邻苯二甲酸和水杨酸在可变电荷土壤中的吸附行为

研究了2种低分子量有机酸邻苯二甲酸和水杨酸在2种代表性可变电荷土壤红壤和砖红壤中的吸附行为。结果表明,可变电荷土壤对有机酸的吸附容量较大,对邻苯二甲酸的吸附亲和力大于对水杨酸的亲和力,在砖红壤中2种有机酸的吸附量大于在红壤中的,这与土壤的游离铁、铝氧化物的含量一致。土壤氧化铁在有机酸吸附中起着重要作用,粘土矿物如高岭石对有机酸的吸附量很小。有机酸的吸附涉及专性吸附和静电吸附2种机制,并以前者为主。当pH小于4.5时,pH的改变对有机酸的吸附影响不大;当pH大于4.5时,有机酸的吸附量随pH的增加而减小。     

Effect of Low Molecular Weight Organic Anions on Adsorption of Aluminum by Variable Charge Soils

To examine the effect of organic anions on adsorption of Al by variable charge soils at different pH values, the adsorption by three soils in the presence of three low-molecular-weight aliphatic carboxylic acids was investigated. The results showed that the effect depended on pH, the type of organic anions and their concentration. The presence of citrate and oxalate led to an increase in the adsorption of Al at low pH and low concentration of organic anions, with citrate showing a stronger effect than oxalate. For example, the maximum increments of Al adsorption in the presence of citrate were 131.9, 104.8 and 32.9% in the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively, whereas in the presence of oxalate it was 36.1% in the Rhodic Ferralsol. At high pH or high concentration of organic anions, they showed an inhibiting effect on the adsorption of Al. For example, citrate caused the increase in Al adsorption by 164.0, 131.0 and 61.0% at pH3.85 and the decrease in Al adsorption by 15.2, 19.5 and 45.6% at pH 4.8 for the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively. In the citrate and oxalate systems, the adsorption of Al increased with the increase in the concentration of organic anions, reaching a maximum values at about 0.4 mmol L^?1, and then decreased. When the concentration of organic anions was higher than about 1.0 mmol L^?1, both citrate and oxalate inhibited the adsorption of Al. The ability of organic anions in increasing the adsorption at low pH and decreasing the adsorption at high pH followed the same order: citrate > oxalate > acetate. The increase of Al adsorption at low pH is caused by the increase in soil negative surface charge as a result of the adsorption of organic anions by variable charge soils, while the decrease of Al adsorption at high pH and high concentration of organic anions is related to the competition of organic ligands for aluminum ions with soil surface. After the removal of free iron oxides from the soil, Al adsorption decreased in the presence of citrate, the anion species most strongly adsorbed by variable charge soils and complexed with aluminum ions. For example, for the Rhodic Ferralsol and the Ferric Acrisol, the removal of free iron oxides caused a decrease in the adsorption of Al in the presence of citrate at pH4.4 by 26.2 and 21.9%, respectively.     

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.     

可变电荷土壤中铜离子的解吸

研究了我国四种可变电荷土壤红壤、赤红壤、砖红壤和铁质砖红壤以及二种恒电荷土壤黄棕壤和黑土中吸附性铜离子的解吸特征。研究结果表明 ,可变电荷土壤吸附的一部分铜离子可以被去离子水解吸 ,而且在pH～解吸率曲线上在一定pH值时出现解吸率最大值。在最大值时不同土壤中铜离子解吸率的大小与土壤中氧化铁的含量有关。氧化铁的含量越高 ,在最大值时铜离子的解吸率越大。当用中性电解质解吸可变电荷土壤吸附的铜离子时 ,电解质的浓度越大 ,解吸率越低。与此相反 ,恒电荷土壤吸附的铜离子不能被去离子水解吸 ,只能被中性电解质解吸 ,且电解质的浓度越高 ,解吸率越大。这表明 ,可变电荷土壤中吸附性铜离子的解吸规律 ,完全不同于恒电荷土壤中者。本文初步讨论了其原因     

Effects of phthalic and salicylic acids on Cu(II) adsorption by variable charge soils

In the present study, the effect of two substituted benzoic acids on Cu(II) adsorption onto two variable charge soils was investigated, with the emphasis on the adsorption and desorption equilibrium of Cu(II). Results showed that the presence of organic acids induced an increase in Cu(II) adsorption onto the two soils. The extent of the effect was related to the initial concentrations of Cu(II) and organic acid, the system pH, and the nature of the soils. The effect of organic acids was greater for Oxisol than for Ultisol. Phthalic acid affected Cu(II) adsorption to a greater extent than salicylic acid did. The effect of organic acids varied with pH. The adsorption of Cu(II) induced by organic acids increased with increasing pH and reached a maximum value at approximately pH 4.5, and then decreased. It can be assumed that the main reason for the enhanced adsorption of Cu(II) is an increase in the negative surface charge caused by the specific adsorption of organic anions on soils because the desorption of Cu(II) adsorbed in organic acid systems was greater than that for the control. The desorption of Cu(II) absorbed in both control and organic acid systems also increased with increasing pH; it reached a maximum value at pH ∼5.25 for control and salicylic acid systems and at pH ∼5.1 for a phthalic acid system, then decreased. This interesting phenomenon was caused by the characteristics of the surface charge of variable charge soils.     

磷酸盐吸附对可变电荷土壤正负电荷的影响

本文研究了华南地区不同类型的可变电荷土壤，并对磷酸盐的吸附量和吸附磷后土壤的正、负电荷的变化，以及ｐＨ和游离氧化铁对这种变化的影响进行了研究。结果表明，土壤吸磷量与土壤游离氧化铁含量成良好的正相关。土壤吸磷后正电荷减少，负电荷增加，土壤电荷量与吸磷量之间呈抛物线状相关。吸附１摩尔磷酸盐对土壤净负电荷的贡献在０．３－１．０摩尔之间。土壤中的游离氧化铁使吸附的磷对土壤负电荷的贡献减少。     

Influence of soil composition on adsorption of glyphosate and phosphate by contrasting Danish surface soils

The herbicide glyphosate and inorganic phosphate are strongly adsorbed by inorganic soil components, especially aluminium and iron oxides, where they seem to compete for the same adsorption sites. Consequently, heavy phosphate application may exhaust soil's capacity to bind glyphosate, which may lead to pollution of drain‐ and groundwater. Adsorption of phosphate and glyphosate to five contrasting Danish surface soils was investigated by batch adsorption experiments. The different soils adsorbed different amounts of glyphosate and phosphate, and there was some competition between glyphosate and phosphate for adsorption sites, but the adsorption of glyphosate and phosphate seemed to be both competitive and additive. The competition was, however, less pronounced than found for goethite and gibbsite in an earlier study. The soil's pH seemed to be the only important factor in determining the amount of glyphosate and phosphate that could be adsorbed by the soils; consequently, glyphosate and phosphate adsorption by the soils was well predicted by pH, though predictions were somewhat improved by incorporation of oxalate‐extractable iron. Other soil factors such as organic carbon, the clay content and the mineralogy of the clay fraction had no effect on glyphosate and phosphate adsorption. The effect of pH on the adsorption of glyphosate and phosphate in one of the soils was further investigated by batch experiments with pH adjusted to 6, 7 and 8. These experiments showed that pH strongly influenced the adsorption of glyphosate. A decrease in pH resulted in increasing glyphosate adsorption, while pH had only a small effect on phosphate adsorption.     

Phosphate adsorption on uncoated and humic acid-coated iron oxides

Purpose

The phosphate adsorption on natural adsorbents is of particular importance in regulating the transport and bioavailability of phosphates in environmental system. In soils, oxides are often associated with organic matter and form mineral-organic complexes. The aim of the present paper was to investigate the mechanisms of phosphate adsorption on these complexes.

Materials and methods

Phosphate adsorption on uncoated and humic acid (HA)-coated iron oxide complexes was investigated at different ionic strengths and pH by isotherm experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy.

Results and discussion

Results showed that HA-coated iron oxide complexes caused a decrease in the specific surface area (SSA) and the isoelectric point (IEP) of oxides. Phosphate adsorption on iron oxides was insensitive to changes of ionic strength, while it increased on the complexes with increasing ionic strength. The presence of HA decreased the maximum adsorption and the affinity of phosphate on the complexes. The zeta potential of phosphate-bound iron oxides linearly reduced with the increment of phosphate surface coverage, while the zeta potential of complexes with adsorbed phosphate kept at the same level. ATR-FTIR analysis suggested the formation of phosphate-metal complexation. The presence of HA promotes the formation of the monodentate phosphate complexes at pH 4.5 and significantly influenced phosphate species at pH 8.5.

Conclusions

The amount of phosphate adsorbed was reduced, and the phosphate speciation was also influenced when phosphate was adsorbed on HA-coated iron oxide complexes compared with phosphate adsorption on pure goethite and hematite.

     

The influence of iron oxides on phosphate adsorption by soil

Soils from Denmark and Tanzania were extracted with ammonium acetate (controls), EDTA to dissolve amorphous iron oxides, and dithionite-EDTA (DE) to dissolve crystalline iron oxides. The phosphate adsorption capacities of the extracted soils were taken as the maximum quantity of phosphate adsorbed computed from the Langmuir equation. The decreases in the phosphate adsorption capacity following EDTA extraction and DE extraction were attributed to the removal of iron oxides. Close correlations (P<0.001) were found (i) between EDTA-extractable iron (amorphous iron oxides) and the decrease in phosphate adsorption capacity following EDTA extraction, and (ii) between the difference between DE-extractable iron and EDTA-extractable iron (crystalline iron oxides) and the further decrease in phosphate adsorption capacity following DE extraction. The phosphate adsorption capacity, estimated to be approximately 2.5 μmol P m^?2, was in good agreement with the capacity of various synthetic iron oxides. The calculated phosphate adsorption capacity of soil iron oxides, obtained from the contents and specific surfaces of amorphous and crystalline iron oxides together with the phosphate adsorption capacity per m² for synthetic iron oxides, compared favourably with the measured phosphate adsorption capacity.     

亚热带土壤不同矿物组分中铬的吸附

Safe application of chromium (Cr)-containing organic industrial wastes to soil requires considering the ability of the soil to adsorb Cr.In this study,the maximum Cr adsorption capacity was assessed for the bulk samples and their clay and iron-free clay fractions of four subtropical soils differing in mineralogy.To this end,the samples were supplied with Cr(Ⅲ) nitrate solutions at pH 4.5 or 5.5.The results of Cr(Ⅲ) adsorption fitted to a Freundlich equation and the adsorption capacity was positively correlated with soil organic matter and iron oxide contents.The clay fractions adsorbed more Cr per unit mass than the bulk soils and the iron-free clay fractions.The Cr(Ⅲ) adsorption capacity increased with increasing soil pH due to more charges on adsorbing surfaces.Our results suggest that the soils rich in organic matter and iron oxides and having a pH above 4.5 are suitable for application of Cr(Ⅲ)-loaded industrial wastes.     

Adsorption of cobalt by soil iron oxides at low solution concentration

Abstract

Eleven selected soils from Denmark and Tanzania were treated with ammonium acetate (controls), EDTA, and dithionite‐EDTA (DE) to fractionate iron and (manganese) oxides. The amounts of cobalt adsorbed were determined from a 3 μM equilibrium cobalt solution, corresponding to the cobalt level in natural soil solutions using sodium nitrate (0.2 M) to suppress non‐specific adsorption, by the extracted soils as well as by two synthetic iron oxides.

No significant correlations were found between cobalt adsorption and the contents of organic matter and extractable manganese, presumably due to their low contents in the soils investigated. Close correlations were, however, found between the amounts of cobalt adsorbed, especially fractions thereof, and the contents of iron oxides.

The amounts of cobalt adsorbed by the DE‐ex‐tracted soils, void of iron (and manganese) oxides, were attributed to the clay silicates. The remaining cobalt adsorption, i.e. the difference between cobalt adsorbed by acetate‐extracted and DE‐extracted samples, was attributed to the iron oxides. This portion of adsorbed cobalt was well described by considering soil iron oxides composed of only two fractions, an EDTA‐extractable fraction of high reactivity and a less reactive fraction corresponding to the difference between DE‐extractable iron and EDTA‐extractable iron.

The amounts of cobalt adsorbed by the soil iron oxides were well predicted from the contents and specific surface of the two iron oxide fractions in soil together with the amount of cobalt adsorbed by the synthetic iron oxides.     

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.     

The adsorption of copper by soil samples from scotland at low equilibrium solution concentrations

At low solution concentrations of copper in the presence of 0.05 M CaCl₂, adsorption isotherms for copper on soil samples were essentially linear. Although no direct correlations were found between isotherm gradients and individual soil properties, the gradients were of the same order of magnitude as predictions based on gradients obtained for some specific soil components. The soil components which appear to be most important in copper adsorption and which were used to obtain the predictions were organic matter and iron and manganese oxides. The amounts of adsorbed copper remaining isotopically exchangeable or extractable with EDTA in the short term increased with the amount of copper adsorbed but the proportions of adsorbed copper estimated by each of these techniques remained constant. Concentrations of copper in solution increased (adsorption decreased) at pH values below 4.5 and above 6.5.     

有机酸对铝氧化物吸附磷的影响

以存在不同配位阴离子 (硫酸根、磷酸根、草酸根、柠檬酸根 )时合成的铝氧化物为对象 ,用平衡吸附法研究了草酸、柠檬酸等的浓度和 pH对铝氧化物吸附磷的影响 ,并讨论有机酸影响磷吸附的机制。结果表明 :六种合成铝氧化物的最大吸磷量 (Xm)介于 0.189～ 0.838mmol/g ,以Al(OH)x的吸磷量最高 ,铝 柠檬酸复合物 (Al-CA)的吸磷量最低 ;有机酸浓度升高时 ,铝氧化物的吸磷量降低 ,且柠檬酸的影响程度高于草酸 ;先加 pH为 2的草酸或酒石酸 ,Al(OH)x对磷的次级吸附量最低 ,而有机酸pH为 3时 ,Al(OH)x对磷的次级吸附量达最高 ,有机酸溶液 pH由 4增至 9,铝氧化物吸磷量变化不大或逐渐降低。有机酸与磷混合加入同单加磷相比 ,pH 3时差异较小 ,pH 4～ 6时差异最显著 ,pH 7～ 8时又减小 ;有机酸降低铝氧化物吸磷量的机理包括酸性溶解和络合竞争两方面 ,在 pH 2时以前者为主 ,pH 3～ 9时以后者为主 ,且铝氧化物表面的吸附点位对供试配位阴离子都是亲合的     

Competitive adsorption of humus acids and phosphate on goethite, gibbsite and two tropical soils

Competition in adsorption between humic acid (HA) or fulvic acid (FA) and phosphate on synthetic goethite, gibbsite and two tropical soils was studied. The results for both goethite and gibbsite showed that HA and FA competed strongly with phosphate for adsorption sites at low pH values. The soils showed a similar result with a reduction in phosphate adsorption resulting from the addition of HA at the pH of the soils. The competition between HA and phosphate at different pH levels is illustrated by comparing the adsorption envelopes for phosphate on goethite, gibbsite and the two soils in the presence and absence of HA. The trends observed may be explained by the relative positions of the maximum buffer-power (buffer capacity) of the organic acids and of phosphoric acid which are shown to lie in different pH ranges.     

Adsorption of Phosphate on Variable Charge Soils

The study about the adsorption of phosphate on four variable charge soils and some minerals revealed that two stage adsorption appeared in the adsorption isotherms of phosphate on 4 soils and there was a maximum adsorption on Al-oxide-typed surfaces between pH 3.5 to pH 5.5 as suspension pH changed from 2 to 9, but the adsorption amount of phosphate decreased continually as pH rose on Fe-oxide typed surfaces. The adsorption amount of phosphate and the maximum phosphate adsorption pH decreased in the order of yellow-red soil > lateritic red soil > red soil > paddy soil, which was coincided with the content order of amorphous Al oxide. The removement of organic matter and Fe oxide made the maximum phosphate adsorption pH rise from 4.0 to 5.0 and 4.5, respectively. The desorption curves with pH of four soils showed that phosphate desorbed least at pH 5. Generally the desorption was contrary to the adsorption with pH changing.     

Effects of air-drying on the adsorption and desorption of phosphate and levels of extractable phosphate in a group of acid soils,New Zealand

The effects of air-drying field-moist soils on the adsorption and desorption of added phosphate and on the levels of extractable native soil phosphate were examined using the A and B horizons of a group of four acid soils.Air-drying increased the capacity of all the soil samples to adsorb phosphate. At an equilibrium solution concentration of 0.5 μg P ml^?1, the increase in the quantity of phosphate adsorbed following drying ranged from 23% to 70% of that adsorbed by the moist samples. Considerable hysteresis in phosphate adsorption—desorption isotherms was observed for both moist and dried soil samples indicating that the additional phosphate adsorbed by the dried samples was held with the same strength as that held by the moist samples.Air-drying the soil samples caused a small decrease in soil pH of approximately 0.1 pH unit and a general increase in levels of EDTA-extractable Fe, Al and organic matter. Quantities of native soil phosphate extractable with EDTA, resin and NaHCO₃ were also increased. Concentrations of oxalate- and pyrophosphate-extractable Fe and Al and exchangeable Al were, however, unaffected by drying.It was also shown that when the phosphate content of NaHCO₃ extracts is measured using the conventional molybdenum blue method, orthophosphate plus a differing amount of acid-hydrolysable organic P present in the extract is measured.     

Influence of low-molecular-weight organic acids on the solubilization of phosphates

A range of low-molecular-weight organic acids were identified in rhizosphere soil, leaf litter, and poultry manure compost. Laboratory and greenhouse experiments were carried out to examine the effects of seven low-molecular-weight organic acids on phosphate adsorption by soils, and the solubilization and plant uptake of P from soil pre-incubated with monocalcium phosphate and North Carolina phosphate rock. Acetic, formic, lactic (monocarboxylic), malic, tartaric, oxalic (dicarboxylic), and citric (tricarboxylic) acids were used in the study. The addition of organic acids decreased the adsorption of P by soils in the order tricarboxylic acid>dicarboxylic acid>monocarboxylic acid. The decreases in P adsorption with organic acid addition increased with an increase in the stability constant of the organic acid for Al (logK _Al). Organic acids extracted greater amounts of P from soils meubated with both monocalcium phosphate and phosphate rock than water did. Although more phosphate was extracted by the organic acids from monocalcium phosphate — than from phosphate rock — treated soils in absolute terms, when the results were expressed as a percentage of dissolved phosphate there was little difference between the two fertilizers. The amount of P extracted by the organic acids from both fertilizers increased with an increase in logK _Al values. The addition of oxalic and citric acids increased the dry matter yield of ryegrass and the uptake of P in soils treated with both fertilizers. The agronomic effectiveness of both fertilizers increased in the presence of organic acids and the increase was greater with the phosphate rock than with the monocalcium phosphate. The results indicated that organic acids increase the availability of P in soils mainly through both decreased adsorption of P and increased solubilization of P compounds.     

Sulfate adsorption by variable charge soils: Effect of low-molecular-weight organic acids

Sulfate (SO₄ ^2–) movement and transport in soils has received considerable attention in recent years. In most soils, SO₄ ^2– coexists with a variety of natural organic compounds, especially organic acids. Studies were conducted to assess the effect of low-molecular-weight organic acids (eight aliphatic and five aromatic acids) on SO₄ ^2– adsorption by variable charge soils from Chile and Costa Rica. The effects of type of organic acid, pH, type of soil, and organic acid concentration were investigated. In one experiment, a 1.0 g soil sample was equilibrated with 25 ml 0, 0.5, 1.0, 2.0, 4.0, or 6.0 mM K₂SO₄ in 1 mM NaCl in the presence or absence of 5 mM citric acid. In the second set of experiments, the adsorption of 2 mM SO₄ ^2– in soils at pH 4 or pH 5 in the presence or absence of one of 13 organic acids at a concentration of 2 mM or 5 mM was studied. Results showed that citric acid significantly decreased SO₄ ^2– adsorption by the two soils. Sulfate adsorption decreased with increasing pH of the equilibrium solution. Aliphatic acids, with the exception of cis-aconitic acid, decreased the amount of SO₄ ^2– adsorbed by the two soils, with oxalic, tartaric, and citric acid showing the greatest effect. The differences in pH values of the equilibrium solutions in the presence and absence of organic acids were significantly, but negatively, correlated with the amount of SO₄ ^2– adsorbed, suggesting chemisorption of SO₄ ^2– and the release of hydroxide ions. The ionization fraction values of the organic acids at the equilibrium pH were correlated with the amounts of SO₄ ^2– adsorbed, suggesting that the protonation of surface hydroxyl groups of the mineral phase increased as the strength of the ionization of the acid increased, thus creating more positively charged surfaces. Received: 12 February 1997     

Effect of organic acids on the adsorption of copper,lead, and zinc by goethite

The adsorption of Cu, Pb, and Zn by synthetic goethite was studied in the absence and presence of oxalic, citric, and glutamic acids at different pH values. It was shown that, in the absence of an acid, the content of adsorbed metals increased with the increasing pH. The content of adsorbed cations at constant pH values decreased in the sequence: Cu > Pb > Zn. The simultaneous addition of metal cations and organic acids to the goethite suspension increased the content of the adsorbed elements. The oxalic and citric acids had similar effects on the adsorption of copper and lead in the studied pH range. The metal: acid concentration ratios significantly affected the adsorption of the heavy metals by goethite. An increase in the metal adsorption was observed to a certain metal: acid ratio, which was followed by a gradual decrease. The adsorption of the metals by goethite also depended on the properties of the metal cations and the organic ligands. The observed tendencies were attributed to the complexation of heavy metals with organic acid anions and the simultaneous sorption of acids at positively charged sites on the goethite surface with the formation of mineral-organic compounds, which significantly modified the surface properties of the mineral. The study of the effect of increasing lead concentrations in the solution on the copper adsorption by goethite in the absence, in the presence, and at the addition of an oxalic acid solution to the goethite suspension one hour before the beginning of the experiment showed that lead decreased the adsorption of copper in all the treatments. The possible mechanisms of the processes occurring in the system were considered.