Cobalt

    group 9 · period 4 · d-block · transition metal

    fullCobalt has no drinking water guideline anywhere, but it was monitored in every large US supply under UCMR 3, is a ZDHC textile wastewater metal and an Abu Dhabi discharge parameter, carries the fission and activation product cobalt-60 into nuclear plant effluent, and reaches water from batteries, catalysts, pigments and metal complex dyes.

    Typical wastewaters

    • textile dyeing (metal complex dyes) 1:1 and 1:2 cobalt azo dye complexes leaving with the dyebath, not broken by pH adjustment; 0.05 to 0.01 mg/L by ZDHC level
    • battery manufacture (cadmium subcategory, electrodeposited anodes) cobalt as a co-pollutant with cadmium, nickel and zinc; mass limited per kg of cadmium used
    • nuclear reactor and fuel cycle liquid effluent cobalt-60, the activation product of steel; removed by ion exchange and reverse osmosis
    • chemical sector effluent with chelating agents Co(II) and Co(III) held in solution by ammonia, cyanide, EDTA and dye ligands, escaping hydroxide precipitation
    • base metal ore processing cobalt as a trace metal of ore processing effluent (MWEI BREF via the element entry) no concentration read
    In the ledger's plant and process records, discharged by: Speciality inorganic pigments (iron oxide, chromium oxide, CIC, zinc sulphide, lithopone) (Chemicals)

    1 · Identity

    Symbol, number
    Co, 27
    Oxidation states in water
    +2, Co²⁺, the pink aquo ion and the state of every simple salt in water; +3 only when held in complexes (ammine, cyanide, cobalamin) or in the oxide and oxyhydroxide solids that form on manganese oxide surfaces. Cobalt-60 is a gamma emitting activation product of reactor steel, half-life about 5.3 years, and the cobalt radionuclide of drinking water regulation.
    Note
    The element entry has the ores, the battery and superalloy uses and the complex chemistry in outline; this chapter is the trace metal in supplies and effluents.

    2 · Occurrence in water

    Natural sources
    Weathering of cobalt bearing nickel and copper sulfides and laterites; cobalt travels with nickel and is sorbed and oxidised on manganese oxide coatings, so dissolved cobalt in natural water is low. In US public water systems under UCMR 3 cobalt was found above the 1 µg/L reporting level in only 833 of 62,982 samples (1.3 percent) and in 247 of 4,922 systems.
    Anthropogenic sources
    Lithium ion battery cathode manufacture and recycling; hydroformylation and hydrodesulfurisation catalysts; cobalt blue and other pigments; 1:1 and 1:2 cobalt complexed azo dyes in textile dyeing (the reason ZDHC lists it); cobalt and nickel electroplating; cobalt as a co-pollutant of cadmium battery manufacture, where 40 CFR 461.12 sets a cobalt mass limit; base metal ore processing (MWEI BREF via the element entry). Cobalt-60 from nuclear fuel cycle facilities (WHO chapter 9).
    matrixtypical rangenote
    US public water systems (finished water), UCMR 3 2013 to 2015below 1 (98.7 percent of samples) µg/L
    national screening data, US only
    833 of 62,982 samples at or above the 1 µg/L minimum reporting level; 3 samples and 3 systems above the 70 µg/L reference concentration
    seawater0.00002 mg/L
    single abundance figure, no range
    estimated oceanic abundance, Jefferson Lab via PubChem
    surface water and groundwaternot read gapno WHO background document exists for cobalt and no survey range was read this session

    3 · Speciation

    Cobalt is Co²⁺ in oxic and anoxic water alike; it hydrolyses only at high pH and precipitates as Co(OH)₂, CoCO₃ or CoS. What distinguishes it from zinc is the strength of its complexes: ammonia, cyanide, EDTA and dye ligands hold cobalt in solution where the free ion would precipitate, and Co(III) complexes once formed are kinetically inert. On manganese oxide surfaces Co(II) is oxidised and fixed as Co(III), which is why manganese nodules and MnO₂ filter media scavenge it.

    conditiondominant speciesnote
    oxic or anoxic water, pH 5 to 9Co²⁺, CoSO₄ and CoHCO₃⁺ ion pairs, cobalt sorbed on manganese and iron oxidesno redox change of the dissolved ion; solubility set by sorption and carbonate
    alkaline precipitation, pH above about 10Co(OH)₂ (s), CoCO₃ (s)hydroxide precipitation with the other base metals; the optimum pH differs from zinc and nickel (CWW BREF on mixed metal precipitation)
    ammoniacal or cyanide plating rinse, EDTA, metal complex dyesCo(NH₃)₆²⁺, Co(CN)₆³⁻, Co-EDTA, 1:2 cobalt dye complexescomplexed cobalt passes hydroxide precipitation and biological treatment
    sulfidic, anaerobic sludge or sedimentCoS (s)sulfide precipitation reaches lower residuals than hydroxide
    manganese oxide surfacesCo(III) oxyhydroxide in the MnO₂ latticesurface oxidation; the basis of cobalt scavenging by manganese oxides
    Solubility
    Cobalt chloride, sulfate, nitrate and acetate are freely soluble (element entry); Co(OH)₂, CoCO₃ and CoS control it in treatment. No solubility products are printed in the sources read.
    Hydrolysis
    Stepwise to CoOH⁺ and Co(OH)₂ at high pH only; constants not printed in the sources read (Stumm and Morgan chapter 6 has them).
    Complexation
    Ammonia, cyanide, EDTA and azo dye ligands form strong Co(II) and inert Co(III) complexes; the CWW BREF notes that chelating agents make hydroxide precipitation incomplete. Constants not quoted.
    Precipitates
    Co(OH)₂, CoCO₃, CoS; Co(III) oxyhydroxide on manganese oxides.
    CoX2++2OHXCo(OH)X2(s)\ce{Co^2+ + 2 OH^- -> Co(OH)2 (s)}
    lime or caustic precipitation at high pH with the other base metals; the sources read give no optimum pH for cobalt (Metcalf and Eddy chapter 6 has the hydroxide solubility curves, not re-read)
    CoX2++HSXCoS(s)+HX+\ce{Co^2+ + HS^- -> CoS (s) + H+}
    sulfide precipitation, chemical or biological; lower residual than the hydroxide (CWW BREF, general statement for metals)
    CoX2++6NHX3Co(NHX3)X6X2+\ce{Co^2+ + 6 NH3 -> Co(NH3)6^2+}
    ammoniacal plating and etching baths; the complex keeps cobalt dissolved through pH adjustment (Stumm and Morgan chapter 6, complex formation, from the chapter, not re-read)
    CoX2++COX3X2CoCOX3(s)\ce{Co^2+ + CO3^2- -> CoCO3 (s)}
    carbonate precipitation with soda ash, the variant used where a hydroxide sludge is unwanted, and the solid that limits cobalt in hard alkaline water; Metcalf and Eddy chapter 6 on chemical precipitation, from the chapter, not re-read
    2CoX2++MnOX2(s)+2HX2O2CoOOH(s)+MnX2++2HX+\ce{2 Co^2+ + MnO2 (s) + 2 H2O -> 2 CoOOH (s) + Mn^2+ + 2 H+}
    the surface oxidation that fixes cobalt on manganese oxide: two Co(II) give up one electron each and Mn(IV) takes both, leaving Co(III) oxyhydroxide in the oxide and releasing Mn^2+ and acid; this is why manganese nodules and manganese oxide filter media scavenge cobalt far beyond what sorption of the divalent ion would give; Stumm and Morgan, from the chapter, not re-read
    4Co(NHX3)X6X2++OX2+4HX+4Co(NHX3)X6X3++2HX2O\ce{4 Co(NH3)6^2+ + O2 + 4 H+ -> 4 Co(NH3)6^3+ + 2 H2O}
    air oxidation of the cobalt(II) ammine in an aerated ammoniacal rinse; standard inorganic chemistry, printed by none of the sources read, and written here because the element entry records that cobalt(III) survives only when held in a complex; once formed the hexaammine is kinetically inert, so pH adjustment and sulfide dosing no longer reach the cobalt

    4 · Role in treatment

    as a problem
    complexed cobalt escapes precipitation
    ammonia, cyanide, EDTA and dye ligands hold Co(II) and Co(III) in solution
    break the complex (cyanide oxidation, ammonia stripping, oxidative destruction of EDTA) before precipitation; the CWW BREF names chelating agents as the reason hydroxide precipitation is incomplete
    4Co(NHX3)X6X2++OX2+4HX+4Co(NHX3)X6X3++2HX2O\ce{4 Co(NH3)6^2+ + O2 + 4 H+ -> 4 Co(NH3)6^3+ + 2 H2O}
    an aerated ammoniacal rinse; the cobalt(III) ammine that forms is inert, so the ligand has to be destroyed rather than displaced before precipitation; the equation is standard inorganic chemistry, not printed by the sources read
    cobalt-60 in nuclear plant liquid effluent
    activation product of steel released in reactor and fuel cycle discharges (WHO chapter 9)
    counted in the EU indicative dose with a derived concentration of 40 Bq/L; in the US within the 4 mrem per year beta and photon MCL; removed by ion exchange and reverse osmosis (40 CFR 141.66 Table B)
    cobalt in textile effluent from metal complex dyes
    1:1 and 1:2 cobalt azo dye complexes leave with the dyebath
    ZDHC limit 0.05 to 0.01 mg/L; the complex is not removed by pH adjustment
    no guideline to design to
    WHO, the EU and the US set no drinking water limit; the EPA UCMR 3 reference concentration of 70 µg/L is a screening value
    region-dependent permits: Abu Dhabi marine 0.2 mg/L and sewer 5 mg/L

    5 · Removal and control

    hydroxide precipitation with lime or caustic, settling and filtration
    Co(OH)₂ precipitated at high pH with zinc, nickel and copper
    CoX2++2OHXCo(OH)X2(s)\ce{Co^2+ + 2 OH^- -> Co(OH)2 (s)}
    the pH ideal for one metal may be wrong for another in a mixed effluent; chelating agents block it (CWW BREF section 3.3.2.3.4.2)
    Efficiency
    not quoted for cobalt; about 1 to 10 mg/L for single metals with lime as reagent (CWW BREF citing VITO 2010)
    Interferences
    ammonia, cyanide, EDTA, dye ligands
    sulfide precipitation
    CoS far less soluble than the hydroxide; sodium sulfide or biologically produced sulfide
    CoX2++HSXCoS(s)+HX+\ce{Co^2+ + HS^- -> CoS (s) + H+}
    closed tanks because hydrogen sulfide can be released
    Efficiency
    not quoted for cobalt; the BREF says sulfide reaches lower concentrations than hydroxide for metals in general
    Interferences
    oxygen; excess sulfide
    ion exchange and reverse osmosis (cobalt-60 and trace cobalt)
    cation exchange of Co²⁺; membrane rejection of the divalent ion
    the US best available technologies for beta particle and photon radioactivity are ion exchange and reverse osmosis (40 CFR 141.66 Table B)
    Efficiency
    not quoted
    Interferences
    complexed cobalt is anionic or neutral and passes cation resin; hardness competes
    sorption and oxidation on manganese oxide media
    Co(II) sorbed and oxidised to Co(III) on MnO₂ surfaces
    2CoX2++MnOX2(s)+2HX2O2CoOOH(s)+MnX2++2HX+\ce{2 Co^2+ + MnO2 (s) + 2 H2O -> 2 CoOOH (s) + Mn^2+ + 2 H+}
    the mechanism behind cobalt removal in manganese removal filters; no engineering data read
    Efficiency
    not quoted

    6 · Analytics

    methodstandarddetection limitnote
    ICP-MSEPA 200.8 (mass 59); ISO 17294-2; Standard Methods 3125EPA 200.8 instrument detection limit 0.03 µg/L scanning and 0.002 µg/L selected ion monitoring; UCMR 3 minimum reporting level 1 µg/L by EPA 200.8the UCMR 3 and ZDHC method
    flame AASISO 8288 (cobalt, nickel, copper, zinc, cadmium, lead); Standard Methods 3111 Bnot read for cobaltISO 8288 scope from the WHO zinc background document reference list
    gamma spectrometry for cobalt-60national radiological methods; Euratom Annex III requires detection limits adequate for the indicative dosenot readcobalt-60 is measured as activity, not mass
    Sampling pitfalls
    Acidify for total cobalt; filter 0.45 µm in the field for dissolved cobalt. Complexed cobalt (cyanide, EDTA) is dissolved but not exchangeable, so speciation matters for treatability tests. Cobalt-60 samples need no preservation beyond acidification but the count needs volume.

    7 · Regulatory limits

    Limits change, and many are set locally. Treat these as the published values to start from, not as your compliance target: check the standard in force at your site and the numbers written into your own permit.

    drinking water
    bodylimitnote
    WHO GDWQ 4th ed. with addenda (2022)no guideline cobalt has no chemical fact sheet and no background document; no cobalt fact sheet exists at the WHO 2022 fact sheet address; cobalt-60 falls under the chapter 9 indicative dose criterion of 0.1 mSv per year but is not among the radionuclides of Table 9.2
    EU DWD 2020/2184not set cobalt is not a parameter of Annex I
    EU Council Directive 2013/51/Euratom40 Bq/L cobalt-60Annex III derived concentration used to show the indicative dose is below 0.1 mSv per year; gross beta screening level 1.0 Bq/L
    US EPA NPDWRnot regulated monitored under UCMR 3 with a 1 µg/L minimum reporting level and a 70 µg/L reference concentration for the data summary; cobalt-60 falls under the 4 mrem per year beta particle and photon MCL of 40 CFR 141.66
    discharge
    bodylimitnote
    EU CWW BREF BAT-AEL (Decision 2016/902)not set cobalt is not a BAT 12 metal; BAT 4 monitoring covers Cr, Cu, Ni, Pb, Zn and other metals if relevant
    US EPA 40 CFR 461.12, battery manufacturing, cadmium subcategory, electrodeposited anodes (BAT)7.38 daily maximum; 3.16 monthly average mg/kg of cadmium usedmass based, not a concentration; with cadmium 11.95 and 5.27, nickel 67.49 and 44.64, zinc 51.32 and 21.44 mg/kg
    Abu Dhabi ADS 23/2017, discharge to the marine environment (EAD)0.2 mg/L
    region-dependent; marine discharge only
    Table 1 maximum allowable concentration at the point of discharge
    Abu Dhabi DoE Trade Effluent Control Regulations 2022, discharge to sewer5 mg/L
    region-dependent; sewer discharge, not receiving water
    Table A₄ maximum allowable concentration for trade effluent to the sewer network
    industry thresholds
    sectorbodylimitnote
    textile and leatherZDHC Wastewater Guidelines v₂.1 (2022), Table 20.05 foundational; 0.02 progressive; 0.01 aspirational mg/Lsame values for textile and leather; sludge total cobalt reporting limit 400 mg/kg dry weight, textile only (Table 4A)

    8 · Health and environmental effects

    Toxicity
    Essential as the centre of vitamin B₁₂ (about 1 mg in the body, element entry); no WHO evaluation for drinking water. The EPA used 70 µg/L as the reference concentration for the UCMR 3 data summary; the health basis of that figure was not read.
    Bioaccumulation
    Not addressed in the sources read.
    Ecotoxicity
    No US EPA national recommended aquatic life criterion for cobalt in the table read; no EU EQS. Not addressed further in the sources read.

    Flags

    • No WHO document on cobalt exists; the absence of a fact sheet is inferred from the WHO 2022 fact sheet address returning nothing for cobalt.
    • The 70 µg/L UCMR 3 reference concentration is a screening value whose derivation was not read.
    • The hydroxide, sulfide and ammine equations are textbook chemistry written here; no source read prints them for cobalt.
    • Cobalt sorption and oxidation on manganese oxides is cited to Stumm and Morgan from memory of the surface chemistry chapters, not re-read.
    • Abu Dhabi values cover two media (marine 0.2 mg/L, sewer 5 mg/L); other GCC states not read.
    • The 40 CFR 461.12 cobalt limit is a mass per kg of cadmium, not a concentration.

    Gaps

    • No natural water concentration range for cobalt was read; only the US UCMR 3 screening data and the ocean abundance figure.
    • No cobalt specific removal efficiency, optimum precipitation pH, solubility product or complex formation constant was read.
    • No cobalt aquatic life criterion or ecotoxicity data was read.
    • The health basis of the EPA 70 µg/L reference concentration and any cobalt entry on the EPA Contaminant Candidate List were not read (the CCL 5 list page did not load).
    • Cobalt in battery and catalyst plant effluents as concentrations is in the ledger's chapters, not here.
    • ISO 8288 was not read; its scope is taken from the WHO zinc document reference list and no catalogue url is given.
    • Other GCC discharge standards were not read.
    • The cobalt carbonate and manganese oxide equations are cited to Metcalf and Eddy chapter 6 and to Stumm and Morgan by chapter, from the chapters, not re-read; no constants are quoted.
    • No source read prints a stoichiometry for the destruction of the cobalt cyanide or cobalt EDTA complexes, so none is written.
    • The hexaammine air oxidation is standard inorganic chemistry written here; the element entry supports only the statement that cobalt(III) survives in complexes.

    Sources

    US EPA, Third Unregulated Contaminant Monitoring Rule (UCMR 3), Table 1 (contaminants, minimum reporting levels and methods)
    US EPA, The Third Unregulated Contaminant Monitoring Rule (UCMR 3): Data Summary, January 2017, EPA 815-S-17-001, Table 3 (reference concentrations and occurrence)
    US EPA Method 200.8, Revision 5.4 (1994), Determination of trace elements in waters and wastes by ICP-MS, Table 1 instrument detection limits
    Council Directive 2013/51/Euratom laying down requirements for the protection of the health of the general public with regard to radioactive substances in water intended for human consumption, Annex I and Annex III (derived concentrations for the indicative dose)
    WHO Guidelines for Drinking-water Quality, 4th ed. incorporating the first and second addenda (2022), chapter 9 Radiological aspects, Table 9.2 guidance levels for common radionuclides (NCBI Bookshelf copy)
    40 CFR 141.66, Maximum contaminant levels for radionuclides, Table A (beta and photon emitters) and Table B (best available technologies)
    40 CFR 461.12, Effluent limitations representing BAT, battery manufacturing, subpart A cadmium subcategory
    Commission Implementing Decision (EU) 2016/902 establishing BAT conclusions for common waste water and waste gas treatment/management systems in the chemical sector (CWW), BAT 4 and BAT 12 Table 3 with footnotes 24 to 29
    Best Available Techniques Reference Document for Common Waste Water and Waste Gas Treatment/Management Systems in the Chemical Sector (CWW BREF 2016), sections 2.4.3.9 (zinc), 3.3.2.3.4.2 (chemical precipitation, Table 3.36), 3.3.2.3.4.3 (crystallisation, Table 3.40), 3.3.2.3.5.3 (biological removal of sulphur compounds and heavy metals, Table 3.112) and Table 3.115 (activated sludge inhibition thresholds)
    Abu Dhabi Specification ADS 23/2017, Environmental Specifications for Land-Based Liquid Discharges to the Marine Environment (Environment Agency Abu Dhabi), Table 1
    Abu Dhabi Department of Energy, Trade Effluent Control Regulations 2022 (DoE/PD/R01/005, effective 1 January 2022), Appendix Table A4
    ZDHC Wastewater Guidelines Version 2.1 (November 2022), Table 1M (organotins), Table 2 (heavy metals) and Tables 4A and 4B (sludge)
    Directive (EU) 2020/2184 on the quality of water intended for human consumption (recast), Annex I Parts B and C and Annex III Table 1
    ISO 17294-2:2023, Water quality. Application of ICP-MS. Part 2: Determination of selected elements including uranium isotopes
    Standard Methods for the Examination of Water and Wastewater (online edition), 3111 Metals by Flame Atomic Absorption Spectrometry
    Standard Methods (online edition), 3125 Metals by Inductively Coupled Plasma-Mass Spectrometry
    Stumm, W. and Morgan, J. J., Aquatic Chemistry, 3rd ed. (Wiley, 1996), chapter 6 (metal ions in aqueous solution: hydrolysis and complexation) and chapter 7 (precipitation and dissolution)
    Metcalf and Eddy, Wastewater Engineering: Treatment and Resource Recovery, 5th ed. (McGraw-Hill, 2014), chapter 6 (chemical precipitation of heavy metals: hydroxide and sulfide solubility)
    The Element Book, own entry for cobalt (data/elements/Co.json and data/reference/text/Co.json)
    PubChem element summary for cobalt; estimated oceanic abundance 2 x 10^-5 mg/L from Jefferson Lab

    Conventions

    Valence electrons are counted by the usual convention: the outer shell for s- and p-block elements, ns and (n-1)d for the d-block, ns, (n-1)d and (n-2)f for the f-block. Lanthanides and actinides are placed in the f-block with no group number. Electrical conductivity is the reciprocal of the printed resistivity. Ionic radii are Shannon effective radii, six-coordinate unless noted. Where a field reads “not in sources” the value was not found; it is a gap, not a zero. Regulatory limits are the published values and change often, so check the standard in force at your site and the numbers written into your own permit before you design to them.

    Data

    Element records, isotopes, radii and the descriptive text come from PubChem (NCBI), the Los Alamos National Laboratory periodic table, IUPAC CIAAW and the IAEA Atomic Mass Data Center. Appearance, thermal conductivity, electrical resistivity, crystal structure, discovery and the origin of each name come from Wikipedia and Periodic-Table-JSON, used under CC BY-SA 4.0. Hazard classifications come from the ECHA C&L inventory via PubChem. Ionic radii follow R. D. Shannon (1976). The water chapters cite their own sources at the foot of each entry, and are written to the level of Snoeyink and Jenkins, Stumm and Morgan, MWH's Water Treatment and Metcalf and Eddy.