北京市BTEX的污染现状及变化规律分析

2008年10～2009年10月,利用前级浓缩-气相色谱/质谱法,对北京市大气中5种苯系物BTEX（苯、甲苯、乙苯、间、对二甲苯、邻二甲苯）的组成及浓度变化进行了采样分析研究.结果表明,北京市大气BTEX平均浓度为13.9～44.0μg.cm-3,其中甲苯的含量最高,苯次之,邻二甲苯含量最低,与国外城市和地区相比北京大气中BTEX浓度较低,研究发现北京市BTEX主要来自机动车排放,城市燃煤和工业溶剂挥发也是BTEX的重要来源.一年的观测结果表明,BTEX春、夏季节浓度较高,秋季浓度较低,季节性排放源的变化是BTEX季节变化的主要原因,同时也不能忽视温度和大风等天气因素对BTEX浓度的影响.受交通排放和边界层高度的影响,BTEX类化合物的日变化形式为夜晚高于白天,呈双峰形,日最低浓度出现在14：00前后.     

苯系物在红壤不同粒径组分上的吸附-解吸行为

根据粒径将红壤组分分为4种(0.002 mm、0.002~0.05mm、0.05~0.25 mm、0.25~2 mm),研究了苯系物(邻二甲苯、对二甲苯和乙苯混合物,BTEX)在不同粒径组分上的吸附-解吸行为。结果表明,两区非平衡模型可以很好地拟合红壤不同粒径组分对BTEX的吸附动力学,吸附量随红壤粒径减小而增大。红壤不同粒径组分对BTEX的吸附-解吸过程接近于线性(R20.98),Kd随粒径减小而增大,表明红壤粒径的差异极大地影响了BTEX的吸附行为。同时,BTEX在红壤不同粒径组分上的解吸存在不同程度的滞后现象,滞后系数HI随粒径减小而增大。BTEX的解吸滞后现象比多环芳烃和石油烃明显,可能是由于BTEX的分子较小,易进入颗粒孔隙内部成为不可逆吸附部分而不容易解吸。通过XRD及FTIR分析了红壤不同粒径组分吸附BTEX前后的特征。XRD的分析结果表明,BTEX主要吸附于高岭石和伊利石表面;FTIR的结果表明,BTEX主要与羧酸酯、酚式羟基等官能团相结合而吸附于土壤颗粒上。     

VOC in an urban and industrial harbor on the French North Sea coast during two contrasted meteorological situations

Two measurement campaigns of volatile organic compounds (VOC) were carried out in the industrial city of Dunkerque, using Radiello passive samplers during winter (16–23 January) and summer (6–13 June) 2007. 174 compounds were identified belonging to six chemical families. Classifying sampling sites with similar chemical profiles by hierarchical ascending classification resulted in 4 groups that reflected the influence of the main industrial and urban sources of pollution. Also, the BTEX (Benzene, Toluene, Ethylbenzene and Xylenes) quantification allowed us to map their levels of concentration. Benzene and toluene (BT) showed high concentrations in Northern Dunkerque reflecting the influence of two industrial plants. Differences among spatial distributions of the BT concentrations over contrasted meteorological conditions were also observed. An atypical ratio of T/B in the summer samples led us to investigate the BTEX origins shedding light on the contribution of pollutants transported across various zones of VOC emissions situated in Europe.     

Assessment of Bacterial Degradation of Aromatic Hydrocarbons in the Environment by Analysis of Stable Carbon Isotope Fractionation

¹³C/¹²C stable carbon isotope fractionation was used to assess biodegradation in contaminated aquifers with toluene as a model compound. Different strains of anaerobic bacteria (Thauera aromatica, Geobacter metallireducens, and the sulfate-reducing strain TRM1) showed consistent ¹³C/¹²C carbon isotope fractionation with fractionation factors between C = 1.0017 and 1.0018. In contrast, three cultures of aerobic organisms, using different mono- and dioxygenase enzyme systems to initiate toluene degradation, showed variable isotope fractionation factors of C = 1.0027 (Pseudomonasputida strain mt-2), C = 1.0011 (Ralstonia picketii), andC = 1.0004 (Pseudomonas putida strain F1). The great variability of isotope fractionation between different aerobic bacterial strains suggests that interpretation of isotope data in oxic habitats can only be qualitative. A soil column was run as a model system for contaminated aquifers with toluene as the carbon source and sulfate as the electron acceptor and samples were taken at different ports along the column. Microbial toluene degradation was calculated based on the ¹³C/¹²C isotope fractionation factors of the batch culture experiments together with the observed ¹³C/¹²C isotope shifts of the residual toluene fractions. The calculated percentage of biodegradation, B, correlated well with the decreasing toluene concentrations at the sampling ports and indicated the increasing extent of biodegradation along the column. The theoretical toluene concentrations as calculated based on the isotope values matched the measured concentrations at the different sampling ports indicating that the Rayleigh equation can be used to calculate biodegradation in quasi closed systems based on measured isotope shifts. A similar attempt was performed to assess toluene degradation in a contaminated, anoxic aquifer. A transect of groundwater wells was monitored along the main direction of the groundwater flow and revealed decreasing concentrations accompanied with an increase in the ¹³C/¹²C stable carbon isotope ratio of the residual toluene. Calculation of the extent of biodegradation based on the isotope values and laboratory derived isotope fractionation factors showed that the residual toluene was degraded to more than 99% by microbial activity. Calculation of the theoretical residual toluene concentrations based on the measured isotope values described the strongly decreasing concentrations along the plume. Other aromatic hydrocarbons like benzene and naphthalene which were analysed in the same course also showed decreasing concentrations along the groundwater flow path accompanied by increasing ¹³C values indicating biodegradation.     

渤海北部典型芳香烃类化合物污染状况及生态风险评价

为探究渤海北部海上油气区及周边近岸海域典型芳香烃类化合物污染状况,2015年5月现场采集了32个站位的海水样品,针对7种苯系物(BTEX)和17种多环芳烃(PAHs)进行测定,并采用商值法和毒性当量法对污染物开展单一和联合生态风险评估。结果显示,研究海域海水中7种苯系物总含量范围为65.1～222.6 ng·L~(-1),以甲苯含量最高,表层含量略低于底层,油气区平均含量低于周边近岸,受到陆源污染输入的影响特征明显。表层海水中ΣPAHs含量范围为98.9～356.0 ng·L~(-1),平均值为184.5 ng·L~(-1),以低环芳烃占优势,总体处于中等水平,比值法判定该海域PAHs可能主要来源于石油及其加工产品。该海域海水中苯并(a)芘的风险商RQ值大于0.1,表现出低度风险,其余3种处于可接受水平。4种芳香烃类化合物联合生态风险等级为低度风险,对生态系统具有潜在的不利影响,但不同区域仍存在一定差异性,海上石油开采与陆源输入是影响该海域个别区域生态风险较高的重要因素。     

Stable isotope fractionation analysis as a tool to monitor biodegradation in contaminated acquifers

The assessment of biodegradation in contaminated aquifers has become an issue of increasing importance in the recent years. To some extent, this can be related to the acceptance of intrinsic bioremediation or monitored natural attenuation as a means to manage contaminated sites. Among the few existing methods to detect biodegradation in the subsurface, stable isotope fractionation analysis (SIFA) is one of the most promising approaches which is pronounced by the drastically increasing number of applications. This review covers the recent laboratory and field studies assessing biodegradation of contaminants via stable isotope analysis. Stable isotope enrichment factors have been found that vary from no fractionation for dioxygenase reactions converting aromatic hydrocarbons over moderate fractionation by monooxygenase reactions (epsilon=-3 per thousand) and some anaerobic studies on microbial degradation of aromatic hydrocarbons (epsilon=-1.7 per thousand) to larger fractionations by anaerobic dehalogenation reactions of chlorinated solvents (epsilon=between -5 per thousand and -30 per thousand). The different isotope enrichment factors can be related to the respective biochemical reactions. Based on that knowledge, we discuss under what circumstances SIFA can be used for a qualitative or even a quantitative assessment of biodegradation in the environment. In a steadily increasing number of cases, it was possible to explain biodegradation processes in the field based on isotope enrichment factors obtained from laboratory experiments with pure cultures and measured isotope values from the field. The review will focus on the aerobic and anaerobic degradation of aromatic hydrocarbons and chlorinated solvents as the major contaminants of groundwater. Advances in the instrumental development for stable isotope analysis are only mentioned if it is important for the understanding of the application.     

不同化学氧化剂对焦化污染场地苯系物的修复效果

采用自制全封闭模拟装置比较研究了Fenton试剂、类Fenton试剂、高锰酸钾以及活化过硫酸钠4种常用的化学氧化剂对焦化工业污染场地中苯系物的去除效果.结果表明,去除土壤BTEX效果较好的是Fenton试剂和类Fenton试剂,在最佳剂量条件下分别能使BTEX的浓度降低83%和73%,且反应过程中经挥发进入到回收液中的...     

BTEX降解嗜盐菌群的多样性及其降解特性

从胜利油田采油井口的盐碱化油污土壤中富集分离出一个高效降解BTEX的嗜盐菌群,通过PCR-DGGE技术和16S rDNA序列分析,确定该菌群主要由海杆菌属(Marinobacter)、盐单胞菌属(Halomonas)、食碱菌属(Alcanivorax),梭菌属(Clostridium)的细菌等组成.在5%盐度的海盐培养基中,该降解菌群可以在56h内将100mg·L-1的苯完全降解,在112h内将20-400mg·L-1的BTEX混合底物完全降解.进一步的研究结果表明,菌群的盐度适应范围为5%～20%,在pH=6.5～9.5的范围内均可以降解苯,最佳pH=7.5.降解菌群在20～45℃下均可高效降解苯,30℃为最佳降饵温度.微量酵母粉(0.01%～0.02%)的添加可以显著提高菌群的降解速率1.3～1.7倍.     

BTEX在地下环境中的自然衰减

通过室内模拟柱实验研究了BTEX在地下环境中的自然衰减过程,发现BTEX通过以细砂为介质的模拟地下环境时确实发生了自然衰减,挥发和生物降解作用是其自然衰减的重要机制.以苯为例,其在水中的质量浓度为11.40 mg/L左右时,挥发和生物降解作用占自然衰减的比例分别是16.36%和4.91%;而甲苯浓度为3.30 mg/L左右时,两者所占比例分别是11.04%和41.50%.可见BTEX中各组分衰减规律不同.BTEX浓度越大,其挥发得也越快,挥发对自然衰减的作用越大.微生物降解作用对甲苯更有效,占自然衰减的41.50%,间、对二甲苯次之占8.49%,而苯和乙苯很难被降解.     

北京市大气中BTEX工作日与非工作日的浓度变化

对2006年北京市大气中苯系物(BTEX)在工作日和非工作日的浓度变化进行研究.结果表明,BTEX在非工作日的平均浓度比工作日低4.8%,其中"五一"和"十一"假期BTEX的浓度分别为54%和13.2%.BTEX在非工作日浓度降低的主要原因是因为非工作日机动车使用量的减少.在工作日BTEX浓度峰值与上下班交通高峰有关,而在非工作日浓度从下午到夜间维持在一个较高浓度.BTEX各物质之间的比值在工作日和非工作日差别不大,但是各物质之间在非工作日的相关性比工作日好.苯和甲苯在工作日和非工作日都具有较好的相关性,乙苯和二甲苯之间在非工作日的相关性比工作日高.