Laser ablation-inductively coupled accuracy

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. 

Laser-ablation, inductively coupled-plasma mass spectrometry (LA-ICPMS) is an instrumental technique in which a laser-ablahon cell and ophcal microscope supplant the spray chamber/nebulizer apparatus of a standard ICP-MS instrument. Subsamples of questioned material are ablated from a solid sample via laser (often a pulsed Nd-YAG tuned to 266 or 213 nm). Ablated specimens are transported in a stream of Ar to a plasma torch for ionization and mass discrimination as per solution ICP-MS. Only minimal sample prep is required, and few restrictions are placed on the nature of questioned solid samples (Brundle et al. 1992 Vickerman 1998). While laser spot sizes can be reduced to several micrometers, sensitivity is degraded as a result, and usual spatial resolutions are on the order of 10-100 pm. Matrix-matched standards are also necessary for accurate trace-element and isotopic quantitative analyses in LA-ICPMS. Depending on the quality of such primary standards, LA-ICPMS accuracies are typically 1-10%, with limits-of-detection in the parts-per-billion (ppb) range (O Table 62.1). 

The corabination of an inductively coupled plasma ion source and a magnetic sector-based mass spectrometer equipped with a multi-collector (MC) array [multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS)] offers precise and reliable isotope ratio data for many solid elements. In fact, MC-ICP-MS provides data, the trueness (accuracy) and precision of which is similar to, or, in some cases, even superior to, that achieved by thermal ionization mass spectrometry (TIMS), considered the benchmark technique for isotope ratio measurements of most solid elements [1], The basic strength of ICP-MS lies in the ion source, which achieves extremely high ionization efficiency for almost all elements [2, 3]. Consequently, MC-ICP-MS is likely to become the method of choice for many geochemists, because it is a versatile, user-friendly, and efficient method for the isotopic analysis of trace elements [4-8], The ICP ion source also accepts dry sample aerosols generated by laser ablation [9-16], The combination of laser ablation (LA) with ICP-MS is now widely accepted as a sensitive analytical tool for the elemental and isotopic analysis of solid samples. 

Gehrels, G.E., Valencia, V.A., and Ruiz, J. (2008) Enhanced precision, accuracy, efficiency, and spatial resolution of U-Pb ages by laser ablation-multicollector-inductively coupled plasma-mass spectrometry. Geochem. Geophys. Geosyst., 9, Q03017. 

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