Distribution of elements in seeds of some wild and cultivated fruits. Nutrition and authenticity aspects.

BACKGROUND: The compositional, functional, and nutritional properties of fruits are important for defining their quality. Fruit seeds should be better exploited as they are also considered to be a good source of bioactive components. Twenty macro, micro, and trace elements were identified and quantified in the seeds of 70 genuine wild and cultivated fruit species/cultivars by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. Sophisticated chemometric techniques were also used to establish criteria for the classification of the analyzed samples. RESULTS: Calcium and P were the most abundant elements, followed by K and Na. The content of microelements and trace elements differed among the different cultivars/genotypes. The content of Ba, Pb, and Sr was significantly higher in wild fruits, whereas Fe, Mg, Mn, Ni and Zn content was higher in cultivated fruits. CONCLUSION: All of the statistical procedures that were used - Kruskal-Wallis, Mann-Whitney U-test, and principal component analysis (PCA) - confirm a unique set of parameters that could be used as phytochemical biomarkers to differentiate fruit-seed samples belonging to different cultivars/genotypes according to their botanical origin. This kind of investigation may contribute to intercultivar/genetic discrimination and may enhance the possibilities of acquiring a valuable authenticity factor. © 2018 Society of Chemical Industry.

Oral cadmium exposure affects skin immune reactivity in rats.

Skin can acquire cadmium (Cd) by oral route, but there is paucity of data concerning cutaneous effects of this metal. Cd acquired by oral route can affect skin wound healing, but the effect of Cd on other activities involved in skin homeostasis, including skin immunity, are not explored. Using the rat model of 30-day oral administration of Cd (5 ppm and 50 ppm) in drinking water, basic aspects of immune-relevant activity of epidermal cells were examined. Dose-dependent Cd deposition in the the skin was observed (0.035 ±â€¯0.02 µg/g and 0.127 ±â€¯0.04 µg/g at 5 ppm and 50 ppm, respectively, compared to 0.012 ±â€¯0.009 µg/g at 0 ppm of Cd). This resulted in skin inflammation (oxidative stress at both Cd doses and dose-dependent structural changes in the skin and the presence/activation of innate immunity cells). At low Cd dose inflammatory response (nitric oxide and IL-1ß) was observed. Other inflammatory cytokines (IL-6 and TNF) response occurred at 50 ppm, which was increased further following skin sensitization with contact allergen dinitro-chlorobenzene (DNCB). Epidermal cells exposed to both Cd doses enhanced concanavalin A (ConA)-stimulated lymphocyte production of IL-17. This study showed for the first time the effect of the metal which gained access to the skin via gut on immune reactivity of epidermal cells. Presented data might be relevant for the link between dietary Cd and the risk of skin pathologies.

Antioxidative responses of the tissues of two wild populations of Pelophylax kl. esculentus frogs to heavy metal pollution.

Heavy metal pollution of the aquatic environment is of great concern worldwide. Heavy metals are capable of inducing oxidative stress by increasing the formation of reactive oxygen species (ROS), and directly affecting the antioxidant defense system (AOS) in living organisms. The frog Pelophylax kl. esculentus is a semiaquatic species with semipermeable skin and a complex lifecycle, and represents a potentially useful bioindicator organism. The aim of this study was to investigate the accumulation of several heavy metals (Cd, Co, Cr, Cu, Fe, Hg, Ni, Pb and Zn), and their effects on selected parameters of the AOS, including the activities of superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GSH-Px), glutathione reductase (GR), phase II biotransformation enzyme glutathione-S-transferase (GST), the total glutathione (GSH) contents and sulfhydryl (SH) group concentrations, as well as cholinesterases (ChEs) activities in the liver, skin and muscle of P. kl. esculentus. Frog samples were collected at two sites (the Danube-Tisza-Danube canal (DTDC) and the river Ponjavica) in Serbia, which are characterized by different levels of metal pollution. Differences between the metal contents in different tissues showed that the skin of frogs from the DTDC accumulated statistically higher concentrations of Cd, Cu, Pb and Zn, while only the Fe concentration was lower. No significant differences between metal concentrations in muscle tissues of frogs from the DTDC and Ponjavica were observed. Examination of the parameters of the AOS revealed that frogs from the DTDC had higher concentrations of GSH in the liver and of SH groups in the skin and muscle, whereas the activities of the antioxidative enzymes SOD, GHS-Px and GR in the liver and of GR in the skin were lower than in frogs from the Ponjavica. The relationship between metal concentrations and AOS parameters showed the highest number of correlations with GSH, GR and CAT, and with Ni, Zn, Hg, Cr and Cd. Based on the results in this study, we concluded that increased concentrations of heavy metals in frog tissues can alter the AOS, which leads to higher concentrations of GSH and SH groups and lower activities of antioxidative enzymes. The response of the AOS to metal pollutants allowed us to make a distinction between different frog tissues, and to conclude that the liver and skin are more suitable for assessing metal-induced oxidative stress in frogs than muscle.

Accumulation of U, Th, Pb, V, Rb, and Ag in wild mushrooms Macrolepiota procera (Scop.) Singer from Goc, Serbia.

In this study, the content of U, Th, Pb, V, Rb, and Ag in 19 soil samples from unpolluted Goc Mountain area (Serbia) was determined. The same elements were determined in 19 Macrolepiota procera samples, separately for caps and stipes. Soil samples were subjected to the BCR sequential extraction procedure. Element contents were determined by inductively coupled plasma mass spectrometry (ICP-MS). Obtained soil values for U were in the range from 0.30 to 0.86 mg/kg and for Th from 1.7 to 13.2 mg/kg. These values are the first for background levels at unpolluted Goc area, and they are lower than the corresponding values for European unpolluted soil. The mean values in soil for Pb, V, Rb, and Ag were 27.6, 57.4, 15.8, and 0.76 mg/kg, respectively. PCA was applied to establish criteria for translocation of the analyzed elements between two parts of the mushroom. Efficient translocation for all elements except Ag as the main amount of the elements was found in caps. The mean content in the caps for U and Th was 4.3 and 63 µg/kg, respectively. Bioconcentration factors were much higher than 1 only for Rb and Ag. M. procera only weakly accumulates U and Th from soil in unpolluted areas. These findings indicate limited role of M. procera in the mycoremediation of the mentioned actinides.

Scandium, yttrium, and lanthanide contents in soil from Serbia and their accumulation in the mushroom Macrolepiota procera (Scop.) Singer.

The mobility (fractionation) of rare earth elements (REEs) and their possible impacts on ecosystems are still relatively unknown. Soil samples were collected from two sites in central Serbia, an unpolluted mountain region (site 1) and a forest near a city (site 2). In order to investigate REE fractions (acid-soluble/exchangeable, reducible, oxidizable, and residual) in soils, BCR sequential extraction was performed. Additionally, the content of REEs was also determined in stipes and caps of the mushroom Macrolepiota procera, growing in the observed sites. Sc, Y, and lanthanide contents were determined by inductively coupled plasma mass spectrometry (ICP-MS), and results were subjected to multivariate data analysis. Application of pattern recognition technique revealed the existence of two distinguished clusters belonging to different geographical sites and determined by greater levels of Sc, Y, and lanthanides in Goc soil compared to Trstenik soil. Additionally, PCA analysis showed that REEs in soil were concentrated in two groups: the first consisted of elements belonging to light REEs and the second contained heavy REEs. These results suggest that the distribution of REEs in soils could indicate the geographical origin and type of soil. The bioconcentration factors and translocation factors for each REE were also calculated. This study provides baseline data on the rare earth element levels in the wild edible mushroom M. procera, growing in Serbia. In terms of bioconcentration and bioexclusion concept, Sc, Y, and REEs were bioexcluded in M. procera for both studied sites.

RuO2/graphene nanoribbon composite supported on screen printed electrode with enhanced electrocatalytic performances toward ethanol and NADH biosensing.

In this work, we aimed to propose a newly synthesized composite material with enhanced electrocatalytic properties as a novel screen-printed sensor for the quantification of NADH. Additionally, the surface was modified with alcohol dehydrogenase for the preparation of an amperometric biosensor for analysis of ethanol. Synthesized material was characterized using several microstructural (FE-SEM, HR-TEM, XRD) and electrochemical (CV, EIS) techniques. The electrochemical response of the tested analytes was investigated as a function of important parameters. Under optimal conditions, the working linear range and limit of detection for ethanol sensing was 1-1800 µM and 0.19 µM, respectively. For NADH, the linear range was from 1 to 1300 µM with limit of detection of 0.52 µM. Moreover, effects of some possible interfering compounds were investigated and the developed procedure was applied to commercial alcoholic beverages. The results obtained showed satisfactory precision and accuracy of the developed method and confirm the proposed approach could be a possible replacement for the currently used techniques for ethanol and NADH quantification.

Characterization of Croatian Rape (Brassica sp.) Honey by Pollen Spectrum, Physicochemical Characteristics, and Multielement analysis by ICP-OES.

Rape (Brassica sp.) unifloral honey from Croatia was characterized by certain physicochemical parameters, micro- and macroelement content, and pollen spectrum, as determined in 21 honey samples. The Brassica sp. pollen type was predominant in the analyzed samples and ranged between 60 and 98%, with Trifolium spp., Robinia pseudoacacia, Rosaceae, Helianthus annuus, Salix spp., and Taraxacum officinale as the main accompanying pollen types. The electrical conductivity mean value was 0.22 ± 0.05 mS/cm and the glucose/fructose ratio mean value was 1.1 ± 0.07, whereas sucrose was absent in the samples. The most abundant macroelement was potassium (K) (268.49 mg/kg), followed by phosphorus (P) (60.23 mg/kg), calcium (Ca) (54.02 mg/kg), sodium (Na) (22.52 mg/kg), sulfur (S) (15.79 mg/kg), and magnesium (Mg) (12.58 mg/kg). Toxic elements were mainly bellow the LODs; only arsenic (As) concentration was detectable in higher amount (0.233 mg/kg), which may be related to the high arsenic concentration in the soil and groundwater of eastern Croatia. The differences between the two harvesting seasons observed in a large number of elements could be related to climatic and soil conditions and different nectar yields originating from the associated plant species.

Study of silver, selenium and arsenic concentration in wild edible mushroom Macrolepiota procera, health benefit and risk.

The content and bioaccumulation of trace (Ag, Se, As) and major elements (Ca, Mg, Na and K) in wild edible mushroom Macrolepiota procera and its corresponding soil substrates, collected from five sites in the Rasina region in central Serbia, were investigated. The content of Ag, As and Se was determined by inductively coupled plasma mass spectrometer (ICP-MS) while the amount of Ca, Mg, Na and K was determined by inductively coupled plasma optical emission spectrometer (ICP-OES). The concentrations of major elements in the mushrooms were at typical levels. As far as trace elements are concerned, M. procera bioaccumulates silver although all samples were collected from unpolluted sites. It was found that the content of Ag depended on the geographical origin and the density of fruiting body on the certain site. Principal component analysis distinguished the mushroom samples from different geographical areas and revealed the influence of soil composition on metal content in fruiting bodies. Also, a linear regression correlation test was performed to investigate correlations between Ag, Cd, Se, Pb and As in caps and stipes at different geographic sites separately. In addition, our results indicated that M. procera could serve as a good dietary source of Mg, K and Se. The content of Ag and As was low, so it could not pose a health risk for consumers.