Grażyna Jarzyńska

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.

Bioconcentration potential of metallic elements by Poison Pax (Paxillus involutus) mushroom

Bioconcentration potential of Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, Sr, Pb, Rb and Zn by Pioson Pax (Paxillus involutus) fungus was investigated in field collections of mushrooms from 12 geographically distant sites in Poland. Caps, stipes and soil (0-15 cm layer) underneath to the fruiting bodies were examined. Inductively coupled plasma – atomic emission spectrometry (ICP-AES) was used to determine the total metallic elements content. Both “labile” (cold 20% HNO3 extraction) and “pseudo-total” (cold and hot 65% HNO3 extraction) fractions of metallic elements of soil were determined. K, Rb and Cu were effectively bio-concentrated by Poison Pax in caps and their BCF values were 1000 ± 520, 740 ± 540 and 100 ± 79, and less were Zn, Na, Mg and Ni with BCF of 40 ± 28, 33 ± 23, 18 ± 10 and 1.9 ± 1.4, respectively. Al, Ba, Co, Cr, Fe, Mn, Sr and Pb were bio-excluded (BCF < 1 in caps and stipes). The “labile” Ag, Cd and Hg content of soil was below detection limit of the analytical method. Ba, Ca, Mn, Na and Sr were more eficiently bio-concentrated in stipes of Poison Pax, while Fe, Mg, Pb and Rb in caps, and Al, Co, Cr, Cu, K, Ni and Zn similarly in caps and stipes. Also Ag and Cd (and Hg) were more effectively bio-concentrated in caps than stipes. Al, Ba, Fe and Pb were bio-excluded by Poison Pax (BCF < 0.2) but were abundant minerals of soil and more or less abundant also in carpophores. Some intermetallic relationships (co-uptake and binding) are evident for Poison Pax. The amount of “labile” fraction of metallic elements contained in soil doesn’t seem to explain the Poissons Pax accumulation potential for these elements. Biological features of species, which are related to its ability to enable, enhance or reduce uptake of metallic elements by mycelium and further translocation and binding in carpophores but in parallel also translocation to symbiotic plant can be major forces impacting amounts accumulated in caps and stipes. Metallic elements concentrations determined in fruiting bodies seem to explain in the best way what is largely bioavailable from the substrate in situ to a given mushroom species.

Survey on composition and bioconcentration potential of 12 metallic elements in King Bolete (Boletus edulis) mushroom that emerged at 11 spatially distant sites

This paper provides data on baseline concentrations, interrelationships and bioconcentration potential of 12 metallic elements by King Bolete collected from 11 spatially distant sites across Poland. There are significant differences in concentrations of metals (Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr, Zn) and their bioconcentration potential in King Bolete Boletus edulis at 11 spatially distant sites surveyed across Poland. These have resulted from significant geographical differences in trace metal concentrations in a layer (0-10 cm) of organic and mineral soil underneath to fruiting bodies and possible local bioavailabilities of macro- (Ca, K, Mg, Na) and trace metals (Al, Ba, Cd, Cu, Fe, Mn, Sr, Zn) to King Bolete. The use of highly appreciated wild-grown edible King Bolete mushroom has established a baseline measure of regional minerals status, heavy metals pollution and assessment of intake rates for wild mushroom dish fanciers against which future changes can be compared. Data on Cd, Cu and Zn from this study and from literature search can be useful to set the maximum limit of these metals in King Bolete collected from uncontaminated (background) areas. In this report also reviewed are data on Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr and Zn accumulation in King Bolete.

Variations in metal levels accumulated in Poison Pax (Paxillus involutus) mushroom collected at one site over four years

K, Ca, Mg, Na, Zn, Al, Fe, Mn, Rb, Cu, Sr, Ag, Ba, Pb, Ni, Cd, Co, Cr and Hg content have been examined in caps and stipes of mature fruiting bodies of Poison Pax (Paxillus involutus) collected from the same site over 4 years in 1999–2002. Cluster analysis (CA) did indicate on a different composition of these mineral constituents in fruiting bodies that emerged in 1999 and 2000, when compared to 2001 and 2002. In light of principal component analysis (PCA), the metals differentiating these two biannual sets of fruiting bodies were Mn (greatest load to PC1) together with Ca, Fe, Al, Cu, Cd and Hg; Ni (greatest load to PC2) together with Zn, Sr, Ba, Pb and Co, and Ag (greatest load to PC3) together with Na. The elements such as Mg, Sr and Cr showed similar contents both in caps and stipes over four years (p > 0.05; U Mann-Whitney test). Depending on a year or years of collection, contents fluctuated (p < 0.05) for K, Ca, Zn, Al, Fe, Mn, Na, Rb, Cu, Ag, Ba, Pb, Ni, Cd, Co and Hg. The values of quotients for K, Ca, Mg, Na, Al, Ba, Rb, Cu, Sr, Mn, Co, Cr and Ni content between caps and stipes (QC/S) remained constant (p > 0.05) over four years, and for Fe, Ag, Cd, Cr, Hg and Pb fluctuated (p < 0.05). The results of this study imply that a potential of mycelium to up-take metallic elements from substratum and their further transportation within fruiting body and sequestration in Poison Pax, even at a stabile geochemical condition (the same stand and probably the same mycelia), can fluctuate over the years or the life-span of mycelium.

Selenium and 17 other largely essential and toxic metals in muscle and organ meats of Red Deer (Cervus elaphus)--consequences to human health.

Concentrations, composition and interrelationships of selenium and metallic elements (Ag, Ba, Cd, Co, Cr, Cs, Cu, Ga, Mn, Mo, Pb, Rb, Sb, Sr, Tl, V and Zn) have been examined in muscle and organ meats of Red Deer hunted in Poland. The analytical data obtained were also discussed in terms of Se supplementation and deficit to Deer as well as the benefits and risk to humans associated with the essential and toxic metals intake resulting from consumption of Deer meat and products. These elements were determined in 20 adult animals of both sexes that were obtained in the 2000/2001 hunting season from Warmia and Mazury in the north-eastern part of Poland. The whole kidneys contained Ba, Cd, Cr, Ga, Pb, Se, Sr and Tl at statistically greater concentrations than liver or muscle tissue from the same animal. Liver showed statistically greater concentrations of Ag, Co, Cu, Mn and Mo than kidneys or muscle tissue, and muscle tissue was richer in Zn, when compared to the kidneys or liver. Cs and Rb were similarly distributed between all three tissue types, while V was less abundant in liver than kidneys or muscle tissue. There were significant associations between some metallic elements retained in Red Deer demonstrated by Principal Component Analysis (PCA) of the data set. In organ and muscle meats (kidneys, liver and muscle tissue considered together) the first principal component (PC1) was strongly influenced by positively correlated variables describing Se, Ba and Cd and negatively correlated variables describing Ag, Co, Cs, Mn, Pb, Tl and V; PC2, respectively, by Cu, Mn and Mo (+) and Zn (-); PC3 by Ga (+) and PC4 by Sb (+). Selenium occurred in muscle tissue, liver and kidneys at median concentrations of 0.13, 0.19 and 4.0mg/g dry weight, respectively. These values can be defined as marginally deficient (< 0.6mg Se/kg liver dw) or satisfactory (≤ 3.0mg Se/kg kidneys dw) for the amount required to maintain the Deers body condition and health, depending on the criterion for supplementation used. In terms of human nutritional needs, a relatively high selenium content of kidneys can be beneficial. The muscle meat, liver and kidneys of Red Deer can be considered as a very good source of essential Co, Cr, Cu, Mo, Mn, Se and Zn in the human diet. Lead is generally considered as toxic, and the concentrations found in Red Deer (via the food chain intake) were well below the European Union tolerance limit. Pb from the lead bullets can always create food hygienic problem, if not well recognized during sanitary inspection, and this was noted for one muscle meat sample in this study (5% surveyed). There is no tolerance limit of Cd in game animal meats. The median values of Cd noted in fresh muscle tissue, liver and whole kidneys were 0.07, 0.18, and 3.3mg/kg wet weight, respectively. Cd exists as a chemical element present at trace levels in plants and mushrooms in Deers food chain in background (uncontaminated) areas. When these are consumed by the Deer, the amount of Cd sequestered with metallothioneins and retained in the organ and muscle meat in this study is low enough to be considered safe for human consumption.

Temporal variability in 20 chemical elements content of Parasol Mushroom (Macrolepiota procera) collected from two sites over a few years

Mature specimens of Parasol Mushroom were collected annually in the outskirts of the Siemiany (2000–2003) and Rafa (2001–2003) sites in the northern part of Poland to examine temporal variations and similarities in the composition of 20 chemical elements. Analysis was done under the same condition and using well-validated analytical methods. Elements were determined by inductively coupled plasma–atomic emission spectroscopy and cold vapour–atomic absorption spectroscopy (Hg). The ranges of Ag, Al, Ba, Ca, Cd, Co, Cu, Cr, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr and Zn concentrations in the caps of fruiting bodies were similar (p > 0.05; Mann-Whitney U test) for both geographically distant sites, and these specimens from Rafa were more contaminated with Pb (p < 0.05; Mann-Whitney U test). The annual collections of caps in the Siemiany site varied in Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, Hg, Na, Rb and Sr and contents (0.05 < p < 0.001), while they were similar in Cr, K, Mg, Mn, Ni, P, Pb and Zn (p > 0.05; Mann-Whitney U test). The annual collections of specimens from the Rafa site varied in contents of Ag, Al, Ba, Ca, Fe, Hg, K, Mg, Mn, P, Rb and Zn (p > 0.05), while they were similar in Cd, Co, Cr, Cu, Na, Ni, Pb and Sr (p < 0.05). The results of this study imply that metallic elements content of Parasol Mushroom collected at the same undisrupted sites, and hence keeping the same geochemical condition for mushroom development and fructification (the same stands and probably the same mycelia), can fluctuate over the years or the life-span of mycelium. Hence, when assessing the nutritional value of essential metallic elements and status of non-essential or toxic metallic elements in Parasols Mushroom caps (and probably also of other mushrooms species) to man, the possible fluctuation in contents over time have to be taken into account.

Mercury in bay bolete (Xerocomus badius): bioconcentration by fungus and assessment of element intake by humans eating fruiting bodies

Concentrations of mercury (Hg) were determined in 221 specimens of bay bolete and in 221 samples of corresponding forest topsoil layer (0–10 cm) collected from 18 sites across geographically and industrially diverse regions of Poland in 2000–2008. Mercury concentrations in caps and stipes of bay bolete were strongly correlated (p < 0.0001), whereas the relationship between the Hg concentrations in soil and mushrooms varied depending on the sampling location. The bay bolete showed a lower bioconcentration potential of Hg at sites with elevated soil Hg concentrations and a higher bioconcentration at sites with lower Hg concentrations in soil. In view of Hg content, the consumption of bay boletes (caps or whole mushrooms) at the regions surveyed at least at a rate up to 2.5 kg per capita weekly in a mushrooming season is safe and will not result in exceeding of currently allowable Hg intake doses.

Profile of trace elements in Parasol Mushroom (Macrolepiota procera) from Tucholskie Forest

The aim of this study was to determine 19 elements contents and bioconcentration potential in fruiting bodies of Parasol Mushroom (Macrolepiota procera) collected from the Tucholskie Forest complex in Poland. Also discussed were Cd, Pb and Hg contents of edible caps in relation to the current regulatory standards. K, P and Mg were particularly abundant in caps and stipes, median values were 38–49, 13, and 1.6–1.6 mg/g dry weight, and followed by Ca, Na and Rb at 110–540, 44–240 and 20–50 μg/g dw, respectively. Concentrations of Al, Fe, Zn, Cu and Mn were from less than 50 to 180 μg/g dw, while concentrations of other elements were ∼l.0 μg/g dw or less. Cu, K, Ag, Cd, Na, Rb, Zn and Hg were bioconcentrated (BCF >1), while Al, Ba, Fe, Mn, Co, Sr, Pb and Cr were not bioaccumulated (BCF <1). Cd and Pb content of Parasol Mushrooms edible caps collected from some sites in the Tucholskie Forest exceed the maximum levels set in the EU for cultivated mushrooms.

Mercury in European Blushers, Amanita rubescens, mushrooms and topsoils: Bioconcentration potential and intake assessment

Total mercury content has been determined in fruiting bodies of European Blushers and topsoils collected from 11 sites across Poland in 2006-2008. Mercury analysis was carried out using a validated analytical method and cold-vapour atomic absorption (CV-AAS). The European Blusher effectively accumulated mercury in fruiting bodies. The mean values of total mercury in caps of European Blushers from background (uncontaminated) areas were from 0.22 to 1.0 (0.067-3.2) and in stipes from 0.16 to 0.65 (0.071-2.7) μg/g dry weight. In topsoil beneath to fruiting bodies, the median Hg concentration at 10 sites in Northern Poland varied between 0.030 and 0.072 (0.0096–0.19) μg/g dw, and in one site in Southern Poland was 0.20 (0.079–0.34) μg/g dw. Data on Hg in European Blushers from different countries were reviewed. The mean concentrations of total Hg in caps of European Blushers from two “pristine” sites in northern part of Poland were ∼1.0 μg/g dw. A meal made with 300–500 g of fresh caps of European Blushers collected at such sites (assuming 90% water content in caps) can result in Hg intake of 0.0003–0.0005 mg Hg/kg bm (assuming a 60 kg bm), which is a dose equipotent to a new provisional tolerable weekly intake (PTWI) value set for inorganic Hg.