Contamination Levels and Preliminary Assessment of the Technical Feasibility of Employing Natural Attenuation in 5 Priority Areas of Presidente Bernardes Refinery in Cubatão, São Paulo, Brazil

Five priority areas of potential impact by contaminants (API) were investigated at the Presidente Bernardes Refinery in Cubatão, São Paulo, Brazil with the following aims: (i) to identify both organic and inorganic contaminants present in soil and groundwater; (ii) to define the environmental conditions relevant for microbial activity at the site and (iii) to evaluate the feasibility of employing natural attenuation for treatment of the hydrocarbon contamination. One area (API 1) was an uncontrolled landfill, where waste materials from the refinery were deposited between 1954 and 1986, and four areas (API 4, 5, 7 and 11) were located in the operational section of the refinery. Soil contamination by regulated BTEX compounds (benzene, toluene, total xylenes) was restricted to two samples from API 1. Nonregulated ethylbenzene was detected in one soil sample from API 4, one from API 5 and two from API 1. No soil contained regulated PAH above threshold levels. Several nonregulated PAHs were found in 6 soil samples from API 1, 3 soil samples from API 4 and 1 soil sample from API 5. Site soils contained very high aluminium concentrations, but metal contamination was restricted to one soil sample from API 1, which contained nickel above threshold limits. BTEX contamination of groundwater was due mostly to benzene. Of the 17 PAH molecules tested, only naphthalene and 2-methylnaphthalene occurred in groundwater. The sum of total BTEX and total PAH exceeded 200 μg/L in only a few monitoring wells in API 4, 5 and 11 and was always below 2.640 μg/L. Be, Cd, Cr, Cu, Hg, Ni, Se, Ag, Tl and Zn were not detected in groundwater, which was contaminated in a few locations by aluminium (mostly below 1 mg/L), lead (<0.066 mg/L) and arsenic (<0.056 mg/L). S, K, Ca, Mg and Fe were present in groundwater in excess of physiological requirements for microbial growth, but low concentrations of N and P could become growth limiting. However, BTEX were efficiently degraded in saturated and unsaturated zone microcosms and nutrient amendments did not stimulate biodegradation rates measurably. The inorganic carbon pool in groundwater was up to one order of magnitude larger than the organic carbon pool. Total inorganic carbon (TIC) in API groundwater exceeded TIC of clean groundwater by factors of 2 (API 4), 6 (API 5, 7 and 11) or 10 (API 1). Most of the inorganic carbon incorporated into groundwater beneath the refinery originated from biodegradation in the unsaturated soil, which contained a microbiota (10⁶ cells/g on average) capable of growth with most of the pure (benzene, toluene, ethylbenzene and xylene) and mixed hydrocarbons tested (diesel oil, gasoline, naphtha, condensate, aromatic residue and fuel oil). A viscous hydrocarbon paste uncovered in API 1 was insoluble in water but dissolved in dichloromethane. Many organic components of this paste were biodegradable as evidenced by weight reduction of the hydrocarbon paste and by the growth of suspended and attached biomass in saturated zone microcosms, where the paste was the only carbon source. This study indicates that monitored natural attenuation may be a technically feasible and efficient means for plume control in API 1, 4 and 5, provided the plumes in API 4 and 5 are not expanding. This technique is not suitable for contaminant reduction in API 11.     

On-line CO, CO2 emissions evaluation and (benzene, toluene, xylene) determination from experimental burn of tropical biomass

Atmospheric pollution and global warming issues are increasingly becoming major environmental concerns. Fire is one of the significant sources of pollutant gases released into the atmosphere; and tropical biomass fires, which are of particular interest in this study, contribute greatly to the global budget of CO and CO₂. This pioneer research simulates the natural biomass burning strategy in Malaysia using an experimental burning facility. The investigation was conducted on the emissions (CO₂, CO, and Benzene, Toluene, Ethylbenzene, Xylenes (BTEX)) from ten tropical biomass species. The selected species represent the major tropical forests that are frequently subjected to dry forest fire incidents. An experimental burning facility equipped with an on-line gas analyzer was employed to determine the burning emissions. The major emission factors were found to vary among the species, and the specific results were as follows. The moisture content of a particular biomass greatly influenced its emission pattern. The smoke analysis results revealed the existence of BTEX, which were sampled from a combustion chamber by enrichment traps aided with a universal gas sampler. The BTEX were determined by organic solvent extraction followed by GC/MS quantification, the results of which suggested that the biomass burning emission factor contributed significant amounts of benzene, toluene, and m,p-xylene. The modified combustion efficiency (MCE) changed in response to changes in the sample moisture content. Therefore, this study concluded that the emission of some pollutants mainly depends on the burning phase and sample moisture content of the biomass.     

Co-adsorption of gaseous benzene, toluene, ethylbenzene, m-xylene (BTEX) and SO2 on recyclable Fe3O4 nanoparticles at 0-101% relative humidities

We herein used Fe3O4 nanoparticles(NPs) as an adsorption interface for the concurrent removal of gaseous benzene, toluene, ethylbenzene and m-xylene(BTEX) and sulfur dioxide(SO2), at different relative humidities(RH). X-ray diffraction, Brunauer–Emmett–Teller, and transmission electron microscopy were deployed for nanoparticle surface characterization.Mono-dispersed Fe3O4(Fe2O3·Fe O) NPs synthesized with oleic acid(OA) as surfactant, and uncoated poly-dispersed Fe3O4 NPs demonstrated comparable removal efficiencies.Adsorption experiments of BTEX on NPs were measured using gas chromatography equipped with flame ionization detection, which indicated high removal efficiencies(up to(95 ± 2)%) under dry conditions. The humidity effect and competitive adsorption were investigated using toluene as a model compound. It was observed that the removal efficiencies decreased as a function of the increase in RH, yet, under our experimental conditions, we observed(40 ± 4)% toluene removal at supersaturation for Fe3O4 NPs, and toluene removal of(83 ± 4)% to(59 ± 6)%, for OA-Fe3O4 NPs. In the presence of SO2, the toluene uptake was reduced under dry conditions to(89 ± 2)% and(75 ± 1)% for the uncoated and coated NPs, respectively, depicting competitive adsorption. At RH 100%,competitive adsorption reduced the removal efficiency to(27 ± 1)% for uncoated NPs whereas OA-Fe3O4 NPs exhibited moderate efficiency loss of(55 ± 2)% at supersaturation.Results point to heterogeneous water coverage on the NP surface. The magnetic property of magnetite facilitated the recovery of both types of NPs, without the loss in efficiency when recycled and reused.     

苯系物对仿刺参catalase基因表达及酶活性的影响

以仿刺参(Apostichopus japonicus)为受试生物,采用半静水式试验方法,设置3种不同浓度(1/5、1/25、1/125的96 h-LC50)的苯、甲苯、乙基苯、邻–二甲苯、间–二甲苯和对–二甲苯处理健康仿刺参,检测仿刺参过氧化氢酶(CAT)基因在呼吸树、肠组织中的表达和酶活性变化情况。结果发现:在各苯系物处理组的仿刺参呼吸树和肠组织中,cat基因的转录表达变化显著;苯、甲苯、乙基苯、邻–二甲苯对呼吸树中CAT活性具有诱导作用,其中乙基苯的诱导倍数最高,为12.0~19.8倍;6种苯系物对肠组织中CAT活性具有抑制作用,抑制程度大小顺序为:邻–二甲苯乙基苯对–二甲苯甲苯间–二甲苯苯。表明苯系物对仿刺参呼吸树、肠具有氧化胁迫作用,可能造成2种组织的氧化损伤。相关性分析表明:苯系物处理后,仿刺参肠组织中cat m RNA相对表达倍数与CAT活性变化呈显著正相关;仿刺参肠和呼吸树中cat m RNA相对表达倍数变化呈显著正相关。以上结果为苯系物对仿刺参的生物毒性评价提供了基础数据。     

河流渗滤系统中苯系物污染去除机理实验模拟研究

河流渗滤是一种自然净化过程，污染河水通过该过程在河流沉积层中发生各种物理、化学和生物作用，使得污染物浓度降低，河水水质得到净化，从而达到增加地下水开采量的目的。通过静态吸附实验和淋滤实验模拟了苯系物（BTEX）在河流渗滤系统中的吸附行为和降解行为。两种环境行为中吸附作用对于BTEX的净化效果较为有限，当吸附达到饱和之后，并存在电子受体的情况下，BTEX能够发生厌氧微生物降解，降解作用能够更有效的去除BTEX污染物。其中去除效率最高的是间二甲苯，其次是乙苯、甲苯，去除率最差的是苯。微生物降解作用相对于BTEX浓度变化存在一个滞后期。BTEX各组分的土壤 水吸附分配系数Kd越大，总的降解效率也就越低。通过河流渗滤系统这一自然净化过程，可以有效地去除浓度较高的BTEX混合污染，在两种电子受体的情况下各组分平均去除效率都超过了60%，最高去除率均超过了80%。对于持续不断入渗的污染河水，当土壤吸附达到饱和、微生物活性受到抑制情况下，去除效率会大大降低，从而使BTEX穿透包气带进入含水层，对地下水产生危害     

东北地区大气BTEX的时空分布特征

在东北地区7个典型城市中25个监测点进行了观测,时间分别为2008年4月、7月、10月和2009年1月,使用吸附剂采样管采集并通过热脱附-气相色谱-质谱联用技术分析了苯系物样品,系统研究了东北地区大气苯系物的时空分布特征。研究结果表明,苯和甲苯年均浓度值最高,分别为(4.19±2.31)μg/m3和(3.22±1.14)μg/m3,共占苯系物浓度近70%;各功能区按苯系物浓度大小顺序排列为混合区工业区交通区居民区文教区对照区;受排放源和气象条件的影响,采暖期苯系物浓度高于非采暖期苯系物浓度;风向频率影响苯系物浓度分布,沿下风向浓度逐渐降低;苯/甲苯比值分析表明,东北地区苯系物的主要来源是煤燃烧。     

Construction and comparison of fluorescence and bioluminescence bacterial biosensors for the detection of bioavailable toluene and related compounds

Environmental pollution with petroleum products such as benzene, toluene, ethylbenzene, and xylenes (BTEX) has garnered increasing awareness because of its serious consequences for human health and the environment. We have constructed toluene bacterial biosensors comprised of two reporter genes, gfp and luxCDABE, characterized by green fluorescence and luminescence, respectively, and compared their abilities to detect bioavailable toluene and related compounds. The bacterial luminescence biosensor allowed faster and more-sensitive detection of toluene; the fluorescence biosensor strain was much more stable and thus more applicable for long-term exposure. Both luminescence and fluorescence biosensors were field-tested to measure the relative bioavailability of BTEX in contaminated groundwater and soil samples. The estimated BTEX concentrations determined by the luminescence and fluorescence bacterial biosensors were closely comparable to each other. Our results demonstrate that both bacterial luminescence and fluorescence biosensors are useful in determining the presence and the bioavailable fractions of BTEX in the environment.     

污水处理过程中BTEX迁移降解与去除途径研究

以某涂料废水为研究对象，采用实验检测废水中BTEX浓度和模式计算挥发量相结合的研究方法，对BTEX污染物在污水处理过程中的迁移降解与去除途径进行研究，分析隔油、气浮、氧化沟工艺对苯系物去除效果，同时研究了吸附、挥发和生物降解3大去除途径对苯系物去除的影响。研究表明，该工艺对BTEX的去除效率高，苯的总去除效率为88.11%，甲苯、乙苯、邻二甲苯和间、对二甲苯总去除率分别高达98.14%、98.09%、97.45%和97.68%。其中苯、甲苯、乙苯、邻二甲苯主要都是在氧化沟中去除，间、对二甲苯在气浮池和氧化沟都有较高的去除率，隔油池工艺对BTEX的去除率较低。去除途径方面，苯以挥发为主，甲苯、乙苯和邻二甲苯都以生物降解为主要去除途径，而挥发和生物降解对间、对二甲苯的去除作用相当。     

车辆限行前后奥运场馆附近空气中苯系物污染特征与来源

在"好运北京"体育赛事车辆限行前后对北京奥运场馆,即四环路健翔桥附近空气中的6种苯系物进行了连续监测。监测结果显示,被测空气的苯系物中甲苯所占比例最大,为32.1%~42.5%,限行后总苯系物平均质量浓度降低了近47%。车辆限行前后,苯系物呈现类似的日变化规律,在交通早、晚高峰时出现峰值。限行前苯系物处于累积状态,日最高值出现在18点,限行后苯系物处于扩散状态,日最高值出现在8点。苯系物来源解析表明,整个交通管制期间苯/甲苯浓度的比值为0.49~0.55,且各苯系物具有良好的相关性,证明被测空气中苯系物具有良好的同源性,均来自汽车尾气。限制车流量可有效降低空气中苯系物浓度。     

不同动力公交流动微环境BTEX的浓度水平及健康风险

用热解析气相色谱法采集分析不同动力公交车微环境中苯系物,研究了江南某旅游城市公交汽油车、柴油车、电车、液化天然气车、油电混合车空气中苯系物的浓度以及主要公交站台的苯系物的浓度。结果表明,公交车微环境中苯系物平均浓度从高到低依次为汽油车>柴油车>油电混合车>液化天然气车>电车,其中汽油车苯含量最高,为(21.02±9.51)μg/m3,各动力公交车的苯暴露对公交司机致癌风险为2.32×10-6～4.79×10-6,超过了美国EPA制定的人体致癌风险限值。