浅层地下水系统石油类污染物的生物降解机制研究
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摘要
地下水是水资源的重要组成部分，是社会经济发展的储备资源和战略资源。然而，在我国近几十年来经济快速增长的过程中，地下水污染问题愈演愈烈，不仅显著加剧了水资源短缺的矛盾，也对生态环境和人类健康产生了极大的威胁。在各种污染物中，石油类组分因其高毒害性而备受关注，尤其是浅层地下水土环境系统中的石油类污染在全世界范围内具有普遍性与严重性，其修复治理迫在眉睫。相比污染物的其他修复净化作用而言，生物降解是能够自然发生、且唯一能降低环境中污染物总量的有效机制，并几乎伴生于所有其他原位修复技术的应用过程中并产生重要的协同修复效应。因此研究地下水中石油污染物的生物降解机制对修复具有重要的科学意义。
本文依托我国东北某油田区野外实际污染场地，针对浅层地下水系统石油类污染物的生物降解作用开展研究，通过野外调研和室内分析研究相结合，在传统的污染水文地质学理论方法基础上，引入新兴的分子生物学技术手段，从污染过程中组分传质-化学演化-微生物响应的协同关系出发，揭示地下水中石油污染组分的迁移转化、污染过程中的地球化学变化和污染胁迫下的微生物群落特征响应（结构、类型、分布等），进而通过数据综合分析，揭示石油污染地下水系统中的物化、生物交互作用对生物降解的控制机制，并在此基础上探讨该石油污染场地原位空气扰动修复对地下水中污染物生物降解的影响。
主要研究成果如下：
(1)对场地污染特征进行10个月（2009年9月~2010年7月）的连续动态监测显示，场地地下水中总石油烃（TPH）平均含量高达5.21mg/L，显著超过国家相关标准，主要的石油类污染物种类主要有烷烃类、芳烃类以及非烃类，其中芳烃类含量较高，在0.53~2.13mg/L之间，其中苯含量在0.01~0.31mg/L之间，二甲苯含量在0.08~0.98mg/L之间，均超过了GB/T5750.8-2006中规定的饮用水标准，亟待采取修复措施；
(2)场地地下水中石油类污染物在时间和空间上均呈现动态变化，在监测时段内TPH浓度整体呈现下降的变化趋势，大幅下降主要出现在2009年末至2010年初，2010年3月后污染物的自然衰减程度明显减弱，另外石油组分变化特征分析结果显示，烷烃与芳烃之比和烃类与非烃类之比均呈下降趋势，这表明随着时间的发展，地下水中石油污染物发生着较为缓慢的生物降解作用；沿地下水径流路径，组分浓度、类异戊二烯类化合物等生物标志物数据同样显示发生了生物降解作用，但上述烷烃、芳烃与非烃类比值却沿径流路径有所升高，表明生物降解作用虽存在但并不突出；
(3)地下水中总石油烃含量在空间上的分布显示该场地存在两个污染较严重区域，为进一步探明场地地下水的污染模式，对不同位置垂向土壤中TPH含量进行了分析，发现TPH在不同地点垂向上呈现两种不同的变化规律，一种是随深度逐渐减小，另一种则在地下水位附近有明显的升高，由此将该地区地下水石油污染来源归结为两种模式：其一是垂向入渗式，主要发生在场地上游污油坑附近；其二是水平扩散迁移式，是场地中下游石油污染来源的主要途径；
(4)对污染场地地下水水化学特征进行了研究，结果发现：虽然场地地下水遭受不同程度的石油污染，但其中主要离子组成相对稳定，水化学类型以HCO3-Na和HCO3-Ca型水为主，通过对水化学离子的平衡计算推测场地地下水中高浓度的HCO3-在一定程度上可能与该地区发生石油污染物的生物降解有关；
(5)为了解场地内石油污染物降解的生物地球化学过程，对地下水氧化还原特征和生物降解过程中的电子受体含量进行了分析，结果表明：场地地下水处于还原环境，石油污染物以厌氧降解为主导，氧化还原电位Eh进一步指示该地区生物降解应处于铁还原和硫酸盐还原阶段，同时，电子受体的动态变化也显示，溶解相铁锰在2010年1月后有不同程度的升高，硫酸盐含量在监测期内一直呈下降态势，至2010年后其下降解程度有所减缓，结合反应产物S2-等的动态变化和Eh-pH分布关系，综合反映出该场地发生了铁锰和硫酸盐还原过程；
(6)利用PCR-DGGE技术对场地内2010年3月后细菌、古细菌群落结构和多样性进行研究，分析发现：细菌群落组成在位于污油坑Z1处变化最为显著，2010年3月与7月结构相似性系数仅为0.261，而在相同时间内，同一流线上的点群落结构相似性较高，最高相似系数为0.714，进一步采用细菌多样性指数来综合反映地下水中群落组成和丰度的变化，将计算结果以时间和空间为因变量进行ANOVA分析，表明细菌多样性指数在时空上的变化不显著，可能受到其他因素的控制，而古细菌指数变化与时间呈显著相关；
(7)对细菌DGGE图谱中的主要条带进行切胶回收、测序以了解该地区地下水微生物物种组成，测序比对结果显示：场地地下水微生物细菌类群主要有三大类，分别为Betaproteobacteria，Gamaproteobactera和Flavobacteria，其中以Betaproteobacteria纲细菌占优势，且以厌氧环境下生存的菌种居多，检测到与场地污染物降解和生物地球化学环境相关的菌种有Dechloromonas sp.，Gallionella sp.，Thiothrix sp.；
(8)采用主成分分析方法（PCA）分别对场地石油污染组分、地下水水化学与微生物群落数据进行降维分析，提取出9个污染主因子、4个化学主因子和8个微生物菌群因子，各因子分别反映了污染物类型、来源、地下水化学环境、生物地球化学过程以及不同特征菌群的分类，随后利用典范对应分析方法（CCA）建立各类环境因子之间的相互关系，通过归纳分析将污染场地按CCA排序图分为苯系物降解区、烷烃降解区和污染背景区，另外，按降解过程分为好氧或微还原区、铁锰还原区、硫酸盐还原区、产甲烷区和弱降解区，进而根据此分区对2010年3月后场地内地下水中生物降解控制因子进行识别，场地上游因受长期污染，降解能力减弱，以产甲烷作用为主，烷烃降解占优势，下游则以芳香烃降解为主，发生铁锰还原和硫酸盐还原过程；
(9)在以上天然条件下场地生物降解机制研究的基础上，结合后期开展的场地原位空气扰动修复工程，对注气扰动下污染物生物降解机制的变化进行了研究，首先通过为期13d的原位单井AS修复试验，修复目标区域地下水中TPH降低达80%，其中各种石油类污染组分浓度均有不同程度的降低，主要以芳烃类组分最为显著，化学方面由于注气使地下水环境由厌氧向好氧转变，氧化还原参数Eh有显著升高，这种转变尤其体现在离注气井最近的N1井，进一步对AS期间微生物特征分析发现，微生物群落的响应主要体现在影响带内物种的丰度上，不会显著改变物种的组成，此外由地下水中芳香烃的氧化基因（TOD）的变化指出，AS可在一定程度上促进注气井周围4m范围内的好氧生物降解，但此范围远小于AS所引起的物理响应指示的影响范围。
As an important part of water resources, groundwater is the reserves and strategic resourcesfor social development. However, with Chinese rapid economic growth in recent decades,groundwater pollution is getting worse, which not only significantly aggravated the contradictionof water shortage, but also greatly threaten ecology and human health. Among numerouspollutants, there is growing concern about petroleum due to its high toxicity. Especially,pollution caused by petroleum became more and more universal and serious in shallowgroundwater and soil environment system, calling for an imminent remediation. Biodegradationis the only process that can reduce pollutants content in the environment, and the mechanism ofpetroleum pollutants biodegradation in groundwater therefore has important scientificsignificance for contaminated water remendiation and water sustainable management.
A site in NE China was selected as a particular case characterised by a long history of oilcontamination. Forensic identification of biodegradation on this contaminated groundwater sitewas studied by multidisciplinary knowledge from traditional contamination hydrogeology andemerging molecular biology. Integrated groundwater modelling, hydrochemical and PCR-DGGEmethods were applied for investigation of the hydrogeologic, hydrogeochemical and microbialcharacteristics of groundwater system. Controlling factors were then recognized by the means ofmulti-factors statistics. Based on these, influences of in situ air sparging on biodegradation werealso discussed.
Main results of this paper are described in detail as follows:
(1)10-month monitoring was carried out for variations of pollutants throughout theinterested site. The average TPH concentration of5.21mg/L largely exceeded the value inrelevant national standards. Pollutants contained alkanes, aromatic hydrocarbons andnon-hydrocarbons. The aromatic hydrocarbon concentration is much higher, at between0.53~2.13mg/L with benzene concentration of between0.010.31mg/L, xylene of between0.08~0.98mg/L, more than their limitations in of drinking water standard (GB/T5750.8-2006).
(2) Dynamic changes of contaminants in time and space showed TPH concentrationdecreased during the whole monitoring period. Rapid drop occurred in late2009till early2010 while natural attenuation of pollutants got weak after March2010. Variations of petroleumcomponents showed the ratio of alkanes and aromatic hydrocarbons, and that of hydrocarbon andnon-hydrocarbon declined with time, indicating the occurrence of biodegradation but in relativeweak degree. biodegradation was also confirmed by biomarker data along the groundwater flowpaths but didn’t dominate as the above two ratios increased along flow lines.
(3) According to the distribution of TPH in this site, two cores of high contaminants can bedistinguished. To find out the contamination patterns of this field site, TPH concentrations of soilin vertical profiles at typical points were analysis. Results showed two sorts of treads existed.One is continuous declination with depth, and the other is obvious peak near groundwater level.So there should be two patterns: first, vertical infiltration, mainly happens near oil-water pond inthe SW of this site; Second, horizontal spread, is the main path in the middle and downstream.
(4) Characteristics of groundwater chemistry at the pollution site were also studied. Wefound that although groundwater there suffered different degrees of oil pollution, the major ionscomposition was relatively stable and defined the water types as HCO3-Na and HCO3-Ca.Moreover, high concentration of HCO3in groundwater may be resulted from biodegradation ofpollutants there according to chemical balance calculation.
(5) To further understand the biogeochemical process at this site, redox conditions andelectron acceptors in groundwater were investigated. Eh indicated a reducing environment ofiron-manganese and/or sulfate reduction stage. Breakthrough of potential REDOX indicatorrevealed dissolved iron and manganese increased after January2010, while sulfate in themonitoring period dropped but slowly in2010. These reflect the site was experiencingiron-manganese and/or sulfate reduction process;
(6) PCR-DGGE method was used to study structure and diversity of bacteria and archaeacommunity in this site after March2010till July2010. Analysis indicated that bacterialcommunity composition at Z1near the oil-water pond varied most with the lowest similaritycoefficient of only0.261between March2010and July, while higher coefficients could be foundamong points along the same flow lines and the highest similarity coefficient was0.714.Furthermore, diversity indices reflecting changes of species composition and abundance werecalculated. Using the calculated results, ANOVA analysis was performed in various time andspaces respectively. Results showed that bacteria diversity index had no significant changes withtime and space, while the archaea presented significant relevance with time.;
(7) Main bands in the DGGE profiles were excised, re-amplified and sequenced for insight into microbial species composition in groundwater. Results of sequence alignment showed thereare three main classes in groundwater: Betaproteobacteria, Gamaproteobactera and Flavobacteria.Betaproteobacteria was dominated and most species were anaerobic. Detected species relevant tobiodegradation and biogeochemical environment are Dechloromonas sp., Gallionella sp.,Thiothrix sp, etc.
(8) Principal Component Analysis (PCA) was performed to reduce the dimensionality ofcomplex pollutants, hydrochemical and microbial data sets.9pollution factors,4chemicalfactors and8bacterial factors were extracted, reflecting the pollutant source types, groundwaterchemical/biogeochemical environment, and flora of different characteristics respectively.Canonical Correspondence Analysis (CCA) was then carried out using the above extractedfactors to investigate relationships among them. Thereby, CCA ordination diagram could bedivided into three partitions of benzene series degradation, alkanes degradation and backgroundlevel according to the pollutants, and five partitions of aerobic or weak reduction,iron-manganese reduction, sulfate reduction, methanogenesis and weak degradation according tothe degradation processes. Controlling factors of biodegradation were judged by the location ofpoints representing groundwater samples in the CCA partitions diagram. Analysis implieddegradation ability in upstream turned quite limited but mainly with several alkanes undermethane-producing process probably due to long-term pollution, while downstream was mainlyexperiencing aromatic hydrocarbons degradation under iron-manganese and sulfate reductionprocesses;
(9) Based on the above natural biological degradation mechanism research, influences ofin-situ biodegradation on pollutants biodegradation were further studied. First, after13-d singlewell AS pilot test, TPH in groundwater of interested zone reduced by80%while differentdecrease degrees varied with different petroleum components, significantly in aromatichydrocarbons. Second, due to air injection, groundwater REDOX condition transformed fromanaerobic to aerobiotic. Oxygen oxidation reduction parameter Eh increased significantly andsuch change was most obvious in N1nearest to air injecting well. Third, changes of microbialcharacteristics during the AS presented species abundance rather than species composition wasaffected by AS. Finally, aromatic oxygenase gene was quantificationally tested by Realtime-PCR,and the results revealed13-d single well AS pilot test could only promote aerobic biodegradation within4mradius around AS injecting well to the largest extent, which is far less than physicalinfluence area by AS.
本文依托我国东北某油田区野外实际污染场地，针对浅层地下水系统石油类污染物的生物降解作用开展研究，通过野外调研和室内分析研究相结合，在传统的污染水文地质学理论方法基础上，引入新兴的分子生物学技术手段，从污染过程中组分传质-化学演化-微生物响应的协同关系出发，揭示地下水中石油污染组分的迁移转化、污染过程中的地球化学变化和污染胁迫下的微生物群落特征响应（结构、类型、分布等），进而通过数据综合分析，揭示石油污染地下水系统中的物化、生物交互作用对生物降解的控制机制，并在此基础上探讨该石油污染场地原位空气扰动修复对地下水中污染物生物降解的影响。
主要研究成果如下：
(1)对场地污染特征进行10个月（2009年9月~2010年7月）的连续动态监测显示，场地地下水中总石油烃（TPH）平均含量高达5.21mg/L，显著超过国家相关标准，主要的石油类污染物种类主要有烷烃类、芳烃类以及非烃类，其中芳烃类含量较高，在0.53~2.13mg/L之间，其中苯含量在0.01~0.31mg/L之间，二甲苯含量在0.08~0.98mg/L之间，均超过了GB/T5750.8-2006中规定的饮用水标准，亟待采取修复措施；
(2)场地地下水中石油类污染物在时间和空间上均呈现动态变化，在监测时段内TPH浓度整体呈现下降的变化趋势，大幅下降主要出现在2009年末至2010年初，2010年3月后污染物的自然衰减程度明显减弱，另外石油组分变化特征分析结果显示，烷烃与芳烃之比和烃类与非烃类之比均呈下降趋势，这表明随着时间的发展，地下水中石油污染物发生着较为缓慢的生物降解作用；沿地下水径流路径，组分浓度、类异戊二烯类化合物等生物标志物数据同样显示发生了生物降解作用，但上述烷烃、芳烃与非烃类比值却沿径流路径有所升高，表明生物降解作用虽存在但并不突出；
(3)地下水中总石油烃含量在空间上的分布显示该场地存在两个污染较严重区域，为进一步探明场地地下水的污染模式，对不同位置垂向土壤中TPH含量进行了分析，发现TPH在不同地点垂向上呈现两种不同的变化规律，一种是随深度逐渐减小，另一种则在地下水位附近有明显的升高，由此将该地区地下水石油污染来源归结为两种模式：其一是垂向入渗式，主要发生在场地上游污油坑附近；其二是水平扩散迁移式，是场地中下游石油污染来源的主要途径；
(4)对污染场地地下水水化学特征进行了研究，结果发现：虽然场地地下水遭受不同程度的石油污染，但其中主要离子组成相对稳定，水化学类型以HCO3-Na和HCO3-Ca型水为主，通过对水化学离子的平衡计算推测场地地下水中高浓度的HCO3-在一定程度上可能与该地区发生石油污染物的生物降解有关；
(5)为了解场地内石油污染物降解的生物地球化学过程，对地下水氧化还原特征和生物降解过程中的电子受体含量进行了分析，结果表明：场地地下水处于还原环境，石油污染物以厌氧降解为主导，氧化还原电位Eh进一步指示该地区生物降解应处于铁还原和硫酸盐还原阶段，同时，电子受体的动态变化也显示，溶解相铁锰在2010年1月后有不同程度的升高，硫酸盐含量在监测期内一直呈下降态势，至2010年后其下降解程度有所减缓，结合反应产物S2-等的动态变化和Eh-pH分布关系，综合反映出该场地发生了铁锰和硫酸盐还原过程；
(6)利用PCR-DGGE技术对场地内2010年3月后细菌、古细菌群落结构和多样性进行研究，分析发现：细菌群落组成在位于污油坑Z1处变化最为显著，2010年3月与7月结构相似性系数仅为0.261，而在相同时间内，同一流线上的点群落结构相似性较高，最高相似系数为0.714，进一步采用细菌多样性指数来综合反映地下水中群落组成和丰度的变化，将计算结果以时间和空间为因变量进行ANOVA分析，表明细菌多样性指数在时空上的变化不显著，可能受到其他因素的控制，而古细菌指数变化与时间呈显著相关；
(7)对细菌DGGE图谱中的主要条带进行切胶回收、测序以了解该地区地下水微生物物种组成，测序比对结果显示：场地地下水微生物细菌类群主要有三大类，分别为Betaproteobacteria，Gamaproteobactera和Flavobacteria，其中以Betaproteobacteria纲细菌占优势，且以厌氧环境下生存的菌种居多，检测到与场地污染物降解和生物地球化学环境相关的菌种有Dechloromonas sp.，Gallionella sp.，Thiothrix sp.；
(8)采用主成分分析方法（PCA）分别对场地石油污染组分、地下水水化学与微生物群落数据进行降维分析，提取出9个污染主因子、4个化学主因子和8个微生物菌群因子，各因子分别反映了污染物类型、来源、地下水化学环境、生物地球化学过程以及不同特征菌群的分类，随后利用典范对应分析方法（CCA）建立各类环境因子之间的相互关系，通过归纳分析将污染场地按CCA排序图分为苯系物降解区、烷烃降解区和污染背景区，另外，按降解过程分为好氧或微还原区、铁锰还原区、硫酸盐还原区、产甲烷区和弱降解区，进而根据此分区对2010年3月后场地内地下水中生物降解控制因子进行识别，场地上游因受长期污染，降解能力减弱，以产甲烷作用为主，烷烃降解占优势，下游则以芳香烃降解为主，发生铁锰还原和硫酸盐还原过程；
(9)在以上天然条件下场地生物降解机制研究的基础上，结合后期开展的场地原位空气扰动修复工程，对注气扰动下污染物生物降解机制的变化进行了研究，首先通过为期13d的原位单井AS修复试验，修复目标区域地下水中TPH降低达80%，其中各种石油类污染组分浓度均有不同程度的降低，主要以芳烃类组分最为显著，化学方面由于注气使地下水环境由厌氧向好氧转变，氧化还原参数Eh有显著升高，这种转变尤其体现在离注气井最近的N1井，进一步对AS期间微生物特征分析发现，微生物群落的响应主要体现在影响带内物种的丰度上，不会显著改变物种的组成，此外由地下水中芳香烃的氧化基因（TOD）的变化指出，AS可在一定程度上促进注气井周围4m范围内的好氧生物降解，但此范围远小于AS所引起的物理响应指示的影响范围。
As an important part of water resources, groundwater is the reserves and strategic resourcesfor social development. However, with Chinese rapid economic growth in recent decades,groundwater pollution is getting worse, which not only significantly aggravated the contradictionof water shortage, but also greatly threaten ecology and human health. Among numerouspollutants, there is growing concern about petroleum due to its high toxicity. Especially,pollution caused by petroleum became more and more universal and serious in shallowgroundwater and soil environment system, calling for an imminent remediation. Biodegradationis the only process that can reduce pollutants content in the environment, and the mechanism ofpetroleum pollutants biodegradation in groundwater therefore has important scientificsignificance for contaminated water remendiation and water sustainable management.
A site in NE China was selected as a particular case characterised by a long history of oilcontamination. Forensic identification of biodegradation on this contaminated groundwater sitewas studied by multidisciplinary knowledge from traditional contamination hydrogeology andemerging molecular biology. Integrated groundwater modelling, hydrochemical and PCR-DGGEmethods were applied for investigation of the hydrogeologic, hydrogeochemical and microbialcharacteristics of groundwater system. Controlling factors were then recognized by the means ofmulti-factors statistics. Based on these, influences of in situ air sparging on biodegradation werealso discussed.
Main results of this paper are described in detail as follows:
(1)10-month monitoring was carried out for variations of pollutants throughout theinterested site. The average TPH concentration of5.21mg/L largely exceeded the value inrelevant national standards. Pollutants contained alkanes, aromatic hydrocarbons andnon-hydrocarbons. The aromatic hydrocarbon concentration is much higher, at between0.53~2.13mg/L with benzene concentration of between0.010.31mg/L, xylene of between0.08~0.98mg/L, more than their limitations in of drinking water standard (GB/T5750.8-2006).
(2) Dynamic changes of contaminants in time and space showed TPH concentrationdecreased during the whole monitoring period. Rapid drop occurred in late2009till early2010 while natural attenuation of pollutants got weak after March2010. Variations of petroleumcomponents showed the ratio of alkanes and aromatic hydrocarbons, and that of hydrocarbon andnon-hydrocarbon declined with time, indicating the occurrence of biodegradation but in relativeweak degree. biodegradation was also confirmed by biomarker data along the groundwater flowpaths but didn’t dominate as the above two ratios increased along flow lines.
(3) According to the distribution of TPH in this site, two cores of high contaminants can bedistinguished. To find out the contamination patterns of this field site, TPH concentrations of soilin vertical profiles at typical points were analysis. Results showed two sorts of treads existed.One is continuous declination with depth, and the other is obvious peak near groundwater level.So there should be two patterns: first, vertical infiltration, mainly happens near oil-water pond inthe SW of this site; Second, horizontal spread, is the main path in the middle and downstream.
(4) Characteristics of groundwater chemistry at the pollution site were also studied. Wefound that although groundwater there suffered different degrees of oil pollution, the major ionscomposition was relatively stable and defined the water types as HCO3-Na and HCO3-Ca.Moreover, high concentration of HCO3in groundwater may be resulted from biodegradation ofpollutants there according to chemical balance calculation.
(5) To further understand the biogeochemical process at this site, redox conditions andelectron acceptors in groundwater were investigated. Eh indicated a reducing environment ofiron-manganese and/or sulfate reduction stage. Breakthrough of potential REDOX indicatorrevealed dissolved iron and manganese increased after January2010, while sulfate in themonitoring period dropped but slowly in2010. These reflect the site was experiencingiron-manganese and/or sulfate reduction process;
(6) PCR-DGGE method was used to study structure and diversity of bacteria and archaeacommunity in this site after March2010till July2010. Analysis indicated that bacterialcommunity composition at Z1near the oil-water pond varied most with the lowest similaritycoefficient of only0.261between March2010and July, while higher coefficients could be foundamong points along the same flow lines and the highest similarity coefficient was0.714.Furthermore, diversity indices reflecting changes of species composition and abundance werecalculated. Using the calculated results, ANOVA analysis was performed in various time andspaces respectively. Results showed that bacteria diversity index had no significant changes withtime and space, while the archaea presented significant relevance with time.;
(7) Main bands in the DGGE profiles were excised, re-amplified and sequenced for insight into microbial species composition in groundwater. Results of sequence alignment showed thereare three main classes in groundwater: Betaproteobacteria, Gamaproteobactera and Flavobacteria.Betaproteobacteria was dominated and most species were anaerobic. Detected species relevant tobiodegradation and biogeochemical environment are Dechloromonas sp., Gallionella sp.,Thiothrix sp, etc.
(8) Principal Component Analysis (PCA) was performed to reduce the dimensionality ofcomplex pollutants, hydrochemical and microbial data sets.9pollution factors,4chemicalfactors and8bacterial factors were extracted, reflecting the pollutant source types, groundwaterchemical/biogeochemical environment, and flora of different characteristics respectively.Canonical Correspondence Analysis (CCA) was then carried out using the above extractedfactors to investigate relationships among them. Thereby, CCA ordination diagram could bedivided into three partitions of benzene series degradation, alkanes degradation and backgroundlevel according to the pollutants, and five partitions of aerobic or weak reduction,iron-manganese reduction, sulfate reduction, methanogenesis and weak degradation according tothe degradation processes. Controlling factors of biodegradation were judged by the location ofpoints representing groundwater samples in the CCA partitions diagram. Analysis implieddegradation ability in upstream turned quite limited but mainly with several alkanes undermethane-producing process probably due to long-term pollution, while downstream was mainlyexperiencing aromatic hydrocarbons degradation under iron-manganese and sulfate reductionprocesses;
(9) Based on the above natural biological degradation mechanism research, influences ofin-situ biodegradation on pollutants biodegradation were further studied. First, after13-d singlewell AS pilot test, TPH in groundwater of interested zone reduced by80%while differentdecrease degrees varied with different petroleum components, significantly in aromatichydrocarbons. Second, due to air injection, groundwater REDOX condition transformed fromanaerobic to aerobiotic. Oxygen oxidation reduction parameter Eh increased significantly andsuch change was most obvious in N1nearest to air injecting well. Third, changes of microbialcharacteristics during the AS presented species abundance rather than species composition wasaffected by AS. Finally, aromatic oxygenase gene was quantificationally tested by Realtime-PCR,and the results revealed13-d single well AS pilot test could only promote aerobic biodegradation within4mradius around AS injecting well to the largest extent, which is far less than physicalinfluence area by AS.
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