Determination of arsenic compounds in beverages by high-performance liquid chromatography-inductively coupled plasma mass spectrometry

Arsenic compounds including arsenous acid (As(III)), arsenic acid (As(V)), dimethylarsinic acid (DMA) and monomethylarsonic acid (MMA) were separated by high-performance liquid chromatography (HPLC) and detected by inductively coupled plasma mass spectrometry (ICP-MS). A Hamilton PRX-100 anionic-exchange column and a pH 8.5 K₂HPO₄/KH₂PO₄ 5.0 × 10⁻³ mol L⁻¹ mobile phase were used to achieve arsenic speciation. The separation of arsenic species provided peaks of As(III) at 2.75 min, DMA at 3.33 min, MMA at 5.17 min and As(V) at 12.5 min. The detection limits, defined as three times the standard deviation of the lowest standard measurements, were found to be 0.2, 0.2, 0.3 and 0.5 ng mL⁻¹ for As(III), DMA, MMA and As(V), respectively. The relative standard deviation values for a solution containing 5.0 μg L⁻¹ of As(III), DMA, MMA and As(V) were 1.2, 2.1, 2.5 and 3.0%, respectively. This analytical procedure was applied to the speciation of arsenic compounds in drinking (soft drink, beer, juice) samples. The validation of the procedure was achieved through the analysis of arsenic compounds in water and sediment certified reference materials.     

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 As(III) and As(V) in soils using sequential extraction combined with flow injection hydride generation atomic fluorescence detection

An analytical procedure for determination of As(III) and As(V) in soils using sequential extraction combined with flow injection (FI) hydride generation atomic fluorescence spectrometry (HG-AFS) was presented. The soils were sequentially extracted by water, 0.6 mol l⁻¹ KH₂PO₄ solution, 1% (v/v) HCl solution and 1% (w/v) NaOH solution. The arsenite (As(III)) in extract was analyzed by HG-AFS in the medium of 0.1 mol l⁻¹ citric acid solution, then the total arsenic in extract was determined by HG-AFS using on-line reduction of arsenate with l-cysteine. The concentration of arsenate (As(V)) was calculated by the difference. The optimum conditions of extraction and determination were studied in detail. The detection limit (3σ) for As(III) and As(V) were 0.11 and 0.07 μg l⁻¹, respectively. The relative standard deviation (R.S.D.) was 1.43% (n=11) at the 10 μg l⁻¹ As level. The method was applied in the determination of As(III) and As(V) of real soils and the recoveries of As(III) and As(V) were in the range of 89.3-118 and 80.4-111%, respectively.     

Determination of arsenic(III) and total inorganic arsenic in water samples using an on-line sequential insertion system and hydride generation atomic absorption spectrometry

A simple and robust on-line sequential insertion system coupled with hydride generation atomic absorption spectrometry (HG-AAS) was developed, for selective As(III) and total inorganic arsenic determination without pre-reduction step. The proposed manifold, which is employing an integrated reaction chamber/gas-liquid separator (RC-GLS), is characterized by the ability of the successful managing of variable sample volumes (up to 25 ml), in order to achieve high sensitivity. Arsine is able to be selectively generated either from inorganic As(III) or from total arsenic, using different concentrations of HCl and NaBH₄ solutions. For 8 ml sample volume consumption, the sampling frequency is 40 h⁻¹. The detection limit is c_L = 0.1 and 0.06 μg l⁻¹ for As(III) and total arsenic, respectively. The precision (relative standard deviation) at 2.0 μg l⁻¹ (n = 10) level is s_r = 2.9 and 3.1% for As(III) and total arsenic, respectively. The performance of the proposed method was evaluated by analyzing the certified reference material NIST CRM 1643d and spiked water samples with various concentration ratios of As(III) to As(V). The method was applied for arsenic speciation in natural waters samples.     

A novel high selective and sensitive para-nitrophenol voltammetric sensor, based on a molecularly imprinted polymer-carbon paste electrode

By using a molecularly imprinted polymer (MIP) as a recognition element, the design and construction of a high selective voltammetric sensor for para-nitrophenol was formed. Para-nitrophenol selective MIP and a non-imprinted polymer (NIP) were synthesized, and then used for carbon paste (CP) electrode preparation. The MIP-CP electrode showed greater recognition ability in comparison to the NIP-CP. It was shown that electrode washing after para-nitrophenol extraction led to enhanced selectivity, without noticeably decreasing the sensitivity. Some parameters affecting sensor response were optimized and a calibration curve was plotted. A dynamic linear range of 8 × 10⁻⁹ to 5 × 10⁻⁶ mol L⁻¹ was obtained. The detection limit of the sensor was calculated as 3 × 10⁻⁹ mol L⁻¹. Thus, this sensor was used successfully for the para-nitrophenol determination in different water samples.     

Non-chromatographic speciation of toxic arsenic in fish

A rapid, sensitive and economic method has been developed for the direct determination of toxic species of arsenic present in fish and mussel samples. As(III), As(V), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) were determined by hydride generation-atomic fluorescence spectrometry using a series of proportional equations without the need of a chromatographic previous separation. The method is based on the extraction of arsenic species from fish through sonication with HNO₃ 3 mol l⁻¹ and 0.1% (m/v) Triton and washing of the solid phase with 0.1% (m/v) EDTA, followed by direct measurement of the corresponding hydrides in four different experimental conditions. The limit of detection of the method was 0.62 ng g⁻¹ for As(III), 2.1 ng g⁻¹ for As(V), 1.8 ng g⁻¹ for MMA and 5.4 ng g⁻¹ for DMA, in all cases expressed in terms of sample dry weight. The mean relative standard deviation values (R.S.D.) in actual sample analysis were: 6.8% for As(III), 10.3% for As(V), 8.5% for MMA and 7.4% for DMA at concentration levels from 0.08 mg kg⁻¹ As(III) to 1.3 mg kg⁻¹ DMA. Recovery studies provided percentages greater than 93% for all species in spiked samples. The analysis of SRM DORM-2 and CRM 627 certified materials evidenced that the method is suitable for the accurate determination of arsenic species in fish.     

Determination of arsenic in gold samples using matrix exchange differential pulse stripping voltammetry

A method comprising matrix exchange differential pulse stripping voltammetry (DPSV) at a gold film electrode has been proposed for the determination of small quantities of arsenic in pure gold. A wall-jet cell (WJC) and an on-line deoxygenation system were used to facilitate matrix exchange. The gold(I) cyanide complex was formed to avoid gold deposition on the electrode together with the arsenic. The pH of the sample solutions were adjusted to 3, as alkaline solutions gold(I) cyanide produced interference and the uncomplexed cyanide led to passivation of the gold film electrode. Matrix exchange electrolytes consisting of 4 mol l⁻¹ hydrochloric acid or a combination of 2 mol l⁻¹ sulphuric acid and 0.2 mol l⁻¹ hydrochloric acid could be utilised. Arsenic concentrations as low as 0.1 mg l⁻¹, could readily be detected in a gold matrix with a 60 s deposition time. While, cobalt and silver did not interfere with the arsenic determination, copper interfered even when present at similar concentrations to that of arsenic.     

Speciation of inorganic arsenic in a sequential injection dual mini-column system coupled with hydride generation atomic fluorescence spectrometry

The separation and speciation of inorganic arsenic(III) and arsenic(V) are facilitated by employing a novel sequential injection system incorporating two mini-columns followed by detection with hydride generation atomic fluorescence spectrometry. An octadecyl immobilized silica mini-column is used for selective retention of the complex between As(III) and APDC, while the sorption of As(V) is readily accomplished by a 717 anion exchange resin mini-column. The retained As(III)-PDC complex and As(V) are effectively eluted with a 3.0 mol L⁻¹ hydrochloric acid solution as stripping reagent, which well facilitates the ensuing hydride generation process via reaction with tetrahydroborate. With a sampling volume of 1.0 mL and an eluent volume of 100 μL for both species, linear ranges of 0.05-1.5 μg L⁻¹ for As(III) and 0.1-1.5 μg L⁻¹ for As(V) are obtained, along with enrichment factors of 7.0 and 8.2, respectively. Precisions of 2.8% for As(III) and 2.9% for As(V) are derived at the concentration level of 1.0 μg L⁻¹. The practical applicability of the procedure has been demonstrated by analyzing a certified reference material of riverine water (SLRS-4), in addition to spiking recovery in a lake water sample matrix.     

A potential visual fluorescence probe for ultratrace arsenic (III) detection by using glutathione-capped CdTe quantum dots

The interaction between mercaptoacetic acid (MA)-capped CdTe QDs, MA-capped CdTe/ZnS QDs or glutathione (GSH)-capped CdTe QDs with As(III) was studied using fluorescence spectrometry. As (III) has a high-affinity to reduced-GSH to form As(SG)₃, and the emission of the GSH-capped CdTe QDs (λ_em. = 612 nm) is quenched effectively. Thus, a novel fluorescence spectrometric method was developed for As (III) determination by using GSH-CdTe QDs. Under optimal conditions, the quenched fluorescence intensity (F₀/F) increased linearly with the concentration of As (III) ranging from 5.0 × 10⁻⁶ to 25 × 10⁻⁵ mol L⁻¹. The limit of detection (3σ) for As (III) was found to be 2 × 10⁻⁸ mol L⁻¹. This method is potentially useful in visual detection of As (III) under irradiation of the ultraviolet light.     

Lithium ions determination by selective pre-concentration and differential pulse anodic stripping voltammetry using a carbon paste electrode modified with a spinel-type manganese oxide

The use of selective pre-concentration and differential pulse anodic stripping voltammetry (DPASV) using a carbon paste electrode modified (CPEM) with spinel-type manganese oxide has been proposed for the determination of lithium ions content in natural waters. The new procedure is based on the effective pre-concentration of lithium ions on the electrode surface containing spinel-type Mn(IV) oxide with the reduction of Mn(IV) to Mn(III) and consequently the lithium ions intercalation (insertion) into the spinel structure. The best DPASV response was reached for an electrode composition of 25% (m/m) spinel-type MnO₂ in the paste, 0.1 mol l⁻¹ tris(hydroxymethyl)aminomethane (TRIS) buffer solution of pH 8.3, scan rate of 5 mV s⁻¹, accumulation potential of 0.3 V versus saturated calomel reference electrode (SCE), pre-concentration time of 30 s and potential pulse amplitude of 50 mV. In these experimental conditions, the proposed methodology responds to lithium ions in the concentration range of 2.8×10⁻⁶ to 2.0×10⁻³ mol l⁻¹ with a detection limit of 5.6×10⁻⁷ mol l⁻¹. The determination of the lithium ions content in different samples of natural waters samples using the proposed methodology and atomic absorption spectrophotometry are in agreement at the 95% confidence level and within an acceptable range of error.     

Voltammetry determination of trace manganese with pretreatment glassy carbon electrode by linear sweep voltammetry

This paper described the determination of trace manganese using linear sweep voltammetry at a pretreatment glassy carbon electrode. The glassy carbon electrode pretreated by electrochemical method in the 0.1 mol l⁻¹ NaOH solution greatly improved the electrode responsibility in the determination of manganese(II). The barrier to the detection of low manganese concentration was overcome by means of autocatalytic effect of manganese oxide deposited on the electrode in advance. Under the optimum experiments condition (0.04 mol l⁻¹ NH₃-NH₄Cl buffer solution, pH 9.0), the linear range was 4×10⁻⁸ to 1×l0⁻⁶ mol l⁻¹ Mn(II) for linear sweep voltammetry and 1×10⁻⁹ to 4×10⁻⁸ mol l⁻¹ Mn(II) for convolution voltammetry. The relative standard deviation for 2×10⁻⁸ mol l⁻¹ Mn(II) is 3.4%. The proposed method is simple, rapid, sensitive and selective. It had been applied to the determination of trace manganese in samples with satisfactory results.     

Extraction of arsenic compounds from lichens

Different extraction procedures were applied to improve the extraction efficiency of arsenic compounds from lichens. Two lichen species were chosen from an arsenic-contaminated environment: epiphytic Hypogymnia physodes (L.) Nyl. and terricolous Cladonia rei Schaer. Samples were extracted with water at temperatures of 20, 60 and 90 °C, using mixtures of methanol/water (9:1, 1:1 and 1:9), Tris buffer and acetone and the extracts speciated. Water and Tris buffer showed the best extraction efficiency of all extractants used; however, the extraction efficiency was still less than 23%. Since a major fraction of arsenic appeared to be associated with trapped soil particles, a sequential extraction procedure originally designed for soils (extraction steps: (1) 0.05 mol l⁻¹ (NH₄)₂SO₄; (2) 0.05 mol l⁻¹ (NH)₄H₂PO₄; (3) 0.2 mol l⁻¹ NH₄-oxalate buffer, pH 3.25; (4) mixture of 0.2 mol l⁻¹ NH₄-oxalate buffer and 0.1 mol l⁻¹ ascorbic acid, pH 3.25; (5) 0.5 mol l⁻¹ KOH) was applied and found to remove 45% of the total arsenic from H. physodes and 83% from C. rei. The lipid-soluble fraction of arsenic was estimated by k₀-INAA analysis of diethylether extracts and was found to be negligible. An HPLC-UV-HGAFS system was used to determine the arsenic compounds extracted. In both lichen species, arsenous acid, arsenic acid, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, trimethylarsine oxide and glycerol-ribose were detected. In addition, phosphate-ribose was found in H. physodes.     

Simultaneous, sensitive and selective on-line chemiluminescence determination of Cr(III) and Cr(VI) by capillary electrophoresis

A novel in-capillary reduction and capillary electrophoretic (CE)-chemiluminescence (CL) method was developed for the sensitive and selective determination of chromium(III) and chromium(VI). The proposed method was based on the in-capillary reduction of Cr(VI) with acidic H₂O₂ to form Cr(III) using the zone-passing technique and chemiluminescence detection of Cr(III). The sample [Cr³⁺ and CrO₄²⁻], hydrochloric acid, and H₂O₂ (reductant) solution segments were injected for specified periods of time in this order from the anodic end of a capillary, followed by application of an appropriate running voltage between both ends. As both chromium species have opposite charges, Cr³⁺ migrates to the cathode while CrO₄²⁻ ion, moving oppositely to the anode, reacts with acidic H₂O_2, resulted in formation of Cr³⁺. Based on the migration time difference of both Cr³⁺ ions, they were separated by zone electrophoresis. Running buffer was composed of 0.02 mol l⁻¹ HAc-NaAc (pH 4.7) with 1×10⁻³ mol l⁻¹ EDTA. Parameters affecting CE-CL separation and detection, such as reductant concentration, mixing mode of the analytes with CL reagent, CL reaction reagent pH and concentration, stability of luminol-hydrogen peroxide mixed solution were optimized. The limits of detection for chromium(III) and chromium(VI) (3σ) were 6×10⁻¹³ mol l⁻¹ (mass concentration 12 zmol) and 8×10⁻¹² mol l⁻¹ (160 zmol), respectively. This method offered potential advantages of simplicity, sensitivity, selectivity and applicability to the determination of Cr(III) and Cr(VI) in environmental water.     

Electrosorption of Os(III)-complex at single-wall carbon nanotubes immobilized on a glassy carbon electrode: application to nanomolar detection of bromate, periodate and iodate

A simple procedure was developed to prepare a glassy carbon electrode modified with single-wall carbon nanotubes (SWCNTs) and Os(III)-complex. The glassy carbon (GC) electrode modified with CNTs was immersed into Os(III)-complex solution (direct deposition) for a short period of time (60 s). 1,4,8,12-Tetraazacyclotetradecane osmium(III) chloride, (Os(III)LCl₂)·ClO₄, irreversibly and strongly adsorbed on SWCNTs immobilized on the surface of GC electrode. Cyclic voltammograms of the Os(III)-complex-incorporated-SWCNTs indicate a pair of well defined and nearly reversible redox couple with surface confined characteristic at wide pH range (1-8). The surface coverage (Γ) and charge transfer rate constant (k_s) of the immobilized Os-complex on SWCNTs were 3.07 × 10⁻⁹ mol cm⁻², 5.5 (±0.2) s⁻¹, 2.94 × 10⁻⁹ mol cm⁻², 7.3 (±0.3) s⁻¹ at buffer solution with pH 2 and 7, respectively, indicate high loading ability of SWCNTs for Os(III) complex and great facilitation of the electron transfer between electroactive redox center and carbon nanotubes immobilized on the electrode surface. Modified electrodes showed higher electrocatalytic activity toward reduction of BrO₃⁻, IO₃⁻ and IO₄⁻ in acidic solutions. The catalytic rate constants for catalytic reduction bromate, periodate and iodate were 3.79 (±0.2) × 10³, 7.32 (±0.2) × 10³ and 1.75 (±0.2) × 10³ M⁻¹ s ⁻¹, respectively. The hydrodynamic amperometry of rotating modified electrode at constant potential (0.3 V) was used for nanomolar detection of selected analytes. Excellent electrochemical reversibility of the redox couple, good reproducibility, high stability, low detection limit, long life time, fast amperometric response time, wide linear concentration range, technical simplicity and possibility of rapid preparation are great advantage of this sensor.     

Determination of cerium ion by polymeric membrane and coated graphite electrode based on novel pendant armed macrocycle

Plasticized membranes using 2,3,4:12,13,14-dipyridine-1,3,5,8,11,13,15,18-octaazacycloicosa-2,12-diene (L₁) and 2,3,4:12,13,14-dipyridine-1,5,8,11,15,18-hexamethylacrylate-1,3,5,8,11,13,15,18-octaazacycloicosa-2,12-diene (L₂) have been prepared and explored as Ce(III) selective sensors. Effect of various plasticizers viz. dibutylphthalate (DBP), tri-n-butylphthalate (TBP), o-nitrophenyloctylether (o-NPOE), dioctylphthalate (DOP), benzylacetate (BA) and anion excluders, sodium tetraphenylborate (NaTPB) and potassium tetrakis p-(chlorophenyl) borate was studied in detail and improved performance was observed. Optimum performance was observed for the membrane sensor having a composition of L₂:PVC:o-NPOE:KTpClPB in the ratio of 6:34:58:2 (w/w, mg). The performance of the membrane based on L₂ was compared with polymeric membrane electrode (PME) as well as with coated graphite electrode (CGE). The electrodes exhibit Nernstian slope for Ce(III) ions with limits of detection of 8.3 × 10⁻⁸ mol L⁻¹ for PME and 7.7 × 10⁻⁹ mol L⁻¹ for CGE. The response time for PME and CGE was found to be 12 s and 10 s respectively. The potentiometric responses are independent of the pH of the test solution in the pH range 3.5-7.5 for PME and 2.5-8.5 for CGE. The CGE could be used for a period of 5 months. The practical utility of the CGE has been demonstrated by its usage as an indicator electrode in potentiometric titration of oxalate and fluoride ions with Ce(III) solution. The proposed electrode was also successfully applied to the determination of fluoride ions in mouthwash solution and oxalate ions in real samples.     

Silver ion imprinted polymer nanobeads based on a aza-thioether crown containing a 1,10-phenanthroline subunit for solid phase extraction and for voltammetric and potentiometric silver sensors

A new nano-sized silver(I) ion-imprinted polymer (IIP) was prepared via precipitation copolymerization using ethyleneglycol dimethacrylate, as a cross-linking agent in the presence of Ag⁺ and an aza-thioether crown containing a 1,10-phenanthroline subunit as a highly selective complexing agent. The imprint silver(I) ion was removed from the polymeric matrix using a 1.0 M HNO₃ solution. The resulting powder material was characterized using IR spectroscopy and scanning electron microscopy. The SEM micrographs showed colloidal nanoparticles of about 52 nm and 75 nm in diameter and slightly irregular in shape for leached and unleached IIPs, respectively. The optimal pH for quantitative enrichment was 6.0 and maximum sorbent capacity of the prepared IIP for Ag⁺ was 18.08 μmol g⁻¹. The relative standard deviation and limit of detection (LOD = 3S_b/m) for flame atomic absorption spectrometric determination of silver(I) ion, after its selective extraction by the prepared IIP nanobeads, were evaluated as 2.42% and 2.2 × 10⁻⁸ M, respectively. The new Ag⁺-IIP was also applied as a suitable sensing element to the preparation of highly selective and sensitive voltammetric and potentiometric sensors for ultra trace detection of silver(I) ion in water samples, with limits of detection of 9.0 × 10⁻¹⁰ and 1.2 × 10⁻⁹ M, respectively.     

A SO2-selective electrode based on a Zn-porphyrin for wine analysis

This work describes the assessment of a SO₂-selective electrode based on the use of the neutral carrier 5,10,15,20-tetraphenyl(porphyrinate)zinc(II) in a PVC membrane plasticized with 2-nitrophenyl phenyl ether. After being conditioned in 2 mol L⁻¹ diethylamine solution for 24 h, the electrode exhibited selective anionic response toward the analyte in a concentration interval of more than four decades, with an slope of −59.5 mV dec⁻¹, a practical detection limit of 3.7 × 10⁻⁶ mol L⁻¹ and a low limit of linear range of 7.2 × 10⁻⁶ mol L⁻¹. The response mechanism is based on the displacement of the diethylamine:metalloporphyrin complex equilibrium within membrane bulk, inducing a variation in the cationic-sites to ionophore ratio. In turn, free hydroxyl ions are complexed by the displaced ionophore in a ratio 1:1 and translated as single negative charge nernstian response. Finally, the selectivity of the electrode is evaluated in view of its application to wine analysis. Results had high accuracy and precision when compared with a reference method.     

Catalytic-adsorptive stripping voltammetric determination of ultra-trace iridium(III). Application to fresh- and sea-water

An extremely sensitive stripping voltammetric procedure for ultra-trace determination of iridium(III) is reported. The method is based on the interfacial accumulation of the iridium(III)-CTAB complex onto the glassy carbon electrode, followed by the catalytic reduction of the adsorbed complex in the presence of bromate. 0.3 mol L⁻¹ acetate buffer pH 4.7 + 6.9 × 10⁻² mol L⁻¹ NaBrO₃ + 2.7 × 10⁻⁵ mol L⁻¹ cetyltrimethylammonium bromide (CTAB) + 0.2 mol L⁻¹ KCl was employed as the supporting electrolyte.The analytical procedure was verified by the analysis of the standard reference materials: Sea Water BCR-CRM 403 and Fresh Water NIST-SRM 1643d.The accuracy, expressed as relative error e%, was satisfactory, being lower than 6%, while precision as repeatability, expressed as relative standard deviation s_r%, was generally lower than 5%. The limit of detection was of the order of 2-3 ng L⁻¹.Once set up on the standard reference materials, the analytical procedure was transferred and applied to superficial water sampled in proximity to superhighway and in the Po river mouth area.     

Determination of trace amount of bismuth(III) by adsorptive anodic stripping voltammetry at carbon paste electrode

A sensitive method is described for the determination of trace bismuth based on the bismuth-bromopyrogallol red (BPR) adsorption at a carbon paste electrode (CPE). The overall analysis involved a three-step procedure: accumulation, reduction, and anodic stripping. Optimal conditions were found to be an electrode containing 25% paraffin oil and 75% high purity graphite powder, a 0.30 mol l⁻¹ HCl solution containing 2.0×10⁻⁵ mol l⁻¹ BPR as supporting medium; accumulation potential and time, −0.10 V, 3 min; reduction potential and time, −0.35 V, 60 s; scan rate 100 mV s⁻¹; scan range from −0.35 to 0.15 V. It was found that the Bi(III)-BPR complex could be accumulated on the electrode surface during the accumulation period. Then the Bi(III) in the Bi(III)-BPR complex on the CPE surface was reduced to Bi(0) during reduction interval and finally reoxidized during the anodic stripping step for voltammetric quantification. Factors affecting the accumulation, reduction, and stripping steps were investigated. Interferences by other ions were studied as well. The detection limit was found to be 5×10⁻¹⁰ mol l⁻¹ with a 3 min accumulation time. The linear range was from 1.0×10⁻⁹ to 5.0×10⁻⁷ mol l⁻¹. Application of the procedure to the determination of bismuth in water and human hair samples gave good results.     

Novel platinum(II) selective membrane electrode based on 1,3-bis(2-cyanobenzene)triazene

A plasticized poly (vinyl chloride) membrane electrode based on 1,3-bis(2-cyanobenzene)triazene (CBT) for highly selective determination of platinum(II) (in PtCl₄²⁻ form) is developed. The electrode showed a good Nernstian response (29.8 ± 0.3 mV decade⁻¹) over a wide concentration range (1.0 × 10⁻⁶ to 1.0 × 10⁻² mol L⁻¹). The limit of detection was 5.0 × 10⁻⁷ mol L⁻¹. The electrode has a response time of about 40 s, and it can be used for at least 1 month without observing any considerable deviation from Nernstian response. The proposed electrode revealed an excellent selectivity toward platinum(II) ion over a wide variety of alkali, alkaline earth, transition, and heavy metal ions, and it could be used in the pH range of 3.2-5.1. The practical utility of the electrode has been demonstrated by its use in determination of platinum ion in, alloy, tap, mineral and river water samples.