Determination of non-ionic surfactants and polar degradation products in influent and effluent water samples and sludges of sewage treatment plants by a generic solid-phase extraction protocol

Non-ionic polyethoxylated surfactants (nonylphenol polyethoxylates, alcohol polyethoxylates), their breakdown products (polyethylene glycol, polyethoxylated nonylphenol carboxylates and polyethoxylated alcohol carboxylates) and other compounds were identified and measured in various waste-water treatment samples (influent, effluent and sludge). A generic protocol involving the use of sequential solid-phase extraction (SSPE) with octadecylsilica and styrene-divinylbenzene cartridges in series and differential elution was used. Fractionated extracts were analyzed by liquid chromatography-mass spectrometry (LC-MS) using atmospheric pressure chemical ionization (APCI) in the positive and negative ionization modes. For sewage treatment plant (STP) sludge, the extraction protocol involved lyophilization of the sludge followed by sonication with MeOH-CH2Cl2 (7 + 3) and final clean-up using the SSPE protocol. Limits of detection for target analytes ranging from 1.1 to 4.1 micrograms L-1 for water samples and from 0.11 to 0.28 mg kg-1 for sludge were achieved. The results obtained demonstrated the inefficient removal of the target analytes in physico-chemical STPs whereas their elimination factors in STPs with biological treatment reached average values of 77, 92 and 98% for alcohol polyethoxylates, nonylphenol polyethoxylates (NPEOs) and polyethylene glycols (PEGs), respectively. Quantitative elimination of coconut fatty acid diethanolamide (CDEA) surfactants in the activated sludge process occurred. In contrast, total removal of NPEOs led to the formation of persistent and toxic metabolites such as nonylphenol which was present in treated effluent as well as in sludge samples with average concentrations ranging from 15.0 to 251.2 micrograms L-1 and from 13.5 to 74.2 mg kg-1, respectively. Polyethoxylated carboxylates and short chain NPEOs were also detected at similar levels in the effluents and sludges. In addition, a linear correlation between the total phenolic concentration (Total Ph) measured by the 4-aminoantipyrine method and the total concentration of nonylphenolic compounds (Total NP) measured by SSPE-LC-APCI-MS was observed.     

Determination of linear alkylbenzene sulfonates and their polar carboxylic degradation products in sewage treatment plants by automated solid-phase extraction followed by capillary electrophoresis-mass spectrometry.

Linear alkylbenzene sulfonates (LAS) were determined by solid-phase extraction (SPE), followed by capillary electrophoresis and mass spectrometry detection (CE-MS). The linear range of the proposed method varied from 33 to 316 and from 215 to 2057 micrograms L-1, depending on the compound, with limits of detection ranging from 4.4 to 23 micrograms L-1 when 200 ml of wastewater were preconcentrated. The analysis and confirmation of the polar carboxylic metabolites of LAS, the sulfophenyl carboxylic acids (SPC) was also achieved, and their presence was detected in both, influent and effluents of the sewage treatment plant (STP). [M - H]- ions were used for CE-MS confirmation and quantification. CE-MS diagnostic ions were the same ones used in LC-electrospray (ESI)-MS and corresponded to m/z 297, 311, 325 and 339 for C10LAS, C11LAS, C12LAS and C13LAS, respectively. For SPC identification, diagnostic ions corresponded to m/z 215 to 369 (with 14 mass unit steps) for C2 to C13SPC, respectively. LAS were determined in wastewater samples of the influent and effluent of three sewage treatment plants (STP), two of them using biological treatment with secondary settlement and receiving mainly domestic wastewater whereas one of the plants was operated with physiochemical treatment and received mainly industrial wastewater. The concentration levels of total LAS varied from 1000 to 1900 micrograms L-1 in the influents of STP, whereas in the effluents the concentrations varied from 125 to 360 micrograms L-1.     

Bioconcentration of linear alkylbenzene sulfonates and their degradation intermediates in marine algae

Sorption experiments using different homologues of linear alkylbenzene sulfonate (LAS) and sulfophenylcarboxylic acid (SPC) on several marine microalgae have been carried out. The steady state seems to be reached in the first 4 hours. Longer exposure times lead to biodegradation of the compound and, therefore, to an overestimation of the bioconcentration factor. Sorption coefficients are higher for Nannochloropsis gaditana, for example, 1,293 Lkg(-1) for C11-LAS and 525 Lkg(-1) for C11-SPC versus 727 Lkg(-1) for C11-LAS and 28 Lkg(-1) for C11-SPC for Dunaliella salina. For both algae an increase in the sorption coefficient is observed when the polarity of the compound decreases (C5-SPC相似文献   

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.     

Handling of marine and estuarine samples for the determination of linear alkylbenzene sulfonates and sulfophenylcarboxylic acids

Due to the physicochemical properties of linear alkylbenzene sulfonates (LAS), an anionic surfactant, it is difficult to obtain representative samples from sampling sites. Further, the high biodegradability of these compounds makes it necessary to study their biodegradation intermediates, sulfophenylcarboxylic acids (SPC) that do not have a surfactant character and show a different behavior. A procedure for determining and quantifying LAS and SPC in different environmental matrices by Soxhlet and solid-phase extractions and high-performance liquid chromatography is presented. The recoveries varied in the range from 85 to 102% for the water samples, and from 75 to 105% for sediment samples, with a standard deviation of between 1 and 7, and 2 and 11, respectively. Detection limits obtained were in the range from 5 to 10 microg kg(-1) for sediment samples (10 g) and from 0.2 to 0.4 microg l(-1) for water samples (250 ml). The method was applied to the simultaneous determination of LAS (C10-C13) and SPC (C4-C13) homologues in water, sediment and interstitial water collected from different areas of Spain.     

An LC-MS method for the determination of pharmaceutical compounds in wastewater treatment plant influent and effluent samples

Pharmaceuticals are continually introduced into the environment as a result of industrial and domestic use. In recent years they have emerged as environmental pollutants. An analytical method has been developed allowing for simultaneous detection and identification of 20 pharmaceutical compounds from various therapeutic classes using solid phase extraction (SPE) followed by liquid chromatography-electrospray ionisation mass spectrometry (LC-MS/MS). The limits of detection and limits of quantitation for the method were in the ng/L-microg/L range. The method was applied to influent and effluent samples from three wastewater treatment plants (WWTPs). Fifteen compounds were identified in the sample matrix with salicylic acid and ibuprofen being the most abundant at 9.17 and 3.20 microg/L respectively.     

Determination of linear alkylbenzene sulfonates in water samples by liquid chromatography-UV detection and confirmation by liquid chromatography-mass spectrometry

A high-performance liquid chromatographic (HPLC) method was developed for the separation and determination of individual (C₁₀-C₁₃) linear alkylbenzene sulfonates (LAS). New sets of conditions have been established for routine analysis of individual chemical forms of four LAS surfactants, i.e. C₁₀-C₁₃ LAS. Under a condition set using a mobile phase containing 1.5 mM ammonium acetate in methanol/water 80:20 (v/v) mixture, detection limits obtained were in the range 1.5 ppb (for C₁₀ LAS) to 11.5 ppb (for C₁₃ LAS). This offers the advantages of significant improvement in resolution, short separation time and using less amount of common salt under isocratic condition. In addition, the use of simple mobile phase containing a simple low amount of salt cannot deposit at the entrance of mass spectrometric detector. The method is applicable to the simultaneous determination of LAS surfactants in various water samples. LAS surfactants presented in these samples were also successfully confirmed by using electrospray mass spectrometry.     

Extraction and isolation of linear alkylbenzene sulfonates and their intermediate metabolites from various marine organisms

A method has been developed for the determination of linear alkylbenzene sulfonates and its degradation intermediates (sulfophenylcarboxylic acids) from different marine organisms, which includes the stages of extraction and analysis by liquid chromatography with fluorescence detection. The extraction stage (Soxhlet and solid-phase extractions) was optimised by the selection of the appropriate solvent, minicolumns and different clean-up stages. Recoveries varied in the range from 80 to 104%, with a standard deviation between 1 and 9%. Detection limits were 15 ng g(-1) wet mass for undecylbezene sulfonate and 30 ng g(-1) wet mass for sulfophenylundecanoic acid using HPLC-fluorescence detection. The complete analytical method was successfully applied to different marine organisms from the Bay of Cadiz (SW Spain).     

Linear alkylbenzene sulfonates (LAS) in sewage sludges, soils and sediments: analytical determination and environmental safety considerations

Linear Alkylbenzenesulphonates (LAS), a major anionic surfactant used in laundry products, can be measured specifically in the environment by instrumental analysis. In addition to a desulphonation-gas chromatography approach, a method based on high performance liquid chromatography has been developed. The main features of the methods are outlined, and LAS concentrations measured in sewage sludge, sediments and sludge amended soils are reported. Knowledge of usage volumes, sewage treatment practices and environmental transport and transformation mechanisms has been used to predict concentrations of LAS. These calculated concentrations were found to agree well with those actually measured in the environment. Both measured and calculated ambient concentrations of LAS are below those which could produce potentially adverse effects in representative surface water, benthic and terrestrial organisms.     

The determination of the linear alkylbenzene sulfonate isomers in water samples by gas-chromatography/mass spectrometry

A number of 20 compounds of linear alkylbenzene sulfonates (LASs) family were identified by electron impact mass spectrometry (EI-MS) in water samples collected from wastewater treatment plants (WWTP). This paper presents the mass spectra of 20 compounds, the proposed mechanism of formation of the diagnostic ions obtained by EI-MS and the distribution of individual isomers in water samples collected from compartments of WWTP. The individual isomers from four homolog series C(10)-, C(11)-, C(12)- and C(13)-LAS were analyzed as methyl derivatives.     

Ion-pair extraction and GC-MS determination of linear alkylbenzene sulphonates in aqueous environmental samples

A GC-MS method was developed for the determination of linear alkylbenzene sulphonates (LAS) and sulphophenylcarboxylic acids (SPC) in aqueous environmental samples. LAS and SPC were isolated from aqueous samples using methylene green (MG) as ion-pair reagent and derivatised with diazomethane for their chromatographic analysis. LAS and SPC were then analysed with GC-MS in EI mode as their methyl esters. The method eliminates positive and negative interferences found by the methylene blue method and considered to be selective and sensitive for the determination of LAS and SPC in aqueous samples. The recovery of LAS was 98% with a relative standard deviation (R.S.D.) of 2.0% and the detection limit obtained from calculations by using GC-MS results based on S/N:3 was lower than 10 ppb. Obtained results revealed that the method can also be employed in the analysis of organic compounds bearing sulphate and sulphonate groups.     

Simultaneous extraction and fate of linear alkylbenzene sulfonates, coconut diethanol amides, nonylphenol ethoxylates and their degradation products in wastewater treatment plants, receiving coastal waters and sediments in the Catalonian area (NE Spain)

A simple, isocratic liquid chromatographic (LC) method using volatile mobile phase constituents for the identification of related substances in erythromycin samples is described. For method development, evaporative light scattering detection (ELSD) was used. An XTerra RP18 column was used at 70 degrees C with a mobile phase consisting of acetonitrile-isopropanol-0.2M ammonium acetate pH 7.0-water (165:105:50:680). Mass spectral data were acquired on an ion trap mass spectrometer equipped with an electrospray interface operated in the positive ion mode. First, a library was created using MS/MS and MS(n) spectra of reference substances available in the laboratory. Using these reference spectra as interpretative templates, eight novel related substances in erythromycin samples were identified: N-demethylerythromycin E, erythromycin E N-oxide, anhydroerythromycin C, N-demethylerythromycin B, anhydro-N-demethylerythromycin A, pseudoerythromycin E enol ether, EF lacking the neutral sugar and EA lacking the neutral sugar.     

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.     

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?°C and –20?°C). The results indicate that disposable SPE cartridges can be recommended for the stabilization of non-ionic surfactants and LAS. Storage at –20?°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?°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.     

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.     

Application of probe sonication extraction for the determination of linear alkylbenzene sulfonates from sewage sludge. Comparison with other extraction methods

A new method based on probe sonication extraction (USP) prior to high performance liquid chromatography (HPLC) has been developed for the determination of linear alkylbenzene sulfonates (LAS) from sewage sludge. The optimized method was designed to be cost effective compared to existing extraction methods (ultrasonic assisted extraction, Soxhlet or pressurized liquid extraction) which may require large quantities of organic solvents, or costly instrumentation or equipment.The main factors affecting the extraction efficiency (extractant volume, ultrasounds power and extraction time) were optimized using compost sludge. The detection limit of total LAS in the sludge was 10 mg kg^− 1. The extraction of C₁₀-C₁₃ homologues is carried out using an extraction time of 7 min with 10 mL of methanol. Liquid chromatography with fluorescence (FL) detector is used for determination of LAS homologues. A mobile phase acetonitrile-water containing 0.1 M NaClO₄ (65:35) and isocratic elution was used. Compounds were eluted over 6 min at a flow rate of 1 mL/min. Polar interferences are eluted between 0 and 2 min and no purification of the samples is required prior to the final determination by high performance liquid chromatography (HPLC). The recoveries of LAS in spiked sewage sludge were between 84.0% and 97.0%, which reflect the efficiency of the method for extraction of these analytes from sewage sludge. Concentration levels found were between 11,858 mg kg^− 1 for digested sludge and 2379 mg kg^− 1 for compost sludge.     

Determination of photodegradation and ozonation by products of linear alkylbenzene sulfonates by liquid chromatography and ion chromatography under controlled laboratory experiments

A Suntest solar simulator with arc xenon lamp was used to irradiate pure linear alkylbenzene sulfonates (LAS) standard and some commercial LAS solutions. The ozonation treatment was carried out in a pilot plant air-lift type reactor. Kinetic degradation curves were obtained showing an apparent first order reaction in both cases. Extraction and preconcentration of samples was carried out by off-line SPE using polymeric an RP-18 cartridges with recoveries varying from 77 to 93% for the LAS compounds. For LC chromatographic elution of LAS and degradation products an ion pair based on 5 mM triethylamine and 5 nM acetic acid had to the acetonitrile-water or methanol-water mobile phases. Fluorescence detection was achieved at 225 and 295 nm as excitation and emission radiation wavelength, respectively. Degradation by products were identified by liquid chromatography electrospray mass spectrometry detection (LC-ESI-MS). Ion chromatography (IC) was used to analyze refractory species such as oxalate, formate and acetate ions which were present in the treated solution even after 3 h of ozone treatment. The LAS mixture was almost totally degraded in less than 20 min using O₃/H₂O₂, the reaction being faster than in the case of catalyzed photodecomposition. TOC removal reached 84% after 3 h of ozonation process.     

Determination of alkylphenols and linear alkylbenzene sulfonates in sediments applying accelerated solvent extraction (ASE)

A time and solvent saving method (accelerated solvent extraction, ASE) for the extraction of anionic surfactants as linear alkylbenzene sulfonates (LAS) and alkylphenols from sediments is presented. The analytes are extracted by methanol at 100 degrees C and 150 atm within 10 min of static and 5 min of dynamic extraction. The presence of methanol and a maximum pressure of 150 atm are essential for the complete extraction of anionic surfactants, whereas the extraction of alkylphenols is independent of both parameters. The extraction of alkylphenolethoxylates yielded only unsatisfactor results. It was demonstrated that the ASE extraction is selective for LAS surfactants, while matrix substances, which are extracted by the methanol extraction and interfere with the target analytes during the HPLC-run, remain in the sample. Thus, a further clean-up procedure of the ASE extract is not necessary.     

Determination of alkylphenols and linear alkylbenzene sulfonates in sediments applying accelerated solvent extraction (ASE)

A time and solvent saving method (accelerated solvent extraction, ASE) for the extraction of anionic surfactants as linear alkylbenzene sulfonates (LAS) and alkylphenols from sediments is presented. The analytes are extracted by methanol at 100° C and 150 atm within 10 min of static and 5 min of dynamic extraction. The presence of methanol and a maximum pressure of 150 atm are essential for the complete extraction of anionic surfactants, whereas the extraction of alkylphenols is independent of both parameters. The extraction of alkylphenolethoxylates yielded only unsatisfactor results. It was demonstrated that the ASE extraction is selective for LAS surfactants, while matrix substances, which are extracted by the methanol extraction and interfere with the target analytes during the HPLC-run, remain in the sample. Thus, a further clean-up procedure of the ASE extract is not necessary.