A 1-dodecanethiol-based phase transfer protocol for the highly efficient extraction of noble metal ions from aqueous phase

A 1-dodecanethiol-based phase-transfer protocol is developed for the extraction of noble metal ions from aqueous solution to a hydrocarbon phase, which calls for first mixing the aqueous metal ion solution with an ethanolic solution of 1-dodecanethiol, and then extracting the coordination compounds formed between noble metal ions and 1-dodecanethiol into a non-polar organic solvent. A number of characterization techniques, including inductively coupled plasma atomic emission spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis demonstrate that this protocol could be applied to extract a wide variety of noble metal ions from water to dichloromethane with an efficiency of >96%, and has high selectivity for the separation of the noble metal ions from other transition metals. It is therefore an attractive alternative for the extraction of noble metals from water, soil, or waste printed circuit boards.     

A 1-dodecanethiol-based phase transfer protocol for the highly efficient extraction of noble metal ions from aqueous phase

A 1-dodecanethiol-based phase-transfer protocol is developed for the extraction of noble metal ions from aqueous solution to a hydrocarbon phase, which calls for first mixing the aqueous metal ion solution with an ethanolic solution of 1-dodecanethiol, and then extracting the coordination compounds formed between noble metal ions and1-dodecanethiol into a non-polar organic solvent. A number of characterization techniques,including inductively coupled plasma atomic emission spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis demonstrate that this protocol could be applied to extract a wide variety of noble metal ions from water to dichloromethane with an efficiency of 96%, and has high selectivity for the separation of the noble metal ions from other transition metals. It is therefore an attractive alternative for the extraction of noble metals from water, soil, or waste printed circuit boards.     

利用31P核磁共振技术优化太湖沉积物有机磷的化学提取方法

以太湖沉积物为研究对象,采用钼酸铵比色方法与液相31P-核磁共振技术(31P-NMR),研究不同浓度NaOH及NaOH与EDTA不同配比(NaOH-EDTA)对沉积物有机磷的提取及31P-NMR组成分析的影响.结果表明:不同浓度NaOH或不同配比的NaOH-EDTA,其提取沉积物总磷和有机磷量均随溶液pH值的增加而增加...     

Origin of the Henze solution/precipitate from morula cells of the blood of the ascidian Phallusia mammillata

 The "Henze solution", derived originally from the aqueous extraction of pelleted whole blood from the ascidian Phallusia mammillata, was examined using spectral studies. The aqueous extraction of fractionated blood cells including compartment cells, signet ring cells, and morula cells obtained using cell separation techniques were also examined. It was found that this Henze solution, and the Henze precipitate itself derived from this solution, emanated solely from the morula cells. Furthermore, it was found that this solution is formed independently of the vanadium metal ions otherwise associated with the vanadocytes. Observation of the Henze precipitate by light microscopy shows that this material partially forms crystallites or microglasses. Received: 27 July 1999 / Accepted in revised form: 28 February 2000     

缅甸皎漂农村地区饮用水源地土壤金属释放特征及水质安全策略

缅甸皎漂农村地区以水塘水为主要饮用水水源,此类水源普遍存在金属离子超标的问题.针对该问题,选取拟新建水塘选址地内不同深度的土壤样品,并对其进行理化指标、金属含量测定,同时对其进行浸泡及金属元素赋存形态提取实验.结果表明,土壤中除Ni元素含量超过农用地土壤污染风险筛选值外,其他金属元素含量均低于筛选值,且在垂直尺度空间上分布较均匀.通过浸泡实验发现,不同土层的浸泡液中Al、Fe、Mn、Ni元素浓度均超过了我国饮用水标准,其中,中层土（1.2~2.4 m）释放的金属离子浓度最高,释放速率最快,而深层土（>2.4 m）释放的Al、Fe、Ni离子较少.比较浸泡前后金属赋存形态发现,不同深度土壤中金属离子的释放与弱酸态、可氧化态含量变化有关,深层土中弱酸态Al、Fe、Ni释放量较少,同时通过弱酸态、可氧化态释放的金属离子被铁锰氧化物大量吸附转化为可还原态,所以其释放量低于浅层土（0~1.2 m）和中层土.Mn主要以弱酸态和可氧化态赋存于不同深度的土壤中,因此具有较高的迁移性.本文提出了以释放金属离子少的深层土作为水塘内壁的分质用土方案,以减少饮用水源金属离子释放风险,保障皎漂农村地区饮用水安全,并可为其他有类似饮用水问题的国家和地区提供参考.     

絮凝学研究的新领域——具有重金属捕集功能的高分子絮凝剂

絮凝是水质净化的重要方法之一.絮凝剂的作用对象主要是水中由不溶性物质形成的憎液溶胶及悬浮颗粒.近年来的研究发现,将重金属离子的某些强配位基团通过化学反应连接到高分子絮凝剂分子上能赋予原有高分子絮凝剂捕集水中溶解性重金属离子的功能,因此制备出具有去除重金属离子功能的高分子絮凝剂.研究表明,这类高分子絮凝剂用于水处理时表现出显著的优点,如去除效率高、沉降速度快,分离效果好,尤其适合于处理重金属离子与浊度共存的体系,显示出很好的研究及应用前景.本项研究拓展了絮凝剂作用对象的种类,开创了水处理絮凝学研究的新领域.     

Immobilization study of biosorption of heavy metal ions onto activated sludge

Activated sludge was immobilized into Ca-alginate beads via entrapment, and biosorption of three heavy metal ions, copper(Ⅱ), zinc(Ⅱ), and chromimum(Ⅱ), from aqueous solution in the concentration range of 10-100 mg/L was studied by using both entrapped activated sludge and inactivated free biomass at pH≤5. A biphasic metal adsorption pattern was observed in all immobilized biomass experiments. The biosorption of metal ions by the biosorbents increased with the initial concentration increased in the medium. The adsorption rate of immobilized pre-treated activated sludge(PAS) was much lower than that of free PAS due to the increase in mass transfer resistance resulting from the polymeric matrix. Biosorption equilibrium of beads was established in about 20 h and the adsorbed heavy metal ions did not change further with time. No significant effect of temperature was observed in the test for free biomass while immobilized PAS appeared to be strong temperature dependent in the test range of 10 and 40℃.Besides, the content of activated sludge in the calcium alginate bead has an influence on the uptake of heavy metals. The sorption equilibrium was well modeled by Langmuir isotherm, implying monomolecular adsorption mechanism. Carboxyl group in cell wall played an important role in surface adsorption of heavy metal ions on PAS.     

藻菌生物膜胞外聚合物与铅锌尾矿重金属的络合配位作用

矿产资源开采冶炼产生大量尾矿渣,其中富含的可溶性重金属引发的生态环境问题日益突显.铅锌矿是我国重要的矿产资源,尾矿露天堆放使得其富含的可溶性重金属淋溶迁移,对矿区周边地表环境造成严重污染.为探明自然水体环境中的藻菌生物膜与重金属的作用机理,采用三维荧光光谱技术研究干旱区天然湖泊中的藻菌生物膜EPS（胞外聚合物）与铅锌尾矿渣中5种重金属离子的络合配位作用.结果表明:①从藻菌生物膜EPS荧光光谱图中可检测出两个荧光峰,均来源于芳香类蛋白酪氨酸物质;②铅锌尾矿淋滤液中的重金属元素主要包括Pb、Co、Ni、Zn和Cd,且这5种金属离子均能有效淬灭EPS的荧光强度;③荧光淬灭滴定试验得出,Pb2+与EPS的络合能力最强,最大络合常数为4.523 1,最大结合位点数为1.177 5;Cd2+与EPS的络合能力最弱,最大络合常数为1.957 1,最大结合位点数为0.684 8;Co2+、Ni2+和Zn2+与EPS的络合能力相似.研究显示,藻菌生物膜EPS中含有的荧光基团与重金属离子的作用强度与金属离子的类型相关,二者的络合配位作用可能会影响重金属在水环境中的化学形态、迁移、生物有效性和生态毒性.      

New insight into adsorption characteristics and mechanisms of the biosorbent from waste activated sludge for heavy metals

The adsorption characteristics and mechanisms of the biosorbent from waste activated sludge were investigated by adsorbing Pb2+and Zn2+in aqueous single-metal solutions. A p H value of the metal solutions at 6.0 was beneficial to the high adsorption quantity of the biosorbent. The optimal mass ratio of the biosorbent to metal ions was found to be 2. A higher adsorption quantity of the biosorbent was achieved by keeping the reaction temperature below 55°C. Response surface methodology was applied to optimize the biosorption processes, and the developed mathematical equations showed high determination coefficients(above 0.99 for both metal ions) and insignificant lack of fit(p = 0.0838 and 0.0782 for Pb2+and Zn2+, respectively). Atomic force microscopy analyses suggested that the metal elements were adsorbed onto the biosorbent surface via electrostatic interaction. X-ray photoelectron spectroscopy analyses indicated the presence of complexation(between –NH2,-CN and metal ions) and ion-exchange(between –COOH and metal ions). The adsorption mechanisms could be the combined action of electrostatic interaction, complexation and ion-exchange between functional groups and metal ions.     

Removal of heavy metals through adsorption using sand

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Adsorption characteristics of copper, lead, zinc and cadmium ions by tourmaline

The adsorption characteristics of heavy metals： Cu（Ⅱ）, Pb（Ⅱ）, Zn（Ⅱ） and Cd（Ⅱ） ions on tourmaline were studied. Adsorption equilibrium was established. The adsorption isotherms of all the four metal ions followed well Langmuir equation. Tourmaline was found to remove heavy metal ions efficiently from aqueous solution with selectivity in the order of Pb（Ⅱ）〉Cu（Ⅱ）〉Cd（Ⅱ）〉Zn（Ⅱ）. The adsorption of metal ions by tourmaline increased with the initial concentration of metal ions increasing in the medium. Tourmaline could also increase pH value of metal solution.The maximum heavy metal ions adsorbed by tourmaline was found to be 78.86, 154.08, 67.25, and 66.67 mg/g for Cu（Ⅱ）, Pb（U）, Zn（Ⅱ） and Cd（U）, respectively. The temperature （25-55℃） had a small effect on the adsorption capacity of tourmaline. Competitive adsorption of Cu（Ⅱ）, Pb（Ⅱ）, Zn（Ⅱ） and Cd（Ⅱ） ions was also studied. The adsorption capacity of tourmaline for single metal decreased in the order of Pb〉Cu〉Zn 〉Cd and inhibition dominance observed in two metal systems was Pb〉Cu, Pb〉Zn, Pb〉Cd, Cu〉Zn, Cu〉Cd, and Cd〉Zn.     

Efficient removal of naphthalene-2-ol from aqueous solutions by solvent extraction

Naphthalene-2-ol is a typical biologically recalcitrant pollutant in dye wastewater.Solvent extraction of naphthalene-2-ol from aqueous solutions using mixed solvents was investigated.Various extractants and diluents were evaluated,and the effects of volume ratio of extractant to diluent,initial p H,initial concentration of naphthalene-2-ol in aqueous solution,extraction time,temperature,volume ratio of organic phase to aqueous phase(O/A),stirring rate and extraction stages,on extraction efficiency were examined separately.Regeneration and reuse of the spent extractant were also investigated.Results showed that tributyl phosphate(TBP) achieved 98% extraction efficiency for naphthalene-2-ol in a single stage extraction,the highest among the 12 extractants evaluated.Extraction efficiency was optimized when cyclohexane and n-octane were used as diluents.The solvent combination of 20% TBP,20% n-octanol and 60% cyclohexane(V/V) obtained the maximum extraction efficiency for naphthalene-2-ol,99.3%,within 20 min using three cross-current extraction stages under the following extraction conditions:O/A ratio of 1:1,initial p H of 3,25°C and stirring rate of 150 r/min.Recovery of mixed solvents was achieved by using 15%(W/W) Na OH solution at an O:A ratio of 1:1 and a contact time of 15 min.The mixed solvents achieved an extraction capacity for naphthalene-2-ol stably higher than90% during five cycles after regeneration.     

氨三乙酸酐改性纤维素对Cd~(2+)的吸附性能

本实验采用氨三乙酸酐改性玉米秸秆纤维素和苎麻纤维素,制备了两种改性纤维素吸附剂NTAA-CS及NTAA-RF,并研究了这两种吸附剂对水中Cd2+的吸附性能.通过元素分析、FTIR及SEM分析发现,纤维材料表面成功引入了氨三乙酸分子中的酯键和氨基基团.在改性纤维素吸附剂投加量为2 g·L-1,Cd2+的初始浓度为200 mg·L-1,p H值为4.0时,NTAA-CS和NTAA-RF对Cd2+的去除率分别为82.6%和90.2%.吸附实验结果表明:改性纤维素吸附剂对Cd2+的吸附是一个快速过程,吸附的最佳p H范围为4.0~7.0.吸附等温线用Langmuir方程的拟合效果优于Freundlich方程.经过5次吸附再生,吸附剂仍可以保持较大的吸附容量.这些结果表明,NTAA-CS和NTAA-RF在去除重金属废水中有较大的应用前景.     

膜萃取处理水溶液中镉、锌离子的工艺

以P204+正庚烷为萃取剂,将中空纤维膜萃取技术用于处理水溶液中镉离子、锌离子.研究了两相流速、初始浓度及溶液pH等因素对传质系数和萃取率的影响,计算了膜萃取器的传质单元高度(HTU)_w,同时还研究了萃取剂的再生问题.实验结果表明,在低浓度下(＜500 mg/L),平衡分配系数较大,传质阻力主要是在水相;在初始浓度较高时(＜2000mg/L),由于分配系数较小,三项传质阻力均不可忽略;在初始浓度很高时(＞2000mg/L),传质由有机相和膜相阻力控制.实验还表明通过膜器串联可以实现萃取剂的再生.对于稀溶液(＜200mg/L),中空纤维膜萃取可以使水溶液中金属离子浓度减小2个数量级,通过计算,中空纤维膜萃取器(HTU)_w在15～30cm之间,大大低于传统的萃取塔.     

柠檬酸对重金属复合污染土壤的浸提效果研究

以浙江富阳某炼铜厂附近受Cd、Cu、Pb和Zn复合污染的土壤为研究对象,采用振荡、静置和超声3种不同浸提方式,通过研究柠檬酸在不同浸提方式下对重金属的去除效果,筛选出最佳柠檬酸浓度、处理时间及功率,并采用Tessier连续提取法分析浸提前后4种重金属形态变化.结果表明,柠檬酸对4种重金属均具有较好的去除效果,其中对Zn的去除效果最好,Cd的去除效果最差,而Cu和Pb的去除效果相当.Pb和Zn的去除率均随着柠檬酸浓度的增加而增加,但增幅随之减小,Cu的去除率则先增加后基本保持不变,而Cd的去除率变化不明显.综合考虑成本和浸提效果后,选用0.2 mol·L-1柠檬酸浸提2次为最优条件,最佳振荡时间和静置时间分别为4 h和24 h,最佳超声时间和功率分别为30 min和500 W.柠檬酸能够在很大程度上改变土壤中重金属的形态分布,主要去除以可交换态和碳酸盐结合态形式存在的Cd及以碳酸盐结合态和铁锰氧化物结合态形式存在的Cu、Pb和Zn.通过对比3种浸提方式,在同等去除效果的前提下,静置浸提相比振荡浸提需要更长的时间,而将超声波应用于重金属污染土壤淋洗,所需时间较少,因此,超声波辅助浸提土壤中重金属是可行的,具有良好的应用前景.     

CTAB改性地聚合物同时去除Cu(II)和Cr(VI)

地聚合物（Geopolymer,简称GP）是由含硅铝酸盐的偏高岭土（Metakaolin,简称MK）或固体废料（如粉煤灰）经碱性激活制备的立体网状结构无机聚合物,对大部分重金属阳离子有良好的吸附作用,但对以阴离子形态存在的重金属吸附效果很差.本研究以偏高岭土为主要原料制备GP,同时用CTAB进行改性,研究其化学组成变化及对典型以阴、阳离子形态存在的重金属Cr（VI）和Cu（II）的同时吸附作用.结果表明,pH为5、吸附时间为24 h、初始浓度为50 mg·L^-1、吸附剂投加量为1 g·L^-1时,CTAB-GP对Cu（II）的去除率达到98.6%,Cr（VI）的最高去除率为25.6%,同时还发现溶液中Cu（II）的存在对吸附Cr（VI）有较大促进作用.整体来看,两种金属混合吸附时很好地符合二级动力学规律,单溶质吸附很好地符合Langmuir和Freundlich等温式,Cu（II）和Cr（VI）的理论最大吸附量分别为147.1 mg·g^-1和63.1 mg·g^-1.XRD、FTIR和BET表征分析结果表明,CTAB-GP中即使存在季铵盐阳离子,但依然属于地聚合物.CTAB-GP可以不牺牲对重金属阳离子吸附性能的同时吸附阴离子,优于常规地聚合物,鉴于CTAB-GP的这种特性,其在重金属污染防治中显示出极大的应用前景.     

Chemically modified silica gel with 1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone: Synthesis, characterization and application as an efficient and reusable solid phase extractant for selective removal of Zn(II) from mycorrhizal treated fly-ash samples

1-{4-[(2-hydroxy-benzylidene)amino]phenyl}ethanone functionalized silica gel was synthesized and used as a highly efficient, selective and reusable solid phase extractant for separation and preconcentration of trace amount of Zn(II) from environmental matrices. The adsorbent was characterized by fourier transform infrared spectroscopy (FT-IR), elemental analysis,¹³C CPMAS NMR spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and BET surface area analysis. The dependence of zinc extraction on various analytical parameters such as pH, type and amount of eluent, sample flow rate and interfering ions were investigated in detail. The material exhibited superior adsorption efficiency for Zn(II) with high metal loading capacity of 1.0 mmol/g under optimum conditions. After adsorption, the recovery (> 98%) of metal ions was accomplished using 1.0 mol/L HNO₃ as an eluent. The sorbent was also regenerated by microwave treatment in milder acidic environment (0.1 mol/L HNO₃). The lower detection limit and preconcentration factor of the present method were found out to be 0.04 μg/L and 312.5 respectively. The modified silica surface possessed excellent selectivity for the target analytes and the adsorption/desorption process remained effective for at least ten consecutive cycles. The optimized procedure was successfully implemented for the extraction of Zn(II) from mycorrhizal treated fly ash and pharmaceutical samples with reproducible results.     

Removal of heavy metals from artificial metals contaminated water samples based on micelle-templated silica modified with pyoverdin I

The micelle-templated silica (MTS) was firstly chemically modified with 3-glycidoxypropyl-trimethoxysilane (GPTMS) before immobilized with pyoverdin I. The characteristics of pyoverdin I-anchored onto the modified MTS were investigated using fluorescence, infrared spectra and scanning electron microscopy. The specific surface area of all materials was calculated by Bnmauer, Emmett and Teller (BET) method using nitrogen isotherm adsorption data. As the results, the surface area of commercial silica gel decreased from 609.2 to 405.4 m2/g, it indicated that the pyoverdin I could be immobilized onto the surface of silica solid support. This adsorbent was used for extraction of Fe(Ⅲ), Cu(Ⅱ), Zn(Ⅱ), and Pb(Ⅱ) in artificial metals contaminated water. Experimental conditions for effective adsorption of trace levels of metal ions were optimized with respect to different experimental parameters using batch procedure. The optimum pH value for the removal of metal ions simultaneously on this adsorbent was 4.0. Complete desorption of the adsorbed metal ions from the adsorbent was carded out using 0.25 mol/L of EDTA. The effcct of different cations and anions on the adsorption of these metals on adsorbent was studied and the results showed that the proposed adsorbent could be applied to the highly saline samples and the sample which contains some transition metals.     

抗生素与重金属复合污染废水处理的研究进展

随着越来越多的污染物进入环境,水体抗生素和重金属复合污染问题已引起学者们的关注.在归纳和总结抗生素和重金属相互作用机理的基础上,综述了抗生素和重金属复合污染废水主要处理技术的研究进展,并总结了其作用机理及优缺点.结果表明:抗生素和重金属的相互作用主要受到抗生素官能团的种类、重金属离子的类型和溶液pH的影响;吸附法是当前应用最多的方法,而光催化法和人工湿地法具有广阔的应用前景,将絮凝剂或零价铁基改性能够增强抗生素和重金属复合污染废水的处理效果,各种方法相结合对处理水体抗生素和重金属复合污染有较大潜力.建议今后研究应着重关注以下几个方面:①各种处理技术在实际环境水体中的应用;②复合污染的环境影响及相关法规标准的制订与完善;③新污染物抗性基因的生成机理及其影响因素.      

Selective adsorption of silver ions from aqueous solution using polystyrene-supported trimercaptotriazine resin

Trimercaptotriazine-functionalized polystyrene chelating resin was prepared and employed for the adsorption of Ag(I) from aqueous solution. The adsorbent was characterized according to the following techniques: Fourier transform infrared spectroscopy, elemental analysis, scanning electron microscopy and the Brunauer-Emmet-Teller method. The effects of initial Ag(I) concentration, contact time, solution pH and coexisting ions on the adsorption capacity of Ag(I) were systematically investigated. The maximum adsorption capacity of Ag(I) was up to 187.1 mg/g resin at pH 0.0 and room temperature. The kinetic experiments indicated that the adsorption rate of Ag(I) onto the chelating resin was quite fast in the first 60 min and reached adsorption equilibrium after 360 min. The adsorption process can be well described by the pseudo second-order kinetic model and the equilibrium adsorption isotherm was closely fitted by the Langmuir model. Moreover, the chelating resin could selectively adsorb more Ag(I) ions than other heavy metal ions including: Cu(II), Zn(II), Ni(II), Pb(II) and Cr(III) during competitive adsorption in the binary metal species systems, which indicated that it was a highly selective adsorbent of Ag(I) from aqueous solution.