RESUMEN

An analytical method for the determination of toxicological relevant species of arsenic in urine was developed and validated using hydride generation microwave-induced emission spectrometry (HG-MP-AES). This strategy can be used as an alternative to HG-HPLC-ICP-MS considered as a reference technique for arsenic speciation. This procedure is notably less expensive than other techniques and sample preparation and requires only a few steps.•Hydride generation with MP-AES detection has proven to be an effective technique for measuring arsenic metabolites in urine, which is relevant for occupational monitoring and health risk assessment purposes.•This method offers simplicity and cost-effectiveness, serving as an alternative to classical analytical procedures typically used for arsenic analysis in urine.•The methodology has been successfully applied for the purpose of workers' health surveillance.

RESUMEN

Given rising traders and consumers concerns, the global food industry is increasingly demanding authentic and traceable products. Consequently, there is a heightened focus on verifying geographical authenticity as food quality assurance. In this work, we assessed pattern recognition approaches based on elemental predictors to discern the provenance of mandarin juices from three distinct citrus-producing zones located in the Northeast region of Argentina. A total of 202 samples originating from two cultivars were prepared through microwave-assisted acid digestion and analyzed by microwave plasma atomic emission spectroscopy (MP-AES). Later, we applied linear discriminant analysis (LDA), k-nearest neighbor (k-NN), support vector machine (SVM), and random forest (RF) to the element data obtained. SVM accomplished the best classification performance with a 95.1% success rate, for which it was selected for citrus samples authentication. The proposed method highlights the capability of mineral profiles in accurately identifying the genuine origin of mandarin juices. By implementing this model in the food supply chain, it can prevent mislabeling fraud, thereby contributing to consumer protection.

RESUMEN

This particular study was aimed to establish the level of heavy metals in different horticultural crops cultivated by irrigation and the soil in two sub-cities of Addis Ababa, Ethiopia, and quantitatively assess the health treat they pose for the consumer. A total of 151 vegetable samples comprised of lettuce (Lactuca sativa), cabbage (Brassica oleracea var. capitate), cucumber (Cucumis sativus), potato (Solanum tuberosum), parsley (Petroselinum crispum), Swiss chard (Beta vulgaris subsp. vulgaris), beetroot (Beta vulgaris), green onion (Allium porrum L.) and 28 soil samples were collected for this study. Six toxic elements were analyzed using microwave plasma atomic emission spectroscopy (MP-AES) after microwave assisted digestion of the samples. The concentrations of examined trace elements in vegetables (mg/kg) were found in the range of 5.50-93.00 for zinc; below detection limit (BDL)- 18.50 for copper; BDL-2.50 for nickel; BDL-17.00 for lead; 5.00-4256.50 for manganese and 22.00-8708.00 for iron. Considering the mean Pb content values, all vegetables exceeded the maximum permissible level set by the joint FAO/WHO commission in both irrigation sites. In case of Mn parsley, swiss chard, and green onion all from site two exceeded the maximum allowable values. With the exception of potato from irrigation site one, all vegetables exceeded the maximum permissible limit set for Fe concentration and out of which parsley, swiss chard, and green onion, all from site two, exceeded by more than double amount. The same trend is observed for the concentration of Mn and Fe in the soil samples. In fact, in both irrigation sites their concentration exceeded the allowable limits set by United Nation Environment Program (UNEP) for agricultural soils. The metal pollution load index revealed that in most of the vegetables studied the overall pollution load of trace metals were higher in Kolfe Keranyo irrigation site. The risk assessment study using indices like estimation of daily/weekly dietary exposure, hazard quotient and metal pollution load index all suggested consumption of the studied vegetables poses a significant health risk for the consumer. For adults the calculated target hazard quotient for the trace element Pb is higher than 1 (one) for all of studied vegetables ranging from 11.086 (cucumber) to 17.881 (beetroot) with a 98.216% and 98.464% contribution to the hazard indices, respectively. For a child consumer, Mn showed a higher target hazard quotient vales ranged from 0.0107 (cucumber) to 0.0495 (green onion) with a 70.86% and 88.85% contribution to the total hazard indices, respectively. The soil pollution indices also indicated that the degree of metal enrichment in soils and sediments are higher than the allowable limits. Therefore, a prompt action is required to curb the problem and ensure the public safety along the food system line.

RESUMEN

Green Analytical Chemistry (GAC) metrics include a variety of criteria, such as the regent amounts and toxicity, energy consumption, generated waste, among others. The analytical greenness metric (AGREE) and its variant for sample preparation (AGREEprep) cover different aspects that contribute to the environmental sustainability of sample preparation. White Analytical Chemistry (WAC) considers not only environmental aspects but also analytical and practical aspects with a holistic vision based on a Red-Green-Blue color model. A case study is presented to assess the green and white profile of a method based on ultrasound-assisted extraction and determination of Mn and Fe in beef using microwave-induced plasma atomic emission spectroscopy (MP AES). The method was validated and resulted simple, fast without external heating using diluted acids. It was concluded that we should think in green sample preparation with the AGREEprep tool, as well as in white holistic assessments (WAC) as both constitute complementary tools.

RESUMEN

Exosomes are small vesicles released by all types of cells, and they have been postulated as a promising natural way to carry information amongst cells. Exosomes might serve as mediators for intercellular communication through the delivery of their endogenous cargo to neighbor or distant cells. Recently, this ability to transfer their cargo has open a new therapeutic approach and exosomes have been investigated as vectors for the delivery of the loaded cargo, for instance nanoparticles (NPs).Currently, several methods to load exosomes with NPs have been described; however, the maintenance of the membrane integrity on the vesicle has to be taken into consideration, in order to choose one or another methodology. Here we describe the NP encapsulation through the incubation of the cells with the NPs and the subsequential methods to determine their cargo and to discard detrimental alterations on the loaded exosomes.

Asunto(s)

RESUMEN

Milk is a complete food useful to promote growth and development of the infant mammals as it contains vital nutrients (proteins, essential fats, vitamins, and minerals) in a balanced proportion. It is also a nutritious food for adults too. Milk can also contain hazardous chemicals and contaminants including heavy metals which can be a risk for health. This study was aimed at determining the level of heavy metals in cow's milk collected from Butajira and Meskan districts, south Ethiopia. Cows' milk was collected from 193 healthy lactating cows. Samples were digested by optimized microwave digestion method using HNO3 and H2O2. Analysis was done using ICP-OES for Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn levels. MP-AES was used for Ca, Mg, K, and Na. Ni was not detected in all samples. Concentrations of heavy metals in the studied samples were Cd (0.0-0.03), Cr (0.0-0.4), Cu (0.03-1.1), Fe (0.0-1.9), Mn (0.0-0.7), Pb (0.0-12.3), Zn (0.0-8.2), Ca (380.1-532.4), Mg (159.6-397.9), K (1114.2-1685.8), and Na (495.9-1298.3) ppm. These values were compared with permissible values prescribed by different international organizations and available literatures. Cd, Cr, Cu, Mn, Pb, Zn, and Mg levels were found above the permissible limits. Thus, special attention needs to be given to the level of heavy metals in cows' milk, as they are difficult to remove from the body. Their accumulation to a level greater than their permissible limit could be deleterious to the health of the user.

Asunto(s)

RESUMEN

The results of the processing of ash from the combustion of fuel oil after roasting with the addition of Na2CO3 followed by aluminothermic melting are presented. As a result, metallic nickel and vanadium slag were obtained. Studies of slag, metal, and deposits on the electrode were carried out. The resulting metal contains about 90 wt% Ni. The main phases of scurf on the electrode are a solid solution based on periclase (Mg1-x-y-zNixFeyVzO), sodium-magnesium vanadate (NaMg4(VO4)3), and substituted forsterite (Mg2-x-yFexNiySiO4). The processing of ash made it possible to significantly increase the concentration of vanadium and convert it into more soluble compounds. Vanadium amount increased from 16.2 in ash to 41.4-48.1 V2O5 wt% in slag. The solubility of vanadium was studied during aqueous leaching and in solutions of H2SO4 and Na2CO3. The highest solubility of vanadium was seen in H2SO4 solutions. The degree of extraction of vanadium into the solution during sulfuric acid leaching of ash was 18.9%. In slag, this figure increased to 72.3-96.2%. In the ash sample, vanadium was found in the form of V5+, V4+ compounds, vanadium oxides VO2 (V4+), V2O5 (V5+), and V6O13, and nickel orthovanadate Ni3(VO4)2 (V5+) was found in it. In the slag sample, vanadium was in the form of compounds V5+, V4+, V3+, and V(0÷3)+; V5+ was presented in the form of compounds vanadate NaMg4(VO4)3, NaVO3, and CaxMgyNaz(VO4)6; V3+ was present in spinel (FeV2O4) and substituted karelianite (V2-x-y-zFexAlyCrzO3). In the obtained slag samples, soluble forms of vanadium are due to the presence of sodium metavanadate (NaVO3), a phase with the structure of granate CaxMgyNaz(VO4)6 and (possibly) substituted karelianite (V2-x-y-zFexAlyCrzO3). In addition, spinel phases of the MgAl2O4 type beta-alumina (NaAl11O17), nepheline (Na4-xKxAl4Si4O16), and lepidocrocite (FeOOH) were found in the slag samples.

RESUMEN

An analytical method for sample preparation of igneous rocks and subsequent determination of Si, Na, K, Ca, Mg, Al, Fe, Mn, Ba, Sr, and Ti by means of microwave induced emission spectrometry (MP-AES) was developed and validated. The proposed sample preparation procedure avoids the use of perchloric acid and provided accurate results even for silicon determination using an acid digestion with hydrofluoric acid. The determination of major elements in rocks is required for the design of classification diagrams that provides relevant information for geochemical analysis.•MP-AES showed to be an adequate technique to measure major and some trace elements that are relevant for classification of igneous rocks.•This method is in better agreement with the principles of the Green Analytical Chemistry and constitutes a reliable alternative to classical analytical and tedious procedures used for geochemical analysis.•The methodology was successfully applied to chemical classification of rocks from Valle Chico (Uruguay) using a Total Alkali-Silica Diagram (TAS).

RESUMEN

Five newly synthetized fac-Re(I) tricarbonyl compounds were explored as prospective antitrypanosomal agents. The biological activity of the whole series was evaluated preliminarily against the epimastigote form of Trypanosoma cruzi. All compounds showed activity against epimastigotes with IC50 values in the low micromolar range. The most active compound [fac-Re(I)(CO)3(tmp)(CTZ)](PF6), with CTZ = clotrimazole and tmp = 3,4,7,8-tetramethyl-1,10-phenantroline, showed good selectivity towards the parasites and thus was selected to carry out further metallomic studies. For this task, a newly bioanalytical method based on microwave plasma atomic emission spectrometry (MP-AES) was developed and validated. The accuracy of the method was ensured by testing a certified reference material. Results of rhenium elemental analysis by MP-AES agreed with the proposed formula of the studied compounds, contributing to the overall validation of the method, which was then applied to evaluate the percentage of rhenium uptaken by the parasites and the association of the compounds with parasite biomacromolecules. Metallomics results showed low total rhenium percentage uptaken by parasites (∼1.2%) and preferential accumulation in the soluble proteins fraction (∼82.8%). Thus, the method based on MP-AES turned out to be an economical and green alternative for metallomics studies involving potential rhenium metallodrugs. Moreover, a comparison against rhenium determination by electrothermal atomic absorption spectrometry (ET-AAS) was included.

Asunto(s)

RESUMEN

In this paper, we present the time-dependent elemental composition and AMS radiocarbon dating results of 36 rape, sunflower and forest honey samples, collected between 1985 and 2018 in geographically close locations. Based on the elemental information, we conclude that bee products regardless the type provide useful environmental information of the previous decades, such as the decreasing trend of airborne Pb emission can be traced. However, radiocarbon results agree less with the atmospheric bomb peak. Random offsets were observed in the specific radiocarbon activity of the honey samples indicating that rape, sunflower and forest honey samples are not as reliable materials for radiocarbon dating as acacia honeys. The radiocarbon results show that the rape, sunflower and forest honey samples can contain non-photosynthetic carbon, presumably derived from the soil. Thus, the complex application of honey samples for environmental reconstruction requires the species-separated investigation of bee products to reveal their adaptability for assessment approaches.

Asunto(s)

RESUMEN

This research aimed at developing an analysis method, which was optimized and validated to determine the content of mercury in skin lightening cream discovered in the market in Bandar Lampung, Indonesia, through the use of microwave plasma atomic emission spectroscopy (MP-AES). The optimization on the analysis method was conducted on pump rate, viewing position, and reductant concentration in order to obtain the highest mercury emission intensity, while the solution stability was optimized to know the stability of mercury in the solution. The result showed that the method developed had precision with a relative standard deviation of 2.67%, recovery value of 92.78%, and linearity with an r value of 0.993, respectively. The sensitivity of the instrument detection had a limit of analysis method detection and quantification of 0.59 and 1.98 µg/L, respectively. The results of the test of the lightening cream (8 of 16 samples) positively contained mercury in the range of 422.61-44,960.79 ng/g. Therefore the method of analysis developed may be used for routine analysis of chemicals in any cosmetics products.

Asunto(s)

RESUMEN

Several studies show that the elemental content of honey entirely depends on the botanical and geographical origin, but the information is incomplete regarding its time-dependent composition changes. Twenty-six acacia and three honey samples with unknown botanical origin were collected between 1958 and 2018 and analysed for elemental composition by Microwave Plasma Atomic Emission Spectrometry (MP-AES). The elemental analysis was coupled with independent dating method by Accelerator Mass Spectrometry (AMS) to confirm the calendar age of the honey samples and test the possibility of radiocarbon based dating of bee products, which has not been applied before. According to the analytical measurements and statistical analysis, we can conclude that the elemental composition shows change with time in the acacia honey during the last five decades. We have proven that honey preserves carbon isotopic and elemental information of its production time and thus can be applied as an environmental indicator (e.g. trace urban pollutants, precipitation, local industrial or agricultural emission) in reconstruction studies by analysing the non-degradable mineral content. Our results further show that acacia honey is a suitable material for radiocarbon dating, proved by the results compared to the atmospheric radiocarbon bomb-peak. The new approach presented for investigation of honey by radiocarbon-based age determination coupled with elemental analysis can be used in biological, dietary, archaeological or other multidisciplinary studies as well. Some samples show slightly depleted radiocarbon content. This could be an indication of local fossil CO2 emission. Based on these depleted 14C results, honey could be used for atmospheric monitoring of fossil CO2 urban or industrial hot-spots.

Asunto(s)

RESUMEN

Human blood is a complex sample matrix when elemental analysis is considered. In this study, the effects of Na, a natural component of serum samples, was investigated in the quantitative determination of Ca, K, Mg, Cu, Zn, and Fe by microwave plasma atomic emission spectrometry. The robustness of the microwave plasma was tested by evaluating MgII 280.271 nm/MgI 285.213 nm by varying two adjustable operating parameters, the read time, and the nebulizer pressure. The read time has no influence on the robustness while the MgII/MgI ratio decreased when the nebulizer pressure was increased during the analysis. The threshold concentrations of the interfering Na were determined at the analytical lines used for the measurement of other elements. The matrix effect of the commercially available microwave plasma was studied by a series of model experiments with human blood. The increasing concentration of Na in the matrix within the normal ranges reported for blood serum increased the intensities of the measured atomic lines. According to a factorial design-where two applied factors were the concentration of Na matrix and the measured elements as well as their levels were considered as factorial points-it was found that the Na concentration in a serum sample after acid digestion and 10 times dilution affected the intensity values of the measured elements. For Ca, Cu, and Fe, a statistically significant effect was observed, while for Zn, Mg, and K, an interaction effect was also found. However, after calculating the percentage errors caused by the shift, the relative difference was observed to be quite small (< 10%).

Asunto(s)

RESUMEN

The behavior of nanoparticles released to the soil has been extensively studied in recent years; however, the effects of nanoparticles on the distribution of soil elements and on sowing are still unknown. To this end, to examine the distribution of selected elements in soil, soil samples were treated weekly with 1.0 mg and 20.0 mg of Al2O3 nanoparticles for 3 weeks. Additionally, different types of plants (including taproot, fibrous root and ornamental bulbous plants) were sowed in the soil samples. After each treatment, surface soil samples were collected and digested with acid digestion. The concentrations of selected elements (Ca, Mg, Fe, Al, Cu, Co, Ni) were determined using a microwave plasma atomic emission spectrometer. Al2O3 treatment for 3 weeks, both low and high doses, had no effect on the Al content in soil samples when compared to the controls. Additionally, Al2O3 showed desorption properties on the analyte elements.

Asunto(s)

RESUMEN

Radon concentration was measured in water samples of 41 different locations from Udhampur district of Jammu & Kashmir, India, by using RAD7 and Smart RnDuo monitor. The variation of radon concentration in water ranged from 1.44 ± 0.31 to 63.64 ± 2.88 Bq L-1, with a mean value of 28.73 Bq L-1 using RAD7 and 0.64 ± 0.28 to 52.65 ± 2.50 Bq L-1, with a mean value of 20.30 Bq L-1 using Smart RnDuo monitor, respectively. About 17.07% of the studied water samples recorded to display elevated radon concentration above the reference range suggested by United Nation Scientific Committee on the Effects of Atomic Radiations (UNSCEAR). The mean annual effective dose of these samples was determined, and 78.95% samples were found to be within the safe limits set by World Health Organisation (WHO) and European Council (EU). The study revealed good agreement between the values obtained with two methods. Heavy metals (Zn, Cd, Fe, Cu, Ni, As, Hg, Co, Pb and Cr) were determined in water samples by microwave plasma atomic emission spectrometer, and their correlation with radon content was also analysed.

Asunto(s)

RESUMEN

Many oxbows are contaminated by Fe and Mn as a consequence of the elemental concentration of sediment and water originating from the Upper Tisza Region of Hungary. The phenomenon is partly caused by anthropogenic activities and mainly due to the geochemical characteristics of the region. The effects of Fe and Mn on the aquatic ecosystem of these wetlands were investigated in a model experiments in this study. Survival, individual body weight and the elemental concentrations of organs were determined in common carp (Cyprinus carpio) juveniles reared in Fe and Mn contaminated media (treatment 1: Fe 0.57 mg L-1, Mn 0.29 mg L-1, treatment 2: Fe 0.57 mg L-1, Mn 0.625 mg L-1, treatment 3: Fe 1.50 mg L-1, Mn 0.29 mg L-1, treatment 4: Fe 1.50 mg L-1, Mn 0.625 mg L-1 and control: Fe 0.005 mg L-1, Mn 0.003 mg L-1), for rearing time of 49 days. The treatment with Fe and Mn did not have any effect on the survival data and individual body weight in the levels tested. The highest concentration of Fe and Mn was found in the liver and brain of carp juveniles, while the lowest concentration of these elements occurred in the muscular tissue and gills. The treatment where Fe and Mn were applied in the highest concentrations resulted in a statistically higher level of these elements in the brain, grills and muscle tissues. The treatment where only Mn was present in the highest concentration caused increased level of Mn only in the liver. We found metal accumulation in almost every organ; however, the applied concentrations and exposure time did not affect the survival and average body weight of carp juveniles.

Asunto(s)

RESUMEN

Odonata larvae are frequently used to assess the contamination of aquatic systems, because they tolerate a wide range of chemical and biological conditions in freshwater systems. In early 2000, the sediments of the Hungarian section of the River Tisza and the River Szamos were strongly enriched with heavy metals by an accidental mining spill. Earlier studies demonstrated higher contamination levels in the Szamos than in the Tisza, based on sediment analysis. The aim of our study was to assess the contamination in the Upper Tisza Region, along the upper reach of the Tisza, and the lower reach of the Szamos, based on the trace element concentrations of the Gomphus flavipes larvae. We collected 269 dragonfly specimens for the analyses. The Al, Ba, Cr, Cu, Fe, Mn, Pb, Sr and Zn element contents were analysed in the dragonfly larvae by microwave plasma atomic emission spectrometry (MP-AES). Significantly higher Ba and Cu concentrations were found in the dragonfly larvae of the Tisza than the Szamos. In spite of this, the Cr, Mn, Pb, Sr and Zn concentration was significantly lower in the dragonfly larvae of the Tisza than the Szamos. For all trace elements significant differences were found along the Tisza. Significant differences were also found in all trace element concentrations of dragonfly larvae among studied localities in the Szamos, except in the cases of Al and Ba. Our results demonstrated that the Szamos was more contaminated with Cr, Mn, Pb, Sr and Zn than the Tisza, but that the Tisza was more contaminated with Ba and Cu than the Szamos, based on the trace element concentrations in Gomphus flavipes larvae, which was likely to have been caused by the tributaries of the Tisza. In summary, our results indicated a continuous pollution of the Tisza and the Szamos and their tributaries.

Asunto(s)

RESUMEN

Short-wavelength infrared radiation has been successfully applied to accelerate the acid digestion of refractory rare-earth ore samples. Determinations were achieved with microwave plasma-atomic emission spectrometry (MP-AES) and dynamic reaction cell - inductively coupled plasma-mass spectrometry (DRC-ICP-MS). The digestion method developed was able to tackle high iron-oxide and silicate matrices using only phosphoric acid in a time frame of only 8min, and did not require perchloric or hydrofluoric acid. Additionally, excellent recoveries and reproducibilities of the rare earth elements, as well as uranium and thorium, were achieved. Digestions of the certified reference materials OREAS-465 and REE-1, with radically different mineralogies, delivered results that mirror those obtained by fusion processes. For the rare-earth CRM OKA-2, whose REE data are provisional, experimental data for the rare-earth elements were generally higher than the provisional values, often exceeding z-values of +2. Determined values for Th and U in this reference material, for which certified values are available, were in excellent agreement.

RESUMEN

Many social celebrations in urban areas are followed by fireworks show. The organic and inorganic pollutants emitted during detonations are expected to affect the ambient air quality of these celebration sites. The environmental aspects of fireworks events are usually investigated by analyzing the concentration and composition of airborne particulate matter, while there is limited information regarding the effect of fireworks on the elemental concentration of deposited dust. In this study, foliage dust samples were collected in the city of Debrecen (Hungary) before and after the fireworks show, organized on the 20th of August for the celebration of a historical event. Leaf samples (Tilia tomentosa) were collected around the location of the area of festivities. The sampling sites were further divided into five areas: city center (center), Southeast (SE), Southwest (SW), Northeast (NE), and Northwest (NW). We found that the amount of deposited dust particles increased significantly after the fireworks show compared to the background; we also found significant differences in the amount of dust deposition between the different locations of the city. A statistically higher level of Ca, Mg, and Sr was detected in samples collected after the display compared to those collected during the previous days, while the concentration of other studied elements were not statistically different from the background level. Our study confirmed previous findings that the relatively high altitude of detonations allows chemicals to disperse in the fine and ultrafine aerosol fractions; thus, the emitted pollutants by fireworks shows do not increase the level of elements as markedly in deposited dust as in the inhalable fraction.

RESUMEN

Over the past few decades, reduction of hexavalent chromium (Cr(VI)) has been studied in many physicochemical contexts. In this research, we reveal the mechanism underlying the favorable effect of Mn(II) observed during Cr(VI) reduction by oxalic acid using liquid chromatography with spectrophotometric diode array detector (HPLC-DAD), nitrogen microwave plasma atomic emission spectrometry (HPLC-MP-AES), and high resolution mass spectrometry (ESI-QTOFMS). Both reaction mixtures contained potassium dichromate (0.67 mM Cr(VI)) and oxalic acid (13.3mM), pH 3, one reaction mixture contained manganese sulfate (0.33 mM Mn(II)). In the absence of Mn(II) only trace amounts of reaction intermediates were generated, most likely in the following pathways: (1) Cr(VI)→ Cr(IV) and (2) Cr(VI)+Cr(IV)→ 2Cr(V). In the presence of Mn(II), the active reducing species appeared to be Mn(II) bis-oxalato complex (J); the proposed reaction mechanism involves a one-electron transfer from J to any chromium compound containing CrO bond, which is reduced to CrOH, and the generation of Mn(III) bis-oxalato complex (K). Conversion of K to J was observed, confirming the catalytic role of Mn(II). Since no additional acidification was required, the results obtained in this study may be helpful in designing a new, environmentally friendly strategy for the remediation of environments contaminated with Cr(VI).