羟基磷灰石除氟的实验地球化学研究

中国和世界上许多国家（地区） 都面临着饮用水氟含量超标的问题,因此研究氟的环境地球化学行为以及探索除氟 技术和原理至关重要。本实验采用廉价的非金属矿物羟基磷灰石作为吸附材料,研究羟基磷灰石吸附溶解态F-的地球化学 行为和机制,考察反应时间、pH、初始F-浓度等环境参数对吸附反应的影响。实验结果发现羟基磷灰石对F-的吸附反应需 进行到48 h以上时才接近反应平衡。在实验条件下（pH≥4）,F-的吸附量随pH升高而降低,羟基磷灰石对F-的吸附受pH 调控。同时还发现羟基磷灰石在pH=6条件下对F-的吸附等温线既满足Langmuir等温模式（R2=0.89） 同时也满足Freundlich 等温模式（R2=0.99）,并推导出该条件的理论最大吸附量为21.6×10-3。本研究还进一步采用了先进的XRD、SEM、 HR-TEM、19F NMR手段,系统地表征了反应前后吸附产物的形态和成分变化,发现在高F-浓度条件下,F-在羟基磷灰石表 面的吸附机制不再是单层的表面配位。核磁共振的结果表明F-可部分取代羟基磷灰石结构中的隧道羟基而形成含氟羟基磷 灰石。研究结果表明羟基磷灰石是一种相当具有潜力的除氟材料,值得进一步开发。     

Adsorption of lead using a new green material obtained from Portulaca plant

In the present study the potential of a new green material obtained from Portulaca oleracea plant was investigated. The material was used without any chemical treatment to study the adsorption behavior of lead ions from aqueous solution. Various batch experiments were carried out using different experimental conditions such as pH, contact time, adsorbent concentration, and metal ion concentration to identify the optimum conditions. The influence of these parameters on the adsorption capacity was studied. Results showed the optimum initial pH for adsorption as 6. Adsorption equilibrium was reached in 120?min. The adsorption data were modeled using both the Langmuir and Freundlich classical adsorption isotherms. Results show ~78% removal of lead from aqueous solution. The kinetic data corresponded well with pseudo second-order equation. From the initial results, the green material obtained from the waste of Portulaca seems to be a potential low-cost adsorbent for removal of lead ions from water.     

含氟废水的粉煤灰处理实验研究

进行了影响粉煤灰处理含氟废水的各种条件实验，（pH、水灰比、氟浓度、振荡平衡时间），结果表明最佳处理条件是pH值为2．5、水灰比为小于20、氟浓度小于500mg/l、振荡平衡时间大于2．5h，并研究了粉煤灰处理含氟废水的机理，给出了其吸附等温式。     

Adsorption of hexavalent chromium from aqueous solutions by wheat bran

In this research, adsorption of chromium (VI) ions on wheat bran has been studied through using batch adsorption techniques. The main objectives of this study are to 1) investigate the chromium adsorption from aqueous solution by wheat bran, 2) study the influence of contact time, pH, adsorbent dose and initial chromium concentration on adsorption process performance and 3) determine appropriate adsorption isotherm and kinetics parameters of chromium (VI) adsorption on wheat bran. The results of this study showed that adsorption of chromium by wheat bran reached to equilibrium after 60 min and after that a little change of chromium removal efficiency was observed. Higher chromium adsorption was observed at lower pHs, and maximum chromium removal (87.8 %) obtained at pH of 2. The adsorption of chromium by wheat bran decreased at the higher initial chromium concentration and lower adsorbent doses. The obtained results showed that the adsorption of chromium (VI) by wheat bran follows Langmuir isotherm equation with a correlation coefficient equal to 0.997. In addition, the kinetics of the adsorption process follows the pseudo second-order kinetics model with a rate constant value of 0.131 g/mg.min The results indicate that wheat bran can be employed as a low cost alternative to commercial adsorbents in the removal of chromium (VI) from water and wastewater.     

Adsorption of chromium and copper in aqueous solutions using tea residue

In this study, adsorption of copper and chromium was investigated by residue of brewed tea (Tea Waste) from aqueous solutions at various values of pH. It was shown that adsorbent dose, copper and chromium ion concentrations in such solutions influence the degree of these heavy metal ions’ obviation. The adsorption level of the prepared solutions was measured by visible spectrophotometer. The tea residue adsorbed copper (II) and chromium (VI) ions at initial solution pH by 25 % and 3 %, respectively. During the experiments the peak adsorption occured in hydrated copper nitrate aqueous solution at pH range of 5–6. Likewise the maximum adsorption appeared in potassium chromate aqueous solution at pH range of 2–3. In addition, tea residue adsorbed about 60 mg/g of copper (II) ion at pH=5, while chromium adsorption was registered at about 19 mg/g at pH=2. The data obtained at the equilibrium state, was compared with Langmuir and Freundlich models. Results showed that regarding the kinetics of adsorption, the uptake of copper (II) and chromium (VI) ions by tea residue was comparatively faster, with the adsorption process exhaustion completed within the first 20 min of the experiments. Furthermore, results revealed that adsorption data concerning the kinetic phase is closely correlated with a pseudo-second order model with R²> 0.99 for copper (II) and chromium (VI) ions     

Studies on the recovery of uranium from nuclear industrial effluent using nanoporous silica adsorbent

In this paper, the sorption of uranium onto nanoporous silica adsorbent in the presence of nitrate, sulfate, chloride, fluoride and phosphate was studied. The effect of contact time between the nanoporous sorbent and aqueous solution, pH and initial concentration of uranium was also investigated. Uranium sorption onto nanoporous silica adsorbent is a very fast process as sorption rate increases with pH increment. Optimum pH for uranium sorption was 4?C8. Experimental sorption isotherm is successfully described by Langmuir and Freundlich models. The results obtained by batch experiments showed that the presence of high concentration of nitrate, sulfate, chloride and phosphate anions alone had no interference with uranium recovery. However, the presence of fluoride ions (>250?mg/L) decreases uranium sorption by about 55?%. The results also showed that the presence of phosphate ions (about 300?mg/L) in solution could remove fluoride interference completely. Finally, the efficiency of the nanoporous silica adsorbent for uranium recovery from wastewater of the uranium conversion facility was investigated.     

Hydrogeochemical processes controlling fluoride enrichment within alluvial and hard rock aquifers in a part of a semi-arid region of Northern India

Rock–water interaction along with mineral dissolution/ precipitation plays a profound role in the control of fluoride ion concentration within the alluvial groundwater in a part of semi-arid northern India. In the premonsoon season, the alluvial region experiences evaporative processes leading to increase in Na⁺ ions which through reverse ion exchange processes are adsorbed onto suitable sites within the aquifer matrix in exchange for Ca²⁺ ion in solution. Increase in Ca²⁺ ions in solution inhibits fluorite mineral dissolution, thereby controlling premonsoon fluoride ion concentration within alluvial groundwaters (1.40?±?0.5 mg/l). In the postmonsoon season, however, higher average fluoride ion concentration within the alluvial aquifer samples (2.33?±?0.80 mg/l) is observed mainly due to increase in silicate weathering of fluoride-bearing rocks and direct ion exchange processes enabling Ca²⁺ ion uptake from solution accompanied with the release of fluoride ions. Combined effect of these processes results in average fluoride ion concentration falling above the WHO drinking water permissible limit (1.5 mg/l). Alternatively, the hard rock aquifer samples within the study area have an average fluoride ion concentration falling below the permissible limit in both the seasons.     

Preliminary investigations on the defluoridation of water using fired clay chips

The adsorption of fluoride ions on ground fired clay pot has been investigated. The maximum efficiency of the adsorbent for defluoridating 1–2 litres of water was found to be 200 mg fluoride kg⁻¹ adsorbent. The investigation showed that 5–20 mg l⁻¹ fluoride, from 1 litre of water, could be reduced to less than 1.5 mg l⁻¹ using 120–240 g of the adsorbing medium. The effects of the dose of the medium, the pH, the contact time and the initial fluoride content were studied in relation to defluoridation efficiency. Comparison of fluoride removal capacity of the adsorbent was also made with those of fired brick, clay soil and red ash. The latter exhibited practically no adsorption. A packed column of the same ground clay pot was saturated with 285 mg fluoride kg⁻¹ of adsorbent when 20 litres of water containing 10 mg l⁻¹ F was allowed to pass through it. This column defluoridated 6 litres of tap water containing 10 ppm F⁻ to below 1.5 mg l⁻¹.     

Uptake of Indosol Dark-blue GL dye from aqueous solution by water hyacinth roots powder: adsorption and desorption study

Adsorption characteristics of water hyacinth roots powder for the removal of Indosol Dark-blue GL dye were investigated in batch mode. Operating variables, such as initial solution pH, presence of detergent, adsorbent dosage, initial concentration and contact time, were studied. The results showed that the adsorption of dye increased with increasing the initial concentration and contact time. The adsorption is highly pH dependent and adsorption capacity increased with decrease in pH. Kinetic study revealed that the uptake of Indosol Dark-blue GL was very rapid within the first 15 min and equilibrium time was independent of initial concentration. Batch equilibrium experiments were carried out at different pH and found that equilibrium data fitted well to Langmuir isotherm model. The maximum sorption capacity of the adsorbent was found as 86 mg g^?1 at pH 3 which reduced to 64 mg g^?1 at pH 5. The presence of detergent reduced the sorption capacity of the adsorbent significantly. Using equilibrium and kinetic data, the forward and backward rate constants were determined from the unified approach model. Desorption study revealed that the dye can be recovered by swing the pH from low to high.     

Adsorption of copper and cobalt from fresh and marine systems

The adsorption of copper and cobalt from aqueous solution on to illite and other substrates has been studied as a function of pH, solution composition and solid phase concentration. The results are interpreted in terms of a model whereby the trace metals are adsorbed in exchange for surface bound H⁺ ions. Adsorption varies with solution ionic strength and the concentrations of complex forming ligands; both of these parameters tend to reduce the trace metal adsorption. The Cu²⁺ is two orders of magnitude more reactive toward solid surfaces than Co²⁺ , which is consistent with the general reactivities of these two metal ions. It is also found that Mg₂₊ interferes with adsorption, presumably by competing with the trace metals for the surface sites. A quantitative model was developed which describes adsorption of these metals from natural waters ranging from river water to sea water as a function of pH, complexing ligands and magnesium activity.     

Cadmium adsorption on hydrous aluminium (III) oxide: effect of adsorbed polyelectrolyte

Freshly precipitated hydrous oxides of Al (flocs) are important sorbents of heavy metal ions and are used in water treatment processes. The addition of chelating agents or polyelectrolytes can increase the efficiency of heavy metal removal by flocs. The polymer polyethylenimine is commonly used as a flocculant aid in water treatment and has been modified with phthalic acid. Adsorption studies have shown that the addition of millimolar concentrations of polyelectrolyte increases the removal of Cd ions from a 29.7 μM aqueous solution by aluminium flocs from ca. 40% to up to 75%. Experiments in which the pH was varied demonstrated that the observed enhancement of Cd adsorption is caused by a shift of the pH edge to lower pH values in the presence of polyelectrolyte. Maximum polyelectrolyte adsorption occurs between pH 6 and pH 7, corresponding to the point of enhanced Cd adsorption in the presence of polyelectrolyte. The enhancement of Cd adsorption observed below pH 7 is therefore likely to be due to the formation of a ternary surface complex. At pH values above pH 8 the polyelectrolyte forms a stable complex with Cd and Al ions in solution causing floc dissolution and decreased Cd adsorption.     

Application of dried plant biomass as novel low-cost adsorbent for removal of cadmium from aqueous solution

Heavy metals are a threat to human health and ecosystem. These days, great deal of attention is being given to green technologies for purification of water contaminated with heavy metal ions. Biosorption is one among such emerging technologies, which utilizes naturally occurring waste materials to sequester heavy metals from wastewater. Cadmium has hazardous impact on living beings; therefore, its removal through green and economical process is an important task. The aim of the present study was to utilize the locally available Portulaca oleracea plant biomass as an adsorbent for cadmium removal from aqueous solution. The biomass was obtained after drying and grinding the portulaca leaves and stem. No chemical treatment was done on the adsorbent so that it remained green in a true sense. Batch experiments were performed at room temperature. The critical parameters studied were effects of pH, contact time, initial metal ion concentration and adsorbent dose on the adsorption of cadmium. The maximum adsorption was found to be 72 %. The kinetic data were found to best fit the pseudo-second-order equation. High adsorption rates were obtained in the initial 45 min, and adsorption equilibrium was then gradually achieved in about 100 min. Adsorption increased with increase in pH for a range 2 and 6. The equilibrium adsorption results closely followed both the Langmuir and Freundlich isotherms. The values of constants were calculated from isotherms. Results indicated that portulaca plant biomass could be developed as a potential material to be used in green water treatment devices for removal of metal ions.     

Kinetic and equilibrium study of Ni(II) sorption from aqueous solutions onto Peganum harmala-L

In this study, the adsorption behavior of Ni(II) in an aqueous solution system using natural adsorbent Peganum harmala-L was measured via batch mode. The prepared sorbent was characterized by scanning electron microscope, Fourier transform infrared spectroscopy, N₂ adsorption–desorption and pH_zpc. Adsorption experiments were carried out by varying several conditions such as contact time, metal ion concentration and pH to assess kinetic and equilibrium parameters. The equilibrium data were analyzed based on the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms. Kinetic data were analyzed using the pseudo-first-order, pseudo-second-order and intra-particular diffusion models. Experimental data showed that at contact time 60 min, metal ion concentration 50 mg/L and pH 6, a maximum amount of Ni(II) ions can be removed. The experimental data were best described by the Langmuir isotherm model as is evident from the high R ² value of 0.988. The adsorption capacity (q _m) obtained was 68.02 mg/g at an initial pH of 6 and a temperature of 25 °C. Kinetic studies of the adsorption showed that equilibrium was reached within 60 min of contact and the adsorption process followed the pseudo-first-order model. The obtained results show that P. harmala-L can be used as an effective and a natural low-cost adsorbent for the removal of Ni(II) from aqueous solutions.     

油页岩对钴离子的吸附性能研究

油页岩中因含有大量的黏土矿物而对金属离子具有一定的吸附能力.采用静态吸附法对油页岩吸附钴离子的影响因素及吸附动力学进行了研究.结果表明,油页岩粒度、溶液浓度、溶液pH值、吸附时间等均对吸附性能有一定影响.油页岩对钴离子的吸附量随样品粒径的减小而增大;随着钴离子初始浓度的增加,油页岩对钴离子的吸附总量增加;溶液pH值在3~8范围内,油页岩对钴离子的吸附量和吸附率随着pH值的增大呈上升趋势.通过吸附动力学研究发现,油页岩对钴离子的吸附过程符合准二级动力学过程和粒子内扩散机理.     

Influence of operating conditions on the removal of Cu, Zn, Cd and Pb ions from wastewater by adsorption

Nile Rose Plant was used to study adsorption of several cations (Cu²+, Zn²+, Cd²+ and Pb²+) from wastewater within various experimental conditions. The dried leaves of Nile Rose Plant were used at different adsorbent/ metal ion ratios. The influence of pH, contact time, metal concentration, and adsorbent loading weight on the removal process was investigated. Batch adsorption studies were carried out at room temperature. The adsorption efficiencies were found to be pH dependent, increasing by increasing the pH in the range from 2.5 to 8.5 exept for Pb. The equilibrium time was attained within 60 to 90 min. and the maximum removal percentage was achieved at an adsorbent loading weight of 1.5 g/50 mL mixed ions solution. Isothermal studies showed that the data were best fitted to the Temkin isotherm model. The removal order was found to be Pb²⁺> Zn²⁺> Cu²⁺> Cd²⁺. The surface IR-characterization of Nile rose plant showed the presence of many functional groups capable of binding to the metal cations.     

Adsorption of Ammonium and Heavy Metal Ions on Industrial Vermiculite from the Yuli Mine in Xinjiang, China

The present work discusses the mineralogy, saturated adsorption of ammonium and adsorption of heavy metal ions （Cu^2＋, Pb^2＋ and Zn^2＋） on industrial vermiculite samples from the Yuli Mine in Xinjiang Autonomous Region. The saturated adsorption capacity of ammonium and the affection factors of adsorption of Cu^2＋, Pb^2＋ and Zn^2＋ are discussed on the basis of the mineralogical characteristics of the industrial vermiculite samples. The saturated adsorption capacities of ammonium are between 56.02 and 98.42 mmol/100g. The time of adsorption equilibrium is about 30-60 min, and the pH values and concentration of the ion solution significantly affect the adsorption capacities of the heavy metal ions. The adsorption capabilities of the heavy metal ions on industrial vermiculite are almost the same in the low ion concentration solutions, characterized by a sequence of Zn^2＋〉Pb^2＋〉Cu^2＋ for adsorption capacity in solutions with relatively high ion concentration. The results have practical significance for the application of the industrial vermiculite to treating wastewater containing ammonium or heavy metal ions.     

活性氧化铝除氟性能的试验研究

通过静态试验,研究了活性氧化铝对F-的吸附性能,分析了原水氟离子浓度、pH值、活性氧化铝的投加量和吸附时间对吸附性能的影响。研究结果表明：在原水浓度0～50mg／L范围内,活性氧化铝吸附量与原水浓度基本成线性增加的关系;活性氧化铝除氟的最佳pH值为5～7,最佳投加量为10g／L。测定了在25℃时活性氧化铝除氟的吸附等温线,并对吸附等温线进行拟合,证明其符合Langmuir吸附等温式。     

Adsorption of lead, zinc and cadmium ions from contaminated water onto Peganum harmala seeds as biosorbent

Peganum harmala seeds were assessed as biosorbent for removing Pb²⁺, Zn²⁺and Cd²⁺ ions from aqueous solutions. The effects of various parameters such as the aqueous solution pH, the contact time, the initial metal concentration and the amount of adsorbent in the process were investigated. The adsorption efficiencies increased with pH. It was found that about 95 % of lead, 75 % of zinc and 90 % of cadmium ions could be removed from 45 ml of aqueous solution containing 20 mg l^?1 of each cation with 2 g of adsorbent at pH 4.5 after 15 min. The quantitative desorption of cadmium from adsorbent surface was achieved using 10 ml of a 0.5 M nitric acid solution. This condition was attained for lead and zinc ions with 10 ml of 1 M hydrochloric acid solution. Kinetic investigation of the process was performed by considering a pseudo-second-order model. This model predicts the chemisorption mechanism of the process. Langmuir, Freundlich, Temkin and Dubinin–Radushkevich models were tested for describing the equilibrium data. It was found that the Freundlich model describes the experimental data resulting from the adsorption of lead ions. However for cadmium and zinc ions, the adsorption equilibria were interpreted with the Langmuir model.     

Fertilization and pH effects on processes and mechanisms controlling dissolved inorganic phosphorus in soils

We used of a set of mechanistic adsorption models (1-pK TPM, ion exchange and Nica-Donnan) within the framework of the component additive (CA) approach in an attempt to determine the effect of repeated massive application of inorganic P fertilizer on the processes and mechanisms controlling the concentration of dissolved inorganic phosphorus (DIP) in soils. We studied the surface layer of a Luvisol with markedly different total concentrations of inorganic P as the result of different P fertilizer history (i.e. massive or no application for 40 years). Soil pH was made to vary from acid to alkaline. Soil solutions were extracted with water and CaCl₂ (0.01 M). The occurrence of montmorillonite led us to determine the binding properties of P and Ca ions for this clay mineral.Satisfactory results were obtained using generic values for model parameters and soil-specific ones, which were either determined directly by measurements or estimated from the literature. We showed that adsorption largely controlled the variations of DIP concentration and that, because of kinetic constrains, only little Ca-phosphates may be precipitated under alkaline conditions, particularly in the P fertilized treatment. The mineral-P pool initially present in both P treatments did not dissolve significantly during the course of the experiments. The adsorption of Ca ions onto soil minerals also promoted adsorption of P ions through electrostatic interactions. The intensity of the mechanism was high under neutral to alkaline conditions. Changes in DIP concentration as a function of these environmental variables can be related to changes in the contribution of the various soil minerals to P adsorption. The extra P adsorbed in the fertilized treatment compared with the control treatment was mainly adsorbed onto illite. This clay mineral was the major P-fixing constituent from neutral to alkaline pH conditions, because the repulsion interactions between deprotonated hydroxyl surface sites and P ions were sufficiently counterbalanced by Ca ions. The drastic increase of DIP observed at acid pH was due to the effect of the lower concentration of surface sites of Fe oxides and kaolinite.In addition to confirming the validity of our approach to model DIP concentrations in soils, the present investigation showed that adsorption was the predominant geochemical process even in the P fertilized soil, and that Ca ions can have an important promoting effect on P adsorption. However the influence of the dissolution of the mineral-P pool under field conditions remained questionable.     

Utilization of ochre as an adsorbent to remove Pb(II) and Cu(II) from contaminated aqueous media

The ability of ochre to remove Pb(II) and Cu(II) from aqueous media has been studied by batch sorption studies varying the contact time, initial metal concentration, initial solution pH and temperature to understand the adsorption behaviour of these metals through adsorption kinetics and isotherms. The pH of the solution and the temperature controlled the adsorption of metal ions by ochre and rapid uptake occurred in the first 30 min of reaction. The kinetics of adsorption followed a pseudo-second-order rate equation (R ² > 0.99) and the isotherms are well described by the Freundlich model. Adsorption of metals onto ochre is endothermic in nature. Between the two metals, Pb(II) showed more preference towards the exchangeable sites on ochre than Cu(II). This study indicates that ochre is a very effective adsorbent in removing Pb(II) and Cu(II) from the aqueous environment with an adsorptive capacity of 0.996 and 0.628 mg g^?1 and removal efficiency of 99.68 and 62.80 %, respectively.