Ján Tomáš

Contamination of wild-grown edible mushrooms by heavy metals in a former mercury-mining area

The aim of this study was to evaluate the contamination of six edible wild species of mushrooms (Boletus pulverulentus, Cantharellus cibarius, Lactarius quietus, Macrolepiota procera, Russula xerampelina and Suillus grevillei) by heavy metals (Hg, Cd, Pb, Zn, Cu, Ni, Cr, Co, Mn and Fe). Mushroom samples were collected from sites contaminated by emissions from mining and processing of polymetallic ores in operation during the period 1969–1993 in Rudňany, southeast Slovakia. The four study sites spanned up to a 5-km distance from the emission source. The collected mushroom samples were analyzed using Flame Atomic Absorption Spectrophotometry and/or Flame Atomic Absorption Spectrophotometry with graphite furnace. Mercury, Cd and, in some samples, also Pb present the highest risks in terms of contamination of the food chain following subsequent consumption. The content of two metals in the dry matter (dm) of the mushrooms exceeded the limits set by the European Union (EU; Cd: 0.5 mg/kg dm, Pb: 1.0 mg/kg dm). The highest mean contents of the eight metals recorded for S. grevillei were 52.2, 2.15, 107, 104, 2.27, 2.49, 81.6 and 434 mg/kg dm for Hg, Pb, Zn, Cu, Ni, Cr, Mn and Fe, respectively. The highest content of Cd was recorded in M. procera (3.05 mg/kg dm) and that of Co in L. quietus (0.90 mg/kg dm). The calculated weekly intake for Hg, Pb and Cd shows that regular consumption of mushrooms from the studied area poses risks to human health.

Human exposure to heavy metals and possible public health risks via consumption of wild edible mushrooms from Slovak Paradise National Park, Slovakia

The contamination level of 92 samples (12 species) of wild edible mushrooms and underlying substrates with heavy metals (Cd, Cu, Hg, Pb and Zn) in the Slovak Paradise National Park that borders with a region of historical mining and processing of polymetallic ores, were determined. The collected samples were analyzed using of atomic absorption spectrophotometry. The metals were determined separately in hymenophore (H) and rest of fruit bodies (RFB). Bioaccumulation factor as well as ratio of metal content in H and RFB were calculated. Cadmium and lead contents in hymenophore exceeded statutory limits of the EU (Cd: 0.5 mg/kg dry weight (dw), Pb: 1.0 mg/kg dw) for edible mushrooms in 96% and 83% of the samples, respectively. The risk from the consumption of the collected mushroom species was calculated based on the provisionally tolerable weekly intake (PTWI) values, and the highest health risk arising with consumption of particularly Macrolepiota procera, Marasmius oreades and Russula vesca from the observed area was demonstrated. It was shown that average weekly consumption of tested mushrooms species results the threat of exceeding of PTWI limits in the case of cadmium values (by 164%, 86% and 4% of PTWI for M. oreades, R. vesca and R. puellaris, respectively) and of mercury (by 96% of PTWI for M. procera) but not lead.

Accumulation and environmental risk assessment of heavy metals in soil and plants of four different ecosystems in a former polymetallic ores mining and smelting area (Slovakia).

ABSTRACT Heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in soils and plants of four different ecosystems (forest, grassland, agro and urban ecosystem) at different distances from the source of the pollution were analyzed in order to assess and compare soil contamination in the various ecosystems and determine the potential accumulation of plants depending on the place they inhabit. Correlation relationships among heavy metals in soils differ depending on the ecosystem, and between soil and plant, the heavy metals showed significant correlation for Cu, Mn, Ni, Pb and Zn. Contamination factor (Cf), degree of contamination (Cd) and pollution load index (PLI) were used in order to determine the level of environmental contamination of the study area. All studied ecosystems were rated as moderately contaminated (except agroecosystem, which was found as low contamination ecosystem) according to Cd and extremely polluted according to PLI. The highest pollution in both cases was found in urban ecosystem, and Cd, Cu and Fe were determined as the biggest pollutants.

Assessment of environmental and health risks in former polymetallic ore mining and smelting area, Slovakia: Spatial distribution and accumulation of mercury in four different ecosystems

Former long-term mining and smelting of pollymetallic ores in the Middle Spiš area caused a serious contamination problem of the environment with heavy metals and metalloids, especially mercury (Hg). Several studies have reported concentration of Hg in the area but this paper provides first detailed characterization of Hg contamination of different environmental components in agricultural, forest, grassland and urban ecosystems. The ecosystems are in different distances from emission sources - former mercury and copper smelting plants in NE Slovakia. Total Hg content was studied in soil/substrate samples (n = 234) and characteristic biological samples (Athyrium filix-femina (L.) Roth, Macrolepiota procera (Scop.) Singer, Boletus edulis Bull., Cyanoboletus pulverulentus (Opat.) Gelardi, Vizzini & Simonini, Triticum aestivum (L.), Poa pratensis (L.)) (n = 234) collected in the above-mentioned ecosystems. The level of contamination and environmental risks were assessed by contamination factor (Cf), index of geoaccumulation (Igeo) and potential environmental risk index (PER). To determine the level of transition of Hg from abiotic to biotic environment, bioconcentration factor (BCF) was used. To determine a health risk resulting from regular and long-term consumption of the locally available species, the results of the Hg content were compared with the Provisional Tolerable Weekly Intake (PTWI) for Hg defined by World Health Organization. The results suggest that almost 63% of the area belong to the very high risk category and 80% of the sampling sites shown very high contamination factor. Geoaccumulation index showed that almost 30% of the area is very strongly contaminated and only 8% is not contaminated with Hg. Spearmans correlation relationship confirmed that the values of PER, BCF, Cf and Igeo decreased with an increasing distance from the pollution source. The percentage of contribution to PTWI ranged between 5.76-69.0% for adults and 11.5-138% for children. Mushroom M. procera showed the highest %PTWI among the tested biological samples. Studied ecotoxicological parameters showed high level of health risk for population living in the area. Consumption of the crops grown in the area and mainly edible wild mushrooms might negatively affect the health of the consumers in the long-term.

Changes of Polyphenolic Substances in the Anatomical Parts of Buckwheat (Fagopyrum esculentum Moench.) during Its Growth Phases

In this study the changes of total polyphenolics in different anatomical parts (stems, leaves, flowers and seeds) of common buckwheat (Fagopyrum esculentum Moench.) during vegetation period were analysed. The content of total polyphenolics was evaluated in growth phase I (formation of buds), phase II (at the beginning of flowering), phase III (full blossoming) and phase IV (full ripeness). In all growth phases (GP) the stems and leaves were evaluated and statistically significant differences in polyphenolics content between the two parts were confirmed. Statistically significant differences (p < 0.01) in polyphenolics content (in GP II and III) between stems and leaves; and between stems and flowers were found. In flowers an average of 13.8 times higher and in leaves 6 times higher concentration of polyphenolics in comparison with stems was measured. In GP III the content of polyphenolics in common buckwheat was following: flowers > leaves > achene > stems. In flowers an average of 11.9 times higher, in leaves 8.3 times higher and in achenes 5.9 times higher contents of polyphenolics compared with stems were found. In GP III and IV (leaves, achenes, stems) the leaves contained in average 20 times higher and achenes 5.6 times higher polyphenolics than stems.

Determination of heavy metals concentration in raw sheep milk from mercury polluted area.

The paper focuses on determining the content of monitored contaminants (Cd, Cu, Hg, Pb and Zn) in 53 samples of raw sheep milk collected in 2013 and 2014 on the sites Porac and Matejovce nad Hornadom (middle Spis). The area is characterized by historical mining and metalworking activity (mining and processing of polymetallic ores rich in Hg, Cd and Pb). Currently, the area is one of the most mercury contaminated areas in Central Europe. All statistical analyses were carried out using the statistical software Statistica 10.0 ( Statsoft, USA). Descriptive data analysis included minimum value, maximum value, arithmetic mean and standard deviation. The results of the studied contaminant content show that the limit value for cadmium (10 μg.kg -1 ) was exceeded in 25 samples. In the case of lead, the limit value of 20 μg.kg -1 was exceeded in 16 cases. The limit value for copper (0.4 mg.kg -1 ) was exceeded in one case. The limit value for zinc is not defined by a legislative standard. The risk level of the studied contaminants in the samples of raw sheep milk decreases as follows: Cd > Pb > Hg > Cu > Zn. It can be concluded that frequent and long-term consumption of the raw sheep milk originating from the studied sites poses a health risk. The content of the contaminants in the milk and their eventual transition into dairy products should be monitored over a longer term in more detail. Normal 0 21 false false false CS JA X-NONE

The relationships between content of heavy metals in soil and in strawberries

ABSTRACT The work was aimed at assessment of quality of strawberry based on the contents of heavy metals as well as the possible correlations between selected heavy metals in soil and strawberries. The results revealed that from all observed metals in soil determined in aqua regia only in the case of cadmium the maximum permissible limit in comparison with the limit resulting from the Law No. 220/2004 as well as threshold values proposed by European Commission (EC) (2006) has been exceeded. In our paper the values of cadmium in the soil representing 1.86 to 2.41 times higher values than limit valid in the Slovak Republic (0.7 mg/kg) and 2.6 to 3.38 times higher in comparison to EC (0.5 mg/kg). In our study in 1 M NH4NO3 the values of lead ranged from 0.125 to 0.205 mg/kg representing values exceeded the limit valid in Slovak Republic (0.1 mg/kg) about 0.037–0.105 mg/kg. Despite exceeded values of heavy metals in soil, no values above the limit directly in strawberries when compared to Food Codex of Slovak Republic as well as to Commission Regulation 1881/2006 were recorded. Among the varieties statistically significant differences (P < 0.05) in intake of heavy metals were found.

Determination of mercury, cadmium and lead contents in different tea and teas infusions (Camelia sinensis, L.)

The present paper deals with assessing the level of contamination of green ( n = 14) and black - fermented ( n = 10) teas of different origins (country of origin) (China, India, Japan, Nepal and Taiwan), which are normally available in Slovakia. The contents of the studied contaminants (mercury, cadmium and lead) were observed in samples of dried teas and their infusions. The contaminant contents were investigated by atomic absorption spectrometry with Zeeman background correction and a graphite furnace GF-AAS (Cd, Pb). The total mercury content was analyzed by CV-AAS method. Concentrations of the studied contaminants in the dried tea samples were as follows: green tea: Hg: 0.0027 ±0.0010 mg.kg -1 (median ± standard deviation); Cd: 0.161 ±0.084 mg.kg -1 , Pb: 0.875 ±0.591 mg.kg -1 , black tea: Hg: 0.0022 ±0.0014 mg.kg -1 , Cd: 0.397 ±0.077 mg.kg -1 , Pb: 1.387 ±0.545 mg.kg -1 . The contents of the contaminants in the tea infusions were as follows: green tea: Hg: 0.03 ±0.04 μg.L -1 , Cd: 0.278 ±0.068 μg.L -1 , Pb: 1.975 ±0.503 μg.L -1 , black tea: Hg: 0.050 ±0.080 μg.L -1 , Cd: 0.291 ±0.054 μg.L -1 , Pb: 1.955 ±1.264 μg.L -1 . According to the currently valid maximum limits for a particular contaminant in Slovakia, it can be stated that the health standards were not exceeded in any of the tea samples. The limit value of the lead content (2.0 mg.kg -1 DM) was exceeded (by 12.4%) only in one sample of the dried black tea from China (Yunnan - Golden Snow), however it is the limit value valid in China. The results of the analysis of 24 tea samples show that even regular consumption does not pose a health risk to consumers. Normal 0 21 false false false SK X-NONE X-NONE Normal 0 21 false false false EN-US X-NONE X-NONE

Intake of heavy metals in selected varieties of onion (Allium cepa l.) Grown in the different locations / Akumulacja metali ciężkich w wybranych odmianach cebuli (Allium cepa L.) uprawianych w różnych warunkach

Abstract The environmental study, carried out in Slovak Republic, was aimed at the assessment of quality of onion based on the contents of selected heavy metals (Zn, Cu, Ni, Pb and Cd) as well as the possible correlations among heavy metals in soil and onions (Allium cepa L.). Gained results showed that in some monitored localities the measured values were exceeded in comparison with limit values given by the Law No. 220/2004 (valid in the Slovak Republic) as well as threshold values proposed by European Commission (2006). In our paper, the values of total cadmium content were in the range from 1.15 to 1.34 mg∙kg-1 and the content of mobile form of lead was in the range from 0.19 to 1.09 mg∙kg-1. The lead content in all samples (except cv. Red matte grown in locality Klasov) of the onions was also exceeded and the values ranged from 0.05 to 0.21 mg∙kg-1. Among the varieties statistically significant differences (P < 0.05) in the intake of heavy metals were found (Multifactorial analysis of variance, LSD-test contrast P < 0.05) was used to process gained data Streszczenie Badania środowiska, przeprowadzone na Słowacji miały na celu ocenę jakości cebuli poprzez oznaczenie zawartości wybranych metali ciężkich (Zn, Cu, Ni, Pb i Cd), jak również możliwych korelacji pomiędzy obecnością metali ciężkich w glebie i cebuli (Allium cepa L.). Uzyskane wyniki wskazują, że w niektórych monitorowanych lokalizacjach zmierzone wartości zostały przekroczone w stosunku do wartości granicznych określonych w Ustawie nr 220/2004 (obowiązującej w Republice Słowackiej), jak również wartości granicznych zaproponowanych przez Komisję Europejską (KE) (2006). Wyniki naszej pracy wskazują, że wartości całkowitej zawartości kadmu wahają się w zakresie od 1,15 do 1,34 mg∙kg-1, a zawartość ołowiu w postaci mobilnej w zakresie od 0,19 do 1,09 mg∙kg-1. Zawartość ołowiu we wszystkich próbkach cebuli (z wyjątkiem odmiany Red mat hodowanej w miejscowości Klasov) jest również przekroczona, a wartości wahają się w zakresie od 0,05 do 0,21 mg∙kg-1. Wśród odmian stwierdzono statystycznie istotne różnice (p<0,05) w pobieraniu metali ciężkich (porównania wielokrotne dla metali ciężkich w zależności od odmiany, przy 95% przedziale ufności).

The role of sulphur on the content of total polyphenols and antioxidant activity in onion (Allium cepa L.)

Sulphur is one of the most important elements in plants. Sulphur also positive influences on growth functions (nitrogen metabolism, enzyme activity and protein and oil synthesis), yield and quality bulbs of onion. In this experiment was watched the progress of making the total polyphenols content in different levels of fertilizer sulphur in onion during vegetation. In the work we watched also the influence of sulphur fertilization on the antioxidant activity. Sulphur was added in amounts 7.3 mg.kg -1 S, 11 mg.kg -1 S and 14,6 mg.kg -1 S. Samples of fresh onion we collected at the beginning, in the middle and in the end of vegetation period and we prepared an extract: 50 g cut onion extracted by 100 ml 80% ethanol according sixteen hours. These extracts were used for experiment. The content of total polyphenols was estimated by using Folin-Ciocalteau reagent. The absorbance was measured at 765 nm of wave length against blank. Antioxidant activity was measured using a compound DPPH˙ (2.2-diphenyl-1-picrylhydrazyl) at 515.6 nm in the spectrophotometer. Our values of total polyphenolic content during vegetation period were in range from 508.16 ±27.59 mg.kg -1 to 638.2 ±12.84 mg.kg -1 . The highest content of total polyphenolics was recorded at the end of the vegetation period (638.32 ±12.84 mg.kg -1 ) in III. sampling (incorporation of sulphur in quantity of 14.6 mg S.kg -1 soil). This increase was statistically significant (P-value = 2.10 -3 ). The lowest content of total polyphenols was measured in the middle of vegetation period (415.41 ±13.32 mg.kg -1 ) in II. sampling (incorporation of sulphur in quantity of 11 mg S.kg -1 soil). Another indicator that has been evaluated and compared was the influence of sulphur fertilization on the antioxidant activity. The highest values of antioxidant activity were recorded at the end of vegetation period in all variants. The lowest value of antioxidant activity (25.41 ±7.67%) was measured in three sampling in II.variant.