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.     

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.     

水溶性有机质对金霉素在猪粪中吸附-解吸附行为的影响

选择来自猪粪和稻草的水溶性有机质（DOM）,用室内模拟试验方法研究了我国常用抗生素金霉素（CTC）在受到内源和外源DOM作用下在猪粪中的吸附和解吸附行为。研究表明,金霉素能被猪粪便快速吸附,等温线呈非线性,用Freundlich方程可以很好地拟合吸附数据;添加DOM能抑制猪粪对CTC的吸附,其能力大小与加入的DOM种类有关,其中内源性猪粪DOM的解吸附效果明显大于外源性稻草DOM;形成阳离子复合体和加入DOM的性质可能是抑制CTC在猪粪便上吸附的主要机制。     

黄棕壤中活性有机碳对Cu吸附的影响

通过盐酸酸化法来去除4种不同利用方式黄棕壤的活性有机碳（AOC）,得到相对稳定的有机碳土壤,用于研究去除活性有机碳前后对Cu2＋吸附行为的影响。结果表明,黄棕壤去除有机碳前后,对Cu2＋吸附量与平衡液浓度的关系符合Langmuir方程和Freundlich方程,其拟合都呈现极显著相关（P〈0.01）,去除AOC后,黄棕壤各层次对Cu2＋的最大吸附量明显降低,是原土Cu2＋最大吸附量的10%～30%。盐酸酸化法对4种不同利用方式的黄棕壤有机碳的去除率为30%～75%,对Cu2＋吸附的减少率为54%～86%。去除活性有机碳前后,有机碳含量与对Cu2＋的吸附量都呈显著线性相关。土壤有机碳的去除率与对Cu2＋吸附的减少率间相关性达到极显著水平。     

Adsorption and Desorption of Copper in Pasture Soils

Abstract

Copper (Cu) is bound strongly to organic matter, oxides of iron (Fe) and manganese (Mn), and clay minerals in soils. To investigate the relative contribution of different soil components in the sorption of Cu, sorption was measured after the removal of various other soil components; organic matter and aluminum (Al) and Fe oxides are important in Cu adsorption. Both adsorption and desorption of Cu at various pH values were also measured by using diverse pasture soils. The differences in the sorption of Cu between the soils are attributed to the differences in the chemical characteristics of the soils. Copper sorption, as measured by the Freundlich equation sorption constants [potassium (K) and nitrogen (N)], was strongly correlated with soil properties, such as silt content, organic carbon, and soil pH. The relative importance of organic matter and oxides on Cu adsorption decreased and increased, respectively, with increasing solution Cu concentrations. In all soils, Cu sorption increased with increasing pH, but the solution Cu concentration decreased with increasing soil pH. The cumulative amounts of native and added soil Cu desorbed from two contrasting soils (Manawatu and Ngamoka) during desorption periods showed that the differences in the desorbability of Cu were a result of differences in the physico‐chemical properties of the soil matrix. This finding suggests that soil organic matter complexes of Cu added through fertilizer, resulted in decreased desorption. The proportions of added Cu desorbed during 10 desorption periods were low, ranging from 2.5% in the 24‐h to 6% in the 2‐h desorption periods. The desorption of Cu decreased with increasing soil pH. The irreversible retention of Cu might be the result of complex formation with Cu at high pH.     

Effect of low-molecular-weight organic acids on Cl- adsorption by variable charge soils

Low-molecular-weight (LMW) organic acids exist widely in soils and have been implicated in many soil processes.The objective of the present paper was to evaluate effect of two LMW organic acids, citric acid and oxalic acid, on Cl^- adsorption by three variable charge soils, a latosol, a lateritic red soil and a red soil, using a batch method. The results showed that the presence of citric acid and oxalic acid led to a decrease in Cl- adsorption with larger decreases for citric acid. Among the different soils Cl- adsorption in the lateritic red soil and the red soil was more affected by both the LMW organic acids than that in the latosol.     

Differential Aluminum Resistance and Organic Acid Anions Secretion in Triticale

Abstract

Triticale (X Triticosecale Wittmack), a hybrid of wheat and rye, shows a high degree of aluminum (Al) tolerance, but variation in Al resistance between cultivars does exist. The mechanisms responsible for differential Al resistance in 10 triticale cultivars were investigated in this study. Triticale roots secreted both malate and citrate in response to Al stress. The amount of organic acid anions secreted was correlated positively to the relative root elongation (an index for Al resistance) and negatively to the Al content in root apices under Al stress, suggesting that the secretion of malate and citrate seems to be involved in the exclusion of Al from root tip. The Al‐induced secretion of malate and citrate was characterized using an Al‐resistant cultivar (ZC 237) and an Al‐sensitive cultivar (OH 1621). Root elongation was significantly inhibited in both ZC 237 and OH 1621 after 24 h of exposure to 30, 50, or 100 µM Al but was more strongly in OH 1621 than in ZC 237 at all Al concentrations tested. A marked lag phase (3 h) between the addition of Al and the secretion of organic acid anions was observed in both triticale cultivars, and the secretion increased with increasing external Al concentration. The two anion‐channel inhibitors, phenylglyoxal and niflumic acid, significantly inhibited the secretion of malate and citrate in ZC 237, with the degree of the inhibition of niflumic acid greater than that of phenylglyoxal. The Al‐induced secretion of malate and citrate decreased to a very low level at low temperature (4°C) in both cultivars. These results indicate that Al‐induced malate and citrate secretion from roots play important roles in excluding Al and thereby detoxifying Al in triticale. The Al‐induced organic acid anions were inhibited by anion‐channel inhibitors and were dependent on temperature.     

Organic Matter Removal on Oxide Determination in Oxisols Via Portable X-ray Fluorescence

Many factors can influence the results obtained by portable X-ray fluorescence analysis (pXRF). The effect of soil organic matter on pXRF results is not satisfactory understood. Thus, we conducted this study to verify the effect of organic matter removal on oxide determination by pXRF in Oxisols. To obtain soil material with different organic matter contents and maintaining the same elemental composition from soil minerals, six contrasting Oxisols were heated in a muffle furnace for 30 min at the following temperatures (°C): 100; 200; 300; 400; 500 and 600. After heating, the soil samples were scanned using a pXRF Bruker® S1 Titan LE model (Dual Soil mode) for 60 s and the contents of SiO₂, Al₂O₃, Fe₂O₃, TiO₂, P₂O₅, and MnO were recorded. The soil organic matter presence underestimated the pXRF results for lightest oxides (Si and Al) compared to heaviest oxides (Fe, Ti, and Mn). These oxides are important for tropical soils classification and for many soil-related studies and pXRF technology has been a useful tool for soil chemical characterization. Our findings contribute to more suitable use of pXRF highlighting the possible effect of organic matter.     

氧化土和老成土中自然产生的有机酸对磷的活化

Citric and malic acids at concentrations of 0.1,1.0,10,and 100 mmol/L were added to three Ultisols and one Oxisol,The amount of P in solution increased with increasing organic acid concentrations,while the amount of Fe-and Al-bound P decreased.This result suggested that naturally occurring products of organicmatter decomposition could increase the P availability to plants in soils where there is a relatively large pool of Fe-and Al-bound P.The interactions between citric and malic acids at the above concentrations,and p added at rates of 10,20,40,and 80mg/kg were determined.At zero levels of organic acids,all added P became either labile or bound ,and greater proportions remained soluble as the concentration of orgaic acids increased,which suggested that organic acids reduced fixation of dissolved P in Fe-and AL-rich soils .Agricultural practices which increase organic matter input on P-deficient acid soild could decrease P deficiency,This would be important in many tropical and subtropical regions where these soils are common,and where the costs of fertilizers and lime are relatively high.     

模拟酸雨对荔枝果园土壤磷素等温吸附与解吸特性的影响

采用等温吸附试验方法研究了模拟酸雨对荔枝果园土壤磷的吸附与解吸特性的影响。试验结果表明,不同处理间土壤对磷的最大吸附量(Xm)为pH2.5>pH4.5>CK=pH6.5,其中pH2.5的酸雨淋溶处理对磷的最大吸附量(Xm)与其它处理间差异显著;土壤吸附磷的解吸量(Xd)分别与相应的吸附量(X)和原平衡溶液浓度(C)呈显著的指数相关和线性相关,随着土壤对吸附量的增加,土壤磷的解吸量呈指数增长。     

Decomposition of Organic Matter with Previous Cadmium Adsorption in Soils

Decomposition of organic matter with previous Cd adsorption (thereafter referred to as OMACd) in soils and in water was studied in order to clarify the mechanism of Cd-induced inhibition of organic matter decomposition in soil. Two types of organic materials (sludge, rice straw) with or without previous Cd adsorption were mixed with a Gley soil or a Light-colored Andosol in a proportion of 1%. In the soils amended with the Cd-free organic materials, a CdCl₂ solution was added to the soils. The decomposition of the organic matter was examined by measuring the CO₂ evolution for 4 weeks at 28°C. Although the same amount of Cd was added to the soils, the decomposition of OMACd was inhibited to a greater extent than that in the soils to which a CdCl₂ solution had been added.

Furthermore the decomposition of sludge with previous Cd adsorption (thereafter referred to as SACd) in water after inoculation of soil microorganisms was investigated. Although the control sludge without Cd was markedly decomposed at 30°C during 4 weeks, SACd was not appreciably decomposed. These results suggest that OMACd cannot be readily decomposed by microorganisms.     

Effect of Soil Organic Matter on Adsorption and Insecticidal Activity of Toxins from Bacillus thuringiensis

With the large-scale cultivation of transgenic crops expressing Bacillus thuringiensis (Bt) insecticidal toxin in the world, the problem of environmental safety caused by these Bt crops has received extensive attention. The effects of soil organic matter (SOM) on the adsorption and insecticidal activity of Bt toxin in variable- and constant-charge soils (red and brown soils, respectively) were studied. Organic carbon in the soils was removed using hydrogen peroxide (H_2O_2). After H_2O_2 treatment, the SOM in the red and brown soils decreased by 71.26% and 82.82%, respectively. Mineral composition of the H_2O_2-treated soils showed no significant changes,but soil texture showed a slight change. After SOM removal, the cation exchange capacity (CEC) and pH decreased, while the specific surface area (SSA), point of zero charge (PZC), and zeta potential increased. The adsorption isotherm experiment showed that the Bt toxin adsorption on the natural and H_2O_2-treated soils fitted both the Langmuir model (R~2≥ 0.985 7) and the Freundlich model (R~2≥ 0.984 1), and the amount of toxin adsorbed on the H_2O_2-treated soils was higher than that on the natural soils. There was a high correlation between the maximum adsorption of Bt toxin and the PZC of soils (R~2= 0.935 7); thus, Bt toxin adsorption was not only influenced by SOM content, but also by soil texture, as well as the SSA, CEC, PZC, and zeta potential. The LC_(50) (lethal concentration required to kill 50% of the larvae) values for Bt toxin in the H_2O_2-treated soils were slightly lower than those in the natural soils, suggesting that the environmental risk from Bt toxin may increase if SOM decreases. As the measurement of insecticidal activity using insects is expensive and time consuming, a rapid and convenient in vitro method of enzyme-linked immunosorbent assays is recommended for evaluating Bt toxin degradation in soils in future studies.     

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。     

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.     

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.     

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.     

土壤吸附可溶性有机碳研究进展

可溶性有机碳(DOC)是土壤有机碳(SOC)中最活跃的部分,虽然所占土壤总有机碳比例仅为0.04%~0.22%,但土壤对于DOC的吸附却被认为是深层土壤固定有机碳的主要过程。由此可见,土壤对DOC的吸附行为对于全球碳循环的研究有着深远的意义。文章以土壤对DOC的吸附行为为主体,综述了土壤对DOC的吸附特征,在此基础上总结出其吸附机理,并提出了目前研究的不足之处及对未来研究方向的展望,旨在为深入了解DOC在土壤环境中的迁移转化行为提供依据。     

硅藻土对磷在红壤中吸附解吸的影响

为提高磷肥利用率和研究磷肥增效技术,通过恒温振荡试验研究了硅藻土对水溶性磷肥(磷酸二氢钙)在红壤中有效性的影响.结果表明,在0.31 mg P/g土和1.25 mg P/g土水平下,硅藻土显著地降低了供试土壤对磷酸二氢钙的吸附,增加了水溶性磷、0.01 mol/L CaCl2溶液解吸磷和Olsen P的含量,且三者随硅藻土用量的增加而增加,其主要归因于硅藻土多孔、比表面积大和富含羟基的结构组成.硅藻土与磷酸二氢钙的施用顺序也显著地影响着供试土壤中磷的有效性,硅藻土先于磷酸二氢钙加入供试土壤处理的水溶性磷和0.01 mol/L CaCl2溶液解吸磷含量高于添加次序相反的处理,Olsen P含量差异不显著.     

水溶性有机还原物质研究: Ⅲ. 稻草分解产物的电化学性质及其与可变电荷土壤的相互作用

Some electrochemical properties,such as pH,Eh,and voltammetric behavior.of the decomposition products of rice straw and the interactions of these products with soils were studied.The pH,Eh,and amounts of organic reducing substances changed markedly during the 6-day anaerobic decomposition.pH decreased sharply to pH 5 on the tenth day and then increased gradually to 7 on the 45rh day.The amounts of organic reducing substances increased almost synchronously with the fall of redox potential during the first 15 days.The differential pulse voltammetric(dpv) behavior changed not only in the peak current but also in the peak potential.The fractions with apparent molecular weights lower than 200 daltons appeared to be active in dpv behavior.The electric charge and positively charged,respectively.The group with a low apparent molecular weight and a negative charge was the main components responsible for the lower anodicpeak potentials.They were oxidized first during the interactions of the organic reducing substances with soils.