LABQ3: Bayesian method for quantification of mineral compositions and nano-scale elemental mapping of 3D synchrotron XCT data

Abstract

Quantitative analysis of mineral compositions is essential in understanding geochemical, mineralogical and environmental processes. Fine-resolution 3D imaging is widely done using synchrotron X-ray computed tomography (XCT), but existing analyses are limited to visualization and segmentation. This paper presents a new method, Linear Attenuation Bayesian Quantitative 3D-mapper (LABQ3), based on the linearity of X-ray attenuation with respect to elemental concentrations. To address the random variability in attenuation measurements, LABQ3 employs Bayesian decision theory to minimize classification error, using reference attenuation distributions from scans of pure mineral standards. To demonstrate LABQ3 and test its performance, we studied precipitated carbonate samples. XCT scans were done at multiple energies using the transmission X-ray microscope (TXM) at beamline 32-ID-C of the Advanced Photon Source at Argonne National Laboratory. The reconstructed 3D images have a voxel size of 20 nm. Analyses revealed rich nano-scale compositional heterogeneity within individual particles. A mixture of calcium and cadmium produced an overall stoichiometric composition of (Ca_0.78,Cd_0.22)CO₃, with some voxels containing nearly pure CdCO₃. The addition of zinc led to an overall stoichiometric composition of 33% Ca, 28% Cd, 39% Zn, with a nearly pure CaCO₃ core and compositional zonation through the rim. These compositional gradients are related to temporal sequences of carbonate mineral formation where Cd precipitated at the beginning in (Ca,Cd)CO₃, while Cd and Zn precipitated at the end in (Ca,Cd,Zn)CO₃. Results differ from bulk analyses using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), showing that LABQ3 provides particle-specific insights. LABQ3 distinguishes itself by quantifying chemical compositions along a continuum, making it different from XCT analyses based on segmentation. LABQ3 allows simultaneous acquisition of morphology and chemical composition in 3D, facilitating the interpretation of chemical gradients of trace elements, quantification of solid solution compositions, inferences about temporal sequences of mineral precipitation, and addressing other concerns about solid-phase chemistry.