Przemysław Niedzielski

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.

Comparison of modifiers for determination of arsenic, antimony and selenium by atomic absorption spectrometry with atomization in graphite tube or hydride generation and in-situ preconcentration in graphite tube

The study was performed to compare the effect of magnesium modifier (magnesium nitrate) with that of other modifiers (palladium nitrate and nickel nitrate) in determination of arsenic, antimony and selenium by atomic absorption spectroscopy with atomization in a graphite tube, with generation of hydrides and in situ preconcentration in a graphite tube. The assumed criterion of a modifier performance was the magnitude of the analytical signal. It was found that in determinations with atomization in a graphite furnace the effects of all these modifiers were comparable, while in those with hydride generation and in situ preconcentration in a graphite tube the magnesium modifier showed poorer performance (25% decrease of the analytical signal). In determinations of arsenic and selenium the analytical signal obtained with magnesium salt as a modifier was comparable with those obtained in the presence of all other modifiers.

Metal status in human endometrium: Relation to cigarette smoking and histological lesions

Human endometrium is a thick, blood vessel-rich, glandular tissue which undergoes cyclic changes and is potentially sensitive to the various endogenous and exogenous compounds supplied via the hematogenous route. As recently indicated, several metals including Cd, Pb, Cr and Ni represent an emerging class of potential metalloestrogens and can be implicated in alterations of the female reproductive system including endometriosis and cancer. In the present study, we investigated the content of five metals: Cd, Cr, Ni, Pb and Zn in 25 samples of human endometrium collected from Polish females undergoing diagnostic or therapeutic curettage of the uterine cavity. The overall mean metal concentration (analyzed using microwave induced plasma atomic emission spectrometry MIP-OES) decreased in the following order: Cr>Pb>Zn>Ni>Cd. For the first time it was demonstrated that cigarette smoking significantly increases the endometrial content of Cd and Pb. Concentration of these metals was also positively correlated with years of smoking and the number of smoked cigarettes. Tissue samples with recognized histologic lesions (simple hyperplasia, polyposis and atrophy) were characterized by a 2-fold higher Cd level. No relation between the age of the women and metal content was found. Our study shows that human endometrium can be a potential target of metal accumulation within the human body. Quantitative analyses of endometrial metal content could serve as an additional indicator of potential impairments of the menstrual cycle and fertility.

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.

Potential of Cultivated Ganoderma lucidum Mushrooms for the Production of Supplements Enriched with Essential Elements

Ganoderma lucidum is an important medicinal mushroom species and there is continuous interest in its bioactive properties. This study evaluated whether it may additionally serve as a nutritional supplement for the trace elements: selenium (Se), copper (Cu), and zinc (Zn). Mushrooms were cultivated on substrates enriched with 0.1 to 0.8 mM of inorganic Se alone or in combination with Zn and/or Cu. Supplementation increased accumulation of the elements in fruiting bodies regardless of the applied cultivation model. G. lucidum demonstrated the ability to accumulate significant amounts of organic Se, maximally amounting to (i) over 44 mg/kg when the substrate was supplemented only with Se, (ii) over 20 mg/kg in the Se+Cu model, (iii) over 25 mg/kg in the Se+Zn model, and (iv) 15 mg/kg in the Se+Cu+Zn model. The accumulation of Cu and Zn steadily increased with their initial substrate concentrations. Maximum concentrations found after supplementation with 0.8 mM amounted to over 55 mg/kg (Se+Zn) and 52 mg/kg (Se+Cu+Zn) of Zn, and 29 mg/kg (Se+Cu) and over 31 mg/kg (Se+Cu+Zn) of Cu. The greater the supplemented concentration and number of supplemented elements, the lower the biomass of G. lucidum fruiting bodies. Nevertheless, it still remained high when the substrate was supplemented up to 0.4 mM with each element. These results highlight that G. lucidum can easily incorporate elements from the substrate and that, when biofortified, its dried fruiting bodies may serve as a nutritional source of these essential elements.

Determination of Sb(III) and Sb(V) in Water Samples by Hydride Generation Atomic Absorption Spectrometry with In-Situ Trapping in a Graphite Tube

Abstract This work presents results of determinations of inorganic Sb(III)/Sb(V) species and total content of antimony in water samples by the method of atomic absorption spectrometry with hydride generation and in-situ concentration in a graphite tube. The achieved determination limit (3σ) was 0.014 ng/mL for determination of Sb(III) species and the total content of antimony. Moreover, the paper reports results of antimony determination in samples of mineral and tap water obtained by the method with the analyte concentration on the atomizer (graphite tube) surface. The content of antimony in the samples studied varied in the range from 0.04 ng/mL to 0.44 ng/mL for Sb(III) and from 0.22 ng/mL to 0.62 ng/mL for Sb(V).

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.

Cadmium and lead toxicity and bioaccumulation in Microcystis aeruginosa

The growth of human population leads to intensification of agriculture and promotes, through eutrophication, development of cyanobacteria. One of the most widespread and bloom-forming species in freshwater is toxic Microcystis aeruginosa (M. aeruginosa). Combustion of fossil fuels and metallurgical processes are the main sources of heavy metals contamination in surface water including cadmium (Cd) and lead (Pb). The following study was conducted in order to determine the effect of 1–20 mg·L−1 of Cd and Pb on photochemistry (using flow cytometry) and growth (based on chlorophyll concentration) of M. aeruginosa as well as to estimate levels of metal bioaccumulation. We have found that 1–10 mg·L−1 of Cd and 1–5mg·L−1 of Pb induced continuous enhancement of chlorophyll fluorescence during 24 h of incubation. No significant degradation of chlorophyll was observed in these samples. At higher concentrations of 20 mg·L−1 of Cd and 10–20 mg·L−1 of Pb chlorophyll level significantly decreased and its fluorescence was quenched. M. aeruginosa demonstrated high capability of Cd and Pb bioaccumulation, proportionally to initial metal concentration. In samples with initial concentration of 20 mg·L−1 of Cd and Pb bioaccumulation of 87.3% and 90.1% was observed, respectively. Our study demonstrates that M. aeruginosa can potentially survive in highly metals polluted environments, be a primary source of toxic metals in the food chain and consequently contribute to enhanced toxicity of heavy metals to living organisms including human.

The Simultaneous Arsenic, Antimony, and Selenium Determination in Water Samples by Batch Hydride Generation Atomic Absorption Spectrometry

The purpose of this paper is to present a procedure for the simultaneous determination of metalloids: arsenic, antimony, and selenium. Hydride generation was provided in a reaction vessel connected with the atomic absorption spectrometer (AAS) in a fast sequential mode. Two different types of water samples were used while developing the application: seawater and groundwater. The methodology of liquid samples analysis was developed with detection limits of 0.05, 0.03, and 0.06 ng · mL−1 for arsenic, antimony, and selenium, respectively, in 10 mL samples. This methodology was used to determine arsenic, antimony, and selenium in natural water samples.