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.

Impact of a severe flood on large-scale contamination of arable soils by potentially toxic elements (Serbia).

Extreme flooding in May, 2014 affected the sub-catchments of six major rivers in Serbia. The goal of the study was to evaluate the contents of potentially toxic elements (PTEs) As, Cd, Pb, Cr, Ni, Cu, and Zn in flood sediments and arable soils within the affected sub-catchments using regulatory guidelines and background levels. The sub-catchment of West Morava was selected to assess the degree of sediments and soils contamination and environmental risk [using the Pollution index (Pi), Enrichment factor, Geo-accumulation index, and Potential ecological risk index (PERI)] as well as to identify main PTEs sources by Principal component (PCA) and cluster analysis. Contents of Ni, Cr, As, Pb, and Cu above both guidelines and background levels, and of Zn and Cd above background levels were detected in the sediments and soils from all the sub-catchments. Pi indicted that about 95% of the soils and sediments were extremely polluted by Ni and about 65% slightly polluted by Cr, whereas about 90% were not polluted by As, Cd, Pb, Cu, or Zn. Ef indicated minor to moderate enrichment of the soils and sediments by Ni, and Cr. PCA differentiated a geogenic origin of Ni, Cr, As, and Pb, a mixed origin of Cd and Zn, and a predominantly anthropogenic origin of Cu. PERI of the soils and sediments suggested a low overall multi-element ecological risk. The ecological risk of the individual elements (E r i ) for soils was Zn < Cr < Pb < Ni < Cu < As < Cd.

Biogeochemistry of Ni and Pb in a periodically flooded arable soil: Fractionation and redox-induced (im)mobilization.

The redox-induced (im)mobilization of nickel (Ni) and lead (Pb) under pre-definite redox conditions and their binding forms were studied in a periodically flooded, slightly acidic arable soil enriched with serpentine minerals at the Velika Morava River valley, Serbia. The total contents of Ni and Pb were 152 and 109 mg kg-1, respectively. Geochemical fractionation of Ni, combined with mineralogical analysis, confirmed its geogenic origin in the soil. Potentially mobile fractions were the dominating binding forms of Pb; thus, indicating anthropogenic sources as prevailing. Risk assessment indicated a low risk of Ni and Pb transfer from soil to other environmental constituents. However, the results imply that geogenic metals might pose higher environmental risk than those from anthropogenic origin, in dependence of their total concentrations and contents in the specific solid-phase fractions. Flooding of the soil was simulated in an automated biogeochemical microcosm system, which allows a control and a continuous measurements of redox potential (EH) and pH. Subsequently, the EH was increased in steps of approximately 100 mV from anoxic to oxic conditions. Concurrently, the concentrations of soluble Ni, Pb, iron (Fe), manganese (Mn), dissolved organic carbon (DOC), and sulfates were measured. The EH was brought from low to high values (-220 to 520 mV) and correlated negative with soluble Ni, Pb, Fe, Mn and DOC. Soluble Ni ranged from 125 to 228 µg l-1 while Pb ranged from 3.0 to 21.4 µg l-1. Concentrations of both metals in solution were high at low EH and decreased with increasing EH. Nickel immobilization may be attributed to sorption to or co-precipitation with re-oxidized Fe-Mn (hydr)oxides, whereas Pb, in addition, might be immobilized via precipitation with inorganic ligands, such as carbonates and phosphates. The results imply that Ni and Pb solubility might also be related to the formation of metal-DOC complexes. The detected dynamic and mechanisms might be useful in providing critical information for assessing the potential environmental risk and creating appropriate environmental management strategies for agricultural areas enriched with Ni and Pb.

Bioassessment of heavy metals in the surface soil layer of an opencast mine aimed for its rehabilitation.

The contemporary reclamation method in an opencast coal mine closure comprises the use of the preserved surface soil layer (SSL) before mining, and can be directly returned to the areas being rehabilitated. The present study emphasizes a risk in the use of such a SSL in mine rehabilitation due to the possible excessive amount of heavy metals which usually derives from a metal-rich sediment or fluvial character of overburden material. This indication was approved by the bioassessment of cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn) in root and aerial parts of maize (Zea mays), alfalfa (Medicago sativa), sweet clover (Melilotus officinalis), wheat (Triticum aestivum), barley (Hordeum sativum), white clover (Trifolium repens), pasture (Poales sp.), tomato (Solanum lycopersicum), potato (Solanum tuberosum) and carrot (Daucus carota) grown on SSL in the opencast mine area. The fluvial layers of the investigated mine SSL revealed the excessive existence of Ni and Cr, probably of geogenic origin, according to the X-ray diffraction (XRD) which detected Ni- and Cr-bearing minerals in soil fractions. In addition, the highest residual fraction of these two heavy metals, obtained by sequential extraction analyses, together with all other tested soil parameters, supported this assumption. Nevertheless, the accumulations of Cr in tomato fruit (2.93 mg kg-1), potato tuber (5.89 mg kg-1) and carrot root (7.35 mg kg-1) grown on the investigated SSL were found to exceed a critical level of this element for human nutrition. However, despite the evident excess of Ni in the investigated SSL, a similar trend was not found in edible part of plants. The transfer and mobility of the investigated metals was evaluated using the accumulation factor (AF < 1.0) where the root were the preferential organ for the storage of heavy metals. This investigation could bring an important input for its acceptability of use in soil restoration after mining for food/fodder production, or it could indicate the potential risks of the presence of heavy metals regarding its possible use in improving the human surrounding.

A bioassessment of soil nickel genotoxic effect in orchard planted on rehabilitated coalmine overburden.

Environmental problems of non-rehabilitated overburden material are present in surrounding of open coal mines worldwide. Ecological restoration of this soil material usually deals with the improvement of its bad physico-chemical properties and its poor nutrient status, sometimes associated with heavy metal problems. Applied overburden restoration by planting orchard (1990) is assumed to be the first of its kind at opencast mines globally, so that present work was aimed at acquiring information about its efficiency of the applied measures concerning their possible use in agriculture. Various physical and chemical properties, together with the pseudo total and DTPA extractable metals (Fe, Mn, Cu, Zn, Co, Ni, Pb, Cr, Cd) as well as sequential Ni extraction analyses, was measured, in order to evaluate the impact of soil's Ni level (76.3-111.7 mg kg⁻¹) on decreasing yields of apples, pears and plums. As a general pattern, reclaimed soil was significantly enriched with organic matter (>2.5 percent) and nutrients compared to the initial (2 m depth) and non-reclaimed adjacent soil, approving this method for overburden restoration. Despite low Ni concentration in organs, Ni accumulation in a fruits' trees qualified these species as suitable for phytostabilization of present heavy metals, with a woody biomass as a large and important sink for Ni, especially in the roots. Applied cytogenetic studies evaluate the lack of genotoxic effect of nickel (Ni) on the gametic cells of investigated species, having no significant effect on meiosis and pollen germination. Most of the found anomalies were in apples, as a kind of aberrations with sticky figures and chromosome lagging, should be ascribed to the environmental and genetic interaction over the aging of trees.

Redox-controlled release dynamics of thallium in periodically flooded arable soil.

To our knowledge, this is the first work to mechanistically study the impact of the redox potential (EH) and principal factors, such as pH, iron (Fe), manganese (Mn), dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), chlorides (Cl-) and sulfates (SO42-), on the release dynamics of thallium (Tl) in periodically flooded soil. We simulated flooding using an automated biogeochemical microcosm system that allows for systematical control of pre-defined redox windows. The EH value was increased mechanistically at intervals of approximately 100 mV from reducing (-211 mV) to oxidizing (475 mV) conditions. Soluble Tl levels (0.02-0.28 µg L-1) increased significantly with increases in EH (r = 0.80, p < 0.01, n = 30). Thallium mobilization was found to be related to several simultaneous processes involving the gradual oxidation of Tl-bearing sulfides, reductive dissolution of Fe-Mn oxides and desorption from mineral sorbents. Manganese oxides did not appear to have a considerable effect on Tl retention under oxidizing conditions. Before conducting the microcosm experiment, Tl geochemical fractionation was assessed using the modified BCR sequential extraction procedure. The BCR revealed a majority of Tl in the residual fraction (77.7%), followed by reducible (13.3%) and oxidizable fractions (5.9%). By generating high levels of Tl toxicity at low doses, Tl released under oxidizing conditions may pose an environmental threat. In the future, similar studies should be conducted on various soils along with a determination of the Tl species and monitoring of the Tl content in plants to achieve more detailed insight into soluble Tl behavior.