AN ABSTRACT OF THE DISSERTATION OF
Matthew W. Loewen for the degree of Doctor of Philosophy in Geology presented on
December 16, 2013.
Title: Volatile Mobility of Trace Metals in Volcanic Systems.
Abstract approved:
_____________________________________________________________________
Adam J.R. Kent
Semi-volatile trace metals like Li, Cu, Mo, Sn, In, and Pb have the potential to
track mobility of a volatile phase in volcanic systems. In this dissertation four studies
are presented that either directly investigate or are motivated by observations of trace
metal behavior in volcanic systems. A common tool for trace element determination
in solid materials is laser ablation-inductively coupled plasma-mass spectrometry
(LA-ICP-MS). Although this technique has the potential to measure concentrations of
many elements to << 1 ppm, it also has the potential to fractionate elements of
different volatility resulting in increased analytical uncertainty. Potential sources of
fractionation in two different laser ablation systems are characterized, including a
previously unrecognized source of fractionation related to differential carrier gas flow
at the site of ablation.
Glass and melt inclusions from the 1959 eruption of Kilauea Iki record little
evidence for volatile behavior of metals, but do record variations related to mixing of
distinct batches of magma. Variations in concentrations of metals like Cu, Zn, and
Mo can be explained with olivine fractionation. Only Sn variations appear to be
compatible with volatile mobility. Lithophile element variations in both glass and
melt inclusions require that the Kilauea Iki magma was a mixture of melts generated
from different mantle sources by variable degrees of melting.
Amphibole phenocrysts from Mt. Pinatubo, Mt. Hood, Mt. St. Helens, and
Shiveluch Volcano record a variety of trace element signatures related to the sources
and fractionation processes acting in each of these systems. Variations in Li and Cu in
amphiboles are decoupled from any other trace element but positively correlate with
each other. Their behavior appears to be consistent with mobility in volatile-rich
fluids followed by rapid equilibration with amphibole phenocrysts.
New 40Ar-39Ar incremental heating age determinations and whole rock major
and trace element analyses from the Curaçao Lava Formation and the Dumisseau
Formation have provided a revision of the timing and geochemical character of the
Caribbean Large Igneous Province. These data provide evidence for almost 30
million years of volcanic history beginning around 94-60 Ma with mantle plume-like
geochemical character. To reconcile the duration of volcanism and the observed
geochemical signature with models of mantle plume impingement, a new model for
development of the Caribbean Large Igneous Province is proposed that calls on
nearby subduction zones to induce asthenospheric flow in the mantle that allows for
continuous tapping of plume-influenced mantle for a 30 million year period.
©Copyright by Matthew W. Loewen
December 16, 2013
All Rights Reserved
Volatile Mobility of Trace Metals in Volcanic Systems
by
Matthew W. Loewen
A DISSERTATION
submitted to
Oregon State University
in partial fulfillment of
the requirements for the
degree of
Doctor of Philosophy
Presented December 16, 2013
Commencement June 2014
Doctor of Philosophy dissertation of Matthew W. Loewen presented on December 16,
2013.
APPROVED:
Major Professor, representing Geology
Dean of the College of Earth, Ocean, and Atmospheric Sciences
Dean of the Graduate School
I understand that my dissertation will become part of the permanent collection of
Oregon State University libraries. My signature below authorizes release of my
dissertation to any reader upon request.
Matthew W. Loewen, Author
ACKNOWLEDGEMENTS
A small acknowledgements section at the beginning of this dissertation cannot
properly thank or even recognize all of the many people who made completing this
work possible and more importantly enjoyable. In each chapter separate
acknowledgement sections address important logistical support, funding, and reviews
that went into each chapter. Here I want to recognize people who were most
important to my completion of this overall degree.
First I want to note my appreciation for Adam Kent, my advisor, and the
members of my thesis committee: Bob Duncan, John Dilles, Frank Tepley, and
Anthony Koppers as well as late substitutes for my defense Anita Grunder and Dave
Graham who stepped in after a beautiful December snowstorm cancelled my original
defense date and required me to reschedule for a time when Bob and John could not
attend. I could not ask for a better advisor than Adam. He trusted me with the
freedom to work out my own problems and work on my own schedule, but also
readily answered questions and gave exceptional guidance on how to write. The data
we collected often was unexpected and quite frankly disappointing, but he kept me
positive and helped to point out the value of whatever results we found. All of my
committee members have provided support beyond their required rolls. Bob has acted
more like a co-advisor, especially with the Caribbean project, and made huge
contributions to publishing that chapter before my defense. I have only been able to
apply a fraction of John’s wealth of knowledge to the discussion of metal behavior in
volcanic systems, and all of his suggestions including those not included here will
help improve the eventual publications of those projects. In addition, I am grateful to
have had the opportunity to learn from him by working as his teaching assistant in
Mineralogy and taking several of his courses. Frank was always a friendly face with
his office down the hall from mine. I probably dropped in on him and asked him for
as much advise as I asked Adam for. Most importantly, he was always willing to help
and take the time to listen. Anthony played the role of a GCR, but actually taught me
how to prepare samples for Ar-Ar dating and gave me my first examination on the
literature of the Caribbean LIP during his isotope geochemistry class.
ACKNOWLEDGEMENTS (Continued)
Beyond my committee, I want to acknowledge the entire VIPER community
of fellow students and faculty. While working at OSU, I had the fortune to work with
a group of genuinely good people who made work fun. The students who were here
when I arrived established a culture of friendliness and excitement. I especially want
to acknowledge the conversation and friendships with Alison Koleszar, Mark Ford,
Allison Weinsteiger, Morgan Salisbury, BJ Walker, and Erin Lieuallen. My cohort of
incoming VIPERs in 2008-09, Ashley Bromley, Amy Lange, and Fede Cernuschi,
still blow me away with their intelligence, but they are also the best people I could
ever hope to work with and are among my best friends. Ashley especially has become
a lifelong friend in all adventures geologic and union. New students have come (and
gone) since I got here and I don’t know half of them as well as I’d like, but I want to
point out some who have been especially helpful as sounding boards and friends
including Dale Burns, Jason Kaiser, Stephanie Grocke, Kyle Krawl, Richard
Bradshaw, Luc Farmer, Christine Chan, Daniel Eungard, Andrew Burleigh, Casey
Tierney, Darrick Boschmann. The good nature of most people who have chosen to
join the VIPER group at OSU is this research programs’ strongest asset.
Outside of the VIPER group, I have been lucky to be involved in the Coalition
of Graduate Employees (CGE 6069). This is the best organization I have ever been a
part of and have been proud to be a member and volunteer. The people I have met in
this organization are some of the most generous people I know and have made
meaningful improvements in both Oregon State University and the
university/research communities around the country. I think the best work I’ve done
while working on a PhD are not in this dissertation but with this organization. I hope
as long as CGE represents graduate employees at OSU people do not hesitate to join
this great union and continue to volunteer to make it better.
ACKNOWLEDGEMENTS (Continued)
Before coming to OSU many important people inspired me to not only study
first in the sciences but then geology. Dr. Kaser was an especially inspiration high
school physics/astronomy teacher. My undergraduate advisor, Jeff Tepper, is a
geologic role model and taught me my core skills in this wonderful subject. Two of
my closest friends as an undergraduate, Eric and Marissa, helped drive my passion
and excitement in all things scientific and academic.
My immediate and extended family has been a big part of my life and gave
me the encouragement and support to get through all my schooling. I have ben
fortunate to have them close the last few years even if school has kept me too busy to
see everyone as much as I would like. I want to especially note my Dad from whom I
inherited a love for debate, thinking, and standing up for what is right, and my Mom
who taught me to love the mountains and the world around me. Studying geology for
almost 10 years now started with exploring the spectacular volcanoes of the central
Cascades in Oregon.
My most important acknowledgement is reserved for my best friend and wife,
Caitlin. When I started at OSU she lived in McMinnville and then Portland. Without
the fun of visiting her almost every weekend my first two years in grad school I
would have burned out and never continued past a masters degree. After marrying me
and living with me she has been my most important companion sharing my
excitement and comforting my dismay through all of my experiences the last few
years. My best memories in graduate school have been adventures with her and those
experiences are what fueled my ability to work hard on my degree. She deserves
more credit than anyone for me completing this degree and I look forward to all of the
adventures we will share in the future.
CONTRIBUTION OF AUTHORS
Adam Kent was involved in the design, interpretation, and writing of all chapters.
Robin Tuohy and Paul Wallace were responsible for major and volatile element
analysis of melt inclusions and olivine in Chapter Three. Robert Duncan was
involved in the design, interpretation, and writing of Chapter Four. In addition, he
was responsible for all 40Ar-39Ar ages from the Dumisseau Formation, Haiti. Kyle
Krawl assisted in data collection for Chapter Four, especially 40Ar-39Ar ages and trace
element analyses for Curacao and major and trace element analyses for the
Dumisseau Formation.
TABLE OF CONTENTS
Page
1. General Introduction ..................................................................................................1
References...........................................................................................................4
2. Sources of Elemental Fractionation and Uncertainty during the Analysis of Semi-
Volatile Metals in Silicate Glasses using LA-ICP-MS...................................................6
Abstract ...............................................................................................................7
Introduction.........................................................................................................7
Experimental .......................................................................................................9
Results and Discussion .....................................................................................11
Elemental fractionation during LA-ICP-MS analysis...........................11
Laser-induced fractionation ..................................................................12
Fractionation within a single-volume ablation chamber.......................13
Fractionation within a two-volume ablation chamber ..........................17
Controls on analytical reproducibility during LA-ICP-MS ..................17
Conclusions.......................................................................................................19
Acknowledgements...........................................................................................19
References.........................................................................................................20
3. Fractionation, Magma Mixing, and Volatile Degassing During the 1959 Eruption of
Kilauea Iki, Hawaii .......................................................................................................32
Abstract .............................................................................................................33
Introduction.......................................................................................................33
Methods.............................................................................................................35
Melt Inclusion Corrections ...............................................................................37
TABLE OF CONTENTS (Continued)
Page
Results and Discussion .....................................................................................39
Control on Major Element Compositions .............................................39
Controls on Lithophile Trace Elements ................................................41
Behavior of Volatile Elements..............................................................44
Semi-Volatile Trace Metal Behavior ....................................................44
Conclusions.......................................................................................................47
Acknowledgements...........................................................................................48
References.........................................................................................................49
4. Trace Metals in Amphibole from Mount St. Helens, Mount Hood, Shiveluch, and Mount Pinatubo: Insight into Metal Mobility in Volcanic Systems .............................69
Abstract .............................................................................................................70
Introduction.......................................................................................................70
Methods.............................................................................................................72
Results...............................................................................................................74
Discussion .........................................................................................................76
General amphibole variations ...............................................................76
Volatile metal behavior.........................................................................77
Mt. St. Helens .......................................................................................78
Mt. Hood ...............................................................................................80
Pinatubo ................................................................................................81
Conclusions.......................................................................................................82
TABLE OF CONTENTS (Continued)
Page
Acknowledgements...........................................................................................83
References.........................................................................................................83
5. Prolonged Plume Volcanism in the Caribbean Large Igneous Province: New Insights
from Curaçao and Haiti...............................................................................................100
Abstract ...........................................................................................................101
Introduction.....................................................................................................101
Geologic Background .....................................................................................103
Curaçao ...............................................................................................103
Dumisseau Formation, Haiti ...............................................................104
Beata Ridge and the Interior of the Caribbean Plate...........................105
Sampling and Methodology............................................................................105
Results.............................................................................................................108
Curaçao Geochronology .....................................................................108
Dumisseau Formation Geochronology ...............................................110
Geochemistry ......................................................................................110
Isotopes ...............................................................................................111
Discussion .......................................................................................................112
Geologic History of Curaçao ..............................................................112
Geologic History of the Dumisseau Formation ..................................115
Timing and Geochemistry of Volcanism Across the CLIP ................115
Tectonic Model ...................................................................................118
Conclusions.....................................................................................................120
TABLE OF CONTENTS (Continued)
Page
Acknowledgements.........................................................................................121
References.......................................................................................................121
6. Conclusions ............................................................................................................138
Bibliography ...............................................................................................................141
Appendices..................................................................................................................158
A. Supplemental Information for Chapter Three............................................159
B. Supplemental Information for Chapter Four..............................................173
C. Supplemental Information for Chapter Five ..............................................203
LIST OF FIGURES
Figure
Page
1.1. Location map of study locations in this dissertation ...............................................5
2.1. Elements analysed in LA-ICP-MS experiments ....................................................24
2.2. Schematic of the single-volume ablation chamber used in this study ...................26
2.3. Fractionation index measured for a 120 second analysis of standard glasses ablated within a single-volume ablation chamber .....................................................................27
2.4. Three chips of GSE-1G glass analyzed in different positions within the single-
volume ablation chamber..............................................................................................28
2.5. Summary of fractionation induced within the chamber for a single-volume ablation cell.................................................................................................................................29
2.6. Results from repeat analyses of GSE-1G from positions across a two-volume
ablation chamber...........................................................................................................30
3.1. Location of Kilauea volcano and Kilauea Iki on the island of Hawaii..................54
3.2. Corrections of melt inclusions for post-entrapment crystallization (PEC) and diffusive Fe-loss............................................................................................................55
3.3. Major element variation diagrams .........................................................................57
3.4. Ratio of CaO over Al2O3 against MgO..................................................................58
3.5. Trace element variation diagrams against MgO ....................................................59
3.6. Trace element variation diagrams..........................................................................60
3.7. Multielement diagrams normalized to chondrite and primitive mantle.................62
3.8. Plots of olivine-incompatible trace element ratios with modes of mantle
melting ..........................................................................................................................63
3.9. Major volatile concentrations measured with EMPA (S) and FTIR (H2O and CO2) .......................................................................................................................................64
3.10. Examination of potentially volatile metal behavior against major volatile
components ...................................................................................................................65
3.11. Selected metal concentrations examined against lithophile trace elements.........66
LIST OF FIGURES (Continued)
Figure
Page
3.12. Metal loss during degassing calculated from studies of volcanic gasses.............68
4.1. Comparison of Ti concentrations by EMPA and LA-ICP-MS..............................88
4.2. Calculated amphibole pressure (P) compared to calculated temperature (T) and molar Al/Si ..............................................................................................................................89
4.3. Rare earth element and muli-element spider diagrams comparing high- and low-Al amphiboles ....................................................................................................................90
4.4. Calculated pressure versus Ce concentrations in amphiboles................................91
4.5. Variation diagrams for Ce versus lithophile trace elements and Eu anomalies.....92
4.6. Comparisons of Eu anomalies (Eu/Eu*) compared to Sr concentrations ..............93
4.7. Variation diagrams for Ce versus potentially volatile trace elements ...................94
4.8. Covariation between Cu and Li shown on a log-log plot ......................................95
4.9. Concentrations of Cu and Li in amphiboles from Mt. St. Helens grouped by sample
.......................................................................................................................................96
4.10. Enclave and host amphibole compositions from Mt. Hood.................................98
4.11. Amphibole concentrations over the course of the 1991 eruption of Mt.
Pinatubo ........................................................................................................................99
5.1. Overview map of prominent Caribbean Large Igneous Province exposures (insert) and simplified geologic map of Curaçao ....................................................................128
5.2. Selected age spectra from the Curaçao Lava Formation .....................................130
5.3. Selected age spectra from the Dumisseau Formation ..........................................132
5.4. Multi-element diagrams for samples from the CLF and Dumisseau Formation .133
5.5. Plume and MOR derived basalts can be differentiated on a plot of Zr/Y and Nb/Y as shown by Fitton (1997) with samples from Iceland ...................................................134
5.6. 40Ar-39Ar plateau ages determined in this study and previous work ...................135
5.7. Conceptual model illustrating prolonged CLIP volcanism with mantle plume
influence......................................................................................................................137
LIST OF TABLES
Table
Page
2.1. LA-ICP-MS instrument setup ................................................................................25
2.2. Summary of uncertainty sources during LA-ICP-MS analysis of GSE-1G ..........31
3.1. Constants and parameters used in melt inclusion correction equations.................56
3.2. Pearson correlation coefficients from glass and melt inclusions ...........................61
3.3. Expected concentration decrease for potentially volatile trace elements during degassing based studies of volcanic gas emissions at Kilauea .....................................67
4.1. Copper-Lithium correlation coefficients for individual samples from Mt. St. Helens
.......................................................................................................................................97
5.1. 40Ar-39Ar age determinations for the Curaçao Lava Formation lavas, dikes, and hyaloclastites...............................................................................................................129
5.2. 40Ar-39Ar age determinations for Dumisseau Formation lavas and sills..............131
LIST OF APPENDIX FIGURES
Figure
Page
C1. Complete 40Ar-39Ar age spectra for the Curaçao Lava Formation.......................208
C2. Complete 40Ar-39Ar age spectra for the Dumisseau Formation ...........................214
LIST OF APPENDIX TABLES
Table
Page
A1. Long-term accuracy of EMPA basaltic glass calibration.....................................160
A2. Trace element accuracy in secondary standards by LA-ICP-MS ........................161
A3. Major and trace element analyses of matrix glass from Kilauea Iki....................164
A4. Major and trace element analyses of melt inclusions from Kilauea Iki...............169
A5. Major and trace element analyses of olivine from Kilauea Iki ............................172
B1. Summary of analytical uncertainty for EMPA amphibole analyses ....................173
B2. Summary of trace element secondary standard accuracy and precision ..............174
B3. Amphibole analyses from the 1991 eruption of Mt. Pinatubo .............................177
B4. Amphibole analyses from the 1980 eruptions of Mt. St. Helens .........................187
B5. Amphibole analyses from Mt. Hood ....................................................................197
B6. Amphibole analyses from Shiveluch volcano......................................................201
C1. Major and trace element whole rock analyses from the Curaçao Lava Formation and the Dumisseau Formation ...........................................................................................204
Volatile Mobility of Trace Metals in Volcanic Systems
CHAPTER ONE
GENERAL INTRODUCTION
The systematics of semi-volatile trace metals (e.g., Li, Cu, Zn, As, Se, Mo, Ag,
Cd, In, Sn, Sb, W, Pb) provide important clues to a number of magmatic and volcanic
processes, although these elements are less frequently used to study magmatic systems
than lithophile trace elements (REE, HFSE, LILE) and major volatile components (e.g.,
H2O, CO2, S, Cl). Despite this, volatile metal systematics highlight a number of key
interactions between silicate and sulfide melts, minerals, and volatile components of a
magma, and thus provide insight into how these processes can influence ore deposit
formation, eruption timing and style, and volcanic interactions within the environment.
The projects of this dissertation are all linked by a desire to measure and understand how
volatile trace metals behave in volcanic environments.
Essential to predicting how semi-volatile metals will behave in volcanic systems
is an understanding of the controls on metal partitioning into a volcanic fluid. Exsolution
of a volatile phase is a ubiquitous process in magmas and a key driver of volcanic
eruptions (Blake, 1984). Volatiles can also fracture wall rocks leading to emplacement of
hydrothermal veins and alteration associated with ore deposits (Hedenquist and
Lowenstern, 1994). Typically the first fluids exsolved from a melt are dominated by CO2
followed by H2O dominant fluids (e.g., Roedder, 1984). Two fundamental processes lead
to separation of a volatile phase from a melt. Simple decompression of ascending
magmas, or “first boiling,” will reduce the solubility of water in the melt resulting in
exsolution of a lower-density fluid. Burnham (1979) also proposed a model of “second
boiling,” where crystallization of anhydrous phases increases the H2O concentration in
the melt until saturation is reached and volatile exsolution occurs. With exsolution of a
volatile phase, minor volatile components (e.g., Cl, S, and F species) as well as semi-
2
volatile trace metals can be partitioned out of the melt and physically separated from a
magma.
Many trace metals have the potential to partition into this fluid phase. Chloride, S,
and F species all can act as complexing anions enabling the transport of many elements
such as Cu. The role of Cl, especially in the transport of Cu, was one of the earliest
recognized complexing agents for trace metals (Candela and Holland, 1984) although
recent work has suggested that S complexes may also play a role in enhancing metal
transport or even complex metals independently (Pokrovski et al., 2008; Seo et al., 2009).
In addition to composition, metal partitioning can be influenced by the number of fluid
components such as a single supercritical fluid, a dense Cl-rich brine, and/or a low
density vapor (Candela and Piccoli, 1995).
In this dissertation, the behavior of different semi-volatile trace metals is
determined in a laser ablation laboratory environment, an ocean island basalt, and in arc
volcanoes. The final project in the Caribbean Large Igneous Province does not directly
examine trace metal behavior, but was motivated by a desire to understand the potential
implications of trace metal release into the oceans during a large submarine eruption.
Specifically, Chapter 2 develops our understanding of how volatile metals behave
during laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS).
These include the level of characterization and homogeneity of the materials used for
standardization together with fractionation of elements of different volatility during
ablation, transport, and within the plasma furnace (e.g., Sylvester, 2008). In this chapter
two different laser ablation systems are compared and a new source of fractionation, and
therefore uncertainty, is documented. This study demonstrated that the laser ablation
technique applied in the subsequent chapters of this dissertation minimized semi-volatile
trace metal fractionation resulting in more precise trace element concentration
determinations.
Chapters 3 and 4 examine trace metal behavior in two different volcanic systems,
ocean island basalts and silicic arc volcanoes. Olivine-hosted melt inclusions and matrix
glasses were examined from the 1959 eruption of Kilauea Iki, Hawaii. The study aimed
to quantify any metal degassing from the magma by comparing metal concentrations in
3
melt inclusions to matrix glasses. Most measured trace metals, with the possible
exception of Sn and B, were shown to have no discernable degassing patterns. Analysis
of fumarolic emissions of trace metals compared to sulfur release suggests that, even
though metals are transported in volcanic gasses in Hawaii, the decrease in metal
concentration in the magma would be well below limits of detection. In addition to
examining trace metal behavior, new lithophile trace element determinations for Kilauea
Iki demonstrated the fractionation and mixing processes that control compositional
variations during this eruption.
In Chapter 4 semi-volatile trace metal concentrations were determined for four
different arc volcanoes: Mt. St. Helens, Mt. Hood, Mt. Pinatubo, and Shiveluch volcano.
Amphibole phenocrysts document systematic lithophile trace element variations
potentially resulting from source variations, crystal fractionation, and mixing processes.
Tin, In, and Zn are shown to be typically enriched in shallow, felsic magmas although no
direct evidence for volatile mobility of these elements was found. Copper and Li,
however, were shown to be decoupled from all other trace elements and behave in a
manner consistent with partitioning into a volatile-rich fluid that can then physically
separate from the magma.
Chapter 5 looks at a Large Igneous Province, where we initially hoped to
document metal release from this massive eruption and relate it to biological impacts
associated with this geologic event (Sinton and Duncan, 1997). The trace metal results
from Hawaii, along with the altered nature of our collected samples in Curaçao and in the
Dumisseau Formation, Haiti, made answering this question impractical. Instead, we fully
characterized the timing and geochemistry of submarine lava flows revealing a
surprisingly long duration for a volcanic formation previously thought to erupt over only
a few million years. Geochemical data are consistent with a mantle plume source and that
are largely unchanged over the volcanic history. We propose a new tectonic model that
can reconcile the longevity of the volcanic province as well as the plume-like
geochemical character.
4
References:
Blake, S., 1984. Volatile oversaturation during the evolution of silicic magma chambers
as an eruption trigger. Journal of Geophysical Research 89, 8237–8244.
Burnham, C.W., 1979. Magmas and hydrothermal fluids. Geochemistry of hydrothermal
ore deposits 2, 63–123.
Candela, P.A., Holland, H.D., 1984. The partitioning of copper and molybdenum
between silicate melts and aqueous fluids. Geochimica et Cosmochimica Acta 48,
373–380.
Candela, P.A., Piccoli, P.M., 1995. Model ore-metal partitioning from melts into vapor
and vapor/brine mixtures. Magmas, fluids, and ore deposits 23, 101–127.
Hedenquist, J., Lowenstern, J.B., 1994. The role of magmas in the formation of
hydrothermal ore deposits. Nature 370, 519–527.
Pokrovski, G.S., Borisova, A.Y., Harrichoury, J.-C., 2008. The effect of sulfur on vapor–
liquid fractionation of metals in hydrothermal systems. Earth and Planetary
Science Letters 266, 345–362.
Seo, J.H., Guillong, M., Heinrich, C.A., 2009. The role of sulfur in the formation of
magmatic–hydrothermal copper–gold deposits. Earth and Planetary Science
Letters 282, 323–328.
Sinton, C.W., Duncan, R.A., 1997. Potential links between ocean plateau volcanism and
global ocean anoxia at the Cenomanian-Turonian boundary. Economic Geology
92, 836–842.
5
Figure 1.1. Location map of study locations in this dissertation. Also shown are active
volcanic systems from the Smithsonian’s Global Volcanism Project.
6
CHAPTER TWO
SOURCES OF ELEMENTAL FRACTIONATION AND UNCERTAINTY DURING THE ANALYSIS OF SEMI-VOLATILE METALS IN SILICATE GLASSES USING LA-ICP-MS
Matthew W. Loewen
Adam J.R. Kent
This manuscript is published in:
Journal of Analytical and Atomic Spectrometry
Royal Society of Chemistry
Thomas Graham House, Science Park, Milton Road, Cambridge, UK CB4 0WF
September 2012, v. 27, no. 9, p. 1502-1508.
7
Abstract
We investigate elemental fractionation and sources of analytical uncertainty
during in situ determination of a range of semi-volatile trace metals (e.g., Cd, Sn, Pb, Zn,
Cu, Mo) in silicate glasses using laser ablation-ICP-MS (LA-ICP-MS), and compare the
performance of single-volume and two-volume ablation chambers. In a single-volume
ablation chamber we document the differential response of volatile and refractory
elements relative to 43Ca at different ablation sites within the ablation chamber as a
primary source of analytical uncertainty. This fractionation is unrelated to interaction
between the laser pulse and solid material during progressive ablation, but does correlate
with the local He velocity at the position of analysis. Evidence suggests that fractionation
relates to differences in behaviour of refractory and volatile elements during
condensation from the laser-induced plasma, and interaction between condensate and the
carrier gas. The dependence of fractionation on local He flow regime results in relatively
poor reproducibility in 43Ca normalized ratios (up to ~ 20%, 2 s) for a number of volatile
metals as well as some with siderophile and chalcophile tendencies (e.g., B, Co, Cu, Zn,
Mo, Ag, In, Sn, Sb, W, Pb). Fractionation of this type may be a major feature of many
single-volume ablation chambers and also may occur in other instances where the He
flow regime varies substantially with location in the ablation chamber. Analyses within a
two-volume sample chamber, where the He flow rate at the site of ablation remains more
uniform across the chamber, show no evidence for this style of elemental fractionation,
and normalized ratios measured for volatile trace metals show reproducibilities for
normalized ratios that are typically < 10% (2 s).
Introduction
Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) has
revolutionized the microanalysis of solid geologic materials over the last two decades
(Durrant, 1999; Fryer et al., 1995; Longerich, 2008) providing the means for rapid and
inexpensive quantification of trace elements with high spatial resolution (typically 30-100
µm). Although many geologic studies focus on determination of refractory and lithophile
trace elements, study of semi-volatile and/or chalcophile or siderophile metals has also
8
provided important information in many areas, including contributions to the
understanding of fundamental petrologic processes such as core-mantle interactions in
plumes (Norman et al., 2004; Witt-Eickschen et al., 2009), volcanic degassing (Collins et
al., 2009; Rowe et al., 2008), magmatic differentiation (Jenner et al., 2010), and the
transport of ore metals in magmatic systems (Zajacz and Halter, 2009).
Nonetheless, there are also limitations for LA-ICP-MS analysis of geologic
materials, many of which may be more critical for study of elements of relatively high
volatility. These include the characterization and homogeneity of the materials used for
standardization together with fractionation of elements of different volatility during
ablation, transport, and within the plasma furnace (Sylvester, 2008). Although somewhat
dependent on the particular laser wavelength employed, UV radiation is generally
absorbed more efficiently in basaltic glass compared to felsic composition glasses
(Günther and Heinrich, 1999; Russo et al., 2000; Yu et al., 2003). This effect appears to
affect determination of elements with lower melting and boiling points more significantly
(Outridge et al., 1997). In addition, there is the longstanding recognition that semivolatile and chalcophile trace elements may exhibit different behaviour during ablation
(Eggins et al., 1998) and during particulate breakdown within the plasma (Gaboardi and
Humayun, 2009; Günther et al., 1999; Kroslakova and Günther, 2006; Wang et al., 2006)
relative to the standard lithophile trace element suites used for many petrologic
investigations, and to the refractory lithophile elements that are typically used as internal
standards (Günther et al., 1999; Günther and Heinrich, 1999; Hirata and Nesbitt, 1995).
Although there are suggestions that femtosecond laser ablation systems may also result in
reduced elemental fractionation, these systems are less common, and a focus on
understanding controls on elemental fraction in longer pulse width lasers remains a high
priority (Borisova et al., 2010; Claverie et al., 2009; Horn, 2008; Koch et al., 2007).
In this contribution we study elemental fractionation during LA-ICP-MS analysis
of a range of trace metals of varying volatility and geochemical affinity, and document
the effect of this on analytical performance. We also highlight the role of ablation
chamber performance during analysis of semi-volatile metals and compare the behaviour
of single-volume and two-volume ablation chambers.
9
Experimental
Analyses used a NewWave DUV 193 nm ArF Excimer Laser system or a Photon
Machines Analyte G2 193 nm ArF “fast” Excimer Laser system. Operating conditions
are shown in Table 2.1. Both 80 and 50 µm spot sizes were used for analyses of samples
of GSE-1G, a synthetic basaltic glass developed by the USGS to fulfil the need for a
basaltic (~ 50 wt.% SiO2) composition glass standard (Guillong et al., 2005). GSE-1G
has sufficient levels of most trace metals (120-400 ppm; GeoReM database, Jochum et al.,
2005) to provide adequate calibrations for a wide range of trace metal compositions, and
to date does not appear to suffer from heterogeneity of volatile metals (Guillong et al.,
2005; Loewen, 2011) as has been demonstrated for the NIST-61X series glasses (Eggins
and Shelley, 2002). Between 30 and 43 masses were measured in each analysis including
elements with a wide range of geochemical affinities (lithophile, chalcophile, and
siderophile) including a number of volatile and semi-volatile elements (based on
condensation temperatures from Lodders, 2003) and are shown in Fig. 2.1.
With a few exceptions, we found little evidence for significant isobaric
interferences for the elements and matrices analysed in this study. Almost all elements in
this study that have multiple isotopes available for measurement exhibit a high level of
accuracy for concentrations measured in GSD-1G glass (using GSE-1G as a calibration
standard) using different isotopes (24,25Mg, 52,53Cr, 63,65Cu, 64,66Zn, 95,98Mo, 107,109Ag,
111,112
Cd, 118,120Sn, 121,123Sb, 182,183W, 185,187Re; Loewen, 2011). Exceptions may exist for
Se where 76Se and 82Se both consistently returned values significantly greater than
reported values for GSD-1G and had unusually large uncertainties calculated for each
individual spot analysis (> 10%). These isotopes both suffer from significant Ar- and Krbased interferences, although these potentially can be largely controlled by the gas blank
subtraction. Selenium may also suffer for relatively poor levels of characterization in
many materials.
We processed data using in-house LaserTRAM software using Visual Basic
running within Microsoft Excel. This software was used to select a 20-30 second
background interval and a ~30 second ablation interval for each analysis. The software
10
corrects for background and normalizes the count rates for each element over the ablation
interval to the selected internal standard (43Ca). The software subdivides the selected
ablation interval into a preselected number (typically 3-5) of subintervals of equal
duration and background-corrected counts recorded in each of these were binned before
calculating normalized ratios for each subinterval. In materials that are homogenous at
the scale of an individual analysis crater this approach reduces error magnification related
to low count rates and short dwell times. Final normalized ratios for each sample are the
median value of the normalized ratios calculated for each subinterval (we use the median
as it is more robust with respect to outliers than the mean). Uncertainties in each
normalized ratio are determined as 2 standard error (2 se) of the results for each
subinterval.
Analyses we report herein include a number of spot analyses of different chips of
GSE-1G glass as well as multi-point transects across individual mm-sized chips of GSE1G. Transects consist of lines of spots rather than continuous rastered traverses. Transects
were also analysed with sample mounts in different locations within the ablation chamber
to study cell transport effects. To simplify comparisons, our data are primarily presented
as 43Ca normalized ratios (X/43Ca) for each isotope instead of calibrated concentrations.
Although this approach does not automatically correct for short-term instrumental drift,
comparison of secondary standard glass analyses before and after the analysis of GSE-1G
were used to monitor significant changes and none were observed.
To assess the role of laser-induced fractionation during progressive ablation,
fractionation factors (Fryer et al., 1995; Mank and Mason, 1999; Sylvester, 2008) were
measured with 80 µm spot sizes over longer ablation intervals (120 seconds with a pulse
rate of 4 Hz) for GSE-1G and NIST-610 glasses. The fractionation index was then
calculated from the ratio of the median X/43Ca ratios measured in the first and last 30
seconds of a 120 second ablation period (Fryer et al., 1995; Mank and Mason, 1999).
This procedure results in fractionation factors that are relative to Ca = 1.
We also conducted experiments in two different styles of ablation chamber in this
study. A schematic of the single-volume ablation chamber used for this study is shown in
Fig. 2.2. For routine analyses samples set in 25 mm diameter epoxy mounts are located in
11
a central position with smaller (~12 mm) mounts used for standards located on either
side. Helium enters and is extracted from the chamber at points located along the axis of
the three sample/standard mount locations. Experiments were also conducted in a twovolume ablation chamber. This unit follows a design developed at Australia National
University (Eggins et al., 1998) where a smaller cone is placed over the sample surface
above the ablated region, and He flow from the chamber transports ablated material into
this cone and then into the tubing that leads to the ICP-MS. The two-volume chamber
used in this study has two separate He carrier gas inputs, one for the entire sample
chamber and another within the cone itself. During routine analyses the two flow rates
are each set at 0.4 L min-1 and the flow rate listed in Table 2.1 represents these two gas
inputs combined. The effect of this design is a much smaller effective volume ablation
chamber with faster signal response rates and more uniform gas flow regime over the
entire sample chamber (Eggins et al., 1998; Müller et al., 2009). In addition the chamber
itself is considerably larger than a single-volume chamber, and the one used herein holds
nine 25 mm diameter sample mounts in a 100 x 120 mm area. As we demonstrate later,
this design also significantly improved precision for volatile element analyses.
Results and Discussion
Element fractionation during LA-ICP-MS analysis
Elemental fractionation is a common occurrence during laser ablation ICP-MS
analysis, particularly when comparing elements with markedly different volatilities
(Hirata and Nesbitt, 1995; Sylvester, 2008). Studies that have investigated this
phenomenon have emphasized the role of fractionation induced during progressive
ablation due to changes in the local condensation regime and laser-induced plasma
extraction as an ablated crater becomes deeper (Eggins et al., 1998; Mank and Mason,
1999). This phenomenon is typically referred to as laser-induced fractionation. Other
workers have focused on the role of transport of the particulate material produced by
ablation and the elemental fractionation produced by incomplete breakdown of larger
particles within the ICP-MS plasma furnace (Guillong et al., 2003; Outridge et al., 1997).
Finally there is also the potential effect of differential carrier gas flow and the
12
corresponding efficiency of condensation and particulate transport within the ablation
chamber. Modern two-volume chamber designs minimize differential particulate
transport (Eggins and Shelley, 2002; Müller et al., 2009), but many ablation systems
currently in use, including one of the two instruments used in this study, have a singlevolume design that exhibits significant variations in carrier gas velocity and flow mode
within the chamber (Bleiner and Bogaerts, 2007; Koch et al., 2008).
In the following sections we investigate the possible origins of elemental
fractionation during laser ablation analysis, focusing on analysis of elements with a range
of volatile and refractory behaviour and geochemical affinity. We also directly compare
performance of a single-volume and two-volume ablation chamber, demonstrating the
improved performance of the two-volume system for analyses of volatile trace elements.
Laser-induced fractionation
To gauge the level of laser-induced fractionation, fractionation factors for
progressive ablation of a single crater were measured using the protocol described above
and are shown in Fig. 2.3. Previous studies have shown that in some instances significant
fractionation of elements of different volatility may occur during extended ablation and
production of deep ablation craters (Eggins et al., 1998; Fryer et al., 1995; Hu et al.,
2011; Jackson, 2001; Mank and Mason, 1999). For this study we determined
fractionation factors for GSE-1G and NIST-610 glasses. To minimize the effects of
sample chamber location (see below) we report only fractionation factors from analyses
within the centre of the single-volume ablation chamber (Fig. 2.2). Estimates of crater
depth using transmitted light microscopy show that transparent glasses ablated to greater
depths than opaque glasses over the 120 second ablation interval; NIST-610 glass ablated
at 4 Hz to 86 ± 2 mm (~170 nm per pulse), whereas the relatively opaque GSE-1G
ablated to 60 ± 2 mm (~125 nm per pulse).
Overall we see little evidence for significant fractionation of elements based on
volatility or other properties during progressive ablation of a single crater (Fig. 2.3).
Fractionation factors in all cases are typically low (0.9-1.1), compared to values reported
elsewhere that range up to three using 266 and 248 nm wavelength ablation systems and
13
longer ablation times (Fryer et al., 1995; Mank and Mason, 1999). In addition, our data
show no consistent relation between volatility or geochemical affinity and fractionation
factor. Our fractionation factors are broadly consistent with previous work that suggests
that laser-induced elemental fractionation is less important when using the shorter
wavelength ArF Excimer lasers and in shorter (up to 40 second) ablation intervals and
larger spot sizes (>44 µm; Günther and Heinrich, 1999; Hu et al., 2011; Kent and
Ungerer, 2005). In addition, ablation craters produced by the 120 second ablation
intervals reported here have depth to width aspect ratios close to one, much less than the
six or greater aspect ratio needed to produce significant volatile fractionation (Mank and
Mason, 1999).
Our data suggest that fractionation of elements on the basis of volatility, related to
differences in condensation and laser-induced plasma or extraction from a deepening
crater or both (Eggins et al., 1998; Mank and Mason, 1999), is negligible with the
instrumental setup and analysis protocol detailed herein. For this reason, and because our
typical analysis protocol for unknown materials uses only 45 seconds of ablation
(producing 20-30 µm deep craters), we believe that laser-induced elemental fractionation
during ablation is likely insignificant (< 10%) for the purposes of measurements of
elemental composition, even where large differences are apparent in the volatility of the
analyte and internal standard element. Calculation of fractionation indices over these
shorter ablation periods confirms that little apparent elemental fractionation occurs.
Fractionation within a single-volume ablation chamber
Although we see little evidence that laser-induced elemental fractionation is
significant using our protocol, our initial results using a single-volume ablation chamber
did show evidence for large variations in degree of volatile/refractory element
fractionation depending on position within the ablation chamber. These data suggested
that differences in fractionation were evident between samples located in the centre of the
ablation chamber, and those in more peripheral locations. We conducted a series of
experiments designed to study this further by systematically varying the analysis location
14
of GSE-1G glass by rotating a mount containing three different chips of glass by 90°
between analyses as shown in Fig. 2.4.
Three distinct sets of behaviour were observed between the three chips dependent
on their position in the sample chamber (Fig. 2.4). When all three chips were aligned in a
direction parallel to the He flow direction (Positions 2 and 4 in Fig. 2.4), the ratios of
elements to 43Ca determined from multiple analyses of each separate chip were broadly
similar and largely within uncertainty of each other. However, when the sample mount is
aligned so that only a single glass chip is positioned along the axis of the sample chamber
(Positions 1, 3) then a number of volatile and/or chalcophile elements (in order of
increasing depletion: Pb, Cd, Sb, Cr, Ag, Bi, Li, Co, Zn, Te, Rb, Si, W, In, As, Sn, Mo,
V, B, Re, Cu, Ir, Au) have distinctly lower X/43Ca ratios (10-15% on average) in the two
glass chips that sit at the top and bottom locations relative to the chip located in the centre
(Fig. 2.4 and 2.5). Conversely, in these positions some refractory elements (e.g., Sc, Zr,
Y) show enrichments (10-22%) relative to those measured in the two adjoining glass
chips, although other refractory elements (e.g., Ti, Ba, Sr) show no consistent offset. The
overall magnitude of these offsets varies from -35% to +15% relative to analyses in the
centre of the chamber and is the most depleted for highly volatile and/or non-lithophile
elements (Fig. 2.5). This effect is also highly reproducible (e.g., Fig. 2.4).
By comparing the relative position of chips and their Ca normalized ratios, it is
clear that a zone of relative depletion of more volatile or sidero- and chalcophile elements
and relative enrichment in some refractory elements exists across the centre of the sample
chamber (Fig. 2.4 and 2.5). This zone is aligned with the He input and output orifices.
While the ablation chamber moves in relation to the laser for different analyses, the
sample does not change its position relative to the He carrier gas intake and outtake from
the ablation chamber (Fig. 2.2). The pattern of enrichment is moderately systematic with
volatility (based on condensation temperature) for most lithophile elements. However the
most volatile lithophile elements (Rb, B) along with chalcophile (e.g., Cu, Pb) and
siderophile (e.g., Mo, W) elements all have depletions within a restricted range between
10-15%.
15
Although determining the detailed mechanism by which our observed elemental
fractionation occurs is beyond the scope of this paper, we can make some important
observations. Given the clear relation of element enrichment/depletion relative to Ca and
location within the sample chamber, the variations observed in the elemental response are
clearly related to differential He carrier gas velocities at the site of ablation. The location
of the He intake and outtake orifices along the axis of the sample chamber results in a
region of distinctly faster He flow along the centre of the ablation chamber (Fig. 2.2).
Computational modelling (Bleiner and Bogaerts, 2007; Bleiner and Chen, 2008; Bleiner
and Günther, 2001) of gas flow within drum-shaped ablation chambers that are similar to
that which we have used in our experiments confirms that this geometry produces a
narrow zone of high velocity flow along the centre of the chamber. This zone closely
corresponds to the region in which we observe the significant elemental enrichment and
depletion (Fig. 2.2 and 2.5). In contrast, along the top and bottom of the sample chamber,
He velocities are slower and locally may even flow back towards the He intake (Bleiner
and Bogaerts, 2007). Koch et al. (2008) demonstrate that this velocity zonation can be
reduced or eliminated by using a narrower He input “nozzle” in conjunction with an Ar
carrier gas and a higher carrier gas flow rate. All experiments with a He carrier gas,
however, demonstrate some level of carrier gas flow heterogeneity.
Although the fractionation we observe appears correlated with He flow rates at
the site of ablation, it is unlikely to be related to increased transport of larger ablated
particulates to the plasma furnace at high He flow rates as: (1) incomplete ionization of
larger particulate in the plasma furnace would preferentially increase the response of
more volatile elements (Jackson, 2008), the reverse of what we observe when ablation
occurs in the high He velocity portion of the ablation chamber where increased extraction
of larger particles is likely to occur (Fig. 2.4), and (2) particles produced by ablation at
the 193 nm wavelength we utilize are dominated by small sizes (< 150 nm; Guillong et
al., 2003) and thus we expect relatively minor contributions from the problematic larger
particles that may experience incomplete breakdown.
We suggest instead that the fractionation we observe relates to flow-rate
dependent variations in condensation and particulate formation and transport at the site of
16
ablation. There are several mechanisms by which this may occur. After a laser pulse
arrives at the sample surface it creates an expanding laser-induced plasma that undergoes
cooling and condensation until the gas pressure within the chamber causes it to partially
collapse back onto the surface (Koch et al., 2007). As suggested by Eggins et al. (1998),
the more refractory elements will condense first during the plasma expansion phase,
forming refractory particulates that enter the He stream preferentially due their higher
intrinsic momentum at this point. In contrast volatile species will tend to remain within
the vapour as the laser-induced plasma plume eventually collapses back to the surface,
and will be preferentially concentrated in the material deposited back onto the sample
surface around the ablation crater. An alternative model, suggested by Outridge et al.
(1997), is that after ablation refractory elements may be preferentially incorporated into
particulates relative to the more volatile elements that tend remain in the vapour phase. In
low He velocity zones, these particulates are more easily deposited back onto the sample
surface due to slower carrier gas velocity and the longer travel times required for ablated
material to exit the sample chamber. This effect would also result in relative depletion of
refractory relative to volatile elements in area of low He velocity at the margins of the
ablation chamber. Although we cannot distinguish between these two possibilities with
our data set, both models emphasize the importance of the interaction between
condensing particulates and the He flow regime near the site of ablation for producing
differences between refractory and volatile element behaviour. In addition, both of these
models also predict that relative depletion of refractory elements and enrichment of
volatile elements should occur preferentially in regions of relatively low He velocity,
consistent with our observations (Fig. 2.5).
The fractionation we observe here also underlines the importance of sample
chamber geometry and He flow regime in controlling precision and accuracy of volatile
and/or siderophile-chalcophile elemental analysis during LA-ICP-MS. Single-volume
ablation chambers similar to the one used herein are used in many commercial ablation
systems. As it may be difficult and inefficient to control the analysis location within the
sample chamber, particularly for natural samples where analysis locations are typically
distributed throughout a specific matrix, differential fractionation within the ablation
17
chamber represents a key limit on the accuracy of measurement for any element that
behaves unlike the internal standard (typically Ca), and may introduce a systematic bias
from samples located away from the calibration standards, which are typically fixed in
one location. For more volatile elements, there is potential to use Si as an alternate
internal standard, however in many geologic samples that are low in Ca (e.g., rhyolite
composition glasses), no viable alternative to Si can be used for internal standardization
resulting in increased uncertainties for typical refractory and lithophile elements (e.g.,
REE).
Fractionation within a two-volume ablation chamber
Two-volume ablation chambers are designed to maintain uniform He flow rates at
the site of ablation over a large ablation chamber. If we are correct in our assertion that
differential He flow rates contribute substantially to elemental fractionation then the more
uniform He flow regime in the two-volume chamber should minimize the effects of
position within the ablation chamber on volatile/refractory element fractionation (Eggins
et al., 1998; Müller et al., 2009). We have analysed sample mounts with chips of GSE-1G
glass located in eight different locations in a two-volume ablation chamber, and also in
chips spread across all parts of a single 25 mm sample mount. In these experiments, we
observed none of the systematic variations that were evident in the single-volume
ablation chamber, despite the increased area covered. Normalized ratios measured using
the two-volume chamber showed no systematic changes with positions in the ablation
chamber shown in Fig. 2.6 or on an individual sample mount and the overall
reproducibility of normalized ratios were broadly similar to those calculated from
analyses restricted only to the central portion of the single-volume chamber where the He
flow regime was broadly uniform (Table 2.2).
Controls on analytical reproducibility during LA-ICP-MS analysis
To quantify investigate the effect of sample chamber design on the reproducibility
43
of Ca normalized ratios during analysis of volatile and refractory elements we have
summarized the results of repeat analyses of GSE-1G glass in Table 2.2 using both
18
single-volume and two-volume ablation chambers. For the single-volume chamber we
report reproducibility (as 2 s) for measurements made only in the central position of the
ablation chamber (see Fig. 2.4) and for analyses from of all positions within the chamber
during a single analytical session. This approach allows us to estimate the effects of
elemental fractionation within the chamber for analyses made in dispersed locations
within the ablation chamber. For the two-volume chamber we include 2 s uncertainties
calculated from multiple analysis of a single 25 mm sample mount, and from analyses
made on eight sample locations within the chamber, again during a single analysis
session.
For both ablation chamber types we see similar reproducibility of 43Ca normalized
ratios for analyses made in restricted locations (Table 2.2). For the single-volume
chamber, if we consider analyses made only the central high He flow rate region (Fig.
2.4), then we see reproducibility of < 10% (2 s) for elements with a range of volatility
and chemical affinity. However if we include analyses made in all locations on the single
25 mm sample mount, which includes analysis locations in both the high and low He
flow rate regions in the middle and peripheral regions of the ablation chamber,
reproducibility of normalized ratios is considerably worse, up to ~20% (2 s) with a factor
of up to three increase, for almost all elements shown in Table 2.2. Routine analysis of
unknown materials within the ablation chamber rarely allows for specific placement of
analysis locations thus the variations in elemental fractionation that we document
represent a primary control over analytical accuracy and precision. The reproducibility
we show provides the best estimate of the long-term accuracy and precision of volatile
and semi-volatile metal analyses in single-volume sample chambers.
For the two-volume chamber we see comparable reproducibility for normalized
ratios that are measured across a single 25 mm sample mount as we see for analyses from
across the entire ablation chamber (Table 2.2). These reproducibilities are also broadly
similar to those evident from the analyses restricted to the central portion of the singlevolume ablation chamber (i.e., < ~10% at 2 s in most cases), although the reproducibility
evident for some volatile elements (e.g., B, Cu) are slightly higher (up to 12%) than
typical for lithophile and refractory elements. Importantly we see no significant increase
19
in reproducibility for analyses made over eight available sample positions within the
ablation chamber, again emphasizing the improved analytical performance resulting from
the uniform He flow regime across the entire sample chamber.
Conclusions
We observe considerable elemental fractionation between different analysis
locations in LA-ICP-MS experiments conducted within a single-volume ablation
chamber. Elemental fractionation is most evident in a range of volatile, chalcophile and
siderophile elements and is correlated with the local He flow rate at the location of the
analysis. Fractionation results from differential behaviour of refractory and volatile
elements during condensation from the laser-induced plasma, and interaction between
condensate and the He carrier gas at the site of ablation. Elemental fractionation of this
type likely represents a primary control over precision and accuracy during LA-ICP-MS
trace metal analyses in single-volume ablation chambers, and in other systems where He
flow rate varies substantially from point to point within the ablation chamber.
Two-volume ablation chambers, designed to produce uniform He flow regimes
during analysis throughout the ablation chamber, show little evidence of this style of
elemental fractionation. While it may be possible to modify single-volume ablation
chambers to homogenize He flow and reduce the impact of this uncertainty (Koch et al.,
2008), this work highlights the need for awareness of this effect as a potential limitation
to any volatile element analysis. Our approach provides a simple methodology for
investigating this effect for different ablation systems.
Acknowledgements
Support for this work was provided by National Science Foundation grants NSFOCE-0452727 and NSF-OCE-1028707 to AJRK. A. Koleszar and A. Ungerer provided
analytical assistance for LA-ICP-MS. We also appreciate discussions on sample chamber
flow dynamics with D. Bleiner and with members of the VIPER group at Oregon State
University. Suggestions by three anonymous reviewers are appreciated and significantly
improved the quality of this manuscript.
20
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composition of the Hawaiian plume. Geochimica et Cosmochimica Acta 68,
3761–3777.
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trace elements during laser sampling of glass and copper. Spectrochimica Acta
Part B: Atomic Spectroscopy 52, 2093–2102.
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Rowe, M.C., Kent, A.J., Thornber, C.R., 2008. Using amphibole phenocrysts to track
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in laser ablation ICP-MS. Journal of Analytical Atomic Spectrometry 15, 1115–
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24
Figure 2.1. Elements analysed in LA-ICP-MS experiments exhibit a wide range of
volatility (50% condensation temperature from a solar nebula composition, after Lodders,
2003) and geochemical affinities (bold elements are siderophile or chalcophile). Volatile
and moderately volatile elements were emphasized in this study to characterize their
fractionation behaviour during LA-ICP-MS. *Denotes elements commonly used as
internal standards.
25
Table 2.1. LA-ICP-MS instrument setup.
Parameter
Description
Instrumentation
Laser Ablation System
VG ExCell NewWave DUV 193
ArF Excimer Laser
Photon Machines Analyte G2
Excimer Laser
ICP-MS System
VG PQ ExCell Quadrupole
Thermoscientific X Series 2
Quadrupole
Wavelength
193 nm
193 nm
Frequency
4-5 Hza
5 Hz
Pulse Duration
20 ns
4 ns
Spot Diameter
50, 80, 100, and 160 mm
50 mm
Ablation Duration
45 seconds (up to 120 seconds for
fractionation tests)
45 seconds
Output Energy
9-12 J cm-2
4.84 J cm-2
Aerosol carrier gas flow
0.8 L min-1 (He)
0.8 L min-1 (He)
Nebulizer gas flow
0.80-0.95 L min-1 (Ar)
0.8-0.9 L min-1 (Ar)
Laser Conditions
Analyzer Conditions
-1
Outer (cool) gas flow
13.00 L min (Ar)
Detector mode
Dual (pulse counting and analogue)
RF power
1300 W
13.00 L min-1 (Ar)
Dual (pulse counting and
analogue)
1380 W
Vacuum Pressure
8-10 x 10-7 mbar (analyzer), 1.5-1.9
mbar (expansion chamber)
8-9 x 10-7 mbar (analyzer), 2.02.2 mbar (expansion chamber)
Dwell time/mass/scan
10 ms
10 ms
Standardization
a
Internal Standard
43
Calibration Standards
GSE-1G, NIST-610
Ca
5 Hz used in transects, 4 Hz used in fractionation tests
26
Figure 2.2. Schematic of the single-volume ablation chamber used in this study. The
chamber is a shallow cylindrical drum approximately 20 cm3 in volume. During
experiments He carrier gas flow was 0.8 L min-1 from left to right. On the right are the
calculated flow velocities modified from Bleiner and Bogaerts (2007) for a similar
geometry sample chamber (drum-shape, 33 cm3, He gas flow of 0.5 L min-1, scaled to
match our sample chamber) illustrating the formation of a distinct high velocity zone
across the centre of the chamber.
27
Figure 2.3. Fractionation index measured for a 120 second analysis of standard glasses
ablated within a single-volume ablation chamber. Data are the mean of 5-6 spot analyses
(± 2 se) calculated as the median ratio of X/43Ca measured over the last 30 seconds of
ablation divided by the first 30 seconds (Fryer et al., 1995; Sylvester, 2008; Mank and
Mason, 1999). Within each geochemical affinity group, elements are ordered by
increasing condensation temperatures (Lodders, 2003). Dashed lines bracket ± 10%
fractionation. No consistent difference was found for fractionation at different element
volatilities or in different matrices despite greater ablation depths in NIST glasses. Note
Ca = 1 by definition.
28
Figure 2.4. Three chips of GSE-1G glass analysed in different positions within the
single-volume ablation chamber. The shaded region is the centre position in the ablation
chamber in each rotation of the sample mount. Arrows highlight significant enrichment
of refractory elements (e.g., Sc) and depletion of volatile elements (e.g., Cu) relative to
43
Ca while chip B was located in this central region. Bars are mean values for each chip
(± 2 s, n = 3).
29
Figure 2.5. Summary of fractionation induced within the chamber for a single-volume
ablation cell. This is quantified by dividing the values measured for X/43Ca ratios of chip
A and C in positions 1 and 3 and chip A, B, and C in positions 2 and 4 (see Fig. 2.4) by
the values of chip B in positions 1 and 3 for each normalized ratio measured. Values
below one represent elements that are enriched in analyses made at the top and bottom of
the sample chamber relative to Ca, while values above one are enriched in the centre of
the chamber. Lithophile elements show some indication of a positive correlation with
volatility (expressed as condensation temperature, Lodders, 2003) while highly volatile
lithophile elements (Rb, B, Li, Cr, Si) and all chalcophile and siderophile elements are
consistently enriched in the top and bottom of the chamber by 10-15% with no relation to
condensation temperature.
30
Figure 2.6. Results from repeat analyses of GSE-1G from positions across a two-volume
ablation chamber. Seven spots were analysed in each mount position (± 2 s). Position
seven held NIST-612 used as a drift monitor and no significant changes with time were
observed. Variations throughout the chamber are smaller than observed in the singlevolume ablation chamber (Fig. 2.4) and do not show any dependence on volatility.
Table 2.2. Summary of uncertainty sources during LA-ICP-MS analysis of GSE-1G.
Single-Volume Chamber
Isotope
11
45
2s%
Ablation
Chamberb
Two-Volume Chamber
2 s % for
Single
Mountc
2s%
Ablation
Chamberd
B
11.0
19.1
10.0
9.9
Sc
3.6
9.2
3.8
4.2
5.6
5.9
2.8
4.3
47
Ti
51
5.7
11.3
8.9
7.1
59
Co
6.8
13.7
11.7
8.0
63
Cu
9.5
19.1
12.6
8.1
65
Cu
8.2
18.0
12.6
7.4
66
95
V
Zn
5.7
16.1
8.2
8.0
Zr
4.1
12.7
6.4
6.7
Mo
8.0
14.7
9.0
8.0
8.5
17.4
7.6
6.7
90
107
Ag
115
7.9
16.0
7.4
6.4
118
Sn
7.2
15.1
8.0
7.7
121
Sb
7.7
15.0
7.9
6.7
Ce
4.2
6.6
5.0
3.8
7.3
12.4
7.4
7.3
6.0
14.5
7.8
7.2
140
182
208
a
2 s % for
Single
Transectsa
In
W
Pb
31
Calculated for a centrally located transect (see Fig. 2.4) of GSE-1G to avoid fractionation related to
position within the single-volume ablation chamber (n = 34). b Calculated on transects across three chips of
GSE-1G located throughout the single-volume ablation chamber (n = 104). c Variations across a single oneinch mount in a two-volume ablation chamber (n = 16). d Variations across eight one-inch mounts in a twovolume ablation chamber (n = 56).
32
CHAPTER THREE
FRACTIONATION, MAGMA MIXING, AND VOLATILE DEGASSING DURING THE 1959 ERUPTION OF KILAUEA IKI, HAWAII
Mathew W. Loewen
Adam J.R. Kent
Robin M. Tuohy
Paul J. Wallace
33
Abstract
We report major and trace element data for glass, olivine, and olivine-hosted melt
inclusions from the 1959 eruption of Kilauea Iki, Hawaii. Major element compositions of
glasses match the results of earlier studies and suggest that crystallization of olivine and
mixing between different magma batches control melt compositional variations.
Lithophile trace element variations result from mixing of magmas with distinct mantle
source regions and/or different degrees of partial melting. Melt inclusions have higher
concentrations of volatile components like sulfur (~0.1-0.13 wt.%), water (0.4-0.7 wt.%),
and CO2 (0-250 ppm) than matrix glass, requiring inclusion entrapment of variably
degassed magma at or near sulfide saturation. A number of transition metals with affinity
to partitioning into a volatile-rich phase were also analyzed including those with a range
of volatility and geochemical affinity. Of these, most (e.g., Mo, Pb) display typical
incompatible behavior in melt compositions whereas others appear to be compatible in
known phases (primarily olivine: Zn, Co). Copper concentrations are variable, and can be
explained by minor compatibility in olivine and potential retention in trace amounts of a
sulfide phase. Boron and Sn show some patterns consistent with degassing. Although
fumarolic condensates at Kilauea and other basaltic volcanoes are commonly enriched in
volatile and semi-volatile metals, mass balance calculations of the changes in magmatic
abundances related to volcanic gas emissions are consistent with very small (< 10%)
compositional changes. These expected changes in melt composition cannot be resolved
by our analyses using LA-ICP-MS.
Introduction
The 1959 eruption of Kilauea Iki, Hawaii, provides an appropriate system to
investigate the fundamental behavior trace elements during melt evolution and degassing
of basaltic magma and to compare the behavior of refractory and semi-volatile trace
elements in a shallow basaltic volcanic system. The compositional evolution of Kilauea
Iki is literally a textbook example of magma diversification by olivine control (e.g.,
Winter, 2001), and thus potentially represents a well-behaved system where more subtle
variations due to degassing or other processes may be identified. The samples examined
34
here are also well suited for olivine-hosted melt inclusion studies as many are picritic
with large olivine phenocrysts. In addition, the sequence of the eruption was extensively
documented and sampled by staff at the USGS Hawaiian Volcano observatory (Murata
and Richter, 1966a; 1966b; Richter et al., 1970; Richter and Murata, 1966). Previous
work has refined our understanding of mixing and fractionation controls on major
element chemistry (Wright, 1973), olivine composition and petrography (Helz, 1987),
and volatile abundances and character of trapped melt inclusions (Anderson and Brown,
1993; Wallace and Anderson, 1998). Despite this work, relatively few data have been
published on trace elements of the magma composition, and no previous trace element
data are available for melt inclusions, glass, or minerals.
Kilauea Iki crater is located on the east side of the Kilauea Caldera on the island
of Hawaii (Fig. 3.1). The summit eruption of Kilauea Iki began on November 14th and
continued through December 20th, 1959, consisting of 17 phases of fire-fountaining, each
of which partially filled the Kilauea Iki crater with a substantial lava lake that partially
drained back into the vent following each phase (Richter et al., 1970). The first phase
followed a 3-month period of precursory seismicity and inflation that began with a deep
(55 km) earthquake swarm August 14-19 followed by intermittent and progressively
shallower earthquakes and rapid inflation in November (Eaton and Murata, 1960). The
eruption began on November 14 as a 750 m long fissure with 30-m-high fire fountains,
but quickly coalesced into a single vent. Over the course of the eruption, the fire
fountains reached a height of 500 m with incandescent scoria observed to over 650 m (3rd
phase, November 28) and spread a wide tephra deposit outside of the Kilauea Iki crater
(Fig. 3.1). Lava temperatures at the vent were variable with the highest recorded (1192
°C) midway through the eruption on December 4. Over the eruption the lava lake filled to
a maximum depth of 125 m on December 10 covering an area of 61 hectares. The
majority of the volume was erupted during the first phase of the eruption (30 million m3)
whereas later phases added smaller volumes (2-10 million m3), most of which drained
back into the vent at the end of each cycle (Murata and Richter, 1966a). On January 13th,
1960, nearly a month after the end of the summit eruption, a flank eruption began and
continued through mid-February. The compositions of this eruption were similar to
35
material from an earlier eruption of Kilauea in 1955 (Murata and Richter, 1966a; Wright
and Fiske, 1971).
The goal of this study was to examine the composition of both lithophile trace
element suites and semi-volatile trace elements of glass and melt inclusions from the
1959 Kilauea Iki eruption with the goal of constraining the effect of crystallization,
magma mixing, and volatile exsolution on trace element variations.
Methods
The Division of Petrology and Volcanology, Department of Mineral Sciences,
Smithsonian Institution provided forty-six glass samples collected by the USGS during
the 1959 eruption. These samples spanned the entire duration of the summit eruption.
Glass samples were picked by binocular microscope to include only glassy material with
few vesicles. Samples were subsequently mounted together in two 25 mm epoxy rounds
and polished with diamond and alumina polishing compounds down to a 1µm grit.
Sixteen melt inclusions were prepared from sample Iki-22 (see Anderson and Brown,
1993) and individually exposed in order to analyze for volatile (H2O, CO2) species as
well as major and trace elements.
Basaltic matrix glass was analyzed by electron microprobe (EMPA) at Oregon
State University using a Cameca SX100 Electron Microprobe Analyzer. For glass
analyses, a focused 1 µm beam with a 15 keV accelerating voltage and 30 nA beam
current was used with variable peak count times: 20 seconds (s) for Si, Al, Na, and Ti; 30
s for K, Ca, Mn, and Fe; 40 s for Cr; and 60 s for P, S, Cl, Ni, Mg, and F. Volatile loos
was corrected by measuring zero time intercepts for Na, K, Al, and S. Melt inclusions
and olivine were analyzed at the University of Oregon also using a Cameca SX 100
Electron Microprobe Analyzer.1 Makaopuhi Lava Lake basaltic glass (USNM 113498/1
VG-A99, “BASL”) was analyzed during calibration and unknown analyses to monitor for
accuracy and stability. Long-term stability of this standard as well as accuracy of
secondary standards (BHVO-2G, BCR-2G, GSD-1G) are shown in the Supplementary
1
Analytical conditions for UO EMPA and FTIR work are not available at this time.
36
Data (Appendix A). Concentrations reported here are generally the averages of 2
analyses.
Trace element analysis was carried out by laser ablation-inductively coupled
plasma-mass spectrometry (LA-ICP-MS) at Oregon State University using a Photon
Machines G2 193 nm Ar-F laser attached to a Thermoscientific Xseries 2 quadrupole
mass spectrometer with instrument conditions and data processing similar to that in
Loewen and Kent (2012). Glass, olivine, and melt inclusions were analyzed using a 50
µm spot at 7 Hz for approximately 30 seconds. GSE-1G was used as a calibration
standard whereas GSD-1G and natural glasses were used as secondary standards. Data
were processed using in-house LaserTRAM and LaserCalc software, which use a Visual
Basic script operated in Microsoft Excel. These programs allow for manual selection of a
20-30 second background interval and a 15-30 second ablation interval. The software
normalizes each analyte mass to the 43Ca internal standard and calculates a concentration
of the analyte using the Ca concentrations determined by EMPA. Standardization is
provided by measurements of GSE-1G once every 5-10 unknowns over the course of an
experiment. Errors displayed on figures in this paper are standard error (se) of the mean
of 5 sub-intervals for each analysis propagated with both the uncertainty in repeated
measurements of the calibration standard (GSE-1G) and uncertainty in Ca concentration
measured by EMPA. Additional propagation of uncertainty in characterization of the
calibration standard doubles reported uncertainties for many elements and is reflective of
the uncertainty in the absolute concentration. The former uncertainty is appropriate for
internal comparison within this study. Reported concentrations are again the average of
2-3 analyses for each glass sample and one analysis for olivine and melt inclusions. A list
of all measured isotopes, concentrations for glass, melt-inclusion, and olivine, and
analysis of secondary standards, is available in the Supplementary Data (Appendix A).
Glass and melt inclusion analyses that exhibited evidence for significant contribution of
the host or from microphenocrysts into the ablated volume are not included here.
37
Melt Inclusion Corrections
Melt inclusions are portions of glass initially trapped as melt inside phenocrysts
during crystal growth. Melt inclusions have the potential to shed light on magma
compositions not expressed at the surface, including pre-eruptive volatile concentrations,
since inclusions are typically trapped at higher pressures than the matrix glass formed
during eruption and quenching (Kent, 2008; Schiano, 2003; Wallace, 2005). Postentrapment crystallization (PEC) of olivine along the walls of the inclusion after
entrapment, however, has modified the major and trace element contents of all analyzed
inclusions from this study. In samples from Kilauea Iki, melt inclusions are not only
lower in Mg, but also lower in Fe compared to what can be predicted using the liquid line
of descent for whole rock and matrix glass compositions (Fig. 3.2). This anomalous loss
of iron is described as diffusive Fe loss by Danyushevsky et al. (2000) and together with
PEC can be corrected to initial compositions by various methods (Danyushevsky et al.,
2000; Gaetani and Watson, 2002; Kent, 2008).
We use an iterative calculation with the geothermometer of Putirka et al. (2007) to
correct measured melt inclusion compositions to equilibrium with their host olivine. In
this experimentally calibrated model, two equations relate the olivine/melt distribution
coefficients of Mg (DMgol/liq) and Fe (DFeol/liq) to pressure (P, in GPa), temperature (T, in
°C), and melt composition (H2O, Na2O, K2O, and SiO2, in wt. %):
(1) ln DMgol/liq = -a + b * (P/T) – c*[H2O] + d/T + e*[ Na2O + K2O]
(2) ln DFeol/liq = -a + b * (P/T) – c*[H2O] + d/T + e*[ Na2O + K2O] + f*[SiO2]
where a, b, c, d, e, and f, are constants defined for each equation in Table 3.1. We use
pressures and water contents from this and previous melt inclusion studies (Anderson and
Brown, 1993; Wallace and Anderson, 1998), total Fe and ferrous Fe (FeO*/FeO) of
whole rock via wet chemical analyses (Murata and Richter, 1966a), MgO and FeO
concentrations measured in host olivine, and Na2O, K2O, and SiO2 from each measured
melt inclusion. The calculation determines an equilibrium Fe and Mg melt concentration
at a given temperature using the measured melt (white circles, Fig. 3.2) and host olivine
38
compositions. The temperature is then iteratively adjusted until calculated Mg-Fe
concentrations lie along the liquid line of descent as defined by whole rock and glass data
(red circles, Fig. 3.2). The difference between the original Mg measured in the melt
inclusion and the calculated equilibrium Mg is used to determine the required amount of
olivine mixed with the measured melt inclusions. All other elements are then corrected
for this amount of crystallization by mixing measured melt inclusion concentrations with
the measured host olivine composition.
We note that FeO* concentrations measured here by EMPA are generally 0.5 wt.
% lower than previous analyses of either glass (Helz, 1987) or whole rock (Murata and
Richter, 1966a) samples from Kilauea Iki, yet slopes of FeO* evolution with MgO are
similar. We use our measured FeO* values for internal consistency, but note that these
may be systematically offset from values determined in other studies due to calibration
settings unique to our analyses (FeO* is calibrated on an Fo83 crystal standard, not basalt
glass). In analyses of secondary standards (Supplementary Data, Appendix A) FeO* is
slightly lower (~3% relative) than the accepted standard values for a number of basaltic
glass standards, but the difference is not enough to explain the offset between the OSU
EMPA and Helz (1987) data.
The resulting corrections range from 8 to 16 wt. % of PEC. For purely
incompatible elements this will result in a dilution of the measured inclusion
concentration by the same amount. The value of this approach is that it also provides an
estimate of the equilibration temperatures that serves as an additional check on the
correction. In addition, by using measured host olivine to correct all elements, we can
provide a reasonable correction for any trace elements that are present in appreciable
quantities in olivine (e.g., Ni, Co, Zn).
It is also important to note that the most important parameters for the calculation
of crystallization temperature (and subsequently, percentage of PEC) in these equations
are the Mg and Fe compositions of olivine. Terms reflecting the influence of the melt
composition (H2O, Na2O + K2O, SiO2) have relatively little influence on the magnitude
of the correction. Pressure also has little importance, as Fe-Mg partitioning in olivine is
not pressure dependent. In addition, formation pressures for melt inclusions from Kilauea
39
Iki are well constrained from previous work (Anderson and Brown, 1993) and by our
H2O-CO2 data.
Results and Discussion
Analyses by EMPA and LA-ICP-MS for matrix glass, corrected melt inclusions,
and host olivine are reported in the Supplementary Data (Appendix A). In the following
sections we discuss the trends and significance of major element variations, standard
trace element compositions, volatile concentrations, and patterns of trace metals. Within
these sections we identify the effects of crystallization, mixing, and volatile exsolution on
compositional variations.
Control on Major Elements Compositions
Most major element variations observed in melt inclusions, glasses, and whole
rock samples can be explained with crystallization of olivine plus Cr-spinel and late
crystallization of clinopyroxene, consistent with previous whole rock (Murata and
Richter, 1966a) and glass (Helz, 1987) studies (Fig. 3.3). Glass compositions range from
9.8 to 5.7 wt. % MgO with a sharp decrease in SiO2 and CaO occurring at ~7 wt. %
MgO, consistent with the onset of clinopyroxene crystallization. Aluminum behaves
incompatibly over the entire compositional range suggesting an absence of plagioclase
crystallization. Whole rock compositions (Murata and Richter, 1966a) do not show the
same inflection in CaO suggesting that clinopyroxene primarily is a groundmass phase
crystallized upon eruption and was generally not removed from the magma.
Corrected melt inclusions record more primitive compositions than matrix glasses
and generally fall along compositional evolution paths defined by glass values and whole
rock compositions. They are more magnesian than matrix glass (up to 12.8 wt. % MgO),
consistent with entrapment of a more primitive magma during early olivine growth.
Whole rock compositions range up to almost 20 wt. % MgO as a result of olivine
accumulation. The most magnesian glasses known from Hawaii are around 15 wt. %
MgO (Clague et al., 1995; 1991), which is compatible with the idea that these melt
inclusion compositions are reasonable.
40
MELTs modeling (Asimow and Ghiorso, 1998; Ghiorso and Sack, 1995) at 1 kb
pressure, QFM redox conditions (matching the measured Fe2O3/FeO from Murata and
Richter, 1966a) and 0.7 wt. % initial water (Wallace and Anderson, 1998) provide a good
match to the observed compositional trends and closely match the volume of olivine
crystallization calculated with lever law principles. The most primitive glass composition
observed represents approximately 8 wt. % olivine crystallization in order to modify
glass compositions from the most primitive corrected melt inclusion. An additional 7-8
wt. % crystallization of olivine is required before initial crystallization of clinopyroxene
and a corresponding compositional inflection of CaO at 7 wt. % MgO in the model.
Temperature outputs from the MELTs model are also consistent with eruption
temperature observations and calculated olivine-hosted melt inclusion entrapment
temperatures (Table 3.1; Putirka et al., 2007). Our highest calculated melt inclusion
trapping temperature was 1315 °C, close to the calculated MELTs liquidus of 1307 °C.
The lowest temperature associated with the most evolved melt inclusion was 1216 °C at
9.3 wt. % MgO, matching the MELTs composition at this point and slightly lower in both
MgO and MELTs predicted temperature than the most primitive glass composition (12.8
wt. % MgO, 1230 °C). Temperatures recorded during the eruption ranged from 11901060 °C consistent with the final groundmass crystallization we observe in the most
evolved glasses but well below the calculated trapping temperatures of observed melt
inclusions.
Some scatter is evident in major element trends that cannot be explained by
olivine crystallization alone. Murata and Richter (1966b; 1966a) recognized two distinct
compositional endmembers in samples from the beginning of the eruption in samples S-1
and S-2 (Fig. 3.4). S-1 lies off olivine control lines and is richer in CaO whereas S-2
marks the least magnesian endmember of the olivine-control line. Glass and melt
inclusion compositions span the composition range between these two components. Low
TiO2 and K2O concentrations in melt inclusions fall out of the compositional range
defined by glass and major element analyses and likewise cannot be explained by olivine
crystallization (Fig. 3.3).
41
Controls on Lithophile Trace Elements
The new data presented in this study greatly expand the previously limited
lithophile trace element data set for Kilauea Iki (Tilling et al., 1987) and provides a
means to evaluate further the role and source of mixing during the 1959 eruption. Trace
elements follow broadly similar patterns to major elements. Olivine-compatible elements
(e.g., Ni, Co) systematically decrease with decreasing MgO consistent with olivine
crystallization as the primary control (Fig. 3.5). Corrected melt inclusions fall along the
same compositional trend as glasses, demonstrating that our method of correction for
PEC reproduces a reasonable trapped melt composition. Scandium decreases at < 7 wt. %
MgO consistent with compatibility at the onset of clinopyroxene crystallization. Elements
incompatible in olivine and clinopyroxene (e.g., Sr, Zr, Ce) broadly increase with
decreasing MgO, but with considerably more variability than observed in incompatible
major elements.
Olivine crystallization cannot alone explain this range of incompatible trace
element compositions. We use a Raleigh fractionation model of 16 wt. % crystallization
of olivine that corresponds to the MELTs output of olivine crystallization before the
onset of clinopyroxene crystallization with partition coefficients from Beattie (1994) or
median olivine/melt values from melt inclusion and olivine pairs analyzed in this study
(Fig. 3.6). Whereas lower MgO glasses do generally have higher concentrations of trace
elements (especially Ce, Sr, and Ba), the full compositional range of trace elements
requires 2-3 times more olivine crystallization than predicted by major element
compositional variations and the MELTs model.
Variable degrees of partial melting of mantle can also generate a range of trace
element concentrations with similar major element characteristics. Rare earth elements
(REE) have characteristic enrichment in light-REE (high La/Yb) consistent with partial
melting of a deep, garnet-bearing source (Fig. 3.7). All elements in Figure 3.6 are
incompatible in olivine, and therefore fractional crystallization should result in linear
correlations between any two the elements. Partial melting, however, can result in nonlinear variations due to variable crystal/melt partition coefficients in mantle source rocks
for many of these elements. Departures from a simple linear correlation between pairs of
42
different trace elements are summarized in the correlation matrix in Table 3.2. Elements
highly incompatible in a garnet peridotite mantle source (Ba, Th, Nb, Ce) strongly
correlate with each other (R > 0.8). Likewise, more compatible elements in garnet
peridotite (Hf, Dy, Y, Yb) are also strongly correlated. Incompatible and compatible
element pairs (e.g., Hf-Ba, Ce-Y), however, have worse (R < 0.6), although significant,
correlations due to increased scatter.
To further evaluate source(s) of the Kilauea Iki magma, we compare trace
element ratios of incompatible elements in order to minimize the effects of olivine
fractionation (Fig. 3.8). The most evolved glass compositions directly overlap the more
primitive compositions on these plots demonstrating the negligible effect of olivine
crystallization on these ratios. Similarly, melt inclusions uncorrected and corrected for
PEC directly overlap each other. Broad compositional arrays on these plots require more
than one source component for the Kilauea Iki magmas. Melt inclusions record more
extreme trace element ratios than glasses, however, they mirror the same compositional
trends. The similarity between melt inclusion and glass compositional trends is consistent
with their record of melt composition, as opposed to inclusion specific processes such as
boundary layer entrapment (Kent, 2008; Lu et al., 1995; Roedder, 1984).
Partial melting models of two different mantle sources following the models of
Pietruszka et al. (2013) bracket the majority of Kilauea Iki compositions (Fig. 3.8). Our
purpose is not to provide a vigorous investigation of source melting in Hawaii, which has
been studied by a number of authors (Feigenson et al., 1996; Frey and Rhodes, 1993;
Hofmann et al., 1984; Hofmann and Jochum, 1996; Pietruszka et al., 2013; Pietruszka
and Garcia, 1999), but to show that the range of compositions we observe could be
reasonably produced by variations in source composition and partial melting percentages.
We use a batch partial melting model with source compositions and partition coefficients
similar to Pietruszka et al. (2013). This model mainly calls on mixtures of recycled crust
and mantle to explain Hawaiian primary melt compositions from Loihi, Kilauea, Mauna
Loa, and Koolau. The model in this study uses simplified mantle sources from those of
Pietruszka et al. (2013) similar to their early 20th century Kilauea source and Mauna Loa
source. We use a mixture of 90-85 wt. % ambient Hawaiian mantle (equal parts depleted
43
and enriched mantle; compositions from McDonough and Sun, 1995) mixed with 10-15%
variably altered and dehydrated MORB crust (see Figure 3.8 caption for more detail).
The MORB component is necessary to explain the high Ba/Th and Sr/Y characteristic of
some melt inclusions. The models are consistent with 3-5 wt. % partial melting for most
glass compositions and up to 10 wt. % partial melting for some melt inclusions.
These ratio plots require that the erupted Kilauea Iki lavas were sourced not only
from magmas generated by variable degrees of partial melt from the Hawaiian mantle,
but also by magmas derived from different mantle sources that contain variable amounts
of recycled oceanic crust (Hofmann and White, 1982; Lassiter and Hauri, 1998; Sobolev
et al., 2000). This heterogeneity has been observed in other Hawaiian eruptions
(Pietruszka and Garcia, 1999), although it is striking here with variations in glass
occurring over a single month-long eruptive episode and an even greater range of
variability recorded in melt inclusions from a single sample collected at the beginning of
the eruption.
The trace element ratios discussed above do not systematically change over the
course of the 1959 eruption. Preservation of diverse melt compositions even in matrix
glass is consistent with conclusion of Helz (1987) that the magma erupted at Kilauea Iki
was not fully equilibrated upon eruption based on observations of heterogeneous glasses
and the timing of deep earthquakes prior to the eruption. Wright (1973) calculated that
variable proportions of the S-1 and S-2 endmembers throughout the 1959 eruptive period
and suggested that some portion of the two magma types remained distinct during the
eruption while each component contributed magma to the conduit. The unusually shallow
trapping pressures (< 1 kb) for the majority of inclusions noted by Anderson and Brown
(1993) is consistent with this model if mixing between thermally distinct magmas
triggered rapid olivine growth during ascent and resulting melt-inclusion entrapment
during the mixing between these two magmas. We note that the Ca/Al variability
characteristic of the S-1 and S-2 component is not correlated with any incompatible
elements. The incompatible trace elements, however, record a more accurate sampling of
the melt source since the degree of crystallization strongly influences major element
composition.
44
Behavior of Volatile Elements
Significant shallow volatile loss of S species (mostly has SO2) and H2O, and
deeper degassing of CO2 characterize Hawaiian magmas (Anderson, 1974; Gerlach,
1986; Gerlach and Graeber, 1985). Chlorine may also form a significant volatile
component of many volcanic systems (Anderson, 1974) but was near EMPA detection
limit in our glass and melt inclusion samples (typically < 200 ppm). All glass
compositions from Kilauea Iki are clearly degassed, with S concentrations near EMPA
detection limits (< 200 ppm) whereas concentrations in melt inclusions range from
similar values to the glass up to 1300 ppm (Fig. 3.9). Melt inclusions record 0.4-0.7 wt.%
H2O and 0-250 ppm CO2 suggesting minimum pressures of 0.5 kb (Newman and
Lowenstern, 2002). Previous melt inclusions studies have recorded a larger range of
inclusion volatile concentrations and average pressures of 1 kb (Haughton et al, 1974;
Anderson and Brown, 1993; Wallace and Anderson, 1998).
Sulfide saturation is commonly related to iron content and uncorrected melt
inclusions lie parallel to and about 300 ppm above a regression of sulfide saturated
MORB samples (Mathez, 1976) and experimental and theoretical sulfide saturation
concentrations (Fig. 3.9; Wallace and Carmichael, 1992). Corrected inclusions lie at or
below sulfide saturation. This pattern is consistent with observations of rare sulfides in
some samples from the erupted scoria (Helz, 1987; Pitcher et al., 2009; Stone and Fleet,
1991). The correlation of FeO* and S in uncorrected inclusions suggests that PEC and/or
diffusive Fe-loss may have driven inclusions to sulfide saturation.
Semi-Volatile Trace Metal Behavior
While lithophile trace elements can be used to constrain the role of partial
melting, mixing and crystallization at Kilauea Iki, semi-volatile chalcophile and
siderophile elements have the potential to record mobility related to subaerial degassing
(Collins et al., 2009; Norman et al., 2004; Zajacz and Halter, 2009). Existing studies
show that S and H2O partition into a volatile phase at low pressures (< 3 MPa) within
subvolcanic systems at Kilauea whereas CO2 begins degassing at much greater depth (>
45
10 MPa; Gerlach, 1986). The observed difference in sulfur concentration between melt
inclusions and matrix glasses is consistent with extensive degassing of sulfur at shallow
pressure during eruption (Fig. 3.9). While pervasive volatile loss of sulfur and other
highly volatile species is a common observation in volcanic eruptions, other studies have
noted several lines of evidence suggested that semi-volatile metals (e.g., Pb, Cd, Cu, Zn)
may also be released into the atmosphere in significant quantities during degassing. This
includes direct measurement of fumarolic gases and condensates (Crowe et al., 1987;
Hinkley et al., 1999; Mather et al., 2012; Olmez et al., 1986) and contents of marine
particulates (Rubin, 1995).
Despite this evidence, there is currently little data that indicates that such
degassing has a detectable effect on metal abundances in lavas. Some studies have
suggested volatile loss of low concentration elements such as Re, Cd, and Bi based on
rock compositions (Norman et al., 2004; Pitcher et al., 2009), but behavior of the more
abundant semi-volatile trace metals like Cu, Pb, Mo, and Zn remains unclear. The
volatile loss of these elements has more significance to potential interactions of volcanic
degassing with the environment (Sinton and Duncan, 1997) or ore deposition.
In this study we use our analyses of metals in glasses and melt inclusions to look
for trace metals abundances that have been affected by degassing by applying the so
called “petrologic method” (Thordarson and Self, 1996). In Figure 3.10, we compare
several potentially volatile metals to major volatile components S, CO2, and H2O. None
of the trace elements measured in this study have clearly higher concentrations in melt
inclusions than in glass as would be expected by degassing trends similar to S vs. FeO
(Fig. 3.9). In fact, glass compositions are typically higher than melt inclusions (e.g., Cu,
Mo, Fig. 3.10). The only trace elements with higher concentrations in melt inclusions
than matrix glass are Ni, Co, Cr, B, and Sn. Nickel, Co, and Cr are higher as a result of
compatibility in olivine (Fig. 3.5). Boron and Sn, however, are not easily explained by
crystallization of any mineral phase. Whereas B has no apparent correlations to volatile
phases, Sn shows a positive correlation with CO2 abundance (R = 0.68, 95% confidence
level; Fig. 3.10).
46
Other workers have also attempted to resolve volatile behavior and degassing of
trace elements by examining their compositional trends compared to more refractory
elements. Collins et al. (2009) argued at Mt. Etna that volatile mobility caused increased
scatter on Ce vs. Cu variation diagrams. We have examined potentially volatile trace
elements with olivine crystallization vectors against Ce and Hf in Figure 3.11. Of the
elements we display, only Mo has strongly incompatible behavior, actually increasing
with melt evolution more rapidly than we would predict with removal of only olivine.
Zinc has a nearly flat trajectory with increases in Ce or Hf, consistent with moderate
partitioning into olivine. Copper also has a nearly flat trajectory and is consistent with
crystallization of olivine, which is able to incorporate some Cu (~ 5 ppm Cu measured in
olivine in this study). Although significantly high and low Cu concentrations of melt
inclusions were analyzed, this range can easily be explained with removal or addition of
<< 1% Cu-sulfide, which have been analyzed at Kilauea Iki (Pitcher et al., 2009; Stone
and Fleet, 1991). Tin values are highly scattered and concentrations in matrix glass are
notably lower than we would predict from crystallization of olivine. This behavior is
consistent with potential volatile loss.
Given that our data suggest that there is little if any loss of volatile metals
associated with subaerial degassing at Kilauea, with the possible exception of Sn and B,
we have also estimated the amounts of volatile element loss predicted in Kilaeua lavas
based on reported compositions of fumarolic gases (Table 3.3). To do this we use
measurements of trace metals in fumarolic gases at Kilauea from Hinkley et al. (1999)
and Mather et al. (2012). In these studies metal abundances are reported as ratios to S. If
the amount of S degassed from a volcanic system is known and we assume that the
fumarole gas compositions represents the metal contents of the degassed phase, then
these ratios can be used to calculate the metal loss from the melt during degassing. We
assume a 1200 ppm loss of S in basaltic liquid at Kilaeau Iki based on differences
between melt inclusions and matrix glass (Fig. 3.9). To calculate the metal loss, the ratio
of metal to S in gas is then multiplied by the S lost from the Kilauea Iki magma. We have
made this calculation using both the average and maximum compositions of metals in
fumarole gases in Table 3.3.
47
Based on the average concentrations of elements measured in glasses from
Kilauea Iki, only Cd, Ag, In, Sn, B, Pb, and Sb would be predicted to have a > 1%
decrease in concentration during degassing, other metals would have lesser decreases
(Table 3.3, Fig. 3.12). Analytical uncertainty is typically 5-10% for most trace elements,
and much greater at concentrations < 0.1 ppm (Ag, Cd, Cs, In, Sb), so LA-ICP-MS
analyses in this study would not be expected to detect degassing losses for most elements
(Zn, Cu, Ni, Mo, Cs, Li, W, Cr, Rb, Ta, Ba, Co, Ga). Of the elements we study here, only
Sn, Pb, and B have concentrations high enough that we could potentially resolve any
degassing (Fig. 3.12). Although the degree of degassing of Cd is predicted to be quite
high, the low abundance (< 0.1 ppm) precludes measurement of this element using the
protocol we describe, however more precise techniques might be expected to detect Cd
loss (Norman et al., 2004). The predicted B concentration loss from the average
fumarolic gas analysis is 0.2 ppm, whereas median B concentrations in melt inclusions
are 0.1 ppm higher than matrix glass. This is consistent with volatile degassing of B
although overlapping compositions of matrix glass and melt inclusions makes this
conclusion less certain. Median Sn concentrations are also 0.1 ppm higher in melt
inclusions than matrix glass. This is closer to the maximum predicted decrease in
concentration from fumarolic studies. This concentration decrease along with a
correlation with CO2 suggests that we may detect the effects of Sn, and possibly B,
degassing in glass compositions at Kilauea Iki.
Conclusions
We have presented the first comprehensive examination of the trace element
character of both glasses and melt inclusions from the 1959 eruption of Kilauea Iki. Our
results refine our understanding of the petrologic evolution of this eruption:
1) We confirm the dominant control of major element composition by a mixture of
olivine fractionation and late clinopyroxene groundmass crystallization.
2) Trace element variations require that the 1959 magma was a mixture of magmas
sourced from different mantle composition by variable degrees of partial melting.
48
3) Less than 10% partial melting of a garnet-peridotite mantle that contains a few
percent of recycled oceanic crust generated these magmas.
We also report a number of potentially volatile trace metals (e.g., B, Cu, Li, Mo, Sn,
Zn) and examine these against major volatile components such as CO2, H2O, and S. Lack
of correlation between known volatile components with most potentially volatile trace
metals (e.g., Cu, Li, Mo, Sn) and compositional variations that are generally consistent
with olivine crystallization suggests there is minimal compositional effects from
partitioning of metals into a volatile-rich fluid. Tin, however, does show significantly
higher average concentrations in melt inclusions than in matrix glass and are consistent
with expected degassing trends. Given the very low concentration of most trace metals
with respect to sulfur in fumarolic gasses and condensates, we would not expect large
(>10%) changes in magma trace metal concentrations during degassing. The data
presented here support broadly incompatible behavior with some evidence for
compatibility in major (Co and Zn in olivine) and trace (Cu in sulfide) phases.
Acknowledgements
National Museum of Natural History generously provided samples of glass from
Kilauea Iki. Rosalind Helz provided discussion and a temporary loan of sulfide sample
(not presented here). Dale Burns, Allison Weinsteiger, Frank Tepley provided assistance
with microprobe analysis. Members of the VIPER (Volcanology, Igneous Petrology, and
Economic Resource) group provided many valuable discussions during the development
of this project, especially reviews provided by John Dilles, David Graham, Robert
Duncan, and Frank Tepley. Financial support for this project was provided by National
Science Foundation grant OCE-1028707 to A.J.R.K and Robert A. Duncan.
49
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54
Figure 3.1. Location of Kilauea volcano and Kilauea Iki on the island of Hawaii. The
1959 summit eruption began as a fissure (red line) and converged to a single vent (black
circle) eventually filling much of the Kilauea Iki Crater (yellow). High fire fountains
spread an unusually large tephra deposit (extent shown in purple) for Hawaiian eruptions.
Figure modified from Richter et al. (1970).
55
Figure 3.2. Corrections of melt inclusions for post-entrapment crystallization (PEC) and
diffusive Fe-loss. Glass and whole rock compositions all lie along a relatively restricted
compositional control line. Our glass and olivine FeO* values measured by EMPA are
consistently offset from previous work by ~0.5 wt.% suggesting a difference in
calibration between the two data sets. For internal consistency, we correct all melt
inclusions relative to our glass analyses, although we use the slope of Fe evolution
calculated with a linear regression of whole rock values since the greater spread of
compositions provides a more accurate regression. All melt inclusions have been
iteratively corrected to this control line using the olivine-melt geothermometer of Putirka
et al. (2007) requiring a median PEC correction of 12% by weight. S1 and S2
endmembers are defined by whole rock analyses (Murata and Richter, 1966) and are
discussed in Figure 3.4.
56
Table 3.1. Constants and parameters used in melt inclusion correction equations.
Equation Constantsa
Eqn 1 Mg
Eqn 2 Fe
a
2.158
3.3
b
55.09
47.57
c
6.213E-02
5.192E-02
d
4430
3344
e
5.115E-02
5.595E-02
f
N/A
1.633E-02
Melt Evolution Control Line
[FeO*]=m*[MgO]+b
m=b
0.0406
b=c
10.572
FeO*/FeO=d
1.13
Physical Conditions
Pressure (GPa)e
H2O (wt.%)e
0.1
0.7
Calculated Temperature (deg. C)
Median=
1275
Range=
1316-1216
a
Olivine-melt thermometer from Putirka et al. (2007)
b
Slope calculated from a linear regression of whole rock analyses in Murata and Richter (1966).
c
Intercept calculated from a linear regression of whole rock analyses minus the systematic offset we observe in FeO* between our data and previous work.
d
FeO*/FeO calculated from wet chemical analyses of Murata and Richter (1966)
e
Pressure and water contents within the range defined by melt inclusions for Anderson and Brown
(1993)
57
Figure 3.3. Major element variation diagrams. Compositions show evidence of olivine
fractionation for whole rock and glass compositions and clinopyroxene crystallization on
glass values < 7 wt. % MgO. Corrections for PEC place melt inclusions at more primitive
values than glass and in line with expected compositional trends. Note linearity of Al2O3
at all MgO values that suggests no involvement of plagioclase. The grey dashed line
shows the results of MELTs modeling at QFM redox, 1 kbar depth, and 0.7 wt.% water.
The model closely follows the compositional trend, although clinopyroxene onset is
slightly later than indicated by compositional variations. Very late plagioclase in the
MELTs model is consistent with observations of rare plagioclase microlites in thin
section observations by Helz (1987).
58
Figure 3.4. Ratio of CaO over Al2O against MgO. This ratio most clearly illustrates
major element mixing variations between the “S-1” and “S-2” components. The dashed
line represents the MELTs output. Our glass and melt inclusion analyses span the
compositional range between these two endmembers while most whole rock
compositions and the MELTs model share affinity with the S-2 component.
59
Figure 3.5. Trace element variation diagrams against MgO. Error bars are 1 se and are
smaller than symbol size if not shown for this and all subsequent trace element diagrams.
Variations generally agree with the major element trends, although more scatter exits
than would be expected by pure fractionation. A Raleigh fractionation model of 16%
olivine crystallization is shown (grey dashed line). The MELTs output was used to
determine the amount of olivine fractionated up to the onset of clinopyroxene
crystallization. The model provides a good match for compatible elements (Ni and Co)
but does not explain the range of incompatible element variation.
60
Figure 3.6. Trace element variation diagrams. Elements with similar compatibility (Sr
and Ba vs. Ce; Y and Zr vs. Hf) in a garnet-bearing mantle source show strong
correlations (R2 ≥ 0.8). Incompatible and compatible elements, however have poor
correlations (R2 ≤ 0.5). Linear regressions are of combined glass and melt inclusion data
and are displayed with a light blue line. The grey dashed line is 16% fractionation of
olivine as in Figure 3.5.
61
Table 3.2. Pearson correlation coefficients from glass and melt inclusions (n=62)
Ba
Ba
Th
0.89
Th
Nb
0.94
0.94
Nb
Ce
0.88
0.85
0.93
Ce
Sr
0.82
0.77
0.83
0.86
Sr
All values are greater than 99% confidence.
Nd
0.70
0.82
0.78
0.80
0.82
Nd
Zr
0.50
0.68
0.57
0.55
0.63
0.89
Zr
Hf
0.59
0.76
0.65
0.57
0.66
0.86
0.94
Hf
Dy
0.52
0.70
0.55
0.43
0.47
0.74
0.86
0.90
Dy
Y
0.50
0.71
0.57
0.47
0.51
0.82
0.91
0.91
0.94
Y
Yb
0.57
0.74
0.62
0.53
0.54
0.74
0.80
0.87
0.86
0.85
Yb
62
Figure 3.7. Multielement diagrams normalized to chondrite and primitive mantle
(McDonough and Sun, 1995). The steep REE pattern (high La/Yb) is typical of other
Hawaiian basalts. Most melt inclusion analyses, with the exception of KIKI-14b, have
lower concentrations of REE consistent with more primitive compositions major element
compositions. Note, fewer trace elements were analyzed for melt inclusions, and not all
odd-numbered HREEs analyzed in glass are plotted to avoid scatter resulting from poor
precision on low abundance elements. Large depletions of W, Pb, and Li are evident.
63
Figure 3.8. Plots of olivine-incompatible trace element ratios with models of mantle
melting. Two mantle sources melt curves are shown with melt fractions (F) indicated by
marks along line. The model uses the same parameters as Pietruszka et al. (1999). Source
1 is a mixture of 10% altered MORB after 4% dehydration mixed with 90% ambient
Hawaiian mantle (a mixture of 50% enriched and 50% depleted mantle). This source is a
simplified version of the early 20th century Kilauea source of Pietruszka et al. (1999).
Source 2 has a larger component of 15% altered MORB with no dehydration and 85%
ambient Hawaiian mantle. This second source is somewhat similar to the Mauna Loa
source of Pietruszka et al. (1999). Kilauea Iki compositions can be explained as 3-10%
partial melting (3-5% for most glasses) and mixing between these two source
compositions.
64
Figure 3.9. Major volatile concentrations measured with EMPA (S) and FTIR (H2O and
CO2). Sulfur is strongly degassed in matrix glass while melt inclusions lie close to or at
sulfide saturation (Mathez, 1976). Isobars calculated with VolatileCalc (Newman and
Lowenstern, 2002).
65
Figure 3.10. Examination of potentially volatile metal behavior against major volatile
components. No clear correlation between potentially volatile trace elements and volatile
components is present, with the exception of a positive correlation between Sn and CO2
(R2 = 0.48, > 99% confidence). Tin concentrations are 10% higher in median melt
inclusions than in the median glass analysis (t-test p < 0.00).
66
Figure 3.11. Selected metal concentrations examined against refractory lithophile trace
elements. Raleigh fractionation vectors are shown with partitioning estimated from the
average composition of host olivine and matrix glasses. Tin values for glass are about 0.5
ppm less than we would expect after continued fractionation of the melt inclusions
suggesting either removal of a Sn-bearing mineral phase or with volatile components.
67
Table 3.3. Expected melt concentration decreases for potentially volatile trace elements
during degassing based on studies of volcanic gas emissions at Kilauea.
Element
Average (ppm)
Max (ppm)
Cd
0.04
0.32
Ag
0.00
0.01
In
0.00
Sn
B
Average
depletion (%)
55
Maximum
depletion (%)
Average Error
(%)
405
25.0
1.4
16
16.7
0.01
1.5
12
12.5
0.03
0.15
2.5
11
4.4
0.21
0.21
9.7
9.7
6.4
Pb
0.05
0.10
4.2
8.3
4.6
Sb
0.00
0.00
1.8
5.8
16.7
Zn
0.18
0.61
0.16
0.52
2.7
Cu
0.04
0.29
0.03
0.22
3.4
Ni
0.11
0.11
0.07
0.07
2.6
Mo
< 0.00
< 0.00
0.06
0.06
4.8
Cs
< 0.00
< 0.00
0.02
0.02
10.0
Li
< 0.00
< 0.00
0.02
0.02
3.7
W
< 0.00
< 0.00
0.02
0.02
10.5
Cr
0.03
0.03
0.009
0.009
3.5
Rb
< 0.00
< 0.00
0.003
0.003
3.3
Ta
< 0.00
< 0.00
0.002
0.002
2.9
Ba
< 0.00
< 0.00
0.001
0.001
2.3
Co
< 0.00
< 0.00
0.001
0.001
2.8
Ga
< 0.00
< 0.00
0.001
0.001
2.8
Zr
< 0.00
< 0.00
0.001
0.001
1.9
Th
< 0.00
< 0.00
0.001
0.001
2.6
La
< 0.00
< 0.00
0.001
0.001
2.2
Estimated degassed concentration using measured metal/S from Hinkley et al. (1999) and Mather et al.
(2012) and assuming a 1200 ppm decrease in S during the 1959 Kilauea Iki eruption. Percentage decrease
calculated using the median glass concentration from our study.
68
Figure 3.12. Metal loss during degassing calculated from studies of volcanic gasses. Also
shown is analytical error during LA-ICP-MS analysis of glass (in red). See Table 3.3 for
details.
69
CHAPTER FOUR
TRACE METALS IN AMPHIBOLE FROM MOUNT ST. HELENS, MOUNT HOOD, SHIVELUCH, AND MOUNT PINATUBO: INSIGHT INTO METAL MOBILITY IN VOLCANIC SYSTEMS
Matthew W. Loewen
Adam J.R. Kent
70
Abstract
Arc magmas associated with subduction zones commonly are the direct source of
fluids that produce many magmatic-hydrothermal ore deposits. Observing the processes
associated with metal mobility and enrichment in active arc volcanoes can elucidate the
controls that lead to the formation of such ore deposits. In addition, the behavior of these
metals in a volcanic system may provide information on the timing and style of volcanic
eruptions. We have used LA-ICP-MS to analyze trace metal abundances (Cu, Li, Mo, Pb,
Sn, Zn, others) in amphibole from Mt. St. Helens, Mt. Hood, Mt. Pinatubo, and Shiveluch
Volcano in order to understand trace metal behavior in arc magmas. Non-volatile
lithophile trace elements from these volcanoes record variations related to source
variability, fractionation, and magma mixing. Many potentially volatile trace metals
appear to follow lithophile trace elements and behave incompatibly. For example, In, Sn,
and Zn are all enriched in low-Al amphiboles that crystallize in a shallow felsic magma
source. Copper and Li are notably decoupled from other trace elements but correlate
strongly with each other. At Mt. St. Helens, Cu and Li concentrations are similar in each
individual sample but vary widely between different samples from the same eruption.
Copper variability is typically greater than Li variability. At Mt. Hood, low-Al amphibole
rim compositions contain higher Cu and Li concentrations that overlap with the range of
Cu and Li concentrations observed in high-Al amphiboles from associated mafic
enclaves. At Mt. Pinatubo, Cu and Li concentrations are higher in low-Al amphiboles
erupted in andesite and basalt inclusions from June 7-12 eruptions than from otherwise
identical low-Al amphiboles erupted during the climatic June 15 eruption. All of these
observations are best explained by some degree of Cu and Li partitioning into a volatilerich fluid that rapidly equilibrated with amphibole phenocrysts, although details of these
processes remain unclear.
Introduction
Separation of a volatile-rich phase in magmas is a key driver of volcanic eruptions
and in some cases can also lead to the formation of magmatic ore deposits (Blake, 1984;
Hedenquist and Lowenstern, 1994). In arc volcanic systems, volatile-rich fluids are
71
typically dominated by H2O and CO2 along with subordinate Cl, S, and F species
(Wallace, 2005). In addition, a number of semi-volatile trace elements may be enriched in
this fluid (Candela and Piccoli, 1995). Common enrichment of economically valuable
elements such as Cu, Au, and Mo in hydrothermal fluids from crystallizing magmas
contributes to the development of porphyry and epithermal ore deposits (Candela and
Holland, 1986; Holland, 1972).
Direct measurement of trace element concentrations in gasses from volcanic
systems can only constrain final near-surface compositions and cannot examine extinct
systems. The so-called “petrologic method” of measuring volatiles and trace elements in
melt inclusions and groundmass glass can provide a useful means of evaluating volatile
behavior during degassing, but is complicated by post-entrapment modification of melt
inclusion compositions, sampling bias of compositions recorded in melt inclusions, and
difficulty of finding and preparing inclusions, as well as the recognition that not all
volatile phases may be initially dissolved in trapped liquid – the so called “excess”
volatile problem (Kent, 2008; Lowenstern, 1992; Thordarson and Self, 1996; Wallace,
2005; Zajacz et al., 2009). Alternatively, several studies have examined concentrations of
semi-volatile trace elements in phenocryst phases (Chambefort et al., 2013; Charlier et al.,
2012; Kent et al., 2007; Rowe et al., 2008). Amphibole provides an especially favorable
target for examination of trace element trends in subduction-related magmatic systems, as
it is widespread in arc-related magmas over a range of compositions and crustal pressures
(e.g., Gill, 1981). The complex crystal structure of the mineral also allows for the
incorporation of a wide variety of trace elements, whereas the major element composition
can be used to estimate crystallization pressures, temperatures, and bulk composition of
the parental melt (Holland and Blundy, 1994; Ridolfi and Renzulli, 2012; Ridolfi et al.,
2010; Rutherford and Devine, 1988).
Herein we examine trace element concentrations in amphiboles from several
Holocene volcanic centers: Mt. Pinatubo, Mt. Hood, Mt. St. Helens, and Shiveluch
Volcano. Each of these volcanic systems have been well-characterized by previous
studies and all of the samples analyzed in this study, except those from Mt. Hood, are
72
from eruptions that were carefully observed and samples that were collected shortly after
eruption to minimize potential complications from weathering.
Methods
Amphibole phenocrysts have been examined from four volcanic centers. These
include the May 18, June 12, July 22, and August 7, 1980 eruptions of Mt. St. Helens,
Washington; the 1991 eruption of Mt. Pinatubo, Philippines; the 2001 eruption of
Shiveluch Volcano, Kamchatka; and samples from the Old Maid eruptive period (~1780
C.E.) of Mt. Hood, Oregon. We report a total of 435 amphibole major and trace element
analyses including 172 from Mt. St. Helens, 174 from Mt. Pinatubo, 57 from Mt. Hood,
and 32 from Shiveluch. All samples except those from Shiveluch are either whole rock
samples mounted in 25 mm epoxy rounds polished with 1 µm diamond grit or are
standard polished petrographic thin sections.
Pumice and cryptodome samples from the May 18, 1980, eruption of Mt. St.
Helens were collected from the pumice plain of Mt. St. Helens. The pumice samples were
deposited during pyroclastic flows from the main Plinian eruptive phase on May 18.
Cryptodome samples were identified as dark grey blocks with breadcrust cooling
fractures within initial blast deposits of the May 18 eruption (Hoblitt and Harmon, 1993).
We also have examined thin sections provided by Kathy Cashman of airfall and
pyroclastic pumice deposited during the June 12, July 22, and August 7, 1980, Plinian
eruptions. These samples are described in Cashman and McConnell (2005).
We examined five samples of andesite and basaltic enclaves from the June 7-12,
1991, eruptions of Mt. Pinatubo provided by John Pallister and described in Pallister et
al. (1996). Five additional pumice samples were examined spanning the climatic eruption
of June 15, 1991. Plagioclase analyses and whole rock 210Pb/226Ra from these samples
were previously reported in Kayzar et al. (2009).
Five thin sections were examined from dome samples and associated mafic
enclaves erupted during the Old Maid eruptive period around 1780 C.E. of Mt. Hood,
Oregon. Previous analyses from these samples have been reported in Kent et al. (2010),
Koleszar (2011), and Koleszar et al. (2012).
73
Amphibole separates provided by Madeline Humphreys from three samples of the
2001 eruption of Shiveluch Volcano, Kamchatka, were analyzed. Previous major element
analyses of these amphiboles were reported in Humphreys et al. (2006, 2007).
Major element analyses of amphibole for Shiveluch Volcano and 16 of the major
element analyses for Mt. Hood were obtained from previous works (Humphreys et al.,
2006; Koleszar, 2011). All other major element analyses of amphibole were obtained for
this study at the Electron Microprobe lab at Oregon State University on a Cameca SX100 Electron Microprobe Analyzer. All analyses used a 1 µm beam diameter, 30 nA
current, and a 15 keV accelerating voltage. Count times were variable with 60 seconds
for Cl, 30 seconds for Mg, Ca, Ti, Mn, Fe, Al, and S, 20 seconds for F, K, and P, and 10
seconds for Na and Si. Sodium, Si, and K were corrected to zero time intercepts.
Background count times were half the peak times. Kakanui hornblende (USNM 143965)
was used as a secondary standard with results reported in Appendix B.
Trace element analyses were by Laser Ablation-Inductively Coupled PlasmaMass Spectrometry (LA-ICP-MS) in the W. M. Keck Collaboratory for Plasma
Spectrometry at Oregon State University using an Ar-F 193 nm Photon Machines G2
laser ablation system and a Thermo Scientific X-series2 quadrupole ICP-MS following
the general procedure and data processing approach outlined in Loewen and Kent (2012).
Amphiboles were analyzed using a 30 or 50 µm spot pulsed at 7 Hz for approximately 30
seconds. Standard reference material GSE-1G was used as a calibration standard and
GSD-1G, BHVO-2G, and BCR-2G were monitored as secondary standards. Calcium
concentrations from EMPA were used as internal standards. Accuracy was generally
within 10% of accepted values and full summaries of secondary standards are provided in
Appendix B. Errors shown on all figures are 1 se and do not include the uncertainty
related to characterization of the calibration standard, GSE-1G, following the procedure
outlined in Loewen and Kent (2012). Many trace elements, especially volatile metals, are
poorly characterized in this and other reference materials (Jochum et al., 2005a; 2005b)
amplifying the uncertainty in our absolute concentrations. Our errors, which do not
include this additional uncertainty, are appropriate for internal comparisons within our
data set of samples all calibrated with the same standard.
74
Amphibole analyses were filtered for evidence of contamination by hidden melt
or mineral inclusions during laser ablation. This was initially done via examination of
time-resolved spectra produced during each analysis. In addition, the comparison of TiO2
determined by LA-ICP-MS and electron microprobe analysis (EMPA) shown in Figure
4.1 shows excellent agreement between the two methods (r = 0.98, > 99% confidence).
Any analyses not within error of a linear regression of the data were rejected (a total of
33 analysis, mostly from Mt. Hood and Shiveluch analyses where microprobe data were
provided by previous studies) and are not reported. Concentrations of TiO2 determined by
LA-ICP-MS are systematically higher than those determined by EMPA at Oregon State
University (LA-ICP-MS/EMPA = 1.15). Major elements determined by Humphreys et al.
(2006) fall closer to a 1:1 line with LA-ICP-MS data. We suggest the offset of TiO2 is
therefore related to an EMPA calibration issue rather than any systematic contamination
during LA-ICP-MS.
Results
All amphibole major and trace element analyses are reported in Appendix B. The
methods of Ridolfi et al. (2010) and Ridolfi and Renzulli (2012) were used to calculate
the pressure and temperature of amphibole crystallization for each analysis. This
geothermobarometer uses the complete major element composition of amphibole (total
and octahedral aluminum, silicon, and magnesium index) to estimate pressure and
temperature, calibrated with experimental data of calc-alkaline and alkaline melts in
equilibrium with amphibole.
Calculated crystallization pressures for amphiboles from this study range from <
100 to almost 1000 MPa and temperatures range from 800 to almost 1000°C (Fig. 4.2).
The pressure determination is largely a function of molar Al/Si. We use a natural break in
our data at Al/Si = 0.27 to divide high- and low-Al amphiboles (Fig. 4.2). This break
corresponds to a liquidus melt composition of 69.5 wt.% SiO2 and pressure of 240 MPa
(Fig. 4.2). Abundant low-Al amphiboles exist for all four volcanic systems examined. Mt.
Hood and Mt. Pinatubo samples have bimodal amphibole populations grouped at 100-200
MPa (Al/Si = 0.15-0.24) and 470-580 MPa (Al/Si = 0.31-0.40). Mt. Pinatubo has a third
75
high-Al group that extends to over 900 MPa. Conversely, pressures and temperatures
recorded by amphiboles from Mt. St. Helens amphiboles are nearly continuous over the
same range as the Mt. Hood amphiboles. Shiveluch amphiboles are also continuous but
extend to only 330 MPa (Al/Si = 0.32).
Trace element compositions are systematically variable with amphibole Al
content (Fig. 4.3). Incompatible trace elements, including the rare earth elements (REE)
and Nb, Y, Sc, and Zn, are consistently higher in the low-Al amphibole populations.
Notable negative anomalies of Sr, Zr, Eu, Ti, and V in the low-Al amphiboles bring
concentrations closer to or even below the concentrations in high-Al amphibole. In
contrast, high-Al amphiboles have positive anomalies in Ba and Ti that bring
concentrations up to and higher than many low-Al amphiboles. Nickel is highly depleted
in all amphiboles although high-Al amphiboles typically have higher Ni concentrations
than low Al amphiboles. Rubidium is depleted in all amphiboles sometimes below
detection limits, with the exception of high-Al Mt. Pinatubo samples that have unusually
high Rb concentrations. Concentrations of Li, Pb, and Cu are all highly variable with no
clear correlation with high- or low-Al amphiboles.
Concentrations of Ce are precisely measured in all amphiboles (10-70 ppm) and
provide a proxy for general melt evolution since Ce is generally incompatible in all
crystal phases (Fig. 4.4). As shown in Figure 4.2, low pressure (and low-Al) amphiboles
are generally in equilibrium with more felsic melts than high-Al amphiboles. Likewise,
more evolved Ce concentrations correspond to low pressure amphiboles (Fig. 4.4).
Comparing Ce variations to other trace elements allows for examination of melt evolution
trends and amphibole population variations. Lithophile elements display systematic
variations with Ce (Fig. 4.5). Many of the same trends inferred from multielement
diagrams (Fig. 4.3) are evident on these plots. In addition, significant differences between
volcanic systems are evident. Yttrium, Nb, and Ce concentrations vary by volcano. In
contrast, Ni and Ti are compatible in amphibole with with higher concentrations in the
low-Ce, high-Al amphiboles.
Zirconium and Sr compositional trends are more complex. Zirconium generally is
positively correlated with Ce, with the notable exception of high-Ce, low-Al Pinatubo
76
amphiboles where Zr is negatively correlated with Ce. Mt. Hood amphiboles from this
same compositional range vary widely with respect to Zr. High-Al amphiboles have two
distinct Sr trends: the first trend has a positive correlation with Ce and is observed in Mt.
Pinatubo, Mt. Hood, and some Mt. St. Helens amphiboles; the second has a negative
correlation between Sr and Ce. All low-Al, high-Ce amphiboles are lower in Sr and
correspondingly have pronounced negative Eu anomalies (Eu/Eu* < ~0.7; Fig 4.6). In
contrast, Eu anomalies are highly variable in high-Al amphiboles.
Potentially volatile trace elements such as Cl, Zn, In, and Sn also have systematic
variations with Ce and are generally present at higher concentrations in high-Ce, low-Al
amphiboles (Fig. 4.7). Low-Al (shallow) amphiboles from Mt. Hood have notably higher
Cl than comparable amphiboles from Pinatubo, and also have higher In, Li, and Cu
concentrations. Conversely, Zn and Sn, are more concentrated in low-Al amphiboles
from Pinatubo.
We observe no systematic variations for Li and Cu with Ce. This is also the case
for Ag and Pb, however, these elements are also present at much lower concentrations (<
1 ppm) and corresponding uncertainties are higher. Whereas Li and Cu do not
systematically vary with any lithophile elements or between amphibole pressure
populations, their concentrations are significantly correlated with each other (Fig. 4.8).
This correlation is significant at > 99% confidence using either a linear correlation of
concentrations (r = 0.72) or a linear correlation after a log transformation of
concentrations (r = 0.82).
Discussion
General amphibole variations
Lithophile trace element variations observed in amphibole phenocrysts provide
valuable information on magmatic processes. The bimodal distribution of amphibole
crystallization pressures at Mt. Hood and Mt. Pinatubo is consistent with magma storage
and amphibole crystallization in separate magma chambers and has been described in
other studies (Kent et al., 2010; Koleszar et al., 2012; Prouteau and Scaillet, 2003; Ridolfi
et al., 2010; Walker et al., 2012). The higher concentrations of incompatible trace
77
elements in the low-Al amphiboles are also broadly consistent with a more evolved
parental melt (Rutherford and Devine, 2008) although some of this variation is likely due
to higher crystal/melt partitioning in more felsic magmas (Cambefort et al., 2013).
Variations in trace element concentrations in amphibole between volcanoes also
suggest differences in source and/or fractionation histories are recorded in amphiboles
from each volcanic system. For example, variable degree of Ba enrichment in high-Al
amphiboles is consistent with Ba mobility in arc fluids. Zirconium variations are most
easily explained by fractionation of zircon in more silicic magmas. For example the tight
decreasing trend of Zr concentrations with increasing Ce concentration in low-Al
amphiboles from Pinatubo is consistent with removal of zircon from the melt during
differentiation. Low Sr concentrations in low-Al amphibole is most easily explained by
significant plagioclase fractionation from the evolved parental melt prior to
crystallization of amphibole. Variations in Sr in high-Al amphiboles are more complex
(Fig. 4.6). Increasing Sr with differentiation suggests these melts may be evolving
without crystallization of Na-rich plagioclase.
Although lithophile trace elements reveal a substantial amount of information
about magmatic processes, the primary focus of this work is on the behavior of
potentially volatile metals. For this reason we do not treat the lithophile element
variations in detail, but use the observed patterns of these elements to provide a baseline
to assess anomalous metal behavior that could be related to mobility within an volatilerich fluid during or after amphibole crystallization.
Volatile metal behavior
For most volatile metals studied here there is little direct evidence for mobility in
a volatile-rich fluid. Positive correlations between Zn, In, and Sn versus Ce are consistent
with generally incompatible behavior in the melt and appear typical of other refractory
incompatible elements (Fig. 4.7). If these metals are eventually incorporated into a
volatile-rich fluid during eruption or hydrothermal release accompanying ore deposit
deposition, these data suggest they are sourced from more felsic melts since their
concentrations are lower in amphiboles crystallized from more mafic melts. In contrast,
78
Li and Cu show behavior that appears inconsistent with typical petrologic processes like
fractionation, partial melting, or magma mixing (Fig. 4.7) since they have no systematic
variations with other lithophile elements that are expected for variations in melt source or
crystallization history. Lead and Ag also show slightly decoupled trends from other
lithophile elements (Fig. 4.7); however, their low abundances (< 1 ppm) result in larger
analytical uncertainty making interpretation of their trends difficult. Positive correlation
between Li and Cu (Fig 4.8) suggests similar processes controls the concentrations of
these two elements. Several previous workers have called on volatile fluids to transport
Cu and especially Li in volcanic systems (Berlo et al., 2004; Charlier et al., 2012; Kent et
al., 2007; Nadeau et al., 2013; Rowe et al., 2008). The following sections examine Cu
and Li behavior in more detail at Mt. St. Helens, Mt. Hood, and Mt. Pinatubo.
Mt. St. Helens
Whereas Li and Cu positively correlate across all samples from Mt. St. Helens,
concentrations of both Li and Cu are strikingly clustered in individual amphiboles
analyzed from within the same samples (Fig. 4.9). Concentrations vary greatly between
samples, however, even where these come from a single eruption. For example, the five
samples analyzed from the June 12 eruption span almost the entire observed range of Li
and Cu variations (5-500 ppm Li, 1-70 ppm Cu). Within a single sample, Cu is generally
more variable than Li as demonstrated by the slope of best fit lines for each sample; only
three out of the eleven samples analyzed have strongly positive slopes while most have
slopes close to zero (Table 4.1).
This sample-to-sample variability in Li and Cu has been observed in other studies,
notably Chiaradia et al. (2012), who attributed it to the effects of fractionation from
variable initial magma compositions. This is unlikely to be the case here, however, as the
bulk composition is similar for many of these samples (Pallister et al., 1992a). In addition
comparison between Cu, Li, and elements that show variations related to fractional
crystallization suggest that Cu and Li are decoupled from other elements during melt
evolution (Figs. 4.5, 4.7).
79
An alternate explanation for sample-to-sample variability is found in Berlo et al.
(2004), Kent et al. (2007), and Rowe et al. (2008), who proposed that Li was transported
in an aqueous fluid. Separation of a vapor phase may allow significant partitioning of Cu
and Li from the melt into the fluid phase (Candela and Holland, 1986; Candela and
Piccoli, 1995). Transport of this phase to other parts of the magma reservoir via
convection, bubble rise, and/or other mechanisms (Kayzar et al., 2009), results in
transport of Li and Cu. These can then rapidly re-equilibrate with minerals, which
preserve a diversity of Li and Cu contents. Although the diffusivity of Li and Cu in
amphibole is presently uncertain, other silicate minerals exhibit rapid Li diffusion
(Coogan et al., 2000; Giletti and Shanahan, 1997; Parkinson et al., 2007). Thus on short
time scales Li can re-equilibrate within individual minerals. The diffusivity of Cu is also
likely rapid (Zajacz et al., 2009), and the pervasive broad similarity of Li and Cu within
samples suggests that diffusive equilibration after removal or addition of a volatile fluid
to a sample must be extremely rapid.
We find no evidence to support Li and Cu variations being inherited from magma
storage conditions. Textural classifications were used by Cashman and McConnell (2005)
to infer the depth of magma storage. If Li and Cu variations were inherited at depth in the
magma, we would expect some correlation of textural types (Cashman and McConnell,
2005) with Li and Cu concentrations. However, no pattern of textural type and Li or Cu
concentration can be observed. In addition, there is no observed correlation of Li and Cu
with calculated amphibole crystallization pressure (Fig. 4.7).
The large compositional variability between pumices from the same eruption and
individual trends of Li and Cu within the same samples suggests that some of this
variation may be due to the depositional history of the individual samples as opposed to
magma storage conditions. Both Li and Cu can rapidly diffuse in silicate phases (Kent et
al., 2007; Rowe et al., 2008; Zajacz et al., 2009). Lithium is smaller than Cu and
therefore should diffuse more rapidly. Thus differences in cooling rate couple with
variations in diffusion of Li and Cu could also modify amphibole trace element contents.
If we assume differential Cu and Li diffusivity, greater Cu variations could be due to the
longer time required for Cu to fully equilibrate within a sample compared to Li.
80
Interestingly, the two steepest slopes on a log plot of Li versus Cu (Fig. 4.9) are for airfall
samples (12af16 and 12af9) that presumably cooled more quickly and could preserve
greater variations in Li concentration. More detailed study of samples from single
depositional units could help clarify the timing and cause of Li and Cu variability.
Our results from Mt. St. Helens demonstrate a need for caution when comparing
Li and Cu variations. Lithium or Cu variability observed by previous workers between
samples of different bulk composition (Chiaradia et al., 2012) or over the course of an
eruptive period (Berlo et al., 2004; Kayzar et al., 2009; Kent et al., 2007; Rowe et al.,
2008) may be due to short-term eruption or depositional history. Lithium and Cu
variations that occur over an eruption or series of eruptions may be masked by much
larger variations occurring during a single event.
Mt. Hood
At Mt. Hood we have examined amphibole compositions from a single mafic
enclave and its associated dacitic host lava (Fig. 4.10). These samples were erupted in
small dome-forming eruptions, and define a highly bimodal magma population that
includes an especially high-Cl, low-Al amphibole population (Koleszar et al., 2012; Fig.
4.7). Amphiboles in the host dacite belong to the low-Al population and also have lower
Sr and higher La and Ce concentrations consistent with growth in an evolved shallow
magma chamber (Fig. 4.10). No consistent zoning was observed in any amphiboles for
major element compositions or lithophile trace element concentrations. In contrast, Cl,
Li, and Cu are all offset to higher concentrations in the rims of amphiboles from the host
dacite (Fig. 4.10). Amphiboles in the mafic enclave are generally small (< 100 µm) and
separate core and rim analyses of single grains were rarely possible. Rim compositions of
Cu in amphiboles from the host dacite overlap the range of Cu concentrations in
amphiboles from the mafic enclave, with both enclave and host rim compositions at
higher Cu concentrations than any host core compositions.
Elevated concentrations of the volatile elements Li, Cu, and Cl in amphibole rims
are not associated with elevated concentrations of any trace element variations and thus
81
are best explained by diffusion. Separation of a volatile fluid could partition all three of
these elements out of the magma and result in diffusion into rims of host amphiboles.
Pinatubo
Little variability in any major or trace element amphibole composition is observed
from the June 15, 1991, climatic eruption of Mt. Pinatubo (Fig. 4.11), the majority of
which are classified as low-Al amphibole. Considerably more variability is evident in
amphiboles from June 7-12, 1991, andesite and basalt inclusions consistent with their
eruption during mixing after a mafic recharge event (Pallister et al., 1996). High- and
low-Al amphiboles were recorded from these early eruptions. Low-Al amphiboles are
compositionally similar in all non-volatile incompatible lithophile elements (e.g., La,
shown in Fig. 4.11). Copper and Li, however, are found with notably higher
concentrations in low-Al amphiboles from June 7-12 than in low-Al amphiboles from the
June 15 climatic eruption. High-Al amphiboles from June 7-12 generally have lower Li
and Cu concentrations than corresponding low-Al amphiboles.
This observation suggests some evidence for the timing and source of Cu and Li
variability at Mt. Pinatubo. Low-Al amphiboles in the June 7-12 andesite probably
crystallized from the existing shallow silicic magma chamber and were mixed with highAl amphiboles derived from a deep magma during mafic recharge (Pallister et al., 1996).
Other than Li and Cu concentrations, these low-Al amphiboles are identical to those from
June 15. If an aqueous fluid with Li and Cu were separated from the magma during the
initial eruptions the remaining amphiboles erupted on June 15 may have equilibrated with
a melt containing considerably less Li and Cu. This explanation suggests that Li and Cu
could diffusively equilibrate through the magma body over period of a few days.
The 1991 eruption of Mt. Pinatubo released over 20 million tons of SO2, more
than any other observed volcanic eruption (Bluth et al., 1992). Comparison of melt
inclusions and matrix glass cannot account for the loss of sulfur (Rutherford and Devine,
1996; Westrich and Gerlach, 1992) resulting in some controversy over the origin of the
SO2 with some arguing for flux from a deeper mafic intrusion (Pallister et al., 1996;
1992b), breakdown of anhydrite in the felsic magma (Rutherford and Devine, 1996),
82
and/or existence of a separate vapor phase (Hattori, 1993; Westrich and Gerlach, 1992)
before the eruption. Our observed decrease in Li and Cu concentrations for samples
erupted after June 7-12 can be explained if Li and Cu were released with SO2 followed by
rapid equilibration with the melt. Melt inclusions from the June 15 dacite have similar Cu
concentrations to the matrix glass (Borisova et al., 2006), however, if Cu is able to
rapidly equilibrate through whole amphibole phenocrysts it also may be equilibrated with
any melt inclusions.
The underlying source of Cu and Li is unclear. The fact that concentrations are
higher in low-Al amphiboles than corresponding high-Al amphiboles from the June 7-12
samples suggests higher concentrations were present in the shallow, felsic magma
chamber. This is also consistent with incompatible Cu behavior inferred by Borisova et
al. (2006).
Conclusions
• Amphiboles track magmatic conditions at these four volcanic centers, including
two distinct magma bodies (a shallow evolved magma and a deep less-evolved
magma) at Mt. Pinatubo and Mt. Hood and more continuous pressure and
temperature conditions at Mt. St. Helens.
• The semi-volatile elements Ag, Mo, Sb, Cd are often above analytical detection
limits in amphiboles in this study, but not at high enough concentrations to
determine clear trends.
• Amphiboles record higher concentrations of In, Sn, and Zn in felsic parental melts
than in mafic parental melts.
• Cu and Li in amphiboles from Mt. Hood, Mt. St. Helens, Mt. Pinatubo, and
Shiveluch are generally correlated and do not match any other compositional
trends.
• Significant Cu-Li variability in amphibole can exist between samples from a
single eruption.
83
•
Both Cu and Li seem to be related to the presence of a volatile phase and may
diffuse very rapidly (on the scale of days?) through amphibole phenocrysts and
the host melt.
Acknowledgments
Samples examined in this project have been provided by Katherine Cashman (Mt.
St. Helens), John Pallister (Mt. Pinatubo), Madeline Humphreys (Shiveluch), and Mt.
Hood (Alison Koleszar). Extraordinary assistance with Electron Microprobe analysis by
Frank Tepley and especially Dale Burns was instrumental in our ability to examine a
large number of amphiboles with limited microprobe time. Discussions with Alison
Koleszar and other members of the VIPER (Volcanology, Igneous Petrology, and
Economic Resources) group at Oregon State University contributed to the development
of this paper.
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Figure 4.1. Comparison of Ti concentrations by EMPA and LA-ICP-MS. Error bars for
this figure are 1 se for LA-ICP-MS data and include uncertainty in characterization of the
calibration standard (GSE-1G). Concentrations by LA-ICP-MS are slightly higher than
EMPA from Oregon State University, while EMPA data from Humphreys et al. (2006)
lie on the 1:1 line. All reported data are within error of a linear regression between the
two methods. Any analyses without agreement between the two methods have been
excluded from the data set.
89
Figure 4.2. Calculated amphibole pressure (P) compared to calculated temperature (T)
and molar Al/Si. Pressure and temperatures are calculated using Ridolfi and Renzulli
(2012) and plotted with amphibole stability zone (dashed black lines), equilibrium melt
SiO2 (grey lines), and representative P-T error bars from Ridolfi et al. (2010). Pressure
and to a lesser extent temperature is largely a function of molar Al/Si and the division
between high and low amphiboles used in this study was chosen from a small natural
break occurring at Al/Si = 0.27.
90
Figure 4.3. Rare earth element and multi-element spider diagrams comparing high- and
low-Al amphiboles. Low-Al, low pressure amphiboles generally have higher
concentrations of trace elements except Li, Rb, Ba, Pb, Sr, Zr, V, Zn, Cu, and Ni.
Shallow amphiboles also have more pronounced Eu anomalies. A clearly bimodal
distribution of amphibole compositions is evident at Mt. Hood and Mt. Pinatubo. Mt. St.
Helens amphiboles have a near continuum of composition between low- and high-Al
amphiboles. Fewer analyses were available for Shiveluch and only define a low-Al
population.
91
Figure 4.4. Calculated pressure versus Ce concentrations in amphiboles. Pressures
calculated from Ridolfi and Renzulli (2012). High-Ce amphiboles are generally low
pressure. Concentration of Ce is a reasonable proxy for magmatic evolution. Error bars
shown for Ce and all future trace element plots are 1 se not including uncertainty in the
calibration standard.
92
Figure 4.5. Variation diagrams for Ce versus lithophile trace elements and Eu anomalies.
Lithophile trace elements have generally systematic variations with Ce that can be
explained by crystal fractionation, melt source variations, and magma mixing.
93
Figure 4.6. Comparison of chondrite normalized Eu anomalies (Eu/Eu*) compared to Sr
concentrations. Eu* calculated as the Eu concentration divided by the chondrite
normalized average of Sm and Gd. Fractionation of low-An plagioclase in oxidizing
systems should decrease Sr and decrease the Eu anomaly of a melt. Plagioclase
fractionation regardless of An content or redox condition is likely to decrease Sr. High-Al
amphiboles from all four volcanoes have higher Sr and Eu/Eu* than low-Al amphiboles,
although they comprise a considerable range in both Sr and Eu/Eu* and show no
correlation between the two parameters. Conversely, low-Al amphiboles are grouped
tightly at Mt. Pinatubo, Mt. St. Helens, and Mt. Hood and have a large range of Eu/Eu*
over a short range of Sr concentration.
94
Figure 4.7. Variation diagrams for Ce versus potentially volatile trace elements. All
elements shown except Cl are measured by LA-ICP-MS. Concentrations of Cl, Zn, In,
and Sn all vary systematically with Ce and are typically higher in amphiboles sourced
from more evolved and shallow magma bodies within any given volcano. Both Cu and Li
are highly variable and have no relationship with Ce concentration or pressure.
Concentrations of Ag and Pb are also variable, but at very low concentration and with
high analytical uncertainties.
95
Figure 4.8. Covariation between Cu and Li shown on a log-log plot. Across all four
volcanic systems Cu and Li are significantly correlated (> 99% confidence) using either a
linear regression of Cu vs. Li or a linear regression on log(Cu) vs. log(Li) (r = 0.72 and
0.82, respectively).
96
Figure 4.9. Concentrations of Cu and Li in amphiboles from Mt. St. Helens grouped by
sample. Compositions are clearly grouped sample-to-sample in addition to an overall
positive correlation between Cu and Li. Different samples from one eruptive episode
have almost the same range of Cu and Li contents as the entire data set. Lines are linear
regressions of log (Cu) and log (Li) for each eruptive episode. Sample names for the June
12-July 22 eruptions are for one thin section each, with lettering describing airfall (af) or
pyroclastic flow (pf) deposition.
Regression for Li and Cu
log (Cu) and log (Li)
Sample
na
Li (ppm)b Cu (ppm)b
rc
CLd
me
rc
CLd
me
18cd01
24
18.9
7.8
0.13
46
0.01
0.09
32
0.01
18pp01
17
3.9
2.3
0.38
87
0.13
0.36
84
0.12
12af16
15
283
41.2
0.77
100
4.76
0.76
100
0.75
12af9
17
12.6
2.5
0.72
100
6.58
0.74
100
1.30
12pf1
13
7.2
2.0
-0.01
3
-0.02
0.08
20
0.04
bl12pf10
21
64.2
16.9
0.91
100
2.99
0.88
100
0.79
22af19
9
3.7
1.9
-0.11
22
-0.13
-0.11
22
-0.07
22af3
3
3.6
1.5
0.92
74
0.62
0.90
71
0.33
22pf17
31
32.7
11.9
0.45
99
0.49
0.50
100
0.22
22pfA6
9
11.4
3.7
0.46
79
0.47
0.48
81
0.20
7wrs16
13
4.0
1.5
-0.19
47
-0.24
-0.21
51
-0.12
a
n is the number of amphibole analyses included in regression; b median amphibole concentrations; c r is the
correlation coefficient; d CL is the confidence limit for calculated r values given n analyses; e m is the slope of the
regression line.
Table 4.1. Copper-Lithium correlation coefficients for individual samples from Mt. St. Helens.
97
98
Figure 4.10. Enclave and host amphibole compositions from Mt. Hood. All analyses are
from an enclave and associated dacite host from the Old Maid eruptive period (host lava
MH09-04 and mafic enclave MH09-04a). High- and low-Al populations are clearly
evident. No significant core-rim zonation is observed in pressure calculations, Sr, or La.
Rims of amphiboles from the low-Al dacite host magma (rims outlined in yellow),
however, have elevated Cl, Cu, and Li concentrations compared to the cores of these
same amphiboles. Core compositions from the amphiboles in the host dacite are lower in
Cu than any amphiboles from the enclave (range of rim compositions outlined in blue).
99
Figure 4.11. Amphibole compositions over the course of the 1991 eruption of Mt.
Pinatubo. June 7-12 samples are arranged by whole rock composition (left to right—
basalt to andesite) while the June 15 dacite samples are arranged by eruptive sequence
(left to right—early to late). Most elements behave like La and have no discernable trends
over the duration of the eruption. Low-Al amphiboles consistently have higher La than
high-Al amphiboles. The low-Al amphiboles erupted June 7-12 however, have notably
higher Cu and Li than any of the June 15 shallow amphiboles (range shown in pink).
High-Al amphiboles from June 7-12 are also higher in Cu and Li than the June 15
samples, although not as high as the low-Al amphiboles from the same period.
100
CHAPTER FIVE
PROLONGED PLUME VOLCANISM IN THE CARIBBEAN LARGE IGNEOUS PROVINCE: NEW INSIGHTS FROM CURAÇAO AND HAITI
Matthew W. Loewen
Robert A. Duncan
Adam J.R. Kent
Kyle Krawl
This manuscript is published in:
Geochemistry, Geophysics, Geosystems
John Wiley & Sons, Inc.
350 Main Street, Malden, MA 02148
October 2013, v. 14, no. 10, p. 4241-4259.
101
Abstract
We present 36 new 40Ar-39Ar incremental heating age determinations from the
Caribbean Large Igneous Province (CLIP) providing evidence for extended periods of
volcanic activity and suggest a new tectonomagmatic model for the province’s timing and
construction. These new 40Ar-39Ar ages for the Curaçao Lava Formation (CLF) and
Haiti’s Dumisseau Formation show evidence for active CLIP volcanism from 94 to 63
Ma. No clear changes in geochemical character are evident over this period. The CLF has
trace element signatures (e.g., Zr/Nb = 10-20) and flat rare earth element (REE) trends
consistent with plume volcanism. The Dumisseau Formation also has plume-like
geochemistry and steeper REE trends similar to ocean island basalts. Volcanism in the
Dumisseau Formation appears to have largely ceased by 83 Ma while at Curaçao it
continued until 63 Ma. A rapidly surfacing and melting plume head alone does not fit this
age distribution. Instead, we propose that the residual Galapagos plume head, following
initial ocean plateau construction, was advected eastward by asthenospheric flow induced
by subducting oceanic lithosphere. Slab rollback at the Lesser Antilles and Central
America subduction zones created an extensional regime within the Caribbean plate.
Mixing of plume with upwelling asthenospheric mantle provided a source for intermittent
melting and eruption through the original plateau over a ~30 Ma period.
Introduction
Large Igneous Provinces (LIPs) represent enormous volumes (> 106 km3) of
mafic magmas, typically emplaced over geologically short intervals of a few million
years (Coffin and Eldholm, 1994). The Caribbean Large Igneous Province (CLIP) is a
large submarine plateau thought to have been constructed initially as a LIP that now
forms a thickened zone of oceanic crust between North America and South America
(Burke et al., 1984; Duncan and Hargraves, 1984). LIPs are generally considered to form
from melting related to a decompressing mantle plume head during the initiation of hot
spots (Morgan, 1981; Richards et al., 1989; Campbell and Griffiths, 1990; Duncan and
Richards, 1991).
102
Geochemical and geochronological evidence strongly associates the Galapagos
hot spot with a ~95-90 Ma initiation of the CLIP. Originally formed in the eastern Pacific
at the initiation of Galapagos mantle plume activity, the CLIP moved northeastward with
the Farallon plate between the North and South American plates until collision with the
Greater Antilles arc (Burke et al., 1984; Duncan and Hargraves, 1984; Kerr et al., 2003).
Volcanism can then be traced from the voluminous CLIP to the Galapagos Islands
through a fragmentary 60 million year history partially preserved as accreted seamounts
along the Central American coast and via the Cocos and Carnegie ridges (Hoernle et al.,
2002; Buchs et al., 2011). Isotopic domains present in the Galapagos Islands can be
matched with similar compositional arrays observed in CLIP lavas (Hauff et al., 2000;
Geldmacher et al., 2003; Thompson et al., 2003). In addition, rare earth element (REE)
patterns and mantle temperature calculations are consistent with melting from a mantle
plume (Sinton et al., 1998; Herzberg and Gazel, 2009; Hastie and Kerr, 2010).
Despite significant evidence for a mantle plume and a Pacific origin of the CLIP,
a number of studies propose alternative models. Pindell et al. (2006) and Wright and
Wyld (2011) suggest formation above a slab window with possible plume influence, and
propose a much older age of CLIP initiation. Conflicting age estimations of CLIP lavas
from the Curaçao Lava Formation (CLF; Beets, 1972) highlight this controversy. 40Ar39
Ar ages of Sinton et al. (1998) at 89.5 Ma and 88 Ma from samples identified as the
bottom and top of a 5 km submarine lava section described by Klaver (1987) suggest a
relatively short emplacement period for the majority of lavas. Fossilized ammonites in
one locality of intercalated sediments, however, have been identified as mid-Albian
(~105 Ma; Wiedmann, 1978). Poikilitic sills and quartz-diorite plugs intruding the CLF
have younger reported ages of 75 Ma (40Ar-39Ar whole rock; Sinton et al., 1998) and 86
Ma (U-Pb zircon; Wright and Wyld, 2011).
Observations at CLIP localities north of Curaçao have led to a more consistent
model of plume activity. The 1.5 km thick Dumisseau Formation of Haiti has previously
reported radiometric ages of 94 to 88 Ma, in agreement with biostratigraphic data (Sinton
et al., 1998). At Beata Ridge, a fault-bounded monocline located just south of Haiti, a
sub-seafloor sill complex is younger at 81 to 74 Ma (Révillon et al., 2000), lying below
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the plateau surface dated at 94 to 89 Ma (Edgar and Saunders, 1973; Sinton et al., 1998).
The light rare earth element (LREE) enriched character of the Dumisseau basalts
compared with the more depleted Beata Ridge basalts led Sinton et al. (1998) and
Révillon et al. (2000) to propose the older phase of activity was the result of initial plume
volcanism and the younger phase was the result of extension and thinning of the plateau
during interaction with the Greater Antilles subduction zone to the east.
The aim of this paper is to present new high precision geochronology and
geochemistry for the CLF, Curaçao and the Dumisseau Formation, Haiti. These two
formations span a N-S transect of the CLIP and are perhaps the best exposures of internal
structure and composition of the eastern portion of this ocean plateau. Combining our
results with extensive geochronology already available for plateau rocks elsewhere in the
Caribbean has allowed us to re-examine the tectonomagmatic origin of this submarine
LIP.
Geologic Background
Curaçao
The CLF forms much of the interior of the island of Curaçao, a tectonically
uplifted part of the southern margin of the CLIP, located off the northern coast of
Venezuela (Fig. 5.1). It was first mapped by Beets (1972) as a late Cretaceous sequence
of submarine lavas more than 1000 m thick, unconformably capped by sedimentary rocks
of the Knip Group and Midden-Curaçao Formation. Klaver (1987) provided the first
detailed study of the petrology of this formation. He proposed a 5 km section of
submarine basalts ranging from picrites and olivine tholeiitic pillow basalts at the bottom
of the sequence to plagioclase-clinopyroxene tholeiitic pillows, hyaloclastites, and
poikilitic sills at the top. The variable thickness proposed for the CLF reported by these
two studies reflects the highly weathered and discontinuous outcrops present on Curaçao
making interpretation of the structural and stratigraphic relationships uncertain. The
major, minor, and trace element geochemistry of these rocks was described in detail by
both Klaver (1987) and Kerr et al. (1996), with both studies concluding that observed
variations could be achieved by crystal fractionation and/or accumulation from a
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common parental melt. Trace element and isotopic signatures are consistent with large
degree melting of a plume-like mantle source, similar to conclusions reached from other
Caribbean locations (Kerr et al., 1996; Hauff et al., 2000).
Limited age constraints on CLF samples have provided inconsistent information.
Ammonites from the only observed sediments intercalated with lava flows were
identified as mid-Albian (~105 Ma; Wiedmann, 1978), although the fossils were broken
and highly deformed and could be reworked deposits (Kerr et al., 2003). Sinton et al.
(1998) analyzed three samples with identified 40Ar-39Ar plateau ages of 89.5 ± 1.0 and
88.0 ± 1.2 Ma from lavas at the top and bottom of the formation and a 75.8 ± 2.0 Ma age
on a diabase sill. The oldest of these ages was reanalyzed by Snow et al. (2005) with a
slightly older and more precise plateau age of 92.8 ± 0.5 Ma. These ages were consistent
with the previously identified volcanic stratigraphy (Klaver, 1987), and consistent with
an interpretation of rapid eruption of lava flows, based on the relative lack of intercalated
sediments, followed by later intrusions. The most recent work on the island is less
conclusive; Wright and Wyld (2011) reported a 86.2 ± 0.8 Ma U-Pb zircon age for a
quartz diorite plug that intrudes the CLF at the north end of the island and Humphrey
(2010) reported an older and less precise age of 112.7 ± 7.3 Ma from U-Pb dating of
baddeleyite from a diabase sill, and suggested an older emplacement age for the CLF.
Dumisseau Formation, Haiti
The Dumisseau Formation of Haiti is exposed by thrust and strike-slip faulting
along the northern margin of the CLIP (Fig. 5.1 insert). The formation consists of a 1.5
km section of massive and pillow basalt and picrite flows with intercalated pelagic
limestones, siltstones, and turbidites, intruded by dolerite sills (Maurrasse et al., 1979).
Sen et al. (1988) showed that the geochemistry of the formation was typical of CLIP
lavas found in the center of the Caribbean Plate from ocean drilling during DSDP Leg 15.
Most samples have trace element signatures and isotopic compositions similar to other
CLIP localities, although many samples show LREE enrichment more characteristic of
ocean island basalts (OIB).
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Sinton et al. (1998) analyzed five whole rock samples from the Dumisseau
Formation using 40Ar-39Ar incremental heating experiments and obtained plateau ages
ranging from 96.2 ± 6.5 to 89.8 ± 1.1 Ma. These ages overlap the Coniacian to Turonian
fossils (94-84 Ma) from interbedded sediments at the bottom of the Dumisseau Formation
and are older than the late Santonian to early Campanian (84-80 Ma) fossils found in
sedimentary interbeds at the top of the formation (Maurrasse et al., 1979). Five additional
samples were analyzed by Snow et al. (2005) with 40Ar-39Ar total fusion ages from 95.192.2 Ma although these analyses were all affected by significant 39Ar recoil and did not
develop age plateaus.
Beata Ridge and the Interior of the Caribbean Plate
The CLIP has also been sampled in an intact central area of the Caribbean Plateau
at the Beata Ridge and several Deep Sea Drilling Program (DSDP) and Ocean Drilling
Program (ODP) sites (Donnelly et al., 1973; Révillon et al., 2000; Sinton et al., 2000;
Kerr et al. 2009; Fig. 5.1 insert). Together, the Dumisseau Formation, CLF, and these
central sites provide a N-S transect through the center of the Caribbean plateau and CLIP
outcrops. Both the LREE enriched, OIB-like basalts of the Dumisseau Formation and flat
REE patterns similar to those found in the CLF are found in the Beata Ridge and DSDP
sites (Sinton et al., 1998; Révillon et al., 2000). The oldest ages are found from DSDP
Site 146 lavas: 40Ar-39Ar whole rock plateau ages of 90.6 ± 3.2, 92.1 ± 4.7, and 94.3 ± 2.8
Ma (Sinton et al., 1998). At the Beata Ridge, where a thick sill complex was sampled by
submersible, considerably younger ages were obtained for whole rock and plagioclase
separates: 9 plateau ages between 81 and 74 Ma, and two plateau ages at ~56 Ma
(Révillon et al., 2000).
Sampling and Methodology
Samples for this study were collected on the island of Curaçao in April 2010 and
supplemented with samples previously described in Kerr et al. (1996) and Klaver (1987).
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1
Coordinates for the collected samples are available in the Supplementary Data while
locations of previously studied samples are estimated from location maps provided within
those references (Fig. 5.1). Samples from the Dumisseau Formation, Haiti, were
previously described in Maurrasse et al. (1979) and Sen et al. (1988).
Age determinations for 22 samples from Curaçao and 14 samples from the
Dumisseau Formation were derived from whole rock, groundmass, plagioclase, or glass
separates. Whole rock samples consisted of 4 mm diameter mini-cores of the fresh and
relatively phenocryst-free portions of rock fragments. The groundmass and plagioclase
samples were crushed and sieved to a 200-300 or 400-500 µm size fraction and subjected
to an extended acid leaching procedure following Koppers et al. (2000). This consisted of
15 minute sequential leaching in 1 N HCl, 6 N HCl, 1 N HNO3, and 3 N HNO3. Before
irradiation, 50-100 mg of material was hand picked from the final leached separate.
Whole rock and glass separates were not subjected to acid leaching. All samples were
irradiated at the Oregon State University 1 MW TRIGA Reactor. Neutron flux was
monitored using a Fish Canyon Tuff biotite (FCT-3) with a monitor age of 28.02 ± 0.16
Ma (Renne et al., 1998). Argon extraction and analysis was achieved with a Merchantek
10 W CO2 laser and an MAP-215-50 mass spectrometer following the methods outlined
in Duncan and Hogan (1994) and Duncan et al. (1997). Data reduction utilized
ArArCALC v.2.2 (Koppers, 2002) using decay constants suggested by Steiger and Jäger
(1977).
Total fusion, plateau, and isochron ages are summarized for all analyzed samples
in Tables 5.1 and 5.2. Total fusion ages incorporate all heating steps in a given
incremental heating experiment and some step ages are clearly influenced by postcrystallization Ar-loss evident in the age spectra. Several samples are affected by
redistribution of 39Ar and 37Ar atoms during neutron irradiation. This occurs in finegrained rocks where 39Ar from K-rich phases that generally release Ar at lower
temperatures (e.g., clays, intersertal glassy matrix) transfers to K-poor phases that
generally release Ar at higher temperatures (e.g., pyroxene, olivine), and 37Ar transfers
1
Supplementary Data can be found in the online version of this article or in Appendix C of this thesis.
107
from relatively Ca-rich phases (e.g., feldspar, pyroxene) to Ca-poor phases (e.g., clays,
intersertal glassy matrix). These so-called recoil effects produce erroneously old ages at
low temperature steps and erroneously young ages at high temperature steps resulting in
descending step ages with gas release (“inverse staircase” age spectra). In such cases, and
where there is no evidence for 40Ar-loss (in low temperature steps), the total fusion ages
are equivalent to K-Ar ages. Isochron ages are calculated from the slopes of linear
regressions through the step isotopic compositions (40Ar/36Ar vs 39Ar/36Ar) and make no
assumption about the initial Ar composition (40Ar/36Ar). Because the step compositions
do not typically show large dispersion, the analytical uncertainties for isochron ages are
larger than for corresponding plateau ages.
All age spectra were examined for evidence of disturbance, namely, 40Ar-loss (at
lower temperature heating steps), and recoil. Conventionally, plateau ages are considered
reliable if they include 3 or more contiguous step ages constituting >50% of the total gas
released. A statistical parameter, mean square of weighted deviations (MSWD),
compares error within step ages with scatter about the mean step age, and has a 2σ (95%)
confidence limit below about 2.5 (depending on the number of heating steps). The
probability, p, combines MSWD and number of heating steps in a chi-square statistic that
expresses the level of confidence that the plateau-forming step ages define a meaningful
age. Values equal to or greater than 5% (95% confidence) indicate statically meaningful
ages.
Our analyzed samples show evidence for low temperature alteration, exposure to
seawater, and subaerial weathering. In such cases the possibility for 40Ar-loss and Kaddition during fluid-rock chemical exchange is significant. Baksi (2007) compared fresh
and altered basalts dated by 40Ar-39Ar incremental heating experiments and developed
several quantitative measures of levels of alteration at which age data may be
compromised. The first is the concentration of 36Ar (atmospheric, corrected for reactor
produced 36Ar from Ca), which lies below about 3x10-14 mol/g for whole rock basalts and
10x10-14 mol/g for plagioclase in samples that produced acceptable (crystallization)
plateau ages. Another parameter, the “alteration index,” calculated from 36Ar/39Ar, also
108
relates the amount of atmospheric-derived Ar to intrinsic K-content, has a threshold value
of <0.0006 for acceptable ages.
New major, minor, and trace element geochemical analyses were performed on
whole rocks. Major and minor elements were analyzed by X-Ray Fluorescence (XRF) for
the Curaçao samples at Pomona College and for the Dumisseau Formation at Washington
State University (WSU) Geoanalytical Lab. All whole rock trace element data were
obtained at WSU using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS).
Sample preparation involved selecting visually unaltered chips of rock and powdering the
samples in a W-Carbide shatterbox, mixing with Li-tetraborate flux, and fusing,
following the general procedure outlined in Johnson et al. (1999). ICP-MS samples were
also dissolved in acid prior to analysis following WSU’s standard procedure (Knaack et
al., 1994). In addition to whole rock analyses, hyaloclastite samples from Curaçao were
analyzed by Electron Microprobe Analysis (EMPA) at the University of Oklahoma and
laser ablation-ICP-MS (LA-ICP-MS) at Oregon State University, using the methodology
described in Loewen and Kent (2012).
Results
Curaçao Geochronology
Of the 22 dated samples from Curaçao, 16 provided reliable plateau ages ranging
from 92 to 63 Ma (Table 5.1). In all cases plateau ages are consistent with isochron ages
and show no evidence for significant recoil, or 40Ar-loss (Fig. 5.2). Within this age range,
there are samples with ages grouped at 92 Ma, 88-84 Ma, 80-75 Ma, and 70-63 Ma (Fig.
5.2). This broad age range does not fit with that expected from the volcanic stratigraphy
described by Klaver (1987; Fig. 5.1) and earlier age determinations of Sinton et al.
(1998). Below we discuss each of the age groupings. Isochron and plateau diagrams for
all analyzed samples are available in the Supplementary Data and Appendix C; full data
files used for age calculations, including tables and plots, can be accessed at the online
database http://earthref.org.
The oldest ages are 92.0 ± 1.0 Ma from a groundmass separate of basaltic lava
collected by Kerr et al. (1996) and 91.8 ± 2.1 Ma from a plagioclase separate from a
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plagioclase-clinopyroxene poikilitic sill. The groundmass sample exhibited a very slight
recoil age spectrum, with MSWD just outside the 95% confidence limit, but with six
heating steps that encompassed over 80% of the total 39Ar released used in the plateau
calculation (Fig. 5.2a). The plagioclase separate returned a plateau with no evidence of
recoil or 40Ar-loss, but low proportions of radiogenic 40Ar resulted in higher uncertainty
on individual steps and the plateau age. Both samples are located on the southeast end of
the island and very near a sample with previously reported plateau ages of 89.5 ± 1.0 Ma
and 92.8 ± 0.5 Ma (Sinton et al., 1998; Snow et al., 2005; Fig. 5.1).
Glass separates from hyaloclastite units (Cao-07 and Cao-35d) returned ages
between 88 and 86 Ma (Fig. 5.2b). Both of these deposits are on the northwest end of the
island adjacent to significantly younger lavas. Hyaloclastites from the southeast end of
the island are generally more altered, and the one attempted age on a glass separate from
this region (BK-79-263) exhibited an 40Ar-loss profile from which no reliable age could
be determined (Table 5.1, Supplementary Data, Appendix C).
Plagioclase separates from two poikilitic sills (Cao-13 and Cao-18) in the
southeast returned good plateaus between 86 and 83 Ma (Fig. 5.2c). While
petrographically and geochemically similar to the 92 Ma plagioclase separate, these two
samples were near the northern extent of CLF outcrops and could represent a
stratigraphically younger position according to Klaver (1987). Sill rock Cao-14
(plagioclase separate) produced a reasonable 79.4 ± 1.9 Ma plateau profile comprising
about 70% of the gas released and passes all criteria for age reliability. However, it is
petrographically similar to and less than 2 km away from the 86 Ma sill sample (Fig. 5.1).
A number of groundmass separates from plagioclase-clinopyroxene-bearing lavas
display a range of plateau ages from 80 to 63 Ma (Fig. 5.2d-f). Several of these samples
with excellent plateau profiles are found near sill and hyaloclastite samples with
significantly older ages. One 74.9 ± 2.1 Ma sample (BK-79-262) is a reanalyzed
groundmass portion of an 88.0 ± 1.2 Ma whole rock analysis (Sinton et al., 1998),
suggesting the possibility that phenocryst phases (olivine ± clinopyroxene) may retain
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mantle-derived Ar (Fig. 5.2d). The youngest of these samples are directly adjacent to
40
the Mid-Albian ammonite fossil locality described by Wiedmann (1978; Fig. 5.2f).
Quantitative measures of alteration proposed by Baksi (2007) have been
calculated from the isotopic data. In general, 36Ar concentrations are below the suggested
cutoff values for whole rocks and plagioclase separates (Table 5.1). Sample BK-79-163
has a much higher 36Ar concentration (28.3 x 10-14 mol/g), consistent with the observed
significant 40Ar-loss. Samples BK-79-118 and Cao-03 have slightly high 36Ar
concentrations, but statistically acceptable plateaus and isochrons, and ages that are not
dissimilar to those of other less altered rocks. The alteration index values for Curaçao
samples are high, 0.02-0.5, and we believe this reflects the very low K-contents of these
rocks, rather than high concentrations of 36Ar. We feel that this parameter is not
appropriate for evaluating age quality in such compositions.
Dumisseau Formation Geochronology
Samples from the Dumisseau Formation, Haiti, exhibit a smaller age range, and
overlap the older ages from Curaçao. We consider eight of the fourteen analyzed samples
to have reliable plateau ages, while the others are compromised by recoil or 40Ar-loss
patterns (Table 5.2). The oldest plateau ages are 94-90 Ma (Fig. 5.3a) while the youngest
is 83 Ma (Fig. 5.3b). With the exception of this youngest age, uncertainties on all of the
other plateau ages are overlapping and yield no conclusive evidence for a hiatus in
activity (Fig. 5.3b-c). In addition to the statistical criteria (MSWD, p > 5%) for
acceptable plateaus, these samples also exhibit low concentrations of 36Ar, consistent
with their petrographically fresh appearance. The one exception is HA-77-245, which has
a very high 36Ar content and displays an 40Ar-loss age spectrum.
Geochemistry
We use trace element analyses of all dated samples to compare the geochemical
character across the broad age range, and with that of the entire CLIP. Major elements
were also analyzed, and are consistent with previous work, demonstrating that the
chemistry of most samples can be modeled as olivine ± clinopyroxene and plagioclase
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cumulates or fractionates from parental melts of similar composition (Klaver, 1987; Kerr
et al., 1996).
Trace element signatures of the CLF are broadly consistent with other CLIP
localities. Rare earth element profiles are generally flat (normalized to chondritic values;
McDonough and Sun, 1995; Fig. 5.4). Elemental ratios associated with plume sources,
such as Zr/Nb, are lower (10-20) than typical mid-ocean ridge basalt (MORB, Zr/Nb
>30) and on the plot of Nb/Y vs. Zr/Y shown in Figure 5.5 almost all CLF samples plot
well within the plume-associated Icelandic Array of Fitton et al. (1997). Mafic samples
have Ba/Nb <10, although more felsic intrusions in the NW corner of the island as well
as nearby basalts (Cao-22) are more arc-like with Ba/Nb > 50, similar to analyses of the
coeval Aruba Batholith (White et al., 1999; Fig. 5.6). While Ba may be sensitive to
hydrothermal alteration, La/Nb, which is less susceptible to low temperature chemical
exchange, shows the same trend. All anomalously high Ba/Nb also having high La/Nb
but most CLF samples having La/Nb < 1 (Fig. 5.6).
The Dumisseau Formation samples have similar major element chemistry to the
other lavas described above, but contrast with CLF lavas in that they exhibit LREE
enriched patterns (Fig. 5.4). Other trace element concentrations are also higher, such as
Ti, Zr, Nb, Sr, Hf, Ta, Th, and U. Overall, trace element contents of Dumisseau
Formation lavas are more similar to typical ocean island basalts (OIB).
Isotopes
Extensive whole rock isotopic work has been conducted on Curaçao by Kerr et al.
(1996), Walker et al. (1999), Hauff et al. (2000), Geldmacher et al. (2003), and White et
al. (1999), while Sr-Nd isotopic analyses have been reported for the Dumisseau
Formation by Sen et al. (1988). Although these compositions were not on the same
samples for which we have age determinations, they likely sample similar units. These
studies all concluded that isotopic values are consistent with melting from plume
influenced mantle sources with similar endmembers as those contributing to the current
Galapagos hot spot. We report one new He isotopic analysis of an olivine separate from a
Dumisseau Formation picrite (HA-77-34), which produced an Ra/R = 12.4 ± 0.21 (2σ)
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within the range of high values obtained from Gorgona and Galapagos (Révillon et al.,
2002; Kurz et al., 2009). These values are all higher than expected for MORB mantle
(Ra/R = 8-10) and at the low range expected for a plume source (Graham, 2002).
Discussion
Geologic History of Curaçao
Our new 40Ar-39Ar age determinations require a revision of models for the
formation of the CLF. In contrast to earlier studies, which argued for rapid formation
(Klaver, 1987; Sinton et al., 1998), our data show a more extended geologic history for
the sequence. Magmatism occurred from 92 to 63 Ma with no clear evidence for breaks
in volcanic activity during this period (Fig. 5.2). These results have several important
implications: (1) The volcanic stratigraphy of Curaçao consists of multiple volcanic
pulses despite a lack of observed erosional horizons or sedimentary interbeds; (2) the
CLF did not form prior to 95 Ma as other workers have proposed (Wiedmann, 1978;
Wright and Wyld, 2011); and (3) the lavas of the CLF were not emplaced in a short 1-5
million year duration typical of LIPs worldwide (Coffin and Eldholm, 1994; Sinton et al.,
1998). Consequently, despite virtually uniform major, minor and trace element patterns
(Klaver, 1987; Kerr et al., 1996), the Curaçao lavas appear to represent continuous or
intermittent magma generation from a broadly similar mantle source over a period of ~30
million years.
Our new data and observations argue that the stratigraphy of the island is more
complex than the relatively simple sequences presented by Klaver (1987) and Beets
(1972). As shown in Figure 5.1, there is no systematic change in age across the island. In
addition, intrusive rocks (sills and plugs) yield ages that span the first half of the volcanic
history (Table 5.1). This includes ages from plagioclase separated from poikilitic sills in
the southeast end of Curaçao and zircon separated from intrusive plugs in the northwest
end of the island (Wright and Wyld, 2011). Field exposures are insufficient to determine
the relationships between outcrops separated by flat areas covered by soil and vegetation
We suggest that the internal structure of the CLF is a sequence of hyaloclastites, pillow
and massive lava flows, and sills, which have been gently folded and offset by WNW-
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ESE faulting. In our field sampling, we did not observe evidence for the simple
stratigraphic sections proposed by Beets (1972) or Klaver (1987). The second of these
studies determined some of the structural orientations on Curaçao by measuring the
bedding of pillow lavas. This method, however, can be problematic since observations of
recent pillow lava flows often show chaotic and steep-sided flow fronts (Jones, 1968;
Moore, 1975). The complex nature of submarine lava flows coupled with the extensively
weathered and discontinuous outcrops within the CLF, low relief, and similarity of rock
types, leads us to conclude that previous stratigraphic reconstructions did not observe the
unconformities between volcanic sequences or faulted sections implied by the age range
of our data.
Similarly, some reconciliation is required between the younger ages identified in
the CLF and previous estimates of the age of overlying sedimentary units. The Knip
Group is unconformably separated from the CLF by a distinct brecciated soil horizon and
is estimated to be Campanian to Maastrichtian in age (~84-66 Ma; Beets, 1972; 1977).
Recent U-Pb dating of detrital zircon grains and 40Ar-39Ar detrital hornblende of both
continental and island arc origin return a maximum age of ~74 Ma for these sediments
(Wright and Wyld, 2011). Our new ages suggest that four lava flows of the CLF are
broadly coeval (66-63 Ma) with the Knip Group sediments. We note, however, that the
sediments accumulated rapidly (>1 km thickness suggested for the Knip Group in NW
Curaçao, in ~8 m.y.) while there is minimal evidence for sediments within the CLF over
30 m.y. of intermittent volcanic activity.
Several key field relationships could help explain the occurrence of young lava
flows (without intercalated sediments) erupted within the time frame of Knip Group
sedimentation. (1) Unrecognized faulting may form some contacts of the CLF. The
collision of the Caribbean Plate and South America has resulted in regional right-lateral
transform motion. The extreme NW outcrops of the CLF are geochemically distinct from
lavas found elsewhere on Curaçao and are similar to samples from the island of Aruba
located nearby to the NW. Deconstruction of right-lateral motion could move this portion
of the CLF closer to Aruba. (2) Erosional unconformities occur between the CLF and
Knip Group and between the Knip Group and younger sedimentary units (Beets, 1972).
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The thickness of the Knip Group is also variable, with thick sequences in the NW
pinching out to the SE. (3) The CLF is exposed in two NW-trending anticlinoria
occupying the elliptical NW and SE highlands of the island, separated by a syncline in
the center of Curaçao. Although previous work suggests these structures developed in the
early Tertiary (Beets, 1972), considerable deformation occurred on Aruba at the same
time as younger CLF lavas erupted (Wright and Wyld, 2011). If some of the folding
began to occur during the late Cretaceous, the young CLF lavas would have erupted on
uplifting regions while CLF lavas with intercalated sediments are hidden below the
surface in the syncline. Hence, the anticlinal crests may have been at or above sea level at
the time of Knip Group sedimentation. Given the poor exposure of outcrops on Curaçao,
these new age determinations should provide motivation to consider alternate
interpretations of the geologic structure of the island.
Our results contradict the recent interpretation by Wright and Wyld (2011) that the
CLF formed earlier than 95 Ma. Their work rejected previous 40Ar-39Ar geochronology
(Sinton et al., 1998) in favor of an imprecise U-Pb microbadellyite age (Humphrey, 2010)
and an early identification of broken and highly deformed Mid-Albian ammonites in
intercalated sediments (Wiedmann, 1978). The large number of new 40Ar-39Ar ages
presented here provides compelling evidence that the CLF formed after 95 Ma, with lavas
adjacent to the ammonite locality returning the youngest ages (Fig. 5.1). These results
also show that instead of two distinct magmatic events proposed by Sinton et al. (1998),
volcanism was intermittent throughout the 30 Ma development of the CLF.
We also observe similar major, minor, and trace element compositions in our CLF
samples through time. These systematic geochemical patterns cannot be the result of the
evolution of a single magma batch over a 30 million year time span. Instead, the
compositional similarities between samples of different ages require a similar mantle
source for melting and common petrogenic processes acting over the time interval from
~92-63 Ma. Trace element ratios such as Zr/Nb or La/Nb (Fig. 5.6) require that the melt
source region is similar in composition through time, and relatively tight major element
trends (Kerr et al., 1996) suggest magma batches follow comparable paths of
compositional modification (olivine fractionation or accumulation followed by
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clinopyroxene and plagioclase fractionation). A notable exception may be the
geochemistry of the picrites, which have notably lower εNd (Kerr et al., 1996). These
samples could not be directly dated due to low potassium contents and heavy alteration.
Their occurrence on the SE end of Curaçao (Klaver, 1987) associates them with the
oldest samples we have dated, and is consistent with high temperature magmatism
expected with the initial impingement of a mantle plume (Hastie and Kerr, 2010).
Geologic History of the Dumisseau Formation
Our new ages fall largely within the expected range of previous radiometric dating
on the Dumisseau Formation (Sinton et al., 1998; Snow et al., 2005) and fossil
assemblages identified in interbedded sediments (Maurrasse et al., 1979). Only 10 million
years of volcanism is evident here compared with 30 million years on Curaçao, although
the earliest lavas of both formations are 93-92 Ma. This initial age is consistent with the
earliest samples from most other CLIP localities (Fig. 5.6) and Turonian to early
Coniacian fossil age estimates of interbedded sediments in the lowest sections of the
Dumisseau Formation. Late Santonian to early Campanian fossils in the basalts from near
the top of the Dumisseau Formation match our youngest radiometric ages (82.8 ± 0.7
Ma).
Geochemically the Dumisseau Formation is distinct from the Curaçao lavas with
LaN/YbN > 3 (Fig. 5.6), and these differences can most easily be related to lower degrees
melting of a plume-influenced mantle source. Trace element ratios that change by smaller
amounts with degree of melting but largely reflect source character (e.g., Zr/Nb) are
similar to the CLF.
Timing and Geochemistry of Volcanism Across the CLIP
The age range and geochemical character of samples from the CLF and the
Dumisseau Formation exemplify the broader character and timing of the CLIP. We
compare our new age and trace element geochemistry with additional published plateau
ages from throughout the Caribbean in Figs. 5.5 and 5.6 (Alvarado et al., 1997; Kerr et
al., 1997; Sinton and Duncan, 1997; Sinton et al., 1998; Lapierre et al., 1999; White et
116
al., 1999; Révillon et al., 2000; Sinton et al., 2000; Hoernle et al., 2002; 2004; EscuderViruete et al., 2011; Serrano et al., 2011). We have restricted our consideration to
samples with well-constrained plateau ages. Figure 5.6 shows that CLIP volcanism on
Haiti and Curaçao, bracketing the eastern CLIP, commenced between 95 and 90 Ma.
Volcanism waned in the northern CLIP localities after ~10 million years but continued in
the southern Caribbean and Central American CLIP localities until approximately 60 Ma.
After this time, geochemically related volcanic activity is found in accreted seamounts on
the Pacific coast of Central America associated with the trail of the Galapagos hot spot
(Hoernle et al., 2002).
In addition to covering the span of CLIP volcanism, CLF and Dumisseau
Formation lavas include some of the earliest examples of CLIP volcanism. Our oldest
dated samples (93.6 ± 1.8 Ma for the Dumisseau Formation and 92.0 ± 1.0 Ma for the
CLF) are also among the earliest ages reported for the entire CLIP (Fig. 5.6). The only
older ages are 94.3 ± 2.8 Ma from DSDP Leg 15 located in the middle of the Caribbean
plate (Sinton et al., 1998) and 98.4 ± 2.4 Ma from Gorgona Island (Serrano et al., 2011).
Two considerably older ages reported from Hoernle et al. (2004; 137 ± 2 and 118.2 ± 1.8
Ma) are limited in occurrence to the Nicoya Peninsula, Costa Rica, which may represent
preexisting oceanic crust of the Farallon plate. The abundance of basalt crystallization
ages from throughout the CLIP starting after 95 Ma and the relative absence of ages
before this time strongly support this time as the initiation of plume volcanism which
continues today in the Galapagos hot spot.
The trace element signature of the vast majority of CLIP samples is that of a plume
source. Ba/Nb is generally < 10 and La/Nb < 1, suggesting no substantial subduction
influence, and Zr/Nb = 10-20, excluding a typical MORB depleted mantle source (Fig.
5.6). Samples also plot clearly within the plume-sourced “Iceland Array” as opposed to
the MORB field of Fitton et al. (1997; Fig. 5.5). The CLF samples as well as most CLIP
lavas have relatively flat REE patterns with LaN/YbN ~ 1 (Fig 5.4). REE patterns such as
these can be formed from either high degrees of melting of an enriched or primitive
mantle source or much lower degrees of melting from a depleted source. Low Zr/Nb (1020), however, cannot be achieved through different degrees of partial melting, but instead
117
requires that melts were generated from at least a partially enriched to primitive source.
There are two noteworthy exceptions to the geochemical trends described above:
(1) high Ba/Nb and La/Nb signatures are found in the Aruba batholith (White et al.,
1999) and samples from NW Curaçao that could suggest a subduction influence on the
magmas or magma differentiation processes; and (2) high LaN/YbN are found in the
northern portions of the CLIP including the Dumisseau Formation and < 65 Ma samples
from Central America (Fig. 5.6) as well as locations in South America (Kerr et al., 2002).
These latter compositions are more typical of ocean island basalts derived from small
degrees of partial melting (Pilet et al., 2008).
The possible subduction influence in rocks of the Aruba batholith and other evolved
plutonic rocks coincides roughly with suggested collision of the CLIP with North and
South America between 90 and 80 Ma (Duncan and Hargraves, 1984; Pindell and
Kennan, 2009). While some subduction signature would be expected in rocks at this time,
it is perhaps most remarkable that none of the other CLIP lavas from this age and
younger exhibit any such influence. It could be that any arc-derived rocks within the
CLIP are underrepresented in existing studies, and/or that a newly initiated subduction
zone (discussed below) would generate very limited volcanism atypical of classic
subduction volcanism or adakitic signatures such as White et al. (1999) described in
Aruba.
Unlike the typical CLIP lavas found in many parts of the Caribbean region,
including Curaçao, the OIB-like signature is primarily restricted to two distinct periods,
95-83 Ma lavas in the Dumisseau Formation and the < 65 Ma lavas of volcanic centers in
Costa Rica and Panama. The Central American samples have been described as accreted
seamounts of the Galapagos hot spot trail formed in the Pacific as the Caribbean Plate
was isolated from the plume with the ~70 Ma initiation of the Central American
subduction zone. The Haitian samples can best be explained as the result of melting
beneath the northern edge of tapered plume head whose center was to the south, closer to
Curaçao.
118
Tectonic Model
Our new data show that the timing and geochemical character of the eastern CLIP
exposed in Curaçao requires melting of a mantle source with a plume component over a
~30 million year period. Lower degrees of melting and a shorter volcanic history is
evident in the northern extent of the CLIP. These observations do not fit a traditional
plume head model for LIP development, which typically calls for a short time span of
volcanism and a rapid transition to ocean island basalt (OIB-type) compositions along a
spatially restricted hot spot track produced by much lower eruption rates (Coffin and
Eldholm, 1994; Kerr et al., 2002). Instead, we propose that the plate tectonic setting of
the plateau and, specifically, the interaction of the residual plume head mantle material
with nearby subduction zones, can explain the prolonged period of plume-influenced
volcanism. Underlying this model is the understanding that mantle plumes can be
strongly advected by ambient asthenospheric flow, particularly coupled flow at the base
of the lithosphere (Richards and Griffiths, 1988).
In our model, volcanism of the CLIP began around 94 Ma in the eastern Pacific
basin during the initial impingement and decompression melting of a plume head at the
base of Farallon plate oceanic lithosphere, just to the west of an east-dipping subduction
zone (Duncan and Hargraves, 1984; Fig. 5.7a). At this time, we see volcanism in almost
all CLIP localities (Fig. 5.6), suggesting mantle melting was widespread and similar to
other LIPs formed from plume heads (Coffin and Eldholm, 1994). However, the chemical
character of volcanism appears to vary with location, probably reflecting distance from
the plume head center with apparently lower degrees of melting in the north of the
province.
Models of mantle flow beneath subduction zones show that an upwelling plume
will be deflected by shear flow in the asthenosphere coupled to the base of a subducting
slab (Druken et al., 2012). Applying this model to initial CLIP volcanism, the
northeastward trajectory of the Farallon plate and underlying asthenosphere dragged the
residual Galapagos plume head with it, thus distributing and mixing plume head material
with ambient asthenosphere in a flow regime dictated by slab subduction. In this
scenario, the OIB-like volcanism observed in the Dumisseau Formation was derived from
119
the cooler, lower melt-fraction edge of the initial plume head, while the classic larger
melt-fraction LIP patterns seen throughout the southern extent of the CLIP are the result
of melting near the hotter main plume axis.
By 85 Ma, reconstructions suggest the Caribbean Plateau collided with the
Greater Antilles Arc between North and South America, blocking the existing subduction
zone and causing a subduction polarity reversal (Duncan and Hargraves, 1984; Fig. 5.7b).
The high La/Nb volcanism we see in Aruba and the NW edge of Curaçao, some of which
has adakitic characteristics, could be the expression of the newly forming west-dipping
subduction zone. After this time the subduction zone rolled back to the east (Fig. 5.7c).
Mantle dynamic models suggest that asthenospheric counterflow will be very strong
behind a rapidly rolling back slab, and eastward flow of the Caribbean region could
capture the residual mantle plume and help drive continued mantle upwelling and
magmatism (Druken et al., 2012; Long et al., 2012). We suggest that this process
entrained the residual head of the Galapagos plume, allowing for plume-like mantle to
continue producing LIP volcanism for another 30 million years.
Around 70 Ma east-dipping subduction began at the western margin of the CLIP,
along what is now the Central American Arc (Fig. 5.7d). This event cut off the plume tail
from the Caribbean region, restricting expression of plume tail OIB volcanism to the
Pacific. Evidence for this activity is found in accreted seamounts along the Central
American west coast (Hoernle et al., 2002; Buchs et al., 2011). This plume tail material is
the result of lower degree melting resulting in observed high LaN/YbN seen in 66 Ma and
younger samples in Central America (Hoernle et al., 2002; Fig. 5.6). The Caribbean
Plateau, now isolated from the Galapagos plume tail, experienced continued CLIP
volcanism in an extensional regime between two subduction zones until ~60 Ma. During
this time melting could no longer be driven by upwelling and decompression of a mantle
plume, but by upwelling associated extension in a back-arc basin and the plume
geochemical signature of lavas resulted from the residual plume head.
The model we present here is able to explain the features observed in the CLIP
although the geodynamic consequences of plume-subduction zone interactions require
further study. However, the results and our interpretations from this study directly
120
contrast some other recent work from the CLIP. Serrano et al. (2011) reported a similar
duration of CLIP volcanism from Gorgona (98-64 Ma) as this study found for the CLF
(92-62 Ma). The Serrano et al. (2011) study, however, called on a magmatism associated
with a slab window for the Gorgona and other CLIP lavas following Pindell et al. (2006),
with “fortuitous” coincidence of a mantle plume to explain high 3He/4He and other
plume-like geochemistry in the region. As discussed in Hastie and Kerr (2011), the
geochemistry of CLIP lavas is not compatible with a slab window environment. Also, the
slab window model does not explain the focusing of volcanism in the southern Caribbean
plate after 80 Ma or the clear cessation of CLIP activity by 60 Ma. In fact, we would
expect a slab window initiated at 90 Ma to expand as it developed rather than contract as
observed in this study.
Conclusions
• We report new 40Ar-39Ar geochronological data and chemical data for the CLIP,
demonstrating plateau volcanism in the CLF from 92-63 Ma and in the
Dumisseau Formation from 94-83 Ma. This age range significantly expands the
period of formation of the CLF and reaffirms the proposed initiation of CLIP
volcanism around 94 Ma.
• Volcanism in the CLF lacks systematic geochemical changes over ~30 Ma,
contradictory to a classic plume-head model where initial large degrees of
voluminous melting transitions to small degree melting in only a few million
years. Spatial patterns in duration and geochemical character are present over the
entire CLIP with lower degrees of melting and only ~10 Ma of volcanism present
along the northern margin as shown in the Dumisseau Formation.
• All CLIP volcanism originates from a plume-like mantle source distinct from
typical MORB mantle (Zr/Nb = 10-20). Most volcanism is the result of a large
degree of partial melt resulting in flat REE patterns, however LREE enrichment
from lower degrees of partial melt occur in the northern portion of early CLIP
lavas (Dumisseau Formation, 94-83 Ma).
121
• We suggest that interaction of a plume with the Greater Antilles subduction zone
could explain the observed geochemistry and longevity of CLIP volcanism.
Acknowledgements
This research was funded by National Science Foundation grant OCE 1028707 to
R.A.D. and A.J.R.K. Kaj Hoernle, Peter Michael and Alan Hastie assisted with sample
collection in Curaçao. Florentin Maurasse provided samples from the Dumisseau
Formation. Chris Sinton and Jade Star Lackey along with students at the Pomona College
provided XRF analyses for Curaçao samples and Peter Michael provided electron
microprobe values for Curaçao glasses. John Huard assisted with 40Ar-39Ar sample
preparation and analysis. David Graham provided the He-isotopic analysis. Valuable
conversations with many members of the VIPER (Volcanology, Igneous Petrology, and
Economic Resources) research group at OSU contributed to the development of this
project. We appreciate detailed and constructive reviews by Andrew Kerr and Folkmar
Hauff that greatly improved the quality of the final manuscript.
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128
Figure 5.1. Overview map of prominent Caribbean Large Igneous Province exposures
(insert) and simplified geologic map of Curaçao (modified after Beets, 1972). Sample
locations along with age determinations (in Ma) are shown. The locations of 89.5 and
88.0 Ma 40Ar-39Ar ages reported by Sinton et al. (1998) are shown with asterisks as
reanalyzed 92.8 Ma (Snow et al., 2005) and 74.9 Ma (this study) ages. The location of a
75.8 Ma age reported by Sinton et al. (1998) for a diabase sill is not known. Also shown
are the locations of U-Pb ages reported in Wright and Wyld (2011; stars) and the location
of a Mid-Albian ammonite (Wiedmann, 1978). NP denotes locations of analyzed samples
with no plateau age. No clear age pattern is discernable in surface exposures as would be
expected if previously proposed stratigraphic relationships were correct (see Klaver,
1987).
pl
gl
gl
pl
pl
pl
gm
gm
gm
gm
gm
gm
gm
gm
gm
gm
gm
gl
gm
gm
gm
Cao-40b
Cao-07
Cao-35d
Cao-13
Cao-18
Cao-14
79-Be-069
BK-79-262
Cao-20
Cao-04a
Cao-03
BK-79-118
Cur-10-02
Cao-30
Cao-10
BK-79-183
BK-79-163
BK-79-263
Cao-32
Cao-22
Cao-21
lava flow
lava flow
lava flow
hyaloclastite
pillow lava
pillow lava
pillow lava
pillow lava
pillow lava
pillow lava
lava flow
pillow lava
pillow lava
sill
pillow lava
sill
sill
sill
hyaloclastite
hyaloclastite
sill
lava flow
Lithology
61.2 ± 0.7
72.4 ± 0.5
118.0 ± 3.5
53.1 ± 1.5
41.2 ± 2.9
53.4 ± 10.8
60.1 ± 0.8
63.2 ± 1.0
62.6 ± 0.8
65.5 ± 2.9
66.3 ± 0.9
69.1 ± 1.2
74.1 ± 2.3
73.7 ± 2.6
74.4 ± 4.6
97.5 ± 3.0
83.9 ± 1.7
85.7 ± 3.0
86.0 ± 2.8
87.4 ± 2.3
91.5 ± 1.7
92.0 ± 1.5
(Ma ± 2s)
Total Fusion
Age
n/a
n/a
n/a
n/a
n/a
66.4 ± 10.7
62.3 ± 0.8
62.8 ± 1.0
63.0 ± 1.0
65.7 ± 2.4
66.7 ± 0.8
70.2 ± 1.1
74.2 ± 2.4
74.9 ± 2.1
79.6 ± 3.6
79.4 ± 1.9
83.9 ± 1.6
86.0 ± 1.9
86.3 ± 2.4
88.4 ± 2.1
91.8 ± 2.1
92.0 ± 1.0
(Ma ± 2s)
Plateau Age
5/9
8/12
9/12
10/12
10/10
12/12
10/11
9/10
10/10
8/10
6/7
7/7
7/7
10/10
9/10
7/7
6/10
steps
N
0.38
1.74
1.42
1.91
0.85
1.20
0.82
1.56
0.78
0.35
1.62
0.40
0.44
0.54
0.61
1.72
2.32
MSWD
83
9
18
5
57
28
60
13
63
93
15
88
85
84
77
11
4
(%)
Probability
n/a
n/a
n/a
n/a
n/a
71.0 ± 22.5
64.6 ± 1.7
62.5 ± 2.1
63.8 ± 2.4
68.0 ± 3.8
67.2 ± 1.2
70.7 ± 2.5
72.9 ± 2.5
77.8 ± 4.1
77.6 ± 6.1
81.0 ± 8.6
83.4 ± 2.1
86.0 ± 1.9
89.0 ± 6.1
83.2 ± 22.9
90.5 ± 3.2
91.9 ± 1.0
(Ma ± 2s)
Isochron Age
0.42
0.45
1.61
2.02
0.64
1.18
0.89
1.19
0.54
0.33
1.83
0.41
0.47
0.47
0.72
1.92
2.42
MSWD
Ar/36Ar
292.3 ± 13.0
281.5 ± 9.0
296.2 ± 7.0
291.1 ± 10.7
293.8 ± 2.2
294.3 ± 2.2
294.0 ± 5.7
298.8 ± 3.8
288.6 ± 8.1
296.5 ± 2.7
291.7 ± 19.7
296.5 ± 3.6
295.1 ± 1.6
278.6 ± 32.5
319 ± 106
299.2 ± 8.7
295.9 ± 2.4
(initial ± 2s)
40
4.8
2.0
0.4
1.5
23.3
1.6
2.6
3.9
3.1
12.2
9.8
4.7
2.6
4.9
5.0
2.8
2.6
7.1
1.0
1.5
2.3
0.8
Ar
(10-14
mol/g)
36
recoil
recoil
recoil
Ar-loss
Ar-loss
low 39Ar
plateau
plateau
plateau
plateau
plateau
plateau
plateau
plateau
plateau
plateau
plateau
plateau
plateau
plateau
plateau
plateau
type
Age
spectrum
Ages calculated using biotite monitor FCT-3 (28.02 Ma; Renne et al., 1998) and the total decay constant λ = 5.530*10-10/yr (Steiger and Jäger, 1977). N is the number of heating steps (defining
plateau/total); MSWD is an F-statistic that compares the variance within step ages with the variance about the plateau age. Material abbreviations are gl = glass, gm = groundmass, pl =
plagioclase, and wr = whole rock. Sample BK-79-183 and below are not considered reliable plateau ages due to low proportions of total 39Ar (< 70%) in the plateau, unusually high uncertainty
on individual heating steps, or an MSWD > 3, although some useful age information may be found in the total fusion or isochron ages.
gm
Material
Cur-21i
Sample
Table 5.1. 40Ar-39Ar age determinations for the Curaçao Lava Formation lavas, dikes and hyaloclastites.
129
130
Figure 5.2. Selected age spectra from the Curaçao Lava Formation. All samples shown
have well-defined age plateaus and are considered reliable estimates of the crystallization
age. Samples shown range from 92 to 63 Ma with no clear evidence of a hiatus in
volcanic activity.
pl
HA-77-178
wr
gm
wr
HA-77-237
HA-77-245
HA-77-110
HA-77-164
91.0 ± 0.6
90.5 ± 1.8
77.7 ± 1.1
89.8 ± 1.1
91.1 ± 0.7
105.2 ± 6.0
75.8 ± 0.8
86.0 ± 1.4
86.4 ± 1.2
86.8 ± 0.8
87.7 ± 1.2
88.7 ± 1.2
92.7 ± 2.1
n/a
n/a
n/a
86.1 ± 0.8
85.5 ± 0.7
105.0 ± 5.3
82.8 ± 0.7
85.2 ± 1.1
86.0 ± 1.1
86.8 ± 0.7
87.1 ± 1.1
88.0 ± 1.2
90.8 ± 1.8
93.6 ± 1.8
(Ma ± 2s)
(Ma ± 2s)
95.4 ± 2.1
Plateau Age
Total
Fusion Age
4/9
6/10
13/13
7/10
9/9
8/8
10/10
7/8
13/13
7/8
9/9
steps
N
1.24
1.02
1.09
1.52
0.54
0.45
0.14
0.45
1.58
0.24
1.90
MSWD
29
40
36
17
83
87
100
84
9
96
6
(%)
Probability
n/a
n/a
n/a
86.4 ± 3.9
85.2 ± 0.9
100.8 ± 7.2
83.4 ± 0.9
84.9 ± 1.2
85.5 ± 1.2
86.9 ± 0.8
86.9 ± 1.2
87.1 ± 1.1
90.2 ± 2.1
92.5 ± 1.8
(Ma ± 2s)
Isochron Age
See Table 5.1 for full explanation. Sample HA-77-62 and below are not considered reliable plateau ages.
wr
gm
HA-76-117
pl
pl
HA-77-144
HA-77-62
pl
HA-76-28
pl
pl
HA-77-29
wr
pl
HA-77-170
HA-77-159
gm
HA-77-109
HA-77-244
Material
Sample
Table 5.2. 40Ar-39Ar age determinations for Dumisseau Formation lavas and sills.
1.24
0.89
1.06
1.03
0.2
0.22
0.15
0.54
0.80
0.08
1.20
MSWD
Ar/36Ar
292.0 ± 49.0
300.4 ± 8.7
298.4 ± 4.1
286.7 ± 9.7
299.4 ± 4.6
302.5 ± 10.7
293.1 ± 18.5
297.8 ± 10.5
310.1 ± 8.9
298.0 ± 4.7
300.6 ± 4.6
(initial ± 2s)
40
5.0
4.8
28.3
3.2
2.3
5.4
2.8
3.6
1.8
1.0
1.3
2.4
5.0
recoil
recoil
Ar-loss
recoil
recoil
low 39Ar
plateau
plateau
plateau
plateau
plateau
plateau
plateau
plateau
type
(10-14 mol/g)
4.0
Age
spectrum
Ar
36
131
132
Figure 5.3. Selected age spectra from Dumisseau Formation. Samples with well-defined
plateau profiles are shown for ages between 94 and 83 Ma, although the youngest of
these (b, HA-77-159) shows some evidence for 40Ar-loss from low temperature steps.
133
Figure 5.4. Multi-element diagrams for samples from the CLF and Dumisseau
Formation. Notable anomalies include low K and Pb in all Dumisseau Formation samples
and most Curaçao samples. Samples with minimal K anomaly also have high Sr possibly
due to greater alteration of these samples, although other fluid-mobile elements such as
Cs, Ba, and U are not enriched. Curaçao samples have mostly flat REE profiles while
Dumisseau Formation samples have notably higher LREE concentrations with the
exception of HA-77-62.
134
Figure 5.5. Plume and MOR derived basalts can be differentiated on a plot of Zr/Y and
Nb/Y as shown by Fitton et al. (1997) with samples from Iceland. Here, trace elements
for the CLF and the Dumisseau Formation are compared to regional samples from
throughout the Caribbean Large Igneous Province with reported 40Ar-39Ar age
determinations (Alvarado et al., 1997; Kerr et al., 1997; Sinton and Duncan, 1997; Sinton
et al., 1998; Lapierre et al., 1999; White et al., 1999; Révillon et al., 2000; Sinton et al.,
2000; Hoernle et al., 2002; 2004; Escuder-Viruete et al., 2011; Serrano et al., 2011).
Rocks from the CLIP consistently plot within the plume portion of this array, consistent
with previous isotopic studies and other trace element ratios (e.g., Zr/Nb, Fig. 5.6).
Figure 5.6 (following page). 40Ar-39Ar plateau ages determined in this study and
previous work (see Fig. 5.5 for references). A histogram fitted with a probability density
function shows clear evidence that CLIP volcanism began 90-95 Ma and largely ceased
by 60 Ma. Samples from the CLF (shown in blue) span this range and are representative
of Caribbean-wide activity while samples from the Dumisseau Formation (shown in red)
are present only during the first 10-15 million years of activity. A few samples <50 Ma
from the western margin of Central America are interpreted as accreted seamounts from
the Galapagos hot spot trail, and also display distinctive trace element signatures.
135
Figure 5.6.
136
Figure 5.7 (following page). Conceptual model illustrating prolonged CLIP volcanism
with mantle plume influence. Plume material is shown in red, oceanic lithosphere in light
blue, CLIP volcanism in dark blue, and arc volcanism in green. Blue arrows depict
movement of oceanic lithosphere and black arrows expected movement of asthenospheric
mantle. (a) Between 95 and 90 Ma and shortly before collision between the American
plates, the initial Galapagos plume head thickened the oceanic lithosphere of the Farallon
plate. Unlike plume head volcanism in a fully intraplate setting, entrainment of upwelling
mantle by the downgoing slab may have mixed residual plume head material diluted and
extended the influence of plume-like mantle. (b) This thickened lithosphere blocked eastdipping subduction, which initiated a subduction polarity reversal between 90-85 Ma.
During this time plateau volcanism continued and some arc activity began with initiation
of a west-dipping subduction zone that continues today at the Lesser Antilles arc. (c) Slab
rollback between 85-70 Ma dragged residual plume material to the east of the plume tail
within the mantle-reference frame, as well as induced upwelling and backarc extension
allowing thinning of the plateau and continued, although less extensive, volcanism. (d &
e) Initiation of east-dipping subduction after 70 Ma created the Central American
volcanic arc CLIP volcanism in waned in a back-arc extensional environment while the
Galapagos plume tail produced OIB seamount trails now observed in the Panama basin
and in accreted seamounts in Central America.
137
Figure 5.7.
CHAPTER SIX
138
CONCLUSIONS
Three chapters of this dissertation have examined trace metal behavior in a
laboratory environment (Chapter 2) and two different natural volcanic settings (ocean
island basalts in Chapter 3 and arc volcanoes in Chapter 4). Another chapter (Chapter 5)
has provided new age and geochemical constraints on one of the largest volcanic
provinces on the earth, the Caribbean Large Igneous Province.
In Chapter 2, a major source of analytical uncertainty in many laser ablation
systems was described for the first time. Variations in local He flow rate in single-volume
ablation chambers were shown to cause different signal intensities depending on the
volatility of an individual analyte. An updated two-volume ablation chamber, designed to
produce uniform He flow regimes during analysis throughout the ablation chamber,
showed little evidence of this style of elemental fractionation. Recognition of this effect
explained the source of large uncertainties for many more volatile or refractory elements
in single-volume ablation chambers. Through recognition of the source(s) of uncertainty
in laser ablation analysis specific to semi-volatile elements, this chapter set the base for
subsequent studies of trace metals in Chapters 3 and 4.
Chapter 3 presented the first comprehensive major and trace element
characterization of both olivine-hosted melt inclusions and matrix glass from the 1959
eruption of Kilauea Iki, Hawaii. Patterns of lithophile trace element concentrations
elucidated the details of crystal fractionation and magma mixing that produced the
chemical variations of lavas during this eruption. The variations of most potentially
volatile trace metals were inconsistent with their mobility in a magmatic volatile phase,
with the possible exception of B and Sn. This work has shown that the mobilization and
release of many trace elements in volcanic gasses associated with mafic eruptions cannot
be detected in geochemical compositions of glass using LA-ICP-MS. Trace metal release
associated with volcanic degassing may in mafic environments may still occur, and direct
139
measurements of volcanic gasses supports this process, however, for most elements the
partitioning of metals into a vapor is insignificant compared to the concentration of the
elements in the melt and/or the analytical uncertainty of LA-ICP-MS.
Chapter 4 presented over 400 new trace element analyses from Mt. Pinatubo, Mt.
Hood, Mt. St. Helens, and Shiveluch Volcano. Trace element compositions in these
amphiboles track magmatic conditions at these four volcanic centers. Both Cu and Li
vary independently of all other potentially volatile trace elements and positively correlate
with each other. Their behavior is consistent with partitioning into a magmatic volatile
phase and rapid diffusivity through amphibole phenocrysts and the melt. This work
highlights the potential for Cu and Li to track separation of a magmatic volatile phase
during eruptions. It does not define where the in a volcanic system the Cu and Li
variations originate from. Variations within and between samples suggest that Cu and Li
are recording relatively late processes occurring during the eruption in the magma
chamber or even after deposition. Future work examining the Cu and Li concentrations
from amphiboles at different locations within a single pyroclastic or lava flow could help
determine if depositional conditions are an important factor. Experimental work to
determine diffusion coefficients for Cu and Li and/or comparison to hydrogen isotope
behavior, which should be even more rapidly diffused in samples, also would help define
when time scales associated with the patterns observed here.
Chapter 5 presents new 40Ar-39Ar geochronological data that require a 94-63 Ma
history of volcanism to produce the Caribbean Large Igneous Province. This duration of
volcanism is inconsistent with classical models of large igneous provinces being initiated
by the impingement of a mantle plume, however the geochemistry of these samples
requires a consistent plume-like mantle source throughout the entire period of volcanism.
Interaction of a plume with the Greater Antilles subduction zone could explain the
observed geochemistry and longevity of CLIP volcanism. This model provides a new
framework to evaluate the geology of the Caribbean region. Even at a local scale, the
range of ages shown for the island of Curaçao will be useful in future evaluation of the
island’s geology. Unlike the previous chapters, this final chapter does not directly address
the behavior of trace metals in volcanic systems. The confirmation of initiation of the
large igneous province at 94 Ma, however, is consistent with this province’s temporal
140
connection to ocean anoxic events that could be related to trace metal release.
The projects presented in this dissertation highlight the utility of examining wellunderstood systems with creative techniques. All of the systems examined here including
laser ablation techniques, Kilauea Iki, Mt. St. Helens and Mt. Pinatubo, and the
Caribbean, have all been extensively studies by previous workers. Despite all that has
been shown previously in these systems, the results presented in this dissertation
contribute critical new observations that refine or challenge the established understanding
of each system.
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APPENDICES
APPENDIX A
SUPPLEMENTAL INFORMATION FOR CHAPTER THREE
Accuracy and precision for major and trace element analyses are shown with
repeat analyses of secondary standards. Table A1 provides an analysis of the EMPA
accuracy and precision with different secondary standards. Table A2 provides similar
data but for trace elements and LA-ICP-MS. Note that in Table A2, all concentrations are
in ppm which accuracy is a % calculated as measured/actual concentrations. Actual
concentrations are estimated with the GeoReM database. Stdev is standard deviation,
stderr is standard error, and n is the number of times each secondary standard was
analyzed for each element. Analyzed isotopes are identified on the left column and are
the same masses monitored during unknown analysis. Secondary glass standards were
also run during olivine and melt inclusions analyses, but followed a similar procedure and
uncertainties are similar to those shown in Table A2.
Major and trace element compositions of matrix glass along with sample
information are provided in Table A3. Table A4 displays major and trace element
compositions for melt inclusions analyzed from olivine separates from sample Iki-22.
Volatile concentrations determined by FTIR are also presented in Table A4. Table A5
displays host olivine compositions from Iki-22. Note that Electron Microprobe analyses
in Table A4 and A5 were performed at the University of Oregon and Table A1 may not
be representative of the uncertainty in these analyses.
159
105.8
2.79
0.02
2.85
0.02
102.1
1.04
0.07
0.97
0.01
93.7
100.4
49.30
0.10
50.54
0.16
102.5
47.50
0.30
48.00
0.15
101.1
101.5
99.9
2.27
0.04
2.40
0.03
4.12
0.10
50.90
0.65
54.40
0.40
54.64
0.04
4.06
TiO2
50.94
SiO2
All concentrations are in wt. %.
BCR-2G
Value
Uncertainty
Measured (n=3)
Std Dev
Accuracy %
(avg/accepted)
BHVO-2G
Value
Uncertainty
Measured (n=3)
Std Dev
Accuracy %
(avg/accepted)
BIR-1G
Value
Uncertainty
Measured (n=3)
Std Dev
Accuracy %
(avg/accepted)
BASL
Value
Uncertainty
Measured (n=15)
Std Dev
Accuracy %
(avg/accepted)
102.7
15.50
0.20
15.92
0.10
103.1
13.60
0.10
14.03
0.04
105.3
13.40
0.40
14.11
0.07
96.9
12.54
0.18
12.94
Al2O3
46.0
0.115
0.007
0.053
0.039
51.5
0.086
0.004
0.044
0.011
123.4
0.005
0.001
0.006
0.034
Cr2O3
98.1
10.40
0.10
10.20
0.09
97.3
11.30
0.10
10.99
0.08
100.2
12.40
0.30
12.43
0.08
97.6
13.16
0.15
13.49
FeO*
80.7
0.19
0.01
0.15
0.03
77.2
0.17
0.03
0.13
0.01
99.6
0.19
0.01
0.19
0.03
126.5
0.19
0.04
0.15
MnO
Table A1. Long-term accuracy of EMPA basaltic glass calibrations.
100.3
9.40
0.10
9.43
0.06
101.1
7.13
0.02
7.21
0.04
100.9
3.56
0.09
3.59
0.01
100.6
5.11
0.03
5.08
MgO
101.2
13.30
0.20
13.46
0.01
101.6
11.40
0.10
11.58
0.02
103.5
7.06
0.11
7.31
0.04
101.2
9.41
0.07
9.3
CaO
95.7
1.85
0.07
1.77
0.06
89.9
2.40
0.10
2.16
0.03
87.2
3.23
0.07
2.82
0.09
91.4
2.43
0.49
2.66
Na2O
150.4
0.03
0.01
0.05
0.01
101.8
0.51
0.02
0.52
0.02
98.1
1.74
0.04
1.71
0.04
96.8
0.81
0.04
0.84
K 2O
107.2
0.03
0.00
0.03
0.01
99.3
0.29
0.02
0.29
0.01
100.9
0.37
0.01
0.37
0.01
119.9
0.46
0.02
0.38
P 2O 5
100.04
99.35
100.33
98.98
99.57
98.62
99.27
99.84
Total
160
161
Table A2. Trace element accuracy in secondary standards by LA-ICP-MS*
7Li
11B
45Sc
47Ti
51V
52Cr
55Mn
59Co
60Ni
65Cu
66Zn
69Ga
85Rb
88Sr
89Y
90Zr
93Nb
98Mo
107Ag
111Cd
115In
120Sn
121Sb
133Cs
137Ba
139La
140Ce
141Pr
146Nd
147Sm
153Eu
157Gd
159Tb
163Dy
165Ho
166Er
169Tm
172Yb
175Lu
178Hf
181Ta
182W
208Pb
232Th
238U
Actual
9
6
33
14100
425
17
1550
38
13
21
125
23
47
342
35
184
12.5
270
0.5
0.2
0.11
2.6
0.35
1.16
683
24.7
53.3
6.7
28.9
6.59
1.97
6.71
1.02
6.44
1.27
3.7
0.51
3.39
0.503
4.84
0.78
0.5
11
5.9
1.69
+/1
1
2
1000
18
2
70
2
2
5
5
1
0.5
4
3
15
1
30
0.4
0.02
0.4
0.08
0.07
7
0.3
0.5
0.4
0.3
0.07
0.02
0.07
0.08
0.06
0.08
0.04
0.04
0.03
0.005
0.28
0.06
0.07
1
0.3
0.12
BCR-2G
Median
Accuracy
8.78
98
4.63
77
35.76
108
14058
100
415
98
16.93
100
1479
95
34.78
92
11.88
91
16.25
77
148
119
38.23
166
42.55
91
323
95
30.09
86
171
93
11.03
88
254
94
1.02
204
0.15
76
0.08
73
1.57
60
0.33
93
1.10
95
659
97
23.11
94
49.19
92
6.04
90
27.14
94
6.14
93
1.83
93
6.27
93
0.89
87
5.75
89
1.12
88
3.43
93
0.43
85
3.04
90
0.44
87
4.38
90
0.63
81
0.49
97
10.16
92
5.47
93
1.54
91
Stddev
0.77
4.87
1.50
312
36.97
2.73
65.95
2.88
1.01
1.24
11.53
5.49
3.65
4.69
0.94
5.41
0.48
20.06
0.32
0.04
0.01
0.13
0.04
0.09
8.90
0.66
1.38
0.18
0.70
0.28
0.05
0.26
0.05
0.25
0.04
0.20
0.03
0.10
0.02
0.16
0.03
0.05
0.97
0.15
0.17
n
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
stderr
0.20
1.30
0.40
83.37
9.88
0.73
17.63
0.77
0.27
0.33
3.08
1.47
0.98
1.25
0.25
1.45
0.13
5.36
0.09
0.01
0.00
0.04
0.01
0.02
2.38
0.18
0.37
0.05
0.19
0.08
0.01
0.07
0.01
0.07
0.01
0.05
0.01
0.03
0.01
0.04
0.01
0.01
0.26
0.04
0.05
162
Table A2. (Continued)
Actual
7Li
11B
45Sc
47Ti
51V
52Cr
55Mn
59Co
60Ni
65Cu
66Zn
69Ga
85Rb
88Sr
89Y
90Zr
93Nb
98Mo
107Ag
111Cd
115In
120Sn
121Sb
133Cs
137Ba
139La
140Ce
141Pr
146Nd
147Sm
153Eu
157Gd
159Tb
163Dy
165Ho
166Er
169Tm
172Yb
175Lu
178Hf
181Ta
182W
208Pb
232Th
238U
+/4.4
0.8
33
16300
308
293
1317
44
116
127
102
22
9.2
396
26
170
18.3
3.8
2
900
19
12
232
2
7
11
6
3
0.04
1
2
7
0.8
0.2
0.1
0.1
2.6
0.3
0.1
131
15.2
37.6
5.35
24.5
6.1
2.07
6.16
0.92
5.28
0.98
2.56
0.34
2.01
0.279
4.32
1.15
0.23
1.7
1.22
0.403
0.02
0.02
0.6
0.13
0.02
2
0.2
0.2
0.22
0.2
0.03
0.01
0.05
0.04
0.05
0.04
0.02
0.02
0.02
0.003
0.18
0.1
0.04
0.2
0.05
0.003
BHVO-2G
Median
Accuracy
4.27
97
3.50
32.60
99
16611
102
315.06
102
290
99
1320
100
42.31
96
119
102
119
93
113
110
22.62
103
8.37
91
385
97
21.38
82
152
90
15.89
87
3.98
105
0.36
0.07
68
0.09
86
1.33
51
0.13
43
0.10
98
129
98
14.32
94
35.79
95
4.88
91
23.18
95
5.72
94
1.97
95
5.61
91
0.76
82
4.66
88
0.83
85
2.30
90
0.28
81
1.75
87
0.23
84
3.87
90
0.92
80
0.23
100
1.70
100
1.09
89
0.40
100
Stddev
0.32
5.91
1.57
254
18.97
16.97
28.35
2.10
6.87
6.70
8.60
1.05
0.52
5.70
0.75
5.41
0.52
0.23
0.12
0.02
0.02
0.09
0.02
0.01
2.65
0.42
0.78
0.15
0.41
0.18
0.07
0.21
0.03
0.15
0.03
0.14
0.02
0.09
0.02
0.20
0.05
0.03
0.15
0.04
0.02
n
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
14
stderr
0.08
1.58
0.42
67.90
5.07
4.53
7.58
0.56
1.84
1.79
2.30
0.28
0.14
1.52
0.20
1.45
0.14
0.06
0.03
0.01
0.00
0.02
0.00
0.00
0.71
0.11
0.21
0.04
0.11
0.05
0.02
0.06
0.01
0.04
0.01
0.04
0.00
0.02
0.01
0.05
0.01
0.01
0.04
0.01
0.01
163
Table A2. (Continued)
Actual
7Li
11B
45Sc
47Ti
51V
52Cr
55Mn
59Co
60Ni
65Cu
66Zn
69Ga
85Rb
88Sr
89Y
90Zr
93Nb
98Mo
107Ag
111Cd
115In
120Sn
121Sb
133Cs
137Ba
139La
140Ce
141Pr
146Nd
147Sm
153Eu
157Gd
159Tb
163Dy
165Ho
166Er
169Tm
172Yb
175Lu
178Hf
181Ta
182W
208Pb
232Th
238U
43
50
52
7434
44
42
220
40
58
42
54
54
37.3
69.4
42
42
42
39
23
18
38
29
43
32
67
39.1
41.4
45
44.7
47.8
41
50.7
47
51.2
49
40.1
49
50.9
51.5
39
40
43
50
41
41
+/6
20
2
360
2
3
20
2
4
2
2
7
0.4
0.7
2
2
3
3
3
4
5
6
7
2
1
0.4
0.4
1
0.5
0.5
2
0.5
2
0.5
2
0.4
2
0.5
0.5
2
4
4
2
2
2
GSD-1G
Median Accuracy
45.37
106
53.76
108
53.46
103
8102
109
44.34
101
47.35
113
223
101
40.27
101
63.17
109
43.08
103
54.59
101
54.71
101
38.35
103
67.09
97
37.74
90
40.88
97
41.46
99
40.92
105
23.09
100
18.40
102
38.55
101
29.75
103
46.12
107
33.73
105
69.35
104
36.91
94
39.93
96
42.52
94
42.96
96
46.01
96
38.95
95
46.61
92
42.14
90
47.49
93
44.01
90
38.05
95
43.93
90
47.56
93
46.22
90
36.64
94
37.26
93
43.99
102
49.60
99
39.73
97
41.75
102
Stddev
3.00
4.26
2.09
167
3.18
2.87
10.60
2.56
4.49
2.91
4.63
3.67
2.36
1.16
1.76
1.89
0.90
2.30
1.33
1.44
2.81
1.93
3.21
2.53
1.01
1.25
1.23
1.49
1.01
1.44
0.65
2.11
1.44
1.69
1.77
2.19
1.94
1.83
1.97
1.41
1.10
2.74
3.45
12.53
3.38
n
25
25
25
25
24
25
25
25
25
25
25
25
25
25
24
24
24
25
25
25
25
25
25
25
25
24
25
24
24
24
24
24
24
24
24
24
24
24
24
24
24
25
25
24
24
stderr
0.60
0.85
0.42
33.35
0.65
0.57
2.12
0.51
0.90
0.58
0.93
0.73
0.47
0.23
0.36
0.39
0.18
0.46
0.27
0.29
0.56
0.39
0.64
0.51
0.20
0.25
0.25
0.30
0.21
0.29
0.13
0.43
0.29
0.35
0.36
0.45
0.40
0.37
0.40
0.29
0.22
0.55
0.69
2.56
0.69
164
Table A3. Major and trace element analyses of matrix glass from Kilauea Iki.
Sample Information
a
Sample a
1
Alias 1
Iki-01
Alias
2
s-2
Eruption
Date
14-Nov-59
Eruption
Time
2
3
5
7
8
9
11
12
13
15
17
18
19
21
24
25
26
27
29
30
31
32
33
34
35
36
38
42
Iki-02
Iki-03
Iki-05
Iki-07
Iki-08
Iki-09
Iki-11
Iki-12
Iki-13
Iki-15
Iki-17
Iki-18
Iki-19
Iki-21
Iki-24
Iki-25
Iki-26
Iki-27
Iki-29
Iki-30
Iki-31
Iki-32
Iki-33
Iki-34
Iki-35
Iki-36
Iki-38
Iki-42
s-4
s-8
s-9
s-10
s-12
s-11
s-14
s-15
s-17
s-18
s-19
s-21
s-22
s-24
s-20
s-25
s-3
17-Nov-59
19-Nov-59
21-Nov-59
21-Nov-59
26-Nov-59
28-Nov-59
26-Nov-59
4-Dec-59
5-Dec-59
7-Dec-59
7-Dec-59
8-Dec-59
8-Dec-59
11-Dec-59
13-Dec-59
14-Dec-59
14-Dec-59
15-Dec-59
16-Dec-59
16-Dec-59
8-Dec-59
17-Dec-59
19-Dec-59
19-Dec-59
17-Dec-59
13-Dec-59
19-Dec-59
16-Nov-59
15:00
8:00
7:10
20:00
4:50
18:15
44
51
53
55
Iki-44
Iki-51
Iki-54
Iki-56
s-7
-
20-Nov-59
21-Nov-59
26-Nov-59
18-Nov-59
7:00
9:30
12:00
12:30
Basalt
Basalt
Basalt
Basalt
56
58
60
61
62
63
64
65
70
72
73
74
76
Iki-57
Iki-59
Iki-61
Iki-65
Iki-66
Iki-71
Iki-73
Iki-74
Iki-75
Iki-77
-
20-Nov-59
7-Dec-59
5-Dec-59
9-Dec-59
15-Dec-59
17-Nov-59
18-Nov-59
26-Nov-59
19-Nov-59
9-Dec-59
20-Nov-59
23-Nov-59
15-Dec-59
13:30
16:20
12:00
11:00
20:30
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt, Olivine
Basalt
9:45
9:30
1:00
23:30
3:30
18:30
6:00
14:00
12:00
14:00
20:00
20:50
14:20
12:00
14:45
6:30
4:30
16:00
12:30
4:50
14:15
11:00
15:00
8:00
Specimen
Name
Basalt
Pumice
(basaltic)
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Basalt
Prefix for Smithsonian catalogue number is NMNM 116111-X.
Texture/Structure
Glassy, Pumiceous
Glassy, Pumiceous
Flow
Flow, Glassy Crust
Glassy
Glassy, Scoriaceous
Glassy, Pumiceous
Glassy, Pumiceous
Glassy, Scoriaceous
Glassy, Pumiceous
Glassy, Pumiceous
Glassy, Pumiceous
Glassy, Pumiceous
Glassy
Olivine, Glassy, Pumiceous
Flow
Glassy, Pumiceous
Glassy, Scoriaceous
Glassy, Pumiceous
Glassy, Pumiceous
Glassy, Scoriaceous
Glassy, Pumiceous
Glassy, Pumiceous
Glassy, Scoriaceous
Glassy, Pumiceous
Glassy, Scoriaceous
Glassy, Pumiceous
Olivine, Glassy,
Scoriaceous
Olivine, Glassy, Pumiceous
Glassy, Pumiceous
Glassy, Scoriaceous
Olivine, Glassy,
Scoriaceous
Glassy, Pumiceous
Olivine, Glassy
Olivine, Vesicular
Glassy, Pumiceous
Glassy, Pumiceous
Olivine
Glassy, Pumiceous
Olivine, Vesicular
Olivine, Vesicular
Olivine, Vesicular
Olivine, Vesicular
Olivine, Vesicular
Analytical
Total
99.00
99.28
99.48
99.58
99.34
99.71
99.36
99.66
98.57
99.24
99.35
98.99
98.94
99.30
99.40
98.97
99.36
99.22
99.90
99.35
99.11
99.30
99.41
99.48
98.99
99.81
99.36
99.61
98.65
99.47
99.00
100.06
99.12
97.99
98.66
98.53
99.59
98.15
98.92
99.05
98.79
99.27
99.13
98.99
98.85
99.11
165
Table A3. (Continued)
Electron Microprobe (wt. %)
Sample
1
2
3
5
7
8
9
11
12
13
15
17
18
19
21
24
25
26
27
29
30
31
32
33
34
35
36
38
42
44
51
53
55
56
58
60
61
62
63
64
65
70
72
73
74
76
SiO2
50.12
50.19
49.64
50.22
50.04
50.51
50.10
50.00
50.33
49.71
49.98
50.25
49.82
50.06
49.85
50.30
50.03
49.89
50.31
49.98
50.14
49.56
50.09
49.97
50.03
50.58
50.24
50.39
50.26
49.74
50.20
50.05
50.25
50.32
50.33
51.34
50.32
50.33
50.31
49.98
50.35
49.72
50.30
50.09
49.69
50.37
TiO2
Al2O3 Cr2O3 FeO*
MnO
MgO
3.14
14.81
0.04
11.51
0.14
5.74
2.73
13.10
0.07
10.91
0.16
8.28
2.59
12.55
0.08
11.09
0.18
9.78
2.87
13.53
0.04
10.97
0.18
7.61
2.75
13.30
0.07
11.08
0.13
8.39
2.91
14.02
0.03
10.83
0.21
6.66
2.96
13.93
0.04
11.12
0.16
6.76
2.79
13.23
0.06
10.99
0.16
8.40
3.10
13.97
0.00
11.19
0.18
6.53
2.75
13.01
0.08
10.99
0.17
8.93
2.82
13.32
0.04
11.00
0.17
8.10
2.94
13.46
0.04
11.14
0.16
7.57
2.72
13.16
0.08
11.00
0.14
8.65
2.79
13.36
0.06
10.79
0.15
8.25
2.73
13.05
0.07
10.95
0.18
8.79
2.72
13.03
0.09
10.65
0.18
8.66
2.76
13.30
0.07
10.82
0.15
8.34
2.75
13.15
0.06
10.92
0.15
8.60
2.73
13.14
0.08
10.77
0.16
8.46
2.78
13.32
0.07
10.80
0.16
8.31
2.80
13.37
0.07
10.63
0.17
8.28
2.75
13.14
0.07
11.06
0.17
8.85
2.78
13.33
0.05
10.76
0.17
8.21
2.75
13.15
0.09
10.77
0.17
8.69
2.82
13.23
0.04
10.74
0.17
8.48
2.89
13.99
0.03
10.46
0.16
6.82
2.89
14.09
0.06
10.77
0.13
6.84
2.93
14.07
0.03
10.90
0.17
6.61
2.95
14.19
0.01
11.39
0.21
6.29
2.77
13.32
0.07
11.10
0.16
8.46
3.15
13.90
0.02
11.48
0.18
6.32
2.79
13.29
0.08
10.92
0.19
8.02
3.08
13.97
0.01
11.69
0.21
6.17
3.15
13.92
0.01
11.33
0.19
6.32
2.87
14.01
0.05
10.79
0.17
6.78
3.21
14.25
0.04
10.49
0.17
6.31
2.91
13.87
0.05
10.69
0.15
6.95
2.92
13.94
0.03
10.65
0.19
6.96
2.93
13.85
0.05
10.72
0.18
6.96
2.65
12.96
0.06
11.01
0.15
8.64
2.90
14.09
0.03
10.85
0.18
6.67
2.58
12.54
0.08
11.02
0.17
9.72
3.00
14.28
0.05
10.89
0.19
6.43
2.80
13.32
0.05
11.04
0.17
8.20
2.66
12.81
0.09
10.90
0.15
9.05
2.92
14.07
0.05
10.71
0.16
6.76
CaO
Na2O
K2 O
10.97
2.53
0.65
11.65
2.13
0.50
11.33
2.02
0.48
11.41
2.32
0.56
11.25
2.19
0.50
11.66
2.34
0.52
11.65
2.38
0.59
11.30
2.20
0.57
11.36
2.41
0.61
11.40
2.16
0.52
11.54
2.23
0.51
11.30
2.22
0.62
11.42
2.21
0.53
11.52
2.18
0.54
11.35
2.21
0.54
11.38
2.18
0.53
11.50
2.23
0.51
11.45
2.19
0.54
11.37
2.18
0.52
11.54
2.21
0.55
11.53
2.22
0.53
11.41
2.17
0.51
11.60
2.19
0.55
11.44
2.17
0.50
11.45
2.20
0.56
11.84
2.34
0.57
11.76
2.37
0.56
11.67
2.33
0.58
11.30
2.45
0.63
11.35
2.21
0.54
11.33
2.48
0.62
11.57
2.25
0.55
11.25
2.45
0.59
11.43
2.41
0.61
11.86
2.27
0.58
10.88
2.33
0.62
11.85
2.37
0.57
11.82
2.31
0.56
11.84
2.31
0.56
11.61
2.14
0.52
11.72
2.33
0.57
11.32
2.10
0.50
11.56
2.36
0.65
11.32
2.18
0.55
11.76
2.11
0.52
11.74
2.35
0.58
P2 O5
0.36
0.26
0.26
0.29
0.28
0.29
0.30
0.29
0.32
0.28
0.30
0.29
0.29
0.31
0.27
0.29
0.28
0.30
0.28
0.29
0.27
0.30
0.27
0.29
0.28
0.30
0.29
0.30
0.31
0.29
0.33
0.30
0.32
0.31
0.30
0.35
0.28
0.29
0.28
0.28
0.30
0.27
0.30
0.28
0.27
0.29
S
0.07
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.00
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.00
0.00
0.00
0.01
0.01
0.02
0.00
0.01
0.01
0.00
Cl
0.02
0.02
0.01
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.02
0.01
0.01
0.02
0.01
0.01
0.01
0.02
0.01
0.01
0.01
0.02
0.01
0.02
0.02
0.02
0.02
0.02
0.01
0.02
0.01
0.02
0.02
0.02
0.02
0.01
0.01
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.01
F
0.05
0.04
0.03
0.01
0.01
0.01
0.04
0.01
0.02
0.02
0.02
0.03
0.04
0.03
0.02
0.04
0.01
0.02
0.00
0.04
0.03
0.03
0.02
0.04
0.04
0.03
0.04
0.03
0.04
0.04
0.04
0.03
0.01
0.03
0.05
0.03
0.06
0.03
0.01
0.02
0.03
0.04
0.02
0.02
0.03
0.04
166
Table A3. (Continued)
LA-ICP-MS (ppm)
Sample
1
2
3
5
7
8
9
11
12
13
15
17
18
19
21
24
25
26
27
29
30
31
32
33
34
35
36
38
42
44
51
53
55
56
58
60
61
62
63
64
65
70
72
73
74
76
Li
5.53
4.68
3.91
4.73
4.14
4.36
5.85
5.79
5.13
4.08
4.76
4.56
3.57
5.16
3.81
4.33
4.82
4.27
4.55
4.52
4.86
5.11
4.42
5.29
4.36
5.06
5.42
4.44
4.73
4.33
4.67
4.72
4.27
5.21
4.71
4.55
3.89
4.77
4.37
4.38
5.17
4.2
4.61
B
2.34
2.42
1.02
2.54
1.86
1.86
2.24
2.4
2.31
1.78
1.42
2.19
2.2
2.16
3.03
1.28
1.79
1.95
2.18
3.09
2.09
2.67
2.39
2.21
1.97
2.19
2.13
2.67
2.11
1.69
1.72
2.81
1.9
2.34
2.26
2.23
2.07
2.12
1.83
1.81
2.33
2.12
2.74
Sc
26.7
33.3
33.6
33.3
34.1
32.6
33.8
32.8
32.5
34.6
33.6
34.5
37.9
32.6
36.7
35.4
36.1
32.5
30.9
32.9
29.1
33.7
34.5
32.3
30.5
35.6
32.8
33.5
28.4
34.3
35.3
33.4
30.1
32.1
33.8
34.6
34.8
33.1
32.9
32.2
32.8
34.4
34.3
Ti
18,161
15,878
15,336
16,523
16,254
16,766
17,550
16,520
16,490
16,287
16,451
15,491
16,402
17,299
16,270
16,075
16,677
16,063
15,776
15,902
15,985
16,151
16,268
15,874
16,019
17,066
17,056
17,756
16,789
15,912
16,595
15,986
16,904
17,257
17,018
16,722
16,970
15,196
16,804
14,960
17,130
16,307
15,721
16,638
V
286
291
303
314
316
336
356
285
325
306
267
323
326
290
335
287
320
310
307
327
293
291
314
326
320
327
291
298
293
312
306
329
341
328
278
315
283
309
355
309
306
Cr
39
386
550
296
387
232
205
439
205
534
412
426
461
393
477
411
454
400
460
388
410
489
416
450
419
255
329
208
98
361
114
449
271
179
307
296
286
420
234
544
194
398
481
261
Mn
1,432
1,328
1,379
1,385
1,373
1,301
1,420
1,467
1,294
1,436
1,367
1,294
1,412
1,497
1,435
1,301
1,444
1,292
1,405
1,345
1,344
1,424
1,356
1,373
1,350
1,285
1,346
1,355
1,278
1,284
1,224
1,352
1,320
1,223
1,379
1,388
1,335
1,316
1,327
1,340
1,281
1,488
1,324
1,263
Co
45
48
54
46
48
41
46
55
41
52
51
46
53
56
57
46
53
46
53
47
47
51
46
51
48
41
44
43
43
47
37
48
42
37
46
44
45
47
43
51
40
54
47
41
Ni
74
158
232
144
170
90
104
196
95
215
173
195
204
177
248
171
199
140
187
166
175
228
152
223
184
111
110
93
85
178
155
105
95
114
118
115
177
96
237
95
177
197
109
Cu
188
112
120
148
134
132
144
144
127
126
112
116
125
145
153
119
153
116
119
159
127
135
129
125
125
132
139
122
135
117
136
129
139
124
148
148
138
115
138
124
134
147
114
139
Zn
122
117
113
162
110
109
126
137
115
118
117
115
121
116
174
101
108
103
123
120
109
132
126
125
111
115
121
117
115
111
125
129
107
116
124
116
110
137
115
115
122
112
118
Ga
24.8
21.4
22.7
23.4
20.7
20.6
25.5
23.9
21.7
22.5
20.7
21.4
21.4
23.7
24.3
20.0
24.4
19.7
22.7
24.8
21.9
25.1
23.1
23.3
21.6
22.7
25.6
24.4
21.2
19.8
22.6
22.9
22.7
24.7
23.6
23.5
21.3
25.4
20.0
19.6
22.7
19.2
22.1
Rb
11.0
7.9
8.7
10.5
9.4
9.6
11.1
11.0
10.1
8.8
9.6
9.6
9.5
10.6
9.8
8.7
10.9
8.7
10.1
10.0
9.9
10.4
9.2
9.7
9.6
10.9
10.8
11.1
11.1
9.0
10.7
10.0
10.4
10.0
11.1
11.4
10.9
8.2
10.9
9.1
10.1
10.6
9.4
10.7
Sr
421
364
355
381
374
400
410
382
395
370
385
380
373
395
373
378
388
379
380
377
378
376
380
378
379
411
419
411
400
377
367
379
401
400
396
393
395
361
399
352
414
372
365
399
Y
Zr
25.4
21.4
22.3
24.8
24.1
24.4
22.0
23.7
22.5
21.6
26.7
20.4
22.1
23.3
22.4
22.2
21.0
21.3
21.9
20.9
23.4
20.7
22.3
22.4
24.1
22.7
25.0
24.4
23.6
23.3
24.2
25.6
20.7
23.0
22.5
22.8
21.7
25.5
20.9
22.1
23.2
168
152
161
166
171
167
161
156
153
158
182
148
152
157
156
160
149
148
152
147
161
137
148
156
162
154
175
163
171
160
170
182
146
169
153
169
150
176
150
146
165
167
Table A3. (Continued)
LA-ICP-MS (ppm)
Sample
1
2
3
5
7
8
9
11
12
13
15
17
18
19
21
24
25
26
27
29
30
31
32
33
34
35
36
38
42
44
51
53
55
56
58
60
61
62
63
64
65
70
72
73
74
76
Nb
16.6
15.9
17.3
17.3
17.8
19.3
17.3
16.4
17.1
16.8
15.6
17.5
17.3
17.2
17.6
17.4
17.0
17.0
16.6
17.2
17.1
16.5
17.2
17.4
17.8
18.3
18.5
16.6
18.0
16.0
17.7
18.7
17.8
17.6
15.7
18.1
15.0
18.6
17.1
15.4
18.3
Mo
0.98
0.83
0.83
1.01
0.88
0.90
0.85
0.91
0.98
1.00
0.89
0.92
0.99
1.02
1.06
0.79
0.96
0.84
0.98
0.95
0.92
0.92
0.87
0.87
0.77
0.93
1.04
0.92
1.03
0.81
0.84
0.89
1.03
0.95
0.86
0.85
0.98
1.06
0.93
0.81
0.85
0.87
0.83
Ag
0.06
0.06
0.03
0.18
0.05
0.03
0.07
0.06
0.06
0.04
0.05
0.08
0.23
0.08
0.08
0.07
0.10
0.07
0.07
0.06
0.04
0.08
0.08
0.07
0.06
0.07
0.03
0.08
0.09
0.04
0.08
0.07
0.02
0.08
0.12
0.05
0.08
0.06
0.19
0.03
0.30
0.02
Cd
0.17
0.08
0.07
0.19
0.08
0.16
0.07
0.11
0.11
0.10
0.08
0.08
0.06
0.10
0.15
0.11
0.08
0.03
0.07
0.06
0.04
0.12
0.15
0.10
0.10
0.07
0.08
0.09
0.07
0.19
0.06
0.07
0.08
0.12
0.11
0.05
0.09
0.10
0.05
0.14
0.12
0.04
In
0.08
0.07
0.08
0.11
0.08
0.04
0.08
0.08
0.09
0.07
0.08
0.07
0.09
0.22
0.09
0.09
0.40
0.07
0.13
0.11
0.06
0.08
0.13
0.09
0.14
0.09
0.09
0.09
0.07
0.09
0.08
0.10
0.08
0.08
0.09
0.09
0.06
0.09
0.06
0.08
0.08
0.08
0.08
Sn
1.48
1.33
1.14
1.58
1.26
1.12
1.44
1.33
1.34
1.33
1.15
1.20
1.29
1.37
1.49
1.25
1.52
1.12
1.22
1.52
1.33
1.48
1.18
1.30
1.14
1.34
1.43
1.29
1.35
1.14
1.30
1.28
1.19
1.37
1.37
1.36
1.24
1.32
1.19
1.38
1.32
1.19
1.35
Sb
0.05
0.06
0.06
0.09
0.04
0.07
0.06
0.05
0.06
0.05
0.07
0.08
0.15
0.07
0.04
0.08
0.48
0.05
0.09
0.05
0.05
0.05
0.11
0.07
0.07
0.07
0.06
0.07
0.05
0.08
0.04
0.06
0.03
0.08
0.05
0.05
0.04
0.07
0.06
0.01
0.06
Cs
0.13
0.08
0.07
0.10
0.09
0.10
0.13
0.11
0.12
0.10
0.08
0.08
0.09
0.12
0.07
0.10
0.08
0.09
0.12
0.08
0.10
0.12
0.09
0.13
0.11
0.10
0.11
0.13
0.11
0.10
0.12
0.12
0.10
0.10
0.12
0.12
0.11
0.10
0.10
0.08
0.10
0.08
0.12
Ba
162
129
132
140
140
147
156
145
148
142
143
142
133
152
138
138
148
140
144
142
144
148
138
146
141
154
151
158
152
139
146
139
150
149
152
140
148
133
146
131
157
140
134
147
La
15.4
14.3
15.7
15.7
16.1
16.2
15.3
16.0
15.5
15.1
16.7
14.7
14.8
15.3
15.4
16.2
15.8
15.3
15.7
15.4
15.7
15.1
16.0
16.7
17.0
16.8
16.9
15.4
16.8
15.9
16.9
17.1
15.7
16.1
14.7
16.0
14.9
17.6
15.5
15.6
16.3
Ce
42.0
33.9
33.8
36.7
35.3
38.5
39.5
37.9
37.1
36.6
37.0
34.4
35.3
37.4
35.6
35.1
37.8
35.4
38.1
36.2
36.9
38.3
35.9
38.1
35.8
38.9
39.3
40.5
38.4
35.0
36.9
36.7
38.6
39.8
39.0
39.3
38.1
33.5
37.7
33.8
39.4
37.0
35.2
37.5
Pr
Nd
Sm
5.0
4.5
4.9
5.1
5.2
5.3
5.0
4.8
4.8
4.9
5.0
4.9
4.9
4.8
5.0
5.0
5.0
5.1
5.0
4.9
4.8
4.9
4.9
5.4
5.5
5.3
5.2
5.0
5.2
4.9
5.2
5.4
5.1
5.0
4.5
5.3
4.7
5.7
5.0
5.1
5.3
24.5
22.3
22.6
23.9
25.5
25.8
23.7
23.6
23.3
22.5
25.0
23.5
24.3
23.7
23.8
24.3
24.4
24.4
23.0
23.0
24.4
22.7
23.2
25.5
26.8
26.0
24.7
23.5
25.0
24.6
26.2
26.2
23.3
25.4
23.0
24.4
22.5
25.7
22.9
24.5
25.2
6.5
5.2
5.5
6.2
6.2
6.6
5.5
5.7
5.7
6.1
6.7
5.4
5.4
5.5
6.0
5.5
5.5
5.6
5.7
5.8
5.6
5.4
6.1
6.3
6.2
6.3
6.2
5.8
6.6
6.2
6.1
7.0
5.5
5.8
5.7
6.0
5.6
6.5
5.6
5.6
6.3
168
Table A3. (Continued)
LA-ICP-MS (ppm)
Sample
1
2
3
5
7
8
9
11
12
13
15
17
18
19
21
24
25
26
27
29
30
31
32
33
34
35
36
38
42
44
51
53
55
56
58
60
61
62
63
64
65
70
72
73
74
76
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
1.91
1.85
2.08
1.85
2.01
2.05
1.97
1.96
1.96
2.00
1.99
1.98
1.80
1.88
1.78
2.07
1.84
1.95
1.81
1.78
1.85
1.86
1.86
2.10
1.86
1.96
1.96
2.06
1.97
1.80
2.05
2.20
1.96
2.04
1.79
1.95
1.81
2.00
1.91
1.82
2.00
6.8
5.7
5.7
6.5
6.2
6.4
5.5
6.0
5.9
5.1
7.3
5.0
5.3
6.0
5.1
6.3
5.0
4.7
5.7
5.3
5.7
5.4
5.8
5.8
6.3
5.9
5.8
6.2
5.9
5.9
6.4
6.5
5.5
6.2
5.7
6.0
5.8
6.2
5.9
5.7
6.0
0.89
0.69
0.79
0.91
0.84
0.82
0.83
0.77
0.74
0.75
0.83
0.78
0.8
0.78
0.83
0.82
0.82
0.79
0.79
0.74
0.83
0.74
0.83
0.88
0.9
0.91
0.83
0.86
0.8
0.83
0.84
0.9
0.76
0.83
0.76
0.84
0.84
0.87
0.77
0.83
0.79
5.3
4.5
4.9
5.4
5.0
5.2
4.7
4.5
4.8
4.8
6.3
5.0
4.6
4.7
4.9
4.7
5.1
4.7
4.8
4.6
5.1
4.5
4.9
5.0
4.7
4.6
5.0
5.0
4.8
4.8
5.2
5.8
4.7
4.9
4.4
5.1
4.6
5.5
4.7
4.8
4.7
0.93
0.83
0.88
0.96
0.96
0.97
0.86
0.89
0.87
0.84
1.18
0.79
0.82
0.84
0.92
0.93
0.90
0.87
0.86
0.81
0.85
0.77
0.79
0.90
1.01
0.84
0.88
0.93
0.90
0.94
0.94
0.94
0.78
0.86
0.86
0.96
0.88
0.96
0.83
0.80
0.88
2.5
2.1
2.5
2.9
2.6
2.6
2.2
2.2
2.4
2.6
3.0
2.3
2.3
2.6
2.3
2.5
2.5
2.2
2.2
2.3
2.6
2.2
2.4
2.6
2.6
2.3
2.4
2.6
2.4
2.2
2.4
2.7
2.2
2.5
2.3
2.4
2.3
2.7
2.2
2.1
2.6
0.28
0.25
0.33
0.38
0.31
0.31
0.32
0.28
0.31
0.30
0.37
0.33
0.28
0.30
0.26
0.27
0.32
0.26
0.25
0.26
0.29
0.24
0.29
0.29
0.28
0.29
0.26
0.37
0.28
0.27
0.29
0.34
0.25
0.24
0.29
0.31
0.30
0.33
0.30
0.26
0.30
1.74
1.88
2.02
2.09
2.22
2.25
1.98
1.56
1.81
2.09
2.47
1.88
1.95
1.88
1.86
1.95
1.78
1.75
1.65
1.84
1.80
1.74
1.91
1.88
1.85
1.86
1.84
1.89
2.01
1.81
2.05
2.16
1.69
1.83
1.68
2.00
1.82
1.92
1.75
1.65
1.79
0.29
0.24
0.24
0.22
0.26
0.29
0.26
0.25
0.27
0.27
0.28
0.26
0.24
0.24
0.24
0.25
0.26
0.21
0.24
0.20
0.26
0.23
0.25
0.26
0.24
0.26
0.28
0.27
0.26
0.25
0.22
0.27
0.22
0.26
0.21
0.28
0.24
0.27
0.27
0.24
0.25
4.2
3.7
4.1
4.7
4.4
4.3
4.3
3.9
4.0
4.2
4.9
4.0
4.0
4.3
4.1
4.1
4.1
3.6
3.8
3.8
4.3
3.6
3.9
4.2
4.0
4.1
4.5
4.3
4.2
4.0
4.5
4.4
3.8
4.2
3.8
4.5
4.0
4.4
4.3
4.0
4.2
1.06
0.99
1.08
1.12
1.16
1.06
0.99
1.02
1.06
1.06
1.09
0.96
0.98
1.05
1.07
1.01
1.00
1.01
0.96
1.00
1.06
1.00
1.02
1.09
0.99
1.08
1.16
0.99
1.13
1.04
1.15
1.04
0.99
1.04
0.98
0.96
0.89
1.22
0.93
0.91
1.07
W
0.20
0.19
0.19
0.25
0.21
0.20
0.32
0.24
0.24
0.21
0.23
0.14
0.25
0.24
0.20
0.22
0.15
0.20
0.29
0.18
0.19
0.28
0.26
0.26
0.22
0.25
0.24
0.18
0.24
0.22
0.21
0.22
0.21
0.26
0.25
0.22
0.19
0.27
0.17
0.22
0.24
0.23
0.20
Pb
1.36
1.03
0.95
5.00
1.09
1.08
1.27
1.20
1.15
1.08
1.10
1.14
2.05
1.47
1.42
1.14
1.14
1.50
1.15
1.66
1.14
1.18
1.29
1.34
1.16
1.15
1.27
1.21
1.30
1.01
1.23
1.28
1.23
1.23
1.16
1.30
0.99
1.32
1.02
1.32
1.22
1.09
1.22
Th
U
1.16
1.16
1.24
1.22
1.33
1.29
1.24
1.12
1.27
1.27
1.37
1.14
1.20
1.21
1.24
1.20
1.23
1.14
1.22
1.10
1.27
1.20
1.21
1.15
1.27
1.24
1.31
1.20
1.35
1.23
1.42
1.37
1.18
1.28
1.18
1.32
1.17
1.47
1.15
1.16
1.25
0.33
0.35
0.34
0.34
0.39
0.39
0.38
0.31
0.39
0.40
0.30
0.42
0.39
0.35
0.38
0.34
0.35
0.37
0.34
0.40
0.34
0.40
0.39
0.41
0.44
0.40
0.40
0.37
0.38
0.39
0.37
0.44
0.43
0.40
0.36
0.42
0.34
0.44
0.41
0.39
0.36
Electron Microprobe (wt. %)
Correction
PEC
Temperature
Sample
SiO2
TiO2
Al2O3
FeO*
%
(°C)
Corrected Melt Inclusions Compositions
1
1,256
9.2 49.78
2.19
12.53 11.00
10a
1,289
12.0 48.79
2.42
12.21 11.05
10b
1,289
12.7 48.83
2.47
12.13 11.05
11a
1,267
11.4 49.42
2.46
12.21 11.01
11b
1,272
9.8 49.39
2.55
12.30 11.02
11c
1,272
9.8 49.39
2.55
12.30 11.02
13
1,216
4.8 50.39
2.36
12.24 10.95
14b
1,294
13.3 48.72
2.48
12.06 11.06
15
1,279
12.3 49.46
2.19
11.92 11.04
2
1,261
11.4 50.04
1.86
12.86 10.99
3a
1,315
14.4 49.49
2.20
11.53 11.08
3b
1,315
16.2 48.97
2.29
11.72 11.09
6
1,275
12.2 49.07
2.23
12.44 11.03
8
1,316
15.3 49.29
2.24
11.82 11.09
9
1,247
8.1 50.59
1.95
11.57 10.98
Uncorrected Melt Inclusion Compositions
1
51.07
2.42
13.80 10.12
10a
50.51
2.75
13.86
9.78
10b
50.69
2.83
13.88
9.65
11a
50.86
2.77
13.78 10.16
11b
50.12
2.83
13.63 11.19
11c
50.12
2.83
13.63 11.19
13
50.61
2.48
12.86 11.35
14b
50.84
2.87
13.90
9.27
15
51.57
2.49
13.58
9.27
2
52.37
2.10
14.52
8.60
3a
51.50
2.57
13.46
9.88
3b
52.00
2.74
13.97
8.26
6
51.15
2.55
14.18
9.17
8
51.37
2.64
13.94
9.96
9
51.73
2.12
12.58 10.29
MgO
10.54
11.77
11.77
10.86
10.90
10.90
9.34
12.01
11.57
10.40
12.59
12.65
11.39
12.83
10.10
7.25
7.48
7.22
6.60
6.91
6.91
7.25
7.38
7.35
6.82
7.31
7.21
7.22
7.10
7.18
MnO
0.13
0.15
0.16
0.17
0.17
0.19
0.14
0.13
0.16
0.13
0.15
0.16
0.17
0.17
0.18
0.14
0.13
0.16
12.18
12.29
12.34
12.54
11.89
11.89
12.43
12.37
12.41
12.00
12.18
12.17
12.74
11.89
12.60
11.07
10.82
10.78
11.12
10.73
10.73
11.83
10.72
10.89
10.65
10.45
10.24
11.21
10.11
11.58
CaO
2.40
2.33
2.35
2.27
2.39
2.39
2.09
2.33
2.36
2.88
2.41
2.60
2.23
2.45
2.51
2.18
2.05
2.05
2.01
2.15
2.15
1.99
2.02
2.07
2.55
2.06
2.18
1.96
2.08
2.31
Na2O
0.48
0.57
0.55
0.55
0.58
0.58
0.48
0.59
0.52
0.44
0.41
0.66
0.49
0.34
0.50
0.44
0.50
0.48
0.49
0.53
0.53
0.46
0.51
0.46
0.39
0.35
0.55
0.43
0.29
0.46
K2 O
0.29
0.31
0.33
0.30
0.29
0.29
0.28
0.31
0.32
0.28
0.28
0.38
0.28
0.30
0.32
0.26
0.27
0.29
0.27
0.27
0.27
0.26
0.27
0.28
0.25
0.24
0.32
0.24
0.26
0.29
P2 O5
0.01
0.15
0.16
0.16
0.13
0.13
0.09
0.15
0.05
0.14
0.15
0.13
0.07
0.15
0.15
0.01
0.14
0.14
0.15
0.12
0.12
0.09
0.13
0.04
0.12
0.13
0.11
0.06
0.13
0.14
S
0.01
0.02
0.02
0.02
0.02
0.02
0.01
0.02
0.01
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.02
0.02
0.01
0.02
0.02
0.01
0.02
0.01
0.01
0.01
0.02
0.01
0.01
0.01
Cl
Table A4. Major and trace element analyses of melt inclusions from Kilauea Iki sample Iki-22.
98.92
97.60
97.50
97.47
97.40
97.40
97.51
97.46
98.10
97.72
98.61
99.07
98.77
98.04
97.58
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Analytical
Total
86.2
87.4
87.4
86.5
86.5
86.5
85.0
87.5
87.1
85.9
87.8
87.9
87.1
88.0
85.6
86.2
87.4
87.4
86.5
86.5
86.5
85.0
87.5
87.1
85.9
87.8
87.9
87.1
88.0
85.6
Host
Fo
0.39
0.52
0.50
0.50
0.57
0.53
0.36
0.46
0.29
0.38
0.71
0.55
0.50
0.36
0.46
0.44
0.44
0.51
0.50
0.32
0.41
0.26
0.33
0.63
0.47
0.46
H2 O
(wt.%)
FTIR
0
143
116
93
141
158
243
59
192
122
0
203
112
0
127
103
83
127
149
214
52
174
106
0
174
103
CO2
(ppm)
169
Sample
Li
B
Sc
Ti
Corrected Melt Inclusions Compositions
1
4.48 2.17 33.5 13,800
10a
3.96 2.51 31.3 15,132
10b
4.14 2.31 31.3 15,034
11a
4.41 2.61 32.4 14,689
11b
4.74 2.38 29.9 15,172
11c
4.10 2.05 28.7 13,407
13
5.39 2.01 33.9 14,583
14b
3.25 4.67 37.2 13,604
15
4.55 2.10 30.6 13,137
2
3.92 2.23 31.6 12,126
3a
4.28 2.92 28.6 14,128
3b
4.71 2.71 30.4 13,719
6
3.87 1.99 32.8 13,744
8
4.03 1.94 28.3 13,192
9
4.31 2.59 36.7 11,310
Uncorrected Melt Inclusion Compositions
1
4.77 2.28 35.9 15,080
10a
4.30 2.70 34.4 16,957
10b
4.48 2.48 34.5 16,990
11a
4.73 2.81 35.5 16,484
11b
5.10 2.54 32.5 16,910
11c
4.38 2.17 31.2 14,943
13
5.61 2.07 35.5 15,423
14b
3.47 5.16 41.2 15,405
15
4.91 2.23 33.6 14,698
2
4.16 2.36 34.0 13,371
3a
4.75 3.22 31.9 16,334
3b
5.22 2.98 34.2 15,874
6
4.13 2.10 36.0 15,371
8
4.50 2.10 31.8 15,389
9
4.56 2.72 39.1 12,245
LA-ICP-MS (ppm)
Table A4. (Continued)
Cr
394
411
379
510
300
389
348
788
477
422
511
391
368
462
420
376
375
343
523
292
394
338
814
453
403
465
343
346
406
407
V
295
285
297
301
302
269
338
218
289
276
263
260
273
259
314
322
318
335
336
336
300
357
246
322
303
303
300
305
301
339
1319
1215
1271
1443
1418
1273
1550
1046
1216
1087
1072
1316
1162
1217
1269
1206
1081
1123
1284
1270
1141
1464
923
1086
985
925
1136
1037
1040
1172
Mn
42.8
40.7
40.6
41.6
43.9
35.7
45.9
29.4
39.9
35.8
36.0
40.3
37.2
37.0
40.9
55.1
56.4
57.5
58.1
58.3
51.0
54.4
47.2
57.5
49.6
54.7
58.3
51.3
57.2
52.6
Co
198
132
147
84
102
74
134
100
124
145
165
146
130
136
137
441
462
480
329
345
317
286
451
443
432
603
612
442
643
369
Ni
113
135
146
123
155
81
153
108
120
53
276
132
130
139
116
104
121
130
110
139
73
145
96
108
48
239
114
116
120
108
Cu
95
100
97
122
123
107
127
44
102
89
88
118
90
109
109
95
100
98
121
122
107
126
51
103
90
89
114
90
108
109
Zn
22.1
25.6
26.6
25.4
26.8
23.7
27.9
24.5
22.1
23.0
27.0
25.6
24.2
21.9
22.3
20.2
22.9
23.6
22.7
24.1
21.3
26.3
21.7
19.7
20.9
23.3
22.2
21.7
18.8
20.6
Ga
7.53
9.03
10.58
9.72
9.82
8.79
9.00
8.25
9.16
6.87
10.55
7.96
6.81
4.44
7.29
6.88
8.04
9.36
8.65
8.81
7.88
8.51
7.28
8.18
6.23
9.11
6.87
6.08
3.79
6.73
Rb
338
378
386
374
394
349
356
377
355
407
437
343
400
308
334
309
337
341
333
354
313
337
333
317
369
378
296
357
264
308
Sr
21.4
20.6
20.3
20.1
21.2
19.5
19.3
35.3
18.5
21.5
20.8
22.0
21.9
20.5
17.4
19.6
18.3
18.0
17.9
19.0
17.5
18.2
31.2
16.6
19.5
18.0
19.0
19.6
17.6
16.1
Y
137
144
148
143
144
122
136
235
132
187
161
143
141
132
132
126
128
131
127
129
110
129
207
118
170
139
124
126
113
122
Zr
170
Sample
Nb
Mo
Ag
In
Corrected Melt Inclusions Compositions
1
10.2 0.63 0.08 0.06
10a
16.1 0.80 0.07 0.08
10b
16.8 0.89 0.07 0.07
11a
14.4 0.79 0.04 0.05
11b
15.1 0.76 0.06 0.07
11c
13.4 0.73 0.05 0.08
13
13.7 0.93 0.06 0.10
14b
14.5 0.53 0.31 0.07
15
11.0 0.75 0.04 0.06
2
10.8 0.68 0.04 0.07
3a
13.5 0.81 0.10 0.06
3b
9.7 0.65 0.06 0.07
6
11.8 0.58 0.04 0.06
8
7.5 0.51 0.05 0.07
9
10.6 0.62 0.05 0.08
Uncorrected Melt Inclusion Compositions
1
11.2 0.67 0.09 0.07
10a
18.0 0.86 0.08 0.08
10b
19.0 0.96 0.08 0.08
11a
16.2 0.86 0.04 0.05
11b
16.9 0.82 0.07 0.07
11c
14.9 0.79 0.05 0.09
13
14.5 0.97 0.06 0.10
14b
16.5 0.56 0.35 0.08
15
12.3 0.81 0.05 0.07
2
11.9 0.72 0.04 0.07
3a
15.6 0.89 0.11 0.07
3b
11.2 0.71 0.07 0.08
6
13.2 0.61 0.05 0.07
8
8.7 0.54 0.06 0.09
9
11.5 0.65 0.05 0.08
LA-ICP-MS (ppm)
Table A4. (Continued)
Ba
106
133
130
131
140
119
118
128
111
89
140
92
102
58
103
116
149
147
147
156
132
124
145
124
98
162
107
114
68
112
Sn
1.36
1.45
1.48
1.34
1.49
1.40
1.65
1.94
1.48
1.85
1.59
1.41
1.27
1.32
1.39
1.44
1.57
1.61
1.46
1.61
1.51
1.72
2.13
1.59
1.98
1.77
1.55
1.36
1.46
1.47
11.5
15.8
16.1
15.9
15.3
13.2
13.4
19.0
11.7
12.9
14.7
11.0
13.1
9.5
11.4
10.5
14.1
14.2
14.2
13.7
11.8
12.7
16.8
10.4
11.7
12.7
9.5
11.7
8.1
10.5
La
28.5
39.7
39.8
37.5
40.3
34.7
37.1
35.3
31.3
36.7
36.8
29.7
30.0
27.5
29.2
26.1
35.4
35.2
33.4
36.2
31.1
35.1
31.2
27.9
33.3
31.8
25.7
26.8
23.6
27.0
Ce
20.4
23.6
24.1
23.1
24.1
20.8
21.3
29.5
19.7
27.0
23.8
21.5
22.0
20.4
19.6
18.6
21.0
21.3
20.6
21.6
18.7
20.2
26.0
17.6
24.4
20.5
18.6
19.7
17.4
18.1
Nd
5.6
5.8
5.6
5.8
6.0
5.3
5.5
8.4
5.6
6.4
5.9
5.6
5.6
5.6
5.4
5.1
5.2
4.9
5.2
5.4
4.7
5.2
7.4
5.0
5.8
5.1
4.8
5.0
4.8
5.0
Sm
4.6
4.6
4.5
4.4
4.5
4.2
4.2
7.7
4.6
4.3
4.9
5.0
4.6
4.4
4.1
4.2
4.1
4.0
3.9
4.1
3.8
4.0
6.8
4.1
3.9
4.2
4.3
4.1
3.7
3.8
Dy
1.97
1.57
1.66
1.66
1.80
1.61
1.58
2.53
1.67
1.69
1.67
1.72
1.53
1.71
1.43
1.80
1.40
1.47
1.48
1.61
1.45
1.50
2.23
1.49
1.53
1.44
1.49
1.38
1.47
1.32
Yb
3.46
3.75
3.57
3.23
3.56
3.05
3.38
5.79
3.20
4.09
4.20
3.68
3.52
3.41
3.30
3.16
3.34
3.16
2.88
3.19
2.73
3.19
5.11
2.86
3.71
3.63
3.18
3.15
2.91
3.05
Hf
0.12
0.25
0.24
0.21
0.16
0.21
0.22
0.21
0.16
0.11
0.16
0.13
0.13
0.11
0.15
0.11
0.22
0.21
0.19
0.14
0.19
0.21
0.19
0.14
0.10
0.14
0.11
0.11
0.09
0.14
W
0.88
1.17
1.27
1.16
1.22
1.11
1.19
1.23
1.05
0.93
1.40
0.93
0.79
0.73
0.91
0.81
1.04
1.12
1.03
1.09
1.00
1.13
1.09
0.94
0.84
1.21
0.81
0.71
0.62
0.84
Pb
0.81
1.32
1.23
1.11
1.14
0.92
0.93
1.35
0.81
0.75
1.03
0.81
0.95
0.60
0.76
0.74
1.17
1.09
0.99
1.02
0.82
0.88
1.19
0.72
0.68
0.89
0.70
0.85
0.51
0.70
Th
171
MnO
0.16
0.16
0.17
0.17
0.17
0.18
0.17
0.16
MgO
45.6
46.34
46.34
45.21
45.21
45.21
44.96
46.74
45.12
46
46.94
46.16
46.61
45.17
CaO
0.27
0.26
0.26
0.24
0.25
0.23
-
Analytical
Total
99.2
98.15
98.15
97.57
97.57
97.57
98.94
99.27
98.62
97.84
99.24
98.47
98.33
98.61
Fo
86.2
87.4
87.4
86.5
86.5
86.5
85.0
87.1
85.9
87.8
87.9
87.1
88.0
85.6
Li
1.41
1.27
1.53
1.84
1.68
1.71
1.79
1.6
1.57
1.34
1.5
1.69
1.27
1.35
Nd
0.12
0.56
0.13
0.14
0.17
0.18
0.14
0.06
0.03
0.12
0.03
0.06
0.14
0.03
LA-ICP-MS (ppm)
FeO*
13.01
11.96
11.96
12.55
12.55
12.55
14.14
12.31
13.15
11.44
11.55
12.23
11.36
13.53
Sample
Ga
Rb
Sr
Y
Zr
Nb
Mo
Sn
Ba
La
Ce
1
0.30
0.02
1.95
0.21
0.82
0.08
0.24
0.45
0.89
0.06
0.22
10a
0.57
0.04
6.08
0.35
2.26
0.26
0.26
0.41
3.37
0.27
0.85
10b
0.37
0.10
2.49
0.29
1.17
0.17
0.31
0.46
1.04
0.09
0.37
11a
0.39
3.62
0.15
0.98
0.08
0.22
0.40
1.34
0.11
0.48
11b
0.41
0.12
2.94
0.18
0.82
0.09
0.24
0.44
1.34
0.11
0.47
11c
0.23
0.04
2.58
0.23
0.80
0.14
0.22
0.44
0.68
0.05
0.34
13
0.41
4.36
0.31
1.34
0.16
0.31
0.48
1.88
0.10
0.43
15
0.33
1.72
0.18
0.71
0.05
0.25
0.53
0.80
0.04
0.26
2
0.24
0.47
0.14
0.28
0.01
0.28
0.52
0.12
0.02
0.04
3a
0.37
3.04
0.22
0.91
0.06
0.26
0.45
1.62
0.07
0.41
3b
0.58
1.10
0.15
0.40
0.06
0.23
0.49
0.73
0.04
0.26
6
0.26
2.19
0.16
0.63
0.04
0.26
0.52
0.88
0.07
0.33
8
0.43
2.72
0.24
1.10
0.09
0.33
0.48
0.74
0.09
0.33
9
0.19
0.06
0.45
0.09
0.29
0.00
0.29
0.47
0.17
0.03
0.05
Dashed spaces indicate measurement not taken, blank values indicate measurement was below detection limits.
Al2O3
0.05
0.05
0.05
0.02
0.02
0.02
0.04
0.04
0.04
0.04
0.06
0.03
0.05
0.05
Ti
177
416
175
207
225
191
241
136
83
169
124
152
226
86
SiO2
40.26
39.64
39.64
39.61
39.61
39.61
39.63
40.01
40.06
40.1
40.45
39.79
40.08
39.7
LA-ICP-MS (ppm)
Sc
7.5
6.6
7.0
7.3
7.2
7.1
7.2
6.0
8.4
7.3
6.7
6.4
7.4
7.7
Sample
1
10a
10b
11a
11b
11c
13
15
2
3a
3b
6
8
9
Electron Microprobe (wt. %)
0.03
0.03
0.06
0.05
0.02
0.02
0.02
0.02
0.02
0.02
0.03
0.03
0.11
0.04
0.01
0.04
Dy
0.03
0.12
0.05
Cr
581
703
656
410
366
338
513
677
614
799
692
553
791
575
Sm
0.01
0.10
V
10.2
13.7
9.7
10.9
9.6
9.4
11.4
9.8
7.8
8.6
9.0
7.4
10.8
9.6
Table A5. Olivine major and trace element compositions from Kilauea Iki sample Iki-22.
0.01
0.05
0.10
0.03
0.02
0.02
0.04
0.06
0.05
Yb
0.05
0.06
0.03
Co
186
183
185
191
182
182
200
204
183
173
172
169
176
192
0.01
0.01
0.01
0.03
0.03
0.07
0.02
Hf
Ni
3026
3119
3012
2303
2435
2404
2890
3101
3200
3368
3554
3046
3636
3159
0.01
0.01
0.02
0.00
Pb
0.01
0.01
Cu
4.5
6.8
5.7
6.5
6.3
5.6
7.2
5.4
4.2
5.0
5.0
5.6
5.8
4.3
Zn
98
101
101
112
109
110
119
111
104
91
92
89
100
110
172
173
APPENDIX B
SUPPLEMENTAL INFORMATION FOR CHAPTER FOUR
Appendix B contains analytical results for experiments during amphibole
analyses. Table B1 summaries repeat EMPA analyses of an amphibole standard using
identical operating conditions as our unknown analyses. Table B2 summarizes repeat LAICP-MS analyses of secondary mafic glass standards at the same settings as unknown
amphibole analyses. Tables B3, B4, B5, and B6 contain major and trace element analyses
from Mt. Pinatubo, Mt. St. Helens, Mt. Hood, and Shiveluch Volcano, respectively. In
each of these tables an asterisk (*) next to the sample ID denotes trace element analyses
with a 30 u µm spot instead of a 50 µm spot for all other analyses.
Table B1. Summary of analytical uncertainty for EMPA analyses of amphibole standard.
Accuracy %
standard standard
Detection
Median (measured/actual) deviation
error
Limit
SiO2
41.0
102
0.3
0.1
0.1
TiO2
4.39
93
0.04
0.01
0.03
Al2O3
14.6
98
0.1
0.0
0.1
FeO
11.0
101
0.4
0.1
0.1
MnO
0.094
104
0.015
0.003
0.061
MgO
13.3
104
0.3
0.1
0.0
CaO
10.0
98
0.1
0.0
0.0
Na2O
2.45
94
0.07
0.01
0.25
K2O
2.05
100
0.04
0.01
0.19
P2O5
0.054
0.032
0.006
0.546
F
0.119
0.032
0.006
0.122
Cl
0.024
0.003
0.001
0.008
SO2
0.036
0.015
0.003
0.044
Total
99.2
All values are wt. % and medians and standard deviations calculated from 25 analyses of Kakanui
amphibole (USNM 143965) run at the same operating conditions as unknown amphibole analyses.
Actual
40.4
4.72
14.9
10.9
0.090
12.8
10.3
2.60
2.05
174
Table B2. Summary of trace element secondary standard accuracy and precision.
GSD-1G
Element
Li
B
Si
Sc
Ti
V
Co
Ni
Cu
Zn
Ga
Ge
Rb
Sr
Y
Zr
Nb
Mo
Ag
Cd
In
Sn
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Dy
Er
Yb
Pb
Accepted
Value
(ppm)
43
50
248691
52
7434
44
40
58
42
54
54
32
37.3
69.4
42
42
42
39
23
18
38
29
67
39.1
41.4
45
44.7
47.8
41
50.7
51.2
40.1
50.9
50
+/6
20
3740
2
360
2
2
4
2
2
7
8
0.4
0.7
2
2
3
3
3
4
5
6
1
0.4
0.4
1
0.5
0.5
2
0.5
0.5
0.4
0.5
2
Median
(ppm)
45.5
53.2
258112
52.7
8044
45.3
40.8
62.1
42.6
55.4
55.0
33.2
37.7
68.0
38.6
40.5
41.7
39.7
23.3
17.1
37.9
29.3
69.3
37.6
40.7
43.6
43.7
46.7
39.8
47.2
48.8
40.3
48.3
50.2
%
Accuracy
(Measured
/ Accepted)
standard
deviation
(ppm)
n
standard
error
(ppm)
106
106
104
101
108
103
102
107
101
103
102
104
101
98
92
96
99
102
101
95
100
101
103
96
98
97
98
98
97
93
95
100
95
100
3.1
4.3
12116
2.0
181
2.2
2.2
4.0
3.2
4.6
3.4
2.3
2.5
1.7
1.7
1.9
1.1
2.8
1.9
1.0
2.5
1.9
2.8
1.3
1.3
1.3
1.8
1.7
1.4
2.3
2.5
3.6
2.3
4.5
72
12
64
72
72
72
72
72
72
72
72
38
72
72
72
72
72
34
72
8
72
72
72
72
72
72
72
72
72
72
72
72
72
72
0.4
1.3
1515
0.2
21
0.3
0.3
0.5
0.4
0.5
0.4
0.4
0.3
0.2
0.2
0.2
0.1
0.5
0.2
0.4
0.3
0.2
0.3
0.1
0.1
0.2
0.2
0.2
0.2
0.3
0.3
0.4
0.3
0.5
175
Table B2. Continued.
Element
Li
B
Si
Sc
Ti
V
Co
Ni
Cu
Zn
Ga
Ge
Rb
Sr
Y
Zr
Nb
Mo
Ag
Cd
In
Sn
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Dy
Er
Yb
Pb
Accepted
Value
(ppm)
9
6
254301
33
14100
425
38
13
21
125
23
1.5
47
342
35
184
12.5
270
0.5
0.2
0.11
2.6
683
24.7
53.3
6.7
28.9
6.59
1.97
6.71
6.44
3.7
3.39
11
BCR-2G
%
Accuracy
(Measured
Median
/
(ppm)
Accepted)
+/1
1
1870
2
1000
18
2
2
5
5
1
0.1
0.5
4
3
15
1
30
0.4
0.02
0.4
7
0.3
0.5
0.4
0.3
0.07
0.02
0.07
0.06
0.04
0.03
1
9.2
5.12
256005
34.87
13937
440
37.90
12.63
17.16
155
59.62
1.99
45.58
325
30.12
169
11.28
266
1.19
0.16
0.08
1.65
664
23.66
50.47
6.26
27.30
6.18
1.82
6.25
5.72
3.50
2.87
10.70
102
85
101
106
99
104
100
97
82
124
259
133
97
95
86
92
90
99
239
78
76
64
97
96
95
93
94
94
92
93
89
95
85
97
standard
deviation
(ppm)
n
standard
error
(ppm)
1.2
3.7
13208
1.74
371
20.53
2.11
1.59
1.44
12.89
13.83
0.23
2.41
7.07
1.14
6.74
0.42
12.83
0.41
0.02
0.02
0.13
21.92
0.97
1.89
0.25
1.34
0.47
0.15
0.77
0.36
0.64
0.36
1.16
29
5
27
29
29
29
29
29
29
29
29
17
29
29
29
29
29
14
29
2
29
29
29
29
29
29
29
29
29
29
29
29
29
29
0.22
1.7
2542
0.32
68.92
3.81
0.39
0.30
0.27
2.39
2.57
0.06
0.45
1.31
0.21
1.25
0.08
3.43
0.08
0.01
0.00
0.02
4.07
0.18
0.35
0.05
0.25
0.09
0.03
0.14
0.07
0.12
0.07
0.21
176
Table B2. Continued.
Element
Li
B
Si
Sc
Ti
V
Co
Ni
Cu
Zn
Ga
Ge
Rb
Sr
Y
Zr
Nb
Mo
Ag
Cd
In
Sn
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Dy
Er
Yb
Pb
Accepted
Value
(ppm)
BHVO-2G
%
Accuracy
(Measured
Median /
(ppm)
Accepted)
+/-
4.4
0.8
230460
33
16300
308
44
116
127
102
22
1.6
9.2
396
26
170
18.3
3.8
467
2
900
19
2
7
11
6
3
0.1
0.04
1
2
7
0.8
0.2
0.1
0.1
2.6
131
15.2
37.6
5.35
24.5
6.1
2.07
6.16
5.28
2.56
2.01
1.7
0.02
0.02
0.6
2
0.2
0.2
0.22
0.2
0.03
0.01
0.05
0.05
0.02
0.02
0.2
4.38
2.88
229142
33.15
16426
323
43.37
120
122
112
23.90
1.66
8.47
387
21.99
156
16.00
3.76
0.35
0.07
0.08
1.35
129
14.68
35.96
4.88
23.74
5.67
1.97
5.72
4.77
2.35
1.73
1.68
99
99
100
101
105
99
104
96
110
109
104
92
98
85
92
87
99
69
82
52
98
97
96
91
97
93
95
93
90
92
86
99
standard
deviation
(ppm)
0.80
0.98
14359
1.10
412
20.71
3.07
9.08
10.75
11.51
3.27
0.27
0.77
8.08
1.37
8.53
0.54
0.29
0.13
0.04
0.01
0.11
3.48
0.65
1.29
0.22
1.36
0.47
0.11
0.60
0.39
0.40
0.21
0.19
n
29
4
27
29
29
29
29
29
29
29
29
17
29
29
29
29
29
14
29
2
28
29
29
29
29
29
29
29
29
29
29
29
29
29
standard
error
(ppm)
0.15
0.49
2763
0.20
77
3.85
0.57
1.69
2.00
2.14
0.61
0.07
0.14
1.50
0.25
1.58
0.10
0.08
0.02
0.02
0.00
0.02
0.65
0.12
0.24
0.04
0.25
0.09
0.02
0.11
0.07
0.08
0.04
0.03
rim
core
rim
core
core
rim
single
rim
core
rim
core
core
single
core
rim
rim
core
core
single
rim
core
rim
core
rim
core
single
rim
core
single
rim
core
rim
core
single
CN6791-i-1-1
CN6791-i-1-2
CN6791-i-1-3
CN6791-i-2-1
CN6791-i-3-1
CN6791-i-3-2
CN6791-i-3-3
CN6791-i-3-4
CN6791-i-4-1
CN6791-i-4-2
CN6791-i-5-1
CN6791-i-6-1
CN6791-i-6-2
CN6791-i-6-3
CN6791-i-6-4
CN6791-i-6-5
CN6791-i-7-1
CN6791-i-7-2
CN6791-i-8-1
Spot Location
P22892-1A-1-1
P22892-1A-1-2
P22892-1A-1-3
P22892-1A-1-4
P22892-1A-2-1
P22892-1A-2-2
P22892-1A-3-2*
P22892-1A-4-1
P22892-1A-4-2
P22892-1A-5-1*
P22892-1A-5-2
P22892-1A-5-5
P22892-1A-6-2
P22892-1A-6-3*
P22892-1A-6-4*
Sample ID
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
basalt inclusion June 7-12
Eruption Date
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hst
Tsch-Prg
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Tsch-Prg
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hbl
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
163
212
159
137
161
176
181
174
154
145
166
411
369
132
160
169
170
148
388
454
840
411
583
174
414
398
720
758
822
727
789
770
787
474
829
855
837
804
830
817
846
843
828
824
836
934
930
813
833
854
826
837
933
939
969
936
963
845
939
933
957
964
951
966
960
968
961
936
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
48.9
46.7
48.7
50.6
49.0
48.1
47.7
48.6
49.1
50.0
49.0
42.9
44.0
50.7
48.8
49.3
49.1
49.4
44.0
42.5
42.7
42.8
41.8
48.6
43.8
43.3
43.1
42.7
42.4
42.6
42.8
42.3
43.4
41.9
0.78
0.85
0.75
0.71
0.76
0.79
0.83
0.76
0.79
0.73
0.85
1.78
1.63
0.79
0.81
0.75
0.80
0.72
1.87
1.85
1.70
1.41
2.13
0.77
1.81
1.59
1.90
1.90
1.75
1.91
1.57
1.88
1.82
1.95
8.0
9.3
7.8
6.9
7.7
8.6
8.5
8.2
7.6
7.2
8.1
12.8
12.2
6.8
7.8
7.9
8.3
7.7
12.6
13.2
13.6
12.8
13.6
8.4
13.0
12.7
13.2
13.6
13.7
13.3
13.3
13.6
13.1
13.8
10.5
10.9
10.7
10.4
10.5
10.9
10.7
10.8
10.6
10.6
10.7
11.7
11.6
10.4
10.8
10.4
10.5
10.9
11.7
11.9
11.6
11.7
11.5
10.8
11.6
11.6
11.8
11.7
11.9
11.7
11.7
11.7
11.9
11.9
13.7
14.7
14.1
13.1
13.2
13.9
14.2
14.1
13.6
13.4
13.6
11.5
10.7
12.7
13.8
14.0
14.4
13.6
11.2
11.3
11.8
11.0
12.4
14.3
12.0
11.5
10.5
11.2
12.1
10.8
10.8
11.3
9.9
13.0
15.2
13.9
15.0
16.0
15.5
14.6
14.6
14.7
15.2
15.5
15.3
14.8
15.8
16.3
15.1
15.1
15.0
15.0
15.3
14.8
14.7
15.4
14.3
14.5
14.7
15.1
15.6
14.9
14.1
15.2
15.4
15.0
15.8
13.5
0.47
0.57
0.59
0.51
0.53
0.46
0.54
0.66
0.55
0.62
0.51
0.15
0.15
0.46
0.59
0.68
0.48
0.60
0.14
0.13
0.16
0.14
0.12
0.61
0.18
0.13
0.09
0.16
0.13
0.14
0.12
0.12
0.11
0.15
1.36
1.43
1.28
0.98
1.21
1.28
1.41
1.26
1.25
1.13
1.34
2.26
2.18
1.20
1.22
1.30
1.25
1.55
2.28
2.26
2.39
2.24
2.29
1.44
2.33
2.30
2.27
2.26
2.43
2.31
2.31
2.31
2.34
2.33
0.26
0.42
0.34
0.16
0.23
0.38
0.33
0.30
0.26
0.22
0.23
0.67
0.68
0.19
0.31
0.24
0.22
0.24
0.68
0.77
0.87
0.77
0.86
0.26
0.73
0.72
0.93
0.94
0.86
0.82
0.87
0.91
0.94
0.71
0.03
0.01
0.00
0.03
0.00
0.01
0.04
0.00
0.00
0.01
0.02
0.07
0.04
0.01
0.07
0.02
0.06
0.00
0.00
0.01
0.08
0.12
0.07
0.00
0.03
0.01
0.01
0.01
0.00
0.01
0.00
0.03
0.02
0.12
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
Table B3. Amphibole analyses from the 1991 eruption of Mt. Pinatubo.
F
0.05
0.05
0.05
0.02
0.12
0.09
0.08
0.07
0.10
0.00
0.10
0.03
0.11
0.16
0.05
0.03
0.06
0.19
0.14
0.12
0.05
0.13
0.04
0.03
0.10
0.06
0.10
0.09
0.08
0.03
0.12
0.12
0.19
0.09
Cl
0.043
0.045
0.033
0.038
0.044
0.035
0.049
0.033
0.039
0.039
0.040
0.017
0.015
0.036
0.043
0.040
0.045
0.035
0.016
0.014
0.016
0.016
0.013
0.030
0.015
0.016
0.013
0.011
0.015
0.015
0.008
0.014
0.007
0.018
SO2
Total
0.010 99.4
0.000 98.9
0.006 99.4
0.000 99.4
0.014 98.8
0.000 99.1
0.010 98.9
0.000 99.5
0.000 99.1
0.004 99.4
0.000 99.8
0.014 98.7
0.000 99.1
0.001 99.7
0.005 99.5
0.000 99.8
0.005 100.3
0.007 99.9
0.007 99.9
0.019 98.9
0.019 99.8
0.016 98.6
0.014 99.1
0.024 99.7
0.023 100.4
0.026 99.1
0.012 99.4
0.014 99.5
0.045 99.4
0.028 99.0
0.016 99.0
0.014 99.3
0.002 99.6
0.009 99.5
177
18.6
2.27
11.8
22.7
33.4
15.7
16.3
54.5
69.3
45.1
59.3
30.7
35.1
31.9
77.8
19.1
13.2
42.7
56.4
70.5
15.8
14.1
38.4
CN6791-i-1-1
CN6791-i-1-2
CN6791-i-1-3
CN6791-i-2-1
CN6791-i-3-1
CN6791-i-3-2
CN6791-i-3-3
CN6791-i-3-4
CN6791-i-4-1
CN6791-i-4-2
CN6791-i-5-1
CN6791-i-6-1
CN6791-i-6-2
CN6791-i-6-3
CN6791-i-6-4
CN6791-i-6-5
CN6791-i-7-1
CN6791-i-7-2
CN6791-i-8-1
13.7
10.2
12.0
12.8
13.2
17.2
17.3
7.88
9.14
22.7
219111
230950
225189
226937
251260
235059
219559
206502
214427
230068
240007
176492
199320
219127
227198
216400
233006
230805
207740
189228
181773
177692
184687
218124
191439
193010
200146
192387
172912
174836
193172
177437
199969
178777
11098
10407
10714
12579
5181
10974
10789
11840
12402
11766
12685
11775
12863
11908
13057
72.1 4860
79.6 4502
99.7 4677
64.9 5037
64.0 5204
96.5 5429
70.3 5284
71.5 5617
71.6 4714
71.5 5482
67.2 5203
64.7 12695
57.9 10609
64.2 5405
71.2 4713
71.0 5095
62.4 5079
87.5 4831
60.3 11327
62.9
50.1
50.5
60.7
78.7
79.4
64.6
81.6
91.7
56.6
88.8
88.7
97.7
85.4
69.4
289
299
265
290
307
323
279
296
273
286
308
531
488
313
276
283
276
267
533
465
460
428
545
309
511
469
553
529
510
518
504
510
505
538
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
P22892-1A-1-1
P22892-1A-1-2
P22892-1A-1-3
P22892-1A-1-4
P22892-1A-2-1
P22892-1A-2-2
P22892-1A-3-2*
P22892-1A-4-1
P22892-1A-4-2
P22892-1A-5-1*
P22892-1A-5-2
P22892-1A-5-5
P22892-1A-6-2
P22892-1A-6-3*
P22892-1A-6-4*
Sample ID
Table B3. Continued.
Co
Ni
Cu
Zn
Ga
Ge
Rb
Sr
Y
Zr
Nb
Mo
Ag
In
Sn
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Dy
55.6
53.5
53.1
55.0
61.1
60.8
49.6
50.3
50.5
56.8
57.6
65.1
66.8
54.9
52.7
52.4
56.1
55.1
69.3
93.1
77.6
70.4
96.3
116
89.1
78.3
66.7
98.5
81.4
96.7
236
268
123
90.2
87.5
100
76.8
214
4.22 246 19.7 3.32 0.75 28.9 74.9 30.8 4.76
0.195 2.36 19.2 12.2 56.0 10.2 58.4 16.8 2.99
9.77 267 18.5 2.79 1.52 28.6 78.3 28.9 4.21
0.220 2.39 23.8 13.2 59.4 11.1 60.4 14.0 3.29
2.60 249 18.3 3.40 0.49 26.4 95.1 32.0 4.59
0.035 0.255 3.01 15.1 12.6 60.1 11.5 63.7 19.4 3.47
2.87 257 17.1 2.79 0.07 28.3 69.3 35.8 4.39
0.009 0.173 2.10 20.8 11.1 48.9 9.23 45.7 15.9 2.46
21.7 281 19.8 3.02 0.76 35.6 64.7 37.2 4.27
0.057 0.222 2.52 22.9 9.46 46.3 8.62 47.2 12.7 2.79
27.0 259 21.2 4.28 2.85 34.4 83.4 30.7 5.55
0.044 0.262 2.92 36.1 11.6 54.9 10.4 61.0 18.5 3.66
20.6 247 18.9 3.59 0.58 33.4 78.7 35.5 4.98 0.06 0.033 0.202 2.37 27.2 13.1 56.2 10.9 60.2 17.4 3.61
8.17 262 18.5 2.67 1.19 34.0 71.6 32.9 4.62
0.189 2.40 27.8 12.9 59.3 11.1 56.7 12.9 2.82
4.89 253 15.6 2.55 1.11 31.1 66.7 34.8 3.64 0.09
0.170 1.96 28.3 9.62 45.7 8.62 44.4 13.2 2.84
5.62 258 18.8 3.49 0.51 33.0 74.6 38.3 4.35
0.004 0.238 2.13 23.5 11.6 52.2 9.97 51.1 15.4 2.87
21.7 263 17.7 2.35 1.43 33.3 73.4 35.4 3.93
0.011 0.190 2.36 25.9 10.3 47.8 8.95 50.5 15.1 3.12
5.15 56.9 18.4 0.95 3.66 304 20.9 38.8 1.74
0.113 1.20 102 4.79 19.0 3.53 20.5 6.63 2.16
17.3 56.1 17.8 1.39 3.59 295 17.2 36.5 1.65
0.058 0.092 1.14 99.2 4.30 16.8 3.09 18.7 7.40 1.62
17.5 196 15.5 2.56 1.74 45.1 46.4 35.5 3.14
0.079 0.151 1.49 30.9 9.04 39.5 6.68 37.4 9.93 2.41
9.05 267 18.1 3.59 0.30 28.0 76.1 33.8 4.51
0.009 0.222 2.46 19.1 12.0 52.1 9.98 52.9 14.5 3.22
41.2 234 18.1 2.88 1.88 31.7 69.5 34.6 4.18
0.171 2.07 31.2 11.2 50.2 9.51 53.5 14.0 2.79
4.81 261 18.4 3.04 0.54 30.5 70.9 33.8 4.29
0.205 2.19 18.2 11.0 53.4 9.93 50.4 15.4 3.26
10.6 275 18.7 3.95 1.44 29.8 87.5 51.8 4.21
0.270 2.38 23.0 12.7 61.2 11.3 66.4 18.0 3.42
4.32 62.5 19.2 1.99 4.84 305 21.6 44.0 1.59
0.098 1.14 107 5.24 18.7 3.50 18.6 6.47 1.70
15.4
15.6
20.4
15.1
11.8
17.5
15.8
15.4
14.5
13.2
15.7
7.51
5.63
11.8
15.1
13.9
14.3
18.1
7.46
14.2
15.1
19.1
11.5
12.3
15.6
13.3
14.0
13.5
14.0
14.3
4.76
4.52
10.6
14.0
13.2
14.5
16.2
4.16
55.0 197 2.31 53.7 16.6 1.32 3.39 319 21.5 41.4 1.88
0.052 0.95 115 6.19 21.5 4.10 23.2 6.63 1.76 5.47 4.13
59.1 136 1.56 60.6 16.3 1.24 3.70 298 21.4 52.5 1.50 0.07
0.080 1.08 111 5.31 20.7 3.91 23.4 5.31 2.06 6.73 4.16
54.9 155 2.80 53.0 15.4 0.72 3.79 344 23.2 53.6 1.84
0.102 1.04 131 7.28 26.0 4.19 26.9 6.46 2.45 8.24 5.66
61.7 108 3.47 57.2 19.4 1.37 4.26 319 23.7 63.6 1.38
0.042 0.122 1.42 143 6.49 22.3 4.09 23.6 8.05 1.74 6.34 5.77
52.8 67.6 12.3 243 18.9 4.21 1.04 30.7 83.2 40.7 4.26
0.256 2.41 18.7 12.9 59.4 10.9 60.2 16.3 2.98 16.8 16.2
68.7 150 5.36 47.9 16.8 1.87 3.71 298 20.0 52.5 2.23
0.036 0.110 1.45 105 4.22 16.8 3.12 16.9 6.43 1.86 5.99 4.91
65.4 221 0.99 60.2 15.7 1.87 4.18 290 21.1 46.7 1.34
0.103 0.84 98.9 4.46 18.6 3.47 20.0 6.28 1.90 7.20 4.94
69.2 197 3.04 45.2 16.7 1.28 3.80 297 18.3 39.1 1.15
0.088 1.28 120 4.01 17.0 2.90 18.7 5.22 1.72 6.66 3.79
66.4 158 3.49 48.4 16.8 1.15 3.85 305 18.3 47.5 1.29
0.103 1.11 114 4.18 18.3 3.35 17.3 6.28 1.94 6.42 4.32
63.2 97.7 2.33 63.6 20.2 2.71 3.80 308 22.6 45.8 1.64
0.087 1.12 120 4.99 18.9 3.49 20.1 7.82 1.83 8.10 3.35
64.9 187 1.63 46.8 16.4
3.39 347 23.0 45.6 1.02
0.068 1.17 130 5.61 18.6 3.98 22.3 6.31 1.94 6.56 4.07
64.8 221 5.81 49.4 17.8 1.92 4.52 299 18.5 39.4 1.17
0.096 1.30 118 4.47 16.3 3.15 18.3 5.80 1.89 6.02 3.35
62.8 185 2.09 46.8 15.9 1.43 3.89 322 21.0 45.5 1.17
0.005 0.145 1.17 123 4.85 18.4 3.35 20.5 5.04 1.91 6.05 4.77
62.3 153 4.79 48.8 19.5 1.91 7.29 331 22.5 77.1 1.26 0.29
0.152 1.11 135 6.30 20.0 4.03 21.9 5.67 1.51 7.24 3.45
65.9 76.3 9.86 59.6 19.4 2.08 4.02 383 25.7 65.4 1.61
0.116 0.93 164 7.36 26.0 4.98 25.5 8.82 1.59 7.80 6.01
Er
8.31
8.22
10.5
7.95
7.00
11.0
7.96
6.89
7.57
9.00
7.94
1.99
2.29
5.29
8.22
8.23
6.87
9.48
2.37
1.77
2.54
2.59
2.72
7.97
2.22
2.77
1.67
2.68
2.03
2.22
1.86
2.26
2.07
3.24
Yb
7.19
8.36
7.87
6.30
5.99
7.64
7.98
7.15
6.58
8.29
6.73
1.79
1.36
5.21
6.61
6.04
7.69
8.92
1.49
1.26
1.72
2.14
1.67
7.95
1.61
1.86
1.35
1.34
1.39
1.93
2.06
1.40
1.76
1.35
Pb
0.58
0.65
0.54
0.49
0.52
0.95
0.53
0.59
0.69
0.54
0.46
0.42
0.53
0.48
0.42
0.70
0.47
0.68
0.69
0.51
0.49
0.50
0.53
0.87
0.66
0.64
0.38
0.44
0.59
0.40
0.47
0.41
0.76
0.61
178
rim
core
single
rim
core
rim
rim
core
rim
core
rim
core
single
core
rim
core
rim
core
core
core
core
rim
rim
core
single
single
rim
core
rim
core
rim
core
rim
core
rim
core
P22892-1A2-1-1
P22892-1A2-1-2
P22892-1A2-1-3
P22892-1A2-1-4
P22892-1A2-2-1
P22892-1A2-2-4
P22892-1A2-2-6
P22892-1A2-2-7
P22892-1A2-3-1
P22892-1A2-3-2
P22892-1A2-4-1*
P22892-1A2-4-2
P22892-1A2-5-1
P22892-1A2-5-2
P22892-1A2-6-1
P22892-1A2-6-2
Spot Location
22892-2A2-1-1
22892-2A2-1-2
22892-2A2-1-3
22892-2A2-2-1*
22892-2A2-2-2
22892-2A2-2-3
22892-2A2-2-4
22892-2A2-2-5
22892-2A2-2-6
22892-2A2-2-7
22892-2A2-3-1
22892-2A2-3-2
22892-2A2-3-3
22892-2A2-3-4
22892-2A2-4-1*
22892-2A2-4-2
22892-2A2-4-3
22892-2A2-4-4
22892-2A2-4-5
22892-2A2-4-7
Sample ID
Eruption Date
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
June 7-12
Table B3. Continued.
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Tsch-Prg
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
Mg-Hst
186
139
167
141
159
145
182
164
139
180
177
423
158
205
182
181
714
923
793
467
759
414
698
804
444
864
584
604
458
595
437
666
440
747
785
660
850
825
827
815
831
830
876
840
823
826
839
939
828
863
828
834
943
984
970
933
969
934
941
962
932
982
950
967
945
955
926
968
931
949
954
961
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
47.2
50.1
48.5
50.0
48.7
49.3
48.0
49.1
50.6
48.4
48.5
43.3
48.7
47.1
47.9
48.3
42.9
41.8
42.7
42.1
41.9
44.1
41.3
42.6
43.4
41.9
42.2
41.6
43.0
42.0
43.1
41.6
43.1
43.9
41.8
41.3
0.77
0.72
0.84
0.70
0.81
0.71
0.87
0.98
0.66
0.86
0.81
1.52
0.79
0.81
0.90
0.88
1.54
1.79
2.00
1.74
2.12
1.64
1.62
1.78
1.70
1.99
1.72
2.08
1.80
2.09
1.64
2.06
1.62
1.55
1.61
1.98
8.4
7.0
8.2
7.1
7.8
7.3
8.1
7.9
7.0
8.6
8.2
12.9
7.9
9.1
8.6
8.8
13.3
14.0
13.7
13.6
13.9
13.0
14.6
14.1
13.2
13.9
13.3
13.7
13.1
13.6
13.0
14.1
13.0
13.0
14.0
14.1
10.7
10.2
10.7
10.4
10.5
10.6
10.2
10.3
10.3
10.9
10.4
11.7
10.9
10.5
10.6
10.9
11.9
11.7
11.7
11.9
11.8
11.8
11.8
11.6
11.9
11.8
11.8
11.6
11.8
11.8
11.9
11.6
11.9
11.7
11.8
11.8
14.0
13.4
13.6
13.4
13.4
13.5
13.7
13.9
13.0
13.9
13.8
9.4
14.0
15.5
14.3
14.3
11.2
11.5
11.0
12.0
11.9
10.5
14.2
12.0
10.7
11.8
11.6
12.2
10.5
11.4
10.9
11.8
10.9
11.0
12.4
11.7
14.3
15.8
15.1
15.5
15.3
15.4
15.2
15.2
15.9
14.7
15.1
15.8
14.6
13.7
14.4
14.1
14.9
14.9
15.1
14.3
14.2
15.5
12.7
14.3
15.4
14.7
14.9
14.5
15.4
14.8
15.2
14.3
15.3
15.5
14.1
14.4
0.65
0.55
0.46
0.57
0.51
0.58
0.60
0.50
0.56
0.50
0.53
0.10
0.59
0.65
0.45
0.52
0.14
0.13
0.10
0.11
0.14
0.12
0.20
0.15
0.10
0.14
0.13
0.13
0.13
0.09
0.11
0.16
0.12
0.13
0.14
0.12
1.27
1.21
1.32
1.09
1.28
1.29
1.47
1.33
1.23
1.30
1.24
2.34
1.33
1.42
1.31
1.52
2.28
2.44
2.36
2.27
2.38
2.36
2.24
2.33
2.24
2.43
2.23
2.31
2.25
2.24
2.18
2.22
2.22
2.32
2.36
2.22
0.34
0.17
0.28
0.20
0.25
0.23
0.31
0.20
0.27
0.41
0.24
0.37
0.35
0.38
0.33
0.39
0.81
0.93
0.86
0.76
0.80
0.77
0.83
0.82
0.83
0.94
0.84
0.84
0.84
0.85
0.86
0.96
0.82
0.87
0.78
0.97
0.00
0.06
0.00
0.02
0.00
0.05
0.00
0.00
0.02
0.02
0.05
0.00
0.01
0.02
0.00
0.00
0.01
0.01
0.00
0.06
0.08
0.02
0.05
0.07
0.04
0.02
0.00
0.06
0.08
0.08
0.04
0.07
0.01
0.07
0.04
0.06
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
F
0.09
0.11
0.08
0.09
0.07
0.04
0.09
0.03
0.00
0.00
0.06
0.12
0.04
0.06
0.07
0.05
0.03
0.12
0.02
0.07
0.13
0.03
0.06
0.11
0.03
0.01
0.03
0.05
0.12
0.15
0.08
0.05
0.06
0.07
0.13
0.13
Cl
0.040
0.034
0.045
0.037
0.041
0.037
0.050
0.044
0.037
0.042
0.049
0.012
0.039
0.044
0.052
0.039
0.014
0.013
0.013
0.016
0.014
0.011
0.026
0.011
0.012
0.010
0.014
0.010
0.010
0.011
0.019
0.010
0.011
0.013
0.018
0.013
SO2
Total
0.012
0.000
0.013
0.000
0.000
0.020
0.004
0.003
0.001
0.004
0.000
0.030
0.010
0.000
0.001
0.003
97.8
99.3
99.1
99.1
98.6
99.1
98.6
99.4
99.6
99.7
99.0
97.6
99.3
99.2
99.0
99.7
0.008 98.9
0.025 99.2
0.013 99.5
0.025 99.0
0.017 99.4
0.000 99.7
0.014 99.6
0.033 100.0
0.018 99.6
0.009 99.7
0.011 98.9
0.019 99.1
0.032 99.1
0.008 99.1
0.000 99.0
0.026 99.0
0.019 99.2
0.021 100.1
0.030 99.1
0.000 98.7
179
0.84
1.87
4.69
3.22
5.28
6.32
31.6
66.9
15.1
24.1
68.4
58.5
55.2
53.4
37.4
103
35.2
10.5
19.1
40.3
33.5
P22892-1A2-1-1
P22892-1A2-1-2
P22892-1A2-1-3
P22892-1A2-1-4
P22892-1A2-2-1
P22892-1A2-2-4
P22892-1A2-2-6
P22892-1A2-2-7
P22892-1A2-3-1
P22892-1A2-3-2
P22892-1A2-4-1*
P22892-1A2-4-2
P22892-1A2-5-1
P22892-1A2-5-2
P22892-1A2-6-1
P22892-1A2-6-2
2.04
3.78
4.47
3.97
6.60
2.87
9.88
2.39
4.54
2.48
8.68
3.47
0.82
2.57
204535
216801
213718
196947
213900
210158
208888
202401
210062
208953
232170
194361
208097
206584
218892
216257
205425
195303
211092
202282
198568
179853
176125
185266
181086
190123
190817
181566
188432
183213
208439
195208
201912
187663
192599
193550
11079
12297
13149
11894
13267
11107
10771
11984
11645
13668
11746
13861
11604
12957
11208
12711
11063
10316
9924
13022
87.7 5404
58.9 5285
69.1 5301
62.1 5470
65.2 4914
69.3 5087
59.4 5283
45.0 6619
58.7 4380
93.0 5190
74.9 5887
94.3 10344
70.3 5151
66.8 5546
68.4 5404
95.7 5498
61.9
84.9
87.3
56.7
82.0
71.6
49.9
67.1
62.2
79.8
75.2
73.2
79.3
77.5
76.9
71.9
59.3
60.0
45.9
71.2
269
270
274
273
240
272
280
284
251
310
316
533
267
276
292
296
517
519
551
530
554
454
489
524
486
555
502
541
503
541
502
543
466
439
452
553
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
22892-2A2-1-1
22892-2A2-1-2
22892-2A2-1-3
22892-2A2-2-1*
22892-2A2-2-2
22892-2A2-2-3
22892-2A2-2-4
22892-2A2-2-5
22892-2A2-2-6
22892-2A2-2-7
22892-2A2-3-1
22892-2A2-3-2
22892-2A2-3-3
22892-2A2-3-4
22892-2A2-4-1*
22892-2A2-4-2
22892-2A2-4-3
22892-2A2-4-4
22892-2A2-4-5
22892-2A2-4-7
Sample ID
Table B3. Continued.
Co
Ni
Cu
Zn
Ga
Ge
Rb
47.3
54.9
55.5
51.9
53.9
55.3
53.8
53.6
52.0
52.0
56.5
58.0
50.4
45.6
57.7
48.2
61.1
99.2
89.5
92.5
83.0
93.9
99.1
110
92.4
80.2
118
162
77.0
56.1
90.9
69.9
323
316
334
382
384
341
353
330
385
330
346
400
321
353
325
329
362
314
305
325
Sr
1.25 245 17.4 3.69 0.45 30.7
1.44 232 16.2 3.16 0.41 32.0
9.07 211 15.7 3.32 0.29 27.0
9.45 215 16.0 2.70 0.43 36.6
2.76 224 14.6 3.45 0.73 26.0
8.77 243 17.7 2.73 0.48 31.2
7.18 224 17.2 2.94 0.46 34.9
7.77 233 18.2 2.33 0.36 38.3
11.4 212 14.8 3.07 1.96 40.7
7.44 240 19.6 3.47 0.82 30.4
13.7 253 16.9 2.75
35.7
3.40 49.7 13.3 1.54 1.11 160
1.07 236 17.4 3.13 0.35 31.0
2.65 224 15.3 2.27 0.50 44.8
2.21 229 18.2 3.02 0.43 37.5
8.01 230 18.0 3.14 1.30 33.1
68.2 202 7.61 62.2 19.1 1.54 4.76
65.0 158 2.01 50.5 19.2 1.71 4.33
67.4 219 3.49 53.3 20.9 2.38 4.94
69.2 121 1.62 70.4 21.0 1.33 4.24
67.1 151 6.42 52.6 21.1 2.06 5.00
60.5 230 2.19 49.4 17.4 1.00 3.18
63.8 90.1 3.70 69.7 20.0 1.68 3.57
67.9 110 2.95 48.7 19.2 1.44 3.97
63.6 156 4.48 61.7 19.6 1.73 3.52
67.7 146 2.47 50.3 20.3 1.55 3.82
66.0 254 1.97 51.6 17.8 1.44 4.32
62.6 105 2.63 50.2 21.3 1.97 3.99
61.1 141 1.71 44.2 18.3 1.32 3.47
64.1 114 2.09 48.1 18.6 1.45 4.13
66.1 260 1.46 56.9 19.4 1.41 4.23
65.5 138 2.60 48.1 21.8 1.58 5.16
63.3 218 5.07 56.6 19.2 1.58 3.27
64.9 188 1.08 53.9 18.1 1.21 2.89
62.3 101 1.31 61.0 20.2 1.87 4.05
71.1 132 6.01 50.5 20.1 1.86 4.22
Y
82.8
67.6
69.7
63.5
83.1
72.6
68.2
74.8
66.3
77.2
63.7
18.6
79.4
59.8
78.0
72.9
19.2
19.9
19.0
21.6
22.8
19.8
23.0
21.7
22.5
19.4
18.8
24.3
19.6
23.1
19.6
23.2
22.7
21.4
22.9
22.2
Zr
34.8
35.3
37.3
39.9
33.4
35.4
37.2
46.0
29.7
32.2
40.6
17.0
38.5
43.2
39.1
30.4
45.4
49.0
44.5
53.5
61.6
41.5
59.7
48.4
57.0
55.1
40.9
60.1
38.4
54.9
40.3
56.2
52.7
44.6
56.5
56.4
Nb
Mo
Ag
In
Sn
123
126
133
149
163
122
135
131
145
139
130
168
120
140
121
143
133
106
116
138
Ba
La
4.76
4.95
4.49
6.06
6.64
5.24
6.14
4.67
7.04
5.84
5.15
6.99
4.21
5.45
4.69
5.12
6.90
5.10
5.84
5.42
Ce
22.5
20.3
18.9
26.9
24.3
20.9
26.1
20.2
28.2
22.0
23.1
27.2
17.3
21.8
20.7
20.3
25.3
20.2
21.1
21.1
Pr
3.95
3.24
3.64
4.89
4.40
3.90
4.81
3.71
4.62
4.06
3.38
4.58
3.35
3.98
3.58
3.94
4.66
3.54
4.02
3.98
4.50
0.042 0.233 2.46 20.4 13.6 56.3 10.9
4.42
0.166 1.91 18.3 10.4 45.0 8.79
4.83
0.012 0.232 1.92 19.4 11.3 51.7 10.1
3.99
0.170 1.61 24.3 10.8 47.5 8.93
5.05
0.181 2.28 19.1 14.5 65.2 12.1
4.37
0.128 2.29 21.3 10.8 50.0 10.3
4.67
0.199 2.16 20.5 10.9 46.0 8.30
4.61
0.035 0.148 2.25 25.9 9.99 47.8 8.98
3.42 0.10
0.110 1.78 25.7 16.0 59.3 10.5
4.65
0.039 0.227 2.80 24.3 12.6 59.8 10.7
4.55 0.25
0.220 2.17 22.4 9.83 43.1 8.32
0.64
0.004 0.073 0.69 38.7 0.82 4.24 0.90
4.99
0.211 2.35 20.2 13.4 55.8 10.7
4.03
0.141 1.57 21.9 11.3 44.5 8.36
4.64
0.132 2.16 22.9 12.5 56.5 10.4
3.99
0.210 2.38 25.3 14.3 60.9 10.8
1.49
0.104 1.25
0.99
0.132 1.22
1.18
0.005 0.112 1.65
2.28 0.17
0.082 1.17
1.49
0.024 0.111 1.66
1.52
0.079 0.94
1.77
0.090 1.31
1.11
0.041 0.092 1.35
1.95
0.006 0.094 1.30
0.99
0.100 1.28
1.95
0.042 0.100 0.77
1.58 0.06 0.036 0.107 1.47
1.13
0.090 1.20
1.47
0.110 1.27
1.65
0.094 1.26
1.39
0.046 0.152 1.50
1.71
0.112 1.33
1.70
0.095 1.20
1.62
0.115 1.38
1.21
0.008 0.071 1.51
Nd
59.5
47.7
57.5
48.5
62.6
52.9
46.3
50.4
52.7
58.4
39.1
7.37
55.8
46.4
57.5
58.6
23.1
20.4
19.8
25.4
25.0
20.2
24.5
21.8
25.9
23.1
19.8
26.6
19.9
22.4
20.5
21.4
26.2
21.7
22.7
21.3
16.6
12.5
14.1
13.8
18.6
15.9
12.1
14.6
14.5
17.7
13.8
2.60
15.5
10.8
17.0
14.8
6.60
6.90
6.04
7.47
6.15
6.56
6.75
6.26
7.68
6.19
6.62
7.80
5.76
7.15
5.96
6.68
7.58
5.55
7.36
7.39
Sm
Eu
3.18
2.97
3.93
3.13
3.41
3.29
2.92
3.64
2.91
3.64
2.42
1.05
3.17
2.65
3.28
3.03
2.01
2.26
1.93
2.29
2.15
1.65
2.43
2.17
2.30
2.07
2.04
2.25
1.91
1.98
1.96
1.81
1.83
1.90
2.05
2.01
Gd
16.8
14.2
17.0
14.6
17.3
15.6
14.3
14.8
16.2
18.4
11.9
3.55
17.9
12.3
16.2
12.9
6.17
6.17
6.63
8.23
7.21
6.37
6.54
7.32
7.21
5.79
5.72
7.03
5.36
6.38
5.25
5.66
6.88
6.29
6.60
6.17
Dy
16.8
12.0
14.4
11.5
16.4
14.4
12.7
14.8
13.8
16.8
12.3
4.46
15.5
11.5
15.6
14.7
4.06
4.59
3.67
6.03
5.44
4.69
4.87
4.82
5.43
5.04
4.19
5.50
3.87
5.30
5.68
4.47
5.06
4.83
5.19
5.28
Er
8.56
7.55
8.62
7.81
10.1
8.34
8.08
7.78
8.13
9.07
6.79
2.33
9.59
6.54
9.31
8.30
2.72
2.38
2.01
2.60
2.47
1.82
3.20
2.49
2.73
2.58
1.84
2.63
1.70
2.67
2.13
2.16
2.01
2.71
2.60
2.54
Yb
7.88
6.31
6.84
6.30
8.55
7.73
7.13
7.68
7.25
8.30
6.46
1.86
9.15
7.22
7.47
7.23
1.23
2.00
1.65
1.59
1.80
1.82
1.96
2.39
1.70
1.99
1.20
1.69
1.62
2.21
0.83
1.72
1.50
1.71
1.87
2.32
Pb
0.67
0.41
0.52
0.56
0.45
0.45
0.43
0.45
0.71
0.61
0.62
0.14
0.49
0.56
0.51
0.59
0.64
0.45
0.61
0.87
0.76
0.52
0.65
0.57
0.69
0.47
0.66
0.61
0.44
0.48
0.46
0.62
0.60
0.53
0.48
0.65
180
core
rim
single
rim
core
rim
core
core
core
core
rim
core
core
core
rim
core
single
rim
core
core
rim
core
rim
rim
core
core
rim
single
core
rim
single
single
single
single
PN-2-1-2
PN-2-1-3
PN-2-1-4
PN-2-2-1
PN-2-2-2
PN-2-2-3
PN-2-3-1
PN-2-3-2
PN-2-4-1
PN-2-4-2
Spot Location
P22692-2A-1-2
P22692-2A-11-2
P22692-2A-11-4
P22692-2A-11-5*
P22692-2A-11-6
P22692-2A-12-1
P22692-2A-12-2
P22692-2A-12-3
P22692-2A-12-4
P22692-2A-12-5
P22692-2A-15-2
P22692-2A-15-3
P22692-2A-15-4
P22692-2A-2-3
P22692-2A-5-1*
P22692-2A-5-2
P22692-2A-6-2
P22692-2A-8-1*
P22692-2A-8-2
P22692-2A-8-3
P22692-2A-9-1
P22692-2A-9-2
P22692-2A-9-4
P22692-2A-9-5*
Sample ID
Eruption Date
dacite early June 15
dacite early June 15
dacite early June 15
dacite early June 15
dacite early June 15
dacite early June 15
dacite early June 15
dacite early June 15
dacite early June 15
dacite early June 15
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
andesite June 7-12
Table B3. Continued.
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hst
Mg-Hst
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hst
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Tsch-Prg
Mg-Hbl
Mg-Hbl
Mg-Hbl
Tsch-Prg
187
147
148
155
161
194
148
160
165
164
207
142
154
448
446
125
185
171
130
170
163
178
200
174
732
200
169
164
163
426
166
135
144
331
832
816
821
832
832
865
817
837
844
826
854
821
833
943
947
797
849
836
802
836
844
847
847
839
965
878
827
849
834
917
838
811
836
896
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
47.4
49.0
48.4
49.0
48.5
47.9
49.2
48.6
48.3
48.2
47.5
49.1
49.4
42.4
41.9
49.7
46.8
47.3
49.1
47.1
48.0
46.8
47.2
47.9
41.5
46.2
48.0
48.3
49.1
44.0
48.8
49.2
48.9
44.6
0.81
0.74
0.74
0.72
0.73
0.85
0.82
0.88
0.76
0.74
0.93
0.81
0.79
2.05
1.97
0.59
0.86
0.78
0.63
0.79
0.79
0.85
0.79
0.79
1.77
0.84
0.78
0.76
0.84
1.69
0.82
0.70
0.72
0.57
8.6
7.3
7.3
7.7
8.1
8.7
7.3
7.6
7.8
7.9
9.1
7.1
7.3
13.0
12.7
6.6
8.5
8.2
6.8
8.2
7.7
8.2
8.9
8.2
13.0
8.8
8.2
7.8
7.7
12.9
7.9
6.8
7.0
11.7
10.6
10.5
10.4
10.7
10.9
10.6
10.4
10.2
10.4
10.5
10.8
10.2
10.3
11.8
11.7
10.8
10.9
10.9
10.8
10.8
10.3
10.5
10.7
10.5
11.7
10.9
10.7
10.5
10.8
11.6
10.2
10.4
10.3
11.3
13.6
13.0
13.0
13.9
14.1
13.8
12.9
13.3
13.4
14.0
14.1
12.8
13.3
11.2
10.6
13.1
14.0
14.2
13.3
14.4
13.6
14.2
14.4
13.9
10.6
14.7
13.9
14.0
10.9
11.0
13.5
12.7
12.9
11.0
14.8
15.9
15.5
15.1
14.7
15.1
15.7
15.5
15.4
14.8
14.5
15.9
15.5
14.7
15.0
15.2
14.0
14.0
14.9
14.0
15.1
14.6
13.8
14.9
15.0
13.7
14.9
15.1
16.8
14.6
15.3
15.9
15.8
15.9
0.45
0.46
0.46
0.57
0.57
0.56
0.47
0.49
0.54
0.52
0.56
0.40
0.60
0.15
0.12
0.61
0.64
0.63
0.61
0.62
0.55
0.54
0.61
0.53
0.14
0.72
0.49
0.59
0.42
0.25
0.49
0.48
0.56
0.16
1.28
1.09
1.20
1.31
1.38
1.44
1.14
1.22
1.28
1.16
1.35
1.28
1.11
2.22
2.26
1.04
1.35
1.30
1.11
1.28
1.26
1.25
1.36
1.27
2.28
1.51
1.26
1.34
1.26
1.98
1.30
1.09
1.20
2.06
0.34
0.21
0.25
0.22
0.36
0.37
0.21
0.22
0.20
0.28
0.37
0.21
0.19
0.69
0.79
0.28
0.37
0.33
0.27
0.34
0.25
0.31
0.42
0.25
0.82
0.43
0.30
0.24
0.22
0.42
0.26
0.19
0.20
0.69
0.04
0.00
0.02
0.00
0.01
0.02
0.05
0.02
0.05
0.01
0.01
0.01
0.04
0.07
0.08
0.00
0.04
0.01
0.01
0.00
0.00
0.01
0.03
0.04
0.00
0.03
0.03
0.02
0.00
0.02
0.00
0.00
0.02
0.18
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
F
0.06
0.01
0.01
0.01
0.03
0.02
0.00
0.07
0.12
0.11
0.00
0.08
0.11
0.13
0.12
0.06
0.11
0.00
0.13
0.07
0.21
0.28
0.08
0.11
0.08
0.06
0.09
0.06
0.05
0.18
0.06
0.02
0.11
0.13
Cl
0.050
0.035
0.040
0.035
0.032
0.054
0.036
0.044
0.042
0.047
0.041
0.041
0.038
0.015
0.012
0.018
0.039
0.036
0.024
0.041
0.040
0.048
0.041
0.047
0.012
0.049
0.041
0.047
0.040
0.017
0.046
0.033
0.038
0.014
SO2
0.000
0.015
0.005
0.000
0.004
0.000
0.000
0.015
0.005
0.014
0.015
0.018
0.000
0.014
0.017
0.014
0.000
0.000
0.011
0.000
0.005
0.000
0.006
0.006
0.012
0.013
0.000
0.000
0.000
0.001
0.000
0.012
0.015
0.045
98.1
98.3
97.3
99.3
99.5
99.3
98.2
98.3
98.2
98.3
99.3
98.0
98.6
98.5
97.3
98.1
97.6
97.8
97.7
97.6
97.9
97.5
98.3
98.5
96.9
98.0
98.7
98.8
98.2
98.5
98.7
97.4
97.7
98.4
Total
181
3.13
6.51
3.70
5.79
5.77
8.25
4.26
7.14
3.20
5.88
5.27
6.03
5.94
6.15
5.90
5.75
7.74
9.33
6.29
PN-2-1-2
PN-2-1-3
PN-2-1-4
PN-2-2-1
PN-2-2-2
PN-2-2-3
PN-2-3-1
PN-2-3-2
PN-2-4-1
PN-2-4-2
7.14
5.78
5.34
6.67
2.03
3.56
4.00
4.28
5.52
4.76
6.41
6.06
5.45
3.03
237684
242960
238828
222161
223875
222929
252290
244666
281345
268322
228559
196718
191732
176102
174708
192556
195528
198301
203006
198007
201743
189145
196750
232173
179532
213920
220237
198797
212146
195017
224675
195531
212842
210112
69.0
61.0
66.7
67.7
82.5
73.9
63.1
60.1
63.7
75.8
61.7
66.1
70.1
74.7
70.6
86.2
84.3
87.9
98.4
88.3
64.6
89.0
82.9
61.4
76.6
98.6
70.4
68.0
77.3
94.9
58.9
62.4
56.8
8.53
4694
5442
5593
4515
4911
5005
5036
4801
4935
4947
5278
5464
5311
11871
12522
4413
5062
4940
4393
4683
5069
5260
5520
5179
11653
4922
4805
5327
6289
10606
5756
5250
5747
3345
280
284
330
264
342
322
306
307
329
366
328
286
264
454
491
234
262
255
247
247
261
267
279
276
493
286
252
270
295
344
255
242
262
218
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
P22692-2A-1-2
P22692-2A-11-2
P22692-2A-11-4
P22692-2A-11-5*
P22692-2A-11-6
P22692-2A-12-1
P22692-2A-12-2
P22692-2A-12-3
P22692-2A-12-4
P22692-2A-12-5
P22692-2A-15-2
P22692-2A-15-3
P22692-2A-15-4
P22692-2A-2-3
P22692-2A-5-1*
P22692-2A-5-2
P22692-2A-6-2
P22692-2A-8-1*
P22692-2A-8-2
P22692-2A-8-3
P22692-2A-9-1
P22692-2A-9-2
P22692-2A-9-4
P22692-2A-9-5*
Sample ID
Table B3. Continued.
Co
59.7
67.1
60.9
50.2
55.0
54.2
66.8
63.9
70.9
65.1
63.5
57.0
49.4
57.2
58.9
43.6
46.2
43.3
43.5
45.5
50.8
44.9
45.6
56.5
61.8
46.3
52.8
52.1
56.7
51.3
53.0
50.3
52.7
60.2
Ni
93.9
90.0
97.3
69.4
75.4
76.9
115
113
135
107
96.3
136
96.4
128
148
59.8
57.3
61.2
55.3
62.1
87.5
67.4
62.3
89.1
172
64.9
71.9
84.3
141
263
74.2
88.6
74.1
264
Cu
0.71
0.77
1.34
1.67
1.39
2.10
0.83
0.94
2.66
2.37
1.60
1.34
0.78
13.3
2.39
1.05
0.65
1.65
0.85
1.50
2.60
1.44
1.17
1.91
3.87
5.39
2.53
2.76
3.62
5.99
15.4
3.72
2.83
6.94
242
219
257
231
254
256
245
268
323
309
246
198
206
73.7
56.2
212
222
219
223
224
209
215
214
248
56.0
246
237
214
216
126
191
201
220
76.9
Zn
Ga
16.3
14.8
19.4
14.7
18.4
18.8
15.7
16.9
20.8
22.4
17.7
15.1
15.2
19.9
17.3
13.2
15.1
15.4
14.3
15.2
14.6
17.4
17.5
15.4
18.4
18.0
17.3
13.9
16.4
16.2
19.7
16.3
18.5
16.5
Ge
3.03
3.34
3.71
3.40
4.04
3.70
3.66
3.72
6.06
5.07
3.62
2.46
2.37
1.31
1.20
3.34
3.19
3.17
2.80
2.99
2.76
3.10
2.89
3.30
2.66
3.20
3.16
2.66
2.71
1.89
2.74
2.68
2.46
1.76
Rb
0.64
0.38
0.58
0.77
0.69
0.70
0.34
0.42
0.64
0.61
0.70
0.21
0.13
6.22
2.35
0.68
0.74
0.41
0.50
0.44
0.66
0.77
0.55
0.49
2.99
0.40
1.94
0.40
0.46
0.76
6.48
0.21
3.35
5.65
Sr
27.5
36.3
30.7
27.9
27.6
28.0
26.3
27.0
28.0
28.5
39.3
35.5
30.2
363
341
24.2
29.0
28.2
25.2
29.3
30.9
32.8
34.5
28.6
285
28.4
31.6
35.3
50.0
197
80.6
37.6
38.3
214
Y
66.3
62.3
64.7
76.8
78.7
79.6
62.1
68.1
63.8
70.6
68.2
59.1
69.4
25.5
21.9
92.4
83.8
86.9
94.9
90.2
70.7
90.8
79.9
72.7
22.0
101
80.5
71.7
64.9
27.6
59.8
64.8
67.3
11.1
Zr
29.9
36.9
34.4
28.6
25.4
35.8
31.4
30.7
33.3
25.4
38.3
41.2
38.6
51.0
47.7
25.3
28.2
30.2
30.4
31.4
37.3
34.5
33.9
34.6
40.7
31.5
34.0
35.5
41.6
28.2
51.8
37.2
45.9
58.9
Nb
Mo
Ag
In
Sn
Ba
La
Ce
56.8
40.0
47.6
26.0
24.4
63.5
63.7
64.5
58.8
62.0
46.1
60.6
60.6
56.2
17.9
67.8
57.7
44.6
42.3
15.7
40.5
41.6
45.7
38.2
Pr
11.6
7.62
8.74
4.19
4.13
12.5
11.5
11.8
11.1
11.2
8.97
11.7
10.9
9.92
3.20
12.8
10.9
8.81
7.87
2.64
7.59
8.43
8.58
5.47
Nd
58.4
41.7
47.4
27.4
22.4
67.4
62.5
66.5
60.1
64.1
46.6
66.9
58.2
54.3
17.4
67.8
58.8
45.7
42.9
17.9
36.3
44.2
45.5
25.6
4.35
0.029 0.217 2.11 20.1 11.3 59.3 10.5 54.5
4.10 0.07 0.021 0.143 1.56 18.6 10.3 48.2 8.09 44.7
4.38
0.034 0.180 2.42 28.1 11.9 59.7 9.99 52.1
4.65
0.194 2.24 20.2 13.0 61.4 11.1 57.4
5.36
0.210 2.76 24.2 13.5 71.0 12.3 64.2
5.52 0.05 0.007 0.240 2.79 21.9 11.7 62.8 11.1 59.1
3.76
0.003 0.169 1.86 15.7 9.40 50.1 9.02 47.9
4.20
0.036 0.210 2.31 17.4 8.97 49.7 9.24 46.7
4.37
0.290 2.84 18.5 9.39 57.3 9.53 48.6
4.65
0.295 3.03 20.0 12.4 63.8 11.1 56.7
4.84
0.218 2.82 26.4 12.5
4.25
0.027 0.132 1.66 21.3 8.93
4.29
0.006 0.154 1.93 19.0 10.8
2.37
0.016 0.087 1.11 141 8.97
1.67
0.035 0.074 1.20 140 6.41
5.21
0.196 2.04 19.7 14.4
4.82
0.174 2.07 24.2 13.4
4.63
0.031 0.198 2.18 20.1 14.0
4.13
0.024 0.171 1.95 14.6 13.0
4.76
0.003 0.180 2.21 18.4 13.6
4.36
0.038 0.155 1.73 22.7 10.4
5.57
0.176 2.45 27.6 13.9
5.13
0.005 0.184 2.40 27.3 13.6
4.37
0.014 0.191 2.17 18.0 10.9
1.53
0.036 0.088 0.96 100 3.79
5.62
0.003 0.184 2.46 24.9 12.9
4.55 0.09
0.188 2.14 32.6 12.6
3.98
0.138 1.88 20.2 10.6
3.97
0.152 1.85 26.0 9.65
1.74
0.064 0.070 1.01 56.7 4.63
4.28 0.15 0.032 0.173 1.61 79.7 10.6
4.25
0.124 1.50 24.6 9.93
4.54 0.01 0.027 0.140 1.92 50.9 10.7
2.69
0.032 0.027 0.91 88.9 12.9
14.5
14.5
14.0
16.6
18.4
17.1
13.8
13.2
12.2
14.5
14.9
11.5
14.0
7.65
7.20
18.8
17.8
17.1
18.3
17.4
13.3
16.7
16.6
13.9
5.50
19.1
15.0
13.8
12.9
5.32
12.1
11.5
13.0
5.31
Sm
Eu
2.97
2.68
2.64
2.91
3.33
3.01
2.66
2.65
3.22
3.25
3.23
2.56
2.99
1.74
1.95
3.18
3.26
3.24
3.11
3.34
3.00
3.58
3.74
3.05
1.59
3.27
3.18
2.74
2.61
1.28
2.72
2.50
2.63
1.32
Gd
14.1
12.5
14.1
16.8
17.4
16.2
13.4
14.7
13.4
13.9
14.7
11.4
15.5
7.24
6.89
17.7
16.1
17.3
19.3
17.7
13.7
17.5
15.3
14.8
6.87
19.3
15.5
11.3
13.7
5.14
11.2
12.8
13.6
2.90
Dy
12.1
12.4
12.8
12.9
16.3
14.5
12.0
12.6
11.2
12.7
13.8
10.9
12.7
6.05
5.22
17.2
15.5
16.7
17.5
17.0
13.1
16.6
14.1
14.4
3.35
19.9
17.3
14.1
12.2
6.23
9.43
11.2
12.0
1.55
Er
6.99
7.27
6.69
8.57
9.07
9.20
6.64
7.45
5.69
6.95
7.36
6.43
6.87
2.87
3.48
9.77
10.2
10.0
11.0
9.14
8.13
10.0
9.15
7.50
2.56
11.0
8.80
8.04
7.02
2.93
6.98
7.38
7.45
0.89
Yb
6.56
6.61
6.55
7.75
8.55
8.20
6.02
6.92
7.18
7.41
5.51
5.33
7.11
2.36
1.43
7.93
8.98
9.25
9.27
8.94
6.75
9.46
7.34
7.03
1.66
9.75
8.68
7.25
6.38
2.61
5.92
6.19
6.51
0.83
Pb
0.55
0.38
0.54
0.66
0.65
0.69
0.42
0.51
0.67
0.70
0.71
0.39
0.51
2.02
0.68
0.47
0.52
0.48
0.45
0.47
0.50
0.60
0.59
0.48
0.52
0.71
0.82
0.41
0.64
0.78
2.13
0.43
0.94
0.96
182
rim
core
core
rim
core
rim
core
core
single
single
single
core
core
rim
rim
core
rim
core
rim
core
rim
single
rim
core
core
single
single
single
single
single
3b-1-1
3b-1-2
3b-1-3
3b-1-4
3b-1-5
3b-2-1
3b-2-2
3b-3-1
3b-3-2
3b-4-1
3b-5-2
3b-6-2
3b-6-3
3b-6-4
3b-6-5
3b-6-6
3b-7-2
3b-7-4
3b-7-5
Spot Location
3a-1-2
3a-1-3
3a-1-4
3a-2-2
3a-2-3
3a-3-1
3a-3-2
3a-3-3
3a-4-1
3a-4-2
3a-5-2
Sample ID
Eruption Date
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite middle June 15
dacite early-middle June 15
dacite early-middle June 15
dacite early-middle June 15
dacite early-middle June 15
dacite early-middle June 15
dacite early-middle June 15
dacite early-middle June 15
dacite early-middle June 15
dacite early-middle June 15
dacite early-middle June 15
dacite early-middle June 15
Table B3. Continued.
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
174
164
149
149
135
141
151
137
136
152
128
156
173
175
150
165
191
139
161
179
178
178
142
190
166
193
157
140
182
138
835
835
827
825
807
808
819
813
804
825
803
819
838
839
813
822
823
815
813
850
848
828
819
862
838
855
844
811
841
819
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
48.4
48.9
50.2
50.1
50.1
49.9
50.1
50.5
51.0
50.5
50.7
49.8
48.3
48.6
49.6
49.0
48.3
50.8
49.1
49.4
48.4
49.5
50.4
48.8
48.8
47.7
49.8
50.5
48.6
50.7
0.81
0.80
0.79
0.71
0.67
0.77
0.74
0.71
0.72
0.79
0.64
0.73
0.81
0.82
0.73
0.81
0.80
0.77
0.82
0.80
0.89
0.83
0.74
0.87
0.75
0.96
0.82
0.67
0.84
0.71
8.5
8.0
7.3
7.4
7.0
7.2
7.6
7.0
7.1
7.5
6.6
7.8
8.2
8.4
7.7
8.1
9.0
7.1
8.1
8.3
8.3
8.4
7.2
8.6
7.9
8.9
7.6
7.1
8.4
7.0
10.9
10.6
10.3
10.5
10.5
10.6
10.5
10.5
10.7
10.5
10.6
10.7
10.9
10.9
11.0
10.8
11.0
10.5
10.8
10.4
10.6
10.6
10.5
10.3
10.6
10.7
10.6
10.5
10.6
10.4
14.2
14.1
13.6
13.4
13.3
13.0
13.9
13.3
13.4
12.7
13.2
13.7
14.1
14.3
14.0
13.7
14.1
12.8
13.2
13.9
14.0
13.9
13.3
14.0
13.9
14.3
13.7
13.2
13.6
13.7
14.7
15.1
15.6
15.8
15.9
16.1
15.3
15.9
15.7
16.3
16.0
15.3
14.8
14.5
15.1
15.2
14.5
16.4
15.4
15.2
15.1
14.9
16.0
15.0
15.1
14.7
15.3
15.8
15.4
15.6
0.53
0.54
0.57
0.53
0.48
0.44
0.54
0.54
0.55
0.48
0.57
0.56
0.61
0.63
0.57
0.50
0.47
0.47
0.41
0.60
0.57
0.53
0.52
0.57
0.61
0.52
0.69
0.53
0.52
0.62
1.40
1.31
1.15
1.21
1.14
1.14
1.19
1.13
1.15
1.19
0.99
1.16
1.23
1.34
1.20
1.23
1.29
1.16
1.26
1.33
1.28
1.25
1.14
1.43
1.21
1.45
1.24
1.14
1.22
1.11
0.39
0.29
0.23
0.29
0.25
0.21
0.28
0.19
0.22
0.23
0.21
0.32
0.32
0.37
0.28
0.36
0.43
0.18
0.26
0.29
0.25
0.31
0.25
0.30
0.28
0.31
0.23
0.21
0.27
0.17
0.02
0.00
0.00
0.00
0.00
0.04
0.01
0.05
0.02
0.00
0.00
0.02
0.00
0.01
0.00
0.03
0.02
0.00
0.06
0.02
0.04
0.01
0.00
0.03
0.01
0.03
0.05
0.04
0.00
0.03
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
F
0.10
0.08
0.02
0.00
0.01
0.02
0.05
0.09
0.11
0.04
0.12
0.11
0.03
0.08
0.18
0.05
0.06
0.16
0.06
0.06
0.06
0.11
0.12
0.19
0.05
0.05
0.11
0.04
0.00
0.10
Cl
0.043
0.052
0.044
0.038
0.044
0.041
0.035
0.034
0.036
0.036
0.037
0.030
0.032
0.030
0.032
0.040
0.048
0.034
0.033
0.054
0.042
0.046
0.035
0.052
0.045
0.045
0.036
0.035
0.051
0.037
SO2
0.000
0.008
0.015
0.007
0.027
0.000
0.013
0.005
0.020
0.010
0.005
0.004
0.008
0.010
0.009
0.000
0.000
0.016
0.013
0.000
0.007
0.011
0.019
0.022
0.011
0.014
0.019
0.009
0.011
0.000
99.9
99.7
99.8
100.0
99.5
99.5
100.3
100.0
100.6
100.3
99.7
100.2
99.3
100.0
100.4
99.8
100.0
100.4
99.5
100.4
99.4
100.5
100.2
100.2
99.2
99.7
100.2
99.9
99.5
100.2
Total
183
6.24
6.97
7.11
5.67
6.77
6.37
5.25
5.02
6.55
5.89
5.75
5.65
6.67
8.13
6.30
6.55
5.86
7.43
6.96
6.22
6.52
6.21
6.39
5.65
5.48
4.53
6.17
6.65
5.89
6.68
3b-1-1
3b-1-2
3b-1-3
3b-1-4
3b-1-5
3b-2-1
3b-2-2
3b-3-1
3b-3-2
3b-4-1
3b-5-2
3b-6-2
3b-6-3
3b-6-4
3b-6-5
3b-6-6
3b-7-2
3b-7-4
3b-7-5
240486
240982
254245
233682
232438
254275
228663
235811
232629
234520
218808
212576
225483
213880
215309
219767
215629
225891
223110
232313
236674
239405
242786
233793
238691
234089
225888
242946
221012
234135
84.1
79.3
57.7
75.0
68.1
70.6
63.0
63.7
83.5
67.9
73.0
95.0
105
83.9
95.7
82.6
87.7
75.3
65.8
66.9
57.5
72.3
62.5
60.6
66.3
70.6
75.1
67.6
59.6
71.8
4746
4858
5252
5237
4721
5056
5070
5047
5077
5215
4454
5015
5058
5519
4954
5384
5354
5019
5083
4994
5879
5534
4840
5206
5478
6019
6135
5042
5821
4600
356
346
311
342
309
342
322
305
312
327
269
322
311
315
321
320
310
312
312
292
360
372
311
336
315
334
334
319
354
313
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
3a-1-2
3a-1-3
3a-1-4
3a-2-2
3a-2-3
3a-3-1
3a-3-2
3a-3-3
3a-4-1
3a-4-2
3a-5-2
Sample ID
Table B3. Continued.
Co
58.6
64.5
67.3
67.3
62.8
74.3
65.3
63.2
62.0
62.4
56.4
61.9
54.6
49.8
56.9
60.3
55.6
63.5
59.1
59.5
65.4
63.0
63.2
62.4
62.2
57.6
56.7
67.8
65.4
59.7
76.3
91.4
113
114
123
119
93.2
97.2
97.7
97.1
84.5
90.7
70.5
65.7
76.2
98.5
93.5
113
104
105
97.6
84.8
101
111
112
91.6
85.5
109
129
93.9
Ni
Cu
2.91
2.97
4.66
0.84
0.82
0.82
0.95
3.14
0.93
0.85
3.16
1.48
0.78
3.22
6.11
2.65
1.14
20.2
0.95
2.75
0.92
0.64
0.90
1.22
1.07
1.22
1.56
1.06
1.36
0.99
269
304
299
273
277
300
282
277
284
279
272
270
274
275
303
274
259
251
252
260
283
286
292
281
274
265
256
285
261
297
Zn
Ga
19.9
20.7
20.5
21.4
17.7
20.0
19.7
18.2
20.0
20.2
16.1
20.7
18.4
20.2
21.2
20.5
19.4
17.3
17.2
19.6
21.3
22.4
18.0
20.1
19.8
20.7
20.1
18.9
19.3
18.3
Ge
4.64
5.24
4.61
4.75
4.07
4.85
3.63
3.95
4.66
4.37
4.05
4.28
3.98
4.32
5.25
4.15
4.09
3.46
3.69
4.05
3.54
4.18
4.13
3.94
4.41
4.07
3.37
4.11
3.49
4.25
Rb
0.75
0.50
1.90
0.64
0.62
0.56
0.54
0.59
0.78
0.47
0.16
0.89
0.75
0.69
0.72
0.82
0.68
0.28
0.45
1.03
0.49
0.72
0.35
0.71
0.45
1.12
0.68
0.47
0.80
0.52
Sr
30.5
27.3
32.9
31.7
28.9
29.2
29.7
31.3
31.1
31.5
25.3
27.8
29.3
30.0
29.5
28.3
31.2
30.3
30.6
29.6
36.4
31.3
26.6
33.4
29.4
38.8
36.9
30.0
45.4
26.0
Y
77.8
70.2
69.8
77.0
64.8
73.1
62.7
66.9
80.7
70.9
74.9
83.9
89.1
86.9
81.5
82.7
85.8
65.7
66.8
68.0
53.7
74.2
65.0
59.1
74.1
67.0
69.4
67.3
52.2
72.1
Zr
31.8
27.6
37.2
30.7
32.4
31.8
31.9
34.3
30.9
33.8
34.6
28.4
32.0
37.1
29.3
34.6
34.1
37.5
36.9
33.4
36.7
30.7
30.4
36.8
35.3
36.4
35.9
31.9
35.3
29.4
Nb
4.89
5.15
4.29
4.78
3.89
4.80
4.43
3.92
4.71
5.17
4.08
4.83
4.65
4.30
5.44
4.77
5.18
3.79
4.12
4.41
3.82
4.73
3.76
3.98
4.51
4.76
4.37
3.88
4.26
4.08
0.09
0.06
0.03
0.09
0.06
0.05
0.04
0.09
0.09
0.05
0.16
Mo
In
Sn
2.49
2.39
3.21
2.27
2.29
2.49
2.43
2.26
2.34
1.98
2.56
0.250 3.21
2.79
2.32
2.92
2.09
2.30
2.10
2.60
2.91
2.59
2.41
3.03
2.85
2.81
3.05
2.78
2.76
1.71
2.51
0.014 0.214
0.208
0.009 0.225
0.045 0.208
0.035 0.210
0.014 0.230
0.033 0.192
0.208
0.007 0.206
0.172
0.009 0.254
0.028 0.262
0.221
0.034 0.190
0.025 0.254
0.214
0.005 0.156
0.035 0.178
0.179
0.212
0.253
0.192
0.167
0.217
0.203
0.211
0.203
0.168
0.009 0.237
Ag
0.035
0.036
0.027
0.010
0.036
0.016
0.006
0.014
0.028
Ba
La
10.9
10.4
12.6
10.4
10.2
11.0
11.3
11.9
10.1
10.2
10.4
20.3 11.7
12.4
9.81
12.5
10.5
11.4
10.5
10.0
13.6
11.8
11.2
12.3
13.3
13.6
12.8
11.6
13.5
8.85
10.6
21.3
37.4
23.5
20.9
22.1
22.4
18.7
22.2
20.6
13.4
21.7
23.7
19.8
23.1
25.9
22.7
18.0
17.2
23.4
23.4
25.8
16.7
21.2
21.4
28.5
31.1
17.5
29.6
19.2
Ce
Pr
9.23
7.92
11.5
10.0
8.89
9.76
9.45
10.3
9.18
8.11
9.11
66.3 10.9
10.8
8.12
11.1
9.31
9.60
8.87
9.16
11.9
10.2
10.6
11.9
12.0
11.5
11.7
10.9
12.2
7.98
9.53
65.8
47.2
63.0
53.7
56.6
53.9
50.5
62.8
59.6
54.1
64.0
64.8
62.6
72.5
63.3
65.1
44.9
51.8
52.7
50.2
68.6
55.5
51.2
54.6
55.9
60.4
53.1
49.1
53.9
Nd
14.0
11.9
15.9
14.0
12.6
15.2
13.2
13.2
13.9
11.1
15.2
Sm
57.4 17.2
16.6
13.8
16.4
12.8
13.4
14.8
13.5
16.6
15.1
15.3
17.7
18.5
16.5
16.9
16.4
17.2
14.2
13.7
57.4
45.7
61.2
50.5
52.1
47.6
48.3
62.0
54.3
54.0
57.8
62.7
59.7
61.7
59.5
59.3
44.4
51.0
49.7
42.8
59.8
49.7
49.3
52.6
50.0
52.4
49.6
42.4
49.6
Eu
Gd
12.8
11.4
15.6
14.6
12.6
14.6
15.4
13.6
14.0
9.76
13.2
3.46 13.3
15.5
14.2
15.0
13.3
15.6
14.6
13.2
15.5
14.4
14.2
17.7
17.5
17.1
17.2
16.6
18.5
13.6
13.1
3.10
2.88
3.42
2.88
3.20
3.11
2.98
3.29
3.13
2.77
3.37
3.02
3.49
3.41
3.12
3.48
2.70
2.93
3.02
2.66
3.20
2.95
2.74
3.24
3.05
3.04
2.91
2.64
3.43
Dy
Er
7.38
5.96
7.76
7.62
6.75
8.60
6.83
7.37
7.37
5.59
6.59
13.2 8.49
7.81
7.89
8.55
6.77
7.48
7.06
7.11
8.88
8.49
8.59
8.19
10.6
9.92
8.51
9.19
8.54
7.22
7.68
14.0
14.0
14.5
12.8
13.6
13.2
12.7
14.2
12.4
14.2
15.9
15.6
15.6
13.4
15.9
14.6
12.5
12.7
12.4
9.38
13.5
12.2
11.1
14.5
11.8
12.9
12.3
9.75
13.4
Yb
Pb
0.80
0.77
0.81
0.45
0.61
0.55
0.71
0.69
0.52
0.62
0.53
7.81 0.68
0.61
0.83
0.70
0.54
0.58
0.64
0.56
0.62
0.71
0.44
0.69
0.67
0.79
0.74
0.62
0.73
0.51
0.55
7.89
7.65
7.49
7.15
7.26
6.68
6.83
7.75
6.76
7.65
8.99
8.56
8.27
8.71
8.27
8.95
5.61
6.13
6.92
5.71
6.95
6.89
5.83
7.68
7.42
7.20
7.01
5.06
7.35
184
single
rim
core
core
rim
core
core
rim
core
single
rim
single
single
single
core
rim
rim
core
core
rim
core
core
core
core
rim
core
core
core
single
rim
core
rim
core
single
core
rim
core
rim
PN-1-1-1
PN-1-1-2
PN-1-1-3
PN-1-2-2
PN-1-2-3
PN-1-3-2
PN-1-3-3
PN-1-3-4
PN-1-3-5
PN-1-4-2
PN-1-4-3
PN-1-4-4
PN-1-5-1
PN-1-5-2
PN-1-5-3
PN-1-5-4
PN-1-5-5
PN-1-6-2
PN-1-7-1
PN-1-7-2
PN-1-7-3
PN-1-7-4
Spot Location
3d-1-3
3d-2-1
3d-2-10
3d-2-2
3d-2-3
3d-2-4
3d-2-5
3d-2-6
3d-2-7
3d-2-8
3d-2-9
3d-3-3
3d-4-1
3d-4-3
3d-5-2
3d-5-3
Sample ID
Eruption Date
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
dacite middle-late June 15
Table B3. Continued.
Mg-Hbl
Mg-Hbl
Tsch-Prg
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Tsch-Prg
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
207
187
315
170
194
165
187
176
169
124
160
372
148
146
167
150
148
148
182
179
198
175
151
136
211
172
151
155
166
167
158
152
167
162
148
177
170
147
861
824
904
847
852
846
846
836
847
800
831
907
829
817
834
819
822
824
845
855
854
843
827
823
883
827
818
830
838
835
830
830
847
829
824
839
834
818
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
47.0
48.0
44.8
48.6
47.5
48.4
47.6
47.6
48.1
50.4
48.1
44.1
49.2
50.1
48.9
50.1
49.4
50.6
48.9
49.5
47.6
49.8
50.2
51.0
48.4
48.7
50.4
49.4
48.3
48.9
48.8
50.0
49.6
49.9
49.6
49.0
48.6
50.0
0.99
0.91
1.50
0.81
0.84
0.81
0.94
0.81
0.84
0.69
0.80
1.39
0.74
0.78
0.77
0.75
0.85
0.86
0.71
0.80
0.83
0.74
0.72
0.77
0.89
0.73
0.78
0.73
0.81
0.74
0.72
0.76
0.76
0.85
0.73
0.87
0.79
0.73
9.2
8.9
11.2
8.0
8.9
7.9
8.6
8.4
8.0
6.6
8.0
12.2
7.3
7.3
8.1
7.5
7.4
7.4
8.5
8.2
9.0
8.2
7.4
6.9
9.0
8.3
7.5
7.7
8.1
8.1
7.9
7.4
7.8
8.0
7.4
8.4
8.2
7.4
10.5
10.9
11.1
10.3
10.8
10.5
10.7
10.7
10.5
10.5
10.8
11.1
10.7
10.5
10.8
10.6
10.6
10.4
10.8
10.3
10.9
10.6
10.5
10.5
10.5
10.9
10.5
10.6
10.8
10.8
10.9
10.5
10.3
10.7
10.6
10.6
10.7
10.7
14.1
14.6
13.4
13.5
14.0
13.8
14.1
13.7
13.8
12.6
14.0
16.0
13.5
12.9
14.0
13.2
13.5
13.1
14.2
13.9
14.6
13.4
13.1
13.4
14.4
14.2
13.4
13.4
13.7
14.1
14.1
13.5
14.2
13.3
13.1
13.6
13.8
13.2
14.5
14.3
13.7
15.3
14.8
15.3
14.7
14.7
15.0
16.4
15.1
12.3
15.6
15.9
14.9
15.7
15.1
15.7
14.4
15.2
14.2
15.4
15.8
16.2
14.6
14.5
15.6
15.6
15.1
14.7
14.9
15.6
15.1
15.7
15.7
15.2
15.1
15.8
0.43
0.44
0.46
0.50
0.49
0.55
0.51
0.51
0.57
0.44
0.50
0.55
0.58
0.49
0.57
0.53
0.57
0.52
0.69
0.62
0.60
0.58
0.56
0.60
0.72
0.62
0.52
0.52
0.53
0.62
0.60
0.59
0.65
0.48
0.52
0.50
0.53
0.55
1.56
1.32
1.76
1.37
1.45
1.30
1.33
1.34
1.29
1.11
1.32
1.72
1.14
1.15
1.33
1.19
1.21
1.26
1.32
1.33
1.43
1.34
1.20
1.11
1.46
1.23
1.17
1.28
1.32
1.29
1.27
1.16
1.22
1.33
1.24
1.35
1.28
1.11
0.35
0.43
0.50
0.31
0.34
0.23
0.34
0.33
0.31
0.16
0.33
0.64
0.22
0.18
0.30
0.23
0.23
0.21
0.33
0.30
0.32
0.29
0.23
0.17
0.31
0.41
0.22
0.23
0.32
0.33
0.28
0.24
0.26
0.26
0.23
0.28
0.30
0.23
0.00
0.00
0.04
0.03
0.00
0.00
0.01
0.00
0.00
0.03
0.02
0.05
0.01
0.00
0.04
0.01
0.05
0.04
0.00
0.01
0.03
0.00
0.02
0.04
0.08
0.00
0.00
0.02
0.01
0.02
0.05
0.00
0.07
0.02
0.00
0.01
0.01
0.02
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
F
0.14
0.12
0.10
0.12
0.05
0.07
0.04
0.12
0.08
0.12
0.02
0.02
0.06
0.03
0.04
0.03
0.06
0.05
0.03
0.08
0.10
0.13
0.04
0.07
0.10
0.05
0.03
0.00
0.08
0.00
0.13
0.10
0.06
0.00
0.06
0.00
0.05
0.08
Cl
0.067
0.049
0.043
0.047
0.045
0.040
0.045
0.036
0.037
0.036
0.038
0.081
0.046
0.039
0.041
0.037
0.038
0.040
0.029
0.043
0.031
0.044
0.038
0.036
0.048
0.035
0.041
0.045
0.037
0.047
0.037
0.036
0.037
0.043
0.036
0.050
0.043
0.037
SO2
0.017
0.005
0.003
0.010
0.000
0.009
0.034
0.000
0.015
0.000
0.005
0.000
0.011
0.010
0.003
0.000
0.000
0.000
0.005
0.019
0.025
0.001
0.009
0.011
0.000
0.008
0.000
0.000
0.002
0.008
0.013
0.004
0.000
0.000
0.000
0.000
0.006
0.000
98.8
100.0
98.6
98.9
99.2
98.9
99.0
98.3
98.5
99.1
99.0
100.2
99.1
99.3
99.7
99.8
99.0
100.1
99.9
100.3
99.7
100.6
99.8
100.8
100.5
99.6
100.2
99.5
99.2
99.7
99.7
99.9
100.1
100.5
99.2
99.9
99.3
99.9
Total
185
5.39
5.88
5.73
5.04
6.51
5.76
5.08
4.91
5.81
6.07
5.47
5.81
5.92
7.27
5.21
6.24
6.48
4.28
5.85
5.37
4.84
6.92
5.11
5.20
4.80
4.86
4.21
3.74
5.71
5.88
7.42
5.36
6.61
6.09
5.05
5.63
5.01
5.29
PN-1-1-1
PN-1-1-2
PN-1-1-3
PN-1-2-2
PN-1-2-3
PN-1-3-2
PN-1-3-3
PN-1-3-4
PN-1-3-5
PN-1-4-2
PN-1-4-3
PN-1-4-4
PN-1-5-1
PN-1-5-2
PN-1-5-3
PN-1-5-4
PN-1-5-5
PN-1-6-2
PN-1-7-1
PN-1-7-2
PN-1-7-3
PN-1-7-4
246265
235376
208809
229313
213437
229032
222444
195378
213375
217834
219132
209496
243980
228406
246584
243113
227049
227308
218275
211740
221106
208558
243445
226413
215155
214761
223654
218144
210702
218135
225408
221197
222993
218213
251506
253496
222344
253276
73.8
74.5
84.1
70.3
75.4
64.3
79.1
88.0
76.5
65.2
78.0
100
70.8
67.5
75.6
76.1
72.7
62.7
109
67.4
111
82.0
69.3
81.1
63.7
84.0
66.2
66.3
79.3
93.5
102
64.9
63.9
62.9
74.9
63.9
74.9
72.7
5822
5373
9191
4968
5467
5561
5754
4897
5418
4764
5082
7774
5109
4947
4751
4904
6527
5497
5040
5154
4916
4691
4873
4628
5603
4600
5209
4925
5049
4806
4208
4892
5157
5320
4842
5270
4887
4665
296
290
367
265
311
305
280
268
262
260
272
402
304
288
299
296
327
303
292
281
314
290
309
273
291
288
281
286
287
285
268
281
289
297
315
327
302
299
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
3d-1-3
3d-2-1
3d-2-10
3d-2-2
3d-2-3
3d-2-4
3d-2-5
3d-2-6
3d-2-7
3d-2-8
3d-2-9
3d-3-3
3d-4-1
3d-4-3
3d-5-2
3d-5-3
Sample ID
Table B3. Continued.
Co
56.9
53.7
47.7
55.4
54.0
57.0
52.9
50.2
50.5
53.9
49.9
51.7
60.7
57.3
56.2
58.0
59.3
63.9
48.2
51.1
49.8
54.3
63.1
55.2
54.4
51.0
58.1
57.3
55.1
50.3
51.6
55.9
53.3
58.3
64.5
67.2
56.9
66.4
103
95.7
196
91.9
83.2
113
80.2
64.2
79.1
97.5
81.5
99.9
80.4
102
98.7
82.3
60.6
111
58.9
82.6
63.9
77.2
119
79.9
85.0
65.7
104
110
79.1
71.4
62.6
91.0
94.9
147
119
118
76.5
105
Ni
Cu
1.98
0.84
0.90
0.76
1.17
0.62
1.12
0.43
0.74
1.03
0.90
1.72
0.74
2.29
2.73
2.10
1.35
1.69
1.88
1.59
1.87
0.77
1.09
1.71
1.15
1.07
1.89
2.03
0.74
2.72
2.10
0.64
0.98
0.89
1.66
1.35
0.71
0.86
203
218
191
224
209
225
222
207
208
204
222
231
261
253
255
264
256
251
247
223
243
213
244
262
252
253
250
242
246
253
255
243
256
231
293
272
241
267
Zn
Ga
21.0
17.8
17.7
16.8
19.6
17.4
17.6
16.7
16.7
14.1
15.6
21.2
18.5
17.9
20.1
18.4
17.9
16.9
21.0
17.2
20.4
18.0
18.4
19.2
21.2
19.6
17.5
17.4
19.6
19.0
17.5
16.8
19.2
17.3
21.3
21.0
19.2
19.9
Ge
3.09
3.83
1.67
2.98
3.64
2.94
3.25
3.43
3.27
2.58
3.46
2.40
4.38
3.81
3.89
3.63
3.24
3.28
4.30
2.87
4.30
3.49
3.42
4.39
3.17
3.72
2.91
3.34
3.38
4.26
4.18
3.14
3.86
3.37
4.60
4.01
3.53
4.14
Rb
5.02
0.89
1.55
0.82
0.68
0.44
1.52
0.37
0.53
0.30
0.59
1.18
0.45
0.39
1.79
0.62
0.42
0.18
0.71
0.45
0.49
0.53
0.65
0.62
0.52
0.73
0.31
0.63
0.55
0.40
0.63
0.17
0.66
0.70
0.41
0.78
0.61
1.09
Sr
52.2
34.7
84.8
30.4
34.6
34.0
36.6
31.0
32.7
30.8
31.4
60.0
28.8
30.2
30.7
29.2
45.9
36.2
27.5
31.9
25.2
28.9
30.2
26.5
37.8
29.5
34.9
33.0
31.6
28.4
24.2
29.2
31.3
43.3
30.1
32.3
30.0
27.7
Y
65.5
80.9
23.5
76.6
85.1
73.0
79.8
84.8
86.4
70.1
80.8
57.9
79.3
73.6
77.0
76.1
66.3
66.2
99.8
70.4
101
80.6
67.4
103
66.5
80.3
72.3
67.2
81.2
92.4
94.3
68.3
71.6
61.5
72.9
69.2
76.6
74.4
Zr
40.7
37.3
35.4
39.8
33.1
39.1
34.5
31.1
35.7
38.6
33.1
35.5
33.7
38.6
31.8
33.6
48.6
36.4
31.5
36.6
29.1
32.7
32.5
31.8
42.2
30.7
41.9
38.2
35.3
31.2
25.4
36.0
35.8
35.4
32.2
33.5
29.8
32.6
Nb
4.54
4.87
1.24
4.47
5.65
4.43
5.10
5.21
4.90
4.01
4.38
3.91
4.28
4.20
4.37
4.28
4.13
4.26
4.82
4.68
5.17
4.21
4.15
4.67
4.45
4.93
4.20
3.92
4.49
4.56
4.44
4.11
4.50
3.82
4.08
4.54
4.69
4.00
Ag
In
0.193
0.229
0.186
0.270
0.162
0.170
0.192
0.269
0.244
0.176
0.175
0.180
0.216
0.220
0.188
0.226
Sn
2.44
2.67
2.44
2.44
2.10
1.94
2.74
2.95
2.40
2.08
2.44
2.14
2.62
2.77
2.58
2.65
Ba
19.4
19.2
26.7
19.6
19.0
20.3
19.5
18.3
16.5
17.5
19.7
24.9
19.6
23.4
20.5
21.8
0.05 0.034 0.160 2.11 73.3
0.003 0.200 2.36 21.9
0.035 0.122 1.36 56.4
0.214 1.99 21.9
0.09 0.011 0.170 2.52 27.7
0.155 2.10 22.1
0.196 2.35 25.6
0.205 2.18 19.8
0.003 0.160 2.08 22.0
0.154 1.85 16.1
0.007 0.191 1.90 20.9
0.08 0.014 0.208 1.97 51.2
0.03
0.207 2.49 17.8
0.241 2.13 19.4
0.190 2.51 33.5
0.019 0.211 2.60 19.3
0.019 0.170 1.85 26.9
0.152 2.12 23.6
0.015 0.265 3.24 20.8
0.011 0.169 1.82 20.2
0.281 3.40 21.1
0.01 0.022 0.156 2.30 19.5
0.011
0.12 0.011
0.017
0.12
0.07 0.024
0.018
0.013
0.011
0.026
0.038
0.08 0.040
Mo
La
12.2
12.9
11.0
11.4
14.6
10.4
14.4
13.5
12.9
13.0
13.3
15.4
13.6
11.7
12.3
12.3
10.9
10.5
13.9
10.4
13.7
11.9
10.3
11.4
10.9
12.7
10.5
10.8
11.9
11.9
12.4
11.0
11.4
9.77
11.0
10.8
12.9
11.9
Ce
46.7
57.2
33.2
49.6
62.2
51.9
58.8
59.7
55.3
48.6
60.2
61.0
62.0
52.4
56.0
55.1
48.9
50.3
65.7
46.9
67.9
57.6
51.7
57.2
49.1
58.9
47.3
47.8
56.8
58.7
59.8
48.4
54.0
44.7
56.6
56.1
63.8
63.4
Pr
8.69
10.3
4.83
9.16
11.7
9.22
11.2
11.4
11.1
9.53
10.9
9.93
11.0
9.54
10.0
10.2
8.37
8.26
12.7
8.95
13.0
10.4
9.35
11.0
8.78
10.9
8.85
8.96
10.5
10.6
11.5
9.23
9.80
8.45
10.1
9.43
11.2
10.4
Nd
43.5
55.0
22.2
48.1
62.8
48.8
62.9
62.3
58.3
51.2
56.9
45.9
59.1
57.9
54.3
55.2
47.0
45.8
70.6
47.9
72.6
58.7
47.3
61.1
49.7
58.2
50.0
47.3
57.3
63.1
66.1
52.0
50.9
45.9
55.2
50.8
58.8
58.6
13.6
15.0
5.19
14.4
17.4
14.5
17.2
16.0
15.7
13.5
16.2
10.6
15.4
16.5
15.2
15.5
13.6
11.2
18.7
14.3
20.7
16.4
13.8
19.2
12.1
16.8
14.6
14.6
15.3
19.1
21.4
13.7
14.1
13.9
15.1
14.4
17.0
15.3
Sm
Eu
2.59
3.19
1.98
2.91
3.50
2.89
3.13
3.28
3.44
2.92
2.95
3.01
3.15
3.28
3.28
3.24
3.23
3.15
3.64
3.25
3.88
2.86
3.00
3.30
3.08
3.32
2.89
2.96
3.12
3.42
2.93
2.94
2.95
2.81
2.97
2.88
3.13
3.41
Gd
11.3
15.3
5.65
14.2
17.4
16.7
18.1
18.7
17.3
13.5
16.7
11.3
16.0
14.7
14.3
14.9
13.4
13.3
20.2
14.8
20.6
14.5
13.4
20.1
12.9
16.4
13.9
13.0
16.4
18.9
19.5
12.9
12.9
13.5
15.4
12.9
15.9
15.2
Dy
11.4
13.9
4.82
13.8
15.8
12.6
15.5
14.8
14.7
13.1
14.4
10.5
15.9
13.4
12.7
14.0
11.6
11.4
18.6
13.5
19.1
14.0
13.3
18.9
12.2
14.3
13.2
14.2
15.1
18.0
20.2
13.2
13.1
11.2
14.3
13.8
15.1
14.7
Er
8.29
10.2
2.70
8.30
10.6
7.93
11.2
10.6
11.5
7.43
9.91
7.04
9.43
10.0
9.41
9.07
8.08
8.07
13.6
8.38
12.6
10.6
8.45
12.8
8.43
10.7
9.42
8.23
10.2
12.4
12.8
9.10
8.99
8.41
9.37
9.47
9.28
9.75
Yb
5.86
7.91
1.81
7.31
8.18
6.48
7.27
8.15
8.38
6.49
8.09
5.44
7.56
6.94
6.89
8.27
6.68
6.14
10.6
6.59
9.65
8.50
7.35
9.87
6.45
8.20
7.46
6.98
7.38
10.4
10.1
6.83
7.07
6.57
7.43
7.16
8.15
7.98
Pb
1.19
0.51
0.80
0.46
0.47
0.50
0.59
0.50
0.43
0.34
0.46
1.16
0.53
0.56
0.92
0.56
0.51
0.43
0.54
0.51
0.66
0.53
0.54
0.54
0.70
0.57
0.45
0.44
0.55
0.57
0.44
0.50
0.62
0.52
0.53
0.64
0.47
0.64
186
rim
core
core
rim
rim
core
core
rim
rim
core
single
core
rim
single
single
rim
core
core
rim
rim
core
single
single
single
rim
core
core
single
single
rim
core
single
single
single
single
single
single
single
single
rim
core
18pp01-1-1
18pp01-1-3
18pp01-1-5
18pp01-2-2
18pp01-4-1
18pp01-5-1
18pp01-5-2
18pp01-6-2
18pp01-7-2
18pp01-8-1
18pp01-9-1
18pp02-2-1
18pp02-3-1
18pp03-1-1
18pp03-2-2
18pp03-3-1
18pp03-3-3
Spot Location
18cd01-1-2
18cd01-1-4
18cd01-1-5
18cd01-1-9
18cd01-2-1
18cd01-2-3
18cd01-2-4
18cd01-2-5
18cd01-3-1
18cd01-3-3
18cd01-4-1
18cd01-5-1
18cd01-5-3
18cd01-6-1
18cd01-6-3
18cd02-1-1
18cd02-1-3
18cd02-2-1
18cd02-2-3
18cd02-3-1
18cd02-3-4
18cd02-4-1
18cd03-1-1
18cd03-2-1
Sample ID
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
May 18
Eruption Date
pumice
pumice
pumice
pumice
pumice
pumice
pumice
pumice
pumice
pumice
pumice
pumice
pumice
pumice
pumice
pumice
pumice
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
cryptodome
Deposit
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
867
974
982
859
885
913
917
882
950
954
929
964
881
918
963
878
936
983
952
935
964
893
975
884
269
906
398
959
493
963
520
975
328
930
362
934
550
995
202
877
543
965
383
936
415
969
219
890
189
877
210
881
520
979
421
944
775 1025
174
444
476
182
238
258
277
248
421
519
290
588
215
295
496
206
346
499
427
371
403
209
536
205
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
44.9
43.5
43.1
43.5
43.8
43.7
44.7
46.0
42.4
43.0
44.2
45.9
46.3
45.7
43.8
43.5
44.2
47.1
43.1
42.6
46.8
45.0
43.7
44.0
45.3
43.7
44.0
44.4
42.4
46.0
43.8
43.4
46.0
43.4
44.7
43.7
43.3
45.0
45.6
44.3
45.5
1.98
2.31
2.40
2.15
1.96
2.06
2.10
1.97
2.22
1.85
2.05
1.96
1.71
2.17
2.24
2.17
2.17
1.67
2.85
2.89
1.78
1.50
2.49
2.68
1.51
2.27
2.07
2.14
2.13
1.99
1.99
2.28
1.94
1.95
2.11
2.09
2.14
1.85
2.03
2.05
2.01
10.9
12.6
13.1
13.1
11.8
12.4
12.8
9.6
13.6
12.7
12.6
10.0
9.1
9.9
13.0
13.3
12.8
8.7
12.8
13.5
9.1
10.6
10.9
11.3
10.9
13.2
13.1
11.3
13.9
10.0
11.3
13.1
9.7
12.3
12.6
13.3
12.5
12.5
9.8
13.1
9.7
10.9
10.4
10.6
10.8
10.8
11.2
11.0
11.0
11.1
11.0
10.8
10.9
10.8
11.0
10.7
11.2
11.0
10.8
11.1
11.1
10.8
11.0
10.7
10.9
10.9
11.4
11.1
10.9
11.1
11.0
10.7
11.0
10.8
10.9
10.8
10.9
11.2
10.8
10.9
11.0
11.0
14.2
14.6
14.9
13.2
14.7
14.1
10.9
14.5
14.5
15.0
11.4
14.8
14.8
14.7
12.1
13.2
10.9
14.4
14.7
14.0
14.8
15.8
16.8
16.8
16.2
12.4
12.2
15.0
15.1
15.2
14.3
12.8
15.0
15.4
11.2
13.0
14.0
11.0
15.0
11.5
14.5
14.3
13.6
13.0
14.3
13.9
14.0
15.7
14.5
13.1
13.4
15.6
14.3
14.5
14.1
15.0
13.9
15.4
14.8
12.9
13.0
14.5
13.7
12.6
12.4
13.5
14.6
14.8
13.6
12.7
14.0
13.9
14.5
14.3
13.4
15.8
14.5
13.9
15.8
14.2
15.3
14.3
0.18
0.15
0.17
0.18
0.22
0.18
0.12
0.24
0.20
0.22
0.09
0.24
0.28
0.21
0.11
0.15
0.11
0.24
0.20
0.17
0.23
0.25
0.19
0.22
0.24
0.13
0.09
0.20
0.21
0.23
0.17
0.12
0.22
0.18
0.10
0.09
0.18
0.11
0.24
0.13
0.20
2.15
2.40
2.49
2.54
2.21
2.31
2.47
1.94
2.48
2.30
2.36
2.09
1.91
2.05
2.55
2.40
2.57
1.88
2.32
2.42
1.86
2.13
2.28
2.29
2.08
2.40
2.49
2.34
2.54
2.01
2.23
2.44
1.97
2.44
2.44
2.36
2.23
2.42
2.16
2.40
2.11
0.26
0.28
0.34
0.28
0.30
0.30
0.30
0.27
0.31
0.43
0.26
0.25
0.30
0.36
0.25
0.28
0.30
0.20
0.39
0.37
0.32
0.21
0.36
0.40
0.22
0.27
0.25
0.32
0.37
0.31
0.29
0.32
0.29
0.33
0.29
0.26
0.28
0.34
0.28
0.33
0.26
0.05
0.02
0.01
0.05
0.00
0.03
0.00
0.06
0.02
0.02
0.02
0.01
0.04
0.00
0.01
0.00
0.03
0.02
0.05
0.02
0.01
0.00
0.03
0.07
0.04
0.02
0.00
0.03
0.03
0.03
0.00
0.01
0.01
0.03
0.01
0.01
0.01
0.00
0.00
0.03
0.00
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
Table B4. Amphibole analyses from the 1980 eruptions of Mt. St. Helens.
F
0.11
0.06
0.06
0.01
0.04
0.04
0.09
0.10
0.06
0.06
0.06
0.02
0.05
0.06
0.06
0.11
0.09
0.11
0.06
0.10
0.05
0.09
0.06
0.03
0.09
0.10
0.03
0.10
0.15
0.06
0.07
0.09
0.04
0.13
0.04
0.09
0.06
0.00
0.08
0.07
0.07
Cl
0.029
0.023
0.028
0.023
0.025
0.016
0.017
0.034
0.027
0.029
0.014
0.030
0.051
0.037
0.022
0.015
0.016
0.044
0.055
0.042
0.044
0.021
0.030
0.032
0.018
0.015
0.012
0.026
0.028
0.050
0.042
0.021
0.045
0.030
0.020
0.016
0.018
0.013
0.050
0.013
0.046
SO2
0.014
0.042
0.026
0.036
0.011
0.025
0.015
0.014
0.019
0.038
0.009
0.014
0.005
0.010
0.010
0.009
0.014
0.002
0.013
0.014
0.000
0.026
0.025
0.012
0.014
0.008
0.012
0.000
0.037
0.020
0.000
0.004
0.007
0.000
0.017
0.001
0.005
0.001
0.014
0.010
0.000
100.0
100.1
100.3
100.2
99.7
100.3
100.5
100.2
100.0
100.0
99.5
100.5
99.9
100.2
99.9
100.2
100.0
100.1
100.6
100.4
100.4
100.3
100.2
101.1
101.0
100.5
100.1
100.5
100.6
100.9
98.9
100.0
100.3
100.5
100.3
100.3
99.8
100.0
100.4
100.3
99.7
Total
187
17.2
20.3
19.2
17.0
19.4
20.9
20.3
19.0
21.8
19.0
18.3
16.6
17.8
20.8
17.8
15.0
17.6
18.9
16.2
18.7
14.1
19.0
19.1
20.9
3.85
4.98
4.09
3.80
3.84
3.96
3.66
4.89
4.23
3.94
5.01
3.44
4.52
3.62
4.22
3.33
2.65
18pp01-1-1
18pp01-1-3
18pp01-1-5
18pp01-2-2
18pp01-4-1
18pp01-5-1
18pp01-5-2
18pp01-6-2
18pp01-7-2
18pp01-8-1
18pp01-9-1
18pp02-2-1
18pp02-3-1
18pp03-1-1
18pp03-2-2
18pp03-3-1
18pp03-3-3
209354
257152
239065
211758
225114
208528
194682
227296
232715
229432
212056
273446
219392
266570
237580
245161
249177
208235
223381
237644
195965
198228
218447
200904
227366
204224
200304
232946
224170
219143
219496
218881
217907
197687
320546
257829
234359
226901
234994
268722
274863
87.0
61.3
66.7
132
122
77.2
79.6
139
68.7
68.7
80.4
85.4
136
140
65.5
72.2
76.2
131
79.2
73.0
118
72.4
97.4
106
73.3
77.0
78.7
139
111
131
72.9
131
128
117
80.1
65.9
80.5
82.7
138
73.3
126
13606
16041
17248
14261
13358
14899
14768
13844
15759
12734
14621
13691
11987
15206
14930
14456
15713
12317
20589
21483
12663
9926
17199
19469
10444
15317
15143
15111
14420
13798
13572
13782
13642
14255
14860
14580
14971
13940
13727
14439
14387
620
520
571
416
485
598
657
413
568
503
672
526
372
457
598
644
764
365
498
509
353
422
548
515
433
595
599
463
487
455
371
454
444
516
637
500
563
676
446
628
465
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
18cd01-1-2
18cd01-1-4
18cd01-1-5
18cd01-1-9
18cd01-2-1
18cd01-2-3
18cd01-2-4
18cd01-2-5
18cd01-3-1
18cd01-3-3
18cd01-4-1
18cd01-5-1
18cd01-5-3
18cd01-6-1
18cd01-6-3
18cd02-1-1
18cd02-1-3
18cd02-2-1
18cd02-2-3
18cd02-3-1
18cd02-3-4
18cd02-4-1
18cd03-1-1
18cd03-2-1
Sample ID
Table B4. Continued.
Co
68.7
71.4
70.4
66.2
70.4
76.3
74.4
70.1
70.4
53.3
84.9
69.8
71.3
68.3
71.8
73.2
86.9
67.8
66.7
62.7
65.0
71.4
74.4
76.2
69.4
76.7
75.5
74.2
73.7
70.6
61.7
70.5
69.0
68.8
77.2
67.6
72.4
75.6
70.5
78.1
74.5
Ni
217
48.7
73.6
73.0
136
146
319
64.8
54.0
29.7
303
120
63.9
89.1
265
246
398
70.4
244
365
57.6
46.1
52.3
51.1
43.6
97.5
124
85.1
93.7
97.5
37.2
97.4
76.4
79.9
254
44.9
91.2
330
80.3
184
71.1
Cu
1.83
2.15
2.39
2.28
3.39
1.76
1.67
1.68
3.25
1.43
5.13
1.60
8.67
2.28
4.48
1.75
2.42
8.79
2.27
6.15
5.94
7.52
8.05
6.31
6.39
12.8
7.83
8.29
7.87
6.63
14.1
6.62
56.5
11.8
2.86
8.73
11.9
2.97
6.23
15.4
132
94.4
112
113
129
135
83.6
64.0
153
95.9
139
84.1
143
176
134
69.7
72.1
84.0
163
144
147
141
133
119
107
119
85.5
75.4
144
133
134
117
134
158
143
74.7
91.4
86.1
69.1
146
89.4
151
Zn
Ga
14.4
18.1
21.2
17.1
18.9
17.0
14.7
17.2
17.7
21.0
17.0
17.7
20.4
17.8
14.9
14.6
20.2
18.2
18.7
16.7
18.0
15.8
18.7
21.0
16.9
18.2
17.1
18.6
19.0
17.9
16.7
17.9
18.1
18.6
15.2
15.7
16.3
15.6
16.6
15.6
20.7
Ge
Sr
80.5
279
298
97.3
119
133
155
116
205
184
115
122
101
137
101
93.6
98.5
166
168
213
160
89.8
164
109
Y
77.1
26.5
23.4
56.0
24.1
54.2
55.1
23.2
22.0
20.7
56.4
48.7
51.2
39.1
51.1
62.9
55.6
18.2
22.6
23.2
17.7
60.2
17.0
50.8
Zr
76.7
58.5
49.7
66.9
51.2
90.7
88.8
57.5
36.7
35.1
64.5
57.8
55.7
57.0
55.7
70.9
65.0
38.5
40.1
39.5
28.3
64.8
30.6
63.6
Nb
7.87
9.33
9.01
5.67
4.38
10.5
10.0
4.75
2.53
2.10
6.24
4.96
4.60
4.09
4.59
6.44
6.36
1.87
2.24
2.64
1.49
6.39
1.89
5.80
0.37 142 24.1 33.5 2.67
0.53 186 28.3 43.3 4.04
1.01 192 30.3 40.2 3.68
0.74 110 53.1 62.5 6.07
0.37 100 57.1 67.9 6.01
0.71 175 21.7 34.5 2.11
0.67 168 16.8 25.7 1.51
0.60 96.8 64.3 69.4 6.41
0.62 198 23.6 36.5 2.22
0.98 170 40.9 63.4 11.4
1.89 162 19.4 38.0 1.81
0.67 93.8 42.0 67.5 4.96
0.58 73.2 72.2 74.2 6.32
0.76 102 50.8 57.8 5.94
0.68 167 15.6 21.9 2.08
0.87 161 16.1 23.9 1.73
0.98 187 16.8 24.0 1.78
0.81
0.94
0.57
0.59
0.88
0.88
0.45
0.75
0.62
0.67
0.54
0.70
0.55
0.70
0.65
0.63
0.70
0.69
0.52
0.70
0.63
0.77
0.70
Rb
Mo
Ag
In
0.281
0.157
0.110
0.219
0.106
0.182
0.214
0.090
0.112
0.118
0.210
0.200
0.210
0.170
0.210
0.300
0.263
0.112
0.109
0.098
0.083
0.220
0.114
0.260
0.126
0.115
0.129
0.250
0.242
0.114
0.080
0.269
0.119
0.175
0.095
0.229
0.264
0.222
0.067
0.043 0.111
0.040 0.110
0.043
0.048
0.023
0.046
0.026
0.059
0.047
0.065
0.028
0.042
0.033
0.010
0.034
0.058
0.013
0.021
0.056
0.065
0.035
0.053
0.060
0.055
0.025
0.018
0.025
0.039
0.029
0.023
0.030
0.014
0.040
0.040
0.040
0.043
0.043
0.064
0.038
Sn
0.95
1.12
1.03
1.41
1.38
0.88
0.59
1.59
1.01
1.53
0.77
1.38
1.72
1.48
0.65
0.65
0.82
1.81
1.10
0.99
1.45
0.67
0.88
0.77
0.75
0.89
0.88
1.42
1.29
1.28
1.22
1.28
1.63
1.61
0.78
1.14
0.99
0.76
1.38
0.80
1.55
Ba
34.7
40.4
49.2
45.0
42.2
31.3
27.9
46.2
45.9
60.5
36.3
47.0
37.1
54.3
34.3
34.5
35.7
40.7
59.5
66.8
41.6
26.9
60.7
67.9
30.4
53.1
34.6
46.0
42.6
41.2
40.5
41.2
51.1
57.8
32.0
38.0
44.6
31.9
43.5
32.1
47.9
La
2.33
1.80
1.92
5.25
5.69
1.87
1.35
5.98
2.09
6.12
2.15
6.30
7.20
5.54
1.30
1.51
1.46
8.32
4.50
3.52
5.50
3.13
5.47
5.21
3.47
2.26
1.79
5.99
5.33
4.54
3.68
4.53
6.53
5.70
1.71
2.26
2.44
1.52
6.00
1.53
5.00
Ce
10.5
8.46
9.66
24.6
26.2
8.01
6.01
27.8
8.70
25.6
7.88
25.9
31.7
23.2
5.59
7.26
7.23
36.1
17.1
13.3
24.0
12.8
24.1
22.0
13.0
10.5
8.52
24.9
21.1
21.1
17.8
21.1
30.6
27.1
7.90
9.64
10.7
7.17
27.2
7.48
24.8
Pr
2.36
1.98
2.09
5.03
5.46
1.82
1.21
5.66
1.86
5.19
1.76
4.98
6.55
4.84
1.26
1.40
1.43
7.58
3.38
2.49
4.80
2.49
4.51
4.20
2.63
2.16
1.78
5.42
4.56
4.65
3.52
4.64
5.98
5.30
1.80
1.98
2.20
1.35
5.44
1.47
5.24
Nd
13.2
12.2
15.2
31.5
33.9
11.1
8.82
35.5
14.2
31.2
10.3
31.2
43.5
31.2
8.51
9.69
8.43
46.0
18.3
16.3
31.9
14.5
28.3
25.9
14.2
13.6
10.5
33.6
29.2
28.2
24.6
28.1
37.9
35.6
11.0
12.5
13.5
11.0
36.6
9.72
32.2
5.89
5.03
4.46
12.2
12.5
4.47
3.37
12.9
4.61
9.04
4.11
9.88
14.4
11.1
3.38
3.38
3.09
18.5
6.31
4.71
11.0
4.24
10.2
8.73
4.35
4.62
4.32
12.2
11.7
10.5
8.16
10.5
14.2
11.7
4.48
4.74
5.44
3.22
12.6
4.19
10.6
Sm
Eu
1.45
1.71
1.61
2.81
2.68
1.41
1.12
3.10
1.57
3.00
1.18
2.71
2.86
2.59
1.05
1.13
1.32
2.98
2.36
1.88
2.81
1.59
2.45
2.11
1.56
1.65
1.37
3.14
2.39
2.42
2.20
2.41
2.83
2.68
1.17
1.57
1.55
1.29
2.66
1.25
2.35
Gd
5.37
6.09
7.17
13.0
13.7
5.25
4.51
17.1
6.49
9.70
4.88
10.7
17.6
13.6
3.40
4.32
3.90
19.0
7.07
6.11
13.0
4.45
11.4
10.9
4.86
6.01
4.89
13.4
13.2
11.3
9.88
11.3
15.2
13.2
4.42
4.61
5.17
4.74
15.2
4.04
13.5
Dy
5.12
5.85
6.33
12.1
12.6
4.53
3.70
15.2
5.66
9.88
4.44
8.57
15.9
11.0
3.75
3.80
3.59
16.3
5.83
4.89
11.3
4.56
11.0
11.3
4.32
4.97
4.40
12.1
10.6
10.7
8.28
10.7
13.6
13.9
4.30
5.36
5.27
4.08
12.7
3.75
12.5
Er
3.10
3.50
3.49
6.36
6.92
2.17
1.78
6.71
2.86
4.83
2.17
4.99
8.13
5.84
1.98
1.50
1.75
9.01
2.88
1.97
5.82
2.87
6.19
6.15
2.49
2.35
2.16
5.92
6.65
5.69
4.48
5.68
7.02
5.87
2.22
2.52
2.60
1.97
6.72
1.86
5.75
Yb
1.73
2.37
2.31
4.30
4.59
1.46
1.29
5.75
2.08
3.49
1.71
3.62
6.05
3.62
1.30
1.29
1.36
6.67
2.07
1.82
4.11
2.19
4.73
4.47
2.61
1.47
1.72
4.17
4.53
3.98
3.34
3.98
4.90
4.46
1.46
1.86
1.61
1.51
5.32
1.52
4.77
Pb
0.34
0.50
0.58
0.47
0.50
0.35
0.30
0.56
0.47
0.54
0.53
0.53
0.55
0.53
0.32
0.35
0.39
0.29
1.26
0.77
0.50
0.31
0.49
0.46
0.37
0.63
0.39
0.49
0.54
0.53
0.50
0.53
0.73
0.54
0.35
0.39
0.41
0.36
0.51
0.31
0.57
188
core
rim
rim
core
core
rim
single
single
single
single
rim
core
single
single
single
rim
core
core
core
core
rim
single
single
rim
core
core
core
core
rim
rim
single
single
12af9-1-1
12af9-1-2
12af9-1-3
12af9-1-4
12af9-1-5
12af9-1-6
12af9-2-2
12af9-2-3
12af9-3-1
12af9-3-2
12af9-5-1
12af9-5-2
12af9-5-3
12af9-5-4
12af9-5-5
12af9-6-2
12af9-6-3
Spot Location
12af16-1-1
12af16-1-2
12af16-2-1
12af16-2-2
12af16-2-3
12af16-2-4
12af16-3-1
12af16-3-2
12af16-4-1
12af16-4-2
12af16-5-1
12af16-5-2
12af16-6-1
12af16-6-2
12af16-7-1
Sample ID
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
Table B4. Continued.
Eruption Date
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
Deposit
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hst
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
279
273
291
291
290
275
300
308
341
318
248
251
251
257
237
298
289
928
919
926
942
945
928
929
929
956
931
914
918
917
920
908
942
949
178
850
179
862
299
942
292
899
181
842
287 1018
172
834
304
922
388
935
381
931
408
928
350
930
340
944
301
916
257
908
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
43.3
44.2
43.0
42.8
43.0
42.7
44.7
43.3
43.5
44.0
43.9
44.9
44.3
44.4
45.1
43.2
43.3
46.2
46.0
44.6
43.8
45.4
41.6
47.2
44.0
44.9
43.4
44.1
43.4
43.6
44.8
44.9
2.67
2.80
2.74
2.94
2.82
2.54
2.60
2.63
2.45
1.81
2.66
2.56
2.52
2.60
2.40
2.38
2.43
2.01
1.94
2.44
2.41
1.96
2.29
1.21
1.90
2.10
2.28
1.68
2.01
2.32
2.34
2.01
11.1
10.9
11.3
11.1
11.1
11.0
11.5
11.5
11.9
11.6
10.4
10.6
10.6
10.6
10.3
11.2
11.1
9.2
9.1
11.4
11.6
9.5
11.3
8.6
11.6
12.4
12.8
12.8
12.1
11.9
11.5
10.7
10.8
10.8
10.8
11.0
10.8
10.8
11.0
11.0
11.3
10.8
10.8
10.9
11.0
10.9
10.9
10.4
10.5
10.9
10.8
11.1
10.9
10.5
9.8
10.6
10.8
10.9
11.1
11.0
10.9
11.1
11.1
10.6
14.7
14.0
14.7
13.8
14.4
15.4
13.5
13.9
11.4
14.5
13.6
13.5
13.6
13.6
13.5
15.2
14.9
15.1
15.3
12.8
16.1
17.9
18.2
15.0
14.7
10.9
13.7
11.7
14.2
12.8
12.5
15.3
13.2
13.5
13.0
13.6
13.5
12.7
13.8
13.6
15.3
13.7
13.5
13.9
13.9
13.8
14.1
13.3
13.1
13.7
13.6
14.7
12.2
12.0
13.6
14.1
13.5
15.1
13.4
14.8
13.7
14.4
14.6
13.5
0.17
0.16
0.16
0.17
0.21
0.23
0.16
0.17
0.12
0.27
0.16
0.18
0.15
0.19
0.18
0.25
0.24
0.20
0.23
0.17
0.20
0.21
0.18
0.35
0.21
0.10
0.10
0.15
0.22
0.16
0.10
0.24
2.37
2.28
2.31
2.33
2.33
2.31
2.46
2.26
2.49
2.31
2.34
2.41
2.40
2.34
2.36
2.30
2.52
1.94
2.05
2.47
2.23
1.99
3.08
1.57
2.36
2.34
2.50
2.17
2.21
2.41
2.33
2.22
0.27
0.31
0.32
0.31
0.28
0.32
0.51
0.48
0.30
0.27
0.46
0.28
0.29
0.30
0.30
0.30
0.24
0.35
0.36
0.24
0.24
0.37
0.53
0.44
0.29
0.28
0.26
0.27
0.27
0.28
0.28
0.35
0.02
0.05
0.05
0.05
0.07
0.05
0.03
0.04
0.01
0.01
0.01
0.04
0.02
0.00
0.03
0.04
0.02
0.04
0.00
0.06
0.06
0.00
0.04
0.02
0.01
0.00
0.02
0.00
0.01
0.00
0.06
0.03
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
F
0.11
0.09
0.07
0.00
0.02
0.02
0.15
0.10
0.18
0.14
0.06
0.03
0.11
0.09
0.09
0.02
0.04
0.07
0.16
0.05
0.15
0.04
0.08
0.05
0.04
0.00
0.16
0.04
0.02
0.09
0.00
0.08
Cl
0.027
0.019
0.020
0.023
0.027
0.026
0.029
0.033
0.028
0.024
0.053
0.030
0.031
0.030
0.034
0.032
0.029
0.054
0.052
0.038
0.020
0.040
0.064
0.211
0.023
0.011
0.020
0.015
0.024
0.017
0.017
0.031
SO2
Total
0.020 98.7
0.013 99.2
0.002 98.5
0.024 98.2
0.011 98.6
0.000 98.2
0.019 100.4
0.018 98.9
0.008 99.1
0.025 99.4
0.008 97.8
0.000 99.4
0.001 99.0
0.025 98.9
0.025 99.4
0.026 98.6
0.000 98.5
0.000 99.7
0.018 99.7
0.009 100.0
0.022 99.9
0.009 99.9
0.002 100.7
0.000 99.4
0.018 99.4
0.021 99.2
0.010 99.7
0.037 98.7
0.011 98.9
0.007 99.1
0.024 99.7
0.014 99.9
189
272
193
213
293
299
211
283
283
389
280
420
379
341
336
276
15.6
17.3
16.0
17.6
15.0
15.9
12.2
10.9
12.9
11.2
10.9
11.1
10.5
9.29
9.31
13.1
12.6
12af9-1-1
12af9-1-2
12af9-1-3
12af9-1-4
12af9-1-5
12af9-1-6
12af9-2-2
12af9-2-3
12af9-3-1
12af9-3-2
12af9-5-1
12af9-5-2
12af9-5-3
12af9-5-4
12af9-5-5
12af9-6-2
12af9-6-3
184237
185102
187309
192559
193330
180285
199384
179933
209614
186136
191373
195493
198235
187538
190786
186786
186855
194664
192306
187136
185763
195733
159263
201742
181872
193047
193600
193792
189379
198339
184068
186548
101
113
110
128
120
92.3
52.5
59.2
97.8
71.7
131
144
145
113
145
108
114
129
98.1
95.0
92.1
73.1
76.2
84.2
71.2
87.3
84.2
85.3
70.4
99.8
108
69.4
18656
19390
18641
20908
19468
18512
18135
17773
15891
11656
18687
17735
17513
17803
16225
16262
16869
13048
12960
16187
15701
12360
14391
7747
12728
15182
14980
12305
12895
15374
16657
15017
549
618
608
734
645
540
500
468
600
290
670
692
694
629
652
545
574
394
361
522
404
485
489
245
305
582
488
521
393
577
579
503
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
12af16-1-1
12af16-1-2
12af16-2-1
12af16-2-2
12af16-2-3
12af16-2-4
12af16-3-1
12af16-3-2
12af16-4-1
12af16-4-2
12af16-5-1
12af16-5-2
12af16-6-1
12af16-6-2
12af16-7-1
Sample ID
Table B4. Continued.
Co
63.6
71.9
72.8
78.6
73.1
66.6
58.6
57.3
76.4
60.5
65.8
65.0
67.5
64.6
64.9
59.8
58.8
66.0
64.4
67.4
60.5
64.9
60.1
58.3
53.5
72.8
69.2
72.3
63.2
73.3
76.2
65.8
Ni
66.9
67.3
69.4
90.1
67.2
65.3
132
127
219
21.9
252
284
291
251
279
189
189
97.1
82.8
109
65.3
72.8
88.7
75.1
19.6
274
79.7
119
73.6
135
179
79.4
Cu
2.58
2.84
2.51
2.86
2.36
2.96
2.60
2.48
2.97
2.09
2.28
2.43
2.22
2.08
2.13
2.73
2.66
39.2
31.7
36.6
48.0
42.7
33.9
33.2
41.2
65.6
55.8
63.0
53.0
37.7
39.8
42.7
91.8
84.8
88.3
86.3
90.1
93.0
98.2
99.8
102
139
106
98.1
102
97.5
108
122
114
137
143
99.2
137
139
75.8
209
123
63.6
82.0
75.1
108
88.4
83.5
117
Zn
Ga
16.9
17.7
17.9
18.3
18.0
18.1
22.5
21.9
20.2
21.1
22.7
20.2
21.0
20.4
20.6
20.2
23.0
18.6
19.0
18.3
19.2
19.7
15.6
20.1
19.2
16.0
16.8
17.5
19.1
18.1
16.9
21.2
Ge
Rb
0.56
0.53
0.73
0.71
0.56
0.52
0.93
1.15
0.70
1.06
0.79
0.71
0.59
0.61
0.65
0.72
0.87
0.56
0.67
0.73
0.68
1.54
1.32
0.59
0.53
0.60
0.73
0.63
0.48
0.62
0.71
0.94
Sr
152
166
174
168
149
148
221
188
183
118
178
172
178
172
172
186
171
83.7
90.4
172
170
88.3
137
72.2
145
198
214
161
154
186
186
113
Y
42.4
41.9
41.3
41.5
42.8
42.0
42.2
43.2
32.5
43.9
78.2
83.6
82.3
71.3
79.4
58.8
74.2
74.0
61.9
39.5
46.2
54.2
26.8
73.6
43.4
20.1
24.2
24.2
32.6
25.9
24.6
56.6
Zr
60.0
55.3
54.1
58.6
57.1
63.4
108
119
55.7
63.2
148
136
135
124
123
107
144
94.3
92.2
70.6
72.2
108
57.3
59.3
64.2
33.1
39.5
41.4
50.6
36.2
35.2
136
Nb
5.85
6.23
6.26
5.42
5.41
6.63
21.3
19.5
3.73
3.45
28.1
24.0
25.2
24.7
25.4
21.1
28.7
9.58
10.2
6.31
5.79
9.89
4.25
8.31
4.15
2.00
2.62
1.43
2.63
2.48
2.75
11.5
Mo
0.058
0.024
0.041
0.034
0.035
0.029
0.044
0.043
0.028
0.046
0.044
0.047
0.033
0.040
0.028
0.039
0.038
0.055
0.035
0.026
0.023
0.031
0.059
0.042
0.047
0.040
0.058
0.033
0.025
0.040
Ag
In
0.124
0.133
0.114
0.142
0.139
0.128
0.127
0.149
0.134
0.158
0.223
0.238
0.228
0.189
0.205
0.140
0.170
0.246
0.212
0.134
0.161
0.153
0.109
0.176
0.141
0.091
0.103
0.110
0.136
0.108
0.124
0.136
Sn
0.69
0.72
0.69
0.76
0.79
0.68
1.30
1.35
0.97
1.33
1.85
1.66
1.62
1.43
1.44
0.89
1.51
1.38
1.26
0.87
1.04
1.11
0.65
2.56
1.07
0.62
0.83
0.80
0.89
0.94
0.82
1.12
Ba
54.6
63.0
66.6
63.8
49.4
48.3
85.9
77.7
57.3
36.4
100
68.8
69.6
59.4
65.2
69.5
102
46.9
49.9
50.0
52.1
50.8
44.5
41.8
44.3
39.2
41.4
31.4
36.4
42.8
46.0
64.6
La
4.27
3.81
4.07
3.75
3.86
4.24
7.60
8.03
3.58
4.02
10.9
9.45
9.49
8.97
8.64
8.08
12.9
8.44
8.02
4.29
4.98
8.17
3.68
12.0
4.37
1.95
2.40
1.86
3.05
1.88
2.25
8.75
Ce
16.7
17.4
16.7
16.1
16.4
18.6
30.6
31.8
16.3
20.0
45.3
39.4
38.9
36.0
35.3
32.2
49.8
35.6
33.2
17.6
20.7
36.2
13.7
58.3
19.4
8.38
8.82
7.52
14.2
9.20
10.3
37.2
Pr
3.47
3.35
3.43
3.40
3.26
3.61
5.22
5.61
3.10
3.95
8.64
7.75
7.58
7.19
7.08
5.87
8.56
7.23
6.61
3.49
3.99
6.60
2.30
11.1
4.24
1.61
1.72
1.76
2.96
2.07
2.07
6.77
Nd
22.7
21.7
21.3
20.2
21.2
22.8
33.0
32.5
18.5
27.1
54.4
46.3
46.4
43.9
45.0
37.9
51.9
45.3
40.0
20.4
25.1
33.1
14.7
62.7
26.5
11.9
12.3
11.7
18.8
13.3
11.9
38.8
8.47
6.86
6.88
7.18
7.93
8.27
9.53
10.1
6.27
8.90
17.0
17.3
16.0
14.0
16.1
12.7
17.6
16.2
13.0
6.99
8.54
9.87
5.06
18.9
9.13
4.71
3.20
4.34
6.62
4.33
4.59
11.1
Sm
Eu
2.07
2.24
1.91
1.98
1.72
2.11
2.61
2.38
1.89
2.93
3.37
3.52
3.55
3.12
3.05
2.38
2.90
2.93
2.36
2.04
2.34
2.23
1.62
3.66
2.74
1.49
1.33
1.38
2.23
1.42
1.61
2.38
Gd
8.89
9.14
9.15
9.38
8.82
9.50
10.3
9.06
7.51
11.7
17.8
19.4
19.5
15.6
17.1
13.6
18.2
16.8
15.0
9.19
8.68
11.3
6.56
18.5
10.2
4.82
6.22
5.38
6.39
6.40
5.80
11.6
Dy
8.89
8.79
8.59
8.65
8.26
9.77
9.40
9.84
7.05
10.3
16.8
18.1
16.2
14.9
16.7
12.8
15.9
16.6
12.7
8.10
9.45
10.7
5.82
16.7
9.68
4.44
5.11
5.10
6.93
5.85
5.48
11.6
Er
4.92
4.93
4.83
4.62
4.80
4.69
5.10
5.31
4.24
5.84
8.72
9.43
9.51
7.98
9.26
6.68
8.05
7.78
7.65
4.61
5.64
7.07
2.90
8.17
4.99
2.34
3.50
2.89
3.56
3.26
3.07
6.36
Yb
4.20
3.49
3.78
3.28
3.44
3.86
3.10
3.81
2.52
4.16
7.06
6.45
6.58
5.97
5.56
4.76
5.57
5.89
5.08
3.14
4.28
5.35
2.46
6.22
4.06
1.58
1.74
2.02
2.77
1.96
2.00
5.26
Pb
0.38
0.42
0.42
0.43
0.45
0.42
0.47
0.48
0.51
0.56
0.54
0.42
0.46
0.42
0.46
0.46
0.55
0.46
0.50
0.49
0.65
0.61
0.44
0.50
0.51
0.30
0.58
0.29
0.42
0.41
0.41
0.52
190
rim
core
core
single
core
core
rim
core
core
single
single
single
single
single
single
single
single
single
single
single
single
rim
core
single
single
single
single
core
rim
core
rim
single
core
rim
bl12pf10-1-1
bl12pf10-10-1
bl12pf10-2-2
bl12pf10-3-1
bl12pf10-4-2
bl12pf10-4-3
bl12pf10-5-1
bl12pf10-5-2
bl12pf10-6-3
bl12pf10-6-4
bl12pf10-7-1
bl12pf10-8-1
bl12pf10-9-1
bl12pf13-1-2
bl12pf13-2-1
bl12pf13-2-2
bl12pf13-3-1
bl12pf13-3-2
bl12pf13-4-1
bl12pf13-5-1
bl12pf13-5-2
Spot Location
12pf1-1-2
12pf1-1-3
12pf1-1-4
12pf1-10-2
12pf1-2-1
12pf1-2-2
12pf1-2-3
12pf1-4-2
12pf1-4-3
12pf1-5-1
12pf1-6-2
12pf1-6-3
12pf1-8-1
Sample ID
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
June 12
Table B4. Continued.
Eruption Date
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
Deposit
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
386
342
307
252
233
410
433
209
285
286
215
189
367
206
225
209
523
513
207
230
201
200
333
317
517
334
331
197
413
417
248
289
209
204
927
937
907
896
897
947
937
882
909
903
883
861
926
877
890
885
963
964
883
886
870
873
924
936
962
944
929
860
940
943
890
905
873
871
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
43.6
44.3
44.4
44.2
45.1
43.3
42.9
45.7
44.2
45.1
45.8
46.2
43.8
45.7
44.8
45.0
43.3
43.8
46.2
44.7
46.0
45.2
42.6
42.9
43.4
42.2
42.8
45.9
44.2
43.0
44.5
44.6
45.2
45.6
2.06
2.13
1.91
2.06
2.00
2.17
2.07
2.01
1.85
1.88
1.86
1.83
1.87
1.95
1.97
2.06
2.00
1.99
1.63
2.06
1.90
2.06
1.94
2.28
2.15
2.45
2.46
1.88
2.03
2.14
2.02
2.04
1.79
1.92
12.9
12.0
11.6
10.7
10.2
12.7
13.4
9.7
11.1
11.1
9.7
9.2
12.2
9.6
10.0
9.7
13.2
12.6
9.7
10.2
9.4
9.4
11.9
11.5
12.6
11.8
11.8
9.3
12.6
12.8
10.4
11.1
9.6
9.4
11.1
11.1
11.0
11.1
10.9
11.0
11.0
10.8
10.8
10.8
10.7
10.7
10.7
10.8
10.6
10.9
10.8
10.9
10.6
10.8
10.8
10.7
11.0
10.7
10.8
11.1
11.0
10.7
10.7
11.0
10.7
10.7
10.7
10.8
14.6
12.6
13.6
14.2
14.3
12.7
13.6
14.3
13.8
13.3
13.5
14.2
13.3
13.8
15.4
14.1
12.1
10.9
14.8
14.3
13.8
13.8
13.8
14.5
10.7
13.8
14.1
13.8
11.1
11.9
13.8
13.2
13.5
13.2
13.0
14.8
14.0
13.8
14.0
14.1
13.3
14.1
14.1
14.5
14.7
14.3
14.0
14.4
13.4
14.2
14.6
15.5
14.4
14.0
14.4
14.1
13.3
13.2
15.1
13.2
12.9
13.9
15.2
14.3
13.8
13.9
14.3
14.3
0.19
0.15
0.17
0.19
0.26
0.17
0.15
0.23
0.16
0.15
0.18
0.20
0.17
0.19
0.25
0.21
0.17
0.10
0.23
0.17
0.21
0.18
0.18
0.23
0.10
0.21
0.20
0.21
0.09
0.14
0.17
0.17
0.19
0.21
2.40
2.36
2.20
2.13
2.11
2.34
2.33
2.08
2.22
2.14
2.05
1.92
2.23
2.02
2.06
2.03
2.30
2.43
2.10
2.06
1.93
2.00
2.34
2.30
2.40
2.45
2.33
1.95
2.24
2.26
2.11
2.19
1.99
1.96
0.32
0.25
0.20
0.37
0.29
0.31
0.35
0.27
0.27
0.33
0.29
0.30
0.27
0.29
0.29
0.23
0.32
0.29
0.28
0.26
0.28
0.29
0.26
0.15
0.26
0.19
0.19
0.27
0.27
0.29
0.31
0.30
0.28
0.30
0.08
0.02
0.00
0.01
0.05
0.00
0.00
0.00
0.00
0.06
0.01
0.03
0.02
0.02
0.05
0.01
0.01
0.03
0.00
0.04
0.01
0.04
0.02
0.02
0.00
0.02
0.03
0.03
0.00
0.10
0.01
0.02
0.02
0.03
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
F
0.00
0.06
0.15
0.16
0.07
0.09
0.10
0.07
0.15
0.08
0.10
0.11
0.07
0.05
0.07
0.09
0.10
0.07
0.09
0.10
0.03
0.08
0.16
0.04
0.08
0.09
0.11
0.12
0.04
0.03
0.11
0.09
0.02
0.11
Cl
0.033
0.018
0.055
0.024
0.023
0.022
0.019
0.037
0.021
0.029
0.039
0.043
0.013
0.043
0.043
0.033
0.011
0.015
0.032
0.034
0.046
0.040
0.018
0.015
0.015
0.017
0.018
0.045
0.014
0.016
0.038
0.033
0.040
0.045
SO2
97.9
97.7
97.7
97.5
97.6
98.0
98.1
98.5
98.0
98.0
98.3
97.6
97.9
Total
0.015 100.4
0.010 99.7
0.017 99.2
0.013 98.9
0.014 99.2
0.022 99.0
0.022 99.2
0.031 99.5
0.018 98.8
0.015 99.6
0.025 99.0
0.000 99.0
0.021 98.7
0.006 98.8
0.013 99.0
0.001 98.5
0.008 99.0
0.013 98.7
0.023 100.0
0.016 98.8
0.020 99.0
0.006
0.022
0.017
0.022
0.019
0.004
0.004
0.035
0.019
0.000
0.016
0.004
0.011
191
7.25
7.89
6.01
6.04
7.32
7.53
9.51
6.85
5.49
11.4
7.26
6.49
6.64
64.2
87.4
76.0
70.4
68.6
72.7
106
96.6
55.4
51.9
68.8
70.6
73.7
22.2
27.5
25.4
24.0
22.7
27.0
28.1
21.6
bl12pf10-1-1
bl12pf10-10-1
bl12pf10-2-2
bl12pf10-3-1
bl12pf10-4-2
bl12pf10-4-3
bl12pf10-5-1
bl12pf10-5-2
bl12pf10-6-3
bl12pf10-6-4
bl12pf10-7-1
bl12pf10-8-1
bl12pf10-9-1
bl12pf13-1-2
bl12pf13-2-1
bl12pf13-2-2
bl12pf13-3-1
bl12pf13-3-2
bl12pf13-4-1
bl12pf13-5-1
bl12pf13-5-2
208612
203773
201361
203965
205321
200957
192467
207990
276655
250228
267992
204248
241214
226703
264136
266227
290100
217014
231534
248539
243117
218256
204697
202455
197150
193772
209573
211183
195359
197173
200285
207060
214419
202761
133
83.3
70.9
100
96.0
69.2
73.5
107
137
91.0
135
142
116
140
111
111
75.8
80.9
130
92.7
131
166
90.7
113
85.4
92.9
101
133
80.8
88.2
129
121
94.9
137
13547
14715
14375
13776
14116
14901
14460
14131
12689
12908
12614
12761
12420
13243
14229
14763
13582
13959
12003
13363
13094
14278
13490
15674
15303
16394
16882
12633
13615
14701
13258
13147
13362
13078
464
526
460
441
409
519
513
470
429
550
444
386
480
449
547
521
607
649
387
532
430
438
399
339
593
352
351
414
618
563
433
391
368
422
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
12pf1-1-2
12pf1-1-3
12pf1-1-4
12pf1-10-2
12pf1-2-1
12pf1-2-2
12pf1-2-3
12pf1-4-2
12pf1-4-3
12pf1-5-1
12pf1-6-2
12pf1-6-3
12pf1-8-1
Sample ID
Table B4. Continued.
Co
67.9
76.1
67.6
53.2
60.5
71.7
72.1
65.2
66.3
69.9
67.0
70.9
65.3
68.5
87.0
85.4
74.3
72.6
69.2
64.0
67.4
72.1
67.5
73.1
71.9
69.4
72.0
73.0
74.3
74.1
66.9
71.2
69.0
63.7
Ni
113
182
84.1
43.7
45.6
78.0
49.5
68.7
88.3
113
89.3
68.2
130
111
83.8
76.0
124
279
66.9
136
63.5
81.7
73.6
66.8
275
91.3
86.2
76.9
376
138
78.7
95.7
54.9
93.3
Cu
141
132
95.1
58.9
87.6
113
159
65.7
75.0
129
124
121
125
Zn
Ga
20.3
17.7
19.6
14.3
16.5
19.6
19.2
14.2
17.0
18.8
18.9
19.5
17.4
6.03 126 18.3
5.38 75.3 16.4
6.25 98.8 18.9
4.72 104 20.0
4.71 119 18.5
6.06 84.3 18.7
8.67 100 19.3
14.8 114 18.3
17.2 145 17.1
21.7 114 17.6
17.5 143 18.6
21.4 157 17.9
18.4 151 17.3
17.2 153 19.9
32.6 180 22.1
28.1 163 21.5
10.6 80.6 15.0
8.54 68.3 15.1
20.7 153 17.6
24.7 109 17.1
16.9 158 18.1
3.21
1.86
3.40
1.53
1.59
1.99
2.20
3.42
1.51
2.58
1.36
1.76
4.83
Ge
Rb
Sr
Y
Zr
Nb
0.55
0.60
0.32
0.79
0.75
0.29
0.61
0.68
0.63
0.52
0.67
0.51
0.63
0.64
0.45
1.24
0.50
0.57
0.44
0.65
0.63
107
173
173
121
121
198
191
144
93.6
130
99.8
84.4
110
95.5
102
108
162
185
82.1
130
99.1
63.7
23.8
32.2
49.6
51.2
21.2
25.3
42.6
64.7
35.5
58.7
65.1
47.6
59.2
44.5
44.1
19.6
18.1
60.4
34.8
55.8
73.7
48.3
52.1
104
97.5
30.7
34.3
53.5
70.4
44.7
65.4
68.0
55.9
67.9
52.6
52.9
30.9
30.4
67.2
46.2
63.6
6.25
2.80
3.60
8.04
8.87
2.58
1.95
4.05
6.37
3.20
5.91
6.38
4.15
6.32
5.61
6.27
1.71
1.59
6.05
3.43
5.99
0.47 94.4 62.1 61.9 6.94
0.54 126 47.6 58.0 4.39
0.47 154 50.0 75.1 3.23
0.55 179 19.3 30.0 1.93
0.42 193 28.1 35.7 3.53
0.44 181 38.0 51.4 3.47
0.61 89.7 62.4 60.8 5.46
0.43 169 16.5 21.8 1.76
0.69 202 23.0 32.3 2.20
1.31 115 51.2 60.4 4.71
0.62 116 54.5 63.7 4.55
0.71 134 45.4 58.6 4.07
0.51 96.8 59.0 62.5 5.81
Mo
Ag
0.026
0.028
0.029
0.049
0.041
0.021
0.028
0.044
0.050
0.019
0.039
0.028
0.023
0.045
0.025
0.054
0.010
0.060
0.102
0.059
0.027
0.030
0.032
0.037
0.028
0.044
0.031
0.029
0.034
0.038
0.042
0.018
0.036
0.033
In
0.198
0.106
0.118
0.141
0.141
0.106
0.110
0.169
0.214
0.149
0.223
0.237
0.184
0.279
0.237
0.305
0.110
0.097
0.249
0.170
0.245
0.245
0.172
0.145
0.084
0.122
0.150
0.250
0.081
0.099
0.211
0.208
0.167
0.201
Sn
1.43
0.77
0.82
2.10
1.79
0.82
0.99
1.12
1.40
1.03
1.61
1.43
1.25
1.50
1.72
1.78
0.71
0.76
1.47
1.09
1.50
1.46
1.14
0.68
0.65
0.54
0.70
1.53
0.57
0.78
1.35
1.29
1.30
1.31
Ba
52.9
38.5
42.7
56.9
56.3
38.7
39.7
44.4
41.9
34.0
41.9
43.8
37.8
43.3
46.6
48.5
31.5
35.6
40.4
38.9
42.5
55.7
44.7
42.8
32.0
44.2
49.3
42.8
31.6
41.0
53.9
44.4
44.3
47.3
La
6.90
2.35
3.12
6.00
5.98
1.83
1.74
4.58
6.54
3.36
6.06
6.70
4.75
6.37
4.99
5.09
1.36
1.78
6.50
3.65
5.69
6.17
5.01
2.92
1.58
2.14
2.57
5.79
1.20
2.16
5.82
5.51
4.52
6.45
Ce
31.5
9.71
14.5
24.8
25.0
7.76
8.98
19.2
28.8
15.0
27.0
29.7
20.4
28.6
25.7
28.9
7.66
7.55
28.9
16.2
25.8
27.9
22.8
12.6
6.83
9.08
12.1
29.0
5.42
9.12
23.0
22.9
18.2
25.3
Pr
6.16
2.05
2.88
4.56
4.28
1.77
1.62
3.43
5.98
3.27
5.40
5.98
4.42
5.77
4.81
5.27
1.62
1.53
5.78
2.98
5.26
5.73
4.53
2.62
1.70
1.93
2.42
5.68
1.18
1.79
4.85
4.67
3.87
5.47
Nd
41.2
12.0
19.6
27.0
27.7
12.1
12.3
27.9
35.2
21.0
32.5
37.7
25.4
36.2
29.6
30.1
10.3
10.6
36.4
19.8
33.5
35.4
28.8
18.8
10.3
12.5
16.0
36.1
7.25
12.3
30.7
33.4
25.6
35.3
14.5
4.96
6.74
8.65
9.28
4.76
5.59
8.99
13.9
8.09
14.1
13.3
9.74
12.2
9.82
9.77
4.32
3.65
12.4
6.60
11.6
14.1
10.2
7.53
3.90
4.74
6.58
11.2
2.13
5.21
12.3
10.5
9.95
13.9
Sm
Eu
3.07
1.55
2.02
2.30
2.29
1.29
1.53
2.03
2.56
1.96
2.70
2.82
2.52
2.90
2.52
2.42
1.72
1.14
2.41
2.08
2.53
2.87
2.47
2.59
1.42
1.76
2.16
2.85
1.13
1.43
2.74
2.67
2.62
2.71
Gd
16.5
5.36
7.78
10.2
11.6
5.32
5.25
10.8
16.9
8.66
13.4
15.2
10.6
13.3
10.3
10.9
4.58
4.32
13.1
8.87
12.9
13.1
10.3
8.91
5.11
6.46
7.62
15.5
3.56
4.87
12.9
12.7
11.2
13.3
Dy
13.7
4.50
6.56
10.4
10.5
4.60
5.11
9.38
13.2
7.89
12.7
13.6
9.74
13.6
9.46
10.2
4.12
4.00
12.2
7.88
12.6
13.3
9.96
10.4
3.72
5.81
8.44
13.0
2.82
4.95
12.8
10.5
9.69
13.3
Er
6.66
2.48
3.52
6.57
6.35
2.62
3.23
5.10
8.75
4.97
8.05
8.26
6.18
8.25
5.98
6.36
2.46
2.61
7.85
4.41
7.56
7.71
5.52
5.50
2.42
3.28
4.72
6.83
1.92
2.74
7.05
6.65
5.53
6.84
Yb
4.92
1.45
3.01
4.76
4.23
1.70
1.99
3.33
5.53
3.00
5.00
5.44
3.56
5.58
3.87
3.92
1.15
1.52
5.04
3.29
4.53
4.63
3.93
3.81
1.52
2.24
3.02
5.60
1.02
1.62
4.20
4.51
4.41
4.98
Pb
0.53
0.34
0.40
0.37
0.39
0.39
0.39
0.55
0.53
0.44
0.56
0.59
0.51
0.56
0.64
0.79
0.34
0.31
0.57
0.43
0.59
0.49
0.43
0.21
0.24
0.29
0.33
0.54
0.26
0.33
0.67
0.44
0.54
0.47
192
single
single
single
sigle
core
rim
single
core
rim
rim
core
single
rim
rim
single
single
single
single
single
single
single
core
rim
single
single
single
single
rim
core
single
single
single
single
single
single
single
single
22af3-1-1
22af3-1-3
22af3-2-2
22pf17-1-1
22pf17-1-3
22pf17-10-1
22pf17-10-2
22pf17-11-2
22pf17-12-1
22pf17-12-2
22pf17-14-1
22pf17-14-2
22pf17-15-1
22pf17-15-2
22pf17-16-1
22pf17-16-2
22pf17-16-3
22pf17-16-4
22pf17-18-1
22pf17-18-2
22pf17-18-4
22pf17-18-5
22pf17-2-2
22pf17-2-3
22pf17-3-1
22pf17-4-1
22pf17-4-2
22pf17-4-3
Spot Location
22af19-1-1
22af19-1-3
22af19-2-1
22af19-3-1
22af19-4-1
22af19-4-2
22af19-5-1
22af19-6-1
22af19-6-3
Sample ID
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
Table B4. Continued.
Eruption Date
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
airfall
Deposit
291
202
192
335
331
403
374
491
524
533
538
551
712
538
378
179
511
194
190
362
196
193
190
198
231
201
200
201
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
invalid
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Mg-Hbl
Mg-Hbl
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
499
217
203
411
414
526
210
386
216
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
926
915
940
936
958
959
959
961
965
982
952
933
867
972
872
868
932
877
859
868
870
888
875
877
877
911
878
861
970
896
882
959
960
958
895
936
894
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
43.5
43.8
43.7
43.7
44.0
44.4
43.9
44.3
44.3
43.9
43.9
43.1
45.9
44.1
46.3
46.5
44.8
45.5
46.2
46.0
46.5
45.0
45.8
45.7
45.6
44.4
45.9
46.5
43.2
45.1
45.8
44.5
44.0
43.3
46.0
44.4
45.3
1.83
1.64
2.13
2.05
1.74
1.94
2.00
1.95
2.08
1.90
2.08
2.25
1.94
1.92
1.91
1.84
1.82
2.04
1.92
1.96
1.88
1.84
2.02
1.87
1.88
1.93
1.97
1.96
2.09
2.12
1.99
2.14
2.08
2.23
2.02
1.82
1.99
12.0
11.9
12.7
12.4
12.7
12.7
12.9
13.1
13.0
12.9
13.3
12.8
9.0
12.8
9.4
9.2
12.3
9.4
9.4
9.3
9.5
10.1
9.6
9.5
9.4
11.3
9.6
9.5
13.0
10.0
9.6
12.6
12.8
13.4
9.7
12.6
9.9
12.6
14.9
14.6
11.7
12.5
13.0
14.0
13.9
14.6
10.9
11.0
10.9
10.8
10.6
11.0
11.0
10.9
11.1
10.8
11.1
11.0
11.0
10.9
11.0
10.9
10.8
11.0
10.9
11.0
10.8
10.6
10.9
10.9
10.8
14.9
14.3
13.0
13.0
11.6
10.5
10.5
11.3
10.8
10.5
11.9
15.6
13.6
11.2
14.0
14.0
12.6
14.2
13.8
13.6
13.8
15.1
14.1
14.3
14.2
10.9 14.4
10.8 14.7
11.0 14.7
10.9
11.0
11.0
10.8
11.0
11.2
11.0
10.8
11.0
13.4
13.8
14.1
14.3
15.4
15.7
15.5
15.2
15.4
15.7
14.7
12.5
14.8
15.7
14.5
14.6
14.6
14.3
14.4
14.8
14.5
13.8
14.3
14.2
14.4
13.9
14.2
14.2
14.7
14.1
14.5
15.4
14.7
14.1
14.6
14.1
14.3
0.21
0.23
0.14
0.12
0.12
0.12
0.09
0.14
0.12
0.13
0.11
0.21
0.17
0.14
0.23
0.23
0.16
0.21
0.19
0.17
0.21
0.23
0.17
0.23
0.23
0.20
0.22
0.19
0.16
0.21
0.23
0.12
0.15
0.15
0.23
0.20
0.24
2.34
2.18
2.32
2.34
2.34
2.39
2.37
2.40
2.47
2.46
2.40
2.40
2.03
2.46
2.01
1.95
2.38
2.05
1.92
1.97
2.03
2.01
2.11
2.03
1.95
2.15
1.99
1.98
2.39
2.17
1.96
2.32
2.42
2.43
2.13
2.28
2.04
0.28
0.28
0.30
0.29
0.24
0.29
0.29
0.31
0.29
0.29
0.25
0.40
0.29
0.26
0.29
0.26
0.27
0.28
0.27
0.26
0.26
0.30
0.27
0.27
0.24
0.25
0.30
0.34
0.28
0.29
0.30
0.25
0.25
0.30
0.26
0.27
0.28
F
0.07
0.05
0.03
0.06
0.07
0.00
0.04
0.04
0.05
Cl
0.018
0.044
0.043
0.016
0.019
0.014
0.041
0.008
0.037
SO2
0.006
0.016
0.008
0.040
0.021
0.016
0.020
0.000
0.017
99.4
100.1
100.1
100.0
100.1
100.1
100.2
100.6
99.7
Total
0.03
0.06
0.03
0.02
0.03
0.00
0.01
0.07
0.03
0.08
0.00
0.05
0.01
0.06
0.02
0.03
0.09
0.01
0.00
0.00
0.00
0.00
0.02
0.01
0.04
0.04
0.00
0.15
0.04
0.15
0.07
0.11
0.05
0.07
0.02
0.15
0.10
0.10
0.07
0.11
0.10
0.21
0.09
0.15
0.05
0.11
0.11
0.19
0.14
0.08
0.020
0.021
0.019
0.019
0.014
0.012
0.015
0.016
0.023
0.009
0.018
0.035
0.038
0.015
0.040
0.039
0.015
0.040
0.042
0.035
0.043
0.038
0.041
0.043
0.043
0.000 99.5
0.004 99.2
0.022 99.6
0.017 99.0
0.022 98.8
0.000 99.2
0.009 98.8
0.003 99.8
0.021 99.7
0.006 98.6
0.000 99.9
0.022 100.5
0.011 98.9
0.023 99.7
0.016 99.9
0.013 99.7
0.019 100.1
0.000 99.1
0.000 99.2
0.023 99.1
0.008 99.6
0.000 99.1
0.000 99.7
0.024 99.2
0.005 99.0
0.01 0.06 0.023 0.020 99.5
0.03 0.00 0.040 0.016 99.8
0.05 0.12 0.043 0.011 100.5
0.00
0.02
0.00
0.01
0.00
0.00
0.02
0.04
0.02
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
193
3.72
3.67
3.69
4.13
2.66
3.77
3.43
3.67
3.24
3.26
3.56
4.12
20.5
36.5
44.1
32.7
32.9
34.5
33.6
29.7
33.5
27.4
31.2
36.5
32.1
55.1
39.0
30.1
44.2
37.8
41.3
30.6
30.7
27.9
27.5
30.3
34.4
22af3-1-1
22af3-1-3
22af3-2-2
22pf17-1-1
22pf17-1-3
22pf17-10-1
22pf17-10-2
22pf17-11-2
22pf17-12-1
22pf17-12-2
22pf17-14-1
22pf17-14-2
22pf17-15-1
22pf17-15-2
22pf17-16-1
22pf17-16-2
22pf17-16-3
22pf17-16-4
22pf17-18-1
22pf17-18-2
22pf17-18-4
22pf17-18-5
22pf17-2-2
22pf17-2-3
22pf17-3-1
22pf17-4-1
22pf17-4-2
22pf17-4-3
209521
223936
204096
209797
205052
217166
205556
201768
216181
205450
208844
220962
230189
210900
228135
220175
223835
215257
217348
223143
221000
236553
216893
216476
218509
184031
195707
204916
203637
215705
196168
211339
224741
205650
197476
198766
208574
14349
14557
13562
13667
13978
15377
14326
13024
13076
83.4
39.1
69.7
70.4
78.6
80.7
77.3
80.9
84.0
73.5
77.0
132
158
78.6
131
137
110
145
146
145
142
128
140
118
130
12253
11296
15071
14988
12988
13854
13612
13798
14603
13033
14200
13912
13618
13344
13114
13401
12763
13354
12941
13295
12859
13128
14295
13149
13566
115 13402
149 12923
150 12611
77.8
113
140
78.0
73.0
75.0
131
110
128
Co
Ni
Cu
327
333
550
564
634
698
661
636
692
606
666
445
451
665
437
484
591
448
436
445
455
432
452
479
469
Zn
Ga
65.0
61.7
75.2
77.3
80.9
82.6
77.0
79.5
81.3
75.7
79.8
79.7
74.7
81.7
71.7
76.8
77.1
71.6
74.5
73.4
77.2
72.3
72.9
72.5
75.9
54.9
79.5
89.5
90.5
243
299
308
274
240
207
313
70.6
81.0
294
67.7
121
241
76.9
76.6
80.7
84.9
65.2
83.1
97.1
95.0
5.25
9.16
11.2
6.69
11.9
23.8
14.8
8.99
8.43
13.8
9.18
11.6
7.44
18.8
31.8
17.7
21.1
16.4
20.1
8.76
16.4
9.72
14.1
19.1
18.6
138
150
93.9
93.2
77.5
70.6
68.7
68.0
70.5
69.0
66.1
156
163
74.4
156
160
145
163
158
155
160
191
144
152
158
20.9
19.7
19.5
19.3
18.3
16.6
17.1
16.6
18.0
17.0
16.9
22.7
22.1
16.5
21.0
20.6
20.2
20.7
20.4
20.1
21.7
23.1
20.1
20.0
20.2
131 16.5
143 16.3
137 15.4
66.5 126 1.43 74.3 16.1
66.0 74.7 1.85 138 18.6
63.4 68.6 1.43 141 16.3
68.0 132 1.95 73.0 15.6
65.2 134 2.10 73.7 14.9
67.7 69.7 2.16 86.7 17.1
64.2 110 2.35 121 15.0
64.9 116 1.80 125 16.5
69.1 122 1.33 114 15.3
405 60.9 61.8 1.53
408 67.2 73.1 1.46
365 59.7 64.6 2.62
587
446
391
542
527
547
459
491
453
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
22af19-1-1
22af19-1-3
22af19-2-1
22af19-3-1
22af19-4-1
22af19-4-2
22af19-5-1
22af19-6-1
22af19-6-3
Sample ID
Table B4. Continued.
Ge
Rb
Sr
Y
Zr
Nb
0.57
0.41
1.03
0.65
0.61
0.80
0.83
0.79
0.87
0.93
0.89
0.80
0.58
0.79
0.69
0.65
0.77
0.77
0.69
0.63
0.69
1.39
0.47
0.62
0.72
124
130
194
169
154
173
160
160
186
158
183
103
83.7
150
91.2
93.9
117
98.4
87.6
94.3
89.0
99.0
103
93.6
85.9
46.1
30.7
22.0
21.1
19.6
16.2
15.5
17.2
19.4
16.7
17.4
62.0
62.5
18.1
61.3
57.0
39.9
59.2
64.2
62.1
64.6
65.7
58.5
61.0
63.0
63.4
63.8
36.9
35.8
40.9
18.7
22.2
26.3
29.3
21.4
24.0
69.0
65.3
31.3
72.5
64.1
53.7
63.9
68.2
73.2
71.6
75.9
64.9
66.9
70.7
3.42
3.59
2.24
2.23
1.64
1.35
1.32
1.60
1.76
1.17
1.58
5.85
6.91
1.48
5.72
6.35
3.88
5.76
6.56
6.60
6.69
7.10
6.53
5.59
6.50
0.56 113 52.5 64.6 5.17
0.36 86.8 65.8 70.9 6.51
0.50 79.8 72.7 71.3 6.14
0.62 200 23.6 45.9 2.01
0.75 123 57.0 68.1 6.00
0.75 97.3 64.6 72.7 6.29
0.58 169 21.8 40.3 1.86
1.00 181 19.7 31.4 1.95
0.79 205 25.1 38.6 2.17
0.72 120 49.9 57.4 4.66
0.90 121 47.2 58.7 4.42
0.65 105 55.5 57.6 5.01
Mo
Ag
In
0.093
0.231
0.259
0.121
0.084
0.114
0.142
0.168
0.205
Sn
0.96
1.46
1.33
0.77
0.71
0.81
1.04
1.23
1.10
Ba
44.2
49.9
45.1
30.8
34.9
42.4
41.7
38.8
37.0
La
2.50
5.93
6.25
1.83
1.51
2.05
4.89
4.27
5.08
Ce
10.4
24.1
26.8
7.80
7.12
8.87
20.0
19.1
22.1
Pr
2.04
5.04
5.72
1.60
1.65
1.89
4.18
4.35
4.52
Nd
13.8
32.7
39.4
12.1
10.9
13.3
28.2
28.2
29.9
4.85
11.8
13.6
4.26
3.99
5.80
10.5
10.1
11.2
Sm
Eu
1.71
2.84
3.26
1.31
1.43
1.67
2.41
2.45
2.37
Gd
6.15
12.5
16.0
6.11
5.41
6.22
11.7
11.8
13.3
Dy
4.98
12.0
14.0
4.95
4.62
5.52
10.1
10.8
11.4
Er
2.82
7.86
8.83
3.54
2.99
3.40
7.07
5.78
7.32
Yb
1.63
4.23
6.01
2.12
1.60
1.96
3.63
3.96
4.52
Pb
1.73
0.56
0.48
0.27
0.30
0.46
0.44
0.43
0.44
0.036
0.086
0.022
0.021
0.038
0.032
0.029
0.021
0.033
0.023
0.016
0.062
0.042
0.128
0.071
0.072
0.042
0.100
0.040
0.060
0.040
0.076
0.023
0.031
0.030
0.199
0.158
0.120
0.110
0.095
0.081
0.075
0.083
0.091
0.076
0.073
0.244
0.271
0.085
0.254
0.246
0.200
0.245
0.280
0.245
0.283
0.246
0.235
0.238
0.258
1.50
1.45
0.89
0.89
0.87
0.58
0.65
0.62
0.77
0.64
0.72
1.64
1.91
0.83
1.54
1.56
1.25
1.55
1.59
1.60
1.63
1.62
1.59
1.64
1.65
37.8
31.8
41.3
34.5
30.3
31.6
29.2
31.3
36.7
28.4
34.3
49.4
51.2
31.5
46.8
46.1
38.4
48.7
46.5
53.0
44.6
74.6
50.1
46.7
43.6
4.56
4.07
2.29
1.78
1.72
1.20
1.18
1.37
1.64
1.38
1.28
6.03
6.71
1.25
6.52
6.39
4.41
6.19
6.82
6.96
6.82
9.64
6.04
6.49
6.60
21.1
18.6
9.21
8.24
7.84
5.66
5.51
6.26
8.03
5.53
6.39
28.5
31.5
6.61
31.8
27.1
19.8
28.7
32.5
30.9
30.5
38.0
28.8
28.7
29.6
4.34
3.70
1.90
1.80
1.54
1.09
0.98
1.15
1.54
1.20
1.26
5.97
6.02
1.29
5.95
5.31
3.90
5.57
5.79
6.09
6.20
6.98
5.75
5.99
5.93
26.6
23.6
12.5
10.7
11.1
7.37
7.03
8.20
10.4
7.45
8.40
35.5
38.0
8.29
36.4
34.6
22.9
35.1
38.7
37.9
41.0
42.0
36.3
35.1
38.7
10.3
6.68
4.01
4.23
3.97
3.19
3.21
2.74
4.15
3.01
2.68
12.9
14.6
3.10
13.3
11.8
8.77
11.8
14.6
13.3
13.7
14.3
11.5
12.6
13.3
2.51
2.42
1.57
1.51
1.32
1.04
1.13
1.14
1.29
1.03
0.92
2.90
2.72
1.15
2.66
2.58
1.96
2.62
2.98
3.04
2.88
2.68
2.71
2.80
2.89
11.3
6.78
5.56
5.06
4.45
3.88
3.85
3.98
4.02
4.24
4.34
14.6
16.7
4.07
16.3
14.0
9.67
13.5
15.0
14.7
16.5
16.4
12.7
14.3
14.7
8.75
6.47
4.69
4.87
4.42
3.65
3.73
3.53
4.21
3.48
3.58
14.0
14.4
4.35
13.0
13.1
8.83
12.9
14.6
13.0
14.4
14.2
12.2
12.8
13.1
5.38
3.82
2.35
2.60
2.29
1.79
1.78
1.69
2.05
1.91
1.68
6.06
7.56
2.39
7.13
6.32
5.34
6.36
7.40
7.89
7.31
7.61
7.52
6.87
6.86
3.39
2.98
1.61
1.72
1.78
1.28
1.62
1.48
1.41
1.39
1.36
5.03
4.72
1.40
4.08
4.66
3.23
4.82
4.88
5.11
4.74
5.21
4.73
4.85
5.24
0.59
0.50
0.42
0.35
0.39
0.33
0.30
0.27
0.39
0.34
0.35
0.58
0.64
0.31
0.67
0.58
0.50
0.58
0.51
0.73
0.61
1.27
0.59
0.57
0.57
0.026 0.209 1.44 45.0 5.05 22.8 4.89 31.0 11.0 2.41 12.5 11.6 6.96 4.40 0.49
0.035 0.252 1.47 42.2 6.41 29.1 5.82 37.1 14.2 2.85 16.6 14.0 9.02 5.24 0.51
0.304 0.235 1.46 40.5 6.84 29.1 6.12 40.3 14.8 2.86 17.5 15.4 10.1 5.75 0.55
0.103
0.055
0.373
0.095
0.074
0.045
0.057
0.067
0.056
194
single
rim
core
rim
single
rim
rim
core
single
single
core
rim
core
single
single
single
single
single
rim
core
core
rim
rim
core
rim
core
single
single
22pfA6-1-1
22pfA6-1-2
22pfA6-2-1
22pfA6-2-2
22pfA6-3-1
22pfA6-3-2
22pfA6-3-3
22pfA6-4-1
22pfA6-6-2
7wrs16-1-1
7wrs16-1-3
7wrs16-2-1
7wrs16-3-1
7wrs16-3-3
7wrs16-4-2
7wrs16-4-4
7wrs16-5-1
7wrs16-5-2
7wrs16-6-2
7wrs16-6-3
7wrs16-7-2
7wrs16-8-1
Spot Location
22pf17-5-1
22pf17-7-1
22pf17-7-2
22pf17-7-3
22pf17-8-1
22pf17-9-2
Sample ID
August 7
August 7
August 7
August 7
August 7
August 7
August 7
August 7
August 7
August 7
August 7
August 7
August 7
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
July 22
Table B4. Continued.
Eruption Date
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
pyroclastic flow
Deposit
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
low-Ca
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
916
932
877
879
925
906
925
949
945
875
917
896
943
935
975
957
832
846
954
966
962
851
192
280
253
371
386
550
423
140
148
455
522
492
138
878
880
872
877
977
919
310
341
218
213
359
307
324
439
346
201
200
192
208
529
353
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
46.4
44.8
45.2
42.9
44.9
43.7
44.0
46.8
46.6
42.7
43.9
44.0
46.7
43.2
43.6
45.4
45.1
43.7
43.0
43.6
43.0
44.4
45.8
45.4
46.1
45.8
43.6
44.0
1.91
1.76
1.80
2.30
1.80
2.26
2.18
1.89
1.96
2.22
2.09
2.00
1.82
1.92
1.89
1.93
1.99
1.89
2.08
1.83
2.06
1.98
2.01
1.98
1.93
1.83
1.97
1.97
9.4
11.0
10.7
12.6
12.4
13.2
12.8
8.2
8.3
13.6
13.1
12.9
8.0
11.5
11.7
9.8
9.8
12.0
11.6
11.5
13.1
11.7
9.5
9.5
9.4
9.7
13.1
12.2
10.8
10.5
10.9
11.1
10.9
11.0
10.8
10.9
10.9
11.1
10.9
10.7
10.9
10.5
9.8
10.8
10.9
11.0
10.5
10.6
10.8
10.8
10.8
10.9
10.7
10.8
10.5
10.9
14.7
14.7
14.7
14.4
11.2
11.9
11.8
16.4
15.4
13.3
11.7
12.7
15.6
15.5
15.9
14.0
14.2
11.8
16.7
13.6
11.4
10.9
14.1
14.0
14.2
14.2
11.9
13.6
14.2
14.1
14.0
13.4
15.5
14.8
15.2
13.4
13.9
13.8
15.2
14.7
14.2
12.8
12.8
14.1
14.1
14.8
11.9
14.0
14.7
15.7
14.3
14.2
14.2
14.2
15.0
13.8
0.24
0.23
0.22
0.16
0.12
0.13
0.16
0.22
0.23
0.14
0.11
0.15
0.22
0.24
0.25
0.19
0.17
0.13
0.23
0.19
0.10
0.12
0.20
0.22
0.19
0.24
0.14
0.18
2.07
2.22
2.14
2.46
2.29
2.54
2.24
2.00
1.98
2.38
2.45
2.41
2.08
2.19
2.17
2.01
2.08
2.20
2.18
2.20
2.23
2.33
2.09
2.08
2.13
2.04
2.46
2.22
0.26
0.24
0.25
0.30
0.27
0.33
0.28
0.43
0.43
0.34
0.28
0.25
0.43
0.20
0.18
0.27
0.30
0.23
0.27
0.26
0.27
0.24
0.29
0.27
0.30
0.26
0.24
0.24
0.03
0.01
0.02
0.02
0.00
0.06
0.03
0.01
0.00
0.06
0.00
0.03
0.01
0.05
0.07
0.07
0.02
0.00
0.07
0.02
0.00
0.00
0.01
0.00
0.06
0.03
0.05
0.01
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
F
0.10
0.07
0.15
0.07
0.06
0.07
0.09
0.10
0.22
0.08
0.03
0.07
0.16
0.02
0.00
0.06
0.06
0.02
0.03
0.07
0.07
0.07
0.07
0.11
0.15
0.20
0.06
0.07
Cl
0.035
0.027
0.027
0.026
0.021
0.022
0.016
0.169
0.119
0.015
0.011
0.015
0.120
0.025
0.023
0.045
0.056
0.021
0.030
0.019
0.019
0.015
0.042
0.040
0.034
0.040
0.019
0.020
SO2
0.024
0.013
0.009
0.014
0.022
0.012
0.015
0.000
0.000
0.016
0.007
0.026
0.011
0.013
0.013
0.020
0.049
0.035
0.015
0.038
0.002
0.026
0.000
0.005
0.012
0.004
0.024
0.031
100.3
99.8
100.1
99.6
99.6
100.0
99.8
100.5
100.1
99.8
99.7
100.0
100.3
98.1
98.4
98.7
98.8
97.7
98.7
97.9
97.8
98.2
99.2
98.6
99.4
99.4
99.1
99.2
Total
195
34.9
26.1
27.8
31.3
31.5
35.8
7.20
7.81
13.0
10.7
11.4
12.3
9.58
12.0
11.7
3.40
3.35
4.49
4.01
3.34
3.79
4.15
4.72
4.83
4.34
4.11
3.65
3.91
22pfA6-1-1
22pfA6-1-2
22pfA6-2-1
22pfA6-2-2
22pfA6-3-1
22pfA6-3-2
22pfA6-3-3
22pfA6-4-1
22pfA6-6-2
7wrs16-1-1
7wrs16-1-3
7wrs16-2-1
7wrs16-3-1
7wrs16-3-3
7wrs16-4-2
7wrs16-4-4
7wrs16-5-1
7wrs16-5-2
7wrs16-6-2
7wrs16-6-3
7wrs16-7-2
7wrs16-8-1
193390
206894
214322
237423
248138
260946
248061
191258
198161
226172
237580
247576
205699
208881
199612
212139
205344
224353
207182
216647
201124
204332
155
77.0
120
101
81.1
73.5
77.1
102
134
75.9
80.0
79.4
133
65.5
66.9
102
103
74.8
53.7
61.8
85.3
86.4
13002
12285
12572
14671
12099
14973
14664
12977
13497
15366
13560
13138
12357
13342
13513
14557
14187
13727
13890
12919
14710
13773
217968 148 13622
225642 134 12991
219655 141 13238
220215 147 12747
197252 78.0 12993
208507 120 13071
378
321
397
543
597
572
605
389
408
550
605
586
361
436
465
468
434
472
323
370
656
612
439
448
447
441
622
514
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
22pf17-5-1
22pf17-7-1
22pf17-7-2
22pf17-7-3
22pf17-8-1
22pf17-9-2
Sample ID
Table B4. Continued.
Co
65.7
60.4
62.6
71.2
75.0
70.8
72.1
71.9
70.2
67.0
69.0
70.2
73.1
61.8
63.6
71.0
72.6
72.2
65.2
70.4
79.4
79.1
72.4
75.9
75.6
71.9
74.6
71.0
Ni
63.1
34.2
91.0
185
237
177
203
126
144
53.4
178
187
137
72.5
98.1
73.0
56.0
128
35.7
20.2
132
170
87.8
86.1
79.8
72.6
241
180
Cu
Zn
Ga
1.48
1.71
2.27
2.02
1.57
1.44
1.51
1.45
1.36
1.27
1.34
2.60
1.97
143
124
144
88.9
71.1
71.0
68.2
152
138
91.2
70.6
64.7
147
17.2
17.9
18.8
16.5
15.8
13.5
14.2
18.1
17.5
17.2
14.3
13.5
16.0
2.62 130 18.6
2.69 126 18.5
4.97 141 20.0
7.73 130 19.7
2.02 95.1 19.1
5.73 140 20.9
1.68 113 19.7
4.24 72.8 18.0
3.69 71.5 16.8
10.4 158 20.5
10.1 158 20.8
13.5 164 22.0
8.12 162 20.4
9.32 71.9 17.4
21.0 116 17.8
Ge
Rb
0.37
0.58
0.63
0.68
0.68
0.87
0.49
0.55
0.55
0.66
0.67
0.35
0.54
0.57
0.35
0.87
0.39
0.52
0.63
0.86
0.76
0.52
0.58
0.59
1.03
0.57
0.86
0.70
Sr
86.7
119
110
152
146
181
170
68.2
72.6
209
162
156
67.3
131
127
125
123
160
156
137
202
171
92.0
90.4
90.9
89.5
164
121
Y
65.5
44.7
53.0
33.9
20.9
19.2
19.9
99.9
115
26.7
20.5
18.6
123
28.7
28.7
46.7
49.3
30.3
44.5
36.5
21.6
20.0
60.4
62.4
64.8
64.0
18.2
42.8
Zr
73.6
58.6
59.3
47.9
31.0
29.8
40.8
163
152
38.7
33.4
43.6
150
63.8
58.7
56.9
61.1
51.5
74.9
57.9
37.9
31.1
64.3
68.9
69.1
67.1
25.3
53.4
Nb
6.46
3.95
4.69
3.25
1.42
1.81
1.73
17.3
16.7
2.27
1.42
1.70
16.1
6.96
6.75
5.27
4.74
2.70
5.70
3.59
1.70
1.74
6.10
6.19
6.18
6.32
1.46
3.82
Mo
Ag
0.211
0.084
0.032
0.194
0.061
0.054
0.040
0.020
0.040
0.247
0.053
0.035
0.106
0.031
0.033
0.028
0.040
0.043
0.076
0.009
0.035
0.111
0.039
0.039
0.049
0.014
0.033
0.032
In
0.231
0.154
0.257
0.124
0.086
0.096
0.094
0.261
0.289
0.120
0.099
0.051
0.269
0.108
0.124
0.187
0.199
0.131
0.154
0.157
0.101
0.099
0.274
0.267
0.267
0.256
0.087
0.204
Sn
1.40
1.32
1.32
0.93
0.72
0.72
0.80
1.65
1.62
0.87
0.74
0.69
1.51
0.82
0.63
1.23
1.31
1.09
1.05
1.10
0.83
0.79
1.61
1.61
1.70
1.61
0.74
1.15
Ba
39.0
35.8
41.4
40.9
27.0
31.3
31.0
73.6
67.1
39.7
30.7
28.6
55.6
40.8
38.3
50.5
48.0
37.0
47.2
37.9
37.9
31.5
45.7
48.0
45.4
49.3
35.2
39.0
La
6.62
3.37
4.67
3.22
1.29
1.44
2.01
19.3
15.9
2.37
1.62
1.67
14.8
4.13
4.42
4.45
4.80
2.39
6.00
3.71
1.89
1.62
6.27
6.31
6.23
5.73
1.29
3.88
Ce
27.2
16.9
20.9
13.6
6.00
6.24
7.28
74.8
64.4
9.75
6.75
6.28
60.7
18.6
17.8
19.8
22.1
12.4
24.3
16.6
8.79
7.28
28.6
30.1
30.8
31.7
6.68
18.8
Pr
5.89
3.55
4.61
2.86
1.37
1.27
1.61
13.8
12.2
2.17
1.54
1.36
12.0
3.23
3.36
4.06
4.18
2.36
4.73
3.27
1.93
1.38
5.66
6.16
6.15
6.14
1.18
3.78
Nd
37.3
24.4
30.9
19.9
10.0
9.91
10.3
72.6
75.1
14.3
10.5
9.63
74.1
18.7
18.4
25.9
29.1
15.6
27.0
22.5
11.4
9.98
35.3
39.3
38.5
38.8
8.54
21.7
13.3
8.34
10.1
6.51
4.49
3.00
4.12
20.4
23.5
4.96
4.04
3.98
23.5
5.25
5.26
9.40
10.9
5.48
8.64
7.21
3.66
3.62
13.6
13.6
13.8
14.6
3.05
8.54
Sm
Eu
2.80
1.97
2.40
1.90
1.23
1.47
1.34
2.99
3.48
1.81
1.29
1.24
3.46
2.19
1.93
2.28
2.56
1.81
2.25
1.87
1.35
1.33
2.77
2.89
2.86
2.73
1.25
2.03
Gd
15.5
9.67
12.6
8.54
4.96
5.01
4.51
21.7
25.0
6.77
4.35
4.18
27.9
5.89
5.15
9.70
11.0
6.61
10.0
7.91
4.30
4.50
15.3
15.6
15.1
15.1
3.94
11.4
Dy
14.1
9.55
10.9
7.99
4.08
4.51
4.57
19.1
23.4
5.77
4.45
3.78
25.8
6.30
5.94
9.77
11.2
6.26
8.42
7.87
4.52
4.67
13.3
14.7
14.3
13.8
3.84
9.05
Er
9.51
5.61
6.70
4.66
2.52
2.80
2.50
14.0
15.4
3.45
2.72
2.76
17.2
3.33
3.30
5.43
6.05
3.15
5.36
3.65
2.29
1.80
6.62
7.05
7.29
7.23
2.14
5.08
Yb
5.53
3.31
4.02
3.02
1.74
1.67
1.63
9.67
9.94
2.15
1.81
1.73
10.2
2.78
2.47
3.72
4.44
2.38
3.85
3.10
1.95
1.24
5.07
5.02
5.13
5.60
1.44
3.66
Pb
0.51
0.49
0.52
0.45
0.35
0.37
0.34
0.60
0.55
0.50
0.33
0.31
0.59
0.42
0.39
0.67
0.48
0.39
0.59
0.46
0.35
0.34
0.61
0.58
0.61
0.58
0.34
0.46
196
rim
core
core
rim
rim
core
rim
rim
core
rim
single
single
core
rim
rim
core
core
core
rim
rim
rim
core
single
single
rim
core
single
single
rim
single
single
core
single
single
single
single
single
rim
core
single
single
MH09-04a-1-1
MH09-04a-1-2
MH09-04a-10-2
MH09-04a-11-1
MH09-04a-12-1
MH09-04a-12-2
MH09-04a-14-3
MH09-04a-15-2b
MH09-04a-16-2
MH09-04a-17-1
MH09-04a-18-4
MH09-04a-2-2
MH09-04a-3-1
MH09-04a-5-2
MH09-04a-5-3
MH09-04a-6-2
MH09-04a-6-4
MH09-04a-7-1
MH09-04a-7-2
MH09-04a-8-1
MH09-04a-9-1
Spot Location
MH09-04-1-1
MH09-04-1-2
MH09-04-1-3
MH09-04-1-4
MH09-04-2-1
MH09-04-2-2
MH09-04-2-3
MH09-04-3-1
MH09-04-3-2
MH09-04-3-3
MH09-04-3-4
MH09-04-3-5
MH09-04-4-2
MH09-04-4-3
MH09-04-5-1
MH09-04-5-2
MH09-04-5-3
MH09-04-5-4
MH09-04-5-5
MH09-04-6-1
Sample ID
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid mafic enclave
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Old Maid
Eruption Date
Mg-Hbl
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Mg-Hst
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Tsch-Prg
Mg-Hbl
Mg-Hbl
142
132
326
422
401
480
314
536
298
370
573
120
341
263
322
336
392
426
340
348
302
217
156
146
142
140
188
145
160
138
170
166
197
161
125
118
158
140
338
130
157
816
814
947
945
938
960
942
985
940
947
969
805
949
959
932
937
979
962
948
956
932
871
830
817
822
811
867
821
834
810
833
838
857
837
815
789
811
809
915
801
824
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
48.4
47.6
43.6
43.7
43.1
41.8
44.1
43.0
43.3
43.5
43.4
49.1
43.0
44.1
43.6
43.8
43.6
44.1
43.7
43.4
43.2
45.2
46.8
47.1
47.9
48.2
46.3
47.1
47.3
47.8
46.9
46.4
46.3
46.9
47.7
48.8
47.4
47.8
43.1
48.5
47.1
1.48
1.40
2.72
2.23
2.18
2.37
3.09
2.48
3.23
2.01
2.18
1.29
2.96
2.75
2.66
2.67
2.65
2.24
2.92
2.86
2.72
1.94
1.68
1.55
1.33
1.50
1.82
1.54
1.70
1.54
1.73
1.63
1.88
1.72
1.28
1.21
1.66
1.60
2.38
1.43
1.62
7.8
7.6
11.7
13.1
12.8
14.1
11.7
13.4
11.4
12.2
13.6
7.0
11.9
11.0
11.6
11.8
12.2
13.1
11.9
12.0
11.5
10.2
8.3
8.0
7.8
7.8
9.1
8.1
8.4
7.7
8.8
8.6
9.5
8.5
7.0
6.9
8.5
7.9
12.0
7.5
8.4
10.9
11.0
11.1
11.3
10.7
11.1
11.3
10.8
11.2
10.1
10.9
10.9
11.1
11.3
11.1
11.0
10.6
11.0
11.1
11.2
10.9
11.1
10.9
10.9
10.9
10.9
11.0
11.0
10.9
10.9
11.1
11.1
11.2
10.9
10.8
10.9
10.8
10.9
11.0
10.9
11.1
13.9
14.0
12.3
11.7
15.2
13.3
12.8
12.0
13.4
15.9
11.5
13.6
13.1
12.8
13.1
12.5
12.0
11.5
12.4
11.9
15.0
15.5
14.5
14.6
13.7
14.1
13.4
13.9
14.0
13.7
14.3
14.0
13.4
13.8
13.3
13.7
15.0
14.2
15.1
14.4
14.0
14.9
15.1
14.8
14.6
12.6
13.3
14.3
14.6
13.9
12.7
14.6
15.5
14.0
14.1
14.2
14.6
15.0
15.1
14.5
14.8
13.2
13.4
14.4
14.5
15.2
14.8
14.8
14.8
14.6
14.8
14.2
14.7
14.5
14.6
15.7
15.5
13.8
14.4
12.4
14.9
14.7
0.28
0.22
0.11
0.14
0.21
0.13
0.12
0.16
0.13
0.27
0.13
0.28
0.14
0.17
0.15
0.10
0.16
0.15
0.13
0.11
0.17
0.22
0.23
0.22
0.26
0.24
0.24
0.19
0.24
0.22
0.23
0.24
0.20
0.19
0.24
0.22
0.21
0.22
0.23
0.24
0.22
1.60
1.64
2.36
2.33
2.36
2.43
2.40
2.45
2.34
2.32
2.41
1.52
2.32
2.99
2.23
2.26
2.45
2.39
2.35
2.40
2.32
2.06
1.68
1.59
1.63
1.57
1.91
1.73
1.70
1.58
1.74
1.64
1.90
1.84
1.50
1.42
1.64
1.66
2.21
1.51
1.62
0.30
0.27
0.20
0.27
0.23
0.20
0.36
0.25
0.24
0.31
0.22
0.30
0.35
0.26
0.24
0.24
0.18
0.19
0.29
0.27
0.25
0.36
0.35
0.36
0.28
0.31
0.36
0.34
0.37
0.28
0.39
0.34
0.35
0.35
0.29
0.27
0.36
0.29
0.25
0.27
0.37
0.02
0.03
0.05
0.04
0.06
0.06
0.02
0.01
0.09
0.01
0.05
0.00
0.09
0.04
0.05
0.02
0.06
0.04
0.01
0.04
0.15
0.11
0.00
0.03
0.02
0.01
0.03
0.02
0.00
0.03
0.03
0.06
0.00
0.01
0.00
0.02
0.04
0.00
0.04
0.00
0.02
Major Elements by EMPA (wt. %)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
Table B5. Amphibole analyses from the 1980 eruptions of Mt. Hood.
F
0.13
0.18
0.00
0.08
0.09
0.05
0.07
0.04
0.10
0.16
0.13
0.22
0.20
0.19
0.07
0.09
0.13
0.05
0.08
0.12
0.16
0.20
0.16
0.29
0.25
0.10
0.20
0.17
0.16
0.15
0.16
0.24
0.18
0.15
0.10
0.20
0.09
0.17
0.05
0.37
0.23
Cl
0.088
0.096
0.023
0.019
0.027
0.019
0.029
0.016
0.031
0.032
0.015
0.086
0.027
0.024
0.026
0.014
0.019
0.015
0.023
0.024
0.028
0.094
0.089
0.093
0.106
0.093
0.077
0.101
0.087
0.092
0.101
0.087
0.075
0.088
0.097
0.087
0.090
0.084
0.039
0.088
0.098
SO2
Total
0.011 99.9
0.000 99.1
0.025 98.9
0.019 99.6
0.027 99.6
0.017 98.9
0.005 100.2
0.008 99.3
0.009 99.3
0.005 99.5
0.025 99.2
0.007 99.9
0.019 99.2
0.016 99.9
0.006 99.1
0.009 99.2
0.020 99.1
0.008 99.8
0.013 99.5
0.013 99.1
0.004 99.5
0.002 100.2
0.017 99.0
0.001 99.3
0.003 99.3
0.000 99.6
0.001 99.3
0.002 98.9
0.020 99.6
0.015 98.9
0.022 99.7
0.006 99.0
0.000 99.5
0.000 99.1
0.014 98.0
0.013 99.2
0.003 99.6
0.008 99.2
0.000 98.8
0.012 100.1
0.020 99.5
197
119
101
88.2
130
126
69.3
119
124
118
135
140
149
90.9
122
118
35.9
77.6
94.8
116
136
121
93.4
91.7
135
132
125
113
94.7
114
79.3
126
114
70.3
73.5
96.1
83.8
119
121
112
172
134
MH09-04a-1-1
MH09-04a-1-2
MH09-04a-10-2
MH09-04a-11-1
MH09-04a-12-1
MH09-04a-12-2
MH09-04a-14-3
MH09-04a-15-2b
MH09-04a-16-2
MH09-04a-17-1
MH09-04a-18-4
MH09-04a-2-2
MH09-04a-3-1
MH09-04a-5-2
MH09-04a-5-3
MH09-04a-6-2
MH09-04a-6-4
MH09-04a-7-1
MH09-04a-7-2
MH09-04a-8-1
MH09-04a-9-1
3.70
9.21
0.83
2.27
7.80
9.78
6.57
5.00
2.52
1.30
25.3
14.4
17.8
5.19
9.94
3.68
1.90
1.69
1.68
2.13
0.06
6.10
3.83
2.31
3.05
14.9
3.81
3.46
213924
216000
196303
207428
205571
219034
198534
194978
189587
195290
200126
218463
228396
221941
208110
204025
190059
209074
194573
212818
199770
115
114
75.9
56.3
59.2
56.2
80.9
64.0
80.7
54.5
55.9
119
71.6
63.3
79.2
87.5
72.8
50.7
88.6
69.4
64.7
9847
9439
19763
15491
16586
16966
19383
16531
22103
15253
16325
9538
20045
16878
19354
20078
19115
15666
19851
18587
18769
182254 105 13808
202301 178 11818
191151 151 10964
214899 105 10013
203119 121 10778
196826 86.8 12988
208938 116 10742
207190 94.4 11339
187506 138 10309
209536 125 10295
217895 111 11193
204474 98.6 14186
202849 125 10763
209106 139 8909
227692 134 9807
202548 136 12127
216592 139 10745
220779 103 15014
225110 135 10863
208443 119 11652
323
307
503
458
426
478
473
458
505
219
444
308
584
456
486
515
477
407
557
593
528
400
381
405
288
317
349
330
340
339
313
359
456
328
288
296
359
325
448
335
340
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
MH09-04-1-1
MH09-04-1-2
MH09-04-1-3
MH09-04-1-4
MH09-04-2-1
MH09-04-2-2
MH09-04-2-3
MH09-04-3-1
MH09-04-3-2
MH09-04-3-3
MH09-04-3-4
MH09-04-3-5
MH09-04-4-2
MH09-04-4-3
MH09-04-5-1
MH09-04-5-2
MH09-04-5-3
MH09-04-5-4
MH09-04-5-5
MH09-04-6-1
Sample ID
Table B5. Continued.
Co
107
115
130
96.6
97.9
71.0
99.8
91.6
98.7
105
111
153
102
120
112
123
117
189
128
105
Ni
Cu
35.0
13.5
12.3
24.4
23.6
8.74
14.8
50.5
14.0
29.1
54.5
37.6
16.1
25.8
28.0
1.32
6.98
8.75
22.6
21.5
143
167
147
158
149
138
153
146
139
163
163
147
141
165
200
174
178
174
196
154
Zn
Ga
17.1
18.1
15.9
16.2
15.1
16.5
16.9
15.2
14.9
16.7
16.7
19.5
16.4
15.9
15.1
19.3
18.1
17.0
15.3
16.1
Ge
0.14
3.47
2.85
2.87
2.50
2.62
2.47
1.95
2.04
3.03
3.25
1.96
2.81
2.17
3.03
2.16
2.09
2.39
3.10
1.72
0.85
0.86
0.69
1.01
0.18
0.61
0.89
0.55
Rb
189
93.5
78.6
75.4
80.4
115
82.8
86.4
74.3
75.3
96.8
135
80.7
55.0
66.7
98.6
80.4
169
80.9
91.1
Sr
Y
57.2
124
112
101
97.8
57.3
97.5
91.2
97.0
108
93.5
64.5
82.4
133
111
108
93.9
70.4
110
97.5
Zr
81.4
93.0
87.7
92.6
84.2
93.2
79.2
94.6
78.5
79.4
85.4
88.7
86.2
70.1
73.9
126
93.1
71.5
81.8
104
Nb
8.15
15.3
13.8
12.6
12.5
10.2
13.3
13.8
13.6
14.5
14.4
10.0
13.2
15.5
13.9
15.1
14.7
10.3
14.1
13.6
67.6 108 19.5 187 17.9 3.38 0.33 70.4 87.7 62.2 11.6
71.4 99.3 9.42 193 19.1 3.07 0.28 66.2 94.8 67.7 13.0
79.1 372 43.5 85.7 19.1 0.94 4.32 255 24.7 45.7 5.15
81.2 412 31.0 89.3 21.9 1.35
290 19.4 69.7 4.17
76.3 204 57.5 92.5 23.0 0.21
283 25.0 56.0 4.18
86.2 321 28.9 98.4 24.0 2.93 0.72 300 21.4 61.1 4.63
78.4 313 49.7 93.7 19.5 1.81
246 25.0 37.4 4.92
71.1 296 35.0 70.6 15.9 2.40
300 25.1 80.1 4.41
72.2 171 32.3 88.2 16.6 2.48 0.37 251 34.4 80.9 6.79
53.2 23.9 19.1 128 18.8 2.90
194 44.8 74.3 7.77
69.9 352 20.5 75.3 16.5 1.08
273 20.4 75.3 5.46
68.2 106 20.7 198 17.6 3.19 0.10 71.5 89.7 69.1 12.0
75.7 352 27.7 97.6 24.9 2.37 4.16 254 24.0 68.4 5.45
80.7 372 36.9 124 23.3 0.51
251 22.8 76.4 5.20
82.8 317 38.0 87.9 21.0 1.64 1.75 248 26.6 51.7 5.18
83.3 328 35.0 89.0 20.5 1.62
252 24.2 48.7 5.87
77.4 387 34.0 88.0 21.6 0.68 0.66 258 23.5 44.6 5.50
76.1 348 33.8 85.1 21.9 1.72 0.03 304 21.4 68.3 4.80
84.9 459 29.4 79.8 19.4 1.64
261 22.0 36.5 4.89
79.6 430 52.8 96.5 22.9 1.74 0.69 264 22.4 43.4 4.33
91.4 251 50.6 104 20.9 0.95
235 22.4 52.2 4.19
62.8
69.2
63.0
62.6
65.6
65.6
67.4
66.1
67.2
65.4
70.9
72.2
65.8
69.1
68.9
69.0
75.1
73.0
78.0
66.1
Mo
Ag
In
Sn
Ba
49.7
62.9
51.0
41.9
47.8
54.8
48.7
47.9
46.5
47.2
47.0
68.2
56.5
29.3
43.3
60.1
47.3
44.5
39.0
54.2
0.037 0.272 2.19 49.9
0.073 0.256 2.37 44.0
0.038 0.120 0.90 64.8
0.125 0.76 58.4
0.154 0.028 1.08 62.6
0.098 1.00 62.5
0.173 0.81 67.2
0.157 0.101 0.68 48.8
0.123 0.086 0.96 85.0
0.181 0.62 47.2
0.006 0.104 0.51 50.2
0.271 2.00 47.3
0.152 1.02 148
0.113 0.072 1.18 62.1
0.122 0.96 66.0
0.138 0.93 70.5
0.107 0.97 62.3
0.111 1.09 58.9
0.086 0.84 58.9
0.107 1.03 70.6
0.106 0.150 0.97 53.1
0.159 0.307 1.57
0.039 0.275 1.98
0.303 1.65
0.251 2.03
0.162 2.00
0.048 0.214 1.36
0.191 1.72
0.234 1.89
0.081 0.255 1.86
0.048 0.250 1.82
0.278 2.27
0.263 1.96
0.035 0.277 1.68
0.240 1.44
0.299 1.91
0.142 0.264 1.60
0.311 1.60
0.201 0.96
0.277 1.92
0.311 2.17
La
13.1
13.0
3.02
2.50
3.05
2.53
2.60
3.38
5.22
4.05
2.53
13.1
4.08
3.17
3.18
2.74
2.32
2.69
1.91
2.88
3.17
7.26
13.2
14.5
14.4
12.3
10.5
13.4
13.0
12.4
14.7
12.7
11.2
13.0
14.4
15.1
15.0
11.1
8.93
14.8
12.4
Ce
60.5
65.4
13.3
12.4
11.3
11.9
13.5
11.0
20.6
18.0
10.2
61.5
16.6
13.6
13.5
12.4
10.7
13.9
10.2
11.7
14.0
30.3
63.3
62.1
57.5
53.5
41.1
57.9
53.9
54.5
67.0
59.5
45.7
54.3
70.0
66.4
62.8
49.8
37.4
59.4
52.3
Pr
11.4
12.6
3.09
2.32
2.19
2.68
2.68
1.97
3.51
4.04
1.94
11.9
3.06
2.21
2.67
2.74
1.87
2.22
2.16
2.27
2.54
6.15
12.2
11.6
12.2
9.36
7.17
11.2
9.99
10.6
13.0
10.6
8.02
11.1
14.3
13.7
12.0
9.51
7.50
10.8
10.7
Nd
66.3
71.7
15.4
13.0
16.5
16.4
18.9
13.0
24.4
27.3
13.8
69.5
18.6
16.7
18.2
16.4
17.5
15.1
15.3
14.9
17.0
31.8
77.6
71.2
69.6
61.9
46.7
61.6
59.7
60.3
73.7
64.0
43.7
52.2
79.9
72.8
75.5
57.0
45.2
77.9
63.5
18.9
22.9
6.14
5.20
4.12
4.60
7.41
4.95
8.46
7.52
5.05
22.7
7.47
3.79
6.31
4.98
5.80
4.39
5.73
4.57
5.44
12.0
25.2
23.3
19.8
20.6
14.1
18.2
19.3
22.2
25.2
17.9
13.2
19.3
26.4
25.5
24.2
19.1
12.0
24.8
16.9
Sm
Eu
3.19
3.66
2.27
1.79
2.66
1.55
2.17
1.89
2.22
2.26
1.38
3.78
1.82
1.63
2.09
2.01
1.68
1.85
2.13
1.70
1.88
2.72
4.15
3.82
3.79
4.09
2.70
3.55
3.18
3.71
3.56
3.26
3.80
3.09
3.51
4.09
3.37
3.44
2.62
3.48
3.68
Gd
18.2
23.3
6.06
4.47
5.37
6.59
6.35
4.86
10.5
12.2
4.93
20.5
9.25
5.53
6.29
8.45
6.65
6.27
6.12
5.80
4.74
14.4
31.2
27.2
19.6
22.2
13.8
23.8
20.5
26.1
27.9
18.3
14.5
17.6
35.5
23.8
28.0
24.4
13.2
23.9
21.2
Dy
22.9
21.4
4.61
4.46
5.98
4.51
5.53
6.05
6.98
8.55
3.87
22.0
5.78
6.82
6.83
6.20
6.78
5.08
6.20
5.83
7.45
12.3
26.5
22.5
18.2
16.7
9.39
18.5
17.9
19.2
21.6
16.5
12.0
19.6
28.7
23.3
22.4
19.5
12.8
21.8
18.3
Er
10.2
12.5
2.09
3.66
2.42
3.71
2.55
3.45
5.38
3.51
0.81
11.3
3.57
2.33
3.13
2.67
3.19
2.91
2.95
2.10
2.81
5.18
14.1
14.4
11.3
10.6
6.78
11.1
11.4
12.0
11.3
10.6
7.49
10.7
14.8
12.2
12.7
12.1
8.71
12.9
10.2
Yb
7.22
9.26
1.68
0.93
2.48
1.78
2.29
0.84
3.18
3.81
1.90
8.44
1.81
2.41
1.98
1.59
1.91
1.58
1.59
1.31
2.84
4.72
8.18
8.27
8.22
7.36
5.17
7.70
6.15
6.72
8.99
6.61
6.06
4.89
9.45
9.49
7.00
6.67
4.37
7.83
6.42
Pb
0.62
0.43
1.89
0.25
0.60
0.37
0.50
0.11
5.84
0.44
0.22
0.40
2.37
0.45
1.06
0.65
0.47
0.29
0.41
0.46
0.51
0.51
0.64
0.60
0.71
0.40
0.73
0.89
0.37
0.23
0.48
0.62
0.78
0.64
0.16
0.31
0.41
0.46
0.41
0.39
0.45
198
core
rim
core
rim
single
rim
single
single
core
rim
rim
core
rim
single
core
rim
MH09-03-02*
MH09-03-03
MH09-03-03
MH09-03-06
MH09-03-07
MH09-03-07
MH09-03a-06
MH09-03a-07
MH09-03a-07
Spot Location
MH08-08-04
MH08-08-04
MH08-08-08
MH08-08-08
MH08-08-10
MH08-08-13
MH08-08-14
Sample ID
Table B5. Continued.
Pollallie mafic enclave
Pollallie mafic enclave
Pollallie mafic enclave
Pollallie
Pollallie
Pollallie
Pollallie
Pollallie
Pollallie
Timberline
Timberline
Timberline
Timberline
Timberline
Timberline
Timberline
Eruption Date
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Tsch-Prg
Tsch-Prg
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Tsch-Prg
831
830
830
831
796
796
832
844
844
153
162
162
939
939
822
822
835
830
866
158
147
147
150
160
160
295
295
142
142
165
147
194
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
47.2
46.6
46.6
46.8
47.0
47.0
46.6
46.5
46.5
44.0
44.0
47.0
47.0
46.5
46.8
45.0
1.80
1.86
1.86
1.58
1.80
1.80
1.67
1.81
1.81
2.62
2.62
1.53
1.53
1.73
1.56
2.01
8.3
8.7
8.7
8.4
8.1
8.1
8.1
8.7
8.7
11.1
11.1
8.0
8.0
8.6
8.0
9.4
14.3
14.0
14.0
13.9
14.5
14.5
13.7
13.7
14.8
14.8
13.9
14.5
14.5
11.2 13.6
11.3 13.7
11.3 13.7
10.9
11.1
11.1
11.0
11.2
11.2
10.7
10.7
11.0
11.0
11.1
10.9
11.2
15.1
15.0
15.0
14.6
14.9
14.9
14.7
13.4
13.4
14.3
14.3
14.6
14.6
14.8
14.6
14.1
0.19
0.17
0.17
0.20
0.20
0.20
0.23
0.17
0.17
0.18
0.18
0.23
0.23
0.22
0.28
0.21
1.70
1.86
1.86
1.72
1.70
1.70
1.66
1.58
1.58
2.25
2.25
1.65
1.65
1.62
1.62
1.88
0.28
0.34
0.34
0.33
0.35
0.35
0.35
0.34
0.34
0.26
0.26
0.35
0.35
0.31
0.31
0.37
Major Elements by EMPA (wt. %), from Koleszar (2011)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
F
Cl
0.077
0.094
0.094
0.107
0.091
0.091
0.031
0.031
0.091
0.091
0.083
0.109
0.059
0.22 0.072
0.25 0.083
0.25 0.083
0.25
0.24
0.24
0.15
0.13
0.13
0.09
0.09
0.14
0.14
0.11
0.14
0.12
SO2
99.6
99.6
99.6
99.0
99.3
99.3
98.5
98.4
98.4
99.2
99.2
99.3
99.3
98.9
98.7
98.8
Total
199
92.3 12.0 215063
91.1 2.93 219235
57.2 1.77 213231
268346
224345
218563
208548
220265
237953
MH09-03a-06
MH09-03a-07
MH09-03a-07
5.73
2.65
2.91
6.11
4.92
4.54
93.4
16.3
83.2
54.2
118
84.7
MH09-03-02*
MH09-03-03
MH09-03-03
MH09-03-06
MH09-03-07
MH09-03-07
0.61
1.18
0.26
3.73
0.44
10604
11364
10888
12375
11848
12111
173 12209
182 12439
180 12445
148
197
143
125
131
115
205480 87.6 17013
214932 89.4 16013
200776 167 11116
223073 111 8866
225900 91.1 11827
202353 151 10706
204854 112 13295
6.00
6.64
28.2
9.05
9.46
6.11
25.8
Co
Ni
Cu
76.9
66.9
65.4
72.4
70.5
72.7
113
114
161
201
158
173
148
Zn
Ga
18.7
18.2
19.1
17.3
17.7
16.5
19.5
Ge
1.78
1.77
2.94
3.62
1.95
2.98
2.04
Rb
Sr
Y
Zr
Nb
0.43 178 43.6 73.2 6.51
0.33 174 46.6 82.0 7.59
0.36 88.2 128 114 14.5
0.34 65.9 118 69.0 13.2
0.37 107 66.8 81.9 9.89
0.43 90.8 115 96.2 13.3
0.42 191 65.4 76.0 9.75
142 19.4 3.00 0.42
138 18.3 2.77 0.38
148 17.8 2.90 0.41
104 98.6 100 13.0
105 99.5 91.4 12.9
103 96.1 93.0 13.0
12.7 169 20.2 3.61 0.28 83.6 111 133 12.1
7.23 152 17.2 3.13 0.20 88.0 138 95.1 13.3
22.0 77.7 18.0 3.12 0.51 84.4 122 82.7 13.3
19.3 149 18.6 3.01 0.28 110 80.5 86.3 11.4
41.4 156 19.7 3.09 0.38 103 103 112 14.2
27.3 158 19.6 3.34 0.32 107 93.3 104 13.7
153 100
152 65.4
156 15.2
155
121
120
113
115
126
69.3 142 11.3
63.7 72.6 1.34
65.8 100 22.0
70.8 106 3.82
64.7 166 15.5
65.2 105 4.78
63.4 172 20.2
354 70.1
363 73.8
373 72.2
341
344
336
411
335
420
447
391
330
305
401
352
378
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
MH08-08-04
MH08-08-04
MH08-08-08
MH08-08-08
MH08-08-10
MH08-08-13
MH08-08-14
Sample ID
Table B5. Continued.
Mo
Ag
In
0.374
0.365
0.322
0.237
0.323
0.231
0.176
0.181
0.339
0.306
0.231
0.313
0.239
Sn
1.87
1.72
1.77
1.81
1.66
1.66
1.12
0.98
2.22
1.99
1.93
1.69
1.77
Ba
48.8
65.4
65.3
57.0
65.4
64.8
53.4
51.9
58.8
46.5
58.6
47.6
64.3
La
14.7
13.5
14.2
9.97
13.6
12.5
4.50
4.75
16.1
16.2
12.7
13.8
8.86
Ce
70.7
61.2
63.5
45.3
64.4
59.6
20.4
22.8
69.4
74.4
52.8
63.5
38.4
Pr
13.3
13.2
12.8
9.19
12.2
11.7
4.30
4.47
13.7
14.6
9.24
12.8
7.54
Nd
80.6
82.5
77.5
53.2
76.6
63.9
26.0
28.2
80.0
83.2
55.3
79.1
48.2
31.0
28.5
27.2
15.7
24.6
19.8
9.79
10.6
28.1
27.6
15.2
28.0
15.7
Sm
Eu
3.94
3.96
3.91
3.39
4.75
3.45
2.81
2.60
4.52
3.56
3.40
3.70
3.14
Gd
20.5
32.0
29.3
18.7
28.3
21.6
10.0
10.7
32.5
28.1
14.1
29.2
15.5
Dy
25.3
29.6
26.1
17.3
27.1
20.2
9.60
10.6
29.2
26.8
13.3
26.8
14.1
Er
14.7
18.7
17.1
11.8
13.4
11.5
6.11
6.10
15.4
16.4
8.84
15.6
8.44
Yb
9.42
10.3
10.4
6.71
8.86
7.78
3.28
4.08
8.99
8.89
6.03
9.38
5.26
Pb
0.38
0.50
0.14
0.46
0.52
0.34
0.35
0.48
0.56
0.65
0.53
0.50
0.058 0.331 1.53 64.9 12.3 54.7 10.8 65.7 22.7 4.27 23.6 22.0 13.3 8.15
0.032 0.310 1.70 58.8 10.9 53.4 10.1 62.5 21.8 3.91 23.7 22.8 13.4 7.53 0.31
0.040 0.309 1.61 58.6 11.6 55.3 10.6 64.2 22.8 4.04 22.9 21.1 13.3 7.53 0.50
0.060
0.043
0.026
0.030
0.032
0.086
0.030
0.027
0.020
0.025
0.036
0.061
0.033
200
m10s41-1
m10s41-2
m10s410-2
m10s410-3
m10s412-2
m10s414-1
m10s414-2
m10s415-1
m10s416-1
m10s42-1
m10s42-2
m10s42-3
m10s43-1
m10s43-2
m10s44-1
m10s44-2
m10s44-3
m15s411-2
m15s412-1
m15s413-1
m15s42-1
m15s43-1
m15s44-1
m15s46-1
m15s46-2
m15s48-1
m15s48-2
m15shv8-1
m15shv8-3
m8s25-1
m8s25-2
m8s26-2
Sample ID
core
core
core
core
rim
core
rim
rim
rim
core
core
rim
rim
core
core
rim
core
core
rim
core
core
core
core
core
core
Spot Location
Mg-Hbl
Tsch-Prg
Mg-Hbl
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Mg-Hbl
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Mg-Hbl
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Tsch-Prg
Mg-Hbl
Tsch-Prg
Mg-Hbl
117
225
114
114
219
332
332
206
165
146
163
210
220
266
232
169
143
142
139
132
195
263
232
293
202
197
197
191
230
237
245
171
824
907
822
822
903
942
942
900
853
854
858
904
893
924
898
861
836
882
830
819
916
958
947
945
923
929
929
911
959
886
917
872
Ridolfi and Renzulli (2012)
Species P (MPa) T (C)
Table B6. Amphibole analyses from Shiveluch volcano.
48.5
44.7
48.7
48.7
44.2
42.8
42.8
45.1
46.0
46.8
46.2
44.3
45.1
43.8
44.4
46.8
48.6
47.6
47.9
48.8
44.9
43.7
43.9
43.9
45.1
45.1
45.1
45.4
43.7
45.6
43.9
46.0
1.59
1.77
1.56
1.56
2.26
1.53
1.53
1.99
1.81
1.79
1.59
2.34
1.65
2.30
1.77
1.47
1.33
1.73
1.64
1.63
2.19
1.79
1.82
1.48
2.04
1.99
1.99
1.92
2.69
1.54
2.49
2.18
6.6
9.7
6.4
6.4
9.7
11.6
11.6
9.4
8.3
7.7
8.3
9.5
9.8
10.6
10.0
8.3
7.4
7.2
7.5
7.3
9.0
10.3
9.7
11.0
9.0
8.9
8.9
8.9
9.7
10.2
10.3
8.5
11.4
11.3
11.2
11.2
11.4
11.2
11.2
11.3
11.1
11.4
11.3
11.4
11.2
11.2
11.3
11.1
10.7
11.1
11.2
11.3
11.3
11.3
11.2
11.4
11.1
11.2
11.2
11.2
11.2
11.6
11.2
11.2
10.8
12.5
11.0
11.0
12.2
13.5
13.5
12.1
13.2
11.5
12.0
12.5
12.5
12.6
13.3
12.0
11.2
11.0
11.5
10.6
11.7
12.4
12.4
11.3
12.3
11.9
11.9
12.2
12.2
9.6
13.2
12.1
16.3
14.5
16.3
16.3
14.5
13.5
13.5
14.9
14.2
15.6
15.2
14.3
14.8
14.1
14.0
15.1
15.3
17.2
15.3
15.6
16.0
15.5
16.1
16.3
15.9
16.3
16.3
16.2
15.8
16.1
13.5
14.8
0.32
0.31
0.32
0.32
0.25
0.34
0.34
0.26
0.34
0.30
0.29
0.28
0.22
0.24
0.34
0.35
0.35
0.33
0.32
0.30
0.26
0.28
0.27
0.22
0.29
0.28
0.28
0.26
0.25
0.12
0.28
0.26
1.60
2.08
1.54
1.54
2.14
2.32
2.32
2.10
1.73
1.78
1.84
2.09
2.12
2.22
2.03
1.81
1.72
1.70
1.65
1.71
2.03
2.17
2.11
2.29
1.99
2.00
2.00
1.97
2.24
2.24
2.24
1.97
0.26
0.37
0.27
0.27
0.38
0.40
0.40
0.41
0.55
0.33
0.34
0.48
0.40
0.46
0.50
0.39
0.37
0.31
0.31
0.30
0.40
0.45
0.38
0.22
0.45
0.36
0.36
0.42
0.43
0.21
0.49
0.41
Major Elements by EMPA (wt. %), from Humphreys et al. (2006, 2007)
SiO2 TiO2 Al2O3 CaO FeO MgO MnO Na2O K2O P2O5
F
Cl
SO2
97.3
97.4
97.3
97.3
97.0
97.3
97.3
97.6
97.3
97.2
97.1
97.2
97.8
97.5
97.6
97.4
97.1
98.3
97.3
97.6
97.8
98.0
97.9
98.2
98.2
98.1
98.1
98.4
98.2
97.2
97.6
97.5
Total
201
m10s41-1
m10s41-2
m10s410-2
m10s410-3
m10s412-2
m10s414-1
m10s414-2
m10s415-1
m10s416-1
m10s42-1
m10s42-2
m10s42-3
m10s43-1
m10s43-2
m10s44-1
m10s44-2
m10s44-3
m15s411-2
m15s412-1
m15s413-1
m15s42-1
m15s43-1
m15s44-1
m15s46-1
m15s46-2
m15s48-1
m15s48-2
m15shv8-1
m15shv8-3
m8s25-1
m8s25-2
m8s26-2
Sample ID
7.28
7.18
8.74
4.72
5.85
8.01
8.52
5.60
8.02
7.20
5.00
7.09
4.53
6.53
5.37
5.94
8.14
5.53
4.03
7.44
9.09
9.28
10.4
7.94
5.28
7.90
8.16
6.61
3.87
12.8
17.7
6.93
60.1
62.3
74.4
63.5
101
62.7
66.3
60.6
69.9
64.0
70.3
74.6
66.9
87.8
72.1
64.9
67.7
71.9
99.4
83.1
65.4
78.9
65.0
68.8
69.5
70.5
64.1
72.8
102
73.0
61.8
85.2
Co
Ni
Cu
Zn
Ga
10325 334 54.9 108 3.17 147 15.3
10340 484 63.1 232 4.02 158 18.2
9671 320 56.2 139 4.16 149 14.2
9049 288 56.4 126 2.72 154 14.0
12170 431 60.8 150 2.54 128 15.6
9253 338 58.3 105 4.39 146 14.7
9208 425 56.5 76.1 5.04 123 14.2
11760 392 56.9 141 6.74 144 16.0
9878 328 60.1 126 4.70 157 15.1
9968 335 60.7 143 3.68 159 15.9
10368 339 67.1 170 3.90 158 16.0
13366 391 57.6 141 3.88 132 18.7
9141 407 58.9 134 4.86 121 16.8
13845 466 67.5 147 6.16 159 16.9
10728 473 60.2 90.6 6.18 173 18.0
9498 341 62.4 105 4.63 177 15.1
8432 350 57.4 107 4.01 160 14.2
9712 309 61.6 114 3.17 169 16.2
11445 408 67.5 199 4.02 155 18.2
12252 389 58.8 137 3.97 148 17.8
12647 448 67.9 188 7.66 133 18.0
10499 458 62.7 181 5.23 149 18.6
11273 469 60.6 169 7.03 138 18.2
9879 391 67.9 233 6.91 141 17.1
12721 487 68.0 169 4.46 166 17.7
12684 428 63.8 202 4.91 150 16.6
12012 439 64.2 194 4.55 141 17.8
11585 465 71.3 165 9.23 147 17.6
15697 440 62.1 142 4.49 132 18.1
8975 372 75.8 183 5.73 95.0 15.6
15095 1092 118 187 33.7 389 43.4
12442 451 71.3 168 4.79 138 17.4
Major Elements by LA-ICP-MS (ppm)
Li
B
Si
Sc
Ti
V
Table B6. Continued.
Ge
Rb
0.48
0.57
1.32
0.41
0.57
0.55
0.91
0.72
0.41
0.51
0.73
0.95
0.66
1.16
0.60
0.10
0.57
0.40
0.46
0.59
0.87
1.46
0.85
0.47
0.80
0.81
0.89
1.07
0.64
0.56
12.3
0.61
Sr
99.7
97.0
53.6
48.1
119
82.8
143
121
72.4
81.6
80.8
121
111
166
98.0
59.5
55.0
52.8
70.5
87.9
115
105
129
114
103
109
108
90.1
112
155
112
65.9
Y
35.6
38.2
45.7
39.3
40.3
35.1
27.8
35.1
41.6
43.7
54.7
65.4
34.4
48.0
35.6
50.1
45.0
52.6
78.9
60.6
46.2
28.1
34.4
29.1
41.2
47.9
37.0
38.3
68.1
19.3
40.3
52.1
Zr
75.6
95.5
66.7
56.6
59.3
83.0
47.5
73.8
63.7
84.6
80.5
83.1
94.5
71.8
85.9
75.5
62.4
63.2
83.8
71.6
81.5
49.0
66.2
59.0
74.8
77.4
84.7
81.1
79.3
55.0
164
88.7
Nb
2.96
4.24
3.90
3.91
2.83
3.11
1.68
3.47
3.76
3.67
4.11
4.31
3.52
2.97
2.73
3.95
3.03
4.15
5.04
3.64
3.93
1.50
2.79
1.96
3.68
3.97
4.02
3.58
4.51
1.54
4.27
4.21
Ag
In
0.03
0.110
0.11 0.042 0.099
0.14
0.124
0.028 0.120
0.04 0.031 0.137
0.08 0.052 0.119
0.023 0.086
0.04 0.062 0.132
0.09 0.028 0.170
0.07 0.029 0.143
0.10
0.140
0.07 0.043 0.154
0.07 0.035 0.116
0.10 0.064 0.134
0.08 0.051 0.141
0.12 0.046 0.169
0.11 0.049 0.135
0.09 0.035 0.162
0.11 0.032 0.228
0.10 0.134 0.213
0.04 0.036 0.140
0.09 0.094 0.170
0.09 0.051 0.117
0.05 0.050 0.143
0.11
0.155
0.10 0.043 0.148
0.12 0.048 0.152
0.27 0.062 0.127
0.10 0.015 0.174
0.06 0.068 0.106
1.04 0.096 0.212
0.09 0.080 0.172
Mo
Sn
1.18
1.51
1.60
1.37
1.33
1.31
1.02
1.31
1.59
1.44
1.66
1.73
1.43
1.29
1.21
1.71
1.61
1.72
2.12
1.58
1.58
1.31
1.13
1.26
1.76
1.67
1.66
1.68
1.74
1.26
2.69
1.75
Ba
57.1
79.0
66.0
43.8
64.1
55.9
52.1
78.8
53.4
56.0
74.3
105
82.3
109
75.0
40.3
57.5
50.9
77.3
64.4
101
49.7
64.1
45.3
93.3
83.5
84.2
81.4
110
40.7
190
78.5
La
4.99
6.23
6.97
6.43
4.12
5.86
2.34
7.79
6.46
6.64
6.79
11.8
6.96
7.03
5.48
7.61
5.83
7.90
7.37
11.9
5.85
5.03
4.49
4.11
5.99
5.18
5.60
5.52
5.25
2.25
8.27
6.20
Ce
20.2
25.4
28.7
28.3
18.7
22.7
11.1
28.1
27.7
27.1
29.1
34.9
26.8
25.2
20.7
30.5
24.8
33.4
36.2
41.0
26.6
20.0
17.5
17.2
26.0
23.7
23.5
24.9
28.0
9.69
30.8
28.6
Pr
4.33
5.38
5.51
5.39
3.78
4.51
2.37
5.23
5.30
5.24
5.86
7.64
4.86
4.55
3.85
5.96
5.05
6.39
7.63
7.09
5.38
3.72
3.52
3.55
5.17
5.17
4.82
4.64
5.71
2.06
5.39
5.28
Nd
23.1
28.0
29.3
28.2
23.8
24.3
14.8
30.3
30.3
29.5
35.2
42.8
25.3
28.5
22.1
33.0
28.8
35.3
46.2
36.1
31.8
18.0
21.7
20.0
27.0
30.8
26.5
24.0
36.8
13.9
27.9
31.8
6.91
7.62
9.10
8.78
8.03
7.09
4.43
7.77
9.25
8.10
10.5
14.3
6.59
9.75
6.46
9.66
9.35
9.55
16.2
11.6
10.0
5.07
6.79
5.58
7.52
10.6
7.62
7.37
11.7
4.40
7.01
9.87
Sm
Eu
1.78
2.07
1.73
1.90
1.91
1.75
1.44
1.96
1.97
2.25
2.61
3.21
1.70
2.44
1.84
2.22
2.03
2.59
3.27
2.90
2.25
1.79
1.82
1.58
2.23
2.45
2.13
1.91
2.78
1.53
1.85
2.40
Gd
7.30
8.65
8.74
7.59
7.93
7.02
5.86
7.86
9.16
8.63
11.8
14.1
6.00
10.0
6.98
9.49
9.37
10.6
16.8
11.9
8.98
6.95
7.31
6.96
8.69
9.29
7.22
6.51
12.1
5.01
7.83
9.69
Dy
6.41
6.82
9.15
7.03
8.66
6.45
5.41
6.91
8.10
7.77
10.5
12.6
6.02
10.4
6.88
9.19
8.18
9.86
15.6
10.8
8.49
5.47
5.93
5.75
7.07
9.69
7.06
5.94
13.5
4.23
7.15
9.58
Er
4.06
4.24
4.87
4.15
4.59
4.34
2.98
4.09
4.39
4.59
5.91
7.88
3.87
4.98
4.14
5.26
4.74
5.94
7.51
6.24
4.71
3.04
3.92
3.22
4.64
5.08
4.52
4.41
7.42
2.31
3.93
5.72
Yb
3.38
4.27
4.32
4.48
4.06
3.72
2.68
3.80
4.12
4.38
4.69
5.56
4.00
4.32
3.49
5.33
4.29
4.75
6.61
5.39
4.50
3.03
3.26
3.24
3.98
4.32
3.65
4.37
5.81
1.64
4.92
5.51
Pb
0.48
0.51
0.60
0.36
0.35
0.40
0.37
0.62
0.44
0.47
0.50
0.66
0.48
0.62
0.64
0.49
0.47
0.50
0.52
0.48
0.57
0.77
0.57
0.56
0.67
0.56
0.50
0.66
0.56
0.32
4.39
0.51
202
203
APPENDIX C
SUPPLEMENTAL INFORMATION FOR CHAPTER FIVE
This appendix includes whole rock compositional data and sample locations
(Table C1) as well as more detailed results of 40Ar-39Ar analysis and major and trace
element data for some of our dated samples. We include plateau and isochron plots for all
dated samples from the Curaçao Lava Formation (Figure C2) and the Dumisseau
Formation (Figure C3). Samples in these files are listed in the same order as in Tables 5.1
and 5.2.
204
Table C1. Major and trace element whole rock analyses from the Curaçao Lava
Formation and the Dumisseau Formation.
Sample
Curaçao Lava Formation
Cao-03
Cao-04a
Cao-07 a
Cao-10
Cao-13
Cao-14
Cao-18
Cao-20
Cao-21
Lat
Long (negative)
12.27329
69.07389
12.26857
69.07848
12.26914
69.07892
12.14768
68.84962
12.12588
68.81816
12.13771
68.83017
12.16639
68.96115
12.28987
69.07974
12.30754
69.13903
66.7
0.8
70.2
1.1
88.4
2.1
62.3
0.8
86.0
1.9
79.4
1.9
83.9
1.6
74.2
2.4
50.88
1.00
14.00
10.16
0.18
8.55
11.78
3.12
0.19
0.09
96.56
51.03
1.52
13.37
12.91
0.21
7.16
11.56
2.05
0.09
0.08
97.82
50.17
1.06
14.71
10.29
0.19
8.64
12.15
2.42
0.23
0.08
189.82
49.95
0.66
15.83
8.23
0.16
9.15
14.05
1.76
0.06
0.07
98.35
50.86
0.98
14.49
10.25
0.19
8.50
11.79
2.70
0.11
0.08
96.50
51.74
1.17
14.58
10.92
0.21
7.72
11.48
2.01
0.06
0.10
97.49
52.37
1.24
14.10
10.72
0.18
7.01
11.61
2.56
0.07
0.10
97.72
50.97
0.89
14.77
9.58
0.17
8.67
11.44
3.10
0.28
0.08
97.49
112
15.5
143
80.3
129
78.1
361
7.2
48.5
80.8
0.55
20.7
3.97
52.4
3.28
8.19
1.23
6.25
2.14
0.89
2.96
0.56
3.88
0.84
2.34
0.35
2.18
0.35
0.00
1.54
0.28
1.06
0.27
0.11
116
15.8
159
85.5
178
81.6
373
24.9
48.2
123
0.96
22.3
4.29
56.4
3.32
8.54
1.30
6.77
2.34
0.90
3.23
0.61
4.09
0.90
2.54
0.37
2.35
0.38
0.01
1.63
0.31
0.82
0.28
0.10
98.8
14.2
125
76.0
374
115
300
11.7
47.8
151
2.71
16.7
2.63
40.9
2.35
6.24
1.00
5.08
1.76
0.71
2.49
0.49
3.28
0.72
2.03
0.31
1.91
0.31
0.24
1.21
0.19
0.20
0.21
0.06
Plateau Age
(Ma)
2s uncertainty
Major Elements by XRF (wt .%)
SiO2
51.61
TiO2
1.25
Al2O3
14.29
FeO*
11.17
MnO
0.20
MgO
7.21
CaO
10.23
Na2O
3.59
K2O
0.29
P2O5
0.13
Total
96.76
Trace Elements by ICP-MS unless * denoting XRF (ppm)
Co*
147
148
44.7
232
91.6
103
Ga*
16.7
13.8
15.3
28.0
13.3
14.4
Cu*
162
124
200
253
143
131
Zn*
86.0
64.0
110
62.7
65.7
65.5
Cr*
157
349
224
740
534
313
Ni*
85.9
102
75.8
248
128
97.3
V*
372
317
378
632
241
318
Ba
18.0
21.0
16.6
15.0
7.9
9.9
Sc
48.1
47.0
56.6
49.8
45.3
48.5
Sr
120
102
77.8
224
88.2
90.8
Rb
3.60
1.80
1.62
0.74
0.44
1.28
Y
22.7
18.6
24.0
19.1
12.8
17.2
Nb
4.15
3.14
4.51
3.55
2.13
2.85
Zr
57.0
46.0
69.9
49.7
30.3
42.0
La
3.25
2.57
3.89
2.76
1.65
2.33
Ce
8.40
6.76
9.56
7.33
4.39
6.11
Pr
1.32
1.10
1.55
1.16
0.71
0.97
Nd
6.79
5.65
8.60
5.95
3.73
4.98
Sm
2.34
2.01
2.73
2.05
1.37
1.77
Eu
0.90
0.77
1.03
0.81
0.56
0.75
Gd
3.22
2.65
3.69
2.87
1.84
2.53
Tb
0.62
0.52
0.63
0.55
0.36
0.48
Dy
4.15
3.41
4.51
3.60
2.36
3.26
Ho
0.89
0.74
0.95
0.78
0.52
0.71
Er
2.53
2.04
2.91
2.16
1.42
1.97
Tm
0.37
0.30
0.37
0.32
0.21
0.29
Yb
2.30
1.83
2.68
1.98
1.32
1.81
Lu
0.38
0.31
0.41
0.32
0.21
0.29
Cs
0.02
0.01
0.00
0.00
0.01
Hf
1.62
1.31
1.90
1.43
0.89
1.23
Ta
0.29
0.22
0.30
0.27
0.15
0.21
Pb
0.19
0.16
0.29
0.63
0.48
0.60
Th
0.29
0.22
0.32
0.23
0.13
0.20
U
0.09
0.07
0.08
0.08
0.05
0.07
a
major elements by EMP and trace elements by LA-ICP-MS;
NP denotes samples without acceptable plateau ages. See Tables 1 and 2 for full age data.
NP
205
Table C1. (Continued)
Sample
Lat
Long (negative)
Plateau Age
(Ma)
2s uncertainty
Curaçao Lava Formation
Cao-22
Cao-30
Cao-32
12.37064
69.13426
NP
12.14723
68.84871
62.8
1.0
12.28911
69.09496
NP
Cur-10-02
Cur-21i b
Cao-35d
Cao-40b
12.30081
69.09429
12.14115
68.96057
12.11720
68.88011
86.3
2.4
91.8
2.1
63.0
1.0
92.0
1.0
51.68
1.21
13.80
11.64
0.20
7.67
11.76
1.82
0.11
0.10
99.48
51.78
1.03
14.26
9.96
0.17
8.08
10.97
3.38
0.19
0.13
98.26
50.07
0.79
14.11
9.55
0.18
10.45
11.08
2.34
0.30
0.07
99.98
102
15.1
144
84.1
279
107
326
26.0
46.8
157
2.76
20.1
2.91
49.2
2.77
7.34
1.17
6.01
2.12
0.85
2.92
0.56
3.76
0.80
2.27
0.33
2.08
0.32
0.02
1.43
0.20
0.20
0.31
0.07
12.4
116.3
78.7
533
187
268
25.8
46.8
91.8
4.45
14.3
3.17
37.2
2.53
6.21
0.95
4.53
1.51
0.57
2.01
0.37
2.55
0.54
1.56
0.24
1.59
0.24
Major Elements by XRF (wt .%)
SiO2
TiO2
Al2O3
FeO*
MnO
MgO
CaO
Na2O
K2O
P2O5
Total
49.84
0.97
14.58
10.42
0.20
9.20
10.69
2.87
0.99
0.20
95.19
50.72
1.04
14.26
10.11
0.18
8.51
12.16
2.62
0.24
0.09
98.50
52.08
1.25
13.93
11.80
0.20
7.41
11.22
1.91
0.09
0.09
95.96
No
Data c
Trace Elements by ICP-MS unless * denoting XRF (ppm)
Co*
97.5
109
148
138
Ga*
15.7
14.2
15.4
15.6
Cu*
125
128
188
163
Zn*
79.2
69.2
63.2
69.5
Cr*
282
384
86.3
59.5
Ni*
73.1
116
81.8
89.1
V*
307
316
382
349
Ba
243
11.0
20.5
23.4
Sc
45.8
47.9
49.5
48.0
Sr
267
222
133
90.6
Rb
12.6
0.66
1.03
1.42
Y
18.0
18.6
21.1
22.7
Nb
2.38
3.31
3.77
4.78
Zr
43.5
47.9
52.3
62.2
La
3.49
2.65
2.98
3.78
Ce
9.36
7.09
7.70
9.91
Pr
1.55
1.12
1.22
1.55
Nd
8.03
5.76
6.28
7.70
Sm
2.63
2.00
2.24
2.64
Eu
0.94
0.78
0.84
0.97
Gd
3.19
2.79
2.98
3.44
Tb
0.55
0.53
0.58
0.64
Dy
3.44
3.56
3.97
4.23
Ho
0.72
0.76
0.86
0.91
Er
1.99
2.09
2.39
2.54
Tm
0.28
0.31
0.35
0.38
Yb
1.75
1.92
2.24
2.35
Lu
0.27
0.31
0.36
0.38
Cs
0.07
0.01
0.01
0.01
Hf
1.32
1.36
1.55
1.78
Ta
0.16
0.24
0.27
0.35
Pb
0.66
0.20
0.33
1.12
Th
0.48
0.23
0.28
0.38
U
0.24
0.06
0.08
0.15
b
Cur-21i data from Kerr et al. (1996); c No major or trace element analysis available.
1.09
0.22
0.17
0.24
0.07
206
Table C1. (Continued)
Dumisseau Formation
Sample
HA-76-117
Plateau Age
(Ma)
2s uncertainty
NP
Major Elements by XRF (wt .%)
SiO2
48.79
TiO2
2.91
Al2O3
15.03
FeO*
13.36
MnO
0.22
MgO
5.16
CaO
11.65
Na2O
2.52
K2O
0.12
P2O5
0.25
Total
98.41
HA-76-28
HA-77109
87.1
1.1
93.6
1.8
49.48
2.48
15.02
11.98
0.18
6.71
11.31
2.40
0.21
0.21
100.71
49.40
2.19
13.75
11.96
0.21
7.90
12.39
1.98
0.06
0.17
98.95
HA-77110
NP
49.13
2.19
13.91
11.80
0.23
7.84
12.68
1.97
0.07
0.17
98.68
Trace Elements by ICP-MS unless * denoting XRF (ppm)
Co*
Ga*
22.1
20.9
19.7
19.8
Cu*
190
170
150
160
Zn*
130
110
102
103
Cr*
128
193
492
475
Ni*
73.8
99.4
156
139
V*
376
335
334
340
Ba
45.0
51.0
21.0
21.0
Sc
35.7
31.9
35.2
35.0
Sr
275
262
211
211
Rb
0.60
1.90
1.00
1.30
Y
31.7
27.8
23.8
23.4
Nb
13.4
11.3
8.78
8.76
Zr
157
135
109
110
La
11.8
9.95
7.61
7.53
Ce
29.8
25.0
19.6
19.6
Pr
4.44
3.76
3.00
3.01
Nd
21.2
18.1
14.8
14.7
Sm
6.04
5.18
4.47
4.48
Eu
2.18
1.89
1.62
1.59
Gd
6.73
5.79
5.03
5.09
Tb
1.15
0.98
0.84
0.85
Dy
6.72
5.85
5.04
5.04
Ho
1.31
1.14
0.97
0.97
Er
3.26
2.83
2.46
2.43
Tm
0.45
0.38
0.33
0.32
Yb
2.60
2.23
1.93
1.93
Lu
0.39
0.34
0.29
0.29
Cs
0.00
0.01
0.09
0.04
Hf
4.26
3.62
2.97
2.96
Ta
0.90
0.75
0.61
0.60
Pb
1.01
0.65
0.50
0.53
Th
0.99
0.81
0.61
0.63
U
0.30
0.25
0.19
0.19
No location coordinates available for the Dumisseau Formation samples.
HA-77144
HA-77159
HA-77164
86.8
0.7
82.8
0.7
NP
50.08
2.94
13.77
13.12
0.20
5.66
11.16
2.45
0.32
0.30
99.29
48.88
3.44
13.26
14.46
0.23
5.82
11.03
2.42
0.14
0.31
98.63
50.02
3.18
13.28
13.83
0.20
5.96
10.63
2.38
0.26
0.27
99.99
24.1
223
146
104
75.7
373
73.0
35.5
259
3.60
35.8
16.9
191
15.6
37.7
5.38
25.4
7.08
2.34
7.69
1.28
7.48
1.46
3.65
0.49
2.84
0.44
0.01
4.99
1.13
2.55
1.38
0.42
24.0
226
140
64.9
74.4
413
62.0
37.4
267
3.00
37.2
17.5
198
15.2
38.1
5.56
26.3
7.45
2.47
8.11
1.32
7.99
1.52
3.82
0.51
3.01
0.45
0.04
5.17
1.19
1.08
1.29
0.38
23.0
212
132
127
74.8
382
54.0
35.3
236
2.70
35.0
14.3
182
12.4
31.9
4.78
23.1
6.85
2.31
7.55
1.26
7.41
1.42
3.62
0.47
2.81
0.42
0.02
4.80
1.01
0.77
1.05
0.33
207
Table C1. (Continued)
Sample
Plateau Age
(Ma)
2s uncertainty
Dumisseau Formation
HA-77HA-77-170 178
90.8
1.8
86.0
1.1
Major Elements by XRF (wt .%)
SiO2
49.92
TiO2
2.67
Al2O3
15.95
FeO*
12.73
MnO
0.20
MgO
4.32
CaO
11.23
Na2O
2.60
K2O
0.14
P2O5
0.24
Total
96.88
49.28
2.77
15.64
12.78
0.22
5.06
11.20
2.61
0.20
0.24
98.31
HA-77237
NP
HA-77244
85.2
1.1
HA-77245
NP
HA-7729
88.0
1.2
HA-7762
NP
49.53
2.80
14.64
13.41
0.18
5.79
10.75
2.47
0.21
0.22
99.23
49.28
2.49
15.22
12.26
0.18
6.18
11.54
2.42
0.23
0.21
99.33
49.35
3.26
15.11
12.35
0.20
5.34
11.22
2.55
0.33
0.29
99.14
50.44
1.32
15.15
11.96
0.20
6.31
12.16
2.26
0.09
0.11
99.41
Trace Elements by ICP-MS unless * denoting XRF (ppm)
Co*
Ga*
23.5
24.4
22.7
Cu*
205
191
209
Zn*
129
124
135
Cr*
95.2
95.7
128
Ni*
81.0
88.6
100
V*
327
345
356
Ba
41.0
53.0
53.0
Sc
30.7
32.0
33.3
Sr
287
280
259
Rb
1.30
1.40
1.80
Y
29.5
30.3
28.1
Nb
12.8
13.3
12.3
Zr
148
153
141
La
11.6
11.8
10.7
Ce
28.6
29.1
26.2
Pr
4.22
4.30
3.91
Nd
20.1
20.4
18.6
Sm
5.59
5.86
5.40
Eu
2.06
2.10
1.92
Gd
6.34
6.54
6.01
Tb
1.06
1.09
1.00
Dy
6.20
6.43
6.00
Ho
1.21
1.25
1.14
Er
3.08
3.15
2.90
Tm
0.41
0.43
0.39
Yb
2.44
2.51
2.32
Lu
0.36
0.37
0.35
Cs
0.03
0.01
0.01
Hf
3.92
4.00
3.76
Ta
0.87
0.89
0.85
Pb
1.59
1.47
1.60
Th
0.93
0.98
0.87
U
0.29
0.30
0.27
23.3
167
109
204
113
338
44.0
32.6
262
3.00
27.4
11.2
134
9.94
25.0
3.72
17.8
5.20
1.90
5.75
0.98
5.76
1.12
2.79
0.39
2.24
0.33
0.01
3.57
0.77
0.60
0.79
0.25
23.7
235
126
171
94.9
368
70.0
34.2
264
4.90
35.9
15.4
185
13.6
34.2
5.07
24.2
6.90
2.36
7.69
1.29
7.56
1.46
3.67
0.49
2.93
0.44
0.04
4.88
1.04
0.83
1.13
0.35
17.8
207
103
128
67.3
373
21.0
51.1
90.0
1.40
31.2
3.46
71.0
3.66
9.48
1.53
8.07
2.88
1.14
4.14
0.82
5.60
1.25
3.52
0.52
3.33
0.53
0.01
2.03
0.24
0.54
0.35
0.11
208
40
39
Figure C1. Complete Ar- Ar age spectra for the Curaçao Lava Formation.
120
Cur-21i gm
110
3000
100
Ar / 36Ar
Age (Ma)
3600
Plateau: 92.0 ± 1.0 Ma
MSWD 2.32
Total Fusion: 92.0 ± 1.5 Ma
1800
Isochron Age: 91.9 ± 1.0 Ma
MSWD 2.42
40
Ar/36Ar initial: 295.9 ± 2.4
40
90
2400
1200
80
600
70
0
20
40
60
80
Cumulative 39Ar Released (%)
110
0
100
Cao-40b pl
60
Ar / 36Ar
80
100
1400
Ar / 36Ar
1000
90
70
40
Age (Ma)
40
1200
Plateau: 91.8 ± 2.1 Ma
MSWD 1.72
Total Fusion: 91.5 ± 1.7 Ma
80
0
20
Plateau: 88.4 ± 2.1 Ma
MSWD 0.61
Total Fusion: 87.4 ± 2.3 Ma
110
0
100
Isochron Age: 90.5 ± 3.2 Ma
MSWD 1.92
40
Ar/36Ar initial: 299.2 ± 8.7
0
6
12
18
24
30
36
Ar / 36Ar
39
Cao-07 gl
800
600
Ar / 36Ar
400
Isochron Age: 83.2 ± 22.9 Ma
MSWD 0.72
40
Ar/36Ar initial: 318.5 ± 106
40
90
80
200
70
0
20
40
60
80
Cumulative 39Ar Released (%)
130
0
100
0
2
4
6
8
10
12
14
16
Ar / 36Ar
39
1200
Cao-35d gl
120
1000
110
800
Ar / 36Ar
100
90
70
40
80
Plateau: 86.3 ± 2.4 Ma
MSWD 0.54
Total Fusion: 86.0 ± 2.8 Ma
60
0
20
40
60
80
Cumulative 39Ar Released (%)
600
Isochron Age: 89.0 ± 6.1 Ma
MSWD 0.47
40
Ar/36Ar initial: 278.6 ± 32.5
400
200
50
40
600
200
100
60
800
400
40
60
80
Cumulative 39Ar Released (%)
120
Age (Ma)
20
39
100
Age (Ma)
0
100
0
0
4
8
12
Ar / 36Ar
39
16
20
24
209
Figure C1. (Continued)
130
1200
1000
Ar / 36Ar
100
90
80
70
0
20
40
60
80
Cumulative 39Ar Released (%)
100
18
24
30
36
1000
Ar / 36Ar
800
85
75
600
Isochron Age: 83.4 ± 2.1 Ma
MSWD 0.41
40
Ar/36Ar initial: 296.5 ± 3.6
400
200
70
0
0
20
40
60
80
Cumulative 39Ar Released (%)
160
0
100
8
Ar / 36Ar
40
60
Isochron Age: 81.0 ± 8.6 Ma
MSWD 1.83
40
Ar/36Ar initial: 291.7 ± 19.7
200
0
100
0
2
4
6
8
Ar / 36Ar
39
700
79-Be-069 gm
120
28
300
100
40
130
24
400
80
40
60
80
Cumulative 39Ar Released (%)
20
500
Plateau: 79.4 ± 1.9 Ma
MSWD 1.62
Total Fusion: 97.5 ± 3.0 Ma
20
16
600
100
0
12
Ar / 36Ar
Cao-14 pl
120
4
39
140
Age (Ma)
12
1200
80
600
110
500
100
Ar / 36Ar
90
80
70
40
Age (Ma)
6
Ar / 36Ar
Plateau: 83.9 ± 1.6 Ma
MSWD 0.40
Total Fusion: 83.9 ± 1.7 Ma
90
0
39
40
Age (Ma)
0
100
Cao-18 pl
95
60
Plateau: 79.6 ± 3.6 Ma
MSWD 0.35
Total Fusion: 74.4 ± 4.6 Ma
50
40
30
Isochron Age: 86.0 ± 1.9 Ma
MSWD 0.47
40
Ar/36Ar initial: 295.1 ± 1.6
200
50
20
600
400
60
40
800
40
Age (Ma)
110
1400
Cao-13 pl
Plateau: 86.0 ± 1.9 Ma
MSWD 0.44
Total Fusion: 85.7 ± 3.0 Ma
120
0
20
40
60
80
Cumulative 39Ar Released (%)
400
Isochron Age: 77.6 ± 6.1 Ma
MSWD 0.33
40
Ar/36Ar initial: 296.5 ± 2.7
300
200
100
100
0
0
2
4
6
Ar / 36Ar
39
8
10
12
210
Figure C1. (Continued)
100
1000
BK-79-262 gm
90
800
70
50
40
0
20
Isochron Age: 77.8 ± 4.1 Ma
MSWD 0.54
40
Ar/36Ar initial: 288.8 ± 8.1
400
40
Plateau: 74.9 ± 2.1 Ma
MSWD 0.78
Total Fusion: 73.7 ± 2.6 Ma
60
600
Ar / 36Ar
Age (Ma)
80
200
40
60
80
Cumulative 39Ar Released (%)
0
100
0
4
8
12
16
24
20
Ar / 36Ar
39
110
Cao-20 gm
100
1000
800
80
Ar / 36Ar
Age (Ma)
90
70
40
60
Plateau: 74.2 ± 2.4 Ma
MSWD 1.56
Total Fusion: 74.1 ± 2.3 Ma
50
40
0
0
20
40
60
80
Cumulative 39Ar Released (%)
90
100
0
6
12
18
24
30
Ar / 36Ar
39
Cao-04a gm
600
80
70
Ar / 36Ar
Age (Ma)
Isochron Age: 72.9 ± 2.5 Ma
MSWD 1.19
40
Ar/36Ar initial: 298.8 ± 3.8
400
200
30
400
Isochron Age: 70.7 ± 2.5 Ma
MSWD 0.89
40
Ar/36Ar initial: 294.0 ± 5.7
40
60
200
Plateau: 70.2 ± 1.1 Ma
MSWD 0.82
Total Fusion: 69.1 ± 1.2 Ma
50
0
40
0
20
40
60
80
Cumulative 39Ar Released (%)
0
100
2
4
6
700
Cao-03 gm
75
8
12
10
Ar / 36Ar
39
80
600
70
500
Ar / 36Ar
65
60
Plateau: 66.7 ± 0.8 Ma
MSWD 1.20
Total Fusion: 66.3 ± 0.9 Ma
55
50
400
Isochron Age: 67.2 ± 1.2 Ma
MSWD 1.18
40
Ar/36Ar initial: 294.3 ± 2.2
300
40
Age (Ma)
600
200
100
45
0
40
0
20
40
60
80
Cumulative 39Ar Released (%)
100
0
2
4
6
8
Ar / 36Ar
39
10
12
14
211
Figure C1. (Continued)
120
Cur-21i gm
110
3000
100
Ar / 36Ar
Age (Ma)
3600
Plateau: 92.0 ± 1.0 Ma
MSWD 2.32
Total Fusion: 92.0 ± 1.5 Ma
1800
Isochron Age: 91.9 ± 1.0 Ma
MSWD 2.42
40
Ar/36Ar initial: 295.9 ± 2.4
40
90
2400
1200
80
600
70
0
20
40
60
80
Cumulative 39Ar Released (%)
110
0
100
Cao-40b pl
60
Ar / 36Ar
80
100
1400
Ar / 36Ar
1000
90
70
40
Age (Ma)
40
1200
Plateau: 91.8 ± 2.1 Ma
MSWD 1.72
Total Fusion: 91.5 ± 1.7 Ma
80
0
20
Plateau: 88.4 ± 2.1 Ma
MSWD 0.61
Total Fusion: 87.4 ± 2.3 Ma
110
0
100
Isochron Age: 90.5 ± 3.2 Ma
MSWD 1.92
40
Ar/36Ar initial: 299.2 ± 8.7
0
6
12
18
24
30
36
Ar / 36Ar
39
Cao-07 gl
800
600
Ar / 36Ar
400
Isochron Age: 83.2 ± 22.9 Ma
MSWD 0.72
40
Ar/36Ar initial: 318.5 ± 106
40
90
80
200
70
0
20
40
60
80
Cumulative 39Ar Released (%)
130
0
100
0
2
4
6
8
10
12
14
16
Ar / 36Ar
39
1200
Cao-35d gl
120
1000
110
800
Ar / 36Ar
100
90
70
40
80
Plateau: 86.3 ± 2.4 Ma
MSWD 0.54
Total Fusion: 86.0 ± 2.8 Ma
60
0
20
40
60
80
Cumulative 39Ar Released (%)
600
Isochron Age: 89.0 ± 6.1 Ma
MSWD 0.47
40
Ar/36Ar initial: 278.6 ± 32.5
400
200
50
40
600
200
100
60
800
400
40
60
80
Cumulative 39Ar Released (%)
120
Age (Ma)
20
39
100
Age (Ma)
0
100
0
0
4
8
12
Ar / 36Ar
39
16
20
24
212
Figure C1. (Continued)
120
500
BK-79-183 gm
400
80
300
Ar / 36Ar
60
40
Plateau: 63.4 ± 10.7 Ma
MSWD 0.38
Total Fusion: 53.4 ± 10.8 Ma
20
0
0
20
100
40
60
80
Cumulative 39Ar Released (%)
100
0
100
0
1
2
3
4
5
Ar / 36Ar
39
400
BK-79-163 gm
80
300
Total Fusion: 41.2 ± 2.9 Ma
60
Ar / 36Ar
Age (Ma)
Isochron Age: 71.0 ± 22.5 Ma
MSWD 0.42
40
Ar/36Ar initial: 292.3 ± 13.0
200
40
Age (Ma)
100
100
20
0
200
40
40
0
20
40
60
80
Cumulative 39Ar Released (%)
0
100
0.0
0.2
0.4
0.6
0.8
Ar / 36Ar
39
200
Cao-32 gm
1200
1000
Total Fusion: 118.0 ± 3.5 Ma
Ar / 36Ar
140
110
80
600
400
50
20
800
40
Age (Ma)
170
200
0
20
40
60
Cumulative 39Ar Released (%)
80
100
0
0
3
6
9
12
15 18 21
Ar / 36Ar
39
24
27
30
33
213
Figure C1. (Continued)
80
Cao-22 gm
4000
3000
70
Ar / 36Ar
Age (Ma)
75
2000
40
65
Total Fusion: 72.4 ± 0.5 Ma
1000
60
55
0
20
40
60
80
0
100
0
20
40
90
100
120
140
1600
1400
Total Fusion: 61.2 ± 0.7 Ma
1200
70
Ar / 36Ar
1000
60
40
Age (Ma)
80
Ar / 36Ar
Cao-21 gm
80
60
39
Cumulative 39Ar Released (%)
50
800
600
400
40
200
30
0
20
40
60
80
0
100
0
10
20
80
30
40
50
60
Ar / 36Ar
39
Cumulative 39Ar Released (%)
BK-79-263 gl
800
70
600
Ar / 36Ar
Total Fusion: 53.1 ± 1.5 Ma
40
30
400
40
Age (Ma)
60
50
20
200
10
0
0
20
40
60
80
Cumulative 39Ar Released (%)
100
0
0
4
8
12
16
Ar / 36Ar
39
20
24
28
214
40
39
Figure C2. Complete Ar- Ar age spectra for the Curaçao Lava Formation.
160
1200
Plateau: 93.6 ± 1.8 Ma
MSWD 1.90
Total Fusion: 95.4 ± 2.1Ma
140
1000
120
Ar / 36Ar
Age (Ma)
1400
HA-77-109 gm
40
100
800
600
Isochron Age: 92.5 ± 1.8 Ma
MSWD 1.2
40
Ar/36Ar initial: 300.6 ± 4.6
400
80
60
200
0
20
40
60
80
Cumulative 39Ar Released (%)
0
100
0
10
20
30
40
Ar / 36Ar
39
140
2800
HA-77-170 pl
2400
120
Plateau: 90.8 ± 1.8 Ma
MSWD 0.24
Total Fusion: 92.7 ± 2.1 Ma
2000
Ar / 36Ar
110
100
40
Age (Ma)
130
1600
1200
90
800
80
400
70
0
20
40
60
80
Cumulative 39Ar Released (%)
130
0
100
Isochron Age: 90.2 ± 2.1 Ma
MSWD 0.08
40
Ar/36Ar initial: 298.0 ± 4.7
0
20
40
60
80
100
8000
HA-77-29 pl
6000
Ar / 36Ar
Plateau: 88.0 ± 1.2 Ma
MSWD 1.58
Total Fusion: 88.7 ± 1.2 Ma
110
100
4000
Isochron Age: 87.1 ± 1.1 Ma
MSWD 0.80
40
Ar/36Ar initial: 310.1 ± 8.9
40
Age (Ma)
120
90
2000
80
0
20
120
0
40
80
240
280
4000
40
Isochron Age: 86.9 ± 1.2 Ma
MSWD 0.54
40
Ar/36Ar initial: 297.8 ± 10.5
2000
80
40
60
80
Cumulative 39Ar Released (%)
200
6000
90
20
120
160
39
Ar / 36Ar
8000
Plateau: 87.1 ± 1.1 Ma
MSWD 0.45
Total Fusion: 87.7 ± 1.2 Ma
100
70
0
0
100
HA-76-28 pl
110
Age (Ma)
40
60
80
Cumulative 39Ar Released (%)
Ar / 36Ar
70
100
0
0
60
120
180
Ar / 36Ar
39
240
300
215
Figure C2. (Continued)
110
12000
HA-77-144 pl
105
95
8000
Ar / 36Ar
Age (Ma)
10000
Plateau: 86.8 ± 0.7 Ma
MSWD 0.14
Total Fusion: 86.8 ± 0.8 Ma
100
90
40
85
6000
Isochron Age: 86.9 ± 0.8 Ma
MSWD 0.15
40
Ar/36Ar initial: 293.1 ± 18.5
4000
80
2000
75
70
0
20
40
60
80
Cumulative 39Ar Released (%)
110
0
100
100
200
39
Ar / 36Ar
300
400
6000
HA-77-178 pl
5000
100
4000
90
Ar / 36Ar
Age (Ma)
0
40
80
Plateau: 86.0 ± 1.1 Ma
MSWD 0.45
Total Fusion: 86.4 ± 1.2 Ma
70
60
0
20
40
60
80
Cumulative 39Ar Released (%)
110
3000
Isochron Age: 85.5 ± 1.2 Ma
MSWD 0.22
40
Ar/36Ar initial: 302.5 ± 10.7
2000
1000
0
100
0
40
80
120
Ar / 36Ar
160
200
39
HA-77-244 pl
8000
105
Plateau: 85.2 ± 1.1 Ma
MSWD 0.54
Total Fusion: 86.0 ± 1.4 Ma
95
90
6000
Ar / 36Ar
Age (Ma)
100
4000
Isochron Age: 84.9 ± 1.2 Ma
MSWD 0.20
40
Ar/36Ar initial: 299.4 ± 4.6
40
85
80
2000
75
70
0
20
120
40
60
80
Cumulative 39Ar Released (%)
0
100
120
180
Ar / 36Ar
240
300
3600
HA-77-159 wr
3000
2400
Ar / 36Ar
80
Plateau: 82.8 ± 0.7 Ma
MSWD 1.52
Total Fusion: 75.8 ± 0.8 Ma
60
40
Age (Ma)
60
39
100
40
20
0
1800
Isochron Age: 83.4 ± 0.9 Ma
MSWD 1.03
40
Ar/36Ar initial: 286.7 ± 9.7
1200
600
0
20
40
60
80
Cumulative 39Ar Released (%)
100
0
0
20
40
60
80
Ar / 36Ar
39
100
120
140
216
Figure C2. (Continued)
160
Plateau: 105.0 ± 5.3 Ma
MSWD 1.09
Total Fusion: 105.2 ± 6.0 Ma
500
400
Ar / 36Ar
120
100
40
Age (Ma)
140
600
HA-77-62 pl
80
0
20
130
40
60
80
Cumulative 39Ar Released (%)
0
100
Age (Ma)
Ar / 36Ar
Isochron Age: 85.2 ± 0.9 Ma
MSWD 0.89
40
Ar/36Ar initial: 300.4 ± 8.7
40
20
110
40
60
80
Cumulative 39Ar Released (%)
0
100
HA-77-237 gm
20
40
60
Ar / 36Ar
40
85
80
140
Isochron Age: 86.4 ± 3.9 Ma
MSWD 1.24
40
Ar/36Ar initial: 292.0 ± 49.0
800
0
40
60
80
Cumulative 39Ar Released (%)
120
1200
400
75
20
100
1600
90
0
80
Ar / 36Ar
2000
Plateau: 86.1 ± 0.8 Ma
MSWD 1.24
Total Fusion: 89.8 ± 1.1 Ma
95
0
39
105
100
8
2000
1000
0
6
3000
Plateau: 85.2 ± 0.7 Ma
MSWD 1.02
Total Fusion: 91.1 ± 0.7 Ma
90
70
4
4000
100
80
2
Ar / 36Ar
HA-76-117 wr
110
0
39
120
Age (Ma)
Isochron Age: 100.8 ± 7.2 Ma
MSWD 1.06
40
Ar/36Ar initial: 298.4 ± 4.1
200
100
60
40
300
100
0
10
20
30
40
Ar / 36Ar
39
50
60
70
217
Figure C2. (Continued)
2400
Total Fusion: 77.7 ± 1.1 Ma
110
Ar / 36Ar
90
70
40
Age (Ma)
3000
HA-77-245 wr
130
1800
1200
50
600
30
10
0
20
40
60
80
Cumulative 39Ar Released (%)
0
100
0
80
100
120
1200
110
105
1000
Total Fusion: 90.5 ± 1.8 Ma
100
Ar / 36Ar
Age (Ma)
60
Ar / 36Ar
39
HA-77-110 gm
115
95
800
600
40
90
85
400
80
200
75
0
20
120
40
60
80
Cumulative 39Ar Released (%)
0
100
0
10
20
30
40
Ar / 36Ar
39
7000
HA-77-164 wr
6000
110
5000
Total Fusion: 91.0 ± 0.6 Ma
Ar / 36Ar
100
90
40
Age (Ma)
40
1400
120
70
20
4000
3000
2000
80
70
1000
0
20
40
60
80
Cumulative 39Ar Released (%)
100
0
0
40
80
120
160
39
Ar / 36Ar
200
240
280