High-sensitivity determination of lead and cadmium based on the Nafion-graphene composite film

Graphene nanosheets, dispersed in Nafion (Nafion-G) solution, were used in combination with in situ plated bismuth film electrode for fabricating the enhanced electrochemical sensing platform to determine the lead (Pb²⁺) and cadmium (Cd²⁺) by differential pulse anodic stripping voltammetry (DPASV). The electrochemical properties of the composite film modified glassy carbon electrode were investigated. It is found that the prepared Nafion-G composite film not only exhibited improved sensitivity for the metal ion detections, but also alleviated the interferences due to the synergistic effect of graphene nanosheets and Nafion. The linear calibration curves ranged from 0.5 μg L⁻¹ to 50 μg L⁻¹ for Pb²⁺ and 1.5 μg L⁻¹ to 30 μg L⁻¹ for Cd²⁺, respectively. The detection limits (S/N = 3) were estimated to be around 0.02 μg L⁻¹ for Pb²⁺ and Cd²⁺. The practical application of the proposed method was verified in the water sample determination.     

Electrodes with extremely high hydrogen overvoltages as substrate electrodes for stripping analysis based on bismuth-coated electrodes

Hydrogen evolution bothers stripping analysis significantly. Dioctyl phthalate-based carbon paste electrode exhibits extremely wide cathodic potential window. It is explored as a powerful substrate electrode to solve the problem of hydrogen evolution and further improve reproducibility for stripping analysis using bismuth-coated electrodes for the first time. It was successfully applied to the simultaneous determination of Zn²⁺, Cd²⁺, and Pb²⁺. Linear responses are obtained for Zn²⁺ in the range of 10–100 μg L⁻¹ and for Pb²⁺ and Cd²⁺ in the range of 5–100 μg L⁻¹. The detection limits for Zn²⁺, Cd²⁺, and Pb²⁺ are 0.1 μg L⁻¹, 0.22 μg L⁻¹ and 0.44 μg L⁻¹, respectively. The method has been successfully applied to the determination of Zn²⁺, Cd²⁺, and Pb²⁺ in waste water samples. The detection strategy based on the combination of dioctyl phthalate-based carbon paste electrode and bismuth-coated electrodes holds great promise for stripping analysis.     

Determination of Hg by on-line separation and pre-concentration with atmospheric-pressure solution-cathode glow discharge atomic emission spectrometry

A simple and sensitive method to determine Hg²⁺ was developed by combining solution-cathode glow discharge atomic emission spectrometry (SCGD-AES) with flow injection (FI) based on on-line solid-phase extraction (SPE). We synthesized l-cysteine-modified mesoporous silica and packed it in an SPE microcolumn, which was experimentally determined to possess a good mercury adsorption capacity. An enrichment factor of 42 was achieved under optimized Hg²⁺ elution conditions, namely, an FI flow rate of 2.0 mL min⁻¹ and an eluent comprised of 10% thiourea in 0.2 mol L⁻¹ HNO₃. The detection limit of FI–SCGD-AES was determined to be 0.75 μg L⁻¹, and the precision of the 11 replicate Hg²⁺ measurements was 0.86% at a concentration of 100 μg L⁻¹. The proposed method was validated by determining Hg²⁺ in certified reference materials such as human hair (GBW09101b) and stream sediment (GBW07310).     

Langmuir-Blodgett film of p-tert-butylthiacalix[4]arene modified glassy carbon electrode as voltammetric sensor for the determination of Hg(II)

The π-A isotherms and UV-vis spectra of the transferred films suggested that the monolayer of p-tert-butylthiacalix[4]arene can coordinate with Hg²⁺ at the air-water surface. From these observations, a glassy carbon electrode coated with Langmuir-Blodgett film of p-tert-butylthiacalix[4] arene as a new voltammetric sensor is designed for the determination of trace amounts of Hg²⁺. Compared with bare glassy carbon electrode and modified glassy carbon electrode using direct coating method, the Langmuir-Blodgett film-modified electrode can greatly improve the measuring sensitivity of Hg²⁺. Under the selected conditions, the Langmuir-Blodgett film-modified electrode in 0.1 mol L⁻¹ H₂SO₄ + 0.01 mol L⁻¹ KCl solution shows a linear voltammetric response for Hg²⁺ in the range of 5.0 × 10⁻¹⁰ to 1.5 × 10⁻⁷ mol L⁻¹, with a detection limit of 2.0 × 10⁻¹⁰ mol L⁻¹. The proposed method was also applied to determine Hg²⁺ in water samples (tap, lake and river water). In addition, the fabricated electrode exhibited a distinct advantage of simple preparation, non-toxicity, good reproducibility and good stability.     

Electrodeposition of gold nanoparticles on indium/tin oxide electrode for fabrication of a disposable hydrogen peroxide biosensor

A novel disposable third-generation hydrogen peroxide (H₂O₂) biosensor based on horseradish peroxidase (HRP) immobilized on the gold nanoparticles (AuNPs) electrodeposited indium tin oxide (ITO) electrode is investigated. The AuNPs deposited on ITO electrode were characterized by UV-vis, SEM, and electrochemical methods. The AuNPs attached on the ITO electrode surface with quasi-spherical shape and the average size of diameters was about 25 nm with a quite symmetric distribution. The direct electron chemistry of HRP was realized, and the biosensor exhibited excellent performances for the reduction of H₂O₂. The amperometric response to H₂O₂ shows a linear relation in the range from 8.0 μmol L⁻¹ to 3.0 mmol L⁻¹ and a detection limit of 2 μmol L⁻¹ (S/N = 3). The value of HRP immobilized on the electrode surface was found to be 0.4 mmol L⁻¹. The biosensor indicates excellent reproducibility, high selectivity and long-term stability.     

Determination of dissolved sulphides in waste water samples by flow-through stripping chronopotentiometry with a macroporous mercury-film electrode

Sulphides in water samples were determined by stripping chronopotentiometry in a computer controlled flow system with a flow-through electrochemical cell. The working electrode was a porous glassy carbon electrode coated with Nafion and mercury. The sample was diluted with 0.1 mol L⁻¹ NaOH and analysed. Sulphides in the sample were collected in the porous electrode as mercury sulphide and then stripped by a current of −500 μA. The limit of detection was found to be 1.6 μg L⁻¹ and 0.5 μg L⁻¹ for 1 mL and 5 mL of preconcentrated sample, respectively. The linear range for 1 mL sample was found to be 5-400 μg L⁻¹. The repeatability and reproducibility was found to be 2.6% and 4.8%, respectively. The method was applied to analyses of waste water samples from a tannery.     

Determination of mercurial species in fish by inductively coupled plasma mass spectrometry with anion exchange chromatographic separation

This work demonstrated the feasibility of mercury speciation analysis by anion exchange chromatographic separation with inductively coupled plasma mass spectrometry detection. For the first time, by complexing with the mobile phase containing 3-mercapto-1-propanesulfonate into negatively charged complexes, fast separation of inorganic mercury (Hg²⁺), monomethylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg) was achieved within 5 min on a 12.5-mm strong anion exchange column. The detection limits for Hg²⁺, MeHg, EtHg and PhHg were 0.008, 0.024, 0.029 and 0.034 μg L⁻¹, respectively. The relative standard deviations of peak height and peak area (5.0 μg L⁻¹ for each Hg species) were all below 3%. The determined contents of Hg²⁺, MeHg and total Hg in a certified reference material of fish tissue by the proposed method were in good accordance with the certified values with satisfactory recoveries. The relative errors for determining MeHg and total mercury were −2.4% and −1.2%, respectively, with an acceptable range for spike recoveries of 94–101%. Mercury speciation in 11 fish samples were then analyzed after the pretreated procedure. The mercury contents in all fish samples analyzed were found compliant with the criteria of the National Standards of China.     

Determination of cadmium with a sequential injection lab-on-valve by anodic stripping voltammetry using a nafion coated bismuth film electrode

This work exploited a sequential injection lab-on-valve (LOV) system for the determination of cadmium by anodic stripping voltammetry (ASV). A miniaturized electrochemical flow cell (EFC) was fabricated in LOV, in which a nafion coated bismuth film electrode was used as working electrode. The cadmium was electrodeposited on the electrode surface in bismuth solution, and measured with the subsequential stripping scan. Under optimal conditions, the proposed system responded linearly to cadmium concentrations in a range 2.0-100.0 μg L⁻¹. The detection limit of this method was found to be 0.88 μg L⁻¹. By loading a sample volume of 800 μL, a sampling frequency of 22 determinations h⁻¹ was achieved. The repeatability expressed as relative standard derivation (R.S.D.) was 3.65% for 20 μg L⁻¹ cadmium (n = 11). The established method was applied to analysis of trace cadmium in environmental water samples and the spiked recoveries were satisfactory.     

Speciation analysis of mercury in sediments, zoobenthos and river water samples by high-performance liquid chromatography hyphenated to atomic fluorescence spectrometry following preconcentration by solid phase extraction

A high-pressure microwave digestion was applied for microwave-assisted extraction (MAE) of mercury species from sediments and zoobenthos samples. A mixture containing 3 mol L⁻¹ HCl, 50% aqueous methanol and 0.2 mol L⁻¹ citric acid (for masking co-extracted Fe³⁺) was selected as the most suitable extraction agent. The efficiency of proposed extraction method was better than 95% with R.S.D. below 6%. A preconcentration method utilizing a “homemade” C18 solid phase extraction (SPE) microcolumns was developed to enhance sensitivity of the mercury species determination using on-column complex formation of mercury-2-mercaptophenol complexes. Methanol was chosen for counter-current elution of the retained mercury complexes achieving a preconcentration factor as much as 1000. The preconcentration method was applied for the speciation analysis of mercury in river water samples. The high-performance liquid chromatography-cold vapour atomic fluorescence spectrometric (HPLC/CV-AFS) method was used for the speciation analysis of mercury. The complete separation of four mercury species was achieved by an isocratic elution of aqueous methanol (65%/35%) on a Zorbax SB-C18 column (4.6 mm × 150 mm, 5 μm) using the same complexation reagent (2-mercaptophenol). The limits of detection were 4.3 μg L⁻¹ for methylmercury (MeHg⁺), 1.4 μg L⁻¹ for ethylmercury (EtHg⁺), 0.8 μg L⁻¹ for inorganic mercury (Hg²⁺), 0.8 μg L⁻¹ for phenylmercury (PhHg⁺).     

An optical sensor for mercury ion based on the fluorescence quenching of tetra(p-dimethylaminophenyl)porphyrin

An optical sensor for mercury ion (Hg²⁺), based on quenching the fluorescence of the sensing reagent porphyrin immobilized in plasticized poly(vinyl chloride) (PVC) membrane, has been developed. The responses to mercury ion were compared for the sensors modified with three porphyrin compounds including 5,10,15,20-tetraphenylporphyrin (TPP), tetra(p-dimethylaminophenyl)porphyrin (TDMAPP) and tetra(N-phenylpyrazole) porphyrin (TPPP). Among them, TDMAPP showed the most remarkable response to Hg²⁺. The drastic decrease of the TDMAPP fluorescence intensity was attributed to the formation of a complex between TDMAPP and Hg²⁺, which has been utilized as the fabrication basis of a Hg²⁺-sensitive fluorescence sensor. The analytical performance characteristics of the TDMAPP modified sensor was investigated. The response mechanism, especially involving the response difference of three porphyrin compounds, was discussed in detail. The sensor can be applied to the quantification of Hg²⁺ with a linear range covering from 4.0 × 10⁻⁸ mol L⁻¹ to 4.0 × 10⁻⁶ mol L⁻¹. The limit of detection was 8.0 × 10⁻⁹ mol L⁻¹. The sensor exhibited excellent reproducibility, reversibility and selectivity. Also, the TDMAPP-based sensor was successfully used for the determination of Hg²⁺ in environmental water samples.     

A new Hg-selective fluorescent sensor based on a dansyl amide-armed calix[4]-aza-crown

A new fluorescent chemosensor for Hg²⁺ based on a dansyl amide-armed calix[4]-aza-crown was reported. It exhibits high sensitivity and selectivity toward Hg²⁺ over a wide range of metal ions in MeCN-H₂O (4:1, v/v). The association constant of the 1:1 complex formation for 2-Hg²⁺ was calculated to be 1.31 × 10⁵ M⁻¹, and the detection limit for Hg²⁺ was found to be 4.1 × 10⁻⁶ mol L⁻¹.     

A fluorescent chemosensor for Hg based on naphthalimide derivative by fluorescence enhancement in aqueous solution

Naphthalimide derivative (compound 1) containing hydrophilic hexanoic acid group was synthesized and used to recognize Hg²⁺ in aqueous solution. The fluorescence enhancement of 1 is attributed to the formation of a complex between 1 and Hg²⁺ by 1:1 complex ratio (K = 2.08 × 10⁵), which has been utilized as the basis of fabrication of the Hg²⁺-sensitive fluorescent chemosensor. The comparison of this method with some other fluorescence methods for the determination of Hg²⁺ indicated that the method can be applied in aqueous solution rather than organic solution. The analytical performance characteristics of the proposed Hg²⁺-sensitive chemosensor were investigated. The chemosensor can be applied to the quantification of Hg²⁺ with a linear range covering from 2.57 × 10⁻⁷ to 9.27 × 10⁻⁵ M and a detection limit of 4.93 × 10⁻⁸ M. The experiment results show that the response behavior of 1 toward Hg²⁺ is pH independent in medium condition (pH 4.0–8.0). Most importantly, the fluorescence changes of the chemosensor are remarkably specific for Hg²⁺ in the presence of other metal ions, which meet the selective requirements for practical application. Moreover, the response of the chemosensor toward Hg²⁺ is fast (response time less than 1 min). In addition, the chemosensor has been used for determination of Hg²⁺ in hair samples with satisfactory results, which further demonstrates its value of practical applications.     

Voltammetric determination of Cu(II) in natural waters and human hair at a meso-2,3-dimercaptosuccinic acid self-assembled gold electrode

An electrochemical sensor for the detection of copper(II) ions is described using a meso-2,3-dimercaptosuccinic acid (DMSA) self-assembled gold electrode. First in ammonia buffer pH 8, copper(II) ions complex with self-assembled monolayer (SAM) via the free carboxyl groups on immobilized meso-2,3-dimercaptosuccinic acid (accumulation step). Then, the medium is exchanged to acetate buffer pH 4.6 and the complexed Cu(II) ions are reduced in negative potential of −0.3 V (reduction step). Following this, reduced coppers are oxidized and detected by differential pulse (DP) voltammetric scans from −0.3 to +0.7 V (stripping step). The effective parameters in sensor response were examined. The detection limit of copper(II) was 1.29 μg L⁻¹ and R.S.D. for 200 μg L⁻¹ was 1.06%. The calibration curve was linear for 3-225 μg L⁻¹ copper(II). The procedure was applied for determination of Cu(II) to natural waters and human hairs. The accuracy and precision of results were comparable to those obtained by flame atomic absorption spectroscopy (FAAS).     

Electrochemiluminescence from Ru(bpy)3 immobilized in poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)-poly(vinyl alcohol) composite films

Electrochemical behavior and electrogenerated chemiluminescence (ECL) of tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺) immobilized in poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate)-poly(vinyl alcohol) (PEDOT/PSS-PVA) composite films via ion-exchange have been investigated with tripropylamine (TPA) as the co-reactant at a glassy carbon electrode. The immobilized Ru(bpy)₃²⁺ performed a surface-controlled electrode reaction. The Ru(bpy)₃²⁺ modified electrode showed a fast ECL response to TPA, and was used for the ECL detection of TPA with high sensitivity. The ECL intensity was linearly related to concentrations of TPA over the range from 0.50 μmol L⁻¹ to 0.80 mmol L⁻¹, and the detection limit was 0.10 μmol L⁻¹ (S/N = 3). The as-prepared electrode exhibited good precision and long-term stability for TPA determination.     

Sensitive pseudobienzyme electrocatalytic DNA biosensor for mercury(II) ion by using the autonomously assembled hemin/G-quadruplex DNAzyme nanowires for signal amplification

Herein, a novel sensitive pseudobienzyme electrocatalytic DNA biosensor was proposed for mercury ion (Hg²⁺) detection by using autonomously assembled hemin/G-quadruplex DNAzyme nanowires for signal amplification. Thiol functionalized capture DNA was firstly immobilized on a nano-Au modified glass carbon electrode (GCE). In presence of Hg²⁺, the specific coordination between Hg²⁺ and T could result in the assembly of primer DNA on the electrode, which successfully triggered the HCR to form the hemin/G-quadruplex DNAzyme nanowires with substantial redox probe thionine (Thi). In the electrolyte of PBS containing NADH, the hemin/G-quadruplex nanowires firstly acted as an NADH oxidase to assist the concomitant formation of H₂O₂ in the presence of dissolved O₂. Then, with the redox probe Thi as electron mediator, the hemin/G-quadruplex nanowires acted as an HRP-mimicking DNAzyme that quickly bioelectrocatalyzed the reduction of produced H₂O₂, which finally led to a dramatically amplified electrochemical signal. This method has demonstrated a high sensitivity of Hg²⁺ detection with the dynamic concentration range spanning from 1.0 ng L⁻¹ to 10 mg L⁻¹ Hg²⁺ and a detection limit of 0.5 ng L⁻¹ (2.5 pM) at the 3S_blank level, and it also demonstrated excellent selectivity against other interferential metal ions.     

ZnO-coated glass fibers for the analysis of trihalomethanes by headspace-solid phase microextraction-gas chromatography

Li₂O-ZrO₂-BaO-SiO₂ glass fibers were produced and their surfaces were coated with zinc oxide. The fibers’ surface morphology was examined by scanning electron microscopy and the zinc oxide layer was characterized by mapping the K_α and L_α lines of zinc by energy dispersive X-ray spectroscopy. The results indicated that a homogeneous and porous layer of ZnO was formed on the fibers’ surface. This layer was subjected to a simultaneous determination of trihalomethanes using headspace-solid phase microextraction-gas chromatography. The study was conducted after evaluating the ideal time of incubation (15 min), extraction (15 min) and desorption (10 min), as well as the effect of the addition of salt (15%, m/v) on the analytical response. A good linear dynamic range was observed individually for trihalomethanes aqueous solutions containing 20 μg L⁻¹ and 500 μg L⁻¹ of trichloromethane, 15 μg L⁻¹ and 250 μg L⁻¹ of dichlorobromomethane and dibromochloromethane and 10 μg L⁻¹ and 100 μg L⁻¹ of tribromomethane, with all the compounds showing correlation coefficients higher than 0.9900.     

Preconcentration of trace elements from water samples on a minicolumn of yeast (Yamadazyma spartinae) immobilized TiO2 nanoparticles for determination by ICP-AES

A trace element preconcentration procedure is described utilizing a minicolumn of yeast (Yamadazyma spartinae) immobilized TiO₂ nanoparticles for determination of Cr, Cu, Fe, Mn, Ni and Zn from water samples by inductively coupled plasma atomic emission spectrometry. The elements were quantitatively retained on the column between pH 6 and 8. Elution was made with 5% (v/v) HNO₃ solution. Recoveries ranged from 98 ± 2 (Cr) to 100 ± 4 (Zn) for preconcentration of 50 mL multielement solution (50 μg L⁻¹). The column made up of 100 mg sorbent (yeast immobilized TiO₂ NP) offers a capacity to preconcentrate up to 500 mL of sample solution to achieve an enrichment factor of 250 with 2 mL of 5% (v/v) HNO₃ eluent. The detection limits obtained from preconcentration of 50 mL blank solutions (5%, v/v, HNO₃, n = 11) were 0.17, 0.45, 0.25, 0.15, 0.33 and 0.10 μg L⁻¹ for Cr, Cu, Fe, Mn, Ni and Zn, respectively. Relative standard deviation (RSD) for five replicate analyses was better than 5%. The retention of the elements was not affected from up to 500 μg L⁻¹ Na⁺ and K⁺ (as chlorides), 100 μg L⁻¹ Ca²⁺ (as nitrate) and 50 μg L⁻¹ Mg²⁺ (as sulfate). The method was validated by analysis of freshwater standard reference material (SRM 1643e) and applied to the determination of the elements from tap water and lake water samples.     

Determination of the steroid hormone levels in water samples by dispersive liquid-liquid microextraction with solidification of a floating organic drop followed by high-performance liquid chromatography

In this study, the steroid hormone levels in river and tap water samples were determined by using a novel dispersive liquid-liquid microextraction method based on the solidification of a floating organic drop (DLLME-SFO). Several parameters were optimized, including the type and volume of the extraction and dispersive solvents, extraction time, and salt effect. DLLME-SFO is a fast, cheap, and easy-to-use method for detecting trace levels of samples. Most importantly, this method uses less-toxic solvent. The correlation coefficient of the calibration curve was higher than 0.9991. The linear range was from 5 to 1000 μg L⁻¹. The spiked environmental water samples were analyzed using DLLME-SFO. The relative recoveries ranged from 87% to 116% for river water (which was spiked with 4 μg L⁻¹ for E1, 3 μg L⁻¹ for E2, 4 μg L⁻¹ for EE2 and 9 μg L⁻¹ for E3) and 89% to 102% for tap water (which was spiked with 6 μg L⁻¹ for E1, 5 μg L⁻¹ for E2, 6 μg L⁻¹ for EE2 and 10 μg L⁻¹ for E3). The detection limits of the method ranged from 0.8 to 2.7 μg L⁻¹ for spiked river water and 1.4 to 3.1 μg L⁻¹ for spiked tap water. The methods precision ranged from 8% to 14% for spiked river water and 7% to 14% for spiked tap water.     

Determination of 4-ethylcatechol in wine by high-performance liquid chromatography-coulometric electrochemical array detection

A HPLC method using a coulometric electrode array detector (CEAD) to analyse 4-ethylcatechol in wine was established. The procedure does not require any sample preparation or analyte derivatisation and performs chromatographic separation in a short time. The assay method is linear up to 1520 μg L⁻¹ and precise (R.S.D. < 3%), with limits of detection and quantitation of 1.34 μg L⁻¹ and 2.2 μg L⁻¹, respectively. Recoveries in spiked wine samples ranged from 95% to 104% with a median value of 102% and matrix effects were not observed. The method was applied to the evaluation of the concentration of 4-EC in 250 commercial Italian wines. The red wines analysed had median, 75° percentile and maximum values of 37 μg L⁻¹, 89 μg L⁻¹ and 1610 μg L⁻¹, respectively. For Sangiovese-based wines the mean ratios of 4-EP and 4-EG to 4-EC were 3.7:1 and 0.7:1, respectively. The feasibility of a cheaper fluorimetric approach to 4-EC quantification was investigated.     

Preparation of a carbon ceramic electrode modified by 4-(2-pyridylazo)-resorcinol for determination of trace amounts of silver

A 4-(2-pyridylazo)-resorcinol (PAR)-modified carbon ceramic electrode (CCE) prepared by the sol-gel technique has been reported for the first time in this paper. By immersing the CCE in aqueous solution of PAR (0.001 mol L⁻¹), after a short period of time, a thin film of PAR was rapidly formed on the surface of the electrode due to its strong adsorption properties. A differential pulse anodic stripping voltammetric (DPASV) method was developed for determination of Ag(I) at the modified carbon ceramic electrode. The analysis procedure consisted of an open circuit accumulation step in a sample solution which was continuously stirred for 12 min. This was followed by replacing the medium with a clean solution where the accumulated Ag(I) was reduced for 15 s in −0.6 V. Then, the potential was scanned from −0.2 to +0.2 V to obtain the voltammetric peak. The detection limit of silver(I) was 0.123 μg L⁻¹, and for seven successive determinations of 10, 100 and 200 μg L⁻¹ Ag(I), the relative standard deviations were 2.1, 1.4 and 1.03%, respectively. The calibration curve was linear for 0.5-300 μg L⁻¹ silver(I). The procedure was applied to determine silver(I) in X-ray photographic films and super-alloy samples.