a geochemical and u-pb isotope study of lower crustal ...€¦ · the earth’s continental crust...
TRANSCRIPT
i
A geochemical and U-Pb isotope study of
lower crustal xenoliths from the Monaro
Volcanic Province, NSW: Implications for
the deep crustal evolution of eastern
Australia
Natasha Barrett (20761355)
School of Earth and Environment
Supervisors: Dr Tony Kemp & Associate Professor Eric Tohver
This thesis is submitted to fulfill the requirements for Master of Science (Geology)
by way of Thesis & Coursework
Faculty of Science
The University of Western Australia
(November 2014)
ii
TABLE OF CONTENTS
1. Acknowledgements………………………………………………..…...….....iv
2. Abstract………………………………………………………………...……..v
3. Introduction……………………………………………………………...…1-8
3.1. Summary of 2013 findings……………………………………...…..2-3
3.2. Geological setting……………………………………………….…..4-7
3.3. Aims and objectives………………………………………….………..8
4. Methodology………………………………………………………………9-17
4.1. LA-ICP-MS……………….………………….……………………9-13
4.1.1. Analytical methods……………………………………………..9-11
4.1.2. Data processing………………………………………….……….13
4.2. Whole rock geochemistry…………………………………….…..13-14
4.2.1. Sample preparation………………………………………………13
4.2.2. Analytical methods…………………………………………....13-14
4.3. Calculations applied to geochemical data………………………...…14
4.4. SHRIMP U-Pb zircon geochronology…………………….……...15-17
4.4.1. Mineral separation…………………………………….………….15
4.4.2. Grain mount preparation…………………………………………15
4.4.3. Electron imaging……………………………………….…………16
4.4.4. Analytical methods………………………………….………….…16
4.4.5. Data processing……………………………………….……….16-17
5. Results……………………………………………...…………...……....…18-54
5.1. Mineral chemistry……………………………..……………...……18-27
5.1.1. Plagioclase…………………………………………….….………21
5.1.2. Scapolite………………………………………………….…….…22
5.1.3. Clinopyroxene…………………………………...……….……23-24
5.1.4. Orthopyroxene……………………………………………………25
5.1.5. Garnet………………………………………………………….…26
5.1.6. Rutile………………………………………………………...……27
5.2. Whole rock geochemistry…………………………………...……28-39
5.2.1. Major element geochemistry………………………….………28-32
5.2.2. Trace element geochemistry………………………….…….…33-39
5.2.2.1. Normalisation to bulk continental crust………………38-39
iii
5.2.2.2. Normalisation to mid ocean ridge basalts (MORB)…...…39
5.3. Mineral/whole rock concentration ratios……………………..…40-43
5.4. Zircon mineralogy………………………………………………..44-46
5.5. U-Pb (SHRIMP II) age determinations – Monaro Volcanic Province
xenoliths…………………………………………...………….…47-52
5.6. Comparison of the dated xenoliths to the Delegate breccia pipe
xenoliths……………………………………………………….…..…52
5.7. Age comparison to the regional lithological units………………52-54
6. Discussion………………………………………………………….…..…54-64
6.1. Origin of xenoliths from the Monaro Volcanic Province ……....54-58
6.1.1. Evidence from trace element geochemistry………...……...…54-56
6.1.2. Evidence from zircon analysis………..…………………….…56-58
6.1.2.1. Textural context and microstructures………….…...…56-57
6.1.2.2. Geochronology…………………………………………...57
6.2. Implications for crustal evolution………………………………..58-62
6.2.1. Relationship with regional granites………………………...…58-59
6.2.2. Implications of the Lachlan Fold Belt/Tasmanides evolution -
evidence from xenoliths…………………………………..……59-61
6.2.3. Implications for general crust forming processes……………...…62
6.3. Conclusions and future research…………………………………….63
7. References………………………….…………………………………..…64-72
APPENDIX 1. Summary of mineralogy and hand samples
APPENDIX 2. Original EMP data
APPENDIX 3. Pressure-temperature estimates
APPENDIX 4. Whole rock geochemistry data
APPENDIX 5A. Photomicrograph of thin sections analysed by LA-ICP-MS
APPENDIX 5B. LA-ICP-MS raw data
APPENDIX 6. Calculated concentration ratios and partition co-efficients
APPENDIX 7. SHRIMP data
APPENDIX 8. 2014 research proposal
iv
1. Acknowledgements
The research conducted for this MSc thesis was made possible by a number of
contributors and departments of whom I would like to express my appreciation
towards. Firstly, I would thank my supervisor Dr Tony Kemp for giving me the
opportunity to work on such an interesting project and for being a supportive and
knowledgeable mentor for the past two years, and to my co-supervisor, Associate
Professor Eric Tohver for his helpful advice and support, and discussions
throughout the year.
Analytical work was made possible by the staff and facilities at the Advanced
Analytical Centre, James Cook University, the Centre of Microscopy,
Characterisation and Analysis, UWA, and the John de Laeter Isotope Research
Centre at Curtin University. I would also like to thank the staff and services of the
GeoAnalytical Laboratory at Washington State University who produced high
quality whole rock geochemical data for this project, and Professor Richard
Arculus from the Australian National University for collecting these samples and
making them available for this study.
Travel costs were covered by a post-graduate student bursary kindly offered by the
Geological Society of Australia (Western Australian division).
v
2. Abstract
Granulite xenoliths are fragments of the Earth’s lower continental crust. These samples
are transported to the Earth’s surface by younger, and explosive volcanic pipes,
providing a unique insight into the composition of rock material at inaccessible crustal
depths. This research builds on a detailed petrological study of granulite xenoliths
collected from alkali basalt pipes in the Monaro Volcanic Province and breccia pipes
near the town of Delegate, both within New South Wales, Australia. Geochemical
signatures indicate that these samples are basaltic cumulates, formed by the
accumulation of plagioclase during basaltic underplating that subsequently underwent
granulite facies metamorphism. Whole rock geochemistry further indicates a magmatic
provenance similar to arc basalts, suggesting that a subduction component has
influenced the composition of the lower crust beneath eastern Australia. Samples are
also depleted in heat producing elements (Th, U), characteristic of a residual lower
crust, with some showing a strong REE enrichment and negative Eu anomaly. These
compositions are suggestive of fractionated melt, perhaps complementary to the
depleted granulites.
Ion microprobe analysis of zircon from two Monaro Volcanic Province samples
(MVP10436 and MVP10437), yields a U-Pb concordia age of 419.4 ± 6.6 Ma and 402.5
± 6.3 Ma respectively. The 402.5 ± 6.3 Ma age is derived from a loose array along
concordia and its significance remains ambiguous. The 419.4 ± 6.6 Ma age is defined
by a tighter cluster of concordant data and is shown to be contemporaneous with the
emplacement of the Late Silurian I-type granites within the eastern Lachlan Fold Belt.
This age relationship provides new evidence for a genetic link between the mafic and
granulitic lower crust, and the more felsic upper crustal granites in eastern Australia,
signifying that arc magmatism and fractionation magma differentiation are key
processes in the growth and evolution of the continental crust during the Palaeozoic.
1
3. Introduction
The Earth’s continental crust is characterised by its bulk andesitic composition (Taylor
and McLennan, 1985). While this is true for much of the Earth’s middle and upper
crust, this classification is biased by the availability of upper crustal material over the
basaltic and inaccessible lower crustal region (>23km depth; Rudnick and Gao, 2003).
The origin of the continental crust remains actively debated, and multiple fields of Earth
science are involved in unravelling its composition, structure and formation. It is much
older than the oceanic crust and contains most rocks in the geological record, thus
preserving an archive of Earth evolution. Calculating the chemical composition of the
lower crust is far more difficult due to the inaccessibility of the Earth’s crust beyond
~12kms depth (Kremenetsky and Ovchinnikov, 1986). Exposed lower crustal material
exists as tectonically exhumed granulite facies terranes or in the form of xenoliths in
volcanic pipes (e.g. Irving, 1974; Francis, 1976). These pipes, forming explosive
diatremes, bring upper mantle and lower crustal fragments to the surface within hours to
days (e.g. Kushiro, 1976), which is ideal for preserving the prograde, high temperature
mineral assemblages of the lower crust. Their mineralogy denotes pressure and
temperature conditions of granulite facies metamorphism, possibly driven, at least in
part, through heat advection from mantle-derived magmas (e.g. Wells, 1980). Lower
crustal xenoliths therefore provide a potential record for the addition of new material to
the continents (Kemp et al., 2007).
The lower continental crust of post-Archean regions is dominantly mafic in composition
(e.g. Voshage et al., 1990; Miller and Christensen, 1994; Ross, 1985; Hart et al., 1990).
The majority of lower crustal xenolith samples are also mafic in composition (e.g.
Rudnick and Presper, 1990; Rudnick, 1992; Downes, 1993), although it is still unclear
how representative these xenoliths are of the lower crust (Rudnick and Gao, 2003). It is
believed that the granulitic lower crust generally represents a residual or cumulate
composition from the crystallisation and extraction of magmas, and thus is refractory,
depleted in radioactive heat producing incompatible elements (K, Th, U), and
mechanically strong due to the dominance of pyroxene over quartz (Taylor and
McLennan, 1985). Formation of the lower crust may therefore be fundamental for the
preservation, strengthening and stabilisation of continents as a whole (Rudnick, 1995).
2
This project will explore these problems through studying deep-seated xenoliths, hosted
in breccia and alkali basalt pipes from southern New South Wales, Australia. By
assessing their geochemical signatures and using geochronology to constrain ages, it is
possible to determine if samples are fragments of lower crust, or represent a younger
magmatic material. This information will provide a unique insight into crustal processes
at inaccessible depths.
3.1. Summary of 2013 findings
Part 1 of this project undertaken in 2013, involved the detailed petrological study of
seventeen xenoliths samples from alkali basalt pipes of the Monaro Volcanic Province
and breccia pipes near the town of Delegate in NSW. These previous results will be
referred to as “Part 1” throughout this thesis. The major rock types from the Monaro
Province were a two pyroxene granulite (cpx+opx+pl±scp±rt±ilm), a garnet granulite
(grt+cpx+pl±scp±rt), and one sample showing disequilibrium textures between cpx,
opx, pl, grt, sp and ilm, referred to as a reaction intermediate (abbreviations after Kretz,
1983). The later suggests a dynamic and complex history in the lower crust, and
potentially provides evidence for larger scale processes of crustal thickening and
extension, as typifies convergent plate margins. Samples from the breccia pipes in
Delegate also included the garnet granulite and two pyroxene granulites and one
eclogite sample (grt+cpx±rt).
The first stages of analysis involved documentation of samples, petrophysical
measurements and preparation of thin sections. A summary of the major mineral
assemblages are provided in Table 1, and a summary of the mineralogy and hand
sample descriptions are presented in Appendix 1. This was followed by scanning
electron microscopy (imaging and semi-quantitative SEM-EDS), and electron
microprobe (WDS-EMP) analysis (Appendix 2). The results from this analysis were
used to analyse the mineralogy and mineral chemistry of the samples, and infer
pressure-temperature conditions of formation through thermobarometry calculations.
3
Table 1. Classification of major rock types from the Delegate breccia pipes and Monaro Volcanic
Province (MVP) alkali basalt pipes. Xenolith classifications based on mineral assemblages in Lovering
and White, (1964) and mineral abbreviations according to Kretz, (1983).
The mineralogy of the xenoliths suggest pressure and temperature conditions of
granulite facies metamorphism (e.g. Wells, 1980), and the derived P-T values
(Appendix 3) are consistent with a thermally perturbed and thickened lower continental
crust. These data thus fitted the experimentally determined P-T conditions on previously
studied samples from Delegate, NSW (Irving, 1974). From this, a lower crustal origin
was suggested by analogy with the Delegate xenoliths (Chen et al., 1998).
Additional findings included the identification of scapolite in textural equilibrium with
granulite minerals. This appears to be a widespread, and possibly even a unique feature,
of deep crust beneath eastern Australia. The inferred primary nature of scapolite and its
crystallographically bound volatiles (CO3 and SO4) at the weight percent level suggest
that this mineral is potentially reservoir for carbon and sulfur in the lower crust.
Rock type Host rock/location Mineral Assemblage
Two-pyroxene
granulite
Alkali Basalt - MVP
Breccia pipe - Delegate
Opx+ Cpx + Pl ± Scp ± Ilm ± Mg ± Rt
Garnet granulite Alkali Basalt - MVP Grt + Cpx + Pl ± Scp ± Rt
Eclogite Breccia pipe - Delegate Cpx + Grt ± Rt
Reaction
intermediate Alkali Basalt - MVP
Cpx, Opx, Grt, Pl, Spl, Ilm
4
3.2. Geological setting
Xenolith samples were collected from two localities in southeastern New South Wales,
Australia (Figure 1). Five samples were from the two diatremes known as the Delegate
breccia pipes outcropping at Airlie Park homestead, 35kms northwest of Delegate,
NSW (Lovering and White, 1969) (Figure 2A). These pipes are Mid-Jurassic in age,
~168 Ma based on K-Ar dating methods (Lovering and Richards, 1964). Twelve
xenolith samples were from alkali basalt pipes, Eocene-Oligocene in age (56-34 Ma;
Taylor et al., 1990) located northwest of Delegate around the town of Nimmitabel,
NSW within the Monaro Volcanic Province. This Monaro Volcanic Province hosts
approximately 65 eruption sites within its basaltic lava field (Roach et al., 1994). The
region has experienced extensive mafic volcanism which began during the late
Palaeocene and lasted for about 20 million years, where at least 630 cubic kilometres of
pyroclasts and lava erupted (Brown et al., 1993). The province is believed to be built up
by eruptions of alkali basalt, basanite and nephelinite (Roach et al., 1994). The surface
geology is dominated by mafic lavas and Tertiary volcanogenic sediments, which
overly Ordovician-Devonian bedrock.
The Delegate breccia pipes intrude the Silurian Snodgrass Adamellite (Chappell et al.,
1991). The pipes are in close proximity to the west of the Delegate and Buckleys Lake
Adamellite, and outcrop slightly north of the Tingaringy Granodiorite, all part of the
Berridale Batholith (Figures 2A and 2B). The Monaro Volcanic Province xenoliths are
taken from pipes within the lava field. The exact location was not specified, except
understood to be taken around the town of Nimmitabel, NSW. The Monaro Volcanic
Province lies within the Bega and the Berridale Batholiths. Nearby granitic units include
the Buckleys Lake Adamellite of the Berridale Batholith and the Glenbog Granodiorite
of the Bega Batholith (Figures 3A and 3B). Both xenolith localities occur within the
Ordovician-Devonian Lachlan Fold Belt of eastern Australia, but are related to a much
younger hot-spot magmatism (Lewis and Glen, 1995). The Lachlan Fold Belt is itself
part of the Terra Australis Orogen, a vast subduction-related accretionary orogenic
system that developed along the eastern Palaeo-pacific margin of Gondwanaland during
the Palaeozoic and Mesozoic (Cawood and Buchan, 2007; Braun and Pauselli, 2004).
This tectonic unit comprises the eastern third of the Australian continent (Gray and
Foster, 2004), as well as comprising a large part of western Antarctica and Argentina.
5
Figure 1. Locations of the Delegate breccia pipes (A) and the Monaro Volcanic Province (B) in
southeastern, NSW. Regional geology is from the Bega-Mallacoota 1:250 000 geological sheet
(Lewis and Glen, 1995). Grid lines indicate 10 000m intervals of the Australian map grid zone 55.
Outline of eastern Australia is modified from Chen et al., (1998).
6
Figure 2A. Enlarged map of region A from Figure 1 showing the location of the Delegate breccia pipes
1 and 2 intruding into the Snodgrass Adamellite. Pipes outcrop at the Airlie Park homestead, 35kms
North of Delegate, NSW. Other lithological regions including the Buckleys Lake Adamellite, Delegate
Adamellite and Tingaringy Granodiorite are also included. Regional geology from Bega-Mallacoota
1:250 000 geological sheet (Lewis and Glen, 1995).
Figure 2B. Simplified map of
the Numbla map sheet (White
and Chappell, 1989), modified
by Chen et al., (1998) showing
the major regional granite types
and the Delegate breccia pipe
localities.
7
Figure 3A. Larger map of region B from Figure 1. Xenoliths are taken from one of the alkali basalt pipes
within the Monaro Volcanic Province near the town of Nimmitabel. Other major lithological regions
include the Glenbog Granodiorite and the Buckleys Lake Adamellite. Regional geology from Bega-
Mallacoota 1:250 000 geological sheet (Lewis and Glen, 1995).
Figure 3B. Simplified outline of
the Monaro Volcanic Province.
Samples were collected around
the town of Nimmitabel. The
shaded region represents mafic
lavas and Tertiary sediments,
while the surrounding area
represents the Ordovician-
Devonian Bedrock. Lava pile
outline is from Lewis et al.,
(1994) modified by Roach,
(2004).
8
3.3. Aims and objectives
The aim of this study is to clarify the origin of granulite xenoliths from the Delegate and
Monaro Volcanic Province in eastern Australia. Particular attention will be on samples
from the Monaro Volcanic Province, as limited geochemical analysis has been
undertaken on these samples. This project will build on the foregoing detailed
petrological study of these xenoliths, and will focus on trace element geochemistry and
U-Pb zircon geochronology. A broader objective is to place new constraints on the
growth and evolution of the continental crust as a whole, from a lower crustal
perspective.
It is proposed that U-Pb geochronology of zircon will date the age of granulite facies
metamorphism by analogy with zircon ages from the Delegate breccia pipe xenoliths by
Chen et al., (1998). This could indicate whether granulite metamorphism in both
samples is driven by heat related to production of voluminous felsic magmatism and
batholith emplacement in this part of the Lachlan Fold Belt (~420 to 380 Ma; Gray and
Foster, 2004). Previous studies across several continents have assumed that xenoliths
contained by similar volcanic pipes represent fragments of lower crust (e.g. Francis,
1976; Selverstone and Stern, 1983; Kempton and Harmon, 1992; Kay and Kay, 1983;
Leyreloup et al., 1982). The exact origin of samples in this project has, however, yet to
be determined. Before interpreting data from the xenoliths in terms of lower crustal
processes, we first need to consider if the study samples did in fact originate from the
lower crust, which can be established from dating the xenolith samples relative to the
younger Eocene-Oligocene aged host rock (Roach, 2004).
Geochemical data will be used to determine the composition of the source magma and
to establish whether the xenolith samples represent cumulates, restites or solidified
basalts possibly related to the host pipes, and were subsequently crystalised under
granulite facies conditions. Determining the mode of formation and the compositional
variation of such samples is key to understanding crustal evolution as a whole.
9
4. Methodology
4.1. Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS)
Preparation of seventeen (50µm) polished thin sections, optical microscopy, scanning
electron microscopy (SEM) and electron microprobe (EMP) analysis was undertaken in
Part 1 of this project (see Appendix 1 and 2). Petrography (optical microscopy and SEM
imaging), and EMP analysis was essential for characterising the mineral assemblages
and major element chemistry prior to LA-ICP-MS analysis.
4.1.1. Analytical methods
Six polished thin sections (MVP10438, MVP10437, DEL99-2-01, DEL2-10434,
MVP99-2-22, MVP99-2-12) were analysed using the LA-ICP-MS at the Advanced
Analytical Centre, James Cook University, Townsville, Australia. In situ trace element
analysis was carried out for 37 elements (Table 2) in garnet, plagioclase, pyroxene,
scapolite and rutile. LA-ICP-MS analysis was conducted using the Varian 820
quadrupole ICP-MS attached to a MicroLas ArF laser system of 193nm wavelength. A
carrier gas of helium (at ~ 0.8 l/min) was used to transport the ablated aerosol particles,
and was mixed with a nebulizer flow of argon (0.95 l/min) in a small glass mixing
chamber (~ 1cm3 volume) before entering the plasma torch. A small Ar sheath gas flow
of 0.1 l/min was used to enhance sensitivity and reduce oxide production. The mass
spectrometer was tuned at plasma conditions of Th/U ~ 1 in a NIST610 silicate glass,
and the production of molecular oxide species monitored by maintaining a low ThO/Th
ratio ~ 0.25%.
The laser system was operated at a 10Hz repetition rate, with an output energy of 100mJ
and laser fluence of 6 J/cm2. Spot sizes varied from 32 to 44µm in diameter, depending
on the size of the analytical target. The dwell time for all analyte elements was set to
10ms (except 139La and 151Eu at 20ms), corresponding to a mass sweep time of 843ms.
The total measurement time was 75 secs, of which the first 30 s was for blank
measurement (laser firing, shutter closed). Element concentrations were calibrated using
silicate glass NIST610 (Table 3) and by using predetermined EMP values of CaO and
TiO2 as internal standards. The silicate glass NIST612 was analysed as a secondary
standard (see Table 4).
10
Element
and
isotope
Dwell
time
(ms)
L.O.D (ppm)
Element
and
isotope
Dwell
time
(ms)
L.O.D (ppm)
Mean Min Max Mean Min Max
7Li 10 1.07
0.35 2.49 140Ce 10 0.0025 0.00053 0.039
24Mg 10 2.55
0.94 5.48 141Pr 10 0.0016
0.00044 0.0042
29Si 10 1426.90
435.22 3615.97 143Nd 10 0.011
0.004 0.033
31P 10 16.82 5.37 40.05 147Sm 10 0.009 0.0024 0.029
43Ca 10 0.013
0.0042 0.033 151Eu 20 0.0026 0.00044 0.013
45Sc 10 0.17 0.055 0.4 157Gd 10 0.01 0.002 0.033
49Ti 10 0.58 0.21 1.44 159Tb 10 0.0014 0.00038 0.0059
51V 10 0.05 0.019 0.12 163Dy 10 0.005 0.0015 0.022
52Cr 10 1.08 0.39 2.57 165Ho 10 0.0014 0.00042 0.0049
60Ni 10 1.37 0.45 3.12 167Er 10 0.007 0.0016 0.021
65Cu 10 1.45 0.15 1.04 169Tm 10 0.001 0.00041 0.0048
85Rb 10 0.022 0.0059 0.074 171Yb 10 0.010 0.0033 0.048
88Sr 10 0.0088 0.0023 0.12 175Lu 10 0.0015 0.00045 0.0056
89Y 10 0.0094 0.0027 0.022 178Hf 10 0.0065 0.0012 0.039
90Zr 10 0.028 0.0069 0.058 181Ta 10 0.0023 0.00047 0.043
93Nb 10 0.0032 0.00085 0.01 208Pb 10 0.0056 0.0013 0.015
133Cs 10 0.0047 0.0011 0.053 232Th 10 0.0028 0.00056 0.018
137Ba 10 0.029 0.01 0.11 238U 10 0.0023 0.00051 0.015
139La 20 0.0024 0.00046 0.015
Table 2. Elements and isotopes analysed by LA-ICP-MS showing Limit of Detection (L.O.D) calculated
to 99% confidence.
11
Element
and
isotope
Mean
(n=14)
±2 SD RSD
%
Values*
(ppm)
Element
and
isotope
Mean
(n=14)
±2 SD RSD
%
Values*
(ppm)
7Li 498.67 89.59 17.97 468.00 ± 24 140Ce 447.47 6.12 1.37 453.00 ± 8
24Mg 480.96 64.93 13.5 432.00 ± 29 141Pr 429.57 5.63 1.31 448.00 ± 7
31P 339.93 19.57 5.76 413.00 ± 46 143Nd 430.42 5.88 1.37 430.00 ± 8
43Ca 11.5 0 0 11.40 ± 0.2 147Sm 449.95 6.21 1.38 453.00 ± 11
45Sc 441.61 2.66 0.6 455.00 ± 10 151Eu 460.06 6.27 1.36 447.00 ± 12
49Ti 434.33 4.02 0.93 452.00 ± 10 157Gd 443.43 6.72 1.52 449.00 ± 12
51V 442.64 4.17 0.94 450.00 ± 9 159Tb 442.5 6.95 1.57 437.00 ± 9
52Cr 405.49 4.65 1.15 408.00 ± 10 163Dy 426.66 7.45 1.75 437.00 ± 11
60Ni 458.55 16.84 3.67 458.70 ± 4 165Ho 448.91 8.89 1.98 449.00 ± 12
65Cu 430.94 9.58 2.22 441.00 ± 15 167Er 425.87 8.47 1.99 455.00 ± 14
85Rb 425.08 5.87 1.38 425.70 ± 1 169Tm 420.07 8.25 1.96 435.00 ± 10
88Sr 514.26 6.74 1.31 515.50 ± 1 171Yb 444.71 8.1 1.82 450.00 ± 9
89Y 449.29 5.14 1.14 462.00 ± 11 175Lu 434.44 6.77 1.56 439.00 ± 8
90Zr 439.24 5.11 1.16 448.00 ± 9 178Hf 431.06 8.11 1.88 435.00 ± 12
93Nb 418.47 4.57 1.09 465.00 ± 34 181Ta 450.76 9.42 2.09 446.00 ± 33
133Cs 360.91 5.68 1.57 366.00 ± 9 208Pb 425.83 11.69 2.75 426.00 ± 1
137Ba 434.73 6.67 1.53 452.00 ± 9 232Th 458.14 13.53 2.95 457.20 ± 1
139La 456.56 6.68 1.46 440.00 ± 10 238U 463.81 17.56 3.79 461.50 ± 1
Table 3. NIST610 primary standard trace element concentrations MDL filtered. Uncertainty on NIST610
literature values from GeoReM (95% CL). Silica values are omitted as NIST610 is a silica glass. Values*
= literature values from Jochum et al., (2011).
12
Table 4. NIST612 primary standard trace element concentrations MDL filtered. Uncertainty on NIST612
literature values from GeoReM (95% CL). Silica values are omitted as NIST612 is a silica glass. Values*
= literature values from the Jochum et al., (2011).
4.1.2. Data processing
Data were processed using the software package ‘Glitter’ (Van Achterberg et al., 2001).
Trace element compositions were calibrated using the major element compositions from
each mineral analysed where available. It is important to note that EMP analysis was
not originally done on sample MVP10437. Later in the project it was found that this
sample was significant as it contained zircon. Subsequently, trace elements in this
Element Mean
(n=9)
± 2 SD RSD% Values*
(ppm)
Element Mean
(n=9)
± 2 SD RSD
%
Values*
(ppm)
7Li 42.85 6.99 16.32 40.20 ±1.30 140Ce 38.31 1.10 2.86
38.40 ± 0.70
24Mg 60.97 7.72 12.66 68.00 ±5.10 141Pr 36.73 1.09 2.96
37.90± 1.00
31P 25.70 6.95 27.03 46.60 ±6.90 143Nd 35.39 1.03 2.92
35.50± 0.70
43Ca 11.85 0.00 0.00 11.90 ±0.10 147Sm 37.59 0.98 2.61
37.70± 0.80
45Sc 37.23 0.29 0.79 39.90 ±2.50 151Eu 37.02 1.03 2.79
35.60± 0.80
49Ti 37.67 1.31 3.47 44.00 ±2.30 157Gd 37.78 1.10 2.90
37.30± 0.90
51V 37.59 0.27 0.72 38.80 ±1.20 159Tb 38.28 1.24 3.24
37.60± 1.10
52Cr 33.73 1.04 3.09 36.40 ±1.50 163Dy 35.15 1.25 3.56
35.50± 0.70
60Ni 39.09 1.57 4.01 38.80 ±0.20 165Ho 38.77 1.45 3.74
38.30± 0.80
65Cu 38.64 0.69 1.79 37.80 ±1.50 167Er 36.42 1.52 4.18
38.00± 0.90
85Rb 31.72 0.49 1.55 31.40 ±0.40 169Tm 36.53 1.49 4.07
36.80± 0.60
88Sr 78.82 1.24 1.57 78.40 ±0.20 171Yb 38.40 1.36 3.55
39.20± 0.90
89Y 37.89 0.63 1.66 38.30 ±1.40 175Lu 36.99 1.18 3.19
37.00± 0.90
90Zr 37.93 0.95 2.50 37.90 ±1.20 178Hf 37.24 1.31 3.51
36.70± 1.20
93Nb 34.85 0.82 2.35 38.90 ±2.10 181Ta 38.30 1.30 3.40
37.60± 1.90
133Cs 41.63 1.13 2.70 42.70 ±1.80 208Pb 38.73 1.78 4.59
38.57± 0.20
137Ba 37.96 1.25 3.29 39.30 ±0.90 232Th 38.32 1.93 5.05
37.79± 0.08
139La 37.77 1.13 2.98 36.00 ±0.70 238U 38.04 2.28 5.99
37.38± 0.08
13
sample analysed by LA-ICP-MS were calibrated using average values from the other
two pyroxene granulites (DEL99-2-01 and MVP10438).
4.2. Whole rock geochemistry
4.2.1. Sample preparation
Sample preparation for whole rock geochemistry was undertaken on twelve samples
(Table 5) at the University of Western Australia’s geotechnical laboratory, and
GeoAnalytical Laboratory, Washington State University. Twelve samples were cut with
a diamond saw, polished, washed in deionised water and placed in an ultrasonic bath to
remove surface contamination (i.e. saw marks, ink or alteration from weathering), that
could potentially affect the geochemical results. Each sample was reduced to rock chips
using a hydraulic tungsten-carbide rock crusher, and the least-altered material was
handpicked for geochemical analysis. This material was then reduced to a powder using
an agate (silica based) ball mill to avoid tungsten carbide contamination, which can
compromise trace elements such as Ta.
Whole rock geochemistry
MVP10436 DEL99-2-01
MVP10438 DEL2-10434
MVP99-2-08 MVP99-2-13
MVP10437 MVP99-2-22
DEL2-10431 MVP99-2-12
DEL2-10430 MVP99-2-04
Table 5. Samples selected and analysed for whole rock geochemistry
4.2.2. Analytical methods
Whole rock major and trace element analysis was undertaken on the twelve xenoliths.
Sample powders were sent to the GeoAnalytical Laboratory at Washington State
University. Each powder (~ 4g) was fused with a di-lithium-tetraborate (Li2B4O7)
(Spectromelt ® A-10, EM Science, Gibbstown, NJ) flux and made into homogenous
glass disks for major and trace elements. A ThermoARL X-ray Fluorescence
Spectrometer (XRF) was used to measure major and some trace elements, and an
Agilent 4500 Quadrupole Inductively Coupled Plasma Mass Spectrometer (Q-ICP-MS)
was used for determination of most trace elements (Appendix 4). For the latter
instrument, fused discs were prepared separately and dissolved in a mixture of HF-
HNO3. Ru, In and Re are used as internal standards to correct for instrumental drift and
14
mass-dependant differences, REEs are standardised using a linear interpolation method
between In and Re (Doherty, 1989). To avoid isobaric interferences, the CeO/Ce ratio
is maintained at <0.5%. Several reference rock powders from USGS international rock
standards (Jenner et al., 1990; Lichte et al., 1987; Longerich et al., 1990), were analysed
concurrently with the samples to assess the accuracy of the results. Volatile components
were determined by loss on ignition, which involved heating ~ 2g of sample powder in a
carbon crucible overnight at 1100°C in a furnace.
4.3. Calculations applied to geochemical data
Equations used for both whole rock and LA-ICP-MS geochemical data in this thesis are
provided here.
Equation 1. Mineral/whole rock concentration ratios (C)
C = Cmini
CWRi
i = element, C = concentration of trace element, min = mineral analysed, WR = whole
rock sample.
Equation 2. Europium anomaly (Eu/Eu*)
Eu/Eu*= (Eu/EuN) /√Sm/SmN ∗ Gd/GdN
Sm/SmN, Gd/GdN and Eu/EuN represent values normalised to CI Chondrite by Sun and
McDonough, (1995).
Equation 3. Magnesium Number (Mg#)
Mg# = 100 x MgO (mol %)
(MgO+FeO)mol %
FeO represents total Fe3+ and Fe2+
15
4.4. SHRIMP II U-Pb zircon geochronology
4.4.1. Mineral separation
Two samples were selected for zircon separation, based on their moderately high
zirconium contents (~ 100 ppm Zr) as ascertained by whole rock geochemistry. For this
purpose, the remaining crushed sample material that was not used for whole rock
geochemical analysis (~ 500 g) was pulverised using a disk mill adjusted to 500µm
grainsize output. Unwanted material was initially removed by carefully decanting
suspended fine particles from a water filled beaker. A hand magnet was run then over
the mineral separates to remove as much strongly magnetic material as possible. The
remaining material was then run through a Frantz magnetic separator, incrementally
increasing the magnetic current (0.4A, 0.8A, 1.0A and 1.2A), and using gradient
settings of tilt angle 10° and side slope of 15°. Zircon was isolated from the non-
magnetic fraction using a LST (Lithium heteropolytungstate) heavy liquid (2.67g/cm3)
and a 26 cm plastic gold pan.
4.4.2. Grain mount preparation
Approximately two hundred zircon grains were hand-picked under a binocular
microscope from each sample and cast into a 25 mm diameter epoxy resin (Buehler
Epoxicure®) disc, which was left to cure overnight. The grain mount was then polished
to expose the centre of the zircon crystals, using a 3µm diamond compound on a
diamond impregnated polishing lap, and then with a 1µm diamond paste on a silk
polishing lap for 3-5 minutes. The polished sample was viewed under a reflected light
microscope to check for small scratches, and polishing continued as appropriate to
remove surface marks, cleaning the sample ultrasonically between each stage.
Gold coating of the grain mount was undertaken at the John de Laeter Centre for
Isotope Research, Curtin University. Prior to coating, the grain mount was cleaned with
propanol, and consecutively placed in an ultrasonic bath of petroleum spirit, soap
solution and de-ionised water before being placed in <60°C oven for 30 mins to dry.
Gold coating was done using an EMITECH K950X vacuum evaporator set to 40nm at a
deposition rate of 1nm/sec. The glass vacuum chamber was cleaned with Kimwipes and
the mount placed in the centre of the dish. Gold was added to the wire basket, and the
current increased (5-6 A) until the gold melts and vaporises, and the target coating
thickness is met.
16
4.4.3. Electron imaging
Zircon grains were characterised using Scanning Electron Microscopy (SEM), applying
both backscattered electron (BSE) and cathodeluminescence (CL) imaging. Electron
imaging was undertaken at UWA’s Centre for Microscopy, Characterisation and
Analysis. SEM operating conditions for BSE imaging were an accelerating voltage of
10kV, beam intensity of 20 Amps, process time of 5 seconds and working distance of
10 mm for the Zeiss 1555 VP-FESEM and 15 mm for the TESCAN VEGA3. CL
imaging was done using the CL detector attached to the TESCAN VEGA3. This was
required to reveal any internal microstructures and to identify areas for spot analysis by
SHRIMP. Conditions for CL imaging were an accelerating voltage of 10kV, beam
intensity of 15 Amps and low magnification (100-150 x Mag).
4.4.4. Analytical methods
U-Pb geochronology of zircon was undertaken at the John de Laeter Centre for isotope
research at Curtin University, using the Sensitive High Resolution Ion Microprobe
(SHRIMP II). Established analytical protocols were followed for this analysis, as
described by Williams, (1998). Sample zircons were mounted with reference zircons
TEMORA 2 (416.8 ± 0.3 Ma; Black et al., 2003) and M257 (561.3 ± 0.3 Ma; Nasdala et
al., 2008), along with NIST610 glass to ensure accurate centring on the small 204Pb
peak. The reference zircons were analysed after every 3-4 spot analysis. Common lead
(204Pb) correction were applied based on the measured background-corrected 204Pb
counts, using the methods applied in Compston et al., (1984).
4.4.5. Data processing
Data reduction and processing was done using SQUID 2.50 and ISOPLOT 3.71 (add-
ins for Microsoft Excel; Ludwig, 2009), using the decay constants by Steiger and Jäger,
(1997). Individual uncertainty analyses are reported at 1σ level and mean ages for
206Pb/238U calculated to 2σ. The isotope ratios were plotted on Tera-Wasserburg
concordia diagrams (Tera and Wasserburg, 1972) to permit data processing without
correction for common 204Pb, allowing for any inaccurate or negative corrections
associated with background interference. Weighted mean ages were determined using
the 206U/238Pb ratios. Common lead (204Pb) corrected values were used when this
correction was positive, and the uncorrected 206U/238Pb values used when this correction
was negative. These values used to calculate the weighted mean ages are shown in
Table 6.
17
Table 6. 204Pb corrected or uncorrected values used to calculate weighted mean ages for samples
MVP10436, MVP10437 and TEMORA-2 zircon standard.
206U/238Pb common lead corrected age
MVP10436 Age (Ma) MVP10437 Age (Ma) TEMORA-2 Age (Ma)
36-01 409±10.7 37-04 372±8 TEM2-09 408±7.4
36-06 385±7.2 37-05 400±9
36-11 431±9.1 37-11 396±7
36-15 440±16.7 37-15 383±8
36-17 424±8.4
36-18 433±8.9
206U/238Pb uncorrected age
MVP10436 Age (Ma) MVP10437 Age (Ma) TEMORA-2 Age (Ma)
36-02 421±7.4 37-01 371±9 TEM2-01 428.9±17.6
36-03 408±8.0 37-02 368±9 TEM2-02 419.8±7.5
36-04 412±7.9 37-03 352±10 TEM2-03 423.0±7.6
36-05 401±8.7 37-06 385±8 TEM2-04 415.8±8.0
36-07 394±8.1 37-07 407±11 TEM2-05 403.1±8.0
36-08 360±11.3 37-08 401±9 TEM2-06 410.0±8.0
36-09 415±10.3 37-09 358±10 TEM2-07 413.8±7.9
36-10 419±21.8 37-10 421±9 TEM2-08 404.4±7.7
36-12 402±14.6 37-12 386±7 TEM2-10 411.8±7.8
36-13 412±7.4 37-13 352±6 TEM2-11 417.1±8.8
36-14 413±7.3 37-14 411±9
36-16 433±8.0 37-16 423±7
37-17 404±9
18
5. Results
5.1. Mineral chemistry
Major element compositions from EMP analysis for plagioclase, orthopyroxene,
clinopyroxene, garnet and scapolite were determined in Part 1 of this study. End
member compositions were also calculated from the EMP data and are summarised in
Table 7.
Sample End member composition
MVP10438
(two pyroxene)
Pl (An92-93Ab9-10Or0.1-0.2) + Cpx (En38Fs12-14Wo49) + Opx (En65-67Fs33-34Wo0.1-1.5) +
Scp (Me83-85Ma16-17)
DEL99-2-01 (two
pyroxene)
Pl (An92-94Ab6-8Or0-0.1) + Cpx (En40Fs9-10Wo50-51) + Opx (En72-77Fs23-24Wo0-1.5)
MVP10437 (two
pyroxene)
(End member compositions unavailable for sample MVP10437 as explained in
methods section 4.1.2.). Pl (An89-91) by optical microscopy.
MVP99-2-22
(garnet granulite) Cpx (En37-38Fs19-20Wo42-43) + Grt (Al39-46Gr15-23Py38-39)
MVP99-2-12
(garnet granulite) Cpx (En39Fs14Wo48) + Grt (Al35-37Gr21-22Py41-43) + Scp (Me83-84Ma16-17)
DEL2-10434
(eclogite)
Cpx (En35-38Fs12-14Wo49) + Grt (Al40-41Gr20-23Py36-39)
Table 7. Summary of mineral assemblages and end members for the samples analysed for LA-ICP-MS.
This year’s research focused on the trace element compositions of these major minerals
by LA-ICP-MS. Analysis was conducted on six thin sections, the two pyroxene
granulites MVP10437, MVP10438 and DEL99-2-01, the garnet granulites MVP99-2-12
and MVP99-2-22, and eclogite DEL2-10434. These samples were chosen as they
showed the least grain boundary alteration without evidence for textural disequilibrium
(e.g. reaction relationships) between phases. It is important to state at the outset that the
major minerals of these samples showed very little variation in major element
composition, and the trace element inventory of each mineral within a given sample was
also remarkably uniform. For this reason, the below descriptions and corresponding
diagrams refer to average compositions of each mineral within a particular xenolith
sample. Trace element averages for each mineral and sample are shown in Tables 8 and
9. Photomicrographs of these thin sections and the original LA-ICP-MS data for all spot
analyses are presented in Appendix 5A and 5B.
19
Ta
ble
8.
Av
erag
e tr
ace
elem
ent
con
cen
trat
ion
s in
cli
nop
yro
xen
e, o
rth
opy
rox
ene
and
sca
po
lite
fro
m L
A-I
CP
-MS
an
aly
sis.
Cli
no
pyro
xen
eO
rth
op
yro
xen
eS
ca
po
lite
Ele
men
tD
EL
2-1
04
34
MV
P9
9-2
-12
MV
P9
9-2
-22
MV
P1
04
38
DE
L9
9-2
-01
MV
P1
04
37
DE
L9
9-2
-01
MV
P1
04
34
8M
VP
10
43
7M
VP
99
-2-1
2M
VP
10
43
8
Li
6.1
01
2.0
57
.88
8.4
52
.15
21
.63
2.2
37
.72
23
.35
11
.56
32
.54
Sc
33
.54
34
.88
44
.04
13
2.5
41
13
.36
16
7.8
33
8.0
45
1.8
84
7.3
80
.58
0.2
1
V4
55
.53
71
7.9
35
42
.53
53
2.6
24
67
.16
35
9.0
42
49
.39
30
3.5
51
53
.79
0.9
20
.19
Cr
47
1.2
73
24
.68
48
2.2
62
87
.92
98
1.3
81
58
.57
74
9.1
02
19
.29
71
.05
--
Ni
17
6.3
22
66
.32
16
1.7
48
8.7
01
01
.85
23
.33
24
8.2
11
96
.74
39
.28
2.9
9-
Cu
2.4
55
.11
3.7
93
.94
1.6
41
.27
3.2
55
.24
2.5
61
.09
0.9
1
Rb
--
0.0
10
.01
0.0
1-
--
0.1
40
.46
Sr
17
9.2
81
26
.73
50
.55
18
.81
15
.73
12
.81
0.0
20
.05
0.0
22
00
3.1
04
82
.46
Y8
.89
1.8
97
.53
20
.06
18
.53
10
9.7
20
.94
1.6
28
.00
0.2
21
.87
Zr
95
.44
67
.68
46
.89
15
.24
9.0
69
5.2
30
.45
0.9
41
.35
0.1
8-
Nb
0.0
60
.23
0.0
10
.00
0.0
10
.05
0.0
00
.00
0.0
10
.03
-
Cs
-0
.11
0.0
00
.06
0.0
00
.00
0.0
0-
-0
.01
0.0
2
Ba
0.0
50
.61
0.0
60
.02
0.0
20
.03
0.0
2-
0.1
26
5.4
72
6.1
0
La
4.3
55
.27
2.0
41
.48
0.3
35
.84
0.0
00
.02
0.0
31
7.3
18
.33
Ce
17
.85
18
.49
6.6
56
.82
1.8
63
4.1
00
.00
0.0
70
.09
28
.94
16
.10
Pr
3.2
22
.93
1.2
81
.42
0.4
77
.77
0.0
00
.01
0.0
22
.79
1.7
6
Nd
18
.06
14
.62
8.3
78
.93
3.7
34
9.2
50
.01
0.1
10
.15
9.4
07
.16
Sm
4.9
42
.95
3.2
43
.29
1.7
91
7.9
70
.01
0.0
30
.13
0.9
71
.01
Eu
1.5
90
.93
1.4
60
.95
0.7
63
.09
0.0
10
.02
0.0
30
.49
0.5
3
Gd
4.4
51
.67
3.4
63
.76
2.7
62
0.8
80
.03
0.0
90
.33
0.3
90
.75
Tb
0.5
80
.17
0.4
60
.64
0.5
03
.56
0.0
10
.02
0.1
00
.02
0.0
8
Dy
2.5
30
.62
2.1
44
.01
3.4
92
1.8
50
.11
0.2
20
.96
0.0
80
.42
Ho
0.3
90
.09
0.3
30
.82
0.7
64
.51
0.0
30
.06
0.3
00
.01
0.0
6
Er
0.7
20
.16
0.6
32
.17
2.0
21
1.6
40
.14
0.2
31
.20
0.0
10
.15
Tm
0.0
70
.02
0.0
70
.32
0.2
91
.58
0.0
30
.05
0.2
50
.00
0.0
2
Yb
0.3
70
.07
0.3
42
.06
1.8
89
.87
0.2
90
.46
2.2
60
.02
0.0
9
Lu
0.0
40
.01
0.0
40
.29
0.2
71
.38
0.0
60
.07
0.4
20
.00
0.0
2
Hf
3.3
42
.74
2.5
40
.69
0.6
53
.55
0.0
30
.05
0.1
00
.01
0.0
0
Ta
0.0
10
.03
0.0
00
.00
0.0
00
.02
0.0
0-
0.0
00
.00
-
Pb
0.0
70
.28
0.1
00
.06
0.0
20
.28
0.0
10
.01
0.0
43
.91
1.2
8
Th
0.0
40
.02
0.0
20
.02
0.0
10
.06
0.0
00
.00
0.0
10
.01
0.0
0
U0
.01
0.0
20
.00
0.0
00
.00
0.0
20
.17
-0
.06
0.0
00
.00
20
Ta
ble
9.
Av
erag
e tr
ace
elem
ent
con
cen
trat
ion
s in
gar
net
, p
lag
iocl
ase
and
ru
tile
fro
m L
A-I
CP
-MS
an
aly
sis.
Ga
rnet
Pla
gio
cla
seR
uti
le
DE
L2
-10
43
4M
VP
99
-2-1
2M
VP
99
-2-2
2M
VP
99
-2-1
2M
VP
99
-2-2
2M
VP
10
43
8A
DE
L9
9-2
-01
MV
P1
04
37
MV
P9
9-2
-22
MV
P9
9-2
-12
DE
L2
-10
43
4
Li
-2
.18
--
--
1.2
91
2.7
1-
--
Sc
64
.91
80
.50
75
.49
0.4
50
.34
0.2
00
.93
0.8
33
.14
5.6
44
.36
V1
36
.73
25
3.1
61
78
.26
0.5
70
.59
0.2
74
.32
1.3
15
76
.70
20
94
.88
72
6.7
9
Cr
53
8.3
04
86
.85
56
6.1
6-
0.9
0-
9.7
9-
51
4.9
97
83
.74
65
8.1
9
Ni
25
.34
35
.98
21
.16
-1
.03
-1
.74
1.5
1-
5.8
2-
Cu
1.0
51
.38
1.4
2-
1.5
0-
0.5
5-
2.3
33
.11
2.5
5
Rb
0.0
30
.08
0.0
40
.28
0.5
20
.13
0.0
60
.04
0.0
20
.03
-
Sr
0.4
90
.50
0.1
12
44
6.4
68
44
.45
58
4.5
86
48
.32
67
4.8
31
.50
1.3
91
.43
Y8
2.8
71
9.3
86
1.1
9-
0.0
40
.14
0.1
81
.13
0.1
20
.12
0.1
0
Zr
49
.36
27
.08
11
.60
-0
.04
0.0
30
.05
0.1
38
89
.41
14
64
.94
13
18
.60
Nb
0.0
10
.02
0.0
00
.01
0.0
00
.00
0.0
00
.00
10
0.2
94
10
3.3
07
18
.73
Cs
0.0
10
.07
--
0.0
00
.00
--
0.0
10
.03
0.0
0
Ba
0.0
30
.23
0.0
41
51
.64
12
1.4
82
6.1
61
4.9
81
31
.21
1.1
3-
0.0
4
La
0.0
30
.04
0.0
14
.11
1.0
61
.79
0.5
61
5.3
90
.03
0.1
5-
Ce
0.3
80
.46
0.1
25
.09
1.2
82
.71
1.0
42
6.2
30
.01
0.0
40
.00
Pr
0.1
70
.19
0.0
60
.42
0.1
20
.26
0.1
22
.50
0.2
70
.01
0.0
0
Nd
2.2
42
.19
0.9
31
.01
0.4
20
.84
0.4
88
.50
0.0
10
.15
-
Sm
2.4
51
.81
1.4
50
.08
0.0
60
.12
0.0
60
.99
--
0.1
0
Eu
1.4
40
.99
1.1
60
.34
0.3
80
.36
0.2
42
.18
-0
.01
0.0
0
Gd
6.7
22
.99
4.7
90
.05
0.0
30
.06
0.0
80
.60
0.0
10
.09
0.4
4
Tb
1.6
90
.53
1.2
30
.01
0.0
00
.00
0.0
10
.05
0.0
0-
0.0
0
Dy
13
.07
3.6
49
.65
0.0
10
.01
0.0
30
.04
0.2
4-
--
Ho
3.3
00
.81
2.4
1-
0.0
00
.00
0.0
10
.03
-0
.00
0.0
1
Er
9.7
02
.25
7.1
20
.01
0.0
10
.01
0.0
20
.08
-0
.01
-
Tm
1.4
80
.34
1.1
1-
0.0
0-
0.0
00
.01
-0
.00
-
Yb
10
.34
2.3
87
.63
0.0
30
.01
0.0
10
.02
0.0
50
.01
-0
.07
Lu
1.5
80
.36
1.2
1-
0.0
0-
-0
.01
0.0
00
.05
0.0
0
Hf
0.6
50
.44
0.2
5-
0.0
1-
0.0
00
.01
33
.34
43
.37
31
.85
Ta
0.0
10
.00
0.0
0-
0.0
0-
0.0
0-
8.7
03
80
.02
67
.65
Pb
0.0
10
.04
0.0
23
.49
1.1
51
.02
0.3
37
.99
0.0
20
.01
-
Th
0.0
00
.00
0.0
0-
0.0
00
.00
-0
.00
0.2
9-
0.0
8
U0
.01
0.0
00
.00
-0
.00
-0
.00
-0
.69
1.2
91
.14
21
5.1.1. Plagioclase
Plagioclase is present in the two pyroxene xenoliths MVP10437, MVP10438, DEL99-
2-01, and garnet granulites MVP99-2-12 and MVP99-2-22. Figure 3A shows that
plagioclase is enriched in Ba (15-152 ppm) and Sr (585-2447 ppm) relatively to other
trace elements in plagioclase. The REE patterns of plagioclase is characterised by a
strong positive Eu anomaly (Eu/Eu* = 8.6- 26.9), and a positive LREE/HREE ratio
(LaN/YbN = 22.3- 246.6) (Figure 3B). Sample MVP10437 shows a similar pattern to
plagioclase in the other samples, but is significantly enriched in the REEs.
Figure 3A & 3B. Multi-element and REE diagrams for trace elements in plagioclase normalised to CI
Chondrite (Sun and McDonough, 1995). Garnet granulites = red and two pyroxene granulites = green.
0.001
0.01
0.1
1
10
100
1000
Cs Rb Ba Th U Nb Ta Pb Sr Hf Zr Y
Min
era
l/C
hon
dri
te
(3A) Plagioclase
0.01
0.1
1
10
100
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Min
eral/
Ch
on
dri
te
(3B)
MVP99-2-12 MVP99-2-22MVP10438 DEL99-2-01MVP10437
22
5.1.2. Scapolite
Scapolite occurs in the two pyroxene granulite MVP10438, and garnet granulite
MVP99-2-12. As with plagioclase, scapolite displays a high concentration of Ba (483-
2003 ppm) and Sr (26 -66 ppm) (Figure 4A). It is also noted that the Ba and Sr
concentrations are greater in scapolite contained by the garnet bearing sample (MVP99-
2-12). Scapolite shows an overall positive LREE/HREE ratio (Figure 4B). Scapolite in
these two samples shows a positive Eu anomaly (Eu/Eu* = 1.9-2.4), and an unusual
relative depletion in Sm. HREEs are depleted in scapolite of the garnet-bearing sample
MVP99-2-22 relative to that in the two pyroxene granulite MVP10438.
Figure 4A & 4B. Multi-element and REE diagrams for trace elements in scapolite normalised to CI
Chondrite (Sun and McDonough, 1995). Garnet granulites = red and two pyroxene granulites = green.
0.001
0.01
0.1
1
10
100
Rb Ba Th U Nb Ta Pb Sr Hf Zr Y Cs Ti V
Min
eral/
Ch
on
dri
te
(4A) Scapolite
0.01
0.1
1
10
100
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Min
eral/
Ch
on
dri
te
(4B)
MVP99-2-12 MVP10438
23
5.1.3. Clinopyroxene
Clinopyroxene occurs in the two pyroxene granulites MVP10437, MVP10438, DEL99-
2-01, the garnet granulites MVP99-2-12 and MVP99-2-22, and the eclogite sample
DEL2-10434. Clinopyroxene in most xenoliths shows relative depletions in Cs, Rb, Ba,
Ni, Pb, Nb and Ta, and enrichments in Sr, Zr, Hf, Ti, Y, Sc and Li (Figure 5A). The two
pyroxene granulites have a Sr content in clinopyroxene ranging from 12-20 ppm,
whereas the garnet granulites show a higher and more variable Sr content ranging from
49 -181 ppm.
REE concentrations in clinopyroxene are highly variable, with the garnet bearing
samples (DEL2-10434, MVP99-2-12 and MVP99-2-22) having a positive LREE/HREE
ratio, and the non-garnet bearing samples (MVP10438, DEL99-2-01 and MVP10437)
with a negative LREE/HREE ratio. Clinopyroxene in the two pyroxene granulites
MVP10437, MVP10438 and DEL99-2-01shows a strong LREE depletion and a
negative Eu anomaly in MVP10437 and MVP10438. Clinopyroxene in MVP10437
show a higher concentration in REEs relative to clinopyroxene in the other analysed
samples. Clinopyroxene in the garnet bearing samples MVP99-2-12 and MVP99-2-22
shows a relative depletion in the HREEs, reflecting the presence of garnet.
24
0.0001
0.001
0.01
0.1
1
10
100
Li Cs Rb Ba Th U Nb Ta Pb Sr Zr Hf Ti V Y Sc Cr Ni
Min
eral/
Cch
on
dri
te
(5A) Clinopyroxene
DEL2-10434 MVP99-2-12 MVP99-2-22
MVP10438A DEL99-2-01 MVP10437
0.1
1
10
100
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Min
era
l/C
hon
dri
te
(5B)
DEL2-10434 MVP99-2-12 MVP99-2-22
MVP10438A DEL99-2-01 MVP10437
Figure 5A & 5B. Multi-element and REE diagrams for trace elements in clinopyroxene
normalised to CI Chondrite (Sun and McDonough, 1995). Garnet granulites = red, two pyroxene
granulites = green and eclogite = black.
25
5.1.4. Orthopyroxene
Orthopyroxene is a major mineral in the two pyroxene granulite MVP99-2-10 and
MVP10438. Most trace elements in orthopyroxene are present in low concentrations,
and measurable elements include U, Y, Sc, Ti an V. Rare earth elements in
orthopyroxene show a strong depletion in LREEs relative to HREEs, and a slight
negative Eu anomaly is observed in MVP10437 (Figure 6B).
Figure 6A & 6B. Multi-element and REE diagrams for orthopyroxene normalised to CI Chondrite (Sun
and McDonough, 1995). Two pyroxene granulites = green.
0.0001
0.001
0.01
0.1
1
10
Ba Th Nb Ta Pb Sr Hf Zr Y Ti Sc V Cr Ni
Min
eral/
Ch
on
dri
te
(6A) Orthopyroxene
0.001
0.01
0.1
1
10
100
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
MIn
eral/
Ch
on
dri
te
(6B)
DEL99-2-01 MVP10438A MVP10437
26
5.1.5. Garnet
Garnet is present in the garnet granulites MVP99-2-12, MVP99-2-22, and the eclogite
sample DEL2-10434. Most non-REE trace elements in Figure 7A are low in
concentrations relative to the high field strength elements Zr, Hf, Ti, Y and Sc. As is
typical of garnet, rare earth elements show a HREE enrichment and depletion in LREEs
(Figure 7B). The degree of fractionation within the LREEs is much more significant
than the HREE fractionation, with sample MVP99-2-12 showing little to no HREE
fractionation.
Figure 7A & 7B. Multi-element and REE diagrams for trace elements in garnet normalised to CI
Chondrite (Sun and McDonough, 1995). Garnet granulite = red and eclogite = black.
0.001
0.01
0.1
1
10
100
Cs Rb Ba Th U Nb Ta Pb Sr Zr Hf Ti V Y Sc
Min
eral/
Ch
on
dri
te
(7A) Garnet
0.01
0.1
1
10
100
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Min
eral/
chon
dri
te
(7B)
DEL2-10434 MVP99-2-12
MVP99-2-22
27
5.1.6. Rutile
Trace elements were determined from rutile of the garnet granulite samples MVP99-2-
12 and MVP99-2-22, and the eclogite sample DEL2-10434. Rutile was analysed for the
full suite of trace elements, with most elements at concentrations below the detection
limits. Chondrite normalised values of the most abundant trace elements show an
enrichment in Zr, Nb, Hf, Ta and U relative to Sc, V, Cr, Cu, Sr and Y (Figure 8). Of
the more enriched elements, Nb and Ta show large variations between rutile grains of
the different rock types (Nb = 100-4141 ppm, Ta = 9-384 ppm).
Figure 8. Multi-element diagram for trace elements in rutile normalised to CI Chondrite (Sun and
McDonough, 1995). Garnet granulites = red and eclogite = black.
0.01
0.1
1
10
100
1000
10000
U Nb Ta Sr Zr Hf V Y Sc Cr Cu
Min
era
l/C
hon
drt
ie
Rutile
DEL2-10434 MVP99-2-12
MVP99-2-22
28
5.2. Whole rock geochemistry
5.2.1. Major element geochemistry
Whole rock major and trace element compositions were determined for eight samples
from the Monaro Volcanic Province, and four samples from the Delegate breccia pipes
(Table 10). All samples are basaltic and metaluminous in composition (ASI = 0.54-
0.95). The SiO2 content ranges from 46.9-51.5 wt. % for the two pyroxene and garnet
granulite samples, while the eclogite sample (DEL2-10434) has a slightly lower silica
content at 45.1 wt. %. Two pyroxene granulites MVP10436 and MVP10437 show a
higher TiO2 concentration (2.0 and 1.8 wt. %), than the other two pyroxene granulites
(<0.3 wt. %), and the garnet granulites (<1.1 wt. %), reflecting the Fe-Ti oxide minerals
in these samples. The magnesium number (Mg#) is variable among the samples,
although MVP10436 and MVP10437 have distinctively lower magnesium numbers
(52.3 and 54.5, respectively). Garnet granulite MVP99-2-22 has a slightly lower Al2O3
content at 15.9 wt. %, compared to the granulite samples.
The two pyroxene granulite from Griffin & O’Reilly, (1986) with later zircon U-Pb age
determinations from Chen et al., (1998), are included in Table 11. The major element
compositions from Griffin & O’Reilly, (1986) show the same characteristics as samples
MVP10436 and MVP10437 determined by this study. Bulk lower crustal compositions
from Rudnick and Presper, (1990) and Rudnick and Fountain, (1995), are also
compared to values from this study. The average silica content for xenoliths from the
Monaro and Delegate samples is 48.5 wt. %, slightly lower than the values from
Rudnick and Presper, (1990) and Rudnick and Fountain, (1995). The average Mg# of
the Monaro and Delegate xenoliths (64.6) is slightly higher than average values given
by Rudnick and Presper, (1990) and Rudnick and Fountain, (1995).
29
Table 10. Whole rock major element wt. % oxides for two pyroxene granulite (2pG), garnet granulite
(GG) and eclogite (Ec) xenoliths. DEL = Delegate breccia pipes, MVP = Monaro Volcanic Province. FeO
= total iron. Mg# calculated following Equation 3 in methods section 4.3.
Rock 2pG 2pG 2pG 2pG GG GG
Sample
MVP10436
MVP10437
MVP10438
MVP99-2-08
MVP99-2-04
MVP99-2-12
SiO2 46.87 47.61 48.44 49.13 50.46 46.99
TiO2 1.98 1.77 0.27 0.15 0.49 0.72
Al2O3 17.22 16.49 20.97 18.55 19.33 18.50
FeO 11.88 11.81 7.15 6.21 6.37 10.69
MnO 0.21 0.22 0.14 0.13 0.13 0.18
MgO 7.30 7.93 8.39 10.96 7.87 9.08
CaO 11.37 10.79 13.13 13.68 11.35 10.91
Na2O 2.54 2.80 1.39 1.14 3.64 2.14
K2O 0.31 0.31 0.11 0.05 0.41 0.72
P2O5 0.32 0.27 0.02 0.01 0.05 0.06
Mg# 52.27 54.48 67.66 75.88 68.77 60.22
Rock GG GG 2pG Ec 2pG 2pG
Sample
MVP99-2-
13
MVP99-2-22
DEL99-2-01
DEL
2-10434
DEL
2-10430
DEL2
-10431
SiO2 48.89 51.53 48.78 45.09 50.22 47.75
TiO2 0.39 1.09 0.24 1.96 0.76 0.60
Al2O3 17.55 15.88 19.06 14.04 17.50 20.18
FeO 7.76 9.32 6.25 11.48 7.42 8.34
MnO 0.16 0.17 0.12 0.20 0.14 0.15
MgO 10.54 7.29 11.37 9.86 9.02 7.38
CaO 11.45 9.95 12.76 14.42 12.12 13.13
Na2O 2.70 4.21 1.35 2.67 2.61 2.12
K2O 0.52 0.56 0.07 0.16 0.13 0.16
P2O5 0.04 0.02 0.01 0.13 0.08 0.20
Mg # 70.77 58.23 76.43 60.49 68.42 61.2
30
Table 11. Whole rock major element wt. % oxides for two pyroxene granulite (2pG), garnet granulite
(GG) and eclogite (Ec) xenoliths from published values on similar rock types (Lovering and White, 1969;
Griffin and O’Reilly, 1986). Bulk lower crustal values from Rudnick and Presper, (1990) and Rudnick
and Fountain, (1995). Average major element compositions from this study for the Monaro Volcanic
Province samples only and Monaro samples including the Delegate breccia pipe xenoliths. FeO = total
iron. Mg# calculated following Equation 3 in methods section 4.3.
Lovering and White, (1969)
Rock 2pG 2pG 2pG GG GG Ec
Sample R18 R52 R112 R130 R46 R11
SiO2 44.46 47.6 51.12 45.93 45.51 45.09
TiO2 0.74 0.33 0.06 0.56 1.96 1.26
Al2O3 17.46 18.17 16.4 16.97 16.58 12.53
FeO 9.02 4.18 4.82 5.8 6.03 8.21
MnO 0.22 0.12 0.15 0.17 0.19 0.23
MgO 10.16 10.18 8.34 7.97 7.57 10.12
CaO 12.72 14.73 11.22 11.96 11.88 12.37
Na2O 0.33 1.19 2.99 3.21 3.1 2.02
K2O 0.53 0.03 0.43 0.21 0.23 0.17
P2O5 0.15 0.09 0.15 0.47 0.76 0.34
Mg# 66.75 81.25 75.52 71.01 69.11 68.72
Rock
Sample
Griffin & O’Reilly, (1986)
2pG
10430/1
Rudnick
and
Presper,
(1990)
Rudnick and
Fountain,
(1995)
Average wt.
%
(MVP
xenoliths)
Average wt.
%
(This study)
SiO2 46.85 52.0 53.4 48.74
48.48
TiO2 1.72 1.13 0.82 0.86 0.87
Al2O3 16.45 17.0 16.9 18.06 17.94
FeO 11.83 9.08 8.57 8.90 8.72
MnO 0.13 0.15 0.10 0.17 0.16
MgO 7.87 7.21 7.24 8.67 8.92
CaO 11.04 10.28 9.59 11.58 12.09
Na2O 2.78 2.61 2.65 2.57 2.44
K2O 0.28 0.54 0.61 0.37 0.29
P2O5 0.27 0.13 0.10 0.10 0.10
Mg # 54.26 58.6 60.09 63.46 64.58
31
Variation diagrams for major elements plotted against Mg# are shown in Figures 9A-
9H. With an increasing Mg# there is a general decrease in TiO2, FeO, P2O5, Na2O and
K2O, and an increase in CaO, Al2O3 and SiO2. Plots of Mg# vs. K2O and CaO (Figure
9E and 9F), separate the garnet and the non-garnet bearing samples. The eclogite has a
high CaO and low Al2O3 and SiO2 compared to the other xenoliths in this study.
Published values from similar rock types (Lovering and White, 1969), are also plotted
on these diagrams. The two pyroxene granulites R112 and R18 in Figures 9E and 9F do
not plot within the non-garnet bearing as do the samples from this study. With literature
values plotted, correlation trends with Mg# become less evident, except Mg# vs. FeO
wt. % (Figure 9D) which still shows a strong negative correlation.
A B
C D
32
Figures 9A-9H. Major element variation plots showing Mg# vs. SiO2, TiO2, Al2O3, FeO, MnO, CaO,
Na2O, K2O and P2O5. Al2O3 vs. SiO2 and FeO. Garnet granulite =red, two pyroxene granulite =green and
eclogite sample =black. FeO calculated as total FeO and Fe2O3. Mg# calculated using Equation 3 in
methods section 4.3. Clear circle show published values for similar rock types by Lovering and White,
(1969).
E F
G H
33
5.2.2. Trace element geochemistry
Trace element concentrations for the xenoliths are given in Table 12. Selected trace
elements from xenolith samples are normalised to bulk continental crust (Figure 10),
and plotted against average lower crustal compositions (Rudnick and Presper, 1990;
Rudnick and Fountain, 1995). Trace elements were similarly normalised to mid ocean
ridge basalt (MORB) compositions from Keleman et al., (2003) (Figure 11), and plotted
against typical basalt types. REEs normalised to chondrite are plotted separately and
shown in Figure 12.
Some general trends in the trace element data are observable in both of these plots.
Trace elements in the two pyroxene xenoliths show a greater range than the garnet
granulites. Significant relative enrichments in Ba, Pb, and Sr, and depletions in Nd, Zr
and Hf are shown by most samples excluding MVP10436, MVP10437 and DEL2-
10434. Some notable features include a cluster Sr values showing similar concentrations
across all samples, a considerably greater Ba concentration in DEL2-10431 compared to
other samples, and a strong K depletion in the eclogite sample (DEL2-10434), relative
to the neighbouring elements. Generally, the garnet and non-garnet bearing xenoliths
can be separated by their K and Rb contents.
Most samples, irrespective of major mineralogy show a slight enrichment in LREE
relative to the HREE (LaN/YbN = 0.5-5.2), the exception being sample MVP99-2-22 and
DEL99-2-01. HREE trends are mostly flat (GdN/LuN = 1.0-1.7), and most samples have
a positive Eu anomaly (Eu/Eu* = 0.8– 1.9; Table 13), these being most conspicuous in
the LREE depleted samples. The eclogite sample has a smooth chondrite normalised
pattern with no significant Eu anomaly, and the two pyroxene granulites MVP10436
and MVP10437 have a negative Eu anomaly and show the greatest REE enrichment.
34
Ta
ble
12
. W
ho
le r
ock
tra
ce e
lem
ent
anal
ysi
s (v
alu
es i
n p
pm
). 2
pG
= t
wo p
yro
xen
e g
ran
uli
te,
GG
= g
arn
et g
ran
uli
te a
nd
Ec
= e
clo
git
e
Ro
ck2p
G2p
G2p
G2p
GG
GG
GG
GG
G2p
GE
c2p
G2p
G
Sam
ple
n
o.
10436
10437
10438
99-2
-08
99-2
-04
99-2
-12
99-2
-13
99-2
-22
DE
L-9
9-2
-
01
DE
L-2
-
10434
DE
L-2
-
10430
DE
L-2
-
10431
Cs
0.0
80.0
80.8
10.1
44
1.2
94.8
0.4
60.4
33.2
90.1
90.6
2
Rb
9.5
83
1.7
7.6
18.3
10.1
11.5
3.9
9.5
2.6
4.1
Ba
80
87
328
63
316
637
770
437
81
527
107
2135
Th
0.1
20.1
40.0
70.1
0.5
30.3
70.2
20.0
70.1
50.7
90.1
90.7
3
U
0.0
60.0
50.0
20.0
20.1
20.0
90.0
50.0
30.0
40.3
20.0
50.1
8
Nb
9.2
28.0
50.3
70.9
13.8
512.1
31.3
1.2
90.9
913.7
42.4
85.4
1
Ta
0.5
90.5
30.0
20.0
60.2
0.6
60.0
70.0
90.0
40.7
0.1
60.2
8
La
13.3
11.9
31.6
42.3
53.5
95.1
11.9
1.5
71.0
28.4
25.4
89.1
9
Ce
34.8
930.9
23.3
74.9
36.5
511.4
33.9
3.9
31.8
820.8
812.3
116.7
9
Pb
3.1
73.1
0.5
50.6
1.0
91.3
20.6
20.5
50.4
30.6
2.1
11.4
5
Pr
5.4
54.8
90.4
90.6
60.8
21.6
20.5
60.6
90.2
63.2
71.7
32.2
Sr
615
655
561
448
548
864
550
445
482
366
424
701
Nd
26.5
623.9
42.4
12.8
23.4
87.3
52.7
74.3
1.4
16.3
77.9
69.5
1
Sm
7.3
76.8
80.7
30.7
60.9
42
0.9
21.9
60.5
34.9
42.4
12.3
4
Zr
103
80
45
11
41
11
32
4106
25
18
Hf
2.5
42.0
20.1
50.1
50.3
41.1
50.3
81.4
10.2
13.0
10.8
70.5
Eu
2.0
81.9
20.4
0.3
80.6
20.8
70.5
51.1
40.3
11.8
10.8
80.9
7
Gd
7.7
77.4
0.8
10.7
81.1
22.1
21.1
12.9
0.7
55.9
42.8
52.4
2
Tb
1.3
1.2
40.1
40.1
30.2
10.3
50.2
0.5
70.1
51.0
50.5
20.3
9
Dy
7.8
37.6
30.9
10.8
61.2
92.2
31.3
63.7
51.0
66.6
3.3
52.4
5
Y
37.9
436.6
24.5
54.3
16.5
210.8
56.9
719.8
95.3
234.0
917.0
513.7
Ho
1.5
71.5
20.1
90.1
80.2
70.4
70.3
0.8
10.2
21.3
90.6
90.5
1
Er
4.0
64.0
30.5
20.4
90.7
11.2
80.8
42.2
50.6
23.6
71.8
71.3
6
Tm
0.5
70.5
50.0
80.0
70.1
0.1
80.1
20.3
20.0
90.5
30.2
70.1
9
Yb
3.3
53.2
30.4
70.4
50.6
41.1
30.7
52.0
50.5
63.2
11.6
61.1
6
Lu
0.4
90.4
70.0
70.0
70.1
0.1
70.1
10.3
10.0
80.4
90.2
50.1
8
Sc
51.5
50.9
36.9
38.8
33.2
49.7
40.5
38.9
39.2
43.1
37.3
39.5
35
36
37
38
Figure 10. Multi-element plot for xenoliths normalised to bulk continental crust (Rudnick and Gao,
2003). Two pyroxene granulites = green, garnet granulites = red, eclogite = black and bulk lower crustal
compositions = pink. Bulk lower crustal values from Rudnick and Presper, (1990) and Rudnick and
Fountain, (1992).
Figure 11. Multi-element plot for xenoliths normalised to mid ocean ridge basalt (Kelemen et al., 2003).
Xenoliths plotted against average ocean island basalts, oceanic arc basalts and continental arc basalts also
compiled by Kelemen et al., (2003). Two pyroxene granulites = green, garnet granulites = red, eclogite =
black and basalts from Kelemen et al., (2003) = blue.
Figure 12. Rare earth element data from whole rock geochemistry normalised to CI Chondrite
(McDonough and Sun, 1995). Two pyroxene granulites = green, garnet granulites = red and eclogite
black.
Sample Rock type Eu/Eu*
10436
2Py
0.84
10437 2Py 0.82 10438 2Py 1.58 99-2-08 2Py 1.51
DEL-2-10430 2Py 1.03 DEL-2-10431 2Py 1.24 DEL-99-2-01 2Py 1.49 99-2-04 GG 1.85
99-2-12 GG 1.29 99-2-13 GG 1.65 99-2-22 GG 1.45 DEL-2-10434 Ec 1.02
Rudnick and Presper, (1990) Bulk lower crust 1.05 Rudnick and Fountain, (1995) Bulk lower crust 1.14
Table 13. Eu/Eu* values calculated using Equation 2 from methods section 4.3. Eu/Eu* for bulk lower
crust calculated using Eu, Sm and Gd values from Rudnick and Presper, (1990) and Rudnick and
Fountain, (1995).
5.2.2.1. Normalisation to bulk continental crust
Normalisation to bulk continental crust shows a general depletion in most trace
elements except Sr, which is enriched in all samples. Ta, Nb and Ti enrichments are also
observed, possibly reflecting the presence of rutile. Lower crustal compositions,
inferred from these xenoliths suggest a greater depletion in radiogenic elements (Th, U)
and a strong Ba enrichment compared to the bulk lower crustal compositions (Rudnick
and Presper, 1990; Rudnick and Fountain, 1995).
39
The Ta/Nb ratio in lower crustal averages based on mafic xenolith compositions
(Rudnick and Presper, 1990), is similar to that of xenoliths analysed in this study. The
Ta/Nb ratio in lower crustal averages by Rudnick and Fountain, (1995) on the other
hand, which are derived mainly from exposed granulite terranes and seismic profiling
show a lower Ta/Nb ratio. The Sr abundance in average lower crustal compositions is
similar to compositions of the bulk continental crust, both of which are slightly lower
than the Sr content in the analysed xenoliths.
5.2.2.2. Normalisation to mid ocean ridge basalts (MORB)
Compared to MORB compositions these granulite xenoliths show an enrichment in Ba,
Sr, Pb and depletion in U, Ta, Nb, Zr and Hf (Figure 12). MORB-normalised trends are
clearly distinct from ocean island basalts, however, show similar trace element
characteristics to oceanic and continental arc basalts. The Ta and Nb depletions relative
to La are characteristic of typical arc basalts and emphasise these similarities. Most
xenoliths are depleted in Th, U, Pb, Zr and Hf, and are enriched in Ba relative to both
the ocean island basalts and arc basalts. The flat HREE pattern of the xenolith samples
is similar to that of MORB and arc basalts, although lack any Eu anomaly or REE
fractionation observed in these xenoliths. The eclogite sample (DEL2-10434), does not
show the same characteristic as the two pyroxene and garnet granulites. It has a smaller
enrichment in Ba and Sr, and generally displays a much flatter trend compared to the
other rock types.
40
5.3. Mineral/whole rock concentration ratios
Trace element concentrations in clinopyroxene, orthopyroxene, plagioclase, garnet and
rutile, were divided by their abundance in the corresponding whole rock sample
(Equation 1 in methods section 4.3). These values, referred to as concentration ratios
(CX/WRi ) can be compared with known mineral-melt partition coefficients in basaltic
rocks and are plotted in Figures 13A-13E. High concentration ratios (C>1) indicate that
trace element concentrations in individual minerals are greater than their concentration
in the whole rocks. Average values for each mineral were calculated, given the small
variation of trace elements within and between the same mineral phase of a given
xenolith sample.
Clinopyroxene in the two pyroxene granulites contain concentration ratios Ccpx >1 for
elements Ni, Cr, Hf, Sc, Zr, Y and the REEs (Figure 13A). The garnet granulites and
eclogite sample show similar concentration ratios in clinopyroxene, apart from a strong
depletion in the HREEs (Ccpx <1) reflecting the presence of garnet. Experimental
mineral-melt partition co-efficients in clinopyroxene (Arth, 1976; Fujimaki et al., 1984)
show an enrichment in Th, U, Nb, Ta, Sr, Ni, Cr and the HREEs, relative to the
concentration ratios of clinopyroxene in these xenoliths (Figure 13A). Trace elements in
orthopyroxene on the other hand, show similar trends between the calculated
concentration ratios and the experimental partition coefficients by Arth, (1976) (Figure
13B). This reflects the minimal input orthopyroxene has on the trace element budget of
the whole rock compositions, and of basaltic rocks in general.
Plagioclase in these samples, particularly in the two pyroxene granulites, show similar
trace element concentration ratios to the experimental partition coefficients from Arth,
(1976) and Fujimaki et al., (1984) (Figure 13C). With the exception of the strong
depletions in Zr, Hf and Nb, concentration ratios for plagioclase in these xenoliths are
typical of crystallising plagioclase from a basaltic melt.
Experimental partition coefficients for trace elements in garnet from Johnson, (1998),
Hauri et al., (1994) and Irving and Frey, (1978), are shown in Figure 13D.
Concentration ratios for garnet in these xenoliths are slightly depleted in Ba and Sr, and
significantly more depleted in Nb compared to the partition coefficients for garnet in a
41
basaltic melt. Garnet also lacks a strong Hf depletion, and show a greater depletion in
the LREEs relative to the HREEs compared to experimental partition coefficients.
Concentration ratios of rutile in these samples are depleted in most elements except U,
Nb, Ta, Hf, Zr. Partition coefficients for rutile in basaltic rock were available for Nb,
Ta, Hf and Zr, and are plotted against the calculated concentration ratios in Figure 13E.
Rutile in these samples, particularly in the garnet granulites show a greater enrichment
in Nb, Ta, Hf and Zr compared to the experimental partition coefficients by Bennett et
al., (2004) and Klemme et al., (2005). Sample MVP99-2-12 also shows a greater Nb/Ta
vs. Zr/Hf fractionation relative to rutile in samples MVP99-2-22 and DEL2-10434.
0.00
0.01
0.10
1.00
10.00
Rb Th U Ta Nb La Ce Sr Nd Zr Hf Sm Eu Gd Dy Y Er Yb Lu Ni Cr
Min
eral/
wh
ole
rock
Clinopyroxene
MVP10437
MVP10438
DEL99-2-01
MVP99-2-12
MVP99-2-22
DEL2-10434
Experimental partition coefficients
Figure 13A. Concentration ratios plotted against experimental mineral/melt partition coefficients for
clinopyroxene. Experimental partition coefficients from Arth, (1976) and Fujimaki et al., (1984).
42
0.001
0.010
0.100
1.000
Nd Zr Sm Eu Gd Dy Y Er Yb Lu
Min
eral/
wh
ole
rock
Orthopyroxene
MVP10437
MVP10438
DEL99-2-01
Experimental partition coefficients
0.000
0.001
0.010
0.100
1.000
10.000
Rb Ba Th U Nb La Ce Sr Nd Zr Hf Sm Eu Gd Dy Y Er Yb Lu
Min
eral/
wh
ole
rock
Plagioclase
MVP10437 MVP10438
DEL99-2-01 MVP99-2-12
MVP99-2-22 Experimental partition coefficients
Figure 13B. Concentration ratios plotted against mineral/melt partition coefficients for
orthopyroxene. Experimental partition coefficients from Arth, (1976).
Figure 13C. Concentration ratios plotted against mineral/melt partition coefficients for
plagioclase. Experimental partition coefficients from Arth, (1976) and Fujimaki et al.,
(1984).
43
0.0000
0.0001
0.0010
0.0100
0.1000
1.0000
10.0000
Rb Ba Th Nb La Ce Sr Nd Zr Hf Sm Eu Gd Dy Y Er Yb Lu
Min
era
l/ w
ho
le r
ock
Garnet
MVP99-2-12
MVP99-2-22
DEL2-10434
Experimental partition coefficients
1
10
100
1000
Nb Ta Zr Hf
Min
eral/
Wh
ole
rock
Rutile
MVP99-2-12
MVP99-2-22
DEL2-10434
Experimental partition coefficients
Figure 13D. Concentration ratios plotted against experimental mineral/melt partition
coefficients for garnet (Johnson, 1998; Hauri et al., 1994; Irving and Frey, 1978).
Figure 13E. Concentration ratios plotted against mineral/melt partition coefficients.
Elements above detection limits are plotted. Experimental partition coefficients from
Bennett et al., (2004) and Klemme et al., (2005).
44
5.4. Zircon mineralogy
Reflected and transmitted light microscopy, and BSE and CL imaging was carried out
on individual zircon grains in the xenolith samples before and after mineral separation.
Zircon grains range from 50 -200µm in size (Figure 14A-14F). Their morphology is
variable, ranging from rounded to elongate to irregular shapes dictated by the geometry
of adjacent minerals. In thin section, zircon exists as inclusions in the major minerals
(Figures 14A, 14B and 14C), and also at the grain boundaries of the major minerals,
particularly ilmenite (Figures 14D, 14E and 14F). These textures show evidence for
zircon crystallisation both before and during/after the formation of the granulite
mineralogy. Internal features observed in CL imaging include irregular zoning patterns,
some sector zoning, and inclusions (Figures 15A – 15F). A generally strong CL
response, observed in these grains is consistent with their low uranium concentrations
(e.g. Kroner et al., 1987). The 206Pb/238U mean weighted ages added on these grains
show no relationship between microstructures or size of the zircons.
45
Figure 14A-14F. In situ zircon imaging of sample MVP10436. A.Transmitted light (PPL) zircon in
plagioclase x 5 Magnification. B. Transmitted light (PPL) zircon in plagioclase x 20 Magnification. C.
BSE image of zircon inclusion in plagioclase (1812 x Mag, 15kV, WD 10mm). D. Transmitted light
(PPL) zircon in contact with plagioclase, ilmenite and clinopyroxene. E. BSE image of image D (Mag
1472 x, WD 10mm, 15Kv). F. Deformed zircon between clinopyroxene and Ilmenite (Mag 710 x, 15kV,
WD 10mm). Abbreviations follow Kretz, (1983).
A B
C D
E F
46
Figures 15A-15F. CL images of zircon grains for sample MVP10437 (A-C), and sample MVP10436 (D-
F). 206Pb/238U mean weighted ages for individual SHRIMP pits are included (see Table 6 in section 4.4.5
in methods for selection criteria). Ages represent the majority, but not all analyses – for the purpose of
relating ages to microstructures.
47
5.5. U-Pb (SHRIMP II) age determinations- Monaro Volcanic Province xenoliths
Seventeen spot analyses were conducted on eleven zircon grains from MVP10437, and
eighteen spot analyses on fifteen zircon grains from MVP10436 (Appendix 7). The
uranium content in samples MVP10436 and MVP10437 are variable, ranging from 23-
465 ppm, and 27-454 ppm respectively. The common lead corrected 206Pb/238U ages
from the zircons in these xenoliths vary from 375 ± 11.3 Ma to 439 ± 16.7 Ma for
MVP10436 and 352 ± 6.3 Ma to 428 ± 9 Ma for sample MVP10437.
Eleven analyses from the TEMORA-2 zircon standard yield a concordia age of 414 ±
4.8 Ma (Figure 16A), and mean weighted ages (Figure 16B) within analytical
uncertainty of the recommended 416.8 ± 0.3 Ma value from Black et al., (2003).
Weighted age averages provided a selection criteria to identify populations of data to
calculate concordia ages for the xenolith samples. These plots showed less variability in
the distribution of age data from sample MVP10436 (Figure 17A) compared to
MVP10437 (Figure 18A).
Sample MVP10436 produced a U-Pb concordia age of 419.4 ± 6.6 Ma based on the
observed cluster of data, and rejecting four analyses with low 206Pb/238U ages attributed
to lead loss (Figures 17B and 17C). Data from sample MVP10437 (Figure 18B) showed
a greater spread along concordia compared to sample MVP10436. The interpretation of
these data is therefore less straightforward. This spread may be interpreted as complete
lead loss, and therefore, none of these data ellipses are representative of the true zircon
age, or alternatively, zircons may have undergone partial lead loss, and the oldest group
of data represents the true zircon age. If the second scenario is true, a U-Pb concordia
age can be calculated from the oldest cluster of data which gives an age of 402.5 ± 6.3
Ma (Figure 18C).
48
Figure 16A. Terra-Wasserburg concordia plot in the TEMORA-2 zircon standards 414 ± 4.8 Ma. (2s,
decay-constant errors included).
Figure 16B. 206Pb/238U results from the TEMORA-2 zircon standard. Mean weighted ages calculated to
95% confidence. 0 of 11 rejected.
385
395
405
415
425
435
445
455
206P
b/2
38U
Ag
es (
Ma
)
box heights are 1sMean age = 413.0 ± 4.8 Ma
MSWD = 0.71
Probability of fit = 0.72
0.049
0.051
0.053
0.055
0.057
0.059
0.061
12.5 13.5 14.5 15.5 16.5
207P
b/2
06P
b
238U/206Pb
TEMORA-2
Age = 414.0 ±4.8 Ma
MSWD = 1.9
Probability = 0.17
data-point error ellipses are 68.3% conf.
380
420
460
49
Figure 17A. 206Pb/238U results from sample MVP10436. Ages calculated to 95% confidence,
including error in standard deviation. 4 of 18 rejected.
330
350
370
390
410
430
450
470
206P
b/2
38U
Ag
es (
Ma
)
box heights are 1s
MVP10436
Mean Age = 419 ± 4.9 Ma
MSWD = 1.19
Probability = 0.28
0.045
0.055
0.065
0.075
11 13 15 17 19
207P
b/2
06P
b
238U/206Pb
MVP10436 data-point error ellipses are 68.3% conf.
350
450
550
Figure 17B. Tera - Wasserburg diagram showing ellipses for all spot analysis of zircons in
the two pyroxene xenolith MVP10436. Red ellipses are excluded from the U-Pb concordia
age calculation.
50
330
350
370
390
410
430
206P
b/2
38U
Ag
es (
Ma
)
box heights are 1s
MVP10437
Mean age = 400.5 ± 9.6 Ma
MSWD = 3.0
Probability = 0.001
0.046
0.050
0.054
0.058
0.062
12 13 14 15 16 17
20
7P
b/
20
6P
b
238U/206Pb
MVP10436 data-point error ellipses are 68.3% conf.
360400
440
480
Concordia age = 419.4 ±6.6 Ma
MSWD = 1.05
Probability = 0.31
N = 14 of 18
Figure 17C. Tera – Wasserburg concordia plot, excluding values with suspected Pb loss shown
from 19A. Concordia age is calculated at 419.4 ±6.6 Ma at 95% confidence, including decay-
constant errors.
Figure 18A. 206Pb/238U results from sample MVP10437. Ages calculated to 95% confidence,
including error in standard deviation. 6 of 17 rejected.
51
Figure 18B. Tera – Wasserburg diagram showing ellipses for all spot analysis of zircons
in the two pyroxene xenolith MVP10437.
Figure 18C. Tera – Wasserburg concordia plot of a possible population of concordant data from
Figure 18B. Age is calculated to 95% confidence, including decay constant errors.
0.04
0.05
0.06
0.07
0.08
13.5 14.5 15.5 16.5 17.5
20
7P
b/2
06P
b
238U/206Pb
MVP10437
Concordia age: 402.5 ±6.3 Ma
MSWD = 0.13,
Probability = 0.72
N= 11 of 17
data-point error ellipses are 68.3% conf.
370410450
340380420460
0.04
0.05
0.06
0.07
0.08
13 15 17 19
207P
b/2
06P
b
238U/206Pb
MVP10437 data-point error ellipses are 68.3% conf.
52
5.6. Comparison of the dated xenoliths to the Delegate breccia pipe xenoliths
The dated xenoliths in this study from the Monaro Volcanic Province (MVP10436 and
MVP10437), and the previously dated Delegate breccia pipe xenoliths by Chen et al.,
(1998) (sample 10430/1) resemble a two pyroxene mineralogy and are geochemically
identical. These samples are geochemically distinct from the non-zircon bearing two
pyroxene granulites. Major element comparisons are presented in Table 11 from section
5.2.1, and available trace elements are provided in Table 14 below.
Table 14. Available trace element comparison between samples from Griffin and O’Reilly, (1986)
(10430/1) and this study (MVP10436 and MVP10437).
Zircon U-Pb concordia ages from the previously studied Delegate xenoliths (using ID-
TIMS) were 398 ± 2 Ma and 391 ± 2 Ma (Chen et al., 1998). The low U concentration
in zircon meant that multiple grains needed to be dissolved together to provide enough
pictograms of Pb for the analyses. Grain fractions for ID-TIMS were selected based on
grains showing a similar morphology as described in Chen et al., (1995). These ages are
younger than the SHRIMP 419.4 ± 6.6 Ma from sample MVP10436 in this study,
however, show a closer relationship with the more obscure 402.5 ±6.3 Ma ages from
sample MVP10437 which showed a spread of data along concordia in Figure 18B.
5.7. Age comparison to the regional lithological units
The 419.4 ± 6.6 Ma U-Pb zircon age from sample MVP10436 is within the ages of the
I-type granites of the Berridale Batholith (Ickert and Williams, 2011), and Bega
Batholith (Chen and Williams, 1990). Unlike sample MVP10436, the 402.5 ±6.3 Ma
age produced by sample MVP10437 does not fall within the ages of the regional
granites, although both ages are significantly older than the Monaro Volcanic Province
alkali basalt pipes, of which they are hosted in (55-34 Ma; Wellman and McDougall,
1974b). The ages of the lithological units near the xenolith pipe localities are
summarised here in Table 15 for comparison with the zircon ages from these xenoliths.
10430/1 MVP10436 MVP10437
Rb 9.1 9.5 8
Sr 602 615 655
Y 41 37.94 36.62
Zr 62 103 80
Nb 9 9.22 8.05
Ba 86 80 87
53
Rock type Dating method Age & reference
Two pyroxene granulite xenoliths
(Monaro Volcanic province).
Zircon U-Pb
(SHRIMP)
419.4 ± 6.6 Ma (this study
MVP10436)
402.5 ±6.3 Ma (this study
MVP10437)
Two pyroxene granulite xenoliths
(Delegate breccia pipes)
Zircon U-Pb
(IDTIMS)
398 ± 2 Ma (Chen et al., 1998)
391 ± 2 Ma (Chen et al., 1998)
Breccia pipes (Delegate) K-Ar 160-170 Ma (Lovering and
Richards, 1964; White and Chappell,
1989)
Alkali basalt pipes (Monaro)
K- Ar 55-34 Ma (Wellman and
McDougall, 1974b)
Berridale Batholith: I Type granites.
Zircon U-Pb
(SHRIMP)
412.6 ± 4.1 Ma – 436.2 ± 4.7 Ma
(Ickert and Williams, 2011).
(Majority ~417 Ma)
Berridale Batholith: S Type granites. Zircon U-Pb
(SHRIMP)
425.5 ± 4.3 to 435.6 ± 5.1 Ma
(Ickert and Williams, 2011)
(Majority ~ 432 Ma)
Delegate Adamellite pluton (I-type)
(within Berridale Batholith)
Zircon U-Pb
(SHRIMP)
419.2 ± 6 Ma (Ickert and Williams,
2011).
Glenbog Granodiorite (Bega
Batholith)
Zircon U-Pb
(SHRIMP)
412 ± 3 Ma and 414 ± 2 Ma (Chen
and Williams, 1990)
Buckleys Lake Adamellite
(Berridale Batholith)
Zircon U-Pb
(SHRIMP)
415.6 ± 4.4 Ma (Ickert and
Williams, 2011).
Tingaringy Granodiorite
(Berridale Batholith)
Zircon U-Pb
(SHRIMP)
425.5 ± 4.3 (Ickert and Williams,
2011).
Table 15. Summary of geological units of the eastern Lachlan Fold belt in close proximity to the xenolith
samples.
54
6. Discussion
6.1. Origin of xenoliths from the Monaro Volcanic Province
Mafic xenoliths of lower crustal derivation may represent (1) cumulates from mantle
derived magmas (e.g. Rogers and Hawkesworth, 1982), (2) restites following partial
melt extraction (e.g. Rudnick, 1986; Rudnick and Taylor, 1987), (3) crystal cumulates
related to their host basalts (e.g. White, 1966), or (4) a combination of these.
The MVP xenoliths show strong preservation of the original cumulate textures (see
Appendix 1). Such features imply a cumulate origin, however, the metamorphic
mineralogy and granulitic textures of these xenoliths suggest they are not direct igneous
cumulates. Samples may also represent orthocumulates with trapped melt phases
(Arculus et al., 1989), which under granulite facies conditions, would be difficult to
distinguish texturally and without geochemical data. Bearing in mind these observed
textural features, the mineral specific trace element chemistry, whole rock
geochemistry, and zircon U-Pb geochronology are discussed in this section to
distinguish melt and crystallisation phases, and understand the crustal growth history
preserved in these samples.
6.1.1. Evidence from trace element geochemistry
Major element compositions provide supporting evidence for a mafic lower crust
composed of predominantly basaltic material. The trace element compositions are
indicative of gabbroic cumulates, exhibiting large positive Sr anomalies and moderate
positive Eu anomalies (Rogers and Hawkesworth, 1982).
Samples are generally depleted in trace element concentrations relative to average lower
crustal compositions, particularly Th, U, Nd, Hf and Sm. These depletions are
characteristic of the mafic lower crust, produced by differentiation of a basaltic magma,
melt loss from cumulates (Rudnick, 1992), or reflecting, at least in part, a pre-existing
feature of the original magma (Roberts and Ruiz, 1989). While low concentrations of
Rb, Zr, Hf and Nd are characteristic of basaltic rocks, significant depletions in these
elements, along with enrichments in Ba, Sr and Pb (shown in Figure 11) are not typical
of common basaltic melts.
55
These signatures suggest that the MVP samples are more complex than simply
representing crystallised basalts under granulite facies conditions, and attest to the
fractionation and/or partial melting in these xenoliths. Strong Nb and Ta depletions
relative to La (Figure 12), observed in these samples is similar to arc magmas, and
suggest subduction zone magmatism may have influenced the compositions of these
xenoliths. While the exact origin of Nb and Ta depletions in the crust still remain
enigmatic (Hermann and Rubatto, 2009), signatures retained from the partitioning of Nb
and Ta into rutile during subduction of oceanic crust are thought to be preserved in
newly formed continental crust. The enrichment and limited concentration range of Sr
reflects the accumulation of plagioclase, however may also be sourced from processes
such as, subduction and recycling (e.g. Sobolev et al., 2000), additions to the lower
crust by mantle degassing (Korringa and Noble, 1971), or contamination with the host
pipe (e.g. Mitchell and Crocket, 1971).
The smooth REE pattern, slight depletion towards the HREEs and positive Eu anomaly
is suggestive of a cumulate origin (Rogers and Hawkesworth, 1982). The zircon bearing
xenoliths (MVP10436 and MVP10437) are geochemically distinct from the non-zircon
bearing two pyroxene granulites. They are enriched in trace elements, particularly the
REEs and characterised by a negative Eu anomaly, more representative of a partial or
extracted melt (e.g. Rudnick et al., 1986; Rudnick, 1992).
Partition coefficients of trace elements within minerals of naturally occurring melts are
derived from experimental results on basaltic rocks and compared to mineral/whole
rock trace element ratios from these xenoliths. The mineralogy and distinct cumulate
layering in these xenoliths suggest the study samples are not basaltic melts, and
significant differences in comparison to experimental values may reflect their
crystallisation and melt history, the accumulation of specific mineral phases (e.g. Frey
and Prinz, 1978), their crustal origin and tectonic setting. While comparisons are made
between similar rock types, it should be noted that variations in mineralogy may also
affect these values.
The mineral chemistry and concentration ratios of plagioclase show enrichments in Ba,
Sr and Eu, elements considered to be compatible in plagioclase crystallising from a
basaltic melt (Arth, 1976). Samples MVP10436 and MVP10437, illustrating whole rock
geochemical characteristics of a melt fraction, still show these enrichments in
56
plagioclase (Figure 3A and 3B, and 13C), and therefore, may have originally
represented cumulates undergone partial melting. If plagioclase crystallised as an
interstitial melt rather than by crystal accumulation, the mineral/whole rock ratios of
other elements apart from Ba, Sr and Eu, may also be enriched.
Positive concentration ratios of Ni and Cr in clinopyroxene show no enrichment relative
to other trace elements, suggesting clinopyroxene did not form by crystal accumulation
as shown by plagioclase. The greater HREE depletion of clinopyroxene within the
garnet bearing samples suggest the crystallisation or recrystallisation of clinopyroxene
in equilibrium with garnet. The flat HREEs are characteristic of garnet under granulite
conditions (e.g. Rubato, 2002) and provide evidence for sub-solidus re-equilibration
under granulite conditions as suggested by Chen et al., (1998). Together with a
cumulate interpretation for these samples (as indicated by plagioclase), garnet is
understood to have grown during granulite facies metamorphism of a basaltic cumulate.
Rutile is an essential component of geochemical signatures in arc magmas (Foley et al.,
2000), and is considered to be a primary mineral causing fractionation in high field
strength elements (Nb, Ta, Hf, Zr) (Ayers and Eggler, 1995; Brenan et al., 1995b; Ayers
et al., 1997; Adam et al., 1997; Stalder et al., 1998). Rutile in these xenoliths are
significantly enriched in high field strength elements Nb, Hf, Ta, and Zr, and these
elements, particularly Nb and Ta are highly compatible in crystallising rutile (Bennett et
al., 2004). The greater enrichment of these elements indicated by the whole rock
chemistry in sample MVP99-2-12 over MVP99-2-22, suggests MVP99-2-22 has
undergone a greater degree of differentiation than MVP99-2-12 and potentially derived
from a more fractionated arc magma.
6.1.2. Evidence from zircon analysis
6.1.2.1. Textural context and microstructures
Understanding the origin of these xenoliths using U-Pb geochronology of zircon
requires knowledge of how the zircon formed, and essentially, how these grains relate to
the major mineralogy. Before assigning geological significance to U-Pb ages, textural
and microstructural features of the zircon grains are discussed.
The microstructures and morphology of the zircons in the granulite samples are
characteristic of metamorphic zircon (e.g. Kroner et al., 1987). Fewer zircons show a
57
more rounded version of the classical prismatic shape, a common feature of
metamorphic zircons in fluid-rich environments (Corfu et al., 2003). The intergrowth of
zircon, often in contact with ilmenite suggests a relationship between the two minerals.
Exsolution lamellae in ilmenite, consistent with the incipient breakdown of this mineral,
may suggest ilmenite is a possible source of Zr for metamorphic zircon growth in the
granulite facies (e.g. Bingen et al., 2001), although this interpretation was made by
observation of a zircon rim around ilmenite, a feature that is not observed in these
samples. Zircon only occurs in samples MVP10436 and MVP10437. These xenoliths
are both characterised by REE enrichment and have undergone greater degrees of
differentiation to produce the elevated Zr contents required to crystallise zircon.
6.1.2.2. Geochronology
The dated xenoliths at 419.4 ± 6.6 Ma (sample MVP10436) and 402.5 ± 6.3 Ma (sample
MVP10437) are significantly older than the alkali basalt pipes of the Monaro Volcanic
Province (55-34 Ma; Wellman and McDougall, 1974b), and the Delegate breccia pipes
(160-170 Ma; Lovering and Richards, 1964), and therefore unrelated to the host magma.
The zircon ages cannot distinguish between a residual or cumulate origin, however, do
provide strong evidence that samples are not fragments of the host pipe basalts (e.g.
White, 1966).
The two pyroxene granulite (10430/1) from the nearby Delegate breccia pipes produced
ID-TIMS ages of 391 ± 2 Ma and 398 ± 2 Ma by Chen et al., (1998), and are
comparable to the 402.5 ± 6.3 Ma ages from sample MVP10437. The spread of data
along concordia shown by sample MV10437 may be due to intracrystalline Pb loss
and/or the redistribution of Pb, common in high-grade metamorphism (McFarlane et al.,
2005). This would imply that this younger age does not have geological significance, in
which case these data provide little information regarding the xenolith origin. The tight
cluster of concordant ages obtained from zircons in sample MVP10436 on the other
hand, and their age similarity with the late Silurian regional granites (Ickert and
Williams, 2011), suggest that this sample formed during the emplacement of the
Lachlan Fold Belt batholiths. It cannot be ruled out that the zircon grains formed prior
to metamorphism. It is important to note that granulite facies conditions denoted by
these samples exceed the closure temperature for the U-Pb Zircon geochronometer
(Cherniak and Watson, 2001). It is possible that zircons are older than their determined
U-Pb age and represent magmatic zircons which have been isotopically reset by the host
58
pipe volcanism or by a separate magmatic event (e.g. Bomparola, 2007). This is,
however, not supported by the REE signatures and grain morphology which suggest
zircon crystallised under granulite facies conditions.
6.2. Implications for crustal evolution
6.2.1. Relationship with regional granites
The mafic compositions of these xenoliths are broadly complementary to the more
felsic upper crustal granites of the eastern Lachlan Fold Belt (Chappell and White,
1992). Similarly, the positive Eu anomaly in majority of these xenoliths complement the
negative Eu anomaly in the Lachlan granites and the post Archean upper continental
crust in general (Taylor and McLennan, 1995). A positive Eu anomaly estimated for the
Earth’s lower crust is often considered to be complementary to the negative Eu anomaly
established for the Earth’s upper crust (Rudnick and Gao, 2003). This positive Eu
anomaly is, however, too small to satisfy this complementary relationship. The mass
balance discrepancy is either an indication of the limited lower crustal material available
for sampling, a lower crust that is not a direct residue of the upper crust, or some other
undetermined process. The MVP samples provide evidence that a more Eu-rich lower
crust exists, which could also help this mass balance problem.
The Monaro Volcanic Province xenoliths have a discrete zircon population producing a
U-Pb concordia age of 419.4 ± 6.6 Ma. In contrast, the previously dated Delegate
breccia pipe xenoliths (Chen at al., 1998) showed no age relationship with any of the
late Silurian regional granites. The U-Pb zircon age from sample MVP10436 reported in
this study, delivers the first geochronological evidence linking the unexposed granulitic
lower crust to the upper crustal granites of the Lachlan Fold Belt. This age association,
along with the trace element signatures exhibited by these xenoliths, implies that crustal
growth is a product of subduction related magmatism, and has significant implications
for understanding crustal processes at inaccessible depths. These may include the timing
of large scale basaltic magmatism and deep fractionation processes, which may provide
important information for the production of the granitic upper crust.
The significance of the younger 402.5 ± 6.3 Ma age can only be assessed by further
isotope analysis, however, if ages were related to separate magmatic events, this would
provide evidence that basaltic magmatism and underplating was episodic, and continued
after the formation of the late Silurian granites of the eastern Lachlan Fold Belt. Such a
59
process is considered imperative for the strengthening and stabilisation of the
continental crust (Rudnick, 1995).
6.2.2. Implications of the Lachlan Fold Belt/Tasmanides evolution - evidence from
xenoliths
The Lachlan Fold Belt has been the focus of extensive geophysical, tectonic and
petrological research (e.g. Collins and Vernon, 1992; Gray and Cull, 1992; Collins,
1998). Its evolution is important in understanding the development of the larger Terra
Australis Orogen, a series of orogenic belts recording the formation of crust along the
eastern margin of Gondwana during the Palaeozoic (Glen, 2005). Information about the
lower crust below this region is limited to xenoliths and seismic profiling, making a
complete understanding of crust-forming processes in this orogen, and particularly the
processes of granitic magma generation, elusive.
During the Silurian to Mid-Devonian, the southern Tasmanides developed a large back-
arc basin as part of the Tabberabberan cycle, and underwent lithospheric extension
caused by roll back of the southern proto-Pacific plate (Glen, 2005). The distribution of
the I-type granites over the S-type in the eastern Lachlan Fold Belt is considered to be a
result of this thinning and extension of the back-arc, following S-type granite plutonism
(Collins and Richards, 2008). Figure 19 shows a model for the S and I-type granite
formation in a subduction zone setting by Collins and Richards, (2008). In the context
of this study, these figures highlight the relationship between basaltic intra/under
plating, the mafic granulitic lower crust and the formation of the I-type granites during
back-arc extension. Following this model, xenoliths representing fragments of the lower
crust, and produced by basaltic magmatic cumulates, show a closer age relationship
with the I-type granites as opposed to the S-type granites shown in Table 15.
The xenoliths of this study represent highly equilibrated granulite textures, and as a
result, evidence from any deformation features (i.e. foliation or deformation
microstructures) which could point towards the wider tectonic setting are absent.
However, complex disequilibrium textures and multiple coronae textures identified in
Part 1 of this study (Appendix 1), provided evidence for isobaric cooling and a dynamic
lower crustal environment.
60
The trace element compositions of these xenoliths are depleted in radioactive heat
producing elements, as expected for the deep crust beneath the I-type granites, and
lower crustal material in general (Sawka and Chappell, 1986; Collins and Hobbs, 2001).
Furthermore, xenoliths show geochemical signatures similar to those of arc basalts,
suggesting the origin of the source magma may be associated with a subduction setting
rather than an intraplate oceanic magma protolith (Griffin and O’Reilly, 1986). The
xenolith geochemistry and age association with the I-type granites provide a significant
relationship for understanding the evolution of the regional granites. The I-type granites
also have a subduction related chemistry, and are understood to be derived from mid to
deep crustal sources as a result of underplating by mafic magmas during extension
(Chappell and White, 1992). Both the geochemical and geochronological data from
these xenoliths provide evidence supporting the proposed model of I-type granite
formation by Collins and Richards, (2008), and supports most crust forming
mechanisms consisting of a mafic lower crust/mantle composition and subduction
component (e.g. Powell, 1983).
61
Figure 19. Tectonic diagram from
Collins and Richards, (2008) showing
how the mafic lower crust might form
from crustal-scale magmatic events.
Xenoliths represent samples from this
basaltic granulitic lower crust
underneath the exposed I-type
granites.
62
6.2.3. Implications for general crust forming processes
The preserved cumulate textures, geochemistry and geochronology collectively point
towards a cumulate origin of these xenoliths, subsequently recrystallised under granulite
facies conditions and significantly different from their host basalt. The basaltic
compositions of the enclaves provide direct evidence for the large amounts of mafic
material beneath eastern Australia (e.g. Chen et al., 1998), and a lower crust consisting
of a granulite and eclogite mineralogy (Foley et al., 2002).These basaltic cumulates
provide key evidence for the addition of new crustal material by magmatic underplating,
typical of subduction zones and intraplate settings during the Palaeozoic (Rudnick et al.,
1986).
These xenoliths represent samples in which the protolith may have been an igneous
cumulate, but after crystallisation they were metamorphosed to granulite facies. It is
possible that this process of cumulate formation was related to granite generation, as
represented by the Collins and Richard model (Figure 19). The results from this study
not only constrained an age of metamorphism as suggested by Chen et al., (1998), but
were able to relate this age to the regional granites, providing both geochemical and
chronological evidence for a residual and granulitic lower crust during batholith
emplacement (Ickert and Williams, 2001).
63
6.3. Conclusions and future research
Conclusions of this study can be summarised as follows:
1. The study samples are basaltic cumulates, formed by the accumulation of
plagioclase during basaltic underplating that subsequently underwent granulite
facies metamorphism.
2. Samples are depleted in heat producing elements (Th, U) characteristic of a
residual lower crust, with some showing a strong REE enrichment and negative
Eu anomaly. These compositions are suggestive of fractionated magma, perhaps
complementary to the depleted granulites.
3. The least fractionated samples on the other hand show a positive Eu anomaly
characteristic of many lower crustal xenoliths, although the presence of samples
with a negative Eu anomaly suggest Eu signatures of the bulk lower crust may
be influenced by sampling bias, or a bulk lower crust that is not a residue
following the extraction of the upper crust.
4. Significant depletions in Nb and Ta suggest subduction processes have
influenced lower crustal compositions, indicating a magmatic provenance
similar to arc basalts beneath eastern Australia.
5. Ion microprobe analysis of zircon from two Monaro Volcanic Province samples
yields a U-Pb concordia age of 419.4 ± 6.6 Ma age contemporaneous with the
emplacement of the Late Silurian I-type granites within the eastern Lachlan Fold
Belt. A second age group was derived from a scatter of data along concordia,
however its significance remains ambiguous.
6. This age relationship provides new evidence for a genetic link between the mafic
and granulitic lower crust, and the more felsic upper crustal granites in eastern
Australia. It further signifies that arc magmatism and magma differentiation are
key processes in the growth and evolution of the continental crust during the
Palaeozoic.
Samples of the granulitic lower crust, in the form of xenoliths provide essential
information regarding the nature and composition of the inaccessible lower crust. The
age association between the regional granites and xenolith samples provide an excellent
opportunity to study isotopic systematics between the upper and lower continental crust.
Future research will focus on S and C isotope signatures in scapolite, along with O and
Lu-Hf isotope analysis in zircon. This may determine if zircon did in fact form during
metamorphism or is magmatic derived, and understand the distribution of stable
64
isotopes at deep crustal levels, and their relationship to global isotope reservoirs. These
studies will help reveal critical processes for the evolution of the granitic upper crust
preserved in such xenoliths.
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35.
73
APPENDIX 1 -SUMMARY OF MINERALOGY AND HAND SAMPLE
DESCRIPTIONS (From Part 1 – 2013 thesis)
Appendix Figure 1 Exposed cut surface (on left) and whole rock (on right) representing each rock type.
(A) and (B) two-pyroxene granulite (MVP10438), (C) and (D) garnet granulite (MVP99-2-12), (D) and
(E) Eclogite (DEL2-10434), (F) and (G) reaction intermediate (MVP10435).
B
H
F
D C
E
G
A
74
Appendix Figure 2 Optical microscope and BSE images. (A) and (B) are the two–pyroxene granulite in
PPL and XPL, (C) and (D) are the two-pyroxene granulite with scapolite in PPL and XPL, (E) and (F)
rutile and Cpx in PPL and BSE imaging, (F) and (G) show the garnet granulite in PPL and BSE imaging.
A B
G
F E
D C
H
75
Appendix Figure 3 (A), (B) and (C) Scapolite in the garnet granulite in PPL, XPL and BSE imaging, (D)
Showing scapolite in garnet granulite which is also in contact with Pl, (E) and (F) show the thick isotropic
rims around garnet of the fassaite eclogite in PPL and BSE imaging.
A B
F E
C D
76
Appendix Figure 4 Image (A) displays coronas of Opx rimmed by Cpx, rimmed by Grt in contact with
Pl. Image (B) shows similar coronas but with Grt exsolution lamellae in the centre grain. In (C) Grt rims
in image (A) at higher magnification under BSE imaging. Image (D) shows the instability between calcic
Pl and Cpx. On the right Cpx is rimmed by sodic Pl and on the development of the Grt rim. In (E) and (F)
Spl symplectite occurs as intergrowths with the Grt rims, the darker grain in the BSE image is the altered
sodic Pl. (G) and (H) show larger grains of Spl rimmed by Grt and its common co-existence with
ilmenite.
A
H G
F E
D C
B
77
Two-pyroxene granulites
Major mineral assemblage: clinopyroxene + orthopyroxene + plagioclase.
The hand specimens are 6x12cm in diameter and shows compositional banding,
characteristic of cumulate layering (Figures 1a & 1b).
Sample MVP10438 contained scapolite (<2%) as part of its mineral assemblage, DEL99-2-
01 was lacking in scapolite.
The mineralogy of this rock type is variable, comprising of approximately 15% pale brown
to apple green clinopyroxene, 30% pale brown to green and distinctly pleochroic
orthopyroxene and 60% plagioclase.
Scapolite occurs as part of polygonal granular assemblages with pyroxenes. The general
appearance of scapolite is distinguished by its high blue to green birefringence (Figure 2c &
2d).
Accessory minerals are magnetite and rutile. Rutile is bronze under optical microscopy and
characterised by a thin alteration to ilmenite around its edges and as thin plates throughout
the rutile grain (Figure 2e & 2f).
Garnet granulites
Major mineral assemblage: garnet + clinopyroxene + plagioclase ± scapolite ± rutile.
Scapolite and non-scapolite
The hand specimen is 4-5cm in diameter and is grey in appearance (Figure 1c & 1d).
Garnet appears orange/red and is easily observed on the outer weathered surface.
Mineralogy is also variable with clinopyroxene approximately 40%, plagioclase 30% and
garnet 25-30%. Medium to coarse grained similar to the two-pyroxene granulite (0.5-2mm).
In contrast to the two-pyroxene granulite, this assemblage lacks orthopyroxene and contains
garnet (Figure 2g & 2h).
Garnet appears pale brown/pink in thin section and contains a thin alteration around its
edges. The appearance of clinopyroxene and plagioclase under thin section are similar to
the two-pyroxene granulite.
Often scapolite shows high birefringence under cross polarised light and distinct alteration
to plagioclase around its rim. Alteration exists around the scapolite rim but remains within
its grain boundary, suggesting it is not a result of a reaction with the co-existing minerals
Eclogite
Major mineral assemblage: garnet + clinopyroxene with accessory rutile, with rutile
showing alteration to ilmenite around its rim.
78
Minor mounts of green spinel are present in some of the grain alteration around
clinopyroxene.
The original sample is roughly 10cm in size but appears to be broken from an originally
larger sample (Figure 1f).
The hand specimen shows a coarser grainsize than the other samples, ranging from 1-5mm
(Figure 1e).
Hand sample is dark grey reflecting the lack of plagioclase.
Under thin section, grains appear highly fractured with secondary alteration contained in
these cracks and along edges of the grains. Garnet contains a dark isotropic rim around its
edges (Figure 3e and 3f), interpreted previously as kelyphite, an isochemical breakdown
product of garnet (Keankeo et al., 2000). While present in all garnet grains, this rim is
thickest in the eclogite sample
Only a few garnet grains show the original unaltered, inclusion-free mineral in the centre.
Reaction intermediate
The rock is distinguished from the other samples in displaying several complex reaction
textures.
Sample MVP10435 is a coarse grained rock (average grainsize 1.5mm) and initially appear
to consisting of plagioclase and pyroxene. In hand specimen, grain boundaries are indistinct
compared to previous rock types, reflecting the disequilibrium textures later observed under
optical microscopy.
Sample shows multiple coronae (Figure 4a) with pale brown orthopyroxene in the centre
rimmed by green clinopyroxene that is, in turn, overgrown by garnet. This thin garnet rim is
also in contact with plagioclase, and separates clinopyroxene and plagioclase throughout the
entire sample. Ilmenite is also present in this sample surrounded by a similar garnet rim.
The reaction texture shown in Figure 4b shows a similar texture to that in Figure 4a, except
inclusions of brown, tabular shaped garnet grains occur within the orthopyroxene.
These grains are <50µm in thickness and appear to represent garnet exsolution lamellae, a
product of isobaric cooling (e.g. Becker 1997).
Figure 4c shows a moat of garnet around the central clinopyroxene grain, all which is
surrounded by plagioclase.
Clinopyroxene and calcic plagioclase are never in direct contact.
The boundary between these minerals is separated by a rim of garnet, and in one instance it
is separated by an indistinct rim/halo or sodic plagioclase, as shown in Figure 4d. The grain
on the right contains a rim of sodic plagioclase separating clinopyroxene and calcic
plagioclase. The left grain also shows this rim, but with garnet beginning to develop
79
suggesting that the formation of the sodic plagioclase is associated with growth of the
garnet rim. Both appear to be products of a reaction involving clinopyroxene and calcic
plagioclase.
Another textural feature of this sample is symplectite intergrowth between garnet and green
(hercynite) spinel (Figure 4e & 4f). This texture appears to be common in garnet rims
surrounding ilmenite and altered sodic plagioclase grains, and does not occur in garnet
rimming orthopyroxene and clinopyroxene. Spinel occurs in two forms, as symplectite
intergrowths within garnet and as larger grains rimmed by garnet (Figure 4g).While the
larger grain appears almost opaque under optical microscopy, the spinel symplectite is dark
green in colour. The opaque appearance may reflect fine intergrowth with ilmenite (Figure
4h) as evident from BSE imaging.
80
APPENDIX 2 – Original EMPA DATA (From Part 1- 2013 thesis)
SAM
PLE
DEL9
9-2-
01
Spot
N°
12
34
56
78
910
1112
1314
1516
1718
1920
2122
2324
25
MIN
ERAL
Opx
Opx
Cpx
PlPl
Opx
Opx
Cpx
Cpx
PlPl
Opx
Opx
Opx
PlPL
Opx
Cpx
PlCp
xCp
xO
pxO
pxPl
Pl
SiO
2 51
.83
51.8
149
.76
45.8
645
.68
51.6
751
.48
49.5
549
.45
45.5
045
.76
51.6
651
.96
51.7
445
.96
46.1
951
.88
49.7
045
.37
48.6
349
.13
51.3
551
.24
44.1
544
.47
TiO
2 0.
070.
080.
71b.
d.b.
d.0.
070.
080.
730.
66b.
d.b.
d.0.
070.
050.
05b.
d.b.
d.0.
070.
74b.
d.0.
770.
740.
050.
06b.
d.b.
d.
Al2O
3 5.
655.
566.
8633
.69
33.5
95.
395.
586.
776.
6833
.89
33.6
85.
585.
475.
4433
.62
33.8
25.
416.
7133
.81
6.81
6.79
5.61
5.41
33.1
133
.63
Cr2O
3 b.
d.0.
070.
15b.
d.b.
d.0.
060.
110.
190.
12b.
d.b.
d.b.
d.b.
d.0.
11b.
d.b.
d.0.
080.
18b.
d.0.
140.
160.
12b.
d.b.
d.b.
d.
FeO
15
.01
14.5
45.
440.
28b.
d.15
.06
14.6
55.
735.
31b.
d.0.
2014
.35
14.1
714
.02
b.d.
0.29
14.5
55.
45b.
d.6.
155.
7013
.92
13.9
00.
41b.
d.
MnO
0.
320.
230.
11b.
d.b.
d.0.
380.
300.
110.
14b.
d.b.
d.0.
270.
280.
29b.
d.b.
d.0.
250.
13b.
d.0.
160.
180.
340.
27b.
d.b.
d.
MgO
26
.52
26.5
213
.01
b.d.
b.d.
26.6
026
.59
12.9
213
.09
b.d.
b.d.
26.4
926
.65
26.4
3b.
d.b.
d.26
.73
13.3
1b.
d.13
.16
13.2
826
.55
26.5
3b.
d.b.
d.
CaO
0.
270.
1722
.63
17.7
017
.97
0.47
0.54
22.9
122
.45
18.2
118
.23
0.47
0.26
0.28
17.6
417
.76
0.55
22.7
717
.71
22.4
022
.72
0.38
b.d.
17.4
818
.25
Na2O
0.
040.
020.
801.
631.
520.
03b.
d.0.
850.
831.
361.
480.
020.
03b.
d.1.
611.
62b.
d.0.
801.
440.
810.
820.
030.
041.
501.
36
K2O
b.
d.b.
d.b.
d.0.
020.
04b.
d.b.
d.b.
d.0.
010.
020.
03b.
d.0.
01b.
d.0.
030.
030.
02b.
d.0.
010.
01b.
d.0.
010.
010.
040.
03
P2O
5 b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.
SO
3 b.
d.b.
d.b.
d.b.
d.0.
02b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.0.
04b.
d.
Cl
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
0.01
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
0.01
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
0.05
0.01
TOTA
L99
.72
99.0
099
.47
99.1
998
.81
99.7
399
.32
99.7
598
.76
98.9
799
.39
98.9
198
.88
98.3
798
.86
99.7
299
.54
99.8
198
.35
99.0
599
.52
98.3
697
.45
96.7
797
.76
Si
1.86
81.
875
1.84
32.
132
2.13
01.
866
1.86
31.
836
1.84
42.
119
2.12
51.
872
1.88
01.
882
2.14
02.
136
1.87
01.
838
2.12
41.
819
1.82
61.
870
1.87
92.
108
2.10
1
Ti
0.00
20.
002
0.02
00.
000
0.00
00.
002
0.00
20.
020
0.01
90.
000
0.00
00.
002
0.00
10.
001
0.00
00.
000
0.00
20.
021
0.00
00.
022
0.02
10.
001
0.00
20.
000
0.00
0
Al
0.24
00.
237
0.29
91.
846
1.84
60.
229
0.23
80.
295
0.29
41.
860
1.84
40.
238
0.23
30.
233
1.84
51.
843
0.23
00.
292
1.86
50.
301
0.29
80.
241
0.23
41.
864
1.87
3
Cr
0.00
00.
002
0.00
50.
000
0.00
00.
002
0.00
30.
006
0.00
40.
000
0.00
00.
001
0.00
10.
003
0.00
00.
000
0.00
20.
005
0.00
00.
004
0.00
50.
003
0.00
10.
000
0.00
1
Fe
0.45
30.
440
0.16
80.
011
0.00
00.
455
0.44
30.
177
0.16
60.
001
0.00
80.
435
0.42
90.
426
0.00
00.
011
0.43
90.
169
0.00
00.
192
0.17
70.
424
0.42
60.
016
0.00
0
Mn
0.01
00.
007
0.00
30.
000
0.00
00.
012
0.00
90.
003
0.00
50.
000
0.00
10.
008
0.00
90.
009
0.00
00.
000
0.00
80.
004
0.00
00.
005
0.00
60.
010
0.00
80.
001
0.00
1
Mg
1.42
51.
431
0.71
90.
000
0.00
01.
432
1.43
40.
714
0.72
80.
000
0.00
01.
431
1.43
71.
433
0.00
00.
000
1.43
70.
734
0.00
00.
734
0.73
61.
441
1.45
00.
000
0.00
0
Ca
0.01
00.
007
0.89
80.
882
0.89
80.
018
0.02
10.
910
0.89
70.
908
0.90
70.
018
0.01
00.
011
0.88
00.
880
0.02
10.
902
0.88
80.
898
0.90
50.
015
0.00
00.
894
0.92
4
Na
0.00
30.
002
0.05
80.
147
0.13
80.
002
0.00
10.
061
0.06
00.
123
0.13
40.
002
0.00
20.
001
0.14
60.
145
0.00
10.
057
0.13
10.
059
0.05
90.
002
0.00
30.
139
0.12
5
K 0.
000
0.00
00.
000
0.00
10.
002
0.00
00.
000
0.00
00.
000
0.00
10.
002
0.00
00.
001
0.00
00.
002
0.00
20.
001
0.00
00.
001
0.00
10.
000
0.00
10.
001
0.00
20.
002
P 0.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
10.
001
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
10.
000
S 0.
000
0.00
00.
000
0.00
00.
001
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
10.
000
Cl
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
10.
000
0.00
00.
000
0.00
00.
000
0.00
00.
001
0.00
10.
000
0.00
00.
000
0.00
00.
000
0.00
10.
004
0.00
1
TOTA
L4.
011
4.00
44.
014
5.01
95.
015
4.01
84.
015
4.02
34.
018
5.01
35.
021
4.00
74.
003
4.00
05.
012
5.01
74.
012
4.02
25.
009
4.03
54.
032
4.00
84.
004
5.03
15.
027
NOX
66
68
86
66
68
86
66
88
66
86
66
68
8
Si C
DL99
0.01
1485
0.01
1934
0.01
015
0.01
2215
0.01
1634
0.01
3626
0.01
4094
0.01
1893
0.00
9323
0.01
2903
0.01
0426
0.00
9079
0.01
2211
0.01
4267
0.01
1916
0.01
1031
0.01
1519
0.01
0891
0.00
9229
0.00
9712
0.01
0955
0.00
9235
0.00
6401
0.01
062
0.01
2827
Ti C
DL99
0.01
9648
0.01
885
0.02
0062
0.01
8666
0.01
9803
0.01
9235
0.01
8802
0.01
984
0.02
0103
0.01
9333
0.01
9114
0.01
9397
0.01
9436
0.01
951
0.02
0007
0.01
9173
0.01
8997
0.01
9732
0.01
9038
0.02
0294
0.02
0157
0.01
9372
0.01
9404
0.01
9464
0.01
9445
Al C
DL99
0.00
9638
0.00
942
0.00
9276
0.01
0419
0.01
0259
0.00
9584
0.00
9426
0.00
9102
0.00
8957
0.01
050.
0102
960.
0095
380.
0095
860.
0095
940.
0099
940.
0101
490.
0094
640.
0093
070.
0102
20.
0090
010.
0091
110.
0096
980.
0095
0.01
0031
0.01
0113
Cr C
DL99
0.04
0065
0.03
9561
0.03
6802
0.03
7541
0.03
6799
0.03
9222
0.03
6415
0.03
9292
0.04
5506
0.04
1712
0.03
7925
0.03
9202
0.03
6547
0.03
3795
0.03
742
0.03
6943
0.03
5881
0.03
7845
0.04
216
0.03
5779
0.03
7689
0.03
888
0.03
792
0.04
0137
0.03
9691
Fe C
DL99
0.01
4257
0.03
7158
0.04
5626
0.01
3632
0.06
1365
0.00
5484
0.02
634
0.04
3607
0.05
6167
0.04
680.
0222
50.
0562
070.
0546
430.
0654
130.
0529
610
00.
0508
770.
0603
10
0.02
0915
0.06
9701
0.05
0177
00.
0675
54
Mn
CDL9
90.
0366
220.
0385
740.
0392
210.
0374
20.
0405
620.
0331
690.
0375
150.
0383
420.
0372
820.
0360
690.
0341
860.
0366
50.
0388
180.
0317
790.
0397
820.
0383
090.
0400
030.
0361
80.
0367
850.
0374
550.
0372
780.
0371
480.
0377
750.
0351
930.
0349
59
Mg
CDL9
90.
0155
140.
0144
340.
0144
240.
0114
240.
0132
210.
0139
370.
0129
380.
0171
970.
0127
520.
0107
480.
0089
040.
0128
0.01
5586
0.01
3299
0.01
010.
0123
750.
0150
960.
0106
460.
0133
930.
0133
720.
0108
720.
0140
470.
0152
60.
0103
890.
0119
21
Ca C
DL99
0.01
1111
0.01
3118
0.00
906
0.01
1751
0.00
3956
0.00
5281
00
0.01
0362
0.00
5667
00.
0053
420.
0109
330.
0101
090.
0117
570.
0087
760
0.00
4998
0.01
5576
0.01
362
0.00
4676
0.00
7723
0.01
6892
0.01
0606
0.00
4571
Na C
DL99
0.01
3425
0.01
3843
0.01
3746
0.01
3586
0.01
4017
0.01
2572
0.01
3887
0.01
3704
0.01
3909
0.01
3381
0.01
2919
0.01
3251
0.01
3762
0.01
4341
0.01
3153
0.01
3567
0.01
4715
0.01
4727
0.01
2599
0.01
4045
0.01
481
0.01
4143
0.01
3661
0.01
3592
0.01
4389
K C
DL99
0.00
8386
0.00
8305
0.00
8027
0.00
792
0.00
7591
0.00
8058
0.00
8069
0.00
7935
0.00
8067
0.00
7903
0.00
7831
0.00
818
0.00
7998
0.00
8117
0.00
7826
0.00
7698
0.00
8158
0.00
8291
0.00
8019
0.00
7822
0.00
8148
0.00
8069
0.00
8362
0.00
7916
0.00
769
P C
DL99
0.01
1866
0.01
3124
0.01
1489
0.01
1691
0.01
1901
0.01
2763
0.01
2101
0.01
0774
0.01
0788
0.01
2124
0.01
0338
0.01
1385
0.01
3765
0.01
2009
0.01
2257
0.01
1698
0.01
163
0.01
2765
0.01
2898
0.01
2125
0.01
1701
0.01
1651
0.01
1536
0.01
0357
0.01
1682
S C
DL99
0.00
814
0.00
7559
0.00
7874
0.00
796
0.00
7761
0.00
7554
0.00
8037
0.00
7937
0.00
7456
0.00
7694
0.00
8202
0.00
8289
0.00
8453
0.00
7889
0.00
7976
0.00
7994
0.00
7857
0.00
8125
0.00
8143
0.00
775
0.00
7672
0.00
8056
0.00
7771
0.00
7019
0.00
7791
Cl C
DL99
0.01
121
0.00
9926
0.01
1053
0.00
967
0.01
0388
0.01
0856
0.01
0957
0.01
0373
0.01
0211
0.00
980.
0100
290.
0107
850.
0108
030.
0104
460.
0102
720.
0089
870.
0105
650.
0105
120.
0102
290.
0110
750.
0112
830.
0111
510.
0112
40.
0099
570.
0094
27
81
SAM
PLE
MV
P9
9-2
-22
SPO
T N
°1
23
45
67
89
10
11
12
13
14
15
16
17
18
19
MIN
ER
AL
Grt
Grt
Grt
Grt
(Rim
)G
rt(R
im)
Cp
xC
px
Pl
Pl
Grt
Grt
Grt
Cp
xP
lP
lG
rtC
px
Grt
Pl
SiO
2
10
.92
11
.05
39
.08
35
.71
44
.93
49
.13
50
.19
59
.28
62
.08
39
.28
39
.16
50
.06
50
.12
61
.99
62
.62
50
.02
49
.96
38
.88
60
.67
TiO
2
0.1
10
.11
0.2
40
.25
0.2
50
.91
0.9
3b
.d.
b.d
.0
.20
0.2
00
.99
0.8
9b
.d.
b.d
.0
.89
0.9
40
.19
b.d
.
Al2
O3
8
.43
8.5
02
1.3
81
2.3
21
8.4
07
.09
7.2
12
1.6
52
2.9
32
1.3
92
1.0
77
.21
7.1
52
2.9
02
3.0
07
.15
7.0
72
0.7
62
2.4
1
Cr2
O3
0
.07
b.d
.b
.d.
0.1
00
.09
b.d
.0
.12
b.d
.b
.d.
0.0
90
.11
0.0
70
.13
b.d
.b
.d.
0.0
60
.08
0.1
1b
.d.
Fe
O
14
.28
13
.42
21
.27
27
.01
15
.63
10
.51
9.7
70
.27
0.2
72
0.8
72
1.3
11
0.3
01
0.4
80
.44
0.1
11
0.5
99
.97
20
.88
0.4
4
Mn
O
0.3
00
.34
0.5
30
.64
0.4
10
.17
0.0
8b
.d.
b.d
.0
.49
0.5
00
.13
0.1
00
.04
b.d
.0
.11
0.1
20
.55
b.d
.
MgO
5
.51
5.4
21
0.5
21
2.5
38
.87
10
.57
10
.83
0.0
3b
.d.
10
.50
10
.43
10
.70
10
.87
0.0
2b
.d.
10
.65
10
.71
10
.41
0.0
6
Ca
O
3.3
73
.02
5.6
51
.43
7.5
71
6.6
71
6.8
91
.41
4.8
55
.99
6.0
41
7.1
11
7.3
04
.70
4.8
41
6.7
81
7.1
95
.81
4.8
3
Na
2O
b
.d.
b.d
.b
.d.
0.1
40
.44
2.2
32
.31
6.2
48
.18
0.0
20
.04
2.3
42
.25
8.3
28
.27
2.1
62
.22
0.0
48
.15
K2
O
b.d
.b
.d.
b.d
.0
.05
0.4
20
.02
b.d
.7
.21
0.5
6b
.d.
b.d
.0
.01
b.d
.0
.54
0.5
3b
.d.
0.0
1b
.d.
0.5
5
P2
O5
0
.04
b.d
.0
.04
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.0
.03
b.d
.0
.04
b.d
.b
.d.
b.d
.b
.d.
0.0
4b
.d.
SO
3
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.
Cl
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
0.0
1b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
0.0
2
TO
TA
L4
3.0
44
1.8
69
8.7
29
0.1
89
7.0
19
7.3
29
8.3
29
6.1
09
8.8
89
8.8
39
8.8
89
8.9
29
9.3
39
8.9
69
9.3
79
8.4
29
8.2
69
7.6
89
7.1
4
Si
4.2
89
4.4
01
5.9
94
6.2
44
6.8
10
1.8
78
1.8
89
2.8
00
2.7
83
6.0
13
6.0
10
1.8
80
1.8
77
2.7
79
2.7
88
1.8
87
1.8
86
6.0
32
2.7
74
Ti
0.0
34
0.0
34
0.0
28
0.0
33
0.0
28
0.0
26
0.0
26
0.0
00
0.0
00
0.0
23
0.0
23
0.0
28
0.0
25
0.0
01
0.0
01
0.0
25
0.0
27
0.0
23
0.0
00
Al
3.9
03
3.9
91
3.8
66
2.5
39
3.2
86
0.3
20
0.3
20
1.2
06
1.2
12
3.8
59
3.8
11
0.3
19
0.3
16
1.2
10
1.2
07
0.3
18
0.3
14
3.7
96
1.2
08
Cr
0.0
22
0.0
14
0.0
06
0.0
14
0.0
11
0.0
00
0.0
04
0.0
00
0.0
00
0.0
11
0.0
13
0.0
02
0.0
04
0.0
01
0.0
00
0.0
02
0.0
03
0.0
14
0.0
01
Fe
4.6
88
4.4
72
2.7
29
3.9
50
1.9
81
0.3
36
0.3
08
0.0
11
0.0
10
2.6
72
2.7
35
0.3
24
0.3
28
0.0
16
0.0
04
0.3
34
0.3
15
2.7
09
0.0
17
Mn
0
.10
00
.11
30
.06
90
.09
50
.05
30
.00
50
.00
20
.00
00
.00
00
.06
30
.06
40
.00
40
.00
30
.00
20
.00
10
.00
40
.00
40
.07
20
.00
1
Mg
3.2
25
3.2
18
2.4
06
3.2
68
2.0
04
0.6
02
0.6
08
0.0
02
0.0
00
2.3
95
2.3
85
0.5
99
0.6
07
0.0
01
0.0
00
0.5
99
0.6
03
2.4
08
0.0
04
Ca
1
.41
91
.29
10
.92
80
.26
81
.22
90
.68
30
.68
10
.07
10
.23
30
.98
20
.99
40
.68
80
.69
40
.22
60
.23
10
.67
80
.69
50
.96
70
.23
7
Na
0
.00
30
.01
50
.00
50
.04
60
.13
00
.16
60
.16
90
.57
20
.71
10
.00
60
.01
20
.17
00
.16
30
.72
30
.71
40
.15
80
.16
20
.01
20
.72
3
K
0.0
00
0.0
00
0.0
00
0.0
12
0.0
82
0.0
01
0.0
00
0.4
35
0.0
32
0.0
00
0.0
00
0.0
00
0.0
00
0.0
31
0.0
30
0.0
00
0.0
01
0.0
00
0.0
32
P
0.0
14
0.0
08
0.0
05
0.0
00
0.0
02
0.0
00
0.0
00
0.0
01
0.0
01
0.0
03
0.0
04
0.0
00
0.0
01
0.0
01
0.0
01
0.0
01
0.0
00
0.0
05
0.0
01
S 0
.00
00
.00
00
.00
10
.00
20
.00
00
.00
00
.00
00
.00
00
.00
00
.00
00
.00
10
.00
00
.00
00
.00
00
.00
00
.00
00
.00
00
.00
00
.00
0
Cl
0.0
00
0.0
03
0.0
00
0.0
00
0.0
00
0.0
01
0.0
00
0.0
00
0.0
01
0.0
02
0.0
01
0.0
00
0.0
00
0.0
00
0.0
00
0.0
01
0.0
00
0.0
00
0.0
01
TO
TA
L1
7.6
96
17
.56
01
6.0
36
16
.47
11
5.6
15
4.0
19
4.0
07
5.0
98
4.9
83
16
.03
01
6.0
54
4.0
16
4.0
18
4.9
91
4.9
78
4.0
06
4.0
09
16
.03
84
.99
9
NO
X2
42
42
42
42
46
68
82
42
46
68
86
62
48
Si C
DL9
90
.01
54
01
0.0
13
90
.01
25
17
0.0
11
87
30
.00
89
93
0.0
07
21
10
.00
90
01
0.0
10
91
70
.01
33
55
0.0
08
38
20
.01
05
32
0.0
07
54
70
.01
06
42
0.0
09
82
0.0
08
98
70
.00
85
32
0.0
10
07
70
.00
87
95
0.0
06
78
Ti C
DL9
90
.01
95
57
0.0
19
85
10
.01
95
58
0.0
19
00
70
.01
97
66
0.0
20
04
90
.02
01
02
0.0
18
62
60
.01
91
29
0.0
20
36
90
.01
97
67
0.0
19
06
80
.02
07
62
0.0
18
70
60
.01
81
79
0.0
20
34
50
.01
95
69
0.0
19
94
90
.01
91
51
Al C
DL9
90
.01
11
86
0.0
11
19
0.0
10
51
10
.00
99
73
0.0
09
93
60
.00
92
95
0.0
09
31
50
.00
92
90
.00
96
01
0.0
10
41
90
.01
03
60
.00
90
63
0.0
09
28
60
.00
96
38
0.0
10
01
10
.00
93
77
0.0
09
35
60
.01
07
65
0.0
09
55
3
Cr
CD
L99
0.0
32
66
20
.03
44
40
.03
74
06
0.0
37
54
80
.03
56
51
0.0
41
57
40
.03
80
33
0.0
36
0.0
36
72
40
.04
04
46
0.0
39
68
30
.04
07
65
0.0
37
60
60
.03
54
61
0.0
39
40
30
.03
68
43
0.0
35
65
80
.03
41
17
0.0
34
26
9
Fe C
DL9
90
0.0
75
81
60
.03
70
08
0.0
52
60
90
0.0
23
54
30
.06
92
67
0.0
13
91
80
.02
38
39
0.0
58
35
50
.02
67
26
0.0
49
64
80
.02
30
51
00
.04
07
49
00
.05
32
92
0.0
65
00
10
Mn
CD
L99
0.0
36
09
70
.04
02
99
0.0
39
74
50
.03
65
33
0.0
35
41
90
.03
68
48
0.0
38
58
60
.03
46
60
.03
51
99
0.0
38
40
40
.03
62
47
0.0
37
31
90
.03
48
11
0.0
32
25
0.0
35
45
70
.04
18
08
0.0
39
44
60
.03
79
59
0.0
37
68
Mg
CD
L99
0.0
17
98
70
.02
05
95
0.0
13
16
30
.00
83
17
0.0
08
08
40
.01
53
29
0.0
09
92
20
.00
77
47
0.0
09
49
50
.01
23
01
0.0
11
34
60
.01
37
60
.01
18
37
0.0
08
39
0.0
10
92
10
.01
59
69
0.0
14
85
90
.01
40
62
0.0
07
25
4
Ca
CD
L99
0.0
07
82
30
.01
44
73
0.0
15
59
70
.00
50
77
0.0
05
55
70
.01
18
91
0.0
12
87
70
.01
71
17
0.0
11
84
90
.00
94
43
0.0
08
42
70
.00
94
12
0.0
05
33
20
.01
45
40
.01
05
59
0.0
11
56
70
0.0
12
28
70
.01
23
83
Na
CD
L99
0.0
17
08
40
.01
59
09
0.0
16
12
10
.01
62
99
0.0
13
80
.01
61
58
0.0
14
34
0.0
15
68
60
.01
61
71
0.0
15
33
80
.01
41
40
.01
48
74
0.0
16
26
80
.01
51
54
0.0
16
56
60
.01
63
54
0.0
14
59
50
.01
44
44
0.0
15
89
1
K C
DL9
90
.00
84
99
0.0
08
45
60
.00
85
22
0.0
08
30
40
.00
82
67
0.0
08
11
90
.00
83
47
0.0
07
77
90
.00
78
64
0.0
08
58
20
.00
85
30
.00
80
85
0.0
08
13
20
.00
76
66
0.0
07
89
90
.00
82
15
0.0
08
02
60
.00
84
19
0.0
07
77
8
P C
DL9
90
.01
08
08
0.0
12
06
50
.01
08
49
0.0
13
37
40
.01
20
60
.01
23
31
0.0
12
44
60
.01
01
75
0.0
11
47
30
.01
16
90
.01
18
96
0.0
12
23
0.0
10
60
90
.01
10
91
0.0
10
01
60
.01
09
93
0.0
12
85
90
.01
10
94
0.0
10
82
3
S C
DL9
90
.00
79
80
.00
80
75
0.0
08
15
60
.00
81
12
0.0
08
17
60
.00
77
32
0.0
08
37
20
.00
74
21
0.0
07
45
0.0
08
27
90
.00
84
10
.00
80
50
.00
83
04
0.0
07
22
80
.00
75
67
0.0
08
17
30
.00
80
07
0.0
07
86
30
.00
78
7
Cl C
DL9
90
.01
05
69
0.0
10
04
40
.01
10
99
0.0
10
98
50
.01
11
85
0.0
09
98
60
.01
14
20
.01
05
56
0.0
09
05
0.0
10
17
20
.01
10
51
0.0
10
17
0.0
10
63
20
.01
08
86
0.0
08
45
10
.01
02
18
0.0
10
64
70
.01
11
83
0.0
10
14
8
82
SAM
PLE
MVP
1043
5
SPO
T N
°1
23
45
67
89
1011
1213
1415
1617
1819
2021
2223
2425
MIN
ERAL
Cpx
Cpx
Grt
Grt
Grt
(Rim
)G
rt(R
im)
Grt
(Rim
)G
rt(R
im)
Grt
(Rim
)Pl
Opx
Opx
Cpx
Cpx
Grt
Grt
Grt
(Rim
)G
rt(R
im)
Grt
(Rim
)G
rt(R
im)
Grt
(Rim
)Pl
IlmG
rtG
rt
SiO
2 50
.06
50.3
839
.28
39.3
039
.56
37.8
717
.34
46.0
047
.55
48.6
645
.20
45.3
644
.26
51.3
339
.07
38.7
136
.82
39.0
438
.18
28.7
843
.91
47.2
30.
1339
.19
39.1
6
TiO
2 0.
300.
31b.
d.0.
06b.
d.b.
d.0.
400.
04b.
d.0.
08b.
d.b.
d.0.
290.
33b.
d.b.
d.0.
05b.
d.0.
080.
08b.
d.b.
d.33
.75
0.03
b.d.
Al2O
3 4.
174.
2421
.36
21.4
221
.75
20.5
617
.31
10.8
233
.49
32.6
11.
741.
803.
524.
3421
.28
20.9
8b.
d.21
.41
19.2
021
.47
27.2
233
.06
1.28
21.3
621
.11
Cr2O
3 b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.0.
110.
06b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.0.
11b.
d.b.
d.
FeO
8.
628.
7721
.13
22.2
221
.07
21.1
921
.57
22.6
01.
692.
6020
.60
21.3
89.
219.
2922
.51
22.5
522
.23
21.5
425
.84
34.8
37.
550.
4156
.07
21.7
721
.87
MnO
b.
d.0.
060.
510.
530.
500.
500.
290.
62b.
d.b.
d.0.
180.
160.
090.
070.
560.
460.
510.
560.
540.
580.
17b.
d.0.
140.
570.
59
MgO
12
.23
12.4
18.
808.
758.
358.
523.
9815
.94
0.05
0.28
21.9
421
.73
11.8
912
.33
8.62
8.68
9.20
8.48
9.72
11.9
93.
81b.
d.2.
149.
509.
56
CaO
21
.07
21.0
57.
777.
907.
656.
524.
592.
2816
.78
13.9
10.
390.
5420
.27
21.0
27.
407.
306.
267.
006.
501.
1713
.21
16.9
1b.
d.6.
776.
86
Na2
O
1.33
1.35
b.d.
b.d.
0.04
0.19
0.15
0.07
1.46
1.61
0.05
0.05
1.34
1.42
b.d.
b.d.
0.28
b.d.
0.12
b.d.
0.97
2.08
b.d.
b.d.
b.d.
K2O
b.
d.b.
d.b.
d.b.
d.b.
d.0.
090.
150.
010.
090.
15b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.0.
01b.
d.0.
030.
08b.
d.b.
d.b.
d.
P2O
5 0.
04b.
d.0.
03b.
d.b.
d.b.
d.0.
20b.
d.0.
060.
03b.
d.b.
d.b.
d.b.
d.b.
d.0.
04b.
d.0.
04b.
d.b.
d.0.
030.
04b.
d.b.
d.b.
d.
SO
3 b.
d.b.
d.b.
d.b.
d.b.
d.0.
021.
18b.
d.0.
050.
19b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.
Cl
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
0.13
b.d.
b.d.
0.01
b.d.
b.d.
b.d.
b.d.
b.d.
0.01
b.d.
b.d.
0.01
b.d.
b.d.
b.d.
0.01
b.d.
b.d.
TOTA
L97
.81
98.5
698
.87
100.
1898
.92
95.4
567
.30
98.3
910
1.21
100.
2390
.16
91.0
190
.86
100.
1499
.44
98.7
475
.35
98.0
710
0.20
98.8
896
.89
99.8
193
.63
99.1
999
.13
Si
1.90
91.
907
6.04
56.
002
6.07
16.
050
4.23
27.
035
2.16
82.
226
1.88
21.
877
1.84
81.
913
6.01
36.
005
7.78
56.
055
5.94
74.
784
6.45
22.
177
0.00
46.
014
6.02
2
Ti
0.00
90.
009
0.00
20.
007
0.00
30.
000
0.07
30.
004
0.00
00.
003
0.00
00.
001
0.00
90.
009
0.00
00.
002
0.00
70.
003
0.00
90.
010
0.00
00.
000
0.73
40.
004
0.00
1
Al
0.18
70.
189
3.87
53.
857
3.93
53.
872
4.97
81.
951
1.79
91.
758
0.08
60.
088
0.17
30.
191
3.86
13.
836
0.00
03.
914
3.52
54.
205
4.71
41.
796
0.04
43.
863
3.82
6
Cr
0.00
00.
001
0.00
00.
000
0.00
00.
003
0.00
00.
000
0.00
10.
004
0.00
20.
000
0.00
00.
000
0.00
10.
004
0.00
30.
000
0.00
20.
001
0.00
50.
001
0.00
20.
004
0.00
0
Fe
0.27
50.
278
2.72
02.
838
2.70
42.
831
4.40
22.
891
0.06
40.
099
0.71
70.
740
0.32
20.
290
2.89
72.
926
3.93
02.
795
3.36
54.
841
0.92
70.
016
1.35
72.
794
2.81
2
Mn
0.00
10.
002
0.06
60.
069
0.06
50.
067
0.06
00.
080
0.00
00.
001
0.00
60.
006
0.00
30.
002
0.07
20.
061
0.09
20.
073
0.07
10.
081
0.02
10.
000
0.00
30.
075
0.07
6
Mg
0.69
50.
700
2.01
91.
992
1.91
02.
028
1.45
03.
634
0.00
40.
019
1.36
21.
341
0.74
00.
685
1.97
82.
008
2.89
91.
961
2.25
62.
970
0.83
40.
000
0.09
22.
173
2.19
1
Ca
0.86
10.
854
1.28
11.
293
1.25
81.
116
1.20
10.
374
0.81
90.
682
0.01
70.
024
0.90
70.
840
1.22
01.
213
1.41
91.
163
1.08
50.
208
2.08
00.
835
0.00
01.
113
1.13
0
Na
0.09
80.
099
0.00
00.
000
0.01
10.
057
0.07
30.
022
0.12
90.
142
0.00
40.
004
0.10
80.
103
0.00
50.
004
0.11
60.
002
0.03
70.
000
0.27
60.
186
0.00
00.
002
0.00
0
K 0.
000
0.00
00.
000
0.00
00.
000
0.01
80.
048
0.00
30.
005
0.00
90.
000
0.00
00.
000
0.00
00.
000
0.00
10.
000
0.00
20.
002
0.00
00.
006
0.00
40.
000
0.00
00.
000
P 0.
001
0.00
00.
004
0.00
00.
003
0.00
00.
040
0.00
10.
002
0.00
10.
000
0.00
10.
000
0.00
00.
003
0.00
50.
002
0.00
60.
000
0.00
10.
004
0.00
20.
000
0.00
30.
003
S 0.
000
0.00
00.
000
0.00
10.
000
0.00
30.
217
0.00
00.
002
0.00
70.
000
0.00
00.
000
0.00
00.
001
0.00
10.
002
0.00
20.
000
0.00
00.
001
0.00
00.
000
0.00
00.
000
Cl
0.00
00.
000
0.00
00.
001
0.00
00.
000
0.05
50.
002
0.00
00.
001
0.00
00.
000
0.00
00.
000
0.00
00.
003
0.00
20.
000
0.00
30.
000
0.00
10.
000
0.00
10.
000
0.00
2
TOTA
L4.
036
4.03
816
.011
16.0
6015
.960
16.0
4516
.828
15.9
984.
993
4.95
24.
076
4.08
04.
110
4.03
316
.052
16.0
6916
.258
15.9
7516
.303
17.1
0115
.322
5.01
72.
238
16.0
4516
.063
NO
X6
624
2424
2424
248
86
66
624
2424
2424
2424
83
2424
Si C
DL9
90.
0087
760.
0117
030.
0123
970.
0088
780.
0141
470.
0085
040.
0076
50.
0098
250.
0108
540.
0123
630.
0127
380.
0099
270.
0117
460.
0124
70.
0115
940.
0107
290.
0092
360.
0115
580.
0131
190.
0092
360.
0108
330.
0081
640.
0087
410.
0112
410.
0127
04
Ti C
DL9
90.
0202
320.
0200
720.
0200
770.
0195
450.
0201
140.
0218
350.
0203
110.
0203
350.
0201
460.
0200
810.
0200
850.
0196
610.
0198
380.
0203
30.
0202
20.
0200
880.
0188
480.
0196
430.
0195
530.
0200
890.
0198
840.
0193
950.
0226
740.
0198
490.
0204
26
Al C
DL9
90.
0093
380.
0091
110.
0103
690.
0107
540.
0105
230.
0102
710.
0093
730.
0099
90.
0103
040.
0107
550.
0096
690.
0093
670.
0089
30.
0092
830.
0102
390.
0105
840.
0107
150.
0106
480.
0109
460.
0109
020.
0099
790.
0103
010.
0111
150.
0107
510.
0101
52
Cr C
DL9
90.
0418
820.
0383
330.
0423
0.04
0942
0.03
8752
0.03
4953
0.03
6746
0.03
8467
0.03
6694
0.03
8274
0.03
4357
0.03
8687
0.03
8287
0.04
3364
0.03
7716
0.03
3673
0.03
6109
0.04
2416
0.03
4712
0.03
8976
0.03
3453
0.03
5778
0.04
468
0.03
4282
0.03
8407
Fe C
DL9
90.
0524
070
0.08
1635
00.
0118
370.
0451
230.
0371
420.
0598
660
0.02
4564
0.07
3183
0.03
1582
0.04
6578
0.03
0012
0.05
0255
0.03
1244
00.
0911
270
0.06
0215
0.04
6205
00.
0678
340.
0350
640.
0472
8
Mn
CDL9
90.
0397
60.
0369
380.
0404
090.
0399
560.
0377
640.
0389
220.
0389
840.
0377
040.
0401
760.
0369
460.
0404
280.
0379
780.
0396
650.
0376
110.
0382
960.
0443
30.
0366
320.
0397
480.
0413
080.
0409
340.
0410
630.
0381
070.
0447
440.
0373
120.
0385
26
Mg
CDL9
90.
0140
160.
0135
990.
0120
260.
0092
720.
0114
20.
0125
220.
0105
330.
0132
540.
0145
760.
0098
630.
0122
470.
0164
390.
0107
920.
0153
080.
0102
520.
0117
080.
0135
20.
0134
850.
0133
840.
0104
450.
0102
090.
0097
970.
0145
690.
0083
620.
0114
12
Ca C
DL9
90.
0118
070.
0125
70.
0056
20.
0084
640.
0160
410.
0027
010
0.01
507
0.01
5741
0.01
5766
0.01
3317
0.00
9437
0.01
0252
00.
0101
570.
0032
220.
0112
960.
0144
080.
0066
140.
0134
10.
0125
280
0.01
1997
0.00
5992
0
Na
CDL9
90.
0153
230.
0152
460.
0153
860.
0158
380.
0154
30.
0147
540.
0159
280.
0157
180.
0151
210.
0147
170.
0146
80.
0157
090.
0153
380.
0146
860.
0152
670.
0151
360.
0167
730.
0142
610.
0150
780.
0171
970.
0142
930.
0144
460.
0236
790.
0149
490.
0146
56
K C
DL9
90.
0080
920.
0078
630.
0087
590.
0084
940.
0083
610.
0083
480.
0081
040.
0084
430.
0079
420.
0081
490.
0084
810.
0083
460.
008
0.00
8168
0.00
8596
0.00
8251
0.00
8468
0.00
8253
0.00
8518
0.00
8945
0.00
8027
0.00
7818
0.00
9237
0.00
8438
0.00
8356
P C
DL9
90.
0101
910.
0117
170.
0105
730.
0130
270.
0123
10.
0118
710.
0109
030.
0115
520.
0108
890.
0108
220.
0134
080.
0113
820.
0114
50.
0134
840.
0112
760.
0119
580.
0119
880.
0104
430.
0125
90.
0122
250.
0113
540.
0107
670.
0125
10.
0123
220.
0118
72
S C
DL9
90.
0077
330.
0080
590.
0085
130.
0077
710.
0080
160.
0079
30.
0069
240.
0085
790.
0077
120.
0082
670.
0085
040.
0082
140.
0079
470.
0081
130.
0083
170.
0075
330.
0083
80.
0078
840.
0082
840.
0085
540.
0075
180.
0072
480.
0085
590.
0082
630.
0085
66
Cl C
DL9
90.
0098
220.
0104
250.
0110
420.
0100
840.
0105
750.
0107
40.
0106
910.
0103
60.
0102
020.
0098
280.
0108
630.
0113
880.
0104
790.
0112
210.
0110
550.
0103
40.
0105
310.
0108
290.
0104
10.
0119
410.
0104
810.
0102
940.
0113
30.
0108
750.
0100
03
83
SA
MP
LE M
VP
10
43
8
SP
OT
N°
12
34
56
78
91
01
11
21
31
4
MIN
ER
AL
Scp
Scp
Scp
Scp
(Rim
)S
cp(R
im)
Op
xP
lP
lP
lP
lO
px
Op
xO
px
Op
x
SiO
2
42
.61
42
.40
50
.34
51
.30
58
.50
50
.65
45
.22
45
.87
45
.14
45
.49
50
.21
50
.54
49
.72
50
.43
TiO
2
b.d
.b
.d.
b.d
.b
.d.
b.d
.0
.10
b.d
.b
.d.
b.d
.b
.d.
0.0
6b
.d.
0.2
00
.05
Al2
O3
2
6.4
82
7.4
72
8.4
72
8.7
71
8.9
34
.29
33
.47
33
.40
33
.43
33
.73
4.2
34
.26
4.2
24
.16
Cr2
O3
b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.
Fe
O
0.4
90
.45
0.2
10
.24
0.6
51
9.6
80
.55
0.1
8b
.d.
0.3
71
9.3
52
0.7
11
9.2
61
9.9
1
Mn
O
b.d
.0
.07
b.d
.b
.d.
b.d
.0
.51
b.d
.b
.d.
b.d
.0
.08
0.4
20
.45
0.4
40
.43
Mg
O
0.1
20
.10
0.0
70
.04
0.1
92
2.6
7b
.d.
b.d
.b
.d.
b.d
.2
2.6
12
2.8
72
2.3
22
2.6
4
Ca
O
19
.32
19
.13
13
.20
12
.67
8.3
1b
.d.
17
.93
17
.76
17
.91
18
.07
0.5
70
.71
1.0
90
.85
Na
2O
2
.54
2.4
63
.36
2.6
13
.28
0.0
31
.58
1.6
81
.59
1.5
1b
.d.
b.d
.0
.06
0.0
2
K2
O
0.0
70
.07
0.4
90
.42
0.2
3b
.d.
0.0
40
.05
0.0
40
.05
b.d
.b
.d.
b.d
.b
.d.
P2
O5
0
.10
0.1
80
.04
0.0
40
.47
b.d
.b
.d.
0.0
4b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.
SO
3
5.3
55
.45
0.1
00
.08
0.3
6b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
C
l b
.d.
b.d
.0
.09
0.1
00
.08
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.
TO
TA
L9
7.0
79
7.7
89
6.3
79
6.2
89
1.0
09
7.9
29
8.8
09
8.9
89
8.1
19
9.3
19
7.4
59
9.5
39
7.3
09
8.5
0
Si
6.9
26
6.8
03
7.1
99
7.2
24
8.6
86
1.9
02
2.1
17
2.1
37
2.1
21
2.1
17
1.8
96
1.8
79
1.8
85
1.8
91
Ti
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
03
0.0
00
0.0
00
0.0
00
0.0
00
0.0
02
0.0
01
0.0
06
0.0
01
Al
5.0
74
5.1
97
4.8
01
4.7
76
3.3
14
0.1
90
1.8
46
1.8
34
1.8
51
1.8
50
0.1
88
0.1
87
0.1
89
0.1
84
Cr
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
02
0.0
00
0.0
02
0.0
01
0.0
01
0.0
01
Fe
0
.06
60
.06
10
.02
50
.02
90
.08
10
.61
80
.02
20
.00
70
.00
00
.01
40
.61
10
.64
40
.61
00
.62
4
Mn
0
.00
00
.00
70
.00
00
.00
00
.00
00
.01
60
.00
00
.00
00
.00
00
.00
30
.01
30
.01
40
.01
40
.01
4
Mg
0
.02
80
.02
30
.01
40
.00
90
.04
11
.26
90
.00
00
.00
00
.00
00
.00
01
.27
31
.26
81
.26
11
.26
5
Ca
3
.36
43
.29
02
.02
31
.91
31
.32
30
.00
00
.90
00
.88
70
.90
10
.90
10
.02
30
.02
80
.04
40
.03
4
Na
0
.80
10
.76
60
.93
10
.71
10
.94
30
.00
20
.14
30
.15
20
.14
50
.13
70
.00
10
.00
00
.00
40
.00
2
K
0.0
15
0.0
15
0.0
90
0.0
76
0.0
43
0.0
00
0.0
02
0.0
03
0.0
03
0.0
03
0.0
00
0.0
00
0.0
01
0.0
00
P
0.0
14
0.0
24
0.0
05
0.0
05
0.0
59
0.0
00
0.0
01
0.0
01
0.0
01
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
S
0.6
52
0.6
56
0.0
11
0.0
08
0.0
40
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
01
0.0
01
0.0
00
Cl
0.0
00
0.0
00
0.0
23
0.0
24
0.0
20
0.0
03
0.0
03
0.0
02
0.0
03
0.0
03
0.0
03
0.0
03
0.0
03
0.0
03
TO
TA
L1
6.9
41
16
.84
31
5.1
21
04
14
.77
51
4.5
50
4.0
04
5.0
34
5.0
23
5.0
26
5.0
29
4.0
11
4.0
27
4.0
19
4.0
19
NO
X1
2 S
i+A
l1
2 S
i+A
l1
2 S
i+A
l1
2 S
i+A
l1
2 S
i+A
l6
88
88
66
66
Si
CD
L99
0.0
09
67
50
.01
69
73
0.0
18
24
0.0
22
32
10
.00
96
26
0.0
21
53
20
.00
94
85
0.0
16
43
0.0
05
74
20
.01
98
39
0.0
14
15
10
.01
87
34
0.0
19
83
50
.01
89
94
Ti
CD
L99
0.0
26
26
80
.02
77
10
.02
71
84
0.0
29
85
80
.02
86
0.0
28
22
90
.02
67
33
0.0
27
79
80
.02
62
71
0.0
28
13
40
.02
80
15
0.0
27
68
70
.02
81
08
0.0
28
34
1
Al
CD
L99
0.0
14
52
30
.01
43
79
0.0
14
13
80
.01
49
44
0.0
14
63
10
.01
41
30
.01
44
22
0.0
13
60
30
.01
38
96
0.0
14
93
70
.01
50
02
0.0
15
09
50
.01
53
43
0.0
13
78
6
Cr
CD
L99
0.0
61
66
90
.04
68
45
0.0
59
18
10
.05
38
20
.06
11
41
0.0
53
79
10
.05
96
11
0.0
52
64
10
.05
68
29
0.0
59
56
80
.06
11
73
0.0
44
20
90
.04
96
11
0.0
53
76
2
Fe
CD
L99
0.0
86
80
90
00
00
.08
81
11
0.0
85
30
90
.04
59
76
0.1
03
10
90
0.0
52
42
0.0
75
12
90
0.1
00
85
1
Mn
CD
L99
0.0
53
38
90
.05
20
82
0.0
52
71
70
.05
75
71
0.0
44
63
40
.05
28
03
0.0
44
63
50
.04
82
36
0.0
52
24
30
.05
92
78
0.0
55
25
20
.05
92
86
0.0
43
11
30
.05
10
35
Mg
CD
L99
0.0
13
37
10
.01
39
39
0.0
10
33
0.0
12
99
30
.01
35
65
0.0
15
89
30
.01
60
74
0.0
11
75
0.0
18
07
10
.01
18
94
0.0
17
58
40
.01
49
28
0.0
20
13
10
.02
40
02
Ca
CD
L99
0.0
18
69
70
.01
02
45
00
00
0.0
22
60
50
0.0
53
22
30
00
00
.01
01
63
Na
CD
L99
0.0
09
31
70
.01
48
66
0.0
14
94
20
.01
38
91
0.0
14
0.0
13
68
90
.01
40
53
0.0
13
58
40
.01
48
92
0.0
13
84
0.0
14
06
70
.01
35
93
0.0
13
36
50
.01
46
94
K C
DL9
90
.01
10
44
0.0
11
34
20
.01
15
35
0.0
11
16
30
.01
14
16
0.0
11
17
60
.01
10
56
0.0
10
91
80
.01
22
0.0
11
19
0.0
10
77
30
.01
13
74
0.0
10
80
50
.01
20
8
P C
DL9
90
.01
64
48
0.0
16
41
90
.01
61
38
0.0
16
74
60
.01
26
75
0.0
14
60
10
.01
56
93
0.0
20
39
50
.01
94
95
0.0
16
47
30
.01
48
21
0.0
13
70
50
.01
85
68
0.0
18
62
4
S C
DL9
90
.01
06
02
0.0
10
29
30
.01
17
42
0.0
10
85
60
.01
18
93
0.0
10
06
40
.01
07
73
0.0
10
50
.01
12
17
0.0
10
06
50
.01
09
69
0.0
10
11
0.0
11
84
50
.01
16
83
Cl
CD
L99
0.0
55
0.0
55
0.0
55
0.0
55
0.0
55
0.0
55
0.0
55
0.0
55
0.0
55
0.0
55
0.0
55
0.0
55
0.0
55
0.0
55
84
SAM
PLE
MV
P1
04
38
SPO
T N
°1
51
61
71
81
92
02
12
22
32
42
52
62
72
82
93
03
1
MIN
ER
AL
Cp
xC
px
Cp
xC
px
Cp
xSc
pSc
pSc
pSc
pSc
pP
lP
lC
px
Pl
Pl
Pl
Pl
SiO
2
48
.72
49
.20
48
.83
13
.44
12
.22
41
.91
42
.31
42
.22
42
.38
42
.56
44
.78
44
.85
48
.64
44
.24
45
.44
45
.49
45
.49
TiO
2
0.6
50
.70
0.5
97
3.5
07
4.9
4b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
0.6
4b
.d.
b.d
.b
.d.
b.d
.
Al2
O3
5
.82
5.9
85
.63
1.1
30
.93
27
.49
27
.46
27
.49
27
.58
27
.48
34
.26
34
.50
5.9
63
4.4
93
3.8
53
3.6
23
3.6
5
Cr2
O3
b
.d.
0.0
80
.10
0.1
7b
.d.
b.d
.b
.d.
b.d
.b
.d.
0.1
0b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
Fe
O
7.9
48
.03
8.3
94
.74
4.4
9b
.d.
b.d
.0
.16
b.d
.0
.40
0.5
20
.77
7.0
5b
.d.
b.d
.0
.09
0.1
6
Mn
O
0.1
60
.20
0.1
30
.11
0.0
9b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
0.1
40
.07
b.d
.b
.d.
b.d
.
MgO
1
2.4
71
2.4
01
2.7
36
.02
5.2
10
.08
0.0
90
.04
b.d
.b
.d.
b.d
.0
.08
12
.31
0.0
4b
.d.
b.d
.0
.13
Ca
O
22
.52
21
.42
21
.53
2.0
20
.98
18
.89
18
.88
19
.12
18
.59
18
.40
17
.70
17
.82
22
.16
17
.44
17
.59
17
.16
17
.27
Na
2O
0
.57
0.5
40
.61
0.0
50
.03
2.4
42
.58
2.6
12
.59
2.5
21
.50
1.4
90
.58
1.6
91
.65
1.7
81
.73
K2
O
b.d
.b
.d.
b.d
.b
.d.
b.d
.0
.09
0.0
80
.07
0.1
20
.08
0.0
20
.03
b.d
.0
.05
0.0
50
.04
0.0
6
P2
O5
0
.04
b.d
.b
.d.
b.d
.b
.d.
0.1
20
.08
0.1
10
.11
b.d
.b
.d.
b.d
.0
.04
b.d
.b
.d.
b.d
.b
.d.
SO
3
b.d
.b
.d.
b.d
.b
.d.
b.d
.5
.06
5.4
75
.34
5.2
54
.79
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.
Cl
b.d
.b
.d.
b.d
.b
.d.
b.d
.0
.06
b.d
.b
.d.
0.0
6b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.
TO
TA
L9
8.8
89
8.5
69
8.5
31
01
.17
98
.89
96
.12
96
.95
97
.18
96
.68
96
.32
98
.79
99
.53
97
.52
98
.03
98
.57
98
.19
98
.50
Si
1.8
39
1.8
56
1.8
49
0.5
21
0.4
84
6.7
67
6.7
98
6.7
89
6.7
91
6.8
14
2.0
93
1.5
64
1.8
51
2.0
82
2.1
22
2.1
32
2.1
26
Ti
0.0
19
0.0
20
0.0
17
2.1
41
2.2
31
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
18
0.0
00
0.0
00
0.0
00
0.0
00
Al
0.2
59
0.2
66
0.2
51
0.0
51
0.0
43
5.2
33
5.2
02
5.2
11
5.2
09
5.1
86
1.8
88
1.4
18
0.2
67
1.9
13
1.8
63
1.8
57
1.8
54
Cr
0.0
02
0.0
02
0.0
03
0.0
05
0.0
01
0.0
00
0.0
00
0.0
00
0.0
00
0.0
12
0.0
00
0.0
00
0.0
01
0.0
00
0.0
02
0.0
00
0.0
00
Fe
0.2
51
0.2
53
0.2
66
0.1
54
0.1
49
0.0
00
0.0
00
0.0
22
0.0
00
0.0
53
0.0
20
0.0
22
0.2
25
0.0
00
0.0
00
0.0
04
0.0
06
Mn
0
.00
50
.00
60
.00
40
.00
40
.00
30
.00
00
.00
00
.00
00
.00
00
.00
00
.00
20
.00
00
.00
50
.00
30
.00
00
.00
20
.00
2
Mg
0.7
01
0.6
98
0.7
19
0.3
48
0.3
08
0.0
19
0.0
21
0.0
09
0.0
00
0.0
00
0.0
00
0.0
04
0.6
98
0.0
03
0.0
00
0.0
01
0.0
09
Ca
0
.91
10
.86
60
.87
40
.08
40
.04
23
.26
83
.25
03
.29
43
.19
33
.15
70
.88
70
.66
60
.90
40
.88
00
.88
00
.86
20
.86
5
Na
0
.04
20
.03
90
.04
40
.00
30
.00
20
.76
30
.80
40
.81
50
.80
50
.78
10
.13
60
.10
10
.04
30
.15
40
.15
00
.16
20
.15
7
K
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
18
0.0
16
0.0
15
0.0
25
0.0
17
0.0
01
0.0
01
0.0
00
0.0
03
0.0
03
0.0
02
0.0
03
P
0.0
01
0.0
00
0.0
01
0.0
00
0.0
00
0.0
17
0.0
11
0.0
15
0.0
14
0.0
00
0.0
01
0.0
00
0.0
01
0.0
01
0.0
01
0.0
00
0.0
01
S 0
.00
10
.00
10
.00
00
.00
00
.00
00
.61
30
.66
00
.64
50
.63
20
.57
50
.00
00
.00
00
.00
10
.00
00
.00
10
.00
00
.00
1
Cl
0.0
02
0.0
03
0.0
03
0.0
03
0.0
03
0.0
15
0.0
00
0.0
00
0.0
16
0.0
00
0.0
03
0.0
02
0.0
03
0.0
03
0.0
04
0.0
04
0.0
03
TO
TA
L4
.03
24
.01
14
.03
23
.31
43
.26
61
6.7
13
16
.76
11
6.8
14
16
.68
51
6.5
95
5.0
31
3.7
79
4.0
17
5.0
42
5.0
24
5.0
25
5.0
27
NO
X6
66
66
12
Si+
Al
12
Si+
Al
12
Si+
Al
12
Si+
Al
12
Si+
Al
88
68
88
8
Si C
DL9
90
.01
19
05
0.0
20
32
30
.01
72
85
0.0
16
15
10
0.0
25
45
20
.01
24
60
.01
18
35
0.0
18
91
90
.01
61
14
0.0
15
20
90
0.0
08
69
40
.01
92
30
.01
88
79
0.0
15
80
80
.01
28
18
Ti C
DL9
90
.02
89
82
0.0
26
10
20
.02
87
23
0.0
28
81
20
.02
92
73
0.0
27
85
0.0
34
18
10
.03
50
03
0.0
27
58
60
.02
67
27
0.0
29
17
0.0
28
21
10
.02
69
21
0.0
27
08
80
.02
82
96
0.0
28
04
0.0
28
04
1
Al C
DL9
90
.01
51
32
0.0
14
16
30
.01
41
56
0.0
13
50
70
.01
28
42
0.0
13
56
30
.01
40
69
0.0
14
67
80
.01
46
69
0.0
14
72
20
.01
50
32
0.0
15
14
40
.01
49
99
0.0
15
49
20
.01
48
32
0.0
13
56
0.0
15
13
8
Cr
CD
L99
0.0
44
50
10
.04
92
98
0.0
50
64
40
.05
14
63
0.0
50
22
60
.05
24
54
0.0
53
86
60
.05
60
02
0.0
45
16
40
.05
15
24
0.0
59
22
0.0
55
72
10
.03
72
35
0.0
59
26
0.0
54
17
50
.05
61
16
0.0
54
57
3
Fe C
DL9
90
0.1
04
83
10
.05
02
32
0.0
55
37
60
.06
42
01
0.0
31
97
30
.06
82
18
0.0
73
72
80
.10
92
19
0.0
85
57
20
.06
39
26
0.1
44
92
60
00
0.1
27
32
20
.12
01
01
Mn
CD
L99
0.0
52
22
60
.04
97
73
0.0
52
89
80
.05
72
03
0.0
50
53
40
.06
10
72
0.0
53
58
90
.05
85
49
0.0
51
51
50
.05
08
66
0.0
52
14
60
.05
64
89
0.0
47
44
10
.04
67
45
0.0
54
60
.05
84
55
0.0
43
84
3
Mg
CD
L99
0.0
15
74
40
.02
69
84
0.0
25
79
10
.01
81
15
0.0
17
99
70
.01
52
34
0.0
02
24
40
.01
97
01
0.0
15
39
30
.01
38
14
0.0
18
19
80
.01
82
10
.01
86
35
0.0
16
73
10
.00
60
80
.01
47
25
0.0
10
71
1
Ca
CD
L99
00
00
0.0
32
07
80
.02
96
02
0.0
16
63
60
.01
95
08
0.0
12
84
20
.01
24
51
00
.01
36
14
0.0
19
99
10
.01
89
66
0.0
17
45
80
.01
22
24
0.0
03
29
3
Na
CD
L99
0.0
15
17
20
.01
32
65
0.0
14
92
10
.01
50
.01
53
71
0.0
13
63
90
.01
70
11
0.0
16
74
30
.01
36
60
.01
53
38
0.0
08
83
30
.01
45
89
0.0
13
55
20
.01
38
33
0.0
12
51
50
.01
43
88
0.0
13
51
3
K C
DL9
90
.01
18
35
0.0
11
91
50
.01
21
85
0.0
11
39
0.0
11
29
70
.01
14
89
0.0
11
10
30
.01
11
58
0.0
10
87
50
.01
11
82
0.0
10
98
70
.00
69
02
0.0
10
72
50
.01
17
34
0.0
11
18
0.0
11
08
50
.01
13
23
P C
DL9
90
.01
73
98
0.0
17
07
70
.01
77
26
0.0
13
43
60
.01
85
18
0.0
15
22
20
.01
76
61
0.0
14
70
30
.01
52
02
0.0
16
15
40
.01
48
55
0.0
13
46
80
.01
73
85
0.0
14
44
60
.01
61
55
0.0
13
83
60
.01
61
61
S C
DL9
90
.01
06
72
0.0
10
78
70
.01
04
56
0.0
10
64
40
.01
09
10
.01
12
35
0.0
11
31
50
.01
14
62
0.0
12
33
70
.01
19
78
0.0
12
12
70
.01
16
82
0.0
11
90
90
.01
05
38
0.0
11
06
50
.01
03
13
0.0
10
85
5
Cl C
DL9
90
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
5
85
SAM
PLE
DEL
2-10
434
SPO
T N
°1
23
45
67
89
1011
1213
1415
1617
1819
2021
2223
2425
MIN
ERAL
Grt
Grt
Grt
(Rim
)G
rt(R
im)
Grt
(Rim
)Cp
xCp
xG
rt(R
im)
Grt
(Rim
)G
rt(R
im)
Cpx
Cpx
Cpx
Grt
Grt
Grt
Grt
Grt
Grt
Grt
Grt
(Rim
)Cp
xCp
xCp
xCp
x
SiO
2 38
.83
37.9
638
.47
38.4
538
.71
42.9
342
.99
37.6
339
.83
39.2
447
.94
47.8
647
.98
39.2
739
.28
39.4
139
.18
39.2
539
.75
39.6
836
.30
48.0
448
.01
48.3
747
.55
TiO
2 0.
410.
420.
370.
420.
401.
941.
990.
140.
410.
362.
022.
001.
980.
440.
410.
490.
410.
360.
370.
390.
362.
052.
061.
912.
00
Al2O
3 22
.63
22.2
522
.25
22.2
422
.53
11.2
111
.13
21.2
520
.97
21.8
111
.11
11.1
211
.15
22.0
722
.02
22.0
022
.68
22.6
522
.13
22.1
119
.41
11.3
011
.21
11.2
111
.21
Cr2O
3 b.
d.b.
d.0.
120.
120.
08b.
d.b.
d.0.
090.
100.
14b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.0.
110.
160.
11b.
d.0.
15b.
d.0.
10
FeO
18
.44
18.9
919
.64
18.2
818
.90
8.40
7.59
20.2
518
.80
19.4
18.
237.
748.
8319
.05
19.2
817
.63
19.4
520
.14
18.8
917
.82
16.4
37.
587.
357.
957.
79
MnO
0.
520.
430.
520.
380.
440.
130.
080.
400.
450.
46b.
d.0.
110.
070.
460.
530.
450.
470.
450.
530.
440.
35b.
d.0.
090.
130.
16
MgO
10
.46
10.2
210
.49
10.0
510
.37
9.42
9.37
10.3
411
.03
10.4
79.
569.
489.
5410
.62
10.5
910
.37
10.6
410
.64
10.6
310
.43
8.75
9.64
9.47
9.60
9.38
CaO
7.
067.
826.
687.
117.
3617
.46
17.6
18.
995.
577.
0818
.06
17.9
718
.14
7.34
7.39
7.94
7.32
8.06
7.82
7.23
6.15
17.8
517
.77
18.1
318
.07
Na2
O
0.07
0.09
0.15
1.91
0.12
2.75
2.76
0.63
0.57
0.24
2.77
2.80
2.82
0.11
0.12
0.13
0.06
0.08
0.09
0.07
1.72
2.82
2.83
2.86
2.78
K2O
b.
d.b.
d.b.
d.0.
10b.
d.b.
d.b.
d.b.
d.0.
14b.
d.b.
d.b.
d.0.
01b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.0.
16b.
d.b.
d.0.
02b.
d.
P2O
5 b.
d.0.
05b.
d.0.
080.
04b.
d.b.
d.0.
110.
120.
09b.
d.b.
d.0.
040.
110.
050.
070.
070.
120.
05b.
d.0.
170.
060.
040.
06b.
d.
SO
3 b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.0.
03b.
d.b.
d.b.
d.0.
04b.
d.b.
d.b.
d.b.
d.
Cl
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
0.09
b.d.
b.d.
b.d.
b.d.
TOTA
L98
.41
98.2
498
.70
99.1
398
.97
94.2
393
.52
99.8
397
.99
99.2
999
.69
99.0
810
0.57
99.4
899
.66
98.5
010
0.30
101.
7510
0.37
98.3
290
.04
99.3
498
.98
100.
2599
.04
Si
5.91
85.
840
5.88
75.
867
5.89
11.
704
1.71
15.
777
6.09
25.
961
1.77
71.
783
1.77
05.
941
5.94
15.
990
5.88
85.
845
5.96
36.
030
6.07
21.
779
1.78
61.
781
1.77
4
Ti
0.04
70.
049
0.04
30.
048
0.04
60.
058
0.06
00.
016
0.04
80.
041
0.05
60.
056
0.05
50.
051
0.04
70.
056
0.04
60.
040
0.04
20.
044
0.04
50.
057
0.05
80.
053
0.05
6
Al
4.06
54.
034
4.01
33.
999
4.04
10.
524
0.52
23.
846
3.78
03.
904
0.48
50.
488
0.48
43.
936
3.92
43.
942
4.01
73.
976
3.91
33.
960
3.82
60.
493
0.49
10.
487
0.49
3
Cr
0.00
80.
004
0.01
50.
014
0.01
00.
001
0.00
20.
011
0.01
20.
017
0.00
20.
001
0.00
10.
004
0.00
90.
001
0.00
00.
002
0.01
30.
019
0.01
50.
002
0.00
40.
001
0.00
3
Fe
2.35
02.
443
2.51
42.
333
2.40
50.
279
0.25
32.
600
2.40
42.
466
0.25
50.
241
0.27
22.
411
2.43
92.
241
2.44
42.
508
2.37
02.
265
2.29
80.
235
0.22
90.
245
0.24
3
Mn
0.06
80.
056
0.06
70.
050
0.05
70.
004
0.00
30.
052
0.05
90.
059
0.00
10.
004
0.00
20.
059
0.06
80.
058
0.06
00.
056
0.06
70.
056
0.05
00.
002
0.00
30.
004
0.00
5
Mg
2.37
82.
343
2.39
22.
287
2.35
40.
557
0.55
62.
366
2.51
52.
371
0.52
80.
526
0.52
52.
396
2.38
82.
351
2.38
42.
362
2.37
72.
362
2.18
30.
532
0.52
50.
527
0.52
2
Ca
1.15
21.
289
1.09
61.
163
1.20
00.
742
0.75
11.
479
0.91
31.
152
0.71
70.
717
0.71
71.
190
1.19
71.
293
1.17
81.
286
1.25
71.
177
1.10
20.
708
0.70
80.
715
0.72
3
Na
0.02
10.
028
0.04
60.
565
0.03
70.
211
0.21
30.
188
0.16
90.
071
0.19
90.
202
0.20
10.
032
0.03
40.
039
0.01
70.
024
0.02
60.
020
0.55
80.
202
0.20
40.
204
0.20
1
K 0.
000
0.00
20.
001
0.02
00.
001
0.00
00.
001
0.00
10.
027
0.00
10.
000
0.00
00.
001
0.00
00.
000
0.00
10.
001
0.00
00.
000
0.00
20.
035
0.00
00.
001
0.00
10.
000
P 0.
000
0.00
60.
001
0.01
00.
006
0.00
00.
001
0.01
50.
016
0.01
10.
000
0.00
00.
001
0.01
40.
007
0.01
00.
008
0.01
60.
006
0.00
20.
024
0.00
20.
001
0.00
20.
001
S 0.
001
0.00
10.
001
0.00
00.
001
0.00
00.
000
0.00
00.
001
0.00
10.
000
0.00
00.
000
0.00
00.
000
0.00
20.
003
0.00
00.
001
0.00
20.
005
0.00
10.
000
0.00
00.
000
Cl
0.01
00.
011
0.01
00.
013
0.01
20.
003
0.00
30.
011
0.01
20.
012
0.00
20.
002
0.00
30.
012
0.01
10.
010
0.00
90.
011
0.01
10.
009
0.02
60.
002
0.00
30.
002
0.00
3
TOTA
L16
.018
16.1
0716
.086
16.3
6816
.059
4.08
44.
075
16.3
6216
.047
16.0
664.
025
4.02
04.
033
16.0
4616
.064
15.9
9416
.056
16.1
2616
.045
15.9
5016
.240
4.01
64.
012
4.02
34.
024
NO
X24
2424
2424
66
2424
246
66
2424
2424
2424
2424
66
66
Si C
DL9
90.
0187
340.
0216
40.
0155
810.
0141
730.
0152
830.
0165
640.
0206
120.
0212
050.
0090
540.
0203
580.
0205
120.
0142
760.
0171
970.
0165
930.
0103
620.
0073
130.
0186
110.
0168
430.
0197
240.
0172
20.
0191
770.
0165
410.
0214
660.
0129
620.
0204
33
Ti C
DL9
90.
0274
680.
0275
180.
0287
790.
0273
760.
0279
920.
0272
150.
0283
10.
0279
0.02
9657
0.02
8204
0.02
8215
0.02
8457
0.02
7012
0.02
7229
0.02
869
0.02
803
0.02
7933
0.02
8551
0.02
9177
0.02
8846
0.02
925
0.02
7989
0.02
7465
0.02
8929
0.02
7754
Al C
DL9
90.
0153
950.
0155
760.
0147
960.
0155
620.
0147
140.
0138
890.
0143
680.
0153
360.
0144
470.
0147
380.
0142
650.
0137
90.
0143
880.
0150
430.
0157
70.
0151
830.
0159
430.
0155
720.
0150
930.
0149
70.
0145
40.
0136
370.
0138
890.
0136
070.
0135
49
Cr C
DL9
90.
0572
280.
0581
540.
0505
230.
0469
630.
0547
430.
0526
610.
0549
610.
0518
450.
0477
310.
0474
630.
0607
210.
0552
530.
0584
010.
0516
920.
0515
220.
0547
180.
0629
540.
0570
240.
0515
270.
0546
340.
0551
570.
0583
460.
0529
990.
0574
580.
0586
24
Fe C
DL9
90.
0825
220
00.
0697
870
00.
0420
610.
0783
260
00
0.07
9788
00.
0645
50
0.13
5943
00
00.
1187
270.
0120
80.
0212
40.
0656
240.
0431
430.
0204
79
Mn
CDL9
90.
0463
420.
0573
040.
0476
590.
0545
40.
0534
270.
0497
120.
0547
80.
0502
510.
0573
70.
0550
650.
0565
480.
0542
170.
0535
480.
0626
210.
0521
580.
0596
70.
0540
020.
0539
770.
0503
390.
0503
860.
0527
910.
0594
340.
0511
850.
0554
0.04
2714
Mg
CDL9
90.
0163
880.
0161
060.
0198
920.
0193
260.
0156
370.
0186
310.
0200
360.
0124
730.
0147
760.
0199
330.
0167
780.
0198
390.
0165
180.
0180
290.
0151
040.
0182
50.
0152
390.
0131
340.
0144
390.
0186
730.
0212
990.
0156
570.
0213
840.
0108
740.
0238
31
Ca C
DL9
90.
0215
860
0.02
2695
0.00
208
0.01
5531
0.01
596
0.01
3929
0.00
3991
00
0.00
5305
0.01
2361
00.
0161
240.
0172
530
0.01
9985
00
0.01
9652
00.
0136
270.
0200
690
0.00
6458
Na
CDL9
90.
0145
030.
0144
780.
0147
630.
0158
270.
0150
90.
0152
370.
0153
310.
0161
170.
0144
680.
0156
150.
0151
0.01
4355
0.01
6726
0.01
4629
0.01
469
0.01
5196
0.01
5128
0.01
4648
0.01
4271
0.01
5301
0.01
492
0.01
4767
0.01
4384
0.01
4474
0.01
4634
K C
DL9
90.
0117
80.
0118
580.
0115
340.
0115
980.
0115
940.
0111
390.
0110
630.
0121
560.
0118
620.
0116
390.
0116
970.
0115
750.
0110
990.
0118
640.
0117
340.
0117
570.
0119
50.
0119
360.
0118
730.
0114
450.
0116
880.
0114
950.
0115
840.
0111
960.
0114
39
P C
DL9
90.
0188
0.02
0086
0.01
9078
0.01
6115
0.01
646
0.02
0088
0.01
7697
0.01
5043
0.01
4475
0.01
6437
0.01
6254
0.01
8597
0.01
4597
0.01
3676
0.01
6753
0.01
5811
0.01
7974
0.01
7046
0.01
6752
0.01
740.
0173
730.
0135
420.
0159
710.
0152
940.
0162
34
S C
DL9
90.
0106
370.
0117
930.
0114
560.
0120
110.
0116
620.
0112
250.
0103
740.
0110
260.
0113
440.
0108
480.
0118
670.
0110
110.
0111
190.
0115
860.
0124
980.
0102
760.
0113
420.
0109
820.
0110
210.
0103
580.
0092
460.
0107
340.
0114
990.
0107
650.
0113
12
Cl C
DL9
90.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
86
SAM
PLE
MV
P9
9-2
-22
SPO
T N
°1
23
45
67
89
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
MIN
ERA
LC
px
Cp
xC
px
Cp
xC
px
Cp
xG
rtG
rtG
rtSc
pSc
pSc
pSc
pSc
pSc
pSc
pG
rtG
rtG
rtC
px
Cp
xC
px
Cp
xSc
p
SiO
2
48
.86
49
.02
49
.19
49
.42
48
.89
b.d
.3
8.6
83
8.8
03
9.0
74
5.9
44
5.9
24
5.9
34
5.7
94
6.5
64
6.9
54
6.6
73
8.8
23
8.1
23
7.9
34
4.3
74
4.2
84
8.3
34
8.2
24
2.3
5
TiO
2
1.1
11
.10
1.0
71
.11
1.0
21
.01
0.1
80
.25
0.2
3b
.d.
0.0
60
.07
b.d
.0
.05
0.0
6b
.d.
0.2
40
.21
0.2
31
.14
1.0
91
.10
1.1
0b
.d.
Al2
O3
9
.59
9.5
29
.53
9.4
29
.50
10
.57
22
.98
22
.81
23
.15
25
.48
25
.39
25
.22
25
.25
24
.91
24
.81
24
.63
22
.96
22
.93
23
.14
9.7
09
.81
9.6
89
.58
26
.36
Cr2
O3
0
.09
b.d
.0
.08
b.d
.b
.d.
0.0
9b
.d.
0.1
1b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.0
.10
b.d
.b
.d.
b.d
.b
.d.
b.d
.
Fe
O
7.0
46
.53
7.1
26
.95
7.2
37
.10
17
.78
16
.81
17
.01
0.3
3b
.d.
0.2
70
.57
0.2
40
.15
0.4
81
7.1
61
6.9
31
6.7
77
.15
7.0
37
.51
6.4
70
.71
Mn
O
0.0
9b
.d.
b.d
.0
.12
0.1
1b
.d.
0.3
00
.39
0.2
8b
.d.
b.d
.b
.d.
b.d
.b
.d.
0.0
8b
.d.
0.3
20
.35
0.3
40
.13
0.0
70
.07
b.d
.b
.d.
MgO
1
0.9
61
0.9
21
1.0
11
1.0
21
1.2
11
1.7
01
1.3
21
1.2
71
1.1
80
.21
0.1
90
.29
0.2
60
.14
0.2
00
.20
11
.44
11
.14
11
.26
10
.66
10
.51
11
.03
11
.14
0.3
1
CaO
1
9.7
61
9.4
92
0.0
12
0.0
31
9.0
11
9.2
48
.29
7.9
18
.20
16
.43
16
.66
16
.48
15
.95
16
.39
16
.08
16
.18
8.1
37
.98
8.1
81
9.4
81
9.1
11
9.3
81
9.5
41
5.7
6
Na2
O
1.6
11
.72
1.6
31
.63
1.6
71
.79
b.d
.0
.04
0.0
43
.60
3.6
63
.59
3.7
03
.60
3.6
83
.64
0.0
30
.05
0.0
51
.67
1.6
91
.72
1.6
43
.55
K2
O
b.d
.0
.01
b.d
.0
.02
b.d
.b
.d.
b.d
.b
.d.
b.d
.0
.20
0.2
20
.21
0.2
10
.22
0.2
20
.21
b.d
.b
.d.
b.d
.b
.d.
0.0
2b
.d.
b.d
.0
.22
P2
O5
b
.d.
b.d
.b
.d.
0.0
4b
.d.
b.d
.0
.05
0.0
50
.05
0.1
30
.13
0.1
30
.15
0.1
50
.13
0.1
10
.07
0.0
50
.05
0.0
5b
.d.
b.d
.b
.d.
0.1
5
SO
3
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.4
.51
4.5
34
.35
4.5
24
.53
4.6
34
.53
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.4
.39
Cl
b.d
.0
.06
b.d
.b
.d.
b.d
.b
.d.
b.d
.b
.d.
b.d
.0
.10
0.0
90
.11
0.1
00
.09
0.0
80
.10
b.d
.0
.06
b.d
.b
.d.
b.d
.b
.d.
b.d
.0
.12
TOTA
L9
9.1
09
8.3
69
9.6
59
9.7
69
8.6
35
1.5
19
9.5
79
8.4
59
9.1
99
6.9
49
6.8
69
6.6
59
6.4
99
6.8
79
7.0
89
6.7
59
9.1
69
7.8
19
8.0
39
4.3
69
3.6
19
8.8
29
7.6
89
3.9
4
Si
1.8
16
1.8
27
1.8
18
1.8
22
1.8
21
0.0
00
5.8
26
5.8
84
5.8
78
7.2
55
7.2
64
7.2
84
7.2
72
7.3
59
7.3
94
7.3
98
5.8
54
5.8
30
5.7
89
1.7
48
1.7
56
1.8
04
1.8
12
6.9
21
Ti
0.0
31
0.0
31
0.0
30
0.0
31
0.0
29
0.0
69
0.0
20
0.0
29
0.0
25
0.0
00
0.0
07
0.0
08
0.0
00
0.0
06
0.0
08
0.0
00
0.0
27
0.0
24
0.0
26
0.0
34
0.0
33
0.0
31
0.0
31
0.0
00
Al
0.4
20
0.4
18
0.4
15
0.4
09
0.4
17
1.1
30
4.0
80
4.0
77
4.1
04
4.7
45
4.7
36
4.7
16
4.7
28
4.6
41
4.6
06
4.6
02
4.0
80
4.1
34
4.1
62
0.4
50
0.4
59
0.4
26
0.4
24
5.0
79
Cr
0.0
03
0.0
02
0.0
02
0.0
02
0.0
01
0.0
07
0.0
06
0.0
13
0.0
05
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
00
0.0
02
0.0
04
0.0
12
0.0
02
0.0
00
0.0
01
0.0
00
0.0
00
Fe
0.2
19
0.2
03
0.2
20
0.2
14
0.2
25
0.5
39
2.2
39
2.1
32
2.1
40
0.0
44
0.0
00
0.0
36
0.0
76
0.0
32
0.0
20
0.0
64
2.1
64
2.1
65
2.1
40
0.2
36
0.2
33
0.2
35
0.2
03
0.0
97
Mn
0
.00
30
.00
20
.00
20
.00
40
.00
40
.00
10
.03
80
.05
00
.03
50
.00
00
.00
00
.00
00
.00
00
.00
00
.00
90
.00
00
.04
00
.04
50
.04
40
.00
40
.00
20
.00
20
.00
10
.00
0
Mg
0.6
07
0.6
07
0.6
06
0.6
06
0.6
23
1.5
83
2.5
42
2.5
48
2.5
09
0.0
49
0.0
46
0.0
68
0.0
61
0.0
32
0.0
47
0.0
46
2.5
71
2.5
39
2.5
62
0.6
26
0.6
21
0.6
14
0.6
24
0.0
76
Ca
0.7
87
0.7
78
0.7
92
0.7
91
0.7
59
1.8
71
1.3
37
1.2
86
1.3
21
2.7
80
2.8
25
2.8
01
2.7
14
2.7
76
2.7
13
2.7
48
1.3
13
1.3
07
1.3
38
0.8
23
0.8
12
0.7
75
0.7
87
2.7
60
Na
0.1
16
0.1
24
0.1
17
0.1
17
0.1
20
0.3
14
0.0
05
0.0
13
0.0
11
1.1
04
1.1
24
1.1
03
1.1
38
1.1
04
1.1
23
1.1
17
0.0
08
0.0
14
0.0
14
0.1
28
0.1
30
0.1
24
0.1
19
1.1
26
K
0.0
00
0.0
01
0.0
00
0.0
01
0.0
00
0.0
00
0.0
00
0.0
00
0.0
01
0.0
40
0.0
45
0.0
43
0.0
43
0.0
44
0.0
43
0.0
43
0.0
00
0.0
00
0.0
01
0.0
00
0.0
01
0.0
00
0.0
00
0.0
46
P
0.0
00
0.0
00
0.0
00
0.0
01
0.0
01
0.0
02
0.0
06
0.0
07
0.0
07
0.0
18
0.0
17
0.0
18
0.0
20
0.0
20
0.0
18
0.0
15
0.0
09
0.0
07
0.0
07
0.0
02
0.0
00
0.0
00
0.0
00
0.0
21
S 0
.00
00
.00
00
.00
00
.00
00
.00
00
.00
00
.00
20
.00
10
.00
10
.53
50
.53
80
.51
80
.53
90
.53
70
.54
70
.53
90
.00
10
.00
10
.00
00
.00
00
.00
00
.00
00
.00
00
.53
8
Cl
0.0
03
0.0
04
0.0
02
0.0
03
0.0
03
0.0
06
0.0
09
0.0
10
0.0
09
0.0
28
0.0
23
0.0
29
0.0
27
0.0
25
0.0
22
0.0
27
0.0
11
0.0
16
0.0
09
0.0
03
0.0
03
0.0
02
0.0
02
0.0
34
TOTA
L4
.00
33
.99
84
.00
44
.00
04
.00
25
.52
31
6.1
10
16
.04
81
6.0
46
16
.59
71
6.6
24
16
.62
41
6.6
18
16
.57
51
6.5
50
16
.60
01
6.0
79
16
.08
71
6.1
04
4.0
56
4.0
50
4.0
16
4.0
05
16
.69
9
NO
X6
66
66
62
42
42
41
2 S
i+A
l1
2 S
i+A
l1
2 S
i+A
l1
2 S
i+A
l1
2 S
i+A
l1
2 S
i+A
l2
42
42
42
46
66
61
2 S
i+A
l
Si C
DL9
90
.01
27
03
0.0
15
90
50
.01
71
86
0.0
08
66
0.0
20
61
20
.01
61
90
.02
07
41
0.0
11
79
70
.01
58
0.0
15
44
70
.01
77
99
0.0
18
99
10
.02
00
26
0.0
15
56
50
0.0
09
67
30
.01
63
66
0.0
20
26
80
.01
73
34
0.0
14
31
90
.01
53
29
0.0
12
78
70
.01
80
08
0
Ti C
DL9
90
.02
79
33
0.0
29
02
0.0
27
03
40
.02
68
07
0.0
28
92
80
.02
89
32
0.0
29
10
90
.02
74
36
0.0
27
70
90
.02
71
13
0.0
27
13
20
.02
69
27
0.0
27
69
10
.02
64
34
0.0
27
29
20
.02
85
41
0.0
27
53
80
.02
78
18
0.0
28
22
30
.02
92
12
0.0
28
33
10
.02
94
36
0.0
28
32
40
.02
86
47
Al C
DL9
90
.01
42
40
.01
39
40
.01
36
28
0.0
13
53
40
.01
43
01
0.0
16
06
90
.01
46
08
0.0
15
59
60
.01
54
88
0.0
14
24
70
.01
48
90
.01
49
78
0.0
14
21
70
.01
43
57
0.0
13
80
10
.01
46
54
0.0
15
14
70
.01
52
81
0.0
14
66
10
.01
41
59
0.0
14
31
30
.01
37
59
0.0
14
30
90
.01
48
67
Cr
CD
L99
0.0
54
08
70
.05
41
27
0.0
47
88
20
.05
58
81
0.0
53
95
0.0
52
40
.04
85
64
0.0
44
34
20
.05
74
80
.05
87
34
0.0
50
10
70
.05
58
37
0.0
56
07
60
.05
19
98
0.0
54
65
50
.04
95
17
0.0
55
52
50
.05
29
82
0.0
45
50
30
.05
39
31
0.0
53
83
40
.05
74
93
0.0
57
84
70
.05
66
24
Fe C
DL9
90
.09
24
59
0.1
12
14
10
.08
67
92
0.0
44
26
20
.06
86
15
0.0
73
34
90
0.0
65
46
20
.05
96
0.0
55
89
30
.10
72
07
0.0
67
55
80
.02
14
17
0.0
69
98
30
.07
31
95
0.0
39
13
0.0
59
61
50
.07
99
70
.07
98
42
0.0
26
87
70
.06
19
03
00
.08
35
70
Mn
CD
L99
0.0
51
18
0.0
55
00
20
.05
72
51
0.0
51
85
20
.05
49
54
0.0
54
19
50
.06
22
60
.04
98
45
0.0
59
20
20
.05
35
02
0.0
50
97
10
.05
99
61
0.0
54
68
80
.05
88
19
0.0
46
85
90
.05
15
98
0.0
57
58
0.0
55
85
90
.05
41
58
0.0
53
06
80
.04
58
37
0.0
49
26
70
.05
61
91
0.0
46
11
2
Mg
CD
L99
0.0
22
55
50
.01
66
75
0.0
18
62
30
.02
24
70
.01
44
06
0.0
14
47
0.0
16
98
10
.01
37
33
0.0
15
80
50
.01
66
21
0.0
16
66
70
.00
86
35
0.0
12
53
80
.02
02
10
.01
80
64
0.0
16
42
10
.01
92
28
0.0
17
57
60
.02
12
30
.02
32
08
0.0
21
75
50
.01
22
14
0.0
15
05
70
.01
37
08
Ca
CD
L99
0.0
11
33
80
.01
25
00
0.0
28
09
40
.00
89
14
00
.01
52
45
0.0
08
98
20
.01
19
01
00
.01
08
60
.02
49
47
0.0
19
75
20
.02
37
85
0.0
17
61
30
.00
43
31
0.0
16
29
10
.00
71
44
00
.02
02
17
0.0
20
56
0.0
18
29
30
.01
36
51
Na
CD
L99
0.0
13
95
20
.01
41
55
0.0
13
82
10
.01
51
21
0.0
14
02
10
.01
52
64
0.0
15
69
80
.01
36
25
0.0
15
44
10
.01
42
24
0.0
15
73
40
.01
40
35
0.0
13
42
20
.01
39
95
0.0
13
27
80
.01
45
95
0.0
15
58
70
.01
42
73
0.0
13
20
60
.01
49
23
0.0
14
74
60
.01
52
51
0.0
14
36
30
.01
43
22
K C
DL9
90
.01
15
95
0.0
11
81
10
.01
12
67
0.0
11
06
40
.01
15
40
.01
08
23
0.0
11
77
30
.01
17
84
0.0
11
92
10
.01
12
16
0.0
10
79
10
.01
09
60
.01
06
55
0.0
11
22
70
.01
10
11
0.0
11
28
60
.01
19
38
0.0
11
62
40
.01
18
27
0.0
11
34
50
.01
12
37
0.0
11
55
70
.01
14
33
0.0
11
13
3
P C
DL9
90
.01
93
83
0.0
18
35
20
.02
09
03
0.0
13
52
40
.01
59
81
0.0
15
10
40
.01
44
26
0.0
15
83
30
.01
40
84
0.0
18
93
80
.01
72
32
0.0
18
11
10
.01
53
53
0.0
14
66
70
.01
63
32
0.0
15
36
20
.01
37
12
0.0
16
78
40
.01
37
06
0.0
15
57
0.0
16
54
90
.01
83
35
0.0
18
06
60
.01
19
61
S C
DL9
90
.01
06
99
0.0
12
16
60
.01
13
95
0.0
10
17
40
.01
12
98
0.0
10
88
20
.01
09
82
0.0
11
63
80
.00
99
41
0.0
11
34
70
.01
05
30
.01
15
06
0.0
12
22
30
.01
19
34
0.0
10
59
90
.01
09
53
0.0
11
46
50
.01
09
43
0.0
11
25
50
.01
10
51
0.0
10
95
50
.01
17
92
0.0
10
25
40
.01
10
86
Cl C
DL9
90
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
50
.05
5
87
SAM
PLE
MV
P99-
2-22
SPO
T N
°25
2627
2829
3031
3233
3435
3637
3839
4041
4243
4445
4647
48
MIN
ERA
LSc
pG
rtG
rtG
rtPl
PlPl
Scp
Scp
Scp
Scp
Scp
Scp
Scp
Scp
Scp
Grt
Grt
Grt
Grt
(Rim
)G
rt(R
im)
PlPl
Pl
SiO
2 42
.14
35.4
536
.01
37.0
754
.99
55.6
656
.20
53.7
751
.46
53.5
142
.80
42.9
643
.15
42.2
445
.54
45.1
439
.88
39.6
039
.54
39.5
139
.50
57.7
057
.65
57.8
0
TiO
2 0.
060.
210.
200.
24b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.0.
08b.
d.b.
d.b.
d.0.
260.
180.
230.
180.
18b.
d.b.
d.b.
d.
Al2
O3
26.3
322
.51
22.9
522
.94
26.2
626
.61
26.5
126
.06
25.4
926
.60
26.2
525
.98
26.3
826
.55
25.9
725
.87
22.8
723
.00
23.1
922
.50
22.4
725
.52
25.6
525
.81
Cr2O
3 b.
d.0.
12b.
d.b.
d.0.
08b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.0.
09b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.
FeO
0.
2816
.73
17.0
316
.70
0.69
0.60
b.d.
b.d.
b.d.
b.d.
0.67
0.24
0.67
0.60
0.49
0.61
16.4
517
.79
17.2
716
.78
16.6
5b.
d.0.
430.
47
MnO
b.
d.0.
390.
350.
30b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.0.
280.
310.
320.
370.
38b.
d.b.
d.b.
d.
MgO
0.
3110
.56
11.1
811
.14
b.d.
b.d.
b.d.
b.d.
b.d.
0.14
0.18
0.22
0.20
0.24
0.27
0.14
11.5
511
.45
11.4
111
.46
11.4
00.
04b.
d.0.
04
CaO
15
.62
7.65
8.07
8.10
7.89
7.89
8.28
8.19
7.65
8.11
16.3
716
.18
16.5
716
.22
16.5
616
.25
8.30
8.24
8.20
7.70
7.90
7.99
8.04
7.79
Na2
O
3.53
0.03
0.03
0.04
6.26
6.32
6.19
6.13
5.71
6.13
3.51
3.56
3.52
3.74
3.58
3.66
0.04
0.04
0.03
0.04
0.03
6.10
6.26
6.40
K2O
0.
22b.
d.b.
d.b.
d.0.
650.
650.
660.
660.
620.
650.
210.
230.
230.
220.
230.
21b.
d.b.
d.b.
d.b.
d.b.
d.0.
660.
650.
67
P2O
5 0.
220.
05b.
d.0.
05b.
d.b.
d.b.
d.b.
d.0.
040.
040.
150.
170.
150.
150.
120.
12b.
d.b.
d.0.
06b.
d.0.
05b.
d.b.
d.b.
d.
SO
3 4.
33b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.4.
384.
404.
424.
324.
534.
34b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.b.
d.
Cl
0.13
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
0.09
0.11
0.09
0.09
0.09
0.10
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
b.d.
TOTA
L93
.19
93.7
195
.81
96.5
796
.81
97.7
397
.84
94.8
190
.98
95.1
794
.60
94.0
495
.45
94.3
897
.38
96.4
499
.71
100.
6010
0.24
98.5
498
.56
98.0
398
.69
98.9
8
Si
6.91
05.
687
5.65
55.
750
2.55
62.
560
2.57
47.
637
7.57
67.
566
6.96
47.
005
6.97
46.
893
7.17
67.
162
5.94
95.
893
5.89
15.
967
5.96
72.
630
2.61
82.
616
Ti
0.00
80.
026
0.02
40.
028
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
90.
000
0.00
00.
000
0.03
00.
020
0.02
50.
021
0.02
10.
000
0.00
00.
000
Al
5.09
04.
256
4.24
74.
193
1.43
81.
443
1.43
14.
363
4.42
44.
434
5.03
64.
995
5.02
65.
107
4.82
44.
838
4.02
14.
035
4.07
34.
005
4.00
11.
371
1.37
31.
377
Cr
0.00
00.
015
0.00
30.
001
0.00
30.
001
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.01
00.
000
0.00
00.
007
0.00
30.
000
0.00
00.
001
Fe
0.03
82.
245
2.23
72.
166
0.02
70.
023
0.00
20.
000
0.00
00.
000
0.09
10.
033
0.09
00.
082
0.06
50.
081
2.05
22.
214
2.15
12.
119
2.10
30.
000
0.01
60.
018
Mn
0.00
00.
053
0.04
70.
039
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.00
00.
000
0.03
50.
039
0.04
10.
047
0.04
80.
000
0.00
00.
000
Mg
0.07
72.
525
2.61
62.
576
0.00
00.
000
0.00
00.
000
0.00
00.
030
0.04
20.
053
0.04
90.
059
0.06
40.
032
2.56
82.
539
2.53
42.
579
2.56
70.
003
0.00
00.
003
Ca
2.74
51.
315
1.35
81.
346
0.39
30.
389
0.40
61.
247
1.20
71.
229
2.85
42.
828
2.87
02.
836
2.79
62.
763
1.32
71.
313
1.30
81.
246
1.28
00.
390
0.39
10.
378
Na
1.12
20.
010
0.00
80.
011
0.56
40.
563
0.55
01.
689
1.63
01.
680
1.10
81.
124
1.10
31.
184
1.09
31.
126
0.01
10.
012
0.00
80.
011
0.00
80.
539
0.55
10.
562
K 0.
047
0.00
10.
000
0.00
00.
039
0.03
80.
038
0.11
90.
117
0.11
60.
044
0.04
70.
047
0.04
50.
046
0.04
30.
001
0.00
00.
001
0.00
00.
000
0.03
80.
038
0.03
9
P 0.
031
0.00
70.
002
0.00
70.
001
0.00
10.
001
0.00
00.
005
0.00
40.
021
0.02
30.
020
0.02
10.
016
0.01
60.
001
0.00
30.
007
0.00
30.
006
0.00
10.
001
0.00
1
S 0.
533
0.00
20.
001
0.00
10.
001
0.00
00.
000
0.00
00.
000
0.00
00.
535
0.53
80.
536
0.52
90.
536
0.51
70.
002
0.00
10.
000
0.00
00.
000
0.00
00.
001
0.00
0
Cl
0.03
70.
009
0.01
20.
012
0.00
30.
003
0.00
30.
000
0.00
00.
000
0.02
50.
030
0.02
60.
024
0.02
50.
027
0.01
30.
011
0.01
30.
011
0.01
10.
003
0.00
30.
004
TOTA
L16
.639
16.1
5216
.208
16.1
305.
025
5.02
15.
005
15.0
5514
.958
15.0
5916
.719
16.6
7616
.750
16.7
8016
.640
16.6
0716
.020
16.0
8016
.053
16.0
1616
.016
4.97
54.
991
4.99
7
NO
X12
Si+
Al
2424
248
88
12 S
i+A
l12
Si+
Al
12 S
i+A
l12
Si+
Al
12 S
i+A
l12
Si+
Al
12 S
i+A
l12
Si+
Al
12 S
i+A
l24
2424
2424
88
8
Si C
DL9
90.
0187
830.
0161
870.
0196
670.
0214
930.
0214
780.
0173
330.
0098
420.
0084
290.
0171
240.
0195
150.
0079
450.
0204
160.
0122
280.
0148
070.
0160
230.
0168
530.
0139
660.
0169
130.
0196
330.
0161
940.
0164
590.
0208
190.
0130
80.
0087
32
Ti C
DL9
90.
0277
580.
0290
710.
0274
060.
0268
870.
0275
760.
0275
380.
0281
760.
0284
920.
0273
920.
0285
450.
0285
390.
0280
790.
0270
920.
0272
660.
0274
010.
0269
890.
0269
040.
0298
220.
0287
260.
0288
730.
0277
570.
0273
470.
0272
470.
0271
91
Al C
DL9
90.
0143
620.
0149
350.
0153
460.
0148
590.
0153
910.
0150
040.
0148
030.
0145
720.
0148
720.
0146
830.
0148
540.
0137
360.
0146
610.
0143
770.
0149
650.
0141
650.
0156
760.
0142
550.
0146
920.
0150
770.
0149
780.
0148
520.
0144
760.
0141
55
Cr C
DL9
90.
0575
620.
0514
910.
0503
480.
0569
770.
0401
050.
0550
550.
0568
30.
0522
590.
0553
480.
0580
140.
0558
090.
0535
530.
0583
350.
0468
0.05
8014
0.05
7195
0.04
6926
0.05
9699
0.05
6427
0.04
8714
0.04
9403
0.05
137
0.04
8123
0.05
5122
Fe C
DL9
90.
0663
860.
0975
960.
0686
720.
0961
780
00.
0593
850.
0819
420.
1099
080.
0572
990
0.07
4604
00.
0078
310.
0259
630
0.09
5422
0.03
1152
00.
0781
570.
0895
240.
0834
010
0
Mn
CDL9
90.
0534
820.
0552
570.
0528
940.
0597
480.
0593
220.
0508
970.
0547
160.
0468
520.
0540
990.
0642
440.
0468
560.
0475
40.
0540
80.
0535
340.
0553
50.
0571
690.
0603
80.
0603
230.
0576
740.
0535
570.
0542
40.
0483
420.
0534
970.
0534
91
Mg
CDL9
90.
0107
980.
0208
920.
0173
380.
0168
150.
0149
010.
0166
790.
0168
940.
0154
730.
0180
020
0.01
754
0.01
4974
0.01
6061
0.01
3766
0.01
2805
0.01
9598
0.01
6408
0.02
0836
0.01
7675
0.01
6367
0.01
4416
0.01
0784
0.01
5908
0.01
1909
Ca C
DL9
90.
0165
250.
0213
420.
0098
910.
0062
990.
0127
870.
0154
660
00.
0198
970
00.
0083
390
00.
0022
370.
0160
270
0.00
6576
0.00
3373
0.02
0247
0.01
7245
0.01
4884
0.01
1352
0.01
5662
Na
CDL9
90.
0142
480.
0147
610.
0148
070.
0145
570.
0146
480.
0145
160.
0151
630.
0153
980.
0154
250.
0148
910.
0156
180.
0141
830.
0143
420.
0147
870.
0140
330.
0141
780.
0141
810.
0140
070.
0153
480.
0148
670.
0144
310.
0139
060.
0150
980.
0141
43
K C
DL9
90.
0109
230.
0118
510.
0117
120.
0114
770.
0108
0.01
1411
0.01
1032
0.01
0618
0.01
1216
0.01
1487
0.01
1249
0.01
1123
0.01
0809
0.01
0803
0.01
1191
0.01
1203
0.01
2289
0.01
1674
0.01
1794
0.01
2399
0.01
1715
0.01
0901
0.01
1333
0.01
0849
P C
DL9
90.
0139
390.
0154
760.
0161
250.
0164
680.
0136
420.
0148
060.
0144
320.
0165
410.
0132
40.
0144
290.
0183
590.
0156
50.
0149
780.
0143
070.
0183
890.
0202
750.
0183
10.
0174
210.
0112
150.
0194
150.
0137
440.
0155
760.
0162
390.
0148
3
S C
DL9
90.
0125
130.
0111
390.
0114
690.
0108
950.
0099
820.
0111
380.
0101
030.
0108
230.
0107
40.
0099
940.
0117
670.
0103
670.
0119
850.
0111
540.
0121
330.
0112
530.
0113
50.
0115
70.
0115
810.
0112
690.
0118
030.
0109
230.
0101
940.
0100
97
Cl C
DL9
90.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
50.
055
0.05
5
88
APPENDIX 3 – PRESSURE-TEMPERATURE ESTIMATES (From Part 1 – 2013
thesis)
Appendix Figure 5. Calculated temperatures for pressures between 7-22Kb and calculated pressures for
temperatures between 950-1150⁰C using the geothermometer calibrated by Ravna (2000) and the
geobarometer calibrated by Newton and Perkins (1982). Sample MVP99-2-12 in red and MVP99-2-22 in
blue and black lines representing experimental P-T limits for this assemblage from Irving (1974) using
Delegate sample R130.
Appendix Figure 6. Calculated temperatures between pressures of 6-16Kb using the geothermometer
calibrated by Brey and Kohler (1990). Dashed lines show temperature paths for sample MVP10438 (blue)
and DEL99-2-01 (red). Black lines represent experimental P-T limits for this assemblage from Irving
(1974) based on Delegate sample R698.
89
Appendix Figure 7. Calculated temperatures between pressures of 13-32Kb using the geothermometer
calibrated by Ravna (2000). Calculated temperatures for sample DEL-2-10434 shown in red. Solid black
lines represent experimental P-T limits and dashed lines for changes in the modal abundance of garnet
based on Delegate sample R392.
90
APPENDIX 4 –WHOLE ROCK GEOCHEMISTRY DATA
Trac
e el
emen
ts Q
-IC
P-M
S an
alys
is (W
SU G
eoA
nal
ytic
al L
ab)
Sam
ple
ID
La p
pm
Ce
pp
mP
r p
pm
Nd
pp
mSm
pp
mE
u p
pm
Gd
pp
mT
b p
pm
Dy
pp
mH
o p
pm
Er
pp
mT
m p
pm
Yb p
pm
Lu p
pm
DE
L99
-2-0
11.
021.
880.
261.
400.
530.
310.
750.
151.
060.
220.
620.
090.
560.
08
DE
L2-1
04
30
5.48
12.3
11.
737.
962.
410.
882.
850.
523.
350.
691.
870.
271.
660.
25
DE
L2-1
04
31
9.19
16.7
92.
209.
512.
340.
972.
420.
392.
450.
511.
360.
191.
160.
18
DE
L2-1
04
34
8.42
20.8
83.
2716
.37
4.94
1.81
5.94
1.05
6.60
1.39
3.67
0.53
3.21
0.49
MV
P1
04
36
13.3
034
.89
5.45
26.5
67.
372.
087.
771.
307.
831.
574.
060.
573.
350.
49
MV
P1
04
37
11.9
330
.92
4.89
23.9
46.
881.
927.
401.
247.
631.
524.
030.
553.
230.
47
MV
P1
04
38
1.64
3.37
0.49
2.41
0.73
0.40
0.81
0.14
0.91
0.19
0.52
0.08
0.47
0.07
MV
P9
9-2
-04
3.59
6.55
0.82
3.48
0.94
0.62
1.12
0.21
1.29
0.27
0.71
0.10
0.64
0.10
MV
P9
9-2
-08
2.35
4.93
0.66
2.82
0.76
0.38
0.78
0.13
0.86
0.18
0.49
0.07
0.45
0.07
MV
P9
9-2
-12
5.11
11.4
31.
627.
352.
000.
872.
120.
352.
230.
471.
280.
181.
130.
17
MV
P9
9-2
-13
1.90
3.90
0.56
2.77
0.92
0.55
1.11
0.20
1.36
0.30
0.84
0.12
0.75
0.11
MV
P9
9-2
-22
1.57
3.93
0.69
4.30
1.96
1.14
2.90
0.57
3.75
0.81
2.25
0.32
2.05
0.31
Sam
ple
ID
Ba
pp
mT
h p
pm
Nb
pp
mY
pp
mH
f p
pm
Ta
pp
mU
pp
mP
b p
pm
Rb
pp
mC
s p
pm
Sr p
pm
Sc p
pm
Zr p
pm
DE
L99
-2-0
181
0.15
0.99
5.32
0.21
0.04
0.04
0.43
3.9
0.43
482
39.2
4
DE
L2-1
04
30
107
0.19
2.48
17.0
50.
870.
160.
052.
112.
60.
1942
437
.325
DE
L2-1
04
31
2135
0.73
5.41
13.7
00.
500.
280.
181.
454.
10.
6270
139
.518
DE
L2-1
04
34
527
0.79
13.7
434
.09
3.01
0.70
0.32
0.60
9.5
3.29
366
43.1
106
MV
P1
04
36
800.
129.
2237
.94
2.54
0.59
0.06
3.17
9.5
0.08
615
51.5
103
MV
P1
04
37
870.
148.
0536
.62
2.02
0.53
0.05
3.10
8.0
0.08
655
50.9
80
MV
P1
04
38
328
0.07
0.37
4.55
0.15
0.02
0.02
0.55
3.0
0.81
561
36.9
4
MV
P9
9-2
-04
316
0.53
3.85
6.52
0.34
0.20
0.12
1.09
7.6
4.00
548
33.2
11
MV
P9
9-2
-08
630.
100.
914.
310.
150.
060.
020.
601.
70.
1444
838
.85
MV
P9
9-2
-12
637
0.37
12.1
310
.85
1.15
0.66
0.09
1.32
18.3
1.29
864
49.7
41
MV
P9
9-2
-13
770
0.22
1.30
6.97
0.38
0.07
0.05
0.62
10.1
4.80
550
40.5
11
MV
P9
9-2
-22
437
0.07
1.29
19.8
91.
410.
090.
030.
5511
.50.
4644
538
.932
91
XR
F D
AT
A (
WS
U G
eo
An
aly
tica
l La
b)
Ro
ck t
yp
eG
G2
pG
2p
GE
c2
pG
2p
G2
pG
GG
2p
GG
GG
GG
G2
pG
Scp
Scp
Scp
Scp
DE
L99
-2-0
1D
EL2
-10
43
0D
EL2
-10
43
1D
EL2
-10
43
4M
VP
10
43
6M
VP
10
43
7M
VP
10
43
8M
VP
99
-2-0
4M
VP
99
-2-0
8M
VP
99
-2-1
2M
VP
99
-2-1
3M
VP
99
-2-2
2D
EL2
-10
43
0
Da
te
1
0-M
ay
-14
10
-Ma
y-1
41
0-M
ay
-14
10
-Ma
y-1
41
0-M
ay
-14
10
-Ma
y-1
41
0-M
ay
-14
10
-Ma
y-1
41
0-M
ay
-14
10
-Ma
y-1
41
1-M
ay
-14
11
-Ma
y-1
41
0-M
ay
-14
Un
no
rma
lize
d M
ajo
r E
lem
en
ts (
We
igh
t %
):
SiO
2
48
.36
4
9.8
7
46
.90
4
3.9
7
45
.98
4
6.5
4
48
.01
4
9.6
4
48
.53
4
6.2
3
47
.37
5
0.3
9
49
.87
TiO
2
0.2
34
0.7
50
0.5
89
1.9
12
1.9
44
1.7
26
0.2
66
0.3
92
0.1
47
0.7
11
0.3
82
1.0
61
0.7
50
Al2
O3
1
8.9
0
17
.38
1
9.8
2
13
.69
1
6.8
9
16
.12
2
0.7
8
19
.01
1
8.3
2
18
.20
1
7.0
1
15
.53
1
7.3
8
Fe
O*
6.2
0
7.3
7
8.1
9
11
.19
1
1.6
5
11
.55
7
.09
6
.27
6
.13
1
0.5
2
7.5
1
9.1
1
7.3
7
Mn
O
0
.12
00
.14
10
.14
70
.19
10
.20
20
.21
00
.13
70
.12
50
.12
70
.17
60
.15
60
.16
20
.14
1
Mg
O
1
1.2
7
8.9
6
7.2
5
9.6
2
7.1
6
7.7
5
8.3
1
7.7
4
10
.83
8
.94
1
0.2
1
7.1
2
8.9
6
Ca
O
1
2.6
5
12
.04
1
2.8
9
14
.06
1
1.1
6
10
.55
1
3.0
1
11
.17
1
3.5
2
10
.73
1
1.0
9
9.7
3
12
.04
Na
2O
1
.34
2
.59
2
.08
2
.60
2
.49
2
.74
1
.38
3
.58
1
.13
2
.11
2
.62
4
.12
2
.59
K2
O
0
.07
0
.13
0
.15
0
.15
0
.31
0
.30
0
.11
0
.40
0
.05
0
.71
0
.50
0
.55
0
.13
P2
O5
0
.00
90
.07
80
.20
00
.12
40
.31
60
.26
60
.01
90
.05
00
.01
00
.06
10
.03
70
.02
30
.07
8
Su
m9
9.1
5
99
.32
9
8.2
3
97
.50
9
8.1
0
97
.76
9
9.1
1
98
.38
9
8.7
9
98
.38
9
6.8
9
97
.79
9
9.3
2
LOI
(%)
1.2
4
1.3
4
1.8
7
1.7
9
1.0
4
1.2
7
0.8
3
1.7
4
1.1
8
1.7
2
2.5
8
1.4
6
1.3
4
No
rma
lize
d M
ajo
r E
lem
en
ts (
We
igh
t %
):
DE
L99
-2-0
1D
EL2
-10
43
0D
EL2
-10
43
1D
EL2
-10
43
4M
VP
10
43
6M
VP
10
43
7M
VP
10
43
8M
VP
99
-2-0
4M
VP
99
-2-0
8M
VP
99
-2-1
2M
VP
99
-2-1
3M
VP
99
-2-2
2D
EL2
-10
43
0
SiO
2
48
.78
5
0.2
2
47
.75
4
5.0
9
46
.87
4
7.6
1
48
.44
5
0.4
6
49
.13
4
6.9
9
48
.89
5
1.5
3
50
.22
TiO
2
0.2
36
0.7
55
0.6
00
1.9
61
1.9
81
1.7
65
0.2
68
0.3
98
0.1
49
0.7
23
0.3
94
1.0
85
0.7
55
Al2
O3
1
9.0
6
17
.50
2
0.1
8
14
.04
1
7.2
2
16
.49
2
0.9
7
19
.33
1
8.5
5
18
.50
1
7.5
5
15
.88
1
7.5
0
Fe
O*
6.2
5
7.4
2
8.3
4
11
.48
1
1.8
8
11
.81
7
.15
6
.37
6
.21
1
0.6
9
7.7
6
9.3
2
7.4
2
Mn
O
0
.12
10
.14
20
.15
00
.19
60
.20
60
.21
50
.13
80
.12
70
.12
90
.17
90
.16
10
.16
50
.14
2
Mg
O
1
1.3
7
9.0
2
7.3
8
9.8
6
7.3
0
7.9
3
8.3
9
7.8
7
10
.96
9
.08
1
0.5
4
7.2
9
9.0
2
Ca
O
1
2.7
6
12
.12
1
3.1
3
14
.42
1
1.3
7
10
.79
1
3.1
3
11
.35
1
3.6
8
10
.91
1
1.4
5
9.9
5
12
.12
Na
2O
1
.35
2
.61
2
.12
2
.67
2
.54
2
.80
1
.39
3
.64
1
.14
2
.14
2
.70
4
.21
2
.61
K2
O
0
.07
0
.13
0
.16
0
.16
0
.31
0
.31
0
.11
0
.41
0
.05
0
.72
0
.52
0
.56
0
.13
P2
O5
0
.00
90
.07
80
.20
40
.12
70
.32
20
.27
20
.02
00
.05
10
.01
00
.06
20
.03
90
.02
40
.07
8
To
tal
10
0.0
0
10
0.0
0
10
0.0
0
10
0.0
0
10
0.0
0
10
0.0
0
10
0.0
0
10
0.0
0
10
0.0
0
10
0.0
0
10
0.0
0
10
0.0
0
10
0.0
0
92
XR
F D
AT
A (
WS
U G
eo
An
aly
tic
al
La
b)
Ro
ck
ty
pe
GG
2p
G2
pG
Ec
2p
G2
pG
2p
GG
G2
pG
GG
GG
GG
2p
G
Sc
pS
cp
Sc
pS
cp
DE
L9
9-2
-01
DE
L2
-10
43
0D
EL
2-1
04
31
DE
L2
-10
43
4M
VP
10
43
6M
VP
10
43
7M
VP
10
43
8M
VP
99
-2-0
4M
VP
99
-2-0
8M
VP
99
-2-1
2M
VP
99
-2-1
3M
VP
99
-2-2
2D
EL
2-1
04
30
Da
te
1
0-M
ay
-14
10
-Ma
y-1
41
0-M
ay
-14
10
-Ma
y-1
41
0-M
ay
-14
10
-Ma
y-1
41
0-M
ay
-14
10
-Ma
y-1
41
0-M
ay
-14
10
-Ma
y-1
41
1-M
ay
-14
11
-Ma
y-1
41
0-M
ay
-14
Un
no
rma
lize
d T
rac
e E
lem
en
ts (
pp
m):
Ni
17
7
10
5
11
8
16
3
27
2
9
64
1
02
6
8
10
1
63
7
9
10
5
Cr
36
2
47
9
12
4
45
5
50
8
3
12
3
24
8
30
5
26
0
37
5
27
0
47
9
Sc
38
3
7
39
4
3
50
5
2
37
3
3
39
5
0
39
3
8
37
V1
69
2
03
2
00
3
30
3
63
3
33
1
65
1
45
1
24
3
06
1
73
2
67
2
03
Ba
81
1
15
2
16
3
53
3
86
9
1
32
9
31
9
63
6
51
7
75
4
46
1
15
Rb
5
4
6
10
1
0
9
4
8
3
20
1
1
12
4
Sr
47
9
42
0
70
0
35
9
60
4
64
0
56
3
54
7
44
6
86
3
54
3
43
5
42
0
Zr
3
25
1
9
10
6
10
2
80
4
1
1
5
42
1
1
32
2
5
Y6
1
8
14
3
4
38
3
6
5
8
5
12
8
2
0
18
Nb
1.0
2.7
5.8
13
.61
0.3
9.1
1.1
3.8
1.1
12
.91
.72
.42
.7
Ga
11
1
4
17
1
7
19
1
9
16
1
4
13
1
9
14
1
6
14
Cu
77
4
0
82
5
2
33
3
5
16
5
8
47
1
9
20
2
1
40
Zn
34
5
9
65
8
5
11
3
11
9
56
5
3
48
9
5
64
6
4
59
Pb
1
2
3
1
4
3
0
1
0
2
0
1
2
La
3
6
12
9
1
4
14
0
2
4
6
2
3
6
Ce
7
17
1
9
20
3
9
32
8
1
1
5
14
6
2
1
7
Th
0
1
1
2
1
1
0
0
0
2
0
0
1
Nd
4
9
8
14
2
7
23
3
4
2
8
2
2
9
U0
1
2
0
1
0
0
0
1
2
0
0
1
su
m t
r.1
45
8
15
57
3
59
6
22
48
1
58
9
16
08
1
39
5
15
68
1
17
8
24
84
2
10
8
17
11
1
55
7
in %
0.1
5
0.1
6
0.3
6
0.2
2
0.1
6
0.1
6
0.1
4
0.1
6
0.1
2
0.2
5
0.2
1
0.1
7
0.1
6
su
m m
+tr
99
.29
9
9.4
7
98
.59
9
7.7
3
98
.26
9
7.9
2
99
.25
9
8.5
3
98
.91
9
8.6
3
97
.10
9
7.9
6
99
.47
M+
To
xid
es
99
.34
9
9.5
2
98
.66
9
7.8
0
98
.31
9
7.9
6
99
.28
9
8.5
7
98
.95
9
8.6
9
97
.15
9
8.0
1
99
.52
w/L
OI
10
0.5
8
10
0.8
6
10
0.5
3
99
.59
9
9.3
4
99
.23
1
00
.11
1
00
.32
1
00
.12
1
00
.41
9
9.7
3
99
.47
1
00
.86
if F
e3
+1
01
.27
1
01
.68
1
01
.44
1
00
.83
1
00
.64
1
00
.51
1
00
.89
1
01
.01
1
00
.80
1
01
.57
1
00
.57
1
00
.48
1
01
.68
NiO
22
5.2
13
3.4
14
9.5
20
7.8
33
.83
6.9
81
.81
29
.98
6.3
12
8.8
80
.41
00
.81
33
.4
Cr2
O3
52
8.7
69
9.6
18
1.9
66
5.5
72
.91
21
.21
79
.93
62
.44
45
.73
80
.15
47
.73
94
.96
99
.6
Sc
2O
35
8.5
57
.05
9.5
65
.47
7.3
79
.45
6.8
50
.56
0.1
76
.25
9.7
58
.35
7.0
V2
O3
24
8.1
29
8.7
29
4.4
48
5.6
53
3.3
49
0.6
24
2.2
21
3.1
18
2.5
45
0.5
25
4.2
39
2.1
29
8.7
Ba
O9
0.5
12
8.7
24
14
.95
94
.99
6.1
10
1.9
36
7.8
35
6.6
70
.57
26
.48
65
.74
98
.31
28
.7
Rb
2O
5.6
4.0
6.9
10
.91
1.4
9.3
4.3
9.0
3.1
21
.61
2.1
13
.44
.0
SrO
56
6.3
49
7.2
82
7.5
42
4.3
71
4.7
75
7.3
66
5.8
64
7.4
52
7.0
10
20
.66
42
.65
14
.54
97
.2
ZrO
24
.63
4.4
25
.21
43
.41
37
.41
08
.25
.31
4.3
6.1
56
.91
5.4
43
.83
4.4
Y2
O3
7.1
22
.91
7.5
43
.74
8.4
45
.87
.01
0.2
6.5
14
.91
0.2
25
.62
2.9
Nb
2O
51
.43
.98
.31
9.5
14
.71
3.0
1.5
5.5
1.5
18
.52
.43
.43
.9
Ga
2O
31
5.1
18
.22
2.7
23
.22
5.0
25
.22
1.2
18
.61
6.9
26
.01
8.6
22
.01
8.2
Cu
O9
6.7
49
.91
02
.46
5.4
41
.54
3.7
20
.67
2.4
59
.42
3.9
25
.32
5.9
49
.9
Zn
O4
2.1
74
.08
0.6
10
6.4
14
0.3
14
7.8
69
.26
6.0
60
.11
18
.47
9.2
80
.37
4.0
Pb
O1
.12
.52
.70
.73
.83
.50
.30
.70
.12
.00
.00
.62
.5
La
2O
33
.47
.01
3.9
10
.51
6.1
16
.10
.22
.64
.46
.82
.33
.67
.0
Ce
O2
8.9
20
.42
3.6
24
.74
7.6
39
.39
.31
3.3
6.3
16
.67
.12
.02
0.4
Th
O2
0.0
0.9
1.0
1.8
0.6
1.2
0.3
0.0
0.0
2.1
0.0
0.1
0.9
Nd
2O
34
.51
0.3
8.9
16
.53
1.8
27
.03
.04
.82
.78
.82
.51
.91
0.3
U2
O3
0.2
0.6
2.2
0.3
1.1
0.5
0.0
0.0
0.6
2.3
0.0
0.0
0.6
Cs2
O0
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.0
As2
O5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
W2
O3
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
su
m t
r.1
90
8
20
64
4
24
4
29
10
2
04
8
20
68
1
73
7
19
77
1
54
0
31
02
2
62
5
21
82
2
06
4
in %
0.1
9
0.2
1
0.4
2
0.2
9
0.2
0
0.2
1
0.1
7
0.2
0
0.1
5
0.3
1
0.2
6
0.2
2
0.2
1
93
APPENDIX 5A – PHOTO MICROGRAPHS OF THIN SECTIONS ANALYSED
BY LA-ICP-MS
MVP10437 MVP99-2-22
MVP10438
DEL99-2-01 MVP99-2-12
DEL2-10434
94
APPENDIX 5B - LA-ICP-MS RAW DATA: Including 1 sigma errors, minimum
detection limits 99% and mean raw cps background subtracted data). Please note that all
values for the internal standard(s) are reported in units of weight% oxide. All other values are
reported in ppm
SA
MP
LE
DE
L2-1
0434
GL
ITT
ER
!: T
race E
lem
en
t C
on
cen
trati
on
s M
DL
fil
tered
.
Ele
men
tD
EL
-2-1
0434-s
pt2
-grt-
aD
EL
-2-1
0434-s
pt2
-grt-
bD
EL
-2-1
0434-s
pt2
-grt-
cD
EL
-2-1
0434-s
pt2
-cp
x-a
DE
L-2
-10434-s
pt2
-cp
x-b
DE
L-2
-10434-s
pt2
-cp
x-c
DE
L-2
-10434-s
pt6
-grt-
a
Li7
<1.8
8<
1.8
0<
1.7
26.3
78.2
11.0
6<
1.9
8
Mg24
69186.4
568133.9
767505.8
861327.5
661485.6
963100.5
667473.7
8
Si2
9239390.9
5250455.3
8232364.3
4255792.4
2265636.4
1280076.0
9222135.8
1
P31
333.3
8330.8
6373.1
1126.6
8125.9
2107.2
6328.3
Ca43
7.3
27.3
27.3
218.0
618.0
618.0
67.3
2
Sc45
61.3
61.2
260.6
633.4
633.6
433.3
762.3
1
Ti4
92314.1
42312.7
62320.8
511109.8
811156.6
811277.9
92329.5
9
V51
137.9
2137.9
6139.1
454.8
8463.7
2457.4
6130.2
7
Cr52
443.0
3439.3
6435.8
2470.7
8481.6
5474.7
5781.9
5
Ni6
024.9
224.3
324.6
6178.7
9187.5
2183.9
223.5
9
Cu
65
<0.5
81.0
2<
0.5
62.4
82.3
53.2
20.8
8
Rb
85
0.0
31
<0.0
29
<0.0
28
<0.0
195
<0.0
205
1.2
35
<0.0
33
Sr88
0.4
64
0.4
55
0.4
6178.2
9180.6
5188.6
30.4
86
Y89
74.2
575.0
175.1
98.6
99.0
59.4
980.9
1
Zr90
46.9
149.5
848.5
593.3
96.6
597.7
46.4
1
Nb
93
0.0
047
0.0
109
0.0
102
0.0
682
0.0
584
0.0
927
0.0
113
Cs1
33
<0.0
0<
0.0
040
0.0
056
<0.0
036
<0.0
033
0.1
717
<0.0
061
Ba137
<0.0
29
0.0
36
<0.0
25
0.0
53
0.0
43
0.5
62
<0.0
33
La139
0.0
225
0.0
265
0.0
275
4.2
4.3
84.4
60.0
23
Ce140
0.3
46
0.3
78
0.3
84
17.2
517.9
818.5
90.3
49
Pr141
0.1
676
0.1
704
0.1
757
3.1
14
3.2
33
3.3
49
0.1
712
Nd
143
2.2
05
2.2
41
2.2
88
17.5
118.1
618.4
41.9
45
Sm
147
2.2
22
2.1
74
2.5
44.7
45.0
35.2
52.3
19
Eu
151
1.3
39
1.3
37
1.3
89
1.5
27
1.6
12
1.6
76
1.3
35
Gd
157
6.1
46.1
46.5
54.4
14.3
64.7
36.1
6
Tb
159
1.5
55
1.5
11.5
62
0.5
79
0.5
58
0.5
77
1.5
93
Dy163
11.2
611.6
12
2.4
12.5
58
2.7
44
12.2
4
Ho165
2.7
81
2.9
06
2.9
89
0.3
67
0.3
91
0.3
86
3.1
34
Er167
8.2
98.4
98.7
20.6
63
0.7
39
0.7
98
9.4
5
Tm
169
1.2
49
1.2
61.2
69
0.0
729
0.0
675
0.0
769
1.4
2
Yb
171
8.7
58.8
9.2
70.3
55
0.3
69
0.3
09
10.1
8
Lu
175
1.2
61
1.2
86
1.3
34
0.0
337
0.0
482
0.0
456
1.6
33
Hf1
78
0.6
12
0.6
71
0.6
54
3.1
93.3
82
3.5
50.6
52
Ta181
<0.0
0170
<0.0
0174
0.0
058
0.0
115
0.0
057
0.0
086
<0.0
0
Pb
208
<0.0
093
<0.0
039
0.0
038
0.0
53
0.0
742
0.0
728
0.0
189
Th
232
0.0
02
0.0
029
<0.0
00.0
336
0.0
389
0.0
256
<0.0
030
U238
0.0
057
0.0
047
<0.0
049
0.0
121
0.0
14
0.0
104
<0.0
029
Pm
147
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
Po208
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
U232
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
Pu
238
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
95
SA
MP
LE
DE
L2-1
0434
GL
ITT
ER
!: T
race E
lem
en
t C
on
cen
trati
on
s M
DL
fil
tered
.
Ele
men
tD
EL
-2-1
0434-s
pt6
-cp
x-a
DE
L-2
-10434-s
pt5
-grt-
aD
EL
-2-1
0434-s
pt5
-grt-
bD
EL
-2-1
0434-s
pt5
-grt-
cD
EL
-2-1
0434-s
pt3
-rt-
aD
EL
-2-1
0434-s
pt3
-rt-
bD
EL
-2-1
0434-s
pt3
-il-
a
Li7
7.0
1<
2.0
6<
2.0
0<
1.8
4<
1.0
5<
1.0
1<
0.9
3
Mg24
58773.4
172496.4
71399.0
972265.6
286.8
390.6
425381.0
5
Si2
9249687.0
6250868.9
7250870.2
2231705.3
<1355.7
3<
1367.5
3<
1186.7
4
P31
98.5
3289.0
3269.2
2239.0
6<
16.6
2<
16.7
7<
15.6
8
Ca43
17.8
57.8
27.8
27.8
2<
92.0
5<
96.5
3<
88.8
3
Sc45
32.5
269.7
69.2
170.0
94.1
94.6
78.7
7
Ti4
911160.5
82542.1
62508.3
32554.1
699.9
99.9
62.5
V51
437.1
4140.8
139.5
9139.1
5748.6
1707.5
8683.9
9
Cr52
662.0
8578.7
1561
566.2
6635.2
7685.8
9699.3
5
Ni6
0178.9
827.6
30.3
428.5
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1.2
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1.2
4452
Cu
65
1.9
21.0
31.5
80.6
73.4
3.3
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85
2.4
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0.0
34
<0.0
30
<0.0
32
<0.0
179
<0.0
198
<0.0
193
Sr88
225.8
30.5
59
0.4
72
0.5
54
1.4
24
1.4
58
1.0
28
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9.2
590.3
690.4
892.3
0.1
059
0.5
19
0.3
8
Zr90
94.1
450.0
551
51.4
41331.7
81316.7
1611.5
7
Nb
93
0.1
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049
0.0
121
0.0
083
724.1
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4
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33
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0.0
055
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057
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062
0.0
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1.5
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<0.0
39
0.0
206
<0.0
35
<0.0
215
0.0
30.0
25
La139
4.2
10.0
30.0
308
0.0
227
<0.0
0221
<0.0
0245
0.0
794
Ce140
17.4
60.3
67
0.4
09
0.3
80.0
029
0.0
051
0.1
15
Pr141
3.1
69
0.1
737
0.1
734
0.1
703
<0.0
0180
0.0
0153
0.0
05
Nd
143
17.6
42.3
74
2.2
76
2.1
79
<0.0
134
<0.0
00.0
266
Sm
147
5.0
22.7
76
2.5
37
2.4
56
<0.0
00.1
19
<0.0
083
Eu
151
1.6
01
1.5
04
1.4
45
1.5
91
<0.0
0277
0.0
0107
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0255
Gd
157
4.3
87.1
57.2
47.0
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0.0
063
0.5
05
0.0
283
Tb
159
0.5
64
1.8
09
1.7
52
1.8
71
0.0
0138
0.0
0052
0.0
08
Dy163
2.6
58
14.0
714.1
414.4
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0.0
038
<0.0
037
0.0
419
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0.3
94
3.5
39
3.5
29
3.7
19
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0098
0.0
146
0.0
183
Er167
0.6
49
10.5
210.2
310.7
<0.0
079
<0.0
039
0.0
934
Tm
169
0.0
795
1.6
95
1.5
99
1.6
62
<0.0
0157
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0178
0.0
21
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171
0.3
39
11.5
911.2
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0.0
134
0.0
81
0.1
43
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175
0.0
386
1.7
81
1.7
58
1.8
18
0.0
0155
0.0
091
0.0
29
Hf1
78
3.2
52
0.6
28
0.5
89
0.6
74
32.1
632.1
716.5
3
Ta181
<0.0
42
<0.0
035
0.0
05
<0.0
019
67.7
768.3
361.8
Pb
208
0.0
512
<0.0
078
0.0
087
0.0
087
<0.0
058
<0.0
057
0.0
619
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232
0.0
384
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022
<0.0
030
0.0
053
<0.0
0143
0.0
871
0.0
753
U238
0.0
124
<0.0
030
0.0
084
0.0
072
1.1
55
1.1
49
0.4
48
Pm
147
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
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<-N
aN
<-N
aN
Po208
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
U232
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
Pu
238
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
96
SA
MP
LE
DE
L2
-10
43
4
GL
ITT
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!: 1
sig
ma
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r.
Ele
men
tD
EL
-2-1
04
34
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t2-g
rt-
aD
EL
-2-1
04
34
-sp
t2-g
rt-
bD
EL
-2-1
04
34
-sp
t2-g
rt-
cD
EL
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04
34
-sp
t2-c
px
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EL
-2-1
04
34
-sp
t2-c
px
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EL
-2-1
04
34
-sp
t2-c
px
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EL
-2-1
04
34
-sp
t6-g
rt-
a
Li7
0.9
20
.78
0.7
81
.44
1.8
2.3
60
.85
Mg
24
77
75
.17
76
74
.01
76
20
.31
69
35
.57
69
70
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71
70
.31
76
90
.44
Si2
93
66
76
12
38
38
49
83
56
25
08
.25
39
23
10
0.7
54
07
55
38
.25
42
98
61
8.5
34
10
57
2.5
P3
12
10
.18
20
8.4
42
34
.81
79
.92
79
.43
67
.73
20
6.2
2
Ca
43
0.1
80
.18
0.1
80
.42
0.4
20
.42
0.1
8
Sc4
51
.53
1.5
31
.51
0.8
30
.84
0.8
31
.56
Ti4
95
8.4
75
8.4
25
8.5
52
75
.84
27
7.1
12
80
.13
58
.95
V5
13
.53
.53
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11
.35
11
.57
11
.41
3.3
1
Cr5
21
2.0
91
1.9
91
1.8
81
2.7
11
3.0
11
2.8
22
1.3
3
Ni6
01
.44
1.4
11
.39
7.7
58
.13
7.9
81
.44
Cu
65
0.2
60
.27
0.2
50
.23
0.2
30
.25
0.3
1
Rb
85
0.0
12
0.0
12
0.0
12
0.0
08
0.0
08
80
.04
60
.01
4
Sr8
80
.02
0.0
20
.01
94
.77
4.8
45
.05
0.0
21
Y8
92
2.0
22
.02
0.2
40
.25
0.2
62
.19
Zr9
01
.24
1.3
11
.29
2.4
32
.52
2.5
51
.24
Nb
93
0.0
02
40
.00
24
0.0
02
20
.00
53
0.0
04
90
.00
63
0.0
02
5
Cs1
33
<0
.00
0.0
02
0.0
02
0.0
01
50
.00
15
0.0
07
60
.00
24
Ba137
0.0
14
0.0
14
0.0
12
0.0
11
0.0
11
0.0
34
0.0
15
La139
0.0
02
80
.00
29
0.0
02
90
.11
0.1
10
.12
0.0
02
9
Ce1
40
0.0
13
0.0
14
0.0
14
0.4
30
.45
0.4
60
.01
3
Pr1
41
0.0
07
20
.00
73
0.0
07
30
.07
80
.08
10
.08
30
.00
74
Nd
14
30
.08
40
.08
50
.08
50
.46
0.4
70
.48
0.0
78
Sm
14
70
.08
0.0
79
0.0
87
0.1
40
.14
0.1
50
.08
3
Eu
15
10
.04
0.0
40
.04
10
.04
10
.04
40
.04
50
.04
Gd
15
70
.18
0.1
80
.19
0.1
30
.13
0.1
30
.18
Tb
15
90
.04
10
.04
0.0
41
0.0
16
0.0
16
0.0
16
0.0
42
Dy
16
30
.29
0.3
0.3
10
.07
0.0
74
0.0
78
0.3
2
Ho
16
50
.07
30
.07
60
.07
80
.01
20
.01
20
.01
20
.08
2
Er1
67
0.2
20
.23
0.2
30
.02
60
.02
90
.03
0.2
5
Tm
16
90
.03
40
.03
40
.03
40
.00
37
0.0
03
60
.00
39
0.0
39
Yb
17
10
.23
0.2
30
.24
0.0
21
0.0
22
0.0
20
.26
Lu
17
50
.03
40
.03
40
.03
50
.00
26
0.0
03
10
.00
30
.04
3
Hf1
78
0.0
28
0.0
30
.02
90
.09
30
.09
90
.10
.03
Ta
18
10
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05
20
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09
10
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16
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0.0
01
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0
Pb
20
80
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0.0
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0.0
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0.0
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31
0.0
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17
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90
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97
SA
MP
LE
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L2
-10
43
4
GL
ITT
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!: 1
sig
ma
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r.
Ele
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tD
EL
-2-1
04
34
-sp
t6-c
px
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EL
-2-1
04
34
-sp
t5-g
rt-
aD
EL
-2-1
04
34
-sp
t5-g
rt-
bD
EL
-2-1
04
34
-sp
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rt-
cD
EL
-2-1
0434
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t3-r
t-a
DE
L-2
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34
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t3-r
t-b
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L-2
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4-s
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a
Li7
1.5
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0.8
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24
67
11
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30
4.6
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20
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15
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16
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453
0.4
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Si2
93
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91
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3.2
53
562
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5.7
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81
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16
8.9
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50
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Ca
43
0.4
20
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0.1
90
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38
.92
41
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5
Sc4
50
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1.7
51.7
31
.75
0.1
40.1
60
.25
Ti4
92
77
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64
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63
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64
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2.3
22.3
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.45
V5
11
0.9
23
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3.5
53
.54
18
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.49
16.9
Cr5
21
7.8
91
5.8
31
5.3
41
5.4
81
6.3
917
.71
8.0
4
Ni6
07
.78
1.6
11
.68
1.5
90
.56
0.5
51
9.9
1
Cu
65
0.2
40
.30
.30
.30
.26
0.2
60
.24
Rb
85
0.0
83
0.0
13
0.0
13
0.0
13
0.0
07
60.0
089
0.0
07
9
Sr8
86
.06
0.0
24
0.0
21
0.0
24
0.0
42
0.0
44
0.0
32
Y8
90
.25
2.4
52
.45
2.5
0.0
07
20.0
19
0.0
15
Zr9
02
.46
1.3
41.3
61
.37
35.7
335
.33
16.4
2
Nb
93
0.0
06
90
.00
26
0.0
027
0.0
02
61
9.6
19
.42
18.2
6
Cs1
33
0.1
50
.00
24
0.0
025
0.0
02
40
.001
40.0
017
0.0
01
5
Ba137
0.0
64
0.0
17
0.0
069
0.0
16
0.0
08
0.0
10
.01
La139
0.1
10
.00
33
0.0
033
0.0
03
0.0
00
87
0.0
008
0.0
04
5
Ce1
40
0.4
40
.01
40.0
15
0.0
14
0.0
00
75
0.0
012
0.0
05
6
Pr1
41
0.0
79
0.0
07
80.0
077
0.0
07
60
.000
67
0.0
007
50
.001
2
Nd
14
30
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0.0
92
0.0
89
0.0
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0.0
06
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0.0
00
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Sm
14
70
.14
0.0
98
0.0
91
0.0
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0.0
13
0.0
04
1
Eu
15
10
.04
40
.04
50.0
43
0.0
47
0.0
00
94
0.0
006
20
.001
Gd
15
70
.13
0.2
10.2
10
.20
.002
70.0
29
0.0
05
2
Tb
15
90
.01
60
.04
80.0
46
0.0
49
0.0
00
75
0.0
003
0.0
01
3
Dy
16
30
.07
70
.37
0.3
70
.38
0.0
01
20.0
017
0.0
05
7
Ho
16
50
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30
.09
30.0
93
0.0
97
0.0
00
50.0
019
0.0
01
8
Er1
67
0.0
26
0.2
80.2
70
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0.0
03
10.0
021
0.0
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2
Tm
16
90
.00
40
.04
60.0
43
0.0
45
0.0
00
61
0.0
006
20
.001
9
Yb
17
10
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10
.30
.29
0.2
90.0
056
0.0
10
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Lu
17
50
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30
.04
70
.04
60
.04
70.0
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20.0
014
0.0
02
4
Hf1
78
0.0
96
0.0
30
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90
.03
11.0
11.0
10
.52
Ta
18
10
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30
.00
17
0.0
015
0.0
01
12.0
92.1
11
.91
Pb
20
80
.00
56
0.0
04
10
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42
0.0
02
50.0
026
0.0
025
0.0
05
9
Th
23
20
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33
0.0
01
10
.00
16
0.0
01
40.0
008
40.0
061
0.0
05
2
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0.0
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L2
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tD
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EL
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04
34
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t2-g
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04
34
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EL
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t2-c
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EL
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04
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t2-c
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04
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t6-g
rt-
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Li7
1.8
81
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1.2
21
.28
1.2
81
.98
Mg
24
2.7
22
.71
2.6
91
.92
.01
2.0
43
.09
Si2
92
10
3.4
82
05
1.0
41
90
4.5
41
39
3.2
41
38
8.2
91
37
3.5
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3.6
22
2.9
32
1.6
81
5.9
51
6.6
17
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26
.33
Ca
43
0.0
18
60
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0.0
16
90
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0.0
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90
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0.0
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Sc4
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70
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.15
60
.16
90
.16
70
.25
8
Ti4
90
.84
80
.64
70
.90
30
.62
60
.57
0.6
10
.66
5
V5
10
.06
12
0.0
72
10
.05
68
0.0
37
90
.04
31
0.0
45
30
.06
25
Cr5
21
.55
1.5
21
.43
1.0
41
.07
1.0
41
.64
Ni6
01
.89
1.8
91
.78
1.2
91
.37
1.3
72
.13
Cu
65
0.5
85
0.5
85
0.5
64
0.4
15
0.4
08
0.3
96
0.7
01
Rb
85
0.0
25
80
.02
94
0.0
28
30
.01
95
0.0
20
50
.01
70
.03
26
Sr8
80
.00
69
20
.00
87
0.0
06
75
0.0
04
44
0.0
06
68
0.0
07
96
0.0
08
58
Y8
90
.01
43
0.0
12
60
.01
26
0.0
08
25
0.0
08
59
0.0
09
22
0.0
14
1
Zr9
00
.02
86
0.0
32
10
.03
18
0.0
21
40
.02
53
0.0
25
20
.03
28
Nb
93
0.0
04
16
<0
.00
00
0<
0.0
00
00
0.0
02
06
<0
.00
00
0<
0.0
00
00
<0
.00
00
0
Cs1
33
0.0
04
44
0.0
04
01
0.0
03
82
0.0
03
60
.00
33
20
.00
33
40
.00
61
3
Ba137
0.0
28
50
.02
67
0.0
25
40
.01
64
0.0
17
40
.02
32
0.0
32
8
La139
0.0
02
47
0.0
01
97
0.0
01
87
0.0
01
10
.00
18
50
.00
14
40
.00
28
4
Ce1
40
0.0
01
54
0.0
01
58
0.0
02
59
0.0
01
08
0.0
01
62
0.0
02
0.0
03
06
Pr1
41
<0
.00
00
00
.00
21
30
.00
20
2<
0.0
00
00
0.0
01
26
0.0
01
56
0.0
01
37
Nd
14
30
.01
45
0.0
10
50
.01
42
0.0
07
21
0.0
10
9<
0.0
00
00
0.0
11
8
Sm
14
7<
0.0
00
00
0.0
08
68
0.0
14
3<
0.0
00
00
0.0
06
33
0.0
09
01
0.0
16
8
Eu
15
10
.00
26
0.0
03
27
0.0
03
59
0.0
03
16
0.0
01
38
0.0
02
40
.00
21
1
Gd
15
70
.01
19
0.0
14
90
.02
17
0.0
08
35
<0
.00
00
0<
0.0
00
00
0.0
13
7
Tb
15
90
.00
12
7<
0.0
00
00
0.0
01
24
0.0
00
89
0.0
01
64
0.0
01
35
0.0
01
46
Dy
16
30
.00
86
70
.00
51
4<
0.0
00
00
0.0
04
97
<0
.00
00
00
.00
65
40
.01
15
Ho
16
5<
0.0
00
00
0.0
01
86
0.0
01
77
0.0
00
9<
0.0
00
00
0.0
01
37
0.0
02
09
Er1
67
0.0
14
70
.00
92
3<
0.0
00
00
0.0
03
65
0.0
06
74
<0
.00
00
00
.01
19
Tm
16
90
.00
16
90
.00
12
20
.00
16
4<
0.0
00
00
0.0
01
26
0.0
01
8<
0.0
00
00
Yb
17
10
.01
24
<0
.00
00
0<
0.0
00
00
<0
.00
00
00
.01
14
0.0
09
37
<0
.00
00
0
Lu
17
50
.00
13
7<
0.0
00
00
0.0
01
33
0.0
01
66
0.0
01
45
0.0
01
46
0.0
02
72
Hf1
78
<0
.00
00
00
.00
88
30
.00
48
50
.00
49
40
.00
64
40
.00
37
5<
0.0
00
00
Ta
18
10
.00
17
0.0
01
74
0.0
02
35
<0
.00
00
00
.00
18
0.0
01
81
<0
.00
00
0
Pb
20
80
.00
93
30
.00
39
1<
0.0
00
00
0.0
03
78
0.0
04
03
<0
.00
00
0<
0.0
00
00
Th
23
20
.00
18
50
.00
26
9<
0.0
00
00
0.0
02
91
0.0
01
39
0.0
02
80
.00
30
2
U2
38
0.0
01
78
0.0
02
59
0.0
04
93
0.0
01
25
0.0
01
89
0.0
01
35
0.0
02
91
Pm
14
7<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
Po
20
8<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
U2
32
<0
.00
<0
.00
<0
.00
<0
.00
<0
.00
<0
.00
<0
.00
Pu
23
8<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
99
SA
MP
LE
DE
L2
-10
43
4
GL
ITT
ER
!: M
inim
um
dete
cti
on
lim
its
(99
% c
on
fid
en
ce).
Ele
men
tD
EL
-2-1
04
34
-sp
t6-c
px
-aD
EL
-2-1
04
34
-sp
t5-g
rt-
aD
EL
-2-1
04
34
-sp
t5-g
rt-
bD
EL
-2-1
04
34
-sp
t5-g
rt-
cD
EL
-2-1
04
34
-sp
t3-r
t-a
DE
L-2
-10
43
4-s
pt3
-rt-
bD
EL
-2-1
04
34
-sp
t3-i
l-a
Li7
1.3
62
.06
21
.84
1.0
51
.01
0.9
33
Mg
24
2.2
83
.31
3.1
83
.15
2.3
42
.22
2.0
5
Si2
91
57
3.9
22
21
1.7
91
96
9.9
22
10
6.4
41
35
5.7
31
36
7.5
31
18
6.7
4
P3
11
9.3
32
7.4
32
6.8
72
6.2
41
6.6
21
6.7
71
5.6
8
Ca
43
0.0
14
0.0
20
20
.02
04
0.0
19
49
2.0
59
6.5
38
8.8
3
Sc4
50
.18
30
.27
10
.25
60
.24
60
.16
50
.16
10
.15
1
Ti4
90
.72
60
.81
10
.82
0.8
31
0.0
00
09
0.0
00
08
0.0
00
08
V5
10
.04
92
0.0
68
50
.06
89
0.0
69
10
.04
43
0.0
38
20
.04
15
Cr5
21
.15
1.6
81
.62
1.5
41
.03
1.0
10
.91
1
Ni6
01
.51
2.1
62
.08
1.9
91
.28
1.2
41
.15
Cu
65
0.4
86
0.6
56
0.6
19
0.6
68
0.4
22
0.3
93
0.3
87
Rb
85
0.0
20
50
.03
38
0.0
29
80
.03
15
0.0
17
90
.01
98
0.0
19
3
Sr8
80
.00
71
10
.01
15
0.0
08
0.0
13
10
.00
55
50
.00
65
0.0
05
46
Y8
90
.00
87
20
.01
42
0.0
13
0.0
11
70
.00
77
40
.00
91
30
.00
77
Zr9
00
.02
36
0.0
38
90
.03
36
0.0
36
10
.02
31
0.0
20
90
.02
03
Nb
93
0.0
02
47
0.0
04
9<
0.0
00
00
0.0
03
30
.00
22
<0
.00
00
0<
0.0
00
00
Cs1
33
0.0
03
04
0.0
05
52
0.0
05
68
0.0
06
22
0.0
02
73
0.0
04
23
0.0
02
9
Ba137
0.0
29
40
.03
89
<0
.00
00
00
.03
46
0.0
21
50
.01
72
0.0
19
8
La139
0.0
01
86
0.0
02
26
0.0
02
22
0.0
03
05
0.0
02
21
0.0
02
45
0.0
01
72
Ce1
40
0.0
01
29
0.0
01
81
0.0
02
51
<0
.00
00
0<
0.0
00
00
0.0
01
13
0.0
01
84
Pr1
41
0.0
01
<0
.00
00
00
.00
24
0.0
02
33
0.0
01
80
.00
12
50
.00
20
3
Nd
14
30
.01
49
0.0
12
10
.01
19
0.0
11
50
.01
34
<0
.00
00
00
.01
23
Sm
14
70
.00
71
0.0
17
30
.01
38
0.0
19
<0
.00
00
00
.01
08
0.0
08
26
Eu
15
10
.00
15
50
.00
37
60
.00
21
30
.00
35
80
.00
27
7<
0.0
00
00
0.0
02
55
Gd
15
7<
0.0
00
00
0.0
09
93
0.0
09
74
0.0
13
40
.00
63
40
.00
62
2<
0.0
00
00
Tb
15
90
.00
18
40
.00
15
0.0
02
07
0.0
02
01
0.0
01
35
<0
.00
00
00
.00
15
3
Dy
16
30
.00
59
50
.00
83
70
.00
58
0.0
09
76
0.0
03
79
0.0
03
72
0.0
06
05
Ho
16
50
.00
15
30
.00
21
50
.00
21
10
.00
14
50
.00
09
80
.00
19
20
.00
09
Er1
67
0.0
07
57
<0
.00
00
00
.01
20
.00
82
70
.00
79
10
.00
38
80
.00
36
4
Tm
16
90
.00
10
.00
24
40
.00
13
8<
0.0
00
00
0.0
01
57
0.0
01
78
0.0
00
84
Yb
17
10
.00
73
9<
0.0
00
00
0.0
17
70
.01
71
0.0
13
4<
0.0
00
00
0.0
08
69
Lu
17
50
.00
25
70
.00
16
20
.00
15
80
.00
15
4<
0.0
00
00
0.0
01
01
0.0
01
35
Hf1
78
0.0
04
18
0.0
08
30
.00
81
40
.00
55
90
.00
53
1<
0.0
00
00
0.0
07
73
Ta
18
10
.04
23
0.0
03
48
0.0
01
97
0.0
01
91
<0
.00
00
00
.00
21
80
.00
16
7
Pb
20
80
.00
32
0.0
07
80
.00
76
5<
0.0
00
00
0.0
05
80
.00
56
90
.00
37
7
Th
23
20
.00
22
10
.00
21
90
.00
30
4<
0.0
00
00
0.0
01
43
0.0
01
40
.00
13
2
U2
38
<0
.00
00
00
.00
29
90
.00
20
7<
0.0
00
00
0.0
01
39
0.0
01
92
0.0
01
28
Pm
14
7<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
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0.0
0<
0.0
0
Po
20
8<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
U2
32
<0
.00
<0
.00
<0
.00
<0
.00
<0
.00
<0
.00
<0
.00
Pu
23
8<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
100
SA
MP
LE
DE
L2
-10
43
4
GL
ITT
ER
!: M
ea
n R
aw
CP
S b
ack
gro
un
d s
ub
tra
cte
d.
Ele
men
tD
EL
-2-1
04
34
-sp
t2-g
rt-
aD
EL
-2-1
04
34
-sp
t2-g
rt-
bD
EL
-2-1
04
34
-sp
t2-g
rt-
cD
EL
-2-1
04
34
-sp
t2-c
px
-aD
EL
-2-1
04
34
-sp
t2-c
px
-bD
EL
-2-1
04
34
-sp
t2-c
px
-cD
EL
-2-1
04
34
-sp
t6-g
rt-
a
Li7
00
03
10
37
65
06
0
Mg
24
21
52
79
52
12
76
01
21
78
55
22
74
37
97
25
77
69
92
62
07
97
18
63
63
3
Si2
92
78
72
93
22
81
64
30
64
19
84
39
32
32
1
P3
12
02
72
02
42
36
61
11
61
04
38
82
18
02
Ca
43
28
79
42
89
60
29
99
41
02
81
59
65
52
95
86
32
58
95
Sc4
52
37
92
23
89
82
45
24
18
79
31
77
44
17
47
82
17
48
Ti4
95
39
76
54
26
15
64
05
37
52
00
35
38
85
35
52
36
48
91
0
V5
15
16
23
51
94
05
42
49
24
65
19
23
60
38
23
12
27
43
88
9
Cr5
21
26
13
41
25
83
21
29
30
21
94
09
61
86
51
91
82
57
02
00
45
0
Ni6
01
35
21
32
91
39
61
40
75
13
87
31
35
20
11
56
Cu
65
29
68
30
23
92
13
29
05
2
Rb
85
21
04
00
11
49
11
Sr8
84
73
46
74
89
26
35
07
25
07
33
25
99
45
44
6
Y8
98
74
77
88
87
99
22
65
14
81
31
44
80
15
09
08
57
00
Zr9
02
59
29
27
55
82
79
49
74
61
57
25
79
72
83
92
30
60
Nb
93
41
01
09
67
71
22
10
Cs1
33
07
11
03
45
10
Ba137
48
21
91
41
87
3
La139
41
49
52
11
20
71
09
72
11
08
33
8
Ce1
40
65
07
15
75
24
69
16
45
90
74
71
02
58
9
Pr1
41
40
44
13
44
11
08
71
10
59
91
08
97
37
1
Nd
14
36
20
63
36
70
71
21
69
33
69
88
49
1
Sm
14
77
58
74
69
02
23
41
23
33
24
14
71
0
Eu
15
11
48
61
49
11
60
42
45
02
42
72
50
61
33
0
Gd
15
72
10
92
12
12
34
12
18
92
03
02
18
81
89
9
Tb
15
93
54
63
46
13
70
71
90
81
72
61
77
23
25
9
Dy
16
36
49
06
72
77
20
42
00
82
00
12
13
16
33
3
Ho
16
56
25
16
56
76
99
31
19
31
19
21
16
96
31
9
Er1
67
46
08
47
44
50
40
53
25
57
59
74
71
2
Tm
16
93
02
43
06
73
19
92
55
22
12
50
30
85
Yb
17
12
87
32
90
43
17
01
68
16
41
36
29
98
Lu
17
52
66
02
72
92
92
91
02
13
81
29
30
93
Hf1
78
35
53
92
39
52
68
02
66
72
78
13
39
Ta
18
10
11
02
81
31
90
Pb
20
84
12
58
76
74
12
Th
23
23
40
75
82
53
0
U2
38
97
02
83
02
20
Pm
14
77
58
74
69
02
23
41
23
33
24
14
71
0
Po
20
84
11
90
58
76
74
12
U2
32
34
61
75
82
53
0
Pu
23
89
70
28
30
22
0
101
SA
MP
LE
DE
L2
-10
43
4
GL
ITT
ER
!: M
ea
n R
aw
CP
S b
ack
gro
un
d s
ub
tra
cte
d.
Ele
men
tD
EL
-2-1
04
34
-sp
t6-c
px
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EL
-2-1
04
34
-sp
t5-g
rt-
aD
EL
-2-1
04
34
-sp
t5-g
rt-
bD
EL
-2-1
04
34
-sp
t5-g
rt-
cD
EL
-2-1
04
34
-sp
t3-r
t-a
DE
L-2
-10
43
4-s
pt3
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bD
EL
-2-1
04
34
-sp
t3-i
l-a
Li7
29
90
02
00
05
2
Mg
24
22
51
07
11
88
12
50
18
85
51
81
99
24
60
32
25
33
79
10
57
65
9
Si2
93
62
42
47
22
52
02
43
40
00
P3
17
52
14
99
14
25
13
25
01
20
Ca
43
87
75
62
61
04
26
62
42
78
58
00
0
Sc4
51
57
75
22
95
72
32
50
24
63
62
25
92
52
75
31
1
Ti4
93
25
69
95
03
82
50
70
95
40
37
19
59
53
64
19
66
66
74
13
75
12
42
V5
12
04
71
24
47
77
45
28
54
72
39
39
29
63
37
27
75
40
27
32
Cr5
22
35
91
71
40
04
41
38
49
11
46
29
62
54
27
82
75
54
13
13
99
7
Ni6
01
22
04
12
78
14
34
14
12
95
54
39
84
3
Cu
65
15
95
89
14
03
10
30
53
20
Rb
85
21
02
00
00
60
Sr8
82
88
26
24
84
41
75
12
20
23
20
79
16
39
Y8
91
36
16
90
30
49
22
19
98
42
71
72
85
06
95
Zr9
06
49
93
23
46
02
43
79
25
72
71
01
76
98
10
09
84
25
24
20
7
Nb
93
12
82
10
79
82
24
39
76
92
41
02
64
53
Cs1
33
12
18
61
00
80
12
Ba137
47
40
42
01
09
La139
96
98
46
49
37
00
22
5
Ce1
40
40
97
25
85
66
46
46
71
33
32
Pr1
41
95
44
35
53
61
37
10
51
8
Nd
14
36
19
15
65
55
25
53
10
11
Sm
14
72
14
08
02
74
87
57
05
52
Eu
15
12
21
71
41
31
38
41
59
50
10
Gd
15
71
87
62
07
92
14
52
17
20
23
71
4
Tb
15
91
60
33
49
13
44
83
85
24
12
7
Dy
16
31
91
06
86
67
03
67
53
30
03
6
Ho
16
51
10
26
72
96
84
07
53
91
44
62
Er1
67
44
94
94
34
90
15
36
40
17
8
Tm
16
92
40
34
72
33
39
36
31
00
77
Yb
17
11
38
32
19
31
73
32
99
03
67
1
Lu
17
51
01
31
82
32
01
34
62
42
69
3
Hf1
78
23
56
30
82
95
35
32
55
14
25
61
21
47
11
Ta
18
10
27
21
57
60
11
59
47
81
61
20
8
Pb
20
84
84
55
10
71
Th
23
27
41
27
21
82
17
5
U2
38
25
21
11
02
48
02
47
71
07
8
Pm
14
72
14
08
02
74
87
57
05
52
Po
20
84
84
55
10
71
U2
32
74
12
72
18
21
75
Pu
23
82
52
11
10
24
80
24
77
10
78
102
SA
MP
LE
MV
P99-2
-12
GL
ITT
ER
!: T
race E
lem
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t C
on
cen
trati
on
s M
DL
fil
tered
.
Ele
men
t99-2
-12-s
pt2
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pt2
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pt2
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a99-2
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pt2
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x-a
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pt2
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pt3
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pt3
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b
Li7
5.8
67.7
8<
2.6
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2.5
811.9
211.2
317.3
220.9
39.0
911.7
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2.4
3
Mg24
1565.0
71502.8
372128.3
471390.3
464432.5
865238.9
81598.6
51573.7
21601.0
61581.3
4173.4
8170.3
6
Si2
9232386.0
9219757.7
3226725.5
216989.6
3237553.7
7243169.6
9213392.6
4221915.8
4232292.6
4232158.8
1301988.4
1301920.4
4
P31
482.7
2480.4
598.3
296.8
870.0
3<
25.3
2417.7
3493.8
7567.7
8585.9
770.8
451.7
3
Ca43
16.0
816.0
88.1
38.1
319.3
819.3
816.0
816.0
816.0
816.0
87.8
97.8
9
Sc45
<0.3
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0.3
778.0
278.9
334.8
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0.3
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20.5
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50.4
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Ti4
9363.3
1365.5
1508.3
91283.4
16114.2
96181.7
369.1
1367.3
3365.0
2370.6
9180.3
9173.9
6
V51
1.0
79
0.7
29
255.2
7228.3
5717.6
1715.7
90.8
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1.0
30.8
27
1.0
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0.4
88
0.6
46
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65
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Rb
85
<0.0
74
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57
<0.0
45
<0.0
43
<0.0
28
<0.0
31
0.1
81
0.1
32
0.1
22
0.0
83
0.2
58
0.3
03
Sr88
1929.2
91957.5
40.2
83
0.3
18
125.2
4126.1
62048.2
12025.3
51984.8
72034.3
62485.6
52409.8
6
Y89
0.2
12
0.2
15
18.7
618.8
41.9
26
1.8
71
0.2
34
0.2
10.2
34
0.2
02
<0.0
188
<0.0
221
Zr90
0.1
67
0.1
79
28.6
524.0
966.1
166.7
30.1
44
0.1
88
0.2
21
0.2
01
<0.0
46
<0.0
49
Nb
93
<0.0
101
0.0
136
0.0
183
<0.0
073
0.2
58
0.1
95
0.0
395
0.0
398
0.0
291
0.0
244
<0.0
082
0.0
092
Cs1
33
0.0
131
<0.0
067
<0.0
078
0.0
121
<0.0
042
<0.0
053
0.0
099
<0.0
080
<0.0
082
<0.0
055
<0.0
086
<0.0
096
Ba137
60.5
962.9
1<
0.0
58
<0.0
46
<0.0
26
<0.0
47
67.0
265.6
264.4
665.9
4153.5
5147.5
3
La139
16.2
716.6
90.0
461
0.0
274
5.1
45.0
517.3
417.4
616.9
117.5
24.1
54.0
1
Ce140
27.4
827.9
20.4
67
0.4
08
17.7
418
28.7
528.8
628.4
829.5
55.1
84.9
4
Pr141
2.6
88
2.6
48
0.1
763
0.1
753
2.8
43
2.8
51
2.7
71
2.7
81
2.7
31
2.9
10.4
17
0.4
14
Nd
143
8.9
59.3
1.9
36
2.0
114.3
114.4
19.7
39.1
19.3
99.1
71.0
41
0.9
75
Sm
147
0.8
15
0.9
76
1.7
37
1.7
64
2.8
71
2.9
71.0
48
0.8
87
0.9
74
1.0
51
0.0
95
0.0
74
Eu
151
0.4
77
0.4
36
0.9
16
0.9
53
0.9
22
0.8
93
0.4
84
0.5
03
0.5
02
0.4
98
0.3
56
0.3
24
Gd
157
0.5
22
0.3
93
2.8
32.5
71.6
51
1.6
15
0.4
0.3
61
0.3
68
0.2
60.0
5<
0.0
200
Tb
159
0.0
152
0.0
267
0.5
08
0.5
06
0.1
757
0.1
553
0.0
272
0.0
248
0.0
254
0.0
277
0.0
056
<0.0
048
Dy163
0.0
88
0.0
578
3.4
83.4
80.5
95
0.5
91
0.0
92
0.0
71
0.0
93
0.0
92
<0.0
081
0.0
121
Ho165
0.0
184
0.0
072
0.7
32
0.7
56
0.0
83
0.0
97
0.0
048
0.0
099
0.0
12
0.0
145
<0.0
036
<0.0
049
Er167
<0.0
156
0.0
124
2.0
47
2.0
61
0.1
45
0.1
46
0.0
247
0.0
127
<0.0
167
0.0
099
0.0
078
<0.0
176
Tm
169
0.0
0201
0.0
0098
0.3
14
0.3
10.0
16
0.0
182
0.0
028
<0.0
043
<0.0
017
<0.0
029
<0.0
019
<0.0
020
Yb
171
<0.0
22
<0.0
214
2.4
36
2.2
26
0.0
82
0.0
7<
0.0
242
0.0
225
0.0
186
<0.0
175
0.0
264
<0.0
210
Lu
175
0.0
023
0.0
055
0.3
38
0.3
19
0.0
035
0.0
056
<0.0
022
<0.0
043
<0.0
0196
0.0
052
<0.0
031
<0.0
023
Hf1
78
<0.0
086
<0.0
121
0.4
93
0.3
47
2.5
64
2.6
34
0.0
079
<0.0
089
<0.0
071
<0.0
121
<0.0
080
<0.0
118
Ta181
<0.0
066
0.0
04
<0.0
030
0.0
086
0.0
202
0.0
27
<0.0
038
<0.0
00.0
0244
<0.0
024
<0.0
039
<0.0
0
Pb
208
3.6
53.6
10.0
402
0.1
01
0.2
30.2
69
43.8
13.6
23.9
13.5
43.3
5
Th
232
0.0
047
0.0
046
<0.0
057
<0.0
073
0.0
153
0.0
149
0.0
06
<0.0
048
<0.0
038
<0.0
045
<0.0
074
<0.0
055
U238
<0.0
054
<0.0
044
<0.0
045
0.0
045
<0.0
025
0.0
114
<0.0
050
<0.0
046
<0.0
037
0.0
036
<0.0
050
<0.0
061
Pm
147
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
Po208
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
U232
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
Pu
238
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
103
SA
MP
LE
MV
P9
9-2
-12
GL
ITT
ER
!: T
ra
ce E
lem
en
t C
on
cen
tra
tio
ns
MD
L f
ilte
red
.
Ele
men
t9
9-2
-12
-sp
t3-g
rt-
a9
9-2
-12
-sp
t3-g
rt-
b9
9-2
-12
-sp
t3-g
rt-
c9
9-2
-12
-sp
t1-s
cp
-a9
9-2
-12
-sp
t1-s
cp
-b9
9-2
-12
-sp
t1-c
px
-a9
9-2
-12
-sp
t1-c
px
-b9
9-2
-12
-sp
t1-c
px
-c9
9-2
-12
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t4-g
rt-
a9
9-2
-12
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t4-g
rt-
b9
9-2
-12
-sp
t4-g
rt-
c9
9-2
-12
-sp
t4-r
t-a
99
-2-1
2-s
pt4
-rt-
b
Li7
<2
.08
<1
.92
3.0
51
51
7.7
31
2.1
21
3.4
15
.05
<1
.51
1.4
8<
1.6
3<
1.0
8<
0.9
6
Mg
24
73
35
7.8
74
65
1.7
37
40
95
.26
16
70
.77
16
77
.18
66
51
0.6
56
93
47
.09
70
20
9.2
47
81
33
.05
78
16
2.9
27
83
21
.48
69
7.0
72
00
.24
Si2
92
33
13
0.5
62
28
24
5.6
32
19
02
3.8
42
33
93
9.2
23
96
16
.69
24
82
97
.77
25
57
68
.91
25
59
76
.11
24
11
66
.06
24
56
55
.78
24
72
55
.42
<1
25
0.8
11
71
7.3
7
P3
16
5.0
21
13
.61
14
6.1
15
73
.73
66
0.7
36
3.9
46
3.2
26
6.9
49
9.2
41
35
.72
11
6.3
62
1.8
3<
16
.68
Ca
43
8.1
8.1
8.1
16
.56
16
.56
19
.38
19
.38
19
.38
8.2
98
.29
8.2
91
54
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89
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Sc4
57
7.8
77
8.7
67
6.8
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0.2
50
.45
34
.74
35
.07
34
.88
3.2
98
3.9
48
4.6
95
.75
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Ti4
91
50
7.0
61
53
9.2
51
46
6.2
43
71
.04
39
2.2
76
04
0.2
26
16
7.5
36
16
8.0
11
42
8.6
51
50
0.3
91
51
0.2
39
9.9
99
9.9
9
V5
12
51
.17
25
1.4
72
46
.71
0.9
71
1.1
13
71
4.5
97
22
.22
73
3.0
42
61
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26
8.0
52
67
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21
20
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23
35
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2.5
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32
0.0
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30
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2.7
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63
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36
95
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2.7
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03
8.8
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63
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2.0
42
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64
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28
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Cu
65
1.1
1.4
51
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<0
.59
0.7
15
.35
5.3
95
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0.9
91
.48
0.7
13
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Rb
85
0.1
27
0.0
91
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20
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94
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0.0
26
0.0
33
0.0
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Sr8
80
.85
91
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71
.09
72
05
0.8
22
11
8.8
41
29
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12
5.1
91
27
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0.3
01
0.3
25
0.3
31
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1.3
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Y8
91
9.7
71
9.8
91
9.3
70
.22
0.1
92
1.8
41
1.8
75
1.9
34
19
.16
19
.84
19
.73
0.2
12
0.1
08
8
Zr9
02
9.9
83
1.9
29
.04
0.1
71
0.1
99
67
.08
68
.93
68
.76
25
.12
26
.13
26
.16
14
68
.99
14
77
.95
Nb
93
0.0
29
20
.02
11
0.0
15
80
.01
82
0.0
44
50
.22
40
.24
70
.20
10
.01
04
0.0
08
60
.01
09
40
81
.72
41
36
.73
Cs1
33
0.2
04
0.0
69
20
.00
76
<0
.00
53
3.9
1<
0.0
03
40
.10
9<
0.0
04
4<
0.0
53
<0
.00
60
<0
.00
68
0.0
28
80
.02
69
Ba137
0.3
61
0.9
48
0.0
85
67
.85
87
.40
.60
3<
0.0
34
<0
.02
9<
0.0
38
<0
.04
2<
0.0
32
<0
.02
8<
0.0
23
4
La139
0.0
45
70
.03
77
0.0
41
31
7.9
71
8.5
65
.21
5.3
55
.43
0.0
35
70
.03
71
0.0
36
30
.17
31
<0
.00
19
Ce1
40
0.4
49
0.4
83
0.4
72
30
.02
31
.71
8.3
21
8.8
11
9.0
20
.47
70
.45
70
.48
50
.08
80
.00
31
Pr1
41
0.2
05
60
.18
90
.18
66
2.8
83
3.0
62
.91
22
.93
43
.00
50
.16
84
0.2
06
10
.21
15
0.0
06
4<
0.0
00
91
Nd
14
32
.30
61
.94
62
.29
99
.67
10
.54
14
.41
4.5
61
4.9
82
.22
72
.25
22
.21
0.2
98
<0
.00
78
Sm
14
71
.64
41
.87
31
.89
61
.01
11
.05
62
.95
2.7
77
3.1
05
1.8
25
1.8
61
1.9
03
<0
.00
94
<0
.00
64
Eu
15
11
.03
30
.99
61
.03
10
.48
30
.51
10
.93
90
.88
40
.96
31
.00
50
.97
10
.99
6<
0.0
02
90
.00
74
Gd
15
73
.26
3.1
13
.21
0.4
19
0.4
06
1.6
53
1.6
65
1.7
23
3.1
22
.86
2.9
40
.10
8<
0.0
1
Tb
15
90
.56
90
.59
90
.56
30
.02
46
0.0
33
0.1
61
90
.17
96
0.1
72
50
.51
30
.54
40
.50
9<
0.0
01
01
<0
.00
Dy
16
33
.53
.88
3.7
50
.05
15
0.0
70
.60
50
.70
.55
93
.64
3.6
63
.75
<0
.00
56
<0
.00
54
Ho
16
50
.82
0.8
48
0.7
97
0.0
07
20
.02
01
0.0
82
90
.08
09
0.0
78
60
.82
20
.80
80
.87
30
.00
16
2<
0.0
0
Er1
67
2.2
59
2.1
02
2.2
81
0.0
14
0.0
26
10
.17
0.1
71
0.1
42
2.4
06
2.2
84
2.2
15
0.0
17
3<
0.0
1
Tm
16
90
.32
70
.37
50
.34
80
.00
41
20
.14
48
0.0
14
30
.02
30
.01
53
0.3
57
0.3
40
.34
20
.00
1<
0.0
01
58
Yb
17
12
.51
42
.45
52
.17
60
.02
03
<0
.00
94
0.0
66
60
.06
55
0.0
52
12
.39
52
.38
92
.38
4<
0.0
17
2<
0.0
11
7
Lu
17
50
.40
80
.39
80
.37
6<
0.0
01
57
0.0
02
50
.01
24
0.0
11
80
.00
54
0.3
47
0.3
91
0.3
51
0.0
62
8<
0.0
02
33
Hf1
78
0.4
29
0.5
08
0.4
97
<0
.00
99
<0
.00
75
2.7
24
2.8
16
2.8
35
0.3
80
.40
30
.48
43
44
.42
Ta
18
10
.00
61
<0
.00
39
0.0
04
60
.00
09
7<
0.0
01
80
.02
09
0.0
22
40
.03
6<
0.0
01
86
0.0
02
97
0.0
02
07
37
8.5
33
85
.73
Pb
20
80
.03
54
0.0
19
40
.03
85
4.3
84
.41
0.3
10
.31
30
.28
4<
0.0
07
30
.00
91
0.0
09
40
.07
35
0.0
10
9
Th
23
2<
0.0
04
6<
0.0
04
3<
0.0
03
5<
0.0
0<
0.0
03
50
.01
84
<0
.01
77
0.0
14
2<
0.0
03
6<
0.0
03
40
.00
34
0.1
15
2<
0.0
01
44
U2
38
<0
.00
45
0.0
02
6<
0.0
02
40
.00
31
<0
.00
19
30
.00
52
0.0
04
90
.05
45
<0
.00
28
<0
.00
19
0.0
04
51
.26
31
.28
8
Pm
14
7<
-NaN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
Po
20
8<
-NaN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
U2
32
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
Pu
23
8<
-NaN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
<-N
aN
104
SA
MP
LE
MV
P99-2
-12
GL
ITT
ER
!: 1
sig
ma e
rror.
Ele
men
t99-2
-12-s
pt2
-scp
-a99-2
-12-s
pt2
-scp
-b99-2
-12-s
pt2
-grt-
a99-2
-12-s
pt2
-grt-
b99-2
-12-s
pt2
-cp
x-a
99-2
-12-s
pt2
-cp
x-b
99-2
-12-s
pt2
-scp
-c99-2
-12-s
pt2
-scp
-d99-2
-12-s
pt3
-scp
-a99-2
-12-s
pt3
-scp
-b99-2
-12-s
pt3
-pl-
a99-2
-12-s
pt3
-pl-
b
Li7
1.7
1.9
61.1
71.2
12.4
92.3
83.6
44.3
72.0
82.5
11.0
21.0
6
Mg24
184.9
2178.1
8573.2
98511.4
47700.1
37821.3
7192.4
3190.0
6193.9
6192.2
21.4
121.1
2
Si2
93584655.5
3391078.5
3499859
3350778.2
53669654
3757762
3298801.2
53431799
3593566.5
3592794
4676827
4677466
P31
300.8
299.1
763.6
862.6
44.6
18.6
9259.3
9306.3
9351.7
5362.7
446.2
235.5
8
Ca43
0.3
80.3
80.2
0.2
0.4
60.4
60.3
80.3
80.3
80.3
80.1
90.1
9
Sc45
0.1
60.1
61.9
92.0
10.8
80.8
80.1
50.1
70.1
40.1
30.1
50.1
6
Ti4
99.7
99.8
439.1
33.3
3153.4
155.2
29.9
39.9
49.7
79.8
65.1
95.0
7
V51
0.0
69
0.0
62
6.5
65.8
718.0
217.9
90.0
67
0.0
69
0.0
57
0.0
61
0.0
55
0.0
6
Cr52
1.1
81.0
79.8
99.7
58.6
68.8
50.9
31.0
30.9
0.8
0.9
0.9
8
Ni6
01.3
21.2
92.1
92.1
611.7
211.9
91.2
41.3
41.0
81.0
41.1
81.2
5
Cu
65
0.4
10.4
10.4
70.4
40.3
60.3
80.4
10.4
20.3
50.3
40.3
80.3
9
Rb
85
0.0
29
0.0
23
0.0
20.0
19
0.0
12
0.0
13
0.0
24
0.0
23
0.0
19
0.0
19
0.0
26
0.0
29
Sr88
52.6
253.4
50.0
19
0.0
23.4
33.4
656.3
455.8
454.7
456.1
769.5
467.6
4
Y89
0.0
15
0.0
16
0.5
30.5
30.0
60.0
59
0.0
16
0.0
16
0.0
15
0.0
14
0.0
086
0.0
097
Zr90
0.0
26
0.0
26
0.8
0.6
71.7
61.7
80.0
26
0.0
27
0.0
25
0.0
24
0.0
20.0
21
Nb
93
0.0
042
0.0
05
0.0
04
0.0
034
0.0
13
0.0
12
0.0
06
0.0
058
0.0
052
0.0
05
0.0
036
0.0
034
Cs1
33
0.0
034
0.0
032
0.0
032
0.0
032
0.0
019
0.0
023
0.0
038
0.0
037
0.0
034
0.0
026
0.0
035
0.0
037
Ba137
1.7
21.7
80.0
27
0.0
18
0.0
13
0.0
21
1.9
11.8
81.8
41.8
84.3
74.2
2
La139
0.4
30.4
40.0
049
0.0
044
0.1
40.1
40.4
60.4
60.4
50.4
60.1
20.1
1
Ce140
0.7
0.7
10.0
19
0.0
17
0.4
50.4
60.7
40.7
40.7
30.7
60.1
40.1
4
Pr141
0.0
72
0.0
71
0.0
092
0.0
089
0.0
73
0.0
74
0.0
74
0.0
75
0.0
73
0.0
77
0.0
15
0.0
16
Nd
143
0.2
80.2
80.0
92
0.0
93
0.3
90.4
0.3
0.2
80.2
80.2
70.0
60.0
58
Sm
147
0.0
48
0.0
55
0.0
80.0
79
0.0
97
0.1
0.0
55
0.0
52
0.0
51
0.0
52
0.0
14
0.0
14
Eu
151
0.0
22
0.0
20.0
35
0.0
35
0.0
30.0
29
0.0
22
0.0
23
0.0
21
0.0
21
0.0
17
0.0
17
Gd
157
0.0
38
0.0
32
0.1
10.1
0.0
64
0.0
63
0.0
34
0.0
33
0.0
29
0.0
24
0.0
10.0
092
Tb
159
0.0
034
0.0
035
0.0
19
0.0
18
0.0
075
0.0
07
0.0
032
0.0
03
0.0
03
0.0
029
0.0
016
0.0
017
Dy163
0.0
12
0.0
09
0.1
10.1
10.0
27
0.0
27
0.0
11
0.0
12
0.0
11
0.0
11
0.0
04
0.0
041
Ho165
0.0
026
0.0
021
0.0
25
0.0
25
0.0
048
0.0
054
0.0
023
0.0
019
0.0
02
0.0
021
0.0
014
0.0
018
Er167
0.0
078
0.0
057
0.0
77
0.0
77
0.0
13
0.0
13
0.0
069
0.0
059
0.0
08
0.0
046
0.0
032
0.0
069
Tm
169
0.0
0082
0.0
0057
0.0
13
0.0
13
0.0
02
0.0
022
0.0
012
0.0
018
0.0
01
0.0
01
0.0
011
0.0
01
Yb
171
0.0
12
0.0
089
0.0
98
0.0
91
0.0
12
0.0
11
0.0
085
0.0
075
0.0
083
0.0
086
0.0
077
0.0
077
Lu
175
0.0
0094
0.0
018
0.0
14
0.0
13
0.0
011
0.0
015
0.0
013
0.0
019
0.0
0083
0.0
017
0.0
014
0.0
011
Hf1
78
0.0
049
0.0
055
0.0
31
0.0
24
0.0
82
0.0
85
0.0
032
0.0
037
0.0
042
0.0
063
0.0
033
0.0
043
Ta181
0.0
023
0.0
019
0.0
013
0.0
024
0.0
025
0.0
031
0.0
012
<0.0
00.0
01
0.0
012
0.0
012
<0.0
0
Pb
208
0.1
60.1
60.0
095
0.0
12
0.0
16
0.0
18
0.1
80.1
70.1
60.1
70.1
60.1
5
Th
232
0.0
016
0.0
015
0.0
022
0.0
024
0.0
026
0.0
022
0.0
017
0.0
02
0.0
014
0.0
019
0.0
023
0.0
026
U238
0.0
019
0.0
018
0.0
023
0.0
02
0.0
012
0.0
021
0.0
015
0.0
021
0.0
019
0.0
012
0.0
016
0.0
021
Pm
147
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
Po208
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
U232
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
Pu
238
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
105
SA
MP
LE
MV
P99-2
-12
GL
ITT
ER
!: 1
sig
ma e
rror.
Ele
men
t99-2
-12-s
pt3
-grt
-a99-2
-12-s
pt3
-grt
-b99-2
-12-s
pt3
-grt
-c99-2
-12-s
pt1
-scp
-a99-2
-12-s
pt1
-scp
-b99-2
-12-s
pt1
-cp
x-a
99-2
-12-s
pt1
-cp
x-b
99-2
-12-s
pt1
-cp
x-c
99-2
-12-s
pt4
-grt
-a99-2
-12-s
pt4
-grt
-b99-2
-12-s
pt4
-grt
-c99-2
-12-s
pt4
-rt-
a99-2
-12-s
pt4
-rt-
b
Li7
0.9
70.8
41.0
33.1
13.6
82.4
92.7
53.0
80.7
30.7
10.7
10.4
90.4
2
Mg24
9038.3
99230.1
99193.6
2208.0
4209.6
88338.2
98726.2
78867.9
9910.1
79951.6
610010.5
4124.4
735.8
Si2
93613054.5
3538628
3396886.7
53629526
3718959.5
3855088.7
53972526.2
53977187.2
53748438.7
53819608.7
53845877.2
56175.5
230260.2
1
P31
42.2
671.2
690.9
5353.6
6407.0
639.9
839.5
741.8
61.9
283.9
772.2
516.5
420.2
Ca43
0.2
0.2
0.2
0.3
90.3
90.4
50.4
50.4
50.2
0.2
0.2
41.3
39.7
5
Sc4
51.9
71.9
91.9
40.1
10.1
20.8
70.8
80.8
82.1
2.1
12.1
40.1
80.1
8
Ti4
939
39.8
537.9
69.8
410.6
9152.7
9156.2
1156.3
937.0
238.8
839.2
12.3
32.3
3
V51
6.4
56.4
66.3
30.0
55
0.0
67
18.0
718.2
818.5
76.7
26.8
96.8
852.3
651.3
5
Cr5
29.4
9.3
39.3
50.7
10.7
8.8
89.1
89.5
418.6
219.4
319.5
920.4
520.1
2
Ni6
02.1
62.1
72.1
20.8
90.9
612.0
612.5
212.9
21.8
61.9
62.0
60.6
90.5
7
Cu
65
0.3
60.3
50.3
50.2
60.3
10.3
40.3
50.3
50.3
0.2
90.3
0.2
80.2
7
Rb
85
0.0
19
0.0
18
0.0
13
0.0
18
0.0
68
0.0
081
0.0
085
0.0
091
0.0
13
0.0
11
0.0
13
0.0
10.0
084
Sr8
80.0
34
0.0
48
0.0
41
57.3
659.5
93.6
43.5
23.6
0.0
16
0.0
17
0.0
17
0.0
42
0.0
42
Y89
0.5
60.5
70.5
50.0
13
0.0
15
0.0
56
0.0
58
0.0
60.5
50.5
70.5
70.0
11
0.0
076
Zr9
00.8
40.8
90.8
10.0
19
0.0
25
1.8
31.8
81.8
80.7
10.7
40.7
439.4
239.6
6
Nb
93
0.0
046
0.0
042
0.0
037
0.0
038
0.0
066
0.0
11
0.0
12
0.0
10.0
032
0.0
026
0.0
036
110.4
4111.9
2
Cs1
33
0.0
11
0.0
06
0.0
029
0.0
024
0.1
30.0
016
0.0
059
0.0
018
0.0
32
0.0
026
0.0
028
0.0
028
0.0
03
Ba137
0.0
40.0
63
0.0
21
1.9
52.5
40.0
36
0.0
14
0.0
10.0
16
0.0
19
0.0
15
0.0
13
0.0
098
La139
0.0
045
0.0
042
0.0
042
0.4
80.5
0.1
40.1
50.1
50.0
037
0.0
038
0.0
037
0.0
081
0.0
01
Ce1
40
0.0
17
0.0
18
0.0
18
0.7
80.8
30.4
70.4
90.4
90.0
17
0.0
17
0.0
18
0.0
051
0.0
0081
Pr1
41
0.0
093
0.0
089
0.0
086
0.0
76
0.0
83
0.0
75
0.0
76
0.0
78
0.0
077
0.0
087
0.0
09
0.0
013
0.0
0028
Nd
143
0.0
96
0.0
85
0.0
94
0.2
80.3
30.3
90.4
0.4
10.0
89
0.0
89
0.0
89
0.0
22
0.0
042
Sm
147
0.0
71
0.0
78
0.0
78
0.0
48
0.0
59
0.0
93
0.0
90.0
99
0.0
72
0.0
73
0.0
76
0.0
045
0.0
02
Eu
151
0.0
35
0.0
34
0.0
35
0.0
19
0.0
24
0.0
28
0.0
28
0.0
29
0.0
33
0.0
32
0.0
33
0.0
011
0.0
018
Gd
157
0.1
20.1
10.1
10.0
29
0.0
34
0.0
59
0.0
60.0
62
0.1
10.1
0.1
0.0
12
<0.0
0
Tb
159
0.0
19
0.0
20.0
19
0.0
027
0.0
037
0.0
063
0.0
07
0.0
068
0.0
17
0.0
18
0.0
17
0.0
0031
<0.0
0
Dy163
0.1
10.1
20.1
20.0
08
0.0
11
0.0
25
0.0
28
0.0
24
0.1
10.1
10.1
10.0
024
0.0
029
Ho165
0.0
26
0.0
27
0.0
25
0.0
018
0.0
03
0.0
042
0.0
042
0.0
042
0.0
26
0.0
25
0.0
27
0.0
0054
<0.0
0
Er1
67
0.0
79
0.0
75
0.0
78
0.0
069
0.0
071
0.0
12
0.0
12
0.0
11
0.0
80.0
76
0.0
75
0.0
051
<0.0
0
Tm
169
0.0
13
0.0
14
0.0
13
0.0
0098
0.0
082
0.0
015
0.0
02
0.0
016
0.0
13
0.0
12
0.0
13
0.0
0041
0.0
0056
Yb
171
0.0
93
0.0
92
0.0
83
0.0
059
0.0
029
0.0
095
0.0
093
0.0
10.0
85
0.0
85
0.0
86
0.0
053
0.0
042
Lu
175
0.0
15
0.0
15
0.0
14
0.0
008
0.0
01
0.0
015
0.0
015
0.0
013
0.0
13
0.0
14
0.0
13
0.0
04
0.0
0079
Hf1
78
0.0
26
0.0
29
0.0
28
0.0
038
0.0
023
0.0
84
0.0
87
0.0
88
0.0
22
0.0
23
0.0
26
1.3
51.4
Ta181
0.0
016
0.0
016
0.0
013
0.0
0056
0.0
011
0.0
022
0.0
026
0.0
031
0.0
0082
0.0
0099
0.0
0085
11.6
711.9
Pb
208
0.0
063
0.0
058
0.0
075
0.2
0.2
0.0
18
0.0
19
0.0
17
0.0
023
0.0
036
0.0
033
0.0
07
0.0
03
Th
232
0.0
016
0.0
017
0.0
015
<0.0
00.0
02
0.0
021
0.0
062
0.0
02
0.0
016
0.0
014
0.0
012
0.0
075
0.0
0077
U238
0.0
023
0.0
015
0.0
014
0.0
014
0.0
0059
0.0
012
0.0
014
0.0
042
0.0
011
0.0
01
0.0
018
0.0
65
0.0
67
Pm
147
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
Po208
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
U232
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
Pu
238
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
106
SA
MP
LE
MV
P99-2
-12
GL
ITT
ER
!: M
inim
um
det
ecti
on
lim
its
(99%
con
fid
ence
).
Ele
men
t99-2
-12-s
pt2
-scp
-a99-2
-12-s
pt2
-scp
-b99-2
-12-s
pt2
-grt
-a99-2
-12-s
pt2
-grt
-b99-2
-12-s
pt2
-cp
x-a
99-2
-12-s
pt2
-cp
x-b
99-2
-12-s
pt2
-scp
-c99-2
-12-s
pt2
-scp
-d99-2
-12-s
pt3
-scp
-a99-2
-12-s
pt3
-scp
-b99-2
-12-s
pt3
-pl-
a99-2
-12-s
pt3
-pl-
b
Li7
2.78
2.66
2.69
2.58
1.54
1.7
2.39
2.7
2.21
1.99
2.37
2.43
Mg24
4.54
4.77
4.91
4.75
2.76
3.53
4.61
5.02
3.94
3.89
4.49
4.63
Si2
935
65.0
332
21.2
628
96.4
832
05.3
216
81.0
720
19.2
327
88.2
734
64.0
525
4324
11.8
628
59.5
2961
.55
P31
40.8
839
.87
41.0
739
.97
22.6
725
.32
35.9
539
.71
32.2
730
.34
34.5
936
.48
Ca43
0.03
30.
0313
0.03
20.
0318
0.01
740.
0202
0.02
850.
0308
0.02
450.
0243
0.02
650.
0285
Sc4
50.
380.
372
0.38
70.
380.
213
0.24
40.
358
0.40
30.
317
0.29
60.
351
0.36
6
Ti4
91.
271.
261.
451.
290.
723
1.04
1.41
1.34
1.15
0.72
71.
231.
16
V51
0.09
530.
104
0.10
60.
103
0.05
850.
0869
0.11
50.
102
0.08
530.
0834
0.10
40.
107
Cr5
22.
592.
452.
512.
41.
371.
52.
172.
412.
011.
882.
142.
27
Ni6
03.
112.
993.
133.
161.
791.
952.
913.
182.
522.
492.
752.
95
Cu
65
0.97
70.
974
0.96
71.
030.
572
0.59
90.
902
1.01
0.79
50.
785
0.88
90.
955
Rb
85
0.07
420.
043
0.04
460.
0427
0.02
760.
0311
0.04
230.
0456
0.03
530.
0395
0.04
390.
049
Sr8
80.
0097
20.
0118
0.01
710.
0178
0.00
627
0.01
640.
0173
0.11
80.
0121
0.01
760.
015
0.02
63
Y89
0.01
690.
021
0.02
10.
0205
0.01
170.
0126
0.01
970.
0186
0.01
60.
0177
0.01
880.
0221
Zr9
00.
0484
0.04
810.
0541
0.05
780.
0275
0.03
660.
0509
0.04
770.
0401
0.04
240.
0458
0.04
87
Nb
93
0.01
010.
0087
2<
0.00
000
0.00
727
0.00
292
0.00
572
0.00
465
<0.
0000
00.
0059
30.
0071
0.00
816
0.00
493
Cs1
33
0.00
571
0.00
672
0.00
780.
0051
90.
0041
70.
0052
70.
0074
20.
0079
80.
0082
0.00
548
0.00
858
0.00
964
Ba137
0.04
50.
049
0.05
790.
0457
0.02
60.
0473
0.04
130.
0663
0.05
280.
040.
0622
0.03
92
La139
0.00
468
0.00
425
0.00
275
0.00
614
0.00
247
0.00
352
0.00
496
0.00
844
0.00
354
0.01
440.
0030
80.
0041
6
Ce1
40
<0.
0000
00.
0045
70.
0038
10.
0026
9<
0.00
000
0.00
423
0.00
344
0.01
290.
0031
10.
0021
50.
0034
90.
0025
8
Pr1
41
0.00
413
0.00
290.
0042
0.00
210.
0023
80.
0030
10.
0026
80.
0037
20.
0024
20.
0037
40.
0019
20.
0034
9
Nd
143
0.01
77<
0.00
000
0.01
80.
0312
<0.
0000
00.
0163
<0.
0000
0<
0.00
000
0.02
08<
0.00
000
0.03
30.
0173
Sm
147
<0.
0000
00.
029
0.02
1<
0.00
000
0.01
880.
0095
10.
0134
0.02
150.
0209
0.02
36<
0.00
000
0.01
42
Eu
151
0.00
550.
0044
70.
0064
6<
0.00
000
0.00
318
0.00
207
0.00
505
0.00
331
0.00
263
<0.
0000
00.
0029
60.
0053
6
Gd
157
0.01
450.
0144
0.03
30.
0256
0.00
839
0.00
947
0.02
670.
0303
<0.
0000
00.
0167
<0.
0000
00.
02
Tb
159
0.00
579
0.00
377
0.00
315
0.00
223
0.00
126
0.00
202
0.00
201
<0.
0000
00.
0025
7<
0.00
000
0.00
204
0.00
478
Dy163
0.01
23<
0.00
000
0.01
250.
0216
<0.
0000
0<
0.00
000
<0.
0000
00.
0128
0.00
719
0.00
703
0.00
808
<0.
0000
0
Ho165
<0.
0000
00.
0031
30.
0022
60.
0032
0.00
129
0.00
205
0.00
457
<0.
0000
0<
0.00
000
<0.
0000
00.
0036
0.00
486
Er1
67
0.01
560.
0089
50.
013
0.02
050.
0090
10.
0083
10.
0082
70.
0093
80.
0167
0.00
73<
0.00
000
0.01
76
Tm
169
<0.
0000
0<
0.00
000
0.00
470.
0029
70.
0016
90.
0019
10.
0019
0.00
431
0.00
171
0.00
290.
0019
30.
0020
2
Yb
171
0.02
150.
0214
0.02
19<
0.00
000
0.01
24<
0.00
000
0.02
42<
0.00
000
0.01
260.
0175
<0.
0000
00.
021
Lu
175
<0.
0000
00.
0023
5<
0.00
000
0.00
340.
0013
70.
0021
80.
0021
70.
0042
70.
0019
60.
0027
10.
0031
20.
0023
1
Hf1
78
0.00
859
0.01
210.
0124
0.00
873
<0.
0000
00.
0097
1<
0.00
000
0.00
895
0.00
712
0.01
210.
0080
10.
0118
Ta181
0.00
657
0.00
292
0.00
299
0.00
298
<0.
0000
00.
0019
20.
0038
1<
0.00
000
<0.
0000
00.
0023
80.
0038
7<
0.00
000
Pb
208
0.01
140.
0065
60.
015
0.00
671
0.00
934
0.00
963
0.00
858
0.01
190.
0094
90.
012
0.01
070.
0064
4
Th
232
<0.
0000
0<
0.00
000
0.00
568
0.00
733
0.00
323
<0.
0000
0<
0.00
000
0.00
476
0.00
379
0.00
454
0.00
739
0.00
546
U238
0.00
539
0.00
437
0.00
448
0.00
316
0.00
254
0.00
203
0.00
496
0.00
460.
0036
6<
0.00
000
0.00
505
0.00
61
Pm
147
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
Po208
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
U232
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
Pu
238
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
107
SA
MP
LE
MV
P99
-2-1
2
GL
ITT
ER
!: M
inim
um
det
ecti
on l
imit
s (9
9% c
onfi
den
ce).
Ele
men
t99
-2-1
2-sp
t3-g
rt-a
99-2
-12-
spt3
-grt
-b99
-2-1
2-sp
t3-g
rt-c
99-2
-12-
spt1
-scp
-a99
-2-1
2-sp
t1-s
cp-b
99-2
-12-
spt1
-cp
x-a
99-2
-12-
spt1
-cp
x-b
99-2
-12-
spt1
-cp
x-c
99-2
-12-
spt4
-grt
-a99
-2-1
2-sp
t4-g
rt-b
99-2
-12-
spt4
-grt
-c99
-2-1
2-sp
t4-r
t-a
99-2
-12-
spt4
-rt-
b
Li7
2.08
1.92
1.87
1.63
1.49
1.12
1.13
1.11
1.51
1.44
1.63
1.08
0.95
9
Mg2
43.
94.
195.
063.
213.
062.
142.
222.
333.
273.
153.
322.
412.
31
Si2
926
31.3
121
40.1
122
55.2
1950
.78
1771
.37
1408
.75
1345
.28
1271
.24
2178
2046
.89
2178
.49
1250
.81
1198
.86
P31
30.3
528
.62
28.1
725
.29
22.7
316
.19
16.6
516
.57
23.8
822
.18
23.9
316
.82
16.6
8
Ca4
30.
0241
0.02
190.
0217
0.02
040.
0181
0.01
240.
0131
0.01
320.
0191
0.01
720.
0181
91.6
789
.51
Sc4
50.
310.
290.
30.
253
0.22
70.
161
0.17
40.
172
0.24
30.
232
0.24
10.
167
0.16
6
Ti4
90.
888
1.11
1.24
0.90
40.
766
0.56
10.
562
0.52
30.
821
0.68
40.
788
0.00
009
0.00
025
V51
0.09
210.
0845
0.09
640.
0727
0.06
550.
0488
0.04
740.
0488
0.06
430.
0699
0.06
470.
0462
0.04
16
Cr5
21.
91.
781.
751.
581.
410.
999
1.03
1.04
1.52
1.41
1.5
1.07
0.97
7
Ni6
02.
52.
372.
32.
041.
861.
351.
371.
421.
961.
881.
981.
351.
3
Cu
650.
785
0.74
40.
764
0.59
10.
595
0.42
50.
432
0.41
80.
643
0.59
40.
666
0.40
70.
409
Rb
850.
0346
0.03
450.
0319
0.03
190.
0257
0.01
940.
020.
0209
0.03
110.
0256
0.02
650.
0185
0.02
08
Sr8
80.
0113
0.00
832
0.01
180.
0096
10.
0119
0.00
792
0.00
690.
0063
10.
0106
0.00
923
0.00
982
0.00
624
0.00
634
Y89
0.01
80.
0168
0.01
490.
0145
0.01
240.
0086
30.
010.
0095
0.01
270.
0124
0.01
640.
0074
30.
0084
3
Zr9
00.
0445
0.04
680.
0416
0.03
140.
0321
0.02
390.
0272
0.02
380.
0326
0.03
20.
036
0.02
010.
0264
Nb
93<
0.00
000
0.00
388
0.00
391
0.00
473
0.00
31<
0.00
000
<0.
0000
00.
0023
30.
0045
20.
0030
50.
0056
2<
0.00
000
0.02
12
Cs1
330.
0076
0.00
621
0.00
559
0.00
535
0.00
520.
0033
50.
0034
60.
0044
10.
0526
0.00
598
0.00
677
0.00
262
0.00
373
Ba1
370.
0499
0.05
360.
0348
0.02
660.
0428
0.03
050.
034
0.02
940.
0382
0.04
210.
0317
0.02
770.
0234
La1
390.
0027
30.
0036
0.00
331
0.00
40.
0023
50.
0026
50.
0084
10.
0021
60.
0029
60.
0034
60.
0021
30.
0026
30.
0018
8
Ce1
400.
0021
90.
0020
40.
0020
50.
0386
<0.
0000
00.
0011
60.
0012
0.00
212
0.00
168
<0.
0000
00.
0017
0.00
211
<0.
0000
0
Pr1
410.
0024
10.
0035
50.
0027
70.
0019
30.
0017
90.
0015
70.
0018
60.
0019
10.
0034
60.
0012
50.
0018
80.
0016
40.
0009
1
Nd
143
0.02
53<
0.00
000
0.01
37<
0.00
000
0.01
540.
0134
0.00
8<
0.00
000
0.01
120.
0151
0.01
61<
0.00
000
0.00
779
Sm
147
<0.
0000
0<
0.00
000
0.01
590.
0096
4<
0.00
000
0.01
280.
0093
0.00
951
<0.
0000
00.
0124
0.01
620.
0094
30.
0063
9
Eu
151
0.00
371
0.00
488
0.00
347
0.00
42<
0.00
000
0.00
197
0.01
310.
0029
30.
0044
90.
0027
10.
0045
60.
0029
10.
0019
7
Gd
157
<0.
0000
00.
0158
<0.
0000
00.
0136
<0.
0000
00.
009
0.00
928
0.00
671
0.01
30.
0087
80.
0162
0.00
667
0.00
904
Tb
159
0.00
181
0.00
292
0.00
170.
0020
5<
0.00
000
0.00
136
0.00
171
0.00
143
0.00
196
0.00
132
0.00
199
0.00
101
0.00
167
Dy1
63<
0.00
000
<0.
0000
00.
0067
10.
0081
2<
0.00
000
0.00
537
0.00
554
0.00
401
<0.
0000
0<
0.00
000
<0.
0000
00.
0056
40.
0054
1
Ho1
650.
0018
40.
0038
30.
0017
30.
0029
50.
0019
4<
0.00
000
<0.
0000
0<
0.00
000
0.00
245
0.00
234
0.00
203
<0.
0000
00.
0017
1
Er1
670.
0105
0.01
20.
0121
0.01
340.
0055
40.
0068
40.
0070
60.
0072
2<
0.00
000
0.00
945
0.00
581
0.00
832
0.00
564
Tm
169
0.00
242
0.00
159
0.00
358
<0.
0000
00.
0022
0.00
091
<0.
0000
0<
0.00
000
0.00
131
0.00
125
0.00
231
<0.
0000
00.
0015
8
Yb
171
0.02
180.
0203
0.02
04<
0.00
000
0.00
937
0.00
945
0.00
689
0.01
41<
0.00
000
0.01
850.
0098
20.
0172
0.01
17
Lu
175
0.00
339
0.00
257
0.00
183
0.00
157
<0.
0000
00.
0010
4<
0.00
000
0.00
189
0.00
212
0.00
286
0.00
264
0.00
188
0.00
233
Hf1
780.
010.
0132
0.00
940.
0098
60.
0074
70.
0037
6<
0.00
000
<0.
0000
00.
0109
0.00
735
0.00
553
0.00
684
0.00
535
Ta1
81<
0.00
000
0.00
391
<0.
0000
0<
0.00
000
0.00
180.
0012
90.
0026
50.
0013
60.
0018
6<
0.00
000
<0.
0000
00.
0013
50.
0046
6
Pb
208
0.00
546
0.00
880.
0102
0.00
759
0.00
406
0.00
410.
0079
10.
0030
60.
0072
60.
0056
60.
0042
60.
0030
50.
0041
3
Th
232
0.00
463
0.00
431
0.00
355
<0.
0000
00.
0034
5<
0.00
000
0.01
770.
0015
0.00
356
0.00
34<
0.00
000
<0.
0000
00.
0014
4
U23
80.
0044
80.
0024
10.
0024
20.
0020
70.
0019
30.
0013
70.
002
0.00
145
0.00
281
0.00
190.
0028
60.
0020
60.
0014
Pm
147
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00
Po2
08<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
U23
2<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
Pu
238
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00
108
SA
MP
LE
MV
P99-2
-12
GL
ITT
ER
!: M
ean
Raw
CP
S b
ack
gro
un
d s
ub
tract
ed.
Ele
men
t99-2
-12-s
pt2
-scp
-a99-2
-12-s
pt2
-scp
-b99-2
-12-s
pt2
-grt
-a99-2
-12-s
pt2
-grt
-b99-2
-12-s
pt2
-cp
x-a
99-2
-12-s
pt2
-cp
x-b
99-2
-12-s
pt2
-scp
-c99-2
-12-s
pt2
-scp
-d99-2
-12-s
pt3
-scp
-a99-2
-12-s
pt3
-scp
-b99-2
-12-s
pt3
-pl-
a99-2
-12-s
pt3
-pl-
b
Li7
128
172
048
446
392
405
454
245
329
20
21
Mg24
28474
27450
1244758
1270721
1951493
1831521
29852
27113
34026
34863
3312
3103
Si2
91638
1558
1522
1505
2809
2671
1562
1501
1942
2018
2282
2181
P31
1812
1816
352
359
442
144
1638
1792
2549
2737
288
201
Ca43
38566
38807
18579
19206
78080
72539
40124
37105
45876
47700
20363
19475
Sc4
50
017594
18401
13862
12901
24
00
170
80
110
Ti4
95182
5246
20507
18040
146596
137715
5482
5046
6201
6549
2773
2558
V51
247
167
55687
51505
276083
255879
194
227
225
295
120
152
Cr5
20
058798
59966
92535
87704
00
00
00
Ni6
00
103
1133
1157
14970
14200
00
00
89
0
Cu
65
00
105
7299
297
45
029
13
40
Rb
85
066
12
57
078
53
60
42
116
131
Sr8
81201670
1226913
167
195
131051
122642
1327455
1213879
1470862
1567511
1666404
1545145
Y89
152
155
12824
13315
2321
2094
174
145
199
179
13
6
Zr9
056
60
9184
7981
37350
35021
50
60
88
83
12
6
Nb
93
08
10
1259
182
24
22
20
18
05
Cs1
33
15
60
14
43
12
60
50
0
Ba137
9109
9515
30
43
10468
9475
11506
12234
24773
22757
La139
18222
18803
49
30
9656
8818
20177
18779
22477
24205
4989
4610
Ce1
40
31364
32054
507
458
33987
32028
34098
31636
38594
41623
6342
5784
Pr1
41
3939
3904
245
252
6991
6511
4218
3913
4750
5263
656
622
Nd
143
1527
1597
314
337
4100
3834
1726
1494
1902
1931
190
170
Sm
147
169
203
343
360
999
960
225
176
240
269
21
15
Eu
151
321
295
587
632
1042
938
338
325
401
414
257
224
Gd
157
108
82
562
526
577
524
86
72
91
66
11
1
Tb
159
21
37
668
688
407
334
39
32
41
47
80
Dy163
30
20
1156
1196
348
321
33
23
38
39
14
Ho165
25
9947
1011
189
205
612
19
24
00
Er1
67
34
655
681
81
76
84
44
20
Tm
169
21
438
446
39
41
40
20
21
Yb
171
40
461
435
27
21
04
42
50
Lu
175
27
411
401
711
20
08
01
Hf1
78
21
165
120
1515
1445
20
25
00
Ta181
04
08
34
43
00
21
00
Pb
208
1674
1663
17
45
176
191
1904
1676
1965
2210
1738
1572
Th
232
44
00
24
21
50
00
02
U238
00
24
117
01
24
00
Pm
147
169
203
343
360
999
960
225
176
240
269
21
15
Po208
1674
1663
17
45
176
191
1904
1676
1965
2210
1738
1572
U232
44
00
24
21
50
00
02
Pu
238
00
24
117
01
24
00
109
SA
MP
LE
MV
P9
9-2
-12
GL
ITT
ER
!: M
ean
Ra
w C
PS
ba
ckg
rou
nd
su
btr
act
ed.
Ele
men
t9
9-2
-12
-sp
t3-g
rt-a
99
-2-1
2-s
pt3
-grt
-b9
9-2
-12
-sp
t3-g
rt-c
99
-2-1
2-s
pt1
-scp
-a9
9-2
-12
-sp
t1-s
cp-b
99
-2-1
2-s
pt1
-cp
x-a
99
-2-1
2-s
pt1
-cp
x-b
99
-2-1
2-s
pt1
-cp
x-c
99
-2-1
2-s
pt4
-grt
-a9
9-2
-12
-sp
t4-g
rt-b
99
-2-1
2-s
pt4
-grt
-c9
9-2
-12
-sp
t4-r
t-a
99
-2-1
2-s
pt4
-rt-
b
Li7
00
92
51
66
60
64
56
84
75
54
95
40
01
4
Mg
24
15
74
55
71
66
45
32
16
90
37
64
30
63
46
49
12
62
19
82
26
03
82
52
57
31
84
20
20
91
72
08
15
32
19
55
83
12
46
17
72
62
Si2
91
98
82
02
61
99
32
41
02
66
03
92
83
86
13
78
02
51
82
64
62
50
25
26
P3
12
99
54
47
19
32
00
39
75
54
85
18
53
75
63
79
66
42
18
20
Ca
43
23
60
92
45
83
25
21
15
83
69
62
92
11
04
96
61
00
21
09
80
45
29
66
83
06
18
28
77
91
12
62
Sc4
52
23
99
23
59
02
35
96
01
66
18
57
11
78
97
17
37
42
94
19
30
59
72
90
15
29
21
29
09
Ti4
92
61
78
27
84
42
72
05
77
97
88
87
19
51
16
19
02
32
18
61
67
30
50
73
30
71
31
29
31
86
44
59
41
91
48
61
0
V5
17
00
07
72
99
27
34
50
32
74
04
37
03
87
35
74
38
35
50
09
89
63
99
48
01
88
89
41
05
80
87
10
65
77
4
Cr5
27
11
61
73
53
07
55
71
00
12
63
80
12
45
26
12
64
76
17
31
67
18
63
67
17
62
47
30
16
52
30
47
95
Ni6
01
59
81
69
31
70
68
71
39
20
29
92
00
67
20
22
01
71
71
90
41
87
75
01
64
Cu
65
53
74
62
20
45
48
74
68
46
85
99
14
13
34
32
9
Rb
85
64
48
08
91
02
30
02
00
19
52
0
Sr8
86
50
10
54
88
71
87
78
22
20
91
44
11
82
43
31
68
17
61
67
91
12
80
31
12
98
18
76
19
32
Y8
91
72
26
18
04
81
80
26
23
12
17
29
80
28
97
29
24
20
48
92
19
02
20
46
53
29
17
3
Zr9
01
22
45
13
56
21
26
62
84
10
55
08
87
49
91
14
87
13
12
58
51
35
12
12
71
11
06
71
20
11
02
64
9
Nb
93
21
15
12
15
42
30
13
17
25
29
79
52
63
10
55
47
82
33
Cs1
33
29
21
03
11
27
31
35
27
70
00
07
37
0
Ba137
65
17
91
61
49
30
20
72
62
03
00
00
34
0
La139
61
53
59
29
44
53
27
76
13
12
51
28
44
12
75
35
96
35
84
15
3
Ce1
40
62
16
95
69
65
01
76
57
09
14
70
19
46
08
44
55
86
80
77
99
79
62
15
7
Pr1
41
36
43
49
35
36
18
47
07
49
59
59
22
69
24
53
66
46
24
46
20
0
Nd
14
34
76
41
95
07
24
16
28
40
55
27
53
34
53
71
56
45
89
54
31
09
1
Sm
14
74
13
49
05
09
30
73
46
13
77
12
38
13
54
56
35
92
56
91
0
Eu
15
18
43
84
68
98
47
75
43
14
23
12
79
13
62
10
05
10
03
96
60
10
Gd
15
78
22
81
58
64
12
71
33
77
37
43
75
29
63
91
28
81
48
0
Tb
15
99
51
10
42
10
06
49
71
50
25
32
49
91
05
01
15
01
01
00
0
Dy
16
31
48
01
70
61
69
02
63
84
73
52
34
08
18
84
19
56
18
80
03
Ho
16
51
34
81
45
01
39
81
44
32
52
23
52
23
16
53
16
76
17
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171
0.33
0.32
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344
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175
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043
1.12
50.
0416
0.04
030.
0433
<0.
0014
60.
0019
70.
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20.
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5
Hf1
782.
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50.
0071
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0.27
70.
326
2.67
72.
617
2.72
20.
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32.9
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8.66
5.85
8.71
Pb
208
0.08
180.
1118
1.22
1.20
80.
0242
0.01
810.
1152
0.11
390.
1127
1.12
31.
118
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0.37
70.
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232
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0.16
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238
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112
SAM
PL
E M
VP
99-2
-22
GL
ITT
ER
!: 1
sig
ma
erro
r.
Ele
men
t99
-2-2
2-sp
t4-g
rt-a
99-2
-22-
spt4
-grt
-b99
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2-sp
t4-g
rt-c
99-2
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spt4
-pl-
a99
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2-sp
t4-p
l-b
99-2
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spt4
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c99
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2-sp
t4-p
l-d
99-2
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spt4
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t4-c
px-a
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2-sp
t4-c
px-c
99-2
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spt5
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2-sp
t5-g
rt-b
Li7
0.63
0.62
0.62
0.34
0.31
0.53
0.61
0.29
1.9
1.56
1.49
0.62
0.63
Mg2
483
05.4
383
89.4
7990
.94
17.5
913
.217
.42
13.2
715
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64.9
188
23.7
588
24.0
487
91.4
283
81.1
1
Si29
3781
681.
2535
9567
1.75
3525
617.
546
4188
946
9204
0.5
4741
772.
546
9703
1.5
4652
524.
541
8474
639
5728
4.75
3851
250.
7534
3555
4.5
3279
689
P31
72.4
510
1.57
72.0
217
.41
16.9
615
.524
.67
24.8
334
.83
26.2
614
.28
86.1
262
.39
Ca4
30.
140.
140.
140.
120.
120.
120.
120.
120.
40.
40.
40.
140.
14
Sc45
1.94
1.95
1.91
0.06
0.05
60.
092
0.09
50.
054
1.14
1.11
1.09
1.93
1.85
Ti4
935
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35.8
135
.41
5.46
5.15
5.66
5.35
5.24
143.
2914
0.64
142.
0536
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35.1
8
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4.61
4.71
4.55
0.03
0.02
70.
039
0.04
20.
027
14.2
713
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744.
44
Cr5
211
.98
12.1
11.8
80.
360.
330.
580.
60.
3110
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819.
6816
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15.3
2
Ni6
01.
341.
31.
360.
450.
420.
730.
770.
48.
637.
77.
751.
441.
41
Cu6
50.
290.
280.
250.
140.
130.
250.
280.
130.
290.
270.
280.
320.
27
Rb8
50.
012
0.01
20.
019
0.02
50.
023
0.02
70.
028
0.02
30.
008
0.00
680.
0062
0.01
20.
012
Sr88
0.00
830.
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8724
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24.3
624
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24.7
11.
561.
471.
50.
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0.00
77
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1.76
1.74
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470.
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580.
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84
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310.
320.
310.
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0.36
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250.
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0.00
130.
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0.00
230.
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130.
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0.00
120.
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0.00
270.
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Ba1
370.
018
0.01
90.
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3.51
3.53
3.59
3.61
3.68
0.02
40.
010.
0097
0.02
0.01
6
La1
390.
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0.00
190.
002
0.03
10.
031
0.03
20.
034
0.03
20.
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058
0.05
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0.00
22
Ce1
400.
0063
0.00
720.
0061
0.03
50.
036
0.03
80.
040.
036
0.18
0.18
0.18
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480.
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0.00
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40.
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Nd1
430.
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30.
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40.
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20.
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230.
240.
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70.
055
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40.
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0.00
70.
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0.01
10.
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0.00
630.
10.
095
0.1
0.06
20.
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Eu1
510.
035
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70.
034
0.01
30.
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0.01
70.
016
0.01
30.
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0.04
10.
040.
037
0.03
7
Gd1
570.
130.
150.
140.
0057
0.00
610.
0089
0.00
810.
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0.11
0.1
0.11
0.16
0.15
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590.
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0.03
40.
033
0.00
066
0.00
091
0.00
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0.00
088
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710.
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210.
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340.
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30.
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0.00
069
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20.
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0.00
260.
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780.
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50.
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0.00
270.
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0.00
150.
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0.00
140.
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0.07
80.
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810.
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0.00
110.
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80.
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10.
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80.
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490.
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80.
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42
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320.
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130.
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50.
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50.
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0.00
60.
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0.00
20.
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80.
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40.
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113
SA
MP
LE
MV
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sig
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t9
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px
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9-2
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t5-p
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99
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b
Li7
1.85
1.44
0.37
0.37
0.36
0.35
1.3
1.64
1.69
0.39
0.42
0.53
0.86
1.38
Mg
24
8870
.37
9469
.88
20.3
13.5
390
08.8
588
69.2
296
31.8
191
30.4
694
49.6
117
.78
24.4
716
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2507
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27.9
4
Si2
940
1571
3.75
3727
457
4960
402.
550
2885
1.5
3256
496.
7533
2973
438
8544
038
9604
2.25
4052
172.
550
0699
8.5
5174
837
2412
9.3
4966
25.6
986
61.1
6
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137
.75
20.9
638
.48
31.6
410
8.18
92.8
621
.89
24.4
622
.538
.41
33.2
9.1
17.4
312
.92
Ca
43
0.4
0.39
0.12
0.12
0.14
0.14
0.4
0.4
0.4
0.12
0.12
37.7
577
.76
37.5
Sc4
51.
11.
10.
065
0.06
31.
941.
941.
111.
131.
110.
070.
066
0.12
0.62
0.12
Ti4
913
8.58
136.
895.
395.
2836
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38.5
714
4.51
143.
7814
5.48
5.56
5.63
2.33
1.45
2.33
V5
113
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13.4
20.
036
0.02
94.
744.
8814
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14.2
214
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0.03
80.
039
15.4
619
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13.0
4
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212
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11.7
40.
370.
3623
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19.6
518
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19.4
40.
40.
3914
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28.6
912
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Ni6
08.
327.
450.
490.
481.
091.
238.
098.
148.
170.
540.
520.
576.
440.
54
Cu
65
0.28
0.22
0.17
0.15
0.2
0.19
0.24
0.23
0.26
0.17
0.17
0.27
0.52
0.24
Rb
85
0.00
80.
0039
0.02
70.
027
0.00
790.
0079
0.00
530.
0092
0.00
50.
027
0.02
80.
0081
0.04
10.
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Sr8
81.
481.
4925
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26.4
60.
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0.00
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541.
581.
5726
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26.9
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043
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6
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240.
240.
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340.
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970.
380.
41.
41.
431.
410.
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Nb
93
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0009
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110.
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140.
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130.
0009
0.00
162.
70.
92.
74
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33
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80.
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170.
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50.
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50.
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150.
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0.00
540.
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Ba137
0.01
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3.82
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840.
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0.00
160.
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10.
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0.00
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015
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27
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40
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630.
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0.03
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0.00
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0.02
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0013
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41
0.03
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0.00
510.
0048
0.00
340.
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0.03
50.
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Nd
14
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Sm
14
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440.
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32
Eu
15
10.
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038
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50.
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40.
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10.
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50.
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Gd
15
70.
110.
099
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580.
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0.15
0.17
0.11
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70.
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38
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15
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16
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0.00
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70.
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840.
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Er1
67
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022
0.00
280.
0025
0.2
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0.02
30.
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50.
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0.00
350.
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Tm
16
90.
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0.00
270.
0007
30.
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30.
029
0.03
20.
003
0.00
30.
003
0.00
055
0.00
057
0.00
049
0.00
60.
0004
6
Yb
17
10.
021
0.01
50.
0026
0.00
30.
180.
190.
017
0.01
70.
016
0.00
40.
0038
0.00
540.
038
0.00
28
Lu
17
50.
0026
0.00
220.
0004
0.00
038
0.02
80.
030.
0024
0.00
230.
0023
0.00
062
0.00
082
0.00
071
0.00
650.
0002
9
Hf1
78
0.08
20.
077
0.00
210.
002
0.01
50.
017
0.08
50.
083
0.08
60.
0033
0.00
111.
040.
671.
06
Ta
18
10.
0006
30.
0005
70.
0003
40.
0003
30.
0005
90.
0007
60.
0006
10.
0005
50.
0006
20.
0007
80.
0006
30.
270.
20.
27
Pb
20
80.
0078
0.00
750.
065
0.06
40.
004
0.00
330.
0082
0.00
820.
008
0.06
20.
062
0.00
290.
034
0.00
39
Th
23
20.
0027
0.00
170.
001
0.00
065
0.00
086
0.00
086
0.00
170.
0016
0.00
210.
0011
0.00
040.
015
0.00
630.
0008
3
U2
38
0.00
120.
0007
20.
0013
0.00
036
0.00
091
0.00
063
0.00
090.
0008
20.
0009
0.00
084
0.00
120.
037
0.01
60.
036
Pm
14
7<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00
Po
20
8<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00
U2
32
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
Pu
23
8<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00<
0.00
<0.
00
114
SA
MP
LE
MV
P99-2
-22
GL
ITT
ER
!: M
inim
um
dete
cti
on
lim
its
(99%
con
fid
en
ce).
Ele
men
t99-2
-22-s
pt4
-grt-
a99-2
-22-s
pt4
-grt-
b99-2
-22-s
pt4
-grt-
c99-2
-22-s
pt4
-pl-
a99-2
-22-s
pt4
-pl-
b99-2
-22-s
pt4
-pl-
c99-2
-22-s
pt4
-pl-
d99-2
-22-s
pt4
-pl-
e99-2
-22-s
pt4
-cp
x-a
99-2
-22-s
pt4
-cp
x-b
99-2
-22-s
pt4
-cp
x-c
99-2
-22-s
pt5
-grt-
a99-2
-22-s
pt5
-grt-
b
Li7
1.4
11.3
71.2
50.7
44
0.7
1.2
31.3
40.6
71
0.8
68
0.7
08
0.7
29
1.4
21.3
Mg24
2.9
93.1
2.7
31.8
81.7
22.9
23.1
41.5
92.1
41.7
1.7
13.4
93.3
7
Si2
91923.5
71678.9
81874.4
41133.1
8948.1
61915.3
31865.6
1915.3
1292.6
11034.2
1101.4
12028.8
2020.3
P31
24.0
923.4
421.1
913.0
812.3
121.2
322.2
711.2
814.8
811.8
211.9
124.4
122.3
4
Ca43
0.0
199
0.0
19
0.0
17
0.0
105
0.0
0955
0.0
174
0.0
176
0.0
0896
0.0
119
0.0
0946
0.0
0923
0.0
19
0.0
171
Sc45
0.2
25
0.2
22
0.2
04
0.1
30.1
19
0.2
07
0.2
22
0.1
17
0.1
48
0.1
20.1
17
0.2
46
0.2
28
Ti4
90.8
21
0.7
18
0.7
01
0.4
57
0.4
15
0.7
05
0.7
06
0.4
06
0.6
21
0.4
06
0.3
74
0.8
10.7
74
V51
0.0
609
0.0
595
0.0
614
0.0
332
0.0
29
0.0
668
0.0
685
0.0
36
0.0
447
0.0
342
0.0
338
0.0
745
0.0
615
Cr52
1.5
11.4
51.3
20.8
0.7
48
1.3
41.3
90.6
99
0.9
34
0.7
39
0.7
32
1.5
51.3
9
Ni6
01.7
61.8
21.6
11
0.9
62
1.6
81.7
80.9
02
1.2
20.9
74
0.9
68
1.9
41.7
8
Cu
65
0.5
68
0.5
84
0.5
19
0.3
21
0.3
12
0.5
10.6
90.3
0.4
03
0.3
07
0.3
16
0.6
37
0.5
87
Rb
85
0.0
29
0.0
276
0.0
487
0.0
168
0.0
153
0.0
273
0.0
278
0.0
146
0.0
183
0.0
164
0.0
147
0.0
277
0.0
299
Sr88
0.0
108
0.0
094
0.0
0816
0.0
0475
0.0
0852
0.0
0949
0.0
105
0.0
0566
0.0
0674
0.0
0516
0.0
0638
0.0
064
0.0
0718
Y89
0.0
112
0.0
123
0.0
123
0.0
0661
0.0
0704
0.0
117
0.0
114
0.0
0635
0.0
0757
0.0
0606
0.0
0726
0.0
115
0.0
137
Zr90
0.0
302
0.0
311
0.0
28
0.0
164
0.0
175
0.0
279
0.0
321
0.0
165
0.0
229
0.0
183
0.0
168
0.0
357
0.0
25
Nb
93
0.0
0521
0.0
0296
0.0
027
0.0
0234
0.0
016
<0.0
0000
<0.0
0000
0.0
0216
0.0
0204
0.0
0163
0.0
0162
0.0
0335
0.0
0614
Cs1
33
0.0
061
0.0
0541
0.0
0512
0.0
0222
0.0
0325
0.0
06
0.0
049
0.0
03
0.0
0273
0.0
0261
0.0
0285
0.0
0589
0.0
0562
Ba137
0.0
45
0.0
427
0.0
324
0.0
229
0.0
169
0.0
229
0.0
244
0.0
173
0.0
399
0.0
226
0.0
225
0.0
464
0.0
476
La139
0.0
0361
0.0
0355
0.0
0324
0.0
0154
0.0
0136
0.0
0243
0.0
0232
0.0
0183
0.0
0189
0.0
0175
0.0
0151
0.0
0312
0.0
0286
Ce140
<0.0
0000
0.0
0312
<0.0
0000
0.0
0213
0.0
0119
0.0
0151
0.0
0278
0.0
0139
0.0
0186
0.0
0171
0.0
0171
0.0
0176
0.0
0162
Pr141
0.0
0276
0.0
0172
0.0
0156
0.0
0068
0.0
0131
0.0
0204
0.0
0177
0.0
014
0.0
0221
0.0
0094
0.0
0149
0.0
0238
0.0
0178
Nd
143
0.0
106
0.0
104
0.0
134
0.0
0824
0.0
0975
0.0
101
0.0
215
<0.0
0000
<0.0
0000
0.0
0573
<0.0
0000
<0.0
0000
0.0
286
Sm
147
0.0
0869
<0.0
0000
0.0
078
0.0
0478
0.0
0462
0.0
143
0.0
0882
<0.0
0000
0.0
0588
0.0
0471
<0.0
0000
0.0
168
0.0
125
Eu
151
0.0
0379
<0.0
0000
0.0
038
<0.0
0000
0.0
0225
0.0
0255
0.0
0272
<0.0
0000
0.0
0181
0.0
0145
0.0
0144
0.0
0517
<0.0
0000
Gd
157
0.0
15
0.0
0854
0.0
156
0.0
0676
0.0
0653
0.0
166
0.0
125
0.0
0882
0.0
118
<0.0
0000
0.0
105
0.0
168
0.0
0887
Tb
159
0.0
0131
<0.0
0000
0.0
0166
0.0
0125
0.0
0121
<0.0
0000
0.0
0188
0.0
0133
0.0
0125
<0.0
0000
0.0
01
0.0
0146
<0.0
0000
Dy163
0.0
0734
0.0
0511
0.0
0806
<0.0
0000
<0.0
0000
<0.0
0000
0.0
0527
0.0
0264
0.0
0352
<0.0
0000
0.0
028
0.0
0579
0.0
075
Ho165
0.0
0189
0.0
0186
0.0
0169
0.0
0104
0.0
0071
0.0
0127
0.0
0192
0.0
0136
0.0
0091
0.0
0102
0.0
0072
<0.0
0000
0.0
0193
Er167
0.0
0764
0.0
0752
0.0
108
0.0
0595
0.0
0498
0.0
0892
<0.0
0000
0.0
0614
0.0
0732
0.0
0293
0.0
0583
0.0
0603
0.0
0782
Tm
169
<0.0
0000
0.0
0211
<0.0
0000
<0.0
0000
0.0
0093
0.0
0118
0.0
0178
<0.0
0000
<0.0
0000
0.0
0067
0.0
0067
0.0
0138
0.0
022
Yb
171
<0.0
0000
<0.0
0000
0.0
0819
0.0
0711
0.0
0972
0.0
195
0.0
131
0.0
0464
0.0
0875
0.0
099
0.0
0493
0.0
144
0.0
0934
Lu
175
0.0
0283
0.0
0311
0.0
0127
<0.0
0000
0.0
0075
0.0
0135
0.0
0203
0.0
0072
<0.0
0000
0.0
0077
0.0
0108
<0.0
0000
<0.0
0000
Hf1
78
0.0
089
0.0
113
0.0
0652
0.0
0566
0.0
0273
0.0
049
0.0
0904
0.0
0369
0.0
0492
0.0
0482
0.0
048
0.0
081
0.0
0525
Ta181
0.0
0351
0.0
0173
<0.0
0000
0.0
0193
0.0
0132
0.0
0334
<0.0
0000
0.0
0089
<0.0
0000
0.0
0134
0.0
0134
0.0
0276
0.0
0179
Pb
208
0.0
097
0.0
0872
0.0
0711
0.0
0436
0.0
0365
0.0
10.0
09
0.0
0403
0.0
0537
0.0
144
0.0
0302
0.0
0625
0.0
0993
Th
232
0.0
0195
0.0
0332
0.0
0247
<0.0
0000
0.0
0147
<0.0
0000
0.0
0443
0.0
161
0.0
0229
0.0
0106
<0.0
0000
0.0
0218
0.0
0346
U238
0.0
0266
0.0
0186
0.0
0415
<0.0
0000
0.0
0174
0.0
018
0.0
0192
0.0
0136
<0.0
0000
0.0
0145
0.0
0204
0.0
0422
0.0
0274
Pm
147
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
Po208
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
U232
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
Pu
238
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
115
SA
MP
LE
MV
P99-2
-22
GL
ITT
ER
!: M
inim
um
dete
cti
on
lim
its
(99%
con
fid
en
ce).
Ele
men
t99-2
-22-s
pt5
-cp
x-a
99-2
-22-s
pt5
-cp
x-b
99-2
-22-s
pt5
-pl-
a99-2
-22-s
pt5
-pl-
b99-2
-22-s
pt6
-grt-
a99-2
-22-s
pt6
-grt-
b99-2
-22-s
pt6
-cp
x-a
99-2
-22-s
pt6
-cp
x-b
99-2
-22-s
pt6
-cp
x-c
99-2
-22-s
pt6
-pl-
a99-2
-22-s
pt6
-pl-
b99-2
-22-r
t-a
99-2
-22-i
lm-a
99-2
-22-r
t-b
Li7
0.9
18
0.4
82
0.8
21
0.7
72
0.8
18
0.8
18
0.5
52
0.5
11
0.5
21
0.8
90.8
44
1.0
20.8
51
0.9
57
Mg24
2.2
71.1
82.1
12
1.9
92.1
81.4
11.4
31.4
72.3
72.2
92.4
52.0
62.3
Si2
91254.0
8693.4
61114.0
31033.5
91097.0
91169.8
766.6
7698.8
9640.4
31231.9
91256.6
11385.1
51055.3
31220.8
4
P31
14.8
28.2
13.5
212.9
913.7
13.6
79.1
68.7
28.3
915.0
414.0
615.3
314
14.6
4
Ca43
0.0
11
0.0
0635
0.0
104
0.0
102
0.0
105
0.0
105
0.0
073
0.0
0699
0.0
0675
0.0
114
0.0
11
85.3
476.8
85.0
6
Sc45
0.1
56
0.0
831
0.1
42
0.1
35
0.1
41
0.1
42
0.0
996
0.0
949
0.0
891
0.1
56
0.1
49
0.1
61
0.1
40.1
47
Ti4
90.4
62
0.2
55
0.4
23
0.4
31
0.4
32
0.3
82
0.2
94
0.3
20.2
68
0.5
12
0.4
40.0
0009
0.0
0009
0.0
0008
V51
0.1
17
0.0
233
0.0
346
0.0
40.0
40.0
431
0.0
304
0.0
25
0.0
264
0.0
526
0.0
412
0.0
509
0.0
412
0.0
43
Cr52
0.9
30.5
14
0.8
52
0.8
34
0.9
01
0.8
79
0.5
90.5
61
0.5
32
0.9
39
0.8
99
1.0
10.8
61
0.9
17
Ni6
01.2
20.6
49
1.1
31.1
1.1
21.1
10.7
64
0.7
35
0.6
84
1.2
41.1
91.3
1.1
21.2
Cu
65
0.3
83
0.2
34
0.3
96
0.3
58
0.3
75
0.3
82
0.2
38
0.2
42
0.2
38
0.4
14
0.3
98
0.4
04
0.3
42
0.4
23
Rb
85
0.0
19
0.0
089
0.0
129
0.0
171
0.0
186
0.0
156
0.0
13
0.0
235
0.0
125
0.0
194
0.0
162
0.0
18
0.0
168
0.0
185
Sr88
0.0
0523
0.0
0309
0.0
0724
0.0
0928
0.0
0407
0.0
0623
0.0
0308
0.0
0364
0.0
0351
0.0
0552
0.0
0618
0.0
0515
0.0
0526
0.0
043
Y89
0.0
0769
0.0
0446
0.0
061
0.0
0764
0.0
0691
0.0
0713
0.0
0558
0.0
0472
0.0
0478
0.0
089
0.0
0916
0.0
0838
0.0
0648
0.0
0804
Zr90
0.0
241
0.0
106
0.0
172
0.0
198
0.0
20.0
198
0.0
119
0.0
146
0.0
125
0.0
205
0.0
192
0.0
203
0.0
222
0.0
215
Nb
93
0.0
0293
<0.0
0000
0.0
0268
0.0
026
0.0
0191
0.0
0197
0.0
0264
<0.0
0000
<0.0
0000
<0.0
0000
0.0
0355
0.0
022
0.0
0276
<0.0
0000
Cs1
33
0.0
0393
0.0
0184
0.0
0373
0.0
0428
0.0
0375
0.0
0245
0.0
0212
0.0
0224
0.0
0207
0.0
189
0.0
039
0.0
0316
0.0
028
0.0
0251
Ba137
0.0
248
0.0
112
0.0
201
0.0
285
0.0
324
0.0
344
0.0
14
0.0
176
0.0
12
0.0
291
0.0
26
0.2
02
0.0
246
0.0
342
La139
0.0
0157
0.0
0087
0.0
0176
0.0
0185
0.0
0217
0.0
028
0.0
0123
0.0
0137
0.0
0104
0.0
0235
0.0
0206
0.0
062
0.0
0128
0.0
023
Ce140
<0.0
0000
0.0
006
0.0
01
<0.0
0000
0.0
0174
0.0
0147
0.0
0069
0.0
0095
<0.0
0000
<0.0
0000
0.0
0108
0.0
0116
0.0
0103
<0.0
0000
Pr141
0.0
0147
0.0
0081
0.0
0174
0.0
0107
<0.0
0000
0.0
0081
0.0
0076
0.0
0157
<0.0
0000
0.0
0201
0.0
0084
0.0
0181
0.0
008
0.0
0165
Nd
143
0.0
103
0.0
057
0.0
163
<0.0
0000
<0.0
0000
0.0
0693
0.0
0656
0.0
0448
<0.0
0000
0.0
0771
0.0
0722
0.0
0774
0.0
097
0.0
0709
Sm
147
0.0
0846
<0.0
0000
0.0
0774
0.0
0531
0.0
0551
0.0
114
0.0
0381
0.0
0367
<0.0
0000
0.0
0632
0.0
103
0.0
127
<0.0
0000
0.0
0582
Eu
151
0.0
0261
0.0
0102
0.0
0119
0.0
0164
0.0
0208
0.0
0175
0.0
0144
0.0
0196
0.0
0134
0.0
039
0.0
0129
0.0
0367
0.0
0174
0.0
022
Gd
157
0.0
0598
0.0
0331
0.0
0548
0.0
0531
0.0
078
0.0
0569
<0.0
0000
0.0
0973
0.0
0502
<0.0
0000
<0.0
0000
0.0
0636
0.0
0796
<0.0
0000
Tb
159
0.0
009
<0.0
0000
<0.0
0000
0.0
0113
0.0
0118
0.0
0149
0.0
0115
0.0
0096
<0.0
0000
0.0
0096
0.0
0127
0.0
0096
0.0
012
0.0
0088
Dy163
0.0
0506
0.0
0198
0.0
0464
0.0
0318
0.0
033
0.0
0482
0.0
0228
0.0
0311
0.0
03
0.0
0536
<0.0
0000
0.0
0659
<0.0
0000
0.0
0348
Ho165
0.0
0092
0.0
0114
0.0
0119
0.0
0082
<0.0
0000
0.0
0124
<0.0
0000
0.0
0057
0.0
0077
0.0
0098
0.0
0129
0.0
0139
0.0
0087
0.0
009
Er167
0.0
0745
0.0
0291
0.0
0683
0.0
0469
0.0
0595
0.0
0615
0.0
0412
0.0
0459
<0.0
0000
0.0
0559
0.0
0827
0.0
056
0.0
0496
0.0
131
Tm
169
0.0
0121
<0.0
0000
0.0
0175
0.0
0132
<0.0
0000
<0.0
0000
0.0
0109
0.0
0091
0.0
0072
0.0
0157
0.0
0085
0.0
0158
<0.0
0000
0.0
0083
Yb
171
0.0
0891
0.0
0603
<0.0
0000
0.0
056
0.0
101
0.0
06
0.0
0803
<0.0
0000
0.0
0374
0.0
116
0.0
108
0.0
0947
<0.0
0000
<0.0
0000
Lu
175
0.0
0098
0.0
0076
<0.0
0000
0.0
0087
0.0
009
0.0
0161
0.0
0124
0.0
006
0.0
0058
0.0
0146
0.0
0137
0.0
0104
0.0
013
0.0
0095
Hf1
78
0.0
0501
0.0
0277
<0.0
0000
0.0
0445
0.0
0326
0.0
0584
0.0
0319
0.0
0218
0.0
0297
0.0
053
0.0
0351
0.0
0376
0.0
0333
<0.0
0000
Ta181
0.0
0171
0.0
0116
0.0
0111
0.0
0107
0.0
0111
0.0
0115
0.0
0133
0.0
0105
0.0
0072
0.0
0221
0.0
012
0.0
0128
0.0
0161
0.0
0204
Pb
208
0.0
0611
0.0
0151
0.0
0501
0.0
0486
0.0
0437
0.0
0368
0.0
0174
0.0
0168
0.0
0281
<0.0
0000
0.0
0543
0.0
0581
0.0
0446
0.0
0461
Th
232
<0.0
0000
0.0
0075
0.0
0247
<0.0
0000
0.0
0176
0.0
0223
0.0
0086
0.0
0083
0.0
0179
0.0
032
<0.0
0000
0.0
0321
0.0
0254
0.0
0186
U238
0.0
0261
0.0
0162
0.0
0169
0.0
0116
0.0
0241
<0.0
0000
0.0
0083
0.0
014
0.0
011
0.0
0241
0.0
0225
0.0
0241
0.0
0213
0.0
0221
Pm
147
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
Po208
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
U232
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
Pu
238
<0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0<
0.0
0
116
SA
MP
LE
MV
P99
-2-2
2
GL
ITT
ER
!: M
ean
Raw
CP
S b
ack
grou
nd
su
btr
acte
d.
Ele
men
t99
-2-2
2-sp
t4-g
rt-a
99-2
-22-
spt4
-grt
-b99
-2-2
2-sp
t4-g
rt-c
99-2
-22-
spt4
-pl-
a99
-2-2
2-sp
t4-p
l-b
99-2
-22-
spt4
-pl-
c99
-2-2
2-sp
t4-p
l-d
99-2
-22-
spt4
-pl-
e99
-2-2
2-sp
t4-c
px-
a99
-2-2
2-sp
t4-c
px-
b99
-2-2
2-sp
t4-c
px-
c99
-2-2
2-sp
t5-g
rt-a
99-2
-22-
spt5
-grt
-b
Li7
00
00
06
03
529
554
529
049
Mg2
417
6354
917
1744
218
1075
763
3349
5837
3526
8460
2424
7497
632
1521
932
1039
415
5993
115
8698
9
Si2
927
6725
5127
8458
8162
4336
3034
2764
7243
6652
3751
2022
4322
99
P31
732
1003
791
291
300
134
234
479
506
484
251
796
617
Ca4
322
776
2210
224
624
3285
834
537
1988
318
968
3618
796
654
1227
0812
3361
1992
321
407
Sc4
529
591
2879
931
549
172
296
145
2122
725
159
3102
130
621
2611
126
976
Ti4
932
019
3097
634
207
8190
8121
4968
4452
8665
1864
5923
2386
2357
0729
184
2999
2
V51
6662
865
859
7107
937
434
117
720
734
329
9334
3702
1237
1716
6085
161
424
Cr5
212
0169
1175
2712
8647
00
00
494
1467
7517
9178
1774
2214
3119
1459
31
Ni6
012
0810
7513
7410
010
3877
9014
291
1615
116
315
1114
1214
Cu
6512
475
810
010
30
036
747
250
012
157
Rb
850
00
633
627
338
342
631
20
00
0
Sr8
884
120
125
1464
716
1543
547
8887
4384
5843
1627
424
7687
792
097
9419
710
886
Y89
7061
967
538
7578
691
6223
3299
1292
015
436
1525
465
293
6901
0
Zr9
058
0056
7361
7613
030
134
3720
145
653
4554
958
9962
81
Nb
930
00
01
02
016
1014
10
Cs1
330
50
150
00
18
20
34
Ba1
370
09
4986
152
745
3046
629
079
5702
965
30
00
La1
3924
715
3189
3418
1864
1899
3670
5302
6649
6744
1519
Ce1
4021
023
722
738
9441
7624
4424
0544
3217
752
2221
022
307
209
228
Pr1
4111
014
914
046
645
326
332
351
343
6153
4454
6111
613
4
Nd
143
269
235
239
203
204
119
112
207
3373
4076
4148
224
225
Sm
147
428
507
450
2743
2219
3015
2518
7621
1542
552
5
Eu
151
1192
1220
1265
662
707
470
402
746
2255
2991
2894
1109
1236
Gd
157
1386
1569
1592
1420
78
717
4120
3821
7014
5815
07
Tb
159
2663
2589
2822
317
71
1315
7718
0118
1524
8626
02
Dy1
6351
2449
4858
5620
238
49
1661
2035
2224
4821
5320
Ho1
6550
7649
0657
508
44
10
1105
1271
1220
4921
5142
Er1
6739
0336
4941
855
60
51
481
558
606
3581
3705
Tm
169
2592
2489
2854
16
70
423
227
929
724
7826
54
Yb
171
2474
2341
2678
30
05
116
719
819
723
5824
81
Lu
175
2634
2375
2931
114
40
011
316
113
623
3925
86
Hf1
7811
910
912
52
30
00
2035
2542
2451
139
136
Ta1
810
31
04
01
32
51
00
Pb
208
49
1514
7315
2688
983
715
7013
269
131
40
Th
232
40
78
04
00
6854
592
0
U23
81
10
40
15
04
51
05
Pm
147
428
507
450
2743
2219
3015
2518
7621
1542
552
5
Po2
084
915
1473
1526
889
837
1570
132
6913
14
0
U23
24
07
80
40
068
5459
20
Pu
238
11
04
01
50
45
10
5
117
SA
MP
LE
MV
P99
-2-2
2
GL
ITT
ER
!: M
ean
Raw
CP
S b
ack
grou
nd
su
btr
acte
d.
Ele
men
t99
-2-2
2-sp
t5-c
px-
a99
-2-2
2-sp
t5-c
px-
b99
-2-2
2-sp
t5-p
l-a
99-2
-22-
spt5
-pl-
b99
-2-2
2-sp
t6-g
rt-a
99-2
-22-
spt6
-grt
-b99
-2-2
2-sp
t6-c
px-
a99
-2-2
2-sp
t6-c
px-
b99
-2-2
2-sp
t6-c
px-
c99
-2-2
2-sp
t6-p
l-a
99-2
-22-
spt6
-pl-
b99
-2-2
2-rt
-a99
-2-2
2-il
m-a
99-2
-22-
rt-b
Li7
516
776
2340
60
598
776
843
220
013
032
4
Mg2
424
7582
849
7856
960
7940
7926
5432
225
9390
141
8025
140
1227
343
4333
946
0066
1732
8558
8011
5941
Si2
941
7373
4156
2257
8436
6437
4365
2166
6472
9751
3255
720
503
0
P31
553
583
619
515
1754
1506
523
599
581
565
512
00
147
Ca4
394
939
1800
6629
776
3024
336
871
3686
115
7760
1608
9016
9504
2706
928
454
5759
90
Sc4
524
043
4606
418
629
045
900
4607
639
474
4099
342
647
213
134
1590
1261
218
06
Ti4
917
9217
3363
3071
5771
3251
072
5321
730
1582
3055
7532
5444
6638
7085
1925
6414
1381
2733
2008
2030
V51
2881
3553
1947
454
269
1060
2210
9039
4847
8748
8512
5180
7635
646
932
2393
4559
8728
3600
Cr5
217
5293
3181
310
2336
3345
3633
1145
1335
4382
9747
8046
284
021
3679
5001
0819
9322
Ni6
013
551
2306
50
4516
1619
0021
057
2152
022
705
3854
7012
172
86
Cu
6534
960
70
015
512
255
352
866
90
032
857
720
7
Rb
850
961
860
20
380
00
521
578
854
923
Sr8
872
111
1372
1713
6052
314
0897
821
821
011
9226
1242
0313
0047
1245
645
1318
960
2004
7388
2244
Y89
1259
623
714
108
6211
2856
1161
0021
075
2160
722
616
5857
210
3191
173
Zr9
036
320
6921
534
2510
653
1129
260
616
6331
365
335
1634
6644
3344
3282
6984
57
Nb
9311
120
01
523
618
31
1325
3948
988
1401
36
Cs1
330
00
00
30
05
00
478
24
Ba1
370
2247
044
4790
90
021
1613
4247
645
529
065
939
0
La1
3952
9398
6631
3632
3827
1787
0789
0994
7628
4529
670
585
69
Ce1
4017
403
3275
237
5237
8739
330
528
528
2968
131
667
3342
3758
115
9020
Pr1
4142
4481
9242
841
223
522
670
8974
5877
6643
841
00
206
913
Nd
143
3291
6368
192
200
395
499
5157
5699
6012
160
189
317
11
Sm
147
1593
2854
3932
792
802
2528
2572
2869
3027
049
1
Eu
151
2185
4204
679
704
1983
2257
3708
3863
4180
596
643
048
3
Gd
157
1627
3091
1423
2680
2996
2743
2787
2920
2124
196
6
Tb
159
1501
2702
223
4506
4558
2410
2444
2589
89
312
14
Dy1
6317
2733
028
1588
6191
0128
1930
3931
172
90
216
1
Ho1
6510
2419
423
480
5384
8717
4417
1617
672
01
265
0
Er1
6750
190
80
357
9960
0678
983
894
47
01
163
0
Tm
169
229
407
00
3684
4064
360
359
409
04
016
61
Yb
171
151
281
31
3407
3667
238
260
265
00
412
43
Lu
175
108
239
30
3347
3611
199
196
223
06
414
60
Hf1
7820
5438
646
024
428
735
3435
2338
597
025
623
1783
827
425
Ta1
810
30
01
41
310
01
1976
515
335
2073
6
Pb
208
8622
314
0614
1327
2019
619
820
611
7212
274
436
22
Th
232
6188
04
10
6155
940
156
668
0
U23
82
111
00
416
717
04
1469
403
1506
Pm
147
1593
2854
3932
792
802
2528
2572
2869
3027
049
1
Po2
0886
223
1406
1413
2720
196
198
206
1172
1227
443
622
U23
261
880
41
061
5594
01
566
680
Pu
238
21
110
04
167
170
414
6940
315
06
118
SAM
PLE
MV
P1
04
38
GLI
TTER
!: T
race
Ele
me
nt
Co
nce
ntr
atio
ns
MD
L fi
lte
red
.
Ele
me
nt
10
43
8A
-sp
t1-o
px-
a1
04
38
A-s
pt1
-op
x-b
10
43
8A
-sp
t1-c
px-
a1
04
38
A-s
pt1
-cp
x-b
10
43
8A
-sp
t4-s
cp-a
10
43
8A
-sp
t4-s
cp-b
10
43
8A
-sp
t2-s
cp-a
10
43
8A
-sp
t2-p
l-a
10
43
8A
-sp
t2-c
px-
a
Li7
5.9
38
.02
7.4
98
.53
2.3
5<0
.86
25
.7<0
.79
6.6
9
Mg2
41
72
10
3.7
17
96
12
.03
80
11
2.1
68
18
86
.09
77
9.7
49
2.5
77
47
99
.71
76
19
1.8
5
Si2
93
18
40
6.7
23
34
38
42
42
18
3.5
52
42
68
9.5
62
14
83
6.0
62
73
94
9.8
82
09
43
9.7
32
75
00
62
32
55
4.7
5
P3
1<1
0.4
5<1
0.9
23
7.8
82
6.6
74
58
.73
12
8.0
24
19
.93
92
.72
63
.25
Ca4
30
.71
0.7
12
2.5
22
2.5
21
9.1
21
9.1
21
8.5
91
7.8
22
2.1
6
Sc4
55
0.6
85
3.0
61
40
.69
13
0.9
0.1
52
0.1
98
0.2
72
<0.1
52
12
5.9
8
Ti4
98
54
.03
69
2.7
54
41
7.2
83
38
22
43
.64
17
.56
12
5.4
92
1.1
63
69
5.5
V5
12
91
.36
31
3.9
85
44
.91
53
9.6
80
.23
30
.26
40
.15
20
.29
25
07
.75
Cr5
22
06
.66
23
0.2
62
91
.99
29
0.0
7<0
.77
<1.0
2<0
.81
<0.9
52
77
.81
Ni6
01
82
.69
20
5.1
38
7.1
48
7.5
5<0
.94
<1.3
2<0
.97
<1.1
58
6.8
8
Cu
65
5.2
5.3
23
.73
4.4
5<0
.35
<0.4
10
.91
<0.4
33
.69
Rb
85
<0.0
12
7<0
.01
40
0.0
09
90
.00
95
0.5
10
.11
30
.41
60
.15
2<0
.00
90
Sr8
80
.06
49
0.0
42
21
8.4
62
0.1
24
89
.76
23
.36
47
4.7
75
87
.71
7.8
1
Y8
91
.58
31
.66
82
0.3
31
9.6
81
.88
60
.16
21
.84
90
.12
63
20
.24
Zr9
00
.99
0.9
02
15
.58
15
.06
<0.0
15
2<0
.02
17
<0.0
16
90
.03
15
.16
Nb
93
0.0
03
8<0
.00
14
9<0
.00
19
10
.00
16
6<0
.00
27
6<0
.00
22
<0.0
00
.00
60
.00
14
7
Cs1
33
<0.0
02
05
<0.0
02
30
.06
52
<0.0
02
14
0.0
19
0.0
04
10
.01
36
0.0
05
1<0
.00
15
4
Ba1
37
<0.0
16
2<0
.02
31
0.0
21
2<0
.01
48
26
.35
26
.72
26
.14
27
.91
<0.0
19
7
La1
39
0.0
14
60
.03
29
1.4
61
1.4
73
8.3
91
.92
38
.35
1.8
04
1.5
2
Ce
14
00
.05
79
0.0
79
26
.89
6.6
91
6.0
62
.89
21
6.2
92
.76
6.9
9
Pr1
41
0.0
09
70
.01
31
.40
31
.44
51
.75
60
.28
1.7
78
0.2
58
1.4
22
Nd
14
30
.08
86
0.1
23
8.9
8.9
27
0.9
35
7.3
90
.80
99
.12
Sm1
47
0.0
21
0.0
44
93
.43
.31
1.0
13
0.1
37
1.0
07
0.1
21
3.1
83
Eu1
51
0.0
20
20
.01
33
0.9
47
0.9
50
.53
10
.38
30
.53
70
.37
30
.97
2
Gd
15
70
.09
99
0.0
80
13
.83
3.7
0.7
33
0.0
65
20
.76
90
.06
18
3.8
2
Tb1
59
0.0
22
40
.02
12
0.6
42
0.6
45
0.0
93
30
.00
49
0.0
75
8<0
.00
20
0.6
56
Dy1
63
0.2
10
.23
44
.12
3.9
90
.42
70
.03
26
0.4
12
0.0
38
94
.01
Ho
16
50
.05
53
0.0
63
40
.82
60
.82
50
.06
95
0.0
01
76
0.0
58
10
.00
69
0.8
39
Er1
67
0.2
09
0.2
62
.18
92
.18
10
.13
30
.01
58
0.1
76
0.0
11
12
.20
6
Tm1
69
0.0
45
0.0
52
10
.32
26
0.3
14
90
.02
62
<0.0
01
31
0.0
19
9<0
.00
40
0.3
31
Yb
17
10
.45
70
.46
61
.99
42
.11
50
.09
80
.00
78
0.0
89
20
.01
04
2.1
27
Lu1
75
0.0
64
70
.08
41
0.2
93
20
.28
83
0.0
17
5<0
.00
10
60
.01
69
<0.0
00
96
0.3
00
8
Hf1
78
0.0
52
30
.04
38
0.7
57
0.6
75
0.0
03
<0.0
08
6<0
.00
65
<0.0
04
90
.64
6
Ta1
81
<0.0
01
11
<0.0
01
23
0.0
03
53
0.0
01
29
<0.0
01
32
<0.0
01
31
<0.0
01
71
<0.0
01
19
<0.0
01
09
Pb
20
80
.00
6<0
.00
84
0.0
67
30
.05
99
1.2
89
1.0
58
1.2
94
1.0
72
0.0
64
9
Th2
32
0.0
06
50
.00
21
90
.01
84
0.0
18
8<0
.00
21
<0.0
00
.00
50
.00
35
0.0
21
U2
38
<0.0
01
21
<0.0
01
90
0.0
02
09
0.0
03
48
0.0
01
1<0
.00
20
2<0
.00
24
1<0
.00
22
4<0
.00
09
7
Pm
14
7<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
Po
20
8<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
U2
32
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN
Pu
23
8<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
119
SAM
PLE
MV
P1
04
38
GLI
TTER
!: 1
sig
ma
err
or.
Ele
me
nt
10
43
8A
-sp
t1-o
px-
a1
04
38
A-s
pt1
-op
x-b
10
43
8A
-sp
t1-c
px-
a1
04
38
A-s
pt1
-cp
x-b
10
43
8A
-sp
t4-s
cp-a
10
43
8A
-sp
t4-s
cp-b
10
43
8A
-sp
t2-s
cp-a
10
43
8A
-sp
t2-p
l-a
10
43
8A
-sp
t2-c
px-
a
Li7
1.3
31
.78
1.6
61
.88
7.1
50
.38
5.7
10
.42
1.5
1
Mg2
42
54
78
.75
26
72
6.0
91
19
49
.41
12
27
4.5
31
17
.55
14
.12
11
3.7
11
5.3
51
17
11
.05
Si2
95
01
26
60
.55
26
61
26
38
15
48
7.7
53
82
48
66
.75
33
87
13
44
32
07
20
.53
30
44
87
.25
43
40
57
4.5
36
71
89
5.5
P3
14
.57
4.8
22
3.1
11
6.4
72
76
.52
77
.44
25
2.8
75
6.2
33
8.1
9
Ca4
30
.01
90
.02
0.5
30
.53
0.4
50
.45
0.4
40
.42
0.5
2
Sc4
51
.38
1.4
63
.56
3.3
10
.06
30
.07
30
.05
70
.07
33
.2
Ti4
92
4.3
31
9.9
21
17
.39
90
.06
6.9
50
.77
3.6
0.9
99
.2
V5
18
.19
8.8
91
4.3
41
4.2
20
.02
60
.02
80
.01
90
.02
81
3.4
7
Cr5
26
.47
7.2
68
.69
8.6
50
.41
0.4
50
.37
0.4
58
.38
Ni6
09
.75
11
.01
4.6
34
.67
0.5
10
.58
0.4
30
.55
4.7
3
Cu
65
0.3
20
.34
0.2
40
.28
0.1
80
.18
0.1
70
.20
.24
Rb
85
0.0
05
40
.00
59
0.0
04
40
.00
42
0.0
29
0.0
12
0.0
22
0.0
15
0.0
03
8
Sr8
80
.00
46
0.0
03
80
.59
0.6
41
5.6
11
9.9
21
5.2
11
8.9
30
.58
Y8
90
.05
50
.05
80
.64
0.6
20
.06
70
.01
0.0
63
0.0
09
20
.65
Zr9
00
.03
70
.03
50
.47
0.4
60
.00
81
0.0
09
80
.00
80
.01
0.4
7
Nb
93
0.0
01
40
.00
04
60
.00
08
10
.00
05
50
.00
08
50
.00
12
<0.0
00
.00
17
0.0
00
49
Cs1
33
0.0
00
95
0.0
01
0.0
03
50
.00
08
20
.00
28
0.0
01
80
.00
20
.00
17
0.0
00
66
Ba1
37
0.0
06
60
.00
85
0.0
06
40
.00
66
0.8
90
.89
0.8
70
.94
0.0
07
2
La1
39
0.0
01
50
.00
24
0.0
45
0.0
45
0.2
50
.06
10
.25
0.0
58
0.0
47
Ce
14
00
.00
31
0.0
04
0.2
0.1
90
.46
0.0
86
0.4
70
.08
40
.2
Pr1
41
0.0
01
10
.00
13
0.0
39
0.0
40
.05
20
.01
0.0
50
.01
0.0
4
Nd
14
30
.00
94
0.0
11
0.2
60
.26
0.2
30
.04
60
.23
0.0
44
0.2
7
Sm1
47
0.0
04
10
.00
63
0.1
0.1
0.0
50
.01
30
.04
20
.01
40
.09
8
Eu1
51
0.0
02
10
.00
18
0.0
27
0.0
27
0.0
21
0.0
15
0.0
18
0.0
16
0.0
27
Gd
15
70
.00
88
0.0
08
20
.11
0.1
10
.04
10
.00
91
0.0
34
0.0
10
.12
Tb1
59
0.0
01
60
.00
16
0.0
18
0.0
18
0.0
05
40
.00
11
0.0
03
80
.00
11
0.0
18
Dy1
63
0.0
11
0.0
12
0.1
20
.12
0.0
24
0.0
05
20
.01
90
.00
59
0.1
2
Ho
16
50
.00
29
0.0
03
20
.02
40
.02
40
.00
47
0.0
00
96
0.0
03
30
.00
13
0.0
25
Er1
67
0.0
11
0.0
13
0.0
67
0.0
67
0.0
12
0.0
03
50
.01
10
.00
47
0.0
68
Tm1
69
0.0
02
40
.00
27
0.0
09
90
.00
97
0.0
02
70
.00
05
90
.00
17
0.0
01
30
.01
Yb
17
10
.02
10
.02
20
.05
80
.06
10
.01
40
.00
44
0.0
09
50
.00
50
.06
1
Lu1
75
0.0
03
90
.00
38
0.0
08
70
.00
86
0.0
02
30
.00
05
80
.00
17
0.0
00
65
0.0
08
8
Hf1
78
0.0
05
0.0
04
70
.02
80
.02
50
.00
17
0.0
02
70
.00
22
0.0
03
0.0
24
Ta1
81
0.0
00
41
0.0
00
61
0.0
00
69
0.0
00
38
0.0
00
92
0.0
00
58
0.0
00
61
0.0
00
62
0.0
00
55
Pb
20
80
.00
19
0.0
03
30
.00
55
0.0
05
10
.07
60
.06
20
.07
40
.06
50
.00
53
Th2
32
0.0
01
10
.00
09
30
.00
17
0.0
01
70
.00
13
<0.0
00
.00
10
.00
14
0.0
01
6
U2
38
0.0
00
66
0.0
00
74
0.0
00
59
0.0
00
73
0.0
00
64
0.0
00
90
.00
08
20
.00
07
0.0
00
51
Pm
14
7<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
Po
20
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
U2
32
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
Pu
23
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
120
SAM
PLE
MV
P1
04
38
GLI
TTER
!: M
inim
um
de
tect
ion
lim
its
(99
% c
on
fid
en
ce).
Ele
me
nt
10
43
8A
-sp
t1-o
px-
a1
04
38
A-s
pt1
-op
x-b
10
43
8A
-sp
t1-c
px-
a1
04
38
A-s
pt1
-cp
x-b
10
43
8A
-sp
t4-s
cp-a
10
43
8A
-sp
t4-s
cp-b
10
43
8A
-sp
t2-s
cp-a
10
43
8A
-sp
t2-p
l-a
10
43
8A
-sp
t2-c
px-
a
Li7
0.5
84
0.5
73
0.4
37
0.4
52
0.6
45
0.8
58
0.6
67
0.7
94
0.4
21
Mg2
41
.47
1.8
21
.28
1.3
71
.78
2.6
41
.92
2.3
41
.26
Si2
97
50
.44
91
3.4
76
69
61
1.7
29
50
.58
12
75
.91
10
35
.41
12
81
.78
61
9.1
2
P3
11
0.4
51
0.9
27
.86
8.2
11
1.4
61
5.2
51
1.9
11
3.7
97
.29
Ca4
30
.00
83
70
.00
91
30
.00
67
20
.00
68
20
.00
88
40
.01
24
0.0
09
45
0.0
11
10
.00
56
9
Sc4
50
.10
20
.10
70
.08
03
0.0
83
70
.11
40
.16
20
.12
30
.15
20
.07
73
Ti4
90
.34
70
.38
80
.26
10
.33
10
.37
80
.58
30
.47
10
.50
10
.26
1
V5
10
.02
79
0.0
31
60
.02
37
0.0
24
20
.03
33
0.0
48
40
.03
46
0.0
39
60
.02
44
Cr5
20
.67
0.6
99
0.5
21
0.5
37
0.7
69
1.0
20
.80
90
.94
60
.48
1
Ni6
00
.79
10
.85
80
.64
70
.68
30
.93
91
.32
0.9
68
1.1
50
.60
9
Cu
65
0.2
38
0.2
73
0.2
13
0.2
22
0.3
46
0.4
10
.33
40
.43
10
.21
9
Rb
85
0.0
12
70
.01
40
.00
96
10
.00
92
30
.01
46
0.0
18
70
.01
55
0.0
17
90
.00
89
8
Sr8
80
.00
38
50
.00
40
10
.00
36
30
.00
36
90
.00
33
90
.02
34
0.0
03
21
0.0
07
47
0.0
04
33
Y8
90
.00
57
0.0
05
09
0.0
04
66
0.0
05
98
0.0
06
35
0.0
09
81
0.0
06
70
.00
84
0.0
04
17
Zr9
00
.01
24
0.0
14
20
.01
03
0.0
12
60
.01
52
0.0
21
70
.01
69
0.0
18
70
.01
2
Nb
93
0.0
02
33
0.0
01
49
0.0
01
91
<0.0
00
00
0.0
02
76
0.0
02
23
<0.0
00
00
<0.0
00
00
<0.0
00
00
Cs1
33
0.0
02
05
0.0
02
27
0.0
02
02
0.0
02
14
0.0
02
69
0.0
03
41
0.0
02
71
0.0
02
52
0.0
01
54
Ba1
37
0.0
16
20
.02
31
0.0
11
70
.01
48
0.0
16
90
.11
30
.01
51
0.0
27
0.0
19
7
La1
39
0.0
01
45
0.0
01
50
.00
11
10
.00
08
90
.00
14
90
.00
33
0.0
01
11
0.0
02
04
0.0
01
29
Ce
14
0<0
.00
00
00
.00
15
70
.00
05
80
.01
54
0.0
01
46
0.0
02
36
0.0
01
26
<0.0
00
00
0.0
00
57
Pr1
41
0.0
01
24
0.0
01
37
0.0
01
01
0.0
01
07
0.0
00
66
0.0
01
84
0.0
01
83
0.0
01
18
0.0
00
44
Nd
14
30
.00
82
20
.00
74
10
.00
54
80
.00
41
20
.00
79
50
.01
58
0.0
10
30
.01
01
0.0
05
34
Sm1
47
0.0
03
89
0.0
06
08
0.0
04
50
.00
33
8<0
.00
00
0<0
.00
00
00
.00
84
3<0
.00
00
00
.00
31
Eu1
51
0.0
01
20
.00
09
40
.00
15
50
.00
16
50
.00
10
10
.00
34
60
.00
21
30
.00
12
80
.00
09
6
Gd
15
70
.00
55
10
.00
60
90
.00
31
90
.00
58
60
.00
46
2<0
.00
00
00
.00
84
50
.00
58
7<0
.00
00
0
Tb1
59
0.0
00
59
<0.0
00
00
0.0
00
68
<0.0
00
00
0.0
01
21
0.0
00
98
0.0
00
74
0.0
01
98
0.0
00
66
Dy1
63
0.0
03
30
.00
25
80
.00
33
10
.00
28
70
.00
27
70
.00
38
80
.00
29
2<0
.00
00
0<0
.00
00
0
Ho
16
50
.00
06
0.0
00
66
0.0
00
70
.00
09
1<0
.00
00
00
.00
17
3<0
.00
00
00
.00
09
10
.00
04
8
Er1
67
0.0
04
22
0.0
03
80
.00
28
10
.00
29
90
.00
28
9<0
.00
00
00
.00
30
50
.00
73
40
.00
19
4
Tm1
69
0.0
00
56
<0.0
00
00
0.0
00
46
0.0
00
69
0.0
01
15
0.0
01
31
<0.0
00
00
0.0
04
04
0.0
00
45
Yb
17
10
.00
58
20
.00
64
30
.00
47
5<0
.00
00
00
.00
48
70
.00
68
3<0
.00
00
00
.00
62
0.0
04
64
Lu1
75
0.0
05
62
0.0
01
22
0.0
00
73
0.0
00
78
0.0
00
75
0.0
01
06
0.0
00
80
.00
09
60
.00
08
8
Hf1
78
0.0
03
27
0.0
03
61
0.0
01
89
0.0
02
01
<0.0
00
00
0.0
08
58
0.0
06
46
0.0
04
92
<0.0
00
00
Ta1
81
0.0
01
11
0.0
01
23
0.0
00
64
<0.0
00
00
0.0
01
32
0.0
01
31
0.0
01
71
0.0
01
19
0.0
01
09
Pb
20
80
.00
30
90
.00
83
70
.00
20
60
.00
26
90
.00
21
20
.00
72
70
.00
50
.00
38
10
.00
28
5
Th2
32
0.0
01
25
0.0
01
69
0.0
01
25
0.0
01
33
0.0
02
1<0
.00
00
0<0
.00
00
00
.00
18
90
.00
07
1
U2
38
0.0
01
21
0.0
01
90
.00
07
0.0
00
75
<0.0
00
00
0.0
02
02
0.0
02
41
0.0
02
24
0.0
00
97
Pm
14
7<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
Po
20
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
U2
32
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
Pu
23
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
121
SAM
PLE
MV
P1
04
38
GLI
TTER
!: M
ean
Raw
CP
S b
ackg
rou
nd
su
btr
acte
d.
Ele
me
nt
10
43
8A
-sp
t1-o
px-
a1
04
38
A-s
pt1
-op
x-b
10
43
8A
-sp
t1-c
px-
a1
04
38
A-s
pt1
-cp
x-b
10
43
8A
-sp
t4-s
cp-a
10
43
8A
-sp
t4-s
cp-b
10
43
8A
-sp
t2-s
cp-a
10
43
8A
-sp
t2-p
l-a
10
43
8A
-sp
t2-c
px-
a
Li7
58
97
34
90
29
98
27
08
42
05
10
88
6
Mg2
41
00
28
30
89
60
35
88
56
00
56
35
54
41
71
37
42
13
21
13
37
74
37
38
56
48
08
0
Si2
98
06
17
78
67
38
97
18
74
52
04
17
54
17
04
55
17
62
5
P3
12
22
86
53
44
65
46
41
10
54
74
38
71
11
79
Ca4
36
24
05
74
02
38
68
92
31
76
71
39
84
41
01
34
71
28
76
41
02
63
42
52
98
1
Sc4
54
39
68
42
34
71
47
20
51
32
98
81
10
10
31
86
74
14
19
77
Ti4
94
50
33
33
61
12
80
99
02
08
92
71
06
98
55
85
22
07
31
25
34
38
V5
12
46
49
52
44
41
15
56
12
05
34
89
81
64
13
41
01
16
15
58
66
4
Cr5
21
33
42
01
36
78
62
27
42
62
19
41
90
00
02
33
33
2
Ni6
02
33
99
24
18
91
34
80
13
15
92
20
03
31
45
37
Cu
65
76
07
15
65
77
62
06
10
50
70
0
Rb
85
00
18
16
65
11
04
50
31
52
3
Sr8
81
48
88
50
87
25
38
42
93
12
53
85
91
25
85
50
74
88
01
43
52
85
9
Y8
94
15
04
02
36
42
76
60
39
94
11
42
56
38
19
21
66
89
06
Zr9
01
21
41
01
82
30
38
21
62
00
31
52
42
41
39
Nb
93
80
04
01
08
4
Cs1
33
44
33
60
67
10
45
14
0
Ba1
37
00
13
31
18
95
87
36
11
16
79
91
20
La1
39
58
12
27
12
36
97
22
82
23
46
86
26
59
04
77
37
97
0
Ce
14
02
39
30
03
43
12
32
29
65
51
15
71
91
52
94
27
45
63
74
10
Pr1
41
51
63
89
62
89
59
77
33
89
37
41
28
92
97
68
Nd
14
35
46
96
62
36
44
33
59
63
47
35
90
32
67
30
4
Sm1
47
15
31
30
89
29
18
63
46
25
96
59
31
09
Eu1
51
49
29
27
86
27
12
10
77
56
31
03
15
96
30
74
Gd
15
77
55
53
46
63
25
44
57
29
45
53
03
71
8
Tb1
59
11
19
73
85
33
75
93
86
14
29
65
42
34
Dy1
63
26
32
69
62
26
58
58
44
52
44
06
31
65
21
Ho
16
52
69
28
44
84
94
70
12
81
52
22
21
52
90
Er1
67
25
12
88
31
75
30
71
13
21
11
66
83
43
8
Tm1
69
23
62
51
20
39
19
32
11
40
82
02
24
9
Yb
17
13
25
30
51
71
21
76
35
73
49
41
96
3
Lu1
75
29
83
56
16
28
15
54
67
16
12
17
96
Hf1
78
66
51
11
57
10
02
30
03
10
62
Ta1
81
02
15
53
00
04
Pb
20
89
01
33
11
41
75
71
04
41
66
91
15
01
37
Th2
32
21
67
37
23
01
27
90
U2
38
40
81
33
00
03
Pm
14
71
53
13
08
92
91
86
34
62
59
65
93
10
9
Po
20
89
01
33
11
41
75
71
04
41
66
91
15
01
37
U2
32
21
67
37
23
01
27
90
Pu
23
84
08
13
30
00
3
122
SAM
PLE
DEL
99
-2-0
1
GLI
TTER
!: T
race
Ele
me
nt
Co
nce
ntr
atio
ns
MD
L fi
lte
red
.
Ele
me
nt
DEL
-99
-2-0
1-s
pt5
-op
x-a
DEL
-99
-2-0
1-s
pt5
-op
x-b
DEL
-99
-2-0
1-s
pt5
-cp
x-a
DEL
-99
-2-0
1-s
pt5
-cp
x-b
DEL
-99
-2-0
1-s
pt3
-cp
x-a
DEL
-99
-2-0
1-s
pt3
-cp
x-b
DEL
-99
-2-0
1-s
pt3
-cp
x-c
DEL
-99
-2-0
1-s
pt3
-op
x-a
DEL
-99
-2-0
1-s
pt3
-op
x-b
DEL
-99
-2-0
1-s
pt3
op
x-c
Li7
1.5
62
.29
2.4
61
.32
1.2
11
.24
2.0
4<0
.52
1.6
41
.98
Mg2
42
41
88
6.3
12
36
05
4.2
28
16
24
.21
84
02
4.5
19
09
00
.38
86
86
2.3
58
60
34
.77
15
27
35
.52
16
93
14
.59
17
04
34
.8
Si2
93
90
57
2.0
34
09
14
7.2
82
56
77
8.1
62
50
36
1.7
72
54
62
1.6
62
46
31
3.7
32
52
76
5.8
32
65
77
2.5
32
92
32
8.2
52
85
09
7.9
4
P3
1<1
1.7
5<1
2.1
21
4.8
9<8
.46
<7.0
2<7
.33
16
.02
11
.28
<7.9
58
.66
Ca4
30
.55
0.5
52
2.7
72
2.7
72
2.7
22
2.7
22
2.7
20
.38
0.3
80
.38
Sc4
54
7.2
14
6.4
51
21
11
3.0
81
13
.45
12
1.0
21
13
.65
30
.43
31
.58
33
.7
Ti4
98
53
.35
84
9.3
47
65
.16
43
75
.54
20
6.9
24
85
9.1
64
28
0.2
15
08
.59
56
3.1
56
08
.78
V5
13
10
.61
30
04
84
.45
46
9.7
94
56
.92
47
3.2
74
61
.43
19
5.2
32
05
.33
22
0.8
4
Cr5
29
06
.67
93
1.2
99
89
.68
97
0.6
49
74
.02
98
0.2
99
82
.31
60
4.7
36
30
.37
66
2.0
8
Ni6
02
82
.69
29
1.4
69
8.5
59
7.0
79
6.7
99
5.8
21
02
.51
18
4.0
32
09
.63
21
3.1
4
Cu
65
4.0
63
.67
1.8
21
.58
1.6
61
.61
1.4
2.6
32
.74
3.4
2
Rb
85
<0.0
14
9<0
.01
45
<0.0
10
2<0
.01
08
<0.0
08
6<0
.01
14
<0.0
11
0<0
.01
00
<0.0
10
6<0
.01
01
Sr8
80
.01
41
0.0
12
51
4.9
11
5.7
91
5.7
71
5.9
21
6.4
90
.02
47
0.0
23
40
.02
29
Y8
91
.15
41
.11
91
9.4
19
.09
17
.97
19
.26
18
.60
.76
50
.80
40
.84
1
Zr9
00
.51
30
.54
99
.85
9.5
69
.67
11
.24
10
.39
0.4
41
0.4
44
0.4
3
Nb
93
0.0
05
90
.00
34
10
.00
88
0.0
15
20
.00
91
0.0
12
50
.00
77
<0.0
01
60
0.0
01
73
0.0
02
44
Cs1
33
<0.0
02
40
.00
31
<0.0
01
67
0.0
03
58
<0.0
01
78
<0.0
01
75
<0.0
01
86
<0.0
01
73
<0.0
02
21
<0.0
02
16
Ba1
37
<0.0
23
<0.0
27
<0.0
15
0<0
.01
59
<0.0
14
0<0
.01
84
<0.0
15
4<0
.02
03
0.0
17
6<0
.01
62
La1
39
<0.0
01
79
<0.0
01
82
0.3
35
0.3
46
0.3
43
0.3
76
0.3
85
0.0
00
87
<0.0
01
43
<0.0
01
38
Ce
14
00
.00
21
60
.00
12
91
.91
91
.89
51
.93
2.0
75
2.0
87
0.0
06
17
0.0
07
25
0.0
02
26
Pr1
41
<0.0
01
46
<0.0
01
05
0.4
81
0.4
73
0.5
0.5
18
0.5
16
<0.0
00
66
<0.0
01
03
<0.0
00
74
Nd
14
30
.01
70
.00
86
3.7
93
.79
3.7
54
.06
3.9
70
.01
76
0.0
12
5<0
.00
64
Sm1
47
0.0
09
40
.02
16
1.9
26
1.8
57
1.6
59
1.8
59
1.8
50
.00
62
0.0
08
30
.01
41
Eu1
51
0.0
08
80
.00
71
0.7
76
0.7
83
0.7
42
0.7
70
.78
4<0
.00
69
0.0
05
50
.00
57
Gd
15
70
.02
80
.03
22
2.7
84
2.9
37
2.5
56
2.9
55
2.9
20
.02
38
0.0
27
10
.02
38
Tb1
59
0.0
11
40
.01
11
0.5
27
0.5
11
0.4
76
0.5
43
0.5
39
0.0
09
07
0.0
07
07
0.0
12
3
Dy1
63
0.1
46
0.1
12
93
.63
3.6
73
.26
43
.72
3.6
0.0
98
20
.09
91
0.0
86
Ho
16
50
.04
14
0.0
41
0.7
96
0.7
88
0.7
59
0.8
07
0.7
71
0.0
30
80
.03
05
0.0
27
1
Er1
67
0.1
90
.16
22
.06
42
.06
91
.98
12
.05
2.1
43
0.1
27
90
.11
21
0.1
45
7
Tm1
69
0.0
34
90
.03
98
0.3
22
0.3
13
0.2
85
20
.30
49
0.3
01
30
.02
40
.02
75
0.0
25
5
Yb
17
10
.33
60
.31
82
.01
71
.99
11
.73
2.0
31
.84
10
.22
20
.35
50
.23
6
Lu1
75
0.0
81
80
.08
04
0.2
87
0.2
64
40
.26
80
.29
73
0.2
74
10
.04
47
0.0
52
20
.05
04
Hf1
78
0.0
40
40
.04
35
0.7
11
0.6
81
0.6
91
0.7
90
.72
80
.02
40
.02
26
0.0
39
1
Ta1
81
<0.0
01
04
<0.0
01
50
<0.0
01
45
<0.0
01
27
0.0
01
53
<0.0
01
16
<0.0
00
96
<0.0
00
94
<0.0
00
.00
10
7
Pb
20
80
.01
65
<0.0
05
40
.02
77
0.0
14
60
.01
57
0.0
20
30
.02
39
0.0
06
60
.00
96
0.0
06
5
Th2
32
<0.0
02
35
0.0
00
56
0.0
04
50
.00
80
.00
53
0.0
07
50
.03
07
<0.0
01
99
<0.0
00
83
<0.0
02
24
U2
38
<0.0
01
62
<0.0
02
01
0.0
04
86
<0.0
02
10
.00
58
70
.00
27
10
.00
28
3<0
.00
19
3<0
.01
52
<0.0
01
65
Pm
14
7<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN
Po
20
8<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN
U2
32
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
Pu
23
8<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN
123
SAM
PLE
DEL
99
-2-0
1
GLI
TTER
!: T
race
Ele
me
nt
Co
nce
ntr
atio
ns
MD
L fi
lte
red
.
Ele
me
nt
DEL
-99
-2-0
1-s
pt3
-pl-
aD
EL-9
9-2
-01
-sp
t3-p
l-b
DEL
-99
-2-0
1-s
pt3
-pl-
cD
EL-9
9-2
-01
-sp
t8-c
px-
aD
EL-9
9-2
-01
-sp
t8-c
px-
bD
EL-9
9-2
-01
-sp
t8-o
px-
aD
EL-9
9-2
-01
-sp
t7-c
px-
aD
EL-9
9-2
-01
-sp
t7-c
px-
bD
EL-9
9-2
-01
-sp
t7-c
px-
c
Li7
<0.8
2<0
.75
1.0
71
.68
1.8
72
.18
69
.99
2.6
79
6.1
4
Mg2
42
16
5.4
41
00
3.4
15
17
.39
16
79
.34
90
98
9.9
72
01
37
8.6
99
75
85
96
86
31
5.8
10
34
42
02
Si2
92
84
15
9.5
62
74
43
5.7
52
93
70
2.1
32
45
72
5.5
32
49
91
7.6
43
33
05
9.3
11
60
90
50
52
63
79
6.4
71
75
28
26
4
P3
11
8.4
8<1
3.5
3<1
3.9
5<6
.74
<6.9
5<9
.02
<43
2.0
1<7
.17
<44
5.8
2
Ca4
31
8.2
51
8.2
51
8.2
52
2.9
12
2.9
10
.47
22
.63
22
.63
22
.63
Sc4
51
.23
50
.99
40
.63
61
04
.39
10
6.3
63
5.8
71
82
8.6
21
13
.71
97
5.5
1
Ti4
95
8.6
26
9.7
94
3.8
73
97
0.3
34
03
4.9
66
27
.76
34
29
7.3
94
40
0.0
93
43
46
.18
V5
15
.66
4.9
82
.72
34
50
.32
45
6.0
32
39
.58
11
63
1.8
44
62
.06
12
96
9.6
8
Cr5
21
4.9
77
.99
6.4
59
53
.34
98
0.3
57
40
.03
33
86
6.2
39
58
.18
36
87
2
Ni6
02
.04
<1.1
1<1
.22
98
.77
10
4.1
62
45
.11
16
10
.15
97
.29
12
48
1.1
6
Cu
65
<0.4
60
.95
<0.3
91
.91
1.6
83
.18
16
0.4
61
.65
15
7.6
Rb
85
0.0
31
60
.09
20
.04
02
0.0
10
2<0
.00
89
<0.0
14
1<0
.63
<0.0
10
2<0
.65
Sr8
85
94
.14
72
2.5
85
87
.33
16
.12
16
.07
0.0
11
10
.31
51
4.7
10
.42
Y8
90
.18
90
.16
30
.17
71
7.0
91
80
.95
84
4.4
11
9.1
54
7.9
8
Zr9
00
.07
50
.04
70
.04
56
.61
6.8
90
.37
62
0.0
88
.51
20
.71
Nb
93
0.0
02
35
<0.0
02
8<0
.00
20
90
.02
56
0.0
14
40
.00
19
10
.10
10
.01
18
0.1
27
Cs1
33
<0.0
0<0
.03
1<0
.00
37
<0.0
01
70
<0.0
01
67
<0.0
02
43
<0.1
35
<0.0
01
94
<0.1
13
Ba1
37
13
.54
16
.59
12
.95
<0.0
16
20
.02
15
<0.0
14
1<1
.03
<0.0
10
8<1
.01
La1
39
0.5
71
0.5
45
0.5
77
0.2
83
0.2
89
0.0
01
24
<0.0
62
0.3
12
<0.0
62
Ce
14
01
.01
81
.07
31
.07
51
.59
91
.65
40
.00
10
60
.12
61
.88
90
.13
8
Pr1
41
0.1
26
90
.13
25
0.1
07
40
.41
0.4
29
<0.0
00
84
<0.0
38
0.4
56
0.1
33
Nd
14
30
.47
80
.50
20
.47
3.3
3.4
9<0
.00
88
<0.3
33
.96
0.7
5
Sm1
47
0.0
81
60
.03
93
0.0
36
51
.74
11
.65
0.0
09
40
.39
1.8
67
0.2
8
Eu1
51
0.2
62
0.2
54
0.2
33
0.7
34
0.7
37
<0.0
02
20
.30
50
.80
.37
8
Gd
15
70
.09
60
.06
80
.08
32
.50
22
.67
80
.02
51
.68
2.9
83
2.2
8
Tb1
59
0.0
10
80
.01
38
0.0
05
54
0.4
58
0.5
0.0
12
0.5
39
0.5
25
0.5
58
Dy1
63
0.0
38
90
.03
89
0.0
28
93
.33
.43
0.1
30
65
.33
.69
5.8
8
Ho
16
50
.00
79
0.0
09
60
.00
78
0.7
15
0.7
52
0.0
33
71
.65
0.7
91
1.8
2
Er1
67
0.0
15
0.0
26
40
.02
52
1.9
44
1.9
91
0.1
55
55
.04
2.1
47
6.5
8
Tm1
69
<0.0
01
60
0.0
02
80
.00
19
50
.26
63
0.2
80
10
.03
32
1.6
0.3
01
1.4
9
Yb
17
10
.01
08
<0.0
06
10
.01
76
1.6
95
1.8
42
<0.0
49
12
.72
.10
31
4.9
4
Lu1
75
<0.0
01
48
<0.0
03
4<0
.00
14
00
.24
11
0.2
62
80
.06
27
2.6
20
.28
18
2.9
2
Hf1
78
0.0
04
0.0
09
90
.00
59
0.5
03
0.5
09
<0.0
40
1.5
20
.60
92
.12
Ta1
81
0.0
00
69
<0.0
01
16
<0.0
02
45
<0.0
01
32
<0.0
00
64
<0.0
05
0<0
.03
9<0
.00
12
9<0
.05
5
Pb
20
80
.32
70
.35
60
.33
10
.02
45
0.0
17
80
.00
86
0.6
80
.03
11
0.3
2
Th2
32
<0.0
0<0
.00
13
2<0
.00
13
90
.00
37
20
.00
74
2<0
.00
13
5<0
.04
40
.00
36
3<0
.08
9
U2
38
<0.0
02
02
<0.0
01
28
<0.0
02
34
0.0
02
61
0.0
04
28
0.0
00
43
17
.30
.00
47
6<0
.06
1
Pm
14
7<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
Po
20
8<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
U2
32
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN
Pu
23
8<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
124
SAM
PLE
DEL
99
-2-0
1
GLI
TTER
!: 1
sig
ma
err
or.
Ele
me
nt
DEL
-99
-2-0
1-s
pt5
-op
x-a
DEL
-99
-2-0
1-s
pt5
-op
x-b
DEL
-99
-2-0
1-s
pt5
-cp
x-a
DEL
-99
-2-0
1-s
pt5
-cp
x-b
DEL
-99
-2-0
1-s
pt3
-cp
x-a
DEL
-99
-2-0
1-s
pt3
-cp
x-b
DEL
-99
-2-0
1-s
pt3
-cp
x-c
DEL
-99
-2-0
1-s
pt3
-op
x-a
DEL
-99
-2-0
1-s
pt3
-op
x-b
DEL
-99
-2-0
1-s
pt3
op
x-c
Li7
0.4
70
.61
0.6
0.3
80
.33
0.3
50
.51
0.2
40
.44
0.5
1
Mg2
43
84
85
.39
37
75
4.7
21
30
75
.92
13
53
1.5
41
47
16
.43
14
13
7.6
11
40
77
.81
25
20
0.1
62
80
97
.07
28
43
8.9
7
Si2
96
18
05
66
64
76
90
1.5
40
66
36
2.2
53
96
62
19
40
35
19
6.7
53
90
49
78
.75
40
08
75
2.7
54
21
65
96
.54
63
96
33
.54
52
65
56
.5
P3
16
.32
5.3
89
.62
5.0
74
.03
3.8
21
0.1
7.4
13
.37
6.2
4
Ca4
30
.01
70
.01
70
.53
0.5
30
.53
0.5
30
.53
0.0
11
0.0
11
0.0
12
Sc4
51
.38
1.3
63
.11
2.9
12
.92
3.1
22
.93
0.8
80
.93
1
Ti4
92
6.0
52
61
29
.78
11
9.3
91
14
.96
13
3.0
21
17
.41
15
.51
7.3
91
8.9
V5
19
.33
9.0
31
3.0
11
2.6
41
2.3
11
2.7
71
2.4
75
.83
6.2
26
.73
Cr5
23
0.3
43
1.2
63
0.4
22
9.9
13
0.0
83
0.3
53
0.5
20
.32
21
.44
22
.64
Ni6
01
6.1
81
6.7
65
.55
5.4
95
.49
5.4
65
.87
10
.81
2.4
12
.67
Cu
65
0.3
10
.29
0.1
60
.15
0.1
40
.14
0.1
40
.20
.21
0.2
5
Rb
85
0.0
06
80
.00
58
0.0
04
30
.00
45
0.0
03
80
.00
46
0.0
04
70
.00
44
0.0
04
40
.00
46
Sr8
80
.00
30
.00
25
0.5
0.5
30
.53
0.5
40
.56
0.0
03
0.0
02
60
.00
25
Y8
90
.04
40
.04
30
.64
0.6
40
.60
.65
0.6
30
.03
0.0
32
0.0
33
Zr9
00
.02
50
.02
60
.32
0.3
10
.31
0.3
60
.34
0.0
20
.02
0.0
2
Nb
93
0.0
01
30
.00
09
90
.00
15
0.0
01
90
.00
13
0.0
01
70
.00
16
0.0
00
81
0.0
00
79
0.0
00
71
Cs1
33
0.0
01
10
.00
12
0.0
00
83
0.0
00
87
0.0
00
74
0.0
00
79
0.0
00
78
0.0
00
76
0.0
00
81
0.0
00
91
Ba1
37
0.0
10
.01
20
.00
72
0.0
06
0.0
06
0.0
07
20
.00
63
0.0
07
70
.00
65
0.0
06
7
La1
39
0.0
00
76
0.0
00
82
0.0
12
0.0
12
0.0
12
0.0
13
0.0
14
0.0
00
44
0.0
00
64
0.0
00
54
Ce
14
00
.00
06
90
.00
06
0.0
59
0.0
58
0.0
59
0.0
63
0.0
64
0.0
00
84
0.0
00
95
0.0
00
5
Pr1
41
0.0
00
72
0.0
00
52
0.0
15
0.0
15
0.0
15
0.0
16
0.0
16
0.0
00
31
0.0
00
47
0.0
00
31
Nd
14
30
.00
56
0.0
04
0.1
20
.12
0.1
20
.13
0.1
30
.00
38
0.0
03
50
.00
34
Sm1
47
0.0
03
50
.00
53
0.0
65
0.0
63
0.0
57
0.0
63
0.0
63
0.0
02
70
.00
31
0.0
02
9
Eu1
51
0.0
01
80
.00
16
0.0
23
0.0
23
0.0
22
0.0
23
0.0
23
0.0
02
40
.00
12
0.0
01
1
Gd
15
70
.00
65
0.0
05
30
.09
0.0
94
0.0
82
0.0
94
0.0
94
0.0
04
60
.00
51
0.0
05
2
Tb1
59
0.0
01
30
.00
13
0.0
16
0.0
15
0.0
14
0.0
16
0.0
16
0.0
00
90
.00
08
50
.00
11
Dy1
63
0.0
09
60
.00
83
0.1
10
.11
0.0
99
0.1
10
.11
0.0
06
50
.00
67
0.0
06
3
Ho
16
50
.00
26
0.0
02
60
.02
50
.02
40
.02
30
.02
50
.02
40
.00
19
0.0
01
90
.00
18
Er1
67
0.0
12
0.0
11
0.0
67
0.0
67
0.0
64
0.0
66
0.0
69
0.0
07
80
.00
75
0.0
08
8
Tm1
69
0.0
02
30
.00
25
0.0
10
.01
0.0
09
20
.00
98
0.0
09
70
.00
16
0.0
01
80
.00
17
Yb
17
10
.02
0.0
19
0.0
61
0.0
60
.05
20
.06
0.0
55
0.0
13
0.0
18
0.0
14
Lu1
75
0.0
04
0.0
04
0.0
08
90
.00
83
0.0
08
20
.00
90
.00
84
0.0
02
40
.00
27
0.0
02
6
Hf1
78
0.0
04
60
.00
54
0.0
28
0.0
27
0.0
27
0.0
30
.02
80
.00
29
0.0
03
0.0
04
7
Ta1
81
0.0
00
59
0.0
00
62
0.0
00
72
0.0
00
64
0.0
00
61
0.0
00
52
0.0
00
48
0.0
00
35
<0.0
00
.00
03
6
Pb
20
80
.00
30
.00
27
0.0
03
40
.00
22
0.0
02
10
.00
27
0.0
02
90
.00
16
0.0
01
70
.00
14
Th2
32
0.0
00
73
0.0
00
33
0.0
01
0.0
01
20
.00
10
.00
11
0.0
02
50
.00
06
20
.00
03
40
.00
07
3
U2
38
0.0
00
73
0.0
00
77
0.0
00
91
0.0
01
0.0
00
87
0.0
00
79
0.0
00
75
0.0
00
64
0.0
08
90
.00
06
4
Pm
14
7<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
Po
20
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
U2
32
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
Pu
23
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
125
SAM
PLE
DEL
99
-2-0
1
GLI
TTER
!: 1
sig
ma
err
or.
Ele
me
nt
DEL
-99
-2-0
1-s
pt3
-pl-
aD
EL-9
9-2
-01
-sp
t3-p
l-b
DEL
-99
-2-0
1-s
pt3
-pl-
cD
EL-9
9-2
-01
-sp
t8-c
px-
aD
EL-9
9-2
-01
-sp
t8-c
px-
bD
EL-9
9-2
-01
-sp
t8-o
px-
aD
EL-9
9-2
-01
-sp
t7-c
px-
aD
EL-9
9-2
-01
-sp
t7-c
px-
bD
EL-9
9-2
-01
-sp
t7-c
px-
c
Li7
0.3
80
.43
0.4
10
.43
0.4
80
.56
19
.99
0.6
72
6.1
2
Mg2
43
62
.11
16
8.7
88
7.4
91
55
80
.84
15
54
8.8
93
46
93
.61
16
90
81
01
49
96
.97
18
13
39
4.2
5
Si2
94
51
33
30
.54
36
05
04
.54
66
83
58
.53
90
72
26
.25
39
75
36
0.7
55
29
98
39
25
61
36
92
84
20
08
08
27
92
31
55
2
P3
11
2.8
47
.76
.12
4.2
32
.99
4.3
11
86
.55
4.7
92
03
.08
Ca4
30
.43
0.4
30
.43
0.5
30
.53
0.0
14
0.6
70
.53
0.7
Sc4
50
.08
30
.08
70
.07
22
.71
2.7
71
.04
53
.61
2.9
75
9.4
6
Ti4
91
.92
.39
1.4
91
10
.36
11
2.4
19
.31
10
62
.75
12
3.3
31
09
1.6
8
V5
10
.17
0.1
70
.09
21
2.3
12
.48
7.2
23
53
.13
12
.71
40
3.4
4
Cr5
20
.65
0.5
40
.47
30
.13
31
.07
25
.26
11
64
.28
30
.61
12
94
.99
Ni6
00
.57
0.5
90
.54
5.8
26
.17
14
.86
70
7.8
55
.84
77
1.5
9
Cu
65
0.1
90
.22
0.1
80
.16
0.1
50
.25
12
.50
.16
13
.08
Rb
85
0.0
08
40
.01
30
.00
82
0.0
04
30
.00
41
0.0
05
60
.28
0.0
04
80
.28
Sr8
82
0.3
72
4.9
12
0.2
90
.56
0.5
60
.00
25
0.0
97
0.5
20
.14
Y8
90
.01
10
.01
20
.01
0.5
90
.62
0.0
38
1.7
80
.67
1.9
7
Zr9
00
.01
10
.01
30
.01
10
.22
0.2
30
.01
91
0.2
91
.09
Nb
93
0.0
00
96
0.0
01
40
.00
09
20
.00
23
0.0
01
90
.00
08
90
.04
40
.00
17
0.0
43
Cs1
33
<0.0
00
.02
30
.00
17
0.0
00
72
0.0
00
71
0.0
00
93
0.0
52
0.0
00
88
0.0
46
Ba1
37
0.5
0.6
20
.48
0.0
06
0.0
07
0.0
05
60
.40
.00
57
0.4
1
La1
39
0.0
21
0.0
22
0.0
21
0.0
10
.01
10
.00
04
50
.02
50
.01
20
.03
Ce
14
00
.03
40
.03
80
.03
60
.05
0.0
52
0.0
00
36
0.0
28
0.0
60
.03
6
Pr1
41
0.0
05
80
.00
71
0.0
05
20
.01
30
.01
40
.00
03
40
.01
60
.01
50
.03
8
Nd
14
30
.03
0.0
37
0.0
29
0.1
10
.12
0.0
04
30
.14
0.1
30
.19
Sm1
47
0.0
09
90
.00
97
0.0
06
50
.06
0.0
58
0.0
03
0.1
40
.06
60
.16
Eu1
51
0.0
12
0.0
14
0.0
11
0.0
22
0.0
22
0.0
01
10
.05
90
.02
50
.08
4
Gd
15
70
.01
20
.01
20
.01
0.0
82
0.0
88
0.0
04
50
.27
0.1
0.3
5
Tb1
59
0.0
01
50
.00
20
.00
09
80
.01
40
.01
50
.00
12
0.0
56
0.0
16
0.0
61
Dy1
63
0.0
05
50
.00
74
0.0
07
50
.10
.11
0.0
08
30
.37
0.1
20
.44
Ho
16
50
.00
13
0.0
01
80
.00
14
0.0
23
0.0
24
0.0
02
20
.11
0.0
26
0.1
3
Er1
67
0.0
04
10
.00
65
0.0
04
90
.06
40
.06
60
.00
97
0.3
70
.07
20
.47
Tm1
69
0.0
00
75
0.0
01
10
.00
07
80
.00
87
0.0
09
30
.00
21
0.1
0.0
10
.11
Yb
17
10
.00
47
0.0
04
0.0
04
60
.05
10
.05
60
.02
0.7
70
.06
40
.93
Lu1
75
0.0
00
72
0.0
01
20
.00
06
90
.00
75
0.0
08
20
.00
32
0.1
40
.00
90
.16
Hf1
78
0.0
02
30
.00
42
0.0
02
0.0
21
0.0
21
0.0
17
0.2
0.0
26
0.2
4
Ta1
81
0.0
00
40
.00
07
50
.00
07
60
.00
06
10
.00
02
70
.00
17
0.0
17
0.0
00
64
0.0
22
Pb
20
80
.02
40
.02
80
.02
40
.00
30
.00
26
0.0
02
20
.12
0.0
03
90
.11
Th2
32
<0.0
00
.00
04
10
.00
07
60
.00
07
70
.00
09
80
.00
05
50
.01
90
.00
09
30
.03
9
U2
38
0.0
00
63
0.0
00
83
0.0
00
84
0.0
00
74
0.0
00
92
0.0
00
25
0.9
70
.00
09
70
.02
5
Pm
14
7<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
Po
20
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
U2
32
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
Pu
23
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
126
SAM
PLE
DEL
99
-2-0
1
GLI
TTER
!: M
inim
um
de
tect
ion
lim
its
(99
% c
on
fid
en
ce).
Ele
me
nt
DEL
-99
-2-0
1-s
pt5
-op
x-a
DEL
-99
-2-0
1-s
pt5
-op
x-b
DEL
-99
-2-0
1-s
pt5
-cp
x-a
DEL
-99
-2-0
1-s
pt5
-cp
x-b
DEL
-99
-2-0
1-s
pt3
-cp
x-a
DEL
-99
-2-0
1-s
pt3
-cp
x-b
DEL
-99
-2-0
1-s
pt3
-cp
x-c
DEL
-99
-2-0
1-s
pt3
-op
x-a
DEL
-99
-2-0
1-s
pt3
-op
x-b
DEL
-99
-2-0
1-s
pt3
op
x-c
Li7
0.7
08
0.6
98
0.4
61
0.5
02
0.4
05
0.4
37
0.4
15
0.5
24
0.4
63
0.4
62
Mg2
42
.04
2.1
41
.48
1.5
21
.28
1.4
11
.47
1.4
41
.61
1.6
5
Si2
91
06
2.4
41
05
8.0
96
15
.22
63
0.7
46
36
.62
71
3.9
96
47
.71
58
6.2
47
87
.27
76
4.0
6
P3
11
1.7
51
2.1
28
.19
8.4
67
.02
7.3
37
.26
7.0
37
.95
8.1
1
Ca4
30
.01
01
0.0
10
10
.00
68
10
.00
66
40
.00
57
20
.00
59
30
.00
57
70
.00
56
80
.00
66
50
.00
69
7
Sc4
50
.12
60
.13
0.0
91
60
.08
66
0.0
75
20
.08
12
0.0
79
50
.07
93
0.0
85
30
.08
89
Ti4
90
.46
80
.47
60
.27
0.2
91
0.2
16
0.2
45
0.2
89
0.3
08
0.3
21
0.2
62
V5
10
.04
18
0.0
37
60
.02
83
0.0
27
20
.02
14
0.0
24
50
.02
31
0.0
23
70
.02
84
0.0
26
3
Cr5
20
.89
20
.86
0.5
83
0.5
76
0.5
02
0.5
13
0.5
08
0.4
93
0.5
42
0.5
57
Ni6
00
.98
41
.02
0.6
98
0.7
18
0.5
94
0.6
17
0.6
51
0.6
28
0.6
89
0.7
07
Cu
65
0.3
49
0.3
64
0.2
34
0.2
45
0.1
99
0.1
99
0.2
17
0.2
09
0.2
41
0.2
25
Rb
85
0.0
14
90
.01
45
0.0
10
20
.01
08
0.0
08
57
0.0
11
40
.01
10
.01
0.0
10
60
.01
01
Sr8
80
.00
53
40
.00
38
40
.00
31
20
.00
35
70
.00
24
50
.00
32
70
.00
34
70
.00
44
30
.00
31
40
.00
27
1
Y8
90
.00
60
80
.00
63
60
.00
46
0.0
04
53
0.0
05
31
0.0
04
36
0.0
04
50
.00
37
50
.00
52
90
.00
52
9
Zr9
00
.02
02
0.0
18
10
.01
37
0.0
12
60
.01
07
0.0
11
30
.01
28
0.0
11
30
.01
06
0.0
13
9
Nb
93
<0.0
00
00
<0.0
00
00
0.0
01
24
0.0
01
25
<0.0
00
00
0.0
01
62
0.0
02
31
0.0
01
60
.00
12
5<0
.00
00
0
Cs1
33
0.0
02
40
.00
22
60
.00
16
70
.00
14
30
.00
17
80
.00
17
50
.00
18
60
.00
17
30
.00
22
10
.00
21
6
Ba1
37
0.0
22
60
.02
72
0.0
15
0.0
15
90
.01
40
.01
84
0.0
15
40
.02
03
0.0
12
30
.01
62
La1
39
0.0
01
79
0.0
01
82
0.0
01
06
0.0
00
68
0.0
01
50
.00
13
80
.00
14
60
.00
07
50
.00
14
30
.00
13
8
Ce
14
00
.00
09
40
.00
09
5<0
.00
00
00
.00
06
60
.00
05
60
.00
06
10
.00
12
20
.00
06
0.0
00
66
<0.0
00
00
Pr1
41
0.0
01
46
0.0
01
05
0.0
00
51
0.0
01
03
0.0
00
61
0.0
01
06
0.0
00
67
0.0
00
66
0.0
01
03
0.0
00
74
Nd
14
30
.00
88
70
.00
63
80
.00
75
90
.00
62
60
.00
64
4<0
.00
00
0<0
.00
00
00
.00
39
90
.00
44
20
.00
63
7
Sm1
47
0.0
05
14
0.0
07
39
<0.0
00
00
0.0
03
62
0.0
05
28
0.0
03
32
<0.0
00
00
0.0
04
63
0.0
05
12
<0.0
00
00
Eu1
51
0.0
02
25
0.0
01
98
0.0
01
11
0.0
01
37
0.0
00
67
0.0
01
45
<0.0
00
00
0.0
06
93
0.0
01
37
0.0
01
14
Gd
15
70
.01
03
<0.0
00
00
0.0
06
24
0.0
07
27
<0.0
00
00
0.0
05
76
0.0
03
36
0.0
06
57
0.0
07
27
0.0
08
29
Tb1
59
0.0
00
78
0.0
01
12
0.0
01
09
0.0
00
95
0.0
00
80
.00
07
1<0
.00
00
0<0
.00
00
00
.00
05
50
.00
05
6
Dy1
63
<0.0
00
00
<0.0
00
00
<0.0
00
00
0.0
02
18
0.0
02
59
<0.0
00
00
0.0
02
02
0.0
01
97
0.0
02
18
0.0
03
14
Ho
16
5<0
.00
00
0<0
.00
00
0<0
.00
00
0<0
.00
00
00
.00
08
20
.00
07
30
.00
05
20
.00
07
2<0
.00
00
00
.00
08
1
Er1
67
0.0
06
45
0.0
07
34
0.0
03
19
0.0
06
83
0.0
02
71
0.0
03
61
0.0
02
98
0.0
02
06
0.0
03
22
<0.0
00
00
Tm1
69
0.0
00
74
0.0
00
75
0.0
00
90
.00
05
20
.00
04
4<0
.00
00
00
.00
06
80
.00
06
70
.00
07
40
.00
05
3
Yb
17
10
.00
77
10
.00
96
0.0
03
81
0.0
06
66
0.0
08
55
0.0
04
98
<0.0
00
00
0.0
06
01
<0.0
00
00
0.0
05
54
Lu1
75
<0.0
00
00
0.0
00
86
0.0
00
59
0.0
01
45
0.0
00
50
.00
07
70
.00
05
50
.00
09
30
.00
08
40
.00
06
Hf1
78
<0.0
00
00
0.0
05
38
<0.0
00
00
<0.0
00
00
0.0
02
56
<0.0
00
00
0.0
02
82
<0.0
00
00
0.0
02
15
0.0
05
81
Ta1
81
0.0
01
04
0.0
01
50
.00
14
50
.00
12
70
.00
10
70
.00
11
60
.00
09
60
.00
09
4<0
.00
00
0<0
.00
00
0
Pb
20
80
.00
33
50
.00
53
90
.00
23
4<0
.00
00
0<0
.00
00
00
.00
21
60
.00
15
40
.00
21
3<0
.00
00
0<0
.00
00
0
Th2
32
0.0
02
35
<0.0
00
00
0.0
01
42
0.0
01
44
0.0
01
40
.00
13
20
.00
32
60
.00
19
90
.00
08
30
.00
22
4
U2
38
0.0
01
62
0.0
02
01
0.0
00
80
.00
21
3<0
.00
00
00
.00
12
80
.00
10
60
.00
19
30
.01
52
0.0
01
65
Pm
14
7<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
Po
20
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
U2
32
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
Pu
23
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
127
SAM
PLE
DEL
99
-2-0
1
GLI
TTER
!: M
inim
um
de
tect
ion
lim
its
(99
% c
on
fid
en
ce).
Ele
me
nt
DEL
-99
-2-0
1-s
pt3
-pl-
aD
EL-9
9-2
-01
-sp
t3-p
l-b
DEL
-99
-2-0
1-s
pt3
-pl-
cD
EL-9
9-2
-01
-sp
t8-c
px-
aD
EL-9
9-2
-01
-sp
t8-c
px-
bD
EL-9
9-2
-01
-sp
t8-o
px-
aD
EL-9
9-2
-01
-sp
t7-c
px-
aD
EL-9
9-2
-01
-sp
t7-c
px-
bD
EL-9
9-2
-01
-sp
t7-c
px-
c
Li7
0.8
21
0.7
52
0.7
07
0.3
70
.38
10
.49
32
4.0
70
.39
32
4.9
3
Mg2
43
.01
2.6
2.8
51
.33
1.4
71
.98
88
.85
1.5
81
00
.82
Si2
91
45
2.7
91
34
9.6
11
42
.45
59
0.6
56
95
.99
69
1.6
54
53
69
.87
60
9.6
42
11
2.9
9
P3
11
4.8
71
3.5
31
3.9
56
.74
6.9
59
.02
43
2.0
17
.17
44
5.8
2
Ca4
30
.01
18
0.0
10
70
.01
08
0.0
05
45
0.0
05
41
0.0
07
05
0.3
49
0.0
05
73
0.3
69
Sc4
50
.15
60
.13
90
.14
90
.07
65
0.0
76
60
.10
24
.60
.07
93
4.7
9
Ti4
90
.49
50
.48
10
.49
10
.27
30
.25
0.3
22
14
.55
0.2
62
16
.61
V5
10
.04
78
0.0
45
0.0
42
0.0
20
90
.02
35
0.0
33
21
.37
0.0
23
31
.67
Cr5
20
.96
80
.89
0.9
34
0.4
82
0.5
0.6
33
29
.66
0.4
98
30
.6
Ni6
01
.25
1.1
11
.22
0.5
65
0.6
20
.79
33
6.4
50
.63
37
.86
Cu
65
0.4
57
0.3
60
.39
0.2
02
0.2
10
.27
31
2.3
10
.21
11
3.5
2
Rb
85
0.0
16
50
.01
66
0.0
14
80
.00
91
20
.00
89
0.0
14
10
.62
70
.01
02
0.6
48
Sr8
80
.00
46
80
.00
65
20
.01
05
0.0
02
70
.00
37
40
.00
45
10
.17
70
.00
27
60
.24
5
Y8
90
.00
96
80
.00
83
70
.00
73
40
.00
38
20
.00
49
70
.00
61
80
.23
20
.00
40
70
.21
4
Zr9
00
.01
88
0.0
21
10
.02
13
0.0
09
61
0.0
09
70
.01
48
0.6
41
0.0
12
60
.72
9
Nb
93
<0.0
00
00
0.0
02
80
.00
20
9<0
.00
00
00
.00
18
90
.00
14
30
.06
60
.00
11
<0.0
00
00
Cs1
33
0.0
03
56
0.0
31
40
.00
36
90
.00
17
0.0
01
67
0.0
02
43
0.1
35
0.0
01
94
0.1
13
Ba1
37
0.0
21
70
.03
57
0.0
34
60
.01
62
0.0
13
20
.01
41
1.0
30
.01
08
1.0
1
La1
39
0.0
01
68
0.0
02
27
0.0
02
39
0.0
01
15
0.0
01
11
0.0
00
55
0.0
61
80
.00
11
10
.06
25
Ce
14
00
.00
16
50
.00
14
80
.00
11
0.0
00
75
0.0
01
<0.0
00
00
<0.0
00
00
<0.0
00
00
0.0
35
3
Pr1
41
0.0
01
29
0.0
01
15
0.0
01
49
0.0
00
59
0.0
00
64
0.0
00
84
0.0
38
50
.00
06
40
.05
51
Nd
14
30
.01
10
.00
7<0
.00
00
00
.00
87
10
.00
54
70
.00
87
90
.33
<0.0
00
00
<0.0
00
00
Sm1
47
<0.0
00
00
0.0
08
11
<0.0
00
00
0.0
05
04
0.0
04
48
0.0
04
15
0.1
91
0.0
04
50
.27
3
Eu1
51
<0.0
00
00
0.0
03
07
0.0
02
95
<0.0
00
00
0.0
01
38
0.0
02
22
0.0
41
80
.00
09
80
.10
3
Gd
15
70
.00
90
6<0
.00
00
00
.00
60
70
.00
50
70
.00
45
0.0
04
17
0.2
71
0.0
03
20
.33
6
Tb1
59
0.0
01
37
<0.0
00
00
<0.0
00
00
<0.0
00
00
0.0
00
48
0.0
00
63
0.0
29
0.0
00
48
<0.0
00
00
Dy1
63
0.0
03
85
0.0
05
99
0.0
13
60
.00
17
60
.00
19
10
.00
25
<0.0
00
00
0.0
03
84
0.2
02
Ho
16
50
.00
09
90
.00
12
60
.00
18
80
.00
04
50
.00
04
90
.00
09
1<0
.00
00
00
.00
05
0.0
52
2
Er1
67
0.0
05
68
0.0
06
25
0.0
05
38
0.0
03
18
0.0
01
99
0.0
05
23
0.1
20
.00
28
40
.12
2
Tm1
69
0.0
01
60
.00
14
30
.00
12
30
.00
07
30
.00
04
60
.00
08
50
.03
91
0.0
00
80
.06
85
Yb
17
10
.00
67
80
.00
60
9<0
.00
00
00
.00
43
80
.00
47
60
.04
90
.28
70
.00
33
80
.41
1
Lu1
75
0.0
01
48
0.0
03
39
0.0
01
40
.00
09
60
.00
09
0.0
01
36
0.0
54
30
.00
07
40
.03
17
Hf1
78
0.0
03
80
.00
48
3<0
.00
00
00
.00
17
30
.00
18
90
.04
0.1
97
0.0
01
9<0
.00
00
0
Ta1
81
<0.0
00
00
0.0
01
16
0.0
02
45
0.0
01
32
0.0
00
64
0.0
04
98
0.0
38
70
.00
12
90
.05
54
Pb
20
80
.00
58
90
.00
37
40
.00
39
50
.00
26
90
.00
25
30
.00
33
20
.12
50
.00
32
90
.17
9
Th2
32
0.0
02
07
0.0
01
32
0.0
01
39
0.0
00
95
<0.0
00
00
0.0
01
35
0.0
44
0.0
01
27
0.0
89
2
U2
38
0.0
02
02
0.0
01
28
0.0
02
34
0.0
01
13
0.0
01
23
<0.0
00
00
0.0
60
60
.00
10
10
.06
14
Pm
14
7<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
Po
20
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
U2
32
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
Pu
23
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
128
SAM
PLE
DEL
99
-2-0
1
GLI
TTER
!: M
ean
Raw
CP
S b
ackg
rou
nd
su
btr
acte
d.
Ele
me
nt
DEL
-99
-2-0
1-s
pt5
-op
x-a
DEL
-99
-2-0
1-s
pt5
-op
x-b
DEL
-99
-2-0
1-s
pt5
-cp
x-a
DEL
-99
-2-0
1-s
pt5
-cp
x-b
DEL
-99
-2-0
1-s
pt3
-cp
x-a
DEL
-99
-2-0
1-s
pt3
-cp
x-b
DEL
-99
-2-0
1-s
pt3
-cp
x-c
DEL
-99
-2-0
1-s
pt3
-op
x-a
DEL
-99
-2-0
1-s
pt3
-op
x-b
DEL
-99
-2-0
1-s
pt3
op
x-c
Li7
12
71
83
28
41
51
16
31
59
26
00
19
52
32
Mg2
41
06
45
01
11
01
87
89
85
03
86
31
51
23
30
66
47
42
56
58
52
25
35
72
90
65
10
21
44
34
10
37
12
51
10
21
29
74
Si2
97
70
87
93
77
14
16
89
38
20
87
52
87
65
48
10
18
18
17
82
3
P3
17
22
92
37
08
26
42
79
19
82
13
7
Ca4
33
78
73
72
42
21
11
22
18
99
32
55
93
32
42
75
52
40
58
24
05
23
72
13
65
0
Sc4
53
20
97
31
04
91
16
00
01
07
36
81
26
16
91
27
66
61
18
81
73
20
39
30
53
53
19
67
Ti4
93
53
33
34
58
42
78
32
32
53
15
52
85
12
93
12
42
62
72
78
13
26
46
33
20
43
52
16
V5
12
06
33
31
95
99
14
53
95
24
36
06
74
96
82
74
88
18
34
71
78
52
01
04
81
94
22
72
04
95
0
Cr5
24
59
87
34
64
57
47
08
16
96
88
02
58
08
81
07
72
25
47
67
07
24
75
63
74
55
44
94
69
33
8
Ni6
02
86
51
29
06
81
41
05
13
77
01
60
92
15
12
21
60
45
29
02
63
03
88
30
33
0
Cu
65
46
34
11
29
32
51
30
92
84
24
54
64
44
35
43
Rb
85
17
00
08
00
50
16
Sr8
82
52
13
76
45
39
49
94
61
99
44
22
84
54
12
68
59
57
Y8
92
36
82
25
85
61
51
54
71
76
03
32
61
33
05
86
80
24
31
23
45
24
06
Zr9
04
92
51
81
33
26
12
81
01
51
80
16
73
81
53
27
65
56
06
57
4
Nb
93
10
52
13
62
53
32
02
45
Cs1
33
41
07
16
04
01
00
Ba1
37
53
60
00
00
10
0
La1
39
01
14
91
15
25
17
71
18
38
18
67
41
0
Ce
14
06
48
72
28
52
51
01
67
10
36
71
03
31
30
33
10
Pr1
41
42
28
05
27
31
33
83
33
23
32
80
12
0
Nd
14
38
42
58
02
54
82
95
33
03
12
93
91
38
4
Sm1
47
51
21
59
81
52
51
59
61
69
61
67
35
61
1
Eu1
51
16
13
20
84
20
82
23
11
22
74
22
94
01
41
5
Gd
15
71
61
82
30
22
40
52
45
02
68
62
63
02
12
21
9
Tb1
59
44
42
28
86
27
67
30
23
32
66
32
11
54
38
66
Dy1
63
14
21
08
50
11
50
08
52
18
56
32
54
03
14
81
37
11
7
Ho
16
51
57
15
24
25
44
16
84
70
44
74
04
48
81
80
16
31
43
Er1
67
17
71
49
27
27
27
06
30
34
29
76
30
82
18
51
48
18
9
Tm1
69
14
21
59
18
54
17
85
19
02
19
28
18
87
15
11
59
14
4
Yb
17
11
86
17
31
57
81
54
31
56
91
74
61
56
91
90
27
91
82
Lu1
75
29
42
84
14
54
13
26
15
74
16
56
15
13
24
82
66
25
2
Hf1
78
40
42
99
29
40
11
17
12
11
11
07
36
31
53
Ta1
81
20
43
70
20
04
Pb
20
82
16
49
26
32
40
46
13
17
11
Th2
32
01
16
28
22
29
12
00
00
U2
38
10
18
62
51
11
10
00
Pm
14
75
12
15
98
15
25
15
96
16
96
16
73
56
11
Po
20
82
16
49
55
61
58
40
46
13
17
11
U2
32
01
16
28
22
29
12
00
00
Pu
23
81
01
86
25
11
11
00
0
129
SAM
PLE
DEL
99
-2-0
1
GLI
TTER
!: M
ean
Raw
CP
S b
ackg
rou
nd
su
btr
acte
d.
Ele
me
nt
DEL
-99
-2-0
1-s
pt3
-pl-
aD
EL-9
9-2
-01
-sp
t3-p
l-b
DEL
-99
-2-0
1-s
pt3
-pl-
cD
EL-9
9-2
-01
-sp
t8-c
px-
aD
EL-9
9-2
-01
-sp
t8-c
px-
bD
EL-9
9-2
-01
-sp
t8-o
px-
aD
EL-9
9-2
-01
-sp
t7-c
px-
aD
EL-9
9-2
-01
-sp
t7-c
px-
bD
EL-9
9-2
-01
-sp
t7-c
px-
c
Li7
29
07
22
40
25
02
26
15
63
43
19
8
Mg2
47
13
84
36
72
61
76
51
65
72
98
86
07
74
15
10
39
29
15
10
74
80
36
54
39
16
71
03
91
58
3
Si2
94
30
04
62
24
62
28
14
57
73
67
98
58
25
37
76
08
24
0
P3
11
61
49
20
00
01
01
2
Ca4
39
67
18
10
76
83
10
06
65
26
62
51
24
87
30
39
53
40
74
23
37
41
37
36
Sc4
56
46
57
83
46
11
97
85
11
40
17
29
79
03
25
04
11
59
54
32
20
8
Ti4
91
87
02
48
01
45
72
78
01
02
63
98
43
18
27
37
21
92
74
00
03
41
97
V5
12
89
72
83
81
45
15
05
87
14
78
64
91
94
86
62
02
50
44
61
59
82
07
16
6
Cr5
25
85
63
47
82
62
78
18
16
27
86
12
64
59
89
14
50
48
67
31
41
04
50
04
2
Ni6
01
59
57
38
17
05
01
68
09
30
66
73
11
10
14
96
73
07
18
Cu
65
09
23
33
67
30
14
42
47
72
82
42
9
Rb
85
29
94
38
20
12
05
14
0
Sr8
88
19
01
51
10
89
99
84
27
06
48
71
74
53
84
24
14
39
53
61
7
Y8
92
98
28
52
91
59
16
45
82
22
24
00
23
80
58
89
02
35
9
Zr9
05
53
83
41
06
90
10
40
74
40
50
31
22
27
47
5
Nb
93
30
07
33
83
43
05
Cs1
33
00
20
00
00
0
Ba1
37
44
04
60
07
43
83
01
40
06
0
La1
39
13
83
14
71
14
54
15
05
14
34
40
14
68
0
Ce
14
02
51
92
95
62
76
88
67
48
37
84
10
90
98
10
Pr1
41
40
34
68
35
42
85
12
78
70
02
81
81
3
Nd
14
31
76
20
71
81
26
79
26
43
30
28
53
8
Sm1
47
36
19
17
17
26
15
28
66
16
43
3
Eu1
51
38
34
13
35
42
35
32
20
83
15
22
78
17
Gd
15
74
33
43
92
46
82
46
81
72
52
61
33
1
Tb1
59
32
45
17
29
92
30
46
56
54
30
40
51
Dy1
63
29
32
22
54
28
52
66
15
51
34
53
87
13
7
Ho
16
52
33
12
34
55
04
47
41
55
16
24
46
81
64
Er1
67
10
21
18
30
60
29
26
17
61
22
29
98
14
6
Tm1
69
19
61
82
61
79
31
64
16
91
82
81
44
Yb
17
14
17
15
80
16
04
01
83
17
40
19
7
Lu1
75
10
11
45
71
48
32
74
24
51
51
22
50
Hf1
78
38
48
36
79
00
39
90
04
9
Ta1
81
11
02
00
02
0
Pb
20
83
20
38
83
37
52
35
13
22
59
9
Th2
32
00
11
62
90
01
30
U2
38
01
01
11
71
11
83
18
0
Pm
14
73
61
91
25
17
26
15
28
66
16
43
3
Po
20
83
20
38
83
37
52
35
13
22
59
9
U2
32
00
11
62
90
01
30
Pu
23
80
10
11
17
11
18
31
80
130
SAM
PLE
MV
P1
04
37
GLI
TTER
!: T
race
Ele
me
nt
Co
nce
ntr
atio
ns
MD
L fi
lte
red
.
Ele
me
nt
10
43
7-s
pt1
-px-
a1
04
37
-sp
t1-p
x-b
10
43
7-s
pt1
-px-
c1
04
37
-sp
t1-p
x-d
10
43
7-s
pt1
-px-
e1
04
37
-sp
t1-p
x-f
10
43
7-s
pt1
-pl-
a1
04
37
-sp
t1-p
l-b
10
43
7-s
pt2
-px-
a1
04
37
-sp
t2-p
x-b
10
43
7-s
pt2
-px-
c
Li7
12
.83
14
.66
16
.92
19
.71
18
.72
82
3.1
21
0.0
31
0.3
20
.47
89
6.8
59
48
.77
Mg2
48
58
62
.45
85
34
2.4
48
67
70
.61
85
41
8.9
18
26
76
.37
52
49
17
.59
31
.05
32
4.5
88
45
95
.66
66
20
34
76
88
29
27
Si2
92
60
82
1.7
82
59
42
7.6
12
55
61
5.6
42
67
25
2.8
42
59
92
3.9
51
60
70
83
93
63
69
6.0
63
87
18
1.7
52
59
63
0.7
81
43
34
79
01
51
16
25
9
P3
17
.95
15
.06
<5.8
1<5
.61
<5.5
8<3
47
.75
42
.71
31
.11
8.0
4<3
52
.81
62
9.8
1
Ca4
32
2.5
22
.52
2.5
22
.52
2.5
22
.51
81
82
2.5
22
.52
2.5
Sc4
51
73
.31
65
.55
16
9.6
31
69
.99
16
5.9
12
18
3.8
70
.88
40
.77
61
80
.62
22
95
.68
23
21
.77
Ti4
92
06
6.3
11
58
4.5
81
64
6.7
61
57
7.2
71
39
8.4
81
21
91
.99
20
.68
60
.03
19
05
.52
17
09
9.0
91
67
25
.24
V5
14
07
.02
35
2.1
36
0.7
43
70
.53
34
0.9
67
01
4.9
81
.39
1.2
02
40
8.4
37
45
7.5
47
41
3.3
1
Cr5
21
61
.82
15
6.6
61
64
.47
16
4.3
31
42
.11
39
02
.52
<1.1
2<1
.14
13
4.9
13
08
3.3
13
09
9.8
7
Ni6
02
0.4
92
0.5
42
3.1
12
3.9
22
2.1
91
94
5.5
91
.48
1.4
12
3.3
71
63
3.3
18
26
.18
Cu
65
1.2
61
.11
.47
1.1
51
.43
12
6.9
7<0
.46
<0.5
81
.39
13
5.1
61
11
.03
Rb
85
0.0
09
10
.01
81
0.0
11
4<0
.00
78
0.0
09
4<0
.46
<0.0
40
0.0
42
0.0
17
3<0
.53
<0.5
2
Sr8
81
2.4
41
1.6
81
3.3
11
3.5
11
2.6
90
.62
67
2.2
96
75
.84
21
.83
1.1
20
.69
Y8
91
07
.15
11
2.7
81
06
.25
10
9.2
61
11
.85
36
2.0
31
.06
61
.19
91
18
.91
39
7.3
23
93
.36
Zr9
09
7.7
29
6.0
99
09
7.2
89
9.4
88
.58
0.0
83
0.1
74
80
.62
65
.13
40
.69
Nb
93
0.0
62
0.0
49
60
.05
86
0.0
53
50
.05
63
0.2
79
<0.0
03
60
.00
42
0.1
30
.40
2<0
.08
4
Cs1
33
<0.0
01
26
0.0
01
22
<0.0
01
83
0.0
02
48
<0.0
02
13
<0.1
01
<0.0
04
9<0
.00
42
0.0
04
99
<0.0
99
<0.1
13
Ba1
37
0.1
86
0.0
19
0.0
63
60
.02
18
0.0
21
3<1
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13
1.6
21
34
.76
0.2
57
5.9
5<0
.72
La1
39
6.3
45
.97
6.0
26
5.6
72
.81
15
.91
5.3
26
.61
0.9
79
0.5
45
Ce
14
03
5.1
93
3.9
73
4.5
93
4.9
93
4.5
5.9
42
6.9
22
6.2
33
8.0
84
.16
2.9
Pr1
41
7.8
27
.77
7.7
88
.05
7.8
51
.15
42
.54
52
.51
68
.46
0.9
82
0.8
48
Nd
14
34
8.0
44
9.7
74
9.2
15
0.5
94
9.8
26
.32
8.6
58
.57
53
.03
9.5
6.1
2
Sm1
47
17
.65
18
.41
17
.59
18
.18
18
.33
7.9
50
.95
61
.03
91
9.7
46
.73
4.4
8
Eu1
51
2.9
63
3.1
89
3.0
26
3.1
32
3.1
66
1.8
72
.21
2.2
13
3.3
31
1.4
81
.69
Gd
15
72
0.4
32
1.6
72
0.3
82
1.3
32
1.3
71
6.8
0.5
64
0.6
63
22
.97
16
15
.24
Tb1
59
3.5
01
3.6
93
.49
53
.63
3.6
64
.49
0.0
47
0.0
54
23
.98
4.8
74
.76
Dy1
63
21
.44
22
.44
21
.76
22
.16
22
.65
45
.44
0.2
25
0.2
62
24
.08
49
.12
45
.71
Ho
16
54
.44
.67
4.4
34
.59
4.7
41
3.9
70
.03
41
0.0
36
65
.04
14
.96
14
.62
Er1
67
11
.34
11
.87
11
.41
11
.95
12
.32
55
.04
0.0
59
10
.10
51
2.8
96
2.0
25
9.8
3
Tm1
69
1.5
67
1.6
25
1.5
36
1.6
51
1.6
59
11
.10
.00
38
0.0
07
11
.77
12
.91
12
.4
Yb
17
19
.49
10
.25
9.7
10
.13
10
.19
10
8.6
10
.04
42
0.0
56
10
.71
11
3.0
51
10
.88
Lu1
75
1.3
09
1.3
87
1.3
72
1.3
89
1.4
72
19
.82
0.0
11
70
.00
47
1.4
88
20
.96
20
.53
Hf1
78
3.6
33
.33
.59
3.8
43
.69
6.5
80
.01
12
<0.0
07
73
.59
4.9
93
.15
Ta1
81
0.0
17
60
.01
51
0.0
16
0.0
13
30
.01
67
0.0
65
<0.0
01
50
<0.0
01
52
0.0
20
7<0
.08
10
.05
9
Pb
20
80
.29
40
.28
50
.22
40
.31
60
.31
91
.16
8.1
18
.24
0.3
61
3.0
11
.05
Th2
32
0.1
26
10
.07
36
0.0
67
10
.05
76
0.0
30
60
.73
10
.00
26
2<0
.00
35
0.0
61
60
.14
20
.10
3
U2
38
0.0
07
80
.07
29
0.0
06
35
0.0
07
50
.00
29
93
.09
<0.0
02
36
<0.0
04
10
.00
61
<0.0
52
<0.0
67
Pm
14
7<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
Po
20
8<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
U2
32
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN
Pu
23
8<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
<-N
aN<-
NaN
131
SAM
PLE
MV
P10
437
GLI
TTER
!: 1
sig
ma
err
or.
Elem
ent
1043
7-sp
t1-p
x-a
1043
7-sp
t1-p
x-b
1043
7-sp
t1-p
x-c
1043
7-sp
t1-p
x-d
1043
7-sp
t1-p
x-e
1043
7-sp
t1-p
x-f
1043
7-sp
t1-p
l-a
1043
7-sp
t1-p
l-b
1043
7-sp
t2-p
x-a
1043
7-sp
t2-p
x-b
1043
7-sp
t2-p
x-c
Li7
3.08
3.52
4.07
4.76
4.53
200.
252.
492.
565.
0122
0.48
233.
86
Mg2
415
085.
3415
078.
1615
416.
9115
262.
5514
856.
2613
6262
2.63
169.
2859
.41
1555
1.43
1226
287.
2512
8231
8.88
Si29
4156
529.
2541
3585
0.5
4076
597
4263
776.
541
4839
7.25
2565
8692
858
0893
561
8635
4.5
4149
904.
522
9211
040
2417
9689
6
P31
5.35
9.29
4.02
2.68
2.85
163.
2326
.41
19.9
35.
4516
7.92
404.
24
Ca4
30.
530.
520.
530.
530.
530.
640.
420.
420.
520.
630.
64
Sc45
4.53
4.33
4.45
4.46
4.36
63.0
80.
085
0.08
54.
7766
.27
67.2
3
Ti49
58.1
844
.71
46.5
744
.739
.73
379.
730.
882.
0454
.52
531.
4652
1.74
V51
11.2
39.
739.
9910
.28
9.47
211.
580.
061
0.05
611
.42
225.
3222
4.75
Cr5
25.
215.
055.
325.
334.
6213
5.57
0.49
0.5
4.44
108.
0710
9.07
Ni6
01.
271.
281.
441.
51.
412
3.71
0.6
0.63
1.49
105.
8111
8.48
Cu
650.
120.
110.
130.
120.
1310
.20.
20.
260.
1310
.86
9.4
Rb
850.
0032
0.00
350.
0037
0.00
360.
0035
0.2
0.01
70.
015
0.00
350.
220.
21
Sr88
0.44
0.42
0.48
0.49
0.46
0.11
24.4
324
.66
0.8
0.13
0.1
Y89
3.78
3.99
3.78
3.9
4.01
13.7
70.
043
0.04
94.
3315
.27
15.1
9
Zr90
3.29
3.24
3.05
3.31
3.39
3.43
0.01
50.
017
2.79
2.6
1.71
Nb
930.
0038
0.00
330.
0037
0.00
350.
0036
0.05
70.
0013
0.00
140.
0063
0.06
20.
03
Cs1
330.
0004
70.
0005
70.
0007
0.00
072
0.00
083
0.03
90.
002
0.00
160.
0008
70.
042
0.04
7
Ba1
370.
014
0.00
570.
0088
0.00
60.
0063
0.42
4.93
5.07
0.01
60.
590.
32
La13
90.
210.
20.
20.
20.
190.
160.
540.
520.
220.
082
0.06
1
Ce1
401.
11.
071.
091.
111.
090.
270.
860.
841.
220.
20.
15
Pr1
410.
230.
230.
230.
240.
230.
080.
079
0.07
80.
250.
070.
066
Nd
143
1.5
1.56
1.55
1.6
1.58
0.54
0.3
0.3
1.7
0.64
0.5
Sm14
70.
550.
570.
550.
570.
570.
540.
046
0.05
0.63
0.49
0.38
Eu15
10.
081
0.08
70.
083
0.08
70.
088
0.14
0.06
70.
067
0.09
30.
120.
13
Gd
157
0.63
0.67
0.63
0.66
0.66
0.88
0.03
20.
037
0.72
0.84
0.81
Tb15
90.
098
0.1
0.09
80.
10.
10.
190.
0033
0.00
370.
110.
20.
2
Dy1
630.
650.
680.
660.
680.
71.
720.
015
0.01
70.
751.
841.
73
Ho
165
0.14
0.14
0.14
0.14
0.15
0.52
0.00
280.
003
0.16
0.56
0.55
Er16
70.
360.
370.
360.
380.
392.
090.
0079
0.01
10.
412.
332.
26
Tm16
90.
047
0.04
80.
046
0.04
90.
050.
410.
0009
60.
0014
0.05
40.
470.
45
Yb17
10.
250.
270.
250.
260.
273.
490.
0078
0.01
0.28
3.6
3.54
Lu17
50.
035
0.03
70.
037
0.03
70.
039
0.63
0.00
170.
001
0.04
0.66
0.65
Hf1
780.
130.
120.
130.
140.
130.
410.
0029
0.00
390.
130.
340.
26
Ta18
10.
0015
0.00
130.
0015
0.00
140.
0015
0.02
40.
0004
60.
0006
60.
0016
0.02
80.
023
Pb
208
0.02
0.02
0.01
70.
022
0.02
20.
150.
540.
550.
026
0.29
0.14
Th23
20.
0051
0.00
340.
0033
0.00
390.
0021
0.07
50.
0008
80.
0011
0.00
310.
034
0.03
U23
80.
0011
0.00
460.
0009
50.
0011
0.00
080.
220.
0008
80.
0017
0.00
088
0.02
10.
027
Pm
147
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
Po
208
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
U23
2<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
Pu
238
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
132
SAM
PLE
MV
P1
04
37
GLI
TTER
!: M
inim
um
de
tect
ion
lim
its
(99
% c
on
fid
en
ce).
Ele
me
nt
10
43
7-s
pt1
-px-
a1
04
37
-sp
t1-p
x-b
10
43
7-s
pt1
-px-
c1
04
37
-sp
t1-p
x-d
10
43
7-s
pt1
-px-
e1
04
37
-sp
t1-p
x-f
10
43
7-s
pt1
-pl-
a1
04
37
-sp
t1-p
l-b
10
43
7-s
pt2
-px-
a1
04
37
-sp
t2-p
x-b
10
43
7-s
pt2
-px-
c
Li7
0.2
84
0.2
85
0.3
16
0.3
06
0.2
94
19
.74
0.9
05
0.9
18
0.3
32
19
.41
20
.74
Mg2
41
.05
1.2
91
.35
1.4
21
.37
98
.67
4.3
3.6
51
.41
84
.52
89
.38
Si2
94
72
.64
44
3.4
65
16
.49
55
7.8
65
47
.26
29
82
0.3
71
50
5.3
71
61
5.1
25
64
.47
34
00
1.9
83
12
59
.93
P3
15
.25
.33
5.8
15
.61
5.5
83
47
.75
16
.55
16
.75
6.1
83
52
.81
36
2.7
5
Ca4
30
.00
41
80
.00
43
40
.00
49
20
.00
46
40
.00
47
80
.29
80
.01
30
.01
34
0.0
04
69
0.2
88
0.3
19
Sc4
50
.05
51
0.0
59
70
.06
50
.06
26
0.0
62
43
.86
0.1
77
0.1
75
0.0
64
83
.79
3.9
Ti4
90
.20
70
.21
90
.21
30
.23
50
.26
51
3.6
70
.60
90
.70
60
.20
71
1.4
11
3.8
6
V5
10
.01
85
0.0
20
60
.02
10
.02
19
0.0
19
41
.25
0.0
61
40
.05
57
0.0
21
31
.28
1.3
3
Cr5
20
.38
30
.38
50
.40
80
.39
0.3
92
4.6
41
.12
1.1
40
.43
24
.65
25
.47
Ni6
00
.43
90
.45
30
.49
80
.48
80
.48
13
0.9
11
.36
1.4
10
.52
93
1.3
13
1.7
8
Cu
65
0.1
50
.16
90
.15
70
.16
20
.17
41
0.0
70
.46
30
.58
10
.18
10
.64
10
.58
Rb
85
0.0
05
94
0.0
06
47
0.0
07
37
0.0
07
77
0.0
07
12
0.4
60
.04
03
0.0
32
60
.00
67
80
.53
0.5
22
Sr8
80
.00
23
30
.00
27
60
.00
24
70
.00
26
30
.00
25
50
.17
30
.01
08
0.0
29
60
.00
55
90
.15
90
.14
8
Y8
90
.00
27
0.0
05
23
0.0
04
38
0.0
04
85
0.0
05
13
0.2
62
0.0
10
80
.00
90
60
.00
37
20
.24
50
.23
5
Zr9
00
.00
68
90
.00
97
20
.00
92
40
.01
05
0.0
11
0.6
39
0.0
27
90
.02
46
0.0
09
46
0.5
61
0.5
93
Nb
93
<0.0
00
00
0.0
01
40
.00
08
7<0
.00
00
00
.00
08
50
.05
50
.00
36
1<0
.00
00
0<0
.00
00
0<0
.00
00
00
.08
36
Cs1
33
0.0
01
26
0.0
01
09
0.0
01
83
0.0
01
21
0.0
02
13
0.1
01
0.0
04
89
0.0
04
17
0.0
01
39
0.0
99
0.1
13
Ba1
37
0.0
12
10
.01
03
0.0
12
60
.01
01
0.0
11
41
.11
0.0
27
30
.04
16
0.0
10
90
.67
70
.71
6
La1
39
0.0
00
47
0.0
01
16
0.0
00
88
0.0
01
24
0.0
00
98
0.0
69
80
.00
30
90
.00
38
20
.00
10
40
.06
77
0.0
64
Ce
14
00
.00
05
30
.00
13
50
.00
10
30
.00
18
80
.00
14
90
.10
9<0
.00
00
00
.00
41
0.0
00
72
0.0
59
2<0
.00
00
0
Pr1
41
0.0
00
77
0.0
00
94
0.0
00
80
.00
07
70
.00
09
30
.05
56
0.0
01
49
0.0
03
19
0.0
01
05
0.0
40
.05
46
Nd
14
30
.00
43
50
.00
75
70
.00
43
50
.00
72
60
.00
67
30
.47
70
.00
90
50
.01
58
0.0
05
88
<0.0
00
00
0.2
96
Sm1
47
0.0
02
91
0.0
03
31
0.0
03
56
0.0
02
42
0.0
04
26
0.1
59
0.0
07
4<0
.00
00
00
.00
27
70
.28
0.1
71
Eu1
51
0.0
00
45
0.0
01
45
0.0
00
95
0.0
01
30
.00
09
30
.09
22
0.0
02
29
0.0
03
65
0.0
01
49
0.0
70
80
.06
49
Gd
15
70
.00
20
70
.00
47
10
.00
50
60
.00
42
20
.00
42
90
.32
0.0
07
45
0.0
13
0.0
02
79
0.2
30
.24
4
Tb1
59
0.0
00
54
0.0
00
62
0.0
00
38
0.0
00
74
0.0
00
65
0.0
42
<0.0
00
00
0.0
01
61
<0.0
00
00
0.0
34
80
.05
21
Dy1
63
0.0
02
15
0.0
02
83
0.0
02
15
0.0
02
54
0.0
01
49
0.2
36
0.0
04
47
<0.0
00
00
0.0
02
91
0.0
97
9<0
.00
00
0
Ho
16
50
.00
05
50
.00
06
30
.00
07
80
.00
08
50
.00
11
50
.04
97
<0.0
00
00
<0.0
00
00
0.0
00
43
0.0
35
80
.04
64
Er1
67
0.0
03
18
0.0
02
56
0.0
01
59
0.0
03
75
0.0
03
11
0.2
25
0.0
08
10
.00
81
8<0
.00
00
0<0
.00
00
00
.18
8
Tm1
69
0.0
00
42
0.0
00
48
0.0
00
52
0.0
00
61
0.0
00
71
<0.0
00
00
0.0
01
07
0.0
01
53
0.0
00
57
0.0
40
70
.04
97
Yb
17
10
.00
43
7<0
.00
00
00
.00
37
90
.00
51
60
.00
37
10
.24
<0.0
00
00
0.0
11
30
.00
41
80
.24
40
.25
8
Lu1
75
0.0
00
58
0.0
00
67
0.0
00
72
0.0
00
80
.00
05
70
.04
53
0.0
01
72
<0.0
00
00
0.0
00
46
0.0
59
50
.04
88
Hf1
78
0.0
01
22
0.0
02
42
<0.0
00
00
0.0
02
04
0.0
04
15
0.0
95
<0.0
00
00
0.0
07
72
0.0
27
10
.16
70
.20
4
Ta1
81
0.0
00
59
0.0
00
47
0.0
01
02
0.0
01
20
.00
05
0.0
32
30
.00
15
0.0
01
52
<0.0
00
00
0.0
80
50
.03
48
Pb
20
80
.00
13
40
.00
24
20
.01
10
.00
25
10
.00
30
20
.10
40
.00
59
40
.00
69
30
.00
28
80
.15
0.1
12
Th2
32
0.0
00
95
<0.0
00
00
0.0
00
58
0.0
05
46
0.0
01
14
0.0
52
1<0
.00
00
00
.00
34
60
.00
14
40
.03
76
0.0
39
7
U2
38
0.0
00
80
.00
05
30
.00
08
0.0
00
95
0.0
01
24
<0.0
00
00
0.0
02
36
0.0
04
13
0.0
00
63
0.0
51
80
.06
71
Pm
14
7<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
Po
20
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
U2
32
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0
Pu
23
8<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
<0.0
0<0
.00
133
SAM
PLE
MV
P1
04
37
GLI
TTER
!: M
ean
Raw
CP
S b
ackg
rou
nd
su
btr
acte
d.
Ele
me
nt
10
43
7-s
pt1
-px-
a1
04
37
-sp
t1-p
x-b
10
43
7-s
pt1
-px-
c1
04
37
-sp
t1-p
x-d
10
43
7-s
pt1
-px-
e1
04
37
-sp
t1-p
x-f
10
43
7-s
pt1
-pl-
a1
04
37
-sp
t1-p
l-b
10
43
7-s
pt2
-px-
a1
04
37
-sp
t2-p
x-b
10
43
7-s
pt2
-px-
c
Li7
22
71
25
52
27
93
32
41
31
30
22
32
60
56
18
33
19
25
00
25
90
Mg2
47
34
40
80
71
42
09
16
84
23
86
66
71
39
76
52
59
65
95
78
93
82
62
42
90
43
63
27
12
68
46
26
50
85
67
12
8
Si2
91
04
65
10
20
99
50
29
86
39
71
99
71
54
88
05
14
89
29
18
78
99
04
7
P3
11
85
34
51
12
33
50
38
33
62
42
16
90
22
2
Ca4
33
17
22
13
11
25
12
94
11
22
92
12
72
96
07
84
78
88
50
62
84
32
52
83
77
34
86
34
74
9
Sc4
52
41
25
12
26
12
82
18
93
82
17
92
72
15
56
84
58
92
41
23
59
22
49
35
49
00
44
83
99
Ti4
91
75
69
01
32
21
61
29
85
81
23
55
81
11
05
11
56
60
58
91
69
71
45
11
72
23
23
21
32
6
V5
15
55
19
64
71
31
94
56
35
64
65
65
44
34
34
51
44
55
06
36
54
54
98
98
81
56
18
81
51
64
3
Cr5
21
68
67
71
60
25
01
59
01
11
57
83
41
38
36
46
14
62
26
61
95
12
59
89
49
36
44
84
75
Ni6
04
30
74
24
14
51
24
64
24
36
76
19
71
04
99
44
21
52
99
57
90
Cu
65
29
22
51
31
82
47
31
04
45
30
28
94
81
38
6
Rb
85
22
43
25
92
10
63
43
80
0
Sr8
84
56
14
42
03
44
52
58
45
62
24
34
39
34
82
66
19
82
38
05
71
64
06
23
7
Y8
94
49
84
94
64
51
44
13
51
34
22
34
54
38
15
52
29
35
14
99
16
71
44
63
91
25
56
32
47
13
Zr9
01
91
72
31
84
95
41
63
67
41
75
70
11
81
94
82
62
25
41
13
14
13
86
19
57
11
94
Nb
93
21
51
69
18
91
71
18
21
40
44
04
21
0
Cs1
33
08
01
50
00
03
00
0
Ba1
37
16
01
65
01
71
70
38
02
73
85
87
19
87
84
La1
39
40
77
73
76
63
35
88
63
55
13
33
98
62
72
34
24
13
26
93
37
98
39
65
2
Ce
14
02
31
26
62
19
01
92
10
68
52
11
58
62
11
43
65
88
59
21
35
71
73
22
34
29
41
72
84
Pr1
41
65
92
76
43
00
60
81
26
24
85
61
74
41
46
71
84
70
38
63
67
51
26
10
6
Nd
14
34
72
31
48
00
64
48
36
45
76
94
56
77
93
28
46
27
93
46
55
71
42
89
Sm1
47
21
20
62
17
05
19
58
62
01
05
20
53
71
44
38
44
14
21
18
81
23
80
Eu1
51
11
51
21
21
53
10
89
41
11
99
11
47
01
09
28
74
28
53
11
55
88
89
8
Gd
15
72
44
20
25
40
42
25
72
23
45
12
38
07
30
22
25
26
22
45
02
29
22
72
Tb1
59
27
68
22
86
48
25
60
42
64
25
27
00
95
35
12
41
41
28
07
45
88
56
1
Dy1
63
42
66
94
38
05
40
13
24
05
81
42
01
41
36
21
49
17
24
27
51
14
94
13
57
Ho
16
53
38
87
35
27
43
16
02
32
50
63
40
22
16
21
87
93
34
63
51
76
11
68
0
Er1
67
21
60
32
21
81
20
12
72
09
35
21
86
71
57
93
76
62
18
96
18
04
16
99
Tm1
69
13
00
61
32
28
11
81
01
26
00
12
82
41
38
61
01
91
30
93
16
36
15
34
Yb
17
11
07
07
11
34
41
01
47
10
52
01
07
23
18
46
16
21
10
77
51
94
91
86
6
Lu1
75
95
82
99
56
93
03
93
56
10
04
02
18
62
81
19
71
92
34
62
24
3
Hf1
78
73
19
65
16
67
02
71
17
69
35
19
97
36
46
11
53
94
Ta1
81
10
48
78
77
29
25
00
10
90
5
Pb
20
87
64
72
45
39
75
47
72
45
70
41
70
88
83
61
19
40
Th2
32
65
63
75
32
32
75
14
85
74
02
85
11
7
U2
38
41
38
13
13
61
42
48
00
28
00
Pm
14
72
12
06
21
70
51
95
86
20
10
52
05
37
14
43
84
41
42
11
88
12
38
0
Po
20
87
64
72
45
39
75
47
72
45
70
41
70
88
83
61
19
40
U2
32
65
63
75
32
32
75
14
85
74
02
85
11
7
Pu
23
84
13
81
31
36
14
24
80
02
80
0
134
APPENDIX 6 – CALCULATED CONCETRATION RATIOS AND PARTITION
CO-EFFICIENTS FROM PUBLISHED DATA.
Cli
nop
yroxen
e m
ineral/
wh
ole
rock
con
cen
trati
on
rati
os
Rb
T
h
U
Ta
Nb
L
a
Ce
Sr
Nd
Z
rH
f S
m
Eu
Gd
D
y
Y
Er
Yb
L
u
Ni
Cr
MV
P10437
0.0
00.3
90.4
60.0
30.0
10.4
91.1
00.0
22.0
61.1
81.7
62.6
11.6
12.8
22.8
63.0
02.8
93.0
62.9
50.8
01.9
1
MV
P10438
0.0
00.2
80.1
70.1
20.0
00.9
02.0
30.0
33.7
13.9
04.4
54.5
02.3
94.6
34.4
24.4
04.2
24.3
83.9
41.3
92.3
4
DE
L99-2
-01
0.0
00.0
60.0
90.0
30.0
10.3
20.9
90.0
32.6
62.2
53.0
83.3
62.4
63.6
73.2
93.4
83.2
63.3
63.1
70.5
82.7
1
MV
P99-2
-12
-0.0
50.0
80.0
30.0
21.0
21.6
00.1
51.9
71.6
52.3
61.4
51.0
50.7
80.2
80.1
70.1
20.0
60.0
52.6
41.2
5
MV
P99-2
-22
-0.3
30.1
20.0
20.0
11.3
01.6
90.1
11.9
51.4
61.8
01.6
51.2
81.1
90.5
70.3
80.2
80.1
60.1
32.0
51.7
9
DE
L2-1
0434
-0.0
50.0
40.0
10.0
00.5
20.8
50.4
91.1
00.9
01.1
11.0
00.8
80.7
50.3
80.2
60.2
00.1
20.0
91.0
81.0
4
Exp
erim
en
tal
parti
tion
coeff
icie
nts
0.0
31
0.0
30.0
40.0
13
0.0
05
0.1
047
0.1
254
0.0
60.2
866
0.1
31
0.1
208
0.4
774
0.5
618
0.5
954
0.6
218
0.9
0.6
356
0.6
01
0.5
602
2.6
3.8
Arth
, (1
976)
Fu
jim
ak
i et
al.
, (1
984)
Myse
n, (1
978)
Hart
an
d D
un
n, 1993
Orth
op
yroxen
e m
ineral/
wh
ole
rock
con
cen
trati
on
rati
os
Ba
Nb
C
e
Nd
Z
rS
m
Eu
Gd
D
y
Y
Er
Yb
L
u
Sc
MV
P10437
0.0
01
0.0
01
0.0
03
0.0
06
0.0
17
0.0
19
0.0
18
0.0
45
0.1
25
0.2
18
0.2
98
0.7
02
0.8
94
0.9
30
MV
P10438
-0.0
10
0.0
20
0.0
44
0.2
42
0.0
45
0.0
42
0.1
10
0.2
43
0.3
57
0.4
53
0.9
74
0.9
97
1.4
06
DE
L99-2
-01
0.0
00
0.0
00
0.0
00
0.0
07
0.1
12
0.0
19
0.0
32
0.0
40
0.1
04
0.1
77
0.2
26
0.5
19
0.7
07
0.9
70
Exp
erim
en
tal
parti
tion
coeff
icie
nts
0.0
13
0.1
50.0
20.0
30.1
80.0
50.0
50.0
90.1
50.1
80.2
30.3
40.4
21.2
Arth
, (1
976)
Pla
gio
lcase
min
eral/
wh
ole
rock
con
cen
trati
on
rati
os
Rb
B
a
Th
U
N
b
La
Ce
Sr
Nd
Z
rH
f S
m
Eu
Gd
D
y
Y
Er
Yb
L
u
MV
P10437
0.0
05
1.5
07
0.0
18
-0.0
01
1.2
90
0.8
48
1.0
31
0.3
55
0.0
02
0.0
05
0.1
44
1.1
38
0.0
82
0.0
31
0.0
31
0.0
20
0.0
15
0.0
17
MV
P10438
0.0
44
0.0
80
0.0
50
-0.0
11
1.0
89
0.8
06
1.0
42
0.3
47
0.0
08
-0.1
69
0.9
11
0.0
75
0.0
38
0.0
30
0.0
25
0.0
18
-
DE
L99-2
-01
0.0
15
0.1
85
-0.0
48
0.0
02
0.5
53
0.5
55
1.3
46
0.3
43
0.0
13
0.0
24
0.1
22
0.7
86
0.1
09
0.0
34
0.0
33
0.0
35
0.0
27
-
MV
P99-2
-12
0.0
15
0.2
38
--
0.0
01
0.8
04
0.4
45
2.8
32
0.1
38
--
0.0
42
0.3
94
0.0
24
0.0
06
-0.0
06
0.0
24
-
MV
P99-2
-22
0.0
46
0.2
78
0.0
31
0.1
33
0.0
02
0.6
75
0.3
24
1.9
00
0.0
98
0.0
00
0.0
05
0.0
30
0.3
34
0.0
11
0.0
04
0.0
02
0.0
04
0.0
06
0.0
06
Exp
erim
en
tal
parti
tion
coeff
icie
nts
0.0
71
0.2
30.0
10.0
10.0
10.1
90.1
21.8
30.0
81
0.0
48
0.0
51
0.0
67
0.3
40.0
63
0.0
55
0.0
30.0
63
0.0
67
0.0
6
Arth
, (1
976)
Fu
jim
ak
i et
al.
, (1
984)
135
Ga
rn
et
min
era
l/w
ho
le r
ock
co
ncen
tra
tio
n r
ati
os
Rb
B
a
Th
N
b
La
Ce
Sr
Nd
Z
rH
f S
m
Eu
Gd
D
y
Y
Er
Yb
L
u
Sc
MV
P9
9-2
-12
0.0
04
0.0
00
0.0
10
0.0
01
0.0
08
0.0
40
0.0
01
0.2
98
0.6
65
0.3
80
0.9
06
1.1
41
1.4
14
1.6
35
1.7
86
1.7
50
2.1
13
2.1
02
1.6
20
MV
P9
9-2
-22
0.0
03
0.0
00
0.0
47
0.0
03
0.0
06
0.0
31
0.0
00
0.2
15
0.3
62
0.1
76
0.7
36
1.0
19
1.6
52
2.5
76
3.0
76
3.1
66
3.7
32
3.8
57
1.9
42
DE
L2
-104
34
0.0
03
0.0
00
0.0
04
0.0
01
0.0
03
0.0
18
0.0
01
0.1
37
0.4
64
0.2
16
0.4
96
0.7
95
1.1
31
1.9
79
2.4
31
2.6
43
3.2
22
3.2
42
1.5
04
Ex
perim
en
tal
pa
rti
tio
n c
oeff
icie
nts
0.0
007
0.0
007
0.0
0137
0.2
40.0
016
0.0
05
0.0
025
0.0
52
0.2
70.0
031
0.2
50.4
0.6
82.2
3.1
3.6
6.6
7.1
2.6
2
Jo
hn
son
, (1
99
8)
Ha
uri
et
al.
, (1
99
4)
Irvin
g a
nd
Frey
, (1
97
8)
McK
en
zie a
nd
O'N
ion
s, (
199
1)
Ru
tile
min
era
l/w
hole
rock
con
cen
trati
on
rati
os
Rb
B
a
Th
U
N
b
Ta
La
Ce
Sr
Nd
Z
rH
f S
m
Eu
Gd
D
y
Y
Ho
Er
Tb
L
u
Yb
MV
P9
9-2
-12
0.0
02
--
14.6
52
338.1
48
573.8
60
0.0
29
0.0
04
0.0
02
0.0
20
35.9
50
37.7
77
-0.0
07
0.0
44
-0.0
11
0.0
03
0.0
11
-0.3
13
-
MV
P9
9-2
-22
0.0
0204
0.0
0257
4.0
8403
27.4
092
77.8
765
101.0
32
0.0
171
0.0
0198
0.0
0337
0.0
0195
27.7
328
23.6
593
--
0.0
0455
-0.0
0598
--
0.0
0223
0.0
0534
0.0
0435
DE
L2
-104
34
-0.0
00
0.0
96
3.5
14
52.3
06
96.9
85
-0.0
00
0.0
04
-12.3
85
10.5
84
0.0
21
0.0
01
0.0
73
-0.0
03
0.0
09
-0.0
00
0.0
09
0.0
22
Ex
perim
en
tal
pa
rti
tio
n c
oeff
icie
nts
28
36
2.8
12
Zr,
Nb
an
d T
a (
Ben
nett
et
al.
, 2
00
4)
Hf
hig
hest
va
lue f
ro
m (
Kle
mm
e e
t a
l.,
200
5)
Sca
po
lite
min
era
l/w
ho
le r
ock
co
ncen
tra
tio
n r
ati
os
La
Ce
Nd
S
m
Eu
Gd
T
b
Dy
H
o
Er
Yb
L
u
Ba
Th
N
b
Y
Hf
Ta
U
R
b
Sr
Sc
Zr
MV
P1
043
8A
5.0
71
4.7
82
2.9
76
1.3
79
1.3
33
0.9
20
0.5
95
0.4
59
0.3
28
0.2
97
0.1
97
0.2
30
0.0
80
0.0
72
-0.4
10
0.0
19
-0.0
69
0.1
56
0.8
60
0.0
06
-
MV
P9
9-2
-12
3.3
87
2.5
33
1.2
79
0.4
85
0.5
60
0.1
86
0.0
71
0.0
35
0.0
23
0.0
12
0.0
18
0.0
25
0.1
03
0.0
14
0.0
02
0.0
20
0.0
07
0.0
04
0.0
39
0.0
07
2.3
19
0.0
12
0.0
04
136
APPENDIX 7 – SHRIMP DATA
U-Pb isotope analyses of zircons from the two pyroxene granulite xenolith MVP10436. (Error for ages
quoted as 1σ). (204 Pb) corrected 206Pb/238U Ma (1σ error)
Zircon U-Pb spot analysis MVP10436
Grain
number
Spot
analysis
U (ppm) Th (ppm) 206Pb/238U Age 1s error
Zrc_1 36-01 23.266 10.11761 409.4373 10.67743
Zrc_1 36-02 320.1134 253.2767 422.4775 7.417539
Zrc_2 36-03 94.29916 65.30674 410.9466 8.042007
Zrc_3 36-04 114.6473 59.65866 414.0471 7.871262
Zrc_4 36-05 70.15758 53.64626 410.9062 8.66768
Zrc_4 36-07 70.22831 58.98187 397.615 8.14862
Zrc_5 36-06 124.3823 101.1763 385.4857 7.239134
Zrc_6 36-08 24.49363 12.0519 375.9392 11.25381
Zrc_7 36-09 40.13716 16.9941 425.8215 10.25929
Zrc_8 36-10 464.7232 407.1909 419.7649 21.80092
Zrc_8 36-11 51.71911 28.74154 430.8182 9.063939
Zrc_9 36-12 190.0077 151.261 405.5114 14.61896
Zrc_10 36-13 234.545 171.198 413.6329 7.399428
Zrc_11 36-14 307.1234 253.2527 414.6151 7.298821
Zrc_12 36-15 292.0162 214.1255 439.5797 16.72235
Zrc_13 36-16 146.7853 119.1733 433.4253 7.975261
Zrc_14 36-17 74.27484 48.48459 424.3781 8.435999
Zrc_15 36-18 63.98417 22.50337 432.5754 8.912881
137
U-Pb isotope analyses of zircons from the two pyroxene granulite xenolith MVP10437. (Error for ages
quoted as 1σ)
Zircon U-Pb spot analysis MVP10437
Grain
number
Spot
analysis
U (ppm) Th (ppm) 206Pb/238U Age 1s
err
Zrc_1 37-01 54.4346 41.46334 386.4381 9.17449
Zrc_1 37-02 55.58839 40.73986 381.1109 8.908048
Zrc_1 37-03 31.45861 30.91883 364.0612 9.961885
Zrc_1 37-04 60.59974 47.84816 371.8599 7.831385
Zrc_1 37-15 57.45387 42.07266 382.8903 8.320198
Zrc_2 37-05 35.68257 24.49753 399.8503 9.366056
Zrc_2 37-07 27.0405 20.20708 415.2181 10.92836
Zrc_3 37-06 56.38366 40.24586 390.1589 8.414634
Zrc_4 37-08 47.22175 17.47131 408.0798 9.362504
Zrc_5 37-09 33.64235 13.59223 378.2102 10.45922
Zrc_6 37-10 69.97747 54.19293 427.5121 8.967268
Zrc_7 37-11 589.6441 498.1413 395.7399 6.827423
Zrc_8 37-12 454.065 467.3586 387.116 6.737261
Zrc_9 37-13 264.6763 239.143 351.9511 6.265138
Zrc_10 37-14 40.41176 28.1932 412.7752 9.183357
Zrc_11 37-16 422.2244 269.0493 423.2044 7.363166
Zrc_11 37-17 63.35662 44.7374 412.4974 8.969504
138
References in Appendix
Keankeo, W., Taylor, W.R., FitzGerald, J,D., 2000. Clinoferrosilite-bearing kelyphite: a
breakdown product of xenolithic garnet, Delegate breccia pipes, New South
Wales, Australia. Mineral. Mag. 64, 469-479
Becker, H., 1997. Sm-Nd garnet ages and cooling history of high-temperature garnet
peridotite massifs and high pressure granulites from Lower Austria. Contrib.
Mineral. Petrol. 127, 224–236.
TEMORA
Grain
number
Spot
analysis
U (ppm) Th (ppm) 206Pb/238U Age 1s
err
Zrc_1 TEM2-01 138.4216 63.49054 435.2258 17.64489
Zrc_1 TEM2-02 281.4164 72.21548 421.1413 7.475124
Zrc_1 TEM2-03 218.6967 55.76253 423.4799 7.563013
Zrc_1 TEM2-04 134.796 62.22951 421.116 7.960547
Zrc_2 TEM2-05 126.683 57.84554 405.7282 8.01859
Zrc_3 TEM2-06 86.21236 24.7627 411.2918 8.045914
Zrc_4 TEM2-07 112.7308 59.25016 416.3577 7.927833
Zrc_5 TEM2-08 121.0498 59.7806 407.2281 7.711487
Zrc_5 TEM2-09 182.6942 84.52465 408.1324 7.446298
Zrc_5 TEM2-10 148.0921 74.09509 415.9314 7.818975
Zrc_5 TEM2-11 65.99863 21.6506 421.5372 8.806397
139
APPENDIX 8 – RESEARCH PROPOSAL
Major and trace element geochemistry,
geochronology and isotopic
compositions of deep-seated xenolith
inclusions from the Monaro Volcanic
Province, NSW Australia
Research proposal and literature review
Natasha Barrett
School of Earth and Environment, University of Western Australia, Crawley
May 2014
Word Count: 4685
Supervisors:
Dr Tony Kemp
A/Prof Eric Tohver (co-supervisor)
Formatted according to Earth and Planetary Science Letters (EPSL)
140
TABLE OF CONTENTS
8. Abstract………………………………………………………………………iii
9. Introduction……..…………………………..………………………….......1-2
10. Review of literature……………….….…………..………………………...2-9
10.1. Chemical composition of the lower continental crust………...……..2-5
10.2. Stable isotope studies……………………………………….….……5-8
10.3. U-Pb geochronology………………………………………..…...…….9
11. Geological setting……………………………………………………..…10-12
12. Summary of 2013 findings…………………………………..….…………..13
13. Aims and objectives…………………………………..……………... .…14-15
14. Significance and outcomes…………………………………………....…15-16
15. Methodology……………………………………..………….…….…..….16-18
8.1. Sample preparation………....…………………..……………....…16-17
8.2. BSE and CL imaging………….……………….…….….………..…...17
8.3. Trace element LA-ICPMS analysis….…………….…….……..……..17
8.4. SHRIMP U-Pb geochronology…………..………….……..….………17
8.5. Sulfur and carbon isotope analysis…………..……………………17-18
16. Conclusion………………………………………………….…….………..…18
17. References……………………...……………………………….……..…19-21
18. Appendices…………………...……………………………….….………22-25
18.1. Budget…………………………………….………………...….….….22
18.2. Timeline 2014…………………...……….………………...….…..….22
141
1. Abstract
Granulite xenoliths are samples of rock formed at deep levels within the Earth. They are
rapidly transported to the surface by volcanic pipes, and potentially represent direct
samples of the lower continental crust. Applying geochronology, along with major and
trace element analysis, to granulite xenoliths from the Monaro Volcanic Province (New
South Wales, Australia) will be the focus of this project. Obtaining high quality
geochemical data from whole rocks and minerals will build on a detailed petrographic
study conducted in 2013, and reveal if samples are lower crustal in origin by association
with the Silurian aged granitoid plutonism of the region. The first phase of this study
recognised primary scapolite, a mineral that is generally rare in exposed granulite
terranes and lower crustal xenoliths, but endemic to deep-seated xenoliths found in
eastern Australia. The structural properties of scapolite make this mineral a potential
stable reservoir for carbon and sulfur in the lower crust. This project will assess the
stable isotope fractionation of sulfur and carbon, and determine if there is any
relationship between volatiles in the lower crust and geochemical cycles observed at the
Earth’s surface. These sulfur and carbon isotope signatures in conjunction with zircon
ages, P-T estimates (from quantitative geothermobarometry) and bulk geochemistry will
form a basis for distinguishing the origin of the lower crust in this region, and provide
constraints on its evolution, chemical composition, and the significance and source of
its volatile reservoir.
1
2. Introduction
The Earth’s continental crust is characterised by its bulk andesitic composition (Taylor
and McLennan, 1985). While this is true for much of the Earth’s middle and upper
crust, this classification is favoured by the availability of upper crustal material over the
basaltic and inaccessible lower crust region (>23km depth; Rudnick and Gao, 2003).
The origin of the continental crust remains actively debated, and multiple fields of Earth
science are involved in unravelling its formation, structure and composition. It is much
older than the oceanic crust and contains most rocks in the geological record, thus
preserving an archive of Earth evolution. Exposed lower crustal material exists as
tectonically exhumed granulite facies terranes or in the form of xenoliths in volcanic
pipes (e.g. Irving, 1974; Francis, 1976).These pipes, forming explosive diatremes, bring
upper mantle and lower crustal fragments to the surface within hours to days (e.g.
Kushiro, 1976), which is ideal for preserving the prograde, high temperature mineral
assemblages of the lower crust.
This study focuses on deep-seated xenoliths, potentially representing samples of lower
crustal material, beneath the Monaro Volcanic Province, NSW Australia. Their
mineralogy denotes pressure and temperature conditions of granulite facies
metamorphism, possibly driven, at least in part, through heat advection from mantle-
derived magmas (e.g. Wells, 1980). Studying lower crustal rocks provides us with a
potential record for the addition of new material to the continents (Kemp et al., 2007) as
well as the petrological and chemical nature of the deep crust (Chen et al., 2001). The
proposed project will build on a detailed petrological study conducted in Part 1 of this
project (in 2013), where characterisation of the Monaro Volcanic Province xenoliths by
optical microscopy, scanning electron microscopy (SEM) and electron microprobe
analysis (EMPA), supported a lower crustal origin by analogy with several xenolith
samples from the previously studied Delegate breccia pipes in NSW (Chen et al., 1998;
Irving, 1974).
The aim of this study is to perform major and trace element geochemical analysis and
geochronology (zircon, U-Pb isotopes) on these xenoliths and key constituent minerals,
to determine the nature and potentially the age of the igneous protolith, or the time that
it was metamorphosed. In particular, primary scapolite identified in two rock types from
the Monaro Volcanic Province (two-pyroxene granulite and garnet-plagioclase-
clinopyroxenite) will be analysed, focusing on the nature of the crystallographic bound
volatile components, specifically carbon dioxide and sulfate. While it is expected that
2
sulfur and carbon in this lower crustal region derives from a magmatic source (e.g.
Hoeffs et al., 1982; Iyer et al., 1992), isotopic data can confirm this hypothesis through
δ34S (‰) and δ13C (‰) variations in scapolite from these samples. (δ34S (‰) denotes the
34S/32S abundance relative to the Canyon Diablo troilite meteorite, and δ13C (‰)
represents 13C/12C relative to the Pee Dee Belemnite Cretaceous marine fossil -
discussed further in later sections). Calculated δ34S (‰) and δ13C (‰) deviations will
reveal if sulfur and carbon originated from the oceanic crust (including evaporite
deposits and marine sediments), or if the source is mantle derived. This information,
together with geochronology, whole rock geochemistry and quantitative pressure-
temperature estimates calculated from whole rock data, will provide insight into the
metamorphic history of the lower crust beneath eastern Australia. Findings will
contribute to characterising the bulk chemical composition of the continental crust, and
by obtaining information on the metamorphic history and potential origin of lower
crustal material, answer existing questions regarding the nature of the continental crust
as a whole, and the processes responsible for its formation and preservation through
time.
3. Review of literature
3.1. Chemical composition of the lower continental crust
The bulk continental crust is currently regarded to be intermediate in composition
(Taylor and McLennan, 1985), and holds the majority of the Earth’s heat producing
incompatible trace elements, e.g., 35-55% of the Rb, Ba, Pb, K, Th and U (Rudnick and
Fountain, 1995). Calculating the chemical composition of the lower crust is far more
difficult due to the inaccessibility of the Earth’s crust beyond 12kms depth
(Kremenetsky and Ovchinnikov, 1986). While granulites studied from xenoliths and
exposed granulite terranes are lithologically heterogeneous, they are mostly mafic,
approaching a basaltic composition (Rudnick and Fountain, 1995). The granulitic lower
crust is generally believed to represent a residual or cumulate composition from the
crystallisation and extraction of magmas, and thus be refractory, depleted in radioactive
heat producing incompatible elements (K, Th, U) (Figure 1), and mechanically strong
due to the dominance of pyroxene over quartz (Taylor and McLennan, 1985). Formation
of the lower crust may therefore be fundamental for the preservation, strengthening and
stabilization of continents as a whole (Rudnick, 1995). Several estimates of the
composition of the lower and bulk continental crust are presented in Table 1.
3
Figure 1. (A) Rare earth element patterns of upper (Taylor and McLennan, 1985), middle and lower
continental crust. (B) Relative enrichment/depletion of elements in the middle and lower crusts compared
with upper crust from Rudnick and Fountain (1995).
4
Lower continental
crust
Lower
continental crust
Continental
crust
Continental
crust
Continental
crust
Taylor and
McLennan (1985)
(wt. %)
Rudnick and
Fountain (1995)
(wt. %)
Taylor and
McLennan
(1985) (wt. %)
Rudnick and
Fountain
(1995) (wt. %)
Wedepohl
(1995) (wt. %)
SiO2 54.4 52.3 57.3 59.1 61.5
TiO2 1.0 0.8 0.9 0.7 0.68
Al2O3 16.1 16.6 15.9 15.8 15.1
FeO 10.6 8.4 9.1 6.6 6.28
MgO 6.3 7.1 5.3 4.4 3.7
CaO 8.5 9.4 7.4 6.4 5.5
Na2O 2.8 2.6 3.1 3.2 3.2
K2O 0.34 0.6 1.1 1.88 2.4
Total 100.04 97.80 100.1 98.08 98.36
Rb
(ppm)
5.3 11 32 58 78
Sr
(ppm)
230 348 260 325 333
Y
(ppm)
19 16 20 20 24
Zr
(ppm)
70 68 100 123 203
Nb
(ppm)
6 5 11 12 19
Cs
(ppm)
0.1 0.3 1.0 2.6 3
Ba
(ppm)
150 259 250 390 584
La
(ppm)
11 8 16 18 30
5
Pb
(ppm)
4.0 4.2 8.0 12.6 14.8
Th
(ppm)
1.06 1.2 3.5 5.6 8.5
U
(ppm)
0.28 0.2 0.91 1.42 1.7
Table 1. Compositional estimates of the lower continental crust and bulk composition of the continental
crust from Yanagi, (2011). (Total Iron as FeO)
Geochemical data will be obtained from the Monaro Volcanic Province xenoliths in
conjunction with samples from the Delegate breccia pipes, to investigate the
heterogeneity of the lower crust beneath eastern Australia. Both suites of volcanically
derived xenoliths reside within the eastern Lachlan Fold Belt, and geochemical analysis
will therefore determine if samples represent fragments of lower crust subject to the
same, or an entirely different, metamorphic history.
The two major rock types from the Delegate pipes, a two-pyroxene granulite and garnet-
plagioclase-clinopyroxenite have a significantly different major and trace element
distribution to other granulites from these xenolith suites (Irving, 1974). Additionally,
some of the previously studied Delegate xenoliths have higher Al and Ca but lower Na
and K contents than typical basalts. These xenoliths have been understood to represent
early cumulates from basaltic magmas, or residues of partial melting, where the amount
of alkalis and SiO2 was reduced by the removal of a more felsic composition melt phase
(White and Chappell, 1989).
Analysing the Delegate samples, in addition to those from the Monaro Volcanic
Province, will ensure the collected data is consistent for comparison with previous
chemical signatures, and produce reliable results for investigation regarding the
composition of the lower crust under eastern Australia. Major and trace element
analysis from both whole rock and minerals (the later by laser ablation ICPMS) will
potentially tell us the nature of the source rock in the deep crust or upper mantle, and
processes by which it was formed or modified.
3.2. Stable isotope studies
6
While it is understood that sulfur and carbon in the oceanic crust and sediments are
introduced into the mantle at subduction zones, much is still unknown about the fate of
this material in the Earth’s interior (Figure 2). An important feature of the Monaro
Volcanic Province xenoliths is the presence of primary scapolite in several of these
samples. The physical properties of scapolite and its ability to sequester SO4 and CO2 in
its structure make it possible to investigate the nature and source of these volatiles in the
lower crust.
The sulfur cycle has been studied over several decades (e.g. Canfield, 2004; Seal, 2006),
although little has been published on its isotopic effects during subduction and high-
pressure metamorphism in the lower crust. Most models on the global sulfur budget are
developed without knowledge of these processes, and leave much to be answered
regarding the nature of geochemical cycles at both lower crustal and mantle depths
(Figure 3). An important question that needs to be addressed is whether sulfur and
carbon in the lower crust originated from the Earth’s surface, and was recycled through
subduction or other crust-mantle exchange processes (e.g. density foundering), or if this
reservoir of sulfur and carbon is derived from the mantle via the emplacement of
primitive magmas.
There are 4 stable isotopes of sulfur 32S,33S, 34S, and 36S. Figure 4 shows a graph of
natural sulfur isotope reservoirs with a summary of isotopic compositions of some
major rock types. The 34S/32S ratio of sample material is conventionally expressed
relative to the S isotope composition of troilite from the from the Canyon Diablo troilite
meteorite, and given by the notation δ34S. This is calculated as follows:
δ34 S [‰] =
(
(S34
S32⁄ )
Sample
(S34
S32⁄ )
CDT
− 1
)
x 1000
With respect to δ34S, there are 3 distinct reservoirs, these are (1) sulfur derived from the
mantle, δ34S ranging 0 ± 3 ‰ (Chaussidon and Lorand, 1990), (2) sulfur derived from
sea water, δ34S ranging from +18.5 to 21.0 ‰ for modern sea water and (3) sedimentary
sulfur showing strong negative to positive δ34S values ranging from -56 to +20 ‰, in
part reflecting fractionation associated with biological activity (see Figure 4). This
proposed study will aim to investigate the isotope composition of sulfur in scapolite
occurring naturally in high pressure rock samples. This will be done by comparing
δ34S‰ values in scapolite with those of natural sulfur reservoirs, and thus determining
7
the potential source for stable sulfur in the lower crust, and to test whether this can only
be explained by an internal magmatic source (e.g. Hoefs et al., 1982; Iyer et al., 1992).
It is also possible that, like sulphur addition, regions of the mantle have been carbonated
by earlier subduction of supracrustal carbonate-rich sediments, and have entered into the
lower crust via CO2 fluxes which caused granulite metamorphism (Harley, 1989).
Carbon has 2 stable isotopes, 13C and 12C, where δ13C‰ represents the ratio of 13C/12C
relative to the Pee Dee Belemnite, a Cretaceous marine fossil used as the reference
standard. This value is given by:
δ13 C [‰] =
(
(C13
C12⁄ )
Sample
(C13
C12⁄ )
PDB
− 1
)
x 1000
δ13C‰ will be analysed to determine if deviations from the standard are consistent with
the crystallization of scapolite from a mafic melt emplaced at the lower crust such as
xenoliths studied in Moecher et al., (1994) producing δ13C ‰ values of -8.2 to -1.2 in
scapolite.
Figure 2. Vertical cross section sketch through the crust and upper mantle showing the sulfur cycle in the
plate tectonic context by Shimizu and Marschall, (2012). Input materials delivered to subduction zones
are shown in blue, and output materials shown in orange. Diagram shows a significant gap in our
knowledge on the sulfur cycle, as no data exists on the processes effecting the sulfur budget and
isotopic composition of materials within subduction zones (outlined in red).
8
The lower crust represents an unconstrained ‘black box’ on the sulfur and carbon
budgets. While it signifies a potential sink for sulfur and carbon, its remains poorly
understood due to the extensive area it covers. The exact amount of these elements in
the lower crust, how they are hosted in rocks, and their origin still remain largely
enigmatic.
Figure 3. Schematic diagram showing the cycle of sulfur/sulfur isotopes between surface reservoirs.
Ocean sulfate (blue), sulfides (yellow) and sulfates (orange) in crustal rocks and the mantle (green) (data
from Canfield, 2004). The isotopic composition of crustal and surface reservoirs are well characterised
whereas subduction-zone input into the mantle and lower crust remain in question (Shimizu and
Marschall, 2012).
9
Figure 4. Natural sulphur isotope reservoirs. Data from Sakai et al., (1982; 1984), Ueda and Sakai,
(1984), Claypool et al., (1980), Kerridge et al., (1983), Chambers, (1982), Coleman, (1977) and
Chaussidon et al., (1989).
3.3. U-Pb geochronology
While geochemistry and thermobarometry provide potential pressure and temperature
conditions for formation, it is not possible to classify samples as fragments of lower
crust without information on their age, distinguishing samples from the host rock, and
thus ruling out the possibility of a magmatic cumulate subject to granulite conditions.
Isotope studies have been done on metamorphic zircons in the two-pyroxene granulite
xenoliths from the Delegate breccia pipes using a thermal ionisation mass spectrometer,
producing U-Pb ages of 398±2 Ma and 391±2 Ma (Chen et al., 1998). Zircon ages have
also been reported from xenoliths hosted by alkali basalts in the McBride Province,
north Queensland giving U-Pb ages of ̴ 320-220 Ma by ion microprobe analysis
(Rudnick and Williams, 1987). Both localities have been interpreted to date granulite
facies metamorphism in the lower crust.
U-Pb geochronology on the Delegate pipe xenoliths by Chen et al., (1998) was
conducted using the VG354 thermal ionisation mass spectrometer (TIMS) at the Royal
Ontario Museum’s Geochronology Laboratory, Canada, while zircon ages from the
McBride Province in north Queensland were analysed using the sensitive high
resolution ion microprobe (SHRIMP) at the Australian National University Research
School of Earth Science. The McBride Province study suggested that the use of the ion
10
microprobe would allow analysis of multiple growth phases within small (approx.
<60µm) zircons, critical to date episodic events of crustal growth (Rudnick, 1992;
Hancher and Rudnick, 1995). Additionally, retaining the analysed zircons from
SHRIMP dating will allow further analysis of trace elements and oxygen isotope
compositions on the same zircon grains. For these reasons, in-situ analysis of zircon by
ion microprobe will be the preferred method for instrumental analysis in this project.
Samples in this study contain mineral assemblages showing both equilibrium and
disequilibrium textures, as established during the first phase of this study completed in
2013. While disequilibrium textures can help decipher a P-T path, it is difficult to apply
quantitative thermobarometry and geochronology to these samples. Nonetheless,
analysing the petrography of the disequilibrium samples along with geochronology
from the other samples within the Monaro Volcanic Province, may provide a unique
insight into the lower crust and a polymetamorphic history.
4. Geological setting
Xenolith samples were collected from two localities in southeastern New South Wales
by Professor Richard Arculus at the Australian National University in 2000, and made
available for this study. Five samples were from the two diatremes known as the
Delegate breccia pipes outcropping at Airlie Park homestead, 35kms northwest of
Delegate, NSW (Lovering and White, 1969) (Figure 5). These pipes are Mid-Jurassic in
age, ̴ 168 Ma based on K-Ar dating methods (Lovering and Richards, 1964). Twelve
xenolith samples were from alkali basalt pipes, Eocene-Oligocene in age (56-34 Ma;
Taylor et al., 1990) located north of the Delegate around the town of Nimmitabel, NSW
within the Monaro Volcanic Province (Figure 6). This Monaro Volcanic Province hosts
approximately 65 eruption sites within its basaltic lava field (Roach et al., 1994). The
region has experienced extensive mafic volcanism which began during the late
Palaeocene and lasted for about 20 million years, where at least 630 cubic kilometres of
pyroclasts and lava erupted (Brown et al., 1993). The province is believed to be built up
by eruptions of alkali basalt, basanite and nephelinite (Roach et al., 1994). The surface
geology is dominated by mafic lavas and Tertiary volcanic sediments which overly
Ordovician-Devonian bedrock (Figure 6). Although much of the volcanic material has
been eroded away, several landmarks still exist showing evidence of a formerly active
11
volcanic province including the Brothers volcanic plugs and several flat topped hills
which represent stacks of lava flows (Brown et al., 1993).
Both localities occur within the Ordovician-Devonian Lachlan Fold Belt of eastern
Australia, but are related to a much younger hot-spot magmatism (Johnson et al., 1999).
The Lachlan Fold Belt is itself part of the Terra Australis Orogen, a vast subduction-
related accretionary orogenic system that developed along the eastern paleo-pacific
margin of Gondwanaland during the Palaeozoic and Mesozoic (Cawood and Buchan
2007; Braun and Pauselli, 2004). This tectonic unit comprises the eastern third of the
Australian continent (Gray and Foster, 2004), as well as comprising a large part of
western Antarctica and Argentina.
12
Figure 5. Map showing the location and regional setting of the Delegate pipes, in southern NSW,
Australia (Lovering and White, 1969).
13
Figure 6. Outline of the Monaro Volcanic Province. Samples were collected around the town of
Nimmitabel. The shaded region represents mafic lavas and Tertiary sediments, while the surrounding area
represents the Ordovician-Devonian Bedrock. Lava pile outline is from Lewis et al., (1994) modified by
Roach, (2004).
14
5. Summary of 2013 findings
This investigation will aim to build on the research project undertaken in 2013 which
focused on characterising the petrography and mineral chemistry of unclassified
xenoliths from the Monaro Volcanic Province. The 2013 study identified 3 rock types, a
two pyroxene granulite, garnet-plagioclase-clinopyroxenite and a reaction intermediate
showing disequilibrium textures between plagioclase, clinopyroxene, orthopyroxene,
garnet, spinel and ilmenite. The two pyroxene granulite and garnet-plagioclase-
clinopyroxenite samples showed the widespread occurrence of scapolite co-existing in
textural equilibrium with granulite minerals. Pressure and temperature ranges for these
samples were constrained from electron microprobe data, and are consistent with
derivation from a thermally perturbed and thickened lower continental crust. Textures
identified in the third sample indicate a dynamic and complex history in the lower crust,
and could potentially provide evidence for larger scale processes of crustal thickening
and extension, as typifies convergent plate margins. Findings from optical microscopy,
secondary electron microscopy and electron microprobe analysis performed in the initial
stages of this project, have provided a basis for more quantitative microanalysis
focusing on whole rock geochemistry, trace element analysis and geochronology, to
further investigate the history of the lower crust and characterise its composition.
15
6. Aims and objectives
The aim of this study is to make progress towards classifying the origin, and eventually,
resolving the genesis of granulite xenoliths from the Delegate and Monaro Volcanic
Province localities. The specific objectives of this project are:
1. Obtaining accurate and precise whole rock, major and trace element data for
each classified rock type, and to interpret this data by constructing REE and
multi-element spider diagrams.
2. To analyse the trace element content in each mineral, including major peak
metamorphic minerals, to further constrain P-T estimates (such as the Zr
exchange between co-existing rutile and zircon) and understand the growth
history and equilibrium/chemical exchange amongst phases.
3. Determine ages of granulite facies metamorphism, and potentially the igneous
protolith, through U-Pb geochronology of zircon.
4. And investigate the stable isotopes of sulfur and carbon in scapolite, and
determine the origin of these elements in the lower crust.
It is proposed that U-Pb geochronology of zircon will date the age of granulite facies
metamorphism, by analogy with similar zircon ages obtained from xenolith from the
Delegate Breccia pipes (Chen et al., 1998). This could suggest whether granulite
metamorphism in both samples is driven by heat related to production of voluminous
felsic magmatism and batholith emplacement in this part of the Lachlan Fold Belt (~420
to 380 Ma; e.g. Gray and Foster, 2004). Previous studies across several continents have
assumed that xenoliths contained by similar volcanic rocks represent fragments of lower
crust (e.g. Francis, 1976; Selverstone and Stern, 1983; Kempton and Harmon, 1992;
Kay and Kay, 1983; Leyreloup et al., 1982). The exact origin of samples in this project
has, however, yet to be determined. Before interpreting data from the xenoliths in terms
of lower crustal processes, we first need to consider if the study samples did in fact
originate from the lower crust, which can be established from dating the xenolith
samples relative to the younger Eocene-Oligocene aged host rock (Roach, 2004).
Whole rock geochemistry will also be used to constrain pressure and temperature
estimates by applying this data to the thermodynamic database THERMOCALC
(Powell and Holland, 1988). Geochronology and whole rock geochemical data will be
analysed in conjunction with mineralogy and textural features to assess changes in P-T
16
conditions through time, as well as making interpretations regarding the chemical
composition of the lower crust relative to the upper crust.
Stable isotope studies of sulfur and carbon (as SO4 and CO2) in scapolite will give
isotopic signatures that will determine if carbon and sulfur in the deep earth originated
from a magmatic source in the deep mantle or a potential upper crustal reservoir. If
isotopic data reveal signatures exclusively generated through atmospheric
photochemical reactions and oceanic sediments, results could confirm the cycling of
sulfur and/or carbon between the major geochemical reservoirs and extend from the
oceans and atmosphere to the lower crust via subduction, and ultimately return these
elements to the Earth’s surface through volcanic pipes. Such results in combination with
geochronology, would additionally reveal that this material must have originated at the
surface prior to the age of metamorphism determined by U-Pb zircon dating, and help
constrain the tectonic setting.
7. Significance and outcomes
The bulk andesitic nature of the Earth’s continental crust is a unique feature in our solar
system (Taylor and McLennan, 1985). Characterising the composition of the lower crust
and the crust as a whole is the first stage in unravelling its nature and development, and
plays an important role in understanding the evolution of our planet. Direct, pristine
samples of lower crustal rock are currently only available in the form of xenoliths
brought to the surface by ascending mantle-derived magmas. Exposed granulite terranes
are generally considered to be less representative of the lower crust, and processes
responsible for their exhumation typically result in samples where little of the prograde
mineral assemblage has been preserved.
There are several unanswered questions relating to the composition, formation and
association of the lower crust with the more felsic upper crust. Linking geochronology
with petrology and geochemistry will help resolve this knowledge gap and make way
for future research. Investigating lower crustal xenoliths from the Lachlan Fold Belt
and wider Terra Australis Orogen, will provide information about magmatic processes
along this margin, as well as the general evolution of the continental crust. This is
important, as magmatic processes during the evolution of this orogenic system formed
the eastern third of the Australian continent, representing an efficient mechanism for
generation and preservation of continental material on Earth.
17
Geochemical cycles, particularly the CO2 budget, are critical for maintaining a habitable
Earth climate through geological time (e.g. Dasgupta and Hirschmann, 2010). The
examination of sulfur and carbon isotopes in scapolite will characterise the source of
volatiles in the lower crust, as well as provide potential evidence for deep crustal
recycling through subduction. This speaks to the mass balance of recycling processes
during subduction, i.e. how much subducted material is returned to the continents via
subduction, and how much of this material disappears into the deep mantle.
8. Methodology
8.1. Sample preparation
Contamination on rock samples (i.e. saw marks, ink or alteration from weathering)
could potentially effect the geochemical results. To avoid this, samples are trimmed,
polished, washed in deionise water and placed in an ultrasonic cleaner bath to remove
excess artefacts. Each sample will then be reduced to rock chips using a hydraulic
tungsten-carbide rock crusher. Only the freshest material will be used for geochemical
analysis. Samples for mineral separation are pulverised using a disk mill adjusted to
500µm grainsize output, and those for geochemical analysis reduced to a powder using
an agate (silica based) mill to avoid tungsten carbide contamination, which can
compromise trace elements such as Ta. Both crushing and milling of samples will be
undertaken in the crushing rooms at the University of Western Australia.
Mineral separation will involve several steps. Initially, the heavy fraction will be pre-
concentrated by hydrodynamic methods (Wilfley Table and/or panning). The magnetic
minerals will be removed from this with a Frantz isodynamic magnetic separator.
Zircon and other accessory minerals are then isolated from the non-magnetic fraction
using a LST heavy liquid (density ~2.9g/cm3). Samples are run through the magnetic
separator a second time to allow the highest quality, crack free zircons to be hand-
picked and mounted into an epoxy resin for in situ microprobe analysis. This work will
be conducted in UWA’s mineral separation laboratory.
The powder for bulk chemical analysis will be sent to the GeoAnalytical Laboratory at
Washington State University, where each powder is fused with a Lithium Tetraborate
flux and made into homogenous glass disks for major and trace element signatures
using X-Ray fluorescence (XRF, for major and some trace elements), and inductively
coupled mass spectrometry (ICPMS, for most trace elements, involves acid digestion of
18
the disc followed by dilution and analysis in solution mode). Volatile components will
be determined by loss on ignition, heating the sample overnight at 1100°C in a furnace.
Several reference rock powders will be analysed as unknowns concurrently with the
samples to assess the accuracy of the results.
8.2. BSE and CL imaging
Zircon grains will be characterised using Scanning Electron Microscopy, applying both
backscattered electron (BSE) and cathodeluminescence (CL) imaging. Both techniques
will show any growth zoning or internal structures in zircon, which is important to
establish before performing SHRIMP analysis. This will be undertaken at UWA’s
Centre for Microscopy, Characterisation and Analysis.
8.3. Trace element LA-ICPMS analysis
In situ trace element analysis of major minerals (e.g., garnet, plagioclase, pyroxene) will
be conducted on 6 polished thin sections using LA-ICPMS in the Advanced Analytical
Centre at James Cook University Townsville, Queensland. Spot analysis will be done
on minerals where previous EMP major element data has been collected to calibrate
areas for trace element analysis (Reed, 2005). Whole rock analysis will also provide
major, trace element and rare earth element geochemical data. This information will be
applied to the thermodynamic database program THERMOCALC for quantitative P-T
values.
8.4. SHRIMP U-Pb geochronology
U-Pb Geochronology in zircon will be undertaken at the John de Laeter Centre for
isotope research at Curtin University, using the Sensitive High Resolution Ion
Microprobe (SHRIMP). This high spatial resolution method will be used for reasons
outlined above. Well established analytical protocols will be followed for this analysis
(Williams, 1998). 8.5. Sulfur and carbon isotope analysis
In order to distinguish deep-seated sulfur from sulfur occurring in secondary minerals
(mainly fines sulphides located in altered areas in the rock), scapolite grains are
individually picked for analysis following magnetic separation of mafic minerals.
Contamination, particularly calcite could affect the δ13Cscap results. Any impurities will
be assessed using optical microscopy, BSE, CL and EMP imaging where possible. CO2
can be extracted from scapolite without fractionating the carbon isotopes by reaction
with phosphoric acid (H3PO4) at 25°C (e.g. Moecher, 1994). Acid extraction of
19
scapolite will yield both CO2 and SO4. The gas from the reaction between scapolite and
H3PO4 and CO2 and SO4 separated by distillation in an n-pentane slush. Isotopic
analysis of CO2 and SO4 will be done at GNS Science, National Isotope Centre, New
Zealand.
9. Conclusion
The main objective of this project will be to obtain high quality geochemical and
geochronological data on deep-seated xenolith samples from the Monaro Volcanic
Province, NSW Australia, and to link this chemical record with petrology and textures.
Such information from lower crustal samples is important for understanding the
dynamics of the Earth’s lithosphere in terms of its metamorphism and orogenesis. The
volatile nature of the lower crust remains a critical knowledge gap, and analysing the
existence of sulfur and carbon in scapolite will characterise their isotopic signatures in
the lower crust and potentially the origin of lower crustal material in this region.
Findings from this project will contribute to further research on these samples including
the application of other isotopic systems (e.g. Lu-Hf, Sm-Nd of garnet, pyroxene) and
dating of other accessory phases to derive additional chronological constraints. In
general, as more similarly derived xenolith suites are characterised around the world we
can more accurately determine the bulk composition of the lower crust and the
continental crust as a whole.
20
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11. Appendices
11.1. Budget
Task and details Anticipated expenditure
CMCA facilities (Zeiss 1555 VP-FESEM, TESCAN
VEGA3 and JEOL 8530F microprobe)
$500.00
AAC facilities (Townsville) (LA-ICPMS and EMPA)
$1000.00
John de Laeter Centre (SHRIMP analysis) $1400.00
Flights/accommodation/transport $1900.00
T
Whole rock major and trace element analysis $2200.00
Sulfur and carbon isotope analysis $1000.00
Crushing and milling facilities $300.00
Postage costs
$100.00
Sandvik sample vials and self-seal plastic bags
$20.00
Printing/Copying $100.00
Total expected costs $8520.00
11.2. Timeline 2014 F M A M J J A S O
Sample preparation for geochemical analysis (by 31st
March)
X X
Sample preparation (mineral separation) X X
Proposal seminar presentation (12th May) X
SEM imaging of zircon X
Trace element analysis LA-ICPMS (by June 30th) X
SHRIMP geochronology/ additional isotope work (by
July 15th)
X
Compilation of results: tables, figures etc. X X
Thesis- draft (by 1st September) X X X
Advanced ore deposits unit (September 1st – 17th) X
Thesis- final (Due 22nd October) X X
Final project seminar (28th October) X