@article{696333,
  abstract     = {{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.}},
  author       = {{Dowsett, Mark and Adriaens, Mieke and Jones, Gareth and Poolton, Nigel and Fiddy, Steve and Nikitenko, Sergey}},
  issn         = {{0003-2700}},
  journal      = {{ANALYTICAL CHEMISTRY}},
  language     = {{eng}},
  number       = {{22}},
  pages        = {{8717--8724}},
  title        = {{Optically detected X-ray absorption spectroscopy measurements as a means to monitor corrosion layers on copper}},
  url          = {{http://dx.doi.org/10.1021/ac800895n}},
  volume       = {{80}},
  year         = {{2008}},
}

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