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Erratum There are several instances of a typographic error in Figure 4.2 (page 79). The references to 'Y/Zr! in the caption and 'Y/Zr' in labels on the diagram are incorrect. They should be 'Zr/Y' in all cases.

AlteredVolcanicRocks A guide to description and interpretation

CathrynGifkins WalterHerrmann RossLarge

Published by the Centre for Ore Deposit Research University of Tasmania, Australia

UTAS

Published by CODES Centre for Ore Deposit Research, University of Tasmania, Private Bag 79, Hobart, Tasmania, Australia 7001 An ARC Special Research Centre

© Centre for Ore Deposit Research, 2005

National Library of Australia Cataloguing-in-Publication Data Gifkins, Cathryn. Altered volcanic rocks : a guide to description and interpretation. Bibliography. Includes index. ISBN 1 86295 219 1. 1. Rocks, Igneous. 2. Hydro thermal alteration. I. Herrmann, Walter, 1951- . II. Large, Ross R. III. University of Tasmania. Centre for Ore Deposit Research. IV. Title.

552.2

another Pongratz Production 2005

Copy editing: Im'press: clear communication Index: Word Wise and Im'press: clear communication Printed in Australia by the Printing Authority of Tasmania

Ill

I CONTENTS PREFACE ACKNOWLEDGEMENTS INTRODUCTION 1

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ALTERATION IN SUBMARINE VOLCANIC SUCCESSIONS

1.1

Submarine volcanic successions Volcanic facies Volcanic facies associations Evidence for submarine environment of emplacement Alteration in submarine volcanic successions Devitrification Alteration processes Characteristics inherited from volcanic facies Geology of the Mount Read Volcanics Stratigraphy of the Mount Read Volcanics Submarine facies associations and architecture Post-depositional alteration processes Mineral deposits and prospects Geology of the Mount Windsor Subprovince Stratigraphy of the Seventy Mile Range Group Submarine facies associations and architecture Post-depositional alteration processes Mineral deposits and prospects

1 1 2 2 2 4 4 6 7 9 10 11 11 12 12 13 14 14

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DESCRIBING ALTERED VOLCANIC ROCKS

15

2.1 2.2

2.6

Frequently asked questions Alteration nomenclature Mineral-based alteration nomenclature Compositional alteration nomenclature Generic alteration nomenclature Descriptive nomenclature — alteration facies Alteraction facies — the recommended method Alteration mineral assemblage Tools for mineralogical determination Alteration intensity Qualitative estimates of alteration intensity Quantitative estimates of alteration intensity An integrated approach to alteration intensity Alteration data sheets

15 19 19 20 20 20 22 23 24 25 25 26 33 36

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COMMON ALTERATION TEXTURES AND ZONATION PATTERNS

37

3.1

Alteration textures Replacement textures

37 37

1.2

1.3

1.4

2

2.3 2.4 2.5

3

v.vii viii ix 1

iv |

CONTENTS

Infill textures Dissolution textures Static recrystallisation textures Dynamic recrystallisation textures Deformation textures Pseudotextures Pseudoclastic textures False polymictic texture False matrix-supported texture False coherent textures Alteration distribution Alteration zonation patterns Regional diagenetic zones Regional metamorphic zones Regional, deep, semi-conformable altered zones Local contact metamorphic or hydrothermally altered halos Local hydrothermally altered halos around ore deposits Vein and fracture altered halos Overprinting relationships and timing of alteration Method Overprinting textures

41 41 52 52 52 54 54 63 63 63 63 64 64 64 66 66 67 67 69 70 70

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GEOCHEMISTRY OF ALTERED ROCKS

73

4.1

Lithogeochemistry Sampling and analytical methods Closure in composition data Chemostratigraphy Mass transfer techniques Rare-earth-element geochemistry related to alteration Mineral chemistry Principles Applications Stable isotopes Theoretical background Isotopic applications in alteration studies

73 73 78 79 81 87 87 87 88 92 92 92

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SEAFLOOR-AND BURIAL-RELATED ALTERATION

97

5.1

Alteration related to sea-floor processes and burial Physical conditions Definitions Hydration Palagonite Perlite Diagenesis (glass to zeolite facies) Diagenetic minerals Diagenetic zones Genesis of diagenetic minerals and zones Regional metamorphism (zeolite to amphibolite facies) Transition from diagenesis to regional metamorphism Burial metamorphism Burial metamorphic facies Burial metamorphic zones Zeolite facies Genesis Diagenetic alteration in the Hokuroku Basin Geological setting Alteration facies and zones Genesis of altered zones Data sheets

3.2

3.3 3.4

3.5

4

4.2

4.3

5

5.2

5.3

5.4

5.5

97 98 98 98 99 100 102 102 105 108 115 115 115 115 115 116 116 118 118 119 120 122

CONTENTS | V

6

5.6

Diagenetic alteration in the Mount Read Volcanics Geological setting Alteration fades and zonation Genesis of alteration fades Data sheets

128 128 128 128 133

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SYNVOLCANIC INTRUSION-RELATED ALTERATION

139

6.1

The role of intrusions in generating hydrothermal systems Subseafloor regional hydrothermal systems Regional altered zones assodated with intrusions Recharge zones Discharge zones Deep, semi-conformable altered zones Altered zones as part of a regional hydrothermal system Altered zones within intrusions Deuteric alteration Hydrothermal alteration Contact altered halos around intrusions Contact altered zones Genesis of contact altered zones Contact altered zones associated with the Darwin Granite Geological setting Alteration fades and zonation Genesis of the alteration system Data sheets

140 140 141 141 141 142 147 148 ' 148 148 149 149 153 154 155 155 156 157

LOCAL HYDROTHERMAL ALTERATION RELATED TO VHMS DEPOSITS

163

6.2

6.3

6.4

6.5

7

|

7.1 7.2

7.3 7.4

7.5

7.6

7.7

Common features of VHMS deposits Hydrothermal alteration halos associated with VHMS deposits Footwall alteration pipes Stratabound altered footwall zones Altered hanging wall zones Chemical reactions and mass changes Alteration box plot trends in altered footwall zones The genesis of footwall alteration pipes Significance of pyrophyllite and kaolinite in VHMS systems Metamorphism of altered zones The spectrum of volcanic-hosted deposits and associated alteration patterns Hydrothermal alteration related to the spectrum of deposits Comparisons between Archaean, Palaeozoic and Cainozoic VHMS alteration systems Australian Palaeozoic VHMS alteration halos Japanese Cainozoic VHMS alteration halos Canadian and Australian Archaean VHMS alteration halos Comparisons : Hellyer: a massive elongate polymetallic lens Geological setting Alteration fades and zonation Ore genesis Data sheets Rosebery: a polymetallic sheet-style deposit Geological setting Alteration facies and zonation Genesis of the ore lenses and alteration system Data sheets Western Tharsis: a hybrid Cu-Au VHMS deposit Geological setting Alteration facies and zonation

163 164 164 166 167 168 169 170 174 174 174 176 178 178 179 179 180 181 182 182 183 184 194 194 195 195 196 202 202 202

Vi | CONTENTS

Ore genesis Data sheets 7.8 Henty: a volcanogenic gold deposit Geological setting Alteration fades and zonation Ore genesis Data sheets 7.9 Thalanga: a polymetallic sheet-style deposit Geological setting Alteration facies and zonation Ore genesis Data sheets 7.10 Highway-Reward: a pipe style Cu-Au VHMS deposit Geological setting Alteration facies and zonation Ore genesis Data sheets

203 204 212 212 212 213 214 221 221 222 222 223 232 232 232 232 233

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FINDING ORE DEPOSITS IN ALTERED VOLCANIC ROCKS

8.1

Principles of discriminating between diagenetic, hydro thermal and metamorphic alteration facies Diagenetic facies Metamorphic facies Hydrothermal alteration facies Exploration vectors and proximity indicators Mineral zonation Major element lithogeochemistry Alteration indices Mass change vectors Mineral chemistry vectors Isotopic vectors

241 241 242 242 243 243 243 244 245 245 246

REFERENCES INDEX

251 271

8.2

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:

241

I vii

PREFACE

Altered volcanic rocks is principally for hands-on geologists, our fortunate colleagues who practise in mineral exploration and mining geology, and the students who may in the future play in those professional fields. We began designing and writing this book in mid 2001 after struggling for several decades to come to terms with a variety of alteration styles in ancient submarine volcanic successions. We realised that although a large number of company and research geologists were working on similar rocks there was no existing text to help guide us through the complexity of altered volcanic rocks. The so-called volcanic rocks we deal with in ancient volcanic successions and around ore deposits frequently bear little resemblance to their fresh counterparts, which are studied in undergraduate igneous petrology and volcanology courses. It is typically only with long experience that geologists develop the confidence and skills to be comfortable working with altered volcanic rocks, to interpret the original volcanic facies, unravel complex alteration histories and determine their significance in terms of mineral deposit prospectivity, particularly in ancient and deformed successions. The topic and content of the book were inspired by problems that we have faced, and in many cases overcome, while working on industry-related volcanic facies, alteration geochemistry and economic geology research projects, particularly in the Mount Read Volcanics. Many of the ideas presented in this book come from the results of CODES research projects, which have been run in collaboration with industry partners and the Australian Research Council (ARC) over the last 15 years. In particular, AMIRA-ARC Linkage project P439 (Studies of VHMS-related alteration: geochemical and mineralogical vectors to ore) provided an

enormous amount of data, case studies and expertise. Some of the results of this project have previously been published as a special issue in Economic Geology (Gemmell and Herrmann, eds., A special issue devoted to alteration associated with volcanichosted massive sulfide deposits, and its exploration significance, August 2001, v. 96, no. 5). We were encouraged by the wide acceptance and success of the CODES publication by Jocelyn McPhie, Mark Doyle and Rod Allen (1993) Volcanic textures: a guide to the interpretation of textures in volcanic rocks, which has been a major factor in improving the description and interpretation of volcanic facies over the last decade. The advance we have made in Altered volcanic rocks is to integrate observations and data on volcanic facies and textures with alteration mineralogy and geochemistry at both regional and local scales in order to provide a multidisciplinary method for the study and discrimination of different alteration types: diagenetic, metamorphic and hydrothermal alteration. We hope that this book will help to equip geologists working in altered and deformed successions with the skill and confidence to interpret the original volcanic facies and encourage the use of altered rocks as discriminants and vectors in mineral exploration. This book may not provide all the answers, but if it gives readers the courage to tackle the study of altered rocks, embrace the problems and pursue the answers it will have been worthwhile.

Cathryn C. Gifkins Wally Herrmann Ross R. Large

viii |

| ACKNOWLEDGEMENTS

While preparing this book, we were fortunate to have valuable support, assistance and advice from many people. We extend our sincere thanks to those people whose discussions and/or reviews of various chapters have helped shape this book. Chapters were peer-reviewed by Stuart Bull, David Cooke, Mark Doyle, Kim Denwer, Allan Galley, Bruce Gemmell, Anthony Harris, Jocelyn McPhie, Andrew Rae, Mike Solomon and Fernando Tornos. Valuable discussions were also held with Ron Berry, Stuart Bull, Jocelyn McPhie, Phil Robinson and Mike Solomon. Although samples and photographs used herein are principally from the authors' collections, we also made use of hand specimens and thin sections from the School of Earth Sciences rock catalogue at the University of Tasmania, and samples and photographs from colleagues. Thank you to those people who contributed: Sharon Allen, Stuart Bull, Kate Bull, Tim Callaghan, Cari Deyell, Bruce Gemmell, George Hudak, Karin Orth and Jocelyn McPhie. We also thank Izzy von Lichtan, Curator at the School of Earth Sciences, for her help in finding and returning hundreds of catalogue samples.

Andrew McNeill very kindly provided a long projection of the Rosebery ore lenses. Tim Callaghan assisted with core specimens and whole-rock geochemical data from Mount Julia. Jon Huntington and Melissa Quigley at CSIRO provided HyMap® images of the Mount Lyell field. We are infinitely grateful for the hard work of the production team. Karin Orth and Simon Stephens helped with sample preparation. Mike Blake and Karin Orth assisted with photography. Rose Pongratz and Izzy von Lichtan prepared the bibliography and checked references. June Pongratz provided expert drafting, design and desktop publishing, and was incredibly tolerant of the endless revisions. Final editing was by Impress: clear communication and indexing by Word Wise and Impress: clear communication. We also appreciate our families, friends and colleagues who have been very understanding of our commitment to this project over the last three years. Thank you for your support and patience.

I ix

r

INTRODUCTION

This book is about the processes and products of alteration in submarine volcanic successions, although many of the concepts presented here can be applied to altered volcanic rocks from almost any environment. Its emphasis is on hydrothermal alteration associated with volcanic hosted massive sulfide (VHMS) deposits. Few volcanic rocks in submarine settings are entirely unaltered, and in hydrothermal environments all rocks are altered to some degree. Recognising, describing and interpreting altered volcanic rocks is not always easy, but the results can have important implications for volcanology, petrology and ore deposit studies, and can improve and accelerate success in mineral exploration. Determining prealteration characteristics and discriminating between primary volcanic, magmatic and secondary alteration features requires knowledge of the alteration processes and their products. Valuable base-metal, gold and silver deposits exist in a variety of modern and ancient submarine volcanic successions. Many of these deposits are surrounded by, or spatially related to, extensive altered zones that record the passage of mineralising hydrothermal fluids and fluid-wall rock reactions. Research into the textural, mineralogical and compositional effects of alteration around VHMS deposits has shown that they can be quantified and used as effective exploration tools for discriminating deposit styles and guiding exploration towards mineralised zones.

An introduction to alteration Guilbert and Park (1986) defined alteration as any change in the mineralogical composition of a rock brought about by physical or chemical means, especially by the interaction with hot or cold aqueous solutions or gases. Alteration typically encompasses mineralogical changes and changes in the rock texture and composition. Components of rocks, including ore metals, can be dissolved, replaced or recrystallised. New minerals may precipitate and isotopic ratios may change. Porosity and permeability may be reduced or increased. Primary volcanic textures are overprinted, and may be destroyed and replaced by new 'false' textures, or enhanced. The resulting altered rock is described as the 'alteration fades' (e.g. Riverin and Hodgson, 1980).

Thus, alteration involves complex modification of a rock. Furthermore, a rock may undergo several episodes of syn- to post-depositional alteration, not all of which are related to mineralising hydrothermal systems. Each alteration episode is influenced by the existing texture and composition of the rock, and may also overprint and modify that texture and composition. As a result the characteristics of altered rocks are highly variable. In ancient volcanic rocks it is a challenge to determine host volcanic facies, unravel complex alteration processes and interpret their significance in terms of mineral prospectivity. That challenge is the focus of this book.

How the book is organised Altered volcanic rockshzs two main themes, which are organised into eight chapters: (1) it describes the basic principles behind recognising and describing altered volcanic rocks; and (2) it discusses the different alteration processes that are common in submarine volcanic successions and their products. Chapter 1 introduces the concepts of alteration in submarine volcanic successions and summarises the main alteration processes and volcanic facies. It outlines the regional geology of two of the most productive Australian submarine volcanic successions: the Cambrian Mount Read Volcanics in western Tasmania and the Cambro-Ordovician Mount Windsor Subprovince in Queensland. This book principally employs examples from these two successions, and includes descriptions of other ancient submarine volcanic successions for comparison. Chapter 2 discusses alteration nomenclature, mineralogy, intensity and indices, and the principles of alteration facies. It proposes an integrated multidisciplinary approach to description and classification. The main elements of alteration facies — mineral assemblage, intensity, texture, distribution, zonation and timing — are described in Chapters 2 and 3. Chapter 4 outlines geochemical methods used in alteration studies and their applications. It emphasises whole-rock lithogeochemistry, mineral chemistry and stable isotope analysis. Chapter 5 concentrates on regional alteration styles including hydration, diagenesis and metamorphism associated with burial, Chapter 6 on intrusion-related alteration styles,

X I INTRODUCTION

and Chapter 7 on hydrothermal alteration and mineralisation associated with VHMS deposits. We present short case studies for these different alteration styles, emphasising hydrothermal alteration associated with a variety of VHMS deposits including Rosebery, Hellyer, Henty and Thalanga. These case studies incorporate pictorial data sheets that present the mineralogical, textural and compositional characteristics of each of the main alteration facies. They combine volcanic facies analysis and alteration mineral assemblages, textures, intensity and geochemistry to interpret the features of different alteration styles. Chapter 8 outlines the methods for discriminating between the products of mineral deposit-related hydrothermal alteration and other alteration processes, and identifying favourable altered zones for mineral exploration. It also discusses geochemical vectors that may guide explorers towards mineralised rock within these altered zones.

.

Significance of altered volcanic rocks to mineral exploration Economic geologists are particularly interested in alteration because hydrothermal mineral deposits are commonly hosted by altered rock. Hydrothermally altered zones around mineral deposits provide much larger targets for mineral exploration than the deposits themselves. The mineral assemblages, and in some cases the chemical composition, of the altered rocks may provide indications of the proximity of an ore deposit, and thus vectors towards mineralised rock. In addition, mineralogical, textural and compositional studies of alteration facies can provide important constraints on the timing, physical and chemical conditions, and origins of hydrothermal systems and related mineralisation (Barnes, 1979). The texture and distribution of alteration facies can also be used to infer changes in porosity, permeability and fluid pathways in the host succession. The results of alteration studies are commonly incorporated into ore deposit models used in mineral exploration. Thus, the identification and interpretation of alteration facies is, and should be, a routine part of exploration for hydrothermal mineral deposits.

11

1 | ALTERATION IN SUBMARINE VOLCANIC SUCCESSIONS

This chapter describes submarine volcanic successions, the common processes of alteration that occur in these successions, and provides two examples of ancient submarine volcanic successions, that have been variably altered and mineralised: the Mount Read Volcanics and the Mount Windsor Subprovince. In submarine volcanic environments, the coincidence of magmatic fluids, heat and abundant seawater generates hydrothermal convection. As a consequence, submarine volcanic successions may host important hydrothermal mineral deposits, commonly referred to as volcanic-hosted massive sulfide (VHMS) deposits. VHMS deposits are a significant source of zinc, copper, lead, silver and gold, and continue to be a target for base-metal exploration. They range in size from less than one million tonnes to over 200 million tonnes, and commonly contain high metal grades. For example, the Hellyer deposit in western Tasmania produced 16.2 Mt at 13.9% Zn, 7.1% Pb, 0.4% Cu, 168 g/t Ag and 2.5 g/t Au in its nine years of operation. VHMS deposits occur mainly in submarine rift environments particularly back arc and mid ocean rifts; however, they can occur in a variety of other submarine environments including continental rifts, oceanic basins or plateaux, and arc-continent or continent-continent collision zones. They are one of the few classes of ore deposits that exist throughout the geological record from early Archaean to Recent.

by sedimentary processes. In addition, volcanic units may be emplaced into the succession as synvolcanic intrusions. This section summarises the main volcanic facies that occur in submarine volcanic successions. For a more detailed discussion of submarine volcanism, volcanic textures, facies and their interpretation, readers are referred to McPhie et al. (1993) Volcanic textures: a guide to the interpretation of textures in volcanic rocks.

Volcanic facies

For descriptive purposes, volcanic facies are divided into two main textural types: coherent and volcaniclastic. Coherent facies consist of solidified magma and are commonly characterised in volcanic rocks by aphyric (fine grained or glassy) or porphyritic textures, where porphyritic refers to evenly distributed euhedral crystals (phenocrysts) in a finegrained or glassy groundmass (McPhie et al., 1993). Volcaniclastic facies are those composed mainly of volcanic particles (Fisher, 1961). Volcanic particles are crystals, crystal fragments, shards, pumice clasts, scoria clasts and dense volcanic clasts, which may be produced by primary volcanic (pyroclastic and autoclastic) or sedimentary (weathering and erosion) processes. Volcaniclastic facies include a spectrum of facies: primary volcanic facies, syneruptive volcanic facies generated by coeval eruptions and deposited from sedimentary processes, and volcanogenic sedimentary facies that show evidence of temporary storage and reworking prior to deposition (McPhie et al., 1993). 1.1 | SUBMARINE VOLCANIC Primary volcaniclastic facies result from volcanic processes SUCCESSIONS of clast formation, transport and deposition and include Submarine volcanic successions are significantly different from hydroclastic, pyroclastic and autoclastic facies. Hydroclastic subaerial volcanic successions, as the processes of eruption, facies is a general term for facies, typically comprising blocky transport, emplacement, and post-emplacement alteration glassy particles, produced by magma-water interactions, may be strongly affected by the presence of water. Typically, whether by explosive steam generation or by non-explosive submarine volcanic successions comprise a wide variety of quench fragmentation of magma (Fisher and Schmincke, coherent and volcaniclastic facies intercalated with mixed 1984; Hanson, 1991). Pyroclastic facies comprise volcanic provenance and non-volcanic sedimentary facies (Fig. 1.1). particles (pyroclasts) that were generated by explosive The volcanic facies may be derived from intrabasinal, extra- eruptions and deposited by primary volcanic processes, by basinal or basin-margin eruptions in submarine or subaerial fallout, flow or surge. Autoclastic facies comprise volcanic settings. Eruption styles may be effusive or explosive and the particles generated by in situ non-explosive fragmentation of products may remain in situ or be redeposited or reworked lava or magma (autobrecciation and quench fragmentation).

2 | CHAPTER 1

Autobrecciation occurs when the more viscous parts of a moving lava respond in a brittle fashion to locally higher strain rates, and fragment into blocky clasts (Fisher, I960). Quench fragmentation occurs in situ where hot lava or magma comes into contact with water, ice or water-saturated sediment (Rittmann, 1962; Pichler, 1965; Yamagishi, 1987). The resulting autoclastic deposits - autobreccia, hyaloclastite or peperite - typically comprise dense blocky or splintery clasts, but they may be pumiceous and have fluidal shapes (Fisher, 1960; Pichler, 1965; Busby-Spera and White, 1987; Gifkins et al., 2002). Syneruptive volcaniclastic fades are composed dominantly of unmodified volcanic clasts that were fragmented by volcanic process such as explosive eruptions, autobrecciation or hydration, but were transported and deposited by sedimentary processes (McPhie et al., 1993; McPhie and Allen, 2003). They can occur directly from eruption when clasts bypass initial deposition as primary deposits and are delivered directly to sedimentary transport and deposition systems, such as subaqueous eruption-fed water-supported gravity currents or water-settled fall (e.g. White, 2000; McPhie and Allen, 2003). They may also occur indirectly by rapid remobilisation and redeposition during or shortly after the eruption (Fisher and Schmincke, 1984; Cas and Wright, 1987; McPhie et al., 1993). Unconsolidated volcanic debris may be remobilised by: the slumping and sliding of gravitationally unstable rapidly accumulated clastic debris; explosive eruptions; local uplift; syn-depositional faulting; and extrusion and intrusion of magma. Volcanogenic sedimentary fades (epiclastic volcanic, Fisher,

1960) contain volcanic particles derived from the posteruptive erosion and reworking of pre-existing volcanic facies and may include a significant proportion of non-volcanic particles (McPhie et al., 1993). In submarine volcanic successions, volcaniclastic facies are dominated by in situ autoclastic and syneruptive volcaniclastic facies where the particles were derived from either autoclastic fragmentation or explosive eruption. Most volcanic and nonvolcanic clastic deposits were emplaced by water-supported density currents (i.e. high- and low-concentration turbidity currents, debris flows and grain flows) and as fallout from suspension in the water column.

Evidence for submarine environment of emplacement VHMS deposits occur in submarine volcanic successions, thus exploration for new deposits is restricted to submarine successions. However, there are few volcanic or sedimentary facies that unequivocally constrain the host depositional environment. A subaqueous setting (marine or lacustrine) may be interpreted based on the presence of: water-supported massflow deposited facies; hemi-pelagic, biogenic, biochemical and chemical sedimentary facies; pillow lavas; and quench fragmented volcaniclastic facies. Also seawater-related diagenetic alteration facies (e.g. widespread albite alteration facies) can suggest a submarine environment. Without fossil evidence, differentiating between marine and lacustrine settings is difficult as few facies are restricted to either environment. Facies with tidal and wave tractional structures, such as bimodal-bipolar ripples, are submarine, whereas lacustrine settings may be indicated by the presence of evaporites. Hummocky cross stratification is more common in, although not restricted to, marine settings. Carbon-oxygen isotope signatures of carbonates can be used to support marine or lacustrine environments. Although bedforms, sedimentary structures and some sedimentary deposits help us to interpret a marine environment, they are of little help in constraining the water depth. Water depth may be an important consideration for mineral exploration as recent research suggests that Au-rich VHMS deposits are restricted to shallow water environments (e.g. Hannington et al., 1999; Hannington and Herzig, 2000; Herzig et al., 2000). Shallow water environments are typically dominated by the tractional processes of tidal and wave action and result in characteristic sedimentary structures and bedforms. In contrast, deep water environments, below storm wave base, generally lack tractional currents: sediment distribution and deposition mainly occurs through the actions of turbidity currents, debris flows and the process of suspension sedimentation. Water depth and depositional setting may be more accurately constrained by the presence of fossiliferous limestone or sedimentary facies that contain marine fossils intercalated in the volcanic succession.

Volcanic facies associations A facies association is a collection of facies that are spatially, mineralogically, compositionally or texturally related, and that may also be genetically related (Cas and Wright, 1987). There are three common types of volcanic units represented by facies associations in submarine volcanic successions (Fig. 1.1): lavas, synvolcanic intrusions (cryptodomes, sills and dykes) and syneruptive volcaniclastic facies. Lavas and synvolcanic intrusions comprise associations of coherent and autoclastic facies. The syneruptive volcaniclastic facies can be divided into two principal categories, those dominated by non- to poorly-vesicular blocky lava clasts and related to the submarine emplacement of lavas and lava domes, and others that contain abundant pumice or scoria clasts produced by explosive eruptions. In addition, there is a wide variety of volcanogenic sedimentary facies.

1.2 | ALTERATION IN SUBMARINE VOLCANIC SUCCESSIONS After emplacement, volcanic facies are commonly subjected to a variety of alteration processes (Fig. 1.2). Alteration occurs when existing components become unstable under changing physical and chemical conditions, and alter to more stable minerals. Volcanic glass, which is the main component of many volcanic facies, is a metastable solid with the structure of a liquid (Carmichael, 1979). It is undercooled to the point where extreme viscosity has prevented crystallisation. As a result, volcanic glass readily devitrifies to minerals that are more stable under surface conditions; generally clay minerals, zeolites, carbonates, feldspar, quartz and oxides (Carmichael, 1979; Henley and Ellis, 1983; Fisher and Schmincke, 1984;

ALTERATION IN SUBMARINE VOLCANIC SUCCESSIONS | 3

FIGURE 1.1 | Facies model of a submarine basin in which a variety of coherent and clastic volcanic facies are intercalated with sedimentary facies. The volcanic facies include primary coherent and autoclastic facies, syneruptive and post-eruptive volcaniclastic facies derived from submarine and subaerial eruptions. Many of the volcanic facies associations are laterally discontinuous. Common facies associations represent (A) lavas and lava domes composed of coherent and autoclastic facies; (B) synvolcanic sills and cryptodomes; (C) syneruptive volcaniclastic facies derived from explosive and effusive submarine eruptions; (D) volcanogenic sedimentary or resedimented volcaniclastic facies derived from pre-existing deposits; (E) syneruptive volcaniclastic facies derived from subaerial explosive eruptions; (F) mixed provenance sedimentary facies; and (G) marine sedimentary facies.

FIGURE 1.2 | Facies model showing the distribution of different styles of altered zones in a submarine volcanic succession that hosts VHMS deposits. See Figure 1.1 legend for the patterns denoting volcanic and sedimentary facies.

4 | CHAPTER 1

Friedman and Long, 1984; Cerling et al., 1985). Alteration of volcanic glass involves not only devitrification, but changes in texture, composition, porosity and permeability, and may simultaneously affect both the chemistry and circulation of pore fluid in the volcanic succession (Noble, 1967; Dimroth and Lichtblau, 1979; Fisher and Schmincke, 1984; Noh and Boles, 1989; Torres et al., 1995). Understanding alteration requires a range of skills that include recognising alteration minerals, textures, paragenesis, distribution, zonation, intensity, mineralogical and chemical changes associated with alteration, pathways and mechanisms for fluid migration, and fluid origin. These characteristics are related to the alteration processes and to the characteristics of the host volcanic succession.

Devitrification The cooling history of volcanic facies may involve primary crystallisation and later devitrification. Primary or hightemperature crystallisation refers to crystallisation of magma resulting in phenocrysts, microcrysts and microlites. In contrast, devitrification refers to crystallisation of glass at low temperatures (i.e. below the glass transition temperature: Lofgren, 1971a). High-temperature devitrification accompanying first cooling may produce spherulites, lithophysae and micropoikilitic or snowflake texture (e.g. Lipman, 1965; Anderson, 1969; Lofgren, 1971b; Bigger and Hanson, 1992; McArthur et al., 1998) and is not considered to be alteration. Low-temperature devitrification results in the gradual conversion of glass to fine-grained granular crystalline aggregates, which may happen over time as a result of alteration during changing physical conditions or in response to interaction with fluid. Devitrification may be accompanied by changes in whole-rock composition (Lipman, 1965; Lofgren, 1971a; Friedman and Long, 1984).

the presence of fluid (seawater, magmatic fluid or a mixture of both). There are gradations from isochemical metamorphism to metasomatism with increasing compositional changes. The different alteration processes, hydration, diagenesis, metamorphism and local hydrothermal alteration, are all part of this continuum in submarine volcanic successions (Fig. 1.3). The effects of each alteration process may be difficult to distinguish. Hydrothermal alteration, diagenesis and metamorphism can result in similar mineral assemblages and textures. In addition, in many cases, different alteration processes, such as diagenetic and hydrothermal alteration, are contemporaneous and their products may be inseparable (Iijima, 1974, 1978; Ohmoto, 1978; Reyes, 1990; Utada, 1991;Paradisetal., 1993). In Chapters 5, 6, and 7 of this book, the common alteration processes are grouped into those related to burial, intrusions and VHMS deposits (Fig. 1.4). Thus, burialrelated alteration styles include hydration, diagenesis and burial metamorphism. Alteration styles associated with intrusions are hydrothermal alteration within intrusions, contact metamorphism and hydrothermal alteration, and regional hydrothermal alteration. Included below is a brief introduction to each of the common alteration processes that operate in submarine volcanic settings.

Hydration of volcanic glass Hydration of glass involves the absorption of external water into glass and modification of the glass structure, either during cooling or at ambient temperatures (Ross and Smith, 1955; Friedman and Long, 1984). Hydration does not directly produce new minerals, but can form perlitic fractures or palagonite in basaltic glass and it can facilitate subsequent alteration (see Chapter 5). Compositional changes

Alteration processes Alteration may result from regional or local processes. It can occur as a result of the interaction with hydrothermal fluid, as a result of changing physical (mainly temperature and pressure) conditions during burial, in association with the emplacement of intrusions, or a combination of all these processes. Submarine volcanic facies, especially glassy facies, are readily altered during hydration, diagenesis, hydrothermal alteration, metamorphism and tectonic deformation. Hydrothermal alteration is defined as the alteration of rocks or minerals by the reaction of hydrothermal fluid with pre-existing solid phases (Henley and Ellis, 1983). Hydrothermal fluid is a hot aqueous solution or gas, with or without demonstrable association with igneous processes. Hydrothermal alteration usually results in significant changes in rock texture, mineralogy and composition. Alteration is either metasomatic or isochemical. Metasomatism involves changes in mineralogy, texture and composition, whereas isochemical alteration (or metamorphism) involves mineralogical and textural changes only. In submarine volcanic successions, almost all alteration involves some degree of metasomatism, which is facilitated by

FIGURE 1.3 | This cartoon depicts the continuum between isochemical and hydrothermal alteration and shows the alteration processes common in submarine volcanic successions. They are positioned based on the relative degrees of chemical exchange for each process.

ALTERATION IN SUBMARINE VOLCANIC SUCCESSIONS | 5

accompanying hydration include gains in H 2 O, and minor losses in silica and alkalis (Noble, 1967; Friedman and Long, 1984; Mungall and Martin, 1994).

Diagenesis Diagenesis encompasses the changes that occur in response to changing temperature and pressure during burial. During diagenesis of volcanic facies, significant textural and mineralogical changes can be produced by precipitation of cement, dissolution and replacement of original components, especially glass, and compaction (Fisher and Schmincke, 1984; Marsaglia and Tazaki, 1992; Torres et al., 1995). In theory, diagenesis in submarine volcanic successions is a metasomatic process involving minor chemical exchange between the host facies and trapped modified seawater at low temperatures (1.5 km thick) are composed of dacitic to basaltic lavas and sills, and polymictic mafic volcaniclastic facies interpreted as resedimented syneruptive hyaloclastite, autobreccia, pillow lava and scoria. The Mount Black Formation is a laterally extensive (>20 km), thick succession (>1.6 km) of mainly feldspar-phyric massive, flowbanded and autobrecciated lavas, domes, cryptodomes and synvolcanic sills (e.g. data sheets CVC1 CVC5 and CVC6). The Kershaw Pumice Formation, which conformably overlies the Mount Black Formation, is a laterally extensive (>16 km), relatively thick (>800 m) succession dominated by non-welded pumice breccia (e.g. data sheets CVC3 and CVC4), pumice-rich sandstone and shard-rich siltstone, with lesser proportions of pumice-lithic clast-rich breccia and sandstone, and massive, flow-banded and brecciated rhyolitic and dacitic lavas and intrusions (e.g. data sheet CVC2). The upper part of the Kershaw Pumice Formation and the base of the overlying White Spur Formation host the Rosebery and Hercules VHMS deposits. Abundant spherulites, lithophysae, micropoikilitic texture and relict perlite indicate that volcanic rocks in the northern Central Volcanic Complex were initially partly crystalline and partly glassy (Gifkins and Allen, 2001).

Alteration facies and zonation Regionally distributed diagenetic albite and epidote zones formed before, or were synchronous with, stylolitic S, compaction foliation. The alteration intensity is generally weak with volcanic textures and albite-altered plagioclase crystals preserved. Locally the distribution and intensity of the diagenetic alteration facies is patchy, reflecting the complexity of the original volcanic facies (Fig. 5.20). The albite zone is characterised by pervasive albite + quartz + sericite (e.g. data sheets CVC2 and CVC5), domainal albite + quartz + sericite with sericite + hematite ± chlorite (e.g. data sheet CVC3) and pervasive sericite (e.g. data sheet CVC4) alteration facies. It is thick (>2 km) and encompasses the Kershaw Pumice Formation and most of the Mount Black Formation (Fig. 5.21). The albite + quartz + sericite-rich facies are associated with minor increases in SiO2, CaO, Na 2 O and total mass, and decreases in K2O and A12O3 consistent with seafloor albitisation (cf. Boles and Coombs, 1977; Boles, 1982). The sericite + hematite + chlorite alteration facies is associated with minor increases in K2O and A12O3 consistent with the conversion of silicic glass to clay minerals (cf. Noh and Boles, 1989; Passaglia et al., 1995). The abundance of hematite may reflect the oxidation of Fe3+ during alteration of glass to clays (e.g. Klein and Lee, 1984). The epidote zone is characterised by pervasive albite + quartz + sericite, pervasive chlorite + sericite, pervasive chlorite + epidote and domainal chlorite + epidote with albite + quartz + sericite (e.g. data sheet CVC6) alteration facies. The epidote zone is less extensive than the albite zone and is restricted to the Mount Black Formation and Sterling Valley Volcanics at the stratigraphic base of the northern Central Volcanic Complex, adjacent to the Henty fault (Fig. 5.19). In the epidote zone, chlorite + sericite and chlorite + epidote altered felsic rocks have gained MgO, consistent with the formation of smectite, chlorite and other Mg-silicates during diagenesis (cf. Hajash and Chandler, 1981; Shiraki and Iiyama, 1990).

Genesis of alteration facies The epidote zone occurs in the core of the regional anticline in the Sterling Valley, suggesting that it is associated with the deepest stratigraphic level in the northern Central Volcanic Complex: the lower Mount Black Formation and Sterling Valley Volcanics (Gifkins, 2001). The change from the albite zone to the epidote zone with stratigraphic depth is consistent with diagenetic alteration zonation (cf. Iijima, 1974, 1978). Thick (>1 km) diagenetic zones with high-temperature mineral assemblages (albite + quartz + sericite and chlorite + epidote) suggest that they developed in response to a highgrade diagenetic alteration system that involved an elevated geothermal gradient (cf. Utada, 1991). Albite + quartz + sericite, sericite + hematite ± chlorite, and sericite alteration facies are the metamorphosed equivalents of diagenetic alteration facies that coated original surfaces, filled primary porosity and replaced glass in the northern Central Volcanic Complex prior to or synchronous with diagenetic compaction. Thin films of sericite, carbonate and hematite replaced clays that had coated original glassy surfaces at the onset of diagenesis. Albite + quartz + sericite,

SEAFLOOR-AND BURIAL-RELATED ALTERATION | 1 2 9

FIGURE 5.19 | Geology of the northern Mount Read Volcanics in western Tasmania, showing the major lithostratigraphic units and altered zones in the northern Central Volcanic Complex (after Gifkins, 2001). Locations of the six data sheets are marked on the map.

FIGURE 5.20 | Detailed cross-section in the Rosebery hanging wall (western Tasmania) showing the complex distribution of volcanic and alteration fades (after Gifkins and Allen, 2001).

FIGURE 5.21 | Schematic cross-section of the northern Central Volcanic Complex stratigraphy and altered zones, western Tasmania (after Gifkins, 2001).

SEAFLOOR- AND BURIAL-RELATED ALTERATION | 1 3 1 Stage 1: Onset of regional synvolcanic diagenesis Thin films of sericite, hematite and calcite coat original surfaces, including vesicle walls, plagioclase crystals, shards and fractures. These films are the metamorphic equivalents of low-temperature smectite, palagonite and calcite rim cements. This early stage probably involved interaction with seawater trapped in the volcanic succession. Modified seawater may have been expelled from the succession in response to overburden pressure, and migrated towards the seafloor as diffuse unfocused flow.

Stage 2: Diagenesis and synchronous hydrothermal alteration and mineralisation Zeolite or clay mineral cements began to fill primary pore spaces, vesicles and perlitic fractures. Subsequently, these were extensively replaced by K-feldspar or albite and chlorite. Zeolitisation probably occurred at temperatures between 40 and 100°C. Locally, hydrothermal fluids altered the succession. Hydrothermal fluid flow was unfocussed and in places ponded beneath the coherent facies of sills and lavas. The Rosebery and Hercules VHMS deposits and their altered halos are interpreted to have formed during this stage at temperatures greater than 300°C.

Stage 3: Continuing diagenetic alteration and compaction synchronous with deposition of the White Spur Formation Dissolution and alteration of glass to clays, sericite and chlorite occurred synchronous with compaction. Replacement of earlier zeolites by Kfeldspar occurred below 150°C, albitisation of plagioclase phenocrysts and albite replacement of K-feldspar occurred at temperatures between 100 and 190°C. Large volumes of fluid were probably displaced as a result of compaction under the weight of the accumulating White Spur Formation. Rapid and variable sedimentation rates may have over-pressured the pore fluid, promoting lateral fluid flow along permeable layers. Weak hanging wall alteration developed during continued hydrothermal alteration associated with the formation of the Rosebery deposit.

Stage 4: Transition between diagenesis and regional metamorphism More stable, higher-temperature mineral assemblages replaced remaining glass, phenocrysts and early alteration minerals. Chlorite + epidote alteration facies developed at depth in both mafic and felsic volcanic facies: probably at high (>200°C) temperatures.

Stage 5: Devonian metamorphism and deformation Greenschist facies mineral assemblages and tectonic fabrics overprinted diagenetic and hydrothermal alteration facies. Deformation modified preexisting volcanic and alteration textures and produced folds, faults and shear zones. The distribution of syn-S2 alteration facies suggests that metamorphic fluid migration was restricted to regional structures such as faults and shear zones. Mineral assemblages in intermediate and mafic rocks in the Mount Read Volcanics indicate that the peak regional metamorphic temperature was between 370 and 450°C.

FIGURE 5.22 | Model for the post-depositional evolution of the northern Central Volcanic Complex, western Tasmania (after Gifkins, 2001). Schematic crosssections are not to scale.

1 3 2 | CHAPTER 5

chlorite + sericite and sericite + hematite + chlorite replaced zeolites and clays that filled pore space and altered glass, prior to and synchronous with diagenetic compaction. In pumicerich facies, a bedding-parallel stylolitic foliation reflects the dissolution of glass during compaction and fiamme are interpreted as diagenetically altered and flattened pumice clasts (Gifkins et al., in press). Diagenetic alteration involved significant mineralogical and textural changes but only minor changes in composition consistent with the interaction of rhyolitic and basaltic glass with seawater during burial. The chlorite + epidote alteration mineral assemblage may be transitional between diagenesis and burial metamorphism. It developed after lithification and compaction but pre-dated regional deformation associated with peak metamorphism. The chlorite + epidote facies replaced earlier clay or chlorite + sericite-rich facies and filled any remaining pore space. Negligible absolute and total mass changes associated with chlorite + epidote alteration suggest that it grew in response to increasing temperature with increasing depth of burial late in the diagenetic history (Gifkins, 2001).

Mineral assemblages in these diagenetic zones reflect the reaction of glass with interstitial fluid at elevated temperatures. The albite zone probably formed at temperatures between 100 and 190°C (cf. Iijima and Utada, 1971; Thompson, 1971; Merino, 1975; Munha et al., 1980; Boles, 1982). The epidote zone is characterised by chlorite + epidote, chlorite + sericite and albite + quartz + sericite indicating formation at temperatures of at least 200°C (cf. Seki, 1972; Kristmannsdottir, 1976). The regional diagenetic alteration and metamorphism of the northern Central Volcanic Complex can be described in five successive stages (Fig. 5.22): (1) the onset of diagenesis; (2) formation of diagenetic cements, and synchronous hydrothermal alteration and mineralisation; (3) diagenetic alteration and compaction synchronous with emplacement of the White Spur Formation; (4) replacement of early diagenetic minerals and remaining glass by more stable mineral assemblages; and (5) regional Devonian metamorphism and deformation.

SEAFLOOR-AND BURIAL-RELATED ALTERATION | 133

CVC1

Subtle, pervasive albite + quartz + chlorite alteration facies Least-altered rhyoiite Sample no.

133921

Alteration facies

subtle, pervasive albite + quartz + chlorite

Alteration zone

albite zone

Location

Mount Black

Formation

Mount Black Formation

Succession

Central Volcanic Complex

Volcanic facies

massive, plagioclase-phyric rhyolite

Relict minerals

plagioclase

Relict textures

porphyritic, micropoikilitic

Primary composition rhyolite Lithofacies massive Interpretation

coherent facies

Alteration minerals

albite + quartz + sericite + chlorite + hematite albite + quartz ± sericite ± chlorite pseudomorphs of plagioclase, micropoikilitic albite + quartz, interstitial chlorite, disseminated hematite

Alteration textures

Distribution

pervasive

Preservation

excellent

Alteration intensity

subtle

Timing

pre-S2

Alteration style

diagenetic

Hand specimen photograph

Geochemistry SiO2 TiO2 AI2O3 Fe2O3 MnO MgO CaO Na2O

74.58 K2O 0.27 P2O5 13.85 S 2.08 Total 0.01 0.38 Rb 0.13 Sr 3.54 Ba

Photomicrograph (ppl)

4.34 0.03 chlorite + pyrite > calcite

Alteration textures

albite ± calcite pseudomorphs of plagiociase, microcrystaiiine groundmass, calcite veins, chlorite filled perlitic fractures

Distribution

pervasive

Preservation

moderate

Alteration intensity

weak

Timing

pre-S2

Alteration style

diagenetic

Hand specimen photograph

Geochemistry SiO2 TiO2 AI2O3 Fe2O3 MnO MgO CaO Na2O

74.01 K2O 0.23 P2O5 12.21 S 2.17 Total 0.09 0.49 Rb 2.41 Sr 4.07 Ba

Photomicrograph (xn)

1.82 0.03 0.01 100.61

Cu Pb Zn Th Zr 76 Nb 113 Y 513

2 4 19 12 258 16 36

Al CCPI Ti/Zr

26 29 5.31

SEAFLOOR- AND BURIAL-RELATED ALTERATION

Moderate, domainal albite + quartz + sericite with sencite + hematite ± chlorite alteration facies Sample no.

147410

Alteration facies Alteration zone

moderate, domainal albite + quartz + sencite albite zone

Location

120R-524.5m

Formation

Kershaw Pumice Formation

Succession

Central Volcanic Complex

Volcanic facies

graded, plagioclase-phyric pumice breccia

Relict minerals

plagioclase

CVC3

Relict textures

tube pumice clasts, fiamme, plagioclase crystal fragments, blocky rhyolite clasts Primary composition rhyolite Lithofacies

normally graded

Interpretation

Distribution

syn-eruptive, mass-flow-emplaced pumice breccia albite + quartz + sericite + chlorite + hematite + calcite sericite fiamme, hematite styioiites, albite veins, recrystallised albite + quartz + sericite pumice clasts and matrix, albite + sericite + calcite altered plagioclase domainal

Preservation

poor

Alteration intensity

moderate

Timing Alteration style

Alteration minerals Alteration textures

Geochemistry SiO2 TiO2 AI2O3 Fe2O3

76.08 0.19 10.66 1.67

S Total

pre-S2

MnO MgO CaO

0.09 0.47 2.39

diagenetic

Na2O

4.71

Hand specimen photograph

K2O

0.88 0.03 0.01 99.93

Cu Pb Zn Th

1 4 27 10

Rb Sr

34 144

Zr Nb Y

210 13 37

Ba

280

P2O5

Photomicrograph (xn)

Al CCPi Ti/Zr

16 26 5.43

|

135

1 3 6 | CHAPTER 5

Weak, pervasive sericite alteration facies Sample no.

147552

Alteration facies

weak, pervasive sericite

Alteration zone

albite zone

Location

Pieman Road

Formation

Kershaw Pumice Formation

Succession

Central Volcanic Complex

Volcanic facies

massive, plagioclase-phyric pumice breccia plagioclase

Relict minerals

CVC4

Relict textures

tube pumice ciasts, bubble wall shards, plagioclase crystal fragments, fiamme Primary composition rhyolite Lithofacies normally graded Interpretation Alteration minerals Alteration textures

syn-eruptive, mass-flow-emplaced pumice breccia sericite + albite + calcite + chlorite + hematite sericite fiamme, hematite stylolites, disseminated calcite rhombs, albite + sericite altered pumice ciasts and shards

Distribution

pervasive

Preservation

good

Alteration intensity

weak

Timing

pre-S2

Alteration style

diagenetic

Hand specimen photograph

Geochemistry SiO2 TiO2 AI2O3 Fe2O3 MnO MgO CaO Na2O

70.91 K2O 0.31 P2O5 14.08 S 2.78 Total 0.07 0.77 Rb 1.66 Sr 2.68 Ba

Photomicrograph (ppl)

3.16 0.07 0.01 99.75

Cu Pb Zn Th Zr 124 Nb 87 Y 786

4 2 48 251 13 28

Al CCPI Ti/Zr

48 36 7.41

SEAFLOOR- AND BURIAL-RELATED ALTERATION | 1 3 7

CVC5

Subtle, pervasive aibite + quartz + chlorite alteration facies Least-altered dacite Sample no.

147435

Alteration facies

subtle, pervasive aibite + quartz + chlorite

Alteration zone

aibite zone

Location

MBD4-18.4m

Formation

Mount Black Formation

Succession

Central Volcanic Complex

Volcanic facies

massive, plagioclase + hornblende-phyric dacite

Relict minerals

plagioclase, hornblende

Relict textures

porphyritic, glomeroporphyritic clusters, micropoikilitic

Primary composition

dacite

Lithofacies

massive

Interpretation

coherent facies

Alteration minerals

aibite + quartz + chlorite + epidote

Alteration textures

aibite + quartz micropoikilitic groundmass with interstitial chlorite + epidote, aibite pseudomorphs of plagioclase, epidote + chlorite altered hornblende

Distribution

pervasive

Preservation

excellent

Alteration intensity

subtle

Timing

pre-S2

Alteration style

diagenetic

Geochemistry SiO2 TiO2 AI2O3 Fe2O3 MnO MgO CaO Na,0

67.53 K2O 0.52 P2O5 14.51 S 4.37 Total 0.06 1.3 Rb 2.38 Sr 3.56 Ba

I Hand specimen photograph

Photomicrograph (ppl)

3.95 0.13 0.01 99.51

Cu Pb Zn Th Zr 102 Nb 242 Y 958

4 4 51 15 216 12 34

Al CCPI Ti/Zr

47 41 14.48

1 3 8 | CHAPTER 5

CVC6

Moderate, domainal chlorite + epidote alteration facies Sample no.

147557

Alteration facies

moderate, domainal chlorite + epidote

Alteration zone

epidote zone

Location

Pieman Road

Formation

Mount Black Formation

Succession

Central Volcanic Complex

Volcanic facies

jigsaw fit, monomictic plagioclase + homblende-phyric dacite breccia plagioclase, hornblende

Relict minerals Relict textures

glomeroporphyritic, perlitic fractures, jigsaw-fit clasts Primary composition dacite Lithofacies

massive

Interpretation

in situ hyaloclastite

Alteration minerals

albite + quartz + chlorite + epidote

Alteration textures

Distribution

microcrystalline groundmass with domainal albite + quartz and chlorite + epidote facies, plagioclase phenocrysts albite or chlorite ± epidote altered, hornblende altered to chlorite + epidote domainal

Preservation

good

Alteration intensity

weak

Timing

pre-S2

Alteration style

diagenetic

Hand specimen photograph

Geochemistry SiO2 TiO2 AI2O3 Fe2O3 MnO MgO CaO Na2O

67.93 K2O 0.59 P2O5 14.32 S 4.57 Total 0.06 1.33 Rb 2.67 Sr 4.97 Ba

Photomicrograph (ppl)

2.05 0.13 0.01 99.65

Cu Pb Zn Th Zr 41 Nb 151 Y 826

10 3 28 201 12 31

Al CCPI Ti/Zr

31 44 17.68

139

6 | SYNVOLCANIC INTRUSION-RELATED ALTERATION

The spatial and genetic associations between intrusions and altered zones are widely appreciated in porphyry and epithermal districts (Lowell and Guilbert, 1970; Titley, 1982; Henley and Brown, 1985). Similar relationships also exist in VHMS districts, where synsedimentary or synvolcanic intrusions are commonly altered and surrounded by halos of altered rocks. In some VHMS districts (e.g. Snow Lake and Sturgeon Lake, Canada), there are spatial associations between synvolcanic intrusions and broad-scale, semi-conformable altered zones and clusters of VHMS deposits in the overlying successions (Spooner and Fyfe, 1973; Campbell et al., 1981; Gibson and Watkinson, 1990; Galley, 1993; Hannington et al., 2003a). It has been suggested that synvolcanic intrusions were heat sources (Spooner and Fyfe, 1973; Ohmoto and Rye, 1974; Solomon, 1976; Cathles, 1977; Franklin et al., 1981; Polya et al., 1986; Galley, 1993; Large et al., 1996), and perhaps also volatile and metal sources (Urabe and Sato, 1978; Stanton, 1990; Yang and Scott, 1996; Hannington et al., 1999) for subseafloor hydrothermal systems that formed altered zones and VHMS deposits. Synvolcanic intrusive sills, cryptodomes, dykes and subvolcanic plutons are volumetrically important in submarine volcanic successions (Polya et al., 1986; McPhie and Allen,

1992; Doyle and Huston, 1999; Galley, 2003). They may be composite intrusions of variable volumes up to 1000 km3, typically emplaced at depths up to 4 km below the seafloor (Nielsen et al., 1981; Galley, 2003; Whalen et al., 2004). Intrusions and intrusion-related altered zones that significantly post-date volcanism are also common in ancient submarine volcanic successions; however, they are not the focus of this chapter. Alteration can occur within intrusions (deuteric and local hydrothermal alteration), locally in the immediate host rocks (contact alteration) or regionally in the host succession (regional hydrothermal alteration) (Fig. 6.1). This chapter describes the role of intrusions in generating regional hydrothermal systems, regional hydrothermally altered zones, altered zones within intrusions and contact altered zones around both small-volume, near-seafloor and larger, deeper intrusions in submarine volcanic successions. The final section presents a case study of contact altered zones associated with the Darwin Granite in the southern Mount Read Volcanics, western Tasmania. The recognition of altered zones related to synvolcanic intrusions can provide insights into fluid-flow and thermal histories of VHMS districts, and thereby assist mineral exploration.

FIGURE 6.1 | A cartoon of the variety of altered zones associated with synvolcanic intrusions. (A) A deuteric altered zone within the top of a large volume intrusion. (B) A fracture-controlled hydrothermally altered zone at the margins of an intrusion and in the surrounding host rocks. (C) Contact-altered zones around synvolcanic sills emplaced into unconsolidated sediment immediately below the seafloor. (D) Concentric contact-altered zones around a large volume intrusion emplaced at depth. (E) Regional hydrothermally altered zones related to emplacement of a subvolcanic pluton. (F) Afootwall alteration pipe beneath a VHMS deposit.

1 4 0 I CHAPTER 6

6.1 | THE ROLE OF INTRUSIONS IN GENERATING HYDROTHERMAL SYSTEMS The most active hydrothermal systems are those related to magma-induced thermal anomalies (Alt, 1999; Butterfleld, 2000). The magma chamber provides heat to overlying strata and active volcanism contributes heat from its eruptive products, intrusions and feeder dykes. The transfer of heat and mass away from the intrusion may occur by either conduction only, or conduction and infiltration. Conduction generally involves only minor diffusion of elements, although Weaver et al. (1990) suggested that at near solidus temperatures vapourphase expulsion may produce local mineral and chemical variations (loss of Na, halogens and REE) in volcanic glass. In contrast, conduction accompanied by infiltration and circulation of hot fluid can remove heat from the magmatic system much faster than conduction alone, and effectively transport elements considerable distances, up to hundreds of kilometres, through the succession. Thermal metamorphism related to the shallowemplacement of synvolcanic intrusions in dry successions typically results in limited alteration with little or no mass transfer. In rare cases, magmatic fluids exsolved from the crystallising magma hydrothermally alter dry host facies. Vapour-phase expulsion of some elemental species as complexes (e.g. fluoride, chloride, hydroxide, sulfide and carbon dioxide) may result in minor losses as glassy rocks devitrify, and glassy clasts may be welded by elevated temperatures in the contact zones (e.g. Christiansen and Lipman, 1966). The effects of intrusions emplaced into water-saturated successions are very different because water mobilises heat and soluble elements. Trapped seawater in submarine volcanic successions is heated by intrusions, initiating convection and metasomatic alteration in the overlying succession. Thus, almost all intrusion-related alteration in submarine volcanic successions involves some degree of metasomatism by magmatic fluid, modified seawater, or both.

Subseafloor regional hydrothermal systems Studies of the petrology, geochemistry and oxygen isotopes of hydrothermally altered volcanic and plutonic rocks from ophiolite complexes provide insight into subseafloor hydrothermal systems, fluid generation and circulation, and

the role of intrusions (e.g. Lydon and Jamieson, 1984; Alt et al., 1986; Gillis and Robinson, 1990; Bettison-Varga et al., 1992; Kelley et al., 1992). The convection cell model for hydrothermal systems and the formation of VHMS deposits is based on observations from VHMS deposits and the upper part of the Cretaceous Troodos Massif in Cyprus, where hydrothermal convection was driven by emplacement of late, high-level gabbro stocks into the fractured and permeable crust (e.g. Spooner et al., 1974; Lydon and Jamieson, 1984; Bettison-Varga et al., 1992). This model involves the circulation of seawater in approximately 10 km diameter cells to depths of 3-5 km within the crust (Fig. 6.2). Initially, increased temperatures in the host succession drive dehydration and decarbonation reactions, and fluids migrate away from the intrusion. Buoyant heated connate seawater rises through the permeable volcanic succession, drawing down cold seawater, which is heated as it descends. In this way, magma drives convective circulation of seawater between the seafloor and the intrusion (Norton, 1984; de-Ronde et al., 1994; Galley, 2003). Fluid flow is focused along joints, fractures and faults formed during extension or in response to intrusive pressures (Bettison-Varga et al., 1992). Alternatively, the multi-tiered convection model involves a high-temperature (450-700°C) cell, which circulates recycled modified seawater in plutonic rocks at depth, overlain by a low-temperature (350-400°C) cell (Gregory and Taylor, 1981; Norton et al., 1984; Alabaster and Pearce, 1985; Kelley et al., 1992). Submarine hydrothermal systems comprise three parts: a down-flow or recharge zone; a high-temperature reaction zone; and an up-flow or discharge zone (Fig. 6.3: Spooner and Fyfe, 1973; Alt, 1999). The locations of the recharge and discharge zones are commonly controlled by faults (Schardt et al., in press). Seawater percolates down through the recharge zone, and is slowly heated and chemically modified by lowtemperature reactions (White, 1970; Gibson et al., 1983; Galley, 1993; Alt, 1999). The reaction zone is a porous reservoir near the heat source where heated seawater reacts with the host rocks, exchanging some elements (Norton, 1984; de-Ronde et al., 1994; von Damm, 1995; Butterfield, 2000; Schardt etal., in press). Hot buoyant hydrothermal fluid (modified seawater) ascends rapidly to the seafloor through the discharge zone, which is characterised by cooling of the fluid, alteration of the host rock, and mineral precipitation (Skirrow and Franklin, 1994; Schardt et al., in press). The rising hydrothermal fluid cools by adiabatic decompression, conductive heat loss, and mixing with cold seawater in the shallow subsurface (Mottl, 1983; Butterfield, 2000). In well-

FIGURE 6.2 | Simple convection cell model for the genesis of the Cyprus VHMS deposits (modified after Heaton and Sheppard, 1977, and Spooner, 1977, in Lydon and Jamieson, 1984).

SYNVOLCANIC INTRUSION-RELATED ALTERATION | 1 4 1

established hydrothermal systems, the discharge zone may be focused, intensely altered and veined. Surface discharge onto the seafloor may produce high-temperature (150—350°C) features such as black smokers (Goodfellow and Franklin, 1993; Rona et al., 1993). The temperature of the discharging fluids on the seafloor initially increases, and then gradually decreases to ambient temperatures, in a time scale of 100 to 10,000 years (Ohmoto, 1996). Regional hydrothermal systems are interpreted to be related to large volume intrusions, as the volume of circulating fluid in a hydrothermal system theoretically cannot be greater than the volume of the intrusion (Cathles, 1981). However, small-volume near-seafloor intrusions, which are unlikely to generate significant hydrothermal systems, may be related to larger plutons or stocks at depth that were capable of generating hydrothermal convection (e.g. Bettison-Varga et al., 1992).

6.2 | REGIONAL ALTERED ZONES ASSOCIATED WITH INTRUSIONS The products of regional-scale hydrothermal alteration systems in ancient submarine volcanic successions are recorded by cross-cutting recharge and discharge zones, and broad, regional-scale, semi-conformable altered zones or reaction zones (Galley, 1993).

Recharge zones Very little is known about altered zones associated with recharge. They are rarely recognised except in studies of modern crustal alteration beneath mid-ocean ridges (e.g. Mottl, 1983; Saccocia et al., 1994; Alt, 1999), hydrothermal

alteration studies in ophiolites (e.g. Schiffman et al., 1987; Schiffman and Smith, 1988), and studies of O- and S-isotope compositions in ancient hydrothermally altered systems (e.g. Cathles, 1993; Davidson and Kitto, 1997). Rocks in modern recharge zones are pervasively altered at low to moderate temperatures. At less than 150°C, oxidation, the fixation of alkalis (mainly Ca and Na), and Mg-metasomatism produces sericite, hematite and clays (Alt, 1999). At higher temperatures (150-350°C) anhydrite precipitates, alkalis are leached and Mg is consumed by chlorite in the rock (Alt, 1999). Schiffman and Smith (1988) proposed that the distribution of epidosites in the Troodos ophiolite represent areas of high-temperature alteration involving high fluid-rock ratios. Epidosites are granoblastic, fine- to medium-grained rocks, with little or no relict igneous textures, composed of epidote, quart and chlorite. They are inferred to record reaction zones in which circulating modified seawater reacted with host rocks to form metal-rich hydrothermal fluids, and appear diagnostic of the up-welling and deep recharge parts of the hydrothermal system beneath VHMS deposits. Co-incident whole-rock O-isotope patterns support their formation in proximal recharge zones and up-flow conduits beneath VHMS deposits. Regionally extensive, depth-dependent 618O profiles in the sheeted dyke complex reflect oxygen exchange during prograde regional hydrothermal alteration involving diffuse down-welling of cold seawater (Fig. 6.4). However, surfaces of equal whole-rock 618O are not horizontal but nearly vertical in the central epidosite zone. This suggests up-flow of hot modified seawater within the epidosite zone. The spatial association between gabbro intrusions and the epidosite zones in the sheeted dyke complex indicates a genetic link between the emplacement of these intrusions and focused high-temperature hydrothermal up-flow (Richardson et al., 1987; Bettison-Varga et al., 1992).

Discharge ZOneS Discordant footwall alteration pipes and feldspar-destructive zones that directly underlie VHMS deposits are widely interpreted as discharge zones through which metal-bearing hydrothermal fluid ascended to the seafloor (Sangster, 1972; Large, 1977; Lydon, 1984; Galley, 1993; Skirrow and Franklin, 1994; Brauhart et al., 1998). They are characterised

FIGURE 6.3 | Model of an active geothermal system illustrating the recharge, reaction or reservoir and discharge zones. Seawater is drawn down in broad recharge zones or along faults and reacts at increasing temperatures. Hightemperature reactions (>350°C) occur in the reaction zone above a subvolcanic intrusion and hot (>300°C) buoyant fluids rise towards the surface in focused or diffuse discharge zones (modified after Alt, 1995a). Not to scale.

FIGURE 6.4 | Cross-section of the Solea graben, Troodos ophiolite, Cyprus, showing surfaces of equal whole-rock d 18 0. Regionally these surfaces are subhorizontal, but in the central epidosite zone they are nearly vertical indicating up-flow of hot, modified seawater during convection. Modified after Schiffman and Smith (1988).

1 4 2 | CHAPTER 6

by Mg-Fe enrichment and Na-Ca depletion and assemblages that include chlorite, sericite, quartz or rare talc (Lydon, 1984; Eastoe et al., 1987; Skirrow and Franklin, 1994; Brauhart et al., 1998). The characteristics and compositional changes associated with discordant footwall alteration pipes are discussed in Section 7.3. Although discordant altered zones typically cut across the regional, deep, semi-conformable altered zones (Galley, 1993; Brauhart et al., 1998), in some successions, they grade laterally into deep, semi-conformable altered zones (Skirrow and Franklin, 1994; Hudak et al., 2000). Gibson et al. (2000) suggested that whether or not deep, semi-conformable altered zones are cut by or transitional with pipe-like altered zones, depends on whether the host succession (footwall) is dominated by coherent volcanic or volcaniclastic facies respectively, or timing of alteration.

Deep, semi-conformable altered zones Since they were first discussed by Franklin et al. (1981), deep, semi-conformable altered zones have been documented in the footwall beneath VHMS deposits in a variety of districts including: Matagami, Snow Lake, Noranda and Sturgeon Lake districts in Canada; Bersglagen and Skellefte districts in Sweden; Iberian pyrite belt in Spain and Portugal; Troodos Ophiolite Complex in Cyprus; Panorama district in Australia; and the Sirohi district in India (MacGeehan, 1978; Gibson et al., 1983, 2000; Lagerbald and Gorbatschev, 1985; Galley, 1993; Skirrow and Franklin, 1994; Tiwary and Deb, 1997; Brauhart et al., 1998; Bailes and Galley, 1999; Hannington et al., 2003a, 2003b). They have not been documented in eastern Australia, possibly because of structural complexities. Thus the following discussions on deep, semi-conformable altered zones are largely based on Canadian examples. Figure 6.5 depicts the characteristics and typical zonation of deep, semiconformable altered zones in the documented examples.

Deep, semi-conformable altered zones typically extend for up to 20 km laterally and 1-4 km depth beneath paleoseafloors and VHMS deposits (Gibson et al., 1983, 2000; Cathles, 1993; Galley, 1993; Skirrow and Franklin, 1994). They comprise vertically stacked, sub-horizontal altered zones (Galley, 1993; Skirrow and Franklin, 1994). Generally these are (Fig. 6.5): an upper background K-Mg metasomatic zone; a transitional Na-Mg metasomatic zone; a central silicified zone; and a basal Ca-Fe metasomatic and base metal-leaching zone (Galley, 1993). In many systems only one or two of these altered zones are recognised. The alteration minerals in the semi-conformable altered zones reflect the primary host rock composition, bulk-rock composition established during synvolcanic hydrothermal alteration, and the subsequent metamorphic grade (Paradis et al., in press). In greenschist facies metamorphosed felsic rocks, these zones are typically, from base to top: albite or carbonate zone, silica or sericite zone and sericite or chlorite zone (Gibson et al., 1983; 2000). In mafic rocks, the zones are: albite zone, silica zone and clinozoisite/epidote + quartz zone (Galley, 1993; Skirrow and Franklin, 1994; Gibson et al., 2000; Hannington et al., 2003a). At higher metamorphic grades, such as in the Snow Lake District, mineral assemblages can include kyanite, staurolite, sillimanite, chlorite, biotite, quartz, plagioclase cordierite, amphibole, epidote and garnet (Paradis et al., 1993, in press; Bailes and Galley, 1999). The semi-conformable altered zones are interpreted to be synvolcanic because they have undergone the same degree of tectonic deformation as the surrounding rocks, have prograde mineral assemblages, are spatially associated with VHMS deposits, and are commonly truncated by unaltered synvolcanic intrusions (Gibson et al., 1983; Paradis et al., 1993; Skirrow and Franklin, 1994). At Snow Lake, Paradis et al. (1993) recognised that deep, semi-conformable altered zones were superimposed on low-temperature (possibly diagenetic) altered zones and also cross cut by discordant feldspar-destructive zones associated with VHMS deposits.

PROCESS AND COMPOSITIONAL CHANGES

ASSEMBLAGE IN MAFIC ROCKS

ASSEMBLAGE IN FELSIC ROCKS

K-Mg metasomatism + Mg, K, Fe -Na, Ca, Cu, Pb, Zn, Si

Mg clays + chlorite + zeolites + Fe-oxides ± K-feldspar

Mg-clays + zeolites ± cristobalite ± adularia ± analcime ± K-feldspar

Na-Mg metasomatism + Na, Mg -Ca, Fe, Zn.Cu ±Si

Albite + quartz + sericite + Mg-chlorite ± calcite

Albite + quartz + sericite + Mg-chlorite

Silicification or sericitisation + Si, Na -Fe, Mg, Mn,Zn ±Ca

Quartz + albite

Quartz ± albite ± sericite

Ca-Fe metasomatism + Ca - M g , Mn, Na, K ± Fe, Si

Clinozoisite/epidote + quartz ± actinolite ± carbonate

Sericite + quartz ± Mg-chlorite or chloritoid + Fe-chlorite

FIGURE 6.5 | A schematic compilation of regional-scale, deep, semi-conformable altered zones and their characteristics. There is a progression, with increasing depths in submarine volcanic successions, from the background Mg-K metasomatic zone to a transitional Na-Mg metasomatic zone characterised by feldspar alteration, a central silicified zone and a basal Ca-Fe metasomatic and base-metal leaching zone that typically includes epidote or chlorite, After Gibson et al. (1983), Galley (1993), Skirrow and Franklin (1994), and Brauhart etal. (1998).

SYNVOLCANIC INTRUSION-RELATED ALTERATION | 1 4 3

They suggested that regional hydrothermal alteration postdated the onset of diagenetic alteration, and pre-dated footwall alteration associated with hydrothermal alteration and mineralisation. In some Canadian examples and at Panorama in western Australia, deep, semi-conformable altered zones are gradational with discordant footwall alteration pipes suggesting that regional hydrothermal alteration was synchronous with the VHMS-related alteration (Gibson et al., 1999). Deep, semi-conformable altered zones are commonly spatially and temporally associated with subsurface synvolcanic intrusions (Galley, 1993, 2003). These intrusions can be individual granitic or porphyritic plutons or sheeted

dyke swarms (e.g. Gibson et al., 1983; de-Ronde et al., 1994; Brauhart et al., 1998). The tops of the subvolcanic intrusions and associated dykes may be included in the basal semiconformable altered zone (e.g. Galley, 1993; Brauhart et al., 1998). One of the best-documented examples of the spatial association between a subvolcanic intrusion, regional-scale semi-conformable altered zones and VHMS deposits comes from the Panorama district in Western Australia. Discordant chlorite + quartz zones directly beneath the VHMS deposits, are spatially associated with feldspar-destructive sericite + quartz zones in the top of the Strelley Granite pluton

FIGURE 6.6 | Geology and altered zones within part of the Strelley succession, Panorama district, Western Australia (modified after Brauhart et al., 1998).

1 4 4 | CHAPTER 6

1994). In the Snow Lake district Skirrow and Franklin (1994) estimated that approximately 1.1 x 107 metric tons of SiO2 was added by a minimum 12 km3 of hydrothermal fluid at 1—2 km depth. Interactions between large volumes of modified seawater and volcanic successions at depth are supported by geochemical and geophysical research at active ocean spreading ridges (e.g. Spooner and Fyfe, 1973; Bischoff andDickson, 1975). Deep, semi-conformable altered zones are characterised by mineral assemblages that reflect the reactions of glass and both primary and secondary minerals with seawater at temperatures up to 400°C (Galley, 1993).

Background K-Mg metasomatic zones

FIGURE 6.7 | Schematic section of the geology and altered zones in the Kangaroo Caves footwall succession, Panorama district, Western Australia (modified after Brauhart et al., 1998). See Figure 6.6 for legend.

(Figs 6.6 and 6.7; Brauhart et al., 1998). Faults bounding the discordant chlorite + quartz zone in the footwall of the Kangaroo Caves deposit (Fig. 6.7) controlled the distribution of the feldspar-destructive sericite + quartz zone in the Strelley Granite (Brauhart et al., 1998). The variations in alteration mineral assemblage down through the semi-conformable altered zones correspond to geochemical gradients in which there are gradual decreases in the Mg/Ca, Mg/Na and Na/Ca ratios of the altered rocks with increasing depths (Galley, 1993). Oxygen-isotope compositions suggest that the altered rocks are 18O enriched with respect to unaltered volcanic rocks (Munha and Kerrich, 1980; Barringa and Kerrich, 1984). The geochemical gradients and O-isotope data are consistent with metasomatic alteration resulting from the interaction of volcanic rocks with seawater (Muehlenbachs and Clayton, 1972; Lagerbald and Gorbatschev, 1985; Cathles, 1993). Although modified seawater is interpreted to be the main component, magmatic fluids may have also contributed to the hydrothermal fluid (Lagerbald and Gorbatschev, 1985). The spatial association between altered zones and subsurface intrusions suggests a genetic link where intrusions may have provided heat and or fluid to the hydrothermal system. The extent and intensity of deep, semi-conformable altered zones implies that very large volumes of fluid must have reacted with the host volcanic rocks (Skirrow and Franklin,

These zones are often described as the least-altered or diagenetically altered zones. At low temperatures (50-140°C) in the shallow subseafloor, the interaction of abundant seawater with the volcanic succession produces Mg-K-rich alteration assemblages (Seyfried and Bischoff, 1977; Galley, 1993). In felsic rocks these mineral assemblages include adularia and Mg-smectite, whereas in mafic rocks they are dominated by zeolites and Mg-smectite. Seawater becomes enriched in Si, Fe3+, Mn and lesser amounts of Ca, Mg and sulfur (Seyfried and Bischoff, 1977). Current mineral assemblages reflect the regional metamorphic grade. For example, at Snow Lake the diagenetically altered zone is characterised by quartz + biotite + garnet, Fe2O3, MgO and K2O gains and CaO, Na 2 O, Cu, Pb, Zn losses (Paradis et al., in press). These compositional changes are consistent with low-temperature seawater-dominated diagenesis of felsic volcanic facies to clays and zeolites (Section 5.3). The current mineral assemblage reflects the overprint of amphibolite facies metamorphism. In the Panorama district the background alteration mineral assemblage includes feldspar + calcite ± ankerite + quartz + pyrite ± sericite consistent with greenschist facies metamorphism of clays and zeolites in felsic volcanic rocks (Brauhart et al., 1998).

Transitional zone or Na-Mg metasomatic zones With increasing stratigraphic depth there is a transition from K-rich zones to Na-rich zones (Munha et al., 1980; Munha and Kerrich, 1980; Lagerbald and Gorbatschev, 1985; Schiffman and Smith, 1988; Brauhart et al., 2001). The NaMg metasomatic zones are characterised by the occurrence of feldspar, usually albite. Greenschist facies assemblages typically include chlorite, sericite, albite, epidote and quartz in mafic rocks, and albite, quartz, sericite ± chlorite ± carbonate (calcite or dolomite) in felsic rocks (Gibson et al., 2000). In the Panorama district, felsic rocks in the feldspar zone have the assemblage K-feldspar or albite + sericite + quartz + ankerite + leucoxene ± pyrite (Brauhart et al., 1998). The transition to Na-rich zones reflects the behaviour of Na and K in seawater at elevated temperatures. Between 140° and 200°C there is a transition between K- and Na-metasomatism (Seyfried and Bischoff, 1977). Munha et al. (1980) suggested that at lower temperatures (1.4 km) halo comprising biotite hornfeis and quartz + sericite + albite zones, which are enriched in K2O, MgO and base metals. Beneath the intrusion is a thinner (230°C) coincided with the known Central, East and Orient massive sulfide lenses. The existence of an additional isotopic-temperature anomaly, about 1 km west of the known resources, stimulated further exploration that turned up a favourable REE geochemical anomaly in the same sector. Subsequent exploratory drilling discovered a 0.23 Mt polymetallic massive sulfide lens. It remains sub-economic, but may represent the first successful VHMS exploration application of O-isotope geochemistry in Australia.

251

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INDEX

A page number in bold indicates that the reference is to a figure. A bold t indicates that the reference is to a table.

AI-CCPI Alteration box plot see Alteration box plot albite alteration 39, 42-44, 61, 65, 69, 133-5, 165-7, 191, 214,216 Alteration box plot 31-4, 36, 169-70, 245 alteration distribution 22, 63-4 alteration facies describing and defining 15—36 diagenetic 241—2 distribution 63-4 hydrothermal 242-3 metamorphic 242 variables 22 alteration fluids 93, 170-3 Alteration Index (AI) 30-2, 34, 169, 245 alteration indices 26-30, 34, 73, 169-70, 244^5 alteration intensity describing 27t estimation, integrated approach 33—6 explained 25—36 illustrated 28-29, 36 lithogeochemical indications of 243-4 alteration mineral assemblages see mineral assemblages alteration nomenclature 16, 19-22, 2It, 22t, 23t alteration pipes 63, 164-74, 176, 182-3 alteration plumes 63, 167, 168, 191-3 alteration processes 4—6 alteration rates 6 alteration textures deformation textures 52, 54-6, 55-7 described 37-63, 37t, 38t, 62t dissolution textures 41, 50-1, 52 dynamic recrystallisation textures 52 illustrated 39-40, 62, 103-4, 110, 111-13 infill textures 41,48-9 overprinting and false/pseudo textures 37, 54-63, 58-61, 62t recrystallisation textures 52, 53 replacement textures 37-8, 41, 42-7 static recrystallisation textures 52, 53

alteration timing 69-71, 7It, 172 alteration zonation boundaries 64 contact altered zones 5, 64, 66-7, 67, 139, 149-56, 242 diagenetic 64, 105-8 facies model 3 greenschist facies zones 115, 116, H6t, 131, 142, 144-5, 152 halos 66-9 Hellyer deposit 178,182-3,184-93 Henty deposit 178, 212-3, 214-20 Highway Reward deposit 14, 167, 178, 232, 233-40 Hokuroku Basin 119-27 hydrothermal 5-6, 66-8, 164-9, 243 mapping 243 metamorphic 64—5, 66—7 Mount Read Volcanics 128-38 patterns 64-9,98, 165-8 regional deep semi-conformable 66, 142-8 regional metamorphic 115-17,140 Rosebery deposit 178,195,196-201 scales described 64t Thalanga deposit 14, 178, 222, 223-31 veins and fractures 67, 69 Western Tharsis deposit 202-3,204-11 amphibolite facies 115-17,140 Amulet deposit see Noranda district analytical techniques electron microprobe 19,25,88 field observations 18 ICP-AES (inductively coupled plasma atomic emission spectrometry) 76-7 ICP-MS (inductively coupled plasma mass spectrometry 76—7 isotope geochemistry 92—5 HyMap® 246, 247 lithogeochemical sampling 73-87 mineral chemistry analysis 87-91 NAA (neutron activated analysis) 76 petrography 24-5, 33-4 PIMA 25, 33, 245

2 7 2 | INDEX

SWIR spectroscopy 19, 24, 25, 33, 88, 90, 202-3, 243, 245 X-ray diffraction (XRD) 19, 24, 25, 33, 88 X-ray fluorescence spectrometry (XRF) 76-7 anhydrous minerals 97

B Bathurst mining camp 164-5,170 Boco prospect 248, 250 burial-related alteration 97-138 see also diagenesis and submarine environments

c carbonates diagenetic 105 in exploration 90-1, 243-4 hydrothermal 47, 91, 166, 178, 188, 201, 217, 229-30 cataclastic texture 52 CCPI (chlorite-carbonate-pyrite index) see also Alteration box plot explained 31, 34 exploration, uses for 169,245 cementation 97, 102, 105, 108-10, 132 Central Volcanic Complex see Mount Read Volcanics chlorite 19-22, 89, 138, 156, 165-8, 187, 239 closure and alteration indices 26 constant sum effect 243—4 explained 78-9,243-5 mass change anomalies 81 compaction 97, 109-10, 132 compositional nomenclature 20 contact alteration 5, 149-62 corrosion vugs 41, 50—1, 52 crystallisation primary 4 textures 52 of zeolite assemblages 105, 110, 114, 121

D Darwin Granite see Mount Read Volcanics data sheets contents of 36 Darwin Granite 157-62 Hellyer deposit 184-93 Henty deposit 214—20 Highway-Reward deposit 233-40 Hokuroku Basin 122-7 Mount Read Volcanics 133-8 Rosebery deposit 196-201 Thalanga deposit 223-31 Western Tharsis deposit 204—11 deep, semi-conformable altered zones 142—6 deformation textures 52, 54-6, 55-7 detection limit explained 75 deuteric alteration 148 devitrification explained 4 texture 37, 39, 62 zones 151

diagenesis explained 5 Hokuroku Basin 118-27 isotope geochemistry analysis 93-4 and metamorphism 16, 98, 102, 114, 115 Mount Read Volcanics 128-38 in submarine volcanic successions 97, 102—14 diagenetic minerals carbonates 105 genesis of 108-14 layered silicates 102,105 other diagenetic minerals 105 zeolites 105, 110, 118, 120-7 diagenetic zones Hokuroku Basin 118—27 Mount Read Volcanics 128-38 zonation 64-5, 105-8 discharge zone 141—2 dissolution 41, 50-1, 52, 97, 102, 108-10, 114, 132 dynamic recrystallisation textures 52

electron microprobe see analytical techniques element concentrations 32-3 eutaxitic texture 54, 57 exploration Alteration box plot 31-4,169-70 alteration identification as tool in 241—50 Alteration Index (AI) 30-2 isotope geochemistry in 92-5, 246-50 lithogeochemistry in 73-87 mineral chemistry in 87-91 sulfide mapping 243 use of chlorite in 89 use of white mica in 90—1 vectors and proximity indicators 32-3, 94-5, 243-50

false textures see pseudotextures fiamme 54, 57 fluid-rock interaction 169, 170-2, 171, 173 foliation 52, 54, 70, 711 footwall alteration 163-74, 179, 182-9 fused zones 151

geochemistry see isotope geochemistry, lithogeochemistry geothermal gradient 98 geothermometers 92-3 glass alteration in submarine volcanic successions 15, 97-8 common alteration minerals 19t crystallisation 4 diagenesis 102—14 disequilibrium assemblages 24 hydration 4-5, 98-102 reactive quality, 6 Green Tuff Belt see Hokuroku district

INDEX | 2 7 3

H halos 5-6, 38, 41, 66-9, 149-56, 157-62, 163-74, 17881 hanging wall alteration 163, 164, 167-8, 190-3 Hellyer deposit see also Mount Read province alteration fades and zonation 178, 182-3, 184—93 Alteration Index (AI) 31, 183 explained 11, 181-93 exploration 245 geological setting 181—2 ore genesis 170, 183 white mica 90 Henty deposit see also Mount Read province alteration facies and zonation 178, 212-13, 214-20 explained 12 geological setting 212 hanging wall alteration 167 isotopic data 248 ore genesis 213 Hercules deposit see also Mount Read province alteration halo 178 explained 12, 128 geological setting 194 Highway-Reward deposit see also Mount Windsor Subprovince alteration facies and zonation 14, 167, 178, 232,

233-40 explained 14 geological setting 12-14, 232 hanging wall alteration 167,178 ore genesis 232 submarine facies associations 13 Hokoroku Basin see Hokuroku district Hokuroku district alteration 64-5, 67, 118-27, 122-7 geological setting 118—20 Green Tuff Belt 52, 64, 107, 118, 150, 151 Kuroko deposits see Kuroko deposits oxygen isotopes 94-5, 246 size of VHMS deposits 164 hydration of volcanic glass 4-5, 98-102 hydrothermal alteration boundaries between zones 64 chemical reactions 168 and diagenetic alteration 128 discharge zone 141-2,156 discriminating 16—19 explained 4 halos 66-7, 164-74 intensity measures 32-3 intrusion-related 140-61 see also intrusions metamorphic assemblages 174, 175t plagioclase destruction 31, 167 recharge zone 141 subseafloor systems 140—1 syntectonic 6 tectonic deformation 6 VHMS deposits 5-6, 163-240 zones 5-6, 66-8, 164-78, 243 hydrothermal convection 1, 94, 140-1, 140

hydrothermal fluid 67, 172-3 HyMap® 246, 247

Iberian pyrite belt 90, 91, 142, 164, 165, 166, 166, 174 ICP-AES (inductively coupled plasma atomic emission spectrometry) 76—7 ICP-MS (inductively coupled plasma mass spectrometry 76-7 indices alteration 26-30, 34, 73, 244-5 Alteration box plot see Alteration box plot Alteration Index (AI) 30-2, 34, 169, 245 CCPI (chlorite-carbonate-pyrite index) 31, 34, 169, 245 molar proportion alteration 30 multi-component and normalised 26, 30 simple ratio 26 induration 150, 151 infill textures 41,48-9 intrusions halos 66—7 cryptodomes 2, 6, 66, 128, 139, 143, 153, 212, 232 dykes 2, 6, 66, 141, 139, 149, 152, 153 plutons 139, 143, 153 sills 66, 70, 100, 128, 148-9, 152-3, 150, 152, 174, 182, 194,202,212,221,232 in submarine volcanic successions 2 , 3 , 139 synvolcanic 139—62 isotope geochemistry applications 92-5 carbon 76, 77, 248 exploration 94-5, 246-50 hydrogen 76, 77, 93 oxygen 94-5, 246,248-50 stable isotopes 92-5 sulfur 76, 77-8, 92, 141, 180, 246, 248 water-rock ratios 93

K kaolinite in VHMS altered zones 88, 150, 174-75, 178-80 keratophyre 98 K-lens see Rosebery deposit Kuroko deposits see also Hokuroku district alteration 164, 179 Alteration Index (AI) 31 alteration model 166, 178—9

least altered see also alteration intensity explained 26 alteration indices 32 lithification 97, 108-10 lithogeochemistry analytical methods 73-8 carbonates 76-7 chemostratigraphy 79-81 C-H-N elemental analyser 76 closure 78-9, 81 compatible elements 79—80

2 7 4 I INDEX

europium 87 explained 73-8, 74t and exploration 243-5 hydrous minerals 76-7 ICP-AES (inductively coupled plasma atomic emission spectrometry) 76-7 ICP-MS (inductively coupled plasma mass spectrometry 76-7 immobile elements 79-81, 85, 87 inaccuracies in 77 incompatible elements 79 limit of detection 75 LOI (loss on ignition) 76 mass change 73, 81-7, 85-6, 87, 97, 165, 180-1, 245-6 NAA (neutron activated analysis) 76 precision and accuracy required 75 recalculating to volatile free 77-8 REE (rare earth elements) 73, 79, 81, 87 reporting data 77 sampling methods 73—8 summing elements 77 use of reference materials 75 XRF (X-ray fluorescence spectrometry) 76-7

M mass change see lithogeochemistry massive sulfide 163—5, 167 Mattabi deposit 91, 180 metamorphism burial metamorphism and diagenesis 16, 97, 98, 102, 114, 115-17 contact metamorphism 5, 11, 12, 64, 66-7, 149-54, 242 explained 4, 5, 20, 24 regional metamorphism 5, 64-6, 115, 139, 140-8 of VHMS-related altered zones 174-5 metasomatic alteration 4, 5, 144-6 microanalysis 24 microprobe see analytical techniques mineral assemblages alteration assemblages 23—5, 34, 165 burial effects on 97, 109 common assemblages 21t, 22t, 109, 165 disequilibrium 23-4, 63 equilibrium 23-4 in exploration 243 igneous 16, 19 isotopic studies of 92—5 nomenclature 19-20 mineral chemistry 87-91, 245-6 minerals defined 87-8 Mount Lyell field see also Mount Read province deposits 12,202,243 geological setting 202 halos 202 hanging wall alteration 167 HyMap system 246, 247 mineral zonation 243, 247 ore genesis 203 Western Tharsis deposit see Western Tharsis deposit

Mount Read province alteration 7-12, 163-164 Chester deposit 90 history 9, 11-12 Hellyer deposit see Hellyer deposit Henty deposit see Henty deposit Hercules deposit see Hercules deposit Mount Lyell field see Mount Lyell field Mount Read Volcanics see Mount Read Volcanics oxygen isotopic exploration 249—50 Que River deposit see Que River deposit Rosebery deposit see Rosebery deposit size of VHMS deposits 164 Western Tharsis deposit see Western Tharsis deposit Mount Read Volcanics see also Mount Read province AI and CCPI ranges 32,34 alteration 128-32, 133-8 Central Volcanic Complex 9-10, 69, 128, 130-32,

157-62 chemostratigraphic discrimination and correlation 80 compaction effects at 110 Darwin Granite 154-6, 157-62 geology of 7-12, 128, 129 Kershaw Pumice Formation 128,134—6 Mount Black Formation 128, 133, 137-8 pyritic alteration systems 89 metamorphic assemblages 11 Sterling Valley Volcanics 128 Mount Windsor Subprovince alteration 14, 164, 222, 232 geology 12-14, 221-40 Highway-Reward deposit see Highway-Reward deposit Thalanga deposit see Thalanga deposit

N NAA (neutron activated analysis) 76 see also analytical techniques naming altered rock see alteration nomenclature Noranda district 66, 142-7, 167, 179-81 numerical fluid-flow modelling 172

o overprinting textures 37, 70-1, 70t, 711 and false/pseudo textures 37, 54-63, 58-61, 62t relationships 69-71, 7It

palagonite 99, 99-100 Panorama district 180, 246, 248-50 paragenetic sequence 69 perlite 37,40,54, 100-1, 101 PIMA (portable infrared mineral analyser) 25, 33, 245 see also analytical techniques plagioclase destruction 31,167-9 pseudotextures 16, 37, 54-63, 58-61, 62t, 63 pyrophyllite in VHMS systems 174, 202, 207-8

Que River deposit 11-12, 70, 90, 167 see also Mount Read province

INDEX I 2 7 5

R regional metamorphism see metamorphism relict textures 14, 16, 19, 24, 25, 37-38, 141 replacement textures 37-38, 41, 42-7 Rio Tinto deposit see Iberian pyrite belt Rosebery deposit see also Mount Read province alteration 70, 128, 131t, 168, 173, 178, 195, 196201 Chlorite-carbonate-pyrite index (CCPI) 195 geochemical alteration parameters 168 geological setting 194 explained 11-12, 194-201 hydrothermal carbonates 91 hydrothermal fluid flow 174 K-lens 30, 34, 68, 91, 174, 244 lithogeochemical data in exploration 82, 244 sericite 70-1

Scuddles deposit 180 sericite alteration 20-2, 70-1, 165-78, 185-6, 198-9, 20611, 218,225, 231, 238 see also white mica Short-wavelength infrared spectroscopy (SWIR) see analytical techniques siliceous alteration 165-9, 182, 189, 199, 219-20 smectites 102, 109, 117 Snow Lake District 142-6 sodium content in volcanic rocks 34—6, 243—4 solution seams 51, 52 spilite 98 stable isotopes see isotope geochemistry stockwork see stringer zones stringer zones 163, 165, 172-3, 179 stylolites 51, 52 submarine environments 2, 97—138 submarine facies associations Mount Read Volcanics 10-11, 214-20 Seventy Mile Range Group 12-13 submarine volcanic successions 1-14, 3, 97-138, 241-9 SWIR spectroscopy see analytical techniques synvolcanic intrusions see intrusions

Thalanga deposit see also Mount Windsor Subprovince alteration facies and zonation 14, 178, 222, 223-31 explained 14 geological setting 12—14, 221—2 mass change estimations 85—6 ore genesis 222 oxygen isotopic exploration 250 thermodynamic alteration model 170-2

vectors exploration 243—50 isotopic 246—50 lithogeochemical 243-4 mass change 245 mineral chemistry 79, 89-91, 245-6 sulfide 243-4

vein-halo alteration 38,41,43,69 VHMS deposits alteration patterns 164—78 classification 163—6 common features 163—4 comparisons 178-81 exploration 241-50 footwall alteration 163-74 halos 5-6, 67-9, 68, 163-8, 175, 178-81 hanging wall alteration 163—4, 167—8 Hellyer deposit see Hellyer deposit Henty deposit see Henty deposit Highway-Reward deposit see Highway-Reward deposit kaolinite, presence of 174 major VHMS provinces 164 Mount Lyell see Mount Lyell field pyrite in 243 pyrophyllite, presence of 174 regional alteration zones 5-6, 139-62 Rosebery deposit see Rosebery deposit Thalanga deposit see Thalanga deposit Western Tharsis deposit see Western Tharsis deposit VMS deposits see VHMS deposits volcanic facies alteration processes 2—6 alteration in submarine environments 97—138 associations 2 changes in 108 clastic facies 1,19 coherent facies 1, 6, 16, 19 common clay minerals in 102 crystalline facies 6 volcaniclastic facies 1, 6, 12, 16—19 volcanic-hosted massive sulphide deposits see VHMS deposits vugs 41,50-1,52

W water-rock ratios 93—4 Western Tharsis deposit see also Mount Read province see also Mt Lyell field alteration facies and zonation 202—3, 204—11 case study 202-11 geological setting 202 ore genesis 203 white mica 91 white mica 20, 89-91, 165, 246 Woodlawn deposit 178

X X-ray diffraction 19, 24, 25, 33, 88 X-ray fluorescence spectrometry (XRF) 76—7

zeolites 105-6, 106t, 110, 114-16, 118, 120-1 zones see alteration zonation

About the authors

Dr Cathryn Gifkins is a Research Fellow at the Centre for Ore Deposit Research at the University of Tasmania. Cathryn brings to the publication a strong background in mapping, describing and interpreting altered and deformed volcanic rocks in submarine successions. Her current research focusses on the textural, mineralogical and compositional effects of alteration in glassy volcanic rocks, the link between volcanic centres and mineralising hydrothermal systems, and the facies architecture and stratigraphy of the Mount Read Volcanics. ' Walter Herrmann is a Research Fellow in economic geology at the Centre for Ore Deposit Research. Wally's background in mineral exploration in Australian volcanic successions, principally the Mount Read Volcanics and the Mount Windsor Subprovince is a valuable asset to the book. He has a special interest in understanding hydrothermal alteration as a method for discriminating and discovering VHMS and porphyry deposits. Professor Ross Large is Director of the Centre for Ore Deposit Research and has a long and celebrated academic and exploration career. Ross has a comprehensive knowledge of VHMS deposits, and has actively promoted and developed the application of geochemical techniques to mineral exploration. This innovative approach has recently produced the Alteration box plot, an alternative way to relate alteration intensity, mineralogy and geochemistry.