Magnetic effervescent tablet-assisted ionic liquid dispersive liquid–liquid microextraction of selenium for speciation in foods and beverages

A novel, simple and rapid method based on magnetic effervescent tablet-assisted ionic liquid dispersive liquid–liquid microextraction (MEA-IL-DLLME) followed by graphite furnace atomic absorption spectrometry (GFAAS) determination was established for the speciation of selenium in various food and beverage samples. In the procedure, a special magnetic effervescent tablet containing CO₂ sources (sodium carbonate and sodium dihydrogenphosphate), ionic liquids and Fe₃O₄ magnetic nanoparticles (MNPs) was used to combine extractant dispersion and magnetic recovery procedures into a single step. The parameters influencing the microextraction efficiency, such as pH of the sample solution, volume of ionic liquid, amount of MNPs, concentration of the chelating agent, salt effect and matrix effect were investigated and optimised. Under the optimised conditions, the limits of detection (LODs) for Se(IV) were 0.021 μg l^–1 and the linear dynamic range was 0.05–5.0 μg l^–1. The relative standard deviation for seven replicate measurements of 1.0 μg l^–1 of Se(IV) was 2.9%. The accuracy of the developed method was evaluated by analysis of the standard reference materials (GBW10016 tea, GBW10017 milk powder, GBW10043 Liaoning rice, GBW10046 Henan wheat, GBW10048 celery). The proposed method was successfully applied to food and beverage samples including black tea, milk powder, mushroom, soybean, bamboo shoots, energy drink, bottled water, carbonated drink and mineral water for the speciation of Se(IV) and Se(VI) with satisfactory relative recoveries (92.0–108.1%).     

Salt-assisted liquid–liquid microextraction for the determination of iodine in table salt by high-performance liquid chromatography-diode array detection

2-Iodosobenzoate and N,N-dimethylaniline have been used at pH 6.4 for selective conversion of iodide to 4-iodo-N,N-dimethylaniline which was extracted with ethanol, when the phase separation occurred by addition of ammonium sulphate, a process called salt-assisted liquid–liquid microextraction (SALLME), and analysed by high-performance liquid chromatography-diode array detection. Iodate was reduced to iodide before derivatisation. The method has been optimised for extracting solvent, salt for phase separation, and reaction time. A linear calibration was obtained for 10 μg-10 mg L⁻¹ of iodide with correlation coefficient of 0.9989 and limit of detection of 3.7 μg L⁻¹. The SALLME produced 280-fold enrichment of the derivative. The commercial iodised table salt samples have been found highly inhomogeneous; the RSD in analysis of different aliquots of the same sample ranged 18.0-78.1%. The average recovery of spiked iodide to real samples was 98.4% with an average RSD of 7.9% (range 5.2-12.4%).     

Use of hollow fibre-based liquid–liquid–liquid microextraction and high-performance liquid chromatography–diode array detection for the determination of phenolic acids in fruit juices

This paper describes a simple method based on three-phase hollow-fibre liquid-phase microextraction (HF-LPME) for the determination of phenolic acids in fruit juices. Analytes including gallic acid, p-hydroxy benzoic acid, caffeic acid, syringic acid, p-coumaric acid, ferulic acid, and cinnamic acid were separated and determined using high-performance liquid chromatography–photodiode array detection (HPLC–DAD). Parameters affecting the enrichment factors (EFs) were investigated. These compounds were extracted from 5 mL aqueous samples (pH 2) to a thin layer of organic solvent (hexyl acetate) phase impregnated into the pores of the polypropylene hollow fibre wall, and then back extracted to a basic acceptor solution (0.02 M NaOH). EFs ranged from 15 (gallic acid) to 408 (cinnamic acid). The RSD of the method for the analysis of spiked water and fruit juice samples varied from 3.1% to 11.3%. The LODs ranged from 0.01 (cinnamic acid) to 2.0 (caffeic acid) μg/L.     

Arsenic speciation analysis in mono-varietal wines by on-line ionic liquid-based dispersive liquid–liquid microextraction

A highly efficient separation and pre-concentration method for arsenic species determination, based on ionic liquid (IL) dispersive microextraction technique implemented in a flow analysis system, is proposed. Highly selective separation of arsenite species [As(III)] was achieved by chelation with sodium diethyldithiocarbamate (DDTC) followed by dispersion with 40 mg of 1-octyl-3-methylimidazolium hexafluorophosphate ([C₈mim][PF₆]) IL. Analyte extraction, retention and separation of IL phase were achieved with a packed microcolumn and As(III) was determined in eluent solution by electrothermal atomic absorption spectrometry (ETAAS). Concentration of As(V) was deduced by the difference between total inorganic arsenic and As(III). Thus, determination of total arsenic was performed by previous degradation of organo-arsenic species, followed by a reduction. Under optimal conditions, As(III) extraction efficiency was 100% and a sensitivity enhancement factor of 46 was obtained with only 4.0 ml of sample The method was successfully applied for arsenic speciation studies in mono-varietal wines.     

Aflatoxin B1 in eggs and chicken livers by dispersive liquid–liquid microextraction and HPLC

A rapid, low-cost and simple technique has been developed for the determination of aflatoxin B₁ (AFB₁) in eggs and livers using high-performance liquid chromatography (HPLC) with UV detection. In this study, the presence of AFB₁ was investigated in 150 eggs and 50 chicken livers from the local market of Tabriz, Iran. AFB₁ was extracted with a mixture of acetonitrile:water (80:20) and cleaned up by dispersive liquid–liquid microextraction which is a very economical, fast and sensitive method. AFB₁ was quantified by HPLC-UV without need for any complex derivatisation in samples to enhance the detection. The results showed that 72% of the liver and 58% of the egg samples were contaminated with AFB₁ ranging from 0.30 to 16.36 µg kg ^?1. limit of detection and limit of quantification for AFB₁ were 0.08 and 0.28 µg kg ^{? 1}, respectively. The proposed method is suitable for fast analysing of AFB₁ in egg and liver samples.     

Multi-residue method for determination of seven neonicotinoid insecticides in grains using dispersive solid-phase extraction and dispersive liquid–liquid micro-extraction by high performance liquid chromatography

A method using dispersive solid-phase extraction and dispersive liquid–liquid micro-extraction cleanup followed by high performance liquid chromatography (HPLC) has been established for determination of seven neonicotinoid insecticides residues in grains including brown rice, maize, millet and oat. Based on an appraisal of the characteristics of HPLC, validation experiments were conducted for seven neonicotinoid insecticides. In the method, dispersive solid-phase extraction was carried out using PSA and bonded C₁₈ coupled with graphitised carbon black with acetonitrile as the eluted solvent. In the linear range of each pesticide, the correlation coefficient was R² ? 0.99. At the low, medium and high three fortification levels of 0.05–0.8 mg kg⁻¹, recoveries fell within 76–123%. The relative standard deviation was between 0.9% and 12.6% for seven neonicotinoid pesticides. Low limits of detection (0.002–0.005 mg kg⁻¹) and quantification (0.007–0.018 mg kg⁻¹) were readily achieved with this method for all tested pesticides.     

Determination of phenolic compounds in olive oil: New method based on liquid–liquid micro extraction and ultra high performance liquid chromatography-triple–quadrupole mass spectrometry

A novel analytical approach has been performed and evaluated for the identification and quantification of phenolic compounds (phenolic alcohols, secoiridoid derivates, lignans, flavonoids, phenolic acids and aldehydes) which can be found in both virgin olive oil (VOO) and extra virgin olive oil (EVOO). An improved liquid–liquid micro extraction (LLME) method combining with ultra high performance liquid chromatography (UHPLC) coupled to electrospray ionization source (ESI) and tandem mass spectrometry (MS/MS) in Dynamic Multiple Reaction Monitoring (DMRM) mode has been developed, reducing the amount of sample, reagents and time consumed. The proposed methodology was applied to standard solutions, and the quality control parameters obtained were compared with those achieved in spiked refined olive oil (SROO). Generally, these parameters showed lower values in SROO than in standard solutions. Matrix effect, recovery and process efficiency have been studied using SROO. The recoveries were around 90% and the process efficiency of the whole method was higher than 80% for most of the phenolic compounds studied. Examination of these parameters revealed that work straight in the olive oil matrix, which is closer to behave as a real sample, provides better results. The applicability and reliability of this methodology have been confirmed using real samples.     

Assessment of strobilurin fungicides’ content in soya-based drinks by liquid micro-extraction and liquid chromatography with tandem mass spectrometry

Seven strobilurin fungicides were pre-concentrated from soya-based drinks using dispersive liquid–liquid micro-extraction (DLLME) with a prior protein precipitation step in acid medium. The enriched phase was analysed by liquid chromatography (LC) with dual detection, using diode array detection (DAD) and electrospray-ion trap tandem mass spectrometry (ESI-IT-MS/MS). After selecting 1-undecanol and methanol as the extractant and disperser solvents, respectively, for DLLME, the Taguchi experimental method, an orthogonal array design, was applied to select the optimal solvent volumes and salt concentration in the aqueous phase. The matrix effect was evaluated and quantification was carried out using external aqueous calibration for DAD and matrix-matched calibration method for MS/MS. Detection limits in the 4–130 and 0.8–4.5 ng g^?1 ranges were obtained for DAD and MS/MS, respectively. The DLLME-LC-DAD-MS method was applied to the analysis of 10 different samples, none of which was found to contain residues of the studied fungicides.     

Determination of caramel colorants’ by-products in liquid foods by ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)

2-Methylimidazole, 4-methylimidazole (2-MI and 4-MI), 2-acetyl-4-(1,2,3,4-tetrahydroxybutyl) imidazole (THI) and 5-hydroxymethylfurfural (5-HMF) are neo-formed compounds generated during the manufacture of caramel colours and are transferred to the processed food. These contaminants are known to have a toxicological profile that may pose health risks. Hence, to characterise THI, 2- and 4-MI and 5-HMF levels in liquid foods, an ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method was developed and sample preparation was divided into two analytical strategies depending on the concentration range expected in the type of foods targeted. For the determination of the imidazole substitutes (THI, 2- and 4-MI), a sample enrichment and clean-up step by strong cation solid-phase extraction was developed. This method is capable of quantifying over a range of 5 ng ml^–1 (LOQ) to 500 ng ml^–1 with recoveries of 75.4–112.4% and RSDs of 1.5–15%. For determination of 5-HMF, a standard addition method was applied covering the linear range of 0.25–30 µg ml^–1 with RSDs from 2.8% (for intraday precision) to 9.2% (for intermediate precision). The validated analytical methods were applied to 28 liquid food samples purchased from local markets. THI was found only in the beer samples at levels up to 141.2 ng ml^–1. For 2-MI, non-quantifiable traces were observed for all samples, while 4-MI was observed in all samples with large concentration variations (from < LOQ to 563.9 ng ml^–1). 5-HMF was found at expected concentrations, except for a sherry vinegar sample (113 µg ml^–1), which required a high level of dilution before following the standard addition protocol.     

A simple,rapid and novel method based on salting-out assisted liquid–liquid extraction for ochratoxin A determination in beer samples prior to ultra-high-performance liquid chromatography coupled to tandem mass spectrometry

A novel, simple, easy and cheap sample treatment strategy based on salting-out assisted liquid-liquid extraction for ochratoxin A (OTA) ultra-trace analysis in beer samples using ultra-high-performance liquid chromatography-tandem mass spectrometry determination was developed. The factors involved in the efficiency of pre-treatment were studied employing factorial design in the screening phase and the optimal conditions of the significant variables on the analytical response were evaluated using a central composite face-centred design. Consequently, the amount of salt ((NH₄)₂SO₄), together with the volumes of sample, hydrophilic (acetone) and nonpolar (toluene) solvents, and times of vortexing and centrifugation were optimised. Under optimised conditions, the limits of detection and quantification were 0.02 µg l^?1 and 0.08 µg l^?1 respectively. OTA extraction recovery by SALLE was approximately 90% (0.2 µg l^?1). Furthermore, the methodology was in agreement with EU Directive requirements and was successfully applied for analysis of beer samples.     

Dispersive liquid–liquid microextraction combined with sweeping micellar electrokinetic chromatography for the determination of some neonicotinoid insecticides in cucumber samples

A rapid, simple and sensitive method has been developed for the analysis of some neonicotinoid insecticides in cucumber samples by using dispersive liquid–liquid microextraction (DLLME) coupled with sweeping in micellar electrokinetic chromatography (MEKC). Under optimised conditions, the enrichment factors were achieved in the range from 4000 to 10,000. The linearity of the method was in the range from 2.7 to 200 ng g⁻¹ for thiacloprid, acetamiprid and imidacloprid, and in the range from 4.0 to 200 ng g⁻¹ for imidaclothiz in cucumber samples, with the determination coefficients (r²) ranging from 0.9924 to 0.9968. The limits of detection (LODs, S/N = 3) ranged from 0.8 to 1.2 ng g⁻¹. The relative standard deviations (RSDs) at the concentration levels of 10.0 and 50.0 ng g⁻¹ each of the neonicotinoid insecticides in cucumber samples varied from 3.8% to 6.3%. The developed method has been successfully applied to the analysis of the neonicotinoid insecticides in cucumbers with a satisfactory result.     

Application of dispersive liquid–liquid microextraction for the determination of selected organochlorine pesticides in honey by gas chromatography–mass spectrometry

Dispersive liquid–liquid microextraction (DLLME) is a rapid and easy technique that consumes minute amounts of organic solvents. In this work, we present chemometric study on optimization of DLLME parameters for the extraction of aldrin, endrin, lindane, α-endosulfan, 4,4′-DDT and its metabolites from honey matrix. Method quantification limits (MQLs) vary between 0.3 ng/g for 2,4′-DDE and 4,4′-DDE to 13.2 ng/g for α-endosulfan and enable determination at levels below EU-established Maximum Residue Limits. The developed method is linear (R ² > 0.994) in the investigated range (MQL—100 ng/g), with preconcentration factors of 13.2–30.5 and good repeatability (CV ≤ 17%). A comparison with other available methods reported in the last decade is provided. The method has been applied to 19 real samples from Poland, and the results show that organochlorine pesticides (OCPs) are present in analysed honeys at levels not posing threat to human health (below 14 ng/g for sum of 4,4′-DDT and metabolites and below 5 ng/g for aldrin, endrin and lindane). To the best of our knowledge, this is the first reported application of DLLME for the determination of OCPs in honey.     

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.     

Speciation of inorganic arsenic species and total inorganic arsenic in rice using microwave-assisted dispersive liquid–liquid micro-extraction and electrothermal atomic absorption spectrometry

Human exposure to inorganic arsenic (iAs) via rice consumption is of increasing concern. In the present study, microwave-assisted dispersive liquid–liquid micro-extraction (MADLLME) and electrothermal atomic absorption spectrometry (ETAAS) were developed for the speciation of iAs in rice samples. After microwave-assisted digestion, the As(III) ion reacted with diethyldithiophosphoric acid (DDTP) to form an As–DDTP complex and was extracted at the same time. Some parameters affecting digestion, complex formation, and extraction were studied and optimised. Under the optimised conditions, a detection limit of 0.2 µg kg^?1 with a correlation coefficient of 0.9901 were obtained with a calibration curve in the range of 0.5–200 µg kg^?1. Total iAs was determined after reduction of As(V) to As(III) with sodium thiosulfate and potassium iodide, and As(V) was calculated by difference. The proposed extraction procedure was successfully applied for the determination of iAs ions in certified reference materials (NIST CRM 1568a and NMIJ CRM 7503a) and 10 rice samples produced in Iran and other Asian countries.     

Determination of trace levels of cobalt ion in different real samples using dispersive liquid–liquid microextraction followed by flame atomic absorption spectrometry

Dispersive liquid–liquid microextraction technique followed by flame atomic absorption spectrometry was used for preconcentration and determination of trace levels of Co(??) in different real samples. Cobalt ion was first complexed by diethyldithiocarbamate (DDTC) followed by the extraction of resulting complex into the extraction solvent by dispersive liquid–liquid microextraction (DLLME). In DLLME, a mixture of 1.5 mL of methanol (as disperser solvent) containing 50 µL of carbon tetrachloride (as extraction solvent) was rapidly injected into the sample solution to extract the hydrophobic complex of Co-DDTC complex. Under the optimum conditions, the calibration curve was linear in the range of 40–300 µg L^?1 of Co(??) with a correlation coefficient of 0.9966. The relative standard deviation based on six replicate analysis of 100 µg L^?1 of Co(??) was 3.6% and the detection limit was 6.6 µg L^?1. The accuracy of the proposed method was evaluated by the analysis of a certified reference material. Also, the proposed method was successfully applied for determination of trace levels of Co(??) in different water, spinach leaves, black and green tea and tomato sauce samples.     

Effervescent-assisted dispersive liquid–liquid microextraction based on the solidification of floating organic droplets for the determination of fungicides in vinegar and juice

ABSTRACT

A method of effervescent-assisted dispersive liquid–liquid microextraction based on the solidification of a floating organic droplet is reported. This approach was used to measure the fungicides myclobutanil, tebuconazole and epoxiconazole in vinegar and juice. Acidic vinegar and juice reacted with the carbonate to produce effervescence in situ, which then promoted contact of the sample with the extraction solvent. The 1-dodecanol extraction solvent helped solidify the floating organic droplets and could be fully dispersed by effervescence. The extraction solvent, salt, carbonate, and extraction time were optimised. The optimal conditions were 200 μL of 1-dodecanol, 100 mg of sodium chloride, 50 mg of sodium bicarbonate, and 30 s of extraction time. The proposed method has good linearity between 10 and 1000 ng mL^?1. Recoveries were between 70.4% and 103.1% in different vinegar and juice samples. This method was successfully used to measure fungicides in vinegar and juice. This system is simple, fast and environmentally friendly.     

Benzoic and sorbic acid in soft drink,milk, ketchup sauce and bread by dispersive liquid–liquid microextraction coupled with HPLC

Benzoic acid and sorbic acid are widely used for food preservation. These preservatives are generally recognised as safe. The aim of this study was to determine the level of benzoic and sorbic acid in food samples that are usually consumed in Iran. Therefore, 54 samples, including 15 soft drinks, 15 ultra-high-temperature milk, 15 ketchup sauces and 9 bread samples, were analysed by high-performance liquid chromatography with UV detection. Benzoic acid was detected in 50 (92.5%) of the samples ranging from 3.5 to 1520 µg mL^?1, while sorbic acid was detected in 29 (50.3%) samples in a range of 0.8 and 2305 µg mL^?1. Limits of detection and limits of quantification for benzoate were found to be 0.1 and 0.5 µg mL^?1, respectively, and for sorbate 0.08 and 0.3 µg mL^?1, respectively. The results showed that benzoic acid and sorbic acid widely occur in food products in Iran.     

Dispersive liquid–liquid microextraction method based on solidification of floating organic droplet for the determination of triazine herbicides in water and sugarcane samples

Dispersive liquid–liquid microextraction method based on solidification of floating organic droplet (DLLME-SFO) was developed for the analysis of triazines. As model compounds four selected triazine herbicides namely, simazine, atrazine, secbumeton and cyanazine were employed to estimate the extraction efficiency. The experimental conditions were comprehensively studied for the DLLME-SFO method. Under the use of 10 μL of 1-undecanol as extraction solvent, 100 μL of acetonitrile as disperser solvent and 5% (w/v) NaCl for 3 min the results demonstrated that the repeatability (RSD%) of the optimised DLLME-SFO method ranged from 0.03% to 5.1% and the linearity in the range of 0.01–100 ppb. Low limits of detection (0.037–0.008 ppb), and good enrichment factors (195–322) were obtained. The DLLME-SFO method applied in water and sugarcane samples showed excellent relative recoveries (95.7–116.9%) with RSDs <8.6% (n = 3) for all samples.