Title: Noninvasive Synchrotron-Based X-ray Raman Scattering Discriminates Carbonaceous Compounds in Ancient and Historical Materials [In situ synchrotron-based X-Ray Raman scattering discriminates carbonaceous compounds in ancient and historical materials]

Abstract

Carbon compounds are ubiquitous and occur in a diversity of chemical forms in many systems including ancient and historic materials ranging from cultural heritage to paleontology. Determining their speciation cannot only provide unique information on their origin but may also elucidate degradation processes. Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge (280–350 eV) is a very powerful method to probe carbon speciation. However, the short penetration depth of soft X-rays imposes stringent constraints on sample type, preparation, and analytical environment. A hard X-ray probe such as X-ray Raman scattering (XRS) can overcome many of these difficulties. Here we report the use of XRS at ~6 keV incident energy to collect carbon K-edge XANES data and probe the speciation of organic carbon in several specimens relevant to cultural heritage and natural history. This methodology enables the measurement to be done in a nondestructive way, in air, and provides information that is not compromised by surface contamination by ensuring that the dominant signal contribution is from the bulk of the probed material. Using the backscattering geometry at large photon momentum transfer maximizes the XRS signal at the given X-ray energy and enhances nondipole contributions compared to conventional XANES, therebymore » augmenting the speciation sensitivity. The capabilities and limitations of the technique are discussed. As a result, we show that despite its small cross section, for a range of systems the XRS method can provide satisfactory signals at realistic experimental conditions. XRS constitutes a powerful complement to FT-IR, Raman, and conventional XANES spectroscopy, overcoming some of the limitations of these techniques.« less

Authors:

Gueriau, Pierre  ^[1];

• Search DOE PAGES for author "Gueriau, Pierre"
• Search DOE PAGES for ORCID "0000-0002-7529-3456"

Rueff, Jean -Pascal ^[2]; Bernard, Sylvain ^[3]; Kaddissy, Josiane A.  ^[4];

• Search DOE PAGES for author "Kaddissy, Josiane A."
• Search DOE PAGES for ORCID "0000-0002-6106-2462"

Goler, Sarah ^[5]; Sahle, Christoph J. ^[6]; Sokaras, Dimosthenis ^[7]; Wogelius, Roy A. ^[8]; Manning, Phillip L. ^[9]; Bergmann, Uwe ^[7]; Bertrand, Loic ^[1]

---

+ Show Author Affiliations

1. Univ. Paris-Saclay, Gif-sur-Yvette (France); Synchrotron SOLEIL, Gif-sur-Yvette (France)
2. Synchrotron SOLEIL, Gif-sur-Yvette (France); College of Charleston, Charleston, SC (United States)
3. Sorbonne Univ., Paris (France)
4. Univ. Paris-Saclay, Gif-sur-Yvette (France)
5. Columbia Univ., New York, NY (United States)
6. ESRF- The European Synchrotron, Grenoble (France)
7. SLAC National Accelerator Lab., Menlo Park, CA (United States)
8. Univ. of Manchester, Manchester (United Kingdom)
9. College of Charleston, Charleston, SC (United States); Univ. of Manchester, Manchester (United Kingdom)

Publication Date:

Wed Sep 13 00:00:00 EDT 2017

Research Org.:

SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Org.:

USDOE

OSTI Identifier:

1457414

Grant/Contract Number:  

654028; 290861; AC02-76SF00515

Resource Type:

Accepted Manuscript

Journal Name:

Analytical Chemistry

Additional Journal Information:

Journal Volume: 89; Journal Issue: 20; Journal ID: ISSN 0003-2700

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY