离子类型对石油污染含水层中微生物去除苯的影响

近来利用微生物原位修复受石油污染的含水层已被广泛关注,然而地下水中含有许多离子成分,这些无机离子对微生物降解有机污染物的影响机制还不清楚。本文采用批量实验研究了淄博齐鲁石化污染地下水中常见的7种无机离子(NO3-、PO4 3-、SO4 2-、Cl-、Ca2+、Mg2+、Fe3+)对微生物生长及生物降解苯的影响规律,利用高通量测序技术进一步探究了苯降解菌的种群特征。结果表明：7种离子都存在一个最适宜微生物生长的离子浓度,低于或超过该浓度苯的去除率明显降低,其中NO3-、SO42-、Fe3+最适宜浓度为0. 4mmol/L,PO4 3-、Cl-、Ca2+、Mg2+最适宜浓度分别为0. 2mmol/L、0. 1mol/L、2. 5mmol/L、2mmol/L;从微生物含量及其变化幅度来看,地下水环境中的NO3-离子对微生物的生长及苯的去除影响最显著,其他离子的影响则较小,但微生物对Cl-的耐受浓度较高。高通量测序结果显示驯化出的苯降解菌主要属于脱硫弧菌属(Desulfovibrio sp)、脱硫芽胞弯曲菌属(Desulfosporosinus sp)、不动杆菌属(Acinetobacter sp)和假单胞菌属(Pseudomonas sp)中的菌株。研究结果可为石油污染地下水的原位生物修复提供一定的科学依据。     

有机膨润土制备条件对其吸附有机污染物性能的影响

以溴化十六烷基三甲铵为改性剂，对天然钙基膨润土进行有机化改性，系统地研究了改性剂用量以及钠化，热活化和酸活化对有机膨润土吸附苯酚、苯胺、苯、甲苯和二甲苯的影响，并初步探讨了有机膨润土与有机物间的作用机理。实验结果表明，改进剂用量是影响有机膨润土对有机物吸附性能的主要因素；改性剂用量相同时，钠化土的吸附效果明显好于直接改性的6.0%土，而热活化和酸活化对于有机膨润土吸附不同的有机物时影响程度也不同。应用有机膨润土建造垃圾填埋场防渗衬层具有一定的可行性。     

胶束电动毛细管色谱法测定海底表层沉积物中的苯系化合物

用胶束电动毛细管色谱法对海底表层沉积物中的苯系化合物进行了分析测定。采用57cm×50μm毛细管柱，以50mmol/L十二烷基硫酸钠-2.0mmol/L四硼酸钠溶液（pH9.16）作为操作缓冲溶液，并加入φ=20%的甲醇作为有机改性剂，电压25kV，检测波长200nm，15min内苯、甲苯、乙苯和二甲苯可获得良好的分离。用峰面积定量，线性范围为2～100mg/L，最小检测浓度分别为0.75mg/L苯，0.45mg/L甲苯，0.39mg/L乙苯，0.1mg/L邻-二甲苯，0.31mg/L对-二甲苯。将该法用来分析石油勘探远景区域海底表层沉积物中的苯系化合物，检测浓度范围为(0.0x～0.x)μg/g。     

Ground-Based and Airborne Measurements of Nonmethane Hydrocarbons in BERLIOZ: Analysis and Selected Results

During the Berlin Ozone Experiment BERLIOZ in July–August 1998 quasi-continuous measurements ofC₂–C₁₂ nonmethane hydrocarbons (NMHCs) were carried out at 10 sites in and around the city of Berlin using on-line gas-chromatographic systems (GCs) with a temporal resolution of 20–120 minutes. Additional airborne NMHCmeasurements were made using canister sampling on three aircraft and an on-line GC system on a fourth aircraft. The ground based data are analyzed to characterize the different sites and to identify the influence of emissions from Berlin on its surroundings. Benzene mixing ratios at the 4 rural sites were rather low (<0.5 ppbv). Berlin (and the surrounding highway ring) was identified as the main source of anthropogenic NMHCs at Eichstädt and Blossin, whilst other sources were important at the furthermost site Menz. The median toluene/benzene concentration ratio in Berlin was 2.3 ppbv/ppbv, agreeing well with measurements in other German cities. As expected, the ratios at the background sites decreased with increasing distance to Berlin and were usually around one or below. On 20 and 21 July, the three northwesterly sites were situated downwind of Berlin and thus were influenced by its emissions. Considering the distance between the sites and the windspeed, the city plume was observed at reasonable time scales, showing decreasing toluene/benzene ratios of 2.3, 1.6 and 1.3 with increasing distance from Berlin. Isoprene was the only biogenic NMHC measured at BERLIOZ. It was themost abundant compound at the background sites on the hotter days, dominating the local NMHC reactivity with averaged contributions to the total OH loss rate of 51% and 70% at Pabstthum and Blossin, respectively. Emissionratios (relative to CO and to the sum of analysed NMHCs) were derived from airborne measurements. The comparison with an emission inventory suggests traffic-related emissions to be the predominating source of the considered hydrocarbon species. Problems were identified with the emission inventory for propane, ethene and pentanes.     

Determination of selected atmospheric aromatic hydrocarbons at remote continental and oceanic locations using photoionization/flame-ionization detection

A new gas chromatographic technique with a modified photoionization detector connected in series with a conventional flame ionization detector was used to determine low concentrations of atmospheric hydrocarbons in remote atmospheres. Average mixing ratios of five aromatic hydrocarbons measured between 42°N and 30°S latitude in the Pacific Ocean in October/November 1983 were highest in the Northern Hemisphere. The average mixing ratios in the northern and southern marine atmospheres were 49±25 ppt (n=35) and 10±2 ppt (n=21) for benzene, 20±12 ppt (n=32) and 5.6±1.6 ppt (n=12) for toluene, 7.6±3.7 ppt (n=35) and 3.7±1.6 ppt (n=21) for ethylbenzene, 25±12 ppt (n=35) and 13±5 ppt (n=20) for the sum of m- and p-xylenes, and 14±6 ppt (n=35) and 6.6±3.0 ppt (n=21) for o-xylene, respectively. The first latitudinal gradients for these five aromatic compounds are reported. Benzene and toluene mixing ratios measured between July 1982 and October 1983 at a rural, mid-latitude continental site in eastern Washington state gave average values of 226±108 ppt and 133±84 ppt, respectively, with higher wintertime than summertime benzene levels. These continental samples gave calculated air mass ages averaging six days based on benzene-to-toluene ratios.     

海水中苯系物的衰减及其微生物降解的贡献

以海水中7种苯系物为研究目标,利用吹扫捕集-气相色谱质谱分析方法准确测定海水中苯系物的含量,研究不同环境条件下海水中苯系物的挥发、降解等衰减过程,探讨海洋微生物对苯系物降解贡献率。结果表明,7种苯系物性质相似,在不同保存条件下,海水中苯系物各组分浓度随时间的变化规律基本一致。海水中苯系物的衰减过程受温度影响明显,室温23°C条件下比低温4°C条件下海水中苯系物衰减更快,低温4°C时苯系物衰减完毕时间约125h,而室温23°C时则为24h。天然海水中间二甲苯、邻二甲苯相对更容易挥发或降解,而苯乙烯、苯则相对滞后。敞口保存下天然海水中苯系物浓度的降低更多是挥发造成的,微生物降解贡献率相对较小;密封保存下以微生物厌氧降解为主,其对苯系物降解贡献率明显高于敞口保存,累计可达83%,室温23°C下微生物降解苯系物时间更短,但低温4°C下微生物降解苯系物更完全。在适宜的温度和密封条件下天然海水中微生物降解对于海水中苯系物的去除将起到更加重要的作用。     

苯和甲苯在土壤中的吸附行为研究

选取某采油厂不同有机碳含量的表层土壤作为吸附剂,采用批实验方法对原油中代表性组分苯和甲苯的单组分吸附和双组分竞争吸附行为进行了研究。研究表明,单组分溶液中,苯和甲苯在土壤中的吸附符合线性规律,吸附能力与土壤有机碳含量成正比;双组分溶液中,苯和甲苯共存时存在竞争吸附,土壤对它们的吸附小于单组分时的情况。竞争吸附的结果说明,除分配吸附以外,介质表面点位对苯和甲苯的吸附也起着重要的作用。     

Irreversible sorption of benzene in sandy aquifer materials

Hydrocarbon compounds in aquifers are generally known to show a retardation effect due to sorption onto the surfaces of solid particles. In this study, we investigated the effect of sorption on the transport of benzene in sandy aquifer materials by conducting batch and column tests for both sandy aquifer materials and sandy materials to which had been added 0·5% powdered activated carbon. The batch test was conducted by equilibrating dry materials with benzene solutions of various initial concentrations, and by analysing the concentrations of benzene in the initial and equilibrated solutions using high‐performance liquid chromatography (HPLC). The column test was performed to monitor the concentrations of effluent versus time, known as a breakthrough curve (BTC). We injected KCl and benzene solutions as tracers into the inlet boundary as two different types of square pulse and step, and monitored the effluent concentrations at the exit boundary under a steady‐state condition using an electrical conductivity meter and HPLC. Simulation of benzene transport was performed using the convective–dispersive equation model with the distribution coefficients obtained from the batch test and the transport parameters of the conservative solute KCl from the column test. The observed BTCs of KCl and benzene for pulse injection showed that the arrival times of the peaks of both tracers coincided well, but the relative peak concentration of benzene was much lower than that of KCl. Comparison of the simulated and observed BTCs showed a great discrepancy for all cases of injection mode and material texture, indicating the absence of retardation effect. These results reveal that the predominant process affecting the benzene transport in the sandy aquifer materials is an irreversible sorption rather than retardation. This tentative conclusion was verified by simulation of benzene transport using an irreversible sorption parameter that led to a good agreement between the simulated and observed BTCs. Copyright © 2002 John Wiley & Sons, Ltd.     

DETERMINATION OF TRACE BENZENE HYDROCARBONS IN JIAOZHOU BAY BY ENRICHMENT AND CAPILLARY COLUMN GAS CHROMATOGRAPHY

Trare amounts of benzene hydrocarbons obtained in Jiaozhou Bay (Qindao) were enriched bysorption on a GDX-102 column and eluted by carbon disulfide. The eluted was concenttaled and then de-temened by capillary column gas cbornatognphy.The contents of virious kinds of benzene hydrocarbons in Jiaozhou Bay coastal water were benzene(22.3-141.6)× 10～(-9)g/L, toluate (15.2-94.0) × 10~(-9) g/L, ethyl benzene(11.8-85.1)×10~(-9) g/L, p -xylene(15.2-78.5) ×10(-9) g/L, m-xylene (10.9-79.4) ×10(-9) g/L, o -xylene (12.4-80.1) x ×10(-9)g/L; iso-propyl(8.4- 73.1) x ×10(-9)g/L, n -propyl (6.9-76.4) ×10(-9) g/L, 1, 3, 5-trimethylbenzene (10.9- 35.9)×10(-9) g/L, 1,2, 4-trimethybenzene (10.0- 38.0)×10(-9) g/L, n - butydriare (8. 1 - 34.6) ×10(-9)g/L. The recovery of benzenehydrocarbons was (85.1 -95.6)%.