Elemental composition of spices and herb products on the Kosovo market

In this work, sample preparation methods for polymer digestion based on microwave-induced combustion (MIC) and microwave-assisted acid digestion (MW-AD) were evaluated for further As, Bi, Cd, Co, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Sr, Ti, V and Zn determination by inductively coupled plasma mass spectrometry (ICPMS) and inductively coupled plasma optical emission spectrometry (ICPOES). Samples of low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET, colorless and green), polyetheretherketone (PEEK) and nylon 6,6 were digested using MIC and MW-AD in closed quartz vessels. The type and concentration of acids used for MIC were investigated and better results were achieved using a 4 mol l−1 HNO3 + 4 mol l−1 HCl solution. Microwave-assisted acid digestion was also evaluated for polymer digestion using concentrated acids. Both sample preparation methods were considered suitable for polymer digestion but MIC was preferable in view of the possibility of using diluted acids as absorbing solution and allowing higher sample mass to be digested and consequently better limits of detection. Residual carbon content in digests of polymers obtained by MIC was lower in comparison with the values obtained after MW-AD. Accuracy for all the analytes determined by ICPOES and ICPMS after MIC digestion was better than 95% (analysis of certified reference materials and by neutron activation analysis). It was possible to digest up to 8 samples by MIC in less time (in 25 min) in comparison with MW-AD (more than 50 min) and also using diluted acids (4 mol l−1 HNO3 and HCl) instead of concentrated acids.

Since the consumption of dairy products, especially ice cream and cream, is very high in Iran and the world, either directly or indirectly, and no study has been conducted so far on measuring elements in different types of ice cream and cream, the aim of the present study was to investigate levels of 15 elements (Co, Mn, Fe, Cr, Se, Mg, P, Ca, Zn, Hg, Al, Ni, Cd, As, and Pb) by using ICP-OES (Inductively Coupled Plasma Optical Emission Spectroscopy) technique in the mentioned products along with a health risk assessment by Monte Carlo Simulation. Based on our findings, in all samples, the highest average level of toxic elements was related to Al (29.2 ± 23.9 µg/kg fw or fresh weight), and the lowest mean level of toxic elements was related to Hg (not found). Moreover, the highest average level of essential elements was related to P (8895 ± 4369 µg/kg fw) and the lowest mean level of essential elements was related to Se (0.610 ± 0.150 µg/kg fw). Also, the highest averages of toxic elements in cream was related to As (12.5 µg/kg fw) and in ice cream was related to Al (43.9 µg/kg fw), and the lowest averages were obtained for Hg (not found) in both products. Also, the highest and lowest averages of essential elements in cream were related to P (10641 µg/kg fw) and Se (not found), respectively, and in the ice cream were related to Ca (8135 µg/kg fw) and Se (0.630 µg/kg fw), respectively. In the end, the levels of elements in all ice cream and cream samples were below the standard level. The Monte Carlo method risk assessment reveals that the non-carcinogenic risks from consuming cream and ice cream pose no threat to children or adults (TTHQ < 1.00), but on the contrary, the outcomes of the carcinogenic risk assessment show the TILCR values for both groups exceed acceptable limits, that this indicating a potential risk threat from these products. The principal component analysis (PCA) results revealed the categorization of various toxic and essential elements in all samples. Based on the results obtained, it can be concluded that the consumption of these products is somewhat safe, but more monitoring is needed in the food cycle from farm to fork.

The determination of rare earth element (REE) content in different natural minerals is of high interest due to their extensive use in modern and sustainable technologies. The REEs occurring in natural zeolites are specific to each deposit. This study presents the validation and evaluation of the measurement uncertainty for the determination of REEs (Ce, Dy, Er, Eu, Gd, La, Lu, Nd, Pr, Sm, Y, and Yb) in natural zeolites using microwave-assisted acid digestion and inductively coupled plasma optical emission spectrometry (ICP-OES) after diffusive gradients in thin-film preconcentration. A mixture of HNO3 : HCl : HF of 3 : 9 : 2 (v/v/v) and microwave digestion provided suitable recoveries for the analysis of two certified reference materials, CRM BCS-CRM 375/1 and CRM OREAS 460. Good linearity over the calibration range of 0-2 μg mL-1, with correlation coefficients of 0.9995-1.0000, was obtained for each REE by ICP-OES. The limits of quantification (LOQS), calculated considering the instrumental LOQs and the sample preparation by microwave digestion, were in the range of 0.20-0.60 mg kg-1. A supplementary step of preconcentration/matrix separation based on the passive sampling by diffusive gradients in thin-films (DGT) technique improved the LOQs by about 20 times after three days of passive accumulation, allowing the measurement of the concentrations of all studied REEs in natural zeolite samples. The proposed methodology is a suitable approach for the measurement of REEs at low concentrations in natural zeolite samples by ICP-OES, and it can be extended to other geological samples. The measurement uncertainty was calculated based on the validation data. The proposed method provides reliable results for the measurement of REEs in natural zeolites and was used to measure the specific concentrations of REEs in natural zeolite samples from three Romanian quarries. The REE concentration can be used as a fingerprint for each deposit.

Due to the small quantity of most of the extracted human urinary stone samples, there is an urgent need for an analytical technique that is able to perform a multi‐elemental quantitative analysis for a small fraction of these samples. In the present work, a few milligrams of different types of urinary stones were microwave digested in ultra‐pure nitric acid, and the elemental determination was achieved by total reflection X‐ray fluorescence (TXRF). The elements P, S, Ca, Fe, Cu, Zn, Se, and Sr were detected in most of the different stones. However, the trace elements: K, Ti, V, Cr, Mn, Ni, As, Pb, and U were also found in a certain number of samples. Furthermore, inductively coupled plasma optical emission spectrometry (ICP‐OES) was used and the elements Mg, Ti, Mn, Cu, Zn, and Cd were determined. A good agreement between the results of TXRF and ICP‐OES was obtained with respect to the elements Ti, Mn, Cu, and Zn. Cadmium and magnesium were only determined by ICP‐OES. More attention was given to the existence and the spectral interference of As‐K α and Pb‐L α as well as As‐K β and Br‐K α in a limited number of urinary stones. Based on the analysis of variance and Pearson's correlation analysis, an additional statistical analysis study was performed in terms of quantified elements and the types of urinary stones. Calcium has a remarkable positive correction with Ni, Zn, and P, whereas a negative correlation was found with K, S, and Cu. Based on the hierarchical cluster analysis, the square Euclidean showed four main groups of urinary stones starting with high to trace amounts of calcium oxalate. Furthermore, the squared Euclidean showed further subgroups of the urinary stones. The role of certain elements in terms of forming or inhabiting the urinary stone formation was discussed. Uranium was determined in a limited number of urinary stones using TXRF and ICP‐OES. The origin of the uranium may be the drinking and groundwater. Uranium could be accumulated in the urinary stones from these sources. In addition, the divalent uranium compounds can deposit on the surface of hydroxyapatite crystal, which is one of the main compounds in the urinary stones.

Background: Multivariate statistical analyses were used to investigate the mineral contents of wines from the mid-São Francisco River valley, located between the northeastern Brazilian States of Bahia and Pernambuco, with those of wines from Rio Grande do Sul State. Methods: Ten elements (Al, Ba, Ca, Fe, K, Mg, Mn, Na, P, and Zn) were determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The results were applied to Principal Components Analysis PCA) and and Hierarchical Cluster Analysis (HCA). Results: Considering the 28 wine samples analyzed, the elements Ca, Mg, K, and P were found in higher concentrations in the northeastern wines, with average contents of 71.6, 85.5, 632.9, and 191.2 mg L-1, respectively, and concentration ranges of 6.7-132.0, 53.7-120.7, 177.8-1071.9, and 79.5-376.1 mg L-1, respectively. Conversely, the elements Al, Ba, Fe, Mn, Na, and Zn were found in lower concentrations in the northeastern wines, with average contents of 0.53, 0.19, 1.31, 1.47, 0.69, and 0.46 mg L-1, respectively, and concentration ranges of 0.17-1.28, 0.03-0.46, 0.26-2.34, 0.41-2.73, 0.29-1.59, and 0.06-0.95 mg L-1, respectively. Conclusion: Principal component analysis and hierarchical cluster analysis revealed a natural distinction between the wines from the mid-Sao Francisco River valley and Rio Grande do Sul. Keywords: Brazilian wines, geographical origin, mineral contents, ICP-OES, PCA, HCA.

Selected multivariate data analysis methods have been used to study chemical features (some minor elements) of surface stream sediments collected from Meshkinshahr, NW Iran, for a geochemical investigation. A total of 630 samples were collected and levels of 22 elements (Au, Hg, Cr, Cu, Mn, Ni, Sr, Zn, Ba, Be, Ti, Ag, As, B, Bi, Co, Mo, Pb, Sb, Se, Sn, and W) were determined in each sample using fire assay for Au and inductively coupled plasma optical emission spectrometry (ICP-OES) for the rest. The data were processed using data-handling tools. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) as unsupervised ordination and clustering methods monitored differences in samples according to the chemical compositions. PCA and HCA were used to express the relationships of the minor element distributions to identify the possible sources of these elements in that area. The results of PCA and HCA classified the samples into three main groups. Partial least squares discriminant analysis (PLS-DA) and support vector machine discriminant analysis (SVM-DA) were implemented as supervised classification models. PLS-DA and SVM-DA were applied to detect the relationship between the chemical contents and to discriminate different samples. Respectively, 545 and 85 samples were selected as calibration and prediction sets for classification methods. The prediction abilities of PLS-DA and SVM-DA models were 91.8 % and 79.0 %, respectively.

A methodology based on inductively coupled plasma optical emission spectrometry (ICP-OES) after microwave-assisted acid digestion was developed to determine the content of traces elements in curry samples from the Spanish market. The methodology was validated in terms of accuracy by the analysis of citrus and tomato leaf reference materials achieving comparable results with the certified values. The trace metal content of curry samples was compared with data available from previously published reports concerning Indian samples, especially in terms of heavy metal composition, in order to guarantee the quality of the commercially available spices in the European countries. Values found for the analysis of arsenic, lead and cadmium were significantly lower than the maximum limit allowed by European Union statutory limits for heavy metals and lower than those obtained for Indian curry leaves reported by Indian research teams by using neutron activation and γ-ray analysis.

Matrix effects were evaluated on the determination of Dy, Eu and Yb used as sheep faecal markers by inductively coupled plasma optical emission spectrometry (ICP-OES) with axially- and radially-viewed configurations. The samples were prepared with microwave-assisted acid digestion using an oven with closed vessels. The analytical performances of the two ICP-OES instruments were compared using Mg II/Mg I intensity ratios at different operating conditions. The values obtained using the axially-viewed ICP were 6.5 (1.3 kW and 0.7 l min−1) and 4.8 (1.0 kW and 0.9 l min−1). These values were higher than those determined using radially-viewed ICP-OES, 5.2 and 2.5, respectively. Under all operating conditions and for all elements measured, the detection limits obtained with the axially-viewed configuration were at least three-fold better, but were more critically affected by incremental background emission increases at a higher plasma power and lower nebulization gas flow rate. The accuracy of the Dy, Eu and Yb determinations in acid-digested faecal samples by axially- and radially-viewed ICP-OES was verified using the INAA technique, and a paired t-test showed that all results were in agreement at a 95% confidence level.

Ba and Sr may occur in relatively high content in natural zeolites and can contribute to the zeolites ion-exchange properties. In addition, some soluble compounds of Ba and Sr can be toxic, thus their determination is important. The aim of this paper was the development and validation of a method for determination of Ba and Sr in zeolites based on microwave-assisted acid digestion and inductively coupled plasma optical emission spectrometry (ICP-OES). For validation, a certified reference material (BCS-CRM 375/1) was used in the accuracy study, and the obtained recoveries were 92 ± 10 % for Ba and 95 ± 12 % for Sr. A mixture of HNO3:HCl:HF of 3:9:2 (v/v/v) and a digestion time of 40 min were found to give recoveries in the range of 80-120 %. The obtained LOQs in ICP-OES allowed the quantification of concentrations above 5.0 mg kg-1 Ba and 3.8 mg kg-1 Sr. The method was applied for the determination of Ba and Sr in five zeolite samples, and concentrations of 422 – 580 mg kg-1 for Ba and 115 – 183 mg kg-1 for Sr were found. The obtained performance parameters were in agreement with the requirements of international guidelines regarding methods validation.

Background: Today, the use of mathematical modeling is crucial in assessing the ecological safety of nutritive herbs. The aim of our research was to examine the mineral composition and assess the ecological purity of raw materials from Ziziphora clinopodioides Lam., collected across various natural and climatic zones in the South Caucasus region. Objective: To conduct an elemental analysis of the mineral composition and assess the ecological safety of nutritive plant raw materials derived from Ziziphora clinopodioides Lam. Methods: The analysis was performed using an Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) instrument, with results reported in micrograms per gram. A multi-standard approach with various dilutions was employed to investigate the quantities of elemental content. The elemental analysis of the obtained ash mass was conducted utilizing the Agilent 5800 VDV ICP-OES instrument ( USA). Mathematical modeling techniques, including Correlation Analysis, Principal Component Analysis, and Hierarchical Cluster Analysis, were used in the study. Results: Experimental data unequivocally demonstrated that the concentration of heavy metals in all analyzed Z. clinopodioides samples falls within the established limits of maximum permissible concentrations. Notably, no toxic metals such as Lead (Pb), Arsenic (As), or Cadmium (Cd) were detected in any of the samples, affirming the ecological safety of the raw materials. Principal component analysis yielded four predominant components, collectively accounting for 91.934% of the overall variability among 13 variables, as based on the variation in elemental concentrations. Furthermore, hierarchical cluster analysis (HCA) enabled the categorization of plant raw material samples into three distinct groups, contingent on the geographical origins of the areas and the methods of cultivation. Conclusions: Chemometric analysis conclusively demonstrates that the variation in elemental composition within the examined samples, as well as the plant's capacity to accumulate biologically active compounds, is contingent not solely upon the altitude of the growth locations above sea level but also by the conditions of cultivation and introduction. Keywords: Ziziphora clinopodioides Lam., nutritive herbs, ash, chemometric approaches, correlation analysis, hierarchical cluster analysis, optical emission spectrum

PROFILE OF INORGANIC ELEMENTS IN HONEY SAMPLES FROM THE MARANHÃO STATE AS A BIOINDICATOR OF GEOGRAPHICAL ORIGIN. Honey is a substance that contains a variety of macro and micro minerals present in the range between 0.02-1.03%. The main objective of this study was to determine the concentration of elements inorganic in 15 honey samples collected in various regions of Maranhão (Northeast Brazil), using highly sensitive analytical techniques, such as inductively coupled plasma optical emission spectrometry (ICP-OES), in addition to applying multivariate statistical tools, such as Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) in the treatment of data. The method presented detection limits between 0.4 to 2.8 mg kg-1. Fifteen samples and 19 metals were analyzed, and two of these samples had high levels of lead, exceeding the limits allowed by Brazilian legislation. Thus, it can be concluded that the presence of potentially toxic metals in honey is an indication that the production areas may be contaminated by different external sources. The chemometric analysis of the data by PCA and HCA allowed to classify honey in two main groups: honey produced in urban areas and honey produced in rural areas with PCA explaining 73% of the data variance with the sum of the first 3 components.

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.

Recreational lakes have variable levels of metal contamination. This study focused on a recreational lake located within a university campus in the Jengka area of Pahang, Malaysia. This lake provides leisure opportunities for the campus residents. This study investigates the levels of metals (iron (Fe), copper (Cu), manganese (Mn), lead (Pb), and zinc (Zn)), determines their potential sources, and predicts the potential health hazards. Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used to evaluate the metal concentrations. The average metal concentrations were determined in the order of Fe (1.71 mg/l) > Mn (0.69 mg/l) > Zn (0.08 mg/l)> Cu (0.019 mg/l) > Pb (0.013 mg/l). The pollution indices indicated substantial levels of cumulative metal contamination based on the contamination index (Cd) and Nemerow pollution index (NPI). However, single metal contamination is at low levels, according to the metal assessment index (MEI). Hierarchical cluster analysis (HCA) and principal component analysis (PCA) revealed that both anthropogenic and natural sources were responsible for the deposition of the metals. Children are more susceptible to both cancer and non-cancer hazards compared to adults. The study suggests that rigorous monitoring of water quality measures, and comprehensive health risk assessments, are required.

A simplified alternative to the wet digestion sample preparation procedure for roasted ground and instant coffees has been developed and validated for the determination of different elements by inductively coupled plasma optical emission spectrometry (ICP-OES) (Al, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, Zn) and flame atomic absorption spectrometry (FAAS) (Ca, Fe, K, Mg, Na). The proposed procedure, i.e. the ultrasound-assisted solubilisation in aqua regia, is quite fast and simple, requires minimal use of reagents, and demonstrated good analytical performance, i.e. accuracy from −4.7% to 1.9%, precision within 0.5–8.6% and recovery in the range 93.5–103%. Detection limits of elements were from 0.086 ng ml−1 (Sr) to 40 ng ml−1 (Fe). A preliminary classification of 18 samples of ground and instant coffees was successfully made based on concentrations of selected elements and using principal component analysis and hierarchic cluster analysis.

One hundred and fifty‐seven sherds of Campanian pottery were analysed by inductively coupled plasma optical emission spectroscopy (ICP‐OES) and flame emission spectroscopy (FES). The sherds were found in the course of archaeological excavations carried out at the sites of Sibari, Cosenza, Crotone, Locri, Reggio and Oppido Mamertina in southern Italy (ancient Bruttium, today Calabria). Analyses were carried out on dissolved samples, determining 15 elements per sample (Al, Fe, Ca, Mg, Ti, Mn, Sr, Ba, Cr, Cu, Y, La and Sc by ICP‐OES, and Na and K by FES). Analytical data were subject to multivariate statistical treatment by hierarchical cluster analysis and principal components analysis. Results indicated different compositional groups, allowing one to separate suspected imports from Campania, Etruria and Sicily from each other and from likely local products. The latter could be further classified into different groups, comprising imitations of foreign forms as well as original local products.