Crosslinking acrylamide with EDTA-intercalated layered double hydroxide for enhanced recovery of Cr(VI) and Congo red: Adsorptive and mechanistic study

• Functional groups of AM and EDTA in composite increased removal of Cr(VI) and CR. • Removal process reached equilibrium within 30 min and was minimally affected by pH. • Elimination of Cr(VI) was promoted by coexisting CR. • Adsorption process of CR was less influenced by the presence of Cr(VI). • Mechanisms were electrostatic attraction, surface complexation and anion exchange. We prepared ethylenediaminetetraacetic acid (EDTA)-intercalated MgAl-layered double hydroxide (LDH-EDTA), then grafted acrylamide (AM) to the LDH-EDTA by a cross-linking method to yield a LDH-EDTA-AM composite; we then evaluated its adsorptive ability for Congo red (CR) and hexavalent chromium (Cr(VI)) in single and binary adsorption systems. The adsorption process on LDH-EDTA-AM for CR and Cr(VI) achieved equilibrium quickly, and the removal efficiencies were minimally affected by initial pH. The maximum uptake quantities of CR and Cr(VI) on LDH-EDTA-AM were 632.9 and 48.47 mg/g, respectively. In mixed systems, chromate removal was stimulated by the presence of CR, while the adsorption efficiency of CR was almost not influenced by coexisting Cr(VI). The mechanisms involved electrostatic attraction, surface complexation, and anion exchange for the adsorption of both hazardous pollutants. In the Cr(VI) adsorption process, reduction also took place. The removal efficiencies in real contaminated water were all higher than those in the laboratory solutions.     

Cr (VI) and Fe (III) removal using Cajanus cajan husk

Husk of tur dal (Cajanus cajan) was investigated as a new biosorbent for the removal of Fe (III) and Cr (VI) ions from aqueous solutions. Parameters like agitation time, adsorbent dosage and pH were studied at different initial Fe (III) and Cr (VI) concentrations. The biosorptive capacity of the Tur dal husk was dependent on the pH of the chromium and iron solution, with pH 2 and 2.5 respectively being optimal. The adsorption data fit well with Langmuir and Freundlich isotherm models. The practical limiting adsorption capacity (qmax) calculated from the Langmuir isotherm was 96.05 mg of Cr(VI)/ g of the biosorbent at an initial pH of 2.0 and 66.65 mg/g at pH 2.5. The infrared spectra of the biomass revealed that hydroxyl, carboxyl and amide bonds are involved in the uptake of Cr (VI) and Fe (III) ions. Characterisation of tur dal husk has revealed that it is an excellent material for treating wastewaters containing low concentration of metal ions.     

Chromium sorption on grape stalks encapsulated in calcium alginate beads

A novel sorbent based on 2% grape stalk wastes encapsulated in calcium alginate beads was investigated for the removal of Cr(VI) and Cr(III) from aqueous solutions. The sorbent proved to be efficient for chromium removal in both hexavalent and trivalent forms from aqueous solution at pH 3.0. In binary mixtures, the presence in solution of one of the forms enhances the sorption of the other which results in an increase of the amount of total chromium removed. This study suggests that the proposed sorbent can be used for the removal of chromium from wastewaters through a cost-effective and environmentally friendly process.     

重金属-柠檬酸-针铁矿三元体系的表面络合模型研究

根际环境产生的柠檬酸等小分子有机酸可能影响重金属的溶出效应.本文研究了4种重金属Cd、Pb、Cu、Ni及柠檬酸在针铁矿表面的三元体系吸附行为,结果发现柠檬酸促进了4种重金属酸性条件下在针铁矿表面的吸附量,而Cu、Ni促进了柠檬酸碱性条件下的吸附.结合红外光谱图发现,重金属-柠檬酸-针铁矿主要存在以下2种三元体系形态,即以柠檬酸为"桥键"的≡Fe2CitMe形态和以重金属为"桥键"的(≡FeOH)2MeCit形态.采用电荷分配-多位点表面配合(CD-MUSIC)模型成功预测了的三元体系重金属及柠檬酸在针铁矿表面的吸附行为,模型结果发现柠檬酸的存在显著改变了重金属的吸附形态,其中≡Fe2CitMe为Cd、Pb、Ni三元体系中酸性条件下的主要形态,(≡FeOH)2CuCit为Cu的主要形态.研究补充完善了根际环境的土壤形态模型数据库,为预测重金属的溶出及生物有效性的模型研究提供了基础数据.     

不同价态铬在不同水分条件下的生物有效性及其对水稻的毒性

氧化还原过程在铬的形态转化中起了重要作用,而铬形态的转化能够影响其生物有效性及毒性。通过温室土培试验研究了六价铬(Cr(Ⅵ))与三价铬(Cr(Ⅲ))在淹水与不淹水条件下在土壤溶液中的动态变化及水稻对其吸收的变化。结果表明,土壤中添加Cr(Ⅲ)时,土壤溶液中检测不出Cr;而随着土壤中添加Cr(Ⅵ)浓度的增加,土壤溶液中Cr(Ⅵ)的浓度增加,但是溶液中检测不出Cr(Ⅲ);淹水处理总体上降低了土壤溶液中Cr(Ⅵ)的浓度。而土壤添加Cr(Ⅲ)、Cr(Ⅵ)和水分处理对土壤溶液p H没有显著影响,p H在7.08.0之间变动。土壤添加Cr(Ⅵ)处理的水稻中,只有90 mg·kg-1Cr(Ⅵ)淹水处理的水稻成活,而其余处理水稻没有成活。土壤中添加Cr(Ⅲ)处理,水稻幼苗生物量随Cr(Ⅲ)浓度的增加而显著降低;除了200mg·kg-1Cr(Ⅲ)处理外,其余淹水处理的水稻幼苗生物量明显高于不淹水处理的。土壤添加Cr(Ⅲ)处理的水稻,在不淹水条件下水稻空壳率比较高,淹水条件下,随着土壤中添加Cr(Ⅲ)浓度水平的增加,水稻各部位Cr含量有增加的趋势,但增加不显著,秸秆最高Cr含量达到33.80 mg·kg-1,籽粒中Cr含量最高0.30 mg·kg-1。土壤固定Cr(Ⅲ)的能力远强于Cr(Ⅵ),添加Cr(Ⅵ)处理的土壤溶液中Cr(Ⅵ)的浓度很高,对水稻表现出较强的生长抑制。     

Reduction of Cr(VI) by peat and coal humic substances

The reduction of Cr(VI) by humic substances from leonardite and peat was investigated by capillary zone electrophoresis at various pHs. Both humic materials reduced Cr(VI) at pH 5.4, but not at basic pH. The capacity of leonardite humic substances to reduce Cr(VI) was lower than that of peat humic substances. Fe(III) accelerated the reduction of Cr(VI) by peat humic substances, but not by leonardite humic substances. Cr(VI) reduction mechanisms are proposed. The coal humic substances seem more suitable for remediation of Cr(VI)-contaminated sites.     

Removal of toxic chromium(VI) from aqueous solution by activated carbon using Casuarina equisetifolia

Highly activated carbon from the seed husk of Casuarina Casuarinas equisetifolia, a worldwide famous plant, have been prepared and tested for the removal of toxic Cr(VI) from its aqueous solution. The adsorbent was investigated for influences of initial chromium concentration (75, 100, 125, and 150 mg l^-1), pH, contact time, and quantity of carbon on removal of Cr(VI) from aqueous solution at room temperature (25±2 °C). The adsorption kinetic of Cr(VI) was studied, and the rates of sorption were found to conform to pseudo-second-order kinetics with a good correlation (R²≥0.99). The Langmuir and Freundlich models fit the isotherm data well. Furthermore, the Gibbs free energy was obtained for each system and was found to be-5.29 kJ mol^-1 for removal of Cr(IV). The negative value of Δ G° indicates the feasibility and spontaneous nature of adsorption. The results indicate that acidic pH (1.05) supported the adsorption of Cr(IV) on activated carbon. The maximum adsorption capacity of Cr(VI) on activated carbon was about 172.4 mg g^-1 at pH 1.05.     

Adsorption of vanadate(V) on Fe(III)/Cr(III) hydroxide waste

Adsorption of vanadate(V) from aqueous solution onto industrial solid ‘waste’ Fe(III)/Cr(III) hydroxide was investigated. HCl treated Fe(III)/Cr(III) hydroxide was found to be more efficient for the removal of vanadate(V) compared to untreated adsorbent. The adsorption follows second-order kinetics. Langmuir and Freundlich isotherms have been studied. The Langmuir adsorption capacity (Q ₀) of the treated and untreated adsorbents was found to be 11.43 and 4.67 mg g⁻¹, respectively. Thermodynamic parameters showed that the adsorption process was spontaneous and endothermic in the temperature range 32–60°C. Maximum adsorption was found at system pH 4.0. The adsorption mechanism was predominantly ion exchange. Effect of other anions such as phosphate, selenite, molybdate, nitrate, chloride, and sulfate on adsorption of vanadium has been examined.     

Removal of selenite using ‘waste’ Fe(III)/Cr(III) hydroxide: Adsorption kinetics and isotherms

Removal of selenite [Se (IV)] from aqueous solution on to industrial solid ‘waste’ Fe(III)/Cr(III) hydroxide as adsorbent was investigated in the present article. Maximum adsorption was found to be at pH 4.0. Pretreated Fe(III)/Cr(III) hydroxide was found to be more efficient for the removal of selenite compared to untreated adsorbent. Langmuir and Freundlich isotherms have been studied. The Langmuir adsorption capacity (Q ₀) of the pretreated and untreated adsorbents was found to be 15.63 and 6.04?mg?g^?1, respectively. The adsorption process fit into the second-order kinetics. Thermodynamic parameters show that the adsorption process is spontaneous and endothermic in the temperature range 32 to 60°C. Coexisting anions vanadate and phosphate significantly affect the adsorption of selenite for both the pretreated and untreated adsorbents. Molybdate, thiocyanate, sulphate, nitrate and chloride do not significantly affect the removal of selenite for pretreated adsorbent.     

改性腐殖酸对铀的吸附的试验研究

通过静态吸附实验,探讨了改性HA对U(Ⅵ)吸附影响。考查pH值、时间、U(Ⅵ)的初始浓度和温度等对吸附的影响。结果表明:pH值对改性腐殖酸的吸附效果影响较大,改性腐殖酸吸附U(Ⅵ)的最佳pH值为6,最大去除率为99.37%,吸附在60 min内基本达到平衡。UO22+在改性腐殖酸上的吸附是放热过程,符合Freundlich等温吸附方程,相关系数达0.99以上,表明IHA对铀的吸附是以表面为主要吸附位,并不是均匀的单层吸附。图8,参9.     

Dual-functional sites for synergistic adsorption of Cr(VI) and Sb(V) by polyaniline-TiO2 hydrate: Adsorption behaviors,sites and mechanisms

• PANI/Ti(OH)_n^(4–n)+ exhibited excellent adsorption capacity and reusability. • Adsorption sites of Cr(VI) were hydroxyl, amino/imino group and benzene rings. • Sb(V) was adsorbed mainly through hydrogen bonds and Ti-O-Sb. • The formation of Cr-O-Sb in dual system demonstrated the synergistic adsorption. • PANI/TiO₂ was a potential widely-applied adsorbent and worth further exploring. Removal of chromium (Cr) and antimony (Sb) from aquatic environments is crucial due to their bioaccumulation, high mobility and strong toxicity. In this work, a composite adsorbent consisting of Ti(OH)_n^(4–n)+ and polyaniline (PANI) was designed and successfully synthesized by a simple and eco-friendly method for the uptake of Cr(VI) and Sb(V). The synthetic PANI/TiO₂ composites exhibited excellent adsorption capacities for Cr(VI) and Sb(V) (394.43 mg/g for Cr(VI) and 48.54 mg/g for Sb(V)), wide pH applicability and remarkable reusability. The adsorption of Cr(VI) oxyanions mainly involved electrostatic attraction, hydrogen bonding and anion-π interactions. Based on X-ray photoelectron spectroscopy and FT-IR analysis, the adsorption sites were shown to be hydroxyl groups, amino/imino groups and benzene rings. Sb(V) was adsorbed mainly through hydrogen bonds and surface complexation to form Ti-O-Sb complexes. The formation of Cr-O-Sb in the dual system demonstrated the synergistic adsorption of Cr(VI) and Sb(V). More importantly, because of the different adsorption sites, the adsorption of Cr(VI) and Sb(V) occurred independently and was enhanced to some extent in the dual system. The results suggested that PANI/TiO₂ is a promising prospect for practical wastewater treatment in the removal of Cr(VI) and Sb(V) from wastewater owing to its availability, wide applicability and great reusability.     

胶原纤维固化黑荆树单宁吸附Cr(VI)的研究

研究了胶原纤维固化黑荆树单宁对Cr(VI)的吸附.采用不同温度、pH值等条件进行吸附研究,并进一步探讨了固化黑荆树单宁的吸附动力学和吸附柱动力学及其吸附机理.结果表明,该材料对Cr(VI)的吸附平衡符合Freundlich方程,温度对吸附平衡的影响不明显;吸附动力学可用拟二级速度方程来描述,该材料同时具有良好的柱动力学特性;Cr(VI)的吸附过程可能存在3个反应,即Cr(VI)与吸附剂之间发生氧化还原反应生成Cr(III),Cr(III)和-COOH之间发生离子交换反应,以及Cr(III)与单宁的邻位羟基发生螯合.图8表2参10     

碱性条件下胡敏酸吸附镉的特征研究

为了探讨胡敏酸在碱性条件下的吸附镉机理,了解碱性盐化土壤中镉污染机理和生态环境之间的关系,实验研究了胡敏酸在碱性条件吸附镉的特征。采用批吸附试验方法,研究不同Cd初始浓度、反应时间、不同pH和离子强度对胡敏酸吸附镉的影响,结果表明：胡敏酸具有较强吸附镉的能力,可以用Langmuir吸附模型和Temkin吸附模型很好地拟合其等温吸附过程（r分别为0.9809和0.9816）;在60 min内的快速反应阶段和60 min至6 h间的慢速反应阶段,胡敏酸对镉的吸附量分别为2.895 mg·g-1和3.342 mg·g-1,吸附反应平衡前6 h的动力学过程可以用Elovich方程进行很好的拟合（r为0.9285）;随着pH增加,吸附率表现出逐步增加趋势,并以pH为4.5和8.5为界,呈现两端增加速度快,中间增加慢的规律性;在较低浓度离子强度下,离子强度的增加促进胡敏酸吸附镉;而在高离子强度下,表现出相反的规律性;在相同的条件下,不同离子强度对胡敏酸吸附镉的影响大小为：氯化钙〉氯化镁〉氯化钾〉氯化钠。土壤在盐化的过程中,由于无机盐浓度的增加,增加了重金属离子的生物可利用性,加大了重金属离子的生态风险。     

Removal of chromium(VI) by ZnCl2 activated coir pith carbon

The adsorption of chromium(VI) onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of contact time, adsorbent dose, Cr(VI) concentration, pH and temperature were investigated. The two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q ₀) was found to be 120.5?mg Cr(VI) per g of the adsorbent. The adsorption followed the second-order kinetics and was found to be maximum at pH 2.0. The pH effect and the desorption studies showed that ion exchange mechanism might be involved in the adsorption process. The effects of foreign ions such as chloride, sulphate, phosphate, selenite, molybdate, nitrate and perchlorate on the removal of Cr(VI) have been investigated. The removal of Cr(VI) from synthetic ground water was also tested. The results show that ZnCl₂ activated coir pith carbon is effective for the removal of Cr(VI) from water.     

Removal of chromium (VI) from water streams: a thermodynamic study

The chemical speciation of water solutions containing chromium oxyanions in various ratios is calculated (with the aid of available computer code Mineql Plus, Geochemist Workbench and Visual Minteq) and discussed. The effect of solution pH, total concentration of each species studied, and the presence of other species in solution are calculated and presented in the form of thermodynamic speciation diagrams. Electrochemical diagram (correlating pH to Eh) has been calculated as well. The conditions of Cr(VI) reduction to Cr(III) and the subsequent solid phase precipitation are given as a function of redox potential and pH. Surface reactions that might occur between the chromate ions in the solution and redox couples as Fe²⁺/Fe³⁺ on the surface of sorbents are also discussed. Moreover, experimental sorption data of hexavalent chromium onto synthetic magnetite are presented and discussed with the aid of the calculated diagrams. A mechanism is elucidated for the efficient removal of Cr(VI) from water streams at low pH values, and zeta potential data of synthetic magnetite with and without Cr(VI) are presented, which agree well with the mechanism proposed.     

Biosorption potential of Cr(VI) by Kocuria sp. ASB107, a radio-resistant bacterium isolated from Ramsar,Iran

Heavy metal pollution in soil and wastewater is a worldwide environmental issue in which microorganisms play a significant role for its removal. In the present study, biosorption of Cr(VI) by the live and dead cells of Kocuria sp. ASB107, a radio-resistant bacterium, was investigated. The effect of contact time, solution pH, initial hexavalent chromium concentration and adsorbent dose on biosorption efficiency was studied. Also, live cells were further immobilised on various matrices by different techniques and then were examined for tolerance to chromium biosorption. Experimental results indicated that the removal efficiency of chromium increased with decrease in pH, initial Cr(VI) concentration, and also increase in adsorbent dose and the contact time. The maximum removal efficiency of live and dead cells at acidic pH of 4–4.5, contact time of 24 hours, adsorbent dose 1.6?g/100?mL and initial chromium concentration 25?mg/L were 82.4% and 69.2%, respectively. The adsorption data was described well by Langmuir isotherm model. Among all immobilisation techniques tested, cross-linking showed the highest biosorption of Cr(VI). Results indicated that live cells of Kocuria sp. ASB107 were better than dead ones.     

Effect of co-existing organic compounds on adsorption of perfluorinated compounds onto carbon nanotubes

Co-existing organic compounds may affect the adsorption of perfluorinated compounds (PFCs) and carbon nanotubes in aquatic environments. Adsorption of perfluorooctane sulfonate (PFOS), perfluorooctane acid (PFOA), perfluorobutane sulfonate (PFBS), and perfluorohexane sulfonate (PFH_xS) on the pristine multi-walled carbon nanotubes (MWCNTs-Pri), carboxyl functionalized MWCNTs (MWCTNs-COOH), and hydroxyl functionalized MWCNTs (MWCNTs-OH) in the presence of humic acid, 1-naphthol, phenol, and benzoic acid was studied. Adsorption kinetics of PFOS was described well by the pseudo-second-order model and the sorption equilibrium was almost reached within 24 h. The effect of co-existing organic compounds on PFOS adsorption followed the decreasing order of humic acid>1-naphthol>benzoic acid>phenol. Adsorbed amounts of PFOS decreased significantly in the presence of co-existing or preloaded humic acid, and both adsorption energy and effective adsorption sites on the three MWCNTs decreased, resulting in the decrease of PFOS adsorption. With increasing pH, PFOS removal by three MWCNTs decreased in the presence of humic acid and phenol. The adsorbed amounts of different PFCs on the MWCNTs increased in the order of PFBSxS相似文献   

Reduction of hexavalent chromium with scrap iron in a fixed bed reactor

The reduction of hexavalent chromium by scrap iron was investigated in continuous long-term fixed bed system. The effects of pH, empty bed contact time (EBCT), and initial Cr(VI) concentration on Cr(VI) reduction were studied. The results showed that the pH, EBCT, and initial Cr(VI) concentration significantly affected the reduction capacity of scrap iron. The reduction capacity of scrap iron were 4.56, 1.51, and 0.57 mg Cr(VI)·g^-1 Fe⁰ at pH 3, 5, and 7 (initial Cr(VI) concentration 4 mg·L^-1, EBCT 2 min, and temperature 25°C), 0.51, 1.51, and 2.85 mg Cr(VI)·g^-1 Fe⁰ at EBCTs of 0.5, 2.0, and 6.0 min (initial Cr(VI) concentration 4 mg·L^-1, pH 5, and temperature 25°C), and 2.99, 1.51, and 1.01 mg Cr(VI)·g^-1 Fe⁰ at influent concentrations of 1, 4, and 8 mg·L^-1 (EBCT 2 min, pH 5, and temperature 25°C), respectively. Fe(total) concentration in the column effluent continuously decreased in time, due to a decrease in time of the iron corrosion rate. The fixed bed reactor can be readily used for the treatment of drinking water containing low amounts of Cr(VI) ions, although the hardness and humic acid in water may shorten the lifetime of the reactor, the reduction capacity of scrap iron still achieved 1.98 mg Cr⁶⁺·g^-1 Fe. Scanning electron microscope equipped with energy dispersion spectrometer and X-ray diffraction were conducted to examine the surface species of the scrap iron before and after its use. In addition to iron oxides and hydroxide species, iron-chromium complex was also observed on the reacted scrap iron.     

In situ synthesis of FeS/Carbon fibers for the effective removal of Cr(VI) in aqueous solution

• FeS/carbon fibers were in situ synthesized with Fe-carrageenan hydrogel fiber. • The double helix structure of carrageenan is used to load and disperse Fe. • Pyrolyzing sulfate groups enriched carrageenan-Fe could easily generate FeS. • The adsorption mechanisms include reduction and complexation reaction. Iron sulfide (FeS) nanoparticles (termed FSNs) have attracted much attention for the removal of pollutants due to their high efficiency and low cost, and because they are environmentally friendly. However, issues of agglomeration, transformation, and the loss of active components limit their application. Therefore, this study investigates in situ synthesized FeS/carbon fibers with an Fe-carrageenan biomass as a precursor and nontoxic sulfur source to ascertain the removal efficiency of the fibers. The enrichment of sulfate groups as well as the double-helix structure in ι-carrageenan-Fe could effectively avoid the aggregation and loss of FSNs in practical applications. The obtained FeS/carbon fibers were used to control a Cr(VI) polluted solution, and exhibited a relatively high removal capacity (81.62 mg/g). The main mechanisms included the reduction of FeS, electrostatic adsorption of carbon fibers, and Cr(III)-Fe(III) complexation reaction. The pseudo-second-order kinetic model and Langmuir adsorption model both provided a good fit of the reaction process; hence, the removal process was mainly controlled by chemical adsorption, specifically monolayer adsorption on a uniform surface. Furthermore, co-existing anions, column, and regeneration experiments indicated that the FeS/carbon fibers are a promising remediation material for practical application.     

氨基化氧化石墨烯(AGO)的制备及其对六价铬的吸附机制

以乙二胺盐酸盐(EDH)为改性剂改性氧化石墨烯(GO),水热法制备氨基化氧化石墨烯(Amino-functionalized;graphene;oxide,AGO).SEM、XRD、FTIR和Zeta电位表征分析发现,AGO表面含有羟基、羧基及氨基基团,Zeta电位为pH=10.14.以水中低浓度六价铬Cr(Ⅵ)为污染物,探讨了乙二胺盐酸盐(EDH)用量、pH、AGO用量、Cr(Ⅵ)初始浓度以及常见干扰离子对AGO吸附Cr(Ⅵ)影响.结果表明,在pH=6.0、7-AGO用量为0.8;mg·L^-1和Cr(Ⅵ)初始浓度为2.0;mg·L^-1,7-AGO对Cr(Ⅵ)去除率可达95.1%;SO₄^2-会明显抑制AGO对Cr(Ⅵ)的吸附.AGO对Cr(Ⅵ)的吸附过程符合二级动力学模型,吸附机制主要为静电作用.