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2 Chemistry, Geochemistry, and Geology of and Chromium Compounds

William E. Motzer and Todd Engineers

CONTENTS 2.1 Chromium Chemistry ...... 24 2.1.1 Background ...... 24 2.1.2 Elemental/Metallic Chromium Characteristics ...... 25 2.1.3 Ionic Radii ...... 29 2.1.4 Oxidation States...... 30 2.1.5 Stable and Radioactive Isotopes ...... 31 2.1.6 Characteristics of Chromium Compounds...... 34 2.2 Natural Chromium Concentrations...... 34 2.2.1 Mantle ...... 46 2.2.2 Chromium ...... 46 2.2.3 Chromium Ore Deposits...... 46 2.2.3.1 Stratiform Mafic-Ultramafic Deposits ...... 62 2.2.3.2 Podiform- or Alpine-Type Chromite Deposits ...... 63 2.2.4 Crude Oil, Tars and Pitch, Asphalts, and Coal...... 63 2.2.5 Rock ...... 64 2.2.6 Soil ...... 66 2.2.7 Precipitation (Rain Water) and Surface Water ...... 67 2.2.8 Groundwater...... 67 2.2.9 Sea Water ...... 67 2.2.10 Air ...... 67 2.2.11 Biogeochemical Cycling ...... 68 2.3 Chromium Geochemistry...... 70 2.3.1 Cr(III) Geochemistry...... 70 2.3.2 Cr(VI) Geochemistry...... 71 2.3.3 Chromium Reaction Rates (Kinetics)...... 73 2.4 Chromium Distribution in Primary Environments ...... 74 2.4.1 Possible Sources of Natural Cr(VI) in Rocks...... 74 2.4.2 Known Sources of Natural Cr(VI) in Rocks ...... 77

1-5667-0608-4/01/$0.00+$1.50 23 © 2004 by CRC Press LLC

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24 Chromium(VI) Handbook

2.5 Chromium Distribution In Secondary Environments ...... 78 2.5.1 Known Natural Cr(VI) Occurrences in Surface Water and Groundwater ...... 78 2.6 Forensic Geochemistry...... 80 2.6.1 Soil ...... 80 2.6.2 Groundwater...... 80 2.6.3 Air ...... 81 2.7 Acknowledgments...... 81 Bibliography ...... 82

2.1 Chromium Chemistry 2.1.1 Background In 1797, the French chemist Nicholas-Louis Vauquelin hypothesized that chromium (Cr) was a separate and distinct element. He had isolated the

oxide of this element from a Siberian known as crocoite (PbCrO4). In 1798, Vauquelin successfully isolated metallic chromium by heating

(reducing) chromic oxide (Cr2O3) with charcoal. He then named the new element after the Greek word χρωµα (chro^ma), pronounced khrma, for color because it produced chemical compounds with distinct and unique colors. Vauquelin also analyzed a Peruvian emerald, determining that its green color was due to the presence of chromium. About two years after chromium’s discovery, Tassaert, a German chemist, determined that chromium was present in an ore that we now know as chromite (Greenwood and Earnshaw, 1998; ChemGlobe, 2000; Papp, 2000; Winter, 2002). Since its discovery, chromium has become a very important industrial metal because of its many applications in ferrous (cast iron and stainless steel) and in nonferrous (aluminum, copper, and nickel) alloy metal fabrica- tion, and in the chemical industry (metal finishing, plating, corrosion control, pigments and tanning compounds, and wood preservatives) (Papp, 2000). Chromium and chromium compounds are used in a wide variety of indus- trial and manufacturing applications including steel alloy fabrication, where they enhance corrosion and heat resistance in other metals, and in plated product fabrication where they are used for metal decoration or increased wear resistance. They are also used in nonferrous alloy metal fabrication to impart special qualities to the alloys; in production and processing of insol- uble salts, as chemical intermediates; in the textile industry for dyeing, silk treating, printing, and moth proofing wool; in the leather industry for tan- ning; in the manufacture of green varnishes, inks, paints, and glazes; as catalysts for halogenation, alkylation, and catalytic cracking of hydrocar- bons; as fuel and propellant additives; and in ceramics (Spectrum Labora- tories, 1998).

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Chemistry, Geochemistry, and Geology of Chromium 25

While chromium in its Cr(III) form is not considered a toxic element and is a required diet nutrient with recommended daily adult dosages ranging from 0.5 to 2 mg per day (required for glucose metabolism), in its Cr(VI) form, it does have toxic effects (see Guertin, Section 6, this volume). Acute exposure to Cr(VI)-laden dust results in skin rashes, ulcers, sores, and eczema in occupational workers. In humans, Cr(VI) exposure caused marked irritation of the respiratory tract and ulceration and perforation of the nasal septum in workers in the chromate producing and -using indus- tries. Ingestion of 1.0 to 5.0 g of Cr(VI) as chromate results in severe acute gastrointestinal disorders, hemorrhagic diathesis, and convulsions. Death may occur following cardiovascular shock. Doses in animals of Cr(VI) greater than 10 mg/kg mainly affect the gastrointestinal tract, kidneys, and hematopic system (IPCS, 1988). Cr(VI) causes cancerous tumors in mice by inhalation and is considered a possible human carcinogen by this route because workers engaged in the production of chromate salts and chromate pigments experience an increased risk of developing bronchial carcinomas. However, ingestion of Cr(VI) has not been observed to cause cancer because it is believed that Cr(VI) is reduced to Cr(III) in the gastrointestinal tract (IPCS, 1988; WHO, 1988 and 1996; Smith and Huyck, 1999; CDHS, 2003). The understanding of chromium chemistry and geochemistry is therefore important in developing remediation systems that can deal with industrial- caused pollution (see Chapter 8). This chapter is a review of the character- istics of chromium in the natural environment; its concentration within the earth’s crust, atmosphere, and biosphere; and its geochemistry.

2.1.2 Elemental/Metallic Chromium Characteristics Chromium (atomic number 24) is a transition metal occurring in Group VIB of the periodic table. General elemental chromium characteristics are sum- marized in Tables 2.1a to 2.1d. Chromium has a ground state electron con- figuration of 1s22s22p63s23p64s13d5 (Table 2.2). In the periodic table, transition metals (Groups IB to XIIIB) occur between the main group elements (Groups IA to IIA and Groups IIIA to VIIA and the inert gases—Group VIIIA) (Drew, 1972; Timberlake, 2003). The atoms of transition elements have electrons filling d subshells consisting of 5d orbitals. The transition metals are noteworthy because they:

1. Form alloys with one another and the main group metals. 2. Commonly are white lustrous metals with high melting and boiling points. The transition metals vary in abundance in the continental crust from iron, which is common at 5.63% to scandium which is rare at 22 (parts per million) ppm (Ronov and Yaroshevsky, 1972). 3. Have high melting points and densities because the electrons in the d orbitals, bind atoms together in the crystal lattice.

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26 Chromium(VI) Handbook C ° C; 1907 ° K) 0.937 ⋅ K) 0.451 ⋅ Cr 52 (most common isotope: 83.789%) Melting point Heat of fusion (kJ/mol)Thermal conductivity (W/cm 0.325 2180 6 5 10 3d × 1 5

) 0.0774 Ω ) 12.7 Ω

8 Properties − Symbol

Mass Number Atomic No. (Z) 24 Fills of subshell 3d in shell 1,2,3,4 configuration 2,8,13,1 {Ar}4s Boiling point 2944 K; 2631 K 2 – – / 1 Effective nuclear chargesEffective 2.1c Table Specific heat capacity (J/g centered /mol) 0.139 e 3 Physical Electrical Thermal Periodic Table at 293 K) 7.19 Electrical conductivity (cm 3 Chemical Registry Atomic volume (cm TABLE 2.1A TABLE Properties Elemental Chromium Atomic no. Atomic mass no. Group 24 name Group 51.9961 Period no. metals Transition Block d 6 B 4 CAS no.Atomic radius (nm) 7440-47-3 Covalent radius (nm) 0.185 0.118Elastic Properties: e modulus (GPa)Young’s Cubicbody Rigidity modulus (GPa) binding energies Electron Bulk modulus (GPa) 279 115 2.1b Table 160 Pauling Heat of vaporization (kJ/g) Absolute (eV) Electronegativity: (10 Electrical resistivity 6.622 3.72 1.66 Density (g/cm Bond length: Cr-Cr (nm)Bond length: Cr-Cr 0.250 L1608_C02.fm Page 53 Thursday, July 15, 2004 6:57 PM

Chemistry, Geochemistry, and Geology of Chromium 53 ) Continued ( species. Physical similar to are properties ilmenite (ilm); found as inclusions in ilm. Not an name. approved IMA schists serpentinite Cr-analog of dundasite Cr-analog 1999-034 Formerly IMA sandstone-hosted U-V deposits Considered a “doubtful” Considered Occurs in quartz-bearing Occurs in bleached Found in oxidized zone Hg exhalative and Shandong, China Zabaikalye Baikal region, Siberia, Russia (Transbaikal) Ural (Sverdlovsk), Mountains, Russia Nevada Washington, CA County, north-northwest of Kalgooolie, Australia Transvaal, Republic of South Transvaal, Africa 4.5 km south of Olkhon Island, Russia Dundas mining field, northwestern Tasmania, Australia Napa Co., CA Slyudyanka complex, Lake missing information. Au: Please check for the 7.2.3.4 nickel deposit, Accord Bon 8.4.1.2 of Lake Baikal, shore Western 16b.2.1 Red Lead mine, Zeehan- 35.1.2.1 Ekaterinburg Berezov, 29.7.3.6 Redington mine, Knoxville, 65.1.3c.5 (clinopyroxenes) chromates group and Ti Nb, Ta, or hydroxyl halogen sulfates 5.24 Multiple oxides 7.11.11.1 (?), area Yimenguan 5.74 Inosilicates 30.65 Multiple oxides — 19.94 Multiple oxides with 20.10 Carbonates — 3.34 Compound sulfates 32.4.3.1 Mt. Keith Ni deposit, 400 km 8.49 Hydrated acid and , 5 2 ⋅ ⋅ +3 3 24 6 9 O O) 12.96 Multiple oxides 7.9.5.2 Red Ledge mine south of , Cr) (Ti, Zr) (Ti, 2 2 2 (OH) O 3+ O ) 3 )(Cr, Fe )(Cr, 2 2 3.5 )Si (H ) 2+ +2 ) O 3 Ti 3 2 16 (Fe +3 2 ) )O 9.52 Anhydrous 11 4 O 22H H +3 2 ⋅ ⋅ ⋅ ⋅ ,Cr 4 (CO 4 4 O , CO ) +3 2 Cr 3+ O 4 4 , V , Mg,Ni)(Cr, Al) , Mg,Ni)(Cr, 6 2 (CrO +3 2+ 12 2 Al) O (SO (OH) (SO 11H Pb Mountkeithite (Mg, Ni) Nichromite (Ni, Co, Fe Redingtonite (Fe Natalyite Na(V Mongshanite Fe (Mg, Cr, OlkhonskitePetterite (Cr Phoenicochroite PbCr Redledgeite BaTi L1608_C02.fm Page 54 Thursday, July 15, 2004 6:57 PM

54 Chromium(VI) Handbook deposits caswellsilverite deposits serpentine and Wolchonskoite Sandstone-hosted U-V Weathering product of product Weathering Atacama Desert, Chile Metamorphosed chromite Alteration product of Alteration product Synonyms: Volchonskoite Type Locality/LocalitiesType Environment/Remarks 20 km ENE of Meeker, 20 km ENE of Meeker, CO Coal Creek, Chile Sierra Gorda, meteorite, Norton County, meteorite, Norton County, KS Sierra Gorda, Chile Sierra Gorda, Henan, China Russia Mordovskaya, Ural (Sverdlovsk), Mountains, Russia Dundas, Tasmania, Dundas, Tasmania, Australia Mountains, Russia Mountains, Russia 35.4.1.1Ana mine, Caracoles, Santa 2.9.17.2 Enstatite achondrite 35.1.1.1Ana mine, Caracoles, Santa 43.4.3.1 Ekaterinberg Berezov, 71.3.1a.4 Mount Efimyatsk, Ural 51.4.3b.3 Bissersk, Saransk, 16b.6.2.2 Adelaide mine, Hill, Dana Classification Mineral Class No. chromates selenides and tellurides chromates garnet group phosphates hydroxyl or hydroxyl halogen group 2.01 Anhydrous 26.7886.66 Anhydrous 20.78 Native elements Nesosilicates — 1.1.17.1 County, Liu Zhuang, Tonbai 15.90 Carbonates — 13.12 Clays — smectite Trace Sorosilicates 58.2.2.9 Bisersk deposit, Ural 7.37 Compound

⋅ ⋅ ) 2 2 2 3 ) ⋅ ) O (?)O 41.15 Multiple oxides 7.11.14.1 Riland carnotite claims 4 2 2 +3 (CO 5H )(OH) ⋅ O 36.87 Sulfides — including 3 16 7 )(PO 2 ) (OH) 4 11 4 O 10 H 2 ,Mg,Fe ⋅ 2 6 O +3 SiO 4 (OH) 6 (SiO 4 2 )(Si 2 4 O O 2 CrS (Cr 2 2 Cr CrO O (Mg,Al)(Cr,Al) Cr 6 Cu(CrO C 2 0.3 2 3 0.3 11 2 3 CrO 2 4H 4H (SiO H (Si,Al) (OH) Pb Cr Pb K Santanaite Schollhornite Na TABLE 2.8A TABLE (Continued) Mineral NameRilandite Formula (Cr,Al) Cr Conc. (%) Shuiskite Ca Tongbaite UvaroviteVauquelinite Ca Volkonskoite Ca StichtiteTarapacaite Mg L1608_C02.fm Page 55 Thursday, July 15, 2004 6:57 PM

Chemistry, Geochemistry, and Geology of Chromium 55 exhalative Hg deposits Oxidized zone of New Idria district, San CA Benito County, Sweden Co., AZ China Anhui, China Russia 7.2.4.1 Stäta, Doverstop, Bergslagen, 7.2.3.6 Karelia, Onega depression, 35.4.2.1 mine, mercury Clear Creek 10.6.3.1 Pinal Mammoth mine, Tiger, chromates hydroxyhalides spinel group 9.47 Anhydrous 11.73 Multiple oxides — 29.19 Multiple oxides44.56 7.4.1.2 Multiple oxides - Shandong, area, Yimengshan 3.17 Oxyhalides and 2 ) +3 19 8 O 6 ,Cr 12 O +3 +6 )(V Cr (O,OH) +2 +2 6 4 O ,Fe 2 +3 4Hg CrCl + 4 6 O Hg Hurlbut (1963); Martin and Blackburn (1999 and 2001); Perroud (2001); Webmineral (2002). Hurlbut (1963); Martin and Blackburn (1999 2001); Perroud (2001); Webmineral Minerals in bold type are Cr(VI) minerals. Minerals in bold type are Yedlinite Pb Wattersite Vuorelainenite (Mn Note: Source: YimengiteZhanghengite K(Cr,Ti,FeMg) Zincochromite (Cu,Zn,Fe,Al,Cr) ZnCr 4.28 Native elements 1.1.6.2 Xiaoyanzhuang, Boxian Co., L1608_C02.fm Page 56 Thursday, July 15, 2004 6:57 PM

Chemistry, Geochemistry, and Geology of Chromium 56 black orange yellow Grayish- Dark brown Yellowish- adamantine metallic greasy 2.0 Pearly White 6.5 Adamantine; − − 3.5 Resinous: Mohs Hardness Luster — 1.5 — 5.5 — 6.0 Metallic — sheets crystals; platy: translucent opaque opaque Translucent to Translucent Physical Properties — Transparent — — dull Vitreous: — 2.1 to Transparent 9.8 Translucent — 3.0–3.5 Adamantine Brownish- 4.12 Opaque — 3.5–4.5 Metallic: dull — Au: Please check spelling. "Diaphaniety" or " Diaphaneity"? (S.G.) Diaphaniety Habit 4.45–4.48 Density (av = 4.46) violet reddish-brown; black gray yellow dark green — Darkreddish-brown; — to Brownish-gray — Gray 5.9 Opaque — 7.0 Metallic — — Reddish-orange — — microscopic — Yellowish-gray 3.21 Opaque — 1.2 Metallic — — to Emerald-green none Black 4.44 Opaque — 6.5 Vitreous: none Cinnamon to black — to Translucent none Lemon yellow 3.142 — — — — Color [001]-perfect pink; pink Violet; [1010]-perfect light violet Violet; 2.025 Transparent — 2.0 glassy Vitreous: Violet dihexagonal dipyramidal dipyramidal dihexagonal dipyramidal dipyramidal dipyramidal hexoctahedral prismatic prismatic hexagonal scalenohedral ditetragonal dipyramidal spheroidal Trigonal- Tetragonal- Hexagonal- Barbertonite TABLE 2.8B TABLE Minerals: Crystallography and Physical Properties Chromium Mineral Name Ankangite Tetragonal- Bracewellite Orthorhombic- Bentorite Hexagonal- Brezinaite Orthorhombic- Calsbergite Isometric- Carmichaelite Monoclinic- Cassendanneite Monoclinic- Caswellsilverite Chromatite ChrombismiteChromceladonite Tetragonal Monoclinic- none orange; Brown; L1608_C02.fm Page 57 Thursday, July 15, 2004 6:57 PM

Chemistry, Geochemistry, and Geology of Chromium 57 ) gray orange green black brown Continued Greenish- ( resinous 5.5 Metallic Brown 2.5–3.0 Adamantine Yellowish- — 7.0–7.4 Vitreous: — — Resinous — — 3.5 Earthy: dull Yellow acicular granular opaque opaque translucent Opaque Massive Translucent Crystalline: 6) = — Transparent— to Transparent — — — — 3.4 to Translucent 5.9–6.1 (av 4.5–5.09 (av = 4.79) dark green black red; reddish-orange red; brown orange Yellow; orangish- Yellow; — White 7.2 Opaque — 4.0 Metallic — — Black 3.81 Opaque — 4.5–5.0 Metallic Brownish- — yellowish- Yellow; None Grayish-white — Opaque — 4.0 Metallic — None Black or brownish- None Black 5.0 — — 6.5–7.0 Metallic Blackish- None Orange 6.45 to Transparent None Black 5.18 Opaque — 8.0–8.5 Metallic Gray Good Orange-red — Transparent — 4.5–5.0 Adamantine — Good Greenish-yellow; Indistinct or Greenish-black Indistinct Black 5.22 Opaque — 7.0 Metallic Green [001]-perfect Emerald green 2.88 Transparent Platy: sheets 3.0 glassy Vitreous: Whitish- [001]-indistinct [100]-indistinct [100]-indistinct Golden yellow 3.617 Transparent — 3.5 glassy Vitreous: Light yellow [110]-distinct hexoctahedral ditrigonal pyramidal hexoctahedral hexoctahedral prismatic hexoctahedral hexoctahedral prismatic pinacoidal prismatic ditrigonal pyramidal ditetragonal dipyramidal prismatic prismatic hexagonal scalenohedral Isometric- Mmonoclinic- Triclinic- Monoclinic- Trigonal- Tetragonal- Monoclinic- Monoclinic- (Chrome iron ore; iron (Chrome iron) chromic ChromferideChromite Isometric- Chromdravite Trigonal- Chromium Isometric- Chromphyllite Monoclinic- Daubreelite Isometric- CochromiteCocroite Isometric- Deanesmithite Dietzeite Dukeite Donathite Edoylerite Embreyite Eskolaite Trigonal- L1608_C02.fm Page 85 Thursday, July 15, 2004 6:57 PM

Chemistry, Geochemistry, and Geology of Chromium 85

Hurst, R.W., 2002, Lead isotopes as age-sensitive genetic markers in hydrocarbons. 3. leaded gasoline, 1923–1990 (ALAS Model), Environ. Geosci., 9, 2, 43–50. Hurst, R.W., Davis, T.E., and Chinn, B.D., 1996, The lead fingerprints of gasoline contamination, Environ. Sci. Technol., 30, 7, 304A–307A. International Programme on Chemical Safety (IPCS), 1988, Environmental Health Cri- teria 61: Chromium, World Health Organization IPCS, v 61, http://www.inchem. org/documents/ehc/ehc/ehc61.htm (accessed August 13, 2002), 266 p. Jennings, C.W., 1985, An Explanatory Text to Accompany the 1:750,000 Scale Fault and Geologic Maps of California, California Division of Mines and Geology Bulletin 201, Sacramento, California, 197 p. Jones, J., 1988, Asbestos in the western San Joaquin valley, Calif. Geol., 41, 7, 160–164. Kaczynski, S.E. and Kleber, R.J., 1993, Aqueous trivalent chromium photoproduction in natural waters, Environ. Sci. Technol., 27, 8, 1572–1576. Kieber, R.J. and Heiz, G.R., 1992, Indirect photoreduction of aqueous chromium(VI), Environ. Sci. Technol., 26, 2, 307–312. King, T. and Rytuba, J.J., 1999, AVIRIS and field imaging spectroscopy of mineral and vegetation distribution in the coast range mercury mineral belt, California, Geol. Soc. Am. Abstr. Programs, 32, 6, A–70. Kitts, K., Podosek, F.A., Nichols, R.H., Jr., Brannon, J.C., Ramezani, J., Korotev, R., and Joliff, B., 2002, Chromium isotopic composition of implanted solar wind from Apollo 16 lunar soils, Washington University, St. Louis, MO, http:// presolar.wustl.edu/ref/LPSC2002_ solarwind.pdf, 2 p. Kohl, W.H., 1967, Handbook of Materials and Techniques for Vacuum Devises, Rheinhold Publishing, New York, 623 p. Kotz, K.T., Yang, H., Snee, P.T., Payne, C.K., and Harris, C.B., 2000, Femtosecond infrared studies of ligand rearrangement reactions: Silyl hydride products from group 6 carbonyls, J. Organomet. Chem., 596, 183–192. Krejci-Graf, K, 1972, Trace elements in sediments, oils, and allied substances, in Fairbridge, R.W., Ed., The Encyclopedia of Geochemistry and Environmental Scienc- es, Van Nostrand Reinhold, New York, pp. 1201–1209. Lawrence Berkeley National Laboratory (LBNL), 2001, Isotopes of Chromium, http:// isotopes.lbl.gov/education/parent/Cr_iso.htm, 2 p. Leventhal, J., 1993, Metals in black shales, in Engel, M.H. and Macko, S.A., Eds., Organic Geochemistry: Principles and Applications, Plenum Press, New York, pp. 581–592. Li, J., Kusky, T.M., and Huang, X., 2002, Archaen podiform chromitites and mantle tectonics in ophiolitic mélange, North china Craton: A record of early oceanic mantle process, GSA Today, 12, 7, 4–11. Lin, C., 2000, A Chemical Kinetic Mechanism for Chromium Transformations in Natural Water, Lamar University, Beaumont, TX, http://even.tamuk.edu/STEC2000/ STEC2000 present/Che-Jenlin.htm, 17 p. Lipin, B.R. and Page, N.J., 1982, Stratiform chromite, in Erikson, R.L., compiler, Characteristics of Mineral Deposit Occurrences: U.S. Geological Survey Open-File Report 82–795, pp. 18–20. Luis, A.L., 2001, Chromium-Catalyzed Oxidations, University of Texas at Austin, www.cm.utexas.edu/academic/courses/Fall2001/CH38oL/termpaper01/ luis.doc, 13 p. Mandarino, J.A., 2001, New Minerals 1995–1999, The Canadian Mineralogist Special Publication 4, Mineralogical Association of Canada, Ottawa, Canada, 275 p. L1608_C02.fm Page 86 Thursday, July 15, 2004 6:57 PM

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