土壤中金属阳离子对Cl-离子吸附的诱导效应

使用三种可变电荷土壤和一种恒电荷土壤 ,研究电解质溶液中金属阳离子对Cl-离子吸附的影响 .结果表明 ,在可变电荷土壤中 ,金属阳离子对Cl- 离子的吸附有明显的诱导效应 ,影响大小次序为 :AlCl3>CuCl2 >KCl>NaCl.而在恒电荷土壤中影响不大     

Sorption of tetracycline to sediments and soils: assessing the roles of pH,the presence of cadmium and properties of sediments and soils

Batch sorption experiments were conducted to evaluate the sorption behavior of tetracycline (TC, H₃L) on sediments and soils in the presence and absence of cadmium (Cd), as affected by pH and properties of sediments and soils. The results indicated stronger nonlinearity and higher capacity of TC sorption on sediments than on soils. Sorption of TC also strongly depended on environmental factors and sediment/soil properties. Lower pH facilitated TC sorption through a cation exchange mechanism, which also took place at pH values above 5.5, where TC existed as a zwitterion (H₂L⁰) or anions (HL^- and L^2-). When pH was above 7, however, ligand-promoted dissolution of TC might occur due to TC weakening the Al-O bond of aluminum oxide and the Fe-O bond of iron oxide. Natural organic matter (NOM) plays a more important role in TC sorption than cation exchange capacity (CEC) and clay contents. The presence of Cd (II) increased TC sorption on both sediments and soils, which resulted from the decrease of equilibrium solution pH caused by Cd²⁺ exchange with H⁺ ions of sediment/soil surfaces. The increase of TC sorption was also related to the formation of TC-Cd complexes, where Cd²⁺ acted as a bridge between the sediment/soil and TC.     

The environmental fate of thymol,a novel botanical pesticide,in tropical agricultural soil and water

In this study, the environmental fate of thymol, including hydrolysis, aqueous photolysis, soil sorption and soil degradation, was studied under conditions that simulated the tropical agricultural environment. This study was undertaken to supply basic information for evaluating the environmental risks of applying this new botanical pesticide to tropical crop production. The results showed that the hydrolysis of thymol was pH-dependent and accelerated by acidic conditions and high temperatures. However, the hydrolysis rate was far lower than the aqueous photolysis rate, indicating that direct photolysis is an important dissipation pathway for thymol in water. The sorption of thymol by three tropical soils was consistently well described by the Freundlich model, and the sorption coefficients increased in the order sandy soil < loamy soil < clay soil, a characterization that depended on the organic carbon contents of the soil. The soil degradation rate of thymol decreased in the order sandy soil > loamy soil > clay soil, which has a negative correlation with the sorption of thymol in soils. We concluded that the degradation rates of thymol in tropical soil and water are fast: thymol in water is photodegraded (50%) by sunlight within 28 h, and the thymol in soils is degraded (50%) within 8.4 d. Therefore, the environmental risk to the surrounding soils and water of thymol application for tropical crop production is low.     

砷酸根在可变电荷土壤颗粒表面的配位吸附

研究了砷在3种可变电荷土壤颗粒表面的吸附对土壤胶体Zeta电位的影响及砷酸根吸附过程中羟基的释放特征.在酸性条件下,土壤胶体吸附砷酸根后土壤表面的负电荷增加,Zeta电位下降.这说明砷酸根在土壤颗粒表面发生了专性吸附,吸附的砷酸根离子进入土壤胶体双电层的紧密层中.亚砷酸根吸附对土壤胶体Zeta电位的影响很小,说明它在土壤颗粒表面主要通过形成外圈型表面络合物而发生非专性吸附.砷酸根在土壤颗粒表面的吸附过程中有羟基释放,说明砷酸根与表面羟基发生了配位交换反应.羟基释放量随砷酸根加入量的增加和pH值的升高而增加.动力学实验结果表明,砷酸根吸附量和羟基释放量随时间具有相似的变化趋势,在开始的20min内,二者均随时间迅速增加,随后变化较小.羟基释放量与砷酸根吸附量的摩尔比也随时间的增加而增加,说明羟基释放反应滞后于砷酸根吸附反应.土壤体系中羟基释放量与砷酸根吸附量的摩尔比小于针铁矿体系,说明除铁铝氧化物外,土壤的其它固相组分也参与了对砷的吸附反应.     

可变电荷土壤和恒电荷土壤CI~-吸附特性的研究

对不同浓度ＫＣＬ和不同ｐＨ下,３种可变电荷土壤和４种恒电荷土壤ＣＩ－吸附量进行了测定。结果表明,土壤ＣＩ－吸附量随平衡 ＣＩ－浓度 Ｃ（ｅ）增加而增大,恒电荷土壤呈线性,可变电荷土壤在添加 ＣＩ－ ０．５－５．０ ｍｍｏｌ／Ｌ．下,符合 Ｌａｎｇｍｕｉｒ吸附等温式。同一浓度下的ＣＩ－吸附量及其随浓度增加的速率均为砖红壤＞红壤＞赤红壤＞黄棕壤＞棕壤、暗棕壤和黑土,与这些土壤所带正电荷量顺序相一致。Ｌａｎｇｍｕｉｒ方程Ｋ值较小且几种土壤差异不大。恒电荷土壤对ＣＩ－的吸附量很小,在浓度较低时常出现负吸附,其吸附机理可能更多的是与Ｋ＋吸附时的同时吸附。７种土壤ＣＩ－吸附量均随ｐＨ增加而降低,但降低强度可变电荷土壤远大于恒电荷土壤。     

可变电荷土壤和恒电荷土壤Cl-吸附特性的研究

对不同浓度KCl和不同pH下,3种可变电荷土壤和4种恒电荷土壤Cl-吸附量进行了测定。结果表明,土壤Cl-吸附量随平衡Cl-浓度C（e）增加而增大,恒电荷土壤呈线性,可变电荷土壤在添加Cl-0.5~5.0mmol/L下,符合Langmuir吸附等温式。同一浓度下的Cl-吸附量及其随浓度增加的速率均为砖红壤>红壤>赤红壤>黄棕壤>棕壤、暗棕壤和黑土,与这些土壤所带正电荷量顺序相一致。Langmuir方程K值较小且几种土壤差异不大。恒电荷土壤对Cl-的吸附量很小,在浓度较低时常出现负吸附,其吸附机理可能更多的是与K+吸附时的同时吸附。7种土壤Cl-吸附量均随pH增加而降低,但降低强度可变电荷土壤远大于恒电荷土壤。     

低分子量有机酸对可变电荷土壤吸附铝的影响机制

通过吸附性铝的解吸实验研究了低分子量有机酸对三种可变电荷土壤(2种砖红壤和1种赤红壤)吸附铝的影响机制，结果表明，柠檬酸、苹果酸和酒石酸等带有3个及3个以上活性官能团的有机酸在低pH条件下可以通过形成土壤一有机酸一铝三元表面络合物和增加土壤的表面负电荷两种机制显著增加土壤对铝离子的吸附量，但以前一种影响机制为主。乳酸、水杨酸、草酸和丙二酸等带有2个活性官能团的有机酸仅通过改变土壤的表面负电荷影响铝的吸附。土壤氧化铁是土壤吸附有机酸的主要载体，当用化学方法将土壤中的氧化铁除去后，有机酸对铝吸附的影响变小。在pH5．0时有机酸主要通过形成可溶性有机铝络合物减小土壤对铝的吸附，但有机酸的存在增加了Al^3 在吸附性铝中所占的比例，导致铝的解吸率增加。土壤中大量氧化铁的存在使其即使在低pH下也能对铝离子发生专性吸附，导致吸附性铝的解吸率减小。     

浙江红壤和黄壤的电荷特性

本文对浙江省红壤和黄壤的电荷特性作了初步研究。结果表明，黄壤的可变负电荷量、正电荷量、有效阳离子交换量（ＥＣＥＣ）和可变电荷零点（ＰＨ０）都高于红壤。红壤和黄壤可变负电荷量占负电荷总量的半数以上。土壤的电荷特性与活性铁铝氧化物密切相关。     

CrO42-对两种可变电荷土壤吸附钾的影响

用一次平衡法研究了CrO4^2-对两种可变电荷土壤吸附钾的影响，用火焰光度法测定平衡溶液中的钾，根据差减法计算土壤对钾的吸附量。结果表明，加入铬酸根能增加土壤对钾的吸附量。铬酸根对钾吸附的影响程度与土壤游离氧化铁含量和土壤对铬酸根的吸附量的大小有关。砖红壤游离氧化铁含量高于红壤，它对铬酸根的吸附量也大于红壤，因此，铬酸根对砖红壤吸附钾的影响程度大于红壤。CrO4^2-主要通过自身的吸附增加土壤的表面净负电荷，并从而增加土壤对钾的吸附量。     

Effect of low molecular weight organic acids on adsorption and desorption of fluoride on variable charge soils

The effect of four low molecular weight organic acids on F⁻ adsorption by two variable charge soils was investigated using a batch method. The organic acids reduced F⁻ adsorption through competition by the acids with F⁻ for sorption sites. Oxalic and malonic acids, both of which have simpler chemical structures, were more effective than citric or malic acid. The effect of organic acids on F⁻ adsorption was more prominent at higher pH values and with larger amounts of the organic acids. The desorption study showed that the organic acids enhanced the desorption of F⁻ adsorbed by the soils. In the control and malic acid systems, desorption increased sharply with decreasing pH, while in the oxalic acid system, desorption rose slightly with decreasing pH. Desorption also increased with increasing amount of organic acid added. There are two possible mechanisms for the effect of the organic acids on F⁻ adsorption and desorption: (1)␣competition of the organic acids with F⁻ for adsorption sites and (2) dissolution of the adsorbents, especially dissolution of soil Al.     

Sorption of aromatic organophosphate flame retardants on thermally and hydrothermally produced biochars

• TPhP showed faster and higher sorption on biochars than TPPO. • Pyrochars had higher sorption capacity for TPPO than hydrochar. • Hydrophobic interactions dominated TPhP sorption by biochars. • The π-π EDA and electrostatic interactions are involved in sorption. Aromatic organophosphate flame retardant (OPFR) pollutants and biochars are commonly present and continually released into soils due to their increasingly wide applications. In this study, for the first time, the sorption of OPFRs on biochars was investigated. Although triphenyl phosphate (TPhP) and triphenylphosphine oxide (TPPO) have similar molecular structures and sizes, TPhP exhibited much faster and higher sorption than TPPO due to its stronger hydrophobicity, suggesting the dominant role of hydrophobic interactions in TPhP sorption. The π-π electron donor–acceptor (EDA) interactions also contributed to the sorption process, as suggested by the negative correlation between the sorption capacity of the aromatic OPFRs and the aromatic index (H/C atomic ratios) of biochar. Density functional theory calculations further showed that one benzene ring of aromatic OPFRs has no electrons, which may interact with biochar via π-π EDA interactions. The electrostatic attraction between the protonated P = O in OPFRs and the negatively charged biochar was found to occur at pH below 7. This work provides insights into the sorption behaviors and mechanisms of aromatic OPFRs by biochars.     

有机质和游离铁对湘南红壤表面电荷性质的影响

用双氧水破坏土壤有机质和用DCB（连二亚硫酸钠／柠檬酸钠／重碳酸钠）脱铁等方法研究湘南第四纪红粘土及其发育的土壤的表面电荷性质．结果表明：去除土壤有机质．使红壤胶体表面的阴离子交换量（AEC）增加、可变负电荷量（CECV）降低，在多数情况下其永久负电荷量（CECP）增加；脱游离氧化铁使红壤AEC减少、CECp增加，CECV增减不一．笔者认为，这与土壤胶体组分之间的相互作用有关．     

我国土壤系统分类中富铁铝土壤的分类

回顾了我国富铁土和铁铝土分类的历史。我国近代土壤分类开始于30年代;从50年代开始,我国土壤分类深受前苏联地理发生分类的影响。在地理发生分类体系中,按生物气候气候条件,热带、亚热带地带性土壤分别为燥红土、红壤、黄壤、赤红壤和砖红壤。从80年代开始,我国土壤科技工作者结合我国实际,引入了土壤系统分类。这一分类的特点是根据土壤诊断层和诊断特性划分土壤类型。据此,这一区域的地带性土壤主要是富铁土和铁铝土。     

中南地区几种土壤的表面电荷特性 Ⅱ.几种测定永久负电荷量的方法的比较

用有效阳离子交换量法、盐滴定-电位滴定法（STPT）、Mehlich法和pfo原理法测定了中南地区几种土壤的永久负电荷量．并与醋酸铵法测定的CEC进行了比较．结果表明：（1）由于醋酸铵法浸提了土壤的部分可变负电荷．它测出的CEC值使其它方法测得的永久负电荷量高．（2）不同方法测得的土壤永久负电荷量差异较大，且用上述四种方法测得的值依次减小．即ECEC＞δP＞CECp＞CECk，这与测定方法和指示离子的本性有关．但都能反映土壤永久负电荷容量的相对大小．（3）不同方法测得的不同的永久负电荷量值．在一定程度上反映着土壤的吸附特性，但有效阳离子交换量法能较好地反映土壤永久负电行量．     

改性土壤对模拟含硝基苯废水的吸附

研究了季铵盐阳离子表面活性剂四甲基铵离子（TMA）和十六烷基三甲基铵离子（HDTMA）改性的土壤（黑土、黄棕壤、红壤）对水中硝基苯的吸附作用。结果表明：改性土壤和改性土壤均能吸附水中的硝基苯。但改性土壤对水中硝基苯的吸附能力明显高于未改性土壤。改必土壤吸附硝基苯能力的顺序为1CEC－HDTMA黑土＞1CEC－HDTMA黄棕壤＞0．7 CEC－HDTMA黄棕壤＞1 CEC－HDTMA红壤＞0．7 CEC－HDTMA红壤＞1 CEC－TMA黄棕壤＞1 CEC－TMA红壤。未改性土壤和HDTMA改性土壤对硝基苯的吸附通过分配来进行，吸附等温线可用Henry方程表示，其lgKSOM为2．27，lgKHDTMA为2．87。     

多环芳烃在全土及其碱提残余物上的吸附行为

以菲和芘为代表性化合物,采用8种有机质含量不同的天然全土样品及其碱提残余物进行吸附实验,并利用不同吸附模型进行数据拟合,藉以探讨有机质含量对土壤吸附行为的影响.结果表明,Freundlich吸附模型的非线性指数n都小于1,显示全土和碱提残余物在多环芳烃的吸附过程中表现出非线性特征.菲和芘的吸附行为随土壤有机质含量不同而变化,碱提残余物的吸附能力强于全土,两者吸附行为的差异主要归因于土壤有机质含量和性状的区别.     

Influence of physico-chemical properties of soil clay fractions on the retention of dissolved organic carbon

This study investigated the effects of surface functional groups, cation exchange capacity (CEC), surface charge, sesquioxides and specific surface area (SSA) of three soil clay fractions (SCFs) (kaolinite–illite, smectite and allophane) on the retention of dissolved organic carbon (DOC) in soils. Physico-chemical properties of the SCFs before and after removing native carbon and/or sesquioxides were characterised, and the DOC adsorption–desorption tests were conducted by a batch method. Native organic carbon (OC)/sesquioxide removal treatments led to a small change in the CEC values of kaolinite–illite, but significant changes in those of smectite and allophane. The net negative surface charge increased in all samples with an increase in pH indicating their variable charge characteristics. The removal of native OC resulted in a slight increase in the net positive charge on soil clay surfaces, while sesquioxide removal increased the negative charge. Changes in the functional groups on the SCF surfaces contributed to the changes in CEC and zeta potential values. There was a strong relationship (R ² = 0.93, p < 0.05) between the Langmuir maximum DOC adsorption capacity (Q _max) and SSA. The Q _max value also showed a moderately strong relationship (R ² = 0.55, p < 0.05) with zeta potential (at pH 7). Q _max was only poorly correlated with CEC and native OC content. Therefore, along with SSA, the surface charge and functional groups of SCFs played the key role in determining the adsorption affinity and hence retention of DOC in soils.     

土壤中镉的吸附解吸研究进展

首先概述了国内外关于土壤对镉的吸附解吸的基本研究方法与实验条件。用于吸附解吸实验的土样以通过20目筛为宜，而不同形式的支持电解质及其离子浓度的选择对实验结果有很大影响，应由实验的具体目的和要求确定合适的实验条件。位于土壤颗粒表面的各吸附点位与镉的结合能的能量高低不一，可将土壤对镉的吸附作用区分为专性吸附和非专性吸附。可用传统的或融入新参数的吸附等温线表达土壤对镉的吸附过程，土壤对镉的吸附性能可用综合因子来形容，如吸附势、吸持率、平均分配系数、Langmuir方程的常数k和Freundlich方程的系数k等表达方式，同时寻找这些综合因子与土壤基本理化性质之间的关系。文章最后讨论了影响吸附过程的主要环境因子，并就土壤pH和水分条件的影响机制进行了分析。     

Selective sorption of perfluorooctane sulfonate on molecularly imprinted polymer adsorbents

Perfluorooctane sulfonate (PFOS), as a potential persistent organic pollutant, has been widely detected in water environments, and has become a great concern in recent years. PFOS is very stable and difficult to decompose using conventional techniques. Sorption may be an attractive method to remove it from water. In this study, the molecularly imprinted polymer (MIP) adsorbents were prepared through the polymerization of 4-vinylpyridine under different preparation conditions in order to remove perfluorooctane sulfonate (PFOS) from water. The MIP adsorbents using perfluorooctanoic acid (PFOA) as the template had good imprinting effects and could selectively remove PFOS from aqueous solution. The sorption behaviors including sorption kinetics, isotherms, and effect of pH, salt, and competitive anions were investigated. Experimental results showed that the sorption of PFOS on the MIP adsorbents was very fast, pH-dependent, and highly selective. The achieved fast sorption equilibrium within 1 h was attributed to the surface sorption on the fine adsorbents. The sorption isotherms showed that the sorption selectivity of PFOS on the MIP adsorbents decreased at high PFOS concentrations, which may be due to the double-layer sorption and the formation of PFOS micelles on the sorbent surface. The sorption of PFOS on the MIP adsorbents was mainly dominated by the electrostatic interaction between the protonated vinylpyridine on the adsorbent surface and the anionic PFOS. The prepared MIP adsorbents can potentially be applied in water and wastewater treatment for selective removal of PFOS.     

对硝基苯酚在沉积物上的吸附特性1

研究了沉积物吸附对硝基苯酚的作用机理及影响因素.结果表明,对硝基苯酚在沉积物上的吸附由其中的有机质含量和结构决定,体系的pH值对对硝基苯酚的吸附有较大的影响,其主要原因是体系的pH值控制着沉积物中有机质的溶出量.在实验浓度范围内,分配作用在沉积物吸附对硝基苯酚中占主导地位.