Permanganate oxidation of sorbed polycyclic aromatic hydrocarbons

The polycyclic aromatic hydrocarbons (PAH) that contaminate soils at many industrial and government sites are resistant to natural biotic and abiotic degradation processes. The recalcitrant nature of these compounds may require aggressive chemical treatment to effectively remediate these sites. This study was conducted to assess the viability of permanganate oxidative treatment as a method to reduce PAH concentration in contaminated soils. Study results demonstrated a reduction in soil sorbed concentration for a mixture of six PAHs that included anthracene, benzo(a)pyrene, chrysene, fluoranthene, phenanthrene, and pyrene by potassium permanganate (KMnO4) oxidative treatment. The greatest reduction in soil concentration was observed for benzo(a)pyrene, pyrene, phenanthrene, and anthracene at 72.1, 64.2, 56.2, and 53.8%, respectively, in 30 min at a KMnO4 concentration of 160 mM. Minimal reductions in fluoranthene and chrysene concentration were observed at 13.4 and 7.8%, respectively, under the same conditions. A relative chemical reactivity order of benzo(a)pyrene>pyrene>phenanthrene>anthracene>fluoranthene>chrysene towards permanganate ion was observed. Aromatic sextet theory was applied to the degradation results to explain the highly variable and compound-specific chemical reactivity order.     

Contributions of common sources of polycyclic aromatic hydrocarbons to soil contamination

Asphalt products, particularly sealants, are prepared using petroleum products that contain a com‐plex mixture of aliphatic and aromatic hydrocarbons, including polycyclic aromatic hydrocarbons (PAHs). Clearly, these products are ubiquitous in urban environments, which raises an issue regard‐ing the potential for PAHs to be transported from parking lots to underlying or adjacent soil, surface‐water bodies, or groundwater. Based on a literature review, there are limited studies focus‐ing on this issue; however, the studies that have been published have fascinating conclusions. The literature shows, as expected, that asphalt‐based products contain PAHs. The highest PAH concen‐trations are present in asphalt sealants, particularly those manufactured using coal tar. Furthermore, due to the low solubility and high partition coefficients of PAHs, the potential for PAHs to leach from asphalt surfaces is negligible, which has been confirmed by leachability studies. Thus, there is little risk that PAHs will be present in stormwater runoff or leach into groundwater from asphalt‐paved areas in a dissolved form. However, asphalt pavement and sealants produce particulate matter that can contain concentrations of PAHs in the sub‐percent range (100s to 1,000s mg/kg total PAHs) that is transported in stormwater runoff. Some studies show that this can cause soil and sediment con‐tamination with total PAH concentrations in the range of 1 to 10 mg/kg. From a remediation per‐spective, many site cleanups are conducted to remediate the presence of PAHs to cleanup goals below 1 mg/kg or, in some cases, 0.1 mg/kg or lower. From a total risk perspective, remediating sites to low PAH cleanup goals may be unwarranted in light of the risk of transportable PAHs produced from paved parking surfaces. In other words, is it reasonable to conduct a cleanup to remediate low PAH concentrations and then redevelop the area with asphalt pavement and sealant, which may pose a greater PAH‐related risk? © 2006 Wiley Periodicals, Inc.     

有机溶剂浸取石油污染土壤中的多环芳烃

采用索氏提取法和气相色谱分析了某炼油厂周边土壤中的多环芳烃的种类及含量,考察了6种有机溶剂对土壤中多环芳烃的浸取效果,探讨了溶剂与溶质溶解度参数差异对浸取效果的影响。结果表明：土壤试样中含有蒽、荧蒽、芘、 、苯并[a]蒽、苯并[b]荧蒽、苯并[k]荧蒽和苯并[a]芘8种多环芳烃,其含量分别为4.20,22.05,10.62,4.26,5.54,0.80,0.94,4.18 mg/kg;筛选出二氯甲烷作为土壤中多环芳烃的浸取溶剂;最佳浸取条件为浸取时间10 min、浸取温度30 ℃、溶剂与土壤的液固比5:1（mL/g）、土壤含水量8%,在此条件下,总多环芳烃浸出率为83.0%,各种多环芳烃的浸出率分别为蒽97.8%、荧蒽78.2%、芘99.9%、 98.5%、苯并[a]蒽81.1%、苯并[b]荧蒽47.6%、苯并[k]荧蒽14.8%、苯并[a]芘58.7%。     

Availability and leaching of polycyclic aromatic hydrocarbons: Controlling processes and comparison of testing methods

We have studied the availability and leaching of polycyclic aromatic hydrocarbons (PAHs) from two contaminated materials, a tar-containing asphalt granulate (Sigma16 US-EPA PAHs 3412mg/kg) and gasworks soil (SigmaPAHs 900mg/kg), by comparing results from three typical types of leaching tests: a column, sequential batch, and two different availability tests. The sequential batch test was found to largely resemble the column test. However, the leaching of particularly the larger PAHs (>5 aromatic rings) was found to be enhanced in the batch test by up to an order of magnitude, probably due to their association with large DOC (dissolved organic carbon) molecules generated by the vigorous mixing. The release of PAHs in the two availability tests, in which the leaching is facilitated by either a high concentration of DOC or Tenax resin, was similar, although the latter test was easier to perform and yielded more repeatable results. The availability was much higher than the amount leached in the column and sequential batch tests. However, biodegradation had apparently occurred in the column test and the total amount of PAHs released by either leaching or biodegradation, 9% and 26% for asphalt granulate and gasworks soil, respectively, did equal the amount leached in the availability tests. Therefore, the availability was found to provide a relevant measure of the PAH fraction that can be released from the solid phase. These results stress the importance of using the available instead of the total amount of contaminant in the risk analysis of solid materials in utilization or disposal.     

燃煤烟气中多环芳烃的富集技术

介绍了燃煤电厂烟气中排放的多环芳烃污染物的富集方法,比较了各种富集技术的特点与使用情况,分析了多环芳烃富集过程中的质量控制与质量保证措施,并探讨了富集采样中的若干注意事项.     

火电厂排烟中颗粒物及多环芳烃的研究

对某火电厂电除尘器前后烟气中颗粒物的形貌、粒径分布及多环芳烃(PAHs)在颗粒物、烟气气相及原煤中的含量进行了研究.结果表明,颗粒物主要呈圆球形,主要成分为Al2O3和SiO2,除尘器前颗粒粒径主要分布在5～10 μm之间,其后以5 μm以下为主;电除尘器对大颗粒有较好的收尘效果,而对小于5 μm颗粒的收尘效果较差;低环PAHs在气相中的含量均高于颗粒物中的含量;电除尘器对PAHs的平均脱除率能达到89.74%,对4环和6环PAHs的脱除率高于90%.     

活性炭固定床吸附分离溶液中表面活性剂和多环芳烃

利用活性炭固定床吸附分离表面活性剂和多环芳烃(PAH)的混合溶液,选取了具代表性的表面活性剂(TX100)和PAH(菲(PHE)等)。实验结果表明,流量越低、活性炭填充量越多、表面活性剂浓度越高、PAH浓度越低,越有利于表面活性剂的回收和PAH的去除。定义了有效回收时间,该时间是指PAH穿透10%的时间与表面活性剂穿透90%的时间之差,该时间越长,越有利于表面活性剂的回收。采用BDST和Thomas模型对TX100和PHE进行了吸附模拟,效果均较好;BDST模型拟合结果表明,当活性炭对TX100的吸附接近饱和时仍对PHE有较强的吸附能力。活性炭固定床吸附分离法可节约运行成本0.06元/L。     

Soil contamination by halogenated polycyclic aromatic hydrocarbons from open burning of e-waste in Agbogbloshie (Accra,Ghana)

Detailed composition of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs) generated during informal recycling of e-waste and their toxic relevance are still poorly understood. This study investigated the occurrence of Cl-PAHs and Br-PAHs in surface soil samples from the Agbogbloshie e-waste recycling site (Accra, Ghana) using quantitative gas chromatography–mass spectrometry (GC–MS) and comprehensive two-dimensional GC–time-of-flight mass spectrometry (GC × GC–ToFMS) profiling. The results of GC–MS analysis showed elevated concentrations in open e-waste burning areas (160–220 and 19–46 ng/g dry weight for Cl- and Br-PAHs, respectively) with substantial contribution from unidentified compounds (respectively, more than 36 and 70%, based on the total areas of potential peaks). Cl- and Br-PAHs from e-waste burning had a distinctive composition dominated by ring–ring compounds. Several homologue groups not monitored with GC–MS were found using GC × GC–ToFMS: PAHs with up to 5Cl or 3Br, mixed halogenated PAHs and chlorinated methylPAHs. The dioxin-like toxic equivalents of the identified Cl-/Br-PAHs in soils, estimated from their in vitro AhR agonist potencies relative to 2,3,7,8-tetrachlorodibenzo-p-dioxin, were much lower than the range reported for chlorinated and brominated dioxins. However, the toxicity of the unidentified halogenated PAHs remained unclear.     

Contaminant mass flux and forensic assessment of polycyclic aromatic hydrocarbons: Tools to inform remediation decision making at a contaminated site in Canada

Polycyclic aromatic hydrocarbons (PAHs) and metal(loid) mass flux estimates and forensic assessment using PAH diagnostic ratios were used to inform remediation decision making at the Sydney Tar Ponds (STPs) and Coke Ovens cleanup project in eastern Canada. Environmental effects monitoring of surface marine sediments in Sydney Harbor indicated significantly higher PAH concentrations during the first year of remediation monitoring compared to baseline. This was equivalent to PAH loadings of ～2,000 kg over a 15‐month period. Increases in sediment PAH concentrations raised serious concerns for regulators, who requested cessation of remediation activities early in the $400 M (CAD) project. Historically, the STPs were reported as the primary source of PAH contamination in Sydney Harbor with estimated discharges of 300 to 800 kg/year between 1989 and 2001. Mass flux estimates of PAHs and metal(loid)s and PAH diagnostic ratios were used to evaluate if increases in PAH concentrations in marine sediments were the result of the STPs remediation activities. PAH mass flux estimates approximated that 17 to 97 kg/year were discharged from the STPs during three years of remediation and were corroborated by an independent PAH flux estimate of 119 kg in year 1. PAH fluxes to the Sydney Harbor were mostly surface water derived, with groundwater contributing negligible quantities (0.002–0.005 kg/year). Fluxes of metal(loid)s to harbor sediments were stable or declining across all years and were mirrored in sediment metal(loid) concentrations, which lacked temporal variation, unlike total PAH concentrations. Flux results were also corroborated using PAH diagnostic ratios, which found a common source of PAHs. Coal combustion was likely the principal source of PAHs and not migration from the STPs during remediation. Although short‐term residual sediment PAH increases during onset of remediation raised concerns for regulators, calls for premature cessation of remediation early in the project were unwarranted based on only one year of monitoring data. Mass flux estimates and forensic assessments using PAH diagnostic ratios proved useful tools to inform remediation decision making that helped environmental protection and reduced costs associated with lost cleanup time.     

Characterisation of polycyclic aromatic hydrocarbons in flue gas and residues of a full scale fluidized bed combustor combusting non-hazardous industrial waste

This paper studies the fate of PAHs in full scale incinerators by analysing the concentration of the 16 EPA-PAHs in both the input waste and all the outputs of a full scale Fluidized Bed Combustor (FBC). Of the analysed waste inputs i.e. Waste Water Treatment (WWT) sludge, Refuse Derived Fuel (RDF) and Automotive Shredder Residue (ASR), RDF and ASR were the main PAH sources, with phenanthrene, fluoranthene and pyrene being the most important PAHs. In the flue gas sampled at the stack, naphthalene was the only predominant PAH, indicating that the PAHs in FBC’s combustion gas were newly formed and did not remain from the input waste. Of the other outputs, the boiler and fly ash contained no detectable levels of PAHs, whereas the flue gas cleaning residue contained only low concentrations of naphthalene, probably adsorbed from the flue gas. The PAH fingerprint of the bottom ash corresponded rather well to the PAH fingerprint of the RDF and ASR, indicating that the PAHs in this output, in contrast to the other outputs, were mainly remainders from the PAHs in the waste inputs. A PAH mass balance showed that the total PAH input/output ratio of the FBC ranged from about 100 to about 2600 depending on the waste input composition and the obtained combustion conditions. In all cases, the FBC was clearly a net PAH sink.     

Metal leachability, heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in fly and bottom ashes of a medical waste incineration facility

Medical waste from hospitals and other healthcare institutions has become an imperative environmental and public safety problem. Medical waste in Greece has become one of the most urgent environmental problems, because there are 14,000 tons produced annually, of which only a small proportion is incinerated. In the prefecture of Attica there is only one modern municipal medical waste incinerator (started 2004) burning selected infectious hospital waste (5-6 tons day(-1)). Fly and bottom residues (ashes) are collected and stored temporarily in barrels. High values of metal leachability prohibit the landfilling of these ashes, as imposed by EU directives. In the present study we determined quantitatively the heavy metals and other elements in the fly and bottom ashes of the medical waste incinerator, by inductively coupled plasma emission spectrometry (ICP) and by energy dispersive X-ray analysis (EDAX). Heavy metals, which are very toxic, such as Pb, Cd, Ni, Cr, Cu and Zn were found in high concentrations in both fly and bottom ashes. Metal leachability of fly and bottom ashes by water and kerosene was measured by ICP and the results showed that toxic metals in both ashes, such as Pb, Cr, Cd, Cu and Zn, have high leaching values. These values indicate that metals can become soluble and mobile if ash is deposited in landfills, thus restricting their burial according to EU regulations. Analysis of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in fly and bottom ashes showed that their concentrations were very low. This is the first known study in Greece and the results showed that incineration of medical waste can be very effective in minimizing the most hazardous and infectious health-care waste. The presence of toxic metals with high leachability values remains an important draw back of incineration of medical waste and various methods of treating these residues to diminish leaching are been considered at present to overcome this serious technical problem.     

Toxicity and source assignment of polycyclic aromatic hydrocarbons in road dust from urban residential and industrial areas in a typical industrial city in Korea

This study analyzed the toxicity and sources of polycyclic aromatic hydrocarbons (PAHs) in road dust from six representative areas (three urban residential areas and three industrial areas) from a typical industrial city in Korea. The concentrations and the toxicity equivalent concentrations (TEQs) in road dust varied by area, depending on the type of traffic and industrial activities and the PAHs identified. High correlations between the total concentration and the TEQ of PAHs in road dust were found in road dust from both the urban and industrial areas. To identify the sources of PAHs, this study utilized a factor loading method in a principal component analysis, the ratio of PAHs from combustion sources to total PAHs (ΣCOMB to ΣPAH), and bivariate plots of phenanthrene/anthracene (PA/Ant) versus fluoranthene/pyrene (FL/Pyr), and ΣCOMB/ΣPAH versus FL/Pyr in road dust. The identified origin of the PAHs was fuel combustion, including gasoline, diesel, oil, and coal, used in urban and industrial areas.     

Literature overview: Emerging organic contaminants in water and their remediation

Emerging organic contaminants (EOCs) are widespread in the environment, and concentrations above the acceptable limits are being detected due to improved detection methods, technologies, and regulations for their monitoring. Increasing use of new consumer, pharmaceutical, and scientific products has introduced EOCs, such as nanomaterials and siloxanes, into the environment. The releases of EOCs into the environment can lead to surface‐water, soil, and groundwater contamination. The presence of pharmaceuticals and their enantiomers can lead to resistant algal strains and, thus, more persistent algal toxins. This review discusses some of the prominent EOCs and the methods for their remediation. This is useful for assessing current remediation technologies and for developing new technologies to treat EOCs in water. © 2008 Wiley Periodicals, Inc.     

离子液体改性活性炭对芳香烃的吸附性能

采用浸渍法和嫁接法分别将1-丁基-3-甲基咪唑双三氟甲烷磺酰亚胺盐（[Bmim]TFSI）、丙基三辛基鏻四氟硼酸盐（[P（C₃H₇）（C₈H₁₇）₃]BF₄）和丙基三辛基鏻双三氟甲烷磺酰亚胺盐（[P（C₃H₇）（C₈H₁₇）₃]TFSI）负载于活性炭上。对产物进行了热重和孔结构分析,并以气相甲苯和二甲苯为代表物,研究了其对芳香烃的静态和动态吸附性能。研究结果表明：活性炭经离子液体改性后,能显著提高其对芳香烃的吸附性能;其中 [P（C₃H₇）（C₈H₁₇）₃]TFSI和[P（C₃H₇）（C₈H₁₇）₃]BF₄）浸渍改性活性炭的甲苯静态吸附量较大,分别为782 mg/g和777 mg/g （25 ℃,0.1 MPa）;[P（C₃H₇）（C₈H₁₇）₃]BF₄浸渍改性活性炭对于3种二甲苯异构体的吸附量最大,且排序依次为邻二甲苯>间二甲苯>对二甲苯。吸附动力学研究表明,在较高的甲苯初始浓度和较低的气体流量下,[P（C₃H₇）（C₈H₁₇）₃]TFSI浸渍改性活性炭具有更好的吸附性能。     

Laboratory studies of the remediation of polycyclic aromatic hydrocarbon contaminated soil by in-vessel composting

The biodegradation of 16 polycyclic aromatic hydrocarbons (PAHs), listed as priority pollutants by the USEPA, present in a coal-tar-contaminated soil from a former manufactured gas plant site was investigated using laboratory-scale in-vessel composting reactors to determine the suitability of this approach as a bioremediation technology. Preliminary investigations were conducted over 16 weeks to determine the optimum soil composting temperature (38, 55 and 70 degrees C). Three tests were performed; firstly, soil was composted with green-waste, with a moisture content of 60%. Secondly, microbial activity was HgCl2-inhibited in the soil green-waste mixture with a moisture content of 60%, to evaluate abiotic losses, while in the third experiment only soil was incubated at the three different temperatures. PAHs and microbial populations were monitored. PAHs were lost from all treatments with 38 degrees C being the optimum temperature for both PAH removal and microbial activity. Calculated activation energy values (E(a)) for total PAHs suggested that the main loss mechanism in the soil-green waste reactors was biological, whereas in the soil reactors it was chemical. Total PAH losses in the soil-green waste composting mixtures were by pseudo-first order kinetics at 38 degrees C (k = 0.013 day(-1), R2 = 0.95), 55 degrees C (k = 0.010 day(-1), R2 = 0.76) and at 70 degrees C (k = 0.009 day(-1), R2 = 0.73).     

Recent trends in the decomposition of chlorinated aromatic hydrocarbons by ultrasound irradiation and Fenton's reagent

Over the past few years, a large number of studies have been conducted on the use of ultrasound for decomposition of harmful organic pollutants, particularly chlorinated aromatic hydrocarbons (CAH) in wastewater. The published reports cover a variety of applications, including both ultrasonic treatment alone and in combination with other methods, e.g., advanced chemical oxidation processes. This article presents a review of recent work on ultrasonic-based methods of CAH decomposition, with emphasis on the applications of ultrasound alone and in combination with Fenton's reagent, as attractive advanced oxidation systems. In the first part of this review, the basic principles of sonochemical treatment are presented, followed by a review of the applications of ultrasound alone for CAH degradation. In the second part, the mechanisms of CAH degradation with Fenton's reagent and its application for CAH degradation are summarized. In the final part, studies on the applications of ultrasound together with Fenton's reagent are reviewed. The reported results suggest that a combination of ultrasound and Fenton's reagent is more attractive for practical application than the use of either method separately. Further studies, however, are required in this area because the reaction mechanism and the relationship between the reaction rates and process parameters for such a combined process are not yet well established.     

利用混合C9重芳烃回收磺酸盐装置的技术经济分析

介绍了回收磺酸盐生产工艺,对其装置的产品成本进行了测算,并对盈亏平衡及其敏感性进行了分析,进而确定了主要经济指标.