芳香类有机物氯化生成消毒副产物的特性研究

选择有代表性的芳香类有机物,在含有腐殖酸的水溶液中进行氯化试验.测定三卤甲烷和卤乙酸的生成特性.并分析有机物的化学结构对生成消毒副产物的影响.结果表明.各受试物氯化生成消毒副产物的活性和反应速率排序为间苯二酚>对苯二酚>邻苯二酚>苯酚>苯胺>苯甲酸>硝基苯;芳香类有机物苯环上官能团的性质、数量和位置等影响消毒副产物的生成;间苯二酚的氯化反应可分为快速反应阶段和慢速反应阶段.     

Environmental monitoring of complex hydrocarbon mixtures in water and soil samples after solid phase microextraction using PVC/MWCNTs nanocomposite fiber

A novel nanocomposite based on incorporation of multiwalled carbon nanotubes (MWCNTs) in polyvinyl chloride (PVC) was prepared. Proposed nanocomposite was coated on stainless steel wire by deep coating. Composition of nanocomposite was optimized based on results of morphological studies using scanning electron microscopy. The best composition (83% MWCNTs:17% PVC) was applied as a solid phase microextraction fiber. Complex mixture of aromatic (BTEX) and aliphatic hydrocarbons (C₅–C₃₄) were selected as model analytes, and performance of proposed fiber in extraction of the studied compounds from water and soil samples was evaluated. Analytical merits of the method for water samples (LODs = 0.10–1.10 ng L⁻¹, r² = 0.9940–0.9994) and for soil samples (LODs = 0.10–0.77 ng kg⁻¹, r² = 0.9946–0.9994) showed excellent characteristics of it in ultra trace determination of petroleum type environmental pollutants. Finally, the method was used for determination of target analytes in river water, industrial effluent and soil samples.     

Polycyclic aromatic hydrocarbons: bees, honey and pollen as sentinels for environmental chemical contaminants

Three beehive matrices, sampled in six different apiaries from West France, were analyzed for the presence of four polycyclic aromatic hydrocarbons (PAH4: benzo[a]pyrene, benzo[a]anthracene, benzo[b]fluoranthene and chrysene). Samples were collected during four different periods in both 2008 and 2009. Honey samples showed the lowest levels of PAH4 contamination (min = 0.03 μg kg⁻¹; max = 5.80 μg kg⁻¹; mean = 0.82 μg kg⁻¹; Sd = 1.17). Bee samples exhibited higher levels of PAH4 contamination (min = 0.32 μg kg⁻¹; max = 73.83 μg kg⁻¹; mean = 7.03 μg kg⁻¹; Sd = 17.83) with a great dispersion of the concentrations due to four main events of high concentrations. Pollen samples showed only one major episode with the highest PAH4 concentration found (min = 0.33 μg kg⁻¹; max = 129.41 μg kg⁻¹; mean = 7.10 μg kg⁻¹; Sd = 22.28). The PAH4 concentrations found were significantly influenced by the landscape context for all beehive samples.     

Factors influencing on the bioaccessibility of polybrominated diphenyl ethers in size-specific dust from air conditioner filters

Size-specific concentrations and bioaccessibility of polybrominated diphenyl ethers (PBDEs) in dust from air conditioner filters were measured, and the factors influencing the PBDE bioaccessibility were determined. Generally, the PBDE concentrations increased with decreasing dust particle size, and BDE209 (deca-BDE) was generally the predominant congener. The bioaccessibility ranged from 20.3% to 50.8% for tri- to hepta-BDEs, and from 5.1% to 13.9% for BDE209 in dust fractions of varied particle size. The bioaccessibility of most PBDE congeners decreased with increasing dust particle size. The way of being of PBDE (adsorbed to dust surface or incorporated into polymers) in dust significantly influenced the bioaccessibility. There was a significant negative correlation between the tri- to hepta-BDE bioaccessibility and organic matter (OM) contents in dust. Furthermore, tri- to hepta-BDE bioaccessibility increased with increasing polarity of OMs, while with decreasing aromaticity of OMs. The tri- to hepta-BDE bioaccessibility significantly positively correlated with the surface areas and pore volumes of dust. Using multiple linear regression analysis, it was found that the OM contents and pore volumes of dust were the most important factors to influence the tri- to hepta-BDE bioaccessibility and they could be used to estimate the bioaccessibility of tri- to hepta-BDEs according to the following equation: bioaccessibility (%) = 45.05 − 0.49 × OM% + 1.79 × pore volume. However, BDE209 bioaccessibility did not correlate to any of these factors.     

Binding of polycyclic aromatic hydrocarbons by humic acids formed during composting

Binding of two model polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, by humic acids (HAs) isolated from an organic substrate at different stages of composting and a soil was investigated using a batch fluorescence quenching method and the modified Freundlich model. With respect to soil HA, the organic substrate HA fractions were characterized by larger binding affinities for both phenanthrene and pyrene. Further, isotherm deviation from linearity was larger for soil HA than for organic substrate HAs, indicating a larger heterogeneity of binding sites in the former. The composting process decreased the binding affinity and increased the heterogeneity of binding sites of HAs. The changes undergone by the HA fraction during composting may be expected to contribute to facilitate microbial accessibility to PAHs. The results obtained also suggest that bioremediation of PAH-contaminated soils with matured compost, rather than with fresh organic amendments, may result in faster and more effective cleanup.     

Reducing plant uptake of PAHs by cationic surfactant-enhanced soil retention

Reducing the transfer of contaminants from soils to plants is a promising approach to produce safe agricultural products grown on contaminated soils. In this study, 0-400 mg/kg cetyltrimethylammonium bromide (CTMAB) and dodecylpyridinium bromide (DDPB) were separately utilized to enhance the sorption of PAHs onto soils, thereby reducing the transfer of PAHs from soil to soil solution and subsequently to plants. Concentrations of phenanthrene and pyrene in vegetables grown in contaminated soils treated with the cationic surfactants were lower than those grown in the surfactant-free control. The maximum reductions of phenanthrene and pyrene were 66% and 51% for chrysanthemum (Chrysanthemum coronarium L.), 62% and 71% for cabbage (Brassica campestris L.), and 34% and 53% for lettuce (Lactuca sativa L.), respectively. Considering the impacts of cationic surfactants on plant growth and soil microbial activity, CTMAB was more appropriate to employ, and the most effective dose was 100-200 mg/kg.     

乙醇对含水层中燃油芳香烃内在生物修复的潜在风险

内在生物修复,是在没有工程措施促进的情况下利用土著微生物降解含水层内灾害性物质的一种修复技术,在燃油烃污染管理方面具有显著的成本效益。该技术需要确定自然衰减过程,并能够继续提供有效的风险保护。针对燃油污染含水层,北美与欧洲认为内在生物修复是值得优先考虑的应用技术。然而,随着乙醇燃油的推广使用,我国在应用这样的经验时需要考虑乙醇的潜在影响。现有的文献研究表明乙醇存在能够阻止燃油主要污染物芳香烃(BTEX)的生物降解,降低水环境的pH值,并可能增强BTEX在水中的溶解性,或存在对生物的毒性,或因为乙醇降解降低介质的渗透性能。因此,需要更好地认识乙醇的潜在风险,为发展乙醇燃油污染含水层修复策略提供科学依据。     

Contaminants in Muscle of Plaice and Halibut Collected From the St. Lawrence Estuary and Northwest Atlantic

Levels of aromatic hydrocarbons in muscle or plaice and halibut were determined by fluorescence, using the chrysene standard, as recommended by the International Oceanographic Commision, for the analysis of PAH in environmental extracts. Concentrations were highest in muscle of halibut collected at the most contaminated, nearshore site, in the Saguenay Fjord of the St. Lawrence Estuary, compared to other locations further from shore. Although concentrations of fluorescing compounds were not statistically different in plaice, the saturated hydrocarbons displayed unquestionably more biodegradation, with a decrease of n-alkanes and increase of branched aliphatics, at the less contaminated site. Synchronous fluorescence indicated the presence of benzenoid and biphenyl hydrocarbons in the extracted mixtures, while GC-MS-TIC analysis tentatively identified the presence of a series of benzenoid (alkyl benzenes), chlorinated (PCB and DDE), N (trialkylamines) and O (phenols) hydrocarbons. These anthropogenic compounds could derive from petroleum products, surfactants and common products used in industry and households. This study emphasizes the importance of a multispectroscopic approach when investigating complex environmental mixtures.     

The chemical basis for trail recognition in Lasius nipponensis (Hymenoptera: Formicidae)

Summary. In this paper we report on the chemical basis for trail recognition in Lasius nipponensis. On and near trails in the field, workers became aggressive against conspecific intruders and succeeded in protective contests, while intruders usually avoided confrontation. Such asymmetric interactions were also observed in the laboratory when two non-nestmate workers were sequentially placed in a clean glass dish, while mutual aggression was observed when they were placed simultaneously. Asymmetric aggression was also observed when the workers were placed in a dish previously conditioned by other workers, or when the dish was treated with the hexane rinse of the conditioned dish. The rinse contained a series of hydrocarbons, in which components and proportion were almost identical to those of the cuticular hydrocarbons of the workers, except for a lack of n-alkanes. Amounts of the hydrocarbons that remained on the dish were very small when all the tarsi of the workers were incapacitated. We therefore consider that the hydrocarbons are not adhesion of the cuticular hydrocarbons but secretion from the tarsi of workers, and serve as a key signal for trail recognition in this ant.     

我国北方典型城市大气中VOCs的组成及分布特征

从2008年4月到2009年1月,利用前级浓缩-气相色谱/质谱法,对天津市和沈阳市大气中的挥发性有机物及浓度变化进行了采样研究.共监测了108种VOCs,包括卤代烷烃39种、苯系物16种、烯烃12种、烷烃30种、醛酯11种,在天津市检测到挥发性有机污染物中,醛酯56.9%,卤代烷烃13.4%,烷烃13.1%,苯系物12.9%,烯烃2.5%,卤代烯烃1.1%.沈阳市醛酯49.3%,卤代烷烃17.8%,烷烃11.8%,苯系物10.3%,卤代烯烃7.8%,烯烃2.9%.2市VOCs的含量季节变化都是春秋季节大于冬夏季节,在不同季节不同点位的VOCs的总量的变化趋势几乎一致,并且分析了天津市和沈阳市苯系物和卤代烃的的主要组成成分以及主要来源,苯系物的主要成分包括苯、甲苯、乙苯、二甲苯,苯系物的主要来源是汽车尾气,卤代烷烃的主要成分是二氯甲烷和氯乙烯,主要来自于汽车尾气和石油化工.