Surface water preparation procedure for chromatographic determination of polycyclic aromatic hydrocarbons and polychlorinated biphenyls

A new sample preparation procedure for the analysis of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in water containing suspended particulate matter (SPM) has been developed. A specially designed filtration vessel coupled directly to an SPE cartridge was used for this purpose. SPM separation and analyte isolation/concentration were carried out in a single step. Both the SPE cartridge and the suspended matter collected on the filter were solvent extracted, and analyte recoveries were determined. Analyte recoveries from the filtrate ranged from 64 to 100% of the spiked amount for PAHs with the highest aqueous solubilities, and did not exceed 20% for those with the lowest solubilities. Total recoveries of PAHs from surface water containing 21 mg l(-1) SPM ranged from 65 to 121%. PCB recoveries from the particulate matter reached over 10% of the spiked amount, while those from the filtrate ranged from 20 to 57%. Total PCBs recoveries ranged from 34 to 69%.     

Sample preparation improvement in polycyclic aromatic hydrocarbons determination in olive oils by gel permeation chromatography and liquid chromatography with fluorescence detection

The determination of 15 polycyclic aromatic hydrocarbons (PAHs) in olive oil samples has been improved in order to obtain a fast methodology with a low limit of detection through the combination of liquid-liquid extraction with acetonitrile and preparative gel permeation chromatography (GPC) prior to the injection of purified extracts into a C18 column. Acetonitrile-water was used as the mobile phase with a gradient from 50 to 95%, w/w, acetonitrile in 30 min. The oven temperature was maintained at 15 degrees C, and fluorometric detection was made at a fixed excitation wavelength of 264 nm and variable, optimal emission wavelength for each analyte ranging from 352 nm for 11-H-benzo(b)fluorene to 500 nm for indeno(1,2,3-cd)pyrene. Recovery for all the compounds studied varied from 75 to 111%, and limit of detection values from 0.05 ng/g for benzo(k)fluoranthene to 0.48 ng/g for indeno(1,2,3-cd)pyrene, corresponding to 0.09 ng/g benzo(a)pyrene. Results were compared with those obtained by liquid-liquid extraction followed by a cleanup on silica and a direct GPC treatment of oil samples diluted in dichloromethane, 2 other methodologies that are appropriate for quantifying PAHs in olive oils. However, the proposed method improves the determination limits, reduces the time of analysis, and provides a highly stable baseline for sample chromatograms.     

Shpol''skii fluorimetric determination of polycyclic aromatic hydrocarbons in complex environmental samples

Summary High-resolution fluorimetry in low-temperature n-alkane Shpol'skii matrices is a powerful technique for the analysis of rigid, non-polar compounds like polycyclic aromatic hydrocarbons. Because of the method's sensitivity and selectivity, sample clean-up, preconcentration and even chromatographic separation can often be left out. The Shpol'skii analysis of pyrene in crude extracts from marine sediments and from bird meat is demonstrated. Special attention is focussed on the extra possibilities acquired when a laser is used as excitation source (Laser Excited Shpol'skii Spectroscopy, LESS).     

MultiSimplex optimisation of the solid-phase microextraction-gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons,polychlorinated biphenyls and phthalates from water samples

Solid-phase microextraction coupled to GC-MS was optimised for the determination of polycyclic aromatic hydrocarbons (PAHs), phthalate esters and polychlorinated biphenyls (PCBs) in water samples. A 30-microm polydimethylsiloxane fiber was immersed in a 30-ml water sample that contained the analytes of interest (PAHs, PCBs and phthalate esters) and the variables studied were extraction time (15-60 min), extraction temperature (30-90 degrees C), desorption time (1-5 min), desorption temperature (220-270 degrees C) and the addition of sodium chloride (0-9 g). The MultiSimplex programme based on the simplex algorithm was used to establish the optimal conditions. MultiSimplex allowed the simultaneous study of the variables mentioned above and considered the answers of all types of compounds studied in this work. Thus, the optimal conditions obtained allowed the simultaneous determination of PAHs, phthalate esters and PCBs. Furthermore, the accuracy and repeatability of the developed method were calculated from water samples spiked at known concentrations of the analytes. Finally, the optimised method was used to analyse water samples from different sampling points of the Urdaibai and Nerbioi-Ibaizabal estuaries (Biscay, Spain).     

Liquid chromatographic method with fluorescence detection for the determination of polycyclic aromatic hydrocarbons in environmental samples

A method for the determination of some polynuclear aromatic hydrocarbons (PAHs) in water samples and air filters is presented. Samples were extracted with light petroleum-diethyl ether (85 + 15) and the extracts were concentrated before analysis. Reversed-phase liquid chromatography with fluorescence detection was applied to separate and determine the PAHs. Recoveries of individual PAHs from spiked water samples were 0.16–0.27 ng ml^?1. Detection limits in the picogram range were obtained for each compound.     

Simultaneous extraction of polycyclic aromatic hydrocarbons and polychlorinated biphenyls in agricultural soils by pressurized liquid extraction and determination by gas chromatography coupled to tandem mass spectrometry

A simple and rapid method based on pressurized liquid extraction has been validated for the simultaneous extraction of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) from agricultural soil samples. Effective extraction was carried out in less than 17 min for all the studied compounds, and good recoveries were obtained for PAHs and PCBs, ranging from 70% to 112%, when blank samples were spiked at 2.5 μg kg⁻¹, except for naphthalene with recoveries close to 40%. The separation and determination were performed by gas chromatography coupled to tandem mass spectrometry using a triple quadrupole mass analyzer. The target compounds were detected by electron impact with selected reaction monitoring, and mass spectrometric conditions were optimized in order to increase selectivity and sensitivity. The developed method was validated, and matrix-matched calibration was used for quantification purposes. Repeatability and interday precision ranged from 0.9% to 16.8% and from 1.6% to 22.3%, respectively. Limits of quantification ranged from 0.07 to 2.50 μg kg⁻¹. The proposed method was applied to the analysis of agricultural soil samples collected from Almeria (Spain), and PAHs and PCBs were detected in some samples at concentrations ranging from 0.1 to 210 μg kg⁻¹.     

用固相萃取技术富集水中多环芳烃

系统地研究了淋洗剂强度、用量和有机改性剂的加入对固相萃取水中多环芳烃回收率的影响。研究表明,二氯甲烷和苯的洗脱效果较好,回收率为８７％～１０２％;当淋洗剂的用量超过１．５ｍＬ时,对多环芳烃的回收率没有明显的影响;向自来水样中加入２０％有机改性剂可明显改善多环芳烃的回收效果,使回收率达到８９％～１０８％。     

Determination of polychlorinated biphenyls by fast chromatography mass-spectrometry in environmental and biological samples

A method for the determination of polychlorinated biphenyls (PCB) by fast gas chromatography coupled with mass-spectrometric detection in selective ion monitoring mode has been developed. Chromatographic separation was carried out with HT-8 column (30 m × 0.25 mm) under sharp temperature increase from 80 to 320°C at a rate of 40°C/min. Duration of chromatography is 10 min. Fast chromatography conditions suggested by authors makes it possible to increase S/N ratios 10 times and so to reduce significantly the representative weight of the sample and develop an effective sample preparation technique. The method was used for PCB determination in Baikal area samples such as soil, snow, sediments from Lake Baikal and its tributaries, tissues of Baikal omul (Coregonus migratorius, Georgi, 1775) and blubber of Baikal seal (Phoca sibirica Gm.). The sample preparation stage includes PCB extraction from environmental samples and hydrolyzate of biological material with the following cleanup of the extract on the compact silica gel and florisil cartridges (0.5 g of the sorbent). The method enables the measurements of total PCBs and isomer groups of the same chlorination level with interlaboratory precision of no greater than 10% and the determination of indicator congeners (PCBs 28, 52, 101, 118, 138, 153, and 180) with a precision not exceeding 15%.     

Miniaturised analytical procedure of determining polycyclic aromatic hydrocarbons and polychlorinated biphenyls in bottom sediments

Rapid analytical methods are described to control quality of honeys, concerning residues of acaricides applied in hives to prevent Varroa jacobsoni infestation. A liquid-liquid extraction with hexane-propanol-2-ammonia (60 ml:30 ml:0.28%) was used for the simultaneous analysis of coumaphos, bromopropylate, amitraz and fluvalinate. For thymol, one clean up on a solid-phase extraction C18 (500 mg, 6 ml) column was performed; for rotenone, a liquid extraction with dichloromethane was realised. Quantitative recoveries obtained with honey were satisfactory and were superior to 80%. All acaricides are identified by reversed-phase high-performance liquid chromatography with photodiode array detection. Quantification limits obtained were below maximal residue limits when these exist.     

Determination of polycyclic aromatic hydrocarbons in environmental samples by high performance thin-layer chromatography and fluorescence scanning densitometry

High performance thin-layer chromatography (HPTLC) with fluorescence scanning densitometry was used for the quantitative determination of polycyclic aromatic hydrocarbons in the soluble organic fraction of air particulate samples. A method using normalized emission response ratios was developed to determine sample identity and to test for peak homogeneity. To preserve the high sample throughput of HPTLC, the two-point calibration method was used for quantitation. The principal advantages of HPTLC as a screening technique for environmental samples are its low cost, methodological simplicity, high sample throughput, and the ability to analyze crude samples with a minimum amount of sample cleanup.     

Characterization of polycyclic aromatic hydrocarbons in environmental samples by selective fluorescence quenching

Selective fluorescence quenching is used to profile polycyclic aromatic hydrocarbons (PAHs) in samples of environmental origin. After separation by high-efficiency capillary liquid chromatography, the PAHs are detected by laser-induced fluorescence spectroscopy. Nitromethane is added to selectively quench the fluorescence of alternant PAHs, whereas diisopropylamine is added to quench nonalternant PAHs. The chromatograms in the absence and presence of fluorescence quenching are evaluated by means of the product moment correlation method to quantify the statistical similarities and differences. This method is demonstrated by application to three samples: a standard mixture of 16 priority pollutants, a coal-derived fluid, and a contaminated soil. The correlation coefficients (r) are typically 0.99 or higher for samples that are identical in origin, 0.90-0.50 for closely related samples, and less than 0.50 for samples that are distinctly unrelated. This method can be used to confirm with high statistical confidence the cause or source of an event with environmental impact, such as an oil leak or spill, contamination or waste by-products from petroleum fuel production and processing, etc.     

Determination of some selected polycyclic aromatic hydrocarbons in environmental samples by high-performance liquid chromatography with fluorescence detection

Summary Analytical methods for the determination in environmental samples, of some selected Polycyclic Aromatic Hydrocarbons (PAH's), which are included on the EPA Priority Pollutant list, have been developed and evaluated. The methodology involves the extraction of PAH's from water samples by solvent extraction with dichloromethane. Solid samples were ultrasonically extracted with acetone/hexane and the extract was cleaned up on a silica gel/alumina column. The concentrated and cleaned up extracts were analysed by HPLC on a polymeric C₁₈ column using a gradient of acetonitrile/water as the mobile phase and fluorescence detection. Typical detection limits lie in the range of 1–30 ng ml^–1 of the analytes, but after sample pretreatment detection limits of 10–300 ng l^–1 were obtained. The extraction, clean-up and HPLC methodology was applied to the determination of selected PAH's in coal washings samples and the method was validated by the quantification of PAH's in a natural contaminated and a spiked sediment.     

Multivariate optimization of a GC-MS method for determination of sixteen priority polycyclic aromatic hydrocarbons in environmental samples

This paper describes the development and optimization, by using multivariate analysis, of a GC-MS-SIM method for evaluation of the 16 polyaromatic hydrocarbons considered as priority pollutants in atmospheric particulate material by the US EPA. In order to assure an adequate separation in the shortest analysis time, a multivariate design was used to set the conditions of the oven temperature program. The optimization process was carried out using factorial fractional design and Box-Behnken design. The following factors were evaluated: initial temperature, temperature rate #1, intermediary temperature, temperature rate #2, and final temperature. The optimized conditions were set at: 70 degrees C (2 min) --> 200 degrees C (30 degrees C/min, 5 min) --> 300 degrees C (5 degrees C/min, 1.67 min). Moreover, we have also optimized the injector temperature as 310 degrees C and sampling time as 0.8 min. The total analysis time was 33 min. Validation of GC-MS-SIM yielded satisfactory results for repetitivity of the detector response and retention times, and linearity of calibration curves. LOD were established as 0.13-0.34 ng/mL (peak area) and 0.18-0.72 ng/mL (peak height). The method has been shown to be appropriate for the analysis of samples of atmospheric particulate material and/or other environmental matrices.     

Isolation and determination of toxic congeners of polychlorinated biphenyls in environmental samples

A Method has been developed for the separation and enrichemen of there non-ortho, eight mono-ortho, and di-ortho substituted polychlorinated biphenyls (PCBs) from Aroclor formulations and environmental samples. The fractionation is accomplished using high performance liquid chromatography (HPLC) with a 2-(1-pyrenyl)ethyldimethylsilysily silca column. GC-MSD with an optimized temperature program was used for quantitation, Hexane, pentane, cyclohexane, iso-octane, and 2-propanol were tested as a mobile phase for the isolation of the thirteen target PCBs in a Aroclor 1242, 1254, and 1260 (1:1:1) misture, Pentane at room temperature with a slow rate of 0.7 ml/min is the condition of choice. The average recovery of thirteen target PCBs spiked in the Aroclor mixture is 99.5% with an average relative standard deviation of 4.5%. The average method detection limit is 8pg/μl. Targer PCBs in the reference solis, incinarator ash, and sediment samples were measured.     

Headspace single drop microextraction combined with HPLC for the determination of trace polycyclic aromatic hydrocarbons in environmental samples

A new method by combining headspace single drop microextraction (HS-SDME) with HPLC fluorescence detection for the determination of trace polycyclic aromatic hydrocarbons (PAHs) in environmental samples was developed. Aqueous solution of saturated beta-cyclodextrin was used as extraction solvent and five PAHs were employed as target analytes. The factors affecting the extraction efficiency were studied in detail and the optimal extraction conditions were established. Beta-cyclodextrin was found to play two important roles, one is the improvement of extraction efficiency of target analytes and the other is the enhancement of their fluorescence intensities in HPLC fluorescence detection. The detection limits for the target analytes were found to be in the range of 0.004-0.247ng/ml and the relative standard deviations (R.S.D.s) of 5.1-7.1% were obtained. The proposed method was applied to the analysis of trace PAHs in environmental samples with satisfactory results.     

Determination of polynuclear aromatic hydrocarbons in environmental samples by Micellar liquid chromatography

A method for the separation of polycyclic aromatic hydrocarbons (PAHs) by high-performance liquid chromatography using a hybrid micellar mobile phase is described. The detection of PAHs was carried out using the fluorescence method with programmable excitation and emission wavelength. The method is applied to the analysis of several environmental samples (sea water, sediments, limpets, sea worms) and several of these compounds are quantitated at concentration below 70 ng L⁻¹(kg⁻¹) in the original samples.     

Oriented ZnO nanoflakes on nickel-titanium alloy fibers for solid-phase microextraction of polychlorinated biphenyls and polycyclic aromatic hydrocarbons

ZnO nanoflakes (ZnONFs) were electrochemically grown on a nickel-titanium alloy (NiTi) wire for use in solid-phase microextraction. Prior to the growth of ZnONFs, the NiTi wire was hydrothermally treated for in-situ growth of TiO₂/NiO nanoflakes as a seeding base. The applied potential was used to control the dimensions of vertically oriented hexagonal ZnONFs. After annealing at 600 °C, the resulting fiber display fairly selective affinity for polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons. The fibers were applied to the preconcentration of PCBs which then were quantified by HPLC with UV detection. Compared to commercial polydimethylsiloxane coatings, the new coating displays high extraction capability, rapid extraction kinetics and superior cycling stability. This is assumed to be due to its high surface-to-volume ratio, double-sided open access structure, and enhanced structural stability. The assay excels by (a) a wide analytical range (0.10 to 200 μg L^?1 of PCBs), (b) low limits of detection (20–17 ng L^?1), and (c) low standard deviations for the single fiber repeatability (<9.8%) and for the fiber-to-fiber reproducibility (<7.5%). Satisfactory accuracy and precision were achieved when PCBs were determined by this method in spiked rain water, river water and wastewater samples.

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Graphical abstract ZnO nanoflakes were fabricated on a superelastic nickel-titanium alloy wire in desired orientation with enhanced extraction capability and good extraction selectivity. The fabricated fiber was suitable for the determination of PCBs in environmental water samples