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1.
An on-line pre-concentration system for the sequential determination of cadmium and lead in drinking water by using fast sequential flame atomic absorption spectrometry (FS-FAAS) is proposed in this paper. Two minicolums of polyurethane foam loaded with 2-(6-methyl-2-benzothiazolylazo)-orcinol (Me-BTAO) were used as sorptive pre-concentration media for cadmium and lead. The analytical procedure involves the quantitative uptake of both analyte species by on-column chelation with Me-BTAO during sample loading followed by sequential elution of the analytes with 1.0?mol?L?1 hydrochloric acid and determination by FS-FAAS. The optimisation of the entire analytical procedure was performed using a Box–Behnken multivariate design utilising the sampling flow rate, sample pH and buffer concentration as experimental variables.

The proposed flow-based method featured detection limits (3σ) of 0.08 and 0.51?µg?L?1 for cadmium and lead, respectively, precision expressed as relative standard deviation (RSD) of 1.63% and 3.87% (n?=?7) for cadmium at the 2.0?µg?L?1 and 10.0?µg?L?1 levels, respectively, and RSD of 6.34% and 3.26% (n?=?7) for lead at the 5.0?µg?L?1 and 30.0?µg?L?1 levels, respectively. The enrichment factors achieved were 38.6 and 30.0 for cadmium and lead, respectively, using a sample volume of 10.0?mL. The sampling frequency was 45 samples per hour. The accuracy was confirmed by analysis of a certified reference material, namely, SRM 1643d (Trace elements in natural water). The optimised method was applied to the determination of cadmium and lead in drinking water samples collected in Santo Amaro da Purificação City, Bahia, Brazil.  相似文献   

2.
A cloud point extraction procedure for pre-concentration and determination of cadmium and lead in drinking water using sequential multi-element flame atomic absorption spectrometry is described. 4-(2-thiazolylazo)-orcinol (TAO) has been used as complexing agent and the micellar phase was obtained using the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114) and centrifugation. The conditions for reaction and extraction (surfactant concentration, reagent concentration, effect of incubation time, etc) were studied and the analytical characteristics of the method were determined. The method allows the determination of cadmium and lead with quantification limits of 0.30?µg?L?1 and 2.6?µg?L?1, respectively. A precision expressed as relative standard deviation (RSD, n?=?10) of 2.3% and 2.6% has been obtained for cadmium concentrations of 10?µg?L?1 and 30?µg?L?1, respectively, and RSD of 1.3% and 1.7% for lead concentrations of 10?µg?L?1 and 30?µg?L?1, respectively. The accuracy was confirmed by analysis of a natural water certified reference material. The method has been applied for the determination of cadmium and lead in drinking water samples collected in the cities of Ilhéus and Itabuna, Brazil. Recovery tests have also been performed for some samples, and results varied from 96 to 105% for cadmium and 97 to 106% for lead. The cadmium and lead concentrations found in these samples were always lower than the permissible maximum levels stipulated by World Health Organization and the Brazilian Government.  相似文献   

3.
《Analytical letters》2012,45(9):1098-1110
Unmodified multi-walled carbon nanotubes (MWCNTs) were demonstrated as hydrophobic sorbent material for flow injection on-line microcolumn preconcentration coupled with flame atomic absorption spectrometry for cadmium determination in natural water samples. The method was based on on-line chelate complex formation between the analyte with sodium diethyldithiocarbamate and retention onto the surface of MWCNTs. Quantitative elution of the analyte was achieved with methanol which was whereupon delivered to the FAAS nebulizer for atomization and measurement. The microcolumn was packed with a mixture of MWCNTs and silica beads in order to minimize the generated back-pressure in the flow system which arises from the nano dimensions of MWCNTs. All factors affecting the performance of the proposed method were studied thoroughly. For a 180 s preconcentration time the enhancement factor was 54, the detection limit (3s) was 0.24 µg L?1, and the precision as relative standard deviation at a 5.0 µg L?1 Cd(II) concentration level was 3.2%. The method was applied to the analysis of environmental water samples and the accuracy evaluated via certified reference material and recovery experiments.  相似文献   

4.
《Analytical letters》2012,45(11):2285-2295
Abstract

Multi‐walled carbon nanotubes (MWNTs) were used as sorbent for flow injection (FI) on‐line microcolumn preconcentration coupled with flame atomic absorption spectrometry (FAAS) for determination of trace cadmium and copper in environmental and biological samples. Effective preconcentration of trace cadmium and copper was achieved in a pH range of 4.5–6.5 and 5.0–7.5, respectively. The retained cadmium and copper were efficiently eluted with 0.5 mol L?1 HCl for on‐line FAAS determination. The MWNTs packed microcolumn exhibited fairly fast kinetics for the adsorption of cadmium and copper, permitting the use of high sample flow rates up to at least 7.8 mL min?1 for the FI on‐line microcolumn preconcentration system without loss of the retention efficiency. With a preconcentration time of 60 sec at a sample loading flow rate of 4.3 mL min?1, the enhancement factor was 24 for cadmium and 25 for copper at a sample throughput of 45 h?1. The detection limits (3σ) were 0.30 and 0.11 µg L?1 for Cd and Cu, respectively. The precision (RSD) for 11 replicate measurements was 2.1% at the 10‐µg L?1 Cd level and 2.4% at the 10‐µg L?1 Cu level. The developed method was successfully applied to the determination of trace Cd and Cu in a variety of environmental and biological samples.  相似文献   

5.
A method was developed for the on-line determination of palladium in complex matrices with flame atomic absorption spectrometry (FAAS) using Amberlite XAD-16 resin functionalized with 2-[2-(5-thiol-1,3,4-thiadiazolyl)]-azonaphthol (TTAN) reagent. Optimum experimental conditions such as pH of sample, type of eluent, amount of resin, volumes of sample and eluent solution, flow rates of sample and eluent, and effect of interfering ions were established. A 0.1?mol?L?1 thiourea solution in 0.5?mol?L?1 HCl was used as the eluent and subsequently transportation the analyte ions into the nebulizer–burner system for atomization. The synthesized chelating resin material showed excellent chemical and mechanical resistance, fast adsorption kinetics permitting the use of high sample flow rates without significant losses of retention efficiency. The detection limit of the method was 1.5?µg?L?1 while the relative standard deviation (RSD%) was 2.4% at 0.1?mg?L?1 Pd(II) level. The developed method was successfully applied to the determination of palladium in the catalytic converter and water samples.  相似文献   

6.
A new and simple column-solid-phase extraction method has been developed to separate and preconcentrate trace cobalt in water and soil prior to its determination by flame atomic absorption spectrometry (FAAS). Different factors such as pH of sample solution, sample volume, amount of resin, flow rate of aqueous solution, volume and concentration of eluent, and matrix effects for preconcentration were optimized. Under optimized experimentally established conditions, an analytical detection limit of 0.44?µg?L?1, precision (RSD) of 1.9%, enrichment factor of 200, and capacity of resin of 82?mg?g?1 were obtained. The method was applied for cobalt determination by FAAS in tap water, natural drinking water, soil, and roadside dust samples. The accuracy of the method is confirmed by analysing standard reference material (Montana Soil, SRM 2711).  相似文献   

7.
An on-line solid phase extraction (SPE) preconcentration system coupled to flame atomic absorption spectrometer (FAAS) was developed for determination of copper and cadmium at μg L−1 level. The method is based on the on-line retention of copper and cadmium on a microcolumn of alumina modified with sodium dodecyl sulfate (SDS) and 1,10-phenanthroline and subsequent elution with ethanol and determination by FAAS. The effect of chemical and flow variables that could affect the performance of the system was investigated. The relative standard deviation (n = 6) at 20 μg L−1 level for copper and cadmium were 1.4 and 2.2% and the corresponding limits of detection (based on 3σ) were 0.04 and 0.14 μg L−1, respectively. The method was successfully applied to determination of copper and cadmium in human hair and water samples.  相似文献   

8.
The method relies on selective complexation of As(III) with a suitable chelating agent followed by dispersive liquid–liquid microextraction (DLLME) method. Flame atomic absorption spectrometry (FAAS) equipped with microsample introduction system was utilised for determination of As(III). 1-Undecanol and acetone were used as extraction solvent and disperser solvent respectively. Some effective parameters on complex formation and extraction have been optimised. Under the optimum conditions, the enrichment factor of 108 for As(III) was obtained from 9.8?mL of water samples. The calibration graph was linear in the range of 2–15?µg?L?1 with detection limits of 0.60?µg?L?1 for As(III). The relative standard deviation (R.S.D.) for ten replicate measurements of 5.00?µ?gL?1 of As(III) was 6.2%. Operation simplicity and high enrichment factors are the main advantages of DLLME for the determination of As(III) without necessity for hydride generation in water samples.  相似文献   

9.
In this study, a simple and efficient method of ligandless-ultrasound-assisted emulsification microextraction (LL-USAEME) followed by inductively coupled plasma-optical emission spectrometry (ICP-OES) has been developed for simultaneous extraction, preconcentration and determination of manganese, cadmium, cobalt and nickel in water samples. In the proposed approach, tetrachloroethylene was selected as extraction solvent. The effect of important experimental factors such as volume of extraction solvent, pH, sonication time, salt concentration, and temperature was investigated by using a fractional factorial design (25?1) to identify important factors and their interactions. In the next step, a Box-Behnken design (BBD) was applied for optimisation of significant factors. The obtained optimal conditions were: 30?µL for extraction solvent, 12 for pH, 5?min for sonication time, and 5% w/v for salt concentration. The limits of detections (LODs) for Cd(II), Co(II), Mn(II) and Ni(II) were 0.20, 0.13, 0.21 and 0.28?µg?L?1, respectively. Relative standard deviations (RSD, C?=?200.0?µg?L?1, n?=?9) were between 3.4–7.5% and the calibration graphs were linear in the range of 0.25 to 1000.0?µg?L?1 for Mn, 0.5–1000.0?µg?L?1 for Co and Ni and 1.0–250.0?µg?L?1 for Cd. The determination coefficients (R 2) of the calibration curves for the analytes were in the range of 0.993 to 0.999. The proposed method was validated by using two certified reference materials, and also the method was applied successfully for the determination of heavy metals in different real water samples.  相似文献   

10.
A rapid and simple on-line method is described for the determination of Au(III) in various samples. The method is based on the sorption of gold(III) on Lewatit MonoPlus TP207 chelating resin including the iminodiacetate group, which is used as sorbent material and packed in a minicolumn. The chemical variables such as the pH of the sample solution, eluent type, interfering ions and concentrations of reagents, and instrumental variables such as sample loading volume, reagents flow rates, and tubing length, which affect the efficiency of the method were studied and optimised. Au(III) was sorbed on the chelating resin, from which it could be eluted with 3 mol L?1 HCl, and then introduced directly to the nebuliser-burner system of FAAS. The limit of detection of the method was 0.2 µg L?1 while the relative standard deviation was <4.0% for 20 µg L?1 Au(III) concentration. The preconcentration factor was found to be 106 while the optimised sample volume was 15.3 mL. The accuracy of the method was verified by analysing the certified reference material. The developed method was applied successfully for the determination of gold in different samples with satisfactory results.  相似文献   

11.
Novel and fast deep eutectic solvent (DES)-based homogeneous liquid–liquid microextraction (HLLME) was applied for the extraction of copper from vegetable samples followed by flame atomic absorption spectrometry (FAAS). 1,5-diphenyl carbazone (DPC) was used as the chelating agent, and a DES was used as the extraction media. The utilized DES was based on benzyl triphenyl phosphonium bromide and ethylene glycol in a 1:8?mole ratio. The phase separation phenomenon was occurred by changing of sample temperature. Several factors influencing the extraction efficiency were investigated and optimized. Under the optimized conditions, an enhancement factor of 64 was obtained. The limit of detection, based on three signal-to-noise ratio, and limit of quantification were found to be 0.13?µg L?1 and 5.0?µg L?1, respectively. The calibration curve was linear within the range of 5.0–250?µg L?1 with r2 > 0.9957. Intra- and inter-day relative standard deviations (%) of 2.1% and 2.6% were obtained at the concentration of 25?µg L?1. The accuracy of the proposed method was evaluated by analyzing a tomato leaves certified reference material and the results were to be in agreement with the certified value. Finally, the feasibility of the method was successfully confirmed by determination of copper in spinach, lettuce, broccoli, potato, carrot and parsley samples.  相似文献   

12.
A novel dual-syringe flow injection (DSFI) on-line column preconcentration system coupled to flame atomic absorption spectrometry (FAAS) has been developed for automatic trace metal determination in natural waters and biological samples. The proposed method was based on the on-line retention of Cd(II), Pb(II), Cu(II), Co(II) and Ni(II) ions onto the surface of a strong cation exchanger resin named HyperSepSCX, in a readily exchangeable micro-cartridge format and subsequent elution with HCl (2?mol?L?1) prior to flame atomization. The sorbent and the micro-cartridge exhibited high long term chemical and mechanical stability with fast kinetics for all analytes. All main chemical and hydrodynamic factors affecting the performance of the proposed method were studied thoroughly. For 15.0?mL sample volume, the enhancement factors were calculated as 92, 97, 93, 99 and 77 for Cd(II), Pb(II), Cu(II), Co(II) and Ni(II) respectively and the detection limits (3?s) were in the range between 0.14 and 2.1?µg?L?1. The precision (RSD) obtained was lower than 3.3% for all five metal ions with a sample throughput of 12?h?1. The developed method was evaluated by analyzing certified reference materials and spiked environmental natural water samples.  相似文献   

13.
Lucigenin chemiluminescence (CL) in conjunction with flow-injection analysis (FIA) is used for the determination of phosphate in freshwater samples. The procedure is based on the formation of molybdophosphoric heteropoly acid (MoP–HPA) by the reaction of phosphate and ammonium molybdate under acidic conditions. CL emission was observed as a result of oxidation of lucigenin in aqueous sodium hydroxide solution in the presence of MoP–HPA. Calibration was linear up to 500?µg?L?1 (r 2?=?0.9998; n?=?8), with a detection limit (S/N?=?3) of 0.95?µg?L?1. An injection throughput of 120 h?1, and relative standard deviation (RSD; n?=?4) of 1.3–3.2% were achieved in the concentration range studied. An on-line chelating column was used to remove interfering cations. The method was applied to freshwater samples, and the results (51?±?1.0 – 107?±?2.0?µg?L?1) did not differ significantly from results obtained using a spectrophotometric method (52.5?±?1.0 – 102?±?2.0?µg?L?1) at 95% confidence level (t-test).  相似文献   

14.
A simple, low-cost and sensitive electroanalytical method was developed for the simultaneous determination of p-nitrophenol and o-nitrophenol isomers in water samples at a glassy carbon electrode (CGE) in the presence of cationic surfactant. The electrochemical behavior of p-nitrophenol and o-nitrophenol was studied by cyclic voltammetry (CV) in 0.1?mol L?1 acetate/acetic acid buffer (pH 3.70) in the presence and absence of cetylpyridinium bromide. The resolution of overlapped cathodic peaks potentials (Epc) of isomers was successfully improved in the presence of 100.0?µmol L?1 cetylpyridinium bromide, thus making this approach ideal for the simultaneous determination of isomers. Under the optimized conditions in 0.05?mol L?1 HEPES buffer at pH 7.0 using differential pulse voltammetry (DPV) at a scan rate of 45?mV s?1, pulse amplitude of 220?mV and modulation time of 10?ms, limits of detection 0.59?µmol L?1 for p-nitrophenol and 1.14?µmol L?1 for o-nitrophenol were obtained with linear ranges from 2.0 to 60.0?µmol L?1 and 3.0 to 60.0?µmol L?1, respectively. The intraday precision was assessed as relative standard deviation (%) for 20.0 and 40.0?µmol L?1 concentrations were 4.30% and 2.41% for p-nitrophenol and 4.87% and 2.20% for o-nitrophenol, respectively. The developed method was applied for the determination of the isomers in lake water samples. The accuracy was attested by comparison with high-performance liquid chromatography with diode array detection (HPLC-DAD) as a reference analytical technique. Recovery values ranging from 90.3% to 111.8% also attested to the accuracy of method for analysis of real samples.  相似文献   

15.
A new sorbent – salen impregnated silica gel – was prepared and characterised for application as a minicolumn packing for flow-injection on-line preconcentration of cadmium(II). The system was coupled with flame atomic absorption spectrometer (FI-FAAS). The optimal pH for Cd(II) sorption was in the range of 7.4–8.8 and nitric acid (1%, v/v) was efficient as eluent. Sorption was most effective within the sample flow rate up to 7?mL?min?1. Sorption capacity of the sorbent found in a batch procedure was 26.3?µmol?g?1 (2.95?mg?g?1). Enrichment factor (EF) and limit of detection (LOD) obtained for 120-second loading time were 113 and 0.26?µg?L?1, respectively. The sorbent stability in the working conditions was proved for at least 100 preconcentration cycles. The evaluated method was applied to Cd(II) determination in various water samples.  相似文献   

16.
In this work, a solidified floating organic drop microextraction was developed based on a vesicular supramolecular solvent consisting of decanoic acid and quaternary ammonium. The method was used for preconcentration of trace amount of cadmium in different rice samples followed by flow-injection analysis–flame atomic absorption spectrometry. Several parameters affecting the extraction efficiency including pH, concentration of 1-(2-pyridylazo)-2-naphthol as the chelating agent, sample and extraction solvent volume, stirring rate, extraction time, salt effect, and interfering ions were investigated and optimized. Under the optimum conditions, a preconcentration factor of 84 was achieved. LOD and LOQ were found to be 0.09 and 0.31 µg L?1, respectively. The calibration curve was linear within the range of 5.0–700 µg L?1 (r2?>?0.9978). Intra- and inter-day precisions (RSD% n?=?3) were estimated 2.7 and 3.9% at the concentration of 20 µg L?1, respectively. The accuracy of the method was successfully validated by analysis of an SRM-1643f standard reference material. Relative recoveries were achieved within the range of 93–107% elucidating suitability of the method for determination of cadmium in rice samples.  相似文献   

17.
A simple and rapid solid phase extraction?Cflow injection procedure is developed for on-line trace determination of Cu(II) and Pb(II) by flame atomic absorption spectrometry (FAAS). Multi-walled carbon nanotubes modified with a new Schiff??s base, 2,2??-(1E, 1E??)-(4-Methyl-1, 2-phenylene) bis (azen-1-yl-1-ylidine) bis (Methane-1-yl-1-ylidene) diphenol was used as a novel adsorbent material. Quantitative simultaneous extraction was obtained at pH 7.0. The retained metal ions were then eluted efficiently with 1.0?M HNO3 into the nebulizer of FAAS for on-line determination. Different variables affecting the preconcentration efficiency, including pH, eluent concentration, sample and eluent flow rates and sample loading time, were optimized. Using 3?min preconcentration of sample solution at flow rate of 5?mL?min?1 provided the enrichment factors of 20 and 21.5 for Cu(II) and Pb(II), respectively, at a sampling frequency of 17?h?1. The detection limits (3??) were found to be 0.80 and 1.80???g?L?1 for Cu(II) and Pb(II), respectively; and the relative standard deviations at 0.05???g?mL?1 of these metal ions were 1.7 and 1.8% (n?=?8), respectively. The accuracy was assessed by analysis of a certified reference material NKK-916 and the obtained results are in good agreement with certified amounts of Cu(II) and Pb(II). The proposed method was successfully applied to the determination of target analytes in different real samples.  相似文献   

18.
A sensitive and simple method for determination of chromium species after separation and preconcentration by solid phase extraction (SPE) has been developed. For the determination of the total concentration of chromium in solution, Cr(VI) was efficiently reduced to Cr(III) by addition of hydroxylamine and Cr(III) was preconcentrated on a column of immobilised ferron on alumina. The adsorbed analyte was then eluted with 5?mL of hydrochloric acid and was determined by flame atomic absorption spectrometery. The speciation of chromium was affected by first passing the solution through an acidic alumina column which retained Cr(VI) and then Cr(III) was preconcentrated by immobilised ferron column and determined by FAAS. The concentration of Cr(VI) was determined from the difference of concentration of total chromium and Cr(III). The effect of pH, concentration of eluent, flow rate of sample and eluent solution, and foreign ions on the sorption of chromium (III) by immobilised ferron column was investigated. Under the optimised conditions the calibration curve was linear over the range of 2–400?µg?L?1 for 1000?mL preconcentration volume. The detection limit was 0.32?µg?L?1, the preconcentration factor was 400, and the relative standard deviation (%RSD) was 1.9% (at 10?µg?L?1; n?=?7). The method was successfully applied to the determination of chromium species in water samples and total chromium in standard alloys.  相似文献   

19.
An automatic on-line system is developed for the trace determination of copper and iron species in fresh waters by flame atomic absorption spectrometry using only 5 and 2?mL of sample, for copper and iron determination, respectively. This system, which includes a home-made minicolumn of commercially available resin containing aminomethylphosphonic acid functional groups (Chelite P), comprises two operational modes. The first, used for the determination of the dissolved labile fraction (free copper and iron ions and their weak complexes) is based on the elution of this fraction from a minicolumn containing the chelating resin loaded in-situ with the sample. The second mode is used for the determination of total trace copper and iron concentrations. This last mode is based on the retention/preconcentration of total metals on the Chelite P resin after on-line sonoassisted digestion of water samples acidified with nitric acid (0.5?mol?L?1 final concentration) to break down metal organic complexes present in fresh waters as river waters. The figures of merit for copper and iron determination in both fractions are given and the obtained values are discussed. The analytical method was characterized and the limit of detection and limit of quantification for the two metals were 0.5 and 1.6?µg?L?1 for Cu and 2.3 and 6.1?µg?L?1 for Fe, respectively. The repeatability, expressed as relative standard deviation, was in the range 1.0–2.1%. The speciation scheme was applied to the analysis of river surface water samples collected in Galicia (Northwest, Spain).  相似文献   

20.
We report on a novel method for on-line cloud point extraction (CPE) for preconcentration of cadmium ions. It is based on electromagnetic induction-assisted heating (EMIH) of iron particles in a packed bed contained in a quartz tube that acts as an on-line CPE enrichment column. The cadmium complex of 1-(2-pyridylazo)-2-naphthol is quantitatively retained by the column under the cloud point temperature with the help of EMIH. The column was then eluted with alcoholic borax buffer at room temperature and on-line coupled to FAAS. Under optimum conditions, the limit of detection (3 sb/b) and limit of quantification (10 sb/b) are 0.21 μg?L?1 and 0.70 μg?L?1 of Cd(II), respectively, and the relative standard deviation is 3.8 % (for n?=?8; at 20 ng?mL?1). An enhancement factor of 76 is typically achieved. The correlation coefficient of the calibration graph using the present method was 0.9986. The method was successfully applied to determine Cd(II) in water samples
Figure
An on-line cloud point extraction method was developed. Iron particles packed bed acts as an enrichment column. The cadmium complex of 1-(2-pyridylazo)-2-naphthol is quantitatively retained by the column under the cloud point temperature with the help of electromagnetic induction-assisted heating technique  相似文献   

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