胺基树脂的合成及对水中重金属离子的吸附特征

研究了使用氯甲基化聚苯乙烯交联微球为前驱体与二乙烯三胺经回流反应合成胺基树脂及其对水中Cd2+和Ni2+的吸附特征。结果表明,胺基官能团成功地嫁接到树脂表面,胺基含量为5.6 mmol/g。胺基树脂对Cd2+和Ni2+的吸附等温线表明,温度的升高有利于吸附,且吸附等温线都符合Langmuir模型。pH值对吸附的影响较大,最佳吸附pH值范围为4~6。2种金属离子在胺基树脂上的吸附都符合准二级动力学方程。     

Facile synthesis of N-doped carbon dots for direct/indirect detection of heavy metal ions and cell imaging

In this study, an approach for the facile, rapid, energy-saving, and sensitive determination of Fe³⁺ and Cr(VI) was developed. L-arginine/D-glucose carbon quantum dots (Arg/Glu-CQDs), with a photoluminescence quantum yield of 21%, were synthesized from L-arginine and D-glucose through a facile, hydrothermal process. The maximum emission wavelength of Arg/Glu-CQDs was observed at 450 nm, under an excitation wavelength of 365 nm. In addition, Arg/Glu-CQDs exhibited a sensitive and selective response to Fe³⁺ compared to Fe²⁺ and other metal ions. The Arg/Glu-CQDs’ fluorescence was noticeably quenched through the inner filter effect (IFE) when Arg/Glu-CQDs were mixed with Fe³⁺. Accordingly, the Arg/Glu-CQDs/Fe²⁺ system could selectively detect Cr(VI); Cr(VI) could oxidize Fe²⁺ to Fe³⁺ and quench the fluorescence. The fluorescence sensor system (i.e., the Arg/Glu-CQDs/Fe²⁺ system) showed high sensitivity and excellent selectivity for the detection of Fe³⁺ and Cr(VI) in river water samples. Satisfactory detection efficiencies ranging from 97.07 to 103.46% were obtained. The cytotoxicity of Arg/Glu-CQDs was evaluated through an MTT assay using A549 cells as the target, to extend the application of Arg/Glu-CQDs to biological systems; the MTT assay indicated that the Arg/Glu-CQDs is non-cytotoxicity. Arg/Glu-CQDs were also successfully imaged in A549 cells indicating further application possibilities in bioimaging.

Graphical abstract

     

Evaluation of pectin binding of heavy metal ions in aqueous solutions

Evaluation of adsorption performance of several industrially manufactured pectins towards some toxic heavy metals was carried out. Adsorption isotherms for divalent cations in simulant aqueous solutions were measured and corresponding distribution coefficients were calculated. The following selectivity sequences we found for pectins: Pb2+ > Cu2+ > Co2+ > Ni2+ > Zn2+ > Cd2+. It was shown that a beet pectin exhibits a high affinity for Pb2+ and Cu2+ ions, an apple pectin for Co2+ ion and a citrus pectin for Ni2+ ion. The binding properties of all pectins towards Zn2+ and Cd2+ ions are extremely poor. The quantitative data on adsorption performance of pectins suggest their applicability as food additives or remedies for efficient removal of Pb2+, Cu2+, Co2+, and Ni2+ ions from different biological systems, including human and animal organisms.     

Removal of heavy metal ions from water by complexation-assisted ultrafiltration

Toxic heavy metals in air, soil and water are global problems that are growing threat to the environment. Therefore, the removal and separation of toxic and environmentally relevant heavy metal ions are a technological challenge with respect to industrial and environmental application. A promising process for the removal of heavy metal ions from aqueous solutions involves bonding the metals to a bonding agent (such as macromolecular species), and then separating the loaded agents from wastewater by separation processes such as membrane filtration. The choice of water-soluble macroligands remains important for developing this technology. The effects of type of complexing agent, pH value and applied pressure on retention coefficients of Zn(II) and Cd(II) complexes were investigated. At best operating conditions (pH=9.0, p=300kPa) using diethylaminoethyl cellulose, the removal of Cd(2+) and Zn(2+) was more than 95% and 99%, respectively.     

Sequestering of heavy metal ions from aqueous solutions by using a lignocellulosic material

The ability of Brown Stock Washer (BSW) unbleached kraft pulp and Chemi-Thermo-Mechanical Pulp (CTMP) to sequester heavy metals was studied. The BSW pulp is chemically produced while the CTM one is produced by mechanical treatment aided by some chemicals. The two pulps were rendered in their protonated form and then equilibrated with two aqueous solutions of metals. One was ocean water and the other was a laboratory prepared solution of metal ions. Both pulps were able to remove metal ions from the solution in a one-stage procedure. The overall metal removal efficiency of CTMP was in general greater than that of the BSW pulp for the low concentration metals.     

Removal of metal ions and humic acid from water by iron-coated filter media

Iron oxide is an excellent, regenerable adsorbent, and often controls free metals through adsorption reaction. The utilization of heating process for coating iron oxide on sand surface allowed the media to be used in a packed column. Iron-coated sand was investigated for adsorbing metal ions and natural organic matter from water by batch and column experiments. Chemical analysis (energy dispersive analysis of X-ray, EDAX) was used for characterizing the copper and lead adsorption sites on iron-coated sand. From the batch experiment results, the copper and lead ions could be removed simultaneously by the iron-coated sand in the competition adsorption system. The interaction between copper, lead ions and iron oxide on sand surface was primarily the chemical bonds. The maximum adsorption capacities of iron-coated sand for copper and lead were 0.259 mg Cu/g-sand and 1.211 mg Pb/g-sand, respectively. The presence of humic acid led to increase the adsorption of copper and lead. Results from column experiments indicated that the copper ions, lead ions and humic acid could be removed completely before the breakpoint. Consequently, the iron-coated sand may be applied for the adsorption/filtration of metal ions and natural organic matters from water.     

A review on detection of heavy metals from aqueous media using nanomaterial-based sensors

Environmental Science and Pollution Research - The extensive release of heavy metals into the natural water bodies has become globally prevalent from past few decades. Heavy metal toxicity is...     

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。     

橘子皮皂化改性及其对重金属离子的吸附

以农林废弃物橘子皮(OP)为原料,经氢氧化钠皂化处理,得到了改性橘子皮生物吸附剂(MOP),并将其用于对水溶液中重金属离子的吸附.研究了氢氧化钠溶液浓度、浸泡时间对改性产物产率和吸附性能的影响;通过扫描电镜、红外光谱分析,化学耗氧量、比表面积、Zeta电位的测定等方法研究了橘子皮皂化改性的机理.结果表明,橘子皮用0.2...     

廉价吸附剂处理重金属离子废水的研究进展

随着现代工业的迅速发展,生产过程中排出的有害重金属离子废水日益增加.寻找较为廉价的废水净化材料,对其中有害重金属离子的有效处理已成为环境保护中亟待解决的问题.廉价吸附剂的使用取代了目前成本较高的从溶液中回收重金属离子的方法,同时吸附剂改性会大大提高其吸附量.阐述了壳聚糖、海泡石、膨润土、海藻和泥炭等结构组成、吸附和离子交换性能等,报道廉价吸附剂对一些重金属离子的最大吸附量是:796 mg Pb/g壳聚糖,1123 mg Hg/g壳聚糖,92 mg Cr(Ⅲ)/g壳聚糖,76 mg Cr(Ⅲ)/g泥炭,41 mg Pb/g膨润土,558 mg Cd/g壳聚糖,215 mg Cd/g海藻.由此展现了廉价吸附剂在重金属离子废水处理过程中的巨大优势和良好的发展前景.     

廉价吸附剂处理重金属离子废水的研究进展

随着现代工业的迅速发展，生产过程中排出的有害重金属离子废水日益增加。寻找较为廉价的废水净化材料，对其中有害重金属离子的有效处理已成为环境保护中亟待解决的问题。廉价吸附剂的使用取代了目前成本较高的从溶液中回收重金属离子的方法，同时吸附剂改性会大大提高其吸附量。阐述了壳聚糖、海泡石、膨润土、海藻和泥炭等结构组成、吸附和离子交换性能等，报道廉价吸附剂对一些重金属离子的最大吸附量是：796mgPb／g壳聚糖，1123mgHg／g壳聚糖。92mgcr（Ⅲ）／g壳聚糖，76mgCr（Ⅲ）／g泥炭，41mgPb／g膨润土，558mgCd／g壳聚糖，215mgCd／g海藻。由此展现了廉价吸附剂在重金属离子废水处理过程中的巨大优势和良好的发展前景。     

An experimental investigation of the absorption of sulphur dioxide by water drops containing heavy metal ions

SO₂ absorption by 2 mm dia. droplets of dilute heavy metal solutions (concentration 10⁻⁶−10⁻⁴ m) exposed to trace concentration of SO₂ in air (10–1000 ppb) was measured at 25 and 8°C. Manganese and iron ions were effective catalysts of SO₂ oxidation in acidic solutions but copper ions were not. Results indicate that the manganese ion Mn²⁺ formed complexes [Mn²⁺(SO₃²⁻)₃]⁻⁴ before taking part in the oxidation reaction. The rate of SO₂ absorption by a droplet of catalyst solution decreased with decreasing pH. Decreasing the temperature of a manganese solution from 25 to 8°C caused a five- to ten-fold decrease in SO₂ absorption rate. The addition of iron ions (Fe²⁺ or Fe³⁺) to solutions of Mn²⁺ not only increased the rate of SO₂ oxidation but also reduced the dependence of absorption rate on temperature. A quantitative estimate of the rate of SO₂ removal by a typical urban cloud led to SO₂ removal rates between 0.08 and 2.0% h⁻¹ depending on temperature and the heavy metal content of the cloud water.     

橘子皮皂化交联改性及其对重金属离子的吸附

以生物废料橘子皮(OP)为原料,经乙醇、NaOH和CaCl2处理,得到皂化交联改性橘子皮(SCOP)生物吸附剂,将其用于对重金属离子Cu2+、pb2+、Cd2+、Zn2+和Ni2+的吸附,并研究了溶液pH、吸附时间和重金属离子初始浓度对SCOP吸附性能的影响.结果表明,重金属离子在改性橘子皮上的吸附速率快,符合准二级动力学方程;改性橘子皮对Cu2+、pb2+、Zn2+和Ni2+的吸附等温线符合Langmuir方程,对Cd2+的吸附等温线符合Freundlich方程,根据Langmuir方程计算对Cu2+、pb2+、Cd2+、Zn2+和Ni2+的饱和吸附量分别为72.73、209.80、85.84、56.18、33.80mg/g,均高于改性前.改性后的橘子皮生物吸附剂可以再生重复使用4次以上,是性能良好的重金属离子吸附剂.     

A rapid and high-throughput quantum dots bioassay for monitoring of perfluorooctane sulfonate in environmental water samples

Currently HPLC/MS is the state of the art tool for environmental/drinking water perfluorooctane sulfonate (PFOS) monitoring. PFOS can bind to peroxisomal proliferator-activated receptor-alpha (PPARα), which forms heterodimers with retinoid X receptors (RXRs) and binds to PPAR response elements. In this bioassay free PFOS in water samples competes with immobilized PFOS in ELISA plates for a given amount of PPARα-RXRα. It can be determined indirectly by immobilizing PPARα-RXRα-PFOS complex to another plate coated with PPARα antibody and subsequent measuring the level of PPARα-RXRα by using biotin-modified PPARα-RXRα probes-quantum dots-streptavidin detection system. The rapid and high-throughput bioassay demonstrated a detection limit of 2.5 ng L⁻¹ with linear range between 2.5 ng L⁻¹ and 75 ng L⁻¹. Detection results of environmental water samples were highly consistent between the bioassay and HPLC/MS.     

Synthesis and characterization of magnetic Fe3O4@CaSiO3 composites and evaluation of their adsorption characteristics for heavy metal ions

A two-component material (Fe₃O₄@CaSiO₃) with an Fe₃O₄ magnetite core and layered porous CaSiO₃ shell from calcium nitrate and sodium silicate was synthesized by precipitation. The structure, morphology, magnetic properties, and composition of the Fe₃O₄@CaSiO₃ composite were characterized in detail, and its adsorption performance, adsorption kinetics, and recyclability for Cu²⁺, Ni²⁺, and Cr³⁺ adsorption were studied. The Fe₃O₄@CaSiO₃ composite has a 2D core–layer architecture with a cotton-like morphology, specific surface area of 41.56 m²/g, pore size of 16 nm, and pore volume of 0.25 cm³/g. The measured magnetization saturation values of the magnetic composite were 57.1 emu/g. Data of the adsorption of Cu²⁺, Ni²⁺, and Cr³⁺ by Fe₃O₄@CaSiO₃ fitted the Redlich–Peterson and pseudo-second-order models well, and all adsorption processes reached equilibrium within 150 min. The maximum adsorption capacities of Fe₃O₄@CaSiO₃ toward Cu²⁺, Ni²⁺, and Cr³⁺ were 427.10, 391.59, and 371.39 mg/g at an initial concentration of 225 mg/L and a temperature of 293 K according to the fitted curve with the Redlich–Peterson model, respectively. All adsorption were spontaneous endothermic processes featuring an entropy increase, including physisorption, chemisorption, and ion exchange; among these process, chemisorption was the primary mechanism. Fe₃O₄@CaSiO₃ exhibited excellent adsorption, regeneration, and magnetic separation performance, thereby demonstrating its potential applicability to removing heavy metal ions.

     

饱和膨润土复合颗粒吸附剂吸附的重金属离子的固定及其再生

采用Na_2S化学再生法对吸附Fe~(2+)、Mn~(2+)、Cu~(2+)和Zn~(2+)饱和的膨润土-钢渣复合颗粒吸附剂分别进行重金属离子的固定及其再生实验研究,探究该吸附剂吸附的重金属离子的固定问题及其再生的可能性和多次再生后的吸附效果,同时根据SEM图进一步揭示固定、再生机理。结果表明:在对Fe~(2+)的固定、再生实验中,可形成Fe S沉淀而实现固定,但再生后再吸附时,膨润土复合颗粒中蒙脱石结构改变使得颗粒坍塌变成粉末状,因此,吸附Fe~(2+)饱和的膨润土复合颗粒吸附剂不适合用Na_2S再生;而对Mn~(2+)、Cu~(2+)和Zn~(2+)的固定、再生实验中,均可形成S化物沉淀而实现固定,颗粒结构未改变,经过3次再生后,吸附剂对Mn~(2+)、Cu~(2+)和Zn~(2+)的去除率还可达到94.22%、83.2%和76.30%,远比未经再生的吸附剂吸附效果好,同时,由SEM表征分析进一步揭示:Na_2S再生溶液既可使重金属离子形成MS沉淀固定,又可使复合颗粒吸附剂获得再生,实现了同步固定、再生的目的,且吸附剂经多次再生后吸附效果保持良好。     

Alternative immunofluorescent labeling of Cryptosporidium parvum in water samples using semiconductor quantum dots

The application of immunofluorescent labeling using quantum dots for detection of inactivated Cryptosporidium parvum oocysts in spiked water samples (reservoir water, treated wastewater effluent, permeate of a membrane bioreactor, and tap water) provided more consistent results compared with the organic fluorophores label. The varying degree of particles present in the different water samples (with turbidity ranging from 0.2 to 6.1 NTU) in nonconcentrated water samples had insignificant interference on the labeled counts (2-sample t-tests, p > 0.236) using the quantum dot label, while the quantum dot label provided an advantage of approximately 50% lower interference in concentrated water samples compared with the organic fluorophores label.     

基于可视角度下重金属污染物在介质中的迁移规律

介质中污染物迁移的可视化研究有助于厘清污染物及介质间微观作用机制。依托透明土的可视化理念,以Cu(Ⅱ)、Cr(Ⅵ)污染土为研究对象,分析电场及温度场驱动作用下重金属污染物在透明土及实际土体中的迁移分布规律,探讨可视化研究的可靠性并建立重金属污染物的界面迁移机制。结果表明,透明土可用于研究多孔介质中重金属污染物的迁移扩散性,电场及温度场作用下同点位污染物质量分数的波动率均在10%以内;电场作用下污染物的迁移由离子赋存状态所带电荷决定,Cu(Ⅱ)、Cr(Ⅵ)分别以阳离子、酸根阴离子状态存在,迁移方向相反。Cu(Ⅱ)因铜胶体絮凝物生成易产生聚集效应,迁移受阻;温度场作用下污染物的迁移取决于温度梯度,因土颗粒高低温处结合水厚度的差异及水分子间的吸力会促使孔隙流体迁移以达平衡,重金属污染物在对流和分子扩散的协调作用下,均表现为向低温处迁移趋势。在同外力驱动作用下,重金属污染物间的迁移存在差异性,Cr(Ⅵ)的迁移性均强于Cu(Ⅱ)的,化学沉淀物质的产生及重金属阳离子静电吸附作用是影响迁移效率的内在关键。本研究结果可为土壤污染预测及修复研究提供参考。     

一步法低温合成二维CNx纳米材料及其对水中重金属离子的吸附性能

利用尿素和乙二胺四乙酸钠盐通过一步法低温固相裂解合成了二维纳米碳氮材料(2-D CN_x),实现了对水中重金属离子的吸附去除。系统地研究了2-D CN_x对水中重金属离子Cd~(2+)、Pb~(2+)和Cu~(2+)的吸附性能,其吸附动力学过程均符合准二级动力学模型,吸附等温线更符合Langmuir模型。结果表明:Cd~(2+)、Cu~(2+)和Pb~(2+)的初始浓度均为40 mg·L~(-1),在25℃下,达到平衡时吸附量分别达到了79.4、 58.5、 72.8 mg·g~(-1); 2-D CN_x在比较广泛的pH范围(3.0～9.0)内对重金属离子都具有比较好的吸附效果;吸附剂在吸附柱过滤穿透实验中表现出很好的吸附效果和可重复利用性,且具有良好的机械稳定性。进一步的机理分析探明,吸附主要基于材料表面的羟基和重金属离子交换及氨基与重金属离子的络合协同作用。     

Pre-concentration and separation of heavy metal ions by chemically modified waste paper gel

Iminodiacetic acid was immobilized on waste paper by chemical modification in order to develop a new type of adsorption gel for heavy metal ions. Adsorption behavior of the gel was investigated for a number of metal ions, specifically Cu(II), Pb(II), Fe(III), Ni(II), Cd(II), and Co(II) at acidic pH. From batch adsorption tests, the order of selectivity was found to be as follows: Cu(II)  Fe(III) > Pb(II) > Ni(II)  Co(II) > Cd(II). Column tests were carried out for pairs of metal ions to understand the separation and pre-concentration behavior of the gel. It was found that mutual separation of Ni(II) from Co(II) and that of Pb(II) from Cd(II) can be achieved at pH 3. Similarly, selective separation of Cu(II) from Cu(II)–Fe(III) and Cu(II)–Pb(II) mixtures at pH 1.5 and 2, respectively, was observed by using this new adsorption gel. In all cases, almost complete recovery of the adsorbed metal was confirmed by elution tests with HCl.