ABSTRACT:The X-ray spectra of pure elements, excited using MeV energy beam of protons from the nuclear microprobe, have known spectra signatures. This makes X-ray spectra for more complex mixtures amenable to decomposition into contributions from the component elements. By devising this procedure as a matrix operation that transforms directly from spectrum vector to elemental concentration vector, the decomposition can be performed very efficiently enabling the real-time projection of the component element signals. In the case of a raster-scanned beam, with data that contain position information for each X-ray event, this approach enables the real-time projection of component element spatial distribution images. This paper describes the matrix transform approach called dynamic analysis (DA), which enables on-line real-time imaging of major and trace elements using proton-induced X-ray emission (PIXE). The method also provides off-line iterative yield corrections to these images to compensate for changing sample composition across an image area. The resulting images are quantitative in two respects: (1) they resolve the pure element components and strongly reject interferences from other elements and (2) they can be directly interrogated for sample composition at each pixel, over areas, or along lines across the image area, with accuracy comparable to microanalytical point analysis methods. The paper describes the DA method, presents tests, and discusses its application to quantitative major and trace element imaging in geology.

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The temperatures and pressures of equilibration of single peridotitic garnet xenocrysts are estimated using a combination of major-and trace-element data, determined using electron microprobe (EMP) and proton induced X ray emission (PIXE). This new method enables the use of xenocrysts found in kimberlites and other volcanic rocks to determine the local paleogeotherm at the time of eruption of the magma which sampled and transported the xenocrysts. The "Ni thermometer" of Griffin et al. [ 1989], based on the strong temperature dependence of the partitioning of Ni between garnet and olivine, is refined using an expanded database. Pressure is calculated from garnet composition using an algorithm that combines a modification of the geobarometer of Nickel [1989], based on Cr solubility in coexisting garnet and orthopyroxene, with the composition of a hypothetical coexisting orthopyroxene. The orthopyroxene composition is estimated by inverting the geothermometry equations of Gasparik [1987], Brey and KOhler [1990], and Harley [1984], and combining these with empirical relationships describing Cr in orthopyroxene in Crsaturated peridotitc (chromite present). The derived pressure (PCr) gives the equilibration pressure of peridotic garnets provided they were in equilibrium with chromite; garnets from Cr-undersaturated rocks will produce underestimates of pressure. Therefore, the locus of maximum PCr at a given TNi defines the "garnet geotherm", and provides a method for the determination of paleogeotherms based solely on PIXE and EMP analyses of garnet grains in concentrates. The assumption of coexisting chromite is tested by comparing the temperature distributions of garnets and chromites from the same concentrate. Chromite equilibration temperature is estimated using the "Zn thermometer", based on the strong temperature dependence of the partitioning of Zn between chromite and olivine. This thermometer is calibrated against the new Ni thermometer using a suite of garnet-chromite intergrowths. The garnet geotherm technique provides an estimate of the geotherm with an accuracy comparable to xenolith-derived geotherms and provides a means of mapping the thermal state of the lithosphere where xenoliths are rare or absent. display major element partitioning between their constituent min-The use of trace-element patterns measured using proton in-eraIs that is widely regarded as quenched from mantle conditions duced X ray emission (PIXE) on the proton microprobe has proand is routinely used to locate the source of these rocks in pres-vided a partial solution to this problem. The concentration of sure (P) and temperature (73 coordinates. However, these poly-trace Ni in peridotitic garnets can be used routinely to estimate the phase mantle samples are rare in many provinces, although rem-equilibration temperature TNi for each garnet in its source rock. nants of disaggregated xeno!iths can be found as discrete grains in This empirical "Ni thermometer" [Griffin et al., 1989] is refined heavy-mineral concentrate. Garnets in these ...

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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.