Critical metals in manganese nodules from the Cook Islands EEZ, abundances and distributions

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  • ta U.S. Geological Survey, PCMSC, 400 Natural Bridges Dr., Sab Sea-Floor Mineral Resources R&D Division, Metals Miningc Seabed Minerals Authority, Avarua, Rarotonga, Cook Islandd SOPAC Division of the SPC, Private Mail Bag, GPO, Suva, Fij

    a r t i c l e i n f o

    Article history:Received 20 August 2014Received in revised form 8 December 2014Accepted 12 December 2014Available online 8 January 2015

    (1,247,834), Mo (186,166), V (356,247), W (30,215), and Zr (195,323). When compared with the Clarion

    0 km2, whereas theEEZ) of the CIs totals

    Ore Geology Reviews 68 (2015) 97116

    Contents lists available at ScienceDirect

    Ore Geology

    j ourna l homepage: www.e lseThe Cook Islands (CIs), located in the central South Pacic, consistof a northern group of six atolls and a southern group of nine islands.

    1,977,000 km , making the CIs a very large marine nation with anocean/land ratio of 8238. The total population of Cook Islanders has var-ied between about 24,600 and 17,300 from 2007 to 2014, including1. Introduction Those 15 islands have a total land area of 24200 nm (360 km) Exclusive Economic Zone (

    2Clipperton Zone, the CIs nodules show higher nodule abundances (N25 kg/m2 over ~123,844 km2), and aremore enriched in the green-tech, high-tech, and energy metals Co, Ti, Te, Nb, REY, Pt, and Zr. The CIs EEZshows a signicant resource potential for these critical metals due to their high prices, high demand, and thehigh nodule abundance, which will allow for a smaller footprint for a 20-year mine site and therefore smallerenvironmental impact.

    Published by Elsevier B.V.Abbreviations: ECS, Extended Continental Shelf; EEZCook Islands; REE, Rare earth elements; REY, Rare earth ele Corresponding author.

    E-mail address: (J.R. Hein). by Elsevier B.V.areas of high abundance; however, Ti, Co, and REY show high contents where nodule abundances are high. Ofthe six areas identied to represent a range of metal contents, one at the northern end of the N-S abundancemain belt optimizes the most metals and would yield the highest dry metric tons for Mn (61,002,292), NiKeywords:Manganese nodulesCook Islands EEZCritical metalsMnTiCoNiREYdi a, Nobuyuki Okamoto b, Kira Mizell a, Darryl Thorburn c, Akuila Tawake d

    nta Cruz, CA 95060, USATechnology Dept., JOGMEC, 2-10-1 Toranomon, Minato-ku, Tokyo 105-0001, Japansi

    a b s t r a c t

    The Cook Islands (CIs) Exclusive Economic Zone (EEZ) encompasses 1,977,000 km2 and includes the Penrhyn andSamoa basins abyssal plainswheremanganesenodulesourish due to the availability of prolic nucleusmaterial,slow sedimentation rates, and strong bottom currents. A group of CIs noduleswas analyzed formineralogical andchemical composition, which include many critical metals not before analyzed for CIs nodules. These noduleshave varying sizes and nuclei material; however all are composed predominantly of -MnO2 and X-ray amor-phous iron oxyhydroxide. The mineralogy, Fe/Mn ratios, rare earth element contents, and slow growth rates(mean 1.9 mm/106 years) reect formation primarily by hydrogenetic precipitation. The paucity of diageneticinput can be explained by low primary productivity at the surface and resultant low organic matter content inseaoor sediment, producing oxic seaoor and sub-seaoor environments. The nodules contain high mean con-tents of Co (0.41%), Ni (0.38%), Ti (1.20%), and total rare earth elements plus yttrium (REY; 0.167%), and also highcontents of Mo, Nb, V, W, and Zr.Compiled data from a series of four cruises by the Japan International Cooperation Agency and theMining agencyof Japan from 1985 to 2000 were used to generate a map that denes the statistical distribution of noduleabundance throughout the EEZ, except the Manihiki Plateau. The abundance distribution map shows a belt ofhigh nodule abundance (1945 kg/m2) that starts in the southeast corner of the EEZ, runs northwest, and alsobifurcates into a SW trending branch. Small, isolated areas contain abundances of nodules of up to 58 kg/m2.Six ~20,000 km2 areas of particularly high abundance were chosen to represent potential exploration areas,and maps for metal concentration were generated to visualize metal distribution and to extrapolate estimatedmetal tonnages within the six sites and the EEZ as a whole. Grades for Mn, Cu, and Ni are low in CIs nodules inJames R. Hein a,, Francesca Spinarabundances and distributions

    Critical metals in manganese nodules from, Exclusive Economic Zone; CIs,ments plus yttriumhe Cook Islands EEZ,


    v ie r .com/ locate /oregeorevboth residents and about a quarter of the population living outside theCIs, mostly in New Zealand.

    The EEZs adjacent to that of the CIs include French Polynesia to theE-SE, Kiribati to the E-NE, Tokelau to the NW, American Samoa to thewest, and Niue to the SW (Fig. 1). International waters lie to the north

  • i k iu

    98 J.R. Hein et al. / Ore Geology Reviews 68 (2015) 97116M a n i hP l a t e a





    '0"S 1:350,000,000


    T o k e l a uand south of the CIs EEZ and also form a donut hole between the EEZsof CIs, Kiribati, and French Polynesia. The CIs has a potential ExtendedContinental Shelf (ECS) north of the northern EEZ boundary, which iscurrently before the Commission on the Limits of the ContinentalShelf. The physiography of the CIs EEZ consists predominantly of theManihiki Plateau (NW quadrant) with associated small seamounts,and parts of the Penrhyn Basin and Samoa Basin abyssal plains with as-sociated abyssal hills and small seamounts.

    The abyssal seabed sediments of the CIs EEZ consist predominantlyof zeolite-rich pelagic redbrown clays, but biogenic silica and carbon-ate increase in the sediment with decreasing latitude and at waterdepths of less than about 4800 m. Carbonate mud/ooze dominates inthe far NE of the EEZ and in the potential ECS. The Manihiki Plateau isblanketed by calcareous and siliceous mud/ooze. The abyssal plainmuds are composed of quartz, clay minerals, zeolites, volcanic glass,iron and manganese oxides, phosphate debris, and minor biogenic car-bonate and silica in places (Cronan et al., 2010).








    0 100

    LegendCook Islands EEZ

    Manihiki Plateau

    EEZ boundaries

    Samples From This Study

    Samples From Other Studies

    N i u e

    A m e r i c a nS a m o a

    Fig. 1. Locationmapof theCook Islands EEZ (inset) and amap showing sample locations analyzeand Okamoto (2003).K i r i b a t i




    10 0


    NFerromanganese nodules (hereafter Mn nodules) from the CIs EEZare compositionally different from those in other nodule elds fromthe global ocean. It has been known for some time that CIs noduleshave relatively high cobalt (Co) contents and low nickel (Ni), copper(Cu), and manganese (Mn) contents (e.g. Cronan et al., 1991; Verlaanet al., 2004; Hein and Petersen, 2013) compared to other nodule elds(Hein et al., 2013). The concentrations of many critical and strategicmetals have not been analyzed previously for CIs nodules, so compari-sons with other nodule elds have been limited. To address this, wepresent here chemical and mineralogical analyses for a set of nodulesdistributed throughout the CIs EEZ (Table 1; Appendix 1; Supplementa-ry Table S.1) for a set of 67 elements, including all of the elements ofpotential economic interest, such as the rare earth elements (REEs)plus yttrium (REY), tellurium (Te), niobium (Nb), zirconium (Zr), tung-sten (W), titanium (Ti), and others (Appendix 1). In addition, werecalculate the tonnages of nodules and contained metals from variousnodule abundance regions (in square kilometers) determined by GIS

    F r e n c hP o l y n e s i a





    '0" S




    200 400 600 800Kilometers

    d for this study in blue andother samples used for this study in red from JICA/MMAJ (2001)

  • 99J.R. Hein et al. / Ore Geology Reviews 68 (2015) 97116Table 1Location of Cook Islands EEZ manganese nodules.

    Sample number Latitude(S)


    Water depth(m)

    CK-76-1 STN-03 FFC-02A 1633.20 15917.50 5089CK-76-1 STN-03 FFG-06A 1633.20 15917.50 5093CK-76-1 STN-03 FFG-06B 1633.20 15917.50 5093CK-76-1 STN-04 FFC-04 1516.00 15908.50 5134CK-76-1 STN-05 FFG-08A 1440.00 15906.00 5092CK-76-1 STN-05 FFG-08B 1440.00 15906.00 5092CK-7-16 STN-06 FFG-09 1404.90 15859.00 5111CK-76-1 STN-07 FFG-10A 1224.00 15844.00 5310CK-76-1 STN-07 FFG-10B 1224.00 15844.00 5310CK-76-1 STN-08 FFG-11 1038.00 15831.50 5286CK-76-1 STN-10 FFG-13 1504.80 16050.00 4999ArcMap calculations. Several assessments of contained metal tonnagesfor CIs EEZ nodules have been made (e.g. Clark et al., 1995; Kingan,1998; JICA/MMAJ, 2001; Okamoto, 2003; Cronan, 2013; Hein andPetersen, 2013). Most of those assessments considered only a fewmetals, so here we present new estimates for the tonnages of 10contained metals of economic interest as well as for total REY.

    2. Samples and methods

    Fifty-four samples and subsamples were analyzed from 27 sites.Each sample was dried and ground to a b75 m powder in an agatemortar and pestle. The nodule nucleuswas included in the bulk analysisof each nodule sample. Element concentrations were determined byseveral methods. The 10 major elements (Fe, Mn, Si, Al, Mg, K, Ca, Na,

    CK-76-1 STN-11 FFG-14A 1640.00 16048.50 4793CK-76-1 STN-11 FFG-14B 1640.00 16048.50 4793CK-76-1 STN-11 FFG-14C-MRT-B0-7 1640.00 16048.50 4793CK-76-1 STN-11 FFG-14C-MRU-B0-13 1640.00 16048.50 4793CK-76-1 STN-11 FFG-14C-MRU-L0-5 1640.00 16048.50 4793CK-76-1 STN-11 FFG-14C-MRU-L5-13 1640.00 16048.50 4