Pavol Trebichalský

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.

Antioxidant activity, phenolic content and colour of the Slovak Cabernet Sauvignon wines.

Antioxidants are specific substances that oxidize themselves and in this way they protect other sensitive bioactive food components against destruction. At the same time, they restrict the activity of free radicals and change them to less active forms. Grapes and wine are a significant source of antioxidants in human nutrition. One of the most important group occuring in grapes and wines are polyphenols. Many of phenolic compounds have been reported to have multiple biological activities, including cardioprotective, anti-inflammatory, anti-carcinogenic, antiviral and antibacterial properties attributed mainly to their antioxidant and antiradical activity. Therefore, it is important to know the content of polyphenols and their antioxidant effects in foods and beverages. Twenty-eight Cabernet Sauvignon wine samples, originated from different Slovak vineyard regions, were analyzed using spectrophotometry for the content of total polyphenols, content of total anthocyanins, antioxidant activity and wine colour density. Determined values of antioxidant activity in observed wines were within the interval 69.0 - 84.2% inhibition of DPPH (average value was 78.8% inhibition of DPPH) and total polyphenol content ranged from 1,218 to 3,444 mg gallic acid per liter (average content was 2,424 mg gallic acid.L-1). Determined total anthocyanin contents were from 68.6 to 430.7 mg.L-1 (average content was 220.6 mg.L-1) and values of wine colour density ranged from 0.756 to 2.782 (average value was 1.399). The statistical evaluation of the obtained results did not confirm any linear correlations between total polyphenol content, resp. total anthocyanin content and antioxidant activity. The correlations between total polyphenol content and total anthocyanin content, resp. the content of total anthocyanins and wine colour density were strong. The results confirmed very strong correlations between wine colour density and total polyphenol content, resp. antioxidant activity.

Minority cereals cultivated under loaded model conditions / Rzadkie gatunki zbóż uprawiane w warunkach obciążenia metalami ciężkimi

Abstract The aim of this work is to evaluate the extent of risk for the transfer of heavy metals from contaminated soil to selected parts of crops. The goal is to be achieved under the model conditions of vegetation pot experiment. Soil taken from the area of Výčapy-Opatovce and three types of cereals - millet (Panicum miliaceum) cv. UNIQUM, oats (Avena sativa) cv. ATEGO and amaranth (Amaranthus caudatus) - were used. For each crop, four variants (A - control with basic ferilization, B, C, D) were made and cadmium in the form of a water-soluble salt of Cd(NO3)2 was applied in gradual specific doses with 5- (variant B), 10- (variant C), 15-fold (variant D) as the limit values by Law no. 220/2004 Z.z. to assess the state of soil contamination. Crops were harvested at ‘full ripeness’ and using the AAS method (VARIAN 240FS) the heavy metal content was determined by the wet mineralization of plant samples. The lowest cadmium content in the aboveground biomass was observed in millet in comparison to other plants, while the highest was recorded in amaranth. The highest increase in the cadmium content in the aboveground biomass in this crop (appr. 18-fold) was noticed in variant C. The lowest cadmium content was also observed in millet seeds. The highest content of Cd in the seeds was recorded in oats in all variants. Streszczenie Celem pracy jest ocena zakresu narażenia na przemieszczenie metali ciężkich z zanieczyszczonej gleby na wybrane części plonów. Ocenę przeprowadzono w doświadczeniu z uprawą roślin w pojemnikach w warunkach modelowych. Zastosowano próbki gleb z obszaru Výčapy- Opatovce oraz trzy typy zbóż: proso (Panicum miliaceum) cv. UNIQUM, owies (Avena sativa) cv. ATEGO oraz szarłat (Amaranthus caudatus). Dla każdego zboża wykonano cztery warianty eksperymentu (A - wariant kontrolny z normalnym nawożeniem, B, C, i D), w których do próbek gleb dodano kadm w postaci rozpuszczalnej soli Cd(NO3)2 w ilości stopniowo wzrastających dawek: 5 (wariant B), 10 (wariant C), i 15 (wariant D) - krotności wartości granicznej ustanowionej przez Ustawę nr 220/2004 Z.z. w celu oceny stopnia zanieczyszczenia gleby. Zboża uprawiano do całkowitej dojrzałości; zawartość metali ciężkich oceniono z zastosowaniem metody AAS (VARIAN 240FS) na próbkach roślin zmineralizowanych na mokro. Najniższą zawartość kadmu w biomasie naziemnej stwierdzono dla prosa. Najwyższą zawartość kadmu w biomasie naziemnej zanotowano dla szarłatu. Najwyższy wzrost zawartości kadmu w biomasie naziemnej w tym zbożu (około 18-krotny) stwierdzono w wariancie C. Najniższą zawartość kadmu zaobserwowano także w nasionach prosa. Najwyższą zawartość kadmu w nasionach stwierdzono dla owsa we wszystkich wariantach eksperymentu.

Vertical Zinc Migration in Various Soil Types

Vertical Zinc Migration in Various Soil Types In this contribution the zinc content in selected soil types and soil reaction on zinc loading in kinetic model conditions with knock-down columns filled with soil samples are evaluated. The total zinc content after their draining, finish and decomposition by HF + HClO4 mixture and its fractions content in extract of 2 mol dm-3 HNO3, in extract of 0.05 mol dm-3 EDTA and in extract of 0.01 mol dm-3 CaCl2 using atomic absorption spectrometry method were determined. The knock-down columns filled with soil samples in model kinetic conditions were used for observation of zinc sorption measure. The maximal water capacity of soils was determined and then solution of 280 mg zinc (ZnSO4.2H2O) per kilogram of soil was applied. The zinc contents in extraction solutions 2 mol dm-3 HNO3, 0.05 mol dm-3 EDTA and 0.01 mol dm-3 CaCl2 in drained 0.05 m high soil columns by atomic absorption spectrometry method were determined. The obtained results were evaluated by mathematical-statistical methods - multiple range analysis and linear regression. Achieved data were compared to allowed limit values. The results show different behavior of individual soil types against zinc loading. The soils showed different properties, where zinc migration to the lower column layers was determined. The accent is given to zinc dynamics in neutral and acid soils. The limit value A (140 mg kg-1) was observed in Luvic Cambisol. The limit value A1 (40 mg kg-1) was observed in Eutric Regosol and Luvic Cambisol in upper layer of soil in column. The obtained results show high mobility of zinc in tested soils and thus its risk for ecosystems.

Copper content in cereals grown in the model condition

The consumption of cereals in Slovakia but also worldwide is increasing by every year. From 30000 to 50000 tons of mercury circulates thought the biosphere that gets into the atmosphere degassing of the earths crust and world oceans. Trace element as copper is one of the most efficient antioxidants in the body, often referred to as an element of beauty. It acts as a powerful catalyst for many enzymes and vitamins, through which already small amounts affects many activities in the body (strengthens immunity, reduces levels of histamine). It accumulates in the barley, beans, cucumber, nuts or milk and so on. The aim of our work was the evaluation of transfer of mercury from sludge to edible part of chosen cereals. The objectives were achieved in simulated conditions of growing pot experiment. We used agricultural soil from the location of Výcapy - Opatovce for the realization of the experiment. The sludge, which was added at various doses, was taken from Central Spis area from locality of Rudňany near the village where minedironore that contains mainly cooper and mercury during last few decades was. We used three types of cereals: barley ( Hordeum sativum L . ) variety PRESTIGE, spring wheat ( Triticum aestivum L . ) variety ISJARISSA and oat ( Avena sativa L . ) variety TATRAN. The length of growing season was 90 days. From the obtained results of two years can be concluded that the accumulation of cooper by seed follows barley ˂ oat ˂ wheat. Even though that the barley is characterized by the highest accumulation of cooper in the seeds, the content did not exceed the maximum level specified by The Codex Alimentarius of the Slovak Republic (CA SR). The results shows that the suitable cultivation of the cereals in localities, which are contaminated with heavy metals, especially by cooper, that the high content of cooper in soil do not pose a risk of accumulation of the metal into the cereal grain.

The content of mercury in various types of cereals that were grown in the model conditions

The consumption of cereals in Slovakia but also worldwide is increasing by every year. From 30000 to 50000 tons of mercury circulates throught the biosphere that gets into the atmosphere degassing of the earths crust and world oceans. Mercury affects CNS and causes its disorders. The high doses of mercury causes a lot of different changes of personality as well as increased agitation, memory lossorinsomnia. It can also affect other organ systems such as the kidney. The exposure level is reflected in the concentration of mercury in blood and urine. The aim of our work was the evaluation of transfer of mercury from sludge to edible part of chosen cereals. The objectives were achieved in simulated conditions of growing pot experiment. We used agricultural soil from the location of Výcapy - Opatovce for the realization of the experiment. The sludge, which was added atvarious doses, was taken from Central Spis area from locality of Rudňany near the village where minedironore that contains mainly copperand mercury during last few decades was. We used three types of cereals: barley ( Hordeum sativum L. ) variety PRESTIGE, spring wheat ( Triticum aestivum L. ) variety ISJARISSA and oat ( Avena sativa L. ) variety TATRAN. The length of growing season was 90 days. From the obtained results of two years can be concluded that the accumulation of mercury by seed follows wheat ˂ barley ˂ oat. Even though that the oat is characterized by the highest accumulation of mercuryin the seeds, the content did not exceed the maximum level sspecified by The Codex Alimentarius of Slovak Republic. The results shows that the suitable cultivation of the cereals in localities, which are contaminated with heavy metals, especially by mercury, that the high content of mercury in soil do not pose a risk of accumulation of the metal into the cereal grain.

Herbicidal effect in relation to the accumulation of macroelements and its regulation by regulators of polyamine synthesis.

Stress effects of triazine herbicide on cumulating of important macroelements (phosphorus, potassium, calcium and magnesium) into the grain of barley variety Kompakt, as well as the elimination of its negative effect through the addition of regulators of polyamine synthesis (γ-aminobutyric acid and propylenediamine) were investigated in pot trial. These morphoregulators are degrading products of polyamines and hypothetically after foliar application they should support their biosynthesis which increased level act against stress in plants. Application of the herbicide alone in comparison to control variant reduced the contents of all mentioned macroelements in grain of barley and also in variants, where the mixtures of herbicide with regulators of polyamine biosynthesis were applied, also the values of contents of all macroelements (except of magnesium) in barley grain were reduced (in comparison to this variant). It could be summarized that the presence of regulators in mixtures with triazine herbicide in comparison to control variant had not positive effects on contents of these biogenic elements in grain. By the comparison of variant with the applied herbicide with variants, where also regulators of polyamine synthesis were applied, there was the most positive influence of these mixtures of morphoregulators on statistically non-significant accumulation of phosphorus into generative organs of spring barley and in the case of positive accumulation of magnesium into these plant tissues there was statistically significant relation only after application of mixtures of herbicide with propylenediamine. Positive influence on accumulation of calcium was evaluated only after using of mixtures of herbicide with propylenediamine (statistically significant relation was recorded at the dose 29.6 g.ha -1 ).

THE EFFECT OF RATIONALIZATION OF GROWING SYSTEMS ON INTAKE OF IRON, POTASSIUM INTO BARLEY GRAIN

The influence of applied inorganic nutrients in soil, the method of tillage (conventional and minimalization) on accumulation of Fe and K into the grain of selected varieties of barley was observed. Small-parcel experiments were carried out on fields with size 14 m2 in three parallels. Four levels of fertilization were done: 1) control – not fertilized variant; 2) N70 + P4,36 + K16,6; 3) N60 + P22,7 + K36; 4) N60 + P22,7 + K36 + Ca25. Fe, K in grain of barley were mineralized by the method of Koppova and their content was assessed by the method of flame AAS at instrument VARIAN 240FS. Content of Fe in dry matter of barley grain in analyzed samples were v interval 34.7-109.0g.kg-1 and of potassium 293,1-658,9g.kg-1. Application of macro elements (N, P, K) into the soil had on the accumulation of Fe into the barley grain reduction effect (beside KM2084 variety) and contrary, in comparison with control variant increased influence on intake of mentioned element in winter varieties (beside variety Malwinta) not dependent on the method of amendments of soil by tillage. Addition of CaCO3 in fertilizers affected with contrary - reducing effect of contents Fe and K in barley grain.

Potential antagonist Zn effect on faba bean (Faba vulgaris m.) contaminated by Pb and Cd / Antagonistyczny wpływ Zn na bób (Faba vulgaris m.) zanieczyszczony Pb i Cd

Abstract The pollution of soil by heavy metals is considered to be a big problem in the world today. Currently, attention is being paid to the content of individual heavy metals in the soil-plant-food system. In our work, mainly the effect of bivalent cations of lead, cadmium and zinc and its uptake by faba bean (Faba vulgaris M.) was surveyed. The results obtained suggest that the incorporation of Pb (200 mg • kg-1 soil) and Cd (10 mg • kg-1) had a negative effect on the quantitative and qualitative parameters of faba bean. The incorporation of Pb in the faba bean crop is statistically significantly decreased by 24.86%, and the reduction of Cd represented 29.91% compared to the control. In the case of common application of zinc, cadmium and lead in soil (variants C, E), there was a slight increase in crop yield compared to the individual incorporation of heavy metals (variants B, D); in the case of Pb, the increase was 13.14%, and in case of Cd 27.77%. A common application of heavy metals with zinc had a positive influence on quality parameters of the faba bean. We have seen a decrease in Cd to 0.15 ± 0,018 mg • kg-1 (a statistically significant decrease) and decrease in Pb to 0.61 ± 0.17 mg • kg-1 (without significant differences). Streszczenie Zanieczyszczenie gleb metalami ciężkimi stanowi jeden z ważniejszych problemów na świecie. Obecnie, uwaga kierowana jest nie tylko na zawartość poszczególnych metali ciężkich w systemie gleba-roślina-żywność. W naszej pracy badaliśmy wpływ i pobór dwuwartościowych kationów ołowiu, kadmu i cynku przez bób (Faba vulgaris M.). Uzyskane wyniki sugerują, że pobranie Pb (200 mg • kg-1 gleby) i Cd (10 mg • kg-1) miało negatywny wpływ na parametry ilościowe i jakościowe bobu. W przypadku pobrania ołowiu, plon bobu zmniejszył się statystycznie istotnie o 24.86% a redukcja Cd stanowiła 29.91% w porównaniu z próbką kontrolną. W przypadku łącznej dostawy Zn, Cd i Pb do gleby (warianty C, E), obserwowano nieznaczne podwyższenie plonu w porównaniu z dostawą poszczególnych metali ciężkich (warianty B, D). W przypadku Pb wzrost plonu wyniósł 13.14% a w przypadku Cd - 27.77%. Łączna dostawa metali ciężkich z cynkiem miała pozytywny wpływ na jakość parametrów bobu. Zaobserwowano obniżenie zawartości Cd do 0.15 ± 0,018 mg • kg-1 (wartość statystycznie istotna) oraz obniżenie zawartości Pb do 0.61 ± 0.17 mg • kg-1 (bez istotnych różnic).