Voltammetric Determination of Pb,Cu and Hg in Biodiesel Using Gold Screen‐printed Electrode: Comparison of Batch‐injection Analysis with Conventional Electrochemical Systems

This article compares the use of batch‐injection analysis (BIA) with a conventional batch system for the anodic stripping voltammetric (ASV) determination of Pb, Cu and Hg in biodiesel using screen‐printed gold electrode (SPGE). The optimized BIA conditions were 200 µL of injection volume of the digested samples at 5 µL s^?1 directly on the working electrode of the SPGE immersed in 0.1 mol L^?1 HCl solution. Therefore, BIA‐ASV presented the advantages of low sample consumption, which extended the SPGE lifetime to a whole working day of analyses, and potential for on‐site analysis using battery‐powered micropipettes and potentiostats. Although presenting lower sensitivity than conventional systems, the BIA‐ASV presented detection limit values of 1.0, 0.5 and 0.7 µg L^?1, respectively for Pb, Cu and Hg, a linear range between 20 and 280 µg L^?1, and adequate recovery values (90–110 %) for spiked biodiesel samples.     

On‐line preconcentration strategy for the simultaneous quantification of three local anesthetics in human urine using CZE

The simultaneous determination of usually employed anesthetics (procaine, lidocaine, and bupivacaine) has been developed and validated using CE with ultraviolet detection at 212 nm. The separation of these three drugs has been achieved in less than 7 min, using a temperature of 25ºC and 25 kV, with a 150 mM citrate buffer (pH 2.5) as BGE. Field‐amplified sample injection (FASI) has been used for on‐line sample preconcentration. Ultrapure water and ACN 50/50 (v/v) mixture gave the greatest enhancement factor when it was employed as an injection solvent. Injection voltage and time were optimized, being 13 kV and 13 s, the optimum values, respectively. To avoid the possible irreproducibility associated with the electrokinetic injection, an internal standard such as tetracaine, was employed. The instrumental detection limits (LOD S/N = 3) for the compounds ranged between 2.6 and 7.0 μg L⁻¹ and the quantitation limits (LOQ S/N = 10) between 37.8 and 55.9 μg L⁻¹. The detection limits obtained in real human urine samples ranged between 55.2 and 83.6 μg L⁻¹ and the quantitation limits between 196.0 and 276.0 μg L⁻¹. The proposed method has demonstrated its applicability to the analysis of these local anesthetics in urine samples without any pretreatment, allowing the rapid determination of these target analytes.     

Total and inorganic mercury determination in fish tissue by flow injection cold vapour atomic fluorescence spectrometry

A simple and reliable method for Hg determination in fish samples has been developed. Lyophilised fish tissue samples were extracted in a 25% (w/v) tetramethylammonium hydroxide (TMAH) solution; the extracts were then analysed by FI-CVAFS. This method can be used to determine total and inorganic Hg, using the same FI manifold. For total Hg determination, a 0.1% (w/v) KMnO₄ solution was added to the FI manifold at the sample zone, followed by the addition of a 0.5% (w/v) SnCl₂ solution, whereas inorganic Hg was determined by adding a 0.1% (w/v) L-cysteine solution followed by a 1.0% (w/v) SnCl₂ solution to the FI system. The organic fraction was determined as the difference between total and inorganic Hg. Sample preparation, reagent consumption and parameters that can influence the FI-CVAFS performance were also evaluated. The limit of detection for this method is 3.7 ng g^?1 for total Hg and 4.3 ng g^?1 for inorganic Hg. The relative standard deviation for a 1.0 µg L^?1 CH₃Hg standard solution (n = 20) was 1.1%, and 1.3% for a 1.0 µg L^–1 Hg²⁺ standard solution (n = 20). Accuracy was assessed by the analysis of Certified Reference Material (dogfish: DORM-2, NRCC). Recoveries of 99.1% for total Hg and 93.9% inorganic Hg were obtained. Mercury losses were not observed when sample solutions were re-analysed after a seven day period of storage at 4°C.     

Nanoporous Gold Microelectrode: A Novel Sensing Platform for Highly Sensitive and Selective Determination of Arsenic (III) using Anodic Stripping Voltammetry

A home‐made gold microelectrode (Au‐μE) was fabricated and its surface was modified with nanoporous gold structures via a facile electrochemical approach (anodization followed by electrochemical reduction method). The fabricated nanoporous Au microelectrode (NPG‐μE) was used as a sensor probe for the determination of As(III) in 1.0 mol L⁻¹ HCl solution using square wave anodic stripping voltammetry (SWASV) technique. Field emission scanning electron microscopy (FE‐SEM) and cyclic voltammetry were used to characterize the surface morphology and assess the electrochemical surface area and the roughness factor of the NPG‐μE. SWASVs recorded with the NPG‐μE in As(III) solutions indicated linear behaviour in the concentration ranges of 10–200 μg L⁻¹ and 2–30 μg L⁻¹, with regression coefficients of 0.996 and 0.999 at a deposition time of 120 s, respectively. The limit of detection (LOD) was found to be 0.62 μg L⁻¹ with high sensitivity of 29.75 μA (μg L⁻¹)⁻¹ cm⁻². Repeatability and reproducibility were also examined and values were determined as 3.2 % and 9.0 %. Negligible interference from major interfering copper ion was noticed, revealing the excellent anti‐interference property of the proposed sensing platform. The developed NPG‐μE was successfully used for As(III) determination in tap water samples.     

Determination and speciation of selenium in water samples collected from Muğla (Turkey) province by hydride generation atomic absorption spectrometry

In this work, determination of selenium in various water samples was done by using hydride generation atomic absorption spectrometry. The most appropriate values of HCl concentration, NaBH₄ concentration, NaOH concentration, flow rate of argon and flow rate of waste solution were determined. The optimum concentration of the HCl, NaBH₄ and NaOH solutions were found to be 7.0 mol L^?1, 1.0% and 0.75%, respectively. The optimum flow rate of Ar gas and waste solution were also found to be 100.9 mL min^?1 and 4.0 mL min^?1, respectively. Values of LOD and LOQ were calculated separately for total Se and Se(IV). LOD and LOQ values were calculated 0.56 μg L^?1, 1.87 μg L^?1 for total Se and 0.72 μg L^?1, 2.40 μg L^?1 for Se(IV), respectively. The precision was evaluated by relative standard deviation (RSD%) was found to be 3.5% for total Se and 3.1% for Se(IV) (n = 11). A standard reference material (NIST 1643e) was used in order to check the accuracy of the proposed method. There was a good agreement between certified and found values for standard reference material. The method was applied to the analysis of total Se and Se(IV) concentrations in tap water samples collected from the various regions of Mu?la. Proposed method showed spike recovery ranges from 92% to 116% in water samples.     

Extraction and preconcentration of residual solvents in pharmaceuticals using dynamic headspace–liquid phase microextraction and their determination by gas chromatography–flame ionization detection

The present study describes a microextraction and determination method for analyzing residual solvents in pharmaceutical products using dynamic headspace–liquid phase microextraction technique followed by gas chromatography–flame ionization detection. In this method dimethyl sulfoxide (μL level) placed into a GC liner‐shaped extraction vessel is used as a collection/extraction solvent. Then the liner is exposed to the headspace of a vial containing the sample solution. The effect of different parameters influencing the microextraction procedure including collection/extraction solvent type and its volume, ionic strength, extraction time, extraction temperature and concentration of NaOH solution used in dissolving the studied pharmaceuticals are investigated and optimized. Under the optimum extraction conditions, the method showed wide linear ranges between 0.5 and 5000 mg L⁻¹. The other analytical parameters were obtained in the following ranges: enrichment factors 240–327, extraction recoveries 72–98% and limits of detection 0.1–0.8 mg L⁻¹ in solution and 0.6–3.2 μg g⁻¹ in solid. Relative standard deviations for the extraction of 100 mg L⁻¹ of each analyte were obtained in the ranges of 4–7 and 5–8% for intra ‐ day (n = 6) and inter ‐ day (n = 4) respectively. Finally the target analytes were determined in different samples such as erythromycin, azithromycin, cefalexin, amoxicillin and co‐amoxiclav by the proposed method.     

Simultaneous determination of cadmium and lead in wine by electrothermal atomic absorption spectrometry

A method has been developed for the direct simultaneous determination of Cd and Pb in white and red wine by electrothermal atomic absorption spectrometry (ET-AAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect background correction. The thermal behavior of both analytes during pyrolysis and atomization stages were investigated in 0.028 mol l⁻¹ HNO₃ and in 1+1 v/v diluted wine using mixtures of Pd(NO₃)₂+Mg(NO₃)₂ and NH₄H₂PO₄+Mg(NO₃)₂ as chemical modifiers. With 5 μg Pd+3 μg Mg as the modifiers and a two-step pyrolysis (10 s at 400°C and 10 s at 600°C), the formation of carbonaceous residues inside the atomizer was avoided. For 20 μl of sample (wine+0.056 mol l⁻¹ HNO₃, 1+1, v/v) dispensed into the graphite tube, analytical curves in the 0.10–1.0 μg l⁻¹ Cd and 5.0–50 μg l⁻¹ Pb ranges were established. The characteristic mass was approximately 0.6 pg for Cd and 33 pg for Pb, and the lifetime of the tube was approximately 400 firings. The limits of detection (LOD) based on integrated absorbance (0.03 μg l⁻¹ for Cd, 0.8 μg l⁻¹ for Pb) exceeded the requirements of Brazilian Food Regulations (decree #55871 from Health Department), which establish the maximum permissible level for Cd at 200 μg l⁻¹ and for Pb at 500 μg l⁻¹. The relative standard deviations (n=12) were typically <8% for Cd and <6% for Pb. The recoveries of Cd and Pb added to wine samples varied from 88 to 107% and 93 to 103%, respectively. The accuracy of the direct determination of Cd and Pb was checked for 10 table wines by comparing the results with those obtained for digested wine using single-element ET-AAS, which were in agreement at the 95% confidence level.     

N‐Doped Hollow Porous Carbon Spheres/Bismuth Hybrid Film Modified Electrodes for Sensitive Voltammetric Determination of Trace Cadmium

In this work, N‐doped hollow porous carbon spheres (N‐HPCSs) were synthesized by silicon dioxide template‐assisted polybenzoxazine (PB) coating strategy. The prepared N‐HPCSs have a smooth hollow ball structure surrounded by a well‐defined porous shell. Combining with in‐situ plating of Bi film, the N‐HPCSs were further fabricated a sensitive electrochemical platform for determination trace levels of Cd(II) by differential pulse anodic stripping voltammetry (DPASV). Under the optimized conditions, the Bi‐N‐HPCSs based sensor displays a linear response to Cd(II) over the range of 0.5 μg L⁻¹ to 150 μg L⁻¹. Meanwhile, the limit of detection (LOD, S/N=3) is estimated to be around 0.16 μg L⁻¹ for Cd(II), which is 31 times lower than the safety values set by United States Environmental Protection Agency (EPA) for the drinking water. Moreover, the proposed method was successfully applied to detection of Cd(II) in tap water and lake water, and the analytical results of the presented method are agreed well with inductively coupled plasma‐mass spectrometry (ICP‐MS) data. Due to the excellent analytical performance, the fabricated electrode is promised for future development in monitoring of cadmium pollution in the environment.     

Simultaneous Determination of 1,4‐Benzodiazepines and Tricyclic Antidepressants in Saliva after Sequential SPE Elution by the Same HPLC Conditions

A new method has been described to determine both benzodiazepines (six) and tricyclic antidepressants (four) simultaneously in saliva by HPLC with a UV detector set at 240 nm using cholchicine as the internal standard. A careful specific sequential solid‐phase elution was optimized and performed to elute benzodiazepines using a mixture of methanol‐acetonitrile (1:1 v/v) followed by the elution of tricyclic antidepressants with methanol. Separation of the compounds was performed on a Kromasil column (250 × 4 mm, 5 μm) by a gradient eluents consisting of 0.05 M CH₃COONH₄‐acetonitrile‐methanol (55:15:30 v/v/v). The results were linear for both benzodiazepines and tricyclic antidepressants up to 20 ng μL^‐1 with the correlation coefficients greater than 0.998. The sensitivity limits, LOD and LOQ were 0.08‐0.34 ng μL^‐1 and 0.28‐1.13 ng μL^‐1, respectively. The method is simple, fast and reliable with good specificity and sensitivity, will be suitable for use in a clinical setting, where there is a concomitant use of 1,4‐benzodiazepines and tricyclic antidepressants.     

Development of a Sensor Based on Modified Carbon Paste with Com Iron(III) Protoporphyrin Immobilized on SiNbZn Silica Matrix for L‐tryptophan Determination

In this work, SiO₂/Nb₂O₅/ZnO prepared by the sol‐gel processing method was used as substrate base for immobilization of the protoporphyrin‐IX ion. Iron(III) ion was inserted into the porphyrin ring (SiNbZn‐PPFe). A simple square wave voltammetry method based on a composite sensor carbon paste electrode of this material,designed as EPC‐SiNbZn‐PPFe, was developed and validated successfully for the determination of L‐tryptophan (Trp). The optimum conditions were obtained by using sensor modified with 18.00 mg SiNbZn‐PPFe material, 12.00 mg graphite powder and 6.0 μL mineral oil and phosphate buffer 0.3 mol L⁻¹ pH 7.0. The sensitivity of the sensor was found to be 0.523 AL mol ⁻¹, linear range from 10 to 70 μmol L⁻¹ and limit of detection of 3.28 μmol L⁻¹. Therefore, the developed method was successfully applied for the Trp determination in real samples of pharmaceutical formulation and can be used for routine quality control pharmaceutical formulations containing Trp.     

Over‐Oxidized Poly (Phenol Red) Film Modified Glassy Carbon Electrode for Anodic Stripping Voltammetric Determination of Ultra‐Trace Antimony (III)

In this study, we introduce a very sensitive and selective method for the differential pulse anodic stripping determination of Sb(III) ion on the over‐oxidized poly(phenol red) modified glassy carbon electrode (PPhRed_ox/GCE) in 0.1 mol L^‐1 HCl medium. The formation of both poly(phenol red) and over‐oxidized poly(phenol red) film on the electrode surfaces were characterized by electrochemical impedance spectroscopy, X‐ray photoelectron spectroscopy and scanning electron microscopy techniques. An anodic stripping peak of Sb(III) was observed at 0.015 V on the PPhRed_ox/GCE. Higher anodic stripping peak current of Sb(III) was obtained at PPhRed_ox/GCE compared with both bare GCE and poly(phenol red) film modified GCE (PPhRed/GCE). The calibration graph consisted of two linear segments of 0.044 ‐ 1.218 μg L⁻¹ and 3.40 – 18.26 μg L⁻¹ with a detection limit of 0.0075 μg L⁻¹. The proposed over‐oxidized polymer film modified electrode was applied successfully for the analysis of antimony in different spiked water samples. Spiked recoveries for water samples were obtained in the range of 93.0–103.0%. The accuracy of the method was also verified through the analysis of standard reference materials (SCP SCIENCE‐EnviroMAT™ EP−L‐2).     

Simultaneous Electrochemical Detection of Co(II) and Cu(II) by 1‐Diazo‐2‐Naphthol‐4‐Sulfonic Acid/MWCNTs Modified Electrode

This work describes a simple preparation of 1‐diazo‐2‐naphthol‐4‐sulfonic acid (1,2,4‐acid) and multiwalled carbon nanotubes (MWCNTs) modified glassy carbon electrode (GCE) for the simultaneous detection of Co(II) and Cu(II). MWCNTs, with their good conductivity and large surface area, were drop‐casted onto the surface of the GCE prior to the electrodeposition of 1,2,4‐acid, a metal chelating agent. Co(II) and Cu(II) were simultaneously measured by differential pulse anodic stripping voltammetry (DPASV) in a batch system. Under optimum conditions, the linear range of Co(II) was between 0.10 and 2.5 μg mL⁻¹ with an LOD of 80 ng mL⁻¹. Two linear ranges were obtained for Cu(II), 0.0050 to 0.030 μg mL⁻¹ and 0.040 to 0.25 μg mL⁻¹,with an LOD of 2.4 ng mL⁻¹. The method offered a high operational stability for up to 52 measurements (RSD=3.4 % for Co(II) and 2.6 % for Cu(II)) and good reproducibility (RSD=1.2 % for Co(II) and 1.7 % for Cu(II)). In the simultaneous detection of Co(II) and Cu(II), there was no effect from common interferences found in wastewater. The method was successfully applied in real water samples with good recoveries (88.2±0.8 to 102.0±0.8 % for Co(II) and 96.5±0.4 to 103.8±0.9 % for Cu(II)) and the results were in good agreement with those obtained from inductively coupled plasma optical emission spectrometry (ICP‐OES) (P >0.05).     

Bi‐enzyme Electrochemical Sensor for Selective Determination of Organophosphorus Pesticides with Phenolic Leaving Groups

An amperometric bi‐enzyme sensor for detection of organophosphorus pesticides (OPs) with phenolic leaving groups, which are not electroactive, is presented in this work. The biosensing platform was created by a simple, controllable, and reproducible one‐step electrodeposition onto the surface of a glassy carbon electrode of a chitosan bionanocomposite with entrapped carboxylated multi walled carbon nanotubes, organophosphorus hydrolase (OPH), and horseradish peroxidase (HRP). The OPs determination involved a sequence of OPH and HRP‐catalyzed reactions resulting in phenolic radicals production, which were quantified by registering the current of their reduction at a potential of −50 mV vs. Ag, AgCl/KCl_sat.The developed sensor was applied for the determination of prothiofos, as an example. At optimized conditions (pH 7.25 and H₂O₂ concentration 200 μmol L⁻¹), a LOD as low as 0.8 μmol L⁻¹ was attained, while the linear concentration range was extended from 2.64 μmol L⁻¹ up to 35 μmol L⁻¹. The main advantage of the proposed bi‐enzyme sensor is its selectivity toward the OPs with phenolic leaving groups, excluding the interference of the nitrophenyl‐substituted OPs.     

Development of a New Voltammetric Methodology for the Determination of Ciprofloxacin in Beef Samples Using a Carbon Paste Electrode Modified with Nafion and Fullerenes

A sensitive, selective, and low cost electrochemical new methodology was developed for the quantification of ciprofloxacin (Cip) in beef samples by cyclic voltammetry and differential pulse voltammetry, using a CPE electrode modified with Nafion and Fullerenes (N−F/CPE). The optimum parameters for the composition of the N−F/CPE electrode are 0.19 g mineral oil, 0.01 g Nafion, 50 μL fullerene, and graphite powder 0.3 g. The electrochemical characterization was carried out by obtaining maximum anodic peak current associated with the oxidation of ciprofloxacin at 1.1 V, where the electrochemical process resulted to be irreversible and diffusion-controlled. The analytical characterization of the proposed methodology was carried out resulting in a LOD of 1.0 μmol L⁻¹, a LOQ of 3.0 μmol L⁻¹, a sensitivity of 0.37±0.006 μA/μmolL⁻¹, and repeatability of 5.38 %.     

Voltammetric Method for the Simultaneous Determination of Melatonin and Pyridoxine in Dietary Supplements Using a Cathodically Pretreated Boron‐doped Diamond Electrode

The simultaneous voltammetric determination of melatonin (MT) and pyridoxine (PY) has been carried out at a cathodically pretreated boron‐doped diamond electrode. By using cyclic voltammetry, a separation of the oxidation peak potentials of both compounds present in mixture was about 0.47 V in Britton‐Robinson buffer, pH 2. The results obtained by square‐wave voltammetry allowed a method to be developed for determination of MT and PY simultaneously in the ranges 1–100 μg mL⁻¹ (4.3×10⁻⁶–4.3×10⁻⁴ mol L⁻¹) and 10–175 μg mL⁻¹ (4.9×10⁻⁵–8.5×10⁻⁴ mol L⁻¹), with detection limits of 0.14 μg mL⁻¹ (6.0×10⁻⁷ mol L⁻¹) and 1.35 μg mL⁻¹ (6.6×10⁻⁶ mol L⁻¹), respectively. The proposed method was successfully to the dietary supplements samples containing these compounds for health‐caring purposes.     

Square Wave‐Anodic Stripping Voltammetric Determination of Copper at a Bismuth Film/Glassy Carbon Electrode Using 3‐[(2‐Mercapto‐Vinyl)‐Hydrazono]‐ 1,3‐Dihydro‐Indol‐2‐One

This study reports a highly sensitive electrochemical sensor based on Bi film modified glassy carbon electrode (BiF/GCE) for total determination and speciation trace concentrations of copper(II) ions in environmental water samples. Square wave‐adsorptive anodic stripping voltammetric (SW‐ASV) experiment was performed for monitoring selective accumulation of copper(II) with reagent 3‐[(2‐mercapto‐vinyl)‐hydrazono]‐1,3‐dihydro‐indol‐2‐one (MHDI) at pH 9–10. The mechanism of the electrode reaction of Cu²⁺‐MHDI complex was safely assigned. The sensor exhibited a wide linear range (3.22×10⁻⁹–2.0×10⁻⁷ mol L⁻¹) with lower limits of detection (LOD) and quantitation (LOQ) of 9.6×1⁻¹⁰ and 3.22×10⁻⁹ mol L⁻¹, respectively (R²=0.9993). The proposed sensor exhibited interference from active metal ions e. g. Cd, Hg. The performance of the proposed method was compared successfully with most of the reported methods and comparable efficiencies were obtained. The analytical utility of the proposed SW‐ASV method has been successfully validated for trace analysis of copper(II) in environmental water samples. The method offers a precise, accurate approach with good reproducibility, robustness, ruggedness, and cost effectiveness.     

Copper‐based Metal‐organic Framework Applied in the Development of an Electrochemical Biomimetic Sensor for Catechol Determination

In this study, the synthesis and characterization of a Cu‐based metal‐organic framework (MOF) [Cu₃(BTC)₂(H₂O)₃]_n (where BTC=benzene‐1,3,5‐tricarboxylate), known as HKUST‐1, were performed. The Cu‐MOF was applied in the modification of a carbon paste to obtain a biomimetic sensor for the electrochemical determination of catechol. Kinetic assays confirmed that the Cu‐MOF acts as a catalyst for the oxidation of catechol and it can be considered as a catechol oxidase mimetic. Under optimized conditions, the calibration curve for catechol presented a linear range of 8.0×10⁻⁷ to 3.2×10⁻⁵ mol L⁻¹, with detection limit of=1.0×10⁻⁷ mol L⁻¹. The sensor demonstrated good intra‐day repeatability and inter‐electrode reproducibility (relative standard deviations of 3.8 % (n=10) and 4.3 % (n=6), respectively). In the selectivity study, an adequate peak‐to‐peak separation was observed for hydroquinone and uric acid in relation to catechol, demonstrating that this sensor has the potential for use in the simultaneous determination of these compounds. This sensor was successfully applied in the determination of catechol in water samples.     

Silica Gel-Immobilized 5-aminoisophthalohydrazide: A novel sorbent for solid phase extraction of Cu,Zn and Pb from natural water samples

A novel silica sorbent, silica gel-immobilized 5-aminoisophthalohydrazide (SiO₂-APH), was prepared by the condensation of 3-chloropropyl-functionalized silica gel with 5-aminoisophthalohydrazide (APH) derived from dimethyl 5-aminoisophthalate as a starting material and used for separation and preconcentration of Cu, Zn, and Pb metals in water samples using Flame Atomic Absorption Spectrometry (FAAS). The characterization of the new sorbent was carried out by Elemental Analysis, Thermogravimetric Analysis (TGA) and Fourier Transform Infrared Spectroscopy (FTIR). Important analytical parameters including as pH, amount of sorbent, type and amount of eluting solvent, sample volume, vortex and ultrasonic bath time, matrix ions that effect the developed SiO₂-APH-solid phase extraction (SPE) method were investigated and optimum parameters were detected. Recoveries of examined metals were obtained as 98% for Cu and Pb and 101% for Zn. The relative standard deviation (RSD, n = 8) of Cu, Zn and Pb metals were 3.2, 2.8 and 1.6%, respectively. Limit of detections (LODs) (n = 10) were found as 2.7 μg L⁻¹ for Cu, 7.4 μg L⁻¹ for Zn and 3.5 μg L⁻¹ for Pb μg L⁻¹. The accuracy of the new method was assessed by analyzing of TMDA-51.4 and TMDA-70.2 certified reference materials. The results obtained for metals were in a good agreement with certified values. Addition/recovery test was applied to the real well, river, dam and stream water samples to check the accuracy of the method. The results showed that the developed SiO₂-APH-SPE method can be effectively used as an alternative method for determination of Cu, Zn, and Pb metals in water samples.     

Application of response surface methodology for optimization of trace amount of diazinon preconcentration in natural waters and biological samples by carbon mesoporous CMK‐3

Preconcentration of trace amounts of diazinon by carbon mesoporous CMK‐3 in water and biological samples and measurement by high‐performance liquid chromatography were investigated. CMK‐3 was prepared using hexagonal SBA‐15 as the template. The synthesized materials were characterized by X‐Ray diffraction (XRD), Fourier transform infrared spectroscopy, Brunaur–Emmet–Teller, transmission electron microscopy and Boehm titration method. The preconcentration procedure was optimized using a multivariate optimization approach following a two‐stage process. The effect of analytical parameters including the amount of the CMK‐3 as an adsorbent, pH, type and volume of eluent and flow rate of eluent and sample were studied by a screening project, then the effective parameters were optimized by response surface methodology based on central composite design. The average extraction efficiency of diazinon under optimal conditions (CMK‐3 dosage = 25 mg, sample flow rate = 2.5 mL min⁻¹, eluent flow rate = 1.25 mL min⁻¹, volume of methanol as an eluent =3.5 mL and initial pH = 6) was 97.11%, which agrees well with the predicted response value (97.93%). The linearity of the method was in the range of 0.5–100 μg L⁻¹ with a correlation coefficient of 0.997. Enrichment factor, limit of detection and limit of quantification were 285.7, 0.09 and 0.23 μg L⁻¹, respectively. The relative standard deviation (RSD) under optimum conditions was 2.21% (n = 5). The proposed method was applied to determine diazinon in real water and biological samples. Recovery of diazinon from real samples was between 95.80 and 104.94% with an RSD of 0.19–4.65%. Thus, this method is suitable for the preconcentration and determination of diazinon in real water and biological samples.     

Renewable Copper and Silver Amalgam Film Electrodes of Prolonged Application for the Determination of Elemental Sulfur Using Stripping Voltammetry

New, renewable copper (Hg(Cu)FE) and silver (Hg(Ag)FE) based amalgam film electrodes applied for the determination of elemental sulfur using differential pulse cathodic stripping voltammetry are presented. With surface areas adjustable from 1 to 12 mm², both electrodes are characterized by very good surface reproducibility (≤2%) and long‐term stability (a few thousand measurement cycles). The mechanical refreshing of the amalgam film takes about 1–2 seconds. The effects of various factors such as instrumental parameters and the supporting electrolyte composition were optimized. Interferences from sulfides are easily removed by the addition of acid, and bubbling with argon, for Hg(Ag)FE. In the case of Hg(Cu)FE, sulfides did not interfere. The calibration graph is linear within the studied range from 16 ng L^?1 to 4.8 μg L^?1 for Hg(Cu)FE, and up to 6.4 μg L^?1 for Hg(Ag)FE (t_acc=15 s). The correlation coefficients for the two electrodes were at least 0.997. The detection limits for a low concentration of S(0) and t_acc=60 s are as low as 14 ng L^?1 for Hg(Cu)FE and 4 ng L^?1 for Hg(Ag)FE. The proposed method was successfully applied and validated by studying the recovery of S(0) from spiked river water.