A Study on the Quantitative Analysis of Portable XRF for the Components Analysis of Metal Cultural Heritage

In this study we conducted component analyses of portable XRF detectors using four Au-Cu alloy standard samples to improve their accuracy by drawing up a calibration curve based on ICP-OES standard values. The portable XRF analysis found absolute errors of 0.3 to 3.7 wt% for Au and 0.2 to 8.2 wt% for Cu, confirming that the error range and standard deviation differed from one detector to another. Furthermore, the calibration curve improved their accuracy, such that the relative error rates of Au and Cu decreased from 9.8% and 14% to 3.5% and 3.7%, respectively. Accordingly, an experiment to confirm the calibration curve was conducted using unknown samples, finding that the measured values of the unknown samples fell on the calibration curve. Therefore, to accurately analyze the components of metal cultural heritage items, it is necessary to prepare a calibration curve for each element after checking whether the detector is suitable for the artifact.

Nickel Uptake by Cypress Pine (Callitris glaucophylla) in the Miandetta Area, Australia: Implications for Use in Biogeochemical Exploration

The uptake of Ni and other elements by Callitris glaucophylla (white cypress pine), from weathered ultramafic rocks under varying depths of transported regolith cover, is examined at two sites in the Miandetta area, New South Wales, Australia. Results show that C. glaucophylla can accumulate elevated Ni concentrations in the needles (leaves or phyllodes) from underlying Ni-enriched regolith up to two orders of magnitude above the normal micronutrient levels required for the species. Such uptake levels occur in areas with high total Ni in the soil and regolith despite the relatively low mobility of the Ni due to its presence in a low availability form. This highlights the importance of biotic processes in extracting Ni from soil. The needles of C. glaucophylla could provide an effective and convenient sampling medium for reconnaissance biogeochemical exploration for Ni mineralisation and anomalies where transported regolith is less than ~3 m thick. The study has also demonstrated the potential for in situ analysis of Ni and other elements in the needles by portable XRF.

Near real-time management of spectral interferences with portable XRF spectrometers: Application to Sc quantification in nickeliferous laterite ores

Since the development of portable XRF (pXRF) spectrometers, few studies have been conducted on the influence of spectral interferences between chemical elements. This study aims to improve the management of these interferences to obtain more reliable geochemical analyses. We specifically investigate Ca-related interferences on Sc analysis for the case of Ni-rich laterite samples using the Niton XL3t GOLDD+ pXRF analyser. Three quantification methods were tested on 59 pelletised samples using the ‘Soil’ mode. The first named ‘Manufacturer’, represents the elemental quantification directly provided by the device based on Regions of Interest (ROI) and multilinear corrections of spectral interferences configured during the spectrometer design. The second, the ‘20 Cu’ method, is based on spectral fitting using the PyMCA software. The third, the ‘18 Fe’ method, combines spectral fitting with modified experimental conditions. For each, a quantification methodology was developed, establishing (i) Ca and Sc calibration lines and (ii) Ca/Sc threshold values delimiting fields of ‘reliable’, 'to be confirmed,’ and ‘unreliable’ measurements. The ‘20 Cu’ and ‘18 Fe’ methods greatly extend the ‘reliable measurements’ field concerning the Ca/Sc ratio compared to the ‘Manufacturer’ method. The ‘18 Fe’ method was also found to provide the most negligible measurement dispersion.Supplementary material:https://doi.org/10.6084/m9.figshare.c.5511838

Pitfalls and Possibilities of Patinated Bronze: The Analysis of Pre-Roman Italian Armour Using pXRF

Despite the importance of weapons and armour as part of material culture in the Mediterranean during the first millennium BCE, such objects have generally not been studied beyond stylistic analyses. Bronze was extensively used in the construction of these materials; however, its characterisation is complicated due to patination and the different manufacturing techniques used. We used portable XRF (pXRF) to non-destructively characterise bronze material in a way that mitigates the distorting effects of patina. Analysis was conducted on 23 pieces of pre-Roman Italian bronze armour. Assays were taken using two different techniques; ‘single point’ assays and ‘cluster’ assays. There is variability visible across assays both on and between items, grouped both geographically and chronologically. We highlight significant trends visible in the results over time and different object types and discuss the utility of pXRF on ancient bronze with recommendations for best practice.

Vectors to ore in replacive VMS deposits of the northern Iberian Pyrite Belt: mineral zoning, whole rock geochemistry, and use of portable XRF

Volcanogenic Massive Sulphide (VMS) deposits represent a major source of base, precious and other metals of economic and industrial importance. As in other mineral systems, progressive exhaustion of the shallowest and most easily accessible deposits is leading to increasingly complex exploration. In this context vectors to ore play a vital role. The Iberian Pyrite Belt (IPB) is an outstanding VMS district located in the SW Iberian Peninsula, which represents the main mining area in Spain and one of the main zones of base metal production in Europe. But the work on vectors to ore in the IPB is far from systematic or complete. In this work we have performed a detailed study of the main vectors to ore related to mineral zoning and whole rock geochemistry that are currently used in the exploration of VMS systems to a representative volcanic rock hosted replacive VMS deposit located in the northern IPB, the Aguas Teñidas deposit. Results have been compared to other deposits in the IPB and in other VMS districts. The investigated vectors include: mineralogical zoning, host sequence characterization and mineralized unit identification based on whole rock geochemistry, the study of the characteristics and behaviour of whole rock geochemical anomalies around the ore (e.g. alteration-related compositional changes, characteristics and extent of geochemical halos around the deposit), with definition of threshold values for the mineralization-related indicative elements, and application of portable XRF analysis to the detection of the previous vectors. In the footwall, a concentric cone-shaped hydrothermal alteration bearing the stockwork passes laterally, from core to edge, from quartz (only locally), to chlorite, sericite–chlorite, and sericite alteration zones. The hydrothermal alteration is also found in the hanging wall despite its thrusted character: a proximal sericite alteration zone is followed by a more distal albite one, which is described here for the first time in the IPB. Whole rock major elements show an increase in alteration indexes (e.g. AI, CCPI) towards the mineralization, with a general SiO2 enrichment, FeO enrichment in the central portion of the system, K2O and Na2O leaching towards the outside areas, and a less systematic MgO behaviour. Copper, Pb and Zn produce proximal anomalies around mineralized areas, with the more mobile Sb, Tl and Ba generating wider halos. Whereas Sb and Tl halos form around all mineralized areas, Ba anomalies are restricted to areas around the massive sulphide body. Our results show that proposed vectors, or adaptations designed to overcome p-XRF limitations, can be confidently used by analysing unprepared hand specimens, including the external rough curved surface of drill cores. The data presented in this work are not only applicable to VMS exploration in the IPB, but on a broader scale they will also contribute to improve our general understating of vectors to ore in replacive-type VMS deposits.