Removal of mercury(II) from aqueous media using eucalyptus bark: Kinetic and equilibrium studies

In this study, eucalyptus camaldulensis bark, a forest solid waste, is proposed as a novel material for the removal of mercury(II) from aqueous phase. The operating variables studied were sorbent dosage, ionic strength, stirring speed, temperature, solution pH, contact time, and initial metal concentration. Sorption experiments indicated that the sorption capacity was dependent on operating variables and the process was strongly pH-dependent. Kinetic measurements showed that the process was uniform and rapid. In order to investigate the mechanism of sorption, kinetic data were modeled using the pseudo-first-order and pseudo-second-order kinetic equations, and intraparticle diffusion model. Among the kinetic models studied, the pseudo-second-order equation was the best applicable model to describe the sorption process. Equilibrium isotherm data were analyzed using the Langmuir and the Freundlich isotherms. The Langmuir model yields a much better fit than the Freundlich model. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy, and entropy of sorption. The maximum sorption capacity was 33.11 mg g⁻¹ at 20 °C and the negative value of free energy change indicated the spontaneous nature of sorption. These results demonstrate that eucalyptus bark is very effective in the removal of Hg(II) from aqueous solutions.     

Multi-functional sorbents for the simultaneous removal of sulfur and lead compounds from hot flue gases

A multi-functional sorbent is developed for the simultaneous removal of PbCl(2) vapor and sulfur dioxide from the combustion gases. The sorbent is tested in a bench-scale reactor at the temperature of 700 degrees C, using simulated flue gas (SFG) containing controlled amounts of PbCl(2) and SO(2) compounds. The removal characteristics of PbCl(2) and SO(2), individually and in combination, are investigated. The results show that the mechanism of capture by the sorbent is not a simple physical adsorption process but seems to involve a chemical reaction between the Ca-based sorbent and the contaminants from the simulated flue gas. The porous product layer in the case of individual SO(2) sorption is in a molten state at the reaction temperature. In contrast, the combined sorption of lead and sulfur compounds generates a flower-shaped polycrystalline product layer.     

Eggshell nano-particle potential for methyl violet and mercury ion removal: Surface study and field application

A nano-scale sorbent was produced from eggshell wastes for sorption of Hg(II) and methyl violet (MV) from aqueous solutions and real wastewaters. The properties of the nano-particles were fully determined using SEM, DLS, FTIR, XRD, BET, TGA, AFM, EDAX, mapping, and TEM analyses. The adsorbent structure mainly contained carbonate and silica. The effects of influential parameters including temperature, contact time, initial contaminants concentration, sorbent dose, and initial pH on the removal efficiency were investigated. The maximum sorption efficiency of Hg(II) and MV occurred at pH of 6 and 9 and temperatures of 25 °C and 55 °C, respectively. Freundlich model could be interpreted the equilibrium data of the sorption process of both contaminants. The maximum sorption capacity of Hg(II) and MV using eggshell nano-particles was obtained as 116.27 mg/g and 123.45 mg/g, respectively. The dynamic behavior of the process was studied using two kinetic models. The sorption system performance was also examined and t_1/2 were determined as 4.34 min for Hg(II) and 4.97 min for MV. The sorption process of Hg(II) and MV was exothermic and endothermic, respectively. Effective sorption after seven cycles and successful treatment of landfill leachate and textile wastewater with eggshell nano-particles confirms its adequacy.     

Efficient Mercury Capture Using Functionalized Porous Organic Polymer

The primary challenge in materials design and synthesis is achieving the balance between performance and economy for real‐world application. This issue is addressed by creating a thiol functionalized porous organic polymer (POP) using simple free radical polymerization techniques to prepare a cost‐effective material with a high density of chelating sites designed for mercury capture and therefore environmental remediation. The resulting POP is able to remove aqueous and airborne mercury with uptake capacities of 1216 and 630 mg g^?1, respectively. The material demonstrates rapid kinetics, capable of dropping the mercury concentration from 5 ppm to 1 ppb, lower than the US Environmental Protection Agency's drinking water limit (2 ppb), within 10 min. Furthermore, the material has the added benefits of recyclability, stability in a broad pH range, and selectivity for toxic metals. These results are attributed to the material's physical properties, which include hierarchical porosity, a high density of chelating sites, and the material's robustness, which improve the thiol availability to bind with mercury as determined by X‐ray photoelectron spectroscopy and X‐ray absorption fine structure studies. The work provides promising results for POPs as an economical material for multiple environmental remediation applications.     

Aluminum drinking water treatment residuals (Al-WTRs) as sorbent for mercury: Implications for soil remediation

The potential of readily available and non-hazardous waste material, aluminum drinking water treatment residuals (Al-WTRs), to efficiently sorb and immobilize mercury (Hg) from aqueous solutions was evaluated. Al-WTR samples with average specific surface area of 48m(2)/g and internal micropore surface area of 120m(2)/g were used in a series of batch sorption experiments. Obtained sorption isotherms indicated a strong affinity of Hg for Al-WTRs. Using the Langmuir adsorption model, a relatively high maximum sorption capacity of 79mg Hg/g Al-WTRs was determined. Sorption kinetic data was best fit to a pseudo-first-order model, while the use of the Weber-Morris and Bangham models suggested that the intraparticle diffusion could be the rate-limiting step. Also, Al-WTRs effectively immoblized Hg in the pH range of 3-8. The results from these short-term experiments demonstrate that Al-WTRs can be effectively used to remove Hg from aqueous solutions. This ability points to the potential of Al-WTRs as a sorbent in soil remediation techniques based on Hg-immobilization.     

Removal and preconcentration of inorganic and methyl mercury from aqueous media using a sorbent prepared from the plant Coriandrum sativum

A sorbent prepared from the plant Coriandrum sativum, commonly known as coriander or Chinese parsley, was observed to remove inorganic (Hg2+) and methyl mercury (CH3Hg+) from aqueous solutions with good efficiency. Batch experiments were carried out to determine the pH dependency in the range 1-10 and the time profiles of sorption for both the species. Removal of both the forms of mercury from spiked ground water samples was found to be efficient and not influenced by other ions. Column experiments with silica-immobilized coriander demonstrated that the sorbent is capable of removing considerable amounts of both forms of mercury from water. The sorption behaviour indicates the major role of carboxylic acid groups in binding the mercury. The studies suggest that the sorbent can be used for the decontamination of inorganic and methyl mercury from contaminated waters.     

Recovery of <Superscript>137</Superscript>Cs and <Superscript>90</Superscript>Sr from wastewater by sorption on finely dispersed minerals under static conditions

The natural minerals clinoptilolite and tripoli were used for sorption treatment of liquid radioactive waste (LRW) to remove ¹³⁷Cs and ⁹⁰Sr. The efficiency of sorption recovery of these radionuclides with finely dispersed mineral sorbents under static conditions was studied in relation to the sorption time, pH, size of mineral granules, sorbent amount, salt content and chemical composition of solutions, and number of successive sorption steps. The distribution coefficient of radionuclides between the sorbent and aqueous phase and the sorption capacity of sorbents for radionuclides were determined. It was found that treatment of real salt-containing LRW from the Leipunskii Institute of Energy Physics, State Scientific Center of the Russian Federation, with the natural sorbents decreased their activity by 2–3 orders of magnitude owing to recovery of ¹³⁷Cs and ⁹⁰Sr.     

Mercury adsorption on a carbon sorbent derived from fruit shell of Terminalia catappa

A carbonaceous sorbent derived from the fruit shell of Indian almond (Terminalia catappa) by sulfuric acid treatment was used for the removal of mercury(II) from aqueous solution. Sorption of mercury depends on the pH of the aqueous solution with maximum uptake occurring in the pH range of 5-6. The kinetics of sorption conformed well to modified second order model among the other kinetic models (pseudo first order and pseudo second order) tested. The Langmuir and Redlich-Peterson isotherm models defined the equilibrium data precisely compared to Freundlich model and the monolayer sorption capacity obtained was 94.43 mg/g. Sorption capacity increased with increase in temperature and the thermodynamic parameters, DeltaH degrees , DeltaS degrees and DeltaG degrees , indicated the Hg(II) sorption to be endothermic and spontaneous with increased randomness at the solid-solution interface. An optimum carbon dose of 4 g/l was required for the maximum uptake of Hg(II) from 30 mg/l and the mathematical relationship developed showed a correlation of 0.94 between experimental and calculated percentage removals for any carbon dose studied. About 60% of Hg(II) adsorbed was recovered from the spent carbon at pH 1.0, while 94% of it was desorbed using 1.0% KI solution.     

Rapid removal of Hg(II) from aqueous solutions using thiol-functionalized Zn-doped biomagnetite particles

The surfaces of Zn-doped biomagnetite nanostructured particles were functionalized with (3-mercaptopropyl)trimethoxysilane (MPTMS) and used as a high-capacity and collectable adsorbent for the removal of Hg(II) from water. Fourier transform infrared spectroscopy (FTIR) confirmed the attachment of MPTMS on the particle surface. The crystallite size of the Zn-doped biomagnetite was ～17 nm, and the thickness of the MPTMS coating was ～5 nm. Scanning transmission electron microscopy and dynamic light scattering analyses revealed that the particles formed aggregates in aqueous solution with an average hydrodynamic size of 826 ± 32 nm. Elemental analyses indicate that the chemical composition of the biomagnetite is Zn(0.46)Fe(2.54)O(4), and the loading of sulfur is 3.6 mmol/g. The MPTMS-modified biomagnetite has a calculated saturation magnetization of 37.9 emu/g and can be separated from water within a minute using a magnet. Sorption of Hg(II) to the nanostructured particles was much faster than other commercial sorbents, and the Hg(II) sorption isotherm in an industrial wastewater follows the Langmuir model with a maximum capacity of ～416 mg/g, indicating two -SH groups bonded to one Hg. This new Hg(II) sorbent was stable in a range of solutions, from contaminated water to 0.5 M acid solutions, with low leaching of Fe, Zn, Si, and S (<10%).     

Preparation and properties of modified spherically granulated chitosan for sorption of <Superscript>137</Superscript>Cs from solutions

A composite sorbent based on spherically granulated chitosan modified with a mixed ferrocyanide K₂Cu₃[Fe(CN₆)]₂ (SGC-FC) was prepared. The sorbent is highly effective toward ¹³⁷Cs. The physicochemical parameters of ¹³⁷Cs⁺ sorption by this sorbent were determined: total and equilibrium static exchange capacity, dynamic exchange capacity, sorption equilibrium constants, etc. The influence of the chemical composition of the solution on the ¹³⁷Cs⁺ sorption by SGC-FC was examined in detail. Based on the calculated value of the dimensionless Biot number Bi, a conclusion was made that the kinetics of ¹³⁷Cs⁺ sorption on SGC-FC is mainly determined by external diffusion of ¹³⁷Cs⁺ ions to reaction centers of the sorbent. The possibility of using the sorbent in monitoring of sea areas was considered.     

Nanosized cation-deficient Fe-Ti spinel: a novel magnetic sorbent for elemental mercury capture from flue gas

Nonstoichiometric Fe-Ti spinel (Fe(3-x)Ti(x))(1-δ)O(4) has a large amount of cation vacancies on the surface, which may provide active sites for pollutant adsorption. Meanwhile, its magnetic property makes it separable from the complex multiphase system for recycling, and for safe disposal of the adsorbed toxin. Therefore, (Fe(3-x)Ti(x))(1-δ)O(4) may be a promising sorbent in environmental applications. Herein, (Fe(3-x)Ti(x))(1-δ)O(4) is used as a magnetically separable sorbent for elemental mercury capture from the flue gas of coal-fired power plants. (Fe(2)Ti)(0.8)O(4) shows a moderate capacity (about 1.0 mg g(-1) at 250 °C) for elemental mercury capture in the presence of 1000 ppmv of SO(2). Meanwhile, the sorbent can be readily separated from the fly ash using magnetic separation, leaving the fly ash essentially free of sorbent and adsorbed mercury.     

Preparation of Exfoliated Graphite Modified with Magnesium Ferrite

A magnetic sorbent based on exfoliated graphite modified with magnesium ferrite has been prepared by impregnating oxidized graphite in a mixed solution of FeCl₃ and Mg(NO₃)₂, followed by heat treatment of the impregnated oxidized graphite in air. X-ray diffraction and Mössbauer spectroscopy results demonstrate that the structure of the magnesium ferrite is an inverse spinel with a degree of inversion of 0.59. The saturation magnetization of the magnesium ferrite-containing exfoliated graphite is 16.1 emu/g, whereas its oil sorption capacity is as high as 54 g/g. Compaction of the exfoliated graphite to a density of 0.03 g/cm³ reduced its sorption capacity to 26 g/g. Further increasing the density of the material led to a considerable decrease in its sorption capacity.     

Influence of the potassium and ammonium ion concentrations on the selective sorption of 137Cs by illite and clinoptilolite

It is suggested to describe the dependence of K _d ^?1 of ¹³⁷Cs on the potassium ion concentration for clinoptilolite and illite with a quasi-Langmuir equation in which the maximal radiocesium interception potential relative to potassium, RIP(K)_max, is used instead of the maximal sorption capacity of the sorbent. For describing the dependence of the selective sorption of ¹³⁷Cs on the concentration of ammonium ions, an approximation equation consisting of two normalized quasi-Langmuir equations is suggested, with one equation describing the ¹³⁷Cs sorption on low-affinity sorption centers for concentrations exceeding 3 mM and the other equation describing the sorption on high-affinity centers for ammonium concentrations of up to 3 mM.     

Capture of mercury ions by natural and industrial materials

In this paper the technical feasibility of various adsorbents for mercury removal from contaminated waters has been studied. Adsorption isotherms of mercury ions in aqueous solution have been experimentally measured on a granular activated carbon (Aquacarb 207EA), a char, a pozzolana and a yellow tuff. The experimental evidences show that the mercury capture capacity of yellow tuff and char is of few tenths of milligrams per gram of sorbent while for the pozzolana and the activated carbon this value is of the order of 1mg/g of sorbent. Moreover, for a mercury concentration as high as 3000 microg/l the pozzolana shows the highest adsorption capacity. This result seems to be quite interesting, especially in consideration of the extremely low cost of this natural sorbent.     

Immobilization of aqueous Hg(II) by mackinawite (FeS)

As one of the major constituents of acid volatile sulfide (AVS) in anoxic sediments, mackinawite (FeS) is known for its ability to scavenge trace metals. The interaction between aqueous Hg(II) (added as HgCl(2)) and synthetic FeS was studied via batch sorption experiments conducted under anaerobic conditions. Due to the release of H(+) during formation of hydrolyzed Hg(II) species which is more reactive than Hg(2+) in surface adsorption, the equilibrium pH decreased with the increase in Hg(II)/FeS molar ratio. Counteracting the loss of FeS solids at lower pH, the maximum capacity for FeS to remove aqueous Hg(II) was approximately 0.75 mol Hg(II) (mol FeS)(-1). The comparison of X-ray power diffraction (XRPD) patterns of synthetic FeS sorbent before and after sorption showed that the major products formed from the interaction between FeS and the aqueous Hg(II) were metacinnabar, cinnabar, and mercury iron sulfides. With the addition of FeS at 0.4 g L(-1) to a 1 mM Hg(II) solution with an initial pH of 5.6, Fe(2+) release was approximately 0.77 mol Fe(2+) per mol Hg(II) removed, suggesting that 77% of Hg(II) was removed via precipitation reaction under these conditions, with 23% of Hg(II) removed by adsorption. Aeration does not cause significant release of Hg(II) into the water phase.     

Adsorption of Mo on γ-Al2O3 Samples of Various Structures

Adsorption of Mo on -Al₂O₃ samples of various structures was studied with the aim of using these sorbents in production of chromatographic 99mTc generators. The sorption capacities of the oxides for Mo were determined. The optimal concentrations of HCl and HNO₃ for converting the sorbent to the H⁺ form were found. In all the cases, treatment with HCl ensures higher sorption capacity than treatment with HNO₃. The sorption capacity of aluminum oxides prepared by ac electrochemical synthesis was studied in relation to pH of sodium polymolybdate solution and sorption time. The sorption capacity of these samples for Mo is several times higher than that of the chromatographic oxide traditionally used in the generator technology.     

Ion-exchange zirconium sorption by functionalized carbon nanofibers

We have studied chemical equilibrium between functionalized carbon nanofibers and an aqueous ZrOCl₂ or ZrOSO₄ solution and evaluated the sorption capacity of the nanofibers as a function of Zr concentration, solid: liquid (S: L) ratio, solution pH, and the degree of nanofiber functionalization. The results demonstrate that the equilibration time at S: L = 1: 10 and 1: 2 is 10 and 30 min, respectively, and that the sorption capacity increases with increasing solution pH or Zr concentration and with decreasing S: L ratio and exceeds 2.0 mg ZrO₂/mg of the sorbent under certain conditions. A saturated sorbent after drying can be used to fabricate nanofiber-ZrO₂ composites.     

Metal-Containing Zeolites as Sorbents for Localization of Radioiodine and CsI Aerosols from Vapor-Air and Aqueous Phases

New sorbents for efficient sorption of radioiodine and radiocesium from the vapor-gas phase and aqueous solutions were prepared by treatment of Cu⁺- and Ag⁺-substituted NaX and NaA zeolites with acetylene in aqueous solution. The distribution factor K _d of radioiodine and radiocesium between the modified sorbents and aqueous solutions is higher than 10³-10⁴ ml g^{- 1}. Decontamination factor of the vapor-gas phase with respect to radioiodine and ¹³⁷CsI aerosols exceeds 10²-10³ and 10³, respectively. The sorption properties of the modified sorbents in both aqueous solutions and the vapor-gas phase are better than those of the initial sorbents. However, localization of radioiodine from the vapor-gas phase with the Cu⁺-containing sorbents is less efficient than with the Ag⁺-containing zeolites. At the same time, in aqueous solutions the sorption capacity of the Cu⁺-containing sorbents for radioiodine is appreciably higher than that of the Ag⁺-containing sorbents. The sorption properties of the modified sorbents were studied as influenced by various factors. Paracomplexes of univalent copper and silver with C₂H₂, H₂O, and anions present in the solution are probably formed during modification of the metal-containing zeolites. The dependence of K _d of radioiodine on the metal concentration in the sorbent, the free pore volume of the sorbent, and the anion nature was revealed.     

Fabrication of a selective mercury sensor based on the adsorption of cold vapor of mercury on carbon nanotubes: Determination of mercury in industrial wastewater

A new sensor for the determination of mercury at μg ml^?1 levels is proposed based on the adsorption of mercury vapor on single-walled carbon nanotubes (SWCNTs). The changes in the impedance of SWCNTs were monitored upon adsorption of mercury vapor. The adsorption behaviour of mercury on SWCNTs was compared with that on multi-walled carbon nanotubes (MWCNTs) and carbon nanofibers (CNFs). Cold vapor of mercury was generated at 65 °C using Sn(II) solution as a reducing agent. The limit of detection was 0.64 μg ml^?1 for Hg(II) species. The calibration curve for Hg(II) was linear from 1.0 to 30.0 μg ml^?1. The relative standard deviation (RSD) of eight replicate analyses of 15 μg ml^?1 of Hg(II) was 2.7%. The results showed no interfering effects from many foreign species and hydride forming elements. The system was successfully applied to the determination of the mercury content of different types of wastewater samples.     

Influence of the concentrations of potassium, sodium, and ammonium ions on the cesium sorption with mixed nickel potassium ferrocyanide sorbent based on hydrated titanium dioxide

The effect of single-charged cations (Na⁺, K⁺, NH ₄ ⁺ ) on the cesium sorption with mixed nickel potassium ferrocyanide sorbent based on hydrated TiO₂ was studied. The K⁺ and Na⁺ ions exert no effect at their concentrations of up to 0.5 M; the Cs⁺ distribution coefficients from KCl and NaCl solutions are (1.1 ± 0.5) × 10⁵ and (8 ± 3) × 10⁴ mL g^?1, respectively. The sorbent is highly specific to Cs⁺ in the presence of ammonium ions. The sorption mechanisms were studied. The concentration ranges in which Cs⁺ and NH ₄ ⁺ are sorbed by independent mechanisms (Cs⁺, by the ferrocyanide phase; NH ₄ ⁺ , by the phase of hydrated TiO₂) and in which the Cs⁺ distribution coefficient decreases owing to competitive filling of the ferrocyanide phase with ammonium ions were determined. At cesium concentrations in solution exceeding 50 mg L^?1, Cs⁺ and NH ₄ ⁺ are absorbed jointly owing to coprecipitation in the mixed ferrocyanide phase in the pore space of the sorbent.