Lidia Kozak

Selected arsenic species: As(III), As(V) and dimethylarsenic acid (DMAA) in Xerocomus badius fruiting bodies

The aim of the study was to determine the content of As(III), As(V) and DMAA (dimethylarsinic acid) in Xerocomus badius fruiting bodies collected from selected Polish forests from areas subjected to very low or high anthropopressure and some commercially available samples obtained from the Polish Sanitary Inspectorate. The arsenic species determination was provided by two independent HPLC-HG-AAS hyphenated systems. The results show high levels (up to 27.1, 40.5 and 88.3 mg kg(-1) for As(III), As(V) and DMAA, respectively) of arsenic and occurrence of different species in mushrooms collected from areas subjected to high anthropopressure and two commercially available samples. For mushroom samples collected from areas not subjected to high anthropopressure and two commercially available samples the arsenic species level was below 0.5 mg kg(-1) for each arsenic form. Therefore, the accumulation of arsenic by mushrooms may lead to high (toxic for humans) arsenic concentrations, and arsenic species levels should be monitored in mushroom foodstuffs.

The methodology and results of determination of inorganic arsenic species in mobile fractions of tsunami deposits by a hyphenated technique of HPLC-HG-AAS

A method of extraction has been proposed for the determination of inorganic species of As(III) and As(V) in the exchangeable fraction of sediments left by the 2004 tsunami. The method combines the fractionation of solid samples with speciation analysis by high performance liquid chromatography with hydride generation and atomic absorption spectrometry (HPLC-HG-AAS). The proposed extraction liquid is a phosphate buffer of Na2HPO4 and KH2PO4, with different concentrations of phosphate ranging from 5 to 50 mmol L−1. This method has been tested for different masses of samples as well as for different times of extraction, pH, temperature, and the presence or absence of mixing. The optimum conditions of extraction have been obtained by the use of buffer (50 mmol L−1 under pH from 5.8 to 6.2) at 80°C. The new technique was applied for the analysis of tsunami deposits left on land and sampled shortly after the tsunami (2005) and after the first (2006) and second rainy seasons (2007). The obtained results show that the exchangeable fraction of tsunami deposits was enriched in arsenic in comparison to reference soil samples. The major changes after the rainy seasons were not in the total concentration of inorganic As species, but in the ratio of As(III) to As(V). More toxic As(III) was removed from the deposits or oxidised, and after two years was hardly detectable in the tsunami deposits.

The microwave induced plasma with optical emission spectrometry (MIP-OES) in 23 elements determination in geological samples

The article presents the optimisation, validation and application of the microwave induced plasma optical emission spectrometry (MIP-OES) dedicated for a routine determination of Ag, Al, B, Ba, Bi, Ca, Cd, Cr, Cu, Fe, Ga, In, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sr, Tl, Zn, in the geological samples. The three procedures of sample preparation has been proposed: sample digestion with the use of hydrofluoric acid for determination of total concentration of elements, extraction by aqua regia for determination of the quasi-total element concentration and extraction by hydrochloric acid solution to determine contents of the elements in acid leachable fraction. The detection limits were on the level 0.001-0.121 mg L(-1) (from 0.010-0.10 to 1.2-12 mg kg(-1) depend on the samples preparation procedure); the precision: 0.20-1.37%; accuracy 85-115% (for recovery for certified standards materials analysis and parallel analysis by independent analytical techniques: X-ray fluorescence (XRF) and flame absorption spectrometry (FAAS)). The conformity of the results obtained by MIP-OES analytical procedures with the results obtained by XRF and FAAS analysis allows to propose the procedures for studies of elemental composition of the fraction of the geological samples. Additionally, the MIP-OES technique is much less expensive than ICP techniques and much less time-consuming than AAS techniques.

Efficacy of supplementation of selected medicinal mushrooms with inorganic selenium salts

The aim of the study was to evaluate the possibility of supplementation with inorganic forms of selenium (Na2SeO4 and Na2SeO3) in concentrations of 0, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0 and 1.5 mM of three medicinal mushroom species: Agrocybe aegerita, Hericium erinaceus and Ganoderma lucidum. Tested mushroom species grew in Se additions of 0–0.6 mM (A. aegerita and H. erinaceus), while growth of G. lucidum bodies was observed for 0–0.8 mM. For the latter mushroom species, the total Se content was the highest. Content of Seorg was diverse; for control bodies it was the highest for G. lucidum (only organic forms were present), lower for A. aegerita (84% organic forms) and the lowest for H. erinaceus (56% organic forms). Accumulation of Se(IV) was generally significantly higher than Se(VI) for all tested mushroom species. There was no significant decrease of A. aegerita or G. lucidum biomass with the exception of G. lucidum bodies growing under 0.8 mM of Se species addition (15.51 ± 6.53 g). Biomass of H. erinaceus bodies was the highest under 0.2 (197.04 ± 8.73 g), control (191.80 ± 6.06 g) and 0.1 mM (185.04 ± 8.73 g) of both inorganic salts. The addition to the medium of Se salts brought about macroscopic changes in the fruiting bodies of the examined mushrooms. Concentrations exceeding 0.4 mM caused diminution of carpophores or even their total absence. In addition, colour changes of fruiting bodies were also recorded. At Se concentrations of 0.4 and 0.6 mM, A. aegerita fruiting bodies were distinctly lighter and those of H. erinaceus changed colour from purely white to white-pink.

Application of the self-organizing mapping in exploration of the environmental impact of a tsunami disaster

A self-organizing map (SOM) algorithm was applied to evaluate the geochemical and environmental impact of 26th December 2004 tsunami, based on interelemental and intersite relations of sediment chemistry. The study was carried out based on data sets, including contents of salts (K, Na, Ca, Mg, Cl and SO4) leached with deionized water, heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in acid leachable fraction, metalloids (As, Sb and Se) in exchangeable fraction, as well as both total Hg and mercury in the form of various species (organomercury, water-soluble, acid-soluble, bound to humic matter and bound to sulfides) in sediment samples. SOM-supported exploration were performed for two separate data sets. The first run was applied for analytical results concerning sediments taken less than 50 days after tsunami event while the second one concerned results obtained for samples collected in the same location one year later, after rainy season. In the case of the “2005-run”, based on mutual linkage, complete set of variables could be conditionally divided into general groups showing of their patterns related to their major source as “salt” and “wastewater.” Classification results revealed natural clusters of sediment samples in relation to their location and to the magnitude of the impact of tsunami wave. Numerous clusters reflect general chemical composition of tsunami sediments while clusters containing isolated sampling locations reflect “site-specific” conditions, partially related to anthropogenic impact. The cleaning effect of the rainy season in Thailand was observed, based on “2006-run” exploaration results. The chemical composition of tsunami sediments was unified for 93% of samples. General patterns related to major source of analytes were analogous compared to the “2005-run.” These studies demonstrate that SOM has the potential to successfully assist the assessment of the environmental impacts of a tsunami disaster and the role of a tsunami sediments as potential carriers of pollution.

Variations of arsenic species content in edible Boletus badius growing at polluted sites over four years

ABSTRACT The content of arsenic (As) in mushrooms can vary depending on the concentration level of this metalloid in the soil/substrate. The present study evaluated the content of arsenic in Boletus badius fruiting bodies collected from polluted and non-polluted sites in relation to the content of this element in overgrown substrate. It was found that mushrooms from the arsenic-polluted sites contained mean concentrations from 49 to 450 mg As kg−1 dry matter (d.m.), with the greatest content found for specimens growing in close proximity of sludge deposits (490±20 mg As kg−1d.m.). The mean content of total arsenic in mushrooms from clean sites ranged from 0.03 to 0.37 mg kg−1 It was found that B. badius could tolerate arsenic in soil substrate at concentrations of up to 2500 mg kg−1, at least. In different years of investigation, shifts in particular arsenic forms, as well as a general increase in the accumulation of organic arsenic content, were observed. The results of this study clearly indicate that B. badius should not be collected for culinary purposes from any sites that may be affected by pollution.

The evolution of December 2004 tsunami deposits: temporal and spatial distribution of potentially toxic metalloids.

The article presents the results of research into the content of metalloid fractions in the tsunami deposits from southern Thailand. The following fractions, which are potentially most easily released from deposits to the environment, have been distinguished: the water soluble fraction, the exchangeable fraction extracted with the phosphate buffer and the fraction eluted with the solution of hydrochloric acid. The analytical technique atomic absorption spectrometry with hydride generation was applied. Spatial variability of the metalloid fractions in deposits and changes occurring in deposits over a period of several years of observation were determined. Based on the statistical analysis of the results, an attempt was made to determine the post-depositional release of deposits components to the environment. Based on the conducted research, the 4 years forming process of the arsenic, antimony and selenium occurrence after the deposition of sediments on land were described, as well as the balance in the amount of deposit components released to the environment.

Environmental impact of flood: The study of arsenic speciation in exchangeable fraction of flood deposits of Warta river (Poland) in determination of "finger prints" of the pollutants origin and the ways of the migration

The paper presents the application of the hyphenated technique - high-performance liquid chromatography with atomic absorption spectrometry detection with hydride generation (HPLC-HG-AAS) - in the determinations of inorganic forms of arsenic: As(III) and As(V) in the exchangeable fraction of flood deposits. The separation of analytical signals of the determined arsenic forms was obtained using an ion-exchange column in a chromatographic system with the atomic absorption spectrometer as a detector, at the determination limits of 5 ngg(-1) for As(III) and 10 ngg(-1) for As(V). Flood deposits were collected after big flood event in valley of the Warta river which took place in summer 2010. Samples of overbank deposits were taken in Poznań agglomeration and vicinity (NW Poland). The results of determinations of arsenic forms in the exchangeable fraction of flood deposits allowed indication of a hypothetical path of deposits migration transported by a river during flood and environmental threats posed by their deposition by flood.

Bioaccumulation of metals and metalloids in medicinal plant Ipomoea pes‐caprae from areas impacted by tsunami

Tsunami events may have an enormous impact on the functioning of aquatic and terrestrial ecosystems by altering various relationships with biotic components. Concentrations of acid-leachable fractions of heavy metals and metalloids in soils and plant samples from areas affected by the December 2004 tsunami in Thailand were determined. Ipomoea pes-caprae, a common plant species growing along the seashore of this region, and frequently used in folk medicine, was selected to assess the presence of selected elements. Elevated amounts of Cd, Pb, Zn, and As in soil samples, and Pb, Zn, As, Se, Cr, and Ni in plant samples were determined from the tsunami-impacted regions for comparison with reference locations. The flowers of Ipomoea pes-caprae contained the highest amounts of these metals, followed by its leaves, and stems. In addition, its bioaccumulation factor (BAF) supports this capability of high metal uptake by Ipomoea pes-caprae from the areas affected by the tsunami in comparison with a reference site. This uptake was followed by the translocation of these elements to the various plant components. The presence of these toxic metals in Ipomoea pes-caprae growing in contaminated soils should be a concern of those who use this plant for medicinal purposes. Further studies on the content of heavy metals and metalloids in this plant in relation to human health concerns are recommended.

Environmental impact of flooding: studies of ‘self-cleaning’ of river ecosystem during consecutive flood events

This article presents the similarities and differences between the chemical compositions of sediments deposited by theWarta river (central Poland) during two consecutive flood events. The studies conducted revealed significant differentiation in the metal content of acid-leached sediment fractions deposited during the summer flood event and subsequent winter flood event. The lower metal content in the sediment deposits during the winter flood event may be evidence of different transport processes and sediment deposition during the consecutive flood stages; as well as the potential ‘purification’ of the river channel from pollutants previously deposited during the summer flood event.