2012年夏季天津城区BTEX污染特征与臭氧潜势分析

采用AMA GC5000BTX在线色谱仪监测天津城区2012年夏季大气中苯、甲苯、乙苯、邻二甲苯和间-对二甲苯(苯系物,BTEX)的浓度,并结合其最大增量活性因子(MIR)计算各组分的最大臭氧生成潜势量.结果表明,观测期间BTEX浓度均值为38.72μg/m3,其中甲苯和间-对二甲苯浓度最高,乙苯和苯次之,邻二甲苯最低, BTEX存在明显的日变化特征,受大气光化学反应和边界层扩散能力共同影响,午后浓度最低,夜间BTEX浓度维持在较高水平,各BTEX日变化趋势一致.苯与甲苯质量浓度的比值为0.77,表明机动车排放是BTEX的主要来源,但石油化工和涂料挥发等因素也对其存在影响.经计算,间-对二甲苯的最大臭氧生成潜势量最高,甲苯、乙苯和邻二甲苯相当,苯最低, 表明BTEX中间-对二甲苯的光化学反应活性最强.     

1株BTEX降解新菌株的分离鉴定及其降解特性研究

取自炼油污水处理厂曝气池的活性污泥经过苯系物定向驯化后,选育到1株能同时高效降解苯、甲苯、乙苯和邻二甲苯(BTEX)的菌株byf-4,基于形态特征、生理生化、16S rDNA序列系统学分析和Biolog鉴定,可确定该菌株为染料分枝杆菌Mycobacterium cosmeticum,其为新发现的1株具有降解BTEX性能的菌株.该菌株最佳生长温度和pH分别为30℃和7.0,其对4种苯系物的降解优先顺序为苯、甲苯、乙苯、邻二甲苯;菌株降解苯、甲苯、乙苯和邻二甲苯的比耗氧速率分别为165.3、170.5、49.3和57.4 mg.(min.mg)-1;菌株降解BTEX的过程遵循Haldane动力学模型,对苯、甲苯、乙苯和邻二甲苯的最大比降解速率分别为0.518、0.491、0.443和0.422 h-1,菌株最大比生长速率分别为0.352、0.278、0.172和0.136 h-1.     

甲苯、邻二甲苯和二氯甲烷混合气体降解菌群构建及其性能研究

挥发性有机物（VOCs）排放导致一系列环境问题,而生物法是一项绿色处理技术.本实验选取3种VOCs（甲苯、邻二甲苯、二氯甲烷）作为模型污染物,利用甲苯、邻二甲苯降解菌Zoogloea resiniphila HJ1（菌株HJ1）及二氯甲烷降解菌Methylobacterium rhodesianum H13（菌株H13）构建复合菌株,采用“专属菌+综合菌”模式以复合菌株和驯化污泥构建复合强化菌群.研究表明,复合菌株可完全降解400 mg·L^-1甲苯、256 mg·L^-1邻二甲苯、200 mg·L^-1二氯甲烷,矿化率分别为74.3%、61.1%、82.7%.复合菌株可完全降解480 mg·L^-1混合污染物（3种污染物浓度比为1∶1∶1）,降解速率依次为甲苯>邻二甲苯>二氯甲烷.经过优化,菌株HJ1和菌株H13最佳配比被确定为1∶5.复合强化菌群不仅大幅提高了 邻二甲苯、二氯甲烷降解速率,还提高了混合污染物矿化率.甲苯、邻二甲苯的存在对二氯甲烷降解产生明显抑制效应,而低浓度二氯甲烷 （< 240 mg·L^-1）对甲苯、邻二甲苯降解无明显抑制作用.本研究为VOCs生物净化过程中菌群构建提供数据支撑.     

诺氟沙星对地下水中反硝化过程的影响:反硝化酶活性的证据

为探究不同初始浓度诺氟沙星对地下水反硝化过程中NO₃^--N和NO₂^--N降解的影响,选取以乙酸钠为电子供体,硝酸盐为电子受体驯化的反硝化细菌进行厌氧反硝化批实验研究,从反硝化细菌生长特性和反硝化酶活性等方面揭示诺氟沙星对反硝化过程的影响机制.结果表明,浓度为10 μg·L^-1和100 μg·L^-1的诺氟沙星对反硝化细菌的生长及NO₃^--N降解均有抑制作用,100 μg·L^-1诺氟沙星对NO₃^--N降解的抑制程度更大,抑制率为77.3%;且100 μg·L^-1诺氟沙星减少了NO₂^--N积累,最大积累量降低了67.9%.诺氟沙星初始浓度大于10 μg·L^-1时抑制了硝酸盐还原酶活性,在此过程中,亚硝酸盐还原酶活性在一定程度上有所增强.反硝化酶活性与NO₃^--N及NO₂^--N降解规律相符.因此,诺氟沙星对反硝化酶活性的控制作用是其影响反硝化过程的主要原因.     

有机碳源条件下厌氧氨氧化ASBR反应器中的主要反应

采用5个已稳定运行在厌氧氨氧化状态的ASBR反应器,通过COD、氨氮、亚硝酸盐氮、硝酸盐氮、pH等指标的监测和好氧硝化菌、异养反硝化菌的测定,研究了不同有机碳源条件下反应器中发生的主要反应.结果表明,反应器中存在好氧硝化菌、异养反硝化菌和厌氧氨氧化菌.在COD、氨氮、亚硝酸盐氮等存在条件下,可发生好氧硝化、厌氧氨氧化和异养反硝化反应,先是好氧硝化反应、厌氧氨氧化反应和异养反硝化反应共存,其后依次是异养反硝化反应和厌氧氨氧化反应占主导地位.当C/NO₂^--N在1.7～1.9范围内时,C/NH₄⁺-N为1.7的1号反应器具有最佳的厌氧氨氧化效果,反应结束时其COD去除率、NH₄⁺-N去除率、NO₂^--N去除率分别为100%、81.7%和74.4%.     

同步反硝化聚磷的试验研究

采用SBR反应器和人工合成废水研究了同步反硝化聚磷的条件和影响因素.试验结果表明,厌氧/好氧方式下驯养的生物除磷污泥,在厌氧期之后供给硝酸盐,则污泥可以很快实现同步反硝化聚磷.聚磷前厌氧阶段的存在是实现反硝化聚磷必不可少的重要前提.在没有NO₃^-干扰而且乙酸钠为唯一碳源下,最佳厌氧时间为60min.先于缺氧期微生物接触硝酸盐,会使反硝化聚磷减弱甚至丧失.缺氧段NO₃^--浓度是影响反硝化聚磷效果的因素之一.在厌氧(2h)-缺氧(1h)-好氧(2h)的试验条件下,当NO₃^--N浓度由5mg/L上升至20mg/L时,其反硝化聚磷效率由11.9%上升至48.7%.但NO₃^--N浓度提高到了20mg/L以上时,其效率提高得不很明显.好氧段的存在不会使诱导形成的反硝化聚磷消失,但缩短好氧时间有助于提高DNPA在除磷中的比例.     

过硫酸盐去除石灰土介质中汽油BTEX的效果及乙醇的影响

为了认识岩溶区石灰土含水介质中化学氧化联合生物降解去除燃油苯系物的效果,以汽油中的苯、甲苯、乙苯和二甲苯（BTEX）作为 污染物,通过批实验研究过硫酸盐（PS）联合硝酸盐去除汽油BTEX的效果,并认识不同浓度乙醇（EtOH）存在时带来的影响及化学氧化与反硝化联合修复的可能性.结果表明,在35 d内各组的BTEX去除率均达到91.00%以上,PS化学氧化能有效地去除BTEX.在不含EtOH及含EtOH 初始浓度为500和5000 mg·L^-1的情况下,BTEX浓度在第65 d时分别为未检出、0.226 mg·L^-1、0.243 mg·L^-1,去除率分别为99.98%、99.00%、98.70%,其中,苯的去除率分别为99.98%、97.01%、93.32%.随着EtOH浓度的增加,苯的去除受到抑制,EtOH对BTEX的化学氧化具有阻碍 作用.石灰土介质中高铁含量对PS具有活化能力,高含量有机质能促进PS分解,并导致pH值回升,出现反硝化作用和硫酸盐还原作用,有利于生物降解作用的恢复.     

单级序批式生物膜反应器（SBBR）多途径生物脱氮研究

利用传统微生物分析技术与PCR、变性梯度凝胶电泳（DGGE）等分子生物学技术相结合的方法,对单级SBBR反应器中的主要生物脱氮途径进行分析.结果表明,亚硝化-厌氧氨氧化-反硝化途径是主要的脱氮途径,通过该途径去除的NH⁺₄-N占总去除量的65%以上;另外2条途径则分别是亚硝化-反硝化途径以及全程硝化-反硝化途径.所有途径都采取同步和分步2种方式完成,同步方式以曝气阶段的氮素亏损形式予以表现.分步方式则依靠各种脱氮微生物在曝气阶段和厌氧阶段不同的活性程度完成,亚硝酸细菌是曝气阶段的主要活性菌种,完成NH⁺₄-N向NO^-₂-N的转化,而厌氧氨氧化细菌和反硝化细菌则在厌氧阶段成为优势菌种,完成完整的生物脱氮过程.     

苯高效降解菌群富集及其降解机理研究

微生物绿色、低耗、原位修复去除污染土壤与地下水中可降解污染物日益受到关注.本研究从江苏某农药厂苯系物污染土壤中以苯为唯一碳源富集获得苯降解菌群.在28℃、pH=8.0、添加100 mg·L^-1酵母粉条件下,该菌群在6 h内完全降解100 mg·L^-1的苯,利用Q-TOF解析出苯酚和邻苯二酚等主要代谢产物,并通过PCR扩增出苯酚单加氧酶基因（GenBank登录号：MW388722）.该菌群30 h内可完全降解30 mg·L^-1的苯、甲苯和乙苯混合物,高通量测序结果显示该菌群主要含有Cupriavidus、Arthrobacter、Dyella、Corynebacterium、Microbacterium等菌属,其中Cupriavidus为优势菌,菌群群落结构稳定且可高效降解苯,具有潜在的应用前景.     

秋季长江口海域海水和大气中BTEX的分布及环境效应

以苯、甲苯、乙苯、间/对二甲苯和邻二甲苯为代表(简称BTEX)的单环芳烃是大气中挥发性有机物(VOCs)的重要组分，它们对臭氧(O₃)和二次有机气溶胶(SOA)的生成具有重要作用.于2020年10月分析了长江口及邻近海域海水和大气中BTEX的分布特征，并评估了其海-气通量及大气环境效应.结果表明，研究海域表层海水中苯、甲苯、乙苯、间/对二甲苯和邻二甲苯的浓度平均值分别为(17.4±21.9)、(91.2±64.0)、(25.9±16.9)、(52.9±34.9)和(26.7±19.3) ng·L^-1.BTEX浓度总体呈现近岸高、外海低的分布趋势，底层海水浓度略高于表层.大气中苯、甲苯、乙苯、间/对二甲苯和邻二甲苯的平均浓度分别为(90.4±46.6)×10^-12、(255±284)×10^-12、(139±115)×10^-12、(196±202)×10^-12和(131±116)×10^-12，在舟山群岛附近海域浓度较高.大气中乙苯和二甲苯...     

Anaerobic biodegradation of benzene series compounds by mixed cultures based on optional electronic acceptors

A series of batch experiments were performed using mixed bacterial consortia to investigate biodegradation performance of benzene, toluene, ethylbenzene and three xylene isomers （BTEX） under nitrate, sulfate and ferric iron reducing conditions. The results showed that toluene, ethylbenzene, m-xylene and o-xylene could be degraded independently by the mixed cultures coupled to nitrate, sulfate and ferric iron reduction. Under ferric iron reducing conditions the biodegradation of benzene and p-xylene could be occurred only in the presence of other alkylbenzenes. Alkylbenzenes can serve as the primary subs＇rates to stimulate the transformation of benzene and p-xylene under anaerobic conditions. Benzene and p-xylene are more toxic than toluene and ethylbenzene, under the three terminal electron acceptors conditions, the degradation rates decreased with toluene 〉 ethylbenzene 〉 m-xylene 〉 o-xylene〉 benzene 〉 p- xylene. Nitrate was a more favorable electron acceptor compared to sulfate and ferric iron. The ratio between sulfate consumed and the loss of benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene was 4.44, 4.51, 4.42, 4.32, 4.37 and 4.23, respectively; the ratio between nitrate consumed and the loss of these substrates was 7.53, 6.24, 6.49, 7.28, 7.81, 7.61, respectively; the ratio between the consumption of ferric iron and the loss of toluene, ethylbenzene, o-xylene, m-xylene was 17.99, 18.04, 18.07, 17.97, respectively.     

BTEX pollution caused by motorcycles in the megacity of HoChiMinh

Monitoring of benzene, toluene and xylenes (BTEX) was conducted along with traffic counts at 17 roadside sites in urban areas of HoChiMinh. Toluene was the most abundant substance, followed by p,m-xylenes, benzene, o-xylene and ethylbenzene. The maximum observed hour-average benzene concentration was 254 μg/m3 . Motorcycles contributed to 91% of the traffic fleet. High correlations among BTEX species, between BTEX concentrations and the volume of on-road motorcycles, and between inter-species ratios in air and in gasoline indicate the motorcycle-exhaust origin of BTEX species. Daily concentrations of benzene, toluene, ethylbenzene, p,m-xylenes and o-xylene were 56, 121, 21, 64 and 23 μg/m 3 , respectively. p,m-xylenes possess the highest ozone formation potential among the BTEX family.     

Pollution characteristics and health risk assessment of benzene homologues in ambient air in the northeastern urban area of Beijing, China

Ambient benzene homologues were measured at a site in the northeastern urban area of Beijing, China, from August 24 to September 4, 2012 by SUMMA canister sampling followed by laboratory determination using cryogenic cold trap pre-concentration-GC-MS/FID, and their health risks were also assessed. Daily total benzene homologues ranged from 0.99 to 49.71 μg/m3with an average of 11.98 μg/m3. Benzene homologues showed higher concentrations in the morning and evening than that at noontime. Comparison with previous studies revealed a trend of decrease for ambient benzene homologues probably due to the efective emission control in Beijing in recent years. Vehicular exhaust was the main source while volatilization of paints and solvents also made substantial contributions. Health risk assessment showed that BTEX(benzene, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene) and styrene had no appreciable adverse non-cancer health risks for the exposed population, while benzene has potential cancer risk of 1.34E-05. Available data from cities in China all implied that benzene imposes relatively higher cancer risk on the exposed populations and therefore strict control measures should be taken to further lower ambient benzene levels in China.     

Anaerobic BTEX degradation in soil bioaugmented with mixed consortia under nitrate reducing conditions

Different concentrations of BTEX, including benzene, toluene, ethylbenzene, and three xylene isomers, were added into soil samples to investigate the anaerobic degradation potential by the augmented BTEX-adapted consortia under niwate reducing conditiom. All the BTEX substrates could be anaerobically biodegraded to non-detectable levels within 70 d when the initial concentrations were below 100 mg/kg in soil. Toluene was degraded faster than any other BTEX compounds, and the high-to-low order ofdegradation rates were toluene>ethylbenzene>m. xylene>o-xylene>benzene>P. xylene. Nitrite was accumulated with nitrate reduction. but the accumulation of nitrite had no inhibitory effect on the degradation of BTEX throughout the whole incubation. Indigenous bacteria in tIle soil could enhance the BTEX biodegradation ability of the enriched mixed bacteria. When the six BTEX compounds were simultaneously present in soil, there was no apparent inhibitory effect on their degradation with lower initial concentrations. Alternatively, benzene, o-xylene, and P-xylene degradation were inhibited with higher initial concentrations of 300 mg/kg. Higher BTEX biodegradation rates were observed in soil samples with the addition of sodium acetate compared to the presence of a single BTEX substrate. and the hypothesis of primary-substrate stimulation or cometabolic enhancement of BTEX biodegradation seems likely.     

硝酸盐和甲烷对覆土中苯系物厌氧氧化的影响

苯系物是填埋场填埋气中恶臭有机气体的重要成分之一,填埋气中的CH4则是重要的温室气体.填埋覆土层中的微生物可以氧化CH4和苯系物,因此,强化微生物的氧化效能有助于削减和控制填埋气的污染.电子受体还原可耦合甲烷和某些有机物的厌氧氧化,从而去除甲烷和有机物.鉴此,本研究通过静态培养试验,分析了电子受体SO2-4共存条件下,NO-3和CH4共存对覆土中苯系物厌氧降解的影响.结果表明不外加NO-3时,苯系物抑制CH4的降解,加入NO-3后,苯系物共存反而有利于CH4的去除;单独添加NO-3或CH4都能促进填埋覆土中苯系物的去除;而同时添加NO-3和CH4能更好地促进苯系物的去除,甲苯、二甲苯和异丙苯的去除率最高可达65%、88%和82%,远高于不添加NO-3和CH4对照处理的53%、76%和31%;NO-3还原与CH4厌氧氧化耦合过程能同步促进苯系物的厌氧氧化.     

天津城区夏冬季典型污染过程中BTEX变化特征及其健康风险评估

利用GC955在线气相色谱仪分别于2019年7月和2020年1月在天津市区开展苯系物（BTEX,包括苯、甲苯、乙苯、间/对-二甲苯和邻-二甲苯）实时在线观测,对典型污染过程中BTEX的浓度水平、组成及演化机制进行了研究,并运用特征物种比值法对BTEX的来源进行了定性分析,最后运用US EPA的人体暴露分析评价方法对BTEX健康风险进行评估.结果表明,臭氧和霾污染过程中BTEX体积分数平均值分别为1.32×10^-9和4.83×10^-9,其中苯的体积分数占比最大,其次是甲苯、乙苯和二甲苯占比最小.2020年1月BTEX体积分数很大程度上受到西南方向短距离传输的影响,而在2019年7月BTEX浓度受到本地排放的影响.BTEX浓度水平在2019年7月受到温度和相对湿度的共同影响,而在2020年1月当温度较低时BTEX浓度对相对湿度的变化更敏感.天津市区BTEX在霾污染过程中受生物质燃烧/化石燃料燃烧/燃煤排放的影响较大,而在臭氧污染过程中除了受到燃烧排放源影响,交通源排放在很大程度上也有影响.臭氧污染和霾污染过程中BTEX的HI分别为0.072和0.29,均处于EPA认定的安全范围内.苯的致癌风险在清洁天和污染过程中均高于EPA规定的安全阈值,需引起高度重视.     

非离子型表面活性剂强化混合菌降解间二甲苯的性能研究

从焦化废水厂的活性污泥中筛选间二甲苯混合降解菌,并研究非离子型表面活性剂吐温80(C_(64)H_(124)O_(26))对混合菌降解间二甲苯的强化作用.研究结果表明:驯化后的间二甲苯混合降解菌以产黄杆菌属(Rhodanobacter sp.)为主,占比41.2%;仅存在吐温80作为单一碳源时,高浓度的吐温80对混合降解菌没有明显的抑制作用;吐温80与间二甲苯共存时,当吐温80浓度为2 CMC,反应72 h后间二甲苯的降解率达到最高,为76%;提前12 h(较混合降解菌)投加浓度为2 CMC的吐温80,最利于菌种的生长繁殖及间二甲苯的降解.     

Benzene, toluene and xylenes levels in new and used vehicles of the same model

The aim of this work was to determine the level of benzene, toluene, o-xylene and m, p-xylene （BTX） in air samples collected from the cabins of new and used vehicles of the same model. Ten new vehicles were examined in order to check interior emission from materials used to equip the passenger compartment. In order to compare and define the impact of exhaust gases, air samples were also collected from two used cars, at different mileages （up to 20,000 kin）. All vehicles tested were of the same type. Samples were collected onto Carbograph 1TD sorbent, thermally desorbed and examined with the use of gas chromatography with flame ionisation and mass spectrometry detectors. All results obtained were referred to Polish and German requirements for indoor air quality （both in public buildings and in workspace environments）. Average benzene, toluene, o-xylene and m, p-xylene concentrations in new cars were determined at the level of 11.8 μg/m^3, 82.7 μg/m^3, 21.2 μg/m^3 and 89.5 μg/m^3, respectively. In the used cars, BTX concentration increased with increasing vehicle mileage. The most significant increase of BTX concentration was observed above 11,000 km mileage.     

南京北郊BTESX特征及健康风险评估

采用AMA GC5000BTX监测2014年1月~2016年12月南京北郊大气中苯、甲苯、乙苯、间/对-二甲苯、邻-二甲苯和苯乙烯（BTESX）的体积分数,分析了BTESX体积分数的变化特征以及气象要素对其的影响,并使用特征比值法（T/B）对BTESX的来源进行了定性分析,最后利用EPA的人体暴露分析评价方法对BTESX健康风险进行评估.结果表明,在观测期间,φ（BTESX）平均值为（7.28±6.63）×10^-9,其中φ（苯）最高,为（2.45±3.91）×10^-9,其他物种体积分数由大到小为：甲苯>乙苯>间/对-二甲苯>邻-二甲苯>苯乙烯,分别为：（2.41±2.61）×10^-9、（1.37±1.28）×10^-9、（0.51±0.48）×10^-9、（0.30±0.36）×10^-9和（0.22±0.42）×10^-9.由于存在稳定的芳烃源,BTESX体积分数的月变化和季节变化均不如其他物种（NO_x、CO、SO₂和PM_2.5等）明显.同时,BTESX及其他污染物的"周末效应"不显著.BTESX体积分数很大程度受到来自东北方向化工等企业以及交通主干道的污染物短距离输送的影响,导致BTESX体积分数在东北方向上较大.BTESX体积分数受到相对湿度和温度的共同影响,其高值区主要位于30%~70%相对湿度范围内,在该相对湿度范围内,温度越高,BTESX体积分数高值区域范围也越大.BTESX在不同季节的HI （危害指数）处于EPA认定的安全范围内,而R（苯致癌风险）值则高于EPA规定的安全阈值,同时HI和R值在夏季较高,因此需要高度重视.     

我国典型城市环境大气挥发性有机物特征比值

城市环境大气挥发性有机物(VOCs)比值能够提供有用信息.基于在我国典型城市进行的7次VOCs观测数据,利用正交最小二乘法(ODR)、线性拟合法等4种方法计算了VOCs组分比值,并探讨其在监测数据质量评估、来源诊断和光化学过程研究中的应用.结果显示:间,对-二甲苯与邻-二甲苯浓度在7次观测中均呈现非常好的相关性(r为0.975~0.997),且不同观测中比值接近(2.78~3.05),这一比值可以用来对城市大气VOCs(尤其是芳香烃)测量数据的可靠性进行评估.以甲苯/苯(T/B)和丙烷/乙烷(P/E)为例初步分析了我国不同城市大气VOCs来源的差异.上海和广州T/B最高,分别为2.37和1.78,高于隧道实验中T/B比值(1.52),说明还受到溶剂涂料等富含甲苯的排放源影响,北京夏季T/B与隧道实验接近,而成都、北京冬季和重庆T/B较低(0.744~1.36),说明受到生物质燃烧、煤燃烧等其他富含苯的排放源影响.P/E分析结果显示,广州P/E(1.27)显著高于其他数据集(0.270~0.645),与2010年广州部分公交车和出租车仍利用液化石油气(LPG)作为燃料有关.另外,基于邻-二甲苯/乙苯变化特征表征光化学反应程度,并初步估算出典型城市大气上午·OH暴露量为(2.70~4.45)×10~(10)molecule·cm~(-3)·s.