Liquid-phase microextraction in a microfluidic-chip – High enrichment and sample clean-up from small sample volumes based on three-phase extraction

In this work, a microfluidic-chip based system for liquid-phase microextraction (LPME-chip) was developed. Sample solutions were pumped into the LPME-chip with a micro-syringe pump at a flow rate of 3–4 μL min⁻¹. Inside the LPME chip, the sample was in direct contact with a supported liquid membrane (SLM) composed of 0.2 μL dodecyl acetate immobilized in the pores of a flat membrane of polypropylene (25 μm thickness). On the other side of the SLM, the acceptor phase was present. The acceptor phase was either pumped at 1 μL min⁻¹ during extraction or kept stagnant (stop-flow). Amitriptyline, methadone, haloperidol, loperamide, and pethidine were selected as model analytes, and they were extracted from alkaline sample solution, through the SLM, and into 10 mM HCl or 100 mM HCOOH functioning as acceptor phase. Subsequently, the acceptor phase was either analyzed off-line by capillary electrophoresis for exact quantification, or on-line by UV detection or electrospray ionization mass spectrometry for time profiling of concentrations. The LPME-chip was found to be highly effective, and extraction efficiencies were in the range of 52–91%. When the flow of acceptor phase was turned off during extraction (stop-flow), analyte enrichment increased linearly with the extraction time. After 10 min as an example, amitriptyline was enriched by a factor of 42 from only 30 μL sample solution, and after 120 min amitriptyline was enriched by a factor of 500 from 320 μL sample solution. This suggested that the LPME-chip has great potentials for very efficient analyte enrichments from limited sample volumes in the future.     

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 Next, the acceptor solution was withdrawn on-line into the HPLC sample loop connected to the HF and then injected directly into the HPLC system for analysis.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.     

Optimization of some experimental parameters in the electro membrane extraction of chlorophenols from seawater

An electro membrane extraction (EME) methodology was utilized to study the isolation of some environmentally important pollutants, such as chlorophenols, from aquatic media based upon the electrokinetic migration process. The analytes were transported by application of an electrical potential difference over a supported liquid membrane (SLM). A driving force of 10 V was applied to extract the analytes through 1-octanol, used as the SLM, into a strongly alkaline solution. The alkaline acceptor solution was subsequently analyzed by high performance liquid chromatography-ultraviolet (HPLC-UV) detection. The parameters influencing electromigration, including volumes and pH of the donor and acceptor phases, the organic solvent used as the SLM, and the applied voltage and its duration, were investigated to find the most suitable extraction conditions. Since the developed method showed a rather high degree of selectivity towards pentachlorophenol (PCP), validation of the method was performed using this compound. An enrichment factor of 23 along with acceptable sample clean-up was obtained for PCP. The calibration curve showed linearity in the range of 0.5–1000 ng/mL with a coefficient of estimation corresponding to 0.999. Limits of detection and quantification, based on signal-to-noise ratios of 3 and 10, were 0.1 and 0.4 ng/mL, respectively. The relative standard deviation of the analysis at a PCP concentration of 0.5 ng/mL was found to be 6.8% (n = 6). The method was also applied to the extraction of this contaminant from seawater and an acceptable relative recovery of 74% was achieved at a concentration level of 1.0 ng/mL.     

Simultaneous extraction of acidic and basic drugs at neutral sample pH: A novel electro-mediated microextraction approach

The simultaneous extraction of acidic and basic analytes from a particular sample is a challenging task. In this work, electromembrane extraction (EME) of acidic non-steroidal anti-inflammatory drugs and basic β-blockers in a single step was carried out for the first time. It was shown that by designing an appropriate compartmentalized membrane envelope, the two classes of drugs could be electrokinetically extracted by a 300 V direct current electrical potential. This method required only a very short 10-min extraction time from a pH-neutral sample, with a small amount (50 μL) of organic solvent (1-octanol) as the acceptor phase. Analysis was carried out using gas chromatography–mass spectrometry after derivatization of the analytes. Extraction parameters such as extraction time, applied voltage, pH range, and concentration of salt added were optimized. The proposed EME technique provided good linearity with correlation coefficients from 0.982 to 0.997 over a concentration range of 1–200 μg L⁻¹. Detection limits of the drugs ranged between 0.0081 and 0.26 μg L⁻¹, while reproducibility ranged from 6 to 13% (n = 6). Finally, the application of the new method to wastewater samples was demonstrated.     

Drop-to-drop microextraction across a supported liquid membrane by an electrical field under stagnant conditions

Electromembrane extraction (EME) of basic drugs from 10 μL sample volumes was performed through an organic solvent (2-nitrophenyl octyl ether) immobilized as a supported liquid membrane (SLM) in the pores of a flat polypropylene membrane (25 μm thickness), and into 10 μL 10 mM HCl as the acceptor solution. The driving force for the extractions was 3–20 V d.c. potential sustained over the SLM. The influence of the membrane thickness, extraction time, and voltage was investigated, and a theory for the extraction kinetics is proposed. Pethidine, nortriptyline, methadone, haloperidol, and loperamide were extracted from pure water samples with recoveries ranging between 33% and 47% after only 5 min of operation under totally stagnant conditions. The extraction system was compatible with human urine and plasma samples and provided very efficient sample pretreatment, as acidic, neutral, and polar substances with no distribution into the organic SLM were not extracted across the membrane. Evaluation was performed for human urine, providing linearity in the range 1–20 μg/mL, and repeatability (RSD) in average within 12%.     

Implementation of droplet-membrane-droplet liquid-phase microextraction under stagnant conditions for lab-on-a-chip applications

In the current work, droplet-membrane-droplet liquid-phase microextraction (LPME) under totally stagnant conditions was presented for the first time. Subsequently, implementation of this concept on a microchip was demonstrated as a miniaturized, on-line sample preparation method. The performance level of the lab-on-a-chip system with integrated microextraction, capillary electrophoresis (CE) and laser-induced fluorescence (LIF) detection in a single miniaturized device was preliminarily investigated and characterized. Extractions under stagnant conditions were performed from 3.5 to 15 μL sample droplets, through a supported liquid membrane (SLM) sustained in the pores of a small piece of a flat polypropylene membrane, and into 3.5-15 μL of acceptor droplet. The basic model analytes pethidine, nortriptyline, methadone, haloperidol, and loperamide were extracted from alkaline sample droplets (pH 12), through 1-octanol as SLM, and into acidified acceptor droplets (pH 2) with recoveries ranging between 13 and 66% after 5 min of operation. For the acidic model analytes Bodipy FL C₅ and Oregon Green 488, the pH conditions were reversed, utilizing an acidic sample droplet and an alkaline acceptor droplet, and 1-octanol as SLM. As a result, recoveries for Bodipy FL C₅ and Oregon Green 488 from human urine were 15 and 25%, respectively.     

Exhaustive extraction of peptides by electromembrane extraction

This fundamental work illustrates for the first time the possibility of exhaustive extraction of peptides using electromembrane extraction (EME) under low system-current conditions (<50 μA). Bradykinin acetate, angiotensin II antipeptide, angiotensin II acetate, neurotensin, angiotensin I trifluoroacetate, and leu-enkephalin were extracted from 600 μL of 25 mM phosphate buffer (pH 3.5), through a supported liquid membrane (SLM) containing di-(2-ethylhexyl)-phosphate (DEHP) dissolved in an organic solvent, and into 600 μL of an acidified aqueous acceptor solution using a thin flat membrane-based EME device. Mass transfer of peptides across the SLM was enhanced by complex formation with the negatively charged DEHP. The composition of the SLM and the extraction voltage were important factors influencing recoveries and current with the EME system. 1-nonanol diluted with 2-decanone (1:1 v/v) containing 15% (v/v) DEHP was selected as a suitable SLM for exhaustive extraction of peptides under low system-current conditions. Interestingly, increasing the SLM volume from 5 to 10 μL was found to be beneficial for stable and efficient EME. The pH of the sample strongly affected the EME process, and pH 3.5 was found to be optimal. The EME efficiency was also dependent on the acceptor solution composition, and the extraction time was found to be an important element for exhaustive extraction. When EME was carried out for 25 min with an extraction voltage of 15 V, the system-current across the SLM was less than 50 μA, and extraction recoveries for the model peptides were in the range of 77–94%, with RSD values less than 10%.     

Direct determination of chlorophenols present in liquid samples by using a supported liquid membrane coupled in-line with capillary electrophoresis equipment

Actually there is a great trend on the development of effective analytical methods for monitoring trace levels of various phenols which can indicate, among others compounds, the water quality. A simple, inexpensive supported liquid membrane (SLM) device was used in combination with commercially available capillary electrophoresis (CE) equipment for the direct determination of chlorophenols in surface water samples. The manifold was used simultaneously to extract and preconcentrate the analytes from liquid samples. In the extraction set-up, the donor phase (4 mL) was placed in the CE vial, where a micro-membrane extraction unit (MMEU) accommodating the acceptor phase (100 μL) in its lumen was immersed. The supported liquid membrane was constructed by impregnating a porous Fluoropore Teflon (PTFE) membrane with a water-immiscible organic solvent (dihexyl ether). The extraction process was optimized with regard to the pH of the donor and acceptor phases, membrane liquid, extraction time and voltage applied to the inlet or outlet vial during extraction. The chlorinated phenols pentachlorophenol (PCP), 2,3,6 trichlorophenol (TCP) and 2,6 dichlorophenol (DCP) were thus efficiently separated by CE, using tris(hydroxymethyl)aminomethane (Tris) and an NaH₂PO₄ solution containing 1% (v/v) methanol at pH 10.5 as running buffer.     

Carbon nanotube reinforced hollow fiber solid/liquid phase microextraction: A novel extraction technique for the measurement of caffeic acid in Echinacea purpurea herbal extracts combined with high-performance liquid chromatography

A new design of hollow fiber solid–liquid phase microextraction (HF-SLPME) was developed for the determination of caffeic acid in medicinal plants samples as Echinacea purpure. The membrane extraction with sorbent interface used in this research is a three-phase supported liquid membrane consisting of an aqueous (donor phase), organic solvent/nano sorbent (membrane) and aqueous (acceptor phase) system operated in direct immersion sampling mode. The multi-walled carbon nanotube dispersed in the organic solvent is held in the pores of a porous membrane supported by capillary forces and sonification. It is in contact with two aqueous phases: the donor phase, which is the aqueous sample, and the acceptor phase, usually an aqueous buffer. All microextraction experiments were supported using an Accurel Q3/2 polypropylene hollow fiber membrane (600 μm I.D., 200 μm wall thicknesses, and 0.2 μm pore size). The experimental setup is very simple and highly affordable. The hollow fiber is disposable, so single use of the fiber reduces the risk of cross-contamination and carry-over problems. The proposed method allows the very effective and enriched recuperation of an acidic analyte into one single extract. In order to obtain high enrichment and extraction efficiency of the analyte using this novel technique, the main parameters were optimized. Under the optimized extraction conditions, the method showed good linearity (0.0001–50 μg/L), repeatability, low limits of detection (0.00005 μg/L) and excellent enrichment (EF = 2108).     

Electro membrane extraction of biological anions with ion chromatographic analysis

A simple and sensitive single step electro membrane extraction (EME) procedure was demonstrated for biological organic anions with determination by ion chromatography (IC). Nitrite, adipate, oxalate, iodide, fumarate, thiocyanate and perchlorate were extracted from aqueous donor solutions, across a supported liquid membrane (SLM) consisting of methanol impregnated in the walls of a porous polypropylene membrane bag and into an alkaline aqueous acceptor solution in the lumen of the propylene envelope by the application of potential of 12 V applied across the SLM. The acceptor solution was analyzed by IC. Parameters affecting the extraction performance such as type of SLM, extraction time, pH of the donor and acceptor solution, and extraction voltage were studied. The most favorable EME conditions were methanol as the SLM, extraction time of 5 min, pH of acceptor and sample solutions of 12 and 4, respectively, and a voltage of 12 V. Portable 12 V batteries were used in the study. Under these optimized conditions, all anions had enrichment factors ranging from 3.6 to 36.2 with relative standard deviations (n = 3) of between 6.6 and 17.5%. Good linearity ranging from 0.1 to 10 μg mL⁻¹ with coefficients of correlation (r) of between 0.9981 and 0.9996 were obtained. The limits of detection of the EME-IC method were from 0.01 to 0.14 μg mL⁻¹. The developed methodology was applied to amniotic fluid samples to evaluate the feasibility of the method for real applications.     

Continuous flow liquid membrane extraction: a novel automatic trace-enrichment technique based on continuous flow liquid-liquid extraction combined with supported liquid membrane

Combining the continuous flow liquid-liquid extraction (CFLLE) and supported liquid membrane (SLM) extraction, a novel aqueous-aqueous extraction technique that we termed continuous flow liquid membrane extraction (CFLME) is developed for trace-enrichment. The analyte was firstly extracted into the organic phase in the CFLLE step, then transported onto the organic liquid membrane that formed on the surface of the micro porous membrane of the SLM equipment. Finally, it passed through the liquid membrane and was trapped by the acceptor. Aspects related to CFLME were studied by using dichloromethane as liquid membrane, and sulfonylurea herbicides as model compounds. An enrichment factor of over 1000 was obtained when 10 μg l⁻¹ of MSM was enriched for 120 min by this technique. The drawbacks of only a few organic solvents can be selected as liquid membrane with a limited lifetime in SLM operation was overcome. In this CFLME method, almost all solvents that used in the conventional liquid-liquid extraction (LLE) can be adopted and the lifetime of liquid membrane is no longer a problem.     

Kinetic electro membrane extraction under stagnant conditions—Fast isolation of drugs from untreated human plasma

Amitriptyline, citalopram, fluoxetine, and fluvoxamine were isolated by electro membrane extraction (EME) from 70 μl of untreated plasma (pH 7.4), through a supported liquid membrane (SLM) of 1-ethyl-2-nitrobenzene immobilized in the pores of a porous polypropylene hollow fiber, and into 30 μl of 10 mM HCOOH as acceptor solution inside the lumen of the hollow fiber. The driving force of the extraction was a 9 V potential sustained over the SLM with a common battery, with the positive electrode placed in the plasma sample and the negative electrode placed in the acceptor solution. Extractions were performed under totally stagnant conditions with a very simple device for 1 min (kinetic regime), and subsequently the acceptor solution was analyzed directly by liquid chromatography–mass spectrometry (LC–MS). Recoveries were 12, 13, 22, and 17% for fluoxetine, amitriptyline, citalopram, and fluvoxamine, respectively. Sample clean-up was comparable to reversed-phase solid-phase extraction (SPE), but EME required substantially less time than SPE. The time advantage of EME was further improved by parallel extraction of three samples (for 1 min) with the same 9 V battery. EME from plasma combined with LC–MS provided limits of quantification (S/N = 10) in the range 0.4–2.3 ng/ml, linearity in the range 1–1000 ng/ml with r²-values of 0.998–0.999, and repeatability in the range 3.2–8.9% RSD in the mid-therapeutic window (100 ng/ml).     

Preconcentration in micro-electromembrane extraction across free liquid membranes

Preconcentration potential of micro-electromembrane extraction (μ-EME) across free liquid membrane (FLM) was examined with an anionic and a cationic dye, 4,5-dihydroxy-3-(p-sulfophenylazo)-2,7-naphthalene disulfonic acid, trisodium salt (SPADNS) and phenosafranine, respectively. For the first time, it was shown that the spatial flexibility of FLMs enabled application of tailored extraction units with mutually different shapes and migration cross-sections for FLMs, donor and acceptor solutions. Thus, e.g. conical units enabled easy and reproducible formation of a three-phase extraction system (donor/FLM/acceptor) with sub-μL volumes of acceptor solutions as well as rapid and highly efficient preconcentration of the two dyes. Quantitative measurements of resulting solutions were carried out by UV–vis spectrophotometry and enrichment factors of up to 98 were achieved for μ-EMEs of 20 μM SPADNS (50 μL) preconcentrated into 0.5 μL of pure water across 1-pentanol at −150 V for 18 min. Visual monitoring of the entire extraction process (with USB microscope camera) was possible across transparent extraction units, moreover, important extraction parameters, such as FLM dimensions and donor-to-acceptor solution volume ratio, which determine the mechanical stability of the membrane and maximum enrichment factor, respectively, were readily adjusted. Combination of μ-EME across FLMs with capillary electrophoresis (CE) was further shown suitable for preconcentration and determination of perchlorate in drinking water samples. Good repeatability of the μ-EME-CE method (RSD values better than 9.5%), linear relationship for the analytical signal vs. concentration (r² better than 0.997) and enrichment factors of up to 30 were achieved for μ-EMEs of perchlorate across 1-pentanol and 1-hexanol based FLMs.     

Electromembrane extraction of polar basic drugs from plasma with pure bis(2-ethylhexyl) phosphite as supported liquid membrane

Electromembrane extraction (EME) of polar basic drugs from human plasma was investigated for the first time using pure bis(2-ethylhexyl) phosphite (DEHPi) as the supported liquid membrane (SLM). The polar basic drugs metaraminol, benzamidine, sotalol, phenylpropanolamine, ephedrine, and trimethoprim were selected as model analytes, and were extracted from 300 μL of human plasma, through 10 μL of DEHPi as SLM, and into 100 μL of 10 mM formic acid as acceptor solution. The extraction potential across the SLM was 100 V, and extractions were performed for 20 min. After EME, the acceptor solutions were analyzed by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). In contrast to other SLMs reported for polar basic drugs in the literature, the SLM of DEHPi was highly stable in contact with plasma, and the system-current across the SLM was easily kept below 50 μA. Thus, electrolysis in the sample and acceptor solution was kept at an acceptable level with no detrimental consequences. For the polar model analytes, representing a log P range from −0.40 to 1.32, recoveries in the range 25–91% were obtained from human plasma. Strong hydrogen bonding and dipole interactions were probably responsible for efficient transfer of the model analytes into the SLM, and this is the first report on efficient EME of highly polar analytes without using any ionic carrier in the SLM.     

Simultaneous conduction of two- and three-phase hollow-fiber-based liquid-phase microextraction for the determination of aromatic amines in environmental water samples

This paper describes a simultaneously performed two-/three-phase hollow-fiber-based liquid-phase microextraction (HF-LPME) method for the determination of aromatic amines with a wide range of pK_a (−4.25 to 4.6) and log K_OW (0.9–2.8) values in environmental water samples. Analytes including aniline, 4-nitroaniline, 2,4-dinitroaniline and dicloran were extracted from basic aqueous samples (donor phase, DP) into the microliter volume of organic membrane phase impregnated into the pores of the polypropylene hollow fiber wall, then back extracted into the acidified aqueous solution (acceptor phase, AP) filling in the lumen of the hollow fiber. The mass transfer of the analytes from the donor phase through the organic membrane phase into acceptor phase was driven by both the counter-coupled transport of hydrogen ions and the pH gradient. Afterwards, the hollow fiber was eluted with 50 μL methanol to capture the analytes from both the organic membrane and the acceptor phase. Factors relevant to the enrichment factors (EFs) were investigated. Under the optimized condition (DP: 100 mL of 0.1 M NaOH with 2 M Na₂SO₄; organic phase: di-n-hexyl with 8% trioctylphosphine oxide (TOPO); AP: 10 μL of 8 M HCl; extraction time of 80 min), the obtained EFs were 405–2000, dynamic linear ranges were 5–200 μg/L (R > 0.9976), and limits of detection were 0.5–1.5 μg/L. The presence of humic acid (0–25 mg/L dissolved organic carbon) had no significant effect on the extraction efficiency. The proposed procedure worked very well for real environmental water samples with microgram per liter level of analytes, and good spike recoveries (80–103%) were obtained.     

Supported liquid membrane extraction with single hollow fiber for the analysis of fluoroquinolones from environmental surface water samples

In this work, the simple analytical method for the determination of four fluoroquinolone antibiotics: ciprofloxacin, enrofloxacin, norfloxacin and danofloxacin, in environmental surface water samples is described. Sample pretreatment step was performed by the application of a technique based on supported liquid membrane extraction with the configuration of single hollow fiber (HF-SLM). The HPLC system with diode array detection was used for final analysis of studied analytes. Various parameters affecting the extraction efficiency during HF-SLM enrichment, such as type of membrane diluent, pH of donor (sample) and acceptor phases, as well as an enrichment time and salt content of sample were studied. Using the presented hollow-fiber extraction high recovery (70–80%) was achieved. It gave enrichment factor above 100. The detection limits in surface water samples, for the four target antibiotics, were at range 0.01–0.02 μg/l, when 10 ml samples were processed. The obtained results demonstrate the applicability of presented method for the selective extraction of fluoroquinolones in environmental water samples at ultratrace level. Errors, expressed as relative standard deviation (RSD) were below 8%, for all tested concentration levels.     

Dynamic supported liquid membrane tip extraction of glyphosate and aminomethylphosphonic acid followed by capillary electrophoresis with contactless conductivity detection

A dynamic supported liquid membrane tip extraction (SLMTE) procedure for the effective extraction and preconcentration of glyphosate (GLYP) and its metabolite aminomethylphosphonic acid (AMPA) in water has been investigated. The SLMTE procedure was performed in a semi-automated dynamic mode and demonstrated a greater performance against a static extraction. Several important extraction parameters such as donor phase pH, cationic carrier concentration, type of membrane solvent, type of acceptor stripping phase, agitation and extraction time were comprehensively optimized. A solution of Aliquat-336, a cationic carrier, in dihexyl ether was selected as the supported liquid incorporated into the membrane phase. Quantification of GLYP and AMPA was carried out using capillary electrophoresis with contactless conductivity detection. An electrolyte solution consisting of 12 mM histidine (His), 8 mM 2-(N-morpholino)ethanesulfonic acid (MES), 75 μM cetyltrimethylammonium bromide (CTAB), 3% methanol, pH 6.3, was used as running buffer. Under the optimum extraction conditions, the method showed good linearity in the range of 0.01–200 μg/L (GLYP) and 0.1–400 μg/L (AMPA), acceptable reproducibility (RSD 5–7%, n = 5), low limits of detection of 0.005 μg/L for GLYP and 0.06 μg/L for AMPA, and satisfactory relative recoveries (90–94%). Due to the low cost, the SLMTE device was disposed after each run which additionally eliminated the possibility of carry-over between runs. The validated method was tested for the analysis of both analytes in spiked tap water and river water with good success.     

In-line coupling headspace liquid-phase microextraction with capillary electrophoresis

An analytical technique of in-line coupling headspace liquid-phase microextraction (HS-LPME) with capillary electrophoresis (CE) was proposed to determine volatile analytes. A special cover unit of the sample vial was adopted in the coupling method. To evaluate the proposed method, phenols were used as model analytes. The parameters affecting the extraction efficiency were investigated, including the configuration of acceptor phase, kind and concentration of acceptor solution, extraction temperature and time, salt-out effect, sample volume, etc. The optimal enrichment factors of HS-LPME were obtained with the sample volume of about half of sample vials, which were confirmed by both the theoretical prediction and experimental results. The enrichment factors were obtained from 520 to 1270. The limits of detection (LODs, S/N = 3) were in the range from 0.5 to 1 ng/mL each phenol. The recoveries were from 87.2% to 92.7% and the relative standard deviations (RSDs) were lower than 5.7% (n = 6). The proposed method was successfully applied to the quantitative analysis of the phenols in tap water, and proved to be a simple, convenient and reliable sample preconcentration and determination method for volatile analytes in water samples.     

Ultrasonic assisted headspace single drop micro-extraction and gas chromatography with nitrogen-phosphorus detector for determination of organophosphorus pesticides in soil

This work describes optimization of headspace single drop micro-extraction for extraction of five organophosphorus pesticides; thionazin, sulfotep, dimethoate, disulfoton and parathion in soil. Ultrasound has also been used successfully to improve and accelerate the extraction of the analytes from the sample. The optimized extraction performance was obtained when the experimental parameters were set as follows; 3.0 μL of octanol as extraction solvent, high ionic strength (20% sodium chloride), 1:1 (w/v) sample dilution with water, extraction temperature at 60 °C for 30 min; applying ultrasound and without any pH adjustment. The optimized method was linear over the calibration range (5–200 and 10–300 for different analytes) with limits of detection of 0.1–2.0 ng g⁻¹. The enrichment factor for OPPs was 1.4–12.7 and the method was also reproducible with the relative standard deviations (RSD%) of 2.1–6.9%.     

Single bubble in-tube microextraction coupled with capillary electrophoresis

Headspace (HS) extraction is a sample pretreatment technique for volatile and semivolatile organic compounds in a complex matrix. Recently, in-tube microextraction (ITME) coupled with CE using an acceptor plug placed in the capillary inlet was developed as a simple but powerful HS extraction method. Here, we present single bubble (SB) ITME using a bubble hanging to the capillary inlet immersed in a sample donor solution as a HS of submicroliter volume (∼200 nL). The analytes evaporated to the bubble were extracted into the acceptor phase through the capillary opening, then electrophoresis of the enriched extract was carried out. Since the bubble volume was much smaller than a conventional HS volume (∼1 mL), it was filled with the evaporated analytes rapidly and the analytes could be enriched much faster compared to conventional HS-ITME. Owing to the high surface-to-volume ratio of the SB, 5 min SB-ITME yielded the enrichment factor values similar to those of 10 min HS-ITME. When 5 min SB-ITME at room temperature was applied to a tap water sample, the enrichment factors of 2,4,6-trichlorophenol (TCP), 2,3,6-TCP, and 2,6-dichlorophenol were 53, 41, and 60, respectively, and the LOQs obtained by monitoring the absorbance at 214 nm were 5.6–8.3 ppb, much lower than 200 ppb, the World Health Organization guideline for the maximum permissible concentration of 2,4,6-TCP in drinking water.