Sorption Capacity For Cu Research Articles

Sorption thermodynamic and kinetic study of Cu(II) onto modified plant stem bark.

In this study, four types of "Juá" stem barks (Ziziphus joazeiro) were investigated for the removal of Cu(II) from aqueous solutions. The tested samples included natural coarse barks, and barks washed with water, ethanol-water, and NaOH solutions. The solvent-modified materials simulated the waste of the industrial extraction of saponins from bark. The valorization of these processing residues as sorbents was evaluated. The NaOH-washed sorbent exhibited the highest sorption capacity for Cu(II) (maximum sorption capacity 32mgg-1). Ion exchange process between copper and exchangeable surface cations and electrostatic attraction of copper with carboxylate and phenolate groups were identified as the primary sorption mechanisms. Desorption tests revealed that a large portion of the metal sorbed (80%) was easily released from the sorbent thus suggesting, in line with the proposed mechanisms, the existence of weak sorbate-sorbent interactions. The sorptive process was found to be exothermic (∆H° = - 48.1 ± 13.5kJ.mol-1) and thermodynamically favorable at lower temperatures.

Selective Removal of Transient Metal Ions from Acid Mine Drainage and the Possibility of Metallic Copper Recovery with Electrolysis

ABSTRACT The low pH and high salinity of acid mine drainage (AMD) fundamentally complicates the sorption processes. We explored the selective removal of Cu, Ni and Co ions present in AMD from the excess of ferrous ions of using a chelating resins Lewatit® MonoPlus TP 220 and Lewatit® TP 208. Also, the recovery of metal copper from desorption solution using electrolysis was investigated. The results showed that the most effective sorption of metal ions was achieved with chelating sorbent Lewatit® TP 220. The dynamic capacity of the sorbent under the given conditions (pH= 2.5 ± 0.03, presence of Fe(II/III), Zn(II), Mn(II)) decreased in the following order: Cu(II) (43.3 ± 1.4 g/L) > Ni(II) (22.1 ± 2.1 g/L) > Co(II) (3.6 ± 0.4 g/L). Chelating resin Lewatit® TP 208 under the same conditions showed lower efficiency: Cu(II) (30.6 ± 1.3 g/L) > Ni(II) (9.1 ± 0.17 g/L) > Co(II) (1.3 ± 0.08 g/L). The weak base anion exchanger Purolite® A 832 was successfully used to take up Cu(II) from ammonia solution and easily regenerated with sulfuric acid. The sorption capacity for Cu(II) was calculated to be 19.2 ± 0.5 g/L. Electrolysis experiments were performed with a fluidized bed electrolysis reactor where metallic copper was regenerated from desorption solutions and purified sulfuric acid solutions were obtained.

Characterization of Cu(II) and Zn(II) Sorption onto Zeolite

In this study, a batch sorption study approach was combined with an instrumental analytical approach of atomic absorption spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) for the sorption of copper and zinc ions from aqueous solution on zeolites. Both copper and zinc are biogenic elements; nevertheless, many industrial processes produce an excessive amount, which is why their efficient removal from water must be studied. Two types of zeolites, Zeolite Micro 20 (Z-M20) and Zeolite Micro 50 (Z-M50), were used. The results showed that the maximum sorption capacities for removal of Cu and Zn were 1.06 for CuSO4, 42.35 for Cu(NO3)2, 1.15 for ZnSO4 and 2.29 for Zn(NO3)2 adsorption onto Z-M20 and 0.45 for CuSO4, 1.67 for Cu(NO3)2, 0.39 for ZnSO4 and 1.51 for Zn(NO3)2 adsorption onto Z-M50. The maximum sorption capacities are higher for sulfates and the sorbent with smaller particle size. The sorption capacities of Cu and Zn for corresponding anion and particle size differ only up to 5–15%. Using XRD and XPS analyses before and after the sorption process, it was found that the content of both Cu and Zn in the surface layer and the bulk are the same for sorption onto sorbent with smaller particle size, but are higher in the surface layer than in the bulk for sorption onto sorbent with larger particle size. One of the main findings of this study is that a zeolite with smaller particles takes Cu and Zn by the whole particle, while with bigger particles, Cu and Zn concentrate in the surface of the particle. The results of the study may be used as an indicator for sorption efficiency of the studied zeolites for their application in the treatment of copper and zinc contaminated effluents.

A Highly Efficient Environmental-Friendly Adsorbent Based on Schiff Base for Removal of Cu(II) from Aqueous Solutions: A Combined Experimental and Theoretical Study.

Removal of heavy metals from drinking water sources and rivers is of strategic health importance and is essential for sustainable ecosystem development, in particular in polluted areas around the globe. In this work, new hybrid inorganic-organic material adsorbents made of ortho- (Si-o-OR) or para-Schiff base silica (Si-p-OR) were synthesized and characterized in depth. These hybrid adsorbents show a high selectivity to Cu(II), even in the presence of competing heavy metals (Zn(II), Cd(II), and Pb(II)), and also demonstrate great reusability after five adsorption-desorption cycles. Maximum sorption capacity for Cu(II) was found for Si-o-OR (79.36 mg g−1) and Si-p-OR (36.20 mg g−1) in no less than 25 min. Energy dispersive X-ray fluorescence and Fourier transform-infrared spectroscopy studies demonstrate that this uptake occurs due to a chelating effect, which allows these adsorbents to trap Cu(II) ions on their surfaces; this result is supported by a theoretical study for Si-o-OR. The new adsorbents were tested against real water samples extracted from two rivers from the Oriental region of Morocco.

Preparation of novel ZnO-NP@Zn-MOF-74 composites for simultaneous removal of copper and tetracycline from aqueous solution

• ZnO-NP@Zn-MOF-74 was prepared using layered porous ZnO as the zinc sources. • ZnO-NP@Zn-MOF-74 showed a smaller framework structure and stronger affinities. • The loaded ZnO nanoparticles on ZnO-NP@Zn-MOF-74 provided more function groups. • The formation of ZnO-NP@Zn-MOF-74-Cu-TC improved the removal of both TC and Cu. • ZnO-NP@Zn-MOF-74 had good ability for the simultaneous removal of Cu and TC. In this study, layered porous ZnO microspheres, instead of traditional zinc ions, were used to obtain a composite of nano-ZnO and a metal organic framework (Zn-MOF-74), namely ZnO-NP@Zn-MOF-74. Compared with the traditional Zn-MOF-74, the ZnO-NP@Zn-MOF-74 showed better removal performances for both copper (Cu) and tetracycline (TC) due to its smaller size and good affinities of the loaded nano-ZnO. Batch experiments showed that the simultaneous removal of Cu and TC by the ZnO-NP@Zn-MOF-74 was rapid and pH-dependent. The removal efficiencies of both Cu and TC increased rapidly during the first 10 min and could reach equilibriums within 2 h. The maximum sorption capacities of Cu and TC on the ZnO-NP@Zn-MOF-74 derived from the Langmuir model were 106.27 and 137.17 mg·g −1 , respectively. The removal mechanisms for Cu and TC involved surface complexation, π-π stacking, ion exchange, and electrostatic interaction. In addition, the formation of the ZnO-NP@Zn-MOF-74-Cu-TC complex on the surface of the ZnO-NP@Zn-MOF-74 improved the removal of both TC and Cu. Given the above results, the ZnO-NP@Zn-MOF-74 has great application prospects for the treatment of Cu and TC polluted water.

Closing the loop in a constructed wetland for the improvement of metal removal: the use of Phragmites australis biomass harvested from the system as biosorbent

Among the numerous clean-up techniques for water treatment, sorption methods are widely used for the removal of trace metals. Phragmites australis is a macrophyte commonly used in constructed wetlands for water purification, and in the last decades, its use as biosorbent has attracted increasing attention. In view of a circularly economy approach, this study investigated improvement of trace metal removal by recycling the biomass of P. australis colonizing a constructed wetland, which operates as post-treatment of effluent wastewater from an activated sludge plant serving the textile industrial district of Prato (Italy). After the annual mowing of the reed plants, the biomass was dried and blended to derive a sustainable and eco-friendly biosorbent and its sorption capacity for Fe, Cu, and Zn was investigated comparing the batch system with the easier-to-handle column technique. The possibility of regeneration and reuse of the biosorbent was also evaluated. The biomaterial showed an interesting sorption capacity for Cu, Fe, and Zn, both in batch and in column experiments, especially for Fe ions. The immobilization of the biosorbent in column filters induced some improvement in the removal efficiency, and, in addition, this operation mode has the advantage of being much more suitable for practical applications than the batch process.

Mechanisms for the removal of Cd(II) and Cu(II) from aqueous solution and mine water by biochars derived from agricultural wastes

The capacity of biochars derived from agricultural wastes to remove Cd(II) and Cu(II) from aqueous solution and contaminated mine water was evaluated using laboratory-based batch sorption experiments. To examine immobilization of heavy metals, biochars produced in a commercial-scale mobile pyrolizer from feedstocks: poultry litter; lucerne shoot; vetch shoot; canola shoot; wheat straws; and sugar-gum wood, were tested in a liquid-based system. Biochars were characterized by FTIR, XPS and XRD before and after the mine water treatment. Lucerne biochar had the highest Langmuir sorption capacity of Cd(II) (6.28 mg g−1) and vetch-derived biochar had the highest Cu(II) sorption capacity (18.0 mg g−1) at pH 5.5. All the biochars exhibited higher sorption capacity for Cu(II) than for Cd(II). The smaller ionic radius and higher electronegativity of Cu(II), and the PO43−, CO32− and N-containing functional groups of biochars enhanced their binding affinity. The results demonstrated that poultry litter-derived biochar was effective at removal of the Cd(II) and Cu(II) from mine water up to the levels recommended by the World Health Organisation. The results revealed that precipitation with CO32− and PO43−, complexation with –OH and –COOH groups and electrostatic interaction with O-containing surface functional groups were the main mechanisms involved in the removal of multi-metals by biochars, and that selection of feedstock materials for biochar production is important to maximise remediation of multi-metals in contaminated water.

Preparation of Economical and Environmentaly Friendly Modified Clay and Its Application for Copper Removal

Copper is toxic and is considered as the hazardous pollutant due to his stability in the environment. Current technologies used for its removal involve materials which can be difficult to synthesize, are expensive or are themselves potentially toxic. Natural clays are abundant worldwide, relatively cheap, possess sorption and ion exchange properties, are candidates as adsorbents. While the Cu(II) sorption capacity of raw bentonite is relatively low, modified bentonites represent a new class of sorbents for effective Cu(II) removal from wastewater. The present study investigates the influence of Algerian clay modification on the capacity of copper removal from water. This montmorillonite, which is a clay mineral of the smectite group, possesses silica tetrahedral sheets layered between alumina octahedral sheets. Several adsorbents were prepared from this bentonite by saturation with sodium, calcium and treatment with sulphuric acid to produce three adsorbents, ARS, ARC and ARH, respectively. The three materials obtained were tested for the Cu(II) adsorption from aqueous solutions. The adsorbents and metal interactions were studied under different conditions of interaction time, pH, concentration of metal ions and amount of clay. It was found that the interactions were dependent on pH, the uptake of pollutant was controlled by the amount of clay and the initial copper concentration. Langmuir and Freundlich models were fitted to experimental isotherms. The Langmuir model shows a better fit to the Cu ions adsorption isotherm for all systems. The largest adsorption capacity is observed for sodium homoionic clay. The Langmuir maximum sorption capacity of Cu(II) ions on ARH, ARC and ARS was found to be 17.241, 18.181 and 24.390 mg/g, respectively. The three adsorbents also showed a high efficiency in the Cu(II) adsorption from much diluted solutions. This work suggested that the modified clays can be promising candidates for the removal of copper ions from aqueous solutions.

Facile Synthesis of Calcite-Impregnated Hydrochar with High Sorption Capacity for Cu(II) from Aqueous Solution.

Calcite-impregnated hydrochar (Ca-HC) was successfully synthesized by a one-step hydrothermal method and used as an adsorbent for Cu(II) remediation. Characterization techniques showed that Ca-HC contained calcite and oxygen-containing functional groups. A series of Cu(II) sorption experiments onto Ca-HC showed that the initial Cu(II) concentration, contact time, sorption temperature, and initial pH of the solution influenced the sorption of Cu(II). The actual achievable sorption capacity of Ca-HC for Cu(II) was 130.57 mg g–1 at 303 K, and the sorption process obeyed the Langmuir model and pseudo-second-order kinetic equation. The precipitation and surface complexation rather than ion exchange were mainly ascribed to the removal of Cu(II) onto Ca-HC. The calcite provided the active site to produce posnjakite precipitation during the sorption process and enhance the sorption capacity of the hydrochar. Therefore, these results demonstrated that Ca-HC is an effective sorbent that can remove Cu(II) from water.

Sorption of Selected Heavy Metals with Different Relative Concentrations in Industrial Effluent on Biochar from Human Faecal Products and Pine-Bark.

The removal of heavy metals from effluents at source could reduce contamination of soil and water bodies. A batch sorption experiment was performed to determine the effects of feedstock of biochars pyrolysed at increasing temperature on sorption capacities of Cu, Cr and Zn from industrial effluent and aqueous solutions. Sewage sludge, latrine faecal waste and pine-bark biochars were used. The sorption data were fitted to the Langmuir isotherm. Maximum sorption capacities of latrine waste, sewage sludge and pine-bark biochar (350 °C) were, respectively, 313, 400 and 233 mg kg−1 for Zn, 102, 98.0 and 33.3 mg kg−1 for Cu, and 18.9, 13.8 and 67.1 mg kg−1 for Cr from industrial effluent. Conversely, sorption capacities from single metal solutions were 278, 227 and 104 mg Zn kg−1, 97.1, 137 and 21.3 mg Cu kg−1, 122, 106 and 147 mg Cr kg−1 on latrine waste, sewage sludge and pine-bark biochar, respectively. Step-wise regression analysis showed that the combined effects of ash, fixed C, pH influenced Zn sorption, ash and fixed C affected Cu sorption, and Cr sorption by ash and specific surface area of the biochar. The findings of the study imply that biochar from human faecal waste, particularly sewage sludge, has the potential to be utilized as sorbents of heavy metals from multiple metal effluent and that the sorption is affected by relative concentrations.

Valorization of Romanian silver fir tree bark (Abies alba Mill.) wastes as low-cost sorbent of Cu(II) ions from polluted waters.

Considering recycling as the first option in the hierarchy of sustainable waste management, and also the demand for efficient processes for wastewater treatment with reduced costs, the potential applicability of Romanian Abies alba bark, the main waste from the industrial processing of the wood of mature silver fir trees, as sorbent for Cu(II) has been studied in batch conditions. It was observed that the extent of Cu(II) sorption is strongly dependent on initial solution pH, sorbent dose, initial Cu(II) ion concentration, temperature and contact time. Equilibrium data fitted very well with both Langmuir and Freundlich isotherm models. The Langmuir maximum sorption capacity of Cu(II) ions on Abies alba bark waste was found to be 7.80 mg/g at 293 K. Kinetic studies showed a high affinity of the sorption experimental data to the pseudo-second order model. Gibbs free energy was spontaneous for all interactions and the sorption process exhibited endothermic enthalpy value. The waste of Abies alba bark was successfully used for the sorption removal of Cu(II) ions from industrial electroplating wastewaters.

Metal adsorption by agricultural biosorbents: Adsorption isotherm, kinetic and biosorbents chemical structures

Biosorption of Cu(II), Co(II) and Fe(III) ions from aqueous solutions by rice husk, palm leaf and water hyacinth was investigated as a function of initial pH, initial heavy metal ions concentration and treatment time. The adsorption process was examined by two adsorption isotherms: Langmuir and Freundlich isotherms. The experimental data of biosorption process were analyzed using pseudo-first order, pseudo-second order kinetic models. The equilibrium biosorption isotherms showed that the three studied biosorbents possess high affinity and sorption capacity for Cu(II), Co(II) and Fe(III) ions. Rice husk showed more efficiency than palm leaf and water hyacinth. Adsorption of Cu(II) and Co(II) was more efficient in alkaline medium (pH 9) than neutral medium due to the high solubility of metal ion complexes. The metal removal efficiency of each biosorbent was correlated to its chemical structure. DTA studies showed formation of metal complex between the biosorbents and the metal ions. The obtained results showed that the tested biosorbents are efficient and alternate low-cost biosorbent for removal of heavy metal ions from aqueous media.

Enhancing Sorption Capacities for Copper(II) and Lead(II) under Weakly Acidic Conditions by l-Tryptophan-Functionalized Graphene Oxide

l-Tryptophan functionalized graphene oxide (GO/l-Trp) was successfully synthesized via the nucleophilic substitution reaction. Its structure was characterized and the performances of GO/l-Trp in the sorption of Cu(II) and Pb(II), including the influence of contact time, initial pH of solution, temperature of the system, and initial metal concentration, were explored. The studies indicated that GO/l-Trp exhibited enhanced sorption capacities for Cu(II) and Pb(II) at the initial pH of 5 and 4, respectively, due to the increased sorption sites. The sorption of Cu(II) and Pb(II) were nearly completed within 40 min and fitted better with Lagergren pseudo-second-order kinetic model, indicating that Cu(II) and Pb(II) sorption on GO/l-Trp were chemical interactions. Langmuir model was more suitable to describe the sorption processes and sorption capacities were 588 mg·g–1 and 222 mg·g–1 for Cu(II) and Pb(II), respectively. Thermodynamic studies revealed that sorption were exothermic and spontaneous. Moreover, it ...

Removal of Heavy Metals from Aqueous Solution Using Natural and Fe(III) Oxyhydroxide Clinoptilolite

AbstractThe increasing levels of industrial wastewater released to the environment present a serious threat to human health, living resources, and ecological systems. Fe-modified zeolites were developed and tested for removal of Cu2+ and Zn2+ from contaminated water. The surfaces of the naturally occurring zeolite, clinoptilolite, were modified with Fe(III) oxyhydroxides using three different methods, denoted I, II, and III (FeCli1, FeCli2, and FeNaCli1, respectively). The oxyhydroxides were prepared in Method I using 0.1 M FeCl3·6H2O in an acetate buffer (pH = 3.6); in Method II, using 10ai] FeCl3·6H2O solution in 0.1 M KOH (pH = 10); and Method III was the same as Method I except the clinoptilolite was pretreated with NaCl. Newly synthesized materials from these three methods were then tested for their ability to enhance the sorption capacity for Cu and Zn compared to the natural sample (Cli). Powder X-ray diffraction measurements and the chemical composition of these modified samples confirmed that clinoptilolite maintained its structure while amorphous Fe3+ species were synthesized. The specific surface area (BET method) of both the natural and modified clinoptilolite increased by 2 and 7.5 times for Methods I and II, respectively. Scanning electron microscopy and energy dispersive X-ray spectroscopy revealed that CaO was formed during Method I (FeClii). Throughout the adsorption process, the hydrolysis of CaO and the release of OH− caused the precipitation of Cu and Zn hydroxide, which made the determination of the sorption capacity of FeClii impossible. This phenomenon was avoided in Method III (FeNaClii) because of the absence of exchangeable Ca2+. The adsorption experiments with Method II resulted in double-enchanced adsoprtion capacity. Laboratory batch experiments revealed that the sorption capacities increased in the following order: Cli < FeCli2 < FeNaCli1, for Cu: 0.121 mmol/g < 0.251 mmol/g < 0.403 mmol/g and for Zn: 0.128 mmol/g < 0.234 mmol/g < 0.381 mmol/g.

Sorption of Cu(II) Ions from Aqueous Solution with Synthesized B-Doped Heptazine-Based g-C/N/H Polymers

In this study, boron doped heptazine-based g-C/N/H polymers (B-doped heptazine-based g-C/N/H polymers) were synthesized by the pyrolysis process of the mixture of low cost H3BO3 and melamine. X-ray power diffractometer (XRD) and Fourier transform infrared spectroscopy (FT-IR) were applied to characterize the successful doping of B atoms into the nanostructure of the graphic-C3N4 (heptazine-based g-C/N/H polymers). The synthesized material was conducted to investigate the sorption capacity for Cu(II) ions from aqueous solution and the sorption conditions including the doped amount, the solution pH, the contact time, and initial concentration were optimized. The results indicated that the sorption process was dependent on solution pH and the optimum pH was from 3.0 to 6.0. The kinetics was well evaluated by pseudo-second-order which indicated that the main rate-determining step was controlled by the chemical sorption process. The maximum sorption capacity calculated from Langmuir model amounted to 149.3 mg g−1 with the initial concentration range from 80 ∼ 800 mg L−1. So, B-doped heptazine-based g-C/N/H polymers have the potential application as a low cost adsorbent for high concentration Cu(II) ions in aqueous solution.

Biosorptive removal of Pb(II) and Cu(II) from wastewater using activated carbon from cassava peels

The ability of activated carbon from cassava peels to remove heavy metals like Cu(II) and Pb(II) from hospital wastewater was investigated. The study showed that a pH of 8 was the best for the sorption of both metal ions onto the biosorbent. The time-dependent experiments for the metal ions showed that the binding of the metal ions to the biomass was rapid and occurred within 20–120 min. Sorption efficiency increased with a rise in adsorbent dosage. It increased from 12 to 73 % for Pb(II) and 26 to 79 % for Cu(II) when the adsorbent dose increased from 2 to 12 g. An increase in temperature led to an increase in sorption for both metal ions. The Langmuir model showed that the biomass has a higher sorption capacity for Cu(II) than Pb(II), with qm = 5.80 mg g−1 for Pb(II) and 8.00 mg g−1 for Cu(II). The Freundlich isotherm Kf was 1.4 for Pb(II) and 1.8 for Cu(II), indicating a preferential sorption of Cu(II) onto the biosorbent. Adsorption capacity was found to decrease with an increase in particle sizes. Sorption occurred by physical mechanisms and was mainly controlled by intraparticle diffusion.

Sorption of heavy metal ions by glass beads-immobilized calix[4]arenes derivative

Glass beads (GB) immobilized, 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-dihydroxycalix[4]arene (CA) are prepared and used as a new sorbent in sorption study of removal heavy metal ions. A calixarene derivative bonded to amino-functionalized glass beads sorbent was synthesized via a self assembly technique for sorbent of selected heavy metal ions in aqueous. In order to absorb selected heavy metal ions in aqueous, a calixarene derivative bonded to amino-functionalized glass beads sorbent was synthesized via a self assembly technique. The sorbent which is named GB-APTS-CA was characterized using infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), elemental analysis and thermal analysis (TGA/DTG). The influences of some experimental parameters including pH of the sample solution, weight of sorbent, concentration and temperature have been investigated. The sorption data were evaluated using the Langmuir, Freundlich and Dubinin Radushkevich (D-R) isotherm. The obtained maximum sorption capacity for Cu(II), and Pb(II) is 0.06 mmol g−1 and 0.02 mmol g−1, respectively. Thermodynamic parameters such as the standard free energy change (ΔG○), enthalpy change (ΔH○) and entropy change (ΔS○) were calculated to determine the nature of sorption process. Thus, GB-APTS-CA is favorable and useful for the removal of Cu(II) and Pb(II) metal ions.

THIOCYANATE-ASSISTED SOLID PHASE ENRICHMENT OF Cu(II) USING PYRIDINE DERIVATIVE WITH X-RAY CRYSTALLOGRAPHIC EVIDENCE

Equimolar mixture of pyridine-2,6-dimethanol (PDM), and thiocyanate ion immobilized on silica serves as an efficient sorbent for selective retention of Cu(II) from other associated metal ions at µg g−1 level. The maximum sorption capacity for Cu(II) was found as 2.44 mmol g−1 at pH 6.0. The sorbed Cu(II) was completely eluted with 3 mol L−1 HNO3 and measured with a flame atomic absorption spectrometer (FAAS). The structure of the extracted Cu(II) complex was confirmed by single-crystal X-ray structure analysis and Fourier transform-infrared (FT-IR) spectroscopy. Thermogravimetric analysis (TGA) of the isolated Cu(II) complex was performed to determine its thermal stability at the extraction temperature. The three sigma detection limit (N = 15) of the method is 0.6 µ g mL−1 with a relative standard deviation (RSD) of 0.1% (N = 15). Pre-concentration factor of the method is 133. Slight interference from Mn2+ ion was eliminated by prior oxidation with potassium periodate. The developed method was tested for trace level separation and estimation of Cu(II) in certified reference materials and environmental samples. [Supplementary materials are available for this article. Go to the publisher's online edition of Chemical Engineering Communications for the following free supplemental resources: two tables providing details of the bond lengths and bond angles of the Cu(II) complex.]

Removal of Cu(II) and Fulvic Acid by Graphene Oxide Nanosheets Decorated with Fe3O4 Nanoparticles

Graphene oxide/Fe(3)O(4) (GO/Fe(3)O(4)) composites were synthesized and characterized by scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The removal of Cu(II) and a natural organic macromolecule (fulvic acid (FA)) by GO/Fe(3)O(4) was investigated. The mutual effects of FA/Cu(II) on Cu(II) and FA sorption onto GO/Fe(3)O(4), as well as the effect of pH, ionic strength, FA/Cu(II) concentrations, and the addition sequences of FA/Cu(II) were examined. The results indicated that Cu(II) sorption on GO/Fe(3)O(4) were strongly dependent on pH and independent of ionic strength, indicating that the sorption was mainly dominated by inner-sphere surface complexation rather than outer-sphere surface complexation or ion exchange. The presence of FA leads to a strong increase in Cu(II) sorption at low pH and a decrease at high pH, whereas the presence of Cu(II) led to an increase in FA sorption. The adsorbed FA contributes to the modification of sorbent surface properties and partial complexation of Cu(II) with FA adsorbed. Different effects of FA/Cu(II) concentrations and addition sequences on Cu(II) and FA sorption were observed, indicating the difference in sorption mechanisms. After GO/Fe(3)O(4) adsorbed FA, the sorption capacity for Cu(II) was enhanced at pH 5.3, and the sorption capacity for FA was also enhanced after Cu(II) sorption on GO/Fe(3)O(4). These results are important for estimating and optimizing the removal of metal ions and organic substances by GO/Fe(3)O(4) composites.

AsO4로 치환된 슈베르트마나이트의 중금속 흡착 특성

산성광산배수에 존재하는 <TEX>$AsO_4$</TEX>는 슈베르트마나이트의 <TEX>$SO_4$</TEX>를 치환하여 강하게 흡착되고 이로 인하여 슈베르트마나이트가 쉽게 침철석으로 전이되지 않게 해준다. 이러한 슈베르트마나이트에 대하여 주요 중금속 흡착에 대한 연구는 일부 이루어져 있으나 실제 <TEX>$AsO_4$</TEX>로 치환된 슈베르트마나이트에 대한 흡착 특성에 대해서는 기존에 연구된 바가 없다. 본 연구에서는 <TEX>$AsO_4$</TEX>로 치환된 슈베르트마나이트에 대하여 Cu, Pb, Zn 등의 대표적인 중금속 세 종류에 대하여 각 중금속의 농도가 3, 10, 30, 100 mg/L에 대하여 pH 4와 6의 두 범위에서 시간에 따른 흡착 실험을 실시하였다. 흡착 실험 결과 모든 중금속에 대하여 pH 6인 경우 pH 4에 비하여 흡착량이 큰 범위로 증가하였다. 전체적인 흡착량에 있어서 두 pH 범위에서 모두 Pb가 가장 큰 흡착량은 보였으며 Cu와 Zn의 흡착량은 비슷하였다. 시간에 따른 흡착속도는 전체적으로 모든 농도에 대하여 시간이 증가하면서 흡착량은 증가하였으나 Zn의 경우 대부분의 흡착이 초기에 일어나 시간이 지나면서 뚜렷한 흡착의 증가는 일어나지 않았다. 이러한 흡착량 증가는 특히 고농도의 용액인 100 mg/L에서 그 증가하는 양상이 뚜렷하였다. 다양한 흡착속도 모델을 적용한 결과 <TEX>$AsO_4$</TEX>로 치환된 슈베르트마나이트에서 일어나는 중금속의 흡착속도는 아마도 확산에 의하여 주로 좌우되는 것으로 나타났다. 기존의 연구에서 순수한 슈베르트마나이트가 pH 6에서 세 중금속에 대하여 거의 비슷한 흡착량을 보이고 pH 4에서는 Cu와 Pb가 비슷하게 Zn보다 높은 흡착량을 보이는 것을 고려하면 본 연구 결과 <TEX>$AsO_4$</TEX> 슈베르트마나이트는 확연하게 다른 흡착 경향을 보이고 이는 <TEX>$AsO_4$</TEX>가 슈베르트마나이트의 <TEX>$SO_4$</TEX>를 치환됨으로 인하여 슈베르트마나이트의 표면 및 흡착특성이 달라짐을 지시한다. 이는 산성광산배수에서 <TEX>$AsO_4$</TEX>의 흡착이 슈베르트마나이트의 안정성뿐만 아니라 각 중금속의 거동에도 큰 영향을 줄 수 있음을 보여준다. The <TEX>$AsO_4$</TEX> ion in acid mine drainage has been known to substitute for <TEX>$SO_4$</TEX> in schwertmannite and prevent schwertmannite from being converted to goethite. There have been studies on the heavy metal sorption on schwertmannite, but no experimental results have been reported on the characteristics of heavy metal sorption on <TEX>$AsO_4$</TEX>-substituted schwertmannite. In this study, we conducted sorption experiments of Cu, Pb, and Zn on the <TEX>$AsO_4$</TEX>-substituted schwertmannite at pH 4 and 6 in the solution of 3, 10, 30, and 100 mg/L concentrations. For all heavy metals, the sorbed heavy metals significantly increase at pH 6 compared with at pH 4. At both pH 4 and 6, Pb shows the highest sorption capacity and those of Cu and Zn are similar. With increasing time, the sorbed heavy meal contents increase too. However, in the case of Zn, the most sorptions occur at the initial stage and no significant increase is observed with time. Among the concentration ranges in which we conducted the experiment, the increasing trend is clear in high concentrated solutions such as 100 mg/L. We applied several sorption kinetic model and it shows that the diffusion process may be the most important factor controlling the sorption kinetics of Cu, Pb, and Zn on <TEX>$AsO_4$</TEX>-substituted schwertmannite. Considering the previous results that pure schwertmannite has similar sorption capacity for all three heavy metals at pH 6 and has higher sorption capacity for Cu and Pb than Zn at pH 4, our experiments indicates that substitution of <TEX>$AsO_4$</TEX> for <TEX>$SO_4$</TEX> on schwertmannite changes surface and sorption characteristics of schwertmannite. It also shows that <TEX>$AsO_4$</TEX> contributes not only to the stability of schwertmannite, but also to the mobility of heavy metals in acid mine drainage.