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Boron - The Crustal Element - Elements
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Boron — The Crustal Element

This photograph, which was acquired on October 30, 2013 by an astronaut on the International Space Station, shows one of the largest borate mines in the world (Rio Tinto Borax Mine). The mine is located northwest of Boron, California (USA). The borate minerals in the deposit—largely borax, Na2B4O5(OH)4·8H2O, kernite, Na2B4O6(OH)2·3H2O, and ulexite, NaCaB5O6(OH)6·5H2O—formed in sediments of a lake fed by thermal springs in an intermontane basin 16 My ago. IMAGE COURTESY OF NASA (PHOTO # ISS037-E-22990)
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Figure 1. This photograph, which was acquired on October 30, 2013 by an astronaut on the International Space Station, shows one of the largest borate mines in the world (Rio Tinto Borax Mine). The mine is located northwest of Boron, California (USA). The borate minerals in the deposit—largely borax,
Na2B4O5(OH)4·8H2O, kernite,  Na2B4O6(OH)2·3H2O, and ulexite, 
NaCaB5O6(OH)6·5H2O — formed in sediments of a lake fed by thermal springs in an intermontane basin 16 My ago. IMAGE COURTESY OF NASA (PHOTO # ISS037-E-22990)

Boron is a quintessential element of the Earth’s upper continental crust. Processes that created the upper continental crust also enriched it in boron, and, as a result, a great diversity of boron minerals are among the most accessible of useful compounds to humankind, even in antiquity. And humankind is most fortunate that crustal processes have been so effective in concentrating boron, as boron is second only to beryllium among elements with Z ≤ 32 in scarcity in the Solar System. We can thank plate tectonic activity and boron’s affinity for fluids, particularly aqueous fluids, for its enrichment. Primitive mantle is estimated to contain 0.26 ppm boron (Palme and O’Neill 2005) and is depleted due to boron’s volatility relative to carbonaceous Ivuna-type (CI) chondrite meteorites, which have 0.775 ppm boron (Lodders 2010). Upper continental crust, with an average boron concentration of 17 ppm (Rudnick and Gao 2005), is produced largely by partial melting of primitive mantle and by the alteration of basaltic rocks crystallized from these melts. However, to form a boron mineral requires concentrations several times the crustal average, something only attainable through further partial melting, adsorption and absorption of boron onto clay minerals, and via leaching by aqueous fluids. Combinations of these processes can produce localized boron concentrations reaching an order of magnitude greater than the crustal average, for example, 30–150 ppm in the illite-dominated component of pelagic sediments (Leeman and Sisson 1996) and 213 ppm in the Tanco pegmatite (Manitoba, Canada; Stilling et al. 2006). However, the evaporation of brines, such as those found in closed basins near active continental margins (such as the deposit worked in the mine shown in FIG. 1), result in even higher concentrations of boron, which can result in a diverse suite of minerals, such as colemanite (FIG. 2).

Figure 2. Colemanite crystal from Corkscrew Canyon Mine, Death Valley National Park, Inyo County, California (E. S. Grew specimen). The white incrustation on two faces is celestine, SrSO4. Colemanite, Ca[B3O4(OH)3]·H2O, is an important “ore” in some nonmarine evaporite borate deposits and has been suggested as a source of borate to stabilize ribose (Ricardo et al. 2004). PHOTO: PRISCILLA GREW
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Figure 2. Colemanite crystal from Corkscrew Canyon Mine, Death Valley National Park, Inyo County, California (E. S. Grew specimen). The white incrustation on two faces is celestine, SrSO4.  Colemanite, Ca[B3O4(OH)3]·H2O, is an important “ore” in some nonmarine evaporite borate deposits and has been suggested as a source of borate to stabilize ribose (Ricardo et al. 2004). PHOTO: PRISCILLA GREW

Presently, there are approximately 280 known mineral species containing boron as an essential constituent. But has it always been so? A review of boron minerals from the evolutionary standpoint, considering the role of geologic time in mineral formation, can address this question (Hazen et al. 2008). The oldest reported boron minerals in the geologic record are four species of tourmaline in the 3.6–3.9 Ga Eoarchean Isua supracrustal belt of Greenland (Nutman et al. 2013). This occurrence is evidence for localized concentrations of boron in seawater and in the continental crust that formed by what could have been the earliest plate tectonic processes (Grew et al. 2011; Nutman et al. 2013). Diversity of boron minerals increased to about 100 species through the Precambrian and accelerated during the Phanerozoic (542–0 Ma). However, this acceleration could be an artifact of preservation: many boron minerals are soluble in water and can be considered ephemeral. Unless isolated from aqueous fluids, soluble boron minerals are lost from the geological record but, if protected, they can persist for as long as other minerals. For example, crystals of sassolite (boric acid, H3BO3) enclosed in quartz from the 2.64 Ga Tanco pegmatite have been preserved (Thomas et al. 2012). It remains highly debatable whether ephemeral boron minerals, such as those found in nonmarine evaporites, were present as early as 3.8 Ga. Yet, this is a critical question because evaporite borate minerals, such as colemanite (FIG. 2), have been used to explain the stabilization of ribose, a critical component for the self-assembly of prebiotic organic compounds in the emergence of life (Ricardo et al. 2004; Benner et al. 2012). Alternatively, ribose stabilization by borate in solution (Furukawa et al. 2013) is more in accord with the formation of tourmaline in the Eoarchean Isua supracrustal belt, which also involved boron-bearing solutions. How and when life arose on Earth is a question that has long intrigued scientists and boron appears to be a crucial player. Evidence for boron minerals on the early Earth, or for localized boron concentrations in seawater, could give scientists further insights as to how and when life originated.

Figure 3. Hope Diamond (25.60 by 21.78 mm, 45.52 carats), which has a total boron content between 0.2 and 8 ppm (Gaillou et al. 2012). PHOTO COURTESY OF JEFFREY POST OF THE SMITHSONIAN INSTITUTION
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Figure 3. Hope Diamond (25.60 by 21.78 mm, 45.52 carats), which has a total boron content between 0.2 and 8 ppm (Gaillou et al. 2012). PHOTO COURTESY OF JEFFREY POST OF THE SMITHSONIAN INSTITUTION

There is more than just scientific interest in boron. This element, which derives its name from borax, has been widely used in a variety of industries. Borax glazes were used in China as early as 300 AD. Lake Yamdok Cho (Tibet) was the only source of borax known to the ancient world and by 1100 AD trade along the Silk Road was bringing borax from Tibet to Arabia, where goldsmiths used it as a flux (Emsley 2001). Boron compounds have also found wide application in the manufacture of abrasives (e.g. “Borazon,” boron nitride, BN), heat-resistant glass (e.g. Pyrex), porcelain enamels, and detergents. Although poisonous in large amounts and used in herbicides and insecticides, boron is an essential element for plants and is used in fertilizers to enhance plant growth (Greenwood and Earnshaw 1991; Emsley 2001). It also is used in medicine, such as boron neutron capture therapy for cancer (e.g. Kueffer et al. 2013). A few boron minerals can be gemstones, of which tourmaline is by far and away the most prized because of its variety of colors. Tourmaline caught the eye of jewelers in the 14th century, nearly 400 years before a gemstone from Ceylon (now Sri Lanka) was recognized as a distinct mineral and given the name turamalin by Amsterdam lapidaries (Pezzotta and Laurs 2011). Another gemstone of interest is the natural type IIb blue diamond. This is the only gemstone that derives its color from boron, caused by electronic absorption in the red portion of the spectrum. This rarest of colors is among the most valuable on the diamond market (Gaillou et al. 2012). A prime example is the Hope Diamond (FIG. 3). Gaillou et al. (2012) wondered about the source of the boron in these diamonds—did it originate in the mantle or could it have been sourced from deeply subducted crustal material? The latter possibility is no longer outlandish: Dobrzhinetskaya et al. (2014) suggested that qingsongite (BN) formed at 10–15 GPa from mantle nitrogen and crustal boron, the latter from a fragment of pelitic rock subducted to mid-mantle depths. Processes associated with formation of Earth’s crust have not only separated and concentrated boron, which then became available for our industrial use, but may also have mixed a little bit of this crustal boron back into Earth’s mantle to create beautiful gemstones.

REFERENCES

Benner SA, Kim H-J, Carrigan MA (2012) Asphalt, water, and the prebiotic synthesis of ribose, ribonucleosides, and RNA. Accounts of Chemical Research 45: 2025-2034

Dobrzhinetskaya LF and 6 coauthors (2014) Qingsongite, natural cubic boron nitride: The first boron mineral from the Earth’s mantle. American Mineralogist 99: 764-772

Emsley J (2001) Nature’s Building Blocks: An A–Z Guide to the Elements. Oxford University Press, Oxford, 539 pp

Furukawa Y, Horiuchi M, Kakegawa T (2013) Selective stabilization of ribose by borate. Origins of Life and Evolution of Biospheres 43: 353-361

Gaillou E, Post JE, Rost D, Butler JE (2012) Boron in natural type IIb blue diamonds: Chemical and spectroscopic measurements. American Mineralogist 97: 1-18

Greenwood NN, Earnshaw A (1997) Chemistry of the Elements. Second Edition. Butterworth-Heinemann, Oxford, 1600 pp

Grew ES, Bada JL, Hazen RM (2011) Borate minerals and origin of the RNA world. Origins of Life and Evolution of Biospheres 41: 307-316

Hazen RM and 7 coauthors (2008) Mineral evolution. American Mineralogist 93: 1693-1720

Kueffer PJ and 8 coauthors (2013) Boron neutron capture therapy demonstrated in mice bearing EMT6 tumors following selective delivery of boron by rationally designed liposomes. Proceedings of the National Academy of Sciences 110: 6512-6517

Leeman WP, Sisson VB (1996) Geochemistry of boron and its implications for crustal and mantle processes. Reviews in Mineralogy 33: 645-707

Lodders K (2010) Solar system abundances of the elements. In: Goswami A, Reddy BE (eds.), Principles and Perspectives in Cosmochemistry. Astrophysics and Space Science Proceedings. Springer-Verlag, Berlin Heidelberg, p 379-417

Nutman AP and 6 coauthors (2013) The Itsaq Gneiss Complex of Greenland: episodic 3900 to 3660 Ma juvenile crust formation and recycling in the 3660 to 3600 Ma Isukasian orogeny. American Journal of Science 313: 877-911

Palme H, O’Neill H St C (2005) Cosmochemical estimates of mantle composition. In: Carlson RW (ed) Treatise on Geochemistry. Volume 2: The Mantle and Core. Elsevier-Pergamon, Oxford, p 1-38

Pezzotta F, Laurs BM (2011) Tourmaline: the kaleidoscopic gemstone. Elements 7: 333-338

Ricardo A, Carrigan MA, Olcott AN, Benner SA (2004) Borate minerals stabilize ribose. Science 303:196

Rudnick RL, Gao S (2005) Composition of the continental crust. In: Rudnick RL (ed) Treatise on Geochemistry. Volume 3: The Crust. Elsevier-Pergamon, Oxford, p 1-64

Stilling A, Cˇerný P, Vanstone PJ (2006) The Tanco pegmatite at Bernic Lake, Manitoba. XVI. Zonal and bulk compositions and their petrogenetic signifi cance. Canadian Mineralogist 44: 599-623

Thomas R, Davidson P, Beurlen H (2012) The competing models for the origin and internal evolution of granitic pegmatites in the light of melt and fl uid inclusion research. Mineralogy and Petrology 106: 55-73

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