Comparison between XRF, TXRF, and PXRF analyses for provenance classification of archaeological bricks

Abstract

Ceramics provenance studies based on minor and trace elements are widely used to help in gathering knowledge of local furnace presence and commercial trades. Most of the times, destructive analyses are allowed because of the high amount of material, but sometimes (integer vessels, architectural decorations, etc.), a nondestructive examination is required. In both cases, X-ray fluorescence (XRF) analysis can be a useful tool.In this work, we compare the classification results obtained on a set of bricks from the medieval Chartusian monastery Certosa di Pavia in the Po valley, northern Italy, exploiting XRF, portable XRF, and total reflection XRF (TXRF) spectrometers.The XRF nondestructive analyses were performed both in situ before sampling and in the laboratory without preparing the shards. Grounded samples were instead used to obtain semi-quantitative TXRF analysis without dissolving the samples but using a suspension in high-purified water. The project aimed at verifying if a correct classification was possible even if a quantitative determination of minor and trace elements is abandoned, allowing a faster response when a large amount of data is concerned. For this reason, weight concentration was determined from laboratory XRF measurements only, whereas semiquantitative results and entire spectra were considered for TXRF and the in situ campaign, respectively. Data were then submitted to different statistical data treatments to obtain provenance classification.

Application of X‐ray fluorescence spectroscopy to provenance studies of Algerian archaeological pottery

“…Data were collected at 25‐kV high voltage and 0.3‐mA tube current, with 500‐s analysis time. Quantitative analyses are performed using a computational method (Lithos 3000 software) based on the fundamental parameters and already tested in previous works . This method considers, in addition to the characteristic X‐ray lines of the elements, also the intensity ratio of the scattered peaks to get information on effective Z of low elements' matrix or at least on its behavior regarding X‐ray absorption .…”

“…Several techniques can be exploited for this aim, such as atomic emission spectroscopy, proton‐induced X‐ray emission, inductively coupled plasma, neutron activation analysis, and Raman and infrared spectroscopy . Also X‐ray fluorescence (XRF) has been used, mostly on ground ceramics, representative of the whole object . Thanks to the development of portable XRF, this technique is particularly suitable to detect the chemical elements of archaeological unmovable objects.…”

Investigation by pXRF of Caltagirone Pottery Samples Produced in Laboratory

“…The present work contributes to this debate regarding pXRF through the study of Caltagirone pottery raw materials. Recently, similar studies undertaking chemical analysis of pottery have been performed using samples derived from Italian archaeological sites (Barone, et al, 2011;Donais, Wojtas, Desmond, Duncan & George, 2012;Bonizzoni, Galli, Gondola & Martini, 2013;Ceccarelli, Rossetti, Primavesi & Stoddart, 2016).…”

“…Concerning the effect of pottery firing conditions on bulk elemental compositions, there are many examples of studies that have used XRF, as well as other techniques (Cogswell, Neff & Glascock, 1996;Perlman & Asaro, 1969;Poole & Finch, 1972;Attas, Yaffe & Fossey, 1977;Kilikoglou, Maniatis & Grimanis, 1988;Storey, 1988;Maritan, et al, 2006;Bonizzoni, et al, 2013). In some studies considering the effect of changes in firing temperature on microstructure and physical properties of clay, XRF has been used for bulk chemical analyses (Cultrone, Rodriguez-Navarro, Sebastian, Cazalla, & De La Torre, 2001;Eramo, Laviano, Muntoni, & Volpe, 2004;Kurama, Kara, & Kurama, 2006;Johari, Said, Hisham, Bakar & Ahmad, 2010).…”

Micro‐invasive approach for non‐destructive XRF analysis on light matrix: inside the Opus Lemovicense

“…Different approaches have been proposed and applied in the last decades [4][5][6][7][8] ; at the same time, attempts to classify light matrix samples avoiding a precise quantitative determination have been made. [9][10][11] Going on in the same direction and starting from a case study of light matrix materials (enamels from a Limoges altar cross datable to the end of the 12th century, held in the Poldi Pezzoli Museum in Milan, Italy), this work combines different techniques, all based on the detection of secondary X-rays produced by the interaction of a primary beam with the sample material. EDXRF, portable Xray fluorescence (PXRF) and electron probe micro-analysis (EPMA) are exploited, each one for its own peculiar trait, to give a complete characterization in terms of composition of low-Z matrix samples.…”