Hollow fiber-based liquid-liquid-liquid microextraction followed by flow injection analysis using column-less HPLC for the determination of phenazopyridine in plasma and urine

Hollow fiber-based liquid-liquid-liquid microextraction (HF-LLLME) followed by flow injection analysis and diode array detection (FIA-DAD) was applied as a simple and sensitive quantitative method for the determination of phenazopyridine in urine and plasma samples. Flow injection system included a conventional HPLC system (without a chromatographic column) and a diode array detector. The extraction of phenazopyridine was carried out using diphenyl ether as the organic phase for filling the pores of the hollow fiber wall, and 0.1 M H(2)SO(4) solution as acceptor phase in the lumen of the fiber. The factors affecting the HF-LLLME and flow injection analysis including type of organic solvent, pH of donor phase, extraction temperature, extraction time, stirring rate, and pH of mobile phase were investigated and the optimal extraction conditions were established. With the consumption of 5 mL of sample solution, the enrichment factor was about 230. The limit of detection was 0.5 μg/L with inter- and intra-day precision being (RSD%) 6.9 and 4.9, respectively. Excellent linearity was found between 5 and 200 μg/L.     

Sensitive determination of phenylarsenic compounds based on a dual preconcentration method with capillary electrophoresis/UV detection

A novel method based on off-line hollow fiber based liquid liquid liquid microextraction (HF-LLLME) combined with on-column anion selective exhaustive injection (ASEI)-capillary electrophoresis/ultraviolet (CE/UV) detection was proposed for the speciation of five phenylarsenic compounds including phenylarsonic acid (PAA), 4-aminophenylarsonic acid (4-APAA), 4-hydroxyphenylarsonic acid (4-HPAA), 4-nitrophenylarsonic acid (4-NPAA) and 3-nitro-4-hydroxyphenylarsonic acid (NHPAA) in this paper. In HF-LLLME, the target analytes were extracted from 5 mL aqueous samples (donor solution pH 2.15) through a thin phase of tributyl phosphate (TBP) inside the pores of a polypropylene hollow fiber and finally into an 18 μL 0.8 mmol/L Tris acceptor solution inside the lumen of the hollow fiber. Following HF-LLLME, the acceptor solutions were directly analyzed by ASEI-CE/UV. For ASEI, a large plug of water (91% length of total capillary) was introduced into the separation capillary before sample injection in order to prolong the sample injection time, and thus enhance the stacking efficiency. Under the optimized ASEI conditions, up to 236-fold of enrichment factor (EF) was obtained for the ASEI-CE/UV determination of target phenylarsenic compounds. By combining HF-LLLME with ASEI-CE/UV, EFs ranging from 155 to 1780-fold were achieved and the limits of detection (LODs) (at a signal-to-noise ratio of 3) were in the range of 0.68-6.90 μg/L for five phenylarsenic compounds; the relative standard deviations (RSDs) of corrected peak area were 5.6-11.8%. The proposed HF-LLLME-ASEI-CE/UV method was applied for the determination of five target phenylarsenic compounds in pig feed from a local pig farm, and storage pig litter, soil in agricultural field and lake water collected near this pig farm, the recoveries for the spiked samples were in the range of 85.7-104.5%, 66.7-96.2%, 28.9-46.9% and 86.9-107.8% for pig feed, pig litter, soil and lake water, respectively.     

Speciation of organomercury compounds by capillary electrophoresis with pre-column derivatization and on-line stacking

A simple capillary electrophoresis method was developed to separate and quantify methylmercury, ethylmercury, and phenylmercury with the enhancement of pre-column derivatization and on-line stacking.     

Mercury speciation in sea food by flow injection cold vapor atomic absorption spectrometry using selective solid phase extraction

An on-line inorganic and organomercury species separation, preconcentration and determination system consisting of cold vapor atomic absorption spectrometry (CV-AAS or CV-ETAAS) coupled to a flow injection (FI) method was studied. The inorganic mercury species was retained on a column (i.d., 3 mm; length 3 cm) packed to a height of 0.7 cm with a chelating resin aminopropyl-controlled pore glass (550 A) functionalized with [1,5-bis (2 pyridyl)-3-sulphophenyl methylene thiocarbonohydrazyde] placed in the injection valve of a simple flow manifold. Methylmercury is not directly determined. Previous oxidation of the organomercurial species permitted the determination of total mercury. The separation of mercury species was obtained by the selective retention of inorganic mercury on the chelating resin. The difference between total and inorganic mercury determined the organomercury content in the sample. The inorganic mercury was removed on-line from the microcolumn with 6% (m/v) thiourea. The mercury cold vapor generation was performed on-line with 0.2% (m/v) sodium tethrahydroborate and 0.05% (m/v) sodium hydroxide as reducing solution. The determination was performed using CV-AAS and CV-ETAAS, both approaches have been used and compared for the speciation of mercury in sea food. A detection limit of 10 and 6 ng l(-1) was achieved for CV-AAS and CV-ETAAS, respectively. The precision for 10 replicate determinations at the 1 microg l(-1) Hg level was 3.5% relative standard deviation (R.S.D.), calculated from the peak heights obtained. Both approaches were validated with the use of two certified reference materials and by spiking experiments. By analyzing the two biological certified materials, it was evident that the difference between the total mercury and inorganic mercury corresponds to methylmercury. The concentrations obtained by both techniques were in agreement with the certified values or with differences of the certified values for total Hg(2+) and CH(3)Hg(+), according to the t-test for a 95% confidence level. It is amazing how this very simple method is able to provide very important information on mercury speciation.     

Organic and inorganic selenium speciation in environmental and biological samples by nanometer-sized materials packed dual-column separation/preconcentration on-line coupled with ICP-MS

A novel, fast, and cheap nonchromatographic method for direct speciation of dissolved inorganic and organic selenium species in environmental and biological samples was developed by flow injection (FI) dual-column preconcentration/separation on-line coupled with ICP-MS determination. In the developed technique, the first column packed with nanometer-sized Al(2)O(3) could selectively adsorb the inorganic selenium [Se(IV), Se(VI)], and the retained inorganic selenium could be eluted by 0.2 mol l(-1) NaOH, while the organic Se [selenocystine (SeCys(2)) and selenomethionine (Se-Met)] was not retained. On the other hand, the second column packed with mesoporous TiO(2) chemically modified by dimercaptosuccinic acid (DMSA) could selectively adsorb Se(IV) and SeCys(2) and barely adsorb Se(VI) and Se-Met. When the sample solution was passed through the column 1, separation of inorganic selenium and organic selenium could be achieved first. Then, the effluent from column 1 was successively introduced into the column 2 and the speciation of organic selenium could be attained due to the different adsorption behaviors of Se-Met and SeCys(2) on DMSA modified TiO(2). After that, the eluent from column 1 contained Se(IV), and Se(VI) was adjusted to desired pH and injected into column 2, and the speciation of Se(IV) and Se(VI) could also be realized thanks to their different retention on column 2. The parameters affecting the separation were investigated systematically and the optimal separation conditions were established. The detection limits obtained for Se(IV), Se(VI), Se-Met and SeCys(2) were 45-210 ng l(-1) with precisions of 3.6-9.7%. The proposed method has been successfully applied for the speciation of dissolved inorganic and organic selenium in environmental and biological samples. In order to validate the methodology, the developed method was also applied to the speciation of selenium in certified reference material of SELM-1 yeast, and the determined values were in good agreement with the certified values.     

Hollow fiber liquid phase microextraction combined with graphite furnace atomic absorption spectrometry for the determination of methylmercury in human hair and sludge samples

Two methods, based on hollow fiber liquid–liquid–liquid (three phase) microextraction (HF-LLLME) and hollow fiber liquid phase (two phase) microextraction (HF-LPME), have been developed and critically compared for the determination of methylmercury content in human hair and sludge by graphite furnace atomic absorption spectrometry (GFAAS). In HF-LPME, methylmercury was extracted into the organic phase (toluene) prior to its determination by GFAAS, while inorganic mercury remained as a free species in the sample solution. In HF-LLLME, methylmercury was first extracted into the organic phase (toluene) and then into the acceptor phase (4% thiourea in 1 mol L^− 1 HCl) prior to its determination by GFAAS, while inorganic mercury remained in the sample solution. The total mercury was determined by inductively coupled plasma-mass spectrometry (ICP-MS), and the levels of inorganic mercury in both HF-LLLME and HF-LPME were obtained by subtracting methylmercury from total mercury. The factors affecting the microextraction of methylmercury, including organic solvent, extraction time, stirring rate and ionic strength, were investigated and the optimal extraction conditions were established for both HF-LLLPME and HF-LPME. With a consumption of 3.0 mL of the sample solution, the enrichment factors were 204 and 55 for HF-LLLPME and HF-LPME, respectively. The limits of detection (LODs) for methylmercury were 0.1 μg L^− 1 and 0.4 μg L^− 1 (as Hg) with precisions (RSDs (%), c = 5 μg L^− 1 (as Hg), n = 5) of 13% and 11% for HF-LLLPME–GFAAS and HF-LPME–GFAAS, respectively. For ICP-MS determination of total mercury, a limit of detection of 39 ng L^− 1 was obtained. Finally, HF-LLLME–GFAAS was applied to the determination of methylmercury content in human hair and sludge, and the recoveries for the spiked samples were in the range of 99–113%. In order to validate the method, HF-LLLME–GFAAS was also applied to the analysis of a certified reference material of NRCC DORM-2 dogfish muscle, and the determined values were in good agreement with the certified values.     

Dynamic three-phase hollow fiber microextraction based on two immiscible organic solvents with automated movement of the acceptor phase

Dynamic three-phase hollow fiber liquid-liquid-liquid microextraction (HF-LLLME) based on two immiscible organic solvents, with automated movement of organic acceptor phase to facilitate mass transfer was introduced for the first time. Polycyclic aromatic hydrocarbons were used as model compounds and extracted from water and soil samples. The extraction involved filling an 8 cm length of hollow fiber with 25 μL of organic acceptor solvent using a microsyringe, followed by impregnation of the pores in the fiber wall with n-dodecane. The fiber was then immersed in 20 mL of aqueous sample solution. During extraction, the organic acceptor phase was repeatedly moved in the lumen of the hollow fiber by movement of the syringe plunger controlled by programmable syringe pump. Following this microextraction, 2 μL of organic acceptor phase was injected into gas chromatography-flame ionization detector. This new technique provided up to 554-fold preconcentration of the analytes under the optimized conditions. Good repeatabilities (with RSDs ≤8.4%) were obtained. Detection limits were in the range of 0.2-0.5 μg/L. The utilization of the proposed method for extraction of the polycyclic aromatic hydrocarbons from different real samples (such as water and soil samples) also gave good precision and recovery.     

Extraction of hydroxyaromatic compounds in river water by liquid-liquid-liquid microextraction with automated movement of the acceptor and the donor phase

Liquid-liquid-liquid microextraction with automated movement of the acceptor and the donor phase technique is described for the extraction of six hydroxyaromatic compounds in river water using a disposable and ready to use hollow fiber. Separation and quantitative analyses were performed using LC with UV detection at 254 nm. Analytes were extracted from the acidified sample solution (donor phase) into the organic solvent impregnated in the pores of the hollow fiber and then back extracted into the alkaline solution (acceptor phase) inside the lumen of the hollow fiber. The fiber was held by a conventional 10 microL LC syringe. The acceptor phase was sandwitched between the plunger and a small volume of the organic solvent (microcap). The acceptor solution was repeatedly moved in and out of the hollow fiber using a syringe pump. This movement provides a fresh acceptor phase to come in contact with the organic phase and thus enhancing extraction kinetics thereby leading to the improvement in enrichment of the analytes. The microcap separates the acceptor phase and the donor phase in addition to being partially responsible for mass transfer of the analytes from the donor solution to the acceptor solution. Under stirring, a fresh donor phase will enter through the open end of the fiber that will also contribute to the mass transfer. Various parameters affecting the extraction efficiency viz type of organic solvent, extraction time, stirring speed, effect of sodium chloride, and concentration of donor and acceptor phases were studied. RSD (3.9-5.6%), correlation coefficient (0.995-0.997), detection limit (2.0-51.2 ng/mL), enrichment factor (339-630), relative recovery (93.2-97.9%), and absolute recovery (33.9-63.0%) have also been investigated. The developed method was applied for the analysis of river water.     

Electrophoretic determination of albumin in urine using on-line concentration techniques

To improve the sensitivity of the UV-detection for the determination of trace amounts of albumin by capillary zone electrophoresis (CZE), five on-line preconcentration techniques, including field-amplified sample stacking (FASS), head-column field-amplified sample stacking (HC-FASS), stacking with a polymer solution, dynamic pH junction and large volume sample stacking (LVSS) with reversed polarity, were compared. Sensitivity enhancement factor and reproducibility were two factors that were used to assess the suitability of each method. To minimize protein adsorption on the capillary wall, capillaries were covalently modified with anionic polymer, poly(sulfopropylmethacrylate) coating. All used methods have good reproducibility. The maximum sensitivity enhancement factor (about 67-fold in terms of peak heights) was achieved with LVSS technique. The concentration limit of detection (LOD) (S/N=3) for the human serum albumin obtained with the optimized LVSS approach was 15 microg/ml with UV-detection. The method was further evaluated for the analysis of urine samples with gel-filtration-based sample-desalting procedure.     

Improving sensitivity by large-volume sample stacking combined with sweeping without polarity switching by capillary electrophoresis coupled to photodiode array ultraviolet detection

An easy, simple, and highly efficient on-line preconcentration method for polyphenolic compounds in CE was developed. It combined two on-line concentration techniques, large-volume sample stacking (LVSS) and sweeping. The analytes preconcentration technique was carried out by pressure injection of large-volume sample followed by the EOF as a pump pushing the bulk of low-conductivity sample matrix out of the outlet of the capillary without the electrode polarity switching technique using five polyphenols as the model analytes. Identification and quantification of the analytes were performed by photodiode array UV (PDA) detection. The optimal BGE used for separation and preconcentration was a solution composed of 10 mM borate-90 mM sodium cholate (SC)-40% v/v ethylene glycol, without pH adjustment, the applied voltage was 27.5 kV. Under optimal preconcentration conditions (sample injection 99 s at 0.5 psi), the enhancement in the detection sensitivities of the peak height and peak area of the analytes using the on-line concentration technique was in the range of 18-26- and 23-44-fold comparing with the conventional injection mode (3 s). The detection limits for (-)-epigallocatechin (EGC), (-)-epicatechin (EC), (+)-catechin (C), (-)-epigallocatechin gallate (EGCG), and (-)-epicatechin gallate (ECG) were 4.3, 2.4, 2.2, 2.0, and 1.6 ng/mL, respectively. The five analytes were baseline-separated under the optimum conditions and the experimental results showed that preconcentration was well achieved.     

Comparison of dispersive liquid–liquid microextraction and hollow fiber liquid–liquid–liquid microextraction for the determination of fentanyl,alfentanil, and sufentanil in water and biological fluids by high-performance liquid chromatography

Dispersive liquid–liquid microextraction (DLLME) and hollow fiber liquid–liquid–liquid microextraction (HF-LLLME) combined with HPLC–DAD have been applied for the determination of three narcotic drugs (alfentanil, fentanyl, and sufentanil) in biological samples (human plasma and urine). Different DLLME parameters influencing the extraction efficiency such as type and volume of the extraction solvent and the disperser solvent, concentration of NaOH, and salt addition were investigated. In the HF-LLLME, the effects of important parameters including organic solvent type, concentration of NaOH as donor solution, concentration of H₂SO₄ as acceptor phase, salt addition, stirring rate, temperature, and extraction time were investigated and optimized. The results showed that both extraction methods exhibited good linearity, precision, enrichment factor, and detection limit. Under optimal condition, the limits of detection ranged from 0.4 to 1.9 μg/L and from 1.1 to 2.3 μg/L for DLLME and HF-LLLME, respectively. For DLLME, the intra- and inter-day precisions were 1.7–6.4% and 14.2–15.9%, respectively; and for HF-LLLME were 0.7–5.2% and 3.3–10.1%, respectively. The enrichment factors were from 275 to 325 and 190 to 237 for DLLME and HF-LLLME, respectively. The applicability of the proposed methods was investigated by analyzing biological samples. For analysis of human plasma and urine samples, HF-LLLME showed higher precision, more effective sample clean-up, higher extraction efficiency, lower organic solvent consumption than DLLME.     

Hollow fiber liquid phase microextraction combined with electrothermal atomic absorption spectrometry for the speciation of arsenic (III) and arsenic (V) in fresh waters and human hair extracts

A new method of hollow fiber liquid phase microextraction (HF-LPME) using ammonium pyrrolidine dithiocarbamate (APDC) as extractant combined with electrothermal atomic absorption spectrometry (ETAAS) using Pd as permanent modifier has been described for the speciation of As(III) and As(V). In a pH range of 3.0-4.0, the complex of As(III)-APDC complex can be extracted using toluene as the extraction solvent leaving As(V) in the aqueous layer. The post extraction organic phase was directly injected into ETAAS for the determination of As(III). To determine total arsenic in the samples, first As(V) was reduced to As(III) by l-cysteine, and then a microextraction method was performed prior to the determination of total arsenic. As(V) assay was based on subtracting As(III) form the total arsenic. All parameters, such as pH of solution, type of organic solvent, the amount of APDC, stirring rate and extraction time, affecting the separation of As(III) from As(V) and the extraction efficiency of As(III) were investigated, and the optimized extraction conditions were established. Under optimized conditions, a detection limit of 0.12 ng mL⁻¹ with enrichment factor of 78 was achieved. The relative standard deviation (R.S.D.) of the method for five replicate determinations of 5 ng mL⁻¹ As(III) was 8%. The developed method was applied to the speciation of As(III) and As(V) in fresh water and human hair extracts, and the recoveries for the spiked samples are 86-109%. In order to validate the developed method, three certified reference materials such as GBW07601 human hair, BW3209 and BW3210 environmental water were analyzed, and the results obtained were in good agreement with the certified values provided.     

Large volume sample stacking in capillary zone electrophoresis for the monitoring of the degradation products of metribuzin in environmental samples

A capillary zone electrophoresis (CZE) method with UV-vis detection has been developed for the simultaneous monitoring of the major degradation products of metribuzin, i.e. deaminometribuzin (DA), deaminodiketometribuzin (DADK) and diketometribuzin (DK). The dissociation acid constants have also been estimated by CE and no significant differences have been observed with the values obtained by applying other techniques. Optimum separation has been achieved in less than 9 min in 40 mM sodium tetraborate buffer, pH 9.5 by applying a voltage of 15kV at 25 degrees C and using p-aminobenzoic acid as internal standard. In order to increase sensitivity, large volume sample stacking (LVSS) with polarity switching has been applied as on-line pre-concentration methodology. Detection limits of 10, 10 and 20 ng/mL for DA, DADK and DK, respectively were obtained. The method has been applied to soil samples, after pressurized liquid extraction (PLE). Samples were extracted at high temperature (103 degrees C and 1500 psi) using methanol as extraction solvent and sodium sulphate as drying agent. This PLE procedure was followed by an off-line pre-concentration and sample clean-up procedure by solid-phase extraction (SPE) using a LiChrolut EN sorbent column. These last two procedures were also suitable for the direct treatment of groundwater samples before CE analysis. The combination of both off-line and on-line pre-concentration procedures provided a significant improvement in sensitivity. LVSS provided pre-concentration factors of 4, 36 and 28 for DK, DA and DADK, respectively and with SPE a pre-concentration of 500-fold for the case of water samples and of 2.5-fold in the case of soil samples was obtained. The method is suitable for the monitoring of these residues in environmental samples with high sensitivity, precision and satisfactory recoveries.     

On-column complexation capillary electrophoretic separation of Fe2+ and Fe3+ using 2,6-pyridinedicarboxylic acid coupled with large-volume sample stacking

On-column complexation of Fe2+ and Fe3+ with 2,6-pyridinedicarboxylic acid (2,6-PDCA) formed anionic complexes, which were then separated by capillary zone electrophoresis with direct UV detection at 214 nm. To achieve reasonable separation selectivity and on-column complexation, the conditions such as pH, the concentration of 2,6-PCDA and the EOF modifiers in the electrolyte were examined. The electrolyte contained 5.0 mM 2,6-PDCA, 0.25 mM tetradecyltrimethlammonium bromide (TTAB) and 5% (v/v) acetonitrile at pH 4.0 was optimised for on-column complexation and the separation of Fe[PCDA]2(2-) and Fe[PCDA]2(-). To enhance the detection sensitivity, large-volume sample stacking (LVSS) was used for the on-line preconcentration of Fe[PCDA]2(2-) and Fe[PCDA]2(-). Under the optimised conditions, satisfactory working ranges (0.5-50 microM), lower detection limits (less than 0.1 microM) and good repeatability of the peak areas (R.S.D.: 5.2-7.8%, n = 5) was achieved using LVSS (300 s). With LVSS, the detection sensitivity was enhanced more than 50-fold compared to conventional hydrodynamic injection. The proposed method was used successfully for the determination of Fe2+ and Fe3+ in water samples.     

Liquid-liquid-liquid microextraction followed by HPLC with UV detection for quantitation of ephedrine in urine

Liquid-liquid-liquid microextraction (LLLME) in combination with HPLC and UV detection has been used as a sensitive method for the determination of ephedrine in urine samples. Extraction process was performed in a homemade total glass vial without using a Teflon ring, usually employed. Ephedrine was first extracted from 3.5 mL of urine sample (pH 12) into a microfilm of toluene/benzene (50:50). The analyte was subsequently back extracted into an acidic microdrop solution (pH 2) suspended in the organic phase. The extract was then injected into the HPLC system directly. An enrichment factor of 137 along with a good sample clean-up was obtained under the optimized conditions. The calibration curve showed linearity in the range of 0.01-50 mg/L with regression coefficient corresponding to 0.998. The LODs and LOQs, based on a S/N of 3 and 10, were 5 and 10 microg/L, respectively. The method was eventually applied for the determination of ephedrine in urine sample after oral administration of 5 mg single dose of drug.     

Effect of NaOH on large-volume sample stacking of haloacetic acids in capillary zone electrophoresis with a low-pH buffer

Large-volume sample stacking (LVSS) is an effective on-capillary sample concentration method in capillary zone electrophoresis, which can be applied to the sample in a low-conductivity matrix. NaOH solution is commonly used to back-extract acidic compounds from organic solvent in sample pretreatment. The effect of NaOH as sample matrix on LVSS of haloacetic acids was investigated in this study. It was found that the presence of NaOH in sample did not compromise, but rather help the sample stacking performance if a low pH background electrolyte (BGE) was used. The sensitivity enhancement factor was higher than the case when sample was dissolved in pure water or diluted BGE. Compared with conventional injection (0.4% capillary volume), 97-120-fold sensitivity enhancement in terms of peak height was obtained without deterioration of separation with an injection amount equal to 20% of the capillary volume. This method was applied to determine haloacetic acids in tap water by combination with liquid-liquid extraction and back-extraction into NaOH solution. Limits of detection at sub-ppb levels were obtained for real samples with direct UV detection.     

Solid-phase extraction and large-volume sample stacking with an electroosmotic flow pump in capillary electrophoresis for determination of methotrexate and its metabolites in human plasma

This paper describes approaches for large-volume sample stacking (LVSS) with an EOF pumpin CE for the determination of methotrexate (MTX) and its metabolites in human plasma. After pretreatment of plasma through a SPE cartridge, a large sample volume was loaded by hydrodynamic injection (3 psi, 70 s) into the capillary filled with phosphate buffer (70 mM, pH 6.0) containing 0.01% polyethylene oxide. Following removal of a large plug of sample matrix from the capillary using polarity switching (-25 kV), the separation of anionic analytes was subsequently performed without changing polarity again, achieving an improvement of sensitivity of around a 100-fold. The method was applied to therapeutic drug monitoring of MTX in one acute lymphoblastic leukemia patient. This study is one of very few applications showing the feasibility of LVSS in analysis of biological samples by CE.     

Solvent bar microextraction combined with electrothermal vaporization inductively coupled plasma mass spectrometry for the speciation of inorganic arsenic in water samples

A new method of solvent bar microextraction (SBME) combined with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) for the speciation of As(III) and As(V) in water samples was developed. The method is based on the chelation of As(III) and ammonium pyrrolidine dithiocarbamate (APDC) under the selected conditions, and the As(III)-PDC complex could be extracted into the organic phase, while As(V) remained in aqueous solution. The post-extraction organic phase was directly injected into ETV-ICP-MS for determination of As(III) with the use of iridium as permanent chemical modifier. As(V) was reduced to As(III) by L-cysteine and was then subjected to SBME prior to total As determination. The assay of As(V) was based on subtracting As(III) from total As. The factors affecting on the SBME, such as organic solvent, sample pH, chelating reagent concentration, stirring rate and extraction time, and chemical modification of iridium in ETV-ICP-MS have been studied. Under the optimized conditions, the enrichment factor of 220-fold could be achieved in 15 min extraction, the limit of detection (LOD) for As(III) was 0.32 pg mL^− 1, and the relative standard deviation (RSD) was 8.8% (0.1 ng mL^− 1, n = 9). Compared with hollow fiber liquid phase microextraction (HF-LPME), SBME has a higher enrichment factor and faster extraction kinetics. In order to validate the accuracy of the method, a Certified Reference Material of GSBZ50004-88 (No. 200420) water sample was analyzed and the results obtained were in good agreement with the certified values. The developed method was also applied to the speciation of inorganic As in environmental waters with satisfactory results.     

Direct determination of chlorophenols in water samples through ultrasound-assisted hollow fiber liquid–liquid–liquid microextraction on-line coupled with high-performance liquid chromatography

In this study we on-line coupled hollow fiber liquid–liquid–liquid microextraction (HF-LLLME), assisted by an ultrasonic probe, with high-performance liquid chromatography (HPLC). In this approach, the target analytes – 2-chlorophenol (2-CP), 3-chlorophenol (3-CP), 2,6-dichlorophenol (2,6-DCP), and 3,4-dichlorophenol (3,4-DCP) – were extracted into a hollow fiber (HF) supported liquid membrane (SLM) and then back-extracted into the acceptor solution in the lumen of the HF. Next, the acceptor solution was withdrawn on-line into the HPLC sample loop connected to the HF and then injected directly into the HPLC system for analysis. We found that the chlorophenols (CPs) could diffuse quickly through two sequential extraction interfaces – the donor phase – SLM and the SLM – acceptor phase – under the assistance of an ultrasonic probe. Ultrasonication provided effective mixing of the extracted boundary layers with the bulk of the sample and it increased the driving forces for mass transfer, thereby enhancing the extraction kinetics and leading to rapid enrichment of the target analytes. We studied the effects of various parameters on the extraction efficiency, viz. the nature of the SLM and acceptor phase, the compositions of the donor and acceptor phases, the fiber length, the stirring rate, the ion strength, the sample temperature, the sonication conditions, and the perfusion flow rate. This on-line extraction method exhibited linearity (r² ≥ 0.998), sensitivity (limits of detection: 0.03–0.05 μg L⁻¹), and precision (RSD% ≤ 4.8), allowing the sensitive, simple, and rapid determination of CPs in aqueous solutions and water samples with a sampling time of just 2 min.     

Analysis of acrylamide in food products by in-line preconcentration capillary zone electrophoresis

Two in-line preconcentration capillary zone electrophoresis (CZE) methods (field amplified sample injection (FASI) and stacking with sample matrix removal (LVSS)) have been evaluated for the analysis of acrylamide (AA) in foodstuffs. To allow the determination of AA by CZE, it was derivatized using 2-mercaptobenzoic acid. For FASI, the optimum conditions were water at pH > or = 10 adjusted with NH3 as sample solvent, 35 s hydrodynamic injection (0.5 psi) of a water plug, 35 s of electrokinetic injection (-10 kV) of the sample, and 6s hydrodynamic injection (0.5 psi) of another water plug to prevent AA removal by EOF. In stacking with sample matrix removal, the reversal time was found to be around 3.3 min. A 40 mM phosphate buffer (pH 8.5) was used as carrier electrolyte for CZE separation in both cases. For both FASI and LVSS methods, linear calibration curves over the range studied (10-1000 microg L(-1) and 25-1000 microg L(-1), respectively), limit of detection (LOD) on standards (1 microg L(-1) for FASI and 7 microg L(-1) for LVSS), limit of detection on samples (3 ng g(-1) for FASI and 20 ng g(-1) for LVSS) and both run-to-run (up to 14% for concentration and 0.8% for time values) and day-to-day precisions (up to 16% and 5% for concentration and time values, respectively) were established. Due to the lower detection limits obtained with the FASI-CZE this method was applied to the analysis of AA in different foodstuffs such as biscuits, cereals, crisp bread, snacks and coffee, and the results were compared with those obtained by LC-MS/MS.