Proposals of guidance values for surface contamination by antineoplastic drugs based on long term monitoring in Czech and Slovak hospitals and pharmacies.

Introduction: The exposures to hazardous antineoplastic drugs (AD) represent serious risks for health care personnel but the exposure limits are not commonly established because of the no-threshold effects (genotoxic action, carcinogenicity) of many ADs. In this study, we discussed and derived practically applicable technical guidance values (TGV) suitable for management of AD risks. Methods: The long-term monitoring of surface contamination by eight ADs was performed in pharmacies and hospitals in the Czech Republic and Slovak Republic in 2008-2021; in total 2,223 unique samples were collected repeatedly in 48 facilities. AD contamination was studied by LC-MS/MS for cyclophosphamide, ifosfamide, methotrexate, irinotecan, paclitaxel, 5-fluorouracil and gemcitabine and by ICP-MS for total Pt as a marker of platinum-based ADs. Results: The study highlighted importance of exposure biomarkers like 5-fluorouracil and especially carcinogenic and persistent cyclophosphamide, which should be by default included in monitoring along with other ADs. Highly contaminated spots like interiors of laminar biological safety cabinets represent a specific issue, where monitoring of contamination does not bring much added value, and prevention of staff and separated cleaning procedures should be priority. Rooms and surfaces in health care facilities that should be virtually free of ADs (e.g., offices, kitchenettes, daily rooms) were contaminated with lower frequency and concentrations but any contamination in these areas should be carefully examined. Discussion and conclusions: For all other working places, i.e., majority of areas in pharmacies and hospitals, where ADs are being prepared, packaged, stored, transported, or administered to patients, the study proposes a generic TGV of 100 pg/cm2. The analysis of long-term monitoring data of multiple ADs showed that the exceedance of one TGV can serve as an indicator and trigger for improvement of working practices contributing thus to minimizing of unintended exposures and creating a safe work environment.

Occurrence, Source and Dietary Exposure of Toxic and Essential Elements in the Indian Food Basket.

In this study, representative urban and peri-urban Indian food baskets have been studied for the presence of toxic and essential elements. The concentration of target toxic and essential elements was used to estimate dietary intakes (EDIs) and health risks. Across all food matrices, toxic elements like Cd and Pb were dominant. The highest concentrations of the target elements were found in vegetables, with Cd, Pb, and Ni being beyond permissible limits of the Food and Agriculture Organization of the United Nations and the World Health organization (0.05 mg/kg, 0.1 mg/kg, and 1.5 mg/kg, respectively) in okra, spinach, and cauliflower. The sum of concentrations of the toxic elements (As, Ni, Hg, Cr, Cd, Pb) in vegetables had a range of 0.54-12.08 mg/kg, the highest sum was found in spinach (median 12.08 mg/kg), followed by okra (median 1.68 mg/kg). The EDI was observed for vegetables with a contribution as high as 92% for Cd. Dairy products were found with the highest loading for Ni with a dietary intake of 3.1 mg/kg/day for adults and twice as much for children. Carcinogenic risk for Ni was the highest and found above the threshold for all food categories, as was the case with As. Cumulative carcinogenic and non-carcinogenic risks were mostly contributed by milk and vegetables, in particular, spinach.

Effect of titanium nanostructured surface on fibroblast behavior.

As the consumption of implants increases, so do the requirements for individual types of implants, for example, improved biocompatibility or longevity. Therefore, the nano-modification of the titanium surface is often chosen. The aim was to characterize the modified surface with a focus on medical applications. The titanium surface was modified by the anodic oxidation method to form nanotubes. Subsequently, the material was characterized and analyzed for medical applications-surface morphology, surface wettability, chemical composition, and release of ions into biological fluids. A human gingival fibroblasts (HGFb) cell line was used in the viability study. A homogeneous layer of nanotubes of defined dimensions was formed on the titanium surface, ensuring the material's biocompatibility-the preparation conditions influence the resulting properties of the nanostructured surface. Nanostructured titanium exhibited more suitable characteristics (e.g., wettability, roughness, ion release) for biological applications than compared to pure titanium. It was possible to understand the behavior of the modified layer on the titanium surface and its effect on cell behavior. Another contribution of this work is the combination of material characterization (ion release) with the study of cytocompatibility (direct contact of cells with metals).

Metals and Trace Elements in Calcified Valves in Patients with Acquired Severe Aortic Valve Stenosis: Is There a Connection with the Degeneration Process?

BACKGROUND: Acquired calcified aortic valve stenosis is the most common valve disease in adulthood. In the etiopathogenesis of this complex pathology, the importance of inflammation is mentioned, in which non-infectious influences represented by the biological effects of metal pollutants may participate. The main goal of the study was to determine the concentration of 21 metals and trace elements-aluminium (Al), barium (Ba), cadmium (Cd), calcium (Ca), chrome (Cr), cobalt (Co), copper (Cu), gold (Au), lead (Pb), magnesium (Mg), mercury (Hg), molybdenum (Mo), nickel (Ni), phosphorus (P), selenium (Se), strontium (Sr), sulfur (S), tin (Sn), titanium (Ti), vanadium (V) and zinc (Zn)-in the tissue of calcified aortic valves and to compare them with the concentrations of the same elements in the tissue of healthy aortic valves in the control group. MATERIAL AND METHODS: The study group consisted of 49 patients (25 men, mean age: 74) with acquired, severe, calcified aortic valve stenosis with indicated heart surgery. The control group included 34 deceased (20 men, median age: 53) with no evidence of heart disease. Calcified valves were explanted during cardiac surgery and deep frozen. Similarly, the valves of the control group were removed. All valves were lyophilized and analyzed by inductively coupled plasma mass spectrometry. The concentrations of selected elements were compared by means of standard statistical methods. RESULTS: Calcified aortic valves contained significantly higher (p < 0.05) concentrations of Ba, Ca, Co, Cr, Mg, P, Pb, Se, Sn, Sr and Zn and-in contrast-lower concentrations of Cd, Cu, Mo, S and V than valves of the control group. Significant positive correlations of concentrations between the pairs Ca-P, Cu-S and Se-S and strong negative correlations between the elements Mg-Se, P-S and Ca-S were found in the affected valves. CONCLUSION: Aortic valve calcification is associated with increased tissue accumulation of the majority of the analyzed elements, including metal pollutants. Some exposure factors may increase their accumulation in the valve tissue. A relationship between exposure to environmental burden and the aortic valve calcification process cannot be ruled out. Advances in histochemical and imaging techniques allowing imaging of metal pollutants directly in valve tissue may represent an important future perspective.

Levels and risks of surface contamination by thirteen antineoplastic drugs in the Czech and Slovak hospitals and pharmacies.

The consumption of hazardous antineoplastic drugs (ADs) used in anticancer chemotherapies is steadily increasing representing thus risks to both human health and the environment. Hospitals may serve as a contamination source, and pharmacists preparing the antineoplastic drugs (ADs) as well as nurses administering chemotherapy and caring for oncology patients are among the healthcare professionals being highly exposed. Here, we present the results of systematic monitoring (2018-2020) of surface contamination by 13 ADs in the pharmacies and hospitals in the Czech Republic (CZ; large-scale monitoring, 20 workplaces) and Slovak Republic (SK; pilot study at 4 workplaces). The study evaluated contamination by three commonly monitored ADs, i.e., 5-fluorouracil (FU), cyclophosphamide (CP), and platinum (total Pt representing cis-, carbo-, and oxaliplatin) together with ten less explored ADs, i.e., gemcitabine (GEM), ifosfamide (IF), paclitaxel (PX), irinotecan (IRI), docetaxel (DOC), methotrexate (MET), etoposide (ETOP), capecitabine (CAP), imatinib (IMAT), and doxorubicin (DOX). Floors and desktop surfaces in hospitals (chemotherapy application rooms, nurse working areas) were found to be more contaminated, namely with CP and Pt, in both countries when compared to pharmacies. Comparison between the countries showed that hospital surfaces in SK are generally more contaminated (e.g., CP median was 20 times higher in SK), while some pharmacy areas in the CZ were more contamined in comparison with SK. The newly studied ADs were detected at lower concentrations in comparison to FU, CP, and Pt, but some markers (GEM, IF, PX, and IRI) were frequently observed, and adding these compounds to routine monitoring is recommended.

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.

Raman Microspectroscopic Analysis of Selenium Bioaccumulation by Green Alga Chlorella vulgaris.

Selenium (Se) is an element with many commercial applications as well as an essential micronutrient. Dietary Se has antioxidant properties and it is known to play a role in cancer prevention. However, the general population often suffers from Se deficiency. Green algae, such as Chlorella vulgaris, cultivated in Se-enriched environment may be used as a food supplement to provide adequate levels of Se. We used Raman microspectroscopy (RS) for fast, reliable, and non-destructive measurement of Se concentration in living algal cells. We employed inductively coupled plasma-mass spectrometry as a reference method to RS and we found a substantial correlation between the Raman signal intensity at 252 cm-1 and total Se concentration in the studied cells. We used RS to assess the uptake of Se by living and inactivated algae and demonstrated the necessity of active cellular transport for Se accumulation. Additionally, we observed the intracellular Se being transformed into an insoluble elemental form, which we further supported by the energy-dispersive X-ray spectroscopy imaging.

The efficiency of antineoplastic drug contamination removal by widely used disinfectants-laboratory and hospital studies.

OBJECTIVE: Antineoplastic drugs (ADs) pose risks to healthcare staff. Surface disinfectants are used in hospitals to prevent microbial contamination but the efficiency of disinfectants to degrade ADs is not known. We studied nine disinfectants on ten ADs in the standardized laboratory and realistic in situ hospital conditions. METHODS: A survey in 43 hospitals prioritized nine most commonly used disinfections based on different ingredients. These were tested on inert stainless steel and in situ on contaminated hospital flooring. The effects against ten ADs were studied by LC-MS/MS (Cyclophosphamide CP; Ifosfamide IF; Capecitabine CAP; Sunitinib SUN; Methotrexate MET; Doxorubicin DOX; Irinotecan IRI; Paclitaxel PX; 5-Fluorouracil FU) and ICP-MS (Pt as a marker of platinum-based ADs). RESULTS: Monitoring of the floor contamination in 26 hospitals showed that the most contaminated are the outpatient clinics that suffer from a large turnover of staff and patients and have limited preventive measures. The most frequent ADs were Pt, PX, FU and CP with maxima exceeding the recommended 1 ng/cm2 limit by up to 140 times. IRI, FU, MET, DOX and SUN were efficiently removed by hydrolysis in clean water and present thus lower occupational risk. Disinfectants based on hydrogen peroxide were efficient against PX and FU (> 70% degradation) but less against other ADs, such as carcinogenic CP or IF, IRI and CAP. The most efficient were the active chlorine and peracetic acid-based products, which however release irritating toxic vapors. The innovative in situ testing of ADs previously accumulated in hospital flooring showed highly problematic removal of carcinogenic CP and showed that alcohol-based disinfectants may mobilize persistent ADs contamination from deeper floor layers. CONCLUSION: Agents based on hydrogen peroxide, peracetic acid, quaternary ammonium salts, glutaraldehyde, glucoprotamine or detergents can be recommended for daily use for both disinfection and AD decontamination. However, they have variable efficiencies and should be supplemented by periodic use of strong chlorine-based disinfectants efficient also against the carcinogenic and persistent CP.

Nitrated monoaromatic hydrocarbons (nitrophenols, nitrocatechols, nitrosalicylic acids) in ambient air: levels, mass size distributions and inhalation bioaccessibility.

Nitrated monoaromatic hydrocarbons (NMAHs) are ubiquitous in the environment and an important part of atmospheric humic-like substances (HULIS) and brown carbon. They are ecotoxic and with underresearched toxic potential for humans. NMAHs were determined in size-segregated ambient particulate matter collected at two urban sites in central Europe, Ostrava and Kladno, Czech Republic. The average sums of 12 NMAHs (Σ12NMAH) measured in winter PM10 samples from Ostrava and Kladno were 102 and 93 ng m-3, respectively, and 8.8 ng m-3 in summer PM10 samples from Ostrava. The concentrations in winter corresponded to 6.3-7.3% and 2.6-3.1% of HULIS-C and water-soluble organic carbon (WSOC), respectively. Nitrocatechols represented 67-93%, 61-73% and 28-96% of NMAHs in PM10 samples collected in winter and summer at Ostrava and in winter at Kladno, respectively. The mass size distribution of the targeted substance classes peaked in the submicrometre size fractions (PM1), often in the PM0.5 size fraction especially in summer. The bioaccessible fraction of NMAHs was determined by leaching PM3 samples in two simulated lung fluids, Gamble's solution and artificial lysosomal fluid (ALF). More than half of NMAH mass is found bioaccessible, almost complete for nitrosalicylic acids. The bioaccessible fraction was generally higher when using ALF (mimics the chemical environment created by macrophage activity, pH 4.5) than Gamble's solution (pH 7.4). Bioaccessibility may be negligible for lipophilic substances (i.e. log KOW > 4.5).

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.

Selenium Incorporation to Amino Acids in Chlorella Cultures Grown in Phototrophic and Heterotrophic Regimes.

Microalgae accumulate bioavailable selenium-containing amino acids (Se-AAs), and these are useful as a food supplement. While this accumulation has been studied in phototrophic algal cultures, little data exists for heterotrophic cultures. We have determined the Se-AAs content, selenium/sulfur (Se/S) substitution rates, and overall Se accumulation balance in photo- and heterotrophic Chlorella cultures. Laboratory trials revealed that heterotrophic cultures tolerate Se doses ∼8-fold higher compared to phototrophic cultures, resulting in a ∼2-3-fold higher Se-AAs content. In large-scale experiments, both cultivation regimes provided comparable Se-AAs content. Outdoor phototrophic cultures accumulated up to 400 µg g-1 of total Se-AAs and exhibited a high level of Se/S substitution (5-10%) with 30-60% organic/total Se embedded in the biomass. A slightly higher content of Se-AAs and ratio of Se/S substitution was obtained for a heterotrophic culture in pilot-scale fermentors. The data presented here shows that heterotrophic Chlorella cultures provide an alternative for Se-enriched biomass production and provides information on Se-AAs content and speciation in different cultivation regimes.

Oxygenated and Nitrated Polycyclic Aromatic Hydrocarbons in Ambient Air-Levels, Phase Partitioning, Mass Size Distributions, and Inhalation Bioaccessibility.

Among the nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are some of the most hazardous substances to public health, mainly because of their carcinogenicity and oxidative potential. Despite these concerns, the concentrations and fate of NPAHs and OPAHs in the atmospheric environment are largely unknown. Ambient air concentrations of 18 NPAHs, 5 quinones, and 5 other OPAHs were determined at two urban and one regional background sites in central Europe. At one of the urban sites, the total (gas and particulate) concentrations of Σ10OPAHs were 10.0 ± 9.2 ng/m3 in winter and 3.5 ± 1.6 ng/m3 in summer. The gradient to the regional background site exceeded 1 order of magnitude. Σ18NPAH concentrations were typically 1 order of magnitude lower than OPAHs. Among OPAHs, 9-fluorenone and (9,10)-anthraquinone were the most abundant species, accompanied by benzanthrone in winter. (9,10)-Anthraquinone represented two-thirds of quinones. We found that a large fraction of the target substance particulate mass was carried by submicrometer particles. The derived inhalation bioaccessibility in the PM10 size fraction is found to be ≈5% of the total ambient concentration of OPAHs and up to ≈2% for NPAHs. For 9-fluorenone and (9,10)-anthraquinone, up to 86 and 18%, respectively, were found at the rural site. Our results indicate that water solubility could function as a limiting factor for bioaccessibility of inhaled particulate NPAHs and OPAHs, without considerable effect of surfactant lipids and proteins in the lung lining fluid.

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.

Assessment of geogenic input into Bilina stream sediments (Czech Republic).

Over the past 100 years, the area along the River Bílina has been influenced by open-cast brown-coal mining, coal processing, petroleum refineries, and chemical plants. As a result, the extensive industrial activity has changed the overall character as well as the morphology of the landscape. A survey was underway to investigate the occurrence and distribution of various elements in the sediments of the River Bílina-a tributary of the River Elbe, a watercourse running through the Czech Republic and Germany-in order to discern the natural background from anthropogenic pollution. The study evaluated the content of selected elements (As, Zn, Pb, Cr, Ni, V, and Cu) in stream sediments of the River Bílina. Samples were taken at 20 sampling sites throughout the 82-km-long watercourse. For all the samples, the content of the elements was determined using ICP-MS after each of the sample was digested using HF and HNO3. The results of analyses of elemental composition of stream sediments were compared with those found through such analyses made within the surrounding geological units-more specifically, Proterozoic crystalline, Tertiary volcanic, Quaternary loess, Neogene sediments, and Neogene coal. All the samples of the stream sediments examined revealed increased amounts of As, V, Ni, Cr, and Pb. Using the enrichment factor established on the basis of the regional geological background values proved that elevated levels of elements in stream sediments are not always the result of industrial contamination.

In vitro bioaccessibility of selenoamino acids from selenium (Se)-enriched Chlorella vulgaris biomass in comparison to selenized yeast; a Se-enriched food supplement; and Se-rich foods.

Selenium (Se) is an indispensable microelement in our diet and health issues resulting from deficiencies are well documented. Se-containing food supplements are available on the market including Se-enriched Chlorella vulgaris (Se-Chlorella) which accumulates Se in the form of Se-amino acids (Se-AAs). Despite its popular uses, data about the bioaccessibility of Se-AAs from Se-Chlorella are completely missing. In the present study, gastrointestinal digestion times were optimized and the in vitro bioaccessibility of Se-AAs in Se-Chlorella, Se-yeast, a commercially available Se-enriched food supplement (Se-supplement) and Se rich foods (Se-foods) were compared. Higher bioaccessibility was found in Se-Chlorella (∼49%) as compared to Se-yeast (∼21%), Se-supplement (∼32%) and Se-foods. The methods used in production of Se-Chlorella biomass were also investigated. We found that disintegration increased bioaccessibility whereas the drying process had no effect. Similarly, temperature treatment by microwave oven also increased bioaccessibility whereas boiling water did not.

Concentrations of Thirteen Trace Metals in Scales of Three Nototheniid Fishes from Antarctica (James Ross Island, Antarctic Peninsula).

In this study, we assessed concentrations of 13 trace metals in the scales of Notothenia coriiceps, Trematomus bernacchii and Gobionotothen gibberifrons caught off the coast of James Ross Island (Antarctic Peninsula). Overall, our results for scales broadly match those of previous studies using different fish and different organs, with most metals found at trace levels and manganese, aluminium, iron and zinc occurring at high levels in all species. This suggests that scales can serve as a useful, non-invasive bioindicator of long-term contamination in Antarctic fishes. High accumulation of manganese, aluminium, iron and zinc is largely due to high levels in sediments associated with nearby active volcanic sites. Manganese, vanadium and aluminium showed significant positive bioaccumulation in T. bernacchii (along with non-significant positive accumulation of iron, zinc, cobalt and chromium), most likely due to greater dietary specialisation on sediment feeding benthic prey and higher trophic species. Levels of significance in bioaccumulation regressions were strongly affected by large-scale variation in the data, driven largely by individual differences in diet and/or changes in habitat use and sex differences associated with life stage and reproductive status. Increased levels of both airborne deposition and precipitation and meltwater runoff associated with climate change may be further adding to the already high levels of manganese, aluminium, iron and zinc in Antarctic Peninsula sediments. Further long-term studies are encouraged to elucidate mechanisms of uptake (especially for aluminium and iron) and possible intra- and interspecific impacts of climate change on the delicate Antarctic food web.

Hypersensitivity to material and environmental burden as a possible cause of late complications of cardiac implantable electronic devices.

Aims: To evaluate whether patients with late complications of pacemakers or implantable cardioverter-defibrillators have hypersensitivity reactions to some of the materials used in generators or in electrodes, or to environmental metal burden. Methods and results: The cohort consisted of 20 men and 4 women (mean age: 62.3 ± 17.2 years) who had a history of late complications of implanted devices. The control group involved 25 men and 8 women (mean age: 64.6 ± 14.0 years) who had comparable devices, but no history of late complications. Lymphocyte transformation test was used to evaluate hypersensitivity to eight metal pollutants (antimony, manganese, mercury, molybdenum, nickel, platinum, tin, and titanium) selected by results of questionnaires on environmental burden, and by material analysis of generators and electrode surfaces. Exposures to metal pollutants were approximately the same in patients and in controls. Titanium alloy used in generators contained at least 99.32% of titanium and trace levels of other metals; higher levels of tin and platinum were detected in electrode surfaces. Hypersensitivity reactions to mercury and tin were significantly more frequent in patients than in controls (patients and controls: mercury: 68.2 and 31.1%, respectively; P = 0.022; tin: 25.0 and 3.2%, respectively; P = 0.035). In contrast, hypersensitivity to manganese was significantly more frequent in controls than in patients (patients and controls: 13.6 and 50.0%, respectively; P = 0.008). Conclusion: Our findings suggest a possible relation between hypersensitivity to metals used in implantable devices or to environmental metal burden and the occurrence of their late complications.

Thin-layer chromatography combined with diode laser thermal vaporization inductively coupled plasma mass spectrometry for the determination of selenomethionine and selenocysteine in algae and yeast.

In this work we present a simple and cost-effective approach for the determination of selenium species in algae and yeast biomass, based on a combination of thin-layer chromatography (TLC) with diode laser thermal vaporization inductively coupled plasma mass spectrometry (DLTV ICP MS). Extraction of freeze-dried biomass was performed in 4M methanesulphonic acid and the selenium species were vaporized from cellulose TLC plates employing a continuous-wave infrared diode laser with power up to 4 W using a simple laboratory-built apparatus. Selenomethionine and selenocysteine were quantified with limits of detection 3 µg L-1 in a Se-enriched microalgae Chlorella vulgaris and yeast certified reference material SELM-1. Results delivered by TLC-DLTV ICP MS were consistent with those obtained by a routine coupling of high-performance liquid chromatography (HPLC) to ICP MS. In addition, the TLC approach is capable of analyzing extract containing even undiluted crude hydrolysates that could damage HPLC columns.

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.