Pillow Basalt On Schreiber Beach

Chemical Geology 326–327 (2012) 145–173
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Chemical Geology
journal homepage: www.elsevier.com/locate/chemgeo
Extreme element mobility during transformation of Neoarchean (ca. 2.7 Ga) pillow
basalts to a Paleoproterozoic (ca. 1.9 Ga) paleosol, Schreiber Beach, Ontario, Canada
Ali Polat a,⁎, Fred Longstaffe b, Chris Weisener a, c, Brian Fryer a, c, Robert Frei d, e, Robert Kerrich f
a
Department of Earth and Environmental Sciences, University of Windsor, Windsor, ON, Canada
b
Department of Earth Sciences, The University of Western Ontario, London, ON, Canada N6A 5B7
c
Great Lakes Institute for Environmental Research, University of Windsor, Windsor, ON, Canada N9B 3P4
d
Institute of Geography and Geology, University of Copenhagen, 1350-Copenhagen, Denmark
e
Nordic Center for Earth Evolution, NordCEE, Denmark
f
Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK., Canada S7N 5E2
a r t i c l e i n f o a b s t r a c t
Article history: This study reports petrographic, major and trace element, and oxygen isotopic data for a subaerial weathering
Received 3 February 2012 profile at Schreiber Beach, Ontario, Canada. The weathering profile developed on Neoarchean (ca. 2.7 Ga)
Received in revised form 22 July 2012 pillow basalts and is unconformably overlain by the Paleoproterozoic (ca. 1.88 Ga) Gunflint Chert and basal
Accepted 27 July 2012
conglomerates. This stratigraphy suggests that the basalts were uplifted and subaerially weathered prior to
Available online 5 August 2012
deposition of the Gunflint Formation. Rocks at Schreiber Beach have been classified as pillow cores, pillow
Editor: U. Brand rims, hyaloclastites, weathered red basalts, and weathered brown to green basalts. There are gradual
textural, mineralogical, and geochemical transitions from unweathered basalts to intensely weathered
Keywords: hematite-bearing basalts with stratigraphic height.
Paleoproterozoic Rocks at Schreiber Beach underwent seafloor hydrothermal alteration and greenschist facies regional meta-
Paleosol morphism in the Neoarchean. Following the subaerial weathering, they were buried and re-metamorphosed
Archean pillow basalt to greenschist facies in the Paleoproterozoic. Given the preservation of primary igneous textures and trace
Gunflint Formation element patterns in pillow cores, they are used as a protolith to estimate element mobility during seafloor
Trace element
alteration, metamorphism, and subaerial weathering. Chloritized pillow rims and hyaloclastites are charac-
Oxygen isotopes
terized by moderate losses or gains of major (Si, Ca, Na, Fe, Ti, K) and trace (LILE, REE, HFSE, and transition
metals) elements during Neoarchean seafloor alteration. Alteration of these rocks at relatively low tempera-
tures is indicated by enrichment in 18O (δ18O = +10.4 to + 12.7‰) relative to fresh basalt (~+ 5.5‰).
Subaerial weathering resulted in significant textural, mineralogical (e.g., hematite precipitation), and
geochemical variations in metamorphosed basalts, causing additional redistribution of most major and
trace elements and further enrichment in 18O. The highest δ18O values (+16.1 to + 17.1‰) occur at the
silica-rich base of the weathering profile. Many elements, including LILE, REE and HFSE, are strongly enriched
(>100%) or depleted (up to 96%) relative to their original abundances. Alkaline metasomatism, which is a
characteristic of Precambrian paleosols, is also evident at Schreiber Beach, where extreme enrichment in K
(280 to 1000%), Rb (390 to 660%), and Cs (1160 to 2560%) occurs in the weathering profile.
© 2012 Elsevier B.V. All rights reserved.
1. Introduction nature of such processes under Precambrian conditions is of special in-

terest. However, while many Archean greenstone belts record chemical
Seafloor alteration and subaerial weathering produce major changes and physical changes resulting from submarine alteration (Feng et al.,
in the compositions of their precursors as well as of the lithosphere, hy- 1993; Polat et al., 2003, 2007), the products of Precambrian subaerial
drosphere and atmosphere, and affect the course of biological evolution weathering are rarely preserved (Retallack, 2001). The chemistry of
and climate change (Nesbitt and Young, 1982; Holland, 1984; Beukes et Precambrian subaerial weathering profiles, including paleosols, was al-
al., 2002; Jablonski, 2003; Lenton, 2003; Nisbet and Sleep, 2003; Veizer most certainly affected by the composition of the ancient atmosphere
and MacKenzie, 2003; Stafford et al., 2005; Navarre-Sitchler and (Holland, 1984; Rye and Holland, 1998; Retallack, 2001; Sheldon,
Brantley, 2007; Reinhard et al., 2009; Sheldon and Tabor, 2009). The 2006; Sheldon and Tabor, 2009; Lahtinen and Nironen, 2010; Mitchell
and Sheldon, 2010). Precambrian subaerial weathering profiles can
⁎ Corresponding author. therefore provide insight into the evolution of the ancient atmosphere
E-mail address: polat@uwindsor.ca (A. Polat). and, as a result, life on land (Holland, 1984; Zbinden et al., 1988;
0009-2541/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.chemgeo.2012.07.018
146 A. Polat et al. / Chemical Geology 326–327 (2012) 145–173
Retallack, 1991a; Horodyski and Knauth, 1994; Gutzmer and Beukes, largest Archean craton in the world, was built by amalgamation of oceanic
1998; Rye and Holland, 1998). and continental fragments, ranging in age from 3700 to 2650 Ma, during
Many Precambrian paleosols have basaltic parental rocks (Macfarlane five discrete tectonothermal events over 40 million years between 2720
et al., 1994; Ohmoto, 1996, 1997; Rye and Holland, 1998, 2000; Retallack, and 2680 Ma (Stott, 1997; Polat and Kerrich, 2000, 2001; Percival et al.,
2001; Yang and Holland, 2003; Driese, 2004), including localities in the 2006a). Linear patterns of approximately east–west striking plutonic, vol-
Canadian Shield (Gay and Grandstaff, 1980; Gall, 1994, 1999; Pan and canic–plutonic (greenstone-granitoid), high-grade gneissic, and sedimen-
Stauffer, 2000; Babechuk and Kamber, 2011). Here, we report new evi- tary subprovinces in the Superior Province reflect lateral accretion of
dence for preservation of a weathering profile atop a Neoarchean (ca. oceanic and continental fragments along Neoarchean convergent plate
2.7 Ga) pillow basalt sequence from the western end of the Schreiber- boundaries over a length of >1000 km (Stott, 1997; Percival et al.,
Hemlo greenstone belt in the Wawa subprovince, Superior Province, 2006a,b; Pettigrew and Hattori, 2006).
Canada (Fig. 1). This profile is located below an unconformity separat- The Wawa subprovince is composed of two linear trends of green-
ing the Paleoproterozoic (ca. 1.88 Ga) basal conglomerate and Gunflint stone belts: a northern trend and a southern trend (see Williams et al.,
Chert from the Archean greenstone basement (Figs. 1–3). These out- 1991; Corfu and Stott, 1998). Polat and Kerrich (2000) interpreted the
crops offer an opportunity to examine the physical, mineralogical, and northern Wawa greenstone belts, which include the study area (Fig. 1),
chemical changes that accompanied transformation of Neoarchean to be part of a ~1000 km subduction–accretion complex formed along
(2.7 Ga) pillow basalts during the successive stages of submarine alter- an intra-oceanic convergent plate margin during trenchward migration
ation, regional metamorphism, and Paleoproterozoic weathering and of the magmatic arc axis. Within this geodynamic framework, the
paleosol formation. komatiite and Mg- to Fe-tholeiitic basalt association, with minor transi-
tional to alkaline basalts, was interpreted as dismembered fragments of
2. Regional geology and field characteristics an oceanic plateau whereas the LREE-enriched and variably HFSE-
depleted bimodal basalt-andesite-dacite-rhyolite suite, with minor
Polat (2009 and references therein) provides a detailed description adakites, magnesian andesites, and Nb-enriched basalts, was interpreted
of the regional geology of the Wawa subprovince overall and Schreiber- as fragments of an intra-oceanic magmatic arc paired with trench
Hemlo greenstone belt specifically. Briefly, the Superior Province, the turbidites.
Fig. 1. (A) Simplified geological map of the Schreiber, Hemlo, Manitouwadge, and White River areas, Wawa Subprovince. The Schreiber Beach profile occurs at the western end of
the Schreiber-Hemlo greenstone belt (modified after Williams et al., 1991). LSHFZ: Lake Superior-Hemlo Fault Zone. (B) Location of sampling area at Schreiber Beach.
A. Polat et al. / Chemical Geology 326–327 (2012) 145–173 147
2.1. Schreiber-Hemlo greenstone belt (LSHFZ), respectively (Fig. 1). These three assemblages are composed
of similar volcanic and siliciclastic sedimentary rocks. The age of the
In the Schreiber-Hemlo greenstone belt volcanism extended from oceanic plateau association is not well constrained. Given that this as-
ca. 2750 to 2688 Ma, a granitoid intrusive phase occurred from 2720 sociation is intruded by 2719 to 2697 Ma tonalite-trondjemite-
to 2677 Ma, and siliciclastic turbidites were deposited from 2705 to granodiorite (TTG) plutons (Beakhouse and Davis, 2005), it may have
2685 Ma (Corfu and Muir, 1989a,b; Williams et al., 1991; Davis et formed between 2750 and 2720 Ma. Both the oceanic plateau and is-
al., 1998; Beakhouse and Davis, 2005; Fralick et al., 2006). The land arc volcanic associations are exposed in the Schreiber-Hemlo
Schreiber-Hemlo greenstone belt was divided into three lithotectonic greenstone belt.
assemblages by Williams et al. (1991): Schreiber, Hemlo-Black River, The Schreiber-Hemlo belt underwent at least three phases of ductile
and Heron Bay. The Schreiber and Hemlo-Black River assemblages are deformation, resulting in folding, faulting, transposition and regional
separated by the Proterozoic Coldwell alkaline complex (Fig. 1). The foliation (Polat et al., 1998; Polat and Kerrich, 1999; Davis and Lin,
Hemlo-Black River and Heron Bay assemblages are located to the 2003; Muir, 2003; Beakhouse and Davis, 2005). Regional metamor-
north and south of the right lateral Lake Superior-Hemlo fault zone phism occurred between 2690 and 2670 Ma (Davis and Lin, 2003;
Fig. 2. Stratigraphy and field photographs of the Schreiber Beach profile, showing Neoarchean pillow basalts, weathering profile, Paleoproterozoic unconformity, and Gunflint Formation.
A gradual increase in the intensity of physical and chemical weathering occurs with stratigraphic height. (A) Gunflint Chert and basal conglomerates and breccia overlying the Neoarchean
pillow basalts and Paleoproterozoic weathering profile. (B) Weathered brown to green and red basalts. (C) Exfoliated and fractured pillow basalts. (D) Unweathered pillow basalts.
Beakhouse and Davis, 2005 and references therein). Metamorphic filled with quartz. Pillow rims are green to black ranging from
grade generally increases from greenschist to amphibolite facies to- 2–3 mm to 2–4 cm in thickness (Figs. 2 and 3). Rims consist predomi-
wards some of the intrusion-supracrustal contacts. nantly of chlorite. Pillow interstitials are filled mainly by hyaloclastites,
chert and calcite. Hyaloclastites include shattered (brecciated) inter-
2.2. Schreiber Beach pillow, inter-flow, pillow core, and pillow rim material (Figs. 2 and 3).
Fragments of hyaloclastite range from 1 mm to 10 cm in length and
Schreiber Beach (Fig. 1) represents one of the lowest-strain domains are cemented mainly by quartz and calcite; cement locally comprises
in the Schreiber-Hemlo greenstone belt. Primary volcanic features at 60–80% of the hyaloclastite. The volcanic sequence at Schreiber Beach
Schreiber Beach are well preserved, including virtually undeformed pil- also contains an association of 10 to 15 m thick tuff, lapillistone, and
lows, hyaloclastites and pyroclastics flows (Figs. 2 and 3; see also Fig. 3 tuff breccia (Polat, 2009).
in Polat, 2009). Pillows range from 20 cm to 1.5 m in diameter, The uppermost part of the volcanic sequence at Schreiber Beach is
containing abundant vesicles and amygdules. Vesicle abundance in- characterized by exfoliated, highly-fractured, and brown to red pillows
creases from centre to edge of pillow cores. Amygdules are composed (Figs. 2 and 3). The intensity of fragmentation and red colour increases
primarily of calcite, chlorite, and quartz. Pillow cores locally display ra- upward towards the Paleoproterozoic unconformity. Disintegrated
dial fractures and central drainage cavities; many drainage cavities are pillows are locally surrounded by fine-grained hematite-rich red
Fig. 3. Stratigraphy and field photographs of the Schreiber Beach profile. A gradual increase in the intensity of physical and chemical weathering occurs with stratigraphic height.
(A) Strongly weathered pillow basalts immediately below the Paleoproterozoic unconformity. (B) Weathered pillow basalts and red soil. (C) Weathered pillow basalts. (D) Unweathered
pillow basalts.
Fig. 4. Sample locations and whole-rock oxygen-isotope compositions.
patches (Figs. 2 and 3). As discussed below, on the basis of field obser- the Schreiber-Hemlo greenstone belt. The age of the Aminikie Group is
vations these red and brown to green patches are interpreted as constrained by a 1878±2 Ma zircon date for its volcaniclastic rocks
paleosols and collectively, the weathered basaltic rocks below the (Fralick et al., 2002). The age of the Schreiber weathering profile is not
ca. 1.88 Ga-unconformity are interpreted to be a subaerial weathering well constrained. It probably formed sometimes between 2.2 Ga
profile. The weathering profile is cut by 1 to 15 cm-thick calcite veins, (Great Oxidation Event) and 1.9 Ga. Given that weathered rocks signifi-
containing pyrite and chalcopyrite. cantly older than 1.9 Ga would have been removed by erosion prior to
Lithologies above the unconformity belong to the Paleoproterozoic the deposition of the basal conglomerates and Gunflint Formation, it is
Animikie Group (Fralick et al., 2002). The Schreiber Beach weathering most likely that the preserved profile at Schreiber Beach originated at
profile is overlain unconformably by a 50 cm to 5 m thick Paleo- about 1.9 Ga.
proterozoic basal conglomerate-breccia layer, or in its absence by
the 20 cm to 1 m thick Gunflint Chert (Figs. 2 and 3). The Gunflint 3. Field description and sampling
Chert is best known for its well-preserved and abundant Paleoproterozoic
microfossils (Schopf, 1999). The basal conglomerate-breccia layer consists On the basis of field characteristics, samples were classified as follows:
mainly of variably weathered greenstone, gneiss, quartz, and granitic (1) pillow cores; (2) pillow rims; (3) hyaloclastite (e.g., fragmented and
rocks. The presence of abundant greenstone in the conglomerate- cemented pillow interstitial, pillow rim, and pillow core material);
breccia layer is consistent with Paleoproterozoic uplift and erosion of (4) weathered red basalts (red soil); and (5) weathered brown to green
basalts (soil). Macroscopic evidence supporting subaerial weathering 4. Analytical methods

includes the gradual increase in the intensity of fracturing, disintegration,
and exfoliation of pillow basalts with stratigraphic height and the gradual 4.1. Major and trace elements
colour transition from fresh green pillow basalts, through brown and then
to weathered red equivalents towards the Paleoproterozoic unconformity Samples were crushed using a hydraulic press and powdered using
(Figs. 2 and 3). Weathered and unweathered rocks at Schreiber Beach an agate mill at the University of Windsor, Windsor, Canada. Major
were sampled at 0.3–5 m intervals to assess mineralogical and geochem- and some trace element analyses were performed by the Geoscience
ical changes with stratigraphic height (Fig. 4). Laboratories (Geo Labs), Ontario Geological Survey, Sudbury, Canada,
Fig. 5. Photomicrographs illustrating the petrographic characteristics of the Schreiber Beach pillow basalts, hyaloclastites, weathered red basalts and weathered brown to green basalts.
(A) Pillow core with a primary igneous texture containing randomly oriented plagioclase (plag) laths. (B) Concentric amygdules within pillow cores consisting of quartz and minor
chlorite. (C) Hyaloclastite consisting of chloritized volcanic glass in a fine-grained quartz matrix. (D) Hyaloclastite displaying chlorite and carbonate alteration. (E) Red hyaloclastite
including Fe-oxides in a fine-grained quartz matrix at the base of the weathering profile. (F) Strongly silicified, brecciated hyaloclastite at the base of the weathering profile. Dark
areas consist mainly of Fe-oxides. Fe-rich veinlets crosscut the quartz fragments. (G) Weathered red basalt (red soil) consisting of Fe-oxide, quartz, and chlorite. (H) Weathered
brown to green basalt.
Fig. 6. SEM‐BSE images showing the petrographic characteristics of the pillow cores, pillow rims, and hyaloclastites. (A) Pillow core displaying relic igneous texture. Dark minerals
are altered plagioclase laths, grey minerals are chlorite, and tiny white minerals are rutile and titanite. (B) Concentric amygdule in the pillow cores consisting of chlorite (chl), cal-
cite (cal) and quartz (qtz). (C) Pyrite (pyt), albite (alb), calcite (cal), and chlorite (chl) in the pillow core. (D) Pyrite (pyt), albite (alb), calcite (cal), and chlorite (chl) in the pillow
rim. (E) Brecciated quartz (qtz) in a hematite matrix at the base of the weathering profile. (F) Quartz (qtz), calcite (cal) and chlorite (chl) including hematite flakes.
following the analytical protocols of Burnham et al. (2002), Burnham and where reproducibility was somewhat poorer (±14%). Similarly, re-
and Schweyer (2004) and Schweyer (2006). Loss on ignition (LOI) producibility of individual trace element analyses (Table 2) was gener-
was determined by weight loss upon heating to 1100 °C over 3 h. ally better than ±5% of the amount present, except for Mo where
Major elements were analysed using X-ray fluorescence spectrome- reproducibility was somewhat poorer (±22%). The ratios of Ce/Ce*
try (XRF); totals for major element oxides are 100 ± 1 wt.% with an and Eu/Eu* were calculated following Taylor and McLennan (1985).
analytical precision of 1 to 2% for most elements. Trace element anal- Mg-numbers (%) were calculated as the molecular ratio of Mg/
yses were performed using an ELAN 9000 ICP-MS (see Supplemental (Mg+Fe2+), where Fe2+ is assumed to be 90% of total Fe. Chemical
Electronic Material 1 for detection limits). Results for MAG-1 (Ma- index of alteration (CIA) values were calculated using the molecular
rine mud, United States Geological Survey) and MRG-1 (Gabbro, Ca- weight of Al2O3, CaO*, Na2O, and K2O and formula of CIA=Al2O3/(Al2-
nadian Certified Reference Material Project) agree well with O3 +CaO*+Na2O+K2O)×100; where, CaO* represents CaO in silicates,
recommended values (see Supplemental Electronic Material 2). Rep- CaO*=CaO−(CO2, calcite)−0.5(CO2, dolomite)−10/3(P2O5, apatite)
licate major element analyses of selected samples performed at (see Nesbitt and Young, 1982 and Fedo et al., 1995).
ACTLABS in Ancaster (Ontario), Canada, using a Thermo Jarrel-Ash induc-
tively coupled plasma – atomic emission spectrometry (ICP‐AES), agreed 4.2. Oxygen isotopes
well with Geo Labs results (see Table 2). Reproducibility of individual
major element analyses between the two laboratories was generally Oxygen-isotope analyses of whole-rock silicates were performed
better than ±6% of the amount present, excepting MnO, K2O and P2O5 at the Laboratory for Stable Isotope Science (LSIS), the University of
Table 1
Schreiber Beach mineral assemblages.
Rock type Mineral assemblage
Pillow cores Chlorite, albite, andesine, calcite, quartz, pyrite, K-feldspar, titanite, ilmenite, rutile, magnetite, biotite
Pillow rims Chlorite, albite, oligoclase, andesine, calcite, quartz, K-feldspar, pyrite, biotite, rutile, chalcopyrite,
titanite, ilmenite (Fe-Ti oxide, Fe-Ti-Mn-oxide, Fe-Ti-Mn-V oxide)
Hyaloclastite Chlorite, albite, quartz, hematite, calcite, magnetite, pyrite, rutile, titanite, ilmenite
(Fe-Ti oxide, Fe-Ti-Mn oxide, Fe-Ti-Mn-V oxide), apatite, chalcopyrite
Weathered red basalts — red soil Chlorite, quartz, hematite, calcite, magnetite (Fe-oxide, Fe-Ti-V oxide, Fe-Co oxide), biotite, ilmenite
(Fe-Ti oxide, Fe-Ti-Mn oxide, Fe-Ti-V oxide), muscovite, rutile, apatite
Weathered brown to green basalts — soil Chlorite, quartz, biotite, K-Feldspar, hematite, calcite, magnetite, albite, andesine, oligoclase, ilmenite
(Fe-Ti oxide, Fe-Ti-Mn oxide, Fe-Ti-Mn-V oxide, Fe-Ti-Ta oxide), rutile, apatite, muscovite, pyrite
Western Ontario, London (Ontario), Canada. Powdered rock samples holders, evacuated overnight at ~ 150 °C, and then loaded into nickel
were treated with 0.3 N HCl for 48 h at 25 °C to remove carbonates, reaction vessels and heated under vacuum at 150 °C for a further 3 h
thoroughly rinsed with distilled water and then dried. Approximately to remove extraneous water. The sample powders were then reacted
8 mg of sample powder were placed into spring-loaded sample overnight at ~ 580 °C with ClF3 to release the silicate-bound oxygen
Fig. 7. SEM‐BSE images showing the petrographic characteristics of weathered red basalts (red soil). (A) Calcite (cal) concretions in a quartz (qtz) matrix. Calcite concretions contain
hematite (hem) flakes. (B) Bundles of hematite (hem) flakes. (C) Bundles of hematite (hem) flakes overprinted by magnetite (mgt) grains. (D) Calcite (cal) concretion, bundles of
hematite (hem) flakes and quartz (qtz). (E) Magnetite (mgt), quartz (qtz) and hematite (hem)-hosting chlorite (chl). (F) Bundles of hematite (hem) flakes, ilmenite (ilm) and chlorite.
Ilmenite overprints hematite-hosting chlorite.
Fig. 8. SEM-BSE images showing the petrographic characteristics of weathered brown to green basalts. (A) Hematite- (hem) rich patches in a chlorite (chl) matrix. (B) Patches of
anhedral quartz (qtz) and chlorite (chl). Chlorite is partly replaced by biotite (bio). (C) Anhedral K-feldspar (K-feld), quartz (qtz) and chlorite (chl). (D) Replacement of chlorite
(chl) by biotite (bio). (E) Chlorite (chl), quartz (qtz) and rutile (rut). (F) Quartz (qtz), biotite (bio), quartz (qtz) and ilmenite (ilm).
(Borthwick and Harmon, 1982 following Clayton and Mayeda, 1963). employing Co Kα radiation (λ = 0.1790210 nm) at 45 kV and
The oxygen was converted to CO2 over red-hot graphite for isotopic 160 mA. Samples were scanned from 2° to 82° 2θ, using a step size
measurement using a Prism II dual-inlet, stable-isotope-ratio of 0.02° 2θ, and a scan rate of 10° 2θ/min.
mass-spectrometer. The oxygen isotopic analyses are reported using BSE images were obtained at the Great Lakes Institute for Environ-
δ-notation in parts per thousand (‰) relative to Vienna Standard mental Research (GLIER), University of Windsor, Windsor (Ontario),
Mean Ocean Water (VSMOW). During these analyses, the δ 18O values Canada using an Environmental Scanning Electron Microscope
obtained for NBS-30 (5.2‰, n = 5), a laboratory standard quartz (EDAX FEI Quanta 200 FEI Environmental SEM) equipped with an En-
(11.4‰, n = 5), and a laboratory standard kaolinite (21.4‰, n = 3) ergy Dispersive X-ray Spectrometry (EDS), operating under high vac-
compared well with their accepted values of 5.1, 11.5 and 21.5‰, uum at an accelerating potential of 15 kV. Spot size and duration for
respectively. Reproducibility of standards and samples was better EDS were 3.9 mm and 20–30 s, respectively. Elemental abundances
than ±0.2‰. were obtained using ‘standardless quantification’, and used for min-
eral identification and to assess compositional variation within
phases.
4.3. pXRD (powder X-ray diffraction) and SEM (scanning electron
microscope)-BSE (backscatter electron) analyses
5. Mineralogy and petrography
For pXRD, powdered samples were backpacked in an Al-holder
and analyzed at LSIS using a high brilliance Rigaku RU-200BVH rotat- Pillow cores from the Schreiber Beach profile display well-
ing anode X-ray diffractometer, operating in step-scan mode and preserved primary magmatic textures and contain abundant vesicles
Table 2
Major oxide (wt.%), trace (ppm) element, and oxygen-isotope (‰) results for pillow cores, rims, hyaloclastites, and weathered pillow basalts in the Schreiber beach area.
Pillow cores
SC2007-29 SC2007-30 SC2007-31 SC2007-31Ra SC2007-32 SC2007-33 SC2008-14 SC2008-15 SC2008-15Ra
SiO2 50.6 46.9 47.4 60.9 53.2 47.4 50.7

Al2O3 15.2 13.7 13.6 14.4 14.0 14.8 14.6
TiO2 1.32 1.15 1.16 1.19 1.39 1.27 1.26
Fe2O3 13.1 16.2 15.5 7.6 12.5 13.8 12.1
MnO 0.29 0.39 0.36 0.18 0.26 0.33 0.30
MgO 3.4 3.7 4.0 2.7 3.7 4.2 3.3
CaO 8.2 10.5 9.1 5.7 7.7 10.1 8.9
Na2O 2.59 1.94 2.04 4.04 2.22 2.65 2.98
K2O 0.42 0.16 0.65 0.52 0.31 0.28 0.30
P2O5 0.156 0.126 0.126 0.195 0.186 0.125 0.125
LOI 3.9 4.7 4.7 2.6 3.2 4.4 3.9
Total 99.1 99.6 98.6 100.0 98.8 99.3 98.5
Mg-number 33.8 31.3 33.6 41.7 37.2 37.8 35.0
δ18Ο (‰) 12.7 12.7 12.3 12.7
Ni 121 83 115 112 129 99 116 109 114
Cr 189 167 160 163 175 155 180 174 179
Co 50 47 60 59 49 57 62 53 55
V 357 317 307 315 291 351 345 335 342
Sc 49 44 44 44 36 46 50 48 50
Cu 116 110 120 121 72 127 125 98 102
Zn 104 100 125 125 81 123 136 117 121
Mo 0.29 0.44 0.69 0.7 0.47 0.26 0.68 0.41 0.43
Li 27.2 26 19.2 19.5 11.5 13.5 16.3 16.6 17.7
Ba 103 60 184 181 237 114 88 85 85
Cs 1.49 0.26 0.47 0.47 0.85 0.78 0.55 0.54 0.54
Rb 16.1 5.1 19.7 19.6 21.4 10.7 9.6 9.6 9.6
Sr 143 93 95 95 124 101 87 106 109
Pb 1.3 0.8 0.6 0.6 0.7 1 0.6 0.6
Ga 18.5 15.9 16.4 16.3 15.3 18.2 17.8 17.6 17.9
Zr 78 69 70 70 80 88 75 75 78
Hf 2.21 1.94 1.95 1.99 2.24 2.4 2.16 2.13 2.16
Nb 3.07 2.68 2.93 2.89 2.8 3.55 3.05 3.04 3.11
Ta 0.2 0.18 0.19 0.19 0.18 0.23 0.2 0.2 0.2
Th 0.33 0.29 0.31 0.31 0.31 0.38 0.33 0.32 0.31
U 0.1 0.09 0.1 0.1 0.09 0.11 0.09 0.09 0.09
Y 25.4 24.3 26.0 25.9 22.2 27.9 26.8 25.7 26.4
La 4.43 4.06 4.47 4.52 3.59 4.44 4.28 3.98 4.03
Ce 11.65 10.29 11.53 11.6 9.96 11.71 11.49 10.71 10.97
Pr 1.82 1.59 1.81 1.82 1.62 1.83 1.83 1.72 1.74
Nd 9.22 8.22 9.41 9.15 8.32 9.61 9.39 8.77 8.93
Sm 2.94 2.64 3.02 2.94 2.71 3.13 3.09 2.85 2.91
Eu 1.06 0.89 1.15 1.17 1.1 1.36 1.14 1.01 1.03
Gd 3.91 3.52 3.79 3.77 3.52 4.08 4.08 3.82 3.9
Tb 0.68 0.62 0.68 0.68 0.61 0.71 0.7 0.65 0.69
Dy 4.58 4.12 4.58 4.51 4.04 4.82 4.8 4.53 4.63
Ho 0.98 0.89 0.97 0.97 0.83 1.04 1.03 0.96 0.98
Er 2.87 2.73 2.93 2.92 2.45 3.04 3.06 2.88 2.99
Tm 0.42 0.4 0.43 0.44 0.36 0.46 0.46 0.43 0.43
Yb 2.75 2.6 2.91 2.9 2.27 2.94 2.97 2.84 2.85
Lu 0.41 0.4 0.44 0.44 0.35 0.45 0.46 0.44 0.44
La/Smcn 0.97 0.99 0.96 0.86 0.92 0.89 0.90

Gd/Ybcn 1.18 1.12 1.08 1.28 1.15 1.14 1.11
La/Ybcn 1.16 1.12 1.10 1.13 1.08 1.03 1.01
Eu/Eu* 0.96 0.89 1.04 1.09 1.16 0.98 0.93
Ce/Ce* 1.01 0.99 0.99 1.01 1.01 1.01 1.00
Al2O3/TiO2 12 12 12 12 10 12 12
Th/U 3.4 3.3 3.3 3.2 3.6 3.7 3.6 3.5 3.5
Zr/Hf 35 36 36 36 37 35 35
Nb/Ta 15 15 15 15 16 15 16
Ti/Al 0.10 0.10 0.10 0.09 0.11 0.10 0.10
Ti/Zr 101 100 100 89 95 102 101
CIA 46 42 43 47 46 42 42
North 48°47′40.6″ 48°47′40.8″ 48°47′41.0″ 48°47′40.8″ 48°47′40.8″ 48°47′41.5″ 48°47′41.6″
West 87°17′34.3″ 87°17′35.5″ 87°17′38.6″ 87°17′41.1″ 87°17′41.1″ 87°17′42.3″ 87°17′42.1″
and amygdules (Figs. 5 and 6). Mineralogically, pillow cores have an calcite and quartz, with minor titanite and rutile (Figs. 5 and 6).
assemblage of chlorite, plagioclase (albite and andesine), calcite, Some amygdules are zoned, with chlorite cores and quartz and calcite
K-feldspar, and quartz plus minor titanite, pyrite, ilmenite, magnetite, rims or vice versa; others comprise alternating concentric zones of
rutile, and biotite (Table 1). Amygdules consist mainly of chlorite, chlorite and quartz. Pillow cores are cut by 1–5 mm thick quartz
Hyaloclastites
Pillow rims Group 1 Group 2

b a
SC2007-20 SC2007-20R SC2008-11 SC2008-11R SC2008-12 SC2007-16 SC2007-17 SC2007-02 SC2007-03A SC2007-03B SC2007-05A
47.9 47.8 36.7 37.16 40.8 42.9 34.0 66.6 66.6 74.9 77.1
13.4 13.3 16.2 16.11 14.6 12.6 11.4 6.65 4.90 2.51 4.3
1.11 1.11 1.34 1.37 1.25 1.08 0.83 0.20 0.19 0.10 0.15
12.0 12.1 25.5 25.29 19.7 18.3 19.4 17.0 16.7 11.4 11.2
0.29 0.29 0.37 0.39 0.39 0.37 0.46 0.07 0.08 0.08 0.05
3.06 3.07 7.47 7.51 6.16 4.88 5.00 2.57 1.87 0.90 1.68
10.5 10.5 3.3 3.34 7.0 9.0 13.0 2.4 4.1 4.8 2.1
2.55 2.55 0.66 0.64 1.27 0.85 0.20 0.12 0.01 0.14 0.13
0.22 0.23 0.18 0.17 0.14 0.22 0.15 0.07 0.06 0.06 0.02
0.090 0.08 0.090 0.090 0.090 0.070 0.090 0.070 0.080 0.050 0.060
8.9 8.9 8.0 8.06 8.7 10.1 14.2 4.3 4.8 4.2 3.2
99.9 99.9 99.7 100.1 100.0 100.2 98.7 100.0 99.4 99.1 100.1
33.5 33.5 36.8 38.2 34.6 33.8 23.1 18.1 13.5 22.9
12.7 10.4 11.6 16.8 16.2
107 145 112 108 84 46 41 21 44
168 211 188 165 139 63 54 53 50
52 77 66 56 51 27 22 11 21
310 421 373 315 250 384 337 250 257
43 55 58 44 41 21 22 16 16
112 61 138 88 138 61 90 86 71
111 243 197 152 158 81 60 32 60
0.57 0.25 0.23 0.46 0.54 0.51 0.57 1.39 0.67
14.1 37.6 18.9 23.7 22.9 16 24.1 21.1 24
108 50 103 97 34 24 15 15 15
0.83 0.76 0.68 0.49 0.34 0.71 0.30 0.29 0.57
9.39 6.52 8.17 7.79 2.31 5.63 2.04 2.02 3.99
134 42 80 65 45 57 107 120 42.5
1.3 3.3 2.3 0.8 0.8 4 1.7 2.2 2.1
16.5 25.0 19.5 16.6 15.9 12.4 9.9 5.0 7.8
70 87 76 69 67 30 20 14 17
1.94 2.44 2.15 1.96 1.84 0.77 0.53 0.36 0.45
2.74 3.56 3.02 2.71 2.37 0.91 0.68 0.5 0.58
0.18 0.22 0.2 0.18 0.16 0.06 0.04 0.02 0.04
0.29 0.37 0.32 0.34 0.5 0.4 0.21 0.18 0.18
0.08 0.12 0.09 0.11 0.14 0.1 0.11 0.09 0.06
22.4 21.5 25.9 22.1 26.1 22.0 35.0 35.1 22.6
3.5 3.29 3.51 3.87 4.51 6.95 10.01 10.17 6.06
8.95 8.96 9.45 9.68 11.32 17.2 24.71 25.83 15.39
1.43 1.42 1.53 1.53 1.73 2.29 3.51 3.68 2.11
7.18 7 7.96 7.6 8.72 10.3 15.99 16.81 9.48
2.36 2.32 2.72 2.4 2.7 2.8 4.57 4.88 2.54
0.7 0.85 0.96 0.92 1.01 1.02 1.51 1.68 0.78
3.15 3.16 3.74 3.08 3.55 3.56 5.71 5.85 3.17
0.56 0.57 0.67 0.56 0.62 0.64 1 1.06 0.6
3.82 4.1 4.54 3.83 4.33 4.47 6.81 6.82 4.26
0.82 0.88 0.99 0.85 0.95 0.92 1.39 1.34 0.93
2.49 2.66 3.04 2.53 2.93 2.58 3.84 3.54 2.79
0.37 0.4 0.46 0.39 0.43 0.33 0.5 0.46 0.38
2.44 2.75 3.1 2.58 2.9 1.88 2.69 2.69 2.23
0.38 0.43 0.48 0.4 0.46 0.26 0.35 0.34 0.3
0.96 0.92 0.83 1.04 1.08 1.60 1.41 1.35 1.54

1.07 0.95 1.00 0.99 1.01 1.57 1.75 1.80 1.18
1.03 0.86 0.81 1.07 1.12 2.66 2.67 2.72 1.95
0.79 0.96 0.92 1.04 1.00 0.98 0.90 0.96 0.84
0.98 1.02 1.00 0.98 0.99 1.06 1.02 1.04 1.06
12 12 12 12 14 34 26 25 28
3.6 3.2 3.5 3.1 3.6 4.3 1.9 1.9 3.0
36 36 35 35 36 39 38 39 38
16 16 15 15 14 16 17 21 17
0.09 0.09 0.10 0.10 0.08 0.03 0.04 0.05 0.04
95 92 99 94 74 40 57 43 54
38 71 52 45 34 64 42 25 57
48°47′40.8″ 48°47′40.8″ 48°47′41.1″ 48°47′40.7″ 48°47′40.7″ 48°47′47.2″ 48°47′47.2″ 48°47′47.2″ 48°47′47.5″
87°17′41.4″ 87°17′39.5″ 87°17′41.1″ 87°17′39.5″ 87°17′39.5″ 87°18′19.2″ 87°18′19.2″ 87°18′19.2″ 87°18′21.6″
(continued on next page)

Table 2 (continued)
Hyaloclastites Weathered red basalts — red soil
Group 2 Group 3 Group 4
SC2007-05B SC2007-05BRa SC2007-06B SC2007-11 SC2007-13 SC2007-14 SC2007-15A SC2007-04 SC2007-21A SC2007-21B
SiO2 79.2 61.4 77.3 86.0 87.5 62.5 48.77 27.8 24.5
Al2O3 3.3 5.4 5.2 0.6 0.5 1.9 9.00 11.1 12.2
TiO2 0.12 0.25 0.33 0.02 0.01 0.14 0.26 0.89 1.04
Fe2O3 8.8 17.3 10.3 4.7 6.3 11.7 26.59 27.9 32.4
MnO 0.07 0.11 0.08 0.10 0.06 0.25 0.13 0.38 0.41
MgO 1.23 2.19 2.12 0.23 0.19 0.82 3.73 4.6 5.4
CaO 3.2 6.8 1.5 5.2 3.1 12.3 3.73 10.1 9.2
Na2O 0.13 0.10 0.11 0.10 0.12 0.12 0.01 0.06 0.11
K2O 0.06 0.13 0.08 0.01 0.01 0.07 0.06 1.80 1.24
P2O5 0.050 0.050 0.050 0.020 0.010 0.020 0.100 0.060 0.140
LOI 3.8 6.2 3.4 4.1 3.0 9.2 6.8 13.3 12.6
Total 99.9 99.9 100.5 100.9 100.7 98.9 99.2 98.0 99.3
Mg-number 21.7 20.0 28.9 8.9 5.6 12.2 21.7 24.8 25.0
δ18Ο (‰) 17.1 16.1 16.2 13.6
Ni 35 33 58 40 25 70 68 95 139 181
Cr 49 50 65 49 5 7 21 82 153 193
Co 16 15 25 28 18 23 41 55 49 64
V 199 189 401 117 16 17 70 651 357 466
Sc 14 14 25 17 4 4 16 26 48 47
Cu 86 84 40 33 43 71 52 8 21 12
Zn 48 49 66 56 10 34 23 103 106 147
Mo 0.94 0.93 1.21 3.5 0.63 1.21 7.15 0.26 0.61 0.53
Li 21.7 21.4 23.1 16.6 0.6 1.1 5.3 41.7 53.4 67.1
Ba 16 16 37 4 5 4 48 31 112 87
Cs 0.68 0.69 1.34 0.14 0.06 0.07 0.3 0.27 14.4 11.8
Rb 4.66 4.62 9.71 1.1 0.29 0.47 3.15 1.12 84 71
Sr 43.1 43.2 267.9 7.3 16.7 11 49 47.5 71 70
Pb 2.5 2.5 1.9 2 0.6 0.9 0.6 1.2 1.9 2.2
Ga 5.6 5.8 10.0 7.5 1.5 2.0 3.6 21.7 18 21
Zr 14 14 22 20 11 29 57 67
Hf 0.37 0.36 0.59 0.56 0.29 0.81 1.65 1.97
Nb 0.45 0.44 0.82 0.83 0.12 0.15 0.48 1.03 2.23 2.61
Ta 0.03 0.03 0.05 0.05 0.02 0.06 0.15 0.17
Th 0.16 0.16 0.17 0.1 0.05 0.34 0.25 0.32
U 0.06 0.06 0.09 0.05 0.03 0.02 0.04 0.14 0.12 0.12
Y 25.1 24.9 51.1 6.9 3.3 2.1 13.5 91.7 58.2 64.3
La 6.16 6.21 14.64 1.19 0.44 0.39 1.8 22 12.52 13.09
Ce 16.45 16.53 35.44 3.06 0.97 0.84 4.25 51.95 31.72 34.63
Pr 2.32 2.33 4.92 0.48 0.15 0.13 0.65 7.4 4.44 5.01
Nd 10.9 10.75 22.44 2.36 0.71 0.64 3.3 33.91 21.44 24.04
Sm 3.06 3.13 6.41 0.83 0.22 0.19 1.1 8.59 6.62 7.59
Eu 1.04 1.03 2.26 0.25 0.06 0.06 0.37 2.63 2.37 2.69
Gd 3.89 3.87 8.01 1.07 0.34 0.27 1.6 10.48 8.54 9.5
Tb 0.7 0.71 1.39 0.2 0.06 0.05 0.29 1.95 1.52 1.73
Dy 4.79 4.81 9.25 1.33 0.45 0.33 2.08 14.77 10.41 12.02
Ho 0.98 0.98 1.81 0.29 0.11 0.08 0.46 3.35 2.15 2.5
Er 2.78 2.74 4.94 0.88 0.36 0.25 1.45 9.54 6.25 7.31
Tm 0.38 0.38 0.63 0.14 0.06 0.04 0.22 1.23 0.91 1.02
Yb 2.3 2.3 3.39 0.94 0.38 0.29 1.53 6.7 5.6 6.39
Lu 0.32 0.32 0.45 0.14 0.06 0.05 0.23 0.92 0.81 0.92
La/Smcn 1.30 1.47 0.93 1.28 1.33 1.06 1.65 1.22 1.11
Gd/Ybcn 1.39 1.95 0.94 0.74 0.78 0.87 1.29 1.26 1.23
La/Ybcn 1.92 3.09 0.91 0.83 0.96 0.84 2.36 1.60 1.47
Eu/Eu* 0.92 0.97 0.79 0.69 0.78 0.86 0.85 0.96 0.97
Ce/Ce* 1.07 1.02 1.00 0.94 0.92 0.96 1.00 1.04 1.05
Al2O3/TiO2 28 21 16 26 56 14 34 13 12
Th/U 2.7 2.6 1.9 2.0 1.1 2.4 2.1 2.7
Zr/Hf 38 37 36 38 36 35 34
Nb/Ta 15 16 16 20 17 15 15
Ti/Al 0.04 0.05 0.07 0.04 0.02 0.08 0.03 0.09 0.10
Ti/Zr 50 69 98 75 55 93 93
CIA 43 34 70 7 9 9 63 38 42
North 48°47′47.5″ 48°47′47.5″ 48°47′38.9″ 48°47′14.0″ 48°47′14.0″ 48°47′40.8″ 48°47′47.2″ 48°47′47.3″ 48°47′47.3″
West 87°18′21.6″ 87°18′21.6″ 87°17′30.3″ 87°17′37.2″ 87°17′37.2″ 87°17′39.1″ 87°18′19.2″ 87°18′20.4″ 87°18′20.4″
Weathered brown to green basalts ̶ soil
Group 1 Group 2
a a,b
SC2007-21R SC2007-22A SC2008-05 SC2008-06 SC2007-24 SC2008-20 SC2008-21 SC2008-23 SC2008-23R SC2008-04
30.7 59.3 60.7 57.2 51.5 57.8 55.7 56.5 60.2

12.1 11.4 11.9 11.7 12.6 10.7 11.2 11.4 12.4
0.92 0.92 1.05 0.94 1.28 0.79 0.96 0.96 1.25
32.8 15.6 15.6 20.4 21.2 21.7 18.9 19.8 8.6
0.20 0.04 0.04 0.05 0.06 0.05 0.05 0.06 0.07
5.4 2.9 2.9 3.9 3.6 4.2 3.6 3.5 2.0
5.4 1.2 0.9 0.3 1.4 0.2 1.4 1.5 4.03
0.11 0.85 0.40 0.12 0.18 0.02 0.50 0.52 1.73
1.48 2.15 2.59 1.4 2.25 0.56 1.53 1.62 4.12
0.130 0.120 0.170 0.100 0.270 0.100 0.120 0.13 0.090
9.6 4.5 4.5 4.7 5.1 5.0 4.9 4.9 5.2
98.7 99.1 100.7 100.7 99.6 101.0 98.8 100.7 99.7
24.8 27.0 27.2 27.3 25.2 27.5 27.1 25.8 31.9
12.8 12.7 15.0 13.3 12.3 16.6 12.8
182 160 83 80 120 125 137 97 101 86
191 169 193 207 146 289 132 120 124 200
64 57 22 21 32 37 37 30 31 23
456.8 539 177 236 186 300 162 92 93 202
47 53 33 35 35 35 36 36 37 40
12 13 5 5 5 2547 15 7 8 12
143 121 60 65 94 96 103 82 83 62
0.53 0.41 0.17 0.09 0.15 0.47 0.19 0.11 0.09 0.63
65.7 73.1 38.4 37 50.5 50.1 50.1 46.7 49.4 26.4
86 76 54 77 41 204 25 49 49 773
11.6 20.9 26.7 30.3 11.3 2.6 4.5 21.1 20.7 13.4
69 91 111 141 67 44 27.9 79.2 80.4 109.6
70 61 22 15 7 32 6 13 13 68
2.2 2.4 0.6 0.8 1.4 0.6 0.6 0.6 0.7
21 23 15 17 16 17 18 14.9 15.0 11.9
68 60 61 67 59 165 50 62 61 84
1.91 1.66 1.73 1.85 1.65 4.35 1.42 1.71 1.71 2.4
2.59 2.36 2.39 2.67 2.31 4.31 2.01 2.38 2.35 3.26
0.17 0.15 0.15 0.17 0.15 0.3 0.13 0.16 0.16 0.22
0.34 0.27 0.25 0.25 0.26 2.43 0.2 0.26 0.26 0.35
0.12 0.15 0.08 0.09 0.09 0.37 0.12 0.09 0.09 0.11
63.2 70.9 38.7 43.4 39.7 70.0 37.7 29.56 28.82 22.05
12.98 11.26 2.93 3.04 3.77 7.98 4.05 5.06 4.85 2.84
34.62 31.05 7.47 7.31 8.7 23.09 10.29 12 11.78 7.17
4.99 4.61 1.23 1.22 1.39 3.39 1.48 1.76 1.74 1.13
24.15 22.38 6.41 6.42 6.83 17.82 7.26 8.37 8.1 5.72
7.54 7.31 2.33 2.34 2.16 5.96 2.29 2.54 2.49 1.85
2.64 2.45 0.92 0.92 0.76 2.17 0.81 0.89 0.86 0.77
9.52 9.39 3.89 4.01 3.43 8.52 3.7 3.57 3.47 2.53
1.71 1.81 0.79 0.82 0.73 1.62 0.71 0.68 0.66 0.47
11.74 12.83 6.03 6.43 5.78 11.74 5.42 4.91 4.89 3.37
2.48 2.86 1.35 1.48 1.38 2.5 1.27 1.11 1.09 0.74
7.27 8.8 4.15 4.6 4.38 7.5 4 3.43 3.45 2.3
1.04 1.28 0.6 0.66 0.64 1.03 0.57 0.5 0.5 0.37
6.41 8.02 3.72 4.1 3.83 6.32 3.43 3.23 3.18 2.69
0.93 1.14 0.56 0.59 0.58 0.91 0.51 0.47 0.48 0.44
0.99 0.81 0.84 1.13 0.86 1.14 1.28 1.26 0.99

0.97 0.86 0.81 0.74 1.12 0.89 0.91 0.90 0.78
1.01 0.56 0.53 0.71 0.91 0.85 1.13 1.09 0.76
0.90 0.94 0.92 0.85 0.93 0.85 0.90 0.90 1.09
1.06 0.97 0.93 0.93 1.09 1.03 0.99 0.99 0.98
13 12 11 12 10 14 12 12 10
2.9 1.9 3.1 2.8 2.9 6.5 1.7 2.9 2.8 3.2
36 35 36 36 38 35 36 35.67 35
16 16 16 16 14 15 15 15.04 15
0.09 0.09 0.10 0.09 0.11 0.08 0.10 0.10
92 90 93 95 46 94 92 94.53 89
55 69 74 86 74 94 72 72 49
48°47′47.3″ 48°47′47.4″ 48°47′47.4″ 48°47′47.3″ 48°47′47.7″ 48°47′47.6″ 48°47′47.4″ 48°47′47.3″
87°18′20.4″ 87°18′22.3″ 87°18′22.3″ 87°18′20.4″ 87°18′21.1″ 87°18′21.1″ 87°18′21.6″ 87°18′21.6″
(continued on next page)

Table 2 (continued)
Weathered brown to green basalts — soil
Group 2 Group 3 Group 4 Group 5
SC2008-07 SC2008-07Rb SC2008-08 SC2008-17 SC2007-23A SC2008-22 SC2008-02 SC2008-18 SC2008-19
SiO2 61.9 62.4 37.3 57.2 56.9 50.4 60.2 62.3 55.2
Al2O3 12.9 12.6 16.5 10.8 11.9 12.5 11.0 9.6 12.1
TiO2 1.3 1.27 1.41 0.96 0.94 0.97 0.98 0.88 1
Fe2O3 9.7 9.6 25.7 20.1 18.6 25.5 12.6 17.2 20.4
MnO 0.06 0.06 0.38 0.05 0.04 0.06 0.06 0.05 0.05
MgO 2.2 2.2 7.6 3.6 3.7 4.5 2.1 3.6 3.8
CaO 2.30 2.29 3.35 0.80 0.48 0.27 3.7 0.5 0.6
Na2O 1.72 1.65 0.74 0.13 0.13 0.09 2.02 0.03 0.12
K2O 4.2 4.2 0.12 1.72 1.92 0.66 2.12 1.17 2.12
P2O5 0.140 0.14 0.100 0.100 0.160 0.160 0.120 0.080 0.180
LOI 3.7 3.5 7.1 4.9 5.0 5.5 5.3 4.4 4.7
Total 100.0 99.8 100.3 100.4 99.8 100.6 100.1 99.8 100.3
Mg-number 30.8 30.8 36.9 26.3 28.2 26.0 25.0 29.3 26.9
δ18Ο (‰) 14.7 13.6 14.9 14.0
Ni 57 58 120 88 130 78 119 119
Cr 198 212 132 118 153 221 148 141
Co 18 19 35 26 39 18 33 33
V 244 439 186 111 200 214 159 159
Sc 37 48 37 34 40 30 30 34
Cu 139 40 5 5 12 12 4 10
Zn 62 59 97 73 119 49 91 95
Mo 0.36 0.53 0.21 0.3 0.08 0.23 0.09 0.08
Li 26.9 32 51.5 52.1 44.8 27.5 58.1 59.6
Ba 812 1020 48 41 26 73 39 122
Cs 9.1 8.4 16.0 33.8 4.8 20.0 10.9 8.9
Rb 92.6 92.0 96.3 115.8 35.1 91.8 56.8 64.6
Sr 47 54 12 11 7 76 8.1 15.1
Pb 0.7 0.6 1 0.6 0.9 0.6 0.6
Ga 9.4 9.0 15.2 14.8 19.6 11.0 12.3 16.2
Zr 79 85 62 59 59 64 55 64
Hf 2.26 2.39 1.75 1.67 1.7 1.79 1.58 1.78
Nb 3.18 3.41 2.39 2.29 2.4 2.45 2.36 2.48
Ta 0.21 0.22 0.16 0.15 0.16 0.16 0.15 0.16
Th 0.34 0.36 0.26 0.25 0.27 0.27 0.24 0.25
U 0.09 0.1 0.09 0.11 0.17 0.09 0.08 0.11
Y 14.81 23.28 14.32 22.83 18.88 25.0 16.1 18.0
La 2.64 3.81 3.61 5.31 4.54 3.66 2.22 1.48
Ce 6.95 9.8 7.85 12.02 11.03 9.43 5.95 4.66
Pr 1.09 1.51 1.29 1.97 1.7 1.48 0.94 0.84
Nd 5.57 7.92 6.16 9.9 8.68 7.54 4.87 4.91
Sm 1.85 2.56 1.86 2.87 2.61 2.39 1.62 1.87
Eu 0.83 1.06 0.65 0.94 0.88 0.9 0.57 0.66
Gd 2.35 3.43 2.43 3.81 3.45 3.24 2.2 2.71
Tb 0.39 0.58 0.41 0.65 0.56 0.57 0.39 0.46
Dy 2.52 3.85 2.84 4.33 3.65 4.01 2.68 3.06
Ho 0.54 0.83 0.61 0.93 0.75 0.86 0.57 0.65
Er 1.72 2.58 1.83 2.73 2.23 2.69 1.81 1.93
Tm 0.27 0.41 0.27 0.39 0.32 0.4 0.27 0.29
Yb 1.88 3.03 1.72 2.41 2.01 2.69 1.74 1.92
Lu 0.3 0.49 0.27 0.36 0.32 0.41 0.26 0.3
La/Smcn 0.92 0.96 1.26 1.19 1.12 0.99 0.88 0.51

Gd/Ybcn 1.04 0.94 1.17 1.31 1.42 1.00 1.05 1.17
La/Ybcn 1.01 0.90 1.51 1.58 1.62 0.98 0.91 0.55
Eu/Eu* 1.22 1.09 0.93 0.87 0.90 0.99 0.92 0.90
Ce/Ce* 1.01 1.00 0.89 0.91 0.97 0.99 1.01 1.02
Al2O3/TiO2 10 12 11 13 13 11 11 12
Th/U 3.6 3.6 2.8 2.2 1.6 2.9 2.9 2.4
Zr/Hf 35 36 35 35 35 36 35 36
Nb/Ta 15 16 15 15 15 15 16 15
Ti/Al 0.11 0.10 0.10 0.09 0.09 0.10 0.10 0.09
Ti/Zr 99 99 92 96 99 92 96 94
CIA 56 74 80 81 93 53 84 81
North 48°47′47.5″ 48°47′47.5″ 48°47′47.3″ 48°47′47.3″ 48°47′47.6″ 48°47′47.2″ 48°47′47.3″ 48°47′47.6″
West 87°18′22.6″ 87°18′22.4″ 87°18′20.7″ 87°18′20.4″ 87°18′21.1″ 87°18′21.6″ 87°18′20.7″ 87°18′21.1″
and calcite veins. Pillow rims are similar to pillow cores mineralogi- pyrite, chalcopyrite, magnetite, titano-magnetite, and Mn- and V-rich
cally, but generally finer grained. They consist of chlorite, plagioclase ilmenite (Table 1). Some samples are strongly chloritized (50–70%).
(albite, oligoclase, and andesine), calcite and quartz plus minor biotite, The majority of hyaloclastite fragments are chloritized, silicified,
K-feldspar, rutile, and titanite (Fig. 6; Table 1). Opaque minerals include and/or carbonated; they also contain albite, quartz, magnetite, pyrite,
rutile, titanite, and (Mn- and V-rich) ilmenite (Table 1). At the base of flakes (Fig. 7). Larger magnetite and ilmenite grains replace the
the weathering profile, hyaloclastites are red, consisting mainly of po- smaller hematite flakes (Fig. 7E, F). This horizon also contains abun-
lygonal, locally hexagonal, brecciated quartz and randomly oriented dant calcified and silicified patches, as well as rounded concretions of
hematite flakes (Figs. 2, 3, 6E). Larger chlorite grains contain numer- quartz and calcite (Figs. 5–8).
ous hematite and biotite flakes aligned mainly along cleavage planes The weathered and fragmented brown to green basalt, which
(Fig. 6F). Chlorite also occurs as irregular patches and veinlets. Some overlies the weathered red basalt, is characterized by chlorite, quartz,
hyaloclastite samples are dominated by chlorite (> 80%), whereas calcite, biotite, K-feldspar, muscovite, albite, andesine, oligoclase, ru-
others are composed mainly of quartz (60–90%). tile, and titanite (Figs. 5 and 8; Table 1). Opaque minerals include he-
The weathered red basalt consists mainly of chlorite, quartz, hematite, magnetite, (Mn, V- and Ta-rich) ilmenite, and pyrite (Fig. 8;
matite, calcite, (V- and Co-rich) magnetite, titano-magnetite, biotite, Table 1). Quartz and calcite occur in irregular patches and chlorite is
(Mn-, V- and Ta-rich) ilmenite, muscovite, rutile, and apatite (Figs. 5 commonly replaced by biotite (Fig. 8D). Amygdules are locally pre-
and 7; Table 1). Hematite occurs as randomly oriented bundles of served in weathered relict pillow cores.
A E
100 100.0
Pillow cores
Rock/Chondrite
Rock/Chondrite
10.0
10
1.0
N-MORB Group 3
N-MORB Hyaloclastites Group 4
1 0.1
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
B F
100 100
Pillow rims
Rock/Chondrite
Rock/Chondrite
10 10 Weathered red basalts–red soil
N-MORB N-MORB
1 1
C G
100 100
Weathered, brown to green basalts–soil
Hyaloclastites Group 1
Rock/Chondrite
Rock/Chondrite
10 10
N-MORB
Group 1
N-MORB
Group 2
1 1
D H
100 100
Hyaloclastites Group 2 Weathered brown to green basalts–soil
Rock/Chondrite
Rock/Chondrite
10 10
Group 3
N-MORB
Group 4
N-MORB Group 5
1 1
Fig. 9. Chondrite-normalized REE patterns for Schreiber Beach pillow cores, pillow rims, hyaloclastites, weathered red basalts (red soil), and weathered brown to green basalts.
Normalization values are from Sun and McDonough (1989). N-MORB values are from Hofmann (1988).
6. Geochemical results (5.7–10.5 wt.%), Na2O (1.94–4.04 wt.%), and K2O (0.16–0.65 wt.%) con-
tents (Table 2). TiO2 (1.15–1.40 wt.%) and Al2O3 (13.6–14.8 wt.%) have
Geochemical variations exhibited by the Schreiber Beach sam- a restricted range of concentrations. Mg-numbers (31–41) are relatively
ples (Table 2) are illustrated here using chondrite-normalized low, consistent with an Fe-tholeiitic basalt affinity. Pillow cores show
(Fig. 9) and primitive mantle-normalized extended trace element moderate variations in transition metal contents (Ni: 82–128 ppm;
diagrams (Figs. 10 and 11). Potential correlations between whole-rock Cr: 155–189 ppm; Co: 47–62 ppm; V: 290–357 ppm; Sc: 36–50 ppm).
δ18O values and certain major and trace elements are illustrated in Ratios of Al2O3/TiO2 (10–12), Zr/Hf (35–37), and Nb/Ta (15–16) are
Fig. 12. restricted. Pillow cores display near-flat REE patterns (La/Smcn =
0.86–0.99; Gd/Ybcn =1.08–1.28), with minor negative to positive Eu
6.1. Pillow cores (Eu/Eu*=0.89–1.16) anomalies (Fig. 9A). Pillow cores also have minor
negative to zero Pb anomalies, large negative K anomalies, and very
Pillow cores are characterized by a moderate range of SiO2 large positive Ba anomalies (Fig. 10A). Pillow cores exhibit a narrow
(46.7–60.9 wt.%), MgO (2.7–4.2 wt.%), Fe2O3 (7.6–16.2 wt.%), CaO range of δ18O values at 12.3–12.7‰ (Table 2).
A
100.0
Pillow cores
Rock/Primitive mantle
10.0
1.0
0.1
Rb Ba Th U Nb Ta K La Ce Pb Pr Sr Nd Zr Hf Sm Eu Ti Gd Tb Dy Y Ho Er Tm Yb Lu
B 100.0
Pillow rims
10.0
1.0
0.1
C 100.0
10.0
1.0
0.1
D 100.0
10.0
1.0
0.1
Fig. 10. Primitive mantle-normalized trace element patterns for Schreiber Beach pillow cores, pillow rims and hyaloclastite (Groups 1 and 2). Normalization values are from
Hofmann (1988).
6.2. Pillow rims 6.3. Hyaloclastites
Pillow rims have lower SiO2 (36.7–47.9 wt.%) but higher Fe2O3 The hyaloclastites are compositionally diverse, and have been
(12.0–25.5%) and MgO (3.0–7.5 wt.%) contents than pillow cores divided into four groups based on their REE and other trace element
(Table 2). Pillow rim TiO2 (1.1–1.3 wt.%), Al2O3 (13.3–16.2 wt.%), patterns (Table 2). Group 1 has the lowest SiO2 (34–43 wt.%) but
CaO (3.0–10.5 wt.%), Ni (106–144 ppm), Cr (168–211 ppm), and the highest Al2O3 (11.4–12.6 wt.%), MgO (4.9–5.0 wt.%), TiO2 (0.8–
Co (52–77 ppm) contents and Al2O3/TiO2 (12), Zr/Hf (35–36), and 1.1 wt.%), Ni (84–108 ppm), Cr (139–165 ppm), Co (51–56 ppm), and
Nb/Ta (15–16) ratios are comparable to those of the cores. Sample Sc (41–44 pm) contents. Concentrations of TiO2, Ni, Co, and Sc in Groups
SC2008-11, which has the lowest SiO2 (36.7 wt.%) but highest Fe2O3 2, 3 and 4 are significantly lower than those in Group 1, whereas Al2O3/
(25.5 wt.%) and MgO (7.5 wt.%) contents, is strongly chloritized. Pillow TiO2 ratios are significantly higher. SiO2 contents reach 87 wt.% in
rims have near-flat REE patterns (La/Smcn = 0.83–0.96; Gd/Ybcn = Group 3, whereas Group 4 has the highest Fe2O3 content (26.6 wt.%).
0.95–1.07) (Fig. 9B), small negative to positive Sr anomalies, positive Group 1 displays (i) flat REE patterns (La/Smcn =1.04–1.08; Gd/Ybcn =
Pb and Ba anomalies, and large negative K anomalies (Fig. 10B). The 0.99–1.01), and (ii) negative Sr, Pb, and K but positive Ba anomalies
δ18O values of pillow rims (10.4–12.7‰) overlap with, but extend to (Figs. 9C and 10C). Group 2 displays (i) moderately enriched LREE pat-
lower values than pillow cores. terns (La/Smcn = 1.30–1.54, (ii) depleted and convex upward HREE
A 100.0
10.0
1.0
Group 3
0.1 Hyaloclastites
Group 4
0.0
B 100.0
10.0
1.0
Weathered red basalts–red soil
0.1
C 100.0
10.0
Group 1
1.0
Group 2
Weathered brown to green basalts–soil
0.1
D 100.0
10.0
Group 3
1.0 Group 4
Weathered brown to green basalts–soil Group 5
0.1
Fig. 11. Primitive mantle-normalized trace element patterns for Schreiber Beach hyaloclastites (Groups 3 and 4), weathered red basalts ― red soil, and weathered brown to green
basalts (soil). Normalization values are from Hofmann (1988).
A 18
E 18
15 15
δ18O (‰)
δ18O (‰)
PC
PR
12 12
RH
WRB
WBGB
9 9
0 15 30 45 60 75 90 0 20 40 60 80
SiO2 (wt.%) Sc (ppm)
B 18
F 18
15 15
δ18O (‰)
δ18O (‰)
12 12
9 9
0 2 4 6 8 0 8 16 24 32 40
MgO (wt.%) Nb/U
C 18
G 18
15 15
δ18O (‰)
δ18O (‰)
12 12
9 9
0 50 100 150 200 0 4 8 12 16
Ni (ppm) TiO2/U
D 18 H
18
15 15
δ18O (‰)
δ18O (‰)
12 12
9 9
0 50 100 150 200 250 0 20 40 60 80 100
Cr (ppm) Zr (ppm)
Fig. 12. δ18O versus SiO2 (wt.%), MgO (wt.%), Ni (ppm), Cr (ppm), Sc (ppm), Nb/U, TiO2/U, and Zr (ppm) for Schreiber Beach pillow cores (PC), pillow rims (PR), red hyaloclastites
(RH), weathered red basalts (WRB), and weathered brown to green basalts (WBGB).
patterns (Gd/Ybcn = 1.18–1.95), and (iii) significant depletion of HFSE negative anomalies of Zr, Hf, Sr, and Pb (Figs. 9E and 11A). Red
(Zr, Hf, Nb, Ta), Sr, Pb, K, and Rb (Figs. 9D and 10D). Group 3 has (i) hyaloclastite samples (Group 2), which are located at the base of the
flat to moderately enriched LREE (La/Smcn = 0.93–1.33), (ii) slightly weathering profile and associated with bundles of hematite flakes,
enriched HREE (Gd/Ybcn = 0.74–0.94) patterns, and (iii) positive Ti, Pb have the highest δ18O values of 16.1–17.1‰ (Table 2). Red hyaloclastites
and U but negative K anomalies (Figs. 9E and 11A). Group 4 exhibits comprise one end of a linear trend on δ18O versus element concentration
(i) a moderately enriched LREE pattern (La/Smcn = 1.65), (ii) a depleted plots, but occupy a more or less separate field from other samples on
and convex upward HREE pattern (Gd/Ybcn = 1.29), and (iii) large δ18O versus Nb/U and TiO2/U diagrams (Fig. 12).
Table 3
Percentage (%) gains and losses (ΔC)* in the Schreiber pillow rims and hyaloclastites, and weathered basalts.
Weathered red
Pillow rims Hyaloclastite Basalts ― red soil Weathered brown to green basalts
Group 1 Group 2 Group 3 Group 4 Group 1 Group 1 Group 2 Group 3 Group 4 Group 5
SiO2 −18 −25 +39 +54 −4 −46 +14 +20 +8 +20 +8

Al2O3 +3 −16 −68 −86 −37 −18 −21 −12 −18 −28 −15
TiO2 −1 −24 −87 −90 −79 −24 −26 +2 −24 −26 −20
Fe2O3 (T) +47 +45 +6 −37 105 +139 +42 −29 +65 +15 +57
MnO +16 +37 −75 −60 −58 +10 −84 −78 −83 −83 −84
MgO +55 +38 −51 −77 +4 +44 −3 −41 +10 −20 +6
CaO −20 +28 −55 −36 −57 −4 −91 −63 −94 −76 −93
Na2O −43 −80 −96 −96 −100 −96 −86 −35 −96 −61 −95
K2O −52 −51 −82 −89 −84 +300 +337 +1004 +280 +337 +463
P2O5 −39 −46 −60 −83 −33 −26 −18 −22 −6 −33 +21
Ni +10 −13 −63 −54 −14 +45 −6 −35 +2 −11 +8
Cr +10 −11 −68 −88 −52 0 −7 +16 −22 +8 −18
Co +20 0 −62 −49 +2 +5 −47 −61 −38 −52 −39
V +12 −14 −7 −83 +98 +38 −48 −32 −50 −43 −52
Sc +15 −5 −58 −77 −43 +10 −22 −14 −18 −34 −26
Cu −5 +3 −34 −55 −93 −86 −93 −31 −93 −93 −91
Zn +64 38 −48 −73 −8 +11 −28 −45 −14 −38 −15
Mo −24 +8 +90 +575 −44 +12 −69 +7 −58 −65 −83
Li +26 25 +16 −68 +124 +247 +139 +43 +166 +130 +220
Ba −30 −47 −84 −88 −75 −26 −61 +537 −69 −55 −2
Cs +7 −41 −8 −80 −62 +2122 +2556 +1489 +2476 +2082 +1160
Rb −39 −62 −64 −90 −91 +522 +548 +669 +526 +465 +391
Sr −21 −49 −1 −80 −56 −37 −88 −47 −91 −61 −86
Pb +176 −4 +188 +23 +44 +160 −22 −16 −4 −10 −28
Ga +19 −5 −51 −79 +27 +20 −6 −38 −3 −32 −5
Zr +2 −11 −74 −80 −62 −20 −22 +7 −21 −22 −16
Hf +1 −12 −76 −80 −62 −18 −22 +9 −21 −22 −17
Nb +3 −16 −78 −87 −66 −20 −22 +7 −22 −20 −18
Ta +2 −13 −80 −80 −70 −20 −24 +9 −21 −22 −17
Th 0 +29 −34 −77 +4 −14 −25 +5 −21 −22 −22
U +3 +33 −10 −61 +49 +37 0 +8 +33 −7 +14
Y −9 −5 +25 −75 +260 +153 +48 −28 −27 −19 −29
La −18 0 +115 −77 +426 +194 −10 −34 +7 −30 −65
Ce −17 −5 +104 −79 +370 +194 −17 −36 −7 −30 −58
Pr −16 −7 +80 −80 +324 +169 −19 −37 −5 −31 −52
Nd −18 −9 +59 −81 +277 +152 −22 −37 −8 −31 −45
Sm −15 −13 +39 −80 +195 +146 −20 −36 −16 −31 −36
Eu −24 −12 +25 −83 +139 +127 −22 −27 −25 −33 −40
Gd −12 −13 +32 −78 +175 +140 −3 −36 −15 −29 −29
Tb −10 −11 +35 −78 +194 +154 +12 −35 −19 −28 −31
Dy −8 −9 +35 −77 +229 +161 +27 −34 −20 −26 −32
Ho −7 −6 +28 −76 +251 +162 +38 −33 −20 −25 −32
Er −4 −4 +20 −74 +235 +161 +44 −29 −21 −21 −32
Tm −3 −3 +5 −73 +192 +153 +40 −24 −23 −21 −32
Yb 0 0 −8 −71 +143 +142 +33 −17 −26 −19 −30
Lu +1 +2 −20 −71 +119 +127 +29 −13 −25 −20 −30
ΔC = [(Cas − Cpc)/Cpc) * 100].

Cas = concentration in altered sample, Cpc = concentration in pillow core.
*Positive (+) ΔC values indicate a gain and negative (−) ΔC values indicate a loss.
6.4. Weathered red basalts (red soil) 6.5. Weathered brown to green basalts (soil)
The weathered red basalts have the lowest SiO2 (24.5–30.7 wt.%) The weathered brown to green basalts have been divided into five
but the highest Fe2O3 (27.8–32.8 wt.%) contents of all samples ana- groups based on their REE patterns. Group 1 is characterized by moder-
lyzed (Table 2). They are characterized by 0.89–1.04 wt.% TiO2, ate variations in SiO2 (51.5–60.7 wt.%), Fe2O3 (15.6–21.7 wt.%), and
11.1–12.2 wt.% Al2O3, 4.64–5.44 wt.% MgO, and 1.24–1.80 wt.% K2O, MgO (2.9–5.4 wt.%), a limited range in Al2O3 (10.8–12.6), TiO2
and moderate ranges of Ni (139–182 ppm), Cr (153–193 ppm), Co (0.8–1.1 wt.%), and Sc (33–37 ppm), and large variations in CaO
(49–64 ppm), and Sc (47–53 ppm). Al2O3/TiO2 (12–13), Zr/Hf (0.2–5.0 wt.%), Na2O (0.0–1.7 wt.%), and K2O (0.6–2.5 wt.%) (Table 2).
(34–36), and Nb/Ta (15–16) ratios are comparable to those of the pil- Nickel (80–137 ppm) and Cr (146–250 ppm) contents are comparable
low cores and rims whereas Mg-numbers are low (~ 25 versus ~ 36). to the pillow cores, whereas Co (21–37 ppm) and V (92–300 ppm) con-
The weathered red basalts also display flat to slightly enriched LREE centrations are lower. Group 1 has moderately depleted to enriched
patterns (La/Smcn = 0.99–1.22), flat to slightly depleted HREE pat- LREE patterns (La/Smcn = 0.81–1.28), enriched to flat HREE patterns
terns (Gd/Ybcn = 0.97–1.26), negative Ti, Zr, Hf, Sr, Nb, and Ta anom- (Gd/Ybcn = 0.74–1.12), and negative Sr but positive K anomalies
alies, and minor positive Ba anomalies (Figs. 9F and 11B). The δ 18O (Figs. 9G and 11C).
(12.6–13.9‰) values of the weathered red basalts overlap with, but In Group 2, the major element compositions of samples SC2008-04
extend to higher values than the cores (Table 2). and SC2008-07 are similar to Group 1, but sample SC2008-08 is more
A2 E 4
Pillow rims Weathered brown to green basalt – soil
Group 1
Sample/Pillow core
Sample/Pillow core
3
1 2
0 0
SiO2 Al2O3 TiO2 Fe2O3 MnO MgO CaO Na2O K2O P2O5 SiO2 Al2O3 TiO2 Fe2O3 MnO MgO CaO Na2O K2O P2O5
B2 F 4
Hyaloclastite Group 1 Group 2 Weathered brown to green basalt – soil
SC2008-20
Sample/Pillow core
Sample/Pillow core
3
1 2
0 0
C2 G4
Weathered brown to green basalt – soil
Hyaloclastite
Group 2 Group 3
Sample/Pillow core
Sample/Pillow core
Group 3 Group 4 3
1 2
0 0
D4 H4
Weathered red basalt – red soil Weathered brown to green basalt – soil
Group 4 Group 5
Sample/Pillow core
Sample/Pillow core
3 3
2 2
1 1
0 0
Fig. 13. Average pillow core-normalized major element column diagrams for the Schreiber Beach pillow rims, hyaloclastites, weathered red basalts (red soil), and weathered brown
to green basalts (soil).
comparable to the weathered red basalts (i.e., very low SiO2, 37.3 wt.%; slightly to moderately fractionated in Group 3 (Fig. 9H). Group 4 has
high Fe2O3, 25.7 wt.%). Group 2 displays concave upward LREE (La/ near-flat REE patterns (La/Smcn = 0.88–0.99; Gd/Ybcn = 1.00–1.08).
Smcn = 0.92–0.99) and HREE (Gd/Ybcn = 0.78–1.04) patterns, negative Group 5 is characterized by depleted LREE (La/Smcn = 0.51) and HREE
Sr but positive K anomalies, and enrichments of Rb and Ba over Th Gd/Ybcn = 1.17) patterns (Figs. 9H and 11D).
(Figs. 9G and 11C). The weathered brown to green basalts have variably elevated
Groups 3, 4 and 5 have similar Al2O3/TiO2, Nb/Ta and Zr/Hf ratios, δ 18O values (12.3–15.6‰) values relative to pillow cores and rims
and display negative Sr but variably positive K and Rb anomalies (Table 2). The lowest values (12.3–12.8‰; samples SC2008-04,
(Figs. 10 and 11). However, Groups 3 and 5 have higher Fe2O3 SC2008-05 and SC2008-21), which are from relict pillow cores,
(18.6–25.5 wt.%) than Group 1 (12.6–17.2 wt.%), and Group 4 has match those of unweathered pillow cores (Table 2). Generally,
greater SiO2 (60.2–62.3 wt.%) than Groups 3 and 5 (50.4–57.1 wt.%). weathered samples have higher δ 18O values than their unweathered
LREE (La/Smcn = 1.12–1.26) and HREE (Gd/Ybcn = 1.17–1.42) are counterparts. The strong positive correlation between δ 18O and SiO2,
and variable but negative correlations between δ 18O, on one hand, whereas the stratigraphic upward trend from well preserved pillow
and MgO, Ni, Cr, Sc and Zr, on the other hand, reflects the addition basalts to intensely altered counterparts immediately subjacent to
of secondary silica during weathering processes (Fig. 12). the Paleoproterozoic Gunflint Formation and basal conglomerates is
readily attributed to subaerial weathering in the Paleoproterozoic.
7. Discussion Given preservation of primary magmatic textures (Figs. 2–6) and
minimally altered REE and HFSE patterns (Figs. 9A and 10A) in
7.1. Element mobility unweathered pillow cores, they have been used as a parental refer-
ence (protolith) for mineralogical and geochemical variations during
The exact timing of element mobility (e.g., Neoarchean submarine subsequent processes. Average percentage gains (+ ΔC) and losses
alteration, Neoarchean greenschist facies regional metamorphism, (−ΔC) in element concentrations for pillow rims, hyaloclastites, weath-
Paleoproterozoic subaerial weathering, and Paleoproterozoic burial ered red basalts, and weathered brown to green basalts, relative to the
greenschist facies metamorphism) cannot be constrained from the unweathered pillow cores, are summarized in Table 3 and illustrated in
existing data. However, the large compositional variability of pillow Figs. 13–16. Following Teagle and Alt (2004), gains are described as
rims relative to cores is most plausibly due to some combination of strongly enriched (>60%), moderately enriched (20 to 60%), slightly
Neoarchean submarine hydrothermal alteration and metamorphism, enriched (10 to 20%), and immobile 0 to 10%. Losses are expressed as
A 2
Pillow rim
Sample/ Pillow core
0
B 3
Hyaloclastite
Sample/ Pillow core
Group 1 Group 2
2
0
C 5
Hyaloclastite Group 3 Group 4
Sample/ Pillow core
0
D 5
Weathered red basalt–red soil
Sample/ Pillow core
0
Fig. 14. Average pillow core-normalized trace element column diagrams for Schreiber Beach pillow rims, hyaloclastites, and weathered red basalts (red soil).
A3
Weathered brown to green basalt–soil
Sample/ Pillow core

Group 1
2
0
B5
Weathered brown to green basalt–soil SC2008-20
Sample/ Pillow core
0
C3
Sample/ Pillow core
Group 2 Group 3
2
0
D3
Sample/ Pillow core
Group 4 Group 5
2
0
Fig. 15. Average pillow core-normalized trace element column diagrams for Schreiber Beach weathered brown to green basalts (soil).
immobile (0 to −10), slightly depleted (−10 to −20%), moderately de- and Sr, the Schreiber Beach pillow cores display smooth trace element
pleted (−20 to −60%), and strongly depleted (>−60%). patterns. Accordingly, we suggest that Ba and K were strongly and Pb
and Sr were moderately mobile during Neoarchean seafloor alteration
7.1.1. Pillow cores of these cores.
Pillow basalts of the Schreiber Beach profile are part of the mantle
plume-derived tholeiitic basalt-komatiite oceanic plateau lithotectonic 7.1.2. Pillow rims
assemblage comprising the Schreiber-Hemlo greenstone belt (Polat et Average percentage gains (+ΔC) and losses (−ΔC), relative to pil-
al., 1998; Polat and Kerrich, 2000). In order to assess element mobility low cores, for pillow rims (Table 3) are illustrated in Figs. 13A, 14A
in pillow cores during seafloor alteration, we have compared the trace and 16A. Rims are characterized by moderate gains of Fe2O3 (+47)
element patterns of the pillow cores with those of plume-derived and MgO (+55), and slight loss of SiO2 (−18), likely reflecting the for-
unaltered lavas. McDonough and Ireland (1993) showed that unaltered mation of Fe-rich clays or chlorite during Neoarchean seafloor hydro-
glass inclusions from the 2.7 Ga Belingwe komatiites from Zimbabwe thermal alteration (see Alt et al., 1998). Al2O3 (+3) and TiO2 are
display smooth REE and LILE patterns. In addition, LILE, REE, and HFSE virtually immobile (cf., Costa et al., 1983). Rims are strongly enriched
in fresh oceanic plateau lavas generally show restricted compositional in Pb (+176) and Zn (+64). They are characterized by moderate de-
variation (Kerr, 2003). Except for Ba and K, and to a lesser extent Pb pletions of LILE including K2O (−52), Na2O (−43), and Rb (−39).
Transition metals are slightly enriched (+10 to +20). LREE, except Eu moderate depletion (Nb: −16; Zr: −11), and there is moderate enrich-
(−24), are slightly depleted (−10 to −18), whereas HREE are essen- ment of Th (+30) and U (+32) (Fig. 14B).
tially immobile (0 to −12). HFSE and Th are the least mobile elements Group 2 hyaloclastites are moderately enriched in SiO2 (+39) and
(TiO2: −1; Nb: +3; Ta: 2; Zr: +2, Hf: +2; Y: −9; Th: 0). slightly enriched in Fe2O3 (+ 6), but strongly depleted of other major
elements (Al2O3: − 68; MgO: − 51; CaO: − 55; Fig. 13B). Like pillow
7.1.3. Hyaloclastites rims, Group 2 is strongly enriched in Pb (+188) but depleted of
Group 1 hyaloclastites are characterized by slight to strong deple- LILE (K2O: −82; Na2O: − 96; Rb: − 64; Ba: − 84; Figs. 13B and
tions of SiO2 (−25), Al2O3 (−16) and P2O5 (−47) but moderate 14B). LREE are moderately to strongly enriched (+ 26 to +105),
enrichments in Fe2O3 (+45), MnO (+37), MgO (+38) and CaO HREE are moderately depleted to moderately enriched (− 20 to
(+20) (Fig. 13B). Group 1 LILE are strongly depleted (K2O: −51; + 32), HFSE are strongly depleted (Nb: − 78; Zr: − 74; Ti: − 87),
Na2O: −80; Rb: −62; Sr: −49; Ba: −47) (Figs. 13B and 14B). Transi- and Th (− 34) and U (− 10) are variably depleted (Fig. 14B). There
tion metals are immobile to slightly depleted (Ni: −11; Cr: −11; are strong to moderate losses of most transition metals (Ni: − 63;
Sc: +5; Fig. 16B). LREE (0 to −12) are immobile to slightly depleted, Cr: − 68; Sc: − 58; Cu: − 34; Zn: − 48) (Fig. 16B). Except for Fe2O3
HREE (0 to −11) and Y (+5) are mainly immobile, HFSE exhibit (− 45%), fractionation of major elements in Group 3 is similar to
A 2 E2
Pillow rim Group 1
Sample/Pillow core
Sample/Pillow core
1 1
0 0
Cr Co Ni V Sc Ti Cu Zn Mo Cr Co Ni V Sc Ti Cu Zn Mo
B 2 F3
Hyaloclastite Weathered brown to green
basalt–soil
Sample/Pillow core
Sample/Pillow core
Group 1 Group 2 SC2008-20

2
0 0
C 3 G2
Hyaloclastite Weathered brown to green basalt–soil
Sample/Pillow core
Sample/Pillow core
Group 3 Group 4
2 Group 2 Group 3
0 0
D 2 H2
Weathered red basalt –red soil Weathered brown to green basalt –soil
Sample/Pillow core
Sample/Pillow core
Group 4 Group 5
1 1
0 0
Fig. 16. Average pillow core-normalized transition metal column diagrams for Schreiber Beach pillow rims, hyaloclastites, weathered red basalts (red soil), and weathered brown to
green basalts (soil).
Group 2 (Fig. 13B, C). Depletions of LILE (K2O: − 92; Rb: − 95) and burial metamorphism cannot be exactly constrained from the existing
transition metals (Ni: − 59; Cr: − 88; Co: − 57; Zn: − 70; Cu: − 56) data.
are also comparable to Group 2 (Figs. 14B, C; 16B, C). Group 3 is
strongly depleted of REE (La: − 84; Gd: − 85; Yb: − 80), Y (−845), 7.1.5. Weathered brown to green basalts (soil)
Th (− 90), U (− 63) and HFSE (Nb: − 88; Ti: − 90; Zr: − 91) All five groups of the weathered brown to green basalts, relative to
(Fig. 14C). Depletion of major and trace elements in Group 3 unweathered pillow cores, are variably enriched in SiO2 (+8 to +20)
hyaloclastites is probably related to dilution by secondary quartz but depleted of Al2O3 (−12 to −28), CaO (−63 to −93), and Na2O
(SiO2: + 54; Fig. 13C). (−35 to −95) (Fig. 13E–H). All groups are also strongly enriched in
Group 4 hyaloclastites are characterized by strong enrichment in K2O (+280 to +1000), Rb (+390 to +670), Cs (+1100 to +2550),
Fe2O3 (+ 105) relative to other groups; most other major elements and Li (+43 to +220), whereas Ba shows gains in Group 2 (+537)
show moderate to strong depletion relative to pillow cores (Al2O3: but losses in Groups 1, 3, and 4 (−2 to −69) (Fig. 15). All groups are
− 37; TiO2: − 79; CaO: − 57; Na2O: − 100; P2O5: − 33) (Fig. 13C). strongly depleted of Sr (−47 to −91), Groups 1, 3, 4, and 5 are depleted
Like the other hyaloclastites, Group 4 shows strong depletion of LILE of HFSE (Nb: −18 to −22; Zr: −16 to −22) and Th (up to −25),
(K2O: − 84; Rb: − 91; Sr: − 56; Ba: − 75) and HFSE (Nb: − 66; Ta: whereas Group 2 displays minor enrichments in these elements
− 70; Zr: − 62; Ti: − 79; Fig. 14C). Transition metals are also general- (Fig. 15). Group 1 shows slight decreases in LREE (−3 to −22) and
ly depleted (Fig. 16C) but unlike Group 3, this change does not reflect moderate decreases in HREE (−13 to −44), whereas Groups 2–5 show
silica enrichment. Also unlike Group 3, Group 4 is strongly enriched in depletion of both LREE and HREE (Fig. 15). Enrichments and depletions
REE (La: + 426; Sm: + 195; Ho: +250; Yb: +144). are variable in Ni (+2 to −35) and Cr (+8 to −22), whereas Co (−38
to −61), V (−32 to −52), and Sc (−14 to −34) show moderate
depletions (Fig. 16). These geochemical variations are attributed to
7.1.4. Weathered red basalts (red soil) Paleoproterozoic subaerial weathering processes.
Fe2O3 (+140) and K2O (+300) are strongly enriched, MgO (+44)
and MnO (+10) are moderately to slightly enriched, and other major 7.2. Neoarchean submarine alteration
elements (SiO2: −46; Al2O3: −18) are moderately to strongly depleted
in the weathered red basalts (Fig. 13E). These samples are also charac- Gradual changes occur in structure, texture, and mineralogy from
terized by strong enrichment in Rb (+550), Li (+247), Pb (+160), the unweathered green pillow basalts to the weathered and fragmented
REE (up to +195) and Y (+153), moderate depletion of U (−37), brown, green, and red basalts below the Paleoproterozoic unconformity
and slight depletion of HFSE (Nb: −20; Zr: −20; Hf: −18) and Th at Schreiber Beach (Figs. 2–8). Despite preservation of undeformed pil-
(−18) (Fig. 14D). Transition metals are variably enriched (Ni: +45; low structures, hyaloclastites, igneous textures, and amygdules, prima-
V: +38; Sc: +10; Fig. 16D). These compositional variations in the ry igneous minerals were not observed in the Schreiber pillow basalts.
weathered red basalts, relative to unweathered pillow cores, are attrib- These phases were likely destroyed during Neoarchean submarine hy-
uted to the effects of Paleoproterozoic subaerial weathering and burial drothermal alteration processes and/or subsequent greenschist facies
metamorphism. The separate effects of the subaerial weathering and regional metamorphism.
Several features are consistent with Neoarchean submarine alteration:
A (1) Abundant quartz and carbonate cements are well known prod-
ucts of basalt–seawater interaction during the brecciation of
pillow rims and pillow interstitial material that created the
hyaloclastites. Chert between pillow flows was also likely de-
posited at this time.
(2) In addition to secondary silica and carbonate, abundant chlorite,
albite, pyrite, and chalcopyrite in the pillow cores, pillow rims,
and hyaloclastites are characteristic products of submarine alter-
ation (Spooner et al., 1977; Humphris and Thompson, 1978;
Unweathered
pillow cores Muehlenbachs, 1986; Alt et al., 1998; Humphris et al., 1998; Alt
and Teagle, 2003; Staudigel, 2003; Teagle and Alt, 2004). In par-
ticular, the large increase in iron content of some rim and
hyaloclastite samples is a likely product of seafloor alteration
(Humphris et al., 1998).
(3) Amygdules in the basalts are filled with secondary calcite, quartz
B and chlorite.
(4) The δ 18O values of the Schreiber Beach pillow cores, pillow rims,
and unweathered hyaloclastites (+10.4 to +12.7‰) are much
higher than fresh mid-ocean ridge basalts (+5.7‰) (Taylor,
1968; Muehlenbachs and Clayton, 1972a, 1976; Spooner et al.,
1977; Humphris and Thompson, 1978; Muehlenbachs, 1986;
K-enrichment
Alt et al., 1998; Humphris et al., 1998; Alt and Teagle, 2003;
Bosch et al., 2004; Teagle and Alt, 2004). Basaltic rocks are
Weathered brown enriched in 18O during interaction with seawater at low temper-
to green basalts atures and high water/rock ratios, as a result of the formation of
clay minerals and other secondary phases as observed in Recent
ocean crust (Muehlenbachs and Clayton, 1972a, 1976; Staudigel,
2003) and Neoarchean volcaniclastic turbidites (Feng et al.,
Fig. 17. A–CN–K (Al2O3–CaO + Na2O–K2O) ternary plots for Schreiber Beach pillow
cores and weathered brown to green basalts. Weathered brown to green basalts plot 1993).
towards Al2O3 apex, displaying a subaerial weathering trend. Weathered brown to (5) Extensive mobilization of alteration-sensitive elements (SiO2,
green basalts also display a K-enrichment. Fe2O3, CaO, Na2O, K2O, Cs, Ba, Rb, Sr, Pb, Zn, Cu, Fe, and LREE)
has occurred. That said – the cause(s) of enrichment versus de- Schreiber Beach profile is no exception, as indicated by the presence
pletion of these elements relative to fresh basalt are not fully of microscopic chlorite veinlets crosscutting hematite, and its partial
constrained in terms of specific processes. On one hand, the replacement by magnetite and ilmenite (Figs. 7 and 8). The appear-
Schreiber Beach and other Archean basalts thought to have un- ance of ilmenite and magnetite in the upper part of the profile suggest
dergone submarine alteration typically are depleted of LREE that ferric oxides were partially converted to ferrous oxides during
and LILE (Polat et al., 2007 and references therein). Teagle and this process (cf., Ohmoto, 1996), which was likely related to deposi-
Alt (2004) have also reported LREE depletion of altered basalts tion of the overlying Paleoproterozoic sedimentary rocks. The ab-
(quartz- and chlorite-rich rocks) from the Middle Valley, Juan sence of clay minerals and other primary weathering products in
de Fuca Ridge. On the other hand, other geochemical studies of the Schreiber profile is not surprising given the recrystallization that
modern seafloor and ophiolitic basalts indicate that LREE and would have accompanied such deep diagenetic/burial metamorphic
LILE are mainly gained during seafloor alteration (Ludden and processes.
Thompson, 1978; Valsami and Cann, 1992; Alt et al., 1998; It can be difficult to distinguish soil-forming/weathering processes
Houghton et al., 2004; Teagle and Alt, 2004). Alkaline elements on one hand and subsequent diagenetic and metamorphic processes
tend to be enriched in basalts during low-temperature seafloor on the other hand within Precambrian paleosols (Rye and Holland,
alteration (see Alt, 1995). 1998; Retallack, 2001). Further confounding this problem, the Schreiber
weathering profile lacks well-developed soil horizons. Their absence
A role for greenschist facies regional metamorphism should also be could indicate an immature, weakly developed paleosol. Alternatively,
considered when interpreting element mobility in the Schreiber Beach much of the soil may have been eroded, leaving only a basal remnant
profile, given that the Schreiber-Hemlo greenstone belt underwent of an eroded paleosol. The Schreiber weathering profile nevertheless
greenschist facies regional metamorphism at about 2700 Ma during shares many of the major mineralogical and geochemical characteristics
oceanic plateau accretion and arc-arc collision (Polat et al., 1998). of Precambrian paleosols (see Maynard, 1992; Rye and Holland, 1998;
HFSE (Y, Zr, Hf, Nb, Ta, and Ti) and transition metals, for example, are Retallack, 2001):
generally considered to be immobile in modern basalts affected by
low and high temperature seawater–rock interaction (Teagle and Alt, (1) Paleosols should be a product of in-situ weathering; (2) they
2004; see reviews by Manikyamba et al., 2008; Said and Kerrich, 2009 should show gradual systematic textural, mineralogical, and chemical
and references therein). These elements, however, appear to have changes from the parent rock to the top of the soil; (3) they should
been mobile in the Schreiber Beach. display soft sediment deformation structures along the contact
between the paleosol and overlying sedimentary sequence; and
7.3. Formation of Paleoproterozoic weathering profile (4) Ti/Al and Ti/Zr ratios in the weathering profile should not deviate
more than 50 and 40%, respectively, from those in the parent rock
Field, petrographic, and geochemical observations suggest that the
(Maynard, 1992; Rye and Holland, 1998).
Schreiber weathering profile developed on Neoarchean greenstone par-
ent rocks prior to deposition of the overlying ca. 1.88 Ga Gunflint Chert The Schreiber weathering profile meets criteria 1, 2, and 4. In par-
and basal conglomerates (Figs. 2–8). The upper part of the weathering ticular, the ratios of Ti/Al and Ti/Zr do not deviate more than 20% from
profile still retains some relic volcanic textural features (e.g., amygdules) the values in the parent greenstone (Table 2). Also, the increase in the
from the parental greenstones. Physical evidence of subaerial weathering Chemical Index of Alteration (CIA) from 42 for unweathered pillow
includes exfoliation and fragmentation of the pillow basalts (Figs. 2 and cores to 93 for weathered pillows (Table 2), and the redistribution
3). The intensity of fracturing increases with stratigraphic height towards of many elements, including LILE, REE, HFSE and transition metals,
the contact with the Paleoproterozoic conglomerate and Gunflint Chert, are typical of soil-forming processes (Braun et al., 1993; Cotten et
suggesting a link between uplift and weathering during profile forma- al., 1995; Hodson, 2002; Neaman et al., 2005; Mitchell and Sheldon,
tion. Some erosion of the Schreiber profile prior to deposition of the 2009, 2010). The increase in δ 18O values from + 10.4 to + 12.7‰ for
Paleoproterozoic sequence is indicated by the presence of weathered unweathered pillow cores and rims to + 12.3 to + 17.1‰ in the
basalt fragments at the base of the overlying conglomerates. weathered pillow rims, cores and hyaloclastites (Table 2) is also con-
Evidence for subaerial chemical weathering includes the colour sistent with low-temperature soil formation processes. Soft sedimen-
change from green to red, likely reflecting formation of secondary tary structures, however, were not observed. There are a couple of
Fe-oxides and Fe-oxyhydroxides, now represented mainly by 5–15 μm possible reasons for their absence that do not invalidate the paleosol
long flakes of hematite (Figs. 5–8). The presence of hematite suggests hypothesis. First, it may be difficult to detect soft sediment deforma-
profile development under oxidizing conditions. The weathered and tion given the limited exposure at Schreiber Beach and compaction
fragmented pillow basalts below the Paleoproterozoic unconformity arising from deposition of the overlying Paleoproterozoic sedimentary se-
are also characterized by increasingly abundant patches of calcification quence. Second, the Schreiber Beach profile developed on a fragmented,
and silicification upwards in the section (Figs. 5F and 7A). On the rugged pillow basalt surface. Recognition of soft sediment structures on
A–CN–K (Al2O3–CaO + Na2O–K2O) diagram (Fig. 17), the Schreiber such an irregular parent surface would be difficult under the best of
weathered and unweathered basalts plot in separate fields, in partic- conditions.
ular, the weathered brown to green basalts display a trend towards
Al2O3 apex, as expected for weathered rocks (Nesbitt and Young, 7.5. Alkaline metasomatism
1989). The very siliceous hyaloclastites at the base of the weathering
profile have the highest δ 18O values (+ 16.1 to + 17.1‰) measured Alkaline metasomatism is one of the major geochemical characteris-
for this profile. Such compositions are typical of secondary silica tics of Precambrian siliciclastic sequences and paleosols, though its origin
formed at low temperatures from fresh water. is not well understood (Farrow and Mossman, 1988; Zbinden et al., 1988;
Nesbitt and Young, 1989; Wiggering and Beukes, 1990; Macfarlane and
7.4. Can the Schreiber weathering profile be interpreted as a paleosol? Holland, 1991; Prasad and Roscoe, 1991; Retallack, 1991b; Maynard,
1992; Sutton and Maynard, 1993; Fedo et al., 1995; Ohmoto, 1996; Rye
Many Precambrian weathering profiles and paleosols have subse- and Holland, 1998; González-Álvarez and Kerrich, 2010, 2011). According
quently undergone greenschist facies metamorphism (Macfarlane to Nesbitt and Young (1989), paleosol K-enrichment occurred during
and Holland, 1991; Retallack and Krinsley, 1993; Ohmoto, 1996; their burial within subsiding sedimentary basins, augmented by produc-
Retallack, 2001; Driese et al., 2011; Murakami et al., 2011). The tion of K-rich clay minerals during the soil-forming processes.
The percentage enrichment of alkali elements in weathered (Pan and Stauffer, 2000; Babechuk and Kamber, 2011), as do most
basalts in the Schreiber Beach profile is very high: K2O (+280 to samples from Schreiber Beach (Th/U = 1.6–3.6). The average Th/U
+ 1000), Rb (+400 to + 700), Li (+40 to +250), and Cs (+ 1100 ratios in the red (2.2) and brown to green weathered basalts (2.8),
to + 2550) relative to unweathered pillow cores (Figs. 14 and 15; and the hematite-rich hyaloclastites (2.2) from Schreiber Beach are
Table 3). The K2O is contained mostly in K-feldspar, biotite, and mus- significantly lower than in its unweathered pillow cores (3.5), indi-
covite. Biotite likely formed by transformation of chlorite during cating addition of U during weathering (Table 2). The lowering of
K-metasomatism. Enrichment of K in weathered basalts, relative to Th/U ratios (and the nature of Ce anomalies, see below) in the weath-
unweathered pillow cores, is well illustrated by the A―CN―K ered versus unweathered basalts at Schreiber Beach may signify an
diagram (Fig. 17). The occurrence of this K-metasomatism is strongly oxic atmosphere at 1.9 Ga. Unlike the Schreiber Beach weathering
supportive of our interpretation of these rocks as paleosols, but the profile, however, HFSEs in the Flin Flon paleosol were relatively
timing of alkaline metasomatism cannot be constrained uniquely immobile during soil formation (Babechuk and Kamber, 2011). The
from our data; based on the results of González-Álvarez and Kerrich Flin Flon paleosol is also characterized by positive Ce anomalies, where-
(2010), this metasomatism is likely the product of interaction with as minor negative to minor positive anomalies (Ce/Ce* = 0.89–1.09) are
K-rich basinal brines. Whole-rock Rb-Sr isotope data for the Schreiber present at Schreiber Beach (Table 2). These differences may reflect the
weathering profile yield an isochron age of 1564 +/− 20 Ma (Frei and extent of oxygenation and leaching at each site.
Polat, unpublished data), potentially dating the onset of K metaso- Comparisons are also possible with the ca. 1.1 Ga Keweenawan
matic alteration, which postdates the deposition of the Gunflint (Minnesota) and Sturgeon Falls (Michigan) paleosols, which developed
Cherts and formation of the weathering profile about 350 Ma. on mid-continental rift basalts around Lake Superior. These paleosols
have not been altered significantly by post-weathering metamorphism,
7.6. Comparison of the Schreiber weathering profile with its modern and though opinions differ on the extent of K metasomatism at Sturgeon
Precambrian counterparts Falls (Zbinden et al., 1988; Mitchell and Sheldon, 2009, 2010). Element
mobility appears to have been greater in Schreiber Beach than in the
Modern soils are dominated mainly by clays (e.g., kaolinite, illite, Keweenawan paleosol, as demonstrated by the moderate loss of Zr in
montmorillonite, and smectite), feldspar, quartz, goethite, hematite, the former (Fig. 15) versus its immobility in the latter. Al2O3/TiO2 ratios
gibbsite, calcite, and gypsum. Not surprisingly, the Schreiber Beach in both the Schreiber Beach weathering profile and Sturgeon Falls
weathering profile is mineralogically different from modern counter- paleosols are similar to those of their parental rocks, indicating that
parts because: (1) its parental rocks underwent extensive submarine these elements were relatively immobile during soil formation. Like-
alteration and greenschist facies metamorphism, resulting in the loss wise, Na and Ca are variably lost and redistributed throughout both pro-
of primary igneous minerals (e.g., olivine, pyroxene, plagioclase); and files. However, Fe shows significant losses in the upper section of the
(2) subaerial weathering products were overprinted during diagene- Sturgeon Falls weathering profile (Mitchell and Sheldon, 2010), which
sis, greenschist facies burial metamorphism, and alkaline (e.g., K, Rb, is not observed in the Schreiber Beach weathering profile. This differ-
Li) metasomatism. Nonetheless, the Schreiber Beach weathering pro- ence may indicate loss of the upper portion of the Schreiber Beach
file shares many geochemical characteristics with modern soils of ba- weathering profile to erosion.
saltic parentage, including: (1) a significant increase in CIA (60–93) Others have used the geochemical composition of Precambrian
values relative to parental basalt (42–49); (2) loss of Mg and Ca; paleosols to calculate atmospheric pCO2 levels (Zbinden et al., 1988;
(3) enrichment in Si and Fe; and to a lesser extent, (4) minor Ce anom- Holland et al., 1989; Kasting, 1993; Rye et al., 1995; Rye and Holland,
alies. The behaviour of other elements (e.g., Al, Na, Mn, Ti, Ba, Sr, Cr, Co, 2000; Sheldon, 2006; Mitchell and Sheldon, 2010). We suggest that
Cu, V, Ni, and REE) at Schreiber Beach is also comparable to modern soils pCO2 values for the Schreiber Beach weathering profile cannot be calcu-
(e.g., Nesbitt and Wilson, 1992; Cotten et al., 1995; Aiuppa et al., 2000; lated with confidence using the existing data. First, the composition of
Sheldon, 2003; Kisakurek et al., 2004; Ma et al., 2007; Navarre-Sitchler pre-metamorphic/metasomatic mineral assemblages in the profile is not
and Brantley, 2007; Wimpenny et al., 2007). well known. Second, the network of 1–15 cm-thick calcite veins cross-
There are some important differences between the Schreiber cutting the profile indicates disturbance of Ca and CO2 concentrations
Beach and modern weathering profiles. Significant enrichment of following weathering. Third, the original thickness of the profile, its
Al2O3 (>30 wt.%), which is observed in many modern bauxite- depth of burial following soil formation, and the duration of soil forma-
bearing soils, is not present at Schreiber Beach and lateritic soil has tion are unknown.
not been recognized. While the Schreiber Beach weathered red
basalts have the colour and Fe2O3 (28–33 wt.%) content of modern 8. Conclusions
laterites, their low Al2O3 (11–12 wt.%) and high CaO (5–10 wt.%)
concentrations are inconsistent with such an origin (see Kisakurek This study presents field, petrographic, major and trace element, and
et al., 2004; Wimpenny et al., 2007). This difference may reflect oxygen isotopic data for unweathered to paleo-weathered Neoarchean
incomplete laterization or later alteration. basalts exposed below the Paleoproterozoic (ca. 1.88 Ga) unconformity
Comparison of the Schreiber Beach weathering profile with Precam- underlying the Gunflint Formation at Schreiber Beach, Ontario. The basalt
brian counterparts is also useful. Rye and Holland (2000) demonstrated profile at Schreiber Beach can be subdivided into pillow cores, pillow
Mg, Mn, Ca, Na, Ni, and Co loss from the top of the ca. 2.2 Ga Hekpoort rims, hyaloclastites, weathered red basalts, and weathered brown to
paleosol, South Africa. Schreiber Beach also displays such losses, except green basalts. Gradual structural, textural, mineralogical, and geochemi-
for Ni, although compared to the Hekpoort paleosol (Beukes et al., cal transitions from the unweathered to weathered basalt suggest in-situ
2002). The Schreiber Beach weathered red basalts have higher Mg subaerial weathering and paleosol formation at ca.1.9 Ga. The profile also
(and Ca) concentrations, lower Al concentrations and lower CIA underwent greenschist facies metamorphism, during its burial by
values. Loss of Ca, Mg, and Na also characterizes the ca. 2.2 Ga Paleoproterozoic sedimentary and volcaniclastic rocks.
Darkenstein paleosol, South Africa (Wiggering and Beukes, 1990), Element mobility in the Schreiber Beach profile during submarine
and like Schreiber Beach, it also displays fluctuating REE concentra- alteration, regional metamorphism, subaerial weathering and burial
tions, LREE enrichment and significant negative Eu anomalies. diagenesis/metamorphism has been assessed relative to pillow cores. Pil-
Like Schreiber Beach, the 1.85 Ga Flin Flon paleosol, Canada, is low cores preserve primary magmatic textures and have trace element
enriched in Si, Fe, K, Cs, and Rb relative to its basaltic parent patterns suggesting only limited disturbance from expected primary
(Holland et al., 1989; Pan and Stauffer, 2000; Babechuk and Kamber, compositions. Changes in pillow core, pillow rim, and unweathered
2011). The Flin Flon paleosol also exhibits marked Th/U fractionation hyaloclastite compositions are consistent with Neoarchean seawater–
rock interaction/submarine alteration. These processes produced signifi- Burnham, O.M., Schweyer, J., 2004. Trace element analysis of geological samples by ICP-
MS at the Geoscience Laboratories: Revised capabilities due to improvements to
cant percent changes (+20 to +80 enrichments or depletions) in Si, Fe, instrumentation. Summary of Field Work and Other Activities 2004; Ontario Geological
Ca, Na, K, Rb, Sr, Pb and LREE. Least mobile were Zr, Hf, Nb, Ta, Y, Th, Cr, Ni, Survey Open File Report 6145, pp. 54-1–54-20.
Co, Sc, and HREE. Whole-rock δ18O values (+10.4 to +12.7‰) preserve Burnham, O.M., Hechler, J.H., Semenyna, L., Schweyer, J., 2002. Mineralogical controls
on the determination of trace elements following mixed acid dissolution. Summary
a record of alteration at low temperatures. of Field Work and Other Activities 2002; Ontario Geological Survey Open File Re-
Weathered red hyaloclastites present at the base of the weathering port 6100, pp. 36-1–36-12.
profile are rich in silica, contain bundles of randomly oriented hematite Clayton, R.N., Mayeda, T.K., 1963. The use of bromine pentafluoride in the extraction of
oxygen from oxides and silicates for isotopic analysis. Geochimica et Cosmochimica
flakes, and have the highest δ18O values (+16.1 to +17.1‰) of the Acta 27, 43–52.
Schreiber Beach profile. Associated hematite-bearing, weathered red Corfu, F., Muir, T.L., 1989a. The Hemlo-Heron Bay greenstone belt and Hemlo Au-Mo
basalts are very Fe-rich (Fe2O3 = 28–33 wt.%). These features are con- deposit, Superior Province, Ontario, Canada. 1. Sequence of igneous activity determined
by zircon U-Pb geochronology. Chemical Geology 79, 183–200.
sistent with formation at low temperature in an oxygenated environ-
Corfu, F., Muir, T.L., 1989b. The Hemlo-Heron Bay greenstone belt and Hemlo Au-Mo
ment. We interpret the weathered red basalts indicative of a warm, deposit, Superior Province, Ontario, Canada. 2. Timing of metamorphism, alteration
humid Paleoproterozoic continental climate. and Au mineralization from titanite, rutile, and monazite U-Pb geochronology.
The weathered red basalts are overlain by the weathered brown to Chemical Geology 79, 201–223.
Corfu, F., Stott, G.M., 1998. Shebandowan greenstone belt, western Superior Province:
green basalts, but well-preserved soil horizons are absent from the U-Pb ages, tectonic implications, and correlations. Geological Society of America
profile. They may have been eroded, or the profile may represent an Bulletin 110, 1467–1484.
only weakly-developed paleosol. Most major and trace elements, Costa, U.R., Barnett, R.L., Kerrich, R., 1983. The Mattagami Lake Mine Archean
Zn-Cu sulfide deposit, Quebec; hydrothermal coprecipitation of talc and sulfides in a
including LILE, REE, HFSE, and transition metals, were highly mobile sea-floor brine pool; evidence from geochemistry, 18O/16O, and mineral chemistry. Eco-
during weathering and soil formation, displaying percent enrichments nomic Geology and Bulletin of the Society of Economic Geologist 78, 1144–1203.
or depletions of >20 relative to unweathered pillow cores. Like most Cotten, J., Le Dez, A.L., Bau, M., Caroff, M., Maury, R.C., Dulski, P., Fourcade, S., Bohn, M.,
Brousse, R., 1995. Origin of anomalous rare-earth element and yttrium enrichment
of its Precambrian counterparts, the Schreiber Beach profile underwent in subaerially exposed basalts: evidence from French Polynesia. Chemical Geology
alkaline metasomatism, which produced significant percent enrich- 119, 115–138.
ments in K (+280 to +1000), Rb (+390 to +660), and Cs (+1160 Davis, D.W., Lin, S., 2003. Unraveling the geological history of the Hemlo Ar-
chean gold deposit, Superior Province, Canada: a U-Pb geochronological
to +2560) relative to unweathered pillow cores. The origin and timing study. Economic Geology and the Bulletin of the Society of Economic Geol-
of the alkaline metasomatism remains to be resolved. ogists 98, 51–67.
Supplementary data to this article can be found online at http:// Davis, D.W., Beakhouse, G.P., Jackson, S.L., 1998. Part 3: U-Pb zircon and titanite
geochronology. In: Jackson, S.L., Beakhouse, G.P., Davis, D.W. (Eds.), Geological setting
dx.doi.org/10.1016/j.chemgeo.2012.07.018.
of the Hemlo gold deposit: an interim report, Ontario Geological Survey, Open File
Report 5977, pp. 1–10.
Driese, S.G., 2004. Pedogenic translocation of Fe in modern and ancient vertisols and
Acknowledgments implications for interpretations of the Hekpoort paleosol (2.25 Ga). Journal of
Geology 112, 543–560.
Driese, S.G., Jirsa, M.A., Ren, M., Brantley, S.L., Sheldon, N.D., Parker, D., Schmitz, M.,
Two anonymous reviewers are acknowledged for their construc-
2011. Neoarchean paleoweathering of tonalite and metabasalt: implications for
tive comments, which have resulted in significant improvements to reconstructions of 2.69 Ga early terrestrial ecosystems and paleoatmospheric
the paper. This research was supported by NSERC grants to A. Polat chemistry. Precambrian Research 189, 1–17.
Farrow, C.E.G., Mossman, D.J., 1988. Geology of Precambrian paleosols at the base of the
and F. Longstaffe. A. Polat thanks Juan C. Ordóñez-Calderón, Mevlüde
Huronian Supergroup, Elliot Lake, Ontario, Canada. Precambrian Research 42, 107–139.
Polat, Hasan Polat and Alp Polat for their assistance in the field. We Fedo, C.M., Nesbitt, H.W., Young, G.M., 1995. Unraveling the effects of potassium metaso-
thank Sharon Lackie for her assistance with SEM analyses and Kim matism in sedimentary rocks and paleosols, with implications for paleoweathering
R. Law for her assistance with oxygen isotope analyses. This is Labora- conditions and provenance. Geology 23, 921–924.
Feng, R., Kerrich, R., Maas, R., 1993. Geochemical, oxygen, and neodymium isotope
tory for Stable Isotope Science Contribution # 280. compositions of metasediments from the Abitibi greenstone belt and Pontiac
Subprovince, Canada; evidence for ancient crust and Archean terrane juxtaposition.
Geochimica et Cosmochimica Acta 57, 641–658.
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Pillow Basalt On Schreiber Beach

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Chemical Geology 326–327 (2012) 145–173

Contents lists available at SciVerse ScienceDirect

1. Introduction nature of such processes under Precambrian conditions is of special in-

Fig. 4. Sample locations and whole-rock oxygen-isotope compositions.

basalts (soil). Macroscopic evidence supporting subaerial weathering 4. Analytical methods

Rock type Mineral assemblage

SC2007-29 SC2007-30 SC2007-31 SC2007-31Ra SC2007-32 SC2007-33 SC2008-14 SC2008-15 SC2008-15Ra

SiO2 50.6 46.9 47.4 60.9 53.2 47.4 50.7

La/Smcn 0.97 0.99 0.96 0.86 0.92 0.89 0.90

Pillow rims Group 1 Group 2

0.96 0.92 0.83 1.04 1.08 1.60 1.41 1.35 1.54

(continued on next page)

Hyaloclastites Weathered red basalts — red soil

Group 2 Group 3 Group 4

Weathered brown to green basalts ̶ soil

30.7 59.3 60.7 57.2 51.5 57.8 55.7 56.5 60.2

0.99 0.81 0.84 1.13 0.86 1.14 1.28 1.26 0.99

(continued on next page)

Weathered brown to green basalts — soil

Group 2 Group 3 Group 4 Group 5

SC2008-07 SC2008-07Rb SC2008-08 SC2008-17 SC2007-23A SC2008-22 SC2008-02 SC2008-18 SC2008-19

La/Smcn 0.92 0.96 1.26 1.19 1.12 0.99 0.88 0.51

10 10 Weathered red basalts–red soil

6.2. Pillow rims 6.3. Hyaloclastites

Weathered brown to green basalts–soil Group 5

SiO2 −18 −25 +39 +54 −4 −46 +14 +20 +8 +20 +8

ΔC = [(Cas − Cpc)/Cpc) * 100].

Sample/ Pillow core

Group 1 Group 2 SC2008-20

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