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Time Scales of a Geothermal Systemfrom Actinolite Fe-Mg Zoning

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Authors McIntire, Michael Zackery

Publisher The University of Arizona.

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Link to Item http://hdl.handle.net/10150/555561

http://hdl.handle.net/10150/555561

3

Abstract

Volume diffusion provides a mechanism to assess the duration, and hence the

timescales of thermal events. In this study, interdiffusion of Fe and Mg across a sharply

zoned interface in actinolite was studied to determine timescales of hydrothermal

activity associated with the Santos deposit in Punta del Cobre, Chile. Petrographic

analysis to identify textures, mineral relations, and mineral orientation was conducted

on several thin sections of drill core from the Santos deposit. Mineral phase relations,

fluid inclusion results from the nearby Candelaria deposit, and comparison with the

modern Salton Sea Geothermal System allow estimation of the maximum temperatures

during ore formation. SEM analyses were performed on the samples to identify strongly

zoned actinolite crystals. Microprobe stage scan analyses were conducted to create a

diffusion profile and determine the diffusion coefficient and time. Although there is

little known about diffusion in actinolite, orthopyroxene (OPX) was chosen as a proxy

because it is a chain silicate and has Fe-Mg diffusion in both of the M sites and thus

broadly analogous to actinolite. Using OPX diffusion coefficients maximum timescales

from 104 to 106 years for maximum temperatures of 350 to 450˚C. These times match

data from some modern geothermal systems.

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Introduction

Timescales of ore formation are commonly limited to geochronological age

determinations on cross cutting features within the ore-forming system. These

relationships provide absolute ages, but often are not sufficiently precise (or accurate)

to constrain durations of the thermal anomalies that may have been related. Volume

diffusion provides an alternative mechanism to assess the duration, and hence the

timescales of related thermal events. This study uses Fe and Mg diffusion in

hydrothermally formed actinolite crystals to assess the maximum duration of the

thermal anomaly associated with iron oxide copper gold (IOCG) systems in Chile. IOCG

systems result from brine-dominated hydrothermal activity that is typically driven by

magmatism (Barton, 2014).

The timing and duration of hydrothermal systems are not well constrained. Currently,

conventional geochronology on cross-cutting events provides this information, however

the precision of the analyses and other uncertainties make it difficult to resolve

differences of much less than 1 m.y. Consequently, many ore-forming systems are

interpreted to last for many millions of years (e.g., Sillitoe and Perello, 2005) whereas

conductive cooling requires that the high-T thermal lifespans of causative igneous

centers almost always is less than 1 m.y. (e.g., Hanson and Barton, 1989). .

Diffusion profiles, which even out as a function of temperature and time, provide one

approach for tightening the timing constraints and placing an improved upper bound on

temperature and time. Actinolite is a common mineral found in IOCG systems, and it

can have considerable variation in Fe and Mg contents. Therefore, if sharp profiles exist,

the extent of diffusion, will reflect temperature and time. Using the mineral associations

present in the samples, fluid inclusions, and modern analogs to constrain the

temperature of the hydrothermal systems it becomes possible to calculate the time of

hydrothermal exposure of the sample based on the extent of diffusion across the Fe and

Mg interface in the actinolite crystal.

5

Geologic background and samples

The Santos deposit in the Punta del Cobre district is located near the town of Copiapó in

the Chilean Coastal Cordillera. The Punta del Cobre district formed east of the Atacama

fault zone, which is an arc-parallel strike slip system of faults and has been active since

the Jurassic (Marschik and Fontbote, 2001). The mineral deposits are IOCG type

deposits and are hosted in arc-derived volcanic rocks of Early Cretaceous age (Marschik

and Fontbote, 2001).

This study began with the observation that very fine-grained actinolite from the Santos

deposit exhibited sharp boundaries when observed in back-scattered electron (BSE)

images in JEOL 6010L SEM. These samples were among many from diamond drill core

obtained at Santos as part of a broader study of that deposit and the Chilean IOCG belt

(e.g., Barton SGA papers). The BSE images highlighted what turns out to be abrupt iron

and magnesium zoning within actinolite grains. These were selected for additional

petrographic and analytical work to determine if the profiles could yield useful

information about diffusion histories.

Analytical Methodology

Beginning with detailed petrography and SEM imaging, the core work in this project

were electron microprobe analyses to determine mineral compositions and their spatial

variation.

The selected samples were first observed through a petrographic microscope. This

process allowed identification of various textures and the location of appropriately sized

and oriented crystals. Crystals oriented with their long axis (C) in the plane of the

section were selected because this direction is both easy to determine and because it

corresponds to best estimates of diffusion data. Petrography was used to identify the

mineral assemblages to better constrain temperatures of formation. The samples were

viewed on a JEOL JSM-6010LA SEM at the University of Arizona, where preliminary data

6

was collected using the energy dispersive spectroscopy (EDS) and BSE imaging to see if

zoning was present. The samples were brought to the University of Arizona Cameca

SX100 electron probe microanalyzer where several overlapping points were setup in a

line spanning across the zonation and from the high Z into the low Z sections of the

actinolite grains (stage scan). Stage scans were run on several different grains and

several different orientations (Fig. 1). The standards used for microprobe analyses are;

albite-cr, ol-fo92, anor-hk, kspar-OR1, rutile1, rod791, fayalite, barite2, MgF2, ap-synap,

scap-s, v_1, chrom_s, scdi, nidi, codi, ZnO, SrTiO3, GGG, SnO2, and ZrO2. There were 2

operating conditions for the microprobe, condition 1 tested for the elements Na, Mg, Al,

Si, K, Ca, Ti, Mn, Fe, Ba, and condition 2 tested for F, S, P, Cl, V, Cr, Sc, Ni, Co, Zn, Sr, Ga,

Sn, Zr. Both conditions operated under 20keV, while condition 1 operated at 20nA and

condition 2 operated at 299nA.

The data obtained from the microprobe stage scan analyses were normalized using the

13eCNK normalization routine for calcic amphibole (Mazdab, 2003; Schumacher, 1997).

This routine assumes that there is no Mn, Fe, or Mg in the M4 site (Spear 1993, p. 104),

and charge balances the formula by assuming that there are 23 atoms of O (Mazdab,

2003). In order for the routine to be considered sound the total amount of calculated

ferric iron must not exceed the total iron and must be greater than zero (Spears 1993,

p. 104), and cations can only occupy structurally and energetically favorable sites

(Spears 1993, p. 104). Some of the uncertainties associated with normalizing data for an

amphibole come from the assumption that there is no deficiency in hydrogen (Spears

1993, p. 103), an unanalyzed element. Another uncertainty comes from the presence of

structural vacancies within the crystal lattice (Spears 1993, p. 103). The Fe+2/Fe+3 ratio is

not fixed for this routine and can vary from point to point within the same stage scan.

This can cause the normalized output to not have a continuous line on the diffusion

profile where the raw data will have a more smooth profile.

Diffusion profile calculations and solving for time

7

The normalized values of the mass fraction of Fe+2 compared to Mg, and the raw

microprobe values of the mass fraction of Fe compared to Mg were then used to solve

for Dt, (diffusion coefficient multiplied by time). Equation 1 is a solution to the diffusion

equation and the derivation can be found in Crank (1986). Equation 1 assumes that the

initial values are from a semi-infinite source (Ganguly, 2002).

Ci(t, x) = Ci(0) +∆C0

2[1 − erf

x

2√Di(EB)t] [1]

Equation 1 was used to fit a line to the normalized and original microprobe results, a

best fit line was obtained by substituting values for Dt. Figure 2 displays the plots of the

raw microprobe data, these data are normalized to the mass fraction of Fe compared to

Mg. Figure 3 shows the plot of the data that was normalized using the 13eCNK

amphibole normalization routine. The iron values of this plot are normalized to the mass

fraction of Fe+2 compared to Mg.

The microprobe electron beam penetrates and spreads out when it comes in contact

with the sample area (Ganguly et al. 1988). This convolutes the data giving values for a

larger area than what is analyzed. Deconvolution corrects for this by subtracting a

calculated additional amount from the convoluted Dt. Deconvolution of the Dt values

Ci(t,x) = The concentration of component i at time t

and position x

Ci(0) = The lower of the two initial values

ΔC0 = Difference between initial compositions

X = Distance from interface

Di(EB) = Effective binary diffusion of component i

8

was performed to account for the added excitation within the grain by the microprobe

beam. The convoluted value can be found by equation 19 from Ganguly et al. (1988).

Dt = Dct − ϵ2

2 [2]

Where D is the deconvoluted diffusion coefficient and Dc is the convoluted diffusion

coefficient found from equation 1. The variable epsilon depends on the concentrations

of the components on either side of the interface, and the slope of the convoluted

profile at the interface (Ganguly et al. 1988). This project used 0.58 for epsilon, which

was experimentally determined by Ganguly et al. (1988) in numerical simulations of

previously step scanned garnet couples (Elphick et al. 1985) in an attempt to find

common epsilon values from microprobe analyses.

Once Dt was determined, a model time could be estimated by first calculating the

diffusion coefficient and assuming that the temperature was constant. Because

diffusion is an unknown in amphibole, the equation for calculating the diffusion

coefficient for orthopyroxene was used as a proxy (Ganguly and Tazzoli 1994).

log D(Fe − Mg)c−b = −5.54 + 2.6XFe −12530

T [3]

Because there is very little information about diffusion in amphiboles a proxy was

needed. A chain silicate would be the most likely proxy. Both OPX and clinopyroxene

(CPX) have diffusion data and were both looked at as possible proxys. Diffusion of Fe

and Mg is considerably slower in CPX than the diffusion in OPX (Muller et al., 2013) and

the diffusion durations found from the analysis of CPX were extraordinarily long and not

feasible. The jump distances (table 3) were looked at and found to be comparable, so

the metal sites available for diffusion were considered. Fe-Mg diffusion can occur

between the M1 through M3 sites in actinolite (Evans and Yang, 1998), both the M1 and

M2 sites in OPX (Ganguly and Tazzoli, 1994), and only in the M1 site in CPX (Muller et al.

2013). Because of the metal sites available for diffusion, OPX was chosen as the best

proxy for actinolite in this study.

9

Results

Petrographic description

Table 1 list the mineral associations found through petrography in samples

DDH673.376.8, DDH643-555.5, DDH628-480.3, and DDH628-593.2.

Table 1: Mineral Associations

Sample Sulfide

Minerals Non-Sulfide

DDH673-376.8

pyrite, chalcopyrite,

bornite

actinolite, epidote, titanite, apatite, magnetite, hematite,

DDH643-555.5

pyrite, chalcopyrite

actinolite, allanite, epidote, calcite, apatite, magnetite, hematite

DDH628-480.3


calcite,actinolite,quartz,apatite,epidote,titanite, allanite, chlorite, magnetite

DDH628-593.2


actinolite, epidote, chlorite, apatite, quartz, magnetite

There are many different textures associated with each individual sample, especially

when considering the actinolite. DDH673-376.8 is an actinolite-epidote-calcite-apatite

matrix supporting rounded magnetite-actinolite-pyrite clasts and rounded actinolite

clasts. Actinolite in matrix can have a fluidized texture, and actinolite is replacing some

of the magnetite clasts. Both the matrix and the clasts are cut by pyrite-chalcopyrite-

epidote ptygmatic veins.

Within the textures of DDH643-555.5 are allanite-actinolite breccia vein supporting

magnetite-pyrite clasts cutting a magnetite-actinolite-pyrite host. Actinolite in matrix

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can have a fluid texture. Pyrite –chalcopyrite-magnetite veins cutting parallel to flow

through actinolite and allanite.

Complex textures are present in sample DDH628-480.3. This sample is defined by an

actinolite-magnetite-epidote-chalcopyrite-pyrite breccia vein supporting magnetite-

pyrite-chalcopyrite clasts. Calcite veins cut through the breccia vein and all of this is cut

by a foliated chlorite-chalcopyrite-calcite vein. This vein cuts perpendicular to the

magnetite-epidote-chalcopyrite-pyrite breccia vein, and is itself cut by actinolite veins.

The actinolite can have flow textures within the matrix.

Sample DDH628-593.2 is an actinolite-magnetite-pyrite supported breccia with

subrounded magnetite-pyrite, actinolite, epidote-magnetite, and magnetite-apatite-

relic feldspar clasts. The breccia and clasts are cut by late sub mm calcite veinlets. The

actinolite can have flow textures in the matrix.

Normalized and raw Dt results

Both the raw and the normalized data for samples DDH673-376.8, DDH643-555.5,

DDH628-480.3, and DDH628-593.2 can be found in the appendix. The Dt values for the

above samples were found for both the raw microprobe data and the normalized data.

Table 2 lists the normalized and raw values of Dt for each related samples after

deconvolution. The raw microprobe data does not take into consideration the amount

of Fe+3 that is present within the crystal structure and the normalized data has an

inconsistent amount of Fe+3. Based on equation 1, Dt is partially dependent on the

concentration of Fe present in the stage scan area. Fe+2 is more likely to diffuse with Mg

than Fe+3 because of like charges, so the raw data overestimates the concentration of

Fe, while the normalized data is more scattered and may overestimate the

concentration of Fe+3. The Dt values for the a and b axis scans were calculated but are

not discussed in this paper because they are not used in the calculation of time. It was

decided that only c axis diffusion would be meaningful due to diffusion along the a and b

11

axes being much slower. The a and b axes are more effected by structure than the c axis

(Ganguly and Tazzoli, 1994).

Table 2: Raw and Normalized Dt values

Sample Dt (raw) Dt

(normalized)

DDH673-376.8 1.33E-08 1.33E-08 DDH643-555.5 8.82E-10 1.33E-08

DDH628-480.3 area 1 1.38E-09 1.58E-09

DDH628-480.3 area 3 1.12E-09 2.32E-09

DDH628-593.2 breccia 1.12E-09 2.82E-09

DDH628-593.2 flow band 1.82E-10 2.82E-09

Discussion

The abrupt transitions between magnesium-rich cores and iron-rich rims in the

actinolite found in these sample represents an evolved interface reflecting some

component of diffusion and some component of original gradient. The latter is an

unknown, it may have been sharp, or it may have been gradational, perhaps similar to

what is observed today. Indeed, there were instances where higher Z (Fe-rich) core and

a lower Z (Mg-rich) rim. The grains found displaying this characteristic were not large

and sufficiently idiomorphic to justify a stage scan.

The model assumes that if there was no diffusion within the grain the profile would be

sharp, with a vertical line separating the iron and magnesium rich portions of the

generated profile. When diffusion starts the profiles will begin to equilibrate starting at

the interface. Complete diffusion would mean equilibrium has been reached and the

profile would be a horizontal line. It is important to find a grain that has a profile that

still has horizontal sections on both sides of the interface, this means that there is a

semi-infinite source for diffusion. These horizontal segments are the initial conditions,

and the slope between them indicates the amount of diffusion that has taken place.

Several of the samples analyzed do not have a semi-infinite source, particularly in

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relation to the iron end rim. This study assumes that the highest concentration of iron

before the interface is the initial condition, but this may not be the case.

Little is known about amphibole diffusion, because amphibole has the tendency to

dehydrate under high pressures and temperatures making experimentation difficult

(Jibamitra Ganguly, pers comm.), because of this a proxy was needed to calculate the

diffusion coefficient of actinolite. The greater the distance between the diffusing metal

sites the more energy is needed to make the jump, and the slower the diffusive process

(Zhang, 2010). A comparison of the jump distances between metal sites for diopside,

enstatite, and actinolite completed to determine if the diffusion time would be similar.

The distances between the metal sites and associated angles between the sites are

listed in Table 3. The sites that are relevant for this study are M1 to M2 and M3 for

actinolite, M1 to M1 for diopside, and M1 to M2 and M1 to M1 for enstatite. Equation

3 was used to calculate the diffusion coefficient associated with orthopyroxene.

Table 3: Jump distances between metal sites Mineral Metal sites compared Distance (Å) Angle (°)

Actinolite Mg1 to Mg2 3.0939 94.782 Mg1 to Mg3 3.0826 95.992 Mg2 to Mg3 3.1998 98.839

Diopside Mg1 to Ca2 3.1827 93.14 Mg1 to Mg1 3.1139 95.379 Mg1 to Ca2 3.4443 101.41

Enstatite Mg1 to Mg1 3.105 95.899 Mg1 to Mg2 3.0313 93.388 Mg1 to Mg2 3.2856 96.786

Table 3: Data for actinolite was from Evans and Yang 1998, diopside data is from Gordan

et al. 1981, and enstatite data is from Yang and Ghose 1995. The data were processed

through the RRUFF project and XTALDRAW software. The data shows that the jump

distances between the relevant sites are similar.

Diffusion depends on temperature, consequently it is necessary to estimate the

maximum temperature of hydrothermal activity and any subsequent thermal events. In

the case of the Santos deposit there is little evidence for a thermal overprint in contrast

to the Candelaria deposit where contact metamorphism substantially modified the

13

original hydrothermal assemblages. Although the actinolite-bearing samples are

products of sodic-calcic metasomatism, their mineralogy is compositionally similar to

the actinolite-epidote-albite-chlorite-titanite assemblages characteristic of the

greenschist metamorphic facies. This mineralogical similarity allows some constrains on

the P-T of the samples (Spear 1993, p. 16-17). The greenschist facies provides a

temperature range of approximately 200°C to about 450°C assuming pressure less than

1kbar. Marschik and Fontbote (2001) reported fluid inclusions filling temperatures in

the Candelaria deposit of 370 to 440°C. These temperatures may be overestimates due

to later contact metamorphism, however they are broadly comparable to a modern day

analog, the Salton Sea Geothermal System, where the temperatures reach 365°C

(McKibben et al. 1988). Figure 4 shows the graphs of both the normalized and raw time

frames when considering a range of temperatures from 365 to 445°C. The maximum

durations estimated by the raw data are generally about an order of magnitude less

than the time scales for the normalized data. This is because equation 3 has a

dependence on the mass fraction of Fe to determine the diffusion coefficient. The mass

fraction for Fe at the interface was used in all calculations. Because the normalized

value for Fe+2 was uneven, this value could be close to the mass fraction of Fe of the raw

value, which is what is expected, or it could be around 60 percent of the raw value. This

decrease in the mass fraction decreases D and increases time.

When looking at the timescales found, Figure 4, and looking at the same sample, but

different textures, Figure 4 E and F, it is obvious that the breccia has been exposed to

more hydrothermal activity than the fluid vein. This implies that the brecciated crystals

formed prior to the flow banding. When looking at the same texture at another point

on the same sample, Figure 4 C and D, the time frames are similar. The timeframes

throughout all samples, in general, suggest that the samples have been exposed to

different degrees and amounts of hydrothermal activity. This could mean that the

actinolite formed at different times, and the hydrothermal activity in the Punta del

Cobre region was constant. This idea would mean that the longer timeframes are more

14

accurate depictions of the duration of hydrothermal activity. It is also possible, and

perhaps more likely, that the hydrothermal activity was varied and would be dormant

for a periods of time. There have been several pulses of magmatic intrusions in the

region since the Jurassic (Marschik and Fontbote, 2001), and possible hydrothermal

activity associated with each pulse. These veins may have been active for more than

one pulse. Reintroduction of hydrothermal fluid into the veins could cause the

mineralization of new actinolite crystals, and the continuation of diffusion in the crystals

already present.

Conclusions

The Santos Deposit has experienced several pulses of magmatic intrusions and volcanic

activity. IOCG type deposits require a heat source for fluid transport, and the magmatic

pulses could be the heat engine that circulated the hydrothermal fluids. Geothermal

systems and associated hydrothermal activity can be an important part of ore

mineralization. Understanding the duration of hydrothermal activity within these

geothermal systems can provide insight into the grade of the ore deposit.

It is possible to constrain the temperatures associated with hydrothermal activity

through use of mineral associations, fluid inclusions, and modern analogs. A look at the

fluid inclusions in the nearby Candalaria deposit, as well as a comparison to the Salton

Sea Geothermal system provides a temperature constraint from 350°C to 450°C, which

is consistent with the mineral associations present that indicate a temperature similar to

a greenschist metamorphic system. Although diffusion in actinolite is not well studied,

it is possible to use OPX as a proxy to determine the timescales of diffusion and

hydrothermal activity. These hydrothermal systems are short lived and happen in

different pulses with different chemistry.

Acknowledgments

I would like to thank Professor Mark Barton for supporting and encouraging this

research. I would also like to thank Professor Jibamitra Ganguly for sharing his

15

knowledge of diffusion, Dr. Ken Domanik for his assistance patience with the

microprobe, Dr. Frank Mazdab for mineralogical and normalization assistance and

editing, and Simone Runyon for her assistance with rock descriptions and editing. This

research would not be possible without the support of Professor Mark Barton by

Freeport-McMoRan in his field and petrographic studies of the Santos deposit, the

Science Foundation of Arizona, and NSF Grant EAR08-38157 to Professor Mark Barton.

20

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Appendix

Table 4: Microprobe oxides and normalized crystal chemistry for DDH673-376.8 Distance (µ) 0 0.51 1.02 1.53 2.04

Na2O 0.519267 0.421319 0.451387 0.332337 0.384591 MgO 14.55967 14.3271 13.67758 14.41045 14.40755

Al2O3 5.05887 4.856478 5.347431 2.496383 2.939853 SiO2 51.0423 51.42751 50.50892 53.55719 52.9565 K2O 0.262932 0.229903 0.283961 0.098917 0.151832 CaO 12.60279 12.69652 12.69211 12.50632 12.53498 TiO2 0.174642 0.131961 0.135765 0.095369 0.15552 MnO 0.20086 0.219796 0.26047 0.272793 0.270221 FeO 14.74549 14.7576 15.62698 15.43123 15.80646

F 0.129364 0.04322 0.063545 0.084477 0.053271 Cl 0.174898 0.163074 0.184493 0.087188 0.140112

Cr2O3 0.013075 0.010241 0.005424 0.026568 0.000015 Total 99.48416 99.28472 99.23808 99.39922 99.8009

Si (T) 7.26 7.34 7.25 7.63 7.53 Al (T) 0.74 0.66 0.75 0.37 0.47

Total T 8.00 8.00 8.00 8.00 8.00

Al (VI) 0.11 0.15 0.15 0.05 0.02 Fe3 (VI) 0.55 0.45 0.49 0.36 0.47 Fe2 (VI) 1.20 1.32 1.39 1.48 1.41 Mg (VI) 3.09 3.05 2.93 3.06 3.05

Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.02 0.03 0.03 0.03 0.03

Ti (VI) 0.02 0.01 0.01 0.01 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00

Fe2 (VIII) 0.00 0.00 0.00 0.00 0.00 Mn2 (VIII) 0.00 0.00 0.00 0.00 0.00 Mg (VIII) 0.00 0.00 0.00 0.00 0.00 Ca (VIII) 1.92 1.94 1.95 1.91 1.91 Na (VIII) 0.08 0.06 0.05 0.09 0.09

Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.06 0.06 0.08 0.00 0.01 K (A) 0.05 0.04 0.05 0.02 0.03

VAC (A) 0.89 0.90 0.87 0.98 0.96 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.90 1.94 1.93 1.94 1.94 F (X) 0.06 0.02 0.03 0.04 0.02 Cl (X) 0.04 0.04 0.04 0.02 0.03 Total 2.00 2.00 2.00 2.00 2.00

Table 4 Continued: Microprobe oxides and normalized crystal chemistry for DDH673-376.8 Distance (µ) 2.55 3.06 3.56 4.07 4.58

Na2O 0.408162 0.423888 0.421482 0.478739 0.473774 MgO 14.55595 14.38833 14.76061 14.88309 15.03837


F 0.00001 0.00001 0.0121 0.00001 0.058975 Cl 0.161335 0.202463 0.196504 0.213148 0.214511

Cr2O3 0.028801 0.000015 0.003083 0.000015 0.014433 Total 100.4689 99.91173 99.83759 100.0592 99.77985

Si (T) 7.47 7.46 7.43 7.42 7.41 Al (T) 0.53 0.54 0.57 0.58 0.59

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.03 0.02 0.02 0.01 0.01

Ti (VI) 0.02 0.02 0.03 0.02 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.03 0.06 0.04 0.06 0.09 K (A) 0.03 0.04 0.03 0.04 0.03

VAC (A) 0.94 0.91 0.93 0.90 0.88 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.96 1.95 1.95 1.95 1.92 F (X) 0.00 0.00 0.01 0.00 0.03 Cl (X) 0.04 0.05 0.05 0.05 0.05 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.442132 0.512275 0.518661 0.479107 0.456026 MgO 15.28259 15.30001 15.39255 15.39272 15.20216


F 0.110959 0.048646 0.227365 0.00001 0.00001 Cl 0.200165 0.200163 0.216837 0.2111 0.199427

Cr2O3 0.00166 0.000015 0.000015 0.007231 0.001538 Total 100.0889 99.97411 100.5634 99.46493 99.14919

Si (T) 7.42 7.42 7.44 7.40 7.45 Al (T) 0.58 0.58 0.56 0.60 0.55

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.02 0.03 0.02 0.03 0.03 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.06 0.06 0.08 0.08 0.08 K (A) 0.04 0.04 0.04 0.04 0.03

VAC (A) 0.91 0.90 0.89 0.88 0.89 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.90 1.93 1.85 1.95 1.95 F (X) 0.05 0.02 0.10 0.00 0.00 Cl (X) 0.05 0.05 0.05 0.05 0.05 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.481154 0.457539 0.388452 0.440991 0.365737 MgO 15.4275 15.67463 15.76145 15.66146 15.75693


F 0.099339 0.209359 0.049038 0.022731 0.00001 Cl 0.209778 0.168208 0.194513 0.198566 0.177945

Cr2O3 0.012142 0.009095 0.009562 0.01807 0.006854 Total 99.40437 99.70496 99.42944 99.06419 99.21752

Si (T) 7.46 7.47 7.50 7.49 7.50 Al (T) 0.54 0.53 0.50 0.51 0.50

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.02 0.02 0.02 0.03 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.08 0.09 0.06 0.06 0.05 K (A) 0.03 0.03 0.03 0.03 0.03

VAC (A) 0.89 0.88 0.90 0.90 0.91 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.90 1.87 1.93 1.94 1.96 F (X) 0.04 0.09 0.02 0.01 0.00 Cl (X) 0.05 0.04 0.05 0.05 0.04 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.397179 0.419068 0.452505 0.431625 0.357185 MgO 15.64601 15.71471 15.67726 15.64084 15.53106


F 0.00001 0.022753 0.00001 0.073503 0.131189 Cl 0.184707 0.165884 0.186138 0.180336 0.194561

Cr2O3 0.002727 0.003686 0.007702 0.004289 0.000015 Total 99.12926 99.1089 99.44077 99.27291 99.2607

Si (T) 7.49 7.49 7.48 7.51 7.50 Al (T) 0.51 0.51 0.52 0.49 0.50

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.03 0.02 0.02 0.03 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.07 0.07 0.06 0.07 0.05 K (A) 0.03 0.03 0.03 0.03 0.03

VAC (A) 0.90 0.90 0.90 0.90 0.91 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.96 1.95 1.96 1.92 1.89 F (X) 0.00 0.01 0.00 0.03 0.06 Cl (X) 0.04 0.04 0.04 0.04 0.05 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.408381 0.351796 0.342956 0.357261 0.380009 MgO 15.60645 15.76653 15.78032 15.86888 15.8658


F 0.005247 0.078773 0.154035 0.056065 0.078919 Cl 0.199725 0.186532 0.17528 0.186033 0.176764

Cr2O3 0.007015 0.000015 0.000015 0.006796 0.000015 Total 99.28426 99.31429 99.12179 99.36452 99.40645

Si (T) 7.49 7.49 7.50 7.52 7.53 Al (T) 0.51 0.51 0.50 0.48 0.47

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.02 0.01 0.01 0.01

Ti (VI) 0.03 0.02 0.03 0.02 0.03 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.07 0.04 0.05 0.04 0.06 K (A) 0.03 0.03 0.03 0.03 0.03

VAC (A) 0.90 0.92 0.92 0.93 0.91 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.95 1.92 1.89 1.93 1.92 F (X) 0.00 0.04 0.07 0.03 0.04 Cl (X) 0.05 0.04 0.04 0.04 0.04 Total 2.00 2.00 2.00 2.00 2.00

The crystal chemistry values are from normalization routine 13eCNK. Values for BaO, S03, P2O5, V2O3, Sc2O3, NiO, CoO, ZnO, SrO, Ga2O3, SnO, and CrO were not analyzed with this sample.

Table 5: Microprobe oxides and normalized crystal chemistry for DDH643-555.5 Distance (µ) 0 0.98 2.2 2.95 3.93

Na2O 0.287009 0.212233 0.269898 0.26797 0.347931 MgO 16.10707 16.16111 15.65491 14.89329 14.52678


F 0.060765 0.021662 0.096337 0.105839 0.056424 Cl 0.282076 0.303644 0.340188 0.372914 0.396501

Cr2O3 0.002818 0.002304 0.001274 0.001424 0.00631 Total 97.13262 98.11849 96.643 96.6788 97.32754

Si (T) 7.56 7.69 7.64 7.55 7.42 Al (T) 0.43 0.30 0.35 0.45 0.57

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.01 0.00 0.00 0.01 0.01 Sc (VI) 0.01 0.01 0.01 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.03 0.06 0.05 0.03 0.04 K (A) 0.03 0.03 0.04 0.04 0.06

VAC (A) 0.94 0.91 0.90 0.92 0.90 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.90 1.92 1.87 1.86 1.88 F (X) 0.03 0.01 0.04 0.05 0.03 Cl (X) 0.07 0.07 0.08 0.09 0.10 Total 2.00 2.00 2.00 2.00 2.00

Table 5 continued: Microprobe oxides and normalized crystal chemistry for DDH643-555.5 Distance (µ) 5.01 5.89 6.88 7.86 8.84

Na2O 0.440451 0.452692 0.477658 0.540967 0.550938 MgO 13.85717 13.59122 13.38689 13.35596 13.22397


F 0.048534 0.040017 0.057415 0.077468 0.010523 Cl 0.437832 0.481076 0.503991 0.524528 0.481575

Cr2O3 0.005244 0.004957 0.006225 0.003828 0.002216 Total 97.5722 97.03063 97.24844 97.39343 97.26689

Si (T) 7.38 7.35 7.33 7.29 7.28 Al (T) 0.62 0.64 0.67 0.71 0.71

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.02

Ti (VI) 0.01 0.01 0.01 0.01 0.01 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.03 0.06 0.06 0.08 0.08 K (A) 0.07 0.07 0.08 0.08 0.09

VAC (A) 0.90 0.87 0.86 0.84 0.83 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.87 1.86 1.85 1.83 1.87 F (X) 0.02 0.02 0.03 0.04 0.00 Cl (X) 0.11 0.12 0.13 0.13 0.12 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.48291 0.193456 0.17523 0.20637 0.202371 MgO 13.51221 15.17494 15.4207 15.94684 16.09793


F 0.044904 0.053833 0.094456 0.06774 0.065609 Cl 0.253767 0.091989 0.087651 0.092139 0.096046

Cr2O3 0.000904 0.004567 0.005012 0.005077 0.003614 Total 97.14985 95.12344 95.63325 96.15733 96.882

Si (T) 7.39 7.89 7.85 7.75 7.75 Al (T) 0.61 0.11 0.15 0.24 0.25

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.02 0.03 0.02 0.01 0.01

Ti (VI) 0.01 0.01 0.01 0.01 0.01 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 4.96 4.98 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.03 0.00 0.01 0.01 0.00 K (A) 0.08 0.02 0.02 0.02 0.02

VAC (A) 0.89 0.98 0.97 0.97 0.98 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.92 1.95 1.93 1.95 1.95 F (X) 0.02 0.03 0.04 0.03 0.03 Cl (X) 0.06 0.02 0.02 0.02 0.02 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.210594 0.235403 0.278751 0.266813 0.218256 MgO 16.19386 16.45159 16.337 16.60188 16.392


F 0.070494 0.06336 0.090613 0.08498 0.086715 Cl 0.093352 0.099834 0.101783 0.100161 0.098169

Cr2O3 0.004845 0.003525 0.003896 0.004302 0.004096 Total 97.0473 97.321 96.52431 97.08208 97.21858

Si (T) 7.72 7.74 7.68 7.72 7.72 Al (T) 0.28 0.26 0.32 0.28 0.28

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.01 0.02 0.02 0.02 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.02 0.07 0.01 0.07 0.00 K (A) 0.02 0.02 0.02 0.02 0.02

VAC (A) 0.96 0.91 0.96 0.90 0.98 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.95 1.95 1.93 1.94 1.94 F (X) 0.03 0.03 0.04 0.04 0.04 Cl (X) 0.02 0.02 0.02 0.02 0.02 Total 2.00 2.00 2.00 2.00 2.00

Table 5 continued: Microprobe oxides and normalized crystal chemistry for DDH643-555.5 Distance (µ) 19.65

Na2O 0.242991

MgO 16.49746

Al2O3 2.281999

SiO2 53.5663

K2O 0.125191

CaO 12.6449

TiO2 0.207579

MnO 0.083351

FeO 11.59051

F 0.084827

Cl 0.096804

Cr2O3 0.001028

Total 97.53289

Si (T) 7.67

Al (T) 0.33

Total T 8.00

Al (VI) 0.05

Fe3 (VI) 0.25

Fe2 (VI) 1.13

Mg (VI) 3.52

Mn3 (VI) 0.00

Mn2 (VI) 0.01

Ti (VI) 0.02

Sc (VI) 0.00

Total (VI) 5.00

Fe2 (VIII) 0.00

Mn2 (VIII) 0.00

Mg (VIII) 0.00

Ca (VIII) 1.94

Na (VIII) 0.06

Total 2.00

Na (A) 0.01

K (A) 0.02

VAC (A) 0.97

Total 1.00

OH (X) 1.94

F (X) 0.04

Cl (X) 0.02

Total 2.00

The crystal chemistry values are from normalization routine 13eCNK. Values for BaO, S03, P2O5, V2O3, Sc2O3, NiO, CoO, ZnO, SrO, Ga2O3, SnO, and CrO were analyzed but the normalized values of

V, Cr, Ga, Co, Ni, Cu, Zn, Zr, S, P, Sn, Sr, Ba, And Y were below 0.01 and not reported in this table.

Table 6: Microprobe oxides and normalized crystal chemistry for DDH628-480.3 area 1 Distance (µ) 0 0.5 1 1.5 2.01

Na2O 0.124188 0.131647 0.161532 0.096286 0.132225 MgO 15.43566 15.82126 15.34364 14.68176 14.42008


F 0.042148 0.045188 0.039173 0.024084 0.037288 Cl 0.024945 0.022554 0.018316 0.026107 0.049583

Cr2O3 0.00383 0.006721 0.003412 0.00453 0.004595 Total 97.01707 97.46828 97.86226 96.28015 97.39112

Si (T) 7.76 7.74 7.75 7.81 7.81 Al (T) 0.24 0.21 0.25 0.19 0.18

Total T 8.00 7.95 8.00 8.00 7.99


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.03 0.03 0.03 0.03 0.03

Ti (VI) 0.00 0.00 0.00 0.01 0.01 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 1.98 2.00 1.98 1.96 1.97

Na (A) 0.00 0.04 0.00 0.00 0.00 K (A) 0.01 0.01 0.01 0.01 0.01

VAC (A) 0.99 0.95 0.99 0.99 0.99 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.97 1.97 1.98 1.98 1.97 F (X) 0.02 0.02 0.02 0.01 0.02 Cl (X) 0.01 0.01 0.00 0.01 0.01 Total 2.00 2.00 2.00 2.00 2.00

Table 6 continued: Microprobe oxides and normalized crystal chemistry for DDH628-480.3 area 1 Distance (µ) 2.51 3.01 3.51 4.01 4.51

Na2O 0.145725 0.145951 0.130504 0.238145 0.290429 MgO 14.25298 14.59661 14.3236 15.3197 16.95057


F 0.012295 0.027248 0.06392 0.013726 0.064553 Cl 0.050561 0.052607 0.048257 0.075143 0.102522

Cr2O3 0.004951 0.004086 0.004618 0.004423 0.002955 Total 96.32806 96.44 96.43168 96.13532 97.10756

Si (T) 7.84 7.81 7.84 7.73 7.55 Al (T) 0.15 0.19 0.15 0.27 0.44

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.03 0.03 0.03 0.03 0.01

Ti (VI) 0.01 0.01 0.01 0.02 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 1.98 1.98 1.98 2.00 2.00

Na (A) 0.00 0.00 0.00 0.02 0.01 K (A) 0.01 0.01 0.01 0.02 0.02

VAC (A) 0.99 0.98 0.98 0.96 0.97 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.98 1.97 1.96 1.98 1.95 F (X) 0.01 0.01 0.03 0.01 0.03 Cl (X) 0.01 0.01 0.01 0.02 0.02 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.288656 0.262609 0.301167 0.278148 0.294483 MgO 16.78955 16.86835 16.87154 16.76071 16.69034


F 0.092443 0.058638 0.067396 0.087349 0.046455 Cl 0.104831 0.105447 0.102102 0.110657 0.109799

Cr2O3 0.003437 0.002452 0.003295 0.003962 0.003684 Total 96.93964 97.09879 97.40619 97.17768 96.89837

Si (T) 7.56 7.56 7.53 7.55 7.53 Al (T) 0.44 0.44 0.47 0.45 0.46

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.02 0.02 0.02 0.02 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 1.99 2.00

Na (A) 0.02 0.01 0.02 0.00 0.03 K (A) 0.03 0.02 0.02 0.02 0.02

VAC (A) 0.95 0.97 0.96 0.97 0.95 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.93 1.95 1.94 1.93 1.95 F (X) 0.04 0.03 0.03 0.04 0.02 Cl (X) 0.03 0.03 0.02 0.03 0.03 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.304051 0.344628 0.36427 0.368279 0.364371 MgO 16.79421 16.62755 16.92573 16.44981 16.40588


F 0.050665 0.099155 0.099519 0.062232 0.084966 Cl 0.112101 0.111036 0.116145 0.11535 0.11951

Cr2O3 0.004291 0.002224 0.001962 0.004483 0.002527 Total 96.89725 96.83778 97.5024 96.97023 97.17344

Si (T) 7.53 7.52 7.50 7.52 7.53 Al (T) 0.47 0.47 0.50 0.48 0.47

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.02 0.02 0.02 0.02 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.01 0.03 0.03 0.05 0.04 K (A) 0.03 0.03 0.03 0.02 0.02

VAC (A) 0.96 0.94 0.94 0.92 0.93 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.95 1.93 1.93 1.94 1.93 F (X) 0.02 0.05 0.04 0.03 0.04 Cl (X) 0.03 0.03 0.03 0.03 0.03 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.347917 0.385058 0.395488 0.363744 0.329936 MgO 16.30459 16.5194 16.36086 16.34169 16.56752


F 0.061113 0.069043 0.055492 0.083942 0.056206 Cl 0.120019 0.119897 0.116166 0.117245 0.135332

Cr2O3 0.003583 0.00342 0.004525 0.003235 0.003316 Total 96.43362 96.75699 96.10753 95.95107 95.9615

Si (T) 7.54 7.50 7.51 7.54 7.54 Al (T) 0.46 0.50 0.48 0.46 0.46

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.02 0.02 0.02 0.02 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.04 0.05 0.05 0.05 0.05 K (A) 0.03 0.03 0.02 0.03 0.03

VAC (A) 0.94 0.92 0.92 0.92 0.92 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.94 1.94 1.95 1.93 1.94 F (X) 0.03 0.03 0.03 0.04 0.03 Cl (X) 0.03 0.03 0.03 0.03 0.03 Total 2.00 2.00 2.00 2.00 2.00

Table 6 continued: Microprobe oxides and normalized crystal chemistry for DDH628-480.3 area 1 Distance (µ) 12.54 13.04

Na2O 0.301774 0.275662

MgO 16.99285 17.17798

Al2O3 2.95508 2.683072

SiO2 52.49677 52.61824

K2O 0.128771 0.135649

CaO 12.60902 12.63974

TiO2 0.220886 0.21595

MnO 0.105415 0.084302

FeO 10.68676 10.4008

F 0.081642 0.086219

Cl 0.119122 0.117599

Cr2O3 0.00493 0.001763

Total 96.7928 96.53176

Si (T) 7.54 7.57

Al (T) 0.46 0.43

Total T 8.00 8.00

Al (VI) 0.04 0.02

Fe3 (VI) 0.38 0.35

Fe2 (VI) 0.90 0.90

Mg (VI) 3.64 3.68

Mn3 (VI) 0.00 0.00

Mn2 (VI) 0.01 0.01

Ti (VI) 0.02 0.02

Sc (VI) 0.00 0.00

Total (VI) 5.00 5.00

Fe2 (VIII) 0.00 0.00

Mn2 (VIII) 0.00 0.00

Mg (VIII) 0.00 0.00

Ca (VIII) 1.94 1.95

Na (VIII) 0.06 0.05

Total 2.00 2.00

Na (A) 0.02 0.02

K (A) 0.02 0.02

VAC (A) 0.95 0.95

Total 1.00 1.00

OH (X) 1.93 1.93

F (X) 0.04 0.04

Cl (X) 0.03 0.03

Total 2.00 2.00


Table 7: Microprobe oxides and normalized crystal chemistry for DDH628-480.3 area 3 Distance (µ) 0 0.5 1 1.51 2.01

Na2O 0.255558 0.18866 0.133751 0.131519 0.082341 MgO 15.6691 15.53198 15.21335 14.89038 14.83903


F 0.005415 0.046859 0.017983 0.023132 0.021232 Cl 0.084691 0.071032 0.07695 0.053098 0.044576

Cr2O3 0.003435 0.003822 0.005636 0.004051 0.004543 Total 96.15991 96.26161 96.23116 96.65363 97.0218

Si (T) 7.69 7.75 7.77 7.75 7.78 Al (T) 0.27 0.23 0.20 0.19 0.19

Total T 7.97 7.98 7.98 7.94 7.96


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.03 0.03 0.03 0.04 0.04

Ti (VI) 0.00 0.00 0.00 0.00 0.00 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 1.98

Na (A) 0.00 0.01 0.03 0.03 0.00 K (A) 0.01 0.01 0.01 0.01 0.01

VAC (A) 0.98 0.97 0.96 0.96 0.99 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.98 1.96 1.97 1.98 1.98 F (X) 0.00 0.02 0.01 0.01 0.01 Cl (X) 0.02 0.02 0.02 0.01 0.01 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.175338 0.256944 0.272841 0.451785 0.480676 MgO 14.55688 14.33457 14.44087 14.84125 15.23904


F 0.070443 0.018598 0.006678 0.008767 0.065758 Cl 0.038964 0.050811 0.029779 0.03239 0.054997

Cr2O3 0.006818 0.005539 0.005035 0.007255 0.004882 Total 97.56429 96.71215 96.7182 96.38569 96.87395

Si (T) 7.67 7.66 7.54 7.37 7.36 Al (T) 0.26 0.32 0.42 0.63 0.64

Total T 7.93 7.97 7.96 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.05 0.04 0.04 0.02 0.01

Ti (VI) 0.01 0.01 0.01 0.02 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 1.99 2.00 2.00 2.00

Na (A) 0.02 0.00 0.00 0.05 0.05 K (A) 0.01 0.02 0.02 0.03 0.03

VAC (A) 0.97 0.98 0.98 0.92 0.91 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.96 1.98 1.99 1.99 1.96 F (X) 0.03 0.01 0.00 0.00 0.03 Cl (X) 0.01 0.01 0.01 0.01 0.01 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.50241 0.474705 0.458216 0.458339 0.421867 MgO 15.54626 15.50916 15.80972 16.09756 16.02263


F 0.038963 0.069048 0.045307 0.02082 0.061375 Cl 0.075196 0.093708 0.107986 0.111386 0.109087

Cr2O3 0.0066 0.004878 0.003981 0.006211 0.006902 Total 96.34139 96.05486 95.97382 96.19466 96.03344

Si (T) 7.33 7.37 7.36 7.33 7.36 Al (T) 0.67 0.63 0.64 0.67 0.64

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.02 0.02 0.02 0.02 0.02 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.08 0.08 0.05 0.06 0.06 K (A) 0.03 0.03 0.03 0.03 0.03

VAC (A) 0.89 0.89 0.92 0.91 0.90 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.96 1.94 1.95 1.96 1.94 F (X) 0.02 0.03 0.02 0.01 0.03 Cl (X) 0.02 0.02 0.03 0.03 0.03 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.493815 0.482232 0.491994 0.428822 0.455158 MgO 16.00585 16.03854 16.14016 16.1452 16.18777


F 0.070174 0.015486 0.113651 0.057423 0.0655 Cl 0.109729 0.105498 0.101517 0.101733 0.104885

Cr2O3 0.008277 0.006145 0.005358 0.003652 0.00523 Total 96.3183 95.87046 96.03848 95.96567 96.24893

Si (T) 7.31 7.33 7.32 7.36 7.34 Al (T) 0.69 0.67 0.68 0.64 0.66

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.01 0.02 0.01 0.02 0.01 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.06 0.07 0.08 0.06 0.06 K (A) 0.03 0.03 0.03 0.03 0.03

VAC (A) 0.91 0.90 0.90 0.91 0.91 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.94 1.97 1.92 1.95 1.94 F (X) 0.03 0.01 0.05 0.03 0.03 Cl (X) 0.03 0.03 0.03 0.03 0.03 Total 2.00 2.00 2.00 2.00 2.00

Table 7 continued: Microprobe oxides and normalized crystal chemistry for DDH628-480.3 area 3 Distance (µ) 10.04 10.54 11.05

Na2O 0.45259 0.456383 0.486985

MgO 16.02625 15.95768 16.076

Al2O3 4.076816 4.116143 4.094569

SiO2 49.93295 50.52214 50.20464

K2O 0.146318 0.147766 0.151819

CaO 12.3561 12.40912 12.39686

TiO2 0.118868 0.120194 0.11411

MnO 0.098932 0.058053 0.077808

FeO 11.71441 11.84327 11.88384

F 0.044294 0.051988 0.050248

Cl 0.107748 0.104214 0.10433

Cr2O3 0.006249 0.004462 0.005574

Total 95.16895 95.88638 95.74671

Si (T) 7.32 7.36 7.32

Al (T) 0.68 0.64 0.68

Total T 8.00 8.00 8.00

Al (VI) 0.03 0.07 0.03

Fe3 (VI) 0.57 0.51 0.57

Fe2 (VI) 0.86 0.93 0.87

Mg (VI) 3.50 3.46 3.49

Mn3 (VI) 0.00 0.00 0.00

Mn2 (VI) 0.01 0.01 0.01

Ti (VI) 0.01 0.01 0.01

Sc (VI) 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00

Fe2 (VIII) 0.00 0.00 0.00

Mn2 (VIII) 0.00 0.00 0.00

Mg (VIII) 0.00 0.00 0.00

Ca (VIII) 1.94 1.94 1.94

Na (VIII) 0.06 0.06 0.06

Total 2.00 2.00 2.00

Na (A) 0.07 0.07 0.07

K (A) 0.03 0.03 0.03

VAC (A) 0.90 0.91 0.90

Total 1.00 1.00 1.00

OH (X) 1.95 1.95 1.95

F (X) 0.02 0.02 0.02

Cl (X) 0.03 0.03 0.03

Total 2.00 2.00 2.00


Table 8: Microprobe oxides and normalized crystal chemistry for DDH628-593.2 breccia Distance (µ) 0 0.5 1 1.5 2

Na2O 0.276688 0.247971 0.28343 0.386046 0.375872 MgO 14.94384 14.86842 14.84999 14.0323 13.99916


F 0.044497 0.029824 0.004461 0.009952 0.019537 Cl 0.300381 0.315351 0.348061 0.446741 0.485622

Cr2O3 0.004521 0.008425 0.006346 0.003757 0.006047 Total 96.05783 95.88361 96.76093 95.37531 95.87373

Si (T) 7.23 7.25 7.21 7.21 7.28 Al (T) 0.70 0.70 0.73 0.77 0.72

Total T 7.93 7.95 7.93 7.98 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.02 0.02

Ti (VI) 0.01 0.01 0.01 0.01 0.01 Sc (VI) 0.01 0.01 0.02 0.01 0.01

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 1.99 1.97 1.96 1.88 1.90

Na (A) 0.00 0.00 0.00 0.00 0.00 K (A) 0.03 0.03 0.03 0.04 0.05

VAC (A) 0.97 0.97 0.97 0.96 0.95 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.91 1.91 1.91 1.88 1.87 F (X) 0.02 0.01 0.00 0.00 0.01 Cl (X) 0.07 0.08 0.09 0.11 0.12 Total 2.00 2.00 2.00 2.00 2.00

Table 8 continued: Microprobe oxides and normalized crystal chemistry for DDH628-593.2 breccia Distance (µ) 2.5 3 3.5 4 4.5

Na2O 0.360837 0.353317 0.44245 0.408322 0.324175 MgO 13.74302 13.73979 13.25991 12.89789 13.20297


F 0.00001 0.00001 0.012224 0.016337 0.005813 Cl 0.492627 0.484903 0.482021 0.428134 0.399134

Cr2O3 0.0062 0.003291 0.003849 0.004142 0.006014 Total 96.54012 97.08603 96.42681 95.85023 96.03987

Si (T) 7.33 7.34 7.30 7.32 7.29 Al (T) 0.66 0.66 0.69 0.68 0.71

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.02 0.02 0.01 0.02 0.02

Ti (VI) 0.01 0.01 0.01 0.01 0.01 Sc (VI) 0.01 0.01 0.01 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 1.98 1.99 2.00 2.00 1.99

Na (A) 0.00 0.00 0.04 0.04 0.00 K (A) 0.05 0.05 0.06 0.06 0.06

VAC (A) 0.95 0.94 0.89 0.90 0.94 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.88 1.88 1.87 1.88 1.90 F (X) 0.00 0.00 0.01 0.01 0.00 Cl (X) 0.12 0.12 0.12 0.11 0.10 Total 2.00 2.00 2.00 2.00 2.00

Table 8 continued: Microprobe oxides and normalized crystal chemistry for DDH628-593.2 breccia Distance (µ) 5 5.5 6 6.5 7

Na2O 0.412872 0.473472 0.44172 0.498757 0.48135 MgO 13.61205 14.35674 14.73616 15.45263 16.01417


F 0.01531 0.064931 0.084333 0.038358 0.031056 Cl 0.305636 0.259389 0.197782 0.162011 0.155887

Cr2O3 0.010055 0.007705 0.010262 0.006072 0.007299 Total 96.78679 96.80303 97.38049 97.6279 97.05824

Si (T) 7.31 7.28 7.28 7.27 7.22 Al (T) 0.69 0.72 0.72 0.73 0.78

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.01 0.01 0.01 0.02 0.03 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.01 0.05 0.04 0.08 0.06 K (A) 0.05 0.05 0.05 0.04 0.04

VAC (A) 0.93 0.90 0.91 0.87 0.90 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.92 1.91 1.91 1.94 1.95 F (X) 0.01 0.03 0.04 0.02 0.01 Cl (X) 0.08 0.06 0.05 0.04 0.04 Total 2.00 2.00 2.00 2.00 2.00

Table 8 continued: Microprobe oxides and normalized crystal chemistry for DDH628-593.2 breccia Distance (µ) 7.5 8 8.5 9 9.5

Na2O 0.476212 0.408232 0.328948 0.345429 0.239461 MgO 15.96565 16.20637 16.45341 16.25948 16.53497


F 0.083075 0.067554 0.073048 0.094763 0.081943 Cl 0.147551 0.144763 0.148952 0.149543 0.151686

Cr2O3 0.008833 0.010285 0.010615 0.00904 0.012669 Total 96.96839 97.15401 97.87651 97.286 97.92731

Si (T) 7.26 7.24 7.24 7.25 7.25 Al (T) 0.74 0.76 0.76 0.75 0.74

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.04 0.04 0.04 0.04 0.04 Sc (VI) 0.00 0.00 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 1.98

Na (A) 0.09 0.05 0.04 0.04 0.00 K (A) 0.04 0.04 0.03 0.03 0.03

VAC (A) 0.87 0.91 0.93 0.92 0.97 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.93 1.93 1.93 1.92 1.93 F (X) 0.04 0.03 0.03 0.04 0.04 Cl (X) 0.04 0.04 0.04 0.04 0.04 Total 2.00 2.00 2.00 2.00 2.00

Table 8 continued: Microprobe oxides and normalized crystal chemistry for DDH628-593.2 breccia Distance (µ) 10 10.5 11

Na2O 0.252799 0.527579 0.451821

MgO 16.53743 16.31207 15.93952

Al2O3 5.120896 5.329885 5.279683

SiO2 51.45661 50.14428 49.8477

K2O 0.150395 0.219891 0.212689

CaO 12.57421 12.54697 12.49679

TiO2 0.365929 0.362766 0.356446

MnO 0.096492 0.11515 0.084571

FeO 11.27621 11.27192 11.29127

F 0.091529 0.076616 0.104753

Cl 0.163998 0.166344 0.165962

Cr2O3 0.007938 0.010275 0.010297

Total 98.25729 97.25082 96.40536

Si (T) 7.27 7.19 7.22

Al (T) 0.73 0.81 0.78

Total T 8.00 8.00 8.00

Al (VI) 0.12 0.09 0.12

Fe3 (VI) 0.61 0.57 0.51

Fe2 (VI) 0.72 0.78 0.86

Mg (VI) 3.48 3.49 3.44

Mn3 (VI) 0.00 0.00 0.00

Mn2 (VI) 0.01 0.01 0.01

Ti (VI) 0.04 0.04 0.04

Sc (VI) 0.00 0.00 0.00

Total (VI) 5.00 5.00 5.00

Fe2 (VIII) 0.00 0.00 0.00

Mn2 (VIII) 0.00 0.00 0.00

Mg (VIII) 0.00 0.00 0.00

Ca (VIII) 1.90 1.93 1.94

Na (VIII) 0.07 0.07 0.06

Total 1.97 2.00 2.00

Na (A) 0.00 0.07 0.07

K (A) 0.03 0.04 0.04

VAC (A) 0.97 0.88 0.89

Total 1.00 1.00 1.00

OH (X) 1.92 1.92 1.91

F (X) 0.04 0.03 0.05

Cl (X) 0.04 0.04 0.04

Total 2.00 2.00 2.00


Table 9: Microprobe oxides and normalized crystal chemistry for DDH628-593.2 fluidized vein Distance (µ) 0 0.49 0.98 1.47 1.96

Na2O 0.616228 0.643948 0.499511 0.557221 0.50212 MgO 14.18896 14.7763 14.65565 14.74578 14.9323


F 0.090465 0.056923 0.030788 0.072783 0.098604 Cl 0.600342 0.574878 0.55484 0.531275 0.522328

Cr2O3 0.012671 0.011122 0.008787 0.008495 0.010705 Total 96.31524 97.17488 97.44309 97.47692 97.99744

Si (T) 7.29 7.28 7.37 7.35 7.34 Al (T) 0.71 0.71 0.62 0.65 0.66

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.02 0.02

Ti (VI) 0.02 0.02 0.02 0.02 0.02 Sc (VI) 0.02 0.02 0.02 0.02 0.02

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.10 0.08 0.06 0.06 0.03 K (A) 0.07 0.06 0.05 0.05 0.06

VAC (A) 0.83 0.85 0.89 0.88 0.92 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.81 1.83 1.85 1.84 1.83 F (X) 0.04 0.03 0.01 0.03 0.05 Cl (X) 0.15 0.14 0.14 0.13 0.13 Total 2.00 2.00 2.00 2.00 2.00

Table 9 cont: Microprobe oxides and normalized crystal chemistry for DDH628-593.2 fluidized vein Distance (µ) 2.45 2.94 3.43 3.92 4.41

Na2O 0.459417 0.447791 0.415261 0.48283 0.410283 MgO 15.43684 16.05642 16.72971 17.19838 17.18


F 0.057643 0.057194 0.044403 0.068381 0.040736 Cl 0.471967 0.450115 0.320313 0.200497 0.174416

Cr2O3 0.010845 0.012147 0.006916 0.009196 0.009414 Total 97.20545 96.74438 96.94944 97.14528 97.14034

Si (T) 7.39 7.43 7.46 7.45 7.49 Al (T) 0.61 0.57 0.54 0.55 0.51

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.02 0.02 0.03 0.03 0.04 Sc (VI) 0.01 0.01 0.01 0.01 0.01

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.06 0.05 0.04 0.05 0.03 K (A) 0.04 0.03 0.03 0.02 0.02

VAC (A) 0.90 0.91 0.93 0.93 0.95 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.86 1.86 1.90 1.92 1.94 F (X) 0.03 0.03 0.02 0.03 0.02 Cl (X) 0.12 0.11 0.08 0.05 0.04 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.372639 0.387697 0.405831 0.365029 0.370687 MgO 17.24808 17.42558 17.37906 17.26682 17.17839


F 0.094852 0.134459 0.043814 0.091815 0.10036 Cl 0.129631 0.108869 0.103667 0.097338 0.098636

Cr2O3 0.009273 0.006635 0.009026 0.008896 0.009968 Total 96.97705 97.58324 97.51756 97.17515 97.01857

Si (T) 7.48 7.47 7.47 7.49 7.51 Al (T) 0.52 0.53 0.53 0.51 0.49

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.04 0.04 0.04 0.03 0.03 Sc (VI) 0.01 0.01 0.01 0.01 0.01

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.04 0.01 0.02 0.03 0.03 K (A) 0.03 0.02 0.02 0.03 0.02

VAC (A) 0.93 0.96 0.96 0.94 0.95 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.93 1.91 1.96 1.94 1.93 F (X) 0.04 0.06 0.02 0.04 0.05 Cl (X) 0.03 0.03 0.02 0.02 0.02 Total 2.00 2.00 2.00 2.00 2.00


Na2O 0.349625 0.39943 0.345135 0.306143 0.357678 MgO 17.33293 17.1598 17.4588 17.09636 17.20603


F 0.108787 0.048736 0.086219 0.098746 0.099773 Cl 0.096674 0.101601 0.102802 0.097193 0.102798

Cr2O3 0.009552 0.008508 0.009371 0.01032 0.008862 Total 97.14782 97.16942 97.50852 96.89342 96.78101

Si (T) 7.48 7.49 7.47 7.54 7.53 Al (T) 0.52 0.51 0.53 0.46 0.47

Total T 8.00 8.00 8.00 8.00 8.00


Mn3 (VI) 0.00 0.00 0.00 0.00 0.00 Mn2 (VI) 0.01 0.01 0.01 0.01 0.01

Ti (VI) 0.04 0.03 0.03 0.03 0.04 Sc (VI) 0.01 0.01 0.01 0.01 0.01

Total (VI) 5.00 5.00 5.00 5.00 5.00


Total 2.00 2.00 2.00 2.00 2.00

Na (A) 0.02 0.03 0.00 0.01 0.02 K (A) 0.02 0.02 0.03 0.03 0.02

VAC (A) 0.96 0.95 0.97 0.97 0.95 Total 1.00 1.00 1.00 1.00 1.00

OH (X) 1.93 1.95 1.94 1.93 1.93 F (X) 0.05 0.02 0.04 0.04 0.05 Cl (X) 0.02 0.02 0.02 0.02 0.02 Total 2.00 2.00 2.00 2.00 2.00

Table 9 cont: Microprobe oxides and normalized crystal chemistry for DDH628-593.2 fluidized vein Distance (µ) 9.79 10.28 10.77

Na2O 0.34311 0.311051 0.369184

MgO 17.25094 17.27954 17.17951

Al2O3 3.435767 3.346753 3.295756

SiO2 52.22982 52.52411 52.48994

K2O 0.128831 0.130831 0.123139

CaO 12.56801 12.58694 12.51267

TiO2 0.317902 0.303304 0.301362

MnO 0.076936 0.104656 0.080555

FeO 10.03776 9.961198 9.859683

F 0.041305 0.100408 0.053834

Cl 0.104773 0.100682 0.097243

Cr2O3 0.009242 0.009254 0.00908

Total 96.70744 96.93014 96.5383

Si (T) 7.48 7.50 7.53

Al (T) 0.52 0.50 0.47

Total T 8.00 8.00 8.00

Al (VI) 0.06 0.07 0.09

Fe3 (VI) 0.40 0.38 0.33

Fe2 (VI) 0.80 0.81 0.85

Mg (VI) 3.68 3.68 3.67

Mn3 (VI) 0.00 0.00 0.00

Mn2 (VI) 0.01 0.01 0.01

Ti (VI) 0.03 0.03 0.03

Sc (VI) 0.01 0.01 0.01

Total (VI) 5.00 5.00 5.00

Fe2 (VIII) 0.00 0.00 0.00

Mn2 (VIII) 0.00 0.00 0.00

Mg (VIII) 0.00 0.00 0.00

Ca (VIII) 1.93 1.93 1.92

Na (VIII) 0.07 0.07 0.08

Total 2.00 2.00 2.00

Na (A) 0.02 0.01 0.03

K (A) 0.02 0.02 0.02

VAC (A) 0.95 0.96 0.95

Total 1.00 1.00 1.00

OH (X) 1.96 1.93 1.95

F (X) 0.02 0.05 0.02

Cl (X) 0.03 0.02 0.02

Total 2.00 2.00 2.00


Abstract - The University of Arizona Campus...

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