Chitosan functionalized with di-2-propanolamine: Its application as solid phase extractant for the determination of germanium in water samples by ICP-MS

Cross-linked chitosan was chemically modified with di-2-propanolamine via an arm of chloromethyloxirane (CCTS-DPA resin). The adsorption behavior of the resin towards 62 elements was examined using a mini-column pretreatment method, and the collected elements were eluted with 1 mol L^− 1 nitric acid before measurement by inductively coupled plasma-mass spectrometry (ICP-MS).The CCTS-DPA resin can adsorb several metal cations and several oxoanionic elements at appropriate pH. However, di-2-propanolamine (DPA) attached to cross-linked chitosan (CCTS) showed excellent ability and selectivity for the adsorption of germanium at pH 6 to 9. The adsorption capacity of the resin for germanium (IV) was found to be 106 mg g^− 1 resin, whereas the adsorption rate constant was 9.82 × 10^− 2 min^− 1. Through the column treatment, alkali and alkaline earth matrices in river water and seawater matrices could be completely removed. The resin can also successfully remove chloride and selenium that can interfere with the direct determination of germanium by ICP-MS. The applicability of the CCTS-DPA resin was further demonstrated for the collection/preconcentration of germanium in environmental water samples and its determination by ICP-MS. The concentrations of germanium in tap water, river water and seawater samples were found in the range of 0.011 to 0.022 μg L^− 1.     

Isotachophoretic determination of hydrosulfite and metabisulfite in technical samples

A method for determination of metabisulfite and hydrosulfite in poultice and decolorant by isotachophoresis was developed. Metabisulfite and hydrosulfite are ionizable oxoanions of sulfur of similar character that can easily be oxidized to sulfates. To protect the analytes from oxidation the solid samples were dissolved in a 1% (w/v) solution of formaldehyde. Hydrosulfite and metabisulfite present in the samples were transformed by the reaction with formaldehyde to stable compounds, hydroxymethanesulfinate and hydroxymethanesulfonate that were determined isotachophoretically without any pretreatment except for sample filtering and degassing. A capillary of 0.4 mm i.d. and 100 mm effective length made of fluorinated ethylene-propylene copolymer was filled with an electrolyte system consisting of 10 mmol L⁻¹ HCl + 11 mmol L⁻¹ imidazole, 0.15% (w/v) hydroxyethylcellulose, pH 6.0 (leading electrolyte) and 5 mmol L⁻¹ benzoic acid + 6 mmol L⁻¹ imidazole, pH 6.5 (terminating electrolyte). Separation was performed at a driving current of 80 μA and for detection current was decreased to 30 μA. Using contactless conductivity detection, the calibration curves in the tested concentration range up to 2.5 mmol L⁻¹ were linear for both metabisulfite and hydrosulfite complexes. The concentration detection limits for metabisulfite and hydrosulfite were 2.9 and 3.4 μmol L⁻¹, respectively. For 1 mmol L⁻¹ concentration, values of R.S.D. (n = 6) were 2.6% for hydrosulfite and 0.8% for metabisulfite. Isotachophoretic determination took about 20 min. The elaborated isotachophoretic procedure is simple to perform, sufficiently sensitive and accurate. In addition to this, low cost of analyses makes the method an alternative procedure to methods used so far for the determination of oxoanions of sulfur.     

Simple and fast spectrophotometric determination of H(2)O(2) in photo-Fenton reactions using metavanadate

This work proposes a spectrophotometric method for the determination of hydrogen peroxide during photodegradation reactions. The method is based on the reaction of H₂O₂ with amonium metavanadate in acidic medium, which results in the formation of a red-orange color peroxovanadium cation, with maximum absorbance at 450 nm. The method was optimized using the multivariate analysis providing the minimum concentration of vanadate (6.2 mmol L⁻¹) for the maximum absorbance signal. Under these conditions, the detection limit is 143 μmol L⁻¹. The reaction product showed to be very stable for samples of peroxide concentrations up to 3 mmol L⁻¹ at room temperature during 180 h. For higher concentrations however, samples must be kept refrigerated (4 °C) or diluted. The method showed no interference of Cl⁻ (0.2-1.3 mmol L⁻¹), NO₃⁻ (0.3-1.0 mmol L⁻¹), Fe³⁺ (0.2-1.2 mmol L⁻¹) and 2,4-dichlorophenol (DCP) (0.2-1.0 mmol L⁻¹). When compared to iodometric titration, the vanadate method showed a good agreament. The method was applied for the evaluation of peroxide consumption during photo-Fenton degradation of 2,4-dichlorophenol using blacklight irradiation.     

Sequential injection determination of orthophosphate as ion associate of 12-molybdophosphate with Astra Phloxine

A simple and fast reaction between 12-molybdophosphate heteropoly anion and the polymethine dye Astra Phloxine was used for the development of a new SIA method for the determination of orthophosphate. The suggested method has higher sensitivity and a broader calibration range than existing SIA methods. It can be used to detect phosphate in the range from 0.2 to 10 μmol L⁻¹ with a detection limit of 0.1 μmol L⁻¹ and an acceptable throughput of 20 samples h⁻¹. The comparably low molybdate (5.6 mmol L⁻¹) and dye (0.1 mmol L⁻¹) concentrations led to an improvement in the stability of the base line. Inter-day reproducibility was better than 5%, while the intra-day RSD was in the range 0.8-3.5%. The method was used for the analysis of natural water samples and phosphorus-containing chemicals having a low content of orthophosphate.     

A novel fused-silica capillary dropping mercury electrode with long drop-time and its application on determination of critical micelle concentration

A novel long drop time mercury electrode has been constructed from common fused-silica capillary (50 μm I.D., 360 μm E.D.). Proposed device provides reproducible mercury drops with typical lifetime 40-120 s. The electrode was used for a set of electrocapillary measurements aimed at determination of critical micelle concentration of anionic surfactants by a convection controlled drop-time technique. A critical micelle concentration of sodium dodecyl sulfate 5.6 ± 0.4 mmol L⁻¹ and 4.3 ± 0.4 mmol L⁻¹ were obtained in 1 mmol L⁻¹ and 5 mmol L⁻¹ phosphate buffer (pH 7.0), respectively. The values were comparable to those obtained from conductometric measurements under the same conditions (7.0 ± 0.1 mmol L⁻¹ and 5.2 ± 0.1 mmol L⁻¹, respectively) and the difference was explained in accordance with theory of hemi-micelle formation.     

Elimination of interferences in determination of platinum and palladium in environmental samples by inductively coupled plasma mass spectrometry

Various approaches were evaluated in order to eliminate the spectral interferences noted when Pt and Pd has to be determined in environmental dust samples by ICP-MS. The chemical separation of Pt and Pd from the matrix components on ion-exchange resins was applied. The performance of cation-exchange resins (Dowex 50 WX-8, Dowex 50 WX-2, Dowex HCR-S, Varion KS, Cellex-P) for the separation of interfering ions was then examined. It was found that Dowex 50 WX-8 shows best performance. The effects of mass, mesh number of resin and concentration of Cl⁻ ions on matrix separation were also studied. Another approach was to use the anion-exchange sorbent Cellex-T, which allows almost total retention of both analytes followed by their elution with 0.1 mol L⁻¹ thiourea in 1 mol L⁻¹ HCl. This procedure however can be used only for platinum determination by ICP-MS. The accuracy of proposed procedures was confirmed by the analysis of certified material BCR-723, and then it was used for determination Pt and Pd in samples of road dust.     

Determination of brominated phenols in water samples by on-line coupled isotachophoresis with capillary zone electrophoresis

A method for determination of nine brominated phenols as environmental risk compounds was developed by on-line coupled capillary isotachophoresis and capillary zone electrophoresis (ITP–CZE). For ITP step, 1 × 10⁻² mol L⁻¹ hydrochloric acid with 3 × 10⁻² mol L⁻¹ ammediol pH 9.1 was used as the leading electrolyte, and 3 × 10⁻² mol L⁻¹ β-alanine with 2 × 10⁻² mol L⁻¹ sodium hydroxide pH 10.05 was used as the terminating electrolyte. As the background electrolyte for CZE separation, 2.5 × 10⁻² mol L⁻¹ β-alanine with 2.5 × 10⁻² mol L⁻¹ lysine pH 9.6 was used. All electrolytes contained 0.05% or 0.1% (m/v) hydroxyethylcellulose to suppress the electroosmotic flow. UV detection at wavelength 220 nm was used. Detection limits in order of tens of nmol L⁻¹ were achieved. Good repeatability of migration times (less than 0.33% RSD) and good repeatability of peak areas (less than 7.19% RSD) at concentration level 5 × 10⁻⁸ mol L⁻¹ were observed. Developed ITP–CZE method was applied to determination of brominated phenols in spiked tap and river water samples.     

Application of sequential injection-square wave voltammetry (SI-SWV) to study the adsorption of atrazine onto a tropical soil sample

Square wave voltammetry automated by sequential injection analysis was applied to determine the Freundlich adsorption coefficients for the adsorption of atrazine onto a clay rich soil. The detection limit in soil extracts was between 0.18 and 0.48 μmol L⁻¹, depending on the medium used to prepare the extracts (0.010 mol L⁻¹ KCl, CaCl₂ or HNO₃ and 0.0050 mol L⁻¹ H₂SO₄), all of them conditioned in 40 mmol L⁻¹ Britton-Robinson buffer at pH 2.0 in presence of 0.25 mol L⁻¹ NaNO₃. Also in soil extracts the linear dynamic range was between 1.16 and 18.5 μmol L⁻¹ (0.25-4.0 μg mL⁻¹), with a sampling frequency of 190 h⁻¹. The K_f Freundlich adsorption coefficient was 3.8 ± 0.2 μmol^1−1/n Lⁿ kg⁻¹ in medium of 0.010 mol L⁻¹ KCl or CaCl₂, but increased to 7.7 ± 0.1 and 9.0 ± 0.3 μmol^1−1/n Lⁿ kg⁻¹ in 0.010 mol L⁻¹ HNO₃ and 0.0050 mol L⁻¹ H₂SO₄, respectively. The increase of K_f was related to the decrease of pH from 6.4-6.7 in KCl and CaCl₂ to 3.7-4.0 in presence of HNO₃ or H₂SO₄, which favors protonation of atrazine, facilitating electrostatic attractions with negative charges of the clay components of the soil. The 1/n parameters were between 0.76 and 0.86, indicating that the isotherms are not linear, suggesting the occurrence of chemisorption at specific adsorption sites. No statistically significant differences were observed in comparison to the adsorption coefficients obtained by HPLC. The advantage of the proposed SI-SWV method is the great saving of reagent because it does not use organic solvent as in the case of HPLC (50% (v/v) acetonitrile in the mobile phase). Additionally the start up of SI-SWV is immediate (no column conditioning necessary) and the analysis time is only 19 s.     

Differential pulse voltammetric simultaneous determination of noradrenalin and acetaminophen using a hematoxylin biosensor

A highly efficient noradrenalin (NA) biosensor was fabricated on the basis of hematoxylin electrodeposited on a glassy carbon electrode, GCE. The cyclic voltammetric responses of the hematoxylin biosensor at various scan rates, which were obtained in a 0.25 mmol L⁻¹ NA solution, showed the characteristic shape typical of an EC_cat process. The kinetic parameters such as electron transfer coefficient, α, the catalytic electron transfer rate constant, k′, and the standard catalytic electron transfer rate constant, k⁰, for oxidation of NA at the hematoxylin biosensor surface were estimated using cyclic and RDE voltammetry. The peaks of differential pulse voltammetric (DPV) for NA and acetaminophen (AC) oxidation at the hematoxylin biosensor surface were clearly separated from each other when they co-exited in the physiological pH (pH 7.0). It was, therefore, possible to simultaneously determine NA and AC in the samples at a hematoxylin biosensor. Linear calibration curves were obtained for 5.0 × 10⁻¹ to 65.40 μmol L⁻¹ and 65.40-274.20 μmol L⁻¹ of NA, and for 12.00-59.10 μmol L⁻¹ and 59.10-261.70 μmol L⁻¹ of AC. The sensitivities of the biosensor to NA in the absence and presence of AC were found virtually the same, which indicates the fact that the electrocatalytic oxidation processes of NA are independent of AC and, therefore, simultaneous or independent measurements of the two analytes (NA and AC) are possible without any interference. The results of 16 successive measurements show an average voltammetric peak current of 1.13 ± 0.03 μA for an electrolyte solution containing 5.00 μmol L⁻¹ NA. The hematoxylin biosensor has been satisfactorily used for the determination of NA and AC in pharmaceutical formulations. The results obtained, using the biosensor, are in very good agreement with those declared in the label of pharmaceutical inhalation products.     

An analytical application of the electrocatalysis of the iodate reduction at tungsten oxide films

Films of non-stoichiometric tungsten oxides have been deposited onto glassy carbon surfaces by electrodeposition from acidic W(VI) solutions and the chemical stability of these oxides was investigated by using the electrochemical quartz crystal microbalance. At these modified surfaces, rotating disc electrode voltammetric experiments indicated that iodate is electrocatalytically reduced in a mass-transport controlled process. The influence of the film thickness on the response to iodate was investigated and the results indicated a linear relationship between catalytic current and film thickness for relatively thin oxide layers. The modified electrode was employed successfully as an amperometric sensor for iodate in a flow injection apparatus. The linear response of the developed method is extended from 5 μmol L⁻¹ to 5 mmol L⁻¹ iodate with a limit of detection (signal-to-noise = 3) of 1.2 μmol L⁻¹. The repeatability of the method for 41 injections of a 1 mmol L⁻¹ iodate solution was 0.8% and the throughput was determined as 123 h⁻¹. Interference from other oxidant anions such as nitrate and nitrite was not noticeable, whereas bromate and chlorate interfere at slight levels. The method was used in the determination of the iodate content in table salt samples.     

Linear polyamines as carriers in thiocyanate-selective membrane electrodes

The polyamines, octyl-[2-(2-octylamino-ethylamino)-ethyl]-amine (L¹) and octyl-{2-[2-(2-octylamino-ethylamino)-ethylamino]-ethyl}-amine (L²), have been used as anion ionophores in PVC-based membrane ion-selective electrodes. Different electrodes were prepared containing L¹, or L², and o-nitrophenyl octyl ether (NPOE) or bis(2-ethylhexyl)sebacate (DOS) as plasticizers. The response of the electrodes was tested in two different buffers, HEPES-KOH (pH 7) and MES-KOH (pH 5.6). Electrodes containing L¹ and L² with NPOE (E1 and E2, respectively) showed a Nernstian response for thiocyanate with a good response time. The detection limit, linear range and slope for electrode E1 were 3.8 × 10⁻⁶ mol dm⁻³, 1 × 10⁻⁵ to 1 × 10⁻¹ mol dm⁻³ and −57.2 mV decade⁻¹ at pH 5.6 and 4.47 × 10⁻⁶ mol dm⁻³, 1.95 × 10⁻⁵ to 1 × 10⁻¹ mol dm⁻³ and −58.1 mV decade⁻¹ at pH 7.0. For electrode E2 the detection limit, linear range and slope found were 2.63 × 10⁻⁶ mol dm⁻³, 7.94 × 10⁻⁶ to 1 × 10⁻¹ mol dm⁻³ and −58.5 mV decade⁻¹ at pH 5.6 and 1.23 × 10⁻⁵ mol dm⁻³, 7.95 × 10⁻⁵ to 1 × 10⁻¹ mol dm⁻³ and −46.0 mV decade⁻¹ at pH 7. In contrast, electrodes containing DOS as plasticizers gave only response at pH 5.6 (detection limit, linear range and slope at pH 5.6 were 3.16 × 10⁻⁵ mol dm⁻³, 1 × 10⁻⁴ to 1 × 10⁻¹ mol dm⁻³ and −52.6 mV decade⁻¹). Selectivity coefficients for different anions with respect to thiocyanate were calculated. The electrode E2 at pH 5.6 was also used for the determination of SCN⁻ by potentiometric titrations with Ag⁺ ions with good results. The electrode E2 was also used to determine concentrations of thiocyanate in biological samples.     

A sensitive post-column photochemical derivatization/fluorimetric detection system for HPLC determination of bisphosphonates

A new reversed-phase ion-pair high-performance liquid chromatographic (HPLC) method has been developed for the determination of the following bisphosphonic acids: alendronic acid (ALEN), etidronic acid (ETID), ibandronic acid (IBAN) and risedronic acid (RISE). Separation was achieved on a C₁₈ column using a mixture of 50 mmol L⁻¹ borate buffer pH 9.0 containing 0.25 mmol L⁻¹ tetrabutylammonium chloride and 0.5 mmol L⁻¹ EDTA and acetonitrile (97:3) as the mobile phase. The sensitive detection of the above bisphosphonic acids was based on their oxidation to orthophosphate by the on-line peroxydisulfate-assisted photolysis followed by post-column reaction with molybdate to yield phosphomolybdate. This subsequently reacted with thiamine to generate thiochrome and, finally, the fluorescence of thiochrome was measured at 440 nm with excitation at 375 nm. The developed method is precise with a mean relative standard deviation of 1.3%, sensitive (with a detection limit at the nmol L⁻¹ level), accurate, specific, rapid (analysis time approximately 13 min) and inexpensive because to the low cost of the reagents. The assay was applied to the analysis of the four bisphosphonic acids in commercial dosage formulations, in which the excipients did not interfere with the determination. The method was also applied to the determination of etidronate, risedronate and ibandronate in human urine. Sample preparation involves precipitation of the analytes from urine along with endogenous phosphates such as calcium salts by addition of calcium chloride at alkaline pH and dissolution of the precipitate in 0.05 mol L⁻¹ ethylene glycol-bis(β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid.     

Tris(2,2'-bipyridyl)ruthenium(II)-Zirconia-Nafion composite modified electrode applied as solid-state electrochemiluminescence detector on electrophoretic microchip for detection of pharmaceuticals of tramadol, lidocaine and ofloxacin

Tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺)-Zirconia-Nafion composite modified glassy carbon disk electrode as a solid-state electrochemiluminescence (ECL) detector is successfully applied to an electrophoretic microchip system with a wall-jet configuration. Pharmaceuticals such as tramadol, lidocaine and ofloxacin were selected to characterize the performance of this microchip capillary electrophoresis (CE)-ECL detection system. Voltammetric and ECL behaviors of immobilized Ru(bpy)₃²⁺ were investigated in lidocaine system. Influences of the separation electric field to cyclic voltammograms (CVs) of the immobilized Ru(bpy)₃²⁺ were also investigated. Tramadol, lidocaine and ofloxacin can be baseline separated without any additives. The detection limits (S/N = 3) were 2.5 × 10⁻⁵ mol L⁻¹ for tramadol, 5.0 × 10⁻⁶ mol L⁻¹ for lidocaine, 1.0 × 10⁻⁵ mol L⁻¹ for ofloxacin under the sample injection of picoliters, and the linear ranges were from 5.0 × 10⁻⁵ to 2.5 × 10⁻³ mol L⁻¹ for tramadol, 1.0 × 10⁻⁵ to 1.0 × 10⁻³ mol L⁻¹ for lidocaine, and 1.0 × 10⁻⁵ to 2.5 × 10⁻³ mol L⁻¹ for ofloxacin, respectively.     

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.     

Implementing stepwise solvent elution in sequential injection chromatography for fluorimetric determination of intracellular free amino acids in the microalgae Tetraselmis gracilis

The concept of sequential injection chromatography (SIC) was exploited to automate the fluorimetric determination of amino acids after pre-column derivatization with o-phthaldialdehyde (OPA) in presence of 2-mercaptoethanol (2MCE) using a reverse phase monolithic C₁₈ stationary phase. The method is low-priced and based on five steps of isocratic elutions. The first step employs the mixture methanol: tetrahydrofuran: 10 mmol L⁻¹ phosphate buffer (pH 7.2) at the volumetric ratio of 8:1:91; the other steps use methanol: 10 mmol L⁻¹ phosphate buffer (pH 7.2) at volumetric ratios of 20:80, 35:65, 50:50 and 65:35. At a flow rate of 10 μL s⁻¹ a 25 mm long-column was able to separate aspartic acid (Asp), glutamic acid (Glu), asparagine (Asn), serine (Ser), glutamine (Gln), glycine (Gly), threonine (Thr), citruline (Ctr), arginine (Arg), alanine (Ala), tyrosine (Tyr), phenylalanine (Phe), ornithine (Orn) and lysine (Lys) with resolution >1.2 as well as methionine (Met) and valine (Val) with resolution of 0.6. Under these conditions isoleucine (Ile) and leucine (Leu) co-eluted. The entire cycle of amino acids derivatization, chromatographic separation and column conditioning at the end of separation lasted 25 min. At a flow rate of 40 μL s⁻¹ such time was reduced to 10 min at the cost of resolution worsening for the pairs Ctr/Arg and Orn/Lys. The detection limits varied from 0.092 μmol L⁻¹ for Tyr to 0.51 μmol L⁻¹ for Orn. The method was successfully applied to the determination of intracellular free amino acids in the green alga Tetraselmis gracilis during a period of seven days of cultivation. Samples spiked with known amounts of amino acids resulted in recoveries between 94 and 112%.     

Speciation of selenomethionine and selenocystine using online micro-column containing Cu(II) loaded nanometer-sized Al2O3 coupled with ICP-MS detection

A flow injection online speciation procedure by using micro-column packed with Cu(II) loaded nanometer-sized Al₂O₃ coupled to inductively coupled plasma mass spectrometry (ICP-MS) for the separation and determination of selenomethionine (SeMet) and selenocystine (SeCys₂) has been developed. The main factors affecting the separation and preconcentration of SeMet and SeCys₂ including pH value, sample flow rate, eluent concentration, eluent volume and flow rate, and interfering ions have been investigated. It was found that SeCys₂ could be selectively retained by micro-column packed with Cu(II) loaded nanometer-sized Al₂O₃ at pH 4.0, and the retained SeCys₂ could be eluted by 1.0 mol L⁻¹ HNO₃, while SeMet was not retained and passed through the micro-column directly at this pH. Both SeMet and SeCys₂ could be quantitatively adsorbed by the micro-column at pH 9.0, and the retained SeMet and SeCys₂ could be easily eluted with 1.0 mol L⁻¹ HNO₃. The content of SeMet was obtained by subtracting the SeCys₂ from the total content of seleno amino acids. With the enrichment factor of 7.8 and 7.7, the limits of detection (LODs) for SeMet and SeCys₂ were found to be 24 pg Se mL⁻¹ and 21 pg Se mL⁻¹, respectively. The relative standard deviations (RSDs) for SeCys₂ and SeMet with seven replicate determinations of 1.0 ng mL⁻¹ SeMet and SeCys₂, were 2.1% and 1.6%, respectively, the sampling frequency of 8 h⁻¹ was obtained. The proposed method was applied to the speciation of SeMet and SeCys₂ in selenized yeast, human urine and serum with satisfactory results.     

Flow injection analysis of ethyl xanthate by in-line dialysis and UV spectrophotometric detection

A simple and sensitive spectrophotometric flow method for determination of low concentrations of the flotation collector O-ethyldithiocarbonate (ethyl xanthate, CH₃CH₂-O-CS₂⁻) in solutions is described. The method is based on ethyl xanthate detection at 301 nm in medium of NaOH 50 mmol L⁻¹. By injection of 200 μL of sample, the analytical method shows linear response for the ethyl xanthate concentration from 0.5 up to 500 μmol L⁻¹. Successive injections of 4 μmol L⁻¹ ethyl xanthate (n = 23) show a coefficient of variation lower than 0.6%, denoting high repeatability. The detection limit is 0.3 μmol L⁻¹. At a flow rate of 2.0 mL min⁻¹, a frequency of 120 injections/h of ethyl xanthate can be attained. By introduction of a tangential dialysis cell in the FIA system, the manual sample filtration step with 0.22 μm filter was eliminated and the residual interference of suspended material, was completely overcome even for unfiltered sludge suspension samples, an important advantage that compensates for the frequency reduction to 25 injections/h elevation and detection limit elevation to 2 μmol L⁻¹, still outreaching for many applications. Potential applications of the method embrace the at line determination of ethyl xanthate in the ore processing industry, control of the concentration at its optimal level during the flotation process, as well as monitoring of residues in the effluents.     

A new high-speed hollow fiber based liquid phase microextraction method using volatile organic solvent for determination of aromatic amines in environmental water samples prior to high-performance liquid chromatography

A new and fast hollow fiber based liquid phase microextraction (HF-LPME) method using volatile organic solvents coupled with high-performance liquid chromatography (HPLC) was developed for determination of aromatic amines in the environmental water samples. Analytes including 3-nitroaniline, 3-chloroaniline and 4-bromoaniline were extracted from 6 mL basic aqueous sample solution (donor phase, NaOH 1 mol L⁻¹) into the thin film of organic solvent that surrounded and impregnated the pores of the polypropylene hollow fiber wall (toluene, 20 μL), then back-extracted into the 6 μL acidified aqueous solution (acceptor phase, HCl 0.5 mol L⁻¹) in the lumen of the two-end sealed hollow fiber. After the extraction, 5 μL of the acceptor phase was withdrawn into the syringe and injected directly into the HPLC system for the analysis. The parameters influencing the extraction efficiency including the kind of organic solvent and its volume, composition of donor and acceptor phases and the volume ratio between them, extraction time, stirring rate, salt addition and the effect of the analyte complexation with 18-crown-6 ether were investigated and optimized. Under the optimal conditions (donor phase: 6 mL of 1 mol L⁻¹ NaOH with 10% NaCl; organic phase: 20 μL of toluene; acceptor phase: 6 μL of 0.5 mol L⁻¹ HCl and 600 m mol L⁻¹ 18-crown-6 ether; pre-extraction and back-extraction times: 75 s and 10 min, respectively; stirring rate: 800 rpm), the obtained EFs were between 259 and 674, dynamic linear ranges were 0.1-1000 μg L⁻¹ (R > 0.9991), and also the limits of detection were in the range of 0.01-0.1 μg L⁻¹. The proposed procedure worked very well for real environmental water samples with microgram per liter level of the analytes, and good relative recoveries (91-102%) were obtained for the spiked sample solutions.     

Development of a spectrophotometric Sequential Injection Analysis (SIA) procedure for determination of ammonium: A Response Surface Methodology (RSM) approach

This paper describes the optimization and use of a Sequential Injection Analysis (SIA) procedure for ammonium determination in waters. Response Surface Methodology (RSM) was used as a tool for optimization of a procedure based on the modified Berthelot reaction. The SIA system was designed to (i) prepare the reaction media by injecting an air-segmented zone containing the reagents in a mixing chamber, (ii) to aspirate the mixture back to the holding coil after homogenization, (iii) drive it to a thermostated reaction coil, where the flow is stopped for a previously established time, and (iv) to pump the mixture toward the detector flow cell for the spectrophotometric measurements. Using a 100 μmol L^− 1 ammonium solution, the following factors were considered for optimization: reaction temperature (25 - 45 °C), reaction time (30 - 90 s), hypochlorite concentration (20 - 40 mmol L^− 1), nitroprusside concentration (10 - 40 mmol L^− 1) and salicylate concentration (0.1 - 0.3 mol L^− 1). The proposed system fed the statistical program with absorbance data for fast construction of response surface plots. After optimization of the method, figures of merit were evaluated, as well as the ammonium concentration in some water samples. No evidence of statistical difference was observed in the results obtained by the proposed method in comparison to those obtained by a reference method based on the phenol reaction.     

A renewable copper electrode as an amperometric flow detector for nitrate determination in mineral water and soft drink samples

A novel approach was developed for nitrate analysis in a FIA configuration with amperometric detection (E = −0.48 V). Sensitive and reproducible current measurements were achieved by using a copper electrode activated with a controlled potential protocol. The response of the FIA amperometric method was linear over the range from 0.1 to 2.5 mmol L⁻¹ nitrate with a detection limit of 4.2 μmol L⁻¹ (S/N = 3). The repeatability of measurements was determined as 4.7% (n = 9) at the best conditions (flow rate: 3.0 mL min⁻¹, sample volume: 150 μL and nitrate concentration: 0.5 mmol L⁻¹) with a sampling rate of 60 samples h⁻¹. The method was employed for the determination of nitrate in mineral water and soft drink samples and the results were in agreement with those obtained by using a recommended procedure. Studies towards a selective monitoring of nitrite were also performed in samples containing nitrate by carrying out measurements at a less negative potential (−0.20 V).