MEKC determination of vanadium from mineral ore and crude petroleum oil samples using precapillary chelation with bis(salicylaldehyde)tetramethyl‐ethylenediimine

An analytical procedure has been developed for the separation of Cu(II), Ni(II), Co(II), Fe(II), Pd(II), Th(IV), V(IV), and determination of Fe(II), Co(II), Ni(II), and V(IV) by MEKC after chelation with bis(salicylaldehyde)tetramethylethylenediimine (H₂SA₂Ten). Uncoated fused silica capillary was used with an applied voltage of 30 kV with photo‐diode array detection at 228 nm. SDS was added as micellar medium at pH 8.2 with sodium tetraborate buffer (0.1 M). Linear calibrations were established within 0.015–1000 μg/mL of each element with LOD within 5–67 ng/mL. The method was applied for the determination of vanadium from crude oil and ore samples in the range 0.34–2.40 and 114.2–720.7 μg/g with RSD 1.7–3.8 and 0.98–2.30% (n = 3), respectively. Fe, Ni, and Co present in crude oil and ore samples were also determined with RSD 1.3–2.8, 1.1–4.1, and 1.2–3.5% (n = 3), respectively. The results were compared with that of supplier's specifications and atomic absorption spectrometry (AAS). Method was evaluated by standard addition technique.     

Determination of cadmium and lead in biological samples by three ultrasonic-based samples treatment procedures followed by electrothermal atomic absorption spectrometry

The development of 3 different ultrasonic-based sample treatment methods, ultrasonic probe-assisted acid extraction, ultrasonic-assisted acid slurry, and ultrasonic-assisted acid pseudodigestion is presented. These methods were compared for the determination of Cd and Pb by electrothermal atomic absorption spectrometry in biological samples (blood and scalp hair) and validated by using certified materials BCR 397 human hair and BCR 185R bovine liver. The sample amounts chosen to perform the analysis were 100 mg and 0.5 mL for solids (human hair and bovine liver) and blood samples, respectively. An acid digestion induced by microwave energy was used to obtain the total metal concentrations and for comparative purposes. The best results were obtained with the ultrasonic-assisted acid pseudodigestion, with which it was possible to perform accurate and precise determination of the Cd and Pb contents in 2 certified reference materials and biological samples of 50 normal males of ages 25-40 years. The precision of the methods, together with their efficiency, rapidity, low cost, and environmental acceptability, make them good alternatives for the determination of trace metals from biological samples. The precision of the methods for accuracy evaluation, resulting in good agreement according to the t-test for a 95% confidence level, and the relative standard deviations were lower than 10% (n=10) for all determinations.     

Determination of uranium, iron, copper, and nickel from ore samples by MEKC using N,N'-ethylene bis(salicylaldimine) as complexing reagent

An analytical procedure has been developed for the separation of dioxouranium(VI), iron(III), copper(II), nickel(II), cobalt(II), cobalt(III), palladium(II), and thorium(IV) by MEKC using N,N'-ethylene bis(salicylaldimine) (H(2)SA(2)en) as a complexing reagent with total runtime <4.5 min. SDS was used as micellar medium at pH 8 with sodium tetraborate buffer (0.1 M). An uncoated fused-silica capillary with an effective length of 50 cm x 75 microm id was used with an applied voltage of 30 kV with photodiode array detection at 231 nm. Linear calibrations were obtained within 0.111-1000 microg/mL of each element with LODs within 37-325 ng/mL. The developed method was tested for analysis of uranium ore samples indicating its presence within 103-1789 microg/g with RSD within 0.79-1.87%. Likewise copper, nickel, and iron in their combined matrix were also simultaneously determined with RSD 0.4-1.6% (n = 6).     

Ultrasound-assisted pseudodigestion for toxic metals determination in fish muscles followed by electrothermal atomic absorption spectrophotometry: multivariate strategy

A simple and efficient procedure for the determination of arsenic (As), cadmium (Cd), and lead (Pb) in the edible parts of freshwater fish by ultrasonic-assisted acid pseudodigestion (USD) was developed. A Plackett-Burman experimental design was used as a multivariate strategy for the evaluation of the effects of several variables at once. Five variables--sonication time, sample mass of muscle tissue, temperature of the ultrasonic bath, mL of nitric acid, and mL of a mixture of acid and oxidant--were regarded as factors. From these studies, certain variables showed up as significant, and they were optimized by a 23+star central composite design, which involved 16 experiments. Optimum values of the variables were selected for the development of USD to determine the contents of As, Cd, and Pb in fish muscles used as pollution bioindicators from Lake Manchar (Sindh, Pakistan). The determination of the 3 toxic metals under study was performed by electrothermal atomic absorption spectrometry. The accuracy of the optimized procedure was evaluated by analysis of certified reference materials BCR 185R bovine liver and by comparison with conventional wet acid digestion methodology. The result obtained by the optimized method showed good agreement with the certified values and sufficiently high recovery. No significant differences were observed for P = 0.05. Relative standard deviation values (average of 10 separate determinations) were 1.21, 5.52, and 5.32% for As, Cd, and Pb, respectively.     

Evaluating the mobility of toxic metals in untreated industrial wastewater sludge using a BCR sequential extraction procedure and a leaching test

The distribution and speciation of toxic metals in industrial wastewater sludge (IWS) was investigated. In this work, the modified BCR three-stage sequential extraction procedure was applied to the fractionation of Cr Pb Ni, and Cd in untreated industrial wastewater sludge from industrial sites in Hyderabad (Pakistan). The extracts were analyzed using electrothermal atomic absorption spectrometry. The procedure was evaluated using a certified reference material for soil mixed with sewage sludge BCR 483. The results from the partitioning study indicate that more easily mobilized forms (acid exchangeable) of Cd were dominant. The oxidizable fraction was dominant for all four toxic metals. Metal recovery was good, with <4% difference between the total metal recovered through the extractant steps and the total metal determined after microwave digestion. Lixiviation tests (DIN 38414-S4) were used to evaluate the leaching of toxic species from IWS, and it was observed that levels of leachable toxic metals were low compared to the amount of metal extracted in the exchangeable fraction of the BCR protocol.     

Sub-ppt level voltammetric sensor for Hg2+ detection based on nafion stabilized l-cysteine-capped Au@Ag core-shell nanoparticles

Journal of Solid State Electrochemistry - Bimetallic nanoparticles (BMNPs) have received considerable attention due to their distinctive properties when compared to the corresponding monometallic...     

A innovative switchable polarity solvent,based on 1,8‐diazabicyclo‐[5.4.0]‐ undec‐7‐ene and decanol was prepared for enrichment of aluminum in biological sample prior to analysis by flame atomic absorption spectrometry

A novel switchable solvent (SS) extraction methodology has been used for the enrichment of aluminium (Al) in acid‐digested blood samples of patients with neurological disorders before proceeding to flame atomic absorption spectrometry. 1,8‐Diazabicyclo[5.4.0]undec‐7‐ene and decanol in combination made a SS which reversibly changes from hydrophobic (nonpolar) to hydrophilic (polar) according to switch‐on and switch‐off phenomena in aqueous medium by exposure to anti‐solvent trigger (CO₂). The SS polar micro‐emulsion was switched on by bubbling CO₂, and switched off by heating from 40 to 70°C with exposure to N₂ gas. The changes obtained in the structure and physical properties of the SS due to switching from lower polarity to higher polarity were investigated using Fourier transform infrared spectroscopic analysis. The SS was effectively analysed as an extractive medium for hydrophobic chelate of Al with 3,5,7,2,4‐pentahydroxyflavone (morin) and extracted in SS. Then hydrophobic enriched Al‐morin‐SS was treated with 1.0 M HNO₃ and CO₂ purging at various time intervals, switch to a miscible polar hydrophilic monophase state. The SS was easily recycled up to six times for further enrichment process. For the developed method, various parameters were optimized such as pH, volume of chelating reagent, CO₂ purging time and pressure, and rate of heating. Under favourable conditions, enhancement factor and limit of detection were observed as 25 and 0.47 μg l^?1, respectively, for 10 ml of samples/standards solution. The accuracy of the developed method was determined using certified reference material (SRM 3101a), with a standard addition procedure. The method was used for the pre‐concentration of Al in blood samples of patients with neurological disorders.     

A tandem ionic liquid-based dispersive microextraction method using in-syringe air-assisted vesicle system for rapid determination of lead and cadmium in artificial sweat extract of facial cosmetic products

In the present study an innovative tandem ionic liquid-based dispersive microextraction method using an in-syringe air-assisted vesicle system was developed to determine the ultra-trace levels of lead (Pb^II) and cadmium (Cd^II) ions in synthetic sweat extract of branded and nonbranded facial cosmetic products. This method is based on injecting 2-amino-3-sulfhydrylpropanoic acid (l -cysteine) (as an eco-friendly chelating agent), hexafluorophosphate ion [PF₆⁻] (as an ion pair agent) and 1-hexyl-3-methylimidazolium hexafluorophosphate [HMIM] [PF₆] (as an acceptor phase) into the synthetic sweat extract of facial cosmetic products (branded and nonbranded). The acceleration of the dispersion process was carried out by rapid pressure in the syringe through the back-and-forth movement of plunger. The sediment phase was removed following centrifugation, and then hydrophobic complexes of analyte were back-extracted into HNO₃ and finally injected into a flame atomic absorption spectrometer. Several factors were systematically optimized. The validity of the methodology was tested by analyzing spiked known standards of both metals in a real sample. The proposed method was applied to the artificial sweat extracts of face makeup products, indicating how much toxic metals from different cosmetics are directly absorbed into skin.     

Analysis of Heavy Metals in Scalp Hair Samples of Hypertensive Patients by Conventional and Microwave Digestion Methods

The abnormal metabolism of metal ions plays an important role in health and disease conditions, and studies about them have been attracting significant interest. The aim of our study was to assess the heavy metals (cadmium, copper, iron, nickel, chromium, lead, and zinc) in scalp hair samples of 200 hypertensive (HT) patients of an urban population together with 215 non‐hypertensive male subjects in the age group of 30–60 years. Hair samples were digested with conventional wet ashing and microwave digestion. Analyses of both digests were done by flame and graphite furnace atomic absorption spectrometry. The validity of methodology was checked by use of the certified reference material (CRM 397) hair, provided the Community Bureau of Reference, Commission of the European Communities. According to a statistical evaluation of the results, the microwave digestion method was a valid alternative to the conventional acid digestion method, p value >0.05, but it gave a faster digestion. The overall metal recoveries were 96–98% of those obtained with microwave digestion. Among the toxic elements determined, levels of nickel, cadmium, copper, chromium, and lead in scalp hair samples of hypertensive patients were significantly higher compared normal male subjects, whereas the essential elements such as iron and zinc were found to be low compared age‐matched non‐hypertensive subjects.     

Determination of Cadmium in Human Serum and Blood Samples after Dispersive Liquid–Liquid Microextraction Using a Task-Specific Ionic Liquid

Task-specific ionic liquid dispersive liquid–liquid microextraction (TSIL-DLLME) is a simple and rapid preconcentration approach for the measurement of cadmium in serum and blood samples of human subjects. In this method a novel task-specific ionic liquid, trioctylmethyl ammonium thiosalicylate (TOMATS), which has dual characteristics as a chelating agent and extractive solvent, was investigated. TOMATS complexes with Cd due to the chelating effect of the ortho-positioned carboxylate relative to the thiol functionality. The assessment of the optimum values of variables including the pH, amount of reagents (TOMATS, diluents, Triton X114, and back extracting acid solution), temperature, and incubation time, which affect the recoveries of analyte by TSIL-DLLME method were studied. After enrichment experiments, acidic solution was used to back extract the metal ions from the ionic liquid rich phase and with determination by electrothermal atomic absorption spectrometry. Using the optimal experimental conditions, the limit of detection (3?s), precision (relative standard deviation), preconcentration, and enhancement factors of developed method for Cd were found to be 0.05?µg/L, greater than 5%, 62.5, and 52.8, respectively. To check the accuracy of the developed method, certified reference material of serum and blood were analyzed by the developed method, and the measured values of Cd were in good agreement with the certified values. The developed method was applied successfully to determine Cd in blood and serum samples of lymphatic cancer patients relative to healthy controls.