Determination of PAHs in Combustion-Related Samples and in SRM 1597, Complex Mixture of PAHs from Coal Tar

Three types of combustion sample extracts, smokeless coal, smoky coal, and wood, were analyzed for a range of polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic sulfur heterocycles (PASH). Standard Reference Material (SRM) 1597, Complex Mixture of PAHs from Coal Tar, was also analyzed as a control sample and for the determination of a larger number of PAHs relative to those determined previously. Target analytes included many alkyl-substituted PAHs such as dimethylphenanthrenes, methylfluoranthenes, and methylpyrenes. The analytical methods included sample clean-up and the selection of specific stationary phases to accomplish unique separations of PAHs. Clean-up involved the use of normal-phase liquid chromatographic isolation of PAHs based on the number of aromatic carbons and a total PAH fraction, PAHs in the resulting fractions were separated by gas chromatography using two stationary phases with different selectivities and analyzed using mass spectrometry. These methods are discussed below and results are presented with an emphasis on the relative concentrations and distribution of PAHs in the combustion samples.     

Rapid determination of heavy polycyclic aromatic hydrocarbons in edible fats and oils

A new rapid method has been developed to determine polycyclic aromatic hydrocarbons (PAHs) in edible fats and oils. Samples are dissolved in isohexane/butylmethylether and PAHs are adsorbed onto a polystyrene solid‐phase extraction cartridge. Triglycerides and non‐aromatic components are eluted stepwise with different mixtures of isohexane and butylmethyether. PAHs finally are eluted with tetrahydrofurane. After evaporation of solvent, PAHs are redissolved in acetonitrile and analysed by RP‐HPLC with fluorimetric detection. Recoveries of 5‐ and 6‐nuclear PAHs are 85—95%, recoveries of 4‐nuclear PAHs are about 60—75%, for 2‐ and 3‐nuclear PAHs the solid‐phase extraction method is not suitable.     

The Effect of Local Cooking Methods on Polycyclic Aromatic Hydrocarbons (PAHs) Contents in Beef,Goat Meat,and Pork as Potential Sources of Human Exposure in Kisumu City,Kenya

Roasted meat is known to be a major source of human exposure to PAHs. The contribution of direct-heat charcoal-roasted, electric- oven grilled, and shallow-pan fried meat to human exposure in Kisumu City was not known although the three modes of cooking meat are very prevalent. This study analyzed the concentrations of the PAHs in raw beef, goat meat, and pork, investigated the effect of direct-heat charcoal roasting, electric-oven grilling, and shallow-pan frying on these concentrations, and compared their concentration levels with international standards for foods in order to assess the potential risks to consumers. Samples were taken from three popular meat-roasting hotels within Kisumu City, Kenya. Extraction of PAHs was done using liquid-liquid partition after saponification with alcoholic potassium hydroxide followed by clean-up on a silica gel column and final analysis by gas chromatography-mass spectrometry (GC-MS). Roasting and shallow-pan frying introduced new PAHs and significantly (P ≤ 0.05) increased the concentrations of those existing in raw meat. Direct-heat charcoal roast beef had 5 new PAHs and a total mean PAH content of 17.88 μg/kg, compared with a mean of 1.39 μg/kg for raw beef, with the potent dibenz(a,h)anthracene also being detected. Direct-heat charcoal roasted goat meat had three new PAHs and a total mean PAH content of 4.77 μg/kg, compared with a mean of 2.13 μg/kg in raw meat, with the potent benzo(a)pyrene concentration being 8.84% of the total mean PAH. Fried pork had 7 new PAHs and a total mean PAH content of 3.47 μg/kg, compared with a mean total of 0.17 μg/kg, detected in the raw meat. Roast beef had the highest individual PAH concentration (5.03 μg/kg) and highest total PAHs concentration (17.88 μg/kg), both being higher than acceptable EU limits. The PAHs from local raw and cooked meat were characterized and quantified for the first time in Kisumu City and the study therefore provided the needed baseline data on PAHs in raw and cooked meat.     

THE LOADS OF PAHS IN WASTEWATER AND SEWAGE SLUDGE OF MUNICIPAL TREATMENT PLANT

Abstract

Sewage and sewage sludge from a municipal wastewater treatment plant were analyzed for 16 EPA-PAHs. This plant is a classic mechanical-biological treatment plant, consisting of activated sludge technology with additional chemical treatment for the removal of phosphorus compounds. The process of sewage sludge treatment is carried out in closed as well as open sludge digesters. Primary and mechanically thickened sludge are passed through the fermentation process. Digested sludge is dewatered on filter-press through addition of flocculent. The measurements were obtained to investigate the effect of different treatment stages on PAH content in wastewater and sewage sludge. The following wastewater samples were collected: crude ones and those after sand trap, primary sedimentation, biological treatment and secondary sedimentation. Sewage sludge samples were collected from: primary sludge, digested sludge and dewatered sludge. PAH load in influent, mechanically and biologically treated sewage, as well as in raw digested and dewatered sludge, were calculated. PAHs were extracted from wastewater and sludge samples, with cyclohexane, dichloromethane using an ultrasonic method. Gas chromatograph equipped with mass spectrometry was used for qualitative and quantitative determination of PAHs. Mechanical and biological treatment proved the removal of 83–85% of PAHs from the influent. Despite this its daily PAH load introduced into the environment was high and reached 27–37% of PAH load in influent. In sewage sludge it was 46–70 g/d of PAHs (carcinogenic PAHs content 4–12%). In waste sludge (filter pressed sludge and sand from detrirer) PAH total load reached 42–68 g/d with (10–17% of carcinogenic PAHs).     

卷烟烟气中多环芳烃的同时测定

在优化卷烟烟气试样前处理技术的基础上,确定了6种多环芳烃分离的最佳条件和测定的最佳荧光激发、发射波长,并进行波长程序编程,采用高效液相色谱编程荧光法（HPLC-FLD）建立了一种同时测定卷烟烟气中6种多环芳烃的分析方法。各多环芳烃在所测定的含量范围内有良好的线性关系,方法的最低检出限可达到0.4 ng/mL,回收率均在87%以上。并利用该方法对国产卷烟样品进行了分析。     

Project Tocoen. The Fate of Selected Organic Compounds in the Environment. Part XXVIII. Levels of PAHs and Some Halogenated POPs in Ambient Air in Czech Republic

Abstract

Concentrations of polyaromatic hydrocarbons (PAHs), chlorinated pesticides, polychlorinated biphenyls, dibenzo-p-dioxins and dibenzo-p-furans (PCDDs/Fs) in ambient air in Ko?etice, a background locality in the South Bohemia, have been estimated in the period from July to December 1994. The 24-hours samples have been taken by the means of a high-volume sampler. Sample analysis involved Soxhlet extraction of polyurethane foam, extract preconcentration and chromatographic clean-up procedure followed by HPLC determination of PAHs with fluorescence detection, GC/ECD determination of chlorinated pollutants, and GC/MS determination of PCDDs/Fs. The results of this first detailed study undertaken in Czech Republic are compared with the data obtained by similar projects in industrial and/or urban areas in the Czech Republic and in rural or urban areas in other European countries.     

Removal of polyaromatic hydrocarbons from scrap tires by solvent extraction

This study analyzes polycyclic aromatic hydrocarbon (PAH) compounds released from scrap tires by GC/MS and introduces a simple extraction process at ambient conditions to remove PAHs from scrap tires. The PAH species released from scrap tires included seven PAH compounds with high molecular weight and 4- and 5-aromatic rings and total-PAH content of 159 mg/L. When scrap tires were extracted using hot water (180 °C) for 3 h, the overall removal efficiency was 53%, indicating that PAHs were not adequately removed by this method. However, using organic solvents, the overall PAH removal efficiency improved to 82% for propionic acid and 70% for acetic acid, because the mass transfer of PAHs within scrap tires increases with decreasing dielectric constant. The PAH removal efficiency was dependent on solvent type and temperature.     

Characteristics of Polynuclear Aromatic Hydrocarbons in Ambient Air through a Long-Term Sampling Program at a Metropolitan City in Taiwan

Polynuclear aromatic hydrocarbon (PAH) concentrations in total suspended particulate (TSP) matter as well as gaseous PAH contents are measured at an urban site adjacent to the capital of Taiwan. Several factors, such as seasonal variation, ring number, G/P (gas/particulate) ratio, and C-atom number, are utilized to characterize the pollution features of 14 PAHs. The results show that the total PAH content in TSP has been reduced gradually. The probable carcinogenic PAH compounds exist primarily in the particulate phase. The concentration distributions of each PAH compound are different, and the quantities and ring distributions of PAHs are significantly affected by seasonal fluctuation. The G/P ratio is highly associated with the C-atom number of PAHs. Factor analysis, along with the characteristic ratios of PAHs, is used to qualitatively identify the probable contributors. The results suggest that traffic exhaust and industrial origins are the predominant contributors.     

The Spatial and Temporal Variations of Polycyclic Aromatic Hydrocarbons (PAHs) in Environmental Matrices in the Czech Republic

The paper is a review of the PAH emission inventories and the results of ambient air measurements of PAHs on regional a local level and determination of PAHs in other abiotic and biotic samples in the Czech Republic (CR). The main sources of polycyclic aromatic hydrocarbons (PAHs) in the country are associated with electric and thermal energy production, waste incineration, road traffic and some industrial processes (e. g. high-temperature coal carbonation, catalytic cracking of crude oil and aluminium production).     

Recertification of Standard Reference Material (SRM) 1649, Urban Dust,for the Determination of Polycyclic Aromatic Hydrocarbons (PAHs)

The National Institute of Standards and Technology (NIST) recently issued SRM 1649a, Urban Dust, with certified and reference values for 44 polycyclic aromatic hydrocarbons (PAHs). This material is a recertification of SRM 1649 which was issued in 1982 with certified values for only five PAHs. The PAHs were determined using the following analytical techniques: (1) reversed-phase liquid chromatography with fluorescence detection (LC-FL) for analysis of the total PAH fraction, (2) reversed-phase LC-FL for analysis of isomeric PAH fractions isolated by normal-phase LC (i.e., multidimensional LC), and (3) gas chromatography/mass spectrometry (GC/MS) for analysis of the PAH fraction using three different stationary phases, each with different selectivity for PAH separations. The results from the different techniques are compared and discussed. SRM 1649a is currently the most extensively characterized environmental matrix SRM with respect to PAH constituents.     

A Coupled-Column HPLC Method for Routine Analysis of Various Chrysene and Benzo[a]Pyrene Metabolites in Urine

The carcinogenic potential of some PAHs leads to the necessity of expressive biological monitoring for people occupationally exposed to PAH. A highly automated, coupled-column, high performance liquid chromatography method for the simultaneous quantification of several chrysene and benzo[a]pyrene metabolites in urine of exposed subjects is presented. After enzymatic hydrolysis of the metabolites, the sample can be directly injected into the HPLC system. The instrumental set-up comprises an analytical column and a precolumn, connected via a 6-port switching valve. Clean-up and analyte preconcentration are automatically performed on the precolumn which is packed with copper-phthalocyanine modified silica. Afterwards, analytes are automatically transferred onto the analytical column where separation is carried out by elution with a methanol-water gradient. Detection of the analytes makes use of their natural fluorescence. Thus, clean-up and analytical separation require little time, making the method suitable for routine analysis in biomonitoring.     

DETERMINATION OF DIBENZO[A,L]PYRENE AND OTHER FJORD-REGION PAH ISOMERS WITH MW 302 IN ENVIRONMENTAL SAMPLES

Polycyclic aromatic hydrocarbons (PAHs) occur in the environment as complex mixtures including compounds with mutagenic and carcinogenic activity. The PAH profile routinely determined in environmental samples at present encompasses isomers with molecular weight (MW) not greater than 300. However, PAHs with MW >300 have been demonstrated for several matrices to contribute up to 50% of the total activity when tested for carcinogenicity in experimental animals. Recent studies indicate that among the dibenzopyrenes with MW 302 dibenzo[a,l]pyrene, possessing a fjord region, is by far the most carcinogenic PAH hitherto identified. To further elucidate the environmental relevance of this compound we have applied the isotope dilution GC/MS technique as analytical procedure to determine this compound and the related fjord region PAH naphtho[1,2-a]- and naphtho[1,2-e]pyrene in various matrices. Identification was based on comparison of UV and mass spectra as well as retention times of authentic reference materials. Determination of these PAHs was achieved after clean-up by several chromatographic steps including fractionation on a modified TABA-silica gel column. Quantitative data for matrices such as two cigarette smoke condensates, motor vehicle exhaust condensate (Otto-type engines), and tar-cork are reported. Based on toxic equivalent factors the relative contribution of dibenzo[a,l]pyrene (5.4–42.3%) to the total carcinogenic activity of a PAH profile will be discussed comprising 14 selected isomers (benzo[b]naphtho[2,1-d]thiophene; cyclopenta[cd]pyrene; benz[a]anthracene; chrysene/triphenylene; sum of benzo[b]-, benzo[k]-, and benzo[j]fluoranthene; benzo[a]pyrene; indeno[1,2,3-cd]pyrene; dibenz[a,h]anthracene; benzo[ghi]perylene; anthanthrene; dibenzo[a,l]pyrene determined in these matrices.     

Revealing the Origin of Polycyclic Aromatic Hydrocarbons in an Urban Snowpack

Polyciclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in urban atmosphere. Several PAHs are known carcinogens or are the precursors to carcinogenic daughter compounds. Understanding the contributions of various PAH emission sources is critical to appropriately managing PAH levels in the environment. The sources of PAHs to urban snowpack in Shelekhov city, Eastern Siberia, characterized by extremely high levels of PAH accumulation in snow were determined by using end-member mixing approach. The best potential to distinguish PAH emission sources is exhibited by ratios of PAH pairs of the principal mass 228, 252, and 276. The ratios of PAH pairs were used as tracers of end-member PAH sources. The contributions of sources were calculated using systems of linear equations. The results obtained using ratios of PAH pairs were compared with those obtained using molecular diagnostic ratios. It was shown that the results obtained using diagnostic ratios as tracers are less reliable than the results obtained using the ratios of the sums of PAHs.     

Polycyclic aromatic hydrocarbons in crude and deodorized vegetable oils

The efficiency of the refining process in removing polycyclic aromatic hydrocarbons (PAH) from crude vegetable oils was studied. Samples of the crude oils (coconut, soybean and rapeseed oils) and the corresponding refined, deodorized oil were taken on-line in three Swedish oil refineries and margarine manufacturing plants and analyzed for 20 different PAHs. Of the crude oils, coconut oil had by far the highest PAH levels. However, the PAH levels in the refined coconut oils were very low. This shows that the activated charcoal treatment used for removing PAHs from coconut oil achieves the desired effect. The crude soybean and rapeseed oils contained relatively low, but varying, amounts of PAH. At present these oils are not purified by activated charcoal. Nevertheless, the PAH levels in the refined oils were considerably lower than those in the corresponding crude oils. This probably is due to evaporation of PAH in the deodorization process, where steam is passed through the hot oil under high vacuum. However, deodorization has only a marginal effect on the high molecular PAHs, of which several are classified as carcinogens.     

Analysis of Polycyclic Aromatic Hydrocarbons in Egyptian Petroleum Condensate Oils

The polycyclic aromatic hydrocarbons (PAH) in Egyptian condensates are analyzed for the first. A solid phase extraction (SPE) followed by gas chromatography-mass selective detection was used for their analysis. The method was calibrated for optimal extraction conditions. Excellent recoveries were found (78–114%) for the PAHs that were identified using a variety of standards and GC-MS spectra. The solid-phase extracted PAH fraction was further separated by HPLC on a Ag(I) mercaptopropanosilica gel to reduce the complexity of the sample by separating the PAHs based on the number of aromatic rings. The analytes were quantified using GC with a flame ionization detector. For this kind of sample SPE is a more convenient separation technique than an open column. PAHs containing two to four rings in the concentration range 0.6–11 μg/L were measured. Some preliminary geochemical hypotheses based on the analyzed PAHs and the previously analyzed S-containing aromatic compounds were formed as to the depositional environment and source rock type.     

Polycyclic aromatic hydrocarbon emissions of non-road diesel engine treated with non-thermal plasma technology

Non-road diesel engines are important polycyclic aromatic hydrocarbon (PAH) sources in the environment due to their high emission concentration compared to on-road diesel engines. Particle- and gas-phase PAH concentrations of a non-road diesel engine were investigated. Non-thermal plasma (NTP) as an effective after-treatment technology was used to reduce PAH emissions. The results showed that particle-phase PAH concentrations were 329.7 µg/m³, 3,206.7 µg/m³, and 1,185.7 µg/m³ without the action of NTP at three different engine loads respectively. Relatively low concentrations were measured for gas-phase PAHs. Excellent linearity was shown for particle-phase with total PAH concentrations both with, and without, NTP. The gas-phase PAH concentrations linearly increased with engine load without NTP. The five most abundant compounds of PAHs were among low molecular weight (LMW) and medium molecular weight (MMW) compounds. Total PAH cleaning efficiency was beyond 50% when treated with NTP at the three different engine loads. We hypothesized that naphthalene (Nap) concentrations increased greatly at 60% and 80% engine loads because it was produced within the plasma zone by decomposition of high molecular weight (HMW) PAHs. The PAHs content of particulate matter (PM) aggregation at 60% load was approximately three times higher than at 40% and 80% loads. High correlation values were observed for MMW PAHs with total PAH concentrations. Correlations of PAH concentration reduction could be important to clarify the PAH reduction mechanism with NTP technology.     

Identification and spectral properties of PAHs in carbonaceous material produced by laser pyrolysis

Carbonaceous materials have been prepared by laser-induced pyrolysis of a mixture of hydrocarbons (C₂H₂, C₂H₄, and benzene) under different conditions. We have investigated the soluble and insoluble part of the condensed carbon powders with several techniques, such as UV/VIS and IR spectroscopy, mass spectroscopy, gas chromatography combined with mass and IR spectrometry and high-performance liquid chromatography (HPLC) in order to obtain information on the total content and composition of the extracted soluble part and on the influence of the soluble component on the spectroscopic properties of the condensed carbon nanopowder. It has been found that the extract contains more than 64 different polycyclic aromatic hydrocarbons (PAHs). The most abundant PAH molecules are those containing 3–5 rings. The total amount of aromatic soluble components depends on the temperature in the condensation zone whereas the ratio between high- and low-mass PAHs is influenced by both, the temperature and the precursor gases. IR spectroscopic investigations of the extract have shown partial hydrogenation of PAHs leading to the formation of CH₂ groups, at the edge of PAH molecules. The IR spectral properties of the carbonaceous materials and of the PAHs are influenced by the adsorption process.     

Concentrations and Source Identification of Polycyclic Aromatic Hydrocarbons (PAHs) in Mangrove Sediments from North of Persian Gulf

The concentrations of 16 Environmental Protection Agency (EPA) priority polyaromatic hydrocarbons (PAHs) were quantified in surface sediments from Hormozgan Province mangroves, south of Iran in dry and wet seasons. Sampling stations were selected in Laft and Khamir mangroves with international importance. Polyaromatic hydrocarbons varied from 75.24 ± 11.24 to 581.94 ± 637.39 ng/g dry weight basis. Pollution sources and their contribution for polyaromatic hydrocarbons pollution in sediments of Hormozgan mangroves were appointed based on molecular ratios and statistical methods, including principal components analysis (PCA) and multiple linear regression/principal components analysis (PCA/MLR) tests. Both of pyrogenic and petrogenic sources contributed in detected concentrations of PAHs. Contribution percentages of pyrogenic and petrogenic origins were estimated at 73.20 and 26.79%, respectively. Temporal variations showed that sediments contained higher levels of ∑PAHs in wet season than dry time. However, the mean detected ∑PAHs was lower than international quality guidelines; the high concentration of PAHs was found in Laft mangrove, suggesting the presence of PAH polluted localized area.     

Aerobic biodegradation and inhibition kinetics of poly‐aromatic hydrocarbons (PAHs) in a petrochemical industry wastewater in the presence of biosurfactants

BACKROUND: In Izmir, Turkey, wastewaters from the petrochemical industry are treated using conventional activated sludge systems. A significant proportion of poly‐aromatic hydrocarbons (PAHs) with high‐molecular weights remains in this treatment system and inhibits the biological activity. Biosurfactants increase PAHs degradation by enhancing the solubility of the petroleum components. The aerobic inhibition kinetics of PAHs has not previously been investigated in the presence of biosurfactants for a real petrochemical industry wastewater. RESULTS: Among the kinetic models used (Monod‐type, zero, first‐order and second‐order) it was found that the Monod kinetic was effective for describing the biodegradation of PAHs in petrochemcal industry wastewater in the presence of three biosurfactants, namely Rhamnolipid (RD), Surfactine (SR) and Emulsan (EM) in an aerobic activated sludge reactor (AASR). The maximum PAH removal rate (R_max) and specific growth rate of PAH degrading bacteria (µ_max) increased, while the half saturation concentration of PAH (K_s) decreased at 15 mg L^?1 RD concentration compared with the control without biosurfactant at a sludge retention time (SRT) of 25 days. CONCLUSION: PAH oxidation is typified by competitive inhibition at RD concentrations > 15 mg L^?1 resulting in increases in K_s values with PAH accumulation. Low inhibition constant (K_ID) values reflect difficulties in the metabolizability of PAHs. Metabolite production decreased at RD = 25 mg L^?1 in the PAHs indeno (1,2,3‐cd) pyrene (IcdP), flourene (FLN), phenanthrene (PHE) and benzo(a)pyrene (BaP). Copyright © 2011 Society of Chemical Industry     

DISTRIBUTION OF PRIORITY POLYCYCLIC AROMATIC HYDROCARBONS IN THE SEDIMENT OF LAKE BALATON,HUNGARY

The determination of 13 PAH pollutants was carried out on sediment samples collected at 27 sites at the Lake Balaton, Hungary. The aim was to investigate the distribution patterns of PAHs and the correlation of source-sink relationship. Sediment samples were collected from the upper 10 cm and from 20 to 70 cm depth. The dry mass ratio of the fine grain-size fraction (<0.063 mm) and the coarse sand sediments (0.063–500 mm) were analyzed. Principal component analysis (PCA) was performed on the PAH compositional data for 110 samples to estimate the distribution of PAHs in different compartments. The average concentration of PAHs was found as 132 μg/kg dry weight (11–1734 μg/kg) for all sites and depth. Considering the harbors, at some sites, 930–950 μg/kg of total PAHs were obtained. The ratio of phenantrene/anthracene (PHE/AN) and fluoranthene/pyrene (FA/PY) indicated that most of the samples showed pyrogenic origin. It can be established that the upper 10 cm of the sediment is significantly more polluted than the deeper layers. The interim sediment quality guideline (ISQG) values and the probable effect level (PEL) were used to compare our findings with other data. No concentrations of PAHs were found higher than either ISQG and PEL values of samples collected inside of the lake, so the sediment has not been associated with adverse biological effects. However, the maximum concentrations of 7 out of 9 PAH compounds found in samples of harbors were higher than ISOG values but lower than PELs. Analysis of the harbor sediments revealed an elevated amount of contamination probably derived from the fuel of ships.