化学氧化法治理焦化厂PAHs污染土壤

针对焦化类工业场地多环芳烃(PAHs)污染土壤治理问题,选取北京某焦化厂PAHs污染土壤,对其进行化学氧化修复治理的室内模拟研究,实验采用高锰酸钾、Fenton试剂、双氧水和过硫酸钠4种氧化剂,测试了氧化剂的土壤氧化剂需求量(SOD),分析了4种氧化剂对15种PAHs的氧化效果以及反应过程中土壤总PAHs浓度和土壤有机质含量(SOM)随反应时间的变化。结果表明,北京某焦化厂PAHs污染土壤过硫酸钠SOD低于高锰酸钾SOD;Fenton试剂和双氧水对PAHs的总去除率分别为59.53%和62.72%,且对三环PAHs的去除率较好,高锰酸钾对PAHs的总去除率为59.24%,对蒽和苯并(a)芘的去除效果较好,活化过硫酸钠对PAHs的总去除率为68.87%;土壤有机质可通过对PAHs的吸附影响氧化剂的处理效果。     

Photolysis of polycyclic aromatic hydrocarbons in water

We have studied the photochemical reactions of eight polycyclic aromatics and heteroatom analogs (PAHs). Quantum yields and rate constants in sunlight and at single wavelengths were measured and half-lives of the PAHs as a function of the time of year were calculated. Product studies and the effect of humic acid and oxygen on rates are reported.     

Halogenated polycyclic aromatic hydrocarbons in the environment

Halogenated polycyclic aromatic hydrocarbons (HPAHs) have been reported to occur in air, sediment, fly ash, and biota samples. This review summarized current existing data on the environmental occurrence, behavior, physicochemical properties, emission sources, and toxic equivalents of HPAHs. Firstly, the physicochemical properties of HPAHs were summarized. Then, an overview of environmental occurrence of HPAHs in ambient matrices including biological samples was reviewed. Meanwhile, the emission sources and possible formation mechanisms of HPAHs were discussed. Apart from that, the aryl hydrocarbon receptor (AhR)-mediated activities were summarized, which indicated that the position and number of halogen atoms on the parent PAHs molecule were important determinant factors affecting the AhR-mediated activity of individual HPAHs congeners. Finally, some research recommendations on HPAHs were given.     

Accumulation of weathered polycyclic aromatic hydrocarbons (PAHs) by plant and earthworm species

Experiments were conducted to assess the bioavailability of polyclycic aromatic hydrocarbons (PAHs) in soil from a Manufactured Gas Plant site. Three plant species were cultivated for four consecutive growing cycles (28 days each) in soil contaminated with 36.3 microg/g total PAH. During the first growth period, Cucurbita pepo ssp. pepo (zucchini) tissues contained significantly greater quantities of PAHs than did Cucumis sativus (cucumber) and Cucurbita pepo ssp. ovifera (squash). During the first growth cycle, zucchini plants accumulated up to 5.47 times more total PAH than did the other plants, including up to three orders of magnitude greater levels of the six ring PAHs. Over growth cycles 2-4, PAH accumulation by zucchini decreased by 85%, whereas the uptake of the contaminants by cucumber and squash remained relatively constant. Over all four growth cycles, the removal of PAHs by zucchini was still twice that of the other species. Two earthworm species accumulated significantly different amounts of PAH from the soil; Eisenia foetida and Lumbricus terrestris contained 0.204 and 0.084 microg/g total PAH, respectively, but neither species accumulated measurable quantities 5 or 6 ring PAHs. Lastly, in abiotic desorption experiments with an aqueous phase of synthetically prepared organic acid solutions, the release of 3 and 4 ring PAHs from soil was unaffected by the treatments but the desorption of 5-6 ring constituents was increased by up to two orders of magnitude. The data show that not only is the accumulation of weathered PAHs species-specific but also that the bioavailability of individual PAH constituents is highly variable.     

Leaf accumulation of trace elements and polycyclic aromatic hydrocarbons (PAHs) in Quercus ilex L

Quercus ilex L. leaves were collected four times in one year at six urban sites and one remote area in order to determine trace element and PAH accumulation through concomitant analyses of unwashed and water-washed leaves. Both unwashed and washed leaves showed the highest amounts of trace elements and PAHs in the urban area. Unwashed leaves showed greater differences between urban and remote areas and among the urban sites than washed leaves for trace element and PAH concentrations. Water-washing resulted in a significant (P<0.001) decrease in leaf concentrations of Cr, Cu, Fe, Pb, V and Zn. By contrast, Cd and total PAH concentrations showed no differences between unwashed and washed leaves.     

我国环境介质中多环芳烃的分布及其生态风险

持久性有机污染物多环芳烃(PAHs)在我国环境介质中广泛分布,美国EPA规定的16种.优先控制多环芳烃大多在我国大气、水体、沉积物、土壤和生物体内检出.总结了我国环境介质中PAHs污染水平及特点,分析了其存在的环境风险.我国大气中PAHs污染较重,尤其是北方.水体已普遍受PAHs污染,其中部分水体污染严重;沉积物多环芳烃污染大多处于低生态风险水平,但沉积记录研究表明有越来越严重的趋势.我国土壤和生物体PAHs含量较低,污染生态风险较小.部分区域蔬菜中PAHs含量较高,存在不可忽视的生态风险.     

Absorption of polycyclic aromatic hydrocarbons to cellulose

Polycyclic aromatic hydrocarbons (PAHs) are widespread toxic chemicals. The environmental fate of these chemicals is in part controlled by sorption to (organic matter in) sediments and soils. One of the most abundant organic matter compounds on earth is cellulose. Remarkably, sorption of PAHs to cellulose has hardly been studied; only two reports on the binding of some low-molecular-weight PAHs exist in the literature. In this study, sorption of PAHs to cellulose was investigated in more detail, by measuring isotherms for a series of 13 PAHs, covering a wide hydrophobicity range. The results indicated that sorption of PAHs to cellulose is a linear partition process for all PAHs investigated (phenanthrene-indeno[1,2,3-cd]pyrene). The affinity of PAHs for cellulose appeared to be about 400 times lower than for octanol and even up to 300000 times lower than for black carbon or coal. Linked to the estimated yearly production of cellulose and black carbon, these results suggest that cellulose is probably not a major environmental sorption domain for PAHs.     

Determination of polycyclic aromatic hydrocarbons in dry tea

Twenty-eight different tea samples sold in the United States were evaluated using high-performance liquid chromatography (HPLC) with fluorescence detection (FLD) for their contamination with polycyclic aromatic hydrocarbons (PAHs). Many PAHs exhibit carcinogenic, mutagenic, and teratogenic properties and have been related to several kinds of cancer in man and experimental animals. The presence of PAHs in environmental samples such as water, sediments, and particulate air has been extensively studied, but food samples have received little attention. Eighteen PAHs congeners were analyzed, with percentage recovery higher than 85%. Contamination expressed as the sum of the 18 analyzed PAHs was between 101 and 1337 μg/kg on dry mass and the average contents in all of the 28 examined samples was 300 μg/kg on dry mass. Seven of the congeners were found in all samples with wide ranges of concentrations as follows: fluorene (7–48 μg/kg), anthracene (1–31 μg/kg), pyrene (1–970 μg/kg), benzo(a)anthracene (1–18 μg/kg) chrysene (17–365 μg/kg), benzo(a)pyrene (1–29 μg/kg), and indeno(1,2,3-cd)pyrene (4–119 μg/kg). The two most toxic congeners benzo(a)pyrene and dibenzo(a,h)anthracene were found at high concentrations only in Earl Grey Twinnings, Earl Grey Harney& Sons Fine Teas, and Chai Ultra Spice Black Tea Twinnings. Six PAH congeners are considered as suspected carcinogens (U.S.EPA), formed the basis of the estimation of the toxic equivalent (TEQ), Chai Ultra-Spice Black Tea Twinnings had the highest TEQ (110.9) followed by two grey tea samples, Earl Grey Harney & Sons Fine Tea (57.7) and Earl Grey Twinnings (54.5). Decaffeinated grey teas had the lowest TEQs, decaffeinated Earl Grey Bigelow (9.4) and Green Tea Honey Lemon Decaffeinated Lipton (9.6).     

Lability of polycyclic aromatic hydrocarbons in the rhizosphere

Remediation of soils containing high concentrations of polycyclic aromatic hydrocarbons (PAHs) seldom results in complete removal of contaminants, but residual toxicity often is reduced. In this study, soil from a former manufactured gas plant site was treated for 12 months by phytoremediation and then tested for total PAHs, Tenax-TA extractable ("labile") PAHs, aqueous soluble PAHs (PAH(wp)) , and biotoxicity assessed by earthworms survival, nematode mortality, emergence of lettuce seedlings, and microbial respiration. Prior to phytoremediation, the soil had toxic impacts on all bioassays (except the nematodes), and 12 months of remediation decreased this response. Change in labile PAHs was a predictor for change in total PAH for 3- and 4-ring compounds but not for the 5- and 6-ring. Decreases in labile PAHs were correlated (r(2)>or=0.80) with toxicity in the bioassays except microbial respiration. PAH(wp) was correlated only with nematode toxicity prior to remediation but with none of the tests after remediation. Total PAHs were not correlated with any of the bioassay tests. Tenax-TA appears to have potential for predicting residual toxicity in remediated soils and is superior to total concentrations for that application.     

Determination of polycyclic aromatic hydrocarbons in roasted coffee

Polycyclic aromatic hydrocarbons (PAHs) are suspected to be carcinogenic and mutagenic. This study describes the presence of PAHs in light, medium and dark roasted coffee including instant and decaffeinated brands. Total PAHs concentration was related to the degree of roasting with light roasted coffee showing the least and dark roasted coffee showing the highest level. Both instant and decaffeinated coffee brand showed lower levels of PAHs. Naphthalene, acenaphthylene, pyrene and chrysene were the most abundant individual isomers. The concentrations ranged from 0 to 561 ng g^?1 for naphthalene, 0 to 512 ng g^?1 for acenaphthylene, 60 to 459 ng g^?1 for pyrene and 56 to 371 ng g^?1 for chrysene. Thus, roasting conditions should be controlled to avoid the formation of PAHs due to their suspected carcinogenic and mutagenic properties.     

Accumulation of polycyclic aromatic hydrocarbons in crankcase oil

The concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in automotive crankcase oils. PAHs were not detected in the new oil; however, concentrations increased rapidly with usage in the gasoline engine of an automobile. The PAH distributions found were dominated by alkylated two- and three-ring compounds. The concentrations of these compounds increased until about 4000 miles and then levelled out. Four-ring compounds continually increased with miles driven, and the five-ring benzopyrenes were only detected in the oil used for the longest distance (about 5800 miles).     

Analysis of polycyclic aromatic hydrocarbons in wastewater treatment plant effluents using hollow fibre liquid-phase microextraction

A simple and efficient method for the enrichment of low molecular weight polycyclic aromatic hydrocarbons (PAHs) in effluents originating from wastewater treatment plants is presented here. The proposed protocol couples the recently introduced hollow fibre liquid-phase microextraction (LPME) method with gas chromatography-mass spectrometry. Method parameters were controlled and the optimised experimental conditions were: 5 ml aqueous samples, containing 2.5% NaCl w/v, stirred at 1000 rpm, extracted with toluene for 15 min. The developed protocol yielded a linear calibration curve in the concentration range from 0.5 to 50 microg l(-1) for all target analytes (namely acenaphthene, phenanthrene, fluoranthene and pyrene) and limits of detection in the low microg l(-1) level (0.005-0.011 microg l(-1)). The repeatability and inter-day precision of the method varied between 2.7% and 11.3% and 7.9% and 14.4% respectively. The relative recoveries from different types of natural water samples revealed that matrix had a small effect on the hollow fibre LPME process. The developed method was then applied for the determination of PAHs contamination in effluent samples taken from two major municipal wastewater treatment plants. The results were compared with those obtained with solid-phase microextraction. The ability of both microextraction methods to concentrate organic analytes was demonstrated as both methods confirmed the presence of PAHs as well as of phthalates in the examined effluent samples.     

Relative proportions of polycyclic aromatic hydrocarbons differ between accumulation bioassays and chemical methods to predict bioavailability

Chemical methods to predict the bioavailable fraction of organic contaminants are usually validated in the literature by comparison with established bioassays. A soil spiked with polycyclic aromatic hydrocarbons (PAHs) was aged over six months and subjected to butanol, cyclodextrin and tenax extractions as well as an exhaustive extraction to determine total PAH concentrations at several time points. Earthworm (Eisenia fetida) and rye grass root (Lolium multiflorum) accumulation bioassays were conducted in parallel. Butanol extractions gave the best relationship with earthworm accumulation (r² ≤ 0.54, p ≤ 0.01); cyclodextrin, butanol and acetone-hexane extractions all gave good predictions of accumulation in rye grass roots (r² ≤ 0.86, p ≤ 0.01). However, the profile of the PAHs extracted by the different chemical methods was significantly different (p < 0.01) to that accumulated in the organisms. Biota accumulated a higher proportion of the heavier 4-ringed PAHs. It is concluded that bioaccumulation is a complex process that cannot be predicted by measuring the bioavailable fraction alone.     

Occurrence and accumulation patterns of polycyclic aromatic hydrocarbons and synthetic musk compounds in adipose tissues of Korean females

Very few studies have reported on the occurrence and accumulation profiles of polycyclic aromatic hydrocarbons (PAHs) and synthetic musk compounds (SMCs) in human adipose tissue. In this study, concentrations of PAHs and SMCs in adipose tissues collected from Korean women in 2007 and 2008 were determined. Total concentrations of PAHs and SMCs in adipose tissues ranged from 15 to 361 (mean: 119) ng g^-1 lipid weight and from 38 to 253 (mean: 106) ng g^-1 lipid weight, respectively. Concentrations of SMCs in Korean adipose tissues were lower than those reported for European countries and the United States. Naphthalene was the most predominant PAH and HHCB was the dominant SMC found in adipose tissues. The concentrations of PAHs and SMCs were not correlated with each other, suggesting that the sources of human exposure to these two classes of compounds are different. No correlation was found between donor’s age and residue levels of PAHs and SMCs. The results of this study provide baseline information on exposure of PAHs and SMCs to the general population in Korea.     

Relative decay index and sources of polycyclic aromatic hydrocarbons

An optimized method for the analysis of polycyclic aromatic hydrocarbons (PAH) in atmospheric aerosols with short sampling times (1h) has been used to determine the daily variations of PAH in the atmosphere. Of the various physicochemical parameters controlling the disappearance of PAH, the most important seem to be the thermic dependence and the chemical reactions with gaseous pollutants (NO_x, O₃, HNO₃, OH). The RDI is used to identify the different sources of urban pollution: domestic heating, vehicle traffic (petrol and diesel), refineries, foundries, incinerators and power stations (coal, gas and oil) and to quantify the results for standard conditions. The characteristic concentration ratios from each source are often different from those in the literature, where the data are based on long sampling times and are affected by PAH reactivity differences. The results obtained are parameters for setting up a mathematical model for calculating concentrations of PAH at any receptor site.     

Volatilization of polycyclic aromatic hydrocarbons from coal-tar-sealed pavement

The effects of the herbicide atrazine on the gill of the freshwater fish Prochilodus lineatus were evaluated after exposure of fish to 2, 10 and 25 μg L⁻¹ atrazine during 48 h (acute exposure) and 14 d (subchronic exposure). Ions and osmolality were measured in plasma and gill samples were taken to determine the Na⁺/K⁺-ATPase (NKA) and carbonic anhydrase (CA) activities and for morphological analysis. Plasma osmolality and Na⁺ and Cl⁻ ions changed depending on atrazine concentration, but atrazine exposure had no effect on the Na⁺/Cl⁻ ratio. NKA activity did not change after atrazine exposure, but CA activity decreased in fish exposed to 25 μg L⁻¹ for 14 d. Gill MRC density decreased after acute exposure but did not change in fish exposed to the subchronic treatment. The MRC density at the epithelial surface increased in fish exposed to 25 μg L⁻¹, and the MRC fractional area (MRCFA) increased in fish exposed to 10 μg L⁻¹. The changes in MRCs provide evidence of morphological adjustments to maintain ionic homeostasis in spite of the inhibition of CA activity at the highest atrazine concentration.     

多环芳烃在低氧沉积物环境中的分布状况

低氧环境普遍存在于底层水体以及表层沉积物中,随着中国水体有机污染加剧,低氧现象将越来越明显.有研究表明,中国水体普遍受到多环芳烃污染,由于其强烈的憎水性和低溶解性,大部分多环芳烃沉积在底泥中.总结了学者们对国内外河流、湿地、河口等水体沉积物中多环芳烃污染的研究成果,探讨了多环芳烃的分布规律,发现沉积物中多环芳烃含量与流域内经济发展状况密切相关,反映了经济发展过程对环境造成的负面影响.相比于国外典型区域的多环芳烃浓度,中国沉积物的多环芳烃污染处于中等水平,但处于快速上升阶段,部分点位浓度已超过生态风险区间低值(4 000 ng/g),对人们的身体健康构成威胁,所以对多环芳烃的生态风险评价、污染物排放控制需进一步加强.     

空气中多环芳烃的研究进展

介绍了国内对大气中气态,颗粒态ＰＡＨｓ的研究概况,室内外空气中ＰＡＨｓ污染与城市交通间的相关性,ＰＡＨｓ总量代表物,硝基ＰＡＨｓ及人体接触ＰＡＨｓ的生物指标。