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Geochemistry, Geophysics, Geosystems

RESEARCH ARTICLE Phosphorites, Co-rich Mn nodules, and Fe-Mn crusts from
10.1002/2015GC005861
Galicia Bank, NE Atlantic: Reflections of Cenozoic
Key Points: tectonics and paleoceanography
 Ferromanganese and phosphorite
mineral deposits discovered on Francisco Javier Gonzalez1, Luis Somoza1, James R. Hein2, Teresa Medialdea1, Ricardo Leo
 n1,
Galicia Bank Victoriano Urgorri3, Jes
us Reyes1, and Juan Antonio Martın-Rubı1
 Paragenesis are controlled by
hydrogenous, diagenetic, and
1
hydrothermal processes Geological Survey of Spain, IGME, Madrid, Spain, 2U. S. Geological Survey, Pacific Coastal and Marine Science Center,
 Cenozoic tectonism and
Santa Cruz, California, USA, 3Estaci
on de Bioloxıa Mari~
na da Gra~
na, Universidade de Santiago de Compostela, Ferrol,
paleoceanography are recorded on
the mineralizations Spain

Supporting Information:
 Supporting Information S1
Abstract A wide variety of marine mineral deposits were recovered from 750 to 1400 m water
 Figure S1
depths on Galicia Bank, Iberian margin. Mineral deposits include: (1) carbonate fluorapatite phosphor-
 Figure S2 ite slabs and nodules that replaced limestone and preserved original protolith fabric. (2) Ferromanga-
 Figure S3
nese vernadite crusts with high Mn and Fe (Mn/Fe 5 1) contents, and thick stratabound layers
consisting mainly of Mn (up to 27% MnO) and Fe (15% Fe2O3), which impregnated and replaced the
Correspondence to: phosphorite. (3) Co-rich Mn nodules are composed of romanechite and todorokite laminae. Mn-rich
F. J. Gonzalez,
[email protected] layers (up to 58% MnO) contain up to 1.8% Co. (4) Goethite nodules with Fe up to 67% Fe2O3 have
low Mn and trace metals. We interpret this mineralization paragenesis to be related to major
Citation: changes in oceanographic and tectonic regimes. Three phosphatization generations formed hard-
Gonzalez, F. J., L. Somoza, J. R. Hein, grounds dated by 87Sr/86Sr isotopes as late Oligocene, early Miocene, and latest early Miocene. Dur-
T. Medialdea, R. Le on, V. Urgorri, ing the latest early Miocene, the hardground was fractured and breached due to regional intraplate
J. Reyes, and J. A. Martın-Rubı (2016),
Phosphorites, Co-rich Mn nodules, and tectonism, which was coeval with a widespread regional erosional unconformity. The stratabound
Fe-Mn crusts from Galicia Bank, layers and Co-rich manganese nodules were derived from low-temperature geothermally driven
NE Atlantic: Reflections of Cenozoic hydrothermal fluids, with fluid conduits along reactivated faults. During middle and late Miocene, the
tectonics and paleoceanography,
Geochem. Geophys. Geosyst., 17, 346– introduction of vigorous deep water flow from the Arctic generated growth of hydrogenetic ferro-
374, doi:10.1002/2015GC005861. manganese crusts. Finally, growth of diagenetic Fe-rich nodules (late Pliocene) was promoted by the
introduction of hypersaline Mediterranean Outflow Water into the Atlantic Ocean.
Received 17 APR 2015
Accepted 19 JAN 2016
Accepted article online 29 JAN 2016
Published online 10 FEB 2016
1. Introduction
Marine mineral deposits are metal-rich chemical sediments that are archives for paleoceanographic proxies
and are potential mineral resources. Several main mineral deposits are found on the seafloor: Fe-Mn crusts
and nodules, phosphorites, and seafloor massive sulphides [e.g., Rona, 2008; Hein et al., 2013]. Traditionally,
marine precipitates are defined as purely hydrogenetic when all constituents are derived from cold sea-
water, as diagenetic when all constituents are derived from cold sediment pore water, and as hydrothermal
when precipitation occurs in the vicinity of hydrothermal vent sites from fluids with temperatures higher
than ambient bottom waters [Bau et al., 2014]. Hydrogenetic Fe-Mn crusts occur throughout the global
ocean on seamounts, ridges, and plateaus where currents have kept the rocks free of sediment for millions
of years [e.g., Aplin and Cronan, 1985; De Carlo et al., 1987; Pichocki and Hoffert, 1987; Usui and Someya,
1997; Hein et al., 2000]. Some ferromanganese (Fe-Mn) crusts and nodules exhibit a mixed origin, primarily
either hydrothermal-hydrogenetic or hydrogenetic-diagenetic [e.g., Baturin and Drovetsova, 2014]. In discus-
sions of Cenozoic marine Fe-Mn oxyhydroxide precipitates, it is common to distinguish between hydrother-
mal deposits, hydrogenetic crusts, and diagenetic nodules [Bau et al., 2014].
In many places, marine phosphorite is accompanied by Fe-Mn mineralization [Baturin, 1982; Hein et al.,
1985; Rao and Burnett, 1992; Benninger and Hein, 2000]. Some thick Fe-Mn crusts also contain carbonate flu-
orapatite (CFA), which was incorporated into the crusts during specific periods prior to middle Miocene
C 2016. American Geophysical Union.
V [Baturin, 1982; Hein et al., 1985; Rao and Burnett, 1992; Benninger and Hein, 2000]. This type of mineralization
All Rights Reserved. seems to have occurred during two main Cenozoic episodes of phosphatization: the Eocene-Oligocene (39–


GONZALEZ ET AL. MINERALIZATIONS FROM GALICIA BANK 346
 Geochemistry, Geophysics, Geosystems 10.1002/2015GC005861

Figure 1. Geological setting of Galicia Bank region. (a) Location of Galicia Bank and pathways of the Mediterranean Outflow undercurrent along the eastern Atlantic margin (modified
from Somoza et al. [2014]). (b) Geological setting of the Iberian Peninsula from the IGME Geological Map at scale 1:1.000.000 [Rodrıguez Fern andez et al., 2016; Capdevila and Mougenot,
1988]. OMZ 5 Ossa-Morena Zone is the onshore geological zone of the Variscan Iberian Massif that seems to continued offshore into the Galicia Bank (GB) offset by left-lateral strike slips
faults. The buried accretionary wedge of the North Iberian margin offset by strike-slip faults is also depicted. Note that Galicia Bank is bounded to the north by the Bay of Biscay oceanic
crust and to the west by the North Atlantic, which are separated by the trajectory of the fossil triple junction between the north Atlantic and the Bay of Biscay spreading ridges (bathym-
etry from GEBCO [2003]).

34 Ma) and Oligocene-Miocene (27–21 Ma) with potentially other minor phosphogenic events, especially
the middle Miocene, about 15 Ma ago [Hein et al., 1993].
Phosphorite deposits are widespread on the seafloor of continental shelves and slopes along the western
continental margins of both the Pacific and Atlantic Oceans. These deposits are related to strong upwelling,
such as along the Pacific Peru-Chile margin and the Atlantic Morocco, Senegal, and Namibia margins [e.g.,
Tooms and Summerhayes, 1968; Burnett, 1977; Pascal et al., 1989; Fo €llmi, 1996]. Phosphogenesis driven by
sulphur bacteria has been recently described in different upwelling areas such as the Namibian shelf [e.g.,
Schulz and Schulz, 2005; Arning et al., 2008]. Phosphorite also occurs on seamounts and plateaus, such as
the Blake Plateau off the southeastern U.S. and on carbonate islands or atolls that occur in the western and
central Pacific or eastern equatorial Atlantic [e.g., Manheim et al., 1980; Baturin, 1982; Hein et al., 1993; Ben-
ninger and Hein, 2000; Jones et al., 2002].
Research on phosphorite and Fe-Mn deposits have traditionally had two main purposes: (1) their economic
importance as potential sources of phosphate for agriculture and metals, rare earth elements plus yttrium
(REY), among others, required for high-tech applications [Hein et al., 2013], and (2) their potential as archives
for the study of paleoceanographic events [Baturin, 1988; Hein et al., 1993; Rona, 2008; Hein et al., 2010;
Baturin and Dubinchuk, 2011]. Phosphorite and Fe-Mn nodule and crust studies from continental-margin
deposits and associated seamounts and banks have been the focus of numerous studies since the 1950s,
however, few of those studies dealt with the mineral paragenesis of phosphatization and Fe-Mn mineraliza-
tion, and their relationships to paleoceanographic events [e.g., Hein and Morgan, 1999; Benninger and Hein,
2000]. Studies of phosphatization in low-organic carbon settings, with moderate to low primary productivity
[Benninger and Hein, 2000] are also not common.
This paper presents the first studies of phosphorite hardgrounds and a suite of Fe-Mn oxyhydroxide depos-
its (nodules and crusts) discovered in the Galicia Bank region (northwest Iberian margin, NE Atlantic). We
present results for a complete suite of mineral deposit types: (1) phosphorite slabs and nodules, (2) Fe-Mn


GONZALEZ ET AL. MINERALIZATIONS FROM GALICIA BANK 347
 Geochemistry, Geophysics, Geosystems 10.1002/2015GC005861

Figure 2. (top) Three-dimensional multibeam bathymetric image (Simrad EM12-120S), Fledermaus visualization of the seabed structure
map in the study area. Viewing direction is from the South. (bottom) Data sets used, including dredge hauls (stars), multichannel seismic
reflection lines (red lines), and simplified bathymetry. Table below: data set of the most relevant morphological characteristics of the
dredge stations selected for this study.

crusts and stratabound deposits, (3) Co-rich Mn nodules, and (4) Fe-rich nodules, based on detailed mineral-
ogy, petrography, and chemical analyses. Furthermore, we present geophysical data including multibeam
bathymetry echo sounder (MBES) mosaics and multichannel high-resolution seismic (MHRS) profiles of the
areas where the hardgrounds, crusts, and nodules were collected. The MHRS profiles allow us to place these
deposits into the framework of Cenozoic seismostratigraphic Units and their ages. Ages of phosphatization
were estimated using strontium isotope stratigraphy and micropaleontology. Finally, we propose genetic


GONZALEZ ET AL. MINERALIZATIONS FROM GALICIA BANK 348
 Geochemistry, Geophysics, Geosystems 10.1002/2015GC005861

models for the different types of mineral deposits and relate those to key paleoceanographic and tectonic
events that occurred in the North Atlantic since the late Oligocene. These events influenced the global Ther-
mohaline Circulation (THC) of the North Atlantic Ocean.

2. Geological and Hydrographic Framework

2.1. Geological Setting and Bank Morphology
Galicia Bank is situated along the northwest Iberia margin 200 km west of Galicia (Figure 1), between
428150 N and 438N and 118300 W and 128150 W at water depths of 700–1800 m. The northwest Iberia margin is
wide (up 350 km) and hosts several seamounts (e.g., Sancho, Garcıa, and Savoye seamounts, Figure 2)
[Ercilla et al., 2011]. Galicia Bank, with an area of 2117 km2, is the main structural high of the northwest Ibe-
rian margin, emerging from a depth of 3800–620 m [e.g., Vanney et al., 1979]. The bank is a horst bounded
to the east by a NW-SE scarp of 800 m relief, to the south by NE-SW normal faults that produced a scarp of
600 m relief, to the west by a N-S normal fault forming a scarp 2000 m high, and to the north by a NE–SW
normal fault [Ercilla et al., 2009, 2011; Vazquez et al., 2009a]. Galicia Bank and other seamounts such as Vasco
de Gama, Porto, and Vigo are Mesozoic structural highs reactivated and uplifted during Cenozoic Pyrenean
tectonics, related to the Iberia-Eurasia convergence during the Paleogene.
Based on stratigraphy determined from dredged samples and micropaleontological studies of the sea-
mounts and banks [Groupe Galicia, 1979], it appears that during the Late Cretaceous, the western Iberian
margin had already undergone strong subsidence, except for Galicia Bank, which probably was a slightly
submerged shoal. Furthermore, micropaleontological data indicate that Galicia Bank continued to be in the
neritic zone at least until the beginning of the Cenozoic [Dupeuble et al., 1976].
Several morpho-tectonic structures testify to tectonic reactivation of Galicia Bank during the Cenozoic
zquez et al., 2008]: (1) faults inherited from the Cretaceous propagating rift (reactivated and non-reacti-
[Va
vated), including reactivated normal (N-S, NW-SE) and strike-slip (NE-SW) faults, and (2) Structures resulting
from episodes of compression during the Paleogene to late Miocene and late Miocene to present, including
(a) late Miocene-Quaternary normal faults, (b) folds, flexures, and (c) reverse faults (NE-SW to ENE-SWS). The
reactivation phase along the NW flank produced 3500 m relief parallel to reverse faults and normal to the
main convergence.

2.2. Present-Day Oceanographic Setting

Several water masses off the northwest Iberian margin affect Galicia Bank [e.g., Rios et al., 1992; Bode et al.,
2002]. Waters above 500 m are dominated by eastern North Atlantic Central Water (ENACW), of which two
subtypes were identified based on origin and temperature and salinity characteristics [McCartney and Talley,
1982; Pollard and Pu, 1985]. The subtropical subtype (ENACWt) ranges from 12.2 to 18.58C and from 35.66 to
36.75& salinity and its origin is located in a front near the Azores [Fi
uza, 1984]. The subpolar type (ENACWp)
formed around 468N with water between 4 and 128C and 34.96–35.66& salinity [Harvey, 1982]. Below the
salinity minimum near 500 m depth, ENACW gradually mixes with intermediate Mediterranean water, which
reaches peak salinity at approximately 1000 m depth. This water mass is characterized by two cores located
at 800 and 1200 m depths showing increased salinity [Ambar and Howe, 1979; Iorga and Lozier, 1999;
Garcia-Lafuente et al., 2008], and moves as a contour current reaching velocities of 5–10 cm/s [Daniault
et al., 1994; Iorga and Lozier, 1999]. Deep water masses below 1500 m include the Labrador Sea Water
(LSW), North Atlantic Deep Water (NADW), and Lower Deep Water (LDW). These water masses result from
the mixing of different water masses depending on density. Below the LSW, and originating from the mix-
ing of southward moving water masses formed in the Arctic Ocean, the NADW reaches to the Galicia mar-
gin moving northward. The core is located along this margin approximately between 2500 and 3000 m
depth [Saunders, 1986]. Below the NADW (about 4000 m water depth), the LDW flows northward [Paillet
and Mercier, 1997; Van Aken, 2000].

3. Data and Methods

Detailed information about the geophysical, sampling, mineralogical, and geochemical techniques can be
found in the supporting information.


GONZALEZ ET AL. MINERALIZATIONS FROM GALICIA BANK 349
 Geochemistry, Geophysics, Geosystems 10.1002/2015GC005861

3.1. Bathymetry and Seismic Reflection Data

The geophysical data sets used here were acquired within the framework of the ERGAP project during two
cruises (ERGAP-1 and ERGAP-2) carried out in 2007 aboard the R/V LAtalante. The geophysical data obtained
during these cruises included multichannel high-resolution seismic (MHRS) and multibeam bathymetry
echo sounder (MBES) records, which allowed us to explore Galicia Bank in detailed.

3.2. Sample Analyses Techniques

Samples were collected aboard the R/V Sarmiento de Gamboa in 2009 via dredging at water depths from
1200 to 700 m during cruise DIVA-ARTABRIA II. Previous MBES backscatter data and MHRS profiles indicated
the presence of deposits sampled: mounds and surfaces of high, 212 to 220 dB, acoustic backscatter, verti-
cal fluid emission structures, and high-amplitude and reflectivity reflectors.
A suite of 16 representative mineralization samples from stations DRR21, DRR37, DRR38, DRR47, and DRR81
were selected for this work (Tables (1–3)). Mineralogical analyses were carried out using X-ray diffraction
(XRD), and optical and electron microscopy (SEM and EPMA). The abundance of major, minor, and trace ele-
ments, as well as REY was determined by spectrometric techniques (XRF, ICP-MS, ICP-AES, and AAS), and
Thermal Ionization Mass Spectrometry (TIMS) was used for Sr and Nd isotopic determinations.

4. Results
Four types of mineral deposits collected from the Galicia Bank region were identified: Type I: phosphorite
slabs and nodules; Type II: Fe-Mn crusts and stratabound layers; Type III: Co-rich Mn nodules; and Type IV:
Fe-rich nodules. These different types of mineralization are distributed in different physiographic environ-
ments over Galicia Bank and Sancho seamount (Figure 2).

4.1. Seismostratigraphic Analysis: Major Discontinuities, Hardgrounds, and Sample Sites

Three seismostratigraphic Units (U1, U2, and U3) are identified for Galicia Bank and Sancho seamount, sepa-
rated by two main discontinuities (D1 and D2) (Figures 3 and 4 and supporting information Figures S1 and
S2). The main unconformity identified along the bank is D1, characterized by high-amplitude reflectors that
constituted a ramp-type seafloor over most of the bank. In places, the high-reflectivity character of the D1
unconformity masks the underlying Units on Galicia Bank, that we call U1 Unit (supporting information Fig-
ure S2). Samples of large phosphorite slabs (<1 m) collected at stations DRR81 and DRR21 are related to
this D1 unconformity, which forms the morphological margin of Galicia Bank (Figure 3). D1 is also identified
at the summit of Sancho seamount overlying the lowermost sedimentary Unit U1. Samples from station
DRR47 along the top of this seamount also yielded large phosphorite slabs with Mn replacement along the
top and underside surfaces (Figure 5).
The D1 unconformity is overlain by Unit U2 along the western side of Galicia Bank. Unit U2 is composed of
a westward up-slope migrating drift developed from 1570 to 1125 m water depths (Figure 3 and supporting
information Figure S2). Unit U2 is also well developed along the foot of southern Galicia Bank and in the
passage between Sancho seamount and Galicia Bank overlying a faulted and deformed D1 reflector (Figure
3 and supporting information Figure S1). The top of Unit U2 is a highly erosive unconformity, D2, seen in
the present morphology as a moat (Figure 3 and supporting information Figure S2).
Seismic chimneys (SC in Figure 4) composed of semitransparent acoustic facies interrupt the sequence of
reflectors of Unit U1 and partially of Unit U2. Furthermore, these seismic chimneys breach the D1 unconfor-
mity and form mounds with internally chaotic acoustic facies that extend laterally overlapping this uncon-
formity (Figures 3 and 4). Phosphorite pebbles (fragmented phosphorite), Co-rich Mn nodules, and Mn-
impregnations of phosphorite slabs occur at stations DRR81 (Figure 3) and DRR47 and DRR21 (Figure 4) and
are related to sites where breaching of horizon D1 occurred at the base of Unit U2.
Unit U3 occurs predominantly along the summit of Galicia Bank and is deposited on erosional unconformity
D2. Unit U3 is composed of fossil and living deep water coral forming along-slope oriented mounds and
ridges and is intercalated with up-slope migrating sediment drifts at water depths from 1125 to 826 m,
which are related to the Mediterranean Outflow Water [Somoza et al., 2014]. Fe-rich nodules recovered at
stations DRR37 and DRR38 are related to Unit U3 (Figure 3).


GONZALEZ ET AL. MINERALIZATIONS FROM GALICIA BANK 350
 Geochemistry, Geophysics, Geosystems 10.1002/2015GC005861

Table 1. Chemical Composition of Selected Phosphorite Samples

(Type I) Phosphorite Slabs and Nodules
DRR47-1A DRR81-5B DRR47-2 DRR81-3 DRR81-4 DRR38-2

Phosphorite Phosphorite
Phosphorite Phosphorite Pebbles Phosphorite Phosphorite Nodule Av. Shalea,b
Al2O3 (wt %) 0.72 1.05 2.35 1.23 1.86 1.14 15.12
SiO2 2.34 2.27 3.35 3.23 4.82 1.38 59.96
P2O5 22.3 32.6 25.8 22.1 30.6 31.1 0.16
K2O 0.15 0.25 0.46 0.35 0.50 0.16 3.21
Na2O 0.62 0.87 0.92 0.68 0.89 0.90 1.3
CaO 48.7 45.2 32.6 46.1 42.5 37.7 3.1
MgO 0.68 0.86 1.92 0.96 1.12 0.95 2.5
TiO2 0.02 0.18 0.23 0.04 0.42 0.24 0.77
Fe2O3 0.28 1.72 8.18 2.83 3.27 8.80 6.75
MnO 0.82 1.1 10.3 0.70 1.79 5.35 0.11
TOC 0.38 0.42 0.36 0.31 0.24
S 0.30 0.50 0.39 0.37 0.56 0.04 0.24
F 0.57 2.03 1.69 1.42 2.08 2.43 0.074
LOI 23.4 13.8 13.0 21.8 12.1 12.3
CaO/P2O5 2.18 1.39 1.26 2.09 1.39 1.21 19.38
F/P2O5 0.03 0.06 0.07 0.06 0.07 0.08 0.46

Ag (lg/g) <DL <DL <DL <DL <DL <DL 0.07

As 8 38 147 50 51 177 13
Ba 71 103 1588 247 123 941 580
B 191 187 256 199 291 359 100
Co 36 113 1420 142 354 1322 19
Cr 2 6 13 31 5 4 90
Cu 52 92 845 57 121 131 45
Li 5 9 56 7 11 6 66
Mo 8 25 90 9 33 71 2.6
Nb 3 8 13 4 6 23 11
Ni 371 449 3798 257 552 734 68
Pb 13 53 572 23 128 911 20
Rb <DL 4 12 8 17 2 140
Sb <DL 5 9 4 2 18 1.5
Sc 3 13 10 10 15 7 13
Se 4 2 3 1 <DL 21 0.6
Sr 785 865 989 897 936 1750 300
Te 20 0.08
Th 0.75 2.7 7.7 2.3 3.6 6.8 12
Tl <DL 1 40 <DL 5 <DL 1.2
U 6.1 6.4 6.5 6.3 5.3 8.3 3.7
V 16 61 272 64 89 282 130
W 4 11 23 4 7 18 1.8
Zn 54 76 478 203 118 208 95
U/Th 8.13 2.41 0.85 2.80 1.47 1.22 0.31

La 17.3 134 368 125 216 275 92

Ce 7.18 35.8 278 28.8 68.5 920 59
Pr 2.23 19.1 50.6 19.7 24.6 32.7 5.6
Nd 8.99 84.2 215 84.9 105 131 24
Sm 1.66 16.8 40.2 16.5 19.9 23.8 6.4
Eu 0.41 4.51 10.4 4.14 5.34 6.14 1.0
Gd 2.05 24.3 57.2 21.5 30.2 37.8 6.4
Tb 0.31 3.78 8.01 3.24 4.48 4.96 1.0
Dy 2.11 25.6 51.5 20.8 30.6 32.4 4.6
Y 27 306 664 178 455 411 26
Ho 0.55 6.17 12.2 4.84 7.61 8.05 1.2
Er 1.94 19.3 36.6 14.6 23.9 25.4 2.5
Tm 0.3 2.68 4.74 2.01 3.29 3.51 0.2
Yb 0.19 17.2 28.4 12.9 21.3 22.1 2.6
Lu 0.4 2.91 4.67 2.11 3.64 3.74 2.8
%HREY 49 59 48 49 57 29 20
Ce* 20.62 20.83 20.37 20.90 20.73 10.3
a
Turekian and Wedepohl [1961].
b
Baturin [1988].


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Table 2. Chemical Composition of Selected Fe-Mn Oxide Samples

(Type IV) Fe-Rich
(Type II) Fe-Mn Deposits (Type III) Co-Rich Mn Nodules Nodules
DRR47-1B DRR81-5A
Stratabound Fe-Mn crust DRR81-1 DRR21-1 DRR21-2 DRR38-5 DRR37-1 Av. Nodulesa
Al2O3 (wt %) 4.06 4.94 1.21 1.51 1.00 1.90 2.66 5.1
SiO2 5.42 1.49 0.97 3.12 2.94 5.23 6.32 16.5
P2O5 10.8 1.17 0.42 0.17 0.15 1.03 0.77 0.85
K2O 0.60 0.25 0.86 1.17 0.85 0.27 0.40 0.88
Na2O 1.04 1.89 1.06 1.24 0.83 0.37 0.37 2.66
CaO 14.0 3.32 16.2 4.25 14.5 0.93 0.57 3.12
MgO 4.52 5.87 2.90 2.83 1.23 3.68 3.38 2.61
TiO2 0.28 0.93 0.07 0.22 0.18 0.12 0.14 1.15
Fe2O3 15.4 23.8 0.45 0.42 1.33 67.4 64.6 17.8
MnO 23.3 27.6 49.9 58.2 54.0 2.08 4.96 24.0
LOI 19.0 26.8 22.2 19.3 18.3 17.0 15.8 -
Mn/Fe 1.7 1.3 123 153 45 0.03 0.09 1.35

Ag (lg/g) <LD <LD <LD <LD <LD <LD <LD 0.09

As 258 500 48 64 46 274 156 140
Ba 2074 1042 25300 31900 58900 55 165 2300
B 337 362 183 205 199 440 519 300
Co 3663 8510 18005 14844 6482 94 86 2700
Cr 17 16 3 130 13 23 15 70
Cu 1539 783 1550 2201 1684 7 16 4500
Li 84 45 9 20 11 8 26 80
Mo 335 387 220 244 236 37 37 380
Nb 22 71 11 11 55 4 <LD 70
Ni 8627 6542 2328 2063 985 54 96 6600
Pb 745 2842 2580 6240 372 21 20 930
Rb 16 4 4 16 12 15 20 17
S 3124 5419 1116 1931 1633 675 532 4700
Sb 23 33 8 12 26 <LD <LD 50
Sc 14 9 2 2 3 9 3 10
Se <LD <LD <LD <LD <LD <LD <LD 0.6
Sr 737 1068 1730 1890 4288 78 109 830
Te 12 14 8 1 10
Th 8.8 25 1.7 6.0 1.4 1.6 1.5 30
Tl 15 81 122 116 42 <LD 7 150
U 6.8 12 2.7 4.1 3.0 3.4 1.7 5
V 700 983 1740 2550 3300 362 267 500
W 55 97 438 622 479 5 3 100
Zn 961 687 169 381 203 81 86 1200

La 146 114 23.5 32.1 21.3 9.69 5.03 157

Ce 217 1154 86.5 314 70.6 20.2 10.3 530
Pr 26 22.9 4.27 5.4 3.53 2.29 1.2 36
Nd 113 91.4 18.3 20.8 14.3 9.57 4.7 158
Sm 23.2 20.8 4.07 4.5 3.39 2.2 1.03 35
Eu 6.09 5.22 3.45 4.11 6.41 0.59 0.27 9
Gd 31.8 27.8 5.75 7.41 4.74 2.64 1.14 32
Tb 4.64 4.18 0.77 0.85 0.54 0.41 0.17 5.4
Dy 29.9 26.6 4.7 4.97 3.15 2.53 0.94 31
Y 245 130 26 20 13 13 5 150
Ho 6.86 5.8 1 1.04 0.62 0.52 0.19 7
Er 20.5 18 2.85 3.03 1.7 1.56 0.55 18
Tm 2.81 2.67 0.39 0.44 0.24 0.23 0.07 2.3
Yb 17.9 17.5 2.52 3.04 1.75 1.63 0.46 20
Lu 2.88 2.7 0.37 0.44 0.24 0.27 0.07 1.8
%HREY 41 15 26 11 23 35 29 21
Ce* 20.11 0.72 0.28 0.73 0.26 0.00 0.00
Y/Ho 36 22 26 13 32 25 26 21
CeSN/CeSN* 0.80 5.18 1.97 5.41 1.84 0.99 0.96
YSN/HoSN 1.32 0.83 0.97 0.71 0.80 0.95 0.96
a
Global mean of oceanic Mn nodules from Baturin [1988].


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Table 3. Sr and Nd Isotopic Compositions, Ages, and Descriptions of Galicia Bank Mineralizationa
Sample
87
Number Type Fossil Age Sr/86Sr Sr Age (Ma) 143
Nd/144Nd eNd(0) Description
DRR47-1A CFA early 0.713355 0.512089 210.71 Hydrothermal(?)
Miocene CFA-replaced white
limestone with foraminifera
DRR47-1Ac Carbonate early 0.708611 17.7 6 0.9 Analysis for Sr isotopes on
fraction Miocene 2.5 N HCl-leached sample
DRR81-3 CFA 0.714808 0.512149 29.54 Hydrothermal(?) CFA-replaced
pale brown limestone
DRR81-3c Carbonate 0.708386 21 6 0.6 Analysis for Sr isotopes on
fraction 2.5 N HCl-leached sample
DRR81-4 CFA 0.713657 Hydrothermal(?) CFA-replaced
reddish limestone
DRR81-4c Carbonate 0.708160 24.85 6 0.9 Analysis for Sr isotopes on 2.5 N
fraction HCl-leached sample
DRR81-5B CFA early 0.712385 0.512146 29.60 Hydrothermal(?) CFA-replaced
Miocene reddish foraminiferal limestone
DRR47-2 Bulk early 0.708576 18.15 6 0.4 0.512198 28.58 CFA in phosphorite replaced by
Miocene? Mn oxide at a later stage
DRR37-1 Bulk 0.710637 0.512184 28.86 Fe-rich nodule
DRR21-1 Bulk Miocene? 0.708239 23.25 6 0.6 0.512169 29.15 Hydrothermal(?) Co-rich Mn nodule
a
The Sr-isotope seawater curve of McArthur and Howarth [2004] was used. The ages of phosphatization could not be determined
from Sr isotopes because the ratios were altered by interaction with hydrothermal fluids; the phosphatization was early diagenetic, so
the depositional ages approximate the phosphatization ages.

4.2. Structure, Petrography, and Mineralogy

4.2.1. Phosphorite Slabs and Nodules
Polished sections of cut samples of phosphorite slabs and nodules (Figure 5) show massive, dense to porous
and mottled internal structures (Figures 5a–5d), and concentric growth patterns around a nucleus in nod-
ules (Figure 5e). The nodules are usually of centimeter size (up to 6 cm diameter), subspherical, and black to
brown. The laminae are porous, from sub-mm to mm thick, with laminar to columnar textures. The nucleus
of these nodules is composed of millimeter to centimeter angular fragments of pale-brown-pink phosphor-
ite slabs (Figure 5e). The layers in the phosphorite nodules are composed of CFA with interlayered lamina
containing abundant Fe-Mn oxyhydroxides that show high backscatter under the electron microscope (Fig-
ure 6j and anal. DRR38-2c supporting information Table S2).
The phosphorite slabs frequently form large pavement-like plates up to several decimeters long and up to
10 cm thick (Figure 5a). The phosphorites vary in color from white to a wide range of browns, and reddish
and pinkish in some rocks. Slabs show dissolution and boring cavities infilled by carbonates and semiconso-
lidated sediment. The phosphorite slabs are usually encrusted on their top surface by millimeter-thick, rarely
centimeter-thick, hydrogenetic Fe-Mn crusts, and hosting benthic organisms (cold-water corals, bryozoans)
(Figure 5a). Fe-Mn replacement of the margins of the slabs is common and may extend to the interior of
the phosphorite slabs, especially across fractures and along bored channels with development of dendritic
features (Figures 5a and 5b). In some samples, brecciated textures are observed at the base of phosphorite
with clasts (sand to pebble size) composed by phosphates cemented by and partially to completely
replaced by Fe-Mn oxyhydroxides (Figure 5c).
Thin sections, polished sections, and electron microscope (EPMA) images of phosphorite slabs show large
areas of microcrystalline apatite and CFA, also identified by XRD (Figure 6). In addition, calcite forms a
micritic relict mosaic, being partially to completely replaced by phosphates. Isotropic collophane extensively
replaced skeletal material and most of the calcite cement in the samples. Intergrowths of collophane with
CFA are common. Calcite filling millimeter-sized to centimeter-sized cavities (borings) in the phosphorite
slabs (Figure 5a) forms a microsparitic to sparitic mosaic. The percentage of bioclasts in the phosphorites
range from zero to 65 vol %. Carbonate bioclasts are composed of phosphatized and well-preserved test
fragments of planktonic and benthic foraminifera (Figure 6), including abundant globigerinoides, globigeri-
nas, globigerinidos, and globorotalias with chambers filled by phosphate. The presence of sparse shell frag-
ments of catalpsydra indicates an early Miocene age for some phosphorite slabs (e.g., sample DRR47-1).
Occasionally, foraminifera chambers are filled by and the test replaced by Fe-Mn oxyhydroxides (Figure 6f).
Nonphosphatic minerals are rare and mostly subangular to subrounded detrital quartz, feldspar, and clay


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Figure 3. (a) S-N A10 multichannel seismic profile across the base and southern slope of Galicia Bank. Vertical exaggeration is X25
(V 5 2.0 km/s). (b) Location of seismic profile and dredge stations. Phosphorites formed hardgrounds linked to the D1 discontinuity. (c)
Phosphorite slab replaced in part by Fe-Mn oxides in veins along fractures; (d) A large suite of phosphorite pebbles; samples in Figures 3c
and 3d were collected on the flanks of the bank. (e) Fe-rich nodule collected on the summit of the Galicia Bank in contourite deposits.

minerals. Different degrees of alteration are observed on the surfaces of some phosphorite slabs giving rise
to the pseudomorphic replacement of phosphates by colloform Fe-Mn oxyhydroxides (Figure 6g).
The phosphorite slabs from station DRR81 on Galicia Bank and station DRR47 on Sancho seamount show
comparable lithology, composition, and age of the limestone that was replaced. Depositional ages of CFA-
replaced carbonates are predominantly middle Miocene and older (Table 3, see isotopic section below).
4.2.2. Fe-Mn Nodules and Crusts
Three types of Fe-Mn deposits have been recognized based on their structure, petrography, and mineral-
ogy: Fe-Mn crusts, Co-rich Mn nodules, and Fe-rich nodules.
Polished cross sections of Co-rich Mn nodules show an internal structure of concentric laminae around a
nucleus (Figure 5f). These nodules are usually centimeter size (up to 4 cm maximum diameter), subspherical
to ellipsoidal, and black with submetallic luster. The nucleus is not visible under the microscope. The con-
centric laminae consist of an intimate intergrowth of poorly crystalline 10 Å manganates (todorokite, roma-
nechite, and coronadite) and 7 Å manganates (birnessite) (supporting information Figures S3c and S3e).
Asbolane may be an accessory mineral. Intercalated lamina of Mn carbonates identified with EPMA show
low backscatter whereas the Mn-oxide lamina show high backscatter (Figure 7c and anal. DRR81-1-8 sup-
porting information Table S3). Abundant well-preserved carbonate bioclasts (miliolidae, other foraminifera,
and abundant radiolarians) are dispersed in the layers. The chambers of foraminifera are filled by fibrous
Mn oxides (Figure 7d). Microfractures filled with micritic to sparitic calcite crosscut the Fe-Mn layers. The


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Figure 4. W-E A05 multichannel seismic profile across mounds and canyons along southern Galicia Bank. Vertical exaggeration is X18
(V 5 2.0 km/s). Mounds with an internal chaotic and indistinct seismic reflection pattern and development of ‘‘seismic chimneys (SC)’’ that
crosscut the D1 discontinuity and affect U1 and partially U2 units. (b) Suite of phosphorite slabs and Co-rich Mn nodules dredged at station
DRR21. (c) Cut sections of Co-rich Mn nodules. (d) Location of seismic profile and dredge station.

percentage of bioclasts ranges from 1 to 20% with an average of 10 vol %. Dispersed detrital grains of
quartz are visible under the microscope.
Fe-rich nodules are centimeter-size brown to orange concretions (5 cm maximum diameter) with variable
shapes (subspherical to irregular; Figure 5g). These nodules show concentric laminae, but tabular samples
with a complex arrangement of layers are also common. The nuclei cannot be differentiated from the layers
under the microscope. These nodules are composed of goethite and lepidocrocite (Figure S3f) forming a
microcrystalline (<12 lm) mosaic of crystals with rhomboidal cross sections (Figures 7e and 7f). In addition,
detrital grains of quartz, feldspar, and clay minerals are dispersed in the nodules. Framboidal pyrite, partially
to completely replaced by Fe-oxyhydroxides, occur in some samples (Figure 7f). These framboids, with a
diameter less than 25 lm and formed by several idiomorphic to subidiomorphic crystals, commonly fill
chambers of foraminifera. The surface of some Fe-rich nodules is stained by thin black-brownish Fe-Mn
crusts.
Black Fe-Mn oxyhydroxide crusts (Figures 5a–5d) show a continuous succession of subparallel laminae cov-
ering rock substrates (nodules, phosphate pavements, and basement or drop stones of igneous, metamor-
phic and sedimentary rocks). The Fe-Mn crusts vary in thickness from a patina to several centimeters. Thin
Fe-Mn crusts (Figure 5d) show a finely laminated structure with colloform laminar to columnar textures.
They have the appearance of typical hydrogenetic crusts, with botryoids and current-smoothed upper sur-
face, which indicate formation at the seafloor. The crusts are composed of poorly crystalline vernadite with
minor amounts of other Mn oxides such as asbolane, and goethite is an accessory minerals.
The underside margin of phosphorite slabs are commonly replaced by todorokite and goethite, which also
commonly infill fractures, giving rise to a thick, Fe-Mn layer with an apparent massive structure (Figures 5a–
5c). These Fe-Mn-oxides are in part replacement layers of phosphorite that formed subseafloor and can be
considered stratabound deposits.

4.3. Chemical Composition

4.3.1. Phosphorite Nodules and Slabs
Composition of phosphorite slabs (samples DRR47-1A, DRR81-3, DRR81-4, and DRR81-5B) and nodules (sam-
ple DRR38-2) from different dredge sites are summarized in the Table 1. The P2O5 contents of the phosphor-
ites range from 22 to 32.6 wt %. Phosphatization is more pervasive on Galicia Bank with P2O5 contents of
more than 30 wt % at stations DRR-38 and DRR-81 and lowest on Sancho seamount (DRR-47 station). The
CaO/P2O5 ratios range from 1.21 to 2.18. These values indicate intense phosphatization, especially those


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Figure 5. Suite of mineralization types from the Galicia Bank region. (a) Cross section of a phosphorite slab composed of dense CFA and
showing replacement by Mn oxides (todorokite (to) and birnessite (bi)) along the underside margin and along fractures, and thin patina of
hydrogenetic vernadite (ver) coats the upper surface; later-stage CFA and carbonate (Ca) fill cavities. (b and c) Cross section of phosphorite
slabs showing parallel fracture set and partial replacement by Fe-Mn oxides in Figure 5B and pervasive replacement in Figure 5C; cavities
are filled by CFA and carbonate. (d) Phosphorite fragment with an 5 mm thick hydrogenetic Fe-Mn crust. (e) Cross section of spheroidal
phosphorite nodule composed of a phosphorite nucleus and concentric layers of CFA and Fe-Mn oxides. (f) Cross section of concentric
layers of Co-rich Mn nodule comprized of romanechite (rom) and calcite bioclasts (cal). (g) Fe-rich nodule formed by goethite (goe) and sil-
icates (silic) showing well-developed concentric pattern.


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Figure 6. Thin and polished-section photomicrographs of phosphorite. (a and b) Sample from Sancho seamount with abundant foraminif-
era and fractures, some microfossil chambers, and patches filled by dendritic Fe-Mn oxides; (c) brecciated phosphorite from Sancho sea-
mount with interclast cement composed of todorokite and birnesite (Fe-Mn ox) and matrix composed of Fe-Mn replaced phosphorite (r.
Phosp.). (d) Phosphorite from Galicia Bank rich in Miocene foraminifera, with some patches and chamber fill of Fe-Mn oxides. (e–g) EPMA
photomicrograph of foraminifera chamber fill by Fe-Mn oxides and CFA replacement fronts; ca-test 5 calcite tests; in Figure 6g, a sharp
replacement front of Fe-Mn oxides replacing the phosphorite. The external Mn-oxide layer is lining a cavity. (h) EPMA photomicrograph of
phosphorite breccia clast cemented by Fe-Mn oxyhydroxides and CFA cavity fill. (i) EPMA photomicrograph of phosphorite slab top-side
edge with biological boring and patina of hydrogenetic Fe-Mn crust (Fe-Mn ox.). (j) EPMA photomicrograph showing the concentric pat-
tern of CFA and Fe-Mn oxides in a phosphorite nodule from Galicia Bank.


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Figure 7. Thin and polished-section EPMA photomicrographs of Fe-Mn deposits. (a) Laminated hydrogenetic Fe-Mn patina composed of
vernadite encrusting phosphorite (Php). (b) Fe-Mn replaced phosphorite (r. Phosphorite) showing the oxide mineralization front that cross-
cuts a foraminifera test; Mn-ox is a thin cavity lining of Mn oxide. (c) Succession of romanechite-rich (rom) and todorokite-rich layers (to) in
a Co-rich Mn nodule; note the relict microfossils. (d) Detail of romanechite-rich layer with dispersed silicates (sil) and carbonate bioclasts
(ca bioc.) filled by fibrous romanechite. (e) Rhombohedral mosaic of goethite (goe) in an Fe-rich nodule; the skeletal rhombs may have
been siderite replaced by goethite. (f) Framboidal texture in pyrite partially replaced by goethite (fr. (goe 6 py)).


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close to CaO/P2O5 5 1.32, characteristic of pure fluorapatite [Manheim and Gulbrandsen, 1979]. Fluorine con-
tents exceed 2% in some samples reflecting the abundance of CFA and need for charge-balancing ele-
ments. The F/P2O5 ratio (0.06) is closer to the fluorapatite end member (0.089) than to the most substituted
francolite (0.148) end-member of the range [McClellan and Van Kauwenbergh, 1990]. The SO22 4 contents
(0.12–1.64%) are lower to slightly greater than the maximum amount (1.2% SO22 4 ) thought to typically sub-
stitute for PO32
4 in CFA. The SiO2 contents are low (less than 4.8 wt %) and SiO2 /Al2 3O ratios range from 1.21
to 3.25, reflecting the presence of aluminosilicates. Total organic carbon (TOC) is less than 0.4 wt % indicat-
ing minor organic matter. Total REY vary widely, from 73 to 1938 lg/g (Table 1) with a mean of 1017 mg/g.
The lowest total is for phosphorite slab DRR47-1A and the highest is for phosphorite nodule DRR38-2. The
Ce/La ratios range from 0.23 to 0.76, except for sample DRR38-2, which is 3.35. These Ce/La ratios except
the last one are similar to the ratios for seawater, indicating that the REY and phosphate host were derived
from seawater, probably within or near an oxygen minimum zone. Finally, the Ce/La ratios 0.71 (sample
DRR47-2) and 3.35 (sample DRR38-2) are higher than ratios found in seawater at any depth, and probably
reflect the postdepositional influence of hydrothermal fluids. Shale-normalized REY patterns [Piper, 1974a,
1974b] support derivation of the REY and phosphorites from seawater (Figure 8). The characteristic patterns
are HREY enriched, strong negative Ce anomaly and positive Gd and Y anomalies, which are found for all
the samples except the phosphorite nodule DRR38-2, which shows a strong positive Ce anomaly (Figure 8).
The phosphorite nodule DRR38-2 has intercalations of Fe-Mn oxides with phosphatic laminations, which is
reflected in the high Fe and Mn contents. All phosphorite samples with high Fe and Mn show higher trace
metal (e.g., Co, Ni, Pb, and Ba) and REY contents, especially notable in sample DRR47-2: Ni (0.38 wt %), Ba
(0.16 wt %), Co (0.14 wt %), Cu (0.09 wt %), and HREY (878 lg/g). These contents are similar to those for
sample DRR47-1B in Table 2: Ni (0.86 wt %), Co (0.37 wt %), Ba (0.21 wt %), Cu (0.15 wt %), and HREY (368
lg/g). Both samples are interpreted to be stratabound Fe-Mn layers formed by different degrees of replace-
ment and impregnation of phosphorite slabs. The degree of replacement increases progressively from the
interior to the margin and along fractures in the phosphorites, progressively increasing the contents in Fe,
Mn, Ba, Pb, Cu, and other metals and decreasing P and Ca (anal. DRR47-2-12, DRR47-2-3, and DRR47-2-4 in
supporting information Table S2).
4.3.2. Fe-Mn Nodules and Crusts
Fe-Mn stratabound DRR47-1B layer and crust DRR81-5A show moderate MnO (23.3 and 27.6 wt %) and
Fe2O3 (15.4 and 23.8 wt %) contents, with Mn/Fe ratios of 1.7 and 1.3 for the bulk samples (Table 2). The
crust shows higher TiO2 and much lower CaO and P2O5 than sample DRR47-1B. With respect to trace ele-
ments, Co (0.85 wt %), Pb (0.28 wt %), and Tl (81 lg/g) are relatively enriched in the crust sample, whereas
Ni (0.86 wt %), Ba (0.2 wt %), and Cu (0.15 wt %) are higher in the stratabound layer; contents of the other
elements are similar for both samples. From an economic standpoint, Ni and Co are significantly high in the
stratabound layer and crust, respectively. The sum of concentrations of potential ore metals (Cu, Co, Ni, V,
and Mo) are 1.5 and 1.7 wt % for bulk samples, respectively. The total REY contents are 894 lg/g for sample
DRR47-1B and 1644 lg/g for crust DRR81-5A. The most striking features of the REY patterns for these sam-
ples are the negative Ce anomaly for the stratabound sample and strongly positive Ce anomaly for the crust
(Figure 8). In addition, both samples show positive Gd anomalies. The Y/Ho ratios vary over a wide range
(13–36), typical of hydrogenetic crusts and hydrothermal manganese deposits in the Pacific Ocean [Hein
et al., 1997], indicating that Y and Ho are fractionated in the marine environment [Bau et al., 2014].
Bulk Co-rich Mn nodules have high MnO contents (up to 58 wt %) and low Fe2O3 (down to 0.42 wt %). The
Mn/Fe ratios vary from 45 to 153. The contents of other major elements are low except for CaO (up to 16.2
wt %), Ba (to 5.9 wt %), and MgO (to 2.90 wt %). The markedly high Ba contents reflect the abundance of
romanechite rather than the presence of barite, which was not detected by EPMA, optical microscopy, or
XRD analyses (supporting information Figures S3c and S3e). The abundance of Pb in some nodules may be
due to sorption on the Mn oxides or formation of a minor amount of coronadite or other Pb-rich Mn oxide
(Figure S3e). The total concentrations of potential ore metals (Cu, Co, Ni, V, Mo, W) are 2.4, 2.3, and 1.3 wt %
for bulk nodules DRR81-1, DRR21-1, and DRR21-2, respectively. From an economic standpoint, Co contents
in two of the nodule samples are remarkable high, among the highest measured in nodules [Hein et al.,
2013; Hein and Koschinsky, 2014]. The distribution patterns of REY show small variations in total contents
(Table 2) with LREE being most abundant in all the samples. The REY plots of Co-rich Mn nodules show
strong positive Eu and Ce anomalies and little fractionation between LREY and HREY (Figure 8).


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Figure 8. PAAS-normalized and NASC-normalized REY element plots for phosphorites, Co-rich Mn nodules, Fe-rich nodules, and Fe-Mn
crusts.

Iron is the most abundant element in the bulk Fe-rich nodules followed by Mn, Si, Mg, and Al (Table 2), with
Mn/Fe ratios of 0.03 and 0.09. Boron, As, Co, Ni, Sr, and Ba are the most abundant trace elements. The aver-
age concentrations of other trace elements (Cr, Cu, Li, Nb, Pb, Rb, Sc, Se, and W) are not higher than 30 lg/g
with Ag, Sb, and Tl below detection limits. The total concentrations of potential ore metals (Cu, Co, Ni, V,


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and Mo) are very low as are the REY contents (RREY < 67 lg/g). REY patterns show positive Eu anomalies
and no Ce anomaly. The patterns also show a moderate HREY enrichment and there is LREY/HREY fractiona-
tion especially in nodule DRR38-5 (Figure 8).

4.4. Isotopes
The samples have Sr and Nd isotope values ranging from 0.708160 to 0.714808 for 87Sr/86Sr and 28.58 to
210.71 for eNd (Table 3). Significant differences in the Sr isotope ratios exist between the CFA-dominant
phase in phosphorites (from 0.712385 to 0.714808) and their pristine relict calcite precursor (0.708160–
0.708611). Apparent maximum ages of phosphatization were determined using the Sr isotope composition
of the carbonate that was not phosphatized, the seawater Sr isotope curve of McArthur and Howarth [2004],
and assuming that phosphatization took place soon after carbonate sedimentation. This assumption is in
accord with what is known about the formation of typical phosphorite hardgrounds in modern continental-
margin settings [e.g., Burnett, 1977; Bentor, 1980; Birch, 1980; Froelich et al., 1988; Glenn and Arthur, 1988;
Burnett and Riggs, 1990; Follmi, 1990]. Sr isotopes for pristine calcite in three phosphorites indicate deposi-
tional ages from 24.85 6 0.9 to 17.7 6 0.9 Ma (late Oligocene to early Miocene); the CFA shows the most
radiogenic values (average 0.713551). These radiogenic Sr ratios may reflect deep-seated fluids venting in
the area of Galicia Bank; the heat source for these hydrothermal fluids would have been geothermal rather
than magmatic. Leaching of granodioritic-granitic basement rocks (Ossa Morena rocks) can explain the high
Sr isotope values. The possibility that the aluminosilicate fraction is the cause of the Sr isotopic ratios and
isotopic-derived apparent ages is not viable because of their low content in the samples; the Fe-Mn oxides
in the phosphorites could have Sr isotope ratios that would lower the apparent Sr isotopic age. Phosphorite
sample DRR47-2, strongly Fe-Mn oxide replaced, could have a questionable isotope-derived age, whereas
the other phosphorites were selected to avoid this contaminant, verified by the low Fe and Mn contents
(Table 1).
Nd and Sr isotopes are powerful tools for exploring paleoenviromental changes [Palmer and Elderfield,
1985a,b; Stille et al., 1996], and the Nd isotopic signature of Fe-Mn oxides indicates the sources of these
oxides. For samples analyzed here, these isotopes do not show a marked similarity to those of the modern
seawater masses in the area, corroborating that these are not recent deposits. The eNd values measured for
the leached Fe-Mn oxide fractions vary from 28.86 for Fe-rich nodules to 29.15 for Co-rich Mn nodules,
higher the current range of NE Atlantic seawater in this region. The eNd signatures of CFA vary from 29.54
to 210.71, above the values than present-day NE Atlantic seawater.

5. Discussion
Data presented here allow us to determine the Cenozoic succession of mineralization preserved on Galicia
Bank: (1) phosphorite slabs and nodules, (2) Fe-Mn crusts and stratabound layers, (3) Co-rich Mn nodules,
and finally (4) Fe-rich nodules. In addition, for each type of mineralization, we constraint the ages of forma-
tion and determine the influence of global and regional environmental/oceanographic conditions on the
mineralization. We find that major changes in the oceanographic regime in the North Atlantic Ocean during
the Cenozoic, driven by intraplate tectonism leading to the establishment of deep water exchange between
the Artic and North Atlantic Oceans, played a role in the mineralization. The integration of mineralization,
tectonics, and oceanography/paleoceanography allow for a comprehensive understanding of this
continental-margin type of mineralization, which has generally not been well studied from the modern
ocean basins.

5.1. Late Oligocene-Early Miocene Phosphorite Slabs

Like other global ocean locations [e.g., Bentor, 1980; Baturin, 1982; Hein et al., 1993; Jones et al., 2002; Arning
et al., 2009], the phosphorites from the Galicia Bank region show a wide variety of morphologies, for exam-
ple, nodules and pavements, and formation by the replacement of carbonate rocks and sediments by CFA.
5.1.1. Age Constraints of Phosphatization and Global Significance
Depositional ages of the carbonate component of the phosphorites from Galicia Bank (station DRR81) and
Sancho seamount (station DRR47) (Table 3) were determined using Sr isotopes and micropaleontology.
Three intervals (Figure 9) showed ages of late Oligocene (25.7–24 Ma), early Miocene (23.8–22.6 Ma) for
Galicia Bank and early Miocene (18.6–16.8 Ma) for Sancho seamount; it is likely that carbonate sedimenta-
tion was continuous during that entire time interval. The timing of phosphatization is not known because


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the Sr isotopes of the CFA have been modified by the mineralizing fluids. The REY pattern of the phosphor-
ites (Figure 8) reflect that of seawater [DeBaar et al., 1985], indicating precipitation from cold seawater. If
phosphatization was early diagenetic, then the carbonate depositional ages (late Oligocene-early Miocene)
may closely approximate the phosphatization ages. This assumption is supported by phosphatization of
seabed surface sediment that formed hardground—this type of early-stage phosphatization is characteristic
of continental-margin phosphorite deposits [e.g., Glenn and Arthur, 1988]. If true, then phosphatization was
comparable in age with the major Cenozoic phosphatization events determined for other phosphorite
deposits in the global ocean [Hein et al., 1993]. These events of phosphatization corresponded to times of
climate transitions from glacial to warm in the late Oligocene-early Miocene [Hein et al., 1993].
Phosphorites on Galicia Bank were likely produced by processes that characterize phosphorites forming
today along continental margins. Marine phosphorites along continental margins typically form by replace-
ment of and cementation of carbonate sediments at or near the seafloor [e.g., Burnett, 1977; Burnett and
Riggs, 1990; Bentor, 1980]. These phosphorites commonly form hardgrounds, nodules, pebbles, and slabs,
such as is found forming today off the Peru-Chile margin [e.g., Froelich et al., 1988; Glenn, 1988]. The phos-
phate is supplied to the sediment by organic matter produced during moderate to high primary productiv-
ity as a result of upwelling. Winnowing by bottom currents of the phosphate sediment can produce more
pure phosphorites free of siliciclastic and biogenic materials. Winnowing can produce pure phosphorite lag
deposits that may then transform into phosphorite hardgrounds through CFA cementation [e.g., Fo €llmi,
1996; Filippelli, 2011]. In addition, deep-sea waters may have acted as a reservoir for dissolved P and other
nutrients during stages of climatic stability and sluggish oceanic circulation. During glacial periods, the P
from the deep-sea reservoir may have been redistributed by upwelling into shallower waters around sea-
mounts and banks due to enhanced global oceanic circulation as a consequence of the increased pole-to-
equator thermal gradient. This process may have augmented the nutrients supplied to the upwelling sys-
tem and further increased primary productivity in surface waters, increased the supply of biophosphate,
and enhanced the expansion of the OMZ around topographic highs [Hein et al., 1993; Koschinsky et al.,
1997].
These examples indicate that phosphogenesis occurred in the equatorial Atlantic and equatorial Pacific
Oceans during the same time intervals [Hein et al., 1993; Jones et al., 2002]. Therefore, it can be inferred that
strong upwelling occurred also in the northeast Atlantic during these late Oligocene to early Miocene phos-
phogenetic events. Although we have not sampled phosphorite of late Eocene to early Oligocene age in
the Galicia Bank area, as occurs in the Pacific Ocean [Hein et al., 1993], we do not disregard the possible
occurrence of phosphatization during that period because chalk samples with middle Eocene coccoliths
were reported by Black [1964] near Station DRR81.
5.1.2. Paleoenvironmental Conditions and Constraints
The types of foraminifera and radiolarians reflect the paleoceanographic conditions that prevailed around
Galicia Bank during phosphatization. Foraminiferal assemblages within phosphorites, such as the occur-
rence of Austrotrillin, indicate deposition of limestone in shallow water during the early Miocene (24–23
Ma), before the bank began to subside. The occurrences of radiolarians and globular planktonic foraminifera
(e.g., Globigerinoides) indicate that the bank was connected to the open ocean. Moreover, abundant radio-
larians indicate high productivity waters around the bank due to upwelling.
The replacement of carbonate minerals by CFA is favored by the high concentrations of P in the pore waters
of carbonate sediment and suboxic redox conditions. For example, sulphur bacteria, which contain large
amounts of intracellular polyphosphates, can drive precipitation of CFA in suboxic-anoxic sediments [Schulz
and Schulz, 2005]. They derive energy by oxidation of sulphide using nitrate or oxygen as the electron
acceptor. Apatite replacement of carbonate by microbially mediated enzymatic reactions promotes PO32 4
21
release from organic matter and CO22 3 and Ca release from carbonates by dissolution via organic acids
[Lamboy, 1993]. The fact that Galicia Bank was located relatively close to the Iberian margin indicates that
plankton-derived organic matter supplied the phosphate to the sediments. In addition, Galicia Bank and
neighboring seamounts should have supported obstructional upwelling as water masses impinged on
those edifices, which would also have promoted upwelling and associated productivity in surface waters.
Strong upwelling is supported by the abundance of foraminifera and radiolarian found in the phosphorites
(Figure 6 and Table 3). Barium, Cu, and Zn are enriched in the phosphorites from high productivity regions
(e.g., Peru and Namibia margins) with an important contribution of plankton-derived organic matter [Price


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and Calvert, 1978; Froelich et al., 1988]. However, moderate concentrations of these elements in the phos-
phorites of Galicia Bank (Table 1) are related to Fe-Mn replacements and encrustations rather than the
involvement of marine plankton.
The low eNd values of phosphorites may be explained by exchange between nonradiogenic bottom waters
and surface waters caused by upwelling of cold, nutrient enriched water. Most eNd(0) values of phosphorites
(Table 3) fall in the range of 27 to 29, characteristic of North Atlantic waters extant from 25 to 17 Ma [Stille
et al., 1996]. However, the progressive decrease in eNd(0) from 28 to 29 for the first phosphatization event
during the late Oligocene-early Miocene (25–22 Ma) to 210.71 in the late-early Miocene event (18–17 Ma)
can be explained by the progressive increasing influence of the Northern Component Water (NCW) pro-
moted by the formation of the northern gateways, the Greenland-Scotland-Ridge [e.g., M€ uller-Michaelis
et al., 2013]. This is discussed further in the next section.
5.1.3. Proposed Genetic Model
Most published phosphogenetic models address phosphorites that formed in organic-matter-rich environ-
ments, particularly areas of strong upwelling along highly productive continental margins (e.g., Peru and
Namibian margins). On the other hand, there are few reports dealing with phosphorites that formed in
moderate to low-productivity environments with organically poor host sediments [Hein et al., 1993; Ben-
ninger and Hein, 2000]. We suggest that formation of phosphorites on Galicia Bank fit a genetic model that
includes parts of both of these models. It is well known that phosphatization is favored under suboxic con-
ditions because P is enriched in suboxic-anoxic sediments by early microbial degradation of organic matter,
and several redox reactions that occur at various depths in the sediment: sulphate-reduction, sulphide-oxi-
dation, and Mn and Fe oxide dissolution and release of incorporated P [e.g., Burnett and Riggs, 1990; Schulz
and Schulz, 2005; Filippelli, 2011]. Fe-Mn-oxide formation is favored under more oxic conditions. If bottom
waters become anoxic, phosphorite typically forms at the upper and lower margins of the anoxic OMZ,
such as off the Peru-Chile margin [e.g., Glenn and Arthur, 1988]. The redox cycling of Fe-Mn oxyhydroxides
may play an important role in concentrating phosphorous around Galicia Bank as reported for other areas
with discontinuous and moderate upwelling [Jarvis, 1992; Benninger and Hein, 2000]. Our phosphogenesis
model follows this sequence: (1) carbonate sediment accumulated on Galicia Bank during the Oligocene
and early Miocene, possibly also the Eocene. Dissolved phosphate in seawater concentrated in a suboxic
OMZ when Galicia Bank was still in relatively shallow water, too shallow for the formation of hydrogenetic
Fe-Mn deposits. The sources of dissolved and colloidal Fe were from the Iberian continental margin and
from leaching of basement rocks by geothermally driven circulation of fluids. This colloidal Fe provided a
substrate for the sorption of P, adding to the available P pool; (2) this suboxic, P-rich environment was ideal
for the early diagenetic replacement of the carbonate sediment, which was phosphatized from pore fluids
below as well as at the seafloor where the OMZ intersected the bank. This phosphatization produced miner-
alization fronts that crosscut depositional fabric (Figures 5a and 6g). The result of phosphatization was the
formation of a hardground, which constitutes the phosphorite slabs described here; (3) after additional sub-
sidence of the bank, and boring of the hardground by benthic fauna, Fe-Mn deposits formed and through
diagenetic processes replaced the margins of the phosphorite slabs and areas adjacent to fractures and
other porosity; (4) at this stage, redox recycling of Fe-Mn oxides and bacterially mediated reactions (e.g., sul-
phide oxidation by Thiomargarita) [Schulz and Schulz, 2005] likely precipitated additional phosphorite; parts
of the older phosphorite and Fe-Mn deposits were redistributed and in the process concentrated economi-
cally important metals. These recycling and diagenetic processes are important in the formation of phos-
phorite in organic-matter-poor environments [O’Brien and Heggie, 1988; O’Brien et al., 1990].
The presence of radiogenic Sr in phosphorites (ratios up to 0.7148) indicates participation of mineralizing
fluids that imprinted their isotopic Sr signature in the phosphorites. We interpret these changes to be
related to input of hydrothermal fluids that may have also promoted remobilization and precipitation of
phosphates as observed in brecciated samples (Figure 6h). These hydrothermal inputs are addressed in sec-
tion 5.3.3.
The phosphate nodules show internal discontinuities (Figure 6j) linked to erosion by currents probably asso-
ciated with sea level low stands during global cooling, which was common in the middle Miocene [Vincent
and Berger, 1985; Flower and Kennet, 1993]. The presence in the nodule of botryoidal fluorapatite and CFA,
atypical of marine phosphorites, may indicate primary precipitation of phosphates in the sediments or
phosphate replacement of Fe-Mn oxyhydroxides. In this way, the high contents in Fe, Mn, and trace metals


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Figure 9. Schematic model for different types of mineralization in the Galicia Bank region and age sequences of tectonic and oceanographic events. The asterisks represent the Sr
inferred ages for mineralizations. See text for detailed explanation.

can be explained either by phosphate replacement of Fe-Mn oxyhydroxides or by the diagenetic inter-
growth of Fe-Mn oxide layers in the nodule. The nucleus of this nodule is an older phosphorite fragment.
Fragmented phosphorite can be interpreted to result from brecciation of older phosphorites through grav-
ity mass movement or tectonic processes during the Miocene, generating the nuclei for growth of new
phosphorite and Fe-Mn nodules (Figure 9).

5.2. The D1 Unconformity: A Significant Early Miocene Paleoceanographic and Tectonic

Reorganization in the North Atlantic
Based on the seismic profiles combined with the location of the dredge stations (e.g., Figure 3), we correlate
the high reflective D1 unconformity with the phosphatized hardground. The age of this hardground is con-
strained by the age of the host sediment dated by Sr isotopes as latest early Miocene (17–16 Ma, Table 3
and Figure 9), and evidence for an early diagenetic origin for the phosphatization. This age correlates with a
regionally significant unconformity preserved in North Atlantic deep water basins and dated from Faroe-
Shetland Rockall Trough to Porcupine Bank as 19–16 Ma [e.g., Stoker et al., 2002; M€ uller-Michaelis et al.,
2013]. This unconformity was first recognized in DSDP cores on Goban Spur and Rockall Trough [de Gracian-
sky et al., 1984] and was related to vigorous bottom currents resulting from the introduction of Norwegian
Sea Water along the North Atlantic margins. The Faroe Conduit developed in the early Miocene and was
suggested to be the first true deep water connection between the Nordic Seas and the Atlantic [Stoker
et al., 2005].
Therefore, we propose that the latest early Miocene D1 unconformity marks the abrupt end to the domi-
nant phases of phosphogenesis, terminated by the marked changes in the oceanographic regime. The
occurrence of a massive contourite drift mega-sequence (Unit U2, supporting information Figure S2) overly-
ing this D1 unconformity confirms the establishment of vigorous bottom currents following the period of
phosphogenesis. We suggest that these strong bottom currents were the result of the onset of the Northern
Component Water (NCW) that impinged directly on Galicia Bank (Figure 10). Therefore, the submergence of
the Greenland-Scotland Ridge resulted in locally vigorous deep water erosion as northern-sourced deep
water flowed through the Faroe-Shetland Channel into the NE Atlantic [e.g., Stoker et al., 2002] (Figure 10).
The fact that the D1 unconformity is extensively faulted on Galicia Bank and Sancho seamount (supporting
information Figure S1) suggests that tectonic reactivation occurred after termination of the main


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phosphatization events and before deposition of the contourite drifts of Unit U2. This tectonic reactivation
is linked to intraplate tectonism dated as early Miocene that occurred in the NE Atlantic, including the open-
ing of the Faro €e-Shetland Channel and Rockall Trough associated with significant basin subsidence [Stoker
et al., 2001].
This tectonic event is reflected in the southern NE Atlantic margins as continent-ocean collision resulting in
northward subduction of the Bay of Biscay oceanic crust beneath the Iberian continental crust. The age of
this event, based on the age of the last deposits involved in the accretionary prism developed along the
North Iberian Margin, was estimated to have been active until the Burdigalian (20.43–15.97 Ma) [Alvarez-
Marron et al., 1997]. Given these constraints, we suggest that the tectonic event affected Galicia Bank
between the last main phosphatization event in the latest early Miocene (18–17 Ma) and the end of the
subduction of the Biscay Bay at early/middle Miocene (15.97 Ma; Figure 9).

5.3. Early/Middle Miocene Geothermal Fluid Circulation, Co-Rich Mn Nodules, and Subseafloor
Mineralization
We interpret the exceptional Co-rich Mn nodules and stratabound Mn replacement and encrustation of
phosphorite deposits collected along the flanks and summits of seamounts from the Galicia Bank region as
having formed through diagenetic processes. The circulation of mineralizing fluids was driven by geother-
mal heat, which produced metal-rich hydrothermal fluids. This suggestion is based on the uncommonly
high Co contents in the nodules compared to hydrogenetic Fe-Mn nodules and crusts, the positive Eu
anomaly, the Nd isotopic signature, and the Sr isotopes.
5.3.1. Age Constraints and Source of Mineralization
Mn-oxide mineralization occurred during at least two time intervals (Table 3 and Figure 10): early Miocene
(23.8–22.6 Ma) for Galicia Bank Co-rich nodules and latest early Miocene (18.5–17.7 Ma) for Mn-oxide
replacement of phosphorite slabs on Sancho seamount. These dates assume that Sr was derived mainly
from seawater. The Co-rich Mn nodules were collected where the D1 phosphatized hardground was
breached by chimneys, which represent fluid and sediment (diapir) upflow zones (Figure 4). The spherical
shape of some of the nodules indicates that they formed either at the seafloor or within water-saturated
unconsolidated sediment.
The seismic-defined chimneys crosscut sedimentary Unit U1, the D1 unconformity, and partially Unit U2.
Even though it is difficult to discern on the seismic profiles, the seismic chimneys appear to be rooted in
zquez et al., 2008; Va
semitransparent acoustic facies interpreted to be black shale [Va zquez et al., 2009b]. A
black shale at the base of the postrift Units (Albian-Cenomanian in age) has been described from Galicia
Bank and surrounding regions [Boillot and Malod, 1988]. The shale is composed of homogeneous to lami-
nated claystone and interbedded mudstone. Rising diapirs and associated fluid venting as a response to
compressional tectonics could be driven by the viscosity of the black shale and abundant hydrocarbons.
Black shales are known to be enriched in metals [e.g., Vine and Tourtelot, 1970], and this source can explain
the high concentration of metals found in the Co-rich Mn nodules and stratabound Mn deposits. In addi-
tion, igneous rocks (granites and granodiorites) and possibly massive sulphides from the Ossa Morena base-
ment of Galicia Bank may have been a supplementary source of metals for the mineralization at the
seafloor. The Galicia Bank area nodules have higher Co than nodules from any other area of the modern
ocean basin [Hein et al., 2015]. These remarkably high Co contents must have a source in addition to sea-
water and our proposal of leaching of black shale and/or basement rocks is a viable explanation.
Therefore, we propose that the abundant metals in the Co-rich Mn nodules and Fe-Mn stratabound depos-
its are related to fluid/sediment upflow structures driven by regional tectonic reactivation during the early
and middle Miocene. In addition, geothermally driven fluid circulation along these structures promoted
transport of metals for mineralization at and near the seafloor (Figure 10 and supporting information Figure
S1).
5.3.2. Paleoenvironment
The Co-rich Mn nodules from the Galicia Bank region show predominantly spheroidal and cylindrical mor-
phologies with abundant microfossils, indicating their formation near but below the water-sediment inter-
face. Cylindrical nodules are similar to tubular concretions formed around burrows that occur in the Black
lez et al., 2012]. It is likely that the cylindrical nodules
Sea and the Gulf of Cadiz [Baturin et al., 2002; Gonza
grew around burrow tubes within sediments. The different types of nucleus in part determine the final


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Figure 10. Paleoceanographic and tectonic events reconstruction of the North Atlantic at the time of mineralization of the Galicia Bank
(GB) region.

morphology of the nodules, including nucleation associated with redox horizons. Foraminifer tests and
detrital grains acted as nucleation sites for the spheroidal Co-rich Mn nodules in areas dominated by bio-
clastic sediments.
5.3.3. Proposed genetic Model
Typically, the precipitation of Mn oxides from hydrothermal fluids occurs below the water-sediment inter-
face as stratabound layers and cement with a large fractionation between Fe and Mn [Hein et al., 1997;
Koschinsky and Hein, 2003; Hein et al., 2005]. These processes occur when the oxides precipitate rapidly from
low-temperature hydrothermal fluids (<1208C), which does not allow time for trace metals to be adsorbed
by the precipitates. However, the oxide minerals can be enriched in one or more of Li, Mo, Zn, Pb, Cu, or Cr,
rarely Co, based on the types of basement rocks leached, the composition of the fluids, and formation of
mineral deposits deeper in the hydrothermal system [Hein et al., 1997]. The Co-rich Mn nodules from Galicia
Bank are characterized by a submetallic luster, presence of 10 and 7 Å manganates, high Mn/Fe ratios, low
REY contents, positive Eu anomalies, and moderate to high Mo, Pb, V, and Tl contents, all characteristic of
hydrothermal Mn deposits from the modern ocean basins. The Mn nodules plot at the almost pure Mn-rich
end-member (Mn/Fe 45–153) on the Mn-Fe-(Co 1 Ni 1 Cu) 3 10 ternary diagram [Bonatti et al., 1972; Lyle,
1981; Dymond et al., 1984]. On the other hand, the very high Co (up to 1.8 wt %), moderate Te, and a posi-
tive Ce anomaly are unusual for hydrothermal Fe-Mn deposits. The positive Ce anomalies can be explained
by the input of a hydrogenetic Fe-Mn component. This component can be identified using the REY plots of
Bau et al. [2014], where the Co-rich nodules plot either in the hydrogenetic (seawater-sourced) field or
between the hydrogenetic and hydrothermal fields (Figure 11). This dual source can also be seen in REY pat-
terns that share features with both hydrogenetic deposits (positive Ce anomaly and negative Y anomaly)
and hydrothermal deposits (positive Eu anomalies). Our data show that hydrothermal and hydrogenetic
deposits form a continuum and that it does not seem to matter whether the hydrothermal system is geo-
thermally or magmatically driven. Continuous REY scavenging from seawater would increase the REY con-
centrations and reduce the YSN/HoSN ratios with time; the CeSN/CeSN* ratios would increase as long as the
Co-rich Mn nodules were exposed to seawater.
The Sr isotopes of CFA in the phosphorite slabs (0.7123–0.7148) are anomalously high compared to Mio-
cene seawater, which we interpret to reflect the hydrothermal-fluid component to the mineralized slabs
(Table 3). The Sr isotopic values are characteristic of continental rocks and indicate that the leached source


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Figure 11. Plot of Fe-Mn deposits on graphs of CeSN/CeSN versus Nd concentration and CeSN/CeSN ratios (after Bau et al. [2014]). The sam-
ples plot into distinctive areas on these diagrams discriminating among the different genetic types of Fe-Mn mineralization. For further
explanation see text.

rocks included either Mesozoic and Cenozoic terrigenous units of the Atlantic passive margin or Paleozoic
granitic-granodioritic rocks of the Ossa Morena Variscan Zone that conform to the basement of Galicia Bank
[Capdevila and Mougenot, 1988]. The Nd isotopes of the Fe-Mn mineralization show nonradiogenic values
of 0.512169 (ENd 5 29.15) and 0.512198 (eNd 5 28.58). We interpret those values to represent either a
hydrothermal mineralizing fluid sourced from a mix of continental crustal rocks, and/or a hydrogenetic
component precipitated from North Atlantic seawater [Stille et al., 1996].
We suggest that besides the hydrothermal and hydrogenetic components in the Co-rich nodules, early-
diagenetic remobilization of components disseminated in the sediment was facilitated by the hydrothermal
fluids. The high contents of Mo and Ba are partly explained by this diagenetic remobilization. All these fac-
tors indicate a mixed hydrothermal-hydrogenetic-diagenetic origin for the Mn nodules.
The Fe-Mn stratabound layers and impregnations also reflect tectonic and hydrothermal processes. Their
textures and mineralogy are indicative of a hydrothermal origin, brecciation by hydrofracturing, and Mn-
oxide precipitation and replacement of the phosphorites (Figures 5b, 5c, 6b, and 6C; anal. DRR47-2, DRR47-
2-12, DRR47-2-3, and DRR47-2-4 in supporting information Table S2). The intense brecciation of phosphorite
may be related to formation of the chimneys (diapirs and domes) impacting the D1 phosphatized hard-
ground shown on seismic profiles (Figures 3 and 4). Thus, we interpret these structures as having been pro-
duced by ascending hydrothermal fluids that brecciated the phosphorite slabs and then cemented and
replaced the brecciated mega-clasts by hydrothermal Mn oxides. The enriched metals (e.g., Mn, Co, Ni, Pb,
Mo, and Tl) in the nodules and stratabound layers may have been carried by these ascending fluids. The sys-
tem of faults generated as a response to the Cenozoic reactivation during the Pyrenean orogeny, which


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zquez et al., 2008], would have provided the conduits for hydrothermal circula-
also affected Galicia Bank [Va
tion that leached the basement rocks.
The Co-rich manganese nodules and diagenetic Fe-Mn replacements of phosphorite show many similarities
in geochemistry and mineralogy (Table 2 and supporting information Figure S3). The Fe-Mn-oxide cements
and replacements show 7 and 10Å manganates, high Mn/Fe ratios, and moderate to high Li contents, char-
acteristics of a hydrothermal component. The high Tl or V can also be interpreted as derived from hydro-
thermal fluids. The difference between Fe-Mn diagenetic layers and Co-rich manganese nodules is clearly
seen in the REY patterns (Figure 8). The Fe-Mn stratabound layers preserve the REY patterns characteristic
of unaltered phosphorites from the Galicia Bank area, whereas Co-rich Mn nodules show significant Eu
anomalies. All these parameters indicate that the Co-rich manganese nodules and Fe-Mn impregnations
and replacements of phosphorites are predominantly of hydrothermal origin with a common mineralization
fluid. We suggest that this difference in REY patterns can be interpreted as different products of mineraliza-
tion from the same hydrothermal fluids: (a) Fe-Mn stratabound replacements of CFA by (Fe)-Mn oxyhydrox-
ides took place by more focused flow of hydrothermal fluids through fracture and fault systems that
mineralized and brecciated the hardgrounds; and (b) Co-rich manganese nodules formed in a diffuse-flow
system of hydrothermal fluids within soft sediment.

5.4. Middle and Late Miocene Hydrogenetic Fe-Mn Crusts

Fe-Mn crusts cover hard rock substrates in the Galicia Bank regions as they do on many other seamounts in
the global ocean [e.g., Manheim and Lane-Bostwick, 1988; Koschinsky et al., 1997; Hein et al., 1997; Hein, 2004;
Hein et al., 2013].
5.4.1. Age Constraints of Mineralization and Contourite Drift Deposits
The Fe-Mn crusts show average thicknesses of 7–8 mm (maximum 15 mm) and high contents of Co, which
indicate slow growth rates (1.6 mm Ma21 for the Fe-Mn crust in Table 2). The age of the Fe-Mn crusts is
estimated to be younger than about 9.5 Ma based on the thickest crust and using the empirical equation of
Manheim and Lane-Bostwick [1988]. This equation does not identify possible growth hiatuses during the
accretion process so the calculated rates of growth are semiquantitative and represent maximum values
and the calculated ages are minimum ages [Hein et al., 1990; Frank et al., 1999]. This indicates that growth
of the hydrogenetic Fe-Mn crusts in the Galicia Bank region was initiated during the late Miocene, coeval
with the formation of the contourite drift of seismic Unit U2 (Figure 10 and supporting information Figure
S2). This giant contourite drift body migrated up slope from 1570 to 1125 m water depths over a ramp
formed by the phosphatized D1 unconformity. Thus, Fe-Mn crusts grew progressively on a nondeposition
surface that was not overlapped by the upslope migration of the contourite drift (supporting information
Figure S2). We suggest that this contourite drift deposited along the foot and slopes of Galicia Bank was
driven by vigorous south-flowing deep water bottom currents due to the introduction of Norwegian Sea
Water into the North Atlantic [e.g., de Graciansky et al., 1984; Stoker et al., 2001; M€
uller-Michaelis et al., 2013].
This indicates that vigorous current activity prevented deposition of sediment and kept bare rock exposed,
necessary for the growth of the crusts.
5.4.2. Paleoenvironmental Constrains and Genesis
All the Fe-Mn crusts show similar petrographic, mineralogical, and chemical compositions: thin colloform
laminations of vernadite and amorphous Fe-Mn oxides, subequal amounts of Fe and Mn (Mn/Fe ratio 1),
strongly positive Ce anomaly, no Eu anomaly, negative Y anomaly, and high contents of REY and trace met-
als (Figure 8). The chemical composition and discrimination plots clearly show a hydrogenetic origin of
these thin crusts (Figure 11), which coat all hard substrates and previously mineralized rocks (Fe-Mn nodules
and phosphorite slabs). Thus, either the hard substrates were relatively recently swept free of sediment or
have been only intermittently exposed. We suggest that during the formation of the drift deposits of Unit
U2, alternate periods of strong and weak bottom currents may have alternated giving rise to exhumation
and burial stages with periods of dissolution or nongrowth alternating with periods of growth of the Fe-Mn
crusts.

5.5. The Pliocene D2 Unconformity, Impingement of Mediterranean Outflow Water, and Formation of
Fe-Rich Nodules
A major erosional unconformity named D2 affected the entire Galicia Bank region (supporting information
Figure S2) and adjacent basin (supporting information Figure S1). This erosional unconformity produced
moats around the banks and seamounts. A sequence of stepped coral mounds intercalated with contourite


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drifts overlies this erosional unconformity, termed R1 by Somoza et al. [2014]; they correlated R1 with the
RD1 erosional unconformity that occurs on Porcupine Bank [Van Rooij et al., 2003]. This was interpreted as a
late Pliocene regional unconformity related to the reintroduction of MOW in the NE Atlantic [e.g., Stow,
1982]. Moreover, data from IOPD Expedition 307 at Porcupine Bank showed that coral growth started
around 2.7 Ma [Kano et al., 2011]. Since the late Pliocene, the MOW has impinged on Galicia Bank creating
initially an abrupt increase in salinity (above 35.9&) and a marked decrease in oxygen (below 5.45 mg/L) at
the seabed with respect to the adjacent Eastern North Atlantic Central Waters (ENACW).
5.5.1. Pliocene-Quaternary Fe-Rich Nodules
We suggest that this change in the oceanographic regime due to the MOW impinging on Galicia Bank
caused a change in the type of seabed mineralization from Miocene to Pliocene. Moreover, along the trajec-
tory of the MOW flow sourced from Gibraltar Strait, the type of mineralization shows the same geochemical
characteristics. For example, the Fe-rich nodules and thin crusts collected from the Gulf of Cadiz along the
Mediterranean undercurrent channels show similar characteristics to the Fe-rich nodules in the Galicia Bank
area [Gonza lez et al., 2012]. The Fe-rich nodules recovered at stations DRR37 and DRR38 are related to the
MOW (supporting information Figures 3 and 5).
The time of Fe-rich nodule formation is constrained to seismic Unit U3, which overlies the regional erosional
unconformity D2. As discussed above, we interpret this unconformity to be caused by the reintroduction of
MOW in the NE Atlantic at least from 2.4 Ma.
5.5.2. Paleoenvironmental Condition and Constrains
Unit U3 is related to the MOW and developed at the summit of Galicia Bank by deep water coral mounds
and intercalated with upslope migrating sediment drifts at water depths from 1125 to 826 m [Somoza et al.,
2014]. The sedimentary cover consists of sand waves 3–7 m high and 120–150 m wavelengths. Current
speed measurements yielded values ranging from 5 to 30 cm/s with average values of 8 cm/s. This environ-
ment was favorable for the diagenetic growth of Fe-rich nodules within muddy-sandy drift bodies. During
glacial-interglacial cycles, alternating periods of nondeposition and/or erosion resulted from alternating
strong and less vigorous bottom currents that allowed for the construction of the sedimentary drifts. These
alternating periods of erosion and sedimentation likely caused variations in the redox boundary, which pro-
moted formation of the Fe-rich nodules and their successive exhumation and burial.
5.5.3. Proposed genetic Model
The tabular Fe-rich nodules contain redox-sensitive minerals, such as pyrite (Figure 7f). The tabular form
reflects mineralization fronts associated with redox boundaries in the sediment column during early diagene-
sis, as also occur in Fe-Mn nodules from the Gulf of Cadiz [Gonza lez et al., 2012]. Compared to average compo-
sitional values reported from deep-sea nodules [Baturin, 1988], the Fe-rich nodules show very low Mn/Fe
ratios (0.03–0.09) and low trace metal and REY contents (Table 2). They are enriched in Fe, Mg, As, V, and B
and are quite similar to nodules collected from the Gulf of Cadiz and Black Sea [Baturin et al., 2002; Gonza lez
et al., 2009]. The nodules are almost pure ironstone (Mn/Fe 5 0.03) end-member based on the classification of
oceanic nodules using the ternary diagram Mn-Fe-(Cu 1 Ni 1 Co) 3 10 [Bonatti et al., 1972; Lyle, 1981;
Dymond et al., 1984]. Abundant references report on nodules from shallow waters and continental margins
where Fe, Mn, and trace metal contents are rather similar to these Galicia Bank Fe-rich nodules [e.g., Calvert
and Price, 1977; Bostro €m et al., 1982; Ingri, 1985; Glasby et al., 1987, 1997; Baturin et al., 2002; Gonza
lez et al.,
2007]. They all show low Mn/Fe ratios as a result of fast growth rates associated with diagenetic processes,
emphasizing the importance of sediment diagenetic processes [Reyss et al., 1982]. This relatively rapid accre-
tion is one of the main causes for the overall low content of transition metals in these nodules.
On bivariate diagram of CeSN/CeSN* versus Nd concentration (Figure 11), the Fe-rich nodules lack Ce anoma-
lies and Nd concentrations are low (5–10 lg/g). In the bivariate diagram of CeSN/CeSN* versus YSN/HoSN ratio
(Figure 11), the Fe-rich nodules show slight negative Y and Ce anomalies. Both diagrams discriminate these
nodules as diagenetic in origin, but overlaps slightly with the hydrothermal field.
The high contents of B, V, and As in these nodules probably reflect contributions from hydrothermal circula-
tion combined with the affinity of these elements for sorption by goethite. We suggest that the origin of
these Fe-rich nodules might be linked to hydrocarbon-rich fluids (perhaps sourced from the underlying
black shale unit) that underwent microbial degradation in the sulphate reduction-methanogenic transitional
diagenetic zone and was oxidized periodically by exhumation due to vigorous MOW currents, as also pro-
posed for the Gulf of Cadiz deposits [Gonza
lez et al., 2012].


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6. Conclusions
In this paper, we analyzed for the first time a sequence of marine mineral deposits discovered on Galicia
Bank (NE Atlantic Iberia margin). The mineral deposits include four types: (1) phosphorite slabs and nodules,
(2) Fe-Mn crusts and stratabound deposits, (3) Co-rich Mn nodules, and (4) Fe-rich nodules. Using a combi-
nation of geophysics, mineralogy, geochemistry, and isotopic analyzes, we were able to relate the different
types of mineralization to tectonic and paleoceanographic events and fluid-transport processes.
1. From the late Oligocene to early Miocene, three growth generations of phosphorites were identified
within the Galicia Bank region (1) late Oligocene (25.7–24 Ma), (2) early Miocene (23.8–22.6 Ma), and (3)
latest early Miocene (18.6–16.8 Ma). The events of phosphatization occurred during transitions from gla-
cial to warm climates in the late Oligocene-early Miocene, coincident with the phosphogenetic episodes
over a wide area of the equatorial Pacific and Atlantic [Hein et al., 1993; Jones et al., 2002]. These phos-
phatization events indicate that moderate upwelling occurred also in the NE Atlantic during those peri-
ods of transition.
2. During the late Oligocene to latest early Miocene, the progressive decrease in eNd values for the phos-
phatization events is interpreted to reflect increasing influence of the Northern Component Water (NCW)
caused by the progressive opening of the northern gateways [e.g., M€ uller-Michaelis et al., 2013].
3. During the latest early Miocene, hydraulic fracturing of the phosphorite hardground was caused by
regional intraplate tectonism in the North Atlantic, forming a widespread North Atlantic erosional uncon-
formity (19–17 Ma), termed D1. This regional unconformity occurring in the deep North Atlantic is asso-
ciated with activity of the Iceland hot spot and opening of the Iceland-Faroe Channel and Rockall
Trough. In the Galicia Bank region, the North Atlantic tectonism was transferred as compressional stress
promoting subduction of the northern Biscay Bay oceanic crust beneath the continental crust of the
North Iberian margin.
4. During this latest early Miocene episode of active tectonism, Mn-impregnations of the phosphorite hard-
grounds formed stratabound layers, and Co-rich manganese nodules with remarkably high Co contents
(to 1.8 wt %) and other trace metals, and with significant Eu anomalies. These deposits are interpreted to
have been derived from metal-rich hydrothermal fluids that leached organic-matter-rich sediments and/
or continent basement rocks underlying the bank and adjacent seamounts. Seismic-delineated chimneys
reflect ascending fluids and sediments (diapirs) in the vicinity of hydrofractured metalliferous phosphor-
ites and Co-rich nodules. Reactivated faults were the main fluid transport pathways and high geothermal
gradients associated with thinned crust drove the hydrothermal circulation cells.
5. During the middle and late Miocene, and once the Scotland-Iceland gateways opened, the introduction
of vigorous deep-sourced water from the Arctic impinged directly on Galicia Bank through Rockall
Trough. This deep water flow promoted precipitation of hydrogenetic Fe-Mn crusts enriched in Co and
Ce by keeping substrate rock free of sediment accumulation. The Fe-Mn crusts are estimated to have
started growth around 9.5 Ma ago.
6. During the late Pliocene, the growth of diagenetic Fe-rich nodules with low contents of Mn and trace
metals was associated with the reintroduction of hypersaline Mediterranean Outflow Water by opening
of the Africa-Europe gateway at about 2.4 Ma. Moreover, along the trajectory of the MOW, sourced from
Gibraltar Strait, mineralization shows the same geochemical characteristics. Thus, the Fe-rich nodules
and crusts collected from the Gulf of Cadiz along the Mediterranean undercurrent channels show similar
lez et al., 2012].
characteristics as the Galicia Bank area Fe-rich nodules [Gonza

We interpret this succession of mineralization as controlled by major changes in the oceanographic and tec-
tonic regimes that triggered the present global thermohaline circulation (THC) during the Cenozoic through
the introduction of Arctic and Mediterranean waters into the North Atlantic Ocean. Traditionally, the
Eocene/Oligocene boundary at about 33.9 Myr ago marks the transition from a greenhouse to icehouse
world [e.g., Abelson et al., 2008]. We conclude based on data for the mineral deposits from Galicia Bank that
the transition between the greenhouse phosphorite mineralization and icehouse Fe-Mn crust mineraliza-
tion, that occurred after the last event of phosphatization, took place during the latest early Miocene
(18.6–16.8 Ma). This marked change in the type of mineralization on Galicia Bank is coeval with a wide-
spread regional unconformity (19–17 Ma) identified in the North Atlantic deep basins linked to the opening
of the gateway for Arctic-sourced deep water flow into the North Atlantic [e.g., Dingle et al., 1982; Stoker


GONZALEZ ET AL. MINERALIZATIONS FROM GALICIA BANK 370
 Geochemistry, Geophysics, Geosystems 10.1002/2015GC005861

et al., 2001; M€
uller–Michaelis et al., 2013]. Furthermore, a major intraplate tectonic event occurred in the NE
Atlantic during this period, the suppression of the Iceland hot spot plume and/or the rifting of Rockall
Trough seem to have played an important role in triggering rapid deepening of the Greenland-Scotland
Ridge, the sill between the Nordic Seas and North Atlantic. We suggest that this major oceanographic/tec-
tonic event promoted the hydrofracturing of the phosphorite hardground and the subsequent Mn replace-
ment of the margins of phosphorite slabs as well as formation of the striking Co enrichment of the
manganese nodules associated with hydrothermal fluids. These types of mineral deposits are testimony of
the abrupt climate transition between a greenhouse and icehouse world and by regional intraplate tecton-
ics that opened the passage of Nordic waters into the Atlantic and triggered the present global thermoha-
line circulation.

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