In Vitro Evaluation of Bioavailability of Cr from Daily Food Rations and Dietary Supplements from the Polish Market.

Only some of the nutrients consumed with food are able to be absorbed from the gastrointestinal (GI) tract and enter the systemic circulation (blood). Because some elements are essential minerals for humans, their beneficial effect on the body depends significantly on their bioavailable amount (the fraction that can be absorbed and used by the organism). The term bioavailability, which is very often used to describe the part of nutrients that is able to be absorbed, is influenced by various factors of exogenous and endogenous origin. The main purpose of the study was to assess the relative bioavailability of Cr from selected dietary supplements in the presence of various types of diets, which significantly influence the level of bioavailability. The research was performed using a previously developed and optimized two-stage in vitro digestion model using cellulose dialysis tubes of food rations with the addition of pharmaceutical products. Cr was determined using the ICP-OES and GF-AAS methods, depending on its concentration in particular fractions. The determined relative bioavailability ranged between 2.97 and 3.70%. The results of the study revealed that the type of diet, the chemical form of the molecule, and the pharmaceutical form of preparations have a significant influence on the bioavailability of Cr.

Determination of chromium in foodstuffs by using novel adsorbent in vortex assisted-dispersive solid phase micro-extraction method: An application of multivariate techniques.

A new graft copolymer composed of polystyrene and polylinoleic acid (PLinas) with the sodium salt of iminodiacetate (Ida) was synthesized and used as an adsorbent. The vortex-assisted dispersive solid-phase micro-extraction (VA-dSPµE) method was used for the extraction and pre-concentration of chromium. Multivariate methodologies, such as factorial design and 3D surface plots, were applied for screening and optimizing effective extraction parameters. The influence of diverse analytical parameters, such as pH, sample volume, and interfering ions, on the extraction of chromium was studied. The calibration standard curve exhibited a linear range from 0.01 to 0.50 µg L-1. The relative standard deviation and limit of detection were found to be 1.65 % and 0.003 µg L-1, respectively. Extraction recoveries were found in the range of 96 to 99 % by using certified reference materials (CRMs). The adsorbent capacity of PLinas-Ida was found to be 112 mg g-1. The VA-dSPµE method demonstrated its effectiveness in the pre-concentration and determination of chromium within samples of foodstuffs by graphite furnace-atomic absorption spectrometry (GF-AAS).

A new method based on extraction induced by emulsion breaking for determination of Co and Ni in chocolate bars by graphite furnace atomic absorption spectrometry.

This paper describes a new experimental configuration of extraction induced by emulsion breaking method to extract and determine Ni and Co in chocolate bars by graphite furnace atomic absorption spectrometry. At optimized conditions, the sample (0.08 g) was mixed with 4 mL of extractant solution (4% m/v Triton X-100 and 10% v/v HNO3) in a plastic syringe to form a solid-oil-water emulsion. Then, emulsion breaking was assisted by membrane filtration. The total extraction procedure took approximately 1 min, in opposition to 25 (centrifugation) and 50 min (heating). Extraction yields ranged from 94.8 to 114.3% for Co and from 85.9 to 108.4% for Ni. The limits of detection and quantification were, respectively, 24.73 and 82.45 µg Kg-1 for Co and 49.05 and 163.5 µg Kg-1 for Ni. Recoveries ranged from 92.1 (Ni) to 105.4% (Co).

Disruption of a three-component solution as a novel strategy for Cu and Ni extraction from vegetable oils for their determination by GF AAS.

In this work, we propose a novel approach for extracting Cu and Ni from vegetable oils (which can be expanded to other metals). The method is based on the transference of the analytes to an aqueous acid phase due to the disruption of a three-component solution. The extraction was carried out in two steps. In the first step, a three-component solution was prepared comprising the sample, 1-octanol, and HNO3 solution. Next, the homogeneous system was disrupted by adding 1.0 mL of deionized water, and two phases were formed. The aqueous extract deposited in the bottom of the flask was collected with a micropipette, and Cu and Ni were determined by graphite furnace atomic absorption spectrometry (GF AAS). The developed method presented limits of quantification (LOQ) of 0.25 and 0.17 ng g-1 for Cu and Ni, respectively, and was successfully applied in the analysis of eleven oil samples from different origins.

Use of slow atomization ramp in high resolution continuum source graphite furnace atomic absorption spectrometry for the simultaneous determination of Cd and Ni in slurry powdered chocolate samples.

A methodology for simultaneous (not sequential) determination of Cd and Ni in powder chocolate samples by high-resolution continuum source graphite furnace atomic absorption spectroscopy (HR-CS-GF-AAS) and slurry sample analysis was developed. Acid digestion of the samples was not necessary, considering the high total fat content of this type of matrix (above 10 %), and no apparent deterioration of the graphite tubes was even observed once these samples were subjected to analysis. Despite the volatilities of both elements are quite different, simultaneous quantification was achieved using a slow heating ramp atomization, covering a convenient and wide temperature gradient for Cd volatilization at low temperatures and subsequent atomization of Ni at elevated temperatures, using the same heating program without an apparent change in sensitivity. This slow heating ramp was essayed between 200 and 1500 °C·s-1 and optimized at 400 °C·s-1, achieving the simultaneous measuring of Cd in the principal line (228.8018 nm) and using a secondary for Ni (228.9984 nm). No stop events for sequential changes in wavelength or temperature additional steps were involved in the method and molecular spectral interferences overlapping the analyte signals were corrected appropriately by a pragmatic strategy taking advantage of the fine structure signals adjacent to analyte signals within the same spectrum recorded. Palladium matrix modifier and aqueous standards were used for the calibration and determination of both elements in the samples. The method accuracy was successfully confirmed using a reference material (NIST SRM 1573a). An improvement in the sensitivity of Ni was found using a greater number of pixels for signal integration, central and five adjacent pixels (CP ± 5), while a lengthening of the linear range of Cd was obtained by using an attenuated signal (±2) or using only one pixel (CP). The limits of detection were 0.027 µg g-1 and 0.22 µg g-1 for Cd and Ni respectively by this simple methodology using aqueous standards for calibration and the simultaneous determination of both elements in the same measurement. The respective limits of quantification for Cd and Ni were 0.090 and 0.72 µg g-1 and the relative standard deviations in samples (n = 5) were about 4-20% and 0.3-11% for Cd and Ni respectively. The optimized method was used for the determination of both elements in real samples purchased from retail supermarkets finding variable concentrations between 0.5 and 5.7 µg g-1 for Cd and 2.1-10.9 µg g-1 for Ni, comparable to levels reported in the literature referred to elsewhere in the world.

Analytical Performance and Validation of a Reliable Method Based on Graphite Furnace Atomic Absorption Spectrometry for the Determination of Gold Nanoparticles in Biological Tissues.

Gold nanoparticles (AuNPs) have a wide-ranging application and are widespread in samples with complex matrices; thus, efficient analytical procedures are necessary to identify and characterize this analyte. A sensitive analytical method for determination of AuNPs content in biological tissues, based on microwave-assisted acid wet digestion and graphite furnace atomic absorption spectrometry (GFAAS) validated in accordance with the requirements of Eurachem guideline and ISO 17025 standard, is presented in this study. The digestion procedure was optimized, and the figures of merit such as selectivity, limit of detection (0.43 µg L-1), limit of quantification (1.29 µg L-1, corresponding to 12.9 µg kg-1 in tissue sample, considering the digestion), working range, linearity, repeatability ((RSDr 4.15%), intermediate precision (RSDR 8.07%), recovery in accuracy study (97%), were methodically evaluated. The measurement uncertainty was assessed considering the main sources of uncertainties and the calculated relative expanded uncertainty (k = 2) was 12.5%. The method was applied for the determination of AuNPs in six biological tissues (liver, small intestine, heart, lungs, brain and kidneys) and the found concentrations were generally at low levels, close or lower than LOQ.

A simple dilute-and-shoot procedure for the determination of platinum in human pleural effusions using HR-CS GF-AAS.

BACKGROUND: High-resolution continuum source AAS is an emerging technique for the determination of trace elements in clinical analysis. We aimed to develop a method for the direct determination of platinum (Pt) in pleural effusions that could deepen the understanding of the dynamics of intrapleural Pt concentration during cytostatic therapy. MATERIALS AND METHODS: Samples were collected by thoracic drainage from five patients with lung cancer undergoing platinum based chemotherapy. A simple dilute-and-shoot method for Pt determination in the pleural effusions was developed. Ashing of the sample in an oxygen flow in a graphite tube allowed for direct analysis without prior mineralization. The trueness of the method was verified using an independent technique (ICP-MS). As platinum derivatives are only active in its free form (not bound to proteins), Pt in samples was further divided into free and protein-bound forms by means of ultrafiltration. RESULTS: Using the proposed method, Pt contents (free and total) were determined in samples collected at different times after the intravenous application of the Pt derivative. The concentration of total Pt reached values of up to 5,000 µg/L and different patterns of its dynamics in intrapleural fluid were observed. CONCLUSIONS: The developed method enables the fast and simple determination of Pt in biological fluids. It may be applied on a large scale to improve the understanding of Pt dynamics during cytostatic therapy, and also to determine the optimal timing of both thoracic drainage and administration of systemic chemotherapy.

Optimization of a GF-AAS method for lead testing in blood and urine: A useful tool in acute abdominal pain management in emergency.

Suspicion of lead poisoning is confirmed by its concentration in blood and protoporphyrin red blood cells. At low concentrations, lead influences the synthesis of the heme in the sense of lowering it. Acute and chronic lead intoxication is extremely polymorphic in regards to its clinical manifestations, with digestive, hematological, cardiovascular, renal hepatic and neurological features. The aim of the study was to evaluate the presence of lead in human whole blood and urine harvested before and during chelation treatment in the case of lead poisoning. An atomic absorption spectroscopic method for the analysis of lead was developed using graphite furnace atomic absorption spectrophotometer (GF-AAS), Varian Spectra AA-880 with a hollow cathode lead lamp and a deuterium lamp for background correction, coupled to a GTA-100 atomizer and a programmable sample dispenser. Standard calibration solutions were used for the range 10-100 µg/l. The linearity range was 10.0 to 100.0 µg/l with the correlation coefficient of 0.999. We established that the method can be applied for the determination of lead in whole blood and urine, and the results obtained are useful for monitoring chelation therapy in cases of acute lead poisoning, a neglected cause of abdominal colic pain in an emergency situation.

Development and Validation of a Spectrometric Method for Cd and Pb Determination in Zeolites and Safety Evaluation.

An analytical method based on microwave-assisted acid digestion and atomic absorption spectrometry with graphite furnace as atomization source was developed and validated for determining trace elements (Cd and Pb) in zeolites used as dietary supplements, for their characterization and safety evaluation. The method was checked for the main performance parameters according to the legislation requirements in the field of dietary supplements. In all cases, the obtained performance parameters were satisfactory. The selectivity study showed no significant non-spectral matrix effect. The linearity study was conducted for the calibration curves in the range of 0-10 ng mL-1 for Cd and 0-30 ng mL-1 for Pb. The obtained limits of detection (LoDs) and the limits of quantification (LoQs) were sufficiently low in order to allow Pb and Cd determination in dietary supplements. For the internal quality control, certified reference materials were analysed and good recoveries were obtained. The precision study was performed in terms of repeatability and reproducibility, considering the requirements imposed by the Commission Decision (2007/333/EC) and the method fulfilled these performance parameters. Expanded measurement uncertainties were estimated to 11% for Cd and 10% for Pb. Cd and Pb content were measured in real zeolite samples and, using these data, a safety evaluation was carried out.

Determination of trace elements in Sergio mirim: an evaluation of sample preparation methods and detection techniques.

In this work, some trace elements (As, Cd, Cr, Cu, and Pb) were determined for the first time in the crustacean Sergio mirim (Decapoda: Thalassinidea: Callianassidae) from Southern Coast (Rio Grande, RS) of Brazil. The trace element determination was carried out by graphite furnace atomic absorption spectrometry (GF AAS) and inductively coupled plasma mass spectrometry (ICP-MS). Different microwave radiation-based sample digestion methods were evaluated. The analyte concentration ranged from 1.45 to 3.70 µg g-1 for As, 0.615 to 0.942 µg g-1 for Cd, 0.884 to 7.20 µg g-1 for Cr, 122 to 275 µg g-1 for Cu, and 0.390 to 0.916 µg g-1 for Pb. The limits of quantification for As, Cd, Cr, Cu, and Pb were 0.12, 0.01, 0.16, 0.92, and 0.06 µg g-1, respectively. The accuracy was evaluated by results comparison between GF AAS and ICP-MS techniques, as well as by analysis of certified reference materials of fish muscle and oyster tissue, with agreement from 92 to 108%. The feasibility of using Sergio mirim as a promising environmental bioindicator candidate was evaluated, since that it is an abundant organism in the studied area (South cost of Brazil) as well as in other places around the world.

Heavy Metals in Tissues of Blue Crabs Callinectes danae from a Subtropical Protected Estuary Influenced by Mining Residues.

This short note aims to report in detail a preliminary assessment of the concentrations of Cd, Hg and Pb in tissues of blue crabs Callinectes danae collected from the Cananéia-Iguape-Peruíbe estuarine complex (CIP), in the South of São Paulo State coast, Brazil. In October 2014, blue crabs were collected from CIP. Tissues were removed by dissection and metal determination was performed by GF-AAS and CV-AAS. According to statistical analysis, Pb and Cd concentrations in gills were significantly higher than those found in muscles and hepatopancreas, respectively. There were no significant differences in Hg concentrations between samples. Cd, Hg and Pb concentrations in gills and hepatopancreas were lower than those reported in a previous study performed at CIP. However, Cd concentration in hepatopancreas was higher than the Brazilian limit for consumption and new efforts to monitor Cd concentrations in C. danae tissues must be performed.

Organic Ion-associate Phase Extraction/Back-microextraction for the Preconcentration and Determination of Lithium Using 2,2,6,6-Tetramethyl-3,5-heptanedione by Liquid Electrode Plasma Atomic Emission Spectrometry and GF-AAS in Environmental Water.

We developed an ion-associate phase (IAP)-extraction/acid back-extraction system for the preconcentration and atomic spectrometric determination of lithium trace amounts in water. The chelating reagent for lithium also works as a constituent of the extraction phase. The lithium in a 10 mL sample solution was converted through a chelate complex reaction with 2,2,6,6-tetramethyl-3,5-heptanedione (HDPM). The addition of a benzyldimethyltetradecylammonium ion caused the formation of IAP suspension in the solution. Centrifugation of the solution led to the isolation of a liquid organic phase and the lithium complex was extracted as the upper phase from the centrifuge tube. After the aqueous phase was removed, lithium was back-extracted with a 400 µL nitric acid solution from the IAP. The acid phase was measured using liquid-electrode-plasma atomic-emission-spectrometry (LEP-AES) or graphite-furnace atomic-absorption spectroscopy (GF-AAS). The detection limits were 0.02 mg/L for LEP-AES and 0.02 µg/L for GF-AAS. This system was applied to the determination of environmental water. The HDPM in the organic phase was reusable.

The HR-CS-GF-AAS determination and preconcentration of palladium in contaminated urban areas, especially in lichens.

The increasing content of platinum group metal particles emitted into the environment by car traffic is gradually attracting the attention of the scientific community. However, the methods for the determination of platinum group metals in environmental matrices are either costly or suffer from low sensitivity. To facilitate the use of less sensitive, but significantly cheaper, devices, the preconcentration of platinum group metals is employed. For platinum, a multitude of preconcentration approaches have been published. On the contrary, the preconcentration approaches for palladium are still rare. In this work, the development, optimization, and testing of a new approach is described; it is based on a preconcentration of palladium on octadecyl modified silica gel together with the complexing agent dimethylglyoxime, and it is then analyzed with the high-resolution continuum-source atomic absorption spectrometry. For comparison, a newly developed sorbent, QuadraSil™ TA, with a high affinity for platinum group metals was also tested. The preconcentraiton approach was tested on the lichen Hypogymnia physodes, which served as a bioindicator of palladium emissions. The case study site was a mid-sized city in central Europe: Brno, Czech Republic. The dry "bag" monitoring technique was used to collect the palladium near roads with a large span of traffic density. The developed analytical approach confirmed an increasing concentration of palladium with increasing exposure time and intensity of the traffic. Consequently, a simple relationship between the amount of bioaccumulated palladium and traffic density was established.

The use of dried matrix spot for determination of Pb and Ni in automotive gasoline by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry.

In this work a simple and practical method for the determination of Pb and Ni in automotive gasoline by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry was investigated. In the proposed method, disks of filter paper were used to pre-concentrate and store Pb, Ni and other trace elements from automotive gasoline samples. For this, a volume of sample was deposited and dried out on a filter paper disk previously adapted into a polytetrafluoroethylene mold, and then the gasoline-embedded filter paper was either cut into small pieces or pulverised and introduced directly into the graphite furnace for trace element determination. Temperature program, use of chemical modifier, chromatographic effect and volume of sample were investigated. Calibration curves using organic and inorganic standards of the analytes as well as external and internal calibration methods were evaluated. Using optimised conditions, characteristic masses and limits of detection of 6 and 11 pg, and 0.5 and 2.1 µg L-1 were found for Pb and Ni, respectively. The accuracy of the method was evaluated with spike-recovery tests and a certified reference material of wear lubricant oil. The spike-recovery tests were accomplished for 9 samples and the best results were obtained with the pulverised filter paper. A second method that employs a transversely heated filter atomiser was applied as a comparative one. The filter paper was shown to be a simple and inexpensive tool for storage and transportation of gasoline samples, and it allowed the pre-concentration of the analytes, since a larger volume of sample can be dried out on it.

High Efficiency Mercury Sorption by Dead Biomass of Lysinibacillus Sphaericus-New Insights into the Treatment of Contaminated Water.

Mercury (Hg) is a toxic metal frequently used in illegal and artisanal extraction of gold and silver which makes it a cause of environmental poisoning. Since biosorption of other heavy metals has been reported for several Lysinibacillus sphaericus strains, this study investigates Hg removal. Three L. sphaericus strains previously reported as metal tolerant (CBAM5, Ot4b31, and III(3)7) were assessed with mercury chloride (HgCl2). Bacteria were characterized by scanning electron microscopy coupled with energy dispersive spectroscopy (EDS-SEM). Sorption was evaluated in live and dead bacterial biomass by free and immobilized cells assays. Hg quantification was achieved through spectrophotometry at 508 nm by reaction of Hg supernatants with dithizone prepared in Triton X-114 and by graphite furnace atomic absorption spectroscopy (GF-AAS). Bacteria grew up to 60 ppm of HgCl2. Non-immobilized dead cell mixture of strains III(3)7 and Ot4b31 showed a maximum sorption efficiency of 28.4 µg Hg/mg bacteria during the first 5 min of contact with HgCl2, removing over 95% of Hg. This process was escalated in a semi-batch bubbling fluidized bed reactor (BFB) using rice husk as the immobilization matrix leading to a similar level of efficiency. EDS-SEM analysis showed that all strains can adsorb Hg as particles of nanometric scale that can be related to the presence of S-layer metal binding proteins as shown in previous studies. These results suggest that L. sphaericus could be used as a novel biological method of mercury removal from polluted wastewater.

Assessment of cadmium and lead in commercial coconut water and industrialized coconut milk employing HR-CS GF AAS.

In this work, an analytical method for the determination of Cd and Pb in natural coconut water samples, industrialized coconut water samples and coconut milk using high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS), after minimum treatment of the sample was developed. The analytical method was applied to 46 samples collected in Salvador, Bahia (Brazil). The ranges of concentrations obtained were: 0.42-18.72 µg L-1 Cd and <0.70-36.32 µg L-1 Pb for natural coconut water samples (n = 14); <0.06-1.49 µg L-1 Cd and 6.57-29.02 µg L-1 Pb for industrialized water coconut samples (n = 16); and <0.10-5.93 ng g-1 Cd and <0.85-22.41 ng g-1 Pb for coconut milk samples (n = 16). For all samples, Cd and Pb concentrations were below the maximum tolerated values recommended by Brazilian Health Surveillance Agency (Agência Nacional de Vigilância Sanitária, ANVISA).

Simultaneous determination of iron and nickel as contaminants in multimineral and multivitamin supplements by solid sampling HR-CS GF AAS.

A methodology to assay simultaneously iron and nickel present as contaminants in multimineral and multivitamin supplements was investigated. High-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sample analysis were used. Measurements were done with the secondary lines of Fe (352.604 nm) and Ni (352.454 nm) to avoid spectral interferences. The best temperatures for pyrolysis and atomization for Fe and Ni were 1000 and 2700 °C, respectively. Chemical modifiers were not necessary and no matrix effects were observed. Aqueous standard solutions were used for calibration. The limit of detection was 0.517 µg g-1 for Fe and 0.011 µg g-1 for Ni. The precision ranged from 4.3% to 17% and 4.4-20% for Fe and Ni, respectively. The method accuracy was confirmed by comparing statistically the results obtained by solid sampling with those of sample acid digestion. The proposed methodology was successfully applied to determine both metals in different multimineral and multivitamin supplements.

Multivariate optimization of ultrasound-assisted extraction using Doehlert matrix for simultaneous determination of Fe and Ni in vegetable oils by high-resolution continuum source graphite furnace atomic absorption spectrometry.

A method for simultaneous determination of Fe (232.036 nm) and Ni (232.195 nm) in vegetable oil samples by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) after an acid extraction of the analytes is proposed. In the extraction step, hydrochloric, nitric and acetic acid solutions were tested. The optimization of the procedure was performed by applying Doehlert matrix, and multiple response was used for simultaneous evaluation of the performance of the extraction. The optimum conditions were: extraction time of 17 min, extraction temperature of 39 °C and sonication amplitude of 42%, employing 0.5 mol L-1 HCl as the extracting solvent. The limits of quantification were 60 and 160 ng g-1 for Fe and Ni, respectively. The method was applied to the analysis of vegetable oil samples and the results were compared with a method employing inductively coupled plasma optical emission spectrometry (ICP OES).

Determination of Cadmium Concentration in Milled and Brown Rice Grains Using Graphite Furnace Atomic Absorption Spectrometry.

Heavy metal pollution is a growing public health concern since it poses a food risk to public health via metal transfer. Cadmium is of particular concern because it is a potential carcinogen if exceed tolerable limits in the grain. Hence, it is important to monitor the cadmium content of rice before it reaches the market to ensure public healthy safety, especially in areas known to have high cadmium levels in soil. In this chapter, the method used to determine the concentration of cadmium in milled and brown rice grain samples is described. This method involves sample digestion with concentrated nitric acid and hydrogen peroxide and analysis of cadmium by Graphite Furnace Atomic Absorption Spectrometry (GF-AAS). Because cadmium concentrations are low in rice grains, quantification of cadmium content requires the use of a more sensitive instrument, such as GF-AAS.

Micro-organic Ion-associate Phase Extraction/micro-volume Back-extraction for the Preconcentration and GF-AAS Determination of Cadmium, Nickel and Lead in Environmental Water.

Micro-organic ion-associate phase (IAP) extraction was combined with a micro-volume back-extraction (MVBE) to reduce coexisting components and viscosity in the concentrates. Heavy metals were converted into a complex with 2-(5-bromo-2-pyridylazo)-5-(N-propyl-N-sulfopropylamino)phenol in a 40-mL sample solution, and were extracted into ion associates. After centrifugation and discarding the aqueous phase, trace metals were stripped from IAP into a nitric acid solution, followed by GF-AAS determination. Only one vessel was required for 400-fold enrichment. The detection limits (3σb) for Cd, Ni, and Pb were 0.6, 3.7, and 0.8 ng/L, respectively. This method was applied in recovery tests in seawater.