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.     

Volatilization Loss of 6 PAHs with 2–4 Rings Related to Coal Extracts

ABSTRACT

With 3 different bottles, the volatilities of 6 polycyclic aromatic hydrocarbons (PAHs), namely, acenaphthylene, acenaphthene, fluorene, phenanthrene, fluoranthene and pyrene, which were used as model compounds of coal here, had been measured by using gas chromatography/mass spectrometer (GC/MS). The results indicate that although these PAHs have a high boiling point (BP), some PAHs such as acenaphthylene and acenaphthene can be lost rapidly through volatilizing. Even pyrene, having a BP as high as 404°C, can also be lost by volatilizing for a longer period, such as 4 days or more. The volatilization loss of the PAHs is also related to the container. PAHs in wide-mouthed bottles will volatilize faster than in narrow-mouthed bottles. The volatilization loss of the PAHs and other compounds may lead to incorrect results in quantitatively analyzing them in coal extraction, if coal extracts are dried. So, the coal extracts by organic solvents should not be dried before measuring by GC/MS.     

Determination of the vapor pressures of select polychlorinated dibenzo-p-dioxins and dibenzofurans at 75-275 °C

Vapor pressures were determined for several polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at 75-275 °C, extending the available literature data to more relevant temperature regions and providing the first experimental data for 2,3,7-trichlorodibenzo-p-dioxin (2,3,7-TriCD). A modification of the effusion technique, based upon controlling the diffusion of the target compound and subsequent high resolution gas chromatography/low resolution mass spectrometry (HRGC/LRMS) analysis, was proven comparable to other accepted methods for determining the vapor pressures of semi-volatile organic compounds (SVOCs). Vapor pressures for octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) were in excellent agreement with those reported in literature. The application of the current method for the vapor pressure determinations of eight polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/PCDFs) in the extended temperature range (up to 275 °C) is reported. The extension of the vapor pressures to such temperatures, unprecedented for the PCDDs/Fs, is important for vapor-particle partitioning modeling in regions relevant to PCDD/F formation and control. Estimates for the melting temperatures and enthalpies of sublimation and vaporization are also reported, the latter for which no experimentally determined values have been found in the literature. The use of the method to deliver reproducible, trace concentrations (ppt-ppb) of targets was applied to the calibration of the jet-REMPI/TOFMS as an online detector for low chlorinated PCDDs/Fs.     

Screening of Aerosol Filter Samples for PAHs and Nitro-PAHs by Laser Desorption Ionization TOF Mass Spectrometry

Direct and selective screening of aerosol particulate matter for polycyclic aromatic hydrocarbons (PAHs) and nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) is achieved using laser desorption ionization time-of-flight (LDI TOF) mass spectrometry. Desorption and ionization of collected aerosol particulate matter was accomplished using pulsed UV radiation at 266 nm. PAHs were detected in positive ion spectra, while nitro-PAHs were selectively detected in negative ion spectra. Direct laser desorption ionization circumvents extraction procedures necessary for HPLC or gas chromatography/mass spectrometry (GC/MS) analyses, and such screening offers potential cost saving by identifying samples which contain too little PAH for GC/MS analyses to be productive. Applicability of the LDI TOF method was demonstrated by collecting aerosol particles of less than 2.5 mu m aerodynamic diameter (PM 2 . 5) on Teflon filters from inside an urban bus terminal. Sampling of small air volumes (0.32-0.98 m3) was sufficient for LDI TOF analysis. Positive ion mass spectra of all collected aerosol samples exhibited peaks attributed to a wide range of PAHs. Of primary importance, selective ionization and detection of less abundant and more toxic nitro-PAHs is demonstrated in the negative ion spectra. GC/MS analyses of duplicate filters confirmed laser desorption ionization analyses and assisted identification of specific PAH isomers.     

Thermal Behavior of PAHs,Hexachlorobenzene and PCDDs/PCDFs Adsorbed on Lignite Coke From Flue-Gas Cleaning in Municipal Waste Incinerators

Abstract

Lignite coke is increasingly employed as an adsorbent for flue-gas cleaning, for example, in waste incinerators. The aim of the studies described here was to verify the assumed deposition reliability of moving bed adsorbers even in the case of operational malfunction. To this end, the occurrence of glow clusters in coke beds loaded with various pollutants such as polyaromatic hydrocarbons (PAHs), hexachlorobenzene (HCB), polychlorinated dibenzodioxins and dibenzofurans (PCDDs, PCDFs) was simulated and the thermal behavior of adsorbed compounds recorded by quantitative measurement of the coke pollutant and of the desorption gases. Assuming an incident that would lead to the spontaneous ignition of the adsorber, the results of our studies show that due to the desorption or decomposition reactions of PAHs, PCDDs and PCDFs, as well as HCB as a model substance for high-chlorinated compounds, only small fractions of pollutants are released.     

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).     

Removal characteristics of PCDDs/Fs from municipal solid waste incinerator by dual bag filter (DBF) system

A dual bag filter (DBF) system was developed for the removal of dioxins (PCDDs/Fs) emitted from a municipal solid waste incinerator (MSWI). A 2000 N m³/h capacity DBF pilot plant was designed, manufactured, and operated with actual MSWI flue gases. The result showed that pressure drop of the filter bag is the most important variable in PCDDs/Fs removal by the DBF system. Removal efficiency of PCDDs/Fs decreased as pressure drop increased in the first bag filter of the DBF system. On the contrary, removal efficiency of PCDDs/Fs increased as the pressure drop of the second bag filter increased. Pressure drop ranges for the most effective operation in the filter bag were 150–200 mm H₂O and 170–200 mm H₂O for first and second bag filter, respectively. The emission of PCDDs/Fs after removal by the DBF system was below 0.05 ng-TEQ/ N m³, when pressure drop of the second bag filter was operated near 200 mm H₂O. Activated carbon consumption was also less in case of DBF (40 mg/N m³) as compared to SBF which discharged about 100 mg/N m³.     

Analytical Methods for Determination of Polycyclic Aromatic Hydrocarbons (PAHs) — A Historical Perspective on the 16 U.S. EPA Priority Pollutant PAHs

The identification of 16 polycyclic aromatic hydrocarbons (PAHs) as priority pollutants by the U.S. Environmental Protection Agency (EPA) in 1976 has been a primary driver for analytical methods development for the determination of PAHs. In this article, the historical development of methods in liquid chromatography (LC) and gas chromatography (GC) to separate these 16 PAHs is discussed. In LC a significant effort was the search for and the fundamental understanding of the unique stationary phase capable of achieving the desired separation of the 16 EPA PAHs. For GC methods, the focus on stationary phase development has been the separation of critical isomers with a broader scope than the 16 EPA PAHs. The current routine LC and GC methods for the 16 EPA PAHs are well established; however, new advances in analytical techniques beyond LC and GC are discussed. Many analysts are now interested in more than just the 16 EPA PAHs (e.g., higher molecular mass PAHs and alkyl-substituted PAHs) and analytical methods have emerged to address these needs. Reference materials and their use in the determination of PAHs are discussed.     

Polycyclic Aromatic Hydrocarbons Determination in Grilled Beef and Chicken

ABSTRACT

Polycyclic aromatic hydrocarbons (PAHs) are principally formed as a result of thermal treatment of food, especially grilling or barbecuing. In the present study, two types of Iranian popular grilled beef and chicken dishes (kebab) were analyzed for toxic PAHs, i.e., naphthalene, fluoranthene, phenanthtrene, anthracene, pyrene, and benzo(a)pyrene applying GC/MS. The differences in PAHs concentrations among grilled beef and chicken (kebab koobide and juje kebab) were found to be significant (p < 0.05), ranging from 0.29 to 21.95 ng·g^?1. Benzo(a)pyrene was found in nearly all samples; the maximum concentration of total PAHs was 21.95 ng·g^?1 found in grilled beef (koobide Khalij fars) and the lowest was 0.29 ng·g^?1 in grilled chicken (juje kebab) of Sahel restaurant.     

Characteristics of PAHs,PCDD/Fs,PCBs and PBDEs in the Sediment of Lake Baikal,Russia

The levels of PAHs, PCDD/Fs, PCBs, and PBDEs in Lake Baikal were monitored for the first time using deep water sediment. The sediment samples were collected from 15 stations in four regions of Lake Baikal: Ol’khon Island (n = 8), the Angara River estuary (n = 2), the Selenga River delta (n = 2), and the Baikal pulp and paper mill (BPPM) (n = 3). The highest average concentrations of PCDD/Fs (20.24 pg/g d.w.) and PCBs (68.72 ng/g d.w.) were found at Ol’khon Island. The highest total PBDE concentrations were found at BPPM, with a mean concentration of 575.76 pg/g d.w. For PCBs, PCB-52, and PCB-69 were dominant, making up 11% of the total 209 PCB congeners. BDE-209 contributed 60% of PBDEs in Lake Baikal. According to the TPEQ concentration of PAHs, PAHs contributed the most to Lake Baikal contamination. The sources of contamination of PAHs, PCDDs, and PCBs in Lake Baikal are identified as combustion, runoff from the use of the pesticides (PCP) and insulating oil, specifically for PCBs. The source of PBDEs is assumed to be production, use and disposal of products containing PBDEs, in addition to atmospheric long-range transport and deposition.     

Dioxin,Dioxin–Like PCBs and Indicator PCBs in Some Medicinal Plants Irrigated with Wastewater in Ismailia,Egypt

Wastewater is often leaden with various contaminants that may accumulate in soils and can under some conditions enter the agricultural food chain. Concentrations of PCDD/Fs, DL-PCBs and NDL-PCBs have been determined using GC/HRMS in three of the commonly used medicinal plant (henna, rosemary, and moghat) grown on raw wastewater. In the case of henna and rosemary plants, all wastewater irrigated samples showed higher content of the studied contaminants than freshwater irrigated samples, while moghat samples, whether irrigated with freshwater or wastewater, had more or less the same content of the studied contaminants. Concentrations in plant samples ranged between 0.00004 and 0.865 pg WHO TEQ/g wet w for PCDDs, and between 0.03 and 1.86 pg WHO TEQ/g wet w for the PCDFs. Levels of PCB TEQ ranged from 0.005 to 0.76 pg/g wet w. In descending order, rosemary, henna, and moghat had the highest concentrations of total TEQ (PCDD/Fs + DL-PCBs). The congeners pattern in henna and rosemary samples was generally characterized by the dominance of PCDFs with a significant contribution from the lower (mono- to tri-) PCDFs. In moghat samples the profile was dominated by PCDDs, with OCDD contributing 100% to PCDDs. PCBs contribution to the total TEQ was on average 25%, 7% and 2% in rosemary, moghat and henna respectively. For NDL-PCBs, the sum concentration of 17 PCBs congeners increased from 2.65 to 4.13 ng/kg wet w in henna, and from 4.64 to 7.16 ng/ kg wet w in rosemary due to the irrigation with wastewater. Congener PCB 28 was the main contributor (60%) to sum 6 indicators in all samples, followed by PCB 52 (18%) and PCB 101 (6%).     

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.     

Comparison of Liquid Chromatography with Fluorescence Detection and Gas Chromatography/Mass Spectrometry for the Determination of Polycyclic Aromatic Hydrocarbons in Environmental Samples

Liquid chromatography (LC) with fluorescence detection and gas chromatography/mass spectrometry (GC/MS) have been compared for the determination of polycyclic aromatic hydrocarbons (PAHs) in a variety of environmental samples. Three sets of data are presented in this paper in which LC/fluorescence and GC/MS were used for the analysis of the same samples. These three data sets include the comparison of results from: (1) certification measurements for three natural matrix Standard Reference Materials (SRM's), (2) an international round robin for the determination of PAHs in air and diesel particulate samples, and (3) the analysis of four marine sediment reference materials. The results from these studies indicate that the two techniques generally provide comparable results for the measurement of PAHs in environmental samples (in the range of 0.1 to 300 ng/g), with differences in the two techniques between 5–20%. However, at low levels, anthracene and perylene are best measured using LC/fluorescence because of their selective and sensitive fluorescence detection characteristics. In contrast, GC/MS provides more accurate results for the determination of benzo[ghi]perylene because of its low fluorescence sensitivity.     

Vehicular Tire as Potential Adsorbent for the Removal of Polycyclic Aromatic Hydrocarbons

ABSTRACT

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants, entering into various water and wastewater systems through various natural and anthropogenic activities. The aim of the work is to convert vehicular tires, a highly available waste material, into potential adsorbent for the removal of PAHs from aqueous solutions. The BET surface area of the prepared vehicular tire activated carbon is 643.86 m²/g. Removal of PAHs using activated carbons and the effect of various parameters such as contact time, adsorbent dose, temperature, and pH on the adsorption have been evaluated. The data were fitted to Freundlich and Langmuir isotherms and values of various constants were evaluated. In all the cases, Freundlich model was found to be better fitted. The equilibrium time for adsorption of PAHs was 120 min. The values of thermodynamic parameters, such as Gibb's free energy change ΔG°, enthalpy change ΔH°, and entropy change ΔS°, were calculated using adsorption equilibrium constants obtained from Langmuir isotherm. The thermodynamic data for adsorption of PAHs revealed spontaneity and endothermic nature of the adsorption process. The samples were analyzed using a UV–vis spectrophotometer for PAH determination. Mixture of sodium hydroxide and ethanol in different proportions was tried for desorption of PAHs and 50% ethanolic NaOH solution was most effective. The developed activated carbon demonstrates good adsorption and desorption capabilities for PAHs, indicating towards its suitability for use in the treatment processes of various industrial effluents or water streams containing PAHs.     

PAHs and Mutagenicity of Inhalable and Respirable Diesel Particulate Matter in Santiago,Chile

Delayed human effects such as cancer could be a consequence of chronic exposure, over long periods of time, to inhalable (PM₁₀) and respirable (PM_2.5) particles containing environmental carcinogen mixtures. Air pollution in Santiago, Chile, is a major public health problem due to the high levels of regulated pollutants such as PM₁₀, CO, and ozone. In this work, we studied the levels of polycyclic aromatic hydrocarbons (PAHs) onto PM₁₀ and PM_2.5 collected in diesel revision plants, in an urban area with a high flow of buses and trucks and in a rural area not exposed to diesel emissions. The PM₁₀ average levels in diesel emission plants were higher than the Chilean PM₁₀ standard and higher than those found in the urban and rural areas. In the urban area the PM₁₀ average levels were lower than the Chilean PM₁₀ standard, although some 24 h levels surpassed the levels established to decree preemergency or emergency and in some cases were higher than the levels reported by all the official monitoring stations. The levels of total PAHs onto PM₁₀ were higher in the diesel plants than in the urban area and rural area, but the levels of six carcinogenic PAHs were similar in the diesel plants to those found in the urban area. Organic extracts from PM₁₀ collected in diesel plants in Salmonella typhimurium TA98 in the presence and in the absence of an S9 activation system were significantly higher than in the urban area and rural area. Mutagenic activity with and without S9 in diesel plants and the urban area showed that indirect (PAHs) and direct (nitro-PAHs) mutagenic compounds are present in organic extracts from PM₁₀. In conclusion, these results showed that in Santiago diesel emission particles were highly mutagenic and contain carcinogenic PAHs. This might represent a risk for long-term respiratory effects in Santiago's inhabitants.     

EXHAUST EMISSIONS OF PAHs OF PASSENGER CARS

Exhaust emissions of 16 PAHs, listed by the U.S. Environmental Protection Agency (USEPA) as priority pollutants, are measured using a vehicle bench on a sample of passenger cars. Thirteen gasoline vehicles and 17 diesel vehicles are tested, complying with ECE 1504 to Euro 3 emission standards, according to three real-world driving cycles based on European driving behavior (2 urban and 1 motorway). HPLC with fluorometric detection is used for their quantification.

The effect of cold or hot start is put to the fore with the short urban INRETS cycle.

The particle and gas-phase distribution is studied for all the vehicles and the hot driving cycles.

In this study, the cars' emissions are shown to be reduced, according to the legislative level (Euro-1, 2, 3 …). The majority of volatile PAHs is mainly observed in the gas phase whereas the less volatile and carcinogenic PAHs are especially adsorbed on particles.     

GC/MS内标法测定全钢载重子午线轮胎中的多环芳短含量

介绍轮胎中多环芳烃的危害以及来源,采用气质联用结合内标法测定了不同品牌和规格的全钢载重子午线轮胎主要部位受限制的8种多环芳烃的含量。各部位样品的超声波萃取液经气质联用的选择离子监测模式采集数据后,根据内标法建立的标准曲线计算其中的多环芳烃含量。本方法灵敏、准确、可靠且适用于轮胎中各部位多环芳烃含量的测定。     

GC/MS内标法测定橡胶制品中的18种多环芳烃含量

介绍了橡胶制品中多环芳烃（PAH）的危害及来源,采用气质联用（GC/MS）结合内标法,建立了测定橡胶制品中18种PAH含量的方法。制品的超声波提取液经GC/MS选择离子监测模式采集数据后,根据内标法建立标准曲线,计算其中的PAH含量。经精密度和回收率验证,本方法灵敏、准确、可靠,适用于橡胶制品中PAH含量的测定。     

Mangrove Oyster (Crassostrea belcheri) as a Biomonitor Species for Bioavailability of Polycyclic Aromatic Hydrocarbons (PAHs) from Sediment of the West Coast of Peninsular Malaysia

ABSTRACT

Rapid industrialization and urbanization in the west coast of Peninsular Malaysia has caused increasing pollution particularly of petroleum and petroleum by-products. Surface sediment and mangrove oyster (Crassostrea belcheri) were collected from five mangrove ecosystems in the west coast of Peninsular Malaysia and investigated for bioavailability of polycyclic aromatic hydrocarbons (PAHs). Sampling locations were selected from both remote areas with few or no previous records of petroleum pollution such as Pulau Merambong and polluted areas that are under international attention such as Klang mangrove ecosystem. PAH fractions were obtained through soxhlet extraction and two-step column chromatography and the fractions were injected to gas chromatography-mass spectrometry (GC-MS) for analysis. The concentrations of PAHs ranged from 151 to 4973 ng g^?1 dw in the sediments, while from 309 to 2225 ng g^?1 dw in the oysters. When tested for diagnostic ratios, a predominance of pyrogenic source PAHs was detected in the sediments, whereas PAHs in the oysters had mixed petrogenic and pyrogenic sources. A significant correlation (p < 0.05) was found between high molecular weight (HMW) PAHs in the sediments and oysters and biota accumulation factors (BAFs) of PAHs were approaching or exceeding unity indicating the ability of mangrove oyster in bioaccumulation of PAHs. Overall, this study indicates that mangrove oyster (C. belcheri) can be used as a biomonitor species for PAHs in an aquatic environment.     

High-Molecular-Weight Polycyclic Aromatic Hydrocarbons in the Area and Vicinity of the Deza Chemical Plant,Czech Republic

Polycyclic aromatic hydrocarbons (PAHs) with molecular weight exceeding 278 amu were analyzed in air, water, and soils from the area and vicinity of the DEZA Chemical Plant (Vala w ské Mezi q í ) í, Czech Republic). Air and water were sampled using semipermeable membrane devices (SPMDs); grab sampling was applied for soils. Laser desorption/ionization-time-of-flight mass spectrometry (LDI-TOF MS) and liquid chromatography/ion trap mass spectrometry with atmospheric pressure chemical ionization (LC/APCI-ITMS) were employed for the quick assessment of PAH distribution and for the identification and quantification of some high-molecular-weight PAHs. Compounds with molecular mass up to 450 u were found. LDI-TOF mass spectra and selected LC/APCI-ITMS profiles (m/z 303, m/z 327, and m/z 351) were compared to identify potential source of contamination in this locality. High-molecular-weight PAHs were found in all environmental compartments in the area studied; their levels were quite high close to their source and decreased sharply with increasing distance from it.