Mechanism of lead adsorption from aqueous solutions using an adsorbent synthesized from natural condensed tannin

Adsorption is a method for removing lead from wastewater. The adsorption of lead on a new adsorbent synthesized from natural condensed tannin has been investigated using a series of batch adsorption experiments. The study on the adsorption mechanism indicates that the adsorbent performed in aqueous solutions as an ionic exchanger whose end group was sodium ion (Na(+)). One lead (II) ion (Pb(2+)) was adsorbed onto the adsorbent by taking the place of two Na(+) ions. The maximum exchangeable Na(+) present on the adsorbent was measured with the proton titration experiments and it was up to 1.0 mmol x Na(+)g(-1) dry adsorbent. To a significant extent, pH influenced the extraction of lead from aqueous solutions. The lead removal efficiency was up to 71%, 87% and 91% with initial solution pH at 3.0, 3.6 and 4.2, respectively. The Langmuir equation fitted the adsorption isotherm data well. The maximum adsorption capacity of lead calculated was 57.5, 76.9 and 114.9 mg lead g(-1) dry adsorbent at initial solution pH of 3.0, 3.6 and 4.2, respectively. Therefore, the adsorbent does offer favorable characteristics in lead removal from acidic wastewater.     

Selection of an adsorbent for lead removal from drinking water by a point-of-use treatment device

The removal of lead from drinking water was investigated to develop a point-of-use water filter that could meet the regulation imposed by the new European Directive 98-83 lowering lead concentration in drinking water below 10 μg L⁻¹. The objective of this research was to assess the potential of different adsorbents (zeolites, resins, activated carbon, manganese oxides, cellulose powder) to remove lead from tap water with a very short contact time. To begin, the repartition of the lead species in a tap water and a mineral water was computed with the computer model CHESS. It showed that in bicarbonated waters lead is mainly under lead carbonate form, either in the aqueous or in the mineral phase. Batch experiments were then conducted to measure the equilibrium adsorption isotherms of the adsorbents. Then, for five of them, dynamic experiments in micro-columns were carried out to assess the outlet lead concentration level. Three adsorbents gave rise to a leakage concentration lower than 10 μg L⁻¹ and were then selected for prototypes experiments: chabasite, an activated carbon coated with a synthetic zeolite and a natural manganese oxide. The proposed method clearly showed that the measurement of equilibrium isotherms is not sufficient to predict the effectiveness of an adsorbent, and must be coupled with dynamic experiments.     

Removal of lead ions from industrial waste water by different types of natural materials

The adsorption capacity of some natural materials for lead such as animal bone powder, active carbon, Nile rose plant powder, commercial carbon and ceramics was studied. The V/m ratio has been chosen to be 500 ml/g. The adsorption process was affected by various parameters such as contact time, pH and concentration of lead solution. The lead uptake percent reaches equilibrium state after 15, 30, 45 and 120 min for bone powder, active carbon, plant powder and commercial carbon, respectively. The uptake percent of lead increased by increasing pH value. The sequence of lead uptake percent (% adsorption) at constant pH from certain concentration of lead nitrate solution by the different natural materials is in the order: bone powder > active carbon > plant powder > commercial carbon. The uptake percent of lead is increased by decreasing the concentration of lead at constant pH. The capacity of lead adsorbed from nitrate solution by the different natural materials increased by increasing pH value. The synthetic and industrial waste-water samples were treated by using the different natural materials (contact time 3h, pH = 4). The percent removal of lead was 100% by bone powder, 90% by active carbon, 80% by plant powder and 50% by commercial carbon. There was no removal of lead by ceramics. This may be due to the presence of high percent of lead in the constituent of ceramics (372 mg/g).     

Removal of probable human carcinogenic polycyclic aromatic hydrocarbons from contaminated water using molecularly imprinted polymer

A molecularly imprinted polymer (MIP) adsorbent for carcinogenic polycyclic aromatic hydrocarbons (PAHs) was prepared using a non-covalent templating technique. MIP particles sized from 2 to 5 μm were synthesized in acetonitrile by using six PAHs mix as a template, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. When compared with the non-imprinted polymer (NIP), the MIP showed an excellent affinity towards PAHs in aqueous solution with binding capacity (B_max) of 687 μg g⁻¹MIP, imprinting effect of 6, and a dissociation constant of 24 μM. The MIP exhibited significant binding affinity towards PAHs even in the presence of environmental parameters such as dissolved organic matter (COD) and total dissolved inorganic solids (TDS), suggesting that this material may be appropriate for removal of carcinogenic PAHs. The feasibility of removing PAHs from water by the MIP demonstrated using groundwater spiked with PAHs. In addition, the MIP reusability without any deterioration in performance was demonstrated at least ten repeated cycles.     

Removal of anionic reactive dyes from water using anion exchange membranes as adsorbers

Two commercial anion exchange membranes, strong basic (SB6407) and weak basic (DE81), were evaluated for the removal of anionic reactive dyes, Cibacron blue 3GA (three sulfonic acid groups per dye molecule) and Cibacron red 3BA (four sulfonic acid groups per dye molecule), from water in this study. The adsorption isotherm results show that the Langmuir maximum adsorption capacities of Cibacron blue 3GA (31.5mg/cm(3) for SB6407 and 25.5mg/cm(3) for DE81) were greater than those of Cibacron red 3BA (24.5mg/cm(3) for SB6407 and 18.5mg/cm(3) for DE81). For each reactive dye, the capacity for SB6407 was higher than DE81 based on the same membrane volume. However, consideration of the number of ion exchange sites interacting with a dye molecule indicates that the DE81 results are close to the theoretical values while the SB6407 membrane had some unused binding sites. In addition, Cibacron red 3BA demonstrated faster and stronger binding with both anion exchange membranes than Cibacron blue 3GA. Both dyes could bind with strong basic SB6407 more quickly and stronger. In the batch desorption process, different desorption solutions were tested and the mixtures of salt, acid, or base in methanol solution (e.g. 1N KSCN in 60% methanol or 1N HCl in 60% methanol) achieved better performance. Finally, in the flow process with one piece of anion exchange membrane (initial dye concentration of 0.05g/L), SB6407 was found superior to DE81 in dye recovery and both membranes retained their original uptake capacities over three cycles of adsorption, washing, and desorption.     

Preparation and preliminary assessment of polymer-supported zirconium phosphate for selective lead removal from contaminated water

In the present study, polymer-supported zirconium phosphate (ZrP-CP) was prepared for selective removal of lead from the contaminated water. ZrP-CP was characterized using nitrogen adsorption technique, scanning electron microscope (SEM), and X-ray diffraction (XRD). Lead sorption on ZrP-CP was found to be pH dependent due to the ion- exchange mechanism. Also, ZrP-CP was proved to be more selective than the polystyrene strong-acid cation exchanger D-001 to remove lead ion from water, where other competing cations such as Na(+), Ca(2+), and Mg(2+) ions coexist at high concentrations. Generally, lead sorption isotherms on ZrP-CP can be divided into two distinct regions at different load levels, and isotherms at both regions can be well elucidated by Langmuir model. The distribution coefficients (K(d)) and binding constants (B(L)) obtained experimentally indicated that stronger sorption affinity of ZrP-CP towards the lead ion occurs at a relatively lower load level. Also, lead sorption onto ZrP-CP was found to be an endothermic and entropy-driven process. High selectivity of ZrP-CP towards the lead ion was possibly attributed to the crystal state of zirconium phosphate and a specific interaction between orthophosphate and lead ion. Fixed-bed column runs showed that lead sorption on ZrP-CP could result in a conspicuous decrease of this toxic metal from 0.5 mg/L to below 0.01 mg/L, which is recommended as the standard of drinking water by WHO (the treatment technique standard set by US EPA is 0.015 mg/L). Also, the spent sorbent can be readily regenerated for reuse by dilute HNO(3) or HCl solution.     

Assessment of Al-Madra clay as an adsorbent of copper ions from aqueous solutions

Al-Madra clay, a local, cheap and readily available material in Qatar, was tested for the removal of copper ions from aqueous solutions. Batch experiments of copper ion adsorption onto natural and treated clay in different conditions were undertaken. Different types of activated Al-Madra clay were used, such as Na-clay, Al-clay, thermal-clay and cyclohexane-clay. Thermally treated clay achieved the highest removal of Cu ions, followed by Al-clay, cyclohexane-clay, and finally Na-clay. A maximum of 50% adsorption of copper ions can be achieved using the natural clay while about 72% adsorption can be achieved when the clay is thermally treated. The amount of copper adsorbed by untreated Al-Madra clay was dependent on the process conditions; increasing with an increase in pH and initial metal concentration but decreasing with an increase in sorbent concentration. The increase in temperature from 5 to 50°C resulted in only a very slight increase in copper uptake by untreated Al-Madra clay.      

Removal of 1,4-dioxane from water using sonication: effect of adding oxidants on the degradation kinetics

This research investigates the effect of adding oxidants such as Fe0, Fe2+ and S2O8(2-) in the sonication of 1,4-dioxane (1,4-D). The results indicate that the degradation pattern of 1,4-D kinetically could be divided into three steps (initiation, acceleration, and stabilization), with the first two steps predominating. The initiation step agreed with zero order rate model, while the acceleration step was the pseudo-first order. In the presence of HCO3- as a radical scavenger, the degradations of 1,4-D and TOC were suppressed, indicating that OH radical is an important factor in the sonolysis, especially at the acceleration step. The overall degradation efficiency of 79.0% in the sonolysis of 1,4-D was achieved within 200 min. While Fe0, Fe2+ and S2O8(2-) were individually combined with sonication, the total degradation efficiency of 1,4-D increased 18.6%, 19.1% and 16.5% after 200 min, respectively. The addition of oxidants not only increased the rate constant in the acceleration step, but also changed the kinetic model from zero to pseudo-first order at the initiation step. The addition of oxidants such as Fe2+, Fe0 and S2O8(2-) in the sonication of 1,4-D also improved the mineralization of 1,4-D. However, the degradation efficiencies of 1,4-D and TOC were not statistically different (p = 0.709, ANOVA) with different oxidants such as Fe2+, Fe0 and S2O8(2-).     

Removal of Pb(ii) from aqueous/acidic solutions by using bentonite as an adsorbent

The ability of bentonite clay to remove Pb(II) from aqueous solutions and from nitric acid, hydrochloric acid and perchloric acid solutions (1.0-1 x 10(-5)) has been studied at different optimized conditions of concentrations, amount of adsorbent, temperature, concentration of electrolyte and pH. Maximum adsorption of Pb(II), i.e. > 98% has been achieved in aqueous solutions, while 86% is achieved from 1.0 x 10(-5) M HCl using 0.5 g of bentonite. The adsorption decreases by increasing the concentration of electrolytes. Flame atomic absorption spectrometer was used for measuring lead concentration. Isotherm analysis of adsorption data obtained at 25 degrees C, 30 degrees C, 40 degrees C and 50 degrees C showed that the adsorption pattern of lead on bentonite followed the langmuir isotherm and freundlich isotherm, respectively. DeltaH(o) and deltaS(o) were calculated from the slope and intercept of ln K(D) vs. I/T plots.     

Removal of antibiotics from water using sewage sludge- and waste oil sludge-derived adsorbents

Sewage sludge- and waste oil sludge-derived materials were tested as adsorbents of pharmaceuticals from diluted water solutions. Simultaneous retention of eleven antibiotics plus two anticonvulsants was examined via batch adsorption experiments. Virgin and exhausted adsorbents were examined via thermal and FTIR analyses to elucidate adsorption mechanisms. Maximum adsorption capacities for the 6 materials tested ranged from 80 to 300 mg/g, comparable to the adsorption capacities of antibiotics on various activated carbons (200-400 mg/g) reported in the literature. The performance was linked to surface reactivity, polarity and porosity. A large volume of pores similar in size to the adsorbate molecules with hydrophobic carbon-based origin of pore walls was indicated as an important factor promoting the separation process. Moreover, the polar surface of an inorganic phase in the adsorbents attracted the functional groups of target molecules. The presence of reactive alkali metals promoted reaction with acidic groups, formation of salts and their precipitation in the pore system.     

Ingestion of lead from ammunition and lead concentrations in white-tailed sea eagles (Haliaeetus albicilla) in Sweden

In this study we show for the first time that lead poisoning from ammunition is a significant mortality factor for white-tailed sea eagle (WSE) (Haliaeetus albicilla) in Sweden. We analyzed 118 WSEs collected between 1981 and 2004 from which both liver and kidney samples could be taken. A total of 22% of all eagles examined had elevated (> 6 µg/g d.w.) lead concentrations, indicating exposure to leaded ammunition, and 14% of the individuals had either liver or kidney lead concentrations diagnostic of lethal lead poisoning (> 20 µg/g d.w.). Lead concentrations in liver and kidney were significantly correlated. In individuals with lead levels < 6 µg/g, concentrations were significantly higher in kidney than in liver; in individuals with lead levels > 20 µg/g, concentrations were significantly higher in liver. The lead isotope ratios indicate that the source of lead in individuals with lethal concentrations is different from that of individuals exhibiting background concentrations of lead (< 6 µg/g d.w.) There were no significant sex or age differences in lead concentrations. A study from the Baltic reported in principle no biomagnification of lead, but background lead concentrations in WSE liver in this study were still four to > 10 times higher than concentrations reported for Baltic fish from the same time period. In contrast to other biota there was no decrease in lead concentrations in WSE over the study period. The proportion of lead poisoned WSE remained unchanged over the study period, including two years after a partial ban of lead shot was enforced in 2002 for shallow wetlands. The use of lead in ammunition poses a threat to all raptors potentially feeding on shot game or offal. The removal of offal from shot game and alternatives to leaded ammunition needs to be implemented in order to prevent mortality from lead in raptors and scavengers.     

Magnetic powder MnO-Fe2O3 composite--a novel material for the removal of azo-dye from water

Fine powder adsorbents or catalysts often show better adsorptive or catalytic properties, but they encounter the difficulties of separation and recovery in application. In this study, four inexpensive magnetic powder MnO-Fe2O3 composites used as adsorbent-catalyst materials were prepared and characterized. These materials could be recovered efficiently by a magnetic separation method. Their adsorptive properties for the removal of an azo-dye, acid red B (ARB), from water and the regeneration of adsorbents containing ARB by catalytic combustion was studied. These powder adsorbents showed excellent adsorption towards ARB under acidic conditions. A very fast adsorption rate was observed and could be well described by a pseudo-second-order kinetics model. The adsorption capacity increased with increasing Fe content and surface area of the adsorbent, and the highest adsorption capacity of 105.3 mg/g was obtained at pH 3.5. The adsorption was not affected by the presence of Cl-, but was significantly affected by SO4(2-). The adsorbent containing ARB can be regenerated by catalytic combustion of adsorbed ARB at 400 degrees C in air. Laboratory experiments demonstrated that this material is reusable.     

Removal of humic substances (HS) from water by electro-microfiltration (EMF)

Humic substances (HS) represent the common agents contributing to flux decline during membrane filtration of natural water. In order to minimize the fouling during microfiltration (MF) of HS, modifying the operation of MF presents a promising alternative. A laboratory-scale electro-microfiltration (EMF) module was used to separate Aldrich HS from water by applying a voltage across the membrane. The presence of an electric field significantly reduced the flux decline. A flux comparable to that of ion-free water was attained when the voltage was near the critical electric field strength (Ecritical), i.e., the electrical field gradient that balances the advective and electrophoretic velocities of solute. At an applied voltage of 100 V (approximately 110 V/cm), it was able to reduce UV absorbance at 254 nm (UV254), total organic carbon (TOC) and trihalomethane formation potential (THMFP) by over 50% in the permeate. Results from 1H nuclear magnetic resonance (1H NMR) analysis suggest that the aromatic and functionalized aliphatic fractions decreased significantly in the permeate. The charged HS have large molecule weight compared with those passing through membrane. Results clearly indicate that a combination of electric force with MF can increase HS rejection and decrease flux decline. Electrophoretic attraction was the major mechanism for the improvement of flux and rejection over time.     

Removal of nitrogen, phosphorus and COD from waste water using sand filtration system with Phragmites Australis

The removal efficiencies of nitrogen, phosphorus and COD from waste water were examined using sand filtration systems with Phragmites australis (Cav.) Trin. ex. Steudel. The quality of effluent waters from the system with plant were far better than those from the one without plant, implying Phragmites could incorporate nitrogen and phosphorus into its tissues and promote phosphorus absorption onto the sand by the release of oxygen from the roots. The P-pot provided with the influent containing 198 mg l^- of total nitrogen and 21 mg l^-1 of total phosphorus had the highest biomass of Phragmites. Harvestable above-ground biomass accounted for about 3.5 kg m^-2 and removable nitrogen and phosphorus accounted for 69 and 6 g m^-2 respectively.The removal rates of total nitrogen and phosphorus in the system with Phragmites receiving variable amounts of COD were almost at the same level and also much better than those of the systems without plant, implying that the different COD concentrations in the influent media do not impair the removal efficiencies of nitrogen and phosphorus. Also Phragmites was found to resist COD concentration as high as 128 mg l^-1, and signs of clogging were not detected in this system throughout the experiment.     

Removal of anionic dye Congo red from aqueous solution by raw pine and acid-treated pine cone powder as adsorbent: equilibrium, thermodynamic, kinetics, mechanism and process design

Pine cone a natural, low-cost agricultural by-product in Australia has been studied for its potential application as an adsorbent in its raw and hydrochloric acid modified form. Surface study of pine cone and treated pine cone was investigated using Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The modification process leads to increases in the specific surface area and decreases mean particle sizes of acid-treated pine cone when compared to raw pine cone biomass. Batch adsorption experiments were performed to remove anionic dye Congo red from aqueous solution. It was found that the extent of Congo red adsorption by both raw pine cone biomass and acid-treated biomass increased with initial dye concentration, contact time, temperature but decreased with increasing solution pH and amount of adsorbent of the system. Overall, kinetic studies showed that the dye adsorption process followed pseudo-second-order kinetics based on pseudo-first-order and intra-particle diffusion models. The different kinetic parameters including rate constant, half-adsorption time, and diffusion coefficient were determined at different physico-chemical conditions. Equilibrium data were best represented by Freundlich isotherm model among Langmuir and Freundlich adsorption isotherm models. It was observed that the adsorption was pH dependent and the maximum adsorption of 32.65 mg/g occurred at pH of 3.55 for an initial dye concentration of 20 ppm by raw pine cone, whereas for acid-treated pine cone the maximum adsorption of 40.19 mg/g for the same experimental conditions. Freundlich constant 'n' also indicated favourable adsorption. Thermodynamic parameters such as ?G(0), ?H(0), and ?S(0) were calculated. A single-stage batch absorber design for the Congo red adsorption onto pine cone biomass also presented based on the Freundlich isotherm model equation.     

Removal of arsenic from water: Effects of competing anions on As(III) removal in KMnO4–Fe(II) process

Effects of sulfate, phosphate, silicate and humic acid (HA) on the removal of As(III) in the KMnO₄–Fe(II) process were investigated in the pH range of 4–9 with permanganate and ferrous sulfate applied at selected dosage. Sulfate decreased the removal of arsenic by 6.5–36.0% at pH 6–9 and the decrease in adsorption did not increase with increasing concentration of sulfate from 50 to 100 mg/L. In the presence of 1 mg/L phosphate, arsenic removal decreased gradually as pH increased from 4 to 6, and a sharp drop occurred at pH 7–9. The presence of 10 mg/L silicate had negligible effect on arsenic removal at pH 4–5 whereas decreased the arsenic removal at pH 6–9 and the decrease was more significant at higher pH. The presence of HA dramatically decreased the arsenic removal over the pH range of 6–9 and HA of higher concentration resulted in greater drop in arsenic removal. The effects of the competing anions on arsenic removal in the KMnO₄–Fe(II) process were highly dependent on pH and the degree of these four anions influencing As(III) removal decreased in the following order, phosphate > humic acid > silicate > sulfate. Sulfate differed from the other three anions because sulfate decreased the removal of arsenic mainly by competitive adsorption while phosphate, silicate and HA decreased the removal of As(III) by competitive adsorption and sequestering the formation of ferric hydroxide derived from Fe(II).