Imperial College London

Department of Earth Science and Engineering

Structural Diagenesis Using Clumped Isotope

Paleothermometry: Applications and Potential Caveats

Adhipa Herlambang

Submitted in part fulfillment of the requirements for the degree of

Doctor of Philosophy
December 2020
Teruntuk Papa dan Mama
Ambu dan Nanu
Abstract
Fluid flow commonly results in mineral precipitation in fractures which can yield a chemical
archive of the physico-chemical conditions during tectonic deformation. However, interpreting
subsurface conditions from traditional geochemical proxies can be ambiguous. Here we test
clumped isotope thermometry as a tool to provide better understanding of the relationship
between deformational structures and diagenetic processes.

Three main questions are addressed by this PhD thesis. The first question regards the reliability
of clumped isotope compared to fluid inclusions in fractures within granites. We selected
calcite veins resulting from deep-biosphere activity in oligotrophic fractures environment in
Sweden. The clumped isotope results demonstrate that the optimal habitat to support microbial
activity was below the detection limit of fluid inclusion. Hence, carbonate clumped isotope in
this case is a valuable tool complementary to fluid inclusions that offers tighter constraints on
the temperature and origin of diagenetic fluid.

The second objective was to investigate potential kinetic fractionation effects due to
precipitation rates in fractures filled with meteoric cements. To address this objective, we apply
clumped isotopes and trace element analysis along a detailed transect of single minerals of
calcite in faults. The strong correlation between the ratio of Mn/Fe with clumped isotope
temperature lead us to argue that this is indicative of variable crystal precipitation rates and in
some cases kinetic fractionation. Thus for the first time we can independently show potential
kinetic fractionation within ancient natural calcite samples that resulted in clumped isotopes
temperature higher than ambient.

The third and final objective of the thesis was to apply clumped isotopes within an integrated
study aiming at understanding the relationship between paleo-temperature, fluid flow and salt-
doming in Jebel Madar, Oman. The results lead us to re-interpret the structural diagenesis of
Jebel Madar, and demonstrate the value of clumped isotopes in structural diagenesis studies in
general.
Declaration
I declare that all work in this thesis is my own, unless otherwise stated or referenced.

Adhipa Herlambang, 2020

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Acknowledgments
All Praise and Thank Be to Allah.

I would like deeply thank to Cédric John for everything: generosity, support, guidance, and ton
of good memories. Your generous support allowed me to touch the finish line of this long PhD
journey. Thank to Prof. John Cosgrove as my second supervisor for trusting me to finish this
PhD.

I thank Imperial College London and Department Earth Science and Engineering, especially to
Emma Watson, Saskia Goes, Peter Fitch, and Amanda Allotey for the support funding to help
me through my difficult circumstances. And also all the professor and staff for sharing their
knowledge.

I would also like to thank Simon Davis, Jonathan Watson, Amelia Davies, Claire Veillard,
Thomas Le Blévec, Maria Gusarevitch, and Sharan Dhami for mentoring me, and all the fun
in the laboratory. Terima kasih banyak Qi Adlan, Harya Dwi Nugraha, Fernando Sitorus,
Ngurah Beni Setiawan, and Aurio Erdi for always being helpful. I thank to all members of the
Carbonate Group: Marta Marchegiano, Gaetano Garfi, Sarah Robinson, Harriet Dawson,
Mahmoud El Yamani, and Saira Baharuddin for sharing the enthusiasm, knowledge, and
happiness. An also thank to all crew members of McDonalds Hammersmith and all my friends
I made along the way.

Finally, I express my deep gratitude to my dearest little family: Risca Mustika Suciati, and
Raihaanu Sarah Hafiyya for always lending your shoulder and holding out your hand to me.
Thank to my parents: Bambang Pamularso, and Herryningrum for believing in me and your
sincere pray. Also thank to my sister, Agita Pramuningrum for your support.
Contents
Chapter 1 - Introduction
1.1. Rationale ......................................................................................................................... 1
1.2. Aims ................................................................................................................................ 4
1.3. Objectives ....................................................................................................................... 5
1.4. Thesis outline .................................................................................................................. 6

Chapter 2 - Theoretical background, methodology, and materials

2.1 Fracture in geology ......................................................................................................... 9
2.1.1. Basic theory ............................................................................................................. 9
2.1.2. Deep biosphere existences along fracture ............................................................. 12
2.2 Oxygen, carbon, and clumped isotope thermometry theoretical background .............. 16
2.2.1. Introduction ........................................................................................................... 16
2.2.2. Oxygen and carbon stable isotope ......................................................................... 18
2.2.3. Clumped isotope thermometry .............................................................................. 18
2.2.4. Clumped isotope thermometry applications in calcite veins ................................. 21
2.3 Experimental protocol ................................................................................................... 24
2.3.1. Sample preparation and CO2 extraction by acid digestion of carbonate samples.. 24
2.3.2. CO2 gas purification .............................................................................................. 25
2.3.2.1. Manual CO2 purification line ......................................................................... 25
2.3.2.2. Automated Imperial Batch Acid Digestion and CO2 Purification Line (IBEX)
26
2.3.3. Isotope ratio mass-spectrometry measurement of the gas sample ......................... 29
2.4 Data processing and correction of δ18O, δ13C, and Δ47 ................................................. 30
2.4.1. Data processing of δ18O, δ13C, and Δ47.................................................................. 30
2.5 Data corrections ............................................................................................................ 34
2.5.1. δ18O and δ13C drift correction ................................................................................ 34
2.5.2. Non-linearity correction ........................................................................................ 35
2.5.2.1. Heated gas correction ..................................................................................... 35
2.5.2.2. Pressure base line correction .......................................................................... 36
2.5.3. Absolute reference frame....................................................................................... 36
2.5.4. Acid fractionation .................................................................................................. 43
2.5.5. The Δ47 to temperature conversion ........................................................................ 43
 2.5.6. The δ18O Fluid [VSMOW] calculation ........................................................................... 44
2.5.7. Metrics of contamination ....................................................................................... 44
2.6 Trace element analysis .................................................................................................. 45
2.7 Materials ....................................................................................................................... 45

Chapter 3 - Clumped isotope temperature of a Palaeozoic ‘deep biosphere’ recorded

within carbonate veins in granitic host rocks
3.1 Abstract ......................................................................................................................... 47
3.2 Introduction ................................................................................................................... 48
3.3 Sites and Materials ........................................................................................................ 49
3.4 Analytical Methods ....................................................................................................... 52
3.5 Result and Discussion ................................................................................................... 52
3.5.1. Clumped and bulk isotope results .......................................................................... 52
3.5.2. Clumped isotope in microbial settings: kinetic fractionation or useful proxy to
constrain deep-biosphere processes? ................................................................................... 56
3.5.3. Constraining the environment of Palaeozoic microbial calcite precipitation within
veins 58
3.6 Conclusions ................................................................................................................... 61

Chapter 4 - Combining clumped isotope and trace element analysis to constrain potential
kinetic effects in calcite
4.1 Abstract ......................................................................................................................... 62
4.2 Introduction ................................................................................................................... 63
4.3 Site and materials .......................................................................................................... 65
4.4 Analytical methods ....................................................................................................... 68
4.5 Result ............................................................................................................................ 68
4.6 Discussion ..................................................................................................................... 74
4.6.1 Relationship between calculated δ18OFluid and clumped isotope temperatures:
Recrystallization or potential kinetic effects? ...................................................................... 74
4.6.2 Trace Element Ratios as Proxy for the Rate of Precipitation of Natural Calcite
Samples 77
4.6.3 Pairing clumped isotopes and trace elements: Direct evidences for kinetic effects
81
4.7 Conclusions ................................................................................................................... 88
Chapter 5 - Structural diagenesis of a salt dome revealed by carbonate clumped isotope
thermometry (Jebel Madar, Oman)
5.1 Abstract ......................................................................................................................... 89
5.2 Introduction ................................................................................................................... 90
5.3 Regional geology .......................................................................................................... 93
5.4 Methods......................................................................................................................... 98
5.4.1 Sample selection and sample preparation .............................................................. 98
5.4.2 Carbonate clumped isotope thermometry .............................................................. 98
5.5 Results ........................................................................................................................... 99
5.6 Discussions ................................................................................................................. 104
5.6.1 Understanding the burial history of the carbonates in the carapace of the salt dome
104
5.6.2 Mechanism of cementation of the barite-calcite association, the thin-veins, and
nature of the associated fluids: potential for recrystallization ........................................... 105
5.6.3 The macro-columnar and ‘fault-zone’ calcite phase and potential kinetic effects
108
5.7 Conclusions ................................................................................................................. 111

Chapter 6 - Conclusions and further work

6.1 Conclusions, main findings, and wider implications .................................................. 112
6.2 Further work................................................................................................................ 114
List of Tables
Table 1. List of standards and isotopic composition ............................................................... 38
Table 2. Result from recent clumped isotopes analysis and fluid inclusion analysis by Drake
et al., 2017 and 2018. ............................................................................................................... 53
Table 3. Result from clumped isotopes and trace element analysis ........................................ 70
Table 4. Experimental conditions of Dromgoole and Walter, 1990b. .................................... 83
Table 5. Calculated ratios of DMn / DFe in calcite for several precipitation rates at 10°, 25°
and 50°C (after Dromgoole and Walter, 1990). ....................................................................... 83
Table 6. Clumped isotope measurement protocols for pilot samples and current samples .. 100
Table 7. Result from clumped isotopes analysis. .................................................................. 101
List of Figures
Figure 1. Two types of fracture that classified by the relative movement occurring over the
fracture surface including extension and shear fractures (picture modified after Twiss and
Moores, 1992). A. Extensional fracture or fracture of mode I, B. Mode II of the shear fracture,
and C. Mode III of the shear fracture. ...................................................................................... 14
Figure 2. Left picture is potential fracture planes developed in laboratory compression tests.
Extension fractures (A) and shear fractures (B and C) are shown (picture modified after Nelson,
2001). Right picture shown hybrid fractures are thought to occur under mixed tensile and
compressive stress conditions (figure modified after Ramsey and Chester, 2004). ................ 14
Figure 3. Simple illustrations of veins characterization by Bons et al. (2012) based on their
growth direction and crystal shape, including: syntaxial veins, stretching veins, and antitaxial
veins. ........................................................................................................................................ 15
Figure 4. Overview of the application of clumped isotope thermometry to calcite fracture from
2012 to November 2020........................................................................................................... 23
Figure 5. Illustration of acid digestion and manual CO2 purification line. The whole procedure
takes about 60 minutes. ............................................................................................................ 27
Figure 6. Illustration of automated IBEX purification line. The whole procedure takes about
25 minutes (modified from IBEX Control Centre Software Manual). .................................... 28
Figure 7. Illustration of mass spectrometer. A sample is inputted into the mass spectrometer,
and the molecules are ionized and accelerated. The ions are then through the electromagnetic
deflection and separated by mass analyzer, then detected ....................................................... 28
Figure 8. Example of linear regression for drift correction. ................................................... 39
Figure 9. Example of HG linear line show increasing Δ47 at heavier δ47. ............................... 40
Figure 10. Scans run showing mass 47 intensities across acceleration voltages 9.30-9.50 kV
(top). Linear regression between the background and the beam intensity used to correct for the
effect of the secondary electrons (bottom). .............................................................................. 41
Figure 11. Correction by comparing the sample with the standards. ..................................... 42
Figure 12. Top left picture is map of Fennoscandian Shield tectonic domain (figure modified
from Koistinen et al, 2001 op. cit. Söderbäck, 2008). The six tectonic domains have been
separated based on differences in the timing of tectonic activity or in the character and intensity
of the strain. Forsmark is situated in tectonic domain 2, and Laxemar and Götemar areas inside
tectonic domain 5. Bottom left picture is core image (figure modified after Drake et al., 2017)
with mineral appearance of coarse-grained calcite (white), apshaltite (black) and pyrite
(metallic cubic crystals) on a fracture surface from Forsmark (KFM06C:103 m). Bottom right
picture is pyrite crystals intergrown with the outermost calcite growth zone (polished crystal
cross-section, KKR02, Götemar. Figure modified after Drake et al., 2017). .......................... 51
Figure 13. Plot between δ13C Calcite [VPDB] and clumped isotopes derived temperature. The
association of lower-temperatures with more depleted δ13C Calcite [VPDB] indicated the most
optimal growth temperatures of the organisms. ....................................................................... 54
Figure 14. Plot between δ18O Fluid [VSMOW] and clumped isotopes derived temperature of nine
samples from Laxemar, Götemar and Forsmark...................................................................... 55
Figure 15. . Simplified model of circulation for brine water along different fracture sets. The
earlier phase of calcite generation happens in a setting similar to the top picture whereas the
later calcite phase precipitated in a setting represented by the bottom picture. The inset image
is modified after Drake et al., 2017 and shows the co-existence of different sets of calcite vein
(separated by a dashed yellow line) in the BSE-SEM-images of polished calcite crystals. The
later calcite phase represents the largest volume of mineral precipitate. ................................. 60
Figure 16. Twenty-one transect points from three different samples location. Point ‘A’ is the
earliest stage of vein growth. ................................................................................................... 67
Figure 17. Images of calcite vein sample under normal (transmitted) light (left pictures) and
cathodoluminescence conditions (right pictures). The two top pictures are macro columnar vein
(Vandeginste et al., 2017) and the two bottom pictures are thin-vein calcite (Hajibeigy, 2017).
.................................................................................................................................................. 67
Figure 18. Plot of bulk isotopic composition between δ13CCalcite [VPDB] and δ18O Calcite [VPDB] from
twenty-one intersect points at three different places. The samples from macro-columnar calcite
(blue color) shows more negative or lighter bulk isotope composition than the samples from
thin-vein calcite (yellow color). ............................................................................................... 71
Figure 19. Plot between δ18O Fluid [VSMOW] and clumped isotopes temperature of twenty-one
transect samples from three different crystals. The samples from macro-columnar calcite (blue
color) shows lighter δ18O Fluid [VSMOW] and lower temperature than the samples from thin-vein
calcite (yellow color). .............................................................................................................. 72
Figure 20. Graph plot between clumped isotope temperature in ºC and Mn composition in ppm
of JMF 1 (top), JMF 12 (middle), and JMG 1 (bottom). ......................................................... 73
Figure 21. Plot between δ18O Fluid [VSMOW] and clumped isotope temperature of macro-columnar
calcite samples. The δ18O Calcite [VPDB] isoline in the background indicating a strong relationship
of increasing in δ18O Calcite [VPDB] and an increasing in estimated precipitation temperature will
result in a heavier calculated δ18O Fluid [VSMOW]. JMF 1 A is plotted outside the trend, because
the sample is too close to the host-rock thus mixing with the host-rock when powdered the
sample using micro-drill is more likely. .................................................................................. 76
Figure 22. DMn values from Dromgoole and Walter, 1990 at the 10, 25, 50°C and are controlled
by the rate of precipitation. ...................................................................................................... 83
Figure 23. Graph plot between clumped isotope temperature and DMn/DFe composition of
macro-columnar calcite samples: JMF 1. The grey lines indicate the log rate of precipitation
(µmol m-2hr-1). ......................................................................................................................... 85
Figure 24. Graph plot between clumped isotope temperature and DMn/DFe composition of
macro-columnar calcite samples JMF 12. The grey lines indicate the log rate of precipitation
(µmol m-2hr-1). ......................................................................................................................... 86
Figure 25. Plot of bulk isotopic composition between δ13C Calcite [VPDB] and δ18O Calcite [VPDB]

(top), and δ18O Fluid [VSMOW] and clumped isotopes derived temperature (bottom) of JMG 1 thin-
vein calcite and host rock samples. .......................................................................................... 87
Figure 26. Picture of the existence of a large network of metric-size fractures filled with
diagenetic calcite crystals in Jebel Madar, Oman. ................................................................... 92
Figure 27. Map view of geological map of study area (modified after Claringbould et al., 2013)
overlaid with elevation model from ASTER GDEM (top) showing sample locations. The 3D
image of Jebel Madar (bottom left) shows the geometry of the triple junction between the three
main fracture corridors in the middle of the salt dome. ........................................................... 95
Figure 28. Stratigraphy of Cretaceous Formations at Jabal Madar. Column A to D is modified
after Vandeginste et al. (2017), Column E is clumped isotope temperature of the matrix and
calculated geothermal gradient from the current thesis (see text for detail). ........................... 96
Figure 29. Tectonic evolution of Jebel Madar. The evolution divided into three different phases
from Late Cretaceous to Miocene (modified after Claringbould et al., 2013). ....................... 97
Figure 30. Sample occurrence for this study, which are: thin-vein calcite (top-left), barite-
associated calcite (top-right), fault zone calcite (bottom-left), and macro-columnar calcite
(bottom-right). ........................................................................................................................ 100
Figure 31. Plot of bulk isotopic composition between δ13CCalcite [VPDB] and δ18O Calcite [VPDB] from
twenty-six calcite vein samples. The background data points are δ13CCalcite [VPDB] and δ18O Calcite
[VPDB] isotopic composition of Vandeginste, et al., 2017; thin-vein calcite, barite-associated
calcite, fault zone calcite, and macro-columnar calcite are plotted in the same colors and shapes
with the current study data plot. Some of the fault zone calcite from current analysis have
similar isotopic composition with macro-columnar calcite, thin-vein, and barite-associated
calcite from the Vandeginste et al, 2017 data. ....................................................................... 102
Figure 32. Clumped isotope results. The vertical axis corresponds to clumped isotope
temperature in ºC; the horizontal axis is calculated δ18O Fluid [VSMOW]. The grey diagonal lines
represent lines of equal δ18O composition for the calcite, in ‰ VPDB. Blue and red arrows
show the different trend of vein precipitation (see text for the detail)................................... 103
Figure 33. Data plot between ratio Mn and Fe (DMn/DFe) and clumped isotope temperature.
The isoline shows the same rate of precipitation in µmol m-2hr-1. The grey isoline is the log of
rate precipitation above 0 µmol m-2hr-1, and the orange line is below 0 µmol m-2hr-1. ......... 103
Chapter 1

Chapter 1

Introduction

1.1. Rationale

There are two main pathways for fluids circulations in rocks, either within pores of the rock

matrix, or within fractures (Bons et al., 2012). Thus the fracture systems can serve as either

barriers or conduits to fluid flow influencing potential hydrocarbons migration pathway and

potential storage (e.g. Eichhubl et al., 2004; Laubach et al., 2010). However, fracture porosity

evolves through interaction between fracture growth and sealing (Laubach and Ward, 2006),

and thus a better understanding of the interaction between the mechanical processes of the

fracture systems and the chemical process that can alter the existing fractures is crucial to

predict subsurface fluid flow. Several works highlight the importance of the study of

deformational structures and chemical changes, known as structural diagenesis (Laubach et al.,

2010), in controlling fluid flow in fracture systems (e.g. Eichhubl et al., 2004, 2009; Laubach

and Ward, 2006). A crucial aspect of this work is that diagenetic cements precipitated along

the fracture or fault preserve information about the history, temperature and origin of the

diagenetic fluids from which they grow. Previous integrated study combining paleo

thermometry analysis, such as stable isotope and fluid inclusion analysis (e.g. Kenis et al.,

2000; Immenhauser et al., 2007; Reuning et al., 2009; Vandeginste and John, 2012;

Vandeginste et al., 2017) have been conducted to reconstruct the fluid origin and temperature

from fracture related samples.

1
Chapter 1

Here we apply clumped isotope thermometry to a suite of samples to unravel information about

the relative structural timing, episodes of fluid flow, the origin and temperature of fluids in

different tectonic settings and their evolutions through time, and also the interaction between

fluid and host-rock. Clumped isotopes are increasingly used to infer the origin and thermal

history of calcite fracture infill (e.g. Swanson et al., 2012; Bergman et al., 2013; Budd et al.,

2013; Luetkemeyer et al., 2016; Hodson et al., 2016; Quesnel et al., 2016; Siman-Tov et al.,

2016; Macdonald et al., 2017; Dennis et al., 2019; MacDonald et al., 2019; Nardini et al., 2019).

Developed in the last decade, the method is based on measurement of Δ47 (clumping of 13C-
18
O bonds in the carbonate lattice (Ghosh et al., 2006; Schauble et al., 2006). Based on

equilibrium thermodynamics, the amount of clumping, i.e. the abundance of Δ47 of CO2 relative

to a stochastic distribution, can be used as a paleo-thermometer. Unlike conventional carbonate

paleo thermometer (e.g. Urey, 1947; McCrea, 1950; Epstein et al., 1953), clumped isotope

thermometry does not require assumption of the composition of the fluid from which the calcite

grew. This beneficial makes clumped isotopes thermometry has been used to a broad array,

including fluid flow and water rock interactions, structural geology, diagenesis (e.g. Bristow et

al., 2011; Huntington et al., 2011; Loyd et al., 2014; Streit et al., 2012; Swanson et al., 2012;

Loyd et al., 2012; Bergman et al., 2013; Budd et al., 2013; Sena et al., 2014; Dale et al., 2014;

Luetkemeyer et al., 2015, 2016; Huntington and Lechler, 2015; Quesnel et al., 2016; Siman-

Tov et al., 2016; Cruset et al., 2016; Hodson et al., 2016; Lu et al., 2017; Macdonald et al.,

2017; Veillard et al., 2019; Dennis et al., 2019), terrestrial paleoclimate (e.g. Affek et al., 2008;

Passey et al., 2010; Csank et al., 2011; Eiler, 2011; Snell et al., 2013; Wang et al., 2013; Eagle

et al., 2013; Brand et al., 2014; Tobin et al., 2014; Frantz et al., 2014; Drury et al., 2016, 2017;

Hönig et al., 2017), basin thermal histories and metamorphism (e.g. Dennis and Schrag, 2010;

Ferry et al., 2011; Passey and Henkes, 2012; Dale et al., 2014; Henkes et al., 2014; John, 2015;

Shenton et al., 2015; Beckert et al., 2016). However, since the clumped isotope thermometer

2
Chapter 1

is also based on equilibrium thermodynamics, it potentially suffers from the same shortcomings

as oxygen isotope thermometry (Watkins and Hunt, 2015), especially for natural carbonates

which often grow in non-equilibrium conditions (Dietzel et al., 2009). This non-equilibrium

condition or kinetic fractionation effect have been observed in fast growing corrals (Saenger et

al., 2012), and are common in speleothems (Affek et al., 2008; Daëron et al., 2011; Wainer et

al., 2011; Kluge and Affek, 2012). In fracture related systems, some potential kinetic effect

could be linked to host rock buffer, precipitation rate of calcite vein, and potential CO2

degassing.

To explore if any particular kinetic isotope fractionation effects impact the clumped isotope

signature of carbonates precipitated within fractures, part of the present thesis thus focuses on

the application of carbonate clumped isotope thermometry to analyze the temperature of calcite

precipitated along the fracture in detail, for instance single phased cements in fractures. This

detailed clumped isotopes work will be integrated with calculation of elemental ratios from

Inductively Coupled Plasma Mass Spectrometry (ICP-MS) to obtain better result of fluid

composition, kinetic fractionation effect and rate of precipitations. Element composition of the

powdered calcite samples will be determined by using ICP-MS. Pairing trace elements with

clumped isotopes makes sense because the abundance and distribution of trace elements is

often used to constrain diagenetic history in carbonates (Veizer et al., 1989; Bruhn et al., 1995),

growth kinetics (Lorens, 1981; Mucci, 1988; Dromgoole and Walter, 1990), and solution

composition (Mucci, 1988).

The general approach of the thesis is to use a multi-proxy approach applied to a number of case

studies where independent data exist, including the Laxemar, Götemar and Forsmark (hereafter

‘LGF’) area in Sweden, and Jebel Madar in Oman. The LGF area is selected in part because of

previous work demonstrating microbial activity at this location, but also because of the

availability of published fluid inclusion (Drake et al., 2017) that can be directly compared to

3
Chapter 1

carbonate clumped isotope thermometry. More important, the LGF study is the first application

of carbonate clumped isotope thermometry to microbial calcite within veins within a granitic

host rock. In terms of the mains reasons for selecting Jebel Madar for our second case study, it

is ideal in part because of the availability of published data (Immenhauser et al., 2007;

Vandeginste et al., 2017) that can complement the current research, but also because the size

of the minerals (up to >20 cm) allows for detailed transects across a single mineral. Another

motivation was preliminary data from an MSci thesis done within the carbonate group

(Hajibeigy, 2017) suggesting that some of kinetic processes discussed above could be taking

place within calcite fracture infill at Jebel Madar, Oman.

The overall work done in the framework of this PhD thesis will serve to better establish the

applications and limitations of clumped isotope analysis in structural diagenesis, focusing on

fractures in different structural setting (deep biosphere and salt diapirism), and also to

investigate whether kinetic effects exist or not for clumped isotopes within fractures.

1.2. Aims

The overall aims of this thesis are to unravel the paleo-temperature and fluid composition that

lead to carbonate precipitation, and also to explore if any particular kinetic isotope fractionation

effects impact the clumped isotope signature of carbonates precipitated within fractures. In

order to achieve the aims, the following key questions will be addressed:

1. How reliable is carbonate clumped isotope thermometry compare to another paleo

thermometer proxy in fracture-related carbonates?

2. What are the major factors that could cause kinetic fractionation in calcite

precipitation along the fracture?

3. How could we detect kinetic fractionation within the carbonate samples?

4
Chapter 1

4. How important is clumped isotope thermometry as a method to investigate relative

structural timing information, series of episodic fluid flow, the origin and temperature

of fluids from different tectonic settings and evolutions through time, and also the

interaction between fluid and host-rock?

These questions form the main aims of the thesis, and will be more explicitly addressed in the

discussion.

1.3. Objectives

The following objectives were undertaken to answer the key questions above. These objectives

are divided based on the result chapters and associated with the questions they help to address.

 Objective 1: Clumped isotope temperature of a Paleozoic ‘deep biosphere’ recorded within

carbonate veins in granitic host rocks is designed to address questions 1. The approach taken

was to:

• Measure Δ47, δ13C, and δ18O of the vein samples using both manual preparation line for

larger sample size and our automated clumped isotope preparation line (the IBEX) to

be able to obtain a similar gas yield whilst reducing the physical sample size in order

to achieve a single clumped isotopes analysis.

• Compare the clumped isotope temperature data with the previously published fluid

inclusion data.

• Constrain the environmental parameters that led to the existence of a deep biosphere.

 Objective 2: Combining Clumped Isotope and Trace Element Analysis to Constrain

Potential Kinetic Effects in Calcite is designed to address questions 2 and 3. The approach

taken was to:

• Systematically sample fine transect section from the different vein.

• Measure Δ47, δ13C, and δ18O of the fine transect section from vein using automated

5
Chapter 1

clumped isotope preparation line (the IBEX).

• Measure trace element using Inductively Coupled Plasma Mass Spectrometry (ICP-

MS) to calculate Mn and Fe elemental ratio from the same samples above.

• Determine correlation between clumped isotope temperature and Mn and Fe elemental

ratio to investigate the rate of precipitation.

• Investigate the relationship between rate of precipitation and kinetic fractionation

within detailed vein samples.

 Objective 3: Structural diagenesis of a salt dome revealed by carbonate clumped isotope

thermometry (Jebel Madar, Oman) is to address question 1 and 4. The approach taken was

to:

• Measure Δ47, δ13C, and δ18O of the vein samples using both manual preparation line for

larger sample size and our automated clumped isotope preparation line (the IBEX).

• Using clumped isotope methodology to distinguish different isotopic signature of each

vein type, investigate paleo-temperature, and fluid source.

• Reconstruct the clumped isotope values of the host-rock in order to estimate

temperature of recrystallization of the matrix and thus minimum estimates of regional

burial depth.

• Investigate the effect of kinetic fractionation in clumped isotope temperature.

1.4. Thesis outline

This thesis consists of six chapters as follows:

Chapter 1: “Introduction”. This chapter provides general introduction, background

information, aims and objectives of thesis.

Chapter 2: “Theoretical background, methodology, and materials”. This chapter presents

literature review of fractures in geology, carbonate clumped isotopes, and oxygen, and carbon

6
Chapter 1

isotope measurement, trace element analysis, instrumental setup and analytical procedures, as

well as the statistical methods used in Stable Isotope Laboratory at Imperial College London,

also the overview of samples material.

Chapter 3: “Clumped isotope temperature of a Paleozoic ‘deep biosphere’ recorded

within carbonate veins in granitic host rocks”. This chapter is the first results chapter, and

is designed to address objective 1. The chapter demonstrates for the first time the application

of carbonate clumped isotope thermometry within veins in a granitic host rock. This chapter

thus focused on how carbonate clumped isotope thermometry significantly reduce uncertainties

in interpreting the environment of a fossil deep-biosphere present within fractures.

This chapter is under review in Earth and Planetary Science Letters:

Herlambang A, John C. M, Drake H. Physicochemical conditions of the ancient continental

deep biosphere tracked by clumped isotope temperatures of granite-hosted carbonate veins.

Chapter 4: “Combining Clumped Isotope and Trace Element Analysis to Constrain

Potential Kinetic Effects in Calcite”. This chapter is the second results chapter, and addresses

objective 2. This chapter demonstrates that a combined clumped isotopes and trace elements

approach could a critical step to future application of the clumped isotope proxy to natural

systems, as it can reveal potential isotopic disequilibrium independently of the temperature

measured by clumped isotopes.

This chapter is accepted and under revision in Geochemica et Cosmochemica Acta:

Herlambang A & John C. M. Combining Clumped Isotope and Trace Element Analysis to

Constrain Potential Kinetic Effects in Calcite.

Chapter 5: “Structural diagenesis of a salt dome revealed by carbonate clumped isotope

thermometry (Jebel Madar, Oman)”. This chapter is the third results chapter, and addresses

objective 3. This chapter focuses on the reconstructing the paleo thermometry of a key study

7
Chapter 1

area (a salt dome), and shows how the knowledge gained in the previous two chapters can be

applied to a case study to (1) identify possible kinetic fractionation in the clumped isotope

analysis, and (2) reconstruct the timing of fluid flow in this complex tectonic setting.

Chapter 6: Conclusion and Further Work. This chapter brings together the studies described

in chapter 3, 4, and 5 to discuss the application of clumped isotope as structural diagenesis

approach in order to obtain the better understanding of paleo-temperature, origin of the fluid,

presence of deep biosphere, relative fluid flow and structural timing information, but also

explore any possible caveats of the methods related to kinetic fractionation effect, including

positive evidence, independent approach to detect, and impact of kinetic fractionation in the

carbonate clumped isotope thermometry along the vein.

8
Chapter 2

Theoretical background, methodology, and

materials

This chapter contains theoretical background based on literature review, methodology, and

sample material for measurements. The methodology subchapter including: experimental

protocol, corrections, and calibration of oxygen and carbon stable isotope analysis, carbonate

clumped isotope thermometry, and trace element analysis. The stable isotope and clumped

isotope analysis were done in the Stable Isotope Laboratory at Imperial College London. The

trace element analysis using inductively coupled plasma mass spectrometry was done in the

Qatar Carbonates and Carbon Storage Research Centre at Imperial College London.

2.1 Fracture in geology

2.1.1. Basic theory

Fracture in Latin word is fractus, which means broken. Fractures are surfaces that cross along

rock or mineral, causing that rock or mineral to lose cohesion (Twiss and Moores, 1992).

According to Nelson (2001) fractures are areas of discontinuity in rocks that lose cohesion,

formed naturally by deformation or diagenesis. Fractures from the geomechanical aspects are

defined as surfaces that lose cohesive forces in a plane (Cosgrove, 1998). Fracture can occur

when the difference between the value of the maximum vector of principal stress and the

minimum vector principal stress is greater than the value of the cohesive strength of a material.

9
Chapter 2

In other definitions, fracture is a failure in a material under brittle conditions (Childs et al.,

1996). The orientation and type of fractures as a brittle failure is outline in many publications

including Anderson (1948), Price and Cosgrove (1990), Cosgrove (1998).

Mainly there are two types of fracture that can be classified by the relative movement occurring

over the fracture surface: extension and shear fractures (Twiss and Moores, 1992). For an

extensional fracture or fracture of mode I, the movement is relatively perpendicular to the

fracture wall (Figure 1a). For shear fractures the movement moves parallel to the fracture

surface. In Mode II of the shear fracture, the movement occurring is a shear motion

perpendicular to the edges of the fracture (Figure 1b); for mode III of shear fracture, the

relative movement parallel to the outer edges of the fracture (Figure 1c).

In addition, according to Nelson’s laboratory compression test (2001), fractures are divided

into three types (Figure 2), which are shear fractures, extension fractures, and tensile fractures.

Both extension and shear fracture formed in compressive condition, which means all of the

principal stress are in positive value. Shear fracture formed in the same way than reverse fault,

with displacement mostly parallel to low angled to slip surface. In contrast, extension fractures

have mostly perpendicular slip to the fracture surface. Extension fractures can also form what

is known as hybrid fracture. Hybrid fractures are thought to occur under mixed tensile and

compressive stress conditions (Ramsey and Chester, 2004). Tensile fractures are similar to

extension fractures in morphology and orientation which is perpendicularly opened to fracture

surface, but at least one of principal stress (σ3) must be negative (tensile).

In general, the fracture forming within the rocks are following the Mohr-Coulomb theory and

summarized as diagram of failure envelope for brittle failure (see Figure 2). There are two

main components of the diagram including failure envelope and Mohr’s circle. The failure

envelope is determined in part by the Navier-Coulomb criteria for shear failure and in part by

10
Chapter 2

Griffith criteria of extensional failure (Brace, 1960; Phillips, 1972; Sibson and Scott, 1998;

Cox, 2010). Mohr’s circle is represented the principal stress, and when the circle touches the

envelope, failure will occur.

Fractures can provide permeability for fluid movement, such as water or hydrocarbons. When

mineral constituents carried by an aqueous solution are deposited through precipitation will

form mineral deposits called veins. Numerous studies have been devoted to the process of vein

formation mainly because of their significance in term of to determine stress, strain,

temperature, pressure, fluid composition and fluid origin during their precipitation. Veins

present a wide range of internal geometries, resulting from different combinations of growth

direction and shape of the crystal. In common, growth direction following the crack-seal

mechanism, which introduced by Ramsay (1980). The Ramsey’s work interpreted that vein

growth controlled by the crack-seal mechanism shows an elongate to fibrous crystal shape.

However, more recent work by the other researchers suggested that not all fibrous veins are

crack-seal veins (Oliver and Bons, 2001; Bons and Montenari, 2005).

Following veins characterization by Bons et al., (2012), there are four types of vein based on

their growth direction and crystal shape, including: syntaxial veins, stretching veins, antitaxial

veins, and fringes. Syntaxial veins are veins where the precipitated minerals grow out from the

wall rock of the vein and grow inward. Typically, vein growth is from both sides of the vein

towards the center, but occasionally that crystals only grew from one side towards the other

(Fisher and Brantley, 1992). Syntaxial veins can form from a single cracking event, which

created the space for minerals to grow into (Wilson, 1994), and can also form by the crack-seal

mechanism (Ramsay, 1980; Urai et al., 1991). The crystal morphology shows elongate shape

or blade-like crystal and also blocky-shape in the growth direction. Different growth rates of

individual crystals due to crystallography result in growth competition where some crystals

outgrow others (Bons, 2001; Bons and Bons, 2003; Nüchter and Stöckhert, 2008; Okamoto

11
Chapter 2

and Sekine, 2011). Individual growth episodes, or seal events in case of crack-sealing, can

often be visualized with cathodoluminescence or can be inferred from inclusion bands

(Ramsay, 1980).

Stretching veins are veins where the crack plane is not always the same material plane and only

can formed by crack-sealing (Ramsay, 1980; Renard et al., 2005). In stretching veins type, the

crack surface can cut through previously precipitated material (localized stretching veins) and

even through the wall rock (delocalized stretching veins). As a result, there is no systematic

trend of the growth directions. The stretched grain can achieve very high length/width ratios

and are therefore often called stretched crystals (Bons et al., 2012). Both of syntaxial veins and

stretching veins can be located within a single fracture as series of multiple crack-seal events.

Antitaxial veins typically have fibrous crystals with sometimes extreme length/width ratios.

The distinguishing feature of antitaxial veins is the presence of median zone (Oliver and Bons,

2001; Bons and Montenari, 2005), which is the substrate from which the vein crystals grow

outwards in both directions as the vein widens.

Pressure shadows and fringes are a special type of veins that form in the pressure shadows

adjacent to relatively rigid objects, typically pyrite grains, in a deforming matrix. The term

pressure shadow in a microstructural sense is used when the soluble-mineral enriched zone has

diffuse boundaries (Passchier and Trouw, 1996 in Bons et al., 2012).

2.1.2. Deep biosphere existences along fractures

The deep biosphere is the part of the biosphere that resides below the first few meters of the

surface (Hoehler and Jørgensen, 2013). These deep and dark biological reservoirs may extend

to several kilometers beneath the seafloor and perhaps deeper in the continental subsurface

(Deep Carbon Observatory, 2015). Some of the microbes that live here, instead of using the

12
Chapter 2

sun’s light as a source of energy, rely on energy from hydrogen and methane (Lollar et al.,

2008) to drive the synthesis of molecules essential for life and reproduction.

Historically, the first occurrence of the microbial existence in subsurface was back to 1920’s

when microbiologist explained why water extracted from the depth in oil fields contained

chemicals (hydrogen sulfide and bicarbonates) which are normally produced by bacteria. Then

in 1930’s to 1950’s the first studies of subsurface life were conducted by Claude E. ZoBell,

considered to be the father of marine microbiology, probed beneath the sea floor and found

microbes wherever the sediments were sampled (Mascarelli, 2009). Since then, intensive

studies of deep boreholes in some places all over the world, such as the Sweden (Pedersen,

1997; Drake et al., 2017), United States (Jimenez et al., 1991; Edwards et al., 2006), Finland

(Haveman et al., 1999), South Africa (Gihring et al., 2006; Lin et al., 2006), and Japan

(Hirayama et al., 2005), using a variety of molecular techniques, have shown an active

biosphere composed of diverse groups of microorganisms. The microbial communities

reported from different subsurface communities vary widely; such differences are due to varied

water origin and chemistry, different host rock types, as well as geography.

Furthermore, related to this current research, investigations over the last two decades confirmed

that microorganisms thrive in oligotrophic fracture system in granitic host rock (Pedersen,

1997) and fractures in deep sub-seafloor igneous crust material (Thorseth et al., 1995). In recent

years, the exploration of the deep biosphere in fractured crystalline basement of continents and

oceanic crust has produced a growing awareness of life extending below the surface, into deep

igneous rock (Pedersen et al., 2008; Heim, 2011; Drake et al., 2017, 2018; Ivarsson et al., 2020;

Suzuki et al., 2020). To our knowledge, this study is the first clumped isotopes thermometry

application to reveal the deep biosphere existence along the fracture system.

13
Chapter 2

Figure 1. Two types of fracture that classified by the relative movement occurring over the fracture surface
including extension and shear fractures (picture modified after Twiss and Moores, 1992). A. Extensional fracture
or fracture of mode I, B. Mode II of the shear fracture, and C. Mode III of the shear fracture.

Figure 2. Left picture is potential fracture planes developed in laboratory compression tests. Extension fractures
(A) and shear fractures (B and C) are shown (picture modified after Nelson, 2001). Right picture shown hybrid
fractures are thought to occur under mixed tensile and compressive stress conditions (figure modified after
Ramsey and Chester, 2004).

14
Chapter 2

Figure 3. Simple illustrations of veins characterization by Bons et al. (2012) based on their growth direction and
crystal shape, including: syntaxial veins, stretching veins, and antitaxial veins.

15
Chapter 2

2.2 Oxygen, carbon, and clumped isotope thermometry theoretical background

2.2.1. Introduction

Isotopes are atoms of the same element that have the same number of protons, but unequal

number of neutrons, thus differ in weight. There are two type of isotopes, namely radiogenic

and stable isotopes. The different between the two is that radioactive isotopes decay over time.

In contrast, stable isotopes do not decay since they have a stable nucleus and their abundance

therefore remain constant through time. The relative abundance of stable isotopes can be

measured experimentally, and is expressed as a stable isotope ratio which is affected by isotope

fractionation in nature. The ratios are measured using mass spectrometry, which split the

different isotopes of an elements based on their mass-to-charge ratio (m/z).

Isotopic fractionation is defined as the relative segregating of the lighter and heavier isotopes

between two coexisting phases (Lindemann, 1919). The popularization of the application of

stable isotopes in geochemical research is credited to Urey (1947) and Bigeleisen and Mayer

(1947), after their pioneering research to calculate equilibrium isotope fractionation. These
18
calculations suggested the possibility of a paleo thermometer based on using O/16O

fractionation in the calcite-water system (Urey, 1947). Isotope fractionations factor (annotated

with “ɑ”) are typically very small, on the order of a few parts per thousand or parts per ten

thousand, thus usually expressed by 1000ln(ɑ) or 1000 (ɑ-1) to magnify the difference between

ɑ and 1. To quantify the isotope fractionation factor for the light (lightX) and heavy isotopes

(heavyX) between two substance XA and XB we can use the following equation in Friedman and

O’Neil (1977):

(heavy𝑋/ light𝑋)XA
ɑXA-XB = (heavy𝑋/ light𝑋)XB
(2.1)

16
Chapter 2

The main isotopic fractionation used in this study are for oxygen and carbon and are defined

with respectively:

(18𝑂/ 16𝑂)XA
ɑ OXA-XB = (18 (2.2)
𝑂/ 16𝑂𝑋)XB

(13𝐶/ 12𝐶)XA
ɑ CXA-XB = (13𝐶/ 12𝐶)XB
(2.3)

In general, there are two different type of isotopic fractionation processes, namely equilibrium

fractionation and kinetic fractionation. Equilibrium fractionation is a chemical equilibrium

reaction, where both reactants and products concentrations have no further tendency to change

with time, usually when the reaction rates of the forward and backward reactions are broadly

equal. In this case, isotope can move to or from the two phases and the equilibrium is attained

when the isotopic ratios does not change any more over time. The equilibrium stable isotope

fractionation is a quantum-mechanical phenomenon, driven mainly by differences in the

vibrational energies of molecules and crystals containing atoms of differing masses (Urey,

1947).

Kinetic isotope fractionation is a separation process of different isotopes from each other by

their mass following a one-directional process under conditions of incomplete isotopic change.

One common systematic behavior in many kinetic fractionations is that light isotopes, being

more reactive, are concentrated in reaction products (Schauble, 2004). Kinetic fractionations

are usually sensitive to a host of factors (such as reaction rates and the presence of exchange

catalysts) in addition to temperature.

Temperature additionally has a robust control on isotope fractionation (Urey, 1947).

Fractionation decreases at elevated temperatures because the system’s entropy counterbalances

the isotope effects. Isotopes also fractionate during precipitation of carbonates from solution.

The δ18O and δ13C of carbonates rely on the kinetics of precipitation in addition to the isotopic

17
Chapter 2

composition of the solution from which they have precipitated. Hence, δ18O and δ13C can

provide the temperature and fluid chemistry from which carbonates precipitated.

2.2.2. Oxygen and carbon stable isotope

The applications of the stable isotopic fractionation that are related to this carbonate study is
18
the relative abundant of O and 13C relative to the most abundant isotopes 12C and 16O. The

abundances of these ‘heavy’ carbon and oxygen isotopes in carbonate are usually in the order

of a few per mill (‰) and are annotated with the “δ”.

Oxygen and carbon isotopes in carbonate are commonly used as paleoclimate proxy. Oxygen

isotopes reflect the temperature dependence of the isotopic fractionation between CaCO 3 and

the water in which it grows (e.g. (McCrea, 1950; Epstein et al., 1953; O’Neil et al., 1969; Kim

and O’Neil, 1997a). Oxygen isotopes, however, do not provide a direct paleo thermometer, and

temperature reconstructions rely on independent estimates of water isotopic compositions. This

is because 18O in carbonates is a function of both origin fluid composition and temperature of

which mineral precipitates. Thus to estimate one of the two parameters one needs to know the

other.

2.2.3. Clumped isotope thermometry

13
Clumped isotope thermometry is based on measuring the clumping of C-18O bonds in the

carbonate lattice with the mass of 47 (indicated as Δ47) (Ghosh et al., 2006; Eiler, 2007; Dennis

et al., 2011). Clumped isotope geochemistry thus involves the measurement of multiply

substituted isotopologues in molecules and minerals (Eiler, 2007). Isotopologues are molecules

of similar chemical composition but different isotopic composition. Isotopologues containing

13 18
more than one rare ‘heavy’ isotopes i.e. C O16O are referred as multiply substituted

isotopologues.

18
Chapter 2

Molecules with rare isotopes have different properties thanks to the change in mass caused by

isotope substitution. The mass increase created by isotope substitution increases the stability

of the molecule by reducing its potential energy. Meaning, isotopic substitution of a heavy for

a light isotope in a chemical bond reduces the vibration frequencies of that bond and, therefore,

its zero-point energy (Bigeleisen and Mayer, 1947; Urey, 1947; Eiler, 2007). According to

quantum theory, molecules always have zero-point energy (n=0) higher than the minimum

energy on the potential curve, even at a temperature of absolute zero. This zero-point energy

(n=0) is caused by the vibration of the atoms. The lower the mass of the isotope involved in

the bond, the higher the zero-point energy is. The fact that the zero-point energy depends on

the atomic mass explains why non-substituted, singly-substituted or multi-substituted

molecules behave differently. Indeed, bonds between light isotopes require less energy to

dissociate than bonds between heavy isotopes and on the contrary, bonds involving heavy

isotopes are more stable than bonds only involving light isotopes. In other word, the multiply

substituted molecules have a lower potential energy than single or non-substituted molecules.

For this reason, isotopic substitution influences thermodynamic stabilities of molecules and

rates of many kinetically-controlled reactions. The ‘rule of the geometric mean’ or simply the

‘rule of the mean’ (Bigeleisen, 1955) implies that the decrease in bond energy associated with

heavy-heavy substitutions is twice that of the heavy substitution for only single atom. However,

this rule is only an approximation and, at ambient temperatures, the energy associated with the

substitution of two isotopes slightly exceed twice the energy required for the substitution of

one isotope (Affek and Eiler, 2006; Eiler, 2007). This departure from the rule of the mean

induces a thermodynamic drive for “clumping” of doubly-substituted isotopes rather than

singly-substituted isotopes. This effect is counterbalanced by the entropy of the system, or the

drive toward the random distribution of isotopes as temperature increases. Beyond a certain

19
Chapter 2

temperature, there is no drive for the formation of heavy-heavy bonds and the abundance of

those can be computed by the rule of the mean.

The principle of clumped isotope thermometry is to take advantage of the departure from rule

of the mean explained in the previous paragraph and use it as a proxy to estimate the

temperature of carbonate precipitation. Clumped isotope thermometry are reported in terms of

Δi which denotes the excess of clumped isotopes compared to the amount predicted when

isotopes are randomly distributed amongst isotopologues (Eiler and Schauble, 2004; Wang et

al., 2004) and defined as:

Ri
Δi = (R * − 1) × 103 (2.4)
i

The variable Δi is expressed in per mil (Eiler and Schauble, 2004). Where Ri expresses the

distribution of isotopologues of interest relative to the isotopically normal isotopologues or

non-substituted. Specifically, R i = mi / m44 are abundance ratio relative to mass 44. Ri* or R47*,

R46*, R45* value represents the same ratio in the same bulk isotopic composition but with the C

and O randomly distributed amongst all the isotopologues. These are calculated using

following equations:

R45* = R13 + 2 . R17 (2.5)

R46* = 2 . R18 + 2 . R13 . R17 + (R17)2 (2.6)

R47* = 2 . R13 . R18 + 2 . R17 . R18 + R13 . (R17)2 (2.7)

Where R13, R17 and R18 are the abundance ratios of 13C/12C, 17O/16O and 18O/16O respectively

for the sample.

20
Chapter 2

2.2.4. Clumped isotope thermometry applications in calcite veins

The first samples related to calcite vein analyzed with clumped isotope thermometry were in

2012 in Nevada by Swanson et al. and Streit et al. in Oman. Since then, the number of

measurements has increased, to our knowledge, to reach a total of 36 published data points

(Streit et al., 2012; Swanson et al., 2012, 2018; Bergman et al., 2013; Loyd et al., 2013; Budd

et al., 2013; Sumner et al., 2015; Crider et al., 2015; Crognier et al., 2015; Hodson et al., 2016b;

Luetkemeyer et al., 2016; Siman-Tov et al., 2016; Cruset et al., 2016, 2018, 2020a, 2020b; Lu

et al., 2017, 2018; Macdonald et al., 2017; Quade et al., 2017; Lacroix et al., 2018; Mering et

al., 2018; Smeraglia et al., 2018; Dennis et al., 2019; MacDonald et al., 2019; Nardini et al.,

2019; Quandt et al., 2019, 2020; Török et al., 2019; Boulton et al., 2020; Fosu et al., 2020; Lee

et al., 2020; Brogi et al., 2020; Muñoz-López et al., 2020; Salomon et al., 2020; Tartaglia et

al., 2020) in less than a decade, and showing a positive trend through the years with the highest

number of publications in 2020 (Figure 4). This impressive dataset was collected in 12

laboratories including Imperial College London, University of Washington, ETH Zurich,

California Institute of Technology, The Hebrew University of Jerusalem, University California

of Los Angeles, Michigan State University, University of Lausanne, Centre for Earth Sciences

Indian Institute of Science, University of East Anglia, Utrecht University, and University of

Bergen. Measurements cover a great variety of fracture locations (see Figure 4). On the first

few years (from 2012 to 2014), the measurements only took place within United States

(Swanson et al., 2012; Bergman et al., 2013; Budd et al., 2013; Loyd et al., 2013; Crider et al.,

2015) and Oman (Streit et al., 2012). Then in 2015, the clumped isotope measurements on

fractures became popular in Europe (Crognier et al., 2015) and since then took place in all

around the world (see Figure 4).

Most of the measurements use veins as a sample derived from precipitated of fluids along the

fractures. Furthermore, occasionally the fluid is categorized as a hydrothermal (Streit et al.,

21
Chapter 2

2012; Cruset et al., 2016, 2018; Dennis et al., 2019; MacDonald et al., 2019; Quandt et al.,

2019, 2020; Török et al., 2019; Brogi et al., 2020; Fosu et al., 2020). By definition,

hydrothermal veins are formed from fluids that are at least 5-10 ⁰C warmer than the host rock

(Machel and Lonnee, 2002).

Although the majority of applications of clumped isotope thermometry in fracture related

settings have focused on calcite, dolomite (Ferry et al., 2011; Loyd et al., 2012; Dale et al.,

2014; Vandeginste et al., 2014, 2017; Sena et al., 2014; Hirani et al., 2018; Honlet et al., 2018;

Lukoczki et al., 2019, 2020; Baldermann et al., 2020; Pan et al., 2020), siderite (Fernandez et

al., 2014), aragonite (Boch et al., 2019), magnesite and hydro-magnesite have been also studied

(Falk and Kelemen, 2015; García del Real et al., 2016; Quesnel et al., 2016; Boskabadi et al.,

2020).

22
Chapter 2

Figure 4. Overview of the application of clumped isotope thermometry to calcite fracture from 2012 to November
2020.

23
Chapter 2

2.3 Experimental protocol

The experimental protocol used to measure clumped isotopes can be summarized into three

main steps (Huntington et al., 2009; Dale et al., 2014):

1. Sample preparation and CO2 extraction by acid digestion of carbonate samples.

2. CO2 gas purification.

3. Measurement of the gas sample for isotopic composition by mass-spectrometry.

Analytical method of each result chapter (chapter 3, 4, and 5) are reported once in this section.

2.3.1. Sample preparation and CO2 extraction by acid digestion of carbonate samples

All measurements were performed in the Stable Isotope Laboratory at Imperial College

London. Calcite samples are selected and the target features (for this study cement within

fractures) were powdered using a micro drill at low speed to avoid the resetting of clumped

isotopes caused by increase temperatures during the process of powdering. The powders were

finely ground in an agate mortar to obtain a homogeneous grain size. A total of 3-3.5mg (for

automated purification line) or 6-6.5 mg (for manual purification line, see the CO2 gas

purification section for the detail) calcite powders were reacted in 105% anhydrous

orthophosphoric acid bath under vacuum to liberate analyte CO2 (McCrea, 1950; Swart et al.,

1991) held at 90°C. The reaction occurs as follows:

H3PO4 + Ca2+CO3 ↔ CO2 + H2O + Ca2+ + HPO42- (2.8)

This reaction was allowed for 10 minutes for calcite samples. Throughout this digesting

process, the product CO2 was cryogenically trapped in a glass spiral trap immersed in liquid

nitrogen (LN2). Under normal atmospheric pressure, nitrogen exists as a liquid between the

temperatures of -210°C and -196°C.

24
Chapter 2

2.3.2. CO2 gas purification

Product CO2 was then purified to eliminate contaminant gasses that produced on acid digestion

of the carbonate samples, such as water vapour, hydrocarbon, sulphide gasses, and short chain

halocarbons. For this study there are two type of CO2 gas purification system, which are: 1)

Manual CO2 purification line, and 2) Automated Imperial Batch Acid Digestion and CO2

Purification Line (IBEX).

2.3.2.1. Manual CO2 purification line

The liberated CO2 gas was passed through several traps: spiral cryogenic trap, silver trap, a

static Porapak-Q glass U-trap (Figure 5). The flow of CO2 through the different traps is driven

by pressure and the temperature differential between each trap, thus no carrier gas is needed.

Following cryogenic trapping (at about -200°C) during the digestion process in trap 1 non-

condensable gasses were pumped away. CO2 was then released by applying ethanol slush at -

85 to -90°C to trap 1. Through this process, the CO2 gas was separated from water contaminant

and released to the next trap 2. The released CO2 flows through a ¼ inch diameter glass tube

containing silver wool to remove sulphur (Guo and Eiler, 2007; Eagle et al., 2010) and through

a glass U-trap filled with Poropak-Q (trap 2) to separate polar gases from non-polar CO2

(Dennis and Schrag, 2010; Petersen et al., 2016; Davies and John, 2017). Poropak QTM is a

divinyl benzene polymer produced by Sigma-Aldrich for use in gas chromatography columns.

The temperature of trap 2 was maintained at -35°C by combine the cold from LN2 and heated

the surrounding copper wire coil which a voltage is applied. The transfer time from trap 1 to

trap 2 is 20 minutes. CO2 gas was cryogenically trapped in trap 3 before again being released

by immersed in ethanol slush at -85 to -90°C then frozen into the micro volume for transfer to

the mass spectrometer. The entire purification process in manual line take about 60 minutes.

25
Chapter 2

2.3.2.2. Automated Imperial Batch Acid Digestion and CO2 Purification Line (IBEX)

The IBEX uses helium as a carrier gas but a trap configuration similar to the manual line

(Figure 6). In contrast with the manual line, all the purification processes using IBEX are

automatic and controlled through the Ibex Control Centre software. Samples were delivered to

the acid reaction vessel by auto sampler then trapped in the first trap. Similar to the manual

line, all the cryogenic trap involved LN2 to freeze the CO2 gas. Analyte CO2 gas was released

by heating the first trap to -80°C and transferred across a 2.5 mm GC column held at -35°C,

using helium as carrier gas with a flow rate of 35 ml min-1 and pressure of 2 psi. The CO2 was

then frozen in the second trap at -192°C, and cryogenically transferred into a micro-volume

prior to mass-spectrometry measurement. Total time taken for sample preparation on the IBEX

was approximately 25 minutes.

26
Chapter 2

Figure 5. Illustration of acid digestion and manual CO2 purification line. The whole procedure takes about 60
minutes.

27
Chapter 2

Figure 6. Illustration of automated IBEX purification line. The whole procedure takes about 25 minutes (modified
from IBEX Control Centre Software Manual).

Figure 7. Illustration of mass spectrometer. A sample is inputted into the mass spectrometer, and the molecules
are ionized and accelerated. The ions are then through the electromagnetic deflection and separated by mass
analyzer, then detected

28
Chapter 2

2.3.3. Isotope ratio mass-spectrometry measurement of the gas sample

The principle of gas source mass spectrometry is to ionize a gas by bombarding it with electrons

in an ionization chamber. This process may cause some of the gas molecules to break into

several ions. An extraction system removes ions from the sample, which are then accelerated

out of the source through a series of progressively charged plates and then deflected by

magnetic or electric field through the mass analyzer and onto the detector or Faraday cup. The

mass analyzer is responsible with sorting the ions according to their mass to charge ratio (m/z).

Ions of the same m/z ratio will undergo the same amount of deflection. In other words, the

strength of magnetic fields and the accelerating voltage determine the trajectory of the ions and

therefore which ions will enter the Faraday cups (Figure 7).

In this study, samples were analyzed using a Thermo Finnigan MAT-253 mass spectrometer

modified with additional cups registered for ions with 44-49 m/z for clumped isotopes

measurement purposes using CO2 molecules species (Eiler and Schauble, 2004). This setup

allows the measurement of conventional isotopes (δ18O and δ13C) and clumped isotopes (Δ47)

on the single aliquot sample. This instrument is run in dual inlet mode. Dual inlet (DI) isotope

ratio mass spectrometry is generally considered the most precise method of measuring the

isotope ratio of light elements. In general, the DI mode determines isotope ratio by alternately

introducing sample gas and reference gas (working gas) of known isotopic composition into

the mass spectrometry under nearly identical condition (Huntington et al., 2009). This is

achieved by introducing the sample gas and reference gas into two different variable volumes

(or bellows) that are connected via a capillary. Within the capillary both gas is crimped, which

allows a small but steady flow of gases to enter the mass spectrometer. This system is designed

to leak gas under viscous flow at an equal rate for a given pressure in the bellows and preventing

isotope fractionation during flow.

29
Chapter 2

Well characterized high purity (HP) carbon dioxide used as reference gas owing to its

proximity in bulk isotopic composition to sample gases measured. The value of reference HP

CO2 gas is δ13CREF [VPDB] = -36.80‰ and δ18OREF [VSMOW] = 8.6‰ (Table 1).

Measurements consisted of 8 acquisitions each with 7 cycles with 26s integration time. Prior

the introduction of the sample to the mass spectrometer, bellow pressure was adjusted to

generate a m/z 44 ion beam signal of approximately 15V that was maintained throughout the

analysis. Before each acquisition, peak-centering and pressure adjustments were automatically

adjusted. A typical acquisition time was about 2 hours for the entire 8 acquisitions.

2.4 Data processing and correction of δ18O, δ13C, and Δ47

2.4.1. Data processing of δ18O, δ13C, and Δ47

All calculation for this work were done using the free software Easotope (John and Bowen,

2016). Several calculation steps are applied to the values in millivolt to define δ18O, δ13C, and

Δ47 of the sample following the detail of calculation in Affek and Eiler (2006). The UIPAC
17 18
recommended terrestrial mass dependent fractionation parameter between O and O (λ)

follow Brand et al. (2010) and Daëron et al. (2016).

To define the isotopic composition δ18O and δ13C of the sample, the abundance ratio of m/z =

i relative to m/z = 44 of reference gas (Ri REF) is calculated. To achieve the Ri REF, four

calculation steps were done. The first step is to calculate the relative abundant ratios of 13C/12C,
17
O/16O, and 18O/16O of the reference gas, known as R13 REF, R17 REF, R18 REF respectively. The

calculations are defined as:

(δ13C REF)
R13 REF = (1 + ( )) × R13VPDB (2.9)
1000

(δ18O REF)
R18 REF = (1 + ( )) × R18VSMOW (2.10)
1000

30
Chapter 2

(R18 REF)
R17 REF = ((R18 )λ × R17VSMOW (2.11)
VSMOW)

Where R13VPDB is 0.01118, R18VSMOW is 0.0020052, R17VSMOW is 0.00038475 following Brand

et al. (2010), and λ = 0.528 (Daëron et al., 2016).

The second calculation is to compute the relative abundant of 12C, 13C and 16O, 17O, 18O isotopes

of CO2 REF, following the equation of:

12 1
C REF = (2.12)
1 + R13 REF

13 R13 REF
C REF = (2.13)
1 + R13 REF

16 1
O REF = (2.14)
1 + R17 REF + R18 REF

17 R17 REF
O REF = (2.15)
1 + R17 REF + R18 REF

18 R18 REF
O REF = (2.16)
1 + R17 REF + R18 REF

The third calculation step is to compute the mass abundance of isotopologues of m/z = 44, 45,

46, 47, 48, 49 of CO2 REF. Assuming that the isotopes are randomly distributed amongst

isotopologues:

44
CO2 REF = [12C16O16O] REF = 12C REF ×16O REF ×16O REF (2.17)

45
CO2 REF = [12C16O17O + 13C16O16O ] REF =

(12C REF ×16O REF ×17O REF) +(13C REF ×16O REF ×16O REF) (2.18)

46
CO2 REF = [12C17O17O + 13C17O16O + 12C18O16O ] REF =

(12C REF ×17O REF ×17O REF) +2(13C REF ×17O REF ×16O REF) + 2(12C REF ×18O REF ×16O REF) (2.19)

31
Chapter 2

47
CO2 REF = [12C17O18O + 13C18O16O + 13C17O17O ] REF =

2(12C REF ×17O REF ×18O REF) +2(13C REF ×18O REF ×16O REF) + (13C REF ×17O REF ×17O REF) (2.20)

48
CO2 REF = [12C18O18O + 13C17O18O ] REF =

(12C REF ×18O REF ×18O REF) +2(13C REF ×17O REF ×18O REF) (2.21)

49
CO2 REF = [13C18O18O ] REF = (13C REF ×18O REF ×18O REF) (2.22)

The last calculation step is to compute the Ri REF or the abundance ratio of m/z = i relative to

m/z = 44 of reference gas:

[i] CO2 REF

Ri REF = 44 (2.23)
CO2 REFF

Where i = [44, 45, 46, 47, 48, 49]

To define the isotopic composition of sample gas (δ18O SAMPLE and δ13C SAMPLE) relative to the

reference gas, five calculation steps were done. The first step is to compute the abundance ratio

(Ri SAMPLE) of m/z = i relative to m/z = 44 using voltage (Vi) value of m/z = i.

(Vi / V44) SAMPLE

Ri SAMPLE = (2.24)
(Vi / V44) REF

Where i = [44, 45, 46, 47, 48, 49]

The second calculation step is to compute the abundance ratio of the different masses (δi):

Ri SAMPLE
δi SAMPLE = ( R − 1) × 1000 (2.25)
i REF

Where i = [44, 45, 46, 47, 48, 49]

The third calculation step is to compute the abundance ratio of R18 SAMPLE (Assonov and

Brenninkmeijer, 2003):

32
Chapter 2

−3 K2(R18 SAMPLE)2λ + 2 K(R45 SAMPLE) (R18 SAMPLE)λ + 2(R18 SAMPLE) - R46 SAMPLE = 0 (2.26)

where,

k= R17 REF / (R18 REF)λ (2.27)

The fourth calculation step is to compute the δ18O SAMPLE from eq. (2.23):

R18 SAMPLE
δ18O SAMPLE = ( R18 − 1) × 1000 (2.28)
VSMOW

The fifth calculation step is to compute the δ13C SAMPLE:

R13 SAMPLE
δ13C SAMPLE = ( − 1) × 1000 (2.29)
R13 VPDB

where,

R13 SAMPLE = R45 SAMPLE − 2 (R17 SAMPLE) (2.30)

R17 SAMPLE = k (R18 SAMPLE )λ (2.31)

To define the Δ47 RAW value, three calculation steps were done. The first calculation step is to

compute the ratio of isotopologues in CO2 SAMPLE as if isotope is randomly distributed amongst

isotopologues. The calculation simply repeats the same equation to calculate CO2 REF (eq 2.12-

2.16).

The second calculation step is to compute the abundance ratio for CO2 SAMPLE as if isotopes

were randomly distributed amongst isotopologues of m/z=45,46,47 (Rm/z*SAMPLE):

45
CO2 SAMPLE
R45* SAMPLE = 44
(2.32)
CO2 SAMPLE

46
CO2 SAMPLE
R46* SAMPLE = 44
(2.33)
CO2 SAMPLE

33
Chapter 2

47
CO2 SAMPLE
R47* SAMPLE = 44
(2.34)
CO2 SAMPLE

The values of Δ47 of CO2 can be calculated as (Eiler, 2007):

R47 SAMPLE R R
Δ47 RAW = ((R
47
* SAMPLE − 1) − (R4646*SAMPLE
SAMPLE
− 1 45 SAMPLE
) − (R *
45 SAMPLE
− 1)) × 103 (2.35)

where R i = mi / m44 or R47, R48, R49 are abundance ratio relative to mass 44. These R i derived

from comparison value with a standard having an accepted composition. R47*, R46*, R45* are

the corresponding ratios for a gas of identical bulk isotope composition but with a stochastic

distribution.

In summary, the resulted δ18O, δ13C, and Δ47 RAW value from these calculations were achieved

from several calculation steps, then the resulted value need to be corrected for the experimental

effects before reported as a final result.

2.5 Data corrections

In general, the δ18O and δ13C raw data resulted from the previous calculation process was

corrected for measurement drift. The Δ47 RAW data was corrected in three steps. Firstly,

correction was carried out for non-linearity of the mass spectrometer. Second, the Δ47 from the

previous correction were translated into the absolute reference frame of Dennis et al. (2011).

The last correction was applied for acid digestion temperature (Defliese et al., 2015).

2.5.1. δ18O and δ13C drift correction

The measurements on a mass spectrometer drift over time for many reasons, such as the ion

source performance (D’Autry et al., 2010) or the presence of the contaminants. The drift was

corrected by plotting the δ18O and δ13C raw data against the inter-laboratory published

carbonate standards (ETH 1 to ETH 4) and internal standard (ICM) with accepted isotopic

value. The isotopic composition (δ18O and δ13C) of ETH 1, ETH 2, ETH 3, and ETH 4 are

34
Chapter 2

shown in the Table 1 below. The both data plotted resulted the linear equation (Figure 8). The

corrected values of δ18O and δ13C (δ18OCORRECTED and δ13CCORRECTED) were obtained by

applying the linear equation:

δ18OCORRECTED = slope (δ18OMEASURED) + intercept (2.36)

δ13CCORRECTED = slope (δ13CMEASURED) + intercept (2.37)

2.5.2. Non-linearity correction

Mass spectrometry can lead to a non-linearity between the measured and the real R47 values

that may lead to significant difference in isotopic composition if the sample and standards differ

significantly (Ghosh et al., 2006; Huntington et al., 2010). This artefact is observed as a

correlation between Δ47 and the isotopic composition of the gas (δ47): normally, the Δ47 should

be independent of the δ47. This correlation exists for all mass-spectrometry analysis, but the

degree of correlation differs through time and the condition of the machine, such as specific

source conditions including cleanliness, filament, and tuning (Bernasconi et al., 2013). There

are two methods generally applied to correct for this effect: the “heated gas correction”

(Huntington et al., 2009) and the “pressure base line correction (PBL)” (He et al., 2012;

Bernasconi et al., 2013). In this study, we use the “heated gas correction” for the samples

purified on the manual line and the “pressure base line correction (PBL)” for samples run on

the IBEX. This reflects a change in our internal procedures in the course of the last 4 years,

and the rise of automation in our lab.

2.5.2.1. Heated gas correction

Heated gas (hereafter referred to as ‘HG’) correction was achieved by measuring heated gases

with a constant ∆47 value and a range of bulk isotopic composition (δ47) (Huntington et al.,

2009) prepared at the temperature of 1000°C following Huntington et al. (2009). Aliquots of

carbon dioxide of varying δ47 were prepared in quartz glass tubes, then equilibrated to a near

35
Chapter 2

stochastic distribution by heating to 1000°C for >2 hours followed by quenched at room

temperature.The HG have a calculated Δ47 value of 0.027‰ (Wang et al., 2004). Theoretically

the HG’s prepared at 1000°C should have the same Δ47. However, mass spectrometric non-

linearity results in increasing Δ47 at heavier δ47 (Figure 9). The positive linear correlation

formed due to this linearity effect is define as:

Δ47 HG = slope (δ47 ) + intercept (2.38)

The corrected Δ47 HG was obtained by projecting the δ47 to 0‰.

2.5.2.2. Pressure base line correction

The pressure base line (PBL) was used for the sample purified with the automated IBEX line

to optimize the non-linearity correction (He et al., 2012; Bernasconi et al., 2013). The PBL

correction removes the effect of secondary electrons on the Faraday cup collectors. These

secondary electrons create a negative baseline signal with an amplitude inversely proportional

to the beam intensity. Following the approach of Bernasconi et al. (2013), daily scans are

acquired using the reference gas at different intensities, 12 kV to 17 kV in 1 kV steps on the

m/z 44 beam. The negative intensity of the background is then plotted against the beam

intensity. The regression then can be used to correct the sample intensity (Figure 10).

2.5.3. Absolute reference frame

The second correction for Δ47 following the correction for mass-spectrometric non-linearity

data (Δ47 HG) is a projection to the absolute reference frame of Dennis et al. (2011). This

correction allows for standardization and inter-laboratory comparison between Δ47 values. This

correct for scale compression, or the redistribution of isotopes amongst isotopologues during

ionization process within the mass-spectrometer. Practically, the Δ47 values of the standards

Carrara marble (“ICM”), Oamaru Limestone (“IOL”), and published inter-laboratory standards

known as “ETH1–ETH4” (Meckler et al., 2014; Müller et al., 2017) are measured every 6 hours

36
Chapter 2

with the same protocol than the samples. We calibrated the values of the ETH standards

internally against equilibrated gases (Davies and John, 2019): our values are different to

reported values using a Thermo Kiel IV device (Meckler et al., 2014; Müller et al., 2017) but

similar to values analysed on dual inlet systems (Schauer et al., 2016; Fiebig et al., 2019). The

difference between the Δ47 of the standards and the measured Δ47 value is applied to correct the

Δ47 (Figure 11). This correction method is described as a projection in the “carbon dioxide

equilibrated scale (CDES)” and allows comparisons between different mass-spectrometers

(Dennis et al., 2011), define as:

Δ47CDES = slope (Δ47 HG) + intercept (2.39)

37
Chapter 2

Table 1. List of standards and isotopic composition

13 18
Standards δ C [VPDB] δ O [VPDB] Δ47 [CDES]
‰ ‰ ‰

ETH 1 2.00 -2.19 0.30

Heated for 10 hours at 600°C
Carrara Marble for inter-laboratory
comparison supplied by Stefano
Bernasconi (ETH Zurich)

ETH 2 -10.20 -18.58 0.30

Heated for 10 hours at 600°C fine-
grained commercial calcite for inter-
laboratory comparison supplied by
Stefano Bernasconi (ETH Zurich)

ETH 3 1.67 -1.75 0.71

Heated for 10 hours at 600°C
Cretaceous chalk from Northern
Germany for inter-laboratory
comparison supplied by Stefano
Bernasconi (ETH Zurich)

ETH 4 -10.22 -18.67 0.56

Fine-grained commercial calcite for
inter-laboratory comparison
supplied by Stefano Bernasconi
(ETH Zurich)

ICM (Imperial Cararra Marble) 2.02 -1.82 0.41

Carrara Marble from Italy heated to
approximately 300⁰C (Molli et al.,
2000)

IOL
Oamaru Limestone Quarry 0.30 0.38 0.74

High Purity (HP) gas -36.80 8.60 0.91

Heated Gas 0.0266

38
Chapter 2

Figure 8. Example of linear regression for drift correction.

39
Chapter 2

Figure 9. Example of HG linear line show increasing Δ47 at heavier δ47.

40
Chapter 2

Figure 10. Scans run showing mass 47 intensities across acceleration voltages 9.30-9.50 kV (top). Linear
regression between the background and the beam intensity used to correct for the effect of the secondary electrons
(bottom).

41
Chapter 2

Figure 11. Correction by comparing the sample with the standards.

42
Chapter 2

2.5.4. Acid fractionation

To speed up the acid digestion process, the acid was heated at 90°C. However, the variation in
13
digestion temperature has a measurable effect on the relative abundance of C-18O of CO2

evolved from the identical isotopic carbonates (Wacker et al., 2014). Moreover, the acid

digestion at 90°C results in increased Δ47 reproducibility. The increase in Δ47 related to the

fractionation in oxygen isotope is caused by the heavy oxygen isotope bond being harder to

dissociate than the lighter oxygen isotope bond. As a result, the CO2 products is richer in heavy

oxygen (18O) and has higher Δ47 than the rock sample (Guo et al., 2009). This offset vary by a

few ‰ with the acid digestion temperature. At the higher temperature the dissociation of heavy

oxygen is easier, which means the acid digestion fractionation is decreasing with increased

temperature for multiply substituted species Δ47, Δ48, Δ49 (Guo et al., 2009). Defliese et al.

(2015) measured the phosphoric acid fractionation factor relative to reaction at 25°C across a

temperature range from 25 to 90°C. Allowing for a single temperature dependent acid

fractionation relationship:

(0.022434±0.001490)× 106
1000lnαCO2 (acid) - Δ47 = − (0.2524 ± 0.0168) (2.40)
T2

Where α is the phosphoric acid fractionation factor, and T is in degrees Kelvin. In this study

the temperature is 90°C, give the acid fractionation factor (AFF∆47) = +0.082‰.

2.5.5. The Δ47 to temperature conversion

The last step to calculated the temperature from the Δ47 is following the equation of Davies and

John, (2019):

106
Δ47 = 0.04028 ± 0.00076 × + (0.23776 ± 0.00759) (2.41)
T2

The equation combines the inorganic calibrations of Kluge et al. (2015) and Kelson et al. (2017)

built with 71 samples (mostly calcite) precipitated with different precipitation methods over a

43
Chapter 2

large range of temperature (4-250°C), then reprocessed using our internal values for the

standards and the ‘Brand’ parameters for the 17O correction (following Daëron et al., 2016).

2.5.6. The δ18O Fluid [VSMOW] calculation

The δ18O Fluid [VSMOW] can be calculated using the calcite δ18O Calcite [VPDB] converted to the

VSMOW scale and the equation from Friedman and O’Neil, 1977. The Vienna Pee Dee

Belemnite (VPDB) scale are converted to the Vienna Standard Mean Ocean Water (VSMOW)

scale, which is a water standard defining isotopic composition of freshwaters using this

following equation:

δ18O Calcite [VSMOW]=1.03086 (δ18O VPDB)+30.86 (2.42)

Then, δ18O Fluid [VSMOW] was calculated using calcite δ18O Calcite [VPDB] scale and temperature in

Kelvin available from clumped isotopic data, using the equation:

(18.03 × 103)
δ18O Fluid [VSMOW] = - 32.42 (2.43)
T

2.5.7. Metrics of contamination

The contamination within the result is defined by a signal on m/z = 48 and m/z = 49 since the

isotopologues of m/z = 48 and m/z = 49 are very rare (Eiler and Schauble, 2004; Eiler, 2007).

The presence of m/z = 48 (Δ48 offset) and m/z = 49 (49param) is calculated following the equation

from John and Bowen, 2016:

∑𝑛
1 Δ48 REF
Δ48 offset = Δ48 SAMPLE − (2.44)
n

49param = R49SAMPLE − R49REF (2.45)

Where n is the number of standards. The standard procedure in the Stable Isotope Laboratory

at Imperial College London is to apply a cut off value of Δ48 offset > 1.5 and 49param > 0.2 (John

and Bowen, 2016) above which samples are considered as contaminated.

44
Chapter 2

2.6 Trace element analysis

Trace element analysis is a technique that measures very small concentrations of specific

elements present in a sample. All samples were analyzed with inductively coupled plasma mass

spectrometry (ICP-MS) in the QCCSRC Laboratory at Imperial College London for Ca, Mg,

and trace elements (Ba, U, Mn, Al, Fe, K, Sr, Na, S). The difference between mass spectrometry

previously described in section 2.2.3 is only at the atomizer. The ICP-MS is designed to ionized

the sample using plasma source in which the energy is from the electric current through the

electromagnetic induction. The ICP-MS is able to sample the analyte continuously, without

interruption.

The standard procedure of analysis is as follows: 3 mg of powder were diluted in 30 mL of

nitric acid in centrifuge tubes. The solutions were centrifuged and filtered to remove any solid

in suspension, and subsequently analyzed with an Agilent ICP-MS equipped with an ASX-500

Series auto sampler. Trace elements were measured first, followed by Ca and Mg after a four-

fold dilution. Three sets of Ca, Mg, and trace elements standards solutions were also prepared

for calibration. The Ca and Mg standard solutions consist of 100 ppm of each component. They

were diluted in 2% nitric acid to create two sets of five solutions at 100, 50, 25, 5, and 0 ppm.

The standard solution containing 1000 ppb of trace elements was diluted to obtain 1000, 500,

250, 50, 20, 10 and 1 ppb solutions.

2.7 Materials
The sample material for the measurements are natural calcite. Total samples for this study are

58 calcite samples. Detail information about sample locations and types are presented on each

chapter. The detail information of preparations, measurements, and data processing are

described on the previous sub-chapter (sub-chapter 2.3 Experimental protocol to 2.5 Data

corrections).

45
Chapter 2

The nine samples for measurements in chapter 3 are derived from boreholes and outcrop in

Laxemar, Götemar and Forsmark areas of Sweden. The samples were collected from open,

semi-open and sealed fractures (veins).

In chapter 4, the samples derived from three different locations in Jebel Madar, Oman. The

samples selected for this study are fault-related calcite veins. Using a dental drill, we drilled a

transect of 21 subsamples, typically <0.5 cm apart, across the three hand-specimen samples.

Also, two more samples derived from the carbonate host rock within the same locations.

In chapter 5, the samples are derived from several outcrop locations in Jebel Madar, Oman.

Twenty-six samples of calcite in large fractures and veins strategically located to cover most

of the study location.

46
Chapter 3

Clumped isotope temperature of a

Palaeozoic ‘deep biosphere’ recorded
within carbonate veins in granitic host rocks
3.1 Abstract

Previous studies have shown that microorganisms thrive in oligotrophic fracture systems,

surviving by consuming and producing methane. In the Laxemar, Götemar and Forsmark areas

of Sweden, ancient microbial activity has previously been demonstrated by large δ13CVPDB

variability of carbonate veins infillings within granitic host rocks. Here we apply carbonate

clumped isotope thermometry to reconstruct the temperature of precipitation of the carbonate

within these veins. The clumped isotope temperatures indicate that mineralization took place

between 46°C to 108°C, in line with previously published fluid inclusion data (<50˚C to

113˚C). The new clumped isotope data more accurately narrows temperatures at the lower end

of this range as fluid inclusions are not easily applicable below 80˚C, a temperature regime of

high importance for paleobiological reconstructions. Our results demonstrate that large

volumes of biogenic carbonate cement were formed from low-temperature microbial processes

in descending meteoric fluids. The known burial and thermal history of the region combined

with our clumped isotope data place the microbial activity at the end of the Variscan orogeny.

Thus, carbonate clumped isotope thermometry reduces uncertainties in deep biosphere studies

47
Chapter 3

by providing more accurate temperature constraints in the low-temperature regime, and thus

for biogenic processes, and for the nature of the diagenetic fluids.

3.2 Introduction

Understanding the ‘deep biosphere’, or microbial community living deep within sediments and

igneous fracture systems, is relevant to how life can be sustained in environments different than

Earth’s surface, which also may apply to other planets (Jones et al., 2018). Investigations over

the last two decades confirmed that microorganisms thrive in oligotrophic fracture system

(Pedersen, 1997), for instance by consuming and producing methane (Ino et al., 2018),an

abundant gas in fractured crystalline rocks (Lollar et al., 2008). The production of microbial

methane causes kinetic isotopic effect for carbon isotope values (expressed in δ13CVPDB, Irwin,

et al., 1977; Dale et al., 2014) leading to very isotopically light bicarbonate ions. Recent studies

of extremely 13C-depleted deep fracture-lining carbonate within granitic host rocks at Laxemar,

Götemar and Forsmark (hereafter ‘LGF’), Sweden suggest that the 13C-depleted values formed

due to the incorporation of bicarbonate into calcite from anaerobic oxidation of methane

(AOM) reactions, a model supported by the analysis of fatty acids shown to be of microbial

descent (Drake et al., 2015 and 2017).

Our goal is to further investigate the LGF veins to constrain the long-term environmental

conditions of the deep biosphere processes. We apply carbonate clumped isotope thermometry

for the first time on authigenic microbially induced calcite within veins in a granitic host rock.
13
Carbonate clumped isotope thermometry is based on measuring the abundance of C-18O

bonds (Δ47) in the carbonate lattice relative to a stochastic distribution of this isotopologue

(Ghosh et al., 2006). Carbonate clumped isotope thermometry only depends on the temperature

of the fluid, not its oxygen isotopic composition, thus enabling applications to fault and fracture

settings where fluid composition is often weakly constrained (Bergman et al., 2013; Dale et al.,

48
Chapter 3

2014). The specific objectives of our study were to (a) explore whether microbial activity

impacts the fractionation of clumped isotope and (b) assuming the clumped isotope

temperatures were at equilibrium, to determine the temperature of the ancient microbial

processes that resulted in 13C-depleted calcite.

The LGF area is selected in part because of previous work here demonstrated

geochronologically-constrained isotopic signs of ancient microbial activity in veins, but also

because of the availability of fluid inclusion results (Drake et al., 2017) that can be directly

compared to clumped isotope. Our results demonstrate that carbonate clumped isotope

thermometry is a useful tool for interpretation of the paleo-environment of the fossil, fracture

hosted deep-biosphere.

3.3 Sites and Materials

Geologically, the nine calcite samples used in this study come from the Svecokarelian orogeny

unit of the Fennoscandian Shield, at three different locations situated in the southeastern part

of Sweden: Forsmark, Götemar, and Laxemar (Figure 12). Forsmark is situated approximately

120 km north of Stockholm and Laxemar and Götemar are located about 300 km south of

Stockholm.

The Svecokarelian unit has been divided into six tectonic domains (Michael B Stephens, 2010)

based on differences in either the timing of tectonic activity or in the character and intensity of

the strain (Figure 12). Forsmark is situated in tectonic domain 2 (Michael B Stephens, 2010)

that contains broad belts of rocks that were affected by strong Paleoproterozoic ductile

deformation. These ductile high-strain belts, which strike approximately WNW−ESE to

NW−SE, are commonly folded and were mostly affected by lower ductile strain. The belts also

contain retrograde deformation zones along which deformation occurred in both the ductile

and brittle regimes. The Laxemar and Götemar areas are located inside the tectonic domain 5

49
Chapter 3

(Michael B Stephens, 2010) that formed after the complex geological evolution observed at

Forsmark took place, and therefore the intrusive rocks at Laxemar and Götemar are better

preserved (Söderbäck, 2008). Paleoproterozoic intrusive rocks belonging to the

Transscandinavian Igneous Belt (TIB) dominate the area and show variable composition

(granite to quartz monzodiorite to diorite-gabbro), grain size and texture that were affected by

magma-mixing processes. The Götemar granite is a Mesoproterozoic A-type granite intrusion

that intruded at ~1430 Ma and the related hydrothermal circulation affected the TIB wall rock,

as seen by greisens and abundant veins (Tillberg et al., 2019).

Sample locations, including boreholes and one outcrop, are dominated by Proterozoic (1.43–

1.89 Ga, Drake et al., 2017) crystalline rocks. The samples were collected from open, semi-

open and sealed fractures (veins) that were analysed using micro-thermometry technique for

fluid inclusion and intra-crystal SIMS analysis for carbon, oxygen, and sulphur isotopes

previously (Drake et al., 2017). Several generations of fracture infilling minerals were

recognized in the study areas (Drake et al., 2009), and micro-scale radiometric dating by Drake

et al. (2017) puts the calcite veins mostly within the Devonian-Carboniferous periods (402–

355 Ma), with some overgrowth of calcite in the Forsmark area and Götemar showing a Jurassic

ages which are 173.2±7.6 Ma and 160.0±3.3/5.6 Ma, respectively (Drake et al., 2017; Ivarsson

et al., 2020). Sample “KLX 14A 80” yields Rb–Sr age of 393±15 Ma (Drake et al., 2018). At

all sites, an early period of Proterozoic precipitation of a high-temperature mineral assemblage,

which includes epidote, was followed by a Mesoproterozoic period of hydrothermal

precipitation of different, lower temperature minerals, including adularia (older generation),

hematite, prehnite, and calcite, followed by several pulses of abundant Phanerozoic

precipitation of calcite, pyrite, adularia, clay minerals, quartz in veins (Drake et al., 2009;

2017).

50
Chapter 3

Figure 12. Top left picture is map of Fennoscandian Shield tectonic domain (figure modified from Koistinen et
al, 2001 op. cit. Söderbäck, 2008). The six tectonic domains have been separated based on differences in the
timing of tectonic activity or in the character and intensity of the strain. Forsmark is situated in tectonic domain
2, and Laxemar and Götemar areas inside tectonic domain 5. Bottom left picture is core image (figure modified
after Drake et al., 2017) with mineral appearance of coarse-grained calcite (white), apshaltite (black) and pyrite
(metallic cubic crystals) on a fracture surface from Forsmark (KFM06C:103 m). Bottom right picture is pyrite
crystals intergrown with the outermost calcite growth zone (polished crystal cross-section, KKR02, Götemar.
Figure modified after Drake et al., 2017).

51
Chapter 3

3.4 Analytical Methods

Total nine samples were analysed for clumped isotope thermometry following the experimental

protocol that previously described in methodology chapter (chapter 2). Five out of nine samples

were purified by passage through a conventional vacuum line with multiple cryogenic traps

and a Porapak-Q trap (Dennis and Schrag, 2010; Dale et al., 2014). For the other samples, we

used a fully automated system (our in-house prototype IBEX system).

3.5 Result and Discussion

3.5.1. Clumped and bulk isotope results

The results of the sample are shown in Table 2. The bulk oxygen isotope composition of the

carbonates (δ18O Calcite [VPDB]) ranges from 15.8±0.07‰ to -9.3±0.11. The carbon isotopic ratio

(δ13C Calcite [VPDB]) range from -24.8±0.23‰ to -7.5±0.03 (Figure 13). The Δ47 values vary

between 0.530±0.015‰ and 0.621±0.012‰ with standard error (SE) for each sample of 0.003–

0.026‰ and standard deviation (SD) for each sample of 0.005–0.045‰, translating into

temperature (T-Δ47) of 51±5 to 98±10°C. The calculated δ18O Fluid [VSMOW] composition ranges

between -6.7±1.9 to 0.9±1.4‰ (Figure 14).

52
 Table 2. Result from recent clumped isotopes analysis and fluid inclusion analysis by Drake et al., 2017 and 2018.

Preparation δ 18 O Fluid
Area and Sample n δ 13 C [VPDB] S.E δ 18 O[VPDB] S.E Δ47 CDES S.E Temperature S.E S.E Fluid Inclusion Fluid Inclusion Type Salinity Calcite Phase
Line [VSMOW]
ID
Current Analysis Drake et al., 2017; 2018
[‰] [‰] [‰] [°C] [‰] [Th °C] [wt. %]
Götemar
KKR02 Manual Line 4 -23.2 ±0.1 -11.4 ±0.16 0.593 ±0.005 64 ±2 -2.0 ±0.2 - - - Later Phase
Forsmark
KFM04A 306 Manual Line 4 -24.8 ±0.23 -12.8 ±0.09 0.59 ±0.003 65 ±2 -3.2 ±0.1 66-91 L ( +V)*** 16.9-18.6 Later Phase
KFM06A 332 Manual Line 4 -17.2 ±0.06 -12.8 ±0.05 0.613 ±0.009 54 ±4 -4.9 ±0.6 <50-87 L ( +V)*** 3.8-20.6 Later Phase
KFM06C 103 Manual Line 7 -22.9 ±0.10 -12.3 ±0.16 0.621 ±0.012 51 ±5 -5.0 ±0.7 <50-87 L ( +V)*** 2.6-20.6 Later Phase
Laxemar
KLX14A 80 Manual Line 5 -7.5 ±0.03 -9.3 ±0.11 0.607 ±0.009 57 ±4 -0.9 ±0.6 <50-96 2.0-22.0 Later Phase
KLX04 513 IBEX 3 -15.0 ±0.11 -14.7 ±0.19 0.547 ±0.003 88 ±2 -1.8 ±0.5 72-86 L + V prim 16.6-18.7 Earlier Phase
KLX04 669 IBEX 3 -13.8 ±0.01 -15.8 ±0.07 0.53 ±0.015 98 ±10 -1.6 ±1.2 <50 L sec - Earlier Phase
KLX06 814 IBEX 3 -11.1 ±0.06 -15.3 ±0.06 0.602 ±0.026 59 ±13 -6.7 ±1.9 59-113 L + V prim 21.9-22.3 Later Phase
OUTCROP03 IBEX 3 -10.7 ±0.08 -13.5 ±0.08 0.55 ±0.018 86 ±11 -0.9 ±1.4 - - - Earlier Phase
L = aqueous liquid. V = vapour. Prim=primary inclusion, Sec=Secondary inclusion.
L (+V)*** = a vapour bubble arises after cooling just before temperature of complete ice melting

53
Chapter 3

Figure 13. Plot between δ13C Calcite [VPDB] and clumped isotopes derived temperature. The association of lower-
temperatures with more depleted δ13C Calcite [VPDB] indicated the most optimal growth temperatures of the
organisms.

54
Chapter 3

Figure 14. Plot between δ18O Fluid [VSMOW] and clumped isotopes derived temperature of nine samples from
Laxemar, Götemar and Forsmark.

55
3.5.2. Clumped isotope in microbial settings: kinetic fractionation or useful proxy to

constrain deep-biosphere processes?

Oxygen and carbon stable isotope compositions can reflect either equilibrium conditions or be

impacted by kinetic effects that mask the environmental signal of interest. Carbonate mineral

precipitation in our study area is driven by microbially mediated reactions (Drake et al., 2017)

involving methane and water, producing bicarbonate ions through CO2

hydration/hydroxylation or dehydration/dehydroxylation reactions. These reactions can

include kinetic effects in carbonate clumped isotopes (Guo et al., 2009; Thiagarajan et al.,

2011). Finally, clumped isotopes in microbially-related carbonates were previously suggested

to show kinetic effects significantly impacting temperature estimates (Loyd et al., 2016). It is

thus important to verify that kinetic effects are absent from our microbially-related carbonates

samples.

In our study we compare two independent paleothermometers in the same samples, i.e. fluid

inclusion data and carbonate clumped isotope thermometry (e.g. Macdonald et al., 2018).

These two proxies rely on completely different properties: fluid inclusions are based on

microscopic bubbles of liquid and gas trapped within the crystal, whereas clumped isotopes

rely on the degree of ‘clumping’ of different isotopes. We thus have an ideal dataset to check

whether or not the T-Δ47 are at equilibrium with the precipitation temperature of the mineral.

We note that for most of samples, the T-Δ47 are in agreement with the reported lower estimates

of fluid inclusion homogenization temperatures, except for one sample: KLX04 513 (Table 2).

We have omitted sample KLX04 669, with a temperature of <50°C, since it contains only

secondary fluid inclusions (Drake et al, 2017). The fluid inclusions data show homogenization

temperatures of 68–96°C and high salinity (up to 22 wt.% CaCl2 eq.) in the older (inner) calcite

phase, but a lower temperature single phase (<50°C) with lower salinity (2–4 wt.% CaCl2 eq.)

56
Chapter 3

in the younger (outer) phases of the calcite coatings (Drake et al., 2018). Clumped isotope

analysis requires relatively large sample volumes, and mixing between the different

generations of calcites is therefore possible: here, it appears that the clumped isotope signal is

dominated by the lower temperature calcite zone for most samples, which is consistent with

petrographic observations (Figure 15).

Because the clumped isotope method records the lower temperature end of the fluid inclusion

temperatures, we conclude that no measurable kinetic fractionation by microbial activity can

be detected. More importantly, we note that the relationship between carbon isotope and

clumped isotope values as a proxy for environmental temperatures is significant: in the LGF

location, the lower clumped isotope derived temperatures are strongly correlated with more

depleted δ13Ccalcite (Figure 13). Microbes can be classified based on their optimal growth

temperatures: Simply thermophiles (50–64 °C), Extreme thermophiles (65–79°C), and

Hyperthermophiles (80°C and beyond, Stetter, 2006). Our observation suggests that simply

thermophilic microorganisms dominated at depth in the LGF system, though we cannot

completely rule out the influence of extreme and hyperthermophile microorganisms in some

samples. A significant advantage of the new clumped isotope results compared to the fluid

inclusion data is that we have better constraints on temperatures below 80°C. This turns out to

be crucial information, as we demonstrate that the lower temperature precipitates indeed

display the more negative carbon isotope values commonly associated with microbial activity.

Thus, clumped isotopes offer a highly valuable geothermometer for the study of the deep

biosphere through time.

57
Chapter 3

3.5.3. Constraining the environment of Palaeozoic microbial calcite precipitation

within veins

The previous fluid inclusions studies (Drake et al. 2017, 2018) determined that the fluid

circulating within the fracture system was a sulphate-rich brine developed in the deep bedrock

aquifer below thick sedimentary successions, which were uplifted between 330 Ma and 250

Ma and eroded in response to mantle dynamics due to Pangaea formation, as evidenced by

thermochronology (Guenthner et al., 2017). Our new results help to further understand the

temperature and nature of the fluids that sustained microbial organisms within the veins: the

reconstructed oxygen isotope signature of the brine is between -8.6 to 0.5‰ (see Figure 14).

Furthermore, two groups can be recognized in a δ18Ofluid VSMOW versus T-Δ47 plot (see Figure

14): the first group has higher T-Δ47 (86±11 to 98±10°C) and heavier δ18Ofluid VSMOW (-1.8±0.5

to 0.9±1.4‰), corresponding to samples dominated by the earlier generation of calcite (Drake

et al., 2018). The heavier δ18Ofluid-VSMOW combined with salinity values from fluid inclusions

of up to 22 wt.% CaCl2 eq. indicated that the fluid is a subsurface brine. Based on Rb–Sr

isochrones overlapped by (U–Th)/He hematite dating, this calcite phase was dated to the

Devonian and Carboniferous periods (Drake et al., 2018). The T-Δ47 are above regional sea

surface temperatures estimates from δ18OVPDB in conodont apatite and brachiopods from the

Eifelian to early Famennian (22 to 32°C, Joachimski et al., 2004). This confirms that the brine

must have circulated at burial depths below the thick sedimentary successions.

The second group of data shows lower T-Δ47 (51±5 to 65±2°C) and lighter δ18Ofluid VSMOW value

from (-0.9±0.6 to -6.7±1.9‰), corresponding to samples dominated by the later generation

(younger than ~260 Ma) of calcite (Drake et al., 2018). The lighter δ18Ofluid VSMOW signature

combined with salinity up to 4 wt.% CaCl2 eq. is surprising, as subsurface brines have more

often a positive δ18Ofluid VSMOW. This new finding leads us to propose that the brine is mixed

58
Chapter 3

with a significant portion of meteoric water modified chemically (Hitchon and Friedman, 1969;

Knauth and Beeunas, 1986) through exchange with surrounding minerals, organic matter, and

gases (Clayton et al., 1966). The main argument for this interpretation is that the δ18Ofluid VSMOW

of the samples interpreted as containing microbial fauna reflect typical modern meteoric water

δ18Ofluid VSMOW. The high salinity can be explained by dissolution at depth of evaporite minerals

from the overlying formations, placing an upper age limit for this calcite phase to the upper

Silurian Öved-Ramsåsa Group in south Sweden (Wigforss-Lange, 2007). The δ13CVPDB

depletion would also indicate that most of the microbial processes leading to calcite

precipitation occurred relatively near surface, where waters are warm but not hot, and perhaps

also charged in organic carbon.

In summary, the new clumped isotope data presented here suggest that the evolution of calcite

veins in the LGF area started with early burial fractures acting as conduits for subsurface fluids,

leading to precipitation of the first calcite generation. These early fractures must have been

reactivated during the Variscan uplift and served as conduits for meteoric fluids; this is when

a microbial ‘deep biosphere’ community was established within the fractures, and leading to

the precipitation of a late calcite generation (see Figure 14Figure 15).

59
Figure 15. . Simplified model of circulation for brine water along different fracture sets. The earlier
phase of calcite generation happens in a setting similar to the top picture whereas the later calcite phase
precipitated in a setting represented by the bottom picture. The inset image is modified after Drake et
al., 2017 and shows the co-existence of different sets of calcite vein (separated by a dashed yellow line)
in the BSE-SEM-images of polished calcite crystals. The later calcite phase represents the largest
volume of mineral precipitate.

60
Chapter 3

3.6 Conclusions

From the LGF dataset we conclude that (1) the combined clumped isotope and fluid inclusion

temperatures dataset seems a priori to rule out any significant kinetic effects of microbial

processes on clumped isotope temperatures. This is important, as it indicates that clumped

isotopes could be applied more broadly to the study of the largely unexplored ancient deep

biosphere. (2) all of the microbial-related calcite with low δ13CVPDB reflecting anaerobic

oxidation of methane or organic matter precipitated at T-Δ47 below 60˚C, which suggest that

the microbial community was composed of ‘simply thermogenic’ organisms, and (3) the fluid

that sustained microbial activity was probably a near-surface meteoric in origin but modified

to brine type by interaction with evaporite minerals, and that the timing of the deep biosphere

existence was related to the Variscan uplift when meteoric fluids circulated through reactivated

fractures. A broader conclusion is that clumped isotope thermometry significantly improves

precision for estimating temperatures, and has proven in the LGF case study to be a valuable

tool to understand environmental processes related to the deep biosphere.

61
Chapter 4

Combining clumped isotope and trace

element analysis to constrain potential
kinetic effects in calcite
4.1 Abstract

The field of clumped isotope paleo thermometry is over a decade old, but the influence of

precipitation rate on the fractionation of clumped isotopes between natural carbonates and their

environmental solutions remains unclear. Here we apply two different proxies, clumped isotope

thermometry and trace element analysis, to investigate whether or not precipitation rates play

a major role on the fractionation of clumped isotopes. Twenty-one transect points from three

calcite samples coming from veins along fractures (Jebel Madar, Oman) were investigated.

Two different types of calcite cements were recognized: i) Lower temperature macro-columnar

calcite, and ii) Higher temperature thin-vein calcite. The Δ47 values vary between 0.513±0.00‰

and 0.667±0.01‰ corresponding to calculated clumped isotope temperatures between 33±4 to

49±10 °C for macro-columnar calcite samples, and 59±9 to 109±1°C for the thin-vein calcite

sample. The calculated δ18O Fluid [VSMOW] composition ranges between -11.2±0.8 to 13.4±0.0‰.

Trace element results reveal a strong correlation between Mn and Fe and the clumped isotope

temperatures. We argue based on previous work on the incorporation of Mn and Fe into calcite

minerals that this is indicative of a change in crystal growth rates, and thus for the first time we

can independently show potential kinetic fractionation in ancient natural samples that resulted

62
Chapter 4

in clumped isotopes temperatures higher than ambient. The new combined clumped isotopes

and trace elements approach is a critical step to future application of the clumped isotope proxy

to natural systems as it can reveal potential isotopic disequilibrium independent of calculated

temperature.

4.2 Introduction

Since McCrea (1950), in his pioneering experiments, observed that precipitation rate can

influence carbon and oxygen isotope fractionation in the CaCO3-HCO3- system, the consensus

is that the δ18O temperature proxy can be affected by non-equilibrium fractionation effects due

to composition of the fluid (e.g. carbonate concentration and pH), biological effects, and/or

precipitation rate (McCrea, 1950; Tarutani et al., 1969; De Villiers et al., 1995; Adkins et al.,

2003; Kim et al., 2006; Dietzel et al., 2009). But the magnitude and direction of this non-

equilibrium fractionation is still not fully constrained. In laboratory inorganic carbonates

precipitates, δ18O values are reported to be independent of precipitation rates (Tarutani et al.,

1969; Kim and O’Neil, 1997a; Jiménez-López et al., 2001) or to decrease with increasing

precipitation rate (Kim et al., 2006). On the other hand, in natural biogenic carbonate, the effect

of growth rate on δ18O values is noticeable and a rapid growth rate results in a lower δ18O

values (McConnaughey, 1989; De Villiers et al., 1995; Adkins et al., 2003).

Non-equilibrium effects are even less well understood in carbonate clumped isotopes (Ghosh

et al., 2006; Schauble et al., 2006). Developed in the last decade, clumped isotopes (Δ47) are
13
based on measuring the abundance of C-18O bonds in the carbonate lattice of a mineral

relative to the stochastic distribution of this isotopologue (Ghosh et al., 2006; Eiler, 2007;

Dennis et al., 2011). Clumped isotopes only depend on the temperature of the fluid, not its

isotopic composition, making this at least in theory a more direct proxy for precipitation

temperatures. However, since the clumped isotope thermometer is also based on equilibrium

63
Chapter 4

thermodynamics, it potentially suffers from the same shortcomings as oxygen isotope

thermometry (Watkins and Hunt, 2015), especially for natural carbonates which often grow in

non-equilibrium conditions (Dietzel et al., 2009). For example, in speleothems fast carbonate

precipitation often does not allow sufficient time for isotopic equilibration and leads to

disequilibrium effects (Affek et al., 2008; Daëron et al., 2011; Wainer et al., 2011; Kluge and

Affek, 2012).

Here, we try to evaluate potential kinetic effects on clumped isotopes associated with

precipitation rates in inorganic calcite in the surficial burial regime, within a near-surface

fracture network. For this, we selected three large crystal samples growing along fracture

planes in the carbonate carapace of a salt dome (Jebel Madar, Oman). Samples at Jebel Madar

are ideal for our study, in part because of the availability of published data (Immenhauser et

al., 2007; Vandeginste et al., 2017) that can complement the current research, but also because

the size of the minerals (up to >20 cm) allows for detailed transects across a single mineral.

We measured clumped isotope values and trace elements composition along high-resolution

transects in three crystals, starting from the host rocks and going to more recent growth phases

on the outer layers of the mineral. The motivation for pairing trace elements with clumped

isotopes is that the abundance and distribution of trace elements is often used to constrain

diagenetic history in carbonates (Veizer et al., 1983; Bruhn et al., 1995), but also importantly

the incorporation of Mn2+ and Fe2+ into calcite is known to be influenced by growth kinetics

(Lorens, 1981; Mucci, 1988; Dromgoole and Walter, 1990a), temperature (Veizer, 1974) and

solution composition (Mucci, 1988). The current consensus is that the slower the precipitation

rate, the closer trace element partitioning is to chemical equilibrium (e.g Dromgoole and

Walter, 1990b). Hence, by investigating trace elements and clumped isotopes in the same

samples we hope to find a qualitative or semi-quantitative way to identify disequilibrium

precipitation, and by extension gain a greater understanding of the temperature of precipitation

64
Chapter 4

of fracture-related calcites. Our results strongly suggest that the coupling of clumped isotopes

and trace elements analysis indeed do reveal possible kinetic fractionations.

4.3 Site and materials

Jebel Madar is a salt-cored dome structure in the Adam Mountains, the foothills of the Oman

Mountains. The stratigraphy of the carapace at Jebel Madar consist of Late Triassic to

Cretaceous carbonates, and it is exposed approximately 500 m above the surrounding

Quaternary plain deposits (Béchennec et al., 1992 op. cit. Claringbould et al., 2013). Jebel

Madar formed by diapirism of the Precambrian-Cambrian Ara salt of the Ghaba Salt Basin

(Mount et al., 1998) during the Miocene (Claringbould et al., 2013). The main axis of the Jebel

is NE-SW oriented, and is interpreted to reflect left-lateral, strike-slip faults in the basement

(Loosveld et al., 1996). The samples selected for this study are fault-related calcite crystals.

Previous study by Immenhauser et al. (2007) and Vandeginste et al. (2017) revealed four

phases of calcite mineralization distinguished by their occurrence and characteristics. From the

oldest to youngest diagenetic phase in the paragenesis (Vandeginste et al., 2017) these are: 1)

thin calcite veins, 2) barite-associated calcite, 3) fault zone calcite, and 4) macro-columnar

calcite. Our samples come from three different locations and two different types of cement:

Sample JMG is from a thin (2 cm thick) calcitic vein which according to Vandeginste et al.

(2017) is an early phase of calcite deposited during deeper burial. Samples JMF 1 and JMF 12

are both described as macro-columnar calcite (Vandeginste et al., 2017) presumably deposited

in phreatic caves (Immenhauser et al., 2007). All the veins are categorized as syntaxial veins

following Bons et al., 2012. Using a dental drill, we drilled a transect of seven subsamples

across JMG-1, and transects of six and eight subsamples in samples JMF-1 and JMF-12,

respectively. In all transects, subsample (or point) ‘A’ designates the earliest stage of vein

growth, and sampled data points are typically <0.5 cm apart (Figure 16). From the previous

65
Chapter 4

study using Cathodoluminescence Energy Dispersive X-ray (Figure 17), the macro-columnar

calcite show a different phases and zoning of cement by the differences in luminescence.

66
Chapter 4

Figure 16. Twenty-one transect points from three different samples location. Point ‘A’ is the earliest stage of
vein growth.

Figure 17. Images of calcite vein sample under normal (transmitted) light (left pictures) and cathodoluminescence
conditions (right pictures). The two top pictures are macro columnar vein (Vandeginste et al., 2017) and the two
bottom pictures are thin-vein calcite (Hajibeigy, 2017).

67
Chapter 4

4.4 Analytical methods

Total of twenty-one samples were analyzed for clumped isotope thermometry and trace

element analysis following the experimental protocol that previously described in methodology

chapter (chapter 2). All sample measurements were purified in the fully automated system (the

prototype IBEX system developed in-house).

4.5 Results

The range in bulk oxygen isotope composition of the calcite (δ18O Calcite [VPDB]) is as follows: -

10.86±019 to -14.61±0.04‰ for sample JMF 1, -14.5±0.02 to -15.58±0.05‰ for sample JMF

12, and -2.68±0.07 to -12.13±0.02‰ for sample JMG 1. The carbon isotopic ratio (δ13C Calcite

[VPDB]) range from -6.2±0.05 to -2.2±0.16‰ for JMF 1, --7.61±0.04 to 4.79±0.01‰ for JMF

12, and 0.46±0.12 to 2.93±0.03‰ for JMG 1 (Figure 18). The results are shown in Table 3.

Hence, macro-columnar calcite samples yield more negative bulk isotope composition than the

thin-vein calcite samples.

The Δ47 values vary between 0.513‰ and 0.667‰ with standard error (SE) of 0.001–0.025‰

and standard deviation (SD) of 0.002–0.044‰, corresponding to calculated clumped isotope

temperatures between 33±4 to 109±1°C. The temperature recorded in macro-columnar calcites

(JMF 1 and JMF 12) are lower (33±4 to 49±10°C) than temperatures in the thin-vein calcite

(JMG 1, 59±9 to 109±1°C). The calculated δ18O Fluid [VSMOW] composition ranges between -

11.2±0.8 to 13.4±0.0‰. Samples from macro-columnar calcite record more negative δ18O Fluid

[VSMOW] composition than samples from thin-vein calcite (Figure 19).

A strong correlation (R2 up to 0.81) between Mn concentrations and clumped temperature exist

(Figure 20), whereas other elemental concentrations do not covary with clumped temperature.

Most macro-columnar calcite samples have lower Mn content (from 0.18 to 12.67 ppb) than

68
Chapter 4

the thin-vein calcite sample (from 15.23 to 22.64 ppb), except for sample JMF 1-B that has the

highest content recorded in this study (53.14 ppb). The macro-columnar calcite samples with

temperature below 50°C (JMF 1 and JMF 12) shows an inverse relationship between clumped

isotope temperature and Mn concentration. However, no trend exists in thin-vein calcite

samples with clumped isotope temperature above 50°C (see Figure 20).

69
Chapter 4

Table 3. Result from clumped isotopes and trace element analysis

δ13C Calcite δ18O Calcite δ18 O Fluid

S. E S. E Δ47 CDES S. E Temperature S. E S. E Mn Fe Ca DMn DFe Mn/Fe
Area and Sample ID n [VPDB ] [VPDB ] [VSMOW]

[‰] [‰] [‰] [°C] [‰] [ppb] [ppb] [ppm] [mmol l -1 ] [mmol l -1 ] [mmol l -1 ]
JMF 1 Macro-Columnar

JMF 1-Host Rock 3 -5.94 ± 0.01 -14.41 ± 0.10 0.601 ± 0.01 60 ± 7 -5.7 ± 0.9
JMF 1-A 3 -2.20 ± 0.16 -10.86 ± 0.19 0.656 ± 0.03 37 ± 10 -6.0 ± 1.6 12.7 32.5 46.3 0.020 0.504 0.396
JMF 1-B 3 -4.59 ± 0.05 -14.07 ± 0.04 0.640 ± 0.01 43 ± 4 -8.2 ± 0.7 53.1 97.8 41.9 0.092 1.674 0.552
JMF 1-C 3 -6.20 ± 0.05 -14.61 ± 0.04 0.633 ± 0.01 46 ± 4 -8.3 ± 0.7 3.1 34.7 38.8 0.006 0.642 0.092
JMF 1-D 3 -5.79 ± 0.05 -13.85 ± 0.11 0.625 ± 0.01 49 ± 4 -6.9 ± 0.6 1.1 75.9 42.3 0.002 1.287 0.015
JMF 1-E 3 -6.13 ± 0.01 -14.04 ± 0.03 0.633 ± 0.01 46 ± 2 -7.7 ± 0.3 0.7 20.3 47.8 0.001 0.305 0.037
JMF 1-F 3 -5.85 ± 0.05 -14.00 ± 0.11 0.650 ± 0.01 39 ± 4 -8.8 ± 0.6 4.9 12.6 37.2 0.010 0.244 0.394

JMF 12 Macro-Columnar

JMF 12-A 3 -7.45 ± 0.02 -15.19 ± 0.02 0.667 ± 0.01 33 ± 4 -11.2 ± 0.8 2.1 12.7 54.2 0.003 0.168 0.170
JMF 12-B 3 -6.39 ± 0.02 -14.94 ± 0.06 0.656 ± 0.01 37 ± 5 -10.2 ± 0.8 2.6 28.2 41.2 0.005 0.492 0.095
JMF 12-C 3 -7.52 ± 0.02 -15.32 ± 0.02 0.643 ± 0.02 42 ± 8 -9.7 ± 1.3 1.8 30.1 43.8 0.003 0.492 0.060
JMF 12-D 3 -5.54 ± 0.01 -14.50 ± 0.02 0.625 ± 0.02 49 ± 10 -7.6 ± 1.6 0.4 8.6 47.2 0.001 0.130 0.050
JMF 12-E 3 -5.59 ± 0.01 -15.08 ± 0.04 0.629 ± 0.02 48 ± 6 -8.5 ± 1.0 0.2 4.2 37.9 0.0003 0.080 0.042
JMF 12-F 3 -6.39 ± 0.03 -14.63 ± 0.04 0.628 ± 0.01 48 ± 5 -7.9 ± 0.9 0.7 16.9 38.2 0.001 0.317 0.044
JMF 12-G 3 -7.61 ± 0.04 -15.44 ± 0.00 0.641 ± 0.02 43 ± 8 -9.7 ± 1.4 1.1 15.1 35.1 0.002 0.308 0.073
JMF 12-H 3 -4.79 ± 0.01 -15.58 ± 0.05 0.642 ± 0.01 43 ± 6 -9.9 ± 1.0 1.3 30.2 38.3 0.002 0.566 0.043

JMG 1 Thin Vein

JMG 1-Host Rock 3 2.95 ± 0.01 -3.11 ± 0.05 0.485 ± 0.01 130 ± 7 15.4 ± 0.7
JMG 1-A 3 2.90 ± 0.05 -2.68 ± 0.07 0.513 ± 0.00 109 ± 1 13.4 ± 0.0 22.6 9.0 40.1 0.041 0.160 2.565
JMG 1-B 3 2.59 ± 0.05 -4.46 ± 0.04 0.558 ± 0.02 82 ± 11 7.8 ± 1.5 17.7 4.7 38.9 0.033 0.087 3.810
JMG 1-C 3 2.93 ± 0.03 -3.63 ± 0.09 0.528 ± 0.01 99 ± 5 11.1 ± 0.5 17.1 9.8 38.8 0.032 0.181 1.771
JMG 1-D 3 0.46 ± 0.12 -10.66 ± 0.09 0.587 ± 0.02 66 ± 11 -0.8 ± 1.5 19.9 67.5 38.9 0.037 1.245 0.300
JMG 1-E 3 0.52 ± 0.02 -12.13 ± 0.02 0.586 ± 0.00 67 ± 2 -2.2 ± 0.2 15.2 15.2 37.6 0.029 0.290 1.017
JMG 1-F 3 0.45 ± 0.08 -11.53 ± 0.02 0.602 ± 0.02 59 ± 9 -2.8 ± 1.4 19.3 21.9 49.1 0.029 0.320 0.898
JMG 1-G 3 0.74 ± 0.07 -10.93 ± 0.01 0.601 ± 0.02 60 ± 7 -2.1 ± 1.1 15.2 10.8 38.8 0.029 0.200 1.432

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Chapter 4

Figure 18. Plot of bulk isotopic composition between δ13CCalcite [VPDB] and δ18O Calcite [VPDB] from twenty-one
intersect points at three different places. The samples from macro-columnar calcite (blue color) shows more
negative or lighter bulk isotope composition than the samples from thin-vein calcite (yellow color).

71
Chapter 4

Figure 19. Plot between δ18O Fluid [VSMOW] and clumped isotopes temperature of twenty-one transect samples from
three different crystals. The samples from macro-columnar calcite (blue color) shows lighter δ18O Fluid [VSMOW] and
lower temperature than the samples from thin-vein calcite (yellow color).

72
Chapter 4

Figure 20. Graph plot between clumped isotope temperature in ºC and Mn composition in ppm of JMF 1 (top),
JMF 12 (middle), and JMG 1 (bottom).

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Chapter 4

4.6 Discussion

4.6.1 Relationship between calculated δ18OFluid and clumped isotope temperatures:

Recrystallization or potential kinetic effects?

From our result we note that macro-columnar calcite results show a very significant (R2 = 0.79)

trend between calculated δ18O Fluid [VSMOW] and clumped isotope temperature (Figure 21), but

temperature does not seem to decrease with progressively younger calcite phases (i.e. further

away from the host rock). This is intriguing, because at equilibrium Δ47 values are independent

of the δ18O and δ13C of the fluid and therefore provide temperature estimates that should be

independent of the isotopic composition of the water (δ18O Fluid [VSMOW]). We also note that data

points with more positive δ18O Fluid [VSMOW] correspond to lower (warmer) Δ47 (see Figure 21).

Also a positive correlation between δ18O Fluid [VSMOW] and clumped isotope temperatures can

sometimes be interpreted as closed-system recrystallization (Huntington and Lechler, 2015;

John, 2015), this is unlikely the case here given that the macro-columnar samples were dated

to the Pleistocene to Holocene (Immenhauser et al., 2007) and show no evidence for

recrystallization. Alternatively, a similar trend was described in speleothem and attributed to

kinetic fractionation during degassing (Clark and Lauriol, 1992; Mickler et al., 2006; Guo and

Eiler, 2007; Daëron et al., 2011): CO2 degassing from a thin film of solution leads to high rates

of precipitation and isotopic disequilibrium in the remaining dissolved inorganic carbon (DIC)

which ends up enriched in δ18O and δ13C and depleted in Δ47. The degassing in speleothems is

a rapid process (only a few second for a film thickness of 0.01 cm, Hansen et al., 2013), which

is faster than the time needed for the oxygen isotope exchange between DIC and water

(Dreybrodt and Scholz, 2011).

The importance of precipitation rate to the fractionation of clumped isotope between natural

carbonates and their environmental solutions remain unclear: Kluge et al. (2014) and Tang et

al. (2014) suggest that, unlike conventional stable isotopes, clumped isotopes are independent

74
Chapter 4

of growth rate in inorganic carbonates. The difficulties in proving equilibrium conditions and

chemical equilibrium between the growing mineral and the solution are often compounded by

the fact that fast mineral growth rates are used during laboratory experiments (Dietzel et al.,

2009; Gabitov et al., 2012; Kluge et al., 2014). Several ideas have been put forth to mimic

natural precipitation condition, but deviations still remain due to the complexity of the different

parameters (Dietzel et al., 2009).The strong relationship between calculated δ18O Fluid [VSMOW]

and temperature observed in our samples could indeed be explained by kinetics, because

mathematically both an increase in δ18O Calcite [VPDB] and an increase in estimated precipitation

temperature will result in a heavier calculated δ18O Fluid [VSMOW] (Kim and O’Neil, 1997). The

setting for our samples (subsurface vein and phreatic caves) is different than a vadose cave

deposit (speleothems) as there is no air and thus precipitation from a thin film of fluid is not a

likely scenario. However, it is possible that rapid degassing of CO2 would have occurred during

tectonic events, and thus kinetic effects due to rapid degassing and high rates of precipitation

are potentially present. To explore whether or not kinetic effects have impacted the temperature

of precipitation, we investigated the trace element composition of the different samples.

Apart from the other samples, the sample JMF 1 A is plotted outside the trend. The possible

explanation for this one is because the sample which too close to the host-rock thus mixing

with the host-rock when powdered the sample using micro-drill is more likely. Consistently

indicated by the larger standard error compare to the other samples.

75
Chapter 4

Figure 21. Plot between δ18O Fluid [VSMOW] and clumped isotope temperature of macro-columnar calcite samples.
The δ18O Calcite [VPDB] isoline in the background indicating a strong relationship of increasing in δ 18O Calcite [VPDB]
and an increasing in estimated precipitation temperature will result in a heavier calculated δ18O Fluid [VSMOW]. JMF
1 A is plotted outside the trend, because the sample is too close to the host-rock thus mixing with the host-rock
when powdered the sample using micro-drill is more likely.

76
Chapter 4

4.6.2 Trace Element Ratios as Proxy for the Rate of Precipitation of Natural Calcite

Samples

Our approach is to follow Dromgoole and Walter (1990) and constrain the rate of precipitation

in our samples using the ratios of Mn and Fe over Ca. The experimental conditions of

Dromgoole and Walter, 1990 shows in Table 4.Combining this information with clumped

isotope data could give an insight on whether precipitation rates lead to kinetic fractionation

for clumped isotopes. The Fe or Mn concentration in calcite is related to the composition of

the initial fluid though a distribution coefficient (hereby ‘D’, Dromgoole and Walter, 1990b).

The value of D for a given metal element (Me) can be defined as (Dromgoole and Walter,

1990b):

DMe = (Me/Ca)calcite / (ɑMe/ ɑCa) (4.1)

where (Me/Ca)calcite is Fe/Ca or Mn/Ca molar ratio, and (ɑMe/ɑCa) is the activity ratio in solution

for this element. Dromgoole and Walter (1990b) report experimental activity ratio in solution

for Mn2+ of 0.01, and 0.001 for Fe2+. Variations in experimental activity ratios with

environment parameters are not significant (Dromgoole and Walter, 1990b): the dependence

of DMn on precipitation rates at 25°C from experiments at 0.001 ɑMe/ɑCa and at 0.01 ɑMe/ɑCa are

the same. Furthermore, Mucci (1988) also stated that the activity coefficients of these aqueous

species are not expected to vary significantly. Hence, it is reasonable to use the reported activity

ratios (Dromgoole and Walter, 1990b) for our samples. The earliest derived values of DMn2+

by Bodine et al. (1965 op. cit. Ichikuni, 1973) were 16.2±2.0 at 40°C. Ichikuni (1973) provided

an empirical determination of k for Mn by comparing the Mn2+ in two samples of travertine

with the Mn2+ and Ca2+ concentrations in the solutions dripping from the growth surfaces.

Ichikuni (1973) estimates of D for Mn in a natural system were 10 and 18 at ~40°C. Moreover,

77
Chapter 4

the DMn values of 10 and 18 (equal to 1000 µmol m-2 hr-1) for calcitic travertine deposited at

40-50°C.

A significant advancement was when (Lorens, 1981; Pingitore et al., 1988; Dromgoole and

Walter, 1990a, 1990b) independently demonstrated that the distribution coefficient of Mn2+ in

calcite varies with precipitation rate of carbonates. In an extensive laboratory study Lorens

(1981) co-precipitated Mn2+ with calcite as an overgrowth on calcite seeds. Precipitation rates

and super saturation were carefully controlled and DMn2+ showed a strong dependence on rate

of precipitation: it varied from 6 to 50 µmol m-2 hr-1 at 25°C. The recrystallization of aragonite

to calcite at 25°C proceeds at the rate of 10's to 100's µmol m -2 hr-1. Furthermore, this study

proposed a coherent rate dependence for incorporation of Mn2+, Co2+ and Cd2+ into calcite

down to his lowest measurable rates, 2 µmol m-2 hr-1. Davis et al. (1987) suggested that the

kinetic control on incorporation of Cd2+ into calcite, and presumably Mn2+ and Fe2+ as well,

extends to precipitation rates 10-100 times slower.

Pingitore et al. (1988) further confirmed that the partition coefficients of Mn2+ exhibit values

ranging from nearly 1 to 18.8 and strongly depend on precipitation rates. DMn values from

Dromgoole and Walter (1990b) range from 3 to 11, 3.8 to 16 and 8 to 22 at the 10, 25, 50°C

respectively, and are controlled by the rate of precipitation (Figure 22).

There is considerably less information on Fe2+ incorporation into calcite. Values of DFe for

calcite at 25°C have been estimated by (Veizer, 1974; DFe = 21), and at ~100°C by (Boles and

Ramseyer, 1987; DFe =10). However, none of these studies permit evaluation of the effects of

temperature or precipitation rates. The more recent work of Dromgoole and Walter (1990b),

reported DFe values ranging from 1.5 to 2.3, 1.9 to 3.7 and 2.8 to 7.7 at 10, 25, 50°C

respectively, and also show a strong control by precipitation rate.

78
Chapter 4

Variations in temperature, precipitation rate and the chemical composition of the precipitated

phase can alter the concentration ratio of a chemical species between two media at equilibrium:

this is known as effective distribution coefficients or partition coefficient of trace elements

(Rimstidt et al., 1998), and which further complicates the interpretation of trace element

abundances in carbonate cements. Here, following Dromgoole and Walter (1990b) we

calculated DMe’s for our samples using an activity ratio of 0.01 mmol l-1 for DMn (ranging from

0.0003 to 0.09 mmol l-1) and 0.001 mmol l-1 for DFe (ranging from 0.08 to 1.67 mmol l-1). We

used the abundance values of Mn and Fe instead of Mn2+ or Fe2+, then consider it as an

uncertainty. In general, the DMn value for the samples derived from macro-columnar calcite is

lower than the calcite vein samples (see Table 3). However, the DMn and DFe values are very

low compared to previously published values by Dromgoole and Walter (1990b). This implies

much faster precipitation rates than laboratory conditions.

One important caveat is that as our samples are natural precipitates of calcite, and it is unclear

if the laboratory derived controls on distribution coefficients are appropriate. Determination of

distribution coefficients or partition coefficient by direct measurement requires knowledge of

the initial molar composition of the fluid, the activity ratio in solution, duration of precipitation,

amount of material precipitated, and effective surface area available for precipitation. These

values are impossible to determine for natural calcite cements. One approach is to assume that

the natural samples are similar to calcite precipitated from experimental solutions with similar

parameters Dromgoole and Walter (1990b), or by comparing the ratios of the two analyzed

trace element composition (e.g. DMn compare to DFe.) By combining the equations for DMn and

DFe (eq. 1) we can relate the Mn/Fe ratio in the precipitated calcite to the Mn/Fe activity ratio

in solution. In most cases activity coefficients for Fe and Mn will be approximately the same,

and concentrations, rather than activities can be used Dromgoole and Walter (1990b):

DMn / DFe = (Mn/Fe)calcite / (ɑMn/ɑFe)solution (4.2)

79
Chapter 4

Calculated ratios of DMn / DFe in calcite for several precipitation rates at 10°, 25° and 50°C

(Table 5) are based on linear regression equation from the Dromgoole and Walter (1990b)

experimental data. This calculation is limited to temperatures up to 50°C, thus is applicable to

our lower temperature (macro-columnar calcite) samples, but not the thin-vein calcite. The

linear regression of precipitation rate at 10°, 25° and 50°C define as:

log precipitation rate (10°C) = -5.4483 (log DMn / DFe) + 5.8241 (4.3)

log precipitation rate (25°C) = -9.2315 (log DMn / DFe) + 8.6762 (4.4)

log precipitation rate (50°C) = -42.29 (log DMn / DFe) + 23.081 (4.5)

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Chapter 4

4.6.3 Pairing clumped isotopes and trace elements: Direct evidences for kinetic effects

Our result from the lower temperature calcite samples indicate very low value of DMn/DFe (from

0.015 to 0.393 mmol l-1), which would translate as a rapid rate of precipitation (more than

100,000 µmol m-2 hr-1). Moreover, the lower value of DMn/DFe (interpreted as higher rate of

precipitation) correlates with increasing clumped isotope temperature (Figure 23 and Figure

24) and δ18Ofluid SMOW. We thus argue that the correlation between DMn/DFe, clumped isotope

temperature and δ18Ofluid SMOW can be best explained by kinetic fractionation during rapid

precipitation of calcite along the fractures. In other words, the higher rate of precipitation at

temperatures <50˚C along the fractures may result in isotopic disequilibrium and an apparent

clumped isotope temperature higher than the true temperature.

Kinetic fractionation due to high precipitation rates of calcite and the time needed for the

oxygen exchange to regain the oxygen isotopic equilibrium is temperature dependent (attained

faster at higher temperature). We note that the sample showing a higher temperature (thin-vein

calcite) shows no trend between elemental concentration and clumped isotope temperature

above 50°C (see Figure 20). This could be because at these higher temperatures equilibrium is

reached faster and thus this sample is less affected by kinetic effects compared to the macro-

columnar calcite.

The detailed transect reveal that the clumped isotope temperature value of all samples evolves

within a single sample, similar to what Immenhauser et al. (2007) had reported for the macro-

columnar calcites bulk isotope composition. This observation also extends to the one thin-vein

calcite samples, which probably indicates that multiple generation of cements were formed

through repeated fracturing and sealing (e.g. crack seal mechanism, Ramsay, 1980; Labaume

et al., 2005) of the host-rock during episodic fluid flow. The higher temperature thin-vein

calcite sample shows evidence of successive micro-cracks filled with calcite isotopically

81
Chapter 4

similar to the host rock (Figure 25), and which were probably derived by local chemical

solution and transfer at the sample (e.g. host rock buffered, Veillard et al., 2019). These

observations alongside our understanding of clumped isotope disequilibrium during rapid

degassing leads us to the working hypothesis that calcite precipitation in our system could have

happened during seismic events, when the confining pressure on the fluids was released and

CO2 degassed from solution.

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Chapter 4

Figure 22. DMn values from Dromgoole and Walter, 1990 at the 10, 25, 50°C and are controlled by the rate of
precipitation.

Table 4. Experimental conditions of Dromgoole and Walter, 1990b.

Temperature PCO2 Ca2+ Mn2+

pH
⁰C atm mol/l mol/l
10 0.099 0.1 1
25 0.097 0.1 1
25 0.97 0.01 0.1
Mn2+ 25 0.97 0.1 0.1
25 0.97 0.1 1
25 0.97 0.1 5 5.5-6.7
50 0.88 0.1 1
10 0.099 0.1 0.1
25 0.97 0.1 0.022
Fe2+
25 0.97 0.1 0.1
50 0.88 0.1 0.1

Table 5. Calculated ratios of DMn / DFe in calcite for several precipitation rates at 10°, 25° and 50°C (after
Dromgoole and Walter, 1990).

83
Chapter 4

2+ 2+ 2+ 2+
Precipitaion rate log rate DMn / DFe log DMn / DFe
µmol m-2 hr -1 10°C 25°C 50°C 10°C 25°C 50°C

1 0 11.7 8.7 3.5 1.07 0.94 0.54

10 1 7.7 6.8 3.3 0.89 0.83 0.52
100 2 5 5.3 3.2 0.70 0.72 0.51
1000 3 3.3 4.1 3 0.52 0.61 0.48
10000 4 2.2 3.2 2.8 0.34 0.51 0.45
100000 5 1.4 2.5 2.7 0.15 0.40 0.43

84
Chapter 4

Figure 23. Graph plot between clumped isotope temperature and DMn/DFe composition of macro-columnar calcite samples: JMF 1. The grey lines indicate the log rate of
precipitation (µmol m-2hr-1).

85
Chapter 4

Figure 24. Graph plot between clumped isotope temperature and DMn/DFe composition of macro-columnar calcite samples JMF 12. The grey lines indicate the log rate of
precipitation (µmol m-2hr-1).

86
Chapter 4

Figure 25. Plot of bulk isotopic composition between δ13C Calcite [VPDB] and δ18O Calcite [VPDB] (top), and δ18O Fluid
[VSMOW] and clumped isotopes derived temperature (bottom) of JMG 1 thin-vein calcite and host rock samples.

87
Chapter 4

4.7 Conclusions

From the Jebel Madar dataset we conclude that (1) There are two type of calcites recognized

from the analysis, which are lower temperature macro-columnar calcite with the lighter

δ18Oliquid SMOW, and the higher temperature thin-vein calcite with heavier δ18Oliquid SMOW (2) Our

lower temperature (macro-columnar calcite) samples are precipitated in disequilibrium

condition, where δ18O and Δ47 values are impacted by rapid rates of precipitation, (3) the

combined clumped isotope and trace element analysis was shown for the first time here to

potential significantly help identify kinetic effects due to high rate of precipitation in natural

systems. The methods and approaches presented here can be applied in a range of other case

studies that involve fluid migration along structures, but also potentially more broadly to

biogenic carbonates. Potential remaining areas of uncertainty derived from using total

abundance of the trace elements and future research could be focused on quantifying the

different speciation of chemical elements to acquired closer experimental parameter of

Dromgoole and Walter (1990b).

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Chapter 5

Structural diagenesis of a salt dome

revealed by carbonate clumped isotope
thermometry (Jebel Madar, Oman)
5.1 Abstract

A better understanding of paleo fluid circulated along fractures remains a challenge. The

complexity of the tectonic evolution and diagenetic process of salt domes in particular, such as

at Jebel Madar (Northern Oman), makes them ideal case study for paleo fluid flow. Here, we

apply carbonate clumped isotope on different generations of calcite precipitated in fractures

and veins and on the host rock to reconstruct paleo temperatures and paleo-fluids evolution at

this location. The clumped isotope temperatures indicate that calcite vein precipitation took

place between 48-171°C. Assuming temperature of recrystallization are faithfully captured by

our clumped isotope data, the geothermal gradient during the Campanian was 32.6˚C km-1. We

argue that the structural diagenesis history in the study area comprise two very distinct episodes

of fluid circulation. The first episode is deposition of a high temperature calcites indicating

deposition along fractures at depth followed by closed-system recrystallization during the

emplacement of the Hawasina Nappe. The second episode of fluid flow correspond to the lower

temperature calcite member represent meteoric diagenesis that also contains evidence for

kinetic fractionation of the clumped isotopes. Our results bring a new understanding of paleo

89
Chapter 5

fluid circulation along the fractures in salt domed setting. It also highlights the potential of the

clumped isotope proxy for structural diagenesis studies.

5.2 Introduction

Understanding structural diagenesis, i.e. the relationship between fluid flow and structural

elements, remains a challenge. This is in part because the nature of the fracture/fault

contribution to fluid flow (e.g. hydrocarbon entrapment, migration and flow) varies widely

(López and Smith, 1995; Knipe et al., 1998; Odling et al., 1999; Aydin, 2000). A better

understanding of how fluids move within fractures as well as of the interaction between fluid

and host-rock is particularly needed for accurate predictions in hydrocarbon and water

exploration in order to produce these resources in an efficient way. In particular, the movement

of fluids through the fracture systems in salt diapir setting is of interest but is complicated due

to the combination between episodic fluid flow and fracturing event. Jebel Madar is a dome-

shaped diapiric salt dome (Claringbould et al., 2013) and is an ideal location to study paleo-

fluid circulation along fractures because of the exposed carbonate carapace and the existence

of a large network of metric-size fractures filled with diagenetic calcite crystals (Figure 26).

Carbonate precipitated in the vein and fractures can be used as an archive of the oxygen isotopic

composition of the diagenetic fluid, and of the temperature of precipitation of the mineral

(Moore and Wade, 2013). Jebel Madar is also an ideal location because several studies were

conducted to investigate the relationship between halokinesis and fracture evolution on the

Jebel, as well as diagenetic studies using petrographic and cathodoluminescence (CL)

microscopy, x-ray diffraction (XRD), elemental geochemistry, and bulk stable isotope analysis

(Immenhauser et al., 2007; Claringbould et al., 2013; Vandeginste et al., 2013, 2017). Here,

we take advantage of the wealth of existing data and for the first time apply carbonate clumped

isotope thermometry to improve our understanding of structural diagenetic processes in salt

90
Chapter 5

domes. Carbonate clumped isotope thermometry is based on measuring the abundance of 13C-
18
O bonds (Δ47) in the carbonate lattice relative to a stochastic distribution of this isotopologue

(Ghosh et al., 2006). Carbonate clumped isotope thermometry only depends on the temperature

of the fluid, not its isotopic composition, thus enabling applications to faults and fractures

settings where fluid composition is often weakly constrained (Bergman et al., 2013; Dale et al.,

2014).

The specific objectives of our study were to (a) reconstruct the clumped isotope values of the

host-rock in order to estimate temperature of recrystallization of the matrix and thus minimum

estimates of regional burial depth, (b) constrain the carbonate clumped isotope thermometry of

the various calcite phases that infill the fractures on the salt dome, and finally (c) based on our

previous work (see chapter 3), and the result of (a) and (b), reconstruct the evolution of

diagenetic fluid circulation in fractures around Jebel Madar including accounting for the

presence of any kinetic fractionation or recrystallization of fracture infills. Our results

demonstrate that carbonate clumped isotope thermometry, combined with other approaches,

provides new insight when reconstructing diagenetic fluid flow in dynamic structural setting

impacted by diapiric salt movement.

91
Figure 26. Picture of the existence of a large network of metric-size fractures filled with diagenetic calcite crystals in Jebel Madar, Oman.

92
Chapter 5

5.3 Regional geology

Jebel Madar is a salt-cored dome structure, that formed by salt diapirism of the Precambrian-

Cambrian Ara (Mount et al., 1998) of the Ghaba Salt Basin. Jebel Madar is situated in the

Adam Foothills of the Oman Mountains in Northern Oman (Figure 27). The stratigraphy of

the exposed ̴ 500 m roof strata at Jebel Madar consist of Late Triassic to Cretaceous carbonates,

and is surrounded by quaternary plain deposits (Béchennec et al., 1992 op. cit. Claringbould et

al., 2013). The oldest formations cropping out in the center of the Jebel, at a junction between

the three main fracture corridors are the Triassic Akhdar Group dolostone and Jurassic Sahtan

Group sandstone and limestone. But most of the Jebel Madar outcrops comprise Cretaceous

Formations (Figure 28). The Lower Cretaceous consists of the Rayda, Salil, Habshan,

Lekhwair, Kharaib and Shuaiba Formations. The latter is overlain by the Kharaib Formation

and (above that) the Shuaiba Formation. The Nahr Umr Formation (a mud-rich seal) and the

Natih Formation are located stratigraphically above the Shuaiba Fm (Claringbould et al., 2013;

Vandeginste et al., 2017).

The tectonic evolution of Jebel Madar involved three phases (Figure 29) from Late Cretaceous

to Miocene as proposed by Claringbould et al. (2013) with some modification following

Vandeginste et al. (2017). The first phase is linked to the obduction of the Semail Ophilolites

and the Hawasina complex during Santonian times (Figure 29a). This phase is related to the

development of NE-SW oriented structural features including grabens, half-grabens and

fractures, and also initial doming which was interrupted according to Claringbould et al. (2013)

once the Hawasina Complex was emplaced at the location of Jebel Madar in the Campanian

(Figure 29b). The second phase in the evolution of Jebel Madar occurred as a result of the

WNW oriented obduction of the Masirah ophiolites on the Eastern margin of Oman during the

Early Palaeocene and development of E-W oriented dextral strike-slip faults and fractures

(Figure 29c). Finally, the third phase occurred during the Miocene when the main doming

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Chapter 5

occurred and NE-SW trending fractures and faults were reactivated in a compressional regime

caused by the Arabian plate colliding with the Eurasian plate. Major deposition of barite and

calcite along fractures are thought to have started at this stage and continued until recent time

(Figure 29d, Immenhauser et al., 2007; Vandeginste et al., 2017).

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Chapter 5

Figure 27. Map view of geological map of study area (modified after Claringbould et al., 2013) overlaid with
elevation model from ASTER GDEM (top) showing sample locations. The 3D image of Jebel Madar (bottom left)
shows the geometry of the triple junction between the three main fracture corridors in the middle of the salt dome.

95
Chapter 5

Figure 28. Stratigraphy of Cretaceous Formations at Jebel Madar. Column A to D is modified after Vandeginste
et al. (2017), Column E is clumped isotope temperature of the matrix and calculated geothermal gradient from the
current thesis (see text for detail).

96
Chapter 5

Figure 29. Tectonic evolution of Jebel Madar. The evolution divided into three different phases from Late
Cretaceous to Miocene (modified after Claringbould et al., 2013).

97
Chapter 5

5.4 Methods

5.4.1 Sample selection and sample preparation

The samples selected are a selection of the samples previously published in Vandeginste et al

(2017), allowing us to directly combine previous results with our new clumped isotope results.

Four types of calcite crystals were recognized in the paragenesis (Vandeginste et al., 2017)

based on their occurrence and characteristics, which are (Figure 30): (1) thin calcite veins:

calcite veins opening by 1-2 cm in the host rocks, filled with calcite crystals <1 cm in size; (2)

barite-associated calcite: calcite in meter-scale barite patches and meter-scale fractures that

contain barite; (3) fault zone calcite: large calcite crystals with a main crystallographic axis up

to tens of centimeters long occurring along major faults; and (4) macro-columnar calcite:

transparent calcite crystal (up to 5 cm in size) that can contain reddish colored zones or co-

occur with reddish brown silt layers. All the veins are categorized as syntaxial veins following

Bons et al., 2012. We selected twenty-six samples of calcite in large fractures and veins

strategically located to cover most of the Jebel (see Figure 27). All samples were powdered

using an agate mortar. Five out of twenty-six samples were used for a pilot study and analyzed

for clumped isotopes in 2012 (Dr. Anne-Lise Jourdan) using a manual vacuum line, whereas

the remaining twenty-one samples were analyzed in 2019 on an automated clumped isotope

line (Table 6).

5.4.2 Carbonate clumped isotope thermometry

All samples measurements were performed in the Stable Isotope Laboratory at Imperial

College London. The five samples used in the 2012 pilot study were analyzed on a manual

vacuum line following the method described in Dale et al. (2014). For the remaining twenty-

five samples measured in 2019, a maximum of 3 replicate measurements per sample were

analyzed using our fully automated system (the prototype IBEX system developed at Imperial

98
Chapter 5

College London) (see Table 6). All samples measurement following the experimental protocol

that previously described in methodology chapter (chapter 2).

5.5 Results

The results are shown in Table 7. The bulk oxygen isotope composition of the calcite (δ18O

Calcite [VPDB]) for thin-vein, barite-associated, fault zone, and macro-columnar calcite samples

range from -4.69 ± 0.06 to -8.1‰ ± 0.19, -5.17 ± 0.04 to -6.0 ± 0.01‰, -4.5 ± 0.12 to -14.2 ±

0.01 ‰, and -12.29 ± 0.04 to -14.85 ± 0.01 ‰ respectively (Figure 31). The bulk oxygen

isotope composition of the calcite (δ18O Calcite [VPDB]) for host rock range from -5.6 ± 0.10 to -

6.01 ± 0.19‰. The carbon isotopic composition (δ13C Calcite [VPDB]) is ranging from 1.42 ± 0.07

to 2.78 ± 0.04 ‰ for thin-vein calcite, 1.88 ± 0.09 to 2.55 ± 0.29‰ for barite-associated calcite,

-4.18 ± 0.04 to 2.50 ± 0.00 ‰ for fault zone calcite, -6.45 ± 0.05 to -1.21 ± 0.02‰ for macro-

columnar calcite, and 2.27 ± 0.03 to 1.23 ± 0.18‰ for host rock. (see Figure 31).

The Δ47 values vary between 0.471 ± 0.029 ‰ and 0.621 ± 0.007‰ with standard error (SE)

of 0.001–0.029‰ and standard deviation (SD) of 0.002–0.059‰, corresponding to calculated

clumped isotope temperatures range of 93 ± 7 to 121 ± 8ºC for thin-vein calcite, 74 ± 0 to 142

± 29 ºC for barite-associated calcite, 51 ± 3 to 105 ± 9ºC for fault zone calcite, 54 ±1 to 68 ±

8ºC for macro-columnar calcite, and 106 ± 15 to 71 ± 13ºC for the host rock (Figure 32). The

calculated δ18O Fluid [VSMOW] composition for the thin-vein, barite-associated, fault zone, and

macro-columnar calcite samples range from ranges between 6.4 ± 0.4 to 12.7 ± 0.8‰, 5.9 ± 0

to 14.3 ± 1.9‰, -5.3 ± 1.0 to 11.0 ± 1.0‰, and -7.1 ± 0.2 to -3.0 ± 0.6‰. The calculated δ18O

Fluid [VSMOW] composition for the host rock ranges from 4.7 ± 1.7 to 10.0 ± 1.7‰ (see Figure

32).

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Chapter 5

Figure 30. Sample occurrence for this study, which are: thin-vein calcite (top-left), barite-associated calcite (top-
right), fault zone calcite (bottom-left), and macro-columnar calcite (bottom-right).

Table 6. Clumped isotope measurement protocols for pilot samples and current samples

Sample Year of Preparation Sample Corrections

Analysis Line Size

Pilot 2012 Manual 6-6.5 mg 1. Non-linearity correction: Heated gasses (Davies and John, 2017)
sample vacuum line 2. Projecting to reference frame (Dennis et al., 2011)
3. Adding acid fractionation factor: 0.082‰ (Defliese et al., 2015)

Current 2019 Prototype 3-3.5 mg 1. Non-linearity correction: Pressure Base Line (Bernasconi et al., 2013)
sample automated 2. Projecting to reference frame (Dennis et al., 2011)
IBEX 3. Adding acid fractionation factor: 0.082‰ (Defliese et al., 2015)

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Table 7. Result from clumped isotopes analysis.

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Figure 31. Plot of bulk isotopic composition between δ13CCalcite [VPDB] and δ18O Calcite [VPDB] from twenty-six calcite
vein samples. The background data points are δ13CCalcite [VPDB] and δ18O Calcite [VPDB] isotopic composition of
Vandeginste, et al., 2017; thin-vein calcite, barite-associated calcite, fault zone calcite, and macro-columnar
calcite are plotted in the same colors and shapes with the current study data plot. Some of the fault zone calcite
from current analysis have similar isotopic composition with macro-columnar calcite, thin-vein, and barite-
associated calcite from the Vandeginste et al, 2017 data.

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Figure 32. Clumped isotope results. The vertical axis corresponds to clumped isotope temperature in ºC; the
horizontal axis is calculated δ18O Fluid [VSMOW]. The grey diagonal lines represent lines of equal δ18O composition
for the calcite, in ‰ VPDB. Blue and red arrows show the different trend of vein precipitation (see text for the
detail).

Figure 33. Data plot between ratio Mn and Fe (DMn/DFe) and clumped isotope temperature. The isoline shows the
same rate of precipitation in µmol m-2hr-1. The grey isoline is the log of rate precipitation above 0 µmol m-2hr-1,
and the orange line is below 0 µmol m-2hr-1.

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5.6 Discussions

5.6.1 Understanding the burial history of the carbonates in the carapace of the salt

dome

Geomechanical properties of rocks are key aspect when evaluating strategies for well drilling

and reservoir production, stimulation and monitoring (Bjørlykke and Høeg, 1997). Importantly,

rocks change properties during increasing burial depth as a function of various diagenetic

processes including compaction, cementation, and recrystallization which are also controlled

by the primary composition of the sediment. Carbonate rock are of particular interest because

of the wide variety of diagenetic modifications that can occur during progressive burial (Croizé

et al., 2013). Thus, a better approach to predict burial depth is necessary. Here, the clumped

isotope temperatures offer a chance to extract quantitative burial estimates by providing

maximum estimate of burial depth. Previous studies have demonstrated that the clumped

isotope temperature of fine grained carbonate such as early dolomites and micrite is

representative of recrystallization at depth (e.g. John, 2015; Macdonald et al., 2018; Veillard

et al., 2019). The petrographic analysis of Al-Dabbas et al. (2013) of the Nahr Umr Formation

demonstrates that micrite transform partially or completely to sparite (4–10 μm) or

psuodosparite (10–50 μm) regionally, supporting the use of clumped isotope to estimate burial

temperatures in our case. The clumped isotope temperature can be used as a proxy for the

temperature of recrystallization assuming that calcite completely recrystallizes at equilibrium.

Previous works has shown that the temperature of recrystallization tend to be close to the

maximum burial temperatures (Veillard et al., 2019) and can be used as a minimum estimate

of the maximum burial temperature (John, 2015). The maximum temperature at which the

sample was buried is a function of: (a) the paleo-geothermal gradient; and (b) the difference

between the maximum temperature recorded in host rock and the Earth surface temperature.

The temperature range recorded in the younger Cretaceous host-rock formation, Natih Fm.

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(JME 5B Host) is 45ºC, and the average temperature of the older Cretaceous formation, the

Jurassic Salil Fm. is 76 ºC, with the lowest temperature at 51ºC and the highest at 106ºC.

Estimating the thickness of sediments between the Natih to Salil Fm. at about 950 m

(Claringbould et al., 2013; Vandeginste et al., 2017), yields a calculated paleo-geothermal

gradient during burial time (Campanian) of 32.6ºC km-1 (see Figure 28). Using this paleo-

thermal gradient and the temperatures of the samples we can estimate a maximum burial depth

of 1.4 km for the Natih and 2.3 km for the Salil Fm. This result is compatible to the estimated

overburden thickness of the Hawasina complex and Semail Nappe above the Natih Fm.

proposed by Claringbould et al. (2013) based on seismic sections from within a ten km range

from Jebel Madar. Hence, our clumped isotope data confirm the models suggesting

emplacement of the Hawasina Nappe as far East as the area of Jebel Madar.

5.6.2 Mechanism of cementation of the barite-calcite association, the thin-veins, and

nature of the associated fluids: potential for recrystallization

The barite-calcite association and calcite within thin-veins were first reported by Vandeginste

et al. (2017), who recognized that these were some of the oldest fracture infills at Jebel Madar.

This also implies that the barite-calcite and thin-vein calcite are older than the macro-columnar

calcite: this latter phase was dated as Pleistocene to Holocene using Uranium-series

(Immenhauser et al., 2007). But is it possible to put more quantitative constraints on the age of

these older phases? The clumped isotope data confirm that both the barite-associated calcite

and thin-vein calcite have the highest temperatures measured in this study, ranging from 74 to

171ºC (Figure 32). These phases also yield heavier calculated δ18O Fluid [VSMOW] up to +16.2‰.

that could be interpreted as derived from basinal hydrothermal fluid. Previously, based on

mostly single-phased fluid inclusions in barite and barite-calcite and in part on our pilot study’s

clumped isotope data presented in a conference paper (John et al., 2014), Vandeginste et al.

(2017) interpreted the barite and barite-associated calcites as being deposited at around 110˚C.

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Furthermore, Immenhauser et al. (2007) deducted from fluid inclusions that the much colder

macro-columnar calcites must have been formed by the mixing of a meteoric fluid and a higher

salinity fluid. Based on that as well as the temperature and high salinity data from the fluid

inclusions in the barite, Vandeginste et al. (2017) suggested that the entire suite of calcite

infilling fractures at Jebel Madar (i.e. from the barite-associated calcite all the way to the

macro-columnar calcite) could be explained by a simple model of fluid mixing. In the

Vandeginste et al. (2017) model, a hot saline deep fluid would be responsible for the

precipitation of barite and barite-associated calcite at depth, and when this saline fluid ascends

along the fractures of the salt dome, it would mix with meteoric fluids leading to the

precipitation of the fault-related calcite and macro-columnar calcites. Our new clumped isotope

data challenges the current published model.

First, some of the high (>120-140˚C) clumped isotope temperatures obtained in the barite-

calcite and thin-vein calcites (and indeed the 110˚C homogenization temperature reported by

Vandeginste et al. (2017) are hard to explained in a salt dome setting: because of the cooling

effect of the salt, saline (5-20 wt% NaCl eq.) fluid in this type of settings are usually at a

temperature range of 70 to 100ºC (Morrison and Parry, 1986). Second, our bulk isotope results

for the host rock samples close to the thin-vein calcite (JMC 6 Host) and barite-associated

calcite (JMC 9 Host) are in the range of typical Lower Cretaceous limestone (Celestino et al.,

2017). The fact that both the thin-vein and barite-associated calcite samples δ13C and δ18O Calcite

[VPDB] are similar to the host rock (see Figure 31) is a strong indication that host-rock buffering

is impacting these samples (e.g. Meyers and Lohmann, 1985; Veillard et al., 2019). It also

appears from our data that the barite-associated calcite and calcite veins both plot in a clumped

isotope temperature - δ18O Fluid [VSMOW] space along a path characteristic of closed-system

recrystallization (e.g. John, 2015). The δ18OCalcite [VPDB] for both sample types remains constant

even if the temperature and back-calculated δ18O Fluid [VSMOW] vary (see Figure 32). We know

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from our clumped isotope measurements of the matrix that the host-rock was recrystallized at

an approximate burial depth of about 2-2.2 kilometer: the similarity between the barite-calcite

/ vein calcite and the matrix clumped isotope temperatures, as well as the evidence for closed-

system recrystallization (see Figure 32) strongly suggest that the barite and barite-associated

calcite were early phases that were emplaced before obduction of the Hawasina nappe, and

were subsequently recrystallized at depth during the maximum burial phase of the obduction.

Significantly, the fault-zone calcite (with the exception of 2 samples) and macro-columnar

calcite also show a trend, but very different to the older calcite phases. The U-series dating

from Immenhauser et al. (2007) places the formation of the macro-columnar calcite within the

Pleistocene to Holocene: hence, these later phase are much younger than the Cretaceous, and

cannot have been recrystallized during the emplacement of the Hawasina nappe. By extension,

the Vandeginste et al. (2017) proposed model of a deep fluid responsible for the barite-calcite

association mixing with meteoric fluids to form the macro-columnar calcite does not reconcile

with the new clumped isotope data we present. We suggest instead that there are two very

distinct episodes of fluid circulation within the Jebel: during tectonic phase 1 (Santonian –

Campanian) of Claringbould et al. (2013), fluids supersaturated with respect to barite and

calcite must have circulated in the early fractures associated with the initial doming phase (see

Figure 29b). Later in the Campanian, the emplacement of the Hawasina Nappe would have

buried these early phases down to 2.3 kilometers, explaining the closed-system recrystallization

trend we observe (trend 1, Figure 32). The second pulse of fluid is associated with Miocene

and recent halokinesis (Claringbould et al., 2013) and led to the current situation at Jebel

Madar, where meteoric fluids circulate downwards along existing fractures (with potential

admixture of a warmer, more saline fluid) leading to the formation of the fault-zone calcite and

macro-columnar calcite (trend 2, Figure 32).

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5.6.3 The macro-columnar and ‘fault-zone’ calcite phase and potential kinetic effects

Hence, our clumped isotope data reveal a more complicated history of fluid flow at Jebel Madar

than previously proposed. If it is clear that the lower temperature end member samples (from

46 to 80ºC) represented by the fault-zone and macro-columnar calcite indicate higher meteoric

influx (the calculated δ18O Fluid [VSMOW] of -7.3‰ is comparable to regional meteoric

precipitation values for the Pleistocene, Burns et al., 1998), the measured temperatures are well

above annual ground temperature at the water table (33° ± 0.3°C) in Northern Oman

(Weyhenmeyer et al., 2000). This is compounded by the fact that fluid inclusions analyses were

not able to derive a temperature for these samples, primarily because only single-phase

inclusions were present which suggests low temperatures (Vandeginste et al., 2017). We also

note that a subtle trend exists between calculated δ18O Fluid [VSMOW] and clumped isotope

temperatures (see Figure 32), although as highlighted above this is a very different trend to the

recrystallization trend observed in older minerals and cannot be explained by recrystallization

because of the young age of the sediments (Immenhauser et al., 2007) and very well preserved

crystal growth patterns in CL images (Vandeginste et al., 2017).

Several hypotheses other than recrystallization can be explored to explain why the macro-

columnar and fault-zone calcite show relatively high clumped isotope temperatures. First, we

need to explore the possibility that the elevated temperatures simply reflect precipitation at

depth along the fractures, and thus heating of the meteoric fluid following the geothermal

gradient before calcite precipitation. Assuming the geothermal gradient in Oman is about 32°C

km-1, the temperature difference between the samples temperatures and modern meteoric water

is 14 to 48°C, which depending on assumptions related to the geothermal gradient, translates

into a burial depth of 0.3 km down to 1.5 km for the hottest samples. If the precipitation at the

shallower end of this depth range is possible, the fact that the entire Cretaceous sedimentary

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column is at most 1 km implies that at least for the hottest samples some other mechanism must

play a role.

The second hypothesis, following the interpretation from Immenhauser et al. (2007) for the

macro-columnar calcite in the phreatic caves at Jebel Madar, is formation by mixing of a saline

hydrothermal fluid and a meteoric fresh water fluid (with incorporation of soil-derived 12C-rich

carbon). Mixing with a hot hydrothermal fluid may explain the higher clumped isotope

temperatures and the elevated salinities from fluid inclusions (1.6 to 7.3 wt.% NaCl equivalent,

Immenhauser et al., 2007) also strongly suggest involvement of the ascending deep seated

waters, potentially as deep as the upper Precambrian to Lower Cambrian Ara Formation

evaporites (Peters et al., 2003) which form much of the salt dome underneath Jebel Madar. The

fluid mixing model is supported by a strong trend of decreasing of δ18O Fluid [VSMOW] with

decreasing clumped isotope temperature (see Figure 32), which in this case could mean

increased amount of cool meteoric water. But to attribute trend 2 on Figure 4 to fluid mixing

implies that the source of the two fluids and their initial temperatures have not change over the

time of precipitation of the minerals, and more importantly, that the ascending fluid must have

experienced no loss of heat during their transport in the fault: only thus can both the δ18O Fluid

[VSMOW] and clumped isotope temperature mix in a congruent way. This would imply almost

instantaneous movement of fluid along faults, followed by very rapid precipitation of calcite

along the fracture. If the ascending fluid were to cool down, it would need to be much hotter

(and thus come from much deeper) to account for a mixing temperature of 80˚C. Hence,

although mixing with a deeper fluid is possible, this alone cannot easily explain the warm

temperatures. Furthermore, these warm temperatures could be at least in part captured in fluid

inclusions (Vandeginste et al., 2017).

The last hypothesis to account for the strong correlation between increasing temperature and

heavier δ18O Fluid [VSMOW] is kinetic fractionation. Mathematically, both an increase in δ18O Calcite

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[VPDB] and a biased increase in estimated precipitation temperature will result in a heavier

calculated δ18O Fluid [VSMOW] (Kim and O’Neil, 1997). Based on detailed analysis of transect

along three cements at Jebel Madar, Herlambang and John (in prep., chapter 4) suggested that

clumped isotopes and trace elements revealed strong evidence for kinetic effects in macro-

columnar calcite, but not in the thin-vein calcite. The work of Herlambang and John (in prep.,

chapter 3) thus provide a new framework to assess kinetic fractionation for all of the samples

measured in this study. By following Herlambang and John (in prep., chapter 4) we can plot

our clumped isotope temperatures obtained from bulk mineral analysis against the published

Fe and Mn trace element composition from Vandeginste et al. (2017). We note that a full suite

of trace element measurement was planned for this PhD, but it was not possible to finish this

work because of shutting down of all laboratories due to the COVID-19 pandemic. Hence, we

rely here on a subset of data, that will eventually be expended for publication. Even though

there is only a few data plotted, since most of the published Fe concentrations of Vandeginste

et al. (2017) are below detection limit, this reveals that most macro-columnar calcites and fault-

zone calcite must have been precipitated rapidly (Figure 33). Even though the isoline of

precipitation rates on the Figure 33 is derived from the extrapolated equation of lower

temperature precipitation rates (see chapter 4 for the detail) thus requires further work in the

future, the barite-calcite and thin calcite vein show lower rates of precipitation and no

correlation between temperature and trace elements composition. This strongly suggests that

the warmer end of the temperature range in the cooler macro-columnar and fault-zone calcite

are influenced by kinetic effects, and that the lower temperatures are more representative of

formation condition at around 40˚C, and burial depth of < 1 km. We also note that the fault-

zone calcite from Vandeginste et al. (2017) actually is mostly similar to the macro-columnar

calcite phase, but that it sometimes contains calcite that was deposited earlier during the calcite-

barite / thin-vein calcite phase (see Figure 31 and Figure 32). Hence, though our data does not

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preclude the existence of two fluid sources mixing in the study area, the increasing temperature

associated with heavier δ18OFluid [VSMOW] is not necessarily a strong evidence of mixing of these

two fluids.

5.7 Conclusions
From the dataset we conclude that 1) Paleo temperature derived from clumped isotope in Jebel

Madar, Oman vary between 48 to 171˚C, 2) assuming temperature of recrystallization are

faithfully captured by our clumped isotope data, the geothermal gradient during the Campanian

was 32.6˚C km-1, 3) The evolution of fluid flow in the study area comprise two very distinct

episodes of fluid circulation, 4) The early calcite phases in the thin-vein calcite and barite-

associated calcite with temperature between 74 to 171˚C are associated with burial and closed-

system recrystallization during Campanian age. 5) The later phases of calcite precipitated

during the Pleistocene to Holocene and reflect meteoric diagenesis with lower precipitated

temperature range from 46 to 80˚C, the latter temperatures indicating the presence of kinetic

effects.

This study highlights the evolution of paleo fluid flow in the fracture system within a salt

diapirism tectonic setting. The temperature derived from the clumped isotope proxy

significantly improves our regional understanding of fluid circulation and the interaction of

fluid with the host rock through time. We argue that our case study is a proof of concept for

this type of approach. It shows that more detailed samples and a broader range of analytical

methods (trace elements, petrography, other isotope systems) are required in order to obtain a

more accurate knowledge of the history of paleo fluid flow and diagenesis along fractures.

Crucially, even recrystallization temperatures can provide important clue on the relative timing

of diagenetic phases.

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Chapter 6

Conclusions and further work

This chapter contains the conclusions and major findings of this research project, as well as

wider implication, unresolved issues and suggested further work. This chapter starts by

summarizing the entire thesis and also the contribution to the knowledge through findings in

this research. Second, the applications of the findings are presented in the broader context of

the field. Finally, I highlight the current limitations of this work, and potential further work that

could be done.

6.1 Conclusions, main findings, and wider implications

The carbonate clumped isotope thermometry is a useful proxy in paleo temperature

reconstruction, especially in environment where the δ18O of fluid from which carbonates

precipitate is poorly constrained, such as faults and fractures systems (Streit et al., 2012;

Swanson et al., 2012, 2018; Bergman et al., 2013; Loyd et al., 2013; Budd et al., 2013; Sumner

et al., 2015; Crider et al., 2015; Crognier et al., 2015; Hodson et al., 2016b; Luetkemeyer et al.,

2016; Siman-Tov et al., 2016; Cruset et al., 2016, 2018, 2020a, 2020b; Lu et al., 2017, 2018;

Macdonald et al., 2017; Quade et al., 2017; Lacroix et al., 2018; Mering et al., 2018; Smeraglia

et al., 2018; Dennis et al., 2019; MacDonald et al., 2019; Nardini et al., 2019; Quandt et al.,

2019, 2020; Török et al., 2019; Boulton et al., 2020; Fosu et al., 2020; Lee et al., 2020; Brogi

et al., 2020; Muñoz-López et al., 2020; Salomon et al., 2020; Tartaglia et al., 2020). This thesis

aims were to unravel the paleo-temperature and fluid composition that lead to carbonate

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Chapter 6

precipitation along fractures, and also to explore if any particular kinetic isotope fractionation

effects impacted the clumped isotope signature of those carbonates. This is achieved through

conducting the work laid down in chapters 3 to 5 of the thesis, summarized in the following

paragraph.

1. The clumped isotope thermometry significantly improves the precision for estimating

temperatures in the subsurface, and has proven in the first case study (chapter 3) to be

a valuable tool to understand environmental processes related to the deep biosphere.

The combined clumped isotope and fluid inclusion temperatures dataset seems a priori

to rule out any significant kinetic effects of microbial processes on clumped isotope

temperatures. Moreover, significant advantage of the new clumped isotope results

compared to the fluid inclusion data is that we have better constraints on temperatures

below 80°C. This turns out to be crucial findings, as we are able to demonstrate that it

is precisely the lower temperature precipitates that display the more negative carbon

isotope values commonly associated with bacterial activity. For wider implications, the

carbonate clumped isotopes has proven to significantly improves precision for

estimating temperatures and fluid origin. This is important, as it indicates that clumped

isotope could be applied more broadly to the study of a wide range of temperatures and

settings.

2. In chapter 4, we demonstrate that trace element results reveal a strong correlation

between Mn and Fe and the clumped isotope temperatures. We argue that the

incorporation of Mn and Fe into calcite minerals is indicative of a change in crystal

growth rates that leads to kinetic fractionation and could biased the resulted temperature

values. Thus this is an important finding, as for the first time we can independently

show potential kinetic fractionation in ancient natural samples from subsurface

fractures that resulted in clumped isotopes temperatures higher than the environment of

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deposition. The new combined clumped isotopes / trace elements approach is a critical

step to future applications of the clumped isotope proxy to natural systems as it can

reveal potential isotopic disequilibrium independently of the temperature measured.

The methods and approaches presented on that chapter can be applied in a range of

other case studies that involve fluid migration along fractures, but also potentially more

broadly to biogenic carbonates to assess the authenticity of the clumped temperatures

in this setting.

3. In chapter 5, we show that the temperature derived from the clumped isotope proxy

significantly improves our regional understanding of fluid circulation and the

interaction of fluid with the host rock through time. We argue that our case study is a

proof of concept for this type of approach. Furthermore, the other important findings

through this chapter are that the clumped isotope temperatures of recrystallization offer

a tighter constraint time interval of relative structural diagenetic events before the

emplacement of Hawasina-Nappe at Campanian. Similar tectonic, hydrologic, and

episodic fluid flow evolution as derived for Jebel Madar can be expected in salt dome

strata in other location world-wide. Moreover, the temperature of recrystallization can

be a powerful proxy to distinguish between older and earlier phases of fluid flow and

mineralization in fracture systems.

6.2 Further work

The result and discussion on the second result chapter (chapter 4) have drawn attention to the

application of clumped isotope in fractures and the possibility of kinetic fractionation effect

due to precipitation rates. The result from this study derived from the equation relating trace

element composition to precipitation rates for calcite precipitation at 10, 25, and 50°C, as a

consequence the precipitation rates at temperature >50°C remain unsolved. Future work could

be focussed on further laboratory simulation that enabling us to be more precise in calculate

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the relation of precipitation rate, temperature, and the trace elements composition at the higher

temperature samples. In addition, in the laboratory experiments pH, temperature, isotopic

composition, and precipitation rates could be simulated.

Another unresolved issue is to consider the other variable that may affect the precipitation rates

and the Δ47 values, such as speciation of chemical elements. Future consideration could be

given to detailed sample analysis using a broader range of analytical methods in order to obtain

a more accurate knowledge of the different variables. For instance, it may be possible to

determine the speciation of chemical elements using Leucoberbeline blue dye (Sigma-Aldrich,

CAS 52748-86-4; Boogerd and De Vrind, 1987).

In order to further advance our understanding of the fluid flow system at Jebel Madar (chapter

5), absolute ages of cementation of individual diagenetic phases are needed. Ages of

cementation phases suggested by Immenhauser et al. (2007), Claringbould et al. (2013),

Vandeginste et al. (2017) and this current study differ remarkably. Immenhauser et al. (2007)

already dated the macro-columnar calcite, using the U-Th methods to determine a Pleistocene

to Holocene age. For further work, the application of U-Pb dating methods for the diagenetic

products in the fracture system at Jebel Madar is recommended. U-Pb dating of carbonates is

applicable to almost the entire geologic time scale and is suitable for carbonates (Rasbury and

Cole, 2009). It would help to determine the evolution of the fracture and better knowledge of

episodic fluid flow, or in our case, the age of the interpreted recrystallization of our veins.

Lastly, one work that could not be completely finished in this PhD is to analyze the Jebel Madar

samples for trace element. This proved impossible to do because of instrument problems in late

2019, followed by the shutting down of all laboratories due to the COVID-19 pandemic. The

further work should focus on continue our trace element analysis approach to obtain a better

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understanding of kinetic fractionation effect from the relationship between elemental ratio,

temperature, and rate of precipitation.

116
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Appendices
Appendix A – Raw data of result chapter 3
Appendix

d13C d13C d18O d18O D47 D47

d13C d18O D47
VPDB VPDB VPDB VPDB CDES CDES 49 D48
ID VPDB VPDB CDES
(Final) (Final) (Final) (Final) (Final) (Final) Param Offset
(Final) (Final) (Final)
SD SE SD SE SD SE
S1 KKR2 -23.17 0.2 0.1 -11.43 0.33 0.16 0.593 0.01 0.005
2017-07-18
R1 -23.35 -11.78 0.586 -0.161 -0.45
14:29
2018-05-06
R2 -23.27 -11.49 0.593 -0.061 -0.059
11:23
2018-07-10
R3 -22.9 -11 0.608 0.015 0.062
10:58
2018-07-10
R4 -23.13 -11.43 0.586 0.005 -0.36
13:30
S2 KFM04A -24.82 0.45 0.23 -12.79 0.17 0.09 0.59 0.006 0.003
2018-01-19
R1 -25.23 -12.76 0.582 -0.055 -0.786
15:33
2018-04-30
R2 -25.18 -12.56 0.589 0.228 0.001
15:04
2018-05-13
R3 -24.34 -12.88 0.596 0.102 0.057
12:38
2018-07-17
R4 -24.53 -12.96 0.593 0.088 0.035
13:14
S3 KFM06A -17.17 0.11 0.06 -12.76 0.1 0.05 0.613 0.019 0.009
2018-05-07
R1 -17.01 -12.87 0.588 0.117 0.09
10:44
2018-05-13
R2 -17.17 -12.64 0.633 0.113 0.082
17:31
2018-05-20
R3 -17.22 -12.72 0.617 0.033 -0.11
15:05
2018-07-17
R4 -17.27 -12.8 0.612 0.099 -0.111
17:20
S4 KFM06C -22.94 0.26 0.1 -12.3 0.42 0.16 0.621 0.032 0.012
2018-05-07
R1 -22.72 -12.47 0.564 0.092 -0.283
13:17
2018-05-20
R2 -23.06 -11.73 0.605 -0.001 -0.507
17:35
Appendix

2018-05-27
R3 -23.21 -11.77 0.622 0.098 -0.268
15:42
2018-06-03
R4 -23.01 -12.16 0.607 0.092 0.206
12:48
2018-07-22
R5 -23.23 -12.71 0.641 0.136 0.057
17:31
2018-07-27
R6 -22.52 -12.6 0.655 0.2 -0.092
05:09
2018-07-27
R7 -22.83 -12.67 0.652 0.179 -0.138
19:23
S5 KLX 14A -7.52 0.06 0.03 -9.29 0.26 0.11 0.607 0.02 0.009
2018-01-19
R1 -7.49 -9.11 0.613 -0.18 -0.643
12:31
2018-05-06
R2 -7.49 -9.02 0.576 0.134 -0.188
16:42
2018-05-13
R3 -7.44 -9.21 0.628 0.152 0.034
15:01
2018-05-20
R4 -7.55 -9.53 0.606 0.036 -0.304
12:31
2018-07-22
R5 -7.61 -9.6 0.615 0.164 0.011
19:51
S6 KLX04 513 -14.98 0.2 0.11 -14.69 0.33 0.19 0.547 0.005 0.003
2018-07-27
R1 -15.08 -14.77 0.547 0.215 -0.212
14:34
2018-07-28
R2 -15.11 -14.97 0.542 0.15 0.015
04:57
2018-09-10
R3 -14.75 -14.32 0.551 0.01 0.802
12:43
S7 KLX04 669 -13.82 0.02 0.01 -15.8 0.12 0.07 0.53 0.026 0.015
2018-07-27
R1 -13.81 -15.68 0.52 0.182 -0.092
07:36
2018-07-28
R2 -13.84 -15.8 0.511 0.177 -0.015
00:04
2018-09-10
R3 -13.81 -15.92 0.56 -0.009 0.859
15:17
S8 KLX06 814 -11.14 0.1 0.06 -15.31 0.11 0.06 0.602 0.045 0.026
Appendix

2018-07-27
R1 -11.11 -15.43 0.55 0.214 -0.034
17:03
2018-08-19
R2 -11.05 -15.27 0.62 0.019 0.348
13:12
2018-09-03
R3 -11.25 -15.22 0.635 0 -0.114
15:52
S9 OUTCROP03 -10.72 0.13 0.08 -13.53 0.14 0.08 0.55 0.031 0.018
2018-07-27
R1 -10.77 -13.55 0.538 0.196 -0.199
09:55
2018-07-28
R2 -10.81 -13.67 0.586 0.202 0.078
02:27
2018-08-19
R3 -10.57 -13.38 0.527 0.051 0.741
16:00
Appendix B – Raw data of result chapter 4
Appendix

d13C d13C d18O d18O D47 D47

d13C d18O D47
VPDB VPDB VPDB VPDB CDES CDES 49 D48
ID VPDB VPDB CDES
(Final) (Final) (Final) (Final) (Final) (Final) Param Offset
(Final) (Final) (Final)
SD SE SD SE SD SE
S1 JMF 1 1 -5.85 0.08 0.05 -14 0.19 0.11 0.65 0.017 0.01
2019-03-26
R1 -5.92 -14.17 0.654 0.072 0.015
17:45
2019-03-31
R2 -5.88 -14.03 0.664 0.129 0.041
05:48
2019-04-08
R3 -5.76 -13.8 0.632 0.11 0.133
14:36
S2 JMF 1 2 -5.79 #NUM! #NUM! -13.85 #NUM! #NUM! 0.625 #NUM! #NUM!
2019-08-04
R1 -5.79 -13.85 0.625 0.171 0.112
19:14
S3 JMF 1 3 -4.59 #NUM! #NUM! -14.07 #NUM! #NUM! 0.64 #NUM! #NUM!
2019-08-04
R1 -4.59 -14.07 0.64 0.173 0.065
23:32
S4 JMF 1 A -6.13 0.02 0.01 -14.04 0.05 0.03 0.633 0.009 0.005
2019-03-08
R1 -6.15 -13.99 0.627 0.109 0.053
00:10
2019-03-10
R2 -6.12 -14.09 0.629 0.103 0.037
19:01
2019-03-16
R3 -6.13 -14.02 0.644 0.176 0.126
18:43
S5 JMF 1 B -6.2 0.09 0.05 -14.61 0.08 0.04 0.633 0.018 0.01
2019-03-08
R1 -6.2 -14.62 0.643 0.113 -0.004
02:23
2019-03-11
R2 -6.3 -14.68 0.643 0.124 -0.028
04:14
2019-03-15
R3 -6.11 -14.53 0.612 0.104 0.036
14:30
S6 JMF 1 C -2.2 0.28 0.16 -10.86 0.34 0.19 0.656 0.044 0.025
2019-03-26
R1 -1.9 -10.49 0.609 0.104 0.121
15:42
2019-03-31
R2 -2.25 -10.93 0.697 0.14 0.197
00:45
Appendix

2019-04-08
R3 -2.46 -11.15 0.663 0.107 0.283
12:31
S7 JMF 12 1 -7.52 0.04 0.02 -15.32 0.04 0.02 0.643 0.032 0.019
2019-03-27
R1 -7.56 -15.36 0.68 0.131 0.212
18:18
2019-03-30
R2 -7.48 -15.31 0.628 0.138 0.115
12:19
2019-04-08
R3 -7.52 -15.28 0.621 0.138 0.003
20:40
S8 JMF 12 2 -5.54 0.02 0.01 -14.5 0.03 0.02 0.625 0.039 0.023
2019-03-27
R1 -5.55 -14.52 0.67 0.119 0.108
20:17
2019-03-30
R2 -5.54 -14.51 0.601 0.076 0.062
14:24
2019-04-08
R3 -5.52 -14.46 0.605 0.147 -0.024
22:46
S9 JMF 12 3 -5.59 0.01 0.01 -15.08 0.07 0.04 0.629 0.026 0.015
2019-03-27
R1 -5.6 -15.1 0.659 0.124 0.174
22:18
2019-03-30
R2 -5.58 -15.13 0.608 0.084 0.009
16:21
2019-04-09
R3 -5.58 -15 0.622 0.134 0.017
00:42
S10 JMF 12 4 -7.61 0.07 0.04 -15.44 0.01 0.0 0.641 0.035 0.02
2019-03-28
R1 -7.68 -15.45 0.672 0.116 0.138
06:38
2019-03-30
R2 -7.54 -15.44 0.646 0.099 0.035
20:41
2019-04-09
R3 -7.63 -15.44 0.604 0.107 0.01
04:55
S11 JMF 12 5 -4.79 0.02 0.01 -15.58 0.08 0.05 0.642 0.025 0.014
2019-03-28
R1 -4.8 -15.68 0.666 0.151 0.205
10:49
2019-03-30
R2 -4.76 -15.54 0.643 0.134 0.1
22:47
2019-04-09
R3 -4.79 -15.53 0.616 0.133 0.361
07:01
Appendix

S12 JMF12 A -6.39 0.05 0.03 -14.63 0.08 0.04 0.628 0.023 0.013
2019-03-08
R1 -6.44 -14.7 0.623 0.119 0.022
08:44
2019-03-10
R2 -6.37 -14.54 0.607 0.146 -0.141
16:48
2019-03-16
R3 -6.36 -14.65 0.653 0.105 0.205
07:51
S13 JMF12 B -6.39 0.04 0.02 -14.94 0.1 0.06 0.656 0.02 0.012
2019-03-07
R1 -6.35 -14.82 0.658 0.103 0.097
15:28
2019-03-11
R2 -6.4 -15.01 0.635 0.124 -0.007
01:57
2019-03-16
R3 -6.42 -14.99 0.675 0.132 0.198
23:01
S14 JMF12 C -7.45 0.04 0.02 -15.19 0.03 0.02 0.667 0.021 0.012
2019-03-07
R1 -7.49 -15.22 0.645 0.063 0.108
17:47
2019-03-11
R2 -7.41 -15.16 0.668 0.121 -0.019
11:00
2019-03-16
R3 -7.44 -15.18 0.688 0.141 0.262
05:51
S15 JMG 1 1 2.9 0.08 0.05 -2.68 0.11 0.07 0.513 0.002 0.001
2019-03-27
R1 2.88 -2.67 0.511 0.135 -0.176
01:58
2019-03-29
R2 3 -2.57 0.513 0.168 -0.196
13:17
2019-04-09
R3 2.83 -2.8 0.515 0.201 0.047
13:00
S16 JMG 1 2 2.93 0.05 0.03 -3.63 0.16 0.09 0.528 0.012 0.007
2019-03-27
R1 2.94 -3.71 0.541 0.137 -0.164
03:59
2019-03-29
R2 2.98 -3.44 0.524 0.128 -0.024
15:24
2019-04-09
R3 2.88 -3.73 0.518 0.205 -0.032
15:08
S17 JMG 1 3 0.46 0.21 0.12 -10.66 0.15 0.09 0.587 0.037 0.021
Appendix

2019-03-27
R1 0.55 -10.51 0.582 0.129 -0.126
05:58
2019-03-29
R2 0.61 -10.67 0.553 0.118 -0.007
17:29
2019-04-09
R3 0.23 -10.81 0.626 0.233 0.185
17:08
S18 JMG 1 4 0.45 0.14 0.08 -11.53 0.04 0.02 0.602 0.032 0.019
2019-03-27
R1 0.57 -11.53 0.583 0.136 0.024
10:04
2019-03-29
R2 0.5 -11.49 0.639 0.131 0.096
21:40
2019-04-09
R3 0.29 -11.57 0.584 0.196 0.025
21:15
S19 JMG 1 5 0.74 0.12 0.07 -10.93 0.01 0.01 0.601 0.026 0.015
2019-03-27
R1 0.84 -10.92 0.573 0.133 -0.052
12:10
2019-03-29
R2 0.77 -10.92 0.604 0.132 0.136
23:42
2019-04-09
R3 0.61 -10.95 0.625 0.209 0.075
23:24
S20 JMG 1 A 2.59 0.08 0.05 -4.46 0.07 0.04 0.558 0.032 0.019
2019-03-07
R1 2.51 -4.54 0.549 0.154 -0.049
19:48
2019-03-10
R2 2.67 -4.39 0.531 0.194 -0.17
21:11
2019-03-16
R3 2.6 -4.46 0.593 0.184 0.235
01:34
S21 JMG 1 B 0.52 0.03 0.02 -12.13 0.04 0.02 0.586 0.006 0.003
2019-03-08
R1 0.48 -12.13 0.586 0.131 -0.023
04:29
2019-03-11
R2 0.54 -12.17 0.581 0.142 -0.186
06:30
2019-03-16
R3 0.54 -12.1 0.592 0.186 0.082
14:19
Appendix

Sample 9 Be [ He ] 11 B [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0 N/A 20.905 35.2
10:40
JMF1-2.d 8/1/2019 Sample 0 N/A 15.004 28.3
10:43
JMF1-3.d 8/1/2019 Sample 0 N/A 4.413 57
10:47
JMF1-A.d 8/1/2019 Sample 0 N/A 9.083 46.1
10:50
JMF1-B.d 8/1/2019 Sample 0 N/A 13.187 55.2
10:54
JMF1-C.d 8/1/2019 Sample 0.209 173.2 6.764 88.6
10:57
JMF12-1.d 8/1/2019 Sample 0.177 173.2 0.98 769.9
11:01
JMF12-2.d 8/1/2019 Sample 0.354 173.2 5.794 67.4
11:04
JMF12-3.d 8/1/2019 Sample 0.164 173.2 3.184 213
11:08
JMF12-4.d 8/1/2019 Sample 0 N/A 4.418 57.8
11:11
JMF12-5.d 8/1/2019 Sample 0.219 173.2 1.797 138.8
11:15
JMF12-A.d 8/13/2019 Sample 0 N/A 20.706 35.8
16:30
JMF12-B.d 8/13/2019 Sample 0.423 91.5 16.424 47
16:33
JMF12-C.d 8/13/2019 Sample 0.127 173.2 6.314 85.3
16:37
JMG1-1.d 8/13/2019 Sample 0.186 173.2 3.047 213.9
16:40
JMG1-2.d 8/13/2019 Sample 0.175 173.2 2.723 63
16:44
JMG1-3.d 8/13/2019 Sample 0 N/A 1.552 339.7
16:47
JMG1-4.d 8/13/2019 Sample 0.324 89.4 5.852 16.7
16:51
JMG1-5.d 8/13/2019 Sample 0 N/A 4.545 24.1
16:54
JMG1-A.d 8/13/2019 Sample 0.153 173.2 8.812 3.1
16:58
JMG1-B.d 8/13/2019 Sample 0 N/A 2.341 212.4
17:02
Appendix

Sample 23 Na [ He ] 24 Mg [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppm ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample <0.000 N/A 0.181 3.5
10:40
JMF1-2.d 8/1/2019 Sample <0.000 N/A 0.216 2.6
10:43
JMF1-3.d 8/1/2019 Sample <0.000 N/A 0.194 1.8
10:47
JMF1-A.d 8/1/2019 Sample <0.000 N/A 0.231 4.2
10:50
JMF1-B.d 8/1/2019 Sample <0.000 N/A 0.199 0.6
10:54
JMF1-C.d 8/1/2019 Sample <0.000 N/A 0.24 3.8
10:57
JMF12-1.d 8/1/2019 Sample <0.000 N/A 0.546 2
11:01
JMF12-2.d 8/1/2019 Sample <0.000 N/A 0.505 2.2
11:04
JMF12-3.d 8/1/2019 Sample <0.000 N/A 0.51 3
11:08
JMF12-4.d 8/1/2019 Sample <0.000 N/A 0.481 1.9
11:11
JMF12-5.d 8/1/2019 Sample <0.000 N/A 0.68 3
11:15
JMF12-A.d 8/13/2019 Sample <0.000 N/A 0.501 2
16:30
JMF12-B.d 8/13/2019 Sample <0.000 N/A 0.362 1.7
16:33
JMF12-C.d 8/13/2019 Sample <0.000 N/A 0.482 7.3
16:37
JMG1-1.d 8/13/2019 Sample <0.000 N/A 0.231 1.4
16:40
JMG1-2.d 8/13/2019 Sample <0.000 N/A 0.139 2.9
16:44
JMG1-3.d 8/13/2019 Sample <0.000 N/A 0.334 5.4
16:47
JMG1-4.d 8/13/2019 Sample <0.000 N/A 0.291 1.5
16:51
JMG1-5.d 8/13/2019 Sample <0.000 N/A 0.173 5
16:54
JMG1-A.d 8/13/2019 Sample <0.000 N/A 0.157 2.7
16:58
JMG1-B.d 8/13/2019 Sample <0.000 N/A 0.211 7.1
17:02
Appendix

Sample 27 Al [ He ] 31 P [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 4.775 26 <0.000 N/A
10:40
JMF1-2.d 8/1/2019 Sample 6.609 12.8 <0.000 N/A
10:43
JMF1-3.d 8/1/2019 Sample 13.994 8.2 <0.000 N/A
10:47
JMF1-A.d 8/1/2019 Sample 5.383 21.6 <0.000 N/A
10:50
JMF1-B.d 8/1/2019 Sample 14.853 18.2 <0.000 N/A
10:54
JMF1-C.d 8/1/2019 Sample 35.858 6.5 <0.000 N/A
10:57
JMF12-1.d 8/1/2019 Sample 10.619 5.7 <0.000 N/A
11:01
JMF12-2.d 8/1/2019 Sample 2.862 50.4 <0.000 N/A
11:04
JMF12-3.d 8/1/2019 Sample 3.887 50.5 <0.000 N/A
11:08
JMF12-4.d 8/1/2019 Sample 16.791 12.7 <0.000 N/A
11:11
JMF12-5.d 8/1/2019 Sample 23.43 9.5 <0.000 N/A
11:15
JMF12-A.d 8/13/2019 Sample 17.615 4.2 6.312 35.4
16:30
JMF12-B.d 8/13/2019 Sample 11.076 8.2 4.827 294.4
16:33
JMF12-C.d 8/13/2019 Sample 9.598 9.3 13.947 93.2
16:37
JMG1-1.d 8/13/2019 Sample 5.974 9.2 18.037 22.4
16:40
JMG1-2.d 8/13/2019 Sample 6.161 23.8 9.509 97.4
16:44
JMG1-3.d 8/13/2019 Sample 59.476 0.3 17.583 71.9
16:47
JMG1-4.d 8/13/2019 Sample 25.248 5.8 13.671 49.6
16:51
JMG1-5.d 8/13/2019 Sample 8.955 29.9 15.229 65
16:54
JMG1-A.d 8/13/2019 Sample 0.946 81.2 10.396 111.7
16:58
JMG1-B.d 8/13/2019 Sample 6.463 23.6 16 83.7
17:02
Appendix

Sample 39 K [ He ] 43 Ca [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppm ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample <0.000 N/A 37.166 5.5
10:40
JMF1-2.d 8/1/2019 Sample 14.994 97.8 42.292 0.8
10:43
JMF1-3.d 8/1/2019 Sample <0.000 N/A 41.933 2
10:47
JMF1-A.d 8/1/2019 Sample 211.702 6.2 47.797 5.3
10:50
JMF1-B.d 8/1/2019 Sample 42.353 17.6 38.752 2.1
10:54
JMF1-C.d 8/1/2019 Sample 8 82.5 46.334 1.7
10:57
JMF12-1.d 8/1/2019 Sample <0.000 N/A 43.816 1.9
11:01
JMF12-2.d 8/1/2019 Sample <0.000 N/A 47.162 4.1
11:04
JMF12-3.d 8/1/2019 Sample <0.000 N/A 37.929 3.2
11:08
JMF12-4.d 8/1/2019 Sample <0.000 N/A 35.138 3.7
11:11
JMF12-5.d 8/1/2019 Sample 55.632 42.6 38.286 1.2
11:15
JMF12-A.d 8/13/2019 Sample <0.000 N/A 38.190 2.1
16:30
JMF12-B.d 8/13/2019 Sample <0.000 N/A 41.203 5.8
16:33
JMF12-C.d 8/13/2019 Sample <0.000 N/A 54.245 1.9
16:37
JMG1-1.d 8/13/2019 Sample <0.000 N/A 40.136 4
16:40
JMG1-2.d 8/13/2019 Sample 11.553 31.8 38.815 1.7
16:44
JMG1-3.d 8/13/2019 Sample 13.113 140.1 38.897 2.2
16:47
JMG1-4.d 8/13/2019 Sample <0.000 N/A 49.137 2.1
16:51
JMG1-5.d 8/13/2019 Sample <0.000 N/A 38.831 1.3
16:54
JMG1-A.d 8/13/2019 Sample <0.000 N/A 38.865 3.7
16:58
JMG1-B.d 8/13/2019 Sample <0.000 N/A 37.589 3.9
17:02
Appendix

Sample 44 Ca [ He ] 51 V [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppm ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 36.737 2.3 0.067 23.8
10:40
JMF1-2.d 8/1/2019 Sample 41.461 2.4 0.03 12.3
10:43
JMF1-3.d 8/1/2019 Sample 41.146 1 1.208 10.5
10:47
JMF1-A.d 8/1/2019 Sample 47.62 2.6 0.018 77.1
10:50
JMF1-B.d 8/1/2019 Sample 38.332 2.3 0.126 23.1
10:54
JMF1-C.d 8/1/2019 Sample 45.423 1.7 0.335 5.9
10:57
JMF12-1.d 8/1/2019 Sample 43.559 0.8 0.023 81.7
11:01
JMF12-2.d 8/1/2019 Sample 45.54 3.2 0.011 137.9
11:04
JMF12-3.d 8/1/2019 Sample 35.788 0.2 0.003 635
11:08
JMF12-4.d 8/1/2019 Sample 34.978 1.7 0.018 52.3
11:11
JMF12-5.d 8/1/2019 Sample 37.251 2.7 0.071 17.4
11:15
JMF12-A.d 8/13/2019 Sample 37.892 1.5 0.037 56.2
16:30
JMF12-B.d 8/13/2019 Sample 41.400 2 0.094 21
16:33
JMF12-C.d 8/13/2019 Sample 54.890 1.8 0.036 4.9
16:37
JMG1-1.d 8/13/2019 Sample 40.423 2.1 0.113 17.4
16:40
JMG1-2.d 8/13/2019 Sample 38.485 3.1 0.172 15
16:44
JMG1-3.d 8/13/2019 Sample 39.141 0.6 0.129 8.5
16:47
JMG1-4.d 8/13/2019 Sample 48.196 1.8 0.064 60.4
16:51
JMG1-5.d 8/13/2019 Sample 38.873 1.3 0.018 35.8
16:54
JMG1-A.d 8/13/2019 Sample 38.491 1.7 0.069 36.1
16:58
JMG1-B.d 8/13/2019 Sample 37.862 0.3 0.041 34.4
17:02
Appendix

Sample 52 Cr [ He ] 55 Mn [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0.349 23.6 4.866 6
10:40
JMF1-2.d 8/1/2019 Sample 0.544 5 1.138 8.2
10:43
JMF1-3.d 8/1/2019 Sample 0.424 13.5 53.143 3.3
10:47
JMF1-A.d 8/1/2019 Sample 0.442 8.1 0.733 13.4
10:50
JMF1-B.d 8/1/2019 Sample 0.356 16.8 30.145 3.6
10:54
JMF1-C.d 8/1/2019 Sample 0.595 15.5 12.67 1.8
10:57
JMF12-1.d 8/1/2019 Sample 0.473 7.2 1.767 63
11:01
JMF12-2.d 8/1/2019 Sample 0.435 19 0.417 11.6
11:04
JMF12-3.d 8/1/2019 Sample 0.415 26.5 0.176 20.5
11:08
JMF12-4.d 8/1/2019 Sample 0.5 1.1 1.083 16
11:11
JMF12-5.d 8/1/2019 Sample 1.215 13.8 1.291 13.6
11:15
JMF12-A.d 8/13/2019 Sample 0.92 7.2 0.723 6.8
16:30
JMF12-B.d 8/13/2019 Sample 0.102 75.7 20.628 1
16:33
JMF12-C.d 8/13/2019 Sample 0.151 13.2 2.126 14.1
16:37
JMG1-1.d 8/13/2019 Sample 0.203 32.1 22.644 4
16:40
JMG1-2.d 8/13/2019 Sample 0.243 23.1 17.069 2.4
16:44
JMG1-3.d 8/13/2019 Sample 0.366 22.2 19.936 8
16:47
JMG1-4.d 8/13/2019 Sample 0.209 27 19.338 2.7
16:51
JMG1-5.d 8/13/2019 Sample 0.094 104.6 15.232 2.3
16:54
JMG1-A.d 8/13/2019 Sample 0.197 36.3 17.707 2
16:58
JMG1-B.d 8/13/2019 Sample 0.151 81.4 15.166 6.3
17:02
Appendix

Sample 56 Fe [ He ] 59 Co [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 12.62 4.2 0.054 7.5
10:40
JMF1-2.d 8/1/2019 Sample 75.866 3.5 0.01 125.8
10:43
JMF1-3.d 8/1/2019 Sample 97.828 1.7 0.233 11.2
10:47
JMF1-A.d 8/1/2019 Sample 20.335 2.3 0.077 21.1
10:50
JMF1-B.d 8/1/2019 Sample 34.675 1.8 0.13 12.5
10:54
JMF1-C.d 8/1/2019 Sample 32.516 4.7 0.069 35.7
10:57
JMF12-1.d 8/1/2019 Sample 30.053 1.5 0.021 101.2
11:01
JMF12-2.d 8/1/2019 Sample 8.551 4.8 0.016 92.4
11:04
JMF12-3.d 8/1/2019 Sample 4.243 4.1 0.006 10.6
11:08
JMF12-4.d 8/1/2019 Sample 15.091 6.1 0.028 12.9
11:11
JMF12-5.d 8/1/2019 Sample 30.187 4.3 0.096 20.3
11:15
JMF12-A.d 8/13/2019 Sample 16.886 5.7 0.039 21.6
16:30
JMF12-B.d 8/13/2019 Sample 28.241 2.4 0.357 7.6
16:33
JMF12-C.d 8/13/2019 Sample 12.724 4 0.042 30.3
16:37
JMG1-1.d 8/13/2019 Sample 8.973 5.3 0.018 21.2
16:40
JMG1-2.d 8/13/2019 Sample 9.796 6.8 0.043 20.9
16:44
JMG1-3.d 8/13/2019 Sample 67.479 2.8 0.125 9.7
16:47
JMG1-4.d 8/13/2019 Sample 21.878 1.3 0.044 6.6
16:51
JMG1-5.d 8/13/2019 Sample 10.809 7.7 0.003 348.1
16:54
JMG1-A.d 8/13/2019 Sample 4.724 4.9 0.008 33.6
16:58
JMG1-B.d 8/13/2019 Sample 15.165 6.3 0.02 21.3
17:02
Appendix

Sample 60 Ni [ He ] 63 Cu [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0.6 13.2 0.245 17.5
10:40
JMF1-2.d 8/1/2019 Sample 0.287 62.1 0.63 11.7
10:43
JMF1-3.d 8/1/2019 Sample 0.488 15.7 2.406 2.4
10:47
JMF1-A.d 8/1/2019 Sample 0.694 20.8 0.661 8.7
10:50
JMF1-B.d 8/1/2019 Sample 0.375 2.7 0.542 2.7
10:54
JMF1-C.d 8/1/2019 Sample 0.505 19 1.946 7.8
10:57
JMF12-1.d 8/1/2019 Sample 0.984 16 1.856 1.4
11:01
JMF12-2.d 8/1/2019 Sample 0.227 39.8 0.011 299.1
11:04
JMF12-3.d 8/1/2019 Sample 0.688 87.1 0.183 8.7
11:08
JMF12-4.d 8/1/2019 Sample 0.577 13.8 0.095 51.1
11:11
JMF12-5.d 8/1/2019 Sample 1.001 23.1 2.066 1.4
11:15
JMF12-A.d 8/13/2019 Sample 0.818 5 0.189 13.5
16:30
JMF12-B.d 8/13/2019 Sample 1.309 13.8 0.355 15.2
16:33
JMF12-C.d 8/13/2019 Sample 1.069 8.5 0.346 4.9
16:37
JMG1-1.d 8/13/2019 Sample 1.208 1.9 0.837 3.3
16:40
JMG1-2.d 8/13/2019 Sample 3.783 6.3 0.15 15.3
16:44
JMG1-3.d 8/13/2019 Sample 1.834 5 0.278 19.8
16:47
JMG1-4.d 8/13/2019 Sample 0.555 14.4 0.271 22.2
16:51
JMG1-5.d 8/13/2019 Sample 0.531 12.8 0.289 13.5
16:54
JMG1-A.d 8/13/2019 Sample 1.27 4.1 0.194 11.9
16:58
JMG1-B.d 8/13/2019 Sample 2.668 6.2 0.073 22.7
17:02
Appendix

Sample 66 Zn [ He ] 71 Ga [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 1.616 16.2 0.019 173.2
10:40
JMF1-2.d 8/1/2019 Sample 5.466 6.5 0.02 101.4
10:43
JMF1-3.d 8/1/2019 Sample 1.692 5.4 0.037 132.6
10:47
JMF1-A.d 8/1/2019 Sample 4.459 9.6 0.053 114.5
10:50
JMF1-B.d 8/1/2019 Sample 2.745 10.6 0.006 173.2
10:54
JMF1-C.d 8/1/2019 Sample 4.557 4.7 0.038 98.5
10:57
JMF12-1.d 8/1/2019 Sample 4.245 3.9 0.03 71.3
11:01
JMF12-2.d 8/1/2019 Sample 8.641 2.7 0.038 173.2
11:04
JMF12-3.d 8/1/2019 Sample 3.437 13 0.026 42.6
11:08
JMF12-4.d 8/1/2019 Sample 4.281 3.5 0.019 173.2
11:11
JMF12-5.d 8/1/2019 Sample 6.19 10.5 0.04 94.7
11:15
JMF12-A.d 8/13/2019 Sample 4.186 3.5 0 3331
16:30
JMF12-B.d 8/13/2019 Sample 7.819 4.7 0.001 1269.6
16:33
JMF12-C.d 8/13/2019 Sample 14.01 3.3 <0.000 N/A
16:37
JMG1-1.d 8/13/2019 Sample 0.261 116.2 <0.000 N/A
16:40
JMG1-2.d 8/13/2019 Sample <0.000 N/A 0.025 122.6
16:44
JMG1-3.d 8/13/2019 Sample 0.968 29.8 0.061 32.9
16:47
JMG1-4.d 8/13/2019 Sample 2.267 22.4 0.028 81.9
16:51
JMG1-5.d 8/13/2019 Sample <0.000 N/A <0.000 N/A
16:54
JMG1-A.d 8/13/2019 Sample 0.164 176 0.011 71.7
16:58
JMG1-B.d 8/13/2019 Sample <0.000 N/A 0.002 792.8
17:02
Appendix

Sample 72 Ge [ He ] 75 As [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0.75 69.4 2.135 17.8
10:40
JMF1-2.d 8/1/2019 Sample 0.481 98 2.379 4.3
10:43
JMF1-3.d 8/1/2019 Sample 0.854 93 3.56 1.1
10:47
JMF1-A.d 8/1/2019 Sample 1.809 88.5 2.064 5.1
10:50
JMF1-B.d 8/1/2019 Sample 1.261 23.4 2.426 6.9
10:54
JMF1-C.d 8/1/2019 Sample 1.87 90.4 2.557 5.3
10:57
JMF12-1.d 8/1/2019 Sample 0.682 35.5 1.793 11.7
11:01
JMF12-2.d 8/1/2019 Sample 0.437 106.9 2.19 5.7
11:04
JMF12-3.d 8/1/2019 Sample 0.602 41.9 1.922 4.8
11:08
JMF12-4.d 8/1/2019 Sample 1.007 24.1 9.908 141.8
11:11
JMF12-5.d 8/1/2019 Sample 0.429 146.4 2.299 1.5
11:15
JMF12-A.d 8/13/2019 Sample 0.671 48.2 1.687 8
16:30
JMF12-B.d 8/13/2019 Sample 0.172 317.8 1.923 11.9
16:33
JMF12-C.d 8/13/2019 Sample <0.000 N/A 1.543 14.1
16:37
JMG1-1.d 8/13/2019 Sample <0.000 N/A 1.387 9
16:40
JMG1-2.d 8/13/2019 Sample 1.041 80.3 1.514 11.4
16:44
JMG1-3.d 8/13/2019 Sample 0.999 49.5 1.523 2.6
16:47
JMG1-4.d 8/13/2019 Sample 1.133 67.4 1.367 11.2
16:51
JMG1-5.d 8/13/2019 Sample 0.58 90.4 1.179 11.4
16:54
JMG1-A.d 8/13/2019 Sample 0.43 141.9 1.386 10.7
16:58
JMG1-B.d 8/13/2019 Sample 0.222 352.3 1.576 4.9
17:02
Appendix

Sample 78 Se [ He ] 85 Rb [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 1.235 51.3 0.08 43.7
10:40
JMF1-2.d 8/1/2019 Sample 0.62 170.2 0.179 35.7
10:43
JMF1-3.d 8/1/2019 Sample 0.857 30.2 0.089 53.2
10:47
JMF1-A.d 8/1/2019 Sample 0.567 234.8 0.069 30.3
10:50
JMF1-B.d 8/1/2019 Sample 0.819 84.9 0.066 98.8
10:54
JMF1-C.d 8/1/2019 Sample 0.647 68.8 0.127 11.2
10:57
JMF12-1.d 8/1/2019 Sample 0.262 236.3 0.047 17.3
11:01
JMF12-2.d 8/1/2019 Sample 0.355 142.7 0.064 58.3
11:04
JMF12-3.d 8/1/2019 Sample 0.647 114.2 0.025 317.2
11:08
JMF12-4.d 8/1/2019 Sample 0.695 191.2 0.062 178.1
11:11
JMF12-5.d 8/1/2019 Sample 1.019 102.1 0.116 68.5
11:15
JMF12-A.d 8/13/2019 Sample 0.682 146.7 0.017 174.1
16:30
JMF12-B.d 8/13/2019 Sample 0.041 2548.1 0.048 135.1
16:33
JMF12-C.d 8/13/2019 Sample <0.000 N/A 0.053 30.9
16:37
JMG1-1.d 8/13/2019 Sample 0.132 730.4 0.054 92.5
16:40
JMG1-2.d 8/13/2019 Sample <0.000 N/A <0.000 N/A
16:44
JMG1-3.d 8/13/2019 Sample <0.000 N/A 0.135 9.6
16:47
JMG1-4.d 8/13/2019 Sample 0.956 12.7 0.065 71
16:51
JMG1-5.d 8/13/2019 Sample <0.000 N/A <0.000 N/A
16:54
JMG1-A.d 8/13/2019 Sample <0.000 N/A 0.002 2291.4
16:58
JMG1-B.d 8/13/2019 Sample <0.000 N/A 0.048 5.2
17:02
Appendix

Sample 88 Sr [ He ] 95 Mo [ He ]
Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 13.297 3.7 77.866 112.5
10:40
JMF1-2.d 8/1/2019 Sample 19.826 4.8 36.928 208.3
10:43
JMF1-3.d 8/1/2019 Sample 65.432 3 51.344 76.3
10:47
JMF1-A.d 8/1/2019 Sample 19.094 3.1 46.651 162
10:50
JMF1-B.d 8/1/2019 Sample 31.27 2.2 67.898 50.9
10:54
JMF1-C.d 8/1/2019 Sample 30.999 0.5 44.332 126.3
10:57
JMF12-1.d 8/1/2019 Sample 12.856 2.3 38.455 96.4
11:01
JMF12-2.d 8/1/2019 Sample 20.617 2.5 <0.000 N/A
11:04
JMF12-3.d 8/1/2019 Sample 18.204 2.7 7.949 659.3
11:08
JMF12-4.d 8/1/2019 Sample 12.664 3 <0.000 N/A
11:11
JMF12-5.d 8/1/2019 Sample 27.437 3.9 46.469 87.9
11:15
JMF12-A.d 8/13/2019 Sample 14.974 1.1 36.342 149.5
16:30
JMF12-B.d 8/13/2019 Sample 14.476 3.1 20.175 107.3
16:33
JMF12-C.d 8/13/2019 Sample 13.892 2.6 26.401 117.7
16:37
JMG1-1.d 8/13/2019 Sample 21.152 3.6 <0.000 N/A
16:40
JMG1-2.d 8/13/2019 Sample 15.241 1.9 <0.000 N/A
16:44
JMG1-3.d 8/13/2019 Sample 49.673 0.7 88.47 20.3
16:47
JMG1-4.d 8/13/2019 Sample 56.275 1.1 <0.000 N/A
16:51
JMG1-5.d 8/13/2019 Sample 31.229 1.2 <0.000 N/A
16:54
JMG1-A.d 8/13/2019 Sample 16.871 1.1 <0.000 0
16:58
JMG1-B.d 8/13/2019 Sample 46.912 2.3 <0.000 N/A
17:02
Appendix

Sample 105 Pd [ He ] 107 Ag [ He ]

Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 328.892 176.6 <0.000 N/A
10:40
JMF1-2.d 8/1/2019 Sample 305.798 240.4 <0.000 N/A
10:43
JMF1-3.d 8/1/2019 Sample <0.000 N/A <0.000 N/A
10:47
JMF1-A.d 8/1/2019 Sample <0.000 N/A 0.012 100.1
10:50
JMF1-B.d 8/1/2019 Sample <0.000 N/A <0.000 N/A
10:54
JMF1-C.d 8/1/2019 Sample <0.000 N/A <0.000 N/A
10:57
JMF12-1.d 8/1/2019 Sample 381.165 70.5 <0.000 N/A
11:01
JMF12-2.d 8/1/2019 Sample 216.523 218 <0.000 N/A
11:04
JMF12-3.d 8/1/2019 Sample <0.000 N/A <0.000 N/A
11:08
JMF12-4.d 8/1/2019 Sample <0.000 N/A <0.000 N/A
11:11
JMF12-5.d 8/1/2019 Sample 213.215 97.5 <0.000 N/A
11:15
JMF12-A.d 8/13/2019 Sample <0.000 N/A 0.016 54.5
16:30
JMF12-B.d 8/13/2019 Sample 67.977 550.7 0.028 27.7
16:33
JMF12-C.d 8/13/2019 Sample 335.949 72.4 0.026 39.8
16:37
JMG1-1.d 8/13/2019 Sample 397.636 119.1 0.009 83.1
16:40
JMG1-2.d 8/13/2019 Sample <0.000 N/A 0.013 81.4
16:44
JMG1-3.d 8/13/2019 Sample <0.000 N/A <0.000 N/A
16:47
JMG1-4.d 8/13/2019 Sample 302.525 168.2 <0.000 N/A
16:51
JMG1-5.d 8/13/2019 Sample 593.997 166.3 <0.000 N/A
16:54
JMG1-A.d 8/13/2019 Sample 64.409 186 <0.000 N/A
16:58
JMG1-B.d 8/13/2019 Sample <0.000 N/A 0.004 82.9
17:02
Appendix

Sample 111 Cd [ He ] 133 Cs [ He ]

Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0.121 49.9 <0.000 N/A
10:40
JMF1-2.d 8/1/2019 Sample 0.163 10.7 0.022 33.1
10:43
JMF1-3.d 8/1/2019 Sample 0.11 65.7 <0.000 N/A
10:47
JMF1-A.d 8/1/2019 Sample 0.157 19.5 0.042 311.1
10:50
JMF1-B.d 8/1/2019 Sample 0.054 41.5 <0.000 N/A
10:54
JMF1-C.d 8/1/2019 Sample 0.127 16.4 <0.000 N/A
10:57
JMF12-1.d 8/1/2019 Sample 0.026 173.2 <0.000 N/A
11:01
JMF12-2.d 8/1/2019 Sample 0.014 173.2 <0.000 N/A
11:04
JMF12-3.d 8/1/2019 Sample 0.013 173.2 <0.000 N/A
11:08
JMF12-4.d 8/1/2019 Sample 0.006 173.2 <0.000 N/A
11:11
JMF12-5.d 8/1/2019 Sample 0 N/A 0.026 18.5
11:15
JMF12-A.d 8/13/2019 Sample 0.016 173.2 0.032 49.6
16:30
JMF12-B.d 8/13/2019 Sample 0.115 32.8 0.022 107.9
16:33
JMF12-C.d 8/13/2019 Sample 0.068 51.3 0.021 159.5
16:37
JMG1-1.d 8/13/2019 Sample 0.038 113.3 0.023 116.2
16:40
JMG1-2.d 8/13/2019 Sample 0.009 173.2 0.041 117.9
16:44
JMG1-3.d 8/13/2019 Sample 0.009 173.2 0.049 43.8
16:47
JMG1-4.d 8/13/2019 Sample 0.013 173.2 0.02 167.1
16:51
JMG1-5.d 8/13/2019 Sample 0.025 100.4 0.003 429.3
16:54
JMG1-A.d 8/13/2019 Sample 0.018 86.6 0.005 199.1
16:58
JMG1-B.d 8/13/2019 Sample 0 N/A 0.055 2.6
17:02
Appendix

Sample 137 Ba [ He ] 140 Ce [ He ]

Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 1.82 5.2 0.023 24.6
10:40
JMF1-2.d 8/1/2019 Sample 1.898 12.6 0.012 44.9
10:43
JMF1-3.d 8/1/2019 Sample 31.593 1.5 0.04 6.6
10:47
JMF1-A.d 8/1/2019 Sample 1.61 9.4 0.023 17.7
10:50
JMF1-B.d 8/1/2019 Sample 33.572 3.1 0.017 7.9
10:54
JMF1-C.d 8/1/2019 Sample 42.145 4.6 0.17 4.5
10:57
JMF12-1.d 8/1/2019 Sample 1.737 6.5 0.017 40.4
11:01
JMF12-2.d 8/1/2019 Sample 1.493 6.8 0.012 34.9
11:04
JMF12-3.d 8/1/2019 Sample 0.861 27.1 0.007 77.2
11:08
JMF12-4.d 8/1/2019 Sample 1.793 10.5 0.014 43.4
11:11
JMF12-5.d 8/1/2019 Sample 2.981 10.4 0.036 28.3
11:15
JMF12-A.d 8/13/2019 Sample 2.757 8.3 0.012 50.6
16:30
JMF12-B.d 8/13/2019 Sample 4.913 5.3 0.031 4.4
16:33
JMF12-C.d 8/13/2019 Sample 3.248 12 0.015 8.9
16:37
JMG1-1.d 8/13/2019 Sample 0.438 4.6 0.037 25.3
16:40
JMG1-2.d 8/13/2019 Sample 1.185 5.6 0.637 3.7
16:44
JMG1-3.d 8/13/2019 Sample 8.617 5.6 0.653 1.7
16:47
JMG1-4.d 8/13/2019 Sample 3.921 3.4 0.304 5.6
16:51
JMG1-5.d 8/13/2019 Sample 1.532 1.7 0.042 5.6
16:54
JMG1-A.d 8/13/2019 Sample 0.267 48.8 0.087 10.1
16:58
JMG1-B.d 8/13/2019 Sample 0.346 6.4 0.279 4.5
17:02
Appendix

Sample 141 Pr [ He ] 146 Nd [ He ]

Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0.005 57.7 0.024 101
10:40
JMF1-2.d 8/1/2019 Sample 0.006 60 0.026 78.2
10:43
JMF1-3.d 8/1/2019 Sample 0.009 50.5 0.046 38.6
10:47
JMF1-A.d 8/1/2019 Sample 0.014 25.1 0.079 44.9
10:50
JMF1-B.d 8/1/2019 Sample 0.012 14.6 0.034 26.7
10:54
JMF1-C.d 8/1/2019 Sample 0.032 39.7 0.176 8.9
10:57
JMF12-1.d 8/1/2019 Sample 0.002 48.7 0.028 34.9
11:01
JMF12-2.d 8/1/2019 Sample <0.000 N/A <0.000 N/A
11:04
JMF12-3.d 8/1/2019 Sample <0.000 N/A <0.000 N/A
11:08
JMF12-4.d 8/1/2019 Sample 0.004 80.3 0.017 105.5
11:11
JMF12-5.d 8/1/2019 Sample 0.003 115.2 0.022 110.5
11:15
JMF12-A.d 8/13/2019 Sample 0.002 49.6 0.011 50.4
16:30
JMF12-B.d 8/13/2019 Sample 0.012 30.7 0.078 13.2
16:33
JMF12-C.d 8/13/2019 Sample 0.006 10.1 0.018 32.9
16:37
JMG1-1.d 8/13/2019 Sample 0.005 42.4 0.029 84
16:40
JMG1-2.d 8/13/2019 Sample 0.121 15.2 0.561 4.1
16:44
JMG1-3.d 8/13/2019 Sample 0.087 3.4 0.369 17.5
16:47
JMG1-4.d 8/13/2019 Sample 0.04 10.5 0.203 15.9
16:51
JMG1-5.d 8/13/2019 Sample 0.007 22.4 0.023 14.8
16:54
JMG1-A.d 8/13/2019 Sample 0.019 7.7 0.081 27
16:58
JMG1-B.d 8/13/2019 Sample 0.042 16.4 0.195 23.5
17:02
Appendix

Sample 147 Sm [ He ] 153 Eu [ He ]

Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0.018 92.2 0.001 355.4
10:40
JMF1-2.d 8/1/2019 Sample 0.004 173.2 <0.000 N/A
10:43
JMF1-3.d 8/1/2019 Sample 0.007 86.6 0.002 401.2
10:47
JMF1-A.d 8/1/2019 Sample 0.041 41 0.007 79.6
10:50
JMF1-B.d 8/1/2019 Sample 0.014 115.1 0.005 157.7
10:54
JMF1-C.d 8/1/2019 Sample 0.039 43.6 0.012 20.9
10:57
JMF12-1.d 8/1/2019 Sample 0 N/A <0.000 N/A
11:01
JMF12-2.d 8/1/2019 Sample 0.004 173.2 <0.000 N/A
11:04
JMF12-3.d 8/1/2019 Sample 0.004 173.2 0.002 100.8
11:08
JMF12-4.d 8/1/2019 Sample 0.017 124.9 0.001 412.8
11:11
JMF12-5.d 8/1/2019 Sample 0.004 173.2 0 3150
11:15
JMF12-A.d 8/13/2019 Sample 0 4256 0 11921.4
16:30
JMF12-B.d 8/13/2019 Sample 0.011 103.9 0.006 55.8
16:33
JMF12-C.d 8/13/2019 Sample 0.017 73.4 0.004 107.3
16:37
JMG1-1.d 8/13/2019 Sample 0.021 84.2 0.004 91.3
16:40
JMG1-2.d 8/13/2019 Sample 0.281 11 0.06 13.2
16:44
JMG1-3.d 8/13/2019 Sample 0.104 36.5 0.023 30.5
16:47
JMG1-4.d 8/13/2019 Sample 0.092 14.6 0.017 49.5
16:51
JMG1-5.d 8/13/2019 Sample 0.012 74 0.003 58.2
16:54
JMG1-A.d 8/13/2019 Sample 0.05 55.3 0.012 31.8
16:58
JMG1-B.d 8/13/2019 Sample 0.057 30.1 0.028 9.5
17:02
Appendix

Sample 157 Gd [ He ] 163 Dy [ He ]

Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0.004 86.7 0.002 173.2
10:40
JMF1-2.d 8/1/2019 Sample 0.013 52.5 0.011 53.1
10:43
JMF1-3.d 8/1/2019 Sample 0.008 43.8 0.015 33.6
10:47
JMF1-A.d 8/1/2019 Sample 0.024 41.6 0.014 77.6
10:50
JMF1-B.d 8/1/2019 Sample 0.017 43.8 0.004 86.6
10:54
JMF1-C.d 8/1/2019 Sample 0.037 60.6 0.023 49.5
10:57
JMF12-1.d 8/1/2019 Sample 0.002 173.2 0.008 33.3
11:01
JMF12-2.d 8/1/2019 Sample 0.002 173.2 0.002 173.2
11:04
JMF12-3.d 8/1/2019 Sample 0.008 40.8 0.005 101.4
11:08
JMF12-4.d 8/1/2019 Sample 0.004 86.7 0.007 86.7
11:11
JMF12-5.d 8/1/2019 Sample 0.007 96.2 0.006 99.9
11:15
JMF12-A.d 8/13/2019 Sample 0.005 114.5 0.004 43
16:30
JMF12-B.d 8/13/2019 Sample 0.022 1.7 0.021 51.4
16:33
JMF12-C.d 8/13/2019 Sample 0.006 124.7 0.008 41.6
16:37
JMG1-1.d 8/13/2019 Sample 0.018 51.5 0.015 32.6
16:40
JMG1-2.d 8/13/2019 Sample 0.269 7.5 0.285 12.7
16:44
JMG1-3.d 8/13/2019 Sample 0.121 11.3 0.083 22.3
16:47
JMG1-4.d 8/13/2019 Sample 0.082 11.8 0.073 10.7
16:51
JMG1-5.d 8/13/2019 Sample 0.021 32.1 0.018 44.5
16:54
JMG1-A.d 8/13/2019 Sample 0.041 46.1 0.053 32
16:58
JMG1-B.d 8/13/2019 Sample 0.094 19.7 0.082 5.8
17:02
Appendix

Sample 165 Ho [ He ] 166 Er [ He ]

Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0.002 105.6 0.006 58.3
10:40
JMF1-2.d 8/1/2019 Sample 0.002 156.2 0.003 5.7
10:43
JMF1-3.d 8/1/2019 Sample 0.004 35.4 0.002 159.7
10:47
JMF1-A.d 8/1/2019 Sample 0.006 56.3 0.003 152.8
10:50
JMF1-B.d 8/1/2019 Sample 0.005 38.7 0.007 77.6
10:54
JMF1-C.d 8/1/2019 Sample 0.008 13.1 0.016 46.4
10:57
JMF12-1.d 8/1/2019 Sample 0.002 117.8 0.002 163.1
11:01
JMF12-2.d 8/1/2019 Sample 0.001 2.8 0.001 187.7
11:04
JMF12-3.d 8/1/2019 Sample 0.001 152.9 <0.000 0
11:08
JMF12-4.d 8/1/2019 Sample <0.000 N/A <0.000 0
11:11
JMF12-5.d 8/1/2019 Sample 0.001 10.1 0.002 324
11:15
JMF12-A.d 8/13/2019 Sample 0.001 59.7 0.004 173.2
16:30
JMF12-B.d 8/13/2019 Sample 0.006 23.6 0.006 56.4
16:33
JMF12-C.d 8/13/2019 Sample 0.003 64.8 0.002 98.8
16:37
JMG1-1.d 8/13/2019 Sample 0.004 12.6 0.006 31.3
16:40
JMG1-2.d 8/13/2019 Sample 0.06 14.5 0.168 14.8
16:44
JMG1-3.d 8/13/2019 Sample 0.017 15.5 0.036 25.6
16:47
JMG1-4.d 8/13/2019 Sample 0.012 13 0.03 27.2
16:51
JMG1-5.d 8/13/2019 Sample 0.003 27.7 0.008 43.6
16:54
JMG1-A.d 8/13/2019 Sample 0.008 24 0.022 18.2
16:58
JMG1-B.d 8/13/2019 Sample 0.013 41.3 0.029 16.6
17:02
Appendix

Sample 169 Tm [ He ] 172 Yb [ He ]

Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample <0.000 N/A 0.008 105.4
10:40
JMF1-2.d 8/1/2019 Sample 0.001 118.3 0.005 58.4
10:43
JMF1-3.d 8/1/2019 Sample 0.001 64.6 0.003 159.7
10:47
JMF1-A.d 8/1/2019 Sample 0.002 77.4 0.007 44.1
10:50
JMF1-B.d 8/1/2019 Sample 0.001 161.4 0.005 59.7
10:54
JMF1-C.d 8/1/2019 Sample 0.001 101.1 0.013 74.9
10:57
JMF12-1.d 8/1/2019 Sample 0.001 99.3 0.001 204.9
11:01
JMF12-2.d 8/1/2019 Sample <0.000 0 0.003 154.7
11:04
JMF12-3.d 8/1/2019 Sample 0 355.8 <0.000 N/A
11:08
JMF12-4.d 8/1/2019 Sample <0.000 0 0.003 161.2
11:11
JMF12-5.d 8/1/2019 Sample <0.000 N/A <0.000 0
11:15
JMF12-A.d 8/13/2019 Sample 0 1.4 <0.000 N/A
16:30
JMF12-B.d 8/13/2019 Sample 0.001 145.7 0.008 64.9
16:33
JMF12-C.d 8/13/2019 Sample 0.001 52.8 0.006 26.7
16:37
JMG1-1.d 8/13/2019 Sample 0.002 20.6 0.016 60
16:40
JMG1-2.d 8/13/2019 Sample 0.022 17.8 0.16 7.4
16:44
JMG1-3.d 8/13/2019 Sample 0.005 39.1 0.039 18.9
16:47
JMG1-4.d 8/13/2019 Sample 0.005 19.3 0.022 31.5
16:51
JMG1-5.d 8/13/2019 Sample 0.001 54.9 0.006 77.4
16:54
JMG1-A.d 8/13/2019 Sample 0.003 25.3 0.024 9
16:58
JMG1-B.d 8/13/2019 Sample 0.004 37.5 0.027 31.2
17:02
Appendix

Sample 175 Lu [ He ] 205 Tl [ He ]

Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample <0.000 N/A 0.008 43.9
10:40
JMF1-2.d 8/1/2019 Sample <0.000 N/A 0.014 34.3
10:43
JMF1-3.d 8/1/2019 Sample 0.003 781.9 0.011 38.6
10:47
JMF1-A.d 8/1/2019 Sample <0.000 N/A 0.005 134
10:50
JMF1-B.d 8/1/2019 Sample <0.000 N/A 0.011 54.4
10:54
JMF1-C.d 8/1/2019 Sample <0.000 N/A 0.006 5.5
10:57
JMF12-1.d 8/1/2019 Sample 0 9980.3 <0.000 N/A
11:01
JMF12-2.d 8/1/2019 Sample <0.000 N/A 0.001 514
11:04
JMF12-3.d 8/1/2019 Sample <0.000 N/A <0.000 N/A
11:08
JMF12-4.d 8/1/2019 Sample <0.000 N/A 0 1446.7
11:11
JMF12-5.d 8/1/2019 Sample <0.000 N/A 0.004 64.5
11:15
JMF12-A.d 8/13/2019 Sample 0.014 85.9 0.007 16.7
16:30
JMF12-B.d 8/13/2019 Sample <0.000 N/A 0.01 37.7
16:33
JMF12-C.d 8/13/2019 Sample 0.003 281 0.006 47.8
16:37
JMG1-1.d 8/13/2019 Sample 0.011 204 0.003 23.1
16:40
JMG1-2.d 8/13/2019 Sample <0.000 N/A 0.002 118
16:44
JMG1-3.d 8/13/2019 Sample <0.000 N/A 0.007 48.8
16:47
JMG1-4.d 8/13/2019 Sample <0.000 N/A 0.001 111.1
16:51
JMG1-5.d 8/13/2019 Sample 0.015 172.8 0.002 104
16:54
JMG1-A.d 8/13/2019 Sample 0.011 193.9 0.002 124.2
16:58
JMG1-B.d 8/13/2019 Sample <0.000 N/A 0.004 101.5
17:02
Appendix

Sample 208 Pb [ He ] 232 Th [ He ]

Acq.
Conc. Conc.
Data File Date- Type Conc. [ ppb ] Conc. [ ppb ]
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0.211 24.6 0.132 21
10:40
JMF1-2.d 8/1/2019 Sample 0.231 4.7 0.097 19.3
10:43
JMF1-3.d 8/1/2019 Sample 0.497 3.3 0.071 14.5
10:47
JMF1-A.d 8/1/2019 Sample 0.294 8.2 0.071 10.7
10:50
JMF1-B.d 8/1/2019 Sample 0.209 9.4 0.061 7.4
10:54
JMF1-C.d 8/1/2019 Sample 0.345 9.4 0.048 14.4
10:57
JMF12-1.d 8/1/2019 Sample 0.131 19.2 0.041 4
11:01
JMF12-2.d 8/1/2019 Sample 0.082 7.9 0.041 37.4
11:04
JMF12-3.d 8/1/2019 Sample 0.082 22 0.039 15.2
11:08
JMF12-4.d 8/1/2019 Sample 0.083 21.4 0.034 16.5
11:11
JMF12-5.d 8/1/2019 Sample 0.101 40.8 0.034 19.6
11:15
JMF12-A.d 8/13/2019 Sample 0.082 29.2 0.347 3.6
16:30
JMF12-B.d 8/13/2019 Sample 0.232 11.4 0.13 14.8
16:33
JMF12-C.d 8/13/2019 Sample 0.102 9.2 0.193 11.5
16:37
JMG1-1.d 8/13/2019 Sample 0.182 10 0.121 5
16:40
JMG1-2.d 8/13/2019 Sample 0.109 22.8 0.081 7.9
16:44
JMG1-3.d 8/13/2019 Sample 0.376 15.4 0.114 2.1
16:47
JMG1-4.d 8/13/2019 Sample 0.24 20.7 0.093 5.7
16:51
JMG1-5.d 8/13/2019 Sample 0.079 19.5 0.072 12.5
16:54
JMG1-A.d 8/13/2019 Sample 0.115 15 0.048 6.3
16:58
JMG1-B.d 8/13/2019 Sample 0.022 65.1 0.107 11.3
17:02
Appendix

Sample 238 U [ He ] 6 Li ( ISTD ) [ He ]

Acq.
Conc. CPS
Data File Date- Type Conc. [ ppb ] CPS
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 0.025 18.1 121.67 23.7
10:40
JMF1-2.d 8/1/2019 Sample 0.004 48 133.33 22
10:43
JMF1-3.d 8/1/2019 Sample 0.027 25.9 123.33 8.4
10:47
JMF1-A.d 8/1/2019 Sample 0.005 67.7 118.33 12.9
10:50
JMF1-B.d 8/1/2019 Sample 0.007 24.8 86.67 13.3
10:54
JMF1-C.d 8/1/2019 Sample 0.034 27 86.67 29
10:57
JMF12-1.d 8/1/2019 Sample 0.008 28.6 123.33 24.8
11:01
JMF12-2.d 8/1/2019 Sample 0.007 71.7 110 49.2
11:04
JMF12-3.d 8/1/2019 Sample 0.005 47.7 131.67 17.9
11:08
JMF12-4.d 8/1/2019 Sample 0.004 49.1 140 18.6
11:11
JMF12-5.d 8/1/2019 Sample 0.007 66.5 106.67 16.5
11:15
JMF12-A.d 8/13/2019 Sample 0.003 36.8 185 17.7
16:30
JMF12-B.d 8/13/2019 Sample 0.006 22.4 190 20.9
16:33
JMF12-C.d 8/13/2019 Sample 0.007 34.7 191.67 19.8
16:37
JMG1-1.d 8/13/2019 Sample 0.002 74.6 165 3
16:40
JMG1-2.d 8/13/2019 Sample 0.008 78.3 176.67 4.3
16:44
JMG1-3.d 8/13/2019 Sample 0.011 5.8 181.67 27.2
16:47
JMG1-4.d 8/13/2019 Sample 0.021 48.5 191.67 14.8
16:51
JMG1-5.d 8/13/2019 Sample 0.004 103.6 143.33 15.7
16:54
JMG1-A.d 8/13/2019 Sample 0.001 169.7 190 4.6
16:58
JMG1-B.d 8/13/2019 Sample 0.037 22.4 175 13.1
17:02
Appendix

Sample 45 Sc ( ISTD ) [ He ] 89 Y ( ISTD ) [ He ]

Acq.
CPS CPS
Data File Date- Type CPS CPS
RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 25029.84 2.4 100677.37 2.7
10:40
JMF1-2.d 8/1/2019 Sample 24532.37 2 95099.94 3.8
10:43
JMF1-3.d 8/1/2019 Sample 26402.12 1.1 105167.55 0.7
10:47
JMF1-A.d 8/1/2019 Sample 24121.63 1.6 96436.71 1
10:50
JMF1-B.d 8/1/2019 Sample 25637.44 3.9 99543.37 0.8
10:54
JMF1-C.d 8/1/2019 Sample 25553.96 4.5 100796.52 2.6
10:57
JMF12-1.d 8/1/2019 Sample 26315.41 1.5 106731.9 2.1
11:01
JMF12-2.d 8/1/2019 Sample 25463.79 2.9 100182.47 1.8
11:04
JMF12-3.d 8/1/2019 Sample 25677.52 2 99937.33 3
11:08
JMF12-4.d 8/1/2019 Sample 26148.35 3.6 105275.87 3
11:11
JMF12-5.d 8/1/2019 Sample 20891.65 3.5 83524.54 6.8
11:15
JMF12-A.d 8/13/2019 Sample 32808.93 0.7 150423.04 0.5
16:30
JMF12-B.d 8/13/2019 Sample 34597.32 2.7 142838.9 1.7
16:33
JMF12-C.d 8/13/2019 Sample 32694.94 1.8 143702.6 2.4
16:37
JMG1-1.d 8/13/2019 Sample 32067.09 4 144185.29 2.7
16:40
JMG1-2.d 8/13/2019 Sample 29899.13 5.3 139255.98 4.9
16:44
JMG1-3.d 8/13/2019 Sample 31926.68 1 139610.96 3.7
16:47
JMG1-4.d 8/13/2019 Sample 31310.33 3.8 140874.08 4.7
16:51
JMG1-5.d 8/13/2019 Sample 34594.35 5.6 149012.37 1.7
16:54
JMG1-A.d 8/13/2019 Sample 30854.6 1.7 137423.93 1.7
16:58
JMG1-B.d 8/13/2019 Sample 31155.01 2.7 136094.66 4.4
17:02
Appendix

Sample 115 In ( ISTD ) [ He ] 159 Tb ( ISTD ) [ He ] 209 Bi ( ISTD ) [ He ]

Acq.
CPS CPS CPS
Data File Date- Type CPS CPS CPS
RSD RSD RSD
Time
JMF1-1.d 8/1/2019 Sample 112143.36 2.8 321242.78 2.8 235424.93 1.8
10:40
JMF1-2.d 8/1/2019 Sample 107198.97 3.4 305124.36 3.8 223903.45 2.7
10:43
JMF1-3.d 8/1/2019 Sample 116763.05 1.4 330464.7 1.7 239036.28 2.6
10:47
JMF1-A.d 8/1/2019 Sample 105854.02 1.2 304214.64 2.2 217626.32 1.7
10:50
JMF1-B.d 8/1/2019 Sample 111268.05 1.9 315678.73 0.3 233239.37 1.4
10:54
JMF1-C.d 8/1/2019 Sample 113208.73 2.2 324851.76 2.5 234658.53 3.4
10:57
JMF12-1.d 8/1/2019 Sample 118387.94 1.8 337084.79 1.6 242144.4 0.2
11:01
JMF12-2.d 8/1/2019 Sample 111042.74 1.8 313416.23 2 228055.94 2.8
11:04
JMF12-3.d 8/1/2019 Sample 111913.26 4.8 318016.96 3.9 229999.51 2.4
11:08
JMF12-4.d 8/1/2019 Sample 116201.21 3.2 329046.01 1.8 233332.55 1
11:11
JMF12-5.d 8/1/2019 Sample 94128.85 7.2 263018.04 8.5 187228.65 7.1
11:15
JMF12-A.d 8/13/2019 Sample 179801.24 1.5 567757.71 1.2 435626.97 1.8
16:30
JMF12-B.d 8/13/2019 Sample 163804.93 1.1 520500.5 2.3 411976.7 2.4
16:33
JMF12-C.d 8/13/2019 Sample 166773.47 5.5 523038.6 6.3 399650.02 1.8
16:37
JMG1-1.d 8/13/2019 Sample 168828.45 3.2 534703.04 2 396477.39 1.9
16:40
JMG1-2.d 8/13/2019 Sample 160277.16 4.5 494376.03 5.5 365740.81 6.4
16:44
JMG1-3.d 8/13/2019 Sample 162362.08 4.6 494452.13 5.6 370688.09 2.2
16:47
JMG1-4.d 8/13/2019 Sample 165068.65 4 517600.38 3.6 377589.75 4.6
16:51
JMG1-5.d 8/13/2019 Sample 173568.08 3 547283.29 3.2 416668.26 2.9
16:54
JMG1-A.d 8/13/2019 Sample 164276.17 1.8 527715.98 2.8 409360.83 1.7
16:58
JMG1-B.d 8/13/2019 Sample 157357.37 4.8 490142.12 5.1 369083.83 3.1
17:02
Appendix C – Raw data of result chapter 5
Appendix

d13C d13C d18O d18O D47 D47

d13C d18O D47
VPDB VPDB VPDB VPDB CDES CDES 49 D48
ID VPDB VPDB CDES
(Final) (Final) (Final) (Final) (Final) (Final) Param Offset
(Final) (Final) (Final)
SD SE SD SE SD SE
S1 JMC 1 0.2 0.03 0.02 -12.52 0.15 0.08 0.551 0.018 0.01
2019-01-25
R1 0.22 -12.36 0.556 0.143 -0.189
18:08
2019-02-19
R2 0.17 -12.62 0.531 0.413 -0.055
16:33
2019-02-22
R3 0.2 -12.6 0.565 0.333 -0.255
07:18
S2 JMC 11 2.01 0.25 0.14 -4.5 0.21 0.12 0.519 0.023 0.013
2019-07-18
R1 2.14 -4.48 0.522 0.227 -0.125
19:33
2019-07-23
R2 1.73 -4.71 0.494 0.261 -0.14
02:28
2019-08-03
R3 2.17 -4.29 0.54 0.204 -0.078
21:57
S3 JMC 11 Host -8.79 0.03 0.02 -10.86 0.2 0.14 0.622 0.032 0.023
2019-07-20
R1 -8.81 -10.72 0.644 0.181 -0.009
01:51
2019-07-23
R2 -8.77 -11 0.599 0.261 -0.214
14:07
S4 JMC 2 2.55 0.5 0.29 -5.4 1.49 0.86 0.471 0.051 0.029
2019-01-25
R1 2.88 -4.49 0.432 0.173 -0.319
13:40
2019-02-19
R2 2.8 -4.58 0.453 0.37 0.049
11:50
2019-02-22
R3 1.97 -7.11 0.529 0.295 0.106
12:16
S5 JMC 3 1.88 0.15 0.09 -6 0.01 0.01 0.514 0.03 0.017
2019-02-07
R1 1.75 -6 0.549 0.142 -0.075
18:54
2019-02-15
R2 1.86 -6.01 0.5 0.175 -0.285
18:05
2019-02-20
R3 2.05 -5.99 0.493 0.464 0.1
20:02
Appendix

S6 JMC 4 2.27 0.03 0.02 -5.17 0.06 0.04 0.503 0.02 0.011
2019-02-08
R1 2.3 -5.14 0.524 0.114 0.056
06:21
2019-02-15
R2 2.23 -5.24 0.499 0.109 -0.006
20:29
2019-02-20
R3 2.27 -5.12 0.486 0.506 0.463
10:57
S7 JMC 6 1.99 0.06 0.03 -8.11 0.32 0.19 0.529 0.013 0.007
2019-02-08
R1 2.01 -7.91 0.53 0.154 -0.129
22:12
2019-02-17
R2 2.04 -7.94 0.516 0.373 -0.059
22:30
2019-02-21
R3 1.93 -8.48 0.541 0.229 -0.057
19:39
S8 JMC 6 Host 2.27 0.05 0.03 -5.6 0.18 0.1 0.518 0.036 0.021
2019-07-20
R1 2.22 -5.42 0.549 0.218 0.062
03:51
2019-07-23
R2 2.27 -5.63 0.479 0.464 -0.46
18:47
2019-08-04
R3 2.31 -5.77 0.527 0.228 0.002
17:07
S9 JMC 9 2.15 #NUM! #NUM! -5.31 #NUM! #NUM! 0.572 #NUM! #NUM!
2019-07-18
R1 2.15 -5.31 0.572 0.218 0.177
11:07
S10 JMC 9 Host 1.23 0.31 0.18 -6.01 0.34 0.19 0.578 0.041 0.024
2019-04-08
R1 1.24 -5.93 0.531 0.174 0.005
16:35
2019-07-19
R2 1.54 -5.72 0.608 0.234 0.43
15:12
2019-07-23
R3 0.92 -6.38 0.596 0.217 0.135
08:49
S11 JME 2 -1.41 0.03 0.02 -14.2 0.02 0.01 0.567 0.019 0.011
2019-02-08
R1 -1.43 -14.19 0.582 0.095 -0.089
04:04
2019-02-18
R2 -1.43 -14.22 0.573 0.341 0.114
00:42
Appendix

2019-02-21
R3 -1.37 -14.2 0.545 0.273 -0.251
17:20
S12 JME 5 B Host -6.58 0.05 0.03 -14.01 0.09 0.05 0.636 0.015 0.008
2019-03-27
R1 -6.52 -13.91 0.647 0.118 0.079
14:11
2019-03-30
R2 -6.59 -14.07 0.619 0.126 0.037
01:36
2019-04-09
R3 -6.63 -14.06 0.642 0.144 -0.013
08:57
S13 JME 5A -2.88 0.1 0.06 -14.1 0.13 0.07 0.577 0.015 0.009
2019-02-08
R1 -2.79 -13.96 0.574 0.068 0.105
19:58
2019-02-15
R2 -2.87 -14.2 0.593 0.131 -0.136
22:29
2019-02-20
R3 -2.99 -14.13 0.563 0.381 0.17
02:04
S14 JME 5B -6.43 0.08 0.05 -14.18 0.12 0.07 0.602 0.031 0.018
2019-02-09
R1 -6.34 -14.05 0.627 0.106 -0.028
07:28
2019-02-16
R2 -6.47 -14.27 0.611 0.111 -0.122
14:48
2019-02-20
R3 -6.47 -14.23 0.567 0.421 0.2
15:36
S15 JMF 1 -5.94 0.02 0.01 -14.41 0.18 0.1 0.601 0.024 0.014
2019-02-07
R1 -5.92 -14.2 0.596 0.092 -0.125
21:10
2019-02-18
R2 -5.95 -14.47 0.58 0.321 0.203
09:52
2019-02-22
R3 -5.96 -14.54 0.627 0.222 -0.028
04:54
S20 JMF 10 -0.43 0.04 0.02 -12.38 0.1 0.06 0.621 0.013 0.007
2019-07-19
R1 -0.45 -12.4 0.636 0.243 0.233
13:07
2019-07-23
R2 -0.46 -12.47 0.617 0.197 0.041
06:45
2019-08-03
R3 -0.39 -12.27 0.611 0.186 0.074
15:50
Appendix

S21 JMF 13 -4.18 0.06 0.04 -13.74 0.22 0.15 0.604 0.021 0.015
2019-07-22
R1 -4.22 -13.9 0.589 0.235 -0.107
19:36
2019-08-03
R2 -4.14 -13.59 0.619 0.212 0.051
19:53
S22 JMF 3 1.42 0.13 0.07 -6.88 0.28 0.16 0.539 0.019 0.011
2019-02-08
R1 1.55 -6.58 0.553 0.151 -0.142
08:23
2019-02-18
R2 1.44 -6.91 0.548 0.385 0.047
03:06
2019-02-21
R3 1.29 -7.14 0.517 0.272 -0.257
21:48
S23 JMF 6B -6.45 0.09 0.05 -14.16 0.1 0.06 0.588 0.024 0.014
2019-01-26
R1 -6.41 -14.06 0.61 0.104 0.025
12:30
2019-02-16
R2 -6.4 -14.15 0.591 0.153 -0.397
07:54
2019-02-20
R3 -6.55 -14.26 0.562 0.364 0.121
06:33
S24 JMF 8 -3.49 0.13 0.07 -13.95 0.06 0.03 0.584 0.027 0.016
2019-02-09
R1 -3.63 -13.88 0.613 0.127 -0.087
03:03
2019-02-16
R2 -3.38 -13.99 0.56 0.175 -0.342
03:10
2019-02-20
R3 -3.46 -13.97 0.579 0.375 0.256
04:18
S25 JMF 9 -5.76 0 0 -14.51 0.05 0.04 0.577 0.014 0.01
2019-01-26
R1 -5.75 -14.47 0.567 0.102 -0.223
03:21
2019-02-19
R2 -5.76 -14.54 0.587 0.332 0.075
18:51
S26 JMG 1 2.95 0.01 0.01 -3.11 0.08 0.05 0.485 0.015 0.008
2019-02-07
R1 2.95 -3.05 0.499 0.167 -0.153
23:19
2019-02-16
R2 2.97 -3.09 0.47 0.17 -0.123
05:38
Appendix

2019-02-20
R3 2.95 -3.2 0.486 0.445 0.261
13:16
S27 JMG 2 0.67 0.07 0.04 -11.11 0.15 0.09 0.557 0.021 0.012
2019-02-08
R1 0.73 -10.96 0.549 0.107 0.666
17:43
2019-02-16
R2 0.6 -11.27 0.581 0.159 -0.252
12:37
2019-02-19
R3 0.68 -11.11 0.54 0.411 0.21
21:12
S28 JMG 4 -2.2 0.06 0.04 -12.69 0.09 0.05 0.595 0.059 0.034
2019-02-09
R1 -2.14 -12.64 0.663 0.113 0.151
05:24
2019-02-18
R2 -2.26 -12.63 0.558 0.391 0.207
07:26
2019-02-22
R3 -2.2 -12.79 0.564 0.271 -0.265
02:22
S29 MAD 3 1.32 0.09 0.06 -10.78 0.06 0.04 0.563 0.011 0.008
2019-01-25
R1 1.26 -10.82 0.555 0.141 -0.288
22:44
2019-02-22
R2 1.38 -10.74 0.571 0.307 -0.079
21:02
S3 JMC5* 2.78 0.07 0.04 -4.69 0.11 0.06 0.497 0.018 0.01
2012-09-02
R1 2.85 -4.57 0.518 0.045 -0.104
15:51
2012-09-03
R2 2.77 -4.78 0.486 0.043 0.279
12:55
2012-09-04
R3 2.72 -4.72 0.488 0.04 3.261
13:36
S5 JME3A* -1.21 0.04 0.02 -12.29 0.08 0.04 0.594 0.016 0.009
2012-08-24
R1 -1.18 -12.36 0.576 0.011 -0.289
18:53
2012-08-31
R2 -1.19 -12.3 0.6 0.022 -0.039
13:22
2012-08-31
R3 -1.26 -12.21 0.606 0.013 0.076
16:42
S6 JMF2* -6.15 0.04 0.02 -14.85 0.02 0.01 0.613 0.004 0.003
Appendix

2012-09-05
R1 -6.19 -14.86 0.618 0.004 -0.202
19:19
2012-09-14
R2 -6.15 -14.85 0.613 0.002 -0.153
15:39
2012-09-19
R3 -6.11 -14.83 0.609 0.015 1.482
12:14
S10 MAD2* 2.5 #NUM! #NUM! -7.05 #NUM! #NUM! 0.575 #NUM! #NUM!
2012-10-06
R1 2.5 -7.05 0.575 0.039 0.648
18:04
S11 MAD47* 1.39 0.01 0.01 -11.57 0.02 0.01 0.576 0.004 0.003
2012-09-20
R1 1.39 -11.56 0.573 0.021 0.84
17:08
2012-10-02
R2 1.38 -11.58 0.579 0.03 1.992
15:44