一组含氟取代苯化合物土壤吸附系数的QSPR分析

为了研究含氟取代苯化合物的环境行为,测定１４个含氟取代苯化合物的土壤有机碳吸附系数Ｋｏｃ的值,运用正辛醇／水分配系数Ｋｏｗ及分子连接性指数和量子化学参数进行了定量结构－性质相关分析,得到２个回归方程。回归方程表明Ｋｏｗ与分子连接性指数结合可较好地预测含氟取代苯化合物的Ｋｏｃ而量子化学参数的引入证明了极性作用地土壤吸际过程的影响。     

Lead sorption by a Mexican,clinoptilolite-rich tuff

Goal, Scope and Background The retention of lead by a Mexican, clinoptilolite-rich tuff from Oaxaca (Mexico) at different pH values was evaluated and the lead sorption mechanisms on the zeolitic material in this work were discussed. Methods Isotherms were determined using lead nitrate solutions (initial pH values between 2 and 5) at 303 K. After the equilibrium was reached, the content of lead in the liquid phases was determined by atomic absorption spectrometry. The elemental composition of the clinoptilolite-rich tuff before and after the lead sorption process was evaluated by electron microscopy. Results The maximum ion exchange capacity of the Mexican, clinoptilolite-rich tuff for lead was 1.4 meq/g at pH 3, considering an ion exchange mechanism in the absence of any precipitated or hydrolyzed lead species in the sorption process or any change in the zeolite network. Langmuir and Freundlich isotherms were also considered in this work for comparison purposes. Discussion It is important to consider the nature of the sorption processes before choosing a model to describe the interaction between the metal ions and the sorbent. Conclusions The chemical lead speciation, the pH, as well as the characteristics of the clinoptilolite-rich tuff are important factors to be considered on the lead sorption process by natural zeolites. The chemical species involved in that process are Na⁺ from the zeolite and Pb²⁺ from the aqueous solution at pH 2 and 3, so that the ion exchange mechanism explains the lead sorption processes by the clinoptilolite-rich tuff through the ion exchange isotherms. The sodium, Mexican, clinoptilolite-rich tuff is a potential adsorbent for lead from aqueous solutions. Recommendations and Perspectives The natural zeolite-rich tuffs are very important as ion exchangers for the treatment of polluted water due to their sorption properties and low cost. The sorption behavior of each natural material depends on their composition. Mexican, clinoptilolite-rich tuff from Oaxaca (Mexico) could be used for the treatment of waste water contaminated with lead. It would be important to propose this material as an alternative as waste water treatment, because it shows good selectivity for the removal of heavy metals from water.     

纳米零价铁对水中芴的去除研究

研究了实验室自制的纳米零价铁在不同投加量、初始浓度、pH及温度条件下,对芴溶液的吸附效果、吸附等温线及吸附动力学.结果表明,随着纳米铁投加量的增加,芴的去除率升高;增加芴的初始浓度,去除率则相应下降,同时平衡吸附量增加.另一方面,纳米铁对芴的吸附能力随pH的升高而下降;温度为15~35℃时,芴的平衡吸附量随温度的升高而增加,但变化不大.纳米铁对芴的吸附等温线符合Langmuir和Freundlich方程;纳米铁对芴的吸附过程很好地符合准二级速率方程,吸附速率随芴初始浓度的增大而减小,平衡吸附量随芴初始浓度的增大而增大.除上述结果以外,本文还对此反应体系的吸附机理进行了初步探讨.     

Pb(II) adsorption from aqueous solutions by raw and treated biomass of maize stover – A comparative study

The potential to remove Pb(II) ion from wastewater treatment systems using raw and treated maize stover through adsorption was investigated in batch experiments. To achieve this, batch mode experiments were conducted choosing specific parameters such as pH (2–8), dosage concentration (2–30 g L⁻¹), contact time (5–180 min), temperature (20–45 °C) and metal ion concentrations (10–50 mg L⁻¹). Adsorption was pH-dependent showing a maximum at pH value 5. The equilibrium sorption capacities of raw and treated maize stover were 19.65 and 27.10 mg g⁻¹, respectively. The adsorption data fitted well to the Langmuir isotherm model. Kinetic studies revealed that the adsorption process followed pseudo-second-order model. The calculated thermodynamic parameters showed that the adsorption of Pb(II) was spontaneous and exothermic in nature. Consequently, this study demonstrated that both raw and treated maize stover could be used as adsorbents for the treatment of Pb(II) from industrial wastewaters.     

活化剩余污泥对Pb2+的吸附热力学研究

以城市污水处理厂脱水干污泥为原料,以浓硫酸为活化剂,制备活化剩余污泥吸附剂,采用正交试验法考察了Pb2+初始质量浓度、初始pH值、吸附温度、活化剩余污泥投加量对活化剩余污泥吸附性能的影响.结果表明,活化剩余污泥对Pb2+的最佳吸附条件为pb2+初始质量浓度60 mg/L、初始pH值5、活化剩余污泥投加量100mg、吸附温度288 K,影响从高到低的各因素为Pb2+初始质量浓度、吸附温度、初始pH值、活化剩余污泥投加量.采用Langmuir、Freundlich、D-K-R吸附等温方程对不同温度下的吸附平衡试验数据进行拟合.Langmuir吸附等温方程可以较好地描述活化剩余污泥对pb2+的吸附平衡过程.其吸附过程吉布斯自由能△G为-3.35 ～-0.32 kJ/mol,焓变△H和熵变△S均为负值,表明活化剩余污泥对pb2+的吸附是自发的、以物理吸附为主的放热反应.     

炔雌醇和壬基酚在土壤中的吸附-解吸特征

通过吸附动力学研究和批量平衡试验,以炔雌醇(EE2)和壬基酚(NP)为代表,考察内分泌干扰物在3种不同性质的天然土壤中的吸附-解吸特征.结果表明,双室一级动力学模型比单室一级动力学模型更适合描述EE2、NP在土壤中的动态吸附过程.快吸附过程在吸附初期占据主导地位,之后慢吸附室的相对贡献逐渐增大,直至达到吸附平衡.土壤对NP的吸附速率是EE2的2.0～4.7倍.Freundlich模型和DA模型均能较好地拟合EE2与NP的吸附等温线,但DA模型拟合效果更佳.饱和吸附容量与土壤有机质含量呈显著正相关,EE2的饱和吸附容量(0.85～7.67μg·g-1)明显低于NP(10.47～110.15μg·g-1).吸附自由能计算表明,土壤对EE2和NP的吸附以物理作用为主.此外,3种受试土壤对EE2和NP的解吸附均存在滞后现象,需要预防其潜在的环境风险,其中有机质含量最高、比表面积最大的土样滞后性最明显.     

Role of sorbent surface functionalities and microporosity in 2,2’,4,4’-tetrabromodiphenyl ether sorption onto biochars

The study provides insight into the combined effect of sorbent surface functionalities and microporosity on2,2 ′,4,4 ′-tetrabromodiphenyl ether (BDE-47) sorption onto biochars. A series of biochars prepared underdifferent conditionswere used to test their sorption behaviorswith BDE-47. The extents of sorption behaviorswere parameterized in terms of the single-point adsorption equilibrium constant (Koc ) at three equilibrium concentration (C e ) levels (0.001Sw (solubility), 0.005Sw , and 0.05Sw )whichwasdetermined using the Freundlich model. To elucidate the concentration-dependentdominant mechanisms for BDE-47 sorption onto biochars, K ocwas correlatedwith four major parameters using multiple parameter linear analysis accompaniedwith significance testing. The results indicated that at low concentration (Ce = 0.001Sw ), the surface microporosity term,which represented a pore-filling mechanism, contributed significantly to this relationship,while as concentrationwas increased to higher levels, surface functionality related to surface adsorption began to take thedominant role,whichwas further confirmed by the results of Polanyi-based modeling. Given the above results, adual mode model based on Dubinin-Radushkevich andde Boer-Zwikker equationswas adopted to quantitatively assess the changes of significance of surface adsorption aswell as that of pore fillingwith sorption processdevelopment. In addition, UV spectra of four typical aromatic compoundswhich represented the key structural fragments of biochars before and after interactionswith BDE-47were analyzed todetermine the active functional groups and supply complementary evidence for thedominant interaction force for surface adsorption, based onwhich π-π electron-donor-acceptor interactionwas proposed to contribute greatly to surface adsorption.     

水动力条件对太湖底泥吸附苯胺性能的影响

应用平衡研究法研究不同水动力条件下苯胺在太湖底泥中的吸附特性及其吸附动力学特征。结果表明,太湖底泥对苯胺具有较强的吸附能力,苯胺在太湖底泥上的最大吸附量为1.131 mg/g,其吸附行为可以用Freundlich型吸附等温式描述。采用Lagrange伪一级动力学和伪二级动力学模型对不同水动力条件下的苯胺吸附动力学数据进行了拟合,结果表明,沉积物对苯胺的吸附动力学更符合Lagrange伪二级动力学模型,且吸附速率随着初始浓度的增大而显著增大。此外,自吸附开始至1 h左右,吸附速率与水动力条件呈明显的正相关性。说明水动力条件的增大,增加了苯胺与沉积物的接触面积,使其扩散系数相对增大,更有利于沉积物对苯胺的表面吸附。自1 h过后,随着时间的延长,吸附速率基本不受水动力条件的影响。     

不同结构有机磷在(氢)氧化铝表面的吸附与解吸特征

研究了4种不同分子结构的有机磷[甘油磷酸(GP)、葡萄糖六磷酸(G6P)、三磷酸腺苷(ATP)和肌-肌醇六磷酸(植酸,IHP)]在无定形Al(OH)3、勃姆石和α-Al2O3等3种(氢)氧化铝表面的吸附解吸特征,并探讨了相关机制.结果表明,单位质量(氢)氧化铝对有机磷最大吸附量顺序为:无定形Al(OH)3>勃姆石>α-Al2O3,这与矿物的结晶度和表面异质性有关.除IHP在无定形Al(OH)3上的吸附外,有机磷在(氢)氧化铝表面的吸附密度随相对分子质量增大而减小:GP>G6P>ATP>IHP.而无定形Al(OH)3对最大分子尺寸的IHP吸附量却远大于其他有机磷,这是由于IHP表面络合物转化成了表面沉淀,大大促进了吸附.吸附动力学表明,有机磷吸附起始经历快速吸附阶段,极短时间内达到一定的吸附量,随后是一个较长时间的慢吸附过程,无定形Al(OH)3对有机磷的起始快速吸附密度最大,不同有机磷在铝氧化物表面的起始快速吸附密度与相对分子质量呈反比.KCl和柠檬酸对有机磷的解吸能力取决于磷化合物和勃姆石的表面亲和力.KCl初始解吸率大小顺序是:G6P(10.53%)>GP(6.91%)>ATP(3.06%)>IHP(0.8%).柠檬酸对有机磷的最大解吸率是KCl的4~5倍.KCl对磷的解吸过程经历了几个小时的快速解吸后达到最大解吸率,随后是慢速的扩散再吸附,解吸率反而逐渐下降.对IHP,除扩散再吸附外,表面沉淀也促进了再吸附.因此,有机磷与(氢)氧化铝界面发生较强的专性吸附反应,其分子结构和尺寸以及矿物的结晶度和晶体结构等是影响有机磷的界面反应和环境行为的重要因素.     

沙土不同有机矿质复合体对磷的吸附特征影响

采用平衡吸附法研究了沙土不同有机矿质复合体对磷的吸附特征影响.结果表明,去除腐殖质后的沙土对磷的吸附能力大大降低,其饱和吸附量Qm和吸附分配系数K分别只能达到原样的38.41％和7.42％,说明有机矿质复合体是影响磷在沙土上吸附特征的主要因素;钙键有机矿质复合体的碳标化饱和吸附量为388.35 mg·kg-1,相当于原样的1.51倍,在其所形成的有机矿质复合体中存在着孔隙填充方式的磷吸附;铁铝键有机矿质复合体在对磷吸附中发挥着重要作用,其碳标化饱和吸附量可达500.23 mg·kg-1,相当于原样的1.93倍,其吸附机制除孔隙填充方式外,还存在铁铝氧化物及水化氧化物对磷的配位吸附.因此,考查土壤对磷的吸附能力时不仅要考虑腐殖质的含量,更要考虑腐殖质的复合形态,它也是影响土壤对磷吸附特征的重要因素.以原样的磷饱和吸附量为基准,钙键有机矿质复合体和铁铝键有机矿质复合体携载的吸附态磷可分别按原样的1.51和1.93倍进行估算.