141 resultados para PLYCYCLIC AROMATIC HYDROCARBONS


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A simple method, based on the technique of capillary column switching-back flushing, has been developed for the detailed analysis of aromatic compounds in gasoline. The sample was first separated on a 30-m long OV-2330 polar precolumn and then backflushed onto a nonpolar analytical column. The early eluting components from the precolumn and the components of interest (aromatic compounds plus heavier compounds) eluting from the analytical column are all directed to the same flame ionization detection system through a T piece, which permits the quantitative analysis of aromatic hydrocarbons in gasoline by a normalization method using correcting factors. The switching time window of the method is +/-5 s, resulting in easier operation and higher reliability. The reproducibility of the quantitative analysis was less than or equal to3% RSD for real gasoline samples. (C) 2002 Elsevier Science B.V. All rights reserved.

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黑碳(BC)是生物质和化石燃料不完全燃烧产生的高度聚合的碳质混合物,包括木炭 (char/charcoal)和烟炱碳(soot)等形式。黑碳产生后大部分储存在燃烧原地,而烟炱碳 由于粒径较小,易进入大气,滞留一到数周后回到地表。部分土壤黑碳随河流和大气的搬 运作用进入海洋环境,主要汇集在海岸带沉积物中。由于黑碳涉及到气候变化、碳循环、 环境危害、人体健康等诸多问题而成为当前气候与环境领域的研究热点。黑碳在环境介质 中比较稳定,因而可以较好的指示人类能源使用及其对环境质量的影响;同时黑碳具有很 强的吸附性,能显著影响周围介质中持久性有机污染物(如多环芳烃等)的赋存状态和生态 毒理效应。 多环芳烃(PAHs)是指两个或两个以上的苯环以稠环形式结合的芳香族化合物,主要 来源于含碳物质的不完全燃烧过程,在环境中广泛存在。由于PAHs 具有潜在的致癌性、 致畸性和致突变性(“三致”效应)而在环境研究领域中备受关注。另外由于具有主体的 同源性,PAHs 可以指示BC 的来源和环境过程。 海岸带沉积物是包括BC 和PAHs 在内的众多污染物在环境地球化学迁移过程中的主 要载体和归宿,由于受到陆地和海洋双重作用,海岸带对环境污染物尤其敏感。环渤海地 区是我国北方的社会经济中心,工业、农业和交通发达、人口稠密,污染严重。前人的研 究表明渤海湾的BC 和PAHs 污染程度明显高于我国其他海岸带,但受限制于采样区域和 样品数量,不能全面地反应BC 和PAHs 在渤海湾海岸带的分布状况及人类活动对海岸带 环境质量的影响。 本次研究在渤海湾海岸带潮间带、近海及主要入海河流系统布设了多条采样剖面,采 集表层沉积物样品85 个。首先,对国际上较为常用的化学热氧化法(CTO-375)处理沉积 物黑碳样品的方法进行了比对实验和优化,然后对全部样品进行黑碳分析;利用GC-MS 方法对样品中的PAHs(USEPA 的16 种优控物)进行了定量检测;对全部沉积物样品还进 行了粒度分析。 结果表明,该区域内黑碳的含量为0.09 到22.8 mg/g dw,其中,潮间带样品的BC 平 均含量为0.52 ± 0.39 mg/g dw,近海样品为0.84 ± 0.38 mg/g dw,河流样品(海河样品除外) 为1.88 ± 0.89 mg/g dw。BC占总有机碳的比例在潮间带、近海、河流区域分别为18.4 ± 8.3%、 14.5 ± 5.3%、14.2 ± 4.1%。潮间带黑碳存在明显的“北高南低”的趋势(以天津港码头和 海河为界),与近海和河流样品的BC 浓度有相似的变化趋势,反映了BC 在海岸带的运移 扩散具有一定的继承性;河流输入可能是近岸沉积物BC 的主要来源。同时,潮间带沉积 物粒度分析结果表明“北区细”(以粘土质粉砂主)而“南区粗”(以砂为主),反映了两个区 域不同的水动力条件和沉积环境,可能是造成BC 浓度空间分异的主要原因。 摘要 II 多环芳烃的含量分布为33.1-7658.7 ng/g dw,其中,潮间带样品的PAHs 平均含量为 147.0 ng/g dw,近海样品为170.9 ng/g dw,河流样品(海河样品除外)为1228.5 ng/g dw。 主要成分均为三环和四环多环芳烃。PAHs 也呈现出了与BC 相似的“北高南低”的趋势, 多环芳烃与黑碳的相关性研究表明两者相关性较好(R2=0.59),表明多环芳烃和黑碳的同 源性和继承性。运用比值法(菲/蒽,荧蒽/芘,低环/高环等)对多环芳烃的来源解析显示, 整个研究区域内多环芳烃主要为燃烧源。

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To characterize the contamination of anthropogenic organic contaminants in the aquatic environment of Chaohu Lake, China, 7 samples for both water and surface sediment were collected in the lake. Organic contaminants were extracted by solid phase extraction (SPE) and Soxhlet extraction from the water and surface sediment samples, respectively, and then analyzed by GC-MS. One hundred and twenty kinds of organic chemicals were detected in these samples including phenol, benzene series, benzaldehydes, ethanol, polycyclic aromatic hydrocarbons (PAHs), sulfur compounds, alcoholic halides, amines, ketones, esters, alkenes and alkanes. Among them, 13 kinds of chemicals were identified as priority pollutants listed by the U.S. Environmental Protection Agency (EPA), such as phthalate esters (PAEs) and PAHs. Besides, the concentrations of 19 of PAEs and PAHs including, priority pollutants identified were also determined. Bis(2-ethylhexyl)phthalate, the predominant component of the analyzed pollutants, was in the range from 72.34 ng g(-1) DW to 613.71 ng g(-1) DW, 14.80 ng L-1 to 47.05 ng L-1 in sediment and water, respectively. The results indicated that the northwest part of the lake was heavily polluted by domestic and industrial wastewater.

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Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) were measured in the water column from Three Gorges Reservoir (TGR) collected in May 2008 using semipermeable membrane devices (SPMDs). The sampling sites spanned the whole reservoir from the upstream Chongqing to the great dam covering more than 600 km long distance with water flow velocities ranging from <0.05 to 1.5 m s(-1). This is the first experience of SPMD application in the biggest reservoir in the world. The results of water sampling rates based on performance reference compounds (PRC) were tested to be significantly correlated with water flow velocities in the big river. Results of back-calculated aqueous concentrations based on PRC showed obvious regional variations of PAH, PCB and OCP levels in the reservoir. Total PAH ranged from 13.8 to 97.2 ng L-1, with the higher concentrations occurring in the region of upstream and near the dam. Phenanthrene, fluoranthene, pyrene and chrysene were the predominant PAH compounds in TGR water. Total PCB ranged from 0.08 to 0.51 ng L-1, with the highest one occurring in the region near the dam. PCB 28, 52, 101, 138, 153, 180, 118 were the most abundant PCB congeners in the water. The total OCP ranged from 2.33 to 3.60 ng L-1 and the levels showed homogenous distribution in the whole reservoir. HCH, DDT and HCB, PeCB were the major compounds of OCP fingerprints. Based on water quality criteria, the TGR water could be designated as being polluted by HCB and PAH. Data on PAH, PCB and OCP concentrations found in this survey can be used as reference levels for future POP monitoring programmes in TGR. (C) 2009 Elsevier Ltd. All rights reserved.

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The concentrations of major anions and cations, nitrogen and phosphorus, dissolved and particulate trace elements, and organic pollutants were determined for the middle and lower reaches of the Yangtze River (Changjiang) from below the Three Gorges Dam (TGD) to the mouth at Shanghai in November 2006. The concentration of dissolved inorganic phosphate (DIP) was constant at a low level of 6-8 mu gP/L, but the concentration of nitrate (NO3-) approximately doubled downstream and was closely correlated with K+. This translated to a daily load of well over 1000 It of dissolved inorganic nitrogen (DIN) at Datong. The average concentrations of dissolved Pb (0.078 +/- 0.023 mu g/L), Cd (0.024 +/- 0.009 mu g/L), Cr(0.57 +/- 0.09 mu g/L), Cu (1.9 +/- 0.7 mu g/L), and Ni (0.50 +/- 0.49 mu g/L) were comparable with those in other major world rivers, while As (3.3 +/- 1.3 mu g/L) and Zn (1.5 +/- 0.6 mu g/L) were higher by factors of 5.5 and 2.5, respectively. The trace element contents of suspended particles of As (31 +/- 28 mu g/g), Pb (83 +/- 34 mu g/g), and Ni (52 +/- 16 mu g/g) were close to maximum concentrations recommended for rivers by the European Community (EC). The average concentrations of Cd (2.6 +/- 1.6 mu g/g), Cr (185 +/- 102 mu g/g), Cu (115 +/- 106 mu g/g), and Zn (500 +/- 300 mu g/g) exceeded the EC standards by a factor of two, and Hg (4.4 +/- 4.7 mu g/g) by a factor of 4 to 5. Locally occurring peak concentrations exceed these values up to fourfold, among them the notorious elements As, Hg, and Tl. All dissolved and particulate trace element concentrations were higher than estimates made twenty years ago [Zhang, J., Geochemistry of trace metals from Chinese river/estuary systems: an overview. Estuar Coast Shelf Sci 1995; 41: 631-658.]. The enormous loads of anthropogenic pollutants disposed to the river were diluted by the large water discharge of the Yangtze even during the lowest flow resulting in the relatively low concentration levels of trace elements and organic pollutants observed. We estimated loads of e.g. As, Pb and Ni to the East China Sea to be about 4600 kg As d(-1), 3000 kg Pb d(-1), and 2000 kg Ni d(-1). About 6000 t d(-1) of dissolved organic carbon (DOC) was delivered into the sea at the time of our cruise. We tested for 236 organic pollutants, and only the most infamous were found to be barely above detection limits. We estimated that the load of chlorinated compounds, aromatic hydrocarbons, phenols, and PAHs were between 500 and 3500 kg d(-1). We also detected eight herbicides entering the estuary with loads of 5-350 kg d(-1). The pollutant load, even when at low concentrations, are considerable and pose an increasing threat to the health of the East China Sea ecosystem. (c) 2008 Elsevier B.V. All rights reserved.

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针对传统游离微生物修复技术的缺点和弊端,提出了采用固定化微生物技术修复受多环芳烃污染的非流体介质的新课题。本文筛选出2株高效降解菌,并进行了固定化载体筛选,优化并确定了3种固定化工艺。通过实验室模拟实验,考察了固定化菌对PAHs污染非流体介质的修复能力,最后通过扫描电子显微镜(SEM)分析,对固定化微环境强化修复机制进行了初步探讨。 细菌芽孢杆菌(Bacillus sp.,SB02)和真菌毛霉(Mucor sp.,SF06)对土壤中的Pyr、BaP降解率高,降解速率快,为高效降解微生物。 碱化后的泥炭土适宜作为细菌固定化载体;玉米芯适宜作为真菌固定化载体;改性后蛭石适宜作为混合菌固定化载体。这些载体来源广泛,成本低廉,工艺简单,安全无毒。 将固定化菌应用于Pyr、BaP污染土壤的修复,考察了初始接种量、环境温度、土壤含水量对固定化菌降解Pyr、BaP的影响,固定化菌对不同系列浓度Pyr、BaP的降解,以及固定化菌在不灭菌土壤中对Pyr、BaP的降解,表明固定化菌对土壤中Pyr和BaP的降解率均高出游离菌20%,固定化混和菌降解效果最好,其次是固定化真菌,再次是固定化细菌。 SEM分析了固定化颗粒的微观结构和微生物在颗粒内部的形态变化,结果表明颗粒内部丰富的疏松多孔结构和巨大的比表面积为微生物提供了适宜的生存空间,使吸附固定化成为可能。 固定化菌对沈抚灌区PAHs污染土壤修复效果非常理想,经过6个月,土壤中总PAHs的去除率达70.3%,高于游离菌。

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本文以土壤为介质,以三环的菲(Phe)、四环的芘(Pyr)和五环的苯并[a]芘(BaP)为目标污染物,研究了紫外灯照射下土壤中多环芳烃(PAHs)的降解,并以半导体纳米TiO2和Fe2O3为催化剂研究了土壤中PAHs的催化降解,对光降解及光催化降解的动力学进行了研究,在室内条件下考察了土壤条件和环境因子对光降解及光催化降解PAHs的影响;研究了太阳光照条件下土壤pH值对光降解和催化降解的影响和腐殖酸对光降解的影响;初步探讨了纳米TiO2催化光降解土壤中PAHs的机制。 研究结果表明:土壤中PAHs的紫外光降解符合一级动力学模型,土壤中PAHs光降解与土壤厚度呈显著负相关,土壤粒径对紫外光解PAHs有显著影响,温度从20 ℃升高到30 ℃,光解速率逐渐增加,在PAHs污染土壤的光降解中腐殖酸起敏化作用,随着紫外辐射强度的增加,光降解速率加快。 纳米TiO2和Fe2O3均能促进土壤中PAHs的紫外光降解,PAHs光催化降解符合一级动力学模型,在酸性和碱性土壤条件下,光催化降解PAHs的速率均高于中性,在不同光质条件下,TiO2 、Fe2O3催化光降解PAHs的速率发生变化,随着紫外辐射强度的增加,光催化降解速率常数增加,半衰期减少;腐殖酸促进TiO2 、Fe2O3催化土壤中PAHs的光降解,腐殖酸在这个过程中起着敏化作用。 在太阳光照射下酸性和碱性土壤中PAHs的降解快于中性,PAHs污染土壤中在加入腐殖酸后光降解速率加快,在酸性条件下催化降解最快,在碱性和中性条件下相差不大。 土壤中PAHs存在着PAH的光致电离、电子向O2的转移的两种降解途径;在有催化剂TiO2条件下,由于催化剂在光照后形成的电子-空穴能够氧化还原污染物,PAH的光致电离、电子向O2的转移的引起的降解,共同促进了土壤中PAHs的光催化降解。

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本文以多环芳烃污染土壤为研究对象,以菲(Phe)、芘(Pyr)和苯并[a]芘(BaP)为目标污染物,以建立生态、经济、高效污染土壤修复技术为目标,在研究植物与微生物联合修复多环芳烃污染土壤效果的基础上,重点研究了植物与微生物联合修复污染土壤过程中多环芳烃的去除机制。 研究结果表明:种植苜蓿和黑麦草能够促进土壤中多环芳烃的去除,提高土壤中多环芳烃的去除率。植物根际土壤中多环芳烃的去除速度快于于非根际土壤。在植物与高效降解菌联合作用过程中,植物的存在强化了菌剂对土壤中多环芳烃的去除作用。苜蓿和黑麦草与高效降解菌的联合作用使菲、芘和苯并[a]芘去除率分别比对照土壤提高了26.64%、30.41%、32.04%和26.93%、27.43%、30.15%。 植物根和茎叶中菲、芘和苯并[a]芘的含量与土壤污染物浓度正相关,但其吸收积累作用对土壤中多环芳烃去除的贡献率小于0.34%。植物对土壤多环芳烃污染的修复作用主要源于植物生长显著提高了根际微生物的降解活性。 植物根际微生物的数量和土壤酶活性显著高于非根际土壤。植物根系的存在提高了土壤中微生物的数量和酶活性,从而提高了土壤中PAHs的去除率。这是根际土壤中多环芳烃去除的主要机制。 模拟根际修复,研究了添加根系分泌物对土壤中芘降解的影响。添加20mg/kg根系分泌物土壤中细菌数量为未添加根系分泌物土壤的19.43-36.29倍,真菌为3.05-6.60倍,土壤中芘的半衰期比未添加根系分泌物处理减少10.91天。植物根系分泌物是影响根际修复的一个重要原因。

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研究用植物油淋洗修复多环芳烃污染土壤的效果、植物油淋洗剂再生与回用的可行性、植物油的生态效应。采用了批处理法和土柱法对多环芳烃污染土壤进行修复,结果表明:油土比1:1的条件下,批处理法可以去除土壤中90%以上的多环芳烃,多环芳烃的质量转移过程可以用经验模型模拟。恰当的运行条件下,土柱法可去除土壤中90%以上的多环芳烃,但是根据土壤中多环芳烃浓度的高低,植物油的用量是批处理法的2~4倍。无论是批处理法,还是土柱法,土壤水分含量都影响了植物油去除土壤中多环芳烃的能力。采用了化学氧化法、溶剂提取法和吸收剂吸收法对植物油进行再生,结果表明:臭氧和双氧水能氧化植物油中的多环芳烃,但不理想,紫外线及双氧水在pH=3的条件下可氧化植物油中76.5%的多环芳烃。按植物油/乙醇1:3的比例对植物油进行6级处理可氧化植物油中87%的多环芳烃。活性炭二级处理可去除植物油中87%的多环芳烃,实现植物油的再生。高等植物生长实验说明土壤中的植物油对燕麦及萝卜的生长起了抑制作用,土壤呼吸实验证明,残留在土壤中的植物油可被生物降解,但是必须保证良好的氧气及营养供应。用植物油修复多环芳烃污染土壤具有可行性。

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A sol-gel coating method for the preparation of extractive phase on bars used in sorptive microextraction is described. The extraction phase of poly(dimethylsiloxane) is partially crosslinked with the sol-gel network, and the most part is physically incorporated in the network. Three aging steps at different temperatures are applied to complete the crosslinking process. Thirty-micrometer-thick coating layer is obtained by one coating process. The improved coating shows good thermal stability up to 300degreesC. Spiked aqueous samples containing n-alkanes, polycyclic aromatic hydrocarbons and organophosphorus pesticides were analyzed by using the sorptive bars and GC. The results demonstrate that it is suitable for both aploar and polar analytes. The detection limit for chrysene is 7.44 ng/L, 0.74 ng/L for C-19 and 0.9 ng/L for phorate. The extraction equilibration can be reached in less than 15 min by supersonic extraction with the bars of 30 mum coating layer. (C) 2004 Elsevier B.V. All rights reserved.

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A capillary electrochromatography (CEC) monolithic column with zwitterionic stationary phases was prepared by in situ polymerization of butyl methacrylate, ethylene dimethacrylate, methacrylic acid, and 2-(dimethyl amino) ethyl methacrylate in the presence of porogens. The stationary phases have zwitterionic functional groups, that is, both tertiary amine and acrylic acid groups, so the ionization of those groups on the zwitterionic stationary phase was affected by the pH values of the mobile phase, and further affects the strength and direction of the electroosmotic flow (EOF). Separations of alkylbenzenes and polycylic aromatic hydrocarbons based on the hydrophobic mechanism were obtained. Separation of various types of polar compounds, including phenols, anilines, and peptides, on the prepared column were performed under CEC mode with anodic and cathodic EOF, and different separation selectivities of those polar analytes were observed on the monolithic capillary column by using mobile phases with different pH values.

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A novel ion-bonded discotic complex was prepared from 2,3,6,7,10,11-hexakis(N,N-dimethylaminopropylaminocarbonylmethoxy)triphenylene (HDTP) and 4'-dodecyloxybiphenyl-4-carboxylic acid (DBC) by ionic self-assembly (ISA) route and characterized by Fourier transform infrared (FTIR) spectrum. We found that the complex can self-assemble into stable gels in aromatic hydrocarbons. Nanofibers with diameters of 50-130 nm were observed in the gels by transmission electron micrograph (TEM).

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The influences of additive, diluents, temperature, acidity of the aqueous phase on the interfacial behavior of primary amine N1923 in sulfate media have been investigated using the Du Nouy ring method. In addition, the effect of concentration of thorium(IV) loaded in the organic phase on the interfacial tension has also been studied. The interfacial tension isotherms are processed by matching different adsorption equations such as the Gibbs and the Szyszkowski. The surface excess at the saturated interface (Gamma (max)) and the minimum bulk concentration of the extractant necessary to saturate the interface (C-min) under different conditions are calculated according to two adsorption equations to be presented in comprehensive tables and figures. It appears that primary amine N1923 has strong interfacial activity and behaves very differently in various diluents systems. The surface excess at saturated interface increase with the type of diluerits in the following order: chloroform < aromatic hydrocarbons < aliphatic hydrocarbons. The relationship between the interfacial activity and kinetics of thorium extraction by primary amine N1923 has been discussed by considering different factors. However, the interfacial activity of primary amine N1923 is only a qualitative parameter suggesting the interfacial mechanism for thorium extraction, it cannot give strong evidence quantitatively supporting this mechanism.