Determination of polycyclic aromatic hydrocarbons in Athens atmosphere

Concentrations of total suspended particulates (TSP), benzene soluble fraction (BSF) and polycyclic aromatic hydrocarbons (PAH) have been determined in ambient air from four different sites in Athens, situated in urban, semi-industrial and industrial areas. GLC analysis has been applied for the determination of PAH, while the CGC/MS technique was used in order to confirm the obtained results. The same PAH pattern was observed for all stations. The identified PAH have been fluoranthene (FLA), pyrene (PYR), benzo(a)anthracene (BaA), chrysene (CHR), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), benzo(e)pyrene (BeP) and benzo(ghi)perylene (B(ghi)P). The concentrations of individual PAH ranged from traces to 33 ng m-3 (e.g. same or lower comparing to other large cities). The higher values of PAH were found during adverse meteorological conditions.     

Solvents and Techniques For The Extraction Of Polynuclear Aromatic Hydrocarbons From Filter Samples Of Diesel Exhaust

Abstract

The amounts of five polynuclear aromatic hydrocarbons-fluoranthene, pyrene, benzo(a)anthracene, benzo(k)fluoranthene, and benzo(a)pyrene-extracted by six solvents with four extraction techniques have been determined for diesel exhaust particulate collected on Teflon-coated glass fiber filters. Samples were analyzed by high pressure liquid chromatography with fluorescence detection. Toluene and methylene chloride gave higher recoveries than methanol, isopropanol, acetonitrile, and acetone for benzo(a)anthracene, benzo(k)fluoranthene, and benzo(a)pyrene. Soxhlet extraction for two hours (approximately 48 cycles) with toluene or acetonitrile was more effective than simple mechanical agitation, ultrasonic agitation for 15 minutes or immersion in refluxing ‘solvent’ for two hours.     

Solid-surface phosphorescence characterization of polycyclic aromatic hydrocarbons and selective determination of benzo(a)pyrene in water samples

This paper presents the phosphorescence characterization of polycyclic aromatic hydrocarbons (PAHs) on solid-surface for obtaining new flow-through phosphorescence optosensors for PAHs-based on-line, immobilized onto a non-ionic resin solid support coupled to a continuous flow system and the applications for the selective determination of benzo(a)pyrene (BaP). The phosphorescent characterization of 15 PAHs, described as major pollutants by the Environmental Protection Agency (EPA) (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-cd)pyrene, benzo(g,h,i)perylene and dibenzo(a,h)anthracene) has been carried out. The experimental variables (heavy atom, deoxygenation and organic solvent in samples) for obtaining different possibilities for developing mono and multi-parameter PAH sensors and the conditions for PAH screening have been carefully studied and the experimental conditions to determination of BaP in presence of other PAHs in water samples have been optimized.     

Determination of Polycyclic Aromatic Hydrocarbons in Traditional Chinese Medicine Raw Material,Extracts, and Health Food Products

The four polycyclic aromatic hydrocarbon markers (PAH4) of benzo[a]anthracene (BaA), chrysene (Chr), benzo[b]fluoranthene (BbF), and benzo[a]pyrene (BaP) are indicators showing polycyclic aromatic hydrocarbon (PAH) contamination levels in Chinese medicine raw materials (CMRMs), extracts and health food products; Samples of herbal medicine, herbal extracts, and food supplements were extracted with n-hexane, then cleaned up sequentially on Florisil and EUPAH solid-phase extraction (SPE) columns. A gas chromatography–mass spectrometry method for the determination of four polycyclic aromatic hydrocarbon markers in Chinese medicine raw material, extracts, and health food products was established; In spiked-recovery experiments, the average recovery was about 78.6–107.6% with a precision of 2.3–10.5%. The limit of quantification (LOQ) and limit of detection (LOD) of the PAH4 markers in this method were 2.0 μg/kg and 0.7 μg/kg, respectively. When the developed method was utilized to determine PAH4 contents in 12 locally available health food products, 3 samples contained over 10.0 μg/kg BaP, and 5 samples contained over 50.0 μg/kg PAH4. The European Union (EU) limits for BaP and PAH4 are 10 and 50.0 μg/kg, respectively; therefore, more attention must be drawn to the exposure risk of BaP and PAH4 in CMRMs, their extracts, and health food products. According to the risk assessment based on the Margin of Exposure (MOE) method, it is recognized that the products mentioned in this study pose a low risk.     

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。     

Improved analysis of Polycyclic Aromatic Hydrocarbons in atmospheric particulate matter by HPLC-fluorescence

An improved method is reported for determination of Polycyclic Aromatic Hydrocarbons (PAHs) in atmospheric particulate matter by HPLC-FLD. The sampling step (air volume collected during each sampling period varies in the range 10/13 m3) is carried out by means of a medium-flow pumping system (15 L min(-1)) on a glass fiber filter (47 mm diameter) placed as collecting substrate in the sampling-cassette. After sampling, the filter is extracted with 3 ml of acetonitrile in an ultrasonic bath for 30 minutes. As for extraction of PAHs from loaded filters a new criterion here is proposed to evaluate the recovery efficiency of PAHs from the sample, instead of the usual spiking method of standard solution. The extract was then reduced to 100 microL and analysed by HPLC-FLD on line spectra system. The method is rapid (about one hour for extraction and analysis), reproducible and enables to measure with good accuracy the atmospheric concentration of benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), benzo(ghi)perylene (BghiP), carcinogenic compounds always present in the urban airborne particulate matter. So it is useful for routine pollution studies and suitable to substitute the official method used now. Monthly average air concentrations, for the four PAHs above mentioned, measured in Rome from July 2001 to June 2002, are reported.     

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.     

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.     

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.     

Analytical Determination of Polycyclic Aromatic Hydrocarbons in Gases from Coal Conversion by Synchronous Fluorescence Spectrometry.

Abstract

A method to analyze the most hazardous Polyclyclic Aromatic Hydrocarbons (PAH) (acenaphtene, anthracene, benzo(a) anthracene, benzo(a)pyrene, biphenyl, coronene, chrysene, dibenzo (a,h) anthracene, phenantrene, fluoranthene, fluorene, naphtalene and pyrene), by using excitation and energy constant synchronic fluorescence has been researched in depth in this study.

Spectral studies carried out allow characteristic peaks to be obtained for the qualitative identification of 8 from 11 PAH tested. From the quantitative and interference studies, the most important analytical characteristics (linear range, detection limit and reproduciblity) for the determination of ten of these compounds have been obtained.

The method was applied to the PAH determination in two different samples: 1) air filter samples for urban pollution control and 2) air samples from a laboratory scale coal carbonization oven. Fluorene (in the first type) and benzo (a) pyrene (in the second type), were identified and quantified.     

Isolation of Stable Mutagenic Photodecomposition Products of Benzo(a)pyrene by Thin-Layer Chromatography

Abstract

Polycyclic aromatic hydrocarbons (PAH) are widespread in the atmosphere, the soil, waterways and oceans, as well as in the food chain. Major sources of PAH include emissions from transportation systems, heat and power generating plants, refuse burning and industrial processes (1,2,3). A significant number of these PAH are known to be carcinogenic (2,4,5). Epidemiological studies indicate that the environment is a significant factor in the incidence of human cancer, although many of the specific causal agents remain to be identified. One widely studied PAH i s benzo(a)pyrene (BaP), which is a carcinogen, and one of the most common PAH contaminants of the environment (6). Occupational exposure t o BaP has been documented (4). Mailath and Morik (7) studied the effect of sunlight and dark-room storage on BaP and reported that six and eight compounds, respectively, were observed when BaP was exposed to sunlight or left in the dark. There have been several reports of the degradation of BaP adsorbed on soot or smoke particles (8,9,10).     

Dibenzopyrenes,other PAHs with molecular weight 302, and selected carcinogenic PAHs seldom determined: identification and one-year quantification in urban air

The unambiguous identification in environmental samples of the potent carcinogen dibenzo[a,l]pyrene (DBalP) and the other DBPs (DBaeP, DBaiP, DBahP), whose evidence of carcinogenicity was recently re-evaluated by the International Agency for Research on Cancer (IARC), is an analytical challenge. This is attributed to their low concentrations in the environment and to the co-presence of several 302?MW isomers. In this study the four DBPs were identified in air, together with further four isomers with MW 302, based on an overall evaluation of five acceptance criteria. Their annual mean concentrations were quantified, for the first time to our knowledge. Thirteen other isomers were tentatively identified by comparison with previously published gas chromatographic profiles. The determinations were performed on PM10 samples collected every sixth day at a site in Rome, solvent extracted and analysed using GC/LRMS. The primary objective was to determine the mean DBP concentrations the population may be exposed to, and their consequent carcinogenic risks relative to benzo[a]pyrene (BaP) taken as a reference polycyclic aromatic hydrocarbon (PAH). The mean concentrations of DBalP, DBaeP, DBaiP and DBahP were, respectively, 0.014, 0.07, 0.02 and 0.01?ng?m^?3 (BaP: 0.65?ng?m^?3). Based on the available toxicity equivalence factors, DBalP contributed the carcinogenic risk of the PAH mixture by a factor of 2 relative to the risk attributable to BaP. DBaeP, DBahP and DBaiP contributed by, respectively, 11%, 1% and 0.3% of BaP. The instrumental conditions used to determine the 302?MW isomers allowed to unambiguously identify and to quantify other PAHs, ‘possibly carcinogenic’ to humans according to IARC, whose atmospheric concentrations reported in literature are scarce or missing: benzo[c]phenanthrene, 5-methylchrysene and benzo[j]fluoranthene (the latter being baseline resolved from isomers b and k). Finally, for completeness of information on PAHs recently upgraded by IARC to ‘possibly carcinogenic’, the concentrations of cyclopenta[cd]pyrene are reported.     

Cigarette filter as sorbent for on-line coupling of solid-phase extraction to high-performance liquid chromatography for determination of polycyclic aromatic hydrocarbons in water

An on-line solid-phase extraction (SPE) protocol using the cigarette filter as sorbent coupled with high-performance liquid chromatography (HPLC) was developed for simultaneous determination of trace naphthalene (NAPH), phenanthrene (PHEN), anthracene (ANT), fluoranthene (FLU), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), and benzo(ghi)perylene (BghiP) in water samples. To on-line interface solid-phase extraction to HPLC, a preconcentration column packed with the cigarette filter was used to replace a conventional sample loop on the injector valve of the HPLC for on-line solid-phase extraction. The sample solution was loaded and the analytes were then preconcentrated onto the preconcentration column. The collected analytes were subsequently eluted with a mobile phase of methanol-water (95:5). HPLC with a photodiode array detector was used for their separation and detection. The detection limits (S/N = 3) for preconcentrating 42 mL of sample solution ranged from 0.9 to 58.6 ng L(-1) at a sample throughput of 2 samples h(-1). The enhancement factors were in the range of 409-1710. The developed method was applied to the determination of trace NAPH, PHEN, ANT, FLU, BbF, BkF, BaP and BghiP in local river water samples. The recoveries of PAHs spiked in real water samples ranged from 87 to 115%. The precisions for nine replicate measurements of a standard mixture (NAPH: 4.0 microg L(-1), PHEN: 0.40 microg L(-1), ANT: 0.40 microg L(-1), FLU: 2.0 microg L(-1), BbF: 1.6 microg L(-1), BkF: 2.0 microg L(-1), BaP: 2.0 microg L(-1), BghiP: 1.7 microg L(-1)) were in the range of 1.2-5.1%.     

Collection and analytical characterisation of the atmospheric particulate in the city of Bari

In this paper an application of new procedures for atmospheric particulate analysis is illustrated. PM10, PAHs (benzo[a]anthracene (BaA), benzo[b]fluoranthene (BbF), benzo[j]fluoranthene (BjF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1, 2, 3-cd]pyrene (Ip), dibenzo[a, h]anthracene (DbA)) and heavy metals (Cu, Ni, Zn, Co, Mn, Cd, Fe and Pb) were investigated. PM10 determination was performed by gravimetric method, PAHs were measured by GC-MS, and heavy metals by HPIC. An air quality monitoring campaign on the territory of Bari municipality has been organised, and its results are shown.     

Ceramic Alumina in The HPLC Determination of Benzo(a)Pyrene in Air Particulate Material

Abstract

A fast room-temperature extraction by mechanical shredding of airborne particulate material collected on Hi-Vol filters is described. The polar compounds in the extract are quickly removed by test-tube adsorption. A group separation of polynuclear aromatic hydrocarbons (PAH) is made on Corning controlled pore ceramic alumina in stainless steel columns with methylene chloride in cyclohexane as the solvent. The pentacyclic fraction is taken at the same elution time as BaP and is evaporated to dryness under a stream of nitrogen. BaP is determined fluorometrically in concentrated sulfuric acid at F 538/553. It can also be dissolved in a polar solvent and separated and quantitated by reverse phase HPLC or gas chromatography. Total analysis time is approximately 2 hours, much of which is waiting time.     

Resolution of benzo[a]pyrene in complex mixtures of other polycyclic aromatic hydrocarbons. Comparison of two spectrofluorimetric methods applied to water samples

Two spectrofluorimetric methods, second-derivative constant-energy synchronous luminescence (SDCESL) and constant-wavelength synchronous luminescence (CWSL) in combination with multiple linear regression (MLR), for the quantification of benzo[a]pyrene (BaP) at sub-ng mL-1 levels, in the presence of benzo[b]fluoranthene (BbFt), benzo[k]fluoranthene (BkFt), benzo[ghi]perylene (BghiP) and indeno[1,2,3-cd]pyrene (IP), were developed and compared in detail. SDCESL presents lower limits of detection and quantification than CWSL/MLR and also gives more exact and precise results for levels close to the quantification limit. For BaP, SDCESL achieved quantification limits of 0.019 ng mL-1 in river waters and 0.007 ng mL-1 in drinking waters. This work offers a sensitive, precise, accurate, rapid, simple and economic methodology for monitoring BaP in waters for public consumption, meeting all the requirements of the EC Directive 98/83/CE that fixes the maximum admissible limit for this polycyclic aromatic hydrocarbon in drinking waters at of 0.010 ng mL-1.     

大气漂尘中苯并[a]芘的简单同步荧光测定

通过选择合适的能量差(Δ-υ=1 400 cm-1),建立了大气漂尘中苯并[a]芘的恒能量同步荧光分析法。苯并[a]芘在甲醇与十二烷基磺酸钠(SDS)溶液中均有良好的线性关系(R>0.999),检出限分别达到1.34 nmol/L与0.40 nmol/L。该法亦可应用于18种多环芳烃混合物中苯并[a]芘的鉴别。     

焦炉降尘中多环芳烃的毛细管超临界流体色谱分析

研究了９个多环芳烃混合样品的超临界流体色谱分析条件，并与毛细管气相色谱法做了比较。超临界流体色谱的条件是：柱温１１０℃；程序升压９．０ＭＰａ（５ｍｉｎ）１．４ＭＰａ／ｍｉｎ２８．０ ＭＰａ。各组分保留时间的相对标准偏差为 １．４％～３．０％，定量分析的相对误差为１．４％～６．０％，比毛细管气相色谱法具有明显的优越性。试验了焦炉降尘样品，发现该样品主要由双环和三环的多环芳烃类物质组成。其中萘含量约占８０％。     

Comparison of traditional cloud-point extraction and on-line flow-injection cloud-point extraction with a chemiluminescence method using benzo[a]pyrene as a marker

In this work, using benzo(a)pyrene (BaP) as marker, the analytical merits of on-line flow-injection cloud-point extraction (FI CPE), including preconcentration factor, extraction efficiency, sample throughput, and analysis time were evaluated by use of peroxyoxalate chemiluminescence (CL) detection. Moreover, by detailed discussion of several preconcentration conditions for traditional and on-line FI CPE the advantages of on-line FI CPE became conspicuously apparent. When coupled with separation techniques such as high-performance liquid chromatography (HPLC) or capillary electrophoresis (CE), on-line FI CPE–CL has much potential for analysis of low concentrations of polycyclic aromatic hydrocarbons (PAH) in environmental samples.     

Desorptivity versus chemical reactivity of polycyclic aromatic hydrocarbons (PAHs) in atmospheric aerosols collected on quartz fiber filters

Nine polycyclic aromatic hydrocarbons (PAHs) contained in air samples collected on quartz fiber filters inside an urban tunnel and in a nearby mixed commercial residential area in the city of Rio de Janeiro, Brazil, were exposed to scrubbed air (to measure desorption loss) and to particle-free ambient air (to measure chemical reaction losses in the absence of desorption). The exposures were conducted for 5.5 to 9 hour periods at ambient temperature (22-26 degrees C) at face velocities typical of high volume sampling. Under prevailing atmospheric conditions all nine PAHs experienced filter losses which (for most of them) followed first order kinetics. For the ambient samples, in a 6 hour exposure period, the following five PAHs showed filter losses (% in parantheses) attributed exclusively to chemical reaction: benzo(b)fluoranthene (43), benzo(k)fluoranthene (39), benzo(a)pyrene (70), benzo(ghi)perylene (44), and indeno (1,2,3-cd)pyrene (41). The other four showed the following unassigned losses: pyrene (100), fluoranthene (65), crysene (72), and benzo(a)anthracene (71). The results are discussed in the light of possible filter artifacts in PAH sampling and the use of PAH profile signatures for source identification of atmospheric particulate matter in receptor modeling.