Magnetic nanostructures functionalized with a derived lysine coating applied to simultaneously remove heavy metal pollutants from environmental systems

ABSTRACT

The pollution of environmental systems with heavy metals is becoming a serious problem worldwide. These contaminants are one of the main issues in sludge (which is considered waste) and can even have harmful effects if the sludge is not treated properly. Thus, the development of a novel functional magnetic nanoadsorbent based on a derived lysine is reported here, which can be efficiently applied for metal removal from sludge. Magnetic nanoparticles were coated with silica layer and further modified by covalent bonding of derived lysine. The morphology of the nanomaterial, its nano-size and the silica layer thickness were analyzed by transmission electron microscopy. The successful silanization of the lysine derivative to the silica-coated magnetic nanostructures was investigated by several physicochemical characterization techniques, while the magnetic properties were measured with a vibrating sample magnetometer. The synthesized nanostructures were used as adsorbents for simultaneous removal of most critical heavy metals (Cr, Zn, Cu) from real complex sludge suspensions. The main practical adsorption parameters, pH of the native stabilized sludge, adsorbent amount, time, and adsorbent regeneration were investigated. The results show promising adsorption properties among currently available adsorbents (the total equilibrium adsorption capacity was 24.5 mg/g) from the sludge with satisfactory nanoadsorbent reusability and its rapid removal. The stability of the nanoadsorbent in the sludge, an important but often neglected practical parameter for efficient removal, was verified. This work opens up new possibilities for the development of high-quality magnetic nanoadsorbents for metal pollutants applied in various complicated environmental fields and enables waste recovery.     

Facile preparation of magnetic sodium alginate/carboxymethyl cellulose composite hydrogel for removal of heavy metal ions from aqueous solution

A novel magnetic polysaccharide composite hydrogel was successfully constructed by using sodium alginate (SA) and carboxymethyl cellulose (CMC) as the backbone and filled with in situ Fe₃O₄ nanoparticles, which was then employed for removal of heavy metal ion from aqueous solution. The obtained magnetic SA/CMC composite hydrogel was characterized by Fourier transform infrared spectroscopy, fluorescence microscope, thermogravimetric and vibrating sample magnetometer. Effect of contact time, pH and adsorbent dosage on the adsorption of heavy metal ions by the magnetic SA/CMC hydrogel have also been studied. The results show that the prepared magnetic SA/CMC hydrogel can be effectively utilized in the removal of heavy metal ions from aqueous solution. The maximal adsorption capacity of Mn(II), Pb(II), and Cu(II) as calculated from the Langmuir model were 71.83, 89.49, and 105.93 mg/g, respectively. The adsorption process of the magnetic SA/CMC hydrogel on the heavy metal ions can be attributed to ion exchange and chemical adsorption. What’s more, the magnetic hydrogel exhibited high efficiency after four cycles, which indicating it offers great potential for practical application in the removal of heavy metal ions from aqueous solution.

     

Water-soluble magnetic-carbon nanotubes nanocomposites for efficient adsorption of Cu(II) from aqueous solution

In this study, the water-soluble magnetic-multi-walled carbon nanotubes nanocomposites were fabricated via a facile and efficient approach and were characterized by X-ray diffraction, energy-dispersive X-ray, and transmission electron microscopy in detail. The nanocomposites could be employed as an effective adsorbent for removal of heavy metal ions, Cu(II) ions, from aqueous solution. It is noteworthy that the novel adsorbent displayed good water-dispersibility, rapid absorption rate, high absorption capacity, and convenient magnetic separation. Furthermore, the nanocomposites could be recovered and recycled for 10 consecutive trials without significant loss of its activity.     

Adsorbents made from waste ashes and post-consumer PET and their potential utilization in wastewater treatment

This study was carried out to prepare low-cost adsorbents from different types of waste ashes and post-consumer PET for use in industrial wastewater treatment. PET was melted and blended with ashes. The mixture was then carbonized to form different types of adsorbents. Heavy metal leaching from the adsorbents was greatly reduced compared to leaching from the bulk ashes. The BET surface area of the adsorbents ranged from 115 to 485m(2)/g. The acidic sites on the adsorbents varied from 0.84 to 1.56meq./g, higher than that of the PET carbon. The adsorption of methylene blue (MB) or heavy metals on the adsorbents was not in accordance with their surface areas because acidic sites reaction, affinity adsorption and cation exchange all contribute to the adsorption of the adsorbents. The isotherm for MB adsorption on the adsorbents can be well described by the Langmuir or Freundlich equation but heavy metal adsorption cannot. It is believed that the adsorbents produced in this manner can be used in wastewater treatments for discoloration and heavy metal removal.     

Low-cost adsorbents for heavy metals uptake from contaminated water: a review

In this article, the technical feasibility of various low-cost adsorbents for heavy metal removal from contaminated water has been reviewed. Instead of using commercial activated carbon, researchers have worked on inexpensive materials, such as chitosan, zeolites, and other adsorbents, which have high adsorption capacity and are locally available. The results of their removal performance are compared to that of activated carbon and are presented in this study. It is evident from our literature survey of about 100 papers that low-cost adsorbents have demonstrated outstanding removal capabilities for certain metal ions as compared to activated carbon. Adsorbents that stand out for high adsorption capacities are chitosan (815, 273, 250 mg/g of Hg(2+), Cr(6+), and Cd(2+), respectively), zeolites (175 and 137 mg/g of Pb(2+) and Cd(2+), respectively), waste slurry (1030, 560, 540 mg/g of Pb(2+), Hg(2+), and Cr(6+), respectively), and lignin (1865 mg/g of Pb(2+)). These adsorbents are suitable for inorganic effluent treatment containing the metal ions mentioned previously. It is important to note that the adsorption capacities of the adsorbents presented in this paper vary, depending on the characteristics of the individual adsorbent, the extent of chemical modifications, and the concentration of adsorbate.     

Copper and cadmium adsorption on pellets made from fired coal fly ash

Studies on the utilization of low cost adsorbents for removal of heavy metals from wastewaters are gaining attention. Fired coal fly ash, a solid by-product that is produced in power plants worldwide in million of tonnes, has attracted researchers' interest. In this work, fly ash was shaped into pellets that have diameter in-between 3-8mm, high relative porosity and very good mechanical strength. The pellets were used in adsorption experiments for the removal of copper and cadmium ions from aqueous solutions. The effect of agitation rate, equilibration time, pH of solution and initial metal concentration were studied. The adsorption of both cations follows pseudo-second order kinetics reaching equilibrium after an equilibration time of 72 h. The experimental results for copper and cadmium adsorption fit well to a Langmuirian type isotherm. The calculated adsorption capacities of pellets for copper and cadmium were 20.92 and 18.98 mg/g, respectively. Desorption experiments were performed in several extraction media. The results showed that both metals were desorbed substantially from pellets under acidic solutions. For this reason, metal saturated pellets were encapsulated in concrete blocks synthesized from cement and raw pulverized fly ash in order to avoid metal desorption. The heavy metals immobilization after encapsulation in concrete blocks was tested through desorption tests in several aqueous media. The results showed that after 2 months in acidic media with pH 2.88 and 4.98 neither copper nor cadmium were desorbed thus indicating excellent stabilization of heavy metals in the concrete matrix. As a conclusion, the results showed that fly ash shaped into pellets could be considered as a potential adsorbent for the removal of copper and cadmium from wastewaters. Moreover, the paper proposes an efficient and simple stabilization process of the utilized adsorbents thus guarantying their safe disposal in industrial landfills and eliminating the risk of pollution for groundwater and other natural water receivers.     

Optimization,Kinetics, and Equilibrium Studies on the Removal of Lead(II) from an Aqueous Solution Using Banana Pseudostem as an Adsorbent

Natural adsorbents such as banana pseudostem can play a vital role in the removal of heavy metal elements from wastewater. Major water resources and chemical industries have been encountering difficulties in removing heavy metal elements using available conventional methods. This work demonstrates the potential to treat various effluents utilizing natural materials. A characterization of banana pseudostem powder was performed using environmental scanning electron microscopy (ESEM) and Fourier-transform infrared (FTIR) spectroscopy before and after the adsorption of lead(II). Experiments were carried out using a batch process for the removal of lead(II) from an aqueous solution. The effects of the adsorption kinetics were studied by altering various parameters such as initial pH, adsorbent dosage, initial lead ion concentration, and contact time. The results show that the point of zero charge (PZC) for the banana pseudostem powder was achieved at a pH of 5.5. The experimental data were analyzed using isotherm and kinetic models. The adsorption of lead(II) onto banana pseudostem powder was fitted using the Langmuir adsorption isotherm. The adsorption capacity was found to be 34.21 mg·g^–1, and the pseudo second-order kinetic model showed the best fit. The optimum conditions were found using response surface methodology. The maximum removal was found to be 89%.     

Removal and recovery of heavy metals from electroplating wastewater by using Kyanite as an adsorbent

Kyanite, a commercial mineral has been utilized as an adsorbent for the removal of heavy metals, such as Ni(II), Zn(II), Cr(VI) and Cu(II) from electroplating wastewater. The effect of contact time, pH, concentration, adsorbent doses, particle size of the adsorbent, salinity and hardness, both in natural and wastewater on the adsorption of Cu(II) have been studied in detail. The adsorption of metal ions seems to be an ion exchange process. The adsorbed metals ions from electroplating wastewater were recovered by batch as well as column operation using dilute HCl solution. The column operation was found to be more effective compared to batch process.     

Multi-component sorption of Pb(II), Cu(II) and Zn(II) onto low-cost mineral adsorbent

Multi-component sorption studies were carried out for attenuation of divalent heavy metal cations (Pb2+, Cu2+ and Zn2+) by a low-cost mineral adsorbent from the aqueous solution. Kinetic and equilibrium batch-type sorption experiments were conducted under variable conditions for multi-component using low-grade (<12%P2O5) phosphate rock. Percentage of multiple heavy metal species removal increases with decreasing initial metals concentration and particle size. The equilibrium data were well described to a lesser extent by Freundlich model but Langmuir model seemed to be more appropriate with the fixation capacity obtained at room temperature for Pb2+, Cu2+ and Zn2+ was 227.2, 769.2 and 666.6 micromol g(-1), respectively. Two simple kinetic models were tested to investigate the adsorption mechanism. Rate constants have been found nearly constant at all metal concentrations for first order. The comparison of adsorption capacity of low-grade phosphate rock decreases in multi-component system as compared to single component due to ionic interactions. X-ray powder diffraction (XRPD) technique was used to ascertain the formation of new metal phases followed by surface complexation. Used adsorbents have been converted into a value added product by utilizing innovative Zero-waste concept to solve the used adsorbents disposal problem and thus protecting the environment.     

Cu2+, Cd2+ and Pb2+ adsorption from aqueous solutions by pyrite and synthetic iron sulphide

In this study, removal of Cu(2+), Cd(2+) and Pb(2+) from aqueous solutions by adsorption onto pyrite and synthetic iron sulphide (SIS) was investigated as a function of pH, contact time, adsorbent dosage, initial metal concentration and temperature. It has been determined that the adsorption of metal ions onto both adsorbents is pH dependent and the adsorption capacities increase with the increasing temperature. The mechanisms governing the metal removal processes were determined as chemical precipitation at low pH (<3) due to H(2)S generation and adsorption at high pH (in the range of 3-6). The metal adsorption yields also increased with the increasing adsorbent dosage and contact time and reached to equilibrium for both adsorbents. The Cu(2+), Cd(2+) and Pb(2+) adsorption capacities of both adsorbents decrease in the order of Pb(2+)>Cu(2+)>Cd(2+). Except for cadmium, little fraction of copper and lead in the solid adsorption residues was desorbed in acidic media.     

Removal of heavy metal ions from aqueous solutions using various low-cost adsorbents

The removal of single heavy metals Co and Zn from aqueous solutions using various low-cost adsorbents (Fe(2)O(3), Fe(3)O(4), FeS, steel wool, Mg pellets, Cu pellets, Zn pellets, Al pellets, Fe pellets, coal, and GAC) was investigated. Experiments were performed at different solution pH values (1.5-9) and metal concentrations (0.67-333 mg/l). The effect of solution pH on metal adsorption using Fe(2)O(3) and Fe(3)O(4) was significant, but was negligibly small using steel wool, Mg pellets, Fe pellets, and Al pellets over the entire pH range. Steel wool and Mg pellets were the most excellent adsorbents; for example, the removal of Zn and Co from dilute solutions (<35 mg/l) was greater than 94% at an adsorbent dose of 1.7 g/l. A mass transfer model, which involves two parameters tau (50% breakthrough time) and k (proportionality constant), was proposed to describe breakthrough data of Co in the fixed beds packed with steel wool and Mg pellets. The calculated breakthrough curves agreed well with the measured data (standard deviation < 6%). The value of tau decreased with increasing the flow rate. The effects of flow rates on the value of k and adsorption capacity are discussed.     

Adsorption of chromium(VI) on low cost adsorbents derived from agricultural waste material: a comparative study

Two low cost adsorbents were prepared by using groundnut husk and were tested for the removal of chromium. All the experiments were carried out in batch process with chromium spiked samples of drinking water. Silver impregnated groundnut husk carbon and groundnut husk carbon were tested for the removal of chromium(VI). Effects of adsorbent quantity, pH, contact time and agitation rate were investigated on removal of chromium. The adsorption data were fitted well by Freundlich adsorption isotherm. Approximately, 97% of hexavalent chromium was removed at pH 3 within 5h. It was found that adsorbents chemically modified with an oxidizing agent demonstrated better chromium removal capabilities as compared to pure adsorbents in terms of their adsorption rate. On the basis of present studies, it can be concluded that groundnut husk carbon oxidized with silver treatment, has a higher chromium adsorption capacities.     

Removal of cadmium (II) from aqueous solutions by adsorption on agricultural waste biomass

This paper reports the feasibility of using various agricultural residues viz. sugarcane bagasse (SCB), maize corncob (MCC) and Jatropha oil cake (JOC) for the removal of Cd(II) from aqueous solution under different experimental conditions. Effect of various process parameters, viz., initial metal ion concentration, pH, and adsorbent dose has been studied for the removal of cadmium. Batch experiments were carried out at various pH (2-7), adsorbent dose (250-2000 mg), Cd(II) concentration (5-500 mg l(-1)) for a contact time of 60 min. The maximum cadmium removal capacity was shown by JOC (99.5%). The applicability of Langmuir and Freundlich isotherm suggests the formation of monolayer of Cd(II) ions onto the outer surface of the adsorbents. Maximum metal removal was observed at pH 6.0 with a contact time of 60 min at stirring speed of 250 rpm with an adsorbent dose of 20 g l(-1) of the test solution. The maximum adsorption of cadmium (II) metal ions was observed at pH 6 for all the adsorbents viz; 99.5%, 99% and 85% for JOC, MCC, and SCB, respectively. Order of Cd(II) removal by various biosorbents was JOC>MCC>SCB. JOC may be an alternative biosorbent for the removal of Cd(II) ions from the aqueous solution. FT-IR spectra of the adsorbents (before use and after exhaustion) were recorded to explore number and position of the functional groups available for the binding of Cd(II) ions on to studied adsorbents. These results can be helpful in designing a batch mode system for the removal of cadmium from dilute wastewaters.     

Removal of Cu(II) from water by tetrakis(4-carboxyphenyl) porphyrin-functionalized mesoporous silica

Various adsorbents are available for the removal of heavy and toxic metals, silica-based materials have been the most popular. Recently, there has been considerable interest for the modification of organic moieties and mesostructured materials to enable their use as efficient adsorbent for metal removal. In this study, here we are reporting successful incorporation of tetrakis(4-carboxyphenyl)porphyrin (TCPP) in mesoporous silica by the post-synthetic method. TCPP-SBA-15 has been found to be an effective material for the removal of Cu(II) from aqueous solution due to the chelating nature of the porphyrin-bridging group. A comparative study on adsorption of copper(II) ion over NH(2)-SBA-15 silica and TCPP-SBA-15 was performed. The results show that TCPP-SBA-15 material has higher adsorption capacity than NH(2)-SBA-15 silica and it reaches the adsorption maxima around 13 mmol g(-1).     

Electrokinetic and adsorption properties of sepiolite modified by 3-aminopropyltriethoxysilane

Surface modification of clay minerals has become increasingly important for improving the practical applications of clays such as fillers and adsorbents. An investigation was carried out on the surface modification of sepiolite with aminopropylsilyl groups in 3-aminopropyltriethoxysilane (3-APT). The zeta potential of the modified sepiolite suspensions was measured as a function of initial electrolyte concentration and equilibrium pH using a Zeta Meter 3.0 for modified sepiolite. The utility of the 3-APT-modified sepiolite was investigated as an adsorbent for removal of various heavy metal ions such as Fe, Mn, Co, Zn, Cu, Cd and Ni from aqueous solutions. The effects of various factors on the adsorption, such as pH, ionic strength and temperature of the solution were studied. The results showed that the amount adsorbed increases with solution pH in the pH range of 1.5 and 7.0; indicated that the modified sepiolite adsorbed Fe and Mn ions more than other metal ions such as Co, Zn, Cu, Cd and Ni. It was found that the temperature had an important effect on metal ion adsorption by the modified sepiolite. The adsorption isotherm has been determined and data have been analyzed according to the Langmuir and Freundlich models.     

Preparation of a novel zwitterionic graphene oxide-based adsorbent to remove of heavy metal ions from water: Modeling and comparative studies

A novel zwitterionic graphene oxide-based adsorbent was first synthesized in a multistep procedure including the successive grafting of bis(2-pyridylmethyl)amino groups (BPED) and 1,3-propanesultone (PS) onto graphene oxide (GO) sheets. Then, the as-prepared materials were used as adsorbent for the removal of metal ions from aqueous solutions. The influence of solution pH, contact time, metal ion concentration, and temperature onto the adsorption capacity of the zwitterionic GO-BPED-PS adsorbent was investigated and compared with the GO-BPED adsorbent. In particular, it was shown that the maximum adsorption capacities of the GO-BPED-PS adsorbent were as high as 4.174 ± 0.098 mmol.g^?1 for the Ni(II) ions and 3.902 ± 0.092 mmol.g^?1 for the Co(II) ions under optimal experimental conditions (metal ion concentration = 250 mg.L^?1, pH = 7 and T = 293 K). In addition, the adsorption behaviors of Ni(II) and Co(II) ions onto both the GO-BPED and GO-BPED-PS adsorbents fitted well with a pseudo-second-order kinetic model and a Jossens isotherm model. Moreover, adsorption thermodynamics of Ni(II) and Co(II) ions have been studied at various temperatures and confirmed the exothermic adsorption nature of the adsorption process onto the GO-BPED-PS adsorbent. Furthermore, the zwitterionic GO-BPED-PS adsorbent retained good adsorption properties after recycling 18 times which is much better than the conventional adsorbents.     

Reuse of waste silica as adsorbent for metal removal by iron oxide modification

Silica gel is widely used in research laboratories, especially for the purification of organic compounds. Consequently, waste silica gel is generated in increasing amounts. In this work, waste silica was modified by coating its surface with iron oxide aiming to obtain an effective adsorbent for metal removal from wastewater. In the preparation of the adsorbent, the optimal pretreatment temperature and iron concentration were investigated. The coated waste silica was characterized for BET surface area, pore size, specific pore volume and iron content. Iron oxide-coated waste silica was tested for the adsorption of Pb(II), Cu(II), Cd(II) and Ni(II) from solutions in a batch system. The effect of contact time, pH and salt concentration on metal adsorption was investigated. It was found that the adsorption of metals occurred rapidly and reached equilibrium within 30 min. The pH suitable for metal adsorption was between 6 and 7 and leaching of iron from the coating was observed only at pH 3 or lower. The presence of salt reduced the adsorption efficiency of the adsorbent. The adsorption behavior followed both Langmuir and Freundlich isotherms (25 degrees C). Finally, the efficacy of the adsorbents was investigated using aqueous lab waste where removal efficiencies ranging from 62 to 89% were achieved when the initial metal concentrations ranged from 13 to 42 mg L(-1).     

An investigation into the sorption of heavy metals from wastewaters by polyacrylamide-grafted iron(III) oxide

An adsorbent for heavy metals was synthesized by introducing carboxylate functional group into polyacrylamide-grafted hydrous iron(III) oxide. The product exhibits a very high adsorption potential for Pb(II), Hg(II) and Cd(II). The removal of metal ions by adsorption on adsorbent has been found to be contact time, concentration, pH and temperature dependent. The process follows first-order reversible kinetics. The intraparticle diffusion of metal ions through pores in the adsorbent was shown to be the main rate-limiting step. The optimum pH range for the removal of metal ions was found to be 5.0-6.0. The thermodynamic parameters such as free energy change, enthalpy change and entropy change have been calculated to predict the nature of adsorption. The adsorption data were fitted using the Langmuir equation and maximum adsorption for each metal was estimated using their respective Langmuir equation constants. The method was applied for synthetic wastewaters. NaCl regeneration has been tried for several cycles with a view to recover the adsorbed metal ions and also to restore the sorbent to its original state.     

纤维素改性材料对重金属吸附性能的研究进展

近年来,工农业排放的重金属离子产生了严重的水体污染;这些重金属离子浓度低,通过吸附法可以有效处理这些污染问题。吸附法的关键在于高效吸附材料的设计和制备。纤维素是可再生的高分子聚合物,具有储量丰富、来源广泛等优点,纤维素材料经过改性后对重金属离子具有良好的吸附能力。介绍了纤维素的结构特点、吸附原理和不同改性方法,重点比较了纤维素的物理改性、直接化学改性和接枝改性等不同改性方法和对重金属离子的吸附的影响,并展望了纤维素基吸附材料的发展前景和方向。     

Removal of cationic dyes from aqueous solution using magnetic multi-wall carbon nanotube nanocomposite as adsorbent

A magnetic multi-wall carbon nanotube (MMWCNT) nanocomposite was synthesized and was used as an adsorbent for removal of cationic dyes from aqueous solutions. The MMWCNT nanocomposite was composed of commercial multi-wall carbon nanotubes and iron oxide nanoparticles. The properties of this magnetic adsorbent were characterized by scanning electron microscopy, X-ray diffraction and BET surface area measurements. Adsorption characteristics of the MMWCNT nanocomposite adsorbent were examined using methylene blue, neutral red and brilliant cresyl blue as adsorbates. Experiments were carried out to investigate adsorption kinetics, adsorption capacity of the adsorbent and the effect of adsorption dosage and solution pH values on the removal of cationic dyes. Kinetic data were well fitted by a pseudo second-order model. Freundlich model was used to study the adsorption isotherms. The prepared MMWCNT adsorbent displayed the main advantage of separation convenience compared to the present adsorption treatment.