A Raman spectroscopic study on the structural disorder of monazite–(Ce)

Abstract

This study addresses whether Raman spectra can be used to estimate the degree of accumulated radiation damage in monazite-(Ce) samples whose chemical composition was previously determined. Our results indicate that the degree of disorder in monazite–(Ce), as observed from increasing Raman band broadening, generally depends on both the structural state (i.e., radiation damage) and the chemical composition (i.e., incorporation of non-formula elements). The chemical effects were studied on synthetic orthophosphates grown using the Li-Mo flux method, and non radiation-damaged analogues of the naturally radiation-damaged monazite–(Ce) samples, produced by dry annealing. We found that the “chemical” Raman-band broadening of natural monazite–(Ce) can be predicted by the empirical formula, $$ {\hbox{FWHM}} {\hbox{[c}}{{\hbox{m}}^{ - {1}}}{]} = {3}{.95} + {26}{.66} \times {\hbox{(Th}} + {\hbox{U}} + {\hbox{Ca}} + {\hbox{Pb)}} {\hbox{[apfu]}} $$ where, FWHM = full width at half maximum of the main Raman band of monazite–(Ce) (i.e., the symmetric PO4 stretching near 970 cm−1), and (Th+U+Ca+Pb) = sum of the four elements in apfu (atoms per formula unit). Provided the chemical composition of a natural monazite–(Ce) is known, this “chemical band broadening” can be used to estimate the degree of structural radiation damage from the observed FWHM of the ν1(PO4) band of that particular sample using Raman spectroscopy. Our annealing studies on a wide range of monazite–(Ce) reference materials and other monazite–(Ce) samples confirmed that this mineral virtually never becomes highly radiation damaged. Potential advantages and the practical use of the proposed method in the Earth sciences are discussed.