A miniaturized liquid-liquid extraction method for further Na, K, Ca, and Mg determination in crude oil by FAAS.

In this study, a miniaturized liquid-liquid extraction (LLE) method for pre-concentration of Na, K, Ca, and Mg in crude oil was proposed. Analytes in crude oil were quantitatively extracted to the aqueous phase, followed by flame atomic absorption spectrometry (FAAS) determination. The following parameters were evaluated: type of extraction solution, sample mass, heating temperature and time, stirring time, centrifugation time, and the use of toluene and chemical demulsifier. Accuracy was evaluated by comparing the results obtained by the proposed method (LLE-FAAS) with those obtained after high-pressure microwave-assisted wet digestion and FAAS determination (reference values). No statistical difference was observed between the reference values and those using the optimized conditions for LLE-FAAS: 2.5 g of sample; 1000 µL of 2 mol L-1 HNO3, 50 mg L-1 of chemical demulsifier in 500 µL of toluene, 10 min of heating at 80 °C, 60 s of stirring, and 10 min of centrifugation. Relative standard deviations were lower than 6%. The limits of quantification (LOQ) were 1.2, 1.5, 5.0, and 0.50 µg g-1 for Na, K, Ca, and Mg, respectively. The proposed miniaturized LLE method presents several advantages, such as ease-of-use, high throughput (up 10 samples can be processed per 1 h), uses a high sample mass reaching low LOQs. In addition, the use of a diluted solution for extraction reduces the amount of reagents (around 40 times) and consequently laboratory residue generation, becoming an environmental friendly method. Suitable LOQs were achieved for analyte determination at low concentration even using a simple and low-cost sample preparation system (miniaturized LLE method) and a relatively low-cost determination technique (FAAS), avoiding the use of microwave ovens and more sensitivity techniques, which are required for routine analyses.

Ultrasound-assisted adsorption on porous ceramic for removal of iron in water.

This study proposes the use of an ultrasound-assisted adsorption system coupled to porous ceramic fragments to improve the removal of iron from FeSO4 aqueous solution. Ultrasound was applied using an ultrasound bath at a low frequency (37 kHz, 330 W). The optimized conditions for Fe removal were achieved by 7 g of adsorbent, 40 min of sonication, 20 mg L-1 of initial Fe concentration, and 30 °C of reaction temperature. After optimizing the conditions, the method was applied for the removal of iron in groundwater. A central composite design and response surface methodology were used to evaluate the degree to which different variables had a significant effect on iron removal. The efficiency of iron removal using the selected conditions for FeSO4 solution was near to 100%. However, for groundwater samples, the maximum iron removal efficiencies of the system with and without ultrasound were 80.7% and 51.1%, respectively, indicating that the adsorption with ultrasound was significantly higher than that without ultrasound. It was shown that the proposed ultrasound-assisted adsorption system can be used to enhance the removal of inorganic iron from groundwater.

Environmental and human health risks associated with exposure to hazardous elements present in urban dust from Barranquilla, Colombian Caribbean.

Urban dust is a mixture of deposited particles from different sources usually linked to potentially toxic elements (PTEs). Despite the industrialization of many South American countries, little is known about the impact of particulate matter in large cities; these data are necessary to promote environmental policies aiming to protect human health. The main objective of this work was to evaluate the particle size distribution, composition, and environmental and human health risks of settled dust particles from Barranquilla, a Colombian Caribbean industrialized area. Trace elements were analyzed by inductively coupled plasma-mass spectrometry from 35 different sites, covering all city areas. Dust was mostly composed of 10-to-70-µm particles. The average concentrations of V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Sn, Sb, Pb, and Bi were above background. High spatial heterogeneity was observed for Cu, Zn, As, Se, Mo, Ag, Sn, Sb, and Bi. Concentration factors suggest that urban dusts are extremely contaminated by Zn and Cu. The ecological risk associated with specific elements decreased in the order Cd > Cu > As > Hg > Pb > Ni > Co ≈ Zn ≈ Cr, and the contamination load index showed that 91% of the samples are polluted by PTEs. Although the carcinogenic risks of Cr, Ni, As, Co, and Cd were low, chronic exposure to several PTEs may affect quality of life. Educational programs, as well as monitoring and greater control on traffic, industry, and construction activities are needed to protect environmental and human health.

A solid sampling approach for direct determination of Cl and S in flour by an elemental analyzer.

Direct analysis of flour was proposed for the determination of Cl and S by an elemental analyzer for the first time. The main operational conditions of the direct solid sampling elemental analysis (DSS-EA) were optimized and calibrated by standard solutions, rather than by certified reference material (CRM). Accuracy was evaluated by the analysis of CRM of rice flour and by comparison with analyte determination by independent techniques, i.e., ion chromatography and inductively coupled plasma optical emission spectrometry; both were carried out after microwave-induced combustion. Sample mass from 0.5 to 260 mg was used and limits of quantification of 1.2 µg g-1 for Cl and 0.2 µg g-1 for S were achieved. Wheat, whole wheat, potato and corn flour were analyzed by DSS-EA. Concentrations of Cl and S ranged from 4.8 to 685 µg g-1 and from 13 to 1328 µg g-1, respectively.

Determination of halogens and sulfur in honey: a green analytical method using a single analysis.

The halogen determination is important in view of their biological and environmental roles, but their determination has still been considered a challenge, especially at low concentrations. Therefore, a method for honey decomposition using microwave-induced combustion (MIC) combined with ion chromatography and conductimetric detection (for Cl, F, and S determination) or mass detection (for Br and I determination) (IC-CD-MS) is proposed. Trueness was evaluated by adding reference materials (RMs) or a standard solution in the sample. By using 50 mmol L-1 NH4OH as the absorbing solution, recoveries for all analytes were between 94 and 103%, in both tests. Moreover, no statistical difference (t test, confidence level of 95%) was observed for the results obtained by IC in comparison with those obtained by inductively coupled plasma optical emission spectroscopy (Cl and S) and by inductively coupled plasma mass spectrometry (Br and I). Finally, the proposed method was applied to 19 honey samples from different origins. The concentrations ranged from < 0.45 to 2.39 mg kg-1 (Br), 21.8 to 671 mg kg-1 (Cl), and 11 to 154 mg kg-1 (S), while the F and I concentrations were below that their quantification limits (LOQs) in all analyzed samples. The LOQs for Br, Cl, F, I, and S were 0.45, 21, 3.7, 0.077, and 8.7 mg kg-1, respectively. The MIC method provided a compatible solution to IC for the halogen and S determination in honey by a single analysis. Graphical abstract.

Challenges and trends for halogen determination by inductively coupled plasma mass spectrometry: A review.

RATIONALE: In this review, works published in the past 25 years for fluorine, chlorine, bromine, and iodine determination in several matrices by inductively coupled plasma mass spectrometry (ICP-MS) were covered. Usually, the determination of halogens has been performed by ICP-MS using a previous sample preparation step or, more recently, by direct analysis of solid or liquid samples. METHODS: Methods based on combustion, extraction, pyrohydrolysis, sample dilution in organic or aqueous medium, and wet digestion, among others, are discussed. Moreover, the recent applications of methods based on laser ablation (LA) and electrothermal vaporization (ETV) coupled to ICP-MS are discussed. RESULTS: The main challenge for methods using sample preparation has been to obtain a final solution compatible with ICP-MS, as well as to overcome problems related to analyte losses and contamination. Interferences due to the presence of dissolved organic compounds in solution, enhancement or suppression of ionization of analytes, and related matrix effects have been of concern when using ICP-MS. For the determination of halogens by ICP-MS using LA and ETV systems, some limitations related to the difficulty of calibration are pointed out, impairing the widespread use of this approach. CONCLUSIONS: A critical view is presented for further halogen determination by ICP-MS, mainly for matrices considered difficult to digest using conventional protocols.

A simple, rapid and low cost reversed-phase dispersive liquid-liquid microextraction for the determination of Na, K, Ca and Mg in biodiesel.

In this work a method based on reversed-phase dispersive liquid-liquid microextraction (RP-DLLME) as sample preparation for the extraction and preconcentration of Na, K, Ca and Mg in biodiesel samples was developed. The analytes determination was performed by flame atomic absorption spectrometry (FAAS), operating in emission mode for Na and K and in absorption mode for Ca and Mg. The extraction/preconcentration step of the analytes was performed by using a mixture of dispersant and extractant solvents (isopropanol and HNO3, respectively) and the aqueous phase containing the analytes was separated by centrifugation. Some parameters such as sample mass, type and volume of dispersant and extractant solutions, HNO3 concentration (extraction solution), use of ultrasound, centrifugation time and temperature were evaluated. During the optimization of RP-DLLME, biodiesel samples were spiked with a multi-element biodiesel B100 (Conostan®) with final concentration of 1.0 µg g-1 of the analytes. Analytes determination was performed by FAAS using external calibration with aqueous reference solutions. The limits of quantification (LOQ) for Na, K, Ca and Mg were 0.04; 0.02; 0.05 and 0.08 µg kg respectively. The accuracy was evaluated by recovery tests, which ranged from 93.9% to 108.1%, with relative standard deviation lower than 3% for all analytes. Then, the proposed method was applied for analytes determination in five biodiesel samples produced from different raw materials. Comparing to conventional methods for elements determination in biodiesel (e.g., dilution with organic solvent, sample digestion, etc.), RP-DLLME combined to FAAS is simple, low cost, low reagents consumption and provides LOQs values significantly below compared to the limits established in the legislation for these elements in biodiesel.

An in situ pre-concentration method for fluorine determination based on successive digestions by microwave-induced combustion.

A new strategy based on successive digestions by microwave-induced combustion (MIC) in the same reaction vessel with a single absorbing solution was proposed. As a proof of concept, F was determined by ion-selective electrode (ISE) in seafood digests. Samples were pressed as pellets (up to 0.7 g) and combusted in closed quartz vessels pressurized with oxygen. Sequential digestions were each performed (up to 4 combustion cycles) in the same vessel and using the same absorbing solution. In each cycle, a new filter paper, igniter and sample pellet (0.7 g of sample) were used. Ammonium hydroxide solutions (10-100 mmol L-1) were evaluated for F absorption. Accuracy of the proposed method was evaluated using certified reference material of oyster tissue (NIST 1566a) and also by comparison of results after pyrohydrolysis method. Up to 3 digestion cycles (total mass of 2.1 g) could be used with 50 mmol L-1 NH4OH as absorbing solution. Results were in agreement with those obtained using pyrohydrolysis and also with certified reference value; the coefficient of variation after 3 cycles was below 5%, which was considered as suitable for F determination even at low concentration. The residual carbon in digests was lower than 25 mg L-1, allowing F determination by ISE virtually free of interferences due to dissolved organic matter. The limit of quantification (LOQ) for F was 1.3 µg g-1 (using 2.1 g of seafood), which is almost 4 times lower than the LOQ obtained using the reference method (pyrohydrolysis). Contrary to the reference method, this relatively low LOQ allowed the determination of F in all the seafood samples analysed. Taking into account that only 6 mL of diluted NH4OH solution (50 mmol L-1) were used and the suitable LOQ, the proposed sequential digestion MIC method can be recommended for further F determination in trace levels in seafood, even using a low-cost technique such as ISE, instead of other, more powerful techniques, such as ion chromatography.

Hyperglycemia elicits anxiety-like behaviors in zebrafish: Protective role of dietary diphenyl diselenide.

Diabetes mellitus (DM) is a chronic metabolic disease that may comorbid with various psychiatric disorders, such as anxiety and depression. The search for effective therapeutics to alleviate hyperglycemia and complications resulting from DM is continuous. Here we investigate the effects of diphenyl diselenide (DD), an organoselenium compound with several pharmacological properties, in a zebrafish model of hyperglycemia. Fish were fed for 74 days with a diet containing 3 mg/Kg DD, a concentration chosen after experiments based in a dose-response curve (DD 1, 2 and 3 mg/Kg) that did not cause overt toxicity (mortality, weight loss and neurobehavioral deficits). In the last 14 days of the experimental period, fish were concomitantly exposed to a glucose solution (111 mM). Afterwards, blood glucose levels, brain selenium (Se) content, and behavioral analysis aiming to assess anxiety-like behaviors and locomotor/exploratory activities were performed. In the novel tank diving test, glucose decreased vertical exploration and fish spent less time in the lit area when tested in the light-dark test, suggesting increased anxiety-like behavior. Moreover, DD decreased blood glucose levels in hyperglycemic fish as well as prevented the development of anxiety-related symptoms. DD diet alone did not change glycemia and behavioral parameters, but increased Se levels in the brain without affecting the cellular viability. Collectively, our findings highlight the growing utility of this zebrafish hyperglycemia model as a valuable strategy for further research in DM field and neuroprotective approaches.

Feasibility of halogen determination in noncombustible inorganic matrices by ion chromatography after a novel volatilization method using microwave-induced combustion.

A microwave-induced combustion (MIC) system based on the volatilization process was applied for subsequent halogen determination from noncombustible inorganic matrices. Portland cement samples were selected to demonstrate the feasibility of the proposed method, allowing the subsequent determination of Cl and F by ion chromatography (IC). Samples were mixed with high-purity microcrystalline cellulose, wrapped with a polyethylene film and combusted in quartz closed vessels pressurized with oxygen (20bar). Water and NH4OH (10, 25 or 50m mol L(-1)) were evaluated for Cl and F absorption, but water was selected, using 5min of reflux after volatilization. Final solutions were also suitable for analysis by pontentiometry with ion-selective electrode (ISE) for both analytes, and no difference was found when comparing the results with IC. The accuracy of the proposed method for Cl was evaluated by analysis of certified reference materials (CRMs), and agreement with certified values ranged from 98% to 103%. Results were also compared to those using the procedure recommended by the American Society of Testing and Materials (ASTM) for the determination of total chlorides (C114-13), and no difference was found. Volatilization by MIC using a mixture of cement, cellulose and a biological CRM was carried out in order to evaluate the accuracy for F, and recovery was about 96%. The proposed method allowed suitable limits of detection for Cl and F by IC (99 and 18mg kg(-1), respectively) for routine analysis of cement. Using the proposed method, a relatively low standard deviation (<7%), high throughput (up to eight samples can be processed in less than 30min) and lower generation of laboratory effluents, when compared to the ASTM method, were obtained. Therefore, the method for volatilization of Cl and F by MIC and subsequent determination by IC can be proposed as a suitable alternative for cement analysis.

Microwave-assisted ultraviolet digestion of petroleum coke for the simultaneous determination of nickel, vanadium and sulfur by ICP-OES.

A method for the simultaneous determination of Ni, V and S in petroleum coke by inductively coupled plasma optical emission spectrometry (ICP-OES) after microwave-assisted ultraviolet digestion (MW-UV) in closed vessels was proposed. Digestion was performed using electrodeless discharge lamps positioned inside quartz vessels and turned on by microwave radiation. The following parameters were evaluated: HNO3 concentration (15 mL of 1, 4, 7, 10 or 14.4 mol L(-1)), volume of H2O2 (30%, 1 or 3 mL), sample mass (100, 250 or 500 mg) and heating time (40 or 60 min) with or without the use of UV lamps. Digestion efficiency was evaluated by the determination of the residual carbon content (RCC) in digests. Using UV lamps lower RCC was obtained and the combination of 4 mol L(-1) HNO3 with 3 mL of H2O2 and 60 min of heating allowed a suitable digestion of up to 500 mg of petroleum coke (RCC< 21%). The agreement with the reference values for Ni, V and S (obtained by digestion of petroleum coke by microwave-induced combustion) and with a certified reference material of petroleum coke was between 96 and 101%. The proposed method was considered as advantageous when compared to American Society for Testing and Materials method because it allowed the simultaneous determination of Ni, V and S with lower limit of detection (0.22, 0.12 and 8.7 µg g(-1) for Ni, V and S, respectively) avoiding the use of concentrated nitric acid and providing digests suitable for routine analysis by ICP-OES.

Feasibility of ultra-trace determination of bromine and iodine in honey by ICP-MS using high sample mass in microwave-induced combustion.

This work demonstrates the feasibility of ultra-trace determination of halogens in biological samples by inductively coupled plasma mass spectrometry (ICP-MS) after decomposition by microwave-induced combustion (MIC). The conventional MIC method was improved to allow the combustion of samples with mass higher than that used in previous works in order to achieve better limits of detection (LODs). The applicability of the proposed method for ultra-trace determination of bromine and iodine in organic samples was demonstrated here using honey. It was possible to decompose up to 1000 mg of honey using microcrystalline cellulose as a combustion aid and polyethylene film for sample wrapping. After combustion, analytes were absorbed using 50 mmol L(-1) NH4OH and recoveries for Br and I were between 99 and 104 %, and relative standard deviations were lower than 5 %. Microwave-assisted alkaline dissolution (MA-AD) was also evaluated for honey sample preparation using NH4OH or tetramethylammonium hydroxide solutions. However, the LODs for the MA-AD method were unsuitable because the high carbon content in digests required a dilution step prior to the analysis by ICP-MS. The LODs obtained by MIC were improved from 1143 to 34 ng g(-1) for Br and from 571 to 6.0 ng g(-1) for I, when compared to the MA-AD method. Furthermore, it was possible to decompose up to eight samples simultaneously in 30 min (including the cooling step) with very low reagent consumption and consequently lower generation of effluents, making MIC method well suited for routine ultra-trace determination of Br and I in honey. Graphical Abstract A high mass of honey was efficiently digested by MIC for subsequent Br and I determination by ICP-MS.

Simple and fast method for iron determination in white and red wines using dispersive liquid-liquid microextraction and ultraviolet-visible spectrophotometry.

This work reports the development of a method for Fe extraction in white and red wines using dispersive liquid-liquid microextraction (DLLME) and determination by ultraviolet-visible spectrophotometry. For optimization of the DLLME method, the following parameters were evaluated: type and volume of dispersive (1300 µL of acetonitrile) and extraction (80 µL of C(2)Cl(4)) solvents, pH (3.0), concentration of ammonium pyrrolidinedithiocarbamate (APDC, 500 µL of 1% m/v APDC solution), NaCl concentration (not added), and extraction time. The calibration curve was performed using the analyte addition method, and the limit of detection and relative standard deviation were 0.2 mg L(-1) and below 7%, respectively. The accuracy was evaluated by comparison of results obtained after Fe determination by graphite furnace atomic absorption spectrometry, with agreement ranging from 94 to 105%. The proposed method was applied for Fe determination in white and red wines with concentrations ranging from 1.3 to 4.7 mg L(-1).