Palladium and platinum sorption using chitosan-based hydrogels

Two chitosan hydrogels (prepared by NaOH neutralization and by polyphosphate ionotropic gelation) have been tested in the dry state for Pd(II) and Pt(IV) sorption at pH 2. Similar sorption isotherms with maximum sorption capacities close to 190 mg Pd g⁻¹ and 235 mg Pt g⁻¹ were achieved. The sorption mechanism involves electrostatic attraction of the chloro-anionic species onto protonated amine groups; the drastic decrease of sorption capacity with the addition of chloride ions supports this hypothesis. SEM-EDAX analysis suggests that sorption proceeds, in kinetic terms, through a shrinking core mechanism. Metal ions can diffuse throughout all the sorbent volume. The main differences between the sorbents are revealed by kinetics. The hydrogels prepared by ionotropic gelation in polyphosphate (C-PPh) allows reaching equilibrium much faster than the hydrogels prepared by the neutralization process (C-NaOH). While for C-PPh sorbent the chemical reaction rate seems to control sorption profiles, in the case of C-NaOH a combination of mechanisms including intraparticle diffusion resistance controls uptake kinetics. Metal desorption from loaded sorbents is possible using thiourea alone or in association with HCl solutions. The recycling of the sorbents is possible but for a limited number of cycles.     

Mercury(II) Biosorption Using <Emphasis Type="Italic">Lessonia</Emphasis> sp. Kelp

Lessonia nigrescens and Lessonia trabeculata kelps have been tested for the sorption of mercury from aqueous solutions. A pretreatment (using CaCl₂) allowed stabilizing the biomass that was very efficient for removing Hg(II) at pH 6–7. Sorption isotherms were described by the Langmuir equation with sorption capacities close to 240–270 mg Hg g⁻¹ at pH 6. The temperature had a negligible effect on the distribution of the metal at equilibrium. The presence of chloride anions had a more marked limiting impact than sulfate and nitrate anions. The uptake kinetics were modeled using the pseudo-second-order equation that fitted better experimental data than the pseudo-first-order equation. The particle size hardly influenced sorption isotherms and uptake kinetics, indicating that sorption occurs in the whole mass of the biosorbent and that intraparticle mass transfer resistance was not the limiting rate. Varying the sorbent dosage and the initial metal concentration influenced the equilibrium, but the kinetic parameters were not drastically modified. Metal can be eluted with hydrochloric acid, citric acid, or acidic KI solutions.     

Influence of the Degree of Chitosan Sulfoethylation on the Sorption of Palladium(II) Chloride Complexes from Multicomponent Solutions

The influence exerted by the degree of substitution of sulfoethylated chitosan cross-linked with glutaraldehyde on the sorption of Pd(II) chloride complexes from multicomponent solutions containing Pt(IV), Cu(II), Ni(II), Co(II), Cd(II), and Zn(II) was studied. The sorption of transition metal ions under the conditions of the experiment at pH 0.5–5.0 is virtually fully suppressed. The strongest interfering effect on the Pd(II) sorption is exerted by Pt(IV). Calculation of the selectivity coefficients K_Pd/Pt shows that the selectivity of the Pd(II) sorption relative to Pt(IV) increases with an increase in the degree of substitution of chitosan from 0.3 to 0.5. Integral kinetic curves of the Pd(II) sorption were obtained, and the dependences were subjected to mathematical processing using the models of diffusion and chemical kinetics. The equilibrium in the palladium(II) chloride solution–sorbent system is attained within 40 min. Pd and Pt are quantitatively desorbed from the sorbent surface under dynamic conditions with 3.5 M HCl solution.     

Analytical characterization of a silica gel sorbent with thioetheric sites

The sorption behavior of a newly synthesized silica gel sorbent with thioetheric sites (STS) towards microgram levels of Au(III), Pt(IV) and Pd(II) was studied. Au(III) is quantitatively (>95%) sorbed in the pH region of 1–9. The sorption of Pt(IV) starts at pH 1 and does not exceed 25% in the entire pH region examined. The sorption of Pd(II) starts at pH 7 and reaches 80% at pH 9. The sorption of Au(III) on STS at pH 1 is not affected by milligram amounts of Ni(II), Zn(II), Fe(III), Cu(II), Pb(II), Cd(II) or Co(II). Au(III) is quantitatively eluted with a 5% aqueous solution of thiourea. The adsorption capacity of STS towards Au(III) is 195 mg g⁻¹. The detection limit (DL) of Au(III) (3σ, n = 9) is 25 ng mL⁻¹. The RSD at a level of 10 × DL is about 2%. Solid-phase extraction of trace amounts of Au(III) on the STS sorbent, followed by its flame AAS determination in the eluate was applied to the determination of gold in geological samples. The results obtained for the gold content in the samples were in good agreement with those of the ICP-AES analysis.     

Preconcentration of uranium(VI) and thorium(IV) from aqueous solutions using low-cost abundantly available sorbent

Olive cake as low-cost abundantly available sorbent has been characterized by N₂ at 77 K adsorption, porosity analysis, elemental analysis and IR spectra and has been used for preconcentrating of uranium(VI) and thorium(IV) ions prior to their determination spectrophotometrically. The optimum pH values for quantitative sorption of U(VI) and Th(IV) are 4–7 and 3–7, respectively. The enrichment factor for the preconcentration of U(VI) and Th(IV) were found to be 125 and 75 in the given order. The sorption capacity of olive cake is in the range of 2,260–15,000 μg g⁻¹ for Th(IV) and in the range of 1,090–17,000 μg g⁻¹ for U(VI) at pH 3–7. The sorbent exhibits good reusability and the uptake and stripping of the studied ions were fairly rapid. The elution of U(VI) and Th(IV) was performed with 0.3–1 M HCl/1–2 M HNO₃ and 0.3–0.8 M HCl/1 M HNO₃, respectively. The precision of the method was 1.8 RSD% for U(VI) and 2.5 RSD% for Th(IV) in a concentration of 1.00 μg mL⁻¹ for 10 replicate analysis. The influence of some electrolytes and cations as interferents was discussed. Separation of U(VI) and Th(IV) from other metal ions in synthetic solution was achieved.     

Column solid phase extraction and determination of ultra-trace Au,Pd and Pt in environmental and geological samples

A new sorbent based on cysteine modified silica gel (SiG-cys) was prepared and studied for preconcentration and separation of noble metals Au(III), Pd(II), Pt(II), Pt(IV). Its extraction efficiency was examined by batch and column solid phase extraction procedures. Laboratory experiments performed showed that sorbent is characterized with high selectivity, permiting quantitative sorption (93–97%) of noble metals Au, Pd and Pt from acidic media 0.1–2 mol L^? 1 HCl and unsignificant sorption (less than 2%) for common base metals like Cu, Fe, Mn and Zn. The analytes retained on the sorbent are effectively eluted with 0.1 mol L^? 1 thiourea in 0.1 mol L^? 1 HCl and measured by ETAAS or ICP OES under optimal instrumental parameters. The sorbent showed high mechanical and chemical stability and extraction efficiency was not changed after 500 cycles of sorption/desorption. The sorbent was successfully applied in analyticals procedures for preconcentration and determination of Au, Pd and Pt in geological and soil samples. Detection limits (3σ criteria) achieved, depending on the instrumental methods used are: ETAAS (0.005 μg L^? 1 for Au in river and sea water, 0.002 μg g^? 1 for Au in copper ore and copper concentrate); ICP OES (0.03 μg L^? 1 for Pd and 0.06 μg L^? 1 for Pt in river and sea water, 0.006 μg g^? 1 for Pd in copper ore and copper concentrate and 0.002 μg g^? 1 for soluble Pt in soil). The accuracy of the procedures developed was confirmed by added/found method for sea and river water; by the analysis of national certified materials (copper ore and copper concentrate for Au and Pd) and by determination of the sum of soluble Pt(II) + Pt(IV) in spiked soil samples.     

Sorption behavior of Sn(II) onto Haro river sand from aqueous acidic solutions

The sorption behavior of Sn(II) onto Haro river sand has been examined with respect to nature of electrolyte, agitation time, dosage of sorbent and concentration of sorbate. Maximum sorption (95.5%) has been achieved from 0.034M hydrochloric acid solution after equilibrating sorbate (2·10⁻⁵M) and sorbent (50 mg) for 120 minutes at aV/W ratio of 90 cm³·g⁻¹. The kinetic data have been subjected to Morris-Weber and Lagergren equations. The kinetics of sorption proceeds a two stage process consisting of a relatively slow initial uptake followed by a much rapid increase in the sorption. The rate constant of intraparticle transport, K_d, comes out to be 8.75·10⁻⁸ mol·g⁻¹·min^−1/2 and the first order rate constant for sorption is 0.0416 min⁻¹. The sorption data of Sn(II) onto Haro river sand followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) type isotherms. The Langmuir constant,Q, related to sorption capacity and,b, related to sorption energy are computed to be 10.6±1.1 μmol·g⁻¹ and 1123±137 dm³·mol⁻¹, respectively. The D-R isotherm yields the values ofC _m=348±151 μmol·g⁻¹ and β=−0.01044±0.0008 mol²·kJ⁻² and ofE=6.9±0.3 kJ·mol⁻¹. In all three isotherms correlation factor (γ) is ≥0.99. The influence of common anions and cations on the sorption has been investigated. Zn(II), Mg(II), oxalate, Pb(II), Mn(II) and tartrate reduce the sorption significantly whereas Fe(II) causes substantial increase in the sorption. It is essential that all ions causing a decrease in the sorption of Sn(II) must be absent from the sorptive solution otherwise low sorption yields would result.     

Synthesis,spectroscopic analysis and structure deduction of gold(III), palladium(II) and platinum(II) complexes with the tripeptide glycyl-<Emphasis Type="SmallCaps">l</Emphasis>-phenylalanyl-glycine

The coordination behaviour of the tripeptide glycyl-l-phenylalanyl-glycine (H-Gly-Phe-Gly-OH) with Au(III), Pd(II), and Pt(II) in both solution and in the solid state has been investigated experimentally. In addition, quantum chemical calculations have been carried out with a view to obtain the structures and spectroscopic properties of the ligand and its complexes. Both in solution and in the solid state the tripeptide interacts in a tetradentate manner with the Au(III) and Pd(II) ions through the NH₂, two deprotonated amide N atoms and the COO⁻group, forming [Au(H-Gly-Phe-Gly-OH)H₋₂)] × H₂O and [Pd(H-Gly-l-Phe-Gly-OH)H₋₂)]Na × H₂O complexes. The MN₃O chromophores are calculated to be near planar. Interaction with cisplatin leads to the formation of a mononuclear complex with tridentate coordination of the ligand by NH₂ and two N- atoms from the deprotonated amide groups ([Pt(H-Gly-l-Phe-Gly-OH)H₋₂)NH₃] × 2H₂O). The fourth coordination position of the Pt(II) is occupied by an NH₃ ligand. The PtN₄ chromophore is flat with a deviation from planarity of 0.3°. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

<Emphasis Type="Italic">p</Emphasis>-<Emphasis Type="Italic">tert</Emphasis>-Butylcalix[8]arene loaded silica gel for preconcentration of uranium(VI) via solid phase extraction

This paper reports silica gel loaded with p-tert-butylcalix[8]arene as a new solid phase extractor for determination of trace level of uranium. Effective extraction conditions were optimized in column methods prior to determination by spectrophotometry using arsenazo(III). The results showed that U(VI) ions can be sorbed at pH 6 in a mini-column and quantitative recovery of U(VI) (>95–98%) was achieved by stripping 0.4 mol L⁻¹ HCl. The sorption capacity of the functionalized sorbent is 0.072 mmol uranium(VI) g⁻¹ modified silica gel. The relative standard deviation and detection limit were 1.2% (n = 10) for 1 μg uranium(VI) mL⁻¹ solution and 0.038 μg L⁻¹, respectively. The method was employed to the preconcentration of U(VI) ions from spiked ground water samples.     

Highly efficient adsorbing noble metal ions by 3,4-dihydroxycinnamic acid-modified activated carbon

A method was established for the preconcentration of trace Au(III), Pd(II) and Pt(IV) by activated carbon modified with 3,4-dihydroxycinnamic acid. The separation and preconcentration conditions of analytes were investigated, such as effects of pH, the contacting time, the sample ?ow rate and volume, the elution condition and the interfering ions. At a pH of 1.0, the maximum static sorption capacity of the sorbent was found to be 374.8, 96.6 and 137.5 mg g^?1 for Au(III), Pd(II) and Pt(IV), respectively. The adsorbed metal ions were effectively eluted with 2.0 mL of 4% thiourea in 0.5 M HCl solution and determined by inductively coupled plasma optical emission spectrometry. The detection limit (3σ) of this method defined by IUPAC was found to be 0.12, 0.18 and 0.32 ?g L^?1 for Au(III), Pd(II) and Pt(IV), respectively. The relative standard deviation (RSD) was lower than 3.0% (n = 8) towards standard solutions. The method has been validated by analysing certified reference materials and successfully applied to the determination of trace Au(III), Pd(II) and Pt(IV) in road sediments samples.     

Sorption of cesium from water solutions on potassium nickel hexacyanoferrate-modified <Emphasis Type="Italic">Agaricus bisporus</Emphasis> mushroom biomass

In order to gain biosorbent that would have the ability to bind cesium ions from water solution effectively, potassium nickel hexacyanoferrate(II) (KNiFC) was incorporated into the mushroom biomass of Agaricus bisporus. Cesium sorption by KNIFC-modified A. bisporus biosorbent was observed in batch system, using radiotracer technique using ¹³⁷Cs radioisotope. Kinetic study showed that the cesium sorption was quite rapid and sorption equilibrium was attained within 1 h. Sorption kinetics of cesium was well described by pseudo-second order kinetics. Sorption equilibrium was the best described by Freundlich isotherm and the distribution coefficient was at interval 7,662–159 cm³ g⁻¹. Cesium sorption depended on initial pH of solution. Cesium sorption was very low at pH₀ 1.0–3.0. At initial pH 11.0, maximum sorption of cesium was found. Negative effect of monovalent (K⁺, Na⁺, NH₄ ⁺) and divalent (Ca²⁺, Mg²⁺) cations on cesium sorption was observed. Desorption experiments showed that 0.1 M potassium chloride is the most suitable desorption agent but the complete desorption of cesium ions from KNiFC-modifed biosorbent was not achieved.     

The kinetics of the reduction of tetraoxoiodate(VII) by <Emphasis Type="Italic">n</Emphasis>-(2-hydroxylethyl)ethylenediaminetriacetatocobaltate(II) ion in aqueous perchloric acid

The stoichiometries, kinetics and mechanism of the reduction of tetraoxoiodate(VII) ion, IO₄ ⁻ to the corresponding trioxoiodate(V) ion, IO₃ ⁻ by n-(2-hydroxylethyl)ethylenediaminetriacetatocobaltate(II) ion, [CoHEDTAOH₂]⁻ have been studied in aqueous media at 28 °C, I = 0.50 mol dm⁻³ (NaClO₄) and [H⁺] = 7.0 × 10⁻³ mol dm⁻³. The reaction is first order in [Oxidant] and [Reductant], and the rate is inversely dependent on H⁺ concentration in the range 5.00 × 10⁻³ ≤ H⁺≤ 20.00 × 10⁻³ mol dm⁻³ studied. A plot of acid rate constant versus [H⁺]⁻¹ was linear with intercept. The rate law for the reaction is:

Polymer supported 5,10,15,20-tetrakis(phenoxy acetic acid)porphyrin derivative for separation and preconcentration of d- and f-electron metals

5,10,15,20-tetrakis(phenoxy acetic acid) porphyrin (PAAP) was covalently linked to Merrifield chloromethylated resin. Characterization of PAAP and the modified polymeric matrix were performed by ¹H NMR, FTIR and elemental analysis. The sorbent was used for the separation and enrichment of the d-electron metals (Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)) at pH 6–8 and of the f-electron metals U(VI) and Th(IV) at pH 4–5. The metals ions were preconcentrated with a concentration factor range of 115–215 and then determined by flame atomic absorption spectrometry or visible spectrophotometry using Arsenazo(III). The retained metals were eluted with 2.0 mol L⁻¹ HNO₃ in the case of the d-electron metals and 0.1/0.25 mol L⁻¹ HCl in the case of the f-electron metals. The procedure was validated by analyzing the NIST standard reference material 2709 (San Joaquin Soil). Correspondence: Melek Merdivan, Chemistry Department, Faculty of Arts and Sciences, Dokuz Eylul University, 35160 Buca, Izmir, Turkey     

Selective solid-phase extraction and separation of trace gold, palladium and platinum using activated carbon modified with ethyl-3-(2-aminoethylamino)-2-chlorobut-2-enoate

Activated carbon was chemically modified with ethyl-3-(2-aminoethylamino)-2-chlorobut-2-enoate to obtain a material for selective solid-phase extraction of trace Au(III), Pd(II) and Pt(IV) prior to their determination by inductively coupled plasma atomic emission spectrometry. Experimental conditions such as effects of pH, shaking time, sample flow rate and volume, elution and interfering ions were studied. The ions Au(III), Pd(II) and Pt(IV) can be quantitatively adsorbed on the new sorbent from solution of pH 1. The adsorbed ions were then eluted with 0.1 mol L^?1 hydrochloric acid and containing 4% thiourea. Many common ions do not interfere. The adsorption capacity of the material is 305, 92, and 126 mg g^?1 for Au(III), Pd(II) and Pt(IV), respectively, and the detection limits are 5, 11 and 9 ng mL^?1. The relative standard deviation is less than 3.0% (n?=?8) under optimum conditions. The method was validated by analyzing two certified reference materials and successfully applied to the preconcentration and determination of these ions in actual samples with satisfactory results.

Complexing of Pd(II) and Pt(II) by dithiooxamide immobilized on SiO2

It is shown that dithiooxamide immobilized on SiO₂ can bind Pd(II) and Pt(II) from aqueous chloride solutions by complexing. Values have been derived for the effective Pd(II) and Pt(II) sorption constants for dithiooxamide immobilized on SiO₂, which represent stronger binding of Pd(II) than Pt(II). L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, Kiev 252039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 34, No. 6, pp. 366–370, November–December, 1998.     

Synthesis of N-Methyl-2-Thioimidazole Resin and Its Complex Behavior for Noble Metal Ions

The functional group capacity and the percentage of functional group conversion of crosslinked polystyrene resin bearing N-methyl-2-thioimidazole (MTIR) synthesized under optimum conditions are as high as 4.08 mmol/g resin and 96.0%, respectively. The apparent activation energies of sorption of MTIR for Au(III) and Pt(IV) are 13.1 and 13.4 kJ/mol, respectively. The sorption behavior of MTIR for Au(III), Pt(IV), and Pd(II) obeys the Freundlich and Langmuir isotherms. The sorption capacities of MTIR for Au(III), Pt(IV), and Pd(II) are as high as 4.33, 2.12, and 2.33 mmol/g resin, respectively. Au(III), Pt(IV), and Pd(II) adsorbed on MTIR can be eluted quantitatively by the eluant. The resin can be regenerated easily and reused without an obvious decrease in the sorption capacity for Au(III) and Pd(II). The resin has high sorption selectivity for noble metal ions. Au(III) can be separated quantitatively in the presence of high concentrations of Cu²⁺, Fe³⁺, Ni²⁺, and Mn²⁺. The recovery of platinum from the spent industrial catalysts is 98.6% by MTIR. The preconcentration and separation of palladium and platinum from the anode deposits of electrolysis of crude copper have been investigated. The resin may have potential industrial uses.     

Impacts of calcium-alginate density on equilibrium and kinetics of lead(II) sorption onto hydrogel beads

Chronic exposure to Pb²⁺ above the 15-μg/L US Environmental Protection Agency action level for drinking water has been shown to cause a host of health problems in humans. Thus, it is important to study new methods available for the treatment and removal of Pb²⁺ from drinking water and wastewater, where elevated levels of heavy metals are found. Alginate-based beads represent one such possible method for heavy metal removal. The impact of alginate density on the equilibrium and kinetics of Pb²⁺ sorption onto hydrogel beads was investigated using Ca-alginate beads ranging from 1% to 8% (w/v) and exposed to Pb²⁺ concentrations ranging from 100 to 1,000 mg/L. When Ca-alginate beads were characterized using Fourier transform infrared analysis, the carboxylic acid groups of the mannuronate and guluronate residues in alginate were the primary functional groups that interacted with Pb²⁺. Hydration of Ca-alginate beads was also examined and found to decrease as Ca-alginate density increased. A positive correlation was observed between Ca-alginate hydration and Pb²⁺ sorption. Sorption of Pb²⁺ was fast, reaching equilibrium after approximately 4 h, and is well described by the Langmuir adsorption isotherm. Maximum sorption capacities for 1%, 4%, and 8% beads were 500 ± 100, 360 ± 30, and 240 ± 20 mg/g (dry weight), respectively. The kinetics of sorption were best described by the pseudo-second-order Lagergren model, with rate constants determined as 3.2 ± 0.1 × 10⁻⁴, 1.0 ± 0.1 × 10⁻⁴, and 1.6 ± 0.1 × 10⁻⁴ g mg⁻¹ min⁻¹ for 1%, 4%, and 8% beads, respectively.     

Selective solid-phase extraction of trace Au(III), Pd(II) and Pt(IV) using activated carbon modified with 2,6-diaminopyridine

A new sorbent was prepared by immobilization of 2,6-diaminopyridine on activated carbon and then used as a solid-phase extractant for trace Au(III), Pd(II) and Pt(IV) before their determination by ICP-AES. Effects of pH, the shaking time, the sample flow rate and volume, the elution condition and the potentially interfering ions were investigated. The optimum pH value is 1. The maximum static adsorption capacity for the three ions is 202.7, 38.5 and 30.1?mg?g^?1, respectively. The adsorbed metal ions can be completely eluted by 2?mL of the eluent solution that contains 0.05?mol?L^?1 HCl and 5% thiourea. Common other ions do not interfere. The detection limits (3??) are 0.16, 0.33 and 0.29?ng?mL^?1, respectively. The relative standard deviation (RSD) was lower than 3.0% (n?=?8). The new sorbent was applied to the preconcentration of the three ions in ore and rock samples with satisfactory results.

Reactions of chiral phosphoramidites with complexes Pd(COD)Cl2 and Pt(COD)Cl2

Reactions of phosphoramidites based on (−)-ephedrine and [(1S)-endo]-(−)-borneol with the complexes M(COD)Cl₂ (M is Pd or Pt, and COD is cycloocta-1,5-diene) were studied. The formation ofcis andtrans complexes of the general formulas MCl₂L₂ and M₂Cl₂(μ-Cl)₂L₂ was observed. The structures of the resulting compounds were established by³¹P,¹³C, and¹⁹⁵Pt NMR and IR spectroscopy and by plasma desorption mass spectrometry. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1627–1630, August, 1998.     

Preparation of morin modified nanometer SiO<Subscript>2</Subscript> as a sorbent for solid-phase extraction of trace heavy metals from biological and natural water samples

Morin was successful as a chemical modifier to improve the reactivity of the nanometer SiO₂ surface in terms of selective binding and extraction of heavy metal ions. This new functionalized nanometer SiO₂ (nanometer SiO₂-morin) was used as an effective sorbent for the solid-phase extraction (SPE) of Cd(II), Cu(II), Ni(II), Pb(II), Zn(II) in solutions prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of trace levels of metal ions were optimized with respect to different experimental parameters using static and dynamic procedures in detail. The pH 4.0 was chosen as the optimum pH value for the separation of metal ions on the newly sorbent. Complete elution of the adsorbed metal ions from the nanometer SiO₂-morin was carried out using 2.0 mL of 0.5 mol L⁻¹ of HCl. Common coexisting ions did not interfere with the separation and determination at pH 4.0. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 22.36, 36.8, 40.37, 33.21 and 25.99 mg metal/g SiO₂-morin for Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), respectively. The time for 95% sorption for Cu(II) and Ni(II) and 70% sorption for Cd(II), Pb(II) and Zn(II) was less than 2 min. The relative standard deviation (RSD) of the method under optimum conditions was lower than 5.0% (n = 11). The procedure was validated by analyzing the certified reference river sediment material (GBW 08301, China), the results obtained were in good agreement with standard values. The nanometer SiO₂-morin was successfully employed in the separation and preconcentration of trace Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) from the biological and natural water samples yielding 75-folds concentration factor.