Polydopamine Nanoparticles as a New and Highly Selective Biosorbent for the Removal of Copper (II) Ions from Aqueous Solutions

The adsorption and desorption of copper (II) ions from aqueous solutions were investigated using polydopamine (PD) nanoparticles. The nanoscale PD nanoparticles with mean diameter of 75?nm as adsorbent were synthesized from alkaline solution of dopamine and confirmed using scanning electron microscopy and X-ray diffraction analysis. The effects of pH (2?C6), adsorbent dosage (0.2?C0.8?g?L^?1), temperature (298?C323?K), initial concentration (20?C100?mg?L^?1), foreign ions (Zn²⁺, Ni²⁺, Cd²⁺, Fe²⁺, and Ag⁺), and contact time (0?C360?min) on adsorption of copper ions were investigated through batch experiments. The isotherm adsorption data were well described by the Langmuir isotherm model. The maximum uptake capacity of Cu²⁺ ions onto PD nanoparticles was found to 34.4?mg/g. The kinetic data were fitted well to pseudo-second-order model. Moreover, the thermodynamic parameters of the adsorption (the Gibbs free energy, entropy, and enthalpy) were studied.     

Preparation of Activated Carbon from Sugarcane Bagasse Soot and Methylene Blue Adsorption

Sugarcane bagasse soot is an agro-industrial residue rich in carbon that can be transformed into value-added materials, such as activated carbons. Therefore, this work aimed at producing activated carbon from sugarcane bagasse soot, using CO₂ at 800, 850, and 900 °C, and investigating its efficiency to adsorb methylene blue as model contaminant. The results showed that the surface area and pore volume increased in the obtained carbons, with high specific areas (up to 829 m²/g), and the isotherms of the N₂ adsorption describe mesoporous materials. The morphology of the prepared activated carbons showed that sugarcane bagasse soot and the activated carbons kept the fibrous structure of sugarcane bagasse, but after activation, they have cavities that resemble a honeycomb. Adsorption studies with methylene blue dye showed that the activation process resulted in adsorption capacities up to 11 times higher than sugarcane bagasse soot, which is comparable with commercial activated carbon. Dye adsorption kinetics could be described by a pseudo-second-order dependency in the studied materials, and the adsorption isotherms were better fitted by the Langmuir model. It is emphasized that cost-effective materials that are similar to commercial activated carbon were obtained.     

Zinc Removal from the Aqueous Solutions by the Chemically Modified Biosorbents

Biosorbents are the natural origin adsorbents, which popularity in environmental engineering is steadily increasing due to their low price, ease of acquisition, and lack of the toxic properties. Presented research aimed to analyze the possibility of chemical modification of the straw, which is a characteristic waste in the Polish agriculture, to improve its biosorption properties with respect to removal of selected metals from aquatic solutions. Biosorbents used during the tests was a barley straw that was shredded to a size in the range of 0.2–1.0 mm. The biosorption process was performed for aqueous solutions of zinc at a pH 5. Two different modifications of straw were analyzed: esterification with methanol and modification using the citric acid at elevated temperature. The results, obtained during the research, show a clear improvement in sorption capacity of the straw modified by the citric acid. In the case of straw modified with methanol, it has been shown that the effectiveness of zinc biosorption process was even a twice lower with respect to the unmodified straw. Moreover, it was concluded that the removal of analyzed metals was based mainly on the ion-exchange adsorption mechanism by releasing a calcium and magnesium ions from the straw surface to the solution.

Open image in new window

Graphical Abstract ?

     

镁铝双氢氧化物和镁铁铝改性蒙脱土去除水体中磷的吸附效果研究

通过间歇式批实验和动力学实验研究了不同pH条件下磷酸盐在镁铝双氢氧化物（Mg-Al-LDH）、钠基膨润土（Na-Mt）及镁铁铝改性膨润土（Mg-Al-Mt、Fe-Mt和Fe-Al-Mt）的吸附特征。结果表明,在pH4.5～9.0范围内,随着pH的升高,Na-Mt,Fe-Mt和Fe-Al-Mt3种矿物对磷的吸附率相应减少,镁铝双氢氧化物对磷的吸附率有所增加;Mg-Al-LDH、Fe-Mt和Fe-Al-Mt的对磷吸附率约为95%,比Mg-Al-Mt高40%,比Na-Mt高80%。用Langmuir方程描述磷的等温吸附过程,最大吸附容量（Qm）大小顺序为Fe-Al-Mt〉Fe-Mt〉Mg-Al-LDH〉Mg-Al-Mt〉Na-Mt,b值大小依次为Mg-Al-LDH〉Fe-Mt〉Fe-Al-Mt〉Mg-Al-Mt〉Na-Mt,最大缓冲容量（Qmb）以Mg-Al-LDH的为最大,Na-Mt的为最小;Freundlich等温吸附方程参数KF代表相对吸附容量,以Mg-Al-LDH的KF值最高,依次是Fe-Mt、Fe-Al-Mt和Mg-Al-Mt,Na-Mt的KF值最小,这与Qmb的结果一致;决定系数（R2）表明,Langmuir等温吸附方程能更好地拟合铁改性蒙脱土和铁铝改性蒙脱土,而Freundlich方程对钠蒙脱土,双氢氧化物和镁铝改性蒙脱土的拟合效果要好。磷酸盐吸附过程分为快反应和慢反应,用动力学实验数据进行拟合,准二级动力学方程能够更好的拟合改性蒙脱土和Mg-Al-LDH对磷的动力学吸附数据,其决定系数为0.999;Elovich方程拟合改性蒙脱土磷酸盐的吸附数据也有很好的相关性（R2为0.89～0.94）。Na-Mt矿物磷酸盐的吸附用抛物线扩散方程描述最为合适,原因可能是磷酸盐镶嵌在矿物层间是一个扩散过程,不涉及化学吸附过程。     

Chemically Modified Crop Residues as a Low-Cost Technique for the Removal of Heavy Metal Ions from Wastewater

Batch adsorption experiments were carried out to evaluate the effect of type of crop residues and chemical pretreatment solutions on the removal efficiency of heavy metal ions at different concentrations of synthetic wastewater solutions. Rice straw, cotton stalks, and maize stalks were pretreated with different solutions (i.e., sulfuric acid, oxalic acid, sodium hydroxide, and distilled water as the control treatment) in order to increase their metal-binding capacity. Results indicated that cotton stalks were the best biosorbent material according to their efficiency in removal of heavy metal ions. Sodium hydroxide was the best chemical pretreatment method for stimulating the biosorption capacity of crop residues. Ions of Pb²⁺ had the highest biosorption ratio among all competitive ions, whereas Mn²⁺ ions had the lowest. The removal efficiency decreased as the concentration of heavy metal ions increased in aqueous solutions. Sorption equilibrium isotherms could be described by the Langmuir model in most cases, whereas an isotherm of S shape was observed in other cases, which did not follow the Langmuir isotherm model. In conclusion, cotton stalks pretreated with sodium hydroxide could be used as an efficient technique for wastewater remediation prior to irrigation due to its low-cost, little processing, and high biosorption capacity.     

Removal of Mercury Ions from Mixed Aqueous Metal Solutions by Natural and Modified Zeolitic Minerals

Research works on the removal of mercury from water by zeolitic mineralshow that small quantities of this element are sorbed. In this work the mercury sorption from aqueous solutions in the presence and absence of Cu(II), Ni(II) and Zn(II) onto a Mexican zeolitic mineral unmodified and modified with cysteamine hydrochloride or cystamine dihydrochloride was investigated in acidic pH. The zeolitic minerals were characterized by thermogravimetric analysis, scanning electron microscopy, X-ray diffraction and FTIR. The sorption kinetics behavior and the retention isotherms for mercury were determined in the natural and treated zeolitic mineral samples. It was found that the amounts of sulfur on the modified zeolitic minerals were 0.375 (cysteamine hydrochloride) and 0.475 (cystamine dihydrochloride) mmol g^-1, which were not saturated to their total capacities of adsorption for the maximum concentration used (0.310 mM). Under the experimental conditions, the retention of mercury was the highest for the zeolitic minerals treated with the organic compounds, with adsorption capacities ranging from 0.0107 to 0.0509 mmol Hg g^-1.The retention was not affected by the presence of others heavy metals studied in this work as expected.     

Adsorption of Petroleum Monoaromatics from Aqueous Solutions Using Granulated Surface Modified Natural Nanozeolites: Systematic Study of Equilibrium Isotherms

Petroleum monoaromatics including benzene, toluene, ethylbenzene, and xylenes (BTEX) are among the notorious volatile organic compounds that contaminate water and soil. In this study, a surfactant- modified natural zeolite and its relevant granulated nanozeolites were evaluated as potential adsorbents for removal of petroleum monoaromatics from aqueous solutions. All experiments performed in batch mode at constant temperature of 20°C and pH of 6.8 for 48 h. The results revealed that the amount of BTEX uptake on granulated zeolites nanoparticles were remarkably higher than the parent micron size natural zeolite (in the order of four times). The isotherms data were analyzed using five models namely, Langmuir, Fruendlich, Elovich, Temkin, and Dubinin?CRadushkevich models. It was concluded that the Langmuir model fits the experimental data. The measured adsorption capacities were 3.89 and 4.08 mg of monoaromatics per gram of hexadecyltrimethylammonium-chloride and n-cetylpyridinium bromide (CPB)-modified granulated nanozeolite, respectively. Considering the type of surfactant, adsorbents modified with CPB showed greater tendency for the adsorption of the adsorbates.     

Removal of Copper and Cadmium Ions from Diluted Aqueous Solutions by Low Cost and Waste Material Adsorbents

The sorption of copper and cadmium ions using activated carbon,kaolin, bentonite, diatomite and waste materials such as compost,cellulose pulp waste and anaerobic sludge as sorbents is reported. Equilibrium isotherms were obtained for the adsorption of these metals in single and binary solutions. Bentonite presented the highest adsorption capacities for both copper and cadmium. A competitive uptake was observed when both metals are present; copper being preferentially adsorbed by all materials with theexception of anaerobic sludge. Equilibrium data were fitted toLangmuir and Freundlich models, with satisfactory results for most of the adsorbent-metal systems studied.Of all the adsorbents studied, bentonite and compost presentedthe highest removal efficiencies, reaching 99% for copper whencadmium is also present, for initial solution concentrations ofup to 100 mg L^-1. Anaerobic sludge has a greater preferencefor cadmium, even in the presence of copper, with removal efficiencies of 98% for similar concentrations to those mentioned above.     

Removal of Copper Ions from Simulated Wastewaters Using Different Bicomponent Polymer Membranes

Polybrominated diphenyl ethers (PBDEs) are a class of global flame retardants whose residues have markedly increased in fish and human tissues during the last decade. They belong to persistent and toxic contaminants which need more attention and toxicological study as their degradation in the environment is not well understood. This study characterizes 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) bioconcentration, elimination and biotransformation in juvenile turbot Psetta maxima, in order to evaluate the risk of its bioaccumulation in the marine environment. During this study, juvenile turbot were exposed to environmentally relevant BDE-47 concentrations from 0.001 to 1 μg/L for 16 days via aqueous exposure. This study found that juvenile turbot bioconcentrated and biotransformed BDE-47. There was no difference in standard length or weight between control and exposed fish. Uptake and elimination of BDE-47 by the turbot during exposure were examined in controlled laboratory experiments. Bioconcentration of BDE-47 was similar in fish from all treatment groups. Bioconcentration was rapid and increased with exposure time, since the bioconcentration factor (BCF) was higher. However, elimination was slower in comparison and low elimination was detected after 10 days in clean water. BDE-47 concentration in water influences the BCF. Half-life ranged between 37 and 108 days and theoretical times t ₉₀ could range from 120 to 358 days. The present study demonstrates a stepwise debromination of BDE-47 to BDE-28.

     

Cell-Associated Adsorption of Thorium or Uranium from Aqueous System Using Various Microorganisms

The cell-associated adsorption of thorium or uranium from the solution containing each metal only at pH 3.50 using various microorganisms was examined. Among the species tested, high thorium adsorption abilities were exhibited by strains of the gram-positive bacteria Arthrobacter nicotianae IAM12342, Bacillus megaterium IAM1166, B. Subtilis IAM1026, Micrococcus luteus IAM1056, Rhodococcus erythropolis IAM1399, and Streptomyces levoris HUT6156. And high uranium adsorption abilities were found in some gram-positive bacterial strains S. albus HUT6047, S. levoris HUT6156, and A. nicotianae IAM12342. Among these highly efficient thorium and uranium adsorbing microorganisms, S. levoris, which could adsorb the largest amount of uranium from the aqueous solution at pH 3.50, could adsorb about 383 mol thorium and 390 mol uranium per gram dry weight of microbial cells from the solution containing thorium or uranium at pH 3.50. The amount and time course of thorium adsorbed were almost unaffected by co-existing uranium; however, the adsorption of thorium was faster when carried out after the adsorption of uranium. Thorium adsorption also became faster when uranium was added after thorium adsorption. The effect of pH on thorium adsorption was also discussed.     

Selective Adsorption of Silver Ions from Highly Acidic Aqueous Solutions by Polymers Containing Multiple Sulfur Groups

A polymer (PDMTD) containing multiple sulfur groups is prepared and used for selective adsorption of silver ion from aqueous solution. The batch adsorption experiments are conducted to research the effects of the different parameters on adsorption of silver ion, including pH, adsorption time, and initial Ag(I) concentration. The maximum uptake of Ag(I) is 127.89 mg/g at pH?=?1. The adsorption equilibrium data are fitted with different isotherm and kinetics models. The results show that the adsorption process of Ag(I) follows a pseudo-second-order kinetic model and Langmuir isotherm mode. Chelation interaction between Ag(I) and sulfur and nitrogen atom is the main adsorption mechanism. PDMTD shows the good selectivity from the coexisting ions and can be reused at least five times. The polymers containing multiple sulfur groups have wide application prospect to selectively capture silver ions from highly acidic aqueous solutions.     

Kinetic and Thermodynamic Behavior on the Sorption of Clindamycin from an Aqueous Medium by Modified Surface Zeolitic Tuffs

Clindamycin (CLD), an antibiotic derivate of lincomycin, is widely used; the presence of this drug in the wastewater and the environment could produce resistance in bacteria. In this work, the sorption of this drug by two surfactant-modified zeolitic tuffs was studied considering contact time, initial concentration, pH, and temperature. The kinetic behavior indicates that the equilibrium times were between 15 and 12 h for all materials, and the results were best adjusted to Ho and Mc Kay model. The highest adsorption was obtained with the hexadecyltrimethylammonium-modified zeolitic tuff from Oaxaca, Mexico (1.56 mg/g). The sorption isotherms obtained showed a linear behavior, indicating a partition mechanism. The thermodynamic parameters were determined from the isotherms at different temperatures and Van Ho equation; the processes are exothermic and not spontaneous. The best pH for the adsorption is between 8 and 11. The results show that the modified zeolitic tuffs are potential materials for the adsorption of CLD from water.     

Adsorption of Copper(II) Ion from Aqueous Solution Using Biochar Derived from Rambutan (Nepheliumlappaceum) Peel: Feedforward Neural Network Modelling Study

Biochars, derived from rambutan (Nepheliumlappaceum) peel through slow pyrolysis, were characterised and investigated as potential adsorbent for the removal of copper ion, Cu(II) from aqueous solution. Characteristics of five biochars of rambutan peel with different pyrolytic temperatures ranging from 300 to 700 °C (B300, B400, B500, B600, B700) were studied, and adsorption abilities of respective biochars were evaluated. Adsorption experiments were carried out by varying adsorbent dosage (0.2, 0.4, 0.8, 1.0, 2.0, and 4.0 g/L) and initial copper ion, Cu(II) concentrations (50 and 100 mg/L) to determine the optimum pyrolytic temperature of biochar with high adsorption affinity. The adsorption kinetics were best described by the pseudo-second order model for all the tested biochars, while the adsorption equilibrium best fitted by Langmuir isotherm. The overall results showed that biochar derived at 600 °C can be used as an effective adsorbent for removal of Cu(II) from aqueous solutions. Furthermore, feedforward artificial neural network (FFBP) modelling was performed to compare the simulated results with experimental output data of Thermogravimetric analysis (TGA) and atomic absorption spectroscopy (AAS) analysis which were trained using Levenberg-Marquardt (LM) backpropagation algorithm. The FFBP structure for pyrolysis process comprised of TGA temperature as input and biomass final weight as output. The adsorption modelling was simulated using adsorption time, temperature, biochar dosage and initial Cu(II) concentration as input data, while final Cu(II) concentration was used as output data to the network. Finally, modelling structure of 1-9-1 and 4-8-1 gave best performance with regression, R ² value of 0.9999 and 0.9547 for TGA and AAS analysis, respectively.     

Removal and Preconcentration of Cobalt Ions from Aqueous Media Using ImHA Packed Column by On-Line SPE System

This work assesses the use of immobilized humic acid (ImHA) onto aminopropyl silica (APS) as a sorbent for the removal and preconcentration of trace amounts of cobalt ions by on-line solid phase extraction (SPE) technique in the column system prepared in our laboratory. Different parameters, such as the effect of the pH, concentration, and flow rate, were studied and throughput was observed by a UV detector. All SPE steps were monitored by breakthrough curves used to visualize distribution of cobalt concentration between mobile and solid phase. The solutions collected from stripping steps were analyzed in atomic absorption spectrometer (AAS) and the amount of sorbed ions was calculated. Sorption characteristics were evaluated by using common adsorption isotherms and Scatchard plot analysis. From the obtained results, it was seen that sorption mechanism of cobalt ions were fitted to Langmuir model on a large scale and thought to be localized. Mean free energy (E?=?40.82?kJ?mol^?1) calculated from D-R isotherm showed that chemical interactions are more effective than physical interactions. This investigation reveals a new, simple, environmentally friendly, and cost-effective method for removal and preconcentration of cobalt ions from aqueous solutions by a new aminopropyl silica-immobilized humic acid material.     

Removal of Methylene Blue from an Aqueous Medium Using Atemoya Peel as a Low-cost Adsorbent

Water, Air, & Soil Pollution - The objective of the present study was the synthesis and characterization of chitosan-alginate-based cross-linked copolymer (CACC) for the effective removal of...     

Removal of Cu(II) Ions from Aqueous Solution by Magnetic Chitosan-Tripolyphosphate Modified Silica-Coated Adsorbent: Characterization and Mechanisms

A magnetic chitosan-modified Fe₃O₄@SiO₂ with sodium tripolyphosphate adsorbent (MTPCS) was synthesized by surface modification of Fe₃O₄@SiO₂ with chitosan using sodium tripolyphosphate (STPP) as the cross-linker in buffer solution for the adsorption of Cu(II) ions from aqueous solution. The structure and morphology of this magnetic nanoadsorbent were examined by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), BET surface area measurements, Fourier transform infrared spectrometer (FTIR), and X-ray photoelectron spectroscopy (XPS). The effects of initial pH, adsorbent amount, and initial concentration of heavy metal ions were investigated by batch experiments. Moreover, adsorption isotherms, kinetics, and thermodynamics were studied to understand the mechanism of adsorbing metal ions by synthesized MTPCS. The results revealed that adsorption kinetics was best depicted by the pseudo-second-order rate mode and intraparticle-diffusion models. The adsorption isotherm fitted well to the Langmuir model. Moreover, thermodynamic study verified the adsorption process was endothermic and spontaneous in nature. The maximum adsorption occurred at pH 5 ± 0.1, and the adsorbent could be used as a reusable adsorbent with convenient conditions.     

<Emphasis Type="Italic">Caesalpinia ferrea</Emphasis> Fruits as a Biosorbent for the Removal of Methylene Blue Dye from an Aqueous Medium

In the present work, a biosorbent was produced through the alkaline washing of Brazilian ironwood fruits. Infrared and thermogravimetric analyses showed changes in the obtained biosorbent with the removal of extractives, whose micrograph presents a more fibrous structure for the treated material. The biosorption behavior of the methylene blue dye shows efficiency at pH above five, and at alkaline pH, it reaches removal efficiency of up to 90% for five successive cycles. Adsorption kinetics is fast and fits the pseudo-second-order model, which, with the best fit of the Langmuir isotherm model, indicates a chemical adsorption mechanism. The thermodynamic trials express the spontaneity of biosorption and enthalpy and entropy variations of ??10.47 kJ mol^?1 and 51.84 J mol^?1 K^?1, respectively. The maximum biosorption capacity is of 125.2 mg g^?1 for the temperature of 25 °C, consisting in a low-cost alternative for the removal of this type of contaminant from an aqueous medium.     

Adsorption of Acrylonitrile on Some Soils and Minerals from Aqueous Solutions

Equilibrium and kinetic studies have been made on the adsorption of acrylonitrile(CH2=CHCN) on three soils and four minerals from aqueous solutions.It was shown that the organic matter was the major factor affecting the adsorption process in the soils.The conformity of the equilibrium data to linear type(one soil) and Langmuir type(two soils) isotherms indicated that different mechanisms were involved in the adsorption.This behavior appears bo be related to the hydrophobicity of soil organic matter due to their composition and E4/E6 ratio of humic acids.The adsorption kinetics were also different among the soils,indicating the difference in porosity of organic matter among the soils,and the kinetics strongly affected the adsorption capacity of soils for acrylonitrile.Acrylonitrile was slightly adsorbed from aqueous solutions on pyrophyllite with electrically neutral and hydrophobic nature,and practically not on montmorillonite and kaolinite saturated with Ca.However,much higher adsorption occurred on the zeolitized coal ash,probably caused by high organic carbon content(107g/kg).     

Magnetic Solid-Phase Extraction Based on Modified Iron Oxide Nanoparticles for the Preconcentration of Ultra-Trace Amounts of Copper Ions in the Environmental and Plant Samples and its Determination Using FAAS

In the present work, magnetic iron oxide nanoparticles (MIONPs) coated with sodium dodecyl sulfate (SDS) and modified with 1-(2-pyridylazo)-2-naphthol (PAN) as a new nanoparticle were prepared and used as an adsorbent for the extraction and preconcentration of copper ions. After adsorption, copper ions were desorbed with nitric acid (HNO₃), followed by determination with flame atomic absorption spectrometry (FAAS). The extraction conditions0. were investigated systematically. The linear range 3.0–500.0 ng mL^?1 and the detection limit of 0.6 ng mL^?1 were obtained. The relative standard deviation (RSD) of the method for seven replicate determinations of 0.1 µg mL^?1 of Cu(II) was 2.2%. The method was applied for the determination of Cu(II) in different water samples with good trueness. The accuracy was also evaluated through analyses of a certified reference material (CRM TMDW-500).