Selected Ion Chromatograms and Tandem Mass Spectrometry for Detection of Trace Polycyclic Aromatic Hydrocarbons in Diesel Exhaust

Abstract

Polycyclic aromatic hydrocarbon (PAH) measurements are essential for scientists and engineers who investigate these anthropogenic compounds. Diesel engines contribute to the problem, so analysts are measuring PAHs from these sources. However, diesel exhaust presents special problems for precise analytical measurements. The exhaust matrix is very complex; consequently, PAH detection sensitivity deteriorates, especially for trace PAHs in the exhaust. Yet, these are conditions and amounts that exist in real samples. Nonetheless, selected ion chromatogram (SIC) and tandem mass spectrometry (MS/MS) techniques improve trace PAH detection; ion trap technology makes both mass techniques possible. The purpose of this investigation was to evaluate SIC and MS/MS for applications to measure PAHs in diesel exhaust samples. The signal-to-noise ratio for accurate quantitation improves, relative to traditional mass techniques, because these techniques ignore or eliminate interfering components. On a VF-5MS chromatographic column, these techniques improve sensitivity and reproducibility. They produce a superior limit of detection in the useful range for PAH samples extracted from actual engine exhaust, 10–30 pg for the smaller PAHs and 1–6 ng for the larger PAHs. The results with SIC and MS/MS are reproducible, so analysts can report PAH amounts with defined statistical confidence intervals. SIC and MS/MS improve detection for trace PAHs in convoluted diesel exhaust samples.     

Polycyclic aromatic hydrocarbon exhaust emissions from different reformulated diesel fuels and engine operating conditions

The study of light-duty diesel engine exhaust emissions is important due to their impact on atmospheric chemistry and air pollution. In this study, both the gas and the particulate phase of fuel exhaust were analyzed to investigate the effects of diesel reformulation and engine operating parameters. The research was focused on polycyclic aromatic hydrocarbon (PAH) compounds on particulate phase due to their high toxicity. These were analyzed using a gas chromatography–mass spectrometry (GC–MS) methodology.Although PAH profiles changed for diesel fuels with low-sulfur content and different percentages of aromatic hydrocarbons (5–25%), no significant differences for total PAH concentrations were detected. However, rape oil methyl ester biodiesel showed a greater number of PAH compounds, but in lower concentrations (close to 50%) than the reformulated diesel fuels. In addition, four engine operating conditions were evaluated, and the results showed that, during cold start, higher concentrations were observed for high molecular weight PAHs than during idling cycle and that the acceleration cycles provided higher concentrations than the steady-state conditions. Correlations between particulate PAHs and gas phase products were also observed.The emission of PAH compounds from the incomplete combustion of diesel fuel depended greatly on the source of the fuel and the driving patterns.     

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.     

Large-volume injection PTV-GC-MS analysis of polycyclic aromatic hydrocarbons in air and sediment samples

For the analysis of trace organic pollutants in environmental samples using a gas chromatographic (GC) instrument, large-volume injection using the programmable temperature vaporization (PTV) technique has many advantages over the traditional split/splitless injection. By increasing the injection volume from 1 or 2 microL with a split/splitless inlet to 60 microL or higher with the PTV inlet, analytical sensitivity is greatly enhanced for analytes with low concentrations. Results obtained from optimization of instrument operational parameters for analyzing polycyclic aromatic hydrocarbons (PAHs) are reported in this paper. The laboratory method detection limits for 16 PAHs and six deuterated PAH surrogates were determined using seven replicate spike samples. The initial temperature of the inlet was found to be critical in determining the analytical sensitivity of PAHs with two or three rings due to loss of these relatively highly volatile compounds during solvent vaporization. For most PAHs, the response of the mass spectrometry detector increased proportionally as the total injected volume was increased up to 150 microL. Significant interference from rubber material of the sample vial septa was observed.     

The distribution of particle-phase organic compounds in the atmosphere and their use for source apportionment during the Southern California Children''s Health Study

Atmospheric particulate matter (PM) samples from 12 sites in southern California, collected as part of the Southern California Children's Health Study (SCCHS), were analyzed using gas chromatography/mass spectrometry (GC/MS) techniques. Ninety-four organic compounds were quantified in these samples, including n-alkanes, fatty acids, polycyclic aromatic hydrocarbons (PAH), hopanes, steranes, aromatic diacids, aliphatic diacids, resin acids, methoxyphenols, and levoglucosan. Annual average concentrations of all detected compounds, as well as average concentrations for three seasonal periods, were determined at all 12 sites for the calendar year of 1995. These measurements provide important information about the seasonal and spatial distribution of particle-phase organic compounds in southern California. Also, co-located samples from one site were analyzed to assess precision of measurement. Excellent agreement was observed between annual average concentrations for the broad range of organic compounds measured in this study. Measured concentrations from the 12 sampling sites were used in a previously developed molecular-marker source apportionment model to quantify the primary source contributions to the PM10 organic carbon and mass concentrations at these 12 sites. Source contributions to atmospheric PM from six important air pollution sources were quantified: gasoline-powered motor vehicle exhaust, diesel vehicle exhaust, wood smoke, vegetative detritus, tire wear, and natural gas combustion. Important trends in the seasonal and spatial patterns of the impact of these six sources were observed. In addition, contributions from meat smoke were detected in selected samples.     

Emission inventory and sources of polycyclic aromatic hydrocarbons in the atmosphere at a suburban area in Taiwan

The application of a chemical mass balance air pollution model to ambient measurements of polycyclic aromatic hydrocarbons (PAHs) is presented. Sixteen air samples were collected at seven sites in a suburban area in Taiwan and analyzed for the concentration of 21 compounds between July 2001 and September 2001. Each ambient sample was evaluated for the PAH contribution from six sources (heavy oil combustion, natural gas combustion, coal combustion, diesel combustion, vehicles and municipal solid waste incinerator). Average predictions agree well with the emission inventory. By this method, the average contributions are 49%, 14%, 22%, 12%, and 2% from vehicles, heavy oil combustion, natural gas combustion, coal combustion and diesel combustion at these seven receptors. By far, vehicles are the major PAH emission sources and municipal solid waste incinerator is a minor contributor. The calculated result of particulate PAHs is compared with that of total (gaseous and particulate) PAHs. The estimate based on total PAHs is better than the estimate based on particulate PAHs only. Contributions of eight low reactive PAHs for the same emission sources and receptors were calculated. Atmospheric reactivity seems not a problem for source apportionment in this study.     

The Distribution of Particle-Phase Organic Compounds in the Atmosphere and Their Use for Source Apportionment during the Southern California Children’s Health Study

Abstract

Atmospheric particulate matter (PM) samples from 12 sites in southern California, collected as part of the Southern California Children’s Health Study (SCCHS), were analyzed using gas chromatography/mass spectrometry (GC/MS) techniques. Ninety-four organic compounds were quantified in these samples, including n-alkanes, fatty acids, polycyclic aromatic hydrocarbons (PAH), ho-panes, steranes, aromatic diacids, aliphatic diacids, resin acids, methoxyphenols, and levoglucosan. Annual average concentrations of all detected compounds, as well as average concentrations for three seasonal periods, were determined at all 12 sites for the calendar year of 1995. These measurements provide important information about the seasonal and spatial distribution of particle-phase organic compounds in southern California. Also, co-located samples from one site were analyzed to assess precision of measurement. Excellent agreement was observed between annual average concentrations for the broad range of organic compounds measured in this study. Measured concentrations from the 12 sampling sites were used in a previously developed molecular-marker source apportionment model to quantify the primary source contributions to the PM₁₀ organic carbon and mass concentrations at these 12 sites. Source contributions to atmospheric PM from six important air pollution sources were quantified: gasoline-powered motor vehicle exhaust, diesel vehicle exhaust, wood smoke, vegetative detritus, tire wear, and natural gas combustion. Important trends in the seasonal and spatial patterns of the impact of these six sources were observed. In addition, contributions from meat smoke were detected in selected samples.     

Characteristics of trans,trans-2,4-decadienal and polycyclic aromatic hydrocarbons in exhaust of diesel engine fueled with biodiesel

The use of biodiesel fuel as a substitute for fossil fuel in diesel engines has received increasing attention in recent years. This study is the first to investigate and compare the characteristics of mutagenic species, trans,trans-2,4-decadienal (tt-DDE), and polycyclic aromatic hydrocarbons (PAHs) in the diluted exhaust of diesel engines operated with diesel and biodiesel blend fuels. An engine of current design was operated on a dynamometer consistent with the US federal test procedure transient-cycle specifications. Petroleum diesel and a blend of petroleum diesel and biodiesel (B20) were tested. Exhaust sampling was carried out on diluted exhaust in a dilution tunnel with a constant-volume sampling system. Concentrations of tt-DDE and PAHs were analyzed by GC/MS. Although average PAH emission factors decreased from 1403 to 1051 μg bhp-h⁻¹, the results show that tt-DDE is evidently generated (1.28 μg bhp-h⁻¹) in the exhaust of diesel engine using B20 as fuel. This finding suggests that tt-DDE emission from the use of biodiesel should be taken into account in characterization and health-risk assessment. The results also show that tt-DDE is depleted in the diesel engine combustion process and the existence of tt-DDE in biodiesel is the major source of tt-DDE emission. The distribution of tt-DDE in the particulate phase is 55.3% under this study's sampling conditions. For diesel and B20, PAH phase distributions have similar trends. Lower molecular weight PAHs predominate in gaseous phase for both diesel and B20. Cold-start driving has higher tt-DDE and PAH emission factors, as well as a higher percentage of tt-DDE in particulate phase, than for warm-start driving.     

Characterization of atmospheric particulates, particle-bound transition metals and polycyclic aromatic hydrocarbons of urban air in the centre of Athens (Greece)

The concentrations of trace metals and polycyclic aromatic hydrocarbons (PAHs) adsorbed to total suspended particulate (TSP) and finer fractions of airborne particulate matter (PM) were determined from a site in the centre of Athens (Greece), which is characterized by heavy local traffic and is densely populated, during the winter and summer periods in 2003-2004. Also, we collected and analyzed samples of diesel and gasoline exhaust particles from local vehicles (buses, taxis and private cars) and from chimney exhaust of residential central heating appliances. A seasonal effect was observed for the size distribution of aerosol mass, with a shift to larger fine fractions in winter. The most commonly detected trace metals in the TSP and PM fractions were Fe, Pb, Zn, Cu, Cr, V, Ni and Cd and their concentrations were similar to levels observed in heavily polluted urban areas from local traffic and other anthropogenic emissions. Analysis of 16 PAHs bound to PM showed that they are mostly traffic related. In general, the fine particulate PAHs concentrations were higher than coarse particles. The most common PAHs in PM(10.2) and PM(2.1) were pyrene, phenanthrene, acenapthylene and fluoranthene, which are associated with diesel and gasoline exhaust particles. The results of this study underlined the importance of local emission sources, especially vehicular traffic, central heating and other local anthropogenic emissions. Compared with other big cities, Athens has much higher levels of airborne particles, especially of the finer fractions PM(10) and PM(2.5), correlated with traffic-related air pollution.     

Control of diesel gaseous and particulate emissions with a tube-type wet electrostatic precipitator

In this study, experiments were performed with a bench-scale tube-type wet electrostatic precipitator (wESPs) to investigate its effectiveness for the removal of mass- and number-based diesel particulate matter (DPM), hydrocarbons (HCs), carbon monoxide (CO), and oxides of nitrogen (NOx) from diesel exhaust emissions. The concentration of ozone (O3) present in the exhaust that underwent a nonthermal plasma treatment process inside the wESP was also measured. A nonroad diesel generator operating at varying load conditions was used as a stationary diesel emission source. The DPM mass analysis was conducted by means of isokinetic sampling and the DPM mass concentration was determined by a gravimetric method. An electrical low-pressure impactor (ELPI) was used to quantify the DPM number concentration. The HC compounds, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs) were collected on a moisture-free quartz filter together with a PUF/XAD/PUF cartridge and extracted in dichloromethane with sonication. Gas chromatography (GC)/mass spectroscopy (MS) was used to determine HC concentrations in the extracted solution. A calibrated gas combustion analyzer (Testo 350) and an O3 analyzer were used for quantifying the inlet and outlet concentrations of CO and NOx (nitric oxide [NO] + nitrogen dioxide [NO2]), and O3 in the diesel exhaust stream. The wESP was capable of removing approximately 67-86% of mass- and number-based DPM at a 100% exhaust volumetric flow rate generated from 0- to 75-kW engine loads. At 75-kW engine load, increasing gas residence time from approximately 0.1 to 0.4 sec led to a significant increase of DPM removal efficiency from approximately 67 to more than 90%. The removal of n-alkanes, 16 PAHs, and CO in the wESP ranged from 31 to 57% and 5 to 38%, respectively. The use of the wESP did not significantly affect NOx concentration in diesel exhaust. The O3 concentration in diesel exhaust was measured to be less than 1 ppm. The main mechanisms responsible for the removal of these pollutants from diesel exhaust are discussed.     

Large PAHs detected in fine particulate matter emitted from light-duty gasoline vehicles

Emission factors of large PAHs with 6–8 aromatic rings with molecular weights (MW) of 300–374 were measured from 16 light-duty gasoline-powered vehicles (LDGV) and one heavy-duty diesel-powered vehicle (HDDV) operated under realistic driving conditions. LDGVs emitted PAH isomers of MW 302, 326, 350, and 374, while the HDDV did not emit these compounds. This suggests that large PAHs may be useful tracers for the source apportionment of gasoline-powered motor vehicle exhaust in the atmosphere. Emission rates of MW 302, 326, and 350 isomers from LDGVs equipped with three-way catalysts (TWCs) ranged from 2 to 10 (μg L⁻¹ fuel burned), while emissions from LDGVs classified as low emission vehicles (LEVs) were almost a factor of 10 lower. MW 374 PAH isomers were not quantified due to the lack of a quantification-grade standard. The reduced emissions associated with the LEVs are likely attributable to improved vapor recovery during the “cold-start” phase of the Federal Test Procedure (FTP) driving cycle before the catalyst reaches operating temperature. Approximately 2 (μg g⁻¹ PM) of MW 326 and 350 PAH isomer groups were found in the National Institute of Standards and Technology standard reference material (SRM)#1649 (Urban Dust). The pattern of the MW 302, 326, and 350 isomers detected in SRM#1649 qualitatively matched the ratio of these compounds detected in the exhaust of TWC LDGVs suggesting that each gram of Urban Dust SRM contained 5–10 mg of PM originally emitted from gasoline-powered motor vehicles.Large PAHs made up 24% of the total LEV PAH emissions and 39% of the TWC PAH emissions released from gasoline-powered motor vehicles. Recent studies have shown certain large PAH isomers have greater toxicity than benzo[a]pyrene. Even though the specific toxicity measurements on PAHs with MW >302 have yet to be performed, the detection of significant amounts of MW 326 and 350 PAHs in motor vehicle exhaust in the current study suggests that these compounds may pose a significant public health risk.     

Screening of compost for PAHs and pesticides using static subcritical water extraction.

Static subcritical water extraction (SubWE) along with solid phase extraction (SPE) was used for the analysis of PAHs and pesticides in municipal solid waste compost. Yields obtained for PAHs in certified reference sediment (CRM 104) were acceptable. The extraction method was simple, rapid, used small sample sizes, and no sample drying was required. Analysis of samples was performed by GC/MS and HPLC. Recovery of spiked pesticides was greatest at 110 degrees C for 20 min extraction time. The optimum extraction for PAH analysis was achieved at 150 degrees C for 20 min. Addition of C-18 resin as an "alternate sorbent" upon cooling increased recovery of PAHs but not of pesticides, however, it increased the stability of atrazine and propazine at higher temperatures. Analysis of three municipal compost samples from the Dayton, OH (USA) area showed no pesticides above the detection limit, however, PAH totals for 11 PAHs were 15.97, 14.42, and 20.79 microg g(-1). The totals of six of the seven carcinogenic PAHs, for which remediation goals in the United States is 4.6 microg g(-1), were determined to be 9.89, 6.77, and 13.06 microg g(-1) dry weight. The highest PAH totals were obtained from compost containing sewage sludge.     

Preliminary characterization and source assessment of PAHs in tributary sediments of the Athabasca River,Canada

The Athabasca Oil Sands are one of four natural oil sands deposits in Northern Alberta, Canada. As a number of new mines are planned in the area, there is a need to establish background levels of natural hydrocarbon release prior to these developments. To this end, various environmental samples were taken from selected tributaries in the oil sands region of the Athabasca River Basin and analysed by gas chromatography/mass spectrometry (GC/MS) for polycyclic aromatic hydrocarbons (PAHs) and their alkylated analogues. Samples were collected over 3 years (1998–2000) to provide an increased understanding of the spatial distribution, nature and extent of natural hydrocarbon release to the environment. Results indicated that levels of total PAHs were elevated in the tributaries (up to 34·7 μg/g) compared to the main stem Athabasca River (<2 μg/g). As expected, samples from the oil sands deposits contained the greatest amounts of PAHs and alkylated PAHs. Profiles of the alkylated PAH distributions were very similar, indicating that all the samples tested were from a common petrogenic source.     

Control of Diesel Gaseous and Particulate Emissions with a Tube-Type Wet Electrostatic Precipitator

Abstract

In this study, experiments were performed with a bench-scale tube-type wet electrostatic precipitator (wESPs) to investigate its effectiveness for the removal of mass- and number-based diesel particulate matter (DPM), hydrocarbons (HCs), carbon monoxide (CO), and oxides of nitrogen (NO_x) from diesel exhaust emissions. The concentration of ozone (O₃) present in the exhaust that underwent a nonthermal plasma treatment process inside the wESP was also measured. A nonroad diesel generator operating at varying load conditions was used as a stationary diesel emission source. The DPM mass analysis was conducted by means of isokinetic sampling and the DPM mass concentration was determined by a gravimetric method. An electrical low-pressure impactor (ELPI) was used to quantify the DPM number concentration. The HC compounds, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs) were collected on a moisture-free quartz filter together with a PUF/XAD/PUF cartridge and extracted in dichloromethane with sonication. Gas chromatography (GC)/mass spectroscopy (MS) was used to determine HC concentrations in the extracted solution. A calibrated gas combustion analyzer (Testo 350) and an O₃ analyzer were used for quantifying the inlet and outlet concentrations of CO and NO_x (nitric oxide [NO] + nitrogen dioxide [NO₂]), and O₃ in the diesel exhaust stream. The wESP was capable of removing approximately 67–86% of mass- and number-based DPM at a 100% exhaust volumetric flow rate generated from 0- to 75-kW engine loads. At 75-kW engine load, increasing gas residence time from approximately 0.1 to 0.4 sec led to a significant increase of DPM removal efficiency from approximately 67 to more than 90%. The removal of n-alkanes, 16 PAHs, and CO in the wESP ranged from 31 to 57% and 5 to 38%, respectively. The use of the wESP did not significantly affect NO_x concentration in diesel exhaust. The O₃ concentration in diesel exhaust was measured to be less than 1 ppm. The main mechanisms responsible for the removal of these pollutants from diesel exhaust are discussed.     

Polycyclic aromatic hydrocarbons in solid residues from waste incineration

Polycyclic aromatic hydrocarbons (PAH) levels in solid residues from clinical waste incineration were measured using HPLC with fluorescence detection. PAH mass emission rates and emission rates as a function of waste burned are also reported. For bottom ash, PAH levels and physical properties were found to be quite consistent. Levels of high molecular mass PAHs were comparable to levels previously reported in the literature when adjusted for differences in sample preparation techniques. However, levels of low molecular mass PAHs were considerably elevated in this study. Possible reasons for this finding include the composition of the waste, combustion conditions and methods of sample preparation. In contrast, no PAHs were found in fly ash, an unexpected finding which is probably attributable to matrix effects resulting from a surfeit of lime in the fly ash. Factors effecting the partitioning of PAHs and their environmental fate are also discussed.     

Effect of fuel aromatic content on PAH emission from a heavy-duty diesel engine

Polycyclic aromatic hydrocarbons (PAHs) emission tests for a heavy-duty diesel engine fueled with blend base diesel fuel by adding batch fractions of poly-aromatic and mono-aromatic hydrocarbons, Fluorene and Toluene, respectively, were simulated to five steady-state modes by a DC-current dynamometer with fully automatic control system. The main objective of this study is to investigate the effect of total aromatic content and poly-aromatic content in diesel fuels on PAH emission from the HDD engine exhaust under these steady-state modes. The results of this study revealed that adding 3% and 5% (fuel vol%) Fluorene in the diesel fuel increases the amount of total-PAH emission by 2.6 and 5.7 times, respectively and increases the amount of Fluorene emission by 52.9 and 152 times, respectively, than no additives. However, there was no significant variation of PAH emission by adding 10% (vol%) of Toluene. To regulate the content of poly-aromatic content in diesel fuel, in contrast to the total aromatic content, will be more suitable for the management of PAH emission.     

Effect of fuel composition and engine operating conditions on polycyclic aromatic hydrocarbon emissions from a fleet of heavy-duty diesel buses

Emissions from 12 in-service heavy-duty buses powered by low- (LSD) and ultra low-sulfur (ULSD) diesel fuels were measured with the aim to characterize the profile of polycyclic aromatic hydrocarbons (PAHs) in the exhaust and to identify the effect of different types of fuels on the emissions. To mimic on-road conditions as much as possible, sampling was conducted on a chassis dynamometer at four driving modes, namely: mode 7 or idle (0% power), mode 11 (25% power), mode 10 (50% power) and mode 8 (100% power). Irrespective of the type of fuel used, naphthalene, acenaphthene, acenaphthylene, anthracene, phenanthrene, fluorene, fluoranthene and pyrene were found to be the dominant PAHs in the exhaust emissions of the buses. However, the PAH composition in the exhausts of ULSD buses were up to 91±6% less than those in the LSD buses. In particular, three- and four-ringed PAHs were more abundant in the later than in the former. Lowering of fuel sulfur content not only reduced PAH emission, but also decreased the benzo(a)pyrene equivalent (BAP_eq) and hence the toxicity of the exhaust. Result from multicriteria decision-making and multivariate data analysis techniques showed that the use of ULSD afforded cleaner exhaust compositions and emissions with characteristics that are distinct from those obtained by the use of LSD.     

Polycyclic aromatic hydrocarbons (PAHs) in the aerosol in Beijing, China, measured by aminopropylsilane chemically-bonded stationary-phase column chromatography and HPLC/fluorescence detection

We developed a useful analytical method for the determination of polycyclic aromatic hydrocarbons (PAH) concentrations in the aerosol of China. We used an accelerated solvent extraction (ASE) method for the extraction of PAHs from the aerosol samples, in order to reduce the extraction time and the solvent volume used. The optimum purification method was developed, with aminopropylsilane chemically-bonded stationary-phase column chromatography, in order to remove many co-extractives which cannot be removed by conventional purification methods using silica-gel column chromatography. HPLC/fluorescence detection (FLD) was adopted as the analytical method, because it has very high sensitivity to PAH and it is easy to install, operate, and maintain as compared with GC/MS. With the analytical method developed in this study, the recovery and precision (RSD) for most of the PAHs ranged from 75% to 129% and from 2.8% to 22.7%, respectively. The concentrations of PAHs in the aerosol samples collected from October 2003 to April 2005 in Beijing, China were determined using the newly developed method. SigmaPAHs, which is the sum of the concentrations of all detected PAHs, was 177.8 +/- 239.9 ng m(-3) (n = 64). The SigmaPAHs concentration in the heating season (305.1 +/- 279.0 ng m(-3), n = 33) was 7.2 times higher than that in the non-heating season (42.3 +/- 32.0 ng m(-3), n = 31). These strong seasonal variations in atmospheric PAH concentration are possibly due to coal combustion for residential heating in winter.     

Contamination of polycyclic aromatic hydrocarbons (PAHs) in microlayer and subsurface waters along Alexandria coast,Egypt

The residues of seven polycyclic aromatic hydrocarbons (PAHs) pollutants in microlayer and subsurface seawater samples collected from Alexandria coast, Egypt, were analyzed by gas chromatography–electron-impact mass spectrometry-selected ion monitoring mode (GC–MS-SIM). The pollutants studied were, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene and benzo[a]pyrene. Total PAH levels in microlayer ranged from 103 to 523 ng/l, while it ranged in subsurface samples from 13 to 120 ng/l. The Western Harbor location recorded the highest level of PAHs pollutant over all the other location for both subsurface and microlayer waters. The two major PAHs in microlayer water at the Western Harbor were fluorene and phenanthrene, making up 27% and 20% of the total PAHs, while the two major PAHs in subsurface water at the Eastern Harbor were phenanthrene and fluoranthene recording up 21% each of the total PAHs. The total PAH levels were generally in the nano-gram per liter for microlayer and subsurface seawater samples. The dominant PAHs in both subsurface and microlayer samples were fluoranthene, pyrene and benzo[a]pyrene. The microlayer enrichment factor at Alexandria’s Mediterranean coast was ranged from 29 for fluorene to 3 for phenanthrene and benzo[a]pyrene which showed PAHs concentration in the microlayer with an average of five times more than the total PAH in the subsurface samples.     

Quantification of carbamazepine and atrazine and screening of suspect organic contaminants in surface and drinking waters

A new approach for the identification of suspect trace organic contaminants in drinking and surface waters is presented. Samples were initially analyzed using a target determination method for two contamination tracers, carbamazepine (CBZ) and atrazine (ATZ). This method used offline solid-phase extraction and online solid-phase extraction techniques coupled to liquid chromatography-triple quadrupole mass spectrometry to accelerate the sample preparation process and improve method performance. CBZ and ATZ were found respectively in 31% and 56% of the samples, and concentrations were usually <20 ng L⁻¹. These samples were re-analyzed with a similar method on a quadrupole time-of-flight mass spectrometer to identify suspect contaminants by means of exact mass measurements and isotope patterns. A database of 264 common organic contaminants was built and used in conjunction with a Molecular Feature algorithm to identify the presence of these substances in drinking and surface water collected from different sources at various locations across Canada. Several organic contaminants were identified in the samples, but only the presence of caffeine, desethylatrazine, simazine and venlafaxine could be verified by comparison to pure standards. The presence of desethylatrazine was also confirmed by MS/MS experiments. These results suggest that target analysis for tracers of organic contamination may be a helpful tool to prioritize samples which should be further screened for suspect contaminants. This study also shows that the combination of separation techniques (offline and online SPE, LC) contribute to advance the applicability of high-resolution mass spectrometry for the identification of trace organic contaminants by accelerating the preparation step, reducing complexity and increasing analyte concentrations for optimal detection.