β-Proteobacteria菌降解甲基叔丁基醚的条件及中间代谢产物研究

采用可利用甲基叔丁基醚(methyl tert-butyl ether,MTBE)为唯一碳源和能源生长的1株β-Proteobacteria菌进行MTBE在密闭系统中的降解试验,确定了该菌降解MTBE的最适条件为:培养液初始pH值7.2,初始细胞浓度10⁷cells/mL,初始MTBE浓度为25 mg/L.考察了密封培养系统内培养液溶解氧对降解效果的影响,结果表明,在培养系统密闭前充入氧气可提高菌体对MTBE的降解速率.以气相色谱-质谱联用法检测到MTBE降解主要中间代谢产物是叔丁基醇、异丙醇、丙酮.在选择离子扫描模式下定量分析,得到降解过程中主要中间代谢产物的浓度变化曲线,据此推断MTBE的降解途径属于“丙酮途径”.     

Degradation of MTBE and TBA by a new isolate from MTBE-contaminated soil

Methyl ten-butyl ether （MTBE）, a gasoline additive, possesses serious problems to the environmental health. In the present study, a bacterial culture named A-3 which could effectively degrade MTBE was isolated from the MTBE contaminated soil. The isolate was identified as Chryseobacterium sp., a new species capable of degrading MTBE. In order to enhance its degradation ability, selected environment factors were investigated. The results showed that the optimal temperature was in the range of 25-30℃, the pH was 7.0, the inoculum size was 2 × 10^8 CFU/ml and the optimal concentration of MTBE was from 50 to 100 mg/L. The maximum MTBE utilization rate （Vmax） was 102 nmol MTBE/（mg cell protein.h）. Furthermore, it was found that the isolate could also degrade tert-butyl alcohol （TBA）. The degradation rates of TBA were much faster than those of MTBE. The additional TBA would lead to the decrease of the initial MTBE degradation rate and the inhibitory effect of TBA increased with the increase of TBA concentration. Similar protein profiles at least seven peptides were demonstrated after SDS-PAGE analysis of crude extracts obtained from the cells growing in MTBE and TBA culture.     

O3/H2O2法降解甲基叔丁基醚（MTBE）的试验研究

采用自制鼓泡反应器对臭氧/双氧水(O3/H2O2)降解水中甲基叔丁基醚(MTBE)进行了试验研究,考察了进气(含O3)流量、H2O2 投加量、MTBE初始浓度、pH、温度等因素对MTBE降解的影响.结果表明,在MTBE初始浓度为10 mg·L-1,气体流量为0.5 L·min-1,温度293K, pH=6.5, H2O2 添加量为2.4mg·L1 条件下,反应30 min后, MTBE去除率可达75.5%, COD去除率为68.0%.降解得到的中间产物主要有叔丁基甲酯(TBF)、叔丁醇(TBA)、乙酸甲酯(MA)和丙酮(AC)等,据此探讨了O3/H2O2氧化MTBE的可能反应机理和降解途径.     

甲基叔丁基醚(MTBE)的环境毒理学研究进展

甲基叔丁基醚(MTBE)作为一种新型的无铅汽油添加剂被广泛应用以减少含铅汽油对空气的污染。简要介绍了MTBE的理化性质和MTBE的急性毒性、代谢、生殖、遗传毒性,就其对环境的污染以及其防治作了综述,指出了我国开展MTBE有关研究的重要性。     

Sensitivity of green and blue-green algae to methyl tert-butyl ether (MTBE) during a fifteen-day test

The test was designed to assess the toxicity of methyl tert-butyl ether (MTBE) to Chlorella ellipsoidea and Aphanizomenon flos-aquae during 15 d with concentrations of MTBE from high (2.00×104 mg/L) to low (2 mg/L). The results showed that the toxicity was low when the concentration of MTBE was 1.00×104-2.00×104 mg/L (the greatest inhibition of growth-rate was 70%-71%, occurring on day 1-5). Low concentrations (2-500 mg/L) stimulated algal growth up to the greatest effect of 85%-200% when the concentration of MTBE was 50-100 mg/L on day 3-5. The low concentrations may lead to an algal bloom owing to overabundance, which represents an aquatic ecological risk. However, the stimulatory effect occurred only during the day 1-5 and disappeared gradually during the day 13-15. The toxicity of MTBE (72-120 h EC50) is 6.65×103-9.58×103 mg/L for C. ellipsoidea and that is 1.14×104-2.00×104 mg/L for A. spiroides. We found that the toxicity and ecological risk of MTBE for the algal community structure were low. The toxicity was influenced by the duration of the test. We suggest that the duration of the test should not be shorter than half a life-cycle.     

乙醇共代谢降解MTBE好氧颗粒化的实验研究

以絮状活性污泥为接种污泥,乙醇为共代谢基质,通过逐步缩短沉降时间、洗脱沉降性能较差的絮状污泥,在SBR中成功地培养出降解MTBE的好氧颗粒污泥。成熟的好氧颗粒污泥平均粒径为400.5μm,SVI 41.39mL/g,MLVSS 2896mg/L,颗粒表面分布有丰富的球菌、短杆菌及少量丝状菌。好氧污泥实现颗粒化后,反应器进水MTBE浓度为300mg/L时,其出水浓度可维持在10mg/L以下,去除效率高达90%以上(其中挥发部分约占15%)。好氧污泥颗粒化后MTBE的降解速率也明显增加,相比启动初期,一个运行周期内MTBE的降解速率可提高4倍。一个运行周期内pH值的明显降低也表明了好氧颗粒污泥对MTBE的降解。     

Determination of methyl tert-butyl ether (MTBE) in Chinese fuels by gas chromatography/mass spectrometry and gas chromatography/flame ionization detector

A method was developed to determine the concentration of methyl tert-butyl ether(MTBE) in gasoline,diesel and heating oil by gas chromatography(GC) with mass spectrometry(GC-MS) or flame ionization detection(FID). The diluted gasoline was directly injected into the GC, and the complete separation of MTBE from co-eluting hydrocarbons was not required. GC/MS or GC/FID method can be used to analyze MTBE in different concentration range and have good consistency.     

Cost–benefit analysis of methyl tert-butyl ether and alternative gasoline formulations

This paper presents a cost–benefit analysis of the 1990 Clean Air Act Amendments (CAAA) requiring the addition of oxygen content in gasoline, using California as a case study. The valuation and comparison of costs and benefits for several fuel blends (with and without oxygen content) provides a framework to investigate cross-media (air, water, soil) tradeoffs. We use known valuation methods such as the travel cost method to derive recreational value, the averting expenditures approach and cost of illness approach to derive public health costs, and market price method to quantify increases in fuel price and fuel efficiency costs in order to compare the alternatives. We use data from California to evaluate the current fuel blend with methyl tert-butyl ether (MTBE), a fuel blend with ethanol (ethyl alcohol), and a fuel blend without oxygenated compounds. The most expensive option to meet the 1990 CAAA is the current reformulated gasoline blend with MTBE, which results in a net cost to California's economy of between $0.9 and 2.7 billion dollars annually. The cost of treating groundwater contaminated with MTBE is a major cost factor. Our assessment indicates that the non-oxygenated gasoline formulation is the most cost-effective, particularly in the long-term, once refiners are able to implement modifications to their installations or negotiate long-term supply contracts for these additives. Several strategies are identified to transition out of using the current gasoline blend with MTBE.     

吸附法处理甲基叔丁基醚污染物的研究进展

MTBE对地表水和地下水的污染已日益引起国内外的高度重视。对MTBE的性质、污染现状、处理技术及近年来国内外应用吸附法处理MTBE的研究进展作了一般综述,对分子筛、活性炭及吸附树脂这三种吸附剂对MTBE的吸附效果作了评述,对影响MTBE吸附效果的主要因素进行了讨论,并对吸附法处理MTBE的应用前景作了展望。     

甲基叔丁基醚对生态与环境的影响

汽油添加剂甲基叔丁基醚(MTBE)因能提高辛烷值、减少尾气污染物而被广泛使用.虽然MTBE对改善空气质量有积极意义,但因其泄漏并具有稳定性、迁移性和毒性,对水环境和人类造成危害.笔者综述了MTBE的毒性和对生态环境的影响,介绍了MTBE污染的防治现状,并对其研究方向进行了展望.      

珠江三角洲大气中甲基叔丁基醚的污染特征研究

应用先进的大气采样罐、大气样品预浓缩技术和气相色谱/质谱联用仪器,采取长期观测和加强观测方法详细地研究了珠江三角洲大气环境中MTBE的污染浓度水平及其时空分布特征.结果表明,①目前该地区的工业区、交通区以及居住、商业和交通混合区等大气环境中普遍能够检测出MTBE污染物,长期观测的小时浓度均值变化范围从0～1.250 μg·m^-3,夏季污染较冬季更为严重,高浓度的MTBE污染物主要集中在城区,郊区显著受到上风向城市和周边城市污染源排放的影响.②夏季加强观测期间,广州市区的日均浓度为(1.520±0.370) μg·m^-3,约为其下风向郊区花都测点的7倍和清洁区从化监测点的100倍.城区呈现早晚2个污染物浓度峰值,夜间为平均浓度最低值时段,而郊区夜间反而出现高浓度峰值.③冬季加强观测期间,广州市城区的日均浓度为(0.950±0.240) μg·m^-3,为其下风向郊区新垦测点的3.6倍,出现多个峰谷,城区在18:00～22:00点均具有较高的污染物浓度,郊区则在次日的04:00～10:00点具有相对较高的污染物浓度.④在光照比较弱的时段市区交通干线附近的大气MTBE浓度随着距地面高度增加而降低,而在光照比较强的时段则随着距地面高度增加反而有所上升,反映出市区近地面大气MTBE污染物除了主要来自机动车尾气排放之外,还有明显的大气光化学反应生成的二次污染物来源.     

颗粒活性炭吸附工艺对水体中甲基叔丁基醚的去除

通过批式平衡实验考察了各种材质活性炭对MTBE的最大吸附容量以及吸附的影响因素.结果表明各活性炭的吸附能力依次为JHBG1>JHBG2>GCN8303F300>YK>Bamboo,其中2种国产竹炭JHBG1和JHBG2对低浓度污染的地下水处理时的理论耗炭量分别为0.14和0.18g/L;水体中天然有机物对MTBE有一定的竞争吸附,丹宁酸值较大的活性炭比较有利于地下水中MTBE的去除.采用连续流的微型快速穿透实验(MCRB)考察了活性炭的吸附容量利用率,结果证明活性炭吸附可以作为一种有效的地下水中MTBE的去除工艺,这为MTBE污染场地的异位修复提供一个实际可行的参考.     

Rush-hour aromatic and chlorinated hydrocarbons in selected subway stations of Shanghai, China

Air samples were collected simultaneously at platform, mezzanine and outdoor in five typical stations of subway system in Shanghai, China using stainless steel canisters and analyzed by gas chromatography-mass selective detector (GC-MSD) after cryogenic preconcentration. Benzene, toluene, ethylbenzene and xylenes (BTEX) at the platforms and mezzanines inside the stations averaged (10.3 ± 2.1), (38.7 ± 9.0), (19.4 ± 10.1) and (30.0 ± 11.1) μg/m³, respectively; while trichloroethylene (TrCE), tetrachloroethylene (TeCE) and para-dichlorobenzene (pDCB), vinyl chloride and carbon tetrachloride were the most abundant chlorinated hydrocarbons inside the stations with average levels of (3.6 ± 1.3), (1.3 ± 0.5), (4.1 ± 1.1), (2.2 ± 1.1) and (1.2 ± 0.3) μg/m³, respectively. Mean levels of major aromatic and chlorinated hydrocarbons were higher indoor (platforms and mezzanines) than outdoor with average indoor/outdoor (I/O) ratios of 1.1-9.5, whereas no significant indoor/outdoor differences were found except for benzene and TrCE. The highly significant mutual correlations (p < 0.01) for BTEX between indoor and outdoor and their significant correlation (p < 0.05) with methyl tert-butyl ether (MTBE), a marker of traffic-related emission without other indoor and outdoor sources, indicated that BTEX were introduced into the subway stations from indoor/outdoor air exchange and traffic emission should be their dominant source. TrCE and pDCB were mainly from indoor emission and TeCE might have both indoor emission sources and contribution from outdoor air, especially in the mezzanines.     

Simultaneous catalytic removal of NOx and diesel PM over La0.9 K0.1 CoO3 catalyst assisted by plasma

The simultaneous removal of NOx and particulate matter(PM) from diesel exhaust is investigated over a mixed metal oxide catalyst of La0.9 K0.1 CoO3 loaded on γ-Al2O3 spherules with the assistant of plasma. It was found that NOx was reduced by PM in oxygen rich atmosphere, the CO2 and N2 were produced in the same temperature window without considering the N2 formed by plasma decomposition. As a result, the temperature for the PM combustion decreases and the reduction efficiency of NOx to N2 increases during the plasma process, which indicated that the activity of the catalyst can be improved by plasma. The NOx is decomposed by plasma at both low temperature and high temperature. Therefore, the whole efficiency of NOx conversion is enhanced.     

地下水循环井技术处理土壤和地下水中甲基叔丁基醚研究

研究了MTBE在砂土中的静态吸附以及采用地下水循环井技术(GCW)去除砂土和地下水中MTBE的衰减规律。结果表明:MTBE在砂土中的吸附动力学符合准二级动力学方程,相关系数R2为0.99618,在砂土中的吸附平衡时间为24 h;吸附热力学符合Linear平衡吸附,吸附系数为0.00306 m3/kg。GCW运行30 h后,地下水饱和含水层中MTBE浓度由500 mg/L降至72.5 mg/L,去除率为85.5%;砂土中MTBE的吸附量由0.93 mg/g降至0.03 mg/g,去除率达96.4%。水平方向距GCW越近,MTBE的去除效率越快,垂直方向位于GCW上部的MTBE优先会被去除,最佳修复时间为运行15 h。GCW对砂土和地下水中高浓度MTBE具有良好的修复效果。     

植物光合特性及其对湿地DO分布、净化效果的影响

为了研究人工湿地中植物的光合特性及其对湿地系统中溶解氧(DO)分布和污染物净化效果的影响,通过中试试验考察了芦苇、美人蕉、空心菜、富贵竹等几种典型湿地植物的光合作用特性及其与湿地DO分布、污染物去除效果之间的关系,藉此优选湿地植物,改善DO分布,强化脱氮效果.结果表明,植物净光合速率(Pn)对DO分布影响显著,湿地中段DO浓度高于两端,证明了植物对湿地系统存在供氧作用,其中芦苇产氧输氧能力最强,为湿地首选植物;此外,Pn还与湿地TN、NH4 -N去除效果显著相关.因此,可通过优选光合产氧输氧能力强的植物或采用适当增加种植密度等方式加强供氧以强化脱氮效果.     

吸附树脂/铁酞菁对甲基橙的光催化降解

针对铁酞菁在水溶液中易于聚合而降低催化活性,同时在均相光催化体系中分离困难、难以重复利用的问题,将铁酞菁负载在吸附树脂上,制得多相催化剂。该催化剂在可见光的照射下能有效地催化H2O2降解偶氮染料甲基橙。考察了催化剂用量、H2O2投加量、pH值、温度等因素对甲基橙去除效果的影响。结果表明,甲基橙初始浓度为50 mg/L,卤灯功率为100 W,催化剂投加量为1.0 g/L,H2O2用量为0.2 mol/L,pH为3,温度为35℃时,反应10 h,甲基橙去除率达到91%,且催化剂所含铁离子无流失,具有很好的稳定性,可重复使用。     

Sensitivity of green and blue-green algae to methyl tert-butyl ether

The toxicity of methyl tert-butyl ether (MTBE) to Chlorella ellipsoidea and Aphanizomenon flos-aquae was tested and assessed for a 15-d incubation with concentrations of MTBE from high (2.00×104 mg/L) to low (2 mg/L). The results showed that the toxicity was low when the concentration of MTBE was in the range 1.00×104-2.00×104 mg/L (the greatest inhibition of growth-rate was 70%-71%, occurred during the day 1-5). Low concentrations (2-500 mg/L) stimulated algal growth up to the greatest effect of 85%-200% w...     

供氧模式对序批式活性污泥反应器硝化性能的影响

采用非固定氧供给模式和固定氧供给模式对序批式活性污泥反应器的硝化性能进行了研究。结果表明供氧模式对序批式活性污泥反应器的硝化能力、硝化产物和污泥组成有重要影响。在非固定氧供给模式下,亚硝酸化和硝酸化同时进行,最终反应产物为硝酸盐。在固定氧供给模式下,亚硝酸化和硝酸化顺序发生,如果反应时间不足,出流中将含有大量亚硝酸盐。亚硝酸菌具有碳氧化菌的饱食饥饿(feastfamine)能力;而硝酸菌则没有。饥饿对亚硝酸菌在低氧下的氧化起着关键作用。     

紫外强化铜循环催化过硫酸盐降解甲基橙

为增强Cu（Ⅱ）/PMS（PMS为活化过硫酸盐）体系的氧化能力,加速Cu（Ⅰ）和Cu（Ⅱ）之间的循环转化,以MO（甲基橙）为目标污染物,研究了Cu（Ⅱ）/PMS/UV（UV为紫外线）体系氧化降解MO的效果和反应机理,以及UV在Cu（Ⅱ）/PMS体系中的作用.结果表明:反应20 min时,Cu（Ⅱ）/PMS体系中MO的降解率为41.13%,Cu（Ⅱ）/PMS/UV体系中MO的降解率达到100%;通过投加TBA（叔丁醇）和EA（乙醇）发现,在酸性条件下体系的主要氧化物种是SO₄-·（硫酸根自由基）和少量的·OH（羟基自由基）;MO的降解率随pH的增大而减小;提高紫外灯功率和PMS投加量均有利于MO的降解;最佳Cu（Ⅱ）投加量为10.0 μmol/L,超过Cu（Ⅱ）的最佳投量会抑制MO的降解;MO的降解过程符合假一级动力学;紫外可见光谱图分析结果表明,MO最终被降解为共轭二烯类物质.研究显示,在Cu（Ⅱ）/PMS/UV体系中,UV可以有效促进Cu（Ⅱ）向Cu（Ⅰ）的转化,从而显著增强Cu（Ⅱ）/PMS体系的氧化能力,有效降解水中污染物.