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1.
Continuous flow (CF) chemical hydride generation (CHG) and electrochemical hydride generation (ECHG) directly coupled to a novel 40 W, atmospheric pressure, 2.45 GHz microwave microstrip Ar plasma exiting a microstrip wafer has been developed for the emission spectrometric determination of As and Sb using a miniaturized optical fiber spectrometer and a CCD-array detector. The experimental conditions for both procedures were optimized with respect to the relative net intensities of the As I 228.8 nm and Sb I 252.8 nm lines and their signal-to-background intensity ratios. Additionally, the susceptibility to interferences from Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn and other hydride-forming elements in the determination of As and Sb using the CHG and ECHG techniques was investigated in detail. Under the optimized conditions, it was found that ECHG is more prone to interferences compared to CHG. The detection limits (3σ) of As (6 ng mL−1) and Sb (7 ng mL−1) obtained for the ECHG-MSP-OES method are about three times lower than in the case of the CHG-MSP-OES method due to a two-fold lower amount of H2 introduced into the MSP in case of the ECHG, resulting in a better plasma stability and reduced background level. The linearity ranges for both calibration curves to a concentration of up to 5 μg mL−1 and a precision between 2% and 7% (2 μg mL−1 and 0.050 μg mL−1 of As and Sb, respectively) were found for both methods. The developed ECHG-MSP-OES method was validated for As through the analysis of a certified coal fly ash standard reference material (NIST SRM 1633a) after sample dissolution. The derived concentration (140 ± 8 μg g−1) was found to agree well with the certified data (145 ± 15 μg g−1). The method was also successfully applied to the analysis of both a galvanic bath sample, which contained Sb and was spiked with As, and a tap water sample spiked with both analytes. Recovery rates of 99-101% and a Sb concentration of 6.6 μg mL−1 in the galvanic bath sample were revealed. The latter value showed a good agreement with the data obtained from ICP-OES analysis, which was also used for validation purpose.  相似文献   

2.
Study on simultaneous speciation of arsenic and antimony by HPLC-ICP-MS   总被引:1,自引:0,他引:1  
A method was developed for the simultaneous speciation of arsenic and antimony with HPLC-ICP-MS using C30 reversed phase column. Eight kinds of arsenic compounds (As(III), As(V), monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), arsenobetaine (AB), arsenocholine (AsC), trimethylarsine oxide (TMAO) and tetramethylarsonium (TeMA)), Sb(III) and Sb(V) were simultaneously separated by the special mobile phase containing ammonium tartrate. Especially for the species of organic As, a C30 column was better than a C18 column in the effect of separation. Limits of detection (LOD) for these elements were 0.2 ng ml−1 for the species of each As, and 0.5 ng ml−1 for the species of each Sb, when a 10 μl of sample was injected, respectively. The proposed method was applied to a hot spring water and a fish sample.  相似文献   

3.
A simple and sensitive method has been developed for the direct determination of toxic species of antimony in mushroom samples by hydride generation atomic fluorescence spectrometry (HG AFS). The determination of Sb(III) and Sb(V) was based on the efficiency of hydride generation employing NaBH4, with and without a previous KI reduction, using proportional equations corresponding to the two different measurement conditions. The extraction efficiency of total antimony and the stability of Sb(III) and Sb(V) in different extraction media (nitric, sulfuric, hydrochloric, acetic acid, methanol and ethanol) were evaluated. Results demonstrated that, based on the extraction yield and the stability of extracts, 0.5 mol L− 1 H2SO4 proved to be the best extracting solution for the speciation analysis of antimony in mushroom samples. The limits of detection of the developed methodology were 0.6 and 1.1 ng g− 1 for Sb(III) and Sb(V), respectively. The relative standard derivation was 3.8% (14.7 ng g− 1) for Sb(V) and 5.1% (4.6 ng g− 1) for Sb(III). The recovery values obtained for Sb(III) and Sb(V) varied from 94 to 106% and from 98 to 105%, respectively. The method has been applied to determine Sb(III), Sb(V) and total Sb in five different mushroom samples; the Sb(III) content varied from 4.6 to 11.4 ng g− 1 and Sb(V) from 14.7 to 21.2 ng g− 1. The accuracy of the method was confirmed by the analysis of a certified reference material of tomato leaves.  相似文献   

4.
In this study, we present a method for the detection of As and Sb using electrochemical hydride generation (EcHG) under alkaline conditions. Compared to the traditional acid mode, the alkaline mode has better interference tolerance. Moreover, As(III) and Sb(III) could be directly detected by the proposed method. Completely inorganic As and Sb could be detected with a pre-reduction step. The electrolytic reduction process of Sb is studied in detail by cyclic voltammetry. The results indicate that the location for the introduction of carrier gas is the most important factor that influences the desorption process of adsorbed hydrides. The rate-controlling step for stibine (SbH3) formation in an alkaline medium is the desorption process of SbH3 from the cathode surface. The effects of electrolytic conditions and interference ions on EcHG have been studied. Under the optimized conditions, the detection limits (3σ) of As(III) and Sb(III) in aqueous solutions are 0.37 μg L1and 0.32 μg L1, respectively; relative standard deviations (n = 6) of 2.8% and 3.1% for 20 μg L1 As and Sb are obtained. This method has been applied in the determination of different oxidation states of As and Sb in Yangtze River water.  相似文献   

5.
Antimony(V) is volatilized by reaction with potassium bromide in concentrated sulfuric acid media. After volatilization, the gases can be transported to an inductively coupled plasma spectrometer for atomic emission of antimony and its analytical determination. The influent factors, concentrated sulfuric acid volume, concentration and volume of the potassium bromide aqueous solution and carrier gas flow were investigated and optimized using different alternatives. A detection limit of 48 ng ml−1 of Sb was achieved under the optimized conditions with a precision of 7.6% and the calibration graph was linear from 0.10 to 10.0 μg ml−1 for a sample injection of 130 μl.The study of interferences from common cations and anions revealed a good tolerance for most ions, although there was a significant improvement in Sb(V) volatility when As(III) was present. Furthermore, the As(III) sensitization was only produced with Sb(V) species, while the volatility of the Sb(III) bromide species was unaltered.The method was applied to the determination of Sb in real river waters. The results were checked using alternative atomic spectroscopy methods.  相似文献   

6.
Different techniques were selected for comprehensive characterization of seven samples of fly ashes collected from the electrostatic precipitator of the San Nicolás thermal power plant (Buenos Aires, Argentina). Particle size was measured using laser based particle size analyzer. X-ray diffraction powder (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the mineral phase present in the matrix consisting basically of aluminosilicates and large amounts of amorphous material. The predominant crystalline phases were mullite and quartz. Major and minors elements (Al, Ca, Cl, Fe, K, Mg, Na, S, Si and Ti) were detected by energy dispersive X-ray analysis (EDAX). Trace elements (As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Se, V and Zn) content was quantified by inductively coupled plasma optical emission spectrometry (ICP OES). Different acid mixtures and digestion procedures were compared for subsequent ICP OES measurements of the dissolved samples. The digestion procedures used were: i) a mixture of FH + HNO3 + HClO4 (open system digestion); ii) a mixture of FH + HNO3 (MW-assisted digestion); iii) a mixture of HF and aqua regia (MW-assisted digestion). Instrumental neutron activation analysis (INAA) was employed for the determination of As, Ba, Co, Cr, Ce, Cs, Eu, Fe, Gd, Hf, La, Lu, Rb, Sb, Sc, Sm, Ta, Tb, Th, U and Yb. The validation of the procedure was performed by the analysis of two certified materials namely, i) NIST 1633b, coal fly ash and ii) GBW07105, rock. Mean elements content spanned from 41870 μg g− 1 for Fe to 1.14 μg g− 1 for Lu. The study showed that Fe (41870 μg g− 1) ? V (1137 μg g− 1) > Ni (269 μg g− 1) > Mn (169 μg g− 1) are the main components. An enrichment, with respect to crustal average, in many elements was observed especially for As, V and Sb that deserve particular interest from the environmental and human health point of view.  相似文献   

7.
A novel disk electrochemical hydride generator has been developed for the determination of As and Sb. Compared with the traditional thin-layer cell, the disk cell combined the advantages of quick assembly and easy operation. This electrochemical system for hydride generation in neutral buffer solutions has been studied for analytical usefulness in coupling with atomic fluorescence spectrometry. It was found that the use of neutral phosphate buffer solution could markedly increase the fluorescence intensity of As(III) and Sb(III) and reduce the impact of cathode erosion on the stability of signal intensity. At the same time, the fluorescence intensity of As(V) and Sb(V) were almost suppressed totally. The detection limits (3σ) of 0.031 μg L−1 As(III) and 0.026 μg L−1 Sb(III) in aqueous solutions were obtained, respectively. The precisions (n = 11) for 20 μg L−1 As(III) and Sb(III) were 2.0% and 2.7%, respectively. The method was successfully applied for determination of different oxidation states of As and Sb in environmental samples.  相似文献   

8.
The paper presents a procedure for the multi-element inorganic speciation of As(III, V), Se(IV, VI) and Sb(III, V) in natural water with GF-AAS using solid phase extraction technology. Total As(III, V), Se(IV, VI) and Sb(III, V) were determined according to the following procedure: titanium dioxide (TiO2) was used to adsorb inorganic species of As, Se and Sb in sample solution; after filtration, the solid phase was prepared to be slurry for determination. For As(III), Se(IV) and Sb(III), their inorganic species were coprecipitated with Pb-PDC, dissolved in dilute nitric acid, and then determined. The concentrations of As(V), Se(VI) and Sb(V) can be calculated by the difference of the concentrations obtained by the above determinations. For the determination of As(III), Se(IV) and Sb(III), palladium was chosen as a modifier and pyrolysis temperature was 800 °C. Optimum conditions for the coprecipitation were listed for 100 ml of sample solution: pH 3.0, 15 min of stirring time, 40.0 μg l−1 Pb(NO3)2 and 150.0 μg l−1 APDC. The proposed method was applied to the determination of trace amounts of As(III, V), Se(IV, VI) and Sb(III, V) in river water and seawater.  相似文献   

9.
Hsiang MC  Sung YH  Huang SD 《Talanta》2004,62(4):791-799
A simple method was developed for the direct and simultaneous determination of arsenic (As), manganese (Mn), cobalt (Co), and nickel (Ni) in urine by a multi-element graphite furnace atomic absorption spectrometer (Perkin-Elmer SIMAA 6000) equipped with the transversely heated graphite atomizer and longitudinal Zeeman-effect background correction. Pd was used as the chemical modifier along with either the internal furnace gas or a internal furnace gas containing hydrogen and a double stage pyrolysis process. A standard reference material (SRM) of Seronorm™ Trace Elements in urine was used to confirm the accuracy of the method. The optimum conditions for the analysis of urine samples are pyrolysis at 1350 °C (using 5% H2 v/v in Ar as the inter furnace gas during the first pyrolysis stage and pure Ar during the second pyrolysis stage) and atomization at 2100 °C. The use of Ar and matrix-free standards resulted in concentrations for all the analytes within 85% (As) to 110% (Ni) of the certified values. The recovery for As was improved when mixture of 5% H2 and 95% Ar (v/v) internal furnace gas was applied during the first step of a two-stage pyrolysis at 1350 °C, and the found values of the analytes were within 91-110% of the certified value. The recoveries for real urine samples were in the range 88-95% for these four elements. The detection limits were 0.78 μg l−1 for As, 0.054 μg l−1 for Mn, 0.22 μg l−1 for Co, and 0.35 μg l−1 for Ni. The upper limits of the linear calibration curve are 60 μg l−1 (As); 12 μg l−1 (Mn); 12 μg l−1 (Co) and 25 μg l−1 (Ni), respectively. The relative standard deviations (R.S.D.s) for the analysis of SRM were 2% or less. The R.S.D.s of a real urine sample are 1.6% (As), 6.3% (Mn), 7.0% (Ni) and 8.0% (Co), respectively.  相似文献   

10.
A new method was developed for the simultaneous speciation of inorganic arsenic and antimony in water by on-line solid-phase extraction coupled with hydride generation-double channel atomic fluorescence spectrometry (HG-DC-AFS). The speciation scheme involved the on-line formation and retention of the ammonium pyrrolidine dithiocarbamate complexes of As(III) and Sb(III) on a single-walled carbon nanotubes packed micro-column, followed by on-line elution and simultaneous detection of As(III) and Sb(III) by HG-DC-AFS; the total As and total Sb were determined by the same protocol after As(V) and Sb(V) were reduced by thiourea, with As(V) and Sb(V) concentrations obtained by subtraction. Various experimental parameters affecting the on-line solid-phase extraction and determination of the analytes species have been investigated in detail. With 180 s preconcentration time, the enrichment factors were found to be 25.4 for As(III) and 24.6 for Sb(III), with the limits of detection (LODs) of 3.8 ng L− 1 for As(III) and 2.1 ng L− 1 for Sb(III). The precisions (RSD) for five replicate measurements of 0.5 μg L−1 of As(III) and 0.2 μg L−1 of Sb(III) were 4.2 and 4.8%, respectively. The developed method was validated by the analysis of standard reference materials (NIST SRM 1640a), and was applied to the speciation of inorganic As and Sb in natural water samples.  相似文献   

11.
Vanessa G.K. Almeida 《Talanta》2007,71(3):1047-1053
This paper reports the development of a reversed flow injection system for the spectrophotometric determination of Sb(III) and total Sb in antileishmanial drugs. The analytical system is based on the selective reaction between Sb(III) and bromopyrogallol red (BPR) with the decrease of the absorbance at 555 nm. Total Sb concentration was determined after reduction of all Sb(V) to Sb(III) with KI and ascorbic acid. The influence of system variables (chemical and flow type) and the possible interference of high amounts of Sb(V) on Sb(III) was studied as well as the suitable conditions for preparation of samples. It was verified that the use of Triton X-100 enhanced the sensitivity of the methodology and that the previous sonication of the samples was fundamental to achieve accurate results. Under optimized conditions the reversed FIA system was able to process 63 samples per hour with a detection limit of 29 ng ml−1 and a R.S.D. of 3.8% (0.25 μg ml−1 level). Real samples of commercial antileishmanial drugs were analyzed, being observed no statistical difference between the results obtained by the developed system and FAAS or manual methodology in relation to total Sb concentration.  相似文献   

12.
Atomic fluorescence spectrometry was used as an element-specific detector in hybridation with liquid chromatography (LC) and hydride generation for the speciation of Sb(III), Sb(V) and trimethylantimony dichloride (TMSbCl2). The three species were poorly resolved in a single chromatogram but good results were obtained by anion-exchange chromatography, using a mobile phase with 20 mM EDTA and 8 mM hydrogenphthalate to separate Sb(III) and Sb(V) and 1 mM carbonate at pH 10 to separate Sb(V) and TMSbCl2. Calibration graphs were linear between 2 and 100 μg l−1. Detection limits were 0.9, 0.5 and 0.7 μg l−1 for Sb(III), Sb(V) and TMSbCl2, respectively. The method was applied to the speciation of antimony in environmental samples.  相似文献   

13.
In the present paper, we develop a methodology for antimony speciation in occupationally exposed human urine samples by high-performance liquid chromatography with hydride generation atomic fluorescence spectrometry (HPLC-HG-AFS). The methodology was applied to the determination of Sb(V), Sb(III) and (CH3)3SbCl2 (TMSb(V)). Retention time of Sb(V), Sb(III) and TMSb(V) species were 0.88, 2.00 and 3.61 and the detection limits were 0.18, 0.19 and 0.12 μg L− 1, for 100 μL loop injection respectively which is considered useful for elevated/occupationally exposed urine samples. Studies on the stability of antimony species in urine samples on the function of the elapsed time of preservation (4 °C) and storage (− 70 °C) were performed. Results revealed that antimony species are highly unstable at − 70 °C, probably due to co-precipitation reaction. In this kind of matrix transformation during preservation time may occur, such as oxidation of Sb(III) to Sb(V) and transformation into species that do not elute from the column. EDTA shows that it is able to stabilize Sb(III) for more than one week of preservation time at 4 °C avoiding co-precipitation during storage at − 70 °C. Finally the methodology was applied to occupationally exposed human urine samples. 25% of specimens present antimony levels (Sb(V)) of more than 5 μg L− 1.  相似文献   

14.
A new method was developed for simultaneous determination of trace arsenic and antimony in Chinese herbal medicines by hydride generation-double channel atomic fluorescence spectrometry with a Soxhlet extraction system and an n-octanol-water extraction system, respectively. The effects of analytical conditions on the fluorescence intensity were investigated and optimized. A water-dissolving and methanol-water-dissolving capability were compared. The contents of different species in five Chinese herbal medicines and their decoctions were analyzed. The concentration ratios of n-octanol-soluble As or Sb to water-soluble As or Sb were related to the kinds of medicine and the acidity of the decoction. Soxhlet extraction was found to be an effective method for plants pretreatment for determination of arsenic and antimony species in Chinese herbs; the interferences of coexisting ions were evaluated. The proposed method has the advantages of simple operation, high sensitivity and high speed, with 3σ detection limits of 0.094 μg g−1 for As(III), 0.056 μg g−1 for total As, 0.063 μg g−1 for Sb(III) and 0.019 μg g−1 for total Sb in a 1.0 g of the sample.  相似文献   

15.
A novel absorbent was prepared by dimercaptosuccinic acid chemically modifying mesoporous titanium dioxide and was employed as the micro-column packing material for simultaneous separation/preconcentration of inorganic arsenic and antimony species. It was found that both trivalent and pentavalent of inorganic As and Sb species could be adsorbed quantitatively on dimercaptosuccinic acid modified TiO2 within a pH range of 4–7, and only As(III) and Sb(III) could be quantitatively retained on the micro-column within a pH range of 10–11 while As(V) and Sb(V) were passed through the micro-column without the retention. Based on this fact, a new method of flow injection on-line micro-column separation/preconcentration coupled to inductively coupled plasma optical emission spectrometry was developed for simultaneous speciation of trace inorganic arsenic and antimony in natural waters. Under the optimized conditions, an enrichment factor of 10 and sampling frequency of 10 h− 1 were obtained with on-line mode. The detection limits of As(III), As(V), Sb(III), and Sb(V) are 0.53, 0.49, 0.77 and 0.71 ng mL− 1 for on-line mode and as low as 0.11, 0.10, 0.15 and 0.13 ng mL− 1 for off-line mode due to its higher enrichment factor (50), respectively. The relative standard deviations of two modes are less than 6.7% (C = 20 ng mL− 1, n = 7). The concentration ratio of lower oxidation states/higher oxidation states changing from 1:10 to 10:1 has no obvious effect on the recoveries of As(III) and Sb(III). In order to validate the developed method, two certified reference materials of GSBZ5004-88 and GBW(E)080545 water sample were analyzed and the determined values are in good agreement with the certified values. The proposed method was successfully applied to the simultaneous speciation of inorganic arsenic and antimony in natural waters.  相似文献   

16.
B.D. Real  L.A. Sarabia 《Talanta》2007,71(4):1599-1609
Using a central composite design, the signal of the process for the spectrophotometric determination of hexavalent chromium (λ = 543 nm) is maximised and its variability minimised using as complexing agent 1,5-diphenylcarbazide in sufficiently acid medium. To analyse the interference of various analytes (Mo(VI), V(V), Fe(III) and Mn(VII)) on the Cr(VI) as a function of concentration of interferent, a factorial design was prepared at three levels of each (zero, medium and high concentration), which implies performing 81 determinations. However, a D-optimal design with just nine experiments is sufficiently good to estimate the model proposed.The interference of these metals makes it impossible to determine Cr(VI) when they are present in the sample. To avoid prior separation steps, a multivariate regression by partial least squares, PLS, is proposed to calibrate the Cr(VI) in the presence of these analytes varying the concentration of the Cr(VI) between 0.1 and 0.9 μg ml−1 and that of the interferents between 3 and 5 μg ml−1. The average errors obtained were 4.5% and 3.29% fitted and in prediction, respectively, with a standard error in prediction (RMSEP) of 0.016% presenting absence of both constant and proportional bias.The detection limit with the PLS regression in the presence of interferents is 0.1 μg ml−1 with a probability of false positive equal to 5% and less than 5% for false negative. The capability of detection is similar to that obtained with the univariate calibration (absorbance at 543 nm) in absence of interferents.With the PLS regression it is possible to discriminate 0.085 μg ml−1 of Cr(VI) in a sample with 0.5 μg ml−1 of Cr(VI) with probabilities of false compliance and false non-compliance equal to 0.05. For the univariate calibration without interferents, it was established at 0.0971 μg ml−1 of Cr(VI) for the same nominal concentration.In relation to interference of V(V), Fe(III) and Mn(VII), the PLS calibration could be an efficient alternative to the separation step for Cr(VI) spectrophotometric determination using 1,5-diphenylcarbazide.  相似文献   

17.
The direct coupling of continuous hydride generation with both Ar and He microwave induced plasmas (MIP) sustained in a surfatron has been optimized for the simultaneous determination of arsenic, antimony and selenium with atomic emission spectrometry. While a discharge tube of quartz was found suitable for the Ar plasma, the use of an Al2O3 tube led to improved performance of the He plasma. The He MIP was found to be less tolerant to the introduction of hydrogen than the Ar MIP, and correspondingly the hydride generation should be operated at a lower flow rate of 0.5% NaBH4 solution. The introduction of the H2O vapour produced during hydride generation into both discharges was found to greatly decrease the sensitivities and to degrade the measurement precision. It could be effectively removed with trapping by concentrated H2SO4. The detection limits (3σ) for As, Sb and Se are 1, 0.4 and 1 ng ml−1 with the Ar MIP, and 2, 0.3 and 6 ng ml−1 with the He MIP, respectively. The calibration curves are linear over three decades of concentration. The mutual interferences from As(III), Sb(III), Se(IV), Bi(III) and Sn(IV) were found to be negligible at interferent concentrations below 1 μg ml−1 and in most cases the tolerable interferent concentrations are up to 20 μg ml−1. The proposed method has been applied to the determination of As, Sb and Se in tea samples at μg g−1 levels.  相似文献   

18.
A simpler UV-vis spectrophotometric method was investigated for hydroquinone (HQ) determination using KMnO4 as oxidizing agent for conversion of HQ to p-benzoquinone (BQ) as well as signal enhancer. Various parameters such as analytical wavelength, stability time, temperature, pH, solvent effect and interference of chemicals were checked and parameters optimized by using 1 μg ml−1 standard solution of HQ. Beer's Law was applicable in the range of 0.07-2 μg ml−1 and 0.005-0.05 μg ml−1 at 245.5 nm and at 262 nm for aqueous standard solutions of HQ with linear regression coefficient value of 0.9978 and 0.9843 and detection limit of 0.021 μg ml−1 and 0.0016 μg ml−1 HQ, respectively. Standard deviation of 1.7% and 2.4% was true for 1 μg ml−1 and 0.03 μg ml−1 HQ solution (n = 11) run at respective wavelengths. The method was successfully applied to dilute waste photographic developer samples for free HQ determination.  相似文献   

19.
The H-point standard addition method (HPSAM) was applied to kinetic data for simultaneous determination of Sb(V) and Sb(III) and also selectively determines Sb(V) in the presence of Sb(III). The method is based on the differences between rate of complexation of pyrogallol red with Sb(V) and Sb(III) at pH=2. Sb(V) can be determined in the range of 0.3-2.0 μg ml−1 with satisfactory accuracy and precision in the presence of excess Sb(III). Good selectivity was obtained over the variety of metal ions. The proposed method was used for determination of Sb(V) and Sb(III) in river and spring water samples.  相似文献   

20.
A flow-injection chemiluminescence (CL) method, based on the luminescent properties of the Ce(IV)-Na2SO3-lanthanide(III)-grepafloxacin system, was developed for the determination of grepafloxacin {1-cyclopropyl-6-fluoro-1,4-dihydro-5-methyl-7-(3-methyl-1-piperazinyl)-4-oxo-3-quinolinecarboxylic acid}. La(III), Tb(III), and Eu(III) ions were tested as possible chemiluminescence sensitizers. The best results were achieved when Tb(III) was used as lanthanide ion, so the technique was optimised working with this ion. Under the optimum experimental conditions, the linear range was 0.05-2.00 μg ml−1 grepafloxacin, with a 0.01 μg ml−1 detection limit and 2.0% relative standard deviation (n=10). The proposed procedure has been applied to the determination of grepafloxacin in tablets and spiked human urine.  相似文献   

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