Biodegradable metal adsorbent synthesized by graft polymerization onto nonwoven cotton fabric

A fibrous adsorbent for Hg ions was synthesized by radiation-induced emulsion graft polymerization of glycidyl methacrylate (GMA) onto a nonwoven cotton fabric and subsequent chemical modification. The optimal pre-irradiation dose for initiation of the graft polymerization of GMA, which minimized the effects of radiation damage on the mechanical strength of the nonwoven cotton fabric, was found to be 10 kGy. The GMA-grafted nonwoven cotton fabric was subsequently modified with ethylenediamine (EDA) or diethylenetriamine (DETA) to obtain a Hg adsorbent. The resulting amine-type adsorbents were evaluated for batch and continuous adsorption of Hg. In batch adsorption, the distribution coefficients of Hg reached 1.9×10⁵ and 1.0×10⁵ for EDA- and DETA-type adsorbents, respectively. A column packed with EDA-type adsorbent removed Hg from 1.8 ppm Hg solution at a space velocity of 100 h^?1, which corresponds to 16,000 times the volume of the packed adsorbent. The adsorbed Hg on the EDA-type adsorbent could be completely eluted by 1 M HCl solution. A microbial oxidative degradation test revealed that the EDA-type adsorbent is biodegradable.     

Metal adsorbent for alkaline etching aqua solutions of Si wafer

High performance adsorbent is expected to be synthesized for the removal of Ni and Cu ions from strong alkaline solution used in the surface etching process of Si wafer. Fibrous adsorbent was synthesized by radiation-induce emulsion graft polymerization onto polyethylene nonwoven fabric and subsequent amination. The reaction condition was optimized using 30 L reaction vessel and nonwoven fabric, 0.3 m width and 18 m long. The resulting fibrous adsorbent was evaluated by 48 wt% NaOH and KOH contaminated with Ni and Cu ions, respectively. The concentration levels of Ni and Cu ions was reduced to less than 1 μg/kg (ppb) at the flow rate of 10 h^?1 in space velocity. The life of adsorbent was 30 times higher than that of the commercialized resin. This novel adsorbent was commercialized as METOLATE^® since the ability of adsorption is remarkably higher than that of commercial resin used practically in Si wafer processing.     

Adsorption of Cr(VI) using cellulose microsphere-based adsorbent prepared by radiation-induced grafting

Cellulose microsphere (CMS) adsorbent was prepared by radiation-induced grafting of dimethylaminoethyl methacrylate (DMAEMA) onto CMS followed by a protonation process. The FTIR spectra analysis proved that PDMAEMA was grafted successfully onto CMS. The adsorption of Cr(VI) onto the resulting adsorbent was very fast, the equilibrium adsorption could be achieved within 15 min. The adsorption capacity strongly depended on the pH of the solution, which was attributed to the change of both the existed forms of Cr(VI) and the tertiary-ammonium group of PDMAEMA grafted CMS with the pH. A maximum Cr(VI) uptake (ca. 78 mg g^?1) was obtained as the pH was in the range of 3.0–6.0. However, even in strong acid media (pH 1.3), the adsorbents still showed a Cr(VI) uptake of 30 mg g^?1. The adsorption behavior of the resultant absorbent could be described with the Langmuir mode. This adsorbent has potential application for removing heavy metal ion pollutants (e.g. Cr(VI)) from wastewater.     

Adsorption of Apollo reactive dyes on poly(N,N dimethylamino ethylmethacrylate) hydrogels

Poly(N,N-dimethylamino ethylmethacrylate) [P(DMAEMA)] hydrogels were prepared by irradiating the ternary mixtures of dimethylamino ethylmethacrylate (DMAEMA)/ethyleneglycol dimethacrylate (EGDMA)/water (H₂O) by γ-rays at ambient temperature. The swelling of four types of DMAEMA hydrogels in distilled water is higher than the swelling of these hydrogels in dye solutions. The value of equilibrium swelling of P(DMAEMA)1 hydrogel was 338% at pH 7.0 in distilled water, while it was 325% and 326% at pH 7.0 in Apollofix Red (AR) and Apollofix Yellow (AY) solutions, respectively. The adsorption capacity of P(DMAEMA)1 hydrogel was found to increase from 85 to 131 mg for AR g⁻¹ dry gel and from 58 to 111 mg for AY g⁻¹ dry gel with decreasing pH of the dye solutions.     

A study of the removal of selenite and selenate from aqueous solutions using a magnetic iron/manganese oxide nanomaterial and ICP-MS

Selenium (Se) is naturally occurring in the environment and is an essential nutrient in mammals. However, environmental Se can be increased to toxic levels through different industrial practices. The potential adsorption of the Se oxoanions, selenite and selenate, from aqueous solutions onto nanosynthesized MnFe₂O₄ was investigated using batch techniques and DRC-ICP-MS spectroscopy. The nanomaterial (NM) was laboratory synthesized through slow titration of a mixture of Fe²⁺ and Mn²⁺ ions. X-ray diffraction and Scherrer's equation were used to determine the phase of the material and crystallite size, respectively. The effects of pH, reaction time, competitive anions, and the adsorption capacity of the synthesized NM to bind selenite and selenate were investigated. The Langmuir isotherm was used to determine the binding capacity of the NM. Results showed that the phase of the nanomaterial was similar to Jacobsite with a size of 27.5 nm. Results also showed that the sorption of either 100 ppb of selenite or selenate was pH independent in the pH range 2 to 6 and occurred within 5 min of contact time. The introduction of Cl⁻ and NO₃⁻ anions individually added to solution had no significant effect on the sorption of either selenite or selenate. However, it was found that the addition of SO₄²⁻ had a competitive effect only on the sorption of selenate, first seen at 10 ppm and more pronounced at 100 ppm of SO₄²⁻. In the presence of 100 ppm of PO₄³⁻, the adsorption of selenate decreased to 87% while selenite sorption decreased to 20%. From the Langmuir isotherm equation it was determined that the nano-Jacobsite had a selenite and selenate binding capacity of 6573.76 and 769.23 mg Se/kg of NM, respectively.     

Competitive adsorption of toxic heavy metal contaminants by gum kondagogu (Cochlospermum gossypium): A natural hydrocolloid

Gum kondagogu (Cochlospermum gossypium), a naturally occurring tree biopolymer, is exploited as a biosorbent to remove metal ions from aqueous solutions. The removal efficiency of toxic metals by gum kondagogu was determined quantitatively in the order Cd²⁺ > Cu²⁺ > Fe²⁺ > Se²⁺ > Pb²⁺ > total Cr > Ni²⁺ > Zn²⁺ > Co²⁺ > As²⁺ at pH 5.0 ± 0.1 and temperature 25 ± 2 °C by inductively coupled plasma-mass spectrometry (ICP-MS). The biosorption (%) of various metal ions tested was found to be in the range of 97.3–16.7%, at pH 5.0. The morphological and mechanisms of interaction of toxic metal ions with gum kondagogu were assessed by scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM-EDXA) and X-ray diffraction (XRD) spectrum. The analysis indicated that biosorption process included morphological changes, precipitation, complexation and ion exchange mechanism for the removal of metal ions by the gum. XRD analysis indicated the amorphous nature of gum kondagogu, which facilitate metal biosorption. The metal ions adsorption leads to its deposition on the gum kondagogu matrix in a crystalline state.     

Simultaneous removal of copper(II), lead(II), zinc(II) and cadmium(II) from aqueous solutions by multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were used successfully for the removal of heavy metals from aqueous solution. Characterization techniques showed the carbon as nanotubes with an average diameter between 40 and 60 nm and a specific surface area of 61.5 m² g^?1. The effect of carbon nanotubes mass, contact time, metal ions concentration, solution pH, and ionic strength on the adsorption of Cu(II), Pb(II), Cd(II) and Zn(II) by MWCNTs were studied and optimized. The adsorption of the heavy metals from aqueous solution by MWCNTs was studied kinetically using different kinetic models. A pseudo-second order model and the Elovich model were found to be in good agreement with the experimental data. The mechanism of adsorption was studied by the intra-particle diffusion model, and the results showed that intra-particle diffusion was not the slowest of the rate processes that determined the overall order. This model also revealed that the interaction of the metal ions with the MWCNTs surface might have been the most significant rate process. There was a competition among the metal ions for binding of the active sites present on the MWCNTs surface with affinity in the following order: Cu(II) > Zn(II) > Pb(II) > Cd(II).     

The application of Bimetallic metal–organic frameworks for antibiotics adsorption

Fe/Zr-base metal–organic frameworks(Fe/Zr-MOFs) were prepared using a solvothermal method from 1,3,5-phthalic acid (H₃BTC, 98 %) as the organic chain and ferrous heptahydrate (FeSO₄·7H₂O) and zirconium acetate Zr(CH₃COO)₄] as the metal ions. The resulting material was used to remove Doxycycline hydrochloride (DC). The experimental results showed that when the concentration of DC was 10 ppm and the mass of Zr/Fe-MOFs was 100 mg, the maximum removal rate after 5 h was 87.5 %. The results showed that the correlation coefficients (R²) of the pseudo-second-order kinetics model and Freundlich isotherm model of Zr/Fe-MOFs adsorption of DC were greater than 0.99, indicating good consistency. The results showed that the adsorption process of DC by Zr/Fe-MOFs was endothermic and spontaneous. Fe/Zr-MOFs had a high adsorption capacity for DC removal and good application prospects.     

Thermodynamics and kinetics of adsorption of Cu(II) from aqueous solutions onto a new cation exchanger derived from tamarind fruit shell

A novel cation exchanger (TFS-CE) having carboxylate functionality was prepared through graft copolymerization of hydroxyethylmethacrylate onto tamarind fruit shell (TFS) in the presence of N,N′-methylenebisacrylamide as a cross-linking agent using K₂S₂O₈/Na₂S₂O₃ initiator system, followed by functionalisation. The TFS-CE was used for the removal of Cu(II) from aqueous solutions. At fixed solid/solution ratio the various factors affecting adsorption such as pH, initial concentration, contact time, and temperature were investigated. Kinetic experiments showed that the amount of Cu(II) adsorbed increased with increase in Cu(II) concentration and equilibrium was attained at 1 h. The kinetics of adsorption follows pseudo-second-order model and the rate constant increases with increase in temperature indicating endothermic nature of adsorption. The Arrhenius and Eyring equations were used to obtain the kinetic parameters such as activation energy (E_a) and enthalpy (ΔH^#), entropy (ΔS^#) and free energy (ΔG^#) of activation for the adsorption process. The value of E_a for adsorption was found to be 10.84 kJ · mol^?1 and the adsorption involves diffusion controlled process. The equilibrium data were well fitted to the Langmuir isotherm. The maximum adsorption capacity for Cu(II) was 64 · 10 mg · g^?1 at T = 303 K. The thermodynamic parameters such as changes in free energy (ΔG^°), enthalpy (ΔH^°), and entropy (ΔS^°) were derived to predict the nature of adsorption process. The isosteric heat of adsorption increases with increase in surface loading indicating some lateral interactions between the adsorbed metal ions.     

Reversibility of platinum voltammograms in aqueous electrolytes,ionic product and dissociative adsorption of water

Well-known reversibility of platinum voltammograms in supporting aqueous electrolytes formally contradicts the equilibrium defined by the ionic product of water: K_w = [H⁺] · [OH⁻] ≅ 1 × 10¹⁴, since at any pH value, concentration of one of these ions should be too low (⩽10⁷ M) to ensure reversibility in the whole potential region at usual scan rates. This contradiction could be overcome by allowing dissociative water adsorption on platinum. All available relevant data obtained by in situ physical methods appear to provide indirect experimental evidences for this hypothesis.     

Influence of metal ions on the interaction between gatifloxacin and calf thymus DNA

To study the interaction between gatifloxacin (GT), metal ions (Cu²⁺, Cd²⁺, Co²⁺, Mg²⁺) and calf thymus DNA under condition of physiology pH, UV absorption and fluorescence methods were adopted. Result shows that metal ions and DNA are able to react with GT in ground state. In further research, by studying the influence of metal ions on binding of GT with DNA in metal ions–GT–DNA ternary system, we found that influential mechanism of Mg²⁺ on the binding of GT with DNA may be different from the other three. Mg²⁺ can act as a bridge in the binding of GT's carboxyl/carbonyl with DNA phosphate in certain concentration range; while Cu²⁺, Cd²⁺, Co²⁺ can combine directly with GT by reaction between GT carboxyl/carbonyl and DNA base, and enhance the binding ability of GT with DNA. The influence extent and type depend not only on the binding site of DNA with metal ions (phosphate or base), but also the binding ability of which. The stronger the binding ability of metal ions with DNA base is, the larger their promotion to binding of GT with DNA is. The order of metal ions’ influential ability on the binding of GT–DNA is identical to the binding ability order of metal ions with DNA base, that is: Cu²⁺ > Cd²⁺ > Co²⁺ > Mg²⁺.     

Effect of electrolytes on surface tension and surface adsorption of 1-hexyl-3-methylimidazolium chloride ionic liquid in aqueous solution

Surface and bulk properties of 1-hexyl-3-methylimidazolium chloride [C₆mim][Cl] as an ionic liquid (IL) have been investigated by surface tension and electrical conductivity techniques at various temperatures. Results reveal that the ionic liquid behaves as surfactant-like and aggregates in aqueous solution. Critical aggregation concentration (cac) values obtained by conductivity and surface tension measurements are in good agreement with values found in the literature. A series of important and useful adsorption parameters including cac, surface excess concentration (Γ), and minimum surface area per molecule (A_min) at the air + water interface were estimated from surface tension in the presence and absence of different electrolytes. Obtained data show that the surface tension as well as the cac of [C₆mim][Cl] is reduced by electrolytes. Also, values of surface excess concentration (Γ) show that the IL ions in the presence of electrolyte have much larger affinity to adsorption at the surface and this affinity increased in aqueous electrolyte solution in the order of I^? > Br^? > Cl^? for counter ion of salts that was explained in terms of a larger repulsion of chloride anions from interface to the bromide and iodide anion as well as difference in their excess polarizability.     

Synthesis,characterization and batch assessment of groundwater fluoride removal capacity of trimetal Mg/Ce/Mn oxide-modified diatomaceous earth

In this study, trimetal Mg/Ce/Mn oxide-modified diatomaceous earth (DE) was synthesized at optimal conditions. Comparison of the SEM images and the results of EDX analyses of the raw and the modified DE confirmed the surface modification of the raw DE with the trimetal oxide. Groundwater fluoride removal capacity of the sorbent was evaluated by batch method at various defluoridation conditions. At a sorbent dosage of 0.6 g/100 mL (contact time: 60 min, mixing speed of 200 rpm and temperature: 297 K), the fluoride removal was >93% for solutions containing initial fluoride concentration of 10–60 mg/L. Sorbent’s optimum fluoride uptake capacity was 12.63 mg/g at the initial fluoride concentration of 100 mg/L. Fluoride removal was >91% for solutions with initial pH range of ∼4–11 (initial fluoride concentration: 9 mg/L, sorbent dosage: 0.6 g/100 mL). Appraisal of the effect of co-existing anions on fluoride removal showed that CO₃²⁻ would reduce the amount of fluoride removed from solution, while other anions such as PO₄³⁻, NO₃⁻ and SO₄²⁻ had no observable effect. K₂SO₄ solution was found to be most suitable for regeneration of spent Mg/Ce/Mn oxide-modified DE compared to Na₂CO₃ and NaOH. The mechanism of fluoride removal at pH > 5.45 (pHpzc = 5.45) occurred by exchange of hydroxyl groups on surface of sorbent with fluoride ions from solution. Sorption data fitted better to Langmuir isotherm and pseudo-second-order model. External diffusion was observed to be the sorption rate limiting factor.     

Geochemical fractions and modeling adsorption of heavy metals into contaminated river sediments in Japan and Thailand determined by sequential leaching technique using ICP-MS

In order to provide information on the chemical processes in sediment fractions and their adsorption models, we investigated the contaminated sediments of the Sumida River in Tokyo, Japan and the Chao Phraya River in Bangkok, Thailand. Samples were leached through a sequential leaching technique to perform metal concentration analysis for the sediment fraction assessment and then samples were tested for the model adsorption of the highest level of sediments contaminated by heavy metals using the isotherm Langmuir and Freundlich equations. Metal (Pb, Cd, Zn, As, Cu, Ca, Fe, and Mn) concentration in the leached solutions was analyzed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The pattern of geochemical fractions in both sediment samples showed the maxima leached levels of Cd (38.6 %), Ca (55.2%), and Mn (41.3%) in the soluble fraction; Pb (52.1%), and Zn (56.7%) in the reducible fraction; Cu (61.2%) in the oxidizable fraction; and As (47.1%) and Fe (55.9%) in the residual fraction. The total level fractions of Pb (62.6 ppm), Zn (240 ppm), As (27.2 ppm), Fe (16,636 ppm) and Mn (419 ppm) in the Chao Phraya River sediments were higher compared to those in the Sumida River, indicating the high anthropogenic effect in Bangkok. In the most contaminated sediments, the higher adsorption capacity of heavy metal concentrations was contributed by SiO_2, CaCO_3, and Al₂O₃ determined by the X-ray diffraction and organic contents. The model of adsorption of Cd fitted to the linear form of Langmuir’s equation with the correlation coefficients (r² = 0.94), b (0.467) and k (7137), whereas Pb, Cu, Cr, and Zn conformed to the model of the Freundlich equation.     

The removal of uranium (VI) from aqueous solutions onto natural sepiolite

The adsorption of uranium (VI) from aqueous solutions onto natural sepiolite has been studied using a batch adsorber. The parameters that affect the uranium (VI) sorption, such as contact time, solution pH, initial uranium(VI) concentration, and temperature, have been investigated and optimized conditions determined. Equilibrium isotherm studies were used to evaluate the maximum sorption capacity of sepiolite and experimental results showed this to be 34.61 mg · g^?1. The experimental results were correlated reasonably well by the Langmuir adsorption isotherm and the isotherm parameters (Q_o and b) were calculated. Thermodynamic parameters (ΔH° = ?126.64 kJ · mol^?1, ΔS° = ?353.84 J · mol^?1 · K^?1, ΔG° = ?21.14 kJ · mol^?1) showed the exothermic heat of adsorption and the feasibility of the process. The results suggested that sepiolite was suitable as sorbent material for recovery and adsorption of uranium (VI) ions from aqueous solutions.     

Anodic electrochemiluminescence of CdSe nanoparticles coreacted with tertiary amine and halide induced quenching effect

The novel anodic electrochemiluminescence (ECL) behaviors of the CdSe nanoparticles coreacted with tertiary amine were observed. The ECL intensity peak located near +1.2 V, accompanied with a shoulder above +1.5 V. The ECL emission peak estimated at about 580 nm was almost identical with that of the photoluminescence (PL), indicating the passivation of the surfaces of the nanoparticles. The dependence of the ECL on system pH and the concentration of the coreactants were also discussed. The halide ions could quench ECL, with the effective order I^? > Br^? > Cl^?. Based on these results the possible ECL processes were proposed.     

Ion exchange fabric synthesized by graft polymerization and its application to ultra-pure water production

Ion exchange fabric (IEF) having the functional group of sulfonic acid was synthesized by radiation grafting of glycidyl methacrylate on a polyethylene nonwoven fabric and subsequent chemical modification. Total organic carbon eluted from the resulting IEF could be reduced to the concentration less than 1 ppb after washing with organic solvents. Adsorption performance of the obtained IEF was evaluated by 10 ppb Na⁺ solution. The column packed IEF, 7 mm in diameter and 20 mm high, could remove the Na⁺ at the distribution coefficient of 1.2×10⁷ at linear velocity of 400 m/h. At column height of 95 mm, the breakthrough point reached 2.0×10⁵ in bed volume and the degree of column utilization was improved up to 18.7%. From these results, the IEF synthesized by graft polymerization was considered to be applicable for water purification in ultra-pure water production.     

Effective scrap iron particles (SIP) pre-treatment for complete mineralization of benzidine based azo dye effluent

This study proposed that hybrid scrap cast iron particles (SIP)-aerobic biodegradation technology could enhance the biodegradability of toxic wastewater. SIP cleaved the azo linkages of Direct Green1 dye to form benzidine, 4-aminophenol, aniline and 1,2,7-triamino-8-hydroxynapthalene-3,6-disulfonic acid. SIP-mediated dye reduction was effective at wide pH range; however, kinetic analysis revealed fastest pseudo-first order dye reduction rate at acidic pH 3 (k_d = 0.549 min⁻¹) followed by pH 9 (k_d = 0.383 min⁻¹) and pH 7 (k_d = 0.318 min⁻¹). The daughter aromatic amines produced were partially adsorbed onto the SIP surface and maximally at neutral pH. The adsorption process followed pseudo-second order adsorption kinetics and Langmuir isotherm. Benzidine was adsorbed more than 4-aminophenol and aniline. BOD₅ of the SIP-treated effluent increased from 0.93 to 12 mg/L showing improved biodegradability. The daughter amines were rapidly mineralized in the aerobic bioreactor within 6 h. Cost-effective SIP pre-treatment could accelerate mineralization and detoxification of recalcitrant wastewater.     

Equilibrium and kinetics studies on adsorption of Cu(II) from aqueous solutions onto a graft copolymer of cross-linked starch/acrylonitrile (CLSAGCP)

A synthetic graft copolymer of cross-linked starch/acrylonitrile was used as an adsorbent for the removal of Cu(II) ions from an aqueous solution of copper nitrate hexahydrate Cu(NO₃)₂ · 6H₂O at different temperatures and fixed pH. The amount adsorbed increased with increasing concentration of Cu(II) ions and decreasing temperature. The length of time taken to reach equilibrium of the adsorption of Cu(II) ions was the same at all temperatures tested. Kinetics studies showed that the adsorption process obeyed first-order reversible kinetics and the adsorption isotherms followed the Freundlich model. Furthermore, the thermodynamic parameters, i.e. standard free energy (ΔG^∘), standard enthalpy (ΔH^∘), and standard entropy (ΔS^∘), of the adsorption process were calculated and the results are discussed in detail.     

Evaluation of the impact of phosphate salts on the formation of ionic-liquid-based aqueous biphasic systems

The present study aims at evaluating the capability of phosphate-based salts, whose anions can coexist in water depending on the media pH, to promote aqueous biphasic systems (ABS) formation with 1-butyl-3-methylimidazolium-based ionic liquids, as well as to infer on the influence of the ionic liquid anion in the overall process of liquid–liquid demixing. In this context, novel phase diagrams of ABS composed of several imidazolium-based ionic liquids and three phosphate salts and a mixture of salts (K₃PO₄, K₂HPO₄, K₂HPO₄ + KH₂PO₄, and KH₂PO₄) were determined by the cloud point titration method at 298 K and atmospheric pressure. The corresponding tie-line compositions, tie-line lengths, and pH values of the coexisting phases were also determined. The ionic liquids ability to promote ABS is related with the hydrogen-bond basicity of the composing anion – the lower it is the higher the ability of the ionic fluid to undergo liquid–liquid demixing. Moreover, similar patterns on the ionic liquids sequence were observed with the different phosphate salts. The phosphate anion charge plays a determinant role in the formation of ABS. The two-phase formation aptitude (with a similar ionic liquid) decreases in the rank: K₃PO₄ > K₂HPO₄ > K₂HPO₄ + KH₂PO₄ > KH₂PO₄. Yet, besides the charge of the phosphate anion, the pH and ionic strength of the aqueous media also influence the phase separation ability.