Determination of Benzo(a)Pyrene and other Polynuclear Aromatic Hydrocarbons in Airborne Particulate Material by Ultrasonic Extraction and Reverse Phase High Pressure Liquid Chromatography

Abstract

Ultrasonic extraction of airborne particulate material on Hi-Vol filters is described. Almost all of the polar compounds are removed during the extraction by adsorption on the surface of the shredded glass fibers and controlled pore glass powder (CPG). The non-polar polynuclear aromatic hydrocarbons (PAH) in the extract are separated at room temperature by high pressure liquid chromatography (HPLC) on reverse phase Vydac using acetonitrile:water (70:30 v/v) as the chromatographic solvent. There is baseline separation of benzo(a)pyrene (BaP), benzo(k)fluoranthene (BkFt) and of benzo(e)pyrene (BeP), benzo(b)fluoranthene and perylene, the latter three present in one band. Extracts of airborne particulates show the same peaks. BaP elutes in approximately 14 minutes. Precision and accuracy measurements indicate full recovery of PAH and good extraction reproducibility. The detection limit of BaP at F 290/389 is less than 10 pg. Total analysis time is approximately 1 1/2 hr, most of which is waiting time.     

Determination of Polycyclic Aromatic Hydrocarbons in Airborne Particulate by High Performance Liquid Chromatography

This paper presents a trisolvent ultrasonic extraction and HPLC analysis method for the determination of 11 polycyclic aromatic hydrocarbons in air particulate collected on an air filter by a commercial high volume air sampler. A reverse phase column, Vydac 201 TP, and a gradient mobile phase, acetonitrile/water, were used. The 11 PAHs, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a, h]anthracene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene were completely resolved under experimental conditions. All the PAHs except coronene were monitored by fluorescence with λ_ex=270 nm, λ_em>389 nm. Coronene was monitored by UV with λ=300 nm. The methodology was evaluated by spiking SRM 1649 with a PAH standard and then going through different extraction procedures and analyzing the PAH concentrations without clean-up. An external standard method was used for quantitation. The recovery yields for fluoranthene, benz[a]anthracene, benzo[a]pyrene, benzo[ghi]perylene and indeno[l,2,3-cd]pyrene were above 90%. The detection limits of PAH with fluorescence at λ_ex=270 nm, λ_em>389 nm ranged from 5.7 pg to 69.5 pg.     

Supercritical fluid extraction of polycyclic aromatic hydrocarbons from liver samples and determination by HPLC-FL

An extraction/clean-up procedure by SFE was developed for isolating PAHs from liver samples for subsequent HPLC-FL determination of ten PAHs in the enriched extract. Recoveries (90-115%) and RSD % (< or =7.7) were satisfactory. When applied to 11 samples of bird of prey (Tyto alba) protected species and classified of special interest, from the Galicia (Northwest to Spain), benzo[ghi]perylene and indeno[1,2,3-cd]pyrene were undetectable; chrysene and benzo[a]pyrene are only detected in one sample; benzo[a]anthracene and benzo[k]fluoranthene are only quantified in one sample and benzo[b]fluoranthene in two samples. The other PAHs, anthracene, fluoranthene and pyrene are present in almost all the samples.     

Optimization of the extraction of polycyclic aromatic hydrocarbons from wood samples by the use of microwave energy

A simple and rapid microwave-assisted extraction (MAE) procedure was developed and optimized for benzo[a]anthracene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene and benzo[a]pyrene in wood samples. The spiked wood used was prepared 3 months before analysis to simulate weathering processes and to allow the formation of analyte-matrix interaction. The samples, immersed in acetonitrile were irradiated with microwaves in a closed-vessel system. Optimization of the method was achieved by using a factorial design approach on parameters such as extraction time, temperature and sample amount. The analysis of extracts has been carried out by reversed-phase high-performance liquid chromatography with fluorescence detection for quantification and UV-diode-array detection for confirmation. The MAE procedure yielded extracts that could be analyzed directly without any preliminary clean-up or solvent exchange steps.     

A Gas Liquid Chromatographic Fluorescent Procedure for the Analysis of Benzo(A)Pyrene in 24 Hour Atmospheric Particulate Samples

Abstract

This paper describes a selective method for the assay of benzo(a)pyrene (BaP) in 24 hour particulate samples. Benzo(a)pyrene is partially separated from the other polynuclear aromatic hydrocarbons via gas chromatography and then is completely resolved optically from traditionally difficult to resolve compounds (benzo(e)pyrene, perylene, benzo(k)fluoranthene) by means of a gas phase fluorescent detector. Ambient air concentrations as low as 20 picograms per cubic meter of air can be assayed with this gas chromatographic - gas phase fluorescent detection system.     

Determination of polycyclic aromatic hydrocarbons from buzzards (Buteo buteo) and tawny owl (Strix aluco) by liquid chromatography with fluorescence detection

Supercritical fluid extraction was applied to the determination of naturally contaminated polycyclic aromatic hydrocarbons (PAHs) in bird tissue by liquid chromatography with fluorescence detection (LC-FL). Recoveries (> 90%) and relative standard deviations (< or = 7.7%) were satisfactory. The levels of 10 PAHs were analyzed in 6 classes of tissues (heart, liver, intestine, muscle, lung, and kidney) of 10 buzzards and 2 tawny owls, predatory birds from the Galicia (northwest Spain). The PAHs found most abundantly were pyrene, fluoranthene, benzo[a]anthracene, and anthracene. Chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene were not detected. Intestine, kidney, and lung were more polluted than other tissues.     

Admicelle-enhanced synchronous fluorescence spectrometry for the selective determination of polycyclic aromatic hydrocarbons in water

A simple and rapid method for the highly sensitive determination of polycyclic aromatic hydrocarbons (PAHs) in water was developed. Benzo[a]pyrene, benzo[k]fluoranthene, perylene, and pyrene in water were concentrated into sodium dodecyl sulfate (SDS)-alumina admicelles. The collection was performed by adding SDS and alumina particles into the sample solution at pH 2. After gentle mixing, the resulting suspension was passed through a membrane filter to collect the SDS admicelles containing highly concentrated PAHs. The filter was placed on a slide glass and then covered admicellar layer with a fused silica glass plate before setting in a fluorescence spectrometer. Benzo[a]pyrene, benzo[k]fluoranthene, perylene, and pyrene were selectively determined by the synchronous fluorescence scan (SFS) analysis with keeping wavelength intervals between excitation and emission to 98, 35, 29, and 45 nm, respectively. Because of the minimum spectral overlapping, 1-40 ng l⁻¹ of benzo[a]pyrene, benzo[k]fluoranthene, and perylene as well as 10-150 ng l⁻¹ of pyrene were selectively determined with eliminating the interferences of other 12 PAHs. The detection limits were 0.3 ng l⁻¹ for benzo[a]pyrene, benzo[k]fluoranthene, and perylene, and 1 ng l⁻¹ for pyrene. They were 2-3 orders of magnitude lower than the detection limits in normal aqueous micellar solutions. The application to water analysis was studied.     

Supercritical fluid extraction of polycyclic aromatic hydrocarbons from liver samples and determination by HPLC-FL

An extraction/clean-up procedure by SFE was developed for isolating PAHs from liver samples for subsequent HPLC-FL determination of ten PAHs in the enriched extract. Recoveries (90–115%) and RSD % (≤ 7.7) were satisfactory. When applied to 11 samples of bird of prey (Tyto alba) protected species and classified of special interest, from the Galicia (Northwest to Spain), benzo[ghi]perylene and indeno[1,2,3-cd]pyrene were undetectable; chrysene and benzo[a]pyrene are only detected in one sample; benzo[a]anthracene and benzo[k]fluoranthene are only quantified in one sample and benzo[b]fluoranthene in two samples. The other PAHs, anthracene, fluoranthene and pyrene are present in almost all the samples.     

Validation of a method for extraction of polycyclic aromatic hydrocarbons from sewage sludge and analysis by GC-MS

In the present study, the solid–liquid extraction with low temperature purification was validated for the determination of 16 polycyclic aromatic hydrocarbons from sewage sludge by gas chromatography-mass spectrometry. Recoveries ranged 70–114% for naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene and chrysene, while the compounds benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene showed recoveries of between 40 and 70%. The relative standard deviation was less than 13% for all of the compounds. Negative matrix effect was observed on the 10 compounds with less retention time in the chromatographic analysis and positive matrix effect noticed on the others. The limits of quantification were from 2 to 20 μg kg^?1, about 30 times less than the maximum residue limit allowed in sludge by the European Union. The validated method produced quantification of 11 PAHs in one sludge sample at concentrations ranging 20–2000 μg kg^?1.     

Combination of micellar extraction of polycyclic aromatic hydrocarbons from aqueous media with detection by synchronous fluorescence

Summary The application of different non-ionic surfactants for the micellar extraction and enrichment of PAHs from aqueous media was tested. Recoveries were up to 100%. A spectroscopic method for the simultaneous detection of PAH-mixtures by synchronous fluorescence in the micellar phase was developed, with detection limits of 6.8 and 2.6 ng/l for benzo(k)fluoranthene and benzo(a)pyrene, respectively. The method was applied to the extraction and detection of benzo(k)fluoranthene/benzo(a)pyrene mixtures from aqueous solutions and soil suspensions. Genapol X-80 was found to suppress PAH-adsorption on bentonite at surfactant concentrations above 0.1%.Dedicated to Prof. Dr. V. Krivan on the occasion of his 60th birthday.     

Papierchromatographische Trennung und quantitative Bestimmung von Benzo(a)pyren und Benzo(k)fluoranthen in Schwebstoffen

Zusammenfassung Die Leistungsfähigkeit des papierchromatographischen Verfahrens von Wieland und Kracht zur Trennung von Benzo(a)pyren und Benzo(k)fluoranthen wurde an synthetischen Gemischen und Schwebstoffextrakten untersucht, da die Fluoreszenzspektren sowie die Eigenschaften dieser Substanzen sehr ähnlich sind. Die Meßergebnisse zeigen, daß eine einwandfreie Trennung der beiden Substanzen voneinander sowie darüber hinaus von anderen fluoreszierenden Anteilen der Schwebstoffextrakte gelingt. Die Wiederauffindungsrate bei Versuchen mit internem Standard liegt je nach Konzentrationsbereich zwischen 86 und 103%. Das wenig aufwendige Verfahren erscheint damit sowohl zur Bestimmung von Benzo(a)pyren als auch Benzo(k)fluoranthen in der Atmosphäre geeignet.

---

Paper chromatographic separation and quantitative determination of benzo(a)pyrene and benzo(k)fluoranthene in suspended material

Summary The effectiveness of the paper Chromatographic procedure of Wieland and Kracht for separation of benzo(a)pyrene and benzo(k)fluoranthene was investigated on synthetic mixtures and extracts of suspensions since the fluorescence spectra and the properties of these substances are very similar. The results of measurements show that an impeccable separation of the two substances from each other as well as from other fluorescing components of the suspension extract is possible. In trials with internal standard the recovery rate was between 86 and 103% depending on the concentration. The procedure is inexpensive and is thus suitable for determination of benzo(a)pyrene and benzo(k)fluoranthene in the atmosphere.

     

超高效合相色谱快速分析塑料制品中的18种多环芳烃

建立了一种超高效合相色谱-二极管阵列检测器快速分析塑料制品中萘、苊烯、苊、芴、菲、蒽、荧蒽、芘、苯并(a)蒽、(屈艹) 、苯并(b)荧蒽、苯并(k)荧蒽、苯并(j)荧蒽、苯并(e)芘、苯并(a)芘、茚并(1,2,3-cd)芘、二苯并(a,h)蒽、苯并(g,h,i)苝(二萘嵌苯)的方法。以甲苯为溶剂,超声萃取实际塑料制品中的多环芳烃,经超高效合相色谱分析。采用Daicel IB-3手性色谱柱,以CO₂为流动相,甲醇/乙腈(25:75, v/v)为流动相助溶剂,在柱温为40 ℃,背压为15.17 MPa的条件下,18种多环芳烃在8.5 min之内实现基线分离。18种多环芳烃的线性范围为0.05~50 mg/L(r≥0.9995),定量限(S/N> 10)为0.05 mg/L。加标回收率为78.3%~117.6%,相对标准偏差(RSD, n=5)小于5%。该方法具有分析速度快、分离效率高、节约有机溶剂的优点。     

Interpretative optimization and artificial neural network modeling of the gas chromatographic separation of polycyclic aromatic hydrocarbons

An interpretative strategy (factorial design experimentation+total resolution analysis+chromatogram simulation) was employed to optimize the separation of 16 polycyclic aromatic hydrocarbons (PAHs) (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(a)anthracene, benzo(k)fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, indeno(1,2,3-c,d)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perylene) in temperature-programmed gas chromatography (GC). Also, the retention behavior of PAHs in the same GC system was studied by a feed-forward artificial neural network (ANN). GC separation was investigated as a function of one (linear temperature ramp) or two (linear temperature ramp+the final hold temperature) variables. The applied interpretative approach resulted in rather good agreement between the measured and the predicted retention times for PAHs in both one and two variable modeling. The ANN model, strongly affected by the number of input experiments, was shown to be less effective for one variable used, but quite successful when two input variables were used. All PAHs, including difficult to separate peak pairs (benzo(k)fluoranthene/benzo(b)fluoranthene and indeno(1,2,3-c,d)pyrene/dibenzo(a,h)anthracene), were separated in a standard (5% phenyl-95% dimethylpolysiloxane) capillary column at an optimum temperature ramp of 8.0 degrees C/min and final hold temperature in the range of 260-320 degrees C.     

Improved efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) from the National Institute of Standards and Technology (NIST) Standard Reference Material Diesel Particulate Matter (SRM 2975) using accelerated solvent extraction

The efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) with molecular masses of 252, 276, 278, 300, and 302 Da from standard reference material diesel particulate matter (SRM 2975) has been investigated using accelerated solvent extraction (ASE) with dichloromethane, toluene, methanol, and mixtures of toluene and methanol. Extraction of SRM 2975 using toluene/methanol (9:1, v/v) at maximum instrumental settings (200 °C, 20.7 MPa, and five extraction cycles) with 30-min extraction times resulted in the following elevations of the measured concentration when compared with the certified and reference concentrations reported by the National Institute of Standards and Technology (NIST): benzo[b]fluoranthene, 46%; benzo[k]fluoranthene, 137%; benzo[e]pyrene, 103%; benzo[a]pyrene, 1,570%; perylene, 37%; indeno[1,2,3-cd]pyrene, 41%; benzo[ghi]perylene, 163%; and coronene, 361%. The concentrations of the following PAHs were comparable to the reference values assigned by NIST: indeno[1,2,3-cd]fluoranthene, dibenz[a,h]anthracene, and picene. The measured concentration of dibenzo[a,e]-pyrene was lower than the information value reported by the NIST. The measured concentrations of other highly carcinogenic PAHs (dibenzo[a,l]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene) in SRM 2975 are also reported. Comparison of measurements using the optimized ASE method and using similar conditions to those applied by the NIST for the assignment of PAH concentrations in SRM 2975 indicated that the higher values obtained in the present study were associated with more complete extraction of PAHs from the diesel particulate material. Re-extraction of the particulate samples demonstrated that the deuterated internal standards were more readily recovered than the native PAHs, which may explain the lower values reported by the NIST. The analytical results obtained in the study demonstrated that the efficient extraction of PAHs from SRM 2975 is a critical requirement for the accurate determination of PAHs with high molecular masses in this standard reference material and that the optimization of extraction conditions is essential to avoid underestimation of the PAH concentrations. The requirement is especially relevant to the human carcinogen benzo[a]pyrene, which is commonly used as an indicator of the carcinogenic risk presented by PAH mixtures.     

On-site solid phase extraction and coupled-column high-performance liquid chromatographic determination of six polycyclic aromatic hydrocarbons in water

A high-performance liquid chromatographic method for the determination of fluoranthene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, benzo(g,h,i)perylene and indeno(1,2,3-cd)pyrene in water is presented. The analytical procedure consists of on-site solid-phase extraction of the analytes on a selective sample column using a new device, transport and integration of the loaded sample column into a HPLC-system and coupled-column HPLC-analysis. The method allows reliable quantification of the PAHs at the low ng/l-level in particle-free as well as in particle-containing surface water.Dedicated to Professor Dr. Dr. h.c. mult. J. F. K. Huber on the occasion of his 70th birthday     

Optimization of the matrix solid-phase dispersion sample preparation procedure for analysis of polycyclic aromatic hydrocarbons in soils: comparison with microwave-assisted extraction

A fast and simple preparation procedure based on the matrix solid-phase dispersion (MSPD) technique is proposed for the first time for the isolation of 16 polycyclic aromatic hydrocarbons (PAHs) from soil samples. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-c,d]pyrene were considered in the study. Extraction and clean-up of samples were carried out in a single step. The main parameters that affect extraction yield, such as dispersant, type and amount of additives, clean-up co-sorbent and extractive solvent were evaluated and optimized. The addition of an alkali solution in MSPD was required to provide quantitative recoveries. Analytical determinations were carried out by high performance liquid chromatography (HPLC) with fluorescence detection. Quantification limits (between 0.01 and 0.6 ng g(-1) dry mass) were well below the regulatory limits for all the compounds considered. The extraction yields for the different compounds obtained by MSPD were compared with the yields obtained by microwave-assisted extraction (MAE). To test the accuracy of the MSPD technique, the optimized methodology was applied to the analysis of standard reference material BCR-524 (contaminated industrial soil), with excellent results.     

Sample preparation of sewage sludge and soil samples for the determination of polycyclic aromatic hydrocarbons based on one-pot microwave-assisted saponification and extraction

A microwave-assisted sample preparation (MASP) procedure was developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge and soil samples. The procedure involved the simultaneous microwave-assisted extraction of PAHs with n-hexane and the hydrolysis of samples with methanolic potassium hydroxide. Because of the complex nature of the samples, the extracts were submitted to further cleaning with silica and Florisil solid-phase extraction cartridges connected in series. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene, were considered in the study. Quantification limits obtained for all of these compounds (between 0.4 and 14.8 μg kg⁻¹ dry mass) were well below of the limits recommended in the USA and EU. Overall recovery values ranged from 60 to 100%, with most losses being due to evaporation in the solvent exchange stages of the procedure, although excellent extraction recoveries were obtained. Validation of the accuracy was carried out with BCR-088 (sewage sludge) and BCR-524 (contaminated industrial soil) reference materials.     

Vortex‐assisted extraction combined with dispersive liquid–liquid microextraction for the determination of polycyclic aromatic hydrocarbons in sediment by high performance liquid chromatography

A simple, rapid, and efficient method, vortex‐assisted extraction followed by dispersive liquid–liquid microextraction (DLLME) has been developed for the extraction of polycyclic aromatic hydrocarbons (PAHs) in sediment samples prior to analysis by high performance liquid chromatography fluorescence detection. Acetonitrile was used as collecting solvent for the extraction of PAHs from sediment by vortex‐assisted extraction. In DLLME, PAHs were rapidly transferred from acetonitrile to dichloromethane. Under the optimum conditions, the method yields a linear calibration curve in the concentration range from 10 to 2100 ng g^?1 for fluorene, anthracene, chrysene, benzo[k]fluoranthene, and benzo[a]pyrene, and 20 to 2100 ng g^?1 for other target analytes. Coefficients of determinations ranged from 0.9986 to 0.9994. The limits of detection, based on signal‐to‐noise ratio of three, ranged from 2.3 to 6.8 ng g^?1. Reproducibility and recoveries was assessed by extracting a series of six independent sediment samples, which were spiked with different concentration levels. Finally, the proposed method was successfully applied in analyses of real nature sediment samples. The proposed method extended and improved the application of DLLME to solid samples, which greatly shorten the extraction time and simplified the extraction process.     

Resolution of 13 polycyclic aromatic hydrocarbons by constant-wavelength synchronous spectrofluorometry.

A method capable of determining 13 PAHs (acenaphthene, anthracene, benzo[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, chrysene, dibenzo[ah]anthracene, fluoranthene, fluorene, indene[1,2,3-cd]pyrene, phenanthrene and pyrene) in a mixture of 16 EPA PAHs by second derivative synchronous spectrofluorometry in the constant wavelength mode was developed. It has not been possible to determine the following PAHs in the mixture: acenaphthylene, benzo[ghi]perylene and naphthalene. The approach studied allows the sensitive, rapid and inexpensive identification and quantitation of 13 PAHs in a solution of hexane. The detection limits are <1 microg L(-1) (except for chrysene and phenanthrene).     

Second-derivative constant-wavelength synchronous scan spectrofluorimetry for determination of benzo[b]fluoranthene, benzo[a]pyrene and indeno[1,2,3-cd]pyrene in drinking water

The use of derivative constant-wavelength synchronous scan fluorimetry is reported for the determination of three polycyclic aromatic hydrocarbon pollutants in drinking water (linearity range 0.4-4 mug 1(-1)). The limits of detection (LD) and quantification (LQ) (mug 1(-1)) are 0.01 and 0.07 for benzo[b]fluoranthene, 0.03 and 0.12 for benzo[a]pyrene and 0.19 and 0.57 for indeno[1,2,3-cd]pyrene in the presence of three other pollutants, benzo[k]fluoranthene, benzo[ghi]perylene and fluoranthene. The precision (RSD /= 85%) were satisfactory.