Elemental analysis of halogens using molecular emission by laser-induced breakdown spectroscopy in air

Gaft, M.; Nagli, L.; Eliezer, N.; Groisman, Y.; Forni, O.

doi:10.1016/j.sab.2014.05.011

Cited by 92 publications

(50 citation statements)

References 16 publications

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“…By measuring molecular bands in the UV/vis range, e.g., CaCl band at 593.4 nm, superior signal intensities, as compared to atomic chlorine lines, were obtained without the need for vacuum conditions. 9 In LIP of organic substances, molecular emission bands of C 2 and CN are the dominating spectral features. These molecular bands in combination with atomic lines have allowed biological samples, such as bacteria, to be classified.…”

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confidence: 99%

Insight into the Formation of Molecular Species in Laser-Induced Plasma of Isotopically Labeled Organic Samples

2015

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Recently, the detection of molecular species in laser-induced breakdown spectroscopy (LIBS) has gained increasing interest, particularly for isotopic analysis. In LIBS of organic materials, it is predominantly CN and C2 species that are formed, and multiple mechanisms may contribute to their formation. To gain deeper insight into the formation of these species, laser-induced plasma of (13)C and (15)N labeled organic materials was investigated in a temporally and spatially resolved manner. LIBS on fumaric acid with a (13)C labeled double bond allowed the formation mechanism of C2 to be investigated by analyzing relative signal intensities of (12)C2, (12)C(13)C, and (13)C2 molecules. In the early plasma (<5 μs), the majority of C2 originates from association of completely atomized target molecules, whereas in the late plasma, the increased concentration of (13)C2 is due to incomplete dissociation of the carbon double bond. The degree of this fragmentation was found to be up to 80% and to depend on the type of the atmospheric gas. Spatial distributions of C2 revealed distinct differences for plasma generated in nitrogen and argon. A study of the interaction of ablated organics with ambient nitrogen showed that the ambient nitrogen contributed mainly to CN formation. The pronounced anisotropy of the C(15)N to C(14)N ratio across the diameter of the plasma was observed in the early plasma, indicating poor initial mixing of the plasma with the ambient gas. Overall, for accurate isotope analysis of organics, LIBS in argon with relatively short integration times (<10 μs) provides the most robust results. On the other hand, if information about the original molecular structure is of interest, then experiments in nitrogen (or air) with long integration times appear to be the most promising.

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confidence: 99%

Insight into the Formation of Molecular Species in Laser-Induced Plasma of Isotopically Labeled Organic Samples

2015

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“…23 These species are notoriously difficult to detect with their atomic/ionic emission lines, which are not efficiently excited (high upper energy levels) and additionally suffer from unfavorable transition symmetries.…”

Section: Calibration-free Laser-induced Breakdown Spectroscopy Updatementioning

confidence: 99%

Novel Applications of Laser-Induced Breakdown Spectroscopy

Bauer

Buckley

2017

Appl Spectrosc

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The goal of this review article is to provide a description of recent and novel laser-induced breakdown spectroscopy (LIBS) applications and developments, especially those discussed during the NASLIBS Conference, held during SciX in Providence, RI, in September 2015. This topic was selected in view of the numerous recent overall review papers that have successfully given a broad view of the current understanding of laser-material interactions and plasma development and have also discussed the wide landscape of analytical applications of LIBS. This paper is divided into sections that focus on a few of the many applications under development in the LIBS community. We provide a summary of updates to calibrationfree LIBS (CF-LIBS) and associated developments using plasma characteristics to improve quantification in LIBS output, both in a dedicated section and as applications are discussed. We have also described the most recent publications studying the sources, generation, and use of molecular features in LIBS, including those naturally present in the spectra of organic materials, and those induced with the addition of salts to enable the measurement of halogens, not typically present in LIBS signals. In terms of development of applications of LIBS, we focused on the use of LIBS for indirect measurements such as pH and degree of humification in soil and heating value in coal. We also reviewed the extant literature on LIBS analysis of agricultural materials, coal, minerals, and metals. Finally, we discuss the nascent developments of spatially heterodyne spectroscopy, a method that seeks to circumnavigate a serious drawback of most spectrometers -very small optical throughput -through the use of interferometers.

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“…Presently two sources of band emission in LIP are known: plasma-induced luminescence (PIL) [10] and molecular emission [1][2][3][4][5][6]. Danburite and datolite are luminescent minerals with trivalent rare-earth element (REE) luminescence centers, such as Sm 3+ , Eu 3+ , Dy 3+ and Tb 3+ [11].…”

Section: Calcium-and Boron-bearing Mineralsmentioning

confidence: 99%

“…For example, CaF emits in the orange, MgF in the UV and SrF in the red parts of the spectrum [6]. Thus we checked for possible SrBO 2 molecular emission.…”

Section: Strontium and Boron-bearing Matricesmentioning

confidence: 99%