Characterization of Polycyclic Aromatic Hydrocarbons from the

Abstract

Diesel fuels governed by U.S. regulations are based on the index of the total aromatic contents. Three diesel fuels, containing various fractions of light cycle oil (LCO) and various sulfur, total polyaromatic, and total aromatic contents, were used in a heavy-duty diesel engine (HDDE) under transient cycle test to assess the feasibility of using current indices in managing the emissions of polycyclic aromatic hydrocarbons (PAHs) from HDDE. The mean sulfur content in LCO is 20.8 times as much as that of premium diesel fuel (PDF). The mean total polyaromatic content in LCO is 28.7 times as much as that of PDF, and the mean total aromatic content in LCO is 2.53 times as much as that of PDF. The total polyaromatic hydrocarbon emission factors in the exhaust from the diesel engine, as determined using PDF L3.5 (3.5% LCO and 96.5% PDF), L7.5 (7.5% LCO and 92.5% PDF), and L15 (15% LCO and 85% PDF) were 14.3, 25.8, 44, and 101 mg L^?1, respectively. The total benzo(a)pyrene equivalent (BaP_eq) emission factors in the exhaust from PDF, L3.5, L7.5, and L15 were 0.0402, 0.121, 0.219, and 0.548 mg L^?1, respectively. Results indicated that using L3.5 instead of PDF will result in an 80.4% and a 201% increase of emission for total PAHs and total BaP_eq, respectively. The relationships between the total polyaromatic hydrocarbon emission factor and the two emission control indices, including fuel polyaromatic content and fuel aromatic content, suggest that both indices could be used feasibly to regulate total PAH emissions. These results strongly suggest that LCO used in the traveling diesel vehicles significantly influences PAH emissions.     

底泥中多环芳烃的处理技术进展

底泥中多环芳烃（PAHs）的处理方法主要有物化处理和生物处理。物化处理方法有湿式空气氧化、溶剂浸提、热解吸等；生物处理有好氧处理和厌氧处理。物化处理速度快、效果明显，但能耗高、投资大；生物处理方法虽然能耗低，但速度慢、降解率较低。实际运用中宜发展物化和生物的组合工艺。     

Polynuclear Aromatic Hydrocarbons Associated with Particulates in Pittsburgh Air

Pittsburgh air was sampled continuously at one site for 886 hrs./sample at 45 cfm with a high volume sampler equipped with a horizontal elutriator as a first stage of separation, and an MSA 1106B glass fiber filter as a final particulate collection stage. The horizontal elutriator was designed to simulate the particulate deposition characteristics of the human respiratory tract. Samples were collected during the period June 1964 to February 1965. Respirable and non-respirable particulate samples were analyzed for polynuclear aromatic hydrocarbon content by a new technique which utilized dual column, flame ionization gas chromatography. It was possible to quantitatively analyze a concentrated benzene extract of the particulate sample for the following individual components: 1, 2 benzanthracene; chrysene; pyrene; 3,4 benzofloranthene; 1, 12 benzoperylene. It was not possible to distinguish between 3,4 benzopyrene, 1,2 benzopyrene and perylene; only the total quantity of these compounds present was detected. This analytical technique is comparable in sensitivity to formerly reported, more time-consuming methods and is very rapid, requiring less than one hour to perform after benzene extraction. Amounts of the above compounds associated with the two particulate fractions collected are reported and discussed.     

The Automotive Contribution to Air-Borne Polynuclear Aromatic Hydrocarbons in Detroit

The General Motors Research Laboratories and the Sloan-Kettering Institue for Cancer Research are collaborating to determine the contribution by automotive vehicles to the polynuclear aromatic hydrocarbons in city air. Sampling of particulate matter at the rate of 140 M³/min (5000 cfm) was carried out at two heavily-trafficked sites in Detroit and one suburban site in Warren, Michigan. Carbon monoxide was determined continuously, and particulate matter was analyzed for “tar,” polynuclear aromatic hydrocarbons, lead, vanadium, and sulfates. Polynuclear aromatic hydrocarbons in automobile exhaust gas are assumed to be dispersed in air along with carbon monoxide or lead from automobiles. It is further assumed that automobiles are the sole source of carbon monoxide and lead in the atmosphere. Concentrations of carbon monoxide and lead in exhaust gas and in the air are utilized to estimate the percentage of polynuclear aromatic hydrocarbons in the air attributable to automobiles. The mean automobile contributions to benzo(a)pyrene in the air, based on lead concentrations, were 18% at a Freeway Interchange, 5% in a downtown commercial area, and 42% in suburban Warren. The average concentrations of benzo(a)pyrene at the sites were 6 μg/10³ M³, 7 μg/10³ M³ and 1 μg/10³ M³, respectively. Mean contributions based on carbon monoxide concentrations were approximately twice the levels based on lead concentrations. Benzo(a)pyrene and benz(a)anthracene in air were not statistically related to carbon monoxide or lead in air, but were higher in winter than in summer, probably because of the higher levels of these materials emitted in space heating combustion in winter.     

The Fate of Aromatic Hydrocarbons in Photochemical Smog Systems: Toluene

The economic impact of various ozone concentrations on California agriculture is examined using an economic model of crop production that accounts for interdependence among crops. Such interdependence recognizes that net economic effects are determined not only by yield sensitivity to ozone but also by market conditions that affect relative crop prices and profitability. Changes in crop yields due to alternations in ambient ozone concentrations are used to drive the economic model. The predicted yield changes are derived from NCLAN data under a range of assumptions concerning functional form and yield effects. The results indicate that the economic effects of ozone are substantial for 13 included crops. The economic estimates display varying sensitivity to the functional form of the response relationship. The need for additional experimental data to more precisely define the relationship depends on the range of policy actions being considered.     

Using Radiocarbon to Apportion Sources of Polycyclic Aromatic Hydrocarbons in Household Soot

To determine whether polycyclic aromatic hydrocarbons (PAHs) in household soot were derived from the combustion of scrap wood or creosote that was impregnated in the wood (or some combination of both), the molecular composition and radiocarbon ( 14 C) content of the total carbon and several PAHs in the soot was investigated. The 5730-year half-life of 14 C makes it an ideal marker for identifying creosote-derived PAHs ( 14 C-free) versus those derived from the combustion of wood (contemporary 14 C). The 14 C abundance of phenanthrene, fluoranthene, pyrene, and retene was determined by accelerator mass spectrometry after solvent extraction and purification by preparative capillary gas chromatography. The molecular analysis (presence of retene and 1,7-dimethylphenanthrene) and bulk 14 C content (contemporary) of the soot indicated that wood combustion was a strong source of carbon to the soot. The 14 C of retene in two soot samples was also contemporary, indicating that it was derived from the combustion of the scrap wood. These results are consistent with previous work that has suggested that retene is an excellent marker of wood combustion. However, the 14 C content of phenanthrene, fluoranthene, and pyrene in one soot sample was much lower and revealed that these compounds had a mixed creosote and wood source. Using an isotopic mass balance approach, we estimate that 40 to 70% of phenanthrene, fluoranthene, and pyrene were derived from the combustion of the scrap wood. The results of this study show that molecular marker and bulk 14 C analysis can be potentially misleading in apportioning sources of every PAH, and that molecular-level 14 C analysis of PAHs can be a powerful tool for environmental forensics.     

The Reuse of Biosludge as an Adsorbent from a Petrochemical Wastewater Treatment Plant

Abstract

Biosludge was obtained from a petrochemical industry’s biological wastewater treatment plant. Zinc chloride (ZnCl₂) was used as a sludge activation agent during the pyrolytic process. Scanning electron microscope (SEM) image photographs, element composition, surface functional group, and pore structure were analyzed for the sludge adsorbent characteristics. Results indicated the proper ZnCl₂-immersed concentration, pyrolytic temperature, and time could produce adsorbent from the bio-sludge. The optimal conditions for a larger surface area adsorbent were 3 M ZnCl₂-immersed sludge pyrolyzed at 600 °C for 30 min and washed with 3 N hydrochloric acid (HCl) solution and distilled water. The predominant pore size of the sludge adsorbent was the mesopore.     

Basic Research on the Emission of Polycyclic Aromatic Hydrocarbons caused by Waste Incineration

The emission of polycyclic aromatic hydrocarbons (PAH) caused by municipal waste incineration varies according to waste composition and operating parameters such as furnace temperature and excess air. However, to obtain a sample sufficient to measure the emission of PAH at trace levels, it is necessary to operate the incinerator for many hours. Since during these lengthy periods it has not always been possible to maintain stable conditions, it is very difficult to determine the relationship between the emission and waste composition.

In our basic research, therefore, we used municipal waste with an artificially regulated composition for our combustion experiments, and by using an experimental Incinerator we examined the emission behavior of PAH with respect to changes in waste composition and combustion conditions. The following facts were revealed by the results: ? The PAH found in the flue gas were predominantly the more volatile compounds.

? When municipal waste was incinerated at over 850 °C, the concentration of PAH in the flue gas increased rapidly as the proportion of plastics in the waste increased from 0 to 24 percent.

? The elimination of plastics from municipal waste by separate collection and the improvement of combustion conditions can effectively diminish the emission of PAH.

     

Combustion Kinetics and Emission Characteristics of Polycyclic Aromatic Hydrocarbons from Polylactic Acid Combustion

Abstract

This study investigates the combustion kinetics and emission factors of 16 U.S. Environmental Protection Agency priority polycyclic aromatic hydrocarbons (PAHs) in polylactic acid (PLA) combustion. Experimentally, two reactions are involved in the PLA combustion process that potentially result in the release of lactide, acetaldehyde, and n-hexaldehyde. The products may continuously be oxidized to form carbon dioxide (CO₂) and some PAHs produced because of incomplete combustion. The analytical results indicate that the emission factors for PAHs are in the range of not detectable to 98.04 μg/g. The emission factors are much lower than those of poly(ethylene terephalate) (PET) and other combustion of plastics. Results from this work suggest that combustion is a good choice for waste PLA disposal.     

Using Nanoscale Zero-Valent Iron for the Remediation of Polycyclic Aromatic Hydrocarbons Contaminated Soil

Abstract

The sites contaminated with recalcitrant organic compounds, such as polycyclic aromatic hydrocarbons (PAHs) with multiple benzene rings, are colossal and ubiquitous environmental problems. They are relatively nonbiodegradable and mutagenic, and 16 of them are listed in the U.S. Environment Protection Agency priority pollutants. Thus, the efficient and emerging remediation technologies for removal of PAHs in contaminated sites have to be uncovered urgently. In this decade, the zero-valent iron (ZVI) particles have been used successfully in the laboratory, pilot, and field, such as degradation of chlorinated hydrocarbons and remediation of the other pollutants. Nevertheless, as far as we know, little research has investigated for soil remediation; this study used nanoscale ZVI particles to remove pyrene in the soil. The experimental variables were determined, including reaction time, iron particle size, and dosage. From the results, both the micro- and nanoscales of ZVI were capable of removing the target compound in soil, but the higher removal efficiencies were by nanoscale ZVI because of the massive specific surface area. The optimal operating conditions to attain the best removal efficiency of pyrene were obtained while adding nanoscale ZVI 0.1 g/g soil within 60 min and 150 rpm of mixing. Thus, nanoscale ZVI has proved to be a promising remedy for PAH-contaminated soil in this study, as well as an optimistically predictable application for additional pilot and field studies.     

三株优势菌对多环芳烃的降解性能研究

多环芳烃具有毒性、生物蓄积性和半挥发性,并能在环境中持久存在。生物修复处理具有费用低、效果好、污染物残留量低、不产生二次污染、能够保持或改善植物生长的土壤结构等优点。实验分别在对单一菌株、两两混合菌株及三株菌混合等三种情形下,对蒽、菲、芘的降解作用进行了研究。研究结果表明：单一菌株对蒽、菲、芘有一定的降解能力,菌株混合时,对蒽、菲的降解率有所提高;三株菌种混合时,黄杆菌对放线菌、红球菌的生长过程有抑制作用;蒽、菲、芘的降解过程会不断交替进行着产酸和脱羧过程,使降解液pH值出现波动;同时在降解过程中,菌体能产生表面活性物质,这有利于蒽、菲、芘的生物降解转化。     

Medium scale spatial structures of Polycyclic Aromatic Hydrocarbons in the topsoil of Tianjin area

The spatial distribution patterns of Polycyclic Aromatic Hydrocarbons (PAHs) in soil are important to regional environmental assessment. In this paper, the spatial structural features of sixteen prior PAH compounds in the topsoil of Tianjin area, as well as soil properties, were studied. Results shown that medium scale spatial autocorrelations were well revealed. Spherical models with sills could be used to fit all experimental variograms. The spatial structures of PAHs contents demonstrated significant anisotropy. Air precipitation caused by the combustion of coal was the key factor in the formation of the spatial structural patterns of PAHs in the topsoil of Tianjin area.     

Medium Scale Spatial Structures of Polycyclic Aromatic Hydrocarbons in the Topsoil of Tianjin Area

The spatial distribution patterns of Polycyclic Aromatic Hydrocarbons (PAHs) in soil are important to regional environmental assessment. In this paper, the spatial structural features of sixteen prior PAH compounds in the topsoil of Tianjin area, as well as soil properties, were studied. Results shown that medium scale spatial autocorrelations were well revealed. Spherical models with sills could be used to fit all experimental variograms. The spatial structures of PAHs contents demonstrated significant anisotropy. Air precipitation caused by the combustion of coal was the key factor in the formation of the spatial structural patterns of PAHs in the topsoil of Tianjin area.     

Factors Influencing the Emissions of Nitrated-Polynuclear Aromatic Hydrocarbons(Nitro-PAH) from Diesel Engines

The potential problem of 1-nitropyrene (1-NP) formation during filter sampling of diesel emissions from dilution tubes is assessed. Rates of formation are calculated using data generated from several independent filter exposure studies. A portion of the 1-NP (12% average) found in participates collected from light-duty (LDD) and heavy-duty diesels (HOD) was found to be due to formation on the filter under average sampling conditions of 10-15/1 dilution at 44°C with 3 ppm NO₂ for 23 min. On the average, the concentration of 1-NP in participates emitted from HDD is 16 times less than that found in LDD run under similiar transient conditions. The average emission rate of 1-NP generated from the LDD and HDD was 4.7 μg/km and 1.5 μg/km, respectively for the vehicles operating under Federal Test Procedure (FTP)-transient conditions. Under operating conditions which increase exhaust temperature (increased speed and load), the concentration of nitro-PAH is significantly reduced with a concurrent increase in the concentration of partially oxidized nitro-PAH and dinitro-PAH. The concentration of 1-NP in the particulates measured from HDD in these dilution tube studies (0.33-0.95 ppm, depending upon engine load) is comparable to that measured in highway tunnel experiments (0.54 ppm average).     

Source Resolution of Fine Particulate Polycyclic Aromatic Hydrocarbons Using a Receptor Model Modified for Reactivity

This paper provides source contribution estimates from vehicular and meat-cooking emissions to particulate polycyclic aromatic hydrocarbon (PAH) and elemental carbon (EC) concentrations measured at two Los Angeles sites during a field study in 1989. The source concentration matrix for PAH was based on new data for vehicular emissions and literature data for meat-cooking operations. The chemical mass balance (CMB 7.0) receptor model was used, and source profiles were modified to reflect reactive decay of PAH in the atmosphere. The calculations indicate that the Pico Rivera site was dominated by auto emissions, which account for more than 90 percent of all the PAH (except chrysene), carbon monoxide (CO), and 61 percent of the EC concentrations. In contrast, emissions from meat cooking contributed significantly (20 to 75 percent) to the concentrations of four-ring PAH measured at a residential site at Upland. The five-ring and larger PAH were attributed to auto emissions at Upland as well.     

Compositional Changes of Aromatic Steroid Hydrocarbons in Naturally Weathered Oil Residues in the Egyptian Western Desert

Naturally weathered oil residues from an arid dumpsite in Al-Alamein, Egypt were analyzed for monoaromatic and triaromatic steranes to demonstrate the utility of biomarker compounds in assessing the chemical composition changes during the degradation of the released oil residues in a terrestrial environment. The characterizations of individual aromatic compounds were based on gas chromatography/mass spectrometry (GC/MS) analyses. The results showed that triaromatic sterane distributions were similar in the oil residues of varying weathering degradation extents and correlated with a fresh crude oil sample of the Western Desert-sourced oil. Molecular ratios of triaromatic sterane compounds (ratios of C₂₈20R /C₂₈20S, C₂₇20R /C₂₈20R, and C₂₈20S /[C₂₆20R + C₂₇20S ]) were proved to be suitable for source identification. Major changes in chemical compositions during weathering of the oil residues were the depletion of short chain mono- and tri-aromatic steranes in samples that had undergone extensive degradation. The results of triaromatic sterane distribution are in good agreement with weathering classification based on the analyses of saturate and aromatic hydrocarbons and the ratios of n -alkanes, PAHs and saturate biomarker compounds.     

Effects of Open Burning of Rice Straw on Concentrations of Atmospheric Polycyclic Aromatic Hydrocarbons in Central Taiwan

Abstract

The sizes and concentrations of 21 atmospheric polycyclic aromatic hydrocarbons (PAHs) were measured at Jhu-Shan (a rural site) and Sin-Gang (a town site) in central Taiwan in October and December 2005. Air samples were collected using semi-volatile sampling trains (PS-1 sampler) over 16 days for rice-straw burning and nonburning periods. These samples were then analyzed using a gas chromatograph with a flame-ionization detector (GC/FID). Particle-size distributions in the particulate phase show a bimode, peaking at 0.32–0.56 μm and 3.2–5.6 μm at the two sites during the nonburning period. During the burning period, peaks also appeared at 0.32–0.56 μm and 3.2–5.6 μm at Jhu-Shan, with the accumulation mode (particle size between 0.1 and 3.2 μm) accounting for approximately 74.1% of total particle mass. The peaks at 0.18–0.32 μm and 1.8–3.2 μm at Shin-Gang had an accumulation mode accounting for approximately 70.1% of total particle mass. The mass median diameter (MMD) of 3.99–4.35 μm in the particulate phase suggested that rice-straw burning generated increased numbers of coarse particles. The concentrations of total PAHs (sum of 21 gases + particles) at the Jhu-Shan site (Sin-Gang site) were 522.9 ± 111.4 ng/m? (572.0 ± 91.0 ng/m?) and 330.1 ± 17.0 ng/m? (or 427.5 ± 108.0 ng/m?) during burning and nonburning periods, respectively, accounting for a roughly 58% (or 34%) increase in the concentrations of total PAHs due to rice-straw burning. On average, low-weight PAHs (about 87.0%) represent the largest proportion of total PAHs, followed by medium-weight PAHs (7.1%), and high-weight PAHs (5.9%). Combustion-related PAHs during burning periods were 1.54–2.57 times higher than those during nonburning periods. The results of principal component analysis (PCA)/absolute principal component scores (APCS) suggest that the primary pollution sources at the two sites are similar and include vehicle exhaust, coal/wood combustion, incense burning, and incineration emissions. Open burning of rice straw was estimated to contribute approximately 5.0–33.5% to the total atmospheric PAHs at the two sites.     

Compositional Changes of Aromatic Steroid Hydrocarbons in Naturally Weathered Oil Residues in the Egyptian Western Desert

Naturally weathered oil residues from an arid dumpsite in Al-Alamein, Egypt were analyzed for monoaromatic and triaromatic steranes to demonstrate the utility of biomarker compounds in assessing the chemical composition changes during the degradation of the released oil residues in a terrestrial environment. The characterizations of individual aromatic compounds were based on gas chromatography/mass spectrometry (GC/MS) analyses. The results showed that triaromatic sterane distributions were similar in the oil residues of varying weathering degradation extents and correlated with a fresh crude oil sample of the Western Desert-sourced oil. Molecular ratios of triaromatic sterane compounds (ratios of C 28 20R /C 28 20S , C 27 20R /C 28 20R , and C 28 20S /[C 26 20R + C 27 20S ]) were proved to be suitable for source identification. Major changes in chemical compositions during weathering of the oil residues were the depletion of short chain mono- and tri-aromatic steranes in samples that had undergone extensive degradation. The results of triaromatic sterane distribution are in good agreement with weathering classification based on the analyses of saturate and aromatic hydrocarbons and the ratios of n -alkanes, PAHs and saturate biomarker compounds.     

Effects of Heating Season on Residential Indoor and Outdoor Polycyclic Aromatic Hydrocarbons, Black Carbon, and Particulate Matter in an Urban Birth Cohort

Exposure to air pollutants has been associated with adverse health effects. However, analyses of the effects of season and ambient parameters such as ozone have not been fully conducted. Residential indoor and outdoor air levels of polycyclic aromatic hydrocarbons (PAH), black carbon (measured as absorption coefficient [Abs]), and fine particulate matter <2.5 μm (PM)(2.5) were measured over two-weeks in a cohort of 5-6 year old children (n=334) living in New York City's Northern Manhattan and the Bronx between October 2005 and April 2010. The objectives were to: 1) characterize seasonal changes in indoor and outdoor levels and indoor/outdoor (I/O) ratios of PAH (gas + particulate phase; dichotomized into Σ(8)PAH(semivolatile) (MW 178-206), and Σ(8)PAH(nonvolatile) (MW 228-278)), Abs, and PM(2.5); and 2) assess the relationship between PAH and ozone. Results showed that heating compared to nonheating season was associated with greater Σ(8)PAH(nonvolatile) (p<0.001) and Abs (p<0.05), and lower levels of Σ(8)PAH(semivolatile) (p<0.001). In addition, the heating season was associated with lower I/O ratios of Σ(8)PAH(nonvolatile) and higher I/O ratios of Σ(8)PAH(semivolatile) (p<0.001) compared to the nonheating season. In outdoor air, Σ(8)PAH(nonvolatile) was correlated negatively with community-wide ozone concentration (p<0.001). Seasonal changes in emission sources, air exchanges, meteorological conditions and photochemical/chemical degradation reactions are discussed in relationship to the observed seasonal trends.     

江苏盐城滩涂土壤中多环芳烃的测定

文中采用江苏盐城滩涂响水到滨海一带的滩涂土壤样品,利用索氏提取法提取、硅胶柱净化、高效液相色谱法分离检测土壤样品中的多环芳烃(PAHs),并用优化洗脱程序对滩涂土壤中PAHs的含量进行了测定。结果表明:11个滩涂土壤样品中检出萘、苊烯、菲、蒽、荧蒽、芘六种PAHs,其含量较低,说明该段滩涂土壤尚未受到多环芳烃的污染。