Jerzy Falandysz

Polychlorinated naphthalenes: an environmental update

Polychlorinated naphthalenes (PCNs; CNs) form a complex mixture of up to 75 congeners containing from one to eight chlorine atoms per naphthalene molecule. Chloronaphthalenes are widespread global environmental pollutants which accumulate in biota. All chloronaphthalenes are planar compounds and can contribute to the aryl hydrocarbon (Ah) receptor-mediated mechanism of toxicity with a combination of various 2,3,7,8-tetrachlorodibenzo-p-dioxin like toxic responses. There are three known main sources of environmental pollution with PCNs: technical PCN formulations, technical polychlorinated biphenyl formulations, and thermal and other processes in the presence of chlorine. The purpose of this paper is to briefly review the most recent data on environmental pollution, chemistry, analysis, sources, formation, persistence, toxicity and behavior of PCNs.

ICP/MS and ICP/AES elemental analysis (38 elements) of edible wild mushrooms growing in Poland

Thirty-eight elements, including toxic cadmium, lead, mercury, silver and thallium, were determined in 18 species of wild edible mushrooms collected from several sites in Pomorskie Voivodeship in northern Poland in 1994. Elements were determined by double focused high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES), after wet digestion of the dried samples with concentrated nitric acid in closed PTFE vessels using a microwave oven. K, P and Mg were present at levels of mg/g dry matter; Na, Zn, Ca, Fe, Cu, Mn, Rb, Ag, Cd, Hg, Pb, Cs, Sr, Al and Si were present at μg/g levels, while Tl, In, Bi, Th, U, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, La, Lu and Ba were present at ng/g levels.

Macro and trace mineral constituents and radionuclides in mushrooms: health benefits and risks.

This article reviews and updates data on macro and trace elements and radionuclides in edible wild-grown and cultivated mushrooms. A huge biodiversity of mushrooms and spread of certain species over different continents makes the study on their multi-element constituents highly challenging. A few edible mushrooms are widely cultivated and efforts are on to employ them (largely Agaricus spp., Pleurotus spp., and Lentinula edodes) in the production of selenium-enriched food (mushrooms) or nutraceuticals (by using mycelia) and less on species used by traditional medicine, e.g., Ganoderma lucidum. There are also attempts to enrich mushrooms with other elements than Se and a good example is enrichment with lithium. Since minerals of nutritional value are common constituents of mushrooms collected from natural habitats, the problem is however their co-occurrence with some hazardous elements including Cd, Pb, Hg, Ag, As, and radionuclides. Discussed is also the problem of erroneous data on mineral compounds determined in mushrooms.

Selenium in edible mushrooms.

Selenium is vital to human health. This article is a compendium of virtually all the published data on total selenium concentrations, its distribution in fruitbody, bioconcentration factors, and chemical forms in wild-grown, cultivated, and selenium-enriched mushrooms worldwide. Of the 190 species reviewed (belonging to 21 families and 56 genera), most are considered edible, and a few selected data relate to inedible mushrooms. Most of edible mushroom species examined until now are selenium-poor (< 1 μ g Se/g dry weight). The fruitbody of some species of wild-grown edible mushrooms is naturally rich in selenium; their occurrence data are reviewed, along with information on their suitability as a dietary source of selenium for humans, the impact of cooking and possible leaching out, the significance of traditional mushroom dishes, and the elements absorption rates and co-occurrence with some potentially problematic elements. The Goats Foot (Albatrellus pes-caprae) with ∼ 200 μ g Se/g dw on average (maximum up to 370 μ g/g dw) is the richest one in this element among the species surveyed. Several other representatives of the genus Albatrellus are also abundant in selenium. Of the most popular edible wild-grown mushrooms, the King Bolete (Boletus edulis) is considered abundant in selenium as well; on average, it contains ∼ 20 μ g Se/g dw (maximum up to 70 μ g/g dw). Some species of the genus Boletus, such as B. pinicola, B. aereus, B. aestivalis, B. erythropus, and B. appendiculus, can also accumulate considerable amounts of selenium. Some other relatively rich sources of selenium include the European Pine Cone Lepidella (Amanita strobiliformis), which contains, on average, ∼ 20 μ g Se/g dw (up to 37 μ g/g dw); the Macrolepiota spp., with an average range of ∼ 5 to < 10 μ g/g dw (an exception is M. rhacodes with < 10 μ g/g dw); and the Lycoperdon spp., with an average of ∼ 5 μ g Se/g dw. For several wild-grown species of the genus Agaricus, the selenium content (∼ 5 μ g/g dw) is much greater than that from cultivated Champignon Mushroom; these include A. bisporus, A. bitorquis, A. campestris, A. cesarea, A. campestris, A. edulis, A. macrosporus, and A. silvaticus. A particularly rich source of selenium could be obtained from selenium-enriched mushrooms that are cultivated on a substrate fortified with selenium (as inorganic salt or selenized-yeast). The Se-enriched Champignon Mushroom could contain up to 30 or 110 μ g Se/g dw, while the Varnished Polypore (Ganoderma lucidum) could contain up to 72 μ g Se/g dw. An increasingly growing database on chemical forms of selenium of mushrooms indicates that the seleno-compounds identified in carpophore include selenocysteine, selenomethionine, Se-methylselenocysteine, selenite, and several unidentified seleno-compounds; their proportions vary widely. Some aspects of environmental selenium occurrence and human body pharmacokinetics and nutritional needs will also be briefly discussed in this review.

Polybrominated Dibenzo-p-Dioxins, Dibenzofurans, and Biphenyls: Inclusion in the Toxicity Equivalency Factor Concept for Dioxin-Like Compounds

In 2011, a joint World Health Organization (WHO) and United Nations Environment Programme (UNEP) expert consultation took place, during which the possible inclusion of brominated analogues of the dioxin-like compounds in the WHO Toxicity Equivalency Factor (TEF) scheme was evaluated. The expert panel concluded that polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), and some dioxin-like biphenyls (dl-PBBs) may contribute significantly in daily human background exposure to the total dioxin toxic equivalencies (TEQs). These compounds are also commonly found in the aquatic environment. Available data for fish toxicity were evaluated for possible inclusion in the WHO-UNEP TEF scheme (van den Berg et al., 1998). Because of the limited database, it was decided not to derive specific WHO-UNEP TEFs for fish, but for ecotoxicological risk assessment, the use of specific relative effect potencies (REPs) from fish embryo assays is recommended. Based on the limited mammalian REP database for these brominated compounds, it was concluded that sufficient differentiation from the present TEF values of the chlorinated analogues (van den Berg et al., 2006) was not possible. However, the REPs for PBDDs, PBDFs, and non-ortho dl-PBBs in mammals closely follow those of the chlorinated analogues, at least within one order of magnitude. Therefore, the use of similar interim TEF values for brominated and chlorinated congeners for human risk assessment is recommended, pending more detailed information in the future.

Perfluorinated compounds in streams of the Shihwa industrial zone and Lake Shihwa, South Korea

Concentrations of perfluorinated alkyl compounds (PFAs), including perfluorooctane sulfonate (PFOS), perfluorohexanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonamide, perfluorodecanoate, perfluorononanoic acid, perfluorooctanoate (PFOA), perfluoroheptanoate, and perfluorohexanoate, were measured in the streams of the Shihwa and Banweol industrial areas on the west coast of South Korea as well as the adjacent Lake Shihwa (an artificial lake) and Gyeonggi Bay. Perfluorinated alkyl compounds were concentrated from water using solid-phase extraction and were identified and quantified by liquid chromatography/ triple-quadrapole tandem mass spectrometry. Of the PFAs measured, PFOS and PFOA occurred at the greatest concentrations. Concentrations of PFOS ranged from 2.24 to 651 ng/L, and concentrations of PFOA ranged from 0.9 to 62 ng/L. The concentrations of PFOS observed in Lake Shihwa were among the greatest ever measured in the environment. These results suggest local industrial sources of PFOS and PFOA as well as other PFAs. Because of dilution, the greatest concentrations occur in a rather restricted area, near the points of discharge of the streams that empty into the lake. The greatest measured concentration of PFOS exceeded the threshold for effects predicted for predatory birds consuming aquatic organisms continuously exposed to this level.

The concentrations and bioconcentration factors of mercury in mushrooms from the Mierzeja Wiślana sand-bar, northern Poland.

The total concentration of mercury was determined in 15 species of wild growing mushrooms, each represented by 15 specimens including underlying substrate, collected from the unpolluted area of the sand-bar Mierzeja Wiślana in the northern part of Poland in 1993-1994. Mercury was measured by cold vapour atomic absorption spectrometry (CV-AAS) after wet digestion of the samples with concentrated nitric acid in a glass system. The mushroom species examined showed a wide range of mercury concentrations, i.e. from 5.6 +/- 2.1 micrograms/g dry wt. in Scleroderma citrinum to 1100 +/- 240 micrograms/g in the edible Macrolepiota procera. No bioconcentration of mercury was observed in Xerocomus badius, Paxilus involutus, Russula queletii and Lactarius rufus. In Hygrophorius aurantiaca, Armilariella mellea and Amanita vaginata the bioconcentration factor (BCF) values of mercury were close to one. Accumulation of mercury was slight in Oudemansiella platyphylla and Amanita citrica (BCF between 2.0 and 3.3 in the caps and 1.7 in the stalks) and high in Leccinum scabrurm, Amanita muscaria and Macrolepiota procera (BCFs between 11 and 35 in the caps and 6.7-18 in the stalks). In the whole fruiting body of Polyporus melanopsuss and Scleroderma citrinum the BCF values of mercury were 4.4 and 0.083, respectively. There was a high correlation between the concentrations of mercury in the caps and stalks of Macrolepiota procera and in the underlying substrate (P < 0.001), a slight correlation for Polyporus melanopsuss, and also for the caps of Leccinum scabrum, Oudemansiella platyphylla and Russula aeruginea and the stalks of Hygrophoropsis aurantiaca (P < 0.01) and L. scabrum (P < 0.05). For the other mushroom species investigated there was no correlation between mercury concentration in the fruiting bodies and underlying substrate.

Metals bioaccumulation by bay bolete, Xerocomus badius, from selected sites in Poland

The concentrations of 14 elements (Pb, Cd, Ag, Cu, Mn, Cr, Co, Ni, Fe, Zn, Na, K, Ca, Mg) were determined in fruiting bodies of bay bolete, Xerocomus badius, and the underlying soil substratum collected from northern and north-eastern Poland. The total metals content was determined by flame atomic absorption spectrometry (AAS), using deuterium-background correction. The caps of the mushroom examined showed greater concentrations of some metals than the stalks, and the values of the cap to stalk ratio were similar despite different sampling sites. In order to estimate the degree of accumulation of each element by mushrooms, bioconcentration factor values (BCFs) were calculated. Significant correlation coefficients (P<0.001, P<0.01 and P<0.05) were found between concentrations of metals in the caps, stalks of Xerocomus badius and the associated soil as a substratum. Cluster analysis (CA) and discriminant function analysis (DFA) were applied to the concentration data obtained. Some spatial differences in metal concentrations, especially concerning Pb were identified.

Multivariate analysis of mineral constituents of edible Parasol Mushroom (Macrolepiota procera) and soils beneath fruiting bodies collected from Northern Poland

Caps and stipes of 141 fruiting bodies of Parasol Mushroom (Macrolepiota procera) and surface layer of soils collected from 11 spatially distant and background (pristine) areas in Northern Poland were analyzed for Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr, and Zn by inductively coupled plasma optical emission spectroscopy and cold vapor atomic absorption spectroscopy. In terms of bioconcentration and bioexclusion concept, K, Ag, Cu, Rb, and P were highly bioconcentrated in caps, and their bioconcentration factor values varied for the 11 sites between 120 and 500—67–420, 70–220, 10–170, and 45–100, respectively. Cd, Zn, Mg, and Na showed bioconcentration factors (BCFs) between 3.3 and 36, 3.7–15, 0.92–6.3, and 1.4–44 while Al, Ba, Ca, Co, Cr, Mn, Ni, Pb, and Sr were excluded (BCF < 1). The Parasol Mushroom is a species harvested in the wild, and its caps are of unique taste and can contain a spectrum of essential and hazardous mineral compounds accumulated at elevated concentrations, even if collected at the background (pristine) areas. These elevated mineral concentrations of the caps are due to the efficient bioconcentration potential of the species (K, Ag, Cu, Rb, P, Cd, Zn, Mg, and Na) and abundance in the soil substrates (Al, Ca, Fe, Mn). The estimated intake rates of Cd, Hg, and Pb contained in Parasol Mushroom’s caps show a cause for concern associated with these metals resulting from the consumption of between 300- and 500-g caps daily, on a frequent basis in the mushrooming season.

The determination of mercury in mushrooms by CV-AAS and ICP-AES techniques

This research presents an example of an excellent applied study on analytical problems due to hazardous mercury determination in environmental materials and validity of published results on content of this element in wild growing mushrooms. The total mercury content has been analyzed in a several species of wild-grown mushrooms and some herbal origin certified reference materials, using two analytical methods. One method was commonly known and well validated the cold-vapour atomic absorption spectroscopy (CV-AAS) after a direct sample pyrolysis coupled to the gold wool trap, which was a reference method. A second method was a procedure that involved a final mercury measurement using the inductively-coupled plasma atomic emission spectroscopy (ICP-AES) at λ 194.163 nm, which was used by some authors to report on a high mercury content of a large sets of wild-grown mushrooms. We found that the method using the ICP-AES at λ 194.163 nm gave inaccurate and imprecise results. The results of this study imply that because of unsuitability of total mercury determination using the ICP-AES at λ 194.163 nm, the reports on great concentrations of this metal in a large sets of wild-grown mushrooms, when examined using this method, have to be studied with caution, since data are highly biased.