research activities conducted in the period of 2011-2014 and briefly describes the daily routine at a scientific polar station in Antarctica.

Analysis of mercury and other heavy metals accumulated in lichen Usnea antarctica from James Ross Island, Antarctica.

The study was designed to investigate the content and distribution of selected heavy metals (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Fe, Pb and Zn) in samples of fruticose macrolichen Usnea antarctica from James Ross Island. A special emphasis was devoted to mercury and its species (elemental mercury and methylmercury). It was found that mercury contents were relatively high (up to 2.73 mg kg(-1) dry weight) compared to other parts of the Antarctic Peninsula region, while the concentrations of most other elements were within reported ranges. Mercury contents in lichens originating from the interior were higher than those from the coast, which is probably the result of local microclimate conditions. Similar trends were observed for Hg(0) and MeHg(+), whose contents were up to 0.14 and 0.098 mg kg(-1) dry weight, respectively. While mercury did not show a significant correlation with any other element, the mutual correlation of some litophile elements probably refers to the influence on thalli of resuspended weathered material. The influence of habitat and environmental conditions could play an essential role in the bioaccumulation of contaminants rather than just the simple presence of sources. Thus, the study of the thalli of this species can bring a new perspective on the interpretation of contaminant accumulation in lichens of the polar region.