表面活性剂在北京碱性土壤中的吸附行为研究

通过静态吸附实验,研究了北京碱性土壤对阴离子表面活性剂SDS、阳离子表面活性剂CTAB和非离子表面活性剂Tween80的吸附行为,考察了温度对表面活性剂吸附的影响.结果表明:7种不同土样对SDS、CTAB和Tween80的吸附等温线均较好地符合Langmuir吸附模式,其吸附能力的大小顺序为2号轻壤土》轻粘土》中壤土》砂壤土》5号轻壤土》重壤土》紧砂土,这主要是由于7种土样的pH、有机质含量和机械组成不同的缘故;同一土壤中,CTAB的吸附量》Tween80的吸附量》SDS的吸附量;温度的升高,不利于SDS和CTAB在土壤中的吸附,而有利于Tween80的吸附.     

Studies on the sorption and desorption characteristics of Zn(II) on the surface soils of nuclear power plant sites in India using a radiotracer technique

Zinc adsorption was studied in the soils of three nuclear power plant sites of India. 65Zn was used as a radiotracer to study the sorption characteristics of Zn(II). The sorption of zinc was determined at 25 and 45 degrees C at pH 7.8+/-0.2 in the solution of 0.01 M Ca(NO3)2 as supporting electrolyte. The sorption data was tested both in Freundlich and Langmuir isotherms and could be described satisfactorily. The effect of organic matter and other physico-chemical properties on the uptake of zinc was also studied in all the soil samples. The results showed that the cation exchange capacity, organic matter, pH and clay content were the main contributors to zinc sorption in these soils. The adsorption maximum was found to be higher in the soil on Kakarpara Atomic Power Plant sites soils having high organic matter and clay content. The zinc supply parameters of the soils are also discussed. In the desorption studies, the sequential extraction of the adsorbed zinc from soils showed that the diethylene triamine penta acetic acid extracted maximum amount of adsorbed zinc than CaCl2 and Mg(NO3)2. The zinc sorption on the soil and amount of zinc retention after extractants desorption shows a positively correlation with vermiculite and smectite mineral content present in the clay fraction of the soil. The amount desorbed by strong base (NaOH) and demineralised water was almost negligible from soils of all the sites, whereas the desorption by strong acid (HNO3) was 75-96% of the adsorbed zinc.     

天然土壤对水溶液中Pb~(2+)的吸附

以天然土壤为吸附材料,处理水溶液中的Pb2+,研究3种土壤对水溶液中Pb2+的吸附过程并结合土壤的理化性质对吸附规律进行初步分析。结果表明,棕壤和钙层土对Pb2+的吸附能力远大于红壤,3种土壤对Pb2+的吸附动力学曲线与二次动力学方程有较好的拟合性;3种土壤吸附Pb2+的吸附等温线用Langmuir方程描述最为合适,其次是Temkin方程,再次是Frenudlich方程,钙层土对Pb2+的吸附受温度影响较为明显;由实验数据得出的反应热力学参数说明3种土壤对Pb2+的吸附是自发的吸热过程;Pb2+在饱和吸附的土壤表面覆盖率并不高;土壤对Pb2+的吸附能力受各种土壤理化性质的综合影响。     

Sorption of lead in soil as a function of pH: a study case in México

Reactions of lead sorption onto soil are largely affected by properties and composition of soil and its solution. In this study, the lead sorption onto regosol eutric soil from Francisco I. Madero, Zacatecas, Mexico is evaluated at different pH values. Soil samples were suspended in lead solutions of 10, 25, 50, 100, 150, 200, 300, and 400 mg/l (as Pb(NO3)2). The pH was adjusted at 2, 3, 4, and 5.5 with nitric acid for each of the lead solution concentrations. In all the cases the ionic strength was I=0.09 M with calcium nitrate. The solid-liquid-ratios were fixed in 1:100 and 1:200 g/ml. The results show that lead sorption increases when pH increases. Experimental isotherms were adjusted by both Langmuir and Freundlich models. The Langmuir affinity parameter, K, indicates that the lead sorption capacity of Francisco I. Madero soils is largely perceptible to pH changes.     

Effect of fly ash on sorption behavior of metribuzin in agricultural soils

This investigation was undertaken to determine the effect of two different fly ashes [Kota and Inderprastha (IP)] amendment on the sorption behavior of metribuzin in three Indian soil types. The IP fly ash was very effective in increasing the metribuzin sorption in the soils. The sorption with IP amendment was increased by 15-92%, whereas with the Kota fly ash an increase in sorption by 13-38% was noted. The adsorption isotherms fitted very well to the Freundlich adsorption equation and, in general, slope (1/n) values less then unity were observed. Although both the fly ashes significantly decreased metribuzin desorption, the IP fly ash was comparatively more effective in retaining metribuzin in the soils. Metribuzin sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to K(f)/K(d) values, K(FA) values (sorption normalized to fly ash content) showed less variation. Metribuzin sorption-desorption did not correlate to the organic carbon content of the soil-fly ash mixture. The study demonstrates that all coal fly ashes may not be effective in enhancing the sorption of metribuzin in soils to the same extent. However, among the fly ashes used in this study, the IP fly ash was observed to be significantly effective in enhancing the sorption of metribuzin in soils. This may play an important role in reducing the run off and leaching losses of the herbicide by retaining it in the soil.     

Sorptive behavior of the phenylamide fungicides,mefenoxam and metalaxyl,and their acid metabolite in typical Cameroonian and German soils

Laboratory soil sorption experiments were conducted on mefenoxam, formulated metalaxyl (F-metalaxyl), pure metalaxyl (P-metalaxyl) and metalaxyl acid metabolite to elucidate differences in their sorptive behaviour on typical Cameroonian forest soil (sand clay loam, pH 4.8 and 3.01% OC) and German soil (sandy loam, pH 7.2, 1.69% OC) using a batch equilibrium method. The data obtained on all test chemicals conformed to linear and Freundlich adsorption isotherms. The Langmuir equation failed to describe the sorption of the substances tested. All substances were adsorbed to a greater extent by the Cameroonian soil. The average percentage adsorptions for mefenoxam, F-metalaxyl, P-metalaxyl and the acid metabolite on the Cameroonian soil were 27.8%, 28.3%, 31.8% and 46.8% respectively while for the German soil they were 21.7%, 21.5%, 24.7% and 9.8% respectively. The KD and KF parameters and the Freundlich exponential term (1/n) were low, indicating that the interactions between soil particles and the fungicides were weak. The sorption parameters were lower in the German soil. P-metalaxyl exhibited a higher adsorption capacity than F-metalaxyl in both soils. Mefenoxam and F-metalaxyl exhibited similar sorption parameters in soils, whereas those of P-metalaxyl and acid metabolite differed. Differences observed in the adsorption between the two soils could be attributed to their properties. Desorption studies revealed that the adsorbed fungicides were not firmly retained by soil particles and their adsorption was reversible. Desorption of adsorbed mefenoxam, P-metalaxyl and of the acid metabolite from German soil was almost completely reversible with percentage desorption rates of more than 91.0%, whereas the rate for F-metalaxyl was 74.1%. All compounds exhibited some resistance to desorption from the Cameroonian soil, with percentage desorption rates less than 77.0%. Therefore if degradation in the soil is slow the fungicides described have a potential to leach to lower soil horizons.     

外源硅对不同pH水田土壤吸附铅的影响

通过等温吸附实验,研究了加硅对2种不同pH水田土壤吸附铅特性的影响。实验中用硝酸中和硅酸钠的碱性,各处理间钠离子和硝酸根离子的差异以硝酸钠补齐,消除了因硅酸盐的加入改变体系pH及伴随离子对土壤吸附铅可能产生的影响。结果表明,在本实验条件下,Langmuir方程、Freundlich方程和Temkin方程都能较好地描述不同硅浓度条件下两种土壤对铅的吸附特征,但以Freundlich模型为最优;加硅促进了酸性土壤对铅的吸附,抑制了碱性土壤对铅的吸附。     

Geochemical modeling of cadmium sorption to soil as a function of soil properties

Cadmium sorption experiments were conducted to infer Cd sorption mechanisms to a reference smectite and three fractions of a Vertisol soil. Untreated Vertisol has a higher adsorption capacity for Cd than that of reference smectite. Surface complex modeling was used to calculate the potential contributions of Cd complexation reactions with permanent charge sites and pH-dependent charge sites over ranges in pH, for soils with given surface areas, and sorption site densities. The Langmuir model produced relatively good predictions of Cd sorption on reference smectite and Vertisol. However, the results of the triple-layer model (TLM) were inadequate to describe Cd adsorption on fixed-charge sites because the model could not account for the ion-exchange reaction on the basal plane. Based upon the two geochemical models of Cd adsorption to the reference smectite and Vertisol, it appears that the basal plane siloxane cavities are the most important sites for Cd complexation at pH < 6.5. For the pH-dependent sites, the edge-site aluminol appears to be the dominant surface functional group responsible for Cd adsorption at pH > 6.5.     

Adsorption and desorption processes of MCPA in Polish mineral soils

Studies on the adsorption and desorption of MCPA (4-chloro-2-methylophenoxyacetic acid) were performed in soil horizons of three representative Polish agricultural soils. The Hyperdystric Arenosol, the Haplic Luvisol and the Hypereutric Cambisol were investigated in laboratory batch experiments. Initially, both the adsorption and desorption proceeded rapidly, and either the equilibrium was reached after approximately 30 min or the process slowed down and continued at a slow rate. In the latter case, the equilibrium was reached after 8 hours. Data on the adsorption/desorption kinetics fitted well to the two-site kinetic model. The measured sorption and desorption isotherms were of L-type. The sorption distribution coefficients (K(ads) (d)) were in the range of 0.75--0.97 for Ap soil horizons and significantly lower in deeper soil layers. The corresponding desorption coefficients (K(des) (d)) were higher and ranged from 1.02 to 2.01. Both the adsorption and desorption of MCPA in all soil horizons was strongly and negatively related to soil pH. It appears that hydrophobic sorption plays a dominant role in the MCPA retention in topsoils whereas hydrophilic sorption of MCPA anions is the dominant adsorption mechanism in subsoils.     

Sorption of phenanthrene by soils contaminated with heavy metals

The fate of polycyclic aromatic hydrocarbons (PAHs) in soils with co-contaminants of heavy metals has yet to be elucidated. This study examined sorption of phenanthrene as a representative of PAHs by three soils contaminated with Pb, Zn or Cu. Phenanthrene sorption was clearly higher after the addition of heavy metals. The distribution coefficient (K(d)) and the organic carbon-normalized distribution coefficient (K(oc)) for phenanthrene sorption by soils spiked with Pb, Zn or Cu (0-1000 mg kg(-1)) were approximately 24% larger than those by unspiked ones, and the higher contents of heavy metals added into soils resulted in the larger K(d) and K(oc) values. The enhanced sorption of phenanthrene in the case of heavy metal-contaminated soils could be ascribed to the decreased dissolved organic matter (DOM) in solution and increased soil organic matter (SOM) as a consequence of DOM sorption onto soil solids. Concentrations of DOM in equilibrium solution for phenanthrene sorption were lower in the case of the heavy metal-spiked than unspiked soils. However, the decreased DOM in solution contributed little to the enhanced sorption of phenanthrene in the presence of metals. On the other hand, the sorbed DOM on soil solids after the addition of heavy metals in soils was found to be much more reactive and have far stronger capacity of phenanthrene uptake than the inherent SOM. The distribution coefficients of phenanthrene between water and the sorbed DOM on soil solids (K(ph/soc)) were about 2-3 magnitude larger than K(d) between water and inherent SOM, which may be the dominant mechanism of the enhanced sorption of phenanthrene by soils with the addition of heavy metals.     

不同利用方式土壤中磷的吸附与解吸特性

研究不同利用方式土壤对磷的吸附解吸特性及其影响因素。采用室内恒温培养法研究了湖南典型土壤(红壤、潮土和紫色土)的不同利用方式(旱地、水田)土壤对P的吸附和解吸过程。土壤对磷的吸附解吸过程是分阶段进行的,用Langmuir方程拟合程度比Freundlich方程高,相关系数均在0.90(P<0.05)以上;从最大吸附量(Qm)、吸附反应常数(K)和最大缓冲容量(MBC)3项吸附参数综合考虑,旱地对P的吸附无论在强度还是容量方面均大于同母质的水田土壤;解吸率随着吸附量的增加而增大,其大小为旱地<水田。Qm与<0.002 mm粘粒及无定形铁含量呈正相关,相关系数分别为0.95和0.94(P<0.05)。不同利用方式土壤P吸附解吸特性差别较大,针对不同土壤应采取不同的磷素管理措施以实现作物增产和保护环境的双重效益。     

Sorption of 3,4-dichloroaniline on four contrasting Greek agricultural soils and the effect of liming

Sorption of 3,4-dichloroaniline (3,4-DCA) on four typical Greek agricultural soils, with distinct texture, organic matter content and cation exchange capacities, was compared by using sorption isotherms and the parameters calculated from the fitted Freundlich equations. The sorption process of 3,4-DCA to the soil was completed within 48-72 h. The 3,4-DCA sorption on all soils was well described by the Freundlich equation and all sorption isotherms were of the L-type. The sandy clay loam soil with the highest organic matter content and a slightly acidic pH was the most sorptive, whereas the two other soil types, a high organic matter and neutral pH clay and a low organic matter and acidic loam, had an intermediate sorption capacity. A typical calcareous soil with low organic matter had the lowest sorption capacity which was only slightly higher than that of river sand. The 3,4-DCA sorption correlated best to soil organic matter content and not to clay content or cation exchange capacity, indicating the primary role of organic matter. The distribution coefficient (K(d)) decreased with increasing initial 3,4-DCA concentration and the reduction was most pronounced with the highly sorptive sandy clay loam soil, suggesting that the available sorption sites of the soils are not unlimited. Liming of the two acidic soils (the sandy clay loam and the loam) raised their pH (from 6.2 and 5.3, respectively) to 7.8 and reduced their sorption capacity by about 50 %, indicating that soil pH may be the second in importance factor (after organic matter) determining 3,4-DCA sorption.     

Evaluation of impacts of soil fractions on phenanthrene sorption

Phenanthrene sorption to soils and soil fractions was investigated using two contrasting soils with different clay mineral and organic carbon (OC) contents in an attempt to evaluate the contribution of each soil fraction to phenanthrene sorption and the applicability of the carbon-normalized distribution constant (K(OC)) in soils. Sorbents were characterized using surface analysis, solid-state (13)C NMR analysis, and glass transition temperature (T(g)) analysis to gain a insight into the chemical nature of OC in soils. Dissolved organic carbon (DOC) in the soil solution impeded the phenanthrene sorption, while humins accounted for the predominant phenanthrene sorption in soils. The contribution of OC to phenanthrene sorption in soil would be overestimated if only a K(OC)-approach was adopted, since clay minerals could account for much of the sorption, especially when OC was low in soils. Nitrogen gas was shown to be inappropriate for probing non-polar sorption capacity. The results obtained highlight the importance of clay minerals in governing the sorption of phenanthrene in soil, and emphasize the inapplicability of the carbon-normalized distribution coefficient K(OC) in soils.     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

Study of sorption kinetics of some ionic liquids on different soil types

In the present contribution sorption kinetics experiments under static conditions were utilized in three selected ionic liquids cations (1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium chlorides) study with five type of soil, differing in total organic carbon (TOC) content. The experimental results indicate the sorption capacity growth with increase in TOC content and hydrophobicity of ionic liquid cation. The obtained kinetic sorption parameters as well as distribution coefficients (K_d) were used to estimate the sorption properties of the soil types towards the ionic liquids in question. The Gibbs free energy values indicate that ionic liquid cations sorption on soils could be generally considered as a physical adsorption with exothermic effect. But the values of −dG for studied cations sorption on soil with very high of TOC content in soil (45%) may testify to nature of chemical adsorption. Sorption of the analyzed compounds occurs probably by means of hydrogen bonds, electrostatic and π  π interaction with the organic matter and the clay minerals of the soils.     

Competitive sorption of heavy metal by soils. Isotherms and fractional factorial experiments

Competing ions strongly affect heavy metal sorption onto the solid surfaces of soil. This study evaluated competitive sorption of Cd, Cu, Ni, Pb and Zn on three soils: Calcixerollic Xerochrept, Paralithic Xerorthent and Lithic Haplumbrept. Monometal and competitive sorption isotherms were obtained at 25 degrees C. The individual effect of ions on retention of the others was ascertained by a fractional factorial analysis design. Most of the sorption isotherms belonged to type L subtype 2 in the classification of Giles. In competitive sorption the initial linear part was shorter and the knee sharper when compared with monometal sorption isotherms. Parameters related to sorptive capacity, such as Point B, Langmuir monolayer and Freundlich distribution coefficient, were higher in monometal than in competitive sorption, and in basic soils than in acidic soil. Calcium desorbed at different points of the sorption isotherms indicated that cationic exchange with Ca was the main retention mechanism in calcareous soils. For Pb, the ratio Ca desorbed/Pb sorbed was close to one; for Cu, Ni and Zn the ratio ranged from 1.20 to 1.37, probably due to partial dissolution of calcium carbonates by hydrolytic processes during retention. On the other hand, Cd had a ratio around 0.6 reflecting another additional retention mechanism, probably surface complexation. Fractional factorial design confirmed that the presence of the cations investigated reduced the amount of the five metals retained, but the presence of Cu and Pb in the system depressed Ni, Cd and Zn sorption more than the inverse. Cation mobility was enhanced when equilibrium concentration increased and the effect was higher in Ca-saturated soils.     

Adsorption characteristics of pesticides methamidophos and glyphosate by two soils

Contributions of organic matter and minerals in soil were evaluated by comparing changes in adsorption of methamidophos (MDP) and glyphosate (GPS) before and after removal of organic matter from argaltoll (mollisol) and typustalf (alfisol) soils. Adsorption isotherms of MDP and GPS by the two soils comforted to Freundlich equation, and the adsorption capacity of GPS by argaltoll soil was higher than that of MDP. Due to the removal of organic matter from soils, K(f) values of MDP and GPS adsorbed by argaltoll soil, which were calculated from Freundlich equations and the measure of adsorption capacity, decreased by 46.1% and 75.0%, and these by typustalf soil decreased by 34.9% and 52.5%, respectively. Results from this study suggested that soil organic matter made greater contributions to adsorption of GPS, but soil minerals could provide more available adsorption sites for MDP.     

Effects of temperature on sorption-desorption processes of imidacloprid in soils of Croatian coastal regions

Sorption-desorption behavior of imidacloprid in six soils collected from five coastal regions in Croatia at 20, 30 and 40°C was investigated using batch equilibrium technique. Isothermal data were applied to Freundlich, Langmuir and Temkin equations, and the thermodynamic parameters ΔH°, ΔG°, ΔS° were calculated. The sorption isotherm curves were non-linear and may be classified as L-type, suggesting a relatively high sorption capacity for imidacloprid. Our results showed that the K( sor ) ( F ) values decreased for all the tested soils as the temperature increased, indicating that the temperature strongly influences the sorption. Values of ΔG° were negative (-4.65 to -2.00 kJ/mol) indicating that at all experimental temperatures the interactions of imidacloprid with soils were spontaneous processes. The negative and small ΔH° values (-19.79 to -8.89 kJ/mol) were in the range of weak forces, such as H-bonds, consistent with interactions and partitioning of the imidacloprid molecules into soil organic matter. The ΔS° values followed the range of -57.12 to -14.51 J/molK, suggesting that imidacloprid molecules lose entropy during transition from the solution phase to soil surface. It was found that imidacloprid desorption from soil was concentration and temperature-dependent, i.e. at lower imidacloprid concentrations and temperature, lower desorption percentage occurred. Desorption studies revealed that hysteretic behavior under different temperature treatments existed, and it was more pronounced at 20°C in the soils with higher OC content. The study results emphasize the importance of thermodynamic parameters in controlling soil pesticide mobility in different geographical locations, seasons and greenhouse conditions.     

Appendix

Abstract

The interaction of glyphosate [N‐(phosphonomethyl)‐glycine] with four typical European soils is reported. Results of adsorption and desorption isotherms show that the interaction of glyphosate with these soils was mainly related to content of iron and aluminium amorphus hydroxides. Moreover, it was found that the presence of divalent cations in 2: 1 clay minerals also contribute to glyphosate adsorption. The S‐type form of the adsorption isotherms revealed the existence of two different binding sites. These were exchangeable cations at low herbicide concentration and Fe and Al at higher glyphosate concentrations. The K maximum values of adsorption provided by the linear form of the Langmuir equation were found to be more consistent with soil parameters than those calculated by the Freundlich equation. The order of desorption from the soils was the reverse of that found for adsorption. Moreover, desorption varied from around 15 to 80% of the adsorbed herbicide according to the soil characteristics. This indicated that glyphosate adsorption on soils is far from being permanent and leaching to lower soil horizons with limited biological activity may occur.