Atmospheric emissions of particulate matter-bound heavy metals from industrial sources.

Although industrial activities are significant contributors to atmospheric releases of particulate matter (PM) and associated toxic substances that lead to adverse human health effects, a knowledge gap exists concerning the human health risk resulting from such activities owing to lack of evaluation of industrial emissions. Here, we comprehensively characterized and quantified PM from 118 full-scale industrial plants. The dominant (97.9 %) PM showed diameters of <2.5 µm; 79.0 % had diameters below 1 µm. Annual atmospheric releases of Fe and heavy metals (As, Cd, Cr, Cu, Ni, Pb, Zn) contained in fine PM from these global industrial activities are estimated to be 51,161 t and 69,591 t, respectively. Emissions of heavy metals from these industries cause increased cancer risk, estimated to range from 1461 % to 50,752 %. Five crystalline compounds (ZnO, PbSO4, Mn3O4, Fe3O4, Fe2O3) that can indicate specific industrial sources are identified. Global annual emissions of these toxic compounds in fine PM from the industrial sources are estimated to be 78,635 t. The Global South displayed higher emissions than the Global North. These results are significant for recognizing regional health risks of industrial emissions.

Rare earth contamination of edible vegetation: Ce, La, and summed REE in fungi.

The increasing and diversified use of rare earth elements (REE) is considered a potential source of pollution of environmental media including soils. This work documents critically overview data on the occurrence of REE in the fruiting bodies of wild and farmed species of edible and medicinal mushrooms, as this was identified as the largest published dataset of REE occurrence in foodstuff. Most of the literature reported occurrences of cerium (Ce) and lanthanum (La), but a number of studies lacked data on all lanthanides. The Ce, La, and summed REE occurrences were assessed through the criteria of environmental geochemistry, analytical chemistry, food toxicology, mushroom systematics, and ecology. Ce and La accumulate similarly in fruiting bodies and are not fractionated during uptake, maintaining the occurrence patterns of their growing substrates. Similarly, there is no credible evidence of variable REE uptake because the evaluated species data show natural, unfractionated patterns in accordance with the Oddo-Harkins' order of environmental lanthanide occurrence. Thus, lithosphere occurrence patterns of Ce and La as the first and the third most abundant lanthanides are reflected in wild and farmed mushrooms regardless of substrate and show that Ce is around twice more abundant than La. The current state of knowledge provides no evidence that mushroom consumption at these REE occurrence levels poses a health risk either by themselves or when included with other dietary exposure. Macromycetes appear to bio-exclude lanthanides because independently reported bioconcentration factors for different species and collection sites, typically range from < 1 to 0.001. This is reflected in fruiting body concentrations which are four to two orders of magnitude lower than growing substrates. KEY POINTS: •Original REE occurrence patterns in soils/substrates are reflected in mushrooms •No evidence for the fractionation of REE during uptake by fungi •Mushrooms bio-exclude REE in fruiting bodies.

Risks for animal and human health related to the presence of polychlorinated naphthalenes (PCNs) in feed and food.

EFSA was asked for a scientific opinion on the risks for animal and human health related to the presence of polychlorinated naphthalenes (PCNs) in feed and food. The assessment focused on hexaCNs due to very limited data on other PCN congeners. For hexaCNs in feed, 217 analytical results were used to estimate dietary exposures for food-producing and non-food-producing animals; however, a risk characterisation could not be performed because none of the toxicological studies allowed identification of reference points. The oral repeated dose toxicity studies performed in rats with a hexaCN mixture containing all 10 hexaCNs indicated that the critical target was the haematological system. A BMDL20 of 0.05 mg/kg body weight (bw) per day was identified for a considerable decrease in the platelet count. For hexaCNs in food, 2317 analytical results were used to estimate dietary exposures across dietary surveys and age groups. The highest exposure ranged from 0.91 to 29.8 pg/kg bw per day in general population and from 220 to 559 pg/kg bw per day for breast-fed infants with the highest consumption of breast milk. Applying a margin of exposure (MOE) approach, the estimated MOEs for the high dietary exposures ranged from 1,700,000 to 55,000,000 for the general population and from 90,000 to 230,000 for breast-fed infants with the highest consumption of breast milk. These MOEs are far above the minimum MOE of 2000 that does not raise a health concern. Taking account of the uncertainties affecting the assessment, the Panel concluded with at least 99% certainty that dietary exposure to hexaCNs does not raise a health concern for any of the population groups considered. Due to major limitations in the available data, no assessment was possible for genotoxic effects or for health risks of PCNs other than hexaCNs.

An updated global overview of the manufacture and unintentional formation of polychlorinated naphthalenes (PCNs).

This review updates information on the historical manufacture and unintentional production of polychlorinated naphthalenes (PCNs). The direct toxicity of PCNs as a result of occupational human exposure and through contaminated feed in livestock was recognised decades ago, making PCNs a precursor chemical for consideration in occupational medicine and occupational safety. This was confirmed by the listing of PCNs by the Stockholm Convention as a persistent organic pollutant in the environment, food, animals and humans. PCNs were manufactured globally between 1910 ∼ 1980, but reliable data on the volumes produced or national outputs are scarce. A total figure for global production would be useful for the purposes of inventory and control and it is clear that combustion related sources such as waste incineration, industrial metallurgy and use of chlorine are current major sources of PCNs to the environment. The upper bound estimate of total global production has been put at 400,000 metric tons but the amounts (at least, many 10 s of tonnes) that are currently emitted unintentionally every year through industrial combustion processes should also be inventoried along with estimates for emissions from bush and forest fires. This would however require considerable national effort, financing and co-operation from source operators. The historical (1910-1970 s) production and resulting emissions through diffusive/evaporative releases through usage, are still reflected in documented occurrence and patterns of PCNs in human milk in Europe and other locations worldwide. More recently, PCN occurrence in human milk from Chinese provinces has been linked to local unintentional emissions from thermal processes.

Industrial source identification of polyhalogenated carbazoles and preliminary assessment of their global emissions.

Polyhalogenated carbazoles (PHCZs) are emerging global pollutants found in environmental matrices, e.g., 3000 tonnes of PHCZs have been detected in the sediments of the Great Lakes. Recognition of PHCZ emissions from ongoing industrial activities worldwide is still lacking. Here, we identify and quantify PHCZ emissions from 13 large-scale industries, 12 of which previously have no data. Congener profiles of PHCZs from investigated industrial sources are clarified, which enables apportioning of PHCZ sources. Annual PHCZ emissions from major industries are estimated on the basis of derived emission factors and then mapped globally. Coke production is a prime PHCZ emitter of 9229 g/yr, followed by iron ore sintering with a PHCZ emission of 3237 g/yr. China, Australia, Japan, India, USA, and Russia are found to be significant emitters through these industrial activities. PHCZ pollution is potentially a global human health and environmental issue.

Residue Distribution and Daily Exposure of Per- and Polyfluoroalkyl Substances in Indica and Japonica Rice.

Per- and polyfluoroalkyl substances (PFAS) have excellent chemical stability but have adverse environmental impacts of concern. Furthermore, bioaccumulation of PFAS in rice varieties─which is the essential staple food crop in Asia─has not been verified. Therefore, we cultivated Indica (Kasalath) and Japonica rice (Koshihikari) in the same Andosol (volcanic ash soil) paddy field and analyzed the air, rainwater, irrigated water, soil, and rice plants for 32 PFAS residues, throughout the cultivation to human consumption. During the rice cultivation period, the cultivation environment in atmospheric particulate matter (PM) constituted perfluoroalkyl carboxylic acids (PFCAs), with minimal perfluorinated sulfonic acids (PFSAs). Furthermore, perfluorooctanesulfonic acid (PFOS) migrates at a PM > 10 to drop in a cultivation field and was conducive to leakage and accumulation of PFCAs in air particles in the field environment. Moreover, precipitation was a sources of irrigation water contamination, and cultivated soil with a high carbon content could capture PFSAs and PFCAs (over C10). There were no major differences in residual PFAS trends in the rice varieties, but the distribution of PFAS in the growing soil, air, and rainwater differed. The edible white rice part was mainly affected by irrigation water in both varieties. Monte Carlo simulations of daily exposure assessments of PFOS, PFOA, and perfluorononanic acid showed similar results for Indians consuming Indica rice and Japanese consuming Japonica rice. The results indicate that the ultratrace PFAS residue concentrations and their daily exposure were not cultivar-specific.

In vitro gastrointestinal digestion and bioavailability of lithium from processed lithiated and nonlithiated white Agaricus bisporus mushrooms.

AIM: In order to avoid side effects of lithium doses in some patients, some commonly cultivated mushroom species including A. bisporus have been successfully lithiated, with the potential to provide more acceptable sources of Li. This study assessed the in vitro release (potential bioaccessibility) and possible intake of Li using the action of artificial gastrointestinal juices on lithiated and nonlithiated (control) button mushrooms (Agaricus bisporus) that were subjected to certain modes of culinary processing. METHODS: In the in vitro release study, mushrooms were processed using a number of routinely used domestic treatments including rehydrating dried mushrooms, blanching and blanching followed by pickling of fresh or frozen mushrooms. The in vitro digestion procedure used artificial gastrointestinal juices in a two-stage methodology that was adapted from 'The Bioaccessibility Research Group of Europe' method. The Li concentrations were determined using an inductively coupled argon plasma-dynamic reactive cell-mass spectrometer. RESULTS: Lithium was found to be more bioaccessible from caps of lithiated mushrooms compared with nonlithiated. Releases from the caps and stipes of blanched or blanched and then pickled mushrooms through gastric digestion ranged from 32 ± 2 to 50 ± 1% relative to the dried product and was lower for gastrointestinal digestion, which ranged from 16 ± 1 to 20 ± 1%. CONCLUSION: Losses of Li sustained through blanching or blanching followed by pickling of fresh mushrooms (41-87% wet weight) combined with limited accessibility during gastrointestinal release (16-55%) result in much lower bioavailability of the dose from lithiated products. A 300-g meal would provide <5% of the Li (6 mg) required for potential preventative treatments, such as reducing suicide rates and lowering dementia risk.

Scandium, yttrium, and lanthanide occurrence in Cantharellus cibarius and C. minor mushrooms.

There is a dearth of data on rare earth elements (REE), yttrium and scandium in foods which extends also to baseline datasets for edible wild mushrooms, though this has started to change in the last decade. Concentrations and shale normalized patterns of REE and Y (REY) were studied by using inductively coupled plasma-quadrupole mass spectrometer in 22 pools (2235 specimens) of Cantharellus cibarius (Golden Chanterelle) collected in Poland and also a pool of C. minor (Small Chanterelle) (153 specimens) from Yunnan (Chinese Province). The total REY plus Sc varied in C. cibarius from 10 to 593 µg kg-1 dw whereas that for the Yunnan's C. minor was 2072 µg kg-1 dw. C. minor from Yunnan has higher REY and Sc compared to the C. cibarius. Sc concentrations in twenty C. cibarius pools were below 1 µg kg-1 dw, but 17 and 27 µg kg-1 dw were detected at the other two sites and 66 µg kg-1 dw was detected in C. minor. The median Y content of C. cibarius and C. minor was 22 µg kg-1 dw and 200 µg kg-1 dw. The difference in REY and Sc concentrations and shale normalized patterns between mushrooms from Poland and Yunnan seems to reflect the regional difference in concentration and composition of these elements in the soil bedrock.

Letter to the editor: Comment on "multiannual monitoring (1974-2019) of rare earth elements in wild growing edible mushroom species in Polish forests" by Siwulski et al. https://doi.org/10.1016/j.chemosphere.2020.127173. A recurring question - What are the real concentrations and patterns of REE in mushrooms?

Siwulski et al. (2020) investigated the occurrence of the lanthanides (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu), scandium (Sc) and yttrium (Y) in 4 species of wild mushrooms, which were sampled over a 45 years period in Poland. The reported mean lanthanide concentrations for mushrooms were in the range from 539 to 1601 µg kg-1 dry weight. These values are considered as highly elevated in the light of data published earlier for the same species, where the analytical results were assessed as not being biased by errors (these could arise from contamination of the samples with soil dust or unsuitable choice of analytical methodology including the use of unsuitable analytical instrumentation for measurement). It has long been established that the lanthanides are naturally distributed in ores, soil bedrock, soils, natural waters and plants in a pattern that reflects the Oddo-Harkins rule. This pattern is correspondingly reflected in fungi, including the same species and have been published earlier by other authors. However, when the individual lanthanide concentration data of B. edulis, I. badia, L. scabrum and M. procera from the study by Siwulski et al. are plotted, they do not display the expected sawtooth (zigzag) concentration pattern - in other words, the concentration data do not follow the Oddo-Harkins rule. Lanthanides are naturally found in very low concentration in foods including wild mushrooms. There is a striking lack of convergence in the results obtained for ICP-MS techniques, and the results obtained from ICP-OES measurement (as used by Siwulski et al.). If the reasons discussed here for anomalies in the reported lanthanides data hold true, how does this affect the data for other elements in mushrooms reported in the commented article?

Comment on "Worldwide basket survey of multielemental composition of white button mushroom Agaricus bisporus": The credibility of the concentration data reported for REE are questioned - are they reliable enough to be included in the database on nutrients in mushrooms?

The focus of this comment is on the Lanthanides (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) which, together with Sc and Y are also called the rare earth elements (REE). Individual REE have similar chemical properties and can be treated as a group. They behave similarly in the environment and in food webs. However, the determination of REE in foods, including edible mushrooms is analytically very challenging. In study by Siwulski et al. (2020) concentrations were reported for Ce, Nd, Sm, La, Sm and Tm, but the others were not detected above the method quantification limit. The sum of Ce (340-2730 µg kg-1 dw), Nd (10-1220 µg kg-1 dw), Sm (10-420 µg kg-1 dw), La (10-130 µg kg-1 dw), Sm (10-420 µg kg-1 dw), Tm (10-170 µg kg-1 dw) in 32 samples of A. bisporus was in the range of 430-3510 µg kg-1 dry weight. The first visible characteristic is a large difference in the concentrations of Ce, Nd, Sm, La and Tm between the A. bisporus samples and various wild species and cultivated Cyclocybe cylindracea and Pleurotus ostreatus. Secondly, there is no correspondence with the Oddo-Harkins order and the concentrations pattern of Ce, Nd, Sm, La and Tm reported for the A. bisporus samples. The pattern is clearly different from that observed in the wild mushrooms and the two cultivated species reported by other studies. The ICP-OES and also the low resolution ICP-MS determination of REE directly from a fungal digest can suffer from spectral interferences of different types including an effect of the matrix which have to be overcome in the course of reliable and controlled analysis of REE.

A critical review of the occurrence of scandium and yttrium in mushrooms.

Scandium (Sc) and Yttrium (Y) along with the other rare earth elements (REE) are being increasingly extracted to meet the escalating demand for their use in modern high technology applications. Concern has been voiced that releases from this escalating usage may pollute environments, including the habitats of wild species of mushrooms, many of which are foraged and prized as foods. This review collates the scarce information on occurrence of these elements in wild mushrooms and also reviews soil substrate levels, including forested habitats. Sc and Y occurred at lower levels in mushrooms (<1.0-1000 µg kg-1 dw for Sc and<1.8-1500 µg kg-1 dw for Y) compared to the corresponding range for the sum of the lanthanides in the same species (16-8400 µg kg-1 dw). The reported species showed considerably more variation in Y contents than Sc which show a narrow median distribution range (20-40 µg kg-1 dw). Data allowing temporal examination was very limited but showed no increasing trend between the 1970s to 2019, nor were any geographical influences apparent. The study of the essentiality, toxicity or other effects of REE including Sc and Y at levels of current dietary intake are as yet undefined. High intake scenarios using the highest median concentrations of Sc and Y, resulted in daily intakes of 1.2 and 3.3 µg respectively from 300 g portions of mushroom meals. These could be considered as low unless future toxicological insights make these intake levels relevant.

Occurrence, bio-concentration and distribution of rare earth elements in wild mushrooms.

Using validated methodology, this study explores the bioconcentration potential and status of rare earth elements (REE) and yttrium (Y) in wild mushrooms collected from Belarus, China and Poland and in the associated forest topsoil. Baseline data for REE and Y distributions in the morphological parts of the fruiting bodies of Caloboletus calopus, Cantharellus cibarius, Craterellus cornucopioides, Imleria badia, Laccaria amethystina, Lactifluus piperatus, Leccinum scabrum and Suillus grevillei are presented. REE were in the range of 14 to 42 mg kg-1 dw in forest topsoil and from 35 to 48 mg kg-1 dw in profiled soil layers from the Sobowidz site in Poland. Forest topsoil sampled in Belarus contained 67 mg kg-1 dw. Yttrium concentrations in soil ranged from 2.9 to 10 mg kg-1 dw. The median REE concentration in wild mushrooms was around 200 µg kg-1 dw (20 µg kg-1 fresh weight). This implies negligible dietary intake even for high level consumers. The bioconcentration factors (BCF) of individual REE and Y ranged from 0.0002 to 0.0229, showing bio-exclusion. The BCF tended to be similar for groups of REE (La to Tb and Dy to Lu) depending on the mushroom species and site. REE from Dy to Lu were better bioconcentrated than those from La to Tb. The similarity of the BCFs of individual REE by species at a given site implies the same absorption pathway, although a lower concentration in the topsoil favoured bioconcentration. REE and Y concentrations varied between species as well as within the same species between sites. Their accumulation in mushrooms appears to reflect condition at the site of collection, and may also be species-specific but confirming this would require further investigation of different species, topsoils and sites.

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.

Rare Earth Elements in Boletus edulis (King Bolete) Mushrooms from Lowland and Montane Areas in Poland.

Mining/exploitation and commercial applications of the rare-earth elements (REEs: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in the past 3 decades have raised concerns about their emissions to the environment, possible accumulation in food webs, and occupational/environmental health effects. The occurrence and distribution of REEs Y and Sc in the fruitbodies of Boletus edulis collected from geographically diverse regions in Poland were studied in 14 composite samples that were derived from 261 whole fruiting bodies. Individual REE median concentrations ranged from 0.4-95 µg kg-1 dry weight (dw). The summed REE concentrations varied widely, with a median value of 310 µg kg-1 dw and a range of 87 to 758 µg kg-1. The Sc and Y median concentrations (dw) were 35 and 42 µg kg-1, respectively. Ce, La, and Nd, with median values of 95, 51, and 32 µg kg-1, respectively, showed the highest occurrence. B. edulis collected from a forested area formerly used as a military shooting range-possibly a historically contaminated site-had an elevated summed REE content of 1796 µg kg-1. REE concentrations were generally low in Polish King Bolete. Dietary intake from a mushroom meal was negligible, posing no health risk to consumers.

The toxicological profile of polychlorinated naphthalenes (PCNs).

The legacy of polychlorinated naphthalenes (PCNs) manufactured during the last century continues to persist in the environment, food and humans. Metrological advances have improved characterisation of these occurrences, enabling studies on the effects of exposure to focus on congener groups and individual PCNs. Liver and adipose tissue show the highest retention but significant levels of PCNs are also retained by the brain and nervous system. Molecular configuration appears to influence tissue disposition as well as retention, favouring the higher chlorinated (≥ four chlorines) PCNs while most lower chlorinated molecules readily undergo hydroxylation and excretion through the renal system. Exposure to PCNs reportedly provokes a wide spectrum of adverse effects that range from hepatotoxicity, neurotoxicity and immune response suppression along with endocrine disruption leading to reproductive disorders and embryotoxicity. A number of PCNs, particularly hexachloronaphthalene congeners, elicit AhR mediated responses that are similar to, and occur within similar potency ranges as most dioxin-like polychlorinated biphenyls (PCBs) and some chlorinated dibenzo-p-dioxins and furans (PCDD/Fs), suggesting a relationship based on molecular size and configuration between these contaminants. Most toxicological responses generally appear to be associated with higher chlorinated PCNs. The most profound effects such as serious and sometimes fatal liver disease, chloracne, and wasting syndrome resulted either from earlier episodes of occupational exposure in humans or from acute experimental dosing of animals at levels that reflected these exposures. However, since the restriction of manufacture and controls on inadvertent production (during combustion processes), the principal route of human and animal exposure is likely to be dietary intake. Therefore, further investigations should include the effects of chronic lower level intake of higher chlorinated PCN congeners that persist in the human diet and subsequently in human and animal tissues. PCNs in the diet should be evaluated cumulatively with other similarly occurring dioxin-like contaminants.