The mechanisms of removal of heavy metals from water by ionizing radiation

The removal of heavy metal ions from water using electron beam and gamma irradiation has been investigated for the cases of Pb²⁺ and Hg²⁺ ions. These metal ions are reduced by hydrated electrons and hydrogen atoms to lower or zero valence state and eventually precipitate out of solution. Ethanol is applied as a relatively non-toxic additive to scavenge ^·OH radicals, to enhance reduction and inhibit oxidation. Mercury can be completely (>99.9%) removed from aqueous solution of 1×10⁻³ mol L⁻¹ mercury (II) chloride by using a 3 kGy dose. However, a 40 kGy dose is required to remove 96% of lead ions from a 1×10⁻³ mol L⁻¹ of PbCl₂ solution. The effect of dissolved oxygen and carbonate were also investigated. E-beam irradiation of 1×10⁻³ mol L⁻¹ lead ions complexed with ethylenediamine tetraacetic acid (EDTA) in deoxygenated as well as air-saturated solutions in the absence of ethanol resulted in removal of about 97% of the lead.     

Metallothionein-cross-linked hydrogels for the selective removal of heavy metals from water

The diverse functional repertoire of proteins promises to yield new materials with unprecedented capabilities, so long as versatile chemical methods are available to integrate biomolecules with synthetic components. As a demonstration of this potential, we have used site-selective strategies to cross-link polymer chains using the N- and C-termini of a metallothionein derived from a pea plant. This arrangement directly relates the swelling volume of the polymer to the folded state of the protein. The material retains the protein's ability to remove heavy metal ions from contaminated water samples, and can be regenerated through the subsequent addition of inexpensive chelators. The change in hydrogel volume that occurs as metal ions are bound allows the detection of contaminants through simple visual inspection. The utility of this bulk property change is demonstrated in the construction of a low-cost device that can report heavy metal contamination with no external power requirements. Most importantly, the generality of the protein modification chemistry allows the immediate generation of new hybrid materials from a wide range of protein sequences.     

Synthesis of tapioca cellulose-based poly(hydroxamic acid) ligand for heavy metals removal from water

A graft copolymerization was performed using free radical initiating process to prepare the poly(methyl acrylate) grafted copolymer from the tapioca cellulose. The desired material is poly(hydroxamic acid) ligand, which is synthesized from poly(methyl acrylate) grafted cellulose using hydroximation reaction. The tapioca cellulose, grafted cellulose and poly(hydroxamic acid) ligand were characterized by Infrared Spectroscopy and Field Emission Scanning Electron Microscope. The adsorption capacity with copper was found to be good, 210 mg g^?1 with a faster adsorption rate (t_1/2 = 10.5 min). The adsorption capacities for other heavy metal ions were also found to be strong such as Fe³⁺, Cr³⁺, Co³⁺ and Ni²⁺ were 191, 182, 202 and 173 mg g^?1, respectively at pH 6. To predict the adsorption behavior, the heavy metal ions sorption onto ligand were well-fitted with the Langmuir isotherm model (R² > 0.99), which suggest that the cellulose-based adsorbent i.e., poly(hydroxamic acid) ligand surface is homogenous and monolayer. The reusability was checked by the sorption/desorption process for six cycles and the sorption and extraction efficiency in each cycle was determined. This new adsorbent can be reused in many cycles without any significant loss in its original removal performances.     

Magnetite nanoparticles for removal of heavy metals from aqueous solutions: synthesis and characterization

Fe₃O₄ magnetic nanoparticles were synthesized by co-precipitation method. The structural characterization showed an average nanoparticle size of 8 nm. The synthesized Fe₃O₄ nanoparticles were tested for the treatment of synthetic aqueous solutions contaminated by metal ions, i.e. Pb(II), Cu(II), Zn(II) and Mn(II). Experimental results show that the adsorption capacity of Fe₃O₄ nanoparticles is maximum for Pb(II) and minimum for Mn(II), likely due to a different electrostatic attraction between heavy metal cations and negatively charged adsorption sites, mainly related to the hydrated ionic radii of the investigated heavy metals. Various factors influencing the adsorption of metal ions, e.g., pH, temperature, and contacting time were investigated to optimize the operating condition for the use of Fe₃O₄ nanoparticles as adsorbent. The experimental results indicated that the adsorption is strongly influenced by pH and temperature, the effect depending on the different metal ion considered.     

Denitrification and removal of heavy metals from waste water by immobilized microorganisms

Pseudomonas fluorescens, immobilized on soft polyvinyl chloride granules containing up to 35% softeners as carbon source, was used for simultaneous removal of nitrate and heavy metals. In typical continuous column operation, a 100 mg/L nitrate input solution was reduced to a 20 mg/L output at a feeding rate of 1500 mL/h, with a capacity of 14 kg/day/m³, and with an efficiency of 79%. In the same column, Pb(NO₃)₂ concentration was reduced from 1.0 to 0.05−0.1 mg/L and ZnSO₄ concentration was reduced from 10 to 5 mg/L.Pseudomonas aeruginosa immobilized on an O₂ plasma-treated melt blown polypropylene web was used for removing 95% of a 1.7 nCi PuCl₄ activity from a nuclear plant waste water in a batch operation.     

A Zn2GeO4-ethylenediamine hybrid nanoribbon membrane as a recyclable adsorbent for the highly efficient removal of heavy metals from contaminated water

Zn(2)GeO(4)-ethylenediamine (ZGO-EDA) hybrid nanoribbons have been synthesized on a large-scale and directly assembled to membranes, which exhibit an excellent recyclability, high selectivity, and good thermal stability for highly efficient removal of heavy metal ions, i.e., Pb(2+), Cd(2+), Co(2+), and Cu(2+), from contaminated water.     

Synthesis and characterization of PVP/AAc copolymer hydrogel and its applications in the removal of heavy metals from aqueous solution

Chelating poly(vinylpyrrolidone/acrylic acid) (PVP/AAc) copolymer hydrogels were prepared by radiation-induced copolymerization. The effects of preparation parameters such as PVP content in the hydrogel and irradiation dose on the swelling behavior of the hydrogel were studied. The pH dependent swelling was investigated. The thermal stability of the prepared hydrogel and the metal chelated ones was characterized by TGA. The removal of Fe(III), Cu(II), and Mn(II) from aqueous solution by the prepared PVP/AAc chelating hydrogel was examined by batch equilibration technique. The influence of treatment time, pH, and the initial feed concentration on the amount of the metal ions removed was studied. The results show that the removal of the metal ion followed the following order: Fe(III) > Cu(II) > Mn(II). The amounts of the removed metal ions increased with treatment time and pH of the medium. To re-use the hydrogel, the metal ions were stripped by using 2 N HCl.     

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.     

Using Zeolite/Polyvinyl alcohol/sodium alginate nanocomposite beads for removal of some heavy metals from wastewater

Functionalized Polyvinyl alcohol/sodium alginate (PVA/SA) beads were synthesized via blending Polyvinyl alcohol (PVA) with sodium alginate (SA) and the glutaraldehyde was used as a cross-linking agent. The zeolite nanoparticles (Zeo NPs) incorporated PVA/SA resulting Zeo/PVA/SA nanocomposite (NC) beads were synthesized for removal of some heavy metal from wastewater. The synthesizes beads were characterized via Fourier transforms infrared spectroscopy (FTIR), X-ray diffraction (XRD), particle size analyzer (PSA), and scanning electron microscope (SEM). The adsorption kinetics of the selected metal ions onto Zeo/PVA/SA NC beads followed the pseudo-first-order model (PFO) and the adsorption isotherm model was well fitted by the Langmuir model. Moreover, the thermodynamic studies were also examined; the outcomes showed that the adsorption mechanisms of the selective metal ions were endothermic, the chemical in nature, spontaneous adsorption on the surface of the Zeo/PVA/SA NC beads. The removal efficiency using Zeo/PVA/SA NC modified beads reached maximum at the pH value of 6.0 for Pb²⁺, Cd²⁺, Sr²⁺, Cu²⁺, Zn²⁺, Ni²⁺, Mn²⁺ and Li²⁺ with 99.5, 99.2, 98.8, 97.2, 95.6, 93.1, 92.4 and 74.5%, respectively, while the highest removal are achieved at pH = 5 for Fe³⁺ and Al³⁺ with 96.5 and 94.9%, respectively and decreased at lower or higher pH values. The survival count (%) of the E. coli cells were 34% on the SA beads, 11% on the PVA/SA, and 1% on the Zeo/PVA/SA NC modified beads, after 120 min exposure at 25 °C. Reusability experimental displays that the synthesized beads preserved a significant decrease in the sorption capacity after 10 repeating cycles. The Zeo/PVA/SA NC beads were able to eliminate 60–99.8% of Al³⁺, Fe³⁺, Cr³⁺, Co²⁺, Cd²⁺, Zn²⁺, Mn²⁺, Ni²⁺, Cu²⁺, Li²⁺, Sr²⁺, Si²⁺, V²⁺, and Pb²⁺ ions from the natural wastewater samples collected from 10th Ramadan City, Cairo, Egypt.     

Applications of ionizing radiation to the remediation of materials contaminated with heavy metals and polychlorinated biphenyls

We have investigated the removal from water of heavy metals and chelated heavy metal compounds using electron beam and gamma radiation. Parameter analyses include the effect of dissolved oxygen and the influence of adding various buffers and radical scavengers. Complete removal (>99%) of mercury, lead and cadmium ions, both free and chelated within EDTA, was achieved using radiation doses ranging from 3–100 kGy. We have also studied the radiation induced degradation of polychlorinated biphenyls (PCBs) in aqueous-organic and aqueous micellar systems. Rates and extent of dechlorination have been quantified in different solution matrices; reaction by-products and intermediate species have been identified; and the influences of dissolved oxygen and pH have been evaluated. The presence of a carbonate buffer was observed to significantly enhance PCB dechlorination yields by reducing concentrations of H₃O⁺. Ionizing radiation was effective in degrading PCBs in micellar solutions but scavenging of e_aq⁻ by the surfactant lowered reaction efficiencies.     

Use of laterite for the removal of fluoride from contaminated drinking water

The effects of different operational variables on the mechanistic function of laterite in removal of fluoride have been investigated. Thermodynamic parameters such as free energy change, enthalpy, and entropy of the process, as well as the sorption isotherm, were evaluated. The extent of solute removal is determined by initial solute concentration, operational conditions, laterite dose, and solution pH. For a fixed set of experimental conditions, a model equation is developed from which the percent removal corresponding to each load of fluoride is determined. The mechanism of fluoride adsorption is governed by the zero point charge of laterite and follows a first-order rate equation. pH has a vital role influencing the surface characteristics of laterite. To simulate the flow dynamics, fluoride solution was run through a fixed bed column. The pattern of breakthrough curves for different influent fluoride concentration, pH, and column bed height was characterized. The column efficiency was tested from the bed depth-service time model. The elution of the retained fluoride was studied and the effectiveness of column operation was determined by the retention-elution cycles.     

Cellulosic-based hydrogel from biomass material for removal of metals from waste water

Abstract

Cellulose and carboxymethyl cellulose (CMC), prepared from rice straw, were used for hydrogel preparation, separately or in a mixture of both of them in a ratios of 1:1, 1:4, 1:9, 2:3 and 3:7 (by weight).They were polymerized with partially neutralized acrylic acid (AA) in the presence of potassium persulphate, as initiator, and vinylsulphone (VS), as cross-linker. Moreover, glutaraldehyde, N,N-methylene bis acrylamide (MBA) and Epichlorohydrin (ECH) were used as cross-linker for the mixture of 1:1 of Cellulose: CMC. The mechanism of the polymerization was studied and the resulted hydrogels were characterized for their appearances, yields percentage, and water absorbencies. The Fourier transform infrared spectroscopy (FT-IR) and XRD analysis were also investigated for the hydrogel samples. Since the textile industry produces large volumes of wastewaters which contain hazardous compounds such as dyes, heavy metals like Cu(II), and surfactants, so we aimed in this research to use the hydrogel samples for Cu²⁺ absorption that can be presented in the wastewater. The FT-IR spectrum, before and after absorption, indicated that the prepared hydrogels were able to absorb the Cu²⁺. The Cu²⁺ ions can be recovered and dried to be reused again as well as the hydrogel samples can be available again for reuse.     

Novel adsorbent based on silkworm chrysalides for removal of heavy metals from wastewaters

In this contribution, maximum capacity for adsorption of Pb(2+), Ni(2+), and Cu(2+) by silkworm chrysalides (SC) was determined. The raw silkworm chrysalides (SC(r)) and chrysalides after acidic washing (SC(w)) were used. Chitin (CT), extracted from SC, and chitosan (CS), with 85% deacetylation, were employed as reference samples. Adsorption tests showed that all the studied adsorbents exhibited excellent performance in removal of metals. The choice of a more appropriate adsorbent is related to its efficiency for removal of a specific metal. The studied materials presented different intensities for metal adsorption as follows: (i) Ni(2+)>Cu(2+)>Pb(2+) for SC(r); (ii) Pb(2+)>Cu(2+)>Ni(2+) for SC(w); (iii) Ni(2+)>Cu(2+)>Pb(2+) for CT; and (iv) Cu(2+)>Pb(2+)>Ni(2+) for CS. Metal adsorption onto SC(r) and CS was analyzed by Freundlich and Langmuir isotherm equations. Adsorption values for CS-Pb and SC(r)-Ni were provided by the Freundlich model, while the adsorption values for CS-Cu, CS-Ni, SC(r)-Pb, and SC(r)-Cu were provided by the Langmuir model. The studied adsorbents are suitable for use in treatment of wastewater. From the economic point of view, the use of SC(r) as an adsorbent of heavy metals (mainly Ni(2+)) on the large industrial scale would be more appropriate.     

Determination of some heavy metals in sea water by atomic absorption spectrophotometry

Summary Direct determination of trace metals in sea water by flame atomic absorption technique suffers from serious interferences caused by the high salt content. Separation of the metals from the matrix has been effected by chelation and extraction with ammonium pyrrolidine dithiocarbamate and methyl-isobutyl-ketone. Besides a separation preconcentration and increased sensitivity is achieved with this extraction. Organic substances and metal-organic complexes are destroyed with UV-radiation before extraction is carried out. Flameless atomic absorption has been tried using the Heated Graphite Furnace combined with a) a selective volatilization procedure, b) removing of sodium from the samples using hydrated antimon pentoxide (HAP). Both methods were used to remove the interfering substances (mainly sodium salt). All the techniques have been compared by analysing the same sea water samples, some of which were also analysed by other laboratories.

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Bestimmung einiger Schwermetalle in Meereswasser durch Atomabsorptions-Spektralphotometrie

Zusammenfassung Die direkte Bestimmung der Spurenmetalle in Meereswasser durch Flammen-Atomabsorption wird durch den hohen Salzgehalt behindert. Die Abtrennung der Metalle von der Matrix wurde durch Komplexierung und Extraktion mit Ammoniumpyrrolidindithiocarbamat und Methylisobutylketon erreicht, wodurch außerdem eine Anreicherung und Steigerung der Empfindlichkeit erzielt wird. Organische Substanzen und metallorganische Komplexe können durch UV-Bestrahlung vor der Extraktion zerstört werden. Die flammenlose Technik mit Hilfe des erhitzten Graphitrohres wurde in Kombination mit a) einer selektiven Verdampfungsmethode und b) der Entfernung des Natriums mit hydratisiertem Antimonpentoxid eingesetzt. Alle Verfahren wurden an Hand der gleichen Wasserproben verglichen. Tests wurden auch von anderen Laboratorien durchgeführt.

This work was made possible by substantial grants from International Atomic Energy Agencies (IAEA) and from the Royal Norwegian Council for Scientific and Industrial Research.     

水体及土壤污染源氮硫磷及重金属汞砷铅镉综合检测仪的构建

构建了一台集取样、转化、分析的同步在线综合检测仪器,仪器构架原理基于紫外-可见光吸收检测污染源的氮硫磷水平(氨氮,PO43-,SO42-)、基于原子荧光检测Hg,As,Pb,Cd等4种有害重金属.对于水体污染源可以自动采集污水样品后直接检测;于土壤污染水平评价设计了土柱实验单元转移土壤污染物至液相,土柱实验还可协同完成...     

Extraction procedures for the determination of heavy metals in contaminated soil and sediment

Extraction tests are commonly used to study the mobility of metals in soils and sediments by mimicking different environmental conditions or dramatic changes on them. The results obtained by determining the extractable elements are dependent on the extraction procedure applied. The paper summarises state of the art extraction procedures used for heavy metal determination in contaminated soil and sediments. Two types of extraction are considered: single and sequential. Special attention is paid to the Standard, Measurement and Testing projects from the European Commission which focused on the harmonisation of the extraction procedures and on preparing soil and sediment certified reference materials for extractable heavy metal contents.     

Ion chromatographic determination of alkaline earth metals and some heavy metals

The method is described for ion chromatographic determination of Ba, Ca, Cd, Cu, Mn, Ni, Sr, Pb and Zn. Ethylenediammonium chloride or tartrate solutions are used as eluents with a suppressor column. The detection limits for the listed elements are (in μg l^?1): Ba 1.4, Ca 0.045, Cd 0.6, Cu 0.3, Mn 0.8, Ni 0.5, Pb 6.3, Sr 0.3, Zn 1.2. Relative standard deviations are 0.015–0.050 ar the 20 mg l^?1 level (n = 5, p = 0.95). Interferences are considered.     

Synthesis and characterization of substituted aminobiphenylglyoximes and their complexes with some transition metals

In this study, four different new vic-dioximates, [L¹H₂] N-(4-ethylphenyl)amino-biphenylglyoxime, [L²H₂] N-(4-butylphenyl)aminobiphenylglyoxime, [L³H₂] N-(4-aminoacetanilide)aminobiphenylglyoxime, and [L⁴H₂] N-(thiazol-2-yl-aminobiphenylglyoxime are synthesized from anti-4′-biphenylchloroglyoxime and the corresponding substituted aromatic amines. The Co(II), Ni(II), and Cu(II) complexes of these ligands are prepared. The structures of these new ligands and their complexes are proposed based upon IR, ¹H, and ¹³C NMR spectral data, mass spectroscopy, magnetic susceptibility measurement, and elemental analyses. The text was submitted by the authors in English.     

Synthesis of new ionic β-cyclodextrin polymers and characterization of their heavy metals retention

In this study, a new aqueous insoluble ionic β-cyclodextrin polymer (PYR), synthesized by reaction of β-cyclodextrin with pyromellitic anhydride [1], is characterized by IR spectroscopy, showing typical cyclodextrin and carboxylic absorptions. pH-metric titrations of the acidic functions with standard NaOH solutions followed by a refinement of protonation constants, with specific software for equilibrium in solution, have been performed. Through this approach, the pK _a values of the functional groups have been calculated. The complexation capabilities of PYR towards metal ions [Al(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Cd(II), Pt(IV), Tl(I), and U(IV)] have been evaluated in aqueous solution (pH 3–5). The retention is mainly pH dependent and higher than 70% for Al(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Cd(II) and U(IV). For Tl(I) and Pt(IV) the retention is about 60% and 40% respectively.