三氯乙烯在模拟有机质-矿质复合体中的吸附行为研究

土壤中有机质与无机矿物长期共存,其存在形式发生着变化。本文利用批实验的方法对三氯乙烯的吸附行为进行模拟研究,结果表明,土壤中有机质与无机矿物是以有机质-矿质复合体形式存在的,有机质与无机矿物的相互作用影响复合体的吸附性能,与有机质、无机矿物单体相比,复合体Kd、Koc明显发生变化;并提出了有机质-矿质复合体模型。     

C/M及TCE初始浓度对有机-矿物质复合体中有机质的吸附行为影响

有机污染物在有机-矿物质复合体上的吸附行为,是直接影响有机污染物在地质环境中迁移、转化及归宿的重要因素。为研究有机-矿物质复合体的形成及对有机污染物的吸附机理,以蒙脱石和腐植酸分别模拟地质吸附剂中的粘土矿物和有机质,制备成不同有机质含量与粘土矿物比率(C/M)的有机-矿物质复合体,对TCE进行吸附批实验。实验结果表明,腐殖酸与蒙脱石结合后提高了有机-矿物质复合体的界面疏水性,同时两者之间的相互作用也可能使得复合体中部分腐殖酸变的更加紧密,从而在一定程度上影响了整个固相介质的吸附行为;源腐植酸的K_om值为0.587 1 L/g,形成有机-矿物质复合体后K_om值均大于源腐植酸,随着复合体中C/M值的增加K_om值变化较小;TCE初始浓度的高低影响K_om值,以液相初始浓度500 μg/L为分界线,在低浓度段K_om值随着浓度的增加而减小,在高浓度段K_om值随着浓度的增加基本趋于稳定,此时TCE初始浓度对有机-矿物质复合体吸附行为的影响较小。     

三氯乙烯污染土壤和地下水污染源区的修复研究进展

作为现代工业中广泛使用的氯代溶剂,三氯乙烯（TCE）对土壤和地下水的普遍污染及其对人体健康的影响已经引起了人们的重视,关于其处理方法也受到人们的广泛关注。通过查阅国内外文献资料,对化学氧化、热修复及生物修复3种原位修复TCE污染的土壤和地下水污染源区的方法进行了总结,并在此基础上重点讨论了Fenton氧化、过硫酸盐氧化、蒸汽强化提取法及电阻加热法等原位修复方法     

包气带对三氯乙烯的吸附行为研究

有机污染物在包气带的吸附行为,直接影响有机污染物在环境中的迁移、转化等过程。采用浅层和深层包气带样品,利用批实验的方法研究不同有机碳含量的样品对三氯乙烯(TCE)的吸附行为。研究表明,包气带表层土壤比深层土壤的有机碳含量高,可能存在竞争吸附的问题,说明该土壤的吸附行为是以矿物吸附为主、有机质吸附为辅的类型;表层土壤的吸附具有较好的线性行为,不存在饱和吸附量;深层土壤有机碳含量低,其吸附为非线性的。     

模拟土样有机碳和矿物质对TCE吸附贡献的实验研究

为研究均一介质条件下有机碳含量及矿物质对TCE吸附行为的影响,简化了土壤环境的复杂性和异质性,以固定矿物质(高岭土∶石英砂=3∶7)作为土壤基体,添加不同质量分数的腐殖质(foc=0.16%~2.29%)配制成模拟土样,进行矿物质和模拟土样对TCE的吸附批实验。实验结果显示,TCE的吸附等温线呈非线性。随有机碳含量增加,表现为线性吸附增强,矿物质对TCE的吸附贡献随有机碳含量增加而减小。foc>0.82%时,矿物质对吸附作用的贡献率<5%;foc>1%时,可以基本忽略矿物质对吸附的影响。此外,TCE初始浓度也会影响有机碳和矿物质的吸附能力。用Freundlich模型分别拟合TCE吸附等温线的低浓度段和高浓度段(以Ce=500μg/L为浓度高低的分界),Freundlich指数n值呈现由大到小的趋势;TCE初始浓度越高,有机碳的吸附贡献率相对上升,而矿物质的贡献率则下降。TCE初始浓度在50~500μg/L之间、foc由0.16%增大到1%时,矿物质的吸附贡献率范围由28%~16%缩小到3%~1%之间,此时TCE初始浓度对有机碳和矿物质的吸附贡献率基本没有影响。     

北方某城市浅层地下水中有机污染物迁移转化的数值模拟研究

在3次野外取水样分析的基础上，分析了研究区域有机污染特征，并根据室内实验和国内外文献资料所获取的参数，利用地下水模拟系统软件（GMS）对研究区三氯乙烯（TCE）和四氯乙烯（PCE）在地下水中的运移转化进行数值模拟研究，模拟结果表明：研究区地下水中TCE和PCE存在生物降解作用，但是反应速率很小，这表明在相当长的时间内，其浓度仍可能保持在相当的水平上。     

土壤有机碳含量及异质性对三氯乙烯的吸附影响实验

采取北京城区表土样品和土壤标准参考样共7件,对原土样以及经H2O2氧化处理去除低聚合有机碳后的土样分别采用静态批实验方法,研究其对三氯乙烯(TCE)的等温吸附方程。实验结果表明7种土样对TCE的吸附模式均符合线性等温吸附方程,采用H2O2氧化去除土壤样品中的低聚碳,并没改变等温吸附线型,只是方程的参数发生了变化。剩余有机碳的含量仍都大于0.1%,仍然以有机碳的吸附为主;原土样、高聚碳、低聚碳对TCE吸附均表明,有机碳的含量与样品吸附TCE的能力没有明显的关系,证实不管是总有机碳、低聚碳还是高聚碳都有明显的异质性,它们所表现出来的吸附能力并不相同,有机碳结构组成的差异往往是影响其吸附的关键因素。而土壤有机碳经历矿化和腐殖化程度的差异是造成土壤有机碳结构组成差异的主要原因。     

土壤中有机碳含量对三氯乙烯的吸附影响实验

采用某地区土壤样品,利用批实验的方法,研究不同有机碳含量的土壤样品对三氯乙烯(TCE) 的吸附行为.研究表明,土壤样品中,由于有机碳含量不同,有机污染物三氯乙烯(TEC)的吸附量不同,存在有机碳含量的阈值区间(foc*).最小foc*=0.702%,最大foc*=1.831%,当foc<0.702%时,TCE吸附量随土壤样品的有机碳含量变化较小,基本不随foc变化而发生较大变化;在0.702%1.831%时,TCE吸附量随土壤样品的有机碳含量变化又变得平缓,基本上又不随foc升高而发生较大的变化.     

包气带土壤组成对三氯乙烯的吸附影响研究

有机质和矿物质是包气带土壤中的主要吸附介质,其吸附特性直接影响有机污染物在环境中的迁移、转化等过程。分别采用分析纯石英砂和典型粘土矿物高岭石模拟土壤的原生矿物和粘土矿物,利用批实验的方法研究土壤中各组成部分对三氯乙烯(TCE)的吸附行为。土壤有机质的吸附行为通过全土样和矿物质的对比得出。结果表明,粘土矿物是吸附氯代烃的主要矿物质,原生矿物对氯代烃的吸附量很小;土壤有机质含量和土壤吸附量之间有很好的正相关性;土壤有机碳含量与土壤粘土矿物含量的比值是影响吸附行为的另一重要因素,比值越小,Koc值越大,土壤对TCE的亲和力就越强。由于自然界中的土壤有机质大都与矿物质形成有机质-粘土矿物结合体,据此推测有机质-矿物质结合体会影响有机质的组成和形态,从而对其吸附行为有重要作用。     

不同基质中三氯乙烯的好氧代谢研究

本实验选取了苯酚、苯甲酸、苯、甲苯、氯苯等五种化合物作为活性污泥的驯化基质,以瓦呼仪作为测试手段,分析了五种基质在驯化后的活性污泥中的可降解性及三氯乙烯(TCE)在不同基质驯化后的活性污泥中的可生化性,并用计算出的12 h有机物氧化率表征有机物的可生化性难易度.苯酚、苯甲酸、甲苯、苯在40 mg/L时的氧化率达到最大值,分别为93.71%、64.67%、39.24%、9.15%.氯苯仅在20 mg/L时可降解,氧化率为46.09%,据此推断出几种代谢基质的可降解性从易到难的顺序为:苯酚 > 苯甲酸 > 甲苯 > 苯 > 氯苯.在甲苯、苯酚、苯甲酸、氯苯驯化后的活性污泥中TCE在50 μg/L时,其氧化率达到最大值,分别为54.14%、33.69%、23.91%、21.11%.在苯驯化后的活性污泥中TCE仅在10 μg/L时可降解,氧化率为13.8%.据此可推断出TCE在五种代谢基质中的可生化性从高到低的顺序为:甲苯 > 苯酚 > 苯甲酸 > 氯苯 > 苯.     

Sorption of silica by clay minerals

Clay minerals were reacted with silica-spiked solutions of unbuffered distilled water; water buffered at pH 5.5, 8 and 10; alkali chloride solutions; natural and artificial sea water to assess the influence of pH, silica and cation activities. The data are plotted as silica produced by dissolution or sorption of silica by clay surface as a function of initial silica concentration at a given pH and solution composition. This allows the determination of the dissolved silica value at which the clay mineral surface neither dissolves nor sorbs silica. The values of the various activities in different solutions are used to infer the phase equilibria between solution, clay mineral and the surface phase produced either by dissolution or sorption. Most intensively investigated were sorption reactions of kaolinite in sea water and other ionic solutions to form silica-rich, cation-rich surface phases in cationic solutions and silica-rich phases in cation-free solutions.Inferred equilibrium constants imply that silicate reconstitution is doubtful as a mechanism for partial control of silica and cation composition of sea water but is reasonable in silica-rich interstitial waters.     

Sorption of lead by phlogopite-rich mine tailings

The Pb sorption capacity of apatite ore mine tailings and its potential to act as a remediation agent in a Pb polluted areas were investigated. The tailings, originating from the Siilinjärvi carbonatite complex in Finland, consist mainly of phlogopite and calcite accompanied by apatite residues. The ability of the tailings to retain Pb from an aqueous solution was investigated using an isotherm technique. Furthermore, in a 3-month incubation experiment, uncontaminated mineral soil was amended with untreated tailings and with tailings artificially weathered with acid to increase the quantity of Al and Fe (hydr)oxides. Tailings of two particle-sizes (∅ > 0.2 mm and ∅ < 0.2 mm) somewhat differing in their mineralogical composition were investigated as separate amendments. All tailings materials were added to the soil in two dosages (5 g and 10 g of tailings per 125 g of soil). Following incubation, tailings-induced changes in the Pb sorption capacity of the soil were investigated with the isotherm technique. Finally, to investigate the distribution of sorbed Pb among various chemical pools, the soil samples amended with tailings were contaminated with Pb and then subjected to sequential fractionation analysis. The results revealed efficient removal of Pb from an aqueous solution by the tailings, presumably through precipitation and surface complexation mechanisms. Amending the soil with the tailings increased the mass-based maximum Pb sorption capacity from 10.8 mg kg⁻¹ of the control soil to 14–20.5 mg kg⁻¹ for the untreated tailings and to 32.1–72.1 mg kg⁻¹ for the acid-treated material. The tailings transferred Pb from the exchangeable pool to the non-extracted one and thereby substantially decreased its bioavailability. The material with a particle diameter of less than 0.2 mm had a higher mass-based Pb sorption capacity than the large-sized material. The results suggest that the tailings may potentially serve as an immobilizing agent in polluted areas.     

Sorption of lead by chemically modified rice bran

In this work, the effectiveness of native and chemically modified rice bran to remove heavy metal Pb(II) ions from aqueous solution was examined. Chemical modifications with some simple and low-cost chemicals resulted in enhancement of the adsorption capacities and had faster kinetics than native rice bran. Experiments were conducted in shake flasks to monitor the upshot of parameters over a range of pH, initial Pb(II) concentrations and contact times using a batch model study. The sorption capacities q (mg g^?1) increased in the following order: NaOH (147.78), Ca(OH)₂ (139.08), Al(OH)₃ (127.24), esterification (124.28), NaHCO₃ (118.08), methylation (118.88), Na₂CO₃ (117.12) and native (80.24). The utmost uptake capacity q (mg g^?1) was shown by NaOH-pretreated rice bran. The results showed that, using NaOH-modified rice bran, the chief removal of Pb(II) was 74.54 % at pH 5, primary Pb(II) concentration 100 mg L^?1 and contact time 240 min. Equilibrium isotherms for the Pb(II) adsorption were analyzed by Langmuir and Freundlich isotherm models. The Langmuir isotherm model, showing Pb(II) sorption as accessible through the high value of the correlation coefficient (R ² = 0.993), showed a q _max value of 416.61 mg g^?1. The kinetic model illustrated adsorption rates well, depicted by a second order, which gives an indication concerning the rate-limiting step. Thermodynamic evaluation of the metal ion ?G ^o was carried out and led to the observation that the adsorption reaction is spontaneous and endothermic in nature. NaOH chemically modified rice bran was a superb biosorbent for exclusion of Pb(II) and proved to be excellent for industrial applications.     

Sorption of heavy metal ions by a hydrous manganese oxide

Sorption of Co, Zn, Ca and Na by δ-MnO₂ was studied at 24.0 ± 0.5°C and pH 4. During the sorption of Co and Zn, Mn was released to the solution phase; however, Mn release was not detected during the sorption of Ca and Na. On the basis of crystal field theory, it is proposed that Zn may interchange with Mn²⁺ in the δ-MnO₂ structure, whereas Co may interchange with both Mn²⁺ and Mn³⁺. It is suggested that the interchangeable Mn²⁺ and Mn³⁺ sites were in the disordered layers in the δ-MnO₂ structure.Sorption of Co, Zn and Ca at pH 4 fitted single-site Langmuir isotherm expressions at all Ca concentrations, but only at concentrations greater than 10^?4 M for Co and Zn. Mn release by δ-MnO₂ at pH 4 during Co and Zn sorption also fitted single-site Langmuir isotherms. An expression for the case of multisite Langmuir sorption was derived and applied to the cases of Co and Zn sorption and to the case of Mn release during Co sorption. The data of these cases were used to calculate statistically the coefficients of multiple regression equations from which the sum of the capacities of all sites in each case were obtained. From all of these derived capacities, it is proposed that there was only one site where Ca interchanged with surface bound H. Zn was postulated to interchange not only with these bound H sites, but also with another site where it interchanged with structural Mn²⁺. Co was postulated to interchange with both of these sites, and additionally, with a third site where it interchanged with structural Mn³⁺.Using a pH-stat set at pH 4, it was determined that approximately 2 moles of H were released per mole of Co or Zn sorbed at bound H sites.     

羟基磷灰石除氟的实验地球化学研究

中国和世界上许多国家（地区） 都面临着饮用水氟含量超标的问题,因此研究氟的环境地球化学行为以及探索除氟 技术和原理至关重要。本实验采用廉价的非金属矿物羟基磷灰石作为吸附材料,研究羟基磷灰石吸附溶解态F-的地球化学 行为和机制,考察反应时间、pH、初始F-浓度等环境参数对吸附反应的影响。实验结果发现羟基磷灰石对F-的吸附反应需 进行到48 h以上时才接近反应平衡。在实验条件下（pH≥4）,F-的吸附量随pH升高而降低,羟基磷灰石对F-的吸附受pH 调控。同时还发现羟基磷灰石在pH=6条件下对F-的吸附等温线既满足Langmuir等温模式（R2=0.89） 同时也满足Freundlich 等温模式（R2=0.99）,并推导出该条件的理论最大吸附量为21.6×10-3。本研究还进一步采用了先进的XRD、SEM、 HR-TEM、19F NMR手段,系统地表征了反应前后吸附产物的形态和成分变化,发现在高F-浓度条件下,F-在羟基磷灰石表 面的吸附机制不再是单层的表面配位。核磁共振的结果表明F-可部分取代羟基磷灰石结构中的隧道羟基而形成含氟羟基磷 灰石。研究结果表明羟基磷灰石是一种相当具有潜力的除氟材料,值得进一步开发。     

Sorption of Ni on Na-rectorite studied by batch and spectroscopy methods

Sorption of Ni²⁺ on Na-rectorite as a function of contact time, temperature, pH and fulvic acid (FA)/humic acid (HA) was studied under ambient conditions. A pseudo-second-order rate equation was used to simulate the kinetic sorption. The removal of Ni²⁺ increased with increasing pH. The presence of FA/HA enhanced the sorption of Ni²⁺ at low pH values, whereas no drastic effect of FA/HA on Ni²⁺ uptake to rectorite was found at high pH values. The diffuse layer model (DLM) fitted the experimental data of Ni²⁺ sorption in the absence and presence of FA/HA very well with the aid of FITEQL 3.2. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms of Ni²⁺ at different temperatures. The thermodynamic data (ΔH⁰, ΔS⁰, ΔG⁰) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Ni²⁺ on rectorite was spontaneous and endothermic. The sorption and species of Ni²⁺ on rectorite in the presence and absence of FA/HA was also investigated and characterized by XPS. The spectroscopic analysis indicated no drastic structural changes of Na-rectorite and the sorption of Ni²⁺ mainly occurred on the surface and at the edge position of Na-rectorite.     

不同土壤有机质组分对憎水有机物的吸附机理研究

采用完全混合一步平衡反应实验方法，选择菲、萘、三氯苯和二甲苯作为憎水有机物(HOCs)的探针，研究了它们在土壤及其中的胡敏酸、胡敏素等有机质组分中的等温平衡吸附行为，探讨了非线性吸附的机制。结果表明，HOCs在水与土壤体系中表现为非线性吸附，其非线性的吸附行为主要受到土壤有机质(SOMs)的控制。SOMs具有高度不均匀的性质，HOCs表现出非线性吸附行为是其在不同的SOMs相扩散转移以及在相对聚结的胡敏素和“黑炭”的表面吸附的结果。     

Sorption of radium-226 from oil-production brine by sediments and soils

The sorption of²²⁶Ra from oil-production brine by soils and sediments was investigated. Sorption was rapid, and the percentage sorbed increased with brine dilution. Greatest removals of²²⁶Ra from sediments in the laboratory occurred with alkaline DTPA, HCl, and BaCl₂, with lesser removals using CaCl₂ and NaCl solutions. Digestion of sediments with NaOCl indicates that most of the native and sorbed²²⁶Ra is associated with the mineral rather than organic fraction of the sediments. Correlation analysis based on 14 soils indicates that the retention of²²⁶Ra may involve precipitation reactions associated with sulfate-bearing minerals, as well as ion-exchange reactions with the clay mineral fractions of surficial earth materials. Oceanographer, Naval Ocean Research and Development Activity, Code 334; NSTL Station, Mississippi 39529 NORDA Contribution #83:334:01.     

Sorption of heavy metal cations by low-temperature deposits of Pacific hydrothermal fields

Cation exchange reactions with participation of heavy metals Mn, Co, Ni, Cu, Zn, Cd, Ba, and Pb were studed in oceanic low-temperature hydrothermal deposits of various mineral compositions and in hydrogenic Fe-Mn crusts. Individual minerals and their assemblages differ significantly in absorptive capacity, which increases in the following order: hematite ? Si-protoferrihydrite < protoferrihydrite < geothite < nontronite ? Fe-vernadite + Mn-feroxyhyte < Fe-free vernadite < bernessite + Fe-free vernadite < bernessite; i.e., it successively increases from the mineral with a coordination type of lattice to minerals with a layer-type structure. The exchange complex of all minerals includes Na⁺, K⁺, Ca²⁺, and Mg²⁺, i.e., the main cations of seawater. In Mn minerals, Mn²⁺ is the main exchange component. The contribution of all the mentioned cations to the exchange capacity of minerals is as high as 90–98%. The highest absorptive capacity among the examined low-temperature oceanic deposits is characteristic of hydrothermal Mn minerals. Their capacity exceeds substantially that of hydrothermal oxides, hydroxides, Fe-aluminosilicates, and hydrogenic Fe-Mn minerals. The absorptive capacity of all examined Mn minerals relative to heavy metals increases in the same order: Ni < Zn < Cd < Mn < Co < Pb < Cu.