An adsorbent calix[4]arene carboxylic acid was employed as the adsorption material for on-line flow in jection（FI） micro-column preconcentration coupled with flame atomic absorption spectrometry（FAAS） determinatio...An adsorbent calix[4]arene carboxylic acid was employed as the adsorption material for on-line flow in jection（FI） micro-column preconcentration coupled with flame atomic absorption spectrometry（FAAS） determination of trace heavy metals（Cu, Pb, Co, Ni and Cd）. Parameters such as the pH, loading time and flow rate of sample, and the concentration, volume and flow rate of eluent were optimized. The enrichment factors are 50.0, 56.5, 11.6, 12.1 and 19.1 for Cu, Pb, Co, Ni, and Cd, respectively, and a sample throughput of 20 h–1 was obtained. The limits of de tection for Cu, Pb, Co, Ni, and Cd were in a range of 1.56―3.91 μg/L, and the relative standard deviations（RSDs） were less than 2.76%（n=7）. Furthermore, the proposed method was successfully applied to the determination of Cu, Pb, Co, Ni, and Cd in certified reference materials and various water samples.展开更多
A rapid and sensitive on-line preconcentration method for spectrophotometric determination of chromium (VI) in nature water is described. Preconcentration and determination are based on (i) the quantitative and fast a...A rapid and sensitive on-line preconcentration method for spectrophotometric determination of chromium (VI) in nature water is described. Preconcentration and determination are based on (i) the quantitative and fast adsorption of chromium (VI) on the high surface area nanometer-size TiO2 (anatase) powders, which prepared by a sol-gel method from hydrolysis of TiCI4 and (ii) the quantitative and reproducible elution of Cr (VI) by 2. 0 mol. L-1 HCI. A mini-column system for preconcentration is developed, Cr(VI)on the mini-column is eluted and merged with a stream water and DPCB (1, 5-diphenylcarbazide ) as the chromogenic reagent. The Proposed system permits throughputs of 6 sample h--l (0. 001 μg mL-1 Cr(VI) ) or 20 sample h-1 (0. 1 μg mL-1Cr (VI) . The preconcentration factor is 55. The detection limit is 0. 8 ng·mL-1 Cr(VI). The reproducibility is satisfactory with a relative standard deviation of less than 3. 35% (0. Of μg'mL-1Cr (VI), n = 5).展开更多
A flow injection preconcentration system for the flame atomic absorption spectrometric determination of hexavalent chromium has been developed. The method employs on-line preconcentration of Cr(VI) on a minicolumn pac...A flow injection preconcentration system for the flame atomic absorption spectrometric determination of hexavalent chromium has been developed. The method employs on-line preconcentration of Cr(VI) on a minicolumn packed with Cr(VI)-imprinted poly(4-vinyl pyridineco-2-hydroxyethyl methacrylate) placed into a flow injection system. Hexava-lent chromium was eluted with a small volume of diluted hydrochloric acid into the nebulizer-burner system of a flame atomic absorption spectrometer. An enrichment factor of 550 and a 3σ detection limit of 0.04 μg·L-1 along a sampling frequency of 4 h-1 at a sample flow rate of 3.5 mL·min-1. The relative standard deviation is 2.9% for 1 μg·L-1 Cr(VI) (n = 11). The flow injection system proposed has the advantage of being simpler because the use of expensive and sophisticated instruments is avoided. Ease of use, continuous process and selectivity make this method suitable for Cr(VI) determination in different environmental samples such as sea and river waters, soils and sediments.展开更多
The unstable state of nitrite results in its very low concentration in seawater, which is below the limit of detection （LOD） of conventional techniques of analysis. Some sensitivity-enhanced methods have been propos...The unstable state of nitrite results in its very low concentration in seawater, which is below the limit of detection （LOD） of conventional techniques of analysis. Some sensitivity-enhanced methods have been proposed for the determination of nitrite at nanomolar level to illustrate the role of nitrite in the marine nitrogen cycle. However, most of previous reports are not widely accepted, because of their complexity and cost equipment or intensive labor requirement. In this study, a simple automatic system for the determination of nanomolar level nitrite using on-line preconcentration with spectrophotometric detection was described..An Oasis HLB cartridge was adopted to quantitatively enrich the pink-colored azo compound, formed from nitrite via Griess reaction. The cartridge was rinsed with water and ethanol （volume fraction is 55%, the same below）, in turn, then eluted by an eluent containing 50% ethanol and 0.25 M（mol/dm^3） H2SO4, and determined at 543 nm with a 2 cm path-length flow cell. Under the optimized experimental conditions, the calibration curve showed a good linearity in the range of 1.4 85.7 aM, and the LOD （3a） was estimated to be 0.5 nM. The relative standard deviations of 7 measurements were 4.0% and 1.0% for the samples spiked at 7.1 and 28.6 nM, respectively. The recoveries for the different natural water samples were between 92.2%-108.4%. Each HLB cartridge could be reused for at least 50 times. As compared with other SPE methods, the advantages of this method included the free of interference from salinity variation and less sample consuming. The results of the application of the proposed method to natural water showed good agreement with liquid waveguide capillary cell detection method.展开更多
A new method for the determination of trace non-rare earth elements in high purity rare earth oxides by ICP-AES with preconcentration on an active carbon-silica gel microcolumn in a flow injection system is described ...A new method for the determination of trace non-rare earth elements in high purity rare earth oxides by ICP-AES with preconcentration on an active carbon-silica gel microcolumn in a flow injection system is described in this paper. Experimental parameters such as pH, flow rate,reagent concentration,length of reaction coil,eluent acidity,etc. were optimized. In the buffer solution of NH3. H2O/NH4Cl at pH 4. 6,Al,Cr,Cu,Fe, Pb, V and Zn can be preconcentrated and then eluted with 4. 5 mol/L nitric acid utilizing stop-flow technique. The enrichment factors were in range of 8. 1￣12. 6 with detection limits of μg/m level ,and the RSD with metals at μg/g level were 2. 3￣5. 0% (n= 7). The method proposed can reduce the matrix interference effectively , and has been applied to the determination of non-rare earth metals atμg/g level in high purity Eu2O3 with satisfactory results.展开更多
A simple on-line sonodigestion system was successfully used for breakdown organic nickel complexes in environmental waters acidified with diluted nitric acid prior to flow injection total dissolved nickel preconcentra...A simple on-line sonodigestion system was successfully used for breakdown organic nickel complexes in environmental waters acidified with diluted nitric acid prior to flow injection total dissolved nickel preconcentration in a microcolumn containing a chelating resin (Chelite Che with iminodiacetic acid groups) and determination by flame atomic absorption spectrometry. For the determination of the dissolved labile nickel fraction, microcolumns packed with the chelating resin were loaded in-situ with the sample without sample pH modification, and once in the laboratory were inserted in the flow injection device where nickel elution-detection was carried out. The performance of the chelating resin was investigated in order to elucidate its behavior in the presence of dissolved nickel species. The results obtained reveal that the resin, at the experimental employed conditions, retained only dissolved free nickel ions and nickel bound to weak complexes (labile fraction). The figures of merit for determinations in both nickel fractions are given and the obtained values are discussed. The speciation scheme is applied to the analysis of nickel in river and seawater samples collected in Galicia (Northwest, Spain). The results of fractionation showed that Ni are mainly in the dissolved labile fraction in river water, while in seawater samples analyzed was mainly present in the organic fraction.展开更多
A micro-flow injection sorbent extraction preconcentration system was combined with a graphite furnace atomic absorption spectrometry that formed an integrated system for the determination of trace amounts of elements...A micro-flow injection sorbent extraction preconcentration system was combined with a graphite furnace atomic absorption spectrometry that formed an integrated system for the determination of trace amounts of elements. The analytical performances of the prospsed method for determining Cd, Cu and Mn were studied. The analytes were preconcentrated with a thiol resin(Type 190, produced by Nankai University, China) whose active group is -SH. The elements to be determined were preconcentrated onto the column for 60 s and then rinsed with deionized water and eluted with 30 μL of 1 mol/L HCl. The graphite furnace atomic absorption spectrometry(GFAAS) determination of the concentrated analyte was carried out in parallel with the next preconcentration cycle. Enrichment factors 41, 22 and 20 and detection limits(3 σ , n =10) 0.36, 3.8 and 7.0 ng/L for Cd, Cu and Mn, respectively, along with a sampling frequency of 20 h -1 , were obtained with a 60 s loading time at a sample flow rate of 3.5 mL/min. The analytical results for a number of water samples show that the flow-injection semi-online column preconcentration can not only eliminate the effect of some concomitant elements, such as Li, Na, K, Ca and Mg, on the determination of the analyte, but also enhance the sensitivity.展开更多
In this work, a flow injection analysis (FIA) method for the trace determination of lead, cadmium, nickel and cobalt in natural waters by formation of neutral chelates with ammonium pyrrolidine dithiocarbamate (APDC) ...In this work, a flow injection analysis (FIA) method for the trace determination of lead, cadmium, nickel and cobalt in natural waters by formation of neutral chelates with ammonium pyrrolidine dithiocarbamate (APDC) was developed. The neutral chelates formed was retained in a mini-column packed with Linde type A zeolite (LTA) and type Y Faujasite zeolite (FAU) and then eluted with methyl isobutyl ketone (MIBK) to flame atomic absorption spectrometry (EAA) for its detection. Physicochemical characterization of this zeolite was carried out by Fourier Transform infrared spectroscopy and attenuated total reflectance (FTIR and IR-ATR), scanning electron microscopy and energy dispersive X-ray microanalysis (SEM-EDX) and X-ray power diffraction (XRD). Then, a FIA configuration was used with a column preconcentration system coupled to the detection system at room temperature (22?C). The detection limit and the relative standard deviation for 5 determinations of different solutions of Pb2+, Co2+, Ni2+ and Cd2+ for FAU and LTA zeolite were calculated. The sampling frequency ranged from 18-35 h-1 and preconcentration factors from 21-250 were achieved, for a sample volume of 6 mL using 20 mg of sorbents, indicating a high retention of the analytes on the zeolites material. The recoveries obtained in natural waters samples were close to 100% for all ions metal using synthetic zeolites, confirming the applicability of the method. The isotherm models of Langmuir, Scatchard, Freundlich and Dubinin-Radushkevich were used to study the equilibrium data, indicating that successfully followed the Freundlich and Dubinin-Radushkevich (D-R) isotherms at low metal ion concentration. The Freundlich parameter n varied between 0.35-1.01, whereas D-R isotherm yields the sorption free energy E 8 kJ.mol-1 indicating psysisorption.展开更多
A new simple, sensitive and precise green analytical procedure using an automated packed-reactor derivatization technique coupled with on-line solid-phase enrichment （SPEn） has been developed and evaluated to determ...A new simple, sensitive and precise green analytical procedure using an automated packed-reactor derivatization technique coupled with on-line solid-phase enrichment （SPEn） has been developed and evaluated to determine trace levels of methotrexate （MTX）. The method was based on injection of MTX into a flowing stream of phosphate buffer （0.04 M, ptt 3.4）, carried through the packed oxidant reactor of Cerium （IV） trihydroxyhydroperoxide for oxidative cleavage of the drug into highly fluorescent product, 2,4-diaminopteridine- 6-carboxylic acid, followed by SPEn on a head of short ODS column （10mm x 4.6 mm i.d., 5 I＋tm particle size）. The flow rate was 0.25 mL/min and packed reactor temperaturc was 40 ~C. The trapped product was back-flush eluted from the ODS column to the detector by column-switching with an environmentally friendly mobile phase consisting of ethanol and phosphate buffer （0.04 M, pH 3.4） in the ratio of 5：95 （v/v）. The eluent was monitored at emission and excitation wavelengths of 460 and was linear over the concentration range of 1.25-50 360 nm, respectively. The calibration curve ng/mL with a detection limit of 0.08 ug/ml..The method was successfully applied to determine MTX in pharmaceutical formulations with mean percentage recovery ranging from 99.48 to 99.60.展开更多
基金Supported by the Fund of State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemi-stry, Chinese Academy of Sciences(No.RERU2011006)
文摘An adsorbent calix[4]arene carboxylic acid was employed as the adsorption material for on-line flow in jection（FI） micro-column preconcentration coupled with flame atomic absorption spectrometry（FAAS） determination of trace heavy metals（Cu, Pb, Co, Ni and Cd）. Parameters such as the pH, loading time and flow rate of sample, and the concentration, volume and flow rate of eluent were optimized. The enrichment factors are 50.0, 56.5, 11.6, 12.1 and 19.1 for Cu, Pb, Co, Ni, and Cd, respectively, and a sample throughput of 20 h–1 was obtained. The limits of de tection for Cu, Pb, Co, Ni, and Cd were in a range of 1.56―3.91 μg/L, and the relative standard deviations（RSDs） were less than 2.76%（n=7）. Furthermore, the proposed method was successfully applied to the determination of Cu, Pb, Co, Ni, and Cd in certified reference materials and various water samples.
文摘A rapid and sensitive on-line preconcentration method for spectrophotometric determination of chromium (VI) in nature water is described. Preconcentration and determination are based on (i) the quantitative and fast adsorption of chromium (VI) on the high surface area nanometer-size TiO2 (anatase) powders, which prepared by a sol-gel method from hydrolysis of TiCI4 and (ii) the quantitative and reproducible elution of Cr (VI) by 2. 0 mol. L-1 HCI. A mini-column system for preconcentration is developed, Cr(VI)on the mini-column is eluted and merged with a stream water and DPCB (1, 5-diphenylcarbazide ) as the chromogenic reagent. The Proposed system permits throughputs of 6 sample h--l (0. 001 μg mL-1 Cr(VI) ) or 20 sample h-1 (0. 1 μg mL-1Cr (VI) . The preconcentration factor is 55. The detection limit is 0. 8 ng·mL-1 Cr(VI). The reproducibility is satisfactory with a relative standard deviation of less than 3. 35% (0. Of μg'mL-1Cr (VI), n = 5).
基金This work has been funded by the Spain’s Ministry of Science and Innovation,within the framework of Project CTQ2009-12282.
文摘A flow injection preconcentration system for the flame atomic absorption spectrometric determination of hexavalent chromium has been developed. The method employs on-line preconcentration of Cr(VI) on a minicolumn packed with Cr(VI)-imprinted poly(4-vinyl pyridineco-2-hydroxyethyl methacrylate) placed into a flow injection system. Hexava-lent chromium was eluted with a small volume of diluted hydrochloric acid into the nebulizer-burner system of a flame atomic absorption spectrometer. An enrichment factor of 550 and a 3σ detection limit of 0.04 μg·L-1 along a sampling frequency of 4 h-1 at a sample flow rate of 3.5 mL·min-1. The relative standard deviation is 2.9% for 1 μg·L-1 Cr(VI) (n = 11). The flow injection system proposed has the advantage of being simpler because the use of expensive and sophisticated instruments is avoided. Ease of use, continuous process and selectivity make this method suitable for Cr(VI) determination in different environmental samples such as sea and river waters, soils and sediments.
基金The National High Technology Research and Development Program of China under contract Nos 2006AA09Z174 and 2007AA061501the National Natural Science Foundation of China under contract No. 40521003
文摘The unstable state of nitrite results in its very low concentration in seawater, which is below the limit of detection （LOD） of conventional techniques of analysis. Some sensitivity-enhanced methods have been proposed for the determination of nitrite at nanomolar level to illustrate the role of nitrite in the marine nitrogen cycle. However, most of previous reports are not widely accepted, because of their complexity and cost equipment or intensive labor requirement. In this study, a simple automatic system for the determination of nanomolar level nitrite using on-line preconcentration with spectrophotometric detection was described..An Oasis HLB cartridge was adopted to quantitatively enrich the pink-colored azo compound, formed from nitrite via Griess reaction. The cartridge was rinsed with water and ethanol （volume fraction is 55%, the same below）, in turn, then eluted by an eluent containing 50% ethanol and 0.25 M（mol/dm^3） H2SO4, and determined at 543 nm with a 2 cm path-length flow cell. Under the optimized experimental conditions, the calibration curve showed a good linearity in the range of 1.4 85.7 aM, and the LOD （3a） was estimated to be 0.5 nM. The relative standard deviations of 7 measurements were 4.0% and 1.0% for the samples spiked at 7.1 and 28.6 nM, respectively. The recoveries for the different natural water samples were between 92.2%-108.4%. Each HLB cartridge could be reused for at least 50 times. As compared with other SPE methods, the advantages of this method included the free of interference from salinity variation and less sample consuming. The results of the application of the proposed method to natural water showed good agreement with liquid waveguide capillary cell detection method.
文摘A new method for the determination of trace non-rare earth elements in high purity rare earth oxides by ICP-AES with preconcentration on an active carbon-silica gel microcolumn in a flow injection system is described in this paper. Experimental parameters such as pH, flow rate,reagent concentration,length of reaction coil,eluent acidity,etc. were optimized. In the buffer solution of NH3. H2O/NH4Cl at pH 4. 6,Al,Cr,Cu,Fe, Pb, V and Zn can be preconcentrated and then eluted with 4. 5 mol/L nitric acid utilizing stop-flow technique. The enrichment factors were in range of 8. 1￣12. 6 with detection limits of μg/m level ,and the RSD with metals at μg/g level were 2. 3￣5. 0% (n= 7). The method proposed can reduce the matrix interference effectively , and has been applied to the determination of non-rare earth metals atμg/g level in high purity Eu2O3 with satisfactory results.
文摘A simple on-line sonodigestion system was successfully used for breakdown organic nickel complexes in environmental waters acidified with diluted nitric acid prior to flow injection total dissolved nickel preconcentration in a microcolumn containing a chelating resin (Chelite Che with iminodiacetic acid groups) and determination by flame atomic absorption spectrometry. For the determination of the dissolved labile nickel fraction, microcolumns packed with the chelating resin were loaded in-situ with the sample without sample pH modification, and once in the laboratory were inserted in the flow injection device where nickel elution-detection was carried out. The performance of the chelating resin was investigated in order to elucidate its behavior in the presence of dissolved nickel species. The results obtained reveal that the resin, at the experimental employed conditions, retained only dissolved free nickel ions and nickel bound to weak complexes (labile fraction). The figures of merit for determinations in both nickel fractions are given and the obtained values are discussed. The speciation scheme is applied to the analysis of nickel in river and seawater samples collected in Galicia (Northwest, Spain). The results of fractionation showed that Ni are mainly in the dissolved labile fraction in river water, while in seawater samples analyzed was mainly present in the organic fraction.
文摘A micro-flow injection sorbent extraction preconcentration system was combined with a graphite furnace atomic absorption spectrometry that formed an integrated system for the determination of trace amounts of elements. The analytical performances of the prospsed method for determining Cd, Cu and Mn were studied. The analytes were preconcentrated with a thiol resin(Type 190, produced by Nankai University, China) whose active group is -SH. The elements to be determined were preconcentrated onto the column for 60 s and then rinsed with deionized water and eluted with 30 μL of 1 mol/L HCl. The graphite furnace atomic absorption spectrometry(GFAAS) determination of the concentrated analyte was carried out in parallel with the next preconcentration cycle. Enrichment factors 41, 22 and 20 and detection limits(3 σ , n =10) 0.36, 3.8 and 7.0 ng/L for Cd, Cu and Mn, respectively, along with a sampling frequency of 20 h -1 , were obtained with a 60 s loading time at a sample flow rate of 3.5 mL/min. The analytical results for a number of water samples show that the flow-injection semi-online column preconcentration can not only eliminate the effect of some concomitant elements, such as Li, Na, K, Ca and Mg, on the determination of the analyte, but also enhance the sensitivity.
基金The authors are grateful to the FondoNacional de Ciencia y Tecnología(FONACIT)and Consejo de Desarrol-loCientífico,Humanístico,Tecnológico y de lasArtes(CDCHTA)for financial support,Proyects S1-97001192 and C-133105-08B respectively,Laboratorio de Análisis Químico Estructural de Materiales(LAQUEM)and La-boratorio de Cristalografía of the Universidad de Los Andes(ULA)Mérida-Venezuela.
文摘In this work, a flow injection analysis (FIA) method for the trace determination of lead, cadmium, nickel and cobalt in natural waters by formation of neutral chelates with ammonium pyrrolidine dithiocarbamate (APDC) was developed. The neutral chelates formed was retained in a mini-column packed with Linde type A zeolite (LTA) and type Y Faujasite zeolite (FAU) and then eluted with methyl isobutyl ketone (MIBK) to flame atomic absorption spectrometry (EAA) for its detection. Physicochemical characterization of this zeolite was carried out by Fourier Transform infrared spectroscopy and attenuated total reflectance (FTIR and IR-ATR), scanning electron microscopy and energy dispersive X-ray microanalysis (SEM-EDX) and X-ray power diffraction (XRD). Then, a FIA configuration was used with a column preconcentration system coupled to the detection system at room temperature (22?C). The detection limit and the relative standard deviation for 5 determinations of different solutions of Pb2+, Co2+, Ni2+ and Cd2+ for FAU and LTA zeolite were calculated. The sampling frequency ranged from 18-35 h-1 and preconcentration factors from 21-250 were achieved, for a sample volume of 6 mL using 20 mg of sorbents, indicating a high retention of the analytes on the zeolites material. The recoveries obtained in natural waters samples were close to 100% for all ions metal using synthetic zeolites, confirming the applicability of the method. The isotherm models of Langmuir, Scatchard, Freundlich and Dubinin-Radushkevich were used to study the equilibrium data, indicating that successfully followed the Freundlich and Dubinin-Radushkevich (D-R) isotherms at low metal ion concentration. The Freundlich parameter n varied between 0.35-1.01, whereas D-R isotherm yields the sorption free energy E 8 kJ.mol-1 indicating psysisorption.
文摘A new simple, sensitive and precise green analytical procedure using an automated packed-reactor derivatization technique coupled with on-line solid-phase enrichment （SPEn） has been developed and evaluated to determine trace levels of methotrexate （MTX）. The method was based on injection of MTX into a flowing stream of phosphate buffer （0.04 M, ptt 3.4）, carried through the packed oxidant reactor of Cerium （IV） trihydroxyhydroperoxide for oxidative cleavage of the drug into highly fluorescent product, 2,4-diaminopteridine- 6-carboxylic acid, followed by SPEn on a head of short ODS column （10mm x 4.6 mm i.d., 5 I＋tm particle size）. The flow rate was 0.25 mL/min and packed reactor temperaturc was 40 ~C. The trapped product was back-flush eluted from the ODS column to the detector by column-switching with an environmentally friendly mobile phase consisting of ethanol and phosphate buffer （0.04 M, pH 3.4） in the ratio of 5：95 （v/v）. The eluent was monitored at emission and excitation wavelengths of 460 and was linear over the concentration range of 1.25-50 360 nm, respectively. The calibration curve ng/mL with a detection limit of 0.08 ug/ml..The method was successfully applied to determine MTX in pharmaceutical formulations with mean percentage recovery ranging from 99.48 to 99.60.
