Development of continuous dispersive liquid–liquid microextraction performed in home-made device for extraction and preconcentration of aryloxyphenoxy-propionate herbicides from aqueous samples followed by gas chromatography–flame ionization detection

In this study, a rapid, simple, and efficient sample preparation method based on continuous dispersive liquid–liquid microextraction has been developed for the extraction and preconcentration of aryloxyphenoxy-propionate herbicides from aqueous samples prior to their analysis by gas chromatography–flame ionization detection. In this method, two parallel glass tubes with different diameters are connected with a teflon stopcock and used as an extraction device. A mixture of disperser and extraction solvents is transferred into one side (narrow tube) of the extraction device and an aqueous phase containing the analytes is filled into the other side (wide tube). Then the stopcock is opened and the mixture of disperser and extraction solvents mixes with the aqueous phase. By this action, the extraction solvent is dispersed continuously as fine droplets into the aqueous sample and the target analytes are extracted into the fine droplets of the extraction solvent. The fine droplets move up through the aqueous phase due to its low density compared to aqueous phase and collect on the surface of the aqueous phase as an organic layer. Finally an aliquot of the organic phase is removed and injected into the separation system for analysis. Several parameters that can affect extraction efficiency including type and volume of extraction and disperser solvents, sample pH, and ionic strength were investigated and optimized. Under the optimum extraction conditions, the extraction recoveries and enrichment factors ranged from 49 to 74% and 1633 to 2466, respectively. Relative standard deviations were in the ranges of 3–6% (n = 6, C = 30 μg L⁻¹) for intra-day and 4–7% (n = 4, C = 30 μg L⁻¹) for inter-day precisions. The limits of detection were in the range of 0.20–0.86 μg L⁻¹. Finally the proposed method was successfully applied to determine the target herbicides in fruit juice and vegetable samples.     

Simultaneous derivatization and air-assisted liquid–liquid microextraction of some aliphatic amines in different aqueous samples followed by gas chromatography-flame ionization detection

The paper presents a new method based on simultaneous derivatization and air-assisted liquid–liquid microextraction (AALLME) for the extraction and preconcentration of some aliphatic amines prior to gas chromatography-flame ionization detection (GC-FID). Primary aliphatic amines are derivatized and extracted simultaneously by a fast reaction with butylchloroformate (derivatization agent/extraction solvent) under mild conditions. The mixture of butylchloroformate and aqueous sample solution is rapidly sucked into a 10-mL glass syringe and then is injected into a test tube with conical bottom and the procedure is repeated seven times. After centrifuging the resulted cloudy solution, the derivatized analytes in the sedimented phase are determined by GC-FID. The influence of main factors on the efficiency of derivatization/extraction procedure is studied. Under the optimal conditions, the enrichment factors (EFs) for aliphatic amines are obtained in the range of 248–360 and limits of detection (LODs) are between 0.30 and 2.6 μg L⁻¹. The obtained extraction recoveries ranged from 50 to 72% and the relative standard deviation (RSD) was less than 4.8% for intra-day (n = 6) and inter-days (n = 4) precision. The method is successfully applied to determine some aliphatic amines in environmental water samples.     

Ultra-preconcentration and determination of thirteen organophosphorus pesticides in water samples using solid-phase extraction followed by dispersive liquid–liquid microextraction and gas chromatography with flame photometric detection

An ultra-preconcentration technique composed of solid-phase extraction (SPE) and dispersive liquid–liquid microextraction (DLLME) coupled with gas chromatography–flame photometric detection (GC–FPD) was used for determination of thirteen organophosphorus pesticides (OPPs) including phorate, diazinon, disolfotane, methyl parathion, sumithion, chlorpyrifos, malathion, fenthion, profenphose, ethion, phosalone, azinphose-methyl and co-ral in aqueous samples. The analytes were collected from large volumes of aqueous solutions (100 mL) into 100 mg of a SPE C₁₈ sorbent. The effective variables of SPE including type and volume of elution solvent, volume and flow rate of sample solution, and salt concentration were investigated and optimized. Acetone was selected as eluent in SPE and disperser solvent in DLLME and chlorobenzene was used as extraction solvent. Under the optimal conditions, the enrichment factors were between 15,160 and 21,000 and extraction recoveries were 75.8–105.0%. The linear range was 1–10,000 ng L^?1 and limits of detection (LODs) were between 0.2 and 1.5 ng L^?1. The relative standard deviations (RSDs) for 50 ng L^?1 of OPPs in water with and without an internal standard, were in the range of 1.4–7.9% (n = 5) and 4.0–11.6%, respectively. The relative recoveries of OPPs from well and farm water sat spiking levels of 25 and 250 ng L^?1 were 88–109%.     

Simultaneous determination of valproic acid and its main metabolite in human plasma using a small scale dispersive liquid–liquid microextraction followed by gas chromatography–flame ionization detection

A simple, sensitive, and rapid analytical method has been developed and validated for the extraction and quantification of valproic acid and its main metabolite (3-heptanone) in human plasma. Initially, the proteins of plasma were precipitated with trifluoroacetic acid. Then a very small volume of a water-immiscible extractant and acetonitrile was mixed and rapidly injected into the pre-treated plasma sample. For further turbidity (dispersion of the extractant into sample solution), the cloudy solution was vortexed. After centrifugation, the settled phase was injected into gas chromatography-flame ionization detection. The effective parameters, such as type and volume of extraction and disperser solvents, vortex time, and pH were studied and optimized. The limits of detection of valproic acid and 3-heptanone were obtained, 0.065 and 0.015 mg L^?1, respectively. An acceptable precision was obtained for a concentration of 2 mg L^?1 of each analyte (relative standard deviation?≤?8%). The average absolute recoveries (n?=?3) of valproic acid and 3-heptanone were 52?±?2 and 42?±?1%, respectively. The validated method has been successfully used in analysis of the analytes in human plasma samples.     

Utilization of homogeneous liquid–liquid extraction followed by HPLC-UV as a sensitive method for the extraction and determination of phthalate esters in environmental water samples

A simple and sensitive method for the extraction of four phthalate esters including dimethyl phthalate (DMP), diethyl phthalate (DEP), benzyl butyl phthalate (BBP) and di-n-butyl phthalate (DBP) as well as their determination in water samples was developed using homogeneous liquid–liquid extraction (HLLE) and HPLC-UV. The extraction method is based on the phase separation phenomenon by the salt addition to the ternary solvent system. The extraction parameters such as type and volume of extracting and consolute solvent, concentration of salt, pH of sample and extraction time were optimized. Under the optimal conditions (extraction solvent: 100?µL CHCl₃; consolute solvent: 2.0?mL methanol; NaCl 15% (w/v) and pH of sample: 6.5) extraction recovery was in the range of 92–102%. Linearity was observed in the range of 0.5–300?µg?L^?1 for DEP and 0.6–300?µg?L^?1 for DMP, BBP and DBP. Correlation coefficients (r ²), limits of detection (LODs) and relative standard deviations (RSDs) were in the ranges of 0.9976–0.9993, 0.18–0.25 and 1.5–4.8%, respectively. The method was successfully applied for the preconcentration and determination of these phthalate esters in the several environmental water samples.     

Determination of octylphenol and nonylphenol in aqueous sample using simultaneous derivatization and dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry

A simple and fast sample preparation method for the determination of nonylphenol (NP) and octylphenol (OP) in aqueous samples by simultaneous derivatization and dispersive liquid–liquid microextraction (DLLME) was investigated using gas chromatography–mass spectrometry (GC/MS). In this method, a combined dispersant/derivatization catalyst (methanol/pyridine mixture) was firstly added to an aqueous sample, following which a derivatization reagent/extraction solvent (methyl chloroformate/chloroform) was rapidly injected to combine in situ derivatization and extraction in a single step. After centrifuging, the sedimented phase containing the analytes was injected into the GC port by autosampler for analysis. Several parameters, such as extraction solvent, dispersant solvent, amount of derivatization reagent, derivatization and extraction time, pH, and ionic strength were optimized to obtain higher sensitivity for the detection of NP and OP. Under the optimized conditions, good linearity was observed in the range of 0.1–1000 μg L⁻¹ and 0.01–100 μg L⁻¹ with the limits of detection (LOD) of 0.03 μg L⁻¹ and 0.002 μg L⁻¹ for NP and OP, respectively. Water samples collected from the Pearl River were analyzed with the proposed method, the concentrations of NP and OP were found to be 2.40 ± 0.16 μg L⁻¹ and 0.037 ± 0.001 μg L⁻¹, respectively. The relative recoveries of the water samples spiked with different concentrations of NP and OP were in the range of 88.3–106.7%. Compared with SPME and SPE, the proposed method can be successfully applied to the rapid and convenient determination of NP and OP in aqueous samples.     

Pre-concentration of phenolic compounds in water samples by novel liquid–liquid microextraction and determination by gas chromatography–mass spectrometry

Pre-concentration and determination of 8 phenolic compounds in water samples has been achieved by in situ derivatization and using a new liquid–liquid microextraction coupled GC–MS system. Microextraction efficiency factors have been investigated and optimized: 9 μL 1-undecanol microdrop exposed for 15 min floated on surface of a 10 mL water sample at 55 °C, stirred at 1200 rpm, low pH level and saturated salt conditions. Chromatographic problems associated with free phenols have been overcome by simultaneous in situ derivatization utilizing 40 μL of acetic anhydride and 0.5% (w/v) K₂CO₃. Under the selected conditions, pre-concentration factor of 235–1174, limit of detection of 0.005–0.68 μg/L (S/N = 3) and linearity range of 0.02–300 μg/L have been obtained. A reasonable repeatability (RSD ≤ 10.4%, n = 5) with satisfactory linearity (0.9995 ≥ r² ≥ 0.9975) of results illustrated a good performance of the present method. The relative recovery of different natural water samples was higher than 84%.     

Determination of carbohydrates in tobacco by pressurized liquid extraction combined with a novel ultrasound-assisted dispersive liquid–liquid microextraction method

A novel derivatization-ultrasonic assisted-dispersive liquid–liquid microextraction (UA-DLLME) method for the simultaneous determination of 11 main carbohydrates in tobacco has been developed. The combined method involves pressurized liquid extraction (PLE), derivatization, and UA-DLLME, followed by the analysis of the main carbohydrates with a gas chromatography-flame ionization detector (GC-FID). First, the PLE conditions were optimized using a univariate approach. Then, the derivatization methods were properly compared and optimized. The aldononitrile acetate method combined with the O-methoxyoxime-trimethylsilyl method was used for derivatization. Finally, the critical variables affecting the UA-DLLME extraction efficiency were searched using fractional factorial design (FFD) and further optimized using Doehlert design (DD) of the response surface methodology. The optimum conditions were found to be 44 μL for CHCl₃, 2.3 mL for H₂O, 11% w/v for NaCl, 5 min for the extraction time and 5 min for the centrifugation time. Under the optimized experimental conditions, the detection limit of the method (LODs) and linear correlation coefficient were found to be in the range of 0.06–0.90 μg mL⁻¹ and 0.9987–0.9999. The proposed method was successfully employed to analyze three flue-cured tobacco cultivars, among which the main carbohydrate concentrations were found to be very different.     

Polyaniline/graphene oxide nanocomposite as a sorbent for extraction and determination of nicotine using headspace solid-phase microextraction and gas chromatography–flame ionization detector

A solid-phase microextraction fiber was prepared by polyaniline/graphene oxide nanocomposite as sorbent on the surface of a platinized stainless steel wire using electrospinning technique. The nanocomposite structure was characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The polyaniline/graphene oxide nanocomposite fiber was used for the determination of nicotine from tobacco samples using headspace solid-phase microextraction method and gas chromatography–flame ionization detection. Influential experimental variables on the extraction efficiency of nicotine, such as extraction time and temperature, humidity and desorption conditions, were evaluated and optimized. Under the optimal experimental conditions? the limit of detection, linear dynamic range, intraday and inter-days precisions were found to be 0.01 μg g^?1, 0.05–700 µg g^?1 (R²?=?0.996), 6.9 and 8.1%, respectively. Comparison of the polyaniline/graphene oxide nanocomposite sorbent with polyaniline and commercial fibers shows longer durability, larger capacity and higher extraction efficiency. The polyaniline/graphene oxide nanocomposite fiber was successfully applied for the determination of nicotine in tobacco samples.     

Determination of bisphenol A and bisphenol B in canned seafood combining QuEChERS extraction with dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry

A new simple and reliable method combining an acetonitrile partitioning extractive procedure followed by dispersive solid-phase cleanup (QuEChERS) with dispersive liquid–liquid microextraction (DLLME) and further gas chromatography mass spectrometry analysis was developed for the simultaneous determination of bisphenol A (BPA) and bisphenol B (BPB) in canned seafood samples. Besides the great enrichment factor provided, the final DLLME extractive step was designed in order to allow the simultaneous acetylation of the compounds required for their gas chromatographic analysis. Tetrachloroethylene was used as extractive solvent, while the acetonitrile extract obtained from QuEChERS was used as dispersive solvent, and anhydride acetic as derivatizing reagent. The main factors influencing QuEChERS and DLLME efficiency including nature of QuEChERS dispersive-SPE sorbents, amount of DLLME extractive and dispersive solvents and nature and amount of derivatizing reagent were evaluated. DLLME procedure provides an effective enrichment of the extract, allowing the required sensitivity even using a single quadropole MS as detector. The optimized method showed to be accurate (>68?% recovery), reproducible (<21?% relative standard deviation) and sensitive for the target analytes (method detection limits of 0.2?μg/kg for BPA and 0.4?μg/kg for BPB). The screening of several canned seafood samples commercialized in Portugal (total?=?47) revealed the presence of BPA in more than 83?% of the samples with levels ranging from 1.0 to 99.9?μg/kg, while BPB was found in only one sample at a level of 21.8?μg/kg.     

Determination of atranol and chloroatranol in perfumes using simultaneous derivatization and dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry

A new analytical method based on simultaneous derivatization and dispersive liquid–liquid microextraction (DLLME) followed by gas chromatography–mass spectrometry (GC–MS), for the determination of the allergenic compounds atranol and chloroatranol in perfumes, is presented. Derivatization of the target analytes by means of acetylation with anhydride acetic in carbonate buffer was carried out. Thereby volatility and detectability were increased for improved GC–MS sensitivity. In addition, extractability by DLLME was also enhanced due to a less polar character of the solutes. A liquid–liquid extraction was performed before DLLME to clean up the sample and to obtain an aqueous sample solution, free of the low polar matrix from the essential oils, as donor phase. Different parameters, such as the nature and volume of both the extraction and disperser solvents, the ionic strength of the aqueous donor phase or the effect of the derivatization reagent volume, were optimized. Under the selected conditions (injection of a mixture of 750 μL of acetone as disperser solvent, 100 μL of chloroform as extraction solvent and 100 μL of anhydride acetic as derivatization reagent) the figures of merit of the proposed method were evaluated. Limits of detection in the low ng mL⁻¹ range were obtained. Matrix effect was observed in real perfume samples and thus, standard addition calibration is recommended.     

Rapid analysis of six phthalate esters in wine by ultrasound-vortex-assisted dispersive liquid–liquid micro-extraction coupled with gas chromatography-flame ionization detector or gas chromatography–ion trap mass spectrometry

An Ultrasound-Vortex-Assisted Dispersive Liquid–Liquid Micro-Extraction (USVADLLME) procedure coupled with Gas Chromatography-Flame Ionization Detector (GC-FID) or Gas Chromatography-Ion Trap Mass Spectrometry (GC-IT/MS) is proposed for rapid analysis of six phthalate esters in hydroalcoholic beverages (alcohol by volume, alc vol⁻¹, ≤40%). Under optimal conditions, the enrichment factor of the six analytes ranges from 220- to 300-fold and the recovery from 85% to 100.5%. The limit of detection (LOD) and limit of quantification (LOQ) are ≥0.022 μg L⁻¹ and ≥0.075 μg L⁻¹, respectively. Intra-day and inter-day precisions expressed as relative standard deviation (RSD), are ≤8.2% and ≤7.0%, respectively. The whole proposed methodology has demonstrated to be simple, reproducible and sensible for the determination of trace phthalate esters in red and white wine samples.     

Application of dispersive liquid–liquid microextraction followed by gas chromatography/mass spectrometry as effective tool for trace analysis of organochlorine pesticide residues in honey samples

A dispersive liquid–liquid microextraction (DLLME) method followed by gas chromatography/mass spectrometry (GC/MS) was applied for the trace determination of organochlorine pesticides in honey samples. The type and volume of organic extraction and disperser solvents, pH, effect of added salt content and centrifuging time and speed were optimized to find the appropriate extraction conditions. In DLLME, 30 µL of 1,2-dibromomethane (serving as extractant) and 1.5 mL of acetonitrile (serving as disperser) were applied. The limit of detection (3 s) and limit of quantification (10 s) for all the analytes of interest (organochlorine pesticides) varied from 0.004 to 0.07 and from 0.02 to 0.3 ng g^?1, respectively. The extraction recovery ranged from 91 to 100 %, and the enrichment factors ranged from 171 to 199. The relative standard deviation was <6 % for intraday (n = 6) and <8 % interday (n = 4) measurements. The proposed DLLME–GC/MS method was confirmed to be fast, simple to perform, friendly to environment and suitable for analysis of organochlorine pesticide residues at trace levels in honey samples.     

Dispersive solid-phase extraction followed by dispersive liquid–liquid microextraction for the determination of some sulfonylurea herbicides in soil by high-performance liquid chromatography

Dispersive solid-phase extraction (DSPE) combined with dispersive liquid–liquid microextraction (DLLME) has been developed as a new approach for the extraction of four sulfonylurea herbicides (metsulfuron-methyl, chlorsulfuron, bensulfuron-methyl and chlorimuron-ethyl) in soil prior to high-performance liquid chromatography with diode array detection (HPLC-DAD). In the DSPE-DLLME, sulfonylurea herbicides were first extracted from soil sample into acetone–0.15 mol L⁻¹ NaHCO₃ (2:8, v/v). The clean-up of the extract by DSPE was carried out by directly adding C₁₈ sorbent into the extract solution, followed by shaking and filtration. After the pH of the filtrate was adjusted to 2.0 with 2 mol L⁻¹ HCl, 60.0 μL chlorobenzene (as extraction solvent) was added into 5.0 mL of it for DLLME procedure (the acetone contained in the solution also acted as dispersive solvent). Under the optimum conditions, the enrichment factors for the compounds were in the range between 102 and 216. The linearity of the method was in the range from 5.0 to 200 ng g⁻¹ with the correlation coefficients (r) ranging from 0.9967 to 0.9987. The method detection limits were 0.5–1.2 ng g⁻¹. The relative standard deviations varied from 5.2% to 7.2% (n = 5). The relative recoveries of the four sulfonylurea herbicides from soil samples at spiking levels of 6.0, 20.0 and 60.0 ng g⁻¹ were in the range between 76.3% and 92.5%. The proposed method has been successfully applied to the analysis of the four target sulfonylurea herbicides in soil samples, and a satisfactory result was obtained.     

Determination of hormones in milk by hollow fiber-based stirring extraction bar liquid–liquid microextraction gas chromatography mass spectrometry

The hollow fiber-based stirring extraction bar liquid–liquid microextraction was applied to the extraction of hormones, including 17-α-ethinylestradiol, 17-α-estradiol, estriol, 17-β-estradiol, estrone, 17-α-hydroxyprogesterone, medroxyprogesterone, progesterone and norethisterone acetate, in milk. The present method has the advantages of both hollow fiber-liquid phase microextraction and stirring bar sorptive extraction. The stirring extraction bar was used as both the stirring bar of microextraction, and extractor of the analytes, which can make extraction, clean-up and concentration be carried out in one step. When the extraction was completed, the stirring extraction bar was easy isolated from the extraction system with the magnet. Several experimental parameters, including the type of extraction solvent, the number of hollow stirring extraction bar, extraction time, stirring speed, ionic strength, and desorption conditions were investigated and optimized. The analytes in the extract were derived and determined by gas chromatography mass spectrometry. Under optimal experimental conditions, good linearity was observed in the range of 0.20–20.00 ng mL⁻¹. The limits of detection and quantification were in the range of 0.02–0.06 ng mL⁻¹ and 0.07–0.19 ng mL⁻¹, respectively. The present method was applied to the analysis of milk samples, and the recoveries of analytes were in the range of 93.6–104.6% with the relative standard deviations ranging from 1.6% to 6.2% (n = 5). The results showed that the present method was a rapid and feasible method for the determination of hormones in milk samples.     

Determination of UV filters in both soluble and particulate fractions of seawaters by dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry

An analytical method to determine the total content (i.e., not only in the soluble fraction but also in the particulate one) of eight commonly used UV filters in seawater samples is presented for the first time. Dispersive liquid–liquid microextraction (DLLME) is used as microextraction technique to pre-concentrate the target analytes before their determination by gas chromatography–mass spectrometry (GC–MS). In order to release the UV filters from the suspended particles an ultrasound treatment is performed before DLLME. The ultrasound treatment time was studied in order to achieve a quantitative lixiviation of the target analytes. The type and volume of both disperser and extraction solvent, the sample volume, the pH and the ionic strength involved in the DLLME have been optimized to provide the best enrichment factors. Under the optimized conditions, the method was successfully validated showing good linearity, enrichment factors between 112 and 263 depending on the analyte, limits of detection and quantification in the low ng L⁻¹ range (10–30 ng L⁻¹ and 33–99 ng L⁻¹, respectively) and good intra- and inter-day repeatability (RSD <15%). No significant matrix effects were found. Finally, the method was satisfactorily applied to the analysis of three seawater samples from different origin. Results showed significant amounts of UV filters in the particulate fraction that would have been ignored if only the soluble fraction had been considered. This fact shows that the UV filters are also accumulated in the suspended particles contained in water, what should be taken into account from an environmental standpoint.     

Application of dispersive liquid–liquid microextraction with alcoholic solvents followed by HPLC–UV as a sensitive and efficient method for the extraction and determination of citalopram in biological samples using an experimental design

A sensitive and rapid method based on alcoholic-assisted dispersive liquid–liquid microextraction followed by high-performance liquid chromatography for determination of citalopram in human plasma and urine samples was developed. The effects of six parameters (extraction time, stirring speed, pH, volume of extraction and disperser solvents, and ionic strength) on the extraction recovery were investigated and optimized utilizing Plackett–Burman design and Box–Behnken design, respectively. According to Plackett–Burman design results, the volume of disperser solvent, stirring speed, and extraction time had no effect on the recovery of citalopram. The optimized condition was a mixture of 172 µL of 1-octanol as extraction solvent and 400 µL of methanol as disperser solvent, pH of 10.3 and 1% w/v of salt in the sample solution. Replicating the experiment in optimized condition for five times, gave the average extraction recoveries equal to 89.42%. The detection limit of citalopram in human plasma was obtained 4 ng/mL, and the linearity was in the range of 10–1200 ng/mL. The corresponding values for human urine were 5.4 ng/mL with the linearity in the range of 10–2000 ng/mL. Relative standard deviations for inter- and intraday extraction of citalopram were less than 7% for five measurements. The proposed method was successfully implemented for the determination of citalopram in human plasma and urine samples.     

Determination of hydroxylated benzophenone UV filters in sea water samples by dispersive liquid–liquid microextraction followed by gas chromatography–mass spectrometry

A new analytical method for the determination of four hydroxylated benzophenone UV filters (i.e. 2-hydroxy-4-methoxybenzophenone (HMB), 2,4-dihydroxybenzophenone (DHB), 2,2′-dihydroxy-4-methoxybenzophenone (DHMB) and 2,3,4-trihydroxybenzophenone (THB)) in sea water samples is presented. The method is based on dispersive liquid–liquid microextraction (DLLME) followed by gas chromatography–mass spectrometry (GC–MS) determination. The variables involved in the DLLME process were studied. Under optimized conditions, 1000 μL of acetone (disperser solvent) containing 60 μL of chloroform (extraction solvent) were injected into 5 mL of aqueous sample adjusted to pH 4 and containing 10% NaCl. Before injecting into the GC–MS system, the DLLME extracts were evaporated under an air stream and then reconstituted with N,O-bis-(trimethylsilyl)trifluoroacetamide (BSTFA), thus allowing the target analytes to be converted into their trimethylsilyl derivatives. The best conditions for the derivatization reaction were 75 °C and 30 min. High enrichment factors for all the target analytes (ranging from 58 to 64) and good repeatability (RSD around 6%) were obtained. The limits of detection were in the range of 32–50 ng L⁻¹, depending on the analyte. The recoveries obtained by using the proposed DLLME–GC–MS method evidenced the presence of matrix effects for some of the target analytes, and thereby the standard addition calibration method was employed. Finally, the validated method was applied to the analysis of sea water samples.     

Determination of phthalate esters in edible oils by use of QuEChERS coupled with ionic-liquid-based dispersive liquid–liquid microextraction before high-performance liquid chromatography

A selective and low organic-solvent-consuming method of sample preparation combined with high-performance liquid chromatography with diode-array detection is introduced for analysis of phthalic acid esters in edible oils. Sample treatment involves initial liquid–liquid partitioning with acetonitrile, then QuEChERS cleanup by dispersive solid-phase extraction with primary secondary amine as sorbent. Preconcentration of the analytes is performed by ionic-liquid-based dispersive liquid–liquid microextraction, with the cleaned-up extract as disperser solvent and 1-hexyl-3-methylimidazolium hexafluorophosphate as extraction solvent. Under the optimized conditions, correlation coefficients (r) were 0.998–0.999 and standard errors (S _y/x ) were 2.67–3.37?×?10³ for calibration curves in the range 50–1000 ng g^?1. Detection limits, at a signal-to-noise ratio of 3, ranged from 6 to 9 ng g^?1. Intra-day and inter-day repeatability, expressed as relative standard deviation, were in the ranges 1.0–6.9 % and 2.4–9.4 %, respectively. Recovery varied between 84 % and 106 %. The developed method was successfully used for analysis of the analytes in 28 edible oils. The dibutyl phthalate content of four of the 28 samples (14 %) exceeded the specific migration limit established by domestic and international regulations.