发育程度对海南玄武岩发育土壤吸附铬酸根和磷酸根的影响

选择海南岛北部3个不同年代喷发的玄武岩发育的土壤研究了其对铬酸根(CrO42-)和磷酸根(PO43-)的吸附特征,结果表明随着母岩年龄的增加,土壤发育程度提高,土壤游离氧化铁和表面正电荷数量增加,对2种阴离子的吸附量增加。土壤CrO42-的解吸率在19.8%~39.6%之间,表明土壤对CrO42-的吸附涉及静电吸附和专性吸附2种机制,且随着土壤发育程度增加,CrO42-静电吸附所占比例增加。土壤对PO43-的吸附以非静电吸附为主,吸附的PO43-的解吸量非常低,其解吸率不超过6%。吸附PO43-在去离子水中的解吸量高于在0.1 mol/L NaNO3和KNO3中的解析量,KNO3体系中的解吸量低于NaNO3体系中的,电解质主要通过改变胶体表面离子吸附面上的静电电位影响PO43-的解吸。     

不同浓度铜离子土壤的吸附-解吸行为——兼论弱专性吸附态的存在

研究了三种可变电荷土壤和两种恒电荷土壤不同铜离子浓度条件下的吸附-解吸行为。结果表明,不同铜离子浓度下土壤的pH-Cu2+吸附率曲线均在低pH段出现会合,且随着铜离子浓度升高,pH-Cu2+吸附率曲线有向右偏移的趋势。证实了可变电荷土壤中吸附性铜离子可被去离子水解吸,并存在解吸峰现象。针对解吸前后吸附体系pH值的变化研究结果显示,吸附时体系pH低于5.0时,解吸后pH上升;而吸附体系pH高于5.0时,解吸后pH下降,表明pH5.0可能是土壤吸附铜离子机理发生变化的又一个转折点。本文还对专性吸附中弱吸附态的存在和形成原因进行了初步探讨。     

可变电荷土壤中特殊化学现象及其微观机制的研究进展

综述了近年来可变电荷土壤化学研究的进展,着重总结了可变电荷土壤中的盐吸附、铁铝氧化物对土壤自然酸化的抑制作用和离子强度对离子专性吸附的影响等特殊化学现象及其微观机制的研究进展。用颗粒表面扩散层重叠导致有效电荷数量减小的原理解释了盐吸附现象和铁铝氧化物对土壤自然酸化的抑制作用。阐明了可变电荷土壤和矿物中介质离子强度影响离子专性吸附的机制,用四层吸附模型解释了离子专性吸附随离子强度增大而增加的现象,并根据胶体zeta电位随离子强度改变而变化的趋势进一步证明了离子强度增大使胶体专性吸附面上静电电位的绝对值减小,是离子专性吸附随离子强度增大而增加的主要原因。带电颗粒表面双电层结构和双电层相互作用的深入研究,有助于阐明可变电荷土壤中一些特殊化学现象的微观机理,从而进一步完善土壤化学理论。     

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。     

支持电解质浓度对磷酸根在可变电荷土壤表面吸附和解吸的影响

研究了离子强度对2种可变电荷土壤中磷酸根吸附和解吸的影响。结果表明,当pH分别大于3.7和4.0时,红壤和砖红壤对磷酸根的吸附量随离子强度的增加而增加;当pH分别小于3.7和4.0时,红壤和砖红壤对磷酸根的吸附量随离子强度呈相反的变化趋势。电解质主要通过改变离子专性吸附面上的电位来影响磷酸根的吸附。Zeta电位的测定结果表明,当pH大于土壤胶体的等电点(IEP)时,吸附面上电位为负值,且随离子强度增加数值减小,对磷酸根的排斥力减小,土壤表面对磷酸根的吸附量增加;当pH小于IEP时,吸附面上的电位为正值,它随离子强度增加而减小,不利于磷酸根的吸附。解吸实验的结果表明,吸附于可变电荷土壤表面的磷酸根在去离子水中的解吸量高于0.1 mol L-1NaNO3体系中的解吸量。这同样由于电解质浓度对土壤表面吸附面上的电位的影响所致。     

连续解吸中离子强度对可变电荷表面吸附性铜离子解吸的影响 ：高岭石

为了解连续性解吸对可变电荷表面吸附性铜离子解吸的影响,研究了高岭石在去离子水和0.1 mol L~(-1) NaNO_3溶液中吸附铜离子后,依次在去离子水以及浓度由低到高的NaNO_3溶液中连续解吸时,离子强度变化对不同pH段铜离子解吸的影响。结果表明:在去离子水中和不同浓度NaNO_3中解吸吸附性铜离子时,pH-解吸分值曲线的变化趋势完全不同。在去离子水中解吸时可出现重吸附现象,而在NaNO_3中解吸时出现解吸峰现象。高岭石pH-铜离子解吸分值曲线的拐点pH与pH吸附有着对应关系,且pH特征与高岭石pH0关系密切。离子强度变化导致的吸附表面电位变化、高岭石边面的诱导水解作用和土壤表面电荷性质随pH升高的变化被认为是导致这些现象的原因。     

离子强度对可变电荷表面吸附性铜离子解吸的影响:高岭石

为了解连续性解吸对可变电荷表面吸附性铜离子解吸的影响,研究了高岭石在去离子水和0.1 mol L~(-1) NaNO_3溶液中吸附铜离子后,依次在去离子水以及浓度由低到高的NaNO_3溶液中连续解吸时,离子强度变化对不同pH段铜离子解吸的影响。结果表明:在去离子水中和不同浓度NaNO_3中解吸吸附性铜离子时,pH-解吸分值曲线的变化趋势完全不同。在去离子水中解吸时可出现重吸附现象,而在NaNO_3中解吸时出现解吸峰现象。高岭石pH-铜离子解吸分值曲线的拐点pH与pH吸附有着对应关系,且pH特征与高岭石pH0关系密切。离子强度变化导致的吸附表面电位变化、高岭石边面的诱导水解作用和土壤表面电荷性质随pH升高的变化被认为是导致这些现象的原因。     

土壤离子吸附：I.离子吸附的类型及研究方法

阐述了土壤离子专性吸附和非专性吸附的特点，介绍了离子吸附的热力学，仪器学和等瘟线研究方法以及常见等温线的模型及其应用。     

连续解吸中离子强度对可变电荷土壤和高岭石体系pH的影响

研究了两种可变电荷土壤中在去离子水中和0.1 mol L-1 Na NO3溶液中吸附铜离子和钙离子后依次被浓度从低到高的Na NO3溶液连续解吸时,离子强度变化对每次解吸前后体系p H变化(Δp H)的影响,为了进一步了解其相关机理,作为对照,也研究了各种条件下,离子强度变化对高岭石Δp H的影响。结果表明,无论是否有吸附性二价阳离子的存在,或者吸附性阳离子属性(专性吸附型离子或电性吸附型离子)如何,当样品依次被去离子水、0.01 mol L-1 Na NO3、0.1 mol L-1 Na NO3以及1 mol L-1 Na NO3解吸时,在去离子水中和Na NO3溶液中的解吸过程对Δp H的影响截然不同。总体而言,如果解吸时体系离子强度趋于降低,Δp H将为正值,反之则为负值,且Δp H变幅开始增大时的起始点所对应的p H吸附基本相同,该起始点应该与高岭石ZPC(电荷零点)紧密相关。对上述结果的分析表明,解吸过程中,引起上述Δp H变化规律的根本原因之一是连续解吸过程中的离子强度变化导致的可变电荷表面的表面电位变化。     

离子强度对可变电荷表面吸附性铜离子解吸的影响:可变电荷土壤

为进一步了解离子强度对可变电荷表面吸附性铜离子连续性解吸的影响,研究两种可变电荷土壤在去离子水和0.1 mol·L~(-1)NaNO_3溶液中吸附铜离子后,依次在去离子水和浓度由低到高的NaNO_3溶液中连续解吸时,离子强度变化对不同pH段铜离子解吸的影响。结果表明,解吸过程中离子强度变化方向对解吸分值随pH升高的变化趋势的影响完全不同,当离子强度由大变小时,解吸分值曲线的总体趋势是随着pH的升高而降低,反之,曲线呈现为钟形,且当去离子水第一次解吸在0.1mol·L~(-1)NaNO_3溶液中吸附的铜离子时,两种可变电荷土壤的第一次去离子水解吸均可出现重吸附现象,但铁质砖红壤解吸分值绝对值要小于红壤。整个解吸过程中,两种可变电荷土壤的铜离子吸附性铜离子的解吸特征与高岭石基本相似,但可变电荷土壤与高岭石以及两种可变电荷土壤之间,解吸分值的变化规律均存在一定的差异性,可变电荷土壤中的氧化铁含量多少被认为是导致这些差异的主要原因。     

Effects of Oxalate and Humic Acid on Arsenate Sorption by and Desorption from a Chinese Red Soil

Studies on arsenate (As(V)) sorption and desorption have been mainly limited to soil minerals and sorption and desorption reactions in whole soils are poorly understood. In this study the sorption of As(V) by and phosphate-induced desorption from a Chinese red soil were studied in the presence of oxalate and humic acid (HA). Arsenate was strongly sorbed mainly through ligand exchange reactions on the soil. Arsenate sorption decreased in the presence of oxalate or HA. Oxalate and HA influenced As(V) sorption mainly by competing for sorption sites and reducing sorption sites, and oxalate could also decrease sorption through dissolving clay minerals. Oxalate and HA could also facilitate As(V) desorption from the soil. Both sorption and desorption kinetics were two stage processes. Sorption kinetics conducted from 0.2–840 h showed that As(V) sorption increased with increasing residence time. Sorption equilibrium was retarded and the maximum sorption decreased in the presence of oxalate or HA. Phosphate-induced desorption kinetics conducted on the soil with 24 h and 840 h of sorption equilibrium time showed a significant effect of equilibrium time on As(V) desorption. The presence of oxalate or HA during the sorption process resulted in more As(V) desorption. Due to the degradation of oxalate, soil treated with oxalate and with a sorption equilibrium time of 840 h showed no significant difference in desorption kinetics from untreated soil.     

Multi-Step Competitive Sorption and Desorption of Chlorophenols in Surfactant Modified Montmorillonite

Single- and bi-solute sorption and desorption of 2,4-dichlorophenol (2,4-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) in montmorillonite modified with hexadecyltrimethylammonium (HDTMA) were investigated using multi-step sorption and desorption procedure. Effect of pH on the multi-step sorption and desorption was investigated. As expected by the magnitude of octanol-water partition coefficient, K _ow , both sorption and desorption affinity of 2,4,5-TCP was higher than that of 2,4-DCP at pH 4.85 and 9.15. For both chlorophenols, the protonated speciation (at pH 4.85) exhibited a higher affinity in both sorption and desorption than the predominant deprotonated speciation (about 95% and 99% of 2,4-dichlorophenolate and 2,4,5-trichlophenolate anions at pH 9.15, respectively). Desorption of chlorinated phenols was strongly dependent on the current pH regardless of their speciation in the previous sorption stage. Freundlich model was used to analyze the single-solute sorption and desorption data. No appreciable desorption-resistant (or non-desorbing) fraction was observed in organoclays after several multi-step desorptions. This indicates that sorption of phenols in organoclay mainly occurs via partitioning into the core of the pseudo-organic medium, thereby causing desorption nearly reversible. In bisolute competitive systems, sorption (or desorption) affinity of both chlorophenols was reduced compared to that in its single-solute system due to the competition between the solutes. The ideal adsorbed solution theory (IAST) coupled to the single-solute Freundlich model successfully predicted bisolute multi-step competitive sorption and desorption equilibria.     

Groundwater Purification in a Polymetallic Mining Area (SW Sinai,Egypt) Using Functionalized Magnetic Chitosan Particles

A magnetic glycine-grafted chitosan sorbent (Gly) was functionalized to produce a hydrazide derivative (HGly). The two sorbents were tested in batch mode for the sorption of a series of 10 metal ions present in the groundwater collected in three wells in the Wadi (valley) Nasib mining area (SW Sinai, Egypt). HGly is much more efficient for metal recovery than Gly. Under selected experimental conditions (sorbent dosage 1.5 g L^?1), the sorption efficiency is not sufficient for achieving the standard levels for drinking water: the most problematic metal ions in terms of drinkability remain aluminum (too high metal concentration in the groundwater), cadmium, and chromium for the three wells (and nickel in the case of only one well). Increasing the sorbent dosage improves the treatment efficiency. The sorbent (HGly) was tested in fixed-bed columns. The breakthrough curves were compared for the different metals for the groundwater collected in the most contaminated of the three wells. The levels of metal concentration in the treated groundwater are too high for direct use in irrigation. However, they are consistent with the standards for livestock drinking water (based on FAO recommendations, Food and Agriculture Organization of the United Nations). The metals can be readily desorbed using 0.5 M HCl solutions with a relatively high concentrating effect (i.e., 50 times). The re-use of the sorbent for three successive cycles of sorption/desorption cycles shows a progressive but weak decrease in sorption and desorption performances.     

Kinetics of arsenite sorption and desorption in Spanish soils

Abstract

The arsenite (AsO₂ ^‐) sorption and desorption by three Spanish soils were investigated. An Elovich type equation and a modified Freundlich equation were used to describe the kinetics of arsenic [As (III)] sorption and desorption rates. In both cases, the Elovich equation proved to be superior when correlation coefficients were considered. Arsenic (III) sorption and desorption rate increases as the As concentration in the original solution increases. Arsenite sorption was reversible for the soils, initial concentrations, and reaction times used in this study.     

1,1,2,2-四氯乙烷在土壤中的吸附解吸研究及解吸滞后的新型模型模拟

采用室内实验方法,研究了1,1,2,2-四氯乙烷（1,1,2,2-tetrachloroethane,1,1,2,2-TeCA）在4种土壤上的吸附和解吸行为,并用一种新型解吸模型——＂双元平衡解吸（Dual-EquilibriumDesorption,DED）模型＂对其解吸行为进行了预测。结果表明,1,1,2,2-TeCA在4种土壤上的吸附符合传统的线性吸附模型,lgKoc的平均值为1.86;解吸行为则表现出明显的滞后现象,解吸后的lgKo（c平均值约为4.88）显著大于初始值,且与吸附相污染物的初始浓度、土壤性质无相关性。DED模型比传统线性模型能更好地拟合TeCA在土壤中的解吸滞后现象。     

对硝基氯苯在土壤和腐殖酸上的长期吸附与多步解吸的研究

采用批量平衡实验法研究了对硝基氯苯（p-NCB）在土壤和腐殖酸上的长期吸附和多步解吸,比较了连续的多步解吸与一步解吸的差异。结果表明,随着吸附时间的增加吸附量均会有所增加,随吸附时间增加吸附等温线的非线性增强。p-NCB在液相和固相上的初始浓度对吸附速率有一定影响,低浓度比高浓度时达到平衡的速率要低。对于两种受试土壤,两次解吸得到的等温线均无法与吸附等温线重合,表现出很强的吸附不可逆性。而尽管p-NCB在腐殖酸上表现出明显的非线性吸附（n = 0.794）,但4次解吸后所得到的平衡位点与吸附所得的平衡位点基本落在同一条直线上,对数坐标下进行线性拟合的相关系数（R2）可达0.988,说明吸附过程是完全可逆的。     

Effect of liming on hexazinone sorption and desorption behavior in various soils

Liming is a practice commonly used to modify soil acidity, neutralize aluminum, and increase calcium and magnesium in the soil. Liming can change herbicide retention processes and consequently weed control and potential environmental contamination. The effects of liming on the sorption and desorption of hexazinone in different soils were evaluated. Samples from seven Brazilian soils were collected and separated into two subsamples, with and without limestone incubation. Hexazinone was quantified using ultra high-performance liquid chromatography. The sorption and desorption coefficients were determined in soils using Freundlich isotherms. Increasing the pH did not alter the sorption kinetics of hexazinone in the same soil class. The shortest sorption time of hexazinone occurred in soils with higher organic matter (OM) and clay content. Liming reduced the sorption and increased the desorption of hexazinone in the soils, which was caused by the increase in pH and reduction of OM content. Although the application of limestone increased desorption, the rate at which this process occurred was less than the sorption rate of hexazinone in most cases. In alkaline soils, the recommended dose of hexazinone for pre-emergence application should be low to avoid leaching and reduce the contamination of groundwater resources.     

土壤中黑碳对农药敌草隆的吸附-解吸迟滞行为研究

采用批处理振荡法和连续稀释法分别测定了敌草隆在人工添加黑碳土壤和自然形成的不同有机质和黑碳含量的土壤中的吸附一解吸行为。吸附结果表明，人工添加黑碳的土壤对敌草隆的吸附强度和吸附容量以及吸附等温线的非线性均随土壤黑碳添加浓度的增加而逐步增大；自然土壤的吸附容量和吸附强度随土壤总有机质含量增加而增加，但吸附等温线的非线性则与土壤中黑碳对有机质的相对含量有关，黑碳比例越高，等温线非线性越大。解吸实验结果表明，无论是人工添加黑碳的土壤还是自然土壤，对敌草隆的解吸迟滞作用均随土壤黑碳含量增高而愈明显。     

Immobilization of heavy metals in soils amended by nanoparticulate zeolitic tuff: Sorption‐desorption of cadmium

Immobilization of Cd in contaminated soil is a technique to improve soil quality. Zeolites are potentially useful additives to bind heavy metals. This study examines the influence of decreasing the grain size of raw zeolitic tuff to the nano‐range on Cd sorption‐desorption isotherms in a sandy soil. The aim was to evaluate the feasibility of using nanoparticulate zeolitic tuff as a sequestering agent for Cd in soil. Sorption and desorption of Cd on zeolitic nanotuff was investigated in batch experiments. The sandy soil was amended with zeolitic nanotuff, synthetic Al oxide nanoparticles, or raw zeolitic tuff. After a 48 h sorption step, three desorption steps were induced using the sequential dilution method. The measured sorption‐desorption data were adequately described by the Freundlich equation. A nonlinear two‐stage one‐rate model matched well with measured Cd sorption‐desorption isotherms of zeolitic nanotuff, raw zeolitic tuff, Al oxide nanoparticle, and control soil. The batch experiments demonstrated the strong influence of pH on Cd sorption. Zeta‐potential measurements of zeolitic nanotuff indicated that electrostatic interaction was important for sorption. Soil amended with zeolitic nanotuff showed the lowest hysteresis index based on the differences obtained from sorption‐desorption isotherms regarding the amount of Cd sorbed. The index decreased with increasing metal concentration. For soil amended with nanoparticulate zeolitic tuff, the estimated Freundlich coefficient was 4 orders of magnitude higher than in the control soil and 2 orders of magnitude higher than the soil amended with raw zeolitic tuff. In addition, this sorbent decreased the amount of Cd released after three desorption steps by up to 12 and 7 times compared to the control soil and the soil amended with raw zeolitic tuff, respectively. The effect on Cd sorption of grinding the raw zeolitic tuff to the nanorange was considerably more pronounced than the effect of raw zeolitic tuff.     

Sorption of 2,4,6-trichlorophenol in model humic acid-clay systems

Humic acids and clays are important soil components that influence the sorption and desorption of organic contaminants; however, it is unclear how humic acids influence the sorption of organic contaminants onto clays and their subsequent desorption. Sorption and desorption of 2,4,6-trichlorophenol (2,4,6-TCP) by and from humic acid-modified K(+)- and Ca(2+)-montmorillonite and -illite were compared with unmodified clays using batch equilibration methods. Commercial humic acid and the humic acid extracted from forest soil were employed in this experiment. The adsorbed amount of 2,4,6-TCP by commercial humic acid was almost twice as large as that adsorbed by the extracted soil humic acid. More 2,4,6-TCP was sorbed onto K(+)- and Ca(2+)-illite than onto K(+)- and Ca(2+)-montmorillonite. K(+) clays were more effective in adsorbing 2,4,6-TCP than Ca(2+) clays. Sorption of 2,4,6-TCP on humic acid-modified Ca(2+)- and K(+)-montmorillonite and -illite increased as compared with unmodified clays. The sorption nonlinearity of 2,4,6-TCP on humic acid-modified Ca(2+)- and K(+)-illite increased remarkably as compared with the unmodified clays. The sorption nonlinearity of 2,4,6-TCP on humic acid-modified Ca(2+)- and K(+)-montmorillonite increased slightly in contrast to unmodified montmorillonites. By comparing sorption and desorption results, we observed hysteresis for all sorbents including humic acids, clays, and humic acid-modified clays. Sorption nonlinearity and hysteresis were dependent on the structure of humic acids. Higher aromaticity of humic acids resulted in greater sorption nonlinearity and desorption hysteresis. In addition, sorption capacity (K(f)') was positively correlated with the humic acid content of the sorbents. These results show that modification of humic acids on clays can not only increase the adsorption ability of clays but also affect the sorption nonlinearity of 2,4,6-TCP, and the desorption hysteresis was probably due to the structural characteristics of humic acids.