Investigation of Mtbe and Aromatic Compound Concentrations at a Gas Service Station

Methyl tert-butyl ether (MTBE) has been used as a fuel additive at levels of 2–11% in Taiwan for the past decade. The purpose of this additive is to enhance the octane, replace the use of lead-based anti-knock gasoline additives and reduce aromatic hydrocarbons. However, it is possible that oxygenated fuel has a potential health impact. To determine the air quality impact of MTBE, measurements were made of ambient MTBE and other gasoline constituents at a service station. Additionally, environmental conditions (wind speed, wind direction, and temperature, etc.) that could affect concentrations of emission constituents were measured. Gas samples were analyzed for target MTBE and volatile organic compounds, e.g., benzene and toluene. Ambient samples were collected using Tenax adsorbent tubes for mass spectrometric analysis at a service station located in Changhua County, Taiwan. The resulting measured ambient air concentrations were compared with Taiwans regulatory standards for hazardous air pollutants. Subsequently, the factors controlling the formation of high-VOC levels at the service station and in the residential neighborhoods were identified. Additionally, the results can provide the Environmental Protection Agency (EPA) of Taiwan with useful information and prompt them to mandate this gas service station to install a refueling vapor recovery system.     

Development and validation of a thermally regulated atmospheric simulation chamber (THALAMOS): A versatile tool to simulate atmospheric processes

Atmospheric simulation chambers, are unique tools for investigating atmospheric processes in the gas and heterogeneous phases. They can provide a controlled yet realistic environment that simulates atmospheric conditions. In the current study, a Teflon atmospheric simulation chamber of 600 L, named THALAMOS (thermally regulated atmospheric simulation chamber) has been developed and cross-validated. THALAMOS can be operated over the temperature range 233 to 373 K under both static and flow conditions. It is equipped with state of the art instrumentation (selective ion flow tube mass spectrometry (SIFT-MS), long path Fourier transform infrared spectroscopy (FTIR), gas chromatography-mass spectrometry (GC-MS), various analyzers) for the in-line monitoring of both reactants and products. THALAMOS was validated by measuring the rate coefficients of well documented reactions, i.e. the reaction of ethanol with OH radicals and the reaction of dichloromethane with Cl atoms, in a wide temperature range. Two different detection techniques were used in parallel, FTIR and SIFT-MS, to internally cross-validate the obtained results. The measured rate coefficients are in excellent agreement, both between each other and with the literature recommended values. Furthermore, the gas phase oxidation of toluene by Cl atoms (kinetics and product yields) was studied in the temperature range of 253 to 333 K. To the best of our knowledge, THALAMOS is a unique facility on national level and among a few smog chambers internationally that can be operated in such a wide temperature range providing the scientific community with a versatile tool to simulate both outdoor and indoor physicochemical processes.     

Trace analysis of airborne toluene diisocyanate as a pentafluorobenzyl derivative by gas chromatography with electron capture detection

Trace analysis of airborne toluene diisocyanate (TDI) vapor was accomplished by measuring the derivative using gas chromatography with electron‐capture detector after collecting gas samples with a microimpinger containing 2 ml toluene, 1 μl pentafluorobenzyl alcohol, and 1 μl triethylamine. The sampling efficiency was determined to be 99.4% for short‐term exposure level of TDI and the 2,4‐ and 2,6‐isomers of TDI were well separated. The derivative was identified to be a new compound with a molecular weight of 570 by mass spectrometry in fast atomic bombardment mode and nuclear magnetic resonance spectrometry. This method is convenient and can be applied in the field where airborne TDI is in vapor form.     

间歇喷淋营养液对生物滴滤塔净化甲苯的影响

为探索间歇喷淋营养液对生物滴滤塔的影响,以净化甲苯为研究对象,应用FX1N-14MR-001型可编程逻辑控制器(PLC),实现生物滴滤塔的间歇喷淋营养液操作,研究了环境温度、ρ(TN)、营养液喷淋密度和喷/停时间对净化甲苯能力的影响,并对机理进行了分析. 结果表明:当生物滴滤塔系统的气体停留时间为40.70s时,营养液最佳喷淋密度为4.5L/(m2·min),最佳喷/停时间为2min/4min. 当甲苯系统进口负荷小于88.29g/(m3·h)时,甲苯的去除率可达95.0%以上;当进口负荷为186.04g/(m3·h)时,甲苯的去除率为87.6%,系统对甲苯的最大去除能力由连续喷淋时的169.63g/(m3·h)升至248.85g/(m3·h).      

复配表面活性剂水溶液处理甲苯气体的研究

以非离子表面活性剂吐温-20(Tween-20)为主表面活性剂,添加助表面活性剂十二烷基苯磺酸钠(SDBS)以及助剂氯化钠,形成复配水溶液吸收剂处理VOCs废气.以甲苯为VOCs的典型代表,研究了Tween-20,Tween-20/SDBS和Tween-20/SDBS/氯化钠3种水溶液吸收剂的临界胶束浓度(CMC)及其对甲苯去除率的影响.结果表明,当表面活性剂浓度达到CMC时,水溶液对甲苯的吸收效果开始明显增强,加入助表面活性剂SDBS和助剂氯化钠有利于甲苯的去除,同时可降低溶液的CMC,减少表面活性剂的用量,降低水溶液吸收法处理VOCs成本.当空气流量G为300mL/min、液体喷淋量L为75mL/min、进口甲苯浓度800mg/m3、温度T为30℃时,分别以Tween-20、Tween-20/SDBS(摩尔比1/4)和Tween-20/SDBS/氯化钠(摩尔比1/4/0.1)的水溶液为吸收剂,且浓度均为1CMC时,甲苯去除率分别为56%、70%和77%,三元复配表面活性剂水溶液的吸收效果最佳.     

水体甲苯、乙苯和二甲苯对斑马鱼的毒性效应

以斑马鱼(Brachydanio rerio)为实验生物,采用半静态实验方法,研究了甲苯、乙苯和二甲苯的水生生态毒性效应.研究表明,水体中甲苯、乙苯和二甲苯对斑马鱼96h半致死浓度LC50分别为77.5、31.0和34.8mg·L-1,根据化学物质对鱼类毒性分级标准,3种物质均属中等毒性,其毒性大小顺序为:乙苯>二甲苯>甲苯.在最高暴露浓度下,斑马鱼均出现了剧烈、无序游动,并伴有抽搐等现象,其中暴露在甲苯中的斑马鱼行为改变更为严重.分析认为,3种物质对斑马鱼毒性大小与疏/亲水性有关,疏水性越强,对水生生物的毒性作用越大.     

易挥发有毒化合物催化燃烧试验

在富氧条件下以2.0% Ru/Al₂O₃和2.0% Ru/AC(AC为活性炭)为催化剂,在固定床反应装置上研究了甲醇、氨、甲苯的催化氧化活性及反应动力学. 结果表明,Ru/Al₂O₃对3种反应物的催化活性比Ru/AC高,3种反应物的反应活性顺序为甲醇>氨>甲苯,其去除率随反应物浓度的增加呈先增大后减小的趋势. 反应的活化能(Ea)测定结果为甲醇<氨<甲苯. 比表面积检测(BET)和透射电镜(TEM)结果显示,Ru/Al₂O₃与Ru/AC的孔体积(0.54 mL/g)近似相等,而其孔径分别为9.3和2.3 nm;在大孔径的氧化铝上Ru以极细的粒径(<3 nm)形成高度分散体系,在活性炭上Ru则以较大颗粒(4～10 nm)位于活性炭表面,Ru的粒径细化及形成高分散体系可能是Ru/Al₂O₃的催化活性高于Ru/AC的主要原因.      

阳离子表面活性剂对甲苯与水间气-液平衡关系的影响

为探明表面活性剂对水体中挥发性有机物挥发作用的影响,采用顶空气相色谱法并通过改变相比,研究了甲苯与氯代十六烷基吡啶(CPC)溶液间的气-液平衡关系. 结果表明:体系达到平衡后甲苯气相浓度(峰面积)与相比具有良好的线性关系,且二者间的线性关系可通过方程1/ApR_f/H_iC_io+R_f/Cio(V_g/V_L)进行拟合并得到亨利系数值.溶液中CPC浓度的变化对甲苯的亨利系数有明显影响,平衡体系的亨利系数值随着CPC浓度的增大而减小;当CPC浓度小于临界胶束浓度(CMC)时,CPC浓度的增加对亨利系数的影响不明显;当CPC浓度在CMC以上时,随着CPC浓度的增加亨利系数减小趋势明显.温度对亨利系数有显著影响,亨利系数随温度的升高而增大,且二者间存在良好的线性关系,并可通过Van’t Hoff方程进行拟合.      

气相中甲苯的臭氧-光催化降解

初步研究了气相中中低浓度(10～80mg/m³)甲苯的臭氧-光催化联合降解,考察甲苯初始浓度、气体流量和湿度对降解效率及去除负荷的影响,并与单一光催化降解进行了比较.结果表明,臭氧-光催化对甲苯的降解效率大大高于光催化的降解效率,在较高浓度时效果更为显著;甲苯浓度在10～40mg/m³范围时,臭氧-光催化降解效率高达90%以上,但随甲苯初始浓度升高而缓慢地线性下降;湿度对甲苯的臭氧-光催化降解稍有影响,但去除率变化不超过2.5%.     

土壤甲苯、乙苯和二甲苯对蚯蚓及小麦的毒性效应

以赤子爱胜蚓(Eisenia fetida)和小麦(Triticum aestivum L.)为受试生物,研究了土壤中甲苯、乙苯和二甲苯等苯系物(TEX)的毒性效应.结果表明,3种污染物对赤子爱胜蚓和小麦毒性影响呈明显的剂量-效应关系,甲苯、乙苯和二甲苯对蚯蚓的24hLC50分别为583.6,346.8,192.4mg/kg;48h LC50分别为454.3,167.1,127.2mg/kg.甲苯、乙苯和二甲苯对小麦芽伸长的10%抑制率(IC10)分别为342.2,195.4,45.9mg/kg;对小麦根伸长的10%抑制率(IC10)分别为206.7,134.5,26.3mg/kg.小麦芽长、根长均可用于指示土壤被甲苯、乙苯及二甲苯污染的程度,但小麦种子根长对3种污染物胁迫的响应较芽长更为敏感,根长抑制率与芽长抑制率之间呈明显的相关关系.