有机粘土和粘土对p,p'-DDE的吸附/解吸研究

采用批量平衡实验,研究阳离子表面活性剂十六烷基三甲基铵离子(HDTMA)改性的zeo-HDTMA(有机沸石)、mont-HDTMA(有机蒙脱土)和atta-HDTMA(有机凹凸棒土)及其原粘土对典型有机氯农药DDT代谢产物p,p'-DDE的吸附解吸特性.结果表明,随原粘土阳离子交换容量(CEC)的增大,有机粘土吸附量增大,且有机粘土的吸附量比原粘土大大提高;有机粘土和原粘土对p,p'-DDE的吸附能力顺序为:zeo-HDTMA＞mont-HDTMA＞atta-HDTMA≥mont(蒙脱土)＞atta(凹凸棒土)＞zeo(沸石),这一顺序与它们的有机碳质量分数大小顺序一致.原粘土对p,p'-DDE的吸附等温线符合Langmuir吸附等温方程,吸附呈单分子层形式,且存在竞争吸附;有机粘土对p,p'-DDE的吸附等温线符合Linear吸附等温方程,吸附是p,p'-DDE在有机粘土中有机相的分配所致.当CaCl2质量浓度从0增加到50 g/L时,mont-HDTMA对p,p'-DDE吸附量提高了10.3%.有机粘土和原粘土对p,p'-DDE的解吸率大小顺序为:zeo＞atta＞mont＞atta-HDTMA＞mont-HDTMA＞zeo-HDTMA,这一顺序与它们的有机碳质量分数大小顺序相反.     

多环芳烃在淮河、黄河和卫河沉积物上的吸附及解吸行为研究

以淮河沉积物上多环芳烃的吸附研究为主线,以黄河、卫河沉积物为比对,研究菲和芘在3种河流沉积物上的吸附和解吸行为,重点考察吸附剂有机质组分、环境温度、吸附时间和共存物等因素对吸附的影响,找出可以用来预测这3条河流沉积物对多环芳烃吸附作用的模式。结果表明,菲和芘在3种河流沉积物上的吸附均呈非线性,可用Freundlich方程拟合,属放热反应、物理吸附。同一吸附质的有机碳归一化分配系数(Koc)数值相近,说明吸附剂有机质组分对吸附起主导作用;吸附能力随着吸附时间延长而增加,并与吸附质疏水性成正比;多环芳烃共存,有竞争吸附现象;辛醇/水分配系数可用来预测3种河流沉积物对多环芳烃的吸附作用;解吸存在滞后现象,吸附质疏水性强、吸附剂有机质含量高的体系,解吸滞后现象更加明显。     

粘土矿物与重金属界面反应的研究进展

介绍了3种粘土吸附剂:蒙脱石、高岭石和伊利石对重金属的吸附、脱附等界面反应机理,以及粘土矿物对重金属的选择性及对吸附的影响因素.另外,还探讨了为提高其吸附性能而进行的改性方法.     

粘土矿物与重金属界面反应的研究进展

介绍了3种粘土吸附剂：蒙脱石、高岭石和伊利石对重金属的吸附、脱附等界面反应机理，以及粘土矿物对重金属的选择性及对吸附的影响因素。另外，还探讨了为提高其吸附性能而进行的改性方法。     

阴-阳离子有机膨润土制备及其对铅离子的吸附

用十八烷基三甲基溴化铵（STAB）和十二烷基苯磺酸钠（SDBS）共同改性膨润土制备阴．阳离子有机膨润土,并用红外光谱分析法、热分析法和X粉晶衍射分析进行了表征;考察了阴-阳离子有机膨润土对铅离子的吸附性能。结果表明,用0．5CEC（cationexchangecapacity）十八烷基三甲基溴化铵和0．4CEC十二烷基苯磺酸钠改性的膨润土吸附铅的效果最佳;阴-阳离子有机膨润土吸附铅离子的能力比改性前明显增加,达到吸附平衡所需要的时间缩短;pH值强烈影响有机膨润土对铅离子吸附;有机膨润土对铅离子等温吸附过程符合Langmuir吸附模型;吸附热力学分析表明该吸附是一个放热过程,降低温度有利于铅离子的吸附。     

改性陶粒对水中内分泌干扰物的吸附去除

用CTMAB(十六烷三甲基溴化铵)对陶粒进行改性.实验研究了陶粒改性前后对5种内分泌干扰物EDCs(美托洛尔MTP、磺胺甲噁唑SMZ、卡马西平CBZ、对氯苯氧异丁酸CA、17α-乙炔基雌二醇EE2)的吸附特性.结果表明,CTMAB改性处理对陶粒的孔结构和表面性质都有影响,有效吸附的孔径所占比例和陶粒表面极性升高;室温条件下,EDCs初始浓度和吸附剂浓度均为1 mg/L时,实验用改性陶粒和陶粒达到吸附平衡的时间基本相同,均为5 min左右;改性陶粒能提高大部分EDCs的吸附量,5种内分泌干扰物混合物一起吸附时存在竞争,其中SMZ和MTP竞争力强,CA最弱;吸附机理包括表面物理吸附和分配作用.实验研究拟为改性陶粒应用于水中痕量污染物的处理提供理论依据,支撑保障饮用水处理达标的目的.     

改性高炉渣对甲基橙的吸附

以盐酸和十六烷基三甲基溴化铵对包钢高炉渣进行表面改性,通过XRD、SEM和N_2吸附-脱附测试研究其微观结构和孔径分布,并以阴离子型染料甲基橙溶液为模拟染料废水研究其吸附性能,进而探索最佳改性制备条件。研究结果表明:有机改性高炉渣主要化学成分为SiO_2,表面有明显的孔道结构,比表面积高达394.5 m~2·g~(-1),平均孔径为12.4 nm;有机改性高炉渣对甲基橙溶液均具有较强的吸附性能,最佳改性条件为加入改性剂盐酸浓度为3 mol·L~(-1)、十六烷基三甲基溴化铵的最终投加浓度为8 g·L~(-1)、水热温度160℃和16 h,此时所制备的有机改性高炉渣吸附性能最强,吸附率为98.06%,最大吸附量达357.14 mg·g~(-1)。等温吸附实验表明,有机改性高炉渣对甲基橙溶液的吸附属于多分子层吸附。     

表面活性剂改性4A分子筛对Cr(VI)的吸附行为

采用浸渍法对4A分子筛进行表面改性,通过引入阳离子表面活性剂,使4A分子筛表面附着季铵型阳离子,并与反离子Br-形成"阴离子交换膜",从而促使更多的Cr(VI)阴离子通过离子交换吸附到改性4A分子筛上,通过X-射线衍射(XRD)和傅里叶变换红外光谱(FTIR)对样品的物相结构和组成进行表征分析。研究表明,表面活性剂的类型和疏水碳氢链结构会影响4A分子筛的吸附能力,十八烷基三甲基溴化铵(OTAB)碳氢链长,在分子筛表面形成的双分子层密,对Cr(VI)的吸附量最大。采用准一级、准二级、Elovich和Bangham动力学模型对六价铬的吸附数据进行拟合,其中准一级动力学方程最符合十八烷基三甲基溴化铵改性分子筛的吸附行为。同时,分别从Langmuir和Redlich-Peterson等温吸附模型获得六价铬的最大吸附量为13.98 mg/g,且改性分子筛以均一表面吸附为主。     

温度和表面活性剂对菲在土壤中吸附的影响

通过静态吸附实验,研究了北京地区土壤对菲的吸附行为,考察了温度和表面活性剂对菲吸附的影响.结果表明,6种土样对菲的吸附等温线均较好地符合Freundlich吸附模式,其吸附能力的大小顺序为:轻壤土>轻粘土>砂壤土>中壤土>重壤土>紧砂土;温度升高不利于菲在土壤中的吸附;十二烷基苯磺酸钠(LAS)和十六烷基三甲基澳化铵(CTAB)均利于菲在土壤表面的解吸,LAS和CTAB对菲的解吸率最高可达66.2%和31.8%,且LAS的解吸效果更好.     

阳离子表面活性剂改性四氧化三铁-沸石复合材料对水中刚果红的去除作用

制备了四氧化三铁-沸石复合材料(磁性沸石)和阳离子表面活性剂改性磁性沸石(有机改性磁性沸石),采用X射线衍射分析对有机改性磁性沸石进行了表征,通过批量实验考察了有机改性磁性沸石对水中刚果红的吸附性能,并对相关的吸附机制进行了讨论。实验表明,有机改性磁性沸石对水中的刚果红具备良好的吸附能力,且有机改性磁性沸石对刚果红的吸附能力远远高于磁性沸石。有机改性磁性沸石对水中刚果红的吸附动力学符合准二级动力学模型,吸附平衡数据可以采用Langmuir、Freundlich和Dubinin-Radushkevich(D-R)等温吸附模型加以描述。根据Langmuir等温吸附模型计算得到的有机改性磁性沸石对刚果红的最大吸附容量为146 mg/g(pH 7和30℃)。有机改性磁性沸石对水中刚果红的吸附属于自发和放热的过程。有机改性磁性沸石吸附水中刚果红的作用机制包括静电吸引、有机相分配、氢键和表面配位。X射线衍射分析结果表明,有机改性磁性沸石含四氧化三铁,吸附刚果红后的有机改性磁性沸石可以很容易地通过外加磁场的作用快速地从水中分离出来。上述结果表明,有机改性磁性沸石适合作为一种吸附剂去除废水中的刚果红。     

Immobilization of fungal laccase onto a nonionic surfactant-modified clay material: application to PAH degradation

Nonionic surfactant-modified clay is a useful absorbent material that effectively removes hydrophobic organic compounds from soil/groundwater. We developed a novel material by applying an immobilized fungal laccase onto nonionic surfactant-modified clay. Low-water-solubility polycyclic aromatic hydrocarbons (PAHs) (naphthalene/phenanthrene) were degraded in the presence of this bioactive material. PAH degradation by free laccase was higher than degradation by immobilized laccase when the surfactant concentration was allowed to form micelles. PAH degradation by immobilized laccase on TX-100-modified clay was higher than on Brij35-modified clay. Strong laccase degradation of PAH can be maintained by adding surfactant monomers or micelles. The physical adsorption of nonionic surfactants onto clay plays an important role in PAH degradation by laccase, which can be explained by the structure and molecular interactions of the surfactant with the clay and enzyme. A system where laccase is immobilized onto TX-100-monomer-modified clay is a good candidate bioactive material for in situ PAHs bioremediation.     

Sorption of organic contaminants in a fractured chalk formation

Sorption capability of bedrock components from a fractured chalk province was evaluated using ametryn, phenanthrene, m-xylene, 2,4,6-tribromophenol, and 1,2-dichloroethane. Sorption isotherms for the four aromatic compounds were nonlinear on gray (unoxidized) chalk. Over the studied solution ranges, the distribution coefficient decreased by factor of 3 for phenanthrene and m-xylene, a factor 4 for ametryn, and by an order of magnitude for 2,4,6-tribromophenol. In contrast, 1,2-dichloroethane displayed a linear isotherm. The importance of polar interactions for ametryn sorption was evaluated by normalizing sorption to an "inert" solvent, n-hexane. n-Hexane-normalized sorption of ametryn was much greater than that of phenanthrene, presumably due to ametryn participation in hydrogen bonding interactions. In sharp contrast to sorption to gray chalk, sorption to white (oxidized) chalk is 100- to 1000-fold lower at any given solution concentration. The much greater sorption on gray chalk cannot be explained by specific surface area, clay content, or organic matter content; thus, the nature of the organic matter is considered to control sorption in the chalk samples. Gray chalk sorption capacity estimates for ametryn and 2,4,6-tribromophenol are similar, which, together with evidence of competition for sorption sites, suggests that the limited capacity sorption domain for both compounds is similar.     

Dissolved organic matter effects on the performance of a barrier to polycyclic aromatic hydrocarbon transport by groundwater

In order to contain the movement of organic contaminants in groundwater, a subsurface sorption barrier consisting of sand or clay minerals coated with a cationic surfactant has been proposed. The effectiveness of such a sorption barrier might be affected by the presence of dissolved organic matter (DOM) in the groundwater. To study the impact of DOM on barrier performance, a series of batch experiments were performed by measuring naphthalene and phenanthrene sorption onto sand coated with cetylpyridinium chloride (CPC) and bentonite coated with hexadecyltrimethylammonium bromide (HDTMA) in the presence of various concentrations of DOM. The overall soil-water distribution coefficient (K*) of naphthalene and phenanthrene onto CPC-coated sand decreased with increasing DOM concentration, whereas the K* of the compounds onto HDTMA-coated bentonite slightly increased with increasing DOM concentration. To describe the overall distribution of polycyclic aromatic hydrocarbons (PAHs) in the systems, a competitive multiphase sorption (CMS) model was developed and compared with an overall mechanistic sorption (OMS) model. The modeling studies showed that while the OMS model did not explain the CPC-coated sand experimental results, a model that included competitive sorption between DOM and PAH did. The experimental results and the modeling study indicated that there was no apparent competition between DOM and PAH in the HDTMA-coated bentonite system, and indicated that in groundwater systems with high DOM, a barrier using HDTMA-coated bentonite might be more effective.     

Evaluation of methods to determine adsorption of polycyclic aromatic hydrocarbons to dispersed carbon nanotubes

A number of methods have been reported for determining hydrophobic organic compound adsorption to dispersed carbon nanotubes (CNTs), but their accuracy and reliability remain uncertain. We have evaluated three methods to investigate the adsorption of phenanthrene (a model polycyclic aromatic hydrocarbon, PAH) to CNTs with different physicochemical properties: dialysis tube (DT) protected negligible depletion solid phase microextraction (DT-nd-SPME), ultracentrifugation, and filtration using various types of filters. Dispersed CNTs adhered to the unprotected polydimethylsiloxane (PDMS)-coated fibers used in nd-SPME. Protection of the fibers from CNT adherence was investigated with hydrophilic DT, but high PAH sorption to the DT was observed. The efficiency of ultracentrifugation and filtration to separate CNTs from the water phase depended on CNT physicochemical properties. While non-functionalized CNTs were efficiently separated from the water phase using ultracentrifugation, incomplete separation of carboxyl functionalized CNTs was observed. Filtration efficiency varied with different filter types (composition and pore size), and non-functionalized CNTs were more easily separated from the water phase than functionalized CNTs. Sorption of phenanthrene was high (< 70%) for three of the filters tested, making them unsuitable for the assessment of phenanthrene adsorption to CNTs. Filtration using a hydrophilic polytetrafluoroethylene (PTFE) filter membrane (0.1 μm) was found to be a simple and precise technique for the determination of phenanthrene adsorption to a range of CNTs, efficiently separating all types of CNTs and exhibiting a good and highly reproducible recovery of phenanthrene (82%) over the concentration range tested (70–735 μg/L).

     

Electrokinetic enhancement of phenanthrene biodegradation in creosote-polluted clay soil

Given the difficulties caused by low-permeable soils in bioremediation, a new electrokinetic technology is proposed, based on laboratory results with phenanthrene, to afford bioremediation of polycyclic aromatic hydrocarbons (PAH) in clay soils. Microbial activity in a clay soil historically polluted with creosote was promoted using a specially designed electrokinetic cell with a permanent anode-to-cathode flow and controlled pH. The rates of phenanthrene losses during treatment were tenfold higher in soil treated with an electric field than in the control cells without current or microbial activity. Results from experiments with Tenax-assisted desorption and mineralization of 14C-labeled phenanthrene indicated that phenanthrene biodegradation was limited by mass-transfer of the chemical. We suggest that the enhancement effect of the applied electric field on phenanthrene biodegradation resulted from mobilization of the PAH and nutrients dissolved in the soil fluids.     

Sorption of paraquat on clay components in Taiwan's oxisol

The sorption of herbicides in soils is mainly influenced by clay components. The objectives of this study were to evaluate the contribution of clay components on paraquat sorption. The surface soils (0-20 cm) of a Laopi pedon (Fine, mixed, Hyperthermic Typic Hapludox) were separated clays into whole (< 2.0 microm), coarse (0.2-2.0 microm), and fine (< 0.2 microm) fractions with the treatments of removals of organic matter (OM) and free Fe (Fed) oxides. Results indicated that sorption isotherm of paraquat was fitted by the nonlinear Freundlich equation with R2 values ranged in 0.79-0.96, respectively. The shape of paraquat adsorption isotherm on the fine fraction was H-type, but their shapes on the whole and coarse fractions were L-types. The fine clay fractions gave higher contribution on paraquat sorption than the coarse clay fractions identified by their K(f) values. Organic matter associated with fine clay fraction had high CEC contributing to relatively high affinity for paraquat. The DCB treatment created high-affinity sites for paraquat on the fine clay, but had little effect on paraquat sorption for the coarse clay. Chemisorption is the major mechanism for retention of paraquat on clay components, not ion exchange. However, the silicate clay had the highest affinity for paraquat and free Fe compound had the lowest.     

土壤及其主要化学组分对五氯酚吸附特征研究

研究了土壤原样及其去锰氧化物、去铁氧化物、去有机质和去水溶性有机质(DOM)土壤样品对五氯酚(PCP)的吸附规律,分析了土壤及其主要化学组分对PCP的吸附机制.实验结果表明,Langmuir方程可较好地描述PCP在各土壤样品上的热力学吸附过程.PCP在土壤上的吸附行为与自身性质和土壤理化性质密切相关,有机质和铁氧化物对PCP的吸附起到促进作用,而锰氧化物和DOM则能在一定程度上抑制PCP的吸附.通过Langmuir方程得到的拟合结果,可判断PCP在各土壤样品上的最大吸附量为去锰氧化物土壤样品＞去铁氧化物土壤样品＞去DOM土壤样品＞土壤原样＞去有机质土壤样品.     

Evaluation of impacts of soil fractions on phenanthrene sorption

Phenanthrene sorption to soils and soil fractions was investigated using two contrasting soils with different clay mineral and organic carbon (OC) contents in an attempt to evaluate the contribution of each soil fraction to phenanthrene sorption and the applicability of the carbon-normalized distribution constant (K(OC)) in soils. Sorbents were characterized using surface analysis, solid-state (13)C NMR analysis, and glass transition temperature (T(g)) analysis to gain a insight into the chemical nature of OC in soils. Dissolved organic carbon (DOC) in the soil solution impeded the phenanthrene sorption, while humins accounted for the predominant phenanthrene sorption in soils. The contribution of OC to phenanthrene sorption in soil would be overestimated if only a K(OC)-approach was adopted, since clay minerals could account for much of the sorption, especially when OC was low in soils. Nitrogen gas was shown to be inappropriate for probing non-polar sorption capacity. The results obtained highlight the importance of clay minerals in governing the sorption of phenanthrene in soil, and emphasize the inapplicability of the carbon-normalized distribution coefficient K(OC) in soils.     

Interactions between a polycyclic aromatic hydrocarbon mixture and the microbial communities in a natural freshwater sediment

The toxicity of a polycyclic aromatic hydrocarbon (PAH) mixture was assessed on the indigenous microbial communities of a natural freshwater sediment. The fate and effects of the PAH mixture (phenanthrene, fluoranthene and benzo(k)fluoranthene) were studied over 28 days. Bacterial communities were described by bacterial counts (total bacteria and viable bacteria), and by some hydrolytic enzyme activities (beta-glucosidase and leucine-aminopeptidase), PAH concentrations were measured in the overlying waters and in the sediments. No effect of PAH was detected at 30 mg/kg for all bacterial parameters. At 300 mg/kg, the quantity of total bacteria and the proportion of viable bacteria markedly decreased, compared to the control (0 mg PAH/kg). At 300 mg/kg, an increase of the beta-glucosidase activity and a decrease of the leucine-aminopeptidase activity were observed. For all treatments, the benzo(k)fluoranthene concentration in the sediment was stable over 28 days whereas, in the same time, only 3-6% of the initial concentrations of phenanthrene and fluoranthene remained. This study shows that (1) PAH induce perturbations of sediment microbial communities in terms of density and metabolism (but not always as an inhibition), (2) indigenous bacteria of sediments might be used for toxicity assessment of specific organic pollutants, (3) native microorganisms of sediment seem to have a high capacity for PAH degradation, depending on the physico-chemical properties and the bioavailability of the substance encountered.