表面活性剂对苯系物在静水面挥发的影响

以苯、甲苯和乙苯为苯系物(BTEX)的目标化合物 ,研究了十二烷基苯磺酸钠(SDBS)、十六烷基三甲基溴化铵(CTMAB)和月桂醇聚氧乙烯(4)醚(Brij30)共存时,BTEX在静水面的挥发及机理 ,为复合污染的水体中表面活性剂对有机物挥发的影响提供理论依据 .结果表明 ,在所测浓度范围内 ,表面活性剂浓度大于临界胶束浓度 (CMC)且分别达到1000mg/L、2000mg/L和3000mg/L 时 ,乙苯、甲苯和苯的挥发速率分别开始变小 ,挥发半衰期值(t_1/2)变大 .胶束的形成 ,减小了BTEX在液膜和液相中的浓度比(α) ,使BTEX在静水面的挥发速率降低 .CTMAB和Brij30对苯系物在静水面挥发速率的抑制作用明显强于SDBS .相同表面活性剂对BTEX挥发速率的抑制作用与BTEX的辛醇 水分配系数 (Kow)和亨利系数(H)均呈正相关 .     

6种挥发性有机物在甲苯驯化微生物中的好氧生物降解性能

利用振荡摇瓶法测定了6种典型挥发性有机物,甲苯、邻二甲苯、间二甲苯、对二甲苯、苯和氯苯在甲苯驯化微生物中的好氧生物降解性能.结果表明,在本研究的液相浓度范围内(甲苯＜174mg/L,邻二甲苯＜149mg/L,间二甲苯＜129mg/L,对二甲苯＜133mg/L,苯＜234mg/L,氯苯＜146mg/L),3种二甲苯、苯和氯苯的降解速率随其初始浓度的增大而增加,符合一级反应,这5种VOCs未对微生物产生明显的抑制或毒害作用;甲苯的液相浓度大于85mg/L时,其降解速率不随初始浓度的增大而改变,其降解规律符合Monod方程.     

BTEX在乙醇汽油和传统汽油污染地下水中的衰减行为对比

地下燃油储藏罐泄漏造成苯、甲苯、乙苯和二甲苯（BTEX）影响生态环境和公众健康的问题一直备受关注,随着乙醇汽油的推广使用,乙醇对BTEX修复策略的影响成为需要重视的新问题.为揭示乙醇汽油污染地下水中BTEX的衰减行为,本文通过室内两个独立砂槽投注实验和近3年的监测,对比了乙醇汽油和传统汽油中BTEX自然衰减和基于硫酸盐-硝酸盐补充的增强生物修复行为.结果表明,传统汽油BTEX自然衰减较快,乙醇汽油BTEX自然衰减较慢,一级衰减速率常数分别为0.0055~0.0329 d^-1和0.0045~0.0124 d^-1;苯衰减最快,其次为甲苯.补充硫酸盐和硝酸盐能促进生物修复,单独补充硫酸盐时其利用率为89.7%~92.9%,同时补充硝酸盐时硫酸盐利用被抑制,硝酸盐利用率为79.9%~87.2%.水位波动会促进BTEX溶解和迁移,增大质量通量.乙醇汽油不仅能消耗更多电子受体,使得BTEX衰减被抑制,而且可能会扩大水位波动引起的增溶效应.     

生物活性炭去除水中挥发性苯系物的基础研究

采用连续流生物活性炭(BAC)工艺处理水中挥发性苯系物(BTEX,包括苯、甲苯、乙苯、二甲苯),评价进水负荷、活性炭炭型等因素对于BAC处理性能的影响.研究表明,在40d的处理时间内,除苯之外,其余BTEX的BAC出水中均未检出苯系物(进水为6mg/L).为了检验BAC在高BTEX负荷情况时的处理效果,将进水浓度设定为19~32mg/L左右,在EBCT为1.2min条件下同样只有苯的出水浓度上升至10mg/L(C/Cin为0.45),然后略有下降,最终保持在5~10mg/L(C/Cin为0.3以下),其余苯系物出水浓度均一直保持小于5mg/L.这表明BAC可以有效地处理高负荷BTEX(8.68~12.9kgTOC/(m3·d))的进水.生物活性炭对于活性炭吸附容量的恢复有比较明显的作用,煤质炭和椰壳炭的生物再生效率分别为53.6%和26.6%,煤质炭再生效率高的原因可能是其具备更多的大型中孔和大孔.     

不同pH条件下三氯乙烯及其脱氯产物对苯或甲苯厌氧生物降解的影响

将零价铁渗透反应格栅和生物降解格栅联用,先利用氯代烃易还原脱氯的性质通过零价铁渗透反应格栅去除氯代烃,后利用BTEX易生物降解的性质通过生物降解格栅去除BTEX,可以有效去除地下水中由氯代烃和BTEX这两种性质迥异的污染物形成的混合污染羽.但在联合格栅技术中,零价铁渗透反应格栅后的强碱性环境(pH9)、氯代烃脱氯还原中间产物(cis-1,2-DCE)的积累和可能出现的TCE穿透均可对生物降解格栅中BTEX的生物降解产生影响.针对上述问题,本文研究了不同pH条件下TCE和cis-1,2-DCE对苯或甲苯厌氧生物降解的影响.结果发现,碱性pH条件有利于苯或甲苯的生物降解,但不同pH条件下TCE或cis-1,2-DCE的加入对苯或甲苯的生物降解均产生抑制(除pH=7.9,cis-1,2-DCE=100μg·L-1时的甲苯),且TCE对苯和甲苯生物降解的抑制要明显强于cis-1,2-DCE;不同pH条件下,TCE 100和500μg·L-1对苯生物降解的抑制作用没有明显差异,但对甲苯生物降解的抑制却随着TCE浓度的增加而增加;pH=7.9时,cis-1,2-DCE的加入有利于甲苯的生物降解,之后随着pH的增加又转变为抑制.另外,在苯或甲苯厌氧生物降解过程中,可能存在cis-1,2-DCE与苯或甲苯的共代谢生物降解,且甲苯更有利于cis-1,2-DCE的共代谢降解.     

苯或甲苯对粒状铁还原三氯乙烯及其中间产物顺式二氯乙烯的影响

地下水中挥发性氯代烃和石油烃类(主要为苯、甲苯、乙苯和二甲苯,总称为BTEX)混合污染羽可用铁渗透反应格栅(Fe0-PRB)联合厌氧生物降解技术修复;在设计上游Fe0-PRB时,需考虑BTEX存在下是否需增加其厚度.采用柱实验方法研究了苯和甲苯在粒状铁反应系统中吸附平衡后,对粒状铁去除三氯乙烯(TCE)长期运行的影响.结果表明,苯或甲苯(浓度各1～2mg·L-1左右)存在时,TCE(2mg·L-1左右)的去除仍符合准一级反应动力学;苯和甲苯的存在分别使TCE的去除速率平均降低约15.1%和18.5%,而使cis-1,2-DCE的去除速率各提高约4.5%和42.8%.在Fe0-PRB的长期运行中,矿物沉淀的积累仍是影响TCE还原脱氯的主要因素,苯或甲苯对TCE还原脱氯的抑制仅表现在运行初期;无论有无苯和甲苯,TCE的氯代中间产物种类皆相同,其中以顺式二氯乙烯(cis-1,2-DCE)为主,并且各柱中cis-1,2-DCE均首先穿透,出水浓度为2～75μg·L-1,需以cis-1,2-DCE的水力停留时间来确定Fe0-PRB的厚度,因此在设计上游Fe0-PRB时,若仅考虑TCE的修复目标,不考虑cis-1,2-DCE对下游BTEX生物降解的影响,则不需增加Fe0-PRB厚度.     

典型农药污染场地地下水中苯系物监控自然衰减研究

通过对某农药污染场地地下水中苯系物（BTEX）4年的长期监测数据进行分析,识别了该场地地下水中BTEX浓度的空间分布规律,并研究了场地地下水中BTEX的自然衰减规律.结果表明,地下水BTEX污染程度较重,浓度为0.001~180.52 mg·L^-1,平均浓度为13.30 mg·L^-1;BTEX浓度和污染羽面积随时间出现波动式变化,但整体仍呈逐渐减小的趋势,表明地下水中BTEX发生了自然衰减;地下水中氧化还原电位（ORP）与BTEX浓度呈显著负相关,说明研究区中BTEX高浓度区域在发生生物降解;研究区BTEX的衰减速率较小,半衰期较长,说明该场地单纯依靠监控自然衰减的修复时间将较长,需要与化学刺激等其他主动修复技术相结合以提高自然衰减效率.     

乙醇对过硫酸盐去除石灰岩含水介质中汽油组分BTEX的影响

随着乙醇汽油的推广应用,其污染岩溶地下水的环境问题受到越来越多的关注。汽油组分苯、甲苯、乙苯和二甲苯(BTEX)可以被过硫酸盐(PS)化学氧化作用有效去除。然而,乙醇的存在是否影响PS去除BTEX尚缺乏深入研究。利用石灰岩颗粒为介质,以汽油组分BTEX(总浓度为20 mg/L)和乙醇(浓度分别为500,5000 mg/L)为污染物,通过微元体(Microcosm)实验模拟污染的岩溶地下水环境,研究PS分别去除BTEX和乙醇,以及同时去除BTEX和乙醇的效果,讨论了乙醇对PS去除BTEX的影响。结果表明:前28 d,PS可以去除91%的BTEX,准一级动力学常数为0.006~0.349 d-1,其中苯最难去除,其次为甲苯。乙醇能够被PS有效去除,准一级动力学常数为0.003~0.054 d-1,去除速率小于BTEX;乙醇与BTEX共存时能够抑制BTEX的去除,但不会影响BTEX去除的优先性。PS浓度增大,有利于去除乙醇和BTEX,但会抑制微生物活性,促使pH值下降,并导致CaSO₄沉淀。该试验结果可为乙醇汽油污染岩溶地下水的原位化学氧化研究提供科学参考。     

苯系化合物在硝酸盐还原条件下的生物降解性能

运用驯化的反硝化混合菌群进行了苯系化合物(BTEX)的厌氧降解试验.结果表明,混合菌群能够在反硝化条件下有效降解苯、甲苯、乙苯、邻二甲苯、间二甲苯和对二甲苯.BTEX的降解规律符合底物抑制的Monod模型,当初始浓度小于50mg·L^-1时,6种受试基质的厌氧降解速率顺序为:甲苯>乙苯>间二甲苯>邻二甲苯>对二甲苯>苯.整个试验过程中NO₃^-的消耗与苯、甲苯、乙苯、邻二甲苯、间二甲苯及对二甲苯生物降解之间的摩尔比分别为:9.47,9.26,1     

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.     

Groundwater contamination and natural attenuation capacity at a petroleum spilled facility in Korea

As a remedial option, the natural attenuation capacity of a petroleum contaminated groundwater at a military facility was examined. Hydrogeological conditions, such as high water level, permeable uppermost layer and frequent heavy rainfall, were favorable to natural attenuation at this site. The changes in the concentrations of electron acceptors and donors, as well as the relevant hydrochemical conditions, indicated the occurrence of aerobic respiration, denitrification, iron reduction, manganese reduction and sulfate reduction. The calculated BTEX expressed biodegradation capacity ranged between 20.52 and 33.67 mg/L, which appeared effective for the reduction of the contaminants levels. The contribution of each electron accepting process to the total biodegradation was in the order: denitrification > iron reduction > sulfate reduction > aerobic respiration > manganese reduction. The BTEX and benzene point attenuation rates were 0.0058-0.0064 and 0.0005-0.0032 day^-1, respectively, and the remediation time was 0.7-1.2 and 2.5-30 years, respectively. The BTEX and benzene bulk attenuation rates were 8.69 × 10^-4 and 1.05 × 10^-3 day^-1, respectively, and the remediation times for BTEX and benzene were 7.2 and 17.5 years, respectively. However, most of the natural attenuation occurring in this site can be attributed to dilution and dispersion. Consequently, the biodegradation and natural attenuation capacities were good enough to lower the contaminants levels, but their rates appeared to be insufficient to reach the remediation goal within a reasonable time frame. Therefore, some active remedial measures would be required.     

沈阳地区地表水、浅层地下水及沿岸土壤中苯

对沈阳地区主要地表水(浑河、细河、蒲河、沈抚灌渠)及其沿岸地下水和土壤中苯系物(BTEX)的污染特点和分布特征进行了研究.结果表明:细河和沈抚灌渠地表水中BTEX检出率较高(33%～67%),苯和甲苯是该区域的主要污染物,ρ(苯)和ρ(甲苯)分别为<0.30～24.90和<0.30～354.00 μg/L;地表水检出的BTEX均未超过《生活饮用水卫生标准》(GB5749—2006)的限值(1 510 μg/L). 细河两岸的浅层地下水在一定程度上受到BTEX的污染,苯和甲苯的检出率分别为25%～33%和13%～25%,二甲苯和乙苯检出率较低(0～20%). 彰驿镇19个监测井中有2个浅层地下水监测井中的ρ(苯)超过GB5749—2006限值(10 μg/L),夏季ρ(苯)最大值为236.00 μg/L. 沿岸附近土壤中5种BTEX全部被检出,检出率均高于相应的河水. 研究区包气带土壤层虽具有良好的防污性能,但也具有储存和阻碍BTEX挥发和降解的负面效应,对当地的生态系统和人类健康构成了潜在的威胁.      

1,2-二氯乙烷自然衰减过程中模拟饱和含水层的氧化还原条件变化

为研究自然条件下饱和含水层中1,2-DCA(1,2-二氯乙烷)的自然衰减过程及该过程中含水层氧化还原环境的变化特征,利用室内连续水流土柱模拟饱和含水层,研究生物降解作用对1,2-DCA自然衰减的贡献以及饱和含水层环境条件的动态变化规律. 初始ρ(1,2-DCA)为50 mg/L,模拟地下水流速为450 μL/min,模拟试验连续进行30 d,分别监测ρ(1,2-DCA)和水环境指标. 结果表明,1,2-DCA自然衰减的一级速率常数为0.068 9 d-1,其中生物降解作用的贡献率为6.34%. 1,2-DCA自然衰减过程中,NO₃-首先充当生物降解的电子受体,随后Fe3+、SO₄2-依次发生反应,土柱内部不同高度出现了氧化还原分带,分别是硫酸盐还原带、铁盐还原带、硝酸盐还原带.      

包气带砂层中垃圾渗滤液自然衰减作用研究

通过实验定量分析了包气带砂层中影响垃圾渗滤液污染物自然衰减的吸附作用和生物降解作用。通过静态吸附实验计算得到砂层对COD和NH4+的理论最大吸附量为52.36和35.34 mg/kg。在生物降解作用研究中,确定HgCl2为生物作用抑制剂,最佳抑制浓度为10 mg/L。通过模拟柱对比得出包气带砂层中,生物降解是垃圾渗滤液污染物自然衰减的主要机制。生物作用和自然衰减条件下,垃圾渗滤液中COD在包气带砂层中的一级衰减动力学方程分别为:ρ(COD)=642221e-0.0017t和ρ(COD)=642221e-0.0021t。     

Control of petroleum-hydrocarbon contaminated groundwater by intrinsic and enhanced bioremediation

In the first phase of this study, the e ectiveness of intrinsic bioremediation on the containment of petroleum hydrocarbons was evaluated at a gasoline spill site. Evidences of the occurrence of intrinsic bioremediation within the BTEX (benzene, toluene, ethylbenzene, and xylenes) plume included (1) decreased BTEX concentrations; (2) depletion of dissolved oxygen (DO), nitrate, and sulfate; (3) production of dissolved ferrous iron, methane, and CO2; (4) deceased pH and redox potential; and (5) increased methanogens, total heterotrophs, and total anaerobes, especially within the highly contaminated areas. In the second phase of this study, enhanced aerobic bioremediation process was applied at site to enhance the BTEX decay rates. Air was injected into the subsurface near the mid-plume area to biostimulate the naturally occurring microorganisms for BTEX biodegradation. Field results showed that enhanced bioremediation process caused the change of BTEX removal mechanisms from anaerobic biodegradation inside the plume to aerobic biodegradation. This variation could be confirmed by the following field observations inside the plume due to the enhanced aerobic bioremediation process: (1) increased in DO, CO2, redox potential, nitrate, and sulfate, (2) decreased in dissolved ferrous iron, sulfide, and methane, (3) increased total heterotrophs and decreased total anaerobes. Field results also showed that the percentage of total BTEX removal increased from 92% to 99%, and the calculated total BTEX first-order natural attenuation rates increased from 0.0092% to 0.0188% per day, respectively, after the application of enhanced bioremediation system from the spill area to the downgradient area (located approximately 300 m from the source area).     

黄河水体石油类污染物生物降解模拟实验研究

采用模拟实验的方法研究了自然条件下石油类污染物的生物降解规律.结果表明,向泥沙含量为0g/L或0.5g/L的黄河水样中加入大约10mg/L的石油类污染物,经过一星期左右的驯化期后,石油降解菌菌落水平逐步升高;当石油类污染物的初始浓度为11.64mg/L,温度为20℃时,泥沙含量为0.5g/L的黄河水样中大约85%的石油类污染物在63d内能得到微生物降解;水体中泥沙的含量和石油类污染物的初始浓度均显著影响石油类污染物的生物降解速率,且在不同时段的影响不一;水体中泥沙的存在亦影响到石油类污染物的生物降解动力学.     

Optimizing aerobic biodegradation of dichloromethane using response surface methodology

Response surface methodology (RSM) was employed to evaluate the optimum aerobic biodegradation of dichloromethane (DCM) in pure culture. The parameters investigated include the initial DCM concentration, glucose as an inducer and hydrogen peroxide as terminal electron acceptor (TEA). Maximum aerobic biodegradation efficiency was predicted to occur when the initial DCM concentration was 380 mg/L, glucose 13.72 mg/L, and H2O2 115 mg/L. Under these conditions the aerobic biodegradation rate reached up to 93.18%, which was significantly higher than that obtained under original conditions. Without addition of glucose, degradation efficiencies were 6 80% at DCM concentrations < 326 mg/L. When concentrations of DCM were more than 480 mg/L, the addition of hydrogen peroxide did not help to significantly increase DCM degradation efficiency. When DCM concentrations increased from 240 to 480 mg/L, the overall DCM degradation efficiency decreased from 91% to 60% in the presence of H2O2 for 120 mg/L.     

生物活性炭内吸附与生物降解协同去除有机污染物

本研究建立了一个确定BAC内2种机理去除有机物分配比例的试验方法.该方法以BAC进出水中溶解性有机碳（DOC）与可生物降解有机碳（BDOC）浓度变化作为评价参数,并利用此方法确定了臭氧投加量对2种去除机理的影响.臭氧化可以使BDOC浓度增加,臭氧投量为2～8mg/L时,BDOC增加0.12～0.54mg/L;BAC过滤使出水BDOC浓度降低为0.23～0.31mg/L.随着臭氧投量增加（2～8mg/L）,在BAC内生物降解作用去除有机物比例从46%增加到89%.     

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.