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Determination of polycyclic aromatic hydrocarbons in seawater by high-performance liquid chromatography with fluorescence detection following micelle-mediated preconcentration.

In this work, the nonionic surfactant polyoxyethylene-10-lauryl ether has been used for the extraction and preconcentration of 14 polycyclic aromatic hydrocarbons, classified as priority pollutants by the US Environmental Protection Agency, from seawater samples. The cloud-point preconcentration previous separation by HPLC and quantification using fluorimetric detection and wavelength programming allow to determine these pollutants with detection limits ranging from 1.0 to 1.5 x 10(2) ng/l with RSDs better than 10.4%. The methodology is evaluated using well-established extraction and preconcentration methods and GC-MS.

Chromatography, High Pressure Liquid↗

Analysis of ppb levels of organics in water by means of purge-and-trap, capillary gas chromatography and selective detectors.

The Environmental Protection Agency (EPA) has issued a series of methods (500 and 600 series) for the analysis of organics in drinking water and industrial discharges. Methods 601 and 602 employ packed-column gas chromatography (GC) with electrolytic conductivity (E1CD) and photoionization detection (PID), respectively. A purge-and-trap system is used for concentration of volatiles. The EPA is in the process of converting methods 601 and 602 and certain 500-series methods to capillary column analysis. We have also initiated the conversion of a number of these methods, using E1CD and PID and have described them in detail in this paper. We have evaluated both 0.32- and 0.53-mm diameter capillary columns, using helium and nitrogen as carrier gases with each detector. We found that with nitrogen optimum results are obtained at a flow-rate of 15 ml/min, and with helium at 6-8 ml/min. As a result of system optimization, including operation of the two detectors in series, and converting from packed to capillary columns, we found that analysis time could be reduced from 80 min (for two methods separately) to ca. 30 min. In addition, the elution of more than five components in one peak, observed when the packed column specified in method 601 are used, was eliminated.

Chromatography, Gas↗

Retention of eleven priority phenols using micellar electrokinetic chromatography.

The use of micellar electrokinetic chromatography (MECC) for the separation of eleven substituted phenols listed by the United States Environmental Protection Agency as priority pollutants was investigated. Solutions of potassium and sodium dodecyl sulphate in phosphate-borate buffer of pH 6.6, 7.0 and 7.5 were used as the electrophoretic media. Satisfactory separation of the eleven phenols was obtained using a 180-microns capillary at 10 kV and pH 6.6 with a solution containing both sodium and potassium dodecyl sulphate. Observations on the retention behaviour of the phenols in MECC were related to their physico-chemical properties.

Chromatography↗

The effect of cyclohexene, a preservative in dichloromethane on the liquid-liquid extraction and analysis of chlorinated drinking water.

Liquid-liquid extraction with dichloromethane is the Environmental Protection Agency's (EPA) method of choice for the analysis of acid or base neutral organic chemicals in water. Free radical chlorination and oxidation products of cyclohexene (the solvent preservative) in dichloromethane have been observed in extracts of chlorinated drinking water (after 10(5) fold concentration) by gas chromatography and gas chromatography-mass spectrometry. The chlorinated cyclohexene derivatives limit the quantitative and qualitative analysis of compounds eluting at Kovát's index less than 700-1000 and the use of these extracts for organoleptic and mutagenic studies. The effect of residual free chlorine in water on the cyclohexene present in the solvent was studied. Over ten cyclohexene derivatives were produced in every case when any residual free chlorine was present in the water. When chlorine is reduced to chloramine, the cyclohexene derivatives were greatly reduced in number and amount.

Chloramines↗

Elution behaviour of peropyrene-type polycyclic aromatic hydrocarbons in various chemically bonded stationary phases in reversed-phase liquid chromatography.

The elution behaviour of polycyclic aromatic hydrocarbons (PAHs, 13 of the 16 U.S. Environmental Protection Agency priority pollutants and peropyrene types) was studied on several chemically bonded stationary phases (octadecylsilicas, di- and triphenylsilicas, naphthylethylsilica and pyrenylethylsilica) under reversed-phase conditions. The results showed that the elution order of peropyrene-type PAHs is highly dependent on the degree of planarity of the solute and on the orderlines of the bonded phases, whereas no definite differences were found in the retention behaviour of the 13 small PAHs on various stationary phases. The characteristics of all the stationary phases could be classified by statistical cluster analysis.

Chemical Phenomena↗

Analysis of the herbicides paraquat, diquat and difenzoquat in drinking water by micellar electrokinetic chromatography using sweeping and cation selective exhaustive injection.

Optimum conditions for the determination of the herbicides paraquat, diquat and difenzoquat by micellar electrokinetic chromatography (MEKC) using sweeping and cation-selective exhaustive injection (CSEI) as on-line concentration methods were developed. Sodium dodecyl sulfate (80 mM) in 50 mM phosphate buffer (pH 2.5) with 20% acetonitrile was used as a background electrolyte for the methods studied. The limits of detection, based on a signal-to-noise ratio of 3:1, were about 2.6-5.1 mg 1(-1) in purified water when MEKC was applied for the standards. By using an on-line preconcentration method known as sweeping-MEKC, up to a 500-fold increase in detection sensitivity was obtained whereas up to a 50 000-fold increase for CSEI-sweeping-MEKC was achieved. The limits of detection using optimum CSEI-sweeping-MEKC were lower than 1 microg 1(-1) and the method was validated obtaining good reproducibility (relative standard deviation lower than 22%) and linearity. CSEI-sweeping-MEKC was successfully applied to the determination of the three herbicides in spiked tap water below the levels established by the US Environmental Protection Agency.

Cations↗

Solid-phase microextraction coupled to high-performance liquid chromatography to determine phenolic compounds in water samples.

Solid-phase microextraction (SPME) coupled to high-performance liquid chromatography (HPLC) with ultraviolet (UV) and electrochemical detection (ED) has been applied to determine 11 phenolic compounds considered priority pollutants by the US Environmental Protection Agency. 85 microm polyacrylate fibers were used to extract the analytes from the aqueous samples. Two different designs of the liquid chromatograph were compared in combination with SPME. Dynamic and static modes of desorption in both HPLC designs were compared and the variables affecting both absorption and desorption processes in SPME-HPLC were optimized. Static desorption in both HPLC systems showed better recoveries for the phenolic compounds. The performance of the SPME-HPLC-UV-ED method was evaluated with river water and wastewater samples. The method enabled the determination of phenolic compounds at low levels in these water samples.

Chromatography, High Pressure Liquid↗

Study of the feasibility of focused microwave-assisted soxhlet extraction of N-methylcarbamates from soil.

A study of the feasibility of a focused microwave-assisted Soxhlet device for the extraction of N-methylcarbamates from soil has been performed. The main factors contributing to the extraction efficiency-namely microwave power, irradiation time and number of cycles--were optimized by means of a two-level full factorial design. The extracts were analysed by HPLC-post-column fluorescence derivatization-detection at excitation wavelength 340 nm and emission wavelength 445 nm. The method has allowed the extraction of carbamate pesticides from contaminated soil with quantitative recoveries, similar to those provided by the US Environmental Protection Agency method 8318, without degradation of the target compounds during the extraction and using less organic solvent, as 75-80% of the extractant was recycled.

Calibration↗

Detection of explosives and their degradation products in soil environments.

Polynitro organic explosives [hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6-trinitrotoluene (TNT)] are typical labile environmental pollutants that can biotransform with soil indigenous microorganisms, photodegrade by sunlight and migrate through subsurface soil to cause groundwater contamination. To be able to determine the type and concentration of explosives and their (bio)transformation products in different soil environments, a comprehensive analytical methodology of sample preparation, separation and detection is thus required. The present paper describes the use of supercritical carbon dioxide (SC-CO2), acetonitrile (MeCN) (US Environmental Protection Agency Method 8330) and solid-phase microextraction (SPME) for the extraction of explosives and their degradation products from various water, soil and plant tissue samples for subsequent analysis by either HPLC-UV, capillary electrophoresis (CE-UV) or GC-MS. Contaminated surface and subsurface soil and groundwater were collected from either a TNT manufacturing facility or an anti-tank firing range. Plant tissue samples were taken fromplants grown in anti-tank firing range soil in a greenhouse experiment. All tested soil and groundwater samples from the former TNT manufacturing plant were found to contain TNT and some of its amino reduced and partially denitrated products. Their concentrations as determined by SPME-GC-MS and LC-UV depended on the location of sampling at the site. In the case of plant tissues, SC-CO2 extraction followed by CE-UV analysis showed only the presence of HMX. The concentrations of HMX (<200 mg/kg) as determined by supercritical fluid extraction (SC-CO2)-CE-UV were comparable to those obtained by MeCN extraction, although the latter technique was found to be more efficient at higher concentrations (>300 mg/kg). Modifiers such as MeCN and water enhanced the SC-CO2 extractability of HMX from plant tissues.

Azocines↗

Determination of organochlorine pesticides in seawater using liquid-phase hollow fibre membrane microextraction and gas chromatography-mass spectrometry.

The use of hollow fibre membrane microextraction in analytical chemistry has been increasing as the technique is a simple and efficient method for the extraction of trace organic compounds from environmental matrices. A simple liquid-phase microextraction technique using a hollow fibre membrane in conjunction with gas chromatography-mass spectrometry has been developed for the extraction and analysis of organochlorine pesticides (OCPs), i.e. alpha-hexachlorocyclohexane (BHC), lindane, beta-BHC, heptachlor, aldrin, dieldrin, endrin, endosulfan, p,p'-DDD, p,p'-DDT, endrin aldehyde and methoxychlor, from seawater. The technique requires minimal sample preparation time and solvent consumption, and represents a significant advantage over conventional analytical methods. Optimum extraction conditions have been evaluated with respect to sample pH, salt content and stirring rate, as well as solvent type and extraction time. A high level of detection linearity (coefficient of >0.9995, less than 14% RSD) was obtained for OCPs over a range of analyte concentrations between 5 and 100 microg l(-1), with detection limits in the parts per trillion (ppt) to sub-parts per billion range. Comparison between liquid-phase microextraction with hollow fibre membrane and US Environmental Protection Agency Method 508 showed that the novel method has comparable detection limits of between 0.013 and 0.059 microg l(-1) in seawater.

Gas Chromatography-Mass Spectrometry↗

Condensation nucleation light scattering detection with ion chromatography for direct determination of glyphosate and its metabolite in water.

An ion chromatography-condensation nucleation light scattering detection (IC-CNLSD) method was successfully used to directly analyze glyphosate, a polar pesticide, and aminomethylphosaphonic acid, the major metabolite of glyphosate, in water without need of pre-treatment or derivatization. CNLSD gave a LOD of 53 ng/ml for glyphosate, which is much lower than the maximum contaminant level of 700 ng/ml for drinking water issued by the US Environmental Protection Agency. Spiked analytes in different matrixes were tested. A diluted commercial herbicide containing glyphosate was also evaluated. Compared to other reported methods, the IC-CNLSD method has no need of sample derivatization, pre-concentration, and mobile phase conductivity suppression. It is simple, fast and inexpensive. IC-CNLSD is an ideal direct detection technique for such pesticides without chromophores or fluorophores.

Chromatography, Liquid↗

Cyclodextrin-assisted capillary electrophoresis for determination of the cyclic nitramine explosives RDX, HMX and CL-20 comparison with high-performance liquid chromatography.

A sulfobutyl ether-beta-cyclodextrin-assisted electrokinetic chromatographic method was developed to rapidly resolve and detect the cyclic nitramine explosives 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane (CL-20), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and their related degradation intermediates in environmental samples. Development of the electrophoretic method required the measurement of the aqueous solubility of CL-20 which was determined to be 3.59 +/- 0.74 mg/l at 25 degrees C (95% confidence interval, n=3). The performance of the method was then compared to results obtained from existing high-performance liquid chromatography methods including US Environmental Protection Agency method 8330.

Aza Compounds↗

Automated fast extraction of nitrated polycyclic aromatic hydrocarbons from soil by focused microwave-assisted Soxhlet extraction prior to gas chromatography--electron-capture detection.

An approach for the automated fast extraction of nitrated polycyclic aromatic hydrocarbons (nitroPAHs) from soil, using a focused microwave-assisted Soxhlet extractor, is proposed. The main factors affecting the extraction efficiency (namely: irradiation power, irradiation time, number of cycles and extractant volume) were optimised by using experimental design methodology. The reduction of the nitro-PAHs to amino-PAHs and the derivatisation of the reduced analytes with heptafluorobutyric anhydride was mandatory prior to the separation-determination step by gas chromatography--electron-capture detection. The proposed approach has allowed the extraction of these pollutants from spiked and "real" contaminated soils with extraction efficiencies similar to those provided by the US Environmental Protection Agency methods 3540-8091, but with a drastic reduction in both the extraction time and sample handling, and using less organic solvent, as 75-85% of it was recycled.

Chromatography, Gas↗

Optimization, validation and comparison of various extraction techniques for the trace determination of polycyclic aromatic hydrocarbons in sewage sludges by liquid chromatography coupled to diode-array and fluorescence detection.

There is a need for a better characterization of sludges from wastewater treatment plants which are destined to be spread on agricultural lands. Inorganic pollutants are regularly controlled but organic pollutants have received few attention up to now. On this paper, we have been interested on the analysis of the 16 polycyclic aromatic hydrocarbons (PAHs) listed in the US Environmental Protection Agency (US EPA) priority list and more particularly of the six PAHs listed in the European community list (fluoranthene, benzo[b and k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene). The analysis step consists on liquid chromatography with both fluorescence and UV detections as described in the EPA Method 8310. As for the extraction step, several techniques such as supercritical fluid extraction, pressurized liquid extraction, focused microwave extraction in open vessels, Soxhlet and ultrasonic extractions are compared after optimization of the experimental conditions (solvent nature and quantity, temperature, pressure, duration, ... ) and validation with certified sludges. When optimized, these five extraction techniques are as much efficient with similar relative standard deviation. Whatever the extraction techniques used, the whole analysis protocol permits to quantify PAHs in the range of 0.09 to 0.9 mg/kg of dried sludges.

Chromatography, High Pressure Liquid↗

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.

Benzene↗

On-line solid-phase extraction with molecularly imprinted polymers to selectively extract substituted 4-chlorophenols and 4-nitrophenol from water.

Three polymers have been synthesised using 4-chlorophenol (4-CP) as the template, following different protocols (non-covalent and semi-covalent) and using different functional co-monomers, 4-vinylpyridine (4-VP) and methacrylic acid (MAA). The polymers were evaluated to check their selectivity as molecularly imprinted polymers (MIPs) in solid-phase extraction (SPE) coupled on-line to liquid chromatography. The solid-phase extraction procedure using MIPs (MISPE), including the clean-up step to remove any interferences, was optimised. The 4-VP non-covalent polymer was the only one which showed a clear imprint effect. This MIP also showed cross-reactivity for the 4-chloro-substituted phenols and for 4-nitrophenol (4-NP) from a mixture containing the 11 priority EPA (Environmental Protection Agency) phenolic compounds and 4-chlorophenol. The MIP was applied to selectively extract the 4-chloro-substituted compounds and 4-NP from river water samples.

Chlorophenols↗

Determination of phenolic pollutants in drinking water by capillary electrophoresis in the sample stacking mode.

A method for the determination of phenol, chlorophenols and nitrophenols at levels below those allowed by international legislation in water from the public supply is proposed. Ten of the compounds studied are included on the USA Environmental Protection Agency priority list of aquatic pollutants. Samples are concentrated off-line on cross-linked polystyrene and subsequently subjected to capillary electrophoresis using the sample stacking procedure to remove the matrix. The recoveries afforded by the off-line concentration process and the behaviour of the phenols in relation to sample stacking injection were examined.

Chlorophenols↗

Determination of carbaryl, carbofuran and methiocarb in cucumbers and strawberries by monoclonal enzyme immunoassays and high-performance liquid chromatography with fluorescence detection. An analytical comparison.

Carbaryl, carbofuran and methiocarb are three of the most important N-methylcarbamate pesticides. In the present work, the application of laboratory-developed monoclonal antibody-based enzyme-linked immunosorbent assays (ELISAs) to the determination of these compounds in fruits and vegetables is described. Cucumbers and strawberries were spiked with the three carbamates at 10, 50 and 200 ppb. After extraction and clean-up, samples were analyzed by immunoassay and by HPLC with post-column derivatization and fluorescence detection (US Environmental Protection Agency Method 531.1). Results obtained by ELISA correlated well with those obtained by HPLC, both in terms of accuracy and precision. Recoveries were in the 60-90% range by ELISA and in the 50-90% range by HPLC, depending on the particular combination of commodity, pesticide, and fortification level under consideration. ELISAs were also applied to the analysis of non-purified sample extracts with excellent results: recoveries close to 100% were obtained, while maintaining similar precision values. This approach avoids the use of solid-phase extraction columns, saves time, and considerably increases the sample throughput. Results clearly indicate that the developed immunoassays may be suitable for the quantitative and reliable determination of carbaryl, carbofuran and methiocarb in fruits and vegetables even without including clean-up steps. These considerations make these ELISAs very useful analytical tools for monitoring and regulatory programs, without the need of complex and expensive instrumentation.

Antibodies, Monoclonal↗