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1.
聚合羟基铁铝蒙脱石复合体对磷的吸附行为及其动力学   总被引:2,自引:0,他引:2  
在一定条件下利用钠基化蒙脱石合成了聚合羟基铝-蒙脱石复合体(HyA1-Mt)、2个不同铁含量的聚合羟基铁-蒙脱石复合体(HyFe-Mt)和3个不同Fe:Al摩尔比的聚合羟基铁铝-蒙脱石复合体(HyFeAl-Mt),研究了酸性和弱酸性条件下(pH=3.0~6.5)以上蒙脱石复合体对磷的吸附行为和动力学特征。结果表明,HyFeAl-Mt对磷的吸附容量大于HyA1-Mt和HyFe-Mt复合体,且随着Fe:Al摩尔比的增大,对磷的吸附容量依次增加。随pH升高,蒙脱石复合体对磷的吸附量容量变小。但随Fe:Al摩尔比增大,HyFeAl-Mt复合体零电荷点(pHZPC)升高,pH对磷的吸附的影响越来越小,HyFe-Mt对磷的吸附几乎不受pH的影响。随Fe:A1摩尔比的增大,HyFeAl-Mt对磷的吸附能力增强,铁含量是磷吸附量的重要控制因素。磷在各蒙脱石复合体上的吸附实验数据可很好地用Langmuir吸附等温方程拟合。磷在各蒙脱石复合体上的吸附动力学过程可分为快速和慢速两个过程,快速过程中的动力学受铁含量影响明显。动力学数据可同时用准二级动力学方程和Elovich方程拟合。  相似文献   

2.
在模拟的氧化、酸性土壤条件下,用制备的低聚合羟基铁离子-蒙脱石复合体对磷酸根、铬酸根离子的竞争吸附进行实验研究发现:磷酸根离子和铬酸根离子的不同用量、不同添加顺序对竞争吸附的影响。并与蒙脱石和含水氧化铁对磷酸根离子、铬酸根离子的竞争吸附行为进行了对比。研究表明:在实验条件下,磷酸根离子、铬酸根离子在低聚合羟基铁离子蒙脱石复合体表面存在弱的竞争吸附现象。由于低聚合羟基铁离子蒙脱石复合体具有对磷酸根稍强的亲和性,在竞争吸附中,磷酸根离子处于稍有利的位置。  相似文献   

3.
低聚合羟基铁-蒙脱石复合体吸附铬酸根的实验研究   总被引:3,自引:2,他引:3  
摘要:在模拟的酸性土壤条件下,利用制备的低聚合羟基铁蒙脱石复合体对铬酸根进行吸附实验。重点研究了吸附条件对复合体铬吸附能力的影响,对比了蒙脱石和含水氧化铁。结果表明,实验条件下复合体有较强的铬吸附能力,其铬吸附量低于铁沉积物而明显高于蒙脱石。铬初始质量浓度是影响复合体铬吸附量的最主要因素,离子强度次之。吸附时间(12h以上)、温度、pH值对复合体铬吸附量的影响很小;说明在酸性土壤条件下,复合体有强且稳定的铬吸附能力。  相似文献   

4.
低聚合羟基铁离子-蒙脱石复合体吸附磷和氟的实验研究   总被引:4,自引:1,他引:4  
姜浩  廖立兵  王素萍 《地球化学》2003,32(6):573-581
将提纯的钙蒙脱石与羟基铁离子溶液作用,制备了低聚合羟基铁-蒙脱石复合体。在实际土壤的酸度(pH=4~8)和温度(t=34~50℃)条件下,进行了低聚合羟基铁-蒙脱石复合体吸附P和F的实验,探讨了复合体的P和F吸附能力与pH值、温度、吸附时间、P和F的初始浓度、离子强度间的关系,并与蒙脱石和含水氧化铁的P和F吸附行为进行了对比。研究表明,在实验条件下,低聚合羟基铁-蒙脱石复合体对磷具有明显的亲合力,对氟的亲合力较低,只略高于蒙脱石原样。低聚合羟基铁-蒙脱石复合体对P和F的吸附,特别是对磷的吸附行为对该元素在土壤中的迁移过程有重要影响,成果对土壤学和环境学研究有参考价值。  相似文献   

5.
朱茂旭  谢美  于红  姬泓巍 《地球化学》2005,34(3):278-284
在一定条件下利用钠基蒙脱石 (Na- Mt)合成了 OH/Al比为 1.6的聚合羟基铝-蒙脱石 (HyAl- Mt)复合体,并研究了弱酸性和强酸化条件下 HyAl- Mt与氟之间的相互作用及土壤环境意义.结果表明, pH在 5.0~ 9.0之间时, HyAl- Mt对氟的吸附受 pH影响小;当 pH < 4.5时,吸附能力随 pH减小迅速增大. pH 6.62时, HyAl- Mt对氟的吸附主要是络合交换机制,而 pH 3.02及高氟浓度条件下是表面吸附、矿物溶解及共沉淀-卷扫等协同作用机制,并使 HyAl- Mt具有异常高的氟去除能力.与蒙脱石粘土相比, HyAl- Mt的氟吸附能力明显提高,土壤中的 HyAl- Mt组分可有效地降低氟污染土壤中氟的迁移性并减少其生物有效性.在酸性氟污染的土壤中,氟与 HyAl- Mt相互作用还可一定程度抑制土壤的酸化.土壤酸度越大,这种抑制作用越明显.施用合成的 HyAl- Mt 可作为酸性氟污染土壤修复并控制土壤酸化的有效途经之一.  相似文献   

6.
低聚合羟基铁离子-蒙脱石复合体吸附砷的实验研究   总被引:15,自引:2,他引:15  
姜浩  廖立兵  王素萍 《地球化学》2002,31(6):593-601
将提纯的钙蒙脱石与羟基铁离子溶液作用,制备了低聚合羟基铁-蒙脱石复合体,用化学分析,电子探针分析,粉晶X射线衍射分析,差热分析和穆斯堡尔谱分析等手段。对蒙脱石原样,低聚合羟基铁-蒙脱石复合体和相同条件下制备的铁的含水氧化物进行了表征。在实际土壤的酸度(pH=4-7)和温度(18-40℃)条件下,进行了低聚合羟基铁-蒙脱石复合体吸附有害元素砷的实验,探讨了复合体的砷吸附能力与pH值,温度,吸附时间,砷初始浓度,离子强度间的关系,并与蒙脱石和铁的含水氧化物的砷吸附行为进行了对比,研究表明,在实验条件下,低聚合羟基铁-蒙脱石复合体对砷具有明显的亲合力,低聚合羟基铁-蒙脱石复合体吸附砷的过程有可能是地表岩石和土壤中重要的地球化学过程,是影响砷地地表,特别是土壤中迁移,富集的重要因素。  相似文献   

7.
基于当前发生的抗生素污染环境严峻问题,本文开展高活性粘土矿物蒙脱石吸附水中盐酸四环素(TC)的实验研究。采用批处理吸附实验方法,着重考查溶液初始TC浓度、初始pH值、电解质的阳离子类型及其浓度等对蒙脱石吸附性能的影响。结果显示,蒙脱石对TC的吸附行为可用Freundlich吸附等温线进行描述,并表现出显著的非线性特征;Langmuir方程确定其最大吸附量为625 mg/g;在较强酸性介质条件下(pH=2~4)蒙脱石对TC的吸附能力最强,其次为弱酸性-弱碱性环境(pH=5~9);不同阳离子类型也能显著影响蒙脱石对TC的吸附,表现为阳离子价态越高,对TC吸附的影响程度越明显。蒙脱石可被认为是一种TC的高效吸附剂,应用于盐酸四环素污染废水的处理过程。  相似文献   

8.
蒙脱石/胡敏酸复合体对重金属离子吸附实验研究   总被引:2,自引:0,他引:2  
主要研究了蒙脱石吸附胡敏酸后形成的复合体对Cu2 、Cd2 、Cr3 3种重金属离子的吸附.实验结果表明:用胡敏酸对蒙脱石改性后能提高其对3种重金属离子的吸附性能,胡敏酸浓度越大,吸附性能提高程度越大,3种重金属离子的Langmuir吸附等温线线性相关都能达到0.99以上.蒙脱石/胡敏酸复合体对3种重金属离子的吸附量都随pH值的升高而增加,随离子强度的增加而减小.另外还对其吸附动力学进行了研究,发现可用Elovicb方程和双常数方程对吸附过程进行较好地拟合.  相似文献   

9.
Cu2+和Cd2+在蒙脱石-胡敏酸复合体上的吸附及其竞争   总被引:1,自引:0,他引:1  
土壤和水体中的腐殖酸常常与粘土矿物紧密结合成为特殊的复合体.这种粘土矿物-腐殖酸复合体对重金属的吸附作用既有别于粘土矿物,更有别于腐殖酸.以蒙脱石和胡敏酸分别作为粘土矿物和腐殖酸的代表,通过一系列实验研究了Cu2+、Cd2+在单一体系和共存体系条件下在蒙脱石-胡敏酸复合体上的吸附作用,同时探讨了二者的竞争特点.实验结果表明,在单一体系条件下,蒙脱石-胡敏酸复合体对Cu2+的吸附量始终明显大于Cd2+,且二者的吸附量均随其初始浓度的增大而呈线性增大;而在Cu2+和Cd2+共存体系条件下,Cu2+的吸附量始终略大于Cd2+的吸附量,即复合体对Cu2+的吸附有较好的选择性.在吸附过程中,复合体中的蒙脱石与Cd2+和Cu2+的阳离子交换作用处于主导地位.无论是在单一体系还是在共存体系中,Cd2+优先替换电价相同而半径略大的Ca2+,而Cu2+则优先替换半径相近、电价低的Na+.因此,Cd2+的存在使Cu2+在复合体上的吸附量明显地减小,而Cu2+的存在对Cd2+的吸附几乎没有影响.这些实验结果将有助于深入探讨重金属离子在土壤、水体等环境中的迁移-固定行为.  相似文献   

10.
普遍存在环境中的低分子有机酸盐对氧化亚铁硫杆菌的矿化产物(施氏矿和黄钾铁矾等铁矿物)会产生影响,从而导致环境中有毒重金属迁移转化发生变化。本文探讨了低分子有机酸钠盐对铁细菌HX3成长过程中代谢产物铁矿物的影响,并利用XRD、FTIR、FESEM和EDS对形成的铁矿物进行了表征与分析。研究结果表明,低浓度低分子有机酸钠盐的加入对细菌氧化Fe~(2+)的影响不明显,但可加速黄钾铁矾的形成;苹果酸钠的加入较柠檬酸钠和草酸钠更利于施氏矿向黄钾铁矾转变。高浓度低分子有机酸钠盐(苹果酸钠、柠檬酸钠和草酸钠依次为20、40和40mmol/L)的加入对细菌培养过程中Fe~(2+)的氧化有抑制作用;抑制影响从大到小的顺序为:苹果酸钠柠檬酸钠草酸钠。该研究结果可为含氧化亚铁硫杆菌等铁细菌的酸性矿山废水中铁矿物的形成转化和生物矿化机理提供理论参考。  相似文献   

11.
The adsorption of oxalic, phthalic, salicylic, and lactic acids on goethite from 0.53 M NaCl and from synthetic major ion seawater is examined to determine the effect of Mg, Ca, and SO4 on the adsorption behavior of the organic compounds. The comparison shows that organic acid adsorption is suppressed in seawater relative to the NaCl system. Successive additions of SO4, Mg, and Ca in their natural ionic proportions found in seawater to 0.53 M NaCl indicate that sulfate suppresses the adsorption of all the organic acids, especially in the low pH range. The addition of Mg also suppresses the adsorption of oxalic and phthalic acids while the addition of Ca suppresses lactic acid adsorption. The effect of SO4, Mg, and Ca on the adsorption of the organic acids is due to competition for available binding sites and the formation of solution complexes which either do not adsorb or weakly adsorb.  相似文献   

12.
The adsorption of two model siderophores, desferrioxamine B (DFOB) and aerobactin, to lepidocrocite (γ-FeOOH) was investigated by attenuated total reflection infrared spectroscopy (ATR-FTIR). The adsorption of DFOB was investigated between pH 4.0 and 10.6. The spectra of adsorbed DFOB indicated that two to three hydroxamic acid groups of adsorbed DFOB were deprotonated in the pH range 4.0-8.2. Deprotonation of hydroxamic acid groups of adsorbed DFOB at pH values well below the first acid dissociation constant of solution DFOB species (pKa = 8.3) and well below the point of zero charge of lepidocrocite (pHPZC = 7.4) suggested that the surface speciation at the lower end of this pH range (pH 4) is dominated by a surface DFOB species with inner-sphere coordination of two to three hydroxamic acids groups to the surface. Maximum adsorption of DFOB occurred at approximately pH 8.6, close to the first pKa value of the hydroxamic acid groups, and decreased at lower and higher pH values.The spectra of adsorbed aerobactin in the pH range 3-9 indicated at least three different surface species. Due to the small spectral contributions of the hydroxamic acid groups of aerobactin, the interactions of these functional groups with the surface could not be resolved. At high pH, the spectral similarity of adsorbed aerobactin with free aerobactin deprotonated at the carboxylic acid groups indicated outer-sphere complexation of the carboxylate groups. With decreasing pH, a significant peak shift of the asymmetric carboxylate stretch vibration was observed. This finding suggested that the (lateral) carboxylic acid groups are coordinated to the surface either as inner-sphere complexes or as outer-sphere complexes that are strongly stabilized at the surface by hydrogen bonding at low pH.  相似文献   

13.
Batch adsorption and dissolution experiments with lepidocrocite (γ-FeOOH) and two siderophores, desferrioxamine B (DFOB) and aerobactin, were performed between pH 3 and 8 in the dark and under irradiation with UV-visible light. The increase in surface concentrations of adsorbed DFOB with increasing pH was explained in terms of electrostatic interactions between the protonated and charged terminal amine group of DFOB surface complexes and the charged lepidocrocite surface. The adsorption of aerobactin was consistent with the typical anion-like adsorption behavior of low molecular weight organic acids and indicated that the adsorption properties are strongly determined by the carboxylic acid groups. The adsorption experiments revealed furthermore that the Fe(III)-DFOB solution complex has a very low affinity for the surface, in contrast to Fe(III)-aerobactin solution complexes. In accordance with a surface-controlled mechanism of ligand-promoted dissolution, we found a linear correlation between dissolution rates of lepidocrocite and the surface concentrations of adsorbed DFOB. In the dark, 6- to 8-fold lower dissolution rate coefficients were determined for aerobactin in comparison to DFOB. These results suggested that aerobactin forms surface complexes that are less dissolution-active, characterized by a higher degree of multinuclear surface complexation and/or by less dissolution-active coordination modes of the involved iron-binding groups. For both DFOB and aerobactin, dissolution rate coefficients increased significantly under irradiation with UV-visible light. This increase was interpreted in terms of light-induced reduction of surface Fe(III), primarily by intrinsic photochemical processes of the lepidocrocite bulk phase, based on the observed photoreductive dissolution in the absence of organic ligands between pH 3 and 6. We hypothesize that the α-hydroxycarboxylate group of aerobactin may form a surface complex that additionally promotes photoreductive dissolution by a ligand-to-metal charge-transfer (LMCT) reaction, similar to citrate. However, LMCT reactions involving the α-hydroxycarboxylate group of aerobactin are rather ineffective, based on the comparison of light-induced dissolution rate coefficients determined in the presence of aerobactin and citrate.  相似文献   

14.
Los Pijiguaos bauxite deposit is located in Southern Venezuela, in a tropical rain forest environment. Among the various impurities during the bauxite processing (Bayer process), organic matter compounds present in Bayer liquor can slow the rate of alumina precipitation, and reduce product yield and quality. Soil samples were taken from a 37-m-deep core and the distribution of organic carbon (OC) was investigated as well as its relationship with major oxides Al2O3, Fe2O3, SiO2 and with the mineral phases gibbsite, hematite, kaolinite and quartz. Each sample was subjected to an adsorption process of humic acids by interaction with solutions of known concentrations. Maximum adsorption capacity was also studied in each mineral separately, which allowed calculation of the theoretical adsorption capacity of each soil sample. Even if concentrations of OC were higher in the first 5 m of the profile (0.2–0.5%), samples exhibited a low adsorption capacity (0.02%), while at depth between 10 and 37 m, samples showed lower OC concentrations (0.03–0.05%), and a larger OC adsorption capacity (0.08%). The model for the adsorption capacity only works between 10 and 30 m of depth, since in the first 10 m the bauxitic profile seems to be saturated in OC, because the concentration of OC is higher than the maximum predicted by adsorption experiments.  相似文献   

15.
The adsorption of three copper species, the hydrated cupric ion, bisglycine Cu(II) and a Cu(II)-humic acid complex, on montmorillonite and imogolite at pH 7 was investigated by electron paramagnetic resonance (EPR) spectroscopy. The spectra of the supernatant solutions indicated that adsorption of the glycine complexes was very much less than that of the uncomplexed ion for both minerals and that montmorillonite adsorbed significantly more Cu from the humic acid solution than did imogolite. In every case the adsorbed Cu was characterized by more than one type of chemical environment and the spectral parameters show differences between the adsorbed species depending on their freedom of movement and their mode and site of adsorption. Qualitatively similar spectra were obtained when the uncomplexed ion was adsorbed on either of the mineral species and it is suggested that simple Cu(II) ions were involved and that their coordination environments comprised water molecules and hydroxyl groups. With the bisglycine Cu(II) complexes, the spectra were characterized by two components which may be accounted for by adsorption at two different types of site in the structures. In each case one component had parameters that are similar to those of the bisglycine Cu(II) in the solid state, but the second component in the spectra of the montmorillonite sample was quite different to that obtained with imogolite. The Cu(II)-humic acid complex with montmorillonite gave spectra that were similar to that from copper humate, but with imogolite the spectra from the Cu(II)-humic acid system were similar to those obtained with the uncomplexed Cu(II) ion, indicating that imogolite is able to extract copper from humic acid.  相似文献   

16.
Boron is an important micronutrient for plants, but high B levels in soils are often responsible for toxicity effects in plants. It is therefore important to understand reactions that may affect B availability in soils. In this study, Attenuated Total Reflectance Fourier transform Infrared (ATR-FTIR) spectroscopy was employed to investigate mechanisms of boric acid (B(OH)3) and borate (B(OH)4) adsorption on hydrous ferric oxide (HFO). On the HFO surface, boric acid adsorbs via both physical adsorption (outer-sphere) and ligand exchange (inner-sphere) reactions. Both trigonal (boric acid) and tetrahedral (borate) boron are complexed on the HFO surface, and a mechanism where trigonal boric acid in solution reacts to form either trigonal or tetrahedral surface complexes is proposed based upon the spectroscopic results. The presence of outer-sphere boric acid complexes can be explained based on the Lewis acidity of the B metal center, and this complex has important implications for boron transport and availability. Outer-sphere boric acid is more likely to leach downward in soils in response to water flow. Outer-sphere boron would also be expected to be more available for plant uptake than more strongly bound boron complexes, and may more readily return to the soil solution when solution concentrations decrease.  相似文献   

17.
The adsorption of 15 protein amino acids from dilute (~ 10 μM) distilled water solutions onto organic-free kaolinite and montmorillonite clay minerals (1 wt% suspensions) was determined at room temperature over a 48 hour period. The systems came to steady state within 2 hours. Basic (positively charged) amino acids were strongly adsorbed (40–80% removal) by both clay minerals. Neutral (uncharged) amino acids were taken up appreciably (10–15%) by montmorillonite, but little if any (<5%) by kaolinite. Acidic (negatively charged) amino acids were adsorbed (20–35%) only by kaolinite. These adsorption patterns appear to be related in part to electrostatic interactions between the clay mineral surfaces and the different amino acid types. The measured extents and selectivities of adsorption onto these clay minerals are sufficiently great to potentially affect the distributions and reactions of free amino acids in natural environments.  相似文献   

18.
To study the migration and accumulation of Rh(III) in natural systems, we have synthesized complexes of Rh(III) and fulvic acids (FA), which are dominant organic compounds of natural waters. The composition of rhodium hydroxofulvate complexes is determined at pH 7.0, and the stability constant of these complexes is calculated. Data are obtained on interaction of FA and Rh(III) hydroxofulvate complexes with components of naturally occurring reactive barriers (ferrihydrite, quartzite, clay shale, and natural aluminosilicate suspensions) at pH 4.0–8.0. The adsorption behavior of FA and rhodium fulvate complexes at the sorbents was determined to be analogous.  相似文献   

19.
The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite–water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8–9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)–Fe bond distances of ∼2.92–2.94 and 3.41–3.44 Å, respectively. The As–Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As–Fe bonding mechanisms.  相似文献   

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