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1.
Permanent modifiers (V, Ir, Ru, V-Ir, V-Ru, and W-V) thermally coated on to platforms of pyrolytic graphite tubes were employed for the determination of Cd, Pb, and Zn in botanic and biological slurries by electrothermal atomic absorption spectrometry (ETAAS). Conventional Pd + Mg(NO3)2 modifier mixture was also used for the determination of analytes in slurries and digested samples. Optimum masses and mass ratios of permanent modifiers for Cd, Pb, and Zn in slurry sample solutions were investigated. The 280 μg of V, 280 μg of V + 200 μg of Ir, 280 μg of V + 200 μg of Ru or 240 μg of W + 280 μg of V in 0.2% (v/v) Triton X-100 plus 0.5% (v/v) HNO3 mixture was found as efficient as 5 μg of Pd + 3 μg of Mg(NO3)2 modifier mixture for obtaining thermal stabilization, and for obtaining best recoveries. Optimization conditions of analytes, such as pyrolysis and atomization temperature, characteristic masses and detection limits, and atomization and background peak profiles were studied with permanent and 5 μg of Pd + 3 μg of Mg(NO3)2 conventional modifiers and compared with each other. The permanent V-Ir, V-Ru, and W-V modifiers remained stable for approximately 250-300 firings when 20 μl of slurries and digested samples were delivered into the atomizer. In addition, the mixed permanent modifiers increase the tube lifetime by 50-95% when compared with untreated platforms. The characteristic masses and detection limits of analytes (dilution factor of 125 ml g−1) obtained with V-Ir based on integrated absorbance as example for 0.8% (m/v) slurries were 1.0 pg and 3 ng g−1 for Cd, 18 pg and 17 ng g−1 for Pb, and 0.7 pg and 4 ng g−1 for Zn, respectively. The results of analytes obtained by employing V-Ir, V-Ru, and W-V permanent modifier mixtures in botanic and biological certified and standard reference materials were in agreement with the certified values of reference materials.  相似文献   

2.
In this work, methodologies were developed to determine aluminum (Al), cadmium chromium and lead in drinking water by electrothermal atomic absorption spectrometry using permanent modifiers. No use of modifier, iridium, ruthenium, rhodium and zirconium (independently, 500 μg) were tested to each one analyte through the pyrolysis and atomization temperatures curves. As the matrix is very simple, did not had occurred problems with the background for all metals. The best results obtained for cadmium and chromium was with the use of rhodium permanent modifier. For lead and aluminum, the best choice was the use of zirconium. The selection for the modifier took into account the sensitivity, form of the absorption pulse and low atomization temperature (what contributes to elevate the useful life of the graphite tube). For aluminum using zirconium permanent, the best pyrolysis and atomization temperatures were respectively, of 1000 and 2500 °C with a characteristic mass (1% of absorbance, mo) of 19 pg (recommended of 20 pg). For cadmium, with use of rhodium the best temperatures for the pyrolysis and atomization were respectively of 400 and 1100 °C, with a symmetrical peak and with a mo of 1.0 pg (recommended of 1.0 pg). For chromium with rhodium permanent, the best temperatures for pyrolysis and atomization were respectively of 1000 and 2200 °C, with symmetrical peak and mo of 5.3 pg (recommended of 5.5 pg). For lead with zirconium permanent, the best temperatures for pyrolysis and atomization were of 700 and 2400 °C, with symmetrical peak and with mo of 30 pg (recommended of 20 pg). Water samples spiked with each one of the metals in four different levels inside of the acceptable values presented recoveries always close to 100%. The detection limits were of 0.1 μg l−1 for cadmium; 0.2 μg l−1 for chromium; 0.5 μg l−1 for lead and 1.4 μg l−1 for aluminum.  相似文献   

3.
Molybdenum, Ir, Ru, Mo-Ir, Mo-Ru thermally coated on to platforms inserted in pyrolytic graphite tubes as permanent modifiers and Pd + Mg(NO3)2 conventional modifier mixture have been employed for the determination of cadmium and lead in dissolved sediments and soil samples by electrothermal atomic absorption spectrometry (ETAAS). Optimum masses and mass ratios of permanent modifiers for the analysis of Cd and Pb in sample solutions have been investigated. The 280 μg of Mo, 200 μg of Ir, 200 μg of Ru, 280 μg of Mo + 200 μg of Ir or 280 μg of Mo + 200 μg of Ru has been found as efficient as 5 μg of Pd + 3 μg of Mg(NO3)2 for increasing thermal stabilization of analytes and for decreasing the most serious interferences. Pyrolysis and atomization temperatures, atomization and background signal shapes, characteristic masses and detection limits of analytes in dissolved samples with or without permanent and conventional modifiers have been compared. The detection limits and characteristic masses obtained with Mo-Ir coated platform are 0.01 μg g−1 and 1.1 pg for Cd and 0.09 μg g−1 and 19 pg for Pb, respectively. Long-term stabilities for analytes in samples with Mo, Mo-Ir, Mo-Ru and Pd + Mg(NO3)2 have been studied. Cadmium and lead contents have been determined in certified and standard reference materials by using optimum conditions investigated and the results obtained with Mo-Ir or Mo-Ru were in agreement with the values of certified reference materials.  相似文献   

4.
A multi-element graphite furnace atomic absorption spectrometry (GFAAS) method was elaborated and applied for the simultaneous determination of As, Cd, Cr, Cu, and Pb in various kinds of honey samples (acacia, floral, linden, rape, and milkweed) using the transversally heated graphite atomiser (THGA) with end-capped tubes and integrated graphite platforms (IGPs). For comparative GFAAS analysis, direct (without digestion) and indirect (with digestion in a microwave oven) sample preparation procedures were tested. The effects of several chemical modifiers, such as NH4H2PO4, NH4H2PO4-Mg(NO3)2, and Pd(NO3)2-Mg(NO3)2, were studied to obtain optimal pyrolysis and atomization conditions for the set of analytes studied. The most efficient modifier was proved to be the mixture of 5 μg Pd (applied as nitrate) plus 3 μg Mg(NO3)2, allowing the optimal 600 °C pyrolysis and 2300 °C atomization temperatures. To prevent the sputtering and foaming of the matrix during the drying and pyrolysis steps of the furnace heating program, the sample and modifier solutions (20 + 5 μl, respectively) were dispensed together onto the IGP of the THGA pre-heated at 80 °C.The effect of increasing concentration of honey matrix was studied on the integrated absorbance (Aint) signals of analytes. The Aint signals of Cr and Pb were not altered up to 10% (m/v) matrix content in the sample solutions. The matrix effect was slightly suppressive on the Aint signals of As, Cd, and Cu above 2% (m/v) honey concentration. The recovery was found to be ranged between 85 and 115% for Cd, Cr, Cu, and Pb, whereas it was a lower, compromise value of 70-99% for As. The limit of detection (LOD) data were 1, 0.04, 0.09, 0.3, and 0.6 μg l−1 for As, Cd, Cr, Cu, and Pb, respectively, which values correspond to 20, 0.8, 1.8, 5.3, and 12 ng g−1, respectively, in the solid samples. The characteristic masses were found to be 21 pg As, 1.3 pg Cd, 4 pg Cr, 12 pg Cu, and 33 pg Pb. The As, Cd, Cr, Cu, and Pb contents of the studied 42 honey samples varied significantly, i.e. from below the LOD up to 13, 3.3, 109, 445, and 163 ng g−1, respectively.  相似文献   

5.
Three platinum group elements (Pd, Ir and Rh) both in solution and in pre-reduced form, and also combined with Mg(NO3)2 or ascorbic acid, were assessed as possible chemical modifiers on the atomization of As in digest solutions of seafood matrices (clam and fish tissue) by tungsten coil electrothermal atomic absorption spectrometry (TCA-AAS) and compared without a modifier. Of 28 modifier alternatives in study including single form and binary mixtures, and based on maximum pyrolysis temperature without significant As loss and best As absorbance sensitivity during atomization, three modifiers: Rh (0.5 μg), Ir (1.0 μg) and Rh (0.5 μg) + ascorbic acid (0.5 μg), at optimum amounts were pre-selected and compared. The definitive modifier (rhodium (0.5 μg)) was selected by variance analysis. The mean within-day repeatability was 3% in consecutive measurements (25-300 μg l−1) (three cycles, each of n = 6) and showed good short-term stability of the absorbance measurements. The mean reproducibility was 4% (n = 18 in a 3-day period) and the detection limit (3σblank/slope) was 42 pg (n = 16). Quantitation was by standard additions to compensate for matrix effects not corrected by the modifier. Three sample digestion procedures were compared in fish and clam tissue samples: microwave acid digestion alone (A) or combined with the addition of 2% (m/v) K2S2O8 solution followed either by UV photo-oxidation (B) or re-digestion in a thermal block (C). The accuracy was established by determination of As in certified reference material of dogfish muscle (DORM-2). Procedures B and C showed good recoveries (102% (n = 4) and 103% (n = 7), respectively), whereas procedure A was not quantitative (85%). The methodology is simple, fast, reliable, of low cost and was applied to the determination of total As in lyophilized samples of clam and fish collected in the Chilean coast.  相似文献   

6.
The present work reports the development of a methodology for the direct determination of vanadium in high saline waters derived from offshore petroleum exploration employing electrothermal atomic absorption spectrometry. Such waters, usually called produced waters, present complex composition containing various organic and inorganic substances. In order to attain best conditions (highest sensitivity besides lowest background) for the methodology, studies about the effects of several variables (evaluation of pyrolysis and atomization temperatures, type of chemical modifier, concentration of modifier and pyrolysis time) and the convenient calibration strategy were performed. Best conditions were reached with the addition of 10 μg of NH4H2PO4 as chemical modifier employing pyrolysis (during 10 s) and atomization temperatures of 1500 and 2700 °C, respectively. Obtained results indicated that, in this kind of sample, vanadium can be determined by standard addition method or employing an external calibration approach with standard solutions prepared in 0.8 mol l−1 NaCl medium. In order to evaluate possible matrix interferences, a recovery test was performed with five spiked samples of produced waters. The limit of detection, limit of quantification and relative standard deviation in 0.8 mol l−1 NaCl medium were also calculated and the derived values were 1.9 μg l−1, 6.3 μg l−1 and 5.6% (at 10 μg l−1 level), respectively.  相似文献   

7.
A simple, fast, and reliable method was developed for the determination of cadmium in urine specimens by graphite furnace atomic absorption spectrometry (GFAAS). The method involved dilution (1:1) of the specimens with a 4.0% HNO3, direct injection of a 10 μl aliquot of the corresponding solution into a hot transversely-heated graphite atomizer (110 °C), and application of a fast atomization program (42 s) in which the conventional dry-pyrolysis sequence was substituted by a high-temperature (300 °C) drying step. The effect of the injection temperature (A), injection rate (B), pyrolysis’ ramp (C) and hold (D) times over the analyte’s integrated absorbance, peak-shape and repeatability of the measurements was evaluated by means of a 24-1 fractional factorial design. All those individual variables, as well as their first-order interactions (AB-, AC- and AD-type interactions) were found to exert a statistically significant effect (P<0.05). The lack of a chemical modifier other than the nitric acid itself benefited the overall methodology by allowing low-temperature atomization (1200 °C), enhanced atomic and background signals separation, and reduced blank values. A detection limit (3s, n=20) of 0.06 μg l−1 Cd, corresponding to 0.12 μg l−1 Cd in the urine specimen, and a characteristic mass of 1.78 pg/0.0044 s were obtained under the optimized conditions. The standard calibration technique (SCT) was used for quantitation. The successful determination of cadmium in Seronorm™ Trace Elements Urine Batch No. 115 (Nycomed Pharma AS) and in four urine specimens from volunteer donors (recoveries: 91.3-103.4%) attested to the robustness of the proposed method.  相似文献   

8.
Acar O 《Talanta》2005,65(3):672-677
Cadmium, copper and lead in soils, sediments and spiked sea water samples have been determined by electrothermal atomic absorption spectrometry (ETAAS) with Zeeman effect background corrector using NH4NO3, Sc, Pd, Sc + NH4NO3, Pd + NH4NO3, Sc + Pd and Sc + Pd + NH4NO3 as chemical modifiers. A comprehensive comparison was made among the modifiers and without modifier in terms of pyrolysis and atomization temperatures, atomization and background absorption profiles, characteristic masses, detection limits and accuracy of the determinations. Sc + Pd + NH4NO3 modifier mixture was found to be preferable for the determination of analytes in soil and sediment certified and standard reference materials, and sea water samples because it increased the pyrolysis temperature up to 900 °C for Cd, 1350 °C for Cu and 1300 °C for Pb. Optimum masses of mixed modifier components found are 20 μg Sc + 4 μg Pd + 8 μg NH4NO3. Characteristic masses of Cd, Cu and Pb obtained are 0.6, 5.3 and 15.8 pg, respectively. The detection limits of Cd, Cu and Pb were found to be 0.08, 0.57 and 0.83 μg l−1, respectively. Depending on the solid sample type, the percent recoveries were increased up to 103% for Cd, Cu and Pb by using the proposed modifier mixture. The accuracy of the determination of analytes in the sea water samples was also increased.  相似文献   

9.
Electrothermal atomization of beryllium from graphite and tungsten surfaces was compared with and without the use of various chemical modifiers. Tungsten proved to be the best substrate, giving the more sensitive integrated atomic absorption signals of beryllium. Tungsten platform atomization with zirconium as a chemical modifier was used for the determination of beryllium in several NIST SRM certified reference samples, with good agreement obtained between the results found and the certified values. The precision of the measurements (at 10 μg L−1), the limit of detection (3σ), and the characteristic mass of beryllium were 2.50%, 0.009 μg L−1 and 0.42 pg, respectively.  相似文献   

10.
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   

11.
The determination of cadmium (Cd) in fertilizers is of major interest, as this element can cause growth problems in plants, and also affect animals and humans. High-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) with charge-coupled device (CCD) array detection overcomes several of the limitations encountered with conventional line source AAS, especially the problem of accurate background measurement and correction. In this work an analytical method has been developed to determine Cd in fertilizer samples by HR-CS GF AAS using slurry sampling. Both a mixture of 10 μg Pd + 6 μg Mg in solution and 400 μg of iridium as permanent modifier have been investigated and aqueous standards were used for calibration. Pyrolysis and atomization temperatures were 600 °C and 1600 °C for the Pd-Mg modifier, and 500 °C and 1600 °C for Ir, respectively. The results obtained for Cd in the certified reference material NIST SRM 695 (Trace Elements in Multi-Nutrient Fertilizer) of 16.7 ± 1.3 μg g−1 and 16.4 ± 0.75 μg g−1 for the Pd-Mg and Ir modifier, respectively, were statistically not different from the certified value of 16.9 ± 0.2 μg g−1 on a 95% confidence level; however, the results obtained with the Ir modifier were significantly lower than those for the Pd-Mg modifier for most of the samples. The characteristic mass was 1.0 pg for the Pd-Mg modifier and 1.1 pg Cd for the Ir modifier, and the correlation coefficients (R2) of the calibration were > 0.99. The instrumental limits of detection were 7.5 and 7.9 ng g−1, and the limits of quantification were 25 and 27 ng g−1 for Pd-Mg and Ir, respectively, based on a sample mass of 5 mg. The cadmium concentration in the investigated samples was between 0.07 and 5.5 μg g−1 Cd, and hence below the maximum value of 20 μg g−1 Cd permitted by Brazilian legislation.  相似文献   

12.
Cabon JY 《Talanta》2005,65(2):402-407
Hydrofluoric acid, added to seawater, can assist in the removal of chloride in the drying step by precipitating fluoride salts, thus suppressing the chloride interference effects induced on the atomization signals of Cu and Mn. By adding HF to seawater before the analysis, MgF2 and CaF2 are precipitated at the bottom of the sampling flask, without precipitating Cu and Mn, and are consequently not introduced into the graphite furnace. Because sodium salts are eliminated at the pretreatment step, the whole seawater matrix is eliminated before the atomization of Cu or Mn. Therefore, the analyzed volume of seawater can be increased by using the multi-injection procedure without degradation of the limit of detection and risks of spectral interferences. The limit of detection obtained for Cu and Mn are 0.05 and 0.01 μg L−1, respectively, for a 50 μL analyzed seawater volume.  相似文献   

13.
Traces of Cd were determined by electrothermal atomic absorption spectrometry after electrochemical preconcentration on a commercial graphite ridge probe modified with Pd. The Pd electrochemically deposited on the probe surface served not only as the modifier but it also protected the graphite surface. Cd was electrodeposited at a controlled potential − 1.2 V (vs. saturated calomel electrode) using the Pd-modified graphite probe as a working electrode. The sensitivity of Cd determination remained unchanged for 300 electrodeposition and atomization cycles. The detection limit (3σblank) was improved with increasing time of electrolysis and was 1.2 ng l− 1 for a 10 min electrolysis time in the presence of 0.1 mol l− 1 NaNO3. The procedure was applied for the determination of Cd in (1 + 1) diluted seawater and in (1 + 1) diluted urine samples using the standard addition method.  相似文献   

14.
A flow-based procedure was developed for the direct spectrophotometric determination of the iodine value (IV) in biodiesel. The procedure was based on the microextraction/reaction of unsaturated compounds with triiodide ions in an aqueous medium by inserting the reagent solution between the aliquots of biodiesel without any pretreatment. The interaction occurred through the biodiesel film formed on the inner walls of the hydrophobic tube used as the reactor and at the aqueous/biodiesel interfaces. The spectrophotometric detection was based on the discoloration of the I3 reagent in the aqueous phase by using a glass tube coupled to a fiber-optic spectrophotometer as the detection cell. Reference solutions were prepared by dilution of biodiesel samples with previously determined IV in hexane. The analytical response was linear for IV from 13 to 135 g I2/100 g with a detection limit of 5 g I2/100 g. A coefficient of variation of 1.7% (n = 10) and a sampling rate of 108 determinations per hour were achieved by consuming 224 μL of the sample and 200 μg of I2 per determination. The slopes of analytical curves obtained with three different biodiesel samples were in agreement (variations in slopes lower than 3.1%), thus indicating an absence of any matrix effects. Results for biodiesel samples from different sources agreed with the volumetric official procedure at the 95% confidence level. The proposed procedure is therefore a simple, fast, and reliable alternative for estimating the iodine value of biodiesel.  相似文献   

15.
A method was developed for the determination of selenium in human milk using electrothermal atomic absorption spectrometry. The use of chemical modifiers as well as their implications during the pyrolysis step was examined. The chemical modifiers that were studied were Zr, Ir as well as the mixed modifier Zr-Ir. The Ir modifier stabilized selenium at 1000 °C, Zr at 800 °C, while the mixed modifier at 1200 °C. The effect of modifier mass was studied and was found that better results are achieved with addition of 2 μg Zr and 2 μg Ir. The characteristic masses of selenium in the presence of Zr, Ir and the mixed modifier were found to be 73.3, 18.0 and 14.7 pg, respectively, while the corresponding limits of detection were found 2.0, 0.50 and 0.41 μg l−1. Consequently better results were obtained with the mixed modifier. The developed method was applied for the determination of selenium in human milk, which was digested with a HNO3 + H2O2 mixture in a microwave oven. The limit of detection of the method was 1.37 μg l−1, the characteristic mass, m0, was 48.8 pg and the repeatability was less than 5% as R.S.D.(%). Matrix matched calibration was used. Recoveries were estimated to be 93-105%. The method was applied to breast milk of Greek women (n = 9) and the Se content was found to be in the range 16.7-42.6 μg l−1 with mean value 27.4 ± 5.5 μg l−1.  相似文献   

16.
Two analytical methods for the determination of cadmium in wheat flour by electrothermal atomic absorption spectrometry without prior sample digestion have been compared: direct solid sampling analysis (SS) and slurry sampling (SlS). Besides the conventional modifier mixture of palladium and magnesium nitrates (10 μg Pd + 3 μg Mg), 0.05% (v/v) Triton X-100 has been added to improve the penetration of the modifier solution into the solid sample, and 0.1% H2O2 in order to promote an in situ digestion for SS. For SlS, 30 μg Pd, 12 μg Mg and 0.05% (v/v) Triton X-100 have been used as the modifier mixture. Under these conditions, and using a pyrolysis temperature of 800 °C, essentially no background absorption was observed with an atomization temperature of 1600 °C. About 2 mg of sample have been typically used for SS, although as much as 3-5 mg could have been introduced. In the case of SlS multiple injections had to be used to achieve the sensitivity required for this determination. Calibration against aqueous standards was feasible for both methods. The characteristic mass obtained with SS was 0.6 pg, and that with SlS was 1.0 pg. The limits of detection were 0.4 and 0.7 ng g−1, the limits of quantification were 1.3 and 2.3 ng g−1 and the relative standard deviation (n = 5) was 6-16% and 9-23% for SS and SlS, respectively. The accuracy was confirmed by the analysis of certified reference materials. The two methods were applied for the determination of cadmium in six wheat flour samples acquired in supermarkets of different Brazilian cities. The cadmium content varied between 8.9 ± 0.5 and 13 ± 2 ng g−1 (n = 5). Direct SS gave results similar to those obtained with SlS using multi-injections; the values of both techniques showed no statistically significant difference at the 95% confidence level. Direct SS was finally adopted as the method of choice, due to its greater simplicity, the faster speed of analysis and the better figures of merit.  相似文献   

17.
Scaccia S 《Talanta》2005,66(3):805-808
A graphite furnace atomic absorption method is described for the determination of traces of Ni in 52 mole percent (mol.%) Li2CO3 and 48 mol.% Na2CO3 melts after dissolution of the sample in dilute nitric acid. Maximum pyrolysis and optimum atomisation temperatures for the analyte were determined in the presence of the Li and Na matrix constituents. Pre-pyrolysed ascorbic acid (typical amount of 5 μg) has been used as chemical modifier for effectively suppressing the chemical and spectral interferences of the Li/Na matrix, thus that the analysis can be conducted using acid-matched standard solutions. The results of the Ni analysis in synthetic sample solutions by calibration graph against acid-matched standards well agree with those obtained by the method of standard additions. Recoveries ranged from 99 to 101% and the relative standard deviation is around 3% at the 20 μg L−1 level. Moreover, the use of the chemical modifier leads to an improvement of the lifetime of the graphite tube. The Ni detection limit (3σ) in Li/Na carbonate melts for the proposed method is similar to that obtained in aqueous solution, i.e. 5 × 10−8 g analyte per gram of (Li0.52Na0.48) 2CO3 melt. This method is successfully applied to the determination of nickel in real carbonate melt samples.  相似文献   

18.
When tin is to be determined in such a complex matrix like aqua regia extracts of environmental samples by electrothermal atomic absorption spectrometry (ETAAS), spectral interferences occur when deuterium-lamp (D2) background correction is used, even using high pyrolysis temperature of 1400 °C achieved with palladium with citric acid chemical modifier. We have found that the further addition of NH4F to palladium with citric acid chemical modifier is essential for overcoming the above-mentioned problems for which aluminium oxide is most probably responsible. It is supposed, that NH4F enables volatilization of the alumina matrix formed by hydrolysis from the chloride salt and interfering in a gas phase via the formation of AlF3 which could be, in contrast to aluminium oxide, removed from the graphite furnace during the pyrolysis stage. Using the proposed chemical modifier, the direct and accurate determination of Sn in aqua regia extracts from rocks, soils and sediments is possible even when using matrix free standard solutions. This presumption was confirmed by the analysis of certified reference samples and by the comparison with inductively coupled plasma time of flight mass spectrometry (ICP-TOFMS) method. Characteristic mass and LOD value for the original sample (10-μL aliquots of sample) was 17 pg and 0.055 μg g−1, respectively.  相似文献   

19.
The sequential injection (SIA) technique was applied for the on-line preparation of an “oil in water” microemulsion and for the determination of aluminum in new and used lubricating oils by electrothermal atomic absorption spectrometry (ET AAS) with Zeeman-effect background correction. Respectively, 1.0, 0.5 and 1.0 ml of surfactants mixture, sample and co-surfactant (sec-butanol) solutions were sequentially aspirated to a holding coil. The sonication and repetitive change of the flowing direction improved the stability of the different emulsion types (oil in water, water in oil and microemulsion). The emulsified zone was pumped to fill the sampling arm of the spectrometer with a sub-sample of 200 μl. Then, 10 μl of this sample solution were introduced by means of air displacement in the graphite tube atomizer. This sequence was timed to synchronize with the previous introduction of 15 μg of Mg(NO3)2 (in a 10 μl) by the spectrometer autosampler. The entire SIA system was controlled by a computer, independent of the spectrometer. The furnace program was carried out by employing a heating cycle in four steps: drying (two steps at 110 and 130 °C), pyrolisis (at 1500 °C), atomization (at 2400 °C) and cleaning (at 2400 °C). The calibration graph was linear from 7.7 to 120 μg Al l−1. The characteristic mass (mo) was 33.2 pg/0.0044 s and the detection limit was 2.3 μg Al l−1. The relative standard (RSD) of the method, evaluated by replicate analyses of different lubricating oil samples varied in all cases between 1.5 and 1.7%, and the recovery values found in the analysis of spiked samples ranged from 97.2 to 100.4%. The agreement between the observed and reference values obtained from two NIST Standard Certified Materials was good. The method was simple and satisfactory for determining aluminum in new and used lubricating oils.  相似文献   

20.
M. Vilar 《Talanta》2007,71(4):1629-1636
Different analytical methods for the determination of lead in Orujo spirits by electrothermal atomic absorption spectrometry (ETAAS) were developed using permanent modifiers (W, Ir, Ru, W-Ir and W-Ru) thermally deposited on platforms inserted in pyrolitic graphite tubes and Pd-Mg(NO3)2 conventional modifier mixture. In all cases, the Pb determination was performed without any sample pretreatment or preconcentration steps. The comparison between the chemical modifiers employed has been made in terms of pyrolysis and atomization temperatures, characteristic masses, detection limits, and atomization and background signal shapes. The limits of detection obtained were 0.375, 0.387, 0.109, 0.251 and 0.267 ng mL−1 for W, Ir, Ru, W-Ir and W-Ru, respectively and 0.710 ng mL−1 for Pd-Mg(NO3)2. The characteristic masses were 14.1, 11.2, 5.6, 8.3 and 9.3 pg for W, Ir, Ru, W-Ir and W-Ru, respectively and 22.2 pg for Pd-Mg(NO3)2. For all the developed procedures using the different modification systems, the relative standard deviations (<10%) and the analytical recoveries (95-103%) were acceptable. The more suitable methods for Pb determination in distillate spirits were those using permanent modifiers in contrast with classical Pd-Mg(NO3)2. The best analytical performance was achieved for W, Ir and W-Ir methods, which were applied to lead determination in Orujo spirit samples from Galicia (NW Spain). The Pb concentrations found in the analyzed samples were comprised in the range (<LOD to 1.5 μg mL−1).  相似文献   

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