土壤对镉的吸附与解吸——Ⅰ.土壤组份对镉的吸附和解吸的影响

采用选择溶解法研究了有机质、游离铁、无定型硅、铝等土壤组份对青黑土、黄棕壤、红壤和砖红壤胶体吸附和解吸Cd的影响。结果表明,去除有机质后胶体吸附Cd减少,这可能是由于交换吸附的减少所致;游离铁的去除使得黄棕壤、红壤和砖红壤的吸附量显著减少,显示了在这些土壤中游离氧化铁专性吸附的重要性;随着无定形铝含量的上升,吸附量下降,这是因为铝离子占据了高能量的吸附位。经不同处理后的土壤胶体,其Cd的解吸顺序(解吸%)大致为:去无定型硅、铝者>去游离铁者>去有机质者>原胶体,但在不同土壤和不同pH条件下该顺序略有差别。研究结果为控制和改造土壤Cd污染提供了理论依据。     

Azimsulfuron sorption--desorption on soil

The sorption and desorption of the herbicide azimsulfuron, N-[[(4-dimethoxypyrimidin-2-yl)amino]carbonyl]1-methyl-4-(2-methyl-2H-tetrazole-5-yl)1H-pyrazole-5-sulfonamide, were studied using five soils. Sorption isotherms conformed to the Freundlich equation. It was found that pH is the main factor influencing the sorption and that the sorption on soils was negatively correlated with pH. The highest level of sorption was measured on soils with low pH and high organic carbon content. Moreover, inorganic soil colloids, for example, smectite clay minerals and iron oxides, contributed to the sorption of azimsulfuron. Desorption was hysteretic on soils with high organic and inorganic colloid contents.     

氧化还原条件下有机物料对酸性土壤pH、铁形态和铜吸附解吸的影响

研究了添加有机物料对水稻土、红壤和砖红壤在干湿交替一次以后土壤pH、铁的形态和对铜吸附解吸行为的影响。结果表明,添加有机物料使得土壤pH升高,且随着有机物料加入量的增加而升高。与对照相比,添加有机物料可使水稻土、红壤和砖红壤的pH分别上升1.55、0.8和1.33个pH单位。红壤和砖红壤中无定形氧化铁含量增加,而水稻土中变化不大。在铜的平衡浓度为0.2 mmol/L时,添加有机物料培养可使水稻土、红壤和砖红壤铜的吸附量分别增加6.7、10.3和3.6 mmol/kg。     

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.     

苏南水稻土对铜离子专性吸附的初步研究

六十年代以来,土壤对多价离子特别是重金属离子的专性吸附,已日益成为土壤化学领域中一个受人注意的问题。土壤胶体中铁、锰、铝、硅等氧化物及其水合物和土壤有机质是专性吸附的主要载体^{[12,16,17,19,20,21]},它们对许多重金属元素的专性吸附所引起的富集过程,起着控制这些金属元素在土壤溶液和海水中浓度的作用^[9,15,18];一些微盒营养元素在土壤中的移动及其对植物的有效性,也深受土壤中氧化物胶体的专性吸附的影响^[11,14,21]。因此,铁、锰等水合氧化物对重金属离子的专性吸附的研究,不仅是土壤化学领域,而且也是土壤环境保护和地球化学等领域中的重要研究课题。     

Selenium Distribution,Chemical Fractionation and Adsorption in some Egyptian Alluvial and Lacustrine Soils

Fifty-five soil samples representing Egyptian alluvial and lacustrine soils were chemically analyzed for total Se which was found to vary from 0.18 to 0.85 ppm with an average of 0.45 ppm. These levels are positively correlated with organic matter, total carbonate and clay content of the soils. Minimum variation of total Se with soil depth was found. The chemical fractionation of soil Se, expressed as percent of the total, indicates that on the average about 25.4 % exists in 0.2 M K₂SO₄-extractable form, 18.5 % is extracted with 0.5 N NH₄OH, 9.7 % as 6 N HCl-extractable form and 13.8 % as extractable with 9 N HNO₃. Amounts of K₂SO₄-Se and HNO₃-Se in soils correlated significantly with soil organic matter, total carbonate, free iron oxide and clay content. The NH₄OH-Se and HCl-Se fractions correlated significantly only with organic matter and clay content. There is also significant correlation between total Se and the studied Se fractions. Specific adsorption of Se by soils was low as expressed by the Langmiur adsorption maximum values. The high soil pH has a reducing effect on Se adsorption.     

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。     

聚合氨基酸对北方水稻土中氧化铁存在形态的影响

为了解不同类型水稻土中氧化铁含量特征,探明添加外源聚合氨基酸对水稻土中氧化铁形态变化的影响,本研究以中国北方不同类型水稻土(棕壤型、草甸土型和滨海盐渍型)为研究对象,设置添加占供试土壤干重0.05%的γ-聚谷氨酸和聚天冬氨酸处理,以不添加氨基酸作为对照。通过室内恒温厌氧培养30 d后,测定各水稻土全铁、游离氧化铁、无定形氧化铁和络合态铁含量及氧化铁的活化和络合程度。结果表明:供试的北方3种典型水稻土中,游离氧化铁含量为滨海盐渍型草甸土型≥棕壤型,络合态铁含量为棕壤型滨海盐渍型≥草甸土型,而无定形氧化铁含量为棕壤型滨海盐渍型草甸土型。两种外源聚合氨基酸对不同类型水稻土氧化铁形态转化能力影响存在差异,与不添加氨基酸的对照相比,添加γ-聚谷氨酸的棕壤型水稻土无定形氧化铁和络合态铁含量分别增加27.72%和32.25%,聚天冬氨酸对无定形氧化铁和络合态铁含量无显著促进作用;在草甸土型水稻土中,γ-聚谷氨酸和聚天冬氨酸均能显著增加无定形氧化铁含量,且与对照相比,络合态铁含量分别增加136.24%和12.00%;γ-聚谷氨酸能有效促进滨海盐渍型水稻土中无定形氧化铁和络合态铁的生成。总之,添加γ-聚谷氨酸和聚天冬氨酸对水稻土游离氧化铁的含量没有明显影响;而添加γ-聚谷氨酸能有效增加水稻土中无定形氧化铁和络合态铁含量,降低晶胶率,有利于提高土壤中有效铁含量,显著活化铁氧化物,抑制各类型水稻土中铁的结晶老化;而聚天冬氨酸对水稻土无定形氧化铁和络合态铁没有明显的激发效应。     

Phosphorus adsorption by a range of western Australian soils related to soil properties

Abstract

The capacity of 36 Western Australian soils to adsorb phosphorus (P) was measured by three different methods: P retention index (PRI), P buffering capacity (PBC), and P adsorption (PA). The P adsorption values measured by all three methods varied markedly with soil type. When the P adsorption values were correlated with several soil properties, using simple and multiple linear regressions, PRI, PBC, or PA values were found to be significantly correlated with the aluminium oxide content of the soils. In addition, PBC and PRI was correlated with organic carbon content. The role of aluminium oxide (Al₂O₃) in the soil was apparently more important in determining the P adsorption capacity of the soils than that of iron (Fe), even though the iron oxide (Fe₂O₃)content of all the soils studied was consistently higher than the aluminium oxide content. The relationship between P adsorption and the selected soil properties, as determined by multiple linear regression, explained 45–59% of the variation: arabic PRI = ‐10.87 + 9.94 organic C (%) + 160.02 Al₂O₃ (%), r² = 0.45.

arabic PBC = ‐0.004 + 1.532 organic C (%) + 22.26 Al₂O₃ (%), r² = 0.57.

arabic PA = 3.52 + 248.75 Al₂O₃ (%), r² = 0.59.

     

FLUORIDE ADSORPTION BY ILLINOIS SOILS

Fourteen surface and 6 subsurface horizons of Illinois soils adsorbed significant amounts of F^? with release of OH^?. At low concentrations, adsorption was described by both Langmuir and Freundlich isotherms. The calculated Langmuir adsorption capacities were related to pH, clay, organic carbon, and amorphous aluminum contents. Two soils with different gross chemical properties behaved in essentially the same manner, with adsorption maxima occuring between pH 5.5 and 6.5. The similarity between adsorption at different pH values for the soils and those for bauxite, allophane and synthesized ‘soil chlorite’, and the lack of adsorption maxima between pH 5.5 and 6.5 for pure kaolinite and montmorillonite, suggest that F^? adsorption in the soils is due primarily to the presence of amorphous aluminum oxyhydroxides which are common weathering products in these soils.     

Effect of organic amendments on the retention and mobility of imazaquin in soils

The influence of two organic amendments consisting of an urban waste compost (SUW) and a commercial amendment from olive mill wastes (OW) was assessed on the sorption properties and leaching of the ionizable herbicide imazaquin on four soils with different physicochemical characteristics. A loamy sand soil (CR), a loam soil (P44), a silt loam soil (AL), and a clay soil (TM), with low-medium organic matter contents, were chosen. Sorption-desorption experiments were performed on the original soils and on a mixture of these soils with the organic amendments at a rate of 6.25% (w/w). These mixtures were used just after preparation and after aging for 3 months. Imazaquin adsorption was higher on AL soil because of its high content of amorphous iron oxides, whereas it was related to the soils' organic matter (OM) contents on TM and CR soils and to acid pH on P44 soil. Addition of exogenous OM to soils caused a decrease in the adsorption of the herbicide with the only exception of CR soil, due to blocking of adsorptive surfaces and/or equilibrium pH rise. The extent of this decrease was dependent only on the nature of the added amendment on AL soil. The adsorbed amounts of imazaquin on aged organic fertilized soils were usually fairly close to that on original soils. Results of soil column experiments indicate that addition of exogenous organic matter cannot be considered as a regular practice for retarded movement of imazaquin.     

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.     

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.     

Sorption of primisulfuron on soil, and inorganic and organic soil colloids

Inorganic and organic soil colloids are responsible for the sorption of many pesticides. We studied the sorption of the herbicide primisulfuron [methyl 2 N‐[[[[[4,6‐bis(difluoromethoxy)‐2‐pyrimidinyl]amino]carbonyl]amino]sulfonyl]benzoate] on Fe³⁺‐, Al³⁺‐, Ca²⁺‐ and Na⁺‐exchanged montmorillonite, soil organic matter (H⁺‐ and Ca²⁺‐saturated), amorphous iron oxide, and three soils in aqueous media. The sorption on soils was negatively correlated with pH. Ca²⁺‐ and Na⁺‐exchanged montmorillonites are ineffective in the sorption of primisulfuron. The sorption on Fe³⁺‐ and Al³⁺‐exchanged montmorillonite is rapid and follows the Freundlich equation. Fourier transform infrared (FT‐IR) and X‐ray powder diffraction studies of the Fe³⁺‐ and Al³⁺‐montmorillonite samples after the interaction with primisulfuron in chloroform solution suggest that primisulfuron is adsorbed and degraded in the interlayer. Humic acid is more effective in the sorption than is Ca humate, suggesting that the pH of the suspension (3.5 for humic acid and 6.0 for Ca humate) has a strong influence on the sorption of primisulfuron. Experiments on amorphous iron oxide indicate similar pH dependence. Infrared spectra indicate that the protonation of the pyrimidine nitrogen moiety of herbicide and subsequent hydrogen bonding with the surface hydroxyls of Fe oxide is the mechanism acting in the primisulfuron sorption.     

离子强度和pH对可变电荷土壤与铜离子相互作用的影响

研究了离子强度和pH对可变电荷土壤表面电荷与铜离子吸附的影响。作为对照 ,也研究了它们对恒电荷土壤黄棕壤的有关性质的影响。结果表明 ,随pH升高 ,土壤的表面负电荷增加 ,正电荷减少。对于可变电荷土壤 ,可出现电荷零点 (pH0 )。随pH升高 ,土壤对Cu2 的吸附量增大。随着离子强度增大 ,恒电荷土壤对Cu2 的吸附百分率明显降低 ,可变电荷土壤对Cu2 离子的吸附百分率也降低 ,但降低的幅度比恒电荷土壤者小得多。土壤中氧化铁的含量越高 ,降低的幅度越小。对于含 2 1 %左右游离氧化铁的铁质砖红壤 ,即使支持电解质NaNO3的浓度高达 1molL- 1,对Cu2 的吸附仍然几乎没有影响。从离子强度和pH与土壤表面电荷和铜离子吸附的关系 ,可以推测在土壤对铜离子的吸附中 ,既存在电性吸附 ,又存在专性吸附。在可变电荷土壤对铜离子的吸附中 ,专性吸附较为重要     

Adsorption of phthalic acid and salicylic acid by two variable charge soils as influenced by sulphate and phosphate

Low‐molecular‐weight (LMW) organic acids exist widely in soils, especially in the rhizosphere, and the adsorption of these acids may affect their reactions in soils. The adsorption behaviour of phthalic acid and salicylic acid by two variable charge soils (a Rhodic Ferralsol and a Haplic Acrisol) was investigated. Both soils exhibited great adsorption capacity for these organic acids, with a greater affinity for phthalic acid. The Rhodic Ferralsol adsorbed more organic acids of both kinds than the Haplic Acrisol, which was consistent with the content of iron and aluminum oxides in the two soils. The iron oxides in these soils played a significant role in adsorption of the organic acids, whilst the soil aluminosilicate minerals, such as kaolinite, showed a small adsorption capacity. The presence of phosphate and sulphate caused a decrease in the adsorption of both organic acids because of their competition with them for sorption sites. The phosphate showed a bigger inhibition on the adsorption than sulphate as a result of a greater amount of phosphate adsorbed by the soils. The adsorption of both organic acids was affected by pH only slightly at pH < 4.5. However, the adsorption decreased with the increase in pH at pH > 4.5. A similar trend was observed for the phosphate system, but the opposite was seen for the sulphate system. This suggests that the inhibition of sulphate on the adsorption of the organic acids decreased with the increase in pH, because the adsorption of sulphate decreased strongly with increasing pH.     

长期施肥对棕壤铁形态及其有效性的影响

【目的】利用沈阳农业大学棕壤肥料长期定位试验,研究不同施肥处理对耕层土壤酸碱度（pH）、氧化还原电位（Eh）和有机质的影响,探讨不同施肥条件下土壤游离态氧化铁、无定形氧化铁、亚铁总量和有效铁含量的变化以及与pH、Eh和有机质的关系。 【方法】本文选取试验处理为CK（不施肥）、N（氮肥）、NP（氮磷肥配施）、NPK（氮磷钾肥配施）、M（有机肥）、MN（有机肥与氮肥配施）、MNP（有机肥与氮磷肥配施）、MNPK（有机肥与氮磷钾肥配施）。在2014年大豆收获期,采集了不同施肥处理0-20 cm耕层土壤样品,分析了土壤pH、Eh、有机质含量以及游离态氧化铁、无定形氧化铁、亚铁和有效铁含量。 【结果】与1979年原始土壤相比,所有处理土壤pH显著降低了0.6~1.4个单位。不施肥处理土壤有机质下降了11.5%,化肥处理有机质略有下降,而有机肥处理有机质含量显著增加。所有处理有效铁含量显著增加,化肥有机肥配施增加幅度更大;与2014年不施肥处理相比,施用氮肥处理土壤pH最低,而氮肥配施磷、钾和有机肥中的一种或几种pH又有所上升,其中配施有机肥效果最明显;施用化肥处理土壤Eh增加,而施用有机肥处理Eh则下降。施用化肥土壤游离态氧化铁和有效铁含量增加,亚铁含量下降,而施用有机肥土壤游离态氧化铁降低,亚铁总量及有效铁含量增加。 【结论】经过长期耕作和施肥,土壤pH显著下降,有效铁含量显著增加。长期不施肥土壤有机质显著下降。施用氮肥土壤酸化趋势明显,磷、钾和有机肥配施能够缓解氮肥引起的酸化现象。施用有机肥显著降低土壤氧化还原电位,有利于氧化态铁向还原态铁转化,更有利于增加土壤有效性铁的含量。     

干湿交替过程中水稻土铁形态和磷吸附解吸的变化

采用室内培养试验 ,经过连续 3次淹水 落干处理 ,研究了干湿交替过程中土壤中氧化铁形态的变化以及对土壤磷吸附和解吸的影响。结果表明 ,淹水使土壤中结晶态氧化铁含量明显减少 ,无定形氧化铁和土壤对磷的吸附量急剧增加 ,磷解吸下降 ;落干则使之发生相反的变化。土壤中的无定形氧化铁含量与土壤对磷的吸附之间存在着密切的相关关系。因此 ,淹水 落干过程中无定形氧化铁的变化是影响水稻田磷有效性的一个主导因子。     

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.     

磷的吸附和表面电荷特征及其与华南地区某些土壤矿物的关系

The phosphate adsorption and surface charge characteristics of the tropical and subtropical soils derived from different parent materials in China were determined, and their relations to soil mineralogy were analysed. The results showed that all soil phosphate adsorption curves were well fitted by Freundlich equation and Langmuir equation. The maximum buffering capacity of P ranged from 66 to 9 880 mg kg^-1, with an increasing order of purple soil, skeletal soil, red soil, lateritic red soil, yellow soil and latosol; and the highest value was 149 times the lowest value, which indicated great differences among these soils in phosphate adsorption and supplying characteristics. The pH₀ (zero point of charge) values obtained by salt titration-potential titration varied from 3.03 to 5.49, and the highest value was found in the latosol derived from basalt whereas the lowest value was found in the purple soil. The correlation analysis indicated that the main minerals responsible for phosphate adsorption in the soils were gibbsite, amorphous iron oxide and kaolinite; and the pH₀ was mainly controlled by kaolinite, gibbsite and oxides.