Phenols In Aqueous Samples Research Articles

Amino‐Functionalized Metal Organic Framework‐Based Dispersive Micro‐Solid‐Phase Extraction Coupled With HPLC for Sensitive Quantification of Bisphenol A and Alkyl Phenols in Aqueous Samples

ABSTRACTA sensitive analytical procedure for simultaneous extraction and determination of bisphenol A and alkyl phenols, namely, 4‐sec‐butylphenol, 4‐tert‐butylphenol, and 4‐tert‐amylphenol from aqueous samples with metal–organic framework (MOF)‐based dispersive micro‐solid‐phase extraction (D‐µSPE) and high‐performance liquid chromatography (HPLC) technique is developed. Sample contaminants were preconcentrated with amino‐functionalized aluminum MOF and later eluted with acetonitrile. The reconstituted sample was subjected to HPLC analysis. Various procedural parameters related to D‐µSPE were optimized. Under optimized preconcentration and chromatographic conditions, calibration curves with excellent linearity (R2 > 0.9986) in the working range of 0.25–100 ng mL−1 were prepared. Limit of detection (S/N = 3) for every analyte within the range of 0.020–0.022 ng mL−1 was obtained. Analyte's recovery 91.16%–97.01% (RSD = 1.02–3.01) for intraday and 89.86%–95.83% (RSD = 1.15–3.13) for inter‐day analysis was obtained from real water samples.

Development of an ultra-high-performance supercritical fluid chromatography method for the analysis of phenols in the pyrolysis aqueous fraction.

The pyrolysis process consists of the thermal decomposition of biomass in an inert atmosphere, which produces a liquid (bio-oil) composed of a complex mixture of organic compounds, including an oil and water phase. The aqueous fraction can reach up to 45% w/w, and understanding its composition is of utmost importance in determining its intended destination, whether for the reuse of compounds in industrial applications or for treating the effluent for disposal. In this study, a fast, direct, and efficient method using ultra-high-performance supercritical fluid chromatography (UHPSFC) was developed and optimized for monitoring phenols in aqueous samples obtained from the pyrolysis processing of six different biomass sources. The following parameters were evaluated for method optimization: stationary phase type, mobile phase flow, organic modifier, sample diluent, temperature, pressure, and modifier gradient time. With a total analysis time of 26min, out of the fourteen (14) investigated phenolic compounds, eleven (11) were successfully separated after method optimization, and among them, five (5) were quantified in all six aqueous fractions. The aqueous fractions of residue from cowpea pod (1.89mg.mL-1), sugar apple (3.09mg.mL-1), and acerola (4.79mg.mL-1) presented lower concentrations compared to grape (8.16mg.mL-1), pine nuts (6.68mg.mL-1), and guava (6.05mg.mL-1) fractions. However, even at lower concentrations, all biomasses showed promising results regarding the phenolic compound content, analytes that have high added value for the chemical industry.

СЕНСОРНЫЙ КОМПОЗИТ НАНОВОЛОКНА γ-Al2O3 / НАНОАЛМАЗЫ / Cu2+ С УВЕЛИЧЕННОЙ КАТАЛИТИЧЕСКОЙ АКТИВНОСТЬЮ ДЛЯ ДЕТЕКЦИИ ФЕНОЛОВ В ВОДНОЙ СРЕДЕ

A functionalized composite γ-Al2O3 nanofibers / nanodiamond / Cu2+ with improved sensor properties for the detection of phenols in an aqueous medium was obtained by chemical modification with copper ions of a new composite material based on alumina nanofibers and nanodiamonds. The chemical modification of the composite made it possible to increase its catalytic activity more than twice in the co-oxidation of phenols with 4-aminoantipyrine in the presence of H2O2. The obtained effect enabled to reduce the threshold of the minimum detectable concentration of analytes by half when they were tested using a functionalized composite. What was demonstrated by the example of the detection of phenol and 4-chlorophenol. It was shown that the obtained composite provides a linear response in a wide range of concentrations of phenol (0.25–100 μM) and 4-chlorophenol (0.5–25 μM). It is found that the adsorbed Cu2+ ions are firmly bound to composite surface, are not desorbed, and are not inactivated by co-oxidation reagents during repeated use of the composite. The applicability of a functionalized composite as a reusable sensor was shown in model experiments in the course of sequential multiple testing of phenol in aqueous samples. Comparative studies of the kinetics and isotherms of adsorption of Cu2+ ions on a composite material and an alumina matrix, and estimation their sorption capacity were also carried out in the work.

The effect of copper and iron adsorption on the catalytic performance of alumina nanofiber / nanodiamond composite in sensing applications

Phenolic compounds are common environmental pollutants, which are used in many industries and contaminate water environment due to industrial wastewater discharge. Presently, there is an increasing demand for the development and improvement of inexpensive, easy-to-use analytical tools for in-situ detection of phenolic compounds. In this work, we investigate the effect of adsorption of Cu2+ and Fe2+ ions on the catalytic activity of a composite material based on alumina nanofibers (ANF) and detonation nanodiamonds (DND) in the co-oxidation of phenols with 4-aminoantipyrine in the presence of hydrogen peroxide. We have found more than two-fold increase of the catalytic activity for ANF + DND + Cu composite, while the activity of ANF + DND + Fe composite is found to decrease by several times in comparison with the original ANF + DND material. The results of FTIR analysis indicate that the adsorption of iron ions occurs with the formation of hydroxide surface groups and hydrogen bonds, which apparently block their catalytic activity in the Fenton redox cycle. The higher catalytic performance of AND + DND composite functionalized with copper ions makes it possible to detect two times lower concentrations of analytes (phenol and 4-chlorophenol) in comparison with the original composite. It is shown that the AND + DND + Cu composite provides a linear yield of the co-oxidation reaction product in a wide range of analyte concentrations (0.25–100 μM for phenol and 0.5–25 μM for 4-chlorophenol). Model experiments demonstrate the applicability of copper-functionalized composite as a reusable sensor for the determination of phenol in aqueous samples.

Reusable System for Phenol Detection in an Aqueous Medium Based on Nanodiamonds and Extracellular Oxidase from Basidiomycete Neonothopanus nambi.

A reusable system for phenol determination in an aqueous medium was obtained by adsorption of extracellular oxidase from fungus Neonothopanus nambi onto modified nanodiamonds (MND) synthesized by detonation. It was found that the enzyme strongly binds to MND and exhibits catalytic activity in the reaction of co-oxidation of phenol with 4-aminoantipyrine without the addition of hydrogen peroxide. In the presence of the MND-oxidase complex, a significantly (by an order of magnitude) higher yield of the reaction product is recorded as compared to the yield in the presence of a free enzyme; the mechanism of the revealed effect is discussed. Model experiments have demonstrated the multiple use of the MND-oxidase complex for testing phenol in aqueous samples. The immobilized enzyme exhibits functional activity during long-term (2 months) storage of the MND-oxidase complex at 4°C. The data obtained create the prerequisites for using the created system in environmental monitoring of water pollution with phenol.

A simple strategy based on fibers coated with surfactant-functionalized multiwalled carbon nanotubes to improve the properties of solid-phase microextraction of phenols in aqueous solution

Methods and experimentsIn this study, a functionalized multiwalled carbon nanotube (MWCNT)-coated solid-phase microextraction (SPME) fiber was developed for concentrating analytes in aqueous samples. Sodium deoxycholate (NaDC) was used as a dispersing agent for non-covalent modification of MWCNTs. The coating showed porous structure and large adsorption capacity. To investigate the capability of this MWCNTs/NaDC SPME fiber, it was applied to the analysis of phenols in aqueous solution. After extraction, the analytes were desorbed in an acetonitrile–water solution and analyzed using high-performance liquid chromatography.ResultsThe MWCNTs/NaDC fiber exhibited good analytical performance, and fine preparation reproducibility was obtained with the relative standard deviations (RSDs) ranging from 4.9% to 10.2% (n = 6) in one batch, from 5.7% to 11.9% (n = 3) among different batches. Under the optimum extraction conditions, the detection limits were 0.15–0.30 ng/mL(S/N = 3), the linear detection ranges were 1–100 ng/mL (R2 ≥ 0.9997) for these analytes, and good recoveries (80.3–95.4%) were obtained for the spiked samples.ConclusionThis is a simple and accurate pretreatment method for the analysis of phenols in aqueous samples.

Orthogonal array design optimisation of an in situ ionic liquid dispersive liquid–liquid microextraction for the detection of phenol and endocrine-disrupting phenols in aqueous samples

In this paper, a dispersive liquid–liquid microextraction (DLLME) based on the application of in situ ionic liquids (in situ ionic liquid DLLME) was developed for preconcentration and determination of trace amount of phenol and endocrine-disrupting phenols in aqueous samples. The experimental parameters of an in situ ionic liquid DLLME method were investigated and optimised using an orthogonal array design. Several factors affecting extraction efficiency, including percentage concentration of the ionic liquid, the ratio of ionic liquid to the ion exchanger, extraction time as well as centrifugation time, were investigated and optimised. Under the optimal conditions, percentage concentration of the ionic liquid of 5%, the ratio of ionic liquid to the ion exchanger of 1–2, the extraction time of 5 min and centrifugation time of 1 min, the method affords satisfactory recoveries in the range of 99–100%. Consistent repeatability (RSD ≤ 5%) with satisfactory linearity (0.9993 ≥ r2 ≤ 0.9999) of results illustrated a good performance of the present method. The method was applied to the determination of endocrine-disrupting phenols in real seawater samples. The relative recovery of spiked, natural seawater samples was higher than 97%.

Fabrication of a composite based on aluminum oxide nanofibers and nanodiamonds to construct phenol detection systems

A composite based on aluminum oxide nanofibers (AONF) and modified nanodiamonds (MND) synthesized by explosion technique was made by mixing aqueous suspensions of components at a 5:1 weight ratio and incubating the mixture for 15 minutes at 32 C. It is assumed that the formation of a composite is provided by the difference in the zeta-potentials of the components - negative for MND and positive for AONF. Vacuum filtration of the mixture through a fluoroplastic filter (pore diameter of 0.6 m) formed discs with a diameter of 40 mm with subsequent heat treatment at 300 C to impart structural stability to the composite. Using scanning electron microscopy (SEM), it was revealed that the resulting composite has a network structure in which the MND particles are distributed over the AONF surface. It was established that MND incorporated into the composite catalyze the azo coupling reaction (phenol - 4-aminoantipyrine - H2O2) with the formation of a colored product (quinoneimine). The applicability of the composite for the multiple detection of phenol in aqueous samples is demonstrated.

A graphene oxide-based polymer composite coating for highly-efficient solid phase microextraction of phenols

Sensitivity and selectivity of the solid phase microextraction (SPME) in analysis are mostly determined by the coating material of the fiber used. Graphene oxide (GO) has attracted great attention because of its large specific surface area, rich oxygen functional groups, good dispersibility in aqueous solution and high reactivity. However, the low thermal stability of the functional groups limits the wide application of GO in SPME coating design. Highly cross-linked polyoxyethylene (POE) is a substrate widely used for composite material construction, which could significantly improve the thermal stability, water resistance as well as biocompatibility of the functional materials. In this study, we incorporated GO with highly cross-linked POE as a novel fiber coating material for SPME through the gluing approach. The obtained fiber possessed a wrinkled shape surface, which could increase the accessible surface area. In addition, the thermal and chemical stability of the fiber coating were also improved, rendering the fiber rigid enough for more than 100 repetitive extraction cycles. The performance of this developed SPME method for phenols was evaluated by headspace extraction of phenols in aqueous samples. Compared with three commercial fibers, the home-made fiber showed excellent extraction efficiencies towards phenols. Under the optimized conditions, it showed low detection limits (0.12–1.36 ng· L−1), good precision (<8.4%), good fiber-to-fiber repeatability (3.1%–8.1%), wide linear range (almost 5–1000 ng·L−1and correlation coefficients (R2) >99%), as well as good enrichment efficiencies (enrichment factors (EFs), 172–1752). Furthermore, the method was successfully applied in simultaneous analyses of five phenols for real water samples with satisfactory recoveries (81–113% for the Pearl River samples).

Development and application of a simultaneous SPE-method for polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, heterocyclic PAHs (NSO-HET) and phenols in aqueous samples from German Rivers and the North Sea

Polycyclic aromatic hydrocarbons (PAHs), heterocyclic PAHs (NSO-HETs), alkylated PAHs and phenols are known as the prevailing contaminants in groundwater at tar contaminated sites. Besides these local sources, the concentrations and the distribution in particular of NSO-HETs in environmental samples, such as rivers, have received notably less attention. To investigate their occurrence in river basins two sensitive analytical methods for the simultaneous extraction of 86 substances including NSO-HETs, classical EPA-PAHs, alkylated PAHs and phenols were developed: liquid–liquid extraction for the whole water phase and solid phase extraction for the dissolved water phase only. Solely GC–MS or additionally LC–MSMS for fractionated basic nitrogen heterocycles (N-HETs) were used for quantification. Limits of quantification were in the low ngL−1 range. Concentrations were determined in 29 aqueous samples from 8 relatively large rivers located in Lower Saxony (Germany) and the North Sea. NSO-HETs had comparable or even higher sum concentrations than EPA-PAHs. N-HETs, especially acridine and quinolines with concentrations of up to 20ngL−1 per substance, were predominant.

Determination of phenol by flow-injection with chemiluminescence detection based on the hemin-catalysed luminol–hydrogen peroxide reaction

This study established a novel flow injection (FI) methodology for the determination of phenol in aqueous samples based on luminol chemiluminescence (CL) detection. The method was based on the inhibition that phenol caused on the hemin-catalysed chemiluminescence reaction between luminol and hydrogen peroxide in alkaline solution. Optimum conditions and possible mechanisms have been investigated. The linear range was 2.0 × 10 −9 to 4.0 × 10 −7 g mL −1 for phenol. The proposed method is sensitive with a detection limit of 4.0 × 10 −10 g mL −1. The relative standard deviation for 11 measurements was 2.3% for 1.0 × 10 −7g mL −1 phenol. The method was applied for the determination of phenol in waste water samples. The results obtained compared well with those by an official method.

Selective and sensitive optical chemosensor for detection of Ag(I) ions based on 2(4-hydroxy pent-3-en-2-ylideneamine) phenol in aqueous samples

A selective and sensitive chemosensor, based on the 2(4-hydroxy pent-3-en-2-ylideneamine) phenol (HPYAP) as chromophore, has been developed for colorimetric and visual detection of Ag(I) ions. HPYAP shows a considerable chromogenic behavior toward Ag(I) ions by changing the color of the solution from pale-yellow to very chromatic-yellow, which can be easily detected with the naked-eye. The chemosensor exhibited selective absorbance enhancement to Ag(I) ions in water samples over other metal ions at 438 nm, with a linear range of 0.4–500 μM ( r 2 = 0.999) and a limit of detection 0.07 μM of Ag(I) ions with UV–vis spectrophotometer detection. The relative standard deviation (RSD) for 100 μM Ag(I) ions was 2.05% ( n = 7). The proposed method was applied for the determination Ag(I) ions in water and waste water samples.

A Novel Liquid-Liquid Microextraction Based on Solidification of Floating Organic Droplet Method for Determination of Phenols in Aqueous Samples

Pre-concentration and determination of 7 phenolic compounds in water samples has been achieved using a new liquid-liquid microextraction coupled HPLC-DAD. Microextraction efficiency factors have been investigated and optimized: 14 µL 1-undecanol micro drop exposed for 15 min floated on surface of a 20 mL water sample at 55°C, stirred at 1200 rpm, low pH level and saturated salt conditions. Under the selected conditions, limit of detection of 0.5- 3.0 µg L -1 (S/N=3) and linearity range of 0.3-870 µg L -1 have been obtained. A reasonable repeatability (RSD ≤ 10.1%, n=5) with satisfactory linearity (0.9992 ≥ r 2 ≥ 0.9973) of results illustrated a good performance of the present method. The relative recovery of different natural water samples was higher than 84%.

Towards development of colorimetric test-systems for phenols detection based on computationally-designed molecularly imprinted polymer membranes

Colorimetric test-system for the express-control of phenols content in water was developed. The system consisted of free-standing molecularly imprinted polymer (MIP) membranes which contained synthetic binding sites capable of phenol binding. The MIP membranes were obtained by co-polymerisation of a functional monomer (e.g. itaconic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylamide or methacrylic acid) with triethyleneglycoldimethacrylate and oligourethaneacrylate. Rational choice of the functional monomers was based on the results of computational modelling. The phenol-selective MIP membranes were used as a basis for the colorimetric test-system for measuring phenol in aqueous samples. Phenol molecules were selectively adsorbed by the MIP membranes and quantified using color reaction with 4-aminoantipyrine. The intensity of the membranes' staining was proportional to the phenol concentration in the analysed sample. The optimised colorimetric test-system based on MIP membranes demonstrated a low detection limit (50 nM), a wide working range — 50 nM–0.5 mM and an excellent storage stability at room temperature (12 months). As compared to the traditional methods of phenols detection the developed test-system is superior because of simplicity of operation, small size and low cost.

Preparation of solid-phase microextraction fiber coated with single-walled carbon nanotubes by electrophoretic deposition and its application in extracting phenols from aqueous samples

A novel solid-phase microextraction (SPME) Pt fiber coated with single-walled carbon nanotubes (SWCNTs) was prepared by electrophoretic deposition (EPD) and applied to the determination of phenols in aqueous samples by direct immersion (DI)-SPME-HPLC-UV. The results revealed that EPD was a simple and reproducible technique for the preparation of SPME fibers coated with SWCNTs without the use of adhesive. The obtained SWCNT coating did not swell in organic solvents nor strip off from substrate, and possessed high mechanical strength due to the strong Van der Waals attractions between the surfaces of the SWCNTs. The prepared SPME fiber was conductive since both SWCNT coating and Pt wire were conductive. Using Pt wire as substrate, the fiber was unbreakable. Owing to the presence of oxygenated groups on SWCNTs and the high surface area of SWCNTs, the SWCNT fiber was similar to or superior to commercial PA fiber in extracting the studied phenols from aqueous sample. A durability of more than 80 analyses was achieved for one unique fiber. Under optimized conditions, the detection limits for the phenols varied between 0.9 and 3.8ng/mL, the precisions were in the range of 0.7–3.2% (n=3), and linear ranges were within 10 and 300ng/mL. The method was successfully applied to the analysis of spiked seawater and tap water samples with the recoveries from 87.5 to 102.0%.

Oxidized multiwalled carbon nanotubes as a novel solid-phase microextraction fiber for determination of phenols in aqueous samples

A simple and environmentally friendly method for determination of seven phenols using solid-phase microextraction (SPME) coupled to high-performance liquid chromatography (HPLC) has been developed. Several materials were used as stationary phase of SPME fibers and an oxidized multiwalled carbon nanotubes material was found to be effective in carrying out simultaneous extraction of phenols in aqueous samples. Compared with the widely used commercially available SPME fibers, this proposed fiber had much lower cost, longer lifetime (over 150 times), shorter analysis time (30 min of extraction and 3 min of desorption time) and comparable or superior extraction efficiency for the investigated analytes. The extraction and desorption conditions were evaluated and the calibration curves of seven phenols were linear ( R 2 ≥ 0.9908) in the range from 10.2 to 1585 ng mL −1. The limits of detection at a signal-to-noise (S/N) ratio of 3 were 0.25–3.67 ng mL −1, and the limits of quantification calculated at S/N = 10 were 0.83–12.25 ng mL −1 for these compounds. The possibility of applying the proposed method to environmental water samples analysis was validated.

Development of a solid-phase microextraction method for the analysis of phenolic flame retardants in water samples

A solid-phase microextraction (SPME) method for the ultra-trace determination of brominated phenols in aqueous samples has been developed and is reported for the first time to the best of our knowledge. 3,5,3′,5′-tetrabromobisphenol A (TBBPA), the most widely used brominated flame retardant, and other phenolic flame retardants in commercial use, such as 2,4-dibromophenol (2,4-DBP), 2,4,6-tribromophenol (TBP) and pentabromophenol (PBP) have been included as target analytes. The analytical procedure involves the in situ acetylation-SPME and gas chromatography–mass spectrometry (GC–MS) determination of the target analytes. A multi-factor categorical experimental design was created to study the main parameters affecting the extraction efficiency, allowing also the evaluation of interaction effects between factors. The factors studied were type of fiber, extraction mode, exposing the fiber directly into the sample (DSPME) or into the headspace over the sample (HSSPME), and extraction temperature. Carboxen-polydimethylsiloxane (CAR-PDMS) fiber appeared to be the most suitable of the five fibers tested for the extraction of most compounds, excluding PBP and TBBPA for which polydimethylsiloxane (PDMS) was the most efficient coating. The highest response was achieved for both fibers sampling in headspace mode at 100 °C. In order to test the linearity of the method, calibration studies were performed with both CAR-PDMS and PDMS coatings. For both fibers, the method was linear in a range of 2 orders of magnitude, giving relative standard deviation (RSD%) below 10% for most compounds and detection limits at the low pg/mL level. In addition, the feasibility of the method for simultaneous determination of chlorinated and brominated phenols was studied. Finally, the method was applied to several real samples including tap water and effluent and influent waste water samples from an urban treatment plant, in which several phenolic compounds, such as phenol, methylphenols and chlorophenols, could be detected and quantified.

Pervaporation-flow injection analysis of phenol after on-line derivatisation to phenyl acetate

A reverse pervaporation-flow injection (rPFI) method coupled with on-line derivatisation was developed for the determination of trace phenol in aqueous samples. On-line rPFI derivatisation was performed by direct injection of acetic anhydride into a donor stream of standard or sample phenol solution, which had been merged upstream with an alkaline concentrated sodium chloride stream. The reaction mixture was passed through a mixing chamber to generate phenyl acetate, which was then transported to the pervaporation unit. After evaporation into the headspace of the pervaporation unit, phenyl acetate diffused through a hydrophobic membrane into a static alkaline solution in the acceptor chamber where it was trapped for 15 min. Phenyl acetate was converted to phenolate ions and then transported to an electrochemical detector where it was analysed amperometrically at a glassy carbon electrode at +0.62 V (versus Ag/AgCl). The calibration plot was linear over the range of 50–1000 μg l −1 with a sample throughput of 4 h −1. The detection limit was determined to be 25 μg l −1 and 4.85% R.S.D. for n=6 (at 1000 μg l −1). This new method was applied to the analysis of several samples and the data compared with those obtained by the standard 4-aminoantipyrine (4-AAP) method and reversed-phase HPLC.

Determination of phenol in water by pervaporation–flow injection analysis

A pervaporation–flow injection method for the determination of phenol in aqueous samples is described. The method involves sample injection into a concentrated sodium chloride (25 wt.%) donor stream at pH 2 and stopping the flow of the acceptor stream containing 0.1 M KNO 3 and 0.01 M NaOH in the acceptor chamber of the pervaporation unit for 12 min. This period allows the completion of phenol transfer from the headspace of the donor chamber of the pervaporation unit through the membrane into the static solution in the acceptor chamber. After restarting the flow through the acceptor chamber the phenol concentration is detected amperometrically at a glassy carbon electrode set at +0.6 V. At 20°C the linear detection range was found to be 1–50 mg l −1 with R.S.D. varying between 1 and 4% for n=3. The detection limit and sample throughput were determined as 0.9 mg l −1 and 5 h −1, respectively. Excellent agreement with the standard 4-aminoantipyrine (4-AAP) method was observed when validating the method with lake samples containing suspension and spiked with phenol.

Automated derivatization for on‐line solid‐phase extraction‐gas chromatography; phenolic compounds

AbstractAn automated system for derivaatization was coupled on‐line with solid‐phase extraction‐gas‐chromatography (SPE‐GC). The system was optimized for the determination of phenol and chlorinated phenols in aqueous samples. The test analytes were acetylated with acetic anhydride; proper buffering of the sample was a critical factor. Next, the phenol acetates were enriched on a SPE cartridge and transferred to a GC; two appraoaches were studied. In the first approach, the derivatives were enriched on disposable C18 cartridges (ASPEC type) and desorbed with methylacetate. Aan aliquot of the final eluate was injected on‐line the GC by means of a loop‐type interface. In the second approach, trace enrichment was performed on 10 × 2 mm i.d. LC‐type precolumn packed with polystyrenedivinylbenzene copolymer (PLRP‐S) this precolumn was dried with a mitrogen purge and the phenol acetates were desorbed with ethyl acetate which was injectedon‐line into the retention gap of the GC under partially concurrent solvent evaporation (PCSE) conditions. The Derivatization‐SPE‐GC system which was based on the loop‐type interface has the advantage of simplicity and easy operation, the main drawback is the impossibility to determine phenol acetates which elute prior to trichlorophenol acetates. With the derivatization‐SPE‐GC approach using PCSE‐based desorption, even the most volatile analyte of the test series, phenol acetate, can be determined successfully. The entire procedure, including the derivatization step, was fully automated and integrated in one set‐up. The precision data for the integrated on‐line derivatization‐SP‐FID system were fully satisfactory, with RSD values of 1–12 % at the 1 μg/1 level. When a sample volume of 2.2 ml was analyzed, The detection limits for the chlorinated phenol acetates were in the 0.1–0.3 μg/1 range.