有机改性蒙脱石负载纳米零价铁去除水体新兴污染物双氯芬酸

双氯芬酸(DFC)作为一种典型的新兴污染物,进入环境中难以被生物降解和转化,给人类健康造成潜在危害.本研究采用阳离子表面活性剂十六烷基三甲基溴化铵(HDTMAB)改性的蒙脱石(Mt)负载自制的纳米零价铁(nZVI),得到有机改性蒙脱石负载纳米零价铁(H-Mt+nZVI)复合材料,用于去除水中的DFC.利用X射线衍射仪(XRD)、比表面积分析仪(BET)对复合材料进行了表征.结果表明,在XRD图谱中2θ=44.6°附近出现了对应于Fe~0的衍射峰,证明nZVI被成功负载于Mt上;在0.5 CEC、1 CEC、2 CEC改性的Mt比表面积由49.40 m~2·g~(-1)下降到20.86、21.27、26.06 m~2·g~(-1),且Mt的孔径由8.01 nm增大到10.93、11.60、12.40 nm,主要由于nZVI负载到Mt表面或层间,扩充了部分吸附孔洞.同时,采用批次吸附实验比较了Mt、nZVI和H-Mt+nZVI复合材料对DFC的去除效果,研究结果表明,Mt和nZVI对DFC的去除率均低于20%,复合材料对DFC的去除率明显增大,可达90%以上.复合材料对DFC的吸附等温曲线符合Langmuir和Freundlich等温模型,吸附动力学更满足准一级动力学模型.在采用1倍阳离子交换量改性蒙脱石负载纳米零价铁(1 CEC Mt+nZVI)吸附DFC时,饱和吸附量可达1922.78 mg·kg~(-1),吸附平衡时间为30 min.说明H-Mt+nZVI复合材料可应用于水体新兴污染物DFC的快速去除.     

绿色合成膨胀石墨负载纳米零价铁去除水中Cd(Ⅱ)

工业生产中Cd(Ⅱ)对水体的危害,本文合成了两种新型吸附剂,纳米零价铁(nZVI)和膨胀石墨负载纳米零价铁(EG-nZVI).利用FESEM、EDS、TEM、XRD、FTIR及BET比表面积测定对nZVI和EG-nZVI进行表征,探讨了二者对溶液中Cd(Ⅱ)的去除效果.结果 表明,含有100 mg·L-1Cd(Ⅱ)溶液,nZVI和EG-nZVI的投加量分别达到0.4 mg·L-1和2 mg·L-1,在超声波辅助的条件下,常温、pH 8、反应30 min时,Cd(Ⅱ)去除率分别为56.3％和78.4％.EG-nZVI和nZVI去除Cd (Ⅱ)过程均符合伪二级动力学模型和Langmuir吸附等温模型;将吸附剂置于空气中不同时间,测定结果显示EG-nZVI对Cd(Ⅱ)的去除活性明显高于nZVI,说明EG-nZVI较nZVI有更高的去除效能和稳定性.     

二氧化锰基纳米材料对重金属离子的去除及机理研究进展

重金属离子对人类健康和环境安全产生了严重威胁,因此重金属废水高效处理成为了环境领域最具挑战性的热点问题之一.二氧化锰(MnO_2)是一种环境友好型金属氧化物,具有来源广泛、成本低廉、形貌多样、晶型丰富、结构稳定、粒径可控等优异的性质,在重金属离子的去除应用上展现出巨大的潜力.近年来,人们利用MnO_2基纳米材料在重金属离子的有效治理方面开展了大量的研究.本文综述了MnO_2基纳米材料在重金属离子环境修复方面取得的研究进展,包括MnO_2的制备和改性方法,MnO_2基纳米材料在水溶液重金属离子去除中的应用及吸附作用机制,并对研究方向进行了总结和展望,旨在为进一步设计合成对重金属离子的吸附去除具有实际应用价值的MnO_2基纳米材料提供参考.     

纳米零价铁及其在环境介质中氧化后性质演变研究进展

纳米零价铁(nZVI)尺寸小、比表面积大、表面能高、还原性强,对环境污染物具有良好的去除效果,常用于土壤及水体修复领域.而nZVI的上述特性使其在含氧环境介质中易发生氧化现象,导致物理化学性质发生变化并影响污染物的去除.本文综述了nZVI在不同环境介质中氧化后物理化学性质演变研究进展,包括nZVI制备方法及特性综述、nZVI氧化导致的结构组成和性质的演变、氧化后对重金属去除机理探讨和对环境的毒性变化,并对nZVI氧化研究与其环境领域中的应用关系进行了展望,期待为深入研究提供理论借鉴.     

纳米零价铁处理含重金属工业废水研究进展

纳米零价铁材料（nanoscale zero-valent iron, nZVI）是环境领域应用最广泛的纳米材料之一,因其原材料来源丰富、反应产物环境友好,在分离/固定水中重金属方面得到了广泛的研究.实验室研究表明,nZVI能够有效去除复杂实际废水中铜、砷、铅、锌、金等多种重金属,表现出较高的去除负荷.本研究团队在国内首先研究以nZVI技术为核心,开发分离、固定重金属工业废水中重金属的针对性废水处理工艺.构建了废水处理“反应-分离-回用”式纳米零价铁反应器（nano iron reactor, NIR）装置,通过“小试—中试—工程应用”逐级科学放大,将其应用于多种重金属工业废水的处理当中.本文总结了纳米零价铁废水处理工艺,综述了NIR反应器技术处理典型重金属废水的中试和工程应用案例,为nZVI的实际环境应用以及重金属废水处理提供了理论及技术借鉴.     

零价铁去除水中硒的研究进展

硒（Se）在水中主要以SeO₃^2-和SeO₄^2-离子形式存在,具有溶解度高、迁移能力强、毒性高等特点,过量摄入会对生命健康造成严重危害.零价铁（ZVI）是一种绿色、安全、高效且廉价的环境修复材料,通过表面氧化层的吸附作用,以及ZVI、吸附态Fe（Ⅱ）以及绿锈等活性次生矿物的还原作用,将Se（Ⅳ）和Se（Ⅵ）主要还原为低毒性、低溶解度的Se（0）,从而去除水中高毒性的SeO₃^2-和SeO₄^2-.纳米零价铁（nZVI）比表面积大、活性更高,去除Se的速率更快、效率更高,可以将SeO₃^2-和SeO₄^2-更多地还原为Se（-Ⅱ）.利用无机粘土、生物炭等材料负载nZVI,不仅可以解决nZVI易团聚、易迁移、潜在毒性风险高等问题,还可以通过载体材料的吸附、pH稳定、电子传递等作用,进一步增强nZVI对水体中Se的去除效果.实际环境中的缓冲...     

黄麻固定化漆酶去除水中Cd2+和刚果红

本文通过酶固定化技术合成漆酶-黄麻复合材料(L-SJ),以Cd²⁺和刚果红(CR)为模型污染物,通过批处理法研究了黄麻和复合材料对Cd²⁺和CR的等温去除规律,考察了漆酶浓度、温度、pH和离子强度对Cd²⁺和CR去除的影响,并结合红外光谱图探讨其去除机制.研究发现,黄麻和复合材料对Cd²⁺和CR的去除曲线均符合Langmuir等温吸附模型,复合材料对Cd²⁺的去除高于黄麻,增大约1.71—1.96倍,但降低了对CR的去除.黄麻与复合材料对Cd²⁺的去除均表现为放热反应;随pH的增大,黄麻对Cd²⁺的去除先增大后趋于平稳,而复合材料则不断增大;随离子强度的增大,黄麻与复合材料对Cd²⁺的去除不断下降.黄麻与复合材料对CR的去除随温度、离子强度的升高而增大,随pH的增大呈现先增加后降低的趋势.漆酶效能实验发现,NaOH预处理、戊二醛改性和漆酶负载均增大了复合材料对Cd²⁺的去除,NaOH预处理和...     

负载型纳米零价铁对蛋白核小球藻的毒性研究

负载型纳米零价铁不仅能够克服单一纳米零价铁(nanoscale zero-valent iron,nZVI)不稳定、易团聚等缺点,还能提高污染物的去除效率,因此被认为是一类具有广泛应用前景的高效环境修复材料.然而,纳米零价铁及其复合材料在应用过程中可进入环境,对环境及生态系统存在潜在风险.因此,为充分评估其应用对水环境的潜在危害,本文以蛋白核小球藻为受试生物,研究了负载型纳米零价铁(supported nanoscale zero-valent iron)D201-ZVI的藻类毒性及其影响因素.结果表明,负载型D201-ZVI可以显著降低nZVI生物毒性,在pH=6～10的范围内毒性效应会随pH的增加而减弱,共存污染物Cr(Ⅵ)及磺胺甲噁唑(sulfamethoxazole,SMX)均会增加D201-ZVI对蛋白核小球藻的生长抑制作用.D201-ZVI在环境中的老化作用可以减弱其生物毒性,且其毒性作用会随着暴露时间的延长而逐渐消失.D201-ZVI是一种对生物及环境安全友好的新型材料.     

二硫化钼-水滑石复合材料对水中Cu(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)的吸附机制

二维层状纳米材料可以有效去除水中的重金属,而吸附机制一直是研究难点和热点.为进一步提升材料性能,明确吸附反应机制,以典型的水滑石和二硫化钼为原料,采用共沉淀法制备镁铝水滑石,然后利用水热法负载二硫化钼,制备了复合材料(MoS₂-LDH).结果表明,MoS₂-LDH对水中Cd(Ⅱ)、Pb(Ⅱ)和Cu(Ⅱ)的吸附作用机制包括沉淀、络合、同晶置换和静电吸引作用,其中沉淀作用为主导,贡献率占46.57%—58.32%,其次为络合作用(27.15%—32.08%)和同晶置换作用(10.75%—17.86%),静电吸引的贡献最小(3.33%—4.26%);吸附过程与拟二级动力学方程和Langmuir模型相符,最大吸附量达到48.31、71.33、77.16 mg·g^-1.对高效去除重金属的吸附机制的详细研究,可为二维复合材料的设计合成提供理论支撑.     

铅在锆化碳基磁性纳米复合材料上的吸附

采用溶剂热法和沉淀沉积法成功制备锆化碳基磁性纳米复合材料,利用TEM、XRD、VSM和XRF手段对其结构特性进行表征,并研究其对水体中重金属Pb2+的吸附行为.表征结果表明,锆修饰的碳基磁性纳米材料是核壳球形结构,具有良好的超顺磁性,在外加磁场的作用下可实现快速分离.吸附实验结果表明,材料对Pb2+的吸附量随着锆负载量的提高而增多.Pb2+在材料上的吸附等温线符合Freundlich等温吸附模式,属于优惠型吸附;降低离子强度和增加p H均可提高材料对Pb2+的吸附作用.材料脱附再生6次之后仍具有良好的吸附效果.     

Preparation and characterisation of green clay-polymer nanocomposite for heavy metals removal

ABSTRACT

Natural polymer Moringa oleifera seed as coagulant and bentonite clay as adsorbent were used for preparing novel composite coagulant. Results obtained from FTIR, SEM, TEM and P-XRD show that the bentonite clay and M. oleifera seed biopolymers physico-chemically interact with each other during the preparation of clay-polymer composite. The FTIR results show that the major functional groups present in bentonite clay and M. oleifera seed are integrated at nano levels in the novel composite to remove heavy metals from aqueous systems. The coagulo-adsorption using clay-polymer composite may be used for the adsorption of heavy metals ions from the aqueous systems. It becomes possible due to the structural characteristics of the clay crystallites together with the functional attraction of the biopolymer and it results in the formation of clay-polymer metal complexes. The clay-polymer nano-composite of M. oleifera seed and bentonite clay showed considerable cadmium, chromium and lead removal property.     

利用非活体生物质去除废水中重金属的研究

为了解非活体牛物质去除废水中重金属的效果，选择了玉米芯、水稻谷壳、花生壳、松树树皮和茶叶等5种非活体生物质，州室内模拟方法比较研究了它们对重金属的吸附能力。结果表明，生物质对重金属的吸附是一个快速反应，可在20-30min内达到平衡。pH值对牛物质吸附阳离子型重金属有很大的影响，吸附量随pH值上升而增加，pH值在4．5以上时可达到较高水平。5种生物质对重金属都有较高吸附能力，它们吸附重金属的能力依次为：花生壳〉松树树皮〉玉米芯〉水稻谷壳〉茶叶。生物质去除废水中重金属的效果一般为：Cu、Pb〉Cd〉Zn。用碱、柠檬酸和磷酸对生物质进行改性处理可显著增强其对重金属的去除能力。生物质是一种廉价、有效的吸附剂，可替代商品吸附剂用于废水中重金属的去除，主要重金属的移除率在85％以上。     

高分子重金属絮凝剂对 Hg2+的捕集及性能

以含Hg^2 废水作为处理对象,研究了几个影响高分子重金属絮凝剂去除水中Hg^2 的因素,实验表明：(1)pH值对Hg^2 的去除率影响不大;(2)水中某些二价离子的存在不仅不会消耗高分子重金属絮凝剂的用量,而且会促进螯合体MHM-Hg^2 絮凝沉淀,Hg^2 的去除率在99％以上,而一价金属离子对处理效果影响不大;(3)Hg^2 和致浊物质会互相促进彼此的去除,浊度的去除率在98％以上,Hg^2 的去除率在99％以上;(4)高分子重金属絮凝剂对重金属离子具有选择性,可将部分重金属离子从其它离子中分离开、回收再利用．     

Biosorption of chromium(VI), nickel(II) and copper(II) ions from aqueous solutions using Pithophora algae

The biosorption of heavy metals is considered to be one of the best alternatives for the treatment of wastewater. The metal binding capacity of algae and acid-treated algae is investigated to find out the removal characteristics of Cr(VI), Ni(II) and Cu(II) ions from single metal solutions. Batch experiments are conducted and the study is extended to investigate the effect of pH, amount of adsorbent and adsorbate concentration on the extent of biosorption. The results indicate that the adsorption capacity of algae depends strongly on pH. The maximum adsorption of Cr(VI), Ni(II) and Cu(II) occurs at pH values of 2, 7 and 4.3, respectively. The adsorption process follows first-order kinetic equation. The data obtained are correlated with Freundlich and Langmuir adsorption isotherms.     

Removal of Cu2+ and dye from wastewater using the heavy metal precipitant N,N-bis-(dithiocarboxy)piperazine

We found that a new heavy metal precipitant, disodium N,N-bis-(dithiocarboxy)piperazine, both precipitates Cu²⁺ ions removes the dye from wastewater. The precipitation was based on a coordination polymerization reaction while the removal of the dye could be mainly attributed to an hydrophobic adsorption at pH 7.     

花生壳吸附Pb^2＋、Cu^2＋、Cr^3＋、Cd^2＋、Ni^2＋的动力学和热力学研究

以花生壳为生物吸附剂,通过序批式实验研究了吸附剂投量、吸附时间、金属离子初始质量浓度、吸附温度对吸附金属离子的影响,探讨了花生壳吸附的动力学及热力学特性。结果表明,准二级动力学方程能很好地描述花生壳对Pb^2＋、Cu^2＋、Cr^3＋、Cd^2＋、Ni^2＋的吸附过程。Langmuir模型和Freundlich模型均能较好地描述花生壳对5种重金属离子的等温吸附过程,而Langmuir模型拟合的线性更好。Pb2＋、Cu2＋、Cr3＋、Cd2＋、Ni2＋5种金属离子的最大吸附量分别是32.25、7.09、3.82、2.95、2.22 mg.g-1,花生壳可用于处理低质量浓度多种重金属混合的废水。热力学研究表明,花生壳对5种金属离子的吸附具有自发、吸热和熵增的特性。     

Methods to prepare biosorbents and magnetic sorbents for water treatment: a review

Access to drinkable water is becoming more and more challenging due to worldwide pollution and the cost of water treatments. Water and wastewater treatment by adsorption on solid materials is usually cheap and effective in removing contaminants, yet classical adsorbents are not sustainable because they are derived from fossil fuels, and they can induce secondary pollution. Therefore, biological sorbents made of modern biomass are increasingly studied as promising alternatives. Indeed, such biosorbents utilize biological waste that would otherwise pollute water systems, and they promote the circular economy. Here we review biosorbents, magnetic sorbents, and other cost-effective sorbents with emphasis on preparation methods, adsorbents types, adsorption mechanisms, and regeneration of spent adsorbents. Biosorbents are prepared from a wide range of materials, including wood, bacteria, algae, herbaceous materials, agricultural waste, and animal waste. Commonly removed contaminants comprise dyes, heavy metals, radionuclides, pharmaceuticals, and personal care products. Preparation methods include coprecipitation, thermal decomposition, microwave irradiation, chemical reduction, micro-emulsion, and arc discharge. Adsorbents can be classified into activated carbon, biochar, lignocellulosic waste, clays, zeolites, peat, and humic soils. We detail adsorption isotherms and kinetics. Regeneration methods comprise thermal and chemical regeneration and supercritical fluid desorption. We also discuss exhausted adsorbent management and disposal. We found that agro-waste biosorbents can remove up to 68–100% of dyes, while wooden, herbaceous, bacterial, and marine-based biosorbents can remove up to 55–99% of heavy metals. Animal waste-based biosorbents can remove 1–99% of heavy metals. The average removal efficiency of modified biosorbents is around 90–95%, but some treatments, such as cross-linked beads, may negatively affect their efficiency.

     

Efficient removal of heavy metals from electroplating wastewater using polymer ligands

Poly(hydroxamic acid)-poly(amidoxime) chelating ligands were synthesized from poly(methyl acrylate-co-acrylonitrile) grafted acacia cellulose for removing toxic metal ions from industrial wastewaters. These ligands showed higher adsorption capacity to copper (2.80 mmol?g⁻¹) at pH 6. In addition, sorption capacities to other metal ions such as iron, zinc, chromium, and nickel were also found high at pH 6. The metal ions sorption rate (t_1/2) was very fast. The rate of adsorption of copper, iron, zinc, chromium, nickel, cobalt, cadmium and lead were 4, 5, 7, 5, 5, 8, 9 and 11 min, respectively. Therefore, these ligands have an advantage to the metal ions removal using the column technique. We have successfully investigated the known concentration of metal ions using various parameters, which is essential for designing a fixed bed column with ligands. The wastewater from electroplating plants used in this study, having chromium, zinc, nickel, copper and iron, etc. For chromium wastewater, ICP analysis showed that the Cr removal was 99.8% and other metal ions such as Cu, Ni, Fe, Zn, Cd, Pb, Co and Mn removal were 94.7%, 99.2%, 99.9%, 99.9%, 99.5%, 99.9%, 95.6% and 97.6%, respectively. In case of cyanide wastewater, the metal removal, especially Ni and Zn removal were 96.5 and 95.2% at higher initial concentration. For acid/alkali wastewater, metal ions removing for Cd, Cr and Fe were 99.2%, 99.5% and 99.9%, respectively. Overall, these ligands are useful for metal removal by column method from industrial wastewater especially plating wastewater.     

Cerium dioxide and composites for the removal of toxic metal ions

The presence of contaminants in potable water is a cause of worldwide concern. In particular, the presence of metals such as arsenic, lead, cadmium, mercury, chromium can affect human health. There is thus a need for advanced techniques of water decontamination. Adsorbents based on cerium dioxide (CeO₂), also named ‘ceria,’ have been used to remove contaminants such as arsenic, fluoride, lead and cadmium. Ceria and composites display high surface area, controlled porosity and morphology, and abundance of functional groups. They have already found usage in many applications including optical, semiconductor and catalysis. Exploiting their attractive features for water treatment would unravel their potential. We review the potential of ceria and its composites for the removal of toxic metal ions from aqueous medium. The article discusses toxic contaminants in water and their impact on human health; the synthesis and adsorptive behavior of ceria-based materials including the role of morphology and surface area on the adsorption capacity, best fit adsorption isotherms, kinetic models, possible mechanisms, regeneration of adsorbents; and future perspectives of using metal oxides such as ceria. The focus of the report is the generation of cost-effective oxides of rare-earth metal, cerium, in their standalone and composite forms for contaminant removal.     

Effective removal of Cd2+ and Pb2+ pollutants from wastewater by dielectrophoresis-assisted adsorption

Dielectrophoresis (DEP) process could enhance the removal the Cd²⁺ and Pb²⁺ with less absorbent. The removal rates of both Cd²⁺ and Pb²⁺ increased with the increase of voltage. The overall removal rate of Cd²⁺ and Pb²⁺ in the binary system is higher than that of Cd²⁺ or Pb²⁺ in the single system. DEP could cause considerable changes of the bentonite particles in both surface morphology and microstructure. Dielectrophoresis (DEP) was combined with adsorption (ADS) to simultaneously and effectively remove Cd²⁺ and Pb²⁺ species from aqueous solution. To implement the process, bentonite particles of submicro-meter size were used to first adsorb the heavy metal ions. These particles were subsequently trapped and removed by DEP. The effects of the adsorbent dosage, DEP cell voltage and the capture pool numbers on the removal rate were investigated in batch processes, which allowed us to determine the optimal experimental conditions. The high removal efficiency, 97.3% and 99.9% for Cd²⁺ and Pb²⁺, respectively, were achieved when the ions are coexisting in the system. The microstructure of bentonite particles before and after ADS/DEP was examined by scanning electron microscopy. Our results suggest that the dielectrophoresis-assisted adsorption method has a high capability to remove the heavy metals from wastewater.