生物通风技术修复柴油污染土壤的土柱模拟实验

生物通风技术是将土壤气相抽提和生物降解结合起来的原位强迫氧化降解方法,对于修复因地下储油罐泄漏引起的土壤污染具有广阔的应用前景。通过室内土柱模拟柴油泄漏污染土壤,分析了不同历时残余总石油烃(total pe-troleum hydrocarbon,TPH)的平衡分布规律以及土壤中不同深度柴油量、总柴油量的变化。结果表明:(1)各柱残余TPH剖面分布差异的原因受土柱的初始装填情况的影响较大;(2)残余TPH平衡分布曲线呈双峰型的土柱,柴油的去除主要以挥发作用及生物降解作用为主;(3)挥发作用主要是由通风孔隙体积数及土壤含水率来影响的;重力作用则主要是由初始油浓度、土壤含水率、C∶N∶P影响的;除通风方式外,其余4个因素都对生物降解作用有影响;(4)初始油浓度较大,土壤含水率较小的柱8和柱11,生物降解作用最明显,柴油去除效果最好。该成果可为生物通风过程的强化提供理论依据。     

SDBS在土壤中的吸附及对淋洗柴油效果的影响

为考察污染土壤淋洗修复过程中表面活性剂的动态吸附解吸过程及其对淋洗效果影响,以北京潮土为例,采用土柱淋洗实验,对4种浓度(600、1 800、3 000和4 200 mg·L~(-1))的阴离子表面活性剂十二烷基苯磺酸钠(SDBS)淋洗柴油污染土壤的过程进行模拟。结果表明,土柱淋洗过程中北京潮土对SDBS的吸附过程可分3个阶段:快吸附阶段、慢吸附阶段及动态平衡阶段。吸附动力学较好地符合颗粒内扩散方程。SDBS淋洗柴油污染潮土时,初期由于表面活性剂在土壤中的吸附未达到平衡而无法在溶液中形成胶束,导致淋洗液中柴油浓度很低。此后SDBS在土壤中的吸附逐渐达到平衡状态,溶液中SDBS的浓度超过临界胶束浓度(CMC)开始形成胶束,土壤中残留的柴油开始大量解吸。淋洗液中柴油浓度总体呈先升到峰值,而后呈锯齿状波动下降的变化规律。淋洗到400 h时,4种浓度SDBS溶液对柴油的去除率分别为1.06%、1.52%、25.55%和27.99%,柴油去除率与表面活性剂浓度呈正相关。但表面活性剂浓度过高时,会降低土柱中土壤渗透系数,导致淋洗流量显著降低,采用SDBS淋洗柴油污染潮土时,表面活性剂浓度在3 000~4 200 mg·L~(-1)较佳。     

土壤气相抽提去除土壤中汽油烃污染物柱试验研究

原位处理土壤石油污染对于土壤和地下水的有机污染控制具有极其重要的现实意义.通过砂土柱试验研究了原位物理通风的主要工艺形式及运行参数,并初步分析了汽油烃在砂土柱中的迁移和通风去除机制.结果表明,顶部真空抽提与底部注气两种通风方式相比,顶部真空抽提效果较好,砂土柱汽油烃初始质量浓度为2.937 mg/g时,经过104.5 h通风,砂土柱中汽油烃去除率达80.49%.土壤汽油烃初始浓度影响其在土壤中的迁移和去除,土壤汽油烃初始浓度越大,相同通风条件下,物理通风方法去除土壤中挥发性有机物的效率越低.通风及通风方式对砂土中的汽油烃的去除影响很大,连续通风可在砂土柱中形成稳定的负压环境,在汽油烃初始质量浓度为35.730 mg/g时,连续真空抽提264 h,砂土柱中的汽油烃平均去除率达89.29%;间歇通风在砂土柱中形成的负压环境不稳定,但也可以去除砂土柱中的汽油烃.初步分析认为,汽油烃存在负压作用下的向上挥发和重力作用下的向下迁移两个过程,其综合作用的结果导致汽油烃在砂土柱中的分布状况.     

吐温80对柴油污染老化土壤的洗脱特征及影响

研究了柴油污染土壤的老化特性及吐温80(Tween 80)修复柴油污染老化土壤的效率和对总油中含有不同基团物质的洗脱特性,进行了一系列不同浓度的Tween 80洗脱柴油污染老化土壤实验,并使用红外分光光度法对洗脱后的土壤和残留液中的总油及各基团浓度进行测定。结果表明,经过1年时间的老化,约53%的柴油从土壤中挥发,土壤中残留的总油中约40.55%为稳定吸附态。随着洗脱液中Tween 80浓度的提高,老化土壤中总油量不断减少,但当Tween 80浓度超过3 000 mg·L~(-1)时土壤中总油含量的减少速率和Tween 80的增溶效率的增加速率显著降低,因此3 000 mg·L~(-1)浓度的Tween 80作为洗脱液性价比最高,其对吸附态总油的洗脱率为20.30%,对老化土中总油的洗脱率为67.68%。Tween 80溶液洗脱石油污染老化土时,对含烷烃(CH3)基团和含烯烃(CH2)基团的物质洗脱效率较高,而对于含芳烃(CH)基团的物质洗脱效率相对较低。     

粉砂介质包气带中甲苯蒸气挥发的迁移转化

挥发性有机物通过包气带向上迁移到地表或室内引发的蒸气入侵(vapor intrusion,VI)问题越发受到关注。以甲苯作为研究对象,采用土柱实验,对粉砂介质包气带中甲苯蒸气发生的扩散、生物降解的规律进行研究。结果表明,粉砂介质中,甲苯蒸气扩散穿透70 cm土柱时间为24 h,甲苯蒸气在土柱内扩散10 d时,土柱达到短暂的稳态平衡;12~30 d时,处于动态平衡;30~60 d时,土柱内甲苯蒸气浓度下降速率发生变化,土柱内O_2体积分数下降了8%,CO_2体积分数增加了6%;60 d时,甲苯蒸气基本被降解。说明覆盖一定厚度的粉砂对甲苯蒸气的迁移有比较好的阻滞和生物降解作用。     

超声波/紫外线-Fenton反应联用去除克拉玛依土壤中石油类污染物

研究了超声波(ultrasonic)和紫外线(ultraviolet)-Fenton反应联用处理干旱区老化石油污染土壤。土壤TPH含量为30 470 mg/kg,pH值为3,H2O2与Fe比例为50∶1时,H2O2浓度为0.37%、0.74%、1.11%和1.85%在超声波处理6 h土壤TPH去除量分别为4 495、11 983、15 470和19 800 mg/kg;TPH去除量随H2O2/Fe2+增大而增大,H2O2/Fe2+为100∶1时,TPH去除量为12 699 mg/kg。溶液pH值接近中性,H2O2浓度为0.74%,H2O2/Fe2+为50∶1,超声波与UV共同作用2 h和4 h,TPH去除量分别达到14 824和21 821 mg/kg;UV单独作用2 h、4 h对土壤TPH去除量为9 253和12 845 mg/kg。超声波-Fenton反应对1,2-二甲苯降解效果最好,其次为C17-C28的直链及支链烷烃,最低为烃类衍生物。     

厌氧菌群JAC1降解石油烃能力及其群落结构的解析

利用苯酚诱导获得厌氧菌群JAC1强化去除土壤中的石油烃，对其在厌氧条件下的石油烃降解条件进行了优化，得到最适降解条件为：pH 7.5～8.5,土壤总石油烃(TPH)质量浓度50 mg/kg, NaCl质量分数0.3%,JAC1接菌量0.15 mL/g。厌氧菌群JAC1对石油烃的降解符合一级动力学模型。通过气相色谱质谱联用仪分析，芳香烃较直链烷烃更难降解，推测部分长链烷烃在降解过程中会分解为短链烷烃后再进行降解。基于土壤宏基因组测序分析可知，土壤微生物群落多样性与TPH浓度呈负相关，投加JAC1后土壤中与石油烃降解有关的功能菌群相对丰度呈现出不同程度增高，说明JAC1有助于建立一个高效的微生物降解体系来强化石油烃降解。     

活化过硫酸钠原位修复浅层石油烃类污染土壤的模拟研究

以过硫酸钠为氧化剂,硫酸亚铁为活化剂,通过箱体实验,结合农业滴灌技术,原位化学氧化修复浅层石油烃(TPH)污染土壤,考察修复过程中土壤TPH、含水率、电导率、pH的变化情况。结果表明,硫酸亚铁活化过硫酸钠对土壤中TPH具有较好的去除作用,通过40d的原位修复处理,表层土和中层土中的TPH去除率分别达到44.6%、44.1%;修复过程中,表层土含水率、电导率呈先上升后下降的趋势,中层土含水率、电导率则先上升后波动变化,表层土、中层土pH均呈先下降后上升的趋势;土壤TPH与含水率、电导率、pH间均存在相互制约的关系。     

土壤气相抽提法去除红壤中挥发性有机污染物的影响因素研究

土壤气相抽提技术(SVE)是一种安全、经济、高效的土壤治理技术,广泛应用于不饱和土壤中挥发性有机污染物的去除.本实验以我国南方典型土壤红壤(粘性较大的土壤)为实验土样,选用最常见的挥发性有机物苯作为污染物,采用一维土柱通风模拟SVE过程,研究了通风流量、土壤含水率以及间歇操作对苯污染红壤去污过程的影响.结果表明,在各土柱垂向气相中苯浓度变化趋势一致,通风初期浓度迅速降低后进入长时间的拖尾阶段,拖尾阶段初期进行间歇操作可降低能耗达到较经济的治理效果.通风流量与土壤含水率是影响净化时间和修复效果的重要因素,两者均存在最佳值.当通风流量为600 mL/min,含水率为17.2%时本实验净化时间降低为36 h,去除率为99.9%,达到了最佳的治理效果.     

表面活性剂强化甲基营养型芽孢杆菌修复柴油污染土壤

使用吐温80(Tween80)、鼠里糖脂(RL)、十二烷基苯磺酸钠(SDBS)和十二烷基苯硫酸钠(SDS)强化甲基营养型芽孢杆菌(Bacillus methylotrophicus)修复柴油污染土壤,研究了表面活性剂对甲基营养型芽孢杆菌的影响。结果表明:甲基营养型芽孢杆菌可以较好地降解柴油,但由于土壤的吸附,土壤中柴油的修复效率较低,仅为22.68%;因此,需要使用表面活性剂进行强化。浓度为3 000 mg·L~(-1)的SDBS和SDS、2 000 mg·L~(-1)的Tween80、500 mg·L~(-1)的RL具有较好的洗脱效果。微生物毒性实验表明,Tween80和RL对甲基营养型芽孢杆菌具有促进作用,可以用于强化修复柴油污染土壤。2 000 mg·L~(-1)Tween80强化甲基营养型芽孢杆菌修复柴油土壤的修复效果(46.11%)优于500 mg·L~(-1)RL的修复效果(45.32%),同时具有较好的经济性,具有较好的应用前景。     

Long Term Monitoring of Hydrocarbon Contamination Using Multi-Level Vapor Phase Piezometers

This study evaluated the feasibility of supplementing groundwater monitoring protocols by assessing the vadose zone for the extent of residual subsurface contamination. The study also characterized the response of the soil gas signatures with respect to different soil types and degrees of contamination. A field study was conducted at a former gasoline vending station located in Ottawa, Canada. The current state of contamination was determined by analysis of soil samples taken from boreholes. A series of 10 nested soil gas wells with monitoring depths of 0.75, 1.5, 2.25 and 3.0 m were then installed. Using these wells, soil gas surveys were performed at regular intervals over an extended period to quantify Gaseous TPH (TPH g ), oxygen and carbon dioxide concentrations in the soil gas. Results indicate that soil gas wells located near the source term exhibited characteristic soil gas signatures and significant fluctuations in TPH g , oxygen, and carbon dioxide concentrations with time. Soil gas wells located beyond the soil contamination demonstrated limited correlation between TPH g , oxygen and carbon dioxide concentrations and decreased seasonal variability.     

In situ bioremediation of nitrate and perchlorate in vadose zone soil for groundwater protection using gaseous electron donor injection technology.

When present in the vadose zone, potentially toxic nitrate and perchlorate anions can be persistent sources of groundwater contamination. Gaseous electron donor injection technology (GEDIT), an anaerobic variation of petroleum hydrocarbon bioventing, involves injecting electron donor gases, such as hydrogen or ethyl acetate, into the vadose zone, to stimulate biodegradation of nitrate and perchlorate. Laboratory microcosm studies demonstrated that hydrogen and ethanol promoted nitrate and perchlorate reduction in vadose zone soil and that moisture content was an important factor. Column studies demonstrated that transport of particular electron donors varied significantly; ethyl acetate and butyraldehyde were transported more rapidly than butyl acetate and ethanol. Nitrate removal in the column studies, up to 100%, was best promoted by ethyl acetate. Up to 39% perchlorate removal was achieved with ethanol and was limited by insufficient incubation time. The results demonstrate that GEDIT is a promising remediation technology warranting further validation.     

Effects of in-situ ozonation on indigenous microorganisms in diesel contaminated soil: survival and regrowth

Soil column experiments were conducted to investigate the effects of chemical oxidation on the survival of indigenous microbes (i.e., heterotrophic microbes, phenanthrene-degrading microbes, and alkane-degrading microbes) for field soil contaminated with diesel fuel. Rapid decreases of total petroleum hydrocarbons (TPH) and aromatics of diesel fuel were observed within the first 60 min of ozone injection; after 60 min, TPH and aromatics decreased asymptotically with ozonation time. The three types of indigenous microbes treated were very sensitive to ozone in the soil column experiment, hence the microbial population decreased exponentially with ozonation time. The numbers of heterotrophic, alkane-degrading, and phenanthrene-degrading bacteria were reduced from 10(8) to 10(4), 10(7) to 10(3), and 10(6) CFU g soil(-1) to below detection limit after 900 min of ozonation, respectively. Except for the soil sample ozonated for 900 min, incubation of ozone-treated soil samples that were not limited by oxygen diffusion showed further removal of TPH. The soil samples that were ozonated for 180 min exhibited the lowest concentration of TPH and the highest regrowth rate of the heterotrophic and alkane-degrading populations after the 9 weeks of incubation.     

Effects of petroleum contamination on soil microbial numbers, metabolic activity and urease activity

The influence of petroleum contamination on soil microbial activities was investigated in 13 soil samples from sites around an injection water well (Iw-1, 2, 3, 4) (total petroleum hydrocarbons (TPH): 7.5-78 mg kg⁻¹), an oil production well (Op-1, 2, 3, 4, 5) (TPH: 149-1110 mg kg⁻¹), and an oil spill accident well (Os-1, 2, 3, 4) (TPH: 4500-34 600 mg kg⁻¹). The growth rate constant (μ) of glucose stimulated organisms, determined by microcalorimetry, was higher in Iw soil samples than in Op and Os samples. Total cultivable bacteria and fungi and urease activity also decreased with increasing concentration of TPH. Total heat produced demonstrated that TPH at concentrations less than about 1 g kg⁻¹ soil stimulated anaerobic respiration. A positive correlation between TPH and soil organic matter (OM) and stimulation of fungi-bacteria-urease at low TPH doses suggested that TPH is bound to soil OM and slowly metabolized in Iw soils during OM consumption. These methods can be used to evaluate the potential of polluted soils to carry out self-bioremediation by metabolizing TPH.     

A combined approach of physicochemical and biological methods for the characterization of petroleum hydrocarbon-contaminated soil

Main physicochemical and microbiological parameters of collected petroleum-contaminated soils with different degrees of contamination from DaGang oil field (southeast of Tianjin, northeast China) were comparatively analyzed in order to assess the influence of petroleum contaminants on the physicochemical and microbiological properties of soil. An integration of microcalorimetric technique with urease enzyme analysis was used with the aim to assess a general status of soil metabolism and the potential availability of nitrogen nutrient in soils stressed by petroleum-derived contaminants. The total petroleum hydrocarbon (TPH) content of contaminated soils varied from 752.3 to 29,114 mg kg^?1. Although the studied physicochemical and biological parameters showed variations dependent on TPH content, the correlation matrix showed also highly significant correlation coefficients among parameters, suggesting their utility in describing a complex matrix such as soil even in the presence of a high level of contaminants. The microcalorimetric measures gave evidence of microbial adaptation under highest TPH concentration; this would help in assessing the potential of a polluted soil to promote self-degradation of oil-derived hydrocarbon under natural or assisted remediation. The results highlighted the importance of the application of combined approach in the study of those parameters driving the soil amelioration and bioremediation.     

土壤有机污染的原位修复技术

介绍了土壤气相抽提、生物通风和空气喷射等3种土壤原位修复技术的概念,简述了它们修复受污染土壤的适用范围和修复机理,并对影响3种修复方法的各种因素进行了详细论述.展望了土壤气相抽提、生物通风和空气喷射技术在我国的应用前景.     

Root establishment of perennial ryegrass (L. perenne) in diesel contaminated subsurface soil layers

The efficiency of rhizosphere biodegradation of petroleum hydrocarbons heterogeneously distributed in soils is dependent on the ability of plant roots to prospect into contaminated zones. Rhizobox experiments were conducted to study the influence of diesel contaminated layers on the spatial distribution and the development of the roots of perennial ryegrass. Root distribution and root and shoot development were monitored over time. The final root and above ground biomass and the final TPH concentration were determined. The spatial distribution of the contaminant as well as the irrigation method used affected root distribution, plant development and TPH degradation and therefore ryegrass remediation potential. The results show that roots colonise fully uncontaminated soil and grow preferentially between zones of contamination. Conversely, when no immediate uncontaminated soil is available, roots grow through contaminated zones in order to prospect for uncontaminated soil.     

Long Term Monitoring of Hydrocarbon Contamination Using Multi-Level Vapor Phase Piezometers

This study evaluated the feasibility of supplementing groundwater monitoring protocols by assessing the vadose zone for the extent of residual subsurface contamination. The study also characterized the response of the soil gas signatures with respect to different soil types and degrees of contamination.A field study was conducted at a former gasoline vending station located in Ottawa, Canada. The current state of contamination was determined by analysis of soil samples taken from boreholes. A series of 10 nested soil gas wells with monitoring depths of 0.75, 1.5, 2.25 and 3.0 m were then installed. Using these wells, soil gas surveys were performed at regular intervals over an extended period to quantify Gaseous TPH (TPH_g), oxygen and carbon dioxide concentrations in the soil gas.Results indicate that soil gas wells located near the source term exhibited characteristic soil gas signatures and significant fluctuations in TPH_g, oxygen, and carbon dioxide concentrations with time. Soil gas wells located beyond the soil contamination demonstrated limited correlation between TPH_g, oxygen and carbon dioxide concentrations and decreased seasonal variability.     

A bench-scale investigation of land treatment of soil contaminated with diesel fuel.

A bench-scale investigation (soil pan testing) was conducted with the objective of studying degradation rates of diesel contaminated soil (2500 and 10,000 ppm by weight of total petroleum hydrocarbons (TPH) to dry weight of soil) under different treatment conditions over a 17 week testing period. The greatest degradation of the diesel contaminated soil was obtained with the addition of nutrients (Co = 10,000 ppm of TPH; k = 0.19 week-1). 'k' for soil not amended with nutrients was 0.07 week-1. The control cell (C0 = 2500 ppm TPH), with sodium azide (to suppress degradation) was compared with an experimental cell of 2500 ppm initial concentration of TPH without nutrient amendment. The control cell exhibited a relatively low uniform degradation (k = 0.08 week-1) of TPH over the duration of the experiment with reasonable first-order kinetic regression statistics.