Copper Sorption Capacity Research Articles

OPTIMIZATION OF PROCESS PARAMETERS FOR THE REMOVAL OF COPPER METAL USING BROWN ALGA PADINA GYMNOSPORA.

The biosorption of copper on Padina gymnospora was investigated in a batch system. The relationship between the response and the independent variables was developed via the quadratic approximating function of copper sorption capacity of sorbent. From this study, it can be concluded that the copper can be removed by using a brown alga P.gymnospora which is abundant and cheaply available alga. Dry biomass of P.gymnospora proves to be cost effective and efficient to eliminate heavy metal especially copper for aquatic effluents and the process is feasible, reliable and eco-friendly. This brown alga can be recommended for the removal of copper from industrial effluents.

Chitosan-based green sorbent material for cations removal from an aqueous environment

Abstract Herein, we report the development and characterization of a green sorbent material. For the said purpose, the chitosan’s capacity of cation sorption was enhanced by incorporating thiocarabamate group, which ultimately increases active sites for attracting the cationic species. The process was carried out by utilizing acrylomorpholine, carbon disulfide and chitosan in a single stage process. The product (CH-ATC) acquired was well characterized with 13C NMR (solid-form), FTIR spectroscopy, elemental investigation, thermogravimetic analysis and scanning electron microscopy. The novel product’s ability of sorption was evaluated by applying it to lead and copper solution. The modified chitosan (CH-ATC) exhibited greater sorption capacity of lead (1.58 mmol g−1) over raw chitosan when applied to aqueous solution based on Langmuir sorption isotherm. The new material also showed reasonable sorption capacity for copper (1.25 mmol g−1). The experimentally obtained results associated well to Langmuir model than Temkin and Freundlich isotherms using linear regression method. Different linearization of Langmuir model showed different error functions and isothermal parameters. The nonlinear regression analysis showed lower values of error functions as compared to linear regression analysis. The chitosan with thiocarbamate chain is outstanding material for selected cations decontamination form aqueous solution.

Characterization and deployment of surface-engineered chitosan-triethylenetetramine nanocomposite hybrid nano-adsorbent for divalent cations decontamination

The latency of toxic cations in the ecosystem poses serious ecological problems due to its bioaccumulation potential and toxicity to living organisms. The effective removal of these wastewater cations releasing from multi-industries is a bottleneck issue. Therefore, an attempt has been made to design a suitable sorbent for cations sorption from the aqueous environment. The chitosan biopolymer was modified with triethylenetetramine to incorporate active sites in the polymeric sequence to boost up its cations sorption capacity. Triethylenetetramine molecule anchoring chitosan (CH-TET) was authenticated through elemental assay, Fourier-transform infrared spectroscopy and 13C NMR in solid-state, scanning electron microscopy and thermal analysis. The sorption of lead (1.94 mmol g−1), copper (2.79 mmol g−1) and nickel (1.53 mmol g−1) was carried out using the functionalized chitosan from aqueous solution, which showed higher sorption capacity for lead and copper than the pristine chitosan in terms of Langmuir sorption isotherm. To scrutinize the mechanism of sorption and energy of interaction between sorbent and sorbate, Langmuir, Temkin, and Freundlich isotherm models were used for sorption study. The Langmuir model showed the best fitting to the results based on lower error function values and a higher correlation coefficient (R2). It can be concluded that the triethylenetetramine-modified chitosan might be considered as an effective sorbent for cations removal from industrial wastewater.

Chitosan-Based Bio-Composite Modified with Thiocarbamate Moiety for Decontamination of Cations from the Aqueous Media.

Herein, we report the development of chitosan (CH)-based bio-composite modified with acrylonitrile (AN) in the presence of carbon disulfide. The current work aimed to increase the Lewis basic centers on the polymeric backbone using single-step three-components (chitosan, carbon disulfide, and acrylonitrile) reaction. For a said purpose, the thiocarbamate moiety was attached to the pendant functional amine (NH2) of chitosan. Both the pristine CH and modified CH-AN bio-composites were first characterized using numerous analytical and imaging techniques, including 13C-NMR (solid-form), Fourier-transform infrared spectroscopy (FTIR), elemental investigation, thermogravimetric analysis, and scanning electron microscopy (SEM). Finally, the modified bio-composite (CH-AN) was deployed for the decontamination of cations from the aqueous media. The sorption ability of the CH-AN bio-composite was evaluated by applying it to lead and copper-containing aqueous solution. The chitosan-based CH-AN bio-composite exhibited greater sorption capacity for lead (2.54 mmol g−1) and copper (2.02 mmol g−1) than precursor chitosan from aqueous solution based on Langmuir sorption isotherm. The experimental findings fitted better to Langmuir model than Temkin and Freundlich isotherms using linear regression method. Different linearization of Langmuir model showed different error functions and isothermal parameters. The nonlinear regression analysis showed lower values of error functions as compared with linear regression analysis. The chitosan with thiocarbamate group is an outstanding material for the decontamination of toxic elements from the aqueous environment.

Biochar colloids and their use in contaminants removal

In this study, we report on the extraction, characterization, and potential applications of colloidal biochar derived from pyrolyzed wood—an untapped source of carbonaceous particles. A series of characterizations was performed on biochar colloids to unravel their colloidal properties and surface chemistry through which it was found that they have a net negative charge and are stable between pH 3 and 10. Moreover, our initial toxicity tests showed that biochar colloids themselves are not toxic and they can be used in remediation applications, which led us to investigate (1) their copper sorption, a model inorganic contaminant, in a scenario that biochar colloids are released into the environment and (2) their potential use in organic pollutants adsorption and degradation. Copper sorption studies showed that biochar colloids have a copper sorption capacity as high as 22 mg $$\hbox {g}^{-1}$$ in sub-ppm copper solutions. This increased the acute 48 h lethal concentration ( $$\hbox {LC}_{50}$$ ) of copper for Daphnia magna by 21 ppb, which is comparable to the previously reported effect by dissolved organic matter. Adsorption and degradation of methylene blue (MB), an often-used proxy for organic contaminants in water, were studied by coupling the biochar colloids to positively charged $$\hbox {TiO}_{2}$$ nanoparticles and using it as a photocatalyst. The hybrid MB photodegradation efficiency was $$21\%$$ higher than that of $$\hbox {TiO}_{2}$$ nanoparticles alone. Enhancement of demethylation is proposed as the main degradation mechanism of MB, as confirmed by liquid chromatography–mass spectroscopy (LC/MS), and the positive impact of biochar colloids is ascribed to their abundant adsorption sites, which may facilitate MB adsorption and its photocatalytic degradation.

Assessing the effect of pyrolysis temperature on the molecular properties and copper sorption capacity of a halophyte biochar

The capacity of biochar to take up heavy metals from contaminated soil and water is influenced by the pyrolysis temperature. We have prepared three biochar samples from Jerusalem artichoke stalks (JAS) by pyrolysis at 300, 500 and 700 °C, denoted as JAS300, JAS500, and JAS700, respectively. A variety of synchrotron-based techniques were used to assess the effect of pyrolysis temperature on the molecular properties and copper (Cu) sorption capacity of the samples. The content of oxygen-containing functional groups in the biochar samples decreased, while that of aromatic structures and alkaline mineral components increased, with a rise in pyrolysis temperature. Scanning transmission X-ray microscopy indicated that sorbed Cu(II) was partially reduced to Cu(I), but this process was more evident with JAS300 and JAS700 than with JAS500. Carbon K-edge X-ray absorption near edge structure spectroscopy indicated that Cu(II) cations were sorbed to biochar via complexation and Cu-π bonding. With rising pyrolysis temperature, Cu(II)-complexation weakened while Cu-π bonding was enhanced. In addition, the relatively high ash content and pH of JAS500 and JAS700 facilitated Cu precipitation and the formation of langite on the surface of biochar. The results of this investigation will aid the conversion of halophyte waste to useable biochar for the effective remediation of Cu-contaminated soil and water.

Metal removal by pine bark compost using a permeable reactive barrier device at laboratory scale

Environmental contextPermeable reactive barriers are a developing technology to clean up contaminated groundwater. The contaminant plume moves through a reactive material placed below ground that retains or degrades the pollutants. This study shows that pine bark compost strongly adsorbs and retains metals, mostly by interaction with the organic matter of the compost, and thereby serves as a suitable reactive filler material to clean up contaminated groundwater. AbstractPermeable reactive barriers (PRBs) are in situ systems for groundwater remediation, consisting of a screen perpendicular to the flow of contaminated groundwater filled with a material capable of retaining or degrading pollutants. The use of waste materials as reactive substrates in PRBs is of particular interest owing to the possibility of their reutilisation and their generally lower cost. With this aim, the sorption capacity for copper, nickel and zinc of pine bark compost (PBC) was evaluated in competitive batch experiments that showed that metal adsorption is a rapid process and that adsorption capacities followed the sequence Cu>Ni>Zn, with maximum adsorption capacities of 0.157mmolg–1 for Cu2+, 0.052mmolg–1 for Ni2+, 0.046mmolg–1 for Zn2+ and 0.259mmolg–1 for the sum of the three metals. Subsequently, a dynamic percolation experiment was carried out with a multi-metal solution prepared with 50mgL–1 of Cu, Ni and Zn in 0.01M KNO3 as saline background, using an experimental device that reproduced a PRB at laboratory scale. Metal retention ranged from 92 to 99% (Cu>Ni>Zn). The metals were strongly retained by the filling material because low desorption was detected by subsequent leaching with 0.01M KNO3 (0.3, 1.8 and 4.1% of the previously adsorbed metal for Cu, Ni and Zn respectively). The results show that PBC is a potential candidate as a filler material for the retention of cationic metals in permeable reactive barriers.

Preparation and Metal Removal from Chitosan/PEG Blend

Recently the removal of trace element using biodegradable polymers is important. This paper involves the preparation and evaluation of chitosan/ polyethylene glycol blend served as a heavy metal removal system. The author has prepared the various blending system with different composition ratios and different crosslinking density. Experimental results indicate that the swelling degree and thermal property of the blend film are correlated with blend ratio and crosslink density. The blend film is then investigated its metal-binding performance. Copper sorption capacity is one of major potential applications in a field of wastewater treatment.

Sorption of Cu(II) Ions on Chitosan-Zeolite X Composites: Impact of Gelling and Drying Conditions.

Chitosan-zeolite Na-X composite beads with open porosity and different zeolite contents were prepared by an encapsulation method. Preparation conditions had to be optimised in order to stabilize the zeolite network during the polysaccharide gelling process. Composites and pure reference components were characterized using X-ray diffraction (XRD); scanning electron microscopy (SEM); N2 adsorption–desorption; and thermogravimetric analysis (TG). Cu(II) sorption was investigated at pH 6. The choice of drying method used for the storage of the adsorbent severely affects the textural properties of the composite and the copper sorption effectiveness. The copper sorption capacity of chitosan hydrogel is about 190 mg·g−1. More than 70% of this capacity is retained when the polysaccharide is stored as an aerogel after supercrititcal CO2 drying, but nearly 90% of the capacity is lost after evaporative drying to a xerogel. Textural data and Cu(II) sorption data indicate that the properties of the zeolite-polysaccharide composites are not just the sum of the properties of the individual components. Whereas a chitosan coating impairs the accessibility of the microporosity of the zeolite; the presence of the zeolite improves the stability of the dispersion of chitosan upon supercritical drying and increases the affinity of the composites for Cu(II) cations. Chitosan-zeolite aerogels present Cu(II) sorption properties.

Time evolution of the general characteristics and Cu retention capacity in an acid soil amended with a bentonite winery waste

The effect of bentonite waste added to a “poor” soil on its general characteristic and copper adsorption capacity was assessed. The soil was amended with different bentonite waste concentrations (0, 10, 20, 40 and 80 Mg ha−1) in laboratory pots, and different times of incubation of samples were tested (one day and one, four and eight months). The addition of bentonite waste increased the pH, organic matter content and phosphorus and potassium concentrations in the soil, being stable for P and K, whereas the organic matter decreased with time. Additionally, the copper sorption capacity of the soil and the energy of the Cu bonds increased with bentonite waste additions. However, the use of this type of waste in soil presented important drawbacks for waste dosages higher than 20 Mg ha−1, such as an excessive increase of the soil pH and an increase of copper in the soil solution.

Single-step modification of chitosan for toxic cations remediation from aqueous solution

Chitosan was chemically modified with 4-acryloylmorpholine in order to enhance Lewis basic centres in polymeric chain for cations removal. The new material was characterized using elemental analysis, infrared and 13C NMR in solid state and was applied for sorption of copper, lead and cadmium from aqueous solutions. The kinetic parameters were evaluated using pseudo-first- and second-order reaction. Kinetic results showed that the sorption process was best described by the pseudo-second-order model. The experimental data were adjusted to the Langmuir, the Freundlich and the Temkin sorption isotherms using both linear and nonlinear regression methods. The material showed the maximum sorption capacity for copper (3.35 mmol g−1), than lead (1.60 mmol g−1) and cadmium (0.74 mmol g−1), obtained through the Langmuir sorption isotherm. The Langmuir model provided the lowest error values and fit better to the experimental data compared with other models.

Changes in the sorption, desorption, distribution, and availability of copper, induced by application of sewage sludge on Chilean soils contaminated by mine tailings

The effect of mine tailings and sewage sludge was evaluated on sorption, desorption, availability and distribution of copper in two soils, one high (sandy soil) and one low in copper (clay soil). In both soils contaminated by mine tailings the copper sorption capacity and the affinity of the substrate for the metal decreased substantially compared to the uncontaminated soils, however, the sorption remained always high in the clay soil substrates. In the substrates with sandy soil, the high Cu content and lower clay content were determining factors in the lower magnitude of the sorption. Similarly, metal desorption was closely related to these two parameters, and it was higher in clay soil with lower pH. In general, the application of sewage sludge favored the sorption of Cu in soils contaminated and uncontaminated with mine tailings, and in all cases desorption decreased, an effect that remained for at least 30 days. Simple extraction of Cu with CaCl2 and diethylenetriaminepentaacetic acid gave contradictory results, so a careful choice of the procedure is required, depending on the level of metal in the soil and on the acting principle of the extracting agent. In that relation, more complete information on the changes in the metal forms was obtained by application of the sequential extraction procedure proposed by the European Community Bureau of Reference.

Sorption behaviour of copper on chemically modified chitosan beads from aqueous solution

In order to increase the copper sorption capacity (SC) of raw chitosan beads (CB), they were chemically modified into protonated chitosan beads (PCB), carboxylated chitosan beads (CCB) and grafted chitosan beads (GCB) which showed a significant SC of 52, 86 and 126 mg/g respectively while raw chitosan beads (CB) displayed only 40 mg/g. Among the sorbents studied, GCB experienced a higher SC than CB, PCB and CCB. Sorption experiments were performed by varying contact time, pH, presence of co-anions, different initial copper concentrations and temperature for optimization. The nature and morphology of the sorbents were discussed using FTIR and SEM analysis. The copper uptake onto PCB, CCB and GCB obeys the Freundlich isotherm. Thermodynamic studies revealed that the nature of copper sorption is spontaneous and endothermic.

Adsorption of copper onto agriculture waste materials

Mining activities generate large amounts of wastewater, which contain heavy metals of elevated concentration according to legislative threshold values. Therefore, treatment is necessary, and there has been a recent focus on more environmentally friendly methods. One of these is biosorption, where heavy metals are adsorbed from the wastewater via materials of biological origin. In this work copper sorption capacity, kinetics and isotherms of different low-cost residual agricultural materials was studied. Seven different materials were investigated: peanut shells, nut shells, plum seeds, eucalyptus bark, olive pips, peach stones, and pine sawdust. The best sorption results were obtained in acidic pH for olive pips, peach stones and pine sawdust. Furthermore, it was observed that at higher pH, a longer duration of time is required before equilibrium is established. In general, the better biosorbents were found to be peach stones and pine sawdust with a sorption capacity at acidic pH around 10–15 mg Cu g −1 biosorbent. In addition it was found, that the Ho and McKay second order model described the sorption kinetics very satisfactorily. Both Langmuir and Freundlich models described the equilibrium sorption isotherms well for the biosorbents studied – with the last model being slightly better.

Functionalized macroporous copolymer of glycidyl methacrylate: The type of ligand and porosity parameters influence on Cu(II) ion sorption from aqueous solutions

The removal of heavy metals from hydro-metallurgical and other industries' wastewaters, their safe storage and possible recovery from waste- water streams is one of the greater ecological problems of modern society. Conventional methods, like precipitation, adsorption and biosorption, electrowinning, membrane separation, solvent extraction and ion exchange are often ineffective, expensive and can generate secondary pollution. On the other hand, chelating polymers, consisting of crosslinked copolymers as a solid support and functional group (ligand), are capable of selectively loading different metal ions from aqueous solutions. In the relatively simple process, the chelating copolymer is contacted with the contaminated solution, loaded with metal ions, and stripped with the appropriate eluent. Important properties of chelating polymers are high capacity, high selectivity and fast kinetics combined with mechanical stability and chemical inertness. Macroporous hydrophilic copolymers of glycidyl methacrylate and ethylene glycol dimethacrylate modified by different amines show outstanding efficiency and selectivity for the sorption of precious and heavy metals from aqueous solutions. In this study poly(GMA-co-EGDMA) copolymers were synthesized with different porosity parameters and functionalized in reactions with ethylene diamine (EDA), diethylene triamine (DETA) and triethylene tetramine (TETA). Under non-competitive conditions, in batch experiments at room temperature, the rate of sorption of Cu(II) ions from aqueous solutions and the influence of pH on it was determined for four samples of amino-functionalized poly(GMA-co-EGDMA). The sorption of Cu(II) for both amino-functionalized samples was found to be very rapid. The sorption half time, t1/2, defined as the time required to reach 50% of the total sorption capacity, was between 1 and 2 min. The maximum sorption capacity for copper (2.80 mmol/g) was obtained on SGE-10/12-deta sample. The sorption capacity of Cu(II) ions increases with increasing pH and has maximum at pH ~5. In the experimental pH range, the maximum sorption capacity of Cu(II) ions again is reached on SGE-10/12-deta. By comparing literature data and obtained results it is possible to conclude that amino-functionalized macroporous copolymers based on glycidyl methacrylate are efficient for sorption of Cu(II) ions from aqueous solutions and sorption capacity for copper mostly depends on type of amine with which the basic copolymer is functionalized.

Comparison of Copper Sorption on Lignite and on Soils of Different Types and Their Humic Acids

We compared the sorption of copper on South Moravian lignite with that on several soils from Slovakia, using batch adsorption at a laboratory temperature of 25°C followed by a two-step desorption procedure. The results confirmed that lignite has a copper-sorption capacity and copper-binding strength that is comparable to or better than that of the Slovakian soils that we investigated. We compared these results with previously obtained data for sorption on humic acids (HA) isolated from lignite and soils. Although soil constituents other than HA, such as fulvic acids and mineral particles, also control metal sorption, HA bind copper at higher capacity and with greater strength than do the whole matrices of the soils we tested, and lignite showed a greater binding strength for copper than any of these soils. Our results thus far indicate that natural lignite mined in the Czech Republic, or lignite-derived HA, are potential agents for in situ soil remediation.

Determination of trace copper in water samples by flame atomic absorption spectrometry after preconcentration on a phosphoric acid functionalized cotton chelator

This paper reports the preparation of a phosphorylated cotton chelator (PCC) by solid phase esterification of phosphoric acid (PA) onto defatted cotton fibres using urea as the catalyst. The synthesized PCC was employed for the preconcentration of copper from water samples prior to its determination by flame atomic absorption spectrometry (FAAS). The preconcentration of copper was studied under both batch and column techniques. The pH range for the quantitative preconcentration of copper was 4.0-7.0. The sorption time required for each sample was less than 30 min by the batch method. The copper sorption capacity of the PCC was found to be 15.3 mg/g at the optimum pH value. Elution with 1.0 mol dm-3 hydrochloric acid was found to be quantitative. Feasible flow rates of the copper solution for quantitative sorption onto the column packed with PCC were 0.5-4.0 ml min-1, whereas the optimum flow rate of the hydrochloric acid solution for desorption was less than 1.5 ml min-1. An 80-fold preconcentration factor could be achieved under the optimum column conditions. The tolerance limits for common metal ions on the preconcentration of copper and the number of times of column reuse were investigated. The proposed method was successfully applied for the preconcentration and determination of trace copper in natural and drinking water samples by FAAS.

Copper removal from aqueous solutions by sugar beet pulp treated by NaOH and citric acid

Sugar beet pulp was converted into effective copper sorption material by treating subsequently with NaOH and citric acid. Compared with the untreated sugar beet pulp, the cation exchange capacity of the modified sugar beet pulp increased from 0.86 to 3.21 mequiv. g −1. Swelling capacity and COD values of modified sugar beet pulp were found to be decreased in the ratio of 38% and 61%, respectively, compared to the corresponding values of native sugar beet pulp, meaning that modification causes stabilization. Sorption characteristics of the modified sugar beet pulp towards copper ions were studied with batch experiments. Pseudo-first, pseudo-second-order and intraparticle kinetic models were applied to the kinetic data and it was found that the sorption processes followed the pseudo-second-order rate kinetics with activation energy of 16.34 kJ mol −1. The equilibration data fit best with the Langmuir isotherm the maximum copper sorption capacity of which is 119.43 mg g −1. The mean free energy of copper sorption process calculated from Dubinin–Radushkevich model and the Polanyi potential concept was found to be in the range of 10.91–11.95 kJ mol −1 showing that the main mechanism governing the sorption process is ion exchange. The negative values found for enthalpy change (−14.797 kJ mol −1 over the range of 25–55 °C) and free energy change (−19.361 kJ mol −1 for 25 °C) indicate that the sorption process is exothermic and spontaneous in nature.

SORPTION OF COPPER (II) AND NONIONIC SURFACTANT BY ION EXCHANGERS AND ACTIVATED CARBON

Ion exchange resins, which are widely used for the removal of copper (II) ions from effluents, can also sorb nonionic surfactants entering into the wastewater with copper (II) ions simultaneously after various industrial processes. The study of equilibrium sorption of copper (II) and nonionic surfactant Lutensol AO‐10 under laboratory conditions by different types of ion exchangers and activated carbon has shown that the Purolite S950 chelating ion exchanger has the highest sorption capacity for copper (II) ions. Ion exchangers with carboxylic functional groups demonstrate the highest affinity for nonionic surfactant. Purolite C107E weak acid cation exchanger could be suitable for the cosorption of copper (II) ions and nonionic surfactant Lutensol AO‐10. Kinetic study of this ion exchange resin leads to a conclusion that the sorption of copper (II) ions was a fast process, and after 30 min the equilibrium was attained. When the concentration of copper (II) solution decreases, difference between the sorption capacity of various ion exchangers decrease. The influence of nonionic surfactant on the sorption of copper (II) is insignificant.

Effect of Dissolved Organic Matter on Copper - Zinc Competitive Adsorption by a Sandy Soil at Different pH Values

The effect of dissolved organic carbon from sewage sludge on copper and zinc adsorption and interaction on samples from the surface layer (0 - 10 cm) of a sandy soil (Gleyic Podzol) were studied at two pH levels (4 and 7). This soil presented acidification hazards and sewage sludge with a high content of Cu and Zn was used as a fertilizer. Soil samples were treated by solutions of Cu and Zn as nitrate salts with concentration levels up to 30 mg l−1 in a Ca(NO3)2 background at a constant level (180 mg l−1) of dissolved organic carbon (DOC). Copper and zinc sorption capacity decreased in the presence of DOC. As the pH increased, the decrease in Cu adsorption due to interaction with DOC was more obvious. Conversely, without addition of DOC, Cu and Zn adsorption increased with pH. More Cu than Zn was adsorbed. Soil sorption of these cations was described by equilibrium isotherms that fitted both Langmuir and Freundlich type equations, presenting however a better fit to the Freundlich equation (R2>98%). Adsorption dependence on DOC was more noticeable at pH 7.