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New Textural Evidence on the Origin of Carbonado Diamond: an Example of 3-D Petrography Using X-Ray Computed Tomography

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New Textural Evidence on the Origin of Carbonado Diamond: an Example of 3-D Petrography Using X-Ray Computed Tomography New textural evidence on the origin of carbonado diamond: An example of 3-D petrography using X-ray computed tomography Richard A. Ketcham1 and Christian Koeberl2 1High-Resolution X-Ray Computed Tomography Facility, Jackson School of Geosciences, The University of Texas at Austin, Austin, Texas 78712, USA 2Department of Lithospheric Research, University of Vienna, Althanstrasse 14, A-1090 Vienna, Austria, and Natural History Museum, Burgring 7, A-1010 Vienna, Austria ABSTRACT material that comprises them may not be, –32‰, with major modes at –24‰ and –26‰, and may instead be broken-down remains of rare for diamonds and suggestive of organic car- Three-dimensional textural observations the original included phase(s). While further bon (De et al., 2001; Kagi et al., 2007), although of inclusion and porosity patterns in a 23- verifi cation is needed, a model built around the source for light carbon in the mantle remains carat carbonado diamond using high-reso- this hypothesis may provide the simplest an open question (Deines, 2002). The diamond lution X-ray computed tomography reveal explanation to many of the unusual features material contains H (hydrogen) defects indica- new information bearing on the nature and of carbonado. tive of a hydrogen-rich environment (Garai et al., origin of this enigmatic material. A promi- 2006; Nadolinny et al., 2003), and N (nitrogen) nent patinaed surface is texturally linked to INTRODUCTION defects in various states of aggregation (Fukura a banding and grading of inclusions and pore et al., 2005; Garai et al., 2006). Carbonado hosts space beneath, extending several millimeters Carbonado is an enigmatic polycrystalline extensive porosity ranging from the nanometer up into the specimen. In situ observation dem- diamond variety found in placer deposits in to the millimeter scale. Some carbonado material onstrates that almost all inclusions are poly- Brazil and the Central African Republic (Trueb has been found to be enriched in isotopes char- mineralic and show replacement textures, and Butterman, 1969; Trueb and De Wys, 1969, acteristic of the products of spontaneous fi ssion corroborating previous work indicating that 1971). Carbonados are commonly millimeter to of uranium (Ozima and Tatsumoto, 1997), but the pore network is fully three-dimensionally centimeter sized, and the “Carbonado of Sergio” cathodo luminescence imaging suggests that this (3-D) connected, and that virtually all macro- from Brazil is the largest diamond known (Hag- may be a secondary feature caused by infi ltration inclusions are secondary. Large metal inclu- gerty, 1999) at 3167 carats. Age determinations of the pore network by fl uids enriched in radio- sions are only found immediately adjacent range from 2.6 to 3.8 Ga, with large uncertainties active elements (Kagi and Fukura, 2008; Kagi to the margin of the specimen, and are thus (Ozima and Tatsumoto, 1997; Sano et al., 2002). et al., 2007; Rondeau et al., 2008). also likely to be secondary or even tertiary. The confi ned geographic distribution of carbo- The inclusion suite in carbonado has also However, we also report pseudomorphs after nados, on land masses that were likely adjacent proven enigmatic. It hosts enclosed nano- a phase forming pristinely euhedral rhombic at times in the Archean, suggests that they may inclusions of various metal alloys (Fe, Fe-Ni, dodecahedra, individually and in clusters all have been created in a single event (Heaney Ni-Pt, Si, Ti, Sn, Ag, Cu, and SiC), as well as from 0.3 to 1 mm in diameter; although we et al., 2005), although they are in some respects other minerals (calcite, sylvite, smithsonite) could fi nd no evidence of this phase persist- similar to other polymineralic diamond varieties that may be original (De et al., 1998) and some ing, it nevertheless represents the fi rst “true” such as framesites and yakutites (McCall, 2009). (augite, ilmenite, phlogopite) that may pre- macro-inclusion reported in carbonado, Carbonado is set apart from other diamond date the diamond-forming event (Sautter et al., which almost certainly formed syngenetically varieties by several unusual characteristics. The 2011). It also hosts larger metal particles tens with the diamond material. The pore system diamond material is texturally diverse, being of microme ters in diameter within open pore is essentially trimodal, consisting of single dominantly porphyritic and consisting of small space (De et al., 1998; Fitzgerald et al., 2006). and clustered pseudomorphs, oblate pores (10–250 µm) diamonds cemented together by Its macro-inclusion suite principally features 0.1–0.3 mm in length with a clear preferred even smaller (<1 µm) microdiamonds (De et al., minerals of ostensibly crustal origin, such as orientation, and 20 µm to <1 µm pores that 1998; Petrovsky et al., 2010). The smaller crys- orthoclase, goethite, quartz, kaolinite, hematite, form the connected network. Our observa- tals can have subplanar dislocations that may serpentine, and fl orencite, a hydrous rare-earth tions support recent work suggesting that be interpreted as defect lamellae, whereas the phosphate that commonly forms as an altera- carbonado crystallized from a carbon-super- larger ones are mostly defect free. Other, rarer tion product of monazite. The fact that extensive saturated fl uid and suggest that the second textures found in subregions are homogeneous, leaching can extract virtually all compositional stage may correspond with the creation of fl ow texture (Yokochi et al., 2008) and colum- impurities (Dismukes et al., 1988) and magnetic the pore alignment fabric. We further pos- nar crystals reminiscent of vein infi ll (Rondeau components (Fitzgerald et al., 2006; Kletetschka tulate that, although the present-day macro- et al., 2008). Carbonado carbon isotopes are very et al., 2000) suggests that all macro-inclusions inclusions are certainly secondary, the bulk light, with δ13C values ranging from –21‰ to are probably secondary products precipitated Geosphere; October 2013; v. 9; no. 5; p. 1336–1347; doi:10.1130/GES00908.1; 9 fi gures; 14 animations. Received 8 February 2013 ♦ Revision received 22 May 2013 ♦ Accepted 25 July 2013 ♦ Published online 14 August 2013 1336 For permission to copy, contact [email protected] © 2013 Geological Society of America Downloaded from http://pubs.geoscienceworld.org/gsa/geosphere/article-pdf/9/5/1336/3344992/1336.pdf by guest on 27 September 2021 3-D petrography of carbonado by fl uids moving through a connected pore net- 13 mm × 10 mm, with a deltoid shape (Fig. 1). work. None of the inclusion phases found thus One broad side and a smaller adjacent edge have far is typical of kimberlitic diamond, such as a silvery, vitreous patina, a common though not 5 mm pyrope, pyrrhotite, and chromian clinopyroxene ubiquitous feature in carbonados that has been (Heaney et al., 2005), although olivine has been interpreted by some as a fusion crust (e.g., reported (Trueb and De Wys, 1971). Ishibashi Shelkov et al., 1997), although overall the side et al. (2012) report a 0.3 µm void with euhe- is rough. The other side is a dull dark gray and dral walls that they interpreted as a former fl uid rougher. Pores are visible to the naked eye on inclusion, though it was not preserved as such all surfaces. due to sample preparation. We imaged the specimen using the Xradia The origin of these diverse features in carbo- MicroXCT scanner at the University of Texas nado has eluded consensus for over 40 yr. High-Resolution X-Ray CT Facility (http:// Hypotheses have included meteorite impact www.ctlab.geo.utexas.edu). The MicroXCT (Smith and Dawson, 1985); formation during hot has a unique design for a micro–computed Archean subduction of early organic material; tomography scanner. Whereas most instru- volcanic hydrothermal systems with metal-cata- ments utilize large detectors and geometric lyzed diamond growth (McCall, 2009); extrater- magnifi cation from a small X-ray focal spot to restrial origin (Garai et al., 2006); and irradiation achieve high resolution, the MicroXCT derives of carbonaceous materials (Ozima and Tatsu- its resolution from a set of specialized detec- moto, 1997). Recent work has favored formation tors consisting of a 35 mm camera lens or vari- at mantle conditions, likely in the presence of a ous microscope objectives coated with scintil- C-O-H fl uid supersaturated in carbon (Ishibashi lating material. This arrangement produces Figure 1. Carbonado specimen as mounted et al., 2012; Petrovsky et al., 2010), a C-H–rich very sharp imagery and facilitates “zooming for micro–computed tomography (CT) fl uid in lower crust transiently metamorphosed at in” to image small subvolumes within larger imaging, along with samples of calcite, apa- mantle conditions (Sautter et al., 2011), or asso- specimens by simply switching detectors, in tite, and almandine garnet for comparison ciated with komatiite magma intrusion into the much the same manner one switches objec- of X-ray attenuation. The patinaed side of continental lithosphere (Cartigny, 2010). tives with a petrographic microscope (Figs. the specimen is shown. Because carbonado is among the tough- 2A, 2B, and 2C). With each such increase in est substances in nature, it is diffi cult to study magnifi cation, however, acquisition time rises using traditional petrographic techniques. With considerably, due to lower signal and the need Following scanning, a single cut was made in the exception of early X-ray imaging (Trueb to acquire more densely sampled data (i.e., the sample using a laser at the Carnegie Insti- and Butterman, 1969; Trueb and De Wys, more views) to reduce the effect of parts of the tute. After polishing the surface on a diamond 1969, 1971), most studies have concentrated sample not in the region of interest but still in wheel, scanning electron microscopy (SEM) on microchemical analyses of small pieces the X-ray path. images and chemical analyses were obtained of material that were powdered, fractured, The specimen was scanned at a range of reso- using the JEOL JSM-6490LV at the University Focused Ion Beam– (FIB) extracted, laser-cut, lutions with different detectors, using 29.2 µm of Texas.
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