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.     

Cadmium (Cd2+) removal by nano zerovalent iron: surface analysis, effects of solution chemistry and surface complexation modeling

Nano zerovalent iron (nZVI) is an effective remediant for removing various organic and inorganic pollutants from contaminated water sources. Batch experiments were conducted to characterize the nZVI surface and to investigate the effects of various solution properties such as pH, initial cadmium concentration, sorbent dosage, ionic strength, and competitive ions on cadmium removal by nZVI. Energy-dispersive X-ray and X-ray photoelectron spectroscopy results confirmed removal of Cd²⁺ ions by nZVI through adsorption. Cd²⁺ adsorption decreased in the presence of competitive cations in the order: Zn²⁺?>?Co²⁺?>?Mg²⁺?>?Mn²⁺?=?Cu²⁺?>?Ca²⁺?>?Na²⁺?=?K⁺. Higher concentrations of Cl^? significantly decreased the adsorption. Cadmium removal increased with solution pH and reached a maximum at pH 8.0. The effects of various solution properties indicated Cd²⁺ adsorption on nZVI to be a chemisorption (inner-sphere complexation) process. The three surface complexation models (diffuse layer model, constant capacitance model, and triple layer model) fitted well to the adsorption edge experimental data indicating the formation of nZVI–Cd bidentate inner-sphere surface complexes. Our results suggest that nZVI can be effectively used for the removal of cadmium from contaminated water sources with varying chemical conditions.     

矸石基X型分子筛对水中Co2+、Cu2+、Cd2+和Cr3+的去除

以煤矸石为原料,采用碱熔后水热合成法制备X型分子筛并进行XRD、SEM、BET和Zeta电位分析。研究其对水中Co2+、Cu2+、Cd2+和Cr3+4种离子的吸附性能,包括吸附等温线、吸附动力学以及初始金属离子浓度、pH值对吸附性能的影响。所合成的矸石基X型分子筛的BET比表面积为676.02 m2/g,微孔孔容为0.263 cm3/g。吸附实验表明,矸石基X型分子筛能有效去除上述4种离子,同时实现煤矸石的资源化和金属离子的去除。4种离子的平衡吸附量均随初始浓度的增大而增大,相同条件下平衡吸附量的大小顺序为Cd2+>Cr3+>Cu2+>Co2+。准二级动力学模型能很好地描述4种离子的吸附动力行为。Langmuir模型对Co2+、Cu2+和Cd2+吸附的拟合较Freundlich模型高,说明其主要表现为物理吸附过程。4种离子的吸附速率均由液膜扩散和颗粒内扩散共同控制。     

Cu2+、Zn2+对生物脱氮系统的影响

Cu²⁺和Zn²⁺是污水处理工艺中经常遇到的金属离子。在驯化好的活性污泥系统中，研究了金属离子Cu²⁺和Zn²⁺在0～100 mg/L浓度下对活性污泥生物脱氮系统的影响。试验发现Cu²⁺＞5 mg/L、Zn²⁺＞30 mg/L时，对硝化过程具有明显的抑制作用，在同样浓度的试验条件下Cu²⁺对硝化过程的抑制作用比Zn²⁺大。Cu²⁺≤0.5 mg/L时对反硝化过程具有一定的促进作用，有助于提高TN的去除效果；Cu²⁺＞0.5 mg/L时，对反硝化产生抑制作用，随着浓度的增加，TN去除率逐渐下降。Zn²⁺不影响反硝化过程，仅在大于30 mg/L时，对硝化过程产生抑制作用。重金属Cu²⁺对生物脱氮系统的影响明显强于Zn²⁺。     

改性甘蔗渣对Cu2+和Zn2+的吸附机理

研究了均苯四甲酸二酐(PMDA)和乙二胺四乙酸二酐(EDTAD)改性甘蔗渣对重金属离子Cu2+和Zn2+的吸附性能,包括吸附动力学和吸附等温线。结果表明,改性后的甘蔗渣对重金属离子Cu2+和Zn2+的吸附容量有显著提高,对Cu2+和Zn2+吸附等温线均符合Langmuir方程,吸附为单分子层吸附。根据Langmuir方程,PMDA和EDTAD改性甘蔗渣对Cu2+的吸附量分别为60.21和33.45 mg/g,对Zn2+的吸附量分别是70.53和36.53 mg/g。两种改性甘蔗渣对两种金属离子的吸附在30 min内均可完成,用准二级吸附动力学方程模拟动力学过程得到较好的线性相关性。以EDTA溶液为洗脱剂对吸附Cu2+和Zn2+的改性甘蔗渣进行洗脱再生,再生的吸附剂可反复使用。     

木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂对二元重金属离子溶液中Pb2+的吸附

采用自制木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂R1、R2、R3对二元金属离子Cu2 +/pb2和Zn2+/pb2+溶液中的吸附性能进行了较系统考察.pb2+离子溶液中存在竞争离子Cu2+、Zn2+时,随竞争离子浓度增加,3种吸附树脂R1、R2、R3对pb2+的吸附量明显下降,而竞争离子吸附量显著增加.二元溶液中各金属离子浓度相同时,3种树脂对竞争离子Cu2+、Zn2+的吸附量大于对pb2+的吸附量;各溶液中分别加入NaCl及NaNO3、尿素后,对pb2+离子的吸附量下降迅速.随吸附树脂用量增加,竞争离子Cu2+、Zn2+的吸附量逐渐减小,pb2+的吸附量在吸附树脂用量0.10 g/L(Zn2 +/pb2+溶液)或0.15 g/L(Cu2+/pb2+溶液)时出现最大值.溶液pH值对树脂吸附性能有显著影响.3.0＜pH＜5.O时,3种树脂对竞争离子和pb2+的吸附量快速增大;5＜ pH ＜9时,树脂对竞争离子和pb2+的吸附量基本不变;9＜pH＜ll时,树脂对pb2+的吸附量减小,而对竞争离子的吸附量或增大或减小.     

Purification of industrial phosphoric acid (54 %) using Fe-pillared bentonite

The current problem of excess impurities in industrial phosphoric acid (IPA) 54 % P₂O₅ makes phosphates industries look toward low-cost but efficient adsorbents. In the present study, iron-oxide-modified bentonite (Fe-PILB) was prepared and investigated as a possible adsorbent for the removal of organic matter (OM) like humic acid (HA), chromium (Cr(III)), and zinc (Zn(II)) from IPA aqueous solutions. These adsorbents were characterized using XRD, TEM, and BET. The adsorption of impurities is well described by the pseudo-second-order model. The results indicate that Fe-PILB has a good ability to resist co-existing anions and the low-pH condition of IPA and owns a relatively high-removal capacity of 80.42 and 25 % for OM, Cr(III), and Zn(II). The mechanism of adsorption may be described by the ligand and ion exchange that happened on the active sites. The selected order of adsorption OM?>?Cr³⁺?>?Zn²⁺ showed the importance of the competitive phenomenon onto bentonite materials’ pore adsorption. For the adsorption of OM at the low pH of IPA, H-bond complexation was the dominant mechanism. From the adsorption of heavy metals and OM complex compounds contained in IPA 54 % on Fe-PILB, the bridging of humic acid between bentonite and heavy metals (Zn(II) or Cr(III)) is proposed as the dominant adsorption mechanism (bentonite-HA-Me). Overall, the results obtained in this study indicate Fe-pillared bentonite possesses a potential for the practical application of impurity (OM, Zn(II), and Cr(III)) removal from IPA aqueous solutions.     

Antifungal activities against toxigenic Fusarium specie and deoxynivalenol adsorption capacity of ion-exchanged zeolites

Zeolites are often used as adsorbents materials and their loaded cations can be exchanged with metal ions in order to add antimicrobial properties. The aim of this study was to use the 4A zeolite and its derived ion-exchanged forms with Zn²⁺, Li⁺, Cu²⁺ and Co²⁺ in order to evaluate their antifungal properties against Fusarium graminearum, including their capacity in terms of metal ions release, conidia germination and the deoxynivalenol (DON) adsorption. The zeolites ion-exchanged with Li⁺, Cu²⁺, and Co²⁺ showed an excellent antifungal activity against F. graminearum, using an agar diffusion method, with a zone of inhibition observed around the samples of 45.3 ± 0.6 mm, 25.7 ± 1.5 mm, and 24.7 ± 0.6 mm, respectively. Similar results using agar dilution method were found showing significant growth inhibition of F. graminearum for ion-exchanged zeolites with Zn²⁺, Li⁺, Cu²⁺, and Co²⁺. The fungi growth inhibition decreased as zeolite-Cu²⁺>zeolite-Li⁺>zeolite-Co²⁺>zeolite-Zn²⁺. In addition, the conidia germination was strongly affected by ion-exchanged zeolites. With regard to adsorption capacity, results indicate that only zeolite-Li⁺ were capable of DON adsorption significantly (P < 0.001) with 37% at 2 mg mL^?1 concentration. The antifungal effects of the ion-exchanged zeolites can be ascribed to the interactions of the metal ions released from the zeolite structure, especially for zeolite-Li⁺, which showed to be a promising agent against F. graminearum and its toxin.     

Effective adsorbent for arsenic removal: core/shell structural nano zero-valent iron/manganese oxide

Recently, nano zero-valent iron (nZVI) has emerged as an effective adsorbent for the removal of arsenic from aqueous solutions. However, its use in various applications has suffered from reactivity loss resulting in a decreased efficiency. Thus, the aim of this study was to develop an effective arsenic adsorbent as a core/shell structural nZVI/manganese oxide (or nZVI/Mn oxide) to minimize the reactivity loss of the nZVI. As the major result, the arsenic adsorption capacities of the nZVI/Mn oxide for As(V) and As(III) were approximately two and three times higher than that of the nZVI, respectively. In addition, the As(V) removal efficiency of the nZVI/Mn oxide was maintained through 4 cycles of regeneration whereas that of the nZVI was decreased significantly. The enhanced reactivity and reusability of the nZVI/Mn oxide can be successfully explained by the synergistic interaction of the nZVI core and manganese oxide shell, in which the manganese oxides participate in oxidation reactions with corroded Fe²⁺ and subsequently retard the release of aqueous iron providing additional surface sites for arsenic adsorption. In summary, this study reports the successful fabrication of a core/shell nZVI/Mn oxide as an effective adsorbent for the removal of arsenic from aqueous solutions.     

Silver-modified clinoptilolite for the removal of Escherichia coli and heavy metals from aqueous solutions

This paper investigates the potential of using the silver antibacterial properties combined with the metal ion exchange characteristics of silver-modified clinoptilolite to produce a treatment system capable of removing both contaminants from aqueous streams. The results have shown that silver-modified clinoptilolite is capable of completely eliminating Escherichia coli after 30-min contact time demonstrating its effectiveness as a disinfectant. Systems containing both E. coli and metals exhibited 100 % E. coli reduction after 15-min contact time and maximum metal adsorption removal efficiencies of 97, 98, and 99 % for Pb²⁺, Cd²⁺, and Zn²⁺ respectively after 60 min; 0.182–0.266 mg/g of metal ions were adsorbed by the zeolites in the single- and mixed-metal-containing solutions. Nonmodified clinoptilolite showed no antibacterial properties. This study demonstrated that silver-modified clinoptilolite exhibited high disinfection and heavy metal removal efficiencies and consequently could provide an effective combined treatment system for the removal of E. coli and metals from contaminated water streams.     

Removal and recovery of copper and nickel ions from aqueous solution by poly(methacrylamide-co-acrylic acid)/montmorillonite nanocomposites

Nanocomposite hydrogels based on poly(methacrylamide-co-acrylic acid) and nano-sized montmorillonite were prepared by aqueous dispersion and in situ radical polymerization. Optimum sorption conditions were determined as a function of montmorillonite content, contact time, pH, and temperature. The equilibrium data of Cu²⁺ and Ni²⁺ conformed to the Freundlich and Langmuir isotherms in terms of relatively high regression values. The maximum monolayer adsorption capacity of the nanocomposite hydrogel (with 3 wt% montmorillonite content), as obtained from the Langmuir adsorption isotherm, was found to be 49.26 and 46.94 mg g^?1 for Cu²⁺ and Ni²⁺, respectively, at contact time?=?60 min, pH?=?6.8, adsorbent dose?=?100 mg/ml, and temperature?=?318 K. Kinetic studies of single system indicated that the pseudo-second order is the best fit with a high correlation coefficient (R ²?=?0.97–0.99). The result of five times sequential adsorption–desorption cycle shows a good degree of desorption and a high adsorption efficiency.     

4种脂肪多胺修饰硅胶对铅离子的吸附

为了合成高效铅离子吸附剂,了解其对铅离子的吸附规律。采用(3-氯丙基)三甲氧基硅烷(CPTS)架桥法,以硅胶(SG)为载体,乙二胺(EDA)、二乙烯三胺(DETA)、三乙烯四胺(TETA)和四乙烯五胺(TEPA)为表面修饰剂,合成了4种胺化硅胶,测定了它们的红外光谱、热重等性质以及对Cu2+、Zn2+和Pb2+的吸附能力。结果表明,4种胺化硅胶对Pb2+的吸附量均大于Cu2+和Zn2+的吸附量,其中DETA修饰硅胶对Pb2+的吸附量较高。4种胺化硅胶对Pb2+的吸附过程较好地符合拟二级动力学模型以及Langmuir和Scatchart等温吸附热力学模型,其对Pb2+吸附的速率常数、饱和吸附量以及吸附位点数由大到小的顺序一致,均为SG-DETASG-TEPASG-EDASG-TETA。4种胺化硅胶对Pb2+的吸附速率和吸附量呈现"奇数胺"增强效应,亲和常数则依次减小。阐明了脂肪多胺修饰硅胶对Pb2+的吸附规律,并进一步讨论了Scatchart和Langmuir热力学模型的统一性。     

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⁺.     

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。     

Heterogeneous Fenton oxidation of Direct Black G in dye effluent using functional kaolin-supported nanoscale zero iron

This study investigated kaolin-supported nanoscale zero-valent iron (nZVI/K) as a heterogeneous Fenton-like catalyst for the adsorption and oxidation of an azo dye, Direct Black G (DBG). New findings suggest that kaolin as a support material not only reduced the aggregation of nanoscale zero-valent iron (nZVI) but also improved the adsorption of DBG. It consequently improved Fenton oxidation by increasing the local concentration of DBG in the vicinity of nZVI. This was confirmed by scanning electron microscopy and X-ray diffraction for the surface morphology of nZVI/K before and after the Fenton-like reaction. Furthermore, nZVI/K proved to be a catalyst for the heterogeneous Fenton-like oxidation of the DBG process in the neutral pH range. More than 87.22 % of DBG was degraded, and 54.60 % of total organic carbon was removed in the optimal conditions: 0.6 g/L dosage of nZVI/K, 33 mM H₂O₂, 100 mg/L initial DBG concentration, temperature of 303 K and pH of 7.06. Finally, it was demonstrated that nZVI/K removed DBG from dye wastewater through the processes of adsorption and oxidation.     

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.     

Effect of Ca2+-ions on the absorption of Pb2+, Cu2+, Cd2+ and Zn2+ by humic substances

Distribution coefficients for the sorption of Pb²⁺, Cu²⁺, Cd²⁺ and Zn²⁺ by peat were determined as a function of the Ca²⁺-content of peat as well as of the Ca²⁺-concentration in the solution. The amount of heavy metal ions taken up was measured for Cu²⁺, Cd²⁺ and Zn²⁺ by atomic absorption spectrometry and for Pb²⁺ by using Pb-212 as a radioactive tracer.The results show that the distribution coefficients of the heavy metal ions increase, if one increases the initial ratio of the $\text{Ca}{}^{\mathrm{2+}}\text{H}{}^{\mathrm{+}}\text{-}\text{ions}$ in the peat phase. The distribution coefficients for the heavy metal ions decrease, however, if - at constant initial Ca²⁺-content of the peat - the Ca²⁺-concentration of the solution is increased.     

重金属离子在钠基膨润土中的吸附特征与机理

膨润土是一种天然粘土矿物,比表面积大、吸附能力强。通过钠基膨润土对复合重金属离子Cu2+、Zn2+和Cd2+的竞争吸附实验研究,探讨了钠基膨润土对Cu2+、Zn2+和Cd2+的吸附特征。结果表明,钠基膨润土对Cu2+、Zn2+和Cd2+的吸附随离子浓度增加而增大。吸附具有选择性,Cu2+、Zn2+和Cd2+的吸附能力大小顺序为Cu2+>Zn2+>Cd2+。并通过XRD及IR等分析探讨了钠基膨润土的吸附机理主要表现为离子交换吸附。     

Adsorption and desorption of 2,4,6-trichlorophenol onto and from ash as affected by Ag+, Zn2+, and Al3+

Metal cations and organic pollutants mostly co-exist in the natural environment. However, their interactions in adsorption processes have yet to be adequately addressed. In the current study, the effect of inorganic cations with different charges (Ag⁺, Zn²⁺, and Al³⁺) on the adsorption and desorption of 2,4,6-trichlorophenol (TCP) onto and from processed ash derived from wheat (Triticum aestivum L.) straw was investigated. The adsorption and desorption of TCP were both nonlinear; the isotherm and kinetics curves fitted well using the Freundlich equation and a pseudo-second-order model, respectively. The presence of Ag⁺ promoted TCP adsorption, while Zn²⁺ and Al³⁺ reduced TCP adsorption onto ash. The desorption of TCP from ash showed obvious hysteresis, and the presence of Ag⁺, Zn²⁺, and Al³⁺ caused the desorption to be less hysteretic. The suppression of TCP adsorption by Zn²⁺ and Al³⁺ was ascribed to the partial overlapping of adsorption groups between TCP and metal ions. Al³⁺ had a stronger inhibition effect than that of Zn²⁺ due to its higher binding capacity and larger hydrated ionic radius than those of Zn²⁺. Enhanced adsorption of TCP onto ash by Ag⁺ was ascribed to its ability to reduce the competitive adsorption of water molecules on ash surface by replacing the original ions, such as Na⁺ and Ca²⁺, and compressing the hydrated ionic radius of these metal ions. In addition, Ag⁺ was able to bind with the aromatic organic compounds containing π-electrons, which resulted in a further increase of TCP adsorption by ash.     

Growth and metal removal potential of a Phormidium bigranulatum-dominated mat following long-term exposure to elevated levels of copper

The present study explores the tolerance and metal removal response of a well-developed 2-week-old Phormidium mat after long-term exposure to Cu²⁺-enriched medium. Cu²⁺ enrichment inhibited increase in mat biomass in a concentration-dependent manner. Mat area and the number of entrapped air bubbles decreased as Cu²⁺ concentration increased in the medium. Decrease in number of air bubbles obviously reflects the adverse effect of Cu²⁺ on photosynthetic performance of the mat. Metal enrichment did not substantially alter the amount of pigments, such as chlorophyll a, chlorophyll b, carotenoids, and phycocyanin, in the mat. Enhancement of Cu²⁺ concentration in the medium led to changes in species composition of the test mat; however, Phormidium bigranulatum always remained the dominant organism. Relative share of green algae and some cyanobacterial taxa, namely, Lyngbya sp. and Oscillatoria tenuis, in the mat were increased by Cu²⁺ enrichment. The mat successfully removed 80 to 94 % Cu²⁺ from the growth medium containing 10 to 100 μM Cu²⁺. Extracellular polysaccharides, whose share increased in the mat community after metal addition, seem to have contributed substantially to metal binding by the mat biomass.