Testing a mechanistic model. VIII. The effects of time and temperature of incubation on the sorption and subsequent desorption of selenite and selenate by a soil

Several levels of both selenite and selenate were incubated with separate samples of soil for periods of up to 30 d and at temperatures between 5 and 60°C. The concentrations of selenite or of selenate which caused neither desorption nor further sorption–that is, the null-point concentrations–were then measured at 25°C. In addition, the rate of desorption was measured after incubation at 60°C for 10 d. The ability of a mechanistic model to describe the results was tested.
There were large decreases in the null-point concentrations of selenite with both increasing period and increasing temperature of incubation. These effects were modelled as due to a relatively rapid diffusive penetration and a large activation energy for diffusion. Only a small proportion of the sorbed selenite was desorbed within 3 d but, at large solution:soil ratios, desorption appeared to be still continuing. These effects were fairly well predicted by the model applied to the sorption data. For example, the continuing desorption was ascribed to the slow reversal of the diffusive penetration. For selenate, the effects of period and temperature of incubation were much smaller. These effects were modelled as due to a slower diffusive penetration and a lower activation energy. Desorption was quicker and was more nearly complete. According to the model, a large proportion remained in the adsorbed form and was more quickly removed when desorption was induced. It is argued that the behaviour of selenite is consistent with diffusion into a crystal and the large activation energy is required to enable jumps over energy barriers. On the other hand, the lower activation energy for selenate is consistent with diffusion being limited to pores or cracks.
It is suggested that the residual value of selenite fertilizers would decrease because of the continuing reaction, but that this effect would be unimportant for selenate.     

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. 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.     

Testing a mechanistic model. II. The effects of time and temperature on the reaction of zinc with a soil

Samples of a soil were mixed with zinc nitrate solutions and incubated from 1 to 30 days at temperatures from 4 to 60°C. The solution concentration of zinc, which would not have changed on brief mixing with the soil at 25°C, was measured. Background electrolytes for this measurement of null-point concentration were both calcium and sodium nitrate. The effect of the temperature at which null-point concentration was measured was also investigated. After incubation with zinc nitrate, desorption of zinc, and sorption of further zinc, were measured. Null-point concentration of zinc decreased with increasing period of incubation, with the rate of decrease greatest at high temperatures of incubation. The effects of both temperature and time were closely described by a model which postulated an initial rapid adsorption of ZnOH⁺ ions onto heterogenous charged surfaces, followed by a diffusive penetration. Increasing the temperature of incubation increased the rate of diffusive penetration and led to low solution concentrations. In contrast, increasing the temperature at which null-points were measured increased the concentration of ZnOH⁺ ions. This was shown to be consistent with a change in position of the equilibrium of the initial, rapid, adsorption reaction. Curves for desorption of zinc were continuous with curves for sorption of further zinc, but neither desorption nor further sorption coincided with the position of the curves relating retention of previously added zinc to concentration. This result was consistent with the model and occurred because desorption must reverse diffusive penetration. However, the model under-predicted the magnitude of both desorption and sorption of further zinc. Desorption in calcium solutions was greater than in sodium solutions, even when the solution concentration of zinc approached zero. This was consistent with exchange diffusion of calcium ions for some of the penetrated zinc.     

Testing a mechanistic model. I. The effects of time and temperature on the reaction of fluoride and molybdate with a soil

A mechanistic model that had been developed to describe the reaction of phosphate with soil was applied to the reactions of fluoride and molybdate with soil. The model assumes that: there is an initial adsorption reaction between ions and charged surfaces; that the surfaces are not uniform in their properties; and that the initial adsorption is followed by diffusive penetration. The model was developed beyond that previously published to permit the rate of the initial adsorption reaction to be included. The model reproduced the effects of solution concentration, and of increasing period and temperature of incubation, on the retention of both fluoride and molybdate. Increasing the temperature of incubation increased the retention, or decreased the solution concentration, and this was reproduced by the effect of temperature on the rate of diffusive penetration. Desorption of fluoride was also reproduced. This supports the argument that slow desorption is mostly due to the need to reverse the diffusive penetration. After incubation at constant temperature, increasing the temperature at which solution concentration of molybdenum was measured, increased the concentration. The direction of this effect of temperature was also reproduced. It arises because of the effect of temperature on the position of the equilibrium between adsorbed molybdate (in the strict sense of the term) and molybdate in solution.     

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.     

Testing a mechanistic model. VI. Molecular modelling of the effects of pH on phosphate and on zinc retention by soils

Both phosphate and metal cations such as zinc can be retained by oxides of iron and aluminium. Yet the phosphate-retaining and zinc-retaining materials in soil appear to differ in their behaviour from that of pure oxides of iron and aluminium. In most soils, the electrostatic potentials of retaining materials appear to be negative at normal soil pH values. The changes in potential with pH, and consequent change in retention, also appear to differ from those of pure oxides. A model of a pure oxide was modified in an attempt to simulate the observed behaviour of soil. The most effective modification was to include a negative charge in the oxide. Such a charge could have arisen from solid–state diffusion of anions into the oxide, or by close association with permanently charged clays. The inclusion of this charge changes the direction of the effect of pH on phosphate retention. If the amount of negative charge is large enough, the paradoxical situation can arise in which the potential of a ‘variable-charge’ surface is not affected by pH. This is consistent with observed effects of pH on zinc retention by soils.     

Testing a mechanistic model. XI. The effects of time and of level of application on isotopically exchangeable phosphate

A model for the reaction of ions with soil was improved to permit time trends to be followed at a given level of phosphate addition. Difference equations were also developed to describe the rate of reaction of ions with both vacant sites and occupied sites, while diffusive penetration of the surface was occurring. The model was applied to data for the effects of time and of level of application on exchangeable phosphate. Many of the observed values for isotopically exchangeable phosphate could be well-described if it was assumed that equilibration of ³²P with surface sites was very rapid and this was followed by a diffusive penetration into the adsorbing particles. However, for short periods of contact between soil and ³²P, it was necessary to also take into account the rate of the reaction between ³²P and surface sites. This reaction was largely with vacant sites. Reaction with occupied sites–that is, true exchange–was unimportant. It is suggested that the electric potential of the surface may determine whether reaction is with occupied or vacant sites. In contrast to reaction of ³²P with occupied sites, reaction with vacant sites involves a net transfer of charge. Reaction with vacant sites would be slow if the potential was large and negative. It is shown that when reaction with vacant sites is slow, the proportion of previously added ³¹P recorded as exchangeable increases with level of addition of ³¹P. This may explain published observations of slow and non-linear exchange in some soils.     

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.     

不同价态外源硒对小白菜生长及养分吸收的影响

采用土壤外源加入两种不同价态的硒 [Se(Ⅳ)和 Se(Ⅵ)]的盆栽试验,研究了其对小白菜生长、营养元素和硒吸收的影响。结果表明,施硒对小白菜的生长均表现出低浓度(5 mg/kg)促进,高浓度(5 mg/kg)抑制趋势。Se(Ⅵ)处理小白菜地上部硒含量大于地下部;而Se(Ⅳ)处理则与Se(Ⅵ)相反。硒从根部转运到地上部的转移因子Se(Ⅵ)处理大于Se(Ⅳ)。两种价态硒处理,小白菜对氮、磷、钾、硫、镁和锌的吸收也表现出低浓度时为促进作用,高浓度为抑制作用。Se(Ⅵ)显著增加了钙的吸收,Se(Ⅳ)却无显著影响;Se(Ⅳ)和Se(Ⅵ)均能促进小白菜对铁的吸收。相同浓度下, Se(Ⅵ)对各个营养元素吸收的影响显著大于Se(Ⅳ)。综合硒对生长和养分吸收的影响看出,小白菜施硒量以Se(Ⅵ)不超过2.5 mg/kg或Se(Ⅳ)不超过5 mg/kg为宜。     

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.     

Effects of different application methods of selenite and selenate on selenium distribution within wheat

Abstract

The objective of this sand culture experiment was to determine how fertilization methods (i.e., fertigation rates of 0.5, 1, and 2?mg Se·pot^?1, foliar rates of 5, 10, and 20?mg Se· L^?1) and fertilizer type (i.e., selenate or selenite) affected wheat Se concentrations. The results showed that the fertigation and foliar treatments both increased wheat Se content. In the fertigation and foliar treatment total Se content of wheat was greatest in the selenate treatments. In the fertigation treatment, the Selenite had mainly accumulated in the roots, while the Selenate was majority transported to shoot. In the foliar treatment, we found that most of Se was transported to grain. In addition, the organic Se concentration was the most than other Se fractions. In conclusion, selenate was more effective than selenite in both the fertigated and the foliar application treatments. And the foliar application was better than fertigation.     

Chemical effects of pH 3 sulphuric acid on a soil profile

Cores of podzolic soil (monolith lysimeters) were treated for 4.8 yr with 1500 mm yr^?1 of either 0.5 mM H₂SO₄ at pH 3, equivalent to 24 g S m^?2 yr^?1 (acid treated) or distilled water (controls). The acid treatment was about 37 times greater than the average annual input of H₃O⁺ from rain at the site from which the monoliths were taken. Acid treatment acidified the litter (from pH(CaCl₂)3.4 to pH(CaCl₂)2.6) and the mineral soil to a depth of 80 cm (mean pH(CaCl₂) decrease of 0.2 unit). In the litter and upper A horizon, ion-exchange reactions provided the main neutralizing mechanism, resulting in a decrease in the reserves of extractable (in 2.5 % acetic acid) Ca, Mg, and Mn of about 70 to 80 %. Dissolution of solid phase Al from hydrous oxides provided most neutralization below this depth. Al3⁺ was the principal soluble Al species throughout the profile. In the litter and upper A horizon, some of the mobilized Al³⁺ was retained on cation exchange sites resulting in an increase in exchangeable Al. Deeper in the profile, where the exchange sites were effectively saturated with Al³⁺, no increase in exchangeable Al occurred, and Al³⁺ was, therefore, available for leaching. Some reversible adsorption of SO₄ ^2?, associated with hydrous Al oxides, occurred in the Bs and C horizons. The results are discussed in relation to possible effects of acid deposition over regions of Europe and N. America.     

Influence of electrolyte composition and pH on cadmium sorption by an acid sandy soil

Extraction of soil with CaCl₂, has been recommended as a measure of bioavailability of heavy metals. Interpretation of soil extraction data in terms of plant uptake potential may improve when the chemical behaviour of heavy metals in these extracts is ascertained. The effect of pH, Cd complexation by Cl, and competition between Cd and Ca on Cd sorption was studied at an ionic strength of 0.03 m . Sorption of cadmium was measured in 0.01 m CaCl₂, in 0.01 m Ca(NO₃)₂, in a mixture of 0.02 m NaCl and 0.01 m NaNO₃, and in 0.03 m NaNO₃, at different values of pH ranging from 3.8 to 4.9. Adsorption isotherms were all linear, with a negative intercept on the y-axis. This intercept indicated (linear) desorption of only part of the initial soil Cd content. About 50% of the Cd in solution was complexed in the presence of 0.02 m Cl at ionic strength of 0.03. Due to competition between Cd and Ca, sorption of Cd was reduced by 80% in the Ca-electrolytes as compared with the Na-electrolytes. Sorption was highly sensitive to pH as each 0.5 unit increase in pH resulted in twice as much sorption of Cd. An empirical factor in the sorption equation that accounts for this effect of pH showed a similar response to changes in pH as a mechanistic factor. This mechanistic factor was developed by assuming that Cd and protons sorb onto the same sites and that a two-site Langmuir sorption isotherm for protons was able to describe the titration curve of the soil. This similarity may explain the successful application of the empirical factor in this and previous studies.     

酸碱调控对泥浆反应去除土壤中多环芳烃的影响研究

采用摇瓶试验模拟研究了酸碱调控对泥浆反应去除污染土壤中多环芳烃的影响,结果表明,泥浆反应对污染土壤中的多环芳烃具有一定的去除效果,长期污染土壤中多环芳烃的去除率为10.6% ~ 20.7%,模拟污染土壤中的去除率为37.4% ~ 42.1%;酸碱调控对不同性质的多环芳烃的去除影响不同,整体上看,酸性条件有利于高环（五环和六环）多环芳烃的去除,而中性条件有利于低环（三环和四环）多环芳烃的去除。在实际修复中,根据污染土壤中多环芳烃的组成进行适当的酸碱调控,可以促进污染土壤的快速修复。     

The effects of time of incubation on the relation between charge and pH of soil

Samples of two Andisols and two Ultisols from southern Chile were incubated with acid or with lime for up to 60 d at 25°C or for 1 day at 40°C or at 60°C. The changes in positive and negative charge were measured. The Andisols reacted slowly at 25°C. They lost protons to the solution at high _pH, thus increasing the negative charge on the soils and decreasing the pH of the solution. They gained protons at low _pH, thus increasing the positive charge on the soils and increasing the _pH of the solution. The Ultisols reacted more quickly but again charge and _pH changed through time. For all samples, the rate of reaction was increased by incubating at 60°C. Brief incubation at 60°C produces a similar relation to that obtained after longer incubation at 25°C. This provides a convenient means by which measurements can be made more quickly.     

The effects of cations and pH on the phosphatase activity of a mixed enzyme system extracted from soil microorganisms

Enzymes extracted from soil microorganisms exhibited activity with a number of inorganic phosphate substrates. Maximum hydrolysis of sodium and ammonium polyphosphates took place at about pH 8.5 in the presence of magnesium or manganese. Optimum cation concentrations were 2 mM for magnesium and 0.8 mM for manganese. Calcium inhibited both magnesium and manganese activation and was itself a non-activator, but an increase in the amounts of magnesium and manganese beyond their optimum concentrations reduced the inhibitory effects of calcium. There was a decrease in the rate of enzymatic hydrolysis as chain length of the polyphosphates increased, but the substrate cation had no effect.     

A mechanistic model for describing the sorption and desorption of phosphate by soil

A model of phosphate reaction is constructed and its output compared with observations for the sorption and desorption of phosphate by soil. The model has three components: first, the reaction between divalent phosphate ions and a variable-charge surface; second, the assumption that there is a range of values of surface properties and that these are normally distributed; third, the assumption that the initial adsorption induces a diffusion gradient towards the interior of the particle which begins a solid-state diffusion process. The model closely describes the effects on sorption of phosphate of: concentration of phosphate, pH, temperature, and time of contact. It also reproduces the effects on desorption of phosphate of: period of prior contact, period and temperature of desorption, and soil: solution ratio. The model is general and should apply to other specifically adsorbed anions and cations. It suggests that phosphate that has reacted with soil for a long period is not ‘fixed’ but has mostly penetrated into the soil particles. The phosphorus can be recovered slowly if a low enough surface activity is induced.