Jan Kuta

Spatial patterns and temporal changes of heavy metal distributions in river sediments in a region with multiple pollution sources

PurposeThe main purpose of this study was to evaluate temporal and regional variability of contamination by heavy metals (HMs) in river sediments using their enrichment factors (EFs) and benchmarking according to sediment quality guidelines (SQGs). The Zlin region in the Czech Republic (Morava and Drevnice River basins) represents a model area where several regionally specific ecological risk assessment studies have recently been conducted with a focus on organic pollution, eco-toxicity, geological, and geochemical characteristics.Materials and methodsFour consecutive sediment sampling campaigns were undertaken in spring and autumn 2005–2006. Aqua-regia leachable content of Cd, Co, Cr, Cu, Ni, Pb, Sb, V, and Zn in surface sediments from 14 sites was analyzed using ICP-MS, and Hg content was analyzed using AMA-254 analyzer. EFs were calculated to identify the human impact on pollution in the area. Comparisons to SGQs were conducted to identify the areas and HMs of greatest risk.Results and discussionCalculation of EFs contributed to the effective clustering of HMs. Median EFs of Co, Ni, and V ranged from 0.9 to 1.4 at all sites indicating concentrations very close to natural geological background levels. There was greater enrichment at locally polluted sites, the highest in the cases of Cd, Sb, Hg, and Cr. Widespread influence of diffuse HM sources (traffic, agriculture, and urban wastes) was apparent from elevated concentrations of Pb, Cu, and Zn at all sites. EF values also helped to identify the greatest temporal changes and shifts in HMs contamination between adjacent sites caused by 50-year recurrence interval floods in early spring 2006. The impact was most apparent in downstream sites; namely directly below the confluence of the two major rivers.ConclusionsThe overall contamination of HMs in the region was classified as low-to-moderate with significantly contaminated sub-areas. The study showed relatively stable spatial distributions of HMs, indicating potential sources of pollution. Cu was identified as the HM of greatest risk. The study emphasizes the necessity of considering both environmental circumstances and background HM occurrence to prevent misinterpretation of the pollution situation. The use of EFs which include grain size proxy normalization and HM background levels, along with the comparison of the detected concentrations to SQGs, proved an efficient way to identify hazardous contamination from anthropogenic sources.

Effects of combined composting and vermicomposting of waste sludge on arsenic fate and bioavailability

Composting and vermicomposting are traditional processes for the treatment of sludge. During these processes, the humification of organic matter has a significant effect on the physicochemical form and distribution of heavy metals. In this study, industrial sludge (groundwater treatment waste) contaminated by arsenic (396 ± 1 mg kg(-1)) was used. Such sludge poses a significant challenge with respect to effective treatment. Composting, vermicomposting (with Eisenia fetida), and the combined approach of composting and vermicomposting were performed to determine the evolution of arsenic speciation, mobility and bioavailability. The composting/vermicomposting was done with sludge, horse manure, and grass in the ratios of 3:6:1. A solution of 0.1M NH4COOCH3 was used as a single extraction solvent for determination of the mobile arsenic pool and targeted arsenic species (As(III), As(V), monomethylarsenic acid - MMA(V), dimethylarsenic acid - DMA(V)). The analysis of arsenic in the extracts was carried out by means of HPLC-ICP-MS spectrometry. In addition, the earthworm species E. fetida was used for bioaccumulation tests that followed the compost and vermicompost processes. The obtained results indicate a reduction in arsenic mobility and bioavailability in all matured composts and vermicomposts. The combined process exhibited a greater effect than compost or vermicompost alone.

Evaluation of the Efficacy of Additional Measures Introduced for the Protection of Healthcare Personnel Handling Antineoplastic Drugs

OBJECTIVES Due to their adverse effects, antineoplastic drugs are considered as a potential health risk to healthcare personnel. The objective of the study was to compare the surface contamination level of the conventional preparation room and outpatient clinic before and after the implementation of a set of additional protective measures. METHODS The measures were targeted at eliminating potential sources of environmental contamination, and modification of the cleaning procedure. The measures introduced into the preparation room consisted of (i) the introduction of manual cleaning of drug vials before they enter the preparation room, (ii) the modification of the routine cleaning procedure performed at the end of each working day (i.e. shifting the cleaning of the isolators as the most contaminated objects from the beginning of the cleaning process to the end), and (iii) the introduction of regular cleaning of the work table every 2 h. The measures introduced into the outpatient clinic consisted of (i) replacement of the standard infusion sets with multichannel sets for safe drug administration, (ii) the introduction of self-cleaning seats to the patient lavatories supporting hygienic and contamination-free seated urination, and (iii) replacement of standard infusion stands with wall-mounted stands, supporting the regular and proper cleaning of the floor beneath. To determine the surface contamination level with antineoplastic drugs, cyclophosphamide and platinum were determined in wipe samples with high performance liquid chromatography with tandem mass spectrometry and inductively coupled plasma mass spectrometry. RESULTS In the preparation room, depending on the sampling spot and analyte, median concentrations ranged from 5 to 267 pg cm(-2) and from 2 to 368 pg cm(-2) before and after implementation of the measures, respectively. In the outpatient clinic, median concentrations ranged from 5 to 5310 pg cm(-2) and from <0.2 to 574 pg cm(-2) before and after implementation of the measures, respectively. Depending on the sampling spot, median contamination of the outpatient clinic with cyclophosphamide and platinum was reduced by 57-99% and 61-98%, respectively. CONCLUSIONS The measures implemented in the outpatient clinic were shown to reduce workplace contamination effectively. Therefore, they can be recommended also for other workplaces where antineoplastic drugs are administered. In contrast, measures implemented in the preparation room, where relatively strict regulations had already been adopted before the study, were less effective. To decrease the actual contamination of the preparation room, other protective measures (e.g. closed-system transfer devices) should be considered.

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.

Association of Surface Contamination by Antineoplastic Drugs With Different Working Conditions in Hospital Pharmacies

ABSTRACT This study investigates the surface contamination levels of cyclophosphamide and platinum (a marker of platinum-containing drugs) in storage and preparation areas of hospital pharmacies and their relationship to working conditions surveyed by questionnaire. In total, 259 wipe samples were collected in 13 hospital pharmacies over 4 sampling campaigns. After sample extraction with acetate buffer, cyclophosphamide and platinum were determined using high-performance liquid chromatography–tandem mass spectroscopy (HPLC-MS/MS) and inductively coupled plasma mass spectrometry (ICP-MS). Depending on the sampling spot and campaign, median concentrations ranged from <2 to 61 pg/cm2 and from <0.2 to 6.9 pg/cm2 for cyclophosphamide and platinum, respectively. Statistical evaluation of monitoring data revealed that the contamination level was significantly influenced by laboratory throughput (expressed as number of chemotherapies prepared per week), personnel expertise (ie, participation of pharmacists with academic education in drug admixture activities), and surface material.

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.

Developmental neurotoxicants in human milk: Comparison of levels and intakes in three European countries

Developmental neurotoxicants (DNTs), such as methylmercury (MeHg), polychlorinated biphenyls (PCBs) and selected organochlorine pesticides (OCPs), have gained increasing interest recently due to their possible relation to developmental disorders in children, which are increasing worldwide. We analyzed levels of 14 developmental neurotoxicants in human milk samples from Slovakia (n=37), the Netherlands (n=120) and Norway (n=388). Positive identification for most target analytes was >95% in all samples. In all three countries MeHg was measured for the first time in mother milk. The highest MeHg levels were observed in Norway (39pgg-1 ww) with the highest fish consumption. Levels of indicator PCBs (iPCBs, sum of PCB 28, 52, 101, 138, 153 and 180), HCB and DDE+DDT were 2-4 times higher in Slovakia compared to the Netherlands or Norway. The levels of MeHg and organochlorine compounds were used for calculations of weekly or daily intakes (top-down approach) by means of pharmacokinetic modeling. The intakes ranged from 0.014 to 0.142μgkgbw-1week-1 for MeHg and from 0.043 to 17.4ngkgbw-1day-1 for organochlorine compounds in all three countries. Intakes of iPCBs exceeded a tolerable daily intake of 10ngkgbw-1day-1 in 16% of the Slovak participants. The top-down estimates were compared with bottom-up intakes based on national dietary estimates and the results showed good consistency between both approaches, with the bottom-up intakes exceeding the top-down by a factor of maximum 3.8 for iPCBs in the Netherlands and 3.9 for HCB in Slovakia. This confirms that food consumption in all three countries represents the dominant pathway of exposure to these developmental neurotoxicants.

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.

The variability of standard artificial soils: cadmium and phenanthrene sorption measured by a batch equilibrium method

Artificial soil (AS) is used in soil ecotoxicology as a test medium or reference matrix. AS is prepared according to standard OECD/ISO protocols and components of local sources are usually used by laboratories. This may result in significant inter-laboratory variations in AS properties and, consequently, in the fate and bioavailability of tested chemicals. In order to reveal the extent and sources of variations, the batch equilibrium method was applied to measure the sorption of 2 model compounds (phenanthrene and cadmium) to 21 artificial soils from different laboratories. The distribution coefficients (Kd) of phenanthrene and cadmium varied over one order of magnitude: from 5.3 to 61.5L/kg for phenanthrene and from 17.9 to 190L/kg for cadmium. Variations in phenanthrene sorption could not be reliably explained by measured soil properties; not even by the total organic carbon (TOC) content which was expected. Cadmium logKd values significantly correlated with cation exchange capacity (CEC), pHH2O and pHKCl, with Pearson correlation coefficients of 0.62, 0.80, and 0.79, respectively. CEC and pHH2O together were able to explain 72% of cadmium logKd variability in the following model: logKd=0.29pHH2O+0.0032 CEC -0.53. Similarly, 66% of cadmium logKd variability could be explained by CEC and pHKCl in the model: logKd=0.27pHKCl+0.0028 CEC -0.23. Variable cadmium sorption in differing ASs could be partially treated with these models. However, considering the unpredictable variability of phenanthrene sorption, a more reliable solution for reducing the variability of ASs from different laboratories would be better harmonization of AS preparation and composition.

Preparation and testing of phosphate, oxalate and uric acid matrix-matched standards for accurate quantification of 2D elemental distribution in kidney stone sections using 213 nm nanosecond laser ablation inductively coupled plasma mass spectrometry

Matrix-matched calibration for quantitative elemental mapping of kidney stones by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was developed with a 213 nm Nd:YAG laser ablation device and a quadrupole mass spectrometer. The method was applied to the imaging of P, Na, Sr, Zn, Ba and Pb distributions over a section of the kidney stone specimen containing phosphate and oxalate phases. Eighteen kidney stone specimens consisting of phosphate, oxalate and urate phases in various proportions were cut into halves for both preparation of calibration pellets and bulk analysis. Homogeneity of calibration pellets was examined by scanning electron microscopy (SEM) and LA-ICP-MS, concluding that areas of individual biominerals were thoroughly mixed and their size in units of micrometers was well below the size of the used laser spot. Calcium was employed as the internal reference element, being present in sufficient contents in the studied kidney stones. Mean values of calcium contents in oxalate and phosphate phases separately were determined using an electron microprobe (EMP) in the kidney stone section further subjected to the mapping. The actual (time- and space-resolved) Ca sensitivity was computed for each 44Ca+ signal and used as the internal reference for LA-ICP-MS isotopic signals of P, Na, Sr, Zn, Ba and Pb when mapping. Dependences of particular isotopic signal intensity/Ca sensitivity ratios vs. average elemental contents by solution analysis were processed by ordinary least squares linear regression. Despite variable matrices the regression yielded calibration lines with insignificant intercepts, coefficients of determination R2 > 0.9955, and relatively narrow prediction and confidence bands. However, in addition, the applicability of four-point calibration and four single-point calibrations as less time-consuming options was examined on the basis of the NIST SRM 1486 bone meal pellet analysis. Best fit was obtained for the four-point calibration and single-point calibration with the phosphate pellet. Quantitative elemental maps of the kidney stone section were recorded and computed for P, Na, Sr, Zn, Ba and Pb. The feasibility of quantification by matrix-matched single-point calibration was verified by determination of the median elemental contents in phosphate and oxalate phases by LA-ICP-MS and their arithmetic comparison mean values obtained over the same section area using EMP.