Aluminium ions at polyelectrolyte interfaces. II. Role in the surface-area-exclusion chromatography of humic acid

Surface-area-exclusion chromatography using Whatman glass microfibre filters modified by adsorption of aluminium ions as a stationary phase was used to evidence the different interfacial behaviour of aluminium ion complexed (tritium labelled) humic acids. Histograms with adsorption peaks, plateaux and humps on the stationary phase showed the various adsorption characteristics of the modified humic acid. The absence of adsorption for those constituents which were recovered in the effluent showed the very low degrees of complexation by aluminium ions to be responsible for the absence of interaction of the components with the stationary phase. Received: 24 July 2000  Accepted: 20 December 2000     

Impact factors and thermodynamic characteristics of aquatic humic acid loaded onto kaolin

The adsorption of humic acid (HA) on kaolin particles was studied at various conditions of initial solution pH, ionic strength and solid-to-liquid ratio. The resulting affinity of interactions between humic acid and kaolin was attributed to the surface coordination of HA in ambient suspensions of mineral particles and the strong electrostatic force at low pH. Addition of inorganic salt can also influence the adsorption behavior by affecting the HA molecular structure, the clay particle zeta potential and so on. Equilibrium data were well fitted by the Freundlich model and implied the occurrence of multilayer adsorption in the process. In addition, the enthalpy dependent of system temperature was 79.17 kJ/mol, which proved that the mechanism of HA adsorption onto kaolin was comprehensive, including electrostatic attraction, ligand complexation and hydrogen bonding.     

有机改性凹凸棒土对腐殖酸的吸附性能研究

合成了十六烷基三甲基氯化铵(CTAC)改性的凹凸棒土吸附剂,并研究了其对水中腐殖酸的吸附行为。通过FTIR、TG对改性前后凹凸棒土进行表征。结果表明,十六烷基三甲基氯化铵成功结合到凹凸棒土表面,结合到凹凸棒土表面的量为9.78%。在25℃时,腐殖酸在吸附剂上吸附行为符合Freundlich方程,吸附动力学符合拟二级动力学方程,初始浓度为54.60~200.20mg/L时,ATP-CTAC对腐殖酸的最大吸附量为253mg/g;温度对吸附行为影响不大;改性后的凹凸棒土对腐殖酸的吸附随pH的增大而降低;改性后的凹凸棒土显著地提高了对腐殖酸的吸附量。     

天祝褐煤腐植酸对Cr~(6+)吸附性能研究

通过分析天祝褐煤腐植酸吸附重金属Cr6+前后的红外光谱、荧光强度的变化,进行其对重金属离子Cr6+的吸附性能及机理研究。结果表明,在室温条件下(20~25℃),吸附最佳pH=5、吸附平衡时间约为12h,符合Freundlich吸附模型,相关系数R=0.9933,特性常数n为2.3820。腐植酸对Cr6+有较好的吸附性能,其吸附过程可用Ho准二级反应动力学模型描述。     

胺基修饰大孔树脂对腐殖酸的吸附研究

研究了腐殖酸在胺基修饰大孔树脂D-301上的吸附行为,并与胺基修饰超高交联树脂NDA-99和大孔非极性树脂XAD-4作对比,结果表明,带有弱碱性基团的大孔亲水性树脂D-301对腐殖酸的吸附效果优于XAD-4和NDA-99,这主要得益于D-301树脂大孔结构和表面胺基修饰.探讨了溶液pH值和重金属离子对D-301树脂吸附腐殖酸的影响,并对作用机理进行了初步探讨.     

弱碱性大孔吸附树脂对腐殖酸的吸附

研究了腐殖酸分子量对弱碱性大孔树脂吸附腐殖酸的影响, 阐明了溶液中小分子芳环化合物(苯酚)及盐含量对树脂吸附腐殖酸的影响机制. 结果表明, 树脂对低分子量腐殖酸的吸附效果要优于高分子量腐殖酸; 低浓度苯酚在溶液中可以促进树脂吸附腐殖酸, 但溶液中苯酚浓度过高会对树脂吸附腐殖酸产生抑制作用; 溶液中的盐对树脂吸附腐殖酸的影响取决于溶液的pH值.     

吸附树脂对微污染水中有机污染物的吸附研究

以活性炭作为参照,从静态和动态吸附角度,利用3种吸附树脂对微污染水中代表性污染物氯仿、三氯乙烯、2,4-二氯苯酚和腐殖酸进行了吸附去除效果研究。结果表明,吸附树脂对水溶液中有机物吸附去除具有较好的效果,但仍然存在进一步提高吸附容量的问题。     

Humic acid-divalent cation interactions

The adsorption behavior of divalent cations M²⁺ (Cu, Ni, Co and Zn) with commercial humic acid (HAAl) and also with an extracted fraction of peat soil (HAPs) was followed in aqueous solution. The series of adsorption isotherms were fitted to a modified Langmuir equation. The maximum number of moles adsorbed gave: 0.55±0.02, 0.66±0.02, 0.54±0.02, 0.40±0.02 mmol per gram for HAAl and 0.63±0.03, 0.61±0.06, 0.55±0.02, 0.54±0.03 mmol/g for solid HAPs, for copper, nickel, zinc and cobalt, respectively. The same interaction followed calorimetrically gave endothermic values: 2.4±1.0, 8.4±0.9, 18.3±0.9, 10.6±0.9 kJ mol⁻¹ and 18.4±1.2, 15.9±1.4, 15.4±1.2, 15.0±1.2 kJ mol⁻¹ for HAAl and HAPs, respectively, for the same sequence. Because all Gibbs free energies were negative. Complexation must be accompanied by an increase in entropy.     

Influence of some organic ligands on the adsorption of lead by agricultural soil

The adsorption of lead onto agricultural soil in the presence of organic compounds such as, humic acid, gallic acid or phenol was studied. The study included the factors affecting the adsorption process such as contact time, pH, adsorbent dose, metal concentration and organic ligands concentration. The experimental isotherm data were found to fit both Langmuir and Freundlich isotherms. The results show that the pseudo second-order equation provides the best correlation for the adsorption process. The results indicate that both humic acid and phenol increase the adsorption of lead while gallic acid slightly decreases the adsorption.     

Effect of pH and ionic strength on the interaction of humic acid with aluminium oxide

The effect of pH and neutral electrolyte on the interaction between humic acid/humate and γ-AlOOH (boehmite) was investigated. The quantitative characterization of surface charging for both partners was performed by means of potentiometric acid–base titration. The intrinsic equilibrium constants for surface charge formation were logK _a,1 ^int=6.7±0.2 and logK _a,2 ^int = 10.6±0.2 and the point of zero charge was 8.7±0.1 for aluminium oxide. The pH-dependent solubility and the speciation of dissolved aluminium was calculated (MINTEQA2). The fitted (FITEQL) pK values for dissociation of acidic groups of humic acid were pK ₁ = 3.7±0.1 and pK ₂ = 6.6±0.1 and the total acidity was 4.56 mmol g⁻¹. The pH range for the adsorption study was limited to between pH 5 and 10, where the amount of the aluminium species in the aqueous phase is negligible (less than 10⁻⁵ mol dm⁻³) and the complicating side equilibria can be neglected. Adsorption isotherms were determined at pH ∼ 5.5, ∼8.5 and ∼9.5, where the surface of adsorbent is positive, neutral and negative, respectively, and at 0.001, 0.1, 0.25 and 0.50 mol dm⁻³ NaNO₃. The isotherms are of the Langmuir type, except that measured at pH ∼ 5.5 in the presence of 0.25 and 0.5 mol dm⁻³ salt. The interaction between humic acid/humate and aluminium oxide is mainly a ligand-exchange reaction with humic macroions with changing conformation under the influence of the charged interface. With increasing ionic strength the surface complexation takes place with more and more compressed humic macroions. The contribution of Coulombic interaction of oppositely charged partners is significant at acidic pH. We suppose heterocoagulation of humic acid and aluminium oxide particles at pH ∼ 5.5 and higher salt content to explain the unusual increase in the apparent amount of humic acid adsorbed. Received: 20 July 1999 /Accepted in revised form: 20 October 1999     

Study on the influence of humic acid of different molecular weight on basic ion exchange resin's adsorption capacity

In this paper, humic acid (HA) was ultra-filtered into different molecular weight sections and was characterized by multi-element analysis, UV₂₅₄/TOC, FT-IR and three-dimensional fluorescence spectrometric. Since humic acids of different molecular weights have different hydrophilic and molecular size, the maximum adsorption capacity of basic ion exchange resins appears on the humic acid whose molecular weight ranges from 6000 to 10,000 Da.     

Simultaneous analysis of small organic acids and humic acids using high performance size exclusion chromatography

An accurate and fast method for simultaneous determination of small organic acids and much larger humic acids was developed using high performance size exclusion chromatography. Two small organic acids, i.e. salicylic acid and 2,3‐dihydroxybenzoic acid, and one purified humic acid material were used in this study. Under the experimental conditions, the UV peaks of salicylic acid and 2,3‐dihydroxybenzoic acid were well separated from the peaks of humic acid in the chromatogram. Concentrations of the two small organic acids could be accurately determined from their peak areas. The concentration of humic acid in the mixture could then be derived from mass balance calculations. The measured results agreed well with the nominal concentrations. The detection limits are 0.05 mg/L and 0.01 mg/L for salicylic acid and 2,3‐dihydroxybenzoic acid, respectively. Applicability of the method to natural samples was tested using groundwater, glacier, and river water samples (both original and spiked with salicylic acid and 2,3‐dihydroxybenzoic acid) with a total organic carbon concentration ranging from 2.1 to 179.5 mg C/L. The results obtained are promising, especially for groundwater samples and river water samples with a total organic carbon concentration below 9 mg C/L.     

Ferrihydrite的亚微观结构对反应活性的影响

以Fe(III)盐为原料、NaOH为沉淀剂、采用三种方法调控制备了ferrihydrite, 借助X射线衍射(XRD)、红外光谱(IR)、差热分析(DTA)及其在稀盐酸中的溶解速率等手段对其结构进行了表征, 探讨了ferrihydrite的形成环境对其亚微观结构及其反应活性的影响. 结果表明, 不同方法制备的ferrihydrite的亚微观结构不同, 恒pH条件下制备的ferrihydrite结构与α-Fe2O3结构最为相似, 更易转化为α-Fe2O3粒子.     

The effect of humic acid on the adsorption of REEs on kaolin

For a better understanding of adsorption of the rare earth elements (REEs) onto minerals and its controlling factors, adsorption experiments were performed at pH range of from 3 to 10 with kaolin (1500 mg/L) in a matrix of various concentration of NaNO₃ and about 20 μg/L of the total REEs as well as various amounts of humic acid (HA). The adsorption of HA onto the kaolin occurred over a wide pH range and decreases with increasing pH and with increasing HA concentration. The results show that humic acid has ability to either increase or decrease the adsorption of the REEs onto kaolin, depending on pH, which may be related to their speciation distribution, interaction of HA with the mineral surface. Furthermore, the light REEs are more adsorbed onto kaolin in presence of higher concentration of HA, presumably because the increase in HA concentration in the solution enhance stronger complexing of HA with heavy REEs as compare to light REEs. The ionic strength has strong effect on the adsorption of HA and REEs onto the kaolin but little on the REEs fractionation. The results presented here indicate that mineral/water adsorption may generate the enrichment of the dissolved heavy REEs in the presence of a significant amount of humic acid, which is consistent with the fractionation of REEs in the most of natural waters.     

In situ AFM study of sorbed humic acid colloids at different pH

Humic acid colloids adsorbed on the basal plane of cleaved muscovite are investigated under in situ conditions by non-contact mode atomic force microscopy (AFM) in liquid (also called fluid tapping-mode AFM). Structures are found to be of nanometer scale, consisting of flat particles (8–13 nm in diameter), aggregates of particles (20–100 nm), chain-like assemblies, networks and torus-like structures. In contrast to former investigations colloids are investigated in aquatic solution and structures are not influenced by sample preparation. Nanostructure, surface coverage and particle sizes are found to depend on solution pH. Humic colloids can be distinguished from surface roughness and background noise by image processing. Furthermore, an approach to quantify the surface coverage is discussed. Therefore, non-contact mode AFM in liquid is shown to be a powerful method to study the interaction of colloids at solid–liquid interfaces.     

Adsorption of As (V) on iron oxide nanoparticle films studied by in situ ATR-FTIR spectroscopy

Stabilization of arsenic contaminated soils by iron oxides has been proposed as a remediation technique to prevent leaching of arsenate into the environment. Fundamental studies are needed to establish under which conditions the complexes formed are stable. In the present work, a powerful technique, viz. ATR-FTIR spectroscopy, is adapted to the studies of adsorption of arsenate species on iron oxides. This technique facilitates acquisition of both quantitative and qualitative in situ adsorption data.In the present work, about 800 nm thick films of 6-lineferrihydrite were deposited on ZnSe ATR crystals. Arsenate adsorption on the ferrihydrite film was studied at pD values ranging from 4 to 12 and at an arsenate concentration of 0.03 mM in D₂O solution. The amount of adsorbed arsenate decreased with increasing pD as a result of the more negatively charged iron oxide surface at higher pD values. The adsorption and desorption kinetics were also studied. Arsenate showed a higher adsorption rate within the first 70 min and a much lower adsorption rate from 70 to 300 min. The low adsorption rate at longer reaction times was partly due to a low desorption rate of already adsorbed carbonate species adsorbed at the surface. The desorption of carbonate species was evidenced by the appearance of negative absorption bands. The desorption of adsorbed arsenate complexes was examined by flushing with D₂O at pD 4 and 8.5 and it was found that the complexes were very stable at pD 4 suggesting formation of mostly inner-sphere complexes whereas a fraction of the complexes at pD 8.5 were less stable than at pD 4, possibly due to the formation of outer-sphere complexes.In summary, the ATR technique was shown to provide in situ information about the adsorption rate, desorption rate and the speciation of the complexes formed within a single experiment, which is very difficult to obtain using other techniques.     

腐植酸接枝共聚物对赤红壤K~+吸附与解吸的影响

本文研究了经施用硝基腐植酸与丙烯酸、丙烯酰胺三元接枝共聚物的赤红壤中钾离子的吸附和解吸的影响。实验结果表明,施用共聚物的土壤可减少土壤对中钾离子的吸附,增加土壤对钾离子的解吸,提高钾离子的抗淋溶。改良后的土壤可减少土壤钾的损失,提高钾肥的利用率。     

Study of antimony (III) binding to soil humic acid from an antimony smelting site

Soil samples were collected from an antimony smelting site in Guangxi Zhuang Autonomous Region, China, at four locations characterized by different land usage, including two cultivated sites: one formerly cultivated and one uncultivated. Surface soils from all four sites were heavily polluted by toxic metals including antimony (Sb), lead (Pb) and arsenic (As), and their concentrations were 410-3330 mg·kg⁻¹, 410-3690 mg·kg⁻¹ and 200-460 mg·kg⁻¹, respectively. In the uncultivated area metal levels were 1.4-6.2 times higher as compared to the formerly and currently agriculture land. Lower levels at the cultivated sites may have resulted from an accumulation of airborne particles by vegetation and lower contents in the surface soil. However, the elevated mercury (Hg) content may reflect both natural and anthropogenic origins in this smelting site. Soil-derived humic acid (HA) from the smelting site reacted directly with Sb (III) aqueous solutions with concentrations of 12, 71 and 143 mg·g⁻¹. The maximum Sb (III) binding to the soil-derived HA was 253 μmol·g⁻¹ (added concentration of 71 mg·g⁻¹) and showed more binding (up to 50%) at lower Sb content.     

土壤胡敏酸的^13C核磁共振研究

胡敏酸(HA)是土壤有机质的重要组分,其结构性质与土壤形成和肥力特性有密切关系,长期以来一直是土壤化学研究的难点和重点之一。NMR是研究HA结构的有效手段。自Bar-ton和Schnitzer(1963)首次用~1H NMR研究土壤有机质以来,国外已先后应用~1H、~(13)C NMR和CP-MAS-~(13)C NMR等对土壤及其它来源的HA进行了许多研究,并取得引人注目的进展。但在国内,这方面研究还刚刚开始。本文应用~(13)C NMR方法对东北几种主要耕作土壤以及泥炭和猪粪的HA进行了结构表征,为土壤腐殖酸化学的基础研究提供了资料。     

Theoretical study of Sn adsorbed on the MgO(100) surface with defects

In this study, the adsorption of Sn atom at various sites on the MgO(100) surface was characterized using a theoretical approach based on density functional theory calculations. Both regular adsorption centers (O^2? and Mg²⁺) and defects (such as neutral and charged O and Mg vacancies) were considered. Several key parameters for these sites with the adsorbed Sn atom were determined to provide its geometric, energetic, and electronic characterization. The interaction between Sn and the Mg vacancy sites is very strong and is associated with a relatively small distance of the adsorbed Sn atom from the surface and with a large electronic charge transfer from Sn to the surface. A much smaller strength of Sn atom adsorption is observed for the O vacancies and regular sites. Among them, the ${{\text{F}}_{\text{s}}}^{\text{0}}$ center binds the Sn atom strongest and, in consequence, this atom acquires a significant amount of electronic charge.