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.     

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。     

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.     

Source Apportionment and Identification of Polycyclic Aromatic Hydrocarbons (PAHs) in Sediment Cores of Selected Creeks in Delta State,Nigeria

Polycyclic aromatic hydrocarbons (PAHs) seasonal variation and sources in Ubeji, Ifie, and Egbokodo Creeks of the Niger Delta, Nigeria, were predicted using diagnostic ratios (DRs) of parent PAHs (Phe/Phe + Ant; Flu/Flu + Pyr; BaA/BaA + Chry, and Ind/Ind + BghiP) and principal component analysis (PCA). A total of 222 sediment core samples were collected during the wet (August 2010) and the dry seasons (January 2011). The samples were dried and Soxhlet extracted; sample extracts were fractionated and analyzed by gas chromatography/flame ionization detection (GC/FID) to identify individual PAHs. The diagnostic PAH ratios revealed that PAHs in the sediment cores at the three creeks, in both seasons, mainly stemmed from the combustion process (pyrogenic sources). Principal component analysis further confirmed that wood-burning, coal combustion, diesel, gasoline-powered vehicular emissions, and petroleum combustion were the dominant contributors of PAHs sources at the sampling location. This study provided information on the origin and sources of PAHs in sediment cores, which may be useful for regulatory actions, environmental quality management, contamination history, and environmental forensic studies.     

Distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in Sediment Cores of Selected Creeks in Delta State,Nigeria

The spatial and seasonal distribution and concentrations of polycyclic aromatic hydrocarbons (PAHs) were investigated in core sediments of Ubeji, Ifie, and Egbokodo creeks in the Niger Delta, Nigeria. A total of 222 core sediment samples were collected during the wet season (August 2010) and the dry season (January 2011). The samples were dried, Soxhlet extracted, fractionated, and injected into a gas chromatograph with flame ionization detector (GC-FID). The concentrations of PAHs ranged from not detected to 2,654 μg/kg (wet season) and not detected to 3,513 μg/kg (dry season). In general, the concentrations of PAHs for a number of stations in this study are comparable to sites with high anthropogenic activities in the Niger Delta. The toxicity risk assessment based on the total BaP equivalent quotient of the seven carcinogenic PAHs (BaA, Chry, BbF, BkF, BaP, DBA, and Iper) was 97.416 μg/kg and did not exceed the method B cleanup level for benzo(a)pyrene (137 μg/kg), according to toxic equivalency factors, which implied that PAHs in sediments of the present study currently have minimal adverse effects. This study provided information on the concentrations and profiles of PAHs sediment cores, which is useful for source diagnosis, environmental quality management, contamination history, and environmental forensic 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。     

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.     

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.

     

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.     

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。     

Spatio-Temporal Distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in Atmospheric Air of Tamil Nadu,India, and Human Health Risk Assessment

This study analyzed the seasonal distribution and the possible sources of polycyclic aromatic hydrocarbons (PAHs) in the atmospheric environment of Tamil Nadu, India. Passive air sampling was performed at 32 locations during the period from April 2009 to January 2010, and PAHs were quantified using a gas chromatograph-mass spectrometer. Analysis showed that the concentrations of PAHs were in the range of 5–47.5 ng/m³ with uniform distribution in urban areas in all seasons. Pre-monsoon season showed the highest cumulative concentration of PAHs in both agricultural and coastal areas. Among PAHs, phenanthrene, fluoranthene, and pyrene levels were found to be predominant in all the samples, contributing up to 36%, 35.5%, and 24.5% of total PAHs, respectively. The signature of the PAHs obtained through diagnostic ratio and principal component analysis revealed that diesel emissions was the probable source of PAHs in all locations. Based on Word Health Organization guidelines, the human lung cancer risk due to observed level of PAH concentration (i.e., PAHs exposure) is meager. However, the risk is predicted to be more in the coastal area during summer (18 individuals among 0.1 million people). To the knowledge of these authors, this report is the first on the seasonal analysis of PAHs using passive air sampling in India.     

The removal of Polycyclic Aromatic Hydrocarbons in the wastewater treatment process: experimental calculations and model predictions

The removal of PAHs during the wastewater treatment process was examined in an activated sludge mode conventional facility. Concentrations reported are taken from an earlier measuring campaign. Removals of PAHs ranged between 28 and 67% in the primary, <1-61% in the secondary stage, and 37-89% in the whole process. Significant positive relationships were observed for removal efficiencies and the log K(ow) of PAHs in the primary and the log K(H) of PAHs in the secondary stage. Experimental removals were compared to those obtained from the FATE model. In the primary stage, predicted removals were lower than those experimentally calculated while in the secondary stage were higher. Predicted removals were apportioned mainly to sorption with negligible contribution from volatilization and biodegradation. Remarkable consistency between experimental and modeled removal efficiencies (-20-+20%) was observed for almost all PAHs in the whole treatment process.     

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.     

Selected Ion Chromatograms and Tandem Mass Spectrometry for Detection of Trace Polycyclic Aromatic Hydrocarbons in Diesel Exhaust

Abstract

Polycyclic aromatic hydrocarbon (PAH) measurements are essential for scientists and engineers who investigate these anthropogenic compounds. Diesel engines contribute to the problem, so analysts are measuring PAHs from these sources. However, diesel exhaust presents special problems for precise analytical measurements. The exhaust matrix is very complex; consequently, PAH detection sensitivity deteriorates, especially for trace PAHs in the exhaust. Yet, these are conditions and amounts that exist in real samples. Nonetheless, selected ion chromatogram (SIC) and tandem mass spectrometry (MS/MS) techniques improve trace PAH detection; ion trap technology makes both mass techniques possible. The purpose of this investigation was to evaluate SIC and MS/MS for applications to measure PAHs in diesel exhaust samples. The signal-to-noise ratio for accurate quantitation improves, relative to traditional mass techniques, because these techniques ignore or eliminate interfering components. On a VF-5MS chromatographic column, these techniques improve sensitivity and reproducibility. They produce a superior limit of detection in the useful range for PAH samples extracted from actual engine exhaust, 10–30 pg for the smaller PAHs and 1–6 ng for the larger PAHs. The results with SIC and MS/MS are reproducible, so analysts can report PAH amounts with defined statistical confidence intervals. SIC and MS/MS improve detection for trace PAHs in convoluted diesel exhaust samples.     

Atmospheric Polycyclic Aromatic Hydrocarbons at a Point Source of Emissions. Part A: Identification and Determination of Polycyclic Aromatic Compounds in Airborne Particulate Matter Near a Horizontal Stud Soderberg Plant

Abstract

This paper summarizes the sampling and analytical methods developed to identify and measure polycyclic aromatic hydrocarbons (PAH) and related aromatic compounds near a Horizontal Stud Soderberg plant at Jonquiere, Quebec, Canada. The primary source of PAH is the coal tar pitch used as a binder in Soderberg anodes. Twice a week at a number of sampling sites, airborne particulate matter was collected on glass-fiber filters using a Hi-Vol sampler for a twenty-four hour period. Organics on the filter were Soxhlet extracted with benzene.

Identification was done by gas chromatography-mass spectrometry (GC-MS). The vast majority of compounds present were PAH, but small amounts of alkyl PAH and polycyclic aromatic compounds with heteroatoms such as nitrogen, oxygen and sulfur were also identified. Based on the GC-MS identification, a group of 14 PAH was selected for monitoring. Frequent PAH determinations revealed that the ratio of Benzo(a- )Pyrene to total PAH on the Hi-Vol filters is relatively constant in ambient air from one sampling station to another.     

Low-maturity Kulthieth Formation Coal: A Possible Source of Polycyclic Aromatic Hydrocarbons in Benthic Sediment of the Northern Gulf of Alaska

The successful application of forensic geology to contamination studies involving natural systems requires identification of appropriate endmembers and an understanding of the geologic setting and processes affecting the systems. Studies attempting to delineate the background, or natural, source for hydrocarbon contamination in Gulf of Alaska (GOA) benthic sediments have invoked a number of potential sources, including seep oils, source rocks, and coal. Oil seeps have subsequently been questioned as significant sources of hydrocarbons present in benthic sediments of the GOA in part because the pattern of relative polycyclic aromatic hydrocarbon (PAH) abundance characteristic of benthic GOA sediments is inconsistent with patterns typical of weathered seep oils. Likewise, native coal has been dismissed in part because ratios of labile hydrocarbons to total organic carbon (e.g. PAH:TOC) for Bering River coal field (BRCF) sources are too low—i.e. the coals are over mature—to be consistent with GOA sediments. We present evidence here that native coal may have been prematurely dismissed, because BRCF coals do not adequately represent the geochemical signatures of coals elsewhere in the Kulthieth Formation. Contrary to previous thought, Kulthieth Formation coals east of the BRCF have much higher PAH:TOC ratios, and the patterns of labile hydrocarbons in these low thermal maturity coals suggest a possible genetic relationship between Kulthieth Formation coals and nearby oil seeps on the Sullivan anticline. Analyses of low-maturity Kulthieth Formation coal indicate the low maturity coal is a significant source of PAH. Source apportionment models that neglect this source will underestimate the contribution of native coals to the regional background hydrocarbon signature.     

Low-maturity Kulthieth Formation Coal: A Possible Source of Polycyclic Aromatic Hydrocarbons in Benthic Sediment of the Northern Gulf of Alaska

The successful application of forensic geology to contamination studies involving natural systems requires identification of appropriate endmembers and an understanding of the geologic setting and processes affecting the systems. Studies attempting to delineate the background, or natural, source for hydrocarbon contamination in Gulf of Alaska (GOA) benthic sediments have invoked a number of potential sources, including seep oils, source rocks, and coal. Oil seeps have subsequently been questioned as significant sources of hydrocarbons present in benthic sediments of the GOA in part because the pattern of relative polycyclic aromatic hydrocarbon (PAH) abundance characteristic of benthic GOA sediments is inconsistent with patterns typical of weathered seep oils. Likewise, native coal has been dismissed in part because ratios of labile hydrocarbons to total organic carbon (e.g. PAH: TOC) for Bering River coal field (BRCF) sources are too low--i.e. the coals are over mature--to be consistent with GOA sediments. We present evidence here that native coal may have been prematurely dismissed, because BRCF coals do not adequately represent the geochemical signatures of coals elsewhere in the Kulthieth Formation. Contrary to previous thought, Kulthieth Formation coals east of the BRCF have much higher PAH: TOC ratios, and the patterns of labile hydrocarbons in these low thermal maturity coals suggest a possible genetic relationship between Kulthieth Formation coals and nearby oil seeps on the Sullivan anticline. Analyses of low-maturity Kulthieth Formation coal indicate the low maturity coal is a significant source of PAH. Source apportionment models that neglect this source will underestimate the contribution of native coals to the regional background hydrocarbon signature.     

Vapor-Phase and Fine Particulate Matter Concentrations of Polycyclic Aromatic Hydrocarbons Measured during the Winter Months in a Northern Rocky Mountain Urban Airshed

Abstract

A fine particulate matter (PM_2.5) sampling program was conducted in Missoula, MT, to investigate both the particle and vapor phases of PM_2.5-associated polycyclic aromatic hydrocarbons (PAHs) found in a northern Rocky Mountain urban airshed. Twenty-four-hour samples were collected during the cold winter months of January through April 2002, when many of the more volatile organic components of PM_2.5 were expected to be found in the condensed particle form. To meet analytical detection limits, each of the 12 individual sample days were aggregated into four total filter and polyurethane foam (PUF) samples, respectively, with each aggregate containing 3 sample days. Quartz filter (particle-phase PAHs) and PUF (vapor-phase PAHs) aggregates were analyzed separately for 18 individual PAHs and phenolics by gas chromatography/mass spectrometry. Results showed that 87% of the PM_2.5-associated phenolics and PAHs measured in this study were found in the vapor phase. PM_2.5-associated gas/particle partition coefficients (K_p,2.5) ranged from 0 for the lighter phenolics and PAHs to ~0.1 for some of the heavier PAHs, such as fluoranthene and pyrene. Calculating K_p,2.5 for the heaviest measured PAHs was not feasible because of low or undetectable concentrations in the vapor phases of these compounds. Phenolics and two-ringed and three-ringed PAHs were found almost exclusively in the vapor phase. Four-ringed PAHs were distributed between the particle and vapor phases, with more mass measured in the vapor phase. Very little five-ringed and higher PAHs were measured from either the filter or PUF sampling medium. These results provide information on both the concentrations and different phases of PM_2.5-associated PAHs measured during the winter months in a northern Rocky Mountain urban airshed, when concentrations of PM_2.5 are generally at their highest compared with the rest of the year.     

Source Type Evaluation of Polycyclic Aromatic Hydrocarbons (PAHs) in Surface Sediments from the Muar River and Pulau Merambong,Peninsular Malaysia

This article is the most recent report of polycyclic aromatic hydrocarbons (PAHs) in the Muar River and Pulau Merambong, Peninsular Malaysia. A total of 16 priority pollutant PAHs in addition to methylphenanthrene among alkylated PAHs were analyzed in surface sediments during May 2013. Total PAHs ranged from 212 to 440 and 151 to 412 ng g^?1 dw in sediments from the Muar River and the Pulau Merambong, respectively. The Muar River showed an increasing trend of PAH concentrations, while no previous data exist for the Pulau Merambong. Generally, mixed petrogenic and pyrogenic sources of PAHs with predominance of the latter were detected in the study area. Effective management of oil pollution has caused a drastic decrease in petrogenic sources of PAHs.     

Spatial and seasonal variations of polycyclic aromatic hydrocarbons in Haihe Plain, China

A dynamic fugacity model was developed to simulate the spatial and seasonal variations of PAHs in Haihe Plain, China. The calculated and measured concentrations exhibited good consistency in magnitude with deviations within a factor of 4 in air and 2 in soil. The spatial distributions of PAHs in air were mainly controlled by emission while the seasonal variations were dominated by emission and gas-particle partition. In soil, the spatial distributions of PAHs were controlled by the soil organic carbon content while the seasonal variations were insignificant. The severest soil contamination was observed in Shanxi and followed by the southwest of Hebei province. Transfer fluxes of total PAHs between air and soil were calculated. The spatial distribution of air-to-soil flux was closely related to the landcover while the soil-to-air flux changed with soil organic matter content. Monte Carlo simulation was done to evaluate the uncertainty of the estimated results in air.