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Olivier Pourret, Michel-Pierre Faucon

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Olivier Pourret, Michel-Pierre Faucon. Cobalt. Encyclopedia of , 2018, ￿10.1007/978-3- 319-39193-9_271-2￿. ￿hal-02136484￿

HAL Id: hal-02136484 https://hal.archives-ouvertes.fr/hal-02136484 Submitted on 10 Aug 2019

HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. COBALT main oxidation states (2+ and 3+). The Olivier Pourret & Michel-Pierre Faucon common for simple Institut Polytechnique LaSalle Beauvais, France compounds is Co2+. Depending upon

Element Data geometry and environment, Co ionic radii Atomic Symbol: Co : 27 vary between 56 pm and 90 pm. Cobalt is a Atomic Weight: 58.933195 g/mol and Abundances: 59Co 100% transitional, compatible and siderophile 1 Atm : 1495°C 1 Atm : 2927°C (chalcophile and lithophile in the Earth’s Common Valences: 2+, 3+ Ionic Radii: 65 pm (2+, 6-fold crust) element, has a high melting point of coordination) Pauling : 1.88 1495°C and is ferromagnetic. Cobalt has an First : 7.88 eV Chondritic (CI) Abundance: 513 ppma electronegativity of 1.88 on the Pauling Silicate Earth Abundance: 102 ppma Crustal Abundance: 26.6 ppmb scale and displays a first ionization potential Seawater Abundance: ~3-300 pmol/kgc Core Abundance: 0.25%d of 7.88 eV. More details can be found in a. Palme et al. (2014) b. Rudnick and Gao (2014) Blackman (2006), Raveau and Seihk (2012) c. Bruland et al. (2014) d. McDonough (2014) and Haynes (2015). Properties

Cobalt (, Co) is a d- transition , bluish-white. It appears in History and Use Cobalt has been utilized by the society since the first long of the the , mainly to impart a rich between and . Cobalt shares many color to and . It name derives chemical and physical properties with these from the German word Kobald (goblin or two elements. Naturally occurring Co evil ) and Greek word cobalos (mine), consists of a single stable : 59Co, because Co fooled miners with whereas 60Co is an artificial isotope that is their bright colors. However, it was only an important γ-ray source. Cobalt has two isolated as a pure metal by Swedish chemist have been used for centuries to produce

Brandt in 1735. Demand for Co remained brilliant blue colors in , , subdued until the turn of the 20th century glass, and pottery. Cobalt is one of the and the development of cobalt- elements defined as a critical metal to clean alloys. Indeed, the demand for Co increased energy over the next 5-15 years, because of considerably after the Second World War, its use in lithium ion batteries: each electric- driven by the use of high-purity Co in jet powered vehicle will demand 9.4 kg of Co engines and gas turbines. Cobalt demand has (Crundwell et al. 2011). Although Co does further accelerated in the past thirty years. not get a ton of press, it's a pretty important

Indeed, it reflects the increased use of Co as metal in this day and age. The artificial an essential constituent of materials used in 60Co is widely used in high-technology industries including treatment, as a tracer, and for radiotherapy. rechargeable batteries, superalloys and catalysts. Cobalt, like Fe, can be magnetized Geochemical Behavior and so is used to make . It is alloyed Cobalt is often associated with Ni, Ag, with Al and Ni to make particularly Pb, Cu and Fe-Mn , from which it is powerful magnets. Other alloys of Co are most frequently obtained as by-product used in jet turbines and (Gunn 2014). The main known deposits generators, where high- strength are found in Katanga (Democratic Republic is important. Cobalt metal is sometimes used of Congo) whereas some recent discoveries in because of its attractive evidenced that central Pacific Ocean may appearance, hardness and resistance to have Co-rich deposits (i.e., manganese oxidation and thus . Cobalt salts nodules and Co-rich ferromanganese crusts) at relatively shallow depths. Almost 50% of estimated in a few studies are quite the world’s cobalt supply in 2014 was mined consistent, ranging from 500 ppm to 513 in the Democratic Republic of Congo. ppm. The bulk Earth has a Co content of 880

Mining and smelter activities in Katanga ppm, lower than that in the metallic core have contaminated soil, water and urban (0.25%). Cobalt contents in the bulk environments (Pourret et al. 2016). continental crust vary significantly from 15

Cobalt forms a number of minerals: ppm to 30 ppm. In particular, Co is most

[CoAsS], [CoAs3-x], abundant in ultramafic rocks with an

[Co3(AsO4)2.8H2O], average concentration of 110 ppm. During

[CoCO3] and heterogenite [CoO(OH)]. It is differentiation of a basaltic magma most of widely distributed in igneous and Co enters the ferromagnesian minerals. sedimentary rocks, and minerals. Cobalt is Cobalt content of these minerals depends on also present in meteorites (i.e., iron-nickel the total number of Fe-Mg lattice sites and is metal contains a few tenths of a percent independent of the Fe/Mg ratio. Cobalt is cobalt). Its average content in the Earth’s strongly coherent with Mg in granitic rocks crust is approximately 25-30 ppm, though and behaves like Mg in its partition relations widely distributed, stands only 33th in order between metamorphic minerals. The of abundance and is less common than all acceptance of both Co and Mg is more other transition except . It selective at lower grades of metamorphism. is, however, more dispersed in the crust than These aspects have been further reviewed by either of those elements, and concentrated Gunn (2014), McDonough (2014), Palme et deposits are consequently rare. The al. (2014) and Rudnick and Gao (2014). average Co contents of CI chondrites Cobalt is also a naturally occurring element of comprehensive data on aqueous Co in air, soil, plants and water. The mean concentrations in soil porewaters, concentration of Co in the open ocean is groundwater and surface waters, natural Co very low (~40 pmol/kg) which in part concentrations vary mostly from 0.006 µg/L reflects its short residence time. Co2+ is the to 0.43 µg/L (Gaillardet et al. 2014). Cobalt principal aquatic species in seawater is considered as moderately mobile with a

(Bruland et al. 2014). There has been mobility 10 times less than that of Na. considerable speculation on its mode of Cobalt chemistry is dominated by the Co(II) uptake in deep-sea manganese nodules and oxidation state in the aqueous of crusts. Cobalt tends to be associated with terrestrial environments primarily due to the either Mn or Fe oxyhydroxides (Brown and extremely low solubility of Co(III). There is

Calas 2012). Cobalt may substitute as no universal agreement on the importance of exchangeable Co2+ in marine manganates Co(II) complexation in the solution phase of and then be oxidized to Co3+ by Mn4+, terrestrial environments and, furthermore, on whereas Co3+ may substitute for Fe3+ in Fe the nature of the major binding inorganic oxyhydroxide minerals. Cobalt may also be and organic . The kinetics of Co(II) incorporated in birnessite as Co(II) at pH 7 complexation to, and dissociation from, and Co(III) above pH 8. The aqueous natural organic complexing ligands are such speciation and chemistry of Co in terrestrial that the speciation of Co is likely to environments is now an important focus of significantly diverge from estimates based research, as the solution speciation of Co has on thermodynamic equilibrium calculations. a critical influence on its biological activity As a result, an accurate understanding of Co in the environment. Although there is a lack bioavailability, toxicity and transport in terrestrial aquatic environments will only be the general human population (Simonsen et achieved when thermodynamics can be al. 2012). reconciled with reaction kinetics. Understanding the factors which affect Co

uptake by plants across a range of soil types

is essential for food quality as well as for Biological Utilization and Toxicity Cobalt is an essential trace element in life possible remediation of contaminated sites. and plays an important role in biochemical The relevant pedogenic processes reactions essential for life, notably in the contributing to Co uptake from soils by coenzyme cobalamin (Co chelated to four N plants includes total, extractable and at the center of a porphyrin- like exchangeable soil Co concentrations, pH structure; Chivers 2014). Cobalamin has a and other soil chemical parameters, complex biochemistry, and there is a microbial variations as well as number of cobalamin-depend enzymes. anthropogenic inputs. In soils, Co is fixed by

Cobalamin-dependent enzymes influence Mn- in a non-extractable form and its nodulation and N2 fixation in legume plants bioavailability is inversely proportional to that can be used to supply in crops the Mn content of the soil (Collins and

(Underwood 1977). Cobalt deficiency Kinsela 2012). affects development, function and High and frequent Co exposures can affect nitrogen fixation. Cobalamin, also called nervous system and cause an axonopathy

Vitamin B-12, is essential for human and (Flora 2014). Chronic inhalational intake of health, and growth. The cobalt dust can lead to diffuse-inflammatory amount needed is very small. Dietary Co reactions of the bronchial mucosa and intake is estimated to range 5–40 μg/day in chronic respiratory tract disorders (Banza et al. 2009; Cheyns et al. 2014). In large doses, human health, and to assist in developing some Co forms are carcinogenic. Some plant new remediation tools. species, also called metallophytes, have adapted to natural and contaminated Co-rich Cross-References ; soils (Faucon et al. 2007). Among these Siderophile Elements; metallophytes, some are able to Trace Elements; hyperaccumulate Co in plant shoots (>300 Transition Elements; ppm, without toxicity symptoms and growth Fe-Mn Crusts and Nodules; inhibition). Manganese;

Ore deposits; Summary Cobalt production hugely increases in the Complexation. last decade as the global demand for Co increases. However, its exploitation Bibliography Banza CLN, Nawrot TS, Haufroid V, becomes a new urgent environmental issue, Decrée S, De Putter T, Smolders E, Kabyla BI, Luboya OS, Ilunga AN, Mutombo AM, especially in region such as Democratic Nemery B (2009). High human exposure to cobalt and other metals in Katanga, a Republic of Congo. Cobalt has been area of the Democratic Republic of Congo. Environ Res 109: 745-752. suggested to be a potentially dangerous Blackman AG (2006) Cobalt: Inorganic & pollutant and the Coordination Chemistry, Encyclopedia of . John Wiley & Sons, Environmental Protection Agency classifies Ltd.

Co in the priority list of environmental risk Brown GE, Calas G (2012) Section 18. Mineral-Water Interfaces as Driving Forces elements. A better understanding of Co For Metal Concentration: The Example of Cobalt Trapping by Mn-Oxides. biogeochemical behavior may support to Geochemical Perspectives 1: 667-669. assess the risk to the environment and to Bruland KW, Middag R, Lohan MC (2014) Gunn G (2014) Critical Metal Handbook. 8.2 - Controls of Trace Metals in Seawater. Wiley. In: Holland HD, Turekian KK (eds), Treatise on Geochemistry (Second Edition). Haynes WM (2015) CRC Handbook of Elsevier, Oxford, pp. 19-51. Chemistry and Physics, 96th Edition. CRC Press. Cheyns K, Banza Lubaba Nkulu C, Ngombe LK, Asosa JN, Haufroid V, De Putter T, McDonough WF (2014) 3.16 - Nawrot T, Kimpanga CM, Numbi OL, Compositional Model for the Earth's Core. Ilunga BK, et al. 2014. Pathways of human In: Holland HD, Turekian KK (eds), exposure to cobalt in Katanga, a mining area Treatise on Geochemistry (Second Edition). of the D.R. Congo. Sci Total Environ 490: Elsevier, Oxford, pp. 559-577. 313-321. Palme H, Lodders K, Jones A (2014) 2.2 - Chivers PT (2014) CHAPTER 14 Cobalt Solar System Abundances of the Elements. and Nickel. In Maret W, Wedd A (eds) In: Holland HD, Turekian KK (eds), Binding, Transport and Storage of Metal Treatise on Geochemistry (Second Edition). Ions in Biological Cells. The Royal Society Elsevier, Oxford, pp. 15-36. of Chemistry, pp. 381-428. Pourret O, Lange B, Bonhoure J, Colinet G, Collins RN, Kinsela AS (2010) The aqueous Decrée S, Mahy G, Séleck M, Shutcha M, phase speciation and chemistry of cobalt in Faucon M-P (2016) Assessment of soil terrestrial environments. Chemosphere 79: metal distribution and environmental impact 763-771. of mining in Katanga (Democratic Republic of Congo). Appl Geochem 64, 43-55. Crundwell FK, Moats MS, Ramachandran V, Robinson TG, Davenport WG (2011) Raveau B, Seikh MM (2012) Front Matter, Extractive Metallurgy of Nickel, Cobalt and in Cobalt Oxides: From Crystal Chemistry Metals. Elsevier. to Physics, Wiley.

Faucon MP, Shutcha MN, Meerts P. 2007. Rudnick RL, Gao S (2014) 4.1 - Revisiting copper and cobalt concentrations Composition of the Continental Crust. In: in supposed hyperaccumulators from SC Turekian HD, Holland KK (eds), Treatise on : Influence of washing and metal Geochemistry (Second Edition). Elsevier, concentrations in soil. Plant Soil 301: 29-36. Oxford, pp. 1-51.

Flora SJS (2014) Chapter 22 – Metals. In: Simonsen LO, Harbak H, Bennekou P Aronson JK (ed) Side Effects of Drugs (2012) Cobalt metabolism and toxicology— Annual. Elsevier, pp. 397-417. A brief update. Sci Total Environ. 432, 210-

215. Gaillardet J, Viers J, Dupré B (2014) 7.7 -

Trace Elements in River Waters. In: Holland Underwood EJ (1977) 5 – Cobalt. In: HD, Turekian KK (eds.), Treatise on Underwood EJ (ed), Trace Elements in Geochemistry (Second Edition). Elsevier, Human and Animal Nutrition (Fourth Oxford, pp. 195-235. Edition). Academic Press, pp. 132-158.