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  • Rapid, Molecule-Free, in-situ Rare Earth Element Abundances by SIMS-SSAMS
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-19
    Evan Groopman, Kenneth Grabowski, Albert J Fahey, Levke Kööp

    We present a novel method for rapid and high-sensitivity in-situ measurements of the rare earth elements (REE) by combined secondary ion mass spectrometry and single-stage accelerator mass spectrometry (SIMS-SSAMS). Traditional SIMS can be limited in its REE sensitivity by the presence of abundant molecular isobars, whose discrimination is often beyond the range of high mass resolving power, and which require energy filtering and careful calibration to deconvolve. These greatly reduce sensitivity and require a priori assumption of terrestrial isotope ratios for deconvolution, which precludes the analysis of some nuclear forensic materials and presolar stardust grains. With the SSAMS, molecular background is reduced by 5 to 6 orders of magnitude, precluding the need for energy filtering and/or high mass resolution. We demonstrate measurement of Gd isotopes (6 µmol/mol) in the presence of a molecular background more than 4 orders of magnitude more intense from a single 15 µm spot in a sample of Madagascar hibonite. From the same spot we can resolve 7 nmol/mol of Tm from its comparably large background. Traditional SIMS requires the measurement of 47+ masses over 0.5 to 3 hours to perform REE deconvolution, while we collect full REE abundance patterns from several minerals in 10 to 30 minutes per spot. We observe no instrumental mass fractionation (±1%) in either Gd or Dy isotope ratio measurements of NIST610/612 glass. These improvements in sensitivity and measurement rapidity open important new avenues for REE imaging of samples and analyses of particles, nuclear materials, and mineral inclusions.

    更新日期:2017-09-20
  • Development, validation and verification of an ICP-MS procedure for a multi-element analysis of uranium ore concentrates
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-19
    Sergei Boulyga, J Alan Cunningham, Zsuzsanna Macsik, Joe Hiess, Maxim V Peńkin, Stephen J Walsh

    The International Atomic Energy Agency (IAEA) uses information from characterization of uranium-bearing material samples to support the verification of States’ declarations and to look for indications of possible undeclared materials and activities. Parameters of interest include, among others, the concentrations of elemental impurities, the patterns of rare earth elements (REE), and the isotope ratios of uranium and some impurity elements. These data along with other physical and chemical properties are being used to assess material quality, monitor chemical processes, and verify material origin. This manuscript describes a Sector Field – Inductively Coupled Plasma – Mass Spectrometry (SF-ICP-MS) procedure for determination of 67 minor and trace elements, including REE, in uranium ore concentrates (UOC) and related compounds without matrix separation. All elements are measured within one instrumental sequence, which improves the timeliness of the analyses. A particular focus is set on developing a reliable quality control mechanism in the absence of uranium-bearing reference materials with certified concentrations of all analysed elements. In order to provide objective experimental evidence that the particular requirements for each specific parameter are fulfilled the validation process included (i) assessment of measurement uncertainties, (ii) analysis of available certified reference materials with uranium matrix (validated for 31 elements), and (iii) measuring test samples in the frame of four inter-laboratory comparison exercises (validated for 54 elements). The majority of the analysed elements could be measured with a satisfactory accuracy but determination of difficult-to-analyse elements, such as silicon and tungsten, requires a modified sample preparation and measurement procedure. Alternative ‘non-destructive’ analytical method, such as XRF or laser ablation ICP-MS, can be applied for direct analysis of non-dissolved residues that remain in the digests.

    更新日期:2017-09-20
  • Advances in discharge-based microplasma for the analysis of trace species by atomic spectrometry
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-18
    Shuang Liu, Yong-Liang Yu, Jian-Hua Wang

    Microplasma has become an actual topic of interest for research in atomic spectrometric systems. The excellent characteristics including low power consumption, small size and weight make microplasma a promising technique for developing portable analytical instrumentations for the real-time and on-site measurement of trace species. In this review, the current status of the discharge-based microplasma is presented and discussed from the point of the four typical applications in the field of atomic spectrometry, i.e., excitation source, atomizer, ionization source, and induced vapor generation. Microplasma excitation source is not only highlighted on the direct detection of trace species by optical emission spectrometry (OES), but also focused on a series of the coupling techniques with gas chromatograph (GC), microelectrodialysis (μED), capillary electrophoresis (CE), chemical vapor generation (CVG), and electrothermal vaporization (ETV). Besides atomization function, microplasma atomizer could serve as a preconcentration device to achieve the trap and release of analyte in atomizer. Microplasma ionization source is used to ablate compounds from the sample surface for analyte detection and profile analysis. Microplasma-induced vapor generation provides a novel sample introduction approach with the feature of green analytical method. Future perspectives of microplasma application in the field of atomic spectrometry are also described.

    更新日期:2017-09-19
  • Simultaneous speciation of chromate, arsenate, molybdate and vanadate in alkaline samples by HPLC-ICP-MS at different concentration levels of vanadate
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-15
    Ana Drinčić, Janez Ščančar, Tea Zuliani, Irena Nikolić, Radmila Milačič
    更新日期:2017-09-18
  • Isotope pattern deconvolution of different sources of stable strontium isotopes in natural systems
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-15
    Anastassiya Tchaikovsky, Johanna Irrgeher, Andreas Zitek, Thomas Prohaska

    Isotope pattern deconvolution (IPD) was used to determine the contribution of different Sr sources to the Sr isotopic composition of natural samples on the example of sturgeon caviar and otoliths. For this purpose, the Sr isotopic composition of raw and salted sturgeon caviar, otoliths as well as water, fish feed and salt (representing the assumed main contributors to the final isotopic composition of strontium in caviar) were analyzed using MC ICP-MS. The molar fractions and their uncertainties were determined using multiple-linear regression modeling and linear algebra calculations. The optimized approach was applied to caviar and otolith samples of different origin. The Sr isotopic composition of raw caviar and otoliths was formed to 79.8 ± 4.3 % by water and 20.2 ± 4.3 % by fish feed (1 SD, n=5, between sites variation). Deconvolution was possible even when the isotopic difference of the n(87Sr)/n(86Sr) between sources was less than 0.1 %. The influence of salting to the isotopic compostion of processed caviar accounted up to almost 80 % for samples treated with salt containing high concentrations of Sr. The developed methodology provides the basis for the accurate origin determination of samples by n(87Sr)/n(86Sr) isotopic-amount ratios, in cases, where the initial natural signature is modified by known additives.

    更新日期:2017-09-15
  • Simultaneous speciation of chromate, arsenate, molybdate and vanadate in alkaline samples by HPLC-ICP-MS at different concentration levels of vanadate
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-15
    Ana Drinčić, Janez Scancar, Tea Zuliani, Irena Nikolić, Radmila Milacic

    Flay ash, cement and electric arc furnace (EAF) dust are frequently mixed in building composites. From them, chromium (Cr), arsenic (As), molybdenum (Mo) and vanadium (V) may be leached. Concentrations of V in leachates may be significantly higher than those of Cr, As and Mo, making simultaneous speciation analysis particularly difficult. In this work, high performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) procedure was used for simultaneous speciation of chromate, arsenate, molybdate and vanadate. First, the behaviour of Cr, As, Mo and V species in different oxidation states was studied during their separation at acidic (pH 5) and alkaline (pH 12) conditions. At alkaline pHs chromate, arsenate, molybdate and vanadate were simultaneously separated and eluted at retention times from 390 to 450 s, 230 to 270 s, 340 to 430 s and 270 to 380 s, respectively and detected on-line by ICP-MS, recording m/z 52, 75, 95 and 51, respectively. When V species were leached in significantly higher concentrations than those of Cr, Mo and As, their detection was possible at low abundance (0.25%) 50V isotope, which is also a mass of 50Cr isotope (abundance 4.345%), due to selective separation between V and Cr species. Good repeatability of measurement (RSD better than ± 3.0%) and quantitative elution of elemental species (column recoveries 99 – 105%) were obtained. Finally, the procedure was applied in simultaneous speciation analysis of chromate, arsenate, molybdate and vanadate in highly alkaline aqueous leachates from composites consisted of fly ash, cement and EAF dust that contained wide range of concentrations of vanadate.

    更新日期:2017-09-15
  • Quantitative detection of harmful elements in alloy steel by LIBS technique and sequential backward selection-random forest (SBS-RF)
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-04
    Fangqi Ruan, Juan Qi, Chunhua Yan, Hongsheng Tang, Tianlong Zhang, Hua Li
    更新日期:2017-09-15
  • “Non-invasive” portable laser ablation sampling of art and archaeological materials with subsequent Sr - Nd isotope analysis by TIMS using 1013 Ω amplifiers
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-13
    Alice Carolin Susanne Knaf, Janne Marij Koornneef, Gareth Davies

    A new integrated trace element and multi-isotope provenancing methodology is presented that uses a portable “non-invasive” pulsed laser ablation sampling technique. Samples are collected on location onto teflon filters for return to a clean laboratory for low blank (pg) geochemical procedures. Ablation pits approximately 60 or 120 μm in width and depth remove μg amounts of material. Following dissolution, trace element ratios are determined by inductively coupled plasma mass spectrometry and combined Sr-Nd isotopes by thermal ionization mass spectrometry. Use of 1013 Ω resistors allows precise analysis of subnanogram amounts of Sr-Nd isotopes, which coupled with the trace element data, provides highly effective multi-variant discrimination for material provenance and authenticity verification. Monitoring of blank contributions is required.

    更新日期:2017-09-13
  • Assessment of exposure to airborne carbon nanotubes by laser-induced breakdown spectroscopy analysis of filter samples
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-23
    J.-B. Sirven, P. Dewalle, C. Quéré, V. Fauvet, M. Tabarant, S. Motellier, L. Golanski, A. Guiot, M. Amdaoud, S. Clavaguera, A. Roynette, S. Pontreau, F.-X. Ouf, F. Gensdarmes
    更新日期:2017-09-13
  • Quantitative correction of matrix effects in the determination of copper in human serum by isotope dilution quadrupole ICP-MS
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-18
    Liuxing Feng, Jun Wang, Hongmei Li, Yanjie Cui, Hai Lu, Naijie Shi
    更新日期:2017-09-13
  • Novel techniques for enhancing the performance of support vector regression chemo-metric in quantitative analysis of LIBS spectra
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-11
    Taoreed Olakunle Owolabi, Mohammed Gondal

    Laser induced breakdown spectroscopy (LIBS) is an atomic emission spectroscopy through which elemental compositions of materials can be determined with little or no sample preparation. Small sample requirement as well as it capacity for rapid and real time analysis contributes significantly to the wider applicability of the technique. However, quantitative analysis of LIBS spectra remains a challenge and requires non-linear modeling technique that fully captures the complex interactions in the laser induced plasma and ultimately reduces the effect of self-absorption. Support vector regression (SVR) recently attracts significant attention in chemo-metrics due to its sound mathematical background and unique ability to model non-linear systems with reasonable degree of precision. This work proposes two novel techniques by which the performance of SVR can be improved for the quantitative analysis of LIBS spectra. The first technique, referred to as homogeneously hybridized support vector regression (HSVR), combines two SVR algorithms in which the output of the first algorithm serves as the input to the second algorithm while the second technique, referred to as internal reference preprocessing method (IRP), uses the spectra feature that is normalized with the emission line intensity which is not significantly affected by self-absorption. The hyper-parameters of the developed models are optimized using gravitational search algorithm (GSA). On the basis of root mean square error, GSA-HSVR-WIRP (without IRP) performs better than GSA-SVR-WIRP with over 75% performance improvement while GSA-HSVR-IRP performs better than GSA-SVR-IRP with over 95% performance improvement. The outcome of this work would be very useful for precise LIBS quantitative analysis and would eventually promote wide applicability of the technique.

    更新日期:2017-09-11
  • Evaluation of the self-absorption reduction of minor elements in laser-induced breakdown spectroscopy assisted with laser-stimulated absorption
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-21
    Jiaming Li, Yun Tang, Zhongqi Hao, Nan Zhao, Xinyan Yang, Huiwu Yu, Lianbo Guo, Xiangyou Li, Xiaoyan Zeng, Yongfeng Lu
    更新日期:2017-09-11
  • Determination of element concentration in geological samples using nanosecond laser-induced breakdown spectroscopy
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-08
    yang Hu, Zi han Li, Tao Lű

    Laser-induced breakdown spectroscopy (LIBS) can be used for measuring the concentrations or ratios of various trace elements in solid samples. A laser pulse with 532 nm wavelength, 5 ns pulse duration, 100 μm beam spot diameter, and 30 mJ single pulse energy is used for ablating the United States Geological Survey (USGS) series of geological standard samples. The concentrations of iron in different geological samples are obtained using artificial neural networks. In addition, the influence of matrix effects on the measurement error is analyzed. Experiment results reveal that the relative errors of BCR-1G, BHVO-2G, BIR-1G, GSD-1G, and GSE-1G between the measured concentrations and the certified concentrations are 1.86%, 5.73%, 0.27%, 3.86%, and 2.63%, respectively, which indicate that the LIBS method using back propagation artificial neural networks can effectively determine the iron concentrations of USGS geological standard samples. The matrix effects of standard samples are analyzed reasonably, which shows that the matrix effects of GSD-1G and GSE-1G are more different than others. As a result, some significant measurement errors in concentration determination resulted from different matrix effects.

    更新日期:2017-09-08
  • Molecule formation induced by non-uniform plume-air interactions in laser induced plasma
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-08
    Pengxu Ran, Huaming Hou, Shengnian Luo

    Measurements with Laser Ablation Molecular Isotopic Spectrometry (LAMIS) are usually performed in atmosphere for rapid isotope analysis, and understanding of molecule formation via plasma-air chemical reactions is important for quantitative analysis of LAMIS. In this work, the expansion of plasma plume from ablation of pure aluminum in air is studied with time- and space-resolved monochromatic imaging and emission spectroscopy. The distributions of neutral Al and O atoms, and AlO radicals formed through plasma chemical reactions are characterized. The emission spectra of AlO bands of B2Σ+–X2Σ+ system are synthesized, and rotational-vibrational temperature obtained through fitting experimental spectra. Inter-molecular vibrational band interference is well re-constructed, and self-absorption of bandheads, especially for the (0-0) band, is corrected. Interpretation of spatial-temporal evolutions of plasma species and plasma temperature provides insights into the formation mechanism of AlO radicals in laser-induced plasma.

    更新日期:2017-09-08
  • Nanosecond laser ablation tandem inductively coupled plasma mass and optical emission spectrometry for micro-chemical elemental analysis
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-08
    Gelian Gong, Saijun Sun, Jibin Zhou, Congying Li, Libing You, Xu LIANG, Xiaodong Fang, Hongyun Xu, Weidong Sun

    A novel experimental system was designed for micro-chemical elemental analysis using laser ablation technique tandem to both mass and optical emission spectrometry. One new excimer gas laser of wavelength 193 nanometer was constructed to replace the COMPEXPRO 102 laser unit in the RESOlution M50 laser ablation system without changing the ablation cell. The ablated mass (aerosol) was introduced into the inductively coupled plasma mass spectrometer, e.g. Agilent 7500, where optical emission spectrometry was detected simultaneously using Ocean Optics fiber optic spectrometer. The fiber optic spectrometer consists of six channels, which can detect the optical emission lines from plasma and cover wavelength from 190 nm to 800 nm. Standard Reference Materials were measured for demonstrating the elemental analytical method. The constant LA-ICP-MS transient signals, acceptable concentration determinations of MPI DING glass ATHO or T1 samples and negligible differences of elemental fractionation due to replacement of laser source in RESOlution M-50, suggest that our new-constructed excimer gas laser can satisfy LA-ICP-MS micro-chemical analysis. Furthermore, the laser ablated particles resultant inductively coupled plasma optical emission lines can be identified, and the quite good linear correlation of signals in various emission lines of the same element analysed, suggest that wavelength resolution necessary for quantitative elemental analysis by LA-ICP-OES can be achievable using fiber optic spectrometer. Lastly, based on sharing the same inductively coupled plasma configuration in our new LA-ICP-MS & OES system, the linear correlation between signals of LA-ICP-MS and LA-ICP-OES for the same elements can be recognized. The calibration curves for optical emission lines of element manganese, and the coefficient ratios around 0.999, suggest that the novel method of LA-ICP-MS & OES might be a feasible option for micro-chemical elemental analysis through synchronously detecting the stoichiometric composition in the laser ablated mass resultant inductively coupled plasma.

    更新日期:2017-09-08
  • Improved detection sensitivity for heavy trace elements using a miniature laser ablation ionisation mass spectrometer
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-21
    R. Wiesendanger, M. Tulej, A. Riedo, S. Frey, H. Shea, P. Wurz
    更新日期:2017-09-07
  • 更新日期:2017-09-07
  • Effects of H2O- and O2-containing He carrier gases on 206Pb/238U system bias and down-hole fractionation in LA-ICPMS of zircons
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-06
    Steffen Allner, Joachim Koch, Simon E. Jackson, Detlef Gunther

    This paper is dealing with the effects the addition of H2O or O2 to He aerosol carrier gas has on 206Pb/238U ratios during laser ablation inductively-coupled plasma mass spectrometry (LA-ICPMS) of natural zircons and synthetic silicate glass. The following parameters were studied: (i) system bias defined as constant but LA-ICPMS system-dependent shifts in 206Pb/238U ratios, (ii) down-hole fractionation given by the slope of 206Pb/238U ratio vs. LA time, and (iii) the sum of (i) and (ii) referred to as overall elemental fractionation. To isolate and study changes of 206Pb/238U ratios arising independently from either LA sampling or ICPMS analysis of the generated aerosols, a diffusion-based gas exchange device was used. The supply of He + O2 caused relative changes in mean 206Pb/238U values and temporal gradients due to the LA process of less than 40 %. By contrast, addition of H2O to the He carrier gas changed 206Pb/238U ratios by up to 150 % through processes occurring during LA sampling as well as ICPMS analysis. Here, opposing temporal gradients of 206Pb/238U ratios canceled out at relative humidity levels close to the ambient saturation vapor pressure. As a consequence, changes in 206Pb/238U ratios caused by down-hole fractionation could be suppressed. However, the admixture of H2O also affected the system bias at the same time, resulting in increased offsets in 206Pb/238U ratios such that the accuracy of LA-ICPMS analyses worsened by up to 6 % when applied to the age determination of zircons. Neither worsening nor significant improvements in the accuracy of 206Pb/238U-based ages were observed in the case of LA-ICPMS using He + O2 carrier gas mixtures.

    更新日期:2017-09-07
  • Comparison of signal intensities and elemental fractionation in 257 nm femtosecond LA-ICP-MS using He and Ar as carrier gas
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-05
    Tao Luo, Qian Ni, zhaochu hu, Wen Zhang, Quanhui Shi, Detlef Günther, yongsheng liu, Keqing Zong, S. H. Hu

    The signal intensities and elemental fractionation at different ambient gas conditions (He, Ar and pre-mixed He-Ar mixture) were investigated using 257 nm femtosecond (fs)-LA-ICP-MS. The experiments show that the change of ablation carrier gases from argon to helium increases the sensitivities of refractory elements (e.g. rare earth elements) in NIST SRM 610 by a factor of 1.05-1.20. Whereas, the signal intensities of volatile elements (e.g. Tl, Cd, Se, Sn, Te, Zn, Pb, Bi, Ge, Ga, Sb, Ag, Cu) were increased by a factor of 1.5-3.0. The much less deposited aerosol particles around the ablation craters produced in helium when compared to argon may partly account for this phenomenon. Our results also suggest that volatile elements may enriched in small aerosol particles produced by femtosecond laser ablation whose transport efficiencies are increased when using He instead of Ar. The calculated elemental fractionation indices (with respect to Ca) of volatile elements (B, Cu, Zn, Ga, Ge, As, Cd, Mo, Ag, Sn, Sb, Pb and Bi) rapid increased to 1.1-1.2 with increasing the spot size from 24 μm to 60 μm when using helium as carrier gas. In contrast, they remain nearly constant at spot sizes of 24-60 μm when using argon as carrier gas. However, indices of volatile elements (Co, Ni, Cu, Zn, Ga, Ge, As, Ag, Cd, Sn, Sb, Pb, Bi) is less than 1 for all the spot sizes investigated. The signal intensities of all elements obtained in pre-mixed He-Ar mixture is similar to the sensitivities acquired in pure helium. Meanwhile, the calculated elemental fractionation indices for all elements generally remain constant and more close to 1 than in pure He or Ar at different spot sizes. The technique of using the pre-mixed He-Ar mixture as carrier gas has been successfully used for the determination of major and trace elements in USGS and MPI-DING glasses by using fs-LA-ICP-MS.

    更新日期:2017-09-05
  • Characterization of SiO2 Nanoparticles by Single Particle – Inductively Coupled Plasma – Tandem Mass Spectrometry (SP-ICP-MS/MS)
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-05
    Eduardo Bolea Fernandez, Diego Leite, Ana Rua-Ibarz, Lieve Balcaen, Maite Aramendía, Martin Resano, Frank Vanhaecke

    The increase in the use of SiO2 nanoparticles (NPs) is raising concern about their environmental and health effects, thus necessitating the development of novel methods allowing for their straightforward detection and characterization. Single Particle ICP- mass spectrometry (SP-ICP-MS) is able to provide information on the size of NPs, their particle number density and mass concentration. However, the determination of Si via ICP-MS is strongly hampered by the occurrence of spectral overlap from polyatomic species (e.g., CO+ and N2+). The use of tandem ICP-MS (ICP-MS/MS) enables interference-free conditions to be obtained, even in the most demanding applications. Upon testing of several gases, the use of CH3F (monitoring of SiF+, mass-shift approach) and of H2 (monitoring of Si+, on-mass approach) were demonstrated to be the most suitable to overcome the spectral interference affecting ultra-trace Si determination (LoD < 15 ng L-1). By using these approaches, SiO2 NPs (ranging between 80 and 400 nm) can be detected and characterized. For SiO2 NPs > 100 nm, it was possible to provide accurate results in a straightforward way, as the signals they give rise to are well resolved from that of the background. In the case of 80 and 100 nm NPs, the use of a simple deconvolution approach following a Gaussian model was needed to characterize SiO2 NPs apparently showing incomplete distributions as a result of the presence of the background signal. Overall, the methods developed using SP-ICP-MS/MS are sensitive and selective enough for interference-free determination of Si at ultra-trace levels, also under the form of SiO2 NPs.

    更新日期:2017-09-05
  • 更新日期:2017-09-05
  • Quantitative detection of harmful elements in alloy steel by LIBS technique and sequential backward selection-random forest(SBS-RF)
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-09-04
    Fangqi Ruan, Juan Qi, Chunhua Yan, Hongsheng Tang, Tianlong Zhang, Hua Li

    In recent years, LIBS quantitative analysis based on multivariate regression has been received great attention, and variable selection is critical for improve accuracy of multivariate regression analysis of LIBS. In present study, sequential backward selection combined with random forest was proposed to improve the detection accuracy of sulfur and phosphorus element in steel. Firstly, the LIBS spectra line of S and P were identified by the NIST database. Secondly, input variables for RF calibration model were selected and optimized by SBS, and RF model parameters (ntree and mtry) were optimized by out-of-bag (OOB) estimation. Finally, optimized input variables and model parameters were employed to build SBS-RF calibration model for quantitative analysis of P and S in steel. Results showed that the SBS-RF model has a good predictions for S (R2 = 0.9991) and P (R2 = 0.9994) compared with univariate method, PLS model and traditional RF model. LIBS coupled with SBS-RF is an effective method for quality supervision and control of steel products.

    更新日期:2017-09-04
  • Double-spike data reduction in the presence of isotopic anomalies
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-08
    Justin Y. Hu, Nicolas Dauphas
    更新日期:2017-09-04
  • Characterization of zircon reference materials via high precision U–Pb LA-MC-ICP-MS
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-09
    Cristiano Lana, Federico Farina, Axel Gerdes, Ana Alkmim, Guilherme O. Gonçalves, Antonio C. Jardim
    更新日期:2017-09-04
  • Unraveling the mechanism and impact of oxide production in LA-ICP-MS by comprehensive analysis of REE-Th-U phosphates
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-31
    Keita Itano, Tsuyoshi Iizuka
    更新日期:2017-08-31
  • Recent advances in analysis of non-traditional stable isotopes by multi-collector inductively coupled plasma mass spectrometry
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-31
    Dawei Lu, Tuoya Zhang, Xuezhi Yang, Peng Su, Qian Liu, Guibin Jiang

    Non-traditional stable isotopes, with no clear definition yet, generally refer to isotopes beyond C, H, O, N, and S with small variations in natural stable isotopic composition, such as isotopes of transitional and heavy metal elements. With the rapid development in multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) technique, non-traditional stable isotopes have emerged as powerful tracers in geosciences, archaeology, anthropology, and environmental sciences. This article summarizes the recent advances in the analysis of non-traditional stable isotopes by MC-ICP-MS. We review recent efforts on improvement of the sensitivity of MC-ICP-MS and optimization of the sample preparation procedures. Special attention is paid to the “emerging” stable isotopes, e.g., vanadium (V), barium (Ba), potassium (K), platinum (Pt), palladium (Pd), silver (Ag), cerium (Ce), erbium (Er), and silicon (Si). We also introduce some novel aspects of application of non-traditional stable isotopes, e.g., in nanotechnology and environmental health studies. Finally, we discuss current challenges and give our perspectives in this active research area.

    更新日期:2017-08-31
  • Current trends in atomic mass spectrometry for the speciation and imaging of metal-based nanomaterials
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-11
    Judy Tsz-Shan Lum, Kelvin Sze-Yin Leung
    更新日期:2017-08-31
  • Welcome to the fifth special issue dedicated to young analytical scientists in JAAS!
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-24
    Jorge Pisonero
    更新日期:2017-08-30
  • Contributors to the Young Analytical Scientists themed issue
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-24
    更新日期:2017-08-30
  • 2017 atomic spectrometry update – a review of advances in X-ray fluorescence spectrometry and its special applications
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-07-21
    Margaret West, Andrew T. Ellis, Christina Streli, Christine Vanhoof, Peter Wobrauschek
    更新日期:2017-08-30
  • Optimizing the analyte introduction for 14C laser ablation-AMS
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-07-10
    Caroline Welte, Lukas Wacker, Bodo Hattendorf, Marcus Christl, Joachim Koch, Christiane Yeman, Sebastian F. M. Breitenbach, Hans-Arno Synal, Detlef Günther
    更新日期:2017-08-30
  • Feasibility of microwave-assisted ultraviolet digestion of polymeric waste electrical and electronic equipment for the determination of bromine and metals (Cd, Cr, Hg, Pb and Sb) by ICP-MS
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-07-06
    Gabrielle D. Iop, Sindy R. Krzyzaniak, Jussiane S. Silva, Erico M. M. Flores, Adilson B. Costa, Paola A. Mello
    更新日期:2017-08-30
  • Laser ablation-inductively coupled plasma-mass spectrometry for quantitative mapping of the copper distribution in liver tissue sections from mice with liver disease induced by common bile duct ligation
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-06-22
    Marta Costas-Rodríguez, Thibaut Van Acker, Agustina A. M. B. Hastuti, Lindsey Devisscher, Sanne Van Campenhout, Hans Van Vlierberghe, Frank Vanhaecke
    更新日期:2017-08-30
  • Real-time depth measurement in glow discharge optical emission spectrometry via differential interferometric profiling
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-06-21
    S. Gaiaschi, S. Richard, P. Chapon, O. Acher
    更新日期:2017-08-30
  • Atmospheric pressure plasma assisted reaction chemical ionization for analysis of chlorinated compounds separated by liquid chromatography
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-06-19
    Joseph E. Lesniewski, William P. McMahon, Kunyu Zheng, Haopeng Wang, Hamid Badiei, Kaveh Jorabchi
    更新日期:2017-08-30
  • Sample preparation of lipstick for further Cd and Pb determination by ICP-MS: is the use of complexing acids really necessary?
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-06-13
    Marcia Foster Mesko, Diogo La Rosa Novo, Filipe Soares Rondan, Rodrigo Mendes Pereira, Vanize Caldeira Costa
    更新日期:2017-08-30
  • 更新日期:2017-08-30
  • Quantitative distribution of Zn, Fe and Cu in the human lens and study of the Zn–metallothionein redox system in cultured lens epithelial cells by elemental MS
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-06-07
    Héctor González-Iglesias, Carson Petrash, Sara Rodríguez-Menéndez, Montserrat García, Lydia Álvarez, Luis Fernández-Vega Cueto, Beatriz Fernández, Rosario Pereiro, Alfredo Sanz-Medel, Miguel Coca-Prados
    更新日期:2017-08-30
  • 更新日期:2017-08-30
  • A miniature liquid electrode discharge-optical emission spectrometric system integrating microelectrodialysis for potassium screening in serum
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-05-05
    Shuang Liu, Yi Cai, Yong-Liang Yu, Jian-Hua Wang
    更新日期:2017-08-30
  • 更新日期:2017-08-30
  • Natural Fe isotope fractionation in an intestinal Caco-2 cell line model
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-04-28
    María R. Flórez, Yulia Anoshkina, Marta Costas-Rodríguez, Charlotte Grootaert, John Van Camp, Joris Delanghe, Frank Vanhaecke
    更新日期:2017-08-30
  • Laser ablation – inductively couple plasma – mass spectrometry/laser induced break down spectroscopy: a tandem technique for uranium particle characterization
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-04-18
    Benjamin T. Manard, C. Derrick Quarles, Jr., E. Miller Wylie, Ning Xu
    更新日期:2017-08-30
  • Characterization of oxidized Ni-based superalloys by GD-OES
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-04-13
    W. J. Nowak
    更新日期:2017-08-30
  • Argon fluoride LA-LEAF for rapid arsenic quantitation
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-04-05
    J. A. Merten, C. A. Jones, P. D. Tribbett
    更新日期:2017-08-30
  • The production of doubly charged sample ions by “charge transfer and ionization” (CTI) in analytical GD-MS
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-02-23
    Sohail Mushtaq, Edward B. M. Steers, DeAnn Barnhart, Glyn Churchill, Martin Kasik, Silke Richter, Jens Pfeifer, Karol Putyera
    更新日期:2017-08-30
  • Overcoming spectral overlap via inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). A tutorial review
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-02-17
    Eduardo Bolea-Fernandez, Lieve Balcaen, Martín Resano, Frank Vanhaecke
    更新日期:2017-08-30
  • Advances in ICP-MS-based techniques for trace elements and their species analysis in cells
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-01-04
    Han Wang, Man He, Beibei Chen, Bin Hu
    更新日期:2017-08-30
  • Fundamental studies of an atmospheric-pressure microwave plasma sustained in nitrogen for atomic emission spectrometry
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-21
    Nahid Chalyavi, Peter S. Doidge, Richard J. S. Morrison, Guthrie B. Partridge
    更新日期:2017-08-29
  • A comparison of signal suppression and particle size distributions for ns- and fs-LA of metallic samples by LA-ETV-ICPMS
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-08
    Hale Ceren Yilmaz, Bodo Hattendorf
    更新日期:2017-08-25
  • Welcome to the fifth special issue dedicated to young analytical scientists in JAAS!
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-24
    Jorge Pisonero
    更新日期:2017-08-24
  • Contributors to the Young Analytical Scientists themed issue
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-24
    更新日期:2017-08-24
  • Assessment of exposure to airborne carbon nanotubes by laser-induced breakdown spectroscopy analysis of filter samples
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-23
    Jean-Baptiste Sirven, Pascale Dewalle, Céline Quéré, Vincent Fauvet, Michel Tabarant, Sylvie Motellier, Luana Golanski, Arnaud Guiot, Malika Amdaoud, Simon Clavaguera, Audrey Roynette, Sébastien Pontreau, François-Xavier Ouf, Francois Gensdarmes

    Exposure assessment is a key step in the evaluation of the risk induced by the handling of engineered nanomaterials. It is a very complex task, because several properties of nanoparticles are assumed to have an effect on their hazard. For exposure monitoring at workplace, real-time onsite measurements are commonly implemented to measure the particles size and number density, whereas the sampled material is subsequently analysed by electron microscopy. A complementary approach would consist in doing onsite chemical analysis of the filter samples, in order to routinely monitor a potential chronic exposure. Laser-induced breakdown spectroscopy (LIBS) has distinctive advantages for that purpose. Therefore, this work aims at evaluating the performances of LIBS to assess the exposure to airborne carbon nanotubes (CNTs) at workplace. As carbon is a ubiquitous element in the environment, our strategy was to target metal impurities of CNTs, aluminum and iron in our case. Then, we proceeded in three steps. First, we optimized the choice of the filter type to get the lowest detection limit for both elements. Secondly, this filter was used to quantitatively measure deposited CNTs. Eventually, we conducted an onsite measurement campaign in an industrial CNTs production plant to evaluate the exposure in a real situation. We demonstrated that we could reach a detection limit for CNTs compliant with the current NIOSH recommendation of 1 µg/m3, and that the detected CNTs during the onsite campaign in areas accessible to workers were at an extremely low concentration, several orders of magnitude lower than this recommendation.

    更新日期:2017-08-23
  • A portable multi-collector system based on an artificial optical compound eye for stand-off laser-induced breakdown spectroscopy
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-23
    W. T. Li, X. Y. Yang, X. Li, S. S. Tang, J. M. Li, R. X. Yi, P. Yang, Z. Q. Hao, L. B. Guo, X. Y. Li, X. Y. Zeng, Y. F. Lu
    更新日期:2017-08-23
  • Classification and discrimination of coal ash by laser-induced breakdown spectroscopy (LIBS) coupled with advanced chemometric methods
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-03
    Tianlong Zhang, Chunhua Yan, Juan Qi, Hongsheng Tang, Hua Li
    更新日期:2017-08-22
  • Detection of fluorine using laser-induced breakdown spectroscopy and Raman spectroscopy
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-07-31
    Pavel Pořízka, Saara Kaski, Aleš Hrdlička, Pavlína Modlitbová, Lucia Sládková, Heikki Häkkänen, David Prochazka, Jan Novotný, Petr Gadas, Ladislav Čelko, Karel Novotný, Jozef Kaiser
    更新日期:2017-08-22
  • Evaluation of self-absorption reduction of minor elements in laser-induced breakdown spectroscopy assisted with laser-stimulated absorption
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-21
    Jiaming Li, Yun Tang, Zhongqi Hao, Nan Zhao, Xinyan Yang, Huiwu Yu, Lianbo Guo, Xiangyou Li, Xiaoyan Zeng, Yong-Feng Lu

    Reducing self-absorption is one of the most important steps in achieving accurate analyses in laser-induced breakdown spectroscopy (LIBS). In this work, LIBS assisted with laser-stimulated absorption (LSA-LIBS) was used to reduce self-absorption effects in LIBS. A wavelength-tunable laser was used to resonantly excite cold atoms and reduce their amount in laser-induced plasmas, and thus fewer cold atoms at plasma periphery re-absorb light from the plasma center. Accordingly, self-absorption effect was reduced. Copper (Cu) and Chromium (Cr) elements in steels were taken as examples to evaluate and compare the self-absorption effect in LIBS and LSA-LIBS. The results of calculated self-absorption coefficients (SAs) supported the effectiveness in reducing self-absorption and improving analytical linearity using LSA-LIBS.

    更新日期:2017-08-21
  • Fundamental Studies of an Atmospheric-Pressure Microwave Plasma Sustained in Nitrogen for Atomic Emission Spectrometry
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-21
    Nahid Chalyavi, Peter Steven Doidge, Richard J. S. Morrison, Guthrie B. Partridge

    We report the results of fundamental studies of an atmospheric-pressure microwave plasma sustained in nitrogen. Plasma composition was modelled using chemical equilibrium software, with the measured temperature used as input for the program. The modelled electron density agreed well with the electron density measured in Thomson scattering experiments. The various temperatures measured (electronic excitation, electron, and rotational) were comparable, and we argue that the N2 microwave plasma is close to local thermodynamic equilibrium (LTE). This close-to-LTE behaviour was used as a basis to calculate the emission spectra of selected elements; the calculated spectra were compared with measured library spectra, and good agreement was found.

    更新日期:2017-08-21
  • Improved detection sensitivity for heavy trace elements using a miniature laser ablation ionisation mass spectrometer
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-21
    Reto Wiesendanger, Marek Tulej, Andreas Riedo, Samira Frey, Herbert R Shea, Peter Wurz

    Laser ablation ionisation time-of-flight mass spectrometry is a versatile technique to obtain highly sensitive measurement of the element and isotope composition of solid materials. Because of the measurements of nearly all elements in the sample, large ion rates of abundant elements may reduce the detection efficiency of heavier elements arriving later at the detector system. If this occurs, it will affect the capability of quantitative measurements of the heavy species. We demonstrate that by implementation of a short high-volatge (HV) pulse, we can remove the high rate ions that reduce the detection efficiency of the ion detector to measure trace elements, which otherwise would not be detectable. The location of a suitable electrode in the given ion optical system, the timing and the pulse shape were determined with the help of numerical ion trajectory simulations using the SIMION software. An HV pulse removes ions of lighter elements, including Na, K, Mg from the analysed ion beam, which are typically the most abundant species in rocks and soils, allowing sensitive analysis of heavy trace elements. Using standard NIST reference materials we determined detection limits in the sub-ppm range and accomplished isotope ratio measurements of Pb with an accuracy in the per mill range. Further investigations of trace elements of the KREEP material in a lunar sample demonstrate that the miniature LIMS system can be used for in situ analysis of rocks and soils, and for investigations of geological processes and dating.

    更新日期:2017-08-21
  • Capabilities of laser ablation inductively coupled plasma time-of-flight mass spectrometry
    J. Anal. At. Spectrom. (IF 3.379) Pub Date : 2017-08-18
    Marcel Burger, Gunnar Schwarz, Alexander Gundlach-Graham, Debora Käser, Bodo Hattendorf, Detlef Günther
    更新日期:2017-08-21
Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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