Adsorption mechanism of fulvic acid onto freeze dried poly(hydroxo aluminum) intercalated bentonites

Two poly(hydroxo aluminum) intercalated Wyoming bentonites were prepared starting from two different aluminum pillaring solutions. The sorption mechanism of Laurentian fulvic acid (FA) onto these poly(hydroxo aluminum) intercalated bentonites was investigated at different pH values and at different ionic strengths (NaCl or CaCl₂). Three mechanisms contribute to the FA adsorption, depending on the pH and the nature (NaCl or CaCl₂) and ionic strength of the background electrolyte. In the presence of NaCl the FA sorption onto poly(hydroxo aluminum) intercalated bentonites can be mainly ascribed to ligand exchange between the amphoteric poly(hydroxo aluminum) hydroxyl groups and the deprotonated carboxylic groups of the FA. The FA adsorption due to ligand exchange reactions decreases with increasing pH. In presence of Ca²⁺ ions the FA adsorption is enhanced, compared to the presence of Na⁺, due to Ca²⁺ bridging between negatively charged groups on the FA molecules and the poly(hydroxo aluminum) intercalated bentonite. The FA adsorption due to Ca²⁺ bridging increases with increasing pH. A third mechanism is enhanced FA adsorption ascribed to FA-Ca-FA bridging and was detected from the FA adsorption in presence of Ca²⁺ at the zero point of charge of the poly(hydroxo aluminum) bentonite (pH 5).     

Removal of fulvic acid from aqueous media by adsorption onto modified vermiculite

Clay minerals are low cost materials that can be structurally modified and exploited for removal of natural organic matter from freshwaters. The present study shows that vermiculites modified by ion exchange with hexadecyltrimethylammonium or intercalation with poly(hydroxy iron) cations are potential adsorbents for removal of fulvic acid, whereas the adsorption on the raw clay mineral is negligible. The efficiency of the modified vermiculite was evaluated by measuring adsorption isotherms by the batch technique using initial fulvic acid concentrations between 2.5 and 50.0 mg L^− 1, with one hour of contact time. At least 94% of the fulvic acid initially present in a 20 mg L^− 1 solution was sorbed onto either the intercalated poly(hydroxy iron) cations or the organically modified vermiculite. Up to an initial concentration of 5.0 mg L^− 1 the adsorption is irreversible, and no quantifiable fulvic acid was measured in the desorption experiments. For initial fulvic acid concentrations between 10.0 and 50.0 mg L^− 1, desorption was between 2.3% and 4.9% for Fe(III) intercalated vermiculite, and between 1.4% and 9.2% for the organoclay. The adsorption percentages on intercalated poly(hydroxy iron) cations increased upon lowering pH and increasing the ionic strength, indicating the occurrence of strong binding mechanisms such as ligand exchange. Adsorption percentage of fulvic acid onto the organoclay also increased with lowering of pH, but in this case the adsorption percentages showed a small decrease at high ionic strength, suggesting that electrostatic attraction plays an important role in the adsorption process.     

Influence of pH on the aluminum speciation in freeze-dried poly(hydroxo aluminum) intercalated bentonites

Two freeze-dried poly(hydroxo aluminum) intercalated Wyoming bentonites were prepared starting from two different aluminum pillaring solutions. Their charge versus pH properties were studied by zeta potential measurements, potentiometric titrations and calcium sorption measurements in order to determine the speciation of the intercalated Al-species as a function of pH. The structural changes of the intercalated bentonite induced by the pH increase were studied by XRD analysis and N₂ adsorption/desorption measurements. At pH 5 the permanent charge (0.75 meq/g) of the original Wyoming bentonite is completely neutralized by positively charged Al-hydroxo species. With increasing pH the Al-species deprotonate and aggregate until their complete neutralization at pH 9.4. Above this pH the Al-polymers start to dissolve from the clay as Al(OH)₄⁻.     

混凝对垃圾渗滤液中腐殖质的去除特性

通过分别投加混凝剂聚合氯化铝(PAC)、聚合硫酸铁(PFS)和聚合氯化铝铁(PAFC)对垃圾渗滤液进行混凝沉淀处理,考察了3种混凝剂对渗滤液中TOC、CODCr和UV254的去除效果,并且根据单因素试验确定出PAC为最佳混凝剂,最佳投药量为6g/L.对渗滤液腐殖质分离方法进行了简化,并对经3种混凝剂处理后水样内的腐殖酸...     

Adsorption mechanism of humic and fulvic acid onto Mg/Al layered double hydroxides

The adsorption of humic and fulvic acids onto nitrate, chloride and carbonate intercalated layered double hydroxides with Mg/Al ratios ranging from 85/15 to 60/40 was studied by adsorption isotherms at different ionic strengths and the characterization of the preferentially adsorbed humic substance size fractions. The adsorption of humic and fulvic acids onto LDHs occurred by ion exchange with both the intercalated and surface anions of the LDH and ligand exchange reactions with surface groups. The contribution of both mechanisms to the total HA and FA adsorption was estimated. Lower molecular weight humic and fulvic acids were preferentially adsorbed because these fractions can more easily enter the mesoporous LDHs and contain more carboxylic groups, which are known to be involved in ligand exchange reactions with e.g. surface Al-OH groups. Intercalation of the entire HA or FA molecules in-between the LDH sheets is unlikely to occur.     

Enhanced fluoride removal from drinking water by magnesia-amended activated alumina granules

This paper describes the fluoride removal potential of a novel sorbent, magnesia-amended activated alumina (MAAA) from drinking water. MAAA, prepared by calcining magnesium hydroxide impregnated alumina at 450 °C has shown high fluoride sorption potential than activated alumina from drinking water. Batch sorption studies were performed as a function of contact time, pH, initial fluoride concentration, and adsorbent dose. Studies were also performed to understand the effect of various other co-existing ions present in real ground water samples. X-ray powder diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray (EDAX) and a gas adsorption porosimetry analyses were used to characterize the physicochemical properties of MAAA. More than 95% removal of fluoride (10 mg l⁻¹) was achieved within 3 h of contact time at neutral pH. Sorption of fluoride onto MAAA was found to be pH dependant and a decrease in sorption was observed at higher pHs. Among the kinetic models tested, pseudo-second-order model fitted the kinetic data well, suggesting the chemisorption mechanism. Among the various isotherm model tested, Sips model predicted the data well. The maximum sorption capacity of fluoride deduced from Sips equation was 10.12 mg g⁻¹. Most of the co-existing ions studied have negligible effect on fluoride sorption by MAAA. However, higher concentrations of bicarbonate and sulfate have reduced the fluoride sorption capacity.     

接触时间、pH值、土壤中腐植酸／富里酸、离子强度和温度对MX-80膨润土吸附U（Ⅵ）的影响

本文在室温条件下采用批处理的方式,研究了MX-80膨润土对水溶液中U（VI）的吸附行为,考察了接触时间、p H值、离子强度、固体含量、腐植酸（H A）、富里酸（F A）和温度等因素的影响。实验结果表明,M X-80膨润土对U（V I）的吸附能力受p H和离子强度的影响较大。U（V I）从水溶液被吸附到M X-80膨润土上的速度相当快,并且其动力学吸附数据符合准二维速率方程。腐植酸可以显著增强MX-80膨润土对的U（VI）吸附,而富里酸对U（VI）的吸附没有显著影响。从不同温度下计算得到的M X-80膨润土对U（V I）的吸附热力学参数（△H0,△S0和△G0）可以看出, MX-80膨润土对U（VI）的吸附反应是自发的吸热反应。     

Ammonia sorption by peat and N fractionation in some peat-ammonia systems

Ammonia sorption is an important peat property for making composts and peat-mineral fertilizers. In this study, we investigated the influence of moisture content of fibric, hemic and sapric peat materials on ammonia sorption capacity, and we determined the N forms and the amount of solubilized humic substances following peat ammoniation. Ammonia sorption capacity increased curvilinearly with degree of decomposition from the fibric to the sapric peats, and increased with peat moisture content up to 600 g H₂O [kg wet peat]^–1 in the range of 400 to 700 g H₂O [kg wet peat]^–1. The amount of chemically sorbed ammonia was highest in the sapric peat containing [600 g H₂O] [kg wet peat]^–1. On a dry weight basis, maximum sorption capacity was 24 g NH₃-N kg^–1 for the fibric peat, 29 g NH₃-N kg^–1 for the hemic peat and 49 g NH₃-N kg^–1 for the sapric peat. Ammonia loss of physically retained ammonia was greatest at the highest moisture content and for the least decomposed peat. At ammoniation rates exceeding 30 g NH₃ [kg dry peat]^–1, exchangeable ammonium and acid-hydrolyzable N were the dominant N fractions in ammoniated peats. Peat ammoniation increased significantly (p < 0.001) the amounts of water-soluble carbon in all peat materials, of fulvic acid in the fibric peat and of both humic and fulvic acids in the hemic and the sapric peats. At maximum ammonia sorption capacity, the total amount of water-soluble and alkali-extractable organic matter reached 338 g kg^–1 in fibric peat, 683 g kg^–1 in the hemic peat and 848 g kg^–1 in the sapric peat. The hemic and sapric peats appeared more appropriate than the fibric peat for making peat-base fertilizers.     

Effects of Ozonation on Molecular Weight Distribution of Humic Substances and Coagulation Processes – A Case Study: The Úzquiza Reservoir Water

In this article the influence of preozonation on the effectiveness of NOM removal via coagulation processes will be studied (focusing on the influence of the calcium hardness) as well as changes in MW (molecular weight) distribution of humic substances caused by ozonation. Additionally, THMFP removal in both ozonation and preozonation-coagulation processes is assessed. Three different types of water have been used in this study: a natural water from the Úzquiza Reservoir (Burgos, Spain), a synthetic water prepared using natural fulvic acids extracted from the Úzquiza Reservoir and a synthetic water prepared using a commercially supplied humic acid. Molecular weights of humic substances were determined using high-performance size exclusion chromatography (HPSEC); average molecular weights calculated for the unozonated humic substances are 4500 Da for the commercial humic acids and 1000 Da for the natural fulvic acids extracted from the Úzquiza Reservoir. Preozonation shifted the molecular weight distribution of humic substances (both humic and fulvic acids) towards lower average molecular weight values. For the natural water from the Úzquiza Reservoir (with low levels of calcium hardness and hydrophobic fraction (humic substances) being the main fraction of NOM), preozonation has a negative effect on the effectiveness of the coagulation process for NOM removal: the percentages of TOC removal via coagulation decrease with increasing ozone dosage; the maximum TOC removal (33%) is achieved for the unozonated water. Also for this water, ozonation reduced 5–25% of THMFP with ozone doses varying from 0.25 to 2.5 mg O₃/L. A preferential THMFP removal, that is to say, higher reduction in THMFP (43%) relative to TOC (28%) is achieved by the coagulation-flocculation process; this also occurs when preozonation is used, independently of ozone dosage.     

Zn(II) ions removal from aqueous solution by Karachi beach sand, a mixed crystal systems

The aim of this research work is to investigate sorption characteristic of beach sand for the removal of Zn(II) ions from aqueous solutions. The sorption of Zn(II) ions by batch dynamic method is carried out using dilute solutions (10⁻⁴ M) of nitric, hydrochloric and perchloric acids along with deionized water and from buffers of pH 2–10. Maximum sorption is noticed from deionized water (88.3%) using 30 min shaking time. Two equations, i.e. Morris–Weber and Lagergren have been tested to track the kinetics of removal process. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) model are subjected to sorption data to estimate sorption capacity, intensity and energy. The thermodynamic parameters ΔH, ΔS and ΔG are evaluated. The influence of common ions on the sorption of Zn(II) ions is also examined. Some ions reduce the sorption while most of the ions tested have very little effect. It can be concluded that beach sand has potential to remove Zn(II) ions from aqueous solutions at very low concentrations and for the treatment of industrial effluent carrying Zn(II) ions.     

Natural Micas Intercalated with Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Modified with Transition Metals as Catalysts of the Selective Oxidation of Ammonia to Nitrogen

Natural cationic layered clays—vermiculite and phlogopite—pretreated with acids were intercalated with alumina pillars. In next step, transition metals were deposited on the surface of pillared interlayer clays (PILC) by a liquid ion exchange method. The catalyst samples were characterized with respect to: composition (EPMA), structure (XRD), texture (BET), surface acidity (NH₃-TPD) and coordination of deposited transition metals (UV–vis-DRS). The modified clays were tested in the role of catalyst for the selective oxidation of ammonia to nitrogen. In a series of the studied samples the best catalytic performance presented alumina pillared vermiculite modified with copper.     

Removal of Cadmium from Aqueous Solution using Wheat Stem,Corncob, and Rice Husk

Three kinds of agricultural by-products, wheat stem, corncob, and rice husk, were tested as biosorbents for cadmium removal from aqueous solution. The study was focused on the evaluation and comparison of the potential of the agriculture by-products as biosorbents of cadmium with the sorption isotherms determination. The impact of solution pH and kinetic study was also discussed. The result indicated that cadmium removal was strongly dependent on solution pH and the optimum pH range is 4.5 ～ 6.0. The sorption process was fast, and the sorption equilibrium can be attained within 60 min. The kinetic process fit well with the pseudo-second-order kinetic model. For the three kinds of biosorbents, the initial sorption rate as well as the maximum sorption capacity q _max calculated from the Langmuir isotherm equation showed the following tendency: rice husk > wheat stem > corncob. The maximum sorption capacity of the three kinds of biosorbents enhanced after being base treated, especially for wheat stem and corncob. This study indicated that wheat stem, corncob, and rice husk displayed the potential to be used as biosorbents for cadmium removal from aqueous solution.     

Influence of Synthesis Conditions and Cerium Incorporation on the Properties of Zr-Pillared Clays

Zr-pillared clays were prepared from ZrOCl₂ pillaring solutions by adopting different preparative conditions. Ce³⁺ ions are introduced to Zr-pillared clays by co-intercalation method. The resulting samples were characterized by XRD, TGA, N₂ sorption and UV-VIS-Diffuse reflectance spectroscopy techniques. Basal spacings in the range of 18–21 Å were observed depending upon the preparative condition. TG analysis shows three weight loss regions corresponding to removal of various types of water molecules. All pillared clays show Type-I sorption isotherm typical of microporous materials. Pillaring under refluxing condition is found to have beneficial effect on the surface area and pore volume of the Zr-pillared clay. The chemical environment and location of Ce³⁺ ions is studied by UV-VIS-DRS. The Ce³⁺ ions are found to be present in the micropores of the Zr-pillared clays. However heat treatment at higher temperature may result in peripheral interaction between Ce³⁺ ions and Zr-pillars. Catalytic activity of these pillared clays was evaluated for cyclohexanol dehydration which correlates well with the Brønsted acidity of these materials. The Zr-Pillared clay containing Ce³⁺ ions show good catalytic activity and stability with reaction time which has been ascribed to the stabilazition of the Brønsted acidic centers.     

Influence of Ozonation of Humic and Fulvic Acids on Diuron Adsorption on Activated Carbon

The effect of ozonation on the competitor effect of humic and fulvic acids against diuron in adsorption on activated carbon in drinking water process has been studied. Ozonation treatment allows the removal of herbicides from drinking waters by modification of humic and fulvic acids structures. These latest are responsible for their adsorption variation on activated carbon. An ozone dose similar to that used in industrial pre-ozonation (1.3?mg ozone/l) does not cause significant transformations of humic and fulvic acids which could decrease their competitor effect and increase significantly the adsorption capacity of the activated carbon for a well-adsorbed pesticide like diuron.     

Adsorption of fulvic acids from aqueous solutions by carbon nanotubes

Carbon nanotubes (CNTs) were used as adsorbent to remove fulvic acids (FA) from aqueous solutions. The adsorption capacity of CNTs for FA can reach 24 mg g^?1 at 5 °C and equilibrium concentration of 18 mg dm^?3. The kinetic and thermodynamic parameters, such as rate of adsorption, standard free energy changes (ΔG⁰), standard enthalpy change (ΔH⁰) and standard entropy change (ΔS⁰), have been obtained. Acidic conditions (pH = 2–5) favor FA removal. An increase in the ionic strength or the addition of divalent cations increase the adsorption of FA dramatically (FA = 60 mg dm^?3). An increase in the maximum adsorbed amount of FA was observed when treating FA in synthetic seawater. Desorption studies reveal that FA can be easily and quickly removed from CNTs by altering the pH values of the solution. Good adsorption capacity and quick desorption indicate that CNTs are a promising adsorbent to remove FA from aqueous solutions. Copyright © 2007 Society of Chemical Industry     

The Effect of Ozonation on the Removal of Organics by Coagulation – Flocculation

We present here some works which take place in the particular framework of the study of drinking water treatment of reservoir waters which contain high concentrations of organics, mainly humic substances. Previous studies on coagulation of fulvic acid solutions have proved that the optimal removal of organic matter was reached at acidic pH with 2 mg of ferricion per mg or organic carbon (summarized in this paper). The main question in this study is to know what is the impact of preozonation on the removal of organics by iron (III) coagulation.

The study of the behavior of organics, in terms of UV-absorbance and TOC measurements was made on three aquatic fulvic acids and on two raw waters. The experiments carried out with fulvic acids showed that preozonation (at 0.5 mg O₃/mg C) of fulvic acid appeared to have shifted the region of the optimal DOC removal towards the higher coagulant dose. Furthermore, increasing ozone doses led to a slight decreasing of coagulation efficiency at constant coagulant dose. With two raw waters, preozonation at low ozone doses (0.2 mg 0₃/mg C) was found to improve very slightly the elimination of organic matter, while high ozone doses (0.9 mg O₃/mg C) led to a disturbance of TOC elimination by iron coagulation.     

TiO2光催化降解水中天然有机物富里酸的动力学模型

在天津地表水中天然有机物主要是富里酸,它是消毒副产物的主要前驱体,因此对于富里酸的控制非常重要.以粉末态TiO₂为催化剂,在光催化-超滤反应器中对水中天然有机物富里酸进行了光催化氧化研究,考察了富里酸氧化的主要影响因素,包括初始pH值、催化剂浓度、光强、添加剂浓度.结果表明：富里酸降解过程能够用一级反应动力学来表示;最佳的催化剂浓度为0.5 g&#8226;L^-1;在pH值减小、添加剂浓度和光强增大时有助于富里酸的去除.通过分析反应速率常数和影响因素之间的关系,得到富里酸光催化氧化总体动力学模型,试验值基本符合动力学模型.另外试验还表明该反应器可方便地实现有机物降解且具有较高的去除效率.     

As(III) removal from drinking water using manganese oxide-coated-alumina: Performance evaluation and mechanistic details of surface binding

This paper describes the arsenite [As(III)] removal performance of manganese oxide-coated-alumina (MOCA) and its interaction with As(III) in drinking water. MOCA was characterized by XRD, SEM, EDAX, gas adsorption porosimetry, and point of zero charge (pH_pzc) measurements. Raman spectroscopy coupled with sorption experiments were carried out to understand the As(III) interaction with MOCA. As(III) sorption onto MOCA was pH dependent and the optimum removal was observed between a pH of 4 and 7.5. The Sips isotherm model described the experimental equilibrium data well and the predicted maximum As(III) sorption capacity was 42.48 mg g⁻¹, which is considerably higher than that of activated alumina (20.78 mg g⁻¹). The sorption kinetics followed a pseudo-second-order equation. Based on sorption and spectroscopic measurements, the mechanism of As(III) removal by MOCA was found to be a two-step process, i.e. oxidation of As(III) to arsenate (As(V)) and retention of As(V) on MOCA surface, with As(V) forming an inner surface complex with MOCA. The results of this study indicated that MOCA is a promising alternative sorbent for As(III) removal from drinking water.     

Water Sorption,Glass Transition,and Microstructures of Refractance Window– and Freeze-Dried Mango (Philippine “Carabao” Var.) Powder

Water sorption isotherms, glass transition, and microstructures of Refractance Window (RW)– and freeze-dried Philippine “Carabao” mango powders were investigated. Water sorption isotherms were developed by the isopiestic method, while thermal transition of the powders, at various water activities (a _w  = 0.11–0.86), was determined using differential scanning calorimetry (DSC). The sorption isotherms of RW- and freeze-dried (FD) mango powders exhibited a type III sigmoidal curve, showing higher and lower adsorption capacities above and below 0.5 a _w , respectively. A significant difference (p < 0.05) in water content of RW- and freeze-dried mango powders for equivalent water activities was obtained above 0.5 a _w . The onset glass transition temperature (T _gi ) of RW- and freeze-dried mango powder solids decreased as the water content increased. There were no significant differences (p ≥ 0.05) in T _gi of RW- and freeze-dried mango powder solids at constant water activities, except for a _w  = 0.86. Microscopic examination of mango powders indicated that freeze-dried mango powders exhibited greater surface area and porosity in comparison to RW-dried mango powders.     

A model of S,P and N uptake by a perennial pasture

Phosphate sorption curves give useful information about the management of the P fertility in soils. This study was conducted to examine how P sorption characteristics were influenced, and could be predicted from the properties of Mediterranean soils of Spain. The 114 soils studied differed widely in origin and properties and were grouped as calcareous (43) and noncalcareous (71). Citrate-bicarbonate-dithionite extractable Fe (Fe_d) and Al (Al_d) and clay were the properties best correlated with the P sorbed and the P buffer capacity at an equilibrium concentration of 0.2 mg P l^–1. This suggests that Fe oxides and silicate clays play a significant role in P sorption. Stepwise regression analysis showed, however, that clay was not a significant variable in the calcareous group, but active CaCO₃ was. Prediction of the P sorption parameters was better for the noncalcareous than for the calcareous group. This reduced ability to predict P sorption in calcareous soils may be due to the inability of total or active CaCO₃ to adequately measure the reactivity of carbonates towards P sorption. From 53 to 75% of the variation in P sorption parameters could be explained by regression equations including all or several of the following routinely-determined soil properties: clay, pH, Fe_d, and active CaCO₃. These equations could, therefore, provide a simple and rapid estimation of P sorption in soils of Mediterranean regions.