砖红壤吸附低分子量有机酸的初步研究

本文用一次平衡法研究了砖红壤对柠檬酸、草酸和醋酸等 3 种低分子量有机酸的吸附反应。结果表明砖红壤对多元羧酸有很高的吸附容量,3 种有机酸吸附量的大小顺序为:柠檬酸>草酸>醋酸。土壤体系中有机酸的吸附量先随 pH 的增加而增加,约在 pH5.0 左右达最大,然后逐渐减小。土壤中的氧化铁是有机酸吸附的主要载体,当用 DCB 法将土壤游离氧化铁去除后,土壤对有机酸的吸附量大幅度减小。     

低分子量有机酸对可变电荷土壤铝活化动力学的影响

从动力学角度研究了几种低分子量有机酸对2种酸性土壤中铝的活化和活化铝在土壤固/液相之间分配的影响。结果表明:对于络合能力弱的醋酸和乳酸,主要通过质子作用活化铝,且活化作用明显小于盐酸。而络合能力较强的苹果酸、草酸和柠檬酸,主要通过络合作用促进铝的释放,且这种作用随有机酸根阴离子络合能力的增强而增加。在氧化铁含量较高的砖红壤中,苹果酸、草酸和柠檬酸通过专性吸附增加土壤表面负电荷,从而增加土壤交换态铝;但在氧化铁含量较低的红壤中,草酸和柠檬酸主要通过形成可溶性铝络合物降低交换态铝。活化铝在土壤固/液相间的分配主要决定于溶液中有机阴离子与土壤固相表面对铝离子的竞争。醋酸和乳酸活化的铝主要以交换态铝存在;而草酸和柠檬酸活化的铝主要以有机酸-铝络合物存在于溶液中,特别是在氧化铁低的红壤中,这将促进铝在土壤-水体中的迁移。     

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。     

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。     

广西富硒土壤中氧化铁对Se（Ⅳ）吸附解吸的影响机制

为探究游离氧化铁对富硒土壤吸附解吸Se(Ⅳ)的影响机理,以广西富硒赤红壤、红壤为研究对象,通过等温吸附解吸实验,比较去除游离氧化铁前后土壤对Se(Ⅳ)的吸附解吸特征,同时运用Zeta电位、扫描电镜-能谱分析和傅里叶红外光谱技术分析其机理。结果表明：Langmuir和Freundlich等温吸附方程均能较好地拟合供试土壤吸附Se(Ⅳ)过程,相关系数在0.920～0.995之间。供试土壤最大吸附量由高到低依次为：赤红壤(1 399 mg·kg^–1)、红壤(1 336 mg·kg^–1)、去氧化铁赤红壤(444 mg·kg^–1)、去氧化铁红壤(352 mg·kg^–1)。去除游离氧化铁后,红壤、赤红壤的Zeta电位分别由–24.42、–18.06 mV变为–33.06和–26.43 mV,且比表面积减小。红壤、赤红壤及其去氧化铁土对Se(Ⅳ)的解吸率在2%～7%之间,去氧化铁土的解吸率高于红壤、赤红壤。红外光谱分峰拟合分析可知,土壤主要通过-OH、Fe-O、C=O等含氧基团与硒发生反应,土壤去除氧化铁后,Fe...     

蒙山茶园土壤组分对铝吸附解吸热力学特征的影响

采用间歇法和振荡平衡法,通过实验室模拟,研究了蒙山茶园土壤(紫色土和黄壤)原土及各粒级组分对铝吸附解吸的热力学特征,并分析土壤有机质、游离氧化铁和CEC对其吸附解吸的影响。结果表明:(1)不同土壤原土及各粒级组分对铝的吸附量都随铝离子浓度的增大而增加,且各粒级土壤对铝的吸附量不同,表现为土壤颗粒比表面越大,有机质、游离氧化铁和CEC越高,其吸附量越大。紫色土原土及各粒级组分对铝的等温吸附过程用Freundlich方程描述最佳,说明紫色土对铝的吸附是多层吸附;而黄壤原土及各粒级组分对铝的等温吸附过程则用Langmuir方程描述最佳,说明黄壤对铝的吸附以单层吸附为主。(2)紫色土原土及各粒级组分对铝的解吸率表现出以下关系:粗砂粒原土细砂粒粉粒粘粒,黄壤原土及各粒级组分对铝的解吸率则表现出以下关系:细砂粒粗砂粒原土粉粒粘粒,两者解吸率的大小关系均与其有机质及游离氧化铁相反,表明两种土壤的原土及各粒级组分中有机质和游离氧化铁越高,其专性吸附率就越高,从而解吸率越小,说明土壤有机质和游离氧化铁影响土壤对铝的固持能力。(3)土壤最大吸附量与有机质、游离氧化铁含量和CEC都表现出显著或极显著的正相关关系,而其最大解吸率也均与有机质、游离氧化铁含量和CEC表现出显著或极显著的负相关关系。     

川西山地黄壤组分对氟的吸附-解吸特征研究

以川西山地黄壤为例,采用选择溶解和模拟试验方法,研究黄壤各组分对F-的吸附与解吸特性。结果表明:黄壤各组分对F-的吸附可分为快速和慢速两个阶段,去除土壤相关组分后,平衡时间缩短,平均吸附速率变大,最大吸附量显著下降。随着初始浓度增大,吸附量呈增加趋势,吸附平衡液pH值上升。与未去除组分相比,经处理的样品对F-的吸附量均有一定程度的降低,其降低量由小到大的顺序为去无定形氧化铁/铝>去有机质>去游离氧化铁/铝。Langmuir、Freundlich、Temkin方程均可较好的拟合样品对F-的吸附,以Langmuir方程最佳。黄壤吸附的F-可为0.02 mol L-1的KCl大部分解吸,去除土壤组分后,黄壤对氟的专性吸附降低,缓冲能力减弱,解吸率增大,解吸率大小顺序为去游离氧化铁/铝>去有机质>去无定形氧化铁/铝>原土,显示了土壤各组分在F-吸附中的重要性差异。     

不同有机酸对石灰性土壤磷的活化效应及机理

【目的】添加低分子量有机酸是活化土壤难溶性磷有效途径。比较研究几种低分子量有机酸及其组合对土壤磷的活化性能,为土壤磷的高效利用提供依据。【方法】低磷和高磷石灰性土壤选自新疆石河子,设置5个低分子有机酸添加处理：草酸、柠檬酸、黄腐酸、柠檬酸+草酸、草酸+柠檬酸+黄腐酸处理,和一个0.01mmol/L KCl对照。采用吸附平衡实验法测定土壤磷的吸附量;采用土壤吸附动力学实验法测定土壤磷的解吸动力学。采用常规和灭菌土壤培养方法,通过连续浸提法研究低分子有机酸及其组合对磷组分动态转化的影响和pH对磷的活化效应。【结果】Langmuir与Elovich模型均可较好地拟合土壤对磷的吸附热力学(R²=0.852～0.994)与吸附动力学过程(R²=0.882～0.975)。低磷土壤的最大吸附量(Q_max)、最大缓冲容量(MBC)、吸附力常数(K_L)和吸附速率(b)均高于高磷土壤,表明低磷土壤对磷的吸附更强。低分子量有机酸添加均降低了Q_max、MBC和b。草酸对Q_max和...     

低分子量有机酸对砖红壤表面电荷的影响

本文研究了4种低分子量有机酸对砖红壤表面电荷性质的影响,结果表明存在于体系中的有机酸增加了表面负电荷量,同时减少表面正电荷的量。在低有机酸加入量下,有机酸对正电荷的影响程度比其对负电荷的影响程度大得多。4种酸对土壤表面电荷影响的大小顺序为:柠檬酸>苹果酸>草酸>醋酸。有机酸对表面电荷的影响随体系pH而变化,它们对正电荷的影响程序随pH的增加而减小,而对负电荷的的影响呈相反的变化趋势。有机酸主要通过其阴离子在土壤表面的吸附来影响土壤的表面电荷性质。     

有机质、石灰、磷酸盐和淹水对红壤中铝形态的影响

研究了有机质，施用石灰和磷酸盐，以及淹水培育对红壤铝形态的影响。结果表明，用Ｈ２Ｏ２去除有机质，施用石灰和磷酸盐，以及淹水培育，使土壤ｐＨ升高，交换态铝减少，吸附态无机羟基铝增加。而施用腐殖酸使土壤ｐＨ降低，交换态铝增加，有机配合态略有上升。     

Characteristics of organic matter in soil surface horizons derived from calcareous and metamorphic rocks and different vegetation types from the Mediterranean high-mountains in SE Spain

A study was carried out on some basic characteristics of the organic matter in the surface horizons of soils from the two different geological (calcareous and acid metamorphic rocks) and ecological systems under a Mediterranean climate in Southeast Spain. The results show some noticeable differences in soil organic matter composition. This is likely due to typical Mediterranean climate and well adapted vegetation. There is a tendency towards a greater stability for the soil humus formed under slightly alkaline soil in comparison to the slightly acidic environment. The samples taken from the latter environment have a higher content in free organic matter, a lower content in total extractable humin and a greater relative proportion of aliphatic chains and lignin in the humic acids. The results also suggest some differences caused by the type of vegetation (forest and scrubland ecosystems) in the soil humus chemistry, with a more obvious negative effect under reforestations with species of Pinus in an acidic soil environment (a higher content in free organic matter, lesser presence of fungal-derived perylenequinonic pigments in the humic acids, and a higher content in little evolved forms of nitrogen and lignin in the humic acids). In general the organic matter under scrubland and Quercus vegetation is more decomposed and the humus is more evolved than under Pinus vegetation.     

Effect of soil composition on adsorption of lead as reflected by a study on a natural forest soil profile

The adsorption characteristics of lead on each genetic horizon of a natural brown forest soil profile were studied to recognize the possible immobilizing effect of a mineralogical diverse soil profile in the case of a possible lead contamination. Lead adsorption experiments were carried out on whole soil samples, soil clay fractions, as well as on their carbonate and organic matter free variant. TEM-EDS analyses were performed to characterize the adsorption capacity of individual mineral phases. The most important lead adsorbents in order of importance are the organic matter, the clay minerals, and the iron oxides. The most significant process is the ion exchange of calcium by lead with the respect to adsorption. The organic matter adsorbs more lead than clay minerals, and clay fractions adsorb more lead as compared to the whole soil samples. Among mixed layer clay minerals, those containing swelling component have the highest lead adsorption capacity, but the exact distinguishing of the individual clay mineral particles with the respect to their adsorption capacity is not possible. The calcite influences the lead adsorption through its buffering capacity: high calcite content results in lead precipitation. Soils characterized by high amount of organic matter, swelling clay mineral accumulation horizon and calcareous subsoil are suitable medium to immobilize a significant lead pollution.     

Competitive sorption between imidacloprid and imidacloprid-urea on soil clay minerals and humic acids

Soil organic matter and clay minerals are responsible for the adsorption of many pesticides. Adsorption and competitive sorption of imidacloprid on clay minerals and humic acids (HA) were determined using the batch equilibration method. The sorption coefficient of imidacloprid on humic acids was significantly higher than that on Ca-clay minerals, indicating that soil organic matter content was a more important property in influencing the adsorption of imidacloprid. Competitive sorption was investigated between imidacloprid and its main metabolite imidacloprid-urea on HA and Ca-clay minerals. The results showed that the sorption capacity of imidacloprid on clay minerals and HA was reduced in the presence of the metabolite, implying that imidacloprid-urea could occupy or block adsorption sites of imidacloprid on soil, potentially affecting the fate, transport, and bioavailability of imidacloprid in the environment. The interactions between a Ca-clay or HA-clay mixture and adsorption of imidacloprid and imidacloprid-urea were studied using IR differential spectra on thin films made of the adsorbent. The possible mechanisms were discussed from the shift of characteristic IR absorption bands of imidacloprid and imidacloprid-urea after sorption.     

Surface area and CEC as related to qualitative and quantitative changes of forest soil organic matter after liming

Water vapor adsorption isotherms were used for estimation of (apparent) surface areas of samples of limed and unlimed plots of an acidic sandy forest soil. Samples were taken at two microrelief (ridge and furrow) positions from five subsequent 10 cm layers. Values of surface area and CEC correlated linearly with organic matter content but only for four bottom layers. Surface areas and CEC values calculated per the unit mass of organic carbon were higher in upper layers than in lower layers for control samples. For limed samples an opposite trend was observed. The estimated average (apparent) charge densities of organic matter showed a better correlation with humic to fulvic acids ratio. Values of surface charge densities for every investigated profile increased with depth and they were lower in limed than in unlimed profiles.     

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.     

我国几种主要土壤胶体的NH4+吸附特征

本文讨论我国几种主要土壤胶体的NH₄⁺吸附特征。土壤胶体对NH₄⁺的吸附符合两种表面Langmuir方程。土壤胶体对NH₄⁺的结合能力强弱顺序是:黄棕壤>黑土、(土娄)土>红壤>砖红壤,而NH₄⁺的解吸率大小顺序与此相反。Langmuir吸附方程参数K₁与土壤胶体的粘粒矿物组成有关,并与土壤胶体对NH₄⁺的相对偏好性(A值)呈正相关。Langmuir参数(M₁+M₂)与土壤胶体的CEC呈正相关,去有机质(OM.)前后△K₁与△OM.呈反相关。去有机质可增加土壤胶体对NH₄⁺的偏好性。土壤胶体的NH₄⁺吸附和解吸特征决定于其组成和表面性质,并受有机无机复合作用的影响。永久电荷吸附位对NH₄⁺的偏好性较强,而可变电荷吸附位则较弱。     

Analysis of the variable charge of two organic soils by means of the NICA-Donnan model

We have tested to see if the generic set of NICA‐Donnan model parameters, used to describe isolated humic substances, can also describe soil humic substances in situ. A potentiometric back‐titration technique was used to determine the variable surface charge of two organic peat soils at three different ionic strengths. The non‐ideal, competitive‐adsorption NICA‐Donnan model was used to simulate the surface charge, by assuming a bimodal distribution of H⁺ affinity on the soil solid phase. The model provided an excellent fit to the experimental data. The Donnan volume, V_D, varied slightly with ionic strength, although the variation was less than for humic substances in solution. The values obtained for the parameters that define the affinity distributions, the intrinsic proton binding constant (log K_i^int) and the heterogeneity of the site (m_i), were similar to those observed for isolated soil humic acids. The abundance of carboxylic groups in the whole soil represented 30% of the typical value for isolated soil humic acids. The composition of the organic matter of the whole soils, obtained by ¹³C CPMAS NMR, was comparable to the characteristic composition of soil humic acids.     

Poorly ordered hydrous Fe oxides, colloidal dispersion and soil aggregation. I. Effect of humic macromolecules on surface and colloidal properties of Fe (III) polycations

Model humic macromolecules, obtained by auto-oxidation of the catechol-glycine system, were adsorbed on poorly ordered hydrous iron oxides, Fe(OH)_2.8. The pH was nearly constant at c. 6 in order to simulate natural soil and river environments. When the amount of organic carbon adsorbed on 1 g of poorly ordered ferrihydrite increased from 0 to 70 mg, the ligand OH exchange was very small, but the zero point of charge of suspensions progressively shifted from 7.3 to 5.6, and net surface charge, which was initially positive, progressively became negative, suggesting an adsorption mechanism with positive charge neutralization. Consequently, colloidal stability changed from rapid to slow flocculation. The ferrihydrite-haematite exothermic reaction partially shifted from 400°C to higher temperatures as a function of adsorbed organic matter, and ferrihydrite solubility progressively increased by formation of soluble iron-organic complexes. These results were explained more satisfactorily by the concept of colloidal organ- mineral association than by organic coatings on surfaces.     

Mineral surfaces and soil organic matter

The organic carbon content of soil is positively related to the specific surface area (SSA), but large amounts of organic matter in soil result in reduced SSA as determined by applying the Brunauer–Emmett–Teller (BET) equation to the adsorption of N₂. To elucidate some of the controlling mechanisms of this relation, we determined the SSA and the enthalpy of N₂ adsorption of separates with a density > 1.6 g cm^?3 from 196 mineral horizons of forest soils before and after removal of organic matter with NaOCl. Likewise, we investigated these characteristics before and after sorption of increasing amounts of organic matter to four mineral soil samples, oxides (amorphous Al(OH)₃, gibbsite, ferrihydrite, goethite, haematite), and phyllosilicates (kaolinite, illite). Sorption of organic matter reduced the SSA, depending on the amount sorbed and the type of mineral. The reduction in SSA decreased at larger organic matter loadings. The SSA of the mineral soils was positively related to the content of Fe oxyhydroxides and negatively related to the content of organic C. The strong reduction in SSA at small loadings was due primarily to the decrease in the micropores to which N₂ was accessible. This suggests preferential sorption of organic matter at reactive sites in or at the mouths of micropores during the initial sorption and attachment to less reactive sites at increasing loadings. The exponential decrease of the heat of gas adsorption with the surface loading points also to a filling or clogging of micropores at early stages of organic matter accumulation. Desorption induced a small recovery of the total SSA but not of the micropore surface area. Destruction of organic matter increased the SSA of all soil samples. The SSA of the uncovered mineral matrix related strongly to the amounts of Fe oxyhydroxides and the clay. Normalized to C removed, the increase in SSA was small in topsoils and illuvial horizons of Podzols rich in C and large for the subsoils containing little C. This suggests that micropores preferentially associate with organic matter, especially at small loadings. The coverage of the surface of the soil mineral matrix as calculated from the SSA before and after destruction of organic matter was correlated only with depth, and the relation appeared to be linear. We conclude that mineralogy is the primary control of the relation between surface area and sorption of organic matter within same soil compartments (i.e. horizons). But at the scale of complete profiles, the surface accumulation and stabilization of organic matter is additionally determined by its input.