Membrane extraction with a sorbent interface for headspace monitoring of aqueous samples using a cap sampling device

A cap-shaped device was employed for headspace sampling. This sampling device coupled to membrane extraction with a sorbent interface (MESI) is intended to perform on-site and on-line aqueous sample monitoring. A laboratory sampling testwas performed both at the water surface and under water, and it showed some advantages in underwater monitoring. A group of volatile organic compounds (VOCs), varying in PDMS/gas and gas/water distribution constants, benzene, toluene, ethylbenzene, o-xylene, and trichloroethylene (TCE), was used for the sampling study. Magnetic stirring of the sample and circulation of the headspace air with a microfan were used for the enhancement of mass transfer between sample matrix and membrane to obtain higher extraction rate and efficiency. The agitation approaches were investigated individually and compared. The results showed that simultaneous agitation in water and air could greatly improve the extraction efficiency. Good linearity and precision and low detection limits were obtained for water-surface monitoring. The study demonstrated that Cap-MESI is a useful tool for field headspace monitoring of volatile organic compounds.     

Kinetic calibration for automated headspace liquid-phase microextraction

The kinetics of the absorption and desorption of analytes for headspace liquid-phase microextraction (HS-LPME) were studied. It was found that the desorption of analytes from the extraction phase into the sample matrix is isotropic to the absorption of the analytes from the sample matrix into the extraction phase under the same conditions. This therefore allows for the calibration of absorption using desorption. Calibration was accomplished by exposing the extraction phase, which contained a standard, to the sample matrix. The information from the desorption of the standard, such as time constant a, could be directly used to estimate the concentration of the target analyte in the sample matrix. This new kinetic calibration method for headspace LPME was successfully used to correct the matrix effects in the BTEX analysis of an orange juice sample. In this study, the headspace LPME techniques were successfully fully automated, for both static and dynamic methods, with the CTC CombiPal autosampler. All operations of headspace LPME, including sample transfer and agitation, filling of extraction solvent, exposing the solvent in the headspace, withdrawing the solvent to syringe and introducing the extraction phase into injector, were autoperformed by the CTC autosampler. The fully automated headspace LPME technique is more convenient and improved the precision and sensitivity of the method. This automated dynamic headspace LPME technique can be also used to obtain the distribution coefficient between the sample matrix (aqueous or another solution) and the extraction phase (1-octanol or another solvent). The distribution coefficient between 1-octanol and orange juice, at 25 degrees C, was obtained with this technique.     

Thin-film microextraction

The properties of a thin sheet of poly(dimethylsiloxane) (PDMS) membrane as an extraction phase were examined and compared to solid-phase microextraction (SPME) PDMS-coated fiber for application to semivolatile analytes in direct and headspace modes. This new PDMS extraction approach showed much higher extraction rates because of the larger surface area to extraction-phase volume ratio of the thin film. Unlike the coated rod formats of SPME using thick coatings, the high extraction rate of the membrane SPME technique allows larger amounts of analytes to be extracted within a short period of time. Therefore, higher extraction efficiency and sensitivity can be achieved without sacrificing analysis time. In direct membrane SPME extraction, a linear relationship was found between the initial rate of extraction and the surface area of the extraction phase. However, for headspace extraction, the rates were somewhat lower because of the resistance to analyte transport at the sample matrix/headspace barrier. It was found that the effect of this barrier could be reduced by increasing either agitation, temperature, or surface area of the sample matrix/headspace interface. A method for the determination of PAHs in spiked lake water samples was developed based on the membrane PDMS extraction coupled with GC/MS. A linearity of 0.9960 and detection limits in the low-ppt level were found. The reproducibility was found to vary from 2.8% to 10.7%.     

Internal calibrant in the stripping gas. An approach to calibration of membrane extraction with a sorbent interface

A new technique for calibration in membrane extraction processes by adding an analytically noninterfering internal calibrant in the stripping gas is described. Membrane extraction with a sorbent interface (MESI) system was used to evaluate this method. During the membrane extraction process, the internal calibrant present in the carrier (stripping) gas and the target analyte present in the sample matrix will permeate simultaneously through the membrane in opposite directions. The changes of accumulation amounts of internal calibrant in the microtrap can be used as a means of calibration to correct the variations of extraction rate due to the variation in environmental factors, such as the sample velocity and the membrane temperature. Thus, this approach should allow for more accurate estimates of the concentrations of target analytes at various sampling or monitoring conditions during field analysis. Finally, a group of selected compounds was employed to test this calibration strategy, and the results indicated the advantages of the proposed approach for on-site analysis.     

Hollow fiber-protected liquid-phase microextraction of triazine herbicides

A new microextraction technique termed hollow fiber-protected liquid-phase microextraction (LPME) was developed. Triazines were employed as model compounds to assess the extraction procedure and were determined by gas chromatography/mass spectrometry. Toluene functioned as both the extraction solvent and the impregnation solvent. Some important extraction parameters, such as effect of salt, agitation, pH, and exposure time were optimized. The new method provided good average enrichment factors of > 150 for eight analytes, good repeatability (RSDs <3.50%, n = 7), and good linearity (r2 > or = 0.9995) for spiked deionized water samples. The limits of detection (LODs) were in the range of 0.007-0.063 microg/L (S/N = 3) under selected ion monitoring mode. In addition to enrichment, hollow fiber-protected LPME also served as a technique for sample cleanup because of the selectivity of the membrane, which prevented large molecules and extraneous materials, such as humic acids in solution, from being extracted. The utilization of this procedure in the extraction of a slurry sample (mixture of soil and water) also gave good precision (RSDs <5.00%, n = 3) and LODs (0.04-0.18 microg/L, S/N = 3). Finally, the comparison of the new method with the static solvent drop LPME and solid-phase microextraction was performed. The results demonstrated that hollow fiber-protected LPME was a fast, accurate, and stable sample pretreatment method that gave very good enrichment factors for the extraction of triazine herbicides from aqueous or slurry samples.     

Optimization of process parameters for the extraction of chromium (VI) by emulsion liquid membrane using response surface methodology

The emulsion liquid membrane technique was used for the extraction of hexavalent chromium ions from aqueous solution of waste sodium dichromate recovered from the pharmaceutical industry wastewater. The liquid membrane used was composed of kerosene oil as the solvent, Span-80 as the surfactant and potassium hydroxide as internal reagent. Trioctyl amine and Aliquat-336 were used as carriers. The emulsion stability was carried out at different surfactant concentration, agitation speed and emulsification time. Statistical experimental design was applied for the optimization of process parameters for the extraction of chromium by emulsion liquid membrane. The effects of process parameters namely, agitation speed, membrane to emulsion (M/E) ratio and carrier concentration on the extraction of chromium were optimized using a response surface method. The optimum conditions for the extraction of chromium (VI) using response surface methodology for Trioctyl amine were: agitation speed – 201.369 rpm, M/E ratio – 0.5887% (v/v) and carrier concentration – 4.0932% (v/v) and for Aliquat-336: agitation speed – 202.097 rpm, M/E ratio – 0.5873% (v/v) and carrier concentration – 3.9211% (v/v). At the optimized condition the maximum chromium extraction was found to be 89.2% and 96.15% using Trioctyl amine and Aliquat-336, respectively.     

Solid-phase microextraction and headspace solid-phase microextraction for the determination of polychlorinated biphenyls in water samples

A solid-phase microextraction (SPME) method has been developed for the quantification of polychlorinated biphenyls (PCBs) in water samples. Parameters such as sampling time, volume of water, volume of headspace, temperature, addition of salts, and agitation of the sample were studied. Because the time for reaching equilibrium between phases takes several hours or days, depending on the experimental conditions, it was necessary to work in nonequilibrium conditions to keep the sample analysis to a reasonable time. The possibility of sampling the headspace over the water sample (HSSPME), instead of immersing the fiber into the water (SPME), was also investigated, and despite the low partition of PCB into the headspace, HSSPME offered higher sensitivity than SPME at 100 °C. The adsorption kinetics for SPME at room temperature, SPME at 100 °C, and HSSPME at 100 °C were investigated and compared. The proposed HSSPME method exhibits excellent linearity and sensitivity. The detection limit was in the sub-ng/L level. This method has been applied to a real industrial harbor water and compared with liquid-liquid extraction. Both techniques offered similar results, but HSSPME was much more sensitive and considerably faster, by eliminating all the manual process intensive sample workup, and reduces solvent consumption entirely. The only drawback was that matrix effects were observed, but with the addition of deuterated surrogates to the sample or the use of a standard addition calibration, accurate quantification can be achieved.     

Membrane-assisted solvent extraction of triazines, organochlorine, and organophosphorus compounds in complex samples combined with large-volume injection-gas chromatography/mass spectrometric detection

The performance of the fully automated membrane-assisted solvent extraction was investigated for 47 environmental contaminants (among them 30 organochlorine compounds, 9 organophosphorus compounds, and 7 triazines). The extraction took place in a 20-mL headspace vial filled with the aqueous sample and containing a polypropylene membrane bag with 1 mL of cyclohexane as extractant. This device was handled by a multipurpose sampler, which enabled the sample to be mixed at a defined temperature with subsequent large-volume injection of the organic extract taken out of the membrane bag. After optimization of extraction parameters, the method was validated for the three compound classes, triazines and organochlorine and organophosphorus compounds, using spiked distilled water. Then, the extraction yield of these analytes from several complex samples such as a natural and a synthetic wastewater, a bacterial culture, and orange juice was determined and compared to a conventional liquid-liquid extraction. Furthermore, the possibility of reducing matrix interference by adding salt, methanol, or detergent during membrane-assisted solvent extraction was investigated.     

Determination of polychlorinated biphenyls in milk samples by saponification-solid-phase microextraction.

A saponification-HSSPME procedure has been developed for the extraction of PCBs from milk samples. Saponification of the samples improves the PCB extraction efficiency and allows attaining lower background. A mixed-level fractional design has been used to optimize the sample preparation process. Five variables have been considered: extraction time, agitation, kind of microextraction fiber, concentration, and volume of NaOH aqueous solution. Also the kinetic of the process has been studied with the two fibers (100-microm PDMS and 65-microm PDMS-DVB) included in this study. Analyses were performed on a gas chromatograph equipped with an electron capture detector and a gas chromatograph coupled to a mass selective detector working in MS-MS mode. The proposed method is simple and rapid, and yields high sensitivity, with detection limits below 1 ng/mL, good linearity, and reproducibility. The method has been applied to liquid milk samples with different fat content covering the whole commercial range, and it has been validated with powdered milk certified reference material.     

Diffusion-based calibration for SPME analysis of aqueous samples

When an SPME fiber is exposed for a short period of time to a flowing fluid sample, the amount of extracted analyte depends on its diffusion coefficient in the matrix medium, and it can be correlated to its concentration using a simple mathematical model. This work discusses the extension of this approach, already validated for gaseous samples and SPME fibers coated with strong adsorbent coatings, to the diffusion-based quantification of analytes present in aqueous samples. Dilute aqueous solutions of aromatic hydrocarbons were used as model samples and vials were modified to use conventional magnetic agitation with controlled tangential flow of the test solution around the fiber. It was demonstrated that, with proper selection of the stirring speed and sampling time, the same diffusion-based quantitative model used for gas samples could be employed. Under optimal conditions, the concentrations of the evaluated aromatic hydrocarbons were estimated with relative standard deviations between 0.8 and 3.6% and without deviation from the expected values within this precision range. Considering the extraction times involved, between 30 and 60 s, the approach here presented is the fastest possible technique for direct extraction of analytes from liquid samples.     

Development and application of porous membrane-protected carbon nanotube micro-solid-phase extraction combined with gas chromatography/mass spectrometry

A novel, multiwalled carbon nanotube (MWCNT)-supported micro-solid-phase extraction (mu-SPE) procedure has been developed. A 6-mg sample of MWCNTs was packed inside a (2 cm x 1.5 cm) sheet of porous polypropylene membrane whose edges were heat-sealed to secure the contents. The mu-SPE device, which was wetted with dichloromethane, was then placed in a stirred sewage sludge sample solution to extract organophosporous pesticides, used here as model compounds. Tumbling of the extraction device within the sample solution facilitated extraction, and the porous membrane acted as a filter to exclude the extraction of extraneous materials. After extraction, analytes were desorbed in hexane and analyzed using gas chromatography/mass spectrometry. Since the porous membrane afforded protection of the MWCNTs, no further cleanup of the extract was required. The pi-pi electrostatic interaction with the analytes and the large surface area of MWCNTs facilitated the adsorption of analytes, with good selectivity and reproducibility. Under the optimized extraction conditions, the method showed good linearity in the range of 0.1-50 mug/L, repeatability of the extractions (RSD 2-8%, n = 4), and low limits of detection (1-7 pg/g). No analyte carryover effect was observed, and each mu-SPE device could be used for up to 30 extractions. Comparison was made with hollow fiber protected solid-phase microextraction and headspace solid-phase microextraction; mu-SPE was demonstrated to be a fast, accurate, and cost-effective pretreatment method for sewage sludge samples.     

Dynamic diffusion model for tracing the real-time potential response of polymeric membrane ion-selective electrodes

A numerical solution for the prediction of the time-dependent potential response of a polymeric-based ion-selective electrode (ISE) is presented. The model addresses short- and middle-term potential drifts that are dependent on changes in concentration gradients in the aqueous sample and organic membrane phase. This work has important implications for the understanding of the real-time response behavior of potentiometric sensors with low detection limits and with nonclassical super-Nernstian response slopes. As a model system, the initial exposure of membranes containing the well-examined silver ionophore O,O' '-bis[2-(methylthio)ethyl]-tert-butylcalix[4]arene was monitored, and the large observed potential drifts were compared to theoretical predictions. The model is based on an approximate solution of the diffusion equation for both aqueous and organic diffusion layers using a numerical scheme (finite difference in time and finite elements in space). The model may be evaluated on the basis of experimentally available parameters and gives time-dependent information previously inaccessible with a simpler steady-state diffusion model. For the cases studied, the model gave a very good correlation with experimental data, albeit with lower than expected diffusion coefficients for the organic phase. This model may address numerous open questions regarding the response time and memory effects of low-detection-limit ion-selective electrodes and for other membrane electrodes where ion fluxes are relevant.     

Headspace solvent microextraction.

A hanging microliter drop of 1-octanol is shown to be an excellent preconcentration medium for headspace analysis of volatile compounds in an aqueous matrix by gas chromatography (GC) or gas chromatography/mass spectrometry (GC/MS). Model compounds benzene, toluene, ethylbenzene, and o-xylene (BTEX) are conveniently and rapidly preconcentrated in the microdrop. An internal standard, decane, is present in the organic extracting solvent, and linear calibration curves of relative peak area versus aqueous concentration are obtained for the four model compounds. Detailed kinetic studies reveal that the overall rate of mass transfer is limited by both the aqueous-phase stirring rate and the degree of convection within the organic phase. The very low vapor pressure of 1-octanol results in minimal evaporation of the microdrop during the extraction time. This system represents an inexpensive, convenient, and precise sample cleanup and preconcentration method for the determination of volatile organic compounds at trace levels.     

Enhancement of extraction efficiency and reduction of boundary layer effects in pulse introduction membrane extraction

Membrane separation has emerged as an attractive alternative for interfacing an extraction step directly to a gas chromatograph or to a mass spectrometer. In pulse introduction (or flow injection type) membrane extraction, a sample pulse is introduced onto an eluent stream that transports it onto the membrane. Since a fixed sample volume is injected, the detector response is directly proportional to the extraction efficiency. This in turn depends on membrane module design, flow conditions, etc. Also, when water contacts a membrane, a static boundary layer is formed at the membrane surface that serves as an additional diffusional barrier to the permeation process. Consequently, permeation slows down, which lowers the speed of analysis. In this paper, methods of increasing the extraction efficiency and decreasing boundary layer effects are presented. The goal is to have higher sensitivity at a shorter analysis time. A stream of nitrogen is introduced into the membrane after sample elution to eliminate the aqueous boundary layer. This technique is found to be effective not only for faster analysis, but also for increasing extraction efficiency.     

全自动在线HS-SPME-GC-MS/MS检测鱼塘投毒案件水样中的13种有机磷农药

建立全自动在线顶空固相微萃取-气相色谱串联质谱技术(HS-SPME-GC-MS/MS)检测鱼塘投毒案件水样中13种有机磷农药的方法.将2 mL水样中加入0.6 g氯化钠(NaCl)置于20 mL顶空瓶中,使用直径为100μm的聚二甲基硅氧烷(PDMS)萃取纤维,在75℃条件下萃取45 min,采用GC-MS/MS多反应...     

Immunologic trapping in supported liquid membrane extraction

To obtain a high degree of selectivity in sample preparation, supported liquid membrane (SLM) extraction was combined with immunologic recognition. The SLM employs a hydrophobic polymer for supporting the immobilization of an organic solvent, thus forming a nonporous membrane. Said membrane separates the aqueous sample on one side (donor) from a receiving aqueous phase on the other (acceptor). The extraction involves the partitioning of neutral compounds between the sample solution, continuously pumped alongside the membrane, and the membrane. From the membrane, reextraction takes place into a second aqueous phase containing antibodies specific for the target compound(s). Hence, there is a formation of an antibody-antigen complex at the heart of the sample preparation (ImmunoSLM). When the immunocomplex forms, the antigen can no longer redissolve in the organic membrane, thus being trapped in the acceptor. Consequently, the concentration gradient of free antigen over the membrane is ideally unaffected, this being the driving force for the process. With a surplus of antibody, the concentration of analyte in the receiving phase will easily exceed the initial sample concentration. In this work, the so formed immunocomplex was quantified on-line, using a fluorescein flow immunoassay in a sequential injection analysis (SIA) setup. The outlined ImmunoSLM-SIA scheme was successfully applied for the extraction of 4-nitrophenol from spiked water solutions as well as from a spiked wastewater sample, indicating that the immunoextraction can be suitable when dealing with difficult matrixes.     

Miniaturized and automated sample pretreatment for determination of PCBs in environmental aqueous samples using an on-line microporous membrane liquid-liquid extraction-gas chromatography system

A new, fast, and automated sample pretreatment technique for determination of lipophilic organic compounds in aqueous samples has been developed and applied to the determination of polychlorinated biphenyls (PCBs) in environmental river water. It is based on miniaturized microporous membrane liquid-liquid extraction coupled on-line to gas chromatography (GC) with electron capture detection. The heart of the system that simultaneously connects the sample pretreatment step to the final GC analysis has been named the extracting syringe (ESy). The ESy carries a miniaturized membrane extraction card attached to an electrically and mechanically designed installment and is mounted directly over a GC injector for fully automated injection of the extract. A method was developed to extract 10 PCB congeners from 1-mL water samples (after addition of 40% acetonitrile) with an extraction time of 10 min. The optimized methodology showed good linearity (in the dynamic concentration range of 5 ng L(-)(1)-1 microg L(-)(1)), enrichment factors of 33-40 times, repeatable extractions (RSD 2-5%, n = 4), and low detection limits (2-3 ng L(-)(1)). Acetonitrile had to be added to the samples in order to overcome the influence of PCB adsorption on the repeatability of extraction and enrichment and to minimize the overall memory effect (OME). OME and carryover depended not only on the concentration of the organic solvent added to the sample and that used in the washing procedure but also on whether the extracting card was changed or not. When an optimized washing procedure was applied, the OME was approximately 0.2% at high concentrations (i.e., 1 microg L(-)(1)). When each extraction took place in a new extraction card, no OME was detected. Additionally, no significant adsorption onto glass surfaces or a matrix effect on extraction was noticed. The main features of this methodology are good extraction repeatability, low detection limits at short extraction time, and the unsurpassed characteristic of no detectable OME in the entire system when each sample is processed in a new card. The total consumption of organic (nonchlorinated) solvents is less than 5 mL per sample.     

An analytical method for trifluoroacetic Acid in water and air samples using headspace gas chromatographic determination of the methyl ester

An analytical method has been developed for the determination of trace levels of trifluoroacetic acid (TFA), an atmospheric breakdown product of several of the hydrofluorocarbon (HFC) and hydrochlorofluorocarbon (HCFC) replacements for the chlorofluorocarbon (CFC) refrigerants, in water and air. TFA is derivatized to the volatile methyl trifluoroacetate (MTFA) and determined by automated headspace gas chromatography (HSGC) with electron-capture detection or manual HSGC using GC/MS in the selected ion monitoring (SIM) mode. The method is based on the reaction of an aqueous sample containing TFA with dimethyl sulfate (DMS) in concentrated sulfuric acid in a sealed headspace vial under conditions favoring distribution of MTFA to the vapor phase. Water samples are prepared by evaporative concentration, during which TFA is retained as the anion, followed by extraction with diethyl ether of the acidified sample and then back-extraction of TFA (as the anion) in aqueous bicarbonate solution. The extraction step is required for samples with a relatively high background of other salts and organic materials. Air samples are collected in sodium bicarbonate-glycerin-coated glass denuder tubes and prepared by rinsing the denuder contents with water to form an aqueous sample for derivatization and analysis. Recoveries of TFA from spiked water, with and without evaporative concentration, and from spiked air were quantitative, with estimated detection limits of 10 ng/mL (unconcentrated) and 25 pg/mL (concentrated 250 mL:1 mL) for water and 1 ng/m(3) (72 h at 5 L/min) for air. Several environmental air, fogwater, rainwater, and surface water samples were successfully analyzed; many showed the presence of TFA.     

Sample preparation using a miniaturized supported liquid membrane device connected on-line to packed capillary liquid chromatography

A miniaturized supported liquid membrane device has been developed for sample preparation and connected on-line to a packed capillary liquid chromatograph. The device consists of hydrophobic polypropylene hollow fiber, inserted and fastened in a cylindrical channel in a Kel-F piece. The pores of the fiber are filled with an organic solvent, in this study 6-undecanone, thus forming a liquid membrane. The sample is pumped on the outside of the hollow fiber (donor), and the analytes are selectively enriched and trapped in the fiber lumen (acceptor). With this approach, the volume of the acceptor solution can be kept as low as 1-2 μL. This stagnant acceptor solution is then transferred through capillaries attached to the fiber ends to the LC system. The system was tested with a secondary amine (bambuterol), as a model substance in aqueous standard solutions as well as in plasma. The best extraction efficiency in aqueous solution, with an acceptor volume of 1.9 μL, was 32.5% at a donor flow rate of 2.5 μL/min. At flow rates above 20 μL/min, the concentration enrichment per time unit was approximately constant, at 0.9 times/min, i.e., 9 times enrichment in about 10 min. The overall repeatability (RSD) for spiked plasma samples was ～4% (n = 12). Linear calibration curves of peak area versus bambuterol concentration were obtained for both aqueous standard solutions and spiked plasma samples. The detection limit for bambuterol in plasma, after 10 min of extraction at a flow rate of 24 μL/min, was 80 nM.     

Electrochemically modulated liquid-liquid extraction of ions

The development of ion extraction methods under electrochemical control via electrochemistry at the interface between two immiscible electrolyte solutions is discussed. A hydrodynamic flow injection system was used for the potentiostatic extraction of non-redox-active species from a flowing aqueous phase into a stationary organogel phase. The ions tetraethylammonium, 4-octylbenzenesulfonate (4-OBSA-), and p-toluenesulfonate (p-TSA-) were studied as model analytes. The extraction study comprised examination of the influence of extraction potentials, aqueous-phase flow rate, and target species concentration. The extraction process can be monitored in situ by means of the ion-transfer current, which has opposing signs for anions and cations. Hydrodynamic voltammograms were obtained from these experiments. The selective extraction of 4-OBSA-, from its mixture with p-TSA-, as well as coextraction of both anions is shown. The results demonstrate the utility of electrochemical modulation for the controlled extraction of ions from an aqueous phase into an organogel electrolyte phase. This offers potential benefits for various analytical processes including sample preparation and cleanup.