Uncritical application of portable X‐ray fluorescence (PXRF) to non‐destructive analysis of archaeological ceramics has been received with scepticism. In this article, we present a methodological evaluation of the parameters and constraints for PXRF analysis of archaeological ceramics. We use experimental matrices that simulate characteristics of archaeological artefacts to demonstrate the impact of (1) surface morphology, (2) organic surface coatings and (3) grain size and mineralogy on non‐destructive PXRF analysis. We then apply these parameters to PXRF analysis of heterogeneous handmade ceramics from central Turkey. We conclude that with appropriate methodology, non‐destructive PXRF analysis can be demonstrated to provide a high level of accurate and precise geochemical discrimination for archaeological ceramics. Copyright © 2011 John Wiley & Sons, Ltd.

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Portable X-ray fluorescence (PXRF) spectrometry can provide rapid and nondestructive analyses of agriculturally important elements in soil. To assess the applicability of PXRF for total element analysis of Vertisols, 20 soils were collected across northern New South Wales (NSW), Australia. Comparison of PXRF results were made with conventional standard microwave aqua regia (AR) digestion followed by inductively couple plasma optical emission spectroscopy (ICP-OES) analysis, laboratory X-ray fluorescence (LXRF), and neutron activation analysis (NAA). Strong linear correlations were found for As, Ca, Cr, Cu, Fe, K, Mg, Mn, Ni, P, Pb, Si, Ti, and Zn. We demonstrate that nondestructive analyses for total soil element determination, particularly Ca, Fe, Mn, and P, should now allow rapid elucidation of important chemical processes in Vertisols that are commonly only available following rigorous sample preparation and digestion. The integrated and robust character of PXRF instrumentation, requiring minimal or no dedicated laboratory infrastructure, is readily adaptable to a wide range of analytical situations.

Glazed ceramics are ubiquitous in the medieval archaeological record in the Mediterranean. The effects of lead volatilisation during firing of glazed ceramics on non-destructive PXRF (portable X-ray fluorescence) are evaluated using 25 Byzantine Cypriot glazed ceramics. Significant spectral interferences reduce the number of discriminating elements for multivariate statistical analysis, limiting the capacity of non-destructive PXRF to resolve compositional differences. Nonetheless, non-destructive PXRF of glazed wares has the potential to expand provenancing studies where significantly different geology is present or for appropriate archaeological questions.