Sol-gel derived urease-based optical biosensor for the rapid determination of heavy metals

A urease optical biosensor for the determination of heavy metals based on sol-gel immobilization technique was developed. A fluorescent dye, FITC-dextran, was encapsulated and parameters including optical properties of the probe, relative enzyme activity, initial pH value and the buffer concentration for substrate preparation were investigated. In sol-gel immobilization, 1 mM Tris-HCl at pH 7.1 provided a sufficient buffer capacity for metal ion analysis as well as the enzyme activity maintenance. Also, two analytical procedures, incubated and un-incubated systems, were compared to understand the sensitivity and applicability to heavy metal analysis. The developed optical biosensor showed high reproducibility and the relative standard deviation (R.S.D.) of 5.1% (n=10) was obtained. Also, eight measurements can be completed automatically within 36 min. The biosensor has high sensitivity to Cu(II) and Cd(II) and an analytical range of 10-230 μM with a detection limit of 10 μM was achieved. Moreover, biological and environmental samples were examined to evaluate the applicability of the developed biosensor. A 19-82% of inhibition was observed when 20-45 μM metal ions were amended into tested samples, revealing that the developed system has the potential for the determination of heavy metals in real samples.     

Spectrafluorimetric method for the rapid screening of toxic heavy metals in water samples

A fast and inexpensive sensitive screening test for recognising potential wastewater contamination by the presence of highly toxic heavy metals is described. The test is based on the reaction of the toxic heavy metals Hg(II), Cd(II), Pb(II) and Ag(I) with 6-mercaptopurine (6-MP) to produce highly fluorescent complexes.Optimum experimental conditions include a buffer of pH 7.2 (0.1 M citric acid/0.2 M Na₂HPO₄), a chelating reagent concentration of 6×10⁻⁴ M and the addition of 10⁻⁴ M of o-phenanthroline. The fluorescence emitted by the complexes was measured at 380 and 540 nm for excitation and emission wavelengths, respectively.Detection limits of 4, 3, 6 and 3 μg l⁻¹ were achieved for Hg, Cd, Pb and Ag. Relative standard deviation (R.S.D.) were between ±2 and ±6% of the fluorescence signals for five identical samples. Potential interference effects from other heavy metals (Zn, Mn, Co, Fe, Ni and Cu), which could affect the response of the proposed screening test was investigated. Results showed that none of these metals give rise to noticeable fluorescence signals under the above described experimental conditions.Finally, the capability of the proposed heavy metal screening test for the analysis of contaminated water samples is discussed.     

Solution extraction of transition and post-transition heavy and precious metals by chelate and macrocyclic ligands

This review focuses on compounds and methods that can be used for the extraction and separation from solution of two classes of elements that we define as heavy metals and precious metals. These elements are often targeted because they are toxic, costly, and their coordination chemistry has already been well studied, and because there is a need to develop methods of economically extracting, separating and recovering them from waste sites. This review outlines possible strategies that can be used, and reviews the present literature regarding the available methods for their extraction.     

微波消解-电感耦合等离子体原子发射光谱(ICP-AES)法测定含铜污泥中多种重金属

为了填补现有方法的技术空白,本方法采用微波消解和电感耦合等离子体原子发射光谱法（ ICP-AES）相结合,实现对含铜污泥中铅、锌、铬、镉、砷、镁、铝、锑量的同时测定。首先采用盐酸-硝酸-氢氟酸微波消解进行样品的前处理,消解后加入高氯酸置于电热板进行除碳并赶酸,溶样效果理想,且有效避免了高温溶样对易挥发元素砷、锑的损失,整个过程安全、高效、无损。溶样后以电感耦合等离子体发射光谱法（ ICP-AES）进行测定。对含铜污泥的分解方法进行了合理选择,并对测定时的元素分析谱线及各测定元素间干扰情况等进行了讨论。该方法的加标回收率在95.31%~107.28%%,相对标准偏差（RSD）在0.31%~2.05%之间（n=7),结果表明,该方法准确度高,操作简单快捷,可同时测定多种元素,能满足批量的测定含铜污泥中铅、锌、镍、铁、镉、铬、砷、锑含量的测定要求。     

Simultaneous determination of traces of heavy metals by solid-phase spectrophotometry

A coupling sensitive solid phase spectrophotometric (SPS) procedure for determination of traces of heavy metals (Me-SPS) and multicomponent analysis by multiple linear regressions (MA), a simple methodology for simultaneous determination of metals in mixtures was inaugurated. The Me-SPS procedure is based on sorption of heavy metals on PAN-resin and direct absorbance measurements of colour product Me-PAN sorbed on a solid carrier in a 1-mm cell. This methodology (Me-SPS-MA) was checked by simultaneous determination of metals in synthetic mixtures with different compositions and contents of metals important in pharmaceutical practice: Zn, Pb, Cd, Cu, Co, and Ni. Good agreement between experimental and theoretical amounts of heavy metals is obtained from the recovery test (78.3–110.0%). The proposed method enables determination of particular metal ion at the ng mL⁻¹ level and it was successfully applied to the determination impurities from heavy metal traces in pharmaceutical substances (Cu in ascorbic acid, Pb in glucose, and Zn in insulin). The proposed procedure could be possible contribution to the development of pharmacopoeial methodology for a heavy metals test.     

Synthesis of PS/RB-Cs and its use in the treatment of water polluted with heavy metals

Polystyrene waste are non-biodegradable materials that causes harm to the environment. Red brick waste resulting from demolition and reconstruction are an obstacle to its disposal. To solve this problem and meet modern sustainability standards, this study utilized polystyrene (PS) foam and red brick construction waste to prepare composite materials (PS/RB-Cs) as a new efficient adsorbent. The PS/RB-Cs composite as an adsorbent was characterized using a UV–Vis Spectrophotometer, Energy Dispersive X-ray Spectroscopy (EDX), Scanning Electron Microscope (SEM), and transmission electron microscopy (TEM), which showed a clear spectrum shift after using PS/RB-Cs as an adsorbent. The PS/RB-Cs was characterized by a porous structure with higher surface area and high stability. The efficiency of the PS/RB-Cs in treating water contaminated with heavy metals such as cobalt and nickel was verified under different initial concentrations, temperatures, doses, pH, and contact times. The experimental q_e values were consistent with the q_e calculated values and were approximately 8 mg/g. The adsorption isotherm models showed that the adsorption results fit the Langmuir, Freundlich and Flory-Huggins isotherm models and that the process was favorable. By applying pseudo-first-order (PFO) and pseudo-second-order (PSO) kinetic models, the adsorption process was found to follow PSO. The findings of this research validated that the composite material that was prepared serves as a potent adsorbent for the treatment of water that has been polluted by heavy metals.     

Feasibility of the use of disposable optical tongue based on neural networks for heavy metal identification and determination

This study presents the development and characterization of a disposable optical tongue for the simultaneous identification and determination of the heavy metals Zn(II), Cu(II) and Ni(II). The immobilization of two chromogenic reagents, 1-(2-pyridylazo)-2-naphthol and Zincon, and their arrangement forms an array of membranes that work by complexation through a co-extraction equilibrium, producing distinct changes in color in the presence of heavy metals. The color is measured from the image of the tongue acquired by a scanner working in transmission mode using the H parameter (hue) of the HSV color space, which affords robust and precise measurements. The use of artificial neural networks (ANNs) in a two-stage approach based on color parameters, the H feature of the array, makes it possible to identify and determine the analytes. In the first stage, the metals present above a threshold of 10⁻⁷ M are identified with 96% success, regardless of the number of metals present, using the H feature of the two membranes. The second stage reuses the H features in combination with the results of the classification procedure to estimate the concentration of each analyte in the solution with acceptable error. Statistical tests were applied to validate the model over real data, showing a high correlation between the reference and predicted heavy metal ion concentration.     

Development and optimization of magnetic technologies based processes for removal of some toxic heavy metals

In the developing countries where the cost is often a decisive factor, extensive studies were undertaken to test the most effective factors on the preparation, optimization and validation of the magnetic particles (or, more accurately, magnetizable particles) for removal of heavy metals from wastewaters. The objective of the proposed work was focused to provide promising solid-phase materials, which, are relatively in expensive and combine high surface capacity with fast efficient treatment. Four various metal oxides including hydrous ferric oxide (HFO), hydrous stannic oxide (HSO) and mixed ferric/stannic oxide (HMO), were prepared by precipitation with ammonia from metal chloride solutions. Two mixed oxides were prepared with different Sn/Fe ratios of 50% and 20%. Optimal conditions for the activation of these particles and the subsequent mixing of various metals oxides are tested together with the utility of the method to get a new composite material with developed chemical characteristics over their individual metal oxides. Factors affecting the sorption behavior of the prepared samples in basic and acid media were elucidated. The magnetic treatment procedure using the mixed oxide (50%) enables the equilibration step to be carried out rapidly mainly due to ferric oxide during the magnetization process and efficiently due to high capacity of the stannic oxide. A key factor in achieving very high uptake percentage is the reduction of non-specific binding of various heavy metals to the solid phase support. This is usually achieved by increasing the ion exchange capability, in addition to their adsorption process.     

Effects of heavy metals and oxalate on the zeta potential of magnetite

Zeta potential is a function of surface coverage by charged species at a given pH, and it is theoretically determined by the activity of the species in solution. The zeta potentials of particles occurring in soils, such as clay and iron oxide minerals, directly affect the efficiency of the electrokinetic soil remediation. In this study, zeta potential of natural magnetite was studied by conducting electrophoretic mobility measurements in single and binary solution systems. It was shown that adsorption of charged species of Co(2+), Ni(2+), Cu(2+), Zn(2+), Pb(2+), and Cd(2+) and precipitation of their hydroxides at the mineral surface are dominant processes in the charging of the surface in high alkaline suspensions. Taking Pb(2+) as an example, three different mechanisms were proposed for its effect on the surface charge: if pH<5, competitive adsorption with H(3)O(+); if 56, precipitation of heavy metal hydroxides prevails. Oxalate anion changed the associated surface charge by neutralizing surface positive charges by complexing with iron at the surface, and ultimately reversed the surface to a negative zeta potential. Therefore the adsorption ability of heavy metal ions ultimately changed in the presence of oxalate ion. The changes in the zeta potentials of the magnetite suspensions with solution pH before and after adsorption were utilized to estimate the adsorption ability of heavy metal ions. The mechanisms for heavy metals and oxalate adsorption on magnetite were discussed in the view of the experimental results and published data.     

Determination of heavy metals in soil, mushroom and plant samples by atomic absorption spectrometry

The concentrations of heavy metals in the soil, mushroom and plant samples collected from Tokat, Turkey have been determined by flame and graphite furnace atomic absorption spectrometry after dry ashing, wet ashing and microwave digestion. The study of sample preparation procedures showed that the microwave digestion method was the best. Good accuracy was assured by the analysis of standard reference materials. The relative standard deviations for all measured metal concentrations were lower than 10%. In all cases, quantitative analytical recoveries ranging from 95 to 103% were obtained. Metal accumulation factors were calculated for mushroom and plant samples. High ratio of plants to soil cadmium, zinc and copper concentrations indicate that these elements are accumulated by mushrooms. Results obtained are in agreement with data reported in the literature.     

污泥上培植的报春花、冬葵中重金属的原子吸收测定

本文研究报春花、冬葵两种植物对污泥中重金属的吸收情况,样品用(1 4)HClO4 HNO3进行了消化处理,然后在实验选定的最佳的工作条件下,用火焰原子吸收光谱法对铅、汞、铬、镉重金属元素进行了测定。结果表明:种植冬葵和报春花前后,污泥样品重金属含量明显下降。     

Adsorption of a few heavy metals on natural and modified kaolinite and montmorillonite: a review

The feasibility of using two important and common clay minerals, kaolinite and montmorillonite, as adsorbents for removal of toxic heavy metals has been reviewed. A good number of works have been reported where the modifications of these natural clays were done to carry the adsorption of metals from aqueous solutions. The modification was predominantly done by pillaring with various polyoxy cations of Zr4+, Al3+, Si4+, Ti4+, Fe3+, Cr3+or Ga3+, etc. Preparation of pillared clays with quaternary ammonium cations, namely, tetramethylammonium-, tetramethylphosphonium- and trimethyl-phenylammonium-, N'-didodecyl-N, N'-tetramethylethanediammonium, etc, are also common. Moreover, the acid treatment of clays often boosted their adsorption capacities. The adsorption of toxic metals, viz., As, Cd, Cr, Co, Cu, Fe, Pb, Mn, Ni, Zn, etc., have been studied predominantly. Montmorillonite and its modified forms have much higher metal adsorption capacity compared to that of kaolinite as well as modified-kaolinite.     

Determination of heavy metals by inductively coupled plasma-optical emission spectrometry in fish from the Piracicaba River in Southern Brazil

A total of 202 fish, representing 16 species, were collected during 2008 (March–October) in the Tanquan region of the Piracicaba River using nets. Flesh samples were collected and analyzed, using inductively coupled plasma-optical emission spectroscopy for Al, As, Cd, Co Cr, Cu, Mn, Mo, Ni, Pb, Se, Sn, Sr, and Zn. The results showed that the flesh of these fish all contained extremely high levels of Al and Sr, and moderately high levels of Cr, As, Zn, Ni, Mn and Pb. The metals were higher in these fish during rainy season, with fish collected during the months of March and October being the highest. In addition, the accumulation of metals was species-dependent. Cascudos (Hypostomus punctatus) and piranhas (Serrasalmus spilopleura) exhibited high levels of almost all of the metals, while curimbata (Prochilodus lineatus) had moderate levels. A few species, including pacu (Piaractus mesopotamicus) and dourado (Salminus maxillosus), had very low levels of most metals. The results show that the Piracicaba River Basin is widely contaminated with high levels of many toxic heavy metals, and that human consumption of some fish species is a human health concern.     

电感耦合等离子体质谱法测定固体生物质燃料中重金属

为开展重金属监测及环境保护,本文建立了电感耦合等离子体质谱法测定固体生物质燃料中重金属方法。对样品全消解酸溶法进行了实验研究,确定了微波消解酸体系和微波消解程序。采用Ge和In作为内标元素消除仪器干扰,方法线性关系良好,线性系数>0.999,检出限为0.001～0.089mg/kg。采用标准物质对方法准确性和稳定性进行验证,各元素测定值均在标准证书值范围内,相对标准偏差在0.36%～3.96%,Hg的加标平均回收率为104.7%。通过3家实验室协同实验验证了方法准确性,并给出了方法精密度。     

微塑料介导重金属在陆生植物中迁移及生物效应的影响

随着地膜在现代化农业中的广泛应用,微塑料在土壤中的残留问题日益严重。环境中释放的微塑料可能会与先前存在的重金属相互作用,导致生物效应(生物积累/毒性),并对人类健康和农产品安全构成威胁。目前,大多数研究集中于单一影响因素在土壤系统中的暴露和转化分析,有关微塑料和共存金属对环境联合影响的相当有限。本文综述了微塑料与重金属来源、相互作用机理与影响因素的研究现状,阐述了陆生植物对二者联合污染的生理响应。此外,未来的研究还应重点探讨微塑料与重金属共同在植物上暴露的具体分子机制、通过食物链对人类健康的影响、与其他混合污染物联合作用及微塑料老化过程对重金属迁移动态变化过程的影响。     

Magnetically recoverable facile nanomaterials: Synthesis, characterization and application in remediation of heavy metals

The present work reports a facile route for ethylenediaminetetraacetic acid (EDTA) immobilization on the surface of amine-terminated Fe₃O₄ nanoparticles for remediation of heavy metals from aqueous solutions. Transmission electron microscopy images showed both Fe₃O₄–NH₂ and Fe₃O₄–NH₂/PEI-EDTA magnetic nanoparticles with an average diameter of 60 nm. The FT-IR study confirmed the chemical covalent modification of EDTA on the surface of amine-terminated magnetite nanoparticles. XRD analysis demonstrated that the magnetic nanoparticles had a high crystallinity before and after modification. Magnetic measurements indicated that these nanoparticles could be easily removed through external magnetic force. The research work on the adsorption revealed that the concentration of Pb²⁺ altered from 10 to 0.12 mg/L and it indicated that 98.8% of Pb²⁺ could be removed from aqueous solutions at pH 5.05, and Fe₃O₄–NH₂/PEI-EDTA loaded heavy metal ions after being treated with 0.1 M HCl could be used as a reusable nano-adsorbent.     

Removal of some heavy metals and fungicides from aqueous solutions using nano-hydroxyapatite,nano-bentonite and nanocomposite

A batch adsorption experiments were carried out to study the role of nanoparticles and nanocomposite on removal of some heavy metals and fungicides from aqueous solution. Nano-Hydroxyapatite (n-HAP), Nano-Bentonite (n-Bo) and Bentonite-hydroxyapatite nanocomposite (B-HAP NC) evaluated for the removal of some heavy metals and fungicides. The nanoparticles and nanocomposite were characterized by TEM, SEM and AFM, X-ray powder diffraction (XRD) and BET surface area. The batch adsorption was done using nanoparticles with Pb²⁺ and Ni²⁺ as example of heavy metals with concentrations up to 25 mgL⁻¹. Also, the adsorption experiment was conducted using nano-particles (n-HAP, n-Bo and B-HAP NC) with fungicides Stop Feng and Eurozole with concentrations 20 to 200 μg L⁻¹. Langmuir and Freundlich isotherm equations were employed to study the adsorption. The adsorption kinetics were conducted metal ion (Pb²⁺ and Ni²⁺) with residence time. The results indicated the maximum adsorption capacity of Ni⁺² was occurred on (n-HAP). While that maximum adsorption capacity of Pb²⁺ was occurred on (B-HAP NC). The rate of Ni⁺² removal was found to be very rapid during the initial 60 min. The adsorption of Pb⁺² by the n-HAP and (B-HAP NC) was a slow increase with time, it did not bring any remarkable effect. Also, the efficiency of adsorbent compounds used to remove the residue of fungicides Stop Feng and Eurozole shown the highest removal rates obtained with used nano-hydroxyapatite followed by bentonite-hydroxyapatitenanocomposite and nano-bentonite, respectively. The current results are very useful in the treatment of wastewater and the removal of heavy metals and fungicides, consequently making them suitable for agricultural purposes.     

Determination of trace heavy metals in herbs by sequential injection analysis-anodic stripping voltammetry using screen-printed carbon nanotubes electrodes

A method for the simultaneous determination of Pb(II), Cd(II), and Zn(II) at low μg L⁻¹ concentration levels by sequential injection analysis-anodic stripping voltammetry (SIA-ASV) using screen-printed carbon nanotubes electrodes (SPCNTE) was developed. A bismuth film was prepared by in situ plating of bismuth on the screen-printed carbon nanotubes electrode. Operational parameters such as ratio of carbon nanotubes to carbon ink, bismuth concentration, deposition time and flow rate during preconcentration step were optimized. Under the optimal conditions, the linear ranges were found to be 2-100 μg L⁻¹ for Pb(II) and Cd(II), and 12-100 μg L⁻¹ for Zn(II). The limits of detection (S_bl/S = 3) were 0.2 μg L⁻¹ for Pb(II), 0.8 μg L⁻¹ for Cd(II) and 11 μg L⁻¹ for Zn(II). The measurement frequency was found to be 10-15 stripping cycle h⁻¹. The present method offers high sensitivity and high throughput for on-line monitoring of trace heavy metals. The practical utility of our method was also demonstrated with the determination of Pb(II), Cd(II), and Zn(II) by spiking procedure in herb samples. Our methodology produced results that were correlated with ICP-AES data. Therefore, we propose a method that can be used for the automatic and sensitive evaluation of heavy metals contaminated in herb items.     

燃烧过程中碱/碱土金属对重金属迁移转化影响的研究进展

碱/碱土金属广泛存在于各种固体燃料中，在燃烧过程中碱/碱土金属与燃料中重金属及其他矿物发生复杂的物理化学反应，从而影响重金属的迁移和转化。本研究主要介绍了碱/碱土金属对As、Se、Pb和Cr四种重金属迁移转化的影响规律，包括碱金属和碱土金属对重金属迁移转化的影响，颗粒物团聚与黏结对重金属排放的影响三个方面。碱/碱土金属能够抑制重金属的挥发：碱金属与Cl元素的结合，降低了PbCl₂的生成；碱金属的存在有利于提升高岭土对Pb的吸附效率；碱/碱土金属可以与As和Se形成稳定的化合物。但同时需要注意碱/碱土金属与Cr的部分结合产物中，Cr以六价态存在，具有较高的毒性。碱/碱土金属对于团聚现象发生，分别起到了促进和抑制作用，适当含量的碱金属有利于减少重金属的释放。通过总结碱/碱土金属对重金属迁移转化的影响规律，以期为降低重金属的危害提供思路。     

Layer double hydroxides (LDHs)- based electrochemical and optical sensing assessments for quantification and identification of heavy metals in water and environment samples: A review of status and prospects

One of the most severe environmental problems is heavy metal contamination, putting the world's sustainability at risk. Much effort has been put into developing sensors that can be taken anywhere to detect the environmental effects of heavy metals. Sensitivity, selectivity, multiplexed detection ability, and mobility enhance significantly when nanoparticles and nanostructures are incorporated into sensors. LDHs (layered double hydroxides) have gotten much attention in analytical chemistry in recent years because of their benefits, including their large specific surface area, ease of synthesis, low cost, and high catalytic efficiency and biocompatibility. LDHs are often manufactured as nanomaterial composites or created with specialized three-dimensional structures depending on the application. However, in these settings, LDHs (as color indicators, extracting sorbents, and electrochemical sensing) are usually restricted. Upcoming signs of progress and development possibilities of LDHs in analytical chemistry are reviewed in this paper to assist overcome these problems. Furthermore, the approaches used in the design of LDHs, including structural aspects, are defined and assessed in preparation for future analytical applications. The latest advances in optical and electrochemical sensors to detect heavy metals are described in this review. The sorts and characteristics of LDHs will be explored first. We will then go into microelectrode (or nanoelectrode) arrays, nanoparticle-modified electrodes, and microfluidic optical and electrochemical sensing assays in detail. This paper also discusses design strategies for LDH-based nanostructured sensors and the advantages of using nanomaterials and nanostructures.