蒙脱石对不同施肥处理土壤胡敏酸及其级分的吸附特征Ⅰ.蒙脱石对胡敏酸的吸附特征

以17年不同施肥处理土壤胡敏酸为材料,研究了不同性质胡敏酸与钙饱和蒙脱石的 吸附特征。结果表明,钙饱和蒙脱石对土不同施肥处理胡敏酸的吸附曲线可用单表面Langmuir方程、双表面Langmuir方程以及Freundlich方程来描述。由单表面Langmuir方程计算的有机肥处理（厩肥、秸秆）胡敏酸的吸附量和吸附强度大于无肥、化肥处理。温度升高各处理胡敏酸吸附量增加,但吸附强度下降。双表面Langmuir揭示,蒙脱石对胡敏酸的吸附呈现高低两种能位的吸附。高能点位的吸附以化学吸附为主,是吸热反应,低能点位的吸附以物理吸附为主,是放热反应。有机肥处理和无肥、化肥处理相比,高能点位吸附相对减弱,低能点位吸附相对增强。     

腐殖酸对蒙脱石吸附镉离子的影响机理研究

实验研究了腐殖酸存在下重金属元素镉(Cd2 )在蒙脱石表面的吸附过程,对比研究了两种不同腐殖酸对吸附机理的影响。结果表明,重金属离子在蒙脱石表面的吸附作用受介质pH的影响。加入腐殖酸后吸附产生滞后现象,蒙脱石先吸附腐殖酸,之后转变为腐殖酸和蒙脱石共同吸附Cd2 作用,吸附量较单独吸附过程更大。吸附机理与腐殖酸的投加量和投加方式有关。     

蒙脱石-氧化铁二元复合胶体吸附钨的研究

本研究选取代表性层状硅酸盐蒙脱石，两种代表性氧化铁(水铁矿、针铁矿)，合成蒙脱石-水铁矿、蒙脱石-针铁矿二元复合体，通过宏观吸附以及光谱学技术探究钨(WO₄^2-)在蒙脱石-氧化铁复合体上的吸附行为和潜在机制。结果表明：氧化铁紧密覆盖在蒙脱石表面，使表面颗粒更加细小；钨的吸附量随pH升高而降低，3种吸附剂对钨吸附量大小顺序为：蒙脱石-水铁矿>蒙脱石-针铁矿>蒙脱石；原位红外光谱实验表明，钨在蒙脱石表面主要以外圈络合物形式存在，而在蒙脱石-氧化铁复合体上形成内圈络合物(Fe-O-W)，且在低pH时，形成聚合态钨；X-射线光电子能谱进一步表明，针铁矿和水铁矿表面铁羟基参与了钨的络合反应。本研究证实，氧化铁覆盖不仅增大蒙脱石对钨的吸附量，而且使钨由外圈络合物形态转变为内圈络合态，进一步生成聚合态钨。研究结果对预测钨在土壤中的迁移转化、生物有效性和归宿有重要指导意义。     

不同施肥处理土壤胡敏酸及其级分与蒙脱石的吸附特征 Ⅱ. 蒙脱石对胡敏酸不同级分的吸附

采用酒精沉淀法，反不同施肥处理土壤胡敏酸分7个级分，研究了胡敏酸不同级分与钙饱和蒙脱石的吸附特征。结果表明，蒙脱石对胡敏酸各级分的吸附可用单表面Langmuir、双表面Langmuir和Freundlich方程来描述。各级分的吸附量和吸附强度不是随级分数变化单一递增或递减，在7个级分中，级分4、3的吸附量和吸附强度较大，是吸附最佳级分。说明级分4、3具有与蒙脱石胶体最佳的成键吸附状态，是吸附最佳分子状态，有机肥处理，吸附最佳级分的吸附性状（吸附量和吸附强度）优于化肥、无肥处理。     

不同施肥处理土壤胡敏酸及其级分与蒙脱石的吸附特征 Ⅱ. 蒙脱石对胡敏酸不同级分的吸附

采用酒精沉淀法，把不同施肥处理土壤胡敏酸分为7个级分，研究了胡敏酸不同级分与钙饱和蒙脱石的吸附特征。结果表明，蒙脱石对胡敏酸各级分的吸附可用单表面Langmuir、双表面Langmuir和Freundlich方程来描述。各级分的吸附量和吸附强度不是随级分数变化单一递增或递减，在7个级分中，级分4、3的吸附量和吸附强度较大，是吸附最佳级分。说明级分4、3具有与蒙脱石胶体最佳的成键吸附状态，是吸附最佳分子状态。有机肥处理，吸附最佳级分的吸附性状（吸附量和吸附强度）优于化肥、无肥处理。     

蒙脱石对不同施肥处理土壤胡敏酸及其级分的吸附特征Ⅰ.蒙脱石对胡敏酸的

以１７年不同施肥处理土壤胡敏酸为材料,研究不同性质胡敏酸与钙饱和蒙脱石的吸附特征。结果表明,钙饱和蒙脱石对娄土不同施肥处理胡敏酸的吸附曲线可用单表面Ｌａｎｇｍｕｉｒ方程、双表面Ｌａｎｇｍｕｉｒ方程以及Ｆｒｅｕｎｄｉｃｈ方程来描述。由单表面Ｌａｎｇｍｕｉｒ方程计算的有机肥处理（厩肥、秸秆）胡敏酸的吸附量和吸附强度大于无肥、化肥处理。温度升高各处理胡敏酸吸附量增加,但吸附强度下降。双表面Ｌａｎｇｍｕｉｒ揭示,蒙脱石对胡敏酸的吸附呈现高低两种能位的吸附。高能点位的吸附以化学吸附为主,是吸热反应,低能点位的吸附以物理吸附为主,是放热反应。有机肥处理和无肥、化肥处理相比,高能点位吸附相对减弱,低能点位吸附相对增强。     

高岭石,蒙脱石和针铁矿对泥炭腐殖酸的吸附和分离

Sorption of humic acid (HA) on mineral surfaces has a profound interest regarding the fate of hydrophobic organic contaminants (HOCs) and carbon sequestration in soils. The objective of our study is to determine the fractionation behavior of HA upon sorption on mineral surfaces with varying surface properties. HA was coated sequentially on kaolinite (1:1 clay), montmorillonite (2:1 clay), and goethite (iron oxide) for four times. The unadsorbed HA fractions were characterized by elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), and solid state ¹³C nuclear magnetic resonance spectroscopy (NMR). The mineral-HA complexes were characterized by DRIFT. Polarity index [(N+O)/C] revealed higher polarity of the unadsorbed HA fractions after coating on kaolinite, reflecting that relatively higher polarity fractions of HA remain unadsorbed. Sorption of aliphatic alcohol fraction along with carbohydrate was prominent on kaolinite surface. DRIFT results of the unadsorbed HA fractions indicated more sorption of aliphatic moieties on both kaolinite and montmorillonite. DRIFT results of the unadsorbed HA fractions after sorption on kaolinite and goethite showed the sorption of the proteinaceous fractions of HA. The HA fractions obtained after coating on goethite showed significant sorption of carboxylic moieties. The results mentioned above comply reasonably well with the DRIFT spectra of the mineral-HA complexes. ¹³C NMR results showed higher sorption of anomeric C on kaolinite surface. Higher sorption of paraffinic fraction was observed on montmorillonite. NMR data inferred the sorption of carboxylic moieties on goethite surface. Overall, this study showed that aliphatic moieties of HA preferentially sorbed on kaolinite and montmorillonite, while carboxylic functional groups play a significant role in sorption of HA on goethite. The sorbed fractions of HA may modify the mineral surface properties, and thus, the interaction with organic contaminants.     

蒙脱石-氧化铁复合体的表征及其对不同形态磷的吸附特性

制备了蒙脱石-针铁矿复合体(Mt-Goe)和蒙脱石-非/弱晶质氧化铁复合体(Mt-HFO),研究了它们的结构、表面性质及其对无机磷酸盐(Pi)和植酸(IHP)的吸附特性。结果显示,Mt-Goe中少量羟基铁离子进入了蒙脱石晶层间导致其层间距增大,针铁矿颗粒较好地包被在蒙脱石外表面;Mt-HFO中蒙脱石层间则发生了Fe~(3+)水解,生成了(羟基)铁氧化物,并在蒙脱石表面形成非晶质氧化铁颗粒。蒙脱石、Mt-Goe和Mt-HFO的比表面积分别为258.7、185.4和226.4 m~2·g~(–1),其表面分形度、等电点和表面羟基含量均依次升高,pH5.5时的表面Zeta电位分别为–46.1、–13.6和–19.4 mV。3种样品对Pi和IHP的吸附模式以匀质性表面单层吸附为主,Langmuir饱和吸附量(qmax)和吸附亲和力均表现为由大到小依次为Mt-HFO、Mt-Goe、蒙脱石。3种样品对Pi和IHP的动力学吸附过程适合用准二级动力学模型描述,其速率常数由小到大依次为Mt-HFO、Mt-Goe、蒙脱石。与吸附Pi相比,3种样品吸附IHP的动力学速率常数明显减小,吸附量明显增大;Mt-HFO对IHP的吸附速率尤其缓慢,而吸附量远大于对Pi的吸附量。     

蒙脱石载菌的条件优化及其影响因素研究

以天然硅酸盐蒙脱石为材料,附载了具有生物修复功能的复合益生菌并优化了构建条件。此外,研究了蒙脱石载菌的影响因素。结果表明,当蒙脱石重量为0.5g时,载菌量达到较恒定的状态,且随着益生菌浓度和体积的增大而增加。蒙脱石对益生菌的吸附能力随着pH值的升高而逐渐降低,不同离子强度条件下,呈现相同趋势。不同温度条件下,蒙脱石对益生菌的吸附率呈现出先升高后降低的趋势,当温度为30℃时吸附率最高为89.74%。这表明益生菌的吸附不仅依赖于生物体的生物化学属性和表面属性,也受到环境温度等条件的影响。     

钠、钾离子对Bt蛋白在蒙脱石和凹凸棒土表面吸附与解吸的影响

采用静态吸附法研究了钠、钾离子对苏云金杆菌杀虫蛋白在蒙脱石和凹凸棒土表面吸附与解吸特性的影响。结果表明,添加钠、钾离子（0~2 mmol.L-1）均可提高Bt蛋白在两种矿物上的平衡吸附量,但等温吸附曲线的Langmuir方程拟合基本没受影响。添加钠离子或钾离子均能引起矿物粒子Zeta负电位升高,提示钠、钾离子通过减小矿物粒子与Bt蛋白之间斥力的方式促进了Bt蛋白吸附。在蒙脱石吸附Bt蛋白过程中添加钠、钾离子可使Bt蛋白的水解吸率升高,但解吸后的残留量变化不大;在凹凸棒土吸附Bt蛋白过程中添加钠、钾离子可使Bt蛋白的水解吸率减小,且解吸后的残留量增加。     

Adsorption of the Bacillus thuringiensis toxin (Cry1Ab) on Na‐montmorillonite and on the clay fractions of different soils

The adsorption of the toxin from Bacillus thuringiensis (Bt‐toxin), which is synthesized in genetically modified maize, on sterilized Na‐montmorillonite and on H₂O₂‐treated and untreated clay fractions of three soils from different sites were studied. All adsorption isotherms can be described by a linear isotherm. Although all clay fractions from the different soils show nearly the same mineralogical composition, we found different affinities ranging from k = 47.7 to k = 366.7 of the adsorbates for the Bt‐toxin. The H₂O₂‐treated clay fractions show no correlation between the adsorption affinity and the amount of soil organic matter. On the other hand, there is a correlation between the content of organic carbon and the adsorption affinity of the untreated clay fractions. This can be explained by the fact that due to the coatings of soil organic matter on aggregates, the Bt‐toxin polymers are not able to adsorb within the clay aggregates.     

不同阴离子溶液中怀俄明州蒙脱石的Na-Zn交换选择性

The effect of background anion on cation exchange reactions, such as Na-Ca and Na-Cu exchange reactions, on montmorillonites has been studied, but the results are not always clear and discrepancies exist in the literature. In this study, the exchange of zinc (Zn²⁺) for sodium (Na⁺) on Wyoming montmorillonite was investigated at 298°K using Cl^-, ClO₄^-, NO₃^-, OAc^-, and SO₄^2- solution media at a constant total metal charge concentration of 0.0200 molc L^-1. Results indicated that the clay CEC values were essential similar for Cl^-, ClO₄^-, NO₃^- and SO₄^2- solution media with an average CEC of 0.856 ± 0.008 molc kg^-1; in an OAc⁺ solution the clay CEC was much higher than that in other anion media. The specific adsorption of Zn (SAZn), as defined by the extraction of Zn using 0.05mol L^-1 Na₂-EDTA, was different in the various background solutions. The highest value for SAZn was 0.359 ± 0.0350molc kg^-1, which occurred in OAc-solution. There was essentially no difference in the total apparent adsorbed metals (the sum of adsorbed equivalents of Na and Zn per kilogram of clay, Q) among the various background solutions. The average Q for all anion media was 0.807 ± 0.011 mol_c kg^-1 and was independent of exchanger composition. Experimental results indicated that there were no significant monovalent cation complexes such as ZnCl⁺ or ZnNO₃⁺ that were adsorbed by montmorillonite. The Na-Zn exchange isotherms indicated that there was an adsorption preference for Zn over Na on Wyoming montmorillonite.     

Synthesis of highly intercalated urea-clay nanocomposite via domestic montmorillonite as eco-friendly slow-release fertilizer

The present study describes the preparation and characterization of montmorillonite-urea nanocomposites (Mt-Ur) using aqueous suspension technique at various stirring times and different ratio of montmorillonite to urea (Mt/Ur) via an impure and domestic montmorillonite (Mt), without the application of any chemical reagents and high-energy-demand process (environmentally friendly). The intercalation of urea into Mt interlayer was clearly demonstrated by a significant expansion of d₀₀₁ spacing (interlayer space of Mt) from 1.23 to 1.71 nm which has not yet been reported by aqueous suspension technique. Analyses performed by Fourier transform-infrared spectroscopy (FT-IR), Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) also confirmed the effectiveness of this simple process to intercalate the urea into clay lamella. The release pattern demonstrated that the nanocomposite had a slow-release behaviour for urea dissolution. The results also suggested that the Mt type applied in the current study, in a 1:20 Mt/Ur ratio and stirred for 1 h, possessed desirable ecological and economic efficiency in the production of slow-release urea fertilizer due to the application of the impure and domestic clay which is of very low-cost and eco-friendly. Nevertheless, urea was fully intercalated into the interlayer of clay by a simple technique and with a good slow-release behaviour.     

Adsorption and binding of peptides on homoionic montmorillonite and kaolinite

The adsorption and binding (amount retained after extensive washing) of peptides (two, three or four amino acids with isoelectric points ranging from pH 3.31 to 6.81) on montmorillonite (M) and kaolinite (K) made homoionic to H, Na, Ca, Zn, Al or La were studied. The amount of peplide adsorbed or bound varied with the type of clay, the type of cation saturating the clay, and the constitutive amino acids of the peptides. Di-, tri- and tetraglycine were adsorbed to a greater extent on M than on K. A larger amount of the basic peptide, l-alanyl-l-lysine, than of the acidic peptide, l-aspartylglycine, was adsorbed. The heterocyclic peptides, l-histidylglycine and l-prolyl-l-phenylalanylglycyl-l-lysine, were preferentially adsorbed on M homoionic to di- and trivalent cations. Only l-aspartylglycine, l-histidylglycine. l-alanyl-l-lysine and l-prolyl-l-phenylalanylglycyl-l-lysine were bound on M, and only diglycine, tetraglycine and l-prolyl-l-phenylalanylglycyl-l-lysine were bound on K.     

Adsorption and binding of amino acids on homoionic montmorillonite and kaolinite

The adsorption and binding of amino acids (aspartic acid, cysteine, glycine, proline and arginine), ranging in molecular weight from 115 to 174 and in isoelectric point from pH 2.8 to 10.8, to montmorillonite [M] and kaolinite [K] homoionic to H, Na, Ca, Zn, La or Al were studied in unbuffered suspensions. Aspartic acid was adsorbed and bound on M homoionic to Ca or Zn but only adsorbed to K homoionic to Ca or Zn. Cysteine was only adsorbed on M homoionic to Al and adsorbed and bound on M homoionic to Zn and on K homoionic to H or Zn. Proline was adsorbed and bound on M homoionic to H, Ca or Zn and on K homoionic to H; it was adsorbed but not bound on both M and K homoionic to Al. Arginine was adsorbed and bound on M homoionic to H or Al and only adsorbed on K homoionic to Ca or Zn. Glycine was not bound on any of the clays. The amounts of amino acid adsorbed and bound (measured by the loss of amino acid from solution) and the class (Giles et al., 1974a and b) of both the adsorption and binding isotherms (retention against ultimate washing with water) were dependent on the type of amino acid, the type of clay, the type of cation predominant on the clays and the basicity or the additional function moiety (e.g. carboxyl, thiol, guanido) of the amino acid. The relative values of the non-standard free energy of clay-amino acid complexes that had isotherms of the Giles C-class were dependent on the type and molecular weight of the amino acid and on the exchangeable cation on the clay.     

颗粒物对乐果的吸附特征

研究了颗粒物（内蒙古土壤Y2、Y3、Y4和黄河水体表层沉积物Y1）对有机磷农药乐果的吸附规律,观察了颗粒物的性质如有机质、粘粒、CEC（阳离子交换量）和离子强度等因素对吸附行为的影响。结果表明,内蒙古4种颗粒物对乐果的吸附过程可用Freundlich等温式描述,吸附常数在1.4848～1.9550mL·g-1之间;影响颗粒物对乐果吸附的主要因素是CEC、离子强度和有机质,颗粒物对乐果的吸附量与颗粒物的CEC有着极显著的正相关关系,相关系数为0.9812,P〈0.01;随着离子强度的降低,4种颗粒物对乐果的吸附量增大;除黄河水体表层沉积物Y1外,颗粒物的有机质含量越高,对乐果的吸附能力就越强。     

胡敏酸对铵钾在粘土矿物上交互作用的影响

Interaction of ammonium (NH+4) and potassium (K+) is typical in field soils. However, the effects of organic matter on interaction of NH+4 and K+have not been thoroughly investigated. In this study, we examined the changes in major physicochemical properties of three clay minerals (kaolinite, illite, and montmorillonite) after humic acid (HA) coating and evaluated the influences of these changes on the interaction of NH+4 and K+on clay minerals using batch experiments. After HA coating, the cation exchange capacity (CEC) and specific surface area (SSA) of montmorillonite decreased significantly, while little decrease in CEC and SSA occurred in illite and only a slight increase in CEC was found in kaolinite. Humic acid coating significantly increased cation adsorption and preference for NH+4, and this effect was more obvious on clay minerals with a lower CEC. Results of Fourier transform infrared spectrometry analysis showed that HA coating promoted the formation of H-bonds between the adsorbed NH+4 and the organo-mineral complexes. HA coating increased cation fixation capacity on montmorillonite and kaolinite, but the opposite occurred on illite. In addition, HA coating increased the competitiveness of NH+4 on fixation sites. These results showed that HA coating affected both the nature of clay mineral surfaces and the reactions of NH+4 and K+with clay minerals, which might influence the availability of nutrient cations to plants in field soils amended with organic matter.     

蒙脱石纳米复合物的制备及其吸附作用研究

对天然蒙脱石(M)矿物进行钠化改型和柱撑复合,制备了蒙脱石纳米复合物(MN),并对其进行表征,同时研究其对黄曲霉毒素的吸附作用。结果表明：与M相比,MN的层间距和比表面积明显增大,d₍₀₀₁₎值增加到1.96 nm,比表面积达到149.68m²/g,而且孔体积增加,孔直径缩小,微孔比例提高。吸附试验表明：复合改性后,MN对黄曲霉毒素的吸附容量和吸附速率均明显优于M。这些结果提示MN可望成为性能优越的黄曲霉毒素吸附剂。