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1.
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.  相似文献   

2.
Modelling the effects of pH on phosphate sorption by soils   总被引：4，自引：0，他引：4  
Samples of six soils were incubated at 60°C for 24 h with several levels of either calcium carbonate or hydrochloric acid. Phosphate sorption was then measured on sub-samples of the treated soils over 24 h at 25°C. In one set of measurements on all soils, 0.01 M calcium chloride was used as the background electrolyte. In another set, on two soils, 0.01 M sodium chloride was used. An interpolation method was used to give points on the three-dimensional surface relating the final pH of the suspensions to sorption of phosphate at specified solution concentrations of phosphate. The effects of pH on phosphate sorption differed between soils. For unfertilized soils, increases in pH up to about pH 5.5 decreased sorption. Further increases in pH decreased sorption further in one soil and increased it in three others. For fertilized soils, measured sorption increased with pH. When sodium chloride was used instead of calcium chloride, there was a more marked trend for sorption to decrease as pH increased. Differences between the soils were ascribed to differences in two soil properties. One was the rate at which the electrostatic potential in the plane of adsorption decreased as pH increased. Only small differences in the rate of change of potential were needed to reproduce the observed differences between soils. The electrostatic potential would decrease more quickly in solutions of a sodium salt than in solutions of a calcium salt and this explains the observed differences between these media. The other soil property that affected observed sorption was the release of phosphate from the soil. The amount released was largest at low pH. Consequently, for fertilized soils, measured sorption increased with pH.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
Abstracts

Three anion (selenite, phosphate, and fluoride) sorption, and the concomitant release of silicate, sulphate, and organic matters from soils, and proton consumption with sorption were investigated using two andosols in Japan. The following sequence of sorption by the andosols was, fluoride (F) >> phosphate (P) > selenite (Se); concomitant proton consumption with sorption, F >> P > Se; organic matter released, P > Se > F; and sulfate released, P > Se >> F. There was quite a difference between an allophanic and a non‐allophanic andosols in silicate released with anion sorption. Our results suggest that the fluoride sorption mechanism is different from the others and that surface sites with OH groups for inner‐sphere complexes with selenite on soil particles which are restricted as compared to phosphate and fluoride.  相似文献   

6.
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.  相似文献   

7.
《Geoderma》1994,63(1):43-52
The sorption of selenite by two allophanic soils containing high amounts of variable charge materials was studied. Selenite sorption exhibited a maximum near pH 4 and decreased, although not proportionally, with increasing pH. Only negligible amounts of selenite were sorbed above pH 7.In the two soils, the addition of selenite caused a release of sulphate (SO2−4), silicate (Si) and hydroxyl ion (OH−) and an increase in cation (Na+) adsorption. No measurable amount of phosphate (P) was released. Increase in negative charge as measured by Na+ adsorption accounted for 48 and 18% of selenite sorbed (soils 1 and 2, respectively), the rest being accounted for by release of anions. The results presented here are consistent with the widely held view that selenite and phosphate are sorbed onto variable charge surfaces by a similar mechanism (ligand exchange).  相似文献   

8.
The effect of a foliar spray of selenium on potatoes was investigated for 2 years. Amounts of 0, 50, and 150 g of Se ha(-)(1) were applied both as sodium selenate and as sodium selenite in water, either pure or with the addition of 0.15% of soluble leonardite as a source of humic acids (pH 7). Tuber selenium concentration increased with the application levels, both with sodium selenate and with sodium selenite, when only aqueous solutions were used. When humic acids were added, the tuber selenium level rose more markedly after the application of sodium selenate as compared to the case of the aqueous solutions; however, in the case of sodium selenite, the level showed a large increase only after the application of 50 g of Se ha(-)(1). Kinetics showed that humic acids raised the selenate availability, but no differences were found in the distribution of selenium in the tuber fractions. Foliar application of selenium with humic acids was proven to be a good way to increase the selenium content of potatoes, but the assimilation process of selenium was simpler with selenate than with selenite.  相似文献   

9.
Solutions of phosphate and of selenite were gently mixed with a soil, both separately and in combination, for periods ranging from 15 min to 30 days. For both anions, the solution concentration continued to decrease throughout the period, but the decrease was more marked for phosphate. Competitive effects were smallest after brief periods of mixing, and increased with time. Phosphate was a more effective competitor for sorption than selenite, and its competitive advantage increased with time. The observed effects were closely described by a mechanistic model. According to the model, competition was largely through changes in the electric potential of the surface rather than through decreases in the number of vacant adsorption sites. This explained why competition effects were initially small. This was especially so for phosphate, which was modelled as having a marked continuing diffusive penetration of the surface. The decrease in electric potential associated with that penetration decreased the surface concentration of selenite and so decreased the rate of penetration of selenite. By the end of the experiment this was the most important aspect of the competitive effect of phosphate on selenite.  相似文献   

10.
Laboratory experiments were carried out to evaluate the effect of pH, ionic strength and electrolyte composition on zinc sorption–desorption by two Andepts from the Canary Islands (Spain). At the natural soil pH, the soils exhibited little net negative surface charge and small Zn sorption capacities. More than 75% of the sorbed Zn was apparently strongly bonded. The pH greatly influenced the sorption–desorption reactions. Sorption increased with increasing pH, and retention increased abruptly at pH > 6.0. Sorption also occurred at pH values below the point of zero charge (PZC) of the soils, when most of the surface sites are positively charged. Desorption decreased continuously with rising pH and became a trace at pH > 6.0. An increase in the ionic strength of the background electrolyte decreased Zn sorption and enhanced the amount of sorbed metal that could be subsequently released. In the two soils, Zn sorption diminished somewhat in the K and Ca electrolytes as compared with the Na electrolyte. However, this did not happen at small Zn loadings. Desorption was not affected by the type of electrolyte and cation used. The results are consistent with chemisorption being responsible for most of the sorption. The results also suggested a strong affinity sorption or even precipitation at high pHs.  相似文献   

11.
Abstract

Single point phosphate sorption curves effectively estimated phosphate fertilizer requirements while requiring less work than multiple point curves. Correlation coefficients of 0.961 and 0.981 were obtained when phosphate rates, estimated using single point curves, were compared with those from multiple point curves. Reducing the ionic strength of the supporting electrolyte solution by using 0.001 M CaCl2 or water rather than 0.01 M CaCl2 during equilibration increased dissolved inorganic phosphate 73% and 141% on the average thus improving analytical precision. The relative effects of salt concentration were sufficiently independent of pH and phosphorus concentration to suggest that a simple conversion factor can be used to convert external P requirements from one set of equilibrium conditions (salt concentration) to another.  相似文献   

12.
Sorption of phosphate by hydrous oxides of aluminium was studied as a function of pH, presence of chelates of aluminium and of the specific surface areas of the oxides. Aluminon was most effective in reducing P sorption followed by oxalic acid and EDTA. Acetylacetone, 8-hydroxyquinoline, salicylic acid and fluoride affected little P sorption. The sorption was found to be higher the higher the value of the specific surface area of the oxide, but the shape of the sorption curve was the same for all the oxides studied, exhibiting a maximum at about pH 5. This maximum was found to coincide with the point of zero charge as determined in the presence of acetate ions. The sorption data are explained in terms of a ligand exchange mechanism in which phosphate chemisorbs on surface aluminium atoms displacing uncharged surface hydroxyls.  相似文献   

13.
Abstract

The adsorption of selenium (Se) in the selenate form and its desorption by phosphate in four soils with different physiochemical properties were studied in the laboratory. To determine adsorption isotherms for selenate 25 mL of solutions containing 1 to 100 ppm of Se were added to 2.5 g of soil. Desorption isotherms were determined by resuspending the samples in phosphate solution. The selenate sorption process was adequately described by the Freundlich equation. In pine forest and woodland soils, characterized by the highest organic matter content and cation exchange capacity (CEC) values, the isotherms were classified as L type, since the amount of Se sorbed appeared to move towards saturation. The organic matter content played the most important part in the adsorption of Se, while pH appeared to have a small effect on the ability of the soil to adsorb Se. The high CaCO3 content of the pine forest soil may have contributed in increasing the Se adsorption notwithstanding the high pH value. The cultivated and arable soils showed a reduced sorption capacity. The sorption could be described by an S type curve. At low concentrations of Se the affinity of the solid phase was less than that of the liquid phase. By increasing the concentration of Se in solution, the affinity of the solid phase increased and the sorption was favored. Selenate desorption by water was negligible, whereas the amount of Se desorbed by phosphate varied among the different soils. The desorption experiments indicated that a significant portion of the sorbed Se was irreversibly retained. This suggests the existence of linkages which allow the release of Se in the soil solution only after physico‐chemical variation such as exchange with phosphate ions.  相似文献   

14.
Abstract

Selenite adsorption by a variety of oxides consisting of iron (Fe), aluminum (Al), titanium (Ti), manganes (Mn), and silicon (Si), and by two humic acids were investigated in order to grasp selenite behavior and fixation mechanisms in soil. It was found that selenite was apparently adsorbed even by the Mn oxides on which surface negative charge was dominant in normal pH range (pH <4). No selenite adsorption was observed in the silicon dioxide (SiO2) and the two humic acids. A sequential extraction of adsorbed selenite with competitive anions showed the differences of binding force or stability of adsorbed selenite among the minerals. While the goethite fixed selenite strongly, selenite adsorbed on the Mn oxide was easily released to the liquid phase with other anions, such as phosphate. Each mineral had its inherent characteristic in ligand exchange reactions accompanied with selenite sorption. Selenite sorption by the Mn and the Ti oxides resulted in large increase of surface negative charge, while only a little increase in the Fe and Al oxides. Proton consumption with selenite sorption was extremely smaller for the Mn oxide than for the others.  相似文献   

15.
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.  相似文献   

16.
Foliar applications of a fertilizer of selenite or selenate were carried out to determine the influence of selenium on the yield and quality of green tea leaves harvested in early spring. Numbers of sprouts and the yield were significantly increased by the application of selenium. The sweetness and aroma of green tea leaves were also significantly enhanced, and bitterness was significantly decreased by the application of selenium. However, no significant differences were found in sweetness, bitterness, and aroma between tea leaves fertilized with selenite and selenate. Se concentration was significantly increased by selenium fertilization, and tea enriched by sodium selenate had a significantly higher selenium content than did tea enriched by sodium selenite. Total amino acid and vitamin C contents were significantly enhanced by the application of selenium. Tea polyphenol contents were significantly decreased by fertilization with selenium. The marked difference of tea polyphenols was also found between applications of selenite and selenate.  相似文献   

17.
We measured sorption of selenite and phosphate, both separately and in competition, in a Chilean Andisol. We also used previously published data for competitive sorption of arsenate and phosphate by a clay subsoil. We wrote computer programs that allowed us to compare the fits of differing versions of equations to describe individual sorption and competitive sorption. For the selenite–phosphate data, the index term of the Freundlich equation decreased as concentration increased. This was described using the Sibbesen modification of the Freundlich equation. This modification was then included in competition equations. For both the selenite–phosphate and the arsenate–phosphate data, competition was not ‘symmetrical’, that is, the competition terms were not reciprocals of each other. We think this occurred because competition between ions is not only competition for adsorption sites but also involves electrical effects that follow penetration of the surface.  相似文献   

18.
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.  相似文献   

19.
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20.
In soil, adsorption of selenium (Se) onto mineral surfaces is accompanied by poorly known retention via organic matter. The effects of these components on the availability of Se were examined in two pot experiments. Spring wheat was grown with increasing amounts of selenate (SeO4 2–) in one sand and three peat soils, and ryegrass with selenate and selenite (SeO3 2–) in sphagnum peat manipulated by iron (Fe) hydroxide. Selenate persisted in soluble form, whereas selenite was fixed in the soil. In wheat, 5–50% of the selenate addition was recovered in the plant, the proportion increasing with increasing Se. In ryegrass, 30–40% of the added selenate but less than 2% of the selenite was found within the leaves. The Fe hydroxide enrichment enhanced the selenite uptake. Phosphate buffer desorbed a minor proportion of the added selenite, except in peat amply enriched with Fe hydroxide. The results suggest that the retention mechanism of selenite was changed due to the hydroxide amendment.  相似文献   

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