Multi-component adsorption of copper,nickel and zinc from aqueous solutions onto activated carbon prepared from date stones

The removal of Cu²⁺, Ni²⁺, and Zn²⁺ ions from their multi-component aqueous mixture by sorption on activated carbon prepared from date stones was investigated. In the batch tests, experimental parameters were studied, including solution pH, contact time, initial metal ions concentration, and temperature. Adsorption efficiency of the heavy metals was pH-dependent and the maximum adsorption was found to occur at around 5.5 for Cu, Zn, and Ni. The maximum sorption capacities calculated by applying the Langmuir isotherm were 18.68 mg/g for Cu, 16.12 mg/g for Ni, and 12.19 mg/g for Zn. The competitive adsorption studies showed that the adsorption affinity order of the three heavy metals was Cu²⁺?>?Ni²⁺?>?Zn²⁺. The test results using real wastewater indicated that the prepared activated carbon could be used as a cheap adsorbent for the removal of heavy metals in aqueous solutions.     

Rapid and efficient removal of Ni2+ from aqueous solution by the one-pot synthesized EDTA-modified magnetic nanoparticles

A facile one-pot process has been proposed to prepare the novel ethylenediaminetetraacetic acid (EDTA)-modified magnetite nanoparticles (EDTA-MNPs). The bared Fe₃O₄ magnetite nanoparticles and EDTA-MNPs were characterized using FTIR spectroscopy, TEM, VSM, and X-ray diffraction. The application of the modified magnetite nanoparticles for metal ion uptake was studied using Ni²⁺ as a model. The adsorption was fast and the equilibrium was established within 5 min, and the adsorption kinetics of Ni²⁺ onto EDTA-MNPs followed the pseudo second-order chemisorption mechanism. Maximum adsorption capacity for Ni²⁺ reached as high as 41.3 mg/g at pH 6. The successive adsorption–desorption studies indicated that the EDTA-MNPs kept the adsorption and desorption efficiencies constant over ten cycles. Importantly, EDTA-MNPs were able to remove nearly 100 % of Ni²⁺ from real water.     

Removal and mechanism of Cu (II) and Cd (II) from aqueous single-metal solutions by a novel biosorbent from waste-activated sludge

The removal and mechanism of Cu²⁺ and Cd²⁺ from aqueous single-metal solutions were investigated by using a novel biosorbent from waste-activated sludge. A series of adsorption experiments was designed to disclose the effects of the key factors on the adsorption capacity of the biosorbent for the metal ions. The mass ratio of the biosorbent to metal ion was optimized as 2 to balance the adsorption capacity and the removal efficiency. A right shaking speed (150 r/min) not only ensured enough contact frequency between the sorbent and the adsorbate but also reduced the mass transfer resistance. The natural pH value (about 5.5) of the metal solutions benefited a high adsorption capacity of the biosorbent and avoided the consumption of acid or base for pH adjustment. The adsorption reactions belonged to the endothermic process between 15 and 45 °C. As the scanning electron microscopy (SEM) images showed, the meshy structure with long chains and many branches was ideal for the biosorbent to quickly capture the metal ions. The energy-dispersive X-ray (EDX) spectra confirmed that the adsorbed metal ions lay in the precipitates of the adsorption reactions. According to the FTIR analyses, the functional groups responsible for Cu²⁺ adsorption majorly consisted of O–H, N–H, COOH, CONH₂, and the groups containing sulfur and phosphorus, while those for Cd²⁺ adsorption contained O–H, N–H, COOH, and CONH₂. The differences in the responsible functional groups explained the phenomenon that the adsorption capacity of the biosorbent for Cu²⁺ was higher than that for Cd²⁺.     

Removal of heavy metal ions from wastewater by a novel HEA/AMPS copolymer hydrogel: preparation, characterization, and mechanism

This study aims to synthesize 2-hydroxyethyl acrylate (HEA) and 2-acrylamido-2-methylpropane sulfonic (AMPS) acid-based hydrogels by gamma radiation and to investigate their swelling behavior and heavy metal ion adsorption capabilities. The copolymer hydrogels prepared were characterized via scanning electron microscopy, Fourier transformed infrared spectra, thermal gravimetric analysis, and X-ray photoelectron spectroscopy. The research showed that the copolymer hydrogel was beneficial for permeation due to its porous structure. In addition, the experimental group A-2-d [70 % water volume ratio and (n (AMPS)/n (HEA))?=?1:1] was an optimal adsorbent. The optimal pH was 6.0 and the optimal temperature was 15 °C. Pb²⁺, Cd²⁺, Cu²⁺, and Fe³+ achieved adsorption equilibriums within 24 h, whereas Cr³⁺ reached equilibrium in 5 h. Pb²+, Cd²⁺, Cr³⁺, and Fe³⁺ maximum load capacity was 1,000 mg L^?1, whereas the Cu²⁺ maximum capacity was 500 mg L^?1. The priority order in the multicomponent adsorption was Cr³⁺>Fe³⁺>Cu²⁺>Cd²⁺>Pb²⁺. The adsorption process of the HEA/AMPS copolymer hydrogel for the heavy metal ions was mainly due to chemisorption, and was only partly due to physisorption, according to the pseudo-second-order equation and Langmuir adsorption isotherm analyses. The HEA/AMPS copolymer hydrogel was confirmed to be an effective adsorbent for heavy metal ion adsorption.     

Adsorptive removal of Pb2+ form aqueous solution by macrocyclic calix[4]naphthalene: kinetic, thermodynamic, and isotherm analysis

Background

The adsorption characteristics of Pb²⁺ ions from aqueous solutions onto calix[4]naphthalene have been investigated.

Method

Calix[4]naphthalene was prepared by the condensation of 1-naphthol and formaldehyde (1:2) in presence of hydrochloric acid at 80°C. The effect of various operation parameters, such as solution pH, initial metal ion concentration, contact time, and temperature, on the adsorption capacity of calix[4]naphthalene for Pb²⁺ have been investigated.

Result

Experimental results showed that the adsorption of Pb²⁺ ions increased with the increase in solution pH and temperature. Langmuir and Freundlich isotherms models were used to describe the adsorption behavior of Pb²⁺ by calix[4]naphthalene. Equilibrium data fitted well with the Langmuir isotherm model and the maximum adsorption capacity of calix[4]naphthalene for Pb²⁺ at 30°C was found to be 29.15 mg g^?1. Kinetic studies indicated that the adsorption followed pseudo-second order model and the thermodynamic studies revealed that the adsorption process was spontaneous and endothermic in nature. The obtained results demonstrated that calix[4]naphthalene can be used as an effective adsorbent for Pb²⁺ ions removal from water.     

荔枝皮对重金属Ni~(2+)的吸附性能

采用批量实验研究了荔枝皮对水中重金属Ni2+吸附的影响因素(如接触时间、pH和吸附剂量)、吸附等温线、吸附动力学和吸附热力学等,并讨论了其吸附机理。结果表明,未改性荔枝皮和改性荔枝皮对Ni2+的吸附平衡时间均为30min;最适pH为6.0~7.0;最佳吸附剂量均为20 g/L。吸附过程均能用Langmuir和Freundlich等温线模型来很好地描述,且均符合假二次动力学模型。改性荔枝皮和未改性荔枝皮对Ni2+的最大比吸附量分别为11.88和5.19 mg/g。此外,热力学研究结果表明,未改性荔枝皮和改性荔枝皮吸附Ni2+均属于非自发的放热过程。     

胺基树脂的合成及对水中重金属离子的吸附特征

研究了使用氯甲基化聚苯乙烯交联微球为前驱体与二乙烯三胺经回流反应合成胺基树脂及其对水中Cd2+和Ni2+的吸附特征。结果表明,胺基官能团成功地嫁接到树脂表面,胺基含量为5.6 mmol/g。胺基树脂对Cd2+和Ni2+的吸附等温线表明,温度的升高有利于吸附,且吸附等温线都符合Langmuir模型。pH值对吸附的影响较大,最佳吸附pH值范围为4~6。2种金属离子在胺基树脂上的吸附都符合准二级动力学方程。     

三乙二醇二甲基丙烯酸酯为交联剂制备的高吸水树脂对重金属的吸附

以前期工作中合成的树脂PAANa-TE为吸附剂进行重金属吸附测试,考察吸附剂用量、丙烯酸中和度、吸附时间、溶液pH、初始浓度和吸附温度对树脂吸附重金属离子Cu2+、Pb2+、Cr3+和Co2+性能的影响,用原子吸收分光光度计测定了树脂吸附Cu2+、Pb2+、Cr3+和Co2+后的残留浓度,树脂对4种金属离子的吸附容量分别为21.59、2.39、5.66和4.98 mmol/g,吸附容量大小为Cu2+Cr3+Co2+Pb2+,吸附速率顺序为Cr3+Pb2+Cu2+Co2+。结果表明,该树脂对高浓度重金属离子有较快速,高效率的吸附,吸附过程在100 min左右吸附容量达到最大,并用不同浓度的酸对吸附重金属离子的树脂进行脱附处理,脱附量很小,据此可考虑进一步对金属离子进行回收处理。且脱附率较低,因此,可对工业化和城市化进程所产生的各种化学形态的重金属水体污染物造成的生态环境和质量问题起到重要的改善作用。     

改性荞麦壳对水溶液中Cu~(2+)离子吸附效果及机理

以柠檬酸对荞麦壳进行化学改性,改性后荞麦壳吸附剂对Cu2+的吸附量增加。研究了不同pH、吸附剂投入量、浓度和时间对吸附效果的影响。在pH值为5.5,Cu2+初始浓度50 mg/L,吸附剂投入量为1 g,吸附时间为120 min的条件下,Cu2+的吸附量达到较大值。通过用改性荞麦壳吸附剂对Cu2+的热力学吸附过程的分析,结果表明,改性荞麦壳吸附剂符合Langmuir吸附等温模式,改性荞麦壳吸附剂对Cu2+的吸附存在化学吸附,改性荞麦壳的最大吸附量可以达2.26 mg/g。研究改性荞麦壳吸附剂吸附Cu2+的动力学特性,吸附动力学行为可用准二级速率方程进行很好的描述,准二级吸附速率常数随温度升高而增大。准一级速率方程和颗粒扩散模型可以较好地描述吸附初始阶段,Cu2+浓度较高,颗粒内扩散;吸附后期,Cu2+浓度较低,受到颗粒外扩散的控制。总之,整个吸附过程可能是多种动力学机理共同作用的结果。     

Adsorption of ammonium on biochar prepared from giant reed

Giant reed was used as precursor for making biochar in order for the adsorption of NH₄ ⁺–N from aqueous solution. And the adsorption of the product to NH₄ ⁺–N was examined. The surface features of biochar were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy/energy dispersive spectrometer (SEM-EDS), and X-ray diffraction (XRD). XRD patterns showed several peaks and correspond to the high amount of crystalline material. The crystals contain KCl, K₂O, CaO, MgO, and SiO and possess high surface area which enhances adsorption. The influence of different parameters such as initial concentration, adsorption time, pH, and ionic strength has been carried out. The adsorption could reach equilibrium through 24 h reaction and had the best adsorption amount at the solution pH values from 7 to 9. The cation has great influence on the adsorption of NH₄ ⁺–N, whereas the anion exerted a weaker effect. The adsorption followed pseudo-first-order and pseudo-second-order models. And the intraparticle diffusion and desorption studies further elucidated that the mechanism of adsorption on the product was ion exchange. The product equilibrium data was well described by the Langmuir and Freundlich model. The maximum adsorption capacities were 1.490 mg/g. Biochar derived from giant reed at 500 °C was suggested as a promising adsorbent for the removal of NH₄ ⁺–N from slightly polluted wastewater.     

改性玉米秸秆吸附Cu2+的动力学和热力学

本研究用ZnCl2作为活化剂,使用功率640 W的微波照射4 min的方法制备改性玉米秸秆。考察投加量、pH、吸附时间对吸附性能的影响,并对等温吸附特征、吸附动力学和热力学进行了系统研究。结果表明:投加量为0.2 g,pH为6,改性玉米秸秆对Cu2+具有很好的吸附效果,吸附在8 h后达到平衡。该吸附过程符合Langmuir及Freundlich等温吸附模型和准二级动力学方程,其反应的吉布斯自由能△G<0,为自发反应过程。     

木屑黄原酸盐对双离子体系中铜镍的吸附

利用木屑制备木屑黄原酸盐吸附剂,对其进行FTIR、XRD和BET分析,并考察了对双离子体系中铜镍离子的吸附情况,重点研究了木屑黄原酸盐吸附量的预测和吸附初始速率的计算。结果表明,在铜镍双离子体系中,利用扩展的Langmuir模型能很好地预测木屑黄原酸盐对铜镍离子的吸附;吸附之初,吸附速率很快,并且随着干扰离子的浓度增大,所考察离子的初始速率逐渐减小。吸附情况说明,木屑黄原酸盐是一种具有良好吸附性能的吸附材料。     

Phenol removal from wastewater by adsorption on zeolitic composite

It is well known that adsorption is an efficient method of removal of various pollutants from wastewater. The present study examines the phenol removal from water by adsorption on a new material, based on zeolitic volcanic tuff. This compound contains zeolitic tuff and cellulose, another known adsorbent, in a mass ratio of 4 to 1. The performances of the new adsorbent composite were compared with those of a widely used adsorbent material, zeolitic volcanic tuff. The adsorbent properties were tested on batch synthetic solutions containing 1–10 mg L^?1 (1–10 ppm) phenol, at room temperature without pH adjustment. The influence of the adsorbent dose, pH and contact time on the removal degree of phenol from water was investigated. The experimental data were modeled using the Langmuir, Freundlich, and Temkin adsorption isotherms. The Langmuir model was found to best represent our data revealing a monolayer adsorption with a maximum adsorption capacity between 0.12 and 0.53 mg g^?1 at 25 °C, for 2.00 g of adsorbent, depending on the initial phenol concentration. The adsorption kinetic study was performed using a pseudo-first- and pseudo-second-order kinetic models illustrating that phenol adsorption on zeolite composite is well described by pseudo-first kinetic equations. Our results indicated that phenol adsorption on the new adsorbent composite is superior to that on the classic zeolite.     

硅烷化改性沸石对重金属离子的吸附性能

制得一种用于重金属废水处理的新型硅烷化改性沸石吸附剂,成本低、效果显著且稳定。通过对改性沸石表征,分析了改性对沸石结构的影响。结果表明,改性一定程度降低了原沸石的晶体特征,但基本上保持了其结构组成;硅烷化改性成功地在沸石上接枝了氨基。对硅烷化沸石的特性研究,得出硅烷化沸石对Ni2+、Cu2+、Zn2+和Pb2+吸附最佳投加量为1、1、1.6和0.6 g/L,且此时对4种离子的去除率也较好;吸附动力学研究得出,其吸附过程可用二级动力学方程较好地拟合;吸附达到平衡时,4种金属离子的平衡吸附量分别为11.23、17.41、15.45和59.42 mg/g;硅烷化沸石对金属离子的吸附行为更符合Langmuir模型,为化学吸附;在酸性条件下(pH=2～6),硅烷化沸石仍保持一定的吸附能力,具有一定的耐酸性。     

Simultaneous adsorption and degradation of Zn2+ and Cu2+ from wastewaters using nanoscale zero-valent iron impregnated with clays

Clays such as kaolin, bentonite and zeolite were evaluated as support material for nanoscale zero-valent iron (nZVI) to simultaneously remove Cu²⁺ and Zn²⁺ from aqueous solution. Of the three supported nZVIs, bentonite-supported nZVI (B-nZVI) was most effective in the simultaneous removal of Cu²⁺ and Zn²⁺ from a aqueous solution containing a 100 mg/l of Cu²⁺ and Zn²⁺, where 92.9 % Cu²⁺ and 58.3 % Zn²⁺ were removed. Scanning electronic microscope (SEM) revealed that the aggregation of nZVI decreased as the proportion of bentonite increased due to the good dispersion of nZVI, while energy dispersive spectroscopy (EDS) demonstrated the deposition of copper and zinc on B-nZVI after B-nZVI reacted with Cu²⁺ and Zn²⁺. A kinetics study indicated that removing Cu²⁺ and Zn²⁺ with B-nZVI accorded with the pseudo first-order model. These suggest that simultaneous adsorption of Cu²⁺and Zn²⁺ on bentonite and the degradation of Cu²⁺and Zn²⁺ by nZVI on the bentonite. However, Cu²⁺ removal by B-nZVI was reduced rather than adsorption, while Zn²⁺ removal was main adsorption. Finally, Cu²⁺, Zn²⁺, Ni²⁺, Pb²⁺ and total Cr from various wastewaters were removed by B-nZVI, and reusability of B-nZVI with different treatment was tested, which demonstrates that B-nZVI is a potential material for the removal of heavy metals from wastewaters.     

Removal of Cr(VI) onto Ficus carica biosorbent from water

The utilization of sustainable and biodegradable lignocellulosic fiber to detoxify the noxious Cr(VI) from wastewater is considered a versatile approach to clean up a contaminated aquatic environment. The aim of the present research is to assess the proficiency and mechanism of biosorption on Ficus carica bast fiber via isotherm models (Langmuir, Freundlich, Temkin, Harkin’s–Jura, and Dubinin–Radushkevich), kinetic models, and thermodynamic parameters. The biomass extracted from fig plant was characterized by scanning electron microscopy and Fourier-transform infrared spectroscopy. To optimize the maximum removal efficiency, different parameters like effect of initial concentration, effect of temperature, pH, and contact time were studied by batch method. The equilibrium data were best represented by the Langmuir isotherm model, and the maximum adsorption capacity of Cr(VI) onto biosorbent was found to be 19.68 mg/g. The pseudo-second-order kinetic model adequately described the kinetic data. The calculated values of thermodynamic parameters such as enthalpy change (?H ⁰), entropy change (?S ⁰), and free energy change (?G ⁰) were 21.55 kJ/mol, 76.24 J/mol?K, and ?1.55 kJ/mol, respectively, at 30 °C which accounted for spontaneous and endothermic processes. The study of adsorbent capacity for Cr(VI) removal in the presence of Na⁺, Mg²⁺, Ca²⁺, SO ₄ ^2? , HCO ₃ ^? and Cl^? illustrated that the removal of Cr(VI) increased in the presence of HCO^3? ions; the presence of Na⁺, SO ₄ ^2? or Cl^? showed no significant influence on Cr(VI) adsorption, while Ca²⁺ and Mg²⁺ ions led to an insignificant decrease in Cr(VI) adsorption. Further, the desorption studies illustrated that 31.10 % of metal ions can be removed from an aqueous system, out of which 26.63 % of metal ions can be recovered by desorption in first cycle and the adsorbent can be reused. The results of the scale-up study show that the ecofriendly detoxification of Cr(VI) from aqueous systems was technologically feasible.     

Methidathion Complexes with Homoionic and Surfactant-Modified Montmorillonites

Abstract

The formation of the insecticide methidathion (S-[(5-methoxy-2-oxo-1,3,4-thiadiazol-3(2H)-yl)methyl] O,O-dimethyl phosphorodithioate) complexes with inorganic cation-saturated (Mg²⁺, Ca²⁺, Cu²⁺, and Ni²⁺) montmorillonites was investigated. The nature and structure of the complexes was determined by X-ray diffraction and infrared spectroscopy. The arrangement of the pesticide molecule in the interlayer space was also considered from ab initio calculations using simpler related molecules. The insecticide methidathion penetrated the interlayer spaces of the homoionic clay samples. The ligand–cation interactions in these complexes depend on the nature and characteristics of the saturating cations. Mechanisms involving water bridges and direct coordination with the exchange cation were proposed for the adsorption of methidathion by inorganic cation-saturated montmorillonites. The effect of the inorganic cations on the sorption of the cationic surfactant tetradecyltrimethylammonium bromide (TDTMA) by montmorillonite was also studied and the subsequent sorption of methidathion in TDTMA⁺-Montmorillonite determined. Van der Waals bonds constitute the methidathion adsorption mechanism by montmorillonite saturated with TDTMA⁺. The arrangements of methidathion and of the cationic surfactant molecules in the montmorillonite interlayer space were demostrated.     

Soil pH and Anion Abundance Affects on Copper Adsorption

Abstract

Copper (Cu) input to agricultural soils results from Cu containing pesticides and/or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2–9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0–100 mg L^?1 in the equilibration solution, 95–99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl₂ or Ca(NO₃)₂ as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500–2000 mg L^?1, the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2–7.9. In a high pH soil (pH = 9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

Comparative study of adsorption of Pb(II) on native garlic peel and mercerized garlic peel

A comparative study using native garlic peel and mercerized garlic peel as adsorbents for the removal of Pb²⁺ has been proposed. Under the optimized pH, contact time, and adsorbent dosage, the adsorption capacity of garlic peel after mercerization was increased 2.1 times and up to 109.05 mg g^?1. The equilibrium sorption data for both garlic peels fitted well with Langmuir adsorption isotherm, and the adsorbent–adsorbate kinetics followed pseudo-second-order model. These both garlic peels were characterized by elemental analysis, Fourier transform infrared spectrometry (FT-IR), and scanning electron microscopy, and the results indicated that mercerized garlic peel offers more little pores acted as adsorption sites than native garlic peel and has lower polymerization and crystalline and more accessible functional hydroxyl groups, which resulted in higher adsorption capacity than native garlic peel. The FT-IR and X-ray photoelectron spectroscopy analyses of both garlic peels before and after loaded with Pb²⁺ further illustrated that lead was adsorbed on the through chelation between Pb²⁺ and O atom existed on the surface of garlic peels. These results described above showed that garlic peel after mercerization can be a more attractive adsorbent due to its faster sorption uptake and higher capacity.     

Copper (II) adsorption by the extracellular polymeric substance extracted from waste activated sludge after short-time aerobic digestion

The extracellular polymeric substance (EPS) extracted from waste activated sludge (WAS) after short-time aerobic digestion was investigated to be used as a novel biosorbent for Cu²⁺ removal from water. The EPS consisted of protein (52.6 %, w/w), polysaccharide (30.7 %, w/w), and nucleic acid (16.7 %, w/w). Short-time aerobic digestion process of WAS for about 4 h promoted the productivity growth of the EPS for about 10 %. With a molecular weight of about 1.9?×?10⁶ Da, the EPS showed a linear structure with long chains, and contained carboxyl, hydroxyl, and amino groups. The sorption kinetics was well fit for the pseudo-second-order model, and the maximum sorption capacity of the EPS (700.3 mg Cu²⁺/g EPS) was markedly greater than those of the reported biosorbents. Both Langmuir model and Freundlich model commendably described the sorption isotherm. The Gibbs free energy analysis of the adsorption showed that the sorption process was feasible and spontaneous. According to the complex results of multiple analytical techniques, including scanning electron microscopy, Fourier transform infrared spectroscopy, atomic force microscopy, etc., the adsorption process took place via both physical and chemical sorption, but the electrostatic interaction between sorption sites with the functional groups and Cu²⁺ is the major mechanism.