Chapter 7 Sm-Nd-Sr isotope systematics in veins ......Isotope ratios were measured by thermal...

Chapter 7

Sm-Nd-Sr isotope systematics inveins: applications togeochronology and fluid tracing

7.1 Introduction

The study of isotope ratios (e.g. Sr, Nd) in hydrothermal systems is often favouredover the study of the concentrations of trace elements, because ‘high mass’ isotopesystems such as Sr and Nd are unaffected by mass fractionation that may occurduring mineral precipitation. Instead, Sr and Nd isotope ratios are only affected bythe uptake of these elements into solution (i.e. fluid-rock reaction). This means thatisotope ratio changes are often simpler to interpret than changes in trace elementconcentrations or patterns.

Strontium isotopes are not thought to undergo significant mass fractionation dur-ing most geological processes (Faure and Powell, 1972). Hence, the Sr isotope com-position of a hydrothermal fluid will be dependent on the Sr isotope values of therocks with which that fluid has equilibrated, and the extent of isotopic exchangealong fluid flow pathways. Calcite usually contains insignificant Rb concentrationscompared to Sr concentrations (Taemas veins typically have Sr concentrations of1,000–10,000 ppm, whereas Rb concentrations are usually < 1 ppm), meaning thatan age correction is not required to directly compare the Sr isotope composition ofdifferent veins. Similarly to Sr isotopes, Nd isotopes are not thought to undergomass fractionation during geological processes. Therefore, Sm-Nd isotopes may beuseful tracers of fluid-rock reaction. The samarium-neodymium isotope system ischaracterised by the radioactive α-decay of 147Sm to 143Nd. Samarium-neodymiumratios in hydrothermal veins will be dependent on fluid source, fluid-rock reactionsalong flow paths, the initial Sm/Nd ratio, and the age of mineral deposition inthe vein. Several previous studies have explored the application of Sm-Nd iso-topes to hydrothermal systems, with various focuses on characterising the source ofhydrothermal fluids, and determining the age of hydrothermal mineral deposition(Chesley et al., 1991; 1994; Nagler et al., 1995; Relvas et al., 2001; Bau et al., 2003;Marks et al., 2003; Peng et al., 2003; Xu et al., 2003; Munoz et al., 2005; Sanchezet al., 2006). Particular attention has been paid to determining whether Sm-Nd

163

164 7. Nd-Sm-Sr compositions of Taemas veins

isotopes may be used to determine the age of hydrothermal minerals deposition.

Calcite may contain appreciable concentrations of both Sm and Nd (e.g. Lee et al.,2003). Several studies have previously used Sm-Nd to directly date fluorite (Chesleyet al., 1991; 1994; Munoz et al., 2005) and calcite mineralisation (Peng et al., 2003).Samarium and Nd have similar chemical properties, therefore 143Nd produced by α-decay will be retained in the chemical lattice, and Sm/Nd ratios are unlikely to besignificantly influenced by weathering or hydrothermal alteration. The total amountof 143Nd in a mineral will reflect the amount of 143Nd produced by radioactivedecay, as well as 143Nd originally incorporated into the mineral from the parenthydrothermal solution. As such, a single sample cannot provide an unambiguous ageof formation. Therefore, the isochron technique must be used; this technique utilisestwo or more samples and normalizes to non-radiogenic 144Nd. For relatively younghydrothermal systems, a significant range in Sm/Nd ratios is required to accuratelyconstrain mineralisation via an isochron. Furthermore, to constrain an isochron,minerals must deposit from a solution which has the same initial 143Nd/144Nd ratio.If two (or more) fluids with different 143Nd/144Nd ratios mix, then a mixing line (or‘errorchron’) will be produced, rather than an isochron.

Most hydrothermal veins lack minerals readily suitable for isotopic dating of veingrowth (such as zircon, sphene or potassium feldspar). Hence, alternative tech-niques and minerals are used to constrain the age of hydrothermal deposits. Manyof these techniques (e.g. Ar-Ar dating of alteration products are susceptible to sig-nificant errors due to chemical and/or thermal disturbances, which are common inhydrothermal systems. In addition, many techniques date alteration products (suchas clays), which may not be coeval with the deposition of hydrothermal minerals.

Dating minerals deposited from solution (whether ore or gangue) has many ad-vantages over dating alteration products. Direct dating of hydrothermal mineralsallows better correlation of hydrothermal mineralisation with regional events. Fur-thermore, detailed geochronology resolving the age of separate mineral depositionevents has not been possible, leaving significant uncertainty regarding the length oftime that hydrothermal systems remain active, rates of mineral deposition, and thetime scale of individual fluid flow events.

Here a pilot study detailing the Sm-Nd isotopic composition of calcite and fluo-rite in veins from the Taemas Vein Swarm is outlined. This study aims to explorehow Sm-Nd isotopes may be used to elucidate variations in fluid source, fluid-rockreaction along flow paths, and the age of hydrothermal mineral deposition. Theveins analysed were carefully selected on the basis of their structural setting and Srisotope ratios. Six calcite veins with identical (within error) 87Sr/86Sr ratios fromthe same Spirifer yassensis Limestone outcrop (here called “SPY veins”, samplesSP101, SP102, SP103, SP104, SP105, SP110, see Tables 7.1, 7.2) were analysed forNd isotopes and compared on an isochron diagram (samples were from the outcropdetailed in Fig. 5.16). In addition, three veins containing both calcite and fluo-rite were analysed from the Currajong Limestone, with the goal of obtaining threedifferent two-point isochrons utilising calcite and fluorite pairs from each vein.

These veins all preserve massive or blocky textures, and show no evidence forsignificant recrystallisation or dissolution/precipitation after formation (comparedwith some other veins, see Chapter 6). Considering the very slow rates of REE

7.2. Methods 165

diffusion in calcite (Cherniak, 1998), it is unlikely that Sm-Nd isotope ratios havebeen significantly disturbed in these calcite veins.

The SPY veins were chosen for analysis on the basis of their indistinguishable Srisotope ratios, and similar δ13C and δ18O values. These values provide a baseline fordetermining the variability of Sm-Nd values in samples which have similar values forother isotope systems. Voicu et al. (2000) noted that Nd isotopes were decoupledfrom Sr isotope values, and appeared to be principally influenced by the fluid source,while Sr isotope values were heavily influenced by the surrounding host rocks. Thissuggests that Sr equilibrates more rapidly than Nd during fluid migration alongflow pathways (see previous discussion regarding the relative rates of equilibrationfor different elements in §5.4.3). Thus, Nd isotopes may be a useful tracer for largescale fluid-rock reaction processes in hydrothermal systems.

7.2 Methods

Samarium and Nd isotope measurements were carried out at the Research School ofEarth Sciences, The Australian National University. ‘Clean’ reagents were used forall procedures, utilising distilled acids and deionised water ( > 18 MΩ resistance).All lab ware that came in contact with samples was acid-cleaned, and all procedureswere carried out in HEPA-filtered clean air stations. Veins were coarsely crushed (9veins total), and clean calcite and fluorite samples of ∼ 5g were hand-picked. Calcite(9 samples) and fluorite (3 samples) was rinsed in deionised (DI) water, and thencoarsely crushed by hand using an agate mortar and pestle. The fluorite sampleswere then rinsed in 0.2 M HCl to remove any calcite dust. Calcite samples weresubmerged in 0.2 M HCl for 10 s to clean the surface. From these clean samples, aknown quantity (of 100–300 mg of sample) was weighed into clean screw-top teflonvials. A known quantity of ‘ANU-1’, a mixed 147Sm/150Nd spike was added.

Clean calcite samples were then dissolved at room temperature in 0.5 M HCl.Fluorite samples were refluxed with 16 M HNO3, 8 M HCl and HClO4 on a 170C hot plate. Following dissolution, rare earth elements (REEs) were separatedfrom matrix elements by cation-exchange chromatography, using a REE-specificresin (Rehkamper et al., 1996). Neodymium and Sm were further purified usingchromatography columns loaded with HDEHP-coated Teflon powder (Richard et al.,1976).

Isotope ratios were measured by thermal ionisation mass spectrometry followingthe procedures of Wasserburg et al. (1981), using a Finnagan Mat261 for 147Sm/144Ndratios, and a Thermo-Finnagan Triton TI for 143Nd/144Nd ratios. Neodymiumand Sm were loaded in HNO3 and dilute H3PO4, and run on Ta (evaporation) -Re (ionisation) double filaments. Filaments were outgassed at 4A for 30 minutesprior to sample loading. Each analysis consisted of 150 cycles using 8.4 s inte-grations. Samples were corrected for cerium (140Ce/142Ce=7.9928) and samarium(147Sm/144Sm=4.7690, 147Sm/150Sm) interferences. All samples value were correctedby measurement of the La Jolla and Ames nNd-1 standards to adjust for laboratorybias, and standards and samples were normalised to a 143Nd/144Nd value for La Jollaof 0.511860. A procedural blank yielded 85 pg of Nd, which is negligible compared


to the total quantity of Nd in the samples (less than 0.2% of the lowest concen-tration sample, CJ202-fl, and << 0.1% of the remaining samples). Nd isotopiccompositions are reported as εNd, where

εNd =

(143Nd/143Ndsample

143Nd/143Ndstandard

− 1

).10000 (7.1)

where the 143Nd/144Nd standard value for modern-day chondrite is 0.512638 (Jacob-sen and Wasserburg, 1980).

7.3 Results

For the SPY calcite veins, concentrations of Nd vary between 1.7 and 14.1 ppm,generally higher than those reported by Peng et al. (2003) for hydrothermal calcite.The three fluorite samples all have very low Nd concentrations (0.18–0.26 ppm),much lower than fluorite Nd concentrations reported in Chesley et al. (1991) orMunoz et al. (2005). Fluorite samples 147Sm/144Nd range between 0.15 and 0.28.Calcite samples from the fluorite-bearing veins have Nd concentrations of 0.9–2.9ppm, lower than most of the SPY veins.

The calcites are light REE enriched, with 147Sm/144Nd varying between 0.11 and0.16. The other calcite veins are also light REE enriched, with Sm/Nd ratios (0.110-0.155) lower than the chondritic value (0.1967). The measured εNd compositions are-10.0 and -12.6, indicating a crustal source for the Sm and Nd found in these fluids.One calcite sample (SMF-1, from the fluorite-bearing vein) has a slightly differentεNd (-6.06), indicating derivation from a different source. The fluorite samples rangefrom slightly light REE enriched (147Sm/144Nd=0.147-0.164) to strongly light REEdepleted (147Sm/144Nd=0.29). The 3 fluorite samples have εNd of -1.0 to -7.7.

Figure 7.1 shows a Sm-Nd isochron diagram for all of the data collected in thisstudy (produced from ISOPLOT, by Ludwig, 2003). The low spread in 147Sm/144Ndratios means that the isochron age determined from these samples is not robust.Regression of all data yields a ‘errorchron’ (482±220 Ma). Regression of the separatedata sets yields errorchrons of 261 ±330 Ma for the SPY calcite veins, and ages of671 ±68 Ma and 1510 ±86 for two of the calcite-fluorite vein pairs. Only one of thecalcite-fluorite vein pairs has sufficient spread in 147Sm/144Nd values (0.14 to 0.28)to provide a potentially ‘reliable’ isochron (260± 44 Ma).

7.4 Application of Nd isotopes in hydrothermal

systems

Despite the small variation in 147Sm/144Nd, an isochron will result if all samplesformed from a fluid with the same 143Nd/144Nd ratio, over the same period of time.Therefore, an explanation is required for why an isochron was not formed by theminerals analysed for this study.

If we assume that all the SPY veins formed from a fluid with the same initial143Nd/144Nd ratio, then the veins must have formed over a period of at least 145

7.4. Application of Nd isotopes in hydrothermal systems 167

Tab

le7.

1:Sm

-Nd

isot

opic

and

conc

entr

atio

nda

tafo

rca

lcit

ean

dflu

orit

eve

ins

from

the

Spir

ifer

Yas

sens

isan

dC

urra

jong

Lim

esto

nes,

Tae

mas

Min

era

lSam

ple

87Sr/

86Sr

Sm

(ppm

)N

d(p

pm

)147Sm

/144N

d143N

d/

144N

dε1

43N

dC

alci

teSP

101

0.70

8520±

200.

431.

680.

1552

96±

120.

5121

13±

10-1

0.24

Cal

cite

SP

102

0.70

8523±

152.

2711

.71

0.11

7249±

100.

5119

90±

8-1

2.64

Cal

cite

SP

103

0.70

8524±

170.

683.

200.

1293

44±

90.

5120

69±

10-1

1.09

Cal

cite

SP

104

0.70

8492±

201.

155.

380.

1287

10±

130.

5120

76±

9-1

0.96

Cal

cite

SP

105

0.70

8510±

163.

6414

.15

0.15

5356±

180.

5120

87±

12-1

0.75

Cal

cite

SP

110

0.70

8542±

170.

904.

260.

1274

46±

80.

5120

69±

9-1

1.11

Flu

orit

eC

J20

1-fl

N/A

0.06

0.24

0.16

3860±

270.

5122

42±

21-7

.73

Cal

cite

CJ20

1-cc

t0.

7082

60±

210.

532.

910.

1104

52±

90.

5120

07±

13-1

2.31

Flu

orit

eC

J20

2-fl

N/A

0.04

0.18

0.14

6888±

380.

5123

89±

18-4

.86

Cal

cite

CJ20

2-cc

t0.

7082

69±

170.

281.

500.

1111

64±

120.

5120

34±

11-1

1.78

Flu

orit

eSM

F1-

flN

/A0.

130.

260.

2864

19±

450.

5125

89±

33-0

.96

Cal

cite

SM

F1-

cct

N/A

0.21

0.93

0.13

5920±

180.

5123

28±

29-6

.06


Tab

le7.2:

Srand

Nd

isotopedata,

with

δ13C

(relativeto

VP

DB

)and

δ18O

(relativeto

VSM

OW

)values

forcalcite

veinsfrom

theSP

Yanticline,

andselected

traceelem

entconcentrations

(inparts

perm

illion)for

calciteand

fluoritesam

ples.

Sam

ple

87Sr/86Sr

147Sm

/144N

d143N

d/144N

dδ13C

δ18O

Sc

Mn

Fe

Sr

YLa

Ce

Pr

Eu

Gd

Dy

Er

Yb

SP

101

0.7

0852

0.1

553

0.5

12113

0.9

622.4

0.1

1253

2837

1952

1.4

40.5

71.6

40.2

90.4

70.3

50.2

10.0

70.0

3SP

102

0.7

0852

0.1

172

0.5

11990

0.6

922.6

1.1

2232

3353

3963

8.9

09.2

521.1

02.6

70.6

21.9

11.5

90.7

40.5

2SP

103

0.7

0852

0.1

293

0.5

12069

0.9

422.5

0.4

9280

3287

2967

2.8

51.4

23.8

30.6

30.6

50.6

70.4

50.1

70.0

9SP

104

0.7

0849

0.1

287

0.5

12076

0.8

022.5

0.7

2247

3549

3288

2.6

81.8

64.0

80.5

60.5

10.5

40.4

50.2

00.1

4SP

105

0.7

0851

0.1

554

0.5

12087

0.7

622.5

0.9

0229

3723

3751

17.7

39.0

225.1

53.7

80.7

13.8

63.1

11.2

10.6

7SP

110

0.7

0854

0.1

274

0.5

12069

0.9

422.4

0.4

0254

4274

3066

6.6

75.1

715.0

62.1

81.1

01.6

51.1

70.4

00.1

9

CJ201-fl

N/A

0.1

639

0.5

12242

N/A

N/A

0.0

20.1

223

222

0.1

40.0

40.0

70.0

20.0

30.0

30.0

20.0

10.0

1C

J201-cct

0.7

0826

0.1

105

0.5

12007

N/A

N/A

0.2

170

449

2593

0.7

71.8

33.0

70.3

30.1

50.1

70.1

00.0

40.0

2

CJ202-fl

N/A

0.1

469

0.5

12389

N/A

N/A

0.0

30.0

622

212

0.4

00.0

60.1

40.0

30.0

60.0

70.0

40.0

20.0

1C

J202-cct

0.7

0827

0.1

112

0.5

12034

N/A

N/A

0.5

877

989

3426

1.3

51.8

03.2

30.3

70.1

70.2

70.2

30.1

10.0

9

SM

F1-fl

N/A

0.2

864

0.5

12589

N/A

N/A

0.0

20.0

923

343

2.1

70.2

00.4

00.0

40.0

60.2

20.1

20.0

40.0

1SM

F1-cct

N/A

0.1

359

0.5

12328

N/A

N/A

1.1

174

759

3893

2.4

72.8

55.5

70.6

60.1

50.4

40.4

10.2

20.1

8

7.4. Application of Nd isotopes in hydrothermal systems 169

0.06 0.10 0.340.300.260.220.180.14

0.5128

0.5126

0.5124

0.5122

0.5120

0.5118

Age = 482 ±220 MaInitial 143Nd/144Nd =0.51170±0.00022MSWD =12614

3 Nd/

144 N

d

147Sm/144Nd

cc

F

F

F

cc

cc

Figure 7.1: Sm-Nd isochron (147Sm/144Nd versus 143Nd/144Nd)showing results and2 SE from the calcite and fluorite veins. Note that the calcite-fluorite single vein pairsare highlighted in different colours for each pair, and cc=calcite, f=fluorite. The blacksymbols are results from the SPY veins.

million years. No systematic crosscutting relationships were observed for the SPYveins. In addition, fold growth and vein formation appear contemporaneous. Thisstrongly suggests that veins formed at approximately the same time. It seems im-plausible that veins formed over such a prolonged period of time, given that veinsappear to have formed during the same folding event (of perhaps 0.5 to 15 Ma dura-tion, see §4.3.1). Thus, we must conclude that these veins formed from fluids with arange of initial 143Nd/144Nd values. This is despite careful selection of vein sampleswhich occur in the same structural setting, with indistinguishable Sr and oxygenisotope ratios, and similar δ13C values.

The isochrons from the three calcite-fluorite veins (forming three isotope ‘pairs’),yielded three vastly different ages. Two of these ages, 1510 ±68 Ma and 671 ±68Ma, are clearly unreasonable, as they are older than the limestone in which the veinsare hosted. Only one age from a calcite-fluorite vein is geologically ‘reasonable’ (i.e.younger than the rocks it is hosted in 265 ±40 Ma), although this age significantlypostdates the proposed Carboniferous age for deformation (Hood and Durney, 2002).

The lack of agreement between the calcite-fluorite mineral pairs indicates thatfluorite and calcite precipitated from parental solutions with distinct 143Nd/144Ndratios. A plausible explanation is that calcite and fluorite precipitated from twodifferent fluids with distinct 143Nd/144Nd, during the incremental development ofthe hydrothermal veins.

Instead of providing a tool for determining the age of hydrothermal mineralisation,Sm-Nd may instead be an extremely valuable tracer of fluid source, and fluid-rock


reaction during hydrothermal mineralisation. For example, Voicu et al. (2000) ina study of a gold deposit, found that Nd isotope compositions largely reflected thesource of the mineralising fluid, while Sr was more mobile during hydrothermal fluidflow, and underwent equilibration with the surrounding host rocks. A similar casecould be made for this study, whereby the Sr isotope signature of veins reflectsthe immediately surrounding host rocks, and variations in short-length fluid flowpathways (due to more rapid equilibration of Sr with the surrounding host rocks).However, changes in Nd isotope composition may reflect changes in fluid sourceand/or changes in longer length fluid flow paths, due to slower equilibration ratesfor Nd in comparison to Sr.

This study suggests Sm-Nd isochrons in hydrothermal systems should be treatedwith caution. For example, Peng et al. (2003) reported high-precision ages forcalcite veins associated with an antimony deposit. The ‘precision’ of this age isextremely dependent on the large range in 147Sm/144Nd values. However, Sr isotopemeasurements made on these same samples by Peng et al. (2003) reveal a largerange in 87Sr/86Sr, despite the lack of Rb in these samples which could cause thevariations in 87Sr/86Sr. This strongly suggests that these calcite samples may haveformed from fluids with an extremely varied isotopic composition, and the resulting‘isochron’ is actually a mixing line. Meanwhile, Munoz et al. (2005) in their studycould only form a three-point Sm-Nd ‘isochron’ after leaving one analysis out oftheir regression calculation.

The origin of fluids from multiple sources, and/or the flow of fluids which haveundergone variable fluid-rock reaction (and thus having variable initial 143Nd/144Nd)is probably the common scenario in most hydrothermal systems. Previous studiesby Nagler et al. (1995) and Bau et al. (2003) have also raised doubts about theapplicability of Sm-Nd isochrons in hydrothermal systems. This study emphasisesthe need to carefully characterise the structural setting and other chemical infor-mation before interpreting Sm-Nd isotope data for geochronological purposes. Arobust system is required to demonstrate that the initial 143Nd/144Nd is the samefor minerals being targeted for a geochronological study.

7.5 Conclusions

Samarium-neodymium dating has shown promise in previous studies to determinethe timing of hydrothermal mineral deposition. In this study, 9 veins (comprising12 samples in total) were analysed. These samples were chosen on the basis oftheir structural occurrence, and similarity of their strontium and oxygen isotopecompositions. Six veins were analysed from the same outcrop, and three veinscontaining both calcite and fluorite were analysed in an attempt to constrain fourseparate isochrons.

These samples did not yield geologically reasonable isochrons. This is attributedto the veins forming from fluids which had distinct 143Nd/144Nd compositions, whichmay be due to far field changes in fluid source and/or fluid flow pathways affectingNd isotope compositions, whereas Sr and O isotopes equilibrate with the surroundinghost rocks over much shorter distances. In addition, calcite and fluorite within the

7.5. Conclusions 171

same vein deposited from separate fluids, with distinct Nd isotope compositions.This study indicates that despite careful sample collection, veins which formed

in apparent synchrony may deposit from solutions which have a diverse range ofinitial isotope ratios. This study demonstrates that careful documentation of thestructural and textural setting of each sample is required to enable robust inter-pretation of analytical results. Previous studies which report high-precision agesfor hydrothermal mineralisation via Sm-Nd techniques may simply be reporting theisotopic ratios of a series of different fluids, rather than an age of mineralisation.

Chapter 8

Dynamics of fluid flow and fluidchemistry during crustalshortening

The Taemas Vein Swarm (TVS) provides an opportunity to examine the effects of,and interplay between, fold growth, faulting, fluid flow, fluid pressure states, veingrowth and fluid-rock reaction during crustal shortening. The TVS preserves evi-dence for growth of a fracture-controlled flow system at transiently supralithostaticfluid pressures. The degree of fluid-rock reaction varies within individual veins,and between veins in the same outcrop. Variable fluid-rock reaction is attributedto dynamically changing fluid flow pathways due to repeated fracturing events andassociated transitory permeability enhancement, followed by fracture-sealing andpermeability destruction.

The goal of this chapter is to review structural and chemical data presented inearlier chapters, and integrate these results to explain the physical behaviour of theTaemas Vein Swarm. The implications of this behaviour for fluid-rock reaction ina percolation network are explored, with potential implications for seismicity andmineralisation. This chapter is designed to be a ‘stand-alone’ document, althoughmaterial discussed here will be most thoroughly understood if the earlier chaptersof this thesis are also examined.

Firstly, an overview of the main structural features and chemical characteristicsof the Taemas Vein Swarm is provided, with emphasis on the deformation history,controls on vein development, fluid source, fluid pressure states and differentialstress levels during the development of the vein swarm. Secondly, the importanceof microchemical analyses for examining fluid-rock reaction and mineral depositionin hydrothermal systems is highlighted. Thirdly, the importance of episodic flowregimes, and links between vein growth and seismicity are discussed.

8.1 Overview of the Taemas Vein Swarm

The Taemas Vein Swarm is hosted in a series of faults and fractures, and is developedover an area of approximately 20 km2. Veins are composed of calcite ± quartz,

173

174 8. Fluid flow and fluid chemistry during crustal shortening

with minor fluorite and barite present in some veins. The vein swarm is hostedin a limestone-shale sequence, the Murrumbidgee Group, in the Eastern Belt ofthe Lachlan Orogen, in eastern New South Wales, Australia (Glen, 1992). TheMurrumbidgee Group is composed of several formations, comprising massive greymicritic limestones, redbed sandstones and shales, and thinly interbedded (10–20cm scale) limestones and shales.

The sedimentary sequence has been folded into a series of upright, open to closefolds, and was probably deformed during either mid-late Devonian (Browne, 1958),or early Carboniferous (Hood and Durney, 2002), crustal shortening. Crosscuttingand overprinting relationships demonstrate that vein growth was synchronous withfolding, with different vein types related to different fold growth mechanisms.

Flexural slip folding led to the development of bedding-concordant veins (hereaftercalled bedding-parallel veins). Flexural flow in semicompetent to incompetent bedscaused en echelon extension vein arrays to grow. Decoupling between beds, anddilatancy at fold hinges led to significant vein growth and calcite precipitation. Inaddition, fold lock-up led to limb-parallel stretching, and the growth of extensionfractures approximately orthogonal to bedding.

Vein growth is inferred to have occurred in a compressional tectonic regime (i.e.σ3=vertical), with oxygen isotope quartz-calcite thermometry suggesting that veinsformed at temperatures of 150–200 C. The depth of vein formation may have beenbetween 5 and 8 km. Vein textures indicate that growth of veins occurred duringmultiple cycles of permeability enhancement and destruction. Subhorizontal exten-sion fractures, and faults at unfavourable angles for reactivation, imply that fluidpressures exceeded lithostatic levels during the growth of some veins. In addition,coexisting extension and shear fractures imply that differential stress levels tempo-rally varied between σ1 − σ3 < 4T and σ1 − σ3 > 5.66T (where T is the rock tensilestrength).

Vein δ18O compositions systematically increase upwards through the MurrumbidgeeGroup, caused by progressive reaction of a low-δ18O fluid with host limestones. Veinδ18O and 87Sr/86Sr compositions vary spatially and temporally within the same out-crop, which is inferred to be caused by the ascent of packages of fluid along constantlychanging flow pathways. Fluid pathways are inferred to have varied due to repeatedfracture opening and sealing, with permeability being dynamically created and de-stroyed. The low δ18O compositions of vein calcite implies that the fluids from whichveins formed were ultimately derived from a meteoric source.

8.2 Illuminating hydrothermal fluid flow dynam-

ics using chemistry

In this thesis, changes in stable and radiogenic isotope ratios, and trace element con-centrations, have been used to infer changes in the extent of fluid-rock reaction, andchanges in physiochemical conditions during the growth of the Taemas Vein Swarm(Chapter 5), as well as during the growth of individual veins (Chapter 6). In thissection, the use of isotopic and trace element chemistry to illuminate the dynamicsof hydrothermal systems is discussed. Firstly, mechanisms influencing hydrothermal

8.2. Illuminating hydrothermal fluid flow dynamics using chemistry 175

vein textures, and use of vein textures to diagnose mass transfer mechanisms areoutlined. Secondly, the application of techniques utilised in this study to examinechemical dynamics in paleohydrothermal systems is discussed. Finally, the value ofintegrating two or more isotope systems to examine fluid-rock reaction processes ishighlighted.

8.2.1 Interpretation of vein textures

At Taemas, a variety of vein textures is found. Extension veins in massive lime-stones are generally massive, elongate-blocky or fibrous, with elongate-blocky andfibrous veins forming via stretched crystal and/or syntaxial growth mechanisms (e.g.Fig. 4.22c,d). In comparison, extension veins formed in shales are often fibrous,and appear to grow via antitaxial and stretched crystal growth mechanisms (e.g.Fig. 4.22a). Fault-fill veins (both bedding-parallel and bedding-discordant) gener-ally have laminated and massive textures. Despite the marked variation in texturethroughout the Taemas Vein Swarm, all veins formed as part of a large-scale, up-wardly advecting flow system (cf. Cox, 2007).

In this section, I discuss results from the calcite growth experiments presented in§3.4.3, and the implications that these results have for the interpretation of veintextures. The interpretation of vein textures is of fundamental importance, becauseif certain vein textures can only form under certain conditions, then the recognitionof those textures allows the diagnosis of the chemical and/or physical environmentin which a vein formed.

The calcite growth experiments outlined in Chapter 3 demonstrate that markedlydifferent calcite morphologies could be produced by changing the [REE3+]:[Ca2+]ratio in solutions. Solutions with higher [REE3+]:[Ca2+] produced elongate to aci-cular crystals, whereas solutions with lower [REE3+]:[Ca2+] produced more equantcrystals. Lee and Morse (1999) discussed the role that Mn poisoning may play inaltering the morphology of calcite crystals in synthetic veins, with increasing Mnconcentrations promoting the growth of platy calcite crystals. Lee and Morse (1999)concluded that impingement crystal growth (following the model of Dickson, 1992)may explain why crystal size commonly increases away from vein walls (i.e. growthcompetition between adjacent crystals).

The influence of impurity concentrations and supersaturation state on the mor-phology of calcite precipitated from solution is well established. Examples of theinfluence of solution chemistry on calcite crystal morphology include:

1. Paquette et al. (1996) noted that Mg inhibited growth of calcite at the edge ofcrystal faces, while surface reactive phosphate inhibited growth and dissolutionon specific crystallographic surfaces.

2. Pastero et al. (2004) demonstrated that higher calcite supersaturation stateand [Li+] promote increasingly platy calcite crystal morphology.

3. Experimental evidence presented in Chapter 3 documents the influence of vari-able REE concentrations on calcite morphology.


Dickson (1983) demonstrated that initial crystallographic morphology significantlyaffects the resulting texture of calcite veins, with both elongate-blocky and massivetextures developed when the growth of different calcite morphologies was simulated(Figures 9–11 in Dickson, 1983). Thus, a clear cause-and-effect exists between solu-tion chemistry, calcite morphology, and vein texture.

Several recent studies, which attempted to grow experimental veins by advect-ing fluids through a fracture, concluded that advection of fluid through fracturesand accompanying precipitation of material can lead to inlet clogging and cessationof flow (Lee et al., 1996; Hilgers et al., 2004; Nollet et al., 2006). If veins do notrepresent a fracture that was a fluid conduit, then this calls into question the in-terpretation of veins as indicators of paleofluid flow, or as indicators of enhancedcrustal permeability in paleohydrothermal systems.

Various vein textures have traditionally been interpreted in terms of competitionbetween the rate of vein dilation, and crystal growth kinetics (e.g. Ramsay, 1980;Cox and Etheridge, 1983; Cox, 1987; Urai et al., 1991; Oliver and Bons, 2001; Hilgerset al., 2001). There has been a lack of agreement over the origin and significance ofsyntectonic fibrous veins, particularly antitaxial growth veins. Recently, experimen-tal and conceptual studies have suggested that both fibrous and banded ‘crack-seal’vein textures may form via diffusion, without fracturing, or mass transfer via advec-tive fluid flow (Means and Li, 2001; Wiltschko and Morse, 2001). Debate surroundswhether ‘truly’ fibrous textures (Bons, 2000; Oliver and Bons, 2001; Bons and Mon-tenari, 2005) may develop in a fracture through which fluid is advecting, or whetherfibrous textures are diagnostic of growth in a stationary fluid with only diffusionalmass-transport (see discussion in Durney and Ramsay, 1973; Fisher and Brantley,1992; Bons and Jessell, 1997; Bons, 2000; 2001a; Hilgers et al., 2001; Oliver andBons, 2001; Elburg et al., 2002; Bons and Montenari, 2005; Barker et al., 2006).

At least two studies from different areas demonstrate that antitaxial fibrous veinsformed from material that was not derived from the immediately surrounding hostrocks (Elburg et al., 2002; Barker et al., 2006), implying that antitaxial fibrous veinsare connected to, or themselves act as, fluid conduits. Thus, we have a dichotomy;the chemical compositions of natural antitaxial fibrous veins indicate that these veinsform from material which has been transported for distances of tens-to-hundreds ofmetres (almost certainly via transport in advecting fluids), while modelling andexperimental studies suggest that fibrous textures cannot develop in open fractures,and therefore cannot have had fluid advecting through them (implying diffusionalmass transfer over geologically reasonable distances of a few centimetres to a metre;Etheridge et al., 1984).

Vein texture is likely the result of a complex interplay between fracture dilationrate, mineral precipitation rate, solution chemistry (influencing both the degree ofsupersaturation and crystal habit), fracture surface roughness (Urai et al., 1991),number of mineral nucleation points (Dickson, 1983), and the composition of wallrocks and fracture-filling minerals (which will influence whether syntaxial, antitaxialor stretched crystal growth mechanisms dominate). The variety of vein texturesobserved in the Taemas Vein Swarm, which formed in a large-scale advective flowsystem, suggests that specific vein textures are not diagnostic of particular masstransport mechanisms.


8.2.2 Chemical dynamics recorded in hydrothermal veins

The application of microchemical isotopic and trace element techniques to syn-tectonic veins opens an exciting new field of research. Modern analytical tech-niques, coupling laser ablation sampling technology to analytical instruments (e.g.quadrupole ICP-MS, multicollector ICP-MS, GC-IRMS) allow high-spatial resolu-tion data to be collected, enabling variations in mineral chemistry during vein growthto be determined. Such techniques have direct application to the examination ofhydrothermal veins in fracture-hosted ore deposits, and may allow the fluid sourceand/or chemical conditions conducive to the formation of high-grade ore to be dis-cerned.

In Chapters 3 and 6, the application of microanalyses to examine changes inmineral chemistry were presented (e.g. trace element, and Sr, C and O isotoperatios). These chemical changes are used to make inferences about variations in fluidsource, flow pathways and chemical conditions (e.g. trace element complexation,precipitation rate, changes in redox state of fluid) during hydrothermal fluid flow.In this section, I discuss the application of microsampling to illuminate the dynamicsof paleohydrothermal systems.

One of the challenges presented by this study was distinguishing changes in mineralchemistry produced by an extrinsic effect (i.e. a change in the bulk composition ofa fluid) as opposed to changes caused by intrinsic effects due to changing crystalgrowth rates, or crystal surface orientation effects (see §3.1). Indeed, variationsin trace element concentrations likely result from both changes in extrinsic fluidcomposition, as well as crystal growth effects.

Experimental results presented in §3.4.3 (Fig. 3.9) revealed that crystals grownfrom solutions with approximately constant chemistry had significant variations intrace element mineral composition over distances of < 100 µm. This result suggeststhat the fine-scale ( < 100 µm) trace element concentration changes observed innatural veins (e.g. Wogelius et al., 1997; Barker et al., 2006; Allan and Yardley,2007) are strongly influenced by crystal growth processes, rather than variations inthe bulk composition of the hydrothermal fluid.

Changes in the isotopic composition of calcite veins, particularly variations in Srisotope ratios (which are extremely unlikely to be modified by crystal growth pro-cesses) are considered to be robust indicators of changes in the extrinsic compositionof a fluid. Such Sr isotope changes were used to determine that fluid flow pathwaysvaried during the growth of individual veins (§6.7). Three criteria are suggestedto distinguish extrinsic from intrinsic controls on trace element concentrations inminerals:

1. Extrinsic changes in bulk fluid composition are most likely when variations intrace element concentrations are coincident with changes in Sr isotope (par-ticularly), and/or O isotope ratios.

2. Extrinsic changes in fluid chemistry may have occurred if a textural changein a vein (e.g. crossing a crack-seal layer, crossing into a region of differentlyoriented fibres) is coincident with a change in mineral chemistry.


3. Extrinsic changes in fluid chemistry may have occurred if changes in trace ele-ment concentrations are also coincident with changes in REE patterns and/orREE anomalies (which are more likely to be affected by a change in bulk fluidcomposition, rather than a crystal growth effect).

Vein growth rates

In §6.4 (published as Barker et al., 2006), significant fluctuations in trace elementconcentrations were noted over scales of < 100 µm in a natural calcite vein. Twoprocesses were suggested to have caused these fine-scale variations, either changesin bulk fluid chemistry, or a crystal growth-controlled process (e.g. Ortoleva et al.,1987; Watson, 1996; 2004).

Fine-scale variations in trace element concentrations in calcite may be explained bythe growth entrapment model of Watson (1996; 2004), which suggests that the con-centration of a trace element in a growing crystal is controlled by the concentrationof that element in the ‘near-surface’ region of the growing crystal, and competi-tion between crystal growth (trapping surface enriched elements) and ion migrationin the near-surface region (which attempts to rid the crystal lattice of impurities).Therefore, the spacing and amplitude of compositional zones may provide quanti-tative information about the precipitation rate of material in hydrothermal veins.Calcite which precipitated at faster rates would preserve significant compositionalzoning, because variations in the near-surface region of the crystal would be cap-tured by the more rapidly growing crystal. Contrastingly, calcite precipitated moreslowly would have less prevalent compositional zoning, because there is more timefor elements in solution to diffuse through the surface layer and reach equilibriumwith the crystal lattice.

In a recent paper, Gabitov and Watson (2006) suggest that crystal growth ratesslower than 0.5 mm yr−1 are required to reach equilibrium partitioning of Sr betweena growing calcite crystal and fluid at 25C. Therefore, calcite crystals forming in ahydrothermal vein would need to grow at a rate of more than 0.5 mm per yearto capture fine-scale variations in Sr. Indeed, faster growth rates are probablyrequired to preserve compositional variations, as diffusion rates will be faster athigher temperatures.

If the fine-scale Sr variations (such as those seen in the veins described in Chapter6) are indeed caused by a crystal growth effect, then this suggests that these thincalcite veins (perhaps 1 cm thick, extending for metres laterally) grew at ratesof > 0.5 mm yr−1, and thus formed in perhaps twenty to fifty years. Even ifthis estimate is incorrect by an order-of-magnitude, these periods are considerablyshorter than growth rates estimated by Lee and Morse (1999), who used a series ofanalogue vein growth experiments to estimate that thin calcite veins (perhaps 1 m x1 m x 1 cm) would grow in 1,000–100,000 years. Estimates of growth rates could beimproved by examining compositional variations of trace elements in calcite crystalsgrown at different rates in carefully controlled experiments.


Imaging physiochemical changes in hydrothermal solutions

Growth entrapment models provide an explanation for fine-scale ( < 100 µm) traceelement concentration changes in vein calcite. However, growth entrapment doesnot explain changes in REE patterns, with Ce and Eu anomalies developed, andvariable light REE enrichment and depletion occurring. In a fluid with initiallychondritic REE ratios, with all Ce and Eu in the 3+ valency, then the REE willform a flat pattern when normalised to chondrite, and no Ce or Eu anomaly wouldbe observed.

Changes in relative depletion or enrichment of light REE in solution (i.e. changesin the slope of normalised REE patterns) reflect varying REE complexation andsorption (Bau, 1991). In carbonate-dominated solutions, the REE are likely tobe primarily complexed by CO2−

3 (Bau, 1991; Bau and Moller, 1992). Changes inthe slope of REE patterns during the growth of an individual vein (e.g. see §6.4)may be related to changing carbonate concentrations in the hydrothermal fluid, orprogressive sorption or desorption of REE during fluid-rock reaction.

Europium anomalies are most likely caused by reaction of fluid with Eu-rich min-erals (e.g. Ca-plagioclase) or minerals depleted in Eu (i.e. minerals which crys-tallised from a magma that was also crystallising Ca-plagioclase; Schnetzler andPhilpotts, 1970). Negative Eu anomalies could be generated by reduction of fluid,with Eu2+ predicted to be discriminated against during calcite precipitation due toits increased ionic radius. However, Bau (1991) and Bau and Moller (1992) predictthat Eu3+/Eu2+ fractionation will only occur in high temperature hydrothermal so-lutions (i.e. > 200 C), due to the very low fO2 required to cause Eu reductionat lower temperatures. The oxidation state of Ce varies as a function of both pHand fO2 at near-surface conditions (Bau and Moller, 1992), and therefore may bean indicator of changing pH or oxidation state in a hydrothermal solution. In §6.4,low δ13C values were found, which were attributed to the oxidation of 13C-depletedhydrocarbons to CO2. The depleted δ13C values were coincident with a positive Ceanomaly, leading to the suggestion that Ce anomalies may be indicative of changingoxidation state in hydrothermal solutions.

Fluid oxidation state is thought to be critical to the stability of metal-complexesin hydrothermal solution (Seward and Barnes, 1997). Hence, changes in fluid ox-idation state may cause ore-deposition in hydrothermal solutions. The ability to‘image’ changes in fluid oxidation state may provide a useful tool for mineral ex-ploration studies. Cerium and Eu anomalies (especially Eu in higher-temperatureenvironments) may be a means of evaluating changes in fluid oxidation state inhydrothermal systems.

8.2.3 The value of integrated chemical studies

In this study, carbon, oxygen, strontium and samarium-neodymium isotopes, andtrace and rare earth element patterns, have been used to examine fluid-rock reactionprocesses. The application and usefulness of a particular trace element or isotopesystem to examine fluid-rock reaction processes is dependent on the concentrationof that tracer in a fluid, concentration of the tracer in the rock, and the kinetics of


reactions between rock and fluid for that tracer. Thus, fluid-rock exchange processesfor any particular element may change both along a flow pathway, and with time(i.e. as a fluid reaches equilibrium with the surface of minerals; Bau et al., 2003).

Oxygen is an element which is present in most common rock minerals. Oxygenisotopes have been used extensively to examine fluid-rock reaction, and estimate timeintegrated fluid fluxes in hydrothermal systems (e.g. Bickle and McKenzie, 1987;Dipple and Ferry, 1992). However, studies of oxygen isotopes provide little or noinformation on which specific minerals or lithologies underwent reactions with fluids.However, other isotope systems may provide information on the source of fluids,and/or minerals or lithologies with which fluids reacted. For example, Sr isotopesmay reveal whether fluids were reacting with radiogenic minerals (e.g. K-feldsparsor K-rich micas which will contain higher concentrations of radiogenic 87Rb), orwere reacting with less radiogenic minerals, such as carbonates. Strontium and Ndisotopes have been compared in at least two studies, with Nd isotopes generally notreaching equilibrium with the immediately surrounding host rocks, instead providinga record of long-distance fluid flow pathways and/or fluid sources (e.g. Voicu et al.,2000; Bau et al., 2003).

The results from the present study indicate that the chemical and isotopic compo-sition of a fluid is dependent on different fluid-mineral reactions along varying flowpathways. One example may be seen by comparing changes in δ18O and 87Sr/86Srwith stratigraphic height in the Taemas Vein Swarm (Figs. 5.4 and 5.5). It isapparent that δ18O values become equilibrated with respect to host limestone oxy-gen isotope compositions, and do not generally deviate from a value of 23–25 h,even as fluids reacted with different lithologies (i.e. limestone and shale). However,87Sr/86Sr ratios show significant changes as fluids pass through lithologies composedof only limestone, or mixed lithologies of both limestone and shale. The variationsin 87Sr/86Sr were attributed to variable reaction of fluids with clays and feldspars.By combining measurements of Sr and O isotopes in the examination of an fibrousantitaxial vein (see §6.4), it was possible to distinguish variations in the degree offluid-rock reaction. If only measurements of oxygen isotope ratios were made, thenfluid-rock reaction could not be easily distinguished from other factors influencingcalcite δ18O, such as variable fluid temperature.

Bickle (1992) demonstrated that O and Sr isotopes could become decoupled fromone another due to the very different concentrations of these tracers in crustal fluids.Tracers which are strongly partitioned into a fluid display alteration on a larger scale,while tracers partitioned strongly into solid phases are only perturbed over smallerlength scales. At Taemas, even veins with essentially identical isotope ratios fortwo isotope systems (O and Sr) are decoupled with respect to Nd-Sm. Bau et al.(2003) carried out an integrated Sr-Nd-Pb isotope and rare earth element study ofhydrothermal fluorite in a Mississippi Valley Type (MVT) fluorite deposit. Theirresults demonstrated that the Nd, Pb and Sr isotope systems were decoupled fromone another, which was caused by the derivation of different solutes from differentsources. Bau et al. (2003) concluded that the chemical and isotopic compositionof a fluid is not controlled by the ‘last rock’ that the fluid encountered. Thus, bythe integrated analysis of different isotopic systems, different processes altering thechemistry of a fluid may be determined (both far field and near field).

8.3. Fluid pathways and fluid migration 181

This study highlights the importance of integrated multi-isotope and chemicalstudies. Quantification of two or more isotope systems means that in the futuremore sophisticated reactive-transport modelling could be undertaken, which wouldconsider the dissolution (and uptake) of different trace elements into different min-erals along fluid flow pathways. Such information could prove valuable for mineralexploration, or anthropogenic waste sequestration (e.g. estimating how different ra-dioactive elements, such as 90Sr vs 238U might react with different minerals).

8.3 Fluid pathways and fluid migration

Strontium and O isotope ratios change significantly during the growth of individualveins (see results presented in §6.4, §6.5 and §6.6). Such changes are consistentonly with segments of the fluid flow network toggling between low-permeability andhigh-permeability states (Miller and Nur, 2000), leading to changes in the degree offluid-rock reaction along flow pathways. In addition, Sr and O isotope variationsbetween veins in the same outcrop indicate that different veins grew from fluids thatmigrated along episodically changing flow pathways (see §5.4.4).

Dynamic switches in fluid flow pathways could be interpreted in terms of fluidflow through a fault-fracture mesh (Hill, 1977; Sibson, 2001). In such a mesh, it ispredicted that fractures will be transiently permeable after fracturing (promotingrapid migration of fluids), and then this permeability will be destroyed (i.e. viahydrothermal mineral deposition), thus creating a dynamic fluid flow environment.

The structural setting of the Taemas Vein Swarm was outlined in Chapter 4.Overprinting relations demonstrate that bedding-parallel slip (and possibly someflexural flow) occurred early during folding and continued throughout fold growth.Flexural flow folding, bedding-discordant faulting and limb stretching became moredominant failure mechanisms later in fold growth, when some fold limbs locked up.It is noted that bedding-parallel slip probably continued after frictional lock-up,whenever fluid pressures became supralithostatic (Sibson, 1985).

Timing relationships between bedding-parallel slip veins and overprinting flex-ural flow and extension veins, indicate that early during folding, fluids migratedalong bedding surfaces, probably after small, bedding-parallel slip events (i.e. mi-croearthquakes), until a fold hinge, or the end of the fault rupture was reached. Infold hinges, higher fluid pressures may have caused extension fracturing, allowingmigration of fluids through the fold hinge, and higher into stratigraphy. Later infolding, once fold lock-up occurred, fluid flow may have occurred along bedding-discordant faults and extension vein networks associated with fold limb stretching,rather than being isolated along bedding planes.

Generally, fluid flow in fracture systems is expected to be discontinuous, withbreaches of overpressured fluid reservoirs by fault rupture allowing the ascent ofoverpressured fluids (Cox, 2005). During each breach of an overpressured reservoir,a fluid pressure pulse will migrate upwards, and be preferentially transmitted alongthe more permeable, recently ruptured fault zone. The fluid pressure increase willbegin to diffuse into the surrounding rocks, potentially causing a cascade of failure onother faults (i.e. aftershocks), and leading to the tensile failure criterion to be met,


causing extension fracturing (Fitzenz and Miller, 2001; Miller, 2002; Miller et al.,2004). This will in turn generate further permeability as fault slip and fracturingoccur. Fluid-driven fault failure is likely be an integral part of earthquake sequences.

Depending on the stress and fluid pressure states which exist in the rocks, failurecould occur at any point where the migrating fluid pressure wave causes failure(Miller et al., 2004). If fault failure and fluid migration occur multiple times alongthe same fault structure, this will lead to the majority of fluid being channelled alongthese larger fault zones. However, smaller faults and fractures which surround thelarger fault zone may also undergo failure, due to fluid pressure increases followingbreaching of the overpressured fluid reservoir. Changes in seismic wave propertiesin fault zones (Husen and Kissling, 2001; Haney et al., 2005), migrating earthquakeaftershock activity (Miller et al., 2004), and earthquake ‘tremors’ (Kao et al., 2005)have been linked to migrating fluid and/or fluid pressure in and around fault zones.

If the same fault structure(s) repeatedly failed, then fluids would tend to migratealong the same fault structure, and would undergo similar amounts of fluid-rockreaction with similar rocks. This would cause vein clusters at different positionsalong the same fault, or vein clusters being formed around different faults, to havesystematically different chemical compositions from other vein clusters at differentlocations. This model provides an explanation for the measurements of vein chem-ical composition made at two adjacent vein clusters in the Spirifer yassensis Lime-stone which have systematic chemical differences (results presented in §5.4.4, Figs.5.15 and 5.16). If fluids ascended along different (‘random’) flow pathways (ratherthan being preferentially channelled along larger fault structures), then it would bepredicted that no systematic differences would be observed between adjacent veinclusters in the same host rock.

Individual veins in the same outcrop are inferred to have variable chemical compo-sitions because they formed from individual fluid batches, which underwent slightlydifferent degrees of fluid-rock reaction, perhaps controlled by different fluid flow rate,or the amount of reactive-surface area created along faults during individual faultrupture events.

8.4 Fluid percolation in a fold-fracture system:

stress vs fluid pressure

8.4.1 Brittle failure modes

The Taemas Vein Swarm preserves evidence for growth of veins during folding andcrustal shortening. The widespread presence of gently dipping extension fracturesimply that σ3 was approximately vertical, and that the TVS formed in a contrac-tional tectonic environment (Anderson, 1951). The stress and fluid pressure condi-tions required for the formation of extension, extensional-shear (‘hybrid’) and shearfractures was outlined in §2.2. If a constant depth of vein formation is assumed,with the overburden pressure (σv) equal to the least principal stress, σ3, then thebrittle failure mode diagrams of Sibson (2000) may be recast in terms of pore fluidfactor, λv (Cox et al., 2001; Cox, 2005). This allows the examination of the stress

8.4. Fluid percolation in a fold-fracture system 183

and fluid pressure conditions in which different fracture types formed in the TVS.Figure 8.1 shows brittle failure mode plots for the failure of intact rock at depths

of 5 and 8 km (the proposed depth range for the Taemas Vein Swarm). Failuremodes have been calculated for rock tensile strengths of 5 and 10 MPa (typical formany limestones and shales; Lockner, 1995). A tensile strength of around 5 MPamay be a realistic value for rocks in the mid-Crust (Etheridge, 1983).

From these diagrams, the differential stress and fluid pressure states for differentfailure types reveal that:

1. If optimally oriented, cohesionless faults are present, then shear failure willalways occur on these faults before extension fractures, or new faults can form.

2. When optimally oriented, cohesionless faults are not present, then the fracturetype formed will depend on the trajectory of fluid pressure and differentialstress during deformation (see trajectories drawn on Fig. 8.1).

3. For reshear on faults severely misoriented for reactivation (e.g. when θ = 2θr),the fluid pressure must equal or exceed the lithostatic pressure (i.e. λv ≥ 1.0,and differential stress levels must be less than 8T .

4. Extension veins will only form at low differential stresses (σ1 − σ3 < 4T ).

5. Supralithostatic pore fluid pressures are required for extensional or extensional-shear failure.

6. Rocks with higher tensile strengths have a larger differential stress range overwhich extension and extensional-shear failure can occur.

The plots shown in Figure 8.1 are particularly instructive regarding the pore fluidpressure states and differential stress levels which must have occurred to allow bothextensional and shear failure in the TVS. Significant variations in differential stress(between σ1 − σ3 < 4T and σ1 − σ3 > 5.66T ) are required to allow the growth ofextension and shear veins in the same lithology. Many bedding-parallel faults in theTVS are at angles of ∼ 50−70 to the inferred σ1 direction at the time of formation(i.e. poorly oriented for reactivation). To enable bedding-parallel faults to continueto slip at such angles requires supralithostatic fluid pressures.

8.4.2 Network percolation

Cox (2005) compared the dynamics of percolation in stress-driven fault systems (‘or-dinary percolation’) versus percolation in fault systems influenced by overpressuredfluids (‘invasion percolation’). The background to percolation in fault-fracture sys-tems was presented in §2.4.4 (see also Fig. 8.2). In this section, I consider whetherthe Taemas Vein Swarm formed in an ‘ordinary percolation’ or ‘invasion percolation’situation.

Consider these two endmember scenarios for either tectonic stress or overpressuredfluids driving the growth of the Taemas Vein Swarm. In ‘ordinary percolation’(driven by stress) it would be predicted that:


0 50 100 150 200 2500

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id fa

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θ=θrCohesionless, θ=θr

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θ=2θr θ=2θr

New Fault

Differential stress, MPa (σ1-σ3)

Differential stress, MPa (σ1-σ3) Differential stress, MPa (σ1-σ3)

Differential stress, MPa (σ1-σ3)

A B CA B C

A B CA B C

D

D

D

D

Figure 8.1: Brittle failure mode diagrams (after Sibson, 2000) redrawn in termsof pore fluid factor, λv for 5 km and 8 km depth in a thrust faulting regime (i.e.σ3=vertical; Anderson, 1951) with rock density of 2650 kg m−3, and rock tensilestrengths of 5 and 10 MPa. On each failure envelope, A-B is extension failure, B-Cis extensional shear failure, and C-D is failure of a brittle fault. Also plotted arecohesionless faults (dashed lines), both optimally oriented (sloping line) and severelymisoriented (horizontal line) for reactivation. On one plot (top right), a zero differ-ential stress state at hydrostatic fluid pressure is considered (red dot), with potentialstress-fluid pressure trajectories drawn (red arrows). The rate of fluid pressure versusdifferential stress buildup will determine what type of failure occurs.

1. Faults and fractures would be distributed in a relatively homogeneous manner,with more faults and veins predicted where competence contrast is greatestbetween sedimentary layers, and where high strain regions in folds (e.g. hingezones) promote fracture growth.

2. Backbone elements, which allow externally derived fluids to migrate to highlevels in the stratigraphic sequence would develop relatively late in the defor-mation history, because it takes time for connectivity to be established betweenfractures (Fig. 8.2).

3. Early veins would have rock-buffered O-isotope compositions (except fracturesformed immediately adjacent to an external fluid reservoir), because theseveins are not connected to the external fluid reservoir, and do not ‘tap into’

8.4. Fluid percolation in a fold-fracture system 185

these fluids (‘time 1’ and ‘time 2’ in Fig. 8.2).

4. With increasing deformation, higher fluid fluxes occur, and flow pathwayslengthen as backbone elements grow longer. Therefore, oxygen isotope com-positions of veins would become progressively more fluid-buffered as veins be-come connected to the external fluid reservoir. This will be particularly truefor areas spatially isolated from the external fluid reservoir, because it willtake larger amounts of deformation to connect these areas to the externalfluid reservoir (e.g. ‘time 3’ in Fig. 8.2).

5. Many faults and fractures will never be connected to an external fluid reservoir,and instead may only be filled by fluids from the immediately surrounding hostrocks. Minerals filling these veins will have rock-buffered δ18O values.

In comparison, in ‘invasion percolation’ (growth of fracture networks driven byoverpressured fluids) it would be predicted that:

1. Faults and fractures would be locally distributed around the overpressuredfluid reservoir, because invading high-pressure fluid causes shear and/or ex-tensional failure, rather than progressive strain accumulation.

2. Long fluid pathways would develop relatively early in the deformation history,and would always be linked to the overpressured fluid reservoir, because invad-ing overpressured fluids ‘self-generate’ fluid pathways by causing failure in theimmediately surrounding rocks, allowing fluids to intrude up fractures, andcause failure.

3. Early veins will have fluid-buffered compositions, as invading overpressuredfluids cause fault failure and extension fracture growth.

The Taemas Vein Swarm is primarily isolated to the northern half of the TaemasSynclinorium, with veins heavily developed at Tates Straight, Kangaroo Flat andSharks Mouth Peninsula (Fig. 4.1). Veins in the southern half of the synclinoriumare less abundant. In addition, veins in the southern part of the syncline havehigher δ18O than veins in an equivalent stratigraphic position in the north of thesyncline (Cox, 2007). The localisation of the TVS to the north of the synclinorium,and the presence of fluid-buffered veins (with a corresponding lack of rock-bufferedveins), especially in the early stage of deformation, indicate that vein growth wasdriven by the infiltration of externally-derived fluid (Cox, 2007). Further south, veingrowth may have been principally driven by build up of tectonic stress, rather thaninfiltration of overpressured fluid.

The hydraulic connectivity of the vein swarm to the external fluid reservoir,and the presence of fluid-buffered vein compositions throughout the history of veingrowth implies that an invasion-percolation process was responsible for the growthof the Taemas Vein Swarm (Cox, 2007).


Ordinary Percolation Invasion Percolation

Time 1

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low-δ18O fluid low-δ18O fluid



δ18OFl. buff. Rk. buff.

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th Backbone

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th

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(a)

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Figure 8.2: (a) Predictions of whether fault veins growing in ‘ordinary’ or ‘invasion’percolation scenarios above a low-δ18O fluid will have rock-buffered (red) or fluid-buffered (green) compositions. Isolated and dangling segments are dashed lines, whilebackbone segments are solid lines. Faults can only have fluid-buffered compositionsonce they have been connected to the external fluid reservoir. (b) Schematic profilesof depth against vein δ18O composition as flow systems evolve in an ‘ordinary’ (left)percolation environment. On the right graph are shown predicted δ18O profiles forbackbone and dangling segments in an ‘invasion’ percolation setting. The dashed lineson this graph represent the same depth point, and illustrate that veins could haveconsiderably different δ18O values depending on the percolation segment considered(i.e. backbone vs dangling).

8.5. Fluid source 187

8.5 Fluid source

Oxygen isotope compositions of veins suggest that veins formed from a 18O depletedfluid, most likely from a meteoric source (see Sheppard, 1986, for typical isotopiccompositions of fluids from different sources). While formation of some veins fromformation waters is possible, the most 18O depleted veins strongly imply that fluidcame from a meteoric source. This requires that meteoric fluid be transported tosignificant depth in the crust (5–8 km; Chapter 5).

A fluid source involving topographically-driven flow of meteoric waters to depth,followed by overpressuring and upwards expulsion via fault and fracture networksis possible. Very high mountains would be required to drive fluids to depths of5–8 km (comparable to the Southern Alps of New Zealand or higher, see Holmet al., 1989; Upton et al., 1995; Cox, 2007). However, the closest area (Wagga-Omeo Metamorphic Belt) to the Taemas Synclinorium which shows evidence forsignificant crustal thickening lies approximately 50 km or more west of the TVS,and major deformation in this area is significantly older than the proposed age forfolding and growth of the Taemas Vein Swarm (Gray and Foster, 2004). Thus, itseems unlikely that mountains of the height required were located near the TVS.It also seems unlikely that fluids migrated approximately 50 km from the Wagga-Omeo Metamorphic Belt, across several basins and fault zones (flowing across thepredicted permeability anisotropy; Sibson, 2005), and were then localised to formthe Taemas Vein Swarm, while retaining very depleted δ18O values.

The Warroo-Deakin Fault system is considered to be a more likely fluid source.Fault systems which rupture repeatedly have the potential to draw-down hydro-statically pressured, surface-derived fluids (McCaig, 1988; Cox, 2005). During theinterseismic period, compaction of damage products will pressurise fluids trappedin the fault zone, and expel them into the wall-rocks (Sleep and Blanpied, 1992).This will lead to faulting and fracturing in the region adjacent to the fault zone, ashigher fluid pressures trigger extension fracturing and fault slip (Fig. 8.3).

8.6 Influence of fluid flow regimes on seismic be-

haviour

In many ancient tectonic fault systems, relationships between fault displacementand fault frequency may be described by power-law distributions, where the relativenumber of small and large faults is consistent over a broad range of fault displace-ments (Scholz, 1990; Walsh et al., 1991; Manfield and Cartwright, 2001; Walsh et al.,2003; Swanson, 2006). Curiously, at Taemas, there is a scarcity of mapped faultswith displacements of more than 100 m, or lengths exceeding 1 km. Apart fromthe Warroo-Deakin Fault system, most faults can only be traced for distances oftens-of-metres, with only one fault structure mapped for more than 1 km alongstrike. A power-law relationship has also been observed between the frequency andmagnitude of earthquakes (the Gutenberg-Richter Relationship). Similar scaling forfaults and earthquakes is sensible, given that tectonic faults often grow in size by theaccumulation of earthquake events (Walsh and Watterson, 1987; Cowie and Scholz,


1 km

Rising fluid pulses

Warroo Fault

Devil’s PassFault

Blind thrust

Black Range Group

SilurianVolcanics

Figure 8.3: Cartoon showing how a thrust fault at depth (splaying off the WarrooFault) could have guided fluid into the base of the Murrumbidgee Group (Blue), withrising pulses of overpressured fluid causing faulting and vein growth in the TaemasVein Swarm.

1992). The Gutenberg-Richter relationship may be described by the equation:

N(M0) = aM−B0 (8.1)

where a is a variable in time and space, and the exponent B is around 2/3 forglobal earthquakes (Scholz, 1990), and varies depending on the type of faultingenvironment (Schorlemmer et al., 2005). A high B-value means that there are manysmall earthquakes relative to large earthquakes, while a low B-value means thatthere are fewer small earthquakes compared to large earthquakes.

Earthquake swarms are often characterised by high B-values, i.e. an abundanceof small earthquakes relative to larger earthquakes (Scholz, 1968; Sykes, 1970; Hill,1977; Sibson, 2001). If the relative abundance of small faults at Taemas was inter-preted in terms of a seismological Gutenberg-Richter relationship, this would meanthat the TVS was characterised by a high-B value, suggestive of an earthquakeswarm system.

Repeated earthquake mainshocks along the Warroo-Deakin Fault system couldhave caused sustained aftershock activity in the rocks surrounding the fault system,which may have produced the Taemas Vein Swarm. Alternatively, the localisationof the TVS may be due to an underlying fault structure, which is not exposed atthe surface (i.e. a ‘blind thrust’). Such a structure could have acted as a fluid guide,localising flow and bleeding overpressured fluids into the limestones in the faulthanging wall (Fig. 8.3; cf. Miller et al., 2004). Commonly, distributed aftershockbehaviour is observed in the hanging-wall above thrust faults (e.g. Guzofski et al.,2007). Thus, the TVS could have been formed by fluids rising from an underlyingthrust fault during prolonged aftershock activity.

The Taemas Synclinorium is a compressional structure, with Silurian volcanicsoverthrusting the Murrumbidgee Group sediments along the Warroo-Deakin Faultsystem during the tightening of the Taemas Synclinorium. A modern analogue for

8.6. Influence of fluid flow regimes on seismic behaviour 189

the basin inversion and formation of the Taemas Vein Swarm may be found in theNiigata sedimentary basin (NSB), in the eastern margin of the Japan Sea. Here, upto six kilometres of sediments (muddy sediments and turbidites) are being activelyfolded and faulted during basin closure. A recent main shock-aftershock earthquakesequence is instructive with regard to interactions between folding, faulting, seismic-ity and fluid pressure in an active compressional structure (Okamura et al., 2007;Sibson, 2007).

Fold axes in the NSB are discontinuous, and overlap one another. The earthquakesequence itself consisted of a mainshock (Mw = 6.6) with a reverse mechanism,which occurred on a high angle reverse fault (Okamura et al., 2007). The main-shock occurred on a bend in the fault structure, at a depth of 9 km. Aftershocks(largest Mw = 6.3) occurred on crisscrossing reverse-slip rupture planes which wereboth favourably and unfavourably oriented for reactivation, at depths of 7–12 km(see summary in Sibson, 2007). The combined slip of optimally oriented thrusts,and reactivation of existing, unfavourably oriented faults, implies that variable fluid-overpressuring occurs within the sedimentary basin. Anomalous seismological andelectrical signatures, borehole measurements and postseismic effusion of warm, salineformation waters all suggest that fluid overpressuring and fluid migration accompa-nied the earthquake activity (Sibson, 2007). Such fluid-driven seismicity was alsoinferred for the 1997 Umbria-Marche seismic sequence, where an earthquake main-shock was followed by prolonged aftershock activity. The Umbria-Marche earth-quake sequence was modeled as a result of a high pore-fluid pressure pulse diffusingupwards from an overpressured fluid reservoir (Miller et al., 2004).

The geological setting (active folding, discontinuous fold structures, interbeddedsediments) and variation of fluid overpressure inferred for the NBS are similar tocharacteristics of the Taemas Vein Swarm. Notably, at Taemas, the pore-fluid fac-tor and differential stress varied spatially and temporally during the growth of thevein swarm. One obvious difference between the Niigata earthquake sequence andTaemas is that many of the aftershocks in the Niigata sequence are localised aroundmoderately high displacement structures, whereas the Taemas Vein Swarm is lo-calised along innumerable low-displacement faults.

In Chapter 2, fold mechanisms were reviewed, and in Chapter 4 the structuralsetting of the TVS was described. The numerous small faults and veins at Tae-mas have been interpreted as fold-accommodation structures of various types. Animportant conclusion from the review of fold mechanisms, and the structural rela-tionships presented earlier in this thesis (Chapter 4) was that flexural slip continuedthroughout folding at Taemas. This implies that if folds reached angles that ap-proached frictional lock-up (Ramsay, 1974), then flexural slip was still occurringwhen supralithostatic fluid pressures were reached (Sibson, 1985). Therefore, large,bedding-discordant faults were not developed to accommodate strain during folding.

It is suggested that no dominant ‘backbone’ flow network developed in the Tae-mas Vein Swarm. This means that fluid would have been continually channelledinto a distributed mesh of small faults and veins. The upwards infiltration of over-pressured fluids would allow slip to continue along bedding-parallel faults that wereunfavourably oriented for reactivation. Once a ‘backbone’ flow network developed,fluid would predominantly flow along the backbone, which would mean that other


faults and fractures would be effectively ‘disconnected’ from the flow network. Atthis point, further strain accumulation could be not be accommodated by fold tight-ening, as no high-pressure fluids would be available to allow continuing flexural slip.Thereafter, larger faults would develop, which would adjust the fault populationin the TVS to a more ‘typical’ displacement-frequency distribution. This had notoccurred in the Taemas area by the time crustal shortening ceased.

8.7 Implications for mineral deposits

The importance of fluid flow localisation along backbone and dangling elementsof percolation networks has been previously highlighted by Cox (1999), Cox et al.(2001) and Cox (2005). The relative importance of backbone or dangling elementsfor localising mineralisation will be dependent on the process(es) responsible fordestabilising metal-complexes in solution. These could include fluid pressure varia-tions, reaction with wall rock, or mixing with other fluids (Cox, 1999, and referencestherein).

Consider the case where fluid reaction with wall rock was the major factor caus-ing the breakdown of metal-complexes, and ore deposition. In this case, high oregrades would be promoted when fresh host rock was exposed and fluids infiltratedand reacted with wall rock. This could be achieved by the creation of new faults,lengthening of existing faults during fault slip, increasing reactive surface area viabrecciation and cataclasis of wall rock, or opening of extension veins. In such acase, locating high ore grades would be dependent on locating the dangling, down-stream elements of a percolation network (Cox, 1999), rather than the backbonestructure itself, which could become rapidly ‘armored’ by fluid-rock reaction andthe deposition of gangue minerals (Cathles, 1991).

However, the deposition of ore could be caused by fluid mixing (e.g. metamorphicfluid released from depth carrying Au-complexes, mixing with meteoric or basinfluids). Fluid mixing could alter the pH or fO2 of the ore-bearing fluid, and causethe breakdown of ore-bearing complexes (Cox et al., 1995). In such a scenario, highore grades would occur where the maximum amount of fluid mixing occurs over alimited rock volume. Such an environment would be the top of a backbone element ofa percolation network which had few dangling elements, or in a dilational jog, whereflow would be channelled into a narrow zone where fluid mixing could occur. Anotherlocation for fluid mixing would be where dangling elements at the ‘upstream’ end ofa flow system (fluid feeders) intersect the upstream end of a backbone flow network(Cox, 1999).

If a temporal history of vein deposition can be inferred from vein textures and/orcrosscutting relationships, then the chemical evolution of the vein minerals withtime allow the vein to be placed into the larger context of the percolation net-work. For example, a vein which formed part of the backbone network may showrepetitive chemical cycling (and incremental growth textures), with fluid-bufferedsignatures at the start of each growth increment, because backbone elements aremore likely to undergo repeated fault-slip events than isolated or dangling elements(Fig. 8.4). In comparison, a vein formed in a dangling element might show an

8.8. Future directions 191

initially fluid-buffered composition, that would become progressively rock-bufferedwith time (depending on the number of growth increments). If a dangling elementdid not have fluid flowing through it, then enhanced fluid-rock reaction could takeplace. An example of such a dangling element might be the antitaxial growth veindetailed in §6.4. Meanwhile, a vein formed in an isolated element would show con-stant rock buffered compositions, because it would never be exposed to externallyderived fluid.

Wal

l roc

k

Wal

l roc

k

Wal

l roc

k

Wal

l roc

kW

all r

ock

Wal

l roc

k

Inferred growth direction

Oldest Youngest

Distance across vein

δ18O

Fluid buffered

Rock buffered

Wal

l roc

k

Wal

l roc

k

Inferred growth direction

Oldest Youngest

Cra

ck-s

eal b

ands

Distance across vein

Dangling element

Isolated element (rock-buffered)

(a)

(b)

(c)

(d)δ18

O

Figure 8.4: Schematic diagrams showing (a) elongate-blocky vein with (b) predictedδ18O values if vein grew in an isolated or dangling element. (c) Crack-seal vein whichformed in a backbone element which has undergone repeated fracturing and sealingevents. (d) schematic of how δ18O values might vary across such a vein (c) whichgrew in a backbone element, that repeatedly accessed low-δ18O fluid during multiplefault-slip increments.

8.8 Future directions

This thesis has explored the interplay between folding, faulting, fluid flow andfluid chemistry. Particular emphasis has been placed on extracting records of fluidflow from different textured veins using microchemical techniques, and determiningwhether vein textures are diagnostic of a particular fluid flow regime or mass transferprocess.

The variation in calcite crystal morphology presented in Chapter 3, and potentiallinks between fluid chemistry and vein texture discussed in §8.2.1 warrant further


investigation and experiments. Firstly, the preliminary experiments presented inChapter 3 should be extended to determine the influence of varying calcite super-saturation and trace element composition on crystal morphology. Different traceelements could be added into solutions to examine if crystal morphology respondssimply to increased ‘poisoning’ of solutions, or if specific trace element-ligand com-plexes promote specific crystal morphologies. The hypothesis presented in §8.2.1that fluid chemistry is a controlling factor on vein texture may be tested in a fieldsetting. Such a test would involve investigating the trace element chemistry of dif-ferent textured veins within the same outcrop, and determine if fibrous veins haveconsistently different compositions to massive and/or elongate-blocky veins.

Isotopic and trace element analyses of an antitaxial calcite vein presented in §6.4demonstrate that fibrous textured veins may form in advective fluid flow regimes.The studies of Elburg et al. (2002) and Barker et al. (2006) both demonstrate hetero-geneous variations in Sr isotope ratios across different growth regions in antitaxialfibrous veins. The advent of the rapid ( ∼ 10 − 15 minutes per analysis), highprecision in situ laser ablation MC-ICP-MS technique allows many more Sr isotopeanalyses to be carried out than is possible in a similar time period by traditionalTIMS techniques. Future studies should utilise this analytical technique to deter-mine how fluid sources and/or fluid pathways change during the growth of differenttextured veins (particularly veins containing carbonate minerals). It is emphasisedhere that combined textural and (especially in situ) microchemical analyses reveala wealth of information that cannot be extracted from ‘bulk’ analyses of veins andadjacent host rock.

Samarium-neodymium isotope studies have shown promise for dating both fluo-rite and calcite hydrothermal mineralisation (Chesley et al., 1991; Peng et al., 2003).Variations in the kinetics of exchange for different elements, the derivation of differ-ent trace elements from different lithologies and/or minerals during hydrothermalfluid flow, and variations in the ratios of different species in rocks and fluids leadto decoupling of different isotope systems (cf. Bau et al., 2003). It is apparentfrom the analyses presented in Chapter 7 that caution must be used when select-ing samples for dating via isochron techniques in hydrothermal systems. Withoutverification that samples deposited from fluid with the same initial Nd isotopic com-position, no confidence can be placed in an ‘isochron’ determined from veins in ahydrothermal system. Future geochronological studies, particularly of vein carbon-ates, should utilise trace elements and C, O and Sr isotope ratios to establish thatsamples may have been deposited from a fluid with the same initial Nd isotopiccomposition. The samarium-neodymium isotope system may be most useful as atracer of varying fluid sources and fluid pathways in hydrothermal systems, ratherthan as a geochronological tool.

This study highlights the application of modern and emerging analytical tech-niques to explore the dynamics of hydrothermal fluid flow. Many exciting appli-cations of these techniques have been explored in this thesis. Substantial furtherwork is required via experimental calibration (e.g. estimating precipitation rates inhydrothermal veins) and analyses of natural veins from other localities to compareobservations made in this thesis on the Taemas Vein Swarm, with other vein systemsin a range of mid-to-upper crustal conditions.

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Samples - Isotopes

Table 1: Sr, C and O isotope ratios for samples used in Chap-ter 5. The table key is as follows: ‘Samp’ is Sample identifiers,‘Host’ is host rock (CBL=Cavan Bluff Limestone, SYL=Spirifer yassen-sis Limestone, CJL=Currajong Limestone, BFL=Bloomfield Limestone,RCP=Receptaculites Limestone, W=Warroo Fault samples), east and northare the GPS locations of samples (where eastings have 06 before all num-bers, northings have 61 before all numbers), ‘Type’ is vein type (F=fault,E=extension, B=bedding-parallel), Ht is stratigraphic height, where 0 is de-fined as the base of the Cavan Bluff Limestone.

Samp Host Outcrop East North Type Ht (m) δ13C δ18O 87Sr/86Sr ± 2σc1 CBL Tate St 63162 34543 F 30 1.29 17.76 0.70833 0.00003c10 CBL Tate St 63162 34543 E 20 1.37 17.95c12 CBL Tate St 63162 34543 E 20 0.70 17.88 0.70832 0.00002c13 CBL Tate St 63162 34543 B 20 0.59 17.51 0.70832 0.00001c16 CBL Tate St 63162 34543 B 20 -0.70 17.28 0.70830 0.00002c23 CBL Tate St 63199 31328 B -15 -0.86 4.36 0.70820 0.00002c27 CBL Tate St 63156 34124 E 0 1.21 0.76 0.70825 0.00005c27a CBL Tate St 63156 34124 B 0 1.21 0.76 0.70825 0.00005c2a CBL Tate St 63227 31332 E 10 -8.39 14.09 0.70897 0.00002ts15 CBL Tate St 62860 32405 E 22.2 0.50 9.30 0.70831 0.00001ts20 CBL Tate St 62860 32405 E 25 0.72 17.40ts32 CBL Tate St 62860 32405 E 35 1.34 17.78ts37 CBL Tate St 62860 32405 E 30 1.16 17.80LB04 CBL TSFFC 62845 32450 E 30 0.73 17.12 0.70834 0.00002cb101 CBL TSFFC 62845 32450 B 30 0.02 15.51 0.70825 0.00001cb102 CBL TSFFC 62845 32450 B 31 0.89 17.96 0.70833 0.00002cb103 CBL TSFFC 62845 32450 B 32 1.10 17.37 0.70835 0.00002cb104 CBL TSFFC 62845 32450 B 26 1.05 17.79 0.70835 0.00002cb105 CBL TSFFC 62845 32450 E 27 0.95 16.51 0.70831 0.00001cb106 CBL TSFFC 62845 32450 E 28 1.05 18.07 0.70831 0.00002cb107 CBL TSFFC 62845 32450 E 27 0.90 18.64 0.70835 0.00001cb108 CBL TSFFC 62785 32535 B 30 -0.17 19.56 0.70839 0.00002cb109 CBL TSFFC 62795 32500 F 32 1.19 17.84 0.70831 0.00004cb110 CBL TSFFC 62790 32530 B 32 1.17 18.25 0.70834 0.00002cb203 CBL TSFFC 62839 32422 E 31

cb203-2 CBL TSFFC 62839 32422 E 31cb204 CBL TSFFC 62839 32422 E 31 0.70835 0.00001cb205 CBL TSFFC 62839 32422 E 27 0.70834 0.00002cb208 CBL TSFFC 62839 32422 E 27 0.70835 0.00001cb209 CBL TSFFC 62839 32422 E 27 0.70835 0.00001cb210 CBL TSFFC 62839 32422 E 31 0.70834 0.00002cb211 CBL TSFFC 62839 32422 E 31 0.70835 0.0000104/06 CBL Tate St 63325 34590 F 80sp1 SYL E end SM 66201 29311 F 302

sp1-2 SYL E end SM 66201 29311 F 302sp2 SYL E end SM 66201 29311 F 302sp4 SYL E end SM 66201 29311 F 304.5sp7 SYL E end SM 66201 29311 F 303sp13 SYL E end SM 66201 29311 E 298sp14 SYL E end SM 66201 29311 F 298sp18 SYL E end SM 66201 29311 E 298sp19 SYL E end SM 66201 29311 E 298sp101 SYL Roo Flat 64640 31350 B 300 0.96 22.40 0.70852 0.00002sp102 SYL Roo Flat 64641 31350 B 300 0.69 22.63 0.70852 0.00001

213

Table 1 – continued from previous pageSamp Host Outcrop East North Type Ht (m) δ13C δ18O 87Sr/86Sr ± 2σsp103 SYL Roo Flat 64642 31350 B 300 0.89 22.45 0.70852 0.00002sp104 SYL Roo Flat 64643 31350 F 300 0.80 22.49 0.70849 0.00002sp105 SYL Roo Flat 64644 31350 F 300 0.76 22.54 0.70851 0.00002sp106 SYL Roo Flat 64645 31350 E 300 0.98 22.36sp107 SYL Roo Flat 64646 31350 B 300 1.02 22.35 0.70857 0.00002sp108 SYL Roo Flat 64647 31350 E 300 0.85 20.68 0.70845 0.00001sp110 SYL Roo Flat 64648 31350 E 300 0.94 22.36 0.70854 0.00002sp111 SYL Roo Flat 64649 31350 E 300 0.74 21.10sp201 SYL Roo Flat 64653 31379 F 290 0.86 23.04 0.70836 0.00002sp202 SYL Roo Flat 64654 31379 E 290 0.87 23.09 0.70835 0.00002sp204 SYL Roo Flat 64655 31379 F 290 0.70842 0.00002sp205 SYL Roo Flat 64656 31379 B 290 0.69 22.75 0.70837 0.00001sp206 SYL Roo Flat 64657 31379 E 286 0.78 22.77 0.70837 0.00002sp208 SYL Roo Flat 64658 31345 F 275 0.60 21.97 0.70838 0.00001sp209 SYL Roo Flat 64659 31345 F 275 0.63 21.96 0.70836 0.00001sp210 SYL Roo Flat 64660 31345 F 275 0.67 22.65 0.70836 0.00001sp211 SYL Roo Flat 64661 31345 F 275 0.69 22.48 0.70847 0.00002sp212 SYL Roo Flat 64662 31345 F 275 0.70858 0.00001sp213 SYL Roo Flat 64663 31345 F 275 0.60 22.69 0.70842 0.00001sp215 SYL Roo Flat 64664 31345 B 275 1.37 25.46 0.70841 0.00002sp216 SYL Roo Flat 64665 31345 F 275 1.03 14.70 0.70853 0.00002sp216a SYL Roo Flat 64666 31345 F 275 0.70839 0.00003sp218 SYL N side SM 65950 29340 F 275 1.00 22.39 0.70844 0.00002sp219 SYL N side SM 65950 29340 F 315 0.69 22.22sp220 SYL N side SM 65950 29340 E 315 0.79 22.61 0.70832 0.00001sp221 SYL N side SM 65950 29340 E 315 0.70 22.02 0.70834 0.00002sp222 SYL N side SM 65950 29340 B 315 0.76 22.70 0.70830 0.00002sp223 SYL N side SM 65950 29340 F 315 0.41 22.57 0.70836 0.00001sp224 SYL N side SM 65950 29340 F 315 -0.72 23.30 0.70842 0.00001cf1 SYL S side SM 65950 29340 310 1.00 22.50 0.70845 0.00001s1 SYL S side SM 64372 30342 B 260 0.02 20.90

sm62 SYL S side SM 65616 28826 B 275 0.86 21.38 0.70852 0.00004sm67 SYL S side SM 65720 28850 E 275 0.80 21.59 0.70852 0.00002sm78 SYL S side SM 66120 28870 F 293 0.99 22.96 0.70844 0.00002sm81 SYL S side SM 66120 28870 F 293 0.77 22.75 0.70841 0.00001sm84 SYL S side SM 66120 28870 E 295 1.17 22.44sm94 SYL S side SM 66120 28870 F 285 1.01 22.26 0.70854 0.00002cj101 CJL Roo Flat 64655 31413 E 405 1.18 23.95 0.70823 0.00001cj102 CJL Roo Flat 64656 31413 B 400 0.22 24.22 0.70830 0.00001cj104 CJL Roo Flat 64657 31413 E 395 1.39 23.62 0.70820 0.00002cj105 CJL Roo Flat 64658 31413 E 393 0.70822 0.00001cj106 CJL Roo Flat 64659 31413 E 390 1.62 23.41 0.70821 0.00001cj107 CJL Roo Flat 64660 31413 F 385 1.66 20.22 0.70824 0.00002cj108 CJL Roo Flat 64661 31413 F 380 1.38 23.73 0.70824 0.00001cj109 CJL Roo Flat 64662 31413 F 381 0.70826 0.00001cj110 CJL Roo Flat 64663 31413 F 382 1.25 23.85 0.70824 0.00001cj110b CJL Roo Flat 64664 31413 F 382cj111 CJL Roo Flat 64665 31413 F 383 1.16 22.92 0.70822 0.00002cj112 CJL N side SM 65363 29590 B 390 -1.07 20.06 0.70858 0.00002cj113 CJL N side SM 65363 29590 F 405 1.36 22.43 0.70824 0.00001cj114 CJL N side SM 65363 29590 F 405 1.43 22.42 0.70824 0.00001cj115 CJL N side SM 65363 29590 F 405 1.26 22.59 0.70825 0.00001cj116 CJL N side SM 65363 29590 F 405 1.38 22.87 0.70825 0.00002cj117 CJL N side SM 65647 29560 F 380 1.83 22.05 0.70821 0.00002cj118 CJL N side SM 65647 29560 E 385 0.44 24.24 0.70818 0.00002cj119 CJL N side SM 65647 29560 B 390 0.81 22.60 0.70824 0.00001

cj119-2 CJL N side SM 65647 29560 B 390 0.70827 0.00001cj120 CJL N side SM 65647 29560 E 388 1.33 23.22 0.70822 0.00001cj121 CJL N side SM 65647 29560 E 380 1.53 24.06 0.70822 0.00002cj122 CJL N side SM 65647 29560 B 368 1.05 22.87 0.70830 0.00002cj123 CJL N side SM 65647 29560 E 365 0.10 22.48 0.70846 0.00002cj126 CJL Currajong Syncline 66017 29337 B 325 0.94 22.67 0.70844 0.00002

cj126-2 CJL Currajong Syncline 66017 29337 B 325 0.70846 0.70835cj127 CJL Currajong Syncline 66017 29337 F 327 -0.03 22.97 0.70835 0.00001cj129 CJL SM-Curra cliffs 65608 28984 E 390 1.62 22.66 0.70820 0.00004cj132 CJL SM-Curra cliffs 65608 28984 E 392 1.54 22.47 0.70821 0.00001cj201 CJL SM-Curra cliffs 65610 28986 E 385 0.70826 0.00002cj202 CJL SM-Curra cliffs 65610 28986 F 385 0.70827 0.00002

Table 1 – continued from previous pageSamp Host Outcrop East North Type Ht (m) δ13C δ18O 87Sr/86Sr ± 2σ

cj2 CJL Creek bed 63603 32612 F 330 0.90 22.12cj4 CJL Creek bed 63603 32612 F 330 1.17 22.49cj4b CJL Creek bed 63603 32612 F 330cj9a CJL Creek bed 63603 32612 F 330cj11b CJL Creek bed 63603 32612 F 330cj14 CJL Creek bed 63603 32612 F 330 0.33 23.34cj22 CJL Creek bed 63603 32612 F 330cj23 CJL Creek bed 63603 32612 E 330 1.08 23.56cj25 CJL Creek bed 63603 32612 E 330cj45c CJL Creek bed 63603 32612 F 320sm104 CJL SM-Curra cliffs 65608 28984 E 375 0.70824 0.00002sm5 CJL SM-Curra cliffs 65608 28984 E 380 0.70823 0.00002bl101 BFL Roo flat 64680 31485 F 420 0.71 21.79 0.70833 0.00002bl102 BFL Roo flat 64680 31485 F 422 0.53 23.11 0.70849 0.00002bl15 BFL Roo flat 64685 31503 E 432 1.03 22.82 0.70852 0.00002bl17 BFL Roo flat 64685 31503 F 430 1.07 19.57bl20 BFL Roo flat 64685 31503 F 445 0.70861 0.00002bl21 BFL Roo flat 64685 31503 F 445 0.70862 0.00002bl22 BFL Roo flat 64685 31503 E 445 0.70862 0.00002bl23 BFL Roo flat 64685 31503 E 445 0.70861 0.00002bl1 BFL Roo flat 64678 31490 F 460 0.74 20.17 0.70860 0.00002bl3 BFL Roo flat 64678 31490 E 461 0.46 23.04 0.70860 0.00002bl4 BFL Roo flat 64678 31490 F 460 0.70861 0.00002bl4a BFL Roo flat 64678 31490 F 460 0.70870 0.00002bl5 BFL Roo flat 64678 31490 E 440 0.70861 0.00006

18/3 BFL SM-south 64514 33506 F 50018/9 BFL SM-south 64590 33510 F 505R-11 BFL SM-south 65489 32706 E 520 0.98 22.65w13b WL* Warroo F 800 1.19 23.35w13b WL* Warroo F 800 0.68 23.80w13c WL* Warroo F 800 1.44 23.73 0.70836 0.00004w2 WL* Warroo F 700 0.52 17.47w2a WL* Warroo F 700 0.90 10.40 0.70836 0.00001w2d WL* Warroo F 700 1.06 5.33 0.70838 0.00004

w2d-2 WL* Warroo F 700 0.63 17.80 0.70838 0.00001w2d-3 WL* Warroo F 700 0.22 19.70

w4 WL* Warroo F 730 0.25 23.00

Sam

ple

s-

trace

ele

ments

Table

2:

Sam

ple

sw

ith

aver

age

trace

elem

ent

com

posi

tions

(in

part

sper

mil-

lion)

and

Euro

piu

manom

aly

(Eu/E

u*).

Sam

ple

sare

the

sam

eas

those

giv

enin

Appen

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Afo

r‘S

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s-

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pes

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iden

tica

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cation,

host

rock

,st

ratigra

phic

hei

ght.

Sam

pM

gSc

Mn

Fe

Sr

YB

aLa

Ce

Pr

Nd

Sm

Eu

Gd

Dy

Er

Yb

Pb

Eu/Eu*

c13750

0.1

5711

3109

11207

2.9

89.9

647.0

555.5

44.8

014.7

41.8

53.4

41.2

30.5

40.1

40.0

72.0

06.9

5c1

03097

0.1

6583

3402

7570

3.7

35.0

52.2

34.4

30.5

52.2

30.5

60.7

30.7

10.5

80.1

90.1

01.2

13.5

9c1

23322

0.0

5681

3575

11924

1.1

87.1

13.1

24.5

40.4

71.6

80.3

11.1

20.2

60.1

80.0

70.0

41.8

612.2

1c1

32926

0.1

1659

3522

17770

1.6

719.1

39.2

415.5

81.6

96.1

30.9

83.2

60.6

30.2

90.1

00.0

51.6

313.8

9c1

62090

2.3

3756

3226

12264

58.7

87.2

749.4

985.6

19.2

735.6

28.5

82.3

79.4

510.2

24.4

22.4

11.9

30.8

6c2

31789

0.0

41390

3141

7735

5.0

42.8

65.6

29.0

51.1

24.5

71.0

410.6

71.2

80.8

00.2

20.0

70.3

627.9

9c2

71821

0.0

3638

1651

2098

1.5

10.1

80.3

70.5

90.0

70.3

20.0

80.0

40.1

20.1

40.0

90.0

60.0

61.4

7c2

7a

1639

0.0

8597

1643

2572

1.3

20.4

00.2

50.4

90.0

70.3

10.0

80.0

40.1

20.1

40.0

80.0

50.0

61.1

8c2

a2521

0.0

72474

5880

7814

1.5

018.1

110.8

112.3

31.1

43.7

60.5

74.0

90.4

60.2

20.0

50.0

11.5

524.5

0ts

15

2747

0.1

3693

2898

15985

5.1

617.1

712.8

022.3

62.2

88.1

31.4

43.5

41.2

50.8

00.3

00.1

71.1

819.6

5ts

20

1487

0.9

6729

1262

1112

43.8

91.2

827.4

477.3

29.8

439.4

87.5

61.8

07.3

26.9

53.7

52.8

00.2

30.8

0ts

32

2881

0.0

8593

3446

9040

2.1

48.4

47.4

812.1

91.2

74.5

00.7

41.1

20.6

00.3

50.1

00.0

52.8

69.7

2ts

37

2221

0.0

9728

2581

11615

1.1

03.5

34.3

17.2

30.7

52.6

10.4

20.7

60.3

40.1

80.0

60.0

20.3

68.9

1LB

04

2516

0.1

2774

3824

7927

4.0

312.3

016.3

521.4

52.0

36.9

01.1

41.5

31.0

10.6

70.2

30.1

01.2

84.5

6cb

101

2155

0.9

4838

2873

10990

4.7

710.4

417.5

724.7

12.3

78.2

11.3

33.1

91.2

60.8

10.3

30.2

20.6

77.5

8cb

102

2946

0.3

3817

3346

7251

4.6

19.7

63.2

37.4

00.9

33.6

40.8

12.5

50.9

10.7

20.2

70.1

61.5

910.6

0cb

103

2892

0.1

9739

3631

6486

5.1

28.1

618.2

030.2

53.1

110.9

71.8

41.8

21.5

00.9

00.2

80.1

11.5

23.9

3cb

104

2779

1.3

4703

3525

8482

20.9

28.6

227.0

257.2

66.7

125.9

25.2

31.0

94.7

33.6

81.4

90.8

91.3

60.8

2cb

105

2944

0.3

7693

3653

10664

14.7

114.0

252.4

971.4

56.7

823.1

93.9

41.4

73.4

52.5

70.8

80.3

81.2

94.7

6cb

106

3341

1.8

6723

3307

6663

20.4

010.3

818.5

140.3

84.2

216.9

03.7

80.9

43.9

73.5

71.7

31.3

11.9

20.9

2cb

107

3387

0.7

0565

1364

12193

12.0

615.7

437.0

464.0

16.5

323.3

13.9

51.7

03.2

82.1

70.8

90.5

61.2

81.4

5cb

108

2772

0.2

2697

4066

8781

3.5

87.2

010.9

720.8

52.3

48.6

31.4

11.2

81.1

10.6

00.1

90.0

91.7

24.0

3cb

109

3194

4.1

1767

3911

8937

33.8

68.8

048.6

693.6

810.4

239.3

47.7

41.7

27.1

76.1

02.7

92.0

11.4

10.7

1cb

110

3018

2.4

1727

3539

8062

36.9

07.0

837.4

480.5

19.5

437.4

88.0

51.4

37.6

66.4

42.6

11.5

31.6

60.5

8

217

Table

2–

conti

nued

from

previo

us

page

Sam

pM

gSc

Mn

Fe

Sr

YB

aLa

Ce

Pr

Nd

Sm

Eu

Gd

Dy

Er

Yb

Pb

Eu/Eu*

cb203

3109

0.0

6571

2257

12670

4.3

98.8

718.9

527.6

02.5

28.4

01.4

22.3

31.3

10.7

00.1

90.0

80.9

05.5

5cb

203-2

2953

0.0

6537

1326

14518

10.5

317.5

549.2

178.5

07.4

324.9

33.9

63.1

43.2

21.8

40.5

60.2

30.5

65.8

5cb

204

3612

0.8

7658

3564

11367

21.1

510.6

638.7

768.7

47.0

826.1

05.1

52.5

74.9

53.7

01.4

80.9

11.7

12.1

8cb

205

3278

0.0

8542

2461

7052

7.8

010.8

813.6

425.1

72.7

210.4

52.1

02.0

72.0

81.1

80.3

10.1

11.6

14.3

7cb

208

3280

0.3

6646

3018

9547

37.3

37.6

929.5

067.9

28.0

232.3

77.4

82.0

77.6

56.0

52.2

31.2

21.8

22.3

4cb

209

3265

0.7

7599

2816

8004

16.7

77.1

123.8

141.8

04.4

416.8

13.4

71.9

83.4

12.7

81.2

70.8

92.0

95.1

4cb

210

2786

0.1

8602

2508

8549

21.3

16.8

328.5

866.3

07.6

229.7

86.1

72.0

85.5

93.5

61.1

50.6

11.5

11.5

2cb

211

3133

0.3

7531

2454

9114

16.4

910.4

331.3

762.2

26.5

524.3

84.6

31.8

74.0

82.7

41.0

50.6

51.7

21.3

204/06

2904

1.4

0554

4089

7551

18.1

93.3

119.5

144.0

15.3

321.0

24.5

31.3

84.2

23.2

01.1

60.6

51.2

10.9

6sp

12614

0.3

3155

2634

3855

3.0

61.2

06.7

313.6

31.5

95.8

50.9

70.4

50.7

90.5

00.1

80.1

10.2

51.6

6sp

1-2

2474

1.8

9203

2989

4182

6.0

41.8

812.1

721.4

42.3

78.7

61.5

00.6

81.2

61.0

80.5

50.4

40.3

31.5

0sp

22706

1.5

9181

2797

4150

8.1

71.4

010.6

023.1

32.8

410.9

22.0

50.4

61.7

81.5

10.6

90.4

60.2

60.7

8sp

42992

0.5

0226

3411

3428

3.7

91.4

84.4

99.1

81.1

34.4

50.8

90.7

80.8

40.6

40.2

60.1

70.7

83.1

6sp

72803

2.5

3203

3536

3660

8.8

41.8

215.6

135.7

94.3

415.8

12.6

11.1

12.0

21.5

00.6

70.4

90.3

01.6

5sp

13

2631

0.2

3189

2573

4710

6.6

74.4

39.0

620.3

22.4

99.7

31.8

10.4

61.6

31.1

50.4

40.2

30.3

40.8

2sp

14

2855

0.3

6177

2956

4337

3.9

61.7

112.5

422.3

32.4

68.6

81.3

30.6

81.0

50.6

70.2

40.1

30.1

82.0

9sp

18

2819

0.3

5130

1969

3459

1.6

42.3

64.2

47.3

00.7

82.7

80.4

50.2

50.4

00.2

50.1

00.0

60.3

22.0

2sp

19

3263

1.3

8137

3380

3547

4.8

51.4

110.1

918.5

82.0

67.2

61.2

60.4

01.0

70.8

20.3

60.2

50.2

51.1

1sp

101

1706

0.1

1253

2837

1952

1.4

41.0

50.5

71.6

40.2

91.5

30.4

00.4

70.3

50.2

10.0

70.0

30.3

94.0

4sp

102

3174

1.1

2232

3353

3963

8.9

01.6

59.2

521.1

02.6

710.8

52.1

40.6

21.9

11.5

90.7

40.5

20.1

80.9

4sp

103

2558

0.4

9280

3287

2967

2.8

50.8

61.4

23.8

30.6

33.1

10.7

10.6

50.6

70.4

50.1

70.0

90.4

53.9

3sp

104

2840

0.7

2247

3549

3288

2.6

81.0

71.8

64.0

80.5

62.4

10.5

50.5

10.5

40.4

50.2

00.1

40.8

15.0

9sp

105

3131

0.9

0229

3723

3751

17.7

31.5

39.0

225.1

53.7

817.4

74.1

90.7

13.8

63.1

11.2

10.6

70.1

80.6

2sp

106

2596

0.9

9361

4210

3291

9.9

01.4

67.5

717.4

62.4

510.4

72.3

02.1

02.0

51.6

50.7

00.4

60.4

43.0

0sp

107

2773

0.5

7403

4671

2782

8.9

11.8

94.5

413.6

12.2

210.3

82.4

71.0

42.1

11.5

00.5

20.2

80.3

72.0

3sp

108

2604

1.4

8308

3650

4571

10.1

41.7

513.8

134.5

64.7

219.3

73.5

62.2

92.6

71.8

30.7

10.4

10.4

22.3

9sp

110

3144

0.4

0254

4274

3066

6.6

70.7

85.1

715.0

62.1

89.3

31.9

31.1

01.6

51.1

70.4

00.1

90.4

51.9

6sp

111

2397

0.5

1214

3026

2606

4.5

13.4

03.5

69.5

41.3

85.8

71.2

10.4

81.0

50.7

30.2

70.1

40.3

01.3

1sp

201

2825

0.8

0221

2557

4330

7.6

21.8

09.0

220.3

92.7

011.3

22.2

40.7

61.8

61.1

80.4

00.2

10.2

81.5

5sp

202

3145

0.2

6209

2197

4329

2.2

21.1

94.7

19.6

31.0

33.7

10.6

50.3

60.5

30.3

40.1

20.0

60.2

12.0

6sp

204

3405

0.1

8168

2243

4047

1.3

01.6

93.0

25.7

60.6

42.3

40.4

00.2

10.3

20.2

00.0

70.0

50.2

91.8

7sp

205

2737

0.4

8198

2062

4972

4.0

01.7

712.8

623.2

22.5

18.7

81.3

80.5

21.0

40.6

50.2

40.1

40.0

71.3

7sp

206

2984

0.5

7160

1818

3159

1.6

61.1

13.2

95.5

10.5

72.0

60.3

70.1

40.3

30.2

80.1

40.1

20.1

61.5

0sp

208

2082

0.2

7210

2550

3920

5.1

81.3

52.6

37.0

11.1

45.3

31.2

70.8

01.1

80.8

40.3

00.1

40.0

82.1

5sp

209

4643

5.7

7226

3140

4301

22.9

81.3

313.7

242.5

66.3

727.4

75.9

51.1

85.0

94.2

31.8

71.2

60.0

70.6

9sp

210

2632

0.3

4204

2169

4039

1.9

81.0

81.2

13.1

60.4

41.9

10.4

10.3

00.4

00.3

30.1

30.0

90.0

32.3

2sp

211

2511

0.4

1277

3128

4046

5.5

01.2

510.1

024.9

33.1

812.1

92.0

20.9

41.5

40.9

60.3

60.2

20.0

81.6

3sp

212

2718

0.2

5240

3354

3426

3.1

00.4

33.5

18.8

21.1

94.8

90.9

00.7

60.7

40.5

30.1

90.0

80.2

13.6

8sp

213

2728

2.1

5260

3070

4710

11.5

51.8

210.4

625.9

83.5

214.4

32.9

41.0

02.5

82.0

90.9

00.6

00.1

11.1

8sp

215

2640

0.2

3245

2561

4003

4.9

41.2

09.1

217.5

12.2

28.5

31.4

71.0

21.2

00.7

90.3

00.1

50.0

53.5

0sp

216

2181

0.9

9133

829

1995

3.8

10.2

10.3

61.2

50.2

21.1

20.4

20.1

10.5

60.6

20.3

40.2

60.0

10.7

0sp

216a

2736

1.5

0437

3726

3162

11.5

63.1

29.6

224.4

73.3

814.1

82.8

91.1

92.5

62.0

70.9

30.7

40.3

81.6

5sp

218

2914

0.8

0157

2534

3609

3.0

51.2

45.6

99.5

21.0

53.8

40.7

30.4

20.6

30.5

20.2

20.1

80.3

73.5

2

Table

2–

conti

nued

from

previo

us

page

Sam

pM

gSc

Mn

Fe

Sr

YB

aLa

Ce

Pr

Nd

Sm

Eu

Gd

Dy

Er

Yb

Pb

Eu/Eu*

sp219

2696

0.5

4213

2661

3889

5.4

70.8

211.8

319.1

22.0

47.3

11.3

61.6

21.2

10.8

20.2

80.1

40.3

44.3

5sp

220

3188

1.6

5172

2063

6927

3.3

21.3

64.2

28.5

30.9

53.5

50.7

10.2

20.6

30.5

60.3

00.2

70.0

90.9

8sp

221

3157

0.4

8132

1766

5504

1.1

31.5

01.7

63.3

30.3

61.3

50.2

60.1

30.2

20.1

80.0

90.0

70.1

03.0

9sp

222

3152

0.1

1133

1469

7520

0.7

81.0

72.6

94.2

40.4

31.4

80.2

50.1

40.1

90.1

20.0

40.0

20.0

71.9

8sp

223

3177

0.8

4173

1698

9776

2.8

92.2

73.1

65.9

20.6

62.5

10.5

20.2

60.5

20.4

80.2

50.2

20.0

72.0

5sp

224

2379

1.2

3187

1694

5272

4.4

22.7

45.6

512.2

81.4

65.6

41.0

90.3

20.9

30.7

50.3

30.2

40.1

11.2

2cf

12771

0.0

2185

2592

3343

0.1

01.6

90.4

40.6

50.0

70.2

50.0

40.2

60.0

30.0

10.0

00.0

00.1

426.9

4s1

2325

3.8

11660

4383

5192

41.6

21.5

315.9

846.4

87.7

441.6

213.4

68.4

812.4

38.4

52.8

51.7

30.8

32.0

0sm

62

1954

1.5

0115

2079

1983

5.3

51.5

14.8

411.2

01.4

15.5

61.1

50.2

11.0

40.9

40.4

40.3

00.1

60.5

7sm

67

2929

7.2

3331

3747

4126

27.6

80.8

019.6

751.8

26.9

728.9

75.9

50.8

15.4

85.2

22.5

91.9

20.2

90.4

3sm

78

3063

1.6

2149

2603

3158

5.2

20.8

813.9

224.8

52.6

89.3

21.4

60.3

81.1

60.9

10.4

00.3

10.1

00.9

0sm

81

2634

1.3

6191

3053

4244

10.3

61.1

018.7

738.7

94.4

516.1

32.8

10.6

62.3

21.9

10.8

30.5

40.0

60.7

4sm

84

2896

1.8

4127

3100

3582

6.9

00.9

515.4

828.1

83.1

211.0

51.9

00.4

41.5

41.2

50.6

20.4

80.1

80.8

1sm

94

2577

1.9

4196

3462

2695

9.7

01.7

37.1

219.3

72.5

710.5

92.1

90.5

12.0

31.7

30.7

50.4

80.2

10.8

0cj

101

3239

0.0

683

288

3796

0.2

41.2

60.4

80.8

30.0

90.3

20.0

60.0

80.0

50.0

30.0

10.0

00.1

24.4

1cj

102

3019

1.4

0173

1704

6821

3.9

013.6

67.2

116.4

62.0

57.6

61.3

20.6

61.0

60.7

50.3

10.2

10.1

72.6

5cj

104

3157

0.6

544

331

10072

1.5

01.4

82.0

24.4

10.5

42.0

40.3

70.1

00.3

20.2

60.1

20.1

00.0

80.9

3cj

105

2507

0.2

127

133

6562

0.7

61.2

31.0

41.9

50.2

20.8

00.1

50.0

40.1

30.1

20.0

60.0

40.1

31.2

9cj

106

3137

0.1

129

129

7744

0.6

71.4

01.7

93.0

80.3

31.1

20.1

70.0

60.1

40.0

80.0

30.0

10.0

61.2

5cj

107

1640

0.1

334

63

3473

0.4

10.1

20.2

00.5

20.0

70.3

10.0

70.0

10.0

70.0

60.0

30.0

30.1

40.5

2cj

108

2790

1.4

435

239

4077

4.2

61.1

110.3

817.4

01.8

76.6

11.0

90.1

50.9

40.7

70.3

90.3

10.2

60.4

8cj

109

3334

0.5

874

781

3813

2.4

21.5

64.0

37.8

40.9

23.3

30.5

90.2

00.5

20.4

00.1

70.1

10.1

61.4

6cj

110

3089

0.2

591

991

3276

1.4

00.9

73.4

16.2

70.7

12.4

80.4

00.1

70.3

30.2

00.0

70.0

40.0

71.5

8cj

110b

3383

0.5

039

165

7701

1.1

20.7

61.2

92.6

20.3

21.1

90.2

40.0

70.2

20.1

90.0

90.0

60.0

61.0

1cj

111

3095

0.2

144

85

8878

0.7

41.6

03.9

45.8

30.5

81.9

30.2

60.1

00.2

00.1

00.0

40.0

20.1

11.4

2cj

112

3680

1.1

576

444

7571

3.4

64.7

59.3

015.4

41.6

35.6

70.9

80.3

30.7

70.5

70.2

50.1

90.4

11.1

6cj

113

4893

0.2

161

283

5221

1.6

71.6

45.9

110.6

51.0

73.6

20.5

70.2

30.4

40.2

00.0

50.0

20.0

81.4

7cj

114

2965

3.1

258

264

4266

4.9

41.9

34.0

08.8

41.0

64.2

00.8

80.1

80.9

00.9

50.5

80.5

60.1

30.6

0cj

115

2745

1.5

263

211

4283

3.4

31.8

12.8

36.3

80.7

42.8

80.6

30.1

30.5

90.5

60.3

00.2

60.2

90.7

3cj

116

3393

0.1

4155

272

3764

1.1

11.4

60.9

91.9

70.2

40.9

40.1

90.3

10.2

00.1

30.0

30.0

10.0

44.8

3cj

117

2101

0.0

739

45

1942

0.6

50.3

70.7

11.0

80.1

10.4

20.0

80.0

10.0

90.0

80.0

50.0

30.0

20.5

3cj

118

3040

0.2

540

58

12088

1.1

41.0

81.0

41.7

70.2

20.8

50.1

80.0

60.2

00.1

90.1

10.0

80.1

71.2

2cj

119

3035

1.4

273

85

7438

3.4

21.1

07.0

412.8

41.3

75.0

50.8

80.2

10.7

30.6

00.3

00.2

60.0

40.8

0cj

119-2

3006

1.5

475

103

6797

3.2

01.1

16.3

511.2

81.2

34.4

50.8

00.1

80.6

70.5

60.2

80.2

30.0

30.7

7cj

11b

2586

0.2

070

972

6043

0.8

00.8

61.4

22.7

50.2

91.0

40.2

00.1

20.1

70.1

10.0

50.0

30.0

72.2

3cj

120

3453

0.8

667

169

4431

2.6

70.7

03.9

38.2

10.9

63.5

00.6

90.1

80.5

90.4

50.1

90.1

30.0

90.8

8cj

121

2809

0.1

0105

62

6047

1.5

10.5

80.6

51.5

90.2

10.9

10.2

40.2

20.2

60.2

00.0

60.0

30.0

62.6

7cj

122

3453

0.1

742

68

5775

0.7

91.4

76.9

99.0

30.8

42.6

10.3

20.1

70.2

30.1

20.0

40.0

20.1

11.9

3cj

123

2978

0.6

446

96

7268

1.5

22.0

04.1

87.3

40.7

62.5

20.3

90.1

10.3

10.2

40.1

10.0

90.0

61.0

0cj

126

3074

0.6

3261

3369

4411

3.4

70.8

84.7

910.1

91.3

45.2

30.9

61.1

70.8

40.5

60.2

20.1

20.1

95.2

7cj

126

3070

0.2

7253

4080

4449

2.2

40.9

09.2

516.6

11.9

66.7

31.0

01.3

70.7

40.3

60.1

00.0

50.2

44.9

7cj

127

3403

5.9

1141

2201

5653

18.7

02.6

910.0

426.9

53.8

516.1

23.6

80.3

53.5

73.5

81.8

91.6

00.1

70.3

2cj

129

3082

0.0

535

41

4794

0.1

72.1

60.4

10.7

40.0

80.3

00.0

60.0

30.0

50.0

30.0

10.0

10.0

21.9

6

Table

2–

conti

nued

from

previo

us

page

Sam

pM

gSc

Mn

Fe

Sr

YB

aLa

Ce

Pr

Nd

Sm

Eu

Gd

Dy

Er

Yb

Pb

Eu/Eu*

cj132

3076

0.3

855

44

4901

1.1

73.6

62.2

74.0

20.4

51.5

90.2

80.1

70.2

40.1

90.0

80.0

60.0

42.0

0cj

201

2226

0.2

170

449

2593

0.7

70.5

81.8

33.0

70.3

31.1

70.1

90.1

50.1

70.1

00.0

40.0

20.0

82.8

9cj

202

2832

0.5

877

989

3426

1.3

51.0

51.8

03.2

30.3

71.3

80.2

60.1

70.2

70.2

30.1

10.0

90.3

63.6

2cj

22638

0.2

074

862

5701

0.8

81.2

51.4

92.8

10.2

91.0

60.1

90.1

10.1

70.1

20.0

50.0

30.0

51.8

7cj

42468

0.2

171

802

5160

1.1

80.8

12.3

84.0

00.4

01.3

90.2

60.1

50.2

40.1

60.0

70.0

40.0

61.8

9cj

4b

1488

0.0

941

92

1485

1.4

50.2

81.3

42.2

80.2

51.0

00.2

20.0

80.2

70.2

00.1

00.0

60.0

21.0

5cj

9a

3545

1.5

1138

1784

4852

6.3

62.7

36.3

314.6

61.8

06.9

31.4

10.3

31.2

71.1

20.4

80.3

30.2

90.8

5cj

14

2167

0.8

449

514

7376

1.9

11.6

14.1

77.9

90.8

83.1

10.5

30.1

30.4

10.3

20.1

60.1

20.3

10.9

5cj

22

2778

0.1

451

643

5217

0.6

32.0

61.9

93.3

20.3

51.2

20.2

10.1

30.1

50.0

90.0

30.0

20.2

12.3

7cj

23

2547

0.3

662

701

4289

0.9

30.7

61.1

72.2

70.2

50.9

30.2

00.0

90.1

70.1

40.0

70.0

50.2

21.6

2cj

25

1894

0.0

951

488

4842

0.5

71.6

91.8

73.5

00.3

81.2

90.1

90.0

60.1

50.0

90.0

40.0

20.2

41.2

6cj

45c

3077

1.3

1102

1051

4505

9.4

11.4

18.3

721.0

52.6

810.8

22.2

40.4

02.0

41.6

50.6

10.3

50.1

20.6

7sm

104

3236

1.8

267

263

4424

2.9

41.0

03.9

65.5

10.5

82.2

20.4

50.2

30.4

80.4

90.2

70.2

10.0

22.8

2sm

52811

1.7

070

716

3140

20.5

11.7

716.1

022.9

23.2

112.6

02.4

10.6

32.5

42.5

51.5

01.3

10.0

10.7

8bl1

01

2373

2.8

9278

2717

4309

15.0

21.0

527.3

558.4

27.0

425.2

84.1

51.7

33.4

22.6

91.1

30.8

00.0

81.4

1bl1

02

2781

1.5

3307

3920

4025

6.1

11.0

24.1

19.9

41.4

76.6

71.5

40.7

91.3

81.0

60.4

50.3

00.0

91.6

2bl1

52839

0.8

7471

3491

3185

14.3

91.8

311.1

633.0

74.7

920.2

54.1

01.2

63.5

32.4

90.9

40.5

40.3

91.0

9bl1

71869

0.0

2364

2812

2136

0.6

11.7

21.3

92.9

60.3

71.4

10.2

30.4

10.2

00.0

80.0

20.0

10.1

66.1

4bl2

02311

2.6

9492

4102

1786

25.1

01.5

97.8

027.2

55.0

425.8

86.4

51.4

45.6

14.4

61.8

71.2

20.2

20.7

8bl2

12493

0.8

6398

4242

1899

16.0

73.4

69.1

126.3

44.2

519.8

54.3

51.2

13.7

62.6

50.9

80.5

10.1

90.9

6bl2

22484

0.8

8468

5787

1826

20.0

42.0

67.7

626.9

45.1

026.2

06.4

61.5

75.6

13.5

51.1

20.5

50.1

81.2

5bl2

32656

2.4

0473

4390

2647

16.4

51.4

75.3

618.2

13.2

215.8

13.8

80.9

33.5

22.8

81.2

20.7

80.3

31.0

7bl1

2665

0.2

7358

4101

2207

3.5

21.7

63.6

47.7

21.0

04.0

80.8

60.4

00.8

20.5

80.2

10.1

10.1

22.5

6bl3

1230

0.0

8381

1715

2216

1.3

11.0

30.2

50.5

50.1

20.7

40.1

60.0

80.2

00.1

10.0

60.0

40.0

21.3

6bl4

1923

0.6

4367

4787

1812

9.8

30.9

00.9

52.6

50.5

53.4

20.9

90.3

61.3

31.2

40.7

80.5

20.0

20.9

9bl4

a1163

0.2

4316

2921

3276

2.3

80.8

70.5

61.7

60.3

41.9

60.4

10.1

10.4

20.2

90.1

60.1

00.0

30.8

0bl5

2399

0.1

7407

4216

1940

5.7

91.8

96.6

918.4

32.7

411.7

42.1

60.7

51.7

30.8

90.2

50.1

00.3

41.3

418/3

3405

0.2

8343

2955

5907

1.5

03.6

85.1

58.7

50.9

02.9

50.4

40.6

60.3

60.2

50.1

00.0

70.2

46.1

818/9

3350

1.0

1104

1816

4845

6.0

92.8

65.2

210.5

21.2

54.7

80.9

80.3

10.9

70.9

40.4

60.3

20.1

71.2

7R

-11

2329

0.0

346

51

4239

1.1

92.5

61.2

02.1

80.2

50.9

30.1

70.1

30.1

80.1

40.0

60.0

30.0

12.2

3w

13b

3828

0.0

7353

2650

6762

1.9

35.7

35.4

99.1

30.9

33.2

80.5

70.4

00.4

90.2

80.1

10.0

61.1

02.0

8w

13b

2478

0.1

2431

3324

8699

3.0

56.5

47.7

413.9

91.4

75.1

00.9

00.4

90.8

20.4

90.1

70.0

80.9

81.9

9w

13c

3139

0.1

9463

3210

638

3.4

44.5

85.7

911.1

11.1

84.4

50.8

60.3

40.8

40.5

40.2

00.1

01.0

41.2

8w

22735

0.7

860

519

2881

10.6

22.2

09.0

614.2

81.9

57.5

21.4

00.3

61.4

11.2

10.6

30.4

40.0

70.8

2w

2a

1697

0.1

4152

1492

3193

1.3

931.9

70.6

01.1

90.1

50.6

20.1

50.0

30.1

70.1

80.1

20.0

90.0

20.6

8w

2d

1860

0.0

9161

1727

3396

1.2

827.2

60.4

00.9

30.1

30.5

80.1

30.0

30.1

60.1

50.0

90.0

60.0

10.6

3w

2d-2

1770

0.1

4149

1452

3327

1.7

429.2

20.4

50.9

10.1

20.5

70.1

40.0

40.2

00.2

10.1

40.1

10.0

50.6

8w

2d-3

1859

0.0

5133

1577

3000

0.7

216.3

10.1

40.3

50.0

50.2

30.0

60.0

20.0

80.0

80.0

50.0

40.0

10.7

9w

42239

0.1

058

731

2070

1.9

31.2

42.8

73.3

10.4

51.6

20.2

60.1

60.2

60.2

00.0

80.0

50.0

23.1

6

Chapter 7 Sm-Nd-Sr isotope systematics in veins ......Isotope ratios were measured by thermal...

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Transcript of Chapter 7 Sm-Nd-Sr isotope systematics in veins ......Isotope ratios were measured by thermal...