Testing a mechanistic model. VII. The effects of pH and of electrolyte on the reaction of selenite and selenate with a soil

The pH of samples of a soil was altered by mixing them either with acid or lime, and incubating the moistened samples at 60°C for a day. The sorption of selenate and of selenite was then measured using as background electrolytes, 0.01 M, 0.1 M and 1.0 M sodium chloride and also 0.01 M calcium chloride. The results were compared with previous studies with phosphate and fluoride. Selenite was sorbed more strongly than selenate, but not as strongly as phosphate or fluoride. Sorption of both selenite and selenate decreased with increasing pH. This decrease was more marked for selenate than for selenite; more marked in a sodium system than in a calcium one; and more marked with a dilute background electrolyte than a concentrated one. Under certain conditions, the steeper curves for the dilute electrolyte crossed the curves for the concentrated electrolyte giving points of zero salt effect. For selenite, these points of zero salt effect occurred near pH 6 and the greater the sorption the lower the pH for zero salt effect. For phosphate, the analogous value was near pH 5. For selenate, if a point of zero salt effect occurred, it was at such a high pH and such a low amount of sorption that it could not be measured. Thus, the larger the amount of sorption the lower the pH for the point of zero salt effect. This generalization applied both within and between different kinds of sorbates. The results were closely described by a model that had previously been applied to phosphate and fluoride. The model postulates that ions react with charged surfaces. The electric potentials of the reacting surfaces are affected by the identity and concentration of the background electrolyte and this produces the interactions between pH and electrolyte concentration. The model also postulates that there is a distribution of electric potentials. Anions react with surfaces which occur in the more positive tail of this distribution. The smaller the amount of the reaction the more positive the potential of the reacted surface and, therefore, the higher the pH required to decrease this potential to zero.     

Testing a mechanistic model. X. The effect of pH and electrolyte concentration on borate sorption by a soil

Borate sorption by a soil was measured with 0.01, 0.1, or 1.0 M sodium chloride as background electrolyte and samples of soil with a range of pH values achieved by incubating with either calcium carbonate or hydrochloric acid for 24 h at 60°C.
Borate sorption generally increased with increasing pH. The more concentrated the electrolyte, the steeper the increase. At low pH, increasing the salt concentration decreased borate sorption; at high pH, it increased sorption. There was an intermediate pH at which salt had no effect on borate sorption. The point of zero salt effect on borate sorption was at a higher pH than the point of zero salt effect on pH. This result was explained by a mechanism in which borate ions react with variable charge surfaces which are heterogeneous and for which part of the heterogeneity is in the electric potential of the surfaces. It cannot be explained by mechanisms which do not take into account the effects of the electric potential of the reacting surfaces on the reaction with borate ions. Although the behaviour of borate was broadly consistent with that of other anions, it differed in that about half of the heterogeneity had to be allocated to the binding constant for borate ions. It was suggested that this was because reaction with organic matter was more important for borate than for other anions.     

Testing a mechanistic model. V. The points of zero salt effect for phosphate retention, for zinc retention and for acid/alkali titration of a soil

The pH of samples of a soil was altered by adding acid or lime and incubating the moistened soil at 60°C. The effect of varying the concentration of salt on pH, retention of phosphate, and retention of zinc was then measured. At low pH, increasing the concentration of salt decreased phosphate retention; at high pH, it increased it. The pH at which the effects crossed over (that is, the point of zero salt effect on phosphate retention) was higher than the point of zero salt effect on pH. This is opposite to effects observed with uniform surfaces. These results were described by a model in which it was assumed that individual sites varied in their electrostatic potential and that phosphate was retained preferentially by sites with the highest potential. Zinc retention was decreased by high concentrations of salt. This was partly because of effects of salt in decreasing the pH of solutions in contact with soil. There was no indication of a crossing-over of effects at low pH. This suggested that the electrostatic potential of zinc-retaining sites did not vary much with pH.     

Effect of liming on phosphate sorption by acid soils

The sorption of phosphate (P) by four strongly acid Fijian soils from 0.01 M CaCl₂ decreased with increasing pH up to pH 5.5–6.0 and then increased again. The initial decrease in P sorption with increasing pH appears to result from an interaction between added P, negative charge, and the electrostatic potential in the plane of sorption. The results of a sorption study, involving KCl or CaCl₂ of varying concentrations as the background electrolyte and using Nadroloulou soil incubated with KOH or Ca(OH)₂, suggested that the increase in P sorption at pH values > 6.0 was caused by the formation of insoluble Ca-P compounds. For some soils this is consistent with the results of an isotopic-exchange study in which incubation with lime caused marked reductions in the amounts of exchangeable P at high pH.     

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.     

Influence of phosphate sorption on dispersion of a Ferralsol

Abstract

Soil dispersion induces soil erosion and colloidal leaching. Nutrients are lost at the same time and this causes water contamination. Phosphate is an essential element for living organisms. Because phosphate influences soil dispersion and it is an important limited resource, this influence must be evaluated well in order to diminish negative effects on soil structure. In this paper, we firstly evaluated the influence of phosphate sorption on soil dispersion by calculating repulsive potential energy between soil particles. Ferralsol, which is a typical soil in rainy tropical regions, was used as the material. The dispersion-flocculation phenomena were investigated with absorbance of soil suspension under different pH, phosphate adsorption and electrolyte concentration in an Na-NO₃-PO₄ system. The repulsive potential energy was calculated based on the diffuse double layer theory and the measured zeta potential. We indicated that the measured absorbance increased with the increase of the repulsive potential energy. The repulsive potential energy increased with increasing phosphate sorption up to about 5 to 20 mmol kg^?1 at all pH, and it induced the soil dispersion, because phosphate sorption increased the negative charge of the soil. After its peak, it decreased with increasing phosphate sorption because the electrolyte concentration increased and the electrolyte screened the electric field near the soil surface. The repulsive potential energy also increased with increasing pH because of the increase of the negative charge of the soil. Even at low pH, after a certain amount of phosphate sorption, the soil dispersed due to the increase of repulsive potential energy, although the soil flocculated before phosphate application. Because the soil dispersion causes soil and phosphorus loss, the influence of soil pH and phosphate sorption on the soil dispersion should be considered for good soil management.     

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.     

Amendment of drilling fluid-affected soils with calcium salts

Land disposal of waste drilling fluid is an environmental concern because of the high salt content and the presence of potential toxic elements. A water-based drilling fluid was tested in a laboratory column study to determine the feasibility of leaching excessive salt without mobilizing chromium (Cr). The drilling fluid-affected two Alfisols with similar mineralogy, acidity, and texture were treated with gypsum (CaSO₄ · 2H₂O), calcium carbonate (CaCO₃), or calcium phosphate (CaHPO₄) (0 to 2% of weight). The electrical conductivity (EC) increased and the sodium adsorption ratio (SAR) decreased with increasing Ca-salt concentration. The pH did not vary significantly with the changes in the concentrations of gypsum and calcium phosphate. The pH of the mixtures increased in proportion to the concentration of added calcium carbonate. The hydraulic conductivity increased and the mobility of the soil particles decreased with increasing Ca-salt concentration. The Cr mobility decreased by gypsum and CaCO₃ treatments but it increased by calcium phosphate treatment. The soil with a higher content of organic matter and cation exchange capacity (CEC) showed a higher hydraulic conductivity and lower Cr mobility than the other soils at the same levels of the treatment. The results of this study suggest that the amendment of drilling fluid-affected soils with CaCO₃ and gypsum can enhance the leaching of excessive salt and reduce the Cr mobility. Among loamy soil, those with a higher CEC and organic matter content are more suitable for land disposal of drilling fluid.     

Salt effect on the pH profile and kinetic parameters of microbial phytases

The pH profiles of two microbial phytases were determined using four different general purpose buffers at different pH values. The roles of calcium chloride, sodium chloride, and sodium fluoride on activity were compared in these buffers. For Aspergillus niger phytase, calcium extended the pH range to 8.0. A high concentration of sodium chloride affected the activity of fungal phytase in the pH 3-4 range and shifted the pH optimum to 2.0 from 5.5 in Escherichia coli phytase. As expected, both of the microbial phytases were inhibited by sodium fluoride at acidic pH values. Because the Km for phytate increased nearly 2-fold for fungal phytase while Vmax increased about 75% in a high concentration of sodium chloride, it is possible that salt enhanced the product to dissociate from the active site due to an altered electrostatic environment. Modeling studies indicate that while the active site octapeptide's orientation is very similar, there are some differences in the arrangements of alpha-helices, beta-sheets, and coils that could account for the observed catalytic and salt effect differences.     

Effect of pH on Zinc Sorption–Desorption by Soils

The objective of this study was to examine the effect of soil pH on zinc (Zn) sorption and desorption for four surface soils from the Canterbury Plains region of New Zealand. Zinc sorption by the soils, adjusted to different pH values, was measured from various initial solution Zn concentrations in the presence of 0.01 M calcium nitrate [Ca(NO₃)₂]. Zinc desorption isotherms were derived from the cumulative Zn desorbed (µg g^?1 soil) after each of 10 desorption periods by sequentially suspending the same soil samples in fresh Zn‐free 0.01 M Ca(NO₃)₂. Zinc sorption and desorption varied widely with soil pH. Desorption of both native and added Zn decreased continuously with rising pH and became very low at pH values greater than 6.5. The proportion of sorbed Zn that could be desorbed back into solution decreased substantially as pH increased to more than 5.5. However, there were differences between soils regarding the extent of the hysteresis effect.     

Effect of ph on amount of phosphorus extracted by 10 mm calcium chloride from three Rothamsted soils

Abstract

Three silty clay loams from the classical field experiments at Rothamsted Experimental Station (UK) with low phosphorus (P) status were treated with phosphate fertilizer and incubated for 15 days at field capacity with added acid [hydrochloric acid (HCl)] or base [sodium hydroxide (NaOH)] to give pH ranges measured in 1:5 suspensions of soil in 10 mM calcium chloride (CaCl₂) of 6.3–8.7 (Hoosfield A, pH 8.2), 3.8–8.2 (Hoosfield B, pH 6.3), and 2.8–7.1 (Geescroft, pH 5.3). Extractable ? was measured by the 10 mM CaCl₂ extraction procedure. For the Hoosfield ? and Geescroft soils without added phosphate fertilizer, extractable ? was decreased at both ‘low’ and ‘high’ pH values, the maximum being at about 5.4 in both soils. In the calcareous Hoosfield soil, extractable ? decreased with increasing pH over the range studied. These changes in extractable ? were magnified in soils treated with phosphate fertilizer but the maxima and trends were unaltered. The results indicate that native soil ? appears to be changed by pH in the same way as added ? to the soil. In the calcareous Hoosfield A soil, added acid did not reduce soil pH to less than 6.4 (because of its high buffer capacity) and so the pH level for maximum ? solubility was not found.     

Influence of induced salinity and sodicity on manganese sorption in vertisols and aridisols

Abstract

Salinity and sodicity effects on manganese (Mn) sorption in a mixed sodium‐calcium (Na‐Ca) soil system were studied. Soil samples were taken at 0–30 cm depth from Vertisols (El‐Hosh and El‐Suleimi) and Aridisols (El‐Laota) at three sites in Gezira scheme (Sudan). No Mn was applied to these soils. Prior to analysis the soils were equilibrated with NaCl‐CaCL₂ mixed salt solutions to attain SAR values at different salt concentrations. The results indicated that saline soils sorbed less Mn and had higher equilibrium Mn concentrations. Sodic soils retained more Mn but had low equilibrium concentrations. Sodicity had a pronounced effect only on increasing Mn retention at higher SAR values. Salinity tended to alleviate sodicity effects on Mn retention, but soluble salts that increased soil pH decreased Mn concentration.     

氧化还原条件对土壤磷素固定与释放的影响

为探讨水稻土由氧化环境转为还原条件时对土壤磷素固定与释放的影响,选择18种水稻土样品进行室内模拟实验,通过测定不同条件下磷的等温吸附曲线和采用氧化铁试纸测定法进行多次提取以对比淹水前后土壤磷的累计解吸量,发现大部分供试样品的固磷能力在淹水条件下有了显著的提高,全部样品在淹水后磷的释放量都有不同程度的减少。进一步的研究表明淹水条件下土壤对磷的固定与释放的变化主要与淹水后土壤Eh的降低和pH的升高而导致的大量无定形铁的形成有关。     

The effects of pH and chloride concentration on mercury sorption. II. By a soil

The pH of a soil was altered by incubation with either acid or lime, and the sorption of mercury was measured in the absence of chloride and at three chloride concentrations. In the absence of chloride there were only small effects of pH on sorption between pH 4 and 6; sorption decreased at higher pH. Addition of chloride decreased sorption at low pH but had little effect on sorption at high pH. Consequently, in the presence of chloride, sorption increased with increasing pH between pH 4 and 6 and then decreased. Many of the mercury sorption curves were sigmoid. This was explained by assuming that a small amount of complexing material was present in the solution after mixing with the soil. Calculation of the mercury species present in solution was made difficult by uncertainties about the postulated complexing material. Nevertheless, between pH 4 and pH 5.8, it was possible to explain the effects of pH and of chloride concentration on sorption as entirely due to changes in the HgOH⁺ concentration.     

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。     

Phosphate sorption in some representative soils of Bangladesh

An experiment was conducted to observe the phosphate sorption potential of some soils of Bangladesh. Three soil series of calcareous origin, namely Sara (Aquic Eutrochrept), Gopalpur (Aquic Eutrochrept) and Ishurdi (Aeric Haplaquept), and two soil series of non-calcareous origin, namely Tejgaon (Rhodic Paleustult) and Ghatail (Aeric Haplaquept), were selected. The soils were equilibrated with dilute solution of calcium chloride containing graded concentrations of phosphate (0, 1, 2, 5, 10, 25 and 50?μg?P?mL^?1), and the amount of phosphate sorbed or desorbed was determined. Although all the soils showed potential for sorbing phosphate from applied phosphorus, their ability to sorb phosphorus differed. Increasing rates of phosphate application increased the amount of P sorption but reduced phosphate sorption percentage in all soils except Tejgaon. Phosphate was sorbed by the soils in the order: Tejgaon > Ghatail > Ishurdi > Gopalpur > Sara at 50?μg?P?mL^?1 application. Soils possessing higher amounts of free iron oxide and clay sorbed more phosphate from applied phosphorus.     

Soil pH on mobility of imazaquin in oxisols with positive balance of charges

The influence of soil pH on the leaching potential of the ionizable herbicide imazaquin was assessed on the profile of two highly weathered soils having a net positive charge in the B horizon, in contrast to a soil having a net negative charge in the whole profile, using packed soil column experiments. Imazaquin leached to a large extent and faster at Kd values lower than 1.0 L kg(-1), a much more lenient limit than usually proposed for pesticides in the literature (Kd < 5.0 L kg(-1)). The amount of imazaquin leached increased with soil pH. As the soil pH increased, the percentage of imazaquin in the anionic forms, the negative surface potential of the soils, as well as imazaquin water solubility also increased, thus reducing sorption because of repulsive electrostatic forces (hydrophilic interactions). For all surface samples (0-0.2 m), imazaquin did not leach at soil pH values lower than pKa (3.8) and more than 80% of the applied amount was leached at pH values higher than 5.5. For subsurface samples from the acric soils, imazaquin only began to leach at soil pH values > zero point of salt effects (ZPSE > 5.7). In conclusion, the use of surface K(oc) values to predict the amount of imazaquin leached within soil profiles having a positive balance of charges may greatly overestimate its actual leaching potential.     

pH对土壤吸持磷酸根的影响及其原因

本文选择了浙江、江苏15个性质变化范围较大的土壤样品,研究在两种支持电解质、不同pH条件下对磷酸根的吸持反应。结果表明,加碱提高强酸性土壤的pH值,导致交换性铝的水解和羟基铝聚合物的生成,增加对磷的吸持。磷酸根同酸性土壤的反应,可促进交换性铝的水解,释放出H⁺,降低体系的pH。在CaCl₂介质中,当pH>6时,可能有磷酸钙类盐形成,使溶液中磷浓度显著降低。有机质对土壤吸持磷有重要影响。在低pH下有机质通过与Al³⁺形成络合物,阻碍溶液中A1³⁺的水解,并与磷酸根竞争羟基铝化合物表面的反应点位,从而降低酸性土壤对磷酸根的吸附量。     

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.     

Testing a mechanistic model. IV. Describing the effects of pH on zinc retention by soils

Samples of two soils were incubated at 60°C for 24 h with several levels of either calcium carbonate or hydrochloric acid. Zinc retention was then measured on subsamples of the treated soil over 24 h at 25°C. The results were compared with published experiments (Bar-Yosef, 1979; Harter, 1983) in which zinc retention was also measured over a range of concentrations and pH values, but using different experimental conditions. Zinc retention increased as pH increased. In all cases, this effect could be described by assuming that the ZnOH⁺ ion was retained and the effect of pH was due to the increased proportion of this ion in solution. Over most of the pH range it was not necessary to assume any contribution from a decrease in the electrostatic potential of the reacting surfaces with increasing pH. This contrasts with the effects of pH on phosphate and fluoride retention and suggests that the materials that react with zinc differ from those that react with anions. The shape of plots of zinc retention against ZnOH⁺ concentration was reproduced using a model in which it was assumed that there was a range of values of electrostatic potential. A similar model had previously been used for anions. Zinc would tend to react with the most negative end of this range and phosphate with the least negative end. This further suggests that zinc and anions may react with different materials.