Determination of saccharides in atmospheric aerosol using anion-exchange high-performance liquid chromatography and pulsed-amperometric detection

An improved method is described for the quantification of primary sugars, sugar alcohols and anhydrosugars in atmospheric aerosols, making use of separation by high-performance anion-exchange chromatography (HPAEC) with pulsed amperometric detection (PAD). Quartz fibre filters from high-volume samplers were extracted with water and the extract injected directly. Repeatability is typically 4% RSD, for e.g. levoglucosan at 50 ng m(-3) in air, better for winter levels around 700 ng m(-3). Limits of detection for individual sugars are in the range 0.02-0.05 microg mL(-1) in solution, corresponding to 2-5 ng m(-3) from a 20 m(3) air sample. The overlap of arabitol and levogluocosan is overcome by using a Dionex PA-1 column, with appropriate control of eluent composition, and peak deconvolution software, allowing quantification of both sugars in difficult summer samples containing low-levels of levoglucosan. Analysis of a set of ambient aerosol samples by both GC-flame ionization detection and HPAEC-PAD shows good agreement. The new method has the advantage of requiring no sample pretreatment or derivatization and is thus well suited to handling large numbers of samples.     

Quantification of the xenoestrogens 4-tert.-octylphenol and bisphenol A in water and in fish tissue based on microwave assisted extraction, solid-phase extraction and liquid chromatography-mass spectrometry

Extraction methods were developed for quantification of the xenoestrogens 4-tert.-octylphenol (tOP) and bisphenol A (BPA) in water and in liver and muscle tissue from the rainbow trout (Oncorhynchus mykiss). The extraction of tOP and BPA from tissue samples was carried out using microwave-assisted solvent extraction (MASE) followed by solid-phase extraction (SPE). Water samples were extracted using only SPE. For the quantification of tOP and BPA, liquid chromatography mass spectrometry (LC-MS) equipped with an atmospheric pressure chemical ionisation interface (APCI) was applied. The combined methods for tissue extraction allow the use of small sample amounts of liver or muscle (typically 1 g), low volumes of solvent (20 ml), and short extraction times (25 min). Limits of quantification of tOP in tissue samples were found to be approximately 10 ng/g in muscle and 50 ng/g in liver (both based on 1 g of fresh tissue). The corresponding values for BPA were approximately 50 ng/g in both muscle and liver tissue. In water, the limit of quantification for tOP and BPA was approximately 0.1 microg/l (based on 100 ml sample size).     

Determination of trace amounts of off-flavor compounds in drinking water by stir bar sorptive extraction and thermal desorption GC-MS.

A method for the determination of trace amounts of off-flavor compounds including 2-methylisoborneol, geosmin and 2,4,6-trichloroanisole in drinking water was developed using the stir bar sorptive extraction technique followed by thermal desorption-GC-MS analysis. The extraction conditions such as extraction mode, salt addition, extraction temperature, sample volume and extraction time were examined. Water samples (20, 40 and 60 ml) were extracted for 60-240 min at room temperature (25 degrees C) using stir bars with a length of 10 mm and coated with a 500 microm layer of polydimethylsiloxane. The extract was analyzed by thermal desorption-GC-MS in the selected ion monitoring mode. The method showed good linearity over the concentration range from 0.1 or 0.2 or 0.5 to 100 ng l(-1) for all the target analytes, and the correlation coefficients were greater than 0.9987. The detection limits ranged from 0.022 to 0.16 ng l(-1). The recoveries (89-109%) and precision (RSD: 0.80-3.7%) of the method were examined by analyzing raw water and tap water samples fortified at the 1 ng l(-1) level. The method was successfully applied to low-level samples (raw water and tap water).     

Determination of extractable perfluorooctanoic acid (PFOA) in water, sweat simulant, saliva simulant, and methanol from textile and carpet samples by LC/MS/MS

Methods were developed to quantify the amount of perfluorooctanoic acid (PFOA) extracted from textile and carpet samples through contact with water, methanol, and sweat and saliva simulants using LC/MS/MS. The limit of quantitation (LOQ) for samples extracted in water and sweat simulant is 1 ppb (ng PFOA (g sample)(-1)) while the limits of quantitation for samples extracted in saliva simulant and methanol were 3 ppb and 2.5 ppb, respectively. Method validation results are provided for a polyester control textile sample that was extracted in water on two different days by different analysts, which gave an overall recovery of 103% and standard deviation of 5.3% for 30 analyses. However, for routine application of these methods to a large number of sample sets differing in chemical and physical compositions, a complete validation for each sample type is not practical or possible since control samples for fortifications are often not available. Instead, suitable analytical methods and acceptance criteria are described which ensure accurate PFOA quantitation in each of the solvent extract types. During routine use of these methods, post-extraction spike recoveries for the different sample types and solvents are 100 +/- 15% using a dual isotopically labeled (13)C-PFOA internal standard to correct for matrix effects. A comparison of extraction solvent versus time using a wrist action shaker for textile and carpet samples demonstrates that the total extractable amount of PFOA is similar for each of the solvent types. However, as expected the rate of extraction in water and simulants is significantly less than that of methanol. Finally, a comparison of 2 h and 24 h wrist action shaker extractions with a 1.5 h pressurized fluid extraction (PFE) in methanol reveals that the 24 h wrist action shaker yields the highest results. The 2 h wrist action shaker results are similar to those of the 1.5 h PFE extraction.     

Effect of temperature and solvent composition on extraction of fumonisins B1 and B2 from corn products

Fumonisins B1 and B2 were extracted from naturally contaminated corn products by using different extraction solvent compositions (methanol-water, acetonitrile-methanol-water, ethanol-water, and 100% water) and a range of temperatures from ambient to 150 degrees C. Ground samples of several corn products and 1 rice sample were mixed with an adsorbent material (Hydromatrix), and the fumonisins were extracted in 2 sequential 5 min static extractions at various temperatures. The combined extracts were cleaned up and analyzed by reversed-phase liquid chromatography with fluorescence detection after o-phthaldialdehyde-mercaptoethanol derivatization. The results showed a clear influence of temperature and solvent composition on recovery of fumonisins from some matrixes. With acetonitrile-methanol-water (1 + 1 + 2) the quantity of fumonisins extracted from naturally contaminated taco shells almost tripled in going from 23 degrees to 80 degrees C, and increased by another 30% when ethanol-water (3 + 7) was used as extraction solvent at 80 degrees C. Similar results were obtained with nacho chips. These effects were less pronounced with cornmeal, and small differences due to temperature and solvent composition were observed for corn flakes and rice. The ethanol-water extraction solvent combinations were specifically evaluated in an effort to use the cheapest, least toxic, and most environmentally friendly solvents for organic residue analysis. At 80 degrees C, ethanol-water combinations performed equally or better than methanol-water (8 + 2) or acetonitrile-methanol-water (1 + 1 + 2), combinations which are commonly used for fumonisin extractions. Even 100% water was successful for extracting fumonisins from the products, except for rice. However, increased amounts of water created technical problems and required an increased amount of Hydromatrix in the samples prior to extraction.     

The extraction and analysis of 1,4-dioxane from water using solid-phase microextraction coupled with gas chromatography and gas chromatography-mass spectrometry

In this study, two methods are developed for the extraction of 1,4-dioxane (dioxane) from water using 80-microm carboxen-polydimethylsiloxane solid-phase microextraction fibers followed by either gas chromatography (GC)-flame ionization detection (FID) or GC-mass spectrometry (MS). With GC-FID, the lower limit of detection (LOD) for 1,4-dioxane is 2.5 microg/L (ppb) with a linear range of 5 to 10,000 microg/L, obtained by immersing the fiber in the sample for 20 min with agitation. Using GC-MS, the lower limit of quantitation is 0.5 microg/L, and the LOD is 0.25 microg/L. The upper linear range limit is 100 microg/L. Samples are extracted in 20 min using either heated headspace with agitation or direct immersion with agitation.     

A new approach based on a combination of direct and headspace cold-fiber solid-phase microextraction modes in the same procedure for the determination of polycyclic aromatic hydrocarbons and phthalate esters in soil samples

This study describes a new approach to cold-fiber solid-phase microextraction (CF-SPME) based on a combination of different extraction modes in the same extraction procedure. Also, the high quantity of water required to facilitate both the desorption of analytes from the matrix and their transport to the fiber coating is reported. The extraction mode was changed from the direct to the headspace mode in a single extraction while manipulating the extraction times and coating temperature to improve the extraction of compounds with different volatilities. Compounds with low volatility were better extracted in the direct mode, while the headspace mode was more appropriate for volatile compounds. Polycyclic aromatic hydrocarbons (PAHs) and phthalic acid esters (PEs) in sand or soil samples were used as model compounds and matrices in this study. The optimized conditions were: sample pH in the range of 4-7, addition of 12 mL of 194 g L(-1) aqueous NaCl solution in a 15 mL vial, and 80 min total extraction time with a sample temperature of 90°C (50 min in direct mode with coating at 90°C followed by 30 min in headspace mode with coating at 30°C). The proposed procedure was compared with conventional CF-SPME (with and without addition of water) and was found to be more effective for all the analytes, since it is capable of extracting both heavier and lighter compounds from soil samples in a single extraction procedure. The use of an excess of water and a combination of extraction modes in the same CF-SPME procedure are the main factors responsible for this enhancement. The proposed method was applied to the extraction of PAHs and PEs in spiked soil samples and excellent results were obtained for most of the compounds evaluated.     

Selective extraction of emerging contaminants from water samples by dispersive liquid-liquid microextraction using functionalized ionic liquids

Functionalized ionic liquids containing the tris(pentafluoroethyl)trifluorophosphate (FAP) anion were used as extraction solvents in dispersive liquid-liquid microextraction (DLLME) for the extraction of 14 emerging contaminants from water samples. The extraction efficiencies and selectivities were compared to those of an in situ IL DLLME method which uses an in situ metathesis reaction to exchange 1-butyl-3-methylimidazolium chloride (BMIM-Cl) to 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMIM-NTf(2)). Compounds containing tertiary amine functionality were extracted with high selectivity and sensitivity by the 1-(6-amino-hexyl)-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate (HNH(2)MPL-FAP) IL compared to other FAP-based ILs and the BMIM-NTf(2) IL. On the other hand, polar or acidic compounds without amine groups exhibited higher enrichment factors using the BMIM-NTf(2) IL. The detection limits for the studied analytes varied from 0.1 to 55.1 μg/L using the traditional IL DLLME method with the HNH(2)MPL-FAP IL as extraction solvent, and from 0.1 to 55.8 μg/L using in situ IL DLLME method with BMIM-Cl+LiNTf(2) as extraction solvent. A 93-fold decrease in the detection limit of caffeine was observed when using the HNH(2)MPL-FAP IL compared to that obtained using in situ IL DLLME method. Real water samples including tap water and creek water were analyzed with both IL DLLME methods and yielded recoveries ranging from 91% to 110%.     

Determination of phenolic compounds in dietary supplements and tea blends containing Echinacea by liquid chromatography with coulometric electrochemical detection

Analytical methodologies with ultrasonic extraction and liquid chromatography (LC) were developed for the determination of phenolic compounds in dietary supplements containing Echinacea. The phenolic compounds determined by these methods included caftaric acid, chlorogenic acid, cynarin, echinacoside, and cichoric acid. Samples from tablets, capsules, and bags of tea blends were extracted by sonication for < or = 30 min with methanol-water (60 + 40). The extracts were centrifuged and filtered, and the filtrates were diluted and analyzed by LC using a reversed-phase column and coulometric electrochemical (EC) detection. The mobile phase was acetonitrile-ammonium formate buffer, pH 3.5 (15.3 + 84.7) containing tetrabutyl ammonium hydrogen sulfate as an ion-pairing reagent. Extraction conditions (e.g., composition of the extraction solvent and sonication time) were optimized for different types of samples. Intra- and interday analytical variations were determined, and intraday analyses were performed by 2 independent analysts using 2 different LC systems. Results were generally comparable. The LC method with EC detection showed better sensitivity and selectivity when compared with LC with ultraviolet detection, although results were similar for the 2 methods for major compounds, i.e., caftaric acid, echinacoside, and cichoric acid. The identities of these major compounds found in samples were confirmed by LC/electrospray ionization mass spectrometry.     

Carbon stable isotope ratio of phloem sugars in mature pine trees throughout the growing season: comparison of two extraction methods

The study presents a comparison of two phloem sugar extraction methods. The amount of phloem sugar extracted and the carbon isotope composition (δ¹³C) of the total extracts and of the main phloem compounds separated by high‐performance liquid chromatography (sucrose, glucose, fructose and pinitol) are compared. These two phloem sap extraction methods are exudation in distilled water and a new method using centrifugation, which avoids the addition of any solvent. We applied both extraction methods on phloem discs sampled from 38‐year‐old Pinus pinaster trees in south‐western France throughout the period from June 2007 to December 2008 on different time‐scales: hourly, daily and monthly. We found that the centrifugation method systematically extracted ca. 50% less compounds from the phloem discs than the exudation method. In addition, the two extraction methods provided similar δ¹³C values of the total extracts, but the values obtained by the exudation method were 0.6‰ more negative than those calculated from the mass balance using the individual constituents. Over the growing season, both extraction methods exhibited lower total sugar content and more ¹³C‐enriched phloem sap in summer compared with winter values. These findings suggest that both extraction methods can be applied to study the carbon isotope composition of phloem sap, and the centrifugation method has the advantage that no solvent has to be added. The exudation method, however, is more appropriate for the quantification of the amounts of phloem sugars. Copyright © 2009 John Wiley & Sons, Ltd.     

Development of a simple hollow fibre supported liquid membrane extraction method to extract and preconcentrate dinitrophenols in environmental samples at ng L(-1) level by liquid chromatography

An easy and rapid hollow-fibre supported liquid membrane method (HFSLM) has been developed to extract and determinate the total concentration of four dinitrophenols in environmental water at ng L(-1) level. This extraction method provides a high selectivity, short extraction time and very low cost for real samples. It is a three-phase system, aqueous-organic-aqueous, where the organic solvent is held into the fibre pores, being in contact with the two other phases. The organic phase is formed by two different organic solvents, with two different polarities, n-undecane and toluene (1:1). The optimization step was performed using a three-variable Doehler design, involving three factors, stirring speed, fibre length and sample volume. The organic phase composition, as well as the pH of the acceptor and donor phases was also optimized. The extraction equilibrium was reached after 30 min, after which essentially the total amount (90-80%) of the four dinitrophenolic compounds were extracted from the sample. Better repeatability and reproducibility at the expense of lower enrichment factors was obtained compared with other methods, employing incomplete extraction during a fixed time. The matrix effect was tested by performing extractions from leachate water and river water. This method is linear in the range 0.1-100 microgL(-1) in different matrices, with detection limit around 100 ng L(-1), after extraction of 6 mL of sample and using high performance liquid chromatography for final analysis.     

Implementation of solid-phase microextraction with micellar desorption method for priority phenolic compound determination in natural waters

Eleven phenolic compounds considered by the Environmental Protection Agency to be priority pollutants are extracted and determined in different water samples. The method involves the extraction and clean-up step of target compounds by solid-phase microextraction and micellar desorption (SPME-MD) and a second step of determination by liquid chromatography with diode array detection. Different fibers and surfactants are evaluated for the analysis of these target analytes in water samples. In the optimum conditions for the SPME process, recoveries for the target compounds are between 80% and 109%; relative standard deviations are lower than 10%, and detection limits are in the range 0.3-3.5 ng/mL. The main advantages of this method are the combination of time and efficiency, safety, and an environmentally friendly process for sample extraction prior to instrumental determination. This demonstrates that SPME-MD can be used as an alternative to traditional methods for the extraction and determination of priority phenolic compounds in natural waters from different origins.     

Comparison of extraction procedures for the determination of arsenic and other elements in lobster tissue by inductively coupled plasma mass spectrometry

A variety of extraction procedures were evaluated for the extraction of arsenic and other analytes from lobster tissue samples using inductively coupled plasma mass spectrometry (ICP-MS) detection. Soxhlet, room temperature mixing, sonication, microwave assisted, supercritical carbon dioxide and subcritical water extractions were evaluated for a variety of solvent systems and optimum conditions determined using a partially defatted Lobster Hepatopancreas marine certified reference material, TORT-2 (National Research Council of Canada). The solubility trends and solvents into which the analytes extracted gave an indication as to the polar/non-polar nature of the compounds present. Analytes that prefer water are probably more polar or inorganic, while those preferring methanol solutions are less polar or organic in nature. Arsenic, cadmium, cobalt, molybdenum and selenium were probably all present in TORT-2 in both polar inorganic and non-polar organic forms. While TORT-2 may have contained similar amounts of selenium in both forms, the results suggested that more of the arsenic was present as less polar or more organic compounds, and cobalt existed mainly as more polar or inorganic species. Most of the extraction techniques suggested that, although there may be some less polar organic forms present, more of the cadmium was probably present as polar inorganic compounds. Additionally, most techniques indicated that molybdenum was possibly all less polar or more organic in nature. In general, microwave assisted extraction (MAE) yielded comparable or improved recoveries for all of the analytes monitored and usually required less solvent. Additionally, MAE proved to be the mildest, fastest, least complicated and most reproducible extraction technique evaluated. MAE at 75 degrees C for 2 min exposure time yielded quantitative recovery of arsenic from TORT-2. These conditions were evaluated for lobster tissue samples purchased from a local restaurant. Separate evaluation of the lobster meat and organs resulted in quantitative recoveries of arsenic from both tissue samples. The results indicated that the extraction efficiencies might have some dependence upon the extraction technique, extraction conditions, analyte, solvent, and sample matrix.     

Magnetic solid‐phase extraction or dispersive liquid–liquid microextraction for pyrethroid determination in environmental samples

The determination of 15 pyrethroids in soil and water samples was carried out by gas chromatography with mass spectrometry. Compounds were extracted from the soil samples (4 g) using solid–liquid extraction and then salting‐out assisted liquid–liquid extraction. The acetonitrile phase obtained (0.8 mL) was used as a dispersant solvent, to which 75 μL of chloroform was added as an extractant solvent, submitting the mixture to dispersive liquid–liquid microextraction. For the analysis of water samples (40 mL), magnetic solid‐phase extraction was performed using nanocomposites of magnetic nanoparticles and multiwalled carbon nanotubes as sorbent material (10 mg). The mixture was shaken for 45 min at room temperature before separation with a magnet and desorption with 3 mL of acetone using ultrasounds for 5 min. The solvent was evaporated and reconstituted with 100 μL acetonitrile before injection. Matrix‐matched calibration is recommended for quantification of soil samples, while water samples can be quantified by standards calibration. The limits of detection were in the range of 0.03–0.5 ng/g (soil) and 0.09–0.24 ng/mL (water), depending on the analyte. The analyzed environmental samples did not contain the studied pyrethroids, at least above the corresponding limits of detection.     

Ion chromatographic methods for the detection of starch hydrolysis products in ruminal digesta.

Dionex high-performance ion chromatographic methods were evaluated for separation and quantitation of plant sugars and starch digestion products in the ruminal digesta of cattle. Mono- and disaccharides were eluted from a Dionex CarboPac PA1 column with sodium hydroxide used isocratically or as a pH gradient. Maltooligosaccharides which had a degree of polymerization (DP) less than 30 glucose residues were eluted in 60 min by a sodium hydroxide eluent containing a sodium acetate gradient. Carbohydrates were detected amperometrically. Responses were linear (r2 greater than 0.99) for glucose, disaccharides and maltooligosaccharides (DP less than 8). Precipitation and solid-phase extraction methods were evaluated for clean-up of samples of feedstuffs, ruminal contents, and bacterial culture fluids. Perchloric acid precipitation hydrolyzed sucrose but did not affect recoveries of cellobiose, isomaltose or maltose. Ethanol in concentrations of 79 and 86% precipitated maltooligosaccharides having chain lengths larger than 14 and 9 glucose residues, respectively. Maltooligosaccharide recoveries from solid-phase extraction columns varied with maltooligosaccharide size and column packing. Recoveries were greater than 94% for short chains (DP less than 6) eluted from phenyl-substituted columns and variable for all oligosaccharides eluted from C18 columns. Applications of these methods are presented and include: (1) detection of sugars in ruminant feed, (2) monitoring changes in ruminal sugars after feeding and (3) monitoring changes in extracellular sugars and oligosaccharides in the culture fluids of the ruminal bacterium, Bacteroides ruminicola.     

Extracted sweet sorghum substrates as a source of fermentable sugars

Simple sugars of variously prepared sweet sorghum culms were extracted to different extents depending upon water temperature, extraction time, and size of the culm substrate. Sonication of succulent culms (≤15 mm split sections) suspended in water followed by centrifugation extracted 88% of the available sugars. However, hot water extraction of freeze-dried and milled sorghum quantitatively extracted the simple sugars, which were 2/3 sucrose and 1/3 glucose and fructose. Following the sugar removal, the residue was extracted with a 12% NaOH solution to leave a cellulosic residue that was nearly quantitatively converted (98%) to glucose by enzymatic hydrolysis. Ninety percent of the pentosans in the culms were extracted by the alkali treatment, and then 91% of these pentosans were precipitated from the alkaline extract with acidified ethanol.     

Micro-scale quantitation of ten phthalate esters in water samples and cosmetics using capillary liquid chromatography coupled to UV detection: effective strategies to reduce the production of organic waste

We have extracted ten phthalate esters (C1 to C8) using six different micro-scale methods for extraction, and then separated them by capillary liquid chromatography coupled to UV detection. The methods included liquid-liquid extraction, ultrasonic-assisted extraction, microwave-assisted extraction, dispersive liquid-liquidmicroextraction, dispersive liquid-liquid microextraction solidification of floating organic droplets, and cloud point extraction. The linear range of the analytes is from 0.5 to 50 μg mL^?1, and the detection limits range from 0.02 to ~0.17 μg mL^?1. The precision and accuracy of all intra- and inter-day analyses are <5.5%. We find that dispersive liquid-liquid microextraction solidification of floating organic droplet (DLLME-SFO) is the best method for quantification of most phthalate esters in water samples and cosmetics because of its low limit of detection and high extraction efficiencies.

Determination of pesticide residues in coconut water by liquid-liquid extraction and gas chromatography with electron-capture plus thermionic specific detection and solid-phase extraction and high-performance liquid chromatography with ultraviolet detection

Two simple methods were developed to determine 11 pesticides in coconut water, a natural isotonic drink rich in salts, sugars and vitamins consumed by the people and athletes. The first procedure involves solid-phase extraction using Sep-Pak Vac C18 disposable cartridges with methanol for elution. Isocratic analysis was carried out by means of high-performance liquid chromatography with ultraviolet detection at 254 nm to analyse captan, chlorothalonil, carbendazim, lufenuron and diafenthiuron. The other procedure is based on liquid-liquid extraction with hexane-dichloromethane (1:1, v/v), followed by gas chromatographic analysis with effluent splitting to electron-capture detection for determination of endosulfan, captan, tetradifon and trichlorfon and thermionic specific detection for determination of malathion, parathion-methyl and monocrotophos. The methods were validated with fortified samples at different concentration levels (0.01-12.0 mg/kg). Average recoveries ranged from 75 to 104% with relative standard deviations between 1.4 and 11.5%. Each recovery analysis was repeated at least five times. Limits of detection ranged from 0.002 to 2.0 mg/kg. The analytical procedures were applied to 15 samples and no detectable amounts of the pesticides were found in any samples under the conditions described.     

Static pressurised liquid extraction of nitrated polycyclic aromatic hydrocarbons from soils with on-line filtration-preconcentration prior to gas chromatography-mass spectrometry detection

Nitrated polycyclic aromatic hydrocarbons have been extracted from both spiked and natural contaminated soils by using static pressurised liquid extraction. The variables governing the extraction (namely, pressure, extraction time, temperature and number of static extraction cycles) have been optimised using the experimental design methodology. A laboratory-made pressurised liquid extractor has been used allowing its coupling to a filtration-preconcentration system through a flow injection interface, thus providing a partially automated approach. Gas chromatography with MS-MS ion preparation mode has been used for individual separation-identification/quantification providing both high selectivity (no interferences were observed) and sensitivity (detection limits of low pg). The comparison of the proposed approach with the reference EPA Method 3540 has shown that both methods provide similar efficiencies but with dramatic saving of time by the former (30 min vs. 24 h). The use of water as leaching agent avoids the use of organic solvents, thus providing an environmentally friendly method.     

Determination of endocrine disruptors in environmental waters using poly(acrylamide-vinylpyridine) monolithic capillary for in-tube solid-phase microextraction coupled to high-performance liquid chromatography with fluorescence detection

A method for the determination of endocrine disruptors, bisphenol A and 17alpha-ethinylestradiol, in environmental water samples was developed using in-tube solid-phase microextraction followed by liquid chromatography and fluorescence detection. A poly(acrylamide-vinylpyridine) monolithic capillary column was applied as the extraction media in view of its greater phase ratio than open-tubular capillaries and thus higher extraction efficiency. After optimizing the extraction conditions, bisphenol A and 17alpha-ethinylestradiol were extracted directly from water samples in a wide dynamic linear range of 0.5-1000 ng mL(-1), with the detection limits obtained as 0.064 and 0.12 ng mL(-1), respectively. The precision of the method was satisfactory with the intraday and interday RSD values smaller than 7.2%. Environmental water samples of different sources were successfully analyzed with the presented method and the monolithic capillary was proved to be robust and reusable in analyzing real water samples.