甲基叔丁基醚降解菌的驯化与筛选

为了筛选降解甲基叔丁基醚(MTBE)的优势菌种,调查了不同来源土壤土著菌的降解潜力.应用不同的驯化方式以MTBE为惟一碳源,在好氧的条件下,驯化、筛选出高效降解混合菌株,为现场应用打好基础.并从中分离得到6株高降解性的单一菌株,对其进行了初步鉴定,为进一步研究其降解途径做好准备.对单一菌株与混合菌株的降解效果进行了比较.结果表明,混合菌株的降解效果要明显高于单一菌株.     

甲基叔丁基醚(MTBE)在不同粘性土壤中的吸附特性

土壤对有机物的吸附是污染土壤及地下水原位修复技术中的重要参数.通过静态间歇吸附实验研究了甲基叔丁基醚(MTBE)在不同粘性土壤中的吸附特性.结果表明,MTBE在粘性土壤中的吸附行为均可用线性方程很好描述,粘粒是土壤对MTBE吸附的主要影响因素,吸附常数与土壤粘粒含量呈y=4.382×10-3x-0.817 ×10-3直线关系.对不同温度下的吸附数据分析发现,粘性土壤对MTBE的平衡吸附量随温度的升高而降低,由吸附热力学推导可得等量吸附焓变△H与平衡吸附量无关,且△H＜0,表明该吸附为故热过程.     

Persistence of methyl <Emphasis Type="Italic">tertiary</Emphasis> butyl ether (MTBE) against metabolism by Danish vegetation

BACKGROUND: Methyl tertiary butyl ether (MTBE) is the second most highly produced industrial chemical in the US and a frequent groundwater pollutant. At the same time, MTBE is quite persistent to biotic and abiotic decomposition. The goal of this study was to find plant species that could degrade MTBE and might be used in phytoremediation. METHODS: Excised roots and leaves (0.3 g) from more than 24 Danish plant species out of 15 families were kept in glass vessels with 25 ml spiked aqueous solution for 2 to 4 days. MTBE concentrations were 1 to 5 mg/L. Samples were taken directly from the solution with a needle and injected to a purge and trap unit. MTBE and the main metabolite, TBA, were measured by GC/FID. RESULTS AND DISCUSSION: Solutions with roots of poplar (Populus robusta) and a willow hybrid (Salix viminalis x schwerinii) produced TBA in trace amounts, probably stemming from bacteria. Significant MTBE reduction (> 10%) was not observed in any of the tests. Leaves from none of the species (trees, grasses and herbs) reduced the concentration of MTBE in the solution and no TBA, nor any other known metabolite of MTBE, was detected. CONCLUSION: It was not possible to find plants capable of efficiently degrading MTBE. This gives rise to the conclusion that plants probably cannot degrade MTBE at all, or only very slowly. RECOMMENDATIONS AND OUTLOOK: For phytoremediation projects, this has, as consequence, that the volatilization by plants (except with genetically engineered plants) is the only relevant removal process for MTBE. For risk assessment of MTBE, degradation by the plant empire is not a relevant sink process.     

Evaluating the risks of methyl tertiary butyl ether (MTBE) pollution of urban groundwater

MTBE, a fuel oxygenate added to gasoline in parts of the USA, appears to have imposed significant adverse impacts on groundwater. In the UK, the impacts of MTBE are not well known in part because insufficient data has been presented to allow an accurate assessment. With the recognition of urban groundwater as a potentially valuable resource due to the growing pressure on rural groundwater, there is need for pollution risks to urban groundwater to be evaluated for contaminants such as MTBE. This paper presents the application of a risk-based water management tool called Borehole Optimisation System (BOS) in the evaluation of the risk of MTBE to urban groundwater at city scale using Nottingham city as our case study. The risk model was validated by comparison of its predictions with observations of MTBE detections for about 1100 boreholes in England and Wales. The output of the risk analysis was the production of a map showing the predicted MTBE concentration at all locations in the city. The results indicate that MTBE does not currently pose a major risk to urban groundwater although there may be a potential risk to groundwater in the southern part of the city where most industries are concentrated.     

无铅汽油添加剂甲基叔丁基醚(MTBE)的环境化学行为及其分析方法

本文简要介绍了无铅汽油添加剂MTBE的物理化学性质、环境化学行为、地下水的污染状况和对动物的潜在致癌毒理 ,并对其分析方法作了综述 ,指出了我国开展MTBE有关研究的重要性。     

Methyl Tertiary Butyl Ether (MTBE) and Other Volatile Organic Compounds (VOCs) in Public Water Systems,Private Wells,and Ambient Groundwater Wells in New Jersey Compared to Regulatory and Human-Health Benchmarks

Potential threats to drinking water and water quality continue to be a major concern in many regions of the United States. New Jersey, in particular, has been at the forefront of assessing and managing potential contamination of its drinking water supplies from hazardous substances. The purpose of the current analysis is to provide an up-to-date evaluation of the occurrence and detected concentrations of methyl tertiary butyl ether (MTBE) and several other volatile organic compounds (VOCs) in public water systems, private wells, and ambient groundwater wells in New Jersey based on the best available data, and to put these results into context with federal and state regulatory and human-health benchmarks. Analyses are based on the following three databases that contain water quality monitoring data for New Jersey: Safe Drinking Water Information System (SDWIS), Private Well Testing Act (PWTA), and National Water Information System (NWIS). For public water systems served by groundwater in New Jersey, MTBE was detected at a concentration ≥10 μg/L, ≥20 μg/L, and ≥70 μg/L at least once in 30 (2%), 21 (1.4%), and five (0.3%) of sampled systems from 1997 to 2011, respectively. For private wells in New Jersey, MTBE was detected at a concentration ≥10 μg/L, ≥20 μg/L, and ≥70 μg/L at least once in 385 (0.5%), 183 (0.2%), and 46 (0.05%) of sampled wells from 2001 to 2011, respectively. For ambient groundwater wells in New Jersey, MTBE was detected at a concentration ≥10 μg/L, ≥20 μg/L, and ≥70 μg/L at least once in 14 (2.1%), 9 (1.3%), and 4 (0.6%) of sampled wells from 1993 to 2012, respectively. Average detected concentrations of MTBE, as well as detected concentrations at upper-end percentiles, were less than corresponding benchmarks for all three datasets. The available data show that MTBE is rarely detected in various source waters in New Jersey at a concentration that exceeds the State's health-based drinking water standard or other published benchmarks, and there is no evidence of an increasing trend in the detection frequency of MTBE. Other VOCs, such as tetrachloroethylene (PCE), trichloroethylene (TCE), and benzene, are detected more often above corresponding regulatory or human-health benchmarks due to their higher detected concentrations in water and/or greater toxicity values. The current analysis provides useful data for evaluating the nature and extent of historical and current contamination of water supplies in New Jersey and potential opportunities for public exposures and health risks due to MTBE and other VOCs on a statewide basis. Additional forensic or forecasting analyses are required to identify the sources or timing of releases of individual contaminants at specific locations or to predict potential future water contamination in New Jersey.     

地下水浅埋区某加油站特征污染物空间分布简

加油站渗漏污染地下水已经是一个世界性的问题。由于浅埋区加油站储罐与地下水密切接触,更加剧储罐的腐蚀。为揭示加油站渗漏的典型污染物石油烃（TPH）、苯系物（BTEX）、萘和甲基叔丁基醚（MTBE）在该水文地质条件下的迁移变化,在浅埋区某加油站开展了平、枯、丰水期的地下水监测工作。在水平分布上,TPH、BTEX、萘基本相似,均在加油岛附近形成高浓度区,而MTBE则更易随地下水流动而迁移,呈现出不同的污染晕。在垂直分布上,地下水的水位变动是污染物浓度分布的主要影响因素。     

Oxidative transformation of polybrominated diphenyl ether congeners (PBDEs) and of hydroxylated PBDEs (OH-PBDEs)

BACKGROUND, AIM, AND SCOPE: The historical and widespread use of polybrominated diphenyl ethers (PBDEs) as flame retardants in consumer products worldwide has caused PBDEs to now be regarded as pervasive environmental contaminants. Most recently, hydroxylated PBDEs (OH-PBDEs) and methoxylated PBDEs (MeO-PBDEs) have emerged as environmentally relevant due to reports of their natural production and metabolism. An important parameter for assessing the environmental impact of a chemical substance is persistence. By formulating the concept that persistence is the result of the substance's physicochemical properties and chemical reactivity, Green and Bergman have proposed a new methodology to determine the inherent persistence of a chemical. If persistence could be predicted by straightforward methods, substances with this quality could be screened out before large-scale production/manufacturing begins. To provide data to implement this concept, we have developed new methodologies to study chemical transformations through photolysis; hydrolysis, substitution, and elimination; and via oxidation. This study has focused on adapting an oxidative reaction method to be applicable to non-water soluble organic pollutants. MATERIALS AND METHODS: PBDEs and one MeO-PBDE were dissolved in tetrahydrofuran/methanol and then diluted in alkaline water. The OH-PBDEs were dissolved in alkaline water prior to reaction. The oxidation degradation reaction was performed at 50 degrees C using potassium permanganate as described elsewhere. The pH was maintained at 7.6 with disodium hydrogen phosphate and barium hydrogen phosphate, the latter also serving as a trapping agent for manganate ions. The oxidation reactions were monitored by high-performance liquid chromatography and reaction rates were calculated. RESULTS: The OH-PBDEs have very fast oxidative transformation rates compared to the PBDEs. The reaction rates seem to be primarily dependent on substitution pattern of the pi-electron-donating bromine substituents and of bromine content. There are indications that further reactions of OH-PBDEs, e.g., methylation to the MeO-PBDEs, decrease the oxidation rates, and thereby generate more persistent substances. DISCUSSION: The resistance of PBDEs to oxidation, a major degradation pathway in air, should be further investigated, since these compounds do undergo long range transport. With slight modifications, the original method has been adapted to include a larger variety of chemical substances, and preliminary data are now available on the oxidative transformation rates for PBDEs and of OH-PBDEs. CONCLUSIONS: The original oxidation degradation method can now include non-water soluble compounds. This modification, using low concentrations of test chemicals, allows us to measure oxidative transformation rates, for some of the lower brominated DEs, data that can be used to assess their persistence in future model calculations. Oxidative transformation rates for PBDEs are slow compared to those for the OH-PBDEs. This suggests that OH-PBDEs, when released into the environment, undergo faster oxidative metabolism and excretion than the PBDEs. RECOMMENDATIONS AND PERSPECTIVES: To evaluate the modified method, more degradation reactions with non-water soluble compounds should be investigated. Recent studies show that OH-PBDEs are present in rats and in humans and, because of their activity as endocrine disruptors, determining their subsequent environmental fate is of importance. The resistance of PBDEs to oxidative degradation should be acknowledged as of possible future concern. Several other compound classes (such as polychlorinated biphenyls (PCBs), hydroxylated polychlorinated biphenyls (OH-PCBs), and pharmaceuticals) need to be subjected to this screening method to increase the database of transformation rates that can be used with this model.     

一株五溴联苯醚(BDE-99)降解菌的分离、鉴定及降解特性

采用梯度压力驯化法从高海拔地区土壤样品中分离到1株能以BDE-99作为碳源生长的细菌菌株,命名为BHS-4,通过生理生化及对16S rDNA扩增,T/A克隆后测序鉴定,并进一步分析初始pH、温度、碳源、细胞表胞疏水性（MATH法）及共存重金属离子对菌株降解效果的影响。结果表明：菌株BHS-4与产碱杆菌属Alcaligenes cupidus同源性为99%。菌株降解BDE-99最适pH和温度分别为8.0、20 ℃,经11 d培养后,对浓度0.4 mg·L-1的BDE-99,降解率达86.1%,在15~20 ℃范围具有较高降解率。降解特性研究结果显示,乳糖、麦芽糖和葡萄糖的添加促进了BHS-4对BDE-99的降解,而淀粉和乙酸钠添加对降解率产生了显著抑制作用（P4NO3的添加,使细胞表面疏水率（CSH）增加了49.5%,CSH与降解率呈极显著正相关（r=0.99, P2+、Zn2+在0.1~0.3 mg·L-1浓度下促进BDE-99降解;Cr6+在0.1~0.6 mg·L-1范围内对降解作用影响表现为先抑制、再促进、最后抑制。菌株BHS-4能在较低温度下对BDE-99进行高效降解且对Cu2+、Zn2+、Cr6+具有一定的耐性,可应用于低温地区BDE-99的生物处理,同时可为进一步研究低温条件下BDE-99生物降解的代谢途径和机理提供一定的基础资料。     

有机玻璃颗粒流态化热裂解

废弃聚基丙烯酸甲醋（PMMA）的增长及无序堆放会对环境造成严重影响。流化床热裂解技术代表了PMMA处理技术的发展方向。在实验室规模的流化床热解装置上,对PMMA的原料特性、加热方式和温度等多因素对其热解的影响进行了研究。结果表明,PMMA的热解产物主要是气体和液体MMA,液体最大得率为91.8%。在400℃以上时,随着热解温度的升高,CO2和CO的含量增加,而MMA含量下降;采用流化气体预热方式或减小PMMA粒径的操作方式,有利于热解强度和液体产率的提高。     

微波促进含Cr(VI)-H2O2体系降解甲基橙溶液的研究

研究了微波辐射下Cr(VI)－H₂O₂催化降解甲基橙溶液的行为，探索了微波功率、微波辐射时间、pH值、H₂O₂浓度、Cr(VI)等对甲基橙溶液脱色率和COD去除率的影响。研究结果表明，Cr(VI)-H₂O₂能形成类Fenton体系；微波辐射可提高H₂O₂产生羟基自由基(·OH)的效率。1000 mg/L的甲基橙溶液，在Cr(VI)浓度为10.0 mmol/L、pH值为2.5、H₂O₂浓度为20.0 mmol/L、微波功率为700W下加热2 min，甲基橙溶液的脱色率为99.2%，COD去除率为82.8%。     

微生物燃料电池化学阴极与生物阴极处理含铬废水

采用双室微生物燃料电池(MFC)反应器,考察了不同初始Cr(VI)浓度下化学阴极与生物阴极MFC的产电及Cr(VI)去除情况。结果表明,在各Cr(VI)浓度梯度 (20、28、32、36、40和44 mg/L)下生物阴极MFC的产电及Cr(VI)去除性能均较化学阴极MFC更优,生物阴极最大输出电压为180.1 mV,是化学阴极的1.3倍。随着初始Cr(VI)浓度的递增,两者对Cr(VI)去除的差异越明显,最终在Cr(VI)浓度为44 mg/L时,生物阴极MFC的Cr(VI)去除率为66.4%,较化学阴极提高了55.1%。进一步由循环伏安扫描、电镜扫描及X-射线能谱分析证实生物阴极MFC较化学阴极MFC产电及去铬性能优越的主要原因除了生物阴极电极上电化学活性微生物的催化作用外,Cr(VI)还原产生的不导电Cr(III)沉积物在其电极上附着较少也是一个关键因素,该Cr(III)沉积物中含有Cr2O3。     

Wastewater treatment plants and landfills emit volatile methyl siloxanes (VMSs) to the atmosphere: investigations using a new passive air sampler

Volatile methyl siloxanes (VMSs) are a class of chemicals with an increasing range of applications and widespread distribution in the environment. Passive air samplers (PAS) comprising sorbent-impregnated polyurethane-foam (SIP) disks were first calibrated and then deployed around two wastewater treatment plants (WWTPs) and at two landfill sites to investigate inputs of VMSs to air. SIP-derived air concentrations for ΣVMSs (ng/m³) at background sites on the perimeter of the WWTP were 479 ± 82.3 and comparable to results for the upwind samples at the landfills (333 ± 194). Order of magnitude higher concentrations of ΣVMSs (ng/m³) were found for on-site samples at the WWTPs (3980 ± 2620) and landfills (4670 ± 3360). Yearly emissions (kg/yr) to air were estimated and ranged from 60-2100 and 80-250, respectively, for the cyclic VMSs. These findings demonstrate and quantify for the first time, waste sector emissions of VMSs to the atmosphere.     

聚乙烯醇生物降解菌群的结构分析及优势菌株降解特性

对堆肥中降解聚乙烯醇材料的微生物菌群结构进行了分析。结果表明：降解聚乙烯醇材料的优势菌群属于芽胞杆菌科(Bacillaceae)。从降解了3年的材料表面筛选出了1株聚乙烯醇降解菌DG01,鉴定为苏云金杆菌(Bacillus thuringiensis sp.)。分别以聚乙烯醇(poly(vinyl alcohol),PVA)浓度和二氧化碳排放量为指标,对PVA的降解动力学进行了研究。结果表明：PVA生物降解过程符合一级动力学模型,R²分别为0.984 0和0.983 5。对摇瓶培养条件进行了单因素优化实验。最佳降解温度,初始pH和酵母粉浓度分别为41 ℃、7和1.40 g·L⁻¹。优化后,48 h内PVA初始浓度为3 g·L⁻¹的降解率达到了45.21%,提高了2.10倍。     

Positive vs. false detection: A comparison of analytical methods and performance for analysis of cyclic volatile methylsiloxanes (cVMS) in environmental samples from remote regions

Contamination and analytical variation can significantly hinder trace analysis of cyclic methyl volatile siloxanes (cVMS); potentially resulting in the report of false positives at concentrations approaching detection limits. To assess detection and variation associated with trace cVMS analysis in environmental matrices, a co-operative laboratory comparison for the analysis of octametylcyclotetrasiloxane (D4), decamethylcylcopentasiloxane (D5), and dodecametylcyclohexasiloxane (D6) in sediment and biota from the Svalbard Archipelago was conducted. Two definitions of detection limits were evaluated in this study; method detection limits (MDL, matrix defined) and limits of detection (LOD, solvent defined). D5 was the only cVMS detected above both LOD (0.08–0.81 ng g⁻¹ ww) and MDL (0.47–2.36 ng g⁻¹ ww) within sediment by all laboratories where concentrations ranged from 0.55 to 3.91 ng g⁻¹ ww. The percentage of positive detects for D5 decreased by 80% when MDL was defined as the detection limit. D5 was also detected at the highest frequency among all laboratories in fish liver with concentrations ranging from 0.72 to 345 ng g⁻¹ ww. Similar to sediment, percentage of positive detects for D5 decreased by 60% across all laboratories for fish livers when using MDL (0.68–3.49 ng g⁻¹ ww). Similar observations were seen with both D4 and D6, indicating that sample matrix significantly contributes to analytical response variation. Despite differences in analytical methods used between laboratories, good agreement was obtained when using MDL to define detection limits. This study shows the importance of incorporating variation introduced by sample matrices into detection limit calculations to insure data accuracy of cVMS at low concentrations.