Cobalt Rich Ferromanganese Crusts in The

Handbook of
MARINE
MINERAL
DEPOSITS
Edited by
David S. Cronan, Ph.D., D.Sc., FIMM
Professor of Marine Geochemistry
T.H. Huxley School of Environment,
Earth Sciences and Engineering
Royal School of Mines
Imperial College, University of London
London, England
CRC Press
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Handbook of marine mineral deposits I editor, DavidS. Cronan.

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9 Cobalt-Rich Ferromanganese
Crusts in the Pacific
james R. Hein, Andrea Koschinsky, Michael Bau,
Frank T. Manheim, }ung-Keuk Kang, and Leanne Roberts
ABSTRACT
Co-rich Fe-Mn crusts occur throughout the Pacific on seamounts, ridges, and plateaus where
currents have kept the rocks swept clean of sediments at least intermittently for millions of years.
Crusts precipitate out of cold ambient sea water onto hard-rock substrates forming pavements up
to 250 mm thick. Crusts are important as a potential resource for Co, Ni, Pt, Mn, Tl, Te, and other
metals, as well as for the paleoclimate signals stored in their stratigraphic layers. Crusts form at
water depths of about 400 to 4000 m, with the thickest and most Co-rich crusts occurring at depths
of about 800 to 2500 m, which may vary on a regional scale. Gravity processes, sediment cover,
submerged and emergent reefs, and currents control the distribution and thickness of crusts on
seamounts. Crusts occur on a variety of substrate rocks that generally decrease in the order, breccia,
basalt, phosphorite, limestone, hyaloclastite, and mudstone. Because of this wide variety of substrate
types, crusts are difficult to distinguish from the substrate using remotely sensed data, such as
geophysical measurements, but are generally weaker and lighter-weight than the substrate. Crusts
can be distinguished from the substrates, however, by their much higher gamma radiation levels.
The mean dry bulk density of crusts is 1.3 g/cm3 , the mean porosity is 60%, and the mean surface
area is extremely high, 300 m2/g. Crusts generally grow at rates of 1 to 10 mm!Ma. Crust surfaces
are botryoidal, which may be modified to a variety of forms by current erosion. In cross-section,
crusts are generally layered, with individual layers displaying massive, botryoidal, laminated,
columnar, or mottled textures. Characteristic layering is persistent regionally in the Pacific. Crusts
are composed of ferruginous vernadite (o-Mn02 ) and X-ray amorphous Fe oxyhydroxide, with
moderate amounts of carbonate fluorapatite (Cl<f\) in thick crusts arid minor amounts of quartz and
feldspar in most crusts. Elements most commonly associated with the vernadite phase include Mn,
Co, Ni, Cd, and Mo, whereas those most commonly associated with Fe oxyhydroxide are Fe and
As. Detrital phases are represented by Si, Al, K, Ti, Cr, Mg, Fe, and Na; the CPA phase by Ca, P,
Sr, Y, and C0 2 ; and a residual biogenic phase by Ba, Sr, Ce, Cu, V, Ca, and Mg. Crusts contain
Co contents up to about 2.3%, Ni to 1%, and Pt to 3 ppm, with mean Fe/Mn ratios of 0.6 to 1.3.
Fe/Mn decreases, whereas Co, Ni, Ti, and Pt increase in central Pacific crusts and Fe/Mn, Si, and
Al increase in continental margin crusts and in crusts with proximity to west Pacific volcanic arcs.
Vernadite and CPA-related elements decrease, whereas Fe, Cu, and detrital-related elements
increase with increasing water depth of crust occurrence. Cobalt, Ce, Tl, and maybe also Ti, Pb,
and Pt are strongly concentrated in crusts over other metals because of oxidation reactions. Total
rare earth elements (REEs) commonly vary between 0.1% and 0.3% and are derived from sea water
along with other hydrogenetic elements, Co, Mn, Ni, etc. Platinum, Rh, Ir, and some Ru in crusts
are also derived from sea water, whereas Pd and the remainder of the Ru derive from detrital
minerals. The older parts of thick crusts were phosphatized during at least two global phosphogenic
events during the Tertiary, which mobilized and redistributed elements in those parts of the crusts.
0-8493-8429-X/00/$0.00+$.50
© 2000 by CRC Press LLC 239
240 Handbook of Marine Mineral Deposits
Silicon, Fe, Al, Th, Ti, Co, Mn, Pb, and U are commonly depleted, whereas Ni, Cu, Zn, Y, REEs,
Sr, and Pt are commonly enriched in phosphatized layers compared to younger nonphosphatized
layers. The dominant controls on the concentration of elements in crusts include the concentration
of metals in sea water and their ratios, colloid surface charge, types of complexing agents, surface
area, and growth rates. Crusts act as closed systems with regard to the isotopic ratios of Be, Nd,
Pb, Hf, Os, and U-series, which in part have been used to date crusts and in part used as isotopic
tracers of paleoceanographic and paleoclimatic conditions. Those tracers are especially useful in
delineating temporal changes in deep-ocean circulation. Research and development on the tech-
nology of mining crusts are only in their infancy. Detailed maps of crust deposits and a better
understanding of small-scale seamount topography are required to design the most appropriate
mining equipment.
9.1 INTRODUCTION
Iron-manganese oxyhydroxide crusts (Figure 9.1), hereafter called Fe-Mn crusts, are ubiquitous
on hard-rock substrates throughout the ocean basins. They form at the seafloor on the flanks and
summits of seamounts, ridges, plateaus, and abyssal hills where the rocks have been swept clean
of sediments at least intermittently for millions of years. Crusts form pavements up to 250 mm
thick on rock outcrops, or coat talus debris. Fe-Mn crusts form by hydrogenetic precipitation from
cold ambient bottom waters (Figure 9.1A, C, D), or by a combination of hydrogenetic and hydro-
thermal precipitation in areas of hydrothermal venting (Figure 9.1B), such as near oceanic spreading
axes, volcanic arcs, and hotspot volcanoes. Fe-Mn crusts contain subequal amounts of Fe and Mn
and are especially enriched in Mn, Co, Pb, Te, Bi, and Pt relative to their lithospheric and sea water
concentrations (Table 9.1). There are two primary practical interests in Fe-Mn crusts, the first being
their economic potential for Co, but also for Mn, Ni, and Pt, and possibly also Ti, rare earth elements
(REEs), Te, Tl, P, and others. The second interest is the use of crusts as recorders of the past 60
Ma of oceanic and climatic history.
9.1.1 CLASSIFICATION
Up until the late 1970s Fe-Mn crusts were usually not distinguished from Fe-Mn nodules. If a
distinction was made, crusts were called seamount nodules. However, there are distinct differences
between Fe-Mn nodules and crusts, other than just form (Table 9.2). Nodules nucleate on small
bits of rock, bone, or old nodule fragments on the surface of sediments. Nodules commonly form
by both diagenetic and hydrogenetic processes and thus their composition reflects input from both
sea water and sediment pore water sources, the latter being a substrate contribution, which is not
found in crusts. 1 However, some nodules form predominantly by diagenetic or hydrogenetic pro-
cesses. Nodules have sometimes been referred to as hydrogenous, regardless of their origin;
consequently, we use the term hydrogenetic to avoid any confusion about a substrate contribution
to crusts. Generally, crusts and nodules have different mineralogical (vernadite vs. todorokite and
vernadite) and chemical compositions (for example, high Co vs. high Cu) because of their genetic
differences as well as differences in water depths of formation, although there is much overlap.
Iron and manganese hydroxides and oxyhydroxides may also form by hydrothermal processes
below the seafloor (Table 9.2). These deposits usually consist of stratabound layers or manganese-
cemented volcaniclastic sediments and are distinctly different in texture and composition from
hydrogenetic Fe-Mn crusts, especially with regard to the extreme fractionation of Mn and Fe
(Table 9.1) and low multiple-trace metal contents in the hydrothermal deposits. 2 In the hydrothermal
deposits, Fe/Mn varies from about 24,000 (up to 58% Fe) for hydrothermal ironstones to 0.001
(up to 52% Mn) for hydrothermal stratabound Mn oxides (means in Table 9.F). Many other minor
types of iron and manganese mineralization occur in the ocean basins (Table 9.2), but the present
work is confined to a discussion of Co-rich hydrogenetic Fe-Mn crusts (Figure 9.1A, C, D).
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FIGURE 9.1 (A) 180-mm-thick hydrogenetic Fe-Mn crust from Lomilik Seamount, Marshall Islands, which grew on a
phosphatized hyaloclastite substrate and contains fractures filled with CFA; distinct growth layers can be seen, some of
which are very porous, with pores and vugs filled with either carbonate sediment or CFA. (B) Mixed hydrothermal-hydro-
genetic Fe- Mn crust from Gorda Ridge, northeast Pacific; the crust shows distinct growth layers and Fe-rich lami nae near
the base; the substrate is amygdaloidal basalt. (C) Current polished and fluted surface of a botryoidal Fe-Mn crust from the
Marshall Islands, water depth 2,090 m. (D) Same crust as in (C) showing 30- to 50-mm-tall columns in a 40- to 50-mm-
thick crust; note that the columns are separated by detrital-ri9h material (pale gray). Scales are in centimeters.
TABLE 9.1
Contents of Mn, Fe, Co, Ni, and Pt (wt. %) in Marine Fe, Mn, and Fe-Mn Deposits Compared
to Contents in and Enrichments Over Sea Water and the Earth's Crust
Sea Water Lithosphere Fe-Mn Crusts Stratabound Mn Seamount Ironstones
Fe/Mn 1.2 57 0.7 0.04 5100
Mn 5.0 X 10-9 0.095 26 47 0.01

Mn/sea water 1.9 X 107 5.2 X 109 9.4 X 109 2.0 X 106
Mn/lithosphere 274 495
Fe 6.0 X 10-9 5.4 19 1.8 51

Fe/sea water 9.0 X 108 3.2 X 109 3.0 X 108 8.5 X 109
Fe/lithosphere 3.5 9.4
Co 1.0 X JO-IO 2.5 X 10-3 0.70 0.017 <2.3 X 10-4

Co/sea water 2.5 X 106 7.0 X 108 1.7 X 107 <2.3 X 105
Co/lithosphere 280 6.8
Ni 5.0 X 10-8 8.0 X 10-3 0.48 0.10 0.024

Ni/sea water 1.6 X 105 9.6 X 106 2.0 X 106 4.8 X 105
Ni/lithosphere 60 12.5 3.0
Pt 2.4 X 10-ll 4.0 X 10-7 5 X 10-5 3.0 X J0-6 1.1 x w-6

Pt/sea water 1.7 X 104 2.1 X 106 1.3 X 105 4.6 X 104
Pt/lithosphere 125 7.5 2.8
9.1.2 DISTRIBUTION
Fe-Mn crusts have been recovered from seamounts in the Pacific as far north as the Aleutian Trench
and as far south as the Pacific sector of the Circum-Antarctic Ridge. However, the most detailed
studies have been on crusts from the equatorial Pacific, mostly from the Exclusive Economic Zones
(EEZ) of the Federated States of Micronesia, Marshall Islands, Kiribati, and the U.S. (Hawaii,
Johnston Island, and California), and from international waters in the Mid-Pacific Mountains.
Compared to the estimated 50,000 or so seamounts that occur in the Pacific, the Atlantic and Indian
oceans contain fewer seamounts, and most crusts there are associated with the spreading ridges.
Crusts associated with those spreading ridges usually have a hydrothermal component that may be
large near active venting, but which regionally is generally a small (<30%) component of the crusts
formed along most of the ridges. 3 Those types of hydrogenetic-hydrothermal crusts are also
common along the active volcanic arcs in the west Pacific, 4 •5 the spreading ridges in back-arc basins
of the west and southwest Pacific, spreading centers in the south and east Pacific, and active hotspots
in the central (Hawaii) and south (Pitcairn) Pacific. Very few (<15) of the approximately 50,000
seamounts in the Pacific have been mapped and sampled in detail, and none of the larger ones,
which are comparable in size to continental mountain ranges (Figure 9.2).
Fe-Mn crusts occur at water depths of about 400 to 4000 m, but most commonly occur at
depths from about 1000 to 3000 m. The most Co-rich crusts occur at water depths from 800 to
2200 m, which mostly encompasses the oxygen minimum zone (OMZ). The thickest crusts occur
at water depths of 1500 to 2500 m, which corresponds to the depths of the outer summit area and
upper flanks of most Pacific Cretaceous seamounts. The water depths of thick high-Co-content
crusts vary regionally and are generally shallower in the South Pacific where the OMZ is less well
developed; there, the maximum Co contents and thickest crusts occur at about 1000 to 1500 m. 6
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Classification of Marine Ferromanganese Oxide Deposits by Form, Processes of Formation, and Environment of Formation; Most Common OQ
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Nodules Abyssal plains, oceanic Submerged calderas and fracture Abyssal plains, Submerged calderas Abyssal plains, All areas ::::r-
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plateaus, seamounts 1 zones oceanic plateaus oceanic plateaus1 (nodule nuclei) -o
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Crusts Midplate volcanic edifices 2 Active spreading axes, volcanic Active volcanic arcs, Abyssal hills Midplate edifices (crust n
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arcs, fracture zones, midplate spreading axes, off substrate rock) n·
edifices axis seamounts,
fracture zones
Sediment-hosted - Active volCanic arcs, large Continental Continental margins,
stratabound midplate volcanic edifices, margins3 volcanic arcs, midplate
layers and lenses sediment-covered spreading axes edifices
Cements Midplate volcanic Active volcanic arcs, large Midplate volcanic Midplate volcanic Volcanic arcs, midplate
edifices4 midplate volcanic edifices5 edifices4 edifices4 edifices
Mounds and - Back-arc basins, spreading centers,
chimneys volcanic arcs
1Less common on ridges, continental slope and shelf; 2Includes seamounts, guyots, ridges, plateaus; 3Fe and Mn carbonate lenses and concretions; 4 Mostly fracture and vein fill, cement for
volcanic breccia; 5Mostly cement for breccia, sandstone, and siltstone
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FIGURE 9.2 Comparison of the size of typical central Pacific seamounts and ridges sampled for this study
compared to the size of the Sierra Nevada of California. Necker Ridge is in the Hawaii EEZ; Karin Ridge and
Horizon Guyot are in the Johnston Island EEZ; and the others are in the Marshall Islands EEZ.
Crusts become thinner with increasing water depth because of mass movements and reworking of
the deposits on the seamount flanks. Most crusts on the middle and lower seamount flanks consist
of encrusted talus rather than encrusted rock outcrop, the latter however typically has thicker crusts. 7
Many seamounts and ridges are capped by pelagic sediments and therefore do not support the
growth of crusts on the summit. Other volcanic edifices are capped by limestone (drowned reefs),
which commonly supports thinner crusts than nearby volcanic and volcaniclastic rocks 7· 10 because
of the younger age of the limestones and therefore shorter time for crust growth coupled with the
instability and mass wasting of the limestone. Crusts are usually thin down to as much as 3000 m
water depth on the submarine flanks of islands and atolls because of the large amounts of debris
that are shed down the flanks by gravity processes. 11 Reworked crust fragments occur as clasts in
breccia, which is one of the most common rock types on seamount flanks_? Regional mean crust
thicknesses for most of the Pacific fall between 20 and 40 mm. Only rarely are very thick crusts
(>80 mm) found, for which initial growth may approach within 10 to 30 Ma the age of the
Cretaceous substrate rock. Clearly, while most Pacific seamounts are 65 to 95 Ma old, most crusts
collected on those seamounts represent less than 25 Ma of growth because of reworking and episodic
sediment cover.
The distribution of crusts on individual seamounts is poorly known. Seamounts generally have
either a rugged summit with moderately thick to no sediment cover (0 to 150m) or a flat summit
(guyot) with thick to no sediment cover (0 to 500 m). The outer summit margin and the flanks may
be terraced with shallowly dipping terraces headed by steep slopes meters to tens of meters high.
Talus piles commonly accumulate at the base of the steep slopes and at the foot of the seamounts;
Cobalt-Rich Ferromanganese Crusts in the Pacific 245
thin sediment layers may blanket the terraces, alternately covering and exhuming Fe-Mn crusts.
Other seamount flanks may be uniformly steep up to 20°, but most seamount flanks average about
14°.7 •12 The thickest crusts occur on summit outer-rim terraces and on broad saddles on the summits.
Estimates of sediment cover on various seamounts range from 15% to 75%, but sediment cover
probably averages about 50%. Crusts are commonly covered by a thin blanket of sediments in the
summit region and on flank terraces. It is not known how much sediment can accumulate before
crusts stop growing. Crusts have been recovered from under up to 2m of sediment without apparent
dissolution. 13 - 16 Based on coring results, Yamazaki 17 estimated that there are 2 to 5 times more crust
deposits on seamounts than estimates based on exposed crust outcrops because of their coverage
by a thin blanket of sediment. Those thinly veiled crusts would be within reach of mining operations.
9.1.3 HISTORICAL PERSPECTIVE
Ferromanganese crusts are members of a family of Fe-Mn precipitates and accretionary deposits
that form to greater or lesser extents wherever oxygen-containing aqueous solutions occur. Emman-
uel Swedenborg's 18 great monograph on iron (De Ferro) in 1734 was the first, and in some respects
a surprisingly modem, summary of the origin of Fe-Mn concretions. For example, his account of
lake and bog ores, then important raw materials for iron production, correctly attributed their
formation to precipitation from solutions enriched in Fe and Mn by leaching of soils and organic
matter. The next major advance occurred through the discovery of deep-ocean nodules and crusts
by the Challenger Expedition of 1873-6. 19 ·20 The Challenger's dredge hauls yielded not only
classical black Fe-Mn nodules from abyssal depths (4500 to 6000 m), but also recovered a variety
of coatings, layers, and crusts of Fe-Mn oxide material from lesser depths, some as shallow as 370
m. The chemist on board, J.Y. Buchanan, and co-workers demonstrated that those samples contained
significant minor amounts of Cu, Ni, and Co,2 1 as well as the then newly discovered elements such
as Th and Tl, which would not be further investigated for another 60 years.
After World War II, E.D. Goldberg, G. Arrhenius, and co-workers at Scripps Institution of
Oceanography studied Fe-Mn nodules and established the concept of metal scavenging on active
catalytic surfaces of Mn oxides on the seafloor. 22 •23 Most nodules studied were from abyssal depths
and had 0.30% Co or less. A few samples, from ocean ridge areas, had as little as 0.03% Co,
whereas samples from Cape Johnson and Sylvania seamounts had Co contents as high as 0.70%.
Interest in the economic potential of abyssal Fe-Mn nodules, ignited by John Mero in the early
1960s,24•25 developed into massive international activities by many consortia that peaked in the
middle 1970s. Mero26 and Russian investigations led by P.L. Bezrukov27 •28 noted that topographic
highs in the central Pacific had deposits with the highest mean Co contents (1.2%) of any region
in the world's oceans. Based on existing data and new analyses performed as part of a Ph.D.
dissertation at Imperial College, University of London, Cronan29 •30 drew attention to an inverse
correlation between water depth and Co content of nodules recovered from seamounts. The depth
relationship for Co in nodules is apparently not universal, however, as can be seen in statistical
compilations of Fe-Mn nodule data in the Scripps Institution of Oceanography Nodule Data Bank. 31
However, some apparent exceptions to that relationship, for example those noted around the
Hawaiian Islands by Frank et al. 8 and Craig et al., 32 were later shown with additional data to confirm
the Co-water depth relationship. 33
Fe-Mn crusts had begun to be distinguished from nodules in the 1970s, 8•13 •34•35 and their
economic potential was recognized. 32•36 The first systematic investigations of Co-rich crust areas
were carried out in the Line Islands south of Hawaii by the 1981 German Midpac I cruise on the
R. V Sonne, headed by Peter Halbach of the Technical University, Clausthal-Zellerfeld. That cruise
made breakthrough discoveries using large dredges coupled with seismic profiling and bottom
photography. 12 Subsequent German, U.S. Geological Survey, and University of Hawaii cruises to
submarine edifices in the central Pacific refined our knowledge of crust distributions and chemical
relationships. They showed that crusts were especially enriched in Co, Fe, Ce, Ti, P, Pb, As, and
especially Pt, but relatively lower in Mn, Ni, Cu, and Zn than nodules. 33 -37-40
International complications partly linked to the location of abyssal nodules in international
waters contributed to the withdrawal of commercial consortia from active preparations for nodule
mining in the late 1970s. The extensive occurrences of Fe-Mn crusts within the EEZ of coastal
nations (200 nautical miles) provided an incentive for mineral interests within areas of national
jurisdiction.4' This applied not only to Pacific seamount deposits, but also to Fe-Mn crusts on
continental margin terraces that have been kept free of detrital sedimentation by currents. 42 •43
Other systematic Fe-Mn minerals investigations during the 1970s and 1980s included a series
of cruises by the Japanese Geological Survey, directed mainly toward abyssal nodule deposits
[e.g., Reference 44], crust studies centered in the Japanese EEZ (Izu-Bonin arc; see Usui and
Someya5 for compilation of data and references), and in international waters of the Mid-Pacific
Mountains. Other Asian nations like Korea and China initiated Fe-Mn crust research with the
U.S. and other cooperators. [e.g., References 45, 46] A detailed database and review of the
chemical composition of crusts based on data up to 1987 was published in 1989, 47 and is also
available on NOAA and MMS Marine Minerals CD-ROM, NGDC Data Set #0827, and web site
http://www.ngdc.noaa.gov/mgg/geology/mmdb/.
9.2 FE-MN CRUST CHARACTERISTICS

9.2.1 TEXTURES AND PHYSICAL PROPERTIES
Crust surfaces exposed directly to the seafloor are botryoidal, with botryoids varying in size from
microbotryoidal (millimeter size) to botryoidal (centimeter size). Fresh growth surfaces are char-
acterized by a fractal distribution of botryoids with extreme surface area. Under conditions of high
current flow, the botryoids are modified, either by smoothing or by accentuation of the relief by
erosion around the margins of the botryoids, in places producing mushroom-shaped forms. With
strong unidirectional flow, the botryoids become polished and fluted (Figure 9.1C). Crusts on the
sides of rocks are commonly more protected from current activity and grow at a slower rate, thereby
acquiring very high Co contents; textures of those side crusts are very porous and granular.
Crust profiles vary according to thickness and regional oceanographic conditions. Thin crusts
(<40 mm) are usually black and massive, botryoidal, or laminated. Thicker crusts (40 to 80 mm)
commonly have at least two distinct layers, a lower black, massive, dense layer that is phosphatized
and an upper black-to-brown layer that is more porous, with laminated, mottled, botryoidal, and/or
columnar textures. The thickest crusts (>80 mm) may have up to eight distinct macroscopic layers,
the lower several layers of which may be phosphatized. Thick crusts in the equatorial Pacific
typically .have four to five macroscopic layers that are consistent over large regions: (1) the
uppermost layer is black, dense, and has a botryoidal, columnar, or laminated texture; (2) the next
layer is Fe-stained brown, very porous to vuggy with vugs elongate perpendicular to layers; vugs
are filled with infiltered carbonate sediment and the texture is mottled or columnar; (3) black, dense
to sparsely vuggy, with columnar, mottled, laminated, and/or botryoidal textures; (4) Fe-stained
brown along extensive network of microfractures, with columnar, botryoidal, or laminated texture
and impregnated with CFA; and (5) black, dense, laminated, mottled, botryoidal, and columnar
textures; impregnated by CFA and cut by CPA-filled veins.
In polished thin sections, textures consist of alternating laminated, columnar, botryoidal, and
mottled textures. Columns range in height from millimeters to 50 mm (Figure 9.1D48 ), with detrital
grains separating columns and actually promoting columnar growth. 49 Mottled layers are the most
porous and detritus-rich. The various textures probably reflect bottom water conditions at the time
of precipitation of the oxides. Mottled, columnar, botryoidal, and laminated textures probably
represent progressively decreasing energy in the depositional environment. 50
An important consideration in the exploration and exploitation of potential crust resources is

the contrast in physical properties between crusts and substrate rocks. Those comparisons are
complicated by the fact that crusts grow on a wide variety of substrates, including breccia, basalt,
phosphorite, limestone, hyaloclastite, and mudstone, in that order of abundance. Phosphorite and
fresh basalt are strong, competent rocks and contrast significantly with crusts, which are weak,
light-weight, and porous (Table 9.3); the other rock types, including altered basalt, may not contrast
much in physical properties with Fe-Mn crusts. In general, crusts are much more porous (mean
60%) than most substrate rocks and have an extreme amount of specific surface area, which averages
about 300 m2/g (Table 9.3), similar to the surface area of silica gel. Interestingly, the surface area
decreases by up to 20% when measured one month after collection of the crust and up to 40%
after two months. 51 This clearly shows that many physical properties that are measured a long time
after collection of the crusts may not closely approximate in situ crust properties. The mean wet
bulk density of crusts is 1.90 g/cm3, and the mean dry bulk density is 1.30 g/cm3. The P-wave
velocity of crusts may be less or more than that of sedimentary substrate rocks, but is generally
less than that of basalt. This variable contrast will make it difficult to develop sonic devices for
measuring in situ crust thicknesses. The most distinctive property of Fe-Mn crusts is their gamma
radiation level, which averages 475 net counts/min in contrast to sedimentary rock substrates 101
and basalt substrates (Reference 146; Table 9.3). Gamma radiation may be a useful tool for crust
exploration under thin sediment cover and for measuring crust thicknesses in situ.
9.2.2 MINERALOGY
The mineralogy of bulk crusts is relatively simple compared to hydrothermal and diagenetic Fe
and Mn deposits. The dominant crystalline phase is Fe-rich 8-Mn0 2 (ferruginous vernadite 14·52·53 )
with generally two X-ray reflections at about 1.4 A and 2.4 A that vary widely in sharpness as the
result of crystallite size and Mn content. 8-Mn02 generally makes up more than 95% of the X-ray
crystalline phases, the remainder being detrital minerals such as quartz, plagioclase, K-feldspar,
pyroxene, phillipsite, and authigenic carbonate fluorapatite (CFA; Table 9.4). The older parts of
thick crusts are phosphatized and may contain up to 30% CFA in that part of the crust, but CFA
is generally less than 10% of thick bulk crusts. Another major phase in crusts is X-ray amorphous
Fe oxyhydroxide (8-FeOOH, feroxyhyte 52 ), which is commonly epitaxially intergrown with 8-
Mn02.54 It is not clear whether or not small amounts of Mn may substitute for Fe in the FeOOH.
In about 6% of 640 samples analyzed, the feroxyhyte crystallizes as goethite in the older parts of
thick crusts. In Pacific crusts, the quartz and part of the plagioclase are eolian, whereas the remainder
of the plagioclase and the other volcanogenic minerals derive from local outcrops.
Todorokite, which is common in diagenetic Fe-Mn nodules and hydrothermal Mn deposits, is
rare in hydrogenetic crusts. Of 640 XRD analyses done by the USGS on Pacific crusts, only 5%
(2% if offshore California samples are excluded) contain todorokite; 30% of crust samples from
offshore California contain todorokite, which, because of very high biological productivity, may
reflect the lower oxidation potential of sea water there compared to Pacific sites farther to the west.
CFA occurs in 28% of the crust samples analyzed, but not in any crusts from the east (offshore
California) or far north Pacific; if those crusts are excluded, 34% of central and west Pacific samples
contain CFA.
9.2.3 AGES AND GROWTH RATES OF fE-MN CRUSTS
Hydrogenetic Fe-Mn crusts grow at incredibly slow rates of <1 to about 10 mm/Ma, with the most
common rates being from 1 to 6 mm/Ma (Table 9.5; Figure 9.3). These slow growth rates allow
for the adsorption of large quantities of trace metals by the oxyhydroxides at the crust surface.
Growth rates were first measured using either U-series or Be radioisotopes (which give reliable
ages for the outermost 2 and 20 mm of crusts, respectively) or by radiometric or paleontological
TABLE 9.3
Physical Properties of Fe-Mn Crusts and Substrate Rocks
Physical Properties n Fe-Mn Crusts n Sed. Rock Substrate n Basalt Substrate Ref.
Porosity (volume%)
Range 13 52-66 8 18--47 2 15-37 7
Mean 13 61 8 39 2 26 7
41-74 7-69 7-67 118,119
55 35 120
Wet bulk density (g/cm3)
Range 13 1.83-2.04 8 2.04-2.57 2 2.22-2.62 7
Mean 13 1.92 8 2.18 2 2.42 7
Range 18 1.90-2.44 7 1.59-2.68 23 2.06-2.66 121
Mean 18 2.00 7 1.90 23 2.34 121
Dry bulk density (g/cm3)
Range 13 1.18-1.48 8 1.56-2.38 2 1.84--2.46 7
Mean 13 1.29 8 1.78 2 2.15 7
1.31 120
1.04-2.17 1.44--2.92 0.78-2.74 118,119
Grain density (g/cm3)
Range 13 3.03-3.87 7
Mean 13 3.48 7
2.70-3.44 2.54--2.81 2.32-2.95 119
Specific surface area (m2/g)
Range 15 250-381 51
Mean 15 323 51
Compressive strength (MPa) 8.36 3.66-32.6 120
0.5-25.0 36 0.1-52.3 0.37-71.0 118,119
Sea water saturated 5.39-8.92 1.71-12.4 165-219 120
Tensile strength (MPa) 1.75 4.5 120
0.1-2.3 0.1--4.5 0.1-18.9 118,119
Sea water saturated 0.45 0.23-0.48 11.9 120
Cohesive strength (MPa) 2.9 7.8 120
Sea water saturated 1.5 0.4--2.3 26.4 120
Shear strength (MPa) 1.26-2.5 119,122
Angle of internal friction 42° 52° 120
Sea water saturated 76° 61°-77" 76° 120
Young's modulus (GPa) 2.15 0.31-10.1 120
Sea water saturated 3.11--4.25 0.62--4.76 51.3-63.7 120
P-wave velocity (km/s) 2.09-3.39 1.76-5.86 118,119
Range, parallel to bedding 18 2.46--4.19 5 1.80--4.35 23 3.14--5.14 121
Mean, parallel to bedding 18 3.36 5 2.57 23 4.13 121
Range, perpendicular to layers 17 2.07-3.86 4 1.78--4.34 23 3.02--4.93 121
Mean, perpendicular to layers 17 3.16 4 2.56 23 3.99 121
2.26 1.01-3.45 120
Sea water saturated 2.72-2.78 2.07-2.87 5.76-5.80 120
S-wave velocity-saturated (km/s) 1.35-1.83 1.15-1.67 3.46-3.57 120
Gamma radiation (net counts/min)
Range 18 271-800 6 52-137 23 21-366 121
Mean 18 475 6 101 23 146
dash means not reported

TABLE 9.4
Mineralogy of Pacific Fe-Mn Crusts
Dominant Common less Common Uncommon or Uncertain
8-Mn02 CFA, quartz, Phillipsite, goethite, todorokite, Halite, illite, clinoptilolite, lepidocrocite,
(Fe-vernadite), plagioclase, calcite, K-feldspar, pyroxene, manjiroite, manganite, palygorskite, chlorite,
Fe oxyhydroxide smectite opal-A, barite, amphibole, dolomite, stevensite, kutnohorite, mordenite,
(feroxyhyte) magnetite, amorphous natrojarosite, hematite, manganosite,
aluminosilicates maghemite, lithiophorite, analcite
dating of the substrate rock (and assuming that the substrate age is equivalent to the age of the
base of the crust). With both methods, the growth rates and ages of the crusts are extrapolated and
do not take into account changes in growth rates, growth hiatuses, or in the later method, the time
between formation of the substrate rock and the beginning of growth of the crusts. For equatorial
Pacific Cretaceous seamounts, the age of substrate rocks and crusts can vary by as much as 60 Ma,
although in rare circumstances the ages of very thick crusts may approach those of the Cretaceous
substrates. Subsequent to those initial dating techniques, 10Be/9Be ratios were used to date crusts,
and that ratio along with 10Be decay are the most reliable and widely used techniques today.
However, using Be isotope techniques requires that the age of the base of crusts thicker than about
20 mm be determined by extrapolation using the growth rate(s) determined for the outer 20 mm.
Ratios of 87 Sr/86Sr were also used to date crusts by comparing the ratios in the various crust
layers with the ratios that define the Cenozoic sea water curve. 55 That technique (and the other
isotopic techniques) assumes that there has been no post-depositional exchange of the isotopes
between the crust and sea water. Ingram et ai.5 6 showed that in fact there is exchange of Sr with
sea water in some of the most porous, detritus-rich, and CPA-impregnated crust layers. They
provided criteria to choose the most appropriate layers for dating, but, for unknown reasons, using
those criteria still did not produce reliable ages for all the selected crust layers. Consequently, that
technique has been mostly abandoned because Sr is apparently far more mobile in crusts than are
Be, U, and Th. Ratios of 1870sf1 86 0s may provide a reliable dating tool for crusts as old as 65 Ma
by comparing the ratios in various crust layers with ratios that define the Cenozoic sea water curve. 57
However, additional data are required on Os isotopes in the oceans before that technique can be
applied to age-date crusts. Nannofossil biostratigraphy has been used to date crusts from impressions
and molds of nannofossils left in crust layers after replacement of the carbonate by Fe-Mn
oxyhydroxides. 58 ·59 That technique, although reliable, is time consuming to perform and conse-
quently has not been widely used. Finally, empirical equations have been developed to date marine
Fe-Mn oxide deposits by Scott et al., 60 Lyle, 61 Manheim and Lane-Bostwick, 62 and Puteanus and
Halbach, 63 the latter two of which are most commonly used to date hydrogenetic crusts. The Co-
chronometer of Manheim and Lane-Bostwick62 was derived from and applied to both Fe-Mn crusts
and pelagic sediments, whereas the method of Puteanus and Halbach 63 was derived from central
Pacific crusts having Co contents >0.24%. Those equations usually give minimum ages for the
base of crusts and produce growth rates that are generally faster than those determined from isotopic
techniques (compare Tables 9.5 and 9.6), although the Manheim and Lane-Bostwick62 equation
does generally produce rates more in line with those determined by isotopic methods. It is clear
that additional techniques are needed to accurately date thick crusts, and the best opportunity may
be development of Os isotope stratigraphy, although 40Arf3 9Ar, K-Ar, and paleomagnetic reversal
stratigraphy should also be looked into. A significant problem with thick crusts is that the inner
layers were phosphatized by a diagenetic process that promoted the mobilization of many ele-
ments.53·64 However, the remobilization of elements apparently did not affect Nd and Pb isotopic
ratios 65 and also may not have affected Os isotopic ratios.
TABLE 9.5
Isotope-Determined Growth Rates of Hydrogenetic Fe-Mn Crusts
Water Crust Dated Growth Extrap.
Depth Thickness Interval Rates Age
location (m) (mm) (mm) Technique (mm/Ma) (Ma) Ref.
Horizon Guyot 1790 55 3-51 S7Srf"6Sr 3.4-1.6-5.2-1.8-8.8 18 50,55

Horizon Guyot 2400 3 0-2.2 U-series 2.2, 2.5 123
Horizon Guyot 1800 10 0-1.9 U-series 1.1, 2.5, 4.6 4 123
Necker Ridge 2100 51 12-49 87 Sr/86 Sr 5.4-0.7-2.5 23 56
Necker Ridge 2100 25 0-1.4 U-series 2.7, 2.0, 3.1 13 123
Necker Ridge 2350 25 0-0.9 U-series 0.8, 2.0, 3.1 13 123
Marshall Is. 2900 57 1-57 87 Sr/86Sr 1.5-5.0 22 56
Marshall Is. 1863 15 0-1.2 U-series 6.6:6.8, 7.4:7.8 2 66
Marshall Is. 1800 160 0-21 10Be/9Be 1.4-2.7 62 80
Central Pacific 2300 115 0-21 10Be/9Be 2.1 55 80
Central Pacific 1278 30 0-27 lOBe; 10Be/9Be 3.0; 2.7 10 124
25 0-18 10Be; 10Be/9Be 3.2; 3.8 7-8 124
Central Pacific 1809
0-28 10Be; 10Be/9Be 4.0; 3.0 8-10 124
Central Pacific 3196 30
Central Pacific 3280 0-1 U-series 2.7 70
27 0-15 10Be 2.1 13 125
Central Pacific 1510
Central Pacific 1240 12 0-12 10Be 2.5-3.7 4 125
Central Pacific 2100 70 0-8 10Be 1.1 64 125
Central Pacific 1550 50 0-45 10Be 4.3-1.4-4.4 18 125
Same crust 1550 50 0-1 U-series 3.4 15 126
0-10 10Be 125
Central Pacific 5211 1.3
0-11 10Be 1.1 86 89
Central Pacific 2425 95
Central Pacific 1550 55 0-45 10Be 4.3-1.4-4.4 19 63
NW Pacific 1634 40 0-12 10Be 2.0 20 124
NW Pacific 2345 11 0-11 IDBe; 10Be/9Be 8.0; 8.0 124
45 10Be 2-19 8 94
N Equat. Pacific "'4000 0-45
0-17 10Be; 10Bei"Be 1.6; 1.5 31-33 127
NE Pacific 3840 50
230
NE Pacific 4830 250 0-1.5; 0-35; 0-35 Th; 10Be; 10Bei"Be 6.4-1.8; 2.7-4.8; 2.3-3.8 55-65 111
Same crust 4830 250 0-1.4 U-series 6.6-6.1-5.8 40 126
E Equat. Pacific 3500 30 0-1.9 U-series 0.8, 4.6, 2.7 11 123
E Eqnat. Pacific 3710 0-1 U-series 4.3, 9.6 67
Far S Pacific 3700 20 0-2.7 U-series 16 34
SE Pacific 3800 11 0-2.9 U-series 9 34
Cen. S Pacific 4700 3 0-3.0 U-series 5 <1 34
Cen. S Pacific 4020 25 0-24; 0-13 10Be; 26Al 2.8; 2.3 9-11 128
SW Pacific 1120 20 0-16 IDBe; 10Be/9Be 1.0; 1.0 20 124
SW Pacific 5150 0-10 IDBe 1.9 125
South China Sea 1000 3.5 0-3.5 U-series; 10Be 1.5; 1.6 2.3 129
NEAtlantic 38 0-38 10Be 3.0 12 130
NE Atlantic 1500 38 0-38 10 Be 4.5 9 130
Eqnat. E Atlantic 1800 50 0-23 10Be; 10Bei"Be
1.4; 1.3; 36-38 127
Equat. E Atlantic 990 0-0.4 U-series 1.0 131
Equat. E Atlantic 2800 15 0-0.2 U-series 2.0 8 131
Equat. E Atlantic 1800 20 0-0.1 U-series 1.4 14 131
TABLE 9.5
Isotope-Determined Growth Rates of Hydrogenetic Fe-Mn Crusts
Water Crust Dated Growth Ext rap.
Depth Thickness Interval Rates Age
Location (m) (mm) (mm) Technique (mm/Ma) (Ma) Ref.
NW Atlantic 1850 120 0-12 10Be/9Be 1.6 75 132

NW Atlantic 2665 91 0-22 10
Be/9Be 2.4 38 132
SW Atlantic 2394 50 0-41 10Be 1.4 36 124
SW Atlantic 4388 20 0-15 10Be; 10Be/9Be
1.8; 1.3 11-15 124
SE Atlantic 3040 4 0-0.6 U-series 1.2 3 131
Central Indian 5385 30 0-!.3 U-series 2.3 13 133
Central Indian 5250 72 0-1.7 U-series 2.8 26 133
Same crust 5250 72 0-33 10
Be/9Be 2.8 26 132
W Central Indian 5438 35 0-1.2 U-series 2.9:3.8, 7.2:8.4 4-12 67
Same crust 5438 35 0-17 10Bei"Be
1.6 22 132
SW Indian 4325 8 0-0.3 U-Series 1.4 6 131
SW Indian 4052 18 0-18 10
Be; 10Bei"Be 1.9; 1.4 9-13 124
Underside crust 4052 32 0-32 10Be; 10Bei"Be 5.2; 4.0 6-8 124
A dash separating growth rates indicates changes with depth in the crust starting from the surface layer; a semicolon separating
growth rates indicates rates determined by the different techniques listed; growth rates separated by a comma indicate rates
determined by different U-series isotopes; growth rates separated by a colon indicate rates from different profiles in the same
crust; underlined values are preferred by indicated reference; dash means data not available; Extrap. means extrapolated age of
the beginning of crust growth
Various U-series- and Be isotope-generated growth rates of the same crusts may or may not
produce consistent results (Table 9.5). For example, in Table 9.5 the U-series- and Be isotope ratio-
produced growth rates are identical for the same central Indian and South China Sea crusts, but
quite different for the west-central Indian and the northeast Pacific (4830 m) crusts. Those differ-
ences may reflect real differences in growth rates between the outer millimeter and outer centimeters
of the crusts. Different isotopes within the U-series commonly do not produce identical growth
rates, for example, note the east equatorial Pacific sample (3500 m), and may even produce different
rates for different profiles within a single crust (see west-central Indian and Marshall Islands, 1863
m, samples in Table 9.5). Chabaux et al. 66 •67 discussed the efficacy of the various U-series isotopes
and provided criteria to establish whether the U-series isotopes display open- or closed-system
behavior. Beryllium isotope ratios and 10Be decay usually produce similar, but not identical, growth
rates (Table 9.5), and the isotopic ratio may be preferable (see von Blanckenburg et al. 68 for
discussion). The distribution of isotope-determined growth rates does not change with isotopic
technique used or with geographic location (Figure 9.3). No correlation exists in this compiled
dataset between growth rates of the outermost layer of the crusts and water depth of occurrence.
9.2.4 CHEMICAL COMPOSITION
All USGS chemical data in this chapter (Table 9.7) are normalized to 0% Hp- because hygroscopic
water varies markedly depending on analytical conditions. Hygroscopic water can vary up to 30
wt.% and thereby affects the contents of all other elements. Compositions normalized to 0% H20-
can be more meaningfully compared and also more closely represent the grade of the potential ore.
Unfortunately, water contents are not provided in many published reports, so we were unable to
correct compiled data listed in Table 9.7. Mean chemical compositions are provided for crusts that
occur in the areas marked on Figure 9.4, which correspond to the different columns in Table 9.7.
252 Handbook of Mari ne Mineral Deposits
25
Cl GR-Sr-Pac
i] GR-Be-Pac
D GR-U-Pac
• GR-Be-Atl
20 D GR-U-Atl
[J GR-Be-lnd
~ GR-U-Ind
15
(/)
Q)
a..
E
cu
C1) 10
0 5 10 15 20
Growth Rates (mm/Ma)
FIGURE 9.3 Range of isotopically determined growth rates of hydrogenetic Fe-Mn crusts. A hydrothermal
component may exist in the two crusts with the fas test rates; GR = growth rates as determined by Sr, Be, and
U isotopes for the Pacific (Pac), Atlantic (Atl), and Indian (lnd) oceans; sources of data are in Table 9.5
TABLE 9.6
Growth Rates (mm/Ma) Determined from
Empirical Equations
l ocatio n n Equatio n Range Mean Ref
Micronesia 24 MLB 0.9-5.8 2.7 87

Micronesia 24 PH 3.7-130 21.7 87
Micronesia 42 PH 2.1-9.8 5.0 83
Marshall Islands 61 PH 1.5-16.0 4.7 46
Surface scrapes 17 PH 1.7 46
Johnston I. EEZ 97 PH 1.6-10.0 3.8 81
Johnston I. EEZ 12 PH 3.0-32.0 12.0 82
Surface scrapes 14 PH 3.0-13.0 8.0 82
S of Australia 12 MLB 0.5-23.6 8.0 134
MLB = equation of Manheim and Lane-Bostwiclc63; PH = equation

of Puteanus and Halbach62
n
0
o-
TABLE 9.7 Ill
;;+
Mean Chemical Composition of Fe-Mn Crusts from Various Parts of the Pacific Compared to Indian and Atlantic Ocean Crusts ;;o
n
and C-C and Other Abyssal Fe-Mn Nodules ~
,(I)
Far South Far South C--C Other
FSM- Marshall NW of Calif. Ngrth Pacific Pacific Zone Abyssal
3
3
Ill
Palau Is. Marshall Is. johnston I. Borderland NW Pacific Hawaii Pacific 0-25° lat >25° lat Atlantic Indian Nodules Nodules ::J
(1Q
n = 35 n = 77 n = 46 n = 99 n = 60 n = 1478 n = 203 n=5 n = 330 n = 26 n = 21 n=9 n=x n=x Ill
::J
(I)
V>
Fe/Mn 1.02 0.64 0.76 0.72 1.27 0.68 0.77 1.10 0.69 1.00 1.80 !.50 0.27 0.69 (1)
Fewt.% 21.7 16.9 16.7 19.3 21.4 15.1 16.9 19.6 15.8(249) 17.6 22.9 20.2 6.9 12.7 n
2
Mn 21.3 26.3 22.1 26.8 16.8 22.1 22.0 17.8 22.8 17.6 12.7 13.5 25.4 18.5 ~
V>
Si 5.7 3.0 5.4 4.6 11.4 3.7(273) 5.24(79) 5.0 3.5(230) 7.3(7) 5.2 6.8 7.6 8.8 ::J
Na 1.9 1.9 1.7 1.9 2.0 1.6(175) 1.72(79) 2.0 0.97(18) 0.85(17) 1.3 1.8 2.8 2.1 5'-
(I)
AI 1.4 0.70 1.2 0.88 2.1 1.0(328) 1.31(150) 0.7 1.0(247) 3.3(7) 2.2 2.7 2.9 3.0 "'0
Ill
K 0.57 0.53 0.65 0.61 0.14 0.56(177) 0.65(79) 0.5 0.59(99) 0.32(17) 0.5 0.9 1.0 0.93 n
::,.;
Mg 1.2 1.2 1.0 1.2 1.2 1.3(342) 1.21(104) 1.1 1.2(199) 1.3(7) 1.6 1.2 1.7 1.4 ;::;·
Ca 2.9 6.6 3.2 3.4 1.9 4.1(374) 2.5(104) 2.5 3.5(247) 2.3(15) 4.0 2.3 1.7 1.8
Ti 1.1 1.1 1.1 1.3 0.59 0.77(370) 1.2(168) 0.8 1.0(240) 0.79(7) 1.0 0.9 0.53 0.78
p 0.51 1.8 0.63 0.66 0.42 1.2(332) 0.44(76) 0.5 0.83(226) 0.49(7) 0.5 0.3 O.IOA O.IOA
s 0.1(2) 0.2(4) 0.2(2) 0.1(4) 0.3 0.144(1) 0.2(2) 0.2(285) 0.2(10) 0.1(2)
Cl 0.9(2) 0.9(4) 1.1(2) 1.0(4) 0.96(1) 1.0(2) 1.2(285) 1.1(10) 1.3(3)
H20+ 10.3(32) 8.2(73) 8.6 9.3(97) 10.4(56) 6.0(40) 7.5A 7.5A
H2o- 0.0 0.0 0.0 0.0 0.0 14.6(1) O.(l 19.8(3) 0.0 0.0
C0 2 0.75(32) 1.2(73) 0.59 0.69(97) 0.42(56) 0.5(50) 0.16A 0.16A
LOI 36.1(3) 41.2(4) 38.0(2) 30.4(4) 16.4(29) 33.6 36.8(3) 14.9(7) 30.4 30.1
Nippm 3884 5716 3992 4896 3255 5403(1427) 3960 3085 5368 3585 2599 3025 12800 6300
Cu 1023 1057 1369 1185 747 1075(1418) 677 292 1072 713 774 1518 10200 4200
Co 4451 7888 5177 8054 3006 6372(1440) 7774 4323 7534 4485 3515 3346 2400 2400
Zn 751 864 652 771 686 680(335) 684(108) 528 668(57) 777 587 512 1400 900
Ba 1747 2121 1978 2049 4085 1695(266) 1785(104) 1819 1670(130) 1190(10) 1656 1494 2800 2000
Mo 451 569 422 532 379 455(172) 386(76) 737 374(18) 435 334 520 360
Sr 1691 1848 1538 1796 1372 1212(166) 945(51) 1646 995(18) 1371 1066 450 700
Ce 871(32) 1137(73) 1260 1306(97) 1167(56) 1105(48) 1684(50) 1079(35) 696(10) 530A 530A N
VI
""
N
<.11
TABLE 9.7 (continued) ""'

Mean Chemical Composition of Fe-Mn Crusts from Various Parts of the Pacific Compared to Indian and Atlantic Ocean Crusts
and C-C and Other Abyssal Fe-Mn Nodules
Far South Far South C-C Other
FSM- Marshall NWof Calif. North Pacific Pacific Zone Abyssal
Palau Is. Marshall Is. johnston I. Borderland NW Pacific Hawaii Pacific 0-;25° Lat >25' Lat Atlantic Indian Nodules Nodules
n = 35 n = 77 n = 46 n = 99 n = 60 n = 1478 n = 203 n=5 i1 = 33o n = 26 n = 21 n=9 n=x n=x
y ppm 208 267 215 228 175 166(104) 185(51) 204 131(1) 177 154 133A 133A
v 732 724 645 712 616 515(163) 648(104) 748 687(182) 855 573 470 480
Pb 1474 1799 1689 1871 1322 1777(307) 1957(109) !659 741(166) 1654 1133 1027 450 820
Cr 33 15(73) 15.3 9.2(98) 33 22.4(67) 180(16) 17.1(2) 44.2(18) 24.35(6) 26.3(19) 33.9(7) 27 25
Cd 2.8 4.1 3.1 3.5 3.4 4.6(63) 5.8(79) 4.1(2) 3.9(18) 3.6(13) 4.9(4) 12 II
As 279 244 237 289 273 165(106) 1141(76) 245 179(313) 889(10) 312 158 I 59 A I 59 A
Li 4.0(3) 3.6(4) 3.5(2) 15.8(4) 63(2) 5.2(4) 2.3(285) 27.5 16.0(7) 160A 160A
Be 6.3(3) 5.8(4) 7.0(2) 3.7(4) 3(1) 4.8 3.8(18) 8.3 5.7 4A 4A
B 234(2) 129(4) 208(2) 202(4) 115(37) 141(1) 194(2) 148(1) 243(10) 221(3) 273A 273A
Sc 10.1(3) 9.2(4) 9.4(2) 9.6(4) 6.4(64) 5(1) 10.3 13.4(29) 7.91(10) 19.0 14.4 lOA lOA
Ga 10.8(2) 11.2(4) 12.4(2) 16.9(4) 9(1) 13.1(2) 9.0(1) 12.7(11) 14.5(5) 11A llA
Se 0.40(23) 52 A 52A
Br 32.0(2) 32.0(4) 35.9(2) 38.3(4) 43(1) 30.5(2) 10.5(11) 31.75(1 0) 36.5(10) 52.4(3) 0.05A 0.05A
Ag <4 <0.2 <0.2 <0.2 0.717(32) <0.2 <4 <0.2 <0.2 <4 <4 0.10A 0.10A I
OJ
::l
In <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 0.6(1) 0.7(1) 0...
43 3(2) 45.5(4) 45.3(2) 34.7(4) 24.4(47) 39(1) 50.5(2) 32.2(28) 62.7(10) 39.5(3) 37A
u
Sb 31.93(10) 37A 0
0
Hf 7.3(2) 8.4(4) 10.5(2) 9.5(4) 7.4(6) 4.9(1) 6.6(2) 10.1(29) 8.55(7) 14.8(10) 53.8(3) 6A 6A "A
w 102(2) 101(4) 82.8(2) 58.1(4) 93.3(44) 150(1) 136(2) 107(1) 56.44(10) 81.7(10) 82.0(3) 76A 76A s.,
Te 20.1(2) 43.6(4) 20.8(2) 6.6(4) 36(1) 11.2(2) 40(1) 27.4(9) 22.2(2) 216A 216A $:
~
Tl 125(2) 144(4) 130(2) 57.6(4) 186(1) 119(2) 189(1) 81.2(10) 107(3) 169A 169A ::l
(D
Bi 23.7(2) 53.2(4) 41.4(2) 6.2(4) 46.3(1) 12.0(2) 31.8(1) 14.6(10) 23.9(3) 21A 21A
Th 11.4(2) 10.2(4) 17.7(2) 27.9(4) 33.0(12) 37.0 2.1(1) 21.2(10) 54.2 60.2(6) 28A 28A ~
::l
(D
u 12.5(2) 13.3(4) 12.7(2) 8.2(4) 9.6(2) 9.7(1) 16.4(2) 10.2(1) 9.53(8) 11.0(10) 10.3(3) 6.8A 6.8A p;
Rb 14.0(1) 16.5(2) 20.3(3) 14(1) 14.0(3) 15A 15A
0
(D
Zr 649(2) 597(4) 802(2) 662(4) 172(76) 369(1) 611(2) 475(1) 701(10) 722(3) 350 620 -o
49.1(3) 62.8(4) 61.2(2) 41.5(4) 47(1) 33.7(4) 52(1) 0
Nb 54.4 48.6 74A 74A 'J>
;::;:
'J>
-----
n
0
F 0.34(8) 0.013A 0.013A o-
Ill
Cs <2 <2 <2 <2 <2 <2 <2 1.8(3) <2 <2 157A !57A
La 117(17) 237(25) 343(12) 275(14) 251(16) 202(66) 200(35) 185(9) 36A 36A
n
~
Pr 24.9(17) 37.9(25) 60.6(12) 52.5(14) 56.4(15) 106(11) 158A 158A :r-
-n
Nd 108(17) 170(25) 238(12) 210(14) 289(16) 162(25) 226(27) 148(10) 35A 35A [!;
Sm 23.3(17) 30.6(25) 47.0(12) 43.6(14) 50.0(15) 41.6(26) 53.5(28) 23.1(10) 9A 9A 0
Eu 6(17) 7.6(25) 10.7(12) 11.3(14) 12.3(16) 9.90(26) 9.3(35) 72.2(10) 32A 32A 3
Ill
:::l
Gd 26(17) 34.4(25) 49.2(12) 49.3(14) 48.4(15) 26(13) 5.4A 5.4A (JQ
Ill
Tb 4.2(17) 5.3(25) 7.9(12) 7.8(14) 7.8(15) 7.53(26) 6.2(28) 5.99(10) 31A 31A :::l
C1l
Dy 20.1(17) 34.1(21) 47.2(12) 47.8(14) 45.0(15) 57.8(11) 4A 4A "'C1l
Ho 4.7(17) 7.4(25) 9.7(12) 10.0(14) 8.8(16) 6.6(19) 18A 18A n
2
Er 13.1(17) 21.4(25) 27.0(12) 27.8(14) 23.1(15) 31.9(11) 2.3A 2.3A ~
Tm 1.9(17) 3.1(25) 3.9(12) 4.5(14) 3.5(15) 4.3(19) 20A 20A "':::l
Yb 12.3(17) 20.1(25) 23.7(12) 27.0(14) 22.7(16) 17.7(27) 19.8(35) 19.3(10) 1.8A 1.8A g.
C1l
Lu 0.22(17) 3.8(4) 3.8(14) 3.0(15) 3.3(26) 3.3(35) 2.9(10) 0.75A 0.75A v
Ill
Hgppb 10.3(2) 11.0(1) 59.4(1) 360(4) 87(1) 56.6(2) 30.3(1) 154(10) 53.8(3) 0.15A 0.15A n
=+:
Pt 239(32) 634 501(19) 244 82 777(113) 174(25) 97A 97A n·
Pd 1.7(9) 2.6(13) <5.4(19) 2.5(23) 6.2A 6.2A
Rh 11.6(10) 21.6(20) 23.2(19) 14.9(25)
Ru 15.9(10) 14.0(18) 21.3(19)
Ir 4.1(10) 5.9(18) 7.8(19) 9.1A 9.1A
Pacific areas outlined in Figure 9.4; dash means not analyzed; NW Pacific data from Usui and Someya 5 ; Hawaii data from De Carlo et al., 33 Chave eta!., 100 Hein et al., 38 Craig et al., 32
Frank et al. 8 ; South Pacific data from Walter et al., 135 Grau and Kudrass, 91 De Carlo and Fraley, 90 Meylan et al.,13 6 Cronan and Hodkinson, 137 Le Suave et al., 85 Puteanus et al., 93 Cronan
and Hodkinson, 138 Cronan et al., 139 De Carlo et al.,'0 Aplin and Cronan, 97 Lyle et al. 35 ; Far South Pacific data from Exon, 134 Glasby et al., 140 Glasby and Wright, 141 Bolton et al. 14.1 5 ;
C-C Zone (Clarion-Clipperton) and other abyssal nodule data from Haynes et al. 142 : n = 100-1000 for Si, Na, AI, K, Mg, Ca, Ti, Ba, Mo, Sr, V, Cr, Cd, As, P, Ce, Y; n = 1000-2000
Zn, Pb; n = 2000-4000 for Fe, Mn, Ni, Cu, Co; A= means for the entire Pacific 142
USGS data (columns 1-5,8,11,12) normalized to 0% Hp-; n in parentheses differ from those in heading
Hydrogenetic Fe-Mn crusts generally have Fe/Mn ratios between 0.4 and 1.2, most commonly
0.7 ± 0.2, whereas mixed hydrogenetic and hydrothermal crusts and continental margin hydroge-
netic crusts have ratios between 1 and 3, mostly 1.3 to 1.8 (Table 9.7). Cobalt is the metal with
the greatest economic potential in crusts and ranges from about 0.2 to 2.3% in bulk crusts and
averages between 0.3% and 0.8% for various parts of the Pacific (Table 9.7). Cobalt is also
considered the element most characteristic of hydrogenetic precipitation in crusts 12 ·69 and is con-
sidered to maintain a constant flux in the oceans, 70 regardless of water depth. Based on sequential
leaching experiments, Koschinsky and Halbach53 provided the following list of elements with
decreasing degrees of hydrogenesis: Co= Mn>Ni>Zn = Pb = Cu>Fe>Ti. Nickel and Pt are also
considered of economic importance and range up to 1.0% and 1 ppm, respectively, for bulk crusts.
Platinum ranges up to 3 ppm for individual crust layers. 4 •5 Elements most strongly enriched over
abyssal Fe-Mn nodules include Co, Pt, Pb, V, P, Ca, Ti, Sr, Te, and rare earth elements (REEs),
whereas nodules are more enriched in Cu, Ni, Zn, Al, K, and Cd. Crusts are enriched over sea
water in all elements except Br, Cl, and Na; enrichments over sea water between 108 and 10 10 times
include Bi, Co, Mn, Ti, Fe, Te, Pb, and Th, and between 106 and 108 times include Sn, Hf, Zr, AI,
Y, Sc, Tl, Ni, Ca, Nb, In, Cu, Ge, Zn, W, and Ta. Crusts are enriched over lithospheric concentrations
about 30,000 times forTe and 100 to 500 times for Mo, Tl, Sb, Co, Mn, Bi, As, Se, and Pb. Crusts
may not only have an economic potential for Co, Ni, Mn, and Pt, but also forTe, Tl, Zr, P, and Ti.
Elements in crusts have different origins and are associated with different crust mineral
phases. 39•33 A0 •71 Generally, elements are associated with five phases in crusts, o-Mn0 2 , Fe oxyhy-
droxide, detrital or aluminosilicate, CFA, and residual biogenic phases. Manganese, Co, Ni, Cd,
and Mo are invariably associated with the o-Mn0 2 phase. In addition, in more than 40% of the
regions studied, Pb, V, Zn, Na, Ca, Sr, Mg, and Ti are also associated with that phase. Iron and As
are most commonly the only elements associated with the Fe oxyhydroxide phase, although less
commonly V, Cu, Pb, Y, P, Cr, Be, Sr, Ti, and Ce have also been reported to be associated with
that phase. The detrital phase always includes Si, AI, and K, and commonly also Ti, Cr, Mg, Fe,
Na, and Cu. The CFA phase invariably includes Ca, P, and C0 2 , and also commonly Sr andY; Mo,
Ba, Ce, and Zn may also be associated with the CFA phase in some regions. The residual biogenic
phase includes Ba, Sr, Ce, Cu, V, Ca, and Mg, and in some regions also Fe, As, Na, Mo, Y, P, C0 2 ,
Pb, Ti, and Ni. Other phases that have been reported to occur in hydrogenetic crusts from various
regions include Ti hydroxide (Ti, Fe); calcite (Ca, C02 , Sr), chrome spinel (Cr, Mg, As), and
todorokite (Mn, Ni, Cu, Zn). Iron is the most widely distributed element and occurs intermixed in
the o-Mn0 2 phase; is the main constituent in the Fe oxyhydroxide phase; occurs in the detrital
phase in minerals such as pyroxene, amphibole, smectite, magnetite, and spinels; and is in the
residual biogenic phase. The strength of correlations between Fe and other elements depends on
the relative abundance of Fe in the various phases. The CFA phase only occurs in thick crusts
because the inner layers of those crusts have been phosphatized. In thin crusts or the surface scrapes
of thick crusts, Ca, P, and C0 2 are associated with the o-Mn0 2 and/or residual biogenic phases.
CPA-associated elements as well as Pt, Rh, and Ir, generally increase with increasing crust thickness.
In contrast, Co and elements associated with the detrital phase usually decrease with increasing
crust thickness. 12 •71
9.2.4.1 Rare Earth Elements and Yttrium
Hydrogenetic Fe-Mn crusts are characterized by high Y (102 ppm range) and REE (10 3 ppm range)
contents. Concentrations of the trivalent REEs appear to increase in crusts with increasing water
depth of occurrence. 72·73 Irrespective of their specific compositions, hydrogenetic Fe-Mn crusts
from the major oceans show remarkably similar REE patterns. Shale-normalized REE patterns
increase from La to Gd, decrease slightly from Gd to Lu, and commonly show positive anomalies
of La, Ce, Eu, and Gd (Figure 9.5); moreover, Fe-Mn crusts typically display subchondritic Y/Ho
ratios of about 20.74 While Ce isotopic data (138Ce/142Ce) are not yet available for crusts (see
n
0
o-
~
;;:;:-
~
n
:::r
"TT
~
·--· 0
.>" ...... # - ' 3
~
::::;
FAR NORTH
"··:.~ OQ
~
,_-- , J PACIFIC OCEAN ::::;
ro
• •_ . . . . . . . . . . . .J
AMERICA <J'>
ro
n·
ASIA Colifo<ni~ 2
Seam~~--: ~
<J'>
o•N ::::;
,...
:::r
ro
"'0
~
~
n
=+;
C·CZone
i'i'
·--------- Equalor
:, . Marquesas Is.
SOUTH • Q .• ~. Tuwnolu
Fij~·.:
i PACIFIC OCEAN ·.~·; · Ia.
TongaArc ·
FAR SOUTH
PACIFIC OCEAN
1so•w
FIGURE 9.4 Lined boxes are areas with mean Fe-Mn crust compositional data listed in Table 9.7. The far North Pacific data are from the two
indicated boxes, whereas the far South Pacific data cover areas mostly offshore New Zealand and southern Australia; the South Pacific data span
most of the area between South America and the West Pacific arcs and between the equator and 25" South latitude; The crossed-hatched oval area
is the Clarion-Clipperton prime Fe-Mn nodule zone.
Amakawa et al.,7 5 for Fe-Mn nodule data), crust Nd isotopic ratios (' 43 Nd/ 144Nd) cover a range
roughly that of ambient sea water (e.g., Reference 76), indicating that Nd in crusts was derived
from sea water, which in turn was supplied with Nd from fluvial and eolian input from continental
sources.
The apparent bulk coefficients for partitioning of Y and REEs between Fe-Mn crusts and sea
water (KD crust/sea water) are similarly high for La to Sm, decrease from Sm to Lu, display a
strong positive anomaly forCe, and show negative anomalies for La and Gd (Figure 9.6); KD(Y)
is significantly smaller than the KD of any REE. 73 ·74 This indicates that despite the coherent overall
geochemical behavior of Y and REEs, scavenging of those elements from sea water by Fe-Mn
oxyhydroxides is accompanied by pronounced fractionation within the REE series and between Y
and the REE.
Except for redox-sensitive Ce, Y and REE distributions in Fe-Mn crusts represent the exchange
equilibrium between Y and REEs dissolved in sea water andY and REEs sorbed on the surface of
Fe-Mn oxyhydroxide particles. CrustY and REE distributions, therefore, may be described as the
net effect of the two competing processes of solution complexation (predominantly with co~-)
and surface complexation (roughly similar to hydroxide complexation). Although the stabilities of
both types of complexes increase with increasing REE atomic number, the much stronger increase
of the carbonate complexes results in an overall marine particle reactivity that decreases from La
to Lu. 77 Bau et al.7 4 suggested that the negative anomalies for KD(La) and KD(Gd), and the low
value for KD(Y) are due to the anomalously low stability of their respective hydroxide complexes.
Cerium is the only REE that in near-surface environments may occur as a tetravalent ion, and
the contrasting charge and size of Ce4 + compared to its trivalent REE neighbors leads to decoupling
of Ce(IV) from the other REEs. In the marine environment, Ce uptake by Mn and Fe oxyhydroxides
is accompanied by Ce oxidation, which is mediated by microbial processes and/or a surface
catalysis, a reaction that would otherwise be very sluggish. [e.g., Reference 78] Oxidative scav-
enging of Ce results in its preferential uptake and development of positive Ce anomalies on shalec
normalized REE and KD(REE) plots (Figures 9.5 and 9.6). Hence, while uptake of Y(III) and
REEs(III) is governed by the fast kinetics of adsorption-desorption reactions, Ce uptake is addi-
tionally affected by the kinetics of Ce oxidation. The impact of this difference on theY and REE
distributions in Fe-Mn-oxyhydroxide precipitates is most apparent in mixed hydrogenetic-hydro-
thermal Fe-Mn crusts formed from the fallout from hydrothermal plumes. Such mixed-origin crusts
often show distributions ofY(III) and REE(III) that are indistinguishable from those of hydrogenetic
crusts sensu strictu, except they show no or even a negative Ce anomaly and may have less .L:REEs.79
Although part of the Fe and Mn in those crusts is of hydrothermal origin, their Y and REE contents
are derived via scavenging from ambient sea water. Thus, with respect to Fe, Mn, and some trace
metals, those crusts may be of mixed origin, but with respect to Y and REEs they are strictly
hydrogenetic; this clearly indicates that a continuum exists from hydrothermal to hydrogenetic
crusts. Although both types of crusts grow slowly enough to reach exchange equilibrium for Y(III)
and REEs(III), the growth rates of the mixed crusts are too high to allow for a preferential uptake
of Ce that is pronounced enough to compensate for the strong negative Ce anomaly of ambient sea
water.7 9 Consequently, despite oxidative scavenging of Ce in an oxidizing environment as indicated
by positive anomalies for KD(Ce) (Figure 9.6), such crusts show no or negative Ce anomalies in
REE patterns (Figure 9.5).
The short residence time of Nd in the oceans allows for the regional temporal variations of Nd
isotopic ratios recorded during growth of hydrogenetic Fe-Mn crusts to be used as a paleoceano-
graphic proxy. Although such paleoceanographic studies have gained broad attention over recent
years [e.g., References 55 and 80], it should be emphasized that the original Y, REE, and Nd-
isotopic compositions may be obliterated by diagenetic events such as phosphatization. However,
those changes may easily be recognized by a change from subchondritic Y/Ho ratios typical of
hydrogenetic Fe-Mn crusts to superchondritic ratios of up to 50 shown by phosphatized crusts. 64 ·74
100
10
(/)
~
ll..
Gl
a.
E
~ 0.1
-Seawater x 105
--o--Tonga
0.01 -&--Manana
~California
-Johnston
____....._Marshalls
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
-Seawater x 105
--o--Tonga
---tr-- Mar~ana
~California
1000 --+-Johnston
____....._ Marshalls
2 100
~
c
0
..c
0
Gl
a.
E 10
ctS
(/)
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
FIGURE 9.5 Shale (PAAS, Post-Archean Australian shales; 143 )- and chondrite 144-normalized REE patterns
of typical hydrogenetic crusts (Johnston I., California borderland, and Marshall Is.) and mixed hydroge-
netic-hydrothermal crusts (Tonga Arc and Mariana Arc) from the Pacific, compared to the sea water pattern
at 1,250 m water depth. 145
9.5
I=:=~~~~
8.5
:;;c
~
C)
.2
8
7.5
?+--+--~~-+--~~-+--~~-+--~~-+--~;--+~
La Ce Pr Nd Sm Eu Gd Tb Dy Y Ho Er Tm Yb Lu
FIGURE 9.6 Partitioning between nonphosphatized crusts from FSM (Table 9.7) and SCP (South-Central
Pacific data from Bau et al.14 ) and sea water REEs contents averaged from 1000, 1200, 1500, 1600, 1800, and
2000 m water depths. 74
9.2.4.2 Platinum Group Elements
Platinum group elements (PGEs, Pt, Pd, Rh, Ru, Ir) are highly enriched in Fe-Mn crusts over
lithospheric abundances (with the exception of Pd) and over concentrations in Fe-Mn nodules
(Table 9.7). Platinum has been considered a potential by-product of Co mining of crusts and has
mean values for different areas of up to 0.8 ppm and individual sample values of up to 3 ppm. 5•9.46·81 - 85
Rh, Ru, and Ir contents are up to 100, 32, and 22 ppb, respectively, whereas Pd values (1 to 5 ppb)
are usually at or just above lithospheric contents. Most PGEs correlate with crust thickness and
are concentrated in the inner part of thick crusts. Most PGEs commonly correlate inversely with
water depth of occurrence of the crusts. 86
The Marshall Islands EEZ and areas to the north and northwest (Figure 9.4) contain crusts with
the highest PGE contents; crusts from French Polynesia also have high PGE contents. Platinum
contents increase markedly in crusts from the west Pacific compared to the central and east Pacific:
east Pacific (82 ppb), central Pacific (~170 to 250 ppb), and west Pacific (500 to 600 ppb); then
Pt contents decrease again adjacent to the west Pacific arcs (Table 9.7 2). Platinum, Rh, lr, and in
some regions, Ru comprise part of the 8-Mn02 phase, whereas Pd is commonly part of the detrital
phase. 9.46·85 •86 Part of the Ru may also be part of the detrital phase, and both Ir and Ru occur with
the residual biogenic phase in some regions. Platinum, lr, and Rh are derived predominantly from
sea water, whereas Pd and much of the Ru are derived from clastic debris, the remainder of the
Ru being derived from sea water. 9 •46 •81 ·82 •87 The extraterrestrial component (meteorite debris) in bulk
crusts is small. However, meteorite debris may be concentrated locally in the crusts by formation
of dissolution unconformities or by proximity of the crust to meteorite fallout during formation of
the layer. Localized extraterrestrial debris-rich horizons, however, do not alter the overall hydro-
genetic signature of PGEs in crusts. The high Pt and Ir contents in some crust layers occur over
many stratigraphic millimeters of the inner parts of the crusts, which represent millions of years
of accretion of Fe-Mn oxyhydroxides and therefore cannot be explained as the result of meteorite
impacts, as those are essentially instantaneous events and would form only a very thin parting in
crusts. In addition, the PGE ratios are nonchondritic, with Fe-Mn crust compositions showing more
than an order of magnitude more Pt relative to Ir and Rh relative to Ir. The extraterrestrial component
in bulk crusts cannot be more than about 15 to 20% of the total PGEs present. Platinum is a redox-
sensitive element, and its changing concentration probably reflects changing sea water redox
conditions, and diagenesis within the older generation of crusts, including maturation of oxide
phases and phosphatization. 2
The mechanisms of incorporation of hydrogenetic PGEs into crusts are unknown. Both oxida-
tion (Pt2+ <:::> Pt4+ 2 •86) and reduction (Pt2+ <:::> Pt0 84 ) reactions have been proposed as mechanisms
to fix and enrich Pt in crusts. The reduction reaction would be coupled with the oxidation of Mn2+
to Mn4+ after the surface adsorption of Pt and destruction of its tetrachloro complex. 84 However,
as pointed out by Halbach et al., 84 that coupled reaction cannot proceed under present-day dissolved
Mn 2+ sea water concentrations, even in the OMZ where dissolved Mn contents are highest. Con-
sequently, that mechanism does not explain the enrichment of Pt during much of the growth history
of crusts, but may have promoted enrichment of Pt in some of the inner crust layers that formed
when there may have been an expanded and intensified OMZ. Alternatively, Halbach et al. 84
suggested that surface adsorption of the tetrachloro Pt complexes onto positively charged iron
hydroxide particles may occur. However, that explanation is difficult to reconcile with the common
correlation of Pt with the 8-Mn02 phase. Additional research is required to clarify the mechanisms
responsible for the incorporation and enrichment of Pt and the other PGEs in crusts.
9.2.5 PHOSPHATIZATION OF fE-MN CRUSTS
Most thick hydrogenetic Fe-Mn crusts that formed in the open Pacific consist of two growth
generations: a phosphatized older generation and a younger nonphosphatized generation. Phos-
phatization of older crust layers was widespread, and Halbach et ai.3 7 found crusts with an older
phosphatized generation at many locations in the central Pacific. Phosphatized crusts have also
been found on Schumann Seamount, located NE of Hawaii, 59·88 the Hawaiian Archipelago, 89 the
Marshall Islands, 9 and the Johnston Island EEZJ 1 Phosphatized crusts from the South Pacific are
also common in the EEZ of Kiribati, Tuvalu, Cook Islands, and Tuamotu Islands. 40 •48 •49 •64•90-92 Crusts
from relatively deep water (>2,800 m), such as from the Teahitia-Mehetia region93 and from the
Tasman Rise, 14 show only minor or no phosphatization, which is also demonstrated by a decrease
in CPA-associated elements with increasing water depth of crust occurrence (see next section).
Phosphatized crusts are also not found in most continental margin environments, such as in the
EEZ of western North America.
Precipitation of the old crust generation began for various crusts between about 55 and 25 Ma
ago [e.g., References 56, 80, and 94] and was interrupted by several Cenozoic phosphogenic
events. 95 ·96 Phosphogenesis entailed CFA impregnation of the older crust and formation of phos-
phorite partings within and at the top of the older generation of some crusts. Phosphatization took
place by CFA replacement of calcite infiltered into crust pore spaces, by direct precipitation of
CFA in pore space, and by replacement of other crust phases, most commonly Fe oxyhydroxide.
The thickness of the phosphatized layer can be as large as 12 em, and Ca and P concentrations
can increase up to 15 wt.% and 5 wt.%, respectively (Figure 9.7). Growth of the younger crust
generation started during the Miocene and continued to the present without interruption by further
phosphogenic events.
According to Hein et al., 96 two major and possibly several minor Cenozoic episodes of phos-
phogenesis were responsible for formation of phosphorite on equatorial Pacific seamounts. Those
same phosphogenic events are suspected to have phosphatized the older generation of Fe-Mn crusts.
Crust ages would allow for the major phosphogenic events centered on the Eocene-Oligocene (~34
MA) and Oligocene-Miocene boundaries (~24 Ma), as well as the minor middle Miocene event
mm \---··*
--------- ;-..... ----------- _t. .,_----------------------
\.1 ...,lt . ---•--·
20
•• ~------ Mn Ca
40
...
.,:':
l'
·~·.... ---+---·
";,
)
...~
--:...
....
·---~
'•:e
-+- p
60 -~ .. L-- ------ --=-,..._...-

t'
--
,. -- .....
-&~ ...11\.--- -··-···""-::'._-_:------
10 15 20 25 0 10 20 30
concentration (%) concentration (%)
mm
20
40 ------ Si
---+---· Al
60
~·
80~~----.-------,-------~------i
4 0 0.5 1.5
-e-- zn
mm
--+--· Cu
20
~.---------------
•-t
...............
_..... -
40
.. ....
::::::;
------·--·-·. ......··•··
----~~~----
0.05 0.1 0.15 0.20 0.5 1.5

FIGURE 9.7 Element profiles of a strongly phosphatized Fe-Mn crust from the south central Pacific, con-
sisting of an unphosphatized layer, a thick phosphatized layer, and a lower transition layer of phosphatized
crust intergrown with phosphatized limestone substrate. Note in the phosphatized layers a strong increase of
Ca and P contents, a decrease of Fe, AI, Si, and Ti, and a relative enrichment of Ni, Zn, and Cu, compared to Co.
at about 15 Ma, to have affected growth of Pacific Fe-Mn crusts. Extraction and dating of the CFA
from older crust generations support the coeval phosphatization of substrate rocks and crusts (Chan,
Hein, Koschinsky, unpublished data). Hein et ai.9 6 proposed that dissolved phosphorus derived from
intense chemical weathering on continents accumulated in large quantities in the deep sea during
stable, warm climatic conditions when sluggish oceanic circulation prevailed. As Antarctic glaci-
ation expanded and oceanic circulation intensified, the phosphorus-rich deep waters were redistrib-
uted to intermediate water depths by upwelling at the seamounts and may have been temporarily
stored in the OMZ. Koschinsky and Halbach53 proposed that Fe-Mn crust precipitation took place
below the OMZ where Mn2+-rich and 0 2-poor waters mixed with 0 2-rich deep water. Halbach
et al. 12 ·37 and Koschinsky et al. 64 linked the phosphogenesis of crusts with expansion of the OMZ,
which was related to increased surface-water bioproductivity. The suboxic and phosphate-rich water
layer reached down to the crust-covered slopes of the seamounts, inhibiting further crust precipi-
tation and impregnating the crusts with CFA.
Phosphatization of the older Fe-Mn crust layers caused changes in their chemistry and miner-
alogy (Figure 9.7). 63 •64 Besides dilution of the primary crust contents by CFA, certain elements
were added and others removed. Depletion of elements in the phosphatized crust generation
compared to nonphosphatized crust layers occurred in the approximate order
Si>Fe~Al~Th>Ti~Co>Mn~Pb~U. In contrast, Ni, Cu, Zn, Y, REEs, Sr, Pt, and commonly Ba are
enriched in phosphatized crusts. Manganese and Fe were partly fractionated during the dissolution
of Fe-vernadite, and some of the Mn may have been reprecipitated as todorokite, which is more
stable than vernadite under suboxic conditions. The secondary todorokite shows high Ni, Cu, and
Zn contents, which are incorporated in the todorokite lattice in contrast to Co, possibly partly
explaining the relative enrichment of Ni, Cu, and Zn compared to Co in phosphatized crusts
(Figure 9.7), although many phosphatized crusts do not contain todorokite. Metals such as Pb, Sr,
Y, Ba, and REEs may partly precipitate as stable, less soluble phosphate phases during phosphati-
zation, whereas Ba forms barite. Iron released from Fe vernadite may partly reprecipitate as goethite
or as Fe- and Ti-rich laminae. However, general depletions of all hydroxide-dominated elements
(Fe, Al, Si, Ti, Th) are evident in phosphatized crusts (Figure 9.7).
Because primary crust precipitates were reorganized during phosphatization, the phosphatized
layers may not reflect sea water composition at the time of initial crust formation. Consequently,
isotopic and chemical (empirical equations) methods of dating crusts and the use of phosphatized
Fe-Mn crusts in paleoceanographic studies should be done with caution.
9.2.6 LocAL AND REGIONAL VARIATIONS IN CoMPOSITION
The Fe/Mn ratios are lowest in crusts from the central and west-central Pacific and highest in crusts
collected near continental margins and volcanic arcs in the Pacific and throughout the Atlantic and
Indian Oceans. The detrital-associated elements (Si, Al) increase in crusts with proximity to
continental margins (off western North America, far South Pacific) and volcanic arcs in the West
Pacific, which have contents equivalent to those found in most crusts from the Atlantic and Indian
Oceans (Table 9.7; Figure 9.8A). Within the central Pacific region, detrital-related elements are
most abundant in the eastern part, along the Hawaiian and Line Islands. In contrast, Co, Ni, and
Pt contents are highest in crusts from the central Pacific and lowest in crusts from along the
spreading centers in the southeast Pacific, the continental margins, and along the volcanic arcs of
the west Pacific (Table 9.7; Figure 9.8B, C). 39 A7 •62 •71 Cobalt contents in Atlantic and Indian Ocean
crusts are roughly equivalent to those in crusts from along the western margin of North America,
but the Atlantic and Indian Ocean crusts generally have relatively more Fe (Figure 9.8B, C). Copper
contents follow the trends for Co, Ni, and Pt, except for the Indian Ocean, where the highest mean
value (1,518 ppm) is found. The reason for those high values is the much greater mean water depth
for crusts collected from the Indian Ocean. Mean Ba content is about twice as high in northeast
Pacific crusts as anywhere else in the global oceans. Those high Ba contents are the result of intense
upwelling and high bioproductivity in that region? (also Hein et al., unpublished data). Trends for
mean Ti contents do not follow those of Al and Si, but rather follow those of Co, Ni, and Pt, which
supports the idea that much of the Ti in crusts is a hydrogenetic phase. 9 •53 •97 Another interesting
distribution is seen with P because it is not most enriched in areas where upwelling and biopro-
ductivity are greatest (East Pacific, east equatorial Pacific), but rather is highest in crusts from the
Marshall Islands and the northwest Pacific (Figure 9.8A; see also Hein et al. 71 ). It is not clear why
P does not reflect the high bioproductivity in the East Pacific as does Ba, or why CFA does not
occur in crusts from that region. Cerium is generally lower in South Pacific crusts than it is in
A. Mn
• FSM-Palau
• Marshall Islands
+ NW of Marshall Islands
o Johnston Island
X California Borderland
. +.
0
0 o Far North Pacific Ocean
0 Atlantic Ocean
X
• Indian Ocean
o.
p X 10 AI x 10
B. (Co+Ni+Cu) x 10
• FSM-Palau
• Marshall Islands
+ NW of Marshall Islands
o Johnston Island
X California Borderland
o Far North Pacific Ocean
0 Atlantic Ocean
• Indian Ocean
~·
0 • xr:JI
Fe Mn
C (Co+Ni+Cu) X 10
• Pacific Ocean, n=322
o Atlantic/Indian Ocean, n=30
Fe Mn
FIGURE 9.8 (A) Mn-PxlO-AlxlO ternary diagram for mean compositions of USGS data listed in Table 9.7;
note that crusts from all areas except the Marshall Islands have about the same relative amounts of P, but
highly variable relative amounts of Al and Mn, depending on proximity to continental margins for Al and to
the equatorial Pacific for Mn. (B) Mn-Fe-(Co+Ni+Cu)xlO ternary diagram after Bonatti et al.l 46 for data as
in (A); Note that crusts in proximity to continental margins and volcanic arcs are relatively enriched in Fe and
depleted in trace metals, whereas central Pacific crusts are relatively enriched in Mn and trace metals, with
the Marshall Islands crusts showing the greatest enrichments. (C) Complete dataset used in the means in B.
North Pacific crusts. Those elements concentrated in crusts by oxidation reactions (Co, Ce, Tl, and
maybe Pb, Ti, and Pt) should be highest in the West Pacific where sea water oxygen contents are
the highest. However, that relationship is only clearly defined for Pt and the Ce anomaly, probably
because regional patterns are somewhat masked by local conditions where upwelling around
seamounts mixes various water layers. 2
Manganese, manganophile elements, and the Fe oxyhydroxide phase generally decrease,

whereas detrital phase-related elements (Si, AI, Fe, Y) increase with increasing latitude. 38 •71 •98 The
intensification of the OMZ in the equatorial zone of high bioproductivity allows for greater amounts
of Mn remaining in solution in sea water and slower growth rates of crusts. The increase in Fe, Si,
AI, andY to the north is partly due to an increased supply of detritus by the trade winds. The same
trends in Mn and manganophile elements should occur with longitude (increasing to the east) in
the equatorial region because regional bioproductivity increases in that direction. However, a paucity
of seamounts exists between Hawaii and North America, so that trend cannot be confirmed Pacific-
wide; regardless, the trend is generally poorly developed regionally (e.g., Reference 87); contents
of manganophile elements in California continental margin crusts are diluted by detrital and
biogenic inputs, which ameliorates the increased o-Mn02-related elements expected to occur there.
The residual biogenic phase elements generally increase with proximity to the equatorial zone of
high bioproductivity and in the eastern Pacific, where productivity is yet higher. 71
Manganese, manganophile elements, and CPA-related elements decrease, whereas Fe, Cu, and
detrital-related elements increase with increasing water depth of occurrence of crusts. 12•33,37,3&,98
Cobalt and other manganophile elements are enriched more than Mn is in shallow water. 97 Those
relationships have been explained by an enhanced supply of dissolved Mn2+ in the OMZ (about
300 to 1500 m) and an increased supply of Fe in deeper waters (3,500 to 4,500) near the CCD as
the result of dissolution of biogenic calcite. 95 •99 However, the supply of significant amounts of Fe
by biocalcite has been contested, 33 ·97 and much of the increased Fe, AI, and Si with increasing water
depth may be the result of an increased supply of detrital phases. Enhanced Mn and Co supply to
the OMZ may result from advection of metals released from anoxic continental margin sediments
to the east. 97 •100 However, even though that explanation may be valid for some east-central Pacific
crusts, it apparently does not apply to crusts forming farther to the south and west. 62
9.3 Fe-Mn CRUST FORMATION

Even though Fe-Mn crusts form by hydrogenetic precipitation, the exact mechanisms of metal
enrichments in the water column and at the crust surface are poorly understood. The ultimate
sources of metals to the oceans are river and eolian input, hydrothermal input, weathering of basalts,
release of metals from sediments, and extraterrestrial input. Elements in sea water may occur in
their elemental form or as inorganic and organic complexes. Those complexes may in turn form
colloids that interact with each other and with other dissolved metals (e.g., References 53, 74, and
101). Thermodynamic, surface-chemical, and colloidal-chemical models show that most hydroge-
netic elements in crusts occur as inorganic complexes in sea water (Figure 9.9). 53 Hydrated cations
(Co, Ni, Zn, Pb, Cd, Tl, etc.) are attracted to the negatively charged surface of Mn oxyhydroxides,
whereas anions and elements that form large complexes with low charge-density (V, As, P, Zr, Hf,
etc.) are attracted to the slightly positive charge of Fe hydroxide surfaces. _
Mixed Fe and Mn colloids with adsorbed metals precipitate onto hard-rock surfaces as poorly
crystalline or amorphous oxyhydroxides, probably through bacterially mediated catalytic processes.
Continued crust accretion after precipitation of that first molecular layer is autocatalytic but is
probably enhanced to some degree by bacterial processes. Additional metals are incorporated into
the deposits either by coprecipitation, or by diffusion of the adsorbed ions into the Mn and Fe
oxyhydroxide crystal lattices. Cobalt is strongly enriched in hydrogenetic crusts because it is
oxidized from Co 2+ to the less soluble Co 3+ at the crust surface, possibly through a disproportionation
reaction. 102 Lead, Ti, and Tl, as well as Ce are also highly enriched in hydrogenetic deposits,
probably by a similar oxidation mechanism; 53 •72•97 however, sequential leaching studies suggested
that much of the Pb may not be incorporated by that mechanism. 53
Concentrations of elements in sea water are generally reflected in their concentrations in crusts,
although there are many complicating factors. For example, Cu, Ni, and Zn occur in comparable
concentrations in sea water, 103 yet Ni is much more enriched in crusts than either Cu or Zn. Copper
FIGURE 9.9 Colloidal-chemical model for formation of hydrogenetic crusts showing formation of com-
plexes and colloidal phases, adsorption of metals, the pH of the zero point of charge (zpc), and precipitation
of oxides on seamount rock substrates. (Modified from Koschinsky, A. and Halbach, P., Sequential leaching
of ferromanganese precipitates: Genetic implications, Geochimica et Cosmochimica Acta, 59, 5113, 1995.)
contents may be relatively low in hydrogenetic crusts because it occurs mostly in an organically
bound form in deep sea water, which is not readily incorporated into Fe and Mn metal oxyhydrox-
ides.104 Zinc contents may be relatively low in crusts compared to Ni because little Zn may be
adsorbed onto crusts after precipitation of the oxyhydroxides, which follows the order of
Ni>Co>Zn>Cu. 104 In contrast, comparable proportions of Mn:Fe:Co exist in deep sea water (0.5
to 1.0:1:0.02 to 0.05 103 .1°5) as exist in Fe-Mn crusts (0.6 to 1.6:1:0.02 to 0.05; Tables 9.1 and 9.7).
The dominant controls on the concentration of elements in hydrogenetic crusts are the concen-
tration of each element in sea water; element-particle reactivity; element residence times in sea
water; the absolute and relative amounts of Fe and Mn in the crusts, which in tum are related to
their abundance and ratio in colloidal floes in sea water; 97 the colloid surface charge and types of
complexing agents, which will determine the amount of scavenging within the water column;53 the
degree of oxidation ofMn0 2 (0/Mn)- the greater the degree of oxidation the greater the adsorption
capacity- which in turn depends on the oxygen content and pH of sea water; 106 the amount of
surface area available for accretion, which at the surface of growing crusts is extremely large (mean
300 m2/g), but which decreases with maturation of crusts; 51 the amount of dilution by detrital
minerals and diagenetic phases; and growth rates. Elements that form carbonate complexes in sea
water behave independently from those that form hydroxide complexes, which indicates their
different modes of removal from sea water onto crust surfaces. 74 For example, Y and REEs are
removed by formation of surface complexes, whereas Ti is probably removed by precipitation as
a hydroxide. Very slow growth rates promote enrichment of minor elements by allowing time for
extensive scavenging by the major oxyhydroxides. Accretion of oxyhydroxides will be slower where
the OMZ intersects the seafloor than it will be above and below that zone, because Mn is more
soluble in low-oxygen sea water. Crusts exposed at the seafloor may not necessarily be actively
accreting oxyhydroxides 66 because of mechanical erosion or, less commonly in the contemporary
oceans, because of sea water oxygen contents that are insufficient to permit oxidation of the major
metals.
9.4 PALEOCEANOGRAPHIC AND PALEOCLIMATE STUDIES

The composition of Fe-Mn crusts reflects the composition of sea water at the time the metals
precipitated. Therefore, Fe-Mn crusts are condensed stratigraphic sections in which several
stratigraphic millimeters can represent a million years of oceanic history; the crusts reliably store
the records of that history. Our ability to use crusts for paleoceanographic studies depends on
the accuracy of dating techniques (see Section 9.2.3 on Ages and Growth Rates). Detailed
sampling of crusts can possibly be done with a resolution as good as 3000 y, 107 but more
commonly with resolutions of lOs to lOOs of thousands of years. 65 •80 Apparently, the content of
most elements in crusts in addition to crust textures record local oceanographic conditions,
whereas isotopic ratios of elements record regional or global conditions. Crusts should house a
wide variety of records, including paleosea water chemistry and isotopes, paleocirculation pat-
terns (isotopic tracers), paleowinds from incorporated eolian grains, paleoerosion rates of con-
tinents (isotopic tracers), history of hydrothermal input (isotopic and chemical tracers), paleo-
pH and temperature (isotopic tracers), and history of extraterrestrial input (isotopic and chemical
tracers). The isotopic tracers that have been used so far include Be, Nd, Pb, Hf, Os, Li, B, and
U-series isotopes and chemical tracers such as Ba, Co, Pt, and Li. 67 •68 •76 •108- 110 For example, deep
ocean circulation today is characterized by creation of deep water in the North Atlantic that has
a characteristic isotopic composition (Figure 9.10). Then, that deep water travels south and then
east into the Indian Ocean and finally farther east into the Pacific, where its fate in the far North
Pacific is poorly understood. The isotopic compositions of Nd, Pb, and Be change along that
route and temporal changes in the pattern of deep water flow can be mapped via isotopic
signatures of those elements in crusts distributed globally. 68 •76,tos
Many advantages exist in using crust stratigraphy for paleoceanographic studies rather than
using carbonate sections in the deep sea, the heretofore common method of addressing paleocean-
ographic problems. Crusts are more widely distributed geographically and with water depth than
are thick carbonate sections; crusts have higher concentrations of most elements and their isotopes;
crusts are less prone to diagenetic isotopic exchange; and crusts have less detrital contamination.
In contrast, carbonate sections are easier to date and generally have better temporal resolution.
eNd= -3
206PbJ204pb = 18.7
1oeePBe =1.1x1o·7
FIGURE 9.10 Schematic representation of deep water flow in the oceans and characteristic changes in its Be, Pb, and Nd isotopic composition. (Data
from Albarede, F. and Goldstein, S. L., World map of Nd isotopes in seafloor ferromanganese deposits, Geology, 20, 761, 1992; von Blanckenburg, F.,
O'Nions, R. K., Belshaw, N. S., Gibb, A., and Hein, J. R., Global distribution of beryllium isotopes in deep ocean water as derived from Fe-Mn crusts, 0
(1)
Earth and Planetary Science Letters, 141,213, 1996; von Blanckenburg, F., O'Nions, R. K., and Hein, J. R., Distribution and sources of pre-anthropogenic -o
0
lead isotopes in deep ocean water from Fe-Mn crusts, Geochimica et Cosmochimica Acta, 60, 4957, 1996.) "'
;:;:
"'
Crust element contents and crust textures have been used with limited success for the past 15
years in understanding paleoceanographic processes. 50•92 •99 •111 However, the isotopic tracer studies
of crusts began only in the mid 1990s and offer a unique way to solve important problems in
paleoceanography.
9.5 RESOURCE, TECHNOLOGY, AND ECONOMIC CONSIDERATIONS

During the early stages of exploration for Co-rich crusts, the main objectives are to find areally
extensive, thick, and high-grade deposits. In later stages of exploration, the objective is to map the
precise range of minable crusts. Consequently, there is a continuing refinement of detail secured
on each seamount by successive iterations of sampling and surveying. The main field operations
used for exploration include continuous mapping of seamounts using multibeam echosounder, side-
scan sonar, and single- or multichannel seismic systems; systematic sampling using dredges and
corers; bottom photo coverage; water column sampling; and analysis of crusts and substrates for
composition and physical properties. Operations may also include collecting biological and eco-
logical information that can be used in future environmental impact studies. These exploration
activities require use of a large and sophisticated research vessel because of the large number of
bottom acoustic beacons, large towed equipment, and volume of samples collected. During
advanced stages of exploration, manned submersibles or ROV s may be used for closer observations
and sampling of seamount deposits.
Based on data collected during the first six years of Fe-Mn crust studies, Hein et al. 9 listed 11
criteria for the exploration for and exploitation of Fe-Mn crusts: (1) large volcanic edifices shallower
than 1,000 to 1,500 m; (2) substrates older than 20 Ma; (3) areas of strong and persistent current
activity; (4) volcanic structures not capped by large atolls or reefs; (5) a shallow and well-developed
OMZ; (6) slope stability; (7) absence of local volcanism; and (8) areas isolated from input of
abundant fluvial and eolian debris. Exploitation criteria included (9) average Co contents ~0.8%;
(10) average crust thicknesses ~40 mm; and (11) subdued small-scale topography. Depending on
the mining systems used, crust thickness may turn out to be more important than grade; if true,
then the crust thickness criterion would increase and grade criterion would decrease. That relation-
ship is inevitable because Co grade decreases with increasing crust thickness.
9.5.1 MINING SYSTEMS
Crust mining is similar to Fe-Mn nodule mining in some ways and considerably different in others.
Nodule mining concepts developed by mining consortia in the last decades consist of a hydraulic
dredge and a slurry lift system. 112•113 Recovery of the nodules is relatively easy because they sit on
a soft sediment substrate. In contrast, Fe-Mn crusts are weakly to strongly attached to substrate
rock. The key to successful mining will be the ability to attain efficient crust recovery while avoiding
collection of substrate rock, which would significantly dilute crust grade. Five crust mining functions
include fragmentation, crushing, lifting, pickup, and separation. The proposed method for crust
recovery 41 consists of a bottom-crawling vehicle attached to a surface mining vessel by means of
a hydraulic pipe lift system and an electrical umbilical. The mining machine provides its own
propulsion and travels at a speed of about 20 cm/s. The miner has articulating cutting devices that
would allow crusts to be fragmented, while minimizing the amount of substrate collected
(Figure 9.11). The hydraulic suction dredges are similar to trailing suction dredge heads commonly
used with hopper dredges for sand and gravel mining. About 95% of the fragmented material would
be picked up and processed through a gravity separator prior to lifting. Material throughput for the
base-case mining scenario41 is 1,000,000 t/y. That scenario allows 80% fragmentation efficiency
and 25% dilution of crust with substrate during fragmentation as reasonable miner capabilities.
The net recovery of crusts depends on fragmentation efficiency, pickup efficiency, and separation
MAJOR DIMENSIONS·
Length 13m
Width : 8m
Height : 6m Separator
Weight : 100 t
Installed Power : 900 KW
Diffusers
Power Tracks
Hydraulic
Dredge Head
Cutter Heads
FIGURE 9.11 Schematic representation of a deep-sea mining vehicle for Fe-Mn crusts. (From DOI-MMS
and DPED-State of Hawaii, Proposed marine mineral lease sale: Exclusive economic zone, adjacent to Hawaii
and Johnston Island, Final Environmental Impact Statement, vols. I & II, 1990; designed by J. E. Halkyard,
OTC Corporation).
losses. Fragmentation efficiencies depend on microtopography and depth of the cut. Pickup effi-
ciencies also depend on seafloor roughness, but to a lesser extent than fragmentation efficiency,
and on the size of fragmented particles and type of pickup device.
The Japan Resource Association 114 studied the applicability of a continuous line bucket (CLB)
system as a method of crust mining. The CLB could be competitive in an area where crusts are
easily separated from substrate rock, or where the substrate is soft enough to be removed by
washing. 115 While there is some merit in the CLB 's simplicity, the most likely commercial crust
mining systems will probably use hydraulic lift together with a mechanical fragmentation system
attached to a self-propelled collector. That type of system has a better likelihood of efficient crust
recovery and substrate separation. The economics of ocean mining favors efficient mining tech-
niques even at a cost penalty over simpler but less efficient systems. Some new and innovative
systems that have been suggested for Fe-Mn crust mining include water jet stripping of crusts from
the substrate, and in situ leaching techniques. Both suggestions offer promise and need to be further
explored.
9.5.2 EcoNOMICS
The importance of metals contained in Fe-Mn crusts to the world economy is reflected in their
patterns of consumption. 116 The primary uses of Mn, Co, and Ni are in the manufacture of steel to
which they provide unique characteristics. Cobalt is also used in the electrical, communications,
aerospace, and engine and tool manufacturing industries, and its radioisotope is used in modern
diagnostic and therapeutic medicine. Nickel is also used in chemical plants, petroleum refineries,
electrical appliances, and motor vehicles. Supplies of these metals and other rare metals found in
crusts are essential for maintaining the efficiency of modern industrial societies and in improving
the standard of living in the 21st century.
TABLE 9.8
Fe-Mn Crust Mining and Processing,
Estimated Annual Revenues and Costs
Output Prices Amount
Commodity (t) (1985 dollars) ($X 10 6)
Pyrometallurgical Process Revenues

Cobalt 5,710 11.70 133.6
Nickel 2,990 3.29 19.7
Copper 120 0.65 0.2
Fe-Mn 195,000 0.30 117.0
Total Revenues 207.5
Costs -291.0
Net Revenues -20.5
Hydrometallurgical Process Revenues

Cobalt 5,365 11.70 125.5
Nickel 2,900 3.29 19.1
Copper 420 0.65 0.5
Total Revenues 145.1
Costs -204.0
Net Revenues -58.9
Source: DOI-MMS and DPED-State of Hawaii, Proposed

marine mineral lease sale: Exclusive economic zone, adjacent
to Hawaii and Johnston Island, Final Environmental Impact
Statement, vols. I & II, 1990.
Most mineral industry analysts agree that the supply of Co is more uncertain than the supply
of the other crust metals because most Co production has come heretofore from Zaire (57%) and
Zambia (11 %). This uncertainty in supply has caused industry to look for alternatives to Co,
resulting in only a modest growth in the Co market over the past decade, and consequently, relatively
low Co prices. If substantial alternative sources of Co supply are developed, there should be a
greater incentive to reintroduce Co back into products and expand the market. ll7
A preliminary estimate of the economics of crust mining and processing operations for the State
of Hawaii41 indicated that crust mining and processing is not economical under present scenarios
(Table 9.8). The minimum required return on the investment of US$750 million in mining and pro-
cessing is on the order of US$100 million per year. Neither pyrometallurgical or hydrometallurgical
processing options would be commercially viable under the current scenario of 700,000 dry t/y of crust
production. 117 Outside of Japan, there has been limited research and development on mining technol-
ogies for crusts, and therefore economic analysis at this early stage is highly speculative. Despite these
difficulties, China has held discussions with the State of Hawaii about the possibility of placing a plant
on the islands for processing Fe-Mn oxide materials. Several evolving circumstances may change the
economic environment and promote crust mining in the oceans, for example land-use priorities, fresh-
water issues, and environmental concerns in areas of mining on land.
There is a growing recognition that Co-rich Fe-Mn crusts are an important potential resource.
Accordingly, it is necessary to fill the information gap concerning various aspects of crust mining
through research, exploration, and technology development. The Marshall Islands, Johnston I. (U.S.
EEZ), Kiribati, Federated States of Micronesia, and French Polynesia are the Pacific Island areas
with the greatest known potential for crust resources. At present, the Marshall Islands EEZ has
been the area most extensively studied.
9.6 RESEARCH FOR THE 21ST CENTURY

At the end of the 20th century, 20 years will have gone into studies of Co-rich Fe-Mn crusts.
However, many questions remain to be answered and we recommend that research in the 21st
century should include:
• Detailed mapping of selected seamounts, including analysis of microtopography

• Development of better dating techniques for crusts
• Determining the oceanographic and geologic conditions that produce very thick crusts
• Determining what controls the concentration of PGEs and other rare elements in crusts
• Determining how much burial by sediment is required to affect crust growth; and to what
extent crusts occur on seamounts under a thin blanket of sediment
• Determining the role of microbiota in the formation and growth of crusts
• Determining the extent and significance of organic complexing of metals that comprise
crusts
• Studying currents, internal tides, and upwelling around seamounts
• Complete environmental and ecological studies of seamount communities
• Determining to what extent the chemical and isotopic compositions of crusts reflect
paleoceanographic and paleoclimatic conditions, and complete deciphering of those
records
• Development of new mining technologies and processes of extractive metallurgy
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Handbook of

Library of Congress Cataloging-in-Publication Data

Handbook of marine mineral deposits I editor, DavidS. Cronan.

© 2000 by CRC Press LLC

No claim to original U.S. Government works

Fe/Mn 1.2 57 0.7 0.04 5100

Mn 5.0 X 10-9 0.095 26 47 0.01

Fe 6.0 X 10-9 5.4 19 1.8 51

Co 1.0 X JO-IO 2.5 X 10-3 0.70 0.017 <2.3 X 10-4

Ni 5.0 X 10-8 8.0 X 10-3 0.48 0.10 0.024

Pt 2.4 X 10-ll 4.0 X 10-7 5 X 10-5 3.0 X J0-6 1.1 x w-6

Types in Bold :::l

volcanic breccia; 5Mostly cement for breccia, sandstone, and siltstone

9.1.3 HISTORICAL PERSPECTIVE

9.2 FE-MN CRUST CHARACTERISTICS

An important consideration in the exploration and exploitation of potential crust resources is

9.2.3 AGES AND GROWTH RATES OF fE-MN CRUSTS

dash means not reported

Horizon Guyot 1790 55 3-51 S7Srf"6Sr 3.4-1.6-5.2-1.8-8.8 18 50,55

NW Atlantic 1850 120 0-12 10Be/9Be 1.6 75 132

9.2.4 CHEMICAL COMPOSITION

Micronesia 24 MLB 0.9-5.8 2.7 87

MLB = equation of Manheim and Lane-Bostwiclc63; PH = equation

TABLE 9.7 (continued) ""'

9.2.4.1 Rare Earth Elements and Yttrium

9.2.4.2 Platinum Group Elements

9.2.5 PHOSPHATIZATION OF fE-MN CRUSTS

60 -~ .. L-- ------ --=-,..._...-

0.05 0.1 0.15 0.20 0.5 1.5

9.2.6 LocAL AND REGIONAL VARIATIONS IN CoMPOSITION

Manganese, manganophile elements, and the Fe oxyhydroxide phase generally decrease,

9.3 Fe-Mn CRUST FORMATION

9.4 PALEOCEANOGRAPHIC AND PALEOCLIMATE STUDIES

9.5 RESOURCE, TECHNOLOGY, AND ECONOMIC CONSIDERATIONS

9.5.1 MINING SYSTEMS

Pyrometallurgical Process Revenues

Hydrometallurgical Process Revenues

Source: DOI-MMS and DPED-State of Hawaii, Proposed

9.6 RESEARCH FOR THE 21ST CENTURY

• Detailed mapping of selected seamounts, including analysis of microtopography

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