Ion Transport Dynamics in Acid Variable Charge Subsoils

This is a mini-review of the research work conducted by the authors with the objective of studying ion transport in variable charge subsoils collected from different areas around the world. An attempt is made in these studies to relate the unique behavior manifested during ionic transport in these subsoils with their mineralogical, physical and chemical properties, which are markedly different from those in soils from temperate regions. The variable charge subsoils have a relatively high salt sorption capacity and anion exchange capacity (AEC) that retards anions downward movement. The AEC correlates closely with the anion retardation coefficients. Ca²⁺ applied with gypsum in topsoil may be transported to the subsoil and may improve the subsoil chemical properties. These results may help in developing appropriate management strategies under a range of mineralogical, physical, and chemical conditions.     

亚硒酸盐和可变电荷土壤表面羟基离子的交换反应: Ⅰ.电解质种类及pH的影响

Hydroxyl release of red soil and latosol surfaces was quantitatively measured using a self-made constant pH automated titration instrument, to study the changes of hydroxyl release with different added selenite amounts and pH levels, and to study the effects of electrolytes on hydroxyl release. Hydroxyl release increased with the selenite concentration, with a rapid increase at a low selenite concentration while slowing down at a high concentration. The pH where maximum of hydroxyl release appeared was not constant, shifting to a lower valus with increasing selenite concentration. Hydroxyl release decreased with increasing electrolyte concentration, and the decrease was very rapid at a low electrolyte concentration but slow at a high electrolyte concentration. For NaClO₄, NaCl and Na₂SO₄ hydroxyl release was in the order of NaClO₄ > NaCl 》 Na₂SO₄, and the difference was very significant. But for NaCl, KCl and CaCl₂, the order of hydroxyl release was NaCl > KCl > CaCl₂, and the difference was smaller. The amount of hydroxyl release from Xuwen latosol was greater than that from Jinxian red soil. Hydroxyl release existed in a wider range of pH with Xuwen latosol than with Jinxian red soil, due to their difference in soil properties. However, both soils had similar curves of hydroxyl release, indicating the common characteristics of variable charge soils.     

硒酸根与氢氧根离子在可变电荷土壤表面的交换反应: Ⅱ. 氢氧根离子释放的动力学

A self-made constant pH automated titration instrument was used to study the kinetics of hydroxyl release during selenite reacting with variable charge soils. The rate of hydroxyl release was very rapid at the first several minutes, then gradually slowed down, and at last did not change any more. The experimental data was well fitted by the Langmuir kinetic equation, and with increasing selenite concentration or decreasing solution pH, the reaction lasted longer, the maximum of hydroxyl release (x_m) increased, and the binding constant (k) decreased. The time of hydroxyl release with Xuwen latosol was much longer than that with Jinxian red soil.     

酸性条件下可变电荷土壤对铜吸附动力学特征

用自行设计的动力学装置,研究了酸性条件下Cu在可变电荷土壤表面的反应动力学吸附特征。结果表明,在酸性条件下,Cu吸附过程分为快反应和慢反应。从一级动力学方程拟合的参数可知,3种土壤的最大吸附量依次为砖红壤〉赤红壤〉红壤,Cu最大吸附量随酸度增加显著下降;用Elovich方程和抛物线扩散方程常数b值,解释离子的表观扩散速率,3种土壤的b值依次为砖红壤〉赤红壤〉红壤,且随酸度的增大而降低。从相关系数的比较看,Elovich方程在描述Cu的吸附数据比一级动力学方程和抛物线扩散方程要差。在Cu吸附过程中,pH为5．5和4．3时,红壤和赤红壤流出液中有质子释放,质子的释放可能涉及铜离子的水解;而砖红壤在pH为5．5有质子的释放,pH4-3时有质子的消耗。当原液pH为3.3和3．8时,都存在质子的消耗。3种土壤H＋的消耗过程有较大的区别,砖红壤上快速消耗H＋鱼-远远大于红壤和赤红壤。反应初期,H＋质子的消耗是快速反应,主要包括土壤交换阳离子的缓冲作用、土壤表面的质子化及硫酸根专性吸附释放的羟基中和H＋质子;而以后的反应中,H＋质子对矿物的溶解是一缓慢过程。     

电位滴定法研究可变电荷土壤表面酸碱性质的进展

我国长江以南地区的土壤富含铁铝氧化物,其土壤胶体表面电荷具有可变性,显著不同于温带地区的恒电荷土壤,因而称之为可变电荷土壤。开展可变电荷土壤的表面特性研究对农业可持续发展、土壤资源保护等均具有重要的现实意义。电位滴定法是开展可变电荷土壤表面特性研究最直接有效的方法。本文首先总结了电位滴定法的实验条件设置对可变电荷土壤表观电荷零点的影响,在此基础上,归纳了应用电位滴定法结合表面络合模型开展可变电荷土壤酸碱特性的研究进展,分类讨论了黏土矿物组成、氧化物、有机质等相关影响因子对可变电荷土壤酸碱缓冲能力的影响,并展望可变电荷土壤表面酸碱缓冲能力的未来研究。本文将有助于初学者理解可变电荷土壤,呼吁更多学者关注可变电荷土壤的酸碱缓冲特性研究及其在土壤资源可持续利用中所起的重要作用。     

Ion Transport and Permeability in an Allophanic Andisol at Low pH

Allophanic Andisols have a significant pH-dependent charge. The positive charge increases and the negative charge decreases as pH decreases; therefore, anion movement becomes slower and cation movement becomes faster as pH decreases in the soil. At low pH, soil dispersion occurs easily due to electric repulsive force. The permeability of the soil then decreases because of structural changes that occur when dilute HCl or HNO₃ is percolated in the soil. However, soil permeability does not decrease when dilute H₂SO₄ is percolated in the soil. This is because SO₄^2- strongly adsorbs on the soil surface at low pH and the soil remains flocculated.     

Changes in Isoelectric Point as Affected by Anion Adsorption on Two Brazilian Oxisols

Abstract

Iron and aluminum oxides are widespread in tropical environments and increase soil's isoelectric point (IP). Anion adsorption modifies the IP and the surface charge of oxidic materials. This study evaluated IP changes on A‐ and B‐horizon samples of two Brazilian Oxisols upon reaction with acetate, citrate, oxalate, phosphate and sulfate (1 mmol L^?1; soil–solution 1∶100; pH 5.5; ionic strength 30 mmol L^?1 as NaCl). Most anions seemed to be specifically adsorbed, because the IP decreased after the reaction with the ligands. The IP of natural and of the acetate‐, citrate‐, oxalate‐, phosphate‐, and sulfate‐treated samples followed the order: Red Latosol‐A: 2.89,2.86, <2.50, 2.63, 2.79, 2.86; Red Latosol‐B: 5.92, 5.89, 2.79, 3.42, 3.36, 5.84; Red‐yellow Latosol‐A: 2.89, 2.79, <2.50, <2.50, 2.66, 2.89; and Red‐yellow Latosol‐B: 6.38, 6.29, 3.06, 4.36, 3.69, 6.15. The decrease in IP caused by citrate, oxalate, and Phosphate is relevant because this interferes with charge‐dependent soil reactions.     

生化黄腐酸对盐碱土水盐运移特征及盐基离子组成的影响

生化黄腐酸（biochemical fulvic acid,BFA）在改善土壤结构、促进作物生长与提高肥效方面均表现出较好的应用价值。为探讨添加BFA对盐碱土水盐运移规律的影响,揭示BFA淋盐增效机理,基于一维垂直土柱入渗试验,对不同BFA添加量（0,1,2,4,8 g/kg）条件下盐碱土的水盐运移特征、入渗模型参数及土壤交换性盐基离子组成进行了研究。结果表明,入渗条件下增加BFA能够降低土壤水分入渗速率,延长入渗时间,提高土壤保水性能。Kostiakov模型、Philip模型和代数模型均能较好地描述入渗过程,模型参数中经验系数（K）、吸渗率（S）和综合形状系数（α）均随BFA添加量的增加呈先减小后增加的变化趋势。与对照相比,添加BFA均能提高土壤持水效率和相对脱盐率,在2 g/kg BFA添加量条件下,0—20 cm土层内土壤平均体积含水率提高3.38%,平均持水效率提高10.65%,相对脱盐率提高36.32%。此外,相比对照,添加BFA后土壤交换性盐基总量（total exchangeable base,TEB）均有所增加,TEB组成中Ca²⁺浓度增加,Na⁺浓度降低。因此,在盐碱土中添加BFA能够显著影响土壤水分入渗和水盐运移特征,改善土壤水盐分布状况,对盐碱土具有较好的保水和脱盐效果,且添加BFA后土壤TEB显著增加,能够显著改善土壤交换性盐基离子组成,提升土壤质量。     

低分子量有机酸对可变电荷土壤和矿物表面化学性质的影响

低分子量有机酸是土壤中广泛存在的,它们参与土壤中许多化学过程,在营养元素活化、解铝毒和矿物风化等方面发挥重要作用。本文综述了可变电荷土壤和矿物对低分子量有机酸的吸附及这类有机酸对土壤的表面电荷、动电性质和土壤吸附无机阴、阳离子的影响,为从事相关研究工作的同志提供参考。     

Estimating Sorption Affinities of Heavy Metals on Humic Acid and Silica using a Constant Capacitance Model

The adsorption of heavy metals [cadmium (Cd ²⁺), cobalt (Co²⁺), nickel (Ni²⁺), zinc (Zn²⁺), and lead (Pb)] and calcium (Ca²⁺) on humic acid and silica were investigated to understand the adsorptive selectivities of heavy metals on the constituents of soil. The experiments for the adsorption of Cd and Pb were carried out in a 0.1 mol L^?1 (M) sodium nitrate (NaNO₃) background solution, whereas those for the other metals were done in a 0.1 M sodium chloride (NaCl) solution. The adsorptive affinities of the metal ions on the humic acid and silica were ranked by the intrinsic surface complexation constants [K _m ¹(int)] that were calculated approximately from the adsorptive data using a constant capacitance model. The log [K _m ¹(int)] values of the metals were in the order Zn²⁺(?2.29) > Cd²⁺(?2.41) > Co²⁺(?2.74) > Ni²⁺(?2.92) ?> Ca²⁺ (?3.33) for the humic acid and Zn²⁺(?4.23) > Cd²⁺(?4.49) > Ni²⁺(?4.51) ? Co²⁺ (?5.99) > Ca²⁺(?6.37) for silica.     

油田酸化压裂废液中F^-在土壤中的迁移规律研究

通过土柱实验研究了大庆油田酸化压裂废液中氟离子（F^-）对土壤环境的影响,考察了酸化压裂废液中不同浓度的F^-在土壤中的迁移转化规律,以及不同酸度、不同的土壤质地对F^-在土壤中的迁移规律的影响,并探讨了相关作用机理。结果表明,油田酸化压裂废液中F^-对土壤环境产生明显的影响,随着废液中v浓度增加,F^-在黑钙土中的迁移深度增加;沿土壤深度方向发展,土层中F^-含量呈现降低趋势;随着F^-浓度的变化,F^-在黑钙土中的迁移基本符合负指数y=yo＋a·exp（-x/t）规律;而随着压裂废液中酸度的增加,土壤中粘土矿物Ca^2＋、Al^3＋等阳离子浓度增高,与水中氟形成难溶化合物,从而使得F^-在土壤环境中的迁移深度反而降低;F-在大庆地区3种典型土壤中的迁移深度符合黑钙土〉黄土〉碱土的规律;油田酸化压裂废液中F^-主要存在于在10cm深度的土壤表面层。     

模拟再生水灌溉下污灌土壤中盐分离子交换运移的试验研究

为研究再生水灌溉下原污灌区土壤中主要盐分离子交换运移规律,采用有污水灌溉背景的两种质地土壤,根据再生水的基本性质及其盐分离子组分,配制4种浓度水平的入渗液,进行土柱模拟试验。结果表明,不同质地土壤在低Na^＋配制液淋洗下的穿透曲线都出现下凹现象,但Na^＋在壤土中富集的表现并不显著,而在粉质砂壤土中部分Na^＋吸附累积时间较长;模拟再生水入渗溶液中不同组分的盐分离子在不同程度上影响污灌土壤中发生的离子化学反应的进行,导致各处理下Na穿透时间发生显著差异;长期再生水灌溉会对HCO3^-含量较高且粉粒比重大的土壤的入渗等性能产生更为不利的影响。     

华中南部某些土壤针铁矿的形态

The morphologies of goethites in latosol, red soils, yellow-brown soil and the paddy soils developed from red soils were studied in comparison with the morphology of synthetic goethite by means of the X-ray diffraction, transmission electron microscopy and energy dispersive X-ray analysis. The synthetic goethite displayed acicular particles elongated in the c-direction. The goethites in the latosol, red soils and yellow-brown soil were platy particles stretched in two directions or isodimensional particles, and those in the paddy soils from red soils were acicular, short columnar, platy or isodimensional particles. Various morphologies of the goethites probably suggested their different dominant crystal faces, surface charge distribution and surface adsorption characteristics.     

Ion release in the C horizon of a forest soil triggered by Carbonic Acid

Ion release in the C horizon of a Skeletic Umbrisol on gneiss bedrock was investigated by percolation experiments at a water status near field capacity and with adjusted CO₂ partial pressures in soil air. CO₂ partial pressures of 0.001, 0.01, and 0.1 bar with pH‐values of 5.7, 4.9, and 4.5 yielded cation release rates of 3.0, 8.5, and 12.3 kmol_c yr^–1 ha^–1 at a 1 m horizon depth and 800 mm seepage water. Within the pH range of 5.7 to 4.5, the activity of carbonic acid triggers ion release. For the treatment with a CO₂ partial pressure of 0.001, the isolation of a weathering rate (0.5 kmol_c yr^–1 ha^–1) was possible because parallel running processes such as the dissolution of solid compounds could be identified by dissolved anions, and exchange processes only modified internal ratios of mobilized basic cations. The weathering rate at a site‐typical CO₂ partial pressure of 0.01 bar was about 5–10 times higher than usually assumed in the literature. There are three reasons that may account for this: (1) the consideration of actual carbonic acid activities and (2) specific site features such as the richness of basic minerals and/or the presence of a skeletal fraction with micro voids and fissures providing large internal surfaces. Furthermore, (3) it can not be completely excluded that parallel running exchange processes contribute to ion release.     

腐植酸在土壤中迁移的模拟实验研究

浅层地下水中的腐植酸与人体健康密切相关,腐植酸在土壤中的迁移影响土壤和地下水中腐植酸含量。采用土柱模拟实验,研究了不同条件下腐植酸的迁移规律。结果表明,腐植酸的出水浓度随时间逐渐升高,最后趋于稳定;同一时间段内,初始浓度为15mg·L-1时的出水浓度比10mg·L-1时高,且早24h达到稳定浓度;淋滤液pH为9时的出水浓度比pH为4时高,且早16h达到稳定浓度;粉质粘土柱对腐植酸的吸附和阻滞作用大于砂壤土柱,出水浓度较低,晚32h达到稳定浓度;土层厚为5cm的土柱出水浓度高于15cm土柱,早32h达到稳定浓度。分析认为,土壤对腐植酸的吸附作用是出水浓度变化的主要原因,腐植酸和土壤的理化性质是影响腐植酸在土壤中迁移的主要因素。     

Adsorption/Desorption of Organic Anions in Brazilian Oxisols

Abstract

Organic anions affect solute mobility in soils. This study evaluated citrate and oxalate adsorption (0 to 4 mmol L^?1, soil–solution 1∶100, pH 5.5, ionic strength 30 mmol L^?1 as NaCl, 72‐h reaction) and desorption (pH 5.5, 30‐mmol L^?1 NaCl, 72 h) on A‐ and B‐horizon samples of two Brazilian Oxisols. Langmuir and Freundlich isotherms were used to assess adsorption maximum, distribution coefficients (Kf, Ku), and buffer index. Adsorption maximums (mol kg^?1) for red Latossol‐A, red Latosol‐B, red‐yellow Latosol‐A, and red‐yellow Latosol‐B horizons follow: citrate 0.0318, 0.0272, 0.0289, 0.0392; oxalate 0.0641, 0.0329, 0.0538, 0.0380. Kf (mol^1?1/n kg^?1 L^1/n) follows: citrate 0.3550, 0.3781, 0.4211, 0.2024; oxalate 1.0916, 0.0637, 1.8228, 0.0922. Buffer index (mol kg^?1)(mol kg^?1)^?1 follows: citrate 0.0841, 0.0756, 0.0738, 0.0264; oxalate 0.3787, 0.0862, 0.3233, 0.1082. Both anions showed great affinity for variable‐charge soils. The distribution curves for Ku showed higher adsorption energy in B‐ than in A‐horizons.     

可变电荷土壤表面酸碱性质与模型研究进展

可变电荷土壤表面酸碱性质是指土壤与质子的结合能力,主要包括表面质子反应活性位点密度Ds、电荷零点pH_(pzc)以及质子化、去质子平衡常数pK_a。表面酸碱性质对于评估土壤酸碱缓冲能力、揭露酸化机制有重要意义,也是探究阳离子和阴离子在土壤固液间的分配,控制微量元素移动性和生物有效性的重要土壤性质之一。本文综述了通过表面络合模型获取表面酸碱性质参数的方法以及研究复杂土壤体系的两种方法。电荷零点pH_(pzc)主要通过宏观滴定实验获得,但需要不断优化实验操作来减少无意义因素的影响。而表面质子反应活性位点密度D_s和质子化、去质子化平衡常数pK_a,则通常分别通过Gran函数和直线外推法计算等方法得到。目前,土壤活性成分金属氧化物、黏土矿物及腐殖质表面酸碱性质已通过表面络合模型得到广泛研究,研究方法和相关数据已逐渐趋于完善。而随着表面络合模型的发展,土壤混合体系表面酸碱性质的研究也在不断加深。组分添加法通过各组分表面性质的加和来预测质子在土壤和溶液中分配和形态,目前已从矿物聚合模型扩展到矿物-有机物聚合模型,因为有机物和矿物组分之间的相互作用对于研究相当重要。而广义复合法假设土壤表面性质均一,依据实验吸附数据和表面积拟合获得表面酸碱性质,现在已发展为n-site/n-p Ka,并建立了一种通过土壤化学性质预测表面酸碱性质广义回归方程。最后,文章探讨了表面络合模型相关研究应该解决的科学问题,以及土壤表面酸碱性质研究在未来的趋势。     

Effect of Low Molecular Weight Organic Anions on the Adsorption of NO3− by Variable Charge Soils

Low molecular weight organic acids exist widely in soils and have been implicated in many soil processes. The results in the present paper showed that the presence of organic anions led to a decrease in the adsorption of NO₃⁻. The effect of citrate was much larger than that of oxalate and malate. Among different soils, the effect for Hyper-Rhodic Ferralsol and Rhodic Ferralsol was larger than that for Haplic Acrisol, which was related to the content of iron oxides in these soils. The effect of organic anions decreased with the increases in pH value and the amount of organic anions added. The organic anions depressed the adsorption of NO₃⁻ through two mechanisms, the competition of the organic anions for adsorption sites with NO₃⁻ and the change of soil surface charge caused by the specific adsorption of organic anions.     

Interactions between anthropogenic sulphate and marine salts in the Bs horizons of acidic soils in Scotland

In laboratory adsorption experiments, the comparison of podzol Bs horizons from coastal and inland moderately-impacted catchments with those from a severely-acidified inland region has demonstrated the effect of marine inputs on SO₄ ^2– -retention. Moderate sea-salt inputs and low acid deposition leads to the retention of most of the SO₄ ^2– and the release of soluble Mg²⁺; increasing the marine salt loading causes the development of a selectivity towards retention of acidic SO₄ ^2– and the retention of Mg²⁺. In the highly-impacted soil, the marine input caused a decrease in SO₄ ^2– retention in open moorland soils. The opposite occurred under forest, due to the ion-exchange of marine Mg²⁺ for soil Al³⁺, increasing soil acidity towards the pH₀ (Gillman and Uehara, 1980), which is depressed below that of its moorland equivalent.     

可变电荷或永久电荷土壤上的电荷特征与土壤对Cu2+的吸附－解吸之间的交互作用

Charge characteristics and Cu^2 adsorption-desorption of soils with variable charge(latosol)and permanent charge(brown soil)and the relationship between them were studied by means of back-titration and adsorption equilibrium respectively.The amount of variable negative charge was much less in variable-charge soil than in permanent-charge soil and increased with the pH in the system,but the opposite trend occurred in the points of zero charge(PZCs).The amount of Cu^2 ions sorbed by permanent-charge soil was more than that by variable-charge soil and increased with the increase of Cu^2 concentration within a certain range in the equilibrium solution.The amount of Cu^2 ions desorbed with KCl from permanent-charge soil was more than that from variable-charge soil,but the amount of Cu^2 ions desorbed with de-ionized water from permanent-charge soil was extremely low whereas there was still a certain amount of desorption from variable-charge soil.The increase of PZC of soils with variable or permanent change varied with the increment of Cu^2 ions added.When the same amount of Cu^2 ions was added,the increments of PZC and variable negative surface chargc of permanent-charge soil were different from those of variable-charge soil.