生物曝气技术对石油类污染地下水的修复效果及去除机制

针对东北某石油污染场地水文地质条件进行模拟,按照试验场地地层现状进行实验室缩放,研究微生物在含水层介质为砾砂、粗砂和中砂中的迁移速度以及含水层介质吸附的微生物量。选取苯和二甲苯作为目标石油污染物,研究生物曝气技术对被污染地下水的修复效果及其去除污染物的机制。实验结果表明:微生物在介质中的迁移速度从大到小为砾砂、粗砂、中砂;介质吸附微生物量的顺序从大到小为中砂、粗砂、砾砂;生物曝气4个月后,苯和二甲苯去除率分别为86.4%和81.7%,BS对中砂层中的苯和二甲苯去除效果好于砾砂层和粗砂层,苯的去除效果好于二甲苯。由挥发机制去除的污染物为46.24%,生物降解去除的污染物为36.98%,BS技术可以有效去除地下水中石油类污染物。     

顶空气相色谱法测定地层水中的苯系物

利用极性聚乙二醇弹性石英毛细管柱分离苯系物，在线顶空气相色谱法测定地层水中的苯系物。讨论了色谱柱、载气压力、液相体积、顶空压力、顶空加热温度等因素对测定的影响。该方法实现了地层水中苯、甲苯、乙苯、对二甲苯、间二甲苯、邻二甲苯、异丙苯、苯乙烯等各组分的完全分离，方法的检出限在0．07—0．23μg／L，8次测定相对标准偏差在2．98％-4．91％，加标回收率为95．2％-104％。方法可用于地层水等液体样品中苯系物的测定。     

河床含水系统对单环芳烃净化特征室内模拟

为了模拟长期排污河流中单环芳烃在地表水-地下水系统迁移转化规律以及不同含水介质和水动力条件对单环芳烃的净化特征, 室内土柱实验采用3种有代表性的天然砂土为研究对象, 以生活污水模拟纳污河流, 实验历时5个月.单环芳烃的自然净化作用主要发生在河床底下0.4m内, 垂直向下单环芳烃各组分浓度呈由高到低的分布特征; 粗砂对苯、甲苯和单环芳烃总量(TBETX) 总净化率分别为32.06%、21.39%和27.13%;中砂1分别为76.26%、81.40%、87.99%;中砂2分别为68.94%、74.41%、81.69%, 这表明, 河流污染初期河床底含水介质完全饱水, 含水介质颗粒尺寸越大, 对单环芳烃的净化率就越低, 单环芳烃容易迁移进入地下水中; 随着时间的延长, 河床底部淤泥层不断增加, 砂层中的水流处于非饱和状态, 淤泥层和含水介质系统对单环芳烃的净化能力较饱水流时大, 单环芳烃不容易迁移进入地下水.      

典型石油烃组分在地下水中的自然衰减规律

为了解石油烃类污染物在地下水中的自然衰减规律,以苯、萘、菲作为目标污染物,采用实验场地4种天然砂土作为含水层介质进行了室内模拟实验。结果表明：在单组分和混合组分溶液中,苯、萘和菲在地下含水层介质中的自然衰减均符合一级动力学方程;在不同含水层介质中,苯和萘的衰减速率大小顺序为粉砂>中砂≈粗砂>砾砂,而菲的自然衰减速率大小顺序为粉砂≈中砂≈粗砂>砾砂;微生物降解在苯和萘的自然衰减中起重要作用,而固相吸附在菲的自然衰减中起重要作用。3种物质共存时,苯和萘的自然衰减加快,菲的自然衰减减慢。     

去除地下水芳香烃污染物:实验室含水层土柱研究

芳香烃污染地下水以其污染普遍、危害巨大、去除困难及治理费用昂贵而倍受各国环境学者及水文地质学者的关注。以苯及甲苯作为标示污染物,利用室内饱水含水层土柱,通过对污染带的模拟实验发现,苯和甲苯在反硝化条件下产生生物降解,二者的去除率分别大于７７％和８８％;反硝化条件下,苯和甲苯显示出降解性差异,甲苯更易于降解;硫酸还原作用可能是苯和甲苯被去除的另一机理,但实验结果显示,ＮＯ－３高时,对硫酸还原菌的生长具有抑制作用。     

某石化污染场地含水层自然降解BTEX能力评估

地下水污染问题是国家关注的重要环境问题之一,监测与评估含水层自然降解污染物能力是防治地下水污染的基本手段,也是国外地下水中修复技术研究热点课题。以华北平原某石油化工类场地为案例,通过调查场地水文地质条件、土壤及地下水污染现状,监测场地地下水中苯系物(BTEX)浓度及相关化学参数变化,运用微生物水文地球化学方法和水文地质方法,估算了该场地含水层自然降解苯系物量。这一研究成果为评估我国石油类场地地下水污染的自然修复能力提供了实证和基础数据。     

覆膜态Fe（OH）3在厌氧条件下生物降解苯和甲苯的初探

天然条件下氯代烃的污染经常会与石油烃的污染共存,对于这种混合污染羽的治理,第一步采用粒状铁还原氯代烃,后续利用微生物和第一步产生的副产物生物降解石油烃。苯系物是石油烃中毒性较大、存留时间较长的污染物,本文利用批实验的方法研究了厌氧条件下用Fe(OH)3覆膜于石英砂表面的Fe(Ⅲ)作为电子受体降解苯和甲苯。结果表明,Fe(Ⅲ)作为电子受体时苯和甲苯能够发生厌氧生物降解,经过驯化后苯和甲苯的降解速度明显加快。降解实验表明甲苯的降解速度比苯的降解速度快,苯降解的半衰期是4.02d,甲苯降解的半衰期是3.81d。     

空气扰动技术修复氯苯污染地下水的影响因素研究

通过实验室一维砂柱模拟研究了不同影响因素下空气扰动技术(air sparging,AS)修复氯苯污染地下水的效果,包括介质渗透性、曝气方式、共存污染物、残余饱和态氯苯。结果表明:介质渗透性极大地影响着AS的效果,渗透系数越大,去除效果越好。对渗透系数为10-5m/s数量级及其以下的介质应用AS较为困难;在曝气时间相同的情况下,对于渗透系数为5.1×10-4m/s的中砂,脉冲曝气较连续曝气效果好,对于渗透系数为6.2×10-3m/s的粗砂,2种曝气方式效果相仿;苯和氯苯共存时各污染物的去除存在协同作用;AS对残余饱和态氯苯的去除存在着明显的拖尾效应。     

胶粘剂中苯系物的毛细管气相色谱分析

根据气相色谱的原理，以常规方法为对照，在胶粘剂中苯系物检测中，采用SE—30毛细管和AC20毛细柱双柱定性，用内标法，准确测定胶粘剂苯系物，克服了单柱检测产生的误判现象。     

离子类型对石油污染含水层中微生物去除苯的影响

近来利用微生物原位修复受石油污染的含水层已被广泛关注,然而地下水中含有许多离子成分,这些无机离子对微生物降解有机污染物的影响机制还不清楚。本文采用批量实验研究了淄博齐鲁石化污染地下水中常见的7种无机离子(NO3-、PO4 3-、SO4 2-、Cl-、Ca2+、Mg2+、Fe3+)对微生物生长及生物降解苯的影响规律,利用高通量测序技术进一步探究了苯降解菌的种群特征。结果表明：7种离子都存在一个最适宜微生物生长的离子浓度,低于或超过该浓度苯的去除率明显降低,其中NO3-、SO42-、Fe3+最适宜浓度为0. 4mmol/L,PO4 3-、Cl-、Ca2+、Mg2+最适宜浓度分别为0. 2mmol/L、0. 1mol/L、2. 5mmol/L、2mmol/L;从微生物含量及其变化幅度来看,地下水环境中的NO3-离子对微生物的生长及苯的去除影响最显著,其他离子的影响则较小,但微生物对Cl-的耐受浓度较高。高通量测序结果显示驯化出的苯降解菌主要属于脱硫弧菌属(Desulfovibrio sp)、脱硫芽胞弯曲菌属(Desulfosporosinus sp)、不动杆菌属(Acinetobacter sp)和假单胞菌属(Pseudomonas sp)中的菌株。研究结果可为石油污染地下水的原位生物修复提供一定的科学依据。     

不同浅层含水介质系统对排污河渠中磷去除效果影响的模拟实验

通过模拟 3种不同的浅层地下含水介质系统对排污河渠中磷去除实验 ,发现不同的含水介质对排污河渠中的总磷都有去除和净化的功能 ,并随着含水介质厚度的增加 ,总磷的去除率逐渐升高。不同的含水介质对总磷的去除效果不同 ,中砂对总磷的去除效果明显优于粗砂。去除磷的主要机理为吸附和沉淀 ,含水介质对磷去除的主要影响因素有介质的颗粒大小、不均匀系数、粘粒含量等。由于排污河渠长期的污水渗漏会在河床底部形成底泥 ,增强了对磷的去除效果 ,所以排污河渠一般不易造成对地下水的磷污染。     

两种废物材料在地下水环境治理中的应用

实验利用粉煤灰和矿化垃圾两种废物材料作为反应屏障的反应介质用于修复受渗滤液污染的地下水环境。所设计的两个反应器A、B分别填充矿化垃圾和粉煤灰,利用它们的吸附能力、阳离子交换能力以及微生物的作用去除污染质。试验结果表明:A、B两柱COD的去除率最高可达66%和59%,对铵氮的去除率柱A明显优于柱B,最高可达92.7%,并在81%左右保持稳定。另外柱A对硝酸盐氮和亚硝酸盐氮的去除效果也优于柱B。说明矿化垃圾作为反应屏障介质更加经济可行,可以达到以废治废的目的。     

反硝化增强去除乙醇对多孔介质渗透性的影响

随着乙醇混合汽油的不断推广应用,乙醇将成为地下水中与苯、甲苯、乙苯及二甲苯的同分异构体（BTEX）共存的一种新型污染物。通过4 个含水砂柱实验,研究了乙醇存在及其强化去除对含水介质渗透性能的影响。结果表明：在有限溶解氧与反硝化增强修复条件下,乙醇去除率达92% 以上;生物过程对介质渗透能力影响程度随乙醇初始浓度、消耗速率与补充频率而变化：乙醇初始浓度接近1 000 mg/L 和3 000 mg/L 时,乙醇消耗快,补充频率高,渗透系数下降总体上有连续性,最大下降幅度达一个数量级（×10-1 cm/s）;乙醇初始浓度达到5 000 mg/L 时,渗透性下降显著,可下降两个数量级,但乙酸的积累可影响生物活性,并使得渗透性变化出现反复;当不含乙醇时,汽油溶解组分对介质渗透性能的影响相对不明显。     

潮白河受水区再生水入渗盐污染模拟柱试验

根据工程地质勘察及采样测试分析,选取北京市顺义潮白河再生水受水区3种典型代表性土壤介质(砾石含砂、细砂、粉质粘土)装柱,并采用受水区再生水进行淋溶模拟土柱试验。测试结果分析表明,在3种典型土壤介质中,阳离子交换吸附作用主要体现为K+与Ca²⁺之间的交换,且粉质粘土柱中阳离子的离子交换作用较砾石含砂柱和细砂柱更为显著。另外,试验结果还表明,随着土壤介质中粘粒含量、总有机碳含量、阳离子交换容量和粘土矿物总量的增加,典型介质淋溶模拟土柱试验中阳离子交换作用达到平衡时所需要的时间也就越长,分别为砾石含砂72 d、细砂80 d和粉质粘土86 d。定量结果计算也证明：粉质粘土介质的各阴、阳离子本底含量最高,单位质量粉质粘土介质硬度及溶解性总固体(TDS)的贡献量最大,分别为5 767 mg/g和6 952 mg/g。     

应用质量通量评估地下水中BTEX和乙醇的自然衰减

近年来,应用于修复石油烃污染地下水的监测自然衰减技术得到了广泛深入研究,同时质量通量方法已逐渐成为评 估地下水燃油污染场地自然衰减监测修复效能的重要手段。通过在室内砂槽中添加乙醇汽油组分,监测其自然衰减,利用 质量通量方法,得出了BTEX和乙醇的质量减少率、自然衰减速率常数K;结合非反应示踪剂溴离子,评价了BTEX和乙醇 自然衰减因素中吸附和微生物的联合降解效应。结果表明,自然衰减是地下水中燃油组分修复的重要机制,质量通量方法 是评估自然衰减的有效方法之一。BTEX和乙醇在自然衰减过程中被去除的比例分别为78.88%和98.71%,其中约98%的 BTEX 因吸附和生物降解联合作用被去除,接近100%的乙醇因内在生物降解作用被去除;BTEX 的自然衰减速率为 0.077d-1~0.167d-1,乙醇为0.353d-1,自然条件下乙醇比BTEX更容易衰减。     

石灰岩含水介质中苯系物（BTEX） 生物可降解性判识

    岩溶含水系统遭受石油烃污染的环境问题十分普遍。相对于多孔含水介质,石油烃BTEX在石灰岩含水介质中的生 物可降解性还不确定。为此,本研究开展了BTEX在石灰石和岩溶地下水介质中的静态微元体实验。经过77天的实验检测 分析,结果表明：（1） BTEX化合物在可利用电子受体溶解氧或硝酸盐存在条件下具有生物可降解性;（2） 向系统中补充 电子受体硝酸盐,具有促进生物降解的作用,其对BTEX的去除率可高达94%;（3） 未发现补充硫酸盐能够促进BTEX生物 可降解性;（4） 甲苯和二甲苯容易被生物降解,但苯的去除具有一定的难度。     

Mobilization and transport of organic compounds from reservoir rock and caprock in geological carbon sequestration sites

Supercritical CO₂ (scCO₂) is a good solvent for organic compounds such as benzene, toluene, ethyl-benzene, and xylene (BTEX), phenols, and polycyclic aromatic hydrocarbons (PAHs). Monitoring results from geological carbon sequestration (GCS) field tests have shown that organic compounds are mobilized following CO₂ injection. Such results have raised concerns regarding the potential for groundwater contamination by toxic organic compounds mobilized during GCS. Knowledge of the mobilization mechanism of organic compounds and their transport and fate in the subsurface is essential for assessing risks associated with GCS. Extraction tests using scCO₂ and methylene chloride (CH₂Cl₂) were conducted to study the mobilization of volatile organic compounds (VOCs, including BTEX), the PAH naphthalene, and n-alkanes by scCO₂ from representative reservoir rock and caprock obtained from depleted oil reservoirs and coal from an enhanced coal-bed methane recovery site. Results showed that the extent of mobilization for the organic compounds was a function of the source rock. In fate and transport sand column experiments, moisture content was found to have an important influence on the transport of the organic compounds. In dry sand columns the majority of the compounds were retained in the column except benzene and toluene. In wet sand columns the mobility of the BTEX was much higher than that of naphthalene. Based upon the results determined for the reservoir rock, caprock, and coal samples studied here, the risk to aquifers from contamination by organic compounds appears to be relatively low; however, further work is necessary to fully evaluate the risks.     

Transport of BTEX Vapours Through Granular Soils with Different Moisture Contents in the Vadose Zone

The single-ring aromatic hydrocarbons benzene, toluene, ethylbenzene and m-xylene (BTEX) are common and dangerous pollutants in subsurface environments. The diffusive transport of BTEX vapours through the unsaturated zone of the ground is a potential health hazard to humans, living in the vicinity of petroleum fuel contaminated sites. Past studies have shown that gas transport through the vadose zone can be influenced by moisture content due to variations in gaseous permeability, phase partitioning and aerobic biodegradation. In this particular study laboratory soil column experiments were employed to compare the diffusive transport of BTEX vapours through a sand layer of high moisture content, where biodegradation of BTEX compounds occurred, with diffusion through air-dried sand. The presence of a thin soil layer of high moisture content reduced the gaseous concentrations of benzene and toluene and stopped the migration of ethylbenzene and m-xylene vapours, demonstrating its efficiency as a barrier on the diffusive transport of BTEX vapours in unsaturated soil.     

Column test-based features analysis of clogging in artificial recharge of groundwater in Beijing

With the completion of South-North Water Transfer Project in China, plenty of high quality water will be transported to Beijing. To restore the groundwater level in Beijing, part of transferred water is planned to be used for artificial recharge. Clogging is an unavoidable challenge in the artificial recharge process. Therefore, a test is designed to analyse clogging duration and scope of influence and to test the reinjection properties of different recharge media. The test employs the self-designed sand column system with variable spacing and section monitoring, composed of four parts: Sand column, water-supply system, pressure-test system and flow-test system, to simulate the clogging of artificial recharge of sand and gravel pits. The hydraulic conductivity levels of all sand column sections are obtained to analyse the clogging of the injection of different concentrations in media of different particle sizes. In this experiment, two kinds of media are used–round gravel from sand and gravel pit in Xihuang village and the sand from sand and gravel pit by the Yongding River. The concentrations of recharge fluid are respectively 0.5 g/L and 1 g/L. The results show that clogging usually lasts for 20 hrs., and the hydraulic conductivity drops to the original 10%. Clogging usually occurs at 0–12 cm section of the sand column. The scope of influence is 0–60 cm. In column 3 and 4, whose average particle sizes are larger, section 20–50 cm also suffers from clogging, apart from section 0–12 cm. The effective recharge times are respectively 33 hrs. in column 1, 14 hrs. in column 2, 12 hrs. in column 3 and 12 hrs. in column 4. The larger the average particle size is, the quicker the clogging occurs. In media of larger particles, the change in suspension concentration does not have significant influence on the development of clogging. In conclusion, it is suggested that during artificial recharge, the conditions of reinjection medium should be fully considered and effective method of recharge be employed in order to improve effective recharge time.     

Mesoscale experimental study on chemical composition,pore size distribution,and permeability of tailings

To study the seepage characteristics of tailing sand, an indoor sand column test was performed with three kinds of tailing sand obtained from Henan and Shaanxi provinces, China. River sand, quartz sand, and glass beads were also employed for comparison. Using the nuclear magnetic resonance, the researchers studied pore size distribution and permeability under different hydraulic gradients. The chemical composition and particle morphology were analyzed by energy-dispersive spectrometry and X-ray diffraction. The results were as follows. (1) The three kinds of tailings sand are small in diameter, mainly in the range from 0.15 to 0.5 mm. Their diameter distribution is more concentrated than river sand. The surface of tailing sand is rough. As for chemical composition, tailing sand contains many kinds of metal elements. (2) With hydraulic gradient increasing, the micropores in the tailings samples become fewer, the larger pores grow in number, and the peak of the pore size distribution changes to the left; blocking is more obvious. (3) The small pores gradually decrease during the test. Under the influence of groundwater pressure, the smaller gravel could migrate and block tiny pores. The structure of particle arrangement becomes denser. Therefore, it would prevent the seepage liquid from passing through the medium. The permeability coefficient K decreases.