Remediation of Soil Contaminated with Pyrene Using Ground Nanoscale Zero-Valent Iron

Abstract

The sites contaminated with recalcitrant polycyclic aromatic hydrocarbons (PAHs) are serious environmental problems ubiquitously. Some PAHs have proven to be carcinogenic and hazardous. Therefore, the innovative PAH in situ remediation technologies have to be developed instantaneously. Recently, the nanoscale zero-va-lent iron (ZVI) particles have been successfully applied for dechlorination of organic pollutants in water, yet little research has investigated for the soil remediation so far. The objective in this work was to take advantage of nanoscale ZVI particles to remove PAHs in soil. The experimental factors such as reaction time, particle diameter and iron dosage and surface area were considered and optimized. From the results, both microscale and nanoscale ZVI were capable to remove the target compound. The higher removal efficiencies of nanoscale ZVI particles were obtained because the specific surface areas were about several dozens larger than that of commercially microscale ZVI particles. The optimal parameters were observed as 0.2 g iron/2 mL water in 60 min and 150 rpm by nanoscale ZVI. Additionally, the results proved that nanoscale ZVI particles are a promising technology for soil remediation and are encouraged in the near future environmental applications. Additionally, the empirical equation developed for pyrene removal efficiency provided the good explanation of reaction behavior. Ultimately, the calculated values by this equation were in a good agreement with the experimental data.     

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.     

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.     

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.     

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。     

生物泥浆体系修复氯酚污染的土壤

利用生物泥浆体系研究了受氯酚污染土壤的修复特性。结果表明，对4-氯酚污染浓度为300mg／kg的土壤，土著微生物基本没有降解活性；投加高效菌可大大加快4-氯酚的降解进程。生物泥浆体系修复氯酚污染土壤的最佳工艺参数为：温度35℃，水土比3：1，投菌量5％。外加碳源和氮源可明显促进4-氯酚的降解，但外加磷源对降解的影响并不显著。     

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。     

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.

     

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.     

Remediation of DDT-Contaminated Water and Soil by Using Pretreated Iron Byproducts from the Automotive Industry

The objective of this study was to quantify the effectiveness of different pretreated iron byproducts from the automotive industry to degrade DDT [(1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane] in aqueous solutions and soil slurry. Iron byproducts from automotive manufacturing were pretreated by three different methods (heating, solvent and 0.5N HCl acid washing) prior to experimentation. All pretreated irons were used at 5% (wt v^{? 1}) to treat 0.014 mM (5 mgL^{? 1}) of DDT in aqueous solution. Among the pretreated irons, acid pretreated iron results in the fastest destruction rates, with a pseudo first-order degradation rate of 0.364 d^{? 1}. By lowering the pH of the DDT aqueous solution from 9 to 3, destruction kinetic rates increase more than 20%. In addition, when DDT-contaminated soil slurry (3.54 mg kg^{? 1}) was incubated with 5% (wt v^{? 1}) acid-pretreated iron, more than 90% destruction of DDT was observed within 8 weeks. Moreover, DDT destruction kinetics were enhanced when Fe(II), Fe(III) or Al(III) sulfate salts were added to the soil slurry, with the following order of destruction kinetics: Al(III) sulfate > Fe(III) sulfate > Fe(II) sulfate. These results provide proof-of concept that inexpensive iron byproducts of the automotive industry can be used to remediate DDT-contaminated water and soil.     

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.     

Atmospheric Particulate Matter and Polycyclic Aromatic Hydrocarbons for PM10 and Size-Segregated Samples in Bangkok

Abstract

Air samples of particulate matter (PM) with an aerodynamic diameter less than 10 µm (PM₁₀) were collected from six sites in Bangkok, Thailand, using high-volume air samplers. Daily samples were taken at intervals of 12 days from November 1999 to November 2000. Size-selected sampling using a multislit Andersen size-fractionated cascade impactor was undertaken at one site in central Bangkok to identify particulate size distribution. The annual average PM₁₀ concentration at all six sites exceeded the Thailand National Ambient Air Quality Standard (NAAQS) of 50 µg/m³. The daily PM₁₀ concentrations at heavy traffic roadside areas ranged between 30 and 160 µg/m³. The highest PM₁₀ level occurred during the winter period (November–February), which is the dry season. From our results, which are based on a 1-yr survey, it can be observed that the particulate concentrations are associated with traffic volumes and seasonal factors (temperature and rainfall). The relative importance of size fractions in contributing to PM load is presented and discussed. Twenty polycyclic aromatic hydro-carbons (PAHs) associated with PM have been identified and quantified. The summed PAHs based on the 20 species had an average concentration of 60 ng/m³. Benzo(e)pyrene, indeno(123cd)pyrene, and benzo(ghi)perylene were the major compounds with average concentrations of 8, 10, and 13 ng/m³, respectively. Results indicate that more than 97% of PAHs were found in the small particulate size range of <0.95 µm.     

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.     

污染土壤电动修复及供能方式研究进展

污染土壤电动修复是一项新兴的绿色原位修复技术.其原理是在土壤上施加直流电场,利用电迁移和电渗流去除污染物.电动修复的效率主要受到土壤pH、Zeta电位以及土壤化学性质等因素影响.在研究中使用的供能方式有两种控制电位法和控制电流法.这两种供能方式有不同特点和应用范围.控制电压法在理论模型、酸碱增强法以及阳离子膜增强修复方面有着广泛应用;控制电流法在计算目标污染物的迁移数、电渗析修复法以及难溶性重金属污染物的修复中得到应用.     

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.     

电阻加热修复佳乐麝香污染土壤的工艺优化

佳乐麝香(Galaxolide,HHCB)是土壤中的一种新兴的半挥发性有机污染物,具有较高的毒性,需修复治理。电阻加热技术(electrical resistance heating,ERH)因加热均匀、效果好,逐渐被应用于有机污染土壤修复工程。采用自主研制的电阻加热装置,研究了加热过程中电场强度、土壤含水率和土壤粒径等因素对土壤HHCB去除效果的影响,并采用响应面法对工艺参数进行了优化。结果表明,土壤 HHCB去除率随电场强度和含水率的增大先增加后减小,随土壤粒径的增大而增大;在土壤含水率为40%、土壤粒径1~2 mm和电场强度12 V·cm⁻¹的条件下,加热6 h,HHCB去除效果最好,去除率达到了81.35%。通过响应曲面模拟优化得到的最佳工艺参数条件为,含水率39.07%、土壤粒径2.92 mm、电场强度12.64 V·cm⁻¹,在此条件下土壤HHCB的去除率为86.43%;在本实验条件下,3个因素对土壤HHCB去除率的影响为：含水率>土壤粒径>电场强度。本研究结果可为多环麝香污染土壤的修复提供参考。     

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.     

污染土壤的电动力学修复-Lasagna技术

介绍了Lasagna技术的原理和特点,以及目前所存在的问题.并对Lasagna技术的应用前景作了展望.     

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.