Experimental research on adsorption/desorption for petroleum pollutants in the soil in Daqing oilfield

The Daqing oilfield is one of the biggest oilfields in the world. It has been exploited for several decades, which brings serious pollution to local natural environment. The crude oil on ground which is produced in the process of oil production contains various organic pollutants. The petroleum pollutants tend to adsorb, desorb, biodegrade and photolyze and so on in the soil, but adsorption/desorption is a pair of extremely important environment geochemistry behavior. In order to master the rule of petroleum pollutants migration and transformation in the soil environment, and provide scientific evidence for the prevent research project on petroleum pollution treatment in the Daqing oilfield, the chemozem was selected as the experimental sample, which is a kind of representative soil in the Daqing oilfield. The factors affecting adsorbent and desorption＇s characteristics were discussed, including pH of the soil, the concentrations of suspended particulates and temperature. The oscillation-equity was used in the experiment. The mechanism and dynamics process of the adsorption/desorption were researched. The results showed that adsorbing of the petroleum pollutants on the chemozem sediment is a kind of physical adsorption phenomenon. The adsorption function comes from the hydrophobic and sticky character of the petroleum its self. The velocity of adsorption and desorption is almost equivalent, both concentrations of water in the soil are close to the balance in two hours, thus they achieve homeostasis in three hours. The process of adsorption of the petroleum pollutants responses to Herry isothermal model, with increasing pH, concentration of suspended particulates and temperature, the quantity of adsorption show a descending trend. However, desorption is a contrary course of adsorption in the experiment. Due to various influenced phenomena reflect that the soil in the Daqing oilfield has factors, the quantity of desorption shows an ascending trend. These strong adsorption ability to petroleum pollutants.     

Anisotropic Rock Poroelasticity Evolution in Ultra-low Permeability Sandstones under Pore Pressure, Confining Pressure, and Temperature: Experiments with Biot’s Coefficient

This study aimed to show anisotropic poroelasticity evolution in ultra-low permeability reservoirs under pore pressure, confining pressure, and temperature. Several groups of experiments examining Biot’s coefficient under different conditions were carried out. Results showed that Biot’s coefficient decreased with increased pore pressure, and the variation trend is linear, but the decreasing rate is variable between materials. Biot’s coefficient increased with increased confining pressure; the variation trend is linear, but the increasing rate varies by material as well. Generally, Biot’s coefficient remains stable with increased temperature. Lithology, clay mineral content, particle arrangement, and pore arrangement showed impacts on Biot’s coefficient. For strong hydrophilic clay minerals, expansion in water could result in a strong surface adsorption reaction, which could result in an increased fluid bulk modulus and higher Biot’s coefficient. For skeleton minerals with strong lipophilicity, such as quartz and feldspar, increased oil saturation will also result in an adsorption reaction, leading to increased fluid bulk modulus and a higher Biot’s coefficient. The study’s conclusions provide evidence of poroelasticity evolution of ultra-low permeability and help the enhancing oil recovery (EOR) process.     

冻胀过程与冻结缘特性

The complex process of soil freezing which relates to moisture field, temperature and stress field usually accompanies water migration and crystallization. The mechanism of water migration in the -frozen fringe is blurry though there have rather mature theory analyzing water migration in the unfrozen zone and fully-frozen zone. It is a visualized and easy method to calculate the potential gradient of frozen fringe by frost heave amount, the duration of the steady state of frost heaving and the coefficient of permeability based on the Darcy penetration theory, not directly considering water driving force, ice segregation temperature and the thickness of frozen fringe. The method is feasible by comparing the calculated amount of frost-heaving with the test data.     

Mutual effects of fluoride and phosphate on their adsorption and desorption in fluoride-contaminated softs

Phosphate is one of the important nutrients for plant growth. In acidic and highly weathered soils, phosphate is ready to adsorb on Al and Fe oxides and transform into sparsely soluble Fe-P and Al-P solid phases, greatly reducing phosphate bioavailability. Aluminum and iron oxides in soils are important sinks for both phosphate and fluoride. In acidic soils, fluoride adsorption can dramatically facilitate dissolution of Al- and Fe-containing phases, which may influence the distribution and migration of both pollutants and nutrients including phosphate. To date, little information is available on mutual effects of fluoride and phosphate in fluoride-contaminated acidic soils. The objective of this study is to evaluate mutual effects of fluoride and phosphate on their adsorption/desorption in red soil, collected fi＇om Yingtan, Jiangxi Province, China, using a batch equilibrium method. The following results and conclusions were obtained. In heavily fluoride-contaminated soils, the adsorption of both fluoride and phosphate decreases with an increase in solution pH. Phosphate adsorption decreases progressively with increasing concentration of fluoride, suggesting that fluoride competes with phosphate for adsorption sites.     

Microstructure and Photocatalytic Decomposition of Methylene Blue by TiO2-Mounted Halloysite, a Natural Tubular Mineral

On the basis of analysis of structure and properties, halloysite, a natural tubular mineral, was developed for an environmental treatment. TiO2 was mounted into halloysite by using hydrolysis of tetrabutyl titanate at room temperature. The adsorption and photocatalytic performance of halloysite and TiO2-mounted halloysite have been examined in methylene blue aqueous solution in the dark and under ultraviolet ray irradiation, respectively. Their performance of adsorption and photodecomposition was evaluated from the adsorbed and degraded amounts of methylene blue （MB）. Due to the mixture of adsorption and photodecomposition, the concentration of MB, organic pollution, in water decreased rapidly with TiO2-mounted halloysite powder, which is a faster reaction than that with halloysite-only adsorption. This new use of halloysite is leading to many interesting applications in the decomposition and elimination of various pollutants in air and water.     

Dispersion and immobilization of pollutants in Cretaceous sandstones where U ore was mined by sulfuric acid leaching

The uranium deposit Straz pod Ralskem in the northern part of the Czech Republic was exploited by underground acidic leaching between 1968 and 1996. More than 14000 tons of uranium were produced during this period. More than 4 million tons of H2SO4, 300 thousand tons of HNO3, 120 thousand tons of NH3 and other chemicals were injected in Cenomanian sandstones. The mining has resulted in a large contamination of ground waters. Lateral hydrodynamic dispersion of the pollutants and migration of pollutants across aquitard are a potential hazard to drinking water supply and to surface aquatic environment, Chemical leaching was done by forced circulation of a technological acid solution introduced to the sandstones through injection drill holes and withdrawal of the enriched resulting solution by production wells. The solution is reacting not only with uranium ore, but also with minerals of the rock environment. Hydrogen ions are replaced by uranium and other cations leached from the rock, especially Fe, Al, Be and As. Ammonia remaining after the precipitation of the yellow cake （ammonium diuranate） was rejected underground in spite of that it serves no purpose in the underground leaching. High concentrations of Al, Be, As and ammonium ions in ground water became the most serious ecological pollutant. Modelling of the hydrodynamic dispersion of the pollutants predicts the future risks to local water supplies in 200 to 500 years. A possible way to reduce the risk is an immobilization of the pollutants in deeper parts of the sandstone aquifer. We found that modeling of the geochemical reactions using classical hydrochemical models give unrealistic results because of formation of colloidal particles.     

Effect of incubating plant cuticles in soil on their sorptive capabilities

Sorption and desorption are the major processes influencing the fate of hydrophobic organic compounds （HOCs） in soils. Among the natural sorbents in the environment, soil organic matter （SOM） plays a significant role in the overall sorption of many organic compounds. Recently, several reports have emphasized the role of aliphatic-rich sorbents in the binding of HOCs. The main source of aliphatic compounds for SOM is biopolymers derived from above- and below-ground plant cuticular matter. The plant cuticle is a thin layer of predominantly lipid material that covers all primary aerial surfaces of vascular plants. The objective of this study was to examine the effect of decomposition and transformation of plant cuticles on their sorption behavior with triazine herbicides and polycyclic aromatic hydrocarbons （PAHs）. Sorption-desorption behavior was studied during 12 months of incubation of cuticles isolated from tomato fruits and pummelo leaves in sandy soil. Sorption and desorption experiments and spectroscopic and chemical analyses were performed using the samples after 0, 1, 3, 6 and 12 months of incubation. The decomposition of the cuticles （46-49% after 12 months） did not affect the organic carbon-normalized Freundlich distribution coefficient （KFOC） for the PAHs. In addition, throughout the incubation period, the two PAHs exhibited linear and reversible sorption isotherms with both cuticles. However, the isotherms of the triazines were significantly affected by the decomposition of the cuticles from pummelo leaves, whereas only minor changes were recorded for the tomato cuticle samples. For the microcosm with cuticles from the pummelo leaves, the KFOC values of the triazines increased with increasing decomposition.     

Heavy metal retention by soil mineral phases during a potential soil contamination by sewage sludge

The immobilization conditions of heavy metals （Ni, Cu, Zn, Pb） potentially released from sewage sludge to soils were examined. Competitive adsorption experiments, sequential extraction and analytical electron microscopic studies were performed on soils with different compositional characteristics to gain information about the interaction and association of metals with soil minerals. The results showed that Cu and Pb can be characterized by a preferred adsorption in contrast to Zn and Ni independent of initial metal concentrations, ratios, and soil composition. Precipitation is the dominating retardation process in the sample containing carbonates, but it is also characteristic of metals with inhibited adsorption in samples free of carbonate. Both Cu and Pb show high affinity towards organic matter. Differences in metal affinities towards different clay minerals show the immobilization of Cu rather by specific adsorption and that of Pb rather by ion exchange. According to the sequential extraction studies the role of ion exchange is the most important process for the retardation of Zn, and in the sample containing montmorillonite. The specific adsorption is significant mostly for Cu and Pb, and primarily in samples rich in organic matter and containing vermiculite. The co-precipitation of metals with Fe-Mn oxides is significant primarily for Cu, but in some cases Pb and Zn can be also found in this fraction. In general, the strength of immobilization for the studied metals is as follows： Cu〉Pb〉Zn〉Ni. Significantly higher metal adsorption was found by the phases in the sample containing carbonates, as well as in samples characterized by the close association of clay minerals and iron oxides. Smectite and vermiculite are the most important adsorbents in soils for all of the metals. Additionally, iron-oxides immboilize significant amounts of Cu and Zn, too.     

Characterization of organic matter deposited in the oriental zone from Moknine hypersaline environment, oriental Tunisia

The geochemistry data show that the total organic carbon （TOC） contents are high in the surface sediments in the eastern part of the Moknine＇ s Sebkha. Low decreasing of organic matter （ OM ） with increasing depth indicates the good preservation of OM in modern sediments. ＂Lignite levels＂ inserted in the sand sequence and deposited at the edge and in the intermediate zone are considered as lithologic and organic markers. It is characterized by high TOC and poor hydrogen index （HI） , indicating a higher plant origin and good preservation of OM in thin beds under anoxic condition. In all samples low values of HI are typical for strong terrigenous input in the Sebkha. Gas chromatography （GC） of saturate fraction showed that OM in the border zone is provided from plants but in the central zone OM is a mixture of terrestrial fraction and little fraction from microalgae. The study of free lipids indicated that this environment was influenced by intense bacterial and microbial activities, as evidenced by the abundance of n-alkanes and nC18-nC22.     

Comparison of organic pollutants in urban deposits of Guangzhou and Hong Kong metropolitan areas

With the rapid development of industrialization and urbanization in the Pearl River Delta region, organic as well as inorganic pollution is becoming a major environmental concern. Urban deposits including road dusts, corresponding gully sediments and topsoils proved to be useful tools for assessing the level and distribution of contaminants in metropolitan areas. Most of the previous studies utilizing urban deposits, however, focused on inorganic pollutants, while data on organic pollutants are rare. In this study, therefore, the organic pollutants in urban deposits of Hong Kong and Guangzhou were systematically investigated in terms of their abundance, composition and distribution. The road dusts, gully sediments and vehicular tunnel dusts as well as soils from different urban locations with variable traffic volumes （less than 1000 to more than 75000 AADT） were examined. The results indicated that vehicle-emitted particles were the major source of organic pollutants, while the contributions from background soils were very limited. Surprisingly, the soil in a remote island of Hong Kong with no vehicular traffic has also shown signs of pollution from vehicular particles likely through dry-wet atmospheric deposits. In general, the characteristics of organic pollutants in urban dusts from both cities are comparable although there were also some significant differences. For example, the amount of extractable organic matter in urban deposits of Hong Kong was significantly higher than that of Guangzhou. Differences in their extractable asphaltene contents not only reflected the differences in quality and types and fuels used in these cities, but also sample residence times, and thus different extents of weathering processes.     

基于多元回归分析的铬污染地下水风险评价方法

土-水分配系数（K_d）是表征重金属污染物在土壤包气带中迁移能力的重要参数,受污染物质量浓度、pH值、有机质质量分数、铁铝氧化物质量分数等多种因素影响。本文通过实验研究了分配系数与各种影响因素之间的关系,基于多元回归分析方法得到了分配系数与影响因素的关系方程;并以分配系数、泄漏量、土壤孔隙度、初始含水率为风险因子建立了地下水污染风险评价方法。以某工厂铬废液的泄露为案例,采用构建的方法进行地下水污染风险评价。结果表明：该处地下水被污染的风险等级为中等。地下水污染风险评价方法的建立为重金属污染地下水的监测管理提供了一种有效方法。     

有机污染土壤-地下水系统中的微生物场及多场耦合研究

了解污染场地中微生物群落对有机污染物迁移转化的影响是高效修复治理有机污染场地的基础。自然界中的微生物以“场”的形式通过与水动力场、温度场、化学场等耦合作用,发挥其在维护生态稳定性及物质循环过程中的功能。微生物与有机物关联研究的文献计量分析结果显示,近年来关于微生物和有机物的研究主要集中在微生物群落结构、有机物的生物降解及有机物的迁移转化3个方面及一系列的关联研究中,而关于将微生物以“场”的形式定量刻画微生物在物质循环转化和维持生态稳定性方面作用的研究几乎没有。为此,本文通过研究给出了微生物场的定义,提出了有机污染场地中的微生物场概念模型和数学模型,分析了微生物场的主要影响因素及影响机制,构建了微生物场与水动力场、温度场、化学场之间耦合的本构模型。最后,对微生物场下一步的研究提出了展望。     

1,2-二氯乙烷和1,2-二氯丙烷在某污染场地包气带的吸附-解吸特性

1,2-二氯乙烷(1,2-DCA)和1,2-二氯丙烷(1,2-DCP)是某污染场地地下水中检出最高的挥发性有机污染物。文中采用批试验方法,研究污染场地包气带中三种不同深度土壤样品对1,2-DCA和1,2-DCP的吸附-解吸特性。结果表明:土壤中有机质决定其吸附行为,三种土壤对1,2-DCA和1,2-DCP的吸附符合Henry线性等温方程,分配系数在20.49～22.43L.kg-1,1,2-DCA和1,2-DCP在三种土壤中分别具有相似的吸附能力;同一土壤中两种目标污染物的吸附能力为Kd(1,2-DCA)>Kd(1,2-DCP),但差别不大。1,2-DCA和1,2-DCP在三种土壤中的解吸可用Freundlich等温方程拟合,解吸的难易程度与土壤中黏粒含量相关,黏粒含量越高,目标污染物的解吸越困难,第三层(地下4.9～5.1m)土壤的防污能力较强;两种污染物在三种土壤中的解吸都存在明显的滞后效应,1,2-DCP的滞后指数比1,2-DCA的大。     

应用土柱试验求解地下含水介质弥散系数

污染物质在地下含水介质中的运移,除受渗透系数等水文地质条件的制约外,还受到含水介质弥散系数的控制。污染物的扩散,首先是从包气带开始进行的,浑河冲洪积扇地包气带主要岩性是亚粘土及亚砂土,因此,计算出浑河冲洪积扇包气带的弥散系数,对于认识污染物的运移能力是一项必要的工作。本文利用室内动态土柱装置,模拟包气带岩性环境,以0.05 mol/L的NaCl溶液作为示踪剂,经长时间监测,运用弥散系数计算公式进行求参。计算结果是包气带以亚粘土为主要岩性的弥散系数为0.005 71 m2/d,亚砂土的弥散系数为0.012 47 m2/d。     

Pharmaceuticals and personal care products transference-transformation in aquifer system

Pharmaceuticals and personal care products (PPCPs) are a new kind of contaminant widely existing in the surface water and groundwater environment. In recent years, PPCPs have been received widely attention from many researchers. The migration and transformation of PPCPs are mainly photolysis, biodegradation, adsorption and hydrolysis in aquifer environment. The influencing factors of PPCPs migration include PPCPs' own physical and chemical properties, types and contents of organic matter, pH, lithology, geotechnical structure and the thickness of vadose zone, etc. At present, the research of PPCPs in China is still in the primary stage, especially on the contaminant in aquifer system. Therefore, the research in this field needs to be further strengthened.     

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.     

江汉平原过渡带黏性层状土弥散试验与模拟研究

为研究江汉平原—大别山区过渡带黏性层状土中溶质迁移的规律,以保守性阴离子Br-为示踪剂,通过等温吸附试验、一维弥散试验、HYDRUS-1D软件模拟反演手段,研究了Br-在黏性层状土中的吸附参数、迁移规律,模拟反演其弥散参数。结果表明：（1）Freundlich模型和Langmuir模型均能较好的拟合吸附试验结果,随着土壤中黏粒比例的增大,土壤对Br-的饱和吸附量有所增加;（2）层状土中土壤质地与结构均会影响穿透曲线的形状,但一维饱和土柱中的弥散过程主要取决于含水介质系统中黏性颗粒的占比,黏粒的增加会对溶质运移产生阻碍作用;（3）通过HYDRUS-1D软件构建模型反演弥散参数,R2均大于0.991,拟合效果较好,分析发现层状土中无论土壤组成类型还是层厚及排序的影响,其本质都是改变了土壤的平均孔隙流速从而影响弥散作用,平均孔隙流速越小其弥散系数越小;（4）试验中粉质黏土弥散系数约为0.005～0.048 cm2/d,远远小于下部砂土弥散系数0.524～7.477 cm2/d,差值达到了至少两个数量级,表明研究区内厚层黏土为控制地层,会较大程度阻碍地下水中溶质运移,上部含水层中的污染物或有机...     

吗啉废水的生化处理工艺

以含有吗啉、甲基吗啉的高浓度有机废水为研究对象,提出了曝气吹脱-吸附-生物处理的联合工艺,并在室内进行了小试实验。结果表明：原废水经过2次曝气吹脱后,ρ(NH₃-N)从62 500 mg/L降为431 mg/L,ρ(COD)从50 840 mg/L降为26 051 mg/L。通过吸附实验,ρ(COD)从26 051 mg/L降为2 769 mg/L,ρ(NH₃-N)从412 mg/L降为134 mg/L。在生物处理室内小试实验中,采用了活性污泥反应器与曝气生物滤池相结合的处理工艺。在活性污泥反应系统中,当废水pH为7.5、ρ(DO)为4.3 mg/L、水力停留时间为30 h时,COD的去除率最高,可以达到83.1%。在曝气生物滤池中,当ρ(DO)为3.3 mg/L时,COD去除率最高,达到55.8%。在生物处理的最佳参数条件下进行连续监测,当进水ρ(COD)为2 769 mg/L、出水ρ(COD)平均值为387 mg/L时,COD去除率可达到85.9%。吗啉废水经过此联合工艺的处理,ρ(COD)从50 840 mg/L降为387 mg/L。     

好氧颗粒污泥对有机污染物的吸附机制

为探讨好氧颗粒污泥对有机污染物的吸附机制,采用动态吸附方式研究好氧颗粒污泥对有机污染物的初期吸附作用,采用静态吸附方式考察好氧颗粒污泥失活前后对有机污染物吸附效率的差异,分析了好氧颗粒污泥吸附有机污染物前后的热力学参数及红外光谱变化。结果表明,好氧颗粒污泥对有机污染物的吸附过程表现出了明显的初期吸附去除现象,30min内对有机污染物吸附去除率达60.19%。好氧颗粒污泥吸附有机污染物是一个自发、吸热、熵增的过程,且吸附过程是一个以物理吸附为主、生物吸附和化学吸附为辅的复杂过程。     

西南表层岩溶带土壤中砷的迁移规律实验与模拟

岩溶地下河是我国西南地区的重要水源,工业生产过程中产生的砷污染物,除通过落水洞等直接进入并污染地下水外,还会在表层岩溶带溶缝、溶隙内吸附、滞留及富集,并在特定条件下再次迁移,成为"稳定次生污染源".以广西某砷污染事件为例,采用窄缝槽物理模型装置进行砷的动态吸附、解吸实验,并结合地球化学模拟研究砷污染物在表层岩溶带土壤中的迁移规律.实验结果显示表层岩溶带对砷的吸附以物理吸附（扩散过程）为主,相比吸附过程而言解吸速率则显得缓慢,而酸溶液相比去离子水可促进砷的解吸过程.地球化学模拟结果表明土壤矿物中以针铁矿对砷的吸附贡献最大,而酸溶液通过溶蚀针铁矿等矿物削弱对砷的吸附能力.因此在西南岩溶地区,表层岩溶带系统一旦纳入砷污染物,则解吸过程缓慢,易形成砷污染物的滞留、富集;而酸雨作用下砷的解吸、迁移过程加快,则会提高地下水系统的污染风险.