A method for the analysis of methylmercury and total Hg in fungal matrices.

The aim of the study was to develop an efficient method for the determination of monomethyl-mercury (MeHg) and total mercury (THg) content in materials such as fungal sporocarps and sclerotia. Certified Reference Materials (CRMs) with the assigned values of MeHg and THg as well as the control materials (dried mushrooms) with known content of THg were evaluated for method validation. Recovery of MeHg from reference materials was at the following levels: from tuna fish at 87.0 ± 2.3% (THg at 101.9 ± 1.2%), from fish protein at 99.4 ± 1.3% (THg at 92.70 ± 0.41%), and from dogfish liver at 96.45 ± 0.73%. Recovery of THg from the fungal control material CS-M-5 was at 104.01 ± 0.60% (contribution of MeHg in THg content was at 6.2%), from CS-M-4 at 101.1 ± 2.0% (contribution at 3.2%), from CS-M-3 at 100.55 ± 0.67% (contribution at 0.6%), and from CS-M-2 at 101.5 ± 2.7% (contribution at 3.7%). The content of MeHg in randomly selected wild fungi and their morphological parts was in the range from 0.006 to 0.173 mg kg-1 dry weight (dw). In the case of THg, the concentration values were in the range from 0.0108 to 10.27 mg kg-1 dw. The MeHg content in the control materials with the assigned THg values was determined. Since the control materials play an important role in all elements of the quality assurance system of measurement results, they can be used to analyse MeHg as the first control material for fungi. KEY POINTS: • An extraction procedure for MeHg analysis in fungi was developed and optimized. • Recovery of MeHg from the certified reference non-fungal materials was > 87%. • Fungal control materials with assigned THg concentration can serve also for MeHg analysis.

Total mercury and methylmercury (MeHg) in braised and crude Boletus edulis carpophores during various developmental stages.

We collected and processed Boletus edulis (King Bolete) carpophores grouped in four batches based on their developmental stage (button stage, young-white, large-white, and large-yellow). The study aimed, for the first time, to examine the B. edulis content and effect of braising and to estimate the intake of total mercury (THg) and methylmercury (MeHg) from a single meal based on whole (wet) weight (ww) and dry weight (dw). In braised carpophores, THg concentrations ranged from 0.2668 ± 0.0090 to 0.5434 ± 0.0071 mg kg-1 ww at different developmental stages, whereas crude products concentrations ranged from 0.1880 ± 0.0247 to 0.2929 ± 0.0030 mg kg-1 ww. The button stage crude carpophores were more highly contaminated with THg than at later stages of maturity, but MeHg levels were lower (p < 0.0001). On the other hand, braised button stage carpophores showed more MeHg than at later maturity stages. MeHg contributed at 1.9 ± 0.7% in THg in crude mushrooms and at 1.4 ± 0.3% in braised meals. The effect of braising was to increase the average THg and MeHg contents in fresh mushroom meals by 52 ± 31% and 53 ± 122% respectively, but a reduction of 40 ±14% and 40 ± 49% respectively was seen on a dw basis. The potential intakes of THg and MeHg from braised meals of B. edulis studied were small and considered safe.

The effects of different cooking modes on the 137Cs, 40K, and total K content in Boletus edulis (King Bolete) mushrooms.

This study aimed to get an insight into the effects of household processing on the leaching behaviour of 137Cs and 40K from fresh, frozen and dried Boletus edulis (King Bolete) mushrooms. Three processes were investigated-blanching, blanching and pickling, and drying followed by grinding and soaking. The activity concentrations of 137Cs and 40K in the fresh unprocessed mushrooms were 270 Bq kg-1 dry biomass (27 Bq kg-1 whole weight) and 590 Bq kg-1 db (59 Bq kg-1 ww), respectively. Blanching of fresh mushrooms decreased 137Cs activity by 55%, and 40K activity by 34%, and blanching of deep-frozen mushrooms caused a reduction of 52% and 44% (db) (equivalent to whole weight reductions of 37% and 8.5%, and 67% and 22%, respectively). Blanching and pickling of fresh mushrooms decreased 137Cs activity by 83% and 40K activity by 87%, while blanching deep-frozen mushrooms resulted in decreases of 88% and 80% (db) (whole weight decreases of 77% and 81%, and by ~ 84% and 72%, respectively). This study confirms earlier reports that blanching of fresh or frozen mushrooms alone is not as efficient at removing 137Cs as blanching followed by pickling. The study also shows that the initial rate of fruiting body disintegration and pre-preparation (comparing fresh, deep-frozen, or dried and ground) can have an impact on the leaching rate of the water soluble fraction of metallic elements.

137Caesium, 40K and total K in Boletus edulis at different maturity stages: Effect of braising and estimated radiation dose intake.

We studied activity concentrations of artificial 137Cs and natural 40K and concentration of total potassium (K) in Boletus edulis at different maturity stages (button, young - white, large - white and large - yellow), and the effect of braising and human dietary intake. Mushrooms were collected from the northern region of Poland in 2019. The 137Cs activity concentration was significantly higher in raw and braised button stage samples and decreased as the fruitbody matured, but conversely, 40K was lower in the raw button stage than in older fruitbodies. 137Cs activity concentrations in raw, button stage B. edulis were 36 ± 1 Bq kg-1 ww (360 ± 1 Bq kg-1 dw), increasing to 70 ± 2 Bq kg-1 ww (290 ± 7 Bq kg-1 dw) when braised. This activity was around fourteen-fold higher (p < 0.0001) than at higher maturity stages which showed 2.5 ± 0.7 Bq kg-1 ww (25 ± 7 Bq kg-1 dw) in raw and 4.9 ± 0.7 Bq kg-1 ww (19 ± 4 Bq kg-1 dw) in braised fruitbodies. In comparison to raw B. edulis, braising enriched the activity concentrations of 137Cs at 110 ± 69% and 40K at 80 ± 56% on a whole (wet) weight basis.

Mercury in traditionally foraged species of fungi (macromycetes) from the karst area across Yunnan province in China.

The objective of this study is to better quantify the occurrence, intake, and potential risk from Hg in fungi traditionally foraged in SW China. The concentrations and intakes of Hg were measured from 42 species including a "hard" flesh type polypore fungi and a" soft" flesh type edible species that are used in traditional herbal medicine, collected during the period 2011-2017. Three profiles of forest topsoil from the Zhenyuan site in 2015 and Changning and Dulong sites in 2016 were also investigated. The concentrations of Hg in composite samples of polypore fungi were usually below 0.1 mg kg-1 dry weight (dw) but higher levels, 0.11 ± 0.01 and 0.24 ± 0.00 mg kg-1 dw, were noted in Ganoderma applanatum and Amauroderma niger respectively, both from the Nujiang site near the town of Lanping in NW Yunnan. Hg concentrations in Boletaceae species were usually well above 1.0 mg kg-1 dw and as high as 10 mg kg-1 dw. The quality of the mushrooms in this study in view of contamination with Hg showed a complex picture. The "worst case" estimations showed probable intake of Hg from 0.006 µg kg-1 body mass (bm) ("hard" type flesh) to 0.25 µg kg-1 bm ("soft" flesh) on a daily basis for capsulated products, from 17 to 83 µg kg-1 bm ("soft" flesh) in a meal ("hard" type flesh mushrooms are not cooked while used in traditional herbal medicine after processing), and from 0.042 to 1.7 and 120 to 580 µg kg-1 bm on a weekly basis, respectively. KEY POINTS: • Polypore species were slightly contaminated with Hg. • Hg maximal content in the polypore was < 0.25 mg kg-1 dry weight. • Many species from Boletaceae family in Yunnan showed elevated Hg. • Locals who often eat Boletus may take Hg at a dose above the daily reference dose.

Accumulation Pattern of Inorganic Elements in Scaly Tooth Mushroom (Sarcodon imbricatus) from Northern Poland.

Several studies have documented contamination levels and daily intake of metallic elements from foodstuffs including rice, maize, pulses, vegetables, fruits, fish, meat, egg, milk etc., however, limited literature is available on metal contamination levels in wild growing mushrooms and possible human exposure via consumption of it. Sarcodon imbricatus is an edible mushroom, commonly consumed in many parts of the world. Very few studies have been conducted on inorganic elemental composition in fruiting bodies (edible part) of this fungus. In this study, elements such as silver (Ag), aluminum (Al), barium (Ba), calcium (Ca), cadmium (Cd), cobalt (Co,) chromium (Cr), copper (Cu), iron (Fe), mercury (Hg), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), nickel (Ni), phosphorous (P), lead (Pb), rubidium (Rb), strontium (Sr) and zinc (Zn) were measured in caps and stems of fruiting bodies of S. imbricatus collected from the Wdzydze forests in Central and the Augustowska Primeval forest in Eastern Poland. Results revealed that a wide variation in concentrations of various metals in caps and stems samples collected from the two forests. Toxic metallic elements such as Cd and Hg showed preferential accumulation in caps than stems samples from both the forests. However, the concentrations of Cd, Hg and Pb in the mushroom samples were below the established weekly intake tolerance limits.

Occurrence, distribution and estimated intake of mercury and selenium from sclerotia of the medicinal fungus Wolfiporia cocos from China.

The contamination and distribution of mercury and selenium in the Chinese medicinal fungus Wolfiporia cocos was investigated. The sclerotial mercury concentrations ranged from 0.0043 to 0.027 mg kg1 dry biomass (db) in the inner white part and 0.019-0.074 mg kg-1 db in the shell (outer part), while selenium concentrations ranged from < 0.00048 to 0.0040 mg kg-1 db (white) and 0.0034-0.038 mg kg-1 db (shell). Positive correlations were found for mercury, as well as for mercury and selenium but they were not consistent for both morphological parts. Mercury concentrations exceeded selenium in 16 of 17 white part pools (molar quotient 0.53 to > 10) and in 11 of 17 shell pools (quotient 0.37 to 3.2). The estimated maximal exposure to mercury contained in sclerotial products based on 45 g per capita daily intake for a 60 kg individual over one week, was 0.000020 mg kg-1 body mass (bm; white) and 0.000055 mg kg-1 bm (shell) on a daily basis, and 0.00014 mg kg-1 bm (white) and 0.00039 mg kg-1 bm (shell) on a weekly basis. Relative to mercury, the corresponding intake rates of selenium were considered very low, i.e., they averaged on a daily basis at 0.00075 µg kg-1 bm (white) and 0.0097 µg kg-1 bm (shell) with maximum intake at 0.0030 µg kg-1 bm (white) and 0.028 µg kg-1 bm (shell).

Preferential accumulation of inorganic elements in Amanita muscaria from North-eastern Poland.

Concentrations of Al, Ba, Cd, Ca, Co, Cu, Fe, K, Mg, Mn, Hg, Rb, Ag, Na, Sr and Zn were analysed in fruiting bodies of A. muscaria. This mushroom is considered conditionally edible, since parboiling can detoxify its fruiting bodies from the hallucinogens and render it edible. The specific purpose of the research is the little-known phenomenon of the variability of mineral composition of mushrooms for generations harvested in the same forest areas - both in terms of their nutritional value and anthropogenic influences. Fungal materials were digested in nitric acid and analysed by a validated methods using inductively coupled plasma optical emission spectrometer (ICP-OES) and cold - vapor atomic absorption spectroscopy (CV-AAS). A. muscaria collected in the same area over the period of four years showed fluctuations in the concentrations of the essential elements Co, Cu, Fe, K, Mn, Na and Zn (p < 0.05; U Mann-Whitney test), while only Ca and Mg (p > 0.05) levels were similar. In addition, concentrations of Ag, Al, Ba, Cd, Rb and Sr in fruiting bodies fluctuated, while remained at a similar level for Hg. It is important to note that statistically significant variations in levels of several inorganic elements accumulated in A. muscaria would imply a more careful consideration would be required when assessing the nutritional value of mushroom species.

Mercury in forest mushrooms and topsoil from the Yunnan highlands and the subalpine region of the Minya Konka summit in the Eastern Tibetan Plateau.

This study aimed to investigate and discuss the occurrence and accumulation of mercury in the fruiting bodies of wild-growing fungi (Macromycetes) collected from montane forests in two regions of southwestern China with differences in soil geochemistry, climate and geographical conditions. Fungal mycelia in soils of the subalpine region of the Minya Konka (Gongga Mountain) in Sichuan and in the highlands of Yunnan efficiently accumulated mercury in fruiting bodies (mushrooms). The examined sites in Yunnan with highly mineralized red and yellow soils showed Hg contents ranging from 0.066 to 0.28 mg kg-1 dry biomass (db) which is roughly similar to the results obtained for samples collected from sites with dark soils relatively rich in organic matter from a remote, the subalpine region of Minya Konka. Due to the remoteness of the subalpine section of Minya Konka, as well as its elevation and climate, airborne mercury from long-range transport could be deposited preferentially on the topsoil and the Hg levels determined in soil samples taken beneath the fruiting bodies were up to 0.48 mg kg-1 dry matter. In Yunnan, with polymetallic soils (Circum-Pacific Mercuriferous Belt), Amanita mushrooms showed mercury in caps of fruiting bodies of up to 7.3 mg kg-1 dry biomass. Geogenic Hg from the mercuriferous belt seems to be the overriding source of mercury accumulated in mushrooms foraged in the regions of Yunnan, while long-range atmospheric transport and subsequent deposition are the mercury sources for specimens foraged in the region of Minya Konka.

Evaluation of vulnerability of Suillus variegatus and Suillus granulatus mushrooms to sequester mercury in fruiting bodies.

This work determined the mercury (Hg) contents and bioconcentration potential of two Suillus mushrooms, and the probable dietary intake of this element from a mushroom meal. The determination of total Hg content of fungal and soil samples was performed using cold-vapour atomic absorption spectroscopy by a direct sample thermal decomposition coupled with gold wool trap of Hg and its further desorption and quantitative measurement at a wavelength of 253.7 nm. The median values of Hg contents (mg kg(-1) dry biomass) in 213 specimens of S. variegatus from 12 background areas varied widely from 0.087 to 0.51 for caps and from 0.041 to 0.24 for stipes. In 52 specimens of S. granulatus, the Hg contents ranged from 0.30 to 0.41 for caps and from 0.058 to 0.14 for stipes. Both species could be classified as moderate accumulators of Hg and the median bioconcentration factor values ranged from 7.0 to 14 (caps) and 2.1 to 13 (stipes) for S. variegatus and 9.5 (caps) and 1.3 (stipes) for S. granulatus. The estimated intake rates of Hg with the consumption of 300-g caps were from 0.0026 to 0.015 per capita or from 0.000037 to 0.00022 mg kg(-1) body mass and this do not indicate any cause for concern associated with eating a meal once or more in a week during the mushrooming season.

Mercury bioaccumulation by Suillus bovinus mushroom and probable dietary intake with the mushroom meal.

This paper reports the results of the study of the efficiency of accumulation and distribution of mercury (Hg) in the fruiting bodies of fungus Suillus bovinus and the probable dietary intake of Hg and the potential health risk. Fungal fruiting bodies and soil materials were collected from 13 background areas in the northern part of Poland between 1993 and 2013. Mercury in the caps of fruiting bodies varied from 0.10 ± 0.06 to 0.79 ± 0.40 mg kg(-1) dry biomass and in the stipes from 0.083 ± 0.028 to 0.51 ± 0.22 mg kg(-1) dry biomass. The mean values of cap to stipe Hg content quotient varied from 1.3 ± 0.2 to 2.6 ± 0.6. The Hg content in the upper 0-10 cm layer of soil substrate varied from 0.015 ± 0.004 to 0.031 ± 0.019 mg kg(-1) dry biomass. S. bovinus could be considered as an efficient accumulator of Hg, at least from low level polluted soils, and the values of Hg bioconcentration factor (BCF) varied from 6.4 ± 2.2 to 45 ± 20 for caps and from 3.8 ± 1.4 to 29 ± 11 for stipes. A conventional meal (300 g) portion of S. bovinus foraged from background areas provides Hg dose far below the provisionally tolerable weekly intake or recommended reference dose set for this element by authorities. An examination of published data on Hg in fruiting bodies of fungi genus Suillus showed low contamination of specimens foraged from background areas. Also reviewed are published data on Hg in fungi genus Suillus collected worldwide.

Accumulation and distribution of mercury in fruiting bodies by fungus Suillus luteus foraged in Poland, Belarus and Sweden.

Presented in this paper is result of the study of the bioconcentration potential of mercury (Hg) by Suillus luteus mushroom collected from regions within Central, Eastern, and Northern regions of Europe. As determined by cold-vapor atomic absorption spectroscopy, the Hg content varied from 0.13 ± 0.05 to 0.33 ± 0.13 mg kg(-1) dry matter for caps and from 0.038 ± 0.014 to 0.095 ± 0.038 mg kg(-1) dry matter in stems. The Hg content of the soil substratum (0-10 cm layer) underneath the fruiting bodies showed generally low Hg concentrations that varied widely ranging from 0.0030 to 0.15 mg kg(-1) dry matter with mean values varying from 0.0078 ± 0.0035 to 0.053 ± 0.025 mg kg(-1) dry matter, which is below typical content in the Earth crust. The caps were observed to be on the richer in Hg than the stems at ratio between 1.8 ± 0.4 and 5.3 ± 2.6. The S. luteus mushroom showed moderate ability to accumulate Hg with bioconcentration factor (BCF) values ranging from 3.6 ± 1.3 to 42 ± 18. The consumption of fresh S. luteus mushroom in quantities up to 300 g week(-1) (assuming no Hg ingestion from other foods) from background areas in the Central, Eastern, and Northern part of Europe will not result in the intake of Hg exceeds the provisional weekly tolerance limit (PTWI) of 0.004 mg kg(-1) body mass.

Evaluation of Mercury Contamination in Fungi Boletus Species from Latosols, Lateritic Red Earths, and Red and Yellow Earths in the Circum-Pacific Mercuriferous Belt of Southwestern China.

For the first time, highly elevated levels of mercury (Hg) have been documented for several species of the edible Fungi genus Boletus growing in latosols, lateritic red earths, and red and yellow earths from the Yunnan province of China. Analysis of Hg concentrations in the genus suggests that geogenic Hg is the dominant source of Hg in the fungi, whereas anthropogenic sources accumulate largely in the organic layer of the forest soil horizon. Among the 21 species studied from 32 locations across Yunnan and 2 places in Sichuan Province, the Hg was found at elevated level in all samples from Yunnan but not in the samples from Sichuan, which is located outside the mercuriferous belt. Particularly abundant in Hg were the caps of fruiting bodies of Boletus aereus (up to 13 mg kg-1 dry matter), Boletus bicolor (up to 5.5 mg kg-1 dry matter), Boletus edulis (up to 22 mg kg-1 dry matter), Boletus luridus (up to 11 mg kg-1 dry matter), Boletus magnificus (up to 13 mg kg-1 dry matter), Boletus obscureumbrinus (up to 9.4 mg kg-1 dry matter), Boletus purpureus (up to 16 mg kg-1 dry matter), Boletus sinicus (up to 6.8 mg kg-1 dry matter), Boletus speciosus (up to 4.9mg kg-1 dry matter), Boletus tomentipes (up to 13 mg kg-1 dry matter), and Boletus umbriniporus (up to 4.9 mg kg-1 dry matter). Soil samples of the 0-10 cm topsoil layer from the widely distributed locations had mercury levels ranging between 0.034 to 3.4 mg kg-1 dry matter. In Yunnan, both the soil parent rock and fruiting bodies of Boletus spp. were enriched in Hg, whereas the same species from Sichuan, located outside the mercuriferous belt, had low Hg concentrations, suggesting that the Hg in the Yunnan samples is mainly from geogenic sources rather than anthropogenic sources. However, the contribution of anthropogenically-derived Hg sequestered within soils of Yunnan has not been quantified, so more future research is required. Our results suggest that high rates of consumption of Boletus spp. from Yunnan can deliver relatively high doses of Hg to consumers, but that rates can differ widely because of large variability in mercury concentrations between species and locations.

Evaluation of the mercury contamination in mushrooms of genus Leccinum from two different regions of the world: Accumulation, distribution and probable dietary intake.

This study focused on investigation of the accumulation and distribution of mercury (Hg) in mushrooms of the genus Leccinum that emerged on soils of totally different geochemical bedrock composition. Hg in 6 species from geographically diverse regions of the mercuriferous belt areas in Yunnan of SW China, and 8 species from the non-mercuriferous regions of Poland in Europe was measured. Also assessed was the probable dietary intake of Hg from consumption of Leccinum spp., which are traditional organic food items in SW China and Poland. The results showed that L. chromapes, L. extremiorientale, L. griseum and L. rugosicepes are good accumulators of Hg and the sequestered Hg in caps were up to 4.8, 3.5, 3.6 and 4.7 mg Hg kg(-1) dry matter respectively. Leccinum mushrooms from Poland also efficiently accumulated Hg with their average Hg content being an order of magnitude lower due to low concentrations of Hg in forest topsoil of Poland compared to the elevated contents in Yunnan. Consumption of Leccinum mushrooms with elevated Hg contents in Yunnan at rates of up to 300 g fresh product per week during the foraging season would not result in Hg intake that exceeds the provisional weekly tolerance limit of 0.004 mg kg(-1) body mass, assuming no Hg ingestion from other foods.

Mercury contamination of fungi genus Xerocomus in the Yunnan province in China and the region of Europe.

This article presents the results of the study on accumulation, distribution, contamination and probable dietary intake of total mercury (THg) in fruiting bodies of several species of Fungi genus Xerocomus, which emerged in the circum-Pacific mercuriferous belt region in southwestern China in Yunnan and beyond of the mercuriferous belts in the region of Europe. The mushrooms X. puniceus (Boletus amygdalinus), X. spadiceus (Boletus ferrugineus) and X. versicolor (X. rubellus) were from the Yunnan land, and X. badius (Boletus badius) was from the region of Europe in Belarus and X. badius, X. chrysenteron, X. ferrugineus, X. versicolor (X. rubellus) and X. subtomentosus from Poland. The THg in the fungal and soil materials was determined using validated method by cold-vapour atomic absorption spectroscopy. Estimated was also probable dietary intake and health risk from THg in Xerocomus spp. examined by consumers. The data showed that THg content of Xerocomus spp. emerged in the European localizations in Poland and Belarus is at an order of magnitude lower level than determined in samples from the Yunnan Province. A reason for an elevated content of THg in mushrooms from Yunnan can be related to abundance of Hg in the geochemical background of soils there. The assessed doses showed that a single meal composed of 300 g of fresh fruiting bodies of X. spadiceus from the Wuding localization in Yunnan in China if consumed once a week will provide THg at dose close to the provisional tolerable weekly intake (PTWI) value set for THg, while doses will be lower for all other localizations in Yunnan and Europe. In the Wuding localization in Yunnan a frequent consumption of X. spadiceus in volume exceeding 300 g of fresh fruiting bodies per week will provide THg at a dose exceeding the value of PTWI.

Mercury in the fairy-ring of Gymnopus erythropus (Pers.) and Marasmius dryophilus (Bull.) P. Karst. mushrooms from the Gongga Mountain, Eastern Tibetan Plateau.

Gongga Mountain or Minya Konka, like the Himalayan Dimension Mountains, has its own microclimate and a 'circum-polar' climate and hence is sensitive to contamination by persistent pollutants that are trapped by cold temperature and wet precipitation. Elemental mercury (Hg) as vapour easy diffuses into the atmosphere and the rate of Hg deposition from global fallout is dependent on locally ambient temperature and precipitation. We investigated the accumulation and distribution of total Hg in two species of mushrooms, Gymnopus erythropus and Marasmius dryophilus, which grew on Gongga Mountain. The fruiting bodies were collected at a height of 2946m above see level. Both species efficiently accumulated Hg. The median values for caps of M. dryophilus and G. erythropus were 1.168 and 3.078, and for stipes 0.573 and 1.636mg/kg dry matter, respectively, and in the beneath litter and soil were 0.13 and 0.15mg/kg dry matter. The Hg contents of the caps of M. dryophilus and the beneath litter and soils from pristine Himalayan forest of 1.168, 0.132 and 0.116mg/kg dry matter (respectively) is high compared to values reported for similar species and soils from background areas in Poland -0.58-0.70 and 0.047-0.048mg/kg dry matter. The absence of industrial activities, urbanization and Hg ore deposits at Gongga Mountain suggests that long-range atmospheric transport and subsequent deposition is the major source of elevated Hg observed in the mushrooms, litter and surface layer of soils in the outskirts of Gongga Mountain maritime glacier that has a peak of 7556m above sea level.