冻结技术在水土重金属污染净化与修复中的应用及进展

随着工业化进程的加快,水土重金属污染事件逐渐增多,对其治理与修复成为当前的迫切工作。冻结技术在治理修复污染水土时,其修复过程只向地层输入“冷量”,属于绿色修复技术,无二次污染风险,受到越来越多的关注。详细总结了冻结技术的修复机理,及其在污水、污泥、重金属污染土壤治理修复中的应用现状和最新研究进展。冻结修复机理是通过冰的自净作用和固-液相平衡原理来实现污染物的定向驱赶和富集,而黏性土壤颗粒的吸附和阻滞作用使单一技术对重金属污染土壤的修复难度增大,其他修复手段与冻结技术联合处理成为一种新的思路。利用冻结土体的低渗透性,还可有效降低污染物的迁移速度,封闭不同种类污染物,形成阻隔污染物扩散的冻结屏障。冻结修复技术在水土重金属污染净化及修复领域具有良好的应用前景。     

混合重金属离子侵蚀饱和黏性土渗透特性试验研究

渗透特性是表征黏性土层防渗能力及防污性能的关键控制因素,黏土衬垫渗透系数的正确选择对保证垫层的防污效果具有极其重要的意义。采用柔性壁渗透仪,通过室内试验研究了混合重金属离子共存情况下侵蚀饱和黏性土的渗透特性变化规律。试验结果表明,将可溶性铜、铬离子混合与铜、锰离子混合溶液作为渗液,黏性土渗透性均随着掺入离子浓度比例的增大而逐渐增强,且相同试验条件下,铜、铬离子混合溶液作为渗液测得的黏土渗透系数值大于铜、锰离子混合溶液作为渗液测得的渗透系数值。混合重金属离子的存在削弱了黏土垫层作为工程防污屏障服役的能力,并对黏土层的水力传导性起到了劣化作用。试验土样微观结构分析表明,渗液特性的改变影响了土样内部的微观结构,随着渗液混合离子质量比的增大,土样中出现了凝聚体且有效输运孔隙通道增大,与宏观渗透特性的变化规律相吻合。研究结果能够为有效评估黏土防污屏障的防渗隔污能力及研究堆场渗液在黏土垫层中的运移机制提供参考。     

CaCl2溶液对不同黏土基防渗墙渗透性的影响

在垃圾填埋场和场地污染防治工程中,黏土基防渗墙作为原位屏障,已广泛应用于隔离污染物与控制污染地下水的迁移。由黏土与地层混合形成的防渗墙与CaCl2溶液相互作用后,其渗透性会发生怎样的变化。针对这一问题,使用福建标准砂模拟砂性地层,以4种黏土作为混合材料,通过混合、浇筑和固结以后,对其渗透系数和水分特征曲线进行了实测。结果表明,在10%黏土添加量下,当4种砂-黏土混合土经0.2 mol/L CaCl2溶液渗透稳定后,其渗透系数相比渗透液为自来水时都有不同程度的增大,但渗透系数增大的倍数没有超过10。此外,CaCl2溶液在4种砂-黏土混合土中渗透稳定后试样的孔隙率没有发生较大变化,只是小幅地减小了。试验结果分析认为,钙离子与黏土矿物颗粒表面的单价阳离子发生了置换反应,使扩散双电层厚度减小,结合水含量降低,因而有效孔隙率增加,可能是宏观上造成渗透系数变大的主要原因。     

无机盐溶液作用下砂-膨润土竖向隔离屏障材料化学相容性试验研究

土-膨润土竖向隔离屏障广泛应用于城市工业污染场地。化学溶液作用下屏障材料的化学相容性,即渗透系数及其变化程度,是评价防污性能的关键因素。通过柔性壁渗透试验研究重金属铅-锌复合、六价铬作用下砂-膨润土竖向隔离屏障材料渗透系数的变化规律。由于无机盐溶液中铅、锌、钙对膨润土双电层的压缩,铅-锌复合、钙溶液作用下屏障材料试样渗透系数随金属浓度升高而增大。铅-锌复合作用下,金属浓度增至500mmol/L时试样渗透系数增幅达11倍,且无法满足防渗要求。相反,由于铬以阴离子络合形式存在,其对试样渗透系数影响相对小;与未污染状态测定结果相比,渗透系数增幅≤2倍。在膨润土孔隙比基础上,考虑无机盐溶液对膨润土膨胀特性的影响,建立无机盐溶液作用前后砂-膨润土竖向隔离屏障材料渗透系数统一预测方法。     

无机盐溶液作用下砂-膨润土竖向隔离屏障材料化学相容性试验研究

土-膨润土竖向隔离屏障广泛应用于城市工业污染场地。化学溶液作用下屏障材料的化学相容性,即渗透系数及其变化程度,是评价防污性能的关键因素。通过柔性壁渗透试验研究重金属铅-锌复合、六价铬作用下砂-膨润土竖向隔离屏障材料渗透系数的变化规律。由于无机盐溶液中铅、锌、钙对膨润土双电层的压缩,铅-锌复合、钙溶液作用下屏障材料试样渗透系数随金属浓度升高而增大。铅-锌复合作用下,金属浓度增至500 mmol/L时试样渗透系数增幅达11倍,且无法满足防渗要求。相反,由于铬以阴离子络合形式存在,其对试样渗透系数影响相对小;与未污染状态测定结果相比,渗透系数增幅≤2倍。在膨润土孔隙比基础上,考虑无机盐溶液对膨润土膨胀特性的影响,建立无机盐溶液作用前后砂-膨润土竖向隔离屏障材料渗透系数统一预测方法。     

生物化学作用对污泥固化体渗透性的影响

通过固化技术降低污泥的透水性,可以减少二次污染的风险,但是外界生物化学条件的改变会引起污泥固化体渗透性的变化。针对这个问题,采用强化污泥固化体所处的生物化学条件的方法,进行了不同酸性渗透液以及微生物激活环境下固化体渗透性的试验。试验结果表明,提高污泥固化水平可以显著降低污泥的渗透性,但是酸性环境下固化体的透水性将增加;污泥固化体渗透性的改变,不仅取决于酸性渗透液总的渗透量,也受酸的强度的控制;微生物的活动能够明显降低污泥固化体的透水性。     

粗粒土渗透损伤特性试验研究

为深入认识渗透变形对粗粒土渗透性及压缩性的影响,利用自主研发的加载式大型渗透变形仪对不同级配的粗粒土试样进行渗透变形全过程试验及侧限压缩对比试验,获得了不同试件产生渗透变形的临界水力梯度、渗透系数演化规律及损伤变化特性。研究成果表明：渗透变形过程中渗流路径中下游部位产生了渗透挤密效应,引起局部渗透性降低;在后期增加的水头作用下,先前产生渗透挤密部位的渗透性逐渐增大。试样产生渗透变形后,压缩模量减小;颗粒级配不同,渗透破坏引起的压缩损伤程度亦不相同。试件产生渗透变形后,在重力和渗透力作用下,试件结构将产生重构现象。     

利用铝−有机质絮状物降低渗透系数的试验研究

防渗对堤坝等水利工程、地下工程和污染物迁移都具有重要意义。基于自然灰化土层形成过程中因金属离子和有机质络合反应形成不透水土层的过程,提出了利用六水合氯化铝（AlCl3·6H2O）和有机质（OM）相互反应生成Al-OM絮状物来降低渗透系数的方法。开展了系列的注入试验,探究了浆液浓度、注浆速度和砂土颗粒级配对渗透系数降低和形成屏障长度的影响。研究结果表明：该方法可以有效地降低砂土的渗透性;渗透系数降低的速度随着浆液中Al-OM絮状物浓度的增大而增加;由于絮状物浓度的增加,孔隙堵塞的速度增快,从而阻止了其继续扩散,形成的屏障长度随之减小;Al-OM絮状物的尺寸随注浆速度的增大而减小。当注浆速度较大时,Al-OM絮状物的尺寸较小,因此渗透系数降低慢而扩散距离远。砂土的颗粒级配对渗透系数降低有重要影响,粗颗粒含量越大,渗透系数降低越小。     

石灰粉煤灰固化石油污染土的渗透特性及其工程再利用探讨

固化改性污染土的渗透性是推进污染土工程再利用需关注的指标之一。借助GDS环境土柔性壁渗透测试仪,优选兼具吸附与固化作用的石灰粉煤灰作为固化材料,以围压、渗透压、污染强度为变量参数,以固化前后石油污染土的渗透系数及土中残余含油量为指标,结合X射线衍射和扫描电镜,厘清渗透性演变及污染物迁移扩散规律,并以此探讨固化石油污染土的工程再利用性。研究结果表明：固化产物对石油分子的吸附作用弱化了石油斥水性,增加了渗透的有效通道,固化石油污染土的渗透系数较未固化石油污染的提高了两个数量级;土体干密度增大会增强对石油的吸附截流作用,围压、渗透压及污染水平的增大会增强土颗粒间相互作用,均引起石油污染土及固化石油污染土渗透性降低。固化作用可有效控制渗透作用下石油污染物的迁移扩散,各部位的残余含油量均非常接近于初始含油量,避免了渗透污染风险。结合石灰粉煤灰固化石油污染土力学特性(抗压强度为1 280.10 kPa,抗剪强度为388.88 kPa)、渗透性(渗透系数为4.28×10^-6～7.39×10^-6 cm/s)及迁移控制性(波动率为0.30%～4.90%),石灰...     

微生物胶结砂岩型铀矿砂的抗渗性能试验研究

地浸采铀产生的污染物通过渗透迁移作用威胁地下水资源,已成为制约地浸采铀技术发展的瓶颈,而微生物胶结技术能有效地降低砂岩铀矿的渗透性,是目前抑制污染物向采区周围地下水迁移的有效方法。因此,选用巴氏芽孢杆菌,分析其耐酸性;利用自行研制的砂岩型铀矿砂渗透系数试验装置,测得不同胶结液浓度、不同菌液与胶结液体积比以及不同注浆轮次条件下砂岩型铀矿砂的渗透系数,确定其最优的参数配比;采用扫描电镜（scanning election microscopy,简称 SEM）和X射线衍射光谱（X-ray diffraction,简称 XRD）等设备,表征微生物胶结前后铀矿砂的矿物成分及其微观结构,研究其微生物胶结抗渗机制。研究结果表明：巴氏芽孢杆菌在 pH = 4 时仍具有较好的繁殖能力和脲酶活性,能适应铀矿砂的酸性环境;在一定范围内增大胶结液浓度、菌液与胶结液的体积比可以促进碳酸钙的生成,最佳的胶结液浓度为 1 mol/L、菌液与胶结液体积比为1:3、注浆轮次为7时,注浆后铀矿砂的减渗率达到 95.33%;胶结后铀矿砂的渗透系数随注浆轮次的增加而降低,经过11轮注浆后铀矿砂的减渗率高达99.75%,渗透系数下降到 2.8×10⁻⁵ cm/s;沉积的碳酸钙晶型主要为方解石,方解石堵塞铀矿砂粒间孔隙,并将矿砂颗粒胶结成整体,是铀矿砂渗透系数降低的主要原因。微生物诱导碳酸钙沉淀胶结铀矿砂的抗渗机制为控制和减少地下水污染提供重要的理论指导。     

Compacted sewage sludge as a barrier for tailing impoundment

The feasibility of compacted sewage sludge serving as a barrier for tailing impoundment was evaluated by the batch test and hydraulic conductivity test with respect to heavy metal retardation and impermeability. The batch test results showed that the effective removal of heavy metals approached 97.8 and 93.4% for Zn and Cd, respectively. Formation of precipitation of oxy(hydroxide) and carbonate minerals was mainly responsible for the attenuation of heavy metals in the early period of the test. Nevertheless, the further removal of heavy metals can be attributed to the sulfate reduction. The hydraulic conductivity test indicated that almost all of the heavy metals contained in simulated acid pore water were retarded by compacted sewage sludge. The hydraulic conductivity of the compacted sewage sludge ranged from 3.0 × 10⁻⁸ to 8.0 × 10⁻⁸ cm s⁻¹, lower than 1.0 × 10⁻⁷ cm s⁻¹, which is required by regulations for the hydraulic barrier in landfill sites. Thus, this study suggested that compacted sewage sludge could be used as a bottom barrier for tailing impoundment.     

重金属作用下改性水泥系隔离墙化学相容性研究

水泥系隔离墙被广泛应用于工业污染场地修复工程,但其防渗性能有待改善,且在高浓度、毒理性重金属污染作用下的化学相容性有待研究。通过室内试验研究了不同粒化高炉矿渣（GGBS）掺量、膨润土掺量和固化剂总掺量对水泥系隔离墙的强度和渗透特性的影响;综合考虑成墙效果和成本,选出固化剂掺量为20%（水泥、粒化高炉矿渣和膨润土掺量分别为8%、8%和4%）作为改性水泥系竖向隔离墙的最优配比。通过柔性壁渗透试验研究了重金属锌、铅污染作用下改性水泥系隔离墙试样的化学相容性。结果表明,重金属溶液作用下试样防渗性能的下降由重金属种类、重金属浓度以及试样孔隙液pH值三者共同决定。重金属种类对防渗性能的不利影响为：硝酸锌-硝酸铅>硝酸锌>硝酸铅。锌、铅溶液作用下试样的渗透系数为自来水作用下渗透系数的1.49～10.10倍,且重金属溶液的浓度越高渗透系数越大。在满足防渗要求前提下,该配比墙体材料能阻挡50 mmol/L的硝酸锌污染液、100 mmol/L的硝酸铅污染液和10 mmol/L硝酸锌-硝酸铅污染液。     

Immobilization of Cd,Zn and Pb in sewage sludge using red mud

Sewage sludge is an inevitable end by-product of sewage treatment. Land application provides a cost-effective alternative for sewage sludge disposal. However, sewage sludge contains heavy metals that may limit its application. In this work, red mud was employed for the immobilization of heavy metals in sewage sludge. The effect of red mud amendment on heavy metal immobilization was evaluated using Toxicity Characteristic Leaching Procedure (TCLP) method. The TCLP results showed that the immobilization efficiency of Cd, Zn and Pb was 100, 92, and 82%, respectively, when sewage sludge was mixed with 10% red mud. Tests carried out in leaching columns demonstrated that heavy metal concentrations in the leachate of 10% red mud amended sludge were lower than those of the unamended sludge. Moreover, red mud decreased plant available heavy metal (Cd, Zn and Pb) content from 18.1, 17.2 and 14.6% to 6.9, 11.4 and 7.6%, respectively. Sequential chemical extraction experiments showed that after sludge was amended with 10% red mud, exchangeable fraction was reduced and iron and manganese oxides fraction was increased. Red mud amendment can effectively immobilize Cd, Zn and Pb in sewage sludge before land application.     

Effects of gasoline and diesel additives on kaolinite

Centrifuge tests were carried out to confirm and determine the effect of different pure alcohols, methyl t-butyl ether (MTBE) and mixtures of alcohols with gasoline and diesel on a thin disc of consolidated clay. The evolution of changes in the clay hydraulic conductivity with time was investigated and other structural changes due to chemical attack were monitored. The findings presented here demonstrate that the hydraulic conductivity of the clay appear to be generally related to the polarity of the chemicals and the dielectric constant. The cracking effect of butanol and MTBE on consolidated clay at low flow rate and low stress level was observed. The addition of ethanol or MTBE to diesel increased the clay permeability and the migration of organic chemical. The addition of ethanol to gasoline also caused an increase in the clay hydraulic conductivity. The effect of the association of alcohols with gasoline or diesel on the clay hydraulic conductivity is discussed, with a view to improving current pollution remediation techniques.     

黏土固化注浆帷幕控制重金属污染物运移的数值模拟

针对南昌市麦园垃圾卫生填埋场渗滤液防渗的实际情况,分析了重金属污染物在黏土固化注浆帷幕中的迁移转化特征,建立了地下水渗流模型和重金属污染物运移的耦合动力学模型。利用该模型对黏土固化注浆帷幕控制重金属污染物的迁移行为进行了模拟研究。数值模拟结果表明,在填埋场设计使用年限内黏土固化注浆帷幕对重金属污染物的阻滞率可以达到94.5 %以上,重金属污染物在防渗系统中的浓度范围沿地下水水流方向逐渐扩展,同一位置的浓度值随时间的延续呈逐渐增大的趋势,但距离污染源越远,污染物的浓度越低。结合现场检测情况,证明了黏土固化注浆帷幕对重金属污染物具有较强的污染控制能力。     

Experimental investigation on shear strength and permeability of a deeply dewatered sewage sludge for use in landfill covers

This paper presents an experimental study on a deeply dewatered sewage sludge produced by using a new technique of membrane filter press. The experiments involve measurements of sludge composition, basic physical properties, shear strength, water permeability, and leaching toxicity. The measurements of shear strength and permeability were also performed on the sludge specimens soaked in a low acid leachate or distilled water for 1 and 2 months. This is to investigate the influence of chemical change in pore fluid as a result of rainfall infiltration or leachate seepage at landfills. Comparison tests were also carried out on silty clay that is commonly used for landfill cover material. The experimental results show that the deeply dewatered sludge contains 66 % organic content and 85 % water content (dry mass basis). The undrained shear strength of the sludge is >25 kPa even after 2-month soaking in the leachate and distilled water, meeting the requirement of the Chinese standard [CJ/T249-2007, Disposal of sludge from municipal wastewater treatment plant: sludge quality for co-landfilling. Ministry of Building and Construction, P.R. China (in Chinese), 2007]. The measured cohesion and friction angle for the sludge are >20 kPa and 22.3°, respectively. The soaking of sludge specimens in either leachate or distilled water resulted in an increase in frictional angle by several degrees. The water permeability for the sludge ranges from 0.68 × 10^?8 to 1.3 × 10^?8 cm/s, and permeability after 2-month soaking is less than the minimum requirement for the barrier layer of landfill covers (i.e., 1.0 × 10^?7 cm/s). The concentrations of heavy metals leaching from the dewatered sludge are lower than the limit values of leaching toxicity for the wastewater discharge standard of China. The experimental results indicate that deeply dewatered sludge can be used as an alternative material for the barrier layer of landfill covers.     

温度和有效应力对砂岩渗透性影响的试验研究

为探讨温度和有效应力对渗透性的影响,在不同温度水平和不同有效应力水平下进行了砂岩的渗透率试验。根据试验结果,初步分析了温度和有效应力对砂岩渗透率及其水力传导系数的影响。试验结果表明,砂岩的渗透率及其水力传导系数都是温度和有效应力的函数:在温度一定的条件下,砂岩的渗透率和水力传导系数均随有效应力的增加而呈负指数规律减小;在有效应力一定的条件下,砂岩的渗透率随温度的升高而减小,但水力传导系数与温度之间的关系函数并非单调函数。因此,在工程实践中不考虑温度和有效应力对岩石 (体)渗透性的影响是不合适的。      

Bioclogging in porous media under continuous-flow condition

Bioclogging extensively exists in porous media, such as permeable reactive barrier, constructed wetland, reverse osmosis, and biofilter systems. Microorganisms overproduce and affect the efficiency of sewage treatment. In this paper, variations in biochemical and hydraulic parameters during the clogging process were obtained using various column experiments. The hydraulic conductivity first decreased sharply to 18.32 % of the original value at the 12th day and decreased to 2.71 % at the end of the experiment, a reduction of more than an order of magnitude. The hydrodynamic dispersion had the highest increase at 7.13 times the initial value and ultimately decreased to 29 %. The porosity decreased to 47.24 % of the initial value, and the total bacterial count in the inlet of the column increased from 3.4 × 10⁶ to 8.8 × 10⁸ cells/mL. Based on the biochemical and hydraulic parameter variation, the clogging process can be divided into four stages: (1) severe clogging occurs, and aerobic microorganisms reproduce rapidly in the inlet; (2) clogging exists in the entire column, and hydrodynamic dispersion increases sharply as aerobic and anaerobic microorganisms reproduce; (3) anaerobic microorganisms reproduce rapidly and produce more gas, and hydrodynamic dispersion decreases quickly; (4) aerobic and anaerobic microorganisms multiply continuously, and hydrodynamic dispersion, hydraulic conductivity, and porosity decrease steadily. Bioclogging then transforms into a steady stage.