Potential use of Ulva intestinalis-derived biochar adsorbing phosphate ions in the cultivation of winter wheat Tristicum aestivum.

In this work, the properties of biochar produced from green macroalga Ulva intestinalis by pyrolysis were studied at temperatures of 300, 500, and 700 °C. This biochar was characterized in terms of multielemental composition, BET surface area, total pore volume, and biosorption properties toward phosphate ions. Biochar produced at 700 °C-25 m2/g had the highest surface area. The kinetics and isotherms of sorption processes of phosphate ions as sorbate by these sorbents were investigated. Modified biochar was able to remove 84.3% of phosphate ions from wastewater, whereas non-modified biochar-only 40.6%. Hence, biochar enriched with phosphate ions can serve as a valuable soil amendment. Pot experiments performed on winter wheat (Triticum aestivum) with a 3% addition of dry Ulva intestinalis, pristine biochar, and Mg-modified biochar enriched with phosphate ions showed that these amendments stimulated plant growth (length and fresh weight of plants) as well as enlarging the chlorophyll content in leaves. Our results indicate that the production of biochar (pristine and Mg-impregnated) is a sustainable option to valorize the biomass of seaweeds, and to recycle phosphorus from wastewater.

The Identity and Mineral Composition of Natural, Plant-Derived and Artificial Sweeteners.

The qualitative X-ray phase analysis of natural and artificial food sweeteners was applied to trace the authenticity of such food additives. The mineral composition of different sweeteners commonly added to foods was studied to estimate their mineral profiles and assess the risk related to the toxic elements intake caused by sweetener consumption. The concentration of twenty elements (Ag, Al, B, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sr, Ti, V, and Zn) was measured using the inductively coupled plasma-optical emission spectroscopy (ICP-OES) method after the representative samples were wet-digested with a concentrated nitric acid and hydrogen peroxide mixture in a closed-vessel microwave-assisted system. Differences between the mineral compositions of the examined sweeteners were statistically evaluated and discussed. The relationships between the concentrations of the elements determined in the analyzed sweeteners were also investigated. The successful application of the X-ray powder diffraction method proved the identity of all investigated sweeteners; all the analyzed products contained the expected sweetening agent. The results of the quantification of all the elements in the examined sweeteners indicated that these products cannot be considered nutritionally dense. Hence, the presence of toxic elements like Cd, Cr, Ni, and Pb distinctly indicates the need to test such products to guarantee their quality and ensure consumer safety.

Determination and speciation of inorganic As in homeopathic medicines by HG-ICP OES method with no or minimal sample treatment before measurements.

The analysis of homeopathic medicines for the content of total inorganic As by hydride generation (HG) hyphenated with the ICP OES detection was presented. Various forms of medicaments (sugar pellets, tablets, alcohol-based drops), containing Arsenicum album or Arsenicum iodatum in several potencies (C9-200, D6-10), as well as different sample preparation approaches (wet digestion, extraction, dissolution, dilution, direct analysis) before spectrometric measurements were studied. The influence of the undecomposed sample matrix (mainly sugar and alcohol) on the HG process of As was examined in detail. Under optimal conditions found, simplified sample preparation procedures for the determination of As traces were proposed. The suitable sensitivity, the limit of detection of As < 0.1 ng g-1, the precision within 0.31-7.4 % (as RSD), and the adequate trueness (94.9-113 % as confirmed by the recovery test) were achieved. Using the species-selective HG conditions and the developed direct analysis method, the speciation of As in arsenic drops without any prior chromatographic separation of As(III) and As(V) was carried out. The applicability of the developed strategies was demonstrated by the determination of As in 13 homeopathic products available on the Polish market.

Brown seaweed: Fucus vesiculosus as a feedstock for agriculture and environment protection.

A comprehensive approach to the management of brown seaweed-Fucus vesiculosus was presented. An algal extract, which served as a biostimulant of plant growth was produced using ultrasound-assisted extraction (UAE). The concentration of the extract (20, 40, 60, 80, 100%), which had the greatest influence on biometric parameters of radish, was determined in germination tests. The seaweed itself as well as the produced post-extraction residue were used in doses of 2 and 4 g/kg as soil additives, stimulating plant growth in the initial phase. Pot tests for sorghum carried out under optimal conditions (20% extract and 2 g/kg of soil additive) had a positive effect on the plant weight, length and the content of chlorophyll in comparison with the control group treated with distilled water. Additionally, preliminary studies on the bioremediation of soil contaminated with Zn(II) ions with the use of both soil additives were performed. It was shown that the immobilization of Zn(II) ions in the soil by the applied additives reduced the bioaccumulation of zinc in the aerial part of plants as compared with the group cultivated in the contaminated soil but without additive. Accordingly, by producing plant biostimulants by UAE it was also possible to successfully manage the post-extraction residue following the concept of a bio-based economy.

Novel ICP-OES-Based Method for the Reliable Determination of the Total Content of 15 Elements in Yerba Mate Drinks along with the Determination of Caffeine and the In Vitro Bioaccessibility of the Compounds.

A fully validated inductively coupled plasma optical emission spectrometry (ICP-OES)-based method combined with a simplified sample preparation procedure for the determination of up to 15 elements (Al, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn) in caffeinated yerba mate (YM) drinks was proposed. Various "green" treatments (acidification or dilution with a HNO3 solution and direct analysis of untreated YM with or without sonication (US)) that could replace the traditional total sample decomposition before spectrometric measurements were tested and compared. The key selection parameter was the analytical performance of the ICP-OES method obtained with each sample preparation procedure in terms of the precision and the trueness of results and limits of detection (LODs) of elements. It was found that the acidification of YMs with concentrated HNO3 to 5%, supported by US (10 min, room temperature (RT)), provided the best results, i.e., LODs at 0.11-8.5 ng g-1, precision below 5%, and trueness better than 5% (97.0%-105% as recoveries). Eleven YM drinks, commercially available on the Polish market, were analyzed with the proposed method. In addition to the mineral content, the concentration of caffeine in all analyzed YMs was determined and compared. Finally, the studies were completed by determining the bioaccessible fraction of selected elements and caffeine in YMs using in vitro gastrointestinal digestion (GID) in order to evaluate the nutritional value/risk assessment of these drinks. Accordingly, the bioaccessibility of nutritious elements (Ca, Fe, Mg, Mn, Zn) and caffeine was within 40%-59%. Except for Mn, it was established that by drinking daily 1 L of YMs, the recommended dietary intakes (RDIs) of the aforementioned essential elements were covered to a low degree (<4.5%). Hence, they are not an important source of these elements in the human diet. On the other hand, potentially toxic elements (Al, Ba, Sr) were found in a relatively inert form. Opposite to minerals, YMs can supply human organisms with quite high amounts of natural caffeine in bioaccessible form (31-70 mg per serving).

Methods for Rapid Screening of Biologically Active Compounds Present in Plant-Based Extracts.

In recent years, there has been an increased interest in products of natural origin. The extraction procedure of bioactive compounds from plant matrices is a crucial step in the development of useful new bioproducts for everyday life. The utilisation of analyses enabling the rapid identification of the presence of a given group of compounds can be helpful in the early stages of the development of new products in order to save time and reduce costs. Within this article, we have presented a comparison of different, accessible methods for the identification of various bioactive compounds, e.g., saponins, carboxylic acids, oils and fats, proteins and amino acids, steroids, and alkaloids in plant-based extracts. Additionally, the multielemental composition of extracts was also examined. The applied methods allowed for confirmation of the presence of biologically active compounds in bio-products obtained by ultrasound-assisted extraction. At a later stage, these procedures should be supplemented by advanced analytical techniques in order to determine the plant chemicals' content qualitatively and quantitatively.

Rapid and easy ICP OES determination of selected major, minor and trace elements in Pu-erh tea infusions using the response surface methodology along with the joint desirability function approach.

A new analytical method was proposed for multielement (Al, Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Sr and Zn) analysis of Pu-erh teas infusions by inductively coupled plasma optical emission spectrometry. The Box-Behnken response surface design together with individual desirability functions and the joint desirability function approach was applied to develop experimental conditions of this new procedure, being alternative to high-temperature wet digestion. The procedure involved the samples to be just 5-fold diluted with 1.7 mol L-1 HNO3. The proposed method was precise (relative standard deviations within 2-8%), true (relative errors from -8 to +6%) and guaranteed very good detectability (detection limits within 1-6 ng g-1, except for Ca and Fe). It was used for analysis of infusions of Pu-erh teas as well as to verify the effect of their preparation conditions (steeping water temperature, steeping time).

Sensitive determination of Ag, Bi, Cd, Hg, Pb, Tl, and Zn by inductively coupled plasma optical emission spectrometry combined with the microplasma-assisted vapor generation.

A technique of vapor generation assisted by a microplasma was used for sample introduction into inductively coupled plasma optical emission spectrometry (ICP OES). Replacing a pneumatic nebulizer with a novel microplasma device improved the sensitivities of analytical signals for Ag, Bi, Cd, Pb, Tl, and Zn (by 2-13 times), as well as a concomitant reduction in their detection limits (DLs). Moreover, an outstanding improvement (30-fold) was achieved for Hg. The factors contributing to the boosted signal intensities were higher analyte fluxes and less water vapor produced by the microplasma system. The DLs of Ag, Bi, Cd, Hg, Pb, Tl, and Zn in microplasma-ICP OES were 0.4, 4, 0.06, 0.2, 2, 5, and 0.2 µg L-1, respectively, and the measurement precision was within the range of 0.7-2.4% (it was significantly improved as compared to that achievable with pneumatic nebulization). The proposed microplasma-assisted vapor generation eliminates the use of toxic reductants, e.g., sodium tetrahydridoborate, and it is characterized by higher resistance to matrix effects from transition metal ions (as compared to chemical vapor generation (CVG) and photochemical vapor generation (PVG)). To validate the trueness of the SAGD-ICP OES method, certified reference materials of lobster hepatopancreas (TORT-2), cormorant tissue (MODAS-4) as well as spiked tap water and seawater samples were analyzed to determine levels Cd and Hg. The standard additions method was used for calibration in both cases. Recoveries of the analytes in the case of the analysis of TORT-2 and MODAS-4 samples as well as the spiked tap water and seawater was within the range of 98-113%, which indicated that the developed sample introduction system can be successfully used for very sensitive determinations of selected hazardous elements in environmental samples.

Determination of Ag, Bi, Cd, Hg, Pb, Tl, and Zn by inductively coupled plasma mass spectrometry combined with vapor generation assisted by solution anode glow discharge - A preliminary study.

A new technique of vapor generation assisted by a microplasma was proposed for an inductively coupled plasma mass spectrometry (ICP MS). It was found that, by replacing a traditional pneumatic nebulizer with a microplasma (solution anode glow discharge, SAGD), analytical signals of Ag, Bi, Cd, Hg, Pb, Tl, and Zn were improved 8, 4, 13, 13, 9, 10, and 7 times, respectively. The main factor contributing to boosted analytical signal intensities was the higher analyte flux produced by the novel microplasma system. The measurement precision in SAGD-ICP MS was comparable to that achievable for ICP MS (with pneumatic nebulization), and it did not exceed 2%. The detection limits of Ag, Bi, Cd, Hg, Pb, Tl, and Zn in SAGD-ICP MS were 5, 2, 6, 5, 4, 10, and 20 ng L-1, respectively. The analytical performance of this method may be further improved if the observed memory effects could be minimized. To validate the trueness of the novel method, certified reference materials of lobster hepatopancreas (TORT-2), cormorant tissue (MODAS-4), and wastewater (ERM CA-713) were analyzed to determine traces of Cd, Hg, and Pb. Recoveries of certified values for these analytes were ranged from 91 to 111%, which indicated that the studied microplasma system in combination with ICP MS can be successfully used for very sensitive determinations of selected hazardous elements in environmental samples.

Response surface methodology assisted development of a simplified sample preparation procedure for the multielement (Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Sr and Zn) analysis of different coffee brews by means of inductively coupled plasma optical emission spectrometry.

The Box-Behnken response surface design together with the individual desirability functions were used to develop the new and greenish sample preparation procedure of coffee brews prior to their multielement (Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Sr and Zn) analysis by inductively coupled plasma optical emission spectrometry (ICP OES). The developed procedure required only 2-fold dilution of the samples with a 1.8 mol L-1 HNO3 solution and then, the sonication of the resulting samples solutions for 8 min at room temperature. The proposed method was precise (0.6-7.5% as RSD), true (relative errors changing from -5.2% to +4.6%) and guaranteed the limits of detection (LODs) of the studied elements between 0.1 and 5 ng g-1. Finally, this simplified ICP OES based method was applied for the multielement analysis of brews of different Arabica coffees as well as those prepared with seldomly reported devices, i.e., dripper, slow dripper, French press, aeropress and syphon.

Valorization of Cladophora glomerata Biomass and Obtained Bioproducts into Biostimulants of Plant Growth and as Sorbents (Biosorbents) of Metal Ions.

The aim of this study was to propose a complete approach for macroalgae biomass valorization into products useful for sustainable agriculture and environmental protection. In the first stage, the effects of macroalgal extracts and ZnO NPs (zinc oxide nanoparticles) on the germination and growth of radish were examined. Macroalgal extract was produced from freshwater macroalga, i.e., Cladophora glomerata by ultrasound assisted extraction (UAE). The extract was used to biosynthesize zinc oxide nanoparticles. In germination tests, extracts and solutions of ZnO NPs were applied on paper substrate before sowing. In the second stage, sorption properties of macroalga, post-extraction residue, and ZnO NPs to absorb Cr(III) ions were examined. In the germination tests, the highest values of hypocotyl length (the edible part of radish), i.e., 3.3 and 2.6 cm were obtained for 60 and 80% extract (among the tested concentrations 20, 40, 60, 80, and 100%) and 10 and 50 mg/L NPs, respectively. The highest sorption capacity of Cr(III) ions (344.8 mg/g) was obtained by both macroalga and post-extraction residue at a pH of 5 and initial Cr(III) ions concentration of 200 mg/L. This study proves that macroalgae and products based on them can be applied in both sustainable agriculture and wastewater treatment.

Development and Validation of an Analytical Method for Determination of Al, Ca, Cd, Fe, Mg and P in Calcium-Rich Materials by ICP OES.

Four procedures based on closed-vessel microwave-assisted wet digestion with different oxidative reagents, including HNO3 (P1), HNO3 + H2O2 (P2), aqua regia (P3) and Lefort aqua regia (P4), for preparation of calcium (Ca)-rich materials prior to determination of total concentrations of Al, Ca, Cd, Fe, Mg and P by inductively coupled optical emission spectrometry (ICP OES) were compared. It was found that digestion with Lefort aqua regia (P4) provided the best results for all examined elements, i.e., precision of 0.30-4.4%, trueness better than 2%, recoveries of added elements between 99.5-101.9%, and limits of detection within 0.08-1.8 ng g-1. Reliability of this procedure was verified by analysis of relevant certified reference materials (CRMs), i.e., Natural Moroccan Phosphate Rock-Phosphorite (BCR-O32). Additionally, selection of appropriate analytical lines for measurements of element concentrations, linear dynamic ranges of calibration curves and matrix effects on the analyte response were extensively investigated. Finally, the selected procedure was successfully applied for routine analysis of other Ca-rich materials, i.e., CRMs such as NIST 1400 (Bone Ash), CTA-AC-1 (Apatite Concentrate Kola Peninsula) and NCS DC70308 (Carbonate Rock), and six natural samples, such as a dolomite, a phosphate rock, an enriched superphosphate fertilizer, pork bones, pork bones after incineration, and after steam gasification.

Five years of innovations in development of glow discharges generated in contact with liquids for spectrochemical elemental analysis by optical emission spectrometry.

The newest achievements in the field of glow microdischarges generated in contact with a flowing liquid cathode (FLC) and a flowing liquid anode (FLA), used as the excitation sources for optical emission spectrometry (OES), were summarized herein. The design of recently reported discharge systems was compared and comprehensively discussed. A lot of effort was devoted to evaluate the effect of selected operating parameters, i.e., discharge voltage and current, sample flow rate, sample pH, jet-supporting gas flow rate, and discharge gap, on the microplasma stability and the intensity of measurable analytical signals. Furthermore, the influence of chemical modifiers, i.e., organic acids, alcohols, and surfactants, aimed at improving the sensitivity and reducing matrix effects, was referred to as well. Finally, the analytical performance and the application of these promising excitation sources for the elemental analysis of different-matrix samples were presented.

Rapid and simple determination of As in bottled birch saps by hydride generation inductively coupled plasma optical emission spectrometry.

A strategy was developed for the determination of total As in birch saps (BSs) by hydride generation (HG) coupled with inductively coupled plasma optical emission spectrometry (ICP-OES). We proposed and validated a simple and robust HG-ICP-OES method with no need for tedious and long sample preparation before measurements. Corresponding As hydride was generated in reaction with NaBH4 (1.0%) in acidic conditions (10 mol L-1 HCl) after pre-reduction of As(V) to As(III) in a KI (0.5%)-ascorbic acid (2.0%)-HCl (3 mol L-1) mixture. Several different sample preparation procedures, including digestive and non-digestive approaches, were tested in order to improve the detectability of As using HG-ICP-OES. Reactivity of As towards HG under conditions of a real sample was investigated to check potential interfering effects coming from undecomposed sample matrix constituents. The proposed method included the direct analysis of untreated samples (only pre-reduction prior to HG) and precision (<6% as relative standard deviation), accuracy (94.7-108.7% as recoveries) and sensitivity (limit of detection at 0.26 ng mL-1) that was suitable for trace analysis. An absence of matrix effects allowed external calibration for quantification of As. Applicability of the method was demonstrated by determination of As in several commercially available bottled BSs.

Non-chromatographic Speciation of As by HG Technique-Analysis of Samples with Different Matrices.

The applicability of the hydride generation (HG) sample introduction technique combined with different spectrochemical detection methods for non-chromatographic speciation of toxic As species, i.e., As(III), As(V), dimethylarsinate (DMA) and monomethylarsonate (MMA), in waters and other environmental, food and biological matrices is presented as a promising tool to speciate As by obviating chromatographic separation. Different non-chromatographic procedures along with speciation protocols reported in the literature over the past 20 year are summarized. Basic rules ensuring species selective generation of the corresponding hydrides are presented in detail. Common strategies and alternative approaches are highlighted. Aspects of proper sample preparation before analysis and the selection of adequate strategies for speciation purposes are emphasized.

Hanging drop cathode-atmospheric pressure glow discharge as a new method of sample introduction for inductively coupled plasma-optical emission spectrometry.

This work reports the use of hanging drop cathode-atmospheric pressure glow discharge (HDC-APGD) as a new method of sample introduction for inductively coupled plasma-optical emission spectrometry (ICP-OES). The developed arrangement was characterized by a low sample uptake (0.56 mL min-1) and the fact that the entire sample solution volume was consumed by the discharge. This resulted in a very high transport efficiency of analytes from the sample solution into the ICP torch (usually > 80%). Under the optimal operating conditions of HDC-APGD, intensities of emission lines of studied elements were, on average, 2 times higher as compared to those obtained with conventional pneumatic nebulization (PN). Moreover, in the case of I and Y, the observed signal enhancements were even higher, i.e., 6.2 and 6.1 times, respectively. It was also shown that in the case of B and some elements that are known to form different volatile species (Ag, Bi, Cd, Hg, Os, Pb, and Se), the presence of low molecular weight organic compounds in the sample solution, i.e., CH3OH, C2H5OH, HCOOH, CH3COOH, or HCHO, resulted in the additional enhancement of their signals. It was especially evident in the case of Hg for which a 8.6-fold signal enhancement in the presence of HCOOH was noticed. The system presented herein was distinguished from other competitive APGD-type discharges because it could be successfully used for the determination of a vast group of elements, including alkali metals, alkaline earth metals, transition metals, and non-metals.

Simplified ICP OES-Based Method for Determination of 12 Elements in Commercial Bottled Birch Saps: Validation and Bioaccessibility Study.

Commercially bottled birch saps (BSs) were analyzed for several nutrient (Ca, Cu, Fe, Mg, and Zn) and toxic (As, Cd, Ni, and Pb) elements using inductively coupled plasma optical emission spectrometry (ICP OES). The method was validated under the conditions of several sample preparation procedures, including a traditional digestion as well as alternative non-digestion schemes. It was found that the direct analysis of untreated BSs gives the best results, i.e., limits of detection at 0.02-5.8 ng mL-1, precision better than 5%, accuracy from 98.0% to 104.5% and determination of 12 elements in a short time (~1 min per sample). The multi-element analysis of nine commercially available bottled BSs showed that they contained mainly Mg and Ca, small quantities of Mn, Zn, Cu, and Fe, but are free from toxic elements such as As, Cd, Ni, and Pb. Additionally, the nutritional value of BSs was examined using in vitro gastro-intestinal digestion (GID) to determine the bioaccessible fraction of elements. Accordingly, bioaccessibility of nutritious ones (Ca, Cu, Fe, Mg, Zn) was <40%. Drinking daily 1 L of BSs covered <2.5% of recommended dietary intakes (RDIs) of the aforementioned elements. Only the bioaccessibility of Mn highly contributes to its RDI.

Room temperature solvent extraction for simple and fast determination of total concentration of Ca, Cu, Fe, Mg, Mn, and Zn in bee pollen by FAAS along with assessment of the bioaccessible fraction of these elements using in vitro gastrointestinal digestion.

BACKGROUND AND AIM: Bee pollen is recognized to be a source of different nutrients, including minerals. As a food supplement, its quality and safety due to concentrations of essential macro- and microelements, and harmful trace elements has to be verified. Fast and simple element analysis of bee-collected pollen can be regarded as an important part of its quality assurance and control. The present study aimed at developping a new method for determination of selected elements (Ca, Cu, Fe, Mg, Mn, Zn) of bee pollen based on solvent extraction and completely avoiding a high temperature treatment with concentrated reagents. In addition, in vitro gastrointestinal digestion was used to assess bioavailability of elements from this food supplement. METHODS: Bee pollen samples were dried and pulverized. Total concentrations of Ca, Cu, Fe, Mg, Mn, and Zn were determined by flame atomic absorption spectrometry (FAAS) in sample solutions obtained by wet digestion (WD) in concentrated HNO3 or alternatively by solvent extraction (SE) with diluted solutions of HNO3. Gastrointestinal digestion was mimicked using simulated solutions of gastric and intestinal juices followed by determination of Ca, Cu, Fe, Mg, Mn and Zn concentrations in the bioaccessible fraction by FAAS. RESULTS: A new simple and fast method for determination of total concentrations of Ca, Cu, Fe, Mg, Mn, and Zn in bee pollen was developed and validated. The method combined room temperature, two-hour SE with 0.5 mol L-1 HNO3 with FAAS measurements versus simple standard solutions. It provided precision within 1-5 % and trueness better than 8%, and was shown to be suitable for fast analysis of different polyfloral bee pollens. In vitro gastrointestinal digestion revealed that elements were well (70-85 % for Ca, Mg) and fairly (27-43 % for Cu, Fe, Mn, and Zn) bioaccessible from bee pollen. By pouring with water and swelling overnight, bioaccessibility of studied elements from such prepared bee pollen was increased on average by less than 15 % (Mn), 20 % (Ca, Cu, Fe, Zn) or 30 % (Mn). CONCLUSIONS: Avoiding long-lasting, high-temperature wet digestion with concentrated reagents, the proposed sample treatment along with FAAS provided precise and true results of total concentrations of Ca, Cu, Fe, Mg, Mn, and Zn in bee pollen. The method was simple and fast, and enabled to analyze a higher number of samples. Simulated gastrointestinal digestion of bee pollen have shown for the first time that Ca and Mg are the most bioaccessible from this bee product. Bioaccessibility of Cu, Fe, Mg, and Zn from bee pollen are close to or lower than 40 %.

Simplified Method of Multi-Elemental Analysis of Dialyzable Fraction of Tea Infusions by FAAS and ICP OES.

A fast and straightforward sample preparation procedure of the dialyzable fraction of infusions of teas prior to their analysis on Al, Ba, Ca, Cu, Fe, Mg, Mn, Ni, Sr, and Zn contents by flame atomic absorption spectrometry (FAAS) and inductively coupled plasma optical emission spectrometry (ICP OES) was developed and validated. The proposed methodology was based on acidification with HNO3 only and demonstrated good analytical performance, i.e., precision (0.80-5.0%), accuracy (< 5%), recoveries of elements (97.4-105%), and their detection limits (0.075-1.1 µg L-1) along with linearity of calibration curves in the whole studied concentration ranges. Applicability of the evaluated procedure, being a useful alternative to time-consuming wet digestions, was tested by determining bioaccessibility of elements in 20 infusions of black (BT) and green (GT) teas as assessed with the aid of in vitro gastrointestinal digestion. Average contributions of bioaccessible fractions (%) of studied metals were as follows: 1.18 (Al)-40.7% (Ca) and 4.65% (Al)-46.3% (Ca) for BTs and GTs, respectively. Drinking daily four cups (1 L) of tea, recommended dietary intakes (RDIs) of Ca, Cu, Fe, Mg, and Zn were covered to a small degree (< 1.5%). Only bioaccessibility of Mn highly contributed to RDI for this metal. According to provisional tolerable weekly intakes (PTWIs) for toxic elements such as Al and Ni, consumption of both types of teas should not represent any health risk. Additionally, analysis of variance of results clearly indicated that BTs and GTs were mostly differentiated due to concentrations of the bioaccessible fraction of Al, Ba, Cu, and Ni.

New Green Determination of Cu, Fe, Mn, and Zn in Beetroot Juices along with Their Chemical Fractionation by Solid-Phase Extraction.

A new simple and rapid method for the determination of the total concentrations of Cu, Fe, Mn, and Zn in beetroot juices by flame atomic absorption spectrometry was developed and validated. The method included a very simple sample preparation, i.e., the two-fold dilution and acidification of the samples with HNO3 to 1 mol·L-1 and provided the precision within 2%-3% and the trueness better than 6%. The method was applied for the rapid screening analysis of the different commercially available beetroot juices. The chemical fractionation of Cu, Fe, Mn, and Zn was also proposed by the two-column solid-phase extraction with the reversed-phase and cation exchange tubes. It was revealed that Cu, Fe, Mn, and Zn were primarily in beetroot juices in the form of the organically bound forms, contributing to the distinguished hydrophobic and residual fractions. The sums of the mean contributions of both fractions were up to 98% (Cu, Fe, Zn) and 100% (Mn), pointing out that no labile nor unbound forms of the studied metals were present in the matrix of beetroot juices.