High-resolution X-ray diffraction with no sample preparation.

It is shown that energy-dispersive X-ray diffraction (EDXRD) implemented in a back-reflection geometry is extremely insensitive to sample morphology and positioning even in a high-resolution configuration. This technique allows high-quality X-ray diffraction analysis of samples that have not been prepared and is therefore completely non-destructive. The experimental technique was implemented on beamline B18 at the Diamond Light Source synchrotron in Oxfordshire, UK. The majority of the experiments in this study were performed with pre-characterized geological materials in order to elucidate the characteristics of this novel technique and to develop the analysis methods. Results are presented that demonstrate phase identification, the derivation of precise unit-cell parameters and extraction of microstructural information on unprepared rock samples and other sample types. A particular highlight was the identification of a specific polytype of a muscovite in an unprepared mica schist sample, avoiding the time-consuming and difficult preparation steps normally required to make this type of identification. The technique was also demonstrated in application to a small number of fossil and archaeological samples. Back-reflection EDXRD implemented in a high-resolution configuration shows great potential in the crystallographic analysis of cultural heritage artefacts for the purposes of scientific research such as provenancing, as well as contributing to the formulation of conservation strategies. Possibilities for moving the technique from the synchrotron into museums are discussed. The avoidance of the need to extract samples from high-value and rare objects is a highly significant advantage, applicable also in other potential research areas such as palaeontology, and the study of meteorites and planetary materials brought to Earth by sample-return missions.

Phase-targeted X-ray diffraction.

A powder X-ray diffraction (XRD) method to enhance the signal of a specific crystalline phase within a mixture is presented for the first time. Specificity to the targeted phase relies on finding coincidences in the ratios of crystal d spacings and the ratios of elemental characteristic X-ray energies. Such coincidences can be exploited so that the two crystal planes diffract through the same scattering angle at two different X-ray energies. An energy-resolving detector placed at the appropriate scattering angle will detect a significantly enhanced signal at these energies if the target mineral or phase is present in the sample. When implemented using high scattering angles, for example 2θ > 150°, the method is tolerant to sample morphology and distance on the scale of ∼2 mm. The principle of the method is demonstrated experimentally using Pd Lα1 and Pd Lß1 emission lines to enhance the diffraction signal of quartz. Both a pure quartz powder pellet and an unprepared mudstone rock specimen are used to test and develop the phase-targeted method. The technique is further demonstrated in the sensitive detection of retained austenite in steel samples using a combination of In Lß1 and Ti Kß emission lines. For both these examples it is also shown how the use of an attenuating foil, with an absorption edge close to and above the higher-energy characteristic X-ray line, can serve to isolate to some degree the coincidence signals from other fluorescence and diffraction peaks in the detected spectrum. The phase-targeted XRD technique is suitable for implementation using low-cost off-the-shelf components in a handheld or in-line instrument format.

A lightweight near-infrared spectrometer for the detection of trace atmospheric species.

This paper describes the development and deployment of a lightweight in situ near-infrared tunable diode laser absorption spectrometer (TDLAS) for balloon-borne measurements of trace species such as methane in the upper troposphere and stratosphere. The key feature of the instrument design is its ability to provide high sensitivity measurements with better than 1 part in 10(6) Hz(-1/2) optical sensitivity in a lightweight package weighing as little as 6 kg, and maintaining this level of performance over the wide range of conditions experienced during field measurements. The absolute accuracy for methane measurements is approximately 10% limited by uncertainties in determining the gas temperature in the measurement volume. The high sensitivity and high temporal resolution (2.3 s measurement period) enables details of the fine-scale structure in the atmosphere to be measured. The TDLAS instrument has been used on a number of major international measurement campaigns. Intercomparison with other instruments during these campaigns have confirmed the comparability of the results from this instrument with measurements made by a range of other techniques, and demonstrated the instruments suitability for studies of atmospheric dynamics, transport, and mixing processes.

Confirmation of nitric oxide synthesis in active ulcerative colitis by infra-red diode laser spectroscopy.

BACKGROUND: The synthesis of nitric oxide (NO) in the colonic mucosa of patients affected by ulcerative colitis (UC) has been previously investigated using indirect measurements of enzyme activity and non-specific measurements of luminal NO gas. The aim of this study was to determine unequivocally if luminal NO gas in active UC is present in greater concentrations than in healthy control subjects. METHODS: Luminal gas was collected from eight patients with active UC and eight healthy volunteers. NO gas concentration was measured using diode laser spectroscopy. RESULTS: NO gas was detected in four of eight patients with active UC (range 0.13-1.1 nmol) and none of the healthy control subjects. CONCLUSION: NO gas is present in greater concentrations in patients with active UC than in control subjects. This supports the view that mucosal NO synthesis is increased in ulcerative colitis.