Biosorption of Cu(II) and Pb(II) from aqueous solutions by chemically modified spent coffee grains

In this research, spent coffee grains were modified with citric acid solutions (0.1 and 0.6 M) to increase the quantity of carboxylic groups improving its metal adsorption capacity. Added functional groups on modified and non-modified spent coffee grains were identified and quantified by attenuated total reflection Fourier transform infrared analyses and potentiometric titrations, respectively. These adsorbents were used for the removal of lead (II) and copper (II) from aqueous solutions at 30 °C and different pH in batch systems. In addition, adsorption–desorption experiments were conducted to evaluate the possibility of re-using the modified adsorbent. Potentiometric titrations data reveal that the quantity of carboxylic groups was increased from 0.47 to 2.2 mmol/g when spent coffee grains were modified with 0.1 and 0.6 M citric acid. Spent coffee grains treated with 0.6 M citric acid, achieved a maximum adsorption capacity of 0.77 and 1.53 mmol/g for lead (II) and copper (II), respectively, whereas non-modified spent coffee grains only reached 0.24 and 0.19 mmol/g for lead (II) and copper (II), respectively. Desorption of lead (II) and copper (II) achieved around 70 % using 0.1 N HCl for non-modified and modified spent coffee grains with 0.6 M citric acid. It is suggested that lead (II) and copper (II) species were adsorbed mainly on the carboxylic groups of modified spent coffee grains and these metals may be exchanged for hydrogen and calcium (II) ions during adsorption on non-modified spent coffee grains. Finally, the adsorption equilibrium was reached after 400 min for modified spent coffee grains with 0.6 M citric acid. Modified spent coffee grains are a promising option for removing metal cations from aqueous solutions due to its low cost and high adsorption capacity (about 10 times higher than the activated carbons).     

Adsorption of aqueous Pb(II), Cu(II), Zn(II) ions by amorphous tin(VI) hydrogen phosphate: an excellent inorganic adsorbent

Amorphous tin(VI) hydrogen phosphate (ATHP) was synthesized using the liquid phase precipitation method and served as an adsorbent to remove Pb(II), Cu(II), and Zn(II) from aqueous solutions. The ATHP was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption techniques. Adsorption properties were evaluated as a function of pH, reaction time, concentration of reactants, and salinity. Their equilibrium adsorption data were modeled using Freundlich, Langmuir, and Dubinin–Kaganer–Radushkevich isotherms, respectively. The results revealed that adsorption equilibrium reached within 180 min. ATHP indicated good adsorption even below the pH_ZPC, and best adsorption at pH 5 for Pb(II) and Cu(II) and at pH 5.5 for Zn(II) was observed. Equilibrium data fitted better to the Langmuir model for Pb(II) and Cu(II) and fitted better to the Freundlich model for Zn(II). The saturated adsorption capacities deduced from the Langmuir model were 2.425, 1.801, and 0.600 mmol/g for Cu(II), Pb(II), and Zn(II), respectively, indicating an adsorption affinity order of Cu > Pb > Zn. There is a negative correlation between the concentration of NaCl and adsorption capacity of ATHP, yet ATHP still exhibited excellent adsorption having an adsorption capacity of 19.35, 15.16, 6.425 mg/g when the concentration of NaCl was 0.6 mol/L. The free energy (E) was 12.33, 10.70, and 14.74 kJ/mol for Pb(II), Cu(II), and Zn(II), respectively. An adsorption mechanism based on ion exchange between heavy metal ions and H⁺ in the ATHP is proposed. Furthermore, the used ATHP was regenerated by HCl solution and the adsorbent was used repeatedly.     

Modeling the adsorption of Cd (II), Cu (II), Ni (II), Pb (II) and Zn (II) onto montmorillonite

The adsorption of five toxic metallic cations, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), onto montmorillonite was investigated as a function of pH and ionic strength and a two-site surface complexation model was used to predict the adsorption data. The results showed that in the lower pH range, 3∼6 for Cd, Cu, Ni and Zn, and 3∼4.5 for Pb, the adsorption was greatly affected by ionic strength, while in the higher pH range, the adsorption was not. In the lower pH range, the metallic cations were mainly bound through the formation of outer-sphere surface on the permanently charged basal surface sites (≡X⁻), while in the higher pH range the adsorption occurred mainly on the variably charged edge sites (≡SOH) through the formation of inner-sphere surface complexes. Acid-base surface constants and metal binding constants for the two sites were optimized using FITEQL. The adsorption affinity of the five metallic cations to the permanently charged sites of montmorillonite was Pb > Cu > Ni ≈ Zn ≈ Cd, while that to the variable charged sites was Pb ? Cu > Zn > Cd > Ni.     

Surface complexation modelling of Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) adsorption onto kaolinite

Proton binding constants for the edge and basal surface sites of kaolinite were determined by batch titration experiments at 25 °C in the presence of 0.1 M, 0.01 M and 0.001 M solutions of NaNO₃ and in the pH range 3-9. By optimizing the results of the titration experiments, the ratio of the edge sites to the basal surface sites was found to be 6:1. The adsorption of Cd(II), Cu(II), Ni(II), Zn(II) and Pb(II) onto kaolinite suspensions was investigated using batch adsorption experiments and results suggested that in the lower pH range the metallic cations were bound through non-specific ion exchange reactions on the permanently charged basal surface sites (X⁻). Adsorption on these sites was greatly affected by ionic strength. With increasing pH, the variable charged edge sites (SOH) became the major adsorption sites and inner-sphere specifically adsorbed monodentate complexes were believed to be formed. The effect of ionic strength on the extent of adsorption of the metals on the variable charged edge sites was much less than those on the permanently charged sites. Two binding constants, log K_(X2Me) and log K_(SOMe), were calculated by optimizing these constants in the computer program FITEQL. A model combining non-specific ion exchange reactions and inner-sphere specific surface complexations was developed to predict the adsorption of heavy metals onto kaolinite in the studied pH range. Linear free energy relationships were found between the edge site binding constants and the first hydrolysis constants of the metals.     

Adsorptive separation of Pb(II) and Cu(II) from aqueous solutions using as-prepared carboxymethylated waste Lyocell fiber

Adsorptive separation of Pb(II) and Cu(II) using modified waste Lyocell fiber adsorbent was investigated in this research. The waste Lyocell fiber was functionalized through carboxymethylation of the hydroxyl moieties using sodium chloroacetate as modifying agent and was crosslinked with epichlorohydrin to provide water stability. The maximum equilibrium batch uptake in single metal system was 353.45 mg/g for Pb(II) and 98.33 mg/g for Cu(II), according to the Langmuir isotherm model. The adsorption rates were very fast and reached equilibrium within 3 and 5?10 min for Cu(II) and Pb(II), respectively. In competitive binary metal system, the uptake of Cu(II) largely decreased to 38.40 mg/g, and Pb(II) selectivity was observed. Elemental and functional characterization suggested that the adsorption proceeded by ion exchange between the adsorbent and metal ions. In a flow-through column system, adsorption followed by desorption aided in effectively eluting ~260 mg of Pb(II) (out of ~300 mg total adsorbed) from the Pb(II)–Cu(II) binary solution. Finally, the adsorbent was very effective in four successive adsorption–desorption cycles with over 99 % uptake and 94 % desorption efficiencies. The present study may provide an alternative option for waste fiber recycling and could be useful in recovering heavy metal ions from aqueous sources to complement their depleting reserves.     

Goethite adsorption of Cu(II), Pb(II), Cd(II), and Zn(II) in the presence of sulfate: Properties of the ternary complex

Adsorption of Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ onto goethite is enhanced in the presence of sulfate. This effect, which has also been observed on ferrihydrite, is not predicted by the diffuse layer model (DLM) using adsorption constants derived from single sorbate systems. However, by including ternary surface complexes with the stoichiometry FeOHMSO₄, where FeOH is a surface adsorption site and M²⁺ is a cation, the effect of SO₄²⁻ on cation adsorption was accurately predicted for the range of cation, goethite and SO₄²⁻ concentrations studied. While the DLM does not provide direct molecular scale insights into adsorption reactions there are several properties of ternary complexes that are evident from examining trends in their formation constants. There is a linear relationship between ternary complex formation constants and cation adsorption constants, which is consistent with previous spectroscopic evidence indicating ternary complexes involve cation binding to the oxide surface. Comparing the data from this work to previous studies on ferrihydrite suggests that ternary complex formation on ferrihydrite involves complexes with the same or similar structure as those observed on goethite. In addition, it is evident that ternary complex formation constants are larger where there is a stronger metal-ligand interaction. This is also consistent with spectroscopic studies of goethite-M²⁺-SO₄²⁻ and phthalate systems showing surface species with metal-ligand bonding. Recommended values of ternary complex formation constants for use in SO₄-rich environments, such as acid mine drainage, are presented.     

Utilization of ochre as an adsorbent to remove Pb(II) and Cu(II) from contaminated aqueous media

The ability of ochre to remove Pb(II) and Cu(II) from aqueous media has been studied by batch sorption studies varying the contact time, initial metal concentration, initial solution pH and temperature to understand the adsorption behaviour of these metals through adsorption kinetics and isotherms. The pH of the solution and the temperature controlled the adsorption of metal ions by ochre and rapid uptake occurred in the first 30 min of reaction. The kinetics of adsorption followed a pseudo-second-order rate equation (R ² > 0.99) and the isotherms are well described by the Freundlich model. Adsorption of metals onto ochre is endothermic in nature. Between the two metals, Pb(II) showed more preference towards the exchangeable sites on ochre than Cu(II). This study indicates that ochre is a very effective adsorbent in removing Pb(II) and Cu(II) from the aqueous environment with an adsorptive capacity of 0.996 and 0.628 mg g^?1 and removal efficiency of 99.68 and 62.80 %, respectively.     

Metal ion complex formation constants of some sedimentary humic acids with Zn(II), Cu(II) and Cd(II)

Metal ion complex formation constants were determined for several sedimentary humic acids (SHA) derived from a fresh water lake and several coastal marine environments, using a method based on size exclusion chromatography. Only one type of binding site was observed in all cases, and conditional log K_f values of between 5 and 7 (at pH 8, I = 0.01 M) were found. Elemental composition of the SHA was similar to soil HA, except that nitrogen content was significantly higher in the SHA. Other chemical properties of the SHA were consistent with those reported by other workers. While spectroscopic measurements indicated that the SHA may have contained significant amounts of polysaccharide compounds which were not removed by conventional separation and purification procedures, analysis indicated only very low levels of polysaccharides were present in the SHA.     

Effects of pH on isotherm modeling and cation competition for Cd(II) and Cu(II) biosorption on Myriophyllum spicatum from aqueous solutions

The biosorption characteristics of Cd(II) and Cu(II) ions from aqueous solutions obtained using submerged aquatic plant (Myriophyllum spicatum) biomass were investigated in terms of equilibrium, kinetics, thermodynamics, and cation competition. Langmuir and Freundlich models were applied to describe the biosorption isotherm of metal ions by M. spicatum biomass and isotherm constants considering the most important parameter, pH. The variation of sorption isotherm constants showed pH dependence. The Langmuir and Freundlich models fitted the equilibrium data well. The maximum biosorption capacity (q _m) of M. spicatum biomass was determined to be 29.07 mg/g for the Cd(II) ion at pH 5.0 and 12.12 mg/g for the Cu(II) ion at pH 6.0. Chi square analysis showed that the Freundlich model fitted the equilibrium data better than the Langmuir isotherm. Competition of Cd(II) and Cu(II) in a binary solution showed that the Langmuir monolayer capacity of Cd(II) decreased from 29.07 mg/g with only Cd(II) in solution to 12.02 mg/g in the presence of Cu(II). Kinetics results showed that the biosorption processes of both metal ions followed the pseudo-second-order kinetics well. The calculated thermodynamic parameters (?G ⁰, ?H ⁰, and ?S ⁰) showed that biosorption of Cd(II) and Cu(II) ions onto M. spicatum biomass was feasible, spontaneous, and endothermic in nature. Fourier transform infrared spectroscopy spectrum analysis revealed that Cd(II) and Cu(II) sorption was mainly ascribed to carboxyl, hydroxyl, amine, and C–N groups in M. spicatum.     

Biosorption of mercury(II), cadmium(II) and lead(II) ions from aqueous system by microalgae Chlamydomonas reinhardtii immobilized in alginate beads

The potential use of the immobilized microalgae (in Ca-alginate) of Chlamydomonas reinhardtii to remove Hg(II), Cd(II) and Pb(II) ions from aqueous solutions was evaluated using bare Ca-alginate bead as a control system. Ca-alginate beads containing immobilized microalgae were incubated for the uniform growth at 22 °C for 5 days. Effects of pH, temperature, initial concentration of metal ions and biosorbent dosages on the adsorption of Hg(II), Cd(II) and Pb(II) ions were studied. Adsorption of Hg(II), Cd(II) and Pb(II) ions on the immobilized microalgae showed highest values at around pH 5.0 to 6.0. The adsorption equilibrium was represented with Langmuir and Freundlich adsorption isotherms. The adsorption of these ions on the immobilized microalgae followed second-order kinetics and equilibrium was established in about 60 min. The temperature change in the range of 5–40 °C did not affect the adsorption capacities of the immobilized microalgae. The immobilized-algal systems can be regenerated using 2 M NaCl for Hg(II), Cd(II) and Pb(II) ions.     

Coupled mobilization of dissolved organic matter and metals (Cu and Zn) in soil columns

Dissolved organic carbon (DOC) is a key component involved in metal displacement in soils. In this study, we investigated the concentration profiles of soil-borne DOC, Cu and Zn at various irrigation rates with synthetic rain water under quasi steady-state conditions, using repacked soil columns with a metal-polluted topsoil and two unpolluted subsoils. Soil solution was collected using suction cups installed at centimeter intervals over depth. In the topsoil the concentrations of DOC, dissolved metals (Zn and Cu), major cations (Ca²⁺ and Mg²⁺) and anions ( and ) increased with depth. In the subsoil, the Cu and Zn concentrations dropped to background levels within 2 cm. All compounds were much faster mobilized in the first 4 cm than in the rest of the topsoil. DOC and Cu concentrations were higher at higher flow rates for a given depth, whereas the concentrations of the other ions decreased with increasing flow rate. The decomposition of soil organic matter resulted in the formation of DOC, , and and was the main driver of the system. Regression analysis indicated that Cu mobilization was governed by DOC, whereas Zn mobilization was primarily determined by Ca and to a lesser extent by DOC. Labile Zn and Cu²⁺ concentrations were well predicted by the NICA-Donnan model. The results highlight the value of high-resolution in-situ measurements of DOC and metal mobilization in soil profiles.     

Kinetic and equilibrium study of Ni(II) sorption from aqueous solutions onto Peganum harmala-L

In this study, the adsorption behavior of Ni(II) in an aqueous solution system using natural adsorbent Peganum harmala-L was measured via batch mode. The prepared sorbent was characterized by scanning electron microscope, Fourier transform infrared spectroscopy, N₂ adsorption–desorption and pH_zpc. Adsorption experiments were carried out by varying several conditions such as contact time, metal ion concentration and pH to assess kinetic and equilibrium parameters. The equilibrium data were analyzed based on the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherms. Kinetic data were analyzed using the pseudo-first-order, pseudo-second-order and intra-particular diffusion models. Experimental data showed that at contact time 60 min, metal ion concentration 50 mg/L and pH 6, a maximum amount of Ni(II) ions can be removed. The experimental data were best described by the Langmuir isotherm model as is evident from the high R ² value of 0.988. The adsorption capacity (q _m) obtained was 68.02 mg/g at an initial pH of 6 and a temperature of 25 °C. Kinetic studies of the adsorption showed that equilibrium was reached within 60 min of contact and the adsorption process followed the pseudo-first-order model. The obtained results show that P. harmala-L can be used as an effective and a natural low-cost adsorbent for the removal of Ni(II) from aqueous solutions.     

Estimation of heavy metals (Cu,Zn, Pb) input into Punat Bay

The fate of heavy metals (Cu, Pb, Zn) from their sources to the final sink was analysed. Investigations included the identification of sources, the input from each source as well as transport towards their temporary (soil, vegetation, and marine water) and final sink (marine sediments). Research was conducted in the catchment area of Punat Bay on the island of Krk (Northern Adriatic, Croatia). Four sources were identified: long-range transport, traffic, antifouling paints and eroded material which annually introduced about 158 kg of Cu, 175 kg of Pb and 666 kg of Zn into the Bay. Antifouling paints were significant but not the main source of pollution in this area as was considered in previous investigations. Due to long-range transport, the input of Zn was almost four times greater, whereas the input of Pb was almost six times greater than the input from antifouling paints. Aerosols emitted from motor vehicles still represent the mayor source of Pb in this area. Cu originates mostly from antifouling paints and long-range transport. It was estimated that only around 30% of analysed elements introduced into the water column would be deposited in their final sink, i.e. marine sediments.     

Adsorption kinetic models for the removal of Cu(II) from aqueous solution by clay liners in landfills

Liners are commonly used in engineered waste disposal landfill to minimize the potential contamination of the aquatic environment. The adsorption behavior of Cu(II) from aqueous solution onto clay admixed with various mix ratios of quarry fines was investigated. The amount of Cu(II) adsorption increases with increase in contact time. The copper removal efficiencies of the composite mixture gradually decrease from 94.53 % (raw clay) to 85.59 % (20 % of quarry fines with clay), and appreciable decrease in percent removal 75.61 % was found with 25 % of quarry fines with clay. The kinetic adsorption data were analyzed by pseudo-first-order, pseudo-second-order, Bhattacharya–Venkobachar and Natarajan–Khalaf kinetic models to classify adsorption process mechanisms. Kinetic experimental data were good agreement with pseudo-second-order kinetic model with the degree of fitness of the data (R ²) 0.9999 for the adsorption of Cu(II). The results revealed that quarry fines can be used with optimum of 20 % replacement of natural clay for removal of Cu(II) as a liner material in landfills.     

Adsorption of copper(II) from aqueous solution by Beidellite

Dry lakes, degraded sandy grasslands, abandoned farmland and mobile dunes which are widely distributed throughout the arid areas of northern China have been investigated in this work. Gain-size distribution of the surface sediments of Manas lake in Junggar basin, Juyan lake in the Alxa plateau, Zhuye lake in Minqin basin and most deserts (such as Mu Us desert, Otindag desert, Horqin desert and Hulun Buir desert) in China have been analyzed. The results show clay with particle sized <10 μm on the surface sediments of dry lakebed and sandy grassland developed from dry lakebed, respectively, account for >60% and ∼50% of the total mass. Since the tiny particles on the surface of abandoned farmland are blown away easily and rapidly, the content of clay particles in Minqin basin is <14%. The grain-size distribution of mobile dunes in northern China mainly consists of particles >63 μm and few particles <10 μm. Consequently, although sand/dust storms originate primarily in the western deserts, the gobi areas of the Alxa plateau, the north and east of Hexi Corridor and in central Mongolia, the widely distributed dry lakebeds, sandy grasslands and abandoned farmland adjacent to the deserts also contribute to aeolian dusts. Hence, the material sources for sand dust storm in East Asia include inland deserts, but also dry lakes, sandy grasslands and abandoned farmland, which are widely distributed throughout the arid inlands of northern China.