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.     

Determination of Polycyclic Aromatic Hydrocarbons in F-15J,C-130H,and F-4EJ Aircraft Exhaust

There are occupational health concerns at Japan Air Self-Defense Force bases in regard to the exposure of military flightline personnel to carcinogens in aircraft emissions, such as polycyclic aromatic hydrocarbons (PAHs). To characterize the PAHs in military aircraft emissions from different types of engines, aerosol and gas samples were separately collected downwind from aircraft with a turboprop engine (C-130H), turbojet (F-4EJ), and turbofan (F-15J). The gas-phase PAHs were determined by gas chromatography coupled to mass spectrometry and the aerosol-phase PAHs were determined by high-performance liquid chromatography with fluorescence detection. The F-4EJ engine was a source of naphthalene vapor and aerosol PAHs, including carcinogens such as chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, dibenzo (a,h) anthracene, benzo (ghi) perylene, and indeno (1,2,3-cd) pyrene. These heavier (five and six-ring) PAHs were also included in the emissions from the F-15J with its newer, high-temperature F-100 turbofan engine, but the concentrations were approximately one-tenth of those in the F-4EJ. In contrast to these fighter aircraft, the C-130H was found to be a significant aerosol source of the lighter, three-ring (phenanthrene and anthracene) and four-ring (fluoranthene and pyrene) PAHs, but not the heavier ones. These results demonstrate that various aircraft are sources of PAHs in the military flightline environment.     

The Use of Reverse Osmosis in the Removal of PAHs from Municipal Landfill Leachate

Polycyclic aromatic hydrocarbons (PAHs) are relatively well-known organic pollutants and due to their carcinogenic and mutagenic properties their presence in the environment still attracts a lot of attention.

According to literature reports and own research, PAHs presence in wastewaters is common. It was confirmed that PAHs are the components of municipal landfill leachate. Membrane techniques are one of the most interesting ways of removing PAHs from leachate.

The purpose of this article is to monitor PAHs concentration changes during the membrane (reverse osmosis - RO) leachate treatment processes. In the first stage of testing leachates were filtrated on the sand bed (pre-filtration). After the pre-filtration they were directed to the membrane module for the main filtration.

Sixteen PAHs listed by EPA were analyzed. The results with information on PAHs concentration in leachate samples were presented using HPLC with fluorescence detection (FLD). The changes in PAHs concentration were determined in leachate samples before and after pre-filtration as well as after RO. The decrease of PAHs concentration in the samples was observed after these processes. The total concentration of 16 PAHs in raw municipal landfill leachates amounted to 23.64–26.95 μg/L. The research confirmed the high efficiency in removal of PAHs while using a reverse osmosis (59–72%). Including the pre-filtration, the overall level of removed PAHs reached 81–86%. The average PAHs concentration after pre-filtration and RO was in the 4.46–4.99 μg/L range. The municipal landfill leachate with a high concentration of PAHs should be cleaned before it is discharged into the environment.     

Evaluation of Polycyclic Aromatic Hydrocarbons Contamination in the Sediments of the Johor Strait,Peninsular Malaysia

In May 2013, sediment samples were collected from five stations in the Straits of Johor, near the southern tip of Peninsular Malaysia, in order to evaluate the distribution and sources of polycyclic aromatic hydrocarbons (PAHs). The concentrations of 16 United States Environmental Protection Agency PAHs varied from 650.5 to 1441.2 ng g ^?1 dry weight (dw) with a mean value of 985.5 ng g ^?1 dw. PAHs can be classified as moderate level pollution in the collected samples. When comparing PAHs in this study with that of the sediment quality guidelines (SQGs), it was found that the total PAHs, low molecular weight (LMW), and high molecular weight (HMW) PAHs might incur minimal adverse biological effects. The diagnostic ratios of individual PAHs indicated both petrogenic and pyrogenic origins with predominantly pyrogenic sources, the findings of which are further supported by the results from principal component analysis (PCA). The PCA results reveal contributions of 44.44%, 32.3%, and 18.96% for traffic-related, coal combustion, and petroleum-related products, respectively. These findings indicate that the effective monitoring and significant improvement resulting from the implementation of environmental regulations in Malaysia might have caused a shift in the source of petroleum hydrocarbons in the Straits of Johor's aquatic ecosystems from petrogenic to pyrogenic origins.     

Profiles and Sources of PAHs in Sediments from an Open-Pit Mining Area in the Peruvian Andes

The Peruvian Andes are one of the most productive areas for mining and therefore also one of the most exposed to these sources of pollution. This article reports the characterization of Polycyclic Aromatic Hydrocarbons (PAHs) in sediments of Cerro de Pasco area (Peru) located close to a large open-pit mine and, in recent years, several reports have provided evidence of environmental contamination and related health problems. Investigations were carried out into the fifteen PAHs identified by the US-Environment Protection Agency (US-EPA) as requiring priority monitoring, other non US-EPA listed PAHs and perylene were also investigated in order to obtain further information on their origins. By considering the results of all the analysis, the total PAHs concentration varies from 13–1009 μg/Kg with a mean value of 224 μg/Kg. The concentrations of PAHs found in all 12 stations were lower than the effect range low (ERL). PAHs, in the most of the samples, have origin from high temperature processes. Taking into consideration that perylene concentrations were low, a small quantity of polycyclic hydrocarbons may be originated from biological activity.     

Characterization of Gaseous and Particulate Polycyclic Aromatic Hydrocarbons in Ambient Air of Delhi,India

Three seasonal sampling campaigns were undertaken at an urban site of Delhi for collection of PAHs in particulate and gas phase. Sampling was done by using modified Respirable Dust (PM ≤10μm) sampler attached with polyurethane foam (PUF) plugs and compared with conventional Respirable Dust (PM ≤10 μm) sampler. Total 16 EPA PAH (gaseous + particulate) were determined by Gas Chromatograph-Mass Spectrophotometer (GC-MS). The 3-ring PAH constitutes approximately 90% of the gaseous PAHs with phenanthrene, fluoranthene, acenapthylene, and acenaphthene being the most abundant gaseous PAHs. PAHs with 4- to 6- rings accounted for 92%, 87% and 78% in samples collected during winter, summer and monsoon season respectively. Gaseous PAHs, particulate PAHs and total PAHs were higher during winter as compared to summer and monsoon seasons. The contribution of particulate PAHs were 1.4, 2.1, and 2.5 times higher in winter, summer and monsoon, respectively than of gaseous PAHs. Indeno[123-cd]pyrene, benzo[ghi]perylene, dibenzo[ah]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene and chrysene were found to be the most abundant PAH compounds in the particulate PAHs during all the seasons. The result from application of diagnostic ratio suggests that the higher particulate PAHs emissions were predominantly associated with vehicular emissions along with emissions from biomass burning during winter season.     

Polycyclic Aromatic Hydrocarbons in Romanian Baby Foods and Fruits

Levels of polycyclic aromatic hydrocarbons (PAHs) in commercially available baby food and in different sorts of fruits were investigated. PAHs determination was performed by gas chromatography coupled with mass spectrometry (GC/MS). The sum of 15 PAHs varied in baby food from 2.52–6.7 μg/kg and in fruits from 0.40–21.52 μg/kg. Benzo[a]pyrene used as a marker for PAHs contamination was detected in lower levels in baby food than the maximum tolerable limit (1 μg/kg) stated in Commission Regulation no 1881/2006.     

Occurrence and Source Apportionment of Polycyclic Aromatic Hydrocarbons in Urban Residential Soils from National Capital Region,Uttar Pradesh,India

This study aims to investigate the level of priority polycyclic aromatic hydrocarbons (PAHs) and identification of their potential sources in residential soils. During the study, a total 36 soil samples collected from twelve residential locations at Sahibabad-Ghaziabad area of western Uttar Pradesh, India, a constituted part of the National Capital Region of India. Samples extracted using ultrasonication, cleaned with silica and analyzed by diode array detector–high-performance liquid chromatography using acetonitrile/water as mobile phase. The 25th and 75th percentile concentration of ∑PAHs was 264 μg kg^?1 and 584 μg kg^?1, respectively, with mean and median of 445 μg kg^?1 and 421 μg kg^?1. The detection frequency of PAHs in all samples was lower for low molecular weight PAHs (19%) than high molecular weight PAHs (81%). The concentration of seven probable carcinogenic PAHs accounted for 67% of the ∑PAHs. PAHs toxicity potential as benzo(a)pyrene toxicity equivalent ranged between 2.52–253 μg BaP_TEQ kg^?1. Composition profile of PAHs with different aromatic rings and selected diagnostic molecular ratios suggested the local pyrogenic sources of PAHs from vehicular emissions, diesel engines, biomass combustion, gasoline, and coal combustions.     

Polycyclic Aromatic Hydrocarbons in Residential Soils from an Indian City near Power Plants Area and Assessment of Health Risk for Human Population

This article deals with the distribution, composition profiles, and possible sources of sixteen priority polycyclic aromatic hydrocarbons (PAHs) in residential soils from Korba district in Chhattisgarh State, India. Sixteen priority PAHs in soils were analyzed after ultrasonic extraction, silica gel column chromatographic cleanup, and quantitation was performed using HPLC-DAD. The concentrations of ∑16PAHs were within acceptable limits of soil quality guidelines and the study area got classified as weakly contaminated. The concentration of probable human carcinogenic PAHs in soils accounted for 10% of ∑16PAHs. The concentration of Benzo(a)Pyrene (BaP) accounted 1% to total PAHs. Benzo(a)pyrene Toxicity Equivalency (BaP_TEQ) for 16 PAHs was 30 ± 12 μg BaP_TEQ kg^?1. The composition profiles and molecular ratios of PAHs suggested mixed pyrogenic sources of PAHs from combustion of coal, wood, and vehicular exhaust emissions. Human health risk was assessed by calculating the lifetime average daily dose (LADD) and incremental life time cancer risk (ILCR) for human adults and children. Estimated ILCR was within safe limit (10^?6?10^?5), indicating low risk to human population. Potential risk to contaminated ground water from leaching of carcinogenic PAHs was assessed by estimating the Index of Additive Cancer Risk (IACR).     

Polycyclic Aromatic Hydrocarbons Activate the Aryl Hydrocarbon Receptor and the Constitutive Androstane Receptor to Regulate Xenobiotic Metabolism in Human Liver Cells

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants produced by incomplete combustion of organic matter. They induce their own metabolism by upregulating xenobiotic-metabolizing enzymes such as cytochrome P450 monooxygenase 1A1 (CYP1A1) by activating the aryl hydrocarbon receptor (AHR). However, previous studies showed that individual PAHs may also interact with the constitutive androstane receptor (CAR). Here, we studied ten PAHs, different in carcinogenicity classification, for their potential to activate AHR- and CAR-dependent luciferase reporter genes in human liver cells. The majority of investigated PAHs activated AHR, while non-carcinogenic PAHs tended to activate CAR. We further characterized gene expression, protein abundancies and activities of the AHR targets CYP1A1 and 1A2, and the CAR target CYP2B6 in human HepaRG hepatoma cells. Enzyme induction patterns strongly resembled the profiles obtained at the receptor level, with AHR-activating PAHs inducing CYP1A1/1A2 and CAR-activating PAHs inducing CYP2B6. In summary, this study provides evidence that beside well-known activation of AHR, some PAHs also activate CAR, followed by subsequent expression of respective target genes. Furthermore, we found that an increased PAH ring number is associated with AHR activation as well as the induction of DNA double-strand breaks, whereas smaller PAHs activated CAR but showed no DNA-damaging potential.     

REMOVAL OF PAHs BY SORBENT FROM FLUE GAS DURING MSW INCINERATION

The aim of this article is to investigate the removal of polycyclic aromatic hydrocarbons (PAHs) by sorbent injection from the flue gas during municipal solid waste (MSW) incineration. For this purpose, the incineration tests of MSW were performed in a fluidized bed incinerator and the influence of sorbent on PAHs was studied. The samples analyzed were taken from the raw MSW, the flue gas, the fly ash, and the bottom ash. The 16 PAHs specified by the U.S. EPA were analyzed by a high performance liquid chromatography (HPLC). The results obtained show that there were a few PAHs in the raw MSW and the bottom ash. The total PAHs in the fly ash and the flue gas were dominated by 3- to 5-ring PAHs and 2- to 4-ring PAHs, respectively. The removal efficiency of PAHs increased with the rise of activated carbon, and the removal efficiency of PAHs by kaoline was better than activated carbon and activated bauxite. PAHs could be effectively removed by sorbent injection from the flue gas during the MSW incineration.     

Size Distributions of Polycyclic Aromatic Hydrocarbons at Two Receptor Sites in the Pearl River Delta Region,China: Implications of a Dominant Droplet Mode

Size distributions of twelve polycyclic aromatic hydrocarbons (PAHs), elemental carbon (EC), organic carbon (OC) and major inorganic ions were measured at two receptor locations in the Pearl River Delta (PRD) Region in southern China during 2006–2008. The size distributions of three- and four-ring PAHs were characterized with three modes, a condensation mode with a mass median aerodynamic diameter (MMAD) in the range of 0.2–0.3 μm, a droplet mode (MMAD: .7–1.0 μm), and a coarse mode (MMAD: 3–5 μm). The less volatile five- to six-ring PAHs were mainly distributed in the condensation mode and droplet mode, with little presence in the coarse mode. The droplet mode was the most prominent mode for all PAHs at both sites, accounting for more than 70% of the total particle-phase five- and six-ring PAHs and more than 60% of the total particle-phase three- and four-ring PAHs. The dominant droplet mode could be attributed to a result of in-cloud processing of vehicular soot particles and biomass burning particles during the transport of source aerosols to the receptor sites. Presence of sulfate aqueous coating on the droplet-mode particles was hypothesized to make PAHs inaccessible to volatilization from particle phase and to oxidation by gaseous oxidants. Further implications of a dominant droplet-mode PAHs were discussed.     

不同来源污泥热解油中多环芳烃分布特征

分析了4种不同来源污泥的热解油中16种EPA-PAHs生成分布,并探讨了污泥原样中自由赋存PAHs和污泥泥质特性（碳含量、H/C摩尔比、O/C摩尔比及挥发分含量等）的影响。结果表明,4种来源污泥热解油中均不同程度包含16种EPA-PAHs,∑EPA-PAHs含量分布次序为：工业印染污泥热解油（21.72 mg·kg^-1）>生活污泥热解油（14.10 mg·kg^-1）>造纸污泥热解油（13.72 mg·kg^-1）>食品污泥热解油（5.48 mg·kg^-1）,且以低环（2R）和中环（3R和4R）PAHs为主,其总量占∑EPA-PAHs的95%以上。热解油中PAHs含量高低与污泥自身赋存的自由PAHs含量具有一定关联;泥质特性对热解油中EPA-PAHs含量分布也呈现了不同程度影响,随着污泥泥质特性变化,3R和4R-PAHs含量变化规律较相似,均在碳含量为30.96%、H/C摩尔比为1.1、O/C摩尔比为0.33和挥发分为35.5%时达到最高水平;2R-PAHs含量在碳含量为20.75%、H/C摩尔比为1.44、O/C摩尔比为0.6和挥发分为46.3%时达到最高水平。     

神木原煤萃取产物中多环芳烃含量的研究

对神术原煤分别用苯及石油醚作萃取溶剂进行索式萃取,采用硅胶柱层析纯化,利用气相色谱/质谱联用仪（GC／MS）分别对上述萃取液的硅胶层析产物进行了解折,并对其中的9种多环芳烃（PAHs）进行了定量测定;研究了不同萃取剂所得萃取液中多环芳烃的分布。结果表明,神木原煤中的PAHs以两环、三环和四环PAHs为主,苯萃取液与石油醚苹取液中PAHs的分布大体相同,但在丰度上有很大差别。     

Distribution and Sources of Polycyclic Aromatic Hydrocarbons (PAHs) in Surface Sediments from the Northern Part of the Persian Gulf (Hormuzgan Province)

Sediments from the intertidal areas of Hormuzgan province in northern part of Persian Gulf (Iran) were investigated for the levels and possible sources of 15 polycyclic aromatic hydrocarbons (PAHs). Samples of sediments were collected from twelve sampling sites and analyzed for PAHs by gas chromatography–mass spectrometry (GC-MS). The results showed that the total concentrations of PAHs ranged from 765 to 1898 ng/g dry weight. Composition pattern in the sediment samples from 12 sampling sites was dominated by 4-ring PAH compounds. Molecular indices based on ratios of PAH concentrations were used to differentiate PAHs from pyrolitic, petrogenic and mixed origins. The results of study suggested that the main sources of PAHs in the sediment were mixed with pyrolitic and petrogenic inputs. According to the US sediments quality guidelines (SQGs) (ERL/ERM) sediments of the mentioned region did not show any ecotoxicological risk for benthic organisms.     

Characteristics of polycyclic aromatic hydrocarbons emissions of diesel engine fueled with biodiesel and diesel

With mutagenic and carcinogenic potential, polycyclic aromatic hydrocarbons (PAHs) from mobile source exhaust have contributed to a substantial share of air toxics. In order to characterize the PAHs emissions of diesel engine fueled with diesel, biodiesel (B100) and its blend (B20), an experimental study has been carried out on a direct-injection turbocharged diesel engine. The particle-phase and gas-phase PAHs in engine exhaust were collected by fiberglass filters and “PUF/XAD-2/PUF” cartridges, respectively, then the PAHs were determined by a gas chromatograph/mass spectrometer (GC/MS). The experimental results indicated that comparing with diesel, using B100 and B20 can greatly reduce the total PAHs emissions of diesel engine by 19.4% and 13.1%, respectively. The Benzo[a]Pyrene (BaP) equivalent of PAHs emissions were also decreased by 15.0% with the use of B100. For the three fuels, the gas-phase PAHs emissions were higher than particle-phase PAHs emissions and the most abundant PAH compounds from engine exhaust were naphthalene and phenanthrene. The analysis showed that there was a close correlation between total PAHs emissions and particulate matter (PM) emissions for three fuels. Furthermore, the correlation became more significant when using biodiesel.     

The Exposure Profiles,Correlation Factors and Comparison of PAHs and Nitro-PAHs in Urban and Non-Urban Regions in Suspended Particulate Matter in Poland

ABSTRACT

Polycyclic aromatic hydrocarbons (PAHs) and their nitrated derivatives are responsible for mutagenic activation of ambient air. The aim of the study was the assessment of exposure for PAHs and nitro-PAHs in the urbanized region in Poland in comparison with the non-urbanized region and assessment of seasonal variation of PAHs and nitro-PAHs. Concentrations of 12 PAHs, 8 nitrated PAHs in total suspended particulate matter in air of urban and suburban (reference samples-mountain region) region in Poland during four seasons have been shown. The method of solvent extraction of particulate matter, fractionation organic extract and HPLC and GC/MS analysis were applied. The concentrations of PAHs and nitro-PAHs were 10–100 times lower in reference samples than concentrations of PAHs and nitro-PAHs in urban region in summer. The concentrations of PAHs and nitro-PAHs were highest in winter. The exposure profiles of PAHs and nitro-PAHs in four seasons have been shown. The correlation factor between concentrations of PAHs and nitro-PAHs was found. Important influence of ambient air temperature for PAHs and nitro-PAHs concentrations was shown. Obtained results suggest that the coal combustion in Polish households was the main source of PAHs and their nitro derivatives contaminations. Emission from transport sources is a secondary source of air pollution in urban areas.     

Real-Time Monitoring of Polycyclic Aromatic Hydrocarbons in Cigarette Smoke Using Time-Resolved Laser-Induced Fluorescence

Cigarette smoke contains a large number of chemicals and gaseous compounds including polycyclic aromatic hydrocarbons (PAHs). Due to the importance of PAHs and their health effects in cigarettes, development of systems to analyze PAHs in cigarette smoke may become useful in developing a less harmful product. However, the complexity of cigarette smoke chemistry remains a significant obstacle in its analysis: many cigarette smoke components are produced due to reactions such as decomposition and recombination of cigarette components during the smoking process. Methods to analyze these reactions in real-time are needed. In this article the authors report direct monitoring of pyrene in mainstream smoke using time-gated laser-induced fluorescence (LIF) based on fiber optics. The time-gated detection system could provide a reduced background signal of mainstream smoke when using optimized gate delay and gate width parameters. The results demonstrate the feasibility of direct monitoring of PAHs in mainstream smoke.     

Levels of Volatile Polycyclic Aromatic Hydrocarbons in the Atmosphere of Athens,Greece

Eight light polycyclic aromatic hydrocarbons (PAHs) have been measured in the gas and particle phase of the atmosphere of Athens, in one site during an eight-month period (December, 1997-July, 1998). A glass fiber filter-polyurethane foam sheet high volume air sampler was used to collect the particle and vapor phase of the eight PAHs in nineteen samples, taken from the Athens center. Methodology of sampling as well as levels and abundance of PAHs in both phases are discussed. Seasonal variation of very volatile PAHs was found not to be strictly related to high temperatures and explanations are proposed. An unexpected PAHs pattern from two summer photochemical episodes is also discussed.     

BIOTA ACCUMULATION OF POLYCYCLIC AROMATIC HYDROCARBONS IN BENIN COASTAL WATERS

The contamination levels of 12 US-EPA polycyclic aromatic hydrocarbons (PAHs) from the tri-aromatics to the hexa- aromatics in biota and sediment of Cotonou's lagoon and Benin's continental shelf waters are identified in this paper.

PAHs were analyzed by gas-chromatography coupled with mass spectrometry (GC-SM). Total lipid contents (TLC) were measured for biota, and total organic carbon content (TOC) for sediment.

Total PAH concentrations obtained for organisms ranged between 15 and 102ngg^{? 1}, with mussels accumulating the highest concentrations of PAHs. The lower–molecular-weight (LMW) 3 ring PAHs were predominant in all biota and showed similar distribution patterns. Phenanthrene accounts for 76% of total bioaccumulation factors (BAFs). Biota and sediment accumulation factors (BSAFs) showed that the mussels are exposed to the LMW PAHs more than to the hydrophobic higher-molecular-weight (HMW) PAHs in the Benin coastal waters.