2.1. Diamond and Moissanite in Granite from Greifenstein
Based on previous conclusions [
16], the preservation of microdiamonds in granitic rock is extremely unlikely because of the inversion to low-pressure forms during regular transport and emplacement. Therefore, diamond and diamond-bearing moissanite differ from those in Greifenstein granite samples. To eliminate the possibility that diamond and moissanite (SiC) were introduced during cutting and grinding, we also analyzed the materials used for sample preparation (diamond cutting disc, SiC, and diamond polishing powder). The results obtained for natural and technical diamonds are provided in
Table 1.
Our data indicate: 1) a significant difference between the bivariate average values of natural diamond from the Greifenstein granite and diamond cutting discs used for the sample preparation (Diamant Boart, Belgium), at a statistical certainty of 0.999; and 2) all diamonds used for cutting and polishing are cubic, whereas natural diamond from the Greifenstein granite is hexagonal.
The diamond cutting disc (D30-G No. 4716863 Diamant Boart, Belgium) has a mean grain size of 30 µm. The Raman spectra of diamonds from the cutting disk exhibit a peak at 1332.5 ± 0.4 cm-1 with a full width at half maximum (FWHM) of 5.5 ± 0.3 cm-1 (28 measurements), representative of a well-crystallized cubic diamond. The Raman spectra of the 1 µm DP-Spray P diamond polishing powder (SPRON, Struers A/S Peterstrupvej 84, DK-2750 Ballerup) are characterized by a peak at 1336.4 ± 6.9 cm-1 and FWHM of 67.8 ± 17.0 cm-1 (28 measurements). It should be noted that we obtained poor Raman spectra for the ¼ µm DP-Spray P (1334.6 ± 5.80 cm-1; FWHM = 100 ± 6.5 cm-1, n = 28; strong G-band at 1580 cm-1, FWHM = 75 cm-1).
2.2. Natural Diamond and Moissanite in Inclusions in Granite
During the microscopic study of two doubly polished thick sections (3.5 × 2.0 cm; ~300 µm thick) and several small polished chips from the Greifenstein granite, we identified spherical aggregates of moissanite (SiC) in topaz crystals, some of which contain microdiamonds.
Figure 2 shows a large aggregate with an elliptical cross section of 74 × 55 µm. The largest area of diamond in this moissanite in the Greifenstein topaz is ~25 × 7 µm (sample I).
Figure 5 shows another slightly larger aggregate (118 × 73 µm; sample II). This aggregate is not spherical but has strongly rounded peripheries. This aggregate in OH-rich topaz (Toz-2) contains moissanite, quartz, topaz (Toz-1), and diamond as well as smaller diamond grains and microcrystals of coesite and metastable stishovite. The shape and composition indicate the natural origin of this complex SiC aggregate. Such an aggregate cannot be introduced during cutting and grinding. Note that the SiC powder has a grain size of 10 µm and exhibits sharp peripheries.
The diamonds in moissanite in topaz from the Greifenstein granite (
Figure 3) mainly belong to the hexagonal diamond polytype (
Figure 6). Based on 28 measurements, we obtained a value of 1325.4 ± 4.4 cm
-1 for the main Raman peak of diamond. The FWHM is 10.8 ± 4.1 cm
-1. The value for the diamonds in the second moissanite sample was determined to be 1320.9 ± 0.4 cm
-1 (diamond xxx-1). In contrast to diamond polishing powder (D1 and D0.25 µm), Raman spectra of natural diamonds exhibit sharp lines. The Raman spectra of several diamond grains correspond to those of natural lonsdaleite (
Figure 5 and
Figure 6) [
17].
Data for the natural diamond are summarized in
Table 1. Remnants of coesite also occur in the moissanite–diamond–quartz–topaz inclusion (
Figure 3,
Figure 5, and
Figure 6). This is a significant evidence for a high-pressure origin because moissanite, diamond, and coesite are all above their stability fields at the formation depth of the Greifenstein granite. All three phases co-occur in crystal aggregates found as inclusions in topaz. Based on the Raman spectra of coesite (sample I), a mean of 519 ± 0.7 cm
-1 was obtained for the position of the main coesite main. The following rather weak bands can also be used for the identification: 76, 153, 357, and 785 cm
-1. Based on 16 measurements of the symmetric stretching mode [
19] in coesite from sample II, the mean value of the main coesite band is ν
s = 518.8 ± 4.4 cm
-1 (FWHM = 11.2 ± 5.2 cm
-1). The following values (cm
-1) were obtained for the other diagnostic bands: 76.2 ± 0.7, 153.6 ± 0.2, 331.4 ± 0.4, 787.4 ± 1.9, and 1163.7 ± 3.4. In addition to coesite, rare and metastable stishovite was observed. The following values were obtained from the analyses of four stishovite grains: 760.8 ± 1.8, 586.8 ± 2.8, and 232.2 ± 2.4 cm
-1.
A diamond crystal (~20 × 15) µm in sample II yields a value of 1320.9 ± 0.4 cm
-1 with an FWHM of 7.3 ± 0.4 cm
-1 (n = 10), corresponding to the hexagonal diamond polytype lonsdaleite [
17,
20]. This type of diamond is not used for sample preparation.
Based on ten measurements, we obtained a value of 1331.1 ± 1.1 cm
-1 (FWHM = 6.7 ± 1.3 cm
-1) for the diamond in the corroded cristobalite crystal (
Figure 8). All diamond grains from the Greifenstein granite show a prominent G band at ~1590 cm
-1 of carbonaceous material.
In addition to diamond, the small elliptical moissanite inclusion in topaz (sample III) shown in
Figure 9 contains an aggregate of cristobalite with tiny coesite crystals, cristobalite-II, or Si with a very strong dominant Raman band at 518.2 ± 0.8 cm
-1 and FWHM = 6.4 ± 1.3 cm
-1 (n = 24). Note that a clear differentiation between the three minerals is impossible because the strong and broad Raman bands of cristobalite and moissanite overlap. Černok [
21] reported that cristobalite-II has a strong band at ~519 cm
-1 (at 2 GPa), which competes with the main coesite band. The intense and sharp Raman band at 713.7 ± 1.1 cm
-1 (FWHM = 13.4 ± 1.4 cm
-1) indicates the presence of cristobalite-X-I. Further research is necessary in the near future, because the proof of cristobalite-X-I would indicate a significant higher pressure (~10 GPa and more).
The spectrum of the moissanite crystal [SiC] in the inclusion (
Figure 2) of sample I is characterized by strong lines at 774.4 ± 7.2 cm
-1 (FWHM = 24,5 cm
-1) and 945.1 ± 12.0 cm
-1 (FWHM = 24.2 cm
-1). This crystal is significantly larger (67 × 27 µm) than the grains in SiC powder used for grinding (F10 with a 10 µm mean grain size). This technical-grade SiC is of type 6H-SiC and exhibits prominent bands at 784.0 ± 3.6 cm
-1 and 963.1 ± 2.4 cm
-1 with a FWHM of 7.1 ± 1.7 cm
-1 and 19.8 ± 14.0 cm
-1, respectively (15 different grains). Natural and technical SiC significantly differ, not only in size.
Based on the size, spherical form, and diamond type, diamond, lonsdaleite, graphite, moissanite, and kumdykolite do not represent contamination of topaz from the Greifenstein granite that was introduced during sample preparation. We propose that they represent phases that are most likely rapidly transported by a supercritical fluid from a depth corresponding to a pressure of ≥5 GPa or in the case of cristobalite X-I of ~11 GPa to the location of granite crystallization at about 0.21 to 0.1 GPa [
13] in analogy to coesite in prismatine from the Waldheim granulite trapped at about 1.3 GPa at 1000°C [
4].
Based on the assumption that diamond, lonsdaleite, moissanite, graphite, and kumdykolite were transported by a supercritical fluid, energy, volatiles, and a broad spectrum of main and trace elements would also be added to the crystallizing granite. This indicates the necessity of a reassessment of the genetic concept of element enrichment. In addition, the generally accepted origin of the topaz from the Greifenstein granite as a late phase must be scrutinized because the diamond, graphite, SiC, cristobalite, and coesite inclusions in topaz imply a different formation of this topaz type. Note that such hydroxyl-rich topaz has been identified in ultrahigh-pressure metamorphic rocks [
22].