Occurrence, distribution, and associations of essential and non-essential elements in the medicinal and edible fungus "Fuling" from southern China.

In Asian countries, the sclerotia of the wild-grown fungus Pachyma hoelen ("Fuling"), have been used as food and as medicinal products for centuries. To close the knowledge gaps about the value and possible environmental impacts, the occurrence, distribution, and associations of a range of elements (Ag, Al, As, Ba, Cd, Co, Cr, Cs, Cu, Li, Mg, Mn, Ni, Pb, Rb, Sb, Sr, Tl, U, V, and Zn) were studied in the inner (core) and outer (shell) morphological parts of the sclerotia from a diverse collection in Southern China. Quality of forest and agricultural soil in terms of a geogenic element source and composition can be considered as the main factor determining the occurrence of minerals in sclerotia through the host wood, largely of Pinus yunnanensis, while the anthropogenic impact (basically at remote rural areas of cultivation) in Southern China was negligible. In general, the mean concentration of each element in the outer part was significantly higher than that in the inner part (t-test, p < 0.01), except for Ag. The concentration of a given element in the outer part tended to have a positive relationship with that in the inner part, except for Cu, Se, Ag, and Zn. The elements in different morphological parts of sclerotia present different relation patterns. Compared to the outer part, there were stronger associations of elements in the inner part, suggesting homeostatic regulation of multiple elements in the inner parts. Further study on the sclerotia, infected wood substrate, and surrounding soil from a range of wild sample collections and intentional cultivation should provide a more complex view and allow assessment of the relationship between minerals and bioactive organic compounds produced by P. hoelen.

LC/ICP-MS AND COMPLEMENTARY TECHNIQUES IN BESPOKE AND NONTARGETED SPECIATION ANALYSIS OF ELEMENTS IN FOOD SAMPLES.

Chemical elements speciation analysis of food samples has been among the most important scientific topics over the last decades. Food samples are comprised of high variety of chemical compounds, from which many can interact with metals and metalloids, forming complex elemental species with various influence on the human body. It is particularly important not only to determine the amount of certain chemical element in food sample but also to identify the form in which given element occurs in given sample. Employment of bespoke and nontargeted speciation methods, with the use of liquid chromatography inductively coupled plasma mass spectrometry (LC/ICP-MS) and complementary techniques, provides more complete picture on the metals and metalloids speciation in food. This review discusses issues concerning speciation analysis of metals and metalloids in food samples with the use of LC/ICP-MS as a leading technique in elemental speciation nowadays and a complimentary technique intended for their identification. © 2020 John Wiley & Sons Ltd. Mass Spec Rev.

Toxic metals in human milk in relation to tobacco smoke exposure.

Several reports confirm the deleterious effects of tobacco smoking and exposure to second-hand smoke (SHS) resulting in changes in the composition of breast milk. The aim of our study was to compare the levels of selected essential, as well as, toxic metals found in colostrum (collected at day 1 ± 2 post-birth) and mature milk (1 month ± 7 days post-birth) of nonsmoking women (n = 52) compared to those found in women who smoke tobacco (n = 51) and women exposed to second-hand smoke during pregnancy and lactation (n = 47). Women's non-smoking or smoking status was determined by their responses to a questionnaire, including questions about others who may smoke in the home environment, and confirmed by measurement of cotinine in the blood serum by high performance liquid chromatography with diode array detector (HPLC-DAD). Inductively coupled plasma mass spectrometry (ICP-MS) and flame atomic absorption spectroscopy (F-AAS) techniques were used to determine the metal concentrations in colostrum and mature milk previously digested by a microwave mineralizer. We confirmed that exposure to tobacco smoke increases concentrations of heavy metals (cadmium and lead) in colostrum and mature milk. These increased concentrations of heavy metals may disturb the action of bioactive substances necessary for the optimal growth and development of newborns and infants. These findings support the need for increased concern and information to lactating women about preventing their exposure to cigarette smoking and SHS due to the adverse effects of tobacco smoke on breast milk with added risks to their infants.

Arsenic species and their transformation pathways in marine plants. Usefulness of advanced hyphenated techniques HPLC/ICP-MS and UPLC/ESI-MS/MS in arsenic species analysis.

The growing popularity of algae as a foodstuff around the world raises concern for the safety of this food type with respect to arsenic content in algae. The need for determination of total arsenic content and arsenic speciation in algae food has become an important issue. In this paper we have developed a complete analytical procedure for arsenic determination in algae products comprised of 1) total arsenic (tAs) determination in native algae samples after digestion, 2) extraction of As species with the use of two extraction methods with three extracting agents, 3) extracted total arsenic (extracted tAs) determination in algae extracts, 4) bespoke As speciation, 4) mass balance estimation based on extracted tAs and bespoke As speciation results, 5) unknown arsenic (uAs) species identification. Two advanced hyphenated techniques, HPLC/ICP-MS and UPLC/ESI-MS/MS, were employed along with the HPLC/ICP-MS method validation. Total As content in edible algae samples was found to range from (19.28 ± 0.45) mg kg-1 up to (72.6 ± 2.7) mg kg-1. Bespoke arsenic speciation of edible algae samples has revealed the presence of some known inorganic and simple organic As compounds such as As(III) from

Total Versus Inorganic and Organic Species of As, Cr, and Sb in Flavored and Functional Drinking Waters: Analysis and Risk Assessment.

Packing material can release certain elements such as As, Cr, or Sb into its content and, thus, contaminate the drinking water. The effect of As, Cr, and Sb on human health depends highly on the chemical species in which these elements are introduced into the body. For the above reasons quantification and speciation of As, Cr, and Sb in flavored and functional drinking water samples is an important issue. Total, inorganic, and organic species of As, Cr, and Sb including As(III), As(V), Cr(VI), Sb(III), and Sb(V) were studied in flavored and functional drinking waters. Analyses of total As, Cr, and Sb were conducted using inductively coupled plasma mass spectrometry (ICP-MS) according to ISO 17294-2:2016. The speciation analysis of arsenic, chromium, and antimony in bottled flavored and functional drinking waters was conducted with the use of the elemental (HPLC/ICP dynamic reaction cell (DRC) MS) and molecular (electrospray ionization MS/MS) mass spectrometry. Concentrations of total As, Cr, and Sb (µg∙L-1) in waters studied were in the ranges 0.0922 ± 0.0067 to 8.37 ± 0.52, 0.0474 ± 0.0014 to 1.310 ± 0.045, and 0.0797 ± 0.0026 to 1.145 ± 0.019, respectively. Speciation analysis showed that, apart from the toxic ionic species, known and unknown organic species were present in test samples. The risk assessment results proved that there is no risk associated with consumption of these tested beverages in terms of the non-carcinogenic effect of total and inorganic or organic species of As, Cr, and Sb.

Arsenic speciation in mushrooms using dimensional chromatography coupled to ICP-MS detector.

This study concerns total arsenic (TAs) and arsenic species determination in three species of mushrooms collected in Yunnan, China. The purpose of this study was to check concentration level of arsenic in Boletus edulis, Tricholoma matsutake and Suillellus luridus, estimate arsenic bioaccessibility and find out which arsenic species occur in mushrooms to assess if they may pose a threat to human health. An analytical methodology based on ion chromatography (IC) hyphenated to inductively coupled plasma mass spectrometry (ICP-MS) with dynamic reaction cell (DRC) and size exclusion chromatography (SEC) with UV-Vis detection and ICP-DRC-MS detection. Ultrasound assisted extraction (UAE), microwave assisted extraction (MAE) and enzymatic assisted extraction (EAE) were applied. Quantification of As species in extracts was performed by IC/ICP-DRC-MS in the first dimension. Slightly better extraction efficiencies were obtained for MAE (from 75% to 90%) then for UAE. EAE was used for estimation of bioaccessibility by application of a modified BARGE bioaccessibility method (UBM) for in vitro studies. Bioaccessibility values were in the ranges of 73%-102%, 74%-115% and 18%-87% for step 1 (S1), for step 2 (S2) and for step 3 (S3) of EAE, respectively. Extracts obtained after EAE were subjected to SEC-UV-Vis/ICP-DRC-MS analysis as the second dimension. The main signal was obtained in the area of a molecular mass of ∼5 kDa for all mushroom extracts. Monitoring of an 50SO+ ion confirmed that this signal comes from As-protein. In sample of Boletus edulis additional signal occurred which is classified as unknown As-compound. Both signals require identification with another analytical technique.

Associations between the Level of Trace Elements and Minerals and Folate in Maternal Serum and Amniotic Fluid and Congenital Abnormalities.

Congenital birth defects may result in a critical condition affecting the baby, including severe fetal/neonatal handicap and mortality. Several studies have shown that genetic, nutritional, and environmental factors may have an impact on fetal development and neonatal health. The relevance of essential and toxic elements on fetal development has not yet been fully investigated, and the results of recent research indicate that these elements may be crucial in the assessment of the risk of malformations in neonates. We determined the association between essential and toxic elements and the level of folate in maternal serum (MS) and amniotic fluid (AF), along with neonatal abnormalities. A total of 258 pregnant Polish women in the age group of 17⁻42 years participated in this study. AF and MS were collected during vaginal delivery or during cesarean section. An inductively coupled plasma mass spectrometry technique was used to determine the levels of various elements in AF and MS. The results of this exploratory study indicate that the levels of essential and toxic elements are associated with fetal and newborn anatomical abnormalities and growth disorders.

Study on Speciation of As, Cr, and Sb in Bottled Flavored Drinking Water Samples Using Advanced Analytical Techniques IEC/SEC-HPLC/ICP-DRC-MS and ESI-MS/MS.

The main aim of the research was to develop a complementary analytical approach consisting of bespoke speciation analysis and non-targeted speciation analysis of As, Sb, and Cr in flavored bottled drinking water samples using HPLC/ICP-DRC-MS and ESI-MS/MS. The scope of two previously developed analytical procedures, (1) multielemental speciation procedure for AsIII, AsV, CrVI, SbIII, and SbV analysis and (2) arsenic speciation procedure for AsB, AsIII, DMA, MMA, and AsV quantification, was extended to the analysis of a new sample type in terms of bespoke speciation analysis. As for the non-targeted speciation, analysis size exclusion chromatography was used with ICP-MS and a complementary technique, ESI-MS/MS, was used for the organic species of As, Sb, and Cr screening. Full validation of procedures 1 and 2 was conducted. Procedure 1 and 2 were characterized with precision values in the range from 2.5% to 5.5% and from 3.6% to 7.2%, respectively. Obtained recoveries ranged from 97% to 106% and from 99% to 106% for procedures 1 and 2, respectively. Expanded uncertainties calculated for procedures 1 and 2 ranged from 6.1% to 9.4% and from 7.4% to 9.9%, respectively. The applicability of the proposed procedures was tested on bottled drinking water samples. Results for the real samples in procedure 1 were in the range from 0.286 ± 0.027 [µg L-1] to 0.414 ± 0.039 [µg L-1] for AsIII, from 0.900 ± 0.083 [µg L-1] to 3.26 ± 0.30 [µg L-1] for AsV, and from 0.201 ± 0.012 [µg L-1] to 0.524 ± 0.032 [µg L-1] for SbV. CrVI and SbIII were not detected in any sample. As for procedure 2, results were in the range from 0.0541 ± 0.0053 [µg L-1] to 0.554 ± 0.054 [µg L-1] for AsB. Results for AsIII and AsV obtained with procedure 2 were in good accordance with results obtained with procedure 1. DMA and MMA were not detected in any sample.

Evaluation of Essential and Toxic Elements in Amniotic Fluid and Maternal Serum at Birth.

The objective of this study was to determine the concentration and the reference ranges of essential and toxic elements in amniotic fluid (AF) and maternal serum (MS) at birth. This study was conducted among 175 healthy pregnant Caucasian European women aged 18-42. AF and maternal blood samples were collected during delivery. An inductively coupled plasma mass spectrometry (ICP-MS) technique was used to determine the levels of Mg, Co, Cu, Zn, Sr, Cd, Ba, Pb, U, Ca, Cr, Al, Mn, V, Fe, As, Se and Sb in AF and MS. The range of reference values was calculated for all analyzed elements in the serum and AF. The mean concentrations of elements, except Pb, were generally higher in MS than in AF. Multiple regression analysis showed that the maternal/newborn body mass (MBM/NBM) ratio was a strong negative predictor (among maternal age and gravidity) of Mg concentration in amniotic fluid. In the serum, MBN/NBM ratio was a strong positive predictor of Cu concentration. Moreover, regression analysis showed that maternal age was an independent positive predictor of the Se level in maternal serum. The reference value ranges of 18 essential and toxic elements were established in AF and MS among a population of healthy pregnant Polish women at delivery. The level of Mg, Co, Cu, Ca and Se in AF and MS can be determined by maternal age and MBM/NBM ratio. These results can be useful in counseling individuals with pregnancies affected by exposure to one of the parameters under investigation.