Simultaneous determination of methyl tert.-butyl ether and its degradation products,other gasoline oxygenates and benzene,toluene, ethylbenzene and xylenes in Catalonian groundwater by purge-and-trap-gas chromatography-mass spectrometry

In Catalonia (northeast Spain), a monitoring program was carried out to determine methyl tert.-butyl ether (MTBE), its main degradation products, tert.-butyl alcohol (TBA), tert.-butyl formate (TBF), and other gasoline additives, the oxygenate dialkyl ethers ethyl tert.-butyl ether, tert.-amyl methyl ether and diisopropyl ether and the aromatic compounds benzene, toluene, ethylbenzene and xylene (BTEX) in 21 groundwater wells that were located near different gasoline point sources (a gasoline spill and underground storage tank leakage). Purge-and-trap coupled to gas chromatography-mass spectrometry was optimised for the simultaneous determination of the above mentioned compounds and enabled to detect concentrations at ng/l or sub-microg/l concentrations. Special attention was given to the determination of polar MTBE degradation products, TBA and TBF, since not much data on method performance and environmental levels are given on these compounds in groundwater. All samples analysed contained MTBE at levels between 0.3 and 70 microg/l. Seven contaminated hot spots were identified with levels up to US Environmental Protection Agency drinking water advisory (20-40 microg/l) and a maximum concentration of 670 microg/l (doubling the Danish suggested toxicity level of 350 microg/l). Samples with high levels of MTBE contained 0.1-60 microg/l of TBA, indicating (but not proving) in situ degradation of parent compound. In all cases, BTEX was at low concentrations or not detected showing less solubility and persistence than MTBE. This fact confirms the suitability of MTBE as a tracer or indicator of long-term gasoline contamination than the historically used BTEX.     

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%.     

Use of experimental design for the purge-and-trap-gas chromatography-mass spectrometry determination of methyl tert.-butyl ether,tert.-butyl alcohol and BTEX in groundwater at trace level

An efficient method for the simultaneous determination of methyl tert.-butyl ether, tert.-butyl alcohol, benzene, toluene, ethylbenzene and xylene isomers in groundwater by purge-and-trap-gas chromatography-mass spectrometry was developed and validated. Experimental design was used to investigate the effects of temperature of extraction, time of extraction and percentage of salt added to the water samples. Regression models and desirability functions were applied to find the experimental conditions providing the highest global extraction yield. Validation was carried out in terms of limits of detection (LOD), limits of quantitation (LOQ), linearity and precision. LOD values ranging from 2.6 to 23 ng l(-1) were achieved, whereas linearity was statistically verified over two orders of magnitude for each compound. Precision was evaluated testing two concentration levels. Good results were obtained both in terms of intra-day repeatability and intermediate precision: RSD% lower than 4.5% at the highest concentration and lower than 13% at the lowest one were calculated for intra-day repeatability. A groundwater sample suspected of contamination by leaking underground petroleum storage tanks was analysed and some of the analytes were detected and quantitated.     

Analysis of methyl tert.-butyl ether and its degradation products by direct aqueous injection onto gas chromatography with mass spectrometry or flame ionization detection systems.

A method was developed to analyze methyl tert.-butyl ether (MTBE) and its degradation products by gas chromatography with mass spectrometry (GC-MS) or flame ionization detection (FID) with direct aqueous injection. The column had dimensions of 30 m x 0.25 mm with film thickness 0.25 microm and a stationary phase of FFAP (nitroterephthalic acid-modified polyethylene glycol). The optimized GC conditions for non-acid components were as follows: carrier gas flow-rate,l mL/min; oven temperature, 35 degrees C for 5.5 min, ramped to 90 degrees C at 25 degrees C/min, then ramped to 200 degrees C at 40 degrees C/min and held at 200 degrees C for 8 min. The conditions for the acid components were: carrier gas flow-rate, 1 mL/min; oven temperature, 110 degrees C for 2 min, ramped to 150 degrees C at 10 degrees C/min, then ramped to 200 degrees C at 40 degrees C/min. The injection port contained a silanized-glass reverse-cup liner filled with Carbofrit. The minimum concentrations for the linear range for the selective ion monitoring mode were 30 to 100 microg/L, depending on the analytes. The minimum detection limit was 1 mg/L for MTBE and tert.-butanol when using FID. More components could be analyzed with the FFAP-type column than with the cyanopropylphenyl-dimethyl polysiloxane-type column.     

Reversed-phase high-performance liquid chromatographic separation of tert.-butyl hydroperoxide oxidation products of unsaturated triacylglycerols

Triacylglycerols containing monounsaturated fatty acids are known to be relatively resistant to autoxidation and require long periods of exposure to dilute oxidants. Use of concentrated solutions of synthetic hydroperoxides, however, yields in addition to the hydroperoxides also unidentified oxidation by-products. In the present study we have employed synthetic triacylglycerols containing one (18:0/18:1/18:0 and 18:1/16:0/16:0) and two (18:0/18:0/18:2 and 18:1/18:1/18:0) double bonds per molecule to reinvestigate the formation of oxotriacylglycerols using tert.-butyl hydroperoxide as an oxidant. Reversed-phase HPLC was used to separate and tentatively identify the oxidation products based on relative retention times of standards and the estimated elution factors for functional groups and their positional distribution. Hydroperoxides, diepoxides and hydroxides were the major components of the oxidation mixtures (50-95% of total). Previously unidentified peroxide-bridged tert.-butyl adducts were present in significant amounts (5-50% of total oxidation products) in all preparations. In several instances more than one functional group was present on a single fatty chain. The tentative reversed-phase chromatographic identification of the adducts was confirmed by determination of the molecular mass of each component by on-line LC with electrospray MS. The oxidation products were quantified by HPLC with light scattering detection.     

Determination of dichloroacetic acid and trichloroacetic acid by liquid-liquid extraction and ion chromatography

An extraction technique using MTBE (methyl tert. butyl ether) and reagent water in combination with ion chromatography and conductivity determination was developed to quantify dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) concentrations in raw water after chlorination. The detection limit of the method was 0.45 and 1.50 microg/L for DCAA and TCAA, respectively. Mean values of recovery ranged from 90 to 96% for DCAA and 95 to 108% for TCAA. The evaluation of recovery and precision of the method indicates that the performance characteristics are comparable with gas chromatographic (GC) methods reported in literature. In addition, the procedure is simple, fast, and does not need any derivatization step. Application of the analytical method to the determination of DCAA and TCAA in real samples is shown.     

Determination of oxygenated polycyclic aromatic hydrocarbons in atmospheric aerosol samples by liquid chromatography-tandem mass spectrometry

In this paper, the development of an analytical method using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with atmospheric pressure chemical ionization (APCI) for the determination of 17 oxygenated polycyclic aromatic hydrocarbons (OPAH) is described. These OPAH include ketones, pyrones and diketones. The APCI interface parameters have been optimized for maximum sensitivity. Positive ion mode was proved to be most sensitive for ketones and pyrones while negative ion mode gave better detection limits for target diketones. The detection limits of the method ranged from less than 1.20microg L(-1) for several OPAH solutions (between 0.10 and 0.70microg L(-1) for positive mode and between of 0.19 and 1.20microg L(-1) for negative mode). The analytical method was applied particulate matter (PM(2.5)) samples collected over 24-48h periods between March 2005 and June 2005 in Tempe (Arizona, USA). Before analysis aerosol samples were solvent extracted and concentrated to a final volume of 1mL of methanol. OPAH concentrations observed for this urban site ranged from 0.22 to 3.60ngm(-3).     

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.     

Determination of acidic drugs in sewage water by gas chromatography-mass spectrometry as tert.-butyldimethylsilyl derivatives

A procedure is described for the determination of five acidic non-steroidal anti-inflammatory pharmaceuticals (ibuprofen, naproxen, ketoprofen, tolfenamic acid and diclofenac) in sewage water. The analytical method involves the concentration of water samples using a solid-phase extraction polymeric sorbent, functionalized with N-vinylpyrrolidone. Analytes were eluted with ethyl acetate. derivatized using N-methyl-N-(tert.-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) and analyzed by GC-MS. Influence of time, temperature and volume of MTBSTFA in the yield of the derivatization step were studied in detail using a factorial central composite design. Quantification limits of the analytical procedure for 500 ml of sewage water ranged from 20 to 50 ng/l. Recoveries from 90 to 115% were found for sewage water samples spiked with the studied compounds at the low ng/ml level. Results obtained for real samples show the presence of ibuprofen and naproxen in both influent and effluent of a sewage water treatment plant.     

The ritter reaction of poly(acrylonitrile) with tert.-butyl alcohol

The course of the Ritter reaction has been investigated for poly(acrylonitrile) with tert.-butyl alcohol in the presence of sulphuric acid in tetramethylene sulphone. From the rate constants, activation parameters and their dependence on molecular mass, tacticity, concentration of the reaction mixture and extent of the reaction, and from composition of the reaction products, it was concluded that the reaction proceeded by a non-acceleration mechanism with formation of a random copolymer acrylonitrile—N-tert.-butylacrylamide. At about 55% conversion of nitrile groups, the reaction is considerably slowed down, obviously due to a conformational change of the chain.     

Aroma compound analysis of Piper nigrum and Piper guineense essential oils from Cameroon using solid-phase microextraction-gas chromatography,solid-phase microextraction-gas chromatography-mass spectrometry and olfactometry

Three analytical methods were developed for the determination of toxic compounds in recirculating waters of a paper-recycling industry. Three main groups of compounds were considered: (i) wood extractives originated from the raw material; (ii) biocides added during the production process and (iii) surfactants and other adjuvants present in the formulates of these biocides. Wood extractives considered in this study included fatty and resin acids. They were analysed by liquid-liquid extraction using methyl tert.-butyl ether, followed by gas chromatography-mass spectrometry for previous formation of the respective trimethylsilyl esters. Water samples were also extracted with Oasis HLB (copolymer [poly(divinylbenzene-co-N-vinylpyrrolidone]) solid-phase extraction cartridges of 60 mg and analysed by liquid chromatography-electrospray mass spectrometry for the determination of additives and biocides. Using these two approaches levels up to 15 mg/l for total resin and fatty acids, 5 mg/l for alkylbenzene sulfonates and 2-(thiocyanomethylthio)benzotiazol, 100 microg/l for bisphenol A and 2,2-dibromo-3-nitrilepropionamide, and 300 microg/l for nonylphenol ethoxycarboxylate were detected in process waters at different production treatment stages. These levels are of relevance since poor water quality affects the paper-recycling process, the primary water treatment process and eventually, the environmental water quality.     

Investigation of methyl tert-butyl ether levels in river-, ground-, and sewage-waters analyzed using a purge-and-trap interfaced to a gas chromatograph-mass spectrometer

River water collected from 27 sites in 21 rivers, groundwater from 66 sites in 34 cities, and 2 sewage plants in the Niigata Prefecture, Japan (total 301 samples) were analyzed for methyl tert-butyl ether (MTBE) using an improved purge-and-trap-GC-MS method. The amount of MTBE found in water samples from the 27 river sites ranged from 0.003 to 5.3 microg l(-1). MTBE was found in all 27 sites during winter but it was found at only 9 sites and 14 sites, respectively, during the summer. MTBE was found most frequently (in 21 sites) at levels ranging from 0.003 to 0.009 microg l(-1) during February. The highest levels of MTBE were always found in the samples collected from the same site. The amount of MTBE found in sewage water samples ranged from <0.003 to 0.025 microgl(-1). No significant differences were observed between the amounts of MTBE recovered from inflow and outflow waters. Relatively high levels (0.02-0.034 microg l(-1) ) of MTBE were found in January at two sites, which were located on the upper course of the Shinano River. MTBE levels ranged from 0.004 to 0.035 microgl(-l) and from 0.005 to 0.041 microgl(-1) at the mouths of the Shinano River and Agano River, respectively. The levels of MTBE in groundwater collected from 66 sites in 34 cities in Niigata Prefecture ranged from <0.003 to 5.9 microg l(-1).     

Determination of dichloroacetic acid and trichloroacetic acid by liquid-liquid extraction and ion chromatography

An extraction technique using MTBE (methyl tert. butyl ether) and reagent water in combination with ion chromatography and conductivity determination was developed to quantify dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) concentrations in raw water after chlorination. The detection limit of the method was 0.45 and 1.50 μg/L for DCAA and TCAA, respectively. Mean values of recovery ranged from 90 to 96% for DCAA and 95 to 108% for TCAA. The evaluation of recovery and precision of the method indicates that the performance characteristics are comparable with gas chromatographic (GC) methods reported in literature. In addition, the procedure is simple, fast, and does not need any derivatization step. Application of the analytical method to the determination of DCAA and TCAA in real samples is shown.     

Trace-level determination of triazines and several degradation products in environmental waters by disk solid-phase extraction and micellar electrokinetic chromatography

An analytical method combining disk solid-phase extraction with micellar electrokinetic chromatography has been developed for the determination of atrazine, simazine, hydroxyatrazine, deisopropylatrazine, deethylatrazine, propazine and prometryn in water samples. The influence of the buffer and sodium dodecyl sulfate (SDS) concentration, pH and organic modifier on the separation has been studied. Baseline separation of the seven triazines was achieved under the following conditions: 10 mM borate buffer, 60 mM SDS, 20% methanol and pH 9.2. C18-bonded silica and poly(styrene-divinylbenzene) (PS-DVB) disks were evaluated for solid-phase extraction of the selected pesticides (11 of water sample). Using two PS-DVB disks, quantitative recoveries were obtained for all pesticides tested. The method was successfully applied for the determination of the seven triazines in drinking and well water at the 0.1 microg l(-1) and 0.5 microg l(-1) concentration levels, respectively. The detection limits for these analytes using the proposed analytical method were within the 0.02-0.06 microg l(-1) range in drinking water and the 0.06-0.30 microg l(-1) range in well water.     

Development and validation of a multi-residue method for the determination of pesticides in processed fruits and vegetables using liquid chromatography–electrospray ionization tandem mass spectrometry

A sensitive multi-residue analytical method, utilizing ethyl acetate extraction and liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS), has been developed and validated for simultaneous determination of 28 pesticides of different chemical classes (polar organophosphates, carbamates, strobilurines, neonicotinoids, amides, pyrimidines, benzimidazoles, imidazoles and triazoles), and their transformation products, in processed fruit and vegetables. Two precursor-product ion transitions were monitored for each pesticide in selected reaction monitoring (SRM) mode. Linearity (r (2) > or = 0.99) was good over the concentration range 0.5 to 100 microg L(-1) for all the pesticides, and instrumental detection limits ranged from 0.1 to 1 microg L(-1). Mean recovery for fruit and vegetables spiked at 0.010 mg kg(-1) ranged from 65 to 94.4%, and relative standard deviations ranged from 9.0 to 20.0%. When the amount spiked was 0.050 mg kg(-1) recoveries ranged from 72.5 to 90% and relative standard deviations were from 6.1 to 19.0%. Method detection limits were from 0.002 to 0.007 mg kg(-1) for the different food matrices studied. The method was used to monitor pesticide residues in a wide variety of fruits and vegetables.     

Optimization of nonequilibrium liquid-phase microextraction for the determination of nitrobenzenes in aqueous samples by gas chromatography-electron capture detection.

In the present work, a novel method for the determination of nitrobenzenes in water has been described. It is based on nonequilibrium liquid-phase microextraction and gas chromatography-electron capture detection (GC-ECD). Extraction conditions such as solvent selection, organic solvent dropsize, stirring rate, content of NaCl and extraction time were found to have significant influence on extraction efficiency. The optimized conditions were 1.5 microl toluene and 20 min extraction time at 400 rpm stirring rate without NaCl addition. The linear range was 0.1 - 50 microg l(-1) for most nitrobenzenes. The limits of detection (LODs) ranged from 0.02 microg l(-1) (for 2.6-DNT) to 0.4 microg l(-1) (for NB); and relative standard deviations (RSD) for most of the nitrobenzenes at the 10 microg l(-1) level, except for 2,6-DNT in 3 microg l(-1), were below 10%. Natural samples collected from Miyun Reservoir and tap water samples from a laboratory were successfully analyzed using the proposed method, but none of the analytes were detected. The relative recoveries of spiked water samples (at the 10 microg l(-1) level except for 2,6-DNT in 3 microg l(-1)) were from 82.6 to 118.7%.     

Continuous on-line determination of methyl tert-butyl ether in water samples using ion mobility spectrometry

A rapid analytical procedure for the on-line determination of methyl tert-butyl ether (MTBE) in water samples was developed. A new membrane extraction unit was used to extract the MTBE from water samples. The concentration of MTBE was determined using ion mobility spectrometry with 63Ni ionization and corona discharge ionization without chromatographic separation. Both ionization methods permit the sensitive determination of MTBE. A detection limit of 100 microg/L was established for the on-line procedure. Neither the inorganic compounds, humic substances nor gasoline were found to exert a significant influence on the peak intensity of the MTBE. The screening procedure can be used for concentrations of monoaromatic compounds (benzene, toluene, xylene) up to 600 microg/L. No sample preparation is required and the analysis results are available within 5 min. In order to determine concentrations between 10 microg/L and 100 microg/L, a discontinuous procedure was developed on the basis of the same experimental set-up.     

Determination of halogenated mono-alcohols and diols in water by gas chromatography with electron-capture detection

We have developed an analytical method for the detection of halogenated alcohols in water with particular focus on 3-chloro-1,2-propanediol and 3-bromo-1,2-propanediol. In this method the target analytes are extracted from water, derivatized with heptafluorobutyric anhydride, and then analyzed with gas chromatography with electron-capture detection. The effects of water, pH and seawater constituents on the method were investigated. Method detection limits for a 5 ml aqueous sample ranged from 0.14 microg l(-1) for 2-bromo-1,3-propanediol to 1.7 microg l(-1) for 1,3-dichloro-2-propanol (1,3DCP).     

Optimization of chromatographic parameters for the determination of biogenic amines in wines by reversed-phase high-performance liquid chromatography

A method suitable for the determination of eight biogenic amines (histamine, tyramine, phenylethylamine, tryptamine, cadaverine, putrescine, spermidine and spermine) in wines has been developed. The method involves derivatization of the amines by treatment with dabsyl chloride, after which the derivates were analysed by reversed-phase liquid chromatography with gradient elution and spectrophotometric detection at 446 nm. Different variables affecting separation were optimized. Validation of the method included calibration experiments, the addition of standards amines for the determination of recovery and repeatability tests. Good linearity of the responses was obtained up to 500 microg l(-1), except for putrescine (up to 2100 microg l(-1)). The detection limits ranged between 10 and 60 microg l(-1) for standard solutions. The method was successfully applied to the analysis of five Spanish wines.     

Determination of mefloquine in blood, filter paper-absorbed blood and urine by 9-fluorenylmethyl chloroformate derivatization followed by liquid chromatography with fluorescence detection

We describe a method for determination of mefloquine (MQ) in 100-microliters samples of urine, whole blood, and capillary blood collected on filter paper; quantification is by liquid chromatography with fluorescence detection at 475 nm of the 9-fluorenylmethyleneoxycarbonyl derivative. Whole blood and urine samples were prepared by extraction of MQ and internal standard from aqueous base with methyl tert.-butyl ether (MTBE), separation and evaporation of the MTBE layer, and derivatization using a solution of 9-fluorenylmethyl chloroformate in acetonitrile. Filter paper spots were immersed for 16 h in 0.1 M hydrochloric acid, followed by extraction with MTBE from aqueous sodium carbonate. The separated and evaporated organic layer was treated with the derivatizing solution. An aliquot was injected onto a high-performance liquid chromatography system using a C18 reversed-phase column and acetonitrile-water (72:28) mobile phase for filter paper spot extracts as for whole blood and urine extracts. The method has a limit of determination in blood, blood spots, and urine of 50 ng/ml with 100 microliters sample size (coefficient of variation = 16%). Linearity and precision (within-day and between-day) for the method are good. The MQ derivative was isolated and characterized spectroscopically. Values for MQ concentrations in filter paper blood spots compared favorably with values found in corresponding whole blood samples analyzed by a published method.