Considerations About Bi and Pb in the Crystal Structure of Cu-Bearing Tourmaline

Copper- and Mn-bearing elbaitic tourmaline ("Paraiba tourmaline") sometimes contains significant amounts of Pb and Bi. Their position in the tourmaline crystal structure was studied with correlation analysis and bond valence calculations. Correlations between the F content and the X-site charge allow predicting the X-site occupancy. Three sets of tourmaline analyses were studied: (1) Pb-rich tourmalines from the Minh Tien pegmatite, Vietnam; (2) Cu-, Pb- and Bi-bearing tourmalines from the Mulungu mine, Brazil; (3) Cu- and Bi-bearing tourmalines from the Alto dos Quintos mine, Brazil. Two correlations were plotted: (1) the charge by considering only Na1+, Ca(2+)and K1+; (2) the charge by adding Pb(2+)and Bi(3+)to the X-site charge. When plotting correlations for the Minh Tien tourmalines, the correlation significantly improves by adding Pb(2+)to the X site. For the Alto dos Quintos tourmalines, only a slight increase of the correlation coefficient is observed, while such a correlation for tourmalines from Mulungu interestingly shows a slight decrease of the correlation coefficient. Bond valence calculations revealed that Bi(3+)and Pb(2+)can indeed occupy the X site via BiLi(NaAl)(-1,)PbLi(NaCu)(-1)and possibly PbCu(NaAl)(-1)substitutions as seen in the investigated tourmaline samples. At the Y site, Pb(4+)can be substituted via PbLi(AlCu)(-1), and (PbO)-O-V((AlOH)-O-V)(-1), while Bi(5+)does not have any stable arrangement in Cu-bearing fluor-elbaite. The occurrence of Pb(4+)at the Y site could be one explanation for the results of the correlations of the Mulungu tourmalines. Another explanation could be that during the tourmaline crystallization some additional Bi and Pb came into the pegmatitic system and hence disturbed the correlation between the average X-site charge and the F content. Further plots of such correlations in "Paraiba tourmaline" samples might also help to distinguish between the worldwide localities of these rare and sought-after tourmalines.