1. Introduction
In the gemological world we often speak of the “big three”, the three high-value gems that dominate the colored stone market: ruby, sapphire, and emerald (at least in the western world, in much of Asia, jade is the most important gem). Two of the big three, ruby and sapphire, are the same mineral species, corundum, and this special issue is wholly devoted to ruby, the red variety of the mineral corundum. Although they are the same mineralogical species with essentially the same chemical makeup (generally >98 wt% Al2O3), rubies with a vivid, deep red saturated color can be far more desirable than almost any vividly colored blue sapphire.
In our silica-rich Earth, corundum (α-Al
2O
3) is not the easiest mineral to form as any excess alumina tends to react with silica and other components such as alkalis to form other alumina-rich minerals such as feldspars and micas. Corundum therefore forms in a limited range of P-T-x environments (including silica undersaturation), and the number of possible ways in which gem-quality corundum can form is even narrower [
1,
2]. The geological conditions of formation have imparted some gem corundum with a sufficient quantity of the red-coloring agent chromium to pass as a ruby, while some gem corundum is colored by iron and titanium, which impart the blue color seen in sapphires. In fact, considering the geology of the major ruby and sapphire deposits in the world, at first glance it seems to make sense. In metamorphic terranes, rubies often form in marbles derived from platform carbonates. While the exact mechanisms of formation may not be entirely understood, it has been suggested that molten evaporate salts enabled mobilization of chromium and aluminum that enabled crystallization of Cr-rich corundum [
3,
4]. In contrast, metamorphic blue sapphires typically form in settings where a deficiency in chromium is expected, such as from the interaction between syenitic pegmatites and high-grade metamorphic rocks (Mogok, Myanmar) or from amphibolite or granulite facies gneisses (Sri Lanka and Madagascar) [
1,
5].
This contribution will focus on specific gemstone deposits from major gem producing regions around the world which are known for producing both blue sapphires and rubies. This contribution focuses on gem deposits from major gem producing regions. The deposits included are Mogok, Myanmar; Chanthaburi, Thailand; Pailin, Cambodia; Montana, USA; and various gem deposits in Sri Lanka. The gemological properties of the blue sapphires and rubies from these deposits will be described, especially their inclusions and trace element chemistry, with the intent of determining the relationships (if any) between these two varieties of gem corundum and to help understand the possible controls on the geochemical behavior of chromium in the specific formation situation of gem corundum.
2. Materials and Methods
The samples dominantly were derived from the Gemological Institute of America’s (GIA) Colored Stone Reference Collection, which was built up over more than 10 years through the GIA Field Gemology program [
6]. This was supplemented, especially for the Montana sapphires, by samples provided by several trusted contacts who have worked extensively in the sapphire mining areas of Montana including Richard B. Berg from the Montana Bureau of Mines and Geology, John Emmett, a consultant with GIA, Jeff Hapeman, a gem dealer with Earth’s Treasury, and Will Heierman, a gem dealer who has worked with many of the sapphire miners in Montana. The sample set is comprised of 17 Thai/Cambodian rubies, 28 Thai/Cambodian blue sapphires, 18 Sri Lankan rubies, 17 Sri Lankan pink sapphires, 61 Sri Lankan blue sapphires, 43 rubies from Mogok, Myanmar, 143 blue sapphires from Mogok, Myanmar, 16 secondary Montana rubies, 6 secondary Montana pink sapphires, 52 secondary Montana blue sapphires, 8 Yogo, Montana rubies, 9 Yogo, Montana violet sapphires, and 18 Yogo, Montana blue sapphires. Essentially all the samples in this reference collection were collected from secondary alluvial or elluvial deposits which were weathered from primary, hard rock deposits. The main exception is the Yogo sapphires and rubies, which are derived from a primary deposit.
Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses were conducted using a Thermo Scientific iCap-Q ICP-MS (Thermo Fisher Scientific, Waltham, MA, USA) with plasma RF power of 1400 W coupled with a New Wave Research UP-213 laser ablation (New Wave Research, Inc, Bozeman, MT, USA) unit with a frequency-quintupled Nd:YAG laser (213 nm wavelength with 4 ns pulse width). Laser conditions consisted of a 55 µm diameter spot size, a fluence of 10 ± 1 J/cm
2, and a 15 Hz repetition rate using NIST 610 and 612 glasses as external standards and
27Al as an internal standard with a defined value of 529,250 ppm Al. Accuracy of the measurements on the standard reference materials is generally within 5% to 20%. On longer runs lasting more than 2 h, one of the standards was run again as an unknown as a quality control measure to ensure instrument drift was kept at an acceptable level by ensuring that a standard reference material could be measured within 15% of its known values for the relevant elements. The analyses reported here were carried out over the course of several years in the lab at the GIA, and so the detection limits varied over the course of data collection. However, general ranges for detection limits are 0.1–0.3 ppm Mg, 1.2–4.7 ppm Ti, 0.1–0.5 ppm V, 1.3–5.1 ppm Cr, 13.7–54.8 ppm Fe, and 0.1–0.2 ppm Ga. Detection limits were calculated according to the method of Longerich et al. [
7]. Each stone was typically analyzed in three spots, but sometimes, up to 12 spots were obtained if there was significant color zoning or regions with clouds of microscopic inclusions that were targeted to get a statistically significant representation of chemical heterogeneity in these stones.
When possible, mineral inclusions were identified using Raman spectroscopy with a Renishaw inVia Raman microscope system. The Raman spectra of the inclusions were excited using a Stellar-REN Modu Ar-ion laser producing highly polarized light at 514 nm and collected at a nominal resolution of 3 cm−1 in the 2000–200 cm−1 range. Each spectrum was comprised of three accumulations at 20× or 50× magnification. In many cases, the confocal capabilities of the Raman system allowed inclusions beneath the surface to be analyzed. Several other stones were polished to expose the inclusion to the surface.
4. Discussion and Conclusions
As this special issue can attest, the investigation of the geological genesis of important gemstone deposits has become a serious scientific pursuit. Unfortunately, in many cases traditional geological studies are inadequate to understand the formation of gem corundum deposits. This is because most gem corundum is found in secondary deposits formed through millions of years of weathering, and hence, much of the traditional geological context is lost. Therefore, in order to understand these precious stones’ geological story, researchers must turn to clues taken from the stones’ inclusions, trace elements, and isotopes. Inclusions have been especially helpful in many cases especially the study of melt and mineral inclusions [
14,
21,
24,
25,
26]. It can be challenging to build a full geologic model from inclusions that may sparsely populate the gem corundum and which may or may not be fully representative of the initial mineral/fluid assemblage in which the stones formed. However, often inclusions are the only available piece of evidence that can directly link the sapphires and rubies to their geological origins. Inclusion analysis has been useful to study other gemstones as well such as the use of diamond inclusions, which has vastly improved our understanding of the deep Earth [
27,
28].
In contrast, the path from trace element chemistry to geological origin is less well understood. Many previous studies have shown that trace element chemistry of gem corundum is controlled by geological origin [
19,
29,
30,
31]. However, there have been some documented cases where the trace element chemistry classification of stones from certain deposits does not agree with information of their geological origin from either their inclusions or geological field observations [
14,
21,
28,
32,
33]. As described by these authors, while the existing chemical discrimination diagrams can be quite useful, in some cases, they do not always accurately predict geological origin. Even without these specific cases where the existing classification schemes break down, [
15] suggested that even for the classical metamorphic and basalt-related blue sapphires, there is some degree of overlap in their trace element chemistry in the range of Fe and Ga concentrations, where the Fe and Ga are at the high end for metamorphic blue sapphires and at the low end for basalt-related blue sapphires.
When discussing the geological origins of gem corundum, rubies and blue sapphires are often considered separately [
1], with the implication that the geological conditions for sufficient Cr-enrichment to form rubies must be significantly different from the geological conditions that would form low-Cr blue sapphires. The Thai/Cambodian rubies are considered to have formed from rocks that could have been Cr-enriched, while their blue sapphire counterparts likely formed from alkaline igneous rocks such as syenites that should not have been significantly enriched in Cr [
11,
15]. Some of the established trace element geological classification schemes utilize Cr as an essential discriminant between metamorphic and magmatic sapphires with the implication that Cr is expected to partition into corundum differently based on geological origin [
34,
35]. However, how far can this argument go before it breaks down? From the results presented above for gem corundum deposits that produce both rubies and blue sapphires within the same deposit, it is clear there are two types of coexisting blue sapphire/ruby assemblages: monogenetic and polygenetic assemblages.
The polygenetic assemblages are those in which rubies and blue sapphires clearly have different geological origins, and yet, the two geochemically and geologically distinct assemblages happen to occur in the same deposit. In the present work, this includes blue sapphires and rubies from Thailand/Cambodia as well as Mogok, Myanmar. It should be noted that this is not necessarily to say that the origin of the rubies and blue sapphires are completely unrelated. The rubies and blue sapphires in Chanthaburi, Thailand, and Pailin, Cambodia, were clearly transported to the surface by similar alkali basalts; however, the results above and work from other researchers indicate that these two varieties of gem corundum were derived from mineralogically and geochemically distinct environments [
14,
16,
17,
24]. Similarly, rubies and blue sapphires from Mogok, Myanmar, were both derived from regional metamorphism and/or igneous activity directly related to the Himalayan Orogeny, even if their specific modes of formation are distinct. Furthermore, while the rubies and sapphires from both the Thai/Cambodian and Mogok deposits are distinct in many of their properties, there are some similarities in their properties that tend to obscure the documented differences in their geological origins. For instance, although there are differences in their overall inclusions, the short reflective platelet-like silk, occasional long, slender rutile silk, and calcite mineral inclusions are common between the two types of stones. Additionally, for the sapphires and rubies from Mogok, Myanmar, while there are clear differences in their Fe contents, plots involving other elements such as Mg, Ti, and Ga tend to show nearly complete overlap in their compositions.
In contrast, the monogenetic ruby/sapphire assemblages described here are those in which the inclusions and trace element chemistry point toward a single geological origin for rubies and blue sapphires within a single deposit. In this study this includes rubies and blue sapphires from Yogo Gulch, Montana, as well as the secondary Montana sapphires and rubies in addition to the rubies and blue sapphires from Sri Lanka. One notable aspect of the monogenetic assemblages is the continuous transition in Cr concentrations across the blue sapphire-pink sapphire-ruby spectrum. However, the most surprising feature of the trace element relationships in the monogenetic suites is that Cr does not show a correlation with most other trace elements. The main exception seems to be V, which is positively correlated with Cr in most cases. Note, Zaw et al. also discussed the potential correlation between V and Cr in rubies and sapphires from Mogok, Myanmar [
30]. Occasionally, the correlation matrices also show a weak positive correlation with trace elements like Ga and sometimes Mg or Ti. However, the other trace elements in the monogenetic assemblages tend to vary generally by less than two orders of magnitude, while Cr can vary by well over three to nearly four orders of magnitude. Even over this wide range in Cr concentrations, there is typically relatively little variation in the range of the other trace elements (except V as stated above). One surprising observation here is that Cr concentrations can vary between such extremes with little to no variations in the trace element chemistry and inclusions. This presumably indicates similar geological origins for the high- and low-Cr corundum. Apparently, in these environments, Cr behaves independently from the other trace elements commonly found in gem corundum, even when compared to trace elements that share the same valence state as Al
3+ such as Fe
3+ and Ga
3+.
While this study focuses on a small number of deposits where reliably collected reference samples were available, there is ample room for expanding this work to other important deposits. Notably, the Australian sapphire fields, known as one of the most important producers of basalt-related sapphires, have also occasionally produced red rubies, although in significantly lower quantities [
36,
37,
38,
39]. In fact, Sutherland et al. [
39] noted a very similar transition from purple and bluish sapphire to pink sapphire to rubies in the New England, New South Wales, gem fields which had higher Ga and Ga/Mg ratios than other basalt-related rubies such as those from Chanthaburi, Thailand, and Pailin, Cambodia. Additionally, while understudied, the gem corundum deposits of Colombia are known for producing small quantities of rubies in addition to blue and other fancy colored sapphire [
40,
41]. Rubies from many deposits in their natural, untreated state often have distinct blue color zoning either in the cores of the stones as in Mong Hsu stones from Myanmar [
42,
43], Vietnam [
43,
44,
45,
46], or Tajikistan [
43,
47,
48]. While this blue/red zoned corundum may not fit the category of monogenetic ruby/blue sapphire assemblages, they are evidence of the complex geochemical controls on the trace element chemistry of gem corundum and the difficulty of neatly categorizing these stones based on their trace elements.
The reasons for the extreme diversity in Cr concentrations relative to other trace elements in the monogenetic ruby/blue sapphire assemblages are not obvious. One possible explanation is mineralogical heterogeneity in Cr-bearing minerals in the geological environment in which the gem corundum formed. Cr tends to be concentrated in a relatively small number of mineral phases compared to Fe and Ga, and this extreme variance in Cr concentrations could be related to the fortuitous spatial relationship between the growing corundum crystal and nearby Cr-bearing minerals. However, what would be the cause for such extreme heterogeneity in Cr-bearing minerals in the monogenetic assemblages relative to the polygenetic ruby/sapphire assemblages?
One conclusion from this study is that rubies and sapphires do not necessarily represent different tectonic environments or different geological conditions of formation. Whatever environments facilitate the formation of gem corundum in the Earth, they may not always discriminate between Cr-enriched rubies and Cr-poor blue sapphires. The observations and discussion presented here provide a basis for further investigations into the question posited above: what makes a ruby a ruby? With such huge differences in the value placed on these two varieties of gem corundum, we often still need to understand the geochemical constraints that can turn a sapphire into an extraordinary, richly colored red ruby.