Selective preconcentration of trace thorium from aqueous solutions with Th(IV)-imprinted polymers prepared by a surface-grafted technique

A novel ion-imprinted adsorbent for selective solid phase extraction of thorium(IV) based on the surface of silica gel was prepared by a surface-grafted technique with methacrylic acid (MAA) as a functional monomer. After removal of Th(IV) ions with 3?mol?L^?1 HCl solution, the obtained imprinted particles for Th(IV) exhibited specific recognition and relatively rapid kinetic process. The maximum static and total dynamic adsorption capacity of the ion-imprinted polymers (IIPs) for Th(IV) was 33.2 and 17.3?mg?g^?1, respectively. A comparison of the selectivity coefficient of the imprinted polymers with that of non-imprinted polymers showed that the imprinted matrix for Th(IV)/U(VI), Th(IV)/Ce(III), Th(IV)/La(III) and Th(IV)/Zr(IV) was 58.8, 107, 106.4 and 151.7 times greater than non-imprinted matrix, respectively. With a series of samples loading flow rate of 3?mL?min^?1 for preconcentration, an enrichment factor of 14.6 and the detection limit of 0.59?µg?L^?1 were obtained. The relative standard deviation of the method under optimum conditions was 2.1% (n?=?7). The developed method was successfully applied to the determination of trace Th(IV) in real water samples with satisfactory results.     

Synthesis and characterization of an ion-imprinted polymer for selective solid phase extraction of thorium(IV)

A new surface ion-imprinted composite polymer containing 3-methyl-1-phenyl ?4-(cis-acylbutenoic acid)-2-pyrazolin-5-one as the functional reagent is presented that is capable of extracting and preconcentrating traces of Th(IV) ion prior to its photometric determination. Parameters affecting the recovery of Th(IV) such as acidity, shaking time, initial concentration of Th(IV), elution condition, sample flow rate, and influence of potentially interfering ions were investigated. The maximum uptake capacity of this material and that of the non-imprinted polymer at pH 4.5 are 56.8 and 26.3?mg?g^?1, respectively. Recovery exceeds 95% and is complete within 5?min. A Langmuir isotherm fits the experimental data. The relative selectivity factor for Th(IV)/U(VI), Th(IV)/La(III), and Th(IV)/Ce(III) are 50.8, 78.3, and 82.6, respectively. The relative standard deviation is <2.5%, the detection limit is 0.54???g?L^?1 (3??). The imprinted polymer was coupled to spectrophotometry to separate and determine trace levels of Th(IV) in a soil standard material with satisfactory results.

A Ce3+-imprinted functionalized potassium tetratitanate whisker sorbent prepared by surface molecularly imprinting technique for selective separation and determination of Ce3+

A surface molecular imprinting technology was developed to adsorb Ce(III) ions that showed much higher adsorption affinity and selectivity for than for other metal ions. The batch adsorption process was studied with respect to effects of pH value, residence time, temperature, and initial concentration of Ce(III) ion. The maximum adsorption capacity is 43 mg g^?1 at an initial Ce(III) concentration of 300 mg L^?1 and at a sorbent dosage of 1.0 g L^?1. A Langmuir isotherm fits the experimental data. The imprinted sorbent exhibits a much higher separation and selectivity for the target imprinted ion than the non-imprinted polymer. Cerium ion can be desorbed with 1M hydrochloric acid solution which is also proven by scanning electron microoscopy and X-ray diffraction experiments. The limit of detection is 37 ng mL^?1. The sorbent has been applied to the determination of trace cerium in different environmental samples with satisfactory results.     

Determination of antimony(III) and (V) in natural water by cathodic stripping voltammetry with in-situ plated bismuth film electrode

A method is described for the sequential determination of Sb(III) and Sb(V) using Osteryoung square wave cathodic stripping voltammetry. It employs an in-situ plated bismuth-film on an edge-plane graphite substrate as the working electrode. Selective electro-deposition of Sb(III)/Sb(V) is accomplished by applying a potential of ?500 mV vs. Ag/AgCl, followed by reduction to stibine at a more negative potential in the stripping step. Stripping was carried out by applying a square wave waveform between ?500 and ?1400 mV to the antimony deposited. The stripping peak current at ?1150 mV is directly proportional to the concentration of Sb( III)/Sb(V). The calibration plots for Sb (III) were linear up to 12.0?µg L^?1 depending on the time of deposition. The calibration plots for Sb (V) were linear up to 7.0?µg L^?1, also depending on the time of deposition. The relative standard deviation in the determination of 0.1?µg L^?1 of Sb(III) is 4.0% (n?=?5), and the limit of detection is as low as 2 ng L^?1. In case of 0.1?µg L^?1 Sb(V), the relative standard deviation is 3.0% (n?=?5) and the detection limit also is 2 ng L^?1. The method was applied to the analysis of river and sea water samples.     

Preparation and evaluation of an ion imprinted sol–gel material for selective solid-phase extraction of Ni(II)

An ion imprinted silica sorbent was prepared using a sol–gel process for selective extraction of Ni(II) ions from water samples. Bis(dibenzoylmethanto)nickel(II) complex was used as template; phenyltrimethoxysilane and 3-aminopropyltriethoxysilane as functional monomers and tetraethylorthosilicate as reticulating agent. The material was packed in solid-phase extraction (SPE) column. The effect of sampling volume, elution conditions, sample pH and sample flow rate on the extraction of Ni ions from water samples were studied. The relative selectivity coefficients of imprinted sorbent for Ni(II)/Co(II), Ni(II)/Cu(II) and Ni(II)/Cd(II) were 23.7, 30.3 and 24.4, times greater than non-imprinted sorbent, respectively. The relative standard deviation of the eight replicate determinations of Ni(II) was 4.2%. The detection limit was 0.9 µg L^?1 using flame atomic absorption spectrometry. The developed method was successfully applied to the determination of trace nickel in water samples.     

Determination of chromium(III) and total chromium in natural waters using a surface ion-imprinted silica gel as selective adsorbent

A sensitive and selective method has been developed to determine Cr(III) and total Cr in natural water samples by ICP-AES with a Cr(III)-imprinted aminopropyl-functionalised silica gel adsorbent. The Cr(III)-imprinted and non-imprinted adsorbent were prepared by an easy one-step reaction with a surface imprinting technique. Their maximum static adsorption capacities for Cr(III) were 11.12 mg g^?1 and 3.81 mg g^?1, respectively. The relative selectivity factors (α _r) for Cr(III)/Co(II), Cr(III)/Au(III), Cr(III)/Ni(II), Cr(III)/Cu(II), Cr(III)/Zn(II), and Cr(III)/Cr(VI), were 377, 21.4, 15.4, 27.7, 26.4, and 31.9, respectively. Under the optimal conditions, Cr(III) can be absorbed quantitatively, but Cr(VI) was not retained. Total chromium was obtained after reducing Cr(VI) to Cr(III) with hydroxyammonium chloride. The detection limit (3σ) for Cr(III) was 0.11 ng mL^?1. The relative standard deviation was 1.2%. The proposed method has been validated by analysing two certified reference materials and successfully applied to the determination and speciation of chromium in natural water samples with satisfactory results.     

Novel Imprinted Polymer for the Preconcentration of Cadmium with Determination by Inductively Coupled Plasma Mass Spectrometry

A novel Cd(II)-imprinted polymer was prepared with chemical immobilization using N-methacryloyl-L-Histidine as a vinylated chelating agent for online solid-phase extraction of Cd(II) for determination by inductively coupled plasma mass spectrometry. The Cd(II)–monomer complex was synthesized and copolymerized through bulk polymerization method in the presence of ethyleneglycoldimethacrylate cross-linker. The resulting polymer was leached with 1.0?mol?L^?1 HNO₃ to generate the cavities in the polymer for Cd(II) ions. The experimental conditions, including load pH, solution flow rate, and eluent concentration for effective sorption of Cd(II), were optimized using a minicolumn of the imprinted polymer. A volume of 5.0?mL sample 5?µg?L^?1 Cd(II) solution at pH 6.5 was loaded on the column at 2.0?mL?min^?1 using a sequential injection system followed by elution with 1.0?mL of 0.75?mol?L^?1 HNO₃. The relative selectivity coefficients of the imprinted polymer for Cd(II) were 38.5, 3.5, 3.0, 2.5, and 6.0 in the presence of Cu(II), Ni(II), Zn(II), Co(II), and Pb(II), respectively. Computational calculations revealed that the selectivity of the imprinted polymer was mediated by the stability of Cd(II)–N-methacryloyl-L-Histidine complex which was more stable than commonly used monomers including 4-vinyl pyridine, methacrylic acid, and vinylimidazole. The detection limit and relative standard deviation were 0.004?µg?L^?1 and 3.2%, respectively. The method was validated by the analysis of seawater certified reference material (CASS-4) and successfully used for the determination of Cd(II) in coastal seawater and estuarine water.     

Solid-phase extraction of iron(III) with an ion-imprinted functionalized silica gel sorbent prepared by a surface imprinting technique

A new Fe(III)-imprinted amino-functionalized silica gel sorbent was prepared by a surface imprinting technique for selective solid-phase extraction (SPE) of Fe(III) prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES). Compared with non-imprinted polymer particles, the ion-imprinted polymers (IIPs) had higher selectivity and adsorption capacity for Fe(III). The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Fe(III) was 25.21 and 5.10 mg g⁻¹, respectively. The largest selectivity coefficient of the Fe(III)-imprinted sorbent for Fe(III) in the presence of Cr(III) was over 450. The relatively selective factor (α_r) values of Fe(III)/Cr(III) were 49.9 and 42.4, which were greater than 1. The distribution ratio (D) values of Fe(III)-imprinted polymers for Fe(III) were greatly larger than that for Cr(III). The detection limit (3σ) was 0.34 μg L⁻¹. The relative standard deviation of the method was 1.50% for eight replicate determinations. The method was validated by analyzing two certified reference materials (GBW 08301 and GBW 08303), the results obtained is in good agreement with standard values. The developed method was also successfully applied to the determination of trace iron in plants and water samples with satisfactory results.     

Determination of total antimony(III,V) by square-wave anodic stripping voltammetry with in situ plated bismuth-film electrode

A sensitive and reliable method is described for the determination of total Sb(III,?V) at traces levels by Osteryoung square-wave anodic stripping voltammery (OSWASV). This method is based on the co-deposition of Sb(III,?V) with Bi(III) onto an edge-plane pyrolytic graphite substrate at an accumulation step. OSWASV studies indicated that the co-deposited antimony was oxidised with anodic scans to give an enhanced anodic peak at about 450?mV vs. Ag/AgCl (sat. KCl). The anodic stripping peak current was directly proportional to the total concentration of antimony in the ranges of 0.01–0.10?µg?L^?1, 0.10–1.0?µg?L^?1 and 1.0–18.0?µg?L^?1 with correlation coefficient higher than 0.995 when 2.0?mol?L^?1 hydrochloric acid was used. The detection limits calculated as S/N?=?3 was 5.0?ng?L^?1 in 2.0?mol?L^?1 hydrochloric acid at 180?s deposition time. The relative standard deviation was 5% (n?=?6) at 0.10?µg?L^?1 level of antimony. The analytical results demonstrate that the proposed method is applicable to analyses of real water samples.     

Development of carbon paste electrode modified with cadmium ion-imprinted polymer for selective voltammetric determination of Cd2+

A simple and fast voltammetric method based on a new electrode composed of carbon paste electrode/bifunctional hybrid ion imprinted polymer (CPE/IIP) was developed for the quantification of Cd²⁺ in water samples. The voltammetric measurements by Differential Pulse Voltammetry were performed by using CPE containing 11.0 mg of IIP under phosphate buffer solution at concentration 0.1 mol L^?1 and pH 6.5. The electrochemical method was carried out by Cd²⁺ preconcentration at ?1.2 V during 210 s, followed by anodic stripping. The performance of IIP towards Cd²⁺ determination was evaluated by comparison to non-imprinted polymer, whose detectability of IIP was much higher (45%). The sensitivity of the sensor was found to be 0.0105 µA/µg L^?1. The limits of detection and limits of quantification were found to be 4.95 μg L^?1 and 16.4 μg L^?1, respectively. The developed method was successfully applied to Cd²⁺ determination in mineral, tap and lake water samples, whose results are in agreement with thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS) used as reference analytical technique. According to achieved results, the developed method can be used for routine analysis of quality control of water samples from different sources.     

Sensitive determination of Fenamiphos in water samples by flow injection photoinduced chemiluminescence

In this work, a sensitive flow injection chemiluminescence (FI-CL) method for the determination of nematicide Fenamiphos in a rapid and simple way is proposed. Fenamiphos is first photodegraded in basic medium. These photofragments react with Ce(IV) providing the chemiluminescence signal. To the authors’ knowledge, no chemiluminescence method has been described in the literature for the determination of the nematicide Fenamiphos. All physical and chemical parameters in the flow injection chemiluminescence system were optimized in order to obtain the best sensitivity, selectivity and sample throughput. Before the injection of the sample in the FI-CL system, a preconcentration step with solid phase extraction C18 cartridges was performed. By applying solid phase extraction (SPE) to 250?mL of standard (final volume 10?mL), the linear dynamic range was between 3.4 and 60?µg?L^?1, and the detection limit was 1?µg?L^?1. When SPE was applied to 500?mL of standard (final volume 10?mL), the detection limit was 0.5?µg?L^?1. These detection limits are below the emission limit value established by the Spanish Regulations of the Hydraulic Public Domain for pesticides (50?µg?L^?1) and of the same order as the limit established for total pesticides (0.5?µg?L^?1) at European Directive on the quality of water for human consumption. The sample throughput was 126 hour^?1. Intraday and interday coefficients of variation were below 10% in all cases. No interference was registered in presence of usual concentrations of anions, cations and other organophosphorus pesticides. The method was successfully applied to the analysis of environmental water samples, obtaining recoveries between 96 and 107.5%.     

Determination of As(III) using developed dispersive liquid–liquid microextraction and flame atomic absorption spectrometry

The method relies on selective complexation of As(III) with a suitable chelating agent followed by dispersive liquid–liquid microextraction (DLLME) method. Flame atomic absorption spectrometry (FAAS) equipped with microsample introduction system was utilised for determination of As(III). 1-Undecanol and acetone were used as extraction solvent and disperser solvent respectively. Some effective parameters on complex formation and extraction have been optimised. Under the optimum conditions, the enrichment factor of 108 for As(III) was obtained from 9.8?mL of water samples. The calibration graph was linear in the range of 2–15?µg?L^?1 with detection limits of 0.60?µg?L^?1 for As(III). The relative standard deviation (R.S.D.) for ten replicate measurements of 5.00?µ?gL^?1 of As(III) was 6.2%. Operation simplicity and high enrichment factors are the main advantages of DLLME for the determination of As(III) without necessity for hydride generation in water samples.     

Selective solid-phase extraction of lead(II) from biological and natural water samples using surface-grafted lead(II)-imprinted polymers

A new Pb(II)-imprinted amino-functionalized silica gel sorbent was synthesized by an easy one-step reaction by combining a surface imprinting technique for selective solid-phase extraction of trace Pb(II) prior to its determination by inductively coupled plasma optical emission spectrometry. The Pb(II)-imprinted amino-functionalized silica gel sorbent was characterized by Fourier transform infrared spectroscopy. Compared to non-imprinted polymer particles, the ion-imprinted polymers had higher selectivity and adsorption capacity for Pb(II). The maximum static adsorption capacity of the ion-imprinted and non-imprinted sorbent for Pb(II) was 19.66 and 6.20 mg g^?1, respectively. The largest selectivity coefficient of the Pb(II)-imprinted sorbent for Pb(II) in the presence of Cd(II) was over 450. The relative selectivity (α _r) values of Pb(II)/Cd(II) were 49.3 and 46.3, which were greater than 1. The distribution ratio (D) values of Pb(II)-imprinted polymers for Pb(II) were much larger than that for Cd(II). The detection limit (3σ) was 0.20 μg L^?1. The relative standard deviation was 2.0% for 11 replicate determinations. The method was validated for the analysis three certified reference materials (GBW 08301, GBW 08504, GBW 08511), and the results are in good agreement with standard values. The method was also successfully applied to the determination of trace lead in plants and water samples with satisfactory results.     

Speciation of Cr(III) and Cr(VI) using solid phase extraction and determination of total As inductively coupled plasma atomic emission spectrometry

An inductively coupled plasma atomic emission spectrometric (ICP-AES) method was developed for speciation and simultaneous determination of Cr and As, since these two analytes are commonly determined in various water samples in order to assess their toxicity. The objective of this research was to study the speciation of Cr(III), Cr(VI) in the presence of As(III) and/or As(V) using solid phase extraction (SPE) and ICP-AES. For these measurements, four spectral lines were used for each analyte with the purpose of selecting the most appropriate for each element. Finally with the use for first time of a cation-exchange column filled with benzosulfonic acid and elution with HCl, the speciation in solutions which contained [Cr(III)?+?Cr(VI)?+?As(V)] and [Cr(III)?+?Cr(VI)?+?As(III)] was examined. It was demonstrated that the separation of the two chromium species is almost quantitative and the simultaneous determination of chromium species and total arsenic analytes is possible, with very good performance characteristics. The estimated limits of detection for Cr(III), Cr(VI), As(III) and/or As(V) were 0.9?µg?L^?1, 1.1 µg?L^?1, 4.7 µg?L^?1 and 4.5 µg?L^?1 respectively, the calculated relative standard deviations (RSDs) were 3.8%, 4.1%, 5.2% and 5.1% respectively, and finally the accuracy of the methods was estimated using a certified aqueous reference material and found to be 5.6% and 4.8% for Cr(III) and Cr(VI) respectively. The method was applied to the routine analysis of various water samples.     

Enhanced Selectivity and Sensitivity for Flow Injection Spectrophotometric Determination of Cobalt Using Solid Phase Extraction with a 2D Ion-Imprinted Adsorbent

The present work reports the effectiveness of a 2D imprinting method based on a surface imprinting technique for the development of a selective and sensitive flow sorbent preconcentration system for Co²⁺ ion determination. Cobalt ions were determined by UV-vis spectrophotometry exploiting the complexation with 1-(2-piridylazo)-2-naphtol (PAN). Based on a coefficient of relative selectivity (k'), the ion-imprinted amino-functionalized silica gel sorbent (ISG), compared with modified but non-imprinted sorbent (MSG) and silica gel (SG), showed a very high selectivity. A limit of detection of 0.51 µg L^?1 and precision (n = 10) as a relative standard deviation of 2.63 and 1.50% for Co²⁺ concentration of 10.0 and 90.0 µg L^?1, respectively, were achieved. A comparison of the proposed method with other previously published methods shows advantages in terms of sample consumption, sample throughput, and limit of detection. The application of the present method was successfully performed for the direct determination of Co²⁺ content in urine and environmental water samples without any interference and without sample preparation, with satisfactory results.     

Separation,preconcentration and speciation of chromium by solid phase extraction on immobilised ferron

A sensitive and simple method for determination of chromium species after separation and preconcentration by solid phase extraction (SPE) has been developed. For the determination of the total concentration of chromium in solution, Cr(VI) was efficiently reduced to Cr(III) by addition of hydroxylamine and Cr(III) was preconcentrated on a column of immobilised ferron on alumina. The adsorbed analyte was then eluted with 5?mL of hydrochloric acid and was determined by flame atomic absorption spectrometery. The speciation of chromium was affected by first passing the solution through an acidic alumina column which retained Cr(VI) and then Cr(III) was preconcentrated by immobilised ferron column and determined by FAAS. The concentration of Cr(VI) was determined from the difference of concentration of total chromium and Cr(III). The effect of pH, concentration of eluent, flow rate of sample and eluent solution, and foreign ions on the sorption of chromium (III) by immobilised ferron column was investigated. Under the optimised conditions the calibration curve was linear over the range of 2–400?µg?L^?1 for 1000?mL preconcentration volume. The detection limit was 0.32?µg?L^?1, the preconcentration factor was 400, and the relative standard deviation (%RSD) was 1.9% (at 10?µg?L^?1; n?=?7). The method was successfully applied to the determination of chromium species in water samples and total chromium in standard alloys.     

Sensitive voltammetric determination of gallium in aluminium materials using renewable mercury film silver based electrode

Simple cyclic renewable silver amalgam film electrode (Hg(Ag)FE), applied for the determination of gallium(III) using differential pulse anodic stripping voltammetry (DP ASV), is presented. The effects of various factors such as: preconcentration potential and time, pulse height, step potential and supporting electrolyte composition are optimised. The calibration graph is linear from 5?nM (0.35?µg?L^?1) to 80?nM (5.6?µg?L^?1) for a preconcentration time of 60?s, with correlation coefficient of 0.995. For a Hg(Ag)FE with a surface area of 9.9?mm² the detection limit for a preconcentration time of 120?s is as low as 0.1?µg?L^?1. The repeatability of the method at a concentration level of the analyte as low as 3.5?µg?L^?1, expressed as RSD is 3.2% (n?=?5). The proposed method was successfully applied by studying the synthetic samples and simultaneously recovery of Ga(III) from spiked aluminium samples.     

Preconcentration of total chromium on Dowex 50W-X8 resin loaded with 2-amino-benzenethiol

Application of Dowex 50W-X8 loaded with 2-amino-benzenethiol for preconcentration of total chromium (Cr(VI) and Cr(III)) in water samples and subsequent determination by inductively coupled plasma-atomic emission spectrometry was studied. The reagent 2-amino-benzenethiol loaded onto the resin effectively reduced Cr(VI) to Cr(III) and total chromium (both Cr(VI) and Cr(III)) formed chelate complex with the reagent in the Cr(III) valence state. Experimental parameters such as preconcentration time, solution flow rates, pH, and concentration of the eluent were optimized. The method has been applied for the determination of total chromium in seawater samples in the range of 0.1–200?µg?L^?1. A detection limit of 0.3?µg?L^?1 was achieved, and the relative standard deviation was about 5%.     

Determination of trace chromium(VI) by an inhibition-based enzyme biosensor incorporating an electropolymerized aniline membrane and ferrocene as electron transfer mediator

A novel inhibition-based glucose oxidase (GOx) biosensor for environmental chromium(VI) detection is described. An electropolymerized aniline membrane has been prepared on a platinum electrode containing ferrocene as electron transfer mediator, on which GOx is cross-linked by glutaraldehyde. The mechanism of the redox reaction on the electrode and the performance of the sensor are studied. The sensor's response to glucose decreases when it is inhibited by chromium(VI), with a lower detection limit of 0.49?µg?L^?1, and the linear response range is divided into two parts, one of which is 0.49–95.73?µg?L^?1 and the other is 95.73?µg^?1 to8.05?mg?L^?1. The enzyme membrane is shown to be completely reactivated after inhibition, retaining 90% activity over more than forty days. Interference to chromium(VI) determination from lead(II), copper(II), cadmium(II), chromium(III), cobalt(II), tin(II) and nickel(II) is found to be minimal, while high concentrations of mercury(II) and silver(I) may interfere with the determination of trace chromium(VI). The sensor has been used for chromium(VI) determination in soil samples with good results.     

Application of a new ion-imprinted polymer for solid-phase extraction of bismuth from various samples and its determination by ETAAS

A batch process was developed to extract bismuth ions by a novel and selective sorbent. In this study, a new Bi(III)-ion imprinted polymer was prepared by formation of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex for selective preconcentration of ultra trace amounts of bismuth. Polymerization was performed with ethylene glycol dimethacrylate, as crosslinking monomer and methacrylic acid as functional monomer; in the presence of 2,2-azobisisobutyronitrile, as initiator, via bulk polymerization. Optimum pH for maximum sorption was 2.5–3.5. Maximum sorbent capacity and enrichment factor for bismuth were 35.9?mg?g^?1 and 300, respectively. The relative standard deviation and limit of detection the method were evaluated as ±4.1% and 8.6?ng?L^?1. This method is simple, selective and sensitive and can be applied to the determination of bismuth in water, biological and plant samples.