Supplementary Materials for: "Characterization, axial anisotropy and formation conditions of celestine from the Jabal Eghei (Nuqay) late Neogene – Pleistocene volcanic province, southern Libya: Constraints on the mineralogical geothermometer"

Abstract

Figure S1. a The investigated area within the circum-Mediterranean realm; b Geological Mapping campaign of central and southern Libya (marked with green color); c The wider area of the Al Haruj and Jabal Eghei Volcanic Provinces; d Jabal Eghei Volcanic Province; and e The surface-exposed basalts as the result of the three Middle Miocene to Pliocene volcanic events (according to Radivojević et al. 2015). The spots of the celestine sampling locations are marked with the “×” symbol, collected from the area of the sheet NF 34-1, Geological Map of Libya, scale 1:250,000 (marked with red color). Figure S2. SEM photos (column I, left) and sum spectrums (column II, right) of the analyzed 1-5 samples. Figure S3. The observed (column I, left) XRPD patterns of the 1-5 samples. The Le Bail (1988) profile fitting (column II, right) of the XRPD patterns of the 1-5 samples. The observed spectra (red dotted line), fitted spectra (black solid line), difference plot (blue solid line) and Bragg peak positions (green tick marks), are shown as well. Table S1. Observed interplanar spacings (dobs, in Å) and relative intensity ratios-RIR (Iobs, in %) of the studied samples; compared to the reference ICDD-PDF's (ICDD-PDF: International Centre for Diffraction Data-Powder Diffraction File) 89-0953 and 05-0593 data standards. Figure S4. Comparative presentation of the reflections with following Miller's hkl indices: (a) 002; (b) 210; (c) 102; (d) 211; (e) 112 (left) and 020 (right); (f) 122 & 113 (left) and 203 & 401 (right); (g) 004; (h) 323; (i) 040 (left) and 431 (right); and (j) 006. Figure S5. Magnified 24.5-30.5o (column I, left) and 31-90o (column II, right) 2θ angle ranges of the Le Bail (1988) profile fittings (Figure S3, column II). Table S2. Selected profile parameters and reliability factors refined from the Le Bail (1988) profile fitting method. Figure S6. Linear (column I, left) and polynomial [column II, right; C(1)] variations for 1-5 samples of: (a & d) axis a0 (in Å) by axis c0 (in Å); (b & e) axis a0 (in Å) by volume V0 (in Å3); and (c & f) axis c0 (in Å) by volume V0 (in Å3). Marks “+” denote celestine positions (ICDD-PDF: 89-0953). Figure S7. Linear (column I, left) and polynomial [column II, right; C(2)] variations of the axis b0 (in Å) for 1-5 samples by: (a & d) axis a0 (in Å); (b & e) axis c0 (in Å); and (c & f) volume V0 (in Å3). Marks “+” denote celestine positions (ICDD-PDF: 89-0953). Figure S8. Positions of the polynomial variations of the studied samples (Figures S6 and S7) in regard to the celestine, anglesite and barite standards [ICDD-PDF's: 89-0953 (marked as “+”), 36-1461 (marked as “☼”) and 24-1035 (marked as “×”), respectively]: (a) axis b0 (in Å) by axis a0 (in Å); (b) axis a0 (in Å) by axis c0 (in Å); (c) axis b0 (in Å) by axis c0 (in Å); (d) axis a0 (in Å) by volume V0 (in Å3); (e) axis b0 (in Å) by volume V0 (in Å3); and (f) axis c0 (in Å) by volume V0 (in Å3). Celestine-anglesite linear joins were marked with dotted lines, whereas celestine-barite linear joins were marked with interrupted lines. Table S3. Calculated differences (in %) between the UCPs for various solid-solutions series. Figure S9. Infrared spectra of the studied samples. Figure S10. Chromatic diagram of the studied samples. Figure S11. Linear (column I, left) and polynomial [column II, right; C(3)] variations of the calculated ionic radiuses (in Å; Table 2) for 1-5 samples by: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Marks “+” and “×” denote celestine positions (ICDD-PDF's: 89-0953 and 05-0593, respectively). Table S4. Correlations of the different studied variations (see Discussion, for details). Table S5. Determined apfu’s (in at. %) at the 2 (ΣM+S) ions basis from the determined WDS analyses (Table 1). Table S6. Calculated theoretical ionic radiuses (in Å) of the M cations, and calculated occupancies of the twelve-coordination site (in at. %) at basis of the determined apfu’s (Table S5). Figure S12. Linear (column I, left) and polynomial [column II, right; C(4)] variations of the calculated ionic radiuses (in Å; Table S6) for 1-5 samples by: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Table S7. Recalculated (calc1-3) WDS analyses of the 1-5 studied samples (in wt. %). Atoms per formula units (apfu; in at. %) were calculated at 4 oxygen anions basis. Table S8. Recalculated (calc1-3) theoretical ionic radiuses (in Å) of the M cations, and calculated occupancies of the twelve-coordination site (in at. %) at basis of the recalculated (calc1-3) WDS analyses (Table S7). Figure S13. Linear (column I, left) and polynomial [column II, right; C(5)] variations of the calculated ionic radiuses (in Å) for 1-5 samples without calculated anhydrite or gypsum contents (Table S8; calc1,2) by: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Marks “+” denote celestine positions (ICDD-PDF: 89-0953). Figure S14. Linear (column I, left) and polynomial [column II, right; C(6)] variations of the calculated ionic radiuses (in Å) for 1-5 samples without calculated anhydrite, gypsum and other minerals with the X component contents (Table S8; calc3) by: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Marks “+” denote celestine positions (ICDD-PDF: 89-0953). Table S9. Recalculated theoretical ionic radiuses (in Å) of the M+S6+ ions and calculated occupancies of the twelve-coordination site within two possible options for celestines: as monomineral („mono“; Table 2), and without minor anhydrite („A“) or gypsum („G“) contents (Table S8; calc1,2). Figure S15. Linear (column I, left) and polynomial [column II, right; C(7)] variations of the recalculated ionic radiuses (in Å) for 1-5 samples treated as monomineral celestines (Table S9; „mono“) by: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Marks “+” and “×” denote celestine positions (ICDD-PDF's: 89-0953 and 05-0593, respectively). Figure S16. Linear (column I, left) and polynomial [column II, right; C(8)] variations of the recalculated ionic radiuses (in Å) for 1-5 samples treated as major celestines with neglected anhydrite („A“) or gypsum („G“) contents (Table S9) by: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Marks “+” and “×” denote celestine positions (ICDD-PDF's: 89-0953 and 05-0593, respectively). Table S10. Determined (marked as „det“; Table 5) and presumed (marked as „pre“) UCPs of the studied samples (as monomineral, Table 1); and without minor anhydrite („A“) and gypsum („G“) contents (Table S7). Differences (Δ) and ratios between these are also presented. Figure S17. Linear (column I, left) and polynomial [column II, right; C(9)] variations of the calculated ionic radiuses (in Å; Table 2) for monomineral 1-5 samples (Table S10) by: (a & e) ratio of axis a0; (b & f) ratio of axis b0; (c & g) ratio of axis c0; and (d & h) ratio of volume V0. Figure S18. Linear (column I, left) and polynomial [column II, right; C(10)] variations of the calculated ionic radiuses (in Å; Table S8) for 1-5 samples without calculated Ca from anhydrite or gypsum contents (Table S10) by: (a & e) ratio of axis a0; (b & f) ratio of axis b0; (c & g) ratio of axis c0; and (d & h) ratio of volume V0. Figure S19. Linear (column I, left) and polynomial [column II, right; C(11)] variations of the presumed (Table S10) by determined (Table 5) UCPs: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Table S11. UCPs and average <M-O> distances (in Å) of the selected celestines. Table S12. Recalculated apfu’s (in at. %) from Table 1. Table S13. Recalculated theoretical ionic radiuses (in Å) of the M cations, and occupancies of the twelve-coordination site (in at. %) from Table 2. Table S14. Recalculated apfu’s (in at. %) from Table S7 (calc1,2). Table S15. Recalculated theoretical ionic radiuses (in Å) of the M cations, and occupancies of the twelve-coordination site (in at. %) from Table S8. Figure S20. Linear (column I, left) and polynomial [column II, right; C(12)] variations of the recalculated ionic radiuses (in Å) for 1-5 samples treated as monomineral celestines (Table S13) by: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Figure S21. Linear (column I, left) and polynomial [column II, right; C(13)] variations of the recalculated ionic radiuses (in Å) for 1-5 samples treated as major celestines with neglected anhydrite or gypsum contents (Table S15) by: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Table S16. Determined (marked as „obs“; Table 5) and presumed (marked as „calc“) UCPs of the studied samples as monomineral celestines (Table S12). Differences (Δ) and ratios between these are also presented. Figure S22. Linear (column I, left) and polynomial [column II, right; C(14)] variations of the calculated (Table S16; marked as „calc“) by observed (Table 5; marked as „obs“) UCPs: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Table S17. Recalculated variations of temperature dependence by UCPs for the Clt98Ang02, Clt96Ang04 and Clt94Ang06 celestine-anglesite solid-solution series, at the ambient pressure conditions. Table S18. Recalculated variations of temperature dependence by UCPs for the Clt99Brt01, Clt98Brt02 and Clt97Brt03 celestine-barite solid-solution series, at the ambient pressure conditions. Table S19. Relative UCPs of celestine, anglesite and barite, calculated from the ratio of the data at 320K* and 520K (Tables S17 and S18). Figure S23. Five possible different variations (plotted from Figure 3h) of: 1. volume increase by a temperature increase, including the Brt contents increase; 2. volume increase by a constant temperature, including the Brt contents increase; 3. volume increase by a temperature decrease, including the Brt contents increase; 4. constant volume by a temperature increase, including the Brt contents decrease; and 5. volume increase by a temperature increase, having a constant Brt content. Figure S24. Linear (column I, left) and polynomial [column II, right; C(15)] variations of the temperature (in K) for 1-5 samples (Tables 5 and 8) by: (a & e) axis a0 (in Å); (b & f) axis b0 (in Å); (c & g) axis c0 (in Å); and (d & h) volume V0 (in Å3). Table S20. Estimated UCPs of the studied samples at room temperature (23 oC) and ambient pressure conditions, at basis of the extrapolated data presented in Tables S17 and S18; Table 8 and Figure 3. Figure S25. Linear (column I, left) and polynomial [column II, right; C(16)] variations of the average temperature (in K) for 1-5 samples (Table 8) by ratio (Table 9) of: (a & e) axis a0; (b & f) axis b0; (c & g) axis c0; and (d & h) volume V0.