Selective cloud point extraction for the determination of cadmium in food samples by flame atomic absorption spectrometry

A new cloud point extraction (CPE) procedure for preconcentration of cadmium prior to the determination by flame atomic absorption spectrometry (FAAS) was developed. The method is based on the fact that cadmium could form hydrophobic ion-associated complex in the presence of iodide and methyl green (MG), and the hydrophobic ion-associated complex could be extracted into surfactant-rich phase. The main factors affecting CPE procedure, such as pH, concentration of KI, MG and surfactant, equilibrium temperature and incubation time, sample volume were investigated. Potential interference from co-existing ions was largely eliminated as most of co-existing ions can not form extractable ion-associated complex with iodide and MG. Under the optimum conditions, the limit of detection (3σ) and limit of quantity (10σ) were 0.90 ng mL⁻¹ and 3.0 ng mL⁻¹ for cadmium, respectively, and relative standard deviation was 4.2% (c = 50 ng mL⁻¹, n = 7). The proposed method was successfully applied to determination of cadmium in the certified reference rice sample (GBW08510) and food samples with satisfactory results.     

A novel quantum dot-based fluoroimmunoassay method for detection of Enrofloxacin residue in chicken muscle tissue

A rapid indirect competitive fluorescence-linked immunosorbent assay (cFLISA) based on quantum dots (QDs) as the fluorescent marker has been developed for the detection of Enrofloxacin (ENR) in chicken muscle tissue. The end-point fluorescent detection system was carried out using QDs conjugated with goat anti-mouse secondary antibody. The cFLISA method allowed for ENR determination in a liner working range of 1–100 ng mL⁻¹ with the 50% inhibition value (IC₅₀) of 8.3 ng mL⁻¹ and the limit of detection (LOD) of 2.5 ng mL⁻¹. The recoveries for chicken muscle samples spiked with ENR at levels of 50–200 μg kg⁻¹ ranged from 81% to 94% with coefficients of variation (CV) of 10–13%. In real chicken tissue sample analysis, the results of cFLISA were similar to those obtained from an indirect competitive enzyme-linked immunosorbent assay (cELISA) to a high performance liquid chromatography method (HPLC), which indicated that cFLISA is suitable as screening method for the monitoring of veterinary drug residues.     

Determination of copper with 5,5-dimethylcyclohexane-1,2,3-trione 1,2-dioxime 3-thiosemicarbazone in olive oils by adsorptive stripping square wave voltammetry

In the present paper a method for the determination of Cu in olive oil samples by adsorptive stripping square wave voltammetry (Ad-SSWV) is presented. It has been proven that Cu reacts with 5,5-dimethylcyclohexane-1,2,3-trione 1,2-dioxime 3-thiosemicarbazone, DCDT, in strongly acid media giving rise to a complex. In Ad-SSWV the complex Cu–DCDT experiments an adsorptive reductive process which promotes the appearance of a peak at −0.570 V. The extraction process of Cu from olive oil is carried out with hot concentrated HCl. Calibration graph has been constructed from 0 to 35 ng mL⁻¹ and the detection limit was 0.49 ng mL⁻¹. The method has been applied to commercial olive oils samples and the amounts of Cu found are very similar to those obtained when samples are analysed by AAS.     

Determination of formaldehyde in beer based on cloud point extraction using 2,4-dinitrophenylhydrazine as derivative reagent

A cloud point extraction method was developed for extraction of formaldehyde in beer prior to high performance liquid chromatography analysis. The formaldehyde was taken into complex with 2,4-dinitrophenylhydrazine in aqueous nonionic surfactant Triton X-114 medium and concentrated in the surfactant-rich phase by bringing the solution to the temperature of 60 °C. Under optimal conditions, the limit of detection of formaldehyde is 0.7 ng mL⁻¹. The intra- and inter-day precisions expressed as relative standard deviations are 4.2% and 5.5%, respectively. The proposed method was successfully applied for determination of formaldehyde in various beer samples. The contents of formaldehyde in these samples are in the range of 172-385 ng mL⁻¹. The results were in agreement with those obtained by the state standard method (steam-distillation and spectrophotometry analysis) used in China. The developed method was demonstrated to be rapid and sensitive for extraction and determination of formaldehyde in beer.     

Use of a portable time-resolved fluorometer to determine oxytetracycline residue in four fruit crops

Oxytetracycline (OTC) is used worldwide to protect crops against bacterial diseases. The US Environmental Protection Agency approved its use in apple, pear, nectarine, and peach, and set residue tolerance at 350 ng g⁻¹. A europium-sensitised luminescence (ESL) method was developed for in-situ determination of OTC residue in these fruits. After extraction in Na₂EDTA-NaCl-McIlvaine buffer at pH 4 and filtration, cleanup was performed using hydrophilic-lipophilic balance cartridges. ESL was measured using a portable time-resolved fluorometer. The signal responded linearly over three orders of magnitude (10–10000 ng g⁻¹) with 17–50 ng g⁻¹ limits of quantitation and 2% averaged relative standard deviation. Recoveries were 84% and 82% at 100 and 350 ng g⁻¹, respectively. Inter-laboratory validation was performed by HPLC–MS/MS.     

Trace element levels in honeys from different regions of Turkey

A survey of 25 honey samples from different botanical origin, collected all over the Turkey was conducted to assess their trace element contents. The aim of this study was to determine the levels of cadmium (Cd), lead (Pb), iron (Fe), manganese (Mn), copper (Cu), nickel (Ni), chromium (Cr), zinc (Zn), aluminium (Al) and selenium (Se) in honey samples from different regions of Turkey. Trace element contents were determined by a flame and graphite furnace atomic absorption spectrometry technique after dry-ashing, microwave digestion and wet-digestion. The accuracy of the method was corrected by the standard reference material, NIST-SRM 1515 Apple leaves. The contents of trace elements in honey samples were in the range of 0.23–2.41 μg g⁻¹, 0.32–4.56 μg g⁻¹, 1.1–12.7 μg g⁻¹, 1.8–10.2 μg g⁻¹, 8.4–105.8 μg kg⁻¹, 2.6–29.9 μg kg⁻¹, 2.4–37.9 μg kg⁻¹, 0.9–17.9 μg kg⁻¹, 83–325 μg kg⁻¹ and 38–113 μg kg⁻¹ for Cu, Mn, Zn, Fe, Pb, Ni, Cr, Cd, Al and Se, respectively. Iron was the most abundant element while cadmium was the lowest element in the Turkish honeys surveyed. The results showed that trace element concentrations in the honeys from different regions were generally correlated with the degree of trace element contamination of the environment.     

Rapid determination of formaldehyde and sulfur dioxide in food products and Chinese herbals

Simple, sensitive and rapid methods for the determination of formaldehyde and sulfur dioxide were developed. The formaldehyde determination is based on the reaction between formaldehyde and acetylacetone solution, producing yellow 3,5-diacetyl-l-1,4-dihydrolutidine. Sulfur dioxide was detected as the deoxidize of sulfurous acid by zinc in acidic medium, which produces sulfureted hydrogen that make lead acetate paper blackening due to lead sulfide formation. The detection limits were 0.8 μg mL⁻¹ and 6.0 μg mL⁻¹ for formaldehyde and sulfur dioxide, respectively. The linear range were 0.8–20.0 μg mL⁻¹ for formaldehyde and 6.0–100.0 μg mL⁻¹ for sulfur dioxide determination. The main advantages of the new analytical procedure are the low background level, high selectivity, and very little sample preparation for on-site analysis of formaldehyde and sulfur dioxide in food or Chinese herbal samples with reference color card for qualitative or semi-quantitative determination. The results from these methods correlated well with those obtained from the standard methods.     

Automatic determination of nickel in foods by flame atomic absorption spectrometry

A new sensitive and low cost flow injection method that combines acid extraction, preconcentration and flame atomic absorption spectrometric determination of nickel in food samples at μg/g levels is described. The dynamic acid extraction step was carried out by using a continuous ultrasound-assisted extraction system. The acid extract was preconcentrated on-line on a minicolumn packed with a chelating resin (Serdolit Che, with iminodiacetic groups) and nickel was eluted with diluted hydrochloric acid, being continuously monitored by flame atomic absorption spectrometry. An experimental design (Plackett-Burman 2⁶ × 3/16) is used to optimise the methodology proposed. The method allowed a total sampling frequency of 13–28 samples per hour. Good precision of the whole procedure (1.9–3.6% expressed as relative standard deviation) and a detection limit of 0.12 μg/g, for 60 mg of sample were achieved. The method was successfully applied to the determination of trace amounts of nickel in food samples.     

Response surface modelling of lead pre-concentration from food samples by miniaturised homogenous liquid–liquid solvent extraction: Box–Behnken design

In this study, a new method called miniaturised homogenous liquid–liquid extraction, followed by graphite furnace atomic absorption spectrometry, was developed for the extraction and determination of lead from food samples. The procedure was based on the fast extraction of lead from an acetic acid sample solution into 0.5 mL chloroform, as an extraction solvent. After adding water into the mixture, the extracting solvent phase immediately formed a distinct water-immiscible phase below the vial, which could easily be separated, evaporated and re-dissolved in 1.0 mL nitric acid 0.1 mol L⁻¹ for further analysis. The effects of various experimental parameters in extraction step were studied using two optimisation methods, one variable at a time and Box–Behnken design. The results showed that the amount of salt and extraction time did not have effect on the extraction efficiency. Therefore, a three-level Box–Behnken experimental design with three factors, which combined the response surface modelling, was used to optimise lead extraction. Three independent variables, including pH of solution (ranging from 6.5 to 10.5), concentration of dithizone as chelating agent (ranging from 0.05 to 0.5 μg L⁻¹) and extracting solvent volume (ranging from 300 to 900 μL) were respectively coded as pH, D and V at three different levels (−1, 0 and 1). In this study, the optimum condition was determined at pH 8.4, a volume of chloroform at 0.45 mL, and concentration of dithizone at 0.5 μg L⁻¹. Under the optimum condition, the limit of detection (LOD) was 0.05 μg L⁻¹. Furthermore, the relative standard deviation of the ten replicate was <5.0%. The developed procedure was applied to the extraction and determination of lead in the food samples.     

Direct determination of copper,lead and cadmium in aniseed spirits by electrothermal atomic absorption spectrometry

Direct determination of copper, lead and cadmium by electrothermal atomic absorption spectrometry in aniseed spirits was proposed. The methods were validated by studying quality parameters such as trueness, precision, linearity and sensitivity. Recoveries ranging between 96% and 104% were obtained from spiked samples at several concentration levels. Repeatability was less than 5% and intermediate precision was less than 8%. The procedure is fast and shows limits of detection of 0.6, 0.7 and 0.04 μg l⁻¹ for Cu, Pb and Cd, respectively. Samples were just diluted in a water/ethanol/nitric acid mixture. Cu was present at higher concentrations, with values in the range 6–473 μg l⁻¹. Minor levels of Pb and Cd were present with concentrations of less than 6 and 1.4 μg l⁻¹, respectively.     

Application of acetylacetone chelation solid-phase extraction to GFAAS measurements of trace amounts of beryllium in livers and muscles of poultry and livestock

Trace amounts (0.004–0.55 ng) of beryllium (Be) in a dried bovine liver sample (20 mg) can be accurately determined by graphite-furnace atomic absorption spectrophotometry (GFAAS) after treating with microwave digestion (HNO₃/H₂O₂) at 85 °C for 10 min and using acetylacetone as a chelating agent in the presence of an acetate buffer (pH 6.0). The method detection limit (MDL, 3σ) for Be was found to be 0.18 ng g⁻¹ and the limit of quantification (LOQ, 10σ) was found to be 0.60 ng g⁻¹; the calibration graph was linear up to 27 ng g⁻¹. The Be contents measured in four liver and four muscle samples (BCR CRM-185R bovine liver, BCR CRM-384 pork muscle, and six samples collected in Kaohsiung, Taiwan, ROC) were between 2.3 and 4.7 ng g⁻¹. Good spiked recoveries (96.0–103.0%) were obtained for these eight samples with a relative standard deviation (RSD, n = 3) ?3.0%. The method could be applied to measurements of Be in livers and muscles of poultry and livestock.     

Determination of metal contaminations in sea foods from Marmara,Aegean and Mediterranean seas: Twelve fish species

The concentrations of cadmium, cobalt, chromium, copper, iron, manganese, nickel, lead and zinc were determined by ICP-AES in muscles and livers of 12 fish species sampled from the Marmara, Aegean and Mediterranean seas of Turkey. Iron showed the highest levels in examined tissues of all fish species. Following Fe, Zn generally showed the second highest levels. Metal concentrations in edible parts of fish species were 0.02–0.37 mg kg⁻¹ for cadmium, 0.04–0.41 mg kg⁻¹ for cobalt, 0.04–1.75 mg kg⁻¹ for chromium, 0.32–6.48  mg kg⁻¹ for copper, 7.46–40.1 mg kg⁻¹ for iron, 0.10–0.99  mg kg⁻¹ for manganese, 0.02–3.97 mg kg⁻¹ for nickel, 0.33–0.86 mg kg⁻¹ for lead, 4.49–11.2 mg kg⁻¹ for zinc, respectively. All metal concentrations in livers were higher than those in muscles. In some stations, cadmium and chromium concentrations in both muscles and livers, and lead levels in livers of the examined species were higher than permissible safety levels for human uses.     

Trace metal content in nine species of fish from the Black and Aegean Seas,Turkey

Trace metal content of nine fish species harvested from the Black and Aegean Seas were determined by microwave digestion and atomic absorption spectroscopy (MD–AAS). Verification of the MD–AAS method was demonstrated by analysis of standard reference material (NRCC-DORM-2 dogfish muscle). Trace metal content in fish samples were 0.73–1.83 μg/g for copper, 0.45–0.90 μg/g for cadmium, 0.33–0.93 μg/g for lead, 35.4–106 μg/g for zinc, 1.28–7.40 μg/g for manganese, 68.6–163 μg/g for iron, 0.95–1.98 μg/g for chromium, and 1.92–5.68 μg/g for nickel. The levels of lead and cadmium in fish samples were higher than the recommended legal limits for human consumption.     

Hollow fibre-based liquid phase microextraction combined with high-performance liquid chromatography for the analysis of flavonoids in Echinophora platyloba DC. and Mentha piperita

A simple, inexpensive and efficient three phase hollow fibre liquid phase microextraction (HF-LPME) technique combined with HPLC was used for the simultaneous determination of flavonoids in Echinophora platyloba DC. and Mentha piperita. Different factors affecting the HF-LPME procedure were investigated and optimised. The optimised extraction conditions were as follows: 1-octanol as an organic solvent, pH_donor = 2, pH_acceptor = 9.75, stirring rate of 1000 rpm, extraction time of 80 min, without addition of salt. Under these conditions, the enrichment factors ranged between 146 and 311. The values of intra and inter-day relative standard deviations (RSD) were in the range of 3.18–6.00% and 7.25–11.00%, respectively. The limits of detection (LODs) ranged between 0.5 and 7.0 ng mL⁻¹. Among the investigated flavonoids quercetin was found in E. platyloba DC. and luteolin was found in M. piperita. Concentration of quercetin and luteolin was 0.015 and 0.025 mg g⁻¹ respectively.     

Determination of selenium in garlic (Allium sativum) and onion (Allium cepa) by electro thermal atomic absorption spectrometry

A separation/enrichment procedure has been developed for the determination of selenium in garlic and onion samples by electrothermal atomic absorption spectrometry (ET-AAS) as a slurry sampling after preconcentration with 3,3-diaminobenzidine (DAB) reagent on the activated carbon. The influences of pH, time, amount of carbon and complexing reagent were outlined. The effect of acids used in the digestion of samples was also studied and compared. Selenium level was found to be 0.024 μg g⁻¹ for onion (n = 5; LOD – 0.5 μg L⁻¹; LOQ – 1.7 μg L⁻¹) and 0.015 μg g⁻¹ for garlic (n = 5; LOD – 1.3 μg L⁻¹; LOQ – 3.3 μg L⁻¹). Three different samples of garlic were analyzed by k₀-instrumental neutron activation analysis (k₀-INAA) at the Jozef Stefan Institute (JSI). The data obtained by k₀-INAA show that the content of selenium overlapped the results obtained by ET-AAS.     

Spectrophotometric determination of melamine in milk by rank annihilation factor analysis based on pH gradual change-UV spectral data

A new spectrophotometric method has been developed in this paper to determine melamine in milk by applying rank annihilation factor analysis (RAFA) based on pH gradual change-UV spectral data (pH-spectra). In the proposed method, the spectra of the sample solutions at different pH data points were recorded and the pH-spectra bilinear data matrix was generated. Based on these data, the RAFA was then applied to calculate the concentration of melamine in milk. The experiments have been conducted and the results were satisfactory. Under the optimised conditions, linearity of the proposed method was in the range of 0.04–4.0 μg mL⁻¹ for calibration samples, and 0.04–3.5 μg mL⁻¹ for the mixed solutions of melamine with the background milk components. The detection limit (DL) was 12 ng mL⁻¹. The relative predictive error (RPEs) and root mean square error of prediction (RMSEP) of applying RAFA were 0.91% and 0.0151, respectively.     

Analytical application of food dye Sunset Yellow for the rapid kinetic determination of traces of copper(II) by spectrophotometry

A sensitive and rapid kinetic method for trace determination of Cu(II) was developed and validated, based on its catalytic effect on the oxidation of disodium-6-hydroxy-5-[(4-sulphophenyl)azo]-2-naphtalenesulphonic acid (wide used, food colour “Sunset Yellow FCF”, E110, in text selected as SY) by hydrogen peroxide in borate buffer at pH 10.5. The reaction was monitored spectrophotometrically by measuring the decrease in the absorbance of SY at 478.4 nm. The optimum operating conditions regarding concentration of reagents, pH and temperature were established. The calibration curve was linear up to 318 ng mL⁻¹ of Cu(II) and the limit of detection (3σ/S) is 5.0 ng mL⁻¹, and limit of quantification (10σ/S) is 16.67 ng mL⁻¹. The proposed kinetic procedure was successfully applied to monitoring of the concentration of Cu(II) in fruit, wine and milk samples from different areas. The results obtained by the proposed kinetic procedure were compared by those obtained by ICP-OES method, and shown good agreement. The proposed kinetic method could be used for monitoring of quality of drinks or fruit depending on Cu(II) concentration, because of its important role as nutritional element.     

Simultaneous determination of flavor enhancers in stock cube samples by using spectrophotometric data and multivariate calibration

Spectrophotometric data followed by a suitable treatment of chemometric analysis were used for the simultaneous determination of monosodium glutamate (MSG), guanosine 5′-monophosphate (GMP) and inosine 5′-monophosphate (IMP) in stock cube samples, without any previous extraction step. By this way, the overlapping of the absorption spectra was resolved using a PLS-1 model. The concentration for experimental calibration matrix were varied between 5.03–34.2 μg mL⁻¹ for IMP and GMP, and 448–1399 μg mL⁻¹ for MSG. The relative errors of prediction (REPCV %) were 1.8, 2.8 and 3.1 for IMP, GMP and MSG, respectively.     

Microwave-assisted extraction and determination of cyanuric acid residue in infant formula samples by liquid chromatography–tandem mass spectrometry

In the present work, microwave-assisted extraction method in combining with liquid chromatography–tandem mass spectrometry (LC–MS/MS) was proposed for the determination of cyanuric acid (CYA) in infant formula samples. The separation was performed on a MERCK ZIC HILIC column (150 × 2.1 mm i.d., 5 μm) with gradient elution of 20 mM ammonium acetate solution – acetonitrile. The method could respond linearly with cyanuric acid at concentrations from 1.0 to 50 ng mL⁻¹ with a quantification limit of 0.25 mg kg⁻¹. The intra- and inter-day precision was less than 4% and the recovery of the assay was in the range of 86.7–93.1%. In the analysis of practical spiked infant formula samples, the new method yielded satisfactory results. Due to its simplicity and accuracy the straightforward method is particularly suitable for routine cyanuric acid detection.     

Determination of danofloxacin in milk combining second-order calibration and standard addition method using excitation–emission fluorescence data

For this paper we propound a new procedure for fast detection and determination of danofloxacin (DANO) in commercial bovine milks. For this aim, a spectrofluorimetric method coupled with chemometric (PARAFAC) tools has been optimized. This method provides valuable information about the total amount of DANO in the selected sample in a short analysis time. After a cleanup step, consisting in protein precipitation in acidic medium, excitation–emission fluorimetric scans (EMMs) were recorded and a standard addition calibration method, using second order multivariate procedures, was applied. The analytical method has been validated according to the European Community directive related to the decision limit (CCα) and detection capability (CCβ). The obtained values, 7.3 and 12 ng mL⁻¹, respectively calculated are well below the MRL for DANO in milk (30 ng mL⁻¹). This procedure has been applied to different commercial milks in order to accomplish the strength of this methodology by PARAFAC standard addition. Recoveries around 100% were observed for all the samples. The high sensitivity of the fluorimetric technique and the fast cleanup step make this method an easy and fast way for quality and antibiotic residues surveys in commercial milks.