Metal Sorption,Solid Phase Extraction and Preconcentration Properties of Two Silica Gel Phases Chemically Modified with 2-Hydroxy-1-Naphthaldehyde

Active silica gel phase (I) was chemically modified to the corresponding amino- (SiNH₂) and chloro- (SiCl) derivatives via silylation reactions. These were used to synthesize two newly modified silica gel phases (II, III) by direct chemical reaction with 2-hydroxynaphthaldehyde (2-HNA). The surface coverage values are 370, 432µmolg^–1 and 320, 355µmolg^–1 for (II) and (III), on the basis of thermal desorption and metal probe testing method, respectively. The metal sorption properties of silica gel phases (II, III) were studied and compared with active silica gel phase (I). The maximum determined metal capacity values were found to be 10–110, 20–290 and 20–370µmolg^–1 for phases I, II and III, respectively. The distribution coefficient values (K_d) were also determined for a series of metal ions, and the results showed that the two new chemically modified phases (II and III) were highly selective for Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺ and Pb²⁺. The potential applications of silica gel phases (II, III) as solid phase extractors for the same five metal ions spiked in drinking tap water (1.000µgmL^–1) were found to give percentage recovery values in the range of 90.2–96.3±4.1–6.3%, while pre-concentration of the same five metal ions spiked in drinking tap water (50.0ngmL^–1) was successfully accomplished with a percentage recovery range of 92.6–95.8±4.8–5.7%.Received December 16, 2002; accepted May 14, 2003 published online September 1, 2003     

Determination of Some Metal Ions in Aquatic Environs by Atomic Absorption Spectrometry after Concentration with Modified Silica

The uptake behavior of porous silica modified with N‐propylsalicylaldimine (IE11) for Cd(II), Cr(III), Cu(II), Mn(II) and Pb(II) metal ions were studied. The Log k_d values were found to be within the range 2.19–5.16 depending on pH and time of stirring. IE11 was used in the separation and preconcentration of Cd(II), Cr(III), Cu(II), Mn(II) and Pb(II) from some natural water samples. The data were compared with those obtained by the solvent extraction method (APDC/MIBK). The method was found to be accurate and precise and not subject to random error.     

用3,6-双[(2-胂羧基苯)偶氮]-4,5-二羟基-2,7-萘二磺酰苯胺改性硅胶富集、分离痕量元素的研究

本文介绍了3,6-双[(2-胂羧基苯)偶氮]-4,5-二羟基-2,7-萘二磺酰苯胺(偶氮胂-DAL)改性硅胶的制备方法,研究了它的性质及其富集,分离Ti(Ⅳ),Zr(Ⅳ)、Hf(Ⅳ)的工作。研究结果表明,偶氮胂-DAL改性硅胶在6mol/L HClpH4.0的溶液中是稳定的;其对Zr(Ⅳ)的最大吸附量为20.9μmol/g;在1mol/L HCl介质中,经偶氮胂-DAL-SG柱预富集处理后,可将Zr(Ⅳ)、Hf(Ⅳ)与Ti(Ⅳ)、贵金属、常见过渡元素,稀土元素等金属离子直接分离,用普通分光光度法测定人工水样中Zr(Ⅳ)的下限可达10~(-9)g/g。     

镉试剂2B改性硅胶富集和测定水体中的镉

报道了用镉试剂２Ｂ改性的硅胶来富集水体中的痕量镉的各种条件。结果表明,在ＰＨ＝６的条件下,Ｃｄ＾２＋能被Ｃａｄｉｏｎ２Ｂ－ＳＧ定量吸附,其净吸队坦为７．９μｍｏｌ．ｇ＾－１,吸附的Ｃｄ＾２＋可被０．１ｍｏｌ．Ｌ＾－１的ＨＣｌ洗脱。     

Silica Gel Loaded with <Emphasis Type="Italic">o</Emphasis>-Dihydroxybenzene: Design,Metal Sorption Equilibrium Studies and Application to Metal Enrichment Prior to Determination by Flame Atomic Absorption Spectrometry

The aminopropyl silica gel (APSG) prepared by reaction of activated silica gel with 3-aminopropyltriethoxysilane on reaction with 3,4-dihydroxybenzaldehyde has resulted in a new chelating matrix, o-dihydroxybenzene (DHB) anchored silica gel, which is characterized by IR, TGA and elemental analyses. APSG is characterized with ¹³C CPMAS NMR spectroscopy. DHB anchored silica gel sorbs quantitatively (97.4–99.2% recovery) Cu(II), Pb(II), Fe(III), Zn(II), Co(II), Ni(II) and Cd(II) at pH 6.0–7.5, 5.0–7.0, 5.5–7.0, 6.0–8.0, 6.5–8.0, 5.5–7.0 and 6.5–7.5, respectively. The sorption capacity varies from 32 to 348µmolg^–1 and is highest for copper. Desorption was found to be quantitative with 1.0–3.0molL^–1 HCl/HNO₃ (for Pb). The optimum flow rate of the solution for quantitative sorption of metal ions on a column (10cm×10mm) packed with 1g of the modified silica gel is 1.0–4.0mLmin^–1, whereas for desorption it is 2.0 –4.0mLmin^–1. The tolerance limits for NaCl, NaBr, NaI, NaNO₃, Na₂SO₄, Na₃PO₄, humic acid, EDTA, ascorbic acid, citric acid, sodium tartrate, Ca(II) and Mg(II) in the sorption of all the seven metal ions are reported. The preconcentration factors are between 100 and 300 and t_1/2 values 17min. The present matrix coupled with FAAS has been used to enrich and determine the seven metal ions in river and tap water samples (RSD 1.4–7.0%) and in synthetic certified water samples SLRS-4 (NRC, Canada) with an RSD of 2.73–2.83%. The cobalt present in pharmaceutical vitamin tablets and Zn in milk powder was preconcentrated on DHB anchored silica gel and determined by FAAS (RSD of 2.00 to 2.72%).     

Preconcentration and Separation of Trace Amounts of Strontium Ions from Alkali and Alkaline Earth Metal Ions Using Octadecyl Silica Membrane Disks Modified with Decyl-18-Crown-6 and Its Determination by Flame Atomic Absorption Spectrometry

 A simple and reliable method for rapid and selective separation of trace amounts of Sr²⁺ ions from alkali and alkaline earth metal ions by using octadecyl silica membrane disks modified with decyl- 18-crown-6 in the presence of 1.0 × 10⁻³ M picric acid is presented. The influence of picric acid concentration, flow rates and nature and amount of the stripping acid have been investigated. Maximum capacity of the membrane disks modified with 10 mg of the macrocycle was found to be 484 μg of Sr²⁺ ions. The proposed method permitted enrichment factors of about 80 and higher. The limit of detection of the proposed method is 1.5 μg per 1000 ml. The method was successfully applied to the recovery of Sr²⁺ ions from different synthetic and water samples. Received August 10, 2000. Revision April 17, 2001.     

Determination of Trace Amounts of Cobalt in Natural Water Samples as 4-(2-Thiazolylazo) Recorcinol Complex After Adsorptive Preconcentration

ABSTRACT

A chromatographic method has been established for the determination of trace amounts of cobalt by preconcentration on Amberlite XAD-16 resin as cobalt/4-(2-Thiazolylazo) resorcinol (TAR) complexes. The conditions (e.g. pH, resin amounts, matrix ions) affecting the recovery of cobalt from aqueous solution were studied. The method has been employed for the determination of cobalt in natural water samples.     

双硫腙修饰纳米TiO2分离富集石墨炉原子吸收光谱法测定水样中痕量金属离子

建立了双硫腙修饰纳米TiO2分离富集-石墨炉原子吸收光谱法测定水样中痕量镉、铬和铅的新方法,优化了纳米TiO2-双硫腙对试样中这3种痕量物质的吸附和解吸条件。结果表明,在pH 5.0时,镉、铬和铅可被定量吸附,静态饱和吸附容量分别为13.3、5.5、21.8 mg/g。吸附的各种金属离子可用5 mL 0.1mol/L的硝酸完全洗脱。该方法对Cd2+、Cr3+和Pb2+的检出限(3σ,n=11)分别为0.18、0.51、1.92 ng/L,相对标准偏差分别为2.8%、2.3%和1.0%,加标回收率为96%～101%。该方法已成功应用于环境水样中镉、铬和铅的测定。     

2-氨基-5-硝基吡啶在基体辅助激光解吸/电离质谱法测定核酸分子中的应用

报道以2-氨基-5-硝基吡啶为基体用基体辅助激光解吸/电离质谱法(MALDI-MS)对DNA样品进行测定并研究它们的激光质谱特征,结果表明,2-氨基-5-硝基吡啶是DNA的一高效基体.用柠檬酸铵和NH_4~+阳离子交换树脂除去试剂和样品中的碱金属离子,能显著地提高解吸/电离DNA分子的效率.     

Determination of La,Eu and Yb in Water Samples by Inductively Coupled Plasma Atomic Emission Spectrometry After Solid Phase Extraction of Their 1-Phenyl-3-Methyl-4-Benzoylpyrazol-5-one Complexes on Silica Gel Column

A simple preconcentration method has been developed for the determination of trace amounts of rare earth elements (La, Eu, and Yb) in natural water samples by inductively coupled plasma atomic emission spectrometry (ICP-AES). Preconcentration of La, Eu, and Yb was achieved by sorption of their 1-phenyl-3-methyl-4-benzoylpyrazol-5-one (PMBP) complexes on a silica gel column at pH 5 and then eluting with 1.0molL^–1 HNO₃. For the preconcentration of 100mL of aqueous solution, an enrichment of 100 was obtained for all analytes, and the detection limits for La, Eu and Yb were 82, 34 and 45ngL^–1, respectively. The accuracy of this method was demonstrated by analyzing a standard reference material. The method has been successfully applied to the determination of La, Eu and Yb in lake water and synthetic seawater.     

Determination of Antimony in Waters by Electrothermal Atomic Absorption Spectrometry with Preconcentration on a Tantalum Wire

 A preconcentration method for antimony in waters involving adsorption on a tantalum wire, followed by electrothermal atomic absorption spectrometry with a tungsten tube atomizer is described. The best pH for the adsorption of antimony was 2. The optimal immersing time was 120 s. Under the optimal conditions, the detection limit for antimony by the tantalum wire preconcentration method was 50 pg/mL (3S/N) and the relative standard deviation was 9.4%. The effects of large amounts of concomitants on the preconcentration of antimony were evaluated. Even though 10³–10⁴ fold excess of matrix elements existed in water, the antimony response was not significantly affected by the matrix elements. The method with preconcentration on a tantalum wire was applied to the determination of antimony in waters and proved to be sensitive, simple, and convenient. This adsorption method can be utilized in in-situ sampling of ultra-trace antimony in environmental samples (water). Furthermore, after sampling it is easy to carry and store the tantalum wire without contamination for a long time. The technique developed was shown to be useful for the determination of Sb in waste waters at the 1–5 μg/L level. Received March 20, 2002; accepted June 26, 2002     

Voltammetric Determination of Bismuth in Water and Nickel Metal Samples with a Sodium Montmorillonite (SWy-2) Modified Carbon Paste Electrode

A simple and reliable electrochemical method for the determination of bismuth in water and nickel metal samples using a sodium montmorillonite (SWy-2) modified carbon paste electrode was described. Due to its strong cation-exchange ability and adsorptive characteristics, SWy-2 significantly enhances the sensitivity of determination for Bi³⁺. Bi³⁺ is firstly preconcentrated and then reduced on the modified electrode surface at –0.50V. After that, reduced bismuth is stripped from the electrode surface during the positive potential sweep of –0.50V to 0.20V, and a well-defined stripping peak at –0.12V appears. The stripping peak current is proportional to the concentration of Bi³⁺ from 4×10^–9molL^–1 to 1×10^–6molL^–1. The detection limit (signal-to-noise=3) is 1×10^–10molL^–1 after 5min. accumulation. The proposed method was successfully applied to the determination of bismuth in water and nickel metal samples.     

Determination of Some Heavy Metal Ions with a Carbon Paste Electrode Modified by Poly(glycidylmethacrylate‐methylmethacrylate‐divinylbenzene) Microspheres Functionalized by 2‐Aminothiazole

A carbon paste electrode modified with 2‐aminothiazole functionalized poly(glycidylmethacrylate‐methylmethacrylate‐divinylbenzene) microspheres was used for trace determination of mercury, copper and lead ions. After the open‐circuit accumulation of the heavy metal ions onto the electrode, the sensitive anodic stripping peaks were obtained by square wave anodic stripping voltammetry (SWASV)). Many parameters such as the composition of the paste, pH, preconcentration time, effective potential scan rate and stirring rate influence the response of the measurement. The procedures were optimized for most sensitive and reliable determinations of the desired species. For a 10‐min preconcentration time in synthetic solutions at optimum instrumental and experimental conditions, the detection limit (LOD) was 12.3, 2.8 and 4.5 μg L^?1 for mercury, copper and lead, respectively. The limits of detection may be enhanced by increasing the preconcentration time. For example, LOD of mercury and copper was 4.9 and 1.0 μg L^?1 for fifteen minutes preconcentration time. The sensitivity may also considered to be increased by using a more suitable electrode composition targeting the more conductive electrode with lesser amount of modified polymer for sub‐μg L^?1 levels of heavy metal ions. The optimized method was successfully applied to the determination of copper in tap water and waste water samples by means of standard addition procedure. The copper content found was comparable with the certified concentration of the waste water sample. The calibration plots for mercury and lead spiked real samples were also drawn.     

Pyrogallol Immobilized Amberlite XAD-2: A Newly Designed Collector for Enrichment of Metal Ions Prior to their Determination by Flame Atomic Absorption Spectrometry

 Pyrogallol is covalently linked with the benzene ring of Amberlite XAD-2, through an azo (–N=N–) spacer group and the resulting new polymer characterized by elemental analyses, thermogravimetric analysis (TGA) and infrared (IR) spectra. It has been used for separation and preconcentration of Cu(II), Cd(II), Co(II), Ni(II), Pb(II), Zn(II), Mn(II), Fe(III) and U(VI) prior to their determination by flame atomic absorption spectrometry (FAAS) or fluorimetry (for U(VI) only). The pH ranges for quantitative sorption are 5.5–6.5, 5.5–7.5, 5.5–7.0, 5.5–7.0, 5.5–6.5, 5.5–6.5, 5.5–8.0, 5.5–6.2 and 5.5–6.2, respectively, for the nine metal ions, which can be desorbed (recovery 90–99%) with 4 mol L⁻¹ HNO₃ or HCl. The sorption capacity of the resin has been found to be in the range 4.10 to 6.71 mg of metal g⁻¹ of dry resin. The loading half time (t_1/2) was ≤3.3 min for all the metal ions. The effects of NaF, NaCl, NaNO₃, Na₂SO₄, and Na₃PO₄ on the sorption of these metal ions (0.2 μg mL⁻¹) are reported. The Ca(II) and Mg(II) are tolerable up to a concentration level of 40–400 and 25–240 μg mL⁻¹, respectively. The enrichment factor for Cu(II), Cd(II), Co(II), Ni(II), Pb(II), Zn(II), Mn(II), Fe(III) and U(VI) has been found to be 65, 40, 65, 120, 25, 160, 120, 140, and 70 (concentration level 2–25 ng mL⁻¹), respectively. The limit of detection for these nine metal ions is 5.0, 1.3, 5.0, 4.0, 25.0, 0.5, 1.0, 2.0 and 1.0 ng mL⁻¹, respectively. After enrichment on the present matrix, the flame AAS method has been applied to determine these metal ions (except U) in river water samples (RSD ≤ 7%) and well water (RSD ≤ 8%). Uranium present in well water samples has been enriched on the present matrix and determined by a fluorimetric method (RSD ≤ 6%). The cobalt present in pharmaceutical vitamin tablets was also preconcentrated with the aid of the present chelating resin and determined by FAAS to be 1.93 μg g⁻¹ (RSD ∼4%). Received May 16, 2000. Revision April 3, 2001.     

Column Solid-Phase Extraction with 2-Acetylmercaptophenyldiazoaminoazobenzene (AMPDAA) Impregnated Amberlite XAD-4 and Determination of Trace Heavy Metals in Natural Waters by Flame Atomic Absorption Spectrometry

A column solid-phase extraction (SPE) preconcentration method was developed for the determination of Cd, Co, Cu, Ni and Zn ions in natural water samples by flame atomic absorption spectrometry. The procedure is based on the retention of analytes in the form of 2-acetylmercaptophenyldiazoaminoazobenzene (AMPDAA) complexes on a short column of AMPDAA-XAD-4 resin from buffered sample solution and subsequent elution with hydrochloric acid plus sodium chloride. Important SPE parameters were optimized using model solutions. The loading half-time, t_1/2, for Cd, Co, Cu and Zn was found to be less than 5min, and for Ni the value was 12min. The detection limit for Cd, Co, Cu, Ni and Zn was 0.028, 0.064, 0.042, 0.023 and 0.16µgL^–1, respectively, and the quantification limit was 0.043, 0.11, 0.099, 0.044 and 0.29µgL^–1, respectively. The AMPDAA-XAD-4 resin has good selectivity for Cd, Co, Cu, Ni and Zn over several electrolytes, especially over earth alkaline metals with tolerance limits of 0.05molL^–1. The method was validated by analysing a standard reference material (GBW 08301), and it was found that the results agree with those quoted by the manufactures. The developed method was applied to the determination of trace metal ions in tap water and river water samples with satisfactory results.     

Determination of very low levels of dissolved mercury(II) and methylmercury in river waters by continuous flow with on-line UV decomposition and cold-vapor atomic fluorescence spectrometry after pre-concentration on a silica gel-2-mercaptobenzimidazol sorbent

A new, simple and sensitive method for the simultaneous determination of mercury(II) and methylmercury chloride at sub-ng l⁻¹ levels in river waters is described. Inorganic and organic mercury were preconcentrated from fresh water samples simultaneously on a laboratory-made column containing 2-mercaptobenzimidazol loaded on silica gel and then quantitatively eluted with 0.05 M KCN solution and 2.0 M HCl to desorp inorganic and methylmercury species, respectively. After irradiation with an intensive UV source, MeHg⁺ was decomposed and mercury vapours were generated from inorganic and organic mercury using an acidic SnCl₂ solution in a continuous flow system and were subsequently determined with a cold vapour atomic fluorescence (CV-AFS) spectrometer. Detection limits (3σ) were 0.07 and 0.05 ng l⁻¹ (as Hg) for mercury(II) chloride and methylmercury chloride, respectively. Relative standard deviations of method (%R.S.D.) were 8.8 and 10 for inorganic and organomercuric species in the river water, respectively. The analysis of real samples, taken from different rivers, showed that inorganic mercury levels ranged from 4.0±0.6 to 12±1 ng l⁻¹ (as Hg and 95% confidence limit) and methylmercury levels at 0.2±0.02 ng l⁻¹(as Hg).     

A Newly Competitive Electrochemical Sensor for Sensitive Determination of Chrysin Based on Electrochemically Activated Ta2O5 Particles Modified Carbon Paste Electrode

A novel electrochemically activated doped Ta₂O₅ particles modified carbon paste electrode (EA‐Ta₂O₅‐CPE) was prepared and applied for selective and sensitive determination of chrysin. X‐ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) techniques and cyclic voltammetry (CV) were used to characterize the Ta₂O₅ particles and investigate the electrochemical response of the sensor. Compared with bare CPE, the doped Ta₂O₅ modified electrode got much more porous by electrochemical treatment and exhibited larger effective surface area, more reactive site and excellent electrochemical catalytic activity toward the oxidation of chrysin. Under optimum conditions by LSV, the oxidation peak currents responded to chrysin linearly over a concentration range from 5.0×10⁻⁸ to 7.0×10⁻⁶ mol L⁻¹ with a detection limit of 2.0×10⁻⁸ mol L⁻¹ (5.08 ng mL⁻¹). The fabricated sensor showed anti‐interference ability against the biological common interferents (i.e. baicalein, baicalin) and provided to be reliable for the determination of chrysin in Chinese medicinal herb Oroxylum indicum and chrysin capsules samples with satisfactory results.     

Estimation of C2−C5 hydrocarbons in air by pre-concentration on silica gel at dry ice temperature

Summary A short stainless steel column packed with silica gel is cooled to –78°C and atmospheric hydrocarbons are preconcentrated from 3 I of air on it. Desorption to the analytical column is by heating for 10 min to 200°C. Analysis is by GC on OPN-Poracil C at 27°C. The sorption efficiencies were nearly 100% for most of the light hydrocarbons.     

Electrocatalysis of Puerarin on a Nano-CeO2/MWCNTs Composite Modified Electrode and Its Determination in Pharmaceutical Preparations

A good route for the fabrication of CeO₂ nanoparticles (nano‐CeO₂)/multi‐walled carbon nanotubes (MWCNTs) modified glassy carbon electrodes (GCE) was proposed. MWCNTs are used to immobilize nano‐CeO₂. What′s more, with the addition of the MWCNTs, the agglomeration level of CeO₂ nanoparticles can be reduced, the extremely large surface area can be obtained and the electron transfer rate can be increased. The morphological characterization of nano‐CeO₂/MWCNTs was examined by scanning electron microscopy (SEM). The performances of the nano‐CeO₂/MWCNTs/GCE were characterized with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and typical amperometric response (i‐t). The potential utility of the constructed electrodes was demonstrated by applying them to the analytical determination of puerarin concentration. The catalytic oxidation of puerarin has a better result on nano‐CeO₂/MWCNTs/GCE because of the synergistic effect of nano‐CeO₂ and MWCNTs. An optimized limit of detection of 8.0×10^?9 mol/L was obtained at a signal‐to‐noise ratio of 3 and with a fast response time (within 3 s). Additionally, the nano‐CeO₂/MWCNTs/GCE exhibited a wide linear range from 0.04 to 6.0 μmol/L and high sensitivity.     

Determination of trace heavy metals in waters by flame atomic absorption spectrometry after preconcentration with 2,4-dinitrophenyldiazoaminoazobenzene on Amberlite XAD-2

A new column, solid-phase extraction (SPE), preconcentration method was developed for determination of Cd, Co, and Cu ions in natural water samples by flame atomic absorption spectrometry. The procedure is based on the retention of analytes in the form of 2,4-dinitrophenyldiazoaminoazobenzene (DNDAA) complex on a mini column of DNDAA-XAD-2 resin. The effects of pH, eluent type, eluent concentration, eluent volume, resin quantity, sample volume, sample flow rate, and matrix ions (Na, Ca, and Mg) were investigated on the recovery of the metals using model solutions. The detection limit for Cd, Co, and Cu was 0.062, 0.084, and 0.057 μg L⁻¹ and the quantification limit was 0.17, 0.24, and 0.12 μg L⁻¹ respectively. The method was validated by the analysis of a certified reference material with the results being in agreement with those quoted by manufactures. The developed method was applied to the determination of trace metal ions in tap water, river water samples with satisfactory results.