David Paterson

Marine Polyphosphate: A Key Player in Geologic Phosphorus Sequestration

The in situ or authigenic formation of calcium phosphate minerals in marine sediments is a major sink for the vital nutrient phosphorus. However, because typical sediment chemistry is not kinetically conducive to the precipitation of these minerals, the mechanism behind their formation has remained a fundamental mystery. Here, we present evidence from high-sensitivity x-ray and electrodialysis techniques to describe a mechanism by which abundant diatom-derived polyphosphates play a critical role in the formation of calcium phosphate minerals in marine sediments. This mechanism can explain the puzzlingly dispersed distribution of calcium phosphate minerals observed in marine sediments worldwide.

The X‐ray Fluorescence Microscopy Beamline at the Australian Synchrotron

A hard x‐ray micro‐nanoprobe has commenced operation at the Australian Synchrotron providing versatile x‐ray fluorescence microscopy across an incident energy range from 4 to 25 keV. Two x‐ray probes are used to collect μ‐XRF and μ‐XANES for elemental and chemical microanalysis: a Kirkpatrick‐Baez mirror microprobe for micron resolution studies and a Fresnel zone plate nanoprobe capable of 60‐nm resolution. Some unique aspects of the beamline design and operation are discussed. An advanced energy dispersive x‐ray fluorescence detection scheme named Maia has been developed for the beamline, which enables ultrafast x‐ray fluorescence microscopy.

Fluctuation microscopy: a probe of medium range order

Fluctuation microscopy is a hybrid diffraction-imaging technique that detects medium range order in amorphous materials by examining spatial fluctuations in coherent scattering. These fluctuations appear as speckle in images and diffraction patterns. The volume of material contributing to the speckle is determined by the point-spread function (the resolution) of the imaging optics and the sample thickness. The spatial periodicities being probed are related to the diffraction vector. Statistical analysis of the speckle allows the random and non-random (ordered) contributions to be discriminated. The image resolution that gives the maximum speckle contrast, as determined by the normalized variance of the image intensity, is determined by the characteristic length scale of the ordering. Because medium range ordering length scales can extend out to about the tenth coordination shell, fluctuation microscopy tends to be a low image resolution technique.This review presents the kinematical scattering theory underpinning fluctuation microscopy and a description of fluctuation electron microscopy as it has been employed in the transmission electron microscope for studying amorphous materials. Recent results using soft x-rays for studying nanoscale materials are also presented. We summarize outstanding issues and point to possible future directions for fluctuation microscopy as a technique.

The Maia Spectroscopy Detector System: Engineering for Integrated Pulse Capture, Low-Latency Scanning and Real-Time Processing

The Maia detector system is engineered for energy dispersive x‐ray fluorescence spectroscopy and elemental imaging at photon rates exceeding 107/s, integrated scanning of samples for pixel transit times as small as 50μs and high definition images of 108 pixels and real‐time processing of detected events for spectral deconvolution and online display of pure elemental images. The system developed by CSIRO and BNL combines a planar silicon 384 detector array, application‐specific integrated circuits for pulse shaping and peak detection and sampling and optical data transmission to an FPGA‐based pipelined, parallel processor. This paper describes the system and the underpinning engineering solutions.

Megapixel imaging of (micro)nutrients in mature barley grains

Understanding the accumulation and distribution of essential nutrients in cereals is of primary importance for improving the nutritional quality of this staple food. While recent studies have improved the understanding of micronutrient loading into the barley grain, a detailed characterization of the distribution of micronutrients within the grain is still lacking. High-definition synchrotron X-ray fluorescence was used to investigate the distribution and association of essential elements in barley grain at the micro scale. Micronutrient distribution within the scutellum and the embryo was shown to be highly variable between elements in relation to various morphological features. In the rest of the grain, the distribution of some elements such as Cu and Zn was not limited to the aleurone layer but extended into the endosperm. This pattern of distribution was less marked in the case of Fe and, in particular, Mn. A significant difference in element distribution was also found between the ventral and dorsal part of the grains. The correlation between the elements was not consistent between and within tissues, indicating that the transport and storage of elements is highly regulated. The complexity of the spatial distribution and associations has important implications for improving the nutritional content of cereal crops such as barley.

In Situ Distribution and Speciation of Toxic Copper, Nickel, and Zinc in Hydrated Roots of Cowpea

The phytotoxicity of trace metals is of global concern due to contamination of the landscape by human activities. Using synchrotron-based x-ray fluorescence microscopy and x-ray absorption spectroscopy, the distribution and speciation of copper (Cu), nickel (Ni), and zinc (Zn) was examined in situ using hydrated roots of cowpea (Vigna unguiculata) exposed to 1.5 μm Cu, 5 μm Ni, or 40 μm Zn for 1 to 24 h. After 24 h of exposure, most Cu was bound to polygalacturonic acid of the rhizodermis and outer cortex, suggesting that binding of Cu to walls of cells in the rhizodermis possibly contributes to the toxic effects of Cu. When exposed to Zn, cortical concentrations remained comparatively low with much of the Zn accumulating in the meristematic region and moving into the stele; approximately 60% to 85% of the total Zn stored as Zn phytate within 3 h of exposure. While Ni concentrations were high in both the cortex and meristem, concentrations in the stele were comparatively low. To our knowledge, this is the first report of the in situ distribution and speciation of Cu, Ni, and Zn in hydrated (and fresh) plant tissues, providing valuable information on the potential mechanisms by which they are toxic.

X-ray phase imaging: Demonstration of extended conditions with homogeneous objects

We discuss contrast formation in a propagating x-ray beam. We consider the validity conditions for linear relations based on the transport-of-intensity equation (TIE) and on contrast transfer functions (CTFs). From a single diffracted image, we recover the thickness of a homogeneous object which has substantial absorption and a phase-shift of --0.37 radian.

Phosphorus K-edge XANES spectroscopy of mineral standards.

Phosphorus K-edge XANES spectra are presented for a diverse set of 44 phosphate minerals.

The New Maia Detector System: Methods For High Definition Trace Element Imaging Of Natural Material

Motivated by the need for megapixel high definition trace element imaging to capture intricate detail in natural material, together with faster acquisition and improved counting statistics in elemental imaging, a large energy‐dispersive detector array called Maia has been developed by CSIRO and BNL for SXRF imaging on the XFM beamline at the Australian Synchrotron. A 96 detector prototype demonstrated the capacity of the system for real‐time deconvolution of complex spectral data using an embedded implementation of the Dynamic Analysis method and acquiring highly detailed images up to 77 M pixels spanning large areas of complex mineral sample sections.

Quantification of ZnO Nanoparticle Uptake, Distribution, and Dissolution within Individual Human Macrophages

The usefulness of zinc oxide (ZnO) nanoparticles has led to their wide distribution in consumer products, despite only a limited understanding of how this nanomaterial behaves within biological systems. From a nanotoxicological viewpoint the interaction(s) of ZnO nanoparticles with cells of the immune system is of specific interest, as these nanostructures are readily phagocytosed. In this study, rapid scanning X-ray fluorescence microscopy was used to assay the number ZnO nanoparticles associated with ∼1000 individual THP-1 monocyte-derived human macrophages. These data showed that nanoparticle-treated cells endured a 400% elevation in total Zn levels, 13-fold greater than the increase observed when incubated in the presence of an equitoxic concentration of ZnCl2. Even after excluding the contribution of internalized nanoparticles, Zn levels in nanoparticle treated cells were raised ∼200% above basal levels. As dissolution of ZnO nanoparticles is critical to their cytotoxic response, we utilized a strategy combining ion beam milling, X-ray fluorescence and scanning electron microscopy to directly probe the distribution and composition of ZnO nanoparticles throughout the cellular interior. This study demonstrated that correlative photon and ion beam imaging techniques can provide both high-resolution and statistically powerful information on the biology of metal oxide nanoparticles at the single-cell level. Our approach promises ready application to broader studies of phenomena at the interface of nanotechnology and biology.