JD Thesis

Formation and evolution of the Sudbury impact melt sheet
James R. Darling
A dissertation submitted to the University of Bristol in accordance with the requirements of the degree of Doctor of Philosophy in the Faculty of Science.
Department of Earth Sciences University of Bristol January 2010
Advisors Prof. Chris Hawkesworth Dr. Craig Storey Dr. Peter Lightfoot (Vale Inco)
Word count ca. 35000
James R. Darling
All Rights Reserved, 2010
Abstract
A unique terrestrial large impact melt sheet is located within the Sudbury Structure in Ontario, Canada. This study addresses problems relating to the formation and subsequent evolution of the melt sheet, by characterising isotopic variations throughout the various igneous units present. The Pb isotopic compositions of sulphides and feldspars from a range of rock types and sulphide ores were measured by MC-ICPMS. Signicant and systematic vertical and lateral isotopic heterogeneity has been identied throughout the Main Mass of the melt sheet, as well as between early formed Oset Dykes. These ndings demonstrate that the melt sheet was a dynamic system, with chemical variability present from shortly after the impact event through to the nal products of silicate crystallisation, despite vigorous thermal convection. Importantly, the Pb isotope systematics of Oset Dyke quartz diorites, together with trace element and Sr-Nd isotope data, demonstrate that such heterogeneity can be accounted for by mixing of locally exposed target lithologies. As such, and in contrast to many impact model predictions, an upper to mid crustal origin for the igneous complex is apparent. The results have signicant implications for the understanding of melt sheetfootwall interactions, as well as the origins of Sudburys vast Ni-Cu-PGE sulphide ore deposits. The melt sheet also oers a unique analogue for such features on the early Earth. Characterisation of the trace element compositions and inclusion populations of zircons from throughout the melt sheet stratigraphy revealed that large variations in zircon crystallisation temperature and composition will be an inevitable consequence of the evolution of such magmatic systems. Furthermore, it is clear that zircons in mac rocks crystallise in residual liquids of granitic composition. The ndings have signicant implications for the interpretation of the Hadean detrital zircon record.
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Abstract
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Authors Declaration
I declare that the work in this dissertation was carried out in accordance with the requirements of the Universitys Regulations and Code of Practice for Research Degree Programmes and that it has not been submitted for any other academic award. Except where indicated by specic reference in the text, the work is the candidates own work. Work done in collaboration with, or with the assistance of, others, is indicated as such. Any views expressed in the dissertation are those of the author.
James R. Darling
Authors Declaration
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Acknowledgments
This study beneted from the expertise, advice and assistance of many people, all of whom are thanked for their contribution to the scientic content of this theses and my personal development as a scientist. In particular, Chris Hawkesworth, Craig Storey and Peter Lightfoot are thanked for their expert guidance and support throughout the last three years. Many members of Bristol Isotope Group (BIG) contributed to my understanding of geochemical methods and analytical techniques: Chris Coath, Matthias Willbold, Corey Archer, Kirsty Crocket, Bob Steele, Gavin Foster, Phillip Pogge von Strandmann and Tim Elliot. Riccardo Avanzinelli is thanked in particular for his invaluable help and support with the measurement of Pb isotopes. Stuart Kearns is thanked for his help with electron microbeam techniques. Chung Choi for assistance with sample preparation and ICP-OES analyses. Gemma Sherwood and Matthew Cross for their assistance with sample preparation. Fieldwork beneted greatly from the nancial support of Vale Inco and the logistical support of the Sudbury Basin Group of Vale Inco Exploration. Extensive assistance from Enrick Tremblay and Peter Lightfoot is gratefully acknowledged. This project was funded by NERC Studentship NER/S/A/2006/14061, Vale Inco and the Eugene M. Shoemaker Impact Cratering Award.
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Acknowledgments
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Table of Contents
Abstract Authors Declaration Acknowledgments List of Figures 1 Introduction 1.1 1.2 1.3 1.4 1.5 The Sudbury Igneous Complex - a unique terrestrial melt sheet . . . . . . Thesis aims . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Thesis structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Author contributions to published papers . . . . . . . . . . . . . . . . . . Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii v vii xii 1 1 2 5 6 7 9 9 9
2 The geology of the Sudbury Structure 2.1 Regional geological setting . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1 2.1.2 2.2 The Superior Province . . . . . . . . . . . . . . . . . . . . . . . . . The Southern Province
. . . . . . . . . . . . . . . . . . . . . . . . 11 . . . . . . . . . . . . . . . . . . . . . . 14
Geology of the Sudbury Structure 2.2.1 2.2.2 2.2.3 2.2.4 2.2.5
The Sudbury Igneous Complex . . . . . . . . . . . . . . . . . . . . 14 Breccias of the Sudbury Structure . . . . . . . . . . . . . . . . . . 24 Sulphide ore deposits . . . . . . . . . . . . . . . . . . . . . . . . . . 26 The Whitewater Group . . . . . . . . . . . . . . . . . . . . . . . . 27 Deformation of the Sudbury Structure . . . . . . . . . . . . . . . . 29
2.3
Geochemistry of the Sudbury Igneous Complex . . . . . . . . . . . . . . . 30 2.3.1 2.3.2 Major and trace elements . . . . . . . . . . . . . . . . . . . . . . . 31 Isotopic studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 37 ix
3 Methodology
TABLE OF CONTENTS 3.1 3.2 Sample processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 Pb isotope analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 3.2.1 3.2.2 3.2.3 3.2.4 3.2.5 3.2.6 3.2.7 3.2.8 3.2.9 3.3 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Digestion protocols . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 Pb ion exchange chromatography . . . . . . . . . . . . . . . . . . . 42 Procedural blanks . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 Pb isotope mass spectrometry . . . . . . . . . . . . . . . . . . . . . 45 Standards summary . . . . . . . . . . . . . . . . . . . . . . . . . . 49 U/Th/Pb ratios . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53 Calculation of initial Pb isotope ratios . . . . . . . . . . . . . . . . 55
Zircon major and trace element analysis . . . . . . . . . . . . . . . . . . . 57 3.3.1 3.3.2 3.3.3 Electron microprobe protocols . . . . . . . . . . . . . . . . . . . . 58 Laser Ablation ICPMS protocols . . . . . . . . . . . . . . . . . . . 60 Standards summary . . . . . . . . . . . . . . . . . . . . . . . . . . 61 64
4 Isotopic heterogeneity in the Sudbury impact melt sheet 4.1 4.2
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64 Darling J.R. et. al. (2009) Isotopic heterogeneity in the Sudbury impact melt sheet. Earth and Planetary Science Letters . . . . . . . . . . . . . . 65
4.3
Pb isotopes as a tool for sulphide ore exploration? . . . . . . . . . . . . . 80 4.3.1 4.3.2 4.3.3 Sampling strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 Pb isotope results . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 Comparison of Pb isotopes and whole rock geochemistry . . . . . . 81 88
5 Pb isotope systematics of the Oset Dykes 5.1 5.2
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 Darling J.R. et. al. Shallow impact: isotopic insights into crustal contributions to the Sudbury impact melt sheet; in review . . . . . . . . . . . . 89
6 Impact melt sheet zircons 6.1
109
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 x
TABLE OF CONTENTS 6.2 Darling J.R. et al (2009) Impact melt sheet zircons and their implications for Hadean crustal processes; Geology v.37; no.10; p. 927-930 . . . . . . . 111 7 Summary and future directions 7.1 7.2 7.3 117
Melt sheet evolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117 Origin of the melt sheet . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 Implications for sulphide ore formation . . . . . . . . . . . . . . . . . . . . 119 7.3.1 Distinct sources for ores in dierent Oset Dykes? . . . . . . . . . 120
7.4
Zircons in impact melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121 123 135
Bibliography 8 Appendices 8.0.1 Supplementary materials for Darling et al. (2009) Impact melt sheet zircons and their implications for Hadean crustal processes;
Geology; v. 37; no.10; p. 927-930 . . . . . . . . . . . . . . . . . . . 135 8.0.2 Supplementary material to Chapter 7 . . . . . . . . . . . . . . . . 141
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List of Figures
2.1 2.2 Regional geological setting of the Sudbury Structure . . . . . . . . . . . . 10 Summarised stratigraphy and depositional setting of the Huronian Supergroup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 2.3 2.4 Simplied geological map of the Sudbury Structure . . . . . . . . . . . . . 15 Schematic representation of the stratigraphic relationships in the Sudbury Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 2.5 2.6 2.7 Petrology of the North and South Ranges of the Main Mass . . . . . . . . 17 Photographs of thin sections from the main units of the SIC . . . . . . . . 20 Schematic representation of geological relationships in the Worthington Oset Dyke . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 2.8 Photographs of thin sections from the main quartz diorite phases of the Worthington Oset Dyke . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 2.9 Photographs of Sudbury Breccia, Footwall Breccia and Sublayer exposures 25
2.10 Cross-section through the Levack Mine highlighting the dierence between contact and footwall ore deposits . . . . . . . . . . . . . . . . . . . . . . . 27 2.11 Photograph of the Basal Member of the Onaping Formation . . . . . . . . 29 2.12 Cross section through the Sudbury Structure . . . . . . . . . . . . . . . . 31 2.13 Selected major and trace element, and trace element ratio variations throughout the Main Mass and Sublayer . . . . . . . . . . . . . . . . . . . . . . . 33 2.14 Comparison of model initial Pb isotope ratios from the SIC and Sudbury Breccias . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 3.1 3.2 Plagioclase feldspar step leaching procedure, and results for sample FOQD1 41 Comparison of the matrices of elution steps from Pb ion exchange chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 3.3 Representative examples of the drift in uncorrected
206Pb/ 204Pb
ratios of
the NIST SRM 981 standard throughout analytical sessions . . . . . . . . 50 3.4 3.5 Natural logarithm plots of raw NIST SRM 981 Pb isotope ratios . . . . . 51 Individual measurements of the (a) (c)
208Pb/ 206Pb 206Pb/ 204Pb,
(b)
207Pb/ 206Pb,
and
ratios of NIST SRM 612 from this study . . . . . . . . . 52 xii
LIST OF FIGURES 3.6 3.7 3.8 An example of reproducibility for processed samples. . . . . . . . . . . . . 54 Schematic representation of model initial Pb isotope calculation . . . . . . 57 (a) Standard deviation of individual measurements versus counting times in EPMA analyses. (b) Traverse across standard Kim-5 . . . . . . . . . . 59 4.1 Plots of uranogenic and thorogenic Pb isotope ratios of ore samples from throughout the Creighton embayment . . . . . . . . . . . . . . . . . . . . 81 4.2 Model initial
207Pb/ 204Pb
plotted against whole rock assay data (from
Vale Inco Exploration) for samples from the Creighton embayment . . . . 83 4.3 Model initial
207Pb/ 204Pb
plotted against the Ni content of pyrrhotite
separates from the Creighton embayment . . . . . . . . . . . . . . . . . . 84 6.1 Comparison of the record of early Earth processes with models of mass ux to the Moon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 7.1 7.2 8.1 Sampling localities of Oset Dyke ores . . . . . . . . . . . . . . . . . . . . 120 Histogram of model initial Pb isotope ratios of Oset Dyke ore samples . 121 Cathodoluminescence images of representative zircons from each unit of the melt sheet. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139 8.2 Chondrite normalised REE proles of Sudbury impact melt sheet zircons. 140
Note that this list of gures does not include those within the three published and submitted papers.
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LIST OF FIGURES
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1 Introduction
1.1 The Sudbury Igneous Complex - a unique terrestrial melt sheet
Few geological features have been more intensively studied than the Sudbury Structure in Ontario, Canada. Although the rst ore from Sudburys vast nickel and copper sulphide deposits was mined in 1886 (see Giblin, 1984), the origin of the structure remained enigmatic throughout more than a century of research. While early investigations recognised that many of the geological features of the area were unusual, including widespread brecciation of country rocks and the unique nature of the igneous suite, the Sudbury Igneous Complex (SIC) was widely regarded as a magmatic intrusive body that was linked with explosive volcanism (models reviewed in Giblin, 1984). However, following the discovery of shatter cones in the region by Dietz and Butler (1964), the involvement of a meteorite impact in the formation of the Sudbury Structure was widely recognised. There is now an overwhelming body of evidence in support of an impact origin. In addition to shatter cones, which are indicative of shock pressures of 2-10 GPa (Milton, 1977; Roddy and Davis, 1977), many other characteristic features of impact basins have been reported. These include shock deformation and metamorphic features in minerals throughout the footwall (e.g. Dressler 1984a), impact diamonds (Masaitis et al., 1999), and the similarity of pseudotachylites and suevitic breccias to rocks found in well constrained terrestrial impact structures such as Reis and Vredefort (See Peredery and Morrison, 1984). For many years, impact models attributed the SIC to mantle derived magmatism triggered by the impact event (Naldrett, 1984b; and references therein). Not until the application of isotope geochemistry to the various rock types of the SIC, did the intimate association between the impact and the igneous complex become clear. The osmium, neodymium, strontium and lead isotope systematics of the SIC all require an overwhelmingly crustal source (Dickin et al., 1992, 1996; Faggart et al., 1985; Hurst and Wetheril, 1974; Walker et al., 1991), precluding signicant mantle contribution, and consistent with the origin of the SIC as an impact melt sheet. Further developments in the understanding of the physical and geological eects of impact processes, such as the scaling of impact melt volumes (e.g. Grieve and Cintala, 1992), together with more recent geological, geochemical and geophysical studies in Sudbury, have led to the recognition that all of the main features of the Sudbury Structure can be accounted for by impact (e.g. Naldrett, 1999; Zieg and Marsh, 2005; Grieve and Therriault, 2000; and references therein). 1
Introduction The Sudbury impact structure had an original diameter of ca. 250 km (Spray et al.,
2004), making it one of the largest on Earth. The two other terrestrial impact basins of comparable size, the 300 km Vredefort impact structure in South Africa and the 180 km Chicxulub crater in Mexico, are either deeply eroded or deeply buried (see Grieve and Therriault, 2000). As such, Sudbury oers a unique opportunity to study many of the processes and geological eects of large meteorite impacts, a fact that will ensure many more decades of intensive investigation of this enigmatic structure. Of particular interest in this study is the well preserved, if deformed, impact melt sheet, which is by far the largest recognised on Earth. This oers a unique opportunity to study the processes of melt sheet formation and evolution, which are of great importance to crustal evolution on planetary bodies (e.g. Grieve et al., 2006). The Sudbury Structure is also famous for hosting a vast resource of Ni-Cu-Platinum Group Element (PGE) sulphide ore. The historic resource exceeds 1500 million tonnes with an average grade of around 1.2 wt% Ni, 1.1 wt% Cu and 0.4 g/t of Pt and Pd (Keays and Lightfoot, 2004). Long held as a type locality for the study of magmatic sulphide deposits, it is now clear that the processes leading to ore formation in Sudbury were exceptional. Recent developments have begun to understand ore forming processes in the context of an impact melt sheet (Keays and Lightfoot, 2004), however many key issues, such as the distribution of ore around the complex, remain unresolved. This investigation will build upon the recent geological and, in particular, geochemical developments made in the understanding of the Sudbury impact melt sheet. Particular emphasis will be placed on understanding how the melt sheet formed and evolved over time, and the aect of these processes on ore formation. The melt sheet also oers a unique terrestrial proxy for the aects of intense post-accretionary bombardment on the early Earth (Kring and Cohen, 2002), and this will also be explored.
1.2
Thesis aims
The identication of a crustal source for the Sudbury melt sheet was accompanied by the recognition that there are systematic compositional dierences between the two sides of the Sudbury Igneous Complex (SIC), termed the North and South Ranges. These dierences are manifest in the concentrations of certain trace elements (Lightfoot et al., 1997a), however they are most clearly dened in isotopic investigations. Dickin et al. (1996) attributed these dierences to impact melting of dierent target lithologies, and found a strong match between the Pb and Nd isotope ratios of ores and basal silicate rocks with those of nearby pseudotachylites in the footwall. Further investigations of the Os, Sr and Pb isotope systematics of the SIC have conrmed that distinct crustal 2
1.2. THESIS AIMS sources are required to explain the composition of melt sheet lithologies from each side of the SIC (Dickin et al., 1999; Morgan et al., 2002). Theoretical considerations on the violent movement and mixing of superheated, low viscosity shock melt (Phinney and Simonds, 1977; Simonds and Kieer, 1993) suggest that the initial products of impact melting would have been homogenised during crater formation, within minutes to hours of impact (Melosh and Ivanov, 1999). Yet it is clear that the spatial distribution of target lithologies played some part in controlling the variations in composition throughout the SIC. In order to further understand the evolution of the melt sheet, from crater formation to nal crystallisation, it is important to characterise the extent and scales of isotopic heterogeneity. This pertains to the crustal sources of the impact melts, and the degree to which they were homogenised. There is also considerable uncertainty surrounding the controls on the location of sulphide ore deposits in the SIC. Sulphide mineralisation is attributed to early sulphur saturation under superheated conditions. Dense immiscible sulphide liquids accumulated towards the base of the melt sheet by ecient gravitational settling (Keays and Lightfoot, 2004). However, the distribution of ores along the basal margin is highly variable. While concentration by convection and gravitational ow (e.g. Zieg and Marsh, 2005), together with a connection between the thickness of the melt sheet and the mineral potential of the basal margin (Lightfoot et al., 2001), go some way to explain the distribution of ores, the current models are not entirely satisfactory. Chemical heterogeneity could potentially be a signicant, and as yet unexplored, control on the sulphur saturation history of the melt sheet. Sudbury is also a unique analogue for impact melt sheets on the early Earth. The geological record of crustal processes during the rst 600 Myr of Earths history is almost exclusively limited to detrital zircons from the Yilgarn craton. Numerous studies have sought to elucidate the source rocks from which these zircons crystallised. Based upon low crystallisation temperatures, inclusion assemblages dominated by granitic minerals and trace element compositions, a predominantly granitic source has been proposed (Hopkins et al., 2008; Maas et al., 1992; Menneken et al., 2007; Watson and Harrison, 2006, 2005). In contrast to predictions of a long-lived mac crust following magma ocean crystallisation (Kamber, 2007; Kramers, 2007), this suggests that felsic continental crust was widespread on the early Earth. Our ability to interpret the sources of these detrital grains relies upon knowledge of zircon populations from well constrained magmatic and metamorphic rocks. No such ground truth data currently exists for zircons crystallised from impact melt sheets. Given the likely importance of impact processes during intense post accretionary bombardment of the early Earth (e.g. Kring and Cohen, 2002; Grieve et al., 2006), such melts are a potentially signicant source of the ancient zircons. 3
Introduction
Furthermore, whilst inclusions in zircon are often utilised in metamorphic studies, very little data is available for magmatic rocks. By characterising zircons from throughout the SIC, the importance of impact melt sheets in the source of these ancient grains can be addressed. The principal aims of this thesis are therefore to: Understand how the melt sheet evolved, from crater formation through to nal crystallisation. Identify the crustal sources of the melt sheet and the depth of shock melting in the Sudbury impact event. Characterise the extent to which chemical variability in the melt sheet controls sulphide ore formation and explore the implications for exploration strategy. Identify whether impact melt sheet zircons are common in the Hadean detrital zircon record. In Sudbury, the Pb isotope system has proven to be more sensitive to target rock variations than other isotopic systems such as Nd. This is because the two main groups of target rocks are Archean gneisses of the Superior Province and Huronian metasedimentary rocks, which were largely derived from the Superior Province (McLennan et al., 1979, 2000). Due to the dierences in chemical properties of parent and daughter isotopes, fractionation of U and Th from Pb occurs during sedimentary processes. This has resulted in dierent Pb isotope evolution in each target rock group over the time between sedimentation (<2450 Ma; Bennet et al., 1991; Young et al., 2001) and the time of impact (1850 Ma; Krogh et al., 1982). As such, the more specic objectives of this thesis are to: Characterise the scales of Pb isotope heterogeneity throughout the melt sheet Identify variations in metal depletion signatures throughout the melt sheet Test the degree of coherence between the Pb isotope compositions of sulphide ores and the overlying melt sheet Characterise the Pb isotope variability in early formed impact melts from the Oset Dykes Explore isotopic and trace element constraints upon the source of the melt sheet and the metals contained within Sudburys ores 4
1.3. THESIS STRUCTURE Characterise zircons from throughout the melt sheet stratigraphy, with particular emphasis on inclusion populations and trace element compositions.
1.3
Thesis structure
At the core of this thesis are three papers that are either published or under review. These form the majority of the scientic contribution of this doctoral study and are included in chapters 4, 5 and 6, together with some additional results and discussion. Chapter 2 reviews key aspects of the geology of the Sudbury Structure, providing a framework for later discussion. A detailed account of methods employed, in particular for Pb isotope analysis, is provided in chapter 3. In chapter 4 the scales of Pb isotope heterogeneity, and variations in metal depletion signatures, throughout the melt sheet are investigated. The implications for melt sheet evolution and ore forming processes will be explored. This chapter includes the following paper:
Darling J.R., Hawkesworth C.J., Lightfoot P.C., Storey C.D. and Tremblay E. (2009) Isotopic heterogeneity in the Sudbury impact melt sheet. Earth and Planetary Science Letters. doi:10.1016 /j.epsl.2009.11.023
Chapter 5 presents the results of an investigation into the Pb isotope systematics of early formed impact melts in Sudbury, allowing for an assessment of the crustal sources of the melt sheet. The implications for melt sheet formation will be discussed. This chapter is comprised of the following paper:
Darling J.R., Hawkesworth C.J., Storey C.D., and Lightfoot P.C. Shallow impact; isotopic insights into crustal contributions to the Sudbury impact melt sheet. Geochemica et Cosmochimica Acta, in-review
In chapter 6 the characteristics of impact melt sheet zircons are investigated, and the implications for the interpretation of detrital zircon populations are explored. This chapter consists mainly of the following paper:
Darling J.R., Storey C.D. and Hawkesworth C.J. (2009) Impact melt sheet zircons and their implications for Hadean crustal processes; Geology, vol. 37, no. 10, p. 927-930
As a result of including the three papers, chapters 4, 5 and 6 stand alone, and include detailed discussion of results. The ndings of this study are summarised in Chapter 7, along with identied directions for future research. There are a number of local terms for aspects of the geology of the Sudbury Structure, which will be referred to throughout this thesis. To aid the reader, a glossary is provided at the end of this introductory chapter.
Introduction
1.4
Author contributions to published papers
Chapters 4, 5 and 6 contain published papers, for each of which I am the primary author. The research for all three papers has been undertaken during my doctoral studies at the University of Bristol and I have made the predominant contribution to each. The details of author contributions to the papers are as follows:
Darling J.R. et al. (2009) Isotopic heterogeneity in the Sudbury impact melt sheet. Earth and Planetary Science Letters. doi:10.1016/j.epsl.2009.11.023
Building upon the initial PhD project outline, written by C. Hawkesworth and P. Lightfoot, the design of this investigation, including sampling strategy and analytical methodology, was done by J. Darling. Fieldwork was carried out by J. Darling, with assistance from E. Tremblay, P. Lightfoot and the Sudbury Basin Group of Vale Inco Exploration. The preparation and analysis of samples for Pb isotope ratio compositions was undertaken by J. Darling, with technical assistance from C. Storey and R. Avanzinelli. Data evaluation and interpretation, together with the preparation of the manuscript was done by J. Darling, and beneted from discussion with co-authors. The nal paper was written by J. Darling and includes comments, mostly on the clarication of methods and ideas, from co-authors and reviewers.
Darling J.R. et al., Shallow impact; isotopic insights into crustal contributions to the Sudbury impact melt sheet. Geochemical et Cosmochimica Acta, in-review
Similarly to the EPSL paper, the project was designed and implemented by J. Darling. The manuscript was written by J. Darling, incorporating suggestions from coauthors.
Darling J.R. et. al. (2009) Impact melt sheet zircons and their implications for Hadean crustal processes; Geology, vol. 37, no. 10, p. 927-930
The project was designed by J. Darling, following discussions with C. Storey about mineral inclusions in zircon, and was based largely on a proposal written by J. Darling for the Eugene M. Shoemaker impact cratering award. Sampling and analytical work were undertaken by J. Darling. The paper was written by J. Darling, and beneted from discussion with co-authors and H. Marschall. The modelling of residual liquid compositions was suggested by reviewer L. Coogan.
James Darling
1.5. GLOSSARY
1.5
Glossary
Trough like structures in the basal contact of the melt sheet that are often associated with major ore deposits. Polymict, matrix supported, contact metamorphosed breccia that occurs between the Sudbury Igneous Complex and unbrecciated footwall rocks (McCormick et al., 2002).
Embayment Footwall Breccia
Lower Unit
The Lower Unit of the Main Mass consist typically of quartz monzogabbro to quartz gabbro. Throughout much of the previous literature on Sudbury, this sequence was referred to as the Sudbury norite.
Main Mass
The Sudbury impact melt sheet. Typically 2.5 km thick (Keays and Lightfoot, 2004), the Main Mass is divided into the Lower Unit and Upper Unit, separated by the Middle Unit, with the approximate proportions 30:60:10 respectively.
Middle Unit
A transitional unit between the Lower Unit and Upper Unit of the Main Mass. Typically consists of quartz monzogabbro to granodiorite and is often termed the quartz gabbro transition zone in previous literature.
North Range
The northern exposed section of the Sudbury Igneous Compex, underlain by Archean gneisses (the Levack Gneiss Complex) and granitic intrusions of the Superior Province.
Oset Dykes
Radial and concentric dykes of the Sudbury Igneous Complex, containing quartz diorites with variable inclusion and sulphide content. These units were emplaced prior to dierentiation of the melt sheet (e.g. Lightfoot et al., 1997b) and may be representative of the bulk crustal melt (Lightfoot and Farrow, 2002; Lightfoot et al., 1997b; Mungall et al., 2004).
Onaping Formation
A 1400 m thick sequence of impact generated pyroclastic like fall, ow and debris ow deposits, hydroclastic breccias and melt bodies (Ames et al., 2002, 1998; Muir and Peredery, 1984), which immediately overlies the Sudbury Igneous Complex.
Onwatin & Chelmsford Formations South Range
A series of predominantly mudstones and greywackes, deposited within the crater, that overlie the Onaping Formation (Rousell, 1984a). The southern exposed section of the Sudbury Igneous Complex, underlain by metasedimentary and metavolcanic rocks of the Huronian Supergoup, together with the Nipissing gabbro suite and felsic intrusions. Seperated from the North Range by zones of faulting.
Introduction
Sublayer
Discontinuous inclusion and sulphide rich norite to monzogabbro that occurs at the melt sheet - footwall contact and is locally underlain by footwall breccias.
Sudbury Basin
Sedimentary basin containing crater lling rocks of the Onaping, Onwatin and Chelmsford Formations of the Whitewater Group.
Sudbury Breccia
Pseudotachylitic breccia within the footwall to the melt sheet, often occurring as veins or crudely tabular bodies. Formed by communition and melting of target rocks during excavation and modication stages of crater formation (Dressler, 2004, 1984a; LaFrance et al., 2008; Riller, 2005; Thompson and Spray, 1994).
Sudbury Igneous Complex (SIC) Sudbury Structure
Grouping of the igneous rock types in the Sudbury Structure. Incorporating the Main Mass, Sublayer and Oset Dykes. Geological feature now recognised as the Sudbury impact structure. Term includes three main elements; the Sudbury Igneous Complex, the Sudbury Basin and brecciated footwall rocks.
Upper Unit
The Upper Unit of the Main Mass is granitic, with abundant granophyric intergrowths. This unit is often referred to as the Sudbury granophyre throughout previous literature.
2 The geology of the Sudbury Structure

As a result of over a hundred years of geological research and mineral exploration there is a vast literature relating to the Sudbury Structure. There are many fascinating rock types and geological relationships in Sudbury, which are described in detail in volumes edited by Lightfoot and Naldrett (1994) and, in particular, Pye (1984). The aim of this chapter is provide detail of the key geological relationships of the area in order to lay the foundations for further discussion in the following chapters. Important developments in the understanding of the Sudbury Structure from the last twenty years will also be highlighted. During this time signicant advancements have been made in many aspects of Sudbury geology.
2.1
Regional geological setting
The Sudbury Structure is located near the junction of three major geological and structural provinces in the southern Canadian Shield. Straddling the contact between the Archean Superior Province and the Paleoproterozoic Southern Province, the structure also lies within 10 km of the Grenville Front, a zone of shear and thrust faults which marks the edge of the Grenville Province (Figure 2.1). Previous studies have shown that the dierence in footwall rocks on each exposed side of the SIC was an important factor in the evolution of the melt sheet. The northern exposed section of the SIC, termed the North Range, is underlain by Archean gneisses and felsic intrusions of the Superior Province. In contrast, the South Range footwall consists of Paleoproterozoic metasedimentary and metavolcanic rocks of the Huronian Supergroup, together with mac and felsic intrusive bodies.
2.1.1
The Superior Province
The Archaean Superior Province north of Sudbury consists of several major lithostratigraphic components of the Abitibi Subprovince, including metavolcanic and metasedimentary belts, felsic plutons and gneissic terrains (Card, 1972). The massive felsic Algoman plutons (Van Schmus 1965) form much of the Abitibi Subprovince in the Sudbury area. These include the Cartier Batholith, adjacent to the Sudbury Structure, and intrude tonalite-granodiorite-mac gneisses such as those of the Levack Gneiss Complex. East-west trending greenschist to amphibolite facies (e.g. Easton, 2000a) metavolcanic and metasedimentary belts, such as the Benny and Abitibi greenstone belts, also occur. 9
The geology of the Sudbury Structure
82 AB Canada
USA 47 300 km 47
SR
SZ
46
Lake Huron 50 km Palaeoproterozoic Southern Sudbury Province Structure Grenville Province Whitewater Group Sudbury Igneous Complex Nipissing Mafic suite Felsic plutons Huronian Supergroup Archean Superior Province Felsic plutons, gneisses and migmatites Levack Gneiss Complex Metavolcanics and metasedimetary rocks
AB - Abitibi Greenstone Belt
Gr
en
vil
le
Fr
on
46 82
Phanerozoic cover Synform Antiform Thrust fault Fault zone

SRSZ - South Range Shear Zone
Figure 2.1: Regional geological setting of the Sudbury Structure. The simplied geological map
shows the distribution of the main geological provinces and highlights the general trends of major fold and fault structures. SRSZ - South Range Shear Zone. Simplied after Card et al. (1984).
10
2.1. REGIONAL GEOLOGICAL SETTING
Levack Gneiss Complex The footwall at the northern margin of the SIC predominantly consists of high-grade metamorphic rocks, collectively termed the Levack Gneiss Complex (Langford, 1960). These upper amphibolite to granulite facies rocks consist of banded and migmatitic tonalitic, granodioritic and dioritic gneisses, with interspersed metapyroxenite and gabbroic bodies, xenoliths and minor paragneisses (Dressler, 1984b). Furthermore, foliated tonalitic, granodioritic, mac and ultramac intrusions also occur (Card et al., 1984). The complex has primary ages ranging from 2711 to 2647 Ma, with the peak of upper amphibolite to granulite metamorphism occuring at ca. 2645 Ma (Krogh, et al. 1984) at 6-8 kbar and 750-800 C (James et al., 1992). Shock deformation features associated with the Sudbury event extend for up to 17 km from the base of the SIC (Dressler, 1984a), and within 2 km of the SIC the granulites are overprinted by thermal contact metamorphism, with conditions of 4-6 kbar and 800-950 C reported (James et al., 1992). Cartier Batholith The Cartier Batholith forms part of the immediate footwall to the SIC in the west of the Sudbury Structure and is extensive north of the Levack Gneiss Complex. These granitoids are predominantly monzogranitic to granodioritic, generally undeformed and provide a zircon U-Pb age of 2642 1 Ma (Meldrum et al., 1997), marginally younger than the inferred peak of granulite facies metamorphism in the Levack Gneiss Complex. The rocks are metaluminous to mildly peraluminous and enriched in the light rare earth elements (LREE), U and Th (Meldrum et al., 1997).
2.1.2
The Southern Province
The Southern Province represents an exposed remnant of a Paleoproterozoic mobile belt, the Penokean Fold Belt, along the southern margin of the Superior Province (e.g. Card et al., 1972). In the Sudbury region, and forming the footwall to the South Range of the SIC, the Southern Province is comprised of the Huronian Supergroup and various intrusive rock types. There is considerable complexity in the geology of the Southern Province, which is outlined in Card et al. (1972), Card et al. (1984) and Dressler (1984b). An overview of the main lithostratigraphic units is provided below. Huronian Supergroup The Huronian Supergoup comprises a southward and eastward thickening wedge of mainly sedimentary supracrustal rocks, which were deformed during the 1.89-1.80 Ga Penokean orogeny (Young et al., 2001). The sedimentary sequence has a maximum thickness of 11
12 km near Lake Huron and 8 km to the north east of the Sudbury structure (Card et al., 1984; Dressler, 1984b; Young et al., 2001), and consists of cyclical deposits of conglomerate, mudstone, greywacke and quartz-feldspar arenites (Figure 2.2). The lower Huronian, which is divided into the Elliot Lake, Hough Lake and Quirke Lake Groups, was likely deposited in a rift basin (Roscoe and Card, 1992; Young et al., 2001). In contrast, the Cobalt Group of the upper Huronian is thought to represent a passive margin sequence (e.g. Young et al., 2001). The sedimentary rocks are constrained to have been deposited between 2450 Ma and 2219 Ma on the basis of U-Pb zircon and baddeleyite ages of lower Huronian mac volcanic rocks and cross cutting Nipissing gabbro intrusions (Corfu and Andrews, 1986; Krogh et al., 1982). The lowermost Huronian sediments rest unconformably on Archean basement that commonly exhibits a well developed palaeosol (McLennan et al., 1979). On the basis of paleocurrent directions, REE concentrations and Nd and Pb isotope systematics, a provenance for the sedimentary rocks dominated by the Archean Superior Province has been identied (Card et al., 1972; McLennan et al., 2000, 1979; Young et al., 2001). Intrusive igneous bodies A number of intrusions occur within the Huronian Supergroup south of the Sudbury Structure. Three Palaeoproterozoic granitic plutons, the Creighton, Murray and Skead plutons, occur along the southern margin of the SIC, cutting the lower part of the Huronian succession. Zircon U-Pb ages constrain the time of intrusion of these granites to between 2.47 and 2.33 Ga (Krogh et al., 1984). Several 2480-2450 Ma mac intrusive suites, including the large leucogabbroic East Bull Lake and Shakespeare-Dunlop intrusions (Figure 2.1), together with a number of smaller mac sills of similar age also occur (Prevec and Baadsgaard, 2005). Several of the smaller mac sills, the Drury Township, Falconbridge Township and Joe Lake intrusions, occur adjacent to the SIC contact (see Figure 2.3). The most voluminous intrusive rocks in the Southern Province are the 2.2 Ga Nipissing gabbro sills and dykes. Individual intrusions range in thickness from a few hundred meters to over a thousand meters, and consist of dominantly tholeiitic to calc-alkaline rocks ranging from diabase through gabbronorite, gabbro, quartz diorite and granodiorite. The intrusions are considered by Lightfoot et al. (1993) to represent a large igneous gabbroic province that formed the roots to ood type basaltic eruptions. In the Sudbury area a more mac variety occurs, known as the Sudbury Gabbro. These rocks have up to 18 wt% MgO (Lightfoot, 2002).
12
2.1. REGIONAL GEOLOGICAL SETTING
13
Figure 2.2: Summarised stratigraphy of the Huronian Supergroup, simplied cross section and interpretations of depositional environments. From Fedo
et al. (1997).
2.2
Geology of the Sudbury Structure
The Sudbury Structure includes several related geological components: The Sudbury Igneous Complex (SIC): A term encompassing the igneous rock types of the Sudbury Structure. The SIC is comprised of the Main Mass, now recognised as an impact melt sheet, the radial and concentric Oset Dykes, which protrude from the Main Mass into the footwall, and the Sublayer, a discontinuous mac unit that occurs at the Main Mass - footwall contact. Based upon dierences in footwall lithologies, the petrology of the Main Mass and the elliptical outcrop pattern, the SIC is divided into North, East and South Ranges. The Sudbury Basin: the area enclosed by the SIC and containing rocks of the Whitewater Group. The Whitewater group is comprised of three formations: the Onaping, Onwatin and Chelmsford Formations. Stratigraphically, these formations overlie the SIC, and are interpreted as suevitic (fallback) breccias and post impact basin lling siliciclastic rocks (Ames et al., 2002; Dressler et al., 1996; Gibbins et al., 1997; Muir and Peredery, 1984). Breccias: Two distinct types of breccia that are intimately linked to the formation of the Sudbury Strucure occur in the footwall to the SIC. Footwall Breccias are composed of shattered and crushed country rocks that form a layer 10 to 50 m thick at the Main Mass or Sublayer - footwall contact. Pseodotachylitic breccias, locally termed Sudbury Breccias, are extensive throughout the footwall, occuring as dyke like bodies or irregular masses. The distrubution of each of these features in shown in Figure 2.3 and a representation of the stratigraphic relationships provided in Figure 2.4.
2.2.1
The Sudbury Igneous Complex
Main Mass The Main Mass of the Sudbury Igneous Complex has crystallised with a highly regular stratigraphy, and is accordingly divided into the Lower, Middle and Upper Units, with the approximate proportions 30:10:60 respectively. The Main Mass varies considerably in thickness. In areas between embayment structures (see Figure 2.4), thickness varies from 5000 m down to as little as 300 m (Keays and Lightfoot 2004). Despite these variations, the ratio of the Lower Unit to Upper Unit remains relatively constant at nearly 40:60, although the proportion of the Middle Unit varies signicantly. 14
Grenville Front - frontal thrust

Parkin Offset
Fault systems Paleoproterozoic Chelmsford Formation Onwatin Formation Onaping Formation Upper Unit SIC Middle Unit Lower Unit Quartz diorite (Offset Dykes) Nipissing mafic suite Cobalt Group Hough & Quirke Groups Elliot Lake Group Granitic plutons East Bull Lake type mafic intrusions
T ON FR LL VI EN GR E
46 45'
Foy Offset
Hess Offset
Wanapitei Lake
R H
Ministic Offset
CHELMSFORD
46 30'
TRILL
R U
Copper Cliff Offset
A
SUDBURY
Frood Stobie
Huronian Supergroup
Whitewater Group
10 Km
2.2. GEOLOGY OF THE SUDBURY STRUCTURE
Figure 2.3: Simplied geological map of the Sudbury Structure. Modied after Ames et al. (2005)
Superior Province
15
81 00'
Neoarchean Cartier batholith

Massive granodiorite, granite
Worthington Offset
Metavolcanic and metasedimentary rocks

(Benny Belt)
81 30'
Levack Gneiss Complex
Tonalitic-granodiorite and mafic-ultramafic gneisses
Whitewater Gp.
Chelmsford Fm. Onwatin Fm. Onaping Fm.

DM SM Plag rich upper unit
Post-impact basin fill Impactites (~1.4 km)
Main Mass
Upper Unit
Middle Unit Lower Unit Sublayer

Embayment
Melt sheet (~2.5 km)
Footwall Breccia
Footwall
Sudbury Breccia Offset Dykes
Fractured and shocked basement
Figure 2.4: Schematic representation of the stratigraphic relationships in the Sudbury Structure.
Simplied from Ames and Farrow (2007).
Before discussing the petrology of the Main Mass, it is important to note that the terminology and subdivisions of the Main Mass used in this thesis dier from much of the literature on Sudbury geology. Traditionally, the Lower, Middle and Upper Units have been termed the norite, quartz gabbro and granophyre respectively. These terms date back to petrographic studies by Williams (1891) and are somewhat misleading. For example, as shown by Therriault et al. (2002), the Lower Unit (norite) samples do not conform to the IUGS classication of norite (Le Maitre et al., 2005) and are more correctly classied as quartz monzogabbro to quartz gabbro. The Middle Unit typically consists of quartz monzogabbro to granodiorite and the Upper Unit rocks are granites. Dierences in petrology are observed between the North and South Ranges, in particular within the Lower Unit. Previously, the North Range Lower Unit was divided into a mac norite and a felsic norite. This distinction was made on the basis of an increase in orthopyroxene relative to clinopyroxene, and a change from hypidiomorphic granular to poikilitic textures, in the lowermost 300 m of the Lower Unit stratigraphy, although these changes are gradational (Figure 2.5). In contrast, the South Range Lower Unit has typically been divided into the South Range norite and basal quartz rich norite, on the basis of an increase in quartz content (Figure 2.5) and change in texture 16
NORTH RANGE 2000
SOUTH RANGE
?
True Thickness (m)
1500
Upper Unit
e Middl
1000
Unit
500
Lower Unit
50 Modal %
100
50 Modal %
100
Oxides + apatite + titanite Clinopyroxene
Biotite + primary amphibole
Orthopyroxene Quartz + granophyric intergrowths Plagioclase
Figure 2.5: Petrology of the North and South Ranges of the Main Mass. Modied after Naldrett et al. (1970).
towards the basal contact. Again, these changes are gradational over hundreds of meters. The main petrological distinctions between the North Range and South Range Lower Unit rocks are highlighted in Figure 2.5. The South Range rocks are variably altered and towards the top of the Lower Unit little fresh pyroxene is present. Throughout this thesis these rocks will be referred to as the North Range Lower Unit or South Range Lower Unit, with distinction of the basal rock types by use of the terms basal Lower Unit etc. Various petrological features clearly distinguish the Main Mass from other well known igneous bodies such as the Bushveld, Stillwater and Skaergaard complexes. These include: the lack of conspicuous modal layering, the large amount of silicic relative to mac rock, the lack of upper and lower chilled margins, a thick sandwich zone of unusual mac material (the Middle Unit), the uniformity of Lower Unit textures over large distances, and lateral stratigraphic continuity over tens of kilometers (Zieg and Marsh, 2005). South Range petrology Upper Unit rocks in the South Range are, in general, sheared and altered along the South Range Shear Sone (SRSZ). Where least deformed the rocks are seen to consist 17
predominantly of coarse grained quartz and alkali feldspar granophyric intergrowths (6070 %), plagioclase (15-20 %), amphibole (<10 %) and biotite, with minor oxides, apatite and titanite. Plagioclase is developed as tabular grains set in a matrix of granophyric intergrowths. Along the upper contact of the Main Mass a more plagioclase rich variant is exposed (Figure 2.4), and contains fragments of country rocks similar to the Onaping Formation (Muir and Peredery, 1984; Naldrett and Hewins, 1984). The Upper Unit grades, with increasing plagioclase, clinopyroxene, biotite, magnetite and ilmenite into the granodioritic to quartz monzogabbroic Middle Unit. This gradation typically occurs over hundreds of meters, and is often referred to as the Transition Zone (e.g. Therriault et al., 2002). Titaniferous magnetite of the Middle Unit constitutes up to ten percent of the rock. The contact between the Middle Unit and the underlying Lower Unit is also gradational, with decreasing clinopyroxene, titanomagnetite and apatite into the Lower Zone. Also, where least altered this boundary marks the entry of orthopyroxene. For the most part, the predominantly quartz monzogabbroic Lower Unit has a medium to coarse grained hypidiomorphic granular texture, consisting of plagioclase and orthopyroxene (En65-70 ; Naldrett et al., 1970) with clinopyroxene, quartz, biotite, amphibole, magnetite and ilmenite. Clinopyroxene and plagioclase occur as subhedral tabular crystals, whereas orthopyroxene occurs as anhedral masses, and the alignment of plagioclase crystals forms a distinct planar igneous lamination. Although secondary alteration is locally intensive, the hydrous phases biotite and amphibole (hornblende) are considered to be primary (Naldrett et al., 1970). Towards the base of the Lower Unit there is an increase in quartz (up to 20 %) and biotite (up to 20 %) content, as well as a decrease in average grain size, and a loss of igneous lamination. The thickness of this predominantly quartz gabbroic zone varies from tens to hundreds of meters. North Range petrology Upper Unit rocks in the North Range are less deformed and altered than those in the South Range. The granophyric rocks are very similar to the least deformed South Range samples, although occasional clinopyroxenes may be present (Naldrett et al., 1970). It is composed mainly of granophyric intergrowths of quartz and microcline, with albite laths up to 4 mm in length, anhedral quartz, perthite, epidote, biotite and amphibole. The contact between the Upper and Middle Units is gradational, typically over 100-200 m. The Middle Unit is also similar to that of the South Range, consisting of plagioclase, clinopyroxene, amphibole, biotite, titanite and magnetite, together with interstitial granophyric intergrowths. Oxide minerals may be slightly more abundant than in the South Range, with ilmenite commonly occurring as exsolution lamellae rather than discrete
18
2.2. GEOLOGY OF THE SUDBURY STRUCTURE grains. The contact between the Middle Unit and the Lower Unit is again gradational, typically over tens of meters. The Lower Unit is a coarse grained hypidiomorphic granulartextured rock comprised of clinopyroxene and orthopyroxene, plagioclase, biotite, interstitial micrographic intergrowths and minor apatite, ilmenite and ulvospinel. The ratio of clinopyroxene to orthopyroxene is typically around 2:1, although in the lowermost ca. 300 m there is a signicant, gradational, increase in orthopyroxene (up to 50 % of the rock). Similarly to the basal Lower Unit samples in the South Range, the basal rocks do not show igneous lamination, while plagioclase crystals in the overlaying quartz monzogabbros do have a conspicuous alignment. Sublayer The Sublayer contains almost 50 % of the known and historic sulphide ore resource in Sudbury (Keays and Lightfoot, 2004). It occurs as discontinuous lenses along the contact between the Main Mass and the footwall, with thicknesses greatest (hundreds of meters) in trough like radial depressions called embayments (Figure 2.4). Field relationships with the overlying Main Mass are often conicting. For example, inclusions of the quartz rich Lower Unit have been observed in the Sublayer and inclusions of Sublayer have been observed in the Lower Unit (Naldrett 1984, Lightfoot 1995). The contacts with the Lower Unit vary from gradational over tens of meters (Therriault et al., 2002) to sharp, and are never seen to be chilled (Lightfoot et al., 1997c). The Sublayer is comprised of an inclusion and sulphide rich noritic to gabbroic rock with an igneous texture, underlain by local Footwall Breccia with a metamorphic textured matrix (Pattison, 1979). The matrix consists of orthopyroxene and plagioclase, with varying amounts of clinopyroxene and minor quartz, granophyric intergrowths and iron oxides, and has a medium to coarse grained hypidiomorphic to subophitic texture. The sulphide content varies from <1 % to over 60 modal %. Inclusion populations are dominated by locally derived footwall rocks and exotic clasts of ultramac rock (Lightfoot et al., 1997c; Rae, 1975). Oset Dykes When propagated to depth the quartz diorite Oset Dykes have an estimated total volume of 100 km3 (Keays and Lightfoot, 2004). The Oset Dykes group into two main types: radial and concentric. Radial Osets intrude up to 30 km into the footwall rocks, typically following domains of Sudbury Breccia (e.g. the Worthington, Copper Cli, Ministic, Parkin and Foy Oset Dykes; see Figure 2.3) and are linked to embayment structures at the base of the Main Mass. Varying in thickness from hundreds to tens 19
(a) NR Sublayer
(b) SR Sublayer (2 mm)
(c) NR basal Lower Unit
(d) NR Lower Unit
(e) Middle Unit
(f) Upper Unit
Figure 2.6: Photographs of thin sections from the main units of the SIC. NR - North Range, SR
- South Range. Field of view is 4 mm wide unless otherwise stated. (a) Sublayer norite from the Trill Embayment; (b) Sublayer gabbro from the Creighton Embayment; (c) and (d) North Range Lower Unit samples from the 81138 drill core, showing the dierence between orthopyroxene rich basal monzogabbro and overlying monzogabbros; (e) altered Middle Unit quartz monzogabbo from the North Range (plane polarized light); (f) North Range Upper Unit granophyre
20
2.2. GEOLOGY OF THE SUDBURY STRUCTURE of meters, the dykes generally thin away from the Main Mass. Concentric Oset Dykes form ring-like structures centred on the Main Mass. They include ca. 1 km wide Sudbury Breccia belts, which contain discontinuous lenses of quartz diorite (e.g. the Frood-Stobie breccia belt; Scott and Spray, 2000), and more continuous dykes of quartz diorite (e.g. the Hess and Manchester Oset Dykes). The shape and orientation of the Oset Dykes are thought to have been controlled by pre-existing structures and lithological variations in the footwall (Murphy and Spray, 2002; Lightfoot and Farrow, 2002; Lightfoot and Naldrett, 1997). The dykes commonly pinch and swell, and are often discontinuous at the surface. The mineralogy of Oset Dyke quartz diorite is variable, and previous workers classied dierent types based upon their primary mac phases (Grant and Bite, 1984). These include orthopyroxene and clinopyroxene, amphibole and biotite. The most common phase is amphibole-quartz diorite, with the amphiboles considered pseodomorphic after pyroxene (Grant and Bite, 1984) . The rocks are massive, ne- to medium-grained and exhibit granular to sub-granular textures. Mac minerals comprise 45 to 55 % of the rocks, with 30-40 % feldspar, 5-15 % quartz and minor granophyric intergrowths and oxides. According to variations in mineralogy, eld relationships, sulphide content and inclusions, two main phases of quartz diorite can be discerned in many Oset Dykes: (1) an inclusion and sulphide poor marginal phase (QD; Figure 2.8a) that is often chilled against the margins of the dykes; and (2) a ne to medium grained quartz diorite containing sulphide, biotite and inclusions ranging from millimeters to meters in size (IQD; Figure 2.8b). The two phases of quartz diorite are perhaps best dened in the Worthington Oset Dyke. The general eld relationships along the dyke are shown in Figure 2.7. Marginal chilled QD is transitional into medium grained QD. Locally the dyke contains a core of IQD, which can be choked with inclusions surrounded by semi-massive to massive sulphide. The inclusions are predominantly amphibolites, which are petrologically and geochemically similar to Sudbury Gabbros (Lightfoot and Farrow, 2002). The lack of sulphide in the marginal QD is evidence that this unit was emplaced prior to sulphur saturation of the melt sheet, which likely occurred at temperatures in excess of the Lower Unit liquidus (Keays and Lightfoot, 2004). Geochronology of the SIC A summary of the geochronological investigations of the SIC is provided in Table 2.1. The Main Mass, Sublayer and Oset Dykes have indistinguishable magmatic ages of 1849-1850 Ma.
21
Proximal to the Main Mass

20 m Country rocks Arkose Amphibolite Metasedimentary rocks Offset Dyke Sudbury breccia Fine grained quartz diorite with inclusions of greywacke Sulphides
Finely disseminated Blebby to heavily disseminated Semi-massive
Medium-coarse grained quartz diorite IQD (< 20 % inclusions) IQD (> 20 % inclusions dominated by amphibolite) Amphibolite IQD (> 90 % inclusions)
Distal from Main Mass
Figure 2.7: Schematic representation of geological relationships in the Worthington Oset Dyke.
Modied after Lightfoot et al. (1997a). IQD - Inclusion bearing quartz diorite. Note that greywacke inclusions in the marginal quartz diorite are rare.
(a) Quartz diorite (QD)
(b) Inclusion bearing quartz diorite (IQD)
Figure 2.8: Photographs of thin sections from the main quartz diorite phases of the Worthington
Oset Dyke. (a) Medium grained biotite-quartz diorite from the Totten Mine; (b) Fine-medium grained IQD with amphibolite inclusions from the Totten Mine. Width of eld of view in 2 mm and both photos were taken with crossed polarizers
22
Group Main Mass Main Mass Main Mass Main Mass Main Mass Main Mass Main Mass Main Mass Oset Dyke Oset Dyke Sublayer Whistle Embayment Whistle Embayment Whistle Embayment Whistle Embayment Whistle Embayment 1848.7 1.1 1848.4 +3.8/1.8 1848.3 1.0 1848.3 1.0 1848.4 1.4 1849.1 1.1
Lithology Lower Unit Lower Unit Lower Unit Lower Unit Upper Unit Lower Unit Lower Unit Lower Unit quartz diorite quartz diorite norite
Location North Range North Range North Range North Range North Range South Range South Range South Range Copper Cli Foy Whistle Embayment
Age (Ma) 1848.9 +4.0/2.7 1850 +3.4/2.4 1849.53 0.21 1849.6 +3.4/3 1850.5 3.0 1849.7 1.1 1849.11 0.19 1849.4 +1.9/1.8 1849.8 2.0 1852 +4/3 1848.1 1.8
Source Krogh et al. (1984) Krogh et al. (1984) Davis (2008) Krogh et al. (1982) Krogh et al. (1984) Krogh et al. (1984) Davis (2008) Krogh et al. (1982) Corfu and Lightfoot (1996) Corfu and Lightfoot (1996) Corfu and Lightfoot (1996) Corfu and Lightfoot (1996) Corfu and Lightfoot (1996) Corfu and Lightfoot (1996) Corfu and Lightfoot (1996) Corfu and Lightfoot (1996) Ames et al. (1998)
23
Sublayer
Sublayer
Method zircon U-Pb (TIMS) zircon U-Pb (TIMS) zircon U-Pb (TE-TIMS) zircon U-Pb (TIMS) baddeleyite U-Pb (TIMS) zircon U-Pb (TIMS) zircon U-Pb (TE-TIMS) zircon U-Pb (TIMS) zircon U-Pb (TIMS) zircon U-Pb (TIMS) zircon and baddeleyite UPb (TIMS) zircon and baddeleyite UPb (TIMS) zircon U-Pb (TIMS) zircon U-Pb (TIMS) zircon and baddeleyite UPb (TIMS) zircon U-Pb (TIMS) titanite U-Pb (TIMS)
Sublayer Sublayer
olivine melanorite inclusion metapyroxenite inclusion melanorite pod melanorite pod
Sublayer Onaping Formation
diabase amphibole vein (hydrothermal)
Table 2.1: Summary of geochronological investigations of SIC and associated lithologies. TIMS; Thermal Ionisation Mass Spectrometry. TE-TIMS;
Thermal Extraction TIMS.
2.2.2
Breccias of the Sudbury Structure
Sudbury Breccia The most prominent feature of the Sudbury event in the footwall to the Main Mass are zones of Sudbury Breccia. The similarity of these pseudotachylitic breccias (Thompson and Spray, 1994) to the type locality of such rocks, in the Vredefort Structure in South Africa (Shand, 1916), has long been recognised (Speers, 1957). They occur as irregular shaped bodies or dikes that range in size from a few millimeters, to zones hundreds of meters wide, such as the 45 km long South Range Breccia Belt (SRBB; Scott and Spray, 2000). The breccias are most pervasive within 10 km of the North and 15 km of the South Range of the Main Mass. There is also a 10-15 km wide zone of brecciation 20 to 25 km north of the Main Mass and isolated bodies up to 80 km from the SIC (Dressler, 1984a). The breccias are spatially associated with discontinuities such as faults, bedding planes and lithological contacts (Dressler, 1984a; Rousell et al., 2003) and have sharp contacts with their host rocks. The rocks consist of subrounded fragments of predominantly locally derived country rocks, in a ne matrix (100 m; Scott and Spray, 2000), which may be fragmental, recrystallised or locally igneous textured (Rousell et al., 2003). Clast sizes range from milimeters to tens of meters. Geochemical investigations have shown that the composition of the matrix and clasts is similar (Dressler, 1984a) and that the breccias are mostly derived from local host rocks. While there has been signicant debate surrounding the mechanisms that produced the breccias, there is growing consensus that cataclastic milling and frictional melting were the dominant processes (Thompson and Spray, 1994; Rousell et al., 2003; MullerMohr, 1992; Dressler, 1984a). Indeed, preferential communition (Muller-Mohr, 1992) or frictional melting (Thompson and Spray, 1994) has resulted in the Sudbury Breccia matrix being slightly more mac than its local clast population. Footwall Breccia One of the main sulphide hosting units of the Sudbury Structure, the Footwall Breccia is a polymict, matrix-supported, contact metamorphosed breccia that occurs between the SIC and its footwall rocks. Thickness varies from meters up to hundreds of meters in embayment structures. The matrix contains shocked mineral and lithic fragments, clasts of pseudotachylitic breccia and has an igneous texture that has been annealed at temperatures exceeding 1000 C (Lakomy, 1990). 24
(a)
(b)
(c)
(d)
Figure 2.9: Photographs of Sudbury Breccia, Footwall Breccia and Sublayer exposures. (a)
Clast rich Sudbury Breccia from near the Manchester Oset Dyke, with meter scale subrounded clasts of quartzite. Sharp contact with country rocks is seen at the bottom of the picture. (b) Huronian arkose hosted clast poor Sudbury Breccia, again showing sharp contact with coutry rocks. (c) Footwall Breccia in the Levack area (North Range), with angular clasts of local Superior Province felsic gneisses, norite enclave and igneous textured matrix. The scale on the card is in centimeters. (d) The Sublayer norite - Footwall Breccia interface exposed on the Highway 144 Bypass section near Gertrude open pit.
25
2.2.3
Sulphide ore deposits
The Ni-Cu-PGE sulphide ore mineralisation occurs in ve distinct environments: (1) the Sublayer, (2) Footwall Breccias immediately beneath the Sublayer, (3) within veins in the footwall, (4) the Oset Dykes and (5) zones of breccia that host the quartz diorite (Lightfoot et al., 2001; Keays and Lightfoot, 2004). There are a diverse range of mineralisation styles throughout these dierent environments (see Naldrett, 1984a and following chapters). However, three dierent types of orebody can be dened. Contact orebodies, including ores hosted by the Sublayer and Footwall Breccias, occur at the base of the Main Mass of the SIC. The sulphides generally change from massive, semi-massive, blebby and disseminated with height above the footwall contact, over scales of meters to hundreds of meters. Typical sulphide mineral assemblages are pyrrhotite (Fe1-x S), which is the principal host for all other sulphide minerals, pentlandite ((Fe,Ni)9 S8 ) and chalcopyrite (CuFeS2 ). The largest contact deposit is located in the Creighton embayment. Oset Dyke deposits tend to be associated with discontinuities along the radial osets, including swell zones, Sudbury Breccia and changes in country rock (Figure 2.7; Lightfoot and Farrow, 2002). Massive, semi-massive and blebby sulphides occur in association with inclusion bearing quartz diorite, and have mineralogies similar to the contact ore deposits. Footwall deposits, such as the McCreedy, Coleman and Levack mines, are characterised by chalcopyrite rich assemblages hosted by a complex network of veins within brecciated footwall rocks (Morrison, 1984). Genetic models for footwall mineralisation include the mobilisation of metals in the presence of volatiles (Farrow and Watkinson, 1992, 1996; Molnar et al., 1997, 2001; Hanley et al., 2005; Hanley and Mungall, 2003) and the injection of fractionated sulphide (e.g. Li et al., 1992 and Naldrett, 1984a). Sulphide fractionation has been proposed as the primary control on compositional zonation at many orebodies around the SIC. Sulphide minerals undergo changes in the solid state down to relatively low temperatures compared to silicates and oxides. These changes occur because at high temperatures there are extensive elds of solid solution that shrink upon cooling. In the Ni-Cu-Fe-S system, at high temperatures (1190 C; Fleet, 2006) a pyrrhotite-like phase, termed the monosulphide solid solution (mss) crystallises. As cooling continues the mss can no longer accommodate the Ni and Cu and a series of exolutions takes place (Fleet, 2006), with a chalcopyrite-like phase, the intermediate solid solution (iss), formed at 500-400 C (Fleet, 2006). 26

N Levack #2 S Craig Shaft
Contact orebodies
Footwall orebodies
Footwall Breccia Sudbury Breccia Main Mass Footwall rocks
Sulphide ore
Mine shaft/drift
Figure 2.10: Cross-section through the Levack Mine highlighting the dierence between contact
and footwall ore deposits. Modied after Ames and Farrow (2007).
2.2.4
The Whitewater Group
Onaping Formation Directly overlying the Main Mass, the Onaping Formation is a stratied, 1400 m thick, succession of heterolithic breccias and igneous rocks. The formation is typically subdivided from bottom to top into a Basal Member, a Gray Member and a Black Member (Muir and Peredery, 1984). Each member contains a variety of breccias that are comprised of a combination of variably shock metamorphosed country rock fragments, devitried glasses, uidal material, minor sulphide mineralisation and nely comminuted matrix material (Muir and Peredery, 1984; Dressler et al., 1996; Ames et al., 2002). Discordant igneous textured inclusion-bearing melt bodies also occur, and are typically found between the Basal and Gray Members (Muir and Peredery, 1984). It should be noted that an alternative subdivision for the Onaping Formation exists, and is based upon the morphology and percentage of glass shards (Gibbins et al., 1997; Ames et al., 2002), rather than colour and carbon content (Muir and Peredery, 1984). Accordingly, Gibbins et al. (1997) dene a lower Sandcherry Member (equivalent to the Basal and Gray Members) and an upper Dowling Member (Black Member). 27
The geology of the Sudbury Structure The Basal Member is discontinuous, with a thickness typically <150 m and up to
300 m. In the North and East Ranges, it contains a wide variety of fragments derived from the Proterozoic and Archean country rocks set in a ne grained, heterogeneous, matrix composed of recrystalised country rock particles and igneous textured minerals (Muir and Peredery, 1984; Dressler et al., 1996). In the South Range, the Basal Member consists mainly of clasts of quartz arenite, arkose and Proterozoic granite fragments (Muir and Peredery, 1984). The matrix is typically recrystallised and moderately to strongly foliated (Figure 2.11). The contact between the Basal Member and the Upper Unit of the Main Mass is sharp to gradational over tens of meters. The Gray Member is laterally continuous and ranges from 200-700 m in thickness. It has a sharp contact with the Basal Member, or the Main Mass where the Basal Member is absent, and a gradational, to locally sharp, transition into the overlying Black Member. Breccia units of the Gray Member have signicant lithological variety, forming discontinous lens-shaped bodies which range from highly heterolithic to monolithic and from matrix-supported to fragment-supported (Muir and Peredery, 1984). The breccias consist of angular to rounded shock metamorphosed fragments of country rocks, crystal fragments, recrystallised glasses, uidal textured material and minor sulphides. Breccias of the 800-1200 m thick Black Member have similar eld characteristics, clast types and recrystallised glasses, and are distinguished by the presence of: granular carbon, a basal unit rich in chloritised shards, less altered glass fragments, planar bedding towards the top of the member and dierent feldspar clast mineralogies (Dressler et al., 1991). Melt bodies throughout the Onaping Formation are lens shaped to irregular and are typically <35 m long, although clusters of melt bodies are up to 1 km in length. Chilled margins are common, while crystalline cores are commonly ne grained and consist of various proportions of plagioclase, K-feldspar, clinopyroxene, amphibole, quartz and minor ilmenite, titanite, apatite and zircon. Inclusions of country rock account for between <5 and 80 % of the volume of the melt bodies (Muir and Peredery, 1984). A major circulation system of hydrothermal uid pervasively altered the Onaping Formation, resulting in zones of silicication, albitisation, chloritisation, calcitisation and feldspathisation of glass shards and breccia matrices. These zones are associated with Zn-Cu-Pb massive sulphide deposits and have a U-Pb titanite age of 1848.4 +3.8/1.8 Ma (Ames et al., 1998), which is indistinguishable from the age of the Main Mass (Krogh et al., 1982). Onwatin and Chelmsford Formations The geology of the Onwatin and Chelmsford Formations is reviewed in detail by Rousell (1984a), and much of the following brief summary of these rocks is taken from that 28
(a)
Figure 2.11: Photograph of the Basal Member of the Onaping Formation. The outcrop is at
the nothern end of the 144 Highway Bypass traverse in the South Range.
paper. The 600-1000 m thick Onwatin Formation predominantly consists of pelagic sediments, with massive to laminated claystone, siltstone and minor graywacke. In addition, carbonates, cherts and claystones of the Vermillion Member occur near the base of the formation. The sediments are interpreted to have been deposited in a resricted basin, with abundant carbonaceous material and pyrite suggestive of anoxic bottom water conditions. In contrast, the 850 m thick Chelmsford Formation is comprised of layered greywackes and siltstones that are characteristic of turbidite deposits, with paleocurrents indicating a predominantly south-westerly ow direction. Whereas both the Onaping and Onwatin Formations contain shocked clasts and mineral grains, no shock metamorphic features have been described from the Chelmsford Formation. Furthermore, the source region of the formation was dominated by tonalites, such as those exposed to the north-west of the Sudbury Structure (Rousell, 1972).
2.2.5
Deformation of the Sudbury Structure
Orogenic deformation has aected the rocks of the Sudbury area both preceding and following the impact event. In this section the major structural characteristics of the structure are laid out. More detailed reviews are provided by Rousell (1984b) and Riller (2005). The lower contact of each segment of the Main Mass dips inwards towards the centre of the Sudbury Basin (Figure 2.12), dening the elliptical outcrop pattern. In the North Range, the basal contact has a dip of around 30 , the East Range 70 and the South Range varies from 50 to overturned in the south-east and south-west corners (Rousell, 1984b). The rocks of the Sudbury Structure have been heterogeneously deformed under 29
greenschist and, locally, lower amphibolite facies metamorphic conditions (Thompson et al., 1985; Fleet et al., 1987). The metamorphic grade generally decreases to the north, such that the North and East Ranges, as well as much of the Lower and Middle Units of the South Range, have not been aected by the mesocopic ductile strain that is prominent elsewhere. These fabrics are generally attributed to the Paleoproterozoic Penokean orogeny (e.g. Sims et al., 1989). The most prominent Penokean structure is the South Range Shear Zone (SRSZ: Shanks and Schwerdtner, 1991; Rousell; 1975). This southeast dipping ductile thrust system has fabrics that indicate a top to north-west sense of movement (Shanks and Schwerdtner, 1991) and has resulted in the displacement of the South Range by more than 8 km (Figure 2.12). The SRSZ cuts the South Range of the Main Mass in the south-east and southwest corners and has deformed and altered much of the Upper Unit throughout the South Range. The Main Mass has also been deformed by folding, with the prominent north-east lobe having an origin by Penokean folding (Klimczak et al., 2007; Cowan, 1999). The North Range is cut by north striking faults of the Onaping Fault System (Figure 2.3). While these faults are traceable for many tens of kilometers, the vertical component of movement is typically only 100-200 m (Rousell, 1984b). In contrast south-east dipping faults, that run sub-parallel to the SRSZ, have strike separations on the order of 4 km in the south-west corner of the Main Mass. These faults have produced the pronounced thickness variations in the Main Mass in this area (Figure 2.3). The timing of the Penokean orogeny (1.89-1.80 Ga; Sims et al., 1989) overlaps the age of the impact event (1.85 Ga). There is also geochronological evidence that the SRSZ was active during the Mazatzal event 1.7-1.6 Ga ago (Bailey et al., 2004). The later Grenville orogeny (1.1-0.9 Ga; e.g. Easton, 2000b) also imprinted a regional metamorphism in the area. However, based on paleomagnetic overprints in Huronian rocks, Hyodo et al. (1986) estimated that the temperatures of this metamorphic event decreased to less than 400 C beyond a distance of 2 km from the Grenville Front. There is no evidence for Grenville age deformation of the Sudbury Structure.
2.3
Geochemistry of the Sudbury Igneous Complex
Numerous geochemical studies have sought to elucidate both the origin and processes of dierentiation of the SIC. In this section some of the key geochemical characteristics of the Main Mass and Oset Dykes, and important constraints upon their origin, will be laid out. As previously discussed, models have converged upon an impact melting origin 30
2.3. GEOCHEMISTRY OF THE SUDBURY IGNEOUS COMPLEX
NW
North Range
Chelmsford & Onwatin Fm. Onaping Fm. Onaping Fm. SRSZ
South Range
Lower & Middle Units Upper Unit
SE
Lower & Middle Units Levack Gneiss Upper Unit Complex
Huronian Supergroup
?
5
? ?
10 km
10 km
Figure 2.12: Summarised cross section through the Sudbury Structure, based upon the seismic
reection proling by Milkereit et al. (1992). SRSZ - South Range Shear Zone. Modied after Riller (2005).
for the SIC and particular emphasis will be placed on explaining the evidence for such models.
2.3.1
Major and trace elements
It has long been recognised that the rocks of the SIC are compositionally unusual when compared to other layered igneous bodies such as the Stillwater, Skaergaard and Bushveld complexes. For example, they are anomalously rich in SiO2 , have elevated Rb and K2 O and have fractionated rare earth element (REE) patterns (Chai and Eckstrand, 1994; Collins, 1934). A number of key investigations have presented detailed chemical variations throughout the Main Mass (Collins, 1934; Therriault et al., 2002; Naldrett and Hewins, 1984; Lightfoot et al., 1997c; Lightfoot and Zotov, 2005; Lightfoot et al., 1997a; Cooper, 2000) and the Oet Dykes (Lightfoot and Farrow, 2002; Lightfoot et al., 1997b,a) in order to resolve the petrogenesis of the SIC. The Main Mass Various models have been proposed to explain the highly regular stratigraphy of the Main Mass. These include simple crystal fractionation (Naldrett, 1984a), the intrusion of multiple magmas (Chai and Eckstrand, 1994) and crystallisation from a compositionally zoned magma (Golightly, 1994; Zieg and Marsh, 2005). Constraints upon these models can be drawn from geochemical variations throughout the Main Mass, and selected data are presented in Figure 2.13. 31
The geology of the Sudbury Structure A number of compositional breaks are apparant at the base of the Middle Unit and
the base of the Upper Unit, particularly in SiO2 , MgO, TiO2 and trace elements. An upwards decline in incompatible elements and SiO2 (more pronounced from other traverses) throughout the Upper Unit also occurs, which could be explained by crystallisation from the roof downwards. In the North Range, SiO2 increases and MgO decreases from the base of the Lower Unit upwards, indicating that the rocks become more evolved upsection. In the South Range (Figure 2.13) the opposite trends occur. The compositional breaks in the stratigraphy, together with the often conicting major and trace element trends between North and South Ranges, indicate that the chemostratigraphy cannot easily be reconciled with simple in-situ dierentiation by fractional crystallisation. While the concentrations of incompatible elements change signicantly throughout the stratigraphy (Figure 2.13d and 2.13e, the ratios of incompatible elements (e.g. La/Y - Figure 2.13g, Ce/Yb) are relatively constant (Lightfoot and Zotov, 2005; Lightfoot et al., 1997a). Based on this similarity, models invoking distinct sources for the Upper and Lower Units (e.g. Chai and Eckstrand, 1994) have been dismissed. This leaves open the possibility that the Main Mass was compositionally stratied from base to top (Golightly, 1994; Zieg and Marsh, 2005). The mechanisms of this process are not clear, but may have been driven by viscosity and density variations (Golightly, 1994; Zieg and Marsh, 2005). Irrespective of the details, in a two layer model crystallisation would produce the Lower Unit from the base upwards and the Upper Unit from the top downwards (Zieg and Marsh, 2005). Naldrett et al. (1986) provided evidence for a signicant crustal contribution to the SIC, including the high SiO2 , K2 O and Rb concentrations, together with steep REE proles, and suggested that the complex originated by crustal contamination of a mantle derived mac melt. Using major element mixing models, Grieve et al. (1991) showed that a mantle component was not necessary, and that the SIC was consistent with a melt generated by in-situ crustal melting during an impact event. Further observations of crustal trace element concentrations (Keays and Lightfoot, 2004; Lightfoot et al., 2001; Prevec et al., 2000) and Rb/Sr (Hawkesworth et al., 1999) ratios are consistent with an origin by wholesale crustal melting. Lightfoot et al. (1997a) demonstrate that a 20 % component of mantle derived mac rocks could be accomodated in the SIC, however it is not required to explain the chemical variations throughout the Main Mass (Lightfoot et al., 2001). Indeed no unambiguous evidence for signicant mantle input to the SIC has been reported, from either geochemical, eld or petrological studies.
32
5000
5000
5000
4000
UU
4000
4000
RSP (m)
RSP (m)
TZ 2000 MU LU SL 55 60 65 70 75
RSP (m)
3000
3000
3000
2000
2000
1000
1000
1000
0 0 2
SiO2 (wt %)
MgO (wt%)
10
TiO2 (wt %)
(a)
(b)
(c)
5000
5000
5000
4000
UU
4000
4000
RSP (m)
RSP (m)
TZ 2000 MU LU SL 0 5 10 15 20 25
2000
RSP (m)
0 20 40 60 80 100
3000
3000
3000
2000
1000
1000
1000
Nb (ppm)
La (ppm)
200
Sr (ppm)
400
600
(d)
(e)
(f)
5000
5000
5000
4000
UU
4000
4000
RSP (m)
RSP (m)
TZ 2000 MU LU SL 0 0.5 1 1.5 2 2.5 3
2000
RSP (m)
0 50 100 150 200
3000
3000
3000
2000
1000
1000
1000
La/Y
Cu (ppm)
50
Ni (ppm)
100
150
200
(g)
(h)
(i)
Figure 2.13: Selected major and trace element, and trace element ratio variations throughout
the Main Mass and Sublayer. The data is from a traverse of the South Range (Lightfoot and Zotov, 2005). SL, Sublayer; LU, Lower Unit; MU, Middle Unit; TZ; UU, Upper Unit.
33
The Oset Dykes There are broad compositional dierences between Oset Dykes from the North and South Ranges, which appear not to be linked to the major mac mineral phase content (Lightfoot et al., 1997a). These dierences are particularly apparent in TiO2 , Sr and REE ratios, and could represent assimilation of country rocks (Lightfoot et al., 1997a) or primary dierences in the composition of the SIC at the time of injection (Keays and Lightfoot, 1999). From the geological relationships of the Oset Dyke quartz diorite phases (Section 2.2.1) it is clear that the marginal, inclusion free, quartz diorite (QD) was emplaced at temperatures in excess of the Main Mass Lower Unit liquidus. These phases have many compositional traits similar to the Main Mass, including incompatible element ratios, and have compositions intermediate between those of the Lower Unit (felsic norite) and the Upper Unit (Lightfoot and Farrow, 2002; Lightfoot et al., 1997b,a; Tuchscherer and Spray, 2002). As such they are considered to be representative of the bulk SIC melt, emplaced prior to dierentiation of the Main Mass (Lightfoot and Farrow, 2002; Lightfoot et al., 1997b; Tuchscherer and Spray, 2002; Mungall et al., 2004). Despite the high abundance of inclusions in the later, sulphide bearing, phase of quartz diorite (IQD), this unit has very similar geochemical characteristics to QD (Lightfoot and Farrow, 2002). This indicates that it too was likely emplaced prior to signicant dierentiation of the Main Mass, and that assimilation of inclusions did not signicantly aect the composition of this phase.
2.3.2
Isotopic studies
A crustal source of the SIC has been conrmed in a number of investigations of the isotope geochemistry of Main Mass and Sublayer units. These studies include measurements of: Nd isotopes in Main Mass traverses (Faggart et al., 1985), Sublayer norites (Dickin et al., 1996; Prevec et al., 2000) and the Onaping Formation (Deutsch, 1994); Sr isotopes in Main Mass samples (Dickin et al., 1999; Hawkesworth et al., 1999; Hurst and Wetheril, 1974), Sublayer norites (Rao et al., 1985) and the Onaping Formation (Deutsch, 1994) ; Pb isotopes in Main Mass traverses (Dickin et al., 1999) and Sublayer norites and sulphide ores (Dickin et al., 1996); O isotopes in Main Mass samples (Ding and Schwarcz, 1984); Os isotopes in sulphide ores (Dickin et al., 1992; Morgan et al., 2002; Walker et al., 1991). The specic ndings of a number of these studies will be discussed throughout Chapters 4, 5 and 6. All found that either a dominant crustal source was required to explain the isotope systematics, or that data were consistent with a crustal source for the SIC. As such, the Main Mass is now widely regarded as an impact melt sheet, formed from 34
207Pb/204Pb
15.1 10 8 6
15.2
15.3
15.4
15.5
15.6
15.7
Sublayer & ores
Frequency
4 2 Sudbury Breccia
2 1 0 15.1 15.2 15.3 15.4 15.5

m
15.6
15.7
207Pb/204Pb
Figure 2.14: Comparison of model initial Pb isotope ratios of sulphide ores and associated
Sublayer norites with Sudbury Breccia from either side of the complex. Grey bars are North Range samples, white bars are South Range. From Dickin et al. (1996).
shock melting of the crust. Little, if any, mantle input can be accommodated into the SIC. Only the high Ni, Cu and PGE concentrations (80 ppm Ni, 100 ppm Cu and 1 ppb Pd; Lightfoot and Farrow, 2002) relative to the bulk crust (59 ppm Ni, 27 ppm Cu and 1.5 ppb Pd; Rudnick and Gao, 2003) are now regarded as a geochemical feature of the SIC that cannot readily be explained by crustal melting, although Mungall et al. (2004) show that a lower crustal source for the melt sheet can account for the concentrations of these elements. A signicant development in the understanding of the SIC in the context of an impact origin was made by Dickin et al. (1996). These authors found systematic dierences in the Pb isotope ratios of sulphide ores and associated silicate rocks between the North and South Ranges. Pb isotope ratios were found to cluster close to 1850 Ma reference lines on plots of 206Pb/ 204Pb versus 207Pb/ 204Pb, with small degrees of scatter inferred to represent minor isotopic heterogeneity inherited during the Sudbury event. Furthermore, the model initial isotope ratios of samples from each side of the complex were found to fall close to the Pb isotope composition of country rocks and pseudoachylites from each respective range (Figure 2.14). As such signicant dierences in the source of North and South Range melts were identied, consistent with impact melting of dierent target rocks. Distinct crustal sources have also been recognised for ores through studies of Os isotopes (Dickin et al., 1992; Morgan et al., 2002; Walker et al., 1991). Further investigations of the Pb isotope systematics of Main Mass samples also revealed signicant 35
dierences in the model initial Pb isotope ratios of Lower Unit samples from each side of the Complex (Dickin et al., 1999). These studies have further demonstrated that signicant variations in isotopic composition occur on the scale of the North versus South Range.
36
3 Methodology
In Sudbury, the Pb isotope system has proven to be more sensitive to target rock variations than other isotopic systems such as Nd (Dickin et al., 1999, 1996; Faggart et al., 1985). This is because the Huronian metasedimentary sequence, which underlies the South Range of the SIC, was derived from the Superior Province (McLennan et al., 1979, 2000), which underlies the North Range. Due to the dierences in chemical properties of parent and daughter isotopes, fractionation of U and Th from Pb occurs during sedimentary processes. For example U is redox sensitive, and in oxidised environments is transported as dissolved uranyl complexes because U6+ is highly soluble in aqueous solutions (e.g. Langmuir, 1978). The Huronian supergroup records a change from anoxic subaerial weathering in lower stata, with detrital uraninite present in the Elliot Lake Group, to distinctly oxidising conditions in the Cobalt Group (Prasad and Roscoe, 1996). As a result, dierent Pb isotope evolution occured over the time between sedimentation (<2450 Ma; Bennet et al., 1991; Young et al., 2001) and the time of impact (1850 Ma; Krogh et al., 1982) in the North and South Range target rocks. Other isotopic systems, such as Lu-Hf and Sm-Nd, do not fractionate signicantly in this way (McCulloch and Wasserburg, 1978; Patchett et al., 1984; Vervoort et al., 1999), resulting in similar isotopic ratios in each province (Prevec et al., 2000; Naldrett et al., 1986; McLennan et al., 2000). As such, the principal isotopic system of interest in this investigation has been Pb. While whole rock analyses have been undertaken in previous studies on Sudbury, there is evidence for variable recent disturbance of such samples, and signicant in-growth of radiogenic Pb (Cooper, 2000; Dickin et al., 1999). In order to track Pb isotope variations throughout the melt sheet at the time of formation, it would be preferable to analyse phases that preserve close to initial magmatic Pb isotope ratios. Of the common mineral phases present in SIC lithologies, sulphides and feldspars oer the most appealing targets. Both of these mineral groups have low partition ceocients for U and Th, and can incorporate appreciable quantities of Pb (plagioclase felspars typically ppm to hundreds of ppm; Ni-Cu-Fe sulphides typically ppm to thousands of ppm). The details of mineral separation procedures used are presented in Section 3.1, while the ion exchange chromotography technique used to chemically isolate and purify Pb from these matrices is presented in Section 3.2.4. The total range of expected Pb isotope variations throughout the SIC can be estimated from previous investigations. Dickin et al. (1996) found a 2-4 % dierence in model initial
207Pb/ 204Pb
between Sudbury Breccia samples from each side of the com-
37
Methodology
plex. Given the crustal origin of the melt sheet, and the fact that Sudbury Breccia samples provide an average composition of local country rocks (e.g. Dressler, 1984a), this range can be taken as the maximum possible variation. However, variations in the Main Mass are signicantly smaller, with a transect of the North Range having a range of 4 , and the South Range 9 (Dickin et al., 1999). Ideally therefore an analytical technique is required that provides high precision measurements, while allowing for high sample throughput in order to characterise a large number of samples throughout the melt sheet. Accordingly, in this study Pb isotope ratios were measured by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS), using a sample-standard bracketing technique to correct for instrument induced mass fractionation of Pb isotopes. Discussion on alternative methodologies and the details of the measurement protocols are presented in section 3.2.6, along with details of the correction for instrumental mass bias and data from a variety of international standards with dierent matrices. Details of mass spectrometry techniques used to measure U/Th/Pb ratios in the samples are presented in Section 3.2.8. Chapter 6 presents the results of an investigation into the trace element composition and inclusion populations of zircons from throughout the SIC. Trace element compositions were measured by laser ablation (LA) ICPMS, following major element determination by electron microprobe. Details of the analytical protocols employed in this study are presented in Section 3.3.
3.1
Sample processing
Sulphides, feldspars and zircons were seperated from rock samples using a range of techniques. Collected samples were prepared by splitting and cutting, to remove weathered surfaces and inclusions where neccesary, and then crushed using a steel plated jaw crusher. The crushate was sieved to isolate the <500 m fraction and was then passed over a wiley table to separate mineral phases on the basis of density. Further separation techniques included magnetic methods (hand magnet and isodynamic magnetic separator), and additional density separation using heavy liquids (lithium heteropolytungstates - LST; 2.7-2.9 gcm-3 ). Selected physical properties of mineral phases of interest in this study are shown in Table 3.1. Sulphide ore samples were simply crushed, using ceramic or agate pestle and mortars, with dierent sulphide phases separated via hand magnet (pyrrhotite rich fractions magnetic, chalocpyrite and pyrite rich fractions non magnetic). Zircon, plagioclase feldspar 38
3.2. PB ISOTOPE ANALYSIS

Mineral Fe-Ti Oxides Zircon Pyrrhotite Chalcopyrite Titanite Pyroxenes Apatite Hornblende Biotite Plagioclase Quartz Specic gravity (gcm-3 ) 4.7 - 5.3 4.68 4.58 - 4.65 4.1 - 4.3 3.4 - 3.55 3.2 - 3.5 3.15 - 3.2 3.0 - 3.4 2.8 - 3.2 2.62 - 2.76 2.65 (m3 kg-1 ) 10 - 110000 0-1 10 - 30000 0.55 - 10 paramagnetic 43 - 50 (opx) diamagnetic paramagnetic 52 - 98 diamagnetic -0.5 Amperage hand >4 hand >4 3.5 1.0 >4 1.2 0.8 >4 >4
Table 3.1: Physical properties of common minerals in SIC lithologies. Specic gravity data
from Klein and Hurlburt (1999). is the magnetic susceptibility, dened as the ratio of material magnetisation J (per unit mass) to the weak external magnetic eld H (data from Hunt et al., 1995). Diamagnetic minerals have very low or negative magnetic susceptibility; Paramagnetic minerals have small and positive susceptibility. Amperage is the current at which minerals were separated using the isodynamic magnetic separator at the Univeristy of Bristol, with a sideways slope of 10 . Hand - separated with hand magnet.
and sulphide fractions for analysis were hand picked under a binocular microscope, ensuring that grains with the least altered appearance and no inclusions (except zircons) were taken.
3.2
3.2.1
Pb isotope analysis
Reagents
All lab work was carried out in class 100 (ISO 5) clean hoods in Class 10000 (ISO 7) laboratories using Savillex perouroalkoxy (PFA) labware. All reagents were prepared with puried water (MQ) from a Millipore milliQ system, which has a resistivity of 18 Mcm. HCl and HNO3 acids of various concentrations were prepared from VWR AnalaR grade reagents, that were puried by distillation in a sub-boiling quartz still (HCL only) followed by sub-boiling distillation in PFA elbow stills (2). Initially HCl and HNO3 were double distilled in the PFA elbow stills, but after assessing the Pb blank contributions of these reagents it was decided to triple distill them. Concentrated HF and HBr were sourced from ROMIL, and of SpA (sub-ppb) and UpA (sub-ppt) grade respectively. The Pb blanks of reagents used to prepare all samples were regularly checked, by comparing signal intensities on the Element 2 ICPMS with those from the MQ water. All reagents were stored in cleaned FEP bottles. The cleaning procedure involved uxing in 7 M reagent grade HNO3 for at least 3 days on the hotplate, followed by rins39
Methodology
Step 1 2 3 4 5 6 7 Reagent 6 M HCl (reagent grade) Detergent (Extran MA 03) 7 M HNO3 (reagent grade) 6 M HCl (reagent grade) 7 M HNO3 (reagent grade) 6 M HCl (QD - in vial) 6 M HCl (2 - in vial) Hotplate >2 hours at 130 C overnight at 100 C overnight at 140 C overnight at 130 C overnight at 140 C overnight at 130 C overnight at 140 C
Table 3.2: Cleaning procedure for PFA vials. In between each step vials were thoroughly rinsed
with MQ. QD; quartz distilled.
ing 3 times with MQ, overnight reuxing in 2 M HNO3 and further rinsing. Cleaning procedures for PFA screw-top vials are outlined in Table 3.2. Polypropylene (PP) labware, such as pipette tips and centrifuge tubes, was reuxed in 3 M HCl for a minimum of 3 days before rinsing thoroughly with MQ.
3.2.2
Sample preparation
Prior to dissolution the picked mineral fractions were cleaned to remove surface contaminant and loosely bound Pb. Sulphide samples were washed with MQ after picking in isopropanol, and subsequently cleaned in an ultrasonic cleaner using alternate steps of MQ and 2 % HNO3 . A more aggressive protocol was used for feldspar separates. Grains were rst cleaned in the same way as sulphides and then, following Housh and Bowring (1991), were leached in 4 ml of 6M HCl and 7M HNO3 for 20 minutes each at 125 C. The composition of these leaches is discussed below.
3.2.3
Digestion protocols
Following cleaning, sulphide samples of typically 10-20 mg were dissolved in 7 ml screwtop PFA vials. 1 ml of 7 M HNO3 was added to the beaker and placed on the hotplate at 140 C for 24 hours. After drying down, the sample was converted to chloride by adding 0.5 ml of 6 M HCl and the drying down, then 1 ml of HCl was added and the sample returned to the hotplate overnight. Finally samples were converted to bromide (3 x 0.5 ml 0.4 M HBr) in preparation for Pb column chromatrography. Typical samples sizes for feldspar dissolution were 100-200 mg. Following the leaching steps, feldspar fractions were dissolved in 3 ml of 9 M HF and 1 ml of 7 M HNO3 over a 2 day period in closed 15 ml PFA vials on the hotplate at 150 C. Subsequently, the samples were dried down, then converted to nitrate (3 0.5 ml conc. HNO3 ) and then taken up in 3 ml of 6 M HCl. An aliquot (0.5 ml) for U/Th/Pb ratio determination was taken at this stage. After drying down, the samples were converted to bromide form by 40
Step 1 2 3 4 5 6 7 8 9
Procedure 20 mins 4 ml 7 M HNO3 at 125 C 20 mins 4 ml 6 M HCl at 125 C 20 mins 4 ml 5 % HF + 0.5 ml 7 M HNO3 at 125 C repeat step 3 repeat step 3 20 mins 4 ml 10 % HF + 0.5 ml 7 M HNO3 at 125 C repeat step 6 repeat step 6 48 hours 3 ml 29 M HF + 1 ml 14 M HNO3 at 160 C
Mass leached (g) 0.019 0.004 0.109 0.098 0.116 0.240 0.207 0.192 0.021
Cum. wt % 1.9 2.4 13.2 22.9 34.4 58.2 78.7 97.8 99.8
120! 100! 80! 60! 40! 20! 0! 0! 40! 36! 32! 28! 24! 20! 16! 12! 0! 20! 40! 20! 40! 60! 80! 100! Pb! (ng)!
7! 6! 5! 4! 3! 2! 1! 0! 0! 55! 20! 40! 60!
U! (ng)!
80!
100!
206Pb/204Pb!
50! 45! 40! 35! 30!
208Pb/204Pb!
60!
80!
100!
0!
20!
40!
60!
80!
100!
Figure 3.1: Plagioclase felspar step leaching procedure (upper), and results for sample FOQD1
(lower). Between each leaching step, the leachate was pipetted o and the sample rinsed with 3 ml of MQ (added to the leachate). The total sample mass in this experiment was 1.00914 g. Cum. wt % is the cumulative weight percent of sample dissolved. Lower: plots of the Pb and U abundance (excluding step 9), 206Pb/ 204Pb ratio and 208Pb/ 204Pb ratio of each step versus cumulative wt %.
41
Methodology
repeatedly drying down in 0.4 M HBr in preperation for Pb column chemistry. The dilute HF concentrations were used in the feldspar dissolution to avoid dissolution or leaching of <20 m zircon inclusions, which were observed in the residues of two samples. Furthermore, small quantities of U and Th are common in feldspars, which are commonly situated along grain boundaries and distorted lattice sites (Sinha, 1969), or within inclusions (Zartmann and Wasserburg, 1969). Several studies have shown that it is possible to remove Pb produced by in-situ decay of this U and Th, through acid leaching experiments (Bolhar et al., 2007; Frei and Kamber, 1995; Housh and Bowring, 1991). Step leaching experiments, similar to those of Housh and Bowring (1991), were undertaken in order to examine the distribution of U and Th, as well as the homogeneity of Pb isotope compositions, throughout the feldspars. The step leaching procedure, together with results from plagioclase felspar sample FOQD1, are shown in Figure 3.1. The results show that the initial cleaning leaching steps (steps 1 and 2), remove a signicant amount of Th ( 82 % of total mass), U ( 30 % of total mass) and Pb ( 10 % of total mass) with highly radiogenic Pb isotope compositions. While all of the HF leaches (excluding step 9) fall along an 1850 Ma isochron (the age of the SIC), the HCl and HNO3 leaches do not plot along this isochron. These observations are consistent with this Th, U and Pb being foreign, possibly residing along grain boundaries and fractures. In the residue after all steps a 15 m zircon grain was observed, and this is the likely source of the highly radiogenic Pb isotope compositions seen in the nal 29 M HF step. HF leaching steps 4 to 8 (84.6 % of total sample mass) all have Pb isotope compositions, U/Pb ratios and Th/U ratios within analytical uncertanties, indicating that no Pb was leached from the zircon, that the grains are homogenous and that these leaches likely reect initial magmatic U/Pb ratios. 5 % HF leaching step 3 has higher Pb isotope ratios, and likely includes a component of the radiogenic Pb removed by steps 1 and 2.
3.2.4
Pb ion exchange chromatography
Resin and column setup The ion exchange chromatography procedure used in this investigation is adapted from Strelow (1978), who outlined a method that eciently separates Pb from various chalcophile elements. Columns of 50 l volume were made from shrink-t STFE Teon, and used with the anion exchange resin AG1-X8 (Bio-Rad Laboratories). The resin is a quaternary amine anion exchanger on a polystyrene base, and in this investigation a resin of 200-400 mesh size and wet bead diameter of 45-106 l was used. A fresh batch of resin that had been converted to chloride form and cleaned was used for each sample. 42

Step 1 2 3 4 5 6 7 8 9 12 13 Procedure load resin (50 l) in MQ wash resin - 400 l 6 M HCl wash resin - 400 l MQ wash resin - 200 l 6 M HCl wash resin - 400 l MQ precondition - 200 l 0.4 M HBr load sample in 500 l 0.4 M HBr elute with 250 l of 0.2 M HBr + 0.5 N HNO3 repeat step 8 three times collect Pb - 400 l 0.03 M HBr + 0.5 N HNO3 collect Pb - 150 l 0.03 M HBr + 0.5 N HNO3
Table 3.3: Column preparation and elution scheme for Pb ion exchange chromatography. Procedure after C. Taylor and R. Avanzinelli (2007, pers. comm.).
Cleaning procedures involved repeatedly cycling (6 times) in 6 M HCl for 24 hours, followed by rinsing with MQ. The resin was stored in MQ to avoid potential degredation in concentrated HCl. Columns were stored in 6 M HCl when not in use. Elution scheme Prior to loading on the columns, the sample Pb was complexed to bromide form by repeatedly drying down with HBr, and nally taken up in 0.4 M HBr. Following Strelow (1978) matrix elution in a HBr-HNO3 solution was undertaken, since it is preferable to pure HBr elution when sample matrices have high concentrations of chalcophile elements such as Bi, Cd, Zn, In and Cu. This is because the tailing eects on the elution peaks disappear almost completely when 0.5-2.0 M nitric acid is added to the eluting agent. The drawback of adding HNO3 to the eluting agent is that Pb is less strongly absorbed by the resin, an eect which increases with higher nitric acid concentrations. The elution and column preparation scheme used in this investigation is shown in Table 3.3. Comparison of the composition of elution steps in Figure 3.2 shows that ecient separation of Pb, from complex chalcophile element matrices, is achieved. The sample shown was a mixed pyrrhotite-pentlandite-chalcopyrite sulphide ore, and contains wt % of Ni and Cu and Co. Investigations of Pb isotope fractionation during ion exchange chromatography have revealed an enrichment in lighter isotopes by up to 200 ppm/amu in the rst Pb eluted from the columns, and an equivalent depletion in the nal eluted fraction (Baker et al., 2004). While these authors used a dierent elution scheme to this study, their results highlight the need for a high yield from the columns. Fractionation was not signicant in this study, relative to measurement uncertainties, for a number of reasons: Firstly Baker et al. (2004) show that fractionation is greater for larger resin bed sizes and in this 43
Methodology
1.E+09! 1.E+08! Sample! Elution steps 8-11! Elution steps 12-13!
Intensity (cps)!
1.E+07! 1.E+06! 1.E+05! 1.E+04! 1.E+03! 1.E+02! 1.E+01! 1.E+00!
Co! Ni! Cu! Zn! Se! Ru! Rh! Pd! Cd! Te! Re! Os! Ir! Pt! Au! Hg! Tl! Pb! Bi! Th! U!
Figure 3.2: Comparison of the blank corrected signal intensities measured on solutions of a sulphide sample and elution steps from passing the same sample through columns. 20 mg of sample was dissolved and split equally prior to column chemistry. Intensities were measured on an Element 2 ICPMS.
investigation bed sizes are much smaller than those used by these authors; secondly, tests with the standard NIST SRM 981 show that the column yields, obtained by comparing
208Pb
signal intensities of unprocessed and processed standards, were >98 %.
3.2.5
Procedural blanks
The measured Pb blanks for the full sulphide and feldspar procedure, together with the column blank contribution are shown in Table 3.4. The blanks were measured by comparing total Pb signal intensities with standards of known concentration. The full procedural blanks are always less than 100 pg, with a Pb contribution from the ion exchange chromatography averaging 22 pg. The higher blank levels for the sulphide procedure are attributed in part to the distillation procedures for HCl and HNO3 . Changing to triple distillation of these reagents reduced the Pb concentrations in measured aliquots from 11 to 5 pg/g and 20 to 3 pg/g for 12 M HCl and 14 M HNO3 respectively (concentrations measured by external calibration ICPMS). The dierence in the theoretical Pb blank, calculated from the Pb concentrations of reagents, of the two procedures is <20 pg. Irrespective, these Pb blanks are at least three orders of magnitude less than the typical minimum sample or standard mass of Pb processed through columns (100 ng). Table 3.5 shows the deviation that these blank contributions would have on theoretical samples of 100 ng of Pb of varying isotopic compositions. The deviations are small, especially for the column and feldspar procedure where they are signicantly less than the analytical uncertainty for
206Pb/ 204Pb
measurements (>150 ppm). The larger blank 44
3.2. PB ISOTOPE ANALYSIS contribution to the sulphide procedure could have a signicant aect on samples with high values of
206Pb/ 204Pb
(e.g. 25). However, it should be noted that for most sulphide
samples more than 100 ng of Pb was processed (up to 1000 ng), and hence the deviations shown represent maximum possible deviations from the true sample composition.
3.2.6
Pb isotope mass spectrometry
Double focusing multi-collector ICPMS (MC-ICPMS) has become a widely used tool for high precision isotope ratio measurements since its introduction (Walder and Freedman, 1992). The main advantages that the technique oers over thermal ionisation mass spectrometry (TIMS) are: (1) an increased sample throughput, (2) the ability to ionise almost all elements, irrespective of their ionisation potential and (3) higher ionisation eciencies. Various studies have demonstrated that the external reproducibility of Pb isotope ratio measurements by routine MC-ICPMS techniques (<100 ppm; e.g. Baker et al., 2004) are at least as good as TIMS (100 ppm; e.g. Thirlwall, 2000), and also have the advantage that they are not susceptible to dierential loading blanks or anomalous
207Pb
behaviour dependant on the temperature of ionisation (Doucelance and Manhes,
2001; Thirlwall, 2002). Pb isotopes oer a number of analytical challenges for both methods of mass spectrometry. Unlike other radioactive decay systems (e.g. Sr, Nd, Os), Pb only has one non-radiogenic isotope ( 204Pb), and so there is no invariant ratio with which to correct for instrumental mass bias. The precision and accuracy of Pb isotope measurements depends upon the ability to correct for such fractionation. This is particluarly important for MC-ICPMS, where mass bias can be on the percent level (Heumann et al., 1998). Several dierent methods have been proposed in order to correct for Pb isotope mass bias, these include; double spiking, external element doping and sample standard bracketing. Double spiking involves measuring the relative amounts of four isotopes, two of which are enhanced by the addition of enriched isotopic spikes to the sample. It is thought to be the most accurate method (Baker et al., 2004), but requires the preperation of a spike solution and is time consuming. For example, the sample Pb concentration should be known in advance in order to calculate the correct spike aliquot, and an additional mass spectrometer run is required. External element doping involves the addition of Tl to the sample, and the correction of Pb isotope ratios based on the observed fractionation of the natural Tl isotope ratio (Collerson et al., 2002; Rehkamper and Halliday, 1998; Rehkamper and Mezger, 2000). A critical assumption of this method is that Tl isotopes are fractionated in an identical way to Pb. However, there is some uncertainty that this is the case, with poor reproducibility 45
Total procedural (sulphide) Total procedural (feldspar) Column 2 % HNO3 blanks
n 6 3 7 216
Pb blank (pg) 72 25 22 2.6
2 se 26 20 13 0.3
206 Pb/ 204Pb 17.58 17.92 17.09 10.27
2 se 0.30 0.74 0.87 0.19
207 Pb/ 204Pb 15.27 15.72 14.99 8.70
2 se 0.31 0.58 0.76 0.16
208 Pb/ 204Pb 37.01 38.05 36.39 29.54
2 se 0.69 1.42 1.79 3.10
208 Pb/ 206Pb 2.11 2.12 2.13 2.90
2 se 0.01 0.01 0.02 0.30
Table 3.4: Mean measured blank Pb concentrations and isotopic compositions. Total procedural blanks for the sulphide and feldspar procedures are shown, together with the blank contribution from column chemistry. The average composition of 2 % HNO3 measurement blanks are also shown.
Pb blank (pg) 72 25 22
206 Pb/ 204Pb 17.58 17.92 17.09
Total procedural (sulphide) Total procedural (feldspar) Column
ppm deviation (19) 54 22 14
ppm deviation (25) 213 70 70
Table 3.5: The deviation, in parts per million (ppm), that the blank contribution would have on hypothetical samples of 100 ng Pb of 19 and 25 Methodology
206
Pb/ 204Pb ratios
46
3.2. PB ISOTOPE ANALYSIS of Tl corrected Pb isotope ratios attributed to changes in the relative fractionation behaviour of Tl and Pb induced by instrumental stability and matrix eects (Baker et al., 2004; Barling and Weis, 2008). Indeed, Albarede et al. (2004) demonstrate a dierence in Tl and Pb mass fractionation factors on the order of 5-10 %, which is equivalent to 160 ppm/amu mass bias. In addition, it has been identied that Tl undergoes photochemical oxidation from Tl+ to Tl3+ on exposure to UV light, and as a result behaves dierently during desolvation (Kamenov et al., 2004). Accordingly, the reproducibility of routine Tl corrected Pb isotope ratio measurements is typically 300 ppm (Collerson et al., 2002; Rehkamper and Halliday, 1998; Rehkamper and Mezger, 2000). In preference to external element doping, a sample-standard bracketing approach was adopted in this study. This method involves correcting for isotopic fractionation by bracketing the measurement of samples with analyses of a standard solution of well characterised composition. Fractionation is then corrected by interpolating the mass bias factors of the standards to the sample, following the formula (Albarede et al., 2004):
(Rt )smp = (Rt )std
(Rm )smp 1 (Rm )std1 (Rm ) std2
Where is a constant analogous to time and chosen between 0 and 1, Rt and Rm are the true and measured isotopic ratios respectively and the subscripts smp and std refer to the sample and standard. Values of are generally chosen to be 0.5 when samples and standards alternate regularly. Sample-standard bracketing has been shown to provide accurate Pb isotope data that is comparable in precision to double-spike approaches (Baker et al., 2005; Elburg et al., 2005). The main advantage of this methodology is very high sample throughput compared to double spiking and, in particular, TIMS methods. However, there are two prerequisites for the application of the sample-standard bracketing approach. Firstly, mass fractionation must change smoothly and predictably over the timescale between analysis of the bracketing standards. Secondly, given that the mass bias behaviour of samples and standards is assumed to be identical, very ecient seperation of Pb from the sample is required. This is because the sample matrix can signicantly change fractionation behaviour (e.g. Woodhead, 2002). Instrumentation and instrumental protocol All analyses were performed on a Thermo Scientic Neptune double focusing MC-ICPMS at the Bristol Isotope Group (BIG), University of Bristol. A Cetac Aridus desolvating nebuliser was used in all analytical sessions. The typical instrumental operating parameters are shown in Table 3.6 and the cup conguration in Table 3.7. Isotopes were 47
Methodology
Instrument settings: accelerating voltage extraction voltage faraday cups resolution rf power sample cone skimmer cone cool gas auxillary gas sample gas Cetac Aridus desolating nebuliser sweep gas (Ar) N2 spray chamber desolvator temperature nebuliser ow rate 10 kV -2000 V connected to 1011 resistors low ( 400) 1200 W Ni Ni (x-geometry) 15 l min-1 0.8-0.9 l min-1 1.0 l min-1
Argon gas ow rates:
Sample introduction:
from 4-7 l min-1 depending on Aridus used 4-7 ml min-1 PFA at 105 C 160 C 50 l min-1
Table 3.6: Instrumental operating conditions for the Thermo Scientic Neptune MC-ICPMS
and Cetac Aridus desolvating nebuliser.
measured simultaneously in static mode using a multi-Faraday cup array. Data collection consisted of 50 x 4 s integrations. Sequences consisted of alternate analyses of standard NIST SRM 981 with either other standards, samples or blanks. A three minute wash of 2 % HNO3 proceeded all measurements. All samples and standards were introduced in 2 % HNO3 and blank measurements of this reagent were performed every sixth measurement. The average composition of these blanks is shown in Table 3.4 and typically contributed <60 parts per million of the
208Pb
signal.
The concentration of standards and samples was closely matched at 50 ng/g, which resulted in
208Pb
signals between 15 and 32 V and an average sensitivity of 840 V/ppm
Pb. The standard NIST SRM 982 was measured at the start, middle and end of each sequence and used to monitor the accuracy and precision of the sample standard bracketing approach (discussed below). In addition to the isotopes of Pb, isobaric interference of dards, the
203Tl 204Hg 202Hg
was measured to allow for correction of the
on
204Pb.
Although no Tl was added to samples or stanand

186Os/ 16O
and
205Tl
signals were also monitored. Other potential minor interfer186W 16O
ences are listed in Table 3.7. Of these,
are the most important,
because of the eect that they could have on the Hg interference correction. However these were not found to be signicant for a number of reasons: a) the use of N2 during sample introduction minimised the formation of oxides ( 238U 16O
238U
1 %); b) the
W content of samples and standards was negligible and c) the ion exchange chromato48

L3 202 202 Hg
186
Mass Isotope Interference
L2 203 203 Tl
187
L1 204 204 Pb
C 205 205 Tl
187
H1 206 206 Pb
190
H2 207 207 Pb
191
H3 208 208 Pb
192
W 16O 186 Os 16O 162 Dy 40Ar
Re 16O Hg 187 Os 16O 188Os 16O 163 Dy 40Ar 164Dy 40Ar 164 Er 40Ar
Re 18O 189 Os 16O 165 Ho 40Ar
Os 16O 166 Er 40Ar
Ir 16O 167 Er 40Ar
Os 16O 192 Pt 16O 168 Yb 40Ar 168 Er 40Ar
Table 3.7: Faraday cup conguration for the measurement of Pb isotope ratios. Potential interferences on each measured isotope are shown, although in this investigation a correction was only required for the isobaric interference of Hg on 204Pb. graphic procedure used eciently isolated Pb from Os (Figure 3.2), and furthermore the
186Os
constitutes only 1.59 % of Os.
Following o-line wash correction of the raw measured signals, corrections for the isobaric interference of Hg on dances of
204Hg 204Pb
were performed using the ratio of the natural abun-
and
202Hg 204Hg
(6.87/29.86) and a reverse mass bias correction. The contri-
bution of calculated a wash corrected
to the total 204 ion beam was negligible in most samples, with
202Hg
of zero. The maximum contribution in this study was 220 ppm.
Instrumental mass bias was also corrected o-line by external normalisation of sample data to the bracketing NIST SRM 981 standard. The double spike values of Baker et al. (2004) were used for normalisation.
3.2.7
Standards summary
In order for the sample-standard bracketing method to correct accurately and precisely for mass bias, it is important that instrumental mass bias is stable over the duration of an analytical session, and that standards and samples have identical fractionation behaviour. The latter point is particularly important if samples and standards have very dierent matrices, although ecient separation of Pb during ion exchange chromatography should negate this aect. Mass bias in MC-ICPMS is very large relative to TIMS, with typical ranges of 0.1 to 1 % and on the order of per-mil respectively. Comparing the average raw (wash corrected but not mass bias corrected) ratios of NIST SRM 981 with the reference values of Baker et al. (2004), an average mass bias of 0.54 % per amu is seen for this study (Table 3.8). All bar four of the 30 run sequences were undertaken on Neptune 2 in the Bristol Isotope Group. The four sequences run on the older Neptune 1 have an average mass bias of 0.56 % per amu. The stability of mass bias during individual analytical sessions is represented in Figure 3.3. Average drift of the 981 standard over the course of all sequences was 410 ppm (2 relative standard deviations - RSD), but varied between 44 and 1001 ppm per analytical 49
Methodology
Pb/ 204Pb 17.1252 0.0146 0.170 16.9416 1.08 2 0.54
206
Mean (n = 679) 2 sd 2 sd (%) Reference value % dierence ratio amu units % bias/amu
Pb/ 204Pb 15.7524 0.0204 0.259 15.4998 1.63 3 0.54
207
Pb/ 204Pb 37.5263 0.0656 0.350 36.7249 2.18 4 0.55
208
Pb/ 206Pb 0.9218 0.0004 0.093 0.91489 0.54 1 0.54
207
Pb/ 206Pb 2.1913 0.0020 0.185 2.16775 1.09 2 0.54
208
Table 3.8: Pb isotope mass bias in this investigation. The uncorrected NIST SRM 981 data (n = 679) are compared to reference values from Baker et al. (2004).
17.145 17.140 17.135 17.130
206Pb/204Pb
17.125 17.120 17.115 17.110 17.105 17.100 07/03/2008 27/09/2008 25/04/2008 04/10/2008
206
03/06/2008 03/07/2009
Figure 3.3: Representative examples of the drift in uncorrected

SRM 981 standard throughout analytical sessions.
Pb/ 204Pb ratios of the NIST
session. The absolute dierences between 2 adjacent measurements of NIST SRM 981 ranged from 0.2 to 488 ppm. Previous sample-standard Pb isotope investigations in Bristol have proposed a relationship between instrument sensitivity and the magnitude of drift (K. Crocket, 2009, pers. comms). However, no such correlation has been observed in this study. The mass bias behaviour of the MC-ICPMS is investigated in Figure 3.4, by plotting the raw NIST SRM 981 data in ln-ln space. The dened arrays demonstrate that the mass bias behaviour over the course of this study has been normal and constant. The slopes of the arrays are more closely matched by theoretical power law gradients than those for the exponential law (see caption of Figure 3.4). However, the small dierence in gradients indicates that the power law does not fully describe the observed mass bias. NIST SRM 982 was run throughout each analytical session to monitor accuracy and 50
2.760 2.758
y = 1.5111x -1.5355 R2 = 0.99928
y = 2.0251x -2.1275 R2 = 0.99898
3.628
ln (207Pb/204Pb)
2.756
3.624 3.622 3.620 2.837 2.838 2.839 2.840 2.841 2.842 2.839 2.840 2.841 2.842 2.843
2.754
2.752
ln (206Pb/204Pb)
ln (206Pb/204Pb)
Figure 3.4: Natural logarithm plots of raw NIST SRM 981 Pb isotope ratios. Theoretical power
law gradients are 1.5003 and 2.003 (left and right graphs respectively), and more closely match the data than theoretical exponential law gradients of 1.4967 and 1.9906.
precision of the normalisation to NIST SRM 981. 107 mass bias corrected measurements of this standard were made over the course of 30 months, and the results are shown in Figure 3.5. The Pb isotope ratios are all within uncertainty of the double spike values of Baker et al. (2004), with external reproducibility of 160 ppm on ppm on
207Pb/ 204Pb, 206Pb/ 204Pb, 207Pb/ 206Pb
186 ppm on
208Pb/ 204Pb
and 168 ppm on
RSD). The data are presented in Table 3.9. A range of other standards and standard processing methods were also undertaken in order to investigate possible: (a) dierences in mass bias between pure standards and samples of complex matrices, (b) interference issues relating to samples of complex matrices and (c) fractionation of Pb isotopes during chemical separation of Pb. The results of NIST SRM 981 and 982 standards that have been passed though columns, together with basal standards BHVO-2 and BCR-2 are shown in Table 3.9. The standards are all within uncertainty of reference values. Uncertainties in the BHVO-2 and BCR-2 data are signicantly higher than those for the NIST SRM 981 and 982 standards. Baker et al. (2004) attribute this to heterogeneous distribution of contaminant in these rock powders. This is consistent with the observation that dierent dissolved aliquots of these standards have dierent measured Pb isotope ratios, resulting in an overall large uncertainty. For example six analyses of a single aliquot of the BHVO-2 standard gave an external reproducibility of 190 ppm (2 RSD) for
206Pb/ 204Pb.
In order to fully test the reproducibility of sample measurements, a sulphide sample was arbitrarily selected for multiple analyses over a six month duration. The results are shown in Figure 3.6. Four aliquots of sulphide sample 1206010A were dissolved and 51
ln (208Pb/204Pb)
3.626
137 (all 2
Methodology
(a)
(b)
(c)
Individual measurements of the (a) 206Pb/ 204Pb, (b) 207Pb/ 206Pb, and (c) Pb/ Pb ratios of NIST SRM 612 from this study (closed circles). The mean and 2 standard deviation uncertainty of all measurements is shown (closed squares) and compared to the double-spiked values of Baker et al (2004; open squares).
Figure 3.5:
208 206
52

Standard NIST SRM 981 This study Baker et al. (2004) NIST SRM 982 This studya This studyb Baker et al. (2004) BCR-2 This study Baker et al (2004) Woodhead and Hergt (2000) Collerson et al. (2002) BHVO-2 This study Baker et al (2004) Woodhead and Hergt (2000) Collerson et al. (2002)
206 204
Pb/ Pb
207 204
Pb/ Pb
208 204
Pb/ Pb
16.9418 16.9416 36.7496 36.7479 36.7432 18.754 18.765 18.754 18.757 18.633 18.649 18.645 18.645
0.0021 0.0013 0.0059 0.0069
15.4983 15.5000 17.1647 17.1654
0.0027 0.0013 0.0024 0.0034
36.7220 36.7258 36.7550 36.7575
0.0075 0.0031 0.0068 0.0050
6 119 107 6
0.013 0.011 0.021 0.012 0.018 0.019 0.039 0.039
15.628 15.628 15.623 15.624 15.538 15.540 15.545 15.545
0.008 0.005 0.007 0.009 0.019 0.015 0.017 0.017
38.739 38.752 38.716 38.723 38.234 38.249 38.248 38.248
0.032 0.022 0.042 0.018 0.030 0.022 0.042 0.042
14 8
16 5 4 2
Table 3.9: Summary of standard data obtained in this investigation, compared to double-spike reference values. Data for NIST SRM 982 includes aliquots not processed through Pb columns (This studya ). measured at least 3 times each. The resultant external reproducibility on the 15 analyses was 151, 183 and 238 ppm for
206Pb/ 204Pb, 207Pb/ 204Pb
and
208Pb/ 204Pb
respectively.
The internal precision on individual measurements, calculated by propagating the uncertainty on bracketing standards and the sample measurement (2 standard error; tens of ppm), clearly underestimates the true sample reproducibility. While the data from 1206010A could be used as an estimate of reproducibility of sulphide measurements, it is apparent that there are no matrix or column fractionation eects that inuence precision or accuracy. As such the external reproducibility of the standard NIST SRM 982 (n = 107) was taken to be the best representation of true uncertainty in individual sample measurements.
3.2.8
U/Th/Pb ratios
In order to determine the initial Pb isotope ratios of samples it is necessary to correct for in-growth of radiogenic Pb. Sulphides and plagioclase feldspars generally have low U/Pb ratios; for example chalcopyrites from the Creighton mine in Sudbury have U/Pb ratios of 0.031 and two feldspar aliquots from the South Range Main Mass have ratios of 0.025 and 0.087 (Dickin et al., 1996). However, over the 1.85 Gyr since the impact event, signicant in-growth of Pb will occur through U and Th decay. In order to accurately measure U/Pb and Th/Pb ratios by ICPMS, it is necessary to correct for instrumental drift throughout an analytical session and to calibrate the 53
Methodology
16.453!
206Pb/204Pb!
Dissolution! 1!
Dissolution! 2!
Dissolution! 3!
Dissolution! 4!
16.448!
16.443!
16.438! 15.545!
207Pb/204Pb! 208Pb/204Pb!
15.540!
15.535!
15.530! 37.140! 37.130! 37.120! 37.110! 37.100! 37.090!
Figure 3.6: An example of reproducibility for processed samples. Data are shown for sulphide sample 1206010 A. Four aliquots of handpicked sulphide were dissolved over the course of 18 months (dissolutions 1-4). Of these dissolutions, multiple aliquots were processed through Pb columns. Uncertainties on individual measurements are 2 standard errors. The mean of all measurements is shown (closed square), with 2 standard deviation uncertainties (151, 183 and 238 ppm for 206Pb/ 204Pb, 207Pb/ 204Pb and 208Pb/ 204Pb respectively).
54
3.2. PB ISOTOPE ANALYSIS U, Th and Pb signal response against standards of known concentration. Absolute U, Th and Pb concentrations of many of the analysed samples were not determined, due to considerable uncertainty in taking an aliquot of the dissolved sample after dissolution procedures (Section 3.2.3). In order to correct for drift, samples and standards were spiked with 5 ng of internal standards In and Re. An external calibration procedure was adopted, and 25, 5 and 0.5 ng g-1 calibration standards prepared. The internal and calibration standards were made from certied concentration pure element standards, using a Sartorius analytical balance with a readability of 0.01 mg. The U-Th-Pb ratios of samples were measured on a Thermo Scientic Element 2 ICPMS in low resolution (300-400). A tandem quartz glass spray chamber (Cyclonic + Scott double pass) and PFA 100 l/min nebuliser were used to introduce samples, as they provide excellent signal stability. At the beginning of each sequence the 25, 5 and 0.5 ng g-1 calibration standards, along with a 2 % HNO3 blank, were measured in order to dene the relative response (response relative to internal standard Re) versus concentration. These linear calibration curves were used to determine the concentrations of U, Th and Pb in samples and quality control standards. Two quality control standards and up to ve samples were then analysed. Using values for the gradient and intercept of the calibration curves the relative response was then used to calculate analyte concentrations. Calibration curves, blank subtraction, internal standard corrections and concentration calculations were performed online using the Element 2 software. Employing an external calibration, precision of U/Pb ratios on repeat analyses of feldspar samples (Table 3.10) was <0.5 % (2 RSD). Accuracy was monitored using basalt standards BCR-2, BHVO-2 and in-house calibration standards. The average U/Pb and Th/Pb ratios measured in this study are compared to reference values in Table 3.10. Similarly to the ndings of Kamber and Gladu (2009), the two basalt standards were found to be heterogeneous. Individual aliquots of processed sample powder have reproducibilities similar to those of the feldspar samples.
3.2.9
Calculation of initial Pb isotope ratios
In order to resolve Pb isotope variability in igneous rocks it is necessary to calculate initial isotopic ratios, corrected for in-growth of radiogenic Pb since the time of formation. It would be preferable to use U/Pb and Th/Pb ratios to age correct the measured Pb isotope ratios. For example, the initial as follows:
206Pb 204Pb i 206Pb/ 204Pb
ratio ([ 206Pb/ 204Pb]i ) is calculated (et 1)

meas
206Pb 204Pb meas
55
238U 204Pb
Methodology
n BHVO-2 This study Kamber and Gladu (2009) BCR-2 This study Kamber and Gladu (2009) WOIQD1 FSOIQD1 POQD1 WOQD1 Feldspar Feldspar Feldspar Feldspar 9 0.158 0.176 0.02342 0.02079 0.05101 0.02091 0.009 0.010 0.00018 0.00014 0.00058 0.00008 0.538 0.600 0.00635 0.01616 0.00745 0.01346 0.024 0.025 0.00006 0.00014 0.00004 0.00006 7 0.251 0.272 0.049 0.060 0.714 0.755 0.115 0.120 U/Pb 2 Th/Pb 2
3 3 3 3
Table 3.10: Summary of measured U/Pb and Th/Pb ratios for basalt standards BHVO-2 and
BCR-2. Data are compared with the long term average values of Kamber and Gladu (2009), measured by external normalisation ICPMS. Also shown are examples of repeat analyses of feldspar samples from this study.
Whereby subscript meas refers to measured ratios and t is the time (years) since crystallisation. The
238U/ 204Pb
ratio is often referred to as and the
232Th/ 238U
ratio
as . Uncertainty in initial ratios includes propagated uncertanty in the measured Pb isotope ratio, (or ), decay constants (Jaey et al., 1971) and t. An example of this error propagation, using the example of [ 206Pb/ 204Pb]i , is as follows:
2
206Pb 204Pb
206Pb meas
204Pb
+ (1 et )2 a 2 + t2 a 2 + 2 at 2 2 et
Where A is the propagated uncertainty and a is the uncertainty on individual components. Alteration of the U/Pb and Th/Pb ratios, particularly during recent weathering, limit the use of this approach. Pb isotope ratios are considered more resilient to such processes (e.g. Dickin et al., 1996); as such coupled 206Pb/ 204Pb and 207Pb/ 204Pb isotope ratios can be used to model the initial Pb isotope composition. For the Sudbury data, present day Pb isotope compositions are projected back parallel to 1850 Ma reference lines, to a selected
206Pb/ 204Pb
value of 15.464, which is the corresponding value of a

207Pb/ 204Pb,
two stage Pb isotope evolution model at 1850 Ma (Stacey and Kramers, 1975). This provides a robust measure of relative variation in initial as [ 207Pb/ 204Pb]m . which is reported These model initials are not directly comparable to initial ratios
calculated using measured U/Pb and Th/Pb ratios. A schematic representation of the calculation of [ 207Pb/ 204Pb]m is provided in Figure 3.7. The formula is as follows:
207Pb 204Pb m 207Pb 204Pb meas 206Pb 204Pb meas
0.11311 56
15.4635
3.3. ZIRCON MAJOR AND TRACE ELEMENT ANALYSIS
16.0 15.8
207Pb/204Pb
Measured samples
15.6 15.4 15.2 15.0 14
1850 Ma isochron gradient = 0.11311

207Pb/ 204Pb m
206Pb/204Pb = 15.464
16
18
206Pb/204Pb
20
22
Figure 3.7: Schematic representation of model initial Pb isotope calculation. The measured Pb isotope composition of samples is projected along a 1.85 Ga isochron to a 206Pb/ 204Pb value of 15.464, which is the corresponding value of the Stacey and Kramers (1975) model at 1.85. A Stacey and Kramers (1975) Pb isotope evolution model curve is shown from 0 to 2.4 Ga, with 0.5 Ga tick marks.
Because all samples are projected back along parallel 1.85 Ga isochrons, uncertainty in [ 207Pb/ 204Pb]m is only a function of the uncertainties in measured
206Pb/ 204Pb
and
206Pb/ 204Pb,
such that:
2 2
207Pb 204Pb
206Pb 204Pb
meas
+ a
207Pb 204Pb
meas
3.3
Zircon major and trace element analysis
Chapter 6 presents the ndings of an investigation into the composition and inclusion populations of zircons from throughout the melt sheet. A brief account of the analytical protocols is provided in that paper, but more detailed analytical procedures are provided here. Zircons were separated from rock samples following the density and magnetic procedures discussed in Section 3.1. Grains for analysis were then handpicked under a binocular microscope, ensuring that a representative sample of grain morphologies, colours and inclusion abundances was taken, and subsequently mounted in epoxy resin. Polished grain mounts were photographed under reected light and then carbon coated and imaged by secondary electron and cathodoluminescence techniques to reveal internal morphology and textures. These images were used to select measurement sites for the various in-situ analytical techniques employed. 57
Methodology In order to quantify laser ablation measurements of trace elements, it is necessary to
know the concentration of an element to which all others measured can be normalised (an internal standard). There are two predominant approaches that have been used for zircon: a) the measurement of a minor isotope of Si ( 29Si) and normalisation to the stoichiometric SiO2 composition of zircon (32.8 wt %). b) the use of Hf as an internal standard, by rst measuring the Hf concentration by electron microprobe (EPMA). There are several problematic issues with the Si approach: (1) because Si comprises tens of wt % of zircons, even when measuring the minor isotopes
29Si
and
30Si
(4.68 and 3.08
% of Si respectively), signal intensities may overwhelm secondary electon multiplier (SEM) detectors. This is particularly problematic on the Element 2. (2) The large dierence in signal intensities between internal standard and trace elements of interest would cause erroneous corrections if the detector did not behave in a perfectly linear fashion. (3) The use of a low mass internal standard results in long scan times when using a magnetic sector ICPMS to measure the concentration of high mass elements. (4) There are potentially signicant interferences. For example
12C 16O 1H, 14N 1H 2 29Si
cannot be resolved from
and
58Fe ++
at low resolution. (5) The SiO2 content of zircon is not
invariable, and ranges from 30.9 to 36 % in igneous zircon (Belousova et al., 2002). In this study the measured Hf content was used as the internal standard. Because individual zircon crystals are often strongly zoned in Hf content (see Hoskin and Schaltegger, 2003), a key requirement of this approach is that the position of measurements of the Hf content by EPMA and the laser ablation spot are accurately matched on the sample. As such, major element analyses by EPMA were undertaken for all laser ablation analysis positions, often with multiple probe spots around larger laser spot ares in order to ensure homogeneity, using the CL and SE images to guide the location of analyses.
3.3.1
Electron microprobe protocols
Major elements were analysed with a Cameca SX-100 electron microprobe at the University of Bristol. The instrument is equipped with 5 wavelength dispersive spectrometers (WDS), and the typical spectrometer setup is shown in Table 3.11. Calibration standards were polished and re-carbon coated along with samples for each analytical session, in order to minimize dierential x-ray energy loss and absorbtion (Armstrong, 1993). The following calibration standards were used: Kim 5 zircon (Si and Zr), HfO2 (Hf), Durango apatite (Ca and P). Calibration involved measuring on peak for 60 seconds, with background osets of 800, and background measurements for 30 s. Five calibration points for each element were measured. 58

Spec. 1 LPET P (K, 3.171) Spec. 2 PET Zr (L, 2.04) Y (L, 1.922) Spec. 3 LIF Ca (K, 3.69) Spec. 4 TAP Si (K, 1.74) Al (K, 1.49) Spec. 5 LLIF Hf (K, 7.99)
Crystal Element
Table 3.11: Typical spectrometer setup for EPMA analysis of zircons. The analysed x-ray lines and corresponding wavelengths () are also shown. A
0.10!
1.10!
Stdev (wt%)!
Hf (wt %)!
0! 100! 200! 300!
0.08! 0.06! 0.04! 0.02! 0.00!
1.05! 1.00! 0.95! 0.90! 0.85! 0.80! 0! 3! 6! 9! 12! 15!
Counting time (s)!

(a)
Distance (mm)!
(b)
Figure 3.8: (a) Standard deviation of individual measurements versus counting times. This experiment was done with beam currents of 50 nA, and it was found that better precision was achieved with 100 nA. Note that the y-axis is two standard deviations. (b) Traverse across standard Kim-5. Error bars are 2 standard deviations. Horizontal line represents the long term average (see text).
An accelerating voltage of 17 keV was used in order to avoid interference of the Hf K line by second order Zr K x-rays, which have an excitation energy of 17.997 keV (e.g. Agrawal et al., 1994). Beam currents of 100 nA were used to maximise count rates, and spot sizes were 2 m. Corrections for x-ray absorption, secondary uorescence, electron backscattering and the electron stopping power of the sample were performed online using the PAP model (Pouchou and Pichoir, 1985). Achievable precision of the Hf concentration is limited by counting statistics. Figure 3.8a shows that at counting times longer than 120 s the precision of individual measurements is minimised. Once operating conditions were optimised, internal precision of Hf measurements was typically 1.7 % (2 RSD) at 1 wt % Hf. The shard of Kim-5 zircon standard used for calibration was found to be relatively homogenous in major element composition, and was used to monitor accuracy and precision. Over a two year period 112 analyses of the shard were undertaken, with averages of 15.454 0.234 (2sd), 48.491 0.225 and 1.008 0.038 for the wt % content of Si, Zr and Hf respectively. Few studies have published Hf concentration data for this standard, although our Hf results are consistent with the 1.068 0.201 wt % (2sd) measured by Cavosie et al. (2006). A traverse over the 1.5 mm grain emphasises its homogeneity (Figure 3.8), although lower Hf values occur at the edges of the grain. 59
Methodology
Isotope (%)
49
Interference
Comments
96
Ti (5.4) La (99.9) 140 Ce (88.5) 141 Pr (100) 146 Nd (17.9) 149 Sm (13.8) 153 Eu (52.2) 157 Gd (15.7) 159 Tb (100) 161 Dy (18.9) 165 Ho (100) 166 Er (33.6) 169 Tm (100) 172 Yb (21.9) 175 Lu (97.4) 179 Hf (13.6) 232 Th (100) 238 U (99.3)
139
Zr ++ and
48
Ca interferences on
48
Ti (73.7 %)
130
Ba 16O
isobaric int. on isobaric int. on isobaric int. on isobaric int. on
142
152
Nd and Sm and Gd
158
144
154
Nd (27.2 and 23.8 %) Sm (26.8 and 22.8 %) Gd (21, 25, 22 %)
137 141
Ba 16O 113In 40Ar Pr 16O 139La 18O 143 Nd 16O 141Ba 18O 130 Ba 16O 149 Sm 16O 150 Sm 16O 150Nd 16O 153 Eu 16O 156 Gd 16O 159 Tb 16O 135Ba 40Ar 163 Dy 16O
156
Gd
160
162
Dy and
164
Dy (25.5 and 28.2 %)
isobaric interference on
174
Yb (31.8 %)
minor interference free isotope
Table 3.12: Isotopes selected for measurement and the major associated interferences. % is the
relative abundance of the particular isotope. Low abundance 179Hf selected because of the high concentrations of Hf in zircon. Note that there are also various Ru, Rh, Te, Sb, Sn and Cs oxide interferences on the REE.
Although shown in the spectometer setup (Table 3.11) P, Y and Ca were generally not measured, as the concentrations of these elements in the Kim-5 standard and in Sudbury zircons were typically close to or below detection limits.
3.3.2
Laser Ablation ICPMS protocols
Analyses were undertaken with a New Wave 193 nm excimer laser and a Thermo Scientic Element 2 ICPMS. Measured elements were the 14 rare earth elements (REE; La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu), Ti, U and Th, as well as internal standard Hf. A key consideration when designing laser ablation (LA) ICPMS methods is the minimisation of interferences. Table 3.12 displays the isotopes selected for analysis and potential interferences. The formation of light REE oxides, which create interferences on the heavy REE, is of particular concern. These interferences can be resolved at medium (4000) or high (10000) resolution on the Element 2, however there is a corresponding reduction of ion transmission of 80 % and 95 % respectively. In order to maximise detection limits, low resolution (400) analyses were undertaken, and instrument setup and tuning focused upon the reduction of oxide formation. Typical laser and ICPMS operating conditions are shown in Table 3.13. The use of H-geometry skimmer cones and increased torch z-position (i.e. increased distance from the cones), in combination with careful tuning of the sample Ar and He gas ow rates, 60

Laser settings carrier gas energy density repetition rate spot size tubing resolution rf power sample cone skimmer cone scanning mode acquisition mode analysis duration torch z-pos. cool gas auxillary gas sample gas He (0.7-0.8 l min-1 ) 3-4.2 Jcm-2 4 Hz 20-30 m (zircons) and 20-65 m (glasses) FEP lined; mixing bulb at He-Ar connection low 1350 W Ni Ni (H-geometry) mass accuracy time-resolved analysis 90 s (30 s blank and 60 s ablation) 0-1 mm 17 l min-1 0.8 l min-1 1.0-1.1 l min-1
Instrument:
Ar gas ow rates:
Table 3.13: Typical laser ablation and ICPMS operating conditions for trace element analysis
of zircons.
reduces oxide formation signicantly. Oxide formation was quantied by monitoring of the
238U 16O/ 238U
ratio, and was typically <0.5 %.
Sequences involved the bracketing of four samples by analyses of the NIST SRM 612 glass standard ( 40 g g-1 of most elements), which was used to normalise sample analyses. The NIST SRM 612 values of Pearce et al. (1997) were used for normalisation, which was performed o-line, along with blank subtractions and internal standard normalisation, using the Glitter software (Macquarie Research Ltd., 2001). For the majority of analytical sessions all of the elements shown in Table 3.12 were analysed. However, over the course of 18 months, in some analytical sessions Ti, U and Th were measured without simultaneous determination of the REE.
3.3.3
Standards summary
In order to monitor the accuracy and precision of analyses, a range of standard reference materials were analysed. These included the NIST SRM 614 and 612 glass standards, USGS basalt glass standard BCR-2G and the zircon standards 91500 and Temora-2. The measured concentrations of standards are displayed in Table 3.14. All of the standards are within uncertainty of reference values. However, zircon standard 91500 was found to be heterogeneous, with large dierences between analysed grains, as well as dierent domains of individual grains.
61
BCR-2G (n = 18) Mean 2 sd Ref.1 2 sd 0.22 0.76 0.08 0.34 0.08 0.02 0.06 0.08 0.05 0.04 0.01 35.75 1.02 35.89 0.22 38.17 1.47 38.66 0.26 37.14 1.78 38.01 0.30 35.18 2.36 35.63 0.24 36.90 1.40 37.29 0.26 34.36 1.87 35.41 0.20 36.87 2.56 38.32 0.30 36.12 1.43 37.87 1.47 37.72 0.69 35.88 0.74 36.17 0.04 37.64 1.28 39.00 0.20 40.24 2.67 38.60 0.08 37.99 1.87 36.50 1.16 NIST 612 (n = 5) Mean 2 sd Ref.5 2 sd Ti U 9.05 Th 0.44 9.1 223.8 60.8 174 118.4 25.8 71 0.6 140 53 47.53 1.30 48.11 6.02 37.73 2.56 37.23 1.44 36.97 3.12 37.15 2.46 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm 0.49 Yb Lu 0.48 3.45 0.02 0.19 3.34 0.03 0.50 3.36 0.19 3.18 1.20 0.05 6.07 0.25 6.45 0.95 0.03 7.31 0.50 6.79 2.04 0.08 1.95 6.64 0.28 6.57 29.17 1.31 28.82 6.85 0.31 6.88 56.10 2.37 53.75 25.61 1.33 25.26
NIST 612 (n = 9) Mean 2 sd Ref.1 2 sd
NIST 614 (n = 12) Mean 2 sd Ref.1 2 sd 0.68 0.78 0.73 0.77 0.74 0.73 0.74 0.66 0.74 0.67 0.67 0.68 0.77 0.67 0.08 25.26 0.22 0.18 53.75 0.76 0.13 6.88 0.15 6.57 0.13 1.95 0.17 6.79 0.08 0.13 6.45 0.06 0.16 3.18 0.10 0.18 3.34 0.07 0.50 0.08 0.19 28.82 0.34 0.08 0.02 0.06 0.08 0.05 0.04 0.01 NIST 614 (n = 35) Mean 2 sd Ref.6 2 sd 3.82 0.84 0.70 0.35 3.77 0.21 0.83 0.10 0.74 1.60 0.08 0.10
91500 (n = 18) Mean 2 sd Ref.2 2 sd 0.02 2.86 0.03 1.13 0.63 0.29 2.66 0.95 5.01 8.05
0.20
0.01
0.01
0.78
2.56
0.51
0.04
0.02
0.03
0.51
0.24
0.08
0.63
0.50
0.15
0.22
0.24
0.06
1.85
2.21
0.49
0.66
0.86
0.14
13.91 9.38
11.80 1.65
3.30
4.84
0.68
5.24
6.89
0.69
121.8 65.08 73.90 7.39
11.26 6.86
13.10 2.10
Temora 2 (n = 12) Mean 2 sd Ref.3,4 2 sd
Methodology
Table 3.14: Summary of mean measured trace element concentrations of zircon and glass standards, compared to reference values. References: 1 - Kent et al. (2004), 2 - Wiedenbeck et al. (2004), 3 - Hiess et al. (2008), 4 - Black et al. (2004), 5 - Pearce et al. (1997), 6 - Gao et al. (2002).
62
25.75 16.69 24.60 4.92
63
4 Isotopic heterogeneity in the Sudbury impact melt sheet

4.1 Introduction
Central to resolving how the Sudbury melt sheet has evolved over time is an understanding of the scales at which chemical heterogeneity has been preserved. As previously discussed, it has been shown that Pb isotopic dierences are present between ores and basal silicate rocks of the North and South Range Main Mass (Dickin et al., 1996). However, there is currently little understanding of isotopic or trace element variability within each range. In order to characterise such heterogeneity, a Pb isotope investigation of the South Range Main Mass was undertaken. The details and results of which are presented in in the following paper, which is included in this chapter:
Darling J.R., Hawkesworth C.J., Lightfoot P.C., Storey C.D. and Tremblay E. (2009) Isotopic heterogeneity in the Sudbury impact melt sheet. Science Letters. doi:10.1016/j.epsl.2009.11.023 Earth and Planetary
The results of this paper have some signicant implications for models of Ni-Cu-PGE sulphide ore formation in Sudbury. Additional results are presented after the paper that relate to the potential use of Pb isotopes as an exploration tool in Sudbury.
64
Isotopic heterogeneity in the Sudbury impact melt sheet

Darling J.R.a,1 , Hawkesworth C.J.a,2 , Lightfoot P.C.b , Storey C.D.c , Tremblay E.b
a
Department of Earth Sciences, University of Bristol, Wills Memorial Building, Queens Road, Bristol BS8 1RJ, UK b Vale Inco Exploration, Highway 17 West, Copper Cli, Ontario, P0M 1N0, Canada c School of Earth and Environmental Sciences, University of Portsmouth, Portsmouth PO1 3QL, UK
Abstract A unique terrestrial large impact melt sheet is preserved in the 1850 Ma Sudbury Structure, Ontario. We have undertaken a Pb isotope investigation of the southern limb of the melt sheet, termed the South Range Main Mass. The model initial Pb isotope ratios ( 207Pb/ 204Pbm ) vary stratigraphically through the predominantly quartz monzogabbroic Lower Unit, varying from 15.40 to 15.45 at the base to ca. 15.35 at the top of the sequence. Lateral variations of similar range occur in basal Lower Unit samples over scales of less than 5 km. The range of these variations is similar to those of locally exposed upper crustal target rocks, and it is evident that the melt sheet has eciently preserved inherited variability. During the violent phases of crater formation superheated impact melts are expected to be well-mixed mechanically, therefore significant post impact melting of target rocks, fallback material and entrained clasts is required to explain such heterogeneity. The Sudbury Structure hosts world class Ni-Cu-PGE sulphide ore deposits. Systematic variation in Pb/ 204Pbm occurs throughout sulphide ores within the Creighton Embayment, from massive (15.4215.45) to interstitial (ca. 15.40-15.41) and disseminated (ca. 15.39) sulphide. Linking the Pb isotope composition of these ores to the immediately overlying Lower Unit stratigraphy, a protracted sulphide segregation history is apparent. Massive sulphides segregated early, prior to or during initial silicate crystallisation, although the total time involved in sulphide accumulation spanned much of the crystallization of the Lower Unit. It is also shown that lateral variations in Ni depletion throughout the Main Mass correlate with Pb isotopes. Those segments with the strongest chalcophile element depletion signatures, reecting the accumulation of signicant basal sulphides, have high initial Pb isotope values, consistent with early sulphide segregation. The characterisation of Pb isotopic heterogeneity has therefore provided insights into the evolution and scales of mixing of the melt sheet, with the identied chemical variability between melt cells having a signicant inuence on ore forming processes.
207
Key words: Sudbury, impact melt, Pb isotopes, sulphide 1. INTRODUCTION Impact melts have typically been considered to be homogeneous. This view originated in large part from theoretical considerations on the violent movement and mixing of superheated, low viscosity shock melt during crater evolution (Phinney and Simonds, 1977; Simonds and Kieer, 1993), and from studies of melts in some terrestrial impact structures (Floran et al., 1978; See et al., 1998). However, dierentiation and footwall assimilation are known to result in variable major and trace element chemistry (Spray and Thompson, 2008) and melts in the Popagai crater, Siberia (Kettrup et al., 2003), and from the Sudbury structure, Ontario (Dickin et al., 1999, 1996) preserve isotopic heterogeneities associated with variable
j.darling@bristol.ac.uk address: Oce of the Principal, University of St Andrews, North Street, St Andrews, Fife, KY16 9AJ, Scotland
2 Present 1 Correspondence:
target lithologies. Despite these advances, the scale of heterogeneity preserved in larger melt sheets is poorly understood. The 1850 Ma Sudbury Igneous Complex (SIC) is the largest preserved terrestrial impact melt sheet, with an original melt volume of at least 8000 km3 (Grieve and Cintala, 1992), and it has been intensively studied, partly because of its extensive Ni-Cu-PGE sulphide ore deposits. The SIC therefore provides a well-constrained example in which to investigate the scale of heterogeneity in large impact melt sheets. Here we present Pb isotope and whole rock geochemical variations in the southern exposed limb of the Sudbury impact melt sheet. Constraining the scale of heterogeneity is important for the development of impact melting models for the Sudbury event, and for the subsequent evolution of the melt sheet. Moreover, understanding the controls on sulphide formation and accumulation in these areas is key both to models of sulphide ore forma-
EPSL doi:10.1016/j.epsl.2009.11.023
February 12, 2010
8130'
46 45'
8100'
R R T H
Lake Wanapitei
46 30'
S
Sudbury Copper Cliff Offset

t on Fr
2 ure Fig
Footwall Southern Province Superior Province Fault
re G
ille nv
10k m
The Sudbury Igneous Complex
Main Mass
Upper Unit Middle Unit Lower Unit Quartz diorite
Whitewater Group
Figure 1: Simplied geological map of the Sudbury Igneous Complex (SIC), showing the distribution of the Main Mass and Oset Dykes (after Ames et al., 2005), no Sublayer is shown. The location of the study area is outlined. Footwall rocks to the North Range of the complex are Archean Superior Province orthogneisses, and Huronian sedimentary rocks and basalts of the Southern Province to the South Range. Signicant north - south shortening has occurred along shear zones, which cut the centre of current exposure of the complex, resulting in the elliptical outcrop pattern.
tion in Sudbury, and to our understanding of general controls on magmatic sulphide deposits. 1.1. The Sudbury Igneous Complex (SIC) The SIC straddles the contact of Archean orthogneisses of the Superior Province and Proterozoic Huronian supracrustal rocks of the Southern Province (Figure 1), and formed as a result of impact melting of crustal lithologies at 1850 Ma (Dietz, 1964; Krogh et al., 1982). The associated impact basin, known as the Sudbury Basin, had an original diameter of ca. 250 km (Spray et al., 2004), making it one of the largest and oldest known terrestrial impact structures. In addition to containing one of the principal reserves of NiCu-Platinum Group Element (PGE) sulphides on Earth, Sudbury is of great importance in the study of impact processes due to the preservation of multiple features of the impact structure. The highly dierentiated melt sheet (the Main Mass), together with radial and concentric dykes, termed Oset Dykes, comprise the SIC. Overlying the SIC is a sequence of crater lling breccias and clastic sediments of the Whitewater Group. Additionally, within the footwall rocks extensive pseudotachylitic breccia belts occur, known as Sudbury Breccias. Quartz diorites of the Oset Dykes are thought to have been injected into fractures created by readjustment of the crater oor prior to dierentiation of the melt sheet (Lightfoot and Farrow, 2002; Tuchscherer and Spray, 2002), and may be representative in composition of the bulk melt 66
(Lightfoot et al., 1997c). The Main Mass is divisible into the Lower and Upper Unit, separated by the Middle Unit, with the approximate proportions 30:60:10 respectively. The Lower Unit, often termed the Sudbury norite, typically consists of quartz monzogabbro to quartz gabbro, whilst the Upper Unit is granitic. Although highly variable, the Main Mass has an average thickness of ca. 2.5 km (Keays and Lightfoot, 2004). The discontinuous Contact Sublayer occurs at the melt sheet-footwall contact and consists of inclusions and sulphide-rich norite to monzogabbro, locally underlain by footwall breccias. Detailed accounts of the local geology of the SIC are given in the volume edited by Pye (1984). Investigations of the Sr, Nd, Os and Pb isotopic characteristics of SIC lithologies have revealed a strong crustal signature for all units, consistent with generation by impact melting of the crust (Dickin et al., 1999, 1996, 1992; Faggart et al., 1985; Hurst and Wetheril, 1974; Morgan et al., 2002; Walker et al., 1991). Lightfoot et al. (1997d) suggested that a mantle contribution of 20 % can be accommodated in the SIC, however it is not required to explain the chemical variations throughout the Main Mass (Lightfoot et al., 2001). Indeed no unambiguous evidence for signicant mantle input into the melt sheet has been reported, from either geochemical, eld or petrological studies. The relatively constant incompatible element ratios throughout the entire Main Mass stratigraphy have been taken as evidence for a single parent magma for all SIC lithologies (Lightfoot et al., 1997b).
472000
476000
480000
484000
488000
492000
20 9 10 11 12 14 15 16 17 18 19
21
22
23 5152000
UTM N (m)
5140000
Vermillion River
Abandoned Railway North (ABRN) traverse 144 Bypass traverse
1206010 core (402 orebody)
Copper Cliff Mouth (CCM) traverse
Murray traverse
Upper Unit Middle Unit Lower Unit

476000
Sublayer Quartz diorite

480000 484000
Creighton Embayment
Copper Cliff Offset Dyke
5148000
488000
492000
496000
UTM E (m)
Figure 2: Simplied geological map of the study area, showing sample localities for whole rock geochemistry (small grey circles, n = 729) and Pb isotopes (open circles, n = 82). Southern Province footwall rocks (unshaded) are undierentiated. Main Mass traverses are numbered for reference (see Table 1). The approximate surface projection of borehole 1206010 is shown. Note that this borehole was collared from underground at a depth of ca. 2.3 km. The Creighton Embayment is a type example of trough like structures, known as embayments, which occur at irregular intervals along the basal contact (Morrison, 1984). Universal Transverse Mercator (UTM) grid lines shown (zone 17N; scale in meters).
While trace element ratios show only very subtle variations around the Main Mass, isotopic investigations have revealed signicant dierences between the two exposed limbs of the complex, termed the North and South Ranges. While the North Range is underlain by the ca. 2700 Ma Levack Gneiss Complex (Krogh et al., 1984), the South Range country rocks are predominantly Paleoproterozoic Huronian metasedimentary and mac igneous rocks. Useful tools in assessing the isotopic composition of these country rocks are pseudotachylitic breccias (Sudbury Breccias) found throughout the footwall. Since the majority of clasts within the Sudbury Breccia are derived from their host rock (Rousell et al., 2003), the crystalline matrices of these breccias approximate the isotopic composition of local country rocks. Data from Dickin et al. (1996) indicate that Huronian basalts and mixed basalt-sediment sources have model initial Pb isotope signatures ( 207Pb/ 204Pbm ) of 15.34 to 15.42, whereas the Ramsay Lake and McKim sedimentary sequences have higher 207Pb/ 204Pbm (15.4 to 15.6). In contrast, the equivalent matrices from Archean orthogneiss-hosted breccias have much lower initial ratios of 15.0 to 15.2. Dickin et al. (1996) also found systematic Pb isotope dierences between North and South Range ores, and similarities in the initial Pb isotope ratios of Sublayer samples and Sudbury Breccias from each side of the complex. Pb isotope ratios of ore samples were found to cluster close to 1850 Ma reference lines on plots of 206Pb/ 204Pb versus 206Pb/ 204Pb, with small degrees of scatter inferred to represent minor isotopic heterogeneity inherited during the Sudbury event. An origin for the ores cogenetic with basal silicate rocks was proposed, and a marked contrast in the isotopic signatures of the North and South Ranges identied.
1.2. Ni-Cu-PGE sulphide ores Sulphide mineralisation within the SIC is attributed to early sulphur saturation under superheated conditions. Dense immiscible sulphide liquids accumulated towards the base of the melt sheet by ecient gravitational settling, leaving it depleted in chalcophile elements (Keays and Lightfoot, 2004). Sulphide ores are predominantly found along the basal contact of the melt sheet, in close association with Sublayer norites, within the Oset Dykes and in footwall breccias beneath the Sublayer. Major ore deposits are typically associated with depressions or troughs, known as embayment structures (see Figure 2). It has, however, proven dicult to assess why the spatial distribution of ores along the basal margin is so variable. Three mechanisms have been proposed: 1) convection resulting in the concentration of sulphides in embayment structures. 2) The mineral potential of the basal margin may vary with the thickness and extent of metal depletion of the overlying silicate rocks (Keays and Lightfoot, 2004). 3) The existence of magma cells of diering composition could lead to dierent sulphur saturation histories around the melt sheet. 2. Sampling Sampling focused upon a segment of the Main Mass in the South Range, centred on the Creighton Embayment (Figure 2). This area was selected for a number of reasons. Signicant lithological variability occurs in South Range country rocks, which have dierent isotope ratios from their North Range counterparts, oering greater potential for measurable variations. These footwall lithologies can be grouped into four potential compositional end members; i) Huronian metasediments largely derived from the Neoarchean Superior Province (McLennan et al., 1979), ii) Huro67
Traverse Number 1 2 3 4 5 6 7 8 9 10 11 12 13 15 16 17 18 19 20 21 22 23
MgO Ni Ni/ Cu Zr Cu/ Traverse Name (wt%) (ppm) Ni* (ppm) (ppm) Zr Crean Hill 5.99 35.92 0.44 21.50 43.60 0.49 Crean Hill East 5.96 34.85 0.44 20.00 37.70 0.53 Lockerby Mine 6.19 40.60 0.47 26.20 52.54 0.50 ConWest 6.30 45.47 0.51 27.83 60.11 0.46 Graham West 5.36 40.16 0.63 27.40 52.71 0.52 Vermillion River East 5.66 42.27 0.59 38.57 63.27 0.61 Abandoned Railway North 5.39 34.08 0.53 29.28 57.73 0.51 Emma Lake South 5.26 34.92 0.57 31.79 60.83 0.52 Gertrude Echo 6.13 56.60 0.67 40.32 56.45 0.71 Gertrude West 5.95 35.88 0.45 28.14 63.43 0.44 Gertrude Pit 5.83 33.30 0.44 25.90 65.09 0.40 144 Bypass 6.08 40.37 0.48 29.72 60.44 0.49 Creighton 5.70 39.31 0.54 34.00 64.00 0.53 Creighton North East 5.83 41.74 0.55 41.72 65.59 0.64 North Star 5.98 50.80 0.63 33.98 58.13 0.58 North West Tailing 6.24 46.77 0.53 30.62 57.40 0.53 Tam O'Shanter West 6.01 46.14 0.57 34.82 63.42 0.55 Tam O'Shanter 5.58 37.06 0.53 31.41 58.20 0.54 Whitewater Lake South 5.71 47.53 0.65 31.94 62.21 0.51 Pump Lake West 5.90 47.54 0.61 31.70 52.96 0.60 Copper Cliff Mouth 5.90 43.17 0.55 29.30 44.82 0.65 Murray 6.33 47.66 0.52 31.39 55.33 0.57
Table 1: Mean MgO, Ni, Ni/Ni*, Cu, Zr and Cu/Zr for the studied traverses. Mean values were calculated from the thickness weighted mean of Lower Unit samples, in which sulphides do not control the nickel budget (monitored with S and Ni concentrations).
472000
476000
480000
484000
488000
492000
5152000
UTM N (m)
5140000
Crean Hill Mine
N i/ N i*
0.00 0.41 0.51 0.61 0.71 > 1.00
476000
0.40 0.50 0.60 0.70 1.00

480000
Gertrude Mine
Creighton Embayment

5148000
484000
UTM E (m) C
0 .6 5 0 .6 0
488000
492000
496000
1000
Ni (ppm)
100
10
w-
y rra lt a sa ba
Qtz monzogabbro - qtz gabbro Quartz gabbro (basal Lower Unit) Sublayer norite 2 4 6 8 10 12
0 .5 5 0 .5 0 0 .4 5 Cu/Zr Mean Ni/Ni* Mean 475000 480000 485000 490000 495000
MgO (wt % )
UT M E (m)
Figure 3: Metal depletion signatures in the Main Mass Lower Unit. A) Spatial variation in Ni/Ni* in the Lower Unit. For simplicity the Lower Unit is un-shaded and no Sublayer is shown. B) Ni versus MgO content of Lower Unit and Sublayer samples from this study. The curve shows a power law t to the MgO-Ni array, i.e. Ni*, for within-plate (w-p) basalts (Lightfoot et al., 1997a). C) Calculated mean Ni/Ni* and non-model dependant Cu/Zr, plotted against mean east UTM grid reference for each respective traverse (data in Table 1).
68
nian mac volcanics of the Elliot Lake Group, iii) the ca. 2220 Ma Nipissing mac intrusive suite (Corfu and Andrews, 1986), and iv) other Paleoproterozoic intrusions including the intermediatefelsic Creighton and Murray plutons, which are adjacent to the SIC contact. The study area contains some of the least deformed sections in the South Range, and previous workers have characterised traverses in the same region for whole rock geochemistry, Sr, Nd and Pb isotopes, providing a framework for this investigation (Dickin et al., 1999, 1996; Faggart et al., 1985; Lightfoot and Zotov, 2005). In the context of ore forming processes, the area is interesting because of the contrast between segments of the basal contact that host large ore deposits, such as the Copper Cli Oset and Creighton Embayment, and adjacent sections that contain relatively little economic sulphide ore. Surface sampling for whole rock geochemistry was undertaken by Vale Inco Limited as part of a program designed to establish whether the Main Mass geochemistry records the signature of ore formation. Three sets of additional samples were collected for Pb isotope analysis, with the locations shown in Figure 2: 1) Four traverses normal to the basal contact, one throughout the entire Main Mass stratigraphy, and 3 of the Lower Unit stratigraphy, all of which were previously sampled for whole rock geochemistry. 2) Basal Lower Unit quartz gabbros and quartz monzogabbros were sampled to test lateral variability along the southern margin. Two samples were taken at each east-west location at diering distances from the basal contact, allowing for assessment of the sensitivity of Pb isotopes to height above the contact. 3) Sulphide ores from the Creighton Embayment were sampled from Vale Inco diamond drill hole 1206010. The borehole was drilled from the footwall into the Creighton orebody and provides excellent examples of dierent styles of sulphide mineralisation. 3. Methods 3.1. Sulphide Pb isotopes Sulphides were separated from the dierent sample sets using a number of methods. Main Mass samples were crushed and sieved to <500 m. Sulphides were separated utilising a wiley table, hand magnet (for pyrrhotite-rich fractions) and magnetic separator (for chalcopyriteand pentlandite-rich sulphides). Ore samples were simply crushed using an agate pestle and mortar. Sulphide aliquots for analysis were handpicked under a binocular microscope, ensuring that only the least altered crystals were analysed, then cleaned in an ultrasonic bath with 18 M 69
H2 O and 2 % HNO3 to remove surface contamination prior to dissolution. Approximately 5 to 10 mg of sulphide was dissolved in screw top Teon beakers using 7 M HNO3 then dried down and repeatedly converted into chloride and bromide form. Samples were taken up in 0.4 M HBr for chromatographic ionexchange chemistry, and the solutions were loaded onto 50 l Teon columns lled with cleaned Dowex AG-1X8 (200-400 mesh) anion exchange resin. After eluting with a solution of 0.2 M HBr and 0.5 M HNO3 , Pb was collected with a solution of 0.03 M HBr and 0.5 M HNO3 . This HBrHNO3 chemistry is preferable to pure HBr elution schemes when separation of Pb from high concentrations of other chalcophile elements is required, because it reduces the tailing eects on elution peaks (Strelow, 1978). The total procedural blanks were always less than 100 pg and had no eect on the reported numbers. The isotopic composition of Pb was determined on a Thermo Finnigan Neptune multi-collector MC-ICP-MS system at the Department of Earth Sciences, University of Bristol. Samples were introduced using a Cetac Aridus desolvating unit. A sample-standard bracketing method was utilised, since Pb does not have a pair of invariant isotopes that can be used to correct for instrumental mass bias during analysis. Although mass bias corrections can be performed by thallium doping, it has been argued that this procedure can yield inaccurate results (Baker et al., 2004; Thirlwall, 2002). NIST SRM 981 was used as the bracketing standard and the double-spike values of Baker et al. (2004) were used for normalisation. NIST SRM 982 was used as a consistency standard, which yielded averages, over a 9 month period (n = 83), of 36.7484 50 (137 ppm), 17.1649 31 and 36.7557 88 for 206Pb/ 204Pb, 207Pb/ 204Pb and 208 Pb/ 204Pb respectively (uncertainties are 2 standard deviations). Concentrations of analysed standard and sample solutions were closely matched at 50 ppb. In order to test the reproducibility of the sulphide data repeat analyses were made of sample 1206010A2, a massive sulphide ore from Creighton Mine. Four sample aliquots were processed and measured multiple times, yielding averages of 16.445 0.003, 15.538 0.003 and 37.116 0.009 for 206Pb/ 204Pb, 207Pb/ 204Pb and 208 Pb/ 204Pb respectively (n = 16). 3.2. Trace elements Major element oxides and selected trace elements were determined by XRF on glass discs and powder pellets; minor and trace elements including Ni, Cu, and Co were determined by ICP-OES. Accuracy and precision were monitored relative to both Standard Reference Materials (SRMs) and inhouse reference materials.
Sample UTM E UTM N Main Mass Traverses Abandoned Railway North Traverse RX371976 479779 5144015 RX371974 479768 5144097 RX371972 479729 5144162 RX371895 479531 5144737 RX371900 479456 5145085 RX371966 479339 5145346 RX371962 479247 5145617 RX371958 479095 5145866
206
Lithology
Sulphide Trav no.1 RSP2 (m)
Pb/204Pb
2!
207
Pb/204Pb
2!
208
Pb/204Pb
2!
207
Pb/204Pb18503
2!
Model
SR Norite SR Norite SR Norite SR Norite SR Norite SR Norite SR Norite SR Norite
Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy
7 7 7 7 7 7 7 7
50 112 170 691 1006 1243 1489 1715
20.802 22.006 31.012 23.679 20.975 18.199 18.380 22.648
0.003 0.003 0.005 0.004 0.003 0.003 0.003 0.004
15.990 16.128 17.167 16.304 16.009 15.736 15.704 16.201
0.003 0.003 0.004 0.003 0.003 0.003 0.003 0.003
44.648 44.489 58.275 50.203 46.601 40.823 40.950 50.064
0.013 0.013 0.017 0.014 0.013 0.012 0.012 0.014
15.387 15.388 15.409 15.375 15.385 15.427 15.374 15.388
0.005 0.005 0.006 0.005 0.005 0.004 0.004 0.005
16.1 19.7 46.8 24.7 16.6 8.2 8.8 21.6
Highway 144 Bypass Traverse 144IBNR1 484485 144BNR 484448 JDSIC0701 484424 JDSIC0703 JDSIC0702 484346 144NR1 484285 144MLNR1 484215 JDSIC0708 484163 144QGAB 144Gran1 484239 5144962 Sublayer Norite 5145026 Qtz Norite 5145198 SR Norite SR Norite 5146123 SR Norite 5146398 SR Norite 5146825 Melanorite 5147319 SR Norite Quartz Gabbro 5148937 Granophyre 5149416 5149543 5149589 5149807 5150120 5150649 5150949 5151184 5151540 5151725 5151972 5152251 Qtz Norite Qtz Norite Qtz Norite Qtz Norite SR Norite SR Norite SR Norite SR Norite SR Norite SR Norite SR Norite SR Norite Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Po Pn Cpy Po + Pn Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Copper Cliff Mouth Traverse RX374755 493459 RX374752 493426 RX374751 493446 RX374746 493352 RX374742 493338 RX374732 493274 RX374737 493079 RX374741 493081 RX374808 492947 RX374805 492863 RX374802 492791 RX374814 492831
12 12 12 12 12 12 12 12 12 12 22 22 22 22 22 22 22 22 22 22 22 22
0 100 250 500 874 1070 1384 1615 1848 2942 -335 -217 -174 29 322 815 1096 1314 1647 1820 2051 2311
18.412 20.986 18.512 20.854 20.651 23.050 16.990 23.444 20.486 17.061 15.984 15.839 16.031 37.556 19.418 17.058 20.812 20.138 21.118 21.579 17.471 18.045
0.003 0.003 0.003 0.004 0.003 0.004 0.003 0.004 0.003 0.003 0.003 0.002 0.003 0.006 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003
15.652 16.092 15.791 16.036 16.000 16.244 15.578 16.268 15.938 15.498 15.445 15.417 15.440 17.900 15.843 15.558 15.964 15.903 16.018 16.055 15.579 15.590
0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.004 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003
38.868 44.361 41.266 44.920 42.768 49.432 38.449 51.174 46.486 37.145 36.022 36.030 36.544 72.605 40.376 39.005 45.052 43.786 48.660 47.502 39.296 39.672
0.011 0.013 0.012 0.015 0.012 0.014 0.011 0.015 0.013 0.011
15.319 15.467 15.446 15.426 15.414 15.386 15.405 15.365 15.370 15.317
0.004 0.005 0.004 0.005 0.005 0.005 0.004 0.005 0.005 0.004
8.9 16.6 9.2 16.2 15.6 22.8 4.6 24.0 15.1 4.8
0.010 0.010 0.010 0.021 0.011 0.011 0.013 0.012 0.014 0.013 0.011 0.011
15.387 15.375 15.376 15.402 15.396 15.377 15.359 15.375 15.379 15.363 15.352 15.298
0.004 0.004 0.004 0.007 0.005 0.004 0.005 0.005 0.005 0.005 0.004 0.004
1.6 1.1 1.7 66.5 11.9 4.8 16.1 14.1 17.0 18.4 6.0 7.8
70
Sample Murray Traverse RX361042 RX361045 RX361050 RX361128 RX361125 RX361122 RX361120
206 207 208 207
UTM E Po Cpy Pn Cpy Cpy Cpy Cpy Cpy Cpy 23 23 23 23 23 23 23 32 75 260 1031 1187 1333 1437 18.944 21.680 30.488 18.295 17.296 22.113 22.800 0.003 0.003 0.005 0.003 0.003 0.003 0.004 15.796 16.103 17.086 15.698 15.578 16.109 16.173 0.003 0.003 0.004 0.003 0.003 0.003 0.003 42.387 44.952 60.833 41.986 39.263 47.878 49.905 0.012 0.013 0.011 0.012 0.011 0.014 0.014 15.402 15.400 15.387 15.378 15.371 15.357 15.343
UTM N
Lithology
Sulphide Trav no.1 RSP2 (m)
Pb/204Pb
2!
Pb/204Pb
2!
Pb/204Pb
2!
Pb/204Pb18503
2! 0.005 0.005 0.006 0.004 0.004 0.005 0.005
Model 10.5 18.7 45.2 8.5 5.5 20.0 22.1
494189 494322 494295 494037 493974 493954 493946
5150893 5150951 5151199 5152236 5152446 5152642 5152783
Sublayer Norite Qtz Norite SR Norite SR Norite SR Norite SR Norite SR Norite
71
Basal Norites RX361020 RX361020_b RX374696 RX374629 RX374717 RX374719 RX374608 RX374609 JD07SIC10 JD07SIC10_r JDSIC0711 JDSIC0714 JDSIC0712 RX357179 JDSIC0736 JDSIC0735 JDSIC0734 JDSIC0732 JDSIC0731 JDSIC0728 RX374772 RX374774 RX374791 RX374792 Cpy Po Pn Cpy Cpy Cpy Cpy Cpy Cpy Cpy Po Pn Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy Cpy 1 1 2 3 4 4 5 5 6 6 7 9 10 11 15 16 17 18 18 19 20 20 21 21 290 290 240 208 71 155 87 162 96 96 150 121 99 65 110 85 64 76 187 101 65 130 127 163 18.200 18.194 22.818 18.510 22.160 19.833 20.025 16.856 19.675 19.612 20.586 24.841 17.066 20.308 17.405 20.031 22.771 29.577 22.575 18.223 18.355 20.196 17.809 19.745 0.003 0.003 0.004 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.004 0.003 0.003 0.003 0.003 0.004 0.005 0.004 0.003 0.003 0.003 0.003 0.003 15.721 15.722 16.229 15.745 16.147 15.878 15.883 15.527 15.840 15.833 15.963 16.395 15.610 15.950 15.603 15.876 16.205 16.961 16.175 15.683 15.696 15.908 15.592 15.846 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.004 0.003 0.003 0.003 0.003 0.003 0.004 0.003 0.003 0.003 0.003 0.003 0.003
472419 472419 474065 475718 476108 476086 477919 477927 478276 478276 478456 481740 482564 483670 487370 487398 487802 488609 489517 490424 491392 491371 492216 492227
5142299 5142299 5142192 5142373 5142259 5142353 5142948 5142905 5143228 5143228 5143852 5144722 5144871 5144994 5147688 5147498 5147789 5148253 5148618 5148727 5149821 5149886 5150279 5150231
Qtz Norite Qtz Norite Qtz Norite SR Norite Qtz Norite SR Norite Qtz Norite SR Norite Qtz Norite Qtz Norite SR Norite Qtz Norite Qtz Norite Qtz Norite Qtz Norite Qtz Norite Qtz Norite Qtz Norite SR Norite Qtz Norite Qtz Norite SR Norite Qtz Norite SR Norite
37.048 37.051 45.205 40.571 49.461 44.444 46.789 38.046 43.145 42.980 44.673 50.306 37.760 41.538 38.120 42.743 55.548 63.935 48.281 39.945 42.905 43.714 37.889 43.620
0.011 0.011 0.013 0.012 0.014 0.013 0.013 0.011 0.012 0.012 0.013 0.014 0.011 0.012 0.011 0.012 0.016 0.018 0.014 0.011 0.012 0.012 0.011 0.012
15.412 15.413 15.397 15.400 15.389 15.384 15.367 15.369 15.364 15.364 15.384 15.335 15.429 15.402 15.383 15.359 15.378 15.364 15.371 15.370 15.369 15.372 15.327 15.362
0.004 0.004 0.005 0.004 0.005 0.005 0.005 0.004 0.005 0.005 0.005 0.005 0.004 0.005 0.004 0.005 0.005 0.006 0.005 0.004 0.004 0.005 0.004 0.005
8.2 8.2 22.1 9.2 20.1 13.1 13.7 4.2 12.7 12.5 15.4 28.2 4.8 14.6 5.8 13.7 22.0 42.5 21.4 8.3 8.7 14.2 7.1 12.9
Drill Core 1206010 1206010_A 1206010_A 1206010_B 1206010_B 1206010_B 1206010_C 1206010_C 1206010_D 1206010_D 1206010_D 1206010_E 1206010_F 1206010_G A1 A1_r B B_r1 B_r2 C1 C1_r D1 D1_r D2 E F G A2_1 A2_2 A2_3 A2_4 A2_5 A2_6 A2_7 A2_8 A2_9 A2_10 A2_11 A2_12 A2_13 A2_14 A2_15 31 31 31 31 31 31 31 31 31 31 31 31 31 31 31 Po Cpy Po Cpy Po Cpy Po Cpy Po Pn Po Pn Po Pn Po Pn Cpy Cpy Cpy Cpy Po Cpy Pn Po Cpy Pn Po Cpy Pn Aliquot 1 Aliquot 1 Aliquot 1 Aliquot 1 Aliquot 2 Aliquot 2 Aliquot 2 Aliquot 2 Aliquot 3 Aliquot 3 Aliquot 3 Aliquot 3 Aliquot 4 Aliquot 4 Aliquot 4 Mean 2! Po Cpy Po Cpy Po Pn Po Pn Cpy Po Cpy Po Cpy Po Pn Po Pn Cpy Po Cpy Pn Po Cpy Pn Po Pn Aliquot 1 Aliquot 2 Aliquot 1 Aliquot 2 Aliquot 2 Aliquot 1 Aliquot 2 Aliquot 1 Aliquot 1 Aliquot 2 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A 1206010_A
Core Depth4 (m) 31 31 37 37 37 76 76 82 82 82 108 112 128
206 Pb/204Pb 16.382 16.382 16.035 16.087 16.044 17.409 16.066 15.880 15.926 15.963 15.950 15.819 15.836
2! 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 16.446 16.443 16.445 16.443 16.447 16.446 16.444 16.445 16.444 16.445 16.447 16.446 16.447 16.444 16.442 16.445 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003
207 Pb/204Pb 15.535 15.533 15.482 15.492 15.487 15.627 15.478 15.459 15.468 15.468 15.460 15.443 15.430
2! 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 15.539 15.538 15.537 15.535 15.540 15.538 15.537 15.539 15.537 15.538 15.540 15.538 15.540 15.537 15.536 15.538 0.003 0.003 0.004 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003
208 Pb/204Pb 37.197 37.194 36.258 36.326 36.283 36.435 36.212 35.963 36.007 36.030 35.996 35.927 36.093
2! 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.006 0.006 0.006 0.006 0.006 0.006 37.119 37.116 37.114 37.106 37.121 37.116 37.111 37.120 37.115 37.117 37.122 37.118 37.122 37.115 37.114 37.116 0.009
207 Pb/204Pb18503 15.431 15.430 15.417 15.421 15.422 15.407 15.410 15.412 15.416 15.412 15.405 15.403 15.388
2! Model 0.003 2.8 0.003 2.8 0.003 1.7 0.003 1.9 0.003 1.7 0.003 5.9 0.003 1.8 0.003 1.3 0.003 1.4 0.003 1.5 0.003 1.5 0.003 1.1 0.003 1.1
0.011 0.014 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.011 0.011
15.428 15.427 15.426 15.424 15.429 15.427 15.426 15.428 15.426 15.427 15.429 15.427 15.429 15.426 15.425 15.427 0.003
0.004 0.005 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004
3.0 2.9 3.0 2.9 3.0 3.0 2.9 3.0 2.9 3.0 3.0 3.0 3.0 2.9 2.9
Table 2: Pb isotope results from Main Mass traverses, basal Lower Unit samples and ores from the Creighton Embayment. The Lower Unit consists of quartz gabbro to quartz monzogabbro, with a gradual increase in quartz content (up to ca. 20 %) in the lowermost 200 m of stratigraphy. Abbreviations; Cpy (chalcopyrite), Po (pyrrhotite), Pn (pentlandite). Sample locations provided, UTM zone 17N, NAD27. 1 Traverse locations provided in Figure 2. 2 RSP - relative stratigraphic position. 3 Model initial Pb isotope ratios.
72
4. Results 4.1. Whole rock geochemistry The samples have a wide range of Ni and MgO contents (Table 1). The Ni/MgO ratio, which is an index of sulphide control in mac magmas (Lightfoot et al., 1994), falls systematically upward through the stratigraphy. In the Sublayer and lowermost Lower Unit, the ratio is controlled by the modal abundance of sulphide. Higher in the Lower Unit stratigraphy the Ni/MgO ratio falls to <6, indicative of magmas that have been stripped of Ni (Lightfoot et al., 2001). A measure of this depletion is provided by comparison of Ni contents with those expected for rocks of similar MgO contents (Table 1). Expected Ni concentrations (Ni*) were taken from a power law correlation of Ni and MgO from sulphur undersaturated withinplate basalts (Figure 3b), following Lightfoot et al. (2001). The Lower Unit rocks of the SIC all show Ni depletion signatures (low Ni/Ni*) except in the most basal samples where sulphide accumulation has occurred. New data from this study show that the magnitude of depletion varies laterally along the South Range (Figure 3a). An overview of this lateral variability is provided by the mean Ni/Ni* of samples for each individual traverse (Figure 3c). Strikingly, the higher mean Ni/Ni* values (0.6-0.7), i.e. from the least depleted rocks, overlie relatively barren segments of the basal SIC contact, and lower mean Ni/Ni* traverses (0.4-0.5) overlie the heavily mineralised Creighton embayment region. The Cu/Zr ratio is an additional sensitive, non-model dependant indicator of chalcophile element depletion, because typically Cu and Zr behave incompatibly in the absence of sulphide. Comparison of the Ni/Ni* data with Cu/Zr is shown in Figure 3c, with similar trends apparent. 4.2. Pb isotopes The Pb isotope compositions of all analysed samples are given in Table 2. The samples dene a wide range of present day 206Pb/ 204Pb (15.8 to 30) and 208Pb/ 204Pb (36 to 72). In plots of uranogenic and thorogenic Pb, samples cluster around an 1850 Ma reference line (the age of the complex), and a 206Pb/ 204Pb versus 207Pb/ 204Pb isochron of all Lower Unit samples gives an age of 1859 32 Ma (2sd), providing condence that Pb isotope systematics have not been signicantly aected by processes after the emplacement of the SIC. Subtle variations occur, represented by displacement from the 1850 Ma reference lines. In order to resolve these dierences it is useful to calculate initial lead isotope ratios. It would be preferable to use measured U/Pb and Th/Pb to correct for 73
in-growth of radiogenic Pb, however there is evidence for variable recent disturbance of U and Th in sulphide ores (Dickin et al., 1996). Pb isotope ratios are less susceptible to disturbance, and coupled 206Pb/ 204Pb and 206Pb/ 204Pb can be used to estimate model lead isotope ratios at 1850 Ma. A modied version of the methodology of Dickin et al (1996) is used here. Present day Pb isotope compositions are projected back parallel to 1850 Ma reference lines, to a selected 206Pb/ 204Pb value of 15.464, which is the corresponding value of a two stage Pb isotope evolution model at 1850 Ma (Stacey and Kramers, 1975). Such model ratios at 1850 Ma are dierent from initial Pb isotope ratios age calculated using measured U and Th, but they oer a robust measure of the relative variation in 207Pb/ 204Pb at 1850 Ma, and are reported as 207Pb/ 204Pbm . 4.2.1. Basal Main Mass Signicant variations are seen in the model initial Pb isotope ratios of the basal Main Mass Lower Unit samples along strike (Figure 4a). Whilst the total range of 207Pb/ 204Pbm is small (15.32 to 15.44), the dierences are signicant given that uncertainty in the model ratios is 0.003 to 0.005 at 2 standard deviations. Gradual changes in 207Pb/ 204Pbm occur over scales of ca. 5 km, with two exceptions at ca. 482000 m east and ca. 492000 m east, where sharp decreases are observed. The most radiogenic 207Pb/ 204Pbm ratios occur in three sections of the basal contact, in the Crean Hill - Lockerby mine, Gertrude Creighton and Copper Cli areas. The scale of lateral variation is similar to that shown by mean Ni/Ni*. There is a strong negative correlation between 207Pb/ 204Pbm and Ni/Ni*, with sulphides at the base of more Ni depleted traverses having higher 207Pb/ 204Pbm ratios than those associated with less depleted traverses (Figure 4b). The two samples taken at each east-west location at dierent stratigraphic heights have indistinguishable Pb isotope ratios, indicating that the east-west trend is not sensitive to stratigraphic position within the lowermost 200-300 m of the stratigraphy. In samples where chalcopyrite and pyrrhotite could both be separated the two fractions were found to have indistinguishable 207 Pb/ 204Pbm . 4.2.2. Traverses Model initial Pb isotope variations along the four analysed traverses are shown in Figure 5. In three of the traverses a Pb isotope stratigraphy is clearly dened, with a progressive change from more radiogenic compositions of 15.40 to 15.45 in basal Lower Unit samples to ca. 15.35 in the uppermost Lower Unit. No systematic
UTM E (m)
470000 15.44 15.42 15.40 15.38 Crean Hill 475000 480000 Gertrude 485000 144 Bypass 490000 495000
Copper Cliff
Pb/ 2 04 Pb m
15.36 15.34 15.32 15.44 15.42 15.40 15.38 15.36 15.34 15.32 0.4 0.45 0.5 0.55 0.6 0.65 0.7
B r2 = 0.72
2 07
Mean Ni /Ni*
Figure 4: Pb isotope variation in basal Lower Unit samples. A) Model initial Pb isotope ratios plotted against easting (top). Uncertainties at 2 standard deviations are within the data points. Names of associated traverse locations are shown for reference. Broadly, more radiogenic values occur around large orebodies (e.g. Gertrude, Creighton, Copper Cli and Crean Hill). B) Correlation between Ni/Ni* and model initial Pb isotopes.
variation is discernable in the Abandoned Railway North (ABRN) traverse, although deviations outside of analytical uncertainty do occur. The most radiogenic values measured in this study of 207 Pb/ 204Pbm (ca. 15.47) occur at the base of the 144 Bypass traverse. Model initial Pb isotope variations through the entire South Range stratigraphy are shown for the 144 Bypass traverse. The Pb isotope compositions of trace sulphides separated from the Main Mass are indistinguishable from spatially associated feldspar values (Dickin et al., 1999). 207 Pb/ 204Pbm values in the Middle Unit are slightly lower than those at the top of the Lower Unit. The granophyre samples have even lower 207Pb/ 204Pbm values, similar to those of the North Range. Major element trends (Lightfoot and Zotov, 2005) rule out mixing of Upper Unit granitic and Lower Unit monzogabbroic liquids as a mechanism to create either the general decrease in initial Pb isotope ratios up-section, or the intermediate values in the Middle Unit. 4.2.3. Creighton ores A general decrease in 207Pb/ 204Pbm is seen through the 1206010 drill hole (Figure 6), with four distinct groupings. The highest values, near the footwall contact, are from a massive chalcopyrite rich (cpy) vein, followed by massive pyrrhotite (po) and pentlandite (pn), which are intersected over a 10 m core length. A group with lower values includes Cpy and Po+Pn veins, as well as interstitial sulphide in a norite. Disseminated sulphide from a sample of norite at 130 m has the lowest model initial value. The total range of 74
Pb/ 204Pbm from the 1206010 core (ca. 15.38 to 15.43) is similar to that of Lower Unit samples from the overlying 144 Bypass traverse (15.37 to 15.47). At issue is the cause of these variations in Pb isotopes, and the links between the Pb isotope values in the sulphides and the overlying Main Mass. 5. Discussion 5.1. Heterogeneity in the SIC The new Pb isotope data have resolved small, but signicant, isotopic variations both laterally and vertically throughout the SIC. The Pb isotope stratigraphy dened in the traverses indicates variable proportions of melt from diering target lithologies. Lateral variations therefore oer potential for constraining the scale of preserved heterogeneity. Lateral variability in the initial Pb isotope ratios of basal Lower Unit samples may reect the existence of cells of magma of dierent compositions, or be a result of sampling at dierent heights in the melt sheet because of the marked relief along the basal contact. In the latter case, given the stratigraphic changes in Pb isotopes identied, the height in the stratigraphy would determine the isotope composition of the samples analysed. Several lines of evidence suggest that this is not the case; i) the thickness of the Lower Unit does not appear to be the principal control on the total range of Pb isotope stratigraphy (Figure 5). ii) South Range traverses show systematic trends in major element concentrations throughout the Lower Unit
207
Relative Stratigraphic Position (m)
3000
120 100 80 60 40 20 0 15.38 15.40 207 15.42 15.44 15.46
Relative Stratigraphic Position (m)
Typical uncertainty (2) 2500
2000
1500
1000
Pb/
204
500 G E&F D C B A A 15.35 15.40 207Pb/204Pb m 15.45 -
Pbm
-500 15.30
Sulphide blebs in Sublayer norite Interstitial sulphide in Sublayer norite Massive po + pn Chalcopyrite rich vein in Sublayer Massive po + pn Massive sulphide vein in footwall (po) Massive sulphide vein in footwall (cpy)
Lower Unit traverses

144 Bypass Copper Cliff Mouth (CCM) Murray Abandoned Railway N. (ABRN)
Upper and Middle Units

144 Bypass
Sublayer norite
144 Bypass Copper Cliff Mouth
Figure 6: Model initial Pb isotope variation in the 1206010 drill core, Creighton 402 orebody. Note that the borehole was collared at a depth of ca. 2.3 km and drilled northerly from the footwall into the orebody at the base of the melt sheet. Height is the stratigraphic height in the Sublayer norite sequence above the basal contact.
Figure 5: Model initial Pb isotope variation through Main Mass traverses. Samples in the Copper Cli Mouth traverse that plot at negative stratigraphic height are sulphide ores hosted by Sublayer norites. The 144 Bypass traverse includes Middle and Upper Unit samples. Shaded grey squares are feldspar data from Dickin et al. (1999).
stratigraphy (Lightfoot and Zotov, 2005), yet no correlation is observed between whole rock major element concentrations and 207Pb/ 204Pbm . iii) The initial Pb isotope ratios at each sampling location are not sensitive to distance from the contact within the rst ca. 200 m of stratigraphy (Figure 4). It has been suggested that local, late stage, assimilation strongly inuenced Sublayer compositions (Lightfoot et al., 1997d; Prevec et al., 2000; Rao et al., 1985) and that this was the main control on Pb isotope compositions (Dressler and Sharpton, 1998). However, it remains dicult to link the Pb isotope values in the basal Lower Unit samples with the spatial distribution of locally exposed country rocks. There are also examples in which the Pb isotope ratios of Sublayer rocks are markedly dierent from overlying Lower Unit quartz monzogabbros. For example in the 144 Bypass traverse low 207Pb/ 204Pbm values (15.3) occur in the Sublayer, whereas much more radiogenic values are recorded from the immediately overlying Lower Unit (Fig. 5). The Lower Unit rocks of the SIC are LREE enriched, and measures such as (Ce/Yb)CHUR are a useful tool to discriminate between crustal source end member compositions (Lightfoot et al., 1997b; Naldrett and Hewins, 1984; Prevec et al., 2000). The low (Ce/Yb)CHUR value of the 144 Bypass Sublayer (ca. 6) is consistent with a source strongly inuenced by locally exposed Huronian 75
basalts. Such assimilation cannot be responsible for the radiogenic initial Pb ratios in the adjacent overlying Lower Unit quartz gabbros, which have (Ce/Yb)CHUR ratios of 8.9 to 9.1. As indicated by Prevec et al. (2000), it is evident that the composition of the Sublayer magma is chemically distinct from that of the lower Main Mass, and that localised, late stage, assimilation of country rocks does not appear to be the dominant control on the Pb isotope variations in the overlying Lower Unit. Lateral variations in basal Lower Unit samples therefore oer insight into the scale of heterogeneity preserved in the SIC, which we interpret to reect the existence of cells of diering Pb isotope composition. Trends in the mean Ni/Ni* values of sampled traverses and initial Pb isotope ratios of basal Lower Unit samples are very similar, and broad changes in both datasets occur over intervals of 6-8 km (Figures 3 and 4). Superimposed on this broad trend are signicant variations between adjacent basal Lower Unit samples and traverses. For example, at ca. 482000 m east a sample with low 207 Pb/ 204Pbm appears to be an outlier. However, it is matched by a traverse with high average Ni/Ni*. This implies that lateral heterogeneity is preserved on scales of <2 km, a conclusion supported by the dierences between the Copper Cli and Murray traverses, which are approximately 1.2 to 1.3 km apart. 5.2. Physical constraints on the scale of convection From calculated Raleigh numbers Zieg and Marsh (2005) show that vigorous thermal convection was likely in the SIC at temperatures above the liquidus. Mathematical constraints on the scale of convection in the melt sheet can therefore be simply approximated, assuming that the Lower
ABRN
144 Bypass
CCM
Murray
4000m
Creighton Embayment Copper Cliff Offset
Mean Ni/Ni* 0.42 0.46 0.50 0.54 0.58 0.62 0.66
15.35
15.40
Figure 7: Schematic representation of the preservation of cells of diering isotopic composition and metal depletion in the Lower Unit of the South Range. The shading of cells represents the mean Ni/Ni* values for sampled traverses, as shown in Figure 3. The diameters of cells were taken from lateral variations in the Ni/Ni* and Pb isotope datasets, together with the expected scale of convection. Also shown are model initial Pb isotope proles for the studied traverses (as Figure 5), the scales for each prole are identical. ABRN; Abandoned Railway North traverse: CCM; Copper Cli Mouth traverse. Uncertainties in model initial Pb isotopes are within the thickness of the line. Black areas of the basal contact are known heavily mineralised regions.
15.45
Unit monzogabbroic liquid behaves in a Newtonian manner at such temperatures. Given a system in which melt is convecting between two parallel rigid boundaries, driven by a temperature gradient, the horizontal wavelength of velocity and temperature uctuations about the static state should be about twice the melt thickness. In the study region thickness varies between 1500 and 2200 m. Accordingly, the horizontal wavelength of convection would have been in the region of 3 to 4.5 km, similar to the scale of lateral geochemical variations identied. Therefore, such a convective regime was clearly not ecient at laterally homogenising the melt sheet. The scale of preserved heterogeneity is illustrated schematically in Figure 7. The lack of conspicuous modal layering, thermal constraints and interpretations of chemical proles, have led to models invoking in situ crystallisation of a density stratied Sudbury melt sheet, with crystallisation of the Lower Unit occurring from the base upwards via the inward propagation of solidication fronts (e.g. Zieg and Marsh, 2005). It might therefore be expected that the uppermost Lower Unit samples would tend towards homogeneity. Interestingly, whilst the uppermost samples in each traverse have the least radiogenic values, the 207Pb/ 204Pbm ratios of 15.388, 15.365, 15.352 and 15.343 in the ABRN, 144 Bypass, Copper Cli Mouth (CCM) and Murray traverses respectively, dier signicantly. The implication of this west to east decrease is dicult to constrain, although it may be related to general trends in melt contribution from dierent footwall lithologies. 5.3. The origin of heterogeneity Heterogeneities in the Lower Unit rocks of the South Range reect varying contributions from dierent Southern Province target lithologies. As suggested by Simonds and Kieer (1993), it is dicult to envisage a scenario whereby superheated, low viscosity melt produced during the violent contact/compression and excavation stages of crater formation would retain heterogeneity on such a scale. Collapse of the transient cavity 76
would have taken a few minutes (Melosh and Ivanov, 1999). Mixing in this environment is mechanical and driven by shear stresses that are inevitable in the sub-spherical geometry and radial ow typical of impact craters (Melosh, 1989; Phinney and Simonds, 1977; Simonds and Kieffer, 1993). The chemical dierences between the North and South Ranges of the SIC, which were likely separated by tens of kilometres, may have been preserved throughout these processes, but it is much less likely that the sub 5 km lateral heterogeneities identied in this study would have done so. The melt was initially superheated to 2000 K (Ivanov and Deutsch, 1999) and, depending upon the eciency of convective heat loss, may not have cooled to liquidus temperatures for between several years to ca. 10 kyr (Zieg and Marsh, 2005). It is therefore likely that the heterogeneity preserved in the Lower Unit rocks of the SIC relates to continued melting of footwall rocks, fallback material and entrained clasts after crater formation. 5.4. Impact melting models for the Sudbury event The predominance of Huronian Pb isotope compositions for the entire stratigraphy of the South Range (Figure 8) is surprising in the context of some estimates of the depth of melting in the Sudbury event. During impact, the immense kinetic energy of the impactor is transferred to the target by a shock wave. The majority of melted material originates from an approximately spherical volume below the maximum depth of penetration of the impacting body (Melosh, 1989). According to the scaling relations of Grieve and Cintala (1992), a chondritic impactor for the Sudbury event would have been around 8-14 km in diameter, travelling at 20-25 kms-1 . The maximum depth of penetration of such an impactor is approximately equal to its diameter (Grieve and Cintala, 1992). Given total thickness of the Huronian Supergroup of 8-15 km (Dressler, 1984; Young et al., 2001), most of the melting should therefore have taken place below these cover rocks, in the underlying Archean basement (Deutsch et al., 1995; Grieve et al., 1991; Mungall et al., 2004).
4 3 2 1
South Range Upper and Middle Units
40 30
South Range Lower Unit
Frequency
20 10 South Range Ores
trace sulphides from traverses are identical to associated feldspar analyses, this essentially means that Pb isotopes chart the relative timing of sulphide segregation from the Lower Unit. Whilst this model is complicated by the dierences in Pb isotope stratigraphy from dierent traverses, the general trend of each traverse is to higher values at the base. Linking the varying Pb isotope ratios of dierent mineralisation styles in the Creighton 402 orebody to the overlying stratigraphy, it is clear that these sulphides were not derived from a single, instantaneous event (Figure 6). Massive ores, with high 207Pb/ 204Pbm , formed early, consistent with ndings that the Lower Unit was grossly oversaturated in sulphur at its silicate liquidus temperature of ca. 1200 C (Keays and Lightfoot, 2004; Li and Naldrett, 1993; Naldrett, 1989). The ranges of Pb isotope ratios in the 402 orebody, and Sublayer ore samples from the Copper Cli Mouth traverse, cover much of the dened Lower Unit Pb isotope stratigraphy. The total time involved in the genesis of these sulphides must therefore be similar to that involved in the crystallisation of the Lower Unit, consistent with predictions that the melt remained strongly S-saturated throughout the crystallisation of the Lower Unit (Keays and Lightfoot, 2004). It has also been shown that Pb isotopes vary systematically with Ni depletion in the Main Mass (Fig. 4). Those segments in which accumulated basal sulphide has high Pb isotope values, consistent with early segregation, also have the strongest chalcophile element depletion signatures. In addition, these segments correlate spatially with sections of the basal contact that are known to have the largest accumulations of sulphide. The occurrence of this radiogenic Pb isotope component seems integral to early sulphur saturation and maximum metal depletion of the Lower Unit. Given the currently available dataset of Pb isotopes in footwall rocks, the likely sources of this melt component are Huronian metasedimentary rocks. The results of this investigation suggest a protracted S-saturation history of the Main Mass. However, given the lateral variability in basal Lower Unit sulphides, it is apparent that the early saturation events are not ubiquitous, and that some cells probably did not reach sulphur saturation until nearer the onset of silicate crystallisation. These cells also have the lowest metal depletion signatures (e.g. Ni/Ni* and Cu/Zr).
12 8 4
North Range 2 1 0 15.0
Sudbury Breccia
South Range
15.1
15.2
15.3
15.4
15.5 m
15.6
15.7
207Pb/204Pb
Figure 8: Histograms of the model initial Pb isotope composition of Main Mass units and ores, compared to Sudbury Breccia (pseudotachylite) data from Dickin et al. (1996). Sudbury Breccias approximate a regional average of the country rocks (Dressler, 1984).
Major element mixing models have been shown to be consistent with this conclusion. Estimates of the bulk SIC composition can be produced from 95 % Archean basement and 5 % Huronian sediments (Grieve et al., 1991; Mungall et al., 2004), implying that Huronian supracrustal material was vaporised and expelled from the crater. However, neither the South Range Upper Unit nor Lower Unit have initial Pb isotope compositions compatible with sources dominated by Archean basement rocks (Figure 8). Hence, in contrast to the conclusions of Mungall and Hanley (2004), a signicant upper to mid crustal component must be invoked in order to explain the isotopic compositions of the South Range. 5.5. Controls on sulphide forming processes The identication of both lateral and vertical Pb isotope variability in the South Range suggests that the formation and preservation of melt cells may be important for ore forming processes. Sulphide ores, accumulated at the base of the melt sheet, will preserve the isotopic composition of the Lower Unit melts from which they segregated. Sulphides along the basal margin with high 207Pb/ 204Pbm are linked to Lower Unit monzogabbroic rocks lower in the sequence, and samples with low 207Pb/ 204Pbm to higher levels in the stratigraphy. Given that the Lower Unit crystallised from the base upwards (e.g. Zieg and Marsh, 2005), and that the Pb isotope ratios of 77
6. Conclusions Isotopic heterogeneity is present throughout the Sudbury impact melt sheet. Cells of diering chemical composition were generated on lateral scales of less than a few kilometres, and a Pb
isotope stratigraphy formed during crystallisation of the Lower Unit. The range of isotopic variations throughout the Lower Unit of the Main Mass is similar to those of locally exposed footwall rocks. Although the initial products of impact melting may have been homogenised within minutes of impact by violent mechanical mixing during crater development, the superheated melt had signicant potential for continued post-impact melting of the footwall, fallback breccia and entrained clasts. Chemical heterogeneity was thus formed on a scale similar to the estimated scale of convection cells. The relatively radiogenic isotopic signature of all South Range lithologies analysed indicates that Huronian metasedimentary and mac rocks were a dominant source component for the South Range of the melt sheet. Our results indicate a signicant melt contribution from the upper crust, reecting impact melting at shallower levels than previously suggested, or that large volumes of melt may have been generated post impact. As such there is a need to reconcile the geochemical characteristics of SIC lithologies with impact melting models. Pb isotopes provide a relative sense of timing of sulphide segregation from the Main Mass. Early sulphide saturation, at temperatures likely in excess of the Lower Unit liquidus, formed much of the massive Oset Dyke and Contact Sublayer mineralisation, as highlighted by data from the Creighton 402 orebody in the Creighton embayment. However, given that the range of initial Pb isotopes in ores have a similar range to the full Lower Unit stratigraphy, it is apparent that sulphide segregation occurred over a protracted period. Variable chalcophile element depletion throughout the South Range suggests that cells of the Lower Unit have diering sulphur saturation histories. Correlation with Pb isotopes indicates that melt derived from dierent crustal sources has a fundamental control on such processes. Although convection and gravitationally driven ow of sulphide melts may be responsible for the localisation of ores, the preservation of cells of melt of diering composition appears to have a strong inuence on the location of major ore deposits. No attempt has been made in this investigation to ascertain why apparently having higher melt contribution from Huronian sediments leads to earlier sulphur saturation, and further investigations should do so. Furthermore, it is logical that earlier formed sulphides will have access to the most chalcophile element-rich melts, and therefore may be expected to contain the highest metal concentrations (tenor).
7. acknowledgements We thank Vale Inco for their logistical and nancial support throughout this investigation. The Sudbury Basin Group of Vale Inco Exploration are thanked for their scientic contributions and assistance with eldwork. This project was funded by a Natural Environment Research Council studentship to J. Darling. The manuscript beneted from constructive reviews by John Spray, Richard Walker and an anonymous reviewer, as well as helpful comments from editor Rick Carlson.
References
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Hurst, R. W., Wetheril, G., 1974. Rb-Sr study of the Sudbury Nickel Irruptive. Eos, Transactions, American Geophysical Union 55 (4), 466466. Ivanov, B., Deutsch, A., 1999. Sudbury impact event: Cratering mechanics and thermal history. In: Dressler, B. O., Sharpton, V. L. (Eds.), Large Meteorite Impacts and Planetary Evolution II. Vol. 339. Geological Society of America, Boulder, Colorado, pp. 389398. Keays, R. R., Lightfoot, P. C., 2004. Formation of Ni-CuPlatinum Group Element sulde mineralization in the sudbury impact melt sheet. Mineralogy and Petrology 82 (3-4), 217258. Kettrup, B., Deutsch, A., Masaitis, V., 2003. Homogeneous impact melts produced by a heterogeneous target? Sr-Nd isotopic evidence from the Popigai crater, Russia. Geochimica et Cosmochimica Acta 67 (4), 733750. Krogh, T. E., Davis, D., Corfu, F., 1984. Precise U-Pb zircon and baddeleyite ages for the Sudbury area. The Geology and Ore Deposits of the Sudbury Structure Special Volume 1, 431446. Krogh, T. E., McNutt, R. H., Davis, G., 1982. Two high precision U-Pb ages for the Sudbury Nickel Irruptive. Canadian Journal of Earth Sciences 19, 723728. Li, C., Naldrett, A. J., 1993. Sulde capacity of magma a quantitative model and its application to the formation of sulde ores at sudbury, ontario. Econ. Geol. Bull. Soc. 88 (5), 12531260. Lightfoot, P., Hawkesworth, C., Olshefsky, K., Green, T., Doherty, W., Keays, R., 1997a. Geochemistry of tertiary tholeiites and picrites from Qeqertarssuaq (Disko Island) and Nuussuaq, West Greenland with implications for the mineral potential of comagmatic intrusions. Contributions To Mineralogy and Petrology 128 (2-3), 139163. Lightfoot, P. C., Doherty, W., K.Farrell, Keays, R. R., Moore, M. L., Pekeski, D., 1997b. Geochemistry of the Main Mass, Sublayer, Osets and inclusions from the Sudbury Igneous Complex, Ontario. Ontario Geological Survey, Open File Report 5959. Lightfoot, P. C., Farrow, C. E. G., 2002. Geology, geochemistry, and mineralogy of the Worthington Oset Dike: A genetic model for oset dike mineralization in the Sudbury Igneous Complex. Economic Geology 97 (7), 14191446. Lightfoot, P. C., Keays, R. R., Doherty, W., 2001. Chemical evolution and origin of nickel sulde mineralization in the Sudbury Igneous Complex, Ontario, Canada. Economic Geology 96 (8), 18551875. Lightfoot, P. C., Keays, R. R., Morrison, G. G., Bite, A., Farrell, K. P., 1997c. Geochemical relationships in the Sudbury Igneous Complex: Origin of the Main Mass and Oset Dikes. Economic Geology 92 (3), 289307. Lightfoot, P. C., Keays, R. R., Morrison, G. G., Bite, A., Farrell, K. P., 1997d. Geologic and geochemical relationships between the Contact Sublayer, inclusions, and the Main Mass of the Sudbury Igneous Complex: A case study of the Whistle Mine embayment. Economic Geology 92 (6), 647673. Lightfoot, P. C., Naldrett, A. J., Gorbachev, N. S., Federenko, V. A., Hawkesworth, C. J., Hergt, J., 1994. Source and evolution of the Siberian trap lavas, Norilsk district, Russia: Implications for the evolution of suldes. In: Ontario Geological Survey. Spevial volume 5, pp. 283312. Lightfoot, P. C., Zotov, I. A., 2005. Geology and geochemistry of the Sudbury Igneous Complex, Ontario, Canada: Origin of nickel sulde mineralization associated with an impactgenerated melt sheet. Geology of Ore Deposits 47 (5), 349 381. McLennan, S. M., Fryer, B. J., Young, G. M., 1979. Rare-Earth Elements in Huronian (lower Proterozoic) sedimentaryrocks - composition and evolution of the post-Kenoran upper crust. Geochimica et Cosmochimica Acta 43 (3), 375 388. Melosh, H. J., 1989. Impact cratering: A geological process. Oxford University Press, New York. Melosh, H. J., Ivanov, B. A., 1999. Impact crater collapse. Annual Review of Earth and Planetary Sciences 27 (385-415). Morgan, J. W., Walker, R. J., Horan, M. F., Beary, E. S.,
Naldrett, A. J., 2002. Pt-190-Os-186 and Re-187-Os-187 systematics of the Sudbury Igneous Complex, Ontario. Geochimica et Cosmochimica Acta 66 (2), 273290. Morrison, G., 1984. Morphological features of the Sudbury Structure in relation to an impact origin. In: Pye, E., Naldrett, A., Giblin, P. (Eds.), The geology and ore deposits of the Sudbury Structure. Vol. Special Volume 1. Ontario Geological Survey, pp. 513520. Mungall, J. E., Ames, D. E., Hanley, J. J., 2004. Geochemical evidence from the Sudbury Structure for crustal redistribution by large bolide impacts. Nature 429 (6991), 546548. Mungall, J. E., Hanley, J. J., 2004. Origins of outliers of the Huronian Supergroup within the Sudbury Structure. Journal of Geology 112 (1), 5970. Naldrett, A., 1989. Magmatic sulde deposits. Oxford University Press. Naldrett, A. J., Hewins, R. H., 1984. The Main Mass of the Sudbury Igneous Complex. In: Pye, E., Naldrett, A., Giblin, P. (Eds.), The Geology and Ore Deposits of the Sudbury Structure. Ontario Geological Survey, Ch. 10, pp. 236251. Phinney, W. C., Simonds, C. H., 1977. Dynamical implications of the petrology and distribution of impact melt rocks. In: Roddy, J., Pepin, O., Merrill, B. (Eds.), Impact and Explosion Cratering: Planetary and Terrestrial Implications. Pergamon Press, Flagsta, Arizona. Prevec, S. A., Lightfoot, P. C., Keays, R. R., 2000. Evolution of the Sublayer of the Sudbury Igneous Complex: geochemical, Sm-Nd isotopic and petrologic evidence. Lithos 51 (4), 271292. Pye, E. G. (Ed.), 1984. The geology and ore deposits of the Sudbury Structure. Ontario Geological Survey. Rao, B. V., Naldrett, A. J., Evensen, N. M., 1985. Crustal contamination of the sublayer, Sudbury Igneous Complex, and its relevance to the genesis of Ni-Cu suldes. Canadian Mineralogist 23, 329330. Rousell, D. H., Fedorowich, J. S., Dressler, B. O., 2003. Sudbury Breccia (Canada): a product of the 1850 Ma Sudbury Event and host to footwall Cu-Ni-PGE deposits. EarthScience Reviews 60 (3-4), 147174. See, T. H., Wagsta, J., Yang, V., Horz, F., McKay, G. A., 1998. Compositional variation and mixing of impact melts on microscopic scales. Meteoritics and Planetary Science 33 (4), 937948. Simonds, C. H., Kieer, S. W., 1993. Impact and volcanism - a momentum scaling law for erosion. Journal of Geophysical Research - Solid Earth 98 (B8), 1432114337. Spray, J. G., Butler, H. R., Thompson, L. M., 2004. Tectonic inuences on the morphometry of the Sudbury impact structure: Implications for terrestrial cratering and modeling. Meteoritics and Planetary Science 39 (2), 287301. Spray, J. G., Thompson, L. M., Dec. 2008. Constraints on central uplift structure from the Manicouagan impact crater. Meteoritics and Planetary Science 43 (12), 20492057. Stacey, J. S., Kramers, J. D., 1975. Approximation of terrestrial lead isotope evolution by a 2-stage model. Earth and Planetary Science Letters 26 (2), 207221. Thirlwall, M., 2002. Multicollector ICP-MS analysis of Pb isotopes using a (207)pb-(204)pb double spike demonstrates up to 400 ppm/amu systematic errors in Tl-normalization. Chemical Geology 184 (3-4), 255279. Tuchscherer, M. G., Spray, J. G., 2002. Geology, mineralization, and emplacement of the Foy Oset dike, Sudbury impact structure. Economic Geology 97 (7), 13771397. Walker, R. J., Morgan, J. W., Naldrett, A. J., Li, C., Fassett, J. D., 1991. Re-Os isotope systematics of Ni-Cu sulde ores, Sudbury Igneous Complex, Ontario - Evidence for a major crustal component. Earth and Planetary Science Letters 105 (4), 416429. Young, G. M., Long, D. G. F., Fedo, C. M., Nesbitt, H. W., 2001. Paleoproterozoic Huronian basin: product of a Wilson cycle punctuated by glaciations and a meteorite impact. Sedimentary Geology 141, 233254. Zieg, M. J., Marsh, B. D., 2005. The Sudbury Igneous Complex: Viscous emulsion dierentiation of a superheated impact melt sheet. Bulletin of the Geological Society of America 117 (11-12), 14271450.
79
4.3
Pb isotopes as a tool for sulphide ore exploration?
The recognition that sulphide ores at the base of the Main Mass reect a protracted segregation history (see Darling et al., 2010) leads to three principal hypotheses regarding the formation of sulphide ore deposits: 1. Chemical heterogeneity in the Main Mass was a fundamental control on sulphide segregation and the location of major ore deposits. 2. Early sulphide segregation led to the formation of the principal reserves of massive sulphide at the base of the melt sheet. 3. Sulphides that segregate early will have access to the most Ni, Cu and PGE rich melts, and will thus have the highest concentrations of these elements (tenor). The correlation between the Pb isotope composition of basal sulphides (a proxy for timing of segregation) and the extent of chalcophile element depletion in the Lower Unit of the Main Mass, indicates that the timing of sulphide segregation and the volume of sulphide removed are intrinsically linked. In order to further understand the controls on this relationship, it is necessary to better understand the inputs into the melt sheet (i.e. target rock contributions). For example, in addition to temperature and oxidation state (see Naldrett, 1989) sulphur saturation is controlled by a range of compositional variables, principally: sulphur and Fe content (Haughton et al., 1974) and the concentrations of other metal cations that form sulphide phases (e.g. Ni, Cu, Mn; Evans, 2008). An assessment of the main target rock contributions to the melt sheet is presented in the following chapter. The rest of this section focuses upon the third of these hypotheses. In order to test whether sulphides that segregated early have the highest metal tenors, ore samples of varying mineralisation styles and sulphide contents were taken from the Creighton embayment. The Pb isotope compositions of sulphide separates was determined and the model initial Pb isotope ratios (following Darling et al., 2010) compared to whole rock major and minor element concentrations.
4.3.1
Sampling strategy
The basal contact of the Creighton embayment dips 50 to the north, and contains a series of footwall and contact orebodies that have been mined to a depth of 3 km. The sample set analysed in this investigation was selected from a much larger sampling program of the Creighton ore-system undertaken by Vale Inco. Selected samples have a range of mineralisation styles and sulphide contents similar to those sampled from 80
4.3. PB ISOTOPES AS A TOOL FOR SULPHIDE ORE EXPLORATION?
16.0! 15.9!
207Pb/204Pb! 208Pb/204Pb!
46! 44! 42! 40! 38! 36! 34! 15.0! 16.0! 17.0! 18.0! 19.0! 20.0!
206Pb/204Pb ! 206Pb/204Pb
1 Ga! 0 Ga!
15.8! 15.7! 15.6! 15.5! 15.4! 15.5! 16.5! 17.5! 18.5! 19.5! 20.5!
!
Figure 4.1: Plots of uranogenic and thorogenic Pb isotope ratios of ore samples from throughout
the Creighton embayment. A regression line through all samples on the plot of 206Pb/ 204Pb versus 207 Pb/ 204Pb coincides with a 2-stage model Pb isotope evolution (Stacey and Kramers, 1975) reference isochron of 1.856 Ga. Regression line through all samples on the plot of 206Pb/ 204Pb versus 208Pb/ 204Pb intercepts the Stacey and Kramers (1975) growth curve at 1.9 Ga.
the 1206010 drill core (Darling et al., 2010, Figure 6) which is also from the Creighton embayment, and range in depth from the surface (Gertrude Pit) to 1.5 km (402 orebody). The samples were also selected on the basis that whole rock geochemical data was available from Vale inco.
4.3.2
Pb isotope results
The Pb isotope ratios of sulphide separates from the samples are presented in Table 4.1, along with the whole rock geochemistry data provided by Vale Inco. The samples dene linear arrays on plots of both uranogenic and thorogenic Pb, consistent with their having been no signicant disturbance of the Pb isotope system since formation at 1.85 Ga (Figure 4.1). However, there is considerable scatter around the dened reference isochrons that suggests that Pb in the samples does not have a single source. In order to further evaluate these variations, model initial The total range of
207Pb/ 204Pb m 207Pb/ 204Pb
ratios were calculated.
(15.383 - 15.454) is slightly larger than measured in
the 1206010 drill core (15.388 - 15.431) and comparable to the total range of Lower Unit samples from the overlying 144 Bypass traverse (15.365 - 15.467). Consistent with the conclusions drawn from the 1206010 drill core data, this implies a protracted sulphide segregation history for the formation of the ores in the Creighton embayment.
4.3.3
Comparison of Pb isotopes and whole rock geochemistry
Comparison of the 207Pb/ 204Pbm values of the sample sulphide separates with whole rock geochemical data is presented in Figure 4.2. Given that sulphides will dominate the S and Ni budget of the samples, the concentrations of these elements can be taken as a mea81
Sample RX378909 RX378903 RX378926 RX357177 RX357177 RX378910 RX378921 RX378907 RX378927 RX378913 RX378934 RX378942 RX357179 RX378911 RX378922 RX378918 RX378929 RX357182 1033790-2486 1033790-2430 1033790-2029 1033790-1083 1033790-2042 Up-Dip 402 OB 402 OB Up-Dip 402 OB Up-Dip 402 OB Gertrude pit 402 OB B. Gertrude Pit B. Gertrude Pit Up-Dip 402 OB Gertrude Pit 402 402 Up-Dip 402 OB Up-Dip 402 OB Up-Dip 402 OB 0.47 1.07 0.18 0.28 3.43 4.63 0.17 1.17 0.36 0.07 1.45 1.63 1.87 2.04 2.46 2.74 2.87 3.05 4.69 4.09 B. Gertrude Pit 402 OB 2.11 0.32 1.18 1.23 0.05 0.04 0.05 0.05 0.06 0.06 0.08 0.08 0.11 0.09 0.14 0.18 402 OB Up-Dip 402 OB Gertrude Pit Gertrude Pit 402 OB 0.48 0.21 0.25 0.25 1.52 0.52 0.69 0.88 0.88 1.08 0.02 0.03 0.04 0.04 0.04 3.11 5.75 7.49 7.49 7.95 0.166 0.121 0.117 0.117 0.135 12.25 0.096 7.19 0.171 10.45 10.60 12.00 12.55 20.10 22.00 23.50 19.75 30.50 34.50 0.138 0.154 0.156 0.163 0.122 0.125 0.122 0.154 0.154 0.119 402 BLBY MASU BLBY PTCH INSU INSU BLBY MASU INMS BLBY MASU MASU INMS INMS INMS INMS INMS BLBY RGDI RGDI MASU
location
Sulphide
Cuwr Niwr Cowr Swr Ni/S wt.% wt.% wt.% wt.% 0.15 0.27 0.01 1.61 0.169
Co/S 0.008 0.005 0.005 0.005 0.005 0.004 0.004 0.005 0.005 0.005 0.005 0.005 0.004 0.004 0.005 0.004 0.004 0.005
206 Pb/ 2 204 Pb 20.395 0.003
207 Pb/ 2 204 Pb 15.943 0.003
208 Pb/ 2 204 Pb 45.152 0.013
207 Pb/ 2 204 Pbm 15.385 0.005
Nipo wt.%
Copo (ppm)
18.742 16.157 16.694 16.602 16.513
0.003 0.003 0.003 0.003 0.003 17.533 0.003 18.705 0.003 17.218 16.628 17.566 16.982 20.308 16.644 16.789 17.328 16.758 16.818 18.678 16.944 17.229 16.544 16.671 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003
15.779 15.478 15.529 15.514 15.501
0.003 0.003 0.003 0.003 0.003 15.643 0.003 15.781 0.003 15.651 15.559 15.688 15.604 15.950 15.547 15.601 15.617 15.549 15.538 15.813 15.572 15.603 15.522 15.537 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003
42.223 36.706 37.401 37.365 36.649
0.012 0.010 0.011 0.011 0.010
15.408 15.400 15.390 15.386 15.383
0.004 0.004 0.004 0.004 0.004
2.00 1.90 2.01 1.65 2.25
289 447 615 492 414
38.344 0.011 41.506 0.012
15.409 0.004 15.415 0.004
2.39 1.58
651 220
37.988 37.176 38.473 37.546 41.538 37.353 37.626 38.577 37.564 37.230 40.747 38.339 38.313 37.423 37.393
0.011 0.011 0.011 0.011 0.012 0.011 0.011 0.011 0.011 0.011 0.012 0.011 0.011 0.011 0.011
15.452 15.427 15.451 15.432 15.402 15.414 15.451 15.406 15.403 15.385 15.450 15.404 15.404 15.400 15.401
0.004 0.004 0.004 0.004 0.005 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004
3.10 2.02 2.55 2.73
616 381 481 556
2.36 2.39 2.11 2.37 1.74 3.12 1.88 2.17 1.39 2.10
420 687 643 575 920 676 434 509 304 535
Table 4.1: Summary of Pb isotope and major and minor element data for sulphide ore bearing samples from the Creighton embayment. Whole rock Ni, Cu, Co and S values are shown (Cuwr etc.), together with Pb isotope and Ni and Co (Nipo etc.) measurements on pyrrhotite rich sulphide separates. Location relates to the orebody within the Creighton embayment mine system; from surface to depth these are: Gertrude Pit, Below (B.) Gertrude Pit, Up-dip 402 Orebody (OB) and the 402 Orebody. Sulphide mineralisation styles: BLBY - blebby, MASU - massive sulphide, PTCH - patchy, INMS inclusion bearing massive sulphide, RGDI - ragged (inclusions in sulphide matrix).
82
25! 25! 25! 25! 20! 20! 20! 20! 15! 15! 15! 15! 10! 10! 10! 10! 5! 5! 5!5! 0! 0! 0!0! 15.36! 15.38! 15.40! 15.42! 15.44! 15.46! 15.36! 15.38! 15.40! 15.42! 15.44! 15.46! 15.36! 15.38! 207 20715.42! 15.44! 15.46! 15.36! 15.38! 15.40! 15.42!Pb 15.40! 204 204 15.44! 15.46! Pb/
3.5! 3.5! 3.5! 3! 3.5! 3!
S (wt %)! S (wt %)! S (wt %)! S (wt %)!
Ni Ni (wt %)! (wt %)! Ni (wt %)! Ni (wt %)!
3! 2.5!3!2.5! 2.5! 2! 2.5! 2! 2! 1.5!2!1.5! 1.5! 1! 1.5! 1! 1! 0.5!1!0.5! 0.5! 0! 0.5! 0! 0!0! 15.36! 15.38! 15.40! 15.42! 15.44! 15.46! 15.36! 15.38! 15.40! 15.42! 15.44! 15.46! 15.36! 15.38! 207 20715.42! 15.44! 15.46! 15.36! 15.38! 15.40! 15.42!Pb 15.40! 204 204 15.44! 15.46! Pb/
Pb/ Pbm! m! 207Pb/204Pb 207Pb/204Pb (a) m!m!
Pb/ Pbm! m! 207Pb/204Pb 207Pb/204Pb m! m!

(b)
0.20! 0.20! 0.20! 0.18! 0.20! 0.18!
0.009! 0.009! 0.009! 0.009! 0.008! 0.008!
Ni/S! Ni/S! Ni/S! Ni/S!
0.14! 0.12! 0.14! 0.12! 0.12! 0.10! 0.12! 0.10! 0.10! 0.08! 0.10! 0.08! 0.08! 0.08! 0.06! 0.06!
0.06! 0.06! 15.36! 15.38! 15.40! 15.42! 15.44! 15.46! 0.002! 0.002! 15.36! 15.38! 15.40! 15.42! 15.44! 15.46! 15.36! 15.38! 15.40! 15.42! 15.44! 15.46! 15.36! 15.38! 15.40! 15.42! 15.44! 15.46! 207Pb/20415.44! 15.46! 15.36! 15.38! 15.40!204 15.36! 15.38! 15.40! 15.42! 15.44! 15.46! 15.42! Pb 15.36! 15.38! 15.40!Pb/20415.44! 15.46! 15.36! 15.38! 15.40! 15.42! 15.44! 15.46! 207 207 207 15.42! Pb 204

(c)
Co/S! Co/S! Co/S! Co/S!
0.18! 0.18! 0.16! 0.16! 0.16! 0.14! 0.16! 0.14!
0.008! 0.008! 0.007! 0.007! 0.007! 0.007! 0.006! 0.006! 0.006! 0.006! 0.005! 0.005! 0.005! 0.005! 0.004! 0.004! 0.004! 0.004! 0.003! 0.003! 0.003! 0.003! 0.002! 0.002!

(d)
Pb/ 204Pb plotted against whole rock assay data (from Vale Inco Exploration) for samples from the Creighton Mine. (a) and (b) whole rock S and Ni contents ; (c) and (d) metal sulphur ratios. Model initial Pb isotope values calculated as Darling et al. (2010).
Figure 4.2: Model initial
207
sure of sulphide abundance. Figures 4.2a and 4.2b show that, in general, samples with higher sulphide content (i.e. massive sulphide ores) have higher
207Pb/ 204Pb . m
Again
comparing the ore Pb isotope characteristics with the dened Lower Unit Pb isotope stratigraphy, this strongly suggests that the majority of massive sulphides segregated early in the history of the Main Mass. Figures 4.2c and 4.2d compares
207Pb/ 204Pb m
with the chalcophile element ratios
Ni/S and Co/S. These ratios are indicators of the metal content of the sulphide in the rock sample. Clearly there is no systematic variation, which would suggest that there is no link between the timing of sulphide segregation and the metal content (tenor) of the sulphide. However, these metal ratios are particularly sensitive to sulphide fractionation processes. As discussed in Section 2.2.3, upon cooling sulphide melts ex-solve chalcopyrite rich intermediate solid solution (iss), which can be fractionated from the pyrrhorite-pentlandite monosulphide solid solution (mss). As such the mineralogy of sulphides in the selected samples controls the Ni/S and Co/S, and is unlikely to represent 83
3.5"
Ni in Pyrrhotite (wt %)"
3.0" 2.5" 2.0" 1.5" R! = 0.51" 1.0" 15.36" 15.38" 15.40" 15.42"
m"
15.44"
15.46"
207Pb/204Pb
Pb/ 204Pb plotted against the Ni content of pyrrhotite separates. Uncertainties on Ni content are 1 standard deviation.
Figure 4.3: Model initial
207
the bulk sulphide melt that segregated from the Lower Unit. One approach with the potential to avoid this problem is the characterisation of the metal contents of pyrrhotite-pentlandite (Po-Pn) mixtures, which represent the mss. The composition of Po has been shown to reect variations in the original bulk composition of sulphide melts (Vaughan et al., 1971) and, given that in Sudbury Pn occurs almost exclusively as exsolution textures within Po, the combined Ni content of Po-Pn mixtures can be considered representative of the bulk Ni content of the sulphide melt. Pyrrhotite rich fractions were separated using the techniques described in Section 3.1 and analysed for major and minor element concentrations by ICP-OES (inductively coupled plasma optical emission spectroscopy), using a Jobin Yvon Ultima 2 Sequential Spectrometer, operated by Chung Choi (University of Bristol). Ni, Cu, Fe and Co were analysed and calibrated using a series of S-doped standards that were made from single element certied concentration standards. Precision and accuracy were monitored by analysing in-house S-doped standards. The measured Ni and Co contents are shown in Table 4.1. A moderately strong positive correlation is seen between Ni, Co and Fe contents and
207Pb/ 204Pb m
(Figure 4.2). Ni contents in the Po and Pn mixtures range from 1.39

207Pb/ 204Pb m
to 3.12 wt %. Samples with higher have the highest metal tenor.
generally have higher Ni, Co and Fe
contents in Po-Pn mixtures. This suggests that the early formed sulphides do indeed
Preliminary results from this investigation therefore indicate that early (prior to signicant silicate crystallisation of the Main Mass) sulphide segregation is responsible for the majority of massive sulphide ores in the Creighton embayment. Furthermore these early sulphide melts appear to have the highest metal concentrations. However, signicant further work is required to test these relationships. In particular, systematic 84
4.3. PB ISOTOPES AS A TOOL FOR SULPHIDE ORE EXPLORATION? trends in the metal contents of sulphide melts in dierent orebodies in Sudbury are often only well dened in very large data compilations (many tens to hundreds of samples; P. Lightfoot, 2008, pers. comms.). As such a larger sampling population is required to test the statistical signicance of the trends seen between metal content and
207Pb/ 204Pb . m
85
86
87
5 Pb isotope systematics of the Offset Dykes

5.1 Introduction
The results of Chapter 4 show that isotopic heterogeneity is present throughout the Sudbury impact melt sheet. This investigation highlighted two main avenues for further research regarding the formation and evolution of the melt sheet. Firstly, it was noted that the high
207Pb/ 204Pb m
values of samples from throughout the South Range
stratigraphy were not consistent with melt sources dominated by the Superior Province (Grieve et al., 1991; Deutsch et al., 1995) or lower crust (Mungall et al., 2004) as previously suggested. Secondly, while the melt sheet was clearly heterogeneous around the time of the onset of silicate crystallisation, the extent to which the initial superheated products of impact melting were homogenised is unclear. In order to further examine these issues, the Pb isotope systematics of the earliest samples of the melt sheet have been investigated. These are to be found in the Oset Dykes, which contain quartz diorite phases that were emplaced prior to dierentiation of the Main Mass (Lightfoot and Farrow, 2002; Lightfoot et al., 1997b,a; Tuchscherer and Spray, 2002). The details and results of this study are presented in in the following paper, which is included in this chapter:
Darling J.R., Hawkesworth C.J. and Storey C.D. Shallow impact: isotopic insights into crustal contributions to the Sudbury impact melt sheet. in-review.
88
Shallow impact: Isotopic insights into crustal contributions to the Sudbury impact melt sheet
Darling J.R.a,1 , Hawkesworth C.J.a,2 , Storey C.D.b , Lightfoot P.C.c
a
Department of Earth Sciences, University of Bristol, Wills Memorial Building, Queens Road, Bristol BS8 1RJ, UK b School of Earth and Environmental Sciences, University of Portsmouth, Portsmouth PO1 3QL, UK c Vale Inco Exploration, Highway 17 West, Copper Cli, Ontario, P0M 1N0, Canada
Abstract The largest known terrestrial impact melt sheet occurs within the 1850 Ma Sudbury Structure, Ontario. In order to evaluate the relative contributions of dierent target lithologies to the melt sheet, we have investigated the Pb isotope compositions of feldspar separates from early formed quartz diorite magmas, within Oset Dykes from around the impact structure. The samples dene a linear array on plots of age corrected 206Pb/ 204Pb versus 207Pb/ 204Pb. Samples from Oset Dykes hosted by the Huronian Supergroup (South Range) have a range of 206Pb/ 204Pb1850 from 15.424 to 17.255 and 207Pb/ 204Pb1850 from 15.390 to 15.801, whilst those hosted by Archean gneisses of the Superior Province (North Range) cluster around 206 Pb/ 204Pb1850 14.8 and 206Pb/ 204Pb1850 15.1. These values can be approximated by binary mixing between the two major groups of target lithologies. A mix of 60-70 % of Superior Province gneisses with 30-40 % of Huronian metasedimentary material closely matches the Pb isotope compositions of North Range Oset Dyke samples, whereas in the South Range the required Huronian component is up to ca. 80 %. These mixing proportions are consistent with Sr, Nd and Os isotope and trace element constraints. A third minor component, either locally exposed Paleproterozoic mac rocks or the lower crust is also required. However, all of the geochemical characteristics of the melt sheet can be accommodated without the involvement of an average lower crust component. A major component of Huronian supracrustal material, which had a pre-impact thickness of up to 12 km, is required to explain the chemical characteristics of the impact melts, which also have a strong upper crustal anity (e.g. Eu/Sm = 0.22, Rb/Sr = 0.2-0.35). As such, a shallower level of melting is apparent than that predicted by many previous impact models for the Sudbury event. This can be accommodated by considering approach trajectories for the impactor oblique to the Earths surface. In addition, the variability identied indicates that the melt sheet was heterogeneous at an early stage, and may not have been completely homogenised during crater formation. Our ndings have signicant implications for the nature of the Sudbury impact event, evolution of the melt sheet and the crustal sources of metals contained in Sudburys world class Ni-Cu-PGE sulphide ores. Key words: Sudbury, impact melt, Pb isotopes, sulphide, Oset Dyke 1. INTRODUCTION 1.1. The Sudbury Impact Melt Sheet - Some Outstanding Issues There has been much debate regarding the source of the Sudbury melt sheet. Isotopic characteristics of silicates and sulphide ores require a crustal origin (Dickin et al., 1999, 1992, 1996; Faggart et al., 1985; Hurst and Wetheril, 1974; Walker et al., 1997, 1991; Darling et al., 2010), although the depth of melting is currently unclear.
Current impact models for the Sudbury event suggest that the upper crust would have been vaporised and ejected during excavation of the transient cavity (Deutsch et al., 1995; Grieve et al., 1991). This has been supported by the recognition that the concentration of certain transition metals, in particular Ni and the platinum group elements (PGE), in the melt sheet have a lower crustal anity (Mungall et al., 2004). In addition, Grieve et al. (1991) show that the bulk major element composition of the Sudbury Igneous Complex (SIC) can be modelled by whole rock melting of 93 % lower crustal granite-greenstone terrain and 7 % of upper crustal metasedimentary rocks. In contrast, isotopic investigations suggest a more signicant involvement of the upper crust in
Submitted to Geochimica et Cosmochimica Acta
February 12, 2010
8130'
8100'
Parkin
4645'
Foy Hess
Lake Wanapitei
Ministic Manchester FS
4630'
Sudbury
en Gr e vi l l n Fro
Worthington Southern Province Nipissing gabbros Granitic plutons Huronian Supergroup Cartier Batholith Levack Gneiss Complex
Copper Cliff Whitewater Group
10 km Chelmsford Formation Onwatin Formation Onaping Formation Upper Unit Middle Unit Lower Unit Quartz diorite
Superior Province
Figure 1: Summary geological map of the Sudbury Igneous Complex (SIC). Locations of the sampled Oset Dykes are
shown; FS; Frood-Stobie. Modied after Ames et al. (2005).
the source of the melt sheet. For example, the initial Nd isotope composition of the SIC lies on the upper continental crust Nd isotope evolution curve (Faggart et al., 1985), and a signicant contribution of upper crustal material appears to be required to explain the Pb isotopic characteristics of the melt sheet (Darling et al., 2010). As such it is currently dicult to reconcile predictions from impact models with the chemical characteristics of the largest impact melt sheet on Earth. The processes that produce chemical heterogeneity in impact melt sheets are also unclear. It has been recognised that the Sudbury melt sheet contains isotopic heterogeneities inherited from varied target lithologies (Dickin et al., 1999, 1996; Darling et al., 2010). However, the initial products of impact melting are expected to be homogenised by violent mechanical mixing (Phinney and Simonds, 1977; Simonds and Kieer, 1993), within minutes to hours of impact. The assimilation of country rocks, entrained clasts and fallback breccia by superheated impact melts provides a mechanism by which to produce heterogeneity over time (Darling et al., 2010), although whether primary heterogeneity resulting from impact melting of dierent target lithologies can be preserved
is not known. Understanding the timing and scale of inherited variability is important not only for our understanding of the evolution of the Sudbury melt sheet, but also for scaling-laws used to predict melt volumes in impact structures. Resolving these issues is important for our understanding of the mechanisms of crater and impact melt development, and the eects of planetary collisions on the evolution of the crust. There are two predominant questions regarding the origin of the Sudbury melt sheet that this investigation seeks to address: At what depth in the crust did the majority of impact melt originate? To what extent were these early melts homogenous? 1.2. Geology of the Sudbury Igneous Complex The SIC straddles the contact of the Archean Superior Province and Paleoproterozoic Huronian Supergroup (Figure 1), and formed as a result of impact melting of the crust at 1850 Ma (Dietz, 1964; Krogh et al., 1982). The associated impact basin, known as the Sudbury Basin, is thought 90
SIC
to have had a diameter of ca. 250 km (Spray et al., 2004), making it one of the largest and oldest known terrestrial impact structures. In addition to containing one of the principal reserves of Ni-Cu-Platinum Group Element (PGE) sulphides on Earth, Sudbury is of great importance in the study of impact processes due to the preservation of multiple features of the impact structure. The impact melt sheet (the Main Mass), together with radial and concentric dykes, locally termed Oset Dykes, comprise the Sudbury Igneous Complex (SIC). Overlying the SIC is a sequence of crater lling breccias and clastic sediments of the Whitewater Group. Extensive pseudotachylitic breccia belts, known as Sudbury Breccias, occur within the footwall. Detailed accounts of the local geology of the SIC are given in volumes edited by Pye et al. (1984) and Lightfoot and Naldrett (1994). The Main Mass is divisible into Lower, Middle and Upper Units (Figure 1), with the approximate proportions 30:10:60 respectively. The Lower Unit, often termed the Sudbury norite, typically consists of quartz monzogabbro to quartz gabbro, the Middle Unit quartz gabbro to quartz monzogabbro and the Upper Unit is granitic. The discontinuous Sublayer occurs at the melt sheet-footwall contact and consists of inclusion and sulphide-rich norite to monzogabbro, locally underlain by footwall breccias. Although highly variable, the Main Mass is typically ca. 2.5 km thick (Keays and Lightfoot, 2004). The Oset Dykes have an estimated total volume of 100 km3 when propagated to depth (Keays and Lightfoot, 2004) and intrude up to 30 km radially into the footwall rocks. Varying in thickness from hundreds to tens of meters, the dykes generally thin away from the melt sheet. Oset Dykes also occur concentrically, focused around the melt sheet, and are often associated with wide zones of pseudotachylite. There are two principal phases of quartz diorite that can be distinguished in many, but not all, Oset Dykes. Marginal, inclusion and sulphide free, quartz diorite (QD) was emplaced prior to dierentiation of the melt sheet (e.g. Lightfoot et al., 1997b) and before the melt sheet reached sulphide saturation (Lightfoot and Farrow, 2002), which likely occurred at temperatures in excess of the Lower Unit liquidus (Keays and Lightfoot, 2004). This phase may be representative in composition of the bulk crustal melt (Lightfoot et al., 1997b; Lightfoot and Farrow, 2002; Mungall et al., 2004). A second quartz diorite phase contains abundant inclusions and sulphide (inclusion bearing quartz diorite; IQD), but also has geochemical characteristics that suggest it was emplaced prior to dierentiation of the melt sheet (Lightfoot and Farrow, 2002). The exact timing of Oset Dyke emplacement is uncertain, due to ambiguity in geological relation-
ships. For example, there is evidence supporting a violent, energetic mode of emplacement of some Oset Dykes (e.g. Murphy and Spray, 2002), whereas in other areas mingling between QD and IQD suggests a more passive mechanism (Riller, 2005). It is most likely that the Oset Dykes were emplaced after the collapse of the transient cavity (Tuchscherer and Spray, 2002), during formation of the central uplift (Wood and Spray, 1998; Tuchscherer and Spray, 2002) or later readjustment of the crater oor (Hecht et al., 2008; Scott and Benn, 2001; Riller, 2005). The latest time for emplacement is constrained by thermal models for the melt sheet. Cooling rates for the melt sheet depend heavily upon the method of heat loss at the upper contact. If the overlying fallback breccias (Onaping Formation) acted as a purely conductive medium, then vigorous thermal convection in the melt sheet would have dissisipated sucient heat to reach liquidus temperatures in 10000110000 years (Prevec and Cawthorn, 2002; Zieg and Marsh, 2005). However, there was an extensive hydrothermal system in the Onaping Formation (Ames et al., 1998), which allowed for cooling to liquidus temperatures in hundreds of years (Zieg and Marsh, 2005). The elliptical shape, dip of contacts at the surface and the assymetric deep structure of the SIC are a function of post impact deformation, generally attributed to the Paleoproterozoic Penokean orogeny (see Riller, 2005). The two main exposed sections of the melt sheet, termed the North and South Ranges respectively, are separated by a major fault system. Underlying the South Range is the Paleoproterozoic Huronian Supergroup, a series of predominantly metasedimentary rocks intruded by 2.3-2.4 Ga granites (Krogh et al., 1984) and voluminous 2.2 Ga gabbroic sills of the Nipissing suite (Corfu and Andrews, 1986). In contrast, the North range of the melt sheet lies mostly upon 2.71 Ga granulite facies metamorphic rocks of the Levack Gneiss Complex (Krogh et al., 1984), part of the Archean Superior Province. Investigations of the Sr, Nd, Os and Pb isotopic characteristics of SIC lithologies have revealed a strong crustal signature for all units (Dickin et al., 1999, 1992, 1996; Faggart et al., 1985; Hurst and Wetheril, 1974; Walker et al., 1991; Morgan et al., 2002). Lightfoot et al. (1997b) suggest that a mantle contribution of 20 % can be accommodated in the SIC, however it is not required to explain the chemical variations throughout the Main Mass (Lightfoot et al., 2001). Indeed no unambiguous evidence for signicant mantle input into the melt sheet has been reported, from either geochemical, eld or petrological studies. The relatively constant incompatible element ratios throughout the Lower Unit and Upper Unit stratigraphy have been taken as evidence for a single parent magma for all SIC lithologies (Lightfoot et al., 1997a). 91
Trace element data show subtle variations around the Main Mass, whereas systematic dierences in Pb isotope characteristics have been identied between ore and Sublayer samples from the North and South Ranges (Dickin et al. 1996) and between Lower Unit samples from each side of the complex (Dickin et al. 1999). Furthermore Darling et al. (2010) identied signicant stratigraphic and lateral heterogeneity in Pb isotopes throughout the South Range Lower Unit. These ndings indicate varying crustal sources for the melts around the complex, with both broad (North versus South Range) and small spatial scale (intra-Range) variations. 1.3. Impact Melting and Models of the Sudbury Event During an impact event, the immense kinetic energy of the impacting body is transferred to the target via the propagation of shock waves. Resultant compression and heating leads to melting. At pressures greater than ca. 50 GPa, shock waves will deposit sucient energy for total melting of crystalline targets (Melosh, 1989). Modelling of peak shock pressures has shown that the majority of melted material comes from an approximately spherical volume below the maximum depth of penetration of the impacting body (Melosh, 1989). This depth is dependant upon impactor density and velocity (Melosh, 1989; Pierazzo et al., 1997), constraints upon which rely on scaling relationships between impact melt volume and the size of the transient cavity (e.g. Grieve and Cintala, 1992; Melosh, 1989). The transient cavity is the initial product of the excavation phase of an impact event, and undergoes modication as a result of gravitational instability and collapse to form the nal impact basin (Melosh and Ivanov, 1999; Melosh, 1989). Based upon the distribution of shock deformation features, Huronian outliers and pseudotachylites, estimates of the Sudbury transient cavity diameter are 80 to 110 km (Deutsch et al., 1995; Grieve et al., 1991; Pope et al., 2004; Thompson and Spray, 1994). The total impact melt volume in Sudbury has been of much debate. Based primarily on the calculated volume of the melt sheet, suggested total impact melt volumes range from 8000 to 15000 km3 (Grieve et al., 1991; Wu et al., 1995). Taking into account melt in suevites (the Onaping Formation) Stoer et al. (1994) estimate 12000 to 13000 km3 . Using the scaling relationships of Grieve and Cintala (1992) and Melosh (1989), such values can be explained by a vertical impact of a 10-15 km in diameter chondritic body, travelling at 20-25 kms1 . Models of thermal, structural and geochemical processes during the Sudbury event have largely been based upon such parameters (Deutsch et al., 1995; 92
Grieve et al., 1991; Mungall et al., 2004; Ivanov and Deutsch, 1999; Zieg and Marsh, 2005). The maximum depth of penetration of such an impactor is approximately equal to its diameter (Grieve and Cintala, 1992). The upper 10-15 km of crust would have been excavated or vaporised, and the resultant transient cavity ca. 30 km deep (Deutsch et al., 1995). Given estimated total thicknesses of the Huronian Supergroup of 8-12 km (Dressler, 1984; Young et al., 2001) the majority of melt is therefore predicted to have originated below this supracrustal succession, in the underlying Archean basement (Deutsch et al., 1995; Grieve et al., 1991; Mungall et al., 2004). During collapse of the transient cavity, which likely took a few minutes (Melosh and Ivanov, 1999), fragmented target rocks would have been mixed into the superheated impact melt (Ivanov and Deutsch, 1999). This process has been suggested to account for the incorporation of Huronian material into the South Range melt (e.g. Deutsch et al., 1995). 1.4. New Approach Isotope geochemistry is established as a valuable tool in assessing variability in impact melts, inherited from target lithologies (Dickin et al., 1999, 1996; Kettrup et al., 2003; Darling et al., 2010). In Sudbury, the Pb isotope system has proven to be more sensitive to target rock variations than Nd isotopes. This is because the Huronian metasedimentary sequence, which underlies the southern exposed limb of the melt sheet (the South Range), was derived from the Superior Province (McLennan et al., 1979, 2000), which underlies the northern limb (the North Range; see Figure 1). Due to the dierences in chemical properties of parent and daughter isotopes, fractionation of U and Th from Pb occurs during sedimentary processes. For example U is redox sensitive, and in oxidised environments is transported as dissolved uranyl complexes because U6+ is highly soluble in aqueous solutions (e.g. Langmuir, 1978). This results in dierent Pb isotope evolution over the time between sedimentation (<2450 Ma; Bennet et al., 1991; Young et al., 2001) and the time of impact (1850 Ma; Krogh et al., 1982). Other isotopic systems, such as LuHf and Sm-Nd, do not fractionate signicantly in this way (McCulloch and Wasserburg, 1978; Patchett et al., 1984; Vervoort et al., 1999), resulting in similar isotopic ratios in each province (Prevec et al., 2000; Naldrett et al., 1986; McLennan et al., 2000). Sampling of quartz diorites of the Oset Dykes oers the best available insight into early melt heterogeneity and the relative contributions of target lithologies. Therefore our strategy has been to investigate the Pb isotope systematics of quartz diorites from Oset Dykes from around the SIC.
2. SAMPLING AND METHODS 2.1. Sampling Strategy A variety of Oset Dyke environments were sampled. Both radial (e.g. Worthington, Copper Cli, Foy) and concentric (e.g. Hess, Manchester) Oset Dykes, including quartz diorites proximal and distal to the Main Mass were sampled (Figure 1). Where possible, sampling focused upon QD, as this represents the earliest melt phase in the Sudbury Structure. It has been shown that the trace element geochemistry of IQD matrices has not been signicantly aected by assimilation of clasts (Lightfoot et al., 1997a; Lightfoot and Farrow, 2002) , therefore this unit reects early melt composition and was also sampled for Pb isotope analysis. Distinctions between the two quartz diorite phases is perhaps best dened in the Worthington Oset Dyke. Multiple samples were taken in the Totten Mine area (e.g. Lightfoot and Farrow, 2002), in order to identify variability within individual Osets, and test the degree of coherence between QD and IQD Pb isotope systematics. 2.2. Methodology 2.2.1. Sample preperation and chemistry Of those samples that contained inclusions, care was taken to analyse only the quartz diorite matrices. Following careful cutting of each sample and subsequent crushing and sieving (<500 m), plagioclase feldspars were separated by a combination of density and magnetic separation techniques. Feldspars are less susceptible to post crystallisation alteration than whole rock Pb isotopic measurements and have lower U/Pb ratios, resulting in less in-growth of radiogenic Pb and the preservation of near magmatic isotope ratios. Aliquots for analysis (100-400 mg) were handpicked under a binocular microscope. Samples were leached for 20 minutes in both 6 M HCl and 7 M HNO3 to remove surface contamination and loosely bound Pb. Subsequently, samples were dissolved in 9 M HF and 7 M HNO3 . Step dissolution experiments similar to Housh and Bowring (1991) revealed constant U/Th/Pb ratios and isotope compositions after the initial leaching steps. The 6 M HCl and 7 M HNO3 leaches had radiogenic Pb isotope ratios and high U/Pb ratios, but removed less than 10% of the total mass of Pb. The procedures for chemical separation of Pb were modied from Strelow (1978) and were detailed in Darling et al. (2010). Total procedural blanks were between 15 and 40 pg and had no aect on the reported numbers within the quoted uncertainty. 93
2.2.2. Analytical procedures The isotopic composition of Pb was determined on a Thermo Scientic Neptune multi-collector (MC) ICP-MS at the Department of Earth Sciences, University of Bristol. Methods were described in detail by Darling et al. (2010) , and utilised a sample-standard bracketing technique to correct for instrumental mass bias. NIST SRM 981 was used as the bracketing standard and the double-spike values of Baker et al. (2004) used for normalisation. NIST SRM 982 was used as a consistency standard, which yielded averages, over a 9 month period (n = 96), of 36.7484 50 (137 ppm), 17.1649 31 and 36.7557 88 for 206Pb/ 204Pb, 207 Pb/ 204Pb and 208Pb/ 204Pb respectively (uncertainties are 2 standard deviations; 2). Concentrations of analysed standard and sample solutions were closely matched at 50 ppb. Both the BHVO2 and BCR-2 basalt standards were also measured, and were within uncertainty of the values of Baker et al. (2004). Multiple aliquots of BCR-2 (n = 14) yielded averages of 18.754 13, 15.628 8 and 38.739 30 for 206Pb/ 204Pb, 207Pb/ 204Pb and 208 Pb/ 204Pb respectively. U/Th/Pb ratios and concentrations were measured on a Thermo Scientic Element II at the University of Bristol. A tandem quartz glass spray chamber (Cyclonic + Scott double pass) and PFA 100 l/min nebuliser were used, as they provide excellent signal stability. Employing an external calibration, precision of U/Pb ratios was <0.5 % (2) and accuracy was monitored using basalt standards BCR-2, BHVO-2 and in-house calibration standards, all of which were within uncertainty of reference values.
3. RESULTS Lead isotope data, together with U/Pb ratios are presented in Table 1. Plots of 206Pb/ 204Pb versus 207 Pb/ 204Pb and 208Pb/ 204Pb are shown in Figure 2. Quartz diorite samples from North and South Range Oset Dykes respectively dene diering arrays, although there is signicant variation between Oset Dykes from each side of the complex. In general, North range samples have lower 206 Pb/ 204Pb and 207Pb/ 204Pb than South Range samples. In plots of uranogenic Pb, Dickin et al. (1996) found that basal samples of the Lower Unit of the Main Mass and sulphide scattered around 1850 Ma reference lines. Quartz diorites from individual Oset Dykes do lie along 1850 Ma reference lines, although the regressions through all North and South Range samples correspond to two stage model Pb (Stacey and Kramers, 1975) reference lines of ca. 2.5 Ga and 2.2 Ga respectively. It is clear that the Pb isotope compositions of Oset Dykes do not share a common source.
206
Sample
206 207 208
Offset Dyke
Foy Foy Foy Ministic Parkin Parkin Hess IQD IQD IQD IQD QD QD QD IQD QD QD Copper Cliff Manchester Manchester QD QD QD South South South South South South South South South South South South 502020 5155300 464830 5136190 465670 5136940 464830 5136190 465680 5136930 464830 5136100 494200 5146420 494820 5147740 494720 5142300 494200 5146380 521260 5156150 521260 5156150 North 464960 5178370 15.436 15.965 16.402 16.757 16.309 16.743 16.708 29.015 17.647 18.333 16.174 25.312 19.275 IQD North 464960 5178370 20.798 QD North 509900 5184420 16.111 0.003 0.003 0.002 0.003 0.003 0.003 0.003 0.003 0.004 0.005 0.005 0.003 0.004 0.004 0.003 IQD North 509980 5184520 16.896 0.003 IQD North 459620 5154770 15.340 0.002 15.189 15.394 15.332 16.045 15.187 15.457 15.555 15.634 15.534 15.628 15.623 16.835 15.620 15.679 15.441 16.712 16.032 QD North 489530 5176930 15.225 0.002 15.112 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 IQD North 481630 5178320 15.840 0.003 15.196 0.003 QD North 489750 5176860 15.525 0.002 15.192 0.003 35.661 37.006 36.209 36.027 37.580 35.898 38.973 35.661 35.742 35.845 36.136 35.837 36.250 36.315 37.794 37.432 37.742 35.749 43.649 38.564
Range
East1
North1
Pb/204Pb
2!
Pb/204Pb
2!
Pb/204Pb
2!
0.010 0.009 0.010 0.011 0.009 0.010 0.010 0.010 0.010 0.011 0.010 0.009 0.010 0.010 0.011 0.010 0.009 0.010 0.011 0.013
238
U/204Pb
2.227 3.482 0.974 1.193 6.558 3.555 21.921 1.854 1.449 0.669 1.632 0.646 1.457 1.457 47.584 6.135 8.019 1.400 24.254 6.210
2!
0.002 0.010 0.020 0.002 0.002 0.020 0.113 0.007 0.005 0.001 0.006 0.003 0.008 0.008 0.187 0.004 0.004 0.015 0.101 0.003
204
Pb/ Pb1850 2
14.786 14.684 14.902 14.943 14.717 14.931 13.516 14.820 15.484 16.180 16.215 16.094 16.259 16.224 13.208 15.608 15.670 15.709 17.255 17.212
207
2!
204
Pb/ Pb1850 2
207
2!
204
Pb/ Pbm3
2!
JD08SIC03 JD08SIC01 FOQD1 MOIQD1 POIQD1 POQD1 JD08SIC11 JD08SIC11b Hess FSOIQD1
Frood Stobie Worthington Worthington Worthington Worthington Worthington Copper Cliff Copper Cliff Copper Cliff
0.003
15.108
0.023
15.185
0.004
0.007
15.066
0.004
15.154
0.004
0.014
15.075
0.004
15.139
0.004
0.003
15.145
0.004
15.203
0.004
0.003
15.147
0.004
15.232
0.004
0.014
15.199
0.004
15.259
0.004
0.075
15.221
0.009
15.441
0.005
0.005
15.117
0.004
15.190
0.004
0.004
15.402
0.004
15.400
0.004
WOIQD2 WOIQD1 WOQD2 WOQD1 WOQD3 CCOIQD1 JD07SIC25 JD07SIC26 CCOQD1 JD08SIC14 JD08SIC15
0.003
15.530
0.004
15.449
0.004
0.005
15.573
0.004
15.488
0.004
0.003
15.509
0.004
15.438
0.004
0.006
15.573
0.004
15.483
0.004
0.007
15.568
0.004
15.482
0.005
0.125
15.048
0.015
15.302
0.006
0.006
15.390
0.004
15.373
0.006
0.004
15.378
0.004
15.355
0.004
0.011
15.389
0.004
15.361
0.005
0.067
15.801
0.009
15.598
0.005
0.004
15.799
0.004
15.601
0.004
Table 1: Pb isotope data from Oset Dyke quartz diorite (QD) samples and inclusion bearing quartz diorite (IQD). 1 Grid references (easting and northing) are given in UTM coordinates (zone 17N; NAD27). ratios age corrected using measured . 3 Model initial 207Pb/ 204Pb calculated as by Darling et al. (2010) for reference. Oset Dyke locations are shown in Figure 1
Initial Pb isotope
94
44 42 208Pb/204Pb 40 38 36
bance was not recent. The age corrected Pb isotope ratios of these samples are distinct from all other samples, with very unradiogenic initial values. Uncertainty in the initial ratios includes propagated uncertanty in the measured Pb isotope ratios, , decay constants (Jaey et al., 1971) and crystallisation age (Krogh et al., 1984; Ostermann et al., 1996). 4. DISCUSSION
16.5 207Pb/204Pb
4.1. Source of Melt 4.1.1. Pb isotope composition of target lithologies at 1850 Ma In order to evaluate the contributions of target rocks to the melt sheet, it is necessary to constrain the isotopic composition of target rock groups at the time of impact, 1850 Ma. Present day Pb isotope compositions must be back projected using either measured U/Pb, or modelled Pb isotope evolution. Unfortunately, whilst there are a number of Pb isotope studies of locally exposed target rocks, few contain U/Pb element ratio information. The modelling of Pb isotope ratios at the time of impact is represented in Figure 3. The Huronian Supergroup was largely derived from Superior Province gneisses (McLennan et al., 1979, 2000). Following McLennan et al. (2000), the required to evolve Pb isotope compositions from initial Superior Province ratios, constrained by least radiogenic feldspars (Gariepy and Allegre, 1985; Hemming et al., 1996), to measured Huronian values, can be used to model Pb isotope evolution of the Huronian Supergroup. In contrast, values of for the Nipissing gabbro intrusions are poorly constrained. Extensive datasets of the chemistry of these intrusions can be found in the literature (Lightfoot, 2002; Lightfoot et al., 1993), however none report Pb concentrations. These dominantly tholeiitic intrusions show evidence for variable crustal contamination (Lightfoot, 2002). As such a of around 9-10 seems reasonable to model their Pb isotope evolution. Gneisses of the Superior Province have a complex Pb isotope history (Figure 3). Initial ratios at 2.71 Ga are provided by least radiogenic feldspars (Gariepy and Allegre, 1985; Hemming et al., 1996) and galenas (Vervoort et al., 1994). Present day ratios of Levack Gneisses and Sudbury Breccias (pseudotachylites) fall on a 2.7 to 1.1 Ga paleoisochron, potentially indicating U loss occured at 1.1 Ga. Neither ca. 1.85 Ga Penokean (e.g. Sims et al., 1989), 1.85 Ga Sudbury or ca. 1.1 Ga Grenvillian metamorphism (e.g. Card et al., 1984) led to similar U loss in the Huronian Supergroup. As such it is likely that gneisses evolved with variable U/Pb ratios prior to ca. 2.6 Ga partial U loss during granulite facies metamorphism 95
16.0
15.5
15.0 14 16 18 20 22 206Pb/204Pb South Range 24 26
Hess IQD Foy IQD Foy QD Parkin QD Parkin IQD Ministic IQD
North Range
Manchester QD Copper Cliff QD Worthington QD Worthington IQD Frood-Stobie IQD
Figure 2: Plots of Pb isotope data for Oset Dyke
quartz diorites (QD) and inclusion bearing quartz diorites (IQD). Two stage model Pb curves are shown from 0 to 2.8 Ga (Stacey and Kramers, 1975). Regression lines through all North Range (black) and South Range (grey) samples.
There are signicant dierences between the samples from the North and South Ranges, as well as minor isotopic variability between Oset Dykes from each side of the complex. In order to best resolve these variations it is useful to calculate initial ratios at the time of impact, by age correcting using measured U/Pb ratios. Values of 238 204 U/ Pb () are generally well below 8. Samples from Oset Dykes hosted by Huronian Supergroup metasedimentary rocks (South Range) have a range of 206Pb/ 204Pb1850 from 15.484 17.255 and 207Pb/ 204Pb1850 from 15.378 - 15.801, while those hosted by Archean gneisses of the Superior Province (North Range) cluster around 206 Pb/ 204Pb1850 14.8 and 206Pb/ 204Pb1850 15.1. Dickin et al (1996) found variable disturbance of the U/Th/Pb ratios in ores from around the complex. Three samples analysed in this investigation were found to have high values (21-48), which may have been caused by Pb loss or U gain. These samples also have the most radiogenic measured Pb isotope ratios, suggesting that U/Th/Pb distur-
16.2 16.0 15.8 207Pb/204Pb 15.6 15.4 15.2 15.0

2.5 0 1.0
.5 =9
= 22
14.8 14.6 14.4 13.0 14.0 15.0 16.0 17.0 206Pb/204Pb

Model (1.85 Ga)
18.0
19.0
Levack Gneiss NR Sudbury Breccia Superior Province feldspar Nipissing gabbro
Measured
Nipissing gabbro L. Huronian metased. U. Huronian metased.
Figure 3: Modelling of Pb isotope compositions of target rocks at 1850 Ma. North Range (NR) country rocks fall
along a paleoisochron between 2750 and 1000 Ma, anchored by least radiogenic detrital feldspars from the Superior Province (Gariepy and Allegre, 1985; Hemming et al., 1996). Evolution of the Pb isotope composition of Huronian metasedimentary rocks is represented by a = 22 growth curve from the North Range feldspar data. Gray shading represents range of Huronian samples back projected from measured values with variable (data from Dickin et al., 1996 and McLennan et al., 2000). Age corrected Nipissing gabbro acquired by back projecting measured values with an assumed of 9.5. Also shown is the 2-stage model Pb isotope evolution, from 0 to 3000 Ma, of Stacey and Kramers (1975).
(see Easton, 2000). It is not possible to resolve the absolute Pb isotope evolution of these gneisses, although it is evident that at 1850 Ma they would have had Pb isotope ratios evolved little from the least radiogenic feldspar data. 4.1.2. Isotopic constraints on melt sources The age corrected Pb isotope ratios of Oset Dyke samples dene a linear array on plots of 206 Pb/204 Pb versus 207 Pb/204 Pb. When compared to modelled 1850 Ma Pb isotope ratios of target rocks, the variations in initial Pb isotope ratios can be approximated by binary mixing of Superior Province gneisses and Huronian metasedimentary rocks (Figure 4). The relative proportions of each target group required to produce the Pb isotope composition of Oset Dyke samples varies significantly. North Range Oset Dykes require mixing of Superior Province gneisses with a ca. 30% Huronian component. South Range Oset Dykes require a much higher Huronian component of ca. 50% in Copper Cli and Frood Stobie QD, ca. 65% in Worthington QD and ca. 90% in Manchester QD. Deviation of the samples from the binary mixing line, to higher 207 Pb/204 Pb and lower 206 Pb/204 Pb, can be accommodated by the incorporation of variable amounts of Nipissing gabbro. A compilation of strontium and neodymium isotope data for the Main Mass and Sublayer of the melt sheet and locally exposed target rocks is 96
shown in Figure 5. The Main Mass and Sublayer samples have initial Sr and Nd isotope compositions that fall between those of Huronian metasedimentary rocks and the Levack Gneisses. Mixing lines between these two target rock groups satisfactorily model the range of Main Mass initial Sr and Nd isotope compositions. Main Mass samples require a 40-60 % Huronian melt component. Interestingly, whilst Sublayer samples more closely reect their respective footwall rocks, they too require a mixture of Huronian and Superior Province material to explain their Sr isotope compositions. Binary mixing of Superior Province gneisses with Huronian metasedimentary rocks can also explain the Re-Os isotope systematics of sulphide ores from around the complex (Morgan et al., 2002). Variations in initial 187 Os/188 Os suggest a 12 to 55 % Huronian melt contribution to the source of the ores. Morgan et al. (2002) also found suprachondritic 186 Os/188 Os, which likely reects the incorporation of tens of percent of mac Huronian volcanic rocks or Nipissing gabbro. The Sr-Nd, Os and Pb isotope systematics of SIC lithologies can all be accounted for by mixing of locally exposed target lithologies, and are broadly consistent in their constraints on the relative contributions of target lithologies to the melt sheet (Table 2). That the Oset Dyke samples exhibit a greater range of mixing proportions than the Main Mass is interesting, and presumably reects
16. 5
16. 0 207Pb/204Pb
15. 5
15. 0
14. 5 13. 0 14. 0 15. 0 16. 0 206Pb/204Pb North Range Offset Dyke South Range Offset Dyke Nipissing diabase Superior Province feldspar Upper Huronian model Lower Huronian model 17. 0 18. 0 19. 0
Figure 4: Pb isotope data from Oset Dyke samples corrected to 1850 Ma. Samples dene a mixing array between
the modelled 1850 Ma composition of Superior Province gneisses (dary grey shading), and Huronian metasedimentary rocks. A binary mixing line is shown with 10 % graduations. Deviations from this mixing line, to higher 207Pb/ 204Pb1850 , suggests signicant contributions of Nipissing gabbro (Dickin et al., 1996). Age corrected upper and lower Huronian metasedimentary rocks are plotted in the light grey shaded eld. Open squares are least radiogenic North Range feldspars (Gariepy and Allegre, 1985; Hemming et al., 1996). The three samples with low 206Pb/ 204Pb have high (20-40), indicative of relative Pb loss. Error bars are 2 standard deviations.
partial mixing of the melt sheet after Oset Dyke formation. It is clear that a signicant to dominant Huronian melt source is required to explain the isotopic characteristics of the early formed impact melts in Sudbury. 4.1.3. Trace element constraints It is important to reconcile the isotopic constraints upon the melt sources with limits provided by trace elements. Although major element mixing models have previously been utilised to model the bulk SIC composition (Grieve et al., 1991), considerable lithological variations occur within each of the main target groups discussed. As such it is dicult to assign end member compositions to be used in modelling. Given that the Huronian sediments were predominantly derived from the Superior Province (McLennan et al., 1979, 2000) trace element ratios with distinctive fractionation behaviour during sedimentary processes oer particularly discriminatory tools. Representative trace element plots are shown in Figure 6. Ratios such as Eu/Sm, which are only aected by igneous processes (see Kemp and Hawkesworth, 2003), are relatively uniform for all units. However, ratios that fractionate during sedimentary processes (e.g. Th/U and Sr/Yb) show large dierences between target rock groups. Oset Dyke quartz diorites and average Main Mass 97
lie along mixing lines between Huronian metasediments and Superior Province gneisses. End member compositions for the mixing lines, shown in Figure 6a-b, were estimated from available published data. For the Huronian metasediment end member a mix of 2/3 Elliot Lake mudstone (lower Huronian) and 1/3 Gogwanda argillite (upper Huronian) was used, which is geologically reasonable given the estimated thicknesses of Huronian units (Dressler, 1984; Young et al., 2001). For the Superior Province, a mix of 2/3 Levack gneiss and 1/3 Cartier Batholith was used. Assuming bulk melting, such trace element mixing models suggest a Huronian contribution of 30 to 70 % for the Oset Dykes, with the average Main Mass generally requiring intermediate proportions. Reassuringly these estimates are entirely consistent with the isotopic constraints (Table 2). The Pb isotope data, together with Os isotope investigations, suggested that Nipissing mac rocks might have been a signicant contributing target lithology to the melt sheet. This can be further investigated by plotting trace element ratios that are not aected by sedimentary processes or hydrodynamic sorting, i.e. ratios that are good provenance indicators. In Figure 6c Th/Sc conrms the intimate association of Huronian metasediments and Superior Province gneisses. Deviation of Oset Dyke QDs to higher Sc and
5 Main Mass NR Sublayer SR Sublayer Levack Gneiss Huronian metased.
Nd1850
-5
-10
-15 -50
50
100
150
200
250
Sr1850
Figure 5: Sr and Nd isotope compositions of the Main Mass, Sublayer and target rocks of the SIC. Measured values
were recalculated to 1850 Ma. Example mixing curve between Huronian metasediments and Levack gneisses, with 10% graduations, is shown. The bar indicates the total range of Huronian Nd isotope values. Data sources: Levack gneisses (Hurst and Wetheril, 1974; Naldrett et al., 1986); Huronian metasediments (Dickin et al., 1999; Fairbairn et al., 1967; McLennan et al., 2000); Sublayer and Main Mass (Dickin et al., 1999; Faggart et al., 1985; Gibbins and McNutt, 1975; Hurst and Wetheril, 1974; Naldrett et al., 1986).
System Pb isotopes
SIC lithology SR Offset Dykes NR Offset Dykes Main Mass NR Sublayer SR Sublayer Sulphide ores
Huronian Superior Province metased. (%) gneisses (%) 50-90 25-35 30-75 25-40 ~60 12-55 10-50 65-75 25-70 60-75 ~40 45-88
Notes May require tens % of Nipissing gabbros
Sr-Nd isotopes
Os isotopes
186
Tens % of mac rocks (Nipissing gabbro) required to explain Os/188Os systematics. Target rock end members poorly constrained.
Th/U vs. Eu/Sm NR Offset Dykes SR Offset Dykes Av. Main Mass Th/U vs. Sr/Yb NR Offset Dykes SR Offset Dykes Av. Main Mass
~40 50-75 ~50 25-35 55-65 ~45
~60 25-50 ~50 65-75 35-45 ~55
Table 2: Summary of the relative proportions of target rock end members indicate by various isotopic and trace element
mixing models. See text for discussion and data sources.
98
Th/U
0 0.4 0.3 0.2 0.1
U
Th/Sc
8 0.01 0.1 1 10 40
L
6
L
A)
C)
Eu/Sm
30 20 10
400 300
B)
D)
3
L
Sr/Yb
200 100
2
U
1
L
0 2 4 6 8 1 2 3 4
Th/U
Superior Province Huronian metasediments Huronian volcanics Nipissing diabase
(Ce/Yb) n
Main Mass Offset Dyke QD Lower crust Upper crust
L U
Figure 6: Trace element constraints on the contributions of target lithologies. A) Th/U versus Eu/Sm. Mixing line is
shown between estimated Huronian and Superior Province end member compositions (see text for discussion), with 10% graduations. B) Th/U versus Sr/Yb. Mixing line calculated as A. C) Th/Sc versus Sc. D) Average continental crust normalised Ce and Ce/Yb. Data Sources: Huronian metasediments from average Gogwanda Formation argillites (Young, 2001), Elliot Lake Group mudstones (Fedo et al., 1997), Serpent Formation (Fedo et al., 1997; McLennan et al., 1979); Huronian volcanics from average rhyolites, mac end members and intermediate fractionates (Jolly et al., 1992); Superior Province data from average North Range Sudbury Breccias (LaFrance et al., 2008), Levack Gneisses and Cartier Batholith (Meldrum et al., 1997); average chilled Nipissing gabbro (Lightfoot et al., 1997b); average Main Mass (Lightfoot et al., 2001); averages from Oset Dyke quartz diorites (Lightfoot et al., 1997a); average continental crust, upper crust and lower crust (Rudnick and Gao, 2003).
lower Sc/Th could be explained by involvement of Nipissing gabbro, mac end members of Huronian volcanics, or an otherwise unidentied lower crustal source. The Oset Dyke samples are light rare earth element (LREE) enriched (Figure 6d), and measures such as (Ce/Yb)n have previously been used to discriminate between crustal source end member compositions in Sudbury (Lightfoot et al., 1997c; Naldrett and Hewins, 1984; Prevec et al., 2000). Some South Range samples are less LREE enriched than either the Superior Province or Huronian metasediments, suggesting a similar contribution of Nipissing gabbro, mac Huronian volcanics or the lower crust. The upper crustal anity of all SIC samples is clear in Figure 6. Oset Dykes and the average Main Mass have highly fractionated Eu/Sm and Rb/Sr (ca. 0.2 in North Range QD, 0.25-0.36 in South Range QD), which alone are strong indicators of an upper crustal melt. Indeed we nd
it dicult to reconcile the trace element concentrations or ratios of Oset Dyke samples with a source dominated by the lower crust, as proposed by Mungall et al. (2004). Signicant exceptions are the concentrations of certain chalcophile elements, in particular Ni, Pt, Pd, Ru and Rh which have concentrations signicantly higher than those of the average upper crust (Rudnick and Gao, 2003) . 4.1.4. Source of metals The Sudbury melt sheet is host to a vast resource of Ni-Cu-PGE sulphide ore. The historic resource exceeds 1500 million tonnes with an average grade of ca. 1.2 wt% Ni, 1.1 wt% Cu and 0.4 g/t of Pt and Pd (Keays and Lightfoot, 2004). Resolving the source of metals contained in sulphide ores remains a signicant problem for models of ore formation in Sudbury. Important estimates of the initial metal content of the melt sheet are provided 99
Ce n
Sc (ppm)
Ni (ppm)
0 160 140 20 40 60
u=
80 100 120 140 160

0 .5
y bla Su er
(A)
120 100 80 60 40 20
L
u Ni/C =2
(B) Pd (ppb)
10
L
by marginal, chilled quartz diorites. These units contain 60-70 ppm Ni, ca. 60 ppm Cu and 4 ppb of Pt and Pd (Keays and Lightfoot, 2004; Mungall et al., 2004). There is a general lack of published target rock data, however broad constraints upon whether the mixing proportions identied in this investigation can account for the bulk melt sheet metal contents are possible. The Ni and Cu contents of the average Main Mass and Oset Dyke QDs are higher than Huronian metasedimentary rocks or Superior Province gneisses. However, estimating average Huronian metasediment composition as section 4.1.3, and using the average gneiss data of Chai and Eckstrand (1994), it is shown in Figure 7 that addition of a ca. 20 % Nipissing component to an equal mix of Huronian and Superior Province melt can reproduce the Ni and Cu contents, and Ni/Cu ratio, of the bulk SIC. The average lower crustal composition of Rudnick and Gao (2003) has a Ni/Cu ratio of 3.4, suggesting that addition of a signicant component of average lower crustal material cannot reproduce the Cu content or Ni/Cu ratio of the bulk SIC. Platinum group element abundances in the target rocks are not well documented, making a robust assessment of whether sucient PGEs are contained in locally exposed lithologies very dicult. Our ndings indicate that the Ni and Cu contents of the melt sheet can be explained by mixing of known target rocks, and as such we would predict the same for the PGE. It is shown in Figure 7 that a mix of ca. 80 % upper crustal material with ca. 20 % of Nipissing gabbros closely matches the Pt and Pd concentrations of average quartz diorite (3.11 and 2.51 ppb respectively), and the average lower crust. Given the current distribution of the Nipissing mac suite, it is geologically reasonable that it would have contributed tens of percent of the total impact melt volume. The above observations suggest that a large volume of lower crust is not necessary, or indeed ideally suited, to explain the metal contents of the melt sheet. However, there is clearly much scope for a systematic study of Ni, Cu and PGE concentrations of target rocks in the Sudbury area, which would allow for further assessment of the suciency of metal contents in locally exposed target rocks. An important implication of our ndings is that the contribution of Nipissing gabbros (and similar mac rocks) may be fundamental to raising metal contents of the melt sheet. As previously discussed, the Th/Sc ratio is useful in identifying involvement of Nipissing gabbro in the source of QD magmas. Figure 8 compares the Th/Sc ratio with initial Pb isotope composition. Deviation from the Huronian-Superior Province mixing line, to lower Th/Sc in South Range QD, requires up to ca. 30 % Nipissing gabbro. Consistent with the
Cu (ppm)
Ni /C
Pt (ppb)
U M L
10
Av. Nipissing Av. Huronian metased. Av. Main Mass Av. Superior Province Av. Quartz Diorite Huronian volcanics
Av. Upper, Middle & Lower crust
Lower Unit Middle Unit Sublayer
Figure 7: (A) Ni and Cu contents of target rocks and
average SIC lithologies. Light grey shading is the range of ne grained Huronian metasedimentary rocks, with average upper and lower Huronian shown. Dark grey shading is the range of Levack Gneiss and Cartier Batholith samples, with the estimated Superior Province average calculated as per gure 6. Mixing line shown (with 20 % graduations) between an equal mix of Huronian metasedimentary rocks and Superior Province gneisses, with Nipissing mac rocks. Error bars on average Nipissing are 1 standard error. Also shown is the array of Main Mass and Sublayer samples (Lightfoot and Zotov, 2005). Data sources as Figure 6, with additional data from Chai and Eckstrand (1994). (B) Pt and Pd concentrations in average quartz diorite (Mungall et al., 2004), compared to Nipissing mac rocks (Valaincourt et al., 2003) and average crustal concentrations (Rudnick and Gao, 2003). Mixing line between average Nipissing mac rocks and upper crust, with 10 % graduations. Light grey circles are individual Nipissing samples. Note that the average Nipissing Pd content includes samples without corresponding Pt measurements.
100
16.1 15.9 15.7 15.5 15.3 15.1 14.9 14.7 14.5
0.2
0.4
0.6
0.8
Th/Sc
Nipissing Huronian metased. Levack gneiss
Offset Dyke samples
transient cavity diameter and melt volumes to estimate the nature of the impactor. One critical parameter that these models do not take into account is the angle of impact. Whereas vertical impact scenarios are desirable for simplifying modelling, the probability of a vertical impact is negligible. Impact events are expected to occur at an angle to the planetary surface (see Pierazzo and Melosh 2000 for review), with the most likely scenario being 45 , irrespective of the planets gravitational eld (Shoemaker, 1962; Gilbert, 1893). Modelling of oblique impacts demonstrates that the depth and volume of melted target rocks varies signicantly with impact angle. Pierazzo and Melosh (2000b) show that impact angle aects the strength and distribution of the shock wave, with the disposition of peak shock pressures becoming asymmetric and concentrated in the downrange, shallower, portion of the target. As a result, the volume of the target that experiences the required shock pressures for melting (between 50 and 100 GPa) has a maximum depth for vertical impacts and shallows signicantly for non-vertical impacts. In addition, the volume of vaporised material (>100 GPa) decreases signicantly (Pierazzo and Melosh, 2000b). The modelled distribution of peak shock pressures for a range of impact angles of a 10 km in diameter dunite body, travelling at 20 kms1 , is shown in Figure 9. Such an impactor is similar to that predicted for the Sudbury event (Deutsch et al., 1995; Grieve et al., 1991; Mungall et al., 2004; Ivanov and Deutsch, 1999; Zieg and Marsh, 2005). At the most likely impact angle (45 ) there is a signicant shallowing of the volume of melted material, accompanied by only a ca. 20 % reduction in melted volume. The region of total melting is constrained to the upper 20 km of the crust. In the 30 scenario, impact melting is constrained to the upper 16 km of the crust and the volume of vaporised material is far less than in vertical impact, however a melt volume reduction of 50 % also occurs. Oblique impacts can therefore account for the upper crustal nature of the impact melts. Oblique impact events can be recognised by asymmetric distributions of ejecta, shock metamorphism and deformation (Gault and Wedekind, 1978). Erosion and deformation of the Sudbury Structure unfortunately make it unlikely that such evidence has been preserved. 4.2.1. A comet impactor? The estimated impact melt volume for Sudbury of Stoer et al. (1994) (12000 to 13000 km3 ) can easily be accommodated by an oblique impact of an asteroid with density ca. 3 gcm3 , given the modelling results of Pierazzo and Melosh (2000b). However, a re-evaluation of the melt volume in Sudbury by Pope et al. (2004) suggests that current 101
207Pb/204Pb
1850
South Range North Range
Figure 8: Pb isotope and Th/Sc mixing of target rock end
members.
spatial distribution of Nipissing gabbro at current exposure levels, the contribution to North Range QD is lower (<20 %). Such proportions also explain the MgO contents of Oset Dyke quartz diorites (3.7-4.5 wt%), which are higher than Superior Province gneisses (mean ca. 3.5 wt %) and ne grained Huronian metasedimentary rocks (1.1-3.5 wt%) . It would therefore be predicted that the initial Ni Cu, and PGE contents of North Range impact melts were lower than the South Range. 4.2. Accomodating a Shallow Impact It has been shown that the chemistry of the melt sheet can be derived from melting of varying proportions of locally exposed target lithologies. A signicant contribution of Huronian metasediments is required throughout, and dominated the source of South Range impact melts. The Huronian Supergroup was deposited in a rift to passive margin environment on the subsiding margin of the Superior Craton between 2450 and 2219 Ma (McLennan et al., 2000; Young et al., 2001; Mungall and Hanley, 2004). The resultant southward thickening sedimentary wedge, which has since undergone multiple episodes of greenshist to amphibolite facies metamorphism (Riller, 2005), has a maximum total thickness of 8-12 km in the Sudbury region (Dressler, 1984; Young et al., 2001; Corfu and Andrews, 1986). The Oset Dyke quartz diorites therefore record a predominantly upper crustal precursor. Clearly such requirements are not in agreement with models that require near total vaporisation or excavation of the upper crust during the impact event (Deutsch et al., 1995; Grieve et al., 1991; Mungall et al., 2004; Ivanov and Deutsch, 1999; Zieg and Marsh, 2005). There are many factors that can inuence the volume and depth of melting in an impact event. As previously discussed, impact models for the Sudbury event have relied upon scaling between
Peak shock pressure (GPa)

>250 >200 >150 >100 >50 >30 >18
90 deg.
60 deg.
45 deg.
30 deg.
15 deg.
Figure 9: Peak shock pressure contours in the plane of impact for varying impact angles (from Pierazzo and Melosh,
2000b). Models for a 10 km in diameter dunite impactor, travelling at 20 kms1 . Axes units are kilometers. Also shown are the approximate maximum depths of impact melting for each scenario (taken as pressure >50 GPa).
estimates are not entirely satisfactory. The melt volumes in suevites (the Onaping formation) were underestimated by Stoer et al. (1994), and no previous estimates account for melt in the annular trough, or that was expelled from crater. Accordingly Pope et al. (2004) calculate a total impact melt (+ vapour) volume of ca. 30000 km3 . If the largest possible transient cavity (110 km), highest reasonable impact velocity (30 kms1 ), and impact angles >45 are taken, then an asteroid (density = 3 gcm3 ) can produce such large melt volumes. However Pope et al. (2004) suggest that a comet impactor (0.9 gcm3 , 40-50 kms1 ) is more likely, given their calculated melt (+ vapour) volumes for various impact scenarios (Figure 10). A comet impactor does appear to reconcile with estimated melt volumes better than an asteroid, particularly given an oblique impact. The identication of a meteoritic component can be achieved by assessing the refractory platinum group element (PGE) charactersitics of fallback material and distal ejecta (Koeberl, 1998). Although PGE concentrations will be higher in meteorites than comets, the composition of comets is poorly constrained. Given that comets may contain a signicant amount of rocky material similar to CI chondrites, iridium contents have been estimated to be between 113 - 338 ppb for ice contents of 25 75%, a factor of 1 to 8 less than chondrites (Kring et al., 1996) . Iridium concentrations in the On-
aping Formation are enriched relative to the bulk continental crust, with up to 0.5 ppb Ir (Mungall et al, 2004) and distal ejecta, recently recognised in Michigan, has up to 0.8 ppb Ir (Pufahl et al., 2007). It is not clear if these concentrations require a meteoritic impactor, particularly given that total vaporisation of the impacting body may not occur at impact angles of 45 or less Pierazzo and Melosh (2000a). There is much scope for a systematic geochemical investigation into the nature of the Sudbury impactor. 4.3. Heterogeneity of Impact Melts Variability in the Pb isotope composition of North Range Oset Dyke samples is small, and not easily resolved (Figure 4). Several South Range Oset Dykes have dierent initial Pb isotope compositions (Figure 11). The variation in South Range samples could be a result of their source containing variable proportions of Superior Province gneisses (up to 50%), and/or significant contribution from Nipissing gabbros. In either case, it is clear that they do not share common mixes of precursor target lithologies. Assuming all Oset Dykes were formed at the same time this must reect spatial variations in target rock contributions. In the North Range, the relative homogeneity of Oset Dykes likely reects a lack of variation of target rock Pb isotope compositions. 102
50000
1850 207Pb/204Pb
Melt + vapour volume (km3)
Asteroid Comet
Dtc = 100km
16.2 16.0 15.8 15.6 15.4 15.2

40% 60% 80%
40000
Dtc = 90km
30000
Dtc = 110km
20000
Dtc = 80km Dtc = 100km Dtc = 90km Dtc = 80km
14.5 15.0 15.5 16.0 16.5 17.0 17.5 18.0 206Pb/204Pb Frood-Stobie IQD Copper Cliff QD Manchester QD 1850
10000
0 30 45 90
Worthington IQD Worthington QD
Impact angle (degrees)

Figure 10: Modelled melt (+ vapour) volumes from a va-
Figure 11: Age corrected Pb isotope compositions of
riety of possible impact scenarios. Grey band is the estimated melt (+ vapour) volume for the Sudbury Structure. From Pope et al. (2004).
South Range Oset Dyke samples. Mixing line and Huronian end member as Figure 3. QD; quartz diorite: IQD; inclusion rich quartz diorite. Nipissing gabbros are also shown (solid circles).
Multiple samples of both QD and IQD were analysed from the Worthington Oset Dyke. No resolvable dierences in initial Pb isotopes are apparant between QD and IQD, indicating that, as concluded by Lightfoot and Farrow (2002), assimilation of inclusion populations has not signicantly aected the quartz diorite matrices of these samples. Samples of QD from dierent locations on the Oset have initial ratios that are just about resolvable given the analytical uncertainty (Figure 11). However it is clear that the isotopic variability on the scale of individual Osets is small compared to inter-Oset variability. Isotopic heterogeneity has been identied throughout the Main Mass of the melt sheet (Darling et al., 2010), whereby it has been suggested to result from continued assimilation of footwall rocks, fallback material and entrained clasts after the formation of the melt sheet. However, the geochemical variability identied between Oset Dykes shows that the melt sheet was heterogeneous within a relatively short time of impact. Theoretical considerations on the violent movement and mixing of superheated, low viscosity shock melt (Phinney and Simonds, 1977; Simonds and Kieer, 1993) suggest that the initial melt products of impact melting would have been homogenised during collapse of the transient cavity, within minutes of impact (Melosh and Ivanov, 1999). The products of shock melting, i.e. those formed directly by high shock pressures, would have been mixed with material entrained during ow along the transient cavity walls. The large dierences between North and South Range quartz diorites suggests that, on a broad scale, these melts retain chemical variations inherited from dier103
ent target rock precursors, despite extensive mechanical mixing during crater formation. Following collapse of the transient cavity, a melt sheet would have formed with an initial temperature of ca. 2000 K (Ivanov and Deutsch, 1999). Entrained clasts would have been completely digested and the melt sheet had potential to thermally erode hundreds of meters down into the footwall (Prevec and Cawthorn, 2002), as well as digest large volumes of fallback breccia. The identication of isotopic and trace element variability between Oset Dykes from the South Range indicates that at no stage was the melt sheet homogeneous. Indeed, continued assimilation maintained geochemical variabilities throughout the history of the melt sheet (Darling et al., 2010), despite vigorous convective mixing. 4.4. Implications for Crustal Evolution Of the preserved terrestrial impact structures, Sudbury is second in size only to the deeply eroded Vredefort impact structure (Grieve and Therriault, 2000). As such, the ndings of this investigation have some interesting implications for the aect of large meteorite impacts upon the crust. Impact models invoking melting to depths that approach the maximum transient cavity depth of ca. 30 km (Deutsch et al., 1995; Grieve et al., 1991; Mungall et al., 2004), infer that Sudbury sized impact events would have profoundly disturbed the compositionsal layering of the continental crust. If the melt sheet had a lower crustal source, as concluded by Mungall et al. (2004), then complete inversion of the crust would have occured. Furthermore, given a present day crustal thickness of 32-37 km in the southeastern Superior Province (Darbyshire et al., 2007), a 30 km deep transient
cavity would have extended towards the base of the crust. It has been dicult to reconcile such models with the fact that there is no record of decompressive mantle melting in the Sudbury area around the time of impact, or signicant mantle contribution to the melt sheet. The recognition of an upper to mid-crustal source for the melt sheet, and re-evaluation of the Sudbury event in terms of an oblique impact, indicates that the excavation and melting depths are signicantly shallower than previously considered. The compositional layering of the crust would not have been inverted, and the formation of the melt sheet without signicant mantle contribution becomes conceptually easier. 5. CONCLUSIONS The Pb isotope compositions of early formed quartz diorites in the SIC are readily explained by mixing of variable proportions of locally exposed target lithologies. The range of age corrected Pb isotope ratios in these samples can be approximated by binary mixing between Superior Province gneisses and metasedimentary rocks of the Huronian Supergroup. Deviation of samples from the binary mixing line can be explained by the incorporation of Nipissing mac rocks. Such an origin for the impact melts is consistent with previously published Sr, Nd and Os isotope data, together with trace element considerations. A minor lower crustal contribution cannot be excluded, although it is not required to explain the composition of the melt sheet. A Huronian component of up to 40 % is required in North Range samples, whereas in the South Range the Huronian contribution may be up to 80 %. This supracrustal succession had a maximum pre-impact thickness of ca. 12 km, requiring signicantly shallower melting than that predicted in previous impact models for the Sudbury event. This can be accommodated by considering approach trajectories for the impactor that are oblique to the Earths surface. Consistent with shallower impact melting, and in contrast to Mungall et al. (2004), we nd that the bulk composition of melt sheet has a strong upper to mid-crustal anity (e.g. Eu/Sm = 0.22, Rb/Sr = 0.2-0.35). Exceptions to this are the concentration of MgO and certain transition metals, in particular Ni, Cu and Platinum Group Elements. By compiling available target rock data, we nd that the incorporation of 10 to 30 % of Nipissing gabbro into the source of the melt sheet can account for the concentrations of these elements. Indeed, the incorporation of Nipissing mac rocks appears to better reproduce the bulk Ni, Cu and PGE composition of the melt sheet than does a lower crustal component. An important implication of this nding to the formation of sulphide ores in Sudbury is that the metal budget of the 104
Main Mass may be controlled by the spatial distribution of mac target lithologies. A systematic study of Ni, Cu and PGE abundances in target rocks is required to test this hypothesis. The variability in the Pb isotope composition of Oset Dykes from around the complex reveals that the melt sheet was heterogeneous at an early stage. At the time of Oset Dyke formation, the melt sheet was superheated and had signicant potential to generate chemical heterogeneity by assimilation of entrained clasts, footwall rocks and fallback material. However, given the large dierences in the relative proportions of target rocks required to explain the observed variations, it seems unlikely that the impact melts were fully homogenised at any stage. The major geochemical dierences between North and South Range melts probably survived mechanical mixing during collapse of the transient cavity. References
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Pb isotope systematics of the Offset Dykes
108
6 Impact melt sheet zircons

6.1 Introduction
The preceding chapters have focused upon the characterisation of isotopic variations throughout various melt sheet lithologies. The scientic objectives of this chapter are somewhat dierent, centering on the analysis of zircons from throughout the melt sheet stratigraphy. The importance of zircon (ZrSiO4 ) to a wide range of geological problems is well documented (see volume edited by Hanchar, 2003), and a vast literature exists detailing the characteristics and compositions of zircons from a wide range of magmatic and metamorphic environments. However, as yet there is almost no data relating to zircons that have crystallised from impact melt sheets.
Mass (g/years)
108 Oldest zircon (4.4 Ga)1 Oldest diamond bearing zircon (4.25 Ga)2 Oldest rock - Acasta gneisses3
50 100 150
1010 4.5
1012
1014
1016
1018
1020
Accretion of the moon
4.0
Isua supracrustal belt, evidence of oceans4 Oldest Impact spherule layers (3.48 Ga)5 Nectaris (3.9Ga) 3.5
Age in 109 years
3.0
2.5
Vredefort impact (2.02 Ga)6 Sudbury Igneous Complex (1.85 Ga)7 Oldest terrestrial melt sheet.
2.0
Figure 6.1: Selected features from the record of early Earth processes (left), along with a
histogram of >3.94 Ga detrital zircon ages from the Yilgarn Craton (Holden et al., 2009). Right: interpretations of the mass ux to the Moon (simplied after Koeberl, 2003). 1 - Wilde et al. (2001); 2 - Menneken et al. (2007); 3 -Bowring et al. (1989); 4- Fedo et al. (2001); 5 - Byerly et al. (2002); 6 - Kamo et al. (1996); 7 - Krogh et al. (1982).
The importance of such information is particularly related to our understanding of processes on the early Earth (Figure 6.1), given that intense post-accretionary bombardment occurred between 4.5 and 3.9 Ga (e.g. Kring and Cohen, 2002), and that the crustal record of this period is almost exclusively limited to detrital zircons with ages up 109
Orientale (3.82Ga?)
Late Heavy Bombardment ?
Imbrium (3.85Ga)
Impact melt sheet zircons
to 4.4 Ga (e.g. Wilde et al., 2001). As the largest and oldest terrestrial melt sheet, Sudbury oers a unique analogue for such features on the early Earth. Zircons from throughout the main units of the SIC have been characterised, with particular emphasis upon trace element concentrations and inclusion populations. The ndings, together with comparisons between the Sudbury data and the >3.9 Ga detrital zircon population, are presented in the following paper, which is included in this chapter:
Darling J., Storey C. and Hawkesworth C. (2009) Impact melt sheet zircons and their implications for the Hadean crust; Geology, v.37, no. 10, p. 927-930; doi: 10.1130/G30251A.1
110
Impact melt sheet zircons and their implications for the Hadean crust
Darling J.R.a,1 , Storey C.D.b , Hawkesworth C.J.a,2
a
Department of Earth Sciences, University of Bristol, Wills Memorial Building, Queens Road, Bristol BS8 1RJ, UK b School of Earth and Environmental Sciences, University of Portsmouth, Portsmouth PO1 3QL, UK
Abstract Impacts may have been important mechanisms of crustal redistribution and dierentiation, particularly during intense postaccretionary bombardment between 4.5 Ga and 3.9 Ga ago. Evidence of crustal processes during this period is largely provided by detrital zircons from the Yilgarn craton, Australia. Trace element compositions, crystallization temperatures, and inclusion populations of these ancient zircons have been taken as evidence for predominantly granitic source magmas, implying widespread felsic continental crust on the early Earth. However, there is little knowledge of zircons formed in impact melt sheets, a potential source for the Hadean zircons. Here we present Ti thermometry, trace elements, and inclusion populations of zircons from the 1.85 Ga Sudbury impact melt sheet (Ontario, Canada). Our results demonstrate that large variations in zircon crystallization temperature and composition will be an inevitable consequence of the evolution of such magmatic systems. We also show that zircons in mac rocks crystallize in residual liquids of granitic composition, producing inclusion assemblages that are remarkably similar to those reported for the ancient Yilgarn grains. Thus, we conclude that the trace element compositions and inclusion populations of the Hadean zircons are consistent with crystallization from more mac melts than previously recognized, although high crystallization temperature distributions of Sudbury zircons indicate that impact melt sheets were not a dominant source for the grains older than 3.9 Ga. Key words: Sudbury, impact melt, Pb isotopes, sulphide 1. Introduction Given limited exposures of terrestrial rocks older than 3.7 Ga, knowledge of Hadean and Eoarchean crustal processes relies predominantly on studies of detrital zircons, with ages as old as ca. 4.4 Ga (Wilde et al., 2001), from the Jack Hills and Mount Narryer regions in the Yilgarn craton. Hafnium isotope studies of these zircons provide evidence for dierentiation of the silicate Earth from very early in Earths history (Amelin et al., 1999; Harrison et al., 2008), yet the mechanisms of this dierentiation are poorly understood. Signicant emphasis has been placed upon constraining the source magmas from which these zircons crystallized. Studies have highlighted inclusion assemblages dominated by quartz, alkali-feldspar, apatite, plagioclase, biotite and muscovite (Hopkins et al., 2008; Maas et al., 1992; Menneken et al., 2007), while application of recently developed Ti in zircon thermometry revealed a dominant peak in crystallization temperatures at 680 C, considered indicative of prograde minimum wet melting conditions (Watson and Harrison, 2005, 2006). The interpretation of predominantly
granitic source rocks, based on these ndings, implies widespread felsic continental crust formation before 3.9 Ga, in contrast to predictions of long lived mac-ultramac early crust following magma ocean crystallization (Kamber, 2007; Kramers, 2007). Interpretation of detrital zircon populations relies upon understanding of zircons from well constrained magmatic and metamorphic rocks. There is currently little knowledge of zircons crystallized from impact melt sheets, an as yet unexplored origin for the ancient Yilgarn zircons and potentially an important mechanism of crustal redistribution and dierentiation during intense post accretionary bombardment of the early Earth (Grieve et al., 2006; Mungall et al., 2004). Accordingly, we have characterized the morphology, internal structure, inclusion assemblages and trace element composition of zircons from the Sudbury impact melt sheet. Sudbury is one of the largest and oldest terrestrial impact structures, it formed at 1.85 Ga (Krogh et al., 1982), with an original basin diameter of 250 km (Spray et al., 2004) and a melt volume of at least 8000 km3 (Grieve and Cintala, 1992). The associated melt sheet is a unique terrestrial analogue for such environments on the early Earth and terrestrial planets, and it dierentiated into 1-2 km thick silica saturated, hydrous granitic and gabbroic melts.
Geology, 2010, vol. 37, no. 10, 927-930
February 12, 2010
2. Sample suite
5000 UU
Zircons were separated from seven Lower Unit and three Upper Unit samples, along a transect of the southern exposed limb of the melt sheet previously studied by (Lightfoot and Zotov, 2005). Zircons from a quartz diorite from the Worthington Oset Dyke, representing an early melt phase injected into fractures created by re-adjustment of the crater oor (Lightfoot and Farrow, 2002), were also analyzed. Upper Unit samples are granitic, and consist predominantly of quartz and alkali feldspar intergrowths, plagioclase and biotite. The Lower Unit rocks vary from quartz monzogabbro to quartz gabbro, and consist of hypersthene and augite ( 2:1), plagioclase, quartz, biotite and FeTi oxides. Toward the base of the Lower Unit, quartz content increases to a maximum of 20 %. Zircons from all units occupy late interstitial sites, often in association with quartz and biotite. Generally equant, with long axes <300 m and varying denition of crystal faces, the zircons display oscillatory zonation of varying complexity (see Supplementary materials in Appendix, Figure 8.1). Scattered, randomly orientated inclusions up to 20 m and rare polyphase inclusions up to 40 m are apparent. With the exception of some skeletal zircons in samples from the middle of the Lower Unit, the internal structures are typical of magmatic zircons from varying lithologies. Consistent with extreme initial melt temperatures, there is no evidence of inherited zircon in the Sudbury melt sheet, either from this study, or from previous U-Pb investigations (Corfu and Lightfoot, 1996; Davis, 2008; Krogh et al., 1982, 1984; Ostermann et al., 1996).
Relative statigraphic position (m)
4000
3000 MU LU 1000
2000
0 QD 600 650 700 750 800 T (C)

Figure 1: Titanium thermometry results throughout the Sudbury melt sheet stratigraphy. Closed circles are individual analyses, open circles are sample means. Error bars are 2sd. Calculated whole rock Zr saturation temperatures are shown in grey (data from Lightfoot and Zotov, 2005). UU (Upper Unit), MU (Middle Unit; quartz gabbro) and LU (Lower Unit). Quartz diorite (QD) given arbitrary height of -500 m, and an average Zr saturation of Worthington Oset samples is shown (data from Lightfoot and Farrow, 2002).
850 900
4. Results 4.1. Titanium-in-zircon thermometry Measured titanium concentrations were used to calculate Ti-in-zircon thermometry temperatures T (T ziri ), following Watson and Harrison (2005). Given that the thermometer applies strictly to zircon grown in equilibrium with rutile, i.e., titanium activity (TiO2 ) equals one, all temperatures reported here are minimum estimates. However, there is an abundance of titanite and ilmenite throughout the stratigraphy, which Watson and Harrison (2005) argue constrains TiO2 to >0.6, T resulting in a possible underestimation of T ziri by around 50 C. Mean measured temperatures for zircon in the Lower Unit samples vary from 850 C to 750 C, Upper Unit from 760 C to 715 C and the quartz diorite mean is 774 C. The results show a systematic trend in crystallization temperature throughout the stratigraphy of the melt sheet (Fig. 1; Supplementary Table 8.1 in Appendix), and there are signicant within sample ranges of up to 112 C, and within grain variations of up to 36 C. Intracrystalline variations show systematic changes from higher Ti contents in the center of grains to lower in the rims. Interestingly, the spread of temperatures increases upwards through the Lower Unit and, to a lesser extent, the Upper Unit stratigraphy. 112
3. Analytical methods
Trace element analyses were undertaken by LAICPMS at the University of Bristol, utilizing a 193 nm excimer laser and Thermo Fisher Scientic Element 2. Hafnium, determined by electron microprobe, was used as an internal standard and analyses were normalized against NIST 612. Laser spot sizes were between 20 and 30 m. Titanium, measured on the 49Ti peak due to 96Zr ++ interferences on 48Ti, was measured together with U and Th. Accuracy of Ti measurements was monitored using NIST 614 and zircon standard Temora 2, yielding averages of 3.80 ppm 0.34 (2sd, n = 42) and 9.05 ppm 0.44 (2sd, n = 12) respectively. The REE were measured simultaneously in around a third of the analyses, using similar operating conditions. Forty additional REE analyses were undertaken without simultaneous Ti measurement.
Zircon crystallization temperatures of the Lower Unit samples and quartz diorites are consistent with the ndings of previous studies, in that bulk rock Zr saturation temperatures tend to signicantly underestimate the onset of zircon crystallization in an initially Zr under-saturated melt (Harrison et al., 2007). Modelling of liquid compositions during equilibrium crystallization of the Lower Unit magmas using the MELTS algorithm (Ghiorso and Sack, 1995), indicates that Zr saturation temperatures come into the range of upT permost T ziri (with an estimated correction for subunity TiO2 of 50 C) at 85 % crystallization for both the basal and upper samples. Zirconium saturation in the model occurs at very similar degrees of crystallization, and the residual liquid compositions at this stage are granitic (75 % SiO2) and peraluminous. The similar trend in bulk rock Zr T saturation temperatures to that of T ziri throughout the Lower Unit reects the inuence of major element chemistry and Zr content on the temperature at which zircons will crystallize in residual melts. Calculated Zr saturation temperatures in the UpT per Unit are signicantly higher than T ziri , even after correction for TiO2 <1. It is possible that this dierence is related to the composition being outside the experimentally calibrated range of Zr saturation studies (Watson and Harrison, 1983). 4.2. Zircon composition The composition of igneous zircon is sensitive to magmatic dierentiation (e.g., Wark and Miller, 1993), given that typically incompatible elements in magmatic rocks (e.g., Hf, Th, U) are compatible in zircon. Figure 2 shows relationships between T zircon crystallization temperature (T ziri ), (HfO2) and U. At high temperatures the data cluster, with a narrow range of U and Hf, but with decreasing temperature the data fan out. Similar trends are also seen for Th and the rare earth elements (REE). Zircons from each lithology display typical magmatic REE proles (see Supplementary Materials in Appendix, Figure 8.2), with positive Ce anomalies and negative Eu anomalies of varying magnitude, as expected given the signicant role of plagioclase in the evolution of the Sudbury melts. However there is a large range within each sample, and a general increase in the REE content T with decreasing T ziri suggests that a wide spectrum of REE proles is an inherent feature of zircons crystallizing in late interstitial liquids. The use of REE compositions as a tool for discrimination of igneous zircon sources has been questioned in previous studies (Coogan and Hinton, 2006; Hoskin and Ireland, 2000). Although the REE concentrations of Sudbury zircons are somewhat high relative to other mac and intermediate suites (Supplementary Table 8.2 in Appendix), we also nd that REE proles and ratios cannot unambiguously 113
5000 2sd 4000 3000 2000 1000 0 1.2 HfO2 (wt%) 1.1 1.0 0.9 0.8 0.7 700 750 800 T (C ) 850 900 2sd U (ppm)
Figure 2: Titanium thermometry temperature versus zircon composition. Open symbols are Lower Unit samples, closed symbols represent Upper Unit samples.
distinguish between impact melt sheet zircons, numerous well constrained magmatic zircon populations or detrital >3.9 Ga zircons from the Yilgarn Craton.
4.3. Inclusion populations
Inclusion populations of zircons from a quartz diorite (QD), basal Lower Unit (BLU), middle Lower Unit (MLU) and Upper Unit (UU) sample were characterized by energy and wavelength dispersive X-ray spectroscopy. The inclusion populations from all samples are dominated by quartz, plagioclase, k-feldspar, biotite and hornblende, with apatite a major constituent of Lower Unit inclusion assemblages. Six polyphase inclusions were identied within basal Lower Unit sample 144IBNR, consisting of quartz, plagioclase and kfeldspar hornblende biotite. Additional minor phases (<5 %) include muscovite (UU), monazite (MLU, UU) titanite (BLU, MLU), ilmenite (MLU, UU), chlorite (BLU, MLU, UU), Fe-oxide (UU), ourite (UU) and FeS (QD, BLU). Only 1 chlorite bearing grain shows evidence for secondary alteration in CL. Figure 3 shows that the proportion of major inclusion phases does vary between samples, but this distinction can only be made by statistical analysis of relatively large data sets (>40 inclusions from each sample). It is also shown that inclusion assemblages cannot easily be related to whole rock mineralogy.
50 40 Percentage 30 20 10 0 Quartz Plag K-Feld Biotite
Quartz Diorite Middle Lower Unit Basal Lower Unit Upper Unit
Quartz
Hbl
Apatite
Alkali-Feldspar
Plagioclase
Figure 3: Zircon inclusion populations. Left: Relative frequency of the major inclusion phases in each lithology. Right: Streckeisen diagram showing the rock and inclusion mineralogy for each sample. The arrows may not be representative of the exact path of residual melt, but indicate the change in mineralogy from whole rock to zircon inclusions.
5. Discussion The Sudbury impact melt sheet likely had extreme initial temperatures, several hundred degrees in excess of the dry liquidus of both the Lower Unit and Upper Unit ( 1200 C). The results of our investigation reveal that zircons from both units crystallized at temperatures comparable to other mac suites (gure 4). The temperatures are distinctly higher than the 680 C peak in >3.9 Ga zircons, although it should be noted that T 43 % of the >3.9 Ga T ziri data set falls within the temperature range 700-900 C (Fu et al., 2008; Watson and Harrison, 2006). Corrections for subunity TiO2 in Sudbury samples would only increase calculated temperatures, and given that rutile saturation studies indicate that TiO2 is generally >0.5 in magmatic rocks (Hayden and Watson, 2007; Ryerson and Watson, 1987), the correction of the >3.9 Ga zircons would be too small to overlap the peaks in the data sets. It has previously been argued that the 680 C peak for >3.9 Ga grains is signicantly lower than that of mac rocks, indicating a felsic source (Harrison et al., 2007; Watson and Harrison, 2005). Comparison with compilations of granitic and mac rocks indicates signicant overlap between the data sets, with the >3.9Ga peak seemingly lying between the mac and felsic peaks (Fig. 4). Tentatively, an intermediate composition source could be invoked. For example tonalites have a near identical peak in zircon crystallisation temperatures at 685 C (Fu et al., 2008; Hiess et al., 2006). The Sudbury melt sheet crystallized from the bottom upwards and top downwards, via the inward propagation of solidication fronts (Zieg and Marsh, 2005). Increasing ranges of Hf, Th, U and REE concentrations with decreasing crystallisation temperatures indicate that the main controlling factor on the abundance of these elements is the composition of the melt in equilibrium with zircon. As such these trends represent an increase in the potential heterogeneity preserved in residual melts, presumably reecting variable isolation 114
of interstitial melt, resulting in large variations in T T ziri and zircon composition. Accordingly, zircons from the most dierentiated samples yield a wide range of temperatures (>100 C). The overall T range of T ziri in the Lower Unit is 166 C, indicating that individual magmatic bodies can produce T a very wide range of T ziri . This may have significant implications for studies using zircon crystallization temperatures to calculate cooling rates (e.g. Lissenberg et al., 2009) and raises further difculty in interpreting the source of detrital zircon assemblages based on Ti crystallization temperatures. For example, it has been argued that neither T REE, nor T ziri can unambiguously distinguish the >3.9 Ga zircons from those formed by basalt differentiation at mid ocean ridges (Coogan and Hinton, 2006). Mac magmas in Sudbury have crystallised zircon inclusion populations of granitic mineralogy. This is consistent with the results of crystallization modeling, which indicates that zircons grew in late residual liquids that are highly evolved relative to the bulk rock composition. The inclusion populations are remarkably similar to those reported for the >3.9 Ga Yilgarn zircons (Cavosie et al., 2004; Hopkins et al., 2008; Maas et al., 1992; Menneken et al., 2007), with the exception of a signicantly higher proportion of muscovite found by Hopkins et al. (2008). Distinguishing the sources of these inclusion populations based upon the major mineralogy of quartz, alkali-feldspar, plagioclase, biotite, hornblende and apatite is only possible via analysis of large data sets. Clearly this is not possible for detrital grains, unless there is certainty that multiple grains are derived from a single melt. Impact melt compositions will vary depending on target rock lithologies. The bulk composition of impact melt sheets in the Hadean may have differed signicantly from the dioritic bulk composition of the Sudbury melt sheet (Lightfoot et al., 1997), particularly if the Hadean crust was basaltic (e.g. Kramers, 2007). However, dierentiation of basaltic melt sheets would produce signicant volumes of melt of intermediate to felsic composition (Grieve et al., 2006) and inevitably, according to
Relative frequency (%)
22 18 14 10 6 2 16 12 8 4 12 8 4 12 8 4 16 12 8 4 0
A) Sudbury norite (n = 90)
680 C titanium thermometry peak of >3.9 Ga zircons cannot be explained by zircons crystallized in large impact melt sheets. ACKNOWLEDGMENTS We thank P. Lightfoot and E. Tremblay for assistance with eldwork in Sudbury, and S. Kearns for help with electron microbeam techniques. This study was supported by a NERC Studentship to J. Darling, the Geological Society of America Eugene M. Shoemaker Award, and by Vale Inco. C. Storey acknowledges NERC Fellowship NE/D008891/1. The manuscript beneted from reviews by L.A. Coogan and two anonymous reviewers and discussions with H. Marschall. References
B) Sudbury granophyre (n = 46)
C) Mafic (n = 279)
D) Granitic (n = 81)
E) >3.9Ga (n = 191)
600 700 800 900 1000 Temp (C)
Figure 4: Titanium in zircon temperature probability distributions for various suites of rocks. a) and b) are data from the main Sudbury lithologies. c) Complilation of anorthosites, gabbros, norites and diorites from Fu et al. (2008) and Coogan and Hinton (2006). d) compilation of granites and granodiorites from Fu et al. (2008). e) Compilation of >3.9 Ga Yilgarn zircons from Watson and Harrison (2006) and Fu et al. (2008). The bimodal temperature distribution of Lower Unit zircons likely represents a sampling artifact, reecting higher zircon crystallization temperatures of basal Lower Unit samples.
our ndings, a wide range of zircon crystallization temperatures and compositions. As such the highly dierentiated nature of the Sudbury melt sheet is considered to provide broad constraints on the range of zircon crystallization temperatures and compositions likely in such settings. We conclude that titanium in zircon crystallization temperatures broadly correlate with magmatic dierentiation, which in Sudbury has reT sulted in systematic variations in T ziri throughout the melt sheet stratigraphy. Zircons in various mac lithologies from the melt sheet crystallized in residual liquids of granitic composition, producing inclusion assemblages that are remarkably similar to those reported for the ancient Yilgarn zircons. This indicates that it remains dicult to use inclusion assemblages and REE as a discriminator of the source of detrital zircons. Interpretation of source rock characteristics of the >3.9 Ga zircons based upon Ti thermometry is also somewhat ambiguous. However, assuming that the highly dierentiated Sudbury melt sheet oers a T representative spectrum of T ziri in such settings, the 115
Amelin, Y., Lee, D., Halliday, A., Pidgeon, R., 1999. Nature of the Earths earliest crust from hafnium isotopes in single detrital zircons. Nature 399 (6733), 252255. Cavosie, A., Wilde, S., Liu, D., Weiblen, P., Valley, J., 2004. Internal zoning and U-Th-Pb chemistry of Jack Hills detrital zircons: a mineral record of early Archean to Mesoproterozoic (4348-1576 Ma) magmatism. Precambrian Research 135 (4), 251279. Coogan, L. A., Hinton, R. W., 2006. Do the trace element compositions of detrital zircons require Hadean continental crust? Geology 34 (8), 633. Corfu, F., Lightfoot, P. C., 1996. U-Pb geochronology of the Sublayer environment, Sudbury Igneous Complex, Ontario. Economic Geology 91 (7), 12631269. Davis, D. W., 2008. Sub-million-year age resolution of Precambrian igneous events by thermal extraction-thermal ionization mass spectrometer Pb dating of zircon: Application to crystallization of the Sudbury impact melt sheet. Geology 36 (5), 383386. Fu, B., Page, F. Z., Cavosie, A. J., Fournelle, J., Kita, N. T., Lackey, J. S., Wilde, S. A., Valley, J. W., 2008. Ti-in-zircon thermometry: applications and limitations. Contrib Mineral Petrol 156 (2), 197215. Ghiorso, M., Sack, R. O., 1995. Chemical mass-transfer in magmatic processes .4. a revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated-temperatures and pressures. Contributions To Mineralogy and Petrology 119 (2-3), 197212. Grieve, R., Cintala, M. J., Therriault, A., 2006. Large-scale impacts and the evolution of the Earths crust: The early years. In: Reimold, W., Gibson, R. (Eds.), Processes on the Early Earth. Geological Society of America, pp. 2331. Grieve, R. A. F., Cintala, M. J., 1992. An analysis of dierential impact-melt crater-scaling and implications for the terrestrial impact record. Meteoritics 27 (5), 526538. Harrison, T., Schmitt, A., McCulloch, M., Lovera, O., 2008. Early ( 4.5 Ga) formation of terrestrial crust: Lu-Hf, 18O, and Ti thermometry results for Hadean zircons. Earth and Planetary Science Letters 268, 476486. Harrison, T., Watson, E., Aikman, A. B., 2007. Temperature spectra of zircon crystallization in plutonic rocks. Geology 35 (7), 635638. Hayden, L. A., Watson, E. B., 2007. Rutile saturation in hydrous siliceous melts and its bearing on Ti-thermometry of quartz and zircon. Earth and Planetary Science Letters 258 (3-4), 561568. Hopkins, M., Harrison, T. M., Manning, C., 2008. Low heat ow inferred from greater than 4 Gyr zircons suggests Hadean plate boundary interactions. Nature 456 (7221), 493496. Hoskin, P., Ireland, T., 2000. Rare earth element chemistry of zircon and its use as a provenance indicator. Geology 28 (7), 627630.
Kamber, B., 2007. The enigma of the terrestrial protocrust: Evidence for its former existence and the importance of its complete dissapearance. Developments in Precambrian Geology 15, 7589. Kramers, J. D., 2007. Hierarchical Earth accretion and the Hadean eon. J Geol Soc London 164, 317. Krogh, T. E., Davis, D., Corfu, F., 1984. Precise U-Pb zircon and baddeleyite ages for the Sudbury area. The Geology and Ore Deposits of the Sudbury Structure Special Volume 1, 431446. Krogh, T. E., McNutt, R. H., Davis, G., 1982. Two high precision U-Pb ages for the Sudbury Nickel Irruptive. Canadian Journal of Earth Sciences 19, 723728. Lightfoot, P. C., Doherty, W., K.Farrell, Keays, R. R., Moore, M. L., Pekeski, D., 1997. Geochemistry of the Main Mass, Sublayer, Osets and inclusions from the Sudbury Igneous Complex, Ontario. Ontario Geological Survey, Open File Report 5959. Lightfoot, P. C., Farrow, C. E. G., 2002. Geology, geochemistry, and mineralogy of the Worthington Oset Dike: A genetic model for oset dike mineralization in the Sudbury Igneous Complex. Economic Geology 97 (7), 14191446. Lightfoot, P. C., Zotov, I. A., 2005. Geology and geochemistry of the Sudbury Igneous Complex, Ontario, Canada: Origin of nickel sulde mineralization associated with an impactgenerated melt sheet. Geology of Ore Deposits 47 (5), 349 381. Lissenberg, C. J., Rioux, M., Shimizu, N., Bowring, S. A., Mevel, C., 2009. Zircon dating of oceanic crustal accretion. Science 323 (5917), 10481050. Maas, R., Kinny, P. D., Williams, I. S., Froude, D. O., Compston, W., 1992. The Earths oldest known crust - a geochronological and geochemical study of 3900-4200Ma old detrital zircons from Mt Narryer and Jack Hills, Western Australia. Geochimica et Cosmochimica Acta 56 (3), 12811300. Menneken, M., Nemchin, A. A., Geisler, T., Pidgeon, R. T., Wilde, S. A., 2007. Hadean diamonds in zircon from Jack Hills, Western Australia. Nature 448 (7156), 917925. Mungall, J. E., Ames, D. E., Hanley, J. J., 2004. Geochemical evidence from the Sudbury Structure for crustal redistribution by large bolide impacts. Nature 429 (6991), 546548. Ostermann, M., Scharer, U., Deutsch, A., 1996. Impact melt dikes in the sudbury multi-ring basin (canada): Implications from uranium-lead geochronology on the foy oset dike. Meteorit Planet Sci 31 (4), 494501. Ryerson, F., Watson, E., 1987. Rutile saturation in magmas implications for Ti-Nb-Ta depletion in island-arc basalts. Earth and Planetary Science Letters 86 (2-4), 225239. Spray, J. G., Butler, H. R., Thompson, L. M., 2004. Tectonic inuences on the morphometry of the Sudbury impact structure: Implications for terrestrial cratering and modeling. Meteoritics and Planetary Science 39 (2), 287301. Wark, D. A., Miller, C. F., 1993. Accessory mineral behavior during dierentiation of a granite suite - monazite, xenotime and zircon in the Sweetwater Wash Pluton, Southeastern California, USA. Chemical Geology 110 (1-3), 4967. Watson, E. B., Harrison, T., 2005. Zircon thermometer reveals minimum melting conditions on earliest Earth. Science 308 (5723), 841844. Watson, E. B., Harrison, T. M., 1983. Zircon saturation revisited - temperature and composition eects in a variaty of crustal magma types. Earth and Planetary Science Letters 64 (2), 295304. Watson, E. B., Harrison, T. M., 2006. Response to comments on Zircon thermometer reveals minimum melting conditions on earliest Earth. Science 311 (5762). Wilde, S. A., Valley, J. W., Peck, W. H., Graham, C. M., 2001. Evidence from detrital zircons for the existence of continental crust and oceans on the Earth 4.4 Gyr ago. Nature 409 (6817), 175178. Zieg, M. J., Marsh, B. D., 2005. The Sudbury Igneous Complex: Viscous emulsion dierentiation of a superheated impact melt sheet. Bulletin of the Geological Society of America 117 (11-12), 14271450.
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7 Summary and future directions

A number of signicant ndings have been made in this investigation that reveal new insights into the formation and evolution of the Sudbury impact melt sheet, as well as the processes of zircon crystallisation. The aims of this chapter are to summarise the key ndings made and highlight directions for future research.
7.1
Melt sheet evolution
Pb isotopes have proven to be a useful tool in identifying chemical variability within the Main Mass and Oset Dykes. The results presented in Chapters 4 and 5 emphasise that the melt sheet is heterogeneous at a range of scales. Of particular importance is the observation that not only are isotopic dierences preserved between the North and South Ranges (Cooper, 2000; Dickin et al., 1999, 1996), but that signicant variations occur both laterally and vertically throughout the Main Mass, as well as between Oset Dykes, from the same side of the Complex. It is clear that the various units of the melt sheet have not been eciently homogenised by convection over time, as has previously been suggested (Dickin et al., 1999). Instead a dynamic system is apparent, with heterogeneity present early in the history of the melt sheet, as revealed by the Oset Dykes, through to the nal products of silicate crystallisation. Importantly, the Pb isotope systematics of Oset Dyke quartz diorites, together with considerations of previously published trace element and Sr-Nd isotope data, demonstrate that such heterogeneity can be accounted for by mixing of locally exposed target lithologies. Particularly given the initially superheated nature of the melt sheet, the assimilation of fallback breccias, entrained clasts and footwall rocks provide mechanisms to maintain or develop heterogeneity despite probable vigorous thermal convection (Zieg and Marsh, 2005). However, a key question remains to what extent the products of impact melting were homogenised during crater formation. Theoretical considerations on the violent movement and shearing of superheated, low viscosity, shock melt suggest that the initial products of impact melting would have been homogenised during collapse of the transient cavity (Phinney and Simonds, 1977; Simonds and Kieer, 1993). The heterogeneities identied in early formed Oset Dyke lithologies, together with the distinct isotopic compositions of North and South Range Main Mass rocks, indicates that this may not be the case. Without better constraints upon the timing of Oset Dyke emplacement, it is not clear whether further resolution of this issue will be possible in Sudbury. Investigation 117
Summary and future directions
is required of chemical variability in coherent impact melt bodies from smaller craters, where there is less potential for post crater-formation melt interaction and assimilation of target rocks. From the terrestrial crater record, the Morokweng (Koeberl et al., 1997a), Chesapeake Bay (Wittmann et al., 2009) and Chixculub (Schuraytz et al., 1994) structures are known to contain such units of interest, and also have variable target lithologies. It is clear from the ndings of this study that compositionally variable target rocks play a key role in controlling the geochemistry of the melt sheet, with both spatial and temporal variations common. In Chapter 4 it was shown that signicant lateral variations in Pb isotopes occur over distances of a few kilometers. Preliminary investigations of major and trace elements in the same region suggest that similar variations occur (e.g. SiO2 , La/Y), although they are more dicult to resolve given analytical uncertainties. Signicant geochemical dierences between Main Mass and Oset Dyke samples from the North and South Ranges (e.g. Sr, Sc) are also well documented (Lightfoot et al., 1997a). Collectively, these observations indicate that impact melt sheets are not as ecient at mixing as previously suggested. This may have signicant implications for the eects of intense post-accretionary bombardment of early planetary crusts.
7.2
Origin of the melt sheet
Reconciling the geochemical characteristics of the melt sheet in Sudbury with mathematical models of impact processes has revealed new insights into the Sudbury event. Chapter 5 shows that the main geochemical characteristics of the melt sheet can be explained by mixing of locally exposed target lithologies. An upper-mid crustal source for the melt sheet is evident, a nding that conicts with previous predictions of deep seated crustal melting from impact modelling. An oblique impact can accommodate shallower melting, however further research is required in order to consolidate an oblique impact model with the melt volume in Sudbury. Firstly, there are considerable discrepancies between estimates of impact melt volume, and the various approaches should be reviewed in light of ongoing developments in impact research. Secondly, it is possible that given the Sudbury impact melt volume estimate of Pope et al. (2004), a high velocity and low density impactor (comet) may be required. A systematic study of refractory platinum group element abundances in the Onaping Formation, as well as distal ejecta (Pufahl et al., 2007) is required to test whether such an impactor was likely. Previous impact models invoking melting to depths that approached the maximum transient cavity depth of 30 km (Deutsch et al., 1995; Grieve et al., 1991; Mungall et al., 2004), infer that Sudbury sized impact events would have profoundly disturbed 118
7.3. IMPLICATIONS FOR SULPHIDE ORE FORMATION the compositional layering of the continental crust. It has been dicult to reconcile such models with the fact that there is no record of decompressive mantle melting in the Sudbury area around the time of impact, or signicant mantle contribution to the melt sheet (e.g. Lightfoot et al., 2001; this study) . The recognition of an upper to mid-crustal source for the melt sheet, and re-evaluating the Sudbury event in terms of an oblique impact, it is evident that the excavation and melting depths are signicantly shallower than previously considered. The compositional layering of the crust would not have been inverted, and formation of the melt sheet without signicant mantle contribution becomes conceptually easier.
7.3
Implications for sulphide ore formation
The ndings of this study have potentially signicant implications for the formation of sulphide ore deposits in Sudbury. It has previously been recognised that sulphides segregated from the Main Mass and accumulated at the base of the melt sheet (Keays and Lightfoot, 2004), and that the location of ore deposits was controlled by: (a) gravitational and convective accumulation of sulphide in depressions in the basal contact and (b) the thickness of the Lower unit of the Main Mass (Keays and Lightfoot, 2004). In Chapter 4 it is shown that the formation of melt cells of diering composition may have also had a signicant aect on the sulphide segregation history of the Main Mass. Timing of sulphide segregation was estimated by comparing the isotopic composition of ores with that of the overlying Lower Unit stratigraphy, and was found to be highly variable. Early sulphide saturation, at temperatures likely in excess of the Lower Unit liquidus, formed much of the massive Oset Dyke and Contact Sublayer mineralisation, as highlighted by data from the Creighton 402 orebody in the Creighton embayment. However, given that the range of initial Pb isotopes in ores have a similar range to the Lower Unit stratigraphy, it is apparent that sulphide segregation occurred over a protracted period. Those segments in which accumulated basal sulphide has high Pb isotope values, consistent with early segregation, also have the strongest chalcophile element depletion signatures. Given that those sulphides that segregate early will have access to the most chalcophile element enriched melt sheet, it is predicted that these ores will also have the highest metal concentrations (tenor). Preliminary results suggest that this is the case, although further research is required to test this relationship. In particular, the eects of sulphide fractionation on the Ni, Cu and PGE concentrations of samples analysed must be carefully considered. That the geochemical characteristics of the melt sheet can be accommodated by melting of locally exposed footwall rocks also provides constraints upon sulphide ore 119
Main Mass
Worthington Offset Dyke

N
Creighton pluton Elliot Lake Gp. Hough Lake Gp. Nipissing mafic suite
10 km
Figure 7.1: Simplied geological map and sampling localities of sulphide ores from the Copper
Cli and Worthington Oset Dykes
formation. In Chapter 5 it is shown that mac target rocks may be fundamental to raising the metal budget of the melt sheet. Accordingly, the spatial distribution of such mac bodies may inuence the sulphide ore potential around the melt sheet. In order to further investigate this concept, it is necessary to better constrain the isotopic and Ni, Cu and PGE compositions of the various target rocks. This would allow for a more detailed and accurate assessment of the relative contributions of diering target rock groups around the melt sheet. Furthermore, the potential aects of varying target rock contributions to the melt sheet on sulphur saturation (e.g. Fe and S content) require investigation.
7.3.1
Distinct sources for ores in dierent Oset Dykes?
If the distribution of target rocks is a fundemental control on the Ni-Cu-PGE contents of the melt sheet, it would be expected that ores from similar environments, but dierent locations (for example within the South Range) would have distinct crustal sources. Accordingly, inclusion and sulphide bearing quartz diorites were sampled along both the Worthington and Copper Cli Oset Dykes (Figure 7.1). Preliminary data clearly show dierent model initial Pb isotopic compositions from the respective Oset Dykes (Figure 7.2; data in Appendix Table 8.3), consistent with distinct sources. Such studies are required from dierent environments in the melt sheet and should focus upon producing age corrected Pb isotope data (i.e. corrected with measured U-Th-Pb ratios) in order to resolve potential dierences in target rock precursors. 120
7.4. ZIRCONS IN IMPACT MELTS
6! 5! 4! Worthington! Copper Cliff!
n!
3! 2! 1! 0! 15.32!15.34!15.36!15.38! 15.4! 15.42!15.44!15.46!15.48! 15.5! 15.52!

207Pb/204Pb m!
Figure 7.2: Histogram of model initial Pb isotope ratios (calculated as Chapter 4) for sulphide ore samples from inclusion bearing quartz diorites of the Worthington and Copper Cli Oset Dykes. Uncertainty is within the width of the columns.
7.4
Zircons in impact melts
The characterisation of zircons from throughout the Sudbury melt sheet revealed a number of signicant ndings: 1. Titanium in zircon crystallisation temperatures correlate with indexes of magmatic dierentiation. 2. The rare earth element concentrations of zircons from felsic and mac impact melts cannot easily be distinguished. 3. Inclusion populations in zircons from mac rocks in Sudbury are of typically granitic mineralogies. These ndings are particularly important for the interpretation of the source of detrital zircons. In particular, the REE compositions and inclusion populations of Sudburys zircons are very similar to those described in Hadean zircons from the Yilgarn Craton. As such, the characteristics of the Hadean zircons are consistent with crystallization from more mac melts than previously recognized, although high crystallization temperature distributions of Sudbury zircons indicate that impact melt sheets were not a dominant source for the grains older than 3.9 Ga. Further work is required to characterise inclusion populations from the impact melt sheet zircons, in order to test whether characteristic phases are present. For example, diamonds are known from a number of terrestrial impact structures, including Sudbury (Hough et al., 1995; Koeberl et al., 1997b; Langenhorst et al., 1998, 1999; Masaitis et al., 1999), and are likely to be stable in igneous rocks for sucient time to be incorporated in crystallising zircon (Collerson et al., 2000; Haggerty, 1999; Korsakov et al., 2004; Wirth 121
and Rocholl, 2003; De Corte et al., 2000). Thus far, electron microbeam techniques have principally been used for inclusion characterisation. Further developments and more detailed investigations will require the application of spectroscopic methods such as micro-Raman spectroscopy.
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134
8 Appendices
8.0.1 Supplementary materials for Darling et al. (2009) Impact melt sheet zircons and their implications for Hadean crustal processes; Geology; v. 37; no.10; p. 927-930
135
Appendices
RSP (m) Basal norite 0
Sample
Grain/ Spot 16 19 20 28 31 33 35 38 39 42 45 19 20 24 30 30B 31 34A 34B 34C 45 45 46 46B 47 49A 49B 49C 50A 50B 52 60 61 61B 63 1 18 2 20 23 24 26 27 29 3 7 27 28 29 33 49 56 74 39 45 47 5
HfO2
Th U Th/U (ppm) (ppm) 381 479 276 344 226 316 458 460 426 441 355 287 263 548 765 330 357 735 489 347 416 516 254 308 544 372 721 549 628 550 791 764 423 254 470 257 364 179 422 303 398 495 217 349 337 141 861 951 1101 909 1284 1035 2263 751 841 964 1093 465 502 291 366 277 384 469 462 433 485 364 224 190 536 562 273 263 705 502 259 329 498 156 301 490 277 620 563 619 526 787 590 400 211 475 334 620 275 761 383 733 915 361 600 484 150 1364 1451 1475 1199 1744 2352 3831 1349 1751 2394 2340 0.82 0.95 0.95 0.94 0.82 0.82 0.98 1.00 0.98 0.91 0.98 1.28 1.38 1.02 1.36 1.21 1.36 1.04 0.97 1.34 1.26 1.04 1.63 1.02 1.11 1.34 1.16 0.98 1.01 1.05 1.01 1.29 1.06 1.20 0.99 0.77 0.59 0.65 0.55 0.79 0.54 0.54 0.60 0.58 0.70 0.94 0.63 0.66 0.75 0.76 0.74 0.44 0.59 0.56 0.48 0.40 0.47
Ti 2sd (ppm) 30.0 41.6 36.7 28.4 30.8 32.8 30.2 36.5 31.1 32.1 35.3 33.7 31.8 37.5 35.8 35.5 35.9 30.0 38.6 36.5 38.3 39.8 33.0 29.4 36.4 39.8 33.0 38.7 40.3 37.7 36.9 33.2 31.2 29.2 36.0 30.7 31.6 32.9 32.9 35.8 32.4 38.6 29.2 32.8 32.1 32.0 19.8 16.5 23.3 21.0 20.1 27.8 15.6 26.5 20.7 22.2 33.7 3.4 3.6 3.7 3.6 4.4 3.7 3.5 4.0 3.6 1.6 1.8 1.4 1.4 1.5 1.7 1.9 1.5 1.2 1.6 2.0 1.5 2.4 1.7 1.7 1.9 2.2 1.8 2.2 1.6 1.6 1.4 1.9 1.7 1.7 2.0 2.1 2.2 2.9 2.2 2.5 2.2 2.7 2.0 2.3 2.2 2.2 1.2 1.0 1.5 1.6 1.1 1.6 0.9 1.2 1.1 1.3 2.7
T 2sd ( C) 848 884 870 842 850 857 848 869 852 855 865 860 854 872 867 866 867 848 876 869 875 879 858 846 869 879 858 876 880 873 870 859 852 845 868 850 853 858 858 867 856 875 845 857 855 855 805 787 821 811 806 839 782 834 809 816 860 18 16 17 19 21 18 18 18 19 12 12 11 11 11 12 12 11 11 11 13 11 13 12 13 12 13 13 13 11 11 11 13 12 13 13 14 14 16 14 14 14 15 14 14 14 14 12 12 13 14 12 12 12 11 12 12 15
144IBNR
98
144BNR
304
JDSIC0702
874
JDSIC0701
1070
144NR
0.795 0.842 0.785 0.912 0.828 0.781 0.800 0.825 0.806 0.797 0.839 0.906 0.888 0.911 0.851 0.884 0.901 0.901 0.808 0.901 0.900 0.890 0.890 0.808 0.911 0.904 0.808 0.841 0.900 0.841 0.884 0.860 0.832 0.832 0.828 0.921 0.849 0.748 0.751 0.884 0.806 0.853 0.851 0.881 0.906 0.883 0.957 0.952 0.957 0.980 0.965 0.814 0.840 0.864 0.895 0.893 0.874
136
RSP (m) Norite 1070
Sample
Grain/ Spot 50 51 55A 55B 55C 61 65 19 22 28 39 46 68A 68B 68C 69A 69B 1 7 10 18A 18B 31 35 37 48A 48B 49 50 42 44 45 49 50A 50B 51 53 54 56 58 63 76 80 85 87 97 98 99A 10 13 15 18 20 28 29
HfO2
Th U Th/U (ppm) (ppm) 727 780 610 568 673 621 589 564 686 969 639 669 725 650 490 773 767 1080 550 1103 794 940 1143 1020 965 1090 888 1226 1396 162 292 71 188 254 128 109 166 116 184 187 165 164 195 168 175 144 173 200 1070 4700 1787 2851 507 1893 1168 1197 1543 1122 1034 1268 992 1033 551 773 2052 975 906 1203 1147 528 971 1027 2069 852 1623 781 1177 2245 1920 1840 2124 1297 2404 2355 182 407 113 221 268 184 163 201 147 218 228 189 130 142 121 160 111 146 187 1459 4235 2151 3022 938 2306 1634 0.61 0.51 0.54 0.55 0.53 0.63 0.57 1.02 0.89 0.47 0.66 0.74 0.60 0.57 0.93 0.80 0.75 0.52 0.65 0.68 1.02 0.80 0.51 0.53 0.52 0.51 0.68 0.51 0.59 0.89 0.72 0.63 0.85 0.95 0.70 0.67 0.83 0.79 0.84 0.82 0.87 1.26 1.37 1.39 1.09 1.30 1.18 1.07 0.73 1.11 0.83 0.94 0.54 0.82 0.71
Ti 2sd (ppm) 20.1 15.6 16.9 15.2 15.0 17.0 19.1 19.7 21.6 25.5 14.0 12.3 20.9 19.4 14.5 19.9 19.8 16.7 9.4 12.3 12.4 11.7 18.9 17.5 16.6 16.1 16.2 16.2 15.4 13.3 12.0 13.5 12.1 13.5 17.4 19.5 16.1 13.4 14.1 16.2 15.2 19.4 17.2 18.7 16.3 16.4 16.5 13.7 8.6 10.5 7.9 7.0 8.6 9.3 7.0 1.2 1.0 1.0 0.9 0.9 1.0 1.1 2.0 2.1 1.4 0.9 0.8 1.2 1.2 0.9 1.1 1.1 1.6 0.8 1.1 1.4 1.1 1.2 1.6 1.5 1.3 1.2 1.2 1.9 1.5 2.3 1.7 1.7 1.6 1.6 1.7 1.7 1.7 1.8 1.6 1.7 1.3 1.5 1.4 2.0 1.2 1.4 1.8 1.2 1.3 0.7 0.9 0.8 0.9 0.8
T 2sd ( C) 806 781 789 779 778 790 801 804 814 830 772 759 810 803 775 805 805 788 736 760 760 755 800 793 788 785 785 786 781 766 757 768 758 768 792 803 784 767 772 786 779 803 791 799 786 786 787 770 727 746 721 710 728 735 710 12 12 12 11 11 12 12 16 16 12 12 11 12 12 11 12 11 15 13 14 15 14 12 15 14 13 13 13 17 16 22 17 18 17 14 15 16 17 17 15 16 12 14 13 17 13 14 18 17 16 13 15 13 14 14
144NR
1384
144MLNR
1614
JDSIC0708
0.940 0.936 0.862 0.862 0.873 0.985 0.901 0.863 0.851 0.812 1.063 1.028 1.001 0.971 1.017 0.955 0.979 0.927 1.153 1.145 1.169 1.169 0.882 0.848 0.940 0.940 0.940 0.940 0.940 0.694 0.764 0.750 0.739 0.739 0.745 0.741 0.736 0.754 0.734 0.735 0.733 0.744 0.746 0.761 0.778 0.740 0.711 0.710 1.082 1.006 1.058 0.990 1.236 0.957 0.966
Granophyre 2942
144GRAN1
2942
144GRAN1
3300
JDSIC0704
137
Appendices
RSP (m) Granophyre 3300
Sample
Grain/ Spot 29 30 36 36 37 40 5 66A 66B 67A 67B 8 9 9 13A 13B 13C 1A 1B 4 A1a A1b A1c A7a A7b B11 B12 E8 F1 F2 E9 E5
HfO2
Th U Th/U (ppm) (ppm) 941 2968 1689 2089 2564 3351 3133 1857 1431 1339 2502 1649 2374 2817 312 311 153 2381 3222 1080 1500 2055 3640 2961 2103 2831 1437 1699 208 452 1472 2523 1072 2804 2013 2216 2829 3375 2549 1775 1298 983 2353 1493 2944 3883 426 352 112 3823 3964 954 662 826 1202 1095 821 1749 980 727 179 334 683 1015 0.88 1.06 0.84 0.94 0.91 0.99 1.23 1.05 1.10 1.36 1.06 1.10 0.81 0.73 0.73 0.88 1.37 0.62 0.81 1.13 2.27 2.49 3.03 2.70 2.56 1.62 1.47 2.34 1.16 1.35 2.16 2.49
Ti 2sd (ppm) 11.3 9.6 7.9 10.7 11.0 7.2 9.6 6.9 9.4 7.7 7.5 12.7 6.5 11.0 14.8 15.7 15.6 8.8 8.4 7.2 10.6 12.0 15.1 13.4 12.9 13.3 21.5 16.6 19.8 17.7 10.9 12.5 2.2 1.2 0.9 1.3 1.2 1.9 1.8 1.1 0.9 1.1 1.1 1.6 0.7 1.0 1.4 1.2 1.2 1.2 1.6 1.4 1.2 1.1 1.3 0.8 1.3 1.4 1.4 1.4 1.7 1.5 1.2 1.4
T 2sd ( C) 752 737 720 747 750 712 737 709 735 719 717 762 704 749 777 782 782 730 726 713 746 757 778 767 763 767 813 788 805 794 749 761 22 16 15 16 15 26 21 18 14 17 17 17 14 14 15 13 13 16 20 21 15 14 14 11 15 15 13 14 15 14 16 16
JDSIC0704
3800
JDSIC0705
0.966 0.777 0.784 0.784 0.821 0.921 0.763 0.768 0.722 0.951 0.951 0.887 0.812 0.721 0.806 0.772 0.814 0.763 0.763 0.763 0.981 0.958 0.930 0.871 0.871 1.070 0.852 0.952 0.820 0.967 0.952 0.862
Quartz diorite WOQD1
Table 8.1: Summary of HfO2 , Th, U and Ti concentrations for zircons from throughout the Sudbury impact melt sheet stratigraphy.
138
Figure 8.1: Cathodoluminescence images of representative zircons from each studied unit. Ti Laser spot positions and corresponding measured Tzir are shown, along with identied inclusions. K-feld - K-feldspar; Qtz - quartz; plag - plagioclase; bt - biotite; ap - apatite.
La Basal Lower Unit IBNR 0.6

1 0.5
Ce
Pr
Nd Sm 14
3
Eu 1.6
0.3
Gd Tb 67
12
Dy 224
43
Ho 75
14
Er 316
60
Tm 67
11
Yb 596
92
Lu 86
15
Hf 9668
477
n 14 12
28 1.2
2 6 0.4 1.1
17
3
19
3
BNR
1
2.0
1.4
33 1.4
14
9
16
7
0.9
0.6
50
15
18
4
217
48
72
14
302
55
73
12
762
113
80
12
8951
386
Lower Unit JDSIC0701

1
3.7 103 3.1

3.3 4.2 3.0 0.2 22 60 79 81 2.1 4.9 1.3 0.8
31
14
36 11.6 106
11 28 9.6 12.7 2.2 1.3 37 75 130 100
35
12
393 121
130 241 371 350 39 71 110 100
470 107 1081

148 257 399 364 33 51 68 76 313 434 536 683
99
29 45 76 65
5862
596
5 10 8 5
144NR
1
12.4 175 9.3 2.0 145 2.1 0.3 129 1.4
81
39
71 22.3 174 43
22
47
22
487 143 554 168 667 204
532 108
959 108 10166

1354 1934 1676
144MLNR
1
27
11
4.2 167 2.1 169
51
36
634 134 1261 132 10711 785 172 1585 160 10090
JDSIC0708
1
25
14
46
29
58
32
Upper Unit 144GRAN1

1
0.9
1.7 0.8
13 0.7
4 64 0.6 0.7
8
4
10
3
0.8
0.3 0.7
48
16 108
14
4 36
163
50 426
56
17 137
234
66 530
51
14 107
458
119 871
65
15 100
8689
181
12 12
JDSIC0704
1
0.7 115 1.5
24
8
52
20
1.6 280
94 1159 382 1543 331 2825 325 11129

1708
Quartz Diorite WOIQD 5.8

1 5.3
72 2.2
46 1.6
18
10
17
12
3.2
1.3
76
68
23
20
271
236
91
74
378
290
83
58
759 108 10636

473 54 668
Table 8.2: Mean rare earth element concentrations (ppm) for zircons from studies samples.
139
Appendices
100000.0!
Basal Lower Unit!

10000.0! 1000.0! 100.0! 10.0! 1.0! 0.1! 100000.0! 10000.0! 1000.0! 100.0! 10.0! 1.0! 0.1! 100000.0! 10000.0! 1000.0! 100.0! 10.0! 1.0! 0.1! 100000.0! 10000.0! 1000.0! 100.0! 10.0! 1.0! 0.1!
Lower Unit!
Upper Unit!
Quartz diorite!
!"#
$%#
&'#
()#
*+#
,-#
.)#
/0#
12#
34#
,'#
/+#
50#
!-#
Figure 8.2: Chondrite normalised rare earth element proles for zircons analysed in this study. Chondrite values are from (McDonough and Sun, 1995). Zircons from each unit display a wide range of REE concentrations and magnitudes of Ce and Eu anomalies. The Lower Unit zircons with small to no Eu anomalies are from the top of this unit and have similar morphologies and zonation patterns to other Lower Unit zircons. The three QD zircons that have no Eu anomalies show signs of alteration such as spongy textures and no zonation in CL images. 140
8.0.2
Supplementary material to Chapter 7
141
Oset WO WO WO WO WO WO WO WO WO WO WO WO WO WO CCO CCO CCO CCO CCO CCO CCO CCO JD09SIC01 JD09SIC02 JD09SIC03 JD09SIC04 JD09SIC05 JD09SIC06 JD09SIC07 865OB mix mix mix mix mix mix mix mix 16.732 16.008 16.684 15.710 15.797 15.839 16.247 17.274 0.003 0.003 0.003 0.002 0.002 0.003 0.003 0.003 15.553 15.441 15.518 15.388 15.379 15.371 15.452 15.585 JD07SIC19A JD07SIC0719B JD07SIC0720 JD07SIC0721A JD07SIC0721B JD07SIC0722A JD07SIC0722B JD07SIC0723 JD07SIC0727 RX182907 WOIQD1 WOIQD2A WOIQD2B WOMS1 po cpy po cpy Po Po cpy mix po po po cpy po po 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.004 0.003 0.003 0.003
Sample ID
Sulph.
206 Pb/ 204 Pb 21.370 19.330 18.670 18.371 19.872 19.364 16.990 22.000 19.442 19.091 24.784 19.720 20.600 19.630
207 Pb/ 204 Pb 16.176 15.902 15.827 15.770 15.951 15.860 15.601 16.238 15.859 15.873 16.537 15.944 16.029 15.937
2 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.004 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003
208 Pb/ 204 Pb 44.766 40.779 39.367 39.531 42.176 41.734 37.722 44.059 43.324 39.321 46.435 40.110 41.315 39.706
2 0.013 0.012 0.011 0.011 0.012 0.012 0.011 0.013 0.012 0.011 0.013 0.011 0.012 0.011 36.934 35.917 36.763 35.635 35.843 36.147 36.416 37.612 0.011 0.010 0.011 0.010 0.010 0.010 0.010 0.011
208 Pb/ 206 Pb 2.095 2.110 2.109 2.152 2.122 2.155 2.220 2.003 2.228 2.060 1.874 2.034 2.006 2.023
0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000 0.001 0.000 0.000 0.000 0.000 0.000 2.207 2.244 2.203 2.268 2.269 2.282 2.241 2.177
207 Pb/ 204 Pbm 15.508 15.465 15.465 15.442 15.452 15.419 15.428 15.499 15.409 15.463 15.483 15.463 15.448 15.466
0.005 0.005 0.004 0.004 0.005 0.005 0.004 0.005 0.005 0.005 0.005 0.005 0.005 0.005
0.001 0.001 0.001 0.001 0.001 0.001 0.001 0.001
15.409 15.380 15.380 15.360 15.341 15.329 15.364 15.381
0.006 0.005 0.004 0.005 0.003 0.004 0.003 0.005
Appendices
Table 8.3: Pb isotope data for sulphide seperates from inclusion bearing quartz diorite phases of the Worthington (WO) and Copper Cli (CCO) Oset Dykes. The analysed sulphide (Sulph.) phases are specied. Model initial Pb isotope ratios ( 207Pb/ 204Pbm ) were calculated following the method of Darling et al. (2010)
142

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Formation and evolution of the Sudbury impact melt sheet

Department of Earth Sciences University of Bristol January 2010

Word count ca. 35000

All Rights Reserved, 2010

Geology of the Sudbury Structure 2.2.1 2.2.2 2.2.3 2.2.4 2.2.5

4 Isotopic heterogeneity in the Sudbury impact melt sheet 4.1 4.2

5 Pb isotope systematics of the Oset Dykes 5.1 5.2

6 Impact melt sheet zircons 6.1

Zircons in impact melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121 123 135

ratios of NIST SRM 612 from this study . . . . . . . . . 52 xii

plotted against whole rock assay data (from

plotted against the Ni content of pyrrhotite

Author contributions to published papers

Embayment Footwall Breccia

Onwatin & Chelmsford Formations South Range

Sudbury Igneous Complex (SIC) Sudbury Structure

2 The geology of the Sudbury Structure

Regional geological setting

The Superior Province

The geology of the Sudbury Structure

Phanerozoic cover Synform Antiform Thrust fault Fault zone

2.1. REGIONAL GEOLOGICAL SETTING

The Southern Province

The geology of the Sudbury Structure

2.1. REGIONAL GEOLOGICAL SETTING

The geology of the Sudbury Structure

Geology of the Sudbury Structure

The Sudbury Igneous Complex

Grenville Front - frontal thrust

2.2. GEOLOGY OF THE SUDBURY STRUCTURE

Neoarchean Cartier batholith

Metavolcanic and metasedimentary rocks

Levack Gneiss Complex

Tonalitic-granodiorite and mafic-ultramafic gneisses

The geology of the Sudbury Structure

Chelmsford Fm. Onwatin Fm. Onaping Fm.

Post-impact basin fill Impactites (~1.4 km)

Middle Unit Lower Unit Sublayer

Melt sheet (~2.5 km)

Sudbury Breccia Offset Dykes

Fractured and shocked basement

2.2. GEOLOGY OF THE SUDBURY STRUCTURE

NORTH RANGE 2000

True Thickness (m)

Oxides + apatite + titanite Clinopyroxene

Biotite + primary amphibole

Orthopyroxene Quartz + granophyric intergrowths Plagioclase

The geology of the Sudbury Structure

The geology of the Sudbury Structure

(b) SR Sublayer (2 mm)

(c) NR basal Lower Unit

(d) NR Lower Unit

(e) Middle Unit

(f) Upper Unit

The geology of the Sudbury Structure

Proximal to the Main Mass

Distal from Main Mass

(a) Quartz diorite (QD)

(b) Inclusion bearing quartz diorite (IQD)

2.2. GEOLOGY OF THE SUDBURY STRUCTURE

olivine melanorite inclusion metapyroxenite inclusion melanorite pod melanorite pod

Sublayer Onaping Formation