Infiltration characteristics of non-aqueous phase liquids in undisturbed loessal soil cores

The widespread contamination of soils and aquifers by non-aqueous phase liquids (NAPL), such as crude oil, poses serious environmental and health hazards globally. Understanding the infiltration characteristics of NAPL in soil is crucial in mitigating or remediating soil contamination. The infiltration characteristics of crude and diesel oils into undisturbed loessal soil cores, collected in polymethyl methacrylate cylindrical columns, were investigated under a constant fluid head (3 cm) of either crude oil or diesel oil. The infiltration rate of both crude and diesel oils decreased exponentially as wetting depth increased with time. Soil core size and bulk density both had significant effects on NAPL infiltration through the undisturbed soil cores; a smaller core size or a greater bulk density could reduce oil penetration to depth. Compacting soil in areas susceptible to oil spills may be an effective stratage to reduce contamination. The infiltration of NAPL into soil cores was spatially anisotropic and heterogeneous, thus recording the data at four points on the soil core is a good stratage to improve the accuracy of experimental results. Our results revealed that crude and diesel oils, rather than their components, have a practical value for remediation of contaminated loessal soils.     

Differential degradation of crude oil （Bonny Light） by four Pseudomonas strains

Four hydrocarbon degraders isolated from enriched oil- and asphalt-contaminated soils in Lagos, Nigeria, were tested for their petroleum degradation potentials. All the isolates were identified as species of Pseudomonas. Pseudomonas putida P11 demonstrated a strong ability to degrade kerosene, gasoline, diesel, engine oil and crude oil while P. aeruginosa BB3 exhibited fair degradative ability on crude oil, gasoline, engine oil, anthracene and pyrene but weak on kerosene, diesel and dibenzothiophene. Pseudomonas putida WL2 and P. aeruginosa MVL1 grew on crude oil and all its cuts tested with the latter possessing similar polycyclic aromatic potentials as P11. All the strains grew logarithmically with 1–2 orders of magnitude and with generation time ranging significantly between 3.07 and 8.55 d at 0.05 level of confidence. Strains WL2 and MVL1 utilized the oil substrate best with more than 70% in 6 d experimental period, whereas the same feat was achieved by P11 in 12 d period. BB3 on the other hand degraded only 46% within 6 d. Interestingly, data obtained from gas chromatographic analysis of oil recovered from the culture fluids of MVL1 confirmed near-disappearance of major peaks (including aliphatics and aromatics) in the hydrocarbon mixture.     

特殊地质条件下流动相原油在沿海土-水系统中的运移过程及机制研究

原油作为主要能源之一对现代社会的重要作用不言而喻,但其所带来的污染危害同样不容忽视.通过自制的有机玻璃水槽,建立模型模拟自然地层的非均质性,模拟了原油在沿海土-水系统中的运移过程,探讨了局部非渗透性透镜体、底部隔水层、土壤初始含水率、土壤质地、岩性突变界面对原油在砂土中运移速度和路径的影响.结果表明,局部非渗透性透镜体和底部隔水层对原油的运移具有阻碍作用,会改变其运动速度和路径.在一定范围内,土壤初始含水率越高,原油的侧向运移速率和垂向运移速率越大(模拟成层性土层中原油垂向运移速率随含水率增大,由0.43 cm·min~(-1)增大到1.00 cm·min~(-1),在低含水率区域原油侧向运移速率分别为0.08 cm·min~(-1)(粗-细界面)和0.10 cm·min~(-1)(细-粗界面),而在含水率较高的区域则为0.14 cm·min~(-1)),而过高的含水率又会阻碍原油的运移.土壤孔隙越大,垂向运移越快,侧向运移越慢,反之,垂向运移越慢,侧向运移越快(模拟成层性土层中,原油在粗砂中的垂向平均运移速率为0.54 cm·min~(-1),而在细砂中仅为0.33 cm·min~(-1),自然泄漏时原油在粗砂中的最大扩散范围为9.10 cm,在细砂中为12.50 cm).原油在土壤中运移遇到岩性突变界面时,会产生聚集效应,在聚集处产生侧向运移,试验中在粗-细界面扩散宽度为6.70 cm,在细-粗界面扩散宽度为29.00 cm.     

Effect of the chemical forms of selenium on its volatilization from soils in Chinese low-selenium belt

Bio-availability of different forms of selenium and its rate of volatilization from soils in Chinese low-selenium belt were examined. Adding directly solutions of either inorganic or organic selenium compounds to soil could only slightly increase the rate of selenium volatilization from soil. Volatilization of selenium from soil was largely enhanced when certain nutritional solutions along with selenium compounds were added. Garlic water extract and seleno-amino acids, i.e., seleno-methionine and seleno-cysteine, were found more effective for their bio-availability to the volatilization process. Under laboratory simulating conditions, the volatilization rate of selenium from different types of soils in Chinese low-selenium belt was found in the range of 0.10-0.27 ng.kg-1 soil.day-1 over a 17 days period, generally followed by a decline with time of incubation.     

Johnson & Ettinger模型和Volasoil模型在污染物室内挥发风险评价中的应用和比较

在土壤污染和地下水污染的现场,挥发过程是挥发性污染物暴露的重要途径.设置典型土壤污染场景作为研究对象,选取Johnson&Ettinger模型和Volasoil模型进行室内挥发过程的模拟和暴露浓度的计算.对两个模型中污染物的运移机理进行了比较和分析.尽管方法和参数选择有所不同,二者对污染源处三相平衡浓度的计算本质上是一致的.暴露浓度的计算结果表明,两个模型对室内挥发过程的模拟可能会有较大差异,与污染现场的具体情况有关.参数影响的分析表明,污染源顶部埋深对二者暴露浓度的影响一致,Johnson&Ettinger模型对污染土壤含水率的大小非常敏感.建议考虑房屋结构的实际情况,选用或者改进模型进行室内挥发过程的评价.     

采用清洗-热脱附工艺修复石蜡基与环烷基原油污染土壤

石油污染土壤修复工艺的选择及其应用效果受原油属性影响明显。选取石蜡基和环烷基2类原油污染土壤,采用清洗预处理-热脱附方法,研究耦合工艺的修复效能,重点比较清洗对土壤粒级的分离效果,表面活性剂对石油污染物的脱附效率,药剂清洗前后的土壤热脱附修复效果等。结果表明:清洗后2种土壤的砂质组分吸附的石油类脱附率约为59.83%和36.42%,远高于黏质组分。阴离子型α-十六烯基磺酸钠脱附能力更强,石蜡基和环烷基2类油源污染土壤的石油类脱附率为46.5%和39.8%。以环烷基土壤为例,将药剂清洗后分离出的黏粒土进行热脱附,与未清洗的原污染土壤相比,前者脱附所用时间更短。400℃下热脱附3 h,石油类含量降至0.26%。采取清洗-热脱附工艺开展现场试验,清洗后粗粒级砂质土壤的石油类含量为1.56%,黏粒土脱水后热脱附,石油类含量可达到0.57%,清洗-热脱附修复污染土壤能耗低于单纯热脱附工艺。     

Influence of biosurfactant on the diesel oil remediation in soil-water system

There were six high diesel oil degrading bacteria strains isolated from the oil contaminated soil that collected from Linzi City. The strain YI was able to produce biosurfactant rhanmolipid when cultivated on diesel oil as carbon source. The critical micelle concentrations （CMC） of rhanmolipid in water and in the soil were measured respectively according to the correlation between the surface tension of the medium and the added rhamnolipid concentration. The results showed that the CMC of rhanmolipid in water was 65 mg/L, and was 185 mg/L in soil. The tests on diesel oil biodegradation were conducted with the addition of different concentrations of rhamnolipid in water and in soil respectively. When 0.01% rhanmolipid was added to water, the diesel oil degradation was enhanced. On the contrary, when the same concentration of rhanmolipid was added to the soil, the degradation of diesel oil was inhibited. The results suggested that the rhamnolipid could enhance the diesel oil biodegradation, indicating that the concentration of rhamnolipid was higher than the corresponding CMC in the medium. Kinetics parameters for the diesel oil biodegradation parameters such as biodegradation constant （λ）, coefficient of correlation （r） and half life （t1/2） in both tests were numerically analyzed in this paper, indicating that the moderate concentration of rhamnolipid in the medium could not only enhance the extent of diesel oil biodegradation but also shorten the time for oil remediation.     

油田区土壤石油烃组分残留特性研究

为了揭示石油开采区土壤石油烃组成及残留特性,探讨石油污染物的来源与风化程度,采集了胜利油田孤岛和河口采油区共5口油井周边土壤样品及原油样品,利用气相色谱-质谱联用仪(GC-MS)分析原油及土壤样品中的链烷烃(正烷烃+姥鲛烷+植烷)及多环芳烃(polycyclic aromatic hydrocarbons,PAHs)共51种石油烃单体的含量.结果表明,与原油相比,油田区土壤总提取物中链烷烃与PAHs所占的比例明显偏低;土壤石油烃的组分构成与原油相比,链烷烃中碳数小于12的正烷烃比例明显降低,而高碳数正烷烃比例增加.选择正十八烷/植烷作为指示土壤风化程度的标志,利用主成分分析(principal component analysis,PCA)法分析其与土壤中各石油烃组分的关系,结果显示碳数大于33的正烷烃与中环芳香烃具有高残留性.利用主成分分析综合分析用于土壤石油烃来源识别的4个指标,结果表明,土壤中的石油烃具有明显的原油"指纹".研究结果为油田土壤污染特性的认识提供了依据与基础.     

黄淮海平原主要土类中硝态氮水平运移规律

对黄淮海平源的主要土壤类型（黄潮土和风沙土）中硝态氮水平运移规律进行了研究。结果表明：硝态氮水平运移速率随供试示踪剂源的距离增加而迅速减小,其变化趋势呈幂函数关系。由于各土层的土壤性质不同,所以硝态氮的运移风线发生差异,但总的趋势是离示踪剂源20cm距离内,硝态氮的水平运移速率主要由硝态氮的浓度梯度和水势梯度控制,而在20cm以后趋于平稳,则主要由土壤的基质势起作用。硝态氮水平运移速率随土壤含水量的增大而升高,并呈指数曲线变化。硝态氮水平运移的浓度受非饱和土壤水扩散率的影响,并随非饱和土壤水扩散率的升高而呈对数曲线下降。     

汽车尾气中多环芳烃(PAHs)成分谱图研究

采集并测定了不同型号、油品、里程数的汽车尾气中14种多环芳烃,对分析结果归一化处理后确定其多环芳烃成分谱图.研究表明,汽车在30rmin内排放的14种PAHs总浓度为41.53～121.1μg/m³;其中苯并(a)蒽(BaA)浓度最大,占总量的33.3%;萘(Naph)、苯并(ghi) (Bghip)、茚(1,2,3-cd)芘(In)分别为16.8%、12.9%和12.1%.相同里程数的柴油车排放PAHs总量大于汽油车;除BaA和Naph,柴油车主要排放苊(Ac)、芴(Fluor)、Bghip和In,而汽油车主要排放Bghip、In、苯并(k)荧蒽(BkF).柴油车排放3环PAHs的量大于汽油车,但5～6环PAHs的排放量小于汽油车;随着汽车里程数的增加,PAHs(特别是荧蒽(Flur)、芘(Py)、苯并(a)芘(BaP)、Bghip)的排放总量增加.     

五种表面活性剂对柴油污染土壤清洗效果的比较

研究了十二烷基硫酸钠(SDS)、十二烷基苯磺酸钠(SDBS)、皂苷(saponin)、月桂醇聚氧乙烯(23)醚(Brij35)、Triton X-100五种表面活性剂对中度柴油污染土壤的清洗效果,考察柴油和土壤混合后在不同时间段的挥发特点,认为污染时长会直接影响表面活性剂清洗修复的效果,增大清洗剂浓度可以提高对新污染土壤的洗脱率,但对老化污染土壤的效果并不明显;对不同含油量的污染土壤清洗,研究污染程度对洗脱率变化的影响,当达到一定含油量后洗脱效果产生突变。不同表面活性剂在相同CMC倍数下清洗能力存在差异,其顺序为SDS>SDBS>Triton X-100>皂苷>Brij35。     

船舶油运中油气污染，控制及石油发试验研究

船舶装卸运输石油时，油气蒸发是船舶大气污染的主要问题之一。它不仅损失大量货油，也对船舶环境造成严重污染。试验表明， 油气蒸发过程随油种不同。蒸发速率差别较大，第一类如工业汽油、煤油，初始发量高达每小时5％－10％，第一天蒸发逸散量可在50％，第二类如柴油、原油也有较大蒸发速率，第一天的蒸发量可达3％－11％，第三类蒸发量较小，如机油、重油、渣油等。第一天蒸发量仅约0.5％以下，但蒸发衰减不快。前两类油种蒸发衰减较快。油气蒸发过程也与环境温度、风速有关。文中最后讨论了控制油气蒸发造成污染的3项措施。     

长期石油污染对盐碱化土壤中微生物群落分子生态网络的影响

长期石油污染改变了土壤微生物群落组成,降低了群落多样性,对生态系统造成严重的威胁.为了探讨长期石油污染对盐碱化土壤中微生物物种间相互作用关系的影响,采集胜利油田石油污染土壤和未污染土壤,利用随机矩阵方法构建分子生态网络.结果发现,污染土壤和未污染土壤中微生物功能基因组的分子生态网络存在显著差异(P0.001).与未污染土壤相比,污染土壤的网络节点数、连接数、平均连通度、模块数和模块性都显著降低,说明在石油污染的影响下土壤微生物网络拓扑结构发生变化;污染土壤和未污染土壤的模块枢纽基因、连接器基因均没有重叠,模块枢纽基因和连接器基因的网络拓扑角色发生了变化.通过构建烷烃、多环芳烃降解基因网络,发现负相互作用的比例较大,这可能反映了微生物功能群落间的竞争关系.     

包气带油污土层生物修复现场控制性因素的评价

包气带油污土层的生物修复涉及到石油降解微生物、石油污染物的可生物降解性和土壤环境三个方面.本文通过最或然计数法(MPN)、原油族组分柱层析分析方法和色质联机分析等实验手段,研究了淄河滩包气带油污土层的水力学特性、氮磷营养元素、微生物和石油污染物.结果表明,长期受石油污染的土层含有丰富的微生物,其中大部分具有降解石油烃的能力,且土层的渗透性极强,有利于开展油污土层的生物修复.同时,长期的挥发、淋失和转化造成土层中石油污染物主要由高分子、高沸点烃类组成,且油污土层的速效氮、速效磷含量太低,直接增加了生物修复的难度,成为不利于生物修复的影响因素.     

PAHs pollution from traffic sources in air of Hangzhou, China: Trend and influencing factors

Introduction China is experiencing rapid economic and populationgrowth. The rapid growth and increasing fossil fuel energyconsumption have resulted in large amounts of pollutants suchas TSP, SO2, NOx and hydrocarbons to be emitted intoambient atmosphere. Nowadays, national routine monitor haspaid much attention to TSP, SO2 and NOx. Highconcentrations of SO2 and NOx can lead to an increase ofregional levels of acid deposition and tropospheric ozon, thu…     

天津市郊夏季VOCs化学特征及其时间精细化的来源解析

夏季为环境空气中臭氧污染事件的频发时期,针对挥发性有机化合物(VOCs)及其臭氧生成潜势(OFP)的时间精细化的来源解析研究,对有效地进行臭氧污染防控具有非常重要的作用.利用2019年夏季(6～8月)天津市郊区点位监测的小时分辨率VOCs在线数据,分析臭氧污染事件和非臭氧污染时期环境受体中VOCs及其OFP的变化特征,并利用正定矩阵因子分解(PMF)模型进行精细化的来源解析研究.结果表明,夏季环境受体中VOCs平均体积分数为24.42×10-9,臭氧污染事件中的VOCs平均体积分数为27.72×10-9,较非臭氧污染时期增加15.69％.夏季总VOCs(TVOCs)的OFP为87.92×10-9,其中烯烃的OFP最高,对TVOCs的OFP的贡献达58.28％.臭氧污染事件中TVOCs的OFP为102.68×10-9,较非臭氧污染时期增加19.59％.臭氧污染事件中VOCs的来源分别为石化工业及汽油挥发(29.44％)、柴油车尾气(23.52％)、液化石油气及汽油车尾气(22.00％)、天然气及燃烧(13.41％)、溶剂使用(6.14％)和植物排放(5.49％).相比于非臭氧污染时期,液化石油气及汽油车尾气和柴油车尾气分别增长4.84％和5.29％.石化工业及汽油挥发和植物排放的贡献均表现为08:00开始上升,11:00达到最高,这与太阳辐射增强和温度不断上升密切相关.液化石油气及汽油车尾气和柴油车尾气均具有明显的早晚高峰特征,并在夜间(00:00～06:00)保持较高贡献水平.根据PMF结果并结合OFP的计算方法,解析了不同源类对臭氧生成潜势的 贡献.石化工业及汽油挥发(31.01％)和柴油车尾气(36.64％)是较高贡献源类,相比非臭氧污染时期分别增加了 1.74％和8.27％;并且石化工业及汽油挥发贡献率在臭氧污染事件发生过程的上升阶段显著增加,而在下降阶段明显下降.     

地下水位波动及降水对原油在非均质土层中重分布的影响

为研究原油泄漏后在非均质土层中的重分布过程及影响因素,建立3种不同组合的非均质土层物理模型（编号分别为L-a、L-b、L-c）进行原油泄漏后重分布过程的室内模拟,分别代表局部非渗透性透镜体（浅层泄漏）、大面积弱渗透性粉质亚黏土（内部泄漏）和土层界面（浅层泄漏）存在条件.待原油重力渗透稳定后分别进行升降水位和降水的模拟试验,由PET聚酯膜绘制、CCD相机拍摄和基于CMYK的灰度分析等图像采集和分析法获得平面运移分布图、纵剖面灰度变化图,采用风干法和紫外分光光度法获得采样点含水率和含油率对比图,分析原油泄漏后在非均质土层中的运移规律.结果表明:①在水位波动下,局部非渗透性透镜体和大面积粉质亚黏土弱透水层可有效截获原油,使原油在其左右及上侧大量聚集;3组试验中原油的重分布过程以垂向运移为主,但在粗-细界面和细-粗界面会因油水驱替和毛细压力导致其部分横向运移.②模拟降水时,受到淋滤和水位波动的综合效应,原油油聚区不能在短时间内随水位线移动,体现其滞后性;在模拟降水结束后油聚区大量分布于水位线位置和细-粗界面处;降水对土壤中的原油具一定稀释作用.③L-a和L-c组表层泄漏的原油分布面积（分别为800、538 cm2）较大,采样点含油率极差（分别为6.23%、6.80%）较大;而L-b组内部泄漏的原油分布面积（235 cm2）较小,采样点含油率极差（2.99%）较小.研究显示,地下水位波动及降水对非均质土层中原油的周期性聚集和释放有一定影响,尤其是局部非渗透性透镜体、大面积弱渗透性粉质亚黏土及岩性界面存在土层中影响更大.      

Raman spectroscopy of diesel and gasoline engine-out soot using different laser power

We studied engine-out soot samples collected from a heavy-duty direct-injection diesel engine and port-fuel injection gasoline spark-ignition engine. The two types of soot samples were characterized using Raman spectroscopy with different laser powers. A Matlab program using least-square-method with trust-region-reflective algorithm was developed for curve fitting. A DOE (design of experiments) method was used to avoid local convergence. The method was used for two-band fitting and three-band fitting. The fitting results were used to determine the intensity ratio of D (for “Defect” or “Disorder”) and G (for “Graphite”) Raman bands. It is found that high laser power may cause oxidation of soot sample, which gives higher D/G intensity ratio. Diesel soot has consistently higher amorphous/graphitic carbon ratio, and thus higher oxidation reactivity, compared to gasoline soot, which is reflected by the higher D/G intensity ratio in Raman spectra measured under the same laser power.     

砂土中柴油的微生物降解研究

从加油站污染土壤中筛选出对柴油具有较强降解能力的菌株,比较研究菌株及菌群降解柴油的差异,探讨植物苜蓿和芥菜对菌株降解柴油污染物的影响.结果表明:①菌株Q18和菌群对砂土中柴油都具有较强的降解能力,菌群对柴油的降解率明显高于菌株Q18.菌株Q18 和菌群在5 d内对柴油的总降解率分别为40.29%和54.15%.与菌株Q18降解柴油相比,菌群主要是强化了中、长链烷烃化合物的降解.②在砂土中,苜蓿和芥菜都能显著地强化菌株Q18对柴油的降解,但苜蓿强化菌株Q18降解柴油的能力强于芥菜. 5 d内菌株Q18-芥菜和菌株Q18-苜蓿复合体系对柴油总降解率分别达到60.05%和56.68%.③菌群和苜蓿及芥菜复合体系降解柴油的能力也有显著提高,但芥菜强化菌群降解柴油的能力强于苜蓿.5 d内菌群-芥菜和菌群-苜蓿复合体系对柴油总降解率分别为75.53%和70.50%.      

Treatability of volatile chlorinated hydrocarbon-contaminated soils of different textures along a vertical profile by mechanical soil aeration: A laboratory test

Mechanical soil aeration is a simple, effective, and low-cost soil remediation technology that is suitable for sites contaminated with volatile chlorinated hydrocarbons(VCHs). Conventionally, this technique is used to treat the mixed soil of a site without considering the diversity and treatability of different soils within the site. A laboratory test was conducted to evaluate the effectiveness of mechanical soil aeration for remediating soils of different textures(silty,clayey, and sandy soils) along a vertical profile at an abandoned chloro-alkali chemical site in China. The collected soils were artificially contaminated with chloroform(TCM) and trichloroethylene(TCE). Mechanical soil aeration was effective for remediating VCHs(removal efficiency 98%). The volatilization process was described by an exponential kinetic function.In the early stage of treatment(0–7 hr), rapid contaminant volatilization followed a pseudofirst order kinetic model. VCH concentrations decreased to low levels and showed a tailing phenomenon with very slow contaminant release after 8 hr. Compared with silty and sandy soils, clayey soil has high organic-matter content, a large specific surface area, a high clay fraction, and a complex pore structure. These characteristics substantially influenced the removal process, making it less efficient, more time consuming, and consequently more expensive. Our findings provide a potential basis for optimizing soil remediation strategy in a cost-effective manner.