AN ABSTRACT OF THE THESIS OF
Paul Steven Walczak for the degree of Master of Science in Oceanography presented on
May 30, 2006.
Title: Submarine Plateau Volcanism and Cretaceous Ocean Anoxic Event 1a:
Geochemical Evidence from Aptian Sedimentary Sections.
Abstract approved:
_____________________________________________________________________
Robert A. Duncan
Marine sediments exceptionally rich in organic carbon, known as black shales,
occur globally but intermittently in well correlated Cretaceous successions. The presence
of black shales indicates that sporadic, ocean-wide interruption of normal respiration of
marine organic matter during oxygen-deficient conditions has occurred. Submarine
volcanism on a massive scale, related to the construction of ocean plateaus, could be
responsible for the abrupt onset and conclusion of these Ocean Anoxic Events (OAEs),
via the oxidation of magmatic effluent, the stimulation of increased primary productivity,
and the resultant respiration of sinking organic matter. These discrete periods of global
ocean anoxia are accompanied by trace metal enrichments that are coincident with
magmatic activity and hydrothermal exchange during plateau construction.
The link between submarine volcanism associated with the emplacement of the
Ontong Java - Manihiki plateau (~122 Ma) and Cretaceous Ocean Anoxic Event 1a is
explored in this study. Two marine sedimentary sections, recovered in cores from Deep
Sea Drilling Program (DSDP) Site 167 (Magellan Rise) and Site 463 (Mid-Pacific
Mountains), were analyzed for a suite of major, minor, and trace elements. Trace element
abundance patterns for these locations were compared to similar data from the CISMON
core (Belluno Basin, Northern Italy) to determine if a relationship existed between the
timing of trace metal anomalies and global biogeochemical events.
To account for the variable effects of terrestrial input, trace element data were
normalized to Zr and major element data were normalized to Al. Distinct,
stratigraphically correlatable peaks could be seen deviating from background levels in the
trace element data from the three sites. These anomalous trace metal intervals are related
to melt-gas partitioning associated with magmatic degassing and hydrothermal activity
resulting from chemical exchange of seawater with cooling plateau rocks. The
stratigraphic coincidence of trace metals with other biogeochemical events is consistent
with the idea that submarine plateau volcanism, on a massive scale, pushed the global
deep ocean into anoxic conditions at discrete intervals of the Cretaceous period.
©Copyright by Paul Steven Walczak
May 30, 2006
All Rights Reserved
Submarine Plateau Volcanism and Cretaceous Ocean Anoxic Event 1a: Geochemical
Evidence from Aptian Sedimentary Sections
by
Paul Steven Walczak
A THESIS
submitted to
Oregon State University
in partial fulfillment of
the requirements for the
degree of
Master of Science
Presented May 30, 2006
Commencement June 2007
Master of Science thesis of Paul Steven Walczak presented on May 30, 2006.
APPROVED:
_____________________________________________________________________
Major Professor, representing Oceanography
_____________________________________________________________________
Dean of the College of Oceanic and Atmospheric Sciences
_____________________________________________________________________
Dean of the Graduate School
I understand that my thesis will become part of the permanent collection of Oregon State
University libraries. My signature below authorizes release of my thesis to any reader
upon request.
_________________________________________________________________
Paul Steven Walczak, Author
vii
ACKNOWLEDGEMENTS
I would like to thank the many people that have made the last several years
possible. Foremost, I would like to thank Bob Duncan, my advisor. His support and
encouragement have been unwavering, and he has always been on the lookout for
opportunities that would interest me and further expand my experiences in the field of
oceanography. Another thank you to Randy Keller and Nick Pisias, I don’t feel like
my education in oceanography would have been complete without the seagoing
experiences that I have had. Thanks also to Gary Klinkhammer and Fred Prahl for
serving on my committee, providing great feedback, and teaching enjoyable courses.
Without to teachings of Andy Ungerer, Bobbi Conard, and John Huard I would have
been very lost in the lab. Additionally, the assistance of Moya and Coreen made my
life not only easier, but also more entertaining. Thanks to Dr. Leon Clarke at the
University of Wales, Bangor for providing me with samples and data.
Further, I would like to thank everyone else who has been a part of my life
during the last couple of years. Thanks to my classmates for all of the help,
encouragement, and good times. Thanks to Chris for helping me keep my priorities in
order. Thanks to Mike, Kurt, Ken, Scott, Garrett, Barney, Aaron, Faron, Wilo, and all
of my other friends for keeping me aware of the big picture. Thanks to my parents,
well, for everything.
I also shouldn’t forget to mention boys up north, for being a constant in my
changing world and for giving me a wave or two. Finally, I would like to thank Alison
for always being there.
viii
Support for this project was provided by the American Chemical Society’s
Petroleum Research Fund. Without it, none of this would have been possible.
ix
TABLE OF CONTENTS
PAGE
Chapter 1: Ocean Plateau Emplacement and Black Shales .......................................... 1
Introduction ............................................................................................................... 1
Background: .............................................................................................................. 5
Large Igneous Provinces ....................................................................................... 5
Ocean Anoxic Events............................................................................................ 8
Hypotheses for Cretaceous Oceanic Anoxia....................................................... 10
Sedimentary Signatures....................................................................................... 13
Scavenging .......................................................................................................... 19
Diagenesis ........................................................................................................... 21
Cretaceous Metal Anomalies .............................................................................. 22
This Study ............................................................................................................... 23
Chapter 2: Trace Element Abundances in Deep Sea Drilling Project Sites 167 and
463: Their Relationship to the Ontong Java-Manihiki Plateau Emplacement and
Ocean Anoxic Event 1a............................................................................................... 24
Methods................................................................................................................... 24
The Ontong Java Plateau......................................................................................... 24
The Manihiki Plateau .............................................................................................. 27
The Magellan Rise .................................................................................................. 28
Sample Acquisition, Site 167.................................................................................. 29
The Mid-Pacific Mountains .................................................................................... 32
Sample Acquisition, Site 463.................................................................................. 33
Sample Processing .................................................................................................. 35
Crushing .............................................................................................................. 35
Powdering ........................................................................................................... 36
Microwave Dissolution ....................................................................................... 36
x
TABLE OF CONTENTS (CONTINUED)
PAGE
Microwave Evaporation ...................................................................................... 37
Microwave Cleaning ........................................................................................... 38
Sample Analyses ..................................................................................................... 38
Trace and Minor Elements .................................................................................. 38
Major Elements ................................................................................................... 44
Results ..................................................................................................................... 45
Site 167 ............................................................................................................... 45
Site 463 ............................................................................................................... 46
Discussion ............................................................................................................... 49
Degassing, Hydrothermalism, and Trace Metals ................................................ 58
Residence Time, Cretaceous Circulation, and Location ..................................... 64
Chapter 3. Summary, Conclusions, and Future Studies.............................................. 70
Literature…………………………………………………………………………...…73
Appendix 1. Trace Metal Patterns in Marine Sediments……………………………..80
Appendix 2. Deep Sea Drilling Project Site 167 and Site 463 normalized element
abundances……………………………………………………………………………92
xi
LIST OF FIGURES
FIGURE
PAGE
1. The timing of ocean plateau volcanic activity correlates with Cretaceous
biostratigraphic boundaries and plankton evolutionary events, timing of oceanic
plateaus (LIPs), seawater 87Sr/86Sr and δ 13C variations, and changes in sea level . 3
2. A thermally buoyant plume head approaches the base of the lithosphere, broadens
out in a roughly flatttened disk shape, and undergoes adiabatic decompression
producing melt in the area covered by the mushroomed-out plume head. .............. 7
3. A proposed cycling system developed by Erba (2004) to explain Cretaceous
sedimentary biological and geological processes .................................................. 14
4. Schematic from Snow et al. (2005), demonstrates the relationship between near
and far-field elements found in the sedimentary record and the location of the
LIP eruption ........................................................................................................... 16
5. A chart developed to analyze the effects of volatility and mean ocean residence
time of an element in seawater............................................................................... 18
6. Location of global large igneous provinces in their modern day locations ............. 25
7. Locations of DSDP Sites 167 and 463 ( red stars) in the modern day..................... 30
8. δ13C for Site 167....................................................................................................... 31
9. δ13C for Site 463....................................................................................................... 34
10. Minor (Sc, Cu, and Pb) element data from DSDP Site 167................................... 47
11. Minor (Sc, Cu, and Pb) element data from DSDP Site 463................................... 48
12. Trace elements cycle into and out of seawater in various ways ............................ 53
13. Figure is a plot comparing representative elements from the three sites used in
this study, DSDP Sites 167 and 463 as well as CISMON ..................................... 56
14. Volatility versus residence time for DSDP Site 167’s lower (920 mbsf) peak...... 60
15. Volatility versus residence time for DSDP Site 167’s upper (890 mbsf) peak...... 62
16. Volatility versus residence time for DSDP Site 463’s lower (620 mbsf) peak...... 63
17. Volatility versus residence time for DSDP Site 463’s upper (610 mbsf) peak...... 65
18. The Ontong Java-Manihiki plateaus, Mid-Pacific Mountains, Magellan Rise,
and CISMON (in modern-day Italy) shown in their paleo-locations on a
schematic diagram of Cretaceous (~100 Ma) ocean circulation ............................ 66
19. Volatility versus residence time for the CISMON, North Italy “M0” Interval...... 69
xii
LIST OF TABLES
TABLE
PAGE
Table 1. Means and standard deviations for Minor and Trace Element Data…….…40
Table 2. Means and standard deviations for Major Element Data…..………………42
xiii
LIST OF APPENDIX FIGURES
FIGURE
PAGE
A1. This cartoon demonstrates the path that many elements take through seawater…83
A2. Seawater flux and planktonic composition………………………………………88
A3. Hydrothermal and degassing fluxes……………………………………………...89
A4. Trace element abundance anomalies found in Deep Sea Drilling Project Site
167 during this study………………………………………………………….…..90
A5. Trace element abundance anomalies found in Deep Sea Drilling Project Site
463 during this study………………………………………………………...……91
1
Submarine Plateau Volcanism and Cretaceous Ocean Anoxic Event 1a:
Geochemical Evidence from Aptian Sedimentary Sections
Chapter 1: Ocean Plateau Emplacement and Black Shales
Introduction
The early Aptian stage of the Cretaceous period is recognized for its extreme
environmental conditions. The Cretaceous, lasting from 144 to 65 Ma (Harland et al.
1990) time scale, was markedly different from the world we know today. During this
time, CO2 levels were between 3 and 12 times greater than pre-industrial levels,
resulting in temperatures on land and in the ocean that were up to 10-12 ˚C warmer
than today (Berner, 1994). This period was also characterized by a lack of polar ice
caps, a reduced temperature gradient between the equator and the poles, and higher sea
levels due the combination of a lack of glacial ice and shallower (younger) seafloor
(Schlanger et al., 1981). The Cretaceous was a period of exceptional volcanism: the
dramatic increase in seafloor spreading rates and a number of rapidly-erupted large
igneous provinces (LIPs) on land and in all the ocean basins were remarkable.
Eruption of a mantle “superplume” in the Pacific basin increased oceanic crustal
production by approximately 50-100% at this time (Larson 1991 a,b; Duncan and
Richards 1991; Coffin and Eldholm 1994).
For oceanographers, one of the most intriguing features of this period was
discovered during the early years of the Deep Sea Drilling Program (DSDP). At this
time sediments exceptionally rich in organic carbon, known as black shales, and
accompanied by distinct positive δ13C isotopic excursions were recovered from
2
Cretaceous successions in the Atlantic, Indian and Pacific Oceans (Erba, 2004). These
events were soon discovered to be one of the most fascinating features of the
Cretaceous period because intervals of finely laminated, organic-rich sediments
indicated that sporadic, ocean-wide interruption of normal sedimentary respiration
during oxygen-deficient conditions had occurred (Schlanger and Jenkyns, 1976).
These periods, termed Oceanic Anoxic Events (OAEs), and the geological and
climatic processes responsible for their occurrence, have received much attention
during the last three decades but satisfactory explanation has remained elusive.
Recent advances in isotopic measurements as well as plankton speciation and
extinction suggest that other major events seem to be correlated with the OAEs.
Leckie et al. (2002) produced an overview of Cretaceous OAEs in which he correlated
their occurrence with sea level changes, biostratigraphy, seawater 87Sr/86Sr ratios, δ13C
curves, and major volcanic events evident in the formation of large igneous provinces
(Figure 1, Leckie et al., 2002).
It can be seen that both global anoxic events (OAE1a and OAE2) are
accompanied by distinct positive δ13C excursions in carbonate or organic carbon
preserved in marine sediments. Such departures from the long-term compositions are
attributed to the accelerated burial of marine (12C-enriched) organic matter during
episodes of enhanced productivity (Erba, 2004). These OAEs are also marked by a
major decrease in the 87Sr/86Sr record found in carbonates. Volcanism is known to be a
source of unradiogenic Sr, and given the long residence time of Sr in the ocean, abrupt
inputs of Sr will be broadened to intervals of at least 3 Ma in duration. Erba (2004)
3
Figure 1. The timing of ocean plateau volcanic activity correlates with Cretaceous
biostratigraphic boundaries and plankton evolutionary events, timing of oceanic
plateaus (LIPs), seawater 87Sr/86Sr and δ 13C variations, and changes in sea level (from
Leckie et al., 2002). Note the sudden decrease in the 87Sr/86Sr ratio found just after the
Ontong Java-Manihiki plateau formation (~122 Ma) and Caribbean plateau formation
(~93 Ma).
4
attribute this decrease to the input of hydrothermal Sr from submarine volcanism
during the emplacement of the Ontong-Java and Manihiki plateaus (OAE1a).
However, the fundamental relationship between ocean plateau volcanism,
species extinction, and global ocean anoxia remains unclear and the temporal
coincidence of these factors does not necessarily imply that the phenomena are related.
Many theories have been offered to explain the relationship between trends seen and
the deposition of black shales. Perhaps the most intriguing of these hypotheses is that
of Sinton and Duncan (1997) who first proposed that metal rich eruptive “event
plumes” resulting from the emplacement of individual, massive lava flows during the
construction of ocean plateaus may have stimulated black shale deposition.
Snow (2003) and Snow et al. (2005) have expanded upon Sinton and Duncan’s
(1997) hypothesis to better understand the specific links between event plumes and
global ocean anoxia that occurred at the Cenomanian-Turonain boundary (~93 Ma),
which is correlated with Ocean Anoxic Event 2 (OAE2). Snow et al. (2005) measured
the distribution of major, minor, and trace element abundances from pelagic carbonate
and black shale sequences from Pueblo, Colorado, along with four other marine
sedimentary sections from around the world. Anomalies in the metal abundances were
then compared to the types of metal signatures expected from both normal (chronic)
hydrothermal activity and eruptive “event plume” activity for evidence of either.
Finally the stratigraphic position of these metal anomalies was used to determine the
timing of the plateau emplacement with respect to the onset of anoxia, as determined
5
by the δ13C profiles. Snow’s research suggests that the presence and stratigraphic
location of metal anomalies associated with the formation of the Caribbean ocean
plateau could be directly related to OAE2.
The purpose of this study is to determine if the same relationships seen by
Snow et al. (2005) exist in other Cretaceous black shale sequences. In order to realize
this goal a selection of samples from marine sedimentary sections that include Ocean
Anoxic Event 1a (early Aptian) was collected and analyzed for a wide range of major,
minor and trace elements. Elemental abundance anomalies in these sediment records
were then subjected to the same comparisons used by Snow et al. (2005) that seemed
to support the hypothesis of Sinton and Duncan’s (1997).
Background:
Large Igneous Provinces
Large igneous provinces (LIPs) are massive emplacements of basaltic lava
flows, dikes, and sills that formed during very brief eruptive periods (a few million
years) (Coffin and Eldholm, 1994). Continental flood basalts, oceanic plateaus, and
volcanically rifted margins all can form through LIP activity. LIPs apparently
originate by processes unrelated to steady-state plate tectonics (volcanic arcs, midocean ridges), but are instead thought to be erupted at the beginning stages of hotspot
activity (Richards et al., 1989; Campbell and Griffiths, 1989). As such, LIPs are
thought to begin as mantle plumes ascending by thermal buoyancy through the
overlying mantle (Kerr, 2003). Numerical modeling and tank experiments suggest that
when the plume approaches the base of the lithosphere, it broadens out in a roughly
6
flattened disk shape and undergoes adiabatic decompression producing melt in the
area covered by the mushroomed-out plume head (Kerr, 2003). The temperature of the
plume and thickness of the overlying lithosphere dictate the amount of melt produced;
that is, the extent to which upwelling mantle may rise and decompress. For this reason
oceanic plumes, which rise to shallower depths beneath thinner lithosphere, produce
greater amounts of melt than their continental counterparts (Kerr, 2003). A schematic
of LIP formation from Leckie et al., 2002 is shown as Figure 2.
The Cretaceous period includes a number of oceanic plateau LIP events,
several of which appear to be correlated with a distinct decrease in the 87Sr/86Sr record
(Wilson et al., 1998). Seawater 87Sr/86Sr values record the balance between strontium
received in seawater via fluxes of hydrothermal activity (87Sr/86Sr ~0.704), weathering
of old sialic continental rocks (87Sr/86Sr ~0.720), and the weathering of marine
carbonate rocks (87Sr/86Sr ~0.708) (Faure, 1986). As volcanism is a significant source
of unradiogenic strontium it seems that the distinct decrease in seawater 87Sr/86Sr is
due to an increase in submarine volcanic activity of some sort. Moreover, the presence
of dramatically (up to 100 times background) increased concentration of trace metals
found in sediments deposited at this time has been attributed to the enhanced seafloor
7
Figure 2. A thermally buoyant plume head approaches the base of the lithosphere,
broadens out in a roughly flatttened disk shape, and undergoes adiabatic
decompression producing melt in the area covered by the mushroomed-out plume
head. The temperature of the plume and the thickness of the overlying lithosphere
dictate the amount of melt produced, for this reason oceanic plumes produce greater
amounts of melt than their continental counterparts. (After Coffin and Eldholm, 1994).
8
spreading rates (Orth et al., 1993). These metal anomalies have also been shown to
coincide with species extinctions in ammonites and forams as well as ocean-wide
anoxic events (OAEs) (Erba, 2004). Due to the close stratigraphic relationships
between these events, considerable effort has been devoted to determining what the
global responses to increased volcanism would be, as well as what the timing of the
oceanographic, atmospheric, and biotic reactions would be.
Studies of continental flood basalts show that they were formed by the rapid
eruption of massive lava flows, with individual flows amounting to thousands of cubic
kilometers in volume. Each separate flow may have erupted over a period of weeks
(Ho and Cashman, 1997). In addition, Swanson et al. (1975) demonstrated that a
single flow could be as large as 1,500 cubic kilometers. As lavas that formed oceanic
plateaus erupted through relatively thin lithosphere compared to continental flood
basalts, their melt proportions could have been greater due to upwelling of mantle to
shallower depths and greater decompression. Thus, over time scales of 100,000 to
1,000,000 years, the magmatic production of crust at oceanic LIPs is thought to
exceed that of mid-ocean ridge spreading centers (divergent boundaries) (Duncan and
Richards, 1991, Larson, 1991a, b).
Ocean Anoxic Events
While the concept that global anoxia in the deep ocean is responsible for the
exceptional preservation of organic carbon during the Cretaceous is widely accepted
(Schlanger and Jenkyns, 1976), there is still considerable debate as to the process
forcing the ocean into such a condition. Two broad processes have been proposed for
9
the formation of black shales during the Cretaceous time period: markedly increased
productivity and enhanced preservation (Schlanger and Jenkyns, 1976). In an effort to
better understand the Cretaceous events, it is helpful to look for modern analogs.
Anoxic events in the Cretaceous ocean are notable for their excellent preservation of
organic material in the sediment record, this is generally attributed to a complete lack
of oxygen in the seawater - clearly this is not the case in today’s ocean. In fact,
modern-day Earth has few areas of anoxia, and these are located in regions that exhibit
either restricted circulation (like the Black Sea) or extremely high primary
productivity (like the Santa Barbara Basin) (Brumsack, 1989).
Formation of anoxic water occurs in the Black Sea because the circulation of
oxygen supplying waters is restricted due to the presence of a sill at less than 50
meters water depth at the outlet to the Mediterranean Sea. Oxygen initially becomes
depleted in the deep waters due to the settling and decomposition of organic matter.
Next, hydrogen sulfide diffusing from the sediments consumes the remaining oxygen,
thus an anoxic water column is formed (Brumsack, 1989). The Santa Barbara Basin
becomes anoxic in a slightly different manner. Here a basin with somewhat restricted
circulation receives input water from the oceanic oxygen minimum zone (OMZ) in
addition to a high organic flux from the coastal system; decomposition of the organic
matter then depletes the available oxygen (Cannariato et al., 1999).
Cretaceous ocean anoxic events differ from these modern cases due to their
incredible scale. Black shale sequences are found on oceanic plateaus, in ocean basins,
on continental margins, and in shallow and shelf seas. The global extent of these
10
conditions during this time period suggests that they were not formed by means of
restricted circulation and/or decomposition, as these are the result of the local
environment. Instead, it seems indisputable that some fundamental change in ocean
circulation and/or the production and preservation of organic material occurred
(Sarmiento et al., 1988).
Hypotheses for Cretaceous Oceanic Anoxia
As mentioned above, two general methods have been proposed to explain the
formation of these organic-rich shale sequences. Schlanger and Jenkyns (1976)
suggested that the increased sea level during this time increased the area of shallow
banks and inland seas, thus increasing the area receiving large terrestrial nutrient
influxes. This “organic overloading”, in turn, spurred primary productivity which
would have then generated an increase in the depth range and perhaps intensity of the
oxygen minimum zone (OMZ). The “enhanced preservation” model is based on the
principle that diminishing oxygen contents have less capacity to oxidize organic
detrital material, in order for this concept to be realistic a process must be shown to
exist that will deplete the bottom water of oxygen (Schlanger and Jenkyns, 1976). Two
possible environmental conditions have been suggested as possible stimuli for
Cretaceous ocean stagnation. Schlanger and Jenkyns (1976) suggested that increased
global temperatures and the reduction of the poleward temperature gradient during this
time may have reduced the supply of oxygenated bottom water to the oceans.
Saltzman and Barron (1982) suggest that bottom waters of the time reached as high as
15° C, more than 10° C warmer than today. The solubility of oxygen decreases
11
considerably as temperatures increase, so Cretaceous deep ocean waters probably
contained significantly lower dissolved oxygen concentrations than the present.
The scenarios of “organic overloading” and “enhanced preservation” do not,
however, satisfactorily explain all of the facets surrounding global anoxic periods.
Most glaringly, the necessary variables for organic overloading and enhanced
preservation were present throughout much of the Cretaceous era, but black shale
sequences are present only in discrete, short intervals (Herbin et al., 1986). The very
abrupt onset and conclusion of these events suggests that some other intermittent
means of forcing existed, and that it perhaps pressed an already dysoxic ocean towards
abrupt periods of anoxia.
Sinton and Duncan (1997) examined the impacts of catastrophic submarine
volcanism and postulated that the creation of oceanic plateaus (like the Caribbean
plateau whose first pulse of formation occurred ~93 Ma), directly contributed to the
drawdown in seawater O2. They hypothesized that this decrease was due to the
oxidation of reduced metals in hydrothermal effluent “event plumes” and the
stimulation of primary productivity in the surface waters. The most compelling
evidence for this connection is the dramatically (up to 100 times background)
increased concentration of trace metals found in sediments of this time (Orth et al.,
1993; Snow et al., 2005). These metal anomalies coincide with species extinctions in
ammonites and forams (Erba, 2004). In addition, this time frame also shows a distinct
decrease in the 87Sr/86Sr marine carbonate record (Wilson et al., 1998). As ocean floor
volcanism is a significant source of unradiogenic strontium it has been proposed that
12
this distinct decrease is due to an increase in hydrothermal inputs. Sinton and Duncan
(1997) suggest that the short interval of this drop can be explained only by the
emplacement of oceanic plateaus via large igneous provinces. A similar drop could
possibly develop due to increased spreading rates, but in this scenario Sr levels would
then remain at a decreased value.
As oceanic plateaus today are very large, thick, buried under sediments, and
located mostly in submarine environments they are difficult to study. Current studies
are subject to analytical uncertainties ( ≥ 1 Ma) for the existing radiometric ages of the
plateau rocks and the difficulty of directly observing the volcanic stratigraphy.
Consequently, researchers have not yet resolved a precise eruptive history regarding
flow volumes, rates, and duration (Sinton and Duncan, 1997). Instead, Sinton and
Duncan (1997) relied on studies of continental flood basalt provinces as analogies, as
oceanic plateaus are generally regarded as the submarine equivalent of the continental
provinces due to their similar sizes, eruptive time frames, basaltic compositions, and a
shared relation to hotspots. Sinton and Duncan (1997) used a hypothetical maximum
lava flow volume of 10,000 cubic kilometers. Using this volume and modern
hydrothermal compositions Sinton and Duncan (1997) showed that 7.92 x 1015 moles
of O2 would be consumed if all of the material in the vent effluent were completely
oxidized. This is approximately six percent of the total dissolved oxygen in the
modern ocean beneath the mixed layer. Due to its elevated water temperatures (and
resultant lower dissolved oxygen content), the Cretaceous ocean would be even more
affected than the modern ocean. Further calculations illustrated that if five percent of
13
the hydrothermal Fe reached the surface (warm hydrothermal fluids move upwards) of
a high-nitrate, low-chlorophyll zone the amount of organic carbon produced would be
enough to consume all of the seawater O2 and deposit organic-rich sediments on the
seafloor (Sinton and Duncan, 1997).
Erba (2004) suggests that global warming induced by volcanically elevated
CO2 levels would also trigger the melting of gas hydrates. The methane released in
this scenario would further consume oxygen as it converted to carbon dioxide.
Increased carbon dioxide levels in the atmosphere lower the pH of precipitation and
contribute to increased continental weathering and nutrient flux through rivers, and
increased coastal productivity. This scenario, while exhibiting that a small fraction of
some limiting nutrient could produce a significant increase in organic carbon, is an
extreme case and it is quite likely that phytoplankton production would be limited by
some other biologically necessary nutrient before blooming to this extent (Coale et al.,
1996). A schematic diagram illustrating an overview of the above processes is shown
below, in Figure 3.
Sedimentary Signatures
Metal signatures found in sediments are the result of a complex series of
events. Metals enter the seawater either carried by rivers in terrestrial runoff, as dust
blown from continental weathering or volcanic events, and from submarine processes
such as hydrothermal vents and submarine volcanic events (Segar, 1998). These
14
Figure 3. A proposed cycling system developed by Erba (2004) to explain Cretaceous
sedimentary biological and geological processes. As volcanism increased CO2 levels,
global warming would be induced. Additionally, increased atmospheric CO2 would
lower the pH of rainwater, increasing continental weathering. This, in turn, would
have elevated nutrient flux through rivers and resulted in increased coastal
productivity.
15
metals can be transported either in particles or as dissolved ions. Particles are
deposited on the ocean floor as sediments while dissolved ions eventually are
precipitated and reach the sediments as organic detritus (having been used in
biological process), or through a scavenging reaction (where the ions have an affinity
for some other particle or substance and form a larger particle which then settles)
(Pilson, 1998). It has been known for some time that hydrothermal fluxes of chemical
elements to and from the oceans occur as cold seawater circulates through the highly
permeable parts of the crust all along the mid-ocean ridge system and its flanks (Segar,
1998). As the water passes through the crust in these high temperature areas a series of
reactions occurs, depleting this fluid of some elements while enriching it with others.
The composition of these fluids is thus dominated by solubility-driven exchange
between hot water and solidified rock (Rubin, 1997). This fluid then leaves the crust
as a high temperature hydrothermal effluent, taking with it heat and a range of
elements dissolved from high temperature rock. The hot, buoyant vent water rises up
above the ridge, entraining surrounding seawater as it rises to a level of neutral
buoyancy. Currents move this warm plume of water away from the ridge and it mixes
with and finally becomes indistinguishable from the surrounding water. However, a
sedimentary signature is left behind consisting of oxides of the more insoluble
elements (e.g., Fe, Mn) which have short residence times.
Rubin (1997) has described the effects of the mass transfer of chemical
elements to seawater occurring during underwater volcanic eruptions taking place both
along the mid-ocean ridge system and at volcanically active seamounts. The magmatic
16
Figure 4. Schematic from Snow et al. (2005), demonstrates the relationship between
near and far-field elements found in the sedimentary record and the location of the
LIP eruption. The thermally buoyant megaplume rises to the surface caring a load of
trace metals derived from both magmatic degassing and hydrothermal activity, these
trace metals are subsequently fractionated out of the water column depending on their
reactivity. More reactive elements (with shorter residence times) are termed “near
field” elements, while elements more reactive elements are termed “far field”
elements.
17
fluids that are associated with these underwater eruptions, derived from outgassing,
are different in composition from their hydrothermal counterparts, in this case
composition is dominated by volatility (Rubin, 1997). Due the estimated size of
individual eruptive episodes during ocean plateau formation, these magmatic
degassing events can have a much more pronounced thermal impact on the ocean than
that of typical spreading ridge generated hydrothermal vent fluids. In the modern
ocean, hydrothermal megaplumes rising 1000 meters above spreading ridges are
known (Vogt, 1989). Vogt (1989) calculated that eruptions of 15 km3 or more of
magma onto the ocean floor would release enough heat to overcome the oceans
stratification and drive a buoyant plume to the surface. Estimated volumes for single
flows are one to two orders of magnitude larger. Considering also that ocean plateaus
build up well above the ocean floor to shallow depths, it is certain that degassed
magmatic fluids from these events had enough buoyancy to rise to the surface. Plumes
would ultimately bring large amounts of metal-rich magmatic fluid to the surface,
these substances would then undergo biological and chemical reactions, eventually
ending up in the sediment record spread out in a manner dictated by their individual
reactivities. A schematic diagram illustrating this process is shown in Figure 4.
As mentioned above, the abundance patterns of elements released to seawater
hydrothermal fluids is different from that of degassed magmatic fluids. Rubin (1997)
has estimated the general enrichment patterns associated with each group. He
18
Figure 5. A chart developed to analyze the effects of volatility and mean ocean
residence time of an element in seawater (after Rubin, 1997). This diagram is useful in
determining the sources of elements found in pelagic sedimentary signatures.
Hydrothermal waters would be enriched in Sc, Mn, Co, Yb, Cr, Ni, Ba, V, Li, and Sr
while magmatic fluids would have enhanced levels of Pb, In, Zn, Cu, Tl, Ag, Au, Cd,
Bi, Se, Au, and Re.
19
propose that the general enrichment pattern for steady-state hydrothermal events
would be:
alkaline earths & alkali metals Æ transition metals Æ rare earths and actinides Æ main group elements
Degassed magmatic fluids are nearly the reverse of this; their enrichment pattern
would be:
main group elements Æ transition metals Æ alkaline earths and alkali metals Æ rare earths and
actinides
Hydrothermal (water-rock reactions) waters would be enriched in Al, Zn, Fe, Mn, Au,
and Ir while thermally buoyant plumes rich in magmatic fluids would have enhanced
levels of Mo, W, Hg, Bi, Se, Cd, and As (Rubin, 1997). A diagrammatic
representation of this is shown in Figure 5.
The different chemical signatures could thus be used to discriminate
sedimentary metal enrichments generated by the two processes. However, in the case
of ocean plateau eruptive events, one would expect to see a mixture of the two: the
initial magmatic degassing signature, followed by the hydrothermal signature as new
lava flows and subsurface intrusions are infiltrated by seawater. This information
could be used to help infer if the emplacement of the Ontong Java-Manihiki Plateau
had effects that were global in nature.
Scavenging
The low dissolved trace metal content in the modern ocean cannot be attributed
to lack of supply through geologic time, therefore researchers have suggested that
these metals are subject to a rapid and efficient removal process, dubbed scavenging
20
(Balistrieri et al., 1981). Scavenging, or the absorption of chemical elements onto
solid surfaces, has been recognized in recent decades as an important control on the
distribution of these elements in seawater and sediments (Balistrieri et al., 1981,
Bruland, 1983). An analysis of sinking particulate matter in the deep ocean suggests
that the adsorptive properties are controlled by organic coatings on detrital material.
As biological particles fall through the water column, the adsorption of metal ions or
ionic complexes on their surfaces is a very effective means of removing trace elements
from the seawater solution (Brown et al., 1994). Adsorption occurs because charges on
the metal ions or ionic complexes are attracted to suitable bonding sites on particle
surfaces. Scavenging occurs as particles (with their absorbed trace metal loads)
coalesce into larger conglomerates and fall out of the water column and to the seafloor
sediment (Brown et al., 1994). Scavenging is a remarkably efficient means of
transferring elements from the seawater to the sediment, and will collect metals that
are not biologically active as well. In the open ocean this detrital material is primarily
generated by phytoplankton, or as waste products of the zooplankton that prey upon
them (Bruland, 1983). Balistrieri et al. (1981) found that the residence times, with
respect to scavenging, depend on three factors: the competing complexing abilities of
the marine particle groups and the solution ligands, in addition to the flux of
particulate matter in the water column. We therefore assume that scavenging was an
important factor in removing trace metals from the Cretaceous ocean.
21
Diagenesis
Diagenesis is the physical, chemical, or biological alteration of sediments into
sedimentary rock at low temperatures at the ocean floor which can result in changes to
the original mineralogy and texture (Pirie, 2006). The oxidation of organic material
during sedimentary diagenesis has been demonstrated to change the distribution of
certain metals in sedimentary pore waters (Froelich et al., 1979). Some of these metals
can become concentrated as a peak within the sediments, while others can diffuse
across the sediment-water interface and back into the water column (Froelich et al.
1979; Nameroff et al., 2002). Different metals have different sensitivities to redox
changes, meaning that different enrichment patterns will occur depending on the
oxygen content of their depositional environments (Nameroff et al., 2002). Calvert and
Pedersen (1993) demonstrated that some minor and trace elements (Cr, Mo, Re, U, V)
become enriched in ocean bottom sediments during periods of bottom water anoxia,
while other elements (I, Mn) indicate that the sediments accumulated during an
oxygenated stage (Calvert and Pedersen, 1993).
While these elements are shown to accumulate in the upper sediment during
anoxic periods, one can only wonder if the anoxic diagenetic processes can generate
trace element rich bands. However, Algeo and Maynard (2004) state that there is
“little evidence for translocation of trace elements under continuously anoxic
conditions” like those that prevail during the deposition of black shales. As a caveat
they add that remobilization of certain trace elements is possible, but only at a
relatively fine scale (<1cm).
22
Cretaceous Metal Anomalies
Metal abundance peaks immediately below the C/T boundary were described
by Orth et al. (1993). This study reported finding two metal excursions immediately
preceding this boundary in a number of sites from around the world, these anomalies
seem to correlate well with the nannofossil, foraminifera, and radiolaria speciation
events of this time period in addition to excursions in the Sr isotope and 13C records
(Figure 1).
Specifically, the Orth et al. (1993) study discovered enhanced levels of Au, Co,
Cr, Mn, Ni, Pt, Sc, Ti, and V in the same stratigraphic interval as the “Bonarelli
Level” of Italy (Arthur and Premoli-Silva, 1982) and “Black Band” of England (Leary
et al., 1989). This layer has been attributed to Ocean Anoxic Event 2.
Orth et al. (1993) concluded that the metal anomalies discovered in their study
were the result of elevated mid-ocean ridge or hotspot activity. As stated earlier, this
conclusion does not satisfactorily explain the short, discrete nature of these excursions
but the hypothesis of Sinton and Duncan (1997) does. In this particular instance,
metals released during the emplacement of the Caribbean plateau formed in discrete
intervals in the sediment column due to the isolated yet substantial metal loading
associated with event plumes. This combined evidence led Snow (2003) to choose
Cretaceous Ocean Anoxic Event 2, at the Cenomanian-Turonian Boundary, as an
appropriate interval to study in order to evaluate Sinton and Duncan’s (1997) proposed
link between ocean plateau emplacement and ocean anoxic events. Snow determined
the distribution of trace, minor, and major element abundances for a sedimentary
section (Rock Canyon, Colorado) spanning Cretaceous OAE2. By demonstrating that
23
the stratigraphic position of an interval of metal anomalies matched with other events
assocated with OAE2, this studies findings indicated that metal anomalies did exist in
the sedimentary record at the time of OAE2, indicating that similar anomalies should
exist at other OAE events.
This Study
Snow’s (2003) work provided evidence supporting the hypothesis that metalenriched magmatic “event plumes” generated during the emplacement of the
Caribbean plateau pushed the ocean into anoxia, a principal component leading to the
formation of Ocean Anoxic Event 2 and ultimately the creation of black shales that are
seen around the world today. This study’s intention is to provide additional testing of
Sinton and Duncan’s (1997) hypothesis via an examination of the Ocean Anoxic
Event 1a (OAE1a), thus providing evidence that this process was also the causative
agent behind global ocean anoxia at other times during the Cretaceous. The following
chapters will discuss major, minor, and trace elemental abundances found during the
Aptian interval of sediment cores collected from the western mid-Pacific mountains.
These cores, from the Deep Sea Drilling Project’s sites 167 and 463 will provide two
points of comparison for timing and near and far field effects of Ontong-Java plateau
emplacement on local oceanic biogeochemistry. Additionally, data from the Cismon
core (Belluno Basin, northern Italy) will be included in order to see the far field effects
of Ontong Java - Manihiki plateau formation.
24
Chapter 2: Trace Element Abundances in Deep Sea Drilling Project Sites 167
and 463: Their Relationship to the Ontong Java-Manihiki Plateau Emplacement
and Ocean Anoxic Event 1a.
Methods
In recent years it has become increasingly clear that the emplacement of
several oceanic large igneous provinces is, at the very least, coincident with
environmental effects on a global scale (Kerr, 2003). Snow (2003) studied the pattern
and distribution of trace metal abundances in marine sediments deposited around the
Cenomanian-Turonian boundary to establish whether the emplacement of the
Caribbean plateau was related to the creation of Ocean Anoxic Event 2, as proposed
by Sinton and Duncan (1997). This study strongly indicated that metal-rich effluents
from submarine volcanism promoted anoxia. However, supporting evidence from
another Ocean Anoxic Event would further strengthen the validity of this connection.
In order to provide this evidence, this chapter reports the results of a study of
Cretaceous Ocean Anoxic Event 1a, an event that is associated with the largest of the
Cretaceous plateaus.
The Ontong Java Plateau
The Ontong Java Plateau is the largest of the oceanic plateaus formed during
the Cretaceous, covering an area of approximately 1.9 x 106 km2 and having an
25
Figure 6. Location of global large igneous provinces in their modern day locations.
After Coffin and Eldholm (1994), who listed the full names for the abbreviations. Note
the Ontong Java and Manihiki plateaus circled in black (solid) and Caribbean plateau
circled in blue (dashed).
26
estimated total volume of 4.4 x 107 km3, with an average thickness of 32 km (Kerr,
2003). When it formed, the Ontong Java region was located at approximately 43°S
(Fitton et al., 2004). Its current location spans the equator in the western part of the
Pacific basin (see Figure 7). As the Ontong Java Plateau (OJP) collided with the
Solomon arc, the southern margin of the plateau was uplifted, creating on land
exposures of basaltic basement in the Solomon Islands (Fitton et al., 2004). Studies of
these islands reveal a repetitive succession of Early Cretaceous tholeiitic pillow basalt,
sheet flows, and sills (Petterson, 2004; Fitton et al., 2004). Additionally, rare and thin
interbeds of laminated pelagic chert or limestone suggest high eruption frequency and
emplacement into water deeper than 1000 meters.
A precise timing and duration of Ontong Java Plateau magmatism has not been
established due to the difficulty of performing 40Ar/39Ar dating on the low potassium
plateau basalts (Fitton et al., 2004). Studies by Mahoney et al. (1993) and Tejada et al.
(1996, 2002) using 40Ar/39Ar data agree that there was a major episode of plateau
magmatism ~122 Ma and another, smaller episode ~90 Ma. Ages determined using
biostratigraphic data based on forams and nannofossils interbedded in the lava flows
suggest that magmatism occurred from the early to late Aptain, a period corresponding
to ~122-112 Ma on the Harland et al. (1990) time scale.
Alteration of Ontong Java Plateau basalts has occurred. Evidence exists for the
low temperature alteration of these rocks through contact with seawater, and alteration
ranges from slight to complete (Fitton et al., 2004). The replacement of olivine by
clays is the most common, and initial type of alteration seen in the basalts. Later stages
27
of alteration occurred as cold, oxidizing seawater caused limited replacement of
primary phases and mesostasis by smectite and iron oxyhydroxides (Fitton et al.,
2004). These types of alteration have been shown to occur in the same manner as that
of ridge basalts (Fitton et al., 2004). No evidence was recovered to indicate that hightemperature alteration occurred in any of the recovered basalts.
The Manihiki Plateau
Basalts cored at the Manihiki Plateau have been compared to those recovered
from the Ontong Java Plateau. They share many common characteristics including
their vesicular nature, the fact that they contain phyric plagioclase, and that they share
probable oceanic tholeiitic composition (Schlanger et al., 1973). Ontong Java basalts
contain somewhat more altered olivine phenocrysts, but appear identical in texture, in
the presence of small plagioclase phenocrysts, and in the suspected presence of two
pyroxenes in the groundmass (Schlanger et al., 1973). Additionally, based on
radiometric, magnetostratigraphic, and biostratigraphic dating of sediment and
basement, Tarduno et al. (1991) placed the age of the Manihiki Plateau at ~122 Ma.
Finally, radiometric dating and isotopic geochemistry done by Mahoney et al (1993)
identified two common lava series (the Singgalo and Kwaimbaita). This combined
evidence suggests that the Manihinki Plateau may be an additional manifestation of
the Ontong Java large igneous province, if this were the case this LIP would have
affected ~1% of the surface of the Earth (Coffin and Eldholm, 1994).
28
The Magellan Rise
Paleontological evidence has indicated that the oldest sediments found on the
crest of the Magellan Rise are about 135 million years old, making them some of the
oldest material cored in the Pacific. As a consequence this location includes a
sedimentary record that predates the formation of the Ontong Java Plateau (Winterer
et al., 1973). Additionally, the summit of the Rise is above the present calcium
carbonate compensation depth (CCD) allowing for preservation of calcareous
nannofossils; the continued presence of these fossils down-core suggests that the
summit of the rise has always been above the CCD (Winterer et al., 1973). Models
indicate that the initial water depth of the plateau could have ranged anywhere from
approximately 3750 meters (calculated based on a static model accounting for isostatic
subsidence under the load of sediments) to only 400 meters (calculated based on
plateau subsiding apace with typical seafloor in addition to sediment isostatic loading),
depending on model parameters (Winterer et al., 1973). Regardless of depth, no
evidence of resedimented shallow water material was detected in the core (or at this
site), demonstrating that this area remained stable and above the CCD since
Cretaceous times (Winterer et al., 1973).
The Magellan Rise has shared a pattern of movement with the Ontong Java
Plateau, as both ride upon the Pacific Plate. Prior to the Cretaceous period, the
Magellan Rise was located at approximately the same latitude as the Ontong Java
Plateau (~40° S, see above). Based on the shape of the sediment accumulation curve
during the Cretaceous, the Rise moved northward on the Pacific Plate, bringing it to an
equatorial position by the end of this period. Since this time, it has been moving
29
northward at approximately 1° every 4 million years to its present location (Winterer
et al., 1973).
Sample Acquisition, Site 167
One set of samples used in this study is from the Deep Sea Drilling Project
(Winterer et al., 1973) Site 167 Hole recovered from the Magellan Rise at 07°04.1’N ,
176°49.5’W in 3166 meters of water (Winterer et al., 1973). Figure 8 illustrates the
location of this and other drill sites in the Central Pacific Basin. This core was selected
due to its relative completeness (owing to its elevation above the present CCD) in
addition to biostratigraphic and magnetostratigraphic studies that provide an age
model and demonstrate reasonably continuous sedimentation during the Aptian period.
In addition, the core was sampled in a location reasonably close to the Ontong Java
plateau, where trace metal abundances are expected to be very high, especially for
those elements having short residence times (see Figure 5). Cretaceous chalk,
limestone, and chert were cored from about 680 meters to 1165 meters, an interval
covering ~110 Ma to ~125 Ma (Winterer et al., 1973). Sediment accumulation rates
were relatively slow during the Early Cretaceous (~4-10 m/m.y.) but increased during
the Late Cretaceous (~20 m/m.y.) (Winterer et al., 1973). Samples (in 20 cm
intervals), covering the period spanned by cores 63 to 70, from Hole 167 were
obtained from the Ocean Drilling Program core repository. This provided a
sedimentary record from 870 meters below sea floor (mbsf) (core 63) to 935 mbsf
(core 70) during a time interval
30
Site 463
Site 167
Figure 7. Locations of DSDP Sites 167 and 463 ( red stars) in the modern day.
31
Figure 8. δ13C for Site 167. Notice the dramatic positive excursion, beginning at ~920
mbsf. Data from L. Clarke (unpublished data).
32
exhibiting a dramatic positive δ13C excursion (L. Clarke, unpublished data), see
Figures 1 and 9.
Core 63 consists of limestone and chert, the upper part of which is generally
marly and owes its reddish-brown color to hematite and has a total carbon content (%)
ranging from 8.8 (top) to 11.0 (bottom) (Winterer et al., 1973, Bode, 1973). Cores 6467 sampled a layer of dark green material containing volcanic glass and zeolites and
have total organic carbon contents ranging from 10.4 % (top) to 7.6 % (bottom)
(Winterer et al., 1973, Bode, 1973). In the cores 68-70, the limestone is commonly
light in color with clay minerals concentrated into thin shale layers ; some zeolites and
Fe/Mn oxide layers are intermixed as well (Winterer et al., 1973). These cores range
from a low value of 2.9 % total organic carbon in core 68 to a high of 11.1 % in core
70, with an average of about 7.5 % total organic carbon (Bode, 1973).
The basaltic basement reached at this site was highly altered, containing many
small calcite specks, some calcite amygdules, and rare thin calcite veinlets (Thiede et
al., 1981). It was also highly brecciated. The nature of the amygdules, the thickness of
the volcanic glass formed, the fine-grained nature of the basalt, and the brecciation all
support the conclusion that Hole 167 ended in extrusive basalt (Thiede et al., 1981).
The Mid-Pacific Mountains
The Mid-Pacific Mountains are presently located in the central subtropical
north Pacific (Thiede et al., 1981). They represent an ancient (Late Jurassic to Early
Cretaceous) structural high rising between 2 and 3 km above the surrounding abyssal
plain (Thiede et al., 1981). As a result of their position, the Mid-Pacific mountains are
33
a favorable location to collect ancient sedimentary sections, similar to that of the
summit of the Magellan Plateau (see above). Also similar to the Magellan Plateau, the
Mid-Pacific mountains have moved to the northwest, starting at approximately 20°S x
145°E, according to the rotation model of the Pacific plate developed by Lancelot and
Larson (1975). Pringle and Duncan (1995) demonstrated that MIT Guyot, in the same
area was ~123 Ma. All evidence indicates that this region is of early to midCretaceous in age (Thiede et al., 1981).
Sample Acquisition, Site 463
A second set of samples used in this study was collected from the Western
Mid-Pacific Mountains at 21°21.01’N ,174°40.07’E in 2525m water depth (Thiede et
al., 1981). See Figure 8 for a map of this area. The selection criteria for this core are
the same basic ones as those discussed above; e.g. a relatively complete and
continuous sedimentary record existed for the Aptian interval. This core, however,
was collected in an area that was (is) significantly farther (~2700km vs. 1500km to
nearest point, see Figure 8) from the eruptive events forming the Ontong Java Manihiki Plateau and, thus, should see some of the effects of dilution displayed in the
trace element ratios of its sediments.
Multicolored, silicified, tuffaceous, calcareous, pelagic, and clastic limestones
were cored between the Late Albian to Late Barremian stages (Thiede et al., 1981).
The Early Aptian period, between these two stages, demonstrates a predominately
tuffaceous and calcareous lithology (Thiede et al., 1981). Paleo-water depth at this
34
Figure 9. δ13C for Site 463. Notice the dramatic positive excursion, beginning at ~630
mbsf. Data from L. Clarke (unpublished data).
35
time was several hundred meters. Samples were obtained for the section spanning the
sub-bottom depth form approximately 585 mbsf to approximately 660 mbsf (~115 to
~125 Ma respectively), starting with core 67 and ending with core 75. Accumulation
rates on average were ~12 m/m.y. during the Albian and ~27 m/m.y. during the
Aptian. Total organic carbon content is 0.1 (%) in cores 67 and 68, jumps to 1.5-1.6 in
core 69, falls off in Core 70 which has a high value of 0.7 (%) and a low of 0.0
(Thiede et al., 1981). Core 71 has a low of 0.1(%) and a high of 0.4 (%), while core 72
spikes form 0.1(%) to 1.4 (%) and then drops off (Thiede et al., 1981). Cores 73-75
have very similar values, with a dominant value of 0.1% (Thiede et al., 1981). These
samples were processed in 20 to 40 cm intevals, allowing for a higher resolution
picture of particular areas shown by L. Clarke (unpublished data) to have high δ13C
excursions (see Figure 10).The basaltic basement was not reached at this site.
Sample Processing
Crushing
The samples were prepared for microwave dissolution, first with a rigorous
cleaning (using laboratory wipes and analytical grade acetone) of the alumina plates of
a mini jaw-crusher. Once the plates were satisfactorily cleaned, the jaw crusher was
reassembled and a sample was run through the crusher. The crushed material landed in
a plastic weighing dish and was immediately placed into a plastic bag awaiting further
preparation. The jaw crusher was then brushed off prior to the careful cleaning of the
machine in preparation for the next sample. Throughout the entire process, every
effort was made to prevent any outside metal contamination.
36
Powdering
Next, a quarter of all jaw-crushed material was selected for powdering. This
strategy was selected to avoid the possible biases that sieving to a certain size fraction
may have instilled into the sample composition. The selected portion of crushed
material was placed into a previously acetone-cleaned diamonite mortar, and a pestle
of the same material was used to mill the material into a homogenous powder. The
resultant powder was then poured into a vial that had been blown out with canned air.
All parts of this step were designed to provide a sample with the lowest possible
contamination between samples and from ambient dust.
Microwave Dissolution
Finally, the samples were dissolved using a Microwave Accelerated Reaction
System 5 (MARS5). This process begins with 0.0600 g (+/-0.0005g) of sample being
weighed and placed into a Teflon tube (vessel). Twelve tubes are used, tubes one and
two consisting of repeats of the same sample, as tube one is used in the temperature
and pressure monitor vessel and does not provide accurate results. Reagent blanks
were included on nearly every run. Standard reference materials were also prepared in
this manner. After the samples were weighed and placed into the vessels 5 mL of
reagent grade hydrofluoric acid (HF), 3 mL of omni-trace 16 normal nitric acid (16N
HNO3), and 1 mL of omni-trace 6 normal hydrochloric (6N HCl) were added to the
samples to assist in the dissolution process. These vessels were then assembled into
their frames in the following manner: vessels were placed into pressure sleeves and
lids with safety membranes (new each time) were added. This assembly was placed
into the frame and screwed down with 5 ft-lb provided by a torque wrench. A
37
temperature monitor was added and the entire carousel was placed into the MARS
microwave. Digestion was completed using the program SHALE where the
microwave operated at 1200 Watts for a 15 minute ramp to a temperature of 200° C
and a pressure of 250 pounds per square inch. The samples were held at this level for
45 minutes, then allowed to cool to less than 60°C before evaporation.
Microwave Evaporation
Evaporation involved moving the vessels from the dissolution frames into an
evaporation carousel. For the initial evaporation lids were rinsed with 1 mL of double
distilled water which was then added to the digestion mixture. The evaporation
carousel was assembled with a temperature probe and vacuum exhaust and placed into
the microwave for evaporation. A vacuum was generated in the exhaust by a pump,
this vacuum exhaust was directed, via its tube, to a system of three scrubbers. These
scrubbers contained 4% boric acid, 5% sodium hydroxide, and water, samples ran
through each of these scrubbers respectively to neutralize the evacuated gases. In this
case, the program used was EVAP MIXED ACIDS, microwaving the samples at 600
Watts for 4 minutes to a temperature of 105°C, holding the sample at this temperature
until a rapid temperature drop was noticed. Normally the machine was manually
stopped at this time to reduce the risk of damage to the temperature probe. Samples
were allowed to cool to less than 60°C before secondary and tertiary evaporations,
these followed similar methodology to the initial evaporation with some slight
variations. Instead of water, 4 mL of HNO3 was added to the vessels, and the
evaporation program used was EVAP HNO3 featuring a 2 minute ramp to 110°C.
38
Upon completion of the third evaporation sequence, 9 mL of 2N omni-trace HNO3
was used to rinse the sample into weighed 15 mL Nalgene bottles. Upon completion of
this step, samples were ready to run through the mass spectrometer.
Microwave Cleaning
A cleaning run concluded the digestion process. Vessels were filled with 12
mL of 8 N HNO3 and reassembled into the frames as described in the dissolution step.
The CLEAN program used 1200 Watts and ramped the samples for 8 minutes to
200°C. All parts were then washed in double distilled water and placed in the clean
hood to dry before the next run.
Sample Analyses
Trace and Minor Elements
Microwave dissolved samples were analyzed for trace and minor elements
using Oregon State Universities VG PQ-Excell Inductively Coupled Plasma Mass
Spectrometer (ICP-MS). This instrument is located in the College of Oceanic and
Atmospheric Sciences’ W.M. Keck Collaboratory. Analysis starts with pipetting a 25fold dilution into test tubes; 0.2 mL of sample solution is diluted with 5.0 mL of 1%
triple-quartz distilled HNO3. Additionally, 0.1 mL of a In-115/Re-187 internal
39
Table 1. Means and standard deviations for Minor and Trace element data.
Units are ppm.
40
41
standard solution was added to correct for instrument drift, loss of sensitivity, and
matrix effects. All ICP-MS runs for this study followed a similar sample layout. The
first tube of the set is always an analytical blank, this is followed by several standard
reference materials, next a blank, and finally samples were placed in racks, with a
repeat every 10th sample to account for sensitivity effects. Each run contained between
80 and 100 samples. The samples were followed by another blank, and then re-runs of
the standard materials.
Upon completion of the ICP-MS run, calibration curves (developed from the
standard reference materials) are checked for accuracy. Once this step is completed,
two forms of data are available for comparison. Raw ICP-MS results are reported in
“analyte integrated counts per second” (counts), these are converted by the instrument
software using the standard curves to “analyte dilution concentration” (ppm, ppb, or
ppt in solution). Finally, the elemental concentration in liquid is converted manually to
elemental concentration in the solid sample. Analysis of the United States Geological
Survey (USGS) MAG-1 marine sediment and blind duplicates indicates that the
percentage error for most elements is less than 10% (Table 1). Some elements,
however, do have higher errors. These include Bi, Th, and U with percentage errors
averaging between 10 and 20%. The elements Ag, Au, Cd, Co, and Mo have errors
greater than 20%. Due to this larger instrumental uncertainty, inferences made using
data from these elements should be treated with more caution. Analytical errors may
also be introduced because only two internal standards were used during this analysis,
as opposed to the normal three to four.
42
Table 2. Means and standard deviations for Major element data. Units
are ppm.
MAG-1
Accepted
86810.80
480.00
9792.20
47566.20
29471.90
18093.50
759.00
28415.30
698.40
4496.10
Element
Al 167.079
Ba 455.403
Ca 317.933
Fe 259.940
K 766.491
Mg 279.078
Mn 257.610
Na 589.592
P 178.283
Ti 336.122
89691.41
470.09
10049.03
48651.72
29806.55
17898.09
783.77
27590.31
666.82
4682.24
MAG-1
Mean
2584.67
123.27
767.53
4987.48
2491.47
731.97
68.44
1369.75
479.63
389.50
MAG-1
St. Dev.
17.00
9.70
293.46
17.55
2.23
6.47
3.06
2.92
1.77
1.32
0.42
0.04
2.11
0.12
0.43
0.05
0.02
0.37
0.19
0.02
29.11
9.58
301.88
16.48
3.65
6.72
3.06
3.72
2.32
1.24
17.26
0.14
5.38
0.45
0.50
0.12
0.04
0.19
0.60
0.04
167 63R1 0-3 (1) 167 63R1 0-3 (1) 63R 01W 29-31 (1) 63R 01W 29-31 (1)
Mean
St. Dev.
Mean
St. Dev
43
44
Major Elements
Major element concentrations were determined using two different
instruments. The majority of Site 463 major element data was collected using
inductively coupled plasma-atomic emission spectrometry (ICP-AES). This
instrument was subsequently replaced with a new inductively coupled plasma-optical
emission spectrometer (Varian Liberty 150) that was used to collect all of the major
element data for Site 167. Additional samples from Site 463 were also processed on
this instrument. All samples were processed in the same manner, regardless of
instrument. Microwave dissolved standard reference materials, sample solutions, and
procedure blanks were all diluted 100 times; 0.1 mL of sample solution 10 mL of 1%
triple-quartz distilled HNO3. All ICP-AES runs for this study followed a similar
layout. The first tube of the set is always an analytical blank, this is followed by a
group of external standard reference materials.
Next, an acid memory check is run (for extra wash time) followed by the
samples themselves. Throughout the runs, one sample was used as a unknown repeat
between every 10 samples. Results for ICP-AES are reported as intensities which are
proportional to the concentration of that element in the sample. Using calibration
curves developed with the standard reference materials element compositions of a
given sample are quantified. Finally, a correction is applied to account for the dilution
of the sample. Based on the analyses of blind duplicates and standards, the percentage
error for the ICP-AES data used in this study is between 2-8% (Table 2), depending on
the element analyzed and the sample. The elements Ba, Na, and P have
45
errors larger than this in some of the samples, so data concerning these elements
should be treated with more caution.
Results
This study reports abundance measurements for twenty-eight trace and minor
elements using an ICP-MS, and ten elements using ICP-AES instruments. All
measurements for DSDP Sites 167 and 463 were made in Oregon State University’s
Keck Lab for Plasma Mass Spectrometry. Results for these experiments can be seen in
Appendix 2. All minor element concentrations were normalized to zirconium (Zr),
while major element concentrations were normalized to aluminum (Al). The only
significant source of both of these elements to pelagic sediments is from terrigenous
input, therefore this normalization accounts for the variable effects of terrestrial input
into the composition of these sediments (Milnes and Fitzpatrick, 1989). One caveat
must be made, however, about normalizing to Zr. Much of the zirconium found in
pelagic sediments arrives in the form of zircons, which are very difficult to fully
dissolve. However, the dissolution method developed by Snow (2003) proved to be
very effective at fully dissolving the Zr present in shales. The same method was used
for this study, and a comparison to a similar external standard reference material
shows good Zr dissolution (see Table 1).
Site 167
The DSDP Site 167 core data collected during this study show two distinct Zrnormalized trace metal anomalies (Figure 10 and Appendix 2). The first (earliest) and
smaller anomaly occurs in the interval between ~920 and ~910 mbsf. This anomaly
46
can be seen in all elements except Cd, W, Au, Hg, and Bi. A second, larger, anomaly
occurs in the interval between ~890 and ~880 mbsf. This anomaly can be seen in all
elements except W, Cd, and Hg. Major element data appear to remain at background
levels throughout most of this sampling interval (Figure 10 and Appendix 2).
However, the elements P and Ti contain slight positive excursions in the interval
between ~890 and ~880 mbsf.
Site 463
The DSDP Site 463 core data collected during this study show two distinct Zrnormalized trace metal anomalies (Figure 11 and Appendix 2). The first (earliest) and
smaller anomaly occurs in the interval from ~622 mbsf to ~617 mbsf. This anomaly
can be seen in the minor elements V, Zn, Se, As, Y, Mo, In, Sb, Cs, Ba, W and Re. A
second, larger, anomaly begins at ~610 mbsf and extends to ~580 mbsf. A very coarse
sampling interval (due to incomplete core recovery) makes it difficult to determine if
the peak seen in the Figures 11 is a separate occurrence or merely a continuation of the
excursion starting at ~610 mbsf. As the same elements show anomalies in both areas,
it was assumed that the latter is the case. This anomaly can be see in all of the minor
elements with the exception of Y and Hg. Throughout this interval all major elements
except Ti demonstrate a distribution indicative of background levels, no trends are
easily distinguished (Appendix 2).
47
Cu/Zr
Sc/Zr
500
0
Pb/Zr
10000
0
860
860
870
870
870
880
880
880
890
900
910
920
890
900
910
920
Meters Below Sea Floor
860
Meters Below Sea Floor
Meters Below Sea Floor
0
200
890
900
910
920
930
930
930
940
940
940
950
950
950
Figure 10. Minor (Sc, Cu and Pb) element data from DSDP Site 167. Two intervals of
high metal abundance can be seen. The H. sigali/G. blowi. foraminiferal boundary
(which marks the Aptian/Barremian boundary) is shown as a red line for reference.
48
Sc/Zr
Cu/Zr
0
5
Pb/Zr
200
0
580
580
590
590
590
600
600
600
610
620
630
640
610
620
630
640
Meters Below Sea Floor
580
Meters Below Sea Floor
Meters Below Sea Floor
0
1000
2000
610
620
630
640
650
650
650
660
660
660
670
670
670
Figure 11. Minor (Sc, Cu, and Pb) element data from DSDP Site 463. Two intervals of
high metal abundance can be seen. The H. sigali/G. blowi. foraminiferal boundary
(which marks the Aptian/Barremian boundary)is shown as a red line for reference.
49
Discussion
The goal of this study was to assess the geochemistry of early Aptian (~122
Ma ) sediments, deposited at the time of Ocean Anoxic Event 1a (OAE1a) from
several locations, with respect to the hypothesis of Sinton and Duncan (1997).
Specifically, if ocean anoxic events were promoted by plateau volcanism, there should
be an identifiable signature of anomalously high trace metal abundances in the
sediment record. Snow (2003) and Snow et al. (2005) found that trace metal anomalies
in marine sediments that include the Cenomanian/Turonian boundary (~93.5 Ma)
correlate closely with excursions in the δ 13C record, extinctions of benthic species,
and turnover in plankton communities – all of which constitute Ocean Anoxic Event 2
(OAE2). This study is an extension of the previous work by Snow (2003), to evaluate
the proposed link between OAE1a and submarine volcanic construction of the Ontong
Java - Manihiki Plateau (~122 Ma).
Upon entering the ocean trace metals are ultimately removed from the seawater
reservoir to marine sediments (Bruland, 1983). However, trace elements undergo
varying degrees of recycling prior to their final removal to oceanic sediments. This
recycling can involve particle interactions, benthic fluxes, scavenging reactions,
diagenesis, or a combination of these processes (Bruland, 1983). Figure 12 is a
schematic diagram demonstrating trace element sources to seawater. As discussed in
the Introduction, there are several means by which trace metals can become enriched
in sediments. Plankton themselves carry a suite of trace elements into the sediment
50
record, however the composition of planktonic organisms cannot explain the trace
element peaks seen in this study. For a more detailed discussion of how the
composition of plankton affects the sediment record, see Appendix 1. Additionally, as
particles from decomposing plankton and other sources sink through the water
column, they perform a crucial role in the scavenging of trace elements from seawater
by providing suitable binding sites for the absorption of metal ions or ionic complexes.
Scavenging was unquestionably an important factor in the trace metal enrichment of
black shales. Water column oxygen and sediment diagenesis also can mobilize metals
and create concentrations in the sediment record. However, the scope of these
processes is not great enough to explain the anomalies seen in this study. For a more
detailed discussion of these processes, see Appendix 1. Figures in Appendix 1
demonstrate the relationship found between metal fluxes in modern chemistry and
marine planktonic composition, degassing and hydrothermal events, and metal
abundance anomalies found in this study. These figures demonstrate that the element
fluxes generated via degassing and hydrothermal means most closely resemble the
trace metal abundance anomalies seen in the marine sediment record.
It is clear that undersea magmatic and hydrothermal activity due to the
emplacement of the Ontong Java - Manihiki plateaus greatly altered the seawater
chemistry intermittently, over a geologically brief interval in the early Cretaceous, and
that this is what we see reflected in the sediment record containing OAE1a. If
hydrothermal activity and degassing associated with the formation of the plateau were
51
responsible for the metal peaks seen in OAE1a, one would expect these peaks to have
a close stratigraphic relationship to these events at globally distributed sites.
Enrichment in trace metals, seen throughout the global ocean, would certainly be
expected to influence marine life. Experiments done by Coale et al. (1996)
demonstrated that iron fertilization in modern oceanic high-nitrate, low chlorophyll
(HNLC) regions could greatly stimulate primary productivity. Using this experiment
as a guide Sinton and Duncan (1997) calculated that the iron injected into the water
column by ocean plateau formation could have triggered greatly enhanced primary
productivity. Enhanced primary productivity would have had several effects: (1)
increased organic particles falling through the water column depleted seawater oxygen
through respiration; (2) organic particles scavenged trace metals and accumulated as
black shales; (3) eutrophic conditions (and perhaps metal toxicity) would have favored
the most opportunistic nannoplankton taxa, leading to crises of less successful
competitors (Erba, 2004).
As major episodes of organic carbon removal occur, the lighter of the two
carbon isotopes found in seawater (12C and 13C) is preferentially removed from the
oceanic reservoir (Faure, 1986). This relationship leads to a shift to more positive
carbon isotope compositions in marine sediments. Looking at integrated
biostratigraphic and magnetostratigraphic data, together with carbon isotope data and
the trace metal results of this study will help us determine if there was a biological
response (i.e., removal of carbon) at the time of the hydrothermal plumes. Figure 13
shows selected trace metal data for each of the three sites compared with their
52
corresponding δ 13C record, aligned with bio- and magnetostratigraphic information
for this period. All three sites (DSDP Sites 167 and 463, as well as the CISMON
Apticore) reveal remarkably similar profiles. All profiles show a small positive δ 13C
peak followed by an abrupt negative carbon isotope excursion during or just after the
“M0” period. This is then followed by a dramatic increase in the δ 13C composition of
carbonate.
Further comparison of Figures 1 and 13 demonstrate that the δ 13C anomaly is
preceded by a documented worldwide change in nannofloral assemblages (Erba, 2004
and references therein). The nannoplankton response described above was suggested
by Erba (2004) to be a result of a paleoenvironmental crisis. Erba (2004) proposed that
this type of response is likely the result of eutrophication on a global scale. The trace
metal peaks seen in Figure 13 are stratigraphically coincident (occurring both before
and during the events) with the biotic changes reported at this same time (see Leckie,
2002 and Erba, 2004 for an overview of biologic events during this time).
As the trace metal peaks seen in this study have been demonstrated to
be of hydrothermal and magmatic degassing origin, it seems evident that submarine
volcanism had two drastic influences on marine phytoplankton. The “nannoconid
crisis” was a global decrease in the abundance of rock-forming nannoconids marking
the Early Aptian OAE1a (Erba, 2004). Erba (2004) suggested in the same work that
this crisis was the result of selective metal toxicity because the nannoconid decline and
crisis, correlates with metal peaks. The peaks she noted correlate with the larger
(upper) metal peak seen in this study at Sites 167 and 463. Second, submarine
53
Figure 12. Trace elements cycle into and out of seawater in various ways. Sources
include rivers, dust, hydrothermal activity, and magmatic “event plumes”. The main
sink is sediment, although it can be a source under certain circumstances.
54
55
volcanic input of biolimiting metals could have triggered eutrophic conditions. This
study suggests that the influence of the Ontong Java - Manihiki plateau emplacement
affected marine organisms around the world. The eutrophic conditions stimulated by
this event may have spurred primary productivity to the extent that respiration of
organic matter would have depleted global ocean oxygen and promoted preservation
of organic-rich sediments, resulting in OAE1a.
The submarine volcanic activity that formed the Ontong Java - Manihiki
plateau should have left a combination of two patterns of trace metal chemical
signatures in the marine sediment record. The first is from the release of a high
temperature magmatic fluid degassed directly into the submarine environment as a
direct result of eruptive activity (shown as “degassing” in Figure 12). A second
signature is from hydrothermal fluids produced by exchange of heat and elements
between seawater and porous lava flows as spreading centers cooled on the seafloor
(shown as “hydrothermal” in Figure 12). Each of these processes delivers a distinct
suite of elements into seawater (Rubin, 1997). If hydrothermal activity and degassing
associated with the formation of the Plateau was responsible for the metal peaks seen
in the black shales, one would expect these peaks to have a close stratigraphic
relationship to these events.
The positions of representative trace metal anomalies found by this study in
DSDP Sites 167 and 463 were plotted with respect to the δ 13C curves for the same
sites in Figure 13. Figure 13 also includes data obtained from the CISMON Apticore,
northern Italy (Duncan and Erba, pers. comm.). The δ 13C curve is a global signal, so
56
Figure 13. Figure is a plot comparing representative elements from the three sites used
in this study, DSDP Sites 167 and 463 as well as CISMON (data from Duncan and
Erba, unpublished). These sites have been correlated to each other using magenetoand nannofossil- stratigraphy in addition to δ 13C excursions. Blue bar indicates the
M0 period of magnetic anomaly. Organic carbon rich intervals are indicated with light
green boxes. The δ 13C profile is represented by the light blue line with blue stars (L.
Clarke, per. comm.). The dark blue line with circles represents the Zr normalized Sc
data, the pink line with squares represents Zr normalized Zn data, and the green line
with triangles represents the Zr normalized Pb data. In order to fit on the same scale,
data from each site has been adjusted in the following manner: Site 167 (Sc/Zr/125;
Zn/Zr*18; and Pb/Zr/50), Site 463 (Sc/Zr*2; Zn/Zr*2; and Pb/Zr/100), and CISMON
(Zn/Zr/10).
57
58
the plots were aligned to each other using the common features of these profiles.
Additionally, the plots were aligned using nannofossil and magnetostratigraphy. This
provided tie points necessary to match the records and correct for differences in
accumulation rates. Upon inspection of Figure 13, a small trace metal peak can be
seen immediately preceding the first, smaller positive excursion in the carbon isotopic
profile at Site 167. Site 463 demonstrates a small increase in trace metals shortly after
this excursion as well. A trace metal peak is seen in the CISMON core at this same
time. In Site 167 a second, larger trace metal peak can be seen following the larger
positive carbon isotope excursion. Trace metal data for the same interval from the Site
463 and CISMON cores are not yet available for comparison. Comparing Figures 1
and 13 clearly demonstrates that the trace metal peaks seen in DSDP Sites 167 and
463 are stratigraphically coincident with the 87Sr/86Sr isotopic drop, planktonic
evolutionary events, and the timing of the Ontong-Java and Manihiki plateau
emplacement. This indicates that the trace metals released during the emplacement of
oceanic plateaus are coincident the onset of ocean anoxia.
Degassing, Hydrothermalism, and Trace Metals
Hydrothermal activity related to the steady-state volcanic processes at midocean ridges production emits trace metals, but it is unlikely that the effects of this
activity would be confused with the volcanic activity on a massive scale associated
with plateau formation. As noted earlier, the intermittent nature of these metal peaks is
one indication that they are not directly related to the continual process of ridge
formation. Additionally, Vogt (1989) has argued that hydrothermal plumes from
59
spreading ridges do not have enough thermal energy to reach the oceans surface and
therefore cannot contribute metals to OAEs through the surface ocean. Rubin (1997)
has shown that the two processes (hydrothermal and degassing) contribute a broad
suite of metals to the water column.
Figure 5, adapted from Rubin (1997) provides a guide in understanding what
elements are released by these two processes, and what their ultimate fate in seawater
is. This figure shows volatility versus residence time for a number of elements.
Volatility in this context is described as “the concentration difference of an element
between pre-erupted magma and post-erupted lava” (Rubin, 1997). In other words,
those elements that have higher volatilities more easily escape the magma as a fluid
(gas) phase that mixes with seawater. A mean oceanic residence time is determined
from the total mass of a substance dissolved in the oceans divided by the rate of
supply (or removal) of the substance (Brown et al., 1994). Those elements with short
residence times do not remain in the water column for long period of time, while
elements with long residence times do. Hence, we expect to see a shift in the pattern of
trace element abundances with distance from source, as a result of preferential
removal, and an overall decrease in abundance of all such elements as a result of
dilution.
Using the Rubin diagram to classify elemental abundance anomalies, a
selection of elements seen in the ~920 mbsf peak at DSDP Site 167 are plotted (Figure
14). The less volatile, short residence time elements are quite enriched at this
60
Site 167, Magellan Rise – 920 m Peak
Hydrothermal
Magmatic
Less Volatile
Oceanic Residence Time, Years
1E1
Sc
More Volatile
Co
1E2
Sn
1E3
1E4
Cr Ni
Ba
V
Times (x) background
Cu
Green = 0-3
Blue = 3-10
Tl
Cs
W
Sb As
Mo
1E5
1E6
1E7
1E8
In
Zn
Less Soluble
Pb
Cd
Bi
Se
Au
Sr
Purple = 10-20
Ag
Re
Red = 20-40
Black = 40+
More Soluble
Figure 14. Volatility versus residence time for DSDP Site 167’s lower (920 mbsf)
peak. The less volatile, shorter residence time elements are quite enriched at this
interval.
61
interval indicating that sediments in this area reflect significant hydrothermal input.
This is not surprising considering the close proximity of this site to the Ontong Java Manihiki plateaus. Elements having higher volatility and correspondingly short
residence times are also quite enriched, demonstrating that this interval also had
chemical input from magmatic degassing. This same interval also contains a number
of quite enriched, long residence time, hydrothermal elements, and is very enriched in
magmatically degassed elements of long residence time. The most reasonable
interpretation is that magmatic degassing and hydrothermal effluent emanating from
the Ontong Java - Manihiki plateaus are responsible for the metal peaks seen in the
DSDP Site 167 at 920 meters below sea floor.
Plotting elemental abundances for the 890 mbsf peak at DSDP Site 167 (Figure
15) shows a very similar pattern, albeit with even more elevated anomalies. This upper
peak probably had a very similar type of supply of elements as that of the lower, but
larger due to greater eruptivity. This pattern of elements suggests that the residence
time effects and ocean circulation patterns must have remained relatively constant.
This would imply a second period of intense eruptive activity occurring at the Ontong
Java - Manihiki plateaus, following an interval in which ocean chemistry returned to
normal, steady-state composition.
As data from one site may not be sufficient to draw solid conclusions
additional data from other locations were collected. Not only can we examine the
stratigraphic position of these events, but we can also see if significant residence time
effects occur. Figure 16 plots elemental abundance anomalies for the ~620 mbsf peak
62
Site 167, Magellan Rise – 890 m Peak
Hydrothermal
Magmatic
Less Volatile
Oceanic Residence Time, Years
1E1
Sc
More Volatile
Co
1E2
Sn
1E3
1E4
Cr Ni
Ba
V
Times (x) background
Cu
Green = 0-3
Blue = 3-10
Tl
Cs
W
Sb As
Mo
1E5
1E6
1E7
1E8
In
Zn
Less Soluble
Pb
Cd
Bi
Se
Au
Sr
Purple = 10-20
Ag
Re
Red = 20-40
Black = 40+
More Soluble
Figure 15. Volatility versus residence time for DSDP Site 167’s upper (890 mbsf)
peak. The less volatile, shorter residence time elements are very enriched at this
interval.
63
Site 463, Mid-Pacific Mountains – 620 m Peak
Hydrothermal
Magmatic
Less Volatile
Oceanic Residence Time, Years
1E1
Sc
More Volatile
Co
1E2
Sn
1E3
1E4
Cr Ni
Ba
V
Times (x) background
Cu
Green = 0-3
Tl
Cs
W
Sb As
Mo
1E5
1E6
1E7
1E8
In
Zn
Less Soluble
Pb
Blue = 3-10
Cd
Bi
Se
Au
Sr
Purple = 10-20
Ag
Re
Red = 20-40
Black = 40+
More Soluble
Figure 16. Volatility versus residence time for DSDP Site 463’s lower (620 mbsf)
peak. The less volatile, shorter residence time elements are enriched at this interval.
64
at DSDP Site 463. This corresponds to the lower peak seen in Site 167 (see Figure 14).
It is clear that Site 463 is less enriched in all elements when compared to Site 167. The
upper peak (at 610 mbsf) in Site 463 (Figure 17) seems to follow this same general
pattern, having slightly lower values than Site 167’s upper peak (Figure 15). However,
Sc and Cu are exceptions, having higher enrichments in this area; perhaps due to
regeneration effects close to the plateau these heavily recycled elements would tend to
travel somewhat farther in the surface waters before reaching the seafloor. One would
expect to see overall different enrichments in different sites, due to residence time
effects and the variable contributions of degassing and hydrothermal inputs to effluent
plumes. As a general rule, lower concentrations of hydrothermal or degassed elements
in seawater occur with distance as the plume effluent mixes with the surrounding
seawater. Those elements having shorter residence times would not remain in the
water column as long and would be most strongly expressed in near-field sediments,
while they may have lower abundances in more distant areas.
Residence Time, Cretaceous Circulation, and Location
The consequences of dilution and varying residence times are discernable
between DSDP Sites 167 and 463. Figure 18 shows a general upper ocean circulation
model for Early Cretaceous time. This model reconstruction (Poulsen et al., 2001) was
developed for the Albian (~100 Ma) epoch using atmospheric CO2 content of four
times the present day level (1380 vs. 340 ppm). Similar to modern circulation, the
mid-Cretaceous upper ocean was dominated by subtropical and subarctic gyres in
65
Site 463, Mid-Pacific Mountains – 610 m Peak
Hydrothermal
Magmatic
Less Volatile
Oceanic Residence Time, Years
1E1
Sc
More Volatile
Co
1E2
Sn
1E3
1E4
Cr Ni
Ba
V
Times (x) background
Cu
Green = 0-3
Tl
Cs
W
Sb As
Mo
1E5
1E6
1E7
1E8
In
Zn
Less Soluble
Pb
Blue = 3-10
Cd
Bi
Se
Au
Sr
Purple = 10-20
Ag
Re
Red = 20-40
Black = 40+
More Soluble
Figure 17. Volatility versus residence time for DSDP Site 463’s upper (610 mbsf)
peak. The less volatile, shorter residence time elements are enriched at this interval.
66
Mid-Pacific
Mountains
CISMON
Magellan
Rise
Ontong Java – Manihiki plateaus
Figure 18. The Ontong Java-Manihiki plateaus, Mid-Pacific Mountains, Magellan
Rise, and CISMON (in modern-day Italy) shown in their paleo-locations on a
schematic diagram of Cretaceous (~100 Ma) ocean circulation (modified after
Poulsen et al., 2001). Length and orientation of black arrows correspond to surface
current velocity and direction.
67
addition to strong equatorial currents. Poulsen et al. (2001) propose that deep ocean
water originated in two locations of the southern ocean and spread north to fill the
Pacific and Indian basins. Marked on the figure are the paleo-positions of several sites:
Deep Sea Drilling Project Sites 167 and 463 used in this study, as well as the
CISMON Apticore, Tethys ocean.
In the present day ocean the slower eastern boundary currents move at a rate of
approximately 50 kilometers per day (Segar, 1998). The entire ocean can be expected
to mix in 1000 to 2000 years (Berner and Berner, 1996). Cretaceous circulation was
probably slower than this because of reduced temperature gradients between the
equator and the poles. From Figure 18 one can get a general idea of transit times from
the Ontong Java – Manihiki plateau to the sites used in this study. Hydrothermal
plumes would have reached the Magellan Rise (Site 167) in approximately 30 days,
and between 50 (closest point to closest point) and 300 (traveling around the gyre)
days to reach the Mid-Pacific mountains (Site 463). While the above times are gross
estimates, they nonetheless indicate that Cretaceous surface circulation would have
brought seawater with hydrothermal and magmatic signatures to both of these sites in
periods less than the shortest residence time for the metals that they carried. This lends
credence to Figures 14-17, and also clearly demonstrates why Site 167 contains higher
metal abundance anomalies.
To determine if these hydrothermally-dispersed elements created a truly global
seawater signature additional data from the CISMON Apticore were obtained
(Duncan, Erba, unpublished results). These drill cores were collected from a site in the
68
Belluno Basin, Northern Italy. During the emplacement of the Ontong Java - Manihiki
plateau, however, this site was located in the northern Tethys ocean – very far away
from the eruptive area (see Figure 19). Using the same Cretaceous ocean circulation
model, surface waters could take several years to travel to this location. Figure 19
indicates that a metal peak did indeed reach this area during the “M0” interval.
Interestingly, the stronger, upper peak seen in Sites 167 and 463 does not appear as
distinctly at this location. As the upper peak occurred during the stronger positive δ
13
C excursion, it is possible that this period also experienced higher surface
productivity and more complete seawater anoxia, thus more effectively removing
metals from the seawater closer to the source. The water reaching to the most distal
extent may have been very metal barren for this reason, or perhaps dilution effects
were sufficient to explain the smaller abundance anomalies.
Figure 19 shows that overall elemental abundances are lower for the CISMON
“M0” interval than for Sites 167 and 463. This is expected, as element concentrations
in the seawater would have dropped substantially with biogenic uptake, particle
scavenging, and dilution as surface ocean water circulated from the source to the
northern Tethys ocean (northern Italy). From this evidence, it seems clear that the
emplacement of the Ontong Java - Manihiki plateaus had seawater trace element
effects that were truly global.
69
CISMON, North Italy “M0” Interval
Hydrothermal
Magmatic
Less Volatile
Oceanic Residence Time, Years
1E1
Sc
More Volatile
Co
Less Soluble
Pb
1E2
Times (x) background
1E3
Cr Ni
B
1E4
Zn
Cu
Green = 0-3
Blue = 3-10
V
Purple = 10-20
Ag
1E5
1E6
1E7
W
Sb
Mo
Cd
Bi
Se
Au
Red = 20-40
Black = 40+
More Soluble
1E8
Figure 19. Volatility versus residence time for the CISMON, North Italy “M0”
Interval. The less volatile, shorter residence time elements are enriched at this
location as well, but not nearly to the extent that they were at Sites 167 and 463.
70
Chapter 3. Summary, Conclusions, and Future Studies
This study examined three Early Cretaceous marine sedimentary sections, two
of which were located in close proximity (near-field) to the emplacement of the
Ontong Java - Manihiki plateau, and one which was quite distant (far-field) from the
event. Major, minor, and trace element abundance data were obtained in an effort to
determine if a connection exists between the emplacement of submarine large igneous
provinces (the Ontong Java - Manihiki plateau in this instance), the associated
magmatic degassing and hydrothermal activity, and ocean anoxia. The results indicate
that trace metal abundance anomalies are stratigraphically correlated with other
biogeochemical events during this time period, supporting the hypothesis that trace
metals released during magmatic event plumes may trigger the onset of ocean anoxia.
Further, using trace element abundance patterns based on volatility versus
residence time, this study demonstrated that the less volatile and more reactive
(magmatic) elements were somewhat more enriched in the locations closer to the
Ontong Java - Manihiki plateaus and less enriched farther from the source. The
patterns of abundance in DSDP Sites 167 and 463 are similar, with Site 463 showing
some effects of dilution. This is expected as these sites are relatively close to each
other, however some elements would have been more subject to residence time
effects. At the CISMON Apticore site (northern Italy) there is also an elevation in
trace metals in the same interval (M0), however the extent of enrichment is not as
great. This is also logical, owing to its great distance from the eruptive event and the
71
ensuing dilution effect. The pattern of trace elements seen is consistent with the
location of the Ontong Java - Manihiki plateau during this time, and their distribution
is also consistent with a model of Early Cretaceous ocean circulation.
While this study has demonstrated that a connection between Ocean Anoxic
Event 1a and the emplacement of the Ontong Java - Manihiki plateau exists, further
work is needed to reinforce this link. In an effort to demonstrate near- and far-field
effects this study used data from three different locations. This work would benefit
greatly from the inclusion of trace, minor, and major element data from several more
sites of varying distances from the source of volcanic ativity. Possible drilling legs
from which to study additional samples from include Ocean Drilling Program legs 103
(the Galicia Margin) and 143-44 (Northwest Pacific Atolls and Guyots). Leg 103
would provide samples from the (then) proto-Atlantic ocean. These locations would
unquestionably provide useful intermediate submembers, helpful in determining
additional near and far-field effects.
Another exciting area of future work lies in determining if the element
anomalies found in Cretaceous sediments reflect those elements lost by degassing and
hydrothermal fluxes during the same time period. This mass balance could be
calculated by determining the composition of unaltered basalt, and subtracting the
composition of altered basalt from this. The difference between these two
compositions should reflect what is found in the element abundance anomalies seen in
the sediment record. In order to carry out this experiment, the composition of the
parental melts could be determined from melt inclusions trapped in phenocrysts in
72
erupted lava flows. Second, the compositions of altered basalts from Ontong-Java and
Manihiki Plateaus are easily determined from previously recovered cores.
73
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80
Appendix 1: Trace Metal Patterns in Marine Sediments
Plankton and Trace Metals:
Particles are produced primarily by phytoplankton in surface waters, and thus
the uptake of some trace metals in the ocean can be attributed to their function as
essential micro-nurtients (Bruland, 1983). The table below shows the average
chemical composition of plankton/marine organisms. One would expect the chemical
composition of a biogenic sediment (and black shales are known for their high organic
carbon) to have some relationship to the constitution of the organisms that it is
comprised of. Indeed, Piper (1994) showed that some minor element ratios found in
several black shale formations matched minor element ratios found in modern
plankton, demonstrating that seawater could be the source of minor elements to some
black shales. However, in their comparison of the geochemistry of organic matter,
sapropels (organic matter-rich marine sediments), and black shales, Nijenhuis et al.
(1999) concluded that this may not always be the case. As an example they
demonstrated that the globally distributed Cenomanian/Turonian Boundary Event
(CTBE) black shale (and its attendant metal enrichment) was too massive to be
attributed to seawater trace metal enrichment alone; seawater could not have provided
the needed trace element reservoir. The ratios seen are also different from those seen
in the table below.
81
Element
Ag
As
Ba
Bi
Cd
Co
Cr
Cu
Mo
Ni
Pb
Sb
Se
Tl
V
Zn
Mean Value (ppm dry matter)
0.1
5
80
0.1
12
1
1
10
2
8
6
0.5
1
0.1
3
80
Table demonstrates the average chemical composition of modern
plankton/marine organisms. Data from this table can be seen graphically in
figure 14. After Brumsack (1989).
82
Further validation of this conclusion can be found in Brumsack and Thurow’s
(1986) study which found that the abundance of metals seen in CTBE sediments could
not be explained by the deposition of plankton-derived, organic matter-rich particles.
As OAE1a was at least as large (see Figure 1), if not larger than OAE2, it seems
reasonable to assume that normal seawater is not the primary trace element source for
the OAE1a shales analyzed in this study. Further, biogenic sediments cannot account
for the trace metal enrichments seen.
In addition, the Figures A2-A5 below to seem to indicate that the elements
present in seawater/biology have a different abundance pattern than marine sediments
that accumulated during OAE1a. Algeo and Maynard (2004) add validity to this
observation by noting that the trace elements Zn, Cu, and Ni exhibit trace element
patterns indicative of biogenic uptake, while the metals Mo, U, V, and Cr show no
evidence of a bionutrient role in modern marine systems. Finally, Brumsack (1989)
noted that sediments from modern high productivity environments are not
characterized by high trace metal concentrations, due to high water column metal
regeneration, low trace metal concentration of marine plankton, and the high
accumulation rates for these areas.
83
Figure A1. This cartoon demonstrates the path that many elements take through
seawater. First the elements are either used by biological processes. Next, as the
biological particles die and sink, additional particles are adsorbed onto the particles
via a process known as scavenging. Ultimately most of the elements in seawater
reach the sediment in this manner.
84
85
Water Column Oxygen and Trace Metals
In the modern ocean anoxic water column conditions are ideal sinks for many
redox-sensitive and stable sulfide forming elements (Brumsack, 1989). Oxic water
column conditions can also affect the chemical composition of sediments. For
example, those elements coupled with labile nutrients (like Cd and Zn) will have
lower concentrations in oxic sediments than expected from the chemical composition
of marine plankton because they are regenerated into the water column (Brumsack,
1989). Previous studies have shown that the elements Cd, Cu, Mo, Re, U, and V are
enriched in anoxic sediments and not enriched in those that are anoxic (Veeh, 1967;
Bertine and Turekian, 1973; Jacobs and Emerson, 1982; Colodner et al., 1993; Calvert
and Pederson, 1993). Brumsack (1989) concluded that Cretaceous black shale layers,
however, represent periods of enhanced preservation of organic matter rather than
periods of excessively high productivity. This conclusion is based on the premise that
seawater is generally very metal-poor, making long time periods and low sediment
accumulation rates necessary to generate trace metal peaks (Brumsack, 1986). As seen
in the data for ocean drilling sites 167 and 463, this study indicates that there may be
an anomalously high flux of trace metals to the Cretaceous ocean, generating the
peaks seen. It seems that while the biological makeup of plankton itself lacks the
necessary chemistry to provide trace element signatures seen in the OAE1a sediments,
particle scavenging made possible by the sinking of these organisms is an important
additional source of metal removal from the water column. Yet, it still remains to be
seen where the elements seen in this study come from, as continental source fluxes
86
would not appear to be large enough to maintain the trace metal enrichment necessary
for the large temporal and global distribution seen in OAE1a (Morford and Emerson,
1999).
Diagenesis and Trace Metals
Trace element distributions seen in sediments are also affected by diagenetic
processes. Is it possible that the diagenetic remobilization of trace elements in
sediments (having arrived as biological particles complete with their load of
scavenged elements) could provide the peaks that are seen in the results of this study?
Diagenetic processes can do two things: generate metal peaks in the sediment record
(essentially concentrating the metals from an interval into one horizon), or cause them
to diffuse across the sediment-water interface (depending on the redox potential of the
surrounding water column) and be lost from the sediment record (Froelich et al., 1999,
Nameroff et al., 2002). Redox potential is used by chemists to express the tendency of
an environment to receive or supply electrons (Schlesinger, 1997). Oxic environments
are said to have a high redox potential because O2 is available as an electron acceptor
(Schlesinger, 1997). An understanding of the redox potential of the environment is
pertinent because it can have a noticeable effect on the authigenic enrichment or
depletion factors in sediments.
Brumsack and Thurow (1986) evaluated the possibility of diagenetic
enrichment to black shales and concluded that an enrichment due exclusively to these
processes seems highly unlikely. While it seems clear that these elements will be
enriched during periods of anoxia, it should also be noted that under the same
87
conditions any redistribution will occur on a centimeter scale (Algeo and Maynard,
1999., Brumsack and Thurow, 1986). All of the high abundance metal signatures seen
in this study occur over intervals of several meters.
Modern seawater does not have a sufficient inventory of the necessary
elements to maintain the rate of metal deposition seen in this study, so we must look at
additional sources to explain the abundances and patterns. One possibility is that
increased volcanic activity would have increased global levels of CO2, increasing the
acidity of the environment, and thus increasing terrestrial weathering and runoff. If
this were the case, all river-borne elements would increase together, including the inert
(low residence time) elements such as Zr and Al. Our normalizations to Zr and Al (see
methods) should account for this possible extra runoff. In addition, if aluminum levels
in seawater had varied with time, this variation would have been reflected in the plots
of major elements. This is not the case.
88
Appendix 12: Figures comparing Metal Fluxes
Seawater Flux
3.E+11
2.E+11
Flux
2.E+11
1.E+11
5.E+10
0.E+00
Sc V Cr Co Ni Cu Zn As Se Sr Mo Ag Cd In Sn Sb Cs Ba W Re Au Tl Pb Bi
Element
Marine Plankton Composition
Mean Abundance (ppm dry weight)
90
80
70
60
50
40
30
20
10
0
Sc V Cr Co Ni Cu Zn As Se Sr Mo Ag Cd In Sn Sb Cs Ba W Re Au Tl Pb Bi
Element
Figure A2. Seawater flux and planktonic composition. Seawater flux (element in
ocean (g)/ residence time (yr) data developed using information from Johnson (2005).
Some of the residence times were calculated using riverine input, others by
accumulation rate in sediment, and through other means. Marine plankton (entire
organism) chemical composition (no data for elements Sr, In, Sn, W, Re and Au) from
Brumsack (1989).
89
Seafloor Spreading Ridge Hydrothermal Flux
5.00E+08
4.00E+08
Flux (g/yr)
3.00E+08
2.00E+08
1.00E+08
0.00E+00
Sc V Cr Co Ni Cu Zn As Se Sr Mo Ag Cd In Sn Sb Cs Ba W Re Au Tl Pb Bi
-1.00E+08
-2.00E+08
Element
Degassing Flux
1.00E+09
9.00E+08
8.00E+08
Flux (g/yr)
7.00E+08
6.00E+08
5.00E+08
4.00E+08
3.00E+08
2.00E+08
1.00E+08
0.00E+00
Sc V Cr Co Ni Cu Zn As Se Sr Mo Ag Cd In Sn Sb Cs Ba W Re Au Tl Pb Bi
Element
Figure A3. Hydrothermal and degassing fluxes. Data from Rubin (1997). Degassing
flux calculated using parameters developed from known subaerial volcanic production
and emanation coefficients.
90
Site 167 Trace Element Abundance Anomalies, 890 mbsf
Anomaly (peak/background)
140
120
100
80
60
40
20
0
Sc V Cr Co Ni Cu Zn As Se Sr Mo Ag Cd In Sn Sb Cs Ba W Re Au Tl Pb Bi
Element
Site 167 Trace Element Abundance Anomalies, 920 mbsf
Anomaly (peak/background)
140
120
100
80
60
40
20
0
Sc V Cr Co Ni Cu Zn As Se Sr Mo Ag Cd In Sn Sb Cs Ba W Re Au Tl Pb Bi
Element
Figure A4.Trace element abundance anomalies found in Deep Sea Drilling Project
Site 167 during this study.
91
Site 463 Trace Element Abundance Anomalies, 610 mbsf
Anomaly (peak/background)
140
120
100
80
60
40
20
0
Sc V Cr Co Ni Cu Zn As Se Sr Mo Ag Cd In Sn Sb Cs Ba W Re Au Tl Pb Bi
Element
Site 463 Trace Element Abundance Anomalies, 620 mbsf
Anomaly (peak/background)
140
120
100
80
60
40
20
0
Sc V Cr Co Ni Cu Zn As Se Sr Mo Ag Cd In Sn Sb Cs Ba W Re Au Tl Pb Bi
Element
Figure A5. Trace element abundance anomalies found in Deep Sea Drilling Project
Site 463 during this study.
92
Appendix 2. Deep Sea Drilling Project Site 167 and Site
463 normalized element abundances.
93
Site 167 Minor Element Data
Depth (mbsf)
Sc/Zr
V/Zr
Cr/Zr
Co/Zr
Ni/Zr
870.29
870.29
870.48
870.64
870.82
870.99
871.21
871.50
871.50
871.71
871.91
872.10
872.31
872.52
872.52
872.70
873.00
873.22
873.42
873.60
873.79
874.00
874.20
874.40
874.60
874.80
875.00
875.21
875.40
875.60
875.81
875.90
879.88
879.88
880.08
880.28
880.50
880.71
880.89
881.11
881.28
881.50
881.69
881.87
882.11
882.28
23.94
23.94
42.50
27.75
23.13
28.63
50.00
51.82
38.13
30.54
25.82
35.79
23.33
22.78
22.26
24.69
21.83
85.00
21.53
29.20
31.29
25.74
23.03
24.63
19.91
30.32
75.00
40.27
30.50
28.65
29.58
25.63
35.44
25.91
133.00
32.13
43.20
242.00
34.60
81.50
83.75
120.50
206.00
211.00
138.00
83.25
63.53
58.26
52.00
65.11
61.87
54.43
98.33
71.64
49.87
42.67
53.55
52.58
61.02
66.27
59.92
59.76
59.25
232.80
66.73
52.00
52.64
81.74
32.38
76.75
54.41
87.53
227.20
107.18
135.65
92.30
66.58
82.63
205.78
56.12
756.00
53.67
107.80
842.00
83.40
407.75
297.00
428.00
454.00
389.00
663.00
155.75
31.22
32.94
82.00
36.54
33.35
29.60
104.11
72.73
51.07
48.79
31.77
37.29
30.40
29.78
30.54
30.38
28.07
136.20
28.16
44.13
41.93
36.87
25.90
34.05
28.20
39.21
124.40
54.91
48.90
42.83
46.05
40.48
132.11
41.53
408.00
133.13
84.90
553.00
46.60
239.25
159.25
274.50
571.00
445.00
409.00
149.25
103.8
114.5
164.5
161.4
136.9
226.8
305.8
253.8
183.7
121.5
144.9
185.0
196.9
177.1
174.8
182.2
164.7
835.8
145.2
144.8
153.6
285.6
33.8
112.1
94.7
134.7
577.4
279.2
258.9
235.8
225.9
181.0
440.3
135.0
2265.0
272.2
481.8
5685.0
382.5
1678.0
1755.0
3240.5
5589.0
6582.0
4276.5
1749.8
105.8
105.6
120.5
127.8
102.6
108.2
191.1
148.9
100.6
94.7
110.3
98.5
104.8
99.7
101.7
102.8
98.4
342.0
81.0
77.9
74.4
110.9
24.0
73.0
70.2
71.7
167.8
80.6
80.8
79.0
79.8
79.9
248.8
78.7
778.0
80.3
152.1
814.0
90.9
495.8
315.8
453.0
540.0
461.0
723.5
231.8
94
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Sc/Zr
V/Zr
Cr/Zr
Co/Zr
Ni/Zr
882.50
882.70
882.88
883.10
882.70
882.88
883.10
883.28
883.28
883.50
883.70
883.91
884.01
884.30
884.51
884.71
884.89
885.08
885.08
885.26
885.58
885.58
885.80
885.97
886.18
886.29
888.36
888.57
888.75
888.94
889.16
889.36
889.61
889.80
889.80
889.99
890.20
890.40
890.58
890.79
891.08
891.30
891.49
891.69
891.69
891.93
37.91
34.33
65.20
32.46
34.33
65.20
32.46
26.42
88.40
27.14
43.56
91.67
144.50
20.33
234.00
40.91
341.00
18.84
20.67
50.67
24.38
47.25
86.00
84.25
44.44
242.00
317.00
483.00
93.67
282.00
139.33
49.27
35.68
29.25
32.67
25.58
127.50
27.38
432.00
237.00
91.00
122.33
258.00
20.11
20.36
31.63
68.18
50.93
137.00
58.92
50.93
137.00
58.92
57.16
189.80
56.55
117.78
287.33
545.50
52.11
567.00
75.09
1076.00
51.53
50.56
181.25
49.95
123.50
209.33
322.00
88.00
441.50
377.00
951.00
340.33
1075.00
448.33
604.55
178.32
103.25
108.33
84.39
661.50
103.14
1677.00
2038.00
987.00
510.33
1861.00
102.84
87.43
249.93
58.09
45.67
123.60
47.92
45.67
123.60
47.92
45.26
153.20
49.95
87.78
233.33
393.00
35.98
498.00
56.64
808.00
38.92
41.22
121.83
39.62
98.50
192.33
234.25
74.44
353.00
373.00
726.00
278.67
893.00
171.33
142.45
63.42
50.38
55.53
42.55
340.50
44.57
706.00
634.00
314.67
312.33
746.00
38.21
34.82
80.72
590.4
311.4
1295.8
450.6
311.4
1295.8
450.6
308.6
1528.0
297.3
694.4
2426.3
4957.5
233.5
8125.0
709.4
9585.0
263.7
265.3
814.5
349.2
884.8
2250.3
2138.3
841.2
6340.0
15030.0
19490.0
5363.3
12660.0
5066.7
1584.5
724.7
609.4
582.3
317.0
4534.0
458.4
13140.0
9982.0
3790.0
4146.7
11800.0
268.7
200.3
274.6
98.3
98.9
192.8
80.0
98.9
192.8
80.0
96.2
300.2
81.0
149.4
369.0
683.5
69.7
732.0
103.7
1306.0
67.7
69.7
264.2
67.0
165.6
296.3
408.5
126.9
541.5
549.0
1444.0
528.0
1445.0
287.7
256.7
127.1
80.8
94.7
75.2
556.0
74.0
1245.0
1088.0
568.3
591.3
1598.0
48.1
45.2
90.1
95
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Sc/Zr
V/Zr
Cr/Zr
Co/Zr
Ni/Zr
892.11
892.28
892.50
892.69
898.22
898.43
898.62
898.82
899.01
899.23
899.23
899.40
899.61
899.81
900.02
900.22
900.42
900.62
900.79
901.01
908.17
908.17
908.37
908.61
908.81
909.00
909.22
909.40
909.60
909.80
910.03
910.21
910.42
910.42
910.60
911.03
911.21
911.40
911.59
911.80
912.01
912.23
912.40
912.40
912.60
912.81
283.00
64.77
81.84
72.65
34.53
48.16
49.44
30.21
40.03
41.26
40.85
41.25
40.54
36.48
29.66
42.36
39.42
46.50
46.70
44.32
16.00
16.28
16.24
18.35
18.60
13.33
21.31
17.64
23.86
360.00
24.33
23.50
22.93
104.00
60.25
24.33
128.00
36.71
25.50
48.67
178.00
18.30
20.31
208.00
116.00
100.00
1743.00
337.23
515.78
361.63
161.11
234.08
231.60
196.64
248.17
314.75
289.02
246.23
284.33
235.36
294.11
308.18
300.31
406.92
313.48
323.51
45.97
43.24
47.00
74.77
47.88
49.48
52.50
58.24
99.79
997.00
84.00
68.08
62.36
409.00
195.25
67.80
450.00
101.00
85.36
232.00
645.00
45.78
44.63
592.00
348.50
375.00
777.00
243.88
343.56
646.33
187.19
238.16
348.20
226.93
908.87
966.39
925.74
784.06
560.60
466.31
952.68
642.12
578.91
564.42
579.86
437.03
40.97
42.45
55.76
43.50
41.32
34.73
58.13
49.88
52.57
680.00
57.83
58.17
51.14
359.00
206.00
63.93
434.00
115.57
65.57
207.67
754.00
45.78
48.75
693.00
378.50
411.50
9395.0
430.0
410.7
427.1
103.4
150.0
172.9
247.6
163.5
180.2
182.0
160.9
158.5
121.2
210.7
180.2
162.3
226.7
160.4
162.6
58.1
62.3
71.5
68.0
66.2
52.5
84.8
62.0
90.8
2548.0
228.3
167.1
132.6
1094.0
679.0
229.3
1780.5
506.7
243.5
702.0
3996.0
165.5
181.3
3352.0
2177.5
2163.0
713.0
78.1
114.4
147.2
61.6
72.3
114.3
53.8
140.4
182.5
180.7
135.5
125.8
81.1
194.5
146.1
121.8
137.2
100.8
109.0
37.4
36.3
48.7
44.3
45.0
45.6
49.3
47.4
54.9
696.0
68.8
65.7
61.1
419.5
251.3
81.6
527.5
131.0
75.2
265.7
860.0
61.5
58.0
851.0
522.5
512.0
96
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Sc/Zr
V/Zr
Cr/Zr
Co/Zr
Ni/Zr
912.90
917.35
917.84
918.35
918.83
919.36
919.36
919.84
920.33
920.86
921.35
921.85
922.34
922.83
923.33
925.10
925.21
925.31
925.31
925.41
925.50
925.70
925.80
925.90
926.10
926.30
926.71
926.80
927.00
927.20
927.39
927.61
927.80
928.10
928.30
928.50
928.50
928.71
928.90
929.10
929.10
929.10
929.30
929.30
929.60
929.80
110.00
50.60
67.33
235.00
105.00
25.18
23.29
20.39
15.73
16.54
183.00
27.00
17.15
44.67
14.53
20.47
16.83
19.00
18.59
83.67
21.62
21.06
48.83
20.15
37.40
23.89
23.64
30.14
14.10
17.50
19.90
39.25
25.50
62.00
93.75
42.50
24.10
24.00
23.31
20.00
21.64
21.36
13.75
13.57
21.95
18.80
463.50
206.00
372.67
929.00
436.00
48.45
44.50
93.78
63.95
51.08
641.00
107.69
42.25
131.67
70.69
50.67
50.42
53.13
49.53
62.33
60.38
52.94
150.00
52.46
64.20
55.89
69.00
80.43
51.90
48.41
58.00
199.25
97.90
320.25
198.25
193.00
63.90
58.20
58.62
48.27
55.07
52.29
52.62
47.65
51.89
66.80
451.50
176.20
330.33
826.00
403.50
57.55
51.71
105.83
39.73
42.77
615.00
76.92
44.60
123.50
45.19
57.73
48.38
77.20
52.12
714.67
63.08
58.00
163.00
66.23
134.80
126.89
69.64
112.86
48.21
55.27
55.48
121.38
75.10
229.00
1556.50
214.00
79.40
88.60
76.85
59.53
66.93
62.07
41.52
42.28
57.11
60.73
2243.0
714.4
1394.3
4877.0
2410.5
340.6
231.0
187.7
111.1
136.5
3003.0
269.7
156.2
501.3
122.4
70.3
84.0
51.7
57.1
347.3
92.5
101.9
274.3
115.8
237.2
96.1
93.4
175.1
60.0
126.0
136.2
290.0
107.3
648.0
348.3
331.5
129.8
142.6
104.5
102.5
143.0
127.6
58.6
61.0
97.7
91.2
549.5
229.4
422.3
997.0
475.0
69.0
63.9
69.3
50.4
54.4
717.0
81.8
51.3
122.5
46.9
118.5
80.8
542.9
98.6
330.3
127.6
106.4
298.8
126.3
295.2
138.1
162.4
203.3
71.3
90.5
83.1
215.1
153.0
436.8
221.0
371.5
146.2
147.2
129.5
113.0
126.9
119.4
55.3
55.4
87.5
128.1
97
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Sc/Zr
V/Zr
Cr/Zr
Co/Zr
Ni/Zr
929.80
930.01
930.21
930.40
930.60
930.80
935.70
935.91
936.10
936.30
936.61
936.61
936.61
936.79
937.00
937.40
937.60
937.80
938.10
938.30
938.50
938.71
938.71
938.89
939.11
939.30
939.59
939.80
940.01
940.19
940.60
940.79
940.90
19.79
13.84
28.00
27.93
30.86
30.63
22.73
14.31
11.55
19.69
12.25
12.59
12.13
25.50
26.11
13.70
15.11
24.77
18.18
38.00
15.41
19.85
23.36
14.35
23.33
34.33
31.86
18.09
22.64
26.67
58.67
15.13
15.46
68.00
65.73
109.29
120.50
68.71
58.88
53.45
46.94
47.30
63.69
70.02
66.94
67.61
147.07
179.78
94.00
71.51
132.54
50.27
129.50
48.82
48.15
48.36
46.84
59.50
77.17
63.29
49.70
61.00
59.44
94.67
54.48
60.49
65.36
45.11
98.71
73.64
114.57
101.63
76.91
43.63
40.29
79.54
40.04
41.55
41.02
83.36
91.22
44.72
47.80
109.31
53.64
157.17
44.91
73.85
77.64
46.84
84.00
111.50
94.43
58.57
87.18
87.33
204.33
48.29
50.78
91.7
54.7
133.0
196.0
193.7
169.0
133.5
70.6
62.4
75.2
72.9
69.9
72.4
186.1
169.3
61.9
59.0
213.3
81.5
299.3
78.1
103.7
118.2
84.3
126.7
151.2
125.3
89.1
115.8
147.4
665.7
74.0
78.6
115.4
61.4
202.1
111.8
197.9
169.8
147.5
55.0
50.6
105.6
60.5
54.6
54.2
131.6
174.6
60.3
66.1
166.5
84.0
259.0
67.4
220.5
121.8
72.7
120.8
232.8
211.9
78.9
155.1
323.4
549.3
68.5
70.6
98
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Cu/Zr
Zn/Zr
Se/Zr
As/Zr
Se/Zr
870.3
870.3
870.5
870.6
870.8
871.0
871.2
871.5
871.5
871.7
871.9
872.1
872.3
872.5
872.5
872.7
873.0
873.2
873.4
873.6
873.8
874.0
874.2
874.4
874.6
874.8
875.0
875.2
875.4
875.6
875.8
875.9
879.9
879.9
880.1
880.3
880.5
880.7
880.9
881.1
881.3
881.5
881.7
881.9
882.1
882.3
909
917
966
1028
920
896
1208
1085
751
713
825
737
808
789
805
803
786
2534
594
521
524
696
193
413
371
426
925
512
398
430
319
379
1394
410
3598
319
933
4352
493
2960
1817
2847
2655
2597
5570
1077
1.33
1.18
1.00
1.29
1.13
1.10
1.89
2.18
1.13
1.08
1.05
0.96
1.07
1.09
1.26
1.02
1.08
3.20
0.87
0.80
0.71
1.06
0.52
0.95
0.81
1.00
2.80
1.18
1.10
1.09
0.95
1.26
3.89
1.06
9.50
1.00
2.30
12.00
1.13
6.25
4.00
6.50
12.00
8.00
10.00
3.00
1601
1539
1388
1726
1035
1092
2415
2005
1413
1148
1206
1172
1203
1200
1167
1169
1144
4356
1047
1170
977
1245
1013
1437
1387
1656
3933
1886
1343
1379
1232
912
3770
1879
12443
1347
2457
12420
1218
11025
4208
805
6255
3195
8438
3150
147.6
154.9
679.3
197.1
224.2
181.5
508.3
416.3
298.1
11.39
10.29
6.67
12.50
4.78
3.67
11.11
9.09
7.33
5.42
4.77
4.17
4.89
5.11
4.60
4.67
4.83
22.00
4.67
5.33
4.29
5.81
7.59
7.25
8.41
10.53
22.00
12.73
7.50
7.39
7.37
6.90
17.78
13.53
75.00
10.67
14.00
90.00
8.67
37.50
32.50
6.21
40.00
50.00
35.00
20.00
131.9
209.6
137.6
136.9
132.1
137.3
116.0
978.2
141.0
315.4
330.1
199.3
103.0
111.8
80.0
211.1
793.6
373.6
244.1
199.4
224.2
173.0
583.0
163.2
2287.5
272.4
447.8
4233.0
302.1
1285.5
1140.5
2242.0
4218.0
3955.0
2355.5
1133.3
99
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Cu/Zr
Zn/Zr
Se/Zr
As/Zr
Se/Zr
882.5
882.7
882.9
883.1
882.7
882.9
883.1
883.3
883.3
883.5
883.7
883.9
884.0
884.3
884.5
884.7
884.9
885.1
885.1
885.3
885.6
885.6
885.8
886.0
886.2
886.3
888.4
888.6
888.8
888.9
889.2
889.4
889.6
889.8
889.8
890.0
890.2
890.4
890.6
890.8
891.1
891.3
891.5
891.7
891.7
891.9
507
718
1056
489
718
1056
489
366
1293
513
928
2748
5595
473
4917
694
10650
434
441
2418
330
818
1219
4250
632
2747
2674
9583
2957
5852
600
574
362
180
209
184
950
124
1885
2193
1239
2674
1630
274
208
728
1.36
1.48
2.60
1.08
1.48
2.60
1.08
1.21
3.80
1.14
2.11
5.00
10.00
0.96
11.00
1.36
19.00
0.89
0.92
3.33
1.00
2.13
4.00
5.25
1.44
8.00
6.00
15.00
6.00
19.00
3.33
3.45
1.79
1.38
1.20
1.03
6.50
1.05
15.00
14.00
7.33
7.33
15.00
1.00
0.75
0.97
1301
977
3150
1284
977
3150
1284
1149
600
1381
1845
3210
5085
948
7380
1743
6165
894
790
2768
911
2109
2895
4894
1630
1845
0
5625
847
8865
2205
3514
2667
1547
1767
1365
9180
1080
720
14310
6345
5985
15885
1155
1025
278
413.9
188.9
850.0
350.8
188.9
850.0
350.8
252.3
926.6
234.2
533.6
1446.3
2283.5
135.1
4388.0
448.7
4939.0
136.3
156.9
449.9
216.9
603.9
1494.0
1291.5
496.3
2266.0
4154.0
4752.0
1667.3
4914.0
1352.7
375.5
227.8
253.3
265.7
125.4
1982.5
190.0
4035.0
3686.0
1334.7
1327.3
3824.0
105.1
95.3
38.5
9.09
3.70
28.00
9.23
3.70
28.00
9.23
4.74
4.72
7.27
7.78
13.33
0.00
3.91
50.00
12.73
0.00
3.95
5.17
13.33
6.19
10.00
23.33
20.00
8.89
0.00
0.00
0.00
7.50
10.00
13.33
8.18
9.47
6.25
6.00
3.03
20.00
3.81
6.90
40.00
20.00
16.67
70.00
5.00
4.32
0.36
100
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Cu/Zr
Zn/Zr
Se/Zr
As/Zr
Se/Zr
892.1
892.3
892.5
892.7
898.2
898.4
898.6
898.8
899.0
899.2
899.2
899.4
899.6
899.8
900.0
900.2
900.4
900.6
900.8
901.0
908.2
908.2
908.4
908.6
908.8
909.0
909.2
909.4
909.6
909.8
910.0
910.2
910.4
910.4
910.6
911.0
911.2
911.4
911.6
911.8
912.0
912.2
912.4
912.4
912.6
912.8
1945
2029
648
768
883
665
820
316
1328
634
586
568
548
617
714
651
983
713
725
735
359
430
572
286
300
4720
511
421
209
2877
207
255
247
1819
1190
658
3620
538
374
943
2754
326
258
4482
3271
3005
13.00
1.31
1.93
1.71
0.86
0.92
1.24
0.57
0.94
1.11
1.05
0.90
0.91
0.76
1.29
1.11
0.92
1.17
1.07
1.07
0.74
0.69
0.84
0.81
0.72
0.99
0.88
0.88
1.00
12.00
1.25
1.17
1.14
7.00
4.00
1.33
9.00
2.14
1.29
4.50
14.00
1.09
1.13
14.00
9.50
10.00
13275
1848
615
1772
1620
1437
2141
1060
1104
1169
815
735
658
1124
834
893
929
852
864
1230
1221
1357
1374
1273
1121
1266
1253
1392
11790
1316
1245
1244
7718
4928
0
8618
2385
1437
4988
13770
1186
1223
12645
7245
8078
9923
3700.0
145.8
91.6
75.3
91.8
97.2
98.7
336.6
65.2
76.5
76.9
67.5
69.7
61.4
81.0
71.7
69.0
81.5
66.2
63.2
122.1
142.3
173.2
169.8
170.5
75.0
257.4
170.3
306.6
4110.0
358.2
358.8
306.4
2204.0
1093.5
291.8
2233.0
599.6
308.4
741.8
4308.0
199.4
284.6
4378.0
2240.0
2173.5
40.00
3.85
-0.67
0.35
0.82
1.20
0.71
0.56
0.98
0.98
1.01
0.90
1.07
1.25
0.91
1.25
1.35
1.01
0.95
3.82
3.45
2.80
3.46
3.20
1.79
4.38
2.80
4.29
0.00
4.17
3.33
4.29
20.00
15.00
0.00
5.00
8.57
5.00
8.33
30.00
3.91
3.75
20.00
10.00
25.00
20.00
101
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Cu/Zr
Zn/Zr
Se/Zr
As/Zr
Se/Zr
912.9
917.4
917.8
918.4
918.8
919.4
919.4
919.8
920.3
920.9
921.4
921.9
922.3
922.8
923.3
925.1
925.2
925.3
925.3
925.4
925.5
925.7
925.8
925.9
926.1
926.3
926.7
926.8
927.0
927.2
927.4
927.6
927.8
928.1
928.3
928.5
928.5
928.7
928.9
929.1
929.1
929.1
929.3
929.3
929.6
929.8
2393
891
2161
3591
1344
282
270
190
233
287
2949
319
332
455
259
272
266
311
310
1104
383
327
786
293
832
592
467
574
246
411
370
581
781
941
874
1318
403
1910
339
369
500
382
288
283
832
977
9.50
5.60
8.00
17.00
10.00
1.09
1.07
1.06
1.03
1.12
12.00
1.77
1.10
2.50
1.00
1.20
1.04
1.60
1.24
2.67
1.62
1.44
3.50
1.38
3.00
1.11
1.36
1.71
0.97
1.14
1.29
2.25
1.40
4.75
0.75
5.00
1.30
1.30
1.31
1.13
1.64
1.14
1.02
0.91
1.21
1.80
4140
7440
14490
7470
1096
1093
1365
1046
1083
8280
1637
918
2093
982
1321
1316
1713
1438
5007
1512
1306
3813
1291
838
1927
1408
1266
1321
1180
1294
2338
1427
4343
14233
3023
1162
1236
1482
1115
1280
1174
1167
1127
1364
1053
1384
2248.5
925.2
1490.0
4335.0
2202.5
398.5
332.1
281.2
153.4
198.7
4634.0
387.4
259.9
765.2
166.6
278.2
201.1
265.7
243.2
1456.3
319.7
257.0
728.2
313.2
761.2
509.6
326.2
559.6
173.7
202.6
266.2
521.6
395.7
1073.3
3065.0
954.5
372.5
369.4
301.9
273.0
294.1
287.8
97.8
104.4
242.6
262.3
14.00
13.33
30.00
15.00
5.45
4.29
3.33
2.70
2.69
0.00
5.38
3.50
5.00
1.25
19.47
15.04
25.47
20.24
0.00
20.38
15.81
24.00
6.69
10.40
6.22
15.09
15.00
7.97
16.00
11.05
49.00
24.60
49.00
0.00
3.25
13.70
14.40
19.38
14.33
13.36
14.07
12.75
10.72
12.58
15.20
16.00
102
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Cu/Zr
Zn/Zr
Se/Zr
As/Zr
Se/Zr
929.8
930.0
930.2
930.4
930.6
930.8
935.7
935.9
936.1
936.3
936.6
936.6
936.6
936.8
937.0
937.4
937.6
937.8
938.1
938.3
938.5
938.7
938.7
938.9
939.1
939.3
939.6
939.8
940.0
940.2
940.6
940.8
940.9
1086
345
470
378
689
402
605
423
344
619
458
425
450
666
656
402
353
861
360
901
408
544
602
328
545
678
610
513
408
502
925
388
407
1.79
0.89
2.00
1.14
2.29
2.63
1.82
0.82
0.79
0.92
1.08
0.82
0.87
1.86
2.11
1.09
0.91
2.15
0.91
2.50
0.88
1.54
1.36
0.84
1.08
2.83
2.71
1.13
1.27
2.56
5.67
0.84
1.00
1191
1118
1137
1057
1093
1015
1159
1165
1441
1085
1033
1037
1475
1096
0
1207
2503
1162
2258
1177
1031
1054
1092
1251
1058
1128
1119
976
768
0
1190
1345
0
284.4
133.7
543.0
321.9
541.0
478.8
364.4
106.8
85.2
361.8
110.4
104.7
101.2
293.1
440.9
119.4
134.4
371.6
202.5
693.3
146.1
333.0
366.8
148.0
372.3
632.5
562.9
207.9
345.0
441.2
1270.7
151.0
142.5
7.27
11.00
2.14
9.57
8.25
11.45
12.63
7.53
10.69
8.94
10.10
8.07
17.36
20.33
0.00
13.26
13.15
18.00
10.50
16.85
10.69
8.73
8.74
10.00
25.33
31.00
2.87
11.18
9.56
0.00
17.52
12.76
0.00
103
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Rb/Zr
Sr/Zr
Y/Zr
Mo/Zr
Ag/Zr
870.29
870.29
870.48
870.64
870.82
870.99
871.21
871.50
871.50
871.71
871.91
872.10
872.31
872.52
872.52
872.70
873.00
873.22
873.42
873.60
873.79
874.00
874.20
874.40
874.60
874.80
875.00
875.21
875.40
875.60
875.81
875.90
879.88
879.88
880.08
880.28
880.50
880.71
880.89
881.11
881.28
881.50
881.69
881.87
882.11
882.28
271.28
280.41
502.83
296.14
299.70
279.43
740.00
558.55
396.73
338.96
335.23
349.88
316.22
301.33
310.40
314.22
304.83
1307.80
306.89
396.00
372.93
363.55
323.62
414.25
283.33
564.74
1744.00
792.55
607.50
507.39
578.42
494.81
1371.11
430.29
5520.00
618.07
1036.00
8209.00
635.07
3062.50
2301.00
4076.50
7212.00
6715.00
5430.00
1991.25
139.0
136.0
203.0
149.5
160.6
100.7
327.2
213.4
152.0
121.7
62.8
71.3
96.6
103.3
100.5
98.7
90.8
631.8
96.8
171.1
172.1
127.8
80.6
105.8
72.8
143.0
583.4
308.5
136.5
112.7
178.5
131.1
218.4
100.5
1533.5
207.7
280.8
2090.0
201.6
698.5
655.8
1197.0
2056.0
1701.0
1040.0
676.3
2422
2282
2332
2714
1232
752
1882
2071
1567
1319
977
1026
1024
1110
1039
1030
1040
4052
1200
1529
1243
1526
865
934
990
1281
3480
2003
1233
1197
1268
1053
1581
1614
4697
1728
1833
6627
1459
3098
5098
2979
7640
5800
2419
4943
1941
1840
1493
2644
2296
2327
1133
1323
890
656
1183
1114
1805
1814
1834
1782
1708
5090
1176
808
794
1754
411
1355
1398
2501
19956
3568
4626
2851
1008
1470
2182
549
12345
1369
2185
12950
1575
9630
4008
6745
5445
26130
6345
3115
692
697
7017
1004
1109
3083
2944
3236
2447
1683
1275
2200
993
887
818
896
817
3500
816
1073
1064
868
1052
1218
1139
1174
2780
1491
1485
1683
1558
1300
1733
1182
5650
1473
1860
16400
1767
4225
5000
1610
17900
21500
10450
4900
104
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Rb/Zr
Sr/Zr
Y/Zr
Mo/Zr
Ag/Zr
882.50
882.70
882.88
883.10
882.70
882.88
883.10
883.28
883.28
883.50
883.70
883.91
884.01
884.30
884.51
884.71
884.89
885.08
885.08
885.26
885.58
885.58
885.80
885.97
886.18
886.29
888.36
888.57
888.75
888.94
889.16
889.36
889.61
889.80
889.80
889.99
890.20
890.40
890.58
890.79
891.08
891.30
891.49
891.69
891.69
891.93
812.91
450.00
1724.60
696.46
450.00
1724.60
696.46
540.00
2054.00
535.45
1200.00
3223.33
5490.00
419.13
7907.00
845.45
11290.00
410.26
438.06
1412.50
500.00
1346.25
2773.33
3095.00
1079.00
5150.00
7010.00
10410.00
3650.00
11630.00
2644.33
1656.36
826.84
654.38
742.00
496.67
4890.50
577.14
10440.00
9766.00
4076.67
4523.33
11400.00
525.00
491.82
107.55
216.6
111.8
512.4
202.4
111.8
512.4
202.4
115.0
357.6
115.3
259.3
576.0
841.0
58.9
1861.0
241.5
1279.0
61.3
62.7
172.3
115.0
255.5
621.3
503.5
242.7
547.0
1009.0
1036.0
584.0
1556.0
471.7
165.9
151.9
144.3
159.8
75.2
973.0
91.8
1262.0
1800.0
630.7
740.7
2278.0
72.0
67.9
17.8
1910
932
4028
1795
932
4028
1795
1023
1289
1408
2026
1679
914
639
4628
2099
1370
632
624
669
987
1831
2223
2180
1950
1008
1519
1153
1070
1363
2163
399
1001
1038
1187
561
2772
717
1212
2589
1130
945
2683
636
626
85
732
622
1203
475
622
1203
475
665
1436
449
934
3262
3977
709
6162
568
9663
352
338
1091
1724
3938
1811
2155
783
3728
8092
16920
3024
6953
1744
1299
2843
1049
842
488
5120
1673
9173
190100
2783
3903
10230
900
540
512
2000
1459
3660
1877
1459
3660
1877
1916
1664
1786
2622
7900
14050
1650
25000
2991
27800
1400
1469
2408
1771
2400
5700
5125
2411
16850
33900
47200
2014
29800
11267
4327
2263
1963
1820
1524
9800
1814
1824
23400
8300
10033
25300
1571
1377
1287
105
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Rb/Zr
Sr/Zr
Y/Zr
Mo/Zr
Ag/Zr
892.11
892.28
892.50
892.69
898.22
898.43
898.62
898.82
899.01
899.23
899.23
899.40
899.61
899.81
900.02
900.22
900.42
900.62
900.79
901.01
908.17
908.17
908.37
908.61
908.81
909.00
909.22
909.40
909.60
909.80
910.03
910.21
910.42
910.42
910.60
911.03
911.21
911.40
911.59
911.80
912.01
912.23
912.40
912.40
912.60
912.81
11950.00
785.38
186.47
196.67
355.96
317.76
364.20
536.36
161.97
187.21
186.56
112.33
103.37
86.98
159.27
108.91
135.42
164.02
144.42
146.89
402.94
441.03
483.20
471.54
454.80
420.00
486.31
464.00
494.43
6294.00
518.58
533.42
493.50
3593.00
2074.50
636.80
4584.50
1012.29
609.93
2213.33
6745.00
476.09
444.44
6867.00
3897.00
3737.50
1813.0
355.5
65.4
71.6
87.2
137.8
180.8
53.5
66.0
129.5
120.9
84.7
96.6
73.3
63.6
53.8
75.3
70.0
43.2
43.0
109.3
106.8
107.3
147.8
144.2
33.3
228.9
152.3
253.9
1559.0
218.9
229.4
229.1
1502.0
784.3
216.5
1365.5
459.4
244.9
478.0
2212.0
157.2
209.2
2433.0
1206.5
1529.0
2306
618
142
157
259
300
292
420
159
261
247
242
230
220
254
236
244
246
257
249
958
937
777
991
992
477
1395
971
1566
1787
1969
1698
1582
3707
3353
1582
1470
2176
1697
1414
2924
1218
1480
3518
1790
3672
13130
1795
605
442
210
240
196
572
193
569
196
276
184
185
5298
192
191
196
285
262
1434
746
356
413
346
240
499
1719
520
3998
650
554
1347
2028
3268
379
306500
5144
6676
5552
11100
486
1301
6122
5250
3576
29100
2546
2262
909
1422
1692
18079
1439
1592
1648
1526
1675
1569
2027
1520
1534
1773
1430
1278
1274
986
1408
885
900
1049
925
656
629
11700
1667
900
850
2650
2400
0
7600
2686
1279
2617
13300
1165
1200
10800
9850
7750
8250
106
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Rb/Zr
Sr/Zr
Y/Zr
Mo/Zr
Ag/Zr
912.90
917.35
917.84
918.35
918.83
919.36
919.36
919.84
920.33
920.86
921.35
921.85
922.34
922.83
923.33
925.10
925.21
925.31
925.31
925.41
925.50
925.70
925.80
925.90
926.10
926.30
926.71
926.80
927.00
927.20
927.39
927.61
927.80
928.10
928.30
928.50
928.50
928.71
928.90
929.10
929.10
929.10
929.30
929.30
929.60
929.80
4315.50
1829.40
3440.00
8481.00
3889.00
481.36
461.79
445.39
424.05
424.62
4923.00
707.77
415.05
1037.67
428.75
663.33
547.50
678.00
614.71
2067.00
744.54
662.50
1833.33
724.00
1417.60
921.44
797.91
1098.71
516.21
568.64
569.05
1263.75
862.60
2468.75
1421.50
2227.75
865.30
861.10
774.62
659.40
732.14
720.71
422.69
439.57
609.47
620.53
1531.5
821.4
1064.3
2571.0
1273.5
265.8
260.7
157.1
133.4
139.8
1727.0
224.8
166.7
367.2
78.1
164.6
119.9
172.2
161.0
153.3
188.8
146.0
385.5
142.9
317.0
120.1
172.9
257.3
75.5
138.7
105.5
458.1
292.6
758.5
91.5
374.0
184.8
190.9
213.0
165.5
187.2
179.3
67.0
63.8
129.4
146.5
3217
3754
1470
2411
2350
1912
1904
1545
889
1054
6618
2065
1241
2948
668
1901
1289
1903
1751
1705
2079
1614
2717
1485
3700
1407
1806
2850
851
1411
1053
4175
2783
6890
1588
1915
1897
2037
2325
1812
2116
1954
908
858
1333
1733
2704
1622
6000
11410
3958
5172
477
1548
345
326
4085
766
479
1455
373
384
415
967
397
1476
538
419
993
423
2094
745
428
706
332
707
587
1974
764
3190
2640
2868
716
564
439
801
1200
1054
448
470
768
439
3020
5133
21900
9850
1782
1179
1067
781
892
11700
1192
935
1533
722
1678
1743
1915
1664
4737
1701
1894
2922
1951
2752
2402
1816
2460
1299
2309
2247
3448
1524
4745
4283
2326
1629
2167
1798
1835
2141
1724
1614
1525
1861
1955
2655
107
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Rb/Zr
Sr/Zr
Y/Zr
Mo/Zr
Ag/Zr
929.80
930.01
930.21
930.40
930.60
930.80
935.70
935.91
936.10
936.30
936.61
936.61
936.61
936.79
937.00
937.40
937.60
937.80
938.10
938.30
938.50
938.71
938.71
938.89
939.11
939.30
939.59
939.80
940.01
940.19
940.60
940.79
940.90
710.00
483.24
1097.71
747.86
1105.71
992.75
821.18
456.12
426.82
748.31
427.50
423.53
421.30
832.14
910.00
452.56
506.86
1160.77
582.73
1756.67
501.18
682.85
793.82
501.94
741.83
1245.17
1122.57
567.83
833.91
901.44
2085.33
500.32
515.95
161.6
65.8
249.4
116.7
235.3
226.3
202.2
71.6
44.1
128.8
69.8
69.4
69.7
198.6
238.3
79.0
92.0
196.8
113.7
293.0
90.1
124.4
128.5
94.8
167.5
329.7
359.4
75.7
201.8
239.1
548.0
87.0
58.8
1858
863
2626
1245
2537
2249
2142
937
572
1368
761
738
746
1755
2557
1053
1151
1045
1424
1875
1273
1422
1401
988
1717
3602
3434
732
1885
2583
5930
1204
914
440
338
669
1000
712
633
1151
463
277
600
1560
386
411
1114
1468
392
355
894
477
1395
495
555
432
347
1099
904
871
316
1051
1373
3957
315
288
1385
1389
2429
3064
2395
1781
1590
1443
2638
1557
1478
1453
2599
2008
0
1327
1628
1402
2485
1523
1739
1755
1570
2458
1461
1554
7443
1723
2003
0
1532
1668
0
108
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Cd/Zr
In/Zr
Sn/Zr
Sb/Zr
Cs/Zr
870.29
870.29
870.48
870.64
870.82
870.99
871.21
871.50
871.50
871.71
871.91
872.10
872.31
872.52
872.52
872.70
873.00
873.22
873.42
873.60
873.79
874.00
874.20
874.40
874.60
874.80
875.00
875.21
875.40
875.60
875.81
875.90
879.88
879.88
880.08
880.28
880.50
880.71
880.89
881.11
881.28
881.50
881.69
881.87
882.11
882.28
10133
13959
54000
13314
18765
3040
40556
127364
25267
14067
4905
6583
5782
6609
6456
5676
6640
93280
6493
33667
21714
11542
4834
6135
3200
10737
48960
15709
11610
14096
14705
5110
22889
8282
147300
14347
37220
149800
20627
68500
61650
4566
293600
342400
301800
133000
25.58
26.97
151.67
32.39
38.35
29.50
94.67
79.91
59.00
36.54
19.80
36.96
19.31
18.89
17.12
19.87
14.52
187.60
19.82
61.00
68.00
30.10
37.52
25.93
14.81
53.37
208.20
94.27
51.95
43.91
52.47
37.63
117.44
31.85
545.50
75.27
115.10
1159.00
75.93
288.50
288.50
601.00
1144.00
1234.00
590.00
294.50
22100
22492
16304
22065
24827
23303
57886
43698
32717
26339
28895
25716
26924
26859
27502
28405
27598
100100
26917
27343
26696
27635
10075
24440
18464
25692
56745
24700
27934
23838
24358
9559
88219
26076
279825
21688
45825
230100
25415
146819
74019
9291
166400
122200
213850
51513
4583
4628
4625
5223
5498
6295
5750
5768
3460
3813
5185
5156
5827
5760
5778
6037
5788
16050
4153
2970
2904
6740
1283
3420
2737
3829
8970
3532
4800
3509
2700
1329
12983
3159
40650
2270
20145
33600
6560
45788
17700
1221
19500
10800
23850
9900
23.22
24.26
61.17
25.89
27.39
25.97
70.33
54.18
39.13
31.00
28.32
32.33
26.24
24.89
25.64
26.24
24.70
124.00
25.49
39.80
37.86
32.10
20.38
30.93
21.48
37.11
104.20
47.55
43.30
34.57
37.53
34.85
92.11
31.62
365.50
38.53
67.80
481.00
40.93
206.50
145.00
240.00
397.00
352.00
362.50
115.50
109
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Cd/Zr
In/Zr
Sn/Zr
Sb/Zr
Cs/Zr
882.50
882.70
882.88
883.10
882.70
882.88
883.10
883.28
883.28
883.50
883.70
883.91
884.01
884.30
884.51
884.71
884.89
885.08
885.08
885.26
885.58
885.58
885.80
885.97
886.18
886.29
888.36
888.57
888.75
888.94
889.16
889.36
889.61
889.80
889.80
889.99
890.20
890.40
890.58
890.79
891.08
891.30
891.49
891.69
891.69
891.93
33764
14015
364960
30538
14015
364960
30538
10537
4017
12345
28200
99400
184800
3622
300200
22182
168200
4747
4855
15000
10638
20575
86667
28950
26578
111000
232800
196400
4693
155000
52467
10655
5853
11088
15000
4267
80600
7448
5807
156200
40667
34600
102600
4121
2141
2374
108.55
43.22
229.20
88.85
43.22
229.20
88.85
61.63
245.60
54.23
132.11
415.00
639.00
27.15
1223.00
111.82
1253.00
34.00
36.81
109.42
60.86
168.13
453.67
335.25
147.89
708.00
1519.00
1503.00
482.33
1392.00
482.00
126.73
68.58
80.00
88.80
40.73
679.50
64.95
1375.00
1334.00
460.00
463.00
1364.00
35.32
31.52
10.39
40064
19512
48360
21725
19512
48360
21725
29951
7610
21657
42178
104217
198413
20779
195975
26768
470600
19859
9156
76538
21419
54722
81142
157788
33547
176475
169975
490100
10818
570050
82658
81280
40779
27666
31027
33613
143813
32160
10691
333125
156325
184817
402675
48878
62267
12645
3450
4861
8160
2815
4861
8160
2815
3213
1004
3143
5900
12050
23475
2876
25200
3477
41400
2582
1459
9025
4200
5100
8100
15113
3300
17925
12600
34950
1527
45900
7100
9586
5092
2888
3500
3114
15900
3279
1402
31800
17900
16500
37350
2554
2659
1347
49.36
29.48
106.20
43.00
29.48
106.20
43.00
35.00
135.20
36.36
78.00
200.33
356.50
31.09
457.00
53.27
717.00
27.58
31.36
96.75
31.10
84.00
162.33
206.75
65.33
315.00
376.00
654.00
224.00
742.00
147.67
109.73
57.00
39.56
45.93
32.82
289.00
36.62
627.00
577.00
252.00
290.00
712.00
34.55
33.86
3.60
110
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Cd/Zr
In/Zr
Sn/Zr
Sb/Zr
Cs/Zr
892.11
892.28
892.50
892.69
898.22
898.43
898.62
898.82
899.01
899.23
899.23
899.40
899.61
899.81
900.02
900.22
900.42
900.62
900.79
901.01
908.17
908.17
908.37
908.61
908.81
909.00
909.22
909.40
909.60
909.80
910.03
910.21
910.42
910.42
910.60
911.03
911.21
911.40
911.59
911.80
912.01
912.23
912.40
912.40
912.60
912.81
114400
1123
8316
165
2302
1504
614
2685
2439
2698
730
842
1371
696
173
925
977
530
595
7765
7186
7880
8746
8840
5898
16200
9152
17271
272400
27417
25483
17471
110800
50150
0
92600
41457
15443
19700
345200
11122
15188
302000
348100
174400
106000
1517.00
57.23
31.22
30.18
16.40
20.84
21.28
76.43
14.97
18.36
18.11
16.20
16.93
13.63
20.13
16.29
17.34
21.06
15.91
15.00
30.62
34.72
40.84
36.96
38.52
11.25
57.69
36.88
65.07
987.00
77.25
76.08
66.07
457.00
240.00
63.07
462.50
132.43
66.00
157.33
963.00
40.35
57.88
943.00
480.00
477.00
434525
19375
13253
21992
19036
21912
78627
12872
26032
16740
11992
12224
11534
13464
12478
14361
20919
16344
14441
30215
23557
24219
25338
25142
25164
25919
23517
37491
456625
41302
36454
39534
264225
131544
0
316225
78975
48657
142079
551850
37389
42311
815100
282750
364000
351163
43500
1696
1020
1547
1267
1200
16832
547
750
615
589
549
650
600
561
480
473
604
594
1725
1557
5526
1881
1722
4263
1538
1752
1543
17550
2650
1525
1864
11625
5888
#DIV/0!
14850
2507
1886
9800
20250
2374
1903
18150
13950
15150
12450
695.00
27.46
8.04
6.69
15.84
14.82
15.86
39.50
4.86
6.92
6.77
5.84
5.51
5.30
6.68
5.82
5.94
7.21
6.06
5.53
28.53
31.93
34.76
35.19
33.72
27.68
40.81
35.36
43.07
563.00
46.33
46.67
42.29
301.50
167.00
50.47
364.00
85.00
50.57
160.67
590.00
35.87
37.50
582.00
319.00
317.50
111
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Cd/Zr
In/Zr
Sn/Zr
Sb/Zr
Cs/Zr
912.90
917.35
917.84
918.35
918.83
919.36
919.36
919.84
920.33
920.86
921.35
921.85
922.34
922.83
923.33
925.10
925.21
925.31
925.31
925.41
925.50
925.70
925.80
925.90
926.10
926.30
926.71
926.80
927.00
927.20
927.39
927.61
927.80
928.10
928.30
928.50
928.50
928.71
928.90
929.10
929.10
929.10
929.30
929.30
929.60
929.80
52280
77800
231800
109400
25945
24571
13656
5470
13762
346800
69600
17440
106633
10488
17133
4867
11333
11529
6230
10738
13763
23350
17615
78200
65
15500
19286
2310
801818
693810
960375
12190
1685500
5035
49525
12000
10190
11200
36760
16064
19379
287308
221739
11126
15640
13421
483.50
192.00
317.00
981.00
501.50
90.64
68.21
55.44
25.92
37.12
1025.00
75.31
48.55
170.33
31.56
64.60
40.13
64.13
56.94
329.67
74.62
61.44
164.33
78.00
203.40
108.44
90.91
141.29
33.55
44.05
47.38
121.75
97.90
246.75
255.00
246.75
97.50
99.10
75.92
65.60
71.57
72.93
18.56
21.15
51.63
64.73
124540
225333
708175
359613
51645
59104
104939
36409
34925
0
128450
44769
68846
31413
17200
23542
14913
12600
85900
27762
19513
97917
13646
0
23356
17000
42114
21966
2236
2669
0
40150
0
0
170675
41750
29220
50231
0
4720
0
6881
5913
0
30627
20793
6810
11750
32550
14100
2059
2121
4350
2534
1863
17250
4223
1830
3125
2475
2751
2929
4885
2439
24453
2740
2566
8438
3222
3216
15256
2739
3806
4652
2253
8919
3399
2345
7458
54475
7748
2129
3081
2288
2087
2961
2364
2321
2110
6642
2429
2539
358.00
151.80
276.67
732.00
345.00
45.82
41.50
38.28
32.08
33.65
474.00
60.00
35.60
95.83
33.13
41.40
35.67
42.87
39.12
119.00
46.31
43.31
118.33
44.54
82.40
55.67
48.27
67.00
34.14
39.50
38.67
82.75
52.00
160.00
78.00
135.75
53.30
53.00
48.69
42.40
46.43
46.14
30.56
31.70
38.53
38.73
112
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Cd/Zr
In/Zr
Sn/Zr
Sb/Zr
Cs/Zr
929.80
930.01
930.21
930.40
930.60
930.80
935.70
935.91
936.10
936.30
936.61
936.61
936.61
936.79
937.00
937.40
937.60
937.80
938.10
938.30
938.50
938.71
938.71
938.89
939.11
939.30
939.59
939.80
940.01
940.19
940.60
940.79
940.90
2371
18429
6948
19500
22775
25845
148653
1612
3738
5242
8392
4135
920714
28167
0
5077
8977
11800
32500
12721
10746
9800
6990
32908
68000
22986
4604
17418
45700
0
5155
4592
0
69.50
26.05
140.29
70.93
141.71
125.88
92.27
19.29
14.52
74.85
20.04
19.08
18.69
69.50
119.67
22.79
29.91
74.15
44.59
162.67
28.62
75.31
89.09
31.55
82.33
164.17
141.57
42.96
89.82
109.89
331.33
31.35
25.95
16438
38186
0
72271
37713
0
6776
7132
14885
7867
5749
6231
1445
0
0
24109
37000
16595
0
5050
19715
39209
3448
0
32450
40871
22626
49164
0
0
17948
19873
0
3562
2659
9200
2773
3411
2563
2267
2105
9015
3121
2212
2348
3716
2821
0
3091
7474
2554
7387
2907
4975
4381
2382
5599
3590
3884
5965
3367
4863
0
2658
3438
0
45.07
33.24
65.43
52.00
66.86
60.38
49.82
33.10
29.71
46.15
28.85
28.94
29.20
56.36
55.56
31.72
34.91
72.69
37.91
113.50
35.09
41.46
48.09
33.06
45.58
74.33
67.57
37.13
50.73
54.33
125.33
33.39
31.84
113
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Ba/Zr
W/Zr
Re/Zr
Au/Zr
Hg/Zr
870.29
870.29
870.48
870.64
870.82
870.99
871.21
871.50
871.50
871.71
871.91
872.10
872.31
872.52
872.52
872.70
873.00
873.22
873.42
873.60
873.79
874.00
874.20
874.40
874.60
874.80
875.00
875.21
875.40
875.60
875.81
875.90
879.88
879.88
880.08
880.28
880.50
880.71
880.89
881.11
881.28
881.50
881.69
881.87
882.11
882.28
1829.4
1833.8
2191.7
1692.9
2275.7
1535.0
1730.0
1448.2
1052.0
681.3
960.5
480.4
916.7
914.7
932.2
948.2
878.5
2258.0
840.7
334.1
118.6
528.7
520.0
416.0
227.4
247.8
687.8
170.4
352.1
209.1
95.3
191.7
488.0
174.7
603.0
93.9
212.6
1232.0
158.2
951.5
912.0
1284.5
1704.0
2792.0
2458.0
518.3
27229
24860
25288
32196
30783
36400
20300
20141
12695
10009
21341
19341
27317
30100
28080
27467
26388
82380
19433
14125
13859
36073
5527
17856
14228
20195
72750
30798
32565
26592
11637
5366
31342
8874
159225
6045
15083
141225
16180
68681
110269
5519
46650
34200
111713
21938
23.8
25.4
148.0
30.0
36.9
28.3
92.1
77.6
56.5
35.1
19.0
36.3
18.0
17.8
16.0
18.2
13.4
179.8
18.4
59.7
64.4
27.9
36.0
25.7
14.4
51.0
203.0
91.6
50.1
42.3
50.8
36.7
113.3
29.8
522.5
71.1
107.5
1111.0
71.8
269.3
274.3
566.0
1081.0
1168.0
569.0
278.5
3.17
3.68
16.33
3.96
3.39
5.00
6.78
6.82
2.47
4.29
5.55
4.54
4.20
5.04
5.20
5.00
5.42
19.80
5.09
4.67
4.93
4.81
0.90
5.10
3.75
5.00
10.00
6.82
6.10
9.48
5.37
6.11
19.22
5.68
39.00
4.80
12.00
50.00
9.27
40.00
33.75
59.50
28.00
66.00
31.50
12.25
69.78
86.88
175.67
90.46
116.91
124.80
140.67
83.00
89.13
48.08
79.00
116.88
99.80
108.64
97.06
105.60
83.47
515.80
71.84
40.93
85.14
95.48
0.00
38.40
27.97
13.95
99.40
15.55
63.00
51.00
11.47
60.22
33.89
17.29
98.00
0.00
103.00
0.00
147.75
41.00
382.00
0.00
0.00
25.00
0.00
114
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Ba/Zr
W/Zr
Re/Zr
Au/Zr
Hg/Zr
882.50
882.70
882.88
883.10
882.70
882.88
883.10
883.28
883.28
883.50
883.70
883.91
884.01
884.30
884.51
884.71
884.89
885.08
885.08
885.26
885.58
885.58
885.80
885.97
886.18
886.29
888.36
888.57
888.75
888.94
889.16
889.36
889.61
889.80
889.80
889.99
890.20
890.40
890.58
890.79
891.08
891.30
891.49
891.69
891.69
891.93
292.3
351.1
2576.0
973.1
351.1
2576.0
973.1
443.7
1423.4
545.5
1028.1
1680.3
2649.0
395.2
7124.0
1433.6
3908.0
173.6
173.5
650.3
147.6
348.6
660.0
1293.0
254.9
859.5
2528.0
2501.0
834.3
2970.0
1105.0
518.6
513.9
223.2
244.0
202.2
1419.5
237.0
2834.0
2786.0
828.3
2424.0
5159.0
333.7
310.0
1.0
10364
12481
22005
9254
12481
22005
9254
12963
4298
10913
19208
40750
89925
8948
84525
12443
168225
9051
5351
33950
8507
18459
30775
43106
11425
69225
41325
134025
5721
172200
898500
30075
16792
10894
11300
8420
528000
7286
5571
100050
62950
87675
133950
8816
7376
23827
100.6
41.5
218.6
82.5
41.5
218.6
82.5
58.1
228.8
51.0
123.2
384.7
607.5
25.3
1125.0
106.3
1186.0
31.9
33.9
102.8
57.4
154.0
425.7
307.8
140.1
675.0
1417.0
1425.0
450.3
1283.0
447.7
118.5
65.6
76.0
83.0
38.2
637.0
61.2
1268.0
1245.0
424.7
428.7
1283.0
32.7
29.3
9.4
2.64
4.52
7.00
9.77
4.52
7.00
9.77
40.74
16.00
7.73
9.22
24.00
42.00
5.22
59.00
12.55
120.00
7.97
5.94
25.67
1.57
18.50
35.33
25.50
9.00
44.00
84.00
91.00
31.00
156.00
34.33
19.36
8.11
7.13
7.87
6.79
44.50
5.33
81.00
103.00
34.67
43.00
73.00
7.18
8.86
3.16
0.00
20.11
83.20
0.00
20.11
83.20
0.00
59.79
9.00
5.91
50.33
135.33
235.50
28.15
164.00
58.91
0.00
0.00
4.06
73.08
0.00
0.00
149.67
217.75
0.00
0.00
0.00
0.00
899.33
0.00
2038.00
27.00
0.00
0.00
19.33
0.00
688.50
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
58.46
115
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Ba/Zr
W/Zr
Re/Zr
Au/Zr
Hg/Zr
892.11
892.28
892.50
892.69
898.22
898.43
898.62
898.82
899.01
899.23
899.23
899.40
899.61
899.81
900.02
900.22
900.42
900.62
900.79
901.01
908.17
908.17
908.37
908.61
908.81
909.00
909.22
909.40
909.60
909.80
910.03
910.21
910.42
910.42
910.60
911.03
911.21
911.40
911.59
911.80
912.01
912.23
912.40
912.40
912.60
912.81
4781.0
118.7
2.2
5.7
197.2
208.2
188.1
438.4
9.3
57.4
59.0
10.7
24.4
3.5
19.5
6.5
32.1
23.1
9.1
7.8
823.8
788.6
515.6
981.5
783.2
675.1
1241.3
1232.8
1438.6
9098.0
1052.5
999.2
1082.9
7500.0
2627.5
1029.3
12705.0
1947.1
1249.3
2615.0
11740.0
1015.7
1312.5
15640.0
7415.0
6840.0
117525
18868
1423
2943
13459
2637
3474107
1858
25820
24492
11011
1613
1515
1918
1638
2481
5391
7617
15618
9964
8992
191550
11161
10557
8226
14053
11601
16645
182400
14638
14381
15943
102863
836813
0
2059875
24429
1903393
56250
172950
11084
14883
170400
220238
491625
127313
1346.0
52.3
29.3
27.0
15.9
19.8
20.3
73.4
14.1
16.8
16.8
14.9
15.5
12.6
18.5
15.2
15.9
19.6
14.9
13.9
27.9
31.7
37.1
34.4
35.5
10.3
53.6
34.5
61.3
951.0
72.9
72.3
61.0
430.5
223.8
58.5
430.5
122.9
61.1
146.5
900.0
37.8
53.7
893.0
451.5
443.0
171.00
13.58
3.58
4.14
5.12
4.67
5.48
7.79
4.04
3.85
3.72
5.13
3.99
3.63
2.55
4.44
3.39
3.60
3.86
4.32
7.26
5.17
6.12
5.69
5.96
5.52
7.56
5.92
5.00
45.00
3.25
4.25
6.29
19.50
20.25
7.07
58.00
11.43
5.00
19.00
58.00
9.13
5.94
43.00
22.50
24.50
0.00
28.73
0.00
0.00
16.35
32.92
3.88
8678.57
4.97
61.13
61.69
22.10
169.55
2.55
0.00
3.33
2.45
2.94
13.29
30.36
23.41
17.24
470.00
33.08
31.88
29.64
79.69
44.68
68.64
924.00
35.42
35.42
65.07
447.50
2011.00
25.47
4829.50
77.57
4402.14
92.17
204.00
30.30
25.38
696.00
435.50
984.00
116
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Ba/Zr
W/Zr
Re/Zr
Au/Zr
Hg/Zr
912.90
917.35
917.84
918.35
918.83
919.36
919.36
919.84
920.33
920.86
921.35
921.85
922.34
922.83
923.33
925.10
925.21
925.31
925.31
925.41
925.50
925.70
925.80
925.90
926.10
926.30
926.71
926.80
927.00
927.20
927.39
927.61
927.80
928.10
928.30
928.50
928.50
928.71
928.90
929.10
929.10
929.10
929.30
929.30
929.60
929.80
10000.0
4366.0
7933.3
0.0
5755.0
1326.4
1185.7
804.4
1286.8
773.1
5116.0
1511.5
844.0
1375.2
389.4
659.4
620.8
935.3
890.6
176.3
888.5
696.3
1940.0
507.6
746.2
542.3
464.0
1205.9
417.6
723.6
685.2
1978.8
1127.0
2995.0
70.3
1620.8
663.5
807.7
853.8
812.0
928.6
895.7
343.3
331.1
812.1
672.0
55365
100825
1602750
154875
18607
16409
21708
42081
98077
152550
31777
166725
1268750
45398
27007
24113
25793
24082
438667
26946
39631
67267
23169
28380
34433
21591
29814
18110
21859
17371
40863
27220
82150
397000
66950
20610
22720
24031
19873
23293
22307
21481
19813
19816
19047
20664
449.5
175.8
293.3
900.0
471.0
82.6
62.9
49.5
23.5
33.6
945.0
68.2
44.2
157.3
28.8
59.1
36.2
59.8
52.4
298.3
67.2
55.4
147.8
70.6
192.2
102.1
80.8
130.0
30.8
41.5
44.1
114.9
91.5
233.8
234.8
232.5
93.5
90.2
69.0
60.7
68.0
67.9
17.2
19.7
49.5
60.3
26.50
27.00
36.67
92.00
30.00
4.00
5.00
4.72
7.32
4.12
23.00
4.31
4.20
5.67
5.31
447.40
315.21
1451.33
246.41
192.00
150.60
299.33
3966.00
416.00
50.73
17.36
32.33
98.54
257.31
233.00
60.23
371.45
2918.33
92.97
3276.00
2505.00
3194.00
2617.06
36100.00
3407.69
3508.75
5000.00
3144.62
3006.00
6438.89
2886.36
2931.43
1533.45
4246.82
2044.29
6213.75
4143.00
5995.00
34400.00
5695.00
1665.00
2260.00
4119.23
1407.33
1537.86
613.14
1883.08
1732.17
2851.58
1835.33
253.85
333.75
643.67
422.62
396.60
325.22
498.18
431.57
295.86
508.18
256.14
587.75
620.10
1041.75
599.00
958.75
320.30
837.50
302.08
261.80
221.71
252.57
286.54
261.09
275.37
321.13
117
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Ba/Zr
W/Zr
Re/Zr
Au/Zr
Hg/Zr
929.80
930.01
930.21
930.40
930.60
930.80
935.70
935.91
936.10
936.30
936.61
936.61
936.61
936.79
937.00
937.40
937.60
937.80
938.10
938.30
938.50
938.71
938.71
938.89
939.11
939.30
939.59
939.80
940.01
940.19
940.60
940.79
940.90
752.9
411.9
800.0
389.1
628.4
863.6
550.0
555.7
324.4
600.1
420.8
414.3
420.9
770.7
673.8
534.9
407.7
1506.9
615.0
1488.8
563.8
640.7
650.8
418.4
648.8
1365.2
1418.3
312.8
596.1
853.0
964.7
534.5
511.9
19546
21143
21264
22829
22963
18855
17406
16545
23885
17033
15645
15880
24836
20544
0
22609
48569
19773
54350
18912
24869
24009
16516
22483
30150
20943
20317
18445
18178
0
18142
23522
0
63.5
23.8
130.7
66.4
131.4
115.5
86.2
17.7
13.4
69.7
18.7
17.8
17.1
65.8
111.7
21.1
27.3
68.8
41.2
151.8
25.9
69.4
80.5
29.4
76.4
150.7
129.7
39.1
83.4
103.6
320.0
28.4
23.5
218.50
219.68
293.14
277.57
343.86
149.38
260.36
227.35
303.79
380.00
260.21
211.76
288.33
274.71
306.89
236.05
342.29
666.08
192.09
326.00
298.53
502.15
305.73
253.35
301.83
371.67
384.86
305.09
420.09
210.67
321.67
260.32
358.92
2255.00
2083.51
123.00
2475.00
1942.86
3046.25
3480.91
1584.69
1877.27
2886.15
1718.33
1622.55
1191.11
2765.00
3866.67
1290.70
2112.86
7090.00
2549.09
1966.67
1748.82
2047.69
2836.36
1136.77
3403.33
7115.00
1507.14
2015.22
1650.91
313.56
5126.67
1977.74
2424.05
118
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Tl X/Zr
Pb/Zr
Bi/Zr
Th/Zr
U/Zr
870.29
870.29
870.48
870.64
870.82
870.99
871.21
871.50
871.50
871.71
871.91
872.10
872.31
872.52
872.52
872.70
873.00
873.22
873.42
873.60
873.79
874.00
874.20
874.40
874.60
874.80
875.00
875.21
875.40
875.60
875.81
875.90
879.88
879.88
880.08
880.28
880.50
880.71
880.89
881.11
881.28
881.50
881.69
881.87
882.11
882.28
5514
5160
5050
5774
5773
5408
9920
8373
5560
4829
6302
5125
5647
5899
5675
5602
5540
19488
5555
5692
5014
6642
1818
4915
4003
6033
12816
5291
6816
5692
5885
1867
19980
5373
72555
5832
9393
50010
5172
28538
19905
1822
35880
25170
38460
12758
20.53
20.29
14.50
18.82
24.52
19.10
15.44
17.73
10.73
5.96
18.55
17.17
19.00
16.82
16.86
17.44
18.43
57.00
13.91
10.73
12.93
34.13
10.03
15.43
9.45
13.74
24.80
10.45
17.85
14.61
5.42
17.96
31.78
5.79
111.50
3.07
8.20
79.00
13.00
50.25
152.50
88.50
26.00
40.00
200.50
20.25
689.3
671.6
0.0
513.0
650.1
647.2
0.0
0.0
0.0
0.0
753.0
457.0
773.6
753.1
769.0
780.5
862.0
880.8
608.0
0.0
182.6
1344.0
574.3
691.8
531.8
890.5
1128.0
385.1
654.6
550.4
317.1
644.7
1161.3
492.0
4542.0
327.2
961.2
2916.0
419.2
2433.0
2238.0
595.9
960.0
0.0
3156.0
498.0
20208
20109
38155
21664
18639
16700
19687
18824
22640
22275
20905
23213
19980
20827
20382
20567
20160
37026
21547
28540
26293
23487
31484
26921
21722
27805
13965
27095
8498
27483
27600
31655
24617
24428
4673
25190
16800
0
25730
7035
5010
31841
0
0
1545
5453
920.0
932.1
1700.0
917.5
818.7
1264.3
2192.2
1656.4
1171.3
1095.4
1419.1
1681.3
1211.6
1196.2
1242.4
1267.3
1260.7
4772.0
1320.9
1270.7
1100.7
1381.3
556.2
1294.5
947.1
1258.4
2886.0
1280.0
1473.5
1205.2
1241.1
1280.4
4113.3
1204.4
12265.0
1158.7
2211.0
10480.0
1212.7
7647.5
4285.0
5860.0
8113.0
5939.0
12530.0
2897.5
119
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Tl X/Zr
Pb/Zr
Bi/Zr
Th/Zr
U/Zr
882.50
882.70
882.88
883.10
882.70
882.88
883.10
883.28
883.28
883.50
883.70
883.91
884.01
884.30
884.51
884.71
884.89
885.08
885.08
885.26
885.58
885.58
885.80
885.97
886.18
886.29
888.36
888.57
888.75
888.94
889.16
889.36
889.61
889.80
889.80
889.99
890.20
890.40
890.58
890.79
891.08
891.30
891.49
891.69
891.69
891.93
5926
3601
9180
4272
3601
9180
4272
4179
1464
4330
8063
19610
38025
3935
45870
5995
78720
3994
1762
12078
4416
9664
15830
22583
6773
29580
24240
56250
1874
81060
17310
13293
9246
5256
5806
4028
36315
5490
1734
67920
34500
38810
83880
6318
5530
1771
10.09
10.41
27.80
9.62
10.41
27.80
9.62
9.89
34.60
10.41
17.89
42.67
83.00
8.20
94.00
12.00
198.00
7.29
6.86
31.67
7.10
16.13
27.00
39.25
11.00
50.50
48.00
120.00
50.67
148.00
25.00
24.36
17.26
10.25
11.13
8.09
59.50
7.38
140.00
93.00
50.00
43.33
74.00
4.13
3.80
11.93
279.3
251.1
362.4
104.3
251.1
362.4
104.3
279.2
458.3
294.0
321.3
736.0
1116.0
243.9
360.0
162.5
2340.0
191.7
528.8
1401.0
262.3
466.5
572.0
1275.0
236.0
798.0
0.0
444.0
584.6
3240.0
48.0
1081.1
672.0
318.0
347.2
229.8
1422.0
198.9
544.1
936.0
1268.0
1764.0
756.0
295.6
289.9
28.1
9012
20717
2211
27900
20717
2211
27900
26439
26113
13023
8258
18405
3098
14592
24345
8028
1349.1
1136.7
2940.0
1277.7
1136.7
2940.0
1277.7
1484.7
5760.0
1314.1
2882.2
6130.0
13090.0
1315.9
11660.0
1547.3
28540.0
1189.7
1313.1
4177.5
960.5
2650.0
4053.3
6652.5
1782.2
8870.0
6723.0
18080.0
7050.0
22200.0
2891.0
4563.6
2030.5
1226.3
1558.0
1356.7
8325.0
1561.4
23320.0
18420.0
9116.7
9710.0
21340.0
1397.4
1270.5
4115.8
27426
31029
7926
24264
10418
13995
9131
6358
6525
0
0
31216
0
21355
6282
4989
23822
12670
16518
15263
23129
30538
11070
7795
9505
4140
22950
23414
1685
120
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Tl X/Zr
Pb/Zr
Bi/Zr
Th/Zr
U/Zr
892.11
892.28
892.50
892.69
898.22
898.43
898.62
898.82
899.01
899.23
899.23
899.40
899.61
899.81
900.02
900.22
900.42
900.62
900.79
901.01
908.17
908.17
908.37
908.61
908.81
909.00
909.22
909.40
909.60
909.80
910.03
910.21
910.42
910.42
910.60
911.03
911.21
911.40
911.59
911.80
912.01
912.23
912.40
912.40
912.60
912.81
83490
4047
1252
2256
2044
2140
2681
1139
1281
1193
945
1107
1199
1405
1207
1124
1461
1206
988
5053
5014
4420
5848
4796
8918
4905
5465
5638
63960
5515
5360
4980
34350
22643
0
55455
10667
6431
21450
67890
4263
5698
79170
38145
39705
54210
54.00
4.62
4.47
4.00
2.35
2.29
3.02
7.79
3.10
2.02
1.87
1.51
1.24
1.42
1.20
1.30
1.53
0.94
0.93
0.70
9.68
9.24
4.80
6.00
7.16
56.81
7.00
3.96
9.79
75.00
6.33
6.58
6.79
44.00
24.25
7.60
121.50
26.71
13.36
25.33
108.00
7.00
7.88
109.00
68.00
53.50
2760.0
300.5
8.3
221.3
99.2
472.3
0.0
475.3
162.9
78.1
0.0
0.0
0.0
0.0
0.0
78.9
0.0
0.0
0.0
17.3
0.0
0.0
0.0
0.0
616.4
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2880
8804
1574
49368
3139
3272
8764
1399
1739
1703
1385
1458
1226
1546
1415
1494
1582
1266
1180
8082
8069
9192
9362
9100
7363
10538
9200
10893
55720
11500
11392
10236
31365
16873
0
30500
13493
6356
11028
54830
8809
9256
58640
31135
31460
33145
23840.0
1088.8
191.5
230.4
787.9
640.4
695.2
20314.3
1203.7
230.0
211.8
198.0
249.6
322.9
245.5
237.1
313.4
269.6
238.7
207.3
1489.4
1604.1
2376.0
2000.8
1855.2
2879.8
2906.9
2046.8
3054.3
29920.0
2183.3
2051.7
1997.1
14165.0
8412.5
2564.0
17735.0
3907.1
2455.7
8475.0
23320.0
1774.3
1508.8
22580.0
13310.0
13555.0
121
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Tl X/Zr
Pb/Zr
Bi/Zr
Th/Zr
U/Zr
912.90
917.35
917.84
918.35
918.83
919.36
919.36
919.84
920.33
920.86
921.35
921.85
922.34
922.83
923.33
925.10
925.21
925.31
925.31
925.41
925.50
925.70
925.80
925.90
926.10
926.30
926.71
926.80
927.00
927.20
927.39
927.61
927.80
928.10
928.30
928.50
928.50
928.71
928.90
929.10
929.10
929.10
929.30
929.30
929.60
929.80
19422
44370
88620
39285
5755
5331
5400
5218
4236
47400
7555
4692
12020
3601
3049
2776
3403
3205
3837
3059
2584
6980
2199
4052
2337
2715
3389
1805
2817
2435
5656
3490
11178
2935
8953
2961
3674
3565
3066
3504
3199
2673
2541
2707
3197
3609
52.50
26.00
54.00
143.00
110.00
6.18
5.93
5.89
5.59
29.46
75.00
11.31
10.35
28.83
4.75
7.93
6.75
7.33
5.35
49.33
12.00
6.19
16.00
6.69
14.80
5.56
7.27
9.71
5.14
34.23
69.86
63.50
8.20
90.00
18.25
22.50
5.50
26.90
6.31
5.60
8.00
5.57
14.35
12.48
5.00
12.27
0.0
0.0
0.0
0.0
0.0
0.0
0.0
84.3
0.0
0.0
0.0
0.0
0.0
0.0
518.4
1482.5
644.2
516.8
816.7
555.6
477.5
1060.3
400.1
550.2
439.7
359.0
396.9
226.9
401.7
477.1
1030.0
610.0
1507.0
574.0
0.0
869.4
331.0
425.0
269.9
370.5
298.4
345.4
305.0
418.6
369.0
296.1
15206
19457
56340
32800
10836
10507
9722
8470
8408
61630
7085
4482
10685
8741
10153
10600
10460
9394
15863
10415
6161
3778
10346
13584
11933
10000
12676
10810
10636
11019
4068
11040
4380
12165
9415
11160
11540
11923
10273
8736
9843
11540
10741
10042
10200
10964
16185.0
6818.0
12876.7
33490.0
18035.0
1722.7
1780.0
2463.3
1964.3
1795.8
17730.0
3106.2
1777.5
3905.0
1968.4
1913.3
1986.7
1992.0
1832.4
6236.7
2033.8
2060.6
5596.7
1999.2
2700.0
4150.0
2067.3
2395.7
2139.3
2220.5
3042.4
3930.0
2122.0
7625.0
22862.5
6260.0
2243.0
2473.0
2396.9
2082.7
2469.3
2309.3
2103.8
2159.3
2463.2
1936.7
122
Site 167 Minor Element Data (cont.)
Depth (mbsf)
Tl X/Zr
Pb/Zr
Bi/Zr
Th/Zr
U/Zr
929.80
930.01
930.21
930.40
930.60
930.80
935.70
935.91
936.10
936.30
936.61
936.61
936.61
936.79
937.00
937.40
937.60
937.80
938.10
938.30
938.50
938.71
938.71
938.89
939.11
939.30
939.59
939.80
940.01
940.19
940.60
940.79
940.90
2613
4150
3269
4651
3544
3231
2302
1897
2807
2070
1967
2061
4544
4511
0
2889
7257
2812
7453
2728
3432
3696
2031
3346
5018
6400
3328
3435
3848
0
2678
2878
0
10.29
5.46
6.86
17.79
7.57
12.75
10.82
13.08
5.56
9.15
9.17
7.63
8.04
61.64
10.44
8.23
20.34
18.85
7.95
25.17
18.65
7.15
8.64
8.90
10.00
23.00
15.57
7.74
11.55
17.89
132.67
9.16
11.16
316.2
310.3
296.6
277.6
388.8
359.0
355.5
276.5
351.1
313.1
280.4
280.6
512.4
285.8
10381
12046
11821
11497
12105
11436
10841
10261
11300
10156
9812
10048
7407
10166
447.1
902.3
496.8
915.8
452.9
443.8
353.5
292.0
394.2
492.8
484.3
302.6
369.5
337.4
0.0
446.8
467.8
0.0
11526
7977
9718
13290
10821
10662
10555
10268
10775
13573
11753
10517
11209
10734
0
9800
10132
0
2335.7
2246.5
2607.1
4922.9
2702.9
2970.0
2356.4
2306.1
2177.3
3206.2
2118.8
2076.5
2229.6
3315.7
2441.1
2259.5
2419.4
5704.6
2175.9
6323.3
2220.6
2074.6
2255.5
2030.3
3105.0
3166.7
2601.4
3001.7
2290.0
2236.7
3169.7
1851.3
2349.2
123
124
125
126
127
128
Site 167 Major Element Data
129
Depth (mbsf)
Ba/Al
Ca/Al
Fe/Al
K/Al
Mg/Al
870.29
870.29
870.48
870.64
870.82
870.99
871.21
871.50
871.50
871.71
871.91
872.10
872.31
872.52
872.52
872.70
873.00
873.22
873.42
873.60
873.79
874.00
874.20
874.40
874.60
874.80
875.00
875.21
875.40
875.60
875.81
875.90
879.88
879.88
880.08
880.28
880.50
880.71
880.89
881.11
881.28
881.50
881.69
881.87
882.11
882.28
0.61
0.66
0.52
0.55
0.82
0.63
0.29
0.26
0.31
0.23
0.35
0.18
0.31
0.28
0.31
0.32
0.30
0.21
0.28
0.11
0.05
0.17
0.17
0.14
0.29
0.27
0.28
0.18
0.31
0.21
0.11
0.20
0.30
0.19
0.08
0.11
0.13
0.13
0.17
0.17
0.27
0.27
0.24
0.41
0.27
0.22
19.03
19.80
76.48
22.07
32.72
10.72
28.89
24.02
29.18
17.50
5.90
9.35
10.61
11.86
12.31
10.73
9.85
34.01
14.55
42.97
44.49
18.21
12.00
15.68
10.91
38.50
51.67
63.21
26.91
27.16
42.61
32.40
23.69
25.81
43.42
55.72
42.76
45.50
53.70
32.20
52.31
67.53
78.61
80.52
33.11
85.61
4.54
4.61
4.71
4.70
5.05
4.82
3.69
3.27
4.06
3.80
4.00
3.70
3.63
3.28
3.59
3.69
3.55
3.60
3.00
3.47
3.65
3.30
2.50
3.06
3.11
3.56
3.57
3.55
3.32
3.39
3.30
3.27
5.92
3.54
3.56
3.28
3.85
3.78
3.66
3.70
3.91
4.12
4.10
4.26
3.67
3.97
1.25
1.33
0.00
1.16
0.86
0.85
0.74
0.52
0.53
1.00
1.40
0.83
1.50
1.31
1.59
1.48
1.70
0.71
1.56
0.51
0.29
1.35
0.16
1.53
1.69
0.88
0.33
0.30
1.07
0.99
1.00
1.30
2.12
1.44
1.06
0.59
0.90
0.11
0.66
1.22
0.51
0.00
0.00
0.00
1.01
0.00
4.07
4.42
7.83
4.45
5.10
4.27
5.09
4.13
5.19
4.22
3.65
3.98
3.60
3.35
3.53
3.61
3.39
4.70
3.34
5.02
5.09
3.81
3.36
3.55
3.25
4.47
5.33
5.25
4.48
4.48
4.54
4.30
5.27
4.09
4.57
4.74
4.77
5.49
4.91
4.30
5.09
6.05
6.75
7.70
5.16
6.37
Site 167 Major Element Data (cont.)
130
Depth (mbsf)
Ba/Al
Ca/Al
Fe/Al
K/Al
Mg/Al
882.50
882.70
882.88
883.10
883.28
883.28
883.50
883.70
883.91
884.01
884.30
884.51
884.71
884.89
885.08
885.08
885.26
885.58
885.58
885.80
885.97
886.18
886.29
888.36
888.57
888.75
888.94
889.16
889.36
889.61
889.80
889.80
889.99
890.20
890.40
890.58
890.79
891.08
891.30
891.49
891.69
891.69
891.93
892.11
892.28
892.50
0.25
0.28
0.89
0.82
0.32
0.39
0.51
0.47
0.36
0.40
0.37
0.74
0.99
0.33
0.17
0.18
0.21
0.13
0.17
0.21
0.24
0.17
0.23
0.51
0.29
0.18
0.23
0.49
0.17
0.31
0.17
0.21
0.19
0.23
0.23
0.33
0.25
0.16
0.37
0.33
0.33
0.33
0.02
0.35
0.25
0.02
60.05
23.29
62.70
60.86
23.05
25.30
36.29
38.13
44.57
32.82
13.81
72.27
56.52
24.40
18.69
19.57
13.38
33.48
38.44
65.06
26.50
52.32
21.53
49.36
20.45
30.81
28.74
52.11
11.22
24.34
32.92
42.03
18.40
47.99
21.23
26.11
43.87
31.65
21.97
34.56
16.02
16.45
1.44
36.39
29.47
26.01
3.54
3.75
3.55
3.46
2.57
3.45
3.60
3.40
3.79
4.77
3.04
4.55
3.71
5.02
2.78
3.12
3.87
2.53
3.63
4.01
3.61
3.46
6.31
5.60
5.78
4.10
4.76
5.76
3.39
3.93
3.01
3.93
3.42
4.41
3.47
7.26
4.66
4.52
6.24
5.67
4.23
4.42
4.34
1.37
4.28
6.19
0.45
1.14
0.37
0.53
0.65
0.86
1.19
0.99
0.68
1.35
1.73
0.00
0.61
1.45
1.33
1.54
1.65
0.65
0.89
0.03
1.24
0.62
1.22
0.00
1.17
1.09
1.31
1.36
2.42
2.32
1.36
1.90
2.19
1.66
1.82
2.64
1.76
2.23
2.60
2.14
2.88
2.92
1.19
2.59
2.63
2.11
5.54
4.22
5.49
5.44
3.37
4.48
4.72
4.87
5.65
6.56
3.65
7.19
5.24
6.94
3.65
4.00
3.99
3.52
5.02
6.29
4.76
5.11
8.39
9.94
7.92
5.48
6.06
8.07
3.56
3.91
3.65
4.69
3.92
5.51
3.98
7.22
6.05
5.10
5.41
5.65
3.80
3.97
2.18
0.57
1.97
5.66
Site 167 Major Element Data (cont.)
131
Depth (mbsf)
Ba/Al
Ca/Al
Fe/Al
K/Al
Mg/Al
892.69
898.22
898.43
898.62
898.82
899.01
899.23
899.23
899.40
899.61
899.81
900.02
900.22
900.42
900.62
900.79
901.01
908.17
908.17
908.37
908.61
908.81
909.00
909.22
909.40
909.60
909.80
910.03
910.21
910.42
910.42
910.60
910.80
911.03
911.21
911.40
911.59
911.80
912.01
912.23
912.40
912.40
912.60
912.81
912.90
917.35
0.03
0.65
0.56
0.17
0.53
0.09
0.31
0.35
0.09
0.17
0.05
0.03
0.07
0.22
0.15
0.07
0.07
0.25
0.27
0.16
0.29
0.25
0.22
0.35
0.36
0.40
0.36
0.30
0.28
0.25
0.35
0.20
0.46
0.26
0.55
0.30
0.30
0.19
0.30
0.29
0.29
0.45
0.38
0.29
0.36
0.34
27.62
14.50
16.50
3.01
4.06
20.89
18.76
18.67
24.23
34.06
24.13
5.76
21.34
28.18
22.78
20.39
21.05
17.93
19.15
16.34
22.79
24.35
0.27
39.53
23.92
45.08
25.84
52.24
51.60
33.42
42.55
38.66
52.29
33.70
24.29
47.29
39.49
19.96
42.93
33.72
34.40
38.46
31.94
41.53
32.74
38.52
5.92
5.97
5.02
0.99
1.11
5.69
5.33
5.75
5.31
4.98
4.70
1.59
6.04
6.19
7.26
5.41
6.01
2.86
3.39
3.44
3.19
3.40
3.41
3.23
3.36
3.56
5.88
3.53
3.59
2.68
3.93
3.68
4.52
3.53
5.12
3.67
3.24
3.53
4.15
3.47
2.81
4.72
4.69
3.92
3.85
3.76
2.65
2.09
1.52
1.75
1.53
0.98
0.85
0.95
0.64
0.63
0.70
0.20
0.70
0.95
1.12
1.26
1.18
2.19
2.51
2.25
2.42
2.33
2.76
1.90
2.29
1.80
2.18
1.54
1.58
1.36
1.89
1.98
1.35
2.10
2.70
1.74
1.91
2.38
1.76
2.21
1.30
1.97
2.21
1.95
2.10
2.04
5.89
2.75
2.77
0.64
0.42
5.08
5.83
5.90
5.15
5.24
3.80
1.26
6.12
5.79
6.81
4.91
5.43
3.36
4.06
4.03
3.92
4.03
3.52
4.43
4.04
4.69
7.67
5.27
5.17
3.54
5.12
4.66
6.36
4.42
5.84
5.02
4.43
4.11
5.70
4.20
3.53
5.95
5.89
5.23
4.90
4.59
Site 167 Major Element Data (cont.)
132
Depth (mbsf)
Ba/Al
Ca/Al
Fe/Al
K/Al
Mg/Al
917.84
918.35
918.83
919.36
919.36
919.84
920.33
920.86
921.35
921.85
922.34
922.83
923.33
925.10
925.21
925.31
925.31
925.41
925.50
925.70
925.80
925.90
926.10
926.30
926.71
926.80
927.00
927.20
927.39
927.61
927.80
928.10
928.30
928.50
928.50
928.71
928.90
929.10
929.10
929.10
929.80
929.80
930.01
930.21
930.40
930.60
0.36
0.46
0.25
0.27
0.39
0.25
0.39
0.25
0.17
0.27
0.29
0.19
0.13
0.18
0.18
0.22
0.26
0.03
0.23
0.19
0.18
0.14
0.13
0.11
0.12
0.23
0.12
0.20
0.18
0.28
0.27
0.23
0.01
0.18
0.16
0.19
0.20
0.22
0.10
0.10
0.17
0.19
0.12
0.16
0.10
0.13
26.47
26.87
34.98
37.92
57.82
31.76
20.66
33.01
70.81
36.50
40.39
57.74
22.69
38.08
20.18
30.69
35.60
11.42
38.70
34.58
31.00
41.62
87.87
14.23
45.70
61.46
12.04
29.12
15.58
48.65
53.69
50.24
0.76
35.96
46.31
47.80
44.43
49.56
12.18
12.12
37.86
41.47
11.36
67.81
26.55
60.51
3.91
4.07
3.54
2.49
3.51
3.96
3.36
3.60
3.63
2.90
3.40
3.24
3.18
3.62
3.80
3.45
3.92
3.11
4.07
3.50
3.63
3.60
3.67
3.38
3.61
3.59
3.56
3.44
3.09
3.60
4.06
4.19
2.05
4.19
3.52
3.28
3.45
3.49
3.00
3.22
3.13
3.46
3.46
3.73
3.85
3.72
2.37
2.29
2.00
0.80
1.61
1.78
2.48
2.50
1.45
2.17
2.02
1.67
2.37
1.91
2.24
1.66
2.01
0.44
1.88
1.97
2.06
1.74
1.05
1.20
1.61
1.31
2.21
2.21
1.89
1.93
1.60
1.95
0.00
2.01
1.58
1.49
1.93
1.86
2.46
2.57
1.39
1.82
2.42
1.24
1.80
1.18
4.81
5.42
5.09
3.70
5.01
4.62
3.78
4.31
6.30
4.43
4.65
5.42
4.13
4.85
4.12
4.27
4.78
3.63
4.96
4.59
4.66
5.14
6.90
4.37
5.30
5.89
3.95
4.21
3.89
4.73
5.39
5.15
2.15
5.96
5.41
5.24
4.86
5.13
3.47
3.62
4.45
4.97
3.84
6.13
4.75
5.92
Site 167 Major Element Data (cont.)
133
Depth (mbsf)
Ba/Al
Ca/Al
Fe/Al
K/Al
Mg/Al
930.80
935.91
936.10
936.30
936.61
936.61
936.79
937.20
937.40
937.40
937.60
937.80
938.10
938.30
938.71
938.71
938.89
939.30
939.59
939.80
940.01
940.19
940.19
940.41
940.60
940.79
940.90
929.60
929.60
935.70
935.70
935.70
0.19
0.17
0.10
0.14
0.13
0.13
0.15
0.21
0.16
0.16
0.12
0.36
0.18
0.24
0.14
0.17
0.12
0.25
0.28
0.09
0.14
0.20
0.20
0.33
0.14
0.17
0.15
0.22
0.22
0.14
0.14
0.14
50.27
13.08
8.08
20.74
12.83
12.84
31.98
37.30
16.13
16.02
15.75
18.73
29.92
40.04
24.88
28.85
21.99
72.30
68.35
10.80
50.45
72.59
74.26
59.57
116.76
18.16
6.66
22.23
23.02
60.74
62.26
62.12
3.47
3.22
3.33
3.31
2.94
3.16
3.34
3.38
3.15
3.15
3.11
6.64
3.83
5.43
3.07
3.96
3.42
3.94
4.44
3.36
3.86
3.83
3.74
6.85
4.37
3.49
3.60
3.52
3.39
3.81
3.87
3.78
1.21
2.64
2.78
1.55
2.54
2.53
2.05
1.88
2.49
2.58
2.39
4.78
2.27
2.83
1.10
1.41
2.40
1.07
1.31
1.96
1.70
1.34
1.48
2.12
0.30
2.39
2.77
1.93
2.20
1.64
1.80
1.80
5.54
3.61
3.53
4.32
3.53
3.57
4.31
4.63
3.73
3.67
3.71
5.15
4.50
7.06
4.06
5.23
4.11
6.34
6.16
3.92
5.37
6.14
6.02
10.78
8.02
4.00
3.36
4.31
4.04
5.59
5.52
5.50
Site 167 Major Element Data (cont.)
134
Depth (mbsf)
Mn/Al
Na/Al
P/Al
Ti/Al
870.29
870.29
870.48
870.64
870.82
870.99
871.21
871.50
871.50
871.71
871.91
872.10
872.31
872.52
872.52
872.70
873.00
873.22
873.42
873.60
873.79
874.00
874.20
874.40
874.60
874.80
875.00
875.21
875.40
875.60
875.81
875.90
879.88
879.88
880.08
880.28
880.50
880.71
880.89
881.11
881.28
881.50
881.69
881.87
882.11
882.28
0.19
0.21
0.31
0.23
0.26
0.28
0.09
0.07
0.09
0.06
0.16
0.15
0.19
0.17
0.20
0.19
0.19
0.17
0.13
0.11
0.12
0.15
0.05
0.11
0.10
0.15
0.15
0.16
0.16
0.13
0.08
0.11
0.08
0.05
0.11
0.07
0.06
0.11
0.12
0.07
0.15
0.14
0.12
0.17
0.09
0.12
1.40
1.54
1.96
1.63
1.58
2.40
1.95
1.85
2.34
2.10
1.58
2.00
1.73
1.60
1.83
1.71
1.62
1.82
1.68
1.83
1.87
1.76
0.84
1.63
1.65
2.13
1.84
1.76
1.66
1.49
1.64
1.60
2.31
1.56
1.73
1.61
1.87
2.15
1.69
1.56
2.15
2.25
2.52
1.82
1.71
2.70
0.63
0.34
0.22
0.44
0.31
0.18
0.11
0.07
0.22
0.18
0.19
0.31
0.16
0.16
0.16
0.18
0.16
0.26
0.23
0.26
0.17
0.11
0.02
0.15
0.19
0.16
0.23
0.17
0.01
0.24
0.15
0.19
0.48
0.26
0.21
0.15
0.19
0.13
0.18
0.13
0.07
0.18
0.37
0.50
0.29
0.46
0.39
0.45
0.59
0.46
0.47
0.48
0.46
0.40
0.51
0.45
0.45
0.46
0.40
0.35
0.39
0.41
0.39
0.47
0.38
0.48
0.51
0.41
0.25
0.39
0.38
0.48
0.50
0.50
0.44
0.44
0.44
0.42
0.81
0.44
0.46
0.43
0.49
0.55
0.47
0.45
0.50
0.58
0.61
0.66
0.49
0.56
Site 167 Major Element Data (cont.)
135
Depth (mbsf)
Mn/Al
Na/Al
P/Al
Ti/Al
882.50
882.70
882.88
883.10
883.28
883.28
883.50
883.70
883.91
884.01
884.30
884.51
884.71
884.89
885.08
885.08
885.26
885.58
885.58
885.80
885.97
886.18
886.29
888.36
888.57
888.75
888.94
889.16
889.36
889.61
889.80
889.80
889.99
890.20
890.40
890.58
890.79
891.08
891.30
891.49
891.69
891.69
891.93
892.11
892.28
892.50
0.09
0.05
0.10
0.11
0.04
0.06
0.07
0.07
0.10
0.11
0.03
0.19
0.11
0.11
0.04
0.04
0.04
0.06
0.08
0.14
0.07
0.11
0.14
0.30
0.14
0.11
0.10
0.21
0.03
0.06
0.08
0.10
0.05
0.15
0.04
0.15
0.16
0.12
0.08
0.13
0.05
0.05
0.01
0.25
0.17
0.04
1.95
1.64
1.69
1.64
1.63
2.21
1.51
1.63
1.64
2.07
1.31
2.04
1.57
2.37
1.11
1.26
1.39
1.09
1.54
1.85
1.70
1.61
3.22
2.38
2.42
1.83
2.15
2.44
1.51
1.46
1.49
1.89
1.67
2.01
1.75
3.25
2.06
1.99
1.77
2.00
1.42
1.44
1.34
1.90
1.94
1.83
0.34
0.13
0.37
0.34
0.05
0.07
0.30
0.19
0.29
0.29
0.15
0.55
0.29
0.27
0.12
0.15
0.09
0.12
0.17
0.30
0.15
0.27
0.33
0.64
0.16
0.18
0.19
0.06
0.08
0.11
0.11
0.14
0.05
0.08
0.20
0.00
0.09
0.17
0.03
0.13
0.16
0.11
0.17
0.03
0.07
0.03
0.50
0.45
0.50
0.48
0.34
0.49
0.47
0.47
0.54
0.70
0.41
0.65
0.51
0.77
0.37
0.42
0.50
0.33
0.50
0.58
0.49
0.48
1.00
0.95
0.90
0.59
0.69
0.89
0.47
0.46
0.37
0.50
0.41
0.58
0.45
0.88
0.62
0.55
0.61
0.55
0.41
0.43
1.05
0.15
0.35
0.44
Site 167 Major Element Data (cont.)
136
Depth (mbsf)
Mn/Al
Na/Al
P/Al
Ti/Al
892.69
898.22
898.43
898.62
898.82
899.01
899.23
899.23
899.40
899.61
899.81
900.02
900.22
900.42
900.62
900.79
901.01
908.17
908.17
908.37
908.61
908.81
909.00
909.22
909.40
909.60
909.80
910.03
910.21
910.42
910.42
910.60
910.80
911.03
911.21
911.40
911.59
911.80
912.01
912.23
912.40
912.40
912.60
912.81
912.90
917.35
0.03
0.05
0.05
0.01
0.01
0.04
0.04
0.04
0.04
0.04
0.04
0.01
0.04
0.06
0.04
0.03
0.03
0.11
0.13
0.07
0.12
0.11
0.01
0.20
0.10
0.18
0.31
0.20
0.20
0.10
0.16
0.13
0.21
0.11
0.12
0.15
0.12
0.07
0.18
0.10
0.08
0.14
0.13
0.12
0.11
0.09
1.67
1.56
1.79
0.35
0.30
1.52
1.43
1.62
1.69
1.68
1.65
0.42
1.64
1.71
1.80
1.50
1.59
1.30
1.52
1.60
1.62
1.67
1.07
1.79
1.61
1.84
2.71
1.59
1.76
1.26
1.77
1.79
2.04
1.64
2.14
1.92
1.61
1.46
1.98
1.53
1.32
2.06
2.11
1.87
2.08
1.68
0.09
0.26
0.17
0.13
0.02
0.04
0.13
0.17
0.13
0.13
0.19
0.13
0.23
0.24
0.23
0.15
0.27
0.22
0.22
0.14
0.12
0.03
0.16
0.08
0.12
0.05
0.07
0.05
0.18
0.08
0.22
0.12
0.23
0.18
0.01
0.06
0.11
0.05
0.07
0.07
0.20
0.10
0.17
0.03
0.06
0.14
0.44
0.46
0.42
0.07
0.07
0.58
0.44
0.48
0.51
0.51
0.61
0.13
0.49
0.56
0.52
0.52
0.53
0.41
0.45
0.41
0.44
0.43
0.36
0.48
0.42
0.50
0.89
0.49
0.48
0.37
0.53
0.49
0.66
0.45
0.68
0.51
0.47
0.44
0.59
0.41
0.38
0.64
0.63
0.54
0.53
0.46
Site 167 Major Element Data (cont.)
137
Depth (mbsf)
Mn/Al
Na/Al
P/Al
Ti/Al
917.84
918.35
918.83
919.36
919.36
919.84
920.33
920.86
921.35
921.85
922.34
922.83
923.33
925.10
925.21
925.31
925.31
925.41
925.50
925.70
925.80
925.90
926.10
926.30
926.71
926.80
927.00
927.20
927.39
927.61
927.80
928.10
928.30
928.50
928.50
928.71
928.90
929.10
929.10
929.10
929.80
929.80
930.01
930.21
930.40
930.60
0.09
0.10
0.11
0.08
0.13
0.08
0.05
0.07
0.17
0.09
0.09
0.13
0.06
0.09
0.04
0.07
0.08
0.03
0.11
0.09
0.08
0.10
0.22
0.03
0.11
0.17
0.03
0.07
0.03
0.10
0.12
0.13
0.01
0.12
0.09
0.09
0.08
0.09
0.02
0.03
0.07
0.09
0.03
0.15
0.04
0.11
1.50
1.60
1.36
1.12
1.83
1.67
1.50
1.63
2.19
1.80
1.75
1.90
1.72
1.90
1.78
1.81
1.97
1.96
1.89
1.78
1.80
1.97
2.35
2.21
2.06
2.20
1.80
1.75
1.83
2.06
2.34
1.94
1.70
2.58
2.17
1.86
1.84
2.04
1.49
1.58
1.79
2.11
1.44
2.38
2.19
2.20
0.20
0.06
0.26
0.13
0.18
0.19
0.10
0.06
0.16
0.13
0.29
0.18
0.03
0.05
0.14
0.33
0.13
0.19
0.18
0.19
0.25
0.14
0.70
0.19
0.40
0.40
0.12
0.10
0.17
0.28
0.08
0.23
0.08
0.47
0.17
0.47
0.25
0.25
0.13
0.07
0.33
0.20
0.08
0.43
0.17
0.37
0.52
0.62
0.56
0.36
0.50
0.45
0.40
0.43
0.55
0.44
0.47
0.48
0.40
0.47
0.42
0.40
0.47
0.42
0.49
0.46
0.45
0.47
0.55
0.45
0.49
0.52
0.39
0.42
0.41
0.47
0.51
0.47
0.29
0.63
0.50
0.50
0.46
0.45
0.35
0.39
0.40
0.46
0.38
0.53
0.44
0.52
Site 167 Major Element Data (cont.)
138
Depth (mbsf)
Mn/Al
Na/Al
P/Al
Ti/Al
930.80
935.91
936.10
936.30
936.61
936.61
936.79
937.20
937.40
937.40
937.60
937.80
938.10
938.30
938.71
938.71
938.89
939.30
939.59
939.80
940.01
940.19
940.19
940.41
940.60
940.79
940.90
929.60
929.60
935.70
935.70
935.70
0.08
0.03
0.02
0.04
0.02
0.02
0.06
0.08
0.04
0.04
0.03
0.06
0.08
0.14
0.05
0.07
0.04
0.16
0.11
0.02
0.08
0.11
0.11
0.19
0.17
0.03
0.02
0.04
0.04
0.11
0.11
0.11
2.00
1.49
1.31
2.06
1.37
1.37
1.95
1.94
1.44
1.43
1.40
2.98
1.94
2.69
1.46
1.93
1.53
2.30
2.39
1.92
2.08
2.06
2.10
3.59
2.78
1.79
1.33
2.21
2.22
1.86
1.87
1.89
0.17
0.05
0.06
0.25
0.11
0.08
0.16
0.16
0.11
0.07
0.04
0.24
0.16
0.34
0.18
0.36
0.06
0.37
0.11
0.27
0.34
0.34
0.34
0.64
0.62
0.23
0.07
0.23
0.05
0.25
0.18
0.26
0.52
0.38
0.36
0.45
0.37
0.37
0.43
0.45
0.37
0.37
0.39
0.82
0.44
0.72
0.36
0.49
0.39
0.56
0.53
0.41
0.47
0.50
0.48
1.02
0.61
0.41
0.44
0.43
0.40
0.47
0.46
0.46
139
140
141
Site 463 Minor Element Data
Depth (mbsf)
Sc/Zr
V/Zr
Cr/Zr
Co/Zr
Ni/Zr
585.00
585.00
585.38
585.79
586.22
586.50
586.90
587.29
587.71
594.67
604.10
604.50
604.50
604.99
605.22
605.40
605.69
605.84
606.00
606.39
606.69
607.10
607.03
607.28
607.49
607.61
607.89
608.62
608.91
609.20
609.48
609.79
610.01
610.30
610.30
610.58
613.51
613.91
614.23
614.62
614.88
615.03
615.31
615.59
615.89
615.89
0.14
0.19
1.14
2.68
1.63
1.52
4.39
0.63
0.60
1.18
3.06
0.88
3.14
1.11
3.24
0.53
0.71
0.65
0.66
0.20
0.58
0.72
0.11
0.24
2.68
0.16
0.25
0.11
0.21
0.13
0.07
0.12
0.12
0.13
0.12
0.17
0.59
0.08
0.09
0.09
0.13
0.07
0.14
0.09
0.06
0.08
0.84
1.12
5.76
5.87
5.10
7.25
14.41
2.77
4.77
4.83
5.20
2.91
11.24
5.79
6.83
0.90
2.75
4.76
1.73
0.75
2.69
3.58
0.11
0.53
23.46
0.57
0.76
3.48
4.69
3.23
4.07
8.09
1.10
2.02
2.12
6.16
1.12
4.40
3.74
4.40
0.61
1.43
1.93
0.70
0.47
1.60
1.20
2.78
2.42
15.32
5.22
3.22
212.60
56.79
6.11
0.38
10.44
5.82
1.68
2.06
0.93
77.47
1.31
8.84
0.56
0.72
0.50
0.81
0.83
132.58
4.67
1.10
1.39
6.43
15.60
13.07
11.84
44.68
2.55
6.34
5.06
42.27
5.46
23.71
5.99
21.92
3.89
5.39
4.81
10.04
2.63
5.31
13.75
1.00
1.09
10.84
1.40
1.16
15.54
5.79
1.44
0.68
1.43
1.19
0.94
0.99
0.97
18.18
1.29
1.59
0.95
0.89
0.98
1.61
1.02
10.89
1.64
0.7
0.8
3.8
8.1
5.9
4.8
14.3
0.9
2.2
1.1
9.7
1.3
4.3
1.4
5.2
0.7
1.0
1.0
1.2
0.3
0.9
2.7
2.4
2.3
5.3
4.2
2.7
99.6
31.1
5.2
0.3
7.4
4.1
1.3
1.4
0.7
58.5
1.0
6.0
0.5
0.5
0.6
0.7
0.5
70.2
6.7
0.31
1.24
0.30
0.08
0.45
0.77
0.41
0.53
0.50
0.99
5.24
0.43
0.31
0.40
0.78
0.49
0.73
1.01
1.80
1.43
142
Site 463 Minor Element Data (cont.)
Depth (m)
45Sc
51V
52Cr
59Co
60Ni
615.59
615.89
615.89
616.21
616.46
616.60
616.92
617.29
617.60
617.88
618.02
618.02
618.28
618.60
618.90
619.20
619.70
619.70
620.20
620.70
621.20
621.70
622.20
622.50
622.79
623.06
623.01
623.28
623.59
623.88
623.88
624.21
624.50
624.80
625.10
625.40
625.71
626.00
626.00
626.29
626.60
627.00
627.30
627.52
627.52
627.81
0.09
0.06
0.08
0.13
0.12
0.05
0.18
0.10
0.13
0.10
0.08
0.09
0.11
0.27
0.08
0.10
0.41
0.51
0.36
0.27
0.10
0.25
0.57
0.08
0.38
0.17
0.55
0.29
0.05
0.06
0.05
0.06
0.04
0.05
0.05
0.06
0.08
0.19
0.06
0.05
0.04
0.06
0.06
0.05
0.05
0.09
1.01
1.80
1.43
0.65
0.72
0.28
1.13
0.78
1.02
0.75
0.87
0.77
0.88
1.54
0.61
0.69
3.27
3.78
2.60
12.46
6.45
2.36
3.48
0.54
1.90
1.77
3.13
2.28
0.17
0.39
0.39
0.48
0.36
0.47
0.48
0.30
0.41
0.09
0.36
0.41
0.29
0.32
0.42
0.42
0.41
0.37
0.83
132.58
4.67
0.86
0.94
0.28
1.18
0.96
0.99
0.58
0.59
0.57
1.20
2.57
0.84
1.02
2.91
3.60
1.95
2.58
1.51
1.15
2.58
0.77
3.46
2.57
2.93
3.01
0.67
0.40
0.45
4.70
1.02
1.69
1.32
1.50
3.59
2.70
3.22
25.67
15.50
12.47
47.85
2.77
2.63
10.44
1.02
10.89
1.64
0.94
1.02
0.43
1.47
0.76
1.80
1.60
0.58
0.63
1.22
1.60
1.14
1.22
5.28
4.35
3.11
1.93
0.80
1.92
5.40
2.69
2.47
2.46
2.87
2.18
0.98
0.88
0.81
2.12
0.87
1.36
0.95
0.80
1.13
4.86
1.27
2.55
1.50
1.97
4.50
0.79
0.84
2.01
0.5
70.2
6.7
0.6
0.6
0.3
0.7
0.5
0.8
0.7
0.4
0.3
0.7
0.9
0.7
0.8
1.7
2.0
2.2
2.8
1.1
1.7
2.7
1.6
1.8
1.2
1.8
1.4
0.7
0.4
0.5
2.9
0.9
1.5
1.1
1.3
2.8
3.3
2.6
13.9
8.6
9.2
28.3
2.1
2.0
7.1
143
Site 463 Minor Element Data (cont.)
Depth (m)
45Sc
51V
52Cr
59Co
60Ni
628.09
628.38
628.60
632.63
633.52
634.14
635.05
635.60
636.53
636.53
637.10
638.15
642.15
643.04
643.92
644.83
645.13
646.05
646.92
647.82
647.82
651.88
652.81
653.58
661.17
661.74
0.06
0.06
0.07
0.07
0.08
0.07
0.06
0.04
0.05
0.06
0.06
0.03
0.06
0.05
0.07
0.50
0.29
0.05
0.07
0.03
0.04
0.54
0.42
0.35
0.50
0.28
0.30
0.39
0.68
0.65
0.55
0.48
0.62
0.61
0.47
0.48
0.25
0.20
0.28
0.32
0.33
0.60
0.25
0.33
0.03
0.03
0.05
2.99
1.48
1.42
1.82
1.43
4.03
5.03
124.33
83.49
38.05
19.00
97.68
49.87
60.50
76.95
0.24
0.18
0.21
0.23
0.26
0.67
0.25
0.22
0.06
0.16
0.14
1.80
0.94
1.03
1.24
0.96
1.48
1.62
12.42
9.59
4.32
2.94
10.18
6.61
7.46
7.54
0.81
0.57
0.62
0.68
1.01
4.04
1.15
3.40
0.24
0.41
0.47
5.46
3.35
3.67
4.44
2.44
3.2
4.0
75.8
57.4
26.3
15.0
63.2
38.0
46.9
49.3
0.4
0.3
0.3
0.3
0.4
1.3
0.3
1.5
0.1
0.6
0.4
1.7
1.0
0.9
1.2
0.6
144
Site 463 Minor Element Data (cont.)
Depth (mbsf)
Cu/Zr
Zn/Zr
Se/Zr
As/Zr
Rb/Zr
585.00
585.00
585.38
585.79
586.22
586.50
586.90
587.29
587.71
594.67
604.10
604.50
604.50
604.99
605.22
605.40
605.69
605.84
606.00
606.39
606.69
607.10
607.03
607.28
607.49
607.61
607.89
608.62
608.91
609.20
609.48
609.79
610.01
610.30
610.30
610.58
613.51
613.91
614.23
614.62
614.88
615.03
615.31
615.59
615.89
615.89
7.5
9.1
46.6
92.1
179.7
60.1
196.3
18.0
57.9
23.6
43.0
19.5
73.3
63.1
42.9
5.6
13.5
30.3
9.6
6.9
20.3
43.9
7.6
9.6
51.7
13.0
14.1
71.3
37.9
10.6
10.1
28.7
13.5
13.6
13.2
19.5
63.3
16.5
10.2
8.7
10.8
12.2
12.8
17.6
52.7
11.7
1.3
1.6
12.6
19.4
23.1
23.5
40.9
1.6
10.3
4.6
22.4
3.4
7.1
6.6
7.2
1.1
2.9
4.1
2.1
0.6
2.3
4.4
0.9
0.9
3.7
1.3
1.0
1.2
1.5
1.0
0.5
0.5
1.1
0.8
0.6
0.8
2.2
0.5
0.4
0.3
0.3
0.6
1.4
7.5
1.0
0.5
5.52
7.81
44.10
41.30
34.92
51.71
99.23
13.72
25.57
25.62
49.49
10.34
43.58
17.82
30.64
4.38
16.31
20.77
8.47
4.26
18.00
10.62
7.09
6.00
4.64
35.45
7.25
2.28
6.31
19.18
5.41
6.98
9.28
10.12
3.12
10.40
0.00
10.22
9.55
7.69
3.66
5.09
6.54
8.02
3.52
3.90
2.33
2.95
9.83
32.81
20.31
22.17
86.55
5.54
14.33
11.17
81.33
10.05
40.14
8.35
29.93
5.12
7.83
5.94
11.90
2.70
4.63
9.05
0.00
0.00
4.56
0.00
0.00
6.66
0.00
0.00
0.00
0.54
0.47
0.00
0.00
0.00
8.81
0.00
0.00
0.31
1.38
2.45
1.82
1.89
13.26
9.28
0.02
0.03
0.18
0.15
0.13
0.18
0.41
0.04
0.12
0.13
0.24
0.04
0.15
0.06
0.10
0.01
0.07
0.08
0.03
0.02
0.06
0.05
0.20
0.26
0.05
0.10
0.29
0.25
0.12
0.25
0.53
0.44
0.37
0.49
0.54
0.62
0.22
0.38
0.34
0.31
0.48
0.31
0.52
0.40
0.41
0.46
145
Site 463 Minor Element Data (cont.)
Depth (m)
65Cu
66Zn
74Se
75As
85Rb
615.59
615.89
615.89
616.21
616.46
616.60
616.92
617.29
617.60
617.88
618.02
618.02
618.28
618.60
618.90
619.20
619.70
619.70
620.20
620.70
621.20
621.70
622.20
622.50
622.79
623.06
623.01
623.28
623.59
623.88
623.88
624.21
624.50
624.80
625.10
625.40
625.71
626.00
626.00
626.29
626.60
627.00
627.30
627.52
627.52
627.81
17.6
52.7
11.7
20.2
17.4
5.3
16.7
10.9
11.8
16.8
9.1
9.1
15.8
23.5
12.8
12.9
14.9
17.7
14.8
13.5
13.4
26.6
24.7
24.0
13.6
24.8
18.6
22.2
8.8
10.6
10.1
17.4
10.8
13.8
14.6
10.5
10.9
11.5
8.2
13.9
11.0
10.6
21.4
6.0
6.0
19.9
7.5
1.0
0.5
1.4
1.3
0.4
1.1
0.7
0.9
0.3
0.4
0.3
0.4
0.4
0.7
1.0
2.2
2.6
2.3
4.7
4.9
1.9
4.7
0.5
0.7
0.5
1.3
0.9
0.5
0.3
0.5
0.6
0.3
0.6
1.0
0.4
0.5
0.9
0.5
0.4
0.4
0.5
0.6
0.7
0.5
1.1
8.02
3.52
3.90
3.94
3.57
2.96
3.52
5.27
3.60
2.80
3.33
2.30
2.79
5.74
2.13
2.55
11.90
15.73
9.62
6.28
2.14
7.94
16.52
1.77
4.11
2.42
5.43
2.47
3.92
1.19
1.18
8.76
0.79
3.75
0.94
3.32
4.72
20.64
9.08
0.80
2.64
3.96
1.20
7.00
5.54
10.46
1.89
13.26
9.28
3.84
2.14
0.70
2.49
1.01
3.01
1.67
0.09
0.40
0.52
0.62
1.60
1.36
4.71
4.78
3.33
10.87
2.47
2.52
6.49
0.64
0.00
0.00
0.00
0.00
0.00
0.20
0.32
0.99
0.61
0.14
0.96
0.65
0.00
0.00
0.00
0.10
0.15
0.00
0.97
0.00
0.00
0.00
0.40
0.41
0.46
0.43
0.44
0.27
0.46
0.47
0.44
0.51
0.39
0.44
0.41
0.42
0.37
0.40
0.06
0.08
0.05
0.03
0.01
0.04
0.07
0.40
0.40
0.52
0.33
0.48
0.32
0.44
0.39
0.43
0.41
0.44
0.47
0.32
0.46
0.18
0.33
0.37
0.26
0.35
0.21
0.29
0.33
0.23
146
Site 463 Minor Element Data (cont.)
Depth (m)
65Cu
66Zn
74Se
75As
85Rb
628.09
628.38
628.60
632.63
633.52
634.14
635.05
635.60
636.53
636.53
637.10
638.15
642.15
643.04
643.92
644.83
645.13
646.05
646.92
647.82
647.82
651.88
652.81
653.58
661.17
661.74
14.8
11.0
53.4
41.9
23.0
12.2
43.3
46.4
23.7
28.9
6.5
5.1
5.2
6.3
6.7
27.0
14.3
4.9
4.2
4.7
4.6
11.8
7.1
8.7
9.2
9.0
1.1
0.7
1.4
0.9
1.0
0.6
0.8
0.6
0.7
0.7
0.5
0.3
0.4
0.4
0.3
0.7
0.3
0.6
0.1
0.4
0.3
1.9
3.7
6.6
6.9
3.0
5.28
8.55
0.00
0.11
3.00
1.39
0.00
0.17
0.74
0.00
5.12
3.93
4.22
5.69
4.94
10.51
2.01
5.32
1.66
6.90
10.81
18.99
11.55
10.55
13.78
8.70
0.51
0.00
4.16
4.20
3.77
0.00
5.44
6.52
1.18
3.35
0.68
1.18
0.00
0.49
0.00
0.00
0.00
7.15
0.00
0.00
0.00
6.99
5.07
5.86
7.52
4.18
0.34
0.23
0.07
0.26
0.39
0.25
0.18
0.24
0.12
0.11
0.23
0.26
0.32
0.39
0.33
0.56
0.29
0.00
0.02
0.03
0.06
0.12
0.11
0.06
0.07
0.04
147
Site 463 Minor Element Data (cont.)
Depth (mbsf)
Sr/Zr
Y/Zr
Mo/Zr
Ag/Zr
Cd/Zr
585.00
585.00
585.38
585.79
586.22
586.50
586.90
587.29
587.71
594.67
604.10
604.50
604.50
604.99
605.22
605.40
605.69
605.84
606.00
606.39
606.69
607.10
607.03
607.28
607.49
607.61
607.89
608.62
608.91
609.20
609.48
609.79
610.01
610.30
610.30
610.58
613.51
613.91
614.23
614.62
614.88
615.03
615.31
615.59
615.89
615.89
1.4
1.9
12.6
10.2
9.1
12.7
28.6
3.0
8.2
8.8
18.6
3.1
10.6
4.5
6.9
1.1
5.0
5.8
2.1
1.2
4.1
3.5
14.6
16.7
3.4
20.3
18.7
12.7
23.4
13.8
4.5
7.5
9.7
8.1
8.2
8.7
7.7
7.3
9.4
6.4
4.7
4.1
7.2
5.6
1.8
2.0
9.80
4.73
0.00
0.00
26.75
0.00
0.00
0.00
12.38
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.22
0.00
0.00
0.00
13.15
3.73
4.20
58.81
5.98
5.80
4.16
5.94
4.52
1.64
2.52
3.11
2.33
2.20
2.22
0.61
1.90
2.50
2.60
1.11
1.09
1.59
3.25
0.47
0.52
1.33
2.15
17.72
48.49
29.75
29.89
161.14
5.32
11.57
11.37
159.35
12.33
39.84
8.44
33.03
5.24
6.70
5.21
12.10
2.39
3.76
5.27
0.84
10.15
2.60
0.65
0.01
0.01
0.00
0.00
0.01
0.01
0.12
10.00
0.00
0.02
0.02
0.02
0.04
0.04
0.03
0.03
0.04
0.07
0.05
0.02
0.59
0.66
3.61
9.73
4.82
5.34
22.52
1.16
1.60
1.93
20.02
2.41
8.82
1.48
6.54
1.15
1.44
1.03
2.64
0.57
1.00
1.44
4.53
0.00
0.65
6.78
4.17
4.39
4.31
4.14
3.84
4.00
0.97
1.23
9.11
8.52
6.41
8.87
15.93
2.14
7.32
16.59
15.90
9.43
8.63
2.86
11.99
1.00
4.16
3.80
1.21
0.72
3.27
2.84
0.00
0.00
1.95
11.43
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
10.72
136.13
11.74
17.86
9.76
24.25
21.39
8.46
38.82
19.58
53.30
2.14
3.75
4.16
5.81
4.55
5.09
7.36
7.26
4.55
6.83
6.68
7.30
5.03
148
Site 463 Minor Element Data (cont.)
Depth (m)
86Sr
89Y
95Mo
107Ag
111Cd
615.59
615.89
615.89
616.21
616.46
616.60
616.92
617.29
617.60
617.88
618.02
618.02
618.28
618.60
618.90
619.20
619.70
619.70
620.20
620.70
621.20
621.70
622.20
622.50
622.79
623.06
623.01
623.28
623.59
623.88
623.88
624.21
624.50
624.80
625.10
625.40
625.71
626.00
626.00
626.29
626.60
627.00
627.30
627.52
627.52
627.81
5.6
1.8
2.0
4.0
4.4
7.8
6.4
2.9
5.1
3.1
3.1
3.3
4.6
16.2
3.5
2.9
4.5
5.3
3.7
2.0
0.7
2.6
5.0
3.3
10.9
7.2
9.0
8.6
2.8
2.1
1.8
5.5
1.9
4.8
2.7
6.2
9.1
13.4
11.9
5.2
5.5
4.5
5.9
9.4
9.2
12.4
3.25
0.47
0.52
1.66
1.64
0.66
1.56
0.93
0.97
0.96
1.04
1.09
0.97
2.57
0.78
0.85
41.73
49.55
38.53
519.85
348.77
27.37
90.21
0.61
2.25
0.87
2.47
1.45
0.67
0.58
0.49
1.33
0.46
1.29
0.52
2.07
3.57
3.90
3.14
1.22
1.18
1.06
1.99
2.14
2.16
5.23
0.07
0.05
0.02
0.03
0.08
0.02
0.03
0.04
0.01
0.02
0.02
0.03
0.02
0.04
0.04
0.03
2.85
2.92
2.51
7.98
14.84
1.48
7.66
0.04
2.20
0.21
0.03
0.03
0.01
0.15
0.04
0.00
0.82
0.01
0.01
0.01
0.72
1.31
0.00
0.00
0.00
0.00
0.01
0.01
0.05
0.09
6.68
7.30
5.03
5.30
5.99
4.86
7.85
31.55
3.69
6.61
4.40
4.76
5.62
9.87
5.56
7.66
0.97
0.90
0.68
0.44
0.18
0.36
1.33
8.56
10.19
10.29
6.19
6.34
3.69
3.81
5.18
0.00
6.09
6.10
6.41
5.62
10.06
5.12
5.67
2.84
0.37
5.59
5.57
5.87
6.72
6.74
38.82
19.58
53.30
21.97
51.12
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2.93
3.44
2.42
1.52
0.60
2.65
5.54
0.00
11.87
62.15
0.00
8.70
0.00
157.54
13.51
0.00
2.75
1.07
0.61
0.28
23.72
11.15
0.24
51.67
0.00
0.19
0.94
0.00
1.03
1.80
149
Site 463 Minor Element Data (cont.)
Depth (m)
86Sr
89Y
95Mo
107Ag
111Cd
628.09
628.38
628.60
632.63
633.52
634.14
635.05
635.60
636.53
636.53
637.10
638.15
642.15
643.04
643.92
644.83
645.13
646.05
646.92
647.82
647.82
651.88
652.81
653.58
661.17
661.74
8.9
12.6
6.5
4.3
6.1
6.9
2.9
3.9
5.8
4.4
5.0
3.8
3.9
5.1
7.5
23.5
4.9
9.0
1.4
4.5
4.4
7.9
7.4
4.5
5.1
2.6
3.48
5.24
2.86
1.89
3.52
2.24
0.72
1.43
1.73
1.30
2.04
1.04
1.77
1.80
2.19
3.43
1.29
2.15
0.64
1.82
1.81
1.14
0.00
0.00
0.00
0.10
0.05
0.03
0.04
0.15
0.04
0.56
0.03
0.00
3.09
0.02
0.01
0.01
0.05
0.01
0.06
0.02
0.01
0.02
0.02
0.01
0.01
7.85
7.41
8.91
9.22
5.80
6.98
6.46
6.62
6.12
6.63
23.11
6.04
0.00
0.00
11.26
144.86
0.38
0.00
5.33
0.00
15.73
93.31
7.96
2.19
10.46
0.00
31.77
8.46
3.60
3.53
6.13
4.70
3.46
4.26
3.35
2.13
4.87
1.45
32.52
7.00
6.93
7.68
9.22
5.51
18.38
7.84
8.26
7.72
7.51
6.45
6.69
1.85
1.36
1.51
1.73
0.93
150
Site 463 Minor Element Data (cont.)
Depth (mbsf)
In/Zr
Sn/Zr
Sb/Zr
Cs/Zr
Ba/Zr
585.00
585.00
585.38
585.79
586.22
586.50
586.90
587.29
587.71
594.67
604.10
604.50
604.50
604.99
605.22
605.40
605.69
605.84
606.00
606.39
606.69
607.10
607.03
607.28
607.49
607.61
607.89
608.62
608.91
609.20
609.48
609.79
610.01
610.30
610.30
610.58
613.51
613.91
614.23
614.62
614.88
615.03
615.31
615.59
615.89
615.89
0.34
0.46
2.44
2.94
2.10
2.87
6.41
0.75
1.39
1.31
3.61
0.67
2.72
1.10
1.87
0.28
0.95
1.22
0.57
0.25
1.14
0.72
0.00
0.00
0.19
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2.32
3.03
28.77
91.01
37.21
35.72
68.86
6.46
40.43
40.34
60.39
6.62
25.88
24.26
25.98
3.15
24.20
15.67
7.97
0.86
10.98
18.34
5.78
0.00
0.34
0.00
13.57
7.12
0.00
23.24
0.00
11.30
0.00
0.00
0.00
0.00
0.12
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2.32
3.03
28.65
90.76
37.13
35.60
68.95
6.45
37.93
33.14
60.65
6.65
25.98
23.82
26.00
3.16
23.75
15.49
7.99
0.86
10.87
18.15
22.55
0.00
0.34
49.00
3.87
11.85
0.00
10.57
0.00
15.82
0.00
0.00
0.00
0.36
2.46
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.70
2.17
9.62
11.79
9.90
11.18
21.02
3.23
5.65
4.34
11.33
2.28
7.58
5.20
7.62
1.21
2.78
3.90
1.37
1.06
3.08
3.02
1.31
0.00
1.43
3.79
2.39
1.93
0.22
0.15
0.21
0.18
0.00
0.05
0.75
0.92
0.79
0.81
0.53
0.75
0.82
0.58
0.72
0.64
0.69
0.86
0.6
0.6
3.5
9.5
4.7
5.3
22.3
1.1
1.6
2.0
19.7
2.4
8.7
1.5
6.4
1.1
1.4
1.0
2.6
0.6
1.0
1.4
2.1
1.2
0.6
5.6
3.6
4.1
8.5
5.9
3.5
5.3
1.4
1.3
5.6
25.1
20.5
46.0
12.8
37.6
34.4
23.2
37.8
26.0
19.5
28.4
151
Site 463 Minor Element Data (cont.)
Depth (m)
115In
118Sn
121Sb
133Cs
135Ba
615.59
615.89
615.89
616.21
616.46
616.60
616.92
617.29
617.60
617.88
618.02
618.02
618.28
618.60
618.90
619.20
619.70
619.70
620.20
620.70
621.20
621.70
622.20
622.50
622.79
623.06
623.01
623.28
623.59
623.88
623.88
624.21
624.50
624.80
625.10
625.40
625.71
626.00
626.00
626.29
626.60
627.00
627.30
627.52
627.52
627.81
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.98
1.26
0.71
0.48
0.15
0.58
1.22
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
8.67
14.04
7.86
7.75
4.06
11.00
21.14
0.00
49.90
0.00
0.00
0.00
0.00
0.00
0.00
0.00
15.78
23.94
18.88
15.76
34.50
32.97
7.17
25.46
1.82
27.54
7.80
3.00
28.60
29.98
0.00
0.00
0.00
0.00
0.00
0.00
1.87
0.00
0.19
0.00
0.00
0.00
0.00
0.00
0.00
1.84
8.63
13.84
7.77
7.43
3.83
11.21
20.83
0.00
9.82
0.95
1.33
1.36
0.00
0.00
0.00
0.00
21.92
5.48
12.67
15.07
58.16
8.53
0.18
3.66
0.48
10.63
0.30
3.26
4.05
5.61
0.64
0.69
0.86
0.70
0.31
0.83
0.81
1.03
1.58
0.99
0.46
0.70
0.89
0.71
1.02
0.88
4.11
4.85
3.07
1.74
0.53
2.38
4.98
0.90
1.05
0.96
0.93
0.89
1.59
0.77
0.84
0.00
1.22
2.29
1.84
0.14
4.03
0.16
0.19
2.75
0.00
0.11
0.19
1.51
1.75
1.66
26.0
19.5
28.4
23.5
8.0
32.5
25.0
32.7
11.9
27.1
16.4
66.2
21.3
30.6
40.7
34.8
0.9
0.9
0.7
0.4
0.2
0.3
1.3
49.2
14.1
16.9
39.3
29.0
11.9
46.4
33.3
0.0
1.8
3.1
3.5
4.4
5.6
0.6
7.0
0.0
0.0
4.8
2.9
10.4
3.5
3.6
152
Site 463 Minor Element Data (cont.)
Depth (m)
115In
118Sn
121Sb
133Cs
135Ba
628.09
628.38
628.60
632.63
633.52
634.14
635.05
635.60
636.53
636.53
637.10
638.15
642.15
643.04
643.92
644.83
645.13
646.05
646.92
647.82
647.82
651.88
652.81
653.58
661.17
661.74
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.45
0.89
0.78
0.99
0.65
26.97
23.40
25.92
33.05
33.49
55.68
25.94
0.00
124.17
11.27
11.09
2.91
9.11
11.79
30.29
13.10
11.85
13.23
11.36
10.72
8.89
9.72
8.02
5.91
7.78
5.78
4.17
4.10
3.78
3.08
3.02
44.73
2.69
0.00
102.23
1.34
1.24
12.16
12.33
3.31
12.06
4.51
2.77
3.10
2.12
2.43
2.96
9.70
8.00
5.94
7.79
5.76
1.80
1.79
1.63
1.62
1.61
0.00
1.73
18.57
0.00
0.01
0.09
0.02
0.00
1.54
0.89
0.55
0.75
0.67
0.33
0.62
0.46
5.26
2.70
2.22
3.42
2.24
4.7
3.7
3.7
3.6
3.8
32.1
3.2
0.0
48.8
10.6
10.8
4.3
3.6
10.5
90.8
19.8
36.4
33.9
12.4
13.7
10.6
1.8
1.3
1.5
1.7
0.9
153
Site 463 Minor Element Data (cont.)
Depth (mbsf)
W/Zr
Re/Zr
Au/Zr
Hg/Zr
Tl/Zr
585.00
585.00
585.38
585.79
586.22
586.50
586.90
587.29
587.71
594.67
604.10
604.50
604.50
604.99
605.22
605.40
605.69
605.84
606.00
606.39
606.69
607.10
607.03
607.28
607.49
607.61
607.89
608.62
608.91
609.20
609.48
609.79
610.01
610.30
610.30
610.58
613.51
613.91
614.23
614.62
614.88
615.03
615.31
615.59
615.89
615.89
1.02
1.28
7.65
20.75
12.02
38.93
99.14
5.86
8.74
11.28
94.59
10.32
31.34
5.48
20.44
7.63
8.85
6.83
13.97
2.29
4.19
7.05
0.00
0.00
2.83
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.44
1.94
9.01
13.81
14.62
9.45
22.48
2.26
9.95
9.81
4.69
2.30
8.84
4.00
3.95
0.52
5.22
3.82
1.28
0.67
2.28
3.78
0.00
0.00
0.85
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.14
0.19
0.76
1.34
1.38
1.48
8.64
0.91
0.81
0.97
6.47
0.29
0.86
0.51
1.14
0.14
0.30
0.34
0.24
0.08
0.21
1.56
1.04
0.00
0.33
1.54
1.12
0.75
0.50
0.59
1.53
0.48
0.00
0.00
0.38
1.23
1.27
1.12
0.88
1.22
1.21
0.68
0.97
0.78
0.98
1.17
0.15
0.20
0.80
1.37
1.43
1.51
8.86
0.94
0.85
0.98
6.57
0.31
0.88
0.53
1.16
0.14
0.31
0.35
0.24
0.08
0.22
1.60
0.00
0.00
0.35
0.00
0.00
0.00
0.00
0.00
94.14
0.00
0.00
9.79
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.23
0.30
1.81
2.26
1.78
2.30
4.82
0.53
1.60
21.84
3.37
0.42
1.17
1.45
3.34
0.77
3.09
0.89
0.43
0.52
0.71
2.84
36.45
0.00
0.19
11.60
5.87
4.85
4.42
6.44
1.38
1.31
0.00
0.00
2.05
2.39
2.38
3.00
1.18
3.35
2.76
1.04
2.10
2.11
2.17
3.17
154
Site 463 Minor Element Data (cont.)
Depth (m)
182W
187Re
197Au
200Hg
205Tl
615.59
615.89
615.89
616.21
616.46
616.60
616.92
617.29
617.60
617.88
618.02
618.02
618.28
618.60
618.90
619.20
619.70
619.70
620.20
620.70
621.20
621.70
622.20
622.50
622.79
623.06
623.01
623.28
623.59
623.88
623.88
624.21
624.50
624.80
625.10
625.40
625.71
626.00
626.00
626.29
626.60
627.00
627.30
627.52
627.52
627.81
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
4.01
4.93
5.37
3.37
1.59
5.64
12.16
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.01
0.01
0.00
0.06
0.00
0.00
0.00
0.00
0.00
0.57
0.01
0.02
0.02
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.94
2.22
1.44
16.48
5.02
1.86
2.99
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.78
0.98
1.17
0.83
0.42
1.34
1.14
0.96
0.78
1.14
0.64
1.01
1.32
1.16
1.27
1.16
0.28
0.40
0.31
0.30
0.09
0.41
0.65
0.93
1.69
1.03
1.34
1.14
0.64
0.94
0.93
0.00
0.96
1.20
0.70
0.48
1.81
0.35
0.44
0.34
0.28
0.56
1.47
0.77
0.97
1.39
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.29
0.41
0.32
0.31
0.09
0.43
0.68
0.00
28.85
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.44
3.14
1.51
0.26
13.99
2.34
0.13
12.83
6.01
0.12
95.35
1.88
1.25
0.64
2.11
2.17
3.17
2.09
0.67
2.92
3.22
3.75
4.26
3.26
1.98
3.30
3.09
3.08
4.53
3.58
2.20
2.61
1.57
1.48
0.67
4.44
6.71
4.46
5.47
5.93
3.83
3.71
4.22
4.21
4.11
0.00
34.48
5.63
4.60
1.22
12.71
1.23
4.12
0.30
0.36
5.84
1.29
4.28
5.31
5.41
155
Site 463 Minor Element Data (cont.)
Depth (m)
182W
187Re
197Au
200Hg
205Tl
628.09
628.38
628.60
632.63
633.52
634.14
635.05
635.60
636.53
636.53
637.10
638.15
642.15
643.04
643.92
644.83
645.13
646.05
646.92
647.82
647.82
651.88
652.81
653.58
661.17
661.74
0.02
0.02
0.02
0.02
0.02
0.05
0.01
0.00
0.08
0.00
0.00
0.00
0.01
0.01
0.02
0.01
0.01
0.01
0.02
0.01
0.01
16.38
9.92
9.27
9.19
4.65
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.90
1.20
1.04
1.36
1.12
1.37
1.09
1.84
0.91
1.10
6.30
0.94
0.00
77.27
0.72
0.57
0.25
0.82
0.72
1.93
1.12
0.87
1.25
1.67
1.02
0.90
0.99
0.28
0.20
0.32
0.24
1.47
8.04
1.92
0.00
3.73
6.90
4.72
0.00
32.96
0.00
0.00
0.00
0.00
2.18
0.25
0.33
0.48
1.40
2.27
0.88
0.79
1.01
0.29
0.20
0.33
0.25
6.11
5.22
5.22
5.58
5.15
2.23
4.65
0.00
6.73
0.63
0.61
0.29
3.52
4.26
6.38
2.30
3.23
2.97
1.76
2.24
1.72
1.02
0.49
0.35
0.51
0.31
156
Site 463 Minor Element Data (cont.)
Depth (mbsf)
Pb/Zr
Bi/Zr
Th/Zr
U/Zr
585.00
585.00
585.38
585.79
586.22
586.50
586.90
587.29
587.71
594.67
604.10
604.50
604.50
604.99
605.22
605.40
605.69
605.84
606.00
606.39
606.69
607.10
607.03
607.28
607.49
607.61
607.89
608.62
608.91
609.20
609.48
609.79
610.01
610.30
610.30
610.58
613.51
613.91
614.23
614.62
614.88
615.03
615.31
615.59
615.89
615.89
94
117
732
743
584
725
1696
185
389
536
1040
181
657
232
503
77
297
324
157
67
300
199
150
117
32
811
196
198
139
209
43
150
87
120
61
58
59
102
65
93
100
84
81
81
65
53
238
300
1737
2757
1846
2294
6114
523
1389
16593
4837
585
1875
1231
3211
715
2451
776
620
453
631
2266
951
0
206
7563
1285
1292
541
57
81
104
0
0
681
765
1130
4024
1111
1695
1564
1121
2827
1485
2033
1374
8712
11098
69360
56184
50587
64412
127205
17055
38228
52883
63388
13609
49188
21067
38112
5557
28257
32019
10452
5771
29522
17844
28354
4301
1870
50452
44654
34459
58359
129143
15907
13928
5189
4296
16611
22568
19534
22477
11152
18871
19741
10350
19070
12237
17916
19386
2453
3530
8489
15592
10933
10128
29818
2415
7851
3904
45020
3240
13875
4483
8730
1409
3895
4633
3799
1858
4240
6904
243
0
7166
5219
1062
1033
536
538
419
396
0
0
398
274
243
491
349
672
612
315
187
569
260
602
157
Site 463 Minor Element Data (cont.)
Depth (m)
207Pb
209Bi
232Th
238U
615.59
615.89
615.89
616.21
616.46
616.60
616.92
617.29
617.60
617.88
618.02
618.02
618.28
618.60
618.90
619.20
619.70
619.70
620.20
620.70
621.20
621.70
622.20
622.50
622.79
623.06
623.01
623.28
623.59
623.88
623.88
624.21
624.50
624.80
625.10
625.40
625.71
626.00
626.00
626.29
626.60
627.00
627.30
627.52
627.52
627.81
81
65
53
76
67
52
107
91
128
81
30
54
49
112
92
91
197
272
175
114
42
145
290
78
83
99
100
88
128
83
60
1485
2033
1374
2098
1476
1352
1147
1191
1470
1409
367
2311
1115
1143
1387
1619
1658
1949
1189
1094
501
3185
4769
1843
736
459
1557
1190
1419
2896
921
0
835
1181
1164
63
8037
120
487
5975
1842
2
59
1327
930
1091
12237
17916
19386
15537
5961
20409
19014
21759
34414
23843
11701
17855
21420
17792
22161
18268
18073
26050
16454
10727
3941
14114
26178
19769
19279
22011
20601
18380
33835
19027
20481
40143
23734
38117
29015
11508
46070
3244
49735
32616
39741
43484
13062
29409
38081
38749
569
260
602
235
384
655
966
947
828
395
348
576
360
449
711
789
6971
9057
6525
20527
9068
4849
13257
2040
772
893
851
823
824
292
430
14148
14817
1064
1026
348
6465
482
528
11483
14182
489
394
639
0
0
137
177
181
132
422
109
124
0
0
182
39
126
226
236
158
Site 463 Minor Element Data (cont.)
Depth (m)
207Pb
209Bi
232Th
238U
628.09
628.38
628.60
632.63
633.52
634.14
635.05
635.60
636.53
636.53
637.10
638.15
642.15
643.04
643.92
644.83
645.13
646.05
646.92
647.82
647.82
651.88
652.81
653.58
661.17
661.74
308
249
236
222
232
563
177
0
701
81
60
32
145
126
329
117
82
107
87
98
90
266
274
182
278
129
207
909
712
564
410
0
947
0
0
0
0
0
0
1293
0
0
590
11
25
49
97
929
495
416
550
321
42500
40188
37412
37524
39078
0
38273
60122
0
4019
4408
4072
1591
29893
0
15721
14058
10990
11284
12909
12194
23506
25381
15554
24835
11241
0
0
0
0
0
11422
213
0
9554
0
0
384
2841
660
0
0
0
0
0
0
0
3630
7433
6043
5585
4536
159
160
161
162
163
164
Site 463 Major Element Data
Depth (m) Ba/Al
585.00
585.00
585.38
585.79
586.22
586.50
586.90
587.29
587.71
594.67
604.10
604.50
604.50
604.99
605.22
605.40
605.69
605.84
606.00
606.39
606.69
607.10
607.03
607.28
607.49
607.61
607.89
608.62
608.91
609.20
609.48
609.79
610.01
610.30
610.30
610.58
613.51
613.91
614.23
614.62
614.88
615.03
615.31
Ca/Al
0.05
0.07
0.11
0.39
0.18
0.12
0.14
0.07
0.26
0.21
0.24
0.05
0.09
0.18
0.13
0.12
0.21
0.10
0.15
0.04
0.09
0.25
0.13
0.12
0.00
0.08
0.21
0.22
0.21
0.26
0.10
0.18
0.13
0.11
0.12
0.18
0.00
0.14
0.21
0.29
0.07
0.15
0.11
21.38
28.84
33.02
118.28
63.02
48.14
120.98
23.74
20.64
28.32
186.25
42.22
66.35
27.43
81.95
109.91
32.48
14.33
120.08
17.14
11.71
37.40
83.89
56.93
0.32
132.45
62.81
60.52
91.90
71.87
6.98
13.31
23.92
9.23
9.64
8.48
0.36
13.26
20.01
7.01
3.32
6.36
6.31
Fe/Al
K/Al
0.76
1.03
1.10
2.00
2.34
1.32
2.13
0.96
1.06
1.02
2.98
0.83
1.38
1.41
2.01
2.39
1.22
0.89
1.99
1.07
0.86
1.35
1.24
1.39
0.62
1.43
1.43
6.05
2.09
1.46
0.75
0.95
0.84
0.71
0.80
0.95
0.74
0.72
0.92
0.74
0.81
1.33
1.12
Mg/Al
0.12
0.25
0.32
0.07
0.25
0.27
0.00
0.25
0.42
0.38
0.00
0.00
0.05
0.28
0.00
0.00
0.30
0.32
0.00
0.05
0.24
0.07
1.12
0.57
0.15
1.03
0.00
1.06
0.83
0.66
0.50
0.53
0.23
0.21
0.67
0.39
0.22
0.74
0.36
0.32
0.34
0.36
0.39
Mg/Al
0.31
0.42
0.42
0.82
0.58
0.55
0.93
0.36
0.35
0.35
1.20
0.32
0.55
0.44
0.68
0.82
0.37
0.31
0.90
0.37
0.30
0.42
0.60
0.42
0.20
0.74
0.48
0.40
0.58
0.56
0.25
0.27
0.31
0.24
0.26
0.32
0.14
0.28
0.29
0.29
0.22
0.27
0.25
0.30
0.40
0.39
0.81
0.56
0.52
0.91
0.35
0.33
0.33
1.23
0.32
0.54
0.41
0.66
0.80
0.35
0.29
0.89
0.38
0.29
0.42
0.66
0.46
0.19
0.81
0.55
0.43
0.64
0.63
0.29
0.29
0.34
0.27
0.29
0.36
0.16
0.30
0.33
0.32
0.25
0.29
0.27
165
Site 463 Major Element Data (cont.)
Depth (m) Ba/Al
615.59
615.89
615.89
616.21
616.46
616.60
616.92
617.29
617.60
617.88
618.02
618.02
618.28
618.60
618.90
619.20
619.70
619.70
620.20
620.70
621.20
621.70
622.20
622.50
622.95
623.01
623.28
623.59
623.88
623.88
624.21
624.80
625.10
625.40
625.71
626.00
626.29
626.60
627.00
627.30
627.52
627.52
627.81
628.09
628.09
Ca/Al
0.19
0.05
0.06
0.15
0.10
0.07
0.10
0.09
0.08
0.09
0.10
0.12
0.06
0.05
0.15
0.12
0.09
0.11
0.10
0.14
0.22
0.18
0.17
0.17
0.05
0.01
0.04
0.19
0.10
0.09
0.14
0.12
0.11
0.14
0.15
0.25
0.08
0.14
0.06
0.14
0.20
0.22
0.18
0.17
0.14
6.03
0.24
0.22
4.71
3.43
2.62
0.53
2.36
1.09
1.00
0.35
0.36
1.10
4.06
0.66
0.46
1.00
1.00
7.96
7.69
12.96
1.92
0.55
0.14
0.28
4.43
0.67
0.20
0.12
0.12
8.13
6.41
0.27
14.00
19.68
35.80
11.24
14.84
8.37
29.98
18.35
22.42
82.90
37.06
35.12
Fe/Al
K/Al
0.93
3.33
1.16
1.01
1.06
0.57
0.84
0.92
0.88
0.71
0.59
0.63
0.67
0.52
1.00
0.95
0.83
0.79
0.96
2.10
0.96
0.84
1.06
0.59
0.66
1.91
1.27
0.76
0.79
0.83
0.75
0.68
0.61
0.81
0.97
1.12
1.10
0.99
0.66
2.19
0.54
0.67
1.00
1.24
0.85
Mg/Al
0.46
0.46
0.40
0.35
0.39
0.47
0.51
0.36
0.41
0.44
0.50
0.30
0.11
0.20
0.29
0.46
0.12
0.17
0.16
0.20
0.21
0.22
0.12
0.42
0.34
0.23
0.31
0.76
0.45
0.41
0.61
0.25
0.40
0.37
0.60
0.55
0.12
0.00
0.17
0.00
0.00
0.11
0.33
0.69
0.06
Mg/Al
0.27
0.24
0.24
0.23
0.23
0.16
0.24
0.22
0.21
0.24
0.25
0.26
0.24
0.19
0.24
0.25
0.27
0.27
0.31
0.27
0.27
0.26
0.25
0.21
0.23
0.29
0.26
0.28
0.21
0.20
0.25
0.25
0.22
0.26
0.27
0.38
0.26
0.27
0.24
0.29
0.29
0.31
0.57
0.49
0.36
0.30
0.26
0.27
0.26
0.25
0.18
0.26
0.24
0.23
0.27
0.27
0.29
0.26
0.21
0.26
0.28
0.27
0.26
0.30
0.27
0.26
0.25
0.25
0.24
0.26
0.32
0.29
0.31
0.23
0.23
0.28
0.28
0.24
0.28
0.29
0.43
0.26
0.27
0.24
0.29
0.29
0.31
0.55
0.52
0.36
166
Site 463 Major Element Data (cont.)
Depth (m) Ba/Al
628.38
628.38
628.60
632.63
633.52
634.14
635.05
635.60
636.53
636.53
651.88
652.81
653.58
661.17
661.74
Ca/Al
0.24
0.21
0.14
0.08
0.20
0.10
0.07
0.10
0.11
0.12
0.08
0.09
0.10
0.09
0.11
56.10
58.25
55.92
22.84
12.68
23.34
13.71
13.92
27.27
28.78
19.05
30.89
50.23
45.81
45.29
Fe/Al
K/Al
1.35
0.85
4.76
3.00
1.55
1.27
4.31
2.68
2.31
4.02
0.95
1.05
1.28
1.17
1.17
Mg/Al
0.42
0.00
0.02
0.38
0.41
0.00
0.31
0.39
0.14
0.00
0.09
0.09
0.05
0.10
0.17
Mg/Al
0.53
0.48
0.32
0.27
0.26
0.28
0.25
0.25
0.25
0.28
0.36
0.46
0.48
0.49
0.49
0.58
0.48
0.31
0.28
0.26
0.28
0.25
0.25
0.26
0.28
0.36
0.45
0.48
0.47
0.47
167
Site 463 Major Element Data (cont.)
Depth (m) Mn/Al
585.00
585.00
585.38
585.79
586.22
586.50
586.90
587.29
587.71
594.67
604.10
604.50
604.50
604.99
605.22
605.40
605.69
605.84
606.00
606.39
606.69
607.10
607.03
607.28
607.49
607.61
607.89
608.62
608.91
609.20
609.48
609.79
610.01
610.30
610.30
610.58
613.51
613.91
614.23
614.62
614.88
615.03
615.31
Na/Al
0.03
0.04
0.05
0.21
0.10
0.06
0.16
0.04
0.05
0.06
0.40
0.10
0.18
0.06
0.21
0.29
0.07
0.03
0.30
0.05
0.05
0.15
0.16
0.13
0.00
0.33
0.15
0.30
0.26
0.21
0.02
0.06
0.11
0.05
0.05
0.03
0.01
0.09
0.16
0.04
0.02
0.03
0.05
P/Al
0.21
0.32
0.30
0.52
0.49
0.40
0.62
0.26
0.30
0.31
0.83
0.14
0.30
0.31
0.35
0.46
0.23
0.19
0.54
0.24
0.15
0.30
0.43
0.22
0.17
0.42
0.20
0.44
0.39
0.27
0.18
0.17
0.18
0.20
0.22
0.25
0.17
0.28
0.31
0.26
0.16
0.28
0.19
Ti/Al
0.03
0.02
0.02
0.11
0.06
0.03
0.04
0.02
0.06
0.02
0.17
0.03
0.04
0.07
0.05
0.03
0.06
0.03
0.11
0.02
0.04
0.08
0.17
0.08
0.01
0.27
0.12
0.10
0.07
0.04
0.02
0.10
0.03
0.03
0.06
0.01
0.00
0.10
0.07
0.11
0.00
0.00
0.01
0.08
0.10
0.10
0.19
0.15
0.12
0.18
0.09
0.12
0.09
0.26
0.08
0.13
0.13
0.17
0.19
0.11
0.09
0.17
0.12
0.08
0.15
0.11
0.09
0.09
0.13
0.11
0.09
0.09
0.13
0.09
0.10
0.12
0.10
0.10
0.10
0.09
0.14
0.14
0.14
0.14
0.19
0.11
168
Site 463 Major Element Data (cont.)
Depth (m) Mn/Al
615.59
615.89
615.89
616.21
616.46
616.60
616.92
617.29
617.60
617.88
618.02
618.02
618.28
618.60
618.90
619.20
619.70
619.70
620.20
620.70
621.20
621.70
622.20
622.50
622.95
623.01
623.28
623.59
623.88
623.88
624.21
624.80
625.10
625.40
625.71
626.00
626.29
626.60
627.00
627.30
627.52
627.52
627.81
628.09
628.09
Na/Al
0.02
0.09
0.01
0.03
0.05
0.02
0.01
0.02
0.00
0.01
0.00
0.00
0.02
0.13
0.00
0.01
0.01
0.01
0.22
0.11
0.44
0.02
0.01
0.00
0.00
0.09
0.03
0.01
0.01
0.00
0.09
0.06
0.00
0.13
0.18
0.27
0.07
0.07
0.04
0.18
0.06
0.09
0.35
0.14
0.13
P/Al
0.26
0.24
0.24
0.18
0.19
0.30
0.24
0.19
0.24
0.21
0.20
0.22
0.24
0.27
0.21
0.21
0.18
0.21
0.22
0.26
0.22
0.21
0.22
0.24
0.24
0.20
0.24
0.22
0.17
0.18
0.26
0.34
0.27
0.27
0.33
0.52
0.25
0.28
0.34
0.46
0.21
0.24
0.26
0.84
0.25
Ti/Al
0.03
0.03
0.01
0.04
0.02
0.04
0.07
0.02
0.02
0.00
0.02
0.03
0.01
0.04
0.02
0.01
0.01
0.02
0.04
0.02
0.04
0.01
0.01
0.04
0.01
0.02
0.00
0.07
0.00
0.02
0.04
0.04
0.01
0.03
0.05
0.06
0.01
0.04
0.02
0.03
0.01
0.01
0.11
0.06
0.06
0.15
0.12
0.12
0.14
0.12
0.06
0.11
0.12
0.13
0.12
0.13
0.13
0.13
0.09
0.15
0.14
0.16
0.15
0.14
0.11
0.12
0.12
0.12
0.13
0.11
0.10
0.09
0.13
0.12
0.14
0.12
0.11
0.10
0.13
0.13
0.14
0.10
0.12
0.10
0.12
0.10
0.13
0.15
0.15
0.12
169
Site 463 Major Element Data (cont.)
Depth (m) Mn/Al
628.38
628.38
628.60
632.63
633.52
634.14
635.05
635.60
636.53
636.53
651.88
652.81
653.58
661.17
661.74
Na/Al
0.20
0.19
0.30
0.15
0.08
0.08
0.17
0.09
0.12
0.18
0.06
0.07
0.08
0.07
0.05
P/Al
0.50
0.24
0.60
0.39
0.21
0.29
0.57
0.30
0.34
0.59
0.25
0.25
0.26
0.24
0.27
Ti/Al
0.05
0.08
0.03
0.00
0.06
0.05
0.03
0.02
0.03
0.00
0.05
0.06
0.00
0.00
0.04
0.15
0.13
0.12
0.13
0.15
0.12
0.10
0.14
0.09
0.11
0.13
0.11
0.13
0.12
0.15
170
171
172