Comparison of pressurized fluid extraction, Soxhlet extraction and sonication for the determination of polycyclic aromatic hydrocarbons in urban air and diesel exhaust particulate matter

In order to characterize and compare the chemical composition of diesel particulate matter and ambient air samples collected on filters, different extraction procedures were tested and their extraction efficiencies and recoveries determined. This study is an evaluation of extraction methods using the standard 16 EPA PAHs with HPLC fluorescence analysis. Including LC analysis also GC and MS methods for the determination of PAHs can be used. Soxhlet extraction was compared with ultrasonic agitation and pressurized fluid extraction (PFE) using three solvents to extract PAHs from diesel exhaust and urban air particulates. The selected PAH compounds of soluble organic fractions were analyzed by HPLC with a multiple wavelength shift fluorescence detector. The EPA standard mixture of 16 PAH compounds was used as a standard to identify and quantify diesel exhaust-derived PAHs. The most effective extraction method of those tested was pressurized fluid extraction using dichloromethane as a solvent.     

Atmospheric polycyclic aromatic hydrocarbons (PAHs) in the urban air of Delhi during 2003

Atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) in Delhi were evaluated to study particulate PAHs profiles during the different seasons of 2003. Samples of urban suspended particulate matter were collected during January 2003 to December 2003 at three locations (Okhla, Dhaulakuan and Daryaganj), using a high volume sampler provided with glass fiber filters. Samples were analyzed using the gas chromatography technique. The annual average concentrations of total PAHs were found as 1,049.3 ng/m(3) at Okhla, 1,344.37 ng/m(3) at Daryaganj, and 1,117.14 ng/m(3) at Dhaulakuan. The seasonal average concentrations were found to be maximum in winter and minimum during the monsoon season. Principal Component Analysis (PCA) of the data was also carried out and the results indicate that diesel and gasoline driven vehicles are the principal sources of PAHs at all the three sites under investigation. Other sources might come from stationary combustion sources such as cooking fuel combustion and industrial emission.     

郑州大气及颗粒物中多环芳烃的分布特征与来源解析

对2012年郑州市大气中气态和颗粒态多环芳烃(PAHs)的分布特征与来源进行了分析。结果表明,ρ(∑PAHs)(包括气相与颗粒相)为23.27~194.61 ng/m3,气相中∑PAHs高于颗粒相,四环以下的PAHs大都存在于气态中;在夏、春2季,较小分子质量(≤178)的PAHs占比较高,冬季,较大分子质量(≥252)的PAHs占比明显较高;各功能区ρ(PAHs)排序为工业区交通密集区医疗、文化、行政混合区。郑州大气和颗粒物中PAHs可能主要来自煤和液体燃料(汽油柴油)的燃烧。     

Identification of polycyclic aromatic hydrocarbons in unleaded petrol and diesel exhaust emission

Inhalation of emissions from petrol and diesel exhaust particulates is associated with potentially severe biological effects. In the present study, polycyclic aromatic hydrocarbons (PAHs) were identified from smokes released by the automobile exhaust from petrol and diesel. Intensive sampling of unleaded petrol and diesel exhaust were done by using 800-cm³ motor car and 3,455-cm³ vehicle, respectively. The particulate phase of exhaust was collected on Whatman filter paper. Particulate matters were extracted from filter paper by using Soxhlet. PAHs were identified from particulate matter by reverse phase high performance liquid chromatography using C₁₈ column. A total of 14 PAHs were identified in petrol and 13 in case of diesel sample after comparing to standard samples for PAH estimation. These inhalable PAHs released from diesel and petrol exhaust are known to possess mutagenic and carcinogenic activity, which may present a potential risk for the health of inhabitants.     

In vitro genotoxicity of exhaust emissions of diesel and gasoline engine vehicles operated on a unified driving cycle

Acetone extracts of engine exhaust particulate matter (PM) and of vapor-phase semi-volatile organic compounds (SVOCs) collected from a set of 1998-2000 model year normal emitter diesel engine automobile or light trucks and from a set of 1982-1996 normal emitter gasoline engine automobiles or light trucks operated on the California Unified Driving Cycle at 22 [degree]C were assayed for in vitro genotoxic activities. Gasoline and diesel PM were comparably positive mutagens for Salmonella typhimurium strains YG1024 and YG1029 on a mass of PM extract basis with diesel higher on a mileage basis; gasoline SVOC was more active than diesel on an extracted-mass basis, with diesel SVOC more active on a mileage basis. For chromosomal damage indicated by micronucleus induction in Chinese hamster lung fibroblasts (V79 cells), diesel PM expressed about one-tenth that of gasoline PM on a mass of extract basis, but was comparably active on a mileage basis; diesel SVOC was inactive. For DNA damage in V79 cells indicated by the single cell gel electrophoresis (SCGE) assay, gasoline PM was positive while diesel PM was active at the higher doses; gasoline SVOC was active with toxicity preventing measurement at high doses, while diesel SVOC was inactive at all but the highest dose.     

On the effects of the dispersant Corexit 9500© during the degradation process of n-alkanes and PAHs in marine sediments

In many coastal countries, oil spill contingency plans include several alternatives for removal of the spilled oil from the ocean. Frequently, these plans include dispersants. Because this process applies chemical substances that may add toxicity to oil that already contains toxic compounds, it is, at times, a controversial method to fight oil pollution. Additionally, local conditions may result in particular complications. We investigated the possible effects of the dispersant Corexit 9500© under conditions similar to those of subtropical oceans. We used fuel oil #6+ diesel as the test mixture. Under certain conditions, at least part of the dispersed oil may reach the sediment, particularly if the dispersant is applied in coastal waters. Nine experimental units were used in this experiment. Similar conditions of water temperature, salinity, air fluxes into the experimental units, and hydrocarbon concentrations in sediments were used. Two treatments and one control, each one with three replicates, were carried out. We concentrated our investigation on sediment, although measurements of water were also taken. Our results suggest that once the oil has penetrated the sediment, no significant differences exist between oil that contains dispersant and oil without dispersant. Noticeable degradation of aliphatic hydrocarbons occurred mainly in the low molecular weight aliphatic hydrocarbons and not in the others. Apparently, degradation of aromatics was easier than that of alkanes. However, some differences were noticed for the degradation of PAHs in the sediment, suggesting a faster degradation under particular conditions in aerobic environments such as under this experiment.     

Gaseous and particulate emissions from thermal power plants operating on different technologies

This paper presents the assessment of gaseous and particulate emissions from thermal power plants operating on different combustion technologies. Four thermal power plants operating on heavy furnace oil were selected for the study, among which three were based on diesel engine technology, while the fourth plant was based on oil-fired steam turbine technology. The stack emissions were monitored for critical air pollutants carbon monoxide, carbon dioxide, oxides of nitrogen, sulfur dioxide, particulate matter, lead, and mercury. The pollutant emissions were measured at optimum load conditions for a period of 6 months with an interval of 1 month. The results of stack emissions were compared with National Environmental Quality Standards of Pakistan and World Bank guidelines for thermal power plants, and few parameters were found higher than the permissible limits of emissions. It was observed that the emissions carbon monoxide, oxides of nitrogen, and particulate matters from diesel engine-based power plants were comparatively higher than the turbine-based power plants. The emissions of sulfur dioxide were high in all the plants, even the plants with different technologies, which was mainly due to high sulfur contents in fuel.     

Multivariate assessment of polycyclic aromatic hydrocarbons in surface sediments of the Beijiang, a tributary of the Pearl River in Southern China

To estimate the severity of polycyclic aromatic hydrocarbon (PAH) contamination in the upper sediment of the Beijiang River, 42 sediment samples were analyzed for the presence of 16 key PAHs using gas chromatography–mass spectrometry. The concentrations of PAH in the sediment ranged from 44 to 8,921 ng g^?1 dry weight. The four- to six-ring PAHs, contributing >50 % to PAHs in 34 of the 42 sites, were the dominant species. Based on a principal component analysis, combined with multivariate linear regression, it became clear that the most important contributors of PAH were fossil fuel combustion (48 %), diesel emissions plus oil spillage (33 %), and coke combustion (19 %). The surface sediments of Beijiang River were grossly contaminated by PAHs mainly derived from combustion.     

Evaluation of the SKC DPM cassette for monitoring diesel particulate matter in coal mines

In a previous study, the efficacy of commercial and prototype impactors for sampling diesel particulate matter (DPM) in coal mines was investigated. Laboratory and field samples were collected on quartz-fiber filters and analyzed for organic and elemental carbon. Coal dust contributed a minimal amount of elemental carbon when commercial cascade impactors and prototype impactors, designed by the University of Minnesota (UMN) and the US Bureau of Mines (BOM), were used to collect submicrometer dust fractions. Other impactors were not as effective at excluding coal dust. The impactors evaluated in that study were either not commercially available or were multi-stage, expensive, and difficult to use for personal measurements. A commercial version of the BOM impactor, called the DPM Cassette, was recently introduced by SKC. Tests were conducted to evaluate the performance of the DPM Cassette for measuring diesel-source elemental carbon in the presence of coal dust. Bituminous coals from three mines in two different coal provinces were examined. The dust particle diameters were small and the coal dust contained a high percentage of carbon, thereby giving a worst-case condition for non-anthracite coal mines. Results for the DPM Cassette were essentially identical to those obtained by the BOM impactors in a previous study. At a respirable coal dust concentration of 5.46 mg m(-3), which is 3.8 times the regulatory limit, the DPM Cassette collected only 34 microg m(-3) of coal-source elemental carbon.     

Health risk assessment of occupational exposure to particulate-phase polycyclic aromatic hydrocarbons associated with Chinese, Malay and Indian cooking

Food cooking using liquefied petroleum gas (LPG) has received considerable attention in recent years since it is an important source of particulate air pollution in indoor environments for non-smokers. Exposure to organic compounds such as polycyclic aromatic hydrocarbons (PAHs) contained in particles is of particular health concern since some of these compounds are suspected carcinogens. It is therefore necessary to chemically characterize the airborne particles emitted from gas cooking to assess their possible health impacts. In this work, the levels of fine particulate matter (PM(2.5)) and 16 priority PAHs were determined in three different ethnic commercial kitchens, specifically Chinese, Malay and Indian food stalls, where distinctive cooking methods were employed. The mass concentrations of PM(2.5) and PAHs, and the fraction of PAHs in PM(2.5) were the highest at the Malay stall (245.3 microg m(-3), 609.0 ng m(-3), and 0.25%, respectively), followed by the Chinese stall (201.6 microg m(-3), 141.0 ng m(-3), and 0.07%), and the Indian stall (186.9 microg m(-3), 37.9 ng m(-3), and 0.02%). This difference in the levels of particulate pollution among the three stalls may be attributed to the different cooking methods employed at the food stalls, the amount of food cooked, and the cooking time, although the most sensitive parameter appears to be the predominant cooking method used. Frying processes, especially deep-frying, produce more air pollutants, possibly due to the high oil temperatures used in such operations. Furthermore, it is found that frying, be it deep-frying at the Malay stall or stir-frying at the Chinese stall, gave rise to an abundance of higher molecular weight PAHs such as benzo[b]fluoranthene, indeno[1,2,3-cd]pyrene and benzo[g,h,i]perylene whereas low-temperature cooking, such as simmering at the Indian stall, has a higher concentration of lower molecular weight PAHs. In addition, the correlation matrices and diagnostic ratios of PAHs were calculated to determine the markers of gas cooking. To evaluate the potential health threat due to inhalation exposure from the indoor particulate pollution, excess lifetime cancer risk (ELCR) was also calculated for an exposed individual. The findings suggest that cooking fumes in the three commercial kitchens pose adverse health effects.     

Forensic fingerprinting and source identification of the 2009 Sarnia (Ontario) oil spill

This paper presents a case study in which integrated forensic oil fingerprinting and data interpretation techniques were used to characterize the chemical compositions and determine the source of the 2009 Sarnia (Ontario) oil spill incident. The diagnostic fingerprinting techniques include determination of hydrocarbon groups and semi-quantitative product-type screening via gas chromatography (GC), analysis of oil-characteristic biomarkers and the extended suite of parent and alkylated PAH (polycyclic aromatic hydrocarbon) homologous series via gas chromatography-mass spectrometry (GC-MS), determination and comparison of a variety of diagnostic ratios of "source-specific marker" compounds, and determination of the weathering degree of the spilled oil, and whether the spilled oil hydrocarbons have been mixed with any other "background" chemicals (biogenic and/or pyrogenic hydrocarbons). The detailed chemical fingerprinting data and results reveal the following: (1) all four samples are mixtures of diesel and lubricating oil with varying percentages of diesel to lube oil. Both samples 1460 and 1462 are majority diesel-range oil mixed with a smaller portion of lube oil. Sample 1461 contains slightly less diesel-range oil. Sample 1463 is majority lubricating-range oil. (2) The diesel in the four diesel/lube oil mixture samples was most likely the same diesel and from the same source. (3) The spill sample 1460 and the suspected-source sample 1462 have nearly identical concentrations and distribution patterns of target analytes including TPHs, n-alkane, PAHs and biomarker compounds; and have nearly identical diagnostic ratios of target compounds as well. Furthermore, a perfect "positive match" correlation line (with all normalized ratio data points falling into the straight correlation line) is clearly demonstrated. It is concluded that the spill oil water sample 1460 (#1, from the water around the vessel enclosed by a boom) matches with the suspected source sample 1462 (#3, from the vessel engine room bilge pump). (4) From the n-alkane and PAH analysis, it appears that the oil in the spill sample 1460 is slightly more weathered in comparison with sample 1462. The minor differences in fingerprints of two samples were most likely caused by weathering effects. (5) Sample 1461 (#2, from the vessel engine room bilge) and sample 1463 (#4, from the vessel bilge waste collection tank) demonstrated significantly different fingerprints and diagnostic ratios of target compounds from that of spill sample 1460. This was caused most likely by percentages of diesel to lube oil in these two samples different from that in spill sample 1460.     

不同类型机动车尾气挥发性有机化合物排放特征研究

机动车尾气主要成分包括一氧化碳、氮氧化物、碳氢化合物、铅及苯并[a]芘等.其中,挥发性有机化合物由于其对光化学烟雾的贡献及对人体健康的影响而成为近年来大气化学研究的热点.文章首次对北京市9种车辆、5种燃料在不同工况下排放挥发性有机化合物特征进行了定量研究.结果表明,车型、燃料、净化器及工况等因素对排放量产生影响,电喷车比化油器车排放低,其中,夏利比富康与奥迪排放量高;LPG与汽油车排放量最高,柴油车与CNG车排放最低.其中,-10#柴油车比0#柴油车排放更低;使用净化器可以降低挥发性有机化合物排放量;不同工况对排放量的影响随车型、燃料类型的不同而不同.因此,使用清洁燃料、安装净化器和使用电喷装置,可减少尾气中挥发性有机化合物含量.     

Sampling and Analysis of Organic Compounds in Diesel Particulate Matter

The fraction of atmospheric semi-volatile organic compounds (SVOC) is partitioned between the gaseous and particulate phases. Certain of these compounds eg. polynuclear aromatic hydrocarbons (PAH) and their derivatives have been shown to exhibit mutagenic or carcinogenic properties. Emissions from diesel engines are an important source of these contaminants. In a dilution chamber, we studied a diesel engine emissions. It is shown firstly, that the gaseous fraction is predominant (by up to 20 times) with respect to the particulate phase. Secondly, the polar compounds, neglected in the majority of previous studies, are the predominant species. A test campaign was carried out in Paris-Porte d'Auteuil which yielded similar results to the laboratory experiments.     

Polycyclic aromatic hydrocarbons study in atmospheric fine and coarse particles using diagnostic ratios and receptor model in urban/industrial region

Atmospheric fine and coarse particles were collected in Teflon filters in three cities of the region of the Lower Sinos River Basin of Rio Grande do Sul in the year 2010. The filters were Soxhlet extracted, and 14 priority PAHs were analyzed using a gas chromatograph coupled to a mass spectrometer (GC/MS). The principal emission sources of these compounds were assessed by using diagnostic ratios and receptor model: positive matrix factorization (PMF 3.0) of the US Environmental Protection Agency. The results of PAHs concentration for the studied year showed significant levels of high molecular weight (HMW) PAH, Ind, and BghiP, in PM_2.5 in the winter season, showing the influence of mobile sources. The application of receptor model PMF 3.0 revealed that the main sources of PAHs were vehicle fleet (both diesel and gasoline), followed by coal combustion, wood combustion, and resuspension of dust. The results of the receptor modeling are in agreement with the data obtained by the ratio diagnostic.     

Receptor modeling for source apportionment of polycyclic aromatic hydrocarbons in urban atmosphere

This study reports source apportionment of polycyclic aromatic hydrocarbons (PAHs) in particulate depositions on vegetation foliages near highway in the urban environment of Lucknow city (India) using the principal components analysis/absolute principal components scores (PCA/APCS) receptor modeling approach. The multivariate method enables identification of major PAHs sources along with their quantitative contributions with respect to individual PAH. The PCA identified three major sources of PAHs viz. combustion, vehicular emissions, and diesel based activities. The PCA/APCS receptor modeling approach revealed that the combustion sources (natural gas, wood, coal/coke, biomass) contributed 19–97% of various PAHs, vehicular emissions 0–70%, diesel based sources 0–81% and other miscellaneous sources 0–20% of different PAHs. The contributions of major pyrolytic and petrogenic sources to the total PAHs were 56 and 42%, respectively. Further, the combustion related sources contribute major fraction of the carcinogenic PAHs in the study area. High correlation coefficient (R ² > 0.75 for most PAHs) between the measured and predicted concentrations of PAHs suggests for the applicability of the PCA/APCS receptor modeling approach for estimation of source contribution to the PAHs in particulates.     

Polycyclic aromatic hydrocarbons in clams Ruditapes decussatus (Linnaeus, 1758)

The concentration of sixteen individual polycyclic aromatic hydrocarbons (PAHs) was measured in the clam Ruditapes decussatus whole soft tissues from several places of the Ria Formosa lagoon (Portugal). Total PAH (tPAH) concentrations were higher in the summer (August) and winter (January) than in the other months and the distribution pattern of the individual PAHs was generally dominated by the 4 aromatic ring PAHs, followed by the 2 + 3 aromatic rings PAHs. Benzo[a]anthracene and acenaphthene were the most representative PAHs of the two fractions. Principal components analysis (PCA) revealed that, in the Ria Formosa, seasonal variations are more important than spatial variations, due to changes in PAH source. These sources ranged from petrogenic to pyrolytic or a mixture of both. The origin of clam PAHs was also assessed by partial least squares (PLS) analysis using nineteen different PAH signatures, taken from the literature. It was possible to identify boat traffic, especially in the summer, as one of the most relevant PAH sources to the Ria Formosa. The influence of boat traffic was revealed by several signatures including diesel soot, oil and weathered oil and a mixture of different individual PAHs usually found in harbour sediments. Other relevant sources included combustion of organic matter such as forest fires and diverse domestic activities, occurring mainly in the summer. Most of the clams were considered safe for human consumption, except for some point samples, which presented unusually high PAH concentrations, suggesting the need for a regular survey of PAHs in clam tissues.     

Measurements of polycyclic aromatic hydrocarbons at an industrial site in India

Polycyclic Aromatic Hydrocarbon (PAH) concentrations were measured in Total Suspended Particulate Matter (TSPM) from December 2005 to August 2006 at Nunhai, an industrial site in Agra (India). Particulate matter samples were collected on glass fibre filters using High Volume Sampler (HVS-430) and were extracted using dichloromethane with ultrasonication and analyzed by GC. Total PAH concentration varies between 0.04 to 2.5 microg m(-3) accounting only 1.6 x 10(-3)% of TSPM. The mass distribution in air was dominated by high molecular weight DbA, BghiP, BaP, BkF and IP. Combustion PAH (CPAH) except BeP represents 58% of the total PAH mass and IARC classified total carcinogenic PAH accounting 63% of TPAH concentration. Correlation studies between PAH revealed the contribution of low molecular weight PAH was mainly due to primary emission from diesel exhaust while high molecular weight PAH were formed during combustion. The presence of specific tracers and calculation of characteristic molecular diagnostic ratios Fla/(Fla + Pyr), BaP/(BaP + Chy), BaA/(BaA + Chy), IP/(IP + BghiP), BaP/BghiP and IP/BghiP) were used to identify the sources of the emissions of PAHs in the atmospheric samples. Seasonal variation in atmospheric PAH showed four fold increase in winter concentration than summer. The BaP and relative BaP amount calculated from the measurements suggested that photo-oxidation may also be responsible for the variation in PAH concentrations during winter and summer. Seasonal trends in atmospheric PAH concentration in the study area were influenced by fossil fuel usage for domestic heating, boundary height and temperature.     

GC/MS联用仪对几种自来水中有机污染物的分析

采用美国惠普公司色谱—质谱联用仪，研究了武汉市几种自来水中所含有机污染物的种类、组成及相对含量，得出了这几种水中有机物的分布特征，分析了污染物的来源，并从不同角度比较了这几种水的污染情况。     

The distribution and composition of hydrocarbons in sediments from the Fladen Ground, North Sea, an area of oil production

The distribution and composition of hydrocarbons in sediment from the Fladen Ground oilfield in the northern North Sea have been investigated. The total PAH concentrations (2- to 6-ring parent and alkylated PAHs, including the 16 US EPA PAHs) in sediments were relatively low (<100 microg kg(-1) dry weight). The PAH, the Forties crude and diesel oil equivalent concentrations were generally higher in sediment of fine grain size and higher organic carbon concentration. PAH distributions and concentration ratios indicated a predominantly pyrolytic input, being dominated by the heavier, more persistent, 5- and 6-ring compounds, and with a high proportion of parent PAHs. The n-alkane profiles of a number of the sediments contained small, high boiling point, UCMs, indicative of weathered oil arising from a limited petrogenic input. The geochemical biomarker profiles of the sediments that contained UCMs showed a small bisnorhopane peak and a high proportion of norhopane relative to hopane, indicating that there was contamination from both Middle Eastern and North Sea oils. Therefore contamination was not directly as a result of oil exploration activity in the area. The most likely source of petrogenic contamination was from general shipping activity.     

Assessment of cyclodextrin-enhanced extraction of crude oil from contaminated porous media

The purpose of this study was to evaluate the effects of cyclodextrin (CD) on the extraction of Macondo well oil from contaminated porous media over a range of hydroxypropyl-β-CD (HPβCD) concentrations. To our knowledge, this is the first dataset on this type of CD yet assembled for an actual crude oil. The results showed that HPβCD can significantly increase oil extraction efficiency, demonstrated by increasing concentrations of all tested normal alkanes (nC(15)-nC(35)) and polyaromatic hydrocarbons (PAHs) in the aqueous phase with increasing CD concentration. A linear relationship between the extraction enhancement effect and CD concentration were verified experimentally and high correlation coefficients for total PAHs (R(2) = 0.82) and alkanes (R(2) = 0.99) were determined. For a 20% CD solution, 3.13 wt% of alkanes and 32.12 wt% of total PAHs were extracted to the aqueous phase, which was significantly more than what was extracted with water only (0.04% and 0.21% for alkanes and PAHs, respectively). This result shows that the remediation of oil contaminated media can be significantly enhanced through the use of HPβCD solutions in flushing or pump and treat operations to remove sorbed oil. The CD extraction enhancement effect decreases with increasing n-alkane chain length for the carbon number range tested. CD significantly enhanced PAH extraction from sand and the enhancement effect increased in the order of parent compounds < C-1 substituted < C-2 substituted < C-3 substituted for most PAHs tested. This study provides important information to assess the feasibility of using CD as a near-shore agent to enhance the cleanup of oil contaminated porous media.