有机质对三峡库区水体中土壤胶体颗粒凝聚影响机制研究

采用联合测定法和光散射技术分别研究了有机质对土壤颗粒表面电荷性质和水体中胶体颗粒凝聚过程的影响。结果表明:添加有机质能显著改变土壤表面电荷性质,使得土壤颗粒表面电荷数量降低6.8%,比表面积增加12.3%,使颗粒表面电荷密度减小,表面电位降低;进一步理论计算表明添加有机质降低了胶体颗粒间的静电排斥力,使得净引力增大,胶体颗粒更易发生凝聚。通过动态光散射分析水体中土壤胶体颗粒的凝聚特征,发现有机质去除前后的临界聚沉浓度(CCC)分别为91.6 mmol/L和139.3mmol/L,去除有机质土壤显著大于未去除有机质的土壤,相应浓度下的临界电位值计算结果均为-150mV左右,与颗粒间出现净引力的临界浓度值基本一致。有机质对水体中胶体颗粒凝聚特性的影响主要是通过改变颗粒表面性质使得颗粒间的相互作用发生变化而引起。     

有机修饰塿土总酸度和电荷性质的初步研究

土壤表面电荷特性是土壤十分重要的表面特性参数,其不但与土壤溶液中阴阳离子的吸附与解吸具有直接的关系,同时土壤中的离子扩散、土壤有机-无机复合体的形成以及土壤的水分性状在不同程度上也均受到土壤胶体表面电荷性质的影响。近年来国内外开始研究应用阳离子型表面活性剂对黏土矿物或土壤进行修饰,以增大对土壤中有机污染物的吸附能力[1,2],由于采用表面活性剂能够使得土壤的表面疏水性增加而亲水性减弱,其表面电荷性质也必然发生相应的变化,而这种变化对土壤中有机、重金属污染物的吸附固定将会产生本质的影响[3~7]。因此,研究土壤表面修饰后土壤电荷特性的变化,对于深入了解土壤表面修饰的机理,从理论上探讨修饰土样对于     

土壤亲水性的初步研究

土壤的亲水性是土壤胶体的一个重要属性.它不仅与土壤胶体的许多其它重要性质(如胶体的分散、絮固、胶溶、胶凝和老化等)密切相关,而且对土壤的结构特性,水分状况和吸附性能等也有一定的影响.在农业生产上也有其重要的实际意义.土壤胶体颗粒具有亲水性主要在于它的水合作用.     

黄土高原植被恢复过程中土壤表面电化学性质演变特征

土壤胶体表面所带电荷是土壤具有一系列物理、化学性质的根本原因。表面电荷数量、比表面积、表面电荷密度、表面电场强度以及表面电位是土壤胶体颗粒重要性质,影响土壤中物理、化学、生物化学过程。运用带电颗粒表面性质联合分析法,测定黄土高原子午岭地区不同植被类型下土壤表面电荷性质,研究自然植被恢复过程对土壤表面电荷性质的影响。结果表明:随着植被的演替,子午岭林区土壤表面电荷数量、比表面积、表面电荷密度均随植被的恢复增加,变化范围分别为10.88～19.85 cmol·kg~(–1)、40.67～61.71 m~2·g~(–1)和0.22～0.31 c·m~(–2),平均值分别为16.18 cmol·kg~(–1)、54.88 m2·g~(–1)和0.28 c·m~(–2),土壤表面电场强度达108 V·m~(–1)数量级;土壤黏粒、有机碳含量是影响表面电荷性质的主要因素,解释率分别为62.5%和27.9%;土壤基本性质对表面电荷性质的影响由强到弱依次为:黏粒、有机碳、砂粒、全氮、C/N、粉粒、碳酸钙、pH。研究结果对于进一步认识黄土高原土壤颗粒表面性质,加深理解土壤中发生的一系列物理化学过程具有重要意义。     

不同磷水平塿土的表面性质及其对磷素流失特征的影响

为明确不同磷水平塿土的表面电化学性质特征,阐明电解质浓度调控下塿土表面性质的变化及其与土壤磷素流失特征的内在关联,利用物质表面性质联合测定分析技术,结合降雨模拟试验,研究了长期定位配施磷肥条件下不同磷水平塿土的表面电化学性质及其对土壤磷素流失特征的影响。结果表明：（1）长期施磷处理下的塿土全磷含量为不施磷处理的2.46倍,但其表面电位、表面电荷密度、表面电场强度、比表面积以及表面电荷数量均低于不施磷处理塿土;（2）不同磷水平塿土均表现出土壤颗粒及磷素流失量随着土粒表面电位（绝对值）升高而加剧的趋势,颗粒态磷的累积流失量与土壤颗粒累积流失量间呈线性正相关;（3）由于低磷水平塿土表面电位（绝对值）相对较高,所受土壤颗粒间静电排斥力更大,导致土壤团聚体稳定性较差,土壤颗粒及其附着磷素累积流失量更多;（4）本实验条件下土壤中磷素流失以颗粒态磷为主,占流失总量的81%～99%,溶解态磷占比十分有限。本研究阐明了长期定位施磷处理对土壤表面电化学性质的影响,明确了表面性质变化与土壤颗粒及磷素流失特征的关系,为长期施磷土壤的环境风险防控提供了新思路。     

水解聚马来酸酐对森林暗棕壤和草地退化盐碱地土壤 胶体表面结构与组成的影响

水解聚马来酸酐(HPMA)能起到土壤改良的作用,进而促进种子萌发及植物生长,但是其与土壤相互作用的深层机理尚未阐明。基于此本文选用HPMA处理森林暗棕壤和草地退化盐碱地土壤胶体,并用激光粒径仪、原子力显微镜、扫描电镜、X射线衍射、红外光谱、X射线光电子能谱进行分析,探究HPMA对土壤胶体表面结构特征、矿物组成和有机组成的影响,旨在揭示HPMA对不同土壤胶体的影响差异的深层机理。结果显示,HPMA能够改良退化土壤的原因应该与其对土壤胶体表面结构特征、矿物结晶和有机化学元素组分的影响有关,但对森林暗棕壤和草地退化盐碱地土壤的影响存在明显差异。对于森林暗棕壤这种优质土壤,HPMA处理后,矿物质的结晶度有降低的趋势,但并没有产生强烈的化学反应,多数官能团趋向于增加,碳酸盐官能团降低幅度不是很大,约3%~8%,土壤胶体粒径增加了,其中表层增加了13.62%,深层增加了34.96%,但只有深层土壤达到显著水平。而对于草地退化盐碱地土壤,土壤胶体粒径显著增加(27.54%),达到了统计学显著水平(P0.05),除了石英相对结晶度降低了7.10%,其余都降低了30%以上,导致不同土壤矿物的晶粒尺寸显著增加了(水云母、蛭石、高岭石的晶粒尺寸分别增加101.37%、56.16%、50.76%),多数官能团的相对含量降低,其中碳酸盐官能团降低量最大,达到96.79%,这些使得土壤元素配比逐渐趋向于优质土壤(C:O=0.27;C:N=9.98;C:Si=0.91;O:Si=3.38;Si:N=10.93),这可能意味着HPMA与土壤胶体中的碳酸钙等不同土壤矿物发生了强烈的化学反应,从而影响了土壤晶粒结构和化学组成,进而起到土壤改良的作用。     

几种土壤胶体电荷零点(ZPC)的初步研究

研究土壤胶体的性质有着重要的意义,在许多土壤胶体的特性中,电化学性质是一个重要方面。大家知道,被分散在电解质溶液中的胶体颗粒,在与电解质溶液接触时,便产生了双电层,根据胶粒和溶液界面间游离电荷分布的机制,可以把土壤胶体区分为两种基本类型:(1)完全极化界面的胶体称为恒表面电荷胶体;(2)可逆界面胶体称为恒表面电位胶体^[10,14]。     

长期不同施肥的棕壤胶体凝聚动力学比较研究

土壤胶体的凝聚与土壤团聚体的形成密切相关。施肥改变土壤溶液环境，对土壤团聚体形成、土壤结构和土壤物质组成产生影响。探索长期不同施肥影响土壤胶体微观性质和相互作用进而影响土壤宏观现象的关联十分必要。本研究依托三十五年棕壤长期定位施肥监测试验站，选取不施肥处理（CK）、施用氮肥（N）、施用有机肥（M）、氮肥与有机肥配合施用（N+M）四种处理的土壤为研究对象，采用动态光散射技术监测不同施肥处理的土壤胶体凝聚动力学过程，通过对比分析土壤有机质含量、表面化学性质和土壤矿物组成等探究不同施肥处理对土壤胶体凝聚过程的影响。研究发现：四种长期不同施肥处理的棕壤胶体凝聚特征均表现为在低电解质浓度条件下发生慢速凝聚（RLCA）与高电解质浓度条件下的快速凝聚（DLCA）；不同施肥处理胶体在相同电解质体系中的临界聚沉浓度的大小顺序均为M > N+M > CK > N。有机肥的长期施用增加了土壤有机质含量，从而提高了胶体颗粒表面电场强度，加大了胶体颗粒间的静电斥力，加之有机质组分的空间位阻效应使得胶体的凝聚现象减弱；另一方面，长期不同施肥处理并未改变土壤黏土矿物组成类型，但对其相对含量产生影响：其中，有机肥的长期施入使2:1型伊利石的相对含量增加，1:1型高岭石的相对含量减少，长期施用氮肥使伊利石相对含量减少而高岭石相对含量增加。综上，长期不同施肥处理改变棕壤胶体的基本理化性质和矿物组成比例关系，进而影响棕壤胶体的凝聚动力学过程。     

离子界面行为在土壤有机无机复合体形成中的作用

土壤有机物质与土壤矿物质表面之间的相互作用普遍存在,有关土壤有机无机复合体形成理论的研究倍受关注,土壤有机质与矿物质结合的紧密程度直接关系到土壤碳库的稳定性,在环境科学与农业资源利用领域有重要意义。但关于土壤有机无机复合体形成机制还不完善,土壤宏观、介观及微观各尺度间的作用机制未能衔接。本文综述了土壤有机无机复合胶体的形成(形成学说、作用机制与影响因子)及此过程中离子的界面行为;系统地梳理了离子在土壤有机无机复合体形成中的作用机制;回顾了土壤有机无机组分相互作用的研究方法;最后强调了离子特异性效应在土壤有机无机复合体形成中的作用,特别是化合价相同的不同离子对土壤系统的性质与过程具有不同的影响。即离子电子层数和外层电子排布的微小差异在土壤表面附近的强电场中被放大,通过极化作用提高离子的有效电荷,增强离子所受的库仑作用力。离子的有效电荷数可以定量表征该土壤胶体复合过程中界面上离子作用的强弱程度。结论不断完善土壤有机无机复合体形成理论,为土壤培肥和污染土壤修复提供理论依据,对促进土壤有机无机复合体环境化学和微粒污染物迁移动力学的研究具有重要的科学意义与实践意义。     

Cu(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)在红壤胶体和非胶体颗粒上吸附的比较

研究了湖南长沙和海南昆仑的2种红壤胶体和非胶体的矿物组成、阳离子交换量(CEC)及Cu(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)在土壤胶体和非胶体颗粒表面的吸附行为,以明确红壤胶体对土壤表面化学性质的贡献。X射线衍射分析结果表明,两种红壤胶体的矿物组成均以次生矿物为主,次生矿物又以1∶1型高岭石所占比例最高。土壤非胶体颗粒中石英等原生矿物含量较高。土壤铁铝氧化物主要富集在土壤胶体部分,土壤胶体颗粒中游离氧化铁和游离氧化铝含量明显高于非胶体颗粒,如湖南长沙红壤胶体颗粒游离氧化铁的含量为78.03 g kg~(-1),而非胶体颗粒中仅为9.93 g kg~(-1)。土壤胶体颗粒的CEC显著高于非胶体颗粒部分,2种红壤胶体的CEC约为非胶体的12倍。等温吸附实验结果表明,土壤胶体颗粒对Cu(Ⅱ)、Pb(Ⅱ)与Cd(Ⅱ)的最大吸附量和吸附亲和力均显著大于非胶体颗粒,湖南红壤胶体对3种重金属的吸附量大于海南红壤胶体,与土壤胶体的矿物组成和CEC大小一致。Cd(Ⅱ)在红壤胶体和非胶体颗粒表面主要发生静电吸附,而静电吸附和非静电吸附两种机制均对Cu(Ⅱ)和Pb(Ⅱ)的吸附有重要贡献。     

草萘胺在五种土壤及其胶体上的吸附行为

土壤胶体是土壤中颗粒最细小的部分,由于具有巨大的比表面积和较高的吸附容量,是环境中污染物的重要吸附剂,直接影响到污染物的归趋和生物有效性.本文采用批次吸附试验的方法,研究了农药草萘胺在黄棕壤等5种土壤及土壤胶体上的吸附行为.结果表明,草萘胺在供试土壤及胶体上的吸附均能很好地符合Freundlich方程;与本体土壤相比,...     

Size Characterization by Laser Granulometry of Colloids Extracted from Compost at Different Temperatures

The objective of this work was to characterize colloids extracted from composts and their potential retention in soils. Compost made of sludge and green wastes was sampled (i) during the fermentation phase and (ii) after maturation. The same kind of compost was used in a long-term field experiment at Feucherolles (France), near Paris where amended and nonamended soils were sampled. The colloidal fraction was extracted from composts in water at room temperature (20°C) and compared to the colloidal fraction extracted from the soil. Composts were also extracted by pressurized hot liquid water at 50, 125 and 175°C. The total organic carbon of the extracts was measured and the particle size distribution (PSD) of colloidal extracts was analyzed by laser granulometry. The diameters of the colloids extracted from the soil ranged between 0.040 and 0.300 μm, independently of the temperature. For composts, it varied from 0.040 to 3.200 μm when extraction was done at 20°C, while at higher temperatures, much more organic matter was extracted, and colloid diameters ranged from 0.040 μm to 0.200 μm. The water-soluble C decreased and the size of colloids recovered in water at temperatures below 50°C increased when compost maturity increased. The adsorption on soils of colloidal particles extracted from composts was characterized. The largest adsorption (up to 30% of the initial soluble C) occurred with the extracts recovered at high temperature, in relation to the more hydrophobic properties of the colloids extracted with hot water maintained in subcritical conditions. After adsorption, the particle size distribution in the colloidal fraction extracted at 20°C moved towards finer fractions; by contrast, the colloidal fraction extracted at 175°C moved towards coarser fractions. The coarsest colloids coming from the soil disappeared during the adsorption experiment, probably because of the coprecipitation with the finest colloids coming from compost.     

Phosphorus-induced mobilization of colloids: model systems and soils

Increasing the phosphorus (P) saturation of sandy soils may cause an increase in the rate of transport of dissolved P to groundwater. We hypothesize that by increasing sorption of P, soil colloids such as iron (Fe) oxides are also mobilized, because the adsorption of P causes the surface charge to become more negative, which increases the repulsive forces between the colloids and the sand grains, and between the colloids in suspension. Goethite particles adsorbed to fine quartz sand and precipitated goethite coatings on coarse quartz sand were used as model systems to test this hypothesis. Soil samples from a Cambisol Bw horizon and a Gleysol Bg horizon were also investigated. We conducted a series of batch experiments with increasing concentrations of ortho‐P and inositol hexaphosphate (IHP). The adsorption of P and the dispersion of colloids were determined by measuring P, Fe, aluminium and carbon concentrations in supernatants before and after ultracentrifugation. Dispersed colloids were characterized according to their optical density, zeta potential and particle size. The addition of P caused mobilization of goethite and soil colloids when a critical P saturation, corresponding to a zeta potential of about ?20 mV, was exceeded. To induce colloid mobilization in soils, one to two orders of magnitude larger equilibrium concentrations of dissolved P were necessary, compared with those required for the model systems. The adsorption of IHP reduced the zeta potential of colloids more effectively than the adsorption of ortho‐P per mol P. Environmentally significant concentrations of colloidal P (> 0.1 mg P litre^?1) were released from soil samples at equilibrium concentrations of dissolved P < 0.1 mg P litre^?1. We conclude that the sorption and accumulation of P in sandy subsoils that might occur as a result of excessive fertilization might induce the mobilization of colloids and colloidal P.     

Physicochemical principles of the fractal organization of soil colloids

An electron-microscopic study was conducted of gel films collected from aggregates from humus-accumulative horizons of chernozem and soddy-podzolic soils. The aggregates were dried and then capillary-wetted and immersed in water, Solutions obtained by pressing from these soils were also studied. Based on the results obtained, a hypothetical mechanism was proposed for the development of fractal organization of soil colloids, which involves the fixation of micron-size mineral particles in the humus gel and their transformation under the effect of aggressive substances with the formation of colloidal particles of reaction products diffusing in the humus gel. Humus macromolecules contain many polar groups; therefore, the colloidal particles pass some distance and are then fixed on these groups. The greater the distance from a coarse particle in the center of a cluster the smaller the number of colloidal particles capable of traversing it. Therefore, the concentration of colloidal particles decreases when going from the cluster center to its periphery according to an exponential law, which results in the development of the fractal organization in the colloidal soil component. Results of soil studies using the small-angle neutron scattering method were analyzed in terms of the hypothesis proposed.     

瓦碱的碱度与板结

“瓦碱”是一种碱化的浅色草甸土,零星分布于我国黄淮海平原的盐碱土地区。瓦碱的土表板平,呈灰白色,没有盐霜或很少盐霜。早春干旱时,土表易于板结,抑制幼苗生长,常引起缺苗现象,土壤板结严重时,甚至全部死亡,形成光板地。瓦碱上难以出苗,卽使出苗,苗也弱,分蘖少,但是出苗以后植株的生长此在附近盐土上好得多,因此羣众说:“瓦碱发老苗,不发小苗”。黄淮海平原内瓦碱的情况已有报导^[1-6],但少有详细的理化研究。本文拟就瓦碱苗弱和不出苗的原因及其改良原则进行初步研究。     

Structure and properties of soil organic-mineral gel

Changes in the fractal dimension and scattering intensity of colloidal structures in a chernozem, soddy-podzolic soil, and a krasnozem were studied by small-angle neutron scattering at different temperatures and soil water contents. The character of the neutron scattering by soil colloids indicated that the latter were mass fractals in all of the soils studied; i.e., the colloidal particles were located apart from one another even in dry soils. The obtained results confirmed the supposition about the distribution of colloidal particles in the humus gel matrix. The changes in the fractal parameters of the soddy-podzolic soil and chernozem with increasing water contents were nonmonotonic in character, which indicated complex structural rearrangements of the colloidal component in these soils. From the results obtained, a conclusion was drawn that the destruction of the molecular network of reinforced humus gel occurred upon heating the soils to high temperatures: colloidal particles reinforcing the humus gel began to move and coagulate with the formation of dense aggregates. The electron-microscopic study of gel films released from the predried and then capillary wetted aggregates in water showed that the gel films were nonhomogeneous and included zones of humus gel reinforced by colloidal particles and zones almost free from these particles.     

Influence of water-dispersible colloids from organic manure on the mechanism of metal transport in historically contaminated soils: coupling colloid fractionation with high-energy synchrotron analysis

Purpose

Colloid-facilitated transport of metals is widely observed while manure is used for the improvement of contaminated soil. Details on the mechanism of colloid-associated metal transport are still lacking. This work investigated the nature of water-dispersible colloids (WDC) from different organic manures, differentiated the significance of clay and organic colloids in the metal transport, and finally provided direct and quantitative evidence for the importance of WDC in the colloid-facilitated transport of metals.

Materials and methods

Column experiments were conducted to assess the overall significance of WDC from effective microbial inoculated manure (EM) and leaf mulch (LM) for metal transport in alkali-contaminated soil. The properties of organic colloids such as hydrophilicity, aromaticity, and functional characteristics were analyzed by DAX-8 resin column, specific UV absorbance, and Fourier-transform infrared spectroscopy, respectively. Colloid identification and metal species determination were conducted using a combination of X-ray absorption near-edge structure, X-ray fluorescence spectroscopy, and transmission electron microscopy coupled with energy-dispersive X-ray analysis.

Results and discussion

Approximately 100 % of Pb, 69 % of Zn, and 38 % of Cu in the colloidal particles came from soil clay in the presence of EM colloids, while more than 80 % of Pb, Zn, and Cu in the LM colloids. Combined with the quantities of colloidal metals, it revealed that clay release was inhibited in the former and enhanced in the latter. The quantities of Cu and Zn associated with the EM colloids were much higher than that with the LM colloids. The contrary result was observed for Pb. LM colloids increased the quantities of organically associated Pb significantly.

Conclusions

Clay-associated metal transfer was influenced by the nature of WDC. Microbial manure colloids inhibited the clay-associated transfer of metals in the soils probably due to the presence of polysaccharide and microbially derived extracellular proteins. Leaf mulch colloids, with more hydrophobicity and aromaticity, enhanced the clay-facilitated transfer of metals in the soils.

     

不同耕作方式对紫色水稻土团聚体及有机碳分布的影响

The effect of different tillage systems on the size distribution of aggregates and organic carbon distribution and storage in different size aggregates in a Hydragric Anthrosol were studied in a long-term experiment in Chongqing, China. The experiment included three tillage treatments： conventional tillage with rotation of rice and winter fallow （CT-r） system, no-till and ridge culture with rotation of rice and rape （RT-rr） system, and conventional tillage with rotation of rice and rape （CT-rr） system. The results showed that the aggregates 0.02-025 mm in diameter accounted for the largest portion in each soil layer under all treatments. Compared with the CT-r system, in the 0-10 cm layer, the amount of aggregates 0.02 mm was larger under the RT-rr system, but smaller under the CT-rr system. In the 0-20 cm layer, the organic carbon content of all fractions of aggregates was the highest under the RT-rr system and lowest under the CT-rr system. The total organic carbon content showed a positive linear relationship with the amount of aggregates with diameter ranging from 0.25 to 2 mm. The storage of organic carbon in all fractions of aggregates under the RT-rr system was higher than that under the CT-r system in the 0-20 cm layer, but in the 0-60 cm soil layer, there was no distinct difference. Under the CT-rr system, the storage of organic carbon in all fractions of aggregates was lower than that under the CT-r system; most of the newly lost organic carbon was from the aggregates 0.002-0.02 and 0.02-0.25 mm in diameter.