土壤胡敏酸与铜离子络合反应及吸附过程热力学特征的研究

供试三中不同土壤溶解态胡敏酸（ＨＡ）与Ｃｕ＾２＋络合的稳定常数ｌｏｇＫ大小呈：黑垆土ＨＡ＞娄土ＨＡ＞黄绵土ＨＡ，ｌｏｇＫ的大小与ｐＨ、温度（Ｔ）及离了程度（１）有关；络合反应的热和学函数变化：标准自由能变ΔｒＧｍ＾θ＜０，标准焓变ΔｒＨｍ＾θ＜０，标准熵变ΔｒＳｍθ＜０，表明络合是自发的放热反应，体系有序性增大。ΔｒＨｍ＾θ负值大小于ｌｏｇＫ呈相同次序，称为ＨＡ络合Ｃｕ＾２＋过程中ＨＡ分子变形及络     

土壤对铜离子的专性吸附及其特征的研究

供试土壤专性吸附铜的等温线均符合Langmuir方程。红壤吸附量最低,砖红腹与黄泥土最大吸附量相近,但在铜浓度低时砖红壤吸铜量远低于黄泥土,而在高浓度则反之。土壤专性吸附铜是在溶液中Na⁺浓度比Cu²⁺高8.3—100倍条件下,Na⁺离子仍不足以与之竞争的那些专性吸附点所吸持的铜。按其解吸条件区分为松结合铜(可为N NH₄Cl解吸)和紧结合铜(仅能为0.1 N HCl解吸)两种。紧结合铜受平衡溶液铜浓度影响很小,所占据的吸附点对Cu²⁺有较强亲和力。松结合铜则随平衡铜溶液浓度增大而增加,符合Langmuir方程。对于砖红壤和黄泥土,在铜浓度低时紧结合铜>松结合铜;浓度高时则反之。红壤专性吸附铜始终以松结合铜为主。三种土壤比较,紧结合铜是砖红壤>黄泥土>红壤;松结合铜则是黄泥土>砖红壤>红壤。造成这些差别的原因可能与土壤性质、氧化物、有机质和粘土矿物组成等不同有关。用平衡法研究三种土壤专性吸附铜在不同浓度NH₄Cl和HCl溶液中的解吸表明,可进一步区分为三或四种不同的结合状况。红壤对铜吸附容量最小,且最易解吸。     

土壤吸附铜离子的研究进展

对土壤吸附Cu的研究进行了综述。主要讨论了吸附速率,吸附等温线,表面络合模式和影响吸附量的因子等方面的问题。目前对土壤吸附Cu的速率研究主要有两种方法:一是根据实验数据绘制吸附量随时间变化的曲线,根据所绘制的曲线斜率来研究吸附动力学过程;二是选择经验性的化学动力学方程对数据进行拟和,依据较高的相关系数和较低的标准误差选择最优方程,根据吸附速率系数来进行定量的研究。土壤对Cu吸附的定量描述,经验性的吸附等温式仍不失为一个十分有用的方法;考虑到土壤性质和环境因子对吸附的影响,模型中应该加入这些参数使其更能反映土壤对重金属的吸附过程,但这方面的研究相对较少。土壤表面电荷特征、低分子有机酸对土壤吸附Cu的影响和吸附过程中Cu形态的变化等方面研究也较少。     

可变电荷土壤吸附铜离子时氢离子的释放

可变电荷土壤吸附铜离子后 ,土壤的中和曲线上不出现pH突跃 ,而变成一条平缓变化的曲线。当土壤悬液的pH低于一定数值时 ,加入铜离子后不释放氢离子。该pH值与土壤中氧化铁的含量有关。氧化铁的含量越高 ,该pH值越高。对于大多数可变电荷土壤 ,此pH值为 4左右。对可变电荷土壤 ,pH值越接近 4,氢离子释放的快速过程越不明显。在pH 4左右 ,加入铜离子后 1 0分钟时 ,释放的氢离子量仅占 6 5分钟时释放量的 3 0 %左右。但当pH值高于 4 5时 ,在大多数情况下 ,加入铜离子后半分钟时释放的氢离子量即可占 6 5分钟时的 5 0 %以上。恒电荷土壤吸附铜离子时氢离子的释放速度比可变电荷土壤快得多。即使pH值低至 3 8,在加入铜离子后半分钟时氢离子的释放量即占 6 5分钟时的 5 6 %以上。可变电荷土壤吸附铜离子时的H/Cu比比恒电荷土壤大得多。当恒电荷土壤悬液中加入0 1mo1L- 1 NaNO3作支持电解质时 ,吸附铜离子时的H/Cu比增大。     

土壤离子吸附：3.离子吸附的动力学

介绍了土壤离子吸附研究的一次平衡法，混合置换技术和压跳法，论述了主要动力学方程的适用条件及其在离子吸附方面的应用。     

棕壤对铜的吸附特性研究

棕壤对铜的吸附特性以及土壤条件对吸附的影响进行了研究，结果表明，棕壤对铜的吸附随溶液中铜的平衡浓度增加而增加，但在高浓度时增幅渐缓，与处于相同地区的褐土相比棕壤的吸附相对较弱，其吸附可用Langmiur、Frundlich、Temkin及米氏方程进行描述。土壤酸度增强，棕壤对铜的吸附降低，用H^＋浓度对Frundlich方程进行修饰，能更好地描述铜的吸附状况。此外，离子强度、陪伴离子对吸附都有影响，随离子强度增加及高价陪伴离子比例的上升吸附减弱。     

离子强度和pH对可变电荷土壤与铜离子相互作用的影响

研究了离子强度和pH对可变电荷土壤表面电荷与铜离子吸附的影响。作为对照 ,也研究了它们对恒电荷土壤黄棕壤的有关性质的影响。结果表明 ,随pH升高 ,土壤的表面负电荷增加 ,正电荷减少。对于可变电荷土壤 ,可出现电荷零点 (pH0 )。随pH升高 ,土壤对Cu2 的吸附量增大。随着离子强度增大 ,恒电荷土壤对Cu2 的吸附百分率明显降低 ,可变电荷土壤对Cu2 离子的吸附百分率也降低 ,但降低的幅度比恒电荷土壤者小得多。土壤中氧化铁的含量越高 ,降低的幅度越小。对于含 2 1 %左右游离氧化铁的铁质砖红壤 ,即使支持电解质NaNO3的浓度高达 1molL- 1,对Cu2 的吸附仍然几乎没有影响。从离子强度和pH与土壤表面电荷和铜离子吸附的关系 ,可以推测在土壤对铜离子的吸附中 ,既存在电性吸附 ,又存在专性吸附。在可变电荷土壤对铜离子的吸附中 ,专性吸附较为重要     

土壤胡敏素各组分数量及结构特征初步研究

土壤胡敏素（HM）是与矿物质紧密结合的腐殖物质，具有碱不溶性及大分子结构的特性，并呈现不均一性，被认为是土壤中的惰性物质。由于HM的非溶解性和结构复杂性，目前国内外学者对于HM结构特征的研究还很少。对加入大量有机物料培养后新形成的HM数量及性质的研究尚未见报道。本研究选用风沙土、草甸土、黑土、黑土底土加玉米秸秆培养土为材料，根据Pallo分组法，将土壤HM分为铁结合胡敏素（HMi）、粘粒结合胡敏素（HMc）和不溶性胡敏素（HMr）三个组分；对自然土壤中HM各组分以及加入玉米秸秆后新形成的HM各组分的数量及结构特征进行初步研究，为丰富腐殖质化学提供基础性资料。实验结果表明：在自然土壤HM各组分中以HMr为主，其次是HMi，含量最少的是HMc。通过HMi和HMc的光学性质比较得出HMi的分子结构较简单，HMc分子结构相对较复杂，加玉米秸秆培养后新形成的HMi、HMc的分子结构比自然土壤中的简单。红外光谱结果表明，与自然土壤相比加玉米秸秆培养后新形成的HMi、HMc的脂族性最强，自然土壤中HMi、HMc的脂族性强弱顺序为：风沙土〉黑土〉草甸土。     

两种土壤中邻苯二胺对铜离子吸附—解吸平衡影响的研究

采用室内测试方法，研究了低浓度的外源铜离子在两种不同性质土壤中的吸附、解吸过程及其受邻苯二胺的影响。结果发现，外源铜离子在红壤中的吸附随pH的变化明显变化，而在黑土中的吸附则随pH变化改变较小，吸附在红壤中的铜较吸附在黑土中的铜更易于解吸，有机物邻苯二胺对铜在两种土壤中的吸附和解吸过程产生了明显影响。酸性条件下邻苯二胺的存在增加了红壤对铜的吸附量，但同时也增加了铜的解吸百分数。而邻苯二胺基本不改变铜在黑土中的表观吸附量，但显著影响铜的解吸百分数。     

土壤对养分离子吸附特性初步研究

针对土壤本身对养分离子具有吸附固定特性降低了养分的有效性,运用土壤养分状况系统研究法通过吸附试验研究新疆两种土壤对养分离子的吸附固定能力。研究结果表明:棕漠土对P、Zn、Cu的吸附固定能力比潮土强,两种土壤对K、B和Mn吸附固定差异不显著,棕漠土的养分限制因子是N>P>Mn>B,潮土的养分限制因子是N>Mn>P>K,因此施肥时考虑到土壤对养分离子的吸附固定能力确定合理的施肥量。     

暗棕壤吸附铜离子特征及其影响因素研究

应用平衡吸附法,研究了不同pH、离子强度、温度、Cu~(2 )浓度和接触时间条件下,暗棕壤对Cu~(2 )的吸附作用,并利用热力学和动力学方程对实验结果进行了拟合。结果表明:(1)随pH提高,Cu~(2 )的吸附率增加,pH 8时的吸附率约为91%。(2)随体系离子强度增加,Cu~(2 )的吸附量先下降后增加。(3)随溶液中Cu~(2 )浓度增加,Cu~(2 )在暗棕壤上的吸附量也增加,并且在低浓度时增加比较迅速。吸附等温线可用Frendlich,Langmiur和Temkin方程很好的描述,其中又以Langmiur方程拟合程度最好。根据Langmiur方程中平衡常数(k_L)得到的热力学参数指出,反应是自发的、吸热的,但增温却没有改变Cu~(2 )在暗棕壤表面的混乱度。(4)随接触时间延长,暗棕壤对Cu~(2 )的吸附量也增大,具体表现为吸附开始的快速反应阶段和经过一段时间后的慢速反应阶段。双常数能更好地拟合暗棕壤对Cu~(2 )的吸附动力学曲线,根据一级动力学方程的反应速率常数(k_D),计算出了Cu~(2 )吸附的活化能和活化热力学参数,指出温度升高有利于提高反应的速率。     

红壤有机矿物复合体吸附Cu(Ⅱ)的分子机制

采用元素分析、X射线衍射分析（XRD）、同步辐射扫描透射显微术（STXM）等手段,表征湖南祁阳红壤中颗粒态有机质(Particle organic matter, POM)和有机矿物复合体（Organo-mineral complexes, OMC）的元素组成、矿物组成,以及Cu(Ⅱ)在土体土壤（Bulk soil,BS）和OMC表面的吸附行为、元素微区分布和分子固定机制,以明确实际土壤系统有机矿物复合体对铜吸附的能力及其固定机制。元素分析、XRD结果表明,土体土壤主要由OMC组成,富含黏土矿物,且所含有机质矿化度较BS和POM组分高。等温吸附实验结果表明,BS和OMC等温吸附曲线符合Langmuir和Freundlich方程,BS及OMC对Cu(Ⅱ)吸附等温线类似,且理论最大吸附量相当,说明供试土壤对Cu(Ⅱ)的吸附主要由OMC决定。STXM在亚微米尺度上表征了BS和OMC吸附样品中Cu与C、 Fe、Al、Si的微区分布特征,发现Cu在红壤中分布具有空间异质性,Cu主要与羧基碳与铁氧化物形成的有机矿物复合体相结合,控制着红壤中Cu(Ⅱ)的形态分布与有效性。     

Surfactant-Enhanced Removal of Cu (II) and Zn (II) from a Contaminated Sandy Soil

Batch tests were conducted to know the effectiveness of using surfactants only and surfactants with a complexing agent to remove Cu (II) and Zn (II) from an artificially contaminated sandy soil. SDS (sodium dodecyl sulfate), AOT (alpha-olefin sulfonate) and Tx-100 (Triton X-100) were the surfactants selected as the washing liquids. Complexing agent EDTA (ethylenediaminetetraacetic acid) was also selected for washing the soil. To avoid external factors from interfering with the cleaning process, artificial soil formed by a mixture of clean sand and bentonite was used to form contaminated soil samples. The amount of organic matter present was insignificant. Compared to extraction by distilled water, tests indicated that a six-fold increase in copper extraction occurred due to the presence of surfactants and/or the complexing agent EDTA. Compared to extraction by distilled water, zinc extraction by surfactants and or the complexing agent EDTA was nearly 1.2 to 1.3 times more. Effects of competition as well as interference associated with the adsorption and desorption of these metals are also very briefly reported.     

Cu(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)在红壤胶体和非胶体颗粒上吸附的比较

研究了湖南长沙和海南昆仑的2种红壤胶体和非胶体的矿物组成、阳离子交换量(CEC)及Cu(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)在土壤胶体和非胶体颗粒表面的吸附行为,以明确红壤胶体对土壤表面化学性质的贡献。X射线衍射分析结果表明,两种红壤胶体的矿物组成均以次生矿物为主,次生矿物又以1∶1型高岭石所占比例最高。土壤非胶体颗粒中石英等原生矿物含量较高。土壤铁铝氧化物主要富集在土壤胶体部分,土壤胶体颗粒中游离氧化铁和游离氧化铝含量明显高于非胶体颗粒,如湖南长沙红壤胶体颗粒游离氧化铁的含量为78.03 g kg~(-1),而非胶体颗粒中仅为9.93 g kg~(-1)。土壤胶体颗粒的CEC显著高于非胶体颗粒部分,2种红壤胶体的CEC约为非胶体的12倍。等温吸附实验结果表明,土壤胶体颗粒对Cu(Ⅱ)、Pb(Ⅱ)与Cd(Ⅱ)的最大吸附量和吸附亲和力均显著大于非胶体颗粒,湖南红壤胶体对3种重金属的吸附量大于海南红壤胶体,与土壤胶体的矿物组成和CEC大小一致。Cd(Ⅱ)在红壤胶体和非胶体颗粒表面主要发生静电吸附,而静电吸附和非静电吸附两种机制均对Cu(Ⅱ)和Pb(Ⅱ)的吸附有重要贡献。     

Soil Adsorption of Urea II

Soils have generally been considered to adsorb little amounts of urea because it scarcely dissociates in water solution. A few works^1-3) have been reported on this problem. But it should be noticed that an electrostatic adsorption might not be the sole mechanism of soil adsorption of urea. In the previous paper⁴⁾ a correlation between equilibrium concentrations of urea in soil solutions and the amount of adsorbed urea was worked out, using Tanashi paddy soil of volcanic ash origin. An adsorption coefficient of Urea on the soil was calculated from the correlation and it was suggested that the soil possibly adsorbed considerable amounts of urea by a force which was weaker than the electrostatic force. together with experiments⁴⁾ using urea derivatives such as thiourea, methylurea or dimethylurea, it was concluded that the soil adsorption of Urea was possibly due to the formation of hydrogen bondings, principally arising from amino hydrogens and partly from carbonyl oxygen in a urea molecule.     

Preparation, Characterization, and Adsorption Behavior of Cu(II) Ions onto Alkali-Treated Weed (Imperata cylindrica) Leaf Powder

The adsorption of Cu(II) ions by sodium-hydroxide-treated Imperata cylindrica (SoHIC) leaf powder was investigated under batch mode. The influence of solution pH, adsorbent dosage, shaking rate, copper concentration, contact time, and temperature was studied. Copper adsorption was considered fast as the time to reach equilibrium was 40–90 min. Several kinetic models were applied and it was found that pseudo-second-order fitted well the adsorption data. In order to understand the mechanism of adsorption, spectroscopic analyses involving scanning electron microscope (SEM) coupled with energy-dispersive spectroscopy (EDS) and Fourier transform infrared (FTIR) spectrophotometer were carried out. Ion exchange was proven the main mechanism involved as indicated by EDS spectra and as there was a release of light metal ions (K⁺, Na⁺, Mg²⁺, and Ca²⁺) during copper adsorption. Complexation also occurred as demonstrated by FTIR spectra involving hydroxyl, carboxylate, phosphate, ether, and amino functional groups. The equilibrium data were correlated with Langmuir, Freundlich, and Dubinin–Radushkevich isotherm models. Based on Langmuir model, the maximum adsorption capacity was recorded at the highest temperature of 310 K, which was 11.64 mg g^?1.     

Preparation of Titanate Whiskers Starting from Metatitanic Acid and Their Adsorption Performances for Cu(II), Pb(II), and Cr(III) Ions

The accumulation of metals and nutrients in biosolid-amended soils and the risk of their excess uptake by plants is a topic of great concern. This study examines the elemental uptake and accumulation in five vegetable plants grown on biosolid-applied soils and the use of spectral reflectance to monitor the resulting plant stress. Soil, shoot, root, and fruit samples were collected and analyzed for several elemental concentrations. The chemical concentrations in soils and all the plant parts increased with increase in applied biosolid concentrations. The Cu and Zn concentrations in the plant shoots increased in the order of collard?<?radish?<?lettuce?<?tomato?<?pepper. The Cu and Zn concentrations accumulated significantly in the fruits of the tomato plants compared to other plants. Among all the plants, the shoot concentration factor (SCF) of Zn was significantly higher for pepper plants, indicating increase in uptake of Zn. The shoot relative uptake index (SRUI) of Cu and Zn increased in the order of collard?<?radish?<?lettuce?<?tomato?<?pepper. The shoot dry weight and spectral reflectance of the radish plants in the near-infrared (NIR) region (800–1,300 nm) decreased significantly with increase in biosolid concentration compared to other plants. Increase in plant stress with increase in biosolid dose was evident in radish plants through significant reduction in Normalized Difference Vegetative Index (NDVI). This study indicates the potential use of spectral reflectance as a tool for the screening and monitoring of stress-sensitive plant species and their physiology and as a result, indirectly assesses the chemical concentrations in soils and plants.     

Adsorption features of Cu(II), Pb(II), and Zn(II) by an ordinary chernozem from nitrate,chloride, acetate,and sulfate solutions

The effect of Cl^?,SO ₄ ^2? , CH₃COO^?, and NO ₃ ^? anions on the adsorption of copper, lead, and zinc by an ordinary chernozem has been studied. The effect of the anions on the adsorption of Cu²⁺, Pb²⁺, Zn²⁺ ions is significant but uncertain. It has been shown that the attendant anions affect the shape of the adsorption isotherms, which are described by the Langmuir, Freundlich, or Henri equations. The constants of the adsorption from a nitrate solution calculated from the Langmuir equation (K _L) decrease in the following order: Cu²⁺ > Pb²⁺ >> Zn²⁺. The values of the maximum adsorption (C _max) decrease in the following order: Cu²⁺ ≥ Zn²⁺ > Pb²⁺ for acetate solutions and in the series Pb²⁺ > Zn²⁺ ≥ Cu²⁺ for nitrate solutions. The values of the Henry constants (K _H) calculated for the adsorption of the same cations from chloride solutions decrease in the same order as the values of K _L. The CH₃COO^? anion has the highest effect on the constant values. The NO ₃ ^? and Cl^? anions “switch their places” depending on the attendant cation, but their effect is always lower than that of the acetate anion. The values of C _max for copper and zinc are most affected by the CH₃COO^? anion, and the adsorption of zinc is most affected by the Cl^? and NO ₃ ^? anions. The assessment of the mobility of the adsorbed cations from the extraction with ammonium acetate (pH 4.8) has shown that the content of the desorbed metals is always lower than the content of the adsorbed cations and varies from 0.025 to 83%. According to their mobility, the adsorbed metals form the following order: Zn²⁺ > Pb²⁺ > Cu²⁺. The effect of the attendant anions on the extractability of the adsorbed cations decreases in the following order: chlorides > sulfates > acetates > nitrates.     

Competition from Cu(II), Zn(II) and Cd(II) in Pb(II) Binding to Suwannee River Fulvic Acid

This is a study of trace metal competition in the complexation of Pb(II) by well-characterized humic substances, namely Suwannee River Fulvic Acid (SRFA) in model solutions. It was found that Cu(II) seems to compete with Pb(II) for strong binding sites of SRFA when present at the same concentration as Pb(II). However, Cd(II) and Zn(II) did not seem to compete with Pb(II) for strong binding sites of SRFA. These two metals did compete with Pb(II) for the weaker binding sites of SRFA. Heterogeneity of SRFA was found to play a crucial role in metal–SRFA interactions. The environmental significance of this research for freshwater is that even at relatively low Pb(II) loadings, the metals associated with lead in minerals, e.g. Cu(II), may successfully compete with Pb(II) for the same binding sites of the naturally occurring organic complexants, with the result that some of the Pb(II) may exist as free Pb²⁺ ions, which has been reported to be one of the toxic forms of Pb in aquatic environment.