Development of a novel method based on extraction mediated by a semipermeable membrane to determine Cd and Cr in sugar by graphite furnace atomic absorption spectrometry.

This work proposes a novel method to determine the Cd(II) and Cr(III) content in commercial sugar samples. It is based on the extraction of the analytes (as ammonium pyrrolidine dithiocarbamate complexes) into a semipermeable membrane device (SPMD) filled with CHCl3. After extraction, the SPMD was deployed and opened, and the analytes were recovered from the organic phase by back extraction with a 4.2 mol L-1 HNO3 solution. The analytes present in the acid extract were measured with graphite furnace atomic absorption spectrometry. Under optimized conditions, the limit of quantification of the method was 1.2 and 3.1 ng g-1 for Cd(II) and Cr(III), respectively. Twelve samples of different types of sugar were analyzed. In addition, a recovery test was performed to evaluate the accuracy of the method. The recovery percentage was 90 %-102 % for Cd(II) and 85.2 %-103 % for Cr(III).

A reliable method to prepare milligram size environmental samples to quantify metal(loid)s by high-resolution graphite furnace atomic absorption spectrometry.

We searched for an extraction method that would allow a precise quantification of metal(loid)s in milligram-size samples using high-resolution graphite furnace atomic absorption spectrometry (HR-GFAAS). We digested biological (DORM-4, DOLT-5 and TORT-3) and sediment (MESS-4) certified reference materials (CRMs) using nitric acid in a drying oven, aqua regia in a drying oven, or nitric acid in a microwave. In addition, we digested MESS-4 using a mixture of nitric and hydrofluoric acids in a drying oven. We also evaluated the effect of sample size (100 and 200 mg) on the extraction efficiency. Nitric acid extraction in a drying oven yielded the greatest recovery rates for all metal(loid)s in all tested CRMs (80.0 %-100.0 %) compared with the other extraction methods tested (67.3 %-99.2 %). In most cases, the sample size did not have a significant effect on the extraction efficiency. Therefore, we conclude that nitric acid digestion in a drying oven is a reliable extraction method for milligram-size samples to quantify metal(loid)s with HR-GFAAS. This validated method could provide substantial benefits to environmental quality monitoring programs by significantly reducing the time and costs required for sample collection, storage, transport and preparation, as well as the amount of hazardous chemicals used during sample extraction and analysis. •Sample digestion with nitric acid in a drying oven yielded the greatest recovery rates of metal(loid)s from biological and sediment certified reference materials.•The recovery rates of metal(loid)s from biological and sediment certified reference materials using nitric acid digestion in a drying oven ranged from 73 % to 100 %.•Digestion with nitric acid in a drying oven is a simple and reliable method to extract small size environmental samples for metal(loid)s quantification by high-resolution graphite furnace atomic absorption spectrometry.

Biomonitoring of Potentially Toxic Elements in Dyed Hairs and Its Correlation with Variables of Interest.

Hair is good bioindicator of exposure, due to its ability to store and retain trace elements for long periods of time. But it can be especially useful when hair dyes are used since they may contain potentially toxic salts in their composition. In this context, analytical methods for the determination of bismuth, cadmium, lead, and silver in scalp human hair by electrothermal atomic absorption spectrometry were successfully validated. A total of 60 samples obtained from women between 18 and 60 years were analyzed: 34 dyed hairs and 26 untreated hairs (control). Average results expressed in dry weight (dyed/control) for each element were 2.34/0.49 µg g-1 (silver), 0.142/0.139 µg g-1 (bismuth), 0.055/0.054 µg g-1 (cadmium), and 2.09/0.99 µg g-1 (lead), respectively. These results agreed with those previously reported for non-exposed populations. A statistically significant higher Ag concentration in dyed hairs was observed, suggesting the bioaccumulation of this element. The associations between metal concentration and variables of interest (age, education, smoking habit, dye brand, use of dietary supplements) were investigated. A strong Pearson correlation was found for the pair Ag/Pb (r = 0.494, p < 0.05). Also, strong associations between lead levels and all the selected variables were observed (p < 0.05), while strong associations between silver levels with age and dye brand and association between cadmium levels and smoking habit were found. Furthermore, several commercial hair dye brands were analyzed to verify compliance with cosmetic regulations. This constitutes the first study of such characteristics performed in Uruguay, with worldwide relevance.

Environmentally friendly and novel solid-liquid phase microextraction of maneb fungicide in fruits and vegetables.

The dithiocarbamates class has been widely used in agriculture practices because of lower toxicity and instability than organophosphates and carbamates. Among them, the maneb has been used to produce several fruits and vegetables, but its high ingestion can adversely affect human health. This work developed the Solid-Liquid Phase Microextraction (SLPME) for extraction of the maneb in foods sample with posterior determination by Flow injection analysis-Flame Absorption Atomic Spectroscopy (FIA-FAAS). Curve analytical had a linear range from 0.9 to 20.0 µmol L-1 maneb (A = 5.94 × 10-4 C (µmol L-1) + 6.93 × 10-4), good repeatability (4.07%) and reproducibility (3.39%), limits of quantification (5.98 µmol L-1) and detection (0.197 µmol L-1), which was above of the established by regulatory agencies. The extraction of the maneb was performed using 685 µL of the solution of the 1.00 × 10-3 mol L-1 of EDTA, and it has excellent recovery values from 80.85 to 106.51%. Therefore, the developed SLPME demonstrated an alternative environmentally friendly for quickly extracting maneb from food samples (apple, papaya, and tomato).

Direct magnetic sorbent sampling flame atomic absorption spectrometry (DMSS-FAAS) for highly sensitive determination of trace metals.

A procedure of direct magnetic sorbent sampling in flame atomic absorption spectrometry (DMSS-FAAS) was developed in this work. Metal-loaded magnetic sorbents were directly inserted in the flame of the FAAS for direct metal desorption/atomization. Magnetic graphene oxide aerogel (M-GOA) particles were synthesized, characterized, and used as a proof-of-concept in the magnetic dispersive solid phase extraction of Pb2+ ions from water samples. M-GOA was selected because is a light and porous sorbent, with high adsorption capacity, that is quickly burned by the flame. Magnetic particles were directly inserted in the flame by using a metallic magnetic probe, thereby avoiding the need for a chemical elution step. As all the extracted Pb2+ ions arrive to the flame without passing through the nebulization system, a drastic increase in the analytical signal was achieved. The improvement in the sensitivity of the proposed method (DMSS-FAAS) for Pb2+ determination was at least 40 times higher than the conventional procedure in which the Pb2+ is extracted, eluted, and analyzed by conventional flame atomic absorption spectrometry (FAAS) via the nebulization system. The analytical curve was linear from 5.0 to 180.0 µg L-1 and the limit of detection was found to be 1.30 µg L-1. Background measurements were insignificant, and the atomic absorption peaks were narrow and reproducible. Precision assessed as a percentage of the relative standard deviation %RSD was found to be 17.4, 7.1, and 7.8% for 10, 70, and 180 µg L-1 levels, respectively. The method showed satisfactory results even in the presence of other ions (Al3+, Cr3+, Co2+, Cu2+, Fe3+, Mn2+, Ba2+, Mg2+, and Li+). The performance of the new system was also evaluated for Cd2+ ions, as well as by using other magnetic particles available in our lab: magnetic carbon nanotubes (M-CNTs), magnetic restricted access carbon nanotubes (M-RACNT), magnetic poly (methacrylic acid-co-ethylene glycol dimethacrylate) (M-PMA), magnetic nanoparticles coated with orange powder peel (M-OPP), and magnetic nanoparticles covered with SiO2 (M - SiO2). Analytical signals increased for both analytes in all sorbents (increases of about 4-37 times), attesting the high potential and applicability of the proposed method. Simplicity, high analytical frequency, high detectability and reproducibility, low cost, and possibility of being totally mechanized are the most relevant advantages.

Plasma and erythrocyte magnesium levels: from validation of the method to analysis in volunteers diagnosed to migraine

Deficiency of serum magnesium is associated with the incidence of migraine attacks. The present study aimed to evaluate plasma and erythrocyte magnesium levels in a group of patients diagnosed with migraine. Human donors were selected from basic health units (migraine, n = 25) and from a collection and transfusion unit (control, n = 25), both located in the city of Sinop, Brazil. Plasma and erythrocyte magnesium were assessed using flame atomic absorption. Plasma magnesium concentration was significantly lower in the migraine group (0.172 ± 0.018) compared to the control group (0.197 ± 0.020 mg/L), and erythrocyte magnesium concentration was also lower in the migraine group (0.393 ± 0.053 mg/L) compared to the control group (0.432 ± 0.056 mg/L). The method for analysis of magnesium in human plasma and erythrocytes by flame atomic absorption was shown to be in accordance with validation guidelines. This study shows that plasma and erythrocyte magnesium levels were significantly lower in volunteers diagnosed with migraine compared to healthy volunteers. Furthermore, erythrocyte magnesium proved to be a better marker than plasma magnesium for patients with migraine.

Determination of the Ca, Mn, Mg and Fe in honey from multiple species of stingless bee produced in Brazil.

Stingless Bees (SB) honey is a product used for different purposes, and it is worth highlighting the presence of metallic species, which can have a nutritional or toxic effect, depending on the metal present and/or the amount ingested. Therefore, the objective of this work was to quickly determine Fe, Mn, Mg and Ca in SB honey, using slurry sampling and FAAS of 88 honey samples from different regions of Brazil. The concentrations varied from < LOD to 364 µg g-1 (Ca). The order for average concentration in the samples was Ca > Mg > Mn > Fe. Through the principal component analysis, it was verified that the SB honey analyzed in the present study has higher contents of the evaluated metals than the honey of the species Apis mellifera and SB honey from other Brazilian states. Theoretical calculation demonstrated that there is a little contribution of SB honey to human diet in relation to the metals, being more significative for Mn.

Bioconcentración de metales pesados (Zn, Hg, Pb) en tejidos de Ariopsis felis y Diplodus annularis en el río Ranchería, norte de Colombia / Bioconcentration of heavy metals (Zn, Hg, Pb) in tissues of Ariopsis felis and Diplodus annularis in the Ranchería river, Northern Colombia

RESUMEN La contaminación por metales pesados en los ecosistemas acuáticos en el planeta es una de las más severas problemáticas que comprometen la seguridad alimentaria a nivel local, regional y global. En este estudio, se aborda el problema específico de la bioconcentración de mercurio (Hg), plomo (Pb) y Zinc (Zn) en los tejidos orgánicos de 2 de las especies de peces (Ariopsis felis y Diplodus annularis) de mayor importancia alimenticia para los pobladores rivereños del río Ranchería, al norte de Colombia. Las muestras de tejido orgánico se sometieron a una digestión ácida (HNO3 y HClO 4 en relación 3:1) y la cuantificación de los metales se realizó por espectrofotometría de absorción atómica. Adicionalmente, se midieron los niveles de los metales en el sedimento, con el objeto de determinar índices de calidad medioambientales, lo que permitió determinar que los metales pesados no presentan riesgo para los organismos acuáticos que habitan en esta zona. Se encontraron diferentes valores de concentración de metales pesados: en orden decreciente, Zn > Hg > Pb, en sedimento, y Hg > Zn > Pb, en el tejido biológico. Los resultados muestran que las concentraciones de los metales pesados presentes en el tejido de los peces y en el sedimento guardan una correlación positiva y una regresión lineal estadísticamente significativa (p = 0,001, p < 0,05). La presencia de metales pesados en el sedimento del río y de bioconcentrados en los peces podría derivarse de fuentes puntuales y difusas relacionadas con actividades agrícolas, pecuarias, mineras y aguas residuales.

ABSTRACT Heavy metal pollution in aquatic ecosystems in the area is one of the most severe problems that compromise food security at the local, regional and global levels. In this study, the specific problem of the bioconcentration of mercury (Hg), lead (Pb), and Zinc (Zn) in 2 of the higher nutritional importance fish species (Ariopsis felis and Diplodus annularis) for the riverside inhabitants of the Ranchería river, in northern Colombia, is addressed. The organic tissue samples were subjected to acid digestion (HNO3 and HClO4 in a 3:1 ratio), and the quantification of metals was carried out by atomic absorption spectrophotometry. Additionally, the levels of metals in the sediment were measured, in order to determine environmental quality indices. This allow to determine that heavy metals do not present a risk to the aquatic organisms that inhabit this area. Different heavy metal concentration values were found: in decreasing order, Zn> Hg> Pb in sediment, and Hg> Zn> Pb in biological tissue. The results reveal that the concentrations of heavy metals present in fish tissue and sediment show a positive correlation, and a statistically significant linear regression (p = 0,001, p < 0,05). The presence of heavy metals in river sediment and bioconcentrates in fish could derive from point and diffuse sources related to agricultural, livestock, mining and wastewater activities.

Determination of cadmium and lead in tomato (Solanum lycopersicum) and lettuce (Lactuca sativa) consumed in Quito, Ecuador.

Vegetables are one of the most important components in the human diet, but despite their multiple nutritional components, studies have demonstrated the presence of trace metals in their edible parts. In Ecuador, two of the most consumed crops are tomato (Solanum lycopersicum) and lettuce (Lactuca sativa). The importance of these two crops in the Ecuadorian diet, especially in large and touristic locations like the Metropolitan District of Quito, implies food safety-related concerns for locals and visitors. However, no previous studies have quantified the cadmium and lead levels in these two vegetables using samples from Quito markets. Thus, the aim of this study was to determine the cadmium and lead content in both tomato and lettuce products from main nonorganic and organic markets in Quito using a graphite furnace atomic absorption spectrophotometer. The results showed that the cadmium levels were lower than 0.058 in tomatoes and 0.034 mg/kg in lettuce, which are under the respective threshold values (0.100 and 0.200 mg/kg). Regarding lead, levels lower than 0.066 mg/kg were detected in lettuce, which did not exceed the CXS 193-1995 threshold value, while levels in tomatoes were near or exceeded the threshold value (0.100 mg/kg) from four markets (0.209, 0.162, 0.110, 0.099 mg/kg), suggesting a possible risk from tomato consumption. In addition, most vegetables marketed as organic had higher metal content than those coming from nonorganic markets. Based on these results, local health and commercial control authorities should monitor contaminants in food products sold in Quito and other places in Ecuador to ensure their safety.

Feasibility of DS-GF AAS for the determination of metallic impurities in raw material for polymers production.

A new procedure is proposed for the determination of metal contaminants (Cr, Fe, Mg, Mn, Na and Ni) in polymeric diphenylmethane diisocyanate (PMDI), a raw material used to produce polyurethane polymers. The feasibility of using Zeeman-effect background correction graphite furnace atomic absorption spectrometry (GF AAS) and direct sampling (DS) was evaluated. Calibration using aqueous standard solutions was feasible and chemical modifiers as well as reference materials for this purpose were unnecessary. Relatively high sample masses (up to 23 mg) were used allowing very low limits of detection ranging from 0.06 ng g-1 to 1 ng g-1 (Fe and Mg) up to 3  ng g-1 (Ni), with relative standard deviation lower than 15%. The following parameters were evaluated: pyrolysis and atomization temperatures , sample mass, as well as the use of low sensitivity conditions (Zeeman effect background correction magnetic field strength adjustment and the use of a secondary wavelength for Fe and Na determinations, respectively). Results were compared with those obtained by microwave-assisted digestion and microwave-induced combustion with subsequent analytes determination by inductively coupled plasma optical emission spectrometry (ICP-OES) and by inductively coupled plasma mass spectrometry (ICP-MS). No significant difference was observed between the results obtained by DS-GF AAS, ICP-MS and ICP-OES after both digestion systems. The proposed DS-GF AAS method allowed the determination of six elements in PMDI (which is considered as a complex matrix) with limits of detection lower than those achieved by other methods. This new procedure can be used as quality control of polyurethanes industry for ultra-trace inorganic impurities.

Contamination of staple crops by heavy metals in Sibaté, Colombia.

Heavy metal contamination in water resources, soil, and food sources is an issue that compromises food safety in Sibaté, Colombia. In the present study concentration of heavy metals [HMs], such as Cu, As, Pb, Cr, Zn, Co, Cd and Ni, present in vegetables included in the typical Colombian diet were measured. The study was conducted as follows: samples of parsley, artichoke and carrots produced in a location near the Muña dam were collected, where the Bogotá River water is treated for use as a water resource. To determine food safety, national and international [HMs] established limits were compared with quantified [HMs] in samples of different vegetable parts and of the surrounding soil. Fresh samples were separated in their respective parts for cold acid digestion with HCl and HNO3 (1:1) for 15 days. Heavy metal mean ± standard error (SE) were as follows (mg/kg) As 2.36 ± 0.185, Cd 0.16 ± 0.009, Co 0.43 ± 0.019, Cr 12.1 ± 0.453, Cu 13.1 ± 1.68, Ni 0.00, Pb 7.07 ± 0.482 and Zn 3.976 ± 0.332. Cd, Cr, As, Co and Ni showed high transfer factor in Cynara scolymus. Moreover, high Pb, Cu and Zn transfer factor were present in Petroselinum crispum. Except for Daucus carota roots, there was a high metal transfer specifically in Petroselinum crispum leaves and other different plant parts, with high transfer factor for Cr, As, Co, Pb, Cu and Zn.

Synthesis, characterization and application of a novel ion hybrid imprinted polymer to adsorb Cd(II) in different samples.

Two new ionic imprinted hybrid polymers (IIHP) and their corresponding non imprinted hybrid polymers (NIHP) were synthesized. The prepared IIHP was highly selective to Cd2+. To prepare the IIHP, 1-vinylimidazole (VIN) was used as the functional monomer, (3-mercaptopropyl) trimethoxysilane (MP) or (3-aminopropyl) trimethoxysilane (AMP) was used as the functional organosilane, trimethylolpropane (TRIM) was used as the crosslinking agent, AIBN was used as a radical initiator and TEOS was used as a functional precursor. The functional monomer was selected considering calculations based on the density functional theory (DFT). The fabricated materials were characterized via field emission gun scanning electron microscopy (FEG-SEM), Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray spectroscopy (EDX) and thermogravimetric analysis (TGA). The maximum adsorption capacity of Cd2+ was achieved at a pH of 7.2 in the tris-HCl medium. The adsorption test indicated that the reaction followed pseudo second order kinetics, and the equilibrium sorption data fitted well into the Langmuir isotherm model. The relative selectivity coefficients of polymers IIHP-VIN-AMP and IIHP-VIN-MP, as evaluated in binary mixtures of Cd2+ and interferent cations (Pb2+, Zn2+, Hg2+, Cu2+, Ni2+, Ca2+, Mg2+, and Na+) at different molar ratios, were greater than one due to the presence of specific recognition sites for Cd2+ ions. Moreover, the selective materials exhibited a high reusability and reproducibility in the context of Cd2+ adsorption. These adsorbent materials, specifically IIHP-VIN-MP, exhibited a % removal efficiency of more than 90% for the Cd2+ in river water samples.

Determination of lithium in dried blood spots and dried plasma spots by graphite furnace atomic absorption spectrometry: Method development, validation and clinical application.

Therapeutic drug monitoring (TDM) has become a standard of care for the mood stabilizer lithium (Li+). Dried Blood Spots (DBS) and Dried Plasma Spots (DPS) are promising alternative sampling strategies for TDM, which allows simple and cost-effective logistics in many settings, particularly in Developing Countries. DBS and DPS are of particular interest to Li + TDM for allowing the estimation of Li + erythrocyte levels. Thus, the aim of this study was to develop and validate an assay for the determination of Li+ in DBS and DPS by Graphite Furnace Atomic Absorption Spectrometry (GFAAS), and to evaluate its application in a clinical setting. Li+ was extracted from one 8 mm DBS disc punch with nitric acid 4.5% and from one 6 mm DPS disc punch with diluent solution (HNO3 1% + Triton 0.1%) and injected into GFAAS. The method was applied to Li + TDM in 43 patients with mood disorder. The assays were linear from 0.10 to 3.0 mEq L-1 (r > 0.99), precise, with CV 3.6-7.2% for DBS and 4.6-9.3% for DPS samples, and accurate, with accuracy values of 97-109% and 98-106% for DBS and DPS samples, respectively. Li+ was stable in dried samples during twenty days at up to 42 °C. The DBS assay accuracy and recovery were not influenced by blood hematocrit. The patients presented Li + serum concentrations of 0.18-1.1 mEq L-1 and 0.17 to 0.92 mEq L-1 in DBS and 0.15 to 0.99 mEq L-1 in DPS samples. DPS had comparable Li + concentrations to the ones found in fresh serum samples. With DBS samples it was possible to estimate the Li + erythrocyte to plasma concentration ratio (LiR). The findings of this study support the clinical application of DBS and DPS samples for the TDM of Li+.

Atomic Absorption Spectrometry Methods to Access the Metal Solubility of Aerosols in Artificial Lung Fluid.

Recent studies to quantify the health risks that fine particulate matter with an aerodynamic less than 2.5 µm (PM2.5) pose use in vitro approaches. One of these approaches is to incubate PM2.5 in artificial lysosomal fluid for a given period at body temperature. These body fluids used have a high ionic strength and as such can be challenging samples to analyze with atomic spectroscopy techniques. As PM2.5 is a primary health hazard because it is tiny enough to penetrate deep into the lungs and could, in addition, dissolve in the lung fluid it is important to quantify elements of toxic and/or carcinogenic concerns, reliably and accurately. Sophisticated instrumentation and expensive pre-treatment of challenging samples are not always available, especially in developing countries. To evaluate the applicability of graphite furnace atomic absorption spectrometry (GFAAS) without Zeeman correction capability to detect trace quantities of heavy metals leached from PM2.5 on to artificial lung fluid, univariate and multivariate approaches have been used for optimization purposes. The limits of quantification, LOQ, obtained by the optimized method were: 2 µg L-1 (Cu), 3 µg L-1 (Cr), 1 µg L-1 (Mn), and 10 µg L-1 (Pb). The addition/recovery experiments had a mean accuracy of: (Cu) 99 ± 7%; 110 ± 8% (Cr); 95 ± 9% (Mn), and 96 ± 11% (Pb). The average soluble fractions of PM2.5 incubated in artificial lysosomal fluid (ALF) for 1 h were: 1.2 ± 0.01 ng m-3 Cu, 0.4 ± 0.01 ng m-3 Cr, 0.6 ± 0.01 ng m-3 Mn, and 4.8 ± 0.03 ng m-3 Pb. Using historical elemental averages of PM2.5 in Curitiba (Cu 3.3 ng m-3, Cr 2.1 ng m-3, Mn 6.1 ng m-3, Pb 21 ng m-3), the percentage bioaccessibility were determined to be Cu 38%, Cr 20%, Mn 10%, and Pb 23%. The elemental values of the atmospheric soluble fraction of Cu, Cr, and Mn were below the inhalation risk concentrations. However, for Pb, the atmospheric soluble fraction exceeded the inhalation unit risk of 0.012 ng m-3. This robust and straightforward GF AAS method is pivotal for low and middle-income countries were most air pollution adverse effects occur and established lower-cost technologies are likely unavailable.

Fast and effective simultaneous determination of metals in soil samples by ultrasound-assisted extraction and flame atomic absorption spectrometry: assessment of trace elements contamination in agricultural and native forest soils from Paraná - Brazil.

This study proposes a simple and effective method for determination of Al, Cd, Cu, Ni, and Zn in soil samples, associating ultrasound-assisted extraction and flame atomic absorption spectrometry (FAAS). Ultrasound-assisted extraction conditions were optimized using a central composite design. This method required small volumes of HCl, HNO3, and HF as an extraction solvent blend to ensure effective analyte extraction. Limits of detection and quantification were determined to assess the minimum accurate concentration of the studied elements that can be detected and quantified in a soil sample. Therefore, the ultrasound-assisted extraction was concluded as a simple and straightforward pretreatment technique to determine Al, Cd, Cu, Ni, and Zn concentrations in soil samples. Eight sites of agricultural and native forest areas of the city of Ponta Grossa and Guarapuava, State of Paraná, Brazil, were evaluated for metals, and compared with the reference values for trace elements provided by the Brazilian National Environment Council. Environmental assessment of soils from those eight sites was accomplished through Igeo, EF, CF, and PLI parameters, which aimed at the evaluation of agricultural sites in comparison with adjacent natural forest sites with no history of anthropogenic mobilization to determine the degree of the contribution of anthropogenic sources to metal concentrations. According to the Igeo, EF, and CF parameters, all sites were classified as unpolluted to moderately polluted and none or minor enrichment due to anthropogenic activities were noticed. PLI parameter evaluated the concentration of all studied metals in soils to stipulate an order of contamination, which was concluded as site 8

Supplementation with an Inorganic Iron Source Modulates the Metalloproteomic Profile of the Royal Jelly Produced by Apis mellifera L.

This study aimed to evaluate the quality of the royal jelly produced by Apis mellifera bees in the presence of different iron concentrations (ferrous sulfate heptahydrate-0, 25, 50, and 100 mg L-1). Two-dimensional electrophoresis was used for the fractionation of royal jelly proteins, and iron level was quantified using flame atomic absorption spectrometry technique. The proteins were identified using electrospray ionisation mass spectrometry. Analysis of variance followed by the Tukey test (P < 0.05) was utilised. Dietary supplementation with mineral Fe affected the protein content and number of proteins in the experimental period. Further, the diet containing the highest iron concentration showed a greater number of spots containing iron, as well as in the abdomen of the bees. The most protein containing Fe were classified as major royal jelly proteins. These results showed that Fe influenced the quality of royal jelly and can improve its nutritional value.

Evaluation of Chromium and Manganese levels in sports supplements using graphite furnace atomic absorption spectrometry / Avaliação do teor de Cromo e Manganês em suplementos esportivos por meio de espectrometria de absorção atômica em forno de grafite

ABSTRACT Objective In this paper, we studied three different types of ordinary sports supplements containing whey protein: whey protein-based ones, hypercaloric ones, and protein bars. Methods A sample preparation procedure was studied employing microwave-assisted wet digestion in order to determine the Chromium and Manganese levels by graphite furnace atomic absorption spectrometry. Results The developed methods have presented good accuracy (recoveries in the range of 90% to 109%) and precision (Relative standard deviation <8%). Although an adequate detectability was obtained (50ng g-1 for Manganese and 65ng g-1 for Chromium), the sample preparation method was also adequate to inductively coupled plasma mass spectrometry analysis. The method was applied to 26 commercial samples, in which the Chromium concentrations were in the range between 0.22 and 1.0μg g-1 and the Manganese concentrations varied from 2.0 to 37μg g-1. Conclusion The results obtained by atomic absorption for both analytes were in agreement with those obtained by mass spectrometry. In addition, some samples presented concentrations of Chromium above the recommended daily intake and, as a result, we used the X-ray powder diffraction technique as an analytical tool to evaluate the oxidation state of Chromium in such samples.

RESUMO Objetivo Neste trabalho, foram estudados diferentes tipos de suplementos esportivos contendo proteína de soro de leite, conhecidos como: whey protein, hipercalóricos e barras de proteína. Métodos Um procedimento de preparo de amostras foi estudado com o emprego de digestão úmida assistida por micro-ondas, a fim de determinar os teores de cromo e manganês por espectrometria de absorção atômica em forno de grafite. Resultados Os métodos adotados apresentaram boa exatidão (recuperações na faixa de 90 a 109%) e precisão (Desvio padrão relativo <8%). Embora tenha sido obtida uma capacidade de detecção adequada de 50ng g-1 para o manganês e de 65ng g-1 para o cromo, o método de preparo da amostra também se revelou adequado para a utilização em análises por espectrometria de massas com plasma indutivamente acoplado. O método foi aplicado a 26 amostras comerciais, cujas concentrações de cromo variaram entre 0,22 e 1,0μg g-1, e de manganês entre 2,0 e 37μg g-1. Conclusão Os resultados obtidos por absorção atômica, para ambos os analitos, mostraram-se de acordo com aqueles obtidos por espectrometria de massas. Além disso, algumas amostras apresentaram concentrações de cromo acima da recomendação de consumo diário e, como resultado, a técnica de difração de raios-X em pó foi utilizada como ferramenta analítica para avaliar o estado de oxidação do cromo em tais amostras.

Evaluation the Health Impact of Some Heavy Metals in Milk from Markets

This study focuses on the heavy metals concentrations (Fe, Cu, Zn, Pb, and Cd) in certain common milk species are collected from Iraqi markets using Flame Atomic Absorption Spectrophotometer-6300 AA, Shimadzu, Japan, respectively. This study shows the pollution in the environment obtained by heavy metals. The results showed that Cr, Cd, Cu, Zn, and Fe were varying according to the order: Zn>Fe>Cr>Cd>Cu. levels of heavy metals were 0.610(Cr), 0.125(Cd), 0.052(Cu), and 6.902(Zn), and 0.759(Fe). All the heavy metals were observed within maximum limit in milk. Overall, the number of analyzed heavy metals and sample size were limited in present study. Keywords: Heavy metals; Milk; Najaf; Flame atomic absorption; Spectrophotometer This study focuses on the heavy metals concentrations (Fe, Cu, Zn, Pb, and Cd) in certain common milk species are collected from Iraqi markets using Flame Atomic Absorption Spectrophotometer-6300 AA, Shimadzu, Japan, respectively. This study shows the pollution in the environment obtained by heavy metals. The results showed that Cr, Cd, Cu, Zn, and Fe were varying according to the order: Zn>Fe>Cr>Cd>Cu. levels of heavy metals were 0.610(Cr), 0.125(Cd), 0.052(Cu), and 6.902(Zn), and 0.759(Fe). All the heavy metals were observed within maximum limit in milk. Overall, the number of analyzed heavy metals and sample size were limited in present study

Alkaline Extraction for Lead Determination in Different Types of Commercial Paints.

In 2017, the World Health Organization and the United Nations Environment Programme formed the Global Alliance to Eliminate Lead Paint. All alliance member countries have pledged to develop control regulations that include lead threshold limits. To improve regulations and demonstrate compliance of paint industry products, it is necessary to have adequate, locally applicable methodologies. In this sense, the main objective of this research was to validate the methodology of alkaline extraction for the quantification of lead in ten different types of Ecuadorian commercial paints using flame atomic absorption spectrophotometry. Two hundred and fifty samples from different paint industry products were analyzed, and the results were used to evaluate the method's performance and robustness. It was determined that the method could be applied for lead concentrations above 100 mg·kg-1, and results showed relative standard deviation values lower than 14.8% and fortification recoveries between 80.3 and 119.4%, fulfilling the acceptance criteria established in the Environmental Protection Agency's lead-based Paint Laboratory Operations Guidelines.

Distribution, Contents, and Health Risk Assessment of Cadmium, Lead, and Nickel in Bananas Produced in Ecuador.

In this study, cadmium (Cd), nickel (Ni), and lead (Pb) contents were analyzed in sixteen banana composite samples from different commercial establishments from eleven Ecuadorian production provinces using graphite furnace atomic absorption spectrophotometry. The concentrations (fresh weight) in the samples collected (9.3-47.3 µg·kg-1 for Cd, 16.1-105.6 µg·kg-1 for Ni, and 36.9-538.0 µg·kg-1 for Pb) were used to calculate the estimated daily intake (EDI), target hazard quotient (THQ), and target carcinogenic risk (CR) associated with dietary exposure to these potentially toxic metals. Cd and Ni results showed that every sample had EDIs lower than the oral reference dose and THQ values lower than 1, demonstrating that there was no non-carcinogenic risk related to the exposure to Cd and Ni. In the case of Pb, two EDIs results were higher than the reference dose, also their corresponding THQ values were higher than 1. The lead CR in all samples was less than 1 × 10-4, the upper limit used for acceptable cancer risk. Thus, there is no significant health risk to the consumer associated with bananas with contamination levels of Cd, Ni, but there is Pb risk for toddlers (12 kg of body weight) intake comparable to the one detected in the present study.