Optically detected X-ray absorption spectroscopy measurements as a means to monitor corrosion layers on copper

XANES and EXAFS information is conventionally measured in transmission through the energy-dependent absorption of X-rays or by observing X-ray fluorescence, but secondary fluorescence processes, such as the emission of electrons and optical photons (e.g., 200-1000 nm), can also be used as a carrier of the XAS signatures, providing complementary information such as improved surface specificity. Where the near-visible photons have a shorter range in a material, the data will be more surface specific. Moreover, optical radiation may escape more readily than X-rays through liquid in an environmental cell. Here, we describe a first test of optically detected X-ray absorption spectroscopy (ODXAS) for monitoring electrochemical treatments on copper-based alloys, for example, heritage metals. Artificially made corrosion products deposited on a copper substrate were analyzed in air and in a 1% (w/v) sodium sesquicarbonate solution to simulate typical conservation methods for copper-based objects recovered from marine environments. The measurements were made on stations 7.1 and 9.2 MF (SRS Daresbury, UK) using the mobile luminescence end station (MoLES), supplemented by XAS measurements taken on DUBBLE (BM26 A) at the ESRF. The ODXAS spectra usually contain fine structure similar to that of XAS spectra measured in X-ray fluorescence. Importantly, for the compounds examined, the ODXAS is significantly more surface specific, and > 98% characteristic of thin surface layers of 0.5-1.5-mu m thickness in cases where X-ray measurements are dominated by the substrate. However, EXAFS and XANES from broadband optical measurements are superimposed on a high background due to other optical emission modes. This produces statistical fluctuations up to double what would be expected from normal counting statistics because the data retain the absolute statistical fluctuation in the original raw count, while losing up to 70% of their magnitude when background is removed. The problem may be solved in future through optical filtering to isolate the information-containing band, combined with the use of higher input X-ray fluxes available on third-generation light sources

Optical dating in a new light: A direct, non-destructive probe of trapped electrons

Abstract Optical dating has revolutionized our understanding of Global climate change, Earth surface processes, and human evolution and dispersal over the last ~500 ka. Optical dating is based on an anti-Stokes photon emission generated by electron-hole recombination within quartz or feldspar; it relies, by default, on destructive read-out of the stored chronometric information. We present here a fundamentally new method of optical read-out of the trapped electron population in feldspar. The new signal termed as Infra-Red Photo-Luminescence (IRPL) is a Stokes emission (~1.30 eV) derived from NIR excitation (~1.40 eV) on samples previously exposed to ionizing radiation. Low temperature (7–295 K) spectroscopic and time-resolved investigations suggest that IRPL is generated from excited-to-ground state relaxation within the principal (dosimetry) trap. Since IRPL can be induced even in traps remote from recombination centers, it is likely to contain a stable (non-fading), steady-state component. While IRPL is a powerful tool to understand details of the electron-trapping center, it provides a novel, alternative approach to trapped-charge dating based on direct, non-destructive probing of chronometric information. The possibility of repeated readout of IRPL from individual traps will open opportunities for dating at sub-micron spatial resolution, thus, marking a step change in the optical dating technology