Determination of linear alkylbenzensulfonates in aqueous matrices by ion-pair solid-phase microextraction-in-port derivatization-gas chromatography-mass spectrometry

Trace determination (low ng/ml) of linear alkylbenzensulfonates (LASs) in water was achieved by solid-phase microextraction (SPME) of ion-pairs formed with tetrabutylammonium. This ion-pairing reagent served two purposes. First, it allowed the extraction of LAS with the polydimethylsiloxane fiber by counterion association and second, the derivatization of the formed LAS ion pairs in the GC injection port at 300 degrees C to form the corresponding sulfonated butyl esters. The methodology developed allows the isomer specific determination of LAS at low detection limits (0.16-0.8 ng/ml), depending on the alkyl chain lengths of LASs with RSDs of 10-12%. Furthermore, the developed methodology was applied to urban wastewater and sea water and compared with a solid-phase extraction (SPE) method (e.g. C18 and strong anion-exchange sorbent) to obtain concordant values for urban wastewater. Moreover, the developed SPME methodology overcame the procedural blank and matrix-dependent recoveries found in the SPE methodologies at low LAS concentrations.     

Trace Determination of Benzalkonium Chlorides in River and Wastewater by Capillary Electrophoresis following Solid‐Phase Extraction Coupled with Salting‐Out Extraction

Trace levels analysisbenzalkonium chlorides (BAKs) in river water and wastewater treatment plants (WWTP) effluents were determined by capillary electrophoresis (CE) following solid‐phase extraction (SPE) and salting‐out extraction. Salting‐out extraction using an appropriate ratio of sodium chloride (NaCl) and acetonitrile (ACN) mixed with concentrated SPE elutant was capable of providing more than 500‐fold enhancement in detection sensitivity. The ratios of ACN and NaCl for salting‐out extraction were investigated and optimized. Matrix interference was eliminated by salting‐out extraction. Limits of quantitation of BAK homologues were achieved at 0.1 μg/L in 250 mL water samples. Recoveries of BAKs in various spiked water samples ranged from 70% to 84% with relative standard deviation (RSD) less than 9%. Trace amounts of total BAKs were detected in river water and WWTP effluent samples ranging from 27 to 145 μg/L at the first time by CE.     

Analysis of linear alkylbenzenesulfonates in water samples by large-volume injection-port derivatization and gas chromatography-mass spectrometry.

This work presents a modified method to analyze linear alkylbenzenesulfonates (LASs) in water samples. The method involves extraction of samples by a graphitized carbon black (GCB) cartridge, and direct derivatization in the GC injection port using a large-volume (10-20 microl) direct sample introduction (DSI) device with tetraalkylammonium (TAA) salts. The analytes were then identified and quantitated by ion-trap GC-MS. The large-volume DSI injection-port derivatization technique provides sensitivity, fast and reproducible results for LAS residues, to quantitation at 0.1 microg/l in 200 ml of water samples. The retention effect of TAA salts in the injection port was not detected. Enhanced selected mass chromatograms of [M-55]+ ions of butylated C10-C13 LASs by electron impact ionization MS allows one to determine LAS residues at trace levels in environmental samples. Recovery of total LASs in spiked variety water samples ranged from 89 to 112% while RSDs ranged from 2 to 13%.     

Reversed-phase high-performance liquid chromatographic determination of linear alkylbenzenesulphonates in river water at ppb levels by precolumn concentration.

A high-performance liquid chromatography method for the determination of linear alkylbenzenesulphonates (LASs) in river waters has been developed. The ppb levels of LASs can be determined by reversed-phase high-performance liquid chromatography with ultraviolet detection after on-line anion-exchange concentration and successive injection. LASs were quantitatively concentrated on the anion-exchange precolumn and easily cleaned up from river water matrix, because of its specific affinity, for the anion-exchange resin. A weak non-polar reversed-phase column was useful for the determination of LASs. The relationships between concentration and summation of peak areas were linear from 10 to 200 ppb for total LAS concentrated from 5 ml of standard solutions. Overall recovery for total LAS was found to be 99%. Total LAS in the Tama River waters was determined to be around 100 ppb by the proposed method.     

Determination of non-ionic polyethoxylated surfactants in wastewater and river water by mixed hemimicelle extraction and liquid chromatography-ion trap mass spectrometry

The capability of hemimicelles-based solid phase extraction (SPE)/liquid chromatography/atmospheric pressure chemical ionisation in positive mode, ion trap mass spectrometry (LC/(APCl+-IT)-MS) for the concentration, separation and quantitation of non-ionic surfactants has been investigated. Concentration was based on the formation of mixed aggregates of analytes [alkylphenol ethoxylates (APE, octyl and nonyl) and alkyl ethoxylates (AE, C12-C16)] with the anionic surfactant sodium dodecyl sulphate (SDS) that is adsorbed on alumina. Parameters affecting SPE were investigated on the basis that hemimicelles are dynamic entities in equilibrium with the aqueous phase. The performance of ion trap mass spectrometry for MS and MS/MS quantitation of non-ionic homologues was assessed. Recoveries of analytes from wastewater influent and effluent and river water samples ranged between 91 and 98% and were found independent on the length of the alkyl chain under the optimised conditions. Anionic surfactants did not interfere to the levels found in environmental samples. The detection limits ranged between 14 and 111 ng/l for wastewater influent, 10 and 40 for wastewater effluent and 4 and 35 for river water, after concentration of 250, 500 and 750 ml of sample, respectively. The approach was applied to the determination of AE and APE in influent and effluent samples from four wastewater treatment plants and four river samples. The concentrations of individual non-ionic surfactants found ranged between 0.3 and 373 microg/l.     

Highly stable magnetic multiwalled carbon nanotube composites for solid-phase extraction of linear alkylbenzene sulfonates in environmental water samples prior to high-performance liquid chromatography analysis

The magnetic multiwalled carbon nanotubes (MMWCNTs) have been successfully prepared using a one-pot chemical coprecipitation method, in which magnetic nanoparticles (MNPs) were deposited onto multiwalled carbon nanotubes (MWCNTs) by in situ high temperature decomposition of the magnetic precursor of iron(III) in ethylene glycol media. A novel procedure for extraction of linear alkylbenzene sulfonates (LAS) as a model compound was thus developed in an off-line extraction system with detection by HPLC. The procedure includes the separation and preconcentration of LAS homologues onto MMWCNTs at pH 7.0 and their subsequent detection after sonication elution, followed by the separation of the MMWCNTs from the aqueous phase by external magnetic field and washing with ultra pure water. With a sample volume of 500 mL and 100 mg MMWCNTs sorbents, an enrichment factor of about 500, and a detection limit of 0.013-0.021 μg L(-1) were obtained within a linear range of 0.5-100 μg L(-1), together with a correlation coefficient of 0.9938-0.9998 for four LAS homologues. A precision of 2.4-5.6% was obtained for six replicate determinations of 50 μg L(-1) LAS. The recoveries of LAS homologues spiked in environmental water samples ranged from 87.3 to 106.3%, demonstrating the utility of the MMWCNTs adsorbents in a series of water samples. Stability testing demonstrated that the MMWCNTs remained 95.0% recovery for the target LAS even after a run of 50 adsorption and desorption cycles, showing their super operational stability. The MMWCNTs are promising adsorbents, suitable for the long-term repetitive sorption/desorption of target compounds in environmental water samples.     

Characterization and determination of linear alkylbenzenesulfonates in environmental water samples by high-performance liquid chromatography with a hydrophilic polymer column and electrospray ionization mass spectrometric detection.

A liquid chromatography-mass spectrometry (LC/MS) method was developed for the separation and determination of linear alkylbenzenesulfonates (C10-C14 LAS) in environmental water samples using a hydrophilic polymer column (Shodex Mspak GF-310 4D). This method involves a solid-phase extraction of the LAS samples with a Sep-Pak PS-2 cartridge. The LAS components were separated on the column with a mobile phase of 29% (w/v) acetonitrile-water containing 0.8 mM di-n-butylammonium acetate and 0.2 M acetic acid, and were detected by mass spectrometry with electrospray ionization. Detection limits of the developed method based on selected ion monitoring (SIM) technique for the C10-C14 LAS standards were 13-47 ng L(-1). The concentrations of the C10-C14 LAS in the environmental water samples ranged between 5-317 microg L(-1) for a river water sample and 0.4-6.4 microg L(-1) for a seawater sample. Linear relationships between the logarithms of retention factors and the alkyl chain lengths for each phenyl positional isomer of LAS could successfully be used for the identification of the isomer peaks.     

Differentiation and quantification of linear alkyl benzenesulfonate isomers by liquid chromatography-ion-trap mass spectrometry

Discrimination and quantitation of the 20 positional isomers of C10-C13 linear alkyl benzenesulfonates (LASs), based on the use of reversed-phase liquid chromatography-electrospray ionisation in negative ion mode ion-trap mass spectrometry, was undertaken. Discrimination was achieved by LAS MS-MS analysis into the ion trap, by monitoring specific fragment ions resulting from the benzylic cleavage of the carbon alkyl chain on both side of the LAS phenyl group. Parameters affecting the electrospray ionisation source and the ion-trap operation were optimised. Calibration curves for the different isomers were established and this permitted their quantitation by mass spectrometry for the first time. MS-MS responses were dependent on both the position of the phenyl group on the alkyl chain and the length of this alkyl chain, these responses being higher for the external isomers and the longer alkyl chain homologues. The precision, expressed as relative standard deviation ranged between 9 and 13%. Detection limits for LAS isomers were between 0.03 and 0.07 mg/l and therefore the method is sensitive enough to be applied to environmental samples.     

Analysis of tetrabromobisphenol A and other phenolic compounds in water samples by non-aqueous capillary electrophoresis coupled to photodiode array ultraviolet detection

Non-aqueous capillary electrophoresis (NACE) with large-volume sample stacking injection using the electroosmotic flow pump (LVSEP) has been developed for the determination of tetrabromobisphenol A (TBBPA) and other phenolic compounds in environmental matrices. Methanol has been used as run buffer solvent to reduce the electroosmotic flow (EOF). Identification and quantification of the analytes was performed by photodiode array ultraviolet detection. LVSEP-NACE improved sensitivity of the peak height by 90-300-fold. The method developed was applied to the analysis of TBBPA in river water and wastewater samples, using solid-phase extraction (SPE) as sample pretreatment process. The average recoveries of the analytes were in the range of 96-106% and 73-103% for 1 L of river water and 0.5 L of wastewater samples, respectively. When the method was based on off line SPE-LVSEP-NACE, sensitivity was improved by 3300-4500-fold and 1600-2200-fold for river water and wastewater samples, respectively.     

Carboxyl modified multi-walled carbon nanotubes as solid-phase extraction adsorbents combined with high-performance liquid chromatography for analysis of linear alkylbenzene sulfonates

Recently, multi-wall carbon nanotubes (MWCNTs) as adsorbents of solid-phase extraction are attractive because they can be used for enrichment of organic compounds and metal ions at trace levels. In this study, we use the carboxyl modified multi-wall carbon nanotubes (CMMWCNTs) as adsorbents of solid-phase extraction for extraction of linear alkylbenzene sulfonates (LAS), which are widely used anion surfactant with different homologues, and detected by HPLC-UV. The effect of eluent and its volume, sample pH and flow rate, sample volume and the ultrasonic time of sample, the content of the electrolyte (NaCl) were investigated and optimized. The detection limit for LAS homologues was 0.02-0.03 μg L⁻¹ with R.S.D. (n = 6) ranging from 2.04 to 10.03%. The recoveries of LAS homologues in the spiked environmental water samples ranged from 84.8 to 106.1%. The proposed method has been applied successfully to the analysis of LAS in aqueous environmental samples, which demonstrates that CMMWCNTs-based solid-phase extraction is a precision and convenient enrichment method and can be used for analysis of LAS homologues in water samples.     

The stability of non-ionic surfactants and linear alkylbenzene sulfonates in a water matrix and on solid-phase extraction cartridges

The stability of nonylphenol ethoxylates (NPEO), alcohol ethoxylates (AEO), coconut diethanol amides (CDEA) and linear alkylbenzene sulfonates (LAS) in a water matrix and preconcentrated on SPE cartridges was studied. A stability study was carried out in a water matrix (spiked ground water and real-world waste water) comparing different pretreatment procedures (addition of sulfuric acid to pH = 3, preservation with 1% and 3% of formaldehyde). When stored in a water matrix serious qualitative and quantitative changes occurred in waste water during the period of time studied (30 days). The losses of C12-C14 alcohol ethoxylates ranged from 72% to 88% when the sample was preserved with acid and from 17% to 86% when the sample was preserved with formaldehyde (3%). Simultaneously, an enrichment of the shorter alkyl chain homologues (C7EO and C10EO) was observed. The losses of NPEO were from 45% (sample preserved by acidification or by addition of 3% of formaldehyde) to 85% (sample preserved with 1% of formaldehyde). Additionally, an increase in concentration of polyethylene glycols (PEGs) and formation of different acidic forms, such as monocarboxylated (MCPEGs) and dicarboxylated polyethylene glycols (DCPEGs) were observed. The stability of surfactants preconcentrated on SPE cartridges was studied as a function of storage time and storage conditions (room temperature, 4 degrees C and -20 degrees C). The results indicate that disposable SPE cartridges can be recommended for the stabilization of non-ionic surfactants and LAS. Storage at -20 degrees C is feasible for long periods (up to 3 months for ground water and up to 2 months for waste water), while storage at 4 C can be recommended for a maximum of 1 month. When cartridges were kept at -20 degrees C the losses of AEOs (n = 12, 13 and 14), preconcentrated from waste water, ranged from 17 to 29% (after 60 days) and other compounds suffered small losses (maximum of 14% for C13LAS). At room temperature, after 7 days, the losses were less than 11%, indicating that shipping of samples by mail can be done without any special requirements.     

On-line solid phase extraction LC-MS/MS analysis of pharmaceutical indicators in water: A green alternative to conventional methods

A method using automated on-line solid phase extraction (SPE) directly coupled to liquid chromatography/tandem mass spectrometry (LC-MS/MS) has been developed for the analysis of six pharmaceuticals by isotope dilution. These selected pharmaceuticals were chosen as representative indicator compounds and were used to evaluate the performance of the on-line SPE method in four distinct water matrices. Method reporting limits (MRLs) ranged from 10 to 25 ng/L, based on a 1 mL extraction volume. Matrix spike recoveries ranged from 88 to 118% for all matrices investigated, including finished drinking water, surface water, wastewater effluent and septic tank influent. Precision tests were performed at 50 and 1000 ng/L with relative standard deviations (RSDs) between 1.3 and 5.7%. A variety of samples were also extracted using a traditional off-line automated SPE method for comparison. Results for both extraction methods were in good agreement; however, on-line SPE used approximately 98% less solvent and less time. On-line SPE coupled to LC-MS/MS analysis for selected indicators offers an alternative, more environmentally friendly, method for pharmaceutical analysis in water by saving time and costs while reducing hazardous waste and potential environmental pollution as compared with off-line SPE methods.     

LC-MS determination of linear alkylbenzene sulfonates and their carboxylic degradation products in influent and effluent water samples and sludges from sewage-treatment plants

Linear alkylbenzene sulfonates (LAS) have been determined in samples of the influent and the effluent, and in the sludge, from sewage-treatment plants (STP). LAS and sulfophenyl carboxylate compounds (SPC) were isolated by solid-phase extraction (SPE) with the polymeric phase Isolute ENV, then determined by liquid chromatography-electrospray mass spectrometry (LC-ESI-MS). The method enabled unequivocal identification of C10-C13 LAS by monitoring the ion at m/z 183 and the base peak corresponding to the [M-H]- ion. Average recoveries varied from 77-93% and the linear range of the method varied from 0.2 to 10 microg L(-1), with a limit of detection ranging from 10 ng L(-1) to 1.5 microg L(-1) when 200 mL waste water were preconcentrated. For sewage sludge, recoveries varied from 58 to 90% and the linear range was between 0.2 and 100 microg L(-1), with a detection limit ranging from 0.4 to 120 microg kg(-1) when 2.5 g sewage sludge was extracted. Unequivocal identification and determination of some metabolites of the LAS, the sulfophenyl carboxylate compounds (SPC), was achieved by monitoring [M-H]- ions.     

Simultaneous determination of isoflavones and lignans at trace levels in natural waters and wastewater samples using liquid chromatography/electrospray ionization ion trap mass spectrometry

A high-performance liquid chromatography/electrospray ionization ion trap mass spectrometry (HPLC/ESI-MSn) method has been developed for the trace determination of phytoestrogens in aquatic environmental samples. The method includes solid-phase extraction (SPE) and analysis using liquid chromatography/electrospray ionization ion trap mass spectrometry. The aquatic environmental samples, influent of a wastewater treatment plant (WWTP) and creek water, were adjusted to pH approximately 5 before extraction. The analyzed phytoestrogens were identified by an MSn method and quantified against a deuterated internal standard (genistein-3',5',6,8-D4). In negative ion mode, 0.1% formic acid was employed in acetonitrile/water mobile phase. The method detection limits ranged from 0.5 to 10 ng/L in WWTP influent and from 0.1 to 5 ng/L in creek water. Average SPE recoveries for the analyzed phytoestrogens ranged from 85 to 95%, with a relative standard deviation (RSD) (%) ranging from 3.9 to 6.5. The concentrations of the six analyzed phytoestrogens varied from 0.2 to 600 ng/L with high levels of enterolignans (enterolactone and enterodiol) found in the collected wastewater. The method is shown to be suitable for the determination of phytoestrogens in aquatic environmental samples at nano- and sub-nanogram per liter levels.     

Determination of linear alkylbenzene sulfonates by ion-pair solid-phase extraction and high-performance liquid chromatography

In this paper, the potential use of multiwalled carbon nanotubes (MWCNTs) as solid phase extraction (SPE) adsorbent was evaluated for preconcentration of linear alkylbenzene sulfonates (LAS) using ion-pair (IP)-SPE with tetrabutylammonium hydroxide (TBAH). The LAS homologues present in the aqueous sample were ion-paired with TBAH and the solution was passed through the MWCNT cartridges. The analytes retained in the cartridge were eluted with methanol and the concentrated methanol extract was analysed by HPLC-UV. In order to obtain the satisfactory recovery of LAS homologues, various parameters including the type and amount of the ion-pair reagents, the desorption and enrichment conditions such as the effect of eluent and its volume, pH, the flow rate, the ultrasonic time of sample, and the volume of sample solution were systematically optimized. Under the optimal conditions, LAS homologues could be easily extracted by the proposed SPE cartridge. The favorable limits of detection (LOD) for LAS homologues were in the range from 0.02 to 0.03 μg L⁻¹, and the relative standard deviations (RSDs) were 1.55-2.54% for 10 μg L⁻¹ LAS (n = 6). The proposed method has been successfully applied for the analysis of LAS homologues in aqueous environmental samples. A comparison study with ion-pair solid extraction on MWCNTs, C8 and C18 as adsorbents for LAS demonstrated that ion pair-based solid extraction on MWCNTs adsorbent was advantageous over C8 and C18, the widely used traditional adsorbents.     

Multiwalled carbon nanotubes as adsorbents of solid-phase extraction for determination of polycyclic aromatic hydrocarbons in environmental waters coupled with high-performance liquid chromatography

Multiwalled carbon nanotubes (MWCNTs) were used as a novel kind of solid-phase extraction adsorbents in this work as well as an analytical method based on MWCNTs solid-phase extraction (SPE) combined with high-performance liquid chromatography (HPLC) was established for the determination of polycyclic aromatic hydrocarbons (PAHs), some of which belong to typical persistent organic pollutants (POPs) owing to their carcinogenicity and endocrine disrupting activity. Several conditions that probably affected the extraction efficiency including the eluent volume, sample flow rate, sample pH and the sample volume were optimized in detail. The characteristic data of analytical performance were determined to investigate the sensitivity and precision of the method, and the method was applied to the determination of PAHs in environmental water samples such as river water sample, tap water sample and wastewater sample from the constructed wetland effluent. The experimental results indicated that there were excellent linear relationship between peak area and the concentration of PAHs over the range of 0.04-100 microg L(-1), and the precisions (RSD) were 1.7-4.8% under the optimal conditions. The detection limits of proposed method for the studied PAHs were 0.005-0.058 microg L(-1) (S/N=3). The recoveries of PAHs spiked in environmental water samples ranged from 78.7 to 118.1%. It was concluded that MWCNTs packed cartridge coupled with HPLC was an excellent alternative for the routine analysis of PAHs at trace level.     

Trace Determination of Rhodamine B and Rhodamine 6G Dyes in Aqueous Samples by Solid‐phase Extraction and High‐performance Liquid Chromatography Coupled with Fluorescence Detection

A simple and reliable method was developed to detect two basic synthetic dyes, rhodamine B (RB) and rhodamine 6G (R6G), in wastewater and surface water samples by high performance liquid chromatography with fluorescence detection (HPLC‐FLD). These dyes have been reported to be both mutagenic and carcinogenic in various organisms. The contents of these two dyes in water samples were extracted by Oasis HLB solid‐phase extraction (HLB‐SPE), and were then determined by an isocratic HPLC using an Atlantis® T3‐C18 column. Water samples at various pH conditions and the compositions of eluents for SPE were evaluated. The results indicate that the proposed method is precise and sensitive in analyzing these two basic synthetic dyes, and the limits of quantitation were 1.5 ng/L for RB and 0.3 ng/L for R6G in 100 mL of water samples. The recovery of analytes in spiked surface water and municipal wastewater treatment plant (WWTP) effluent samples ranged from 61 to 90% with the precision (RSD) ranging from 2 to 12%. The concentrations of analytes were detected in various water samples ranging from 0.7 to 81 ng/L.     

Application of graphene for the analysis of pharmaceuticals and personal care products in wastewater

A novel and reliable analytical method based on a graphene adsorbent for solid-phase extraction (SPE) derivatized with N-tert-butyldimethylsilyl-N- methyltrifluoroacetamide and analyzed by gas chromatography–mass spectrometry was developed for determination of nine pharmaceuticals and personal care products (PPCPs) in wastewater samples. Different ratios of graphene/silica gel were tested, with 20 % graphene/silica gel giving the best performance as an SPE adsorbent. The mean recoveries of the target analytes obtained by 20 % graphene/silica gel SPE ranged from 58.1 to 87.6 %. The limit of quantification ranged from 30 to 259 ng/L and from 13 to 115 ng/L for the influent and effluent, respectively. By comparing the accuracy and precision of 20 % graphene/silica gel and Oasis HLB SPE cartridges, we demonstrated that the method can be satisfactorily used for the analysis of PPCPs in wastewater samples. We applied the method to wastewater samples from a sewage treatment plant near Riverside, California, to track the concentration change of PPCPs in the treatment processes.     

Parts per trillion level determination of endocrine-disrupting chlorinated compounds in river water and wastewater effluent by stir-bar-sorptive extraction followed by gas chromatography–triple quadrupole mass spectrometry

A new analytical method using stir-bar-sorptive extraction (SBSE) followed by liquid desorption (LD) and gas chromatography with triple-quadrupole mass spectrometric detection (GC-QqQ-MS-MS) has been used for quantitative determination of 25 chlorinated endocrine-disrupting compounds (EDCs) in river water and wastewater. The experimental conditions affecting the SBSE-LD performance were studied and are discussed in detail. Results from systematic assay revealed that a 100-mL water sample, stir bars coated with 47?μL PDMS, an extraction time of 14?h (at 900?rpm), 5?% MeOH as modifier and 10?% NaCl resulted in the best analytical recovery of all the target compounds studied. Use of 1:1 ACN-MeOH as back-extraction solvent and two successive sonication steps, each for 5?min, resulted in the best performance for monitoring EDCs in water matrices. The method detection limits for most of the target compounds were very good- ≤?2?ng?L(-1) and ≤10?ng?L(-1) for river water and wastewater effluents respectively. Experimental recovery for all the compounds was >70?%, with the exception of simazine for which recovery from the matrix was 65?%. Signal enhancement observed for a few of the compounds in wastewater effluents was managed by use of matrix-matched standards and different injection liners. The method was successfully used for analysis of river water samples from Henares River (Spain) and wastewater effluent samples from wastewater-treatment plants (WWTP). Eleven of the 25 compounds studied were detected in both river water and wastewater effluents. Terbutylazine and methoxychlor were detected in almost all the river water and effluent samples; amounts varied between 37-58.5?ng?L(-1) and 15.2-46.8?ng?L(-1), respectively. This method was shown enable reliable, effective, and sensitive monitoring of chlorinated EDCs at nanogram levels in surface water and wastewater effluent.     

Lab-on-valve for the automatic determination of the total content and individual profiles of linear alkylbenzene sulfonates in water samples

Methods for the total content and individual determination of linear alkylbenzene sulfonates (LAS) in water samples based on the use of a lab-on-valve (LOV) module alone or coupled to CE equipment, respectively, have been developed. The total content of LAS has been determined by intrinsic absorption measurements (DA method) and after reaction with a methyl orange-cetylpyridine chloride mixture (MO method) with detection limits (LODs) of 21 ng/L and 15 microg/L, respectively, quantification limits (LOQs) of 70 ng/L, 50 microg/L, and development times of 100 and 124 s, respectively. The method for individual separation-quantification of LAS at very low concentration is based on automatic SPE preconcentration in the LOV module coupled on-line with the CE equipment. The LODs and LOQs thus obtained range between 1-21 and 4-70 ng/L, respectively, with linear dynamic ranges from the LOQ to 10 microg/L. Preconcentration factors of 10,000 and high efficiency to eliminate interferents by SPE enable application of the method to treated effluent, waste, surface and sea waters.