Development of a solid-phase microextraction method for the determination of short-ethoxy-chain nonylphenols and their brominated analogs in raw and treated water

A direct solid-phase microextraction (SPME) procedure has been developed and applied for the simultaneous determination of nonylphenol, nonylphenol mono- and diethoxylates and their brominated derivatives in raw and treated water at low microg l(-1) concentrations. Several parameters affecting the SPME procedure, such as extraction mode (headspace or direct-SPME), selection of the SPME coating, extraction time, addition of organic modifiers such as methanol and temperature were optimized. The divinylbenzene-carboxen-polydimethylsiloxane fiber was the most appropriate one for the determination of nonylphenol ethoxylates (NPEOs) and bromononylphenol ethoxylates (BrNPEOs) by SPME-GC-MS. The optimized method was linear over the range studied (0.11-2.5 microg l(-1)) and showed good precision, with RSD values between 4 and 15% and detection limits ranging from 30 to 150 ng l(-1) depending on the compound. The SPME procedure was compared with a solid-phase extraction-GC-MS method (C18 cartridge) for the analysis of NPEO and BrNPEOs in water samples. There was good agreement between the results from both methods but the SPME procedure showed some advantages such as lower detection limits, a shorter analysis time and the avoidance of organic solvents. The optimized SPME method was applied to determine nonylphenol and brominated metabolites in raw and treated water of Barcelona (NE Spain).     

Evaluation of solid-phase microextraction as an alternative to the official method for the analysis of organic micro-pollutants in drinking water

The objective this study was to compare the official EU liquid-liquid extraction (LLE) method with solid-phase microextraction (SPME) for the analysis of compounds migrating from cross-linked polyethylene into water. A medium polarity polydimethylsiloxane/divinylbenzene (PDMS/DVB) 65 microm fibre proved most efficient for the SPME extraction of nine test compounds and the optimum extraction conditions were an immersion time of 30 min with heating to 60 degrees C. The repeatability of the SPME method was variable: RSD values ranged from approximately 4-18% depending on the individual compound, though correlation coefficients were greater than 0.999 in the concentration range 0.5-1000 microg/l. It would also seem that there is some competition amongst different compounds for sites on the fibre and this is a potential drawback of SPME when applied to unknown samples. However, when applied to water samples in contact with polyethylene, SPME proved to be immensely more sensitive and to have a greater extraction range than LLE. These factors coupled with the rapidity and ease of use of SPME mean that it could be developed for use as an alternative to the existing official method or as an alert system in the routine analysis of materials used to transport domestic water.     

Surface energy characteristics of toner particles by automated inverse gas chromatography

This study develops a method for the analysis of biocides Irgarol 1051 and Sea Nine 211 in environmental water samples, using solid-phase microextraction (SPME). Their determination was carried out using gas chromatography with flame thermionic (FTD), electron-capture (ECD) and mass spectrometric detection. The main parameters affecting the SPME process such as adsorption-time profile, salt additives and memory effect were studied for five polymeric coatings commercially available for solid-phase microextraction: poly(dimethylsiloxane) (100 and 30 microm), polyacrylate, poly(dimethylsiloxane)-divinylbenzene (PDMS-DVB 65 microm) and Carbowax-divinylbenzene (65 microm). The method was developed using spiked natural waters such as tap, river, sea and lake water in a concentration range of 0.5-50 microg/l. All the tested fiber coatings have been evaluated with regard to sensitivity, linear range, precision and limits of detection. Typical RSD values (triplicate analysis) in the range of 3-10% were obtained depending on the fiber coating and the compound investigated. The recoveries of biocides were in relatively high levels 60-118% and the calibration curves were reproducible and linear (R2>0.990) for both analytes. The SPME partition coefficients (Kf) of both compounds were also calculated experimentally in the proposed conditions for all fibers using direct sampling. Finally the influence of organic matter such as humic acids on extraction efficiency was studied, affecting mostly Sea Nine 211 uptake by the fiber. Optimum analytical SPME performance was achieved using the PDMS-DVB 65 microm fiber coating in ECD and FTD systems for Sea Nine 211 and Irgarol 1051, respectively.     

Solid-phase microextraction for the analysis of short-chain chlorinated paraffins in water samples

A novel solid-phase microextraction (SPME) method coupled to gas chromatography with electron capture detection (GC-ECD) was developed as an alternative to liquid-liquid and solid-phase extraction for the analysis of short-chain chlorinated paraffins (SCCPs) in water samples. The extraction efficiency of five different commercially available fibres was evaluated and the 100-microm polydimethylsiloxane coating was the most suitable for the absorption of the SCCPs. Optimisation of several SPME parameters, such as extraction time and temperature, ionic strength and desorption time, was performed. Quality parameters were established using Milli-Q, tap water and river water. Linearity ranged between 0.06 and 6 microg l(-1) for spiked Milli-Q water and between 0.6 and 6 microg l(-1) for natural waters. The precision of the SPME-GC-ECD method for the three aqueous matrices was similar and gave relative standard deviations (RSD) between 12 and 14%. The limit of detection (LOD) was 0.02 microg l(-1) for Milli-Q water and 0.3 microg l(-1) for both tap water and river water. The optimised SPME-GC-ECD method was successfully applied to the determination of SCCPs in river water samples.     

Gas chromatographic determination of 2-hydroxy-4-methoxybenzophenone and octyldimethyl-p-aminobenzoic acid sunscreen agents in swimming pool and bathing waters by solid-phase microextraction

A method has been developed for the trace determination of two sunscreen constituents (2-hydroxy-4-methoxybenzophenone and octyldimethyl-p-aminobenzoic acid) in water samples, which are commonly used in commercial formulations. The method employs solid-phase microextraction (SPME) and gas chromatography with flame ionization and mass spectrometric detection. The technique was developed with headspace and direct sampling in order to demonstrate the applicability of these SPME extraction modes for the identification of these two UV absorbing compounds in waters. The main parameters affecting the SPME process, such as desorption time, extraction time profile, salt additives, pH, and temperature, were investigated. The poly(dimethylsiloxane) 100-microm and polyacrylate 85-microm fiber coatings were found to be the most efficient for the extraction of these compounds from aqueous matrices. Linear calibration curves in the wide range of 10-500 microg/l were obtained for both compounds yielding typical RSD values of 5-9% for both extraction modes. The recoveries were relatively high, 82-98%, with quantitation limits below 1 microg/l. A comparison between the proposed methods and the conventional multiresidue solid-phase extraction revealed that the proposed technique(s) can be reliably used for sunscreen residue measurement in water samples with satisfactory results.     

Determination of fungicides in natural waters using solid-phase microextraction and gas chromatography coupled with electron-capture and mass spectrometric detection

This study develops a method for the analysis of seven fungicides in environmental waters, using solid-phase microextraction (SPME). The analyzed compounds--dicloran, chlorothalonil, vinclozolin, dichlofluanid, captan, folpet and captafol--belong to different classes of chemical compound (chloroanilines, sulphamides, phthalimides and oxazolidines) and are used mainly in agriculture and as antifouling paints. Their determination was carried out by gas chromatography with electron-capture and mass spectrometric detection. To perform SPME, four types of fibre have been assayed and compared: polyacrylate (85 microm), polydimethylsiloxane (100 and 30 microm), carbowax-divinylbenzene (CW-DVB 65 microm) and polydimethylsiloxane-divinylbenzene (65 microm). The main parameters affecting the SPME process such as pH, salt additives, methanol content, memory effect, stirring rate and adsorption-time profile were studied. The method was developed using spiked natural waters such as ground water, sea water, river water and lake water in a concentration range of 0.1-10 microg/l. Limits of detection of studied compounds were determined in the range of 1-60 ng/l, by using electron-capture and mass spectrometric detectors. The recoveries of all fungicides were in relatively high levels (70.0-124.4%) and the average R2 values of the calibration curves were above 0.990 for all the analytes. The SPME conditions were finally optimized in order to obtain the maximum sensitivity. The potential of the proposed method was realized by applying it to the trace-level screening determination of fungicides and antifouling compounds in sea water samples originating from various Greek marinas.     

Determination of aldehydes in drinking water using pentafluorobenzylhydroxylamine derivatization and solid-phase microextraction

A headspace solid-phase microextraction (HS-SPME) procedure followed by gas chromatography and electron capture detection (GC-ECD) has been developed for the determination of aldehydes in drinking water samples at microg/l concentrations. A previous derivatization with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was performed due to the high polarity and instability of these ozonation by-products. Several SPME coatings were tested and the divinylbenzene-polydimethylsiloxane (DVB-PDMS) coating in being the most suitable for the determination of these analytes. Experimental SPME parameters such as selection of coating, sample volume, addition of salt, extraction time and temperature of desorption were studied. Analytical parameters such as precision, linearity and detection limits were also determined. HS-SPME was compared to liquid-liquid microextraction (proposed in US Environmental Protection Agency Method 556) by analyzing spiked water samples; a good agreement between results obtained with both techniques was observed. Finally, aldehydes formed at the Barcelona water treatment plant (N.E. Spain) were determined at levels of 0.1-0.5 microg/l. As a conclusion, HS-SPME is a powerful tool for determining ozonation by-products in treated water.     

Determination of bisphenol A in water by isotope dilution headspace solid-phase microextraction and gas chromatography/mass spectrometry without derivatization

The original solid-phase microextraction (SPME) fibers use an epoxy resin adhesive that releases bisphenol A (BPA) during thermal desorption of the fiber. This adversely affects the method detection limit and accuracy when these products are used for the determination of BPA. In this work, 5 new metal alloy SPME fibers that do not use epoxy resins were compared for the extraction of BPA in water. The performance of the optimum SPME fiber with 60 microm carbowax-polyethylene glycol coating for the headspace SPME of BPA in water was investigated systematically under different extraction conditions. Salt was found to increase the partitioning of BPA from water into the headspace until saturation was reached. Partitioning of BPA from water into the headspace also increased at higher extraction temperatures, as did longer extraction times. However, extraction of BPA from water onto the SPME fiber was not improved for solutions adjusted to pH 2 compared to the unadjusted neutral solutions. The new BPA method showed good linearity over the concentration range of 2.5 to 40 microg/L [correlation coefficient (r2) = 0.995] .The method detection limit for BPA was 0.5 microg/L, while the instrument detection limit was as low as 0.05 microg/L. Good repeatability was observed for BPA at levels of 5 and 20 microg/L with relative standard deviation values < 10%. The automated headspace SPME method developed in this work was used to investigate migration of BPA from polycarbonate bottles into water, and levels of BPA in water ranged from 1.7 to 4.1 microg/L.     

Automated in-tube solid-phase microextraction-high-performance liquid chromatography for carbamate pesticide analysis

In-tube solid-phase microextraction (SPME) is an automated version of SPME that can be easily coupled to a conventional HPLC autosampler for on-line sample preparation, separation and quantitation. It has been termed "in-tube" SPME because the extraction phase is coated inside a section of fused-silica tubing rather than coated on the surface of a fused-silica rod as in the conventional syringe-like SPME device. The new in-tube SPME technique has been demonstrated as a very efficient extraction method for the analysis of polar and thermally labile analytes. The in-tube SPME-HPLC method used with the FAMOS autosampler from LC Packings was developed for detecting polar carbamate pesticides in clean water samples. The main parameters relating to the extraction and desorption processes of in-tube SPME (selection of coatings, aspirate/dispense steps, selection of the desorption solvents, and the efficiency of desorption solvent, etc.) were investigated. The method was evaluated according to the reproducibility, linear range and limit of detection. This method is simple, effective, reproducible and sensitive. The relative standard deviation for all the carbamates investigated was between 1.7 and 5.3%. The method showed good linearity between 5 and 10000 microg/l with correlation coefficients between 0.9824 and 0.9995. For the carbamates studied, the limits of detection observed are lower than or similar to that of US Environmental Protection Agency or National Pesticide Survey methods. Detection of carbaryl present in clean water samples at 1 microg/l is possible.     

Determination of 17 kinds of banned organochlorine pesticides in water by activated carbon fiber-solid phase microextraction coupled with GC-MS.

Activated carbon fiber (ACF) as extraction fiber for solid-phase microextraction (SPME) and its application for the analysis of banned organochlorine pesticides (OCPs) were investigated. Firstly, ACF was activated by different concentration of zinc chloride, which indicated that ACF activated by 60% zinc chloride had a reasonable specific surface area, pore volume and pore distribution. Secondly, the parameters for the ACF-SPME procedure, the adsorption and desorption conditions, were also optimized when coupled with gas chromatography-mass spectrometry (GC-MS). Thirdly, the ACF-SPME was used to analyze 17 kinds of OCPs in water. The linearity of most pesticides was found to be between 0.2 and 50 microg/l with GC-MS under the selected ion monitoring (SIM) acquisition mode. The limits of detection (LOD) at the sub microg/l were obtained. The work demonstrated here shows that ACF is a promising alternative for the SPME procedure.     

Analysis of oxytetracycline, tetracycline, and chlortetracycline in water using solid-phase extraction and liquid chromatography-tandem mass spectrometry

A method using liquid chromatography-tandem mass spectrometry has been developed for determination of trace levels of tetracycline antibiotics in ground water and confined animal feeding operation waste water. Oxytetracycline (OTC), tetracycline (TC), and chlortetracycline (CTC) were extracted from water samples using both polymeric and C18 extraction cartridges. The addition of a buffer containing potassium phosphate and citric acid improved tetracycline recoveries in lagoon water. Method detection limits determined in reagent water fortified with 1 microg l(-1) OTC, TC, and CTC were 0.21, 0.20, and 0.28 microg l(-1). Method detection limits in lagoon water samples fortified at 20 microg l(-1) for OTC, TC, and CTC were 3.6, 3.1, and 3.8 microg l(-1). Variability in recovery from laboratory fortified blanks ranged from 86 to 110% during routine analysis.     

Optimization of headspace solid-phase microextraction by means of an experimental design for the determination of methyl tert.-butyl ether in water by gas chromatography-flame ionization detection

A procedure for determination of methyl tert.-butyl ether (MTBE) in water by headspace solid-phase microextraction (HS-SPME) has been developed. The analysis was carried out by gas chromatography with flame ionization detection. The extraction procedure, using a 65-microm poly(dimethylsiloxane)-divinylbenzene SPME fiber, was optimized following experimental design. A fractional factorial design for screening and a central composite design for optimizing the significant variables were applied. Extraction temperature and sodium chloride concentration were significant variables, and 20 degrees C and 300 g/l were, respectively chosen for the best extraction response. With these conditions, an extraction time of 5 min was sufficient to extract MTBE. The calibration linear range for MTBE was 5-500 microg/l and the detection limit 0.45 microg/l. The relative standard deviation, for seven replicates of 250 microg/l MTBE in water, was 6.3%.     

Solid-phase extraction versus solid-phase microextraction for the determination of chlorinated paraffins in water using gas chromatography-negative chemical ionisation mass spectrometry

Solid-phase extraction (SPE) and solid-phase microextraction (SPME) were evaluated for the analysis of short-chain chlorinated paraffins (SCCPs) in water samples using gas chromatography coupled to negative chemical ionisation mass spectrometry (GC-NCI-MS). For SPE optimisation, four commercially available SPE cartridges were tested and several SPE parameters, such as the elution solvent, elution volume and breakthrough volume were studied. The best results were obtained with Varian Bond Elut-C18. In order to achieve a high selectivity in the determination of SCCPs, GC-NCI-MS was used. Quality parameters of the optimised SPE and SPME procedures were determined, and the best results were obtained for the SPE/GC-NCI-MS method with LODs of 5 and 20 ng l(-1) for tap and river water, respectively. This method was successfully applied to the analysis of SCCPs in river water samples at concentrations below the microg l(-1) level.     

聚甲基三氟丙基硅氧烷固相微萃取涂层的制备及其对海水中酚类化合物的分析

采用溶胶-凝胶技术制备了聚甲基三氟丙基硅氧烷(PTFPMS)涂层,并将其作为萃取     

Determination of organochlorine pesticides in water using microwave assisted headspace solid-phase microextraction and gas chromatography

A coupled technique, microwave-assisted headspace solid-phase microextraction (MA-HS-SPME), was investigated for one-step in situ sample pretreatment for organochlorine pesticides (OCPs) prior to gas chromatographic determination. The OCPs, aldrin, o,p'-DDE, p,p'-DDE, o,p'-DDT, p,p'-DDT, dieldrin, alpha-endosulfan, beta-endosulfan, endosulfan sulfate, endrin, delta-HCH, gamma-HCH, heptachlor, heptachlor epoxide, methoxychlor and trifluralin were collected by the proposed method and analyzed by gas chromatography with electron-capture detection (GC-ECD). To perform the MA-HS-SPME, six types of SPME fibers were examined and compared. The parameters affecting the efficiency in MA-HS-SPME process such as sampling time and temperature, microwave irradiation power, desorption temperature and time were studied to obtain the optimal conditions. The method was developed using spiked water samples such as field water and with 0.05% humic acid in a concentration range of 0.05-2.5 microg/l except endosulfan sulfate in 0.25-2.5 microg/l. The detection was linear over the studied concentration range with r2>0.9978. The detection limits varied from 0.002 to 0.070 microg/l based on S/N=3 and the relative standard deviations for repeatability were <15%. A certified reference sample of OCPs in aqueous solution was analyzed by the proposed method and compared with the conventional liquid-liquid extraction procedure. These results are in good agreement. The results indicate that the proposed method provides a very simple, fast, and solvent-free procedure to achieve sample pretreatment prior to the trace-level screening determination of organochloride pesticides by gas chromatography.     

Multivariate optimization of a solid phase microextraction-headspace procedure for the determination of benzene, toluene, ethylbenzene and xylenes in effluent samples from a waste treatment plant

A method based on solid-phase microextraction (SPME) and gas chromatography with flame ionization detection (GC-FID) has been optimized for the determination of benzene, toluene, ethylbenzene and xylenes (BTEX) in water released from a waste treatment plant. The extraction step was optimized using fractional factorial and central composite designs including the following experimental factors: saline concentration; extraction time; desorption time; agitation velocity; headspace volume. A multiple function was used to describe the experimental conditions for simultaneous extraction of the compounds. The procedure, based on direct SPME at 50 degrees C, using a polydimethylsiloxane fiber, showed good linearity (r>0.997 over a concentration range 2-200 microg L(-1)) and repeatability (relative standard deviation (RSD)<4.23%) for all compounds, with limits of detection ranging from 0.05 to 0.28 microg L(-1), and limits of quantification ranging from 0.14 to 0.84 microg L(-1). Concentrations of the target compounds in these samples were between 145.8 and 1891 microg L(-1).     

Residues of oxytetracycline and its 4'-epimer in edible tissues from turkeys

Residues of oxytetracycline (OTC) in edible tissues (muscle, liver, and kidney) of 18 turkeys were determined after continuous administration of the drug for 3 days in drinking water at the maximum recommended concentration of 400 mg/L. The European Union (EU) maximum residue limits (MRLs) set for OTC are 100 microg/kg in muscle tissues, 300 microg/kg in liver, and 600 microg/kg in kidney, as the sum of the parent compound and its derivative 4'-epi-oxytetracycline (4-epi-OTC). Cleanup of tissue samples was performed by metal chelate affinity chromatography (MCAC), but the original technique was miniaturized by the adoption of a mini solid-phase extraction column, allowing reduction of solvents, time, and hazardous waste. OTC and its 4'-epimer were quantitated by an isocratic liquid chromatography elution with UV detection. After 1 day of withdrawal, OTC plus 4-epi-OTC residues were greater than MRL values in muscle and liver; 3 days after the end of treatment, all tissue residues were far lower than the MRL values. At the first day after the end of treatment, 4-epi-OTC was detected at very low concentrations only in muscle, in liver after 1 and 3 days of withdrawal, and in kidney at all sampling times. The withdrawal time was calculated according to EU recommendations and was set at 5 days.     

Use of solid-phase microextraction/gas chromatography-electron capture detection for the determination of energetic chemicals in marine samples

Gas chromatography with electron capture detection (GC-ECD) is a highly explosive-sensitive analytical technique. However, its application to the analysis of sediment extracts is hampered by the presence of numerous endogenous interferences. In the present study, solid-phase microextraction (SPME) was used both as a purification technique for sediment extracts and as an extraction technique for water samples prior to analysis by GC-ECD. SPME/GC-ECD coupling was optimized and applied to the trace analysis of nine explosives including nitroaromatics and RDX in real seawater and marine sediment samples. Addition of a high concentration of salt (30%, w/v) in the aqueous medium and use of a carbowax/divinylbenzene (CW/DVB) coating led to optimal extraction efficiencies. Method detection limits (MDLs) ranged from 0.05 to 0.81 microg/L in water and from 1 to 9 microg/kg in dry sediment. Except for RDX, spike recoveries in seawater were satisfactory (89-147%) when samples were fortified at 2 microg/L of each analyte. Spike recoveries from dry sediment fortified at 10 microg/kg of each analyte gave lower recoveries but these could also be due to degradation in the matrix. With a smaller volume of aqueous sample required compared to solid-phase extraction (SPE), SPME is an attractive method for the analysis of limited volumes of sediment pore-water. Moreover, the use of SPME eliminated interferences present in sediment extracts thus allowing the detection of the target analytes that were otherwise difficult to detect by direct injection.     

Determination of nitrate esters in water samples Comparison of efficiency of solid-phase extraction and solid-phase microextraction

This paper deals with comparison of efficiency of extraction techniques (solid-phase extraction, SPE and solid-phase microextraction, SPME) used for extraction of nitrate esters (ethyleneglycoldinitrate, EGDN and nitroglycerin, NG), representing the first step of the method of quantitative determination of trace concentrations of nitrate esters in water samples. EGDN and NG are subsequently determined by means of high-performance liquid chromatography with ultraviolet detection (HPLC-UV). Optimization of SPE and SPME conditions was carried out using model water samples. Seven SPE cartridges were tested and the conditions were optimized (type of sorbent, type and volume of solvent to be used as eluent). For both nitrate esters the limit of detection (LOD) and the limit of quantification (LOQ) obtained using SPE/HPLC-UV were 0.23 microg mL(-1) and 0.70 microg mL(-1), respectively. Optimization of SPME conditions: type of SPME fibre (four fibres were tested), type and time of sorption/desorption, temperature of sorption. PDMS/DVB (polydimethylsiloxane/divinylbenzene) fibre coating proved to be suitable for extraction of EGDN and NG. For this fibre the LOD and the LOQ for both nitrate esters were 0.16 microg mL(-1) and 0.50 microg mL(-1), respectively. Optimized methods SPE/HPLC-UV and SPME/HPLC-UV were then used for quantitative determination of nitrate esters content in real water samples from the production of EGDN and NG.     

Hollow fiber membrane-protected solid-phase microextraction of triazine herbicides in bovine milk and sewage sludge samples

A porous polypropylene hollow fiber membrane (HFM)-protected solid-phase microextraction (HFM-SPME) procedure in conjunction with gas chromatography/mass spectrometric analysis for use in the determination of triazine herbicides in bovine milk samples is described. A 65-microm polydimethylsiloxane-divinylbenzne (PDMS-DVB) SPME fiber was protected by an HFM. HFM-SPME experimental parameters such as fiber type, extraction time, extraction temperature and salt concentration were investigated and optimized. The relative standard deviations for the reproducibility of the optimized HFM-SPME method varied from 4.30 to 12.37%. The correlation coefficients of the calibration curves were between 0.9799 and 0.9965 across a concentration range of 0-200 microg l(-1). The method detection limits for triazines in bovine milk were in the range of 0.003-0.013 microg l(-1) and limits of quantification were in the range of 0.006-0.021 microg l(-1). The suitability of HFM-SPME was extended to the analysis of the herbicides in sewage sludge samples. The results demonstrate that HFM-SPME was an efficient pretreatment and enrichment procedure for complex matrices.