Comparative and competitive adsorption of Cu(II), Cd(II) and Pb(II) onto Sepia pharaonis endoskeleton biomass from aqueous solutions

In this research, the possibility of simultaneous removal of lead, cadmium and copper divalent ions from water samples through the use of Sepia pharaonis endoskeleton powder (SPEB) as bio‐material, was investigated. The bio‐sorbent was characterised by Fourier transform infrared spectrum (FT‐IR), atomic force microscopy (AFM) and X‐ray fluorescence (XRF). The different factors affecting the bio‐sorption process were studied. Langmuir and Freundlich isotherm models were applied to analyse the experimental data. The kinetic studies showed that the pseudo‐second order model kinetics were compatible with the investigated systems. It was found that under optimal conditions, this bio‐sorbent was efficient in the uptake of these heavy metal ions from both mono and multi‐metal solutions, and high removal percentages were achieved. This study verified the potential ability of SPEB as an efficient natural adsorbent for removal of Pb(II), Cd(II) and Cu(II) ions from river, tap and mineral water samples.     

Removal of Cu(II) and Cd(II) from aqueous solution by seafood processing waste sludge

Dried waste slurry generated in seafood processing factories has been shown to be an effective adsorbent for the removal of heavy metals from dilute solutions. Characterization of the sludge surface with scanning electron microscope and X-ray microanalyzer were carried out to evaluate the components on the sludge surface that are related to the adsorption of metal ions. Aluminum and calcium, as well as organic carbon are distributed on the surface of sludge. Alkalimetric titration was used to characterize the surface acidity of the sludge sample. The surface acidity constants, pKa1s and pKa2s, were 5.80 and 9.55, respectively. Batch as well as dynamic adsorption studies were conducted with 10(-5) to 5 x 10(-3) M Cu(II) and Cd(II). A surface complexation model with the diffuse layer model successfully predicted Cu(II) and Cd(II) removals in single metal solutions. Predictions of sorption in binary-adsorbate systems based on single-adsorbate data fits represented competitive sorption data reasonably well over a wide range of conditions. The breakthrough capacity found from column studies was different for each metal ion and the data reflect the order of metal affinity for the adsorbent material very well.     

Chemical substitution reaction between Cu(II) and Hg(II) and hydrous CdS(s)

The chemical reaction between hydrous CdS(s) and Cu(II) and Hg(II) were studied by electrophoretic mobility measurements and adsorption experiments. The results show that cation exchange, following readsorption of the released Cd(II) ions onto the freshly-formed CuS(s) and cadmium hydroxide precipitation reactions occur when CdS particles come into contact with these metal ions which have sulfide precipitates less soluble than CdS(s). The effect of organic ligands on the ion exchange reaction, exemplified by EDTA (a strong complexing ligand) and phthalic acid (a weak complexing ligand), was also investigated. Both organic compounds have little effect on the lattice ion exchange reaction unless a large amount of strong complexing agent is present in the system. The dissolution of CdS(s), however, is slightly hindered in the presence of weak complex former such as phthalic acid and greatly enhanced in the presence of strong complex former such EDTA.     

Removal of Cu(II) from aqueous solutions by adsorption process with anatase-type titanium dioxide

The experiment was performed in the reactor with suspended anatase-type titanium dioxide particles. The adsorption amount increased rapidly with an increasing pH value from pH 2 to 5 and remained constant over pH 5. The adsorption amount of Cu(2+) increased with temperature from 15 degrees C to 40 degrees C. The adsorption equilibrium constant (K(ads)) was 0.854 and adsorption isotherm of Cu(2+) adsorption on titanium dioxide was more suitable in Langmuir adsorption isotherm than in Freundlich isotherm. The adsorption rate was rapid with an increasing number of UV lamps of 254 nm.     

The removal of hexacyanoferrate(II) and (III) ions in dilute aqueous solution by activated carbon

The removal of iron cyano-complex ions [hexacyanoferrate(II) and (III) ions] in a dilute aqueous solution by activated carbon was investigated. The maximum adsorption of iron cyano-complex ions on activated carbon occurred at pH around 3. The hexacyanoferrate(III) ion was more adsorbable than the hexacyanoferrate(II) ion. Activated carbon promoted the oxidation of hexacyanoferrate(II) ion to (III) ion with dissolved oxygen in an acidic solution and the reduction of hexacyanoferrate(III) ion to (II) ion in an alkaline solution. The iron cyano-complex ion adsorbed on activated carbon could be eluted with higher concentrated acidic and alkaline solutions. The degree of elution decreased with an increase in potassium hydroxide concentration, since parts of the iron cyano-complexes on activated carbon were decomposed to form the iron hydroxide and the hexacyanoferrate(II) ion with an alkaline solution. The behavior of iron cyano-complexes in the presence of activated carbon, in the lower pH range (pH < 1) and at higher temperatures (80°C), was discussed.     

Phenol oxidation kinetics in water solution using iron(3)-oxide-based nano-catalysts

The influence of inorganic ions (HCO(3), PO(4)/HPO(4)/H(2)PO(4), Cl, SO(4), Ca, Na and Mg) on the advanced chemical oxidation process of organic compounds dissolved in water is reported here. The catalytic behavior of iron(3)-oxide-based nano-particles was investigated together with inorganic ions and hydrogen peroxide concentrations, and pH level. Phenol was chosen as a typical organic contaminant for this study as a simulating pollutant. The limiting concentrations of radical scavengers making the oxidation process inefficient were identified. The strong effect of concentration of radical scavengers HCO(3), PO(4)/HPO(4)/H(2)PO(4), the nano-catalyst and hydrogen peroxide concentrations, and pH on the phenol oxidation rate and lag time period before reaction starts was determined. It was shown that Cl, SO(4), Ca, Na and Mg ions had no significant effect on the kinetics of phenol oxidation.     

Copper(II) removal from aqueous solutions by fly ash

The removal of Cu(II) by adsorption on fly ash has been found to be concentration, pH and temperature dependent. The kinetics of adsorption indicates the process to be diffusion controlled. The Langmuir constants have been calculated at different temperatures, and the adsorption has been found to be endothermic (ΔH = 15.652 kcal mol^?1). The maximum removal is observed at pH 8.0, and variation in adsorption with pH has been explained on the basis of surface ionisation and complexation.     

Adsorption of 2,4,6-trichlorophenol by multi-walled carbon nanotubes as affected by Cu(II)

Adsorption equilibrium of 2,4,6-trichlorophenol (TCP) on multi-walled carbon nanotubes (MWCNTs) was investigated to explore the possibility of using MWCNTs for concentration, detection and removal of TCP from contaminated water. The adsorption of TCP on MWCNTs at pH 4 was nonlinear, reversible and best fit by a Polanyi-Manes model. Oxidation treatment increased surface area and introduced hydrophilic carboxylic groups to the defect sites of MWCNTs, hence increased the sorption of TCP and Cu(II) individually. Cu(II) suppressed the sorption of TCP on oxidized MWCNTs15A, but had little effect on as-grown MWCNTs15. TCP had no influence on Cu(II) sorption to either. The mechanisms of Cu(II) suppression effect on TCP adsorption are ascribed to the formation of surface complexes of Cu(II), which was verified by X-ray absorption spectroscopy. Cu(II) exerts a cross-linking effect of functional groups on adjacent tubes, creating a more tightly knit bundle and suppressing the condensation of TCP in the pore spaces between the tubes. The large hydration sphere around surface complexes of Cu(II) may also intrude or shield hydrophilic sites, leading to the “crowding out” of TCP around the Cu(II)-complexed sites.     

Adsorption and heterogeneous oxidation of As(III) on ferrihydrite

Redox transformation of arsenic strongly influences its fate and transport in the environment. It is of interest to investigate heterogeneous oxidation of As(III) on the surface of major metal oxide in sediments. Whether As(III) can be oxidized on ferrihydrite and the role ferrihydrite plays as catalyst or oxidant are inconsistent in previous researches. In this work, oxidation of As(III) on ferrihydrite was studied by analysis of dissolved and adsorbed As(III) and As(V) quantitatively and qualitatively. X-ray absorption near edge spectroscopy (XANES) and pH_pznpc (point of zero net proton charge) of ferrihydrite with adsorbed As(III) showed clear evidence for partial oxidation on ferrihydrite. Oxidation of As(III) occurred when it was brought to contact with ferrihydrite at high Fe/As molar ratio (i.e. 50, 200). The concentration of As(V) in solid phase increased gradually while adsorbed As(III) concentration dropped. Fe(II) was not detectable during the oxidation of As(III). These results showed that ferrihydrite had the catalytic effect on oxidation of As(III). Only a fraction of As(III) was oxidized even when the system was exposed to air. The effects of ferrihydrite aging, media pH, coexistence of ions on As(III) oxidation were also investigated. The results suggest that catalytic oxidation of As(III) on ferrihydrite may play a role in geochemical cycling of arsenic in environment.     

Removal of arsenic (III) and arsenic (V) from aqueous medium using chitosan-coated biosorbent

A biosorbent was prepared by coating ceramic alumina with the natural biopolymer, chitosan, using a dip-coating process. Removal of arsenic (III) (As(III)) and arsenic (V) (As(V)) was studied through adsorption on the biosorbent at pH 4.0 under equilibrium and dynamic conditions. The equilibrium adsorption data were fitted to Langmuir, Freundlich, and Redlich-Peterson adsorption models, and the model parameters were evaluated. All three models represented the experimental data well. The monolayer adsorption capacity of the sorbent, as obtained from the Langmuir isotherm, is 56.50 and 96.46 mg/g of chitosan for As(III) and As(V), respectively. The difference in adsorption capacity for As(III) and As(V) was explained on the basis of speciation of arsenic at pH 4.0. Column adsorption results indicated that no arsenic was found in the effluent solution up to about 40 and 120 bed volumes of As(III) and As(V), respectively. Sodium hydroxide solution (0.1M) was found to be capable of regenerating the column bed.     

Comparative study of the uses of poly(4-vinylpyridine) and poly(diallyldimethylammonium) chloride for the removal of perchlorate from aqueous solution by polyelectrolyte-enhanced ultrafiltration

An application of polyelectrolyte-enhanced ultrafiltration utilizes cationic polyelectrolytes to electrostatically bind anionic species. The colloid and target anion are then concentrated using an ultrafilter, producing a filtrate with a lower concentration of the target. This study compared the performances of poly(4-vinylpyridine) (P4VP) and poly(diallyldimethylammonium) chloride (PDADMAC) for the removal of perchlorate. Potentiometric titration data revealed that the ionization properties of P4VP in aqueous solution vary as functions of titrant utilized, degree of protonation, and counterion concentration. The greater affinity of perchlorate over chloride for the protonated pyridine residues of P4VP provided up to 95.8% retention of perchlorate under the solution conditions investigated. Through ultrafiltration experiments, the effects solution pH, counterion concentration, and polymer concentration were examined for both P4VP and PDADMAC. In addition, the effectiveness of P4VP recovery and reuse was also assessed.     

Solar disinfection (SODIS): simulation of solar radiation for global assessment and application for point-of-use water treatment in Haiti

Haiti and other developing countries do not have sufficient meteorological data to evaluate if they meet the solar disinfection (SODIS) threshold of 3-5 h of solar radiation above 500 W/m2, which is required for adequate microbial inactivation in drinking water. We have developed a mathematical model based on satellite-derived daily total energies to simulate monthly mean, minimum, and maximum 5-h averaged peak solar radiation intensities. This model can be used to assess if SODIS technology would be applicable anywhere in the world. Field measurements were made in Haiti during January 2001 to evaluate the model and test SODIS efficacy as a point-of-use treatment option. Using the total energy from a measured solar radiation intensity profile, the model recreated the intensity profile with 99% agreement. NASA satellite data were then used to simulate the mean, minimum, and maximum 5-h averaged peak intensities for Haiti in January, which were within 98.5%, 62.5%, and 86.0% agreement with the measured values, respectively. Most of the discrepancy was attributed to the heterogeneous nature of Haiti's terrain and the spatial resolution of the NASA data. Additional model simulations suggest that SODIS should be effective year-round in Haiti. Actual SODIS efficacy in January was tested by the inactivation of total coliform, E. coli, and H2S-producing bacteria. Exposure period proved critical. One-day exposure achieved complete bacterial inactivation 52% of the time, while a 2-day exposure period achieved complete microbial inactivation 100% of the time. A practical way of providing people with cold water every morning that has undergone a 2-day exposure would be to rotate three groups of bottles every morning, so two groups are out in the sun and one is being used for consumption.     

Adsorption of Cu(II), Cd(II) and Pb(II) from aqueous single metal solutions by succinylated twice-mercerized sugarcane bagasse functionalized with triethylenetetramine

This study describes the preparation of two new chelating materials, MMSCB 3 and 5, derived from succinylated twice-mercerized sugarcane bagasse (MMSCB 1). MMSCB 3 and 5 were synthesized from MMSCB 1 using two different methods as described by Gurgel and Gil (2009). In the first method MMSCB 1 was activated with 1,3-diisopropylcarbodiimide and in the second with acetic anhydride (to form an internal anhydride) and later both were reacted with triethylenetetramine in order to obtain MMSCB 3 and 5. New obtained materials were characterized by mass percent gain, concentration of amine groups, FTIR, and elemental analysis. MMSCB 3 and 5 showed mass percent gain of 19.9 and 57.1%, concentration of amine groups of 2.0 and 2.1 mmol/g, and nitrogen content of 5.8 and 4.4%. The capacity of MMSCB 3 and 5 to adsorb Cu²⁺, Cd²⁺, and Pb²⁺ from aqueous single metal ion solutions was evaluated at different contact times, pHs, and initial metal ion concentrations. Adsorption isotherms were well fitted by Langmuir model. Maximum adsorption capacities of MMSCB 3 and 5 for Cu²⁺, Cd²⁺, and Pb²⁺ were found to be 59.5 and 69.4, 86.2 and 106.4, 158.7 and 222.2 mg/g, respectively.     

Iron(III) (hydr)oxide-mediated photooxidation of 2-aminophenol in aqueous solution: a kinetic study

The photooxidation of 2-aminophenol in aqueous solution in the presence of an iron(III) (hydr)oxide (goethite, alpha-FeOOH), used as a heterogeneous catalyst, has been investigated at different pH (3.0-8.0) and catalyst loads (100-500 mg/l) aiming mainly at elucidating the reaction kinetics. A large experimental campaign allowed to rule out the intervention of HO radicals in the photodegradation of 2-aminophenol. The classic Langmuir-Hinshelwood equation has been used for the kinetic analysis, best estimated values of the kinetic parameters being derived by means of an optimization procedure. The dependence of reaction kinetics on the temperature in the range of 285-308K has also been investigated.     

Facilitated transport of Cu with hydroxyapatite nanoparticles in saturated sand: effects of solution ionic strength and composition

Column experiments were conducted to investigate the facilitated transport of Cu in association with hydroxyapatite nanoparticles (nHAP) in water-saturated quartz sand at different solution concentrations of NaCl (0-100 mM) or CaCl₂ (0.1-1.0 mM). The experimental breakthrough curves and retention profiles of nHAP were well described using a mathematical model that accounted for two kinetic retention sites. The retention coefficients for both sites increased with the ionic strength (IS) of a particular salt. However, the amount of nHAP retention was more sensitive to increases in the concentration of divalent Ca²⁺ than monovalent Na⁺. The effluent concentration of Cu that was associated with nHAP decreased significantly from 2.62 to 0.17 mg L⁻¹ when NaCl increased from 0 to 100 mM, and from 1.58 to 0.16 mg L⁻¹ when CaCl₂ increased from 0.1 to 1.0 mM. These trends were due to enhanced retention of nHAP with changes in IS and ionic composition (IC) due to compression of the double layer thickness and reduction of the magnitude of the zeta potentials. Results indicate that the IS and IC had a strong influence on the co-transport behavior of contaminants with nHAP nanoparticles.     

Surface modified bacterial biosorbent with poly(allylamine hydrochloride): Development using response surface methodology and use for recovery of hexachloroplatinate(IV) from aqueous solution

In this study, poly(allylamine hydrochloride) (PAA/HCl) was cross-linked with fermentation bacterial waste (Escherichia coli) in order to introduce a large amount of amine groups as binding sites for potassium hexachloroplatinate(IV), as a model anionic pollutant. The sorption performance of PAA/HCl-modified E. coli was greatly affected by the dosages of PAA/HCl and crosslinker (epichlorohydrin, ECH), and by the pH of the modification reaction medium. These factors were optimized through the response surface methodology (RSM). A three-level factorial Box-Behnken design was performed, and a second-order polynomial model was successfully used to describe the effects of PAA/HCl, ECH and the pH on the Pt(IV) uptake (R² = 0.988). The optimal conditions that were obtained from the RSM were 0.49 g of PAA/HCl, 0.05 mL of ECH and pH 10.02, with 1.0 g of dried E. coli biomass. The biosorption isotherm and kinetics studies were carried out in order to evaluate the sorption potential of the PAA/HCl-modified E. coli that was prepared under the optimized conditions. The sorption performance of the developed bacterial biosorbent was 4.36 times greater than that of the raw E. coli. Desorption was carried out using 0.05 M acidified thiourea and the biosorbent was successfully regenerated and reused up to four cycles. Therefore, this simple and cost-effective method suggested here is a useful modification tool for the development of high performance biosorbents for the recovery of anionic precious metals.     

Detoxification of chlorine dioxide (ClO2) by ascorbic acid in aqueous solutions: ESR studies

Chlorine dioxide (ClO₂) which was easily prepared from dissolving sodium chlorite (NaClO₂) in acidic aqueous solutions can oxidize -ascorbic acid (AsA) to give the short-lived intermediate, ascorbic acid free radical (AFR). The detection of the ascorbate radical was made by using the electron spin resonance (ESR) spectroscopy coupled with a rapid-mixing flow technique which enabled us to detect radicals having a life-time of 5–100 ms at room temperature. This result indicates that the ascorbic acid becomes a suitable reagent for detoxification of the ClO₂, which is remaining in drinking water, in the living body.     

Kinetics of sorptive removal of chromium(VI) from aqueous solutions by calcined Mg-Al-CO(3) hydrotalcite

The sorptive removal of hexavalent chromium from aqueous solutions by calcined Mg-Al-CO(3) hydrotalcite was investigated in a batch mode. The influence of agitation speed, solution pH, initial chromium concentration, sorbent concentration and temperature has been tested in kinetic runs. Three kinetic models have been evaluated to fit the experimental data: the pseudo-first order, the modified-second order and the Elovich equation. It was shown that the first-order model could best describe the sorption kinetics. A Freundlich isotherm was used to fit equilibrium experiments. Hydrotalcite presents a sorption capacity of approximately 120 mg Cr/g, under the investigated experimental conditions. The calculated activation energy for process studied was around 40 kJ/mol.     

Binding of Cu(II) to algae in a metal buffer

The interactions of Cu(II) with algal surfaces and exudates were studied in metal-NTA buffers by a combination of several analytical techniques. Suspensions of living algae in the presence of NTA were titrated at constant pH with Cu(II). The various Cu species were determined as follows: a copper ion selective electrode was used reliably in the pCu range 9–12; differential pulse polarography was used to measure separately Cu(II)-NTA complexes and labile Cu(II) species and to evaluate the complexation of copper by ligands in solution; copper bound to the algal surfaces was extracted by acid treatment and measured by AAS. Thus, we determined both the binding of Cu to the algal surfaces and to exudates excreted by the algae. The results were interpreted in terms of conditional equilibrium constants valid at a given pH; the conditional constants, both for the binding to the surfaces and with the exudates increase in the pH range 5.0–6.5. Simple equilibrium models using the experimentally determined binding capacities and equilibrium constants were able to simulate the results and to evaluate the speciation of copper. Under the experimental conditions used, the binding of Cu(II) to algal exudates has a more significant effect on copper speciation than the binding to the algal surfaces. These extracellular ligands may play an important role in decreasing the concentration of free copper ion and thus mitigating the potential toxic effects in organisms.