The specific adsorption of organic and inorganic phosphates by variable‐charge oxides

We measured the reaction of inorganic phosphate and of four organic phosphates with three aluminium hydroxides or oxides. We compared the fit of the Langmuir equation with that of an equation designed to allow for the feedback effect of adsorption on the electric potential. We also fitted a four‐plane model to describe the effects of pH on adsorption and ζ potential. For inorganic phosphate, the Langmuir equation described adsorption curves poorly, indicating that there was a large feedback effect of adsorption on the electric potential of the adsorption plane. For the organic phosphates, the deviations from the Langmuir equation were not as marked, indicating that there was little feedback effect. Nevertheless, there was a large effect on the ζ potential of the phosphated aluminium (hydr)oxides. We suggest that when a large organic phosphate molecule is adsorbed, the charge conveyed to the surface is repelled electrostatically to the outside of the new surface. There is therefore a large effect on the ζ potential and a small effect on the potential of the adsorption plane. This suggestion was supported by the fit of the four‐plane model, for which, with increasing molecular weight, the mean position of the charge conveyed to the surface by adsorption was moved further from the plane carrying the potential determining ions (H⁺ and OH^?).     

恒电荷土壤及可变电荷土壤与离子间相互作用的研究 Ⅱ.共存体系中Cl-的吸附特性

对 3种可变电荷土壤和 4种恒电荷土壤在陪伴阳离子分别为Na 、K 、NH 4 、Mg2 、Ba2 、Al3 和共存SO2 -4下Cl- 的吸附量进行了测定。结果表明 ,供试土壤的Cl-吸附量顺序均为AlCl3>BaCl2 和MgCl2 >KCl和NH4 Cl>NaCl,其中可变电荷土壤的差异较大。不同电解质溶液中Cl- 吸附量的顺序与土壤所带正电荷量的顺序一致。Langmuir方程的K值较小 ,且在不同介质中的差异不大。随SO2 -4浓度的增大 ,可变电荷土壤对Cl- 的吸附量减少 ,平衡液的pH值增大 ,而恒电荷土壤则变化甚微 ,说明共存的SO2 -4使可变电荷土壤的表面负电荷增加 ,但对恒电荷土壤则影响不大。这些结果说明 ,Cl- 以电性吸附的机理不因介质而变。可变电荷土壤在一价阳离子存在时 ,除土壤本身所带的正电荷外 ,还有一价阳离子吸附后产生的正电荷以及由此引起的对Cl- 的协同吸附。在二、三价阳离子存在时 ,还有Cl- 的离子对吸附 ,而恒电荷土壤在所有介质中 ,似乎总是以与Cl- 的协同吸附为主     

Testing a mechanistic model. III. The effects of pH on fluoride retention by a soil

The pH of a soil was altered by incubating it with either lime or acid at 60°C for 1 day. Subsamples were then mixed with fluoride solutions in order to measure the effects of pH on fluoride retention. The results were compared with those previously obtained with phosphate on the same soil. At equal concentration of total fluorine in solution, fluoride retention was greatest at about pH 5.5 and decreased at both lower and higher pH. The decrease at low pH appeared to be caused by the formation of complexes between fluoride and aluminium in solution. As a result, only a small proportion of the total fluorine in solution was present as fluoride ions. At equal concentrations of fluoride ions, fluoride retention decreased with increasing pH. It was shown that this decrease could be explained by decreases in the electrostatic potential of the variable charge materials. The decrease in potential was steeper than that required to describe phosphate retention. This is consistent with the plane of adsorption of fluoride ions being closer to the plane of adsorption of H⁺ and OH^? ions.     

Adsorption of anionic surfactant (sodium dodecyl sulfate) on silica

The adsorption of an anionic surfactant sodium dodecyl sulfate (SDS) on a negatively charged silica was studied to provide a better understanding of surfactant adsorption phenomena in an electrostatic repulsion environment between surfactant and soil. The adsorption experiment was conducted under different electrolyte concentration and pH. Results indicated that adsorption happened with hydrophobic interaction, although electrostatic repulsion was generated between SDS and silica surface. The adsorption amount decreased with decreasing electrolyte concentration and increasing pH due to the increase of electrostatic repulsion. The influence of electric potential near the silica surface on the adsorption was confirmed with the modified Langmuir adsorption equation, 1-pK basic Stern model and zeta potential. Because silica is ubiquitous in soils and the water environment, the adsorption characteristics of an anionic surfactant is important when we consider the fate of an anionic surfactant in the environment. The result is also useful when considering the fate of agricultural chemicals which contain negative charge and hydrophobic sites.     

ADSORPTION ISOTHERMS: SHOULD THEY BE SPLIT?

Langmuir adsorption isotherms are unlikely to be appropriate when applied to the adsorption of charged phosphate ions on charged oxide surfaces. It is more likely that the adsorption model proposed by Bowden et al. (1973, 1974 and 1977) for adsorption on variable charge variable potential surfaces will be applicable. Theoretical isotherms were calculated from this model for a series of pH values and ionic strengths. It is shown that these isotherms can be split into two or more Langmuir isotherms in much the same way as has been done by various authors for experimental isotherms. The parameters of the Langmuir isotherms behave in the same way as those derived from the experimental isotherms. The charging characteristics of the theoretical isotherms are also similar to that observed experimentally. Because the model which is based on a single type of adsorption site is closely similar to the experimental isotherms, it is erroneous to split the isotherms into a series of Langmuir isotherms unless there are good a priori reasons.     

Ionic strength effects on surface charge and adsorption of phosphate and sulphate by soils

Two surface soils (Patua and Tokomaru) of contrasting mineralogy were incubated with several levels of either CaCO₃ or HC1. The effects of ionic strength on pH, on surface charge, and on the adsorption of phosphate and sulphate were measured in three concentrations of NaCl. The pH at which the net surface charge was zero (point of net zero charge—PZC) was 1.8 for the Tokomaru soil and 4.6 for the Patua soil: differences that can be related to mineralogical composition. There was an analogous point of zero salt effect (PZSE) that occurred at pH 2.8 for the Tokomaru soil and at 4.6 for the Patua soil. The presence of permanent negative charge in the Tokomaru soil resulted in an increase in PZSE over PZC. The effect of ionic strength on adsorption varied greatly between phosphate and sulphate. For phosphate, there was a characteristic pH above which increasing ionic strength increased adsorption and below which the reverse occurred. This pH (PZSE for adsorption) was higher than the PZC of the soil and was 4.1 for the Tokomaru soil and 5.3 for the Patua soil. In contrast, increasing ionic strength always decreased sulphate adsorption and the adsorption curves obtained in solutions of different ionic strengths converged above pH 7.0. If increasing ionic strength decreases adsorption, the potential in the plane of adsorption must be positive. Also, if increasing ionic strength increases adsorption, the potential must be negative. This suggests that, depending upon pH, phosphate is adsorbed when the potential in the plane of adsorption is either positive or negative, whereas sulphate is absorbed only when the potential is positive.     

土壤和氧化铁对氟化物的吸附和解吸

本文研究了两种土壤(砖红壤和黄棕壤)和两种合成氧化铁(无定形氧化铁和针铁矿)对氟化钠溶液的吸附和解吸现象,讨论了氟离子吸附的吸附等温线特征.根据实验资料和吸附等温线的拟合情况,我们认为,砖红壤和无定形氧化铁用Langmuir公式来描述,黄棕壤和针铁矿用Freundlich公式来描述更为适宜.氟离子的解吸量均低于吸附量.研究结果表明,由于水洗和醇洗,一部分以静电引力所吸附的氟离子被洗去,造成氟离子解吸量偏低.     

土壤吸附砷酸盐动力学的初步研究

本研究目的是了解陕西省的几种土壤吸附和解吸附砷酸盐的速率和过程,以及其吸附能量。Kuo和Lotse导出的双常数速率公式拟合试验资料优于一级、二级、三级反应公式,抛物线扩散和Elovich公式等五个公式。用双常数速率公式(C=k·C₀·t^1/m)分两段拟合能进一步提高拟合优度。根据Arrhenius公式计算出的吸附活化能是0.70—3.40千卡/克分子。低的活化能表明,供试土壤对砷酸盐的吸附作用是一种完全不同于真溶液条件化学反应的物理学过程。土壤吸附和解吸附砷酸盐的速度和容量受作用时间、温度、溶液∶土壤比率,加入的砷量和浓度,以及土壤特性的影响。粘土的吸附反应常数(k),吸附量比沙壤土大。而沙壤土有高的解吸附反应速度常数(k_-1^'),砷酸盐容易被解吸附而释放出来。     

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。     

ADSORPTION OF PHOSPHATE BY VARIOUS OXIDES: THEORETICAL TREATMENT OF THE ADSORPTION ENVELOPE

An explanation is put forward for the shape of adsorption envelopes found for phosphate adsorption by various metallic oxides. The equation x_m= C₁ (μH₃PO⁴⁺μ∑anions) is proposed, where μH₃pO₄ is the chemical potential of undissociated H₃PO₄; μ∑anions is the chemical potential of all phosphate anions considered as one. component; C₁ is a constant that includes influences of surface charge, chemical affinity of the metal for phosphate, specific surface area, etc., and x_mis the calculated Langmuir maximum adsorption of P at each pH. The dependence of C₁ on the metal present in the oxide is shown.     

有机肥对磷的吸附-解吸的影响及在红壤发育成的水稻土上的有效性

A field test with the traditional rotation of paddy rice/upland crop (wheat) was carried out on a paddy soil derived from red earth to elucidate the effect of organic manure on the phosphorus adsorption-desorption by soil and its P availability. Soil samples were taken from different treatments at rice harvesting stage and analysed. The isothermal adsorption of P by the samples fitted very well with Langmuir equation, and hence, the parameters in the equation, i.e., maximum adsorption (qm), constant related to bonding energy (k) and their product (k × qm) could be used as a comprehensive index to characterize the potential P adsorptivity of the soil. Organo-inorganic fertilization and organic manuring could decrease qm and k, while mineral P application had little effect on them. The isothermal desorption of P was significantly correlated with initially added and isothermally adsorbed P. Part of P added was fixed, which represented the P fixation capacity of soil, and organic manuring could obviously lower the P fixation. The content of soil available P had a significant negative correlation with qm, k and fixed P. It is concluded that organic manure could increase the P availability of paddy soil derived from red earth by decreasing qm, k, maximum buffering capacity (MBC=k × qm) and fixation capacity.     

Boron adsorption and desorption in some acid soils of West Bengal,India

Laboratory and greenhouse experiments were conducted to determine the influence of soil properties on adsorption and desorption of boron (B) as well as to estimate the degree of reversibility of adsorption reactions. The utility of Freundlich and Langmuir equations for characterizing the plant availability of applied B in soils was established using soybean [Glycine max (L.) Merr.] as a test crop. The adsorption-desorption study revealed that Fe₂O₃ and clay were primarily responsible for retaining added B in all the 25 different soils under investigation. Organic carbon, pH and cation exchange capacity (CEC) positively influenced the adsorption of B while free Fe₂O₃, organic carbon and clay retarded release of B from these soils. The degree of irreversibility (hysteresis) of B adsorption/desorption increased with increase in organic carbon and CEC of these soils. Freundlich isotherm proved more effective in describing B adsorption in soils as compared to Langmuir equation. The split Langmuir isotherm demonstrated that any of the adsorption maxima, calculated from lower, upper or entire isotherm, could be of practical use. Contrary, bonding energy coefficient, calculated either at lower or higher equilibrium concentration failed to show any practical benefit. Regression models as a function of B application rate and adsorption equation parameters to predict B uptake from applied B, demonstrated the utility of Langmuir and Freundlich equation parameters.     

恒电荷土壤胶体对Cu2+ 、Pb2+ 的静电吸附与专性吸附特征

供试土壤胶体对Cu2 、Pb2 的吸附强度用pH50 值表示 ,其大小次序为 :土 >黄绵土、黑垆土 >黄褐土。离子强度实验和表面络合反应机制证明恒电荷土壤胶体对Cu2 、Pb2 的吸附含有专性吸附 ,n值可作为判断专性吸附与静电吸附比例的特征值 ,低pH值时 ,以水解 -络合吸附为主 ;高pH值时 ,以水解 -络合与沉淀吸附为主。静电吸附和专性吸附的比例与pH有关 ,各土壤胶体专性吸附百分数大小为 :黄褐土 >土 >黑垆土 >黄绵土。不同土壤胶体在同一介质中对Cu2 、Pb2 的固有络合常数logKintM 值及固有络合ΔG m 负值大小次序与吸附强度大小一致。在定pH定浓条件下 ,考虑离子之间的相互作用时 ,土壤胶体对重金属离子的吸附过程可用BDM等温式描述。供试土壤胶体对Cu2 、Pb2 专性吸附ΔG m 的大小与固有络合ΔG m 接近且大小次序也一致。     

Adsorption of emerging sodium p-perfluorous nonenoxybenzene sulfonate (OBS) onto soils: Kinetics, isotherms and mechanisms

The widespread use of sodium p-perfluorous nonenoxybenzene sulfonate(OBS), a typical alternative to perfluorooctane sulfonate, has resulted in potential threats to the environment, but the adsorption behavior of OBS in soils has not yet been reported. In this study, the adsorption behaviors of OBS on five soils with different physicochemical properties were investigated. The rate of OBS adsorption was fast, and most of the OBS uptake was completed within 12 h. The good model fit of OBS adsorption to the pseudo-second-order and Elovich models indicated the occurrence of chemical adsorption. The adsorption isotherms of OBS on the soils were better described by the Freundlich model than by the Langmuir model, suggesting that the OBS adsorption sites on the soils were heterogeneous. This is possibly associated with various adsorption mechanisms including hydrophobic, π-π, hydrogen bonding, and electrostatic interactions,further confirmed by the good model fit to the D-R isotherm. Adsorption of OBS occurred on the soils, and the adsorption process was spontaneous and endothermic. In addition, the soils were more suitable for OBS adsorption at lower pH values due to the stronger electrostatic adsorption. The OBS adsorption on the soils decreased with the increase of soil depth from 0 to 30 cm. Moreover, the presence of organic matter and ammonia nitrogen in the soils was favorable for OBS adsorption, and these parameters decreased with increasing soil depth, making OBS adsorption less prominent in the deeper soil. This study indicates that OBS is easily enriched in surface soils, and that soil organic matter and ammonia nitrogen significantly affect OBS migration in soil.     

On the langmuir phosphate adsorption maximum

Abstract

The use of the Langmuir isotherm equation to calculate phosphate (P) adsorption maximum was investigated by studying P adsorption by boehmite (a soil mineral) at pH 3.25, 4.00, and 5.50. This well‐defined simple system was designed to eliminate other influencing reactions and factors in an attempt to study only the adsorption process. The Langmuir adsorption maximum was compared to three other methods (K_d, “concentration null”, and graphical) for determining the value of this constant. There was generally good agreement between methods at the different pH's, except the “concentration null” at pH 3.25 and the Langmuir at pH 4.00. It appears that at least three of the methods (Langmuir included) can be used independently to develop the adsorption envelope, which peaked at pH 4.00. At maximum adsorption, approximately 20% of the surface was covered by P, suggesting monolayer adsorption at specific sites on the surface. Apparently the simple Langmuir isotherm equation, if used correctly, may give valid adsorption maximum values.     

An empirical equation to calculate soil solution electrical conductivity at 25°C from major ion concentrations

The electrical conductivity at 25°C (EC₂₅) of soil solutions or irrigation waters is the standard property for assessing salinity. Many models for soil salinity prediction calculate the major ion composition of the soil solution. The electrical conductivity of a solution can be determined from its composition through several different empirical equations. An assessment of these equations is necessary to incorporate the most accurate and precise equations in such models. Twelve different equations for the EC₂₅ calculation were calibrated by means of regression analyses with data from 133 saturation extracts and another 135 1:5 soil‐to‐water extracts from a salt‐affected agricultural irrigated area. The equations with better calibration parameters were tested with another data set of 153 soil solutions covering a wide range of salt concentrations and compositions. The testing was conducted using the standardized difference t‐test, which is a rigorous validation test used in this study for the first time. The equations based on the ionic conductivity decrement given by Kohlrausch's law presented the poorest calibration parameters. The equations founded on the hypothesis that EC₂₅ is proportional to analytical concentrations had worse calibration and validation parameters than their counterparts based on free‐ion concentrations and ionic activities. The equations founded on simpler mathematical relationships generally gave improved validation parameters. The three equations based on the specific electrical conductivity definition presented a mean standardized difference between observations and predictions indistinguishable from zero at the 95% confidence level. The inclusion of the charged ion‐pair concentrations in the equation based on free‐ion concentrations improved its predictions, particularly at large electrical conductivities. This equation can be reliably used in conjunction with chemical speciation software to assess EC₂₅ from the ion composition of soil solutions.     

恒电荷土壤及可变电荷土壤与离子间相互作用的研究Ⅲ Cu2+和Zn2+的吸附特征

研究了3种典型可变电荷土壤和4种典型恒电荷土壤在不同pH和不同浓度下单纯及共存体系中Cu2 和Zn2 的吸附及其影响因素。结果表明,两类土壤对Cu2 或Zn2 的吸附量均随平衡浓度增加而增大,符合Langmuir吸附等温式;当Cu2 、Zn2 浓度一定时,pH升高使Cu2 、Zn2 吸附量增大,但当pH >5时,Cu2 、Zn2 吸附量随pH变化甚微,出现一个接近最大吸附量的“平台”。当添加Cu2 、Zn2 浓度相同,但二种离子的总浓度不同时,平衡液的Cu2 /Zn2 浓度比均小于1,说明两类土壤对Cu2 的吸附选择性大于Zn2 ,且这种趋势不因pH和离子浓度而改变。当Cu2 、Zn2 共存时,使可变电荷土壤的Zn2 吸附量减小约70 % ,是恒电荷土壤降低量的约1.5倍;可变电荷土壤吸附一个Cu2 或Zn2 时所释放H 的平均数,明显大于恒电荷土壤者,说明可变电荷土壤对Cu2 及Zn2 的吸附中专性吸附的比例较恒电荷土壤大     

镉在土水系统中的迁移特征

本文研究了４种红壤和水体系中镉的迁移特征。结果表明：镉扩散系数Ｄｉ变化在５．７＊１０－８－９．３＊１０＾－７ｃｍ＾２／ｓｅｃ;通过比较单、双表面Ｌａｎｇｍｕｉｒ方程的参数,发现四个土壤的高能位吸附常数远远大于低能位吸附常数,     

蔬菜育苗高压静电吸附播种机理及系统参数优化

针对现有气吸式穴盘育苗播种机对含杂较多且没有丸粒化的不规则小颗粒蔬菜种子存在吸孔堵塞而导致排种精度下降的技术难题,该研究摒弃小孔径、长导程吸孔,设计了一种基于高压静电吸附特性的蔬菜育苗播种机。通过理论分析及电势等值线分布仿真试验确定介电绝缘层材料;构建静电吸附力学模型,明确影响静电吸附力的主要因素及其相互关系,确定影响播种性能的电参数及范围;以型孔加工直径、正向高压静电发生器输出电压和种箱底面倾斜角度为试验因素,以播种合格指数、重播指数和漏播指数为响应指标进行三因素三水平Box-Behnken中心组合试验,得到各试验因素与响应指标间的数学模型,应用 Design-Expert 10.0.4 软件对数学模型进行多目标优化,得到最佳参数组合为：型孔加工直径5.91 mm、正向高压静电发生器输出电压17.67 kV、种箱底面倾斜角度14.69°,此时播种合格指数为91.13%、重播指数为3.02%、漏播指数为5.85%。播种性能验证试验的播种合格指数相较于优化结果降低了0.61%、重播指数相较于优化结果降低了0.17%、漏播指数相较于优化结果增加了0.78%。试验误差在允许范围内,参数优化结果可靠,满足精量播种技术要求。研究结果可为不规则小颗粒蔬菜种子精量播种机械装备的研发提供参考,同时也可为不规则小颗粒物料定量吸附和快速分离方法研究及设备开发提供学术参考。