应用表面活性剂-生物柴油微乳液去除污染土壤中多环芳烃

针对修复焦化厂高浓度多环芳烃污染土壤高成本的现实,采用以非食用性植物油、生物柴油、表面活性剂及其乳化合成的微乳液为淋洗剂,比较不同淋洗剂的淋洗效果。结果表明乳化合成的微乳液对焦化厂土壤中多环芳烃的总去除率高于单独使用表面活性剂为淋洗剂对土壤中多环芳烃的总去除率,说明生物柴油及植物油与表面活性剂乳化形成的微乳液对原污染土壤中的多环芳烃具有显著的增溶作用。1%TW-80和2.5%TW-80对土壤中多环芳烃总去除率分别为11%和14%;以2.5%TW-80为原料乳化合成的微乳液的淋洗去除率较以1%TW-80为原料乳化合成的微乳液高,总去除率分别为15%～30%和11%～18%;以生物柴油为原料乳化合成的微乳液的淋洗去除率较以植物油为原料乳化合成的微乳液高,分别为17%～30%和15%～23%,且对多环芳烃的去除率与其辛醇水分配系数(logKow)呈线性相关关系。     

Assessment of honey contamination with polycyclic aromatic hydrocarbons

The aim of this study was to assess honey contamination by polycyclic aromatic hydrocarbons. Six species of honey were examined, as well as rape blossom and soil from villages P?czerzyno and Przybys?aw in West Pomerania, Poland. The instrumental analysis was performed using a HP 6890 gas chromatograph coupled to a HP 5973 mass spectrometer with selected ion monitoring (SIM). Quantification was done by gas chromatography-mass spectrometry (GC-MS) using perdeuterated internal standards. Both soil samples showed high levels of all 23 PAHs, whereas honey contained mostly non-carcinogenic PAHs of low molecular weight. The most contaminated honey from P?czerzyno contained 0.24 μg kg-1 benzo[a]pyrene. Moreover, despite low contamination of honey, a positive correlation was found between PAH content in honey, blossom and soil.     

表面活性剂增效电动技术修复多环芳烃污染土壤

研究了电动修复过程中修复时间和表面活性剂Triton X-100、鼠李糖脂对多环芳烃芘污染土壤的修复效果的影响。结果表明,在电动修复过程中,随着修复时间的增加,芘的去除率相应提高。通过向电解液中添加表面活性剂Triton X-100,芘的去除率从11.64%提高到了23.42%,当在电解液中添加浓度为40倍CMC的鼠李糖脂后去除率升高至36.29%,阳极附近土壤甚至达到了92.49%,这表明Triton X-100和鼠李糖脂均能促进土壤中芘的溶解和迁移,鼠李糖脂的促进作用高于Triton X-100。     

Lead and polycyclic aromatic hydrocarbons (PAHs) in surface soil from day care centres in the city of Bergen, Norway

Surface soil (0-2cm) quality in 87 day care centres in the city of Bergen, Norway has been studied. Approximately 45% of the day care centres contained Pb and PAH values above recommended action levels. There are clear variations between different areas of the city. The old central part of the city hosts most of the contaminated day care centres. In suburban areas most of the day care centres have Pb and PAH concentrations below action levels. City fires, gas work emission, lead-based paint, and traffic are probably important anthropogenic contamination sources, together with uncontrolled transportation of soil from contaminated to clean areas. Geological or other natural sources are probably not an important contributor to the high levels of lead and PAH.     

人工湿地处理系统中多环芳烃的行为

采用Oasis HLB柱固相萃取的前处理技术,以气相色谱质谱联用仪(GC/MS)的分析方法,对我国北方永定河上游黑土洼人工湿地中多环芳烃污染的特征以及分布规律进行了研究.结果表明,该湿地系统以低环数多环芳烃污染为主,其中浓度最高的是菲和蒽,未检出高环数(5环、6环)多环芳烃.通过比较进水和出水的浓度,湿地系统总体上不能有效去除进水中的多环芳烃.但是比较不同工艺单元进出水浓度,复氧、植物根系及微生物等均影响到多环芳烃的去除效果,去除率在28%～65%之间.     

人工湿地处理系统中多环芳烃的行为

采用Oasis HLB柱固相萃取的前处理技术,以气相色谱质谱联用仪（GC/MS）的分析方法,对我国北方永定河上游黑土洼人工湿地中多环芳烃污染的特征以及分布规律进行了研究.结果表明,该湿地系统以低环数多环芳烃污染为主,其中浓度最高的是菲和蒽,未检出高环数（5环、6环）多环芳烃.通过比较进水和出水的浓度,湿地系统总体上不能有效去除进水中的多环芳烃.但是比较不同工艺单元进出水浓度,复氧、植物根系及微生物等均影响到多环芳烃的去除效果,去除率在28%～65%之间.     

Partitioning of polycyclic aromatic hydrocarbons to solid-sorbed nonionic surfactants

The partition of hydrophobic organic compounds (HOCs) into solid-sorbed surfactant has a crucial role in describing and predicting the distribution of HOCs in solid-water-surfactant systems. The experimental results of this study indicated that the partition coefficients of polycyclic aromatic hydrocarbons (PAHs) into the solid-sorbed surfactant (Ksm) increased with an increase in the sorption amount of surfactants onto solid and reached a stable maximum value (Km sm) at the sorption of surfactants in saturation state, at which the solid surface was completely covered with the surface micelle (or admicelle). The fitted Km sm values for PAHs with different surfactants were found to have a good linear relationship with the corresponding partition coefficient of PAHs to surfactant micelles in solution (Kmc), and then a model was developed to describe and predict the distribution of PAHs in solid-water-surfactant systems. These results are of practical interest for developing effective and safe surfactant-enhanced remediation technologies.     

Anaerobic degradation of five polycyclic aromatic hydrocarbons from river sediment in Taiwan

This study investigated the anaerobic degradation of five polycyclic aromatic hydrocarbons (PAHs) from Erren River sediment in southern Taiwan. The degradation rates of PAH were in the order: acenaphthene > fluorene > phenanthrene > anthracene > pyrene. The degradation rate was enhanced when the five compounds were present simultaneously in river sediment. Comparison of the PAH degradation rates under three reducing conditions showed the following order: sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The addition of electron donors (acetate, lactate and pyruvate) enhanced PAH degradation under methanogenic and sulfate-reducing conditions. However, the addition of acetate, lactate or pyruvate inhibited PAH degradation under nitrate-reducing conditions. The addition of heavy metals, nonylphenol and phthalate esters (PAEs) inhibited PAH degradation. Our results show that sulfate-reducing bacteria, methanogen and eubacteria are involved in the degradation of PAH; sulfate-reducing bacteria constitute a major microbial component in PAH degradation. Of the microorganism strains isolated from the sediment samples, we found that strain ER9 expressed the greatest biodegrading ability.     

Removal of polycyclic aromatic hydrocarbons from soil: a comparison between bioremoval and supercritical fluids extraction

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic substances which are resistant to environmental degradation due to their highly hydrophobic nature. Soils contaminated with PAHs pose potential risks to human and ecological health, therefore concern over their adverse effects have resulted in extensive studies on their removal from contaminated soils. The main purpose of this study was to compare experimental results of PAHs removal, from a natural certified soil polluted with PAHs, by biological methods (using bioaugmentation and biostimulation in a solid-state culture) with those from supercritical fluid extraction (SFE), using supercritical ethane as solvent. The comparison of results between the two methods showed that maximal removal of naphthalene, acenaphthene, fluorene, and chrysene was performed using bioremediation; however, for the rest of the PAHs considered (fluoranthene, pyrene, and benz(a)anthracene) SFE resulted more efficient. Although bioremediation achieved higher removal ratios for certain hydrocarbons and takes advantage of the increased rate of natural biological processes, it takes longer time (i.e. 36 d vs. half an hour) than SFE and it is best for 2-3 PAHs rings.     

Oxidation of polycyclic aromatic hydrocarbons by fungal isolates from an oil contaminated refinery soil

BACKGROUND AND OBJECTIVE: Indigenous soil microorganisms are used for the biodegradation of petroleum hydrocarbons in oily waste residues from the petroleum refining industry. The objective of this investigation was to determine the potential of indigenous strains of fungi in soil contaminated with petroleum hydrocarbons to biodegrade polycyclic aromatic hydrocarbons (PAH). MATERIALS AND METHODS: Twenty one fungal strains were isolated from a soil used for land-farming of oily waste residues from the petrochemical refining industry in Singapore and identified to genus level using laboratory culture and morphological techniques. Isolates were incubated in the presence of 30 mg/L of phenanthrene over a period of 28 days at 30 degrees C. The most effective strain was further evaluated to determine its ability to oxidise a wider range of PAH compounds of various molecular weight i.e acenaphthene, fluorene, fluoranthene, chrysene, benzo(a)pyrene and dibenz(ah)anthracene RESULTS AND DISCUSSION: After 28 days of incubation, 18 of the 21 fungal cultures were capable of oxidising over 50% of the phenanthrene present in culture medium, relative to abiotic controls. Fungal isolate, Penicillium sp. 06, was able to oxidise 89% of the phenanthrene present. This isolate could also oxidise more than 75% of the acenaphthene, fluorene and fluoranthene after 30 days of incubation. However, the oxidation of high molecular weight PAH i.e. chrysene, benzo(a)pyrene and dibenz(ah)anthracene by the Penicillium sp. 06 isolate was limited, where the extent of oxidation was inversely proportional to PAH molecular weight. CONCLUSIONS: Fungal isolate, Penicillium sp. 06, was effective at oxidising a range of PAH in petroleum contaminated soils, but higher molecular weight PAH were more recalcitrant. RECOMMENDATIONS AND OUTLOOK: There is potential for the re-application of this fungal strain to soil for bioremediation purposes.     

改性膨润土对水体中多环芳烃的吸附

改性膨润土被广泛地应用于吸附水体中重金属离子和有机污染物,但关于改性膨润土吸附水体中多环芳烃混合物的动力学研究鲜见报道。利用十二烷基三甲溴化铵和十二烷基磺酸钠对膨润土进行改性,并将之应用于吸附水体中萘、蒽、菲和芘4种多环芳烃,考察了吸附剂投加量、时间和温度等条件对吸附效果的影响。实验结果表明,在25℃、吸附时间40 min、起始浓度为1.25 mg/mL、改性膨润土的投加量为4 g/L的条件下,该吸附剂对萘、蒽、菲和芘的吸附率分别为99.1%、99.6%、98.7%和98.9%。改性膨润土对水体中4种多环芳烃的吸附机理服从准二级动力学方程,该吸附剂吸附等温线服从Langmuir方程。     

产漆酶食用菌的粗酶液对多环芳烃降解研究

漆酶是一种含铜的多酚氧化酶,可以降解多种有机污染物,其中包括多环芳烃。但是由于纯漆酶的价格昂贵,限制了在环境修复中的应用。采用液态和固态2种方式培养了食用菌Pleurotus ostreatus和Coprinus comatus,并考察了固态培养的粗酶液对多环芳烃的降解和去毒能力,结果发现2种真菌均可产漆酶,但不产木质素过氧化物酶和锰过氧化物酶,其中固态培养的漆酶产量高于液态培养,且C.comatus的漆酶产量大于P.ostreatus。2种真菌固态培养的粗酶液对多环芳烃均有一定的降解和去毒作用,且P.ostreatus粗酶液的漆酶活性虽然较低,但是对多环芳烃降解率和去毒效果却优于C.comatus,这可能是P.ostreatus的粗酶液中含有较多的调节物质造成的。P.ostreatus的固态发酵粗酶液对蒽、苯并[a]芘、苯并[a]蒽、苊等均有较高的降解率(50%以上),但是对生物有效性高的萘的降解率却较低,这种降解特征可能与底物的电离势大小有关。     

Removal of polycyclic aromatic hydrocarbons from aged-contaminated soil using cyclodextrins: experimental study

The removal of polycyclic aromatic hydrocarbons (PAHs) from soil using water as flushing agent is relatively ineffective due to their low aqueous solubility. However, addition of cyclodextrin (CD) in washing solutions has been shown to increase the removal efficiency several times. Herein are investigated the effectiveness of cyclodextrin to remove PAH occurring in industrially aged-contaminated soil. Beta-cyclodextrin (BCD), hydroxypropyl-beta-cyclodextrin (HPCD) and methyl-beta-cyclodextrin (MCD) solutions were used for soil flushing in column test to evaluate some influent parameters that can significantly increase the removal efficiency. The process parameters chosen were CD concentration, ratio of washing solution volume to soil weight, and temperature of washing solution. These parameters were found to have a significant and almost linear effect on PAH removal from the contaminated soil, except the temperature where no significant enhancement in PAH extraction was observed for temperature range from 5 to 35 degrees C. The PAHs extraction enhancement factor compared to water was about 200.     

低温电阻加热对土壤多环芳烃去除和细菌群落的影响

针对电阻加热技术修复多环芳烃污染土壤存在能耗高、降低土壤功能性的问题,采用低温条件 (80 ℃) 的电阻加热以降低能耗、减少对土壤肥力和细菌群落的影响。利用自主研制的电阻加热装置,探究低温加热对土壤多环芳烃的去除效果、对土壤理化性质和细菌群落的影响。结果表明,在80 ℃加热180 min条件下,电阻加热对土壤多环芳烃的去除率为21.8%,苯并[a]蒽、苯并[b]荧蒽、苯并[k]荧蒽、䓛、二苯并[a,h]蒽、茚并[1,2,3-cd]芘和萘的质量分数均低于《土壤环境质量建设用地污染风险管控标准 (试行) 》 (GB 36600-2018) 第一类用地筛选值;电阻加热处理后细菌丰度增幅达108%,提高了群落丰富度和多样性,富集了多环芳烃降解菌和功能基因,将厚壁菌门PAHs降解菌的相对丰度放大了近10倍,提高了编码4,5-二羟基邻苯二甲酸酯脱羧酶 (K04102) 和1,4-二羟基-2-萘甲酰-CoA硫酯酶 (K12073) 的功能基因预测丰度,且不会对土壤肥力水平造成负面影响。本研究结果可为低温电阻加热在多环芳烃污染土壤修复中的应用提供参考。     

Size distribution of polycyclic aromatic hydrocarbons in a roadway tunnel in Lisbon, Portugal

Atmospheric aerosols of four aerodynamic size ranges were collected using high volume cascade impactors in an extremely busy roadway tunnel in Lisbon (Portugal). Dust deposited on the tunnel walls and guardrails was also collected. Average particle mass concentrations in the tunnel atmosphere were more than 30 times higher than in the outside urban background air, revealing its origins almost exclusively from fresh vehicle emissions. Most of the aerosol mass was concentrated in submicrometer fractions (65%), and polycyclic aromatic hydrocarbons (PAH) were even more concentrated in the finer particles with an average of 84% of total PAH present in sizes smaller than 0.49 μm. The most abundant PAH were methylated phenanthrenes, fluoranthene and pyrene. About 46% of the total PAH mass was attributed to lower molecular weight compounds (two and three rings), suggesting a strong influence of diesel vehicle emissions on the production of local particulate PAH. The application of diagnostic ratios confirmed the relevance of this source of PAH in the tunnel ambient air. Deposited dust presented PAH profiles similar to the coarser aerosol size range, in agreement with the predominant origin of coarser aerosol particles from soil dust resuspension and vehicle wear products.     

UV-Fenton催化氧化法对采油废水中多环芳烃的处理效果

针对采油废水中含有多环芳烃种类多且较难去除的特点,采用UV-Fenton技术对采油废水中多环芳烃的处理效果进行了研究,通过正交实验和单因素实验,研究了在254 nm波长紫外光照射下,Fe2+投加量、H2O2投加量、pH值和光照时间对水样中多环芳烃中的菲和芴处理效果的影响。实验结果显示,处理初始浓度为1 000μg/L的菲、芴时,反应的最佳工艺条件为:Fe2+浓度为1.8 mmol/L、H2O2投加量为0.15 mmol/L、pH值为4、光照时间1.25 h。在此条件下,菲和芴的去除率可达71.9%。     

紫外光(UV)光解油田采出水中多环芳烃

为了探讨紫外光光解人工模拟油田采出水中多环芳烃的降解效率,利用自制反应装置对油田采出水中多环芳烃(PAHs)的紫外光光解做了一个初步研究。研究结果证明,紫外光光解对油田采出水中的多环芳烃萘和芴有显著的降解能力。实验室的测试表明,与紫外UVA(365 nm)、UVB(308 nm)的光照相比,紫外UVC(254 nm)在光照60 min的条件下,2种多环芳烃各自的去除率都近似达到了99%。可见,在光解效力和暴露时间两方面,紫外UVC对采出水中萘和芴的去除具有相对稳定和比较高的效率。     

Pollution survey of polycyclic aromatic hydrocarbons in surface water of Hangzhou, China

The concentrations of 10 polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured for five times (July and November 1999–2002) in four water bodies of Hangzhou, China. To investigate possible sources of PAH contamination, sediments, soils, runoff water and atmospheric particles of the region were also analyzed for their PAH contents. The maximum levels of PAHs in the water bodies (34.4–67.7 μg/l) were found in July, while significantly lower PAH concentrations (4.7–15.3 μg/l) were measured in November. The contamination is substantial and it may have resulted in acute toxic effects on aquatic organisms. The measured PAH concentrations in sediments and soils (224–4222 ng/g), runoff water (8.3 μg/l) and air particles (2.3 μg/m³) are discussed in relation to concentrations and patterns found in the surface water bodies. Comparison of PAH levels in sediments and soils led to the conclusion that the erosion of soil material does not contribute significantly to the contamination of sediments. The atmospheric PAH deposition to water bodies in the city area of Hangzhou was estimated to be 530 tons/a, while the contribution of surface runoff water was estimated to be 30.7 tons/a. The ratios of selected PAH were then used to illuminate the possible origin of PAHs in the examined samples (petrogenic, pyrogenic).     

Temperature-dependent sorption of polycyclic aromatic hydrocarbons on natural and treated sediments

In aqueous environment temperature is considered to play a significant role in the sorption process of polycyclic aromatic hydrocarbons (PAHs) and its influence on the sorption equilibrium is indicative of sorption energies and mechanisms. In this study, sorptions of five PAHs on three heterogeneous sorbents including one river sediment (YHR), one estuary sediment (YRD) and one treated sediment with organic matter removed (IM) were carried out at a range of temperature from 5 °C to 35 °C. Stronger sorptions were observed at lower temperatures, with the equilibrium sorption coefficient K_d increasing 2-5 times as the temperature decreases 30 °C. The increase of K_d value was attributed primarily to the change of PAH water solubility, which predicted 40-75% of the increase of K_d in the sorption process. To provide insight into the sorption mechanism, enthalpy change (ΔH_S) for the sorption process was calculated and the values were observed to be negative for all of the interactions, suggesting that the exothermal sorption of PAHs inversely dependents on temperature. Based on the values of ΔH_S, van der Waals forces were inferred as the main sorption mechanism for the PAHs, especially on the YHR sediment which contained more organic matter. For sorption of larger size PAHs on the sorbents with low organic matter, specific interactions were deduced to contribute to the overall sorption.     

煤矸石堆积下多环芳烃的淋溶污染特征

淋溶是使有害物质析出的主要途径之一。为查明煤矸石堆放淋溶造成的有机污染效应,对不同风化强度煤矸石进行了动态淋溶模拟实验,系统研究了煤矸石中US EPA优先控制的16种多环芳烃（PAH16）的析出规律和迁移方式。获得煤矸石中多环芳烃（PAHs）淋溶特征如下：煤矸石堆积期遭受短期降雨（500~1 600 mm）作用后,煤矸石溶出的PAH16总质量浓度达125.6~451.2 ng/L。PAH16溶出量初期较高,在一定降雨期后又达到峰值,酸雨条件下,煤矸石山淋溶出的PAH16可由线性累加转为指数快速累加的趋势。淋溶液中优势组分为萘、二氢苊、芴和菲,4种组分之和占所测PAHs总量的80%~90%。煤矸石溶出的PAHs环数分布为2环〉3环〉4环〉5环、6环。迁移方式上,2环PAHs多以溶解相迁移,3环PAHs主要以颗粒态迁移,存在少量溶解形式,而4环以上PAHs则以颗粒相形式迁移。