海洋沉积物中多环芳烃的分离和测定

多环芳烃(Polycyclic Aromatic Hydrocarbons,PAH)组分中,大多数具有致突变和致癌性。大气、土壤等自然环境中已经检测出了多种多环芳烃。近年来,在河流、内湾及沿岸海域的水体、沉积物中,也检测出了各种多环芳烃。多环芳烃在海洋环境中广泛存在,已经引起了人们的普遍重视。     

天津地区表土PAHs含量的多尺度空间相关性

本文应用因子克立格分析方法,分析了天津表土16种PAHs之间多尺度空间结构特征。分析结果显示,天津表土PAHs在空间上可以划分三种尺度:块金尺度(0～5km),小空间尺度(5～10km)和大空间尺度(10～50km)。在不同的空间尺度上,16种PAHs之间表现出不同的空间相关性,具有空间尺度相关性。这种空间尺度相关性,是由于不同的空间污染过程造成的,有助于下一步的多尺度空间污染源的判断和污染物迁移转化规律的识别。     

在可控制的相对湿度下矿物表面上多环芳烃的降解

多环芳香烃由于诱发突变和致癌的性质威胁着人类的健康,近年来,其降解问题得到了广泛的关注。笔者研究了在没有光照的条件下,改变相对湿度(5%至30%之间),苯并芘(一种典型的多环芳烃物质)在石英,矾土,蒙脱石,高岭石,腐殖酸和吸附了腐殖酸的石英上的稳定性,继而可以检测出矿物表面催化多环芳烃降解的效果。苯并芘的稳定性主要是由吸附剂的物化性质决定的。石英表现出很好的催化效果,即便其表面被腐殖酸所包覆。在整个实验过程中(3天)吸附在蒙脱石和腐殖酸表面的苯并芘依然很稳定。实验装置中的湿度影响在某些特定的矿物中的苯并芘的稳定性。特…     

厦门西海域表层沉积物中多环芳烃含量分布及生态风险评价

2004年11月30日至12月1日连续两天采集厦门西海域10个站位表层沉积物样品,参照美国EPA标准方法及采用气相色谱与质谱联用(GC/MS)技术,对表层沉积物样品中的多环芳烃(PAHs)进行测定分析.结果表明,厦门西海域表层沉积物样品中16种PAHs的总含量为198.2-1061.6 ng·g-1,平均值为723.51 ng·g-1,能检出的PAHs均以2-4环的芳香物为主;10个站位中X1、X2、X3、X6及M2站位的PAHs主要来源于化石燃料的不完全燃烧,其他站位以石油泄漏为主要来源.对PAHs的生态风险评价结果表明,厦门西海域表层沉积物中PAHs的环境毒性相对较低,说明该海域表层沉积物中PAHs对生物的危害程度较轻.     

Photoinduced toxicity single and binary mixtures of four polycyclic aromatic hydrocarbons to the marine diatom Skeletonema costatum

Diatom Skeletonema costatum Cleve is one of the main predominant phytoplankton species in the Changjiang Estuary in China. In order to provide some basic information for future assessment of the potential risk on phytoplankton communities in this estuary caused by polycyclic aromatic hydrocarbons(PAHs), this alga was selected as a representative to investigate the photoinduced toxicity of PAHs, in single and mixture. Four PAHs including three-ring phenanthrene and anthracene, four-ring fluoranthene and pyrene were tested in the laboratory. The single toxicity of each PAH on this microalga was compared with and without the simulated solar UV radiation. The results showed that this microalga was sensitive to PAH's photoinduced toxicity. Ratios of the 72 h median effect concentration obtained for fluorescent and UV light tests were about 8.4 for phenanthrene, 13.0 for anthracene, 6.5 for fluoranthene, and 5.7 for pyrene, indicating that UV light enhanced the PAH toxicity to this alga significantly. Under the fluorescent radiation (lacking UV), the dose-response curves based on chemical concentrations revealed that the order of toxic strength was fluoranthene greater than pyrene greater than anthracene greater than phenanthrene; while under the UV radiation (476 μW/cm2 for UVA, 6.5 μW/cm2 for UVB) it became fluoranthene approximately equaling anthracene greater than pyrene greater than phenanthrene, indicating that the UV light also changed its relative toxicity to this alga. The photoinduced toxicity of PAHs to the marine diatom S. costatum might be a synergistic effect of photosensitization reactions (e.g., generation of single-state oxygen) and photomodification (photooxidation and/or photolysis).The combined effects of six binary mixtures on the marine diatom S. costatum were investigated using the additive-index method. Four binary-mixtures (phenanthrene plus anthracene; phenanthrene plus pyrene; anthracene plus fluoranthene; anthracene plus pyrene) were found to be synergistic joint action mode, while two binary-mixtures (phenanthrene plus fluoranthene; fluoranthene plus pyrene) displayed antagonist, revealing a complex pattern of possible interactions. The combined action mode of PAHs might be related to various factors such as the mixture compounds, mixture ratios and test conditions, etc.     

气相色谱-质谱法同时测定河流沉积物中多环芳烃和有机氯农药

建立了用加速溶剂萃取,气相色谱-质谱法同时测定河流沉积物中16种多环芳烃和19种有机氯农药的分析方法,优化了萃取溶剂、萃取温度和时间、凝胶渗透色谱收集时间、固相萃取洗脱溶剂和洗脱体积等条件。16种多环芳烃的方法检出限在0.15~0.59 ng/g,加标回收率为82%~102%,相对标准偏差(RSD,n=5)为1.1%~4.5%。19种有机氯农药的方法检出限在0.14~2.23 ng/g,加标回收率为71%~108%,相对标准偏差(RSD,n=5)为1.0%~4.5%。实际样品的测定结果表明,该方法分离效果较好,能够满足沉积物样品中多环芳烃和有机氯农药的分析要求。     

样品前处理过程中多环芳烃的稳定碳同位素分馏

利用多环芳烃标准样品连续和穿插进样相结合的方式,检验了气相色谱-燃烧-同位素比质谱仪(GC-C-IRMS)测定多环芳烃单体碳同位素比值(δ13C)的稳定性和准确性,观察了测定过程中色谱柱的分离效果。结果表明,出峰面积和分离程度是影响化合物δ13C平行性的主要原因。通过多次实验,分析了样品前处理过程中多环芳烃各个化合物稳定碳同位素的分馏情况,包括凝胶渗透色谱(GPC)和硅胶柱等净化过程,以及旋转蒸发和氮气吹扫等浓缩过程。实验表明,各前处理过程中样品内多环芳烃的稳定碳同位素分馏均不明显,其中硅胶柱净化过程相比GPC过程对样品中多环芳烃的δ13C影响较大,但总体上仍未超过未处理标样δ13C值的2倍标准偏差范围。旋转蒸发和氮吹过程对样品中多环芳烃的δ13C影响程度相当,都位于未处理标样δ13C值1倍标准偏差以内的水平。     

Study on polycyclic aromatic hydrocarbons（PAHs） contents and sources in the surface so~l or l-lmznou City, South China, based on multivariate statistics analysis

Studies of polycyclic aromatic hydrocarbons (PAHs) in the surface soil were conducted in Huizhou City, which is located in the Pearl River Delta, South China. Sixteen PAHs in 42 soil samples were detected. The results showed that 4 components of PAHs were detectable in all soil samples, and other 12 components were also detectable to some extent. The total PAHs contents range from 35.40 to 534.5 μg/kg with the mean value of 123.09 μg/kg. Soil in Huizhou was slightly polluted by PAHs according to Maliszewska-Kordybach’s study. It can be confirmed that the increase of PAHs contents in the surface soil of Huizhou City is closely connected to human activities. Multivariate analysis was also made in this study. Principal component analysis was used to constrain their origins, and 3 principal components (PCs) were extracted. The results showed that coal combustion and oil spilling made the major contributions to PAHs. Cluster analysis was made and 16 priority PAHs were classified as 4 sorts, and the result revealed the differences in environmental behavior, chemical properties and sources of PAHs.     

基于特征比值的原油中PAHs标志物风化规律研究

以渤海某原油作为研究对象进行综合模拟风化实验, 探讨了原油中五类PAHs组分的风化规律并筛选出其中稳定的诊断比值。结果表明: 经过50d风化, 原油中PAHs的分布已经发生了较大的改变, 其中萘系类损失最为严重, 菲系列所占的比例有所提高, 二苯并噻吩、屈、芴系列则保持相对稳定, 这为进一步筛选用于溢油来源鉴别的新诊断比值参数提供了一定依据; 经风化检验, 现有常用6种PAHs诊断比值在风化50d后较稳定, 可用于风化溢油的鉴别; 所选取新诊断比值中, 菲和屈系列、烷基取代二苯并噻吩类、烷基取代芴类抗风化能力较强, 共筛选出34种诊断比值可作为溢油鉴别的有效指标。     

南京北郊气溶胶中多环芳烃的污染特征及来源解析

利用2010年8月采集的南京北郊气溶胶样品,使用GC-MS对美国环保总局推荐的16种优先控制的多环芳烃含量、分布特征进行了研究。在此基础上,用特征比值法、主因子分析法分析得到南京市北郊大气中PAHs的主要来源为车辆尾气、燃煤、天然气和草木秸秆燃烧,并应用绝对因子分析法进一步定量计算主要源对PAHs的浓度贡献率。结果表明:1)大气颗粒物中16种多环芳烃的平均总质量浓度为135.85 ng/m~3,多环芳烃以4环为主,在可吸入颗粒物中的浓度占总浓度的88.7%;2)PM10中多环芳烃呈双模态分布,在9~10μm的粗模态和0.65~1.10μm的积聚模态上各出现一个峰值;3)天然气等对PAHs的贡献率为5.7%~44.1%,燃煤源的贡献率为20.7%~57.8%,汽车尾气的贡献率为4.6%~46.7%,木材燃烧的贡献率为2.9%~38.1%。本地交通排放和燃料燃烧是南京北郊大气颗粒物中PAHs的主要来源,远距离输送也对南京北郊气溶胶中的PAHs有重要贡献。