Ablation, atomic spectroscopy

Evans, R. D. and Outridge, P. M. (1994). Applications of laser ablation inductively coupled plasma mass spectrometry to the determination of environmental contaminants in calcified biological structures. Journal of Analytical Atomic Spectroscopy 9 985-989. 

Raith, A., Hutton, R. C., Abell, I. D., and Crighton, J. (1995). Non-destructive sampling method of metals and alloys for laser ablation-inductively coupled plasma mass spectrometry. Journal of Analytical Atomic Spectroscopy 10 591-594. 

Watling, R. J., Lynch, B. F., and Herring, D. (1997). Use of laser ablation inductively coupled plasma mass spectrometry for fingerprinting scene of crime evidence. Journal of Analytical Atomic Spectroscopy 12 195-203. 

In atomic spectroscopy, a substance is decomposed into atoms in a flame, furnace, or plasma. (A plasma is a gas that is hot enough to contain ions and free electrons.) Each element is measured by absorption or emission of ultraviolet or visible radiation by the gaseous atoms. To measure trace elements in a tooth, tiny portions of the tooth are vaporized (ablated) by a laser pulse1 and swept into a plasma. The plasma ionizes some of the atoms, which pass into a mass spectrometer that separates ions by their mass and measures their quantity. 

Many other types of atomization devices have been used in atomic spectroscopy. Gas discharges operated at reduced pressure have been investigated as sources of atomic emission and as ion sources for mass spectrometry. The glow discharge is generated between two planar electrodes in a cylindrical glass tube filled with gas to a pressure of a few torr. High-powered lasers have been employed to ablate samples and to cause laser-induced breakdown. In the latter technique, dielectric breakdown of a gas occurs at the laser focal point. 

Becker, J.S. (2002) Apphcations of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science. Spectrochimica Acta Part B Atomic Spectroscopy, 57, 1805-1820. 

Giinther, D., Jackson, S.E., Longerich, H.P. (1999) Laser ablation and arc/spark sohd sample introduction into inductively coupled plasma mass spectrometers. Spectrochimica Acta Part B Atomic Spectroscopy, 54,381-409. 

Most of these techniques have either limited applicability or suffer from inconsistent precision and accuracy and therefore have not been adopted as routine approaches. Laser ablation is probably one of the most promising methods in the above list, with high potential to provide an alternative sample introduction route for the different atomic spectroscopy techniques. 

Principles and Characteristics Simultaneous multi-element analysis based on emission from a plasma generated by focussing a powerful laser beam on a sample (solid, liquid, or gas) is known as laser-induced breakdown spectroscopy (LIBS) and under a variety of semantic variations time-resolved LIBS (TRELIBS), laser ablation emission spectroscopy (LAES), laser ablation atomic emission spectrometry (LA-AES), laser ablation optical emission spectrometry (LA-OES), laser plasma emission spectrometry (L-PES), laser-induced plasma spectroscopy (LIPS), laser spark spectroscopy (LSS), and laser-induced emission spectral analysis (LIESA ). Commercial LIBS analysers were already available in the 60/70s the technique now enjoys a renaissance. 

This limitation led to the development of laser ablation as a sampling device for atomic spectroscopy instrumentation, where the sampling step was completely separated from the excitation or ionization step. The major benefit is that each step can be independently controlled and optimized. These early devices used a high-energy laser to ablate the surface of a solid sample, and the resulting aerosol was swept into some kind of atomic spectrometer for analysis. Although initially used with atomic absorption - and plasma-based emission techniques, it was not until... 

Outridge, P. M. (1996). Atomic spectroscopy perspectives Potential applications of laser ablation ICP-MS in forensic biology and exploration geochemistry. Spectroscopy 11(4), 21. 

Wading, R.J. (1999). Atomic spectroscopy perspectives Novel application of laser ablation inductively coupled plasma mass spectrometry in forensic science and forensic archaeology. Spectroscopy 14(6), 16. 

Different analytical techniques are used for detection of the elemental composition of the solid samples. The simplest is direct detection of emission from the plasma of the ablated material formed above a sample surface. This technique is generally referred to as LIBS or LIPS (laser induced breakdown/plasma spectroscopy). Strong continuous background radiation from the hot plasma plume does not enable detection of atomic and ionic lines of specific elements during the first few hundred nanoseconds of plasma evolution. One can achieve a reasonable signal-to-noise ra-... 

Several characteristics of the metal beam have been studied in detail. It is well known that metal clusters and metal oxides are formed as a result of the ablation process. However, these potentially interfering species have been studied in detail130 and it has been concluded that they do not introduce any doubt as to the validity of the experimental results. Much more important than cluster or oxide formation are the atomic electronic state populations of the metal beams. For each metal reactant, these have been characterized using laser-induced fluorescence (LIF) excitation spectroscopy. For Y, only the two spin-orbit states of the ground electronic state (a Dz/2 and a D-3,/2) were observed.123... 

When laser-ablated Ni atoms were reacted with CS2 during cocondensation in excess argon, the C-bonded Ni( /-CS2) and side-on bonded Ni(//2-CS)S complexes were formed on annealing, whereas the inserted SNiCS was formed on photolysis. All species were characterized by IR spectroscopy and DFT calculations.2466 The reaction of low-valent [Ni(CO)J (x=2, 3) with CS2 has been studied by FT-ICR spectroscopy.2467... 

Fabre, C., Boiron, M.-C., Dubessy, J., Moissette, a. 1999. Determination of ions in individual fluid inclusions by laser ablation optical emission spectroscopy development and applications to natural fluid inclusions. Journal of Analytical Atomic Spectrometry, 14(6), 913-922. 

Since the mid-1960s, a variety of analytical chemistry techniques have been used to characterize obsidian sources and artifacts for provenance research (4, 32-36). The most common of these methods include optical emission spectroscopy (OES), atomic absorption spectroscopy (AAS), particle-induced X-ray emission spectroscopy (PIXE), inductively coupled plasma-mass spectrometry (ICP-MS), laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), X-ray fluorescence spectroscopy (XRF), and neutron activation analysis (NAA). When selecting a method of analysis for obsidian, one must consider accuracy, precision, cost, promptness of results, existence of comparative data, and availability. Most of the above-mentioned techniques are capable of determining a number of elements, but some of the methods are more labor-intensive, more destructive, and less precise than others. The two methods with the longest and most successful histoty of success for obsidian provenance research are XRF and NAA. 

AMS = accelerated mass spectroscopy EDTA = ethylene diamine tetra acetic acid GFAAS = graphite furnace atomic absorption spectrometry ICP-AES = inductively coupled plasma - atomic emission spectroscopy NAA = neutron activation analysis ETAAS = electrothermal atomic absorption spectrometry SEC/ICP-MS = size-exclusion chromatography/ICP-AES/mass spectrometry HLPC/ICP-AES = high-performance liquid chromatography/ICP-AES LAMMA = laser ablation microprobe mass analysis NA = not applicable ppq = parts per quadrillion... 

Laser-ablated La atoms were codeposited at 4 K with acetylene in excess Ar. The products La(C2H2), LaCCH2, HLaCCH, and La2(C2H2), were all characterized using IR spectroscopy. DFT calculations gave calculated vibrational frequencies, relative absorption intensities, and isotopic shifts that supported the identification of these molecules from the matrix IR... 

The tetrameric Zr complexes [Zr(0H)2(H20)2L]4X8 (L = bipyridyl, phenanthroline, various Schiff-bases X = Cl, NCS) were the presumed products from the reaction of ZrOCl2 with various heterocyclic bidentate ligands.336 The interaction of H20 with Zr0(C104)2 or Zr0(N03)2 was probed by NMR spectroscopy.337,338 In the latter case, the cation [Zr4(0H)8(H20)i6]8+ (80) was proposed as the product.338 The related trimer [Zr02Ci2H8(/u2-0H)]3(//3-0)Li5(THF)g(H20)5 (81) was isolated from the hydrolysis product of an organometallic precursor. X-ray structural data confirmed the planarity of the six-membered Zr3(/r2-OH)3 core.339 In related work, protometric studies of Zr hydroxide complexes have probed thermodynamic stability,340 while FT IR and theoretical investigations have addressed the details of laser-ablated group IV metal atoms that... 

In the application of atomic emission spectroscopy for quantitative analysis, samples must be prepared in liquid form of a suitable solvent unless it is already presented in that form. The exceptions are solids where samples can be analysed as received using rapid heating electro-thermal excitation sources, such as graphite furnace heating or laser ablation methods. Aqueous samples, e.g. domestic water, boiler water, natural spring, wines, beers and urines, can be analysed for toxic and non-toxic metals as received with... 

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