Single-Slice XRF Mapping of Light Elements in Frozen-Hydrated Allium schoenoprasum via a Self-Absorption-Corrected Hyperspectral Tomographic Reconstruction Approach.

3D and 2D-cross-sectional X-ray fluorescence analysis of biological material is a powerful tool to image the distribution of elements and to understand and quantify metal homeostasis and the distribution of anthropogenic metals and nanoparticles with minimal preparation artifacts. Using tomograms recorded on cryogenically prepared leaves of Allium schoenoprasum, the cross-sectional distribution of physiologically relevant elements like calcium, potassium, manganese, and zinc could be tomographically reconstructed by peak fitting followed by a conventional maximum-likelihood algorithm with self-absorption correction to reveal the quantitative cross-sectional element distribution. If light elements such as S and P are located deep in the sample compared to the escape depth of their characteristic X-ray fluorescence lines, the quantitative reconstruction becomes inaccurate. As a consequence, noise is amplified to a magnitude where it might be misinterpreted as actual concentration. We show that a tomographic MCA hyperspectral reconstruction in combination with a self-absorption correction allows for fitting of the XRF spectra directly in real space, which significantly improves the qualitative and quantitative analysis of the light elements compared to the conventional method as noise and artifacts in the tomographic reconstruction are reduced. This reconstruction approach can substantially improve the quantitative analysis of trace elements as it allows the fitting of summed voxel spectra in anatomical regions of interest. The presented method can be applied to XRF 2D single-slice tomography data and 3D tomograms and is particularly relevant for, but not limited to, biological material in order to help retrieve self-absorption corrected quantitative reconstructions of the spatial distribution of light elements and ultra-trace-elements.

X-ray fluorescence analysis of metal distributions in cryogenic biological samples using large-acceptance-angle SDD detection and continuous scanning at the Hard X-ray Micro/Nano-Probe beamline P06 at PETRA III.

A new Rococo 2 X-ray fluorescence detector was implemented into the cryogenic sample environment at the Hard X-ray Micro/Nano-Probe beamline P06 at PETRA III, DESY, Hamburg, Germany. A four sensor-field cloverleaf design is optimized for the investigation of planar samples and operates in a backscattering geometry resulting in a large solid angle of up to 1.1 steradian. The detector, coupled with the Xspress 3 pulse processor, enables measurements at high count rates of up to 106 counts per second per sensor. The measured energy resolution of ∼129 eV (Mn Kα at 10000 counts s-1) is only minimally impaired at the highest count rates. The resulting high detection sensitivity allows for an accurate determination of trace element distributions such as in thin frozen hydrated biological specimens. First proof-of-principle measurements using continuous-movement 2D scans of frozen hydrated HeLa cells as a model system are reported to demonstrate the potential of the new detection system.

Compact x-ray microtomography system for element mapping and absorption imaging.

We have designed and built a compact x-ray microtomography system to perform element mapping and absorption imaging by exploiting scanning fluorescence tomography and full-field transmission microtomography, respectively. It is based on a low power microfocus tube and is potentially appropriate for x-ray diagnostics in space. Full-field transmission tomography yields the three-dimensional inner structure of an object. Fluorescence microtomography provides the element distribution on a virtual section through the sample. Both techniques can be combined for appropriate samples. Microradiography as well as fluorescence mapping are also possible. For fluorescence microtomography a small and intensive microbeam is required. It is generated using a polycapillary optic. Operating the microfocus tube with a molybdenum target at 12 W, a microbeam with a full width at half maximum lateral extension of 16 microm and a flux of about 10(8) photonss is generated. As an example of application, this beam is used to determine the element distribution inside dried plant samples. For full-field scanning tomography, the x-ray optic is removed and the sample is imaged in magnifying projection onto a two-dimensional position sensitive detector. Depending on the sample size, a spatial resolution down to about 10 microm is possible in this mode. The method is demonstrated by three-dimensional imaging of a rat humerus.

Field intercomparison studies for evaluation and validation of the AESminiSamplR technique for sampling and analysis of total particulate mercury in the atmosphere.

This paper presents new data and reviews literature results from six field intercomparison studies to further evaluate and validate the AESminiSamplR [Anal. Chem., 70 (1998) 2403] technique for sampling and analysis of total particulate mercury in ambient air. The intercomparison studies were carried out at: two remote sites in the Arctic [Alert, Nunavut, Canada (82 degrees 28'N, 62 degrees 18'W) and Ny-Alesund, Svalbard (78 degrees 54'N, 11 degrees 53'E)], one site in Ann Arbor, MI, and three sites in Europe (one in Italy and two in Sweden). The AESminiSamplR was compared with five other methods using different materials, different flow rates, different sample treatment procedures, and/or different detection techniques. Four of the five methods compared were operated by different laboratories. When the compared methods were operated by different laboratories, a difference

Modelling of mercury emissions from background soils.

Emissions of volatile mercury species from natural soils are believed to be a significant contributor to the atmospheric burden of mercury, but only order-of-magnitude estimates of emissions from these sources are available. The scaling-up of mercury flux measurements to regional or global scales is confounded by a limited understanding of the physical, chemical and biochemical processes that occur in the soil, a complex environmental matrix. This study is a first step toward the development of an air-surface exchange model for mercury (known as the mercury emission model (MEM)). The objective of the study is to model the partitioning and movement of inorganic Hg(II) and Hg(0) in open field soils, and to use MEM to interpret published data on mercury emissions to the atmosphere. MEM is a multi-layered, dynamic finite-element soil and atmospheric surface-layer model that simulates the exchange of heat, moisture and mercury between soils and the atmosphere. The model includes a simple formulation of the reduction of inorganic Hg(II) to Hg(0). Good agreement was found between the meteorological dependence of observed mercury emission fluxes, and hourly modelled fluxes, and it is concluded that MEM is able to simulate well the soil and atmospheric processes influencing the emission of Hg(0) to the atmosphere. The heretofore unexplained close correlation between soil temperature and mercury emission flux is fully modelled by MEM and is attributed to the temperature dependence of the Hg(0) Henry's Law coefficient and the control of the volumetric soil-air fraction on the diffusion of Hg(0) near the surface. The observed correlation between solar radiation intensity and mercury flux, appears in part to be due to the surface-energy balance between radiation, and sensible and latent heat fluxes which determines the soil temperature. The modelled results imply that empirical correlations that are based only on flux chamber data, may not extend to the open atmosphere for all weather scenarios.

Comparison of conventional filtration and a denuder-based methodology for sampling of particulate-phase mercury in ambient air.

This paper compares the results of total atmospheric particulate-phase mercury determinations using samples collected by two methods. The conventional filtration method (FM) collects airborne particulate matter first, whereas the denuder-based method (DM) removes gaseous-phase mercury prior to particulate matter collection. In each case, particulate-phase mercury (PM) is collected on a quartz fiber disc held in a miniaturized device and is analyzed using a pyrolysis/gold amalgamation/thermal desorption/cold vapor atomic fluorescence spectrometry (CVAFS) technique. The results show that the concentrations of PM determined using the samples collected by DM are higher than those determined using the samples collected by FM. Evidence presented shows that the higher results are due to mercury-bearing gold particles flaking off from the gold-coated denuder surfaces in the denuder-based sampling system.

A device for sampling and determination of total particulate mercury in ambient air.

A miniaturized device, which serves as both particulate trap and pyrolyzer for airborne particulate mercury species, is described. It has been used in combination with amalgamation/thermal desorption/cold vapor atomic fluorescence spectrometry detection for the determination of total particulate mercury (TPM) associated with atmospheric aerosols. A standard reference material (SRM 1633b, NIST) has been used for validating of the pyrolysis technique, and a relative error smaller than 3% has been obtained. Contrary to most methods currently employed, this new technique does not require any sample preparation (e.g., extraction/digestion), no manual sample transfer or sample handling, and no addition of chemicals or reagents. Hence the risk of contamination is low. The time for complete analysis is less than 10 min per sample. The concentrations of TPM determined in metropolitan Toronto ranged from 3 to 91 pg m(-)(3) with standard deviations of <±2 pg m(-)(3) for simultaneous sets of four samples. These atmospheric TPM concentration values fall within the range reported in the literature. Good agreement was obtained by the three methods compared in a field study at Ny-Ålesund (78°54'N, 11°53'E), Svalbard. The elevated values of TPM concentrations obtained using the method developed in this work may arise from the Arctic springtime conversion of atmospheric mercury from gas-phase to particulate-phase Hg species.