Bioremediation Process and Bioremoval Mechanism of Heavy Metal Ions inAcidic Mine Drainage

Acidic mine drainage(AMD) containing acidity and a broad range of heavy metal ions is classified as hazardous, and must be properly treated. The removal mechanism of heavy metal ions in acidic mine drainage contai- ning Cu²⁺, Fe²⁺, and Zn²⁺ with biological method was studied here. Using 20 mmol/L ethanol as carbon source, Desulfovibrio marrakechensis,one of sulfate reducing bacteria(SRB) species, grew best at 35 ℃ and pH=6.72 with concentrations of 10, 55 and 32 mg/L for Cu²⁺, Fe²⁺ and Zn²⁺, respectively. The removal efficiency for each ion mentioned above was 99.99%, 87.64% and 99.88%, respectively. The mineralogy and surface chemistry of precipitates were studied by means of energy dispersive spectrometer(EDS), X-ray photoelectron spectroscopy(XPS), X-ray diffraction(XRD) combined with control tests. The experimental results demonstrate that the removal mechanism of heavy metal ions by Desulfovibrio marrakechensis is comprehensive function of chemical precipitation, adsorption and bioprecipitation. The biogenic iron sulfide solid was characterized as greigite(Fe₃S₄), while the zinc sulfide solid was characterized as sphalerite(ZnS).     

UiO-66-NH2/wood的设计构筑及高效去除水中微量重金属离子性能

矿山开采、 金属冶炼、 新型金属材料的发展以及城市供水系统老化所造成的重金属(铅、 镉、 汞、 砷、 铬、 铜及锌等)污染问题已日趋严重. 传统的水处理方法很难有效地去除低浓度的重金属污染物. 本文以天然木材为载体, 采用溶剂热合成法, 在木材三维孔道中原位合成UiO-66-NH₂金属有机框架材料(MOFs)纳米颗粒, 制备了UiO-66-NH₂/wood复合膜材料. 该复合膜材料对去除水中微量重金属离子(Hg²⁺, Cu²⁺)表现出优异的性能. 当处理速率为1.1×10² L?m^-2?h^-1时, 该复合膜材料去除水中微量重金属离子的效率仍可达到90%以上, 且处理后水中重金属离子含量低于国家饮用水标准. 这可归因于木材本身独特的三维孔道结构, 在提高水通量的同时, 还可以增加水溶液中重金属离子与MOFs颗粒的接触机会, 以及孔道内均匀分布的UiO-66-NH₂ MOFs颗粒中的—NH₂可以与重金属离子通过配位作用相结合. 该UiO-66-NH₂/wood复合膜材料还具有良好的重复利用性, 在连续6次循环使用后其去除效率无明显变化, 有望进行实际应用.     

11-Mercaptoundecanoic acid functionalized gold nanoclusters as fluorescent probes for the sensitive detection of Cu2+ and Fe3+ ions

Metal ions are physiologically essential,but excessive metal ions may cause severe risk to plants and animals.Here,we prepared gold nanoclusters(Au NCs) protected by 11-mercaptoundecanoic acid(11-MUA),which have excellent fluorescence properties for the detection of metal ions.The results showed that the copper ions(Cu~(2+)) and iron ions(Fe~(3+)) in the solution have obvious quenching effect on the fluorescence intensity of Au NCs.The detection range of Fe~(3+) was 0.8–4.5 mmol/L(R~2= 0.992) and 4.5–11.0 mmol/L(R~2= 0.997).And Cu~(2+) has a lower linear range(0.1–1.0 mmol/L,R2= 0.993).When EDTA was added into the reaction system,it was observed that the quenching effect of Cu~(2+) and Fe~(3+)on Au NCs showed different phenomenon.Then,the effect of metal ions on the fluorescence of Au NCs was investigated.The selective detection of Cu~(2+) was achieved by EDTA masking of Fe~(3+).In addition,we realized the metal ions detection application of Au NCs in the serum     

A highly selective magnetic sensor with functionalized Fe/Fe3O4 nanoparticles for detection of Pb2+

A magnetic sensor for detection of Pb~(2+) has been developed based on Fe/Fe_3O_4 nanoparticles modified by3-(3,4-dihydroxyphenyl)propionic acid(DHCA). The carboxyl groups of DHCA have a strong affinity to coordination behavior of Pb~(2+) thus inducing the transformation of Fe/Fe_3O_4 nanoparticles from a dispersed to an aggregated state with a corresponding decrease, then increase in transverse relaxation time(T_2) of the surrounding water protons. Upon addition of the different concentrations of Pb~(2+) to an aq. solution of DHCA functionalized Fe/Fe_3O_4 nanoparticles(DHCA-Fe/Fe_3O_4 NPs)([Fe] = 90 mmol/L), the change of T_2 values display a good linear relationship with the concentration of Pb~(2+) from 40 μmol/L to 100 μmol/L and from 130 μmol/L to 200 μmol/L, respectively. Owing to the especially strong interaction between DHCA and Pb~(2+), DHCA-Fe/Fe_3O_4 NPs exhibited a high selectivity over other metal ions.     

A Novel Hollow Carbon@MnO2 Electrospun Nanofiber Adsorbent for Efficient Removal of Pb2+ in Wastewater

Lead ion(Pb²⁺) is one of the most hazardous heavy metal ions in aquatic environments. Carbon materials and manganese dio-xide(MnO₂) have been shown to be prospective adsorbents to cope with the lead pollution. In this study, a novel hollow carbon@MnO₂ composite nanofiber adsorbent was prepared by the combination of electrospinning and carbonization. The PAN nanofiber membrane is subjected to a pre-oxidation and carbonization process, and then the obtained carbon nanofibers react with KMnO₄ solution during the hydrothermal process to develop the hollow carbon@MnO₂ nanofibers. The hollow carbon@MnO₂ nanofibers displayed a higher adsorption capacity of Pb²⁺ than carbon and MnO₂/PDA/PAN nanofibers. The maximum adsorption capacity toward Pb²⁺ by hollow carbon@MnO₂ nanofibers was 460.83 mg/g. After 5 adsorption-desorption cycles, the carbon@MnO₂nanofibers had a good recyclability and the removal efficiency remained 81.47%. Moreover, the removal efficiency of the hollow composite nanofibers for Pb²⁺ from real wastewater could reach 94.37%. This work shows a strategy for synthetics of the hollow carbon@MnO₂ nanofibers, which exhibits a promising potential in actual wastewater treatment.     

铈锆复合氧化物修饰电极的制备及用于水样中Pb2+的检测

铅是一种有毒重金属,广泛分布在自然界中,会影响生态环境以及损害人体健康,因此对铅离子的检测十分必要。采用水热法制备了Ce₂Zr₂O_7.04纳米复合材料,将其滴涂在玻碳电极上制成修饰电极。采用X射线衍射仪（XRD）、扫描电子显微镜（SEM）和X射线光电子能谱（XPS）分别对材料的组成、形貌、价态进行了表征。使用方波阳极溶出伏安法（SWASV）对Pb²⁺进行检测,发现该修饰电极对Pb²⁺具有良好的电流响应,同时对缓冲溶液、除氧时间、富集电位和pH值等条件进行了优化。结果表明,在优化的测试条件下,该修饰电极对Pb²⁺的检测线性范围为0.0025~3.5 μmol/L,检测限（LOD）（3S/N）为0.198 nmol/L,回收率在97.6％~104.4％之间。应用于水样中Pb²⁺的检测表现出良好的重现性、稳定性和抗干扰能力,为水样中Pb²⁺的检测提供了一种新的方法。     

镧系金属离子的水化能

一、水化能公式 离子水化能是重要的热化学数据,前人曾作过很多研究^[1-4]。     

蒙脱土表面键合配位体固相萃取填料的制备及其对重金属离子的吸附性能

通过酸洗、硅烷偶联剂表面活化、键合苯甲酰异硫氰酸酯对蒙脱土进行改性,制得新型固相萃取(SPE)材料。 采用红外光谱、扫描电子显微镜、X射线光电子能谱表征了改性蒙脱土的结构和形貌。 考察了制备的SPE填料对水中As³⁺、Bi³⁺、Cu²⁺、Sb³⁺、Sn²⁺和Pb²⁺的吸附性能,确定了最佳固相萃取条件,对6种金属离子吸附容量分别为10.83、11.92、12.67、10.43、10.01及10.54 mg/g。 通过SPE与电感耦合等离子体质谱联用测定了样品中As³⁺、Bi³⁺、Cu²⁺、Sb³⁺、Sn²⁺和Pb²⁺ 6种重金属离子的含量,检出限分别为0.024、0.013、0.075、0.037、0.011和0.064 μg/L。     

6-(N,N-Dimethylamino)-2-naphthoylacryl Acid: a Highly Selective and Sensitive Fluorescent Sensor of Copper(II)

A novel fluorescent probe, 6-(N,N-dimethylamino)-2-naphthoylacryl acid(ACADAN) was designed and synthesized as a fluorescent sensor for Cu²⁺ in aqueous media. Significant amplification of fluorescence signals without causing any discernible change of maximum fluorescence emission wavelength(λ_max) was observed upon the addition of Cu²⁺. Importantly, ACADAN is capable of recognizing Cu²⁺ selectively in aqueous media in the presence of various biologically relevant metal ions and the prevalent toxic metal ions in the environment with high sensitivity(detection limit was 0.1 μmol/L).     

A Highly Selective Fluorescent Chemosensor for Cu2+

A new Zn²⁺ probe L2-Zn(L2=naphthofuran carbonylhydrazone derivant) was synthesized as a fluorescence chemosensor for Cu²⁺, by which Cu²⁺ ion could be detected with high selectivity and sensitivity in a wide pH range via a displacement “turn-off” signaling strategy. Whereas the coordination between Zn²⁺ and L2 resulted in a considerable enhancement of typical luminescence of a naphthalofuran group in complex L2-Zn, the addition of Cu²⁺ ion led to a dramatic decrease in the emission intensity of probe L2-Zn at about 503 nm(excitation at 423 nm). The competitive fluorescent experiments showed that other metal ions, such as Hg²⁺, Fe³⁺, Ag⁺, Ca²⁺, Co²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Zn²⁺, Cr³⁺ and Mg²⁺ could not impact the detection of Cu²⁺. The detection limit of the novel probe L2-Zn for Cu²⁺ ion was as low as 2.3×10^-7 mol/L, which is far lower than the guideline value of 1.6×10^-5 mol/L of the United States Environmental Protection Agency.     

Polyphenylsulfone/multiwalled carbon nanotubes mixed ultrafiltration membranes: Fabrication,characterization and removal of heavy metals Pb2+, Hg2+, and Cd2+ from aqueous solutions

Polyphenylsulfone/multiwalled carbon nanotubes/polyvinylpyrrolidone/1-methyl-2-pyrrolidone mixed matrix ultrafiltration flat-sheet membranes were fabricated via phase inversion process to inspect the heavy metals separation efficacy from aqueous media. Fabricated membranes cross-sectional morphological changes and the topographical alterations were assessed with Scanning electron microscopy (SEM) and atomic force microscopy (AFM). Particularly, MWCNTs assisted membranes exhibited better permeability ability as well as heavy metal removal enactment than virgin membrane. The dead-end filter unit was engaged in current research to examine the permeability and heavy metal removal competence of membranes. With the continuous enhancement of MWCNTs wt% in a polymer matrix, significant enhancement was observed with pure water flux study, from 41.69 L/m² h to >185 L/m² h as well as with the heavy metals separation study. Added additive MWCNTs can impact the pore sizes in membranes. The heavy metal separation results achieved, the membrane with 0.3 wt% of MWCNTs (PCNT-3) exhibited >98%, >76% and >72% for Pb²⁺, Hg²⁺ and Cd²⁺ ions, respectively. Overall, MWCNTs introduced PPSU membranes exposed best outcomes with heavy metals contained wastewater treatment.     

Influence of K+, Na+ or Ca2+ Ions on the Interaction Between AmB and Saturated Phospholipids by Langmuir Technique

Interaction between amphotericin B(AmB) and cell membrane is influenced by different metal cations. In the presence of K⁺, Na⁺ or Ca²⁺ ions, the surface pressure-area isotherms and the elastic modulus of an amphotericindipalmitoylphosphatidylcholine(AmB-DPPC) mixed monolayer were discussed. And the excess free energy and entropies of mixing were calculated according to the surface pressure-area isotherms. The phase transition of the mixed monolayer needed a higher concentration of AmB in the sequence Na⁺ > pure buffer > K⁺ > Ca²⁺. When the molar fraction of AmB(x_AmB) was 0.5, the molecular interaction changed from attraction to repulsion and the mixed monolayer turned to ordered state from disorder state under the induction of K⁺ or Ca²⁺ ions at all surface pressure in our experiment. At high surface pressure, the disorder of monolayer enhanced in the presence of Na⁺ ions at x_AmB > 0.1. At different molar ratios of AmB, the influences of these metal cations were discrepant. These cations may influence AmB molecules to form pores on the monolayer. It is helpful to understand the reduction of AmB's toxicity as theoretical reference.     

Efficient Removal of Lead from Washing Effluent of Lead-contaminated Soil with Garlic Peel

Wastewater produced from the soil washing process contains heavy metals, which limits its reuse for washing. So it is necessary to develop an efficient and economical way to recycle it, and this study presented a biosorption method to realize this goal. A typical soil sample contaminated by lead was taken from the real field near a lead smelting factory, used for the toxic metals extraction with dilute citric acid. A leach liquor was obtained with lead ions at the level of 12.35 mg/L, Cd 1.2 mg/L, Cu 1.5 mg/L, Zn 2.6 mg/L, as well as the coexisting anions, such as sulphate, silicate, chloride at the concentration of several hundred miligram per liter. The garlic peel was modified by a simple chemical saponification process and used as the biosorbent for toxic metal removal. Firstly, the adsorption behavior of lead ions on the saponified garlic peel was systematically investigated using the synthetic solutions, and then the adsorption mechanisms were explored by detailed experiments combining with the thermodynamic calculation reuslts of the aqueous system of Pb(Ⅱ)-citrate-H₂O. It was found that in artificial solution containing 0.01 mol/L citrate, the maximum adsorption capacity of 261.0 mg/g was reached at pH near 3.0, and also at this very pH value the Pb²⁺ and Pb(H₂Cit)⁺ were the dominant lead species, which are favorable for adsorption due to its easier approaching to the -COO^- ligands in the saponified garlic peel partilces via charge attraction, and the appearance of Pb(HCit)⁰ and Pb(Cit)^- at pH above 3.0 inhibits the adsorption. Secondly, the real leach liquor was used for adsorption tests, and twice adsorption under the optimal conditons would decrease the residual concentrations of Pb, Cd, Cu and Zn to zero. After elution by using 0.1 mol/L nitric acid, the adsorbed metals can be recovered and garlic peel can be reused for at least 10 cycles effectively. This study presents a prospective biosorption method for economical and efficient removal of the lead ions from soil washing wastewater with citric acid as the leaching reagent.     

ULTRAVIOLET IRRADIATION OF NUCLEIC ACIDS COMPLEXED WITH HEAVY ATOMS—III. INFLUENCE OF Ag + AND Hg 2+ ON THE SENSITIVITY OF PHAGE AND OF TRANSFORMING DNA TO ULTRAVIOLET RADIATION

Abstract— We have studied the influence of the heavy metal ions Ag⁺ and Hg²⁺ on the photoinactivation and photodimerization of transforming DNA and of bacteriophage. The rate of inactivation of Haemophilus influenzae transforming DNA by ultraviolet (UV) radiation was enhanced by a factor of 30 when it was complexed with Ag⁺. This enhancement was correlated with a comparable increase in the rate of thymine dimerization. In contrast, mercuric ions led to a reduction in the rates of both inactivation and dimerization. When we examined the effects of these metal ions on the photobiology of bacteriophage, we again found that Ag⁺ enhanced and Hg²⁺ reduced the rate of ultraviolet inactivation. These results demonstrate that heavy metals may be useful tools for studying the photochemistry and photobiology of nucleic acids.     

Efficiency of Cd(II) removal from aqueous media using chemically modified polystyrene foam

The removal of Cd(II) using polystyrene foam chemically modified with 2,2′-bipyridine has been investigated. The modified polystyrene foam has been characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis and scanning electron microscopy. The solid was employed as a Cd(II) adsorption from aqueous solutions at room temperature. The effects of several variables (pH, shaking speed, agitation time, metal concentration and presence of other ions in the medium) have been studied using batch technique. Flame atomic absorption spectrometry was used to determine the Cd(II) ion concentration in the filtrate after the adsorption process. Maximum sorption 90% was achieved at pH 7 after 30 min of shaking time. Sorbed metal ions have been desorbed with 5 ml of 2 M HNO₃ with the detection limit of 16.7 ng ml⁻¹. The Langmuir, Freundlich and D–R isotherm equation were used to describe partitioning behavior of the system at room temperature. Kinetic and thermodynamic behavior of modified polystyrene foam for Cd(II) ion removal was also studied. Br⁻, PO₄³⁻, Pb²⁺, Ni²⁺ and Cr(VI) suppress the sorption to some extent. The possible sorption mechanism of Cd(II) ions onto modified sorbent is also discussed. Method was utilized to remove Cd(II) ions from aqueous media.     

基于有机-无机介孔二氧化硅杂化材料对Cu^2和Co2+的选择性测定

合成了一种有机-无机介孔二氧化硅杂化材料(SBA-15-Tpy),通过透射电镜显微镜、X射线衍射、热重分析和N_2吸附-解吸曲线对其进行表征,并基于该材料建立了在水中对Cu²⁺和Co²⁺的选择性识别。研究表明,SBA-15-Tpy与Cu²⁺和Co²⁺结合后会分别在800 nm和510 nm处产生新的吸收峰,加入其它金属离子后不发生明显的吸收峰值变化。在最优条件下,检测Cu²⁺和Co²⁺的线性范围分别为2.0~200.0μmol/L和10.0~200.0μmol/L,检出限分别为0.48μmol/L和4.28μmol/L。将上述方法用于江水中Cu²⁺和Co²⁺的测定,回收率在96.0%~108.5%之间。     

Azomethine-H as a Highly Selective Fluorescent Probe for Fe3+ Detection in 100％ Aqueous Solution and Its Application in Living Cell Imaging

A simple assay for the detection of Fe³⁺ in water by means of fluorescence spectroscopy was developed based on a commercially available reagent, Azomethine-H(A-H), allowing sensing trace levels of Fe³⁺ with high selectivity over other cations. A significant fluorescence quenching of A-H at 424 nm was found after its binding with Fe³⁺ in 100% aqueous solution at pH=7.0, while other physiologically relevant metal ions posed little interference. The fluorescence responses can be well described by the modified Stern-Volmer equation. A good linear relationship(R²=0.9904) was observed up to 1.6×10^-5 mol/L Fe³⁺ ions. The detection limit, calculated via the 3σ IUPAC(international union of pure and applied chemistry) criteria, was 1.95×10^-7 mol/L. Moreover, the colorimetric and fluorescent response of A-H to Fe³⁺ can be conveniently detected by the naked eye, providing a facile method for visual detection of Fe³⁺. The proposed method was used to determine Fe³⁺ in water samples. Moreover, inverted fluorescence microscopy imaging using human umbilical vein endothelial cells shows that A-H can be used as an effective fluorescent probe for detecting Fe³⁺ in living cells.     

在多孔有机聚合物中构筑广谱性重金属离子吸附活性位

以三维刚性结构的三蝶烯为单体, 通过简单的Friedel-Crafts烷基化反应制备得到高比表面积的三蝶烯基多孔有机聚合物(TPOP), 在TPOP中接枝乙二胺和氯乙酸钠, 构建了广谱重金属离子吸附剂(TPOP-CH₂EDTA). 获得的TPOP-CH₂EDTA具有微孔/介孔结构, 其微孔尺寸为1.6 nm, BET比表面积为634 m²/g, 利于重金属离子传递和配位作用的强化. TPOP-CH₂EDTA对重金属离子具有吸附广谱性, 其对Ag(Ⅰ), Cu(Ⅱ), Ni(Ⅱ), Zn(Ⅱ), Co(Ⅱ), Sn(Ⅳ), Pb(Ⅱ), Cd(Ⅱ), Fe(Ⅲ)和Cr(Ⅲ)等10种重金属离子的去除率均高于98%. 以Pb(Ⅱ)为典型的重金属污染物, 通过Langmuir模型计算得到Pb(Ⅱ)的最大吸附容量高达184.5 mg/g; 具有拟二级吸附动力学特征, 吸附速率快, 动力学常数k₂为0.0173 g·mg^?1·min^?1; 经过5次循环使用后, Pb(Ⅱ)的去除效率仍高达95.8%. TPOP-CH₂EDTA对混合溶液中Pb(Ⅱ)和Cu(Ⅱ)的去除率均高于99%, 且对含有大量无机盐[如Ca(Ⅱ), Mg(Ⅱ), K(Ⅰ)和Na(Ⅰ)离子]和有机化合物的复杂真实水体系, Pb(Ⅱ)和Cu(Ⅱ)的去除效率仍高于90%. 因此, 通过调控多孔有机聚合物微观结构(如比表面积、 孔径和吸附位点密度)而构筑的广谱性重金属吸附材料, 为协同去除复杂水系统中混合重金属离子提供了方案.     

Erbium(Ⅲ) PVC membrane sensor based on N-(benzyloxycarbonyloxy)succinimide as a new neutral ionophore

In this study,a new Er³⁺ sensor based on N-（benzyloxycarbonyloxy）succinimide（BCS） as a neutral carrier has been constructed. The sensor exhibits potential linear response with a Nernstian slope of 20.5±0.4 mV/decade in the concentration range of 1.0×10^-6to 1.0×10^-2mol/L of Er³⁺.It has a very short response time（<10 s）,detection limit of 6.3×10^-7 mol/L and a good selectivity relative to a wide variety of other metal ions including common alkali,alkaline earth,heavy,and transition metal ions.It can be used in the pH range of 2.5-10.6 without any considerable divergence in potentials.The proposed sensor was successfully applied for the recovery of Er³⁺ ions spiked in tap and river water samples.     

构象转换型传感器对汞、铅、锶离子的同时检测

将核酸构象转换与纳米孔膜技术联用设计了一种新型高灵敏电化学传感器, 实现了对Hg ²⁺, Pb ²⁺和Sr ²⁺的分步同时检测. 使用2种分别能与Hg ²⁺及Pb ²⁺, Sr ²⁺结合的核酸适体, 将其固定在氧化铝纳米孔膜孔道内以阻碍铁氰化钾离子传导. 利用核酸适体包裹目标物时的蜷缩状态与目标物被洗脱剂洗脱后核酸适体的伸展状态之间的构象转换, 控制纳米孔通道的“开”和“关”, 使铁氰化钾溶液的氧化还原电流发生改变. 通过监测铁氰化钾溶液的电信号变化值, 可实现同时检测此3种金属离子的目的. 实验结果表明, 该传感器对3种金属离子具有很高的灵敏度和选择性, 检测的线性范围均为0.051.50 nmol/L, 对Hg ²⁺, Pb ²⁺和Sr ²⁺的检出限分别为0.013, 0.017和0.022 nmol/L(S/N=3).