Adsorption mechanism of polylysine on hydroxyapatite and its effect on dissolution properties of hydroxyapatite

Adsorbed amounts of poly-l-lysine (pLys) and bromide ion on hydroxyapatite (HAp) from aqueous solutions of poly-l-lysine hydrobromide, and amounts of calcium and phosphate ions liberated concurrently from HAp during the adsorption of pLys were determined at 25 degrees . The pLys was adsorbed on HAp by the mechanism of ion-exchange between its amino groups and calcium ions of HAp. The released amount of calcium ion increased, therefore, with the adsorbed amount of pLys. On the other hand, the released amount of phosphate ion first decreased and then increased after attaining a minimum with the equilibrium concentration of pLys. The analysis using an equilibrium dialysis method revealed that the released phosphate ions were mainly in the bound state to the amino groups of pLys remaining in the solution, and that the concentrations of calcium and phosphate ions free from both HAp and pLys were restricted by each other under the law of the solubility product of HAp. The first decrease in the released amount of phosphate ion was concluded to be attributed primarily to the increase in the released amount of calcium ion because pLys remaining in the solution was little in this region. When sodium hydroxide was added to the solution, the adsorbed amount of pLys increased and then slightly decreased with the equilibrium pH of the solution due to the increase or decrease of the electrostatic attractive force between the adsorbate and the adsorbent. However, conformational change in pLys around pH 10 seemed to have little effect on the adsorption.     

Removal of phosphate by aluminum oxide hydroxide

The development and manufacture of an adsorbent to remove phosphate ion for the prevention of eutrophication in lakes are very important. The characteristics of phosphate adsorption onto aluminum oxide hydroxide were investigated to estimate the adsorption isotherms, the rate of adsorption, and the selectivity of adsorption. Phosphate was easily adsorbed onto aluminum oxide hydroxide, because of the hydroxyl groups. The adsorption of phosphate onto aluminum oxide hydroxide was influenced by pH in solution: the amount adsorbed was greatest at pH 4, ranging with pH from 2 to 9. The optimum pH for phosphate removal by aluminum oxide hydroxide is 4. The selectivity of phosphate adsorption onto aluminum oxide hydroxide was evaluated based on the amount of phosphate ion adsorbed onto aluminum oxide hydroxide from several anion complex solutions. It is phosphate that aluminum oxide hydroxide can selectively adsorb. The selectivity of phosphate onto aluminum oxide hydroxide was about 7000 times that of chloride. This result indicated that the hydroxyl groups on aluminum oxide hydroxide have selective adsorptivity for phosphate and could be used for the removal of phosphate from seawater.     

Protein Adsorption onto Nanosized Hydroxyapatite Particles for Controlled Drug Release

Nanosized hydroxyapatite(nsHAp) was synthesized to examine its possibility as a controlled release carrier of protein. To achieve effective protein release from nanosized hydroxyapatite, the study of the adsorptive properties of protein on nsHAp and different influence parameters such as pH, calcium, and phosphate concentrations during the adsorption process is necessary. Ovalbumin(OVA) was selected as the model of growth factors. The results show that the amount of OVA adsorbed onto nsHAp in acetic buffer(pH=3.6) is more than that in acetic buffer(pH=5.6) because of the electric interaction. The amount of OVA adsorption in phosphate buffer solution(PBS) is smaller than that in acetic buffer because of surface complexation and surface hydroxylation. The presence of Ca2 dramatically increases the adsorbed amount of OVA in acetic buffer on maintaining the same pH. Meanwhile, the release kinetics of OVA adsorbed onto nsHAp(nsHAp-OVA) was also examined. The amount of released OVA in PBS(pH=5.6) was significantly smaller than that released in solution of pH=7.0. All the results suggest that nanosized hydroxyapatite particles could be successfully used as controlled released carrier of protein.     

Adsorption of fluoride, phosphate, and arsenate ions on a new type of ion exchange fiber

A new type of ion exchange fiber for the removal of fluoride, phosphate, and arsenate ions has been developed. A batch adsorption technique for investigating adsorption kinetic and equilibrium parameters and determining pH adsorption edges is applied. It is shown that the adsorption properties of the ion exchange fiber for fluoride, phosphate, and arsenate ions depend on the pH value and anion concentration. The adsorption of arsenate on the sorbent reaches a maximum of 97.9% in the pH value range of 3.5 to 7.0. The adsorption percentage of phosphate is more than 99% in the pH range of 3.0 to 5.5. The adsorption of fluoride on the ion exchange fiber is found to be 90.4% at pH 3.0. The Freundlich model can describe the adsorption equilibrium data of fluoride, arsenate, and phosphate anions. The sorption of the three anions on the ion exchange fiber is a rapid process, and the adsorption kinetic data can be simulated very well by the pseudo-second-order rate equation. The column performance is carried out to assess the applicability of the ion exchange fiber for the removal of fluoride, phosphate, and arsenate ions from synthetic wastewaters with satisfactory removal efficiency. The desorption experiment shows that fluoride ion sorbed by the fiber column can be quantitatively desorbed with 5 mL of 0.50 mol/L NaOH at elution rate of 1 mL/min, and 30 mL of NaOH is necessary for the quantitative recovery of phosphate and arsenate ions.     

Competitive Adsorption of Chloroform and Iron Ion onto Activated Carbon Fiber

Chloroform in tap water has been a significant problem because it may be a carcinogenic substituent. Iron ion exists in tap water because of dissolution from iron water pipes. Iron ions in tap water cause discoloration and a bad odor. The isotherms of chloroform and iron ion adsorption onto activated carbon fibers in a single solution (chloroform or iron ion) and in a binary mixture solution (chloroform and iron ion) were investigated to estimate the competitiveness between chloroform and iron ions. The amount of adsorbed iron ions increased with increasing pore volume of the activated carbon fibers, while that of chloroform decreased. The amount of chloroform adsorbed onto the activated carbon fibers in the binary mixture solution was greater than that in the single solution. These results indicate that the adsorption of chloroform and iron ion onto activated carbon fibers could be competitive.     

Removal of fluoride from aqueous solution using acid and thermally treated bone char

In this work, bone char (BC) was synthesized at different calcination temperatures and modified by using HNO₃ solutions having distinct concentrations. Furthermore, the relationship between the crystalline structure and physicochemical properties of BC on the adsorption capacity of BC towards fluoride from aqueous solution was analyzed. It was noted that the calcination temperature and the acid modification of BC significantly influenced the crystalline phases, crystallite size, and contents of hydroxyapatite, monetite, and other calcium phosphates, which are the main constituents of the BC. Additionally, the surface area diminished by raising both the calcination temperature and acid concentration used in the modification. The adsorption capacity of BC linearly declined as the calcination temperature was increased from 400 to 800 °C. On the other hand, BC modified with HNO₃ solutions showed that the adsorption capacity of BC was enhanced when monetite and hydroxyapatite with low crystallinity were present in these materials. Hence, the adsorption capacity of BC treated with acid was independent of textural properties. The adsorption capacity of BC was enhanced by increasing the solution pH due to the electrostatic interactions between the fluoride in the solution and the surface charge of BC. Finally, DRX, FTIR spectroscopy, and XPS studies corroborated that the fluoride adsorption mechanism on BC modified with acid solutions was influenced by electrostatic interactions and chemisorption between fluoride ions in solution and calcium phosphates from hydroxyapatite and monetite.     

Ozone Degradation by Fluoride onto Plasma-Treated Activated Carbon in CF4

The ozone degradation of fluorine was investigated using the tetrafluoromethane plasma-treated activated carbon (PT-AC). The ozone in the stratosphere has been degraded by the chloride and bromide radicals which are produced from chlorofluorocarbons and bromofluorocarbons, respectively. However, we believe that fluorine also was related to the ozone degradation. The fluoride was introduced onto the activated carbon surface by tetrafluoromethane plasma treatment. The breakthrough curve of ozone onto PT-AC was measured to elucidate the relationship between the ozone and the fluoride. The amount of ozone adsorbed/degraded onto the PT-AC was larger than the amount that was adsorbed/degraded onto the untreated activated carbon. The amount of fluoride ion eluted from the PT-AC before the adsorption/degradation of ozone was larger than that which eluted after the adsorption/degradation of ozone. These results indicated that the ozone was degraded by the fluoride on the PT-AC surface.     

Evaluation of the adsorption affinity of proteins to calcium hydroxyapatites by desorption and pre-adsorption methods

The adsorption affinity of bovine serum albumin (BSA) and lysozyme (LSZ) to calcium hydroxyapatite (CaHAP) was evaluated by desorption and two step adsorption methods. These experiments were carried out at 15°C in a 1×10⁻⁴ mol dm⁻³ KCl solution of pH 6.0. BSA molecules were scarcely desorbed, exhibiting an irreversible adsorption of BSA, though LSZ slightly desorbed. This result supports our previous findings that LSZ adsorbs weakly onto phosphate ions exposed on ac or bc faces of CaHAP while BSA adsorbs strongly onto positively charged sites on ac or bc faces of CaHAP. The amount of adsorbed LSZ was markedly increased by the pre-adsorption of BSA, where LSZ was adsorbed onto BSA-covered CaHAP. On the other hand, the amount of adsorbed BSA was not changed by the pre-adsorption of LSZ. In both pre-adsorption systems it was confirmed by an HPLC method that no protein molecule pre-adsorbed was desorbed after the post-adsorption procedure. Therefore, it was interpreted that the enhancement of adsorption of positively charged LSZ is induced by an electrostatic attractive force through pre-adsorption of negatively charged BSA molecules with a high coverage. However, since the coverage of LSZ onto CaHAP is considerably low, no stimulation of BSA adsorption occurred on the LSZ-covered surface. The formation of double protein adsorbed layers consisting of pre- and post-adsorbed proteins was proposed.     

Characteristics of granular boehmite and its ability to adsorb phosphate from aqueous solution

In this study, we investigated the surface properties of granulated boehmite with vinyl acetate (G-BE20) and measured the amount of phosphate it adsorbed and the effect of contact time and solution pH on the adsorption process. The specific surface area (144.9?m²/g) and the number of surface hydroxyl groups (0.88?mmol/g) of G-BE20 were smaller than those of virgin boehmite (BE), which gave a specific surface area and number of surface hydroxyl groups of 297.0?m²/g and 1.08?mmol/g, respectively. The amount of phosphate adsorbed increased with the temperature. The isotherm model of Langmuir was used to fit experimental adsorption equilibrium data for phosphate adsorption onto G-BE20. The calculated thermodynamic parameters show the spontaneous and endothermic nature of the adsorption process. The equilibrium adsorption onto G-BE20 was reached within 16?h and the amount of phosphate adsorbed was 8.4?mg/g. The kinetic mechanism of phosphate uptake was evaluated with two different models: the Largergren pseudo first- and pseudo second-order models. The data obtained showed a better fit to the pseudo second-order model (0.991) than to the pseudo first-order model (0.967), as indicated by the r values. The rate constants for the adsorption of phosphate onto G-BE20 were calculated as 0.481?1/h and 0.029?g/mg?h. The adsorption of phosphate onto G-BE20 was the maximum in the pH range 3.0-4.0.     

Preliminary results on the immobilisation of radionuclides from waters with specific adsorbers based on phosphate salts

The present paper is focused on the ability of aluminium phosphate (ALPC), magnesium ammonium phosphate (MGPC), magnesium hydrogen phosphate (MGHPC), and calcium hydrogenphosphate (CAHPC), adsorbed onto charcoal, to immobilise actinides by adsorption from natural waters. The objective of this process is to evaluate the environmental pollution due to the actinides. Europium, thorium, protactinium, neptunyl, and uranyl ions were chosen to simulate actinides in the +3, +4, +5 and +6 oxidation state. The adsorbers were tested using natural waters samples. The adsorption trends and capacities were analysed. ALPC and MGPC exhibited a similar behaviour and adsorbed demonstrating that the +5, +4 and +3 actinide ions can be easily immobilised from natural waters and may be successfully used at pH 7-8. MGHPC may be used at a higher pH, whereas CAHPC is effective in the whole pH range. In all cases, thorium, protactinium and europium were strongly     

ATR-FTIR investigation on the complexation of myo-inositol hexaphosphate with aluminum hydroxide

The adsorption isotherm of and the pH effect on the adsorption of myo-inositol hexaphosphate (myo-IP6) on amorphous aluminum hydroxide was investigated. It was found that the adsorption isotherm of myo-IP6 on aluminum hydroxide could be well fitted with the Freundlich isotherm. The amount of myo-IP6 adsorbed remained almost constant in the range of pH 4.0 to 7.0, but it decreased considerably as the initial pH was over 7. The adsorption of myo-IP6 resulted in an increase in the pH level due to the release of OH(-) ions, which suggested that the adsorption of myo-IP6 on aluminum hydroxide was caused by a ligand exchange reaction. ATR-FTIR analysis of myo-IP6 in solution and adsorbed on aluminum hydroxide at different pH were performed. The ATR-FTIR investigation indicated that myo-IP6 was adsorbed onto aluminum hydroxide by forming inner-sphere complexes and adsorption facilitated the deprotonation of phosphate groups. The asymmetric vibration of the PO bond in AlPO(-)(3) appearing at a lower frequency than that in the terminal HPO(-)(3) indicated that Al bound to the O atom not as strongly as the H atom did. The ATR-FTIR investigation and theoretical calculation (with the Gaussian 03 program) revealed that three of the six phosphate groups in myo-IP6 molecules were bound to aluminum hydroxide while the other three remained free when myo-IP6 was adsorbed on aluminum hydroxide.     

Characterization of water adsorption onto carbonaceous materials produced from food wastes

The recycling of organic wastes has become very important and the development of technology for recycling organic wastes needs to sustain industrial development. In this study, techniques for producing carbonaceous materials from organic wastes are described and water adsorption is characterized. The organic wastes used are coffee grounds and oolong tea leaves carbonized at 673 to 1073 K. The iodine adsorption capacity of the carbonaceous materials increased with increased carbonization temperature. The amount of water adsorbed onto the carbonization materials produced from oolong tea leaves at 873 K for 2 h was the highest. The Freundlich constant 1/n and the differential heat of adsorption of the carbonaceous materials produced from oolong tea leaves were greater than that of the carbonaceous materials produced from coffee grounds. The ability to humidity control can be estimated by the difference between the amount of water adsorbed relative pressure 0.90 and that at relative pressure 0.55. The ability to humidity control was the greatest for the carbonaceous materials produced from the oolong tea leaves at 873 K for 2 h and did not depend upon the adsorption temperature. These results indicated that the carbonaceous materials produced from oolong tea leaves at 873 K for 2 h could have more humidity control.     

Performance and Mechanisms of Fluoride Removal from Groundwater by Lanthanum-aluminum-loaded Hydrothermal Palygorskite Composite

Lanthanum-aluminum loaded hydrothermal palygorskite(La-Al-HP) composite was prepared and selected as adsorbent for the fluoride removal from simulated groundwater. The adsorbent was characterized by scanning electron microscopy(SEM), Brunauer-Emmet-Teller(BET) analysis, X-ray diffraction(XRD) analysis and X-ray photoelectron spectroscopy(XPS). SEM visualization shows that the dense surface structure of raw HP appeared loose and presented micro canals after modification. The BET analysis also proved the specific surface area of La-Al-HP composite(95.58 m²/g) was higher than that of the raw HP(34.31 m²/g). Subsequently, the adsorption capacity of La-Al-HP composite was demonstrated in adsorption experiments. The kinetics of fluoride ion adsorption into La-Al-HP composite followed the pseudo-second order with a correlation coefficient of 0.997. The isotherm data was well fitted with the Langmuir model. The monolayer adsorption capacity of La-Al-HP composite was 1.30 mg/g. The XRD and XPS results reveal that the La³⁺ and Al³⁺ ions were loaded on the surface of modified HP and the fluoride ion was adsorbed onto the La-Al-HP composite. A large amount of La-Al-O composite oxide existing on the surface of La-Al-HP composite might be the immanent cause for the excellent adsorption capacity of fluoride ions.     

Calcium-Mediated Adsorption of Neutral Amino Acids to Carboxymethylated Chitin

Among various divalent metal ions, calcium has been found to be adsorbed tightly onto carboxymethylated chitin. The adsorption was completed not only by induced carboxyl groups but also by the support of acetamide, as well as primary and secondary hydroxyl groups. Although the adsorption capacity for transition metal ions was enhanced appreciably by regeneration into fibrous form, only that of calcium ion, among alkali-earth metals, was at the same level as that of transition metals. Since little effect was shown on the adsorption of phenylalanine by the blocking of α-amino and α-carboxyl groups of L-Phe, and since D-Phe was so a little adsorbed, the chiral specific adsorption of phenylalanine might be supported by mediation of calcium ion and by the contribution of hydrophobicity of the β-phenyl group.     

羧甲基纤维素钠和甲基纤维素在ZrO_2微粉上的吸附作用及其对悬浮体稳定性的影响

研究了ZrO2微粉自水中对羧甲基纤维素钠（CMC）和甲基纤维素（MC）的吸附作用及对ZrO2水悬浮作稳定性的影响．结果表明：（1）CMC的吸附等温线为Langmuir型,CMC可能以较为舒展的方式单层吸附于ZrO2。表面,由于有电性吸引作用在pH3．4时的极限吸附量较pH7．0时的略大;（2）MC的极限吸附量远大于CMC的,MC分子可能以线团状吸附,吸附层厚度可达14～56nm;（3）难较大浓度时MC比CMC更易于使ZrO2悬浮作稳定．     

Film-Pore Diffusion Control for the Batch Sorption of Cadmium Ions from Effluent onto Bone Char

The sorption equilibrium and kinetics of cadmium ions from aqueous solution onto bone char have been studied. Equilibrium isotherms for the sorption system were correlated by Langmuir and bi-Langmuir equations. The application of the bi-Langmuir equation was developed because the mechanistic analysis in this research indicated that cadmium removal occurs ion exchange and physical adsorption onto different surface sites. The bi-Langmuir equation provides a better fit to the experimental data. In addition, the removal rates of cadmium ions based on the Langmuir models have been investigated. The effective diffusivity was calculated using the effects of initial metal ion concentration and bone char mass. Two mass-transport models based on film-pore diffusion control have been applied to analyze the concentration decay curves. The film and pore diffusion coefficients using an analytical equation are equal to 1.26x10(-3) cm/s and 5.06x10(-7) cm(2)/s, respectively. The pore diffusion coefficient obtained from the numerical method is 4.89x10(-7) cm(2)/s. A sensitivity analysis showed that the film-pore diffusion model and constant effective diffusivity could be used to describe the mass-transport mechanism of the sorption system with a high degree of correlation. Copyright 2001 Academic Press.     

Critical Evaluation of Adsorption–Desorption Hysteresis of Heavy Metal Ions from Carbon Nanotubes: Influence of Wall Number and Surface Functionalization

Single‐, double‐, and multi‐walled carbon nanotubes (SWCNTs, DWCNTs, and MWCNTs), and two oxidized MWCNTs with different oxygen contents (2.51 wt % and 3.5 wt %) were used to study the effect of the wall number and surface functionalization of CNTs on their adsorption capacity and adsorption–desorption hysteresis for heavy metal ions (Ni^II, Cd^II, and Pb^II). Metal ions adsorbed on CNTs could be desorbed by lowering the solution pH. Adsoprtion of heavy metal ions was not completely reversible when the supernatant was replaced with metal ion‐free electrolyte solution. With increasing wall number and amount of surface functional groups, CNTs had more surface defects and exhibited higher adsorption capacity and higher adsorption–desorption hysteresis index (HI) values. The coverage of heavy metal ions on the surface of CNTs, solution pH, and temperature affect the metal ion adsorption–desorption hysteresis. A possible shift in the adsorption mechanism from mainly irreversible to largely reversible processes may take place, as the amount of metal ions adsorbed on CNTs increases. Heavy metal ions may be irreversibly adsorbed on defect sites.     

Adsorption of lanthanoid ions on calcite

The adsorption of 14 trivalent lanthanoid ions and yttrium ion (denoted by Ln3+) on calcite surfaces was investigated under various solution conditions of pH (pH = 6.8-7.8) and calcium ion concentration (pCa = -log[Ca2+]= 2.0 and 3.0), and different surface conditions of calcite crystals (well-developed and rough surfaces). The lanthanoid ions were equilibrated in a solution of ionic strength 0.1 mol dm-3(NaCl) saturated with calcite at 25.0 degrees C using excess (solid) calcite crystals suspended in solution. The concentrations of the lanthanoid ions on the calcite crystals (C(cry)/mol kg-1) and in solution (C(soln)/mol dm-3) were determined by means of inductively coupled plasma-mass spectrometry (ICP-MS). It is found that the distribution ratio (D=C(cry)/C(soln) decreases as the atomic number of the lanthanoid increases showing the so called Tetrad Effect. D values increase with increasing pH, whereas they are independent of the calcium ion concentration (i.e., carbonate ion concentration). These results indicate that lanthanoid ions are adsorbed on the calcite surface together with hydroxide ions, i.e., the adsorption of hydroxo-complexes. The heavy lanthanoid ions (Er3+ to Lu3+) are adsorbed as monohydroxo-complexes, (Ln(OH)2+), whereas those of the light lanthanoids are predominantly adsorbed as dihydroxo-complexes (Ln(OH)2+). Other lanthanoids show competitive adsorption reactions of mono- and dihydroxo complexes. Both successive adsorption constants of hydroxo complexes increase with decreasing atomic number of the lanthanoid. The rough surface of calcite is quite active and the distribution ratio of the lanthanoid ions on the rough surface is much higher than that on the well-developed crystalline surface. Rates of adsorption of lanthanide ions were measured and mechanisms are being discussed     

Removal of arsenious ion by calcined aluminum oxyhydroxide (boehmite)

Aluminum oxyhydroxide (boehmite, BE) shows adsorption ability of arsenious ion. In this study, we calcined BE in the temperature range 200-1150 degrees C, and examined the amount of arsenious ion adsorbed and adsorption mechanism. As a result, the adsorption amount of arsenious ion by BE calcined at 400 degrees C showed the highest value as compared with those by BE calcined at other temperatures. On the other hand, the amounts of arsenious ion adsorbed onto BE showed lower values at 200, 600, and >1000 degrees C than that by BE before calcination. The amount of surface hydroxyl group of calcined BE showed the highest value at the calcination temperature of 400 degrees C. As a result of X-ray analysis, BE showed boehmite structure at less than the calcination temperature of 300 degrees C, while BE was converted to the transitional state of aluminum oxide at more than 400 degrees C. From the result of the amount of arsenious ion adsorbed and FT-IR, it turned out that calcined BE dissociated water molecule when suspended in the water, hydroxyl group was generated on the surface, and the amount of arsenious ion adsorbed was increased because of the ion exchange of these hydroxyl groups with arsenious ions. It was clarified that an adsorbent with high adsorption ability of arsenious ion was obtained by calcination of BE.     

浓硫酸脱水实验中蔗糖炭化产物对Pb~(2+)的吸附性能研究

将《人教版必修1》浓硫酸脱水实验中蔗糖炭化废弃物经洗涤、水煮、干燥等处理后制得蔗糖炭产物,将处理后的炭产物用于铅离子的吸附实验,探讨了炭产物的用量、浸泡温度、溶液p H值等单因素对吸附铅离子的影响;并将炭产物的吸附效果与一些已经商业化的吸附剂进行对比,实验取得良好的实验结果,表明该废弃炭产物可以有效除去溶液中的铅离子。