A novel analytical system involving hydride generation and gold-coated W-coil trapping atomic absorption spectrometry for selenium determination at ng l level

A novel analytical technique was developed where gaseous hydrogen selenide formed by sodium tetrahydroborate reduction is transported to and trapped on a resistively heated gold-coated W-coil atom trap for in situ preconcentration. Gold coating on W-coil was prepared by using an organic solution of Au. The atom trap is held at 165 °C during the collection stage and is heated up to 675 °C for revolatilization; analyte species formed are transported to an externally heated quartz T-tube where the atomization takes place and the transient signal is obtained. The carrier gas consisted of 112.5 ml min^− 1 Ar with 75 ml min^− 1 H₂ during the collection step and 112.5 ml min^− 1 Ar with 450 ml min^− 1 H₂ in the revolatilization step. The half width of the transient signal obtained is less than 0.5 s. The RSD for the measurements was found to be 3.9% (n = 11) for 0.10 µg l^− 1 Se using peak height measurements.     

Silica modified with zirconium oxide for on-line determination of inorganic arsenic using a hydride generation-atomic absorption system

In the present work, an on-line pre-concentration system, using SiO₂/ZrO₂ as solid phase adsorbent, for the determination of low concentrations of arsenic was developed.In this procedure, total inorganic arsenic present in the sample is reduced to As (III) with l-cysteine and the solution is passed into a glass column (?_i = 3 mm; h = 35 mm) containing 70 mg of SiO₂/ZrO₂ (100-230 mesh) to retain the As (III), with the solution flowing at 3.2 mL min⁻¹. After 2 min, the concentrated species are eluted with 3 mol L⁻¹ HCl (3.2 mL min⁻¹) loading a 150 μL loop while a 1.0% (m/v) sodium borohydride solution loads the other loop of a FI-HG AAS system. The elution step is carried out during 7 s and, at the same time, the SiO₂/ZrO₂ phase is regenerated for the next concentration cycle. The arsine generated is carried with N₂ (flow rate = 90 mL min⁻¹) to a quartz cell where the electrothermal atomization process occurs.Under these conditions, a 20-fold enrichment factor is obtained considering the increase of sensitivity in the analytical curve after the concentration step. The limits of detection and quantification were 0.05 and 0.35 μg L⁻¹, respectively, with an injection frequency of about 28 h⁻¹ and relative standard deviation lower than 8%. Four metallurgical reference materials were analyzed with the proposed method after their acid dissolution. The results obtained were in good agreement with certified values.     

Evaluation of liquid chromatography inductively coupled plasma mass spectrometry for arsenic speciation in water from industrial treatment of shale

This work describes an arsenic speciation analysis in aqueous effluent from a shale industrial plant using liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC–ICP–MS). Arsenic species have been separated through an anion-exchange column and several parameters investigated, such as retention time, pH, flow rate and concentration of the mobile phase (ammonium carbonate), chloride interference and column conditioning time. The best conditions have been found by fixing the pH of the mobile phase at 8.7. Keeping the mobile phase flow rate at 1.5 ml min^− 1, arsenic species were separated by varying the concentration of the mobile phase and the time of elution, as follow: 1.5 mmol l^− 1 for 10 min, 12 mmol l^− 1 for 10 min and 20 mmol l^− 1 for 10 min, respectively. Up to 13 As species present in the samples were separated under these conditions and the following species could be identified and quantified: arsenite [As(III)], dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and arsenate [As(V)]. The limits of detection of the LC–ICP–MS method were 0.02, 0.06, 0.04 and 0.10 μg l^− 1 of As(III), DMA, MMA, and As(V), respectively. The concentration of these species in the samples were from 3.7 to 6.4 μg l^− 1, 6.9 to 13.2 μg l^− 1, 100 to 142 μg l^− 1 and 808 to 1363 μg l^− 1 for As(III), DMA, MMA and As(V), respectively. The accuracy, evaluated by recovery tests, varied from 94 to 105% and the precision, evaluated by the relative standard deviation was typically lower than 10%.     

Single-run ion chromatographic separation of inorganic and low-molecular-mass organic anions under isocratic elution: Application to environmental samples

For the isocratic ion chromatography (IC) separation of low-molecular-mass organic acids and inorganic anions three different anion-exchange columns were studied: IonPac AS14 (9 μm particle size), Allsep A-2 (7 μm particle size), and IC SI-50 4E (5 μm particle size). A complete baseline separation for all analyzed anions (i.e., F⁻, acetate, formate, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, HPO₄²⁻ and SO₄²⁻) in one analytical cycle of shorter than 17 min was achieved on the IC SI-50 4E column, using an eluent mixture of 3.2 mM Na₂CO₃ and 1.0 mM NaHCO₃ with a flow rate of 1.0 mL min⁻¹. On the IonPac AS14 column, it was possible to separate acetate from inorganic anions in one run (i.e., less than 9 min), but not formate, under the following conditions: 3.5 mM Na₂CO₃ plus 1.0 mM NaHCO₃ with a flow rate of 1.2 mL min⁻¹. Therefore, it was necessary to adapt a second run with a 2.0 mM Na₂B₄O₇ solution as an eluent under a flow rate of 0.8 mL min⁻¹ for the separation of organic ions, which considerably enlarged the analysis time. For the Allsep A-2 column, using an eluent mixture of 1.2 mM Na₂CO₃ plus 1.5 mM NaHCO₃ with a flow rate of 1.6 mL min⁻¹, it was possible to separate almost all anions in one run within 25 min, except the fluoride-acetate critical pair. A Certified Multianion Standard Solution PRIMUS for IC was used for the validation of the analytical methods. The lowest RSDs (less than 1%) and the best LODs (0.02, 0.2, 0.16, 0.11, 0.06, 0.05, 0.04, 0.14 and 0.09 mg L⁻¹ for F⁻, Ac⁻, For⁻, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, HPO₄²⁻ and SO₄²⁻, respectively) were achieved using the IC SI-50 4E column. This column was applied for the separation of concerned ions in environmental precipitation samples such as snow, hail and rainwater.     

Sorption characteristics and separation of tellurium ions from aqueous solutions using nano-TiO2

Titanium dioxide nanoparticles (nano-TiO₂) were employed for the sorption of Te(IV) ions from aqueous solution. A detailed study of the process was performed by varying the sorption time, pH, and temperature. The sorption was found to be fast, equilibrium was reached within 8 min. When the concentration of Te(IV) was below 40 mg L⁻¹, at least 97% of tellurium was adsorbed by nano-TiO₂ in the pH range of 1-2 and 8-9. The sorbed Te(IV) ions were desorbed with 2.0 mL of 0.5 mol L⁻¹ NaOH. The sorption data could be well interpreted by the Langmuir model with the maximum adsorption capacity of 32.75 mg g⁻¹ (20 ± 0.1 °C) of Te(IV) on nano-TiO₂. The kinetics and thermodynamics of the sorption of Te(IV) onto nano-TiO₂ were also studied. The kinetic experimental data properly correlated with the second-order kinetic model (k₂ = 0.0368 g mg⁻¹ min⁻¹, 293 K). The overall rate process appeared to be influenced by both boundary layer diffusion and intra-particle diffusion. The mean energy of adsorption was calculated to be 17.41 kJ mol⁻¹ from the Dubinin-Radushkevich (D-R) adsorption isotherm at room temperature. Moreover, the thermodynamic parameters for the sorption were estimated, and the ΔH⁰ and ΔG⁰ values indicated the exothermic and spontaneous nature of the sorption process, respectively. Finally, Nano-TiO₂ as sorbent was successfully applied to the separation of Te(IV) from the environmental samples with satisfactory results (recoveries >95%, relative standard deviations was 2.0%).     

Cu(II)-imprinted styrene-divinylbenzene beads as a new sorbent for flow injection-flame atomic absorption determination of copper

The paper reports preparation and analytical features of a new Cu(II)-imprinted polymer, based on salen-OMe ligand 2,2′-[ethane-1,2-diylbis(nitrilo(E)methylylidene)]bis(6-allyl-4-methoxyphenol) and styrene-divinylbenzene matrix, as well as its application to on-line preconcentration and flame atomic absorption determination of copper. Sorbent beads (average diameter of 60-80 µm) were obtained using suspension polymerization technique and employed as a column filling. Copper sorption was the most effective at pH 6.8, whereas the highest elution effectiveness was observed when 0.5% HNO₃ was applied. The sorbent exhibited good long-term stability and acid resistance. Enrichment factor (EF) of 12 was found for 60 s loading time and loading flow rate of 4 mL min^− 1. EF value may be further increased by expanding the loading time and/or flow rate. Batch sorbent capacity in optimal pH conditions was found to be 0.16 mmol g^− 1 (9.55 mg g^− 1) of a dry polymer. Calcium(II) turned out to be the only significant interferent. Cadmium(II), silver(I), nickel(II), zinc(II) in concentrations lower than about 1 mg L^− 1 did not disturb copper(II) preconcentration. Different calibration methods such as: set of standards method (SSM), standard addition method (SAM) and combinatory calibration method (CCM) were employed for copper(II) determination in tap water, spring mineral water and certified reference material. Analysis of EU-H-3 reference material confirmed good accuracy of the proposed method. Relative standard deviation (RSD) was 3.2 for standard addition method and 2.8% for set of standard calibration method. Detection limit for sample consumption 16 mL was 1.03 and 1.07 µgL^-1 respectively.     

A microwave-assisted sequential extraction of water and dilute acid soluble arsenic species from marine plant and animal tissues

This paper describes the use of dilute nitric acid for the extraction and quantification of arsenic species. A number of extractants (e.g. water, 1.5 M orthophosphoric acid, methanol-water and dilute nitric acid) were tested for the extraction of arsenic from marine biological samples, such as plants that have proved difficult to quantitatively extract. Dilute 2% (v/v) nitric acid was found to give the highest recoveries of arsenic overall and was chosen for further optimisation. The optimal extraction conditions for arsenic were 2% (v/v) HNO₃, 6 min⁻¹, 90 °C. Arsenic species were found to be stable under the optimised conditions with the exception of the arsenoriboses which degraded to a product eluting at the same retention time as glycerol arsenoribose. Good agreement was found between the 2% (v/v) HNO₃ extraction and the methanol-water extraction for the certified reference material DORM-2 (AB 17.1 and 16.2 μg g⁻¹, respectively, and TETRA 0.27 and 0.25 μg g⁻¹, respectively), which were in close agreement with the certified concentrations of AB 16.4 ± 1.1 μg g⁻¹ and TETRA 0.248 ± 0.054 μg g⁻¹.To preserve the integrity of arsenic species, a sequential extraction technique was developed where the previously methanol-water extracted pellet was further extracted with 2% (v/v) HNO₃ under the optimised conditions. Increases in arsenic recoveries between 13% and 36% were found and speciation of this faction revealed that only inorganic and simple methylated species were extracted.     

Non-chromatographic determination of ultratraces of V(V) and V(IV) based on a double column solid phase extraction flow injection system coupled to electrothermal atomic absorption spectrometry

In this work, a non-chromatographic procedure for the on-line determination of ultratraces of V(V) and V(IV) is presented. The method involves a solid phase extraction-flow injection system coupled to electrothermal atomic absorption spectrometry (SPE-FI-ETAAS). The system holds two microcolumns (MC) set in parallel and filled with lab-made mesoporous silica functionalized with 3-aminopropyltriethoxy silane (APS) and mesoporous silica MCM-41, respectively. The pre-concentration of V(V) is performed by sorption onto the first MC (C1) filled with APS at pH 3, whilst that of V(IV) is performed by sorption onto the second column (C2) filled with mesoporous silica MCM-41 at pH 5. Aqueous samples containing both analytes are loaded and, after pre-concentration (pre-concentration factor PCF = 10, sorption flow rate = 1 mL min⁻¹, sorption time = 10 min), they are eluted in separate vessels with hydroxylammonium chloride (HC) 0.1 mol L⁻¹ in HCl 0.5 mol L⁻¹ (elution volume = 1 mL, elution flow rate = 0.5 mL min⁻¹). Afterwards, both analytes are determined through ETAAS with graphite furnace. Under optimized conditions, the main analytical figures of merit for V(V) and V(IV) are, respectively: detection limits (3 s): 0.5 and 0.6 μg L⁻¹, linear range: 2-100 μg L⁻¹ (both analytes), sensitivity: 0.015 and 0.013 μg⁻¹ L and sample throughput: 6 h⁻¹ (both analytes). Recoveries of both species were assayed in different water samples. Validation was performed through certified reference materials for ultratraces of total vanadium in river water.     

Highly selective preconcentration of Cu(II) from seawater and water samples using amidoamidoxime silica

Chemically modified silica containing amidoamidoxime group was studied as a sorbent for solid-phase extraction (SPE) and preconcentration of Cu(II) prior to determination by flame atomic absorption spectrometry (FAAS). The sorbent showed an extremely high selectivity towards Cu(II) in the pH range of 4-6, while the extraction of Pb(II), Cd(II), Ni(II) and Co(II) was low. The adsorption isotherm followed the Langmuir model and the maximum sorption capacity of 0.0163 mmol Cu(II) g⁻¹ was achieved. In the flow system, Cu(II) was completely retained on a column containing 40 mg of the modified silica at the flow rate of 4.0 mL min⁻¹ and quantitatively eluted by 5 mL of 1% (v/v) HNO₃. No interference from Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻ and SO₄²⁻ at 10, 100 and 1000 mg L⁻¹ was observed. When applied for preconcentration and determination of Cu(II) in tap water, pond water, and seawater, the recoveries were 96, 101, and 95%, respectively, with high precision (% relative standard deviation (R.S.D.) < 4) and low method detection limit (9 μg L⁻¹).     

Modified mesoporous silica materials for on-line separation and preconcentration of hexavalent chromium using a microcolumn coupled with flame atomic absorption spectrometry

A modified SBA-15 mesoporous silica material NH₂-SBA-15 was synthesized successfully by grafting γ-aminopropyl-triethoxysilane. The material was characterized using transmission electron microscopy (TEM) and Fourier transform infrared/Raman (FT-IR/Raman) spectroscopy, and used for the first time in a flow injection on-line solid phase extraction (SPE) coupled with flame atomic absorption spectrometry (FAAS) to detect trace Cr (VI). Effective sorption of Cr (VI) was achieved at pH 2.0 with no interference from Cr (III) and other ions and 0.5 mol L⁻¹ NH₃·H₂O solution was found optimal for the complete elution of Cr (VI). An enrichment factor of 44 and was achieved under optimized experimental conditions at a sample loading of 2.0 mL min⁻¹ sample loading (300 s) and an elution flow rate of 2.0 mL min⁻¹ (24 s). The precision of the 11 replicate Cr (VI) measurements was 2.1% at the 100 μg L⁻¹ level with a detection limit of 0.2 μg L⁻¹ (3 s, n = 10) using the FAAS. The developed method was successfully applied to trace chromium determination in waste water. The accuracy was validated using a certified reference material of riverine water (GBW08607).     

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.     

Cellulose microfiber functionalized with N,N'-bis (2-aminoethyl)-1,2-ethanediamine as a solid sorbent for the fast preconcentration of Cd(II) in flow system analysis

The present paper describes the synthesis of a new chemically modified cellulose microfiber through oxidation with sodium periodate and functionalization with N,N′-bis (2-aminoethyl)-1,2-ethanediamine for the fast and selective preconcentration of Cd(II) ions in flow system analysis. The new sorbentsorbent was characterized by FTIR, SEM, and surface area values. The uptake behavior of Cd(II) ions onto this sorbent was evaluated from kinetic data, pseudo-first-order and pseudo-second-order models, as well as from Langmuir, Freundlich and Langmuir-Freundlich adsorption isotherms. The maximum sorption capacity of 4.59 mg g⁻¹ was estimated by the Langmuir-Freundlich model with fast kinetics for the sorption of Cd(II) described by the pseudo-second-order kinetic model. After characterization, the sorbent was packed in a mini-column, and a fast flow injection preconcentration system for Cd(II) determination by FAAS was developed. The best Cd(II) preconcentration condition, obtained by means of factorial design and response surface methodology, was achieved at pH 9.36 and a flow rate of 10 mL min⁻¹ followed by elution with 1.0 mol L⁻¹ nitric acid. By using 78 s preconcentration time, fast and highly sensitive determination of Cd(II) ions could be achieved with a limit of quantification of 0.20 μg L⁻¹, preconcentration factor of 26, consumption index of 0.5 mL, concentration efficiency of 20 min⁻¹, and sample throughput of 39 h⁻¹. The repeatability for 10 replicate determinations was found to be 7.8 and 2.5% for Cd(II) ion concentrations of 5.0 and 100.0 μg L⁻¹, respectively. The new sorbent efficiency for the interference-free preconcentration of Cd(II) ions was assessed by analysis of tap, mineral and lake waters, as well as synthetic seawater and normal saline waters. Furthermore, complex samples, such as biological samples, could be analysed by the proposed method in accordance with the accuracy attested by analysis of certified reference materials, TORT-2 (lobster hepatopancreas), and DOLT-4 (dogfish liver).     

Elimination of chloride interference on arsenic speciation in ion chromatography inductively coupled mass spectrometry using an octopole collision/reaction system

Anion-exchange chromatography with inductively coupled plasma mass spectrometry (ICP-MS) is often used for the speciation of arsenic (As). In this work, either He or H₂ was introduced to the octopole collision/reaction cell to eliminate chloride (Cl⁻) interferences during As speciation by ICP-MS. Polyatomic species, ⁴⁰Ar³⁵Cl and ³⁸Ar³⁷Cl, which are formed in high chloride matrices interfere with the ICP-MS detection of ⁷⁵As. These interferences were reduced or eliminated by introducing He or H₂ to the collision/reaction cell, with some loss in sensitivity when compared to the standard mode (no gas). For example, the sensitivity of As(V) was 30.4 and 17.7% of that observed in standard mode when introducing He and H₂, respectively. Chloride interference was completely eliminated using a flow rate of 3.0 mL min^− 1 with H₂ as a reaction gas with detection limits in the range of 0.3-0.6 μg L^− 1. The developed method was applied to determination of arsenic species in waters containing high concentrations of chloride by following a simple procedure and without modification of the ICP-MS instrument.     

Preconcentration of inorganic antimony(III) in environmental samples by PSTH-Dowex microcolumn and determination by FI-ETAAS

A flow injection on-line sorption preconcentration system has been synchronously coupled to an electrothermal atomic absorption spectrometry (ETAAS) system for the selective determination of trace amounts of Sb(III) in water, soil and plant. The determination was achieved by selective complexation and sorption of Sb(III) with [1,5-bis(2-pyridyl)-3-sulphophenyl methylene thiocarbonohydarzide (PSTH) immobilized on an anion-exchange resin (Dowex 1× 8-200)] at a wide range of pH, quantitative elution with 50 μl of 2 M HNO₃ and subsequent ETAAS detection. ETAAS determination of the analyte was performed in parallel with the preconcentration of the next sample. Using a preconcentration time of 60 s and a sample loading flow rate of 2.8 ml min⁻¹, an enhancement factor of 12 was obtained in comparison with direct injection of 50 μl aqueous solution, resulting in a sampling frequency of 31 samples h⁻¹. The detection limit (3 s) was 2 μg l⁻¹ and the precision was 3.1% (R.S.D.) for 11 replicate determinations at 10 μg l⁻¹. The accuracy of the proposed method was demonstrated by analyzing one certified sample and different spiked samples.     

Sorption characteristics and chromatographic separation of gold (I and III) from silver and base metal ions using polyurethane foams

The influence of different parameters on the sorption profiles of trace and ultra traces of gold (I) species from the aqueous cyanide media onto the solid sorbents ion exchange polyurethane foams (IEPUFs) and commercial unloaded polyurethane foams (PUFs) based polyether type has been investigated. The retention of gold (I) species onto the investigated solid sorbents followed a first-order rate equation with an overall rate constant k in the range 2.2-2.8 ± 0.2 s⁻¹. The sorption data of gold (I) followed Freundlich and Langmuir isotherm models. Thus, the a dual-mode of sorption mechanism involving absorption related to “weak base anion exchanger” and an added component for “surface adsorption” seems the most likely proposed dual mechanism for retention profile of gold (I) by the IEPUFs and PUFs solid sorbents. The capacity of the IEPUFs and PUFs towards gold (I) sorption calculated from the sorption isotherms was found to be 11.21 ± 1.8 and 5.29 ± 0.9 mg g⁻¹, respectively. The chromatographic separation of the spiked inorganic gold (I) from de ionized water at concentrations 5-15 μg mL⁻¹ onto the developed IEPUFs and PUFs packed columns at 10 mL min⁻¹ flow rate was successfully achieved. The retained gold (I) species were then recovered quantitatively from the IEPUFs (98.4 ± 2.4%, n = 5) and PUFs (95.4 ± 3.4%, n = 5) packed columns using perchloric acid (60 mL, 1.0 mol L⁻¹) as a proper eluating agent. Thiourea (1.0 mol L⁻¹)-H₂SO₄ (0.1 mol L⁻¹) system was also used as eluating agent for the recovery of gold (I) from IEPUFS (95.4 ± 5.4%, n = 3) and also PUFs (93.4 ± 4.4%, n = 3) packed columns. The performance of the IEPUFs and PUFs packed columns in terms of the height equivalent to the theoretical plates (HETP), number of plates (N), and critical and breakthrough capacities towards gold (I) species were evaluated. The developed IEPUFs packed column was applied successfully for complete retention and recovery (98.5 ± 2.7) of gold (III) species spiked onto tap- and industrial wastewater samples at <10 μg Au mL⁻¹ after reduction to gold (I). The IEPUFs packed column was applied satisfactorily for complete retention and recovery (98.5 ± 2.7) of total inorganic gold (I) and/or gold (III) species spiked to tap- and industrial wastewater samples at <10 μg mL⁻¹ gold. Chromatographic separation of gold (I) from silver (I) and base metal ions (Fe, Ni, Cu and Zn) using IEPUFS packed columns was satisfactorily achieved. The proposed method was applied successfully for the pre-concentration and separation from anodic slime and subsequent FAAS determination of analyte with satisfactory results (recoveries >95%, relative standard deviations <4.0%).     

Arsenic determination by ICP-QMS with octopole collision/reaction cell. Overcome of matrix effects under vented and pressurized cell conditions

The determination of arsenic by inductively coupled plasma mass spectrometry (ICP-MS) in natural waters with high sodium and chloride content has been investigated. The instrument used is equipped with an octopole collision/reaction cell to overcome spectroscopic interferences. Thus, the optimization of collision/reaction gas flow rates is required when using a pressurized cell. A mixture of 2.9 mL min⁻¹ of H₂ and 0.5 mL min⁻¹ of He has been found to be suitable for the removal of ⁴⁰Ar³⁵Cl⁺ interference.The effect of the introduction of small amounts of alcohol has also been studied in this work under both vented and pressurized cell conditions. It has been observed that the presence of 4% (v/v) of ethanol or methanol results in an increase in arsenic sensitivity. Moreover, under vented cell conditions the addition of alcohol also decreases the formation of polyatomic interference. However, this decrease is not observed under pressurized cell conditions.Different elements have been studied as possible internal standards for arsenic determination in presence of high amounts of sodium. Good results have been obtained for rhodium and yttrium under both vented and pressurized cell conditions. Although the presence of alcohol in the sample matrix also affects their behaviour, rhodium and yttrium are still the most suitable elements to correct for these matrix effects.Different experimental conditions have been compared for arsenic determination in spiked, certified and natural waters with high sodium and chloride content. The best results have been obtained under pressurized cell conditions, in the presence of ethanol and using rhodium as internal standard.     

Determination of Se,Pb, and Sb by atomic fluorescence spectrometry using a new flameless,dielectric barrier discharge atomizer

A flameless atomizer for atomic fluorescence spectrometry (AFS), based on an atmospheric pressure dielectric barrier discharge, has been developed for the atomization of hydride-forming elements, such as Se, Sb and Pb. The atomizer (8 mm o.d, 35 mm length) was operated at a power less than 50 W. The discharge was sustained with argon at the flow rate of 0.85 L min^− 1 after optimization. The characteristics of the atomizer and the effects of different parameters (power, gas flow rate, and KBH₄ concentration) are investigated. The most attractive feature of this atomizer is its low operation temperature (~ 52 °C, detected at the outlet of the atomizer by a thermocouple), allowing both the radiation source and the detector to be placed in close proximity with the atomizer. The analytical performance of the atomizer has been evaluated, and detection limits for Se, Sb and Pb obtained with the present technique were 0.08, 0.11 and 0.27 μg L^− 1, respectively. The accuracy of the system was verified by the determination of Se, Sb and Pb in reference material of spinage GBW 10015. The concentrations of Se, Sb, and Pb determined by the present technique agreed well with the reference values (Se: 92 ± 24 mg kg^− 1, Sb: 43 ± 14 mg kg^− 1, Pb: 11.1 ± 0.9 mg kg^− 1). This detector is very promising for field elements detection with portable AFS.     

Removal of fluoride ions using cuttlefish bones

Because of the high toxicity of fluoride to mankind, there is an urgent need to treat fluoride-contaminated drinking water to make it safe for human consumption. This work investigated the possibility of eliminating, by sorption, the excess of fluoride in overloaded water according to World Health Organization WHO recommendations. We tested the cuttlefish bone as an adsorbent material (available in Tunisia) for the defluoridation of water. Initially, we determined the optimal conditions of use (contact time, pH effect, adsorbent dose, initial fluoride concentration) of the cuttlefish bone on synthetic solutions of sodium fluoride. The second step was to verify the effectiveness of the sorption process on the cuttlefish bone by testing it on natural waters loaded with fluoride. The results obtained showed that sorption on the cuttlefish bone could be an effective method for the removal of fluoride. The efficacy of cuttlefish bone to remove fluoride from water was found to be 80% at pH 7.2, 1 h contact time, 15 g L⁻¹ adsorbent dose and 5 mg L⁻¹ initial fluoride concentration. Despite the different anions (Cl⁻ and SO₄²⁻) generally present in natural waters, a fluoride concentration in agreement with the norm (<1.5 mg L⁻¹) could be reached whatever the water treated. The regeneration of the cuttlefish bone was performed with a NaOH solution (10 g of cuttlefish bone/1000 mL NaOH 3 M). After 1 h of agitation, 95% of fluorides were desorbed. Following regeneration, the adsorbent can be used for further removal of fluoride.     

Sorptive potential of sunflower stem for Cr(III) ions from aqueous solutions and its kinetic and thermodynamic profile

The sorptive potential of sunflower stem (180-300 μm) for Cr(III) ions has been investigated in detail. The maximum sorption (≥85%) of Cr(III) ions (70.2 μM) has been accomplished using 30 mg of high density sunflower stem in 10 min from 0.001 M nitric and 0.0001 M hydrochloric acid solutions. The accumulation of Cr(III) ions on the sorbent follows Dubinin-Radushkevich (D-R), Freundlich and Langmuir isotherms. The isotherm yields D-R saturation capacity X_m = 1.60 ± 0.23 mmol g⁻¹, β = −0.00654 ± 0.00017 kJ² mol⁻², mean free energy E = 8.74 ± 0.12 kJ mol⁻¹, Freundlich sorption capacity K_F = 0.24 ± 0.11 mol g⁻¹, 1/n = 0.90 ± 0.04 and of Langmuir constant K_L = 6800 ± 600 dm³ mol⁻¹ and C_m = 120 ± 18 μmol g⁻¹. The variation of sorption with temperature (283-323 K) gives ΔH = −23.3 ± 0.8 kJ mol⁻¹, ΔS = −64.0 ± 2.7 J mol⁻¹ K⁻¹ and ΔG_298k = −4.04 ± 0.09 kJ mol⁻¹. The negative enthalpy and free energy envisage exothermic and spontaneous nature of sorption, respectively. Bisulphate, Fe(III), molybdate, citrate, Fe(II), Y(III) suppress the sorption significantly. The selectivity studies indicate that Cr(III), Eu(III) and Tb(III) ions can be separated from Tc(VII) and I(I). Sunflower stem can be used for the preconcentration and removal of Cr(III) ions from aqueous medium. This cheaper and novel sorbent has potential applications in analytical and environmental chemistry, in water decontamination, industrial waste treatment and in pollution abatement. A possible mechanism of biosorption of Cr(III) ions onto the sunflower stem has been proposed.     

Simultaneous liquid chromatographic determination of metals and organic compounds in pharmaceutical and food-supplement formulations using evaporative light scattering detection

A novel method for the non-derivatization liquid chromatographic determination of metals (potassium, aluminium, calcium and magnesium) and organic compounds (ascorbate and aspartate) was developed and validated based on evaporative light scattering detection (ELSD). Separation of calcium, magnesium and aluminium was achieved by the cation exchange column Dionex CS-14 and an aqueous TFA mobile phase according to the following time program: 0-6 min TFA 0.96 mL L⁻¹, 6-7 min linear gradient from TFA 0.96-6.4 mL L⁻¹. Separation of potassium, magnesium and aspartate was achieved by the lipophilic C₁₈ Waters Spherisorb column and isocratic aqueous 0.2 mL L⁻¹ TFA mobile phase. Separation of sodium, magnesium, ascorbate and citrate was also achieved by the C₁₈ analytical column, according to the following elution program: 0-2.5 min aqueous nonafluoropentanoic acid (NFPA) 0.5 mL L⁻¹; 2.5-3.5 min linear gradient from 0.5 mL L⁻¹ NFPA to 1.0 mL L⁻¹ TFA. In all cases, evaporation temperature was 70 °C, pressure of the nebulizing gas (nitrogen) 3.5 bar, gain 11 and the flow rate 1.0 mL min⁻¹. Resolution among calcium and magnesium was 1.8, while for all other separations was ≥3.2. Double logarithmic calibration curves were obtained within various ranges from 3-24 to 34-132 μg mL⁻¹, and with good correlation (r > 0.996). Asymmetry factor ranged from 0.9 to 1.9 and limit of detection from 1.3 (magnesium) to 17 μg mL⁻¹ (ascorbate).The developed method was applied for the assay of potassium, magnesium, calcium, aluminium, aspartate and ascorbate in pharmaceuticals and food-supplements. The accuracy of the method was evaluated using spiked samples (%recovery 95-105%, %R.S.D. < 2) and the absence of constant or proportional errors was confirmed by dilution experiments.