Leaves, Infusion, and Grounds-A Three-Stage Assessment of Element Content in Yerba Mate (Ilex paraguariensis) Based on the Dynamic Extraction and Mineralization of Residues.

The more yerba mate infusions that are consumed, the larger the amount of grounds generated. What is more, both the infusion and the residues after brewing remain rich elements. Therefore, a strategy for the three-stage assessment of the element content was presented. A new brewing method was based on dynamic extraction, ensuring both the ease of preparing the infusion and recovering the grounds. In turn, microwave-assisted acid mineralization was used to decompose the leaves and twigs of yerba mate before and after brewing. In total, 30 products were analyzed by ICP OES in three fractions each, i.e., dry yerba mate, infusion, and grounds, to determine up to 25 elements. The elemental composition was considered in terms of the country of origin, type, or composition of yerba mate. The extraction percentages obtained with dynamic extraction were comparable to previously used ultrasound-assisted extraction, as well as data from the literature. The three-stage strategy is a novel approach in yerba mate studies, and it may be a model procedure for the laboratory preparation of yerba mate grounds (waste that can be re-used, e.g., a natural fertilizer).

Chemical composition and physicochemical properties of natural therapeutic mud of Kazakhstan salt lakes: a review.

In recent years, interest in natural therapeutic mud has been growing all over the world. This natural product has a positive therapeutic effect on the skin and has fewer side effects on the human body. There are more than 40 thousand salt lakes in Kazakhstan. Most of them have natural mud sources, the potential of which has not yet been fully explored. The review presents an analysis of the available information on the physical and chemical properties of the main sources of natural mud from salt lakes in Kazakhstan and Kazakh sanatoriums that use natural mud in the treatment. All available publications, presenting the systematic studies, were used for data analysis. A comparative analysis of the mineralization of water, brine, and silt in one reservoir shows that the mineralization of water is not always the least. The available data indicate a point and partial nature of peloid studies, e.g., inorganic composition of natural muds from Western and Southern Kazakhstan is well described in the literature. In turn, there is a lack of these data from Northern and Eastern Kazakhstan. Studies of peloids in these regions seem to be a promising direction of the future research for both local and world scientists. What is more, there is also a big gap in the analysis of organic matter of muds from the Kazakh lakes. Comparing the state of the art, i.e., the studies from other parts of Asia and Europe, the identification of the organic part of muds is another desirable direction as a potential source of biologically active compounds of natural origin.

A Fast and Efficient Procedure of Iron Species Determination Based on HPLC with a Short Column and Detection in High Resolution ICP OES.

The optimization and application of a new hyphenated procedure for iron ionic speciation, i.e., high performance liquid chromatography (HPLC) with short cation-exchange column (50 mm × 4 mm) coupled to high resolution inductively coupled plasma optical emission spectrometry (ICP hrOES), is presented in this paper. Fe(III) and Fe(II) species were separated on the column with the mobile phase containing pyridine-2,6-dicarboxylic acid (PDCA). The total time of the analysis was approx. 5 min, with a significantly low eluent flow rate (0.5 mL min-1) compared to the literature. Additionally, a long cation-exchange column (250 mm × 4.0 mm) was used as reference. Depending on the total iron content in the sample, two plasma views were chosen, e.g., an attenuated axial (<2 g kg-1) and an attenuated radial. The standard addition method was performed for the method's accuracy studies, and the applicability was presented on three types of samples: sediments, soils, and archaeological pottery. This study introduces a fast, efficient, and green method for leachable iron speciation in both geological and pottery samples.

Influence of Brewing Method on the Content of Selected Elements in Yerba Mate (Ilex paraguarensis) Infusions.

In this paper, the effect of the extraction method on the concentrations of selected elements in yerba mate (Ilex paraguariensis) infusions is presented. Seven pure yerba mate samples (without additives) were selected, representing various types and countries of origin. An extensive sample preparation procedure was proposed: ultrasound-assisted extraction using two types of extractants (deionized and tap water) at two different temperatures (room and 80 °C). In parallel, the above extractants and temperatures were carried out for all samples by the classical brewing method (without ultrasound). In addition, microwave-assisted acid mineralization was carried out to determine the total content. All the proposed procedures were thoroughly investigated with certified reference material (tea leaves, INCT-TL-1). For the total content of all the determined elements, acceptable recoveries (80-116%) were obtained. All digests and extracts were analyzed by simultaneous ICP OES. For the first time, it was assessed how tap water extraction affects the percentage of extracted element concentrations.

The Strength and Fire Properties of Paper Sheets Made of Phosphorylated Cellulose Fibers.

Phosphorylated cellulose can be an intrinsic flame retardant and a promising alternative for halogenated fire inhibitors. In this study, the mixture of di-ammonium hydrogen phosphate (DAP) and urea (U), containing phosphate and nitrogen groups, was applied to attain fire inhibitor properties. Functional groups of cellulose were grafted with phosphorous by keeping the constant molar ratio of 1/1.2/4.9 between anhydroglucose units of cellulose/DAP/U in different concentrations of bleached kraft pulp. Phosphorus concentrations were determined using the ICP hrOES method, and paper sheets were made using the Rapid Köthen apparatus. The tensile strength of phosphorylated cellulose increased twice compared with unmodified cellulose when the phosphorous concentration increased to 10,000 g/kg. An increase in the tensile index comes from the higher freeness of pulp and cross-linking of the phosphorous group between cellulose fibers. Remarkable fire retardancy effects were achieved in cellulose concentrations above 5 wt%. The raised phosphorous concentration above 10,000 g/kg due to the phosphorylation process caused the formation of a char layer on a cellulose surface and the nonflammable gas emission. That effect was indirectly confirmed by reducing the combustion temperature and HRR by 50 and 45%, respectively. Due to increasing phosphorus concentration in cellulose sheets, cellulose's fire and strength properties increased significantly.

Recent applications of continuous flow chemical vapor and hydride generation (CVG, HG) coupled to plasma-based optical emission spectrometry (ICP OES, MIP OES).

Chemical vapor or hydride generation (CVG/HG) still plays a significant role in continuous flow sample introduction system. The development and higher accessibility of new commercial CVG/HG accessories (especially modified spray chambers and nebulizers) improves the analytical possibilities of plasma-based optical emission spectrometry for determination of hydride forming analytes. These systems are still designed and widely applied despite the better availability of its alternatives. The commercialization of the first nitrogen microwave induced plasma optical emission spectrometry instrument (MIP OES) also contributes to the increase in popularity of these solutions. The latest achievements in commercial and laboratory-made generators and instruments, as well as new strategies in sample preparation for total content and speciation analysis, are discussed in the review.

Chronic Alcohol Abuse Alters Hepatic Trace Element Concentrations-Metallomic Study of Hepatic Elemental Composition by Means of ICP-OES.

Trace element accumulation varies in different human tissues. Distribution of several elements was found to be disrupted in the case of excessive alcohol consumption, causing negative effects and exacerbation of pathological processes in the liver. In this study, we analyzed the levels and interactions between seven trace elements including calcium (Ca), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), potassium (K), and magnesium (Mg), manganese (Mn), sodium (Na), zinc (Zn), and selenium (Se) in individuals with alcohol-use disorder (AUD) and patients without AUD (control group). The liver samples were collected during autopsy from 39 individuals with AUD and 45 control subjects. Elemental composition inductively coupled plasma optical emission spectrometry (ICP-OES) after wet mineralization by nitric acid was applied for the evaluation of the samples. Positive correlations dominated in the AUD group, mainly in relation to Mg, which strongly positively correlated with Ca, Mn, Fe; K correlated with Mn and Zn, and Cu positively correlated with K and Zn. The strongest positive correlation in the AUD group was observed for the Mg-Mn pair (r = 0.87). Significant statistical differences (p < 0.05) between the groups concerned the average concentration of Co, Cu, Mn, and Mg, which were lower in the AUD group, and Fe, the level of which was significantly higher in the AUD group compared to the control group. Evaluation of the chronic alcohol consumption effect on the accumulation of trace elements in the liver allows a better understanding of the pathological processes taking place in this organ.

Rare Earth Elements Accumulation in the Hair of Malagasy Children and Adolescents in Relation to Their Age and Nutritional Status.

Due to undesired influence, the accumulation of rare earth elements (REE) in the human body has been discussed recently. However, it is usually limited to the study of the population living where REE ores and mines are located. The aim of the experiment presented was to analyse the concentration of REE in the hair of children and teenagers living in two areas of Madagascar in relation to the place of residence, nutritional status, age and sex. REE concentration was determined in scalp hair of 262 of subjects (5-19 years old) by an inductively coupled plasma-optical emission spectrometer. The content of total REE in the Malagasy hair was in the range of 0.79-44.15 mg/kg. The nutritional status was evaluated by Cole's index, and malnutrition of children was observed more often in village areas. The concentration of these elements was also determined in 20 samples for the estimation of environmental exposure. No significant differences were detected in the content of these elements in the studied regions, although the mean value was always higher in soil samples from the Antananariva region. The obtained data suggest dependence between REE concentration in the hair and age, and nutritional status of the examined subjects. Even if the observed correlations are weak, they contribute significant knowledge on the accumulation of REE in the bodies of children living in areas that are not recognised as deposits of these elements.

Concentration of selected elements in the hair of Madagascar girls in relation to nutritional status and place of residence.

Although the children malnutrition in Madagascar and the environmental pollution of this country has been widely discussed, there is no research on the differences in toxic elements accumulation in human body in dependence on nutritional status of Malagasy. Nine elements concentration (Al, As, Cd, Cr, Hg, Ni, Pb, Sn and Sb) was determined in scalp hair of 103 schoolgirls (8­15 years old), living in two areas: urban ­ close to Antananarivo (UR) and rural Berevo region (RU). Samples were analysed by an inductively coupled plasma optical emission spectrometer. The nutritional status was evaluated by Cole's index. Underweight was related to higher accumulation of Al, Cd and Cr in the hair girls, and more common among girls living in RU than UR region (42 % v. 28 %). Two-factor ANOVA showed differences in the Al and Cr content in the girls' hair depending both on their place of residence and nutritional status. This indicates additional consequence of malnutrition to the girls development and health.

Elemental and Speciation Analyses of Different Brands of Yerba Mate (Ilex paraguariensis).

In this work, a methodology for determination of As(III), As(V), dimethylarsinic acid (DMA), Fe(II) and Fe(III) in fifty-eight samples (forty-nine products of thirteen brands from three countries) commercial yerba mate (Ilex paraguariensis) was performed. The hyphenated high performance liquid chromatography inductively coupled plasma optical emission spectrometry (HPLC-ICP OES) technique was used. Arsenic was determined below the quantification limit in 38 samples of yerba mate. As(III) was found at the level 0.09 and 0.08 mg kg-1. The As(V) content was in the range: 0.21 to 0.28 mg kg-1. The content of DMA was found the highest of the three arsenic species in the range: 0.21 to 0.47 mg kg-1. The content of Fe(II) and Fe(III) was found in the range: 0.61 to 15.4 mg kg-1 and 0.66 to 43.1 mg kg-1, respectively and the dominance of Fe(III) was observed. Moreover, total and extractable content of 16 elements were determined. The results have been subjected to statistical analysis in order to establish relationships between samples of the same origin (country), kind (type) and composition (purity).

Iron Forms Fe(II) and Fe(III) Determination in Pre-Roman Iron Age Archaeological Pottery as a New Tool in Archaeometry.

This article presents studies on iron speciation in the pottery obtained from archaeological sites. The determination of iron forms Fe(II) and Fe(III) has been provided by a very simple test that is available for routine analysis involving the technique of molecular absorption spectrophotometry (UV-Vis) in the acid leachable fraction of pottery. The elemental composition of the acid leachable fraction has been determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Additionally, the total concentration of the selected elements has been determined by X-ray fluorescence spectrometry with energy dispersion (EDXRF). The results of the iron forms' determinations in archaeological pottery samples have been applied in the archaeometric studies on the potential recognition of the pottery production technology, definitely going beyond the traditional analysis of the pottery colour.

The Multi-Elemental Composition of the Aqueous Humor of Patients Undergoing Cataract Surgery, Suffering from Coexisting Diabetes, Hypertension, or Diabetic Retinopathy.

The aim of the study was the multi-elemental analysis of aqueous humor (AH) collected from patients undergoing cataract surgery. The study included: 16 patients with age-related macular degeneration AMD (99 controls), 10 patients with retinopathy (105 controls), 61 patients with hypertension (54 controls), and 33 patients with coexisting diabetes (82 controls). The control groups were recruited from patients with a lack of co-existing disease characterizing the specified studied group. The measurements were performed by the use of inductively coupled plasma optical emission spectrometry (ICP-OES). The statistical analysis was carried out using non-parametric testing (Mann-Whitney U). The level of significance was set at p = 0.05. The data obtained revealed substantial variations in elemental composition between the test groups in comparison to the controls. However, the significant variations concerned only a few elements. The phosphorous (P) level and the ratio of P/Ca were significant in retinopathy and diabetes, whereas cobalt (0.091 ± 0.107 mg/L vs. 0.031 ± 0.075 mg/L; p = 0.004) was significant in AMD. In co-existing hypertension, the levels of tin (0.293 ± 0.409 mg/L vs. 0.152 ± 0.3 mg/L; p = 0.031), titanium (0.096 ± 0.059 mg/L vs. 0.152 ± 0.192 mg/L; p = 0.045), and ruthenium (0.035 ± 0.109 mg/L vs. 0.002 ± 0.007 mg/L; p = 0.006) varied in comparison to the controls. The study revealed inter-elemental interactions. The correlation matrices demonstrated the domination of the positive correlations, whereas negative correlations mainly concerned sodium.

Iron species determination by high performance liquid chromatography with plasma based optical emission detectors: HPLC-MIP OES and HPLC-ICP OES.

The paper presents an independent application of two hyphenated techniques, wherein an identical chromatographic system i.e. high performance liquid chromatography (HPLC) was coupled to microwave induced plasma optical emission spectrometry (MIP OES) or inductively coupled plasma optical emission spectrometry (ICP OES). A cation-exchange column and a mobile phase based on pyridine-2,6-dicarboxylic acid (PDCA) were employed to separate Fe(II) and Fe(III) within 300 s. Additionally, two methods of sample preparation were employed. Optimization and validation of both methods were conducted parallel. The applicability was presented with different sample matrix types: post-glacial sediments, archaeological pottery, soils located in the proximity of industry wastes disposal site, river sediments and yerba mate (Ilex paraguariensis). Obtained results were compared in terms of the excitation source (microwave induced or inductively coupled) and supplied gas (nitrogen or argon). The research introduces HPLC-MIP OES for iron speciation analysis and its applicability were critically evaluated with HPLC-ICP OES.

Multi-mode Sample Introduction System (MSIS) as an interface in the hyphenated system 2 HPLC-MSIS-ICP-OES in simultaneous determination of metals and metalloids species.

The paper presents a usage of a new hyphenated technique, wherein a Multi-mode Sample Introduction System (MSIS) was applied as an interface of two high pressure liquid chromatography units and inductively coupled plasma optical emission spectrometry (2 HPLC-MSIS-ICP-OES). Simultaneous separation and detection of non-hydride forming and hydride forming elements was possible due to the application of two different HPLC column, cation-exchange and anion-exchange respectively. The method was able to determine 15 elements quantitatively with a distinction of three arsenic and two iron species and it was validated obtaining acceptable LODs (2.67-28.7 µg L-1) and recoveries (80-120%). The method applicability was presented and confirmed on 5 varied sample matrix types i.e. post-glacial sediments, yerba mate (Ilex paraguariensis), soil samples located in the proximity of industry wastes disposal site, river sediments, and archaeological pottery. In addition to the above, unknown Cu, Fe, Mn and Zn species were detected in real samples (qualitative speciation analysis) and the identification was attempted according to the literature.

Quantifying the functional disparity in pigment spot-background egg colour ICP-OES-based eggshell ionome at two extremes of avian embryonic development.

It is known that a developing avian embryo resorbs micronutrients (calcium and other chemical elements) from the inner layer of the eggshell, inducing thinning and overall changes in the shell's chemical composition. However, an aspect yet to be explored relates to the local changes in the multi-elemental composition (ionome) of the pigment spot and adjacent background colour regions of eggshells resulting from avian embryogenesis (with respect to two extremes of embryonic growth: the maternal level at the moment of egg laying, and after the completion of embryonic growth). To address this problem, we used inductively-coupled plasma optical emission spectrometry (ICP-OES) to establish the elemental profiles of microsamples from the cryptic eggs of Capercaillie Tetrao urogallus and Black Grouse Tetrao tetrix, representing the background colour and pigment spot regions of the shell. We then related these to the developmental stage of the eggs (non-embryonated eggs vs. post-hatched eggshells) and their origin (wild vs. captive hens). Our results show an apparent local disparity between the pigment spot and background colour regions in the distribution of chemical elements: most elements tended to be at higher levels in the speckled regions of the shell, these differences becoming less pronounced in post-hatched eggshells. The trends of changes following embryonic eggshell etching between the pigment spot and background colour shell regions were conflicting and varied between the two species. We hypothesized that one potential working explanation for these interspecific differences could be based on the variable composition of elements (mostly of Ca and Mg), which are the result of the varying thickness of the individual shell layers, especially as the relative difference in shell thickness in the pigment spots and background colour regions was less in Black Grouse eggs. Overall, this investigation strongly suggests that egg maculation plays a functional role in the physiological deactivation of trace elements by incorporating them into the less calcified external shell layer but without participating in micronutrient resorption. Our major critical conclusion is that all research involving the chemical analysis of eggshells requires standardized eggshell sampling procedures in order to unify their colouration and embryonic status.

Colour-assisted variation in elytral ICP-OES-based ionomics in an aposematic beetle.

Very little is known about how the elemental composition (ionome) of an insect cuticle varies as a result of different colouration. Using inductively-coupled plasma optical emission spectrometry (ICP-OES), we established ionomic profiles in microsamples of two adjacent regions of an insect cuticle with a contrasting colour pattern, namely, the black and orange regions of the elytra of the aposematic burying beetle Nicrophorus vespillo. The analysis revealed 53 elements (ranging in atomic weight from Na to Bi) occurring above the detection limit. The frequency of detectability of individual elements varied strongly, and only ten elements (Ba, Cu, Fe, K, Mg, Mn, P, Rb, Sb and Zn) were present in concentrations exceeding the detection limit in all the samples. The sum of concentrations of all elements in the orange regions of the elytra was 9% lower than in the black ones. The opposite distribution was displayed by the rare earth elements (REEs), the sum of which was 17% lower in the black elytral regions than in the orange ones. The concentrations of six elements were significantly higher in the black than in the orange regions: Al (by 97%), Cu (41%), Mn (14%), Na (46%), Se (97%) and W (47%). The concentrations of essential elements measured in both the black and orange regions exhibited very considerable variance: Ca (σ2 = 1834; 1882, respectively), K (145; 82) P (97; 76), Na (84; 53), Mg (24; 26) and Ba (9; 13). This, in part, could be attributed to individual differences, e.g. those resulting from the consumption of animal carcasses of different quality/chemical composition, but interference between elements and the consequent lowering of measurement quality are also possible. We highlight the fact that deeper insight into the basic relationship between insect colouration and variation in elemental composition requires micro-sampling of the homogeneous layers of an exoskeleton.

Correlations Between Trace Elements in Selected Locations of the Human Brain in Individuals with Alcohol Use Disorder.

Trace element distribution varies in different locations of the human brain. Several elements were found to cause various negative effects, such as neurodegeneration. In this paper, we analyzed the interactions between seven trace elements: zinc (Zn), selenium (Se), manganese (Mg), iron (Fe), copper (Cu), chromium (Cr) and cobalt (Co) in individuals with alcohol use disorder (AUD) and individuals without (control group). Brain tissue samples from 31 individuals with AUD and 31 control subjects were harvested. Inductively coupled plasma optical emission spectrometry was used for trace element determination. In the control group, there were several positive correlations between Cr, Cu, Fe and Mn. In the AUD group, positive correlations between Co and Cr, Cu, Fe, Mn, Zn were found. The majority of correlations between Zn and other elements are positive. In the studied group, Mn had strong positive correlations with Co, Cr, Cu and Fe. The strongest positive correlation found between average element concentration was between Cu and Cr. The knowledge of kinetics and metabolism of trace elements as well as the impact of alcohol on these processes is essential for understanding the pathological processes and functioning of human brain tissue.

In-spray chamber hydride generation by multi-mode sample introduction system (MSIS) as an interface in the hyphenated system of high performance liquid chromatography and inductivity coupled plasma optical emission spectrometry (HPLC/HG-ICP-OES) in arsenic species determination.

The paper presents a new usage of a commercial in-spray chamber hydride generator, Multi-mode Sample Introduction System (MSIS) as a connector of high pressure liquid chromatography and inductivity coupled plasma optical emission spectrometry (HPLC/HG-ICP-OES). This hyphenated technique was applied in a determination of inorganic and organic arsenic species. The optimization of a hydride generation process in MSIS and a chromatographic separation (using anion-exchange HPLC column with phosphate buffer as a mobile phase) were carried out compositely. The method allowed to determine three arsenic forms, As(III), As(V) and dimethylarsinate (DMA) within 400s of a single analysis. The obtained limits of detection (LODs) were 2.08   µg L-1 for As(III); 6.97   µg L-1 for As(V); 6.15   µg L-1 for DMA and precision 2.7%, 4.8%, and 5.7%, respectively, for 100   µg L-1. The described method was used for environmental and food samples analyses.

The Effect of Mushroom Extracts on Human Platelet and Blood Coagulation: In vitro Screening of Eight Edible Species.

Cardiovascular diseases remain the leading global cause of mortality indicating the need to identify all possible factors reducing primary and secondary risk. This study screened the in vitro antiplatelet and anticoagulant activities of hot water extracts of eight edible mushroom species (Agaricus bisporus, Auricularia auricularia-judae, Coprinus comatus, Ganoderma lucidum, Hericium erinaceus, Lentinula edodes, Pleurotus eryngii, and Pleurotus ostreatus) increasingly cultivated for human consumption, and compared them to those evoked by acetylsalicylic acid (ASA). The antioxidant capacity and concentration of polysaccharides, phenolic compounds, organic acids, ergosterol, macro elements, and trace elements were also characterized. The most promising antiplatelet effect was exhibited by A. auricularia-judae and P. eryngii extracts as demonstrated by the highest rate of inhibition of adenosine-5'-diphosphate (ADP)-induced and arachidonic acid (AA)-induced aggregation. The response to both extracts exceeded the one evoked by 140 µmol/L of ASA in the ADP test and was comparable to it in the case of the AA test. Such a dual effect was also observed for G. lucidum extract, even though it was proven to be cytotoxic in platelets and leukocytes. The extract of P. ostreatus revealed an additive effect on AA-induced platelet aggregation. None of the mushroom extracts altered the monitored coagulation parameters (prothrombin time, prothrombin ratio, and International Normalized Ratio). The effect of mushroom extracts on platelet function was positively related to their antioxidative properties and concentration of polysaccharides and ergosterol, and inversely related to zinc concentration. The study suggests that selected mushrooms may exert favorable antiplatelet effects, highlighting the need for further experimental and clinical research in this regard.

Levels of Trace Elements in the Aqueous Humor of Cataract Patients Measured by the Inductively Coupled Plasma Optical Emission Spectrometry.

Trace elements play an important role in the pathogenesis of several serious ophthalmological disorders, such as glaucoma, age-related macular degeneration (AMD), diabetic retinopathy, cataract, etc. This study aimed to measure alterations of chemical elements' (67) levels in the aqueous humor of patients undergoing cataract surgery. The pilot study included 115 patients, (age 74 ± 7.27, female 64.35%, male 35.65%). The aqueous levels of elements were measured by the use of the inductively coupled plasma optical emission spectrometry (ICP-OES), quality controlled with certified standards. The classification of elements based on their concentration was achieved by hierarchical cluster analysis. This is the first screening study that quantifies over 60 elements which are present in the fluid from the anterior chamber of the eye of cataract patients. The obtained results can be suitable for understanding and identifying the causes that may play a role in the initiation and progression of lens opacity.