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1.
An improved sheath-flow interface used to couple capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICP-MS) and a microwave-assisted extraction used to extract each arsenic species in seafood were developed in this work. The improved sheath-flow interface completely avoids laminar flow in CE capillary caused by the suction from ICP-MS, makes electric supply more stable in CE, and transports analyte solution to ICP-MS easily and more efficiently. CE-ICP-MS coupled with our interface have two quantitative analysis modes: continuous sample-introduction mode and collective sample-introduction mode. The collective sample-introduction technique greatly reduced the dead volume of interface to approximately zero, obviously avoided the excessive dilution of analyte, and eventually led to a much lower detection limit and a much better electrophoretic resolution. This was demonstrated by the better symmetry and narrow peak widths (10-12 s) and much lower detection limits (0.030-0.042 μg/L) of four species of arsenic determined with collective sample-introduction mode.With the help of this improved sheath-flow interface and the microwave-assisted extraction, we have successfully separated and determined four arsenic species, As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in dried Mya arenaria Linnaeus and Shrimp samples using CE-ICP-MS within 10 min with a relative standard deviation of 2-4% (peak areas, n = 6) and a recovery of 96-105%. 相似文献
2.
《Spectrochimica Acta Part B: Atomic Spectroscopy》2005,60(3):307-318
The feasibility of depth profiling of zinc-coated iron sheets by laser ablation (LA) was studied using an Nd:YAG laser (1064 nm) with inductively coupled plasma optical emission spectrometry (ICP-OES), and an excimer ArF* laser (193 nm) with a beam homogenizer. The latter was coupled to an ICP with mass spectrometry (ICP-MS). Fixed-spot ablation was applied. Both LA systems were capable of providing depth profiles that approach the profiles obtained by glow discharge optical emission spectroscopy (GD-OES) and electron probe X-ray microanalysis (EPXMA). For Nd:YAG laser an artefact consisting of zinc depth profile signal tailing appeared, enlarging thus erroneously diffusional coating–substrate interface profile. However, the ArF* system partially reduced but not suppressed that phenomenon. For both LA systems the Fe signal from the substrate increased with depth as expected and reached a plateau. The depth resolution (depth range corresponding to 84%–16% change in the full signal) achieved was several micrometers. Ablation rate was found to depend on ablation spot area at constant irradiance. Consequently, ablated volume per shot dependence on pulse energy exhibits deviation from linear course. 相似文献
3.
Evan F. Cromwell Peter Arrowsmith 《Journal of the American Society for Mass Spectrometry》1996,7(5):458-466
A novel mass spectrometer system for elemental analysis is described. The instrument combines an inductively coupled plasma (ICP) ion source with a Mattauch-Herzog mass spectrometer and multichannel ion detector. Ion detection is simultaneous and an elemental mass spectrum (20–230 μ) can be acquired in <10 ms. The instrument can be used with either Ar or He plasma sources. The speed of the system makes it well suited for acquisition of fast (10–100-ms duration) transient signals, such as those generated by pulsed laser ablation sample introduction. Preliminary system performance characteristics, which include detection limits, stability, and measurement accuracy, obtained with an Ar ICP are presented. The application of the instrument to the analysis of solid samples by laser ablation is discussed. 相似文献
4.
Linda Zaoralkova Ales Hrdlicka Vitezslav Otruba Petr Sulovsky Nicole Gilon Detlef Günther Viktor Kanicky 《Chemical Papers》2011,65(6):769-781
The applicability of laser ablation (LA) inductively coupled plasma (ICP) spectrometry for assessing elemental distributions
in layered ceramics was investigated and compared with electron probe microanalysis (EPMA). Ordinary glazed wall tiles were
employed as model specimens due to their defined structure and composition. They were used for calibration in the analysis
of ancient pottery. A qualitative depth profile was acquired by single-spot laser drilling perpendicular to coatings with
a Nd:YAG (1064 nm) laser coupled with an ICP optical emission spectrometer (OES). The lower lateral resolution associated
with the laser spot diameter of 1.0 mm led to smoothing of the depth profile due to the averaging of local irregularities.
In addition, transverse line scans by ablation across the tile section using an ArF* (193 nm) laser coupled with an ICP mass
spectrometer (MS) were performed. LA-ICP-OES depth profiles and LA-ICP-MS transverse scans were validated by EPMA section
scans and 2D back-scattered electrons images. The LA-ICP-OES acquisition was less dependent on sample surface and layer irregularities,
whereas the transverse line scan over the tile section with the small-spot beam offered insight into the micromorphology of
the individual layer. The combined approach revealed the occurrence of individual mineral grains, micro-heterogeneities and
the character of interfaces between layers. 相似文献
5.
《Spectrochimica Acta Part B: Atomic Spectroscopy》2005,60(1):73-79
An extended study of different sampling introduction approaches using inductively coupled plasma mass spectrometry (ICP-MS) is presented for the determination of boron in steel samples. The following systems for sample introduction were applied: direct sample solution nebulization by continuous nebulization (CN) using a cross-flow nebulizer and with flow injection (FI), applied to 0.1% (m/v) and 0.5% (m/v) sample solutions, respectively; FI after iron matrix extraction, using acetylacetone–chloroform, and isotopic dilution (ID) analysis as the calibration method; FI with on-line electrolytic matrix separation; and spark ablation (SA) and laser ablation (LA) as solid sampling techniques. External calibration with matrix-matching samples was used with CN, SA, and LA, and only acid solutions (without matrix matching) with FI methods. When FI was directly applied to a sample solution, the detection limit was of 0.15 μg g−1, improving by a factor of 4 that was obtained from the CN measurements. Isotopic dilution analysis, after matrix removal by solvent extraction, made it possible to analyse boron with a detection limit of 0.02 μg g−1 and, with the on-line electrolytic process, the detection limit was of 0.05 μg g−1. The precision for concentrations above 10 times the detection limit was better than 2% for CN, as well as for FI methods. Spark and laser ablation sampling systems, avoiding digestion and sample preparation procedures, provided detection limits at the μg g−1 levels, with RSD values better than 6% in both cases. Certified Reference Materials with B contents in the range 0.5–118 μg g−1 were used for validation, finding a good agreement between certified and calculated values. 相似文献
6.
The combination of inductively coupled plasma atomic emission spectrometry and high resolution inductively coupled plasma mass spectrometry for the determination of 70 elements in coal were studied. Four microwave-assisted digestion procedures with different dissolution mixtures (nitric and hydrofluoric acids, aqua regia and hydrogen peroxide), lithium metaborate fusion with and without previous sample ashing as well as direct sampling by laser ablation (LA) have been tested. Examples of spectral interferences are given and different correction procedures are discussed. Detection limits in the low ng g(-1) range were obtained for most of the elements investigated by using high-purity reagents and by taking special care to prevent sample contamination during preparation. The precision was assessed from replicate analysis (including sample preparation) of coal samples and was found to be, as average values far all elements, 4-5% RSD and 10-15% RSD for procedures including sample digestion and LA sampling, respectively. The accuracy of the overall analytical procedures was estimated by analysis of certified reference materials and of a coal sample obtained from the Interlab Trace round robin test. Among the dissolution mixtures tested, the combination of nitric and hydrofluoric acids with hydrogen peroxide provide the best agreement with certified, recommended, literature-compiled or consensus values, though fusion is necessary to obtain quantitative recoveries for Si, Cr, Hf, W, Zr, Y. In general, results obtained by LA fall within +/-20% of those obtained after digestion. 相似文献
7.
The determination of trace elements in pure quartz glass samples has been performed by coupling an ICP quadrupole mass spectrometer with the LINA-Spark-Atomizer, an IR laser ablation system dedicated to direct bulk and surface analysis of solid samples. Linear calibration curves were obtained for nine elements (Na, Al, Ca, Ti, Cr, Mn, Zr, Ba, and Pb) in the ng g–1 range with detection limits of less than 10 ng g–1 for Ca, Cr, Mn, Zr, Ba, and Pb and in the range of 120–220 ng g–1 for Na, Al, and Ti. The distance between the laser focal point and the sample surface has a significant influence on signal intensity and precision, both of which can be improved by a factor of approximately two by focusing the laser 15 mm behind the sample surface. Aerosol moistening reduced the standard deviation of the signal intensity by a factor of 2–4. Signal instability, which resulted from different ablation rates or variations in the transmission of the mass spectrometer, were compensated by use of the simultaneously measured SiAr+ ion as an internal standard. Under these conditions precision was usually better than 5% RSD. The results were compared with those obtained by use of a commercial LA–ICP–MS system. With this instrumentation linear calibration curves were achieved for three elements only (Al, Ti, and Pb), showing that LA–ICP–MS is less appropriate for bulk analysis in the ng g–1 range. 相似文献
8.
A technique involving the coupling of laser ablation and inductively coupled plasma mass spectrometer has been used for semi-quantitative analysis of glasses without sample dissolution. The characteristic features of this technique is low detection limit and accuracy between a few % up to 20%. An NIST glass standard (SRM 612) was dissolved and then analysed by ICP-MS in semi-quantitative mode. The results were in close agreement with the certified values for elements such as Mn, Sr, Y, Ti...Abbreviations AA
atomic absorption
- ICP-OES
inductively coupled plasma optical emission spectroscopy
- ICP-MS
inductively coupled plasma mass spectrometry
- LA
laser ablation 相似文献
9.
《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(10):1535-1545
Many tasks in bulk analysis, micro analysis and depth profile analysis can be solved advantageously by laser ablation inductively coupled plasma mass spectrometry (Laser ICP-MS) in particular, when both the chemical and elemental distributions in the sample are to be determined. However, the analyst has to take into account that the analytical precision and accuracy of the Laser ICP-MS is influenced decisively by signal standardization, the homogeneity of the samples as well as calibration standards and the mass-spectrometric measuring mode, which is usually sequential when performed with scanning mass spectrometers such as quadrupol- or sector-based instruments. Using the ablated mass as standard, an excellent level of the analytical precision and accuracy (relative standard deviation R.S.D.<0.5%) has been obtained for homogeneous sample materials such as alloys. For inhomogeneous samples, such as pressed pellets, a statistical test is described, which is based upon the auto-correlation function to characterize the sample inhomogeneity. The application of the test allows us to calculate the representative mass for the quantitative analysis at previously defined analytical precision. In the instrumental part of the paper a new type of an ICP—time-of-flight (TOF) mass spectrometer—is described, constructed and built up in our laboratory. For fast signal counting an application-specific integrated circuit (ASIC) was developed, which permits a time resolution of 1 ns. The analytical performance of the TOF when used in combination with an ICP is demonstrated in terms of resolution, ion extraction rate, detection limits and dynamic range. The determination of 39K+ and 40Ca+ at trace level can be realized in a cool plasma condition (high central gas flow) only with a small interference by 40Ar+. Detection limits of 23 elements were measured with typical values in the lower nanograms per liter range. The ion extraction rates, measured for a sample mass of 1 ng in terms of counts per second divided by the relative isotope abundance, are one order of magnitude higher than those obtained with a quadrupol-based instrument. 相似文献
10.
High resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) was applied for multielement-determination in high-purity
copper (approx. 99.99%). The samples were introduced into the instrument by three different introduction systems, which were
studied with respect to high accuracy, low detection limits and fast analysis: continuous nebulization (CN), flow injection
analysis (FIA) and laser ablation (LA). The trueness of the applied method was checked by the analysis of high-purity copper
reference material (BCR Cu074). All values obtained for this CRM using CN were in the range of the stated uncertainty for
the 9 elements determined: Ag, As, Bi, Cr, Fe, Ni, Pb, Sb, and Sn with contents in the range of 0.5–13 μg/g. Another approach
for checking the trueness of the method was to compare the results obtained by this method characterizing the purity of a
4N (99.99% copper content) copper material with those obtained by application of electrothermal atomic absorption spectrometry
(ET-AAS) and inductively coupled plasma optical emission spectrometry (ICP-OES). For further characterizing, the concentrations
of 49 elements were found in this material below detection limits of HR-ICP-MS in the range of low μg/kg and sub μg/kg. The
combination of HR-ICP-MS and a flow injection analysis system (FIAS) improved the robustness of the system in regard to high
matrix concentrations. Therefore, matrix concentrations up to 4 g/L could be used for liquid analysis and detection limits
were lowered by a factor of 2–5. A calibration method for bulk analysis with laser ablation was developed with doped copper
powder as pressed pellets for calibration standards. This method proved to be an excellent fast semi-quantitative method,
which was less time consuming in comparison with the analysis of liquids. After application of correction factors the deviation
between the results obtained by laser ablation and by analysis of liquids was ≈ 15% for most elements. The method offered
the possibility to check for potential losses of analytes occurring during the wet chemical operations.
Received: 23 November 1998 / Revised: 25 February 1999 / Accepted: 2 March 1999 相似文献
11.
High resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) was applied for multielement-determination in high-purity
copper (approx. 99.99%). The samples were introduced into the instrument by three different introduction systems, which were
studied with respect to high accuracy, low detection limits and fast analysis: continuous nebulization (CN), flow injection
analysis (FIA) and laser ablation (LA). The trueness of the applied method was checked by the analysis of high-purity copper
reference material (BCR Cu074). All values obtained for this CRM using CN were in the range of the stated uncertainty for
the 9 elements determined: Ag, As, Bi, Cr, Fe, Ni, Pb, Sb, and Sn with contents in the range of 0.5–13 μg/g. Another approach
for checking the trueness of the method was to compare the results obtained by this method characterizing the purity of a
4N (99.99% copper content) copper material with those obtained by application of electrothermal atomic absorption spectrometry
(ET-AAS) and inductively coupled plasma optical emission spectrometry (ICP-OES). For further characterizing, the concentrations
of 49 elements were found in this material below detection limits of HR-ICP-MS in the range of low μg/kg and sub μg/kg. The
combination of HR-ICP-MS and a flow injection analysis system (FIAS) improved the robustness of the system in regard to high
matrix concentrations. Therefore, matrix concentrations up to 4 g/L could be used for liquid analysis and detection limits
were lowered by a factor of 2–5. A calibration method for bulk analysis with laser ablation was developed with doped copper
powder as pressed pellets for calibration standards. This method proved to be an excellent fast semi-quantitative method,
which was less time consuming in comparison with the analysis of liquids. After application of correction factors the deviation
between the results obtained by laser ablation and by analysis of liquids was ≈ 15% for most elements. The method offered
the possibility to check for potential losses of analytes occurring during the wet chemical operations.
Received: 23 November 1998 / Revised: 25 February 1999 / Accepted: 2 March 1999 相似文献
12.
The performance of a laser ablation mass analyser designed for in-situ exploration of the chemical composition of planetary
surfaces has been investigated. The instrument measures the elemental and isotopic composition of raw solid materials with
high spatial resolution. The initial studies were performed on NIST standard materials using IR laser irradiance (< 1 GW cm−2) at which a high temporal stability of ion formation and sufficiently low sample consumption was achieved. Measurements of
highly averaged spectra could be performed with typical mass resolution of m/Δm ≈ 600 in an effective dynamic range spanning seven decades. Sensitive detection of several trace elements can be achieved
at the ~ ppm level and lower. The isotopic composition is usually reproduced with 1% accuracy, implying good performance of
the instrument for quantitative analysis of the isotopic fractionation effects caused by natural processes. Using the IR laser,
significant elemental fractionation effects were observed for light elements and elements with a high ionization potential.
Several diatomic clusters of major and minor elements could also be measured, and sometimes these interfere with the detection
of trace elements at the same nominal mass. The potential of the mass analyser for application to sensitive detection of elements
and their isotopes in realistic samples is exemplified by measurements of minerals. The high resolution and large dynamic
range of the spectra makes detection limits of ~100 ppb possible. 相似文献
13.
Koellensperger G Hann S Prinz G Stingeder G Bujatti-Narbeshuber M 《Fresenius' Journal of Analytical Chemistry》2001,370(5):559-565
Three different analytical strategies have been evaluated for the quantification of Ir in geological samples. Glassy rock samples from K?fels and reference material WGB-1 were analyzed directly by inductively coupled plasma sector field mass spectrometry (ICP-SFMS) at mass resolution 400 using membrane desolvation and at mass resolution 9500 without membrane desolvation. Matrix separation by anion-exchange pre-concentration was also investigated. The ultrasonic nebulizer USN6000AT+ (Cetac Technologies, Omaha, NE, USA) incorporating a membrane desolvation unit was used as the sample-introduction system. Sample preparation involved complete microwave-assisted acid digestion of the silicate matrix with HNO3-HCl-HF. The results obtained by the three methods of quantification were in good agreement, showing that oxide-type interferences were effectively eliminated solely by membrane desolvation. The limits of detection were 6 pg g for low resolution measurement with use of the membrane, 15 pg g(-1) at a mass resolution of 9500, and 59 pg g(-1) for the ion-exchange procedure. The ultimate precision obtained for the K?felsit Ir data was, however, compromised by the small sample intake (0.3 g), because of the inhomogeneous distribution of Ir in geological samples. 相似文献
14.
Tomoharu Ishida Takanori Akiyoshi Akiko Sakashita Satoshi Kinoshiro Kyoko Fujimoto Atsushi Chino 《Analytical sciences》2008,24(5):563-569
The laser ablation (LA) method is an effective technique for quantitative analysis. In the present work, a new LA system was developed for the high-sensitivity analysis of metal materials using inductively coupled plasma mass spectrometry (ICP-MS). This system consists of a high-frequency Q-switched laser and 2 scanning mirrors for scanning the ablation spot in an adequately large area of the specimen without vacant spaces. The influence of elemental fractionation (non-stoichiometric generation of vapor species) can be eliminated by repetitive irradiation of this pattern on the same area. Particles generated with an average laser power of 0.6 W with the developed LA system gave intensity and stability substantially similar to that of a 500 microg/ml solution steel sample in solution ICP-MS. The analytical performance of the developed LA-ICP-MS was compared with that of a solution ICP-MS using NIST steel SRMs. The performance of the newly-developed system is comparable to that of conventional solution ICP-MS in both accuracy and precision. The correlation coefficients between the contents and the intensity ratios to Fe were over 0.99 for most elements. The relative standard deviation (RSD) obtained by LA-ICP-MS revealed that this system can analyze iron samples with good precision. The results of ultra trace level analysis of high-purity iron showed that developed LA-ICP-MS is capable of analyzing ppm concentration levels with a 20 - 30 ppb level standard deviation. The detection limit was on the order of 10 ppb for most elements. 相似文献
15.
激光剥蚀串联电感耦合等离子体质谱法(LA-ICP-MS)是一种功能强大的化学元素检测方法,它具有样品前处理简单、多元素同时测定、高通量、高灵敏度、宽线性范围以及原位分析等优点。同时,激光剥蚀可以与多接收器电感耦合等离子体质谱仪(MC-ICP-MS)串联用于稳定同位素组成测定,不仅避免了繁琐的样品前处理,同时还可应用于固体样品的微区原位同位素分析,揭示微观尺度上稳定同位素组成的变化。LA-ICP-MS已广泛应用于地质、考古等领域,其在环境科学领域应用相对起步较晚,但近年来发展迅速。该文总结了近年来LA-ICP-MS的环境分析方法开发及其在环境科学中的应用进展,并对其未来发展趋势进行了展望。 相似文献
16.
V. Kanický Vítëzslav Otruba Karel Novotný Petr Musil Jean-Michel Mermet 《Analytical and bioanalytical chemistry》2001,370(4):387-392
Infrared laser ablation (IRLA) was studied as a sample-introduction technique for the analysis of steels by inductively coupled plasma atomic emission spectrometry (ICP–AES). A comparison of two IRLA–ICP–AES systems based on Q-switched nanosecond Nd?:?YAG lasers was performed. The beam of the Lina-Spark atomizer (LSA Sarl, Cully, Switzerland) based on the Surelite I-20 laser (Continuum, USA) was moved along a circle. A Perkin–Elmer Optima 3000 DV ICP system was used both with lateral and axial viewing modes. A laboratory-made ablation system based on the Brilliant laser (Quantel) was coupled to a Jobin-Yvon 170 Ultrace ICP (lateral viewing, polychromator part employed). A sample was rotated along a circle during ablation. Linearity of calibration plots was verified at least up to 19% Cr and 12% Ni without internal standardization for both LA–ICP–AES systems. Other elements examined were Mo up to 3%, Mn up 1.5%, Si up to 1.7%, and Cu up to 0.15%. The reproducibility was in the range 5–1 %RSD for a mass percentage 0.5–20% of steel constituents. The relative uncertainty of the centroids of the calibration lines was in the range from ± 4% to ± 12% for Cr, Ni, Mn, Mo, and Si, and from ± 8% to ± 19% for Cu. The lowest determinable quantities were calculated for calibration dependencies. Performances of both the IR-LA–ICP–AES were comparable. 相似文献
17.
18.
Key performance features of a miniature laser ablation time‐of‐flight mass spectrometer designed for in situ investigations of the chemical composition of planetary surfaces are presented. This mass spectrometer is well suited for elemental and isotopic analysis of raw solid materials with high sensitivity and high spatial resolution. In this study, ultraviolet laser radiation with irradiances suitable for ablation (< 1 GW/cm2) is used to achieve stable ion formation and low sample consumption. In comparison to our previous laser ablation studies at infrared wavelengths, several improvements to the experimental setup have been made, which allow accurate control over the experimental conditions and good reproducibility of measurements. Current performance evaluations indicate significant improvements to several instrumental figures of merit. Calibration of the mass scale is performed within a mass accuracy (Δm/m) in the range of 100 ppm, and a typical mass resolution (m/Δm) ~600 is achieved at the lead mass peaks. At lower laser irradiances, the mass resolution is better, about (m/Δm) ~900 for lead, and limited by the laser pulse duration of 3 ns. The effective dynamic range of the instrument was enhanced from about 6 decades determined in previous study up to more than 8 decades at present. Current studies show high sensitivity in detection of both metallic and non‐metallic elements. Their abundance down to tens of ppb can be measured together with their isotopic patterns. Due to strict control of the experimental parameters, e.g. laser characteristics, ion‐optical parameters and sample position, by computer control, measurements can be performed with high reproducibility. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
19.
Gunda Koellensperger Stephan Hann Günter Prinz Gerhard Stingeder Michael Bujatti-Narbeshuber 《Analytical and bioanalytical chemistry》2001,370(5):559-565
Three different analytical strategies have been evaluated for the quantification of Ir in geological samples. Glassy rock samples from Köfels and reference material WGB-1 were analyzed directly by inductively coupled plasma sector field mass spectrometry (ICP–SFMS) at mass resolution 400 using membrane desolvation and at mass resolution 9500 without membrane desolvation. Matrix separation by anion-exchange pre-concentration was also investigated. The ultrasonic nebulizer USN6000AT+ (Cetac Technologies, Omaha, NE, USA) incorporating a membrane desolvation unit was used as the sample-introduction system. Sample preparation involved complete microwave-assisted acid digestion of the silicate matrix with HNO3–HCl–HF. The results obtained by the three methods of quantification were in good agreement, showing that oxide-type interferences were effectively eliminated solely by membrane desolvation. The limits of detection were 6 pg g–1 for low resolution measurement with use of the membrane, 15 pg g–1 at a mass resolution of 9500, and 59 pg g–1 for the ion-exchange procedure. The ultimate precision obtained for the Köfelsit Ir data was, however, compromised by the small sample intake (0.3 g), because of the inhomogeneous distribution of Ir in geological samples. 相似文献
20.
Christopher M. Barhick John R. Eyler 《Journal of the American Society for Mass Spectrometry》1992,3(2):122-127
A glow discharge (CD) ion source has been coupled to a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer using a four-element electrostatic lens to accelerate and focus ions generated external to the instrument’s high magnetic field into its analyzer cell. Like other CD mass spectrometers, GD-FT-ICR can provide a quantitative measure of bulk analyte concentration with good precision and accuracy. Although detection limits currently attainable are several orders of magnitude higher than the commercially available magnetic sector-based instrument, CD-FT-ICR holds promise for ultrahigh resolving power elemental mass analysis. Several schemes are proposed to lower the detection limits of the technique while still providing high enough resolution to resolve isobaric interferences. 相似文献