Ultrahigh-Pressure Metamorphism: 25 Years After The Discovery Of Coesite And Diamond

Table of Contents

Cover Image

Front-matter

Copyright

Preface

List of Contributors

Reviewers

1. Frontiers of Ultrahigh-Pressure Metamorphism

1.1. Introduction

1.2. Main Achievements: 25 Years On

1.3. Further Directions

1.4. Looking Forward

2. Diamond–Lonsdaleite–Graphite Relations Examined by Raman Mapping of Carbon Microinclusions inside Zircon at Kumdy Kol, Kokchetav, Kazakhstan

2.1. Introduction

2.2. Geological Setting

2.3. Analytical Procedures

2.4. Results

2.5. Discussion

2.6. Conclusions

3. Diamond and Other Possible Ultradeep Evidence Discovered in the Orogenic Spinel-Garnet Peridotite from the Moldanubian Zone of the Bohemian Massif, Czech Republic

3.1. Introduction

3.2. Geological Settings and Some Backgrounds

3.3. Petrography and Mineral Chemistry

3.4. Experimental

3.5. Varying Crystallinity of Graphite

3.6. Diamond

3.7. Crystal Orientation Relationship Between Clinopyroxene Lamellae and Host Chromian Spinel

3.8. Discussion

3.9. Conclusions

4. Diamond Formation from Amorphous Carbon and Graphite in the Presence of COH Fluids

4.1. Introduction

4.2. Materials and Methods

4.3. Results

4.4. Discussion

5. Origin of High-Pressure Disordered Metastable Phases (Lonsdaleite and Incipiently Amorphized Quartz) in Metamorphic Rocks

5.1. Introduction

5.2. Quartz Incipiently Amorphized Under Pressure

5.3. Lonsdaleite

5.4. Discussion

5.5. Conclusion

6. Origin and Metamorphic Evolution of Garnet Clinopyroxenite from the Sulu UHP Terrane, China

6.1. Introduction

6.2. Geological Outline

6.3. Sample Description

6.4. Analytical Methods

6.5. Chemical Composition of Whole Rock

6.6. Mineral Composition

6.7. Mineral Lamellae in Clinopyroxene and EBSD Patterns

6.8. Pressure–Temperature Conditions

6.9. Discussion

6.10. Conclusions

7. The Correlation Between Raman Spectra and the Mineral Composition of Muscovite and Phengite

7.1. Introduction

7.2. Experimental Methods

7.3. Results

7.4. Discussion

7.5. Application

7.6. Conclusions

8. Increasing Chlorinity in Fluids Along the Prograde Metamorphic Path

8.1. Introduction

8.2. Geological Setting and Outcrop Description

8.3. Descriptions of Samples and Occurrence of Apatite

8.4. Compositions of Apatite and Phengite

8.5. P–T Conditions

8.6. Discussion

8.7. Conclusions

9. Trace Element and O-Isotope Composition of Polyphase Metamorphic Veins of the Ile de Groix (Armorican Massif, France)

9.1. Introduction

9.2. Geological Context

9.3. Analytical Techniques

9.4. Sampling

9.5. Petrology of the Veins

9.6. Host Rock Composition

9.7. Mineral Major and Trace Element Chemistry

9.8. Oxygen Isotope Compositions

9.9. Calculation of Fluid Trace Element Composition

9.10. Discussion

9.11. Conclusions

10. Geochronology of the Alpine UHP Rhodope Zone

10.1. Introduction

10.2. Overview of the Rhodope Zone

10.3. Selection of the Most Relevant Geochronological Data for the Rhodope Zone

10.4. Geochronological Data on Metamorphism

10.5. Premetamorphic Geochronological Data

10.6. Discussion

11. Coherence of the Dabie Shan UHPM Terrane Investigated by Lu–Hf and 40Ar/39Ar Dating of Eclogites

11.1. Introduction

11.2. Geological Setting and Sample Selection

11.3. Analytical Techniques

11.4. Results

11.5. Discussion

11.6. Conclusions

12. Distribution and Geological Position of High-/Ultrahigh-Pressure Units Within the European Variscan Belt

12.1. Introduction

12.2. Major Suture Zones in the European Variscan Belt

12.3. Bohemian Massif

12.4. Vosges and Schwarzwald

12.5. The French Massif Central

12.6. The Armorican Massif

12.7. Iberian Massif

12.8. Variscan HP Rocks in the External Crystalline Massifs and Occurring in the Alpine Nappe-Thrust Belt

12.9. Summary and Discussion

13. Ultramafic Cumulates of Oceanic Affinity in an Intracontinental Subduction Zone

13.1. Introduction

13.2. Samples

13.3. Analytical Techniques

13.4. Whole-Rock Chemistry

13.5. Mineral Chemistry

13.6. Discussion

13.7. Conclusions

14. Very High-Pressure Epidote Eclogite from Ross River Area, Yukon, Canada, Records Deep Subduction

14.1. Introduction

14.2. Tectonic Setting of Eclogites

14.3. Petrography

14.4. Analytical Conditions

14.5. Geothermobarometry

14.6. Discussion

15. HP–UHP Metamorphic Belts in the Eastern Tethyan Orogenic System in China

15.1. Introduction

15.2. HP–UHP Metamorphic Belts of the Eastern Tethyan System in China

15.3. HP–UHP Metamorphic Belts in the Proto-Tethyan Orogen

15.4. HP–UHP Metamorphism in the Paleo-Tethyan Orogenic Belt

15.5. HP–UHP Metamorphic Rocks Within the Neo-Tethyan Orogenic Belt

15.6. The Formation and Exhumation Dynamics of HP–UHP Metamorphic Belts in the Eastern Tethyan Orogenic Belt in China

15.7. Conclusions

16. Orogenic Garnet Peridotites

16.1. Introduction

16.2. A Conceptual Model Illustrating How Orogenic Garnet Peridotite Can Be Used to Reconstruct Fossil Geodynamic Environments

16.3. A Test of the Feasibility of the Model in Scandinavia and China

16.4. Discussion and Conclusions

17. Petrology, Geochemistry, Geochronology, and Metamorphic Evolution of Garnet Peridotites from South Altyn Tagh UHP Terrane, Northwestern China

17.1. Introduction

17.2. Geologic Background

17.3. Petrography

17.4. Bulk-Rock Composition

17.5. Zircon U–Pb Dating and Hf Isotope Compositions

17.6. Mineral Chemistry

17.7. Textural and Metamorphic Evolution

17.8. P–T Estimates and P–T Path

17.9. Genesis of the Grt Peridotites and its Tectonic Implications

17.10. Conclusions

18. Metamorphic Evolution of the Gridino Mafic Dyke Swarm (Belomorian Eclogite Province, Russia)

18.1. Introduction

18.2. Geological Setting

18.3. Methods

18.4. Sample Description

18.5. Discussion

18.6. Conclusions

19. The Salma Eclogites of the Belomorian Province, Russia

19.1. Introduction

19.2. Geological Background and Field Occurrence of Eclogites

19.3. Analytical Methods

19.4. Major- and Trace-Element Chemistry

19.5. Petrography and Mineral Chemistry

19.6. Geochronology

19.7. Results

19.8. Discussion

19.9. Conclusions

Front-matter

Ultrahigh-Pressure Metamorphism

Ultrahigh-Pressure Metamorphism

25 Years After the Discovery of Coesite and Diamond

Editors

Larissa F. Dobrzhinetskaya

Shah Wali Faryad

Simon Wallis

Simon Cuthbert

Task Force IV International Lithosphere Program

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO

Copyright

Elsevier

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First edition 2011

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Preface

Larissa F. Dobrzhinetskaya, Shah Wali Faryad, Simon Wallis and Simon Cuthbert

Ultrahigh-pressure metamorphism (UHPM) as a discipline was established about 25 years ago after the discoveries of coesite and diamond in rocks of continental affinities, where the presence of such minerals had been forbidden according to mainstream geological concepts. At that time, both coesite and diamond were thought to be only formed in the Earth’s mantle, on the Earth’s surface as products of meteoritic impact, and in some meteorites.

Coesite was first discovered within metasedimentary rocks in the Dora Maira area of the Western Alps of Italy, but independently, and almost at the same time, it was also discovered in the Western Gneiss Region of Norway. Soon afterward, the first microdiamonds were found in metamorphic rocks of the Kokchetav Massif of Kazakhstan. Both mineralogical discoveries have clearly established that the rocks of continental origin were subjected to UHPM, which required their subduction to a depth of not less that 80–120km.

Since that time, extensive research on UHPM terranes has emerged, and studies are continuing now by geologists from more than 30 countries. These international efforts have led to new findings of coesite and diamond within eclogite and other HP/UHP metamorphic rocks occurring within collisional orogenic belts of Eurasia, Africa, South and North Americas, Greenland, Antarctica, and Papua New Guinea.

We now know that UHPM terranes may include diverse lithological fragments of both continental and oceanic crusts consisting of metamorphosed sediments, granites, diorites, and associated mafic–ultramafic intrusions and/or mantle peridotite, all of which were initially formed in the shallower lithosphere. Such UHPM units that have experienced recrystallization within the coesite and diamond stability fields at a depth of up to ∼200–250km may also include fragments of very-deep-mantle peridotite originating from the base of the upper mantle.

Geologic processes occurring under UHP conditions are difficult to recognize due to intense retrogressive reactions and/or fluid and deformation activities experienced by the rocks during exhumation. However, studies of the rocks in laboratories with the aid of advanced, state-of-the-art analytical instruments and techniques help us to understand in detail the processes operating in the deep Earth at convergent plate boundaries.

The great long-term interest of UHPM research is due to its significance for understanding large-scale mantle dynamics, major elements of plate tectonics such as continental collisions, deep subduction and exhumation, mountain building, geochemical recycling from surface to the core, and the deep storage of light elements.

This book consists of four parts: (I) Diamonds—New Studies; (II) Minerals Chemistry, Reactions, and Microstructures in UHPM Rocks; (III) Geochronological Data of UHPM Terranes; and (IV) Ultrahigh-Pressure Metamorphic Belts and Protolith History of Eclogite and Garnet Peridotite.

We would like to thank all authors for excellent contributions that contain new data, new insights and discoveries, and summaries of existing data up to this time. We are also grateful to the authors for their timely cooperation during the editorial process. This book would not have been possible without referees (including anonymous reviewers) who provided critical but constructive comments, suggestions, insights to ensure the quality of the chapters. This book is part of the activity of Task Force IV of the International Lithosphere Program and Working Group Mineral Equilibria (WGME) of the International Mineralogical Association.

List of Contributors

Tamara B. Bayanova

Geological Institute of the Kola Science Centre RAS, Apatity, Russia

Elena A. Belousova

GEMOC ARC National Key Centre, Department of Earth and Planetary Sciences, Macquarie University, Australia

Fraukje M. Brouwer

Department of Petrology, Faculty of Earth & Life Sciences, VU University Amsterdam, Amsterdam, The Netherlands

Yuting Cao

State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi’an, China;

School of Science, University of the West of Scotland, Paisley, UK

Danling Chen

State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi’an, China

Andrew G. Christy

Research School of Earth Sciences, Australian National University, Canberra, ACT, Australia;Centre for Advanced Microscopy, Australian National University, Canberra, ACT, Australia

Jan C.M. De Hoog

School of GeoSciences, The University of Edinburgh, Edinburgh, UK

Larissa F. Dobrzhinetskaya

Department of Earth Sciences/IGPP, University of California, Riverside, CA, USA

Ksenia A. Dokukina

Geological Institute of the Russian Academy of Sciences, Moscow, Russia

Afifé El Korh

Department of Mineralogy, University of Geneva, Geneva, Switzerland

Philippe Erdmer

Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, AB, Canada

C. Mark Fanning

Research School of Earth Sciences, The Australian National University, Canberra, Australia

Shah Wali Faryad

Institute of Petrology and Structural Geology, Charles University, Prague, Czech Republic

Maria Luce Frezzotti

Dipartimento Scienze della Terra, Università di Siena, Siena, Italy

Dieter Gebauer

Institute of Geochemistry and Petrology, ETH Zurich, Zurich, Switzerland

Edward Ghent

Department of Geoscience, University of Calgary, Calgary, AB, Canada

Gaston Godard

Institut de Physique du Globe de Paris, Université Denis-Diderot, Paris, France

Harry W. Green

Department of Earth Sciences/IGPP, University of California, Riverside, CA, USA

William L. Griffin

GEMOC ARC National Key Centre, Department of Earth and Planetary Sciences, Macquarie University, Australia

Mirek Groen

Department of Petrology, Faculty of Earth & Life Sciences, VU University Amsterdam, Amsterdam, The Netherlands

Keiko H. Hattori

Department of Earth Sciences, University of Ottawa, Ottawa, ON, Canada

Takao Hirajima

Department of Geology and Mineralogy, Graduate School of Science, Kyoto University, Kyoto, Japan

Jason M. Huberty

Department of Geosciences, University of Wisconsin–Madison, Madison, WI, USA

Yoshiyuki Iizuka

Institute of Earth Sciences, Academia Sinica, Nankang, Taipei, Taiwan

Daijo Ikuta

HPCAT, Geophysical Laboratory, Carnegie Institution of Washington, Argonne, IL, USA

Bor-Ming Jahn

Institute of Earth Sciences, Academia Sinica, Nankang, Taipei, Taiwan

Marian Janák

Geological Institute, Slovak Academy of Sciences, Bratislava, Slovak Republic

Hiroyuki Kagi

Geochemical Research Center, Graduate School of Science, University of Tokyo, Tokyo, Japan

Tatiana V. Kaulina

Geological Institute of the Kola Science Centre RAS, Apatity, Russia

Abby Kavner

Department of Earth and Space Sciences/IGPP, University of California, Los Angeles, CA, USA

Tomoyuki Kobayashi

Department of Geology and Mineralogy, Graduate School of Science, Kyoto University, Kyoto, Japan

Alexander N. Konilov

Institute of Experimental Mineralogy of the Russian Academy of Sciences, Chernogolovka, Russia;

Geological Institute of the Russian Academy of Sciences, Moscow, Russia

Atsushi Kubo

Consortium for Advanced Radiation Sources, University of Chicago, Chicago, IL, USA

Huijuan Li

The Key Laboratory of Orogenic and Crustal Evolution, MOE, School of Earth and Space Sciences, Peking University, China;

Research School of Earth Sciences, Australian National University, Canberra, ACT, Australia

Anthi Liati

Institute of Geochemistry and Petrology, ETH Zurich, Zurich, Switzerland

Juhn G. Liou

Department of Geological and Environmental Sciences, Stanford University, Stanford, CA, USA

Fulai Liu

Key Laboratory for Continental Dynamics, MLR, Institute of Geology, Chinese Academy of Geological Sciences, Beijing, China

Jingbo Liu

State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing, China

Liang Liu

State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi’an, China

Kenshi Maki

Institute of Earth Sciences, Academia Sinica, Nankang, Taipei, Taiwan

Qian Mao

State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing, China

Michael V. Mints

Geological Institute of the Russian Academy of Sciences, Moscow, Russia

Kosuke Naemura

Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing

Lev M. Natapov

GEMOC ARC National Key Centre, Department of Earth and Planetary Sciences, Macquarie University, Australia

Oliver Nebel

Department of Petrology, Faculty of Earth & Life Sciences, VU University Amsterdam, Amsterdam, The Netherlands;

Research School of Earth Sciences, ANU, Canberra, ACT, Australia

Shoko Odake

Geochemical Research Center, Graduate School of Science, University of Tokyo, Tokyo, Japan

Shugo Ohi

Department of Geology and Mineralogy, Graduate School of Science, Kyoto University, Kyoto, Japan

Suzanne Y. O’Reilly

GEMOC ARC National Key Centre, Department of Earth and Planetary Sciences, Macquarie University, Australia

Rosaria Palmeri

Museo Nazionale dell’Antartide, Università di Siena, Siena, Italy

Vitali Prakapenka

Consortium for Advanced Radiation Sources, University of Chicago, Chicago, IL, USA

Huaning Qiu

State Key Laboratory of Isotope Geochronology and Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China;

State Key Laboratory of Tectonics and Petroleum Resources, China University of Geosciences, Wuhan, China

Paul T. Robinson

Department of Earth Sciences, Dalhousie University, Halifax, NS, Canada

Susanne Th. Schmidt

Department of Mineralogy, University of Geneva, Geneva, Switzerland

Andrey A. Shchipansky

Geological Institute of the Russian Academy of Sciences, Moscow, Russia

David C. Smith

Laboratoire de Minéralogie et Cosmochimie du Muséum, Muséum National d’Histoire Naturelle, Paris, France

Martin Svojtka

Institute of Geology, Academy of Sciences of the Czech Republic, Praha, Czech Republic

Tadamasa Ueda

Department of Geology and Mineralogy, Graduate School of Science, Kyoto University, Kyoto, Japan

Alexey Ulianov

Institute of Mineralogy and Geochemistry, University of Lausanne, Anthropole, Lausanne, Switzerland

Herman van Roermund

Department of Earth Sciences, Structural Geology and Tectonics, Utrecht University, Utrecht, The Netherlands

Torsten Vennemann

Institute of Mineralogy and Geochemistry, University of Lausanne, Anthropole, Lausanne, Switzerland

Mirijam Vrabec

Department of Geology, University of Ljubljana, Ljubljana, Slovenia

Chao Wang

State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi’an, China;

Xi’an Center of Geological survey, China Geological Survey, Xi’an, China

Jan R. Wijbrans

Department of Petrology, Faculty of Earth & Life Sciences, VU University Amsterdam, Amsterdam, The Netherlands

Cailai Wu

Key Laboratory for Continental Dynamics, MLR, Institute of Geology, Chinese Academy of Geological Sciences, Beijing, China

Yuanbao Wu

State Key Laboratory of Geological Processes and Mineral Resources, Faculty of Earth Sciences, China University of Geosciences, Wuhan, China

Huifang Xu

Department of Geosciences, University of Wisconsin–Madison, Madison, WI, USA

Zhiqin Xu

Key Laboratory for Continental Dynamics, MLR, Institute of Geology, Chinese Academy of Geological Sciences, Beijing, China

Jingsui Yang

Key Laboratory for Continental Dynamics, MLR, Institute of Geology, Chinese Academy of Geological Sciences, Beijing, China

Qijun Yang

State Key Laboratory of Isotope Geochronology and Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China

Kai Ye

State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing, China

Cong Zhang

Key Laboratory of Orogenic Belts and Crustal Evolution, School of Earth and Space Sciences, Peking University, Beijing, China;

Department of Earth Sciences, Structural Geology and Tectonics, Utrecht University, Utrecht, The Netherlands

Jianxin Zhang

Key Laboratory for Continental Dynamics, MLR, Institute of Geology, Chinese Academy of Geological Sciences, Beijing, China

Junfeng Zhang

State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan, China

Lifei Zhang

Key Laboratory of Orogenic and Crustal Evolution, MOE School of Earth and Space Sciences, Peking University, China

Lingmin Zhang

State Key Laboratory of Lithospheric Evolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing, China

Ru Y. Zhang

Department of Geological and Environmental Sciences, Stanford University, Stanford, CA, USA;

Institute of Earth Sciences, Academia Sinica, Nankang, Taipei, Taiwan

Zeming Zhang

Key Laboratory for Continental Dynamics, MLR, Institute of Geology, Chinese Academy of Geological Sciences, Beijing, China

Linghao H. Zhao

State Key Laboratory of Isotope Geochronology and Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China

Reviewers

1. Frontiers of Ultrahigh-Pressure Metamorphism

View from Field and Laboratory

Larissa F. Dobrzhinetskaya¹ and Shah Wali Faryad²

¹Department of Earth Sciences/IGPP, University of California, Riverside, CA, USA

²Institute of Petrology and Structural Geology, Charles University, Prague, Czech Republic

Ultrahigh-pressure metamorphism (UHPM) is a relatively new but fast-growing discipline related to the deep subduction of continental and/or oceanic crust into the Earth’s mantle and their return toward the surface as fragments incorporated within orogenic belts bordering active continental margines. The discipline was established ∼25 years ago after the discoveries of high-pressure minerals, coesite, and diamond in the rocks of the continental affinities, a place where such minerals were forbidden according to the existing mainstream geological concepts at that time. Since then several new directions in studying UHPM terranes were created, and new approaches for studies of microstructures of minerals transformed by decompression were formulated, discovered at first-time nanometric fluid inclusions in microdiamonds, developed diamond synthesis from unusual combination of C+H2O at high P–T conditions, made discoveries of new UHPM terranes, and new minerals, developed new applications of advanced analytical instruments to study solid and fluid inclusions of nanometric scale with high-resolution electron microscopy, nanoscale secondary ion mass spectrometry (nanoSIMS), X-ray in situ, and infrared (IR) spectroscopy assisted with synchrotron technologies and others. This chapter provides summary of main achievements in UHPM researches and formulates further directions.

Key Words

Ultrahigh-pressure metamorphism, orogenic belts, continental collision, phases transformation

1.1. Introduction

Since the first discovery of coesite (Chopin, 1984 and Smith, 1984) and microdiamond (Sobolev & Shatsky, 1990) within eclogite-bearing metamorphic belts, extensive progress has been achieved in understanding the origin of ultrahigh-pressure metamorphic (UHPM) rocks in the context of global tectonics operating through continental subduction, collision, exhumation, mantle–lithospheric slab interactions, and geochemical recycling of subducted/exhumed rocks. Comprehensive review articles and special issues related to UHP metamorphism and plate tectonics are published almost every year (Ernst and Liou, 2000, Ernst and Liou, 2008, Chopin, 2003, Liou et al., 2004, Green, 2005, Ernst et al., 2007, Zhang et al., 2007, Guillot et al., 2008, Liou et al., 2009a and Beltrando et al., 2010). They provide valuable summaries of existing knowledge, outline future directions, and discuss controversial concepts. These papers also summarized recent progress in experimental determination of P–T stability fields of new phases, phase transformations of those minerals which were known before to be stable only at shallow depths of the continental crust, and they reported that the exsolution products of UHPM minerals indicate that continental rocks were subducted to depths exceeding 100–250km. Extensive research in UHP metamorphic rocks led to new constraints and the improvement of many geotectonic models developed for very deep subduction of continental rocks and their exhumation within many well-known orogenic belts. Numerical geodynamic modeling of subduction and exhumation became a powerful tool for understanding mantle dynamics and global continental subduction (Gerya, 2010).

The goal of our review is to update and emphasize those aspects of knowledge related to UHPM studies which were less highlighted in the previous reviews, but, in fact, represent frontier questions that have became possible to recognize and solve only by integration of new experimental technologies, achievements in modern mineral physics, and by using state-of-the-art analytical instruments and facilities. This chapter also raises fundamental questions related to understanding global recycling of the subducted material, in terms of where the nonreturned continental material is stagnated, to what depth continental rocks of different bulk chemistry can be subducted, and how they can be recognized if their relicts or remainders are assimilated within unexpected geological environments. We present here also the most recent findings on UHP minerals and their unusual geological setting and discuss further directions in studies of UHPM phases, products of their replacement, and advanced techniques for their studies.

1.2. Main Achievements: 25 Years On

1.2.1. Deciphering of New UHP Phases or Their Pseudomorphosis

Among many other exciting discoveries, such as coesite and diamond in metamorphic rocks, made in last quarter century, is a recent study of the microstructural reconstruction of a precursor-stishovite in an Al-rich gneiss from the South Altyn Tagh, China (Liu et al., 2007a). These rocks exhibit very unusual textures represented by a polycrystalline quartz associated with oriented inclusions of kyanite and hercynite, indicating their formation from a decompressed precursor-stishovite and suggesting that these continental rocks were subducted to a depth of more than 350km (Liu et al., 2007a).

Reports of coesite and/or clinopyroxene lamellae in ophiolitic chromite (Yamamoto et al., 2009), as well as osbornite (TiN), cubic boron nitride (BN, first time as a mineral), and α-PbO2-structured TiO2 (TiO2 II) included in coesite pseudomorphous after stishovite from the Tibetan chromitite (Yamamoto et al., 2007 and Dobrzhinetskaya et al., 2009a) have opened a new direction for searching relict fragments of continental material amalgamated into harzburgitic mantle of a paleo-mid-ocean spreading center by a deep-mantle plume or large-scale mantle convection (Dobrzhinetskaya et al., 2009a).

Earlier, TiO2 II had been described as a thin twinning lamellae in rutile included in garnet from diamondiferous quartzofeldspathic rocks of the Erzgebirge Massif, Bohemia, by Hwang et al. (2000). Furthermore, Wu et al., 2005 and Wu et al., 2006 have also reported the nanometer-scale α-PbO2-structured TiO2 lamellae in omphacite from a coesite-bearing eclogite in the Shima area, the eastern part of Dabie, China. However, Chen and Fu (2006) have suggested that the nanometer-scale α-PbO2-lamellae of rutile could be formed during extensive mechanical treatment in the course of sample preparation. The minimum pressure for the transformation from rutile TiO2 to α-PbO2-type TiO2 is 6GPa at 850°C for bulk, whereas the minimum pressure drops to 4.5GPa at 900–1000°C for nanophase TiO2 due to the size effect (Olsen et al., 1999). More experimental research is needed to establish the size effect of mineral phases on their stability field during UHP metamorphism.

Multistage formation of majoritic garnet in a single Norwegian UHP garnet peridotite (Scambelluri et al., 2008) and the report of two stages of Erzgebirge diamond crystallization (Dobrzhinetskaya et al., 2010) are also important findings in recent UHPM research. The two stages of Erzgebirge diamond formation were recently established with in situ studies of δ¹³C in these diamonds included in garnet with nanoSIMS (Dobrzhinetskaya et al., 2010). The result provides evidence of the similarity in the history of the Erzgebirge diamond’s crystallization with the two-stage diamond formation in the Kokchetav Massif, Kazakhstan, established earlier by Ogasawara et al. (2005).

K-cymrite (KAlSi3O8nH2O) was recently recognized as the precursor phase of inclusions of K-feldspar aggregates formed at P>3GPa and T∼720°C (Zhang et al., 2009). The inclusions are found in eclogitic garnet from the Dulan area of the North Qaidam terrane, China. The recognition of K-cymrite in UHP eclogite is of great importance, because this mineral may be considered as an important carrier of crustal K and H2O to the upper mantle.

Other important mineralogical findings within UHPM rocks are a supersilicic titanite, Si-rich and/or K-bearing clinopyroxene, and aragonite+magnesite inclusions in microdiamonds (all from the Kokchetav Massif, Kazakhstan), which suggest subduction depths for the continental rocks of ∼190–280km (Katayama et al., 2000, Ogasawara et al., 2002 and Dobrzhinetskaya et al., 2006).

Systematic studies of micro-inclusions and exsolution lamellae in many garnet peridotites from UHPM terranes showed that they often contain features that apparently were formed at much higher pressures than were calculated employing the Grt–Opx geobarometers (Liou et al., 1998; Griffin, 2008). Remarkable, though controversial initially, was the discovery of exsolved ilmenite rods and chromite plates in olivine from a garnet lherzolite in the central Alps (Dobrzhinetskaya et al., 1996). The authors first proposed that a precursor single phase (olivine or wadsleyite) contained >0.6wt% TiO2, implying an apparent depth of origin of ∼300–450km for the peridotite. Later phase-equilibrium experiments demonstrated that >1vol.% TiO2 can be dissolved in olivine at elevated T and at pressures of 9–12GPa (Dobrzhinetskaya et al., 2000, Tinkler and Lesher, 2001 and Bozhilov et al., 2003), removing the need to postulate the former presence of wadsleyite. The surrounding, kyanite-bearing Lepontine gneisses display evidence of partial melting but lack mineralogical relicts indicative of UHP metamorphism, so the garnet peridotite probably represents a later tectonic insertion into the country rock gneisses (Green et al., 2010).

Quartz exsolution lamellae in clinopyroxene, resulting from decomposition of nonstoichiometric UHP pyroxene, reported from many UHP terranes with coesite (Liou et al., 2008, 2009b and Section 1.3.2), have been reported also from the Ballantrae Complex in southwestern Scotland, suggesting that these metamorphic complexes also have evidence of deep subduction (Yamamoto et al., 2007).

1.2.2. New Discoveries of UHP Terranes

In their substantial review paper, Liou et al. (2009a) summarized more than 20 worldwide occurrences of UHPM rocks with ages ranging from Proterozoic (640Ma) in southwestern Brazil (Parkinson et al., 2001) to the most recent (2–3Ma) from Papua New Guinea (Baldwin et al., 2004, Baldwin et al., 2005 and Monteleone et al., 2007). Yet, indeed, the number of occurrences of UHPM rocks continues to increase by the addition of new findings of microdiamonds in the Sideronero area of the Greek Rhodope (Schmidt et al., 2010), the Moldanubian Zone of the Bohemian Massif (Naemura et al., this volume), the Western Alps (Frezotti et al., 2010), and by the finding of new UHP eclogite localities through thermobarometric calculations, for example, the Limousin area in the French Massif Central (Bergen, 2010). In Table 1.1 we summarize new localities that have been classified as UHPM terranes based on thermobarometric evaluation. The map in Figure 1.1 illustrates the worldwide distribution of UHPM terranes.

Whereas the concept of decompression of majoritic garnet derived from experiments (REF) supports only formation of the exsolution lamellae of pyroxenes, a wide range of chemical diversity of materials exsolved from majoritic garnet was reported from UHPM terranes. Liou et al. (2009b) reported that many garnets from UHPM terranes contain topotaxially exsolved needles, rods, or laths of pyroxenes±Rt±Ap. Such garnets with complex compositions have been described among garnet peridotites from the Western Gneiss Region (WGR), Norway (Scambelluri et al., 2008 and van Roermund, 2009), the Dabie–Sulu UHPM terrane of China (Ye et al., 2000), the Bohemian Massif (Massonne and Bautsch, 2002 and Bakun-Czubarow, 2007), the Greek Rhodope (Mposkos & Kostopoulous, 2001), and in eclogite that occurs within garnet peridotite in North Qaidam, western China (Song et al., 2004 and Song et al., 2005.

Because diamond undoubtedly is an indicator of high pressure (Bundy, 1962 and Bundy, 1989), any new locality of metamorphic rocks where diamond is found (if it is not formed by a meteorite impact) brings a new UHPM terrane and extends our knowledge about many aspects of deep subduction. Besides the five well-established UHPM terranes (Kokchetav of Kazakhstan, Qinling and Dabie of China, WGR of Norway, Erzgebirge of Germany, and Rhodope of Greece) containing unconditionally confirmed diamond (Sobolev and Shatsky, 1990, Xu et al., 1992, Dobrzhinetskaya et al., 1995, Massonne, 1999, Mposkos and Kostopoulos, 2001, van Roermund et al., 2002, Yang et al., 2003, Perraki et al., 2006 and Schmidt et al., 2010), there are several reports of localities where diamond is not clearly identified, for example, Sulawesi, Indonesia (Parkinson & Katayama, 1999), and the Kontum, Vietnam (Nakano et al., 2006).

This year is marked by three new reports on diamond discoveries among European metamorphic terranes. One of them found diamond inclusions in garnet from schists near the village of Sideronero of the Greek Rhodope, which is situated about 70km to the west of the nearest UHP locality at Xanthi (Scmidt et al., 2010). In the Greek Rhodope, for the first time, strongly graphitized microdiamonds were found as inclusions in garnet also containing exsolution lamellae of rutile and quartz in schists of the Kimi complex, considered part of the melange zone (Mposkos and Kostopoulos, 2001 and Perraki et al., 2006). Independently, the UHP conditions of 2.5–3GPa and 650–750°C for kyanite-bearing eclogite in the Pirin Mountains, a Bulgarian region of the Rhodope mountains, were estimated by Janák et al. (2010). Age of the HP–UHP metamorphism in the Rhodope is still controversial. The sensitive high-resolution ion microprobe (SHRIMP) U–Pb data on zircon obtained by Liati et al. (2002) yielded an age of 74±3.4Ma, but those obtained by Bauer et al. (2007) suggest ≥160–170Ma for HP–UHP metamorphism.

Naemura et al. (this volume) have identified microdiamonds by Raman spectroscopy in garnet from garnet peridotite classified earlier as HP granulite (Moldanubian zone). With synchrotron X-ray fluorescence analysis, they established that this diamond contains Fe–Ni metal (taenite) and Cu–Zn-rich phases (possibly sulfide).

Discovery of microdiamond in the Western Alps (Frezotti et al., 2010), together with new diamond occurrences in Bohemia and Rhodope, extend our understanding of large-scale elements of deep subduction.

In addition to the above-mentioned localities with relicts of majoritic garnet and/or microdiamond, coesite inclusions or their pseudomorphs were found in garnet, omphacite, kyanite, zircon, and tourmaline in the following UHP terranes: western Alps (Chopin, 1984, Reinecke, 1991, Schertl et al., 1991, Hermann, 2003 and Castelli et al., 2007), western Tian Shan (Zhang et al., 2007), Makbal, western Kyrgyzstan (Tagiri et al., 1995), east Greenland Caledonides (Gilotti and Ravna, 2002 and McClelland et al., 2006), Lanterman Range, Antarctica (Ghiribelli et al., 2002 and Palmeri et al., 2003), Gittidas, Pakistan (O’Brien et al., 2001, Kaneko et al., 2003 and Parrish et al., 2006), Tso Morari, Himalayas (Sachan et al., 2004 and Leech et al., 2005), Papua New Guinea (Baldwin et al., 2004 and Monteleone et al., 2007), and Pohorje, eastern Alps (Janák et al., 2004). Zhang et al. (2009) reported the presence of coesite in eclogite from the western part of the northern Qaidam UHP belt. They estimated peak pressure of 2.25–2.65GPa at 550–610°C for the eclogite facies metamorphism.

Besides mineral pressure indicators, many UHPM terranes are established with the thermobarometric calculations applied to both peridotites and eclogites associated with metamorphic rocks classified earlier as granulites, or even rocks of glaucophane–lawsonite facies. For example, garnet peridotites and garnet pyroxenites occurring as m-to-km sized blocks and lenses among gneisses and granulites have been revisited (Brueckner and Medaris, 1998, Medaris, 1999, Zhang et al., 2004, Zhang et al., 2007, Liou et al., 2007 and Reverdatto et al., 2008). Many of these rocks no longer preserve mineralogical assemblages that would indicate their recrystallization at high pressures. However, microstructural features such as spinel inclusions in garnet, exsolution lamellae of clinoenstatite, or defect micas with domains of 10Å phase in pyroxenes (Zhang and Liou, 2003, Bozhilov et al., 2009 and Faryad et al., 2009) provide constraints on mantle processes and involvement of the mantle wedge in the subduction zone. Similarities in lithologies and metamorphic minerals of garnet peridotites and garnet pyroxenites occurring in different massifs of the European Variscan Belt show that in most the calculated pressure conditions were underestimated (Faryad, this volume).

Recently, new localities of lawsonite eclogites were recognized in different orogenic belts, and in some of them coesite was found, or their P–T conditions estimated by thermobarometry appeared to be close to the lower-temperature part of the coesite stability field (Chent et al., 2009 and Zhang et al., 2009). One such observation from British Columbia, Canada, involved a lawsonite eclogite exposed within blueschists that represents a fragment of the oceanic crust recrystallized at a depth of ∼90km within a cool P–T gradient of ∼5°Ckm−1(Chent et al., 2009). Further studies of the Ross River eclogite in British Columbia (Chent & Edmer, this volume) show one more example that new P–T calculations for the so-called cold eclogite suggest greater depths of burial than were previously considered.

In relation to cold subduction of oceanic material, a second set of observations shows that coesite-bearing eclogite from western Tian Shan, northwestern China, consists of a garnet+omphacite+lawsonite+glaucophene+coesite assembly that was equilibrated at 420–520°C and 27kbar. The finding of lawsonite–coesite-bearing eclogite provides insight into the metamorphic evolution of a cold subduction zone (Zhang et al., 2009).

A new publication (Mints et al., 2010) on the existence of very-old eclogite facies rocks with a gabbroid protolith (Kola Peninsula, Russia) provides convincing evidence that the eclogites were formed during late Mesoarchean time at pressures of 1.75GPa and T=700°C. Mints et al. (2010) and further detailed description of this eclogite-bearing region by Konilov et al. (this volume), challenge the existing paradigm that plate tectonics did not operate until Earth had cooled to a critical point, perhaps around 2.5Ga, which corresponds to the Archean–Proterozoic transition.

1.3. Further Directions

1.3.1. Fate of Continental Crust Beyond the Point of No Return: Visions and Perspectives

The volume of a melt fraction occurring during UHP metamorphic processes is still largely unknown. However, such knowledge is crucial for understanding geochemical and tectonic processes operating during subduction and exhumation. In the case of UHPM rocks, the ubiquitous presence of a larger volume of rocks of continental affinity than the volume of more dense mafic and/or ultramafic rocks strongly suggests that the buoyancy of the continental material, once unstuck from the subducting slab, is sufficient to transport it back to the surface. However, it is unknown if the relative buoyancy of the crustal UHPM rocks persists at depths substantially greater than 150km.

For many years, accepted geological thought taught us that the relatively low-density continental crust (2.7gcm−3 and therefore buoyant in contrast to the denser rocks of the upper mantle at 3.38–3.42gcm−3 (Ringwood, 1991)) cannot be subducted deeply. It was believed, therefore, that fragments of the subducted continental crust of granitic composition are returned promptly to shallow depths or become molten in arc environments, whereas more mafic, lower crust becomes much denser and sinks deeper into the upper mantle and even to the mantle transition zone. This paradigm was broken with the discovery of metamorphic rocks of continental affinities containing coesite (Chopin, 1984 and Smith, 1984) and diamond (Sobolev and Shatsky, 1990, Xu et al., 1992, Dobrzhinetskaya et al., 1995, Massonne, 1999, Nasdala and Massonne, 2000, Mposkos and Kostopoulos, 2001, van Roermund et al., 2002, Yang et al., 2003, Perraki et al., 2006 and Schmidt et al., 2010). Furthermore, other evidence of high pressure was collected: olivine with oriented exsolutions of ilmenite and chromite in garnet peridotite in the Alps (Dobrzhinetskaya et al., 1996, Green et al., 1997, Green et al., 2010 and Bozhilov et al., 1999, 2003) and garnet peridotite of the Qaidam area, China (Song et al., 2004), or magnetite in olivine from peridotite of the Dabie UHPM terrane, China (Zhang et al., 1999), relics of former majoritic garnet in the WGR of Norway (van Roermund and Drury, 1998 and Spengler et al., 2006), and the Sulu area of China (Ye et al., 2000); also titanite and omphacite containing exsolved rods and plates of coesite in the Kokchetav Massif, Kazakhstan (Ogasawara et al., 2002) and Quadam area of China (Zhang, Z-.M. et al., 2005), topaz-OH in Al-rich quartzite of the Sulu (Zhang et al., 2002a), pseudomorphs of stishovite in the Altun Tag UHP metapelite (Liu et al., 2007a), TiO2 II (rutile with α-PbO2 structure) in the Erzgebirge diamondiferous gneisses (Hwang et al., 2000), and metal–Al–Si-bearing xenocrysts with coesite after stishovite, osbornite (TiN), and cubic BN (Dobrzhinetskaya et al., 2009a). All of these mineralogical assemblages suggest that these continental crust fragments, tectonically juxtaposed with mantle rocks, were subjected to recrystallization at high pressures and high temperatures requiring a depth of >100–250km.

It is still poorly understood what volume of deeply subducted crustal material returned to the surface due to exhumation, to reside within collisional orogenic belts, and how much was subducted beyond the point of no return and never returned to the Earth’s surface. Field observations, geological mapping, and geochronological data collected within the largest Central Orogenic Belt (COB) of China, coupled with results of the Chinese Continental Scientific Drilling (CCSD) project, have confirmed that a huge volume of the UHPM continental rocks have been returned due to exhumation. The possibility of large-scale deep subduction of continental crust was also strengthened with the discovery of microdiamonds within the Qinling gneisses and eclogites in the COB (Yang et al., 2003; Yang et al., this volume). The finding of microdiamonds in the Qinling area bridged the earlier recognized Qaidam and Dabie–Sulu UHPM terranes, and confirmed the existence of a larger UHPM belt extending more than 4000km in length and ∼120km in width. Further studies suggested that this 4000-km-long UHPM belt contains evidence of double deep subduction, occurring in the early Paleozoic in the west and the early Mesozoic (Triassic) in the east, recording two separate continental collisions overprinted within the COB (Yang et al., 2003 and Hacker et al., 2004). The cycles of such deep subductions and exhumations occurred with an interval of ca. 200–300Ma. Further evidence that a huge volume of UHPM rocks returned to the Earth’s surface derives from results of the CCSD project, the first deep continental drilling project through UHPM rocks of the Sulu terrane in the vicinity of Ganyu and Donhai villages (Xu, 2004 and Zhang et al., 2005). The main CCSD borehole drilled through the lithological unit composed of felsic gneisses, eclogite, and garnet peridotite to a depth of ∼5.14km from the surface (Xu, 2004, Liou et al., 2009a and Liou et al., 2009b). Coesite as inclusions in zircons and/or in garnets was found through practically all rock types of the unit, confirming the maximal thickness of the exhumed UHPM slab to be, at least, not less than ∼5km (Liu et al., 2005a). Taking into account that the longest UHPM belt is ∼4000km in length (L) and ∼120km in width (W) (on average), and assuming that the thickness (TH) of the UHPM units of the COB is as large as ∼3.5km, we have calculated the volume (VUHPM) of the exhumed UHPM rocks as follows:

(the error of measurements is ±50%).

Our simplified calculations show that more than 1,680,000km³ of UHPM rocks were returned from depths of about 100–250km and were tectonically placed between continental margins of the north and the south China cratons. We realize that at this moment it is not possible to calculate VUHPM for other UHPM terranes because of the absence of information about their thickness, and that even the volume we have calculated for COB has an error of measurement ±50%.

Although the subduction of a continental slab is limited to relatively shallow depths by its buoyancy, small dismembered fragments of metamorphic and magmatic rocks occurring within active continental margins, as well as pelagic and terrigenous shelf sediments, may be transported very deep into the subduction zone by the heavier oceanic plate and remain there, being dissolved or incorporated as xenocrysts or small fragments into the mantle. The idea that materials of continental crust and oceanic sediments may descend into the Earth’s interior and create specific geochemical reservoirs there is widely supported by data on the ratio of stable isotope pairs, such as ²H/¹H, ¹⁸O/¹⁶O, ⁸⁷Sr/⁸⁶Sr, ¹⁷⁶Hf/¹⁷⁷Hf,¹⁸⁷Os/¹⁸⁸Os, and others (Cohen and O’Nions, 1982, Allegre et al., 1987 and Hart et al., 1992). In addition, seismic tomography provides unprecedented images showing that gigantic pieces of the subducted slabs are stagnated at the depth of the 660km discontinuity (van der Hilst et al., 1997), and some of them are subducted even deeper into the lower mantle to a depth of ∼1500–2700km (van der Voo et al., 1999).

The possibility of very deep subduction of crustal materials is also justified by experimental data based on comparison of the densities and viscosities of mantle and crustal minerals synthesized at high pressures and high temperatures (Irifune et al., 1994, Yagi et al., 1994, Nishiyama et al., 2005, Dobrzhinetskaya and Green, 2007a and Wu et al., 2009). The experimental data show that the bulk continental crust continues to be less dense than mantle rocks (pyrolite composition) at temperature ∼900–1000°C and at pressures up to∼8–10GPa. However, at pressures of 10–11GPa the densities of synthetic UHP metamorphic rocks of granite–tonalite composition exceed the densities of the surrounding mantle peridotites. This suggests that the continental rocks are no longer buoyant under those conditions, and because they become heavier than mantle rocks they will continue to move down into the mantle transition zone. Indeed, experiments have demonstrated that subducted rocks of granitic bulk chemistry at the depth of the 410km seismic discontinuity will consist of majoritic garnet, K-hollandite, and stishovite, and therefore will be denser than surrounding mantle rocks by ∼0.2gcm−3 (Nishiyama et al., 2005). At P–T conditions below the 660km seismic discontinuity, these rocks will be less dense than surrounding mantle by ∼0.15gcm−3; therefore, they will not sink further but will stagnate inside of the mantle transition zone and/or at the top of the lower mantle (Nishiyama et al., 2005, Dobrzhinetskaya and Green, 2007b and Wu et al., 2009).

There are also observations showing that small clusters of Al–Si-rich rocks scattered within mantle appear to be incorporated as inclusions of phase Egg, AlSiO3(OH), in a lower mantle diamond from Juina, Brazil (Wirth et al., 2007). Another relevant observation is a new find of polycrystalline coesite (after stishovite) associated with kyanite in a sample from the mantle section of the Luobusa ophiolite, Tibet (Yang et al., 2007 and Dobrzhinetskaya et al., 2009a). The presence of phase Egg as inclusions in the Juina diamonds may suggest that Al–Si-rich crustal material was subducted to the depth of the lower boundary of the mantle transition zone marked by a 610km seismic discontinuity. Minimal depth of the Tibetan sample was determined to be >300km, and large-scale mantle convection was proposed to be the mechanism that brought a small chunk of the continental crust into harzburgitic mantle of the mid-oceanic ridge (Dobrzhinetskaya et al., 2009a).

Another high-pressure Al–Si-rich phase, topaz-OH, was found in quartzite from the Sulu UHPM terrane, China (Zhang et al., 2002a), in the blueschists of Crete (Theye, 1998) and in quartzite from the UHPM terrane of Dabie and Qinling of China (Kang et al., 1992 and Jing et al., 1995). These authors used the minimum interval of pressures at which topaz-OH is stable in experiments (Wunder et al., 1993 and Wunder et al., 1999) and concluded that topaz-OH and its host rocks were metamorphosed in the coesite stability field (650–700°C, 3GPa). However, later experimental studies of the topaz-OH stability field have shown that this mineral is stable up to P=12GPa at T=800–1500°C (Schmidt, 1996, Schmidt et al., 1998 and Sano et al., 2004). Although the presence of the ultra high-pressure topaz-OH (8–12GPa) in metasedimentary rocks from UHPM terranes is not conclusively documented above the minimum conditions, future studies of such rocks might show that they help to elucidate the buoyancy boundary at which UHP metasedimentary rocks may be exhumed back to the Earth’s surface.

One more example of deep subduction and exhumation from a depth ∼350km of metapelitic rocks containing exsolution lamellae of spinel, kyanite, and rutile in SiO2 (quartz), reconstructed as the product of decompression of former stishovite, was described by Liu et al. (2007a) in the Altyn Tagh, China. In this case, the authors emphasize that sediments can be subducted to at least 350km and returned to the surface, and that the depth of their subduction was close to the point of no return. Beyond the point of no return, continental materials would have density comparable to the mantle and would sink to the base of the mantle transition zone, where they could contribute to the continental trace-element record in ocean island basalts (Liu et al., 2007a).

New experimental programs, based on both direct and reversed experiments, should be performed not only on the averaged dominant lithologies of the continental crust but also on more diverse chemical ranges of natural rocks recognized within UHPM terranes. The future high-pressure and high-temperature experiments should be performed on marbles, calc-silicate metasedimentary rocks, Al-rich quartzite, Na- and K-rich granite, diorite, tonalite, and others. Without looking at such a range of natural UHPM rocks, and understanding the behavior of their mineralogical constituents at high pressures and high temperatures, it is not possible to constrain where different lithologies might stop sinking and whether some might penetrate into the lower mantle.

The future UHP experiments on the mineralogical assemblages of a wide range of rock bulk chemistry should also test the effect of light elements on mantle rock melting and/or reactions. The light elements, such as C, N, K, and rare-earth elements, Th, and U are abundant in sediments of both continental and oceanic origin. They are released from deeply subducted sediments into the mantle and continue their migration through the grain boundaries within the mantle material, where they can trigger melting and/or chemical reactions (Hiraga et al., 2004 and Hayden and Watson, 2008). In addition to that, mantle convection of different scales can move mantle material with incorporated small fragments and/or trapped light elements far away from the places of their primary origin. For example, deep melting of mantle material triggered by a small amount of CO2 which can be released easily from subducted carbonates due to decarbonation reaction has been suggested to explain seismic reflections and anisotropy at depths of 260–300km (Dasgupta & Hirschman, 2006). In UHPM terranes, nitrogen (in the form of NH4, ammonium) occurs in micas from metasediments of eclogite facies and in microdiamonds, where it exists in the form of N2 aggregated around carbon atoms. The concentrations of nitrogen in the rocks and microdiamonds reach a few hundred to several thousand parts per million, indicating that a significant amount of nitrogen can be delivered to the deep mantle through subduction (Bebout et al., 1992 and Cartigny et al., 2003).

Watenphul et al. (2009) have synthesized the ammonium analogs of the high-pressure potassium-bearing silicate phases such as K-hollandite, K–Si–wadeite, K–cymrite, and phengite from (NH4)2O(–MgO)–Al2O3–SiO2–H2O, for example, (NMASH) chemical system, using multianvil and piston–cylinder apparatuses. Syntheses included NH4–hollandite (NH4AlSi3O8) crystallized at 12.3GPa and 700°C; NH4–Si–wadeite [(NH4)2Si4O9] at 10GPa and 700°C; NH4–cymrite (NH4AlSi3O8·H2O) at 7.8GPa and 800°C; and NH4–phengite [NH4(Mg0.5Al1.5)(Al0.5Si3.5)O10(OH)2] at 4GPa and 700°C. In these experiments substitution of NH4 for K was confirmed with IR spectroscopy due to the appearance of NH4-vibration modes v4 and v3 occurring at wavelength ranges of 1397–1459cm−1 and 3223–3333cm−1, respectively. These experiments showed one more mechanism of coupled N and H transportation into the deep mantle through the crystallization of potassium–ammonium-rich silicate phases stable at least up to the 410-km seismic discontinuity.

Interesting results were demonstrated recently on solubility of nitrogen in silicate melt at pressures of 1–3GPa and temperatures between 1400°C and 1700°C for six different binary alkali and alkaline-earth silicate liquids and a Ca–Mg–alumino-silicate (Roskosz et al., 2006). Their experiments show that under those conditions 0.7wt% of N is dissolved in the Si-melt, and the amount of dissolved N is increased with increases of both T and P and the polymerization state of the melt. Raman spectroscopy and ¹⁵N solid-state MAS NMR studies confirmed that nitrogen occurs in such a melt in two forms—as N2 within the melt structure like noble gases, and also structurally bonded with the polymerized silicate melt network. Furthermore, Mysen and Fogel (2010) studied nitrogen and hydrogen isotope compositions and their solubility in silicate melts in equilibrium with reduced (N+H)-bearing fluids at high pressure and temperature. They concluded that both N and H, if dissolved in silicate melt, bond structurally with polymerized Si-melt molecules, and that can affect stable isotope fractionation during melting and crystallization at high pressure and temperature.

1.3.2. Exsolution Lamellae in Minerals from UHPM Terranes

Before discoveries of UHPM terranes, fine-scale exsolution lamellae were widely interpreted as the result of cooling processes of silicate minerals in magmatic rocks (Robinson et al., 1971, Lally et al., 1975 and Nord and Calister, 1979). Some of them were even calibrated as cooling-rate speedometers (Grove, 1982), and also were considered as the result of both decompression and cooling (Robinson et al., 1972). Recently, attention has been drawn to any exsolution lamellae observed in pyroxene, garnet, olivine, and other minerals in UHPM rocks because they are helpful in understanding processes of decompression recorded in these rocks as they were uplifted from mantle depths. In spite of the fact that exsolution lamellae are common in minerals from UHPM rocks, there is still much debate related to their interpretation because the processes of phase transformation and/or chemical and microtextural re-equilibration, taking place at shallower depth, especially at lower P–T conditions, make precursor phases unrecognizable. Nevertheless, each set of exsolution lamellae can still provide valuable information on the chemical composition and physical conditions of a precursor and in some cases can be used for the tentative evaluation of the P–T path of the rocks during decompression/exhumation. These considerations, however, must be supported by experimental data to put a better constraint on P–T conditions at which the lamellae are exsolved, and to develop more precise methods of the lamellae volume determination (van Roermund and Drury, 1998, Bozhilov et al., 1999, Bozhilov et al., 2003, Bozhilov et al., 2009, Ogasawara et al., 2002, Dobrzhinetskaya et al., 2005a, Dobrzhinetskaya et al., 2009b, Spengler et al., 2006 and Yamamoto et al., 2009). Below, we consider some well-known cases.

1.3.2.1. Alpe Arami: Exsolution Lamellae of Ilm and Cr–Spinel in Olivine Revisited

The long-term history of discussions and disagreements on the subject of exsolution lamellae interpretation give us and the next generation of scientists many edifying examples. They usually demonstrate that only studies by advanced high-resolution electron microscopy of exsolution lamellae in combination with experimental data are capable of providing a strong foundation for the interpretation (Green, 2005). One long-term discussion centers on exsolution lamellae of ilmenite and Cr–spinel in olivine from the Alpe Arami garnet peridotite that were used to determine the depth of its origin, >300km (Dobrzhinetskaya et al., 1996, Hacker et al., 1997, Bozhilov et al., 1999, Bozhilov et al., 2003, Green et al., 1997 and Green et al., 2010). Dobrzhinetskaya et al. (1996) proposed that in the Alpe Arami garnet peridotite the topotactically oriented ilmenite rods and chromite flakes in olivine are the result of exsolution, and that they imply high solubility of TiO2 in Ol at high pressures and high temperatures. The conclusion that the Alpe Arami peridotite massif originated from great depth remained controversial despite the subsequent discovery of Cpx inclusions in Grt containing exsolution lamellae of clinoenstatite displaying antiphase domains—a product of decompression. The latter observation requires that the originally precipitated pyroxene had a high-pressure C2/c space group structure consistent with an origin from >8GPa (∼250km) (Bozhilov et al., 1999). Confocal laser scanning microscopy to obtain quantitative 3D measurements of ilmenite abundance in olivine showed that ilmenite rods reach >1vol.% (Bozhilov et al., 2003), supporting the earlier contention that ilmenite rods exsolved from olivine at 9–12GPa, for example, >300km. Arguments that ilmenite rods hosted by olivine are products of the breakdown reaction of Ti–clinohumite (Risold et al., 2003) are unconvincing, given that Ti–clinohumite breakdown does not produce the ilmenite+chromite that is characteristic of the Alpe Arami olivine.

Dobrzhinetskaya et al. (2000), likewise, have confirmed the high solubility of TiO2 in olivine (up to 1wt%) at high P–T conditions (6–12GPa, 1200–1300°C) in multianvil experiments. Later, those findings were strengthened by the experiments of Tinker and Lesher (2001), who received a result similar to Dobrzhinetskaya et al. (2000). These independent experiments by Tinker and Lesher (2001) have confirmed that the solubility of TiO2 in olivine increases with increasing pressures under nearly isothermal conditions. Two reactions are proposed to account for these observations (Green et al., 2010). If Ti enters the octahedral site of olivine, either an oxide phase must be formed or a phase richer in SiO2 than olivine must be consumed, leading to Eq. (1.1):

(1.1)

where [] is an octahedral vacancy. If Ti enters the tetrahedral site, then Eq. (1.2) takes place:

(1.2)

During Eq. (1.1) clinoenstatite is consumed, while for Eq. (1.2) clinoenstatite is produced. Since clinoenstatite was a reaction product in these experiments, the authors concluded that the high solubility of TiO2 is best explained by pressure-induced accommodation of Ti in the tetrahedral site of olivine. A more recent discovery in Bixiling, China, of clinoenstatite lamellae in diopside, showed that the angle of misfit between the lamellae and the diopside lattice implies a depth >300km. Similar method of calculation applied to Alpe Arami lamellae implies ∼400km (Liu et al., 2007b).

Attempts to deny experimental data on high solubility of TiO2 in olivine as a function of pressure produced in experiments at 6–12GPa (Dobrzhinetskaya et al., 2000 and Tinkler and Lesher, 2001) using similar experiments, but at lower pressures (3–5GPa) (Herman et al., 2005) should be considered as an appropriate. Indeed, no detectable solubility of TiO2 at pressures <5GPa was found in experiments by Dobrzhinetskaya et al. (2000) or by Tinker and Lesher (2001). A recent publication by Green et al. (2010) devoted to reconsideration of all achievements versus criticisms in regard of the Alpe Arami Massif studies clearly shows that the Alpe Arami garnet peridotite is a representative of deep-seated mantle peridotite.

1.3.2.2. New Challenges: Quartz and Other Exsolution Lamellae in Pyroxenes

Another disagreement existing among many authors is the question of whether quartz exsolution lamellae in clinopyroxenes form UHPM terranes, questioning if they reflect decompression path (Dobrzhinetskaya et al., 2002, Zhu and Ogasawara, 2002 and Liu et al., 2007b) or only cooling stage (Page et al., 2005 and Konzett et al., 2008). A great contribution to clarify this problem was offered by Day and Mulcahy (2007), who modeled three types of reactions responsible for free silica exsolution in eclogitic pyroxene. They showed that there are three possible paths of SiO2 exsolution: (i) by vacancy consumption in nonstoichiometric pyroxene; (ii) by dissolution of Ti-phases in pyroxene or garnet; and (iii) by reactions between accessory phases and either pyroxene or garnet.

Recently, a series of detailed studies with advanced scanning electron microscope (SEM), transmission electron microscope (TEM), focused ion beam (FIB), and synchrotron-assisted IR spectroscopy showed that formation of phlogopite and quartz lamellae in diopside from diamondiferous rocks of the Kokchetav Massif, Kazakhstan, is a complex process (Dobrzhinetskaya et al., 2009b). The authors have pointed out that the process began from the exsolution of phlogopite and SiO2 due to decompression from K–Si–OH-rich precursor-pyroxene, and continued throughout the history of exhumation by adding a fluid to the system. The fluid invaded through grain boundaries of host mineral–exsolution lamellae, reshaped a primary linear configuration of the exsolution lamellae, and made their chemistry more complicated. However, the analysis of electron diffraction patterns from TEM showed that the topotactic relationships between the host mineral and the lamellae remained unchanged (Dobrzhinetskaya et al., 2009b). This important conclusion should be taken into consideration during further studies of any lamellae-like inclusions in pyroxenes, garnets, and other host minerals from UHPM rocks. Bozhilov et al. (2009) have found exsolution lamellae of cation-deficient phlogopitic mica within diopside of a garnet peridotite drill-core sample recovered from the Sulu UHPM terrane, China, during pre-pilot drilling under auspices of the CCSD project. Detailed TEM studies showed that these precipitates, phlogopitic micas, are highly complex (both structurally and compositionally), with a significant component of the 10Å phase, a talc-like phase stable only at quite high pressures (∼6GPa) (Chinnery et al., 1999). Several mica polytypes are found in the dippside inclusion in garnet from the Sulu garnet peridotite drill-core sample, the simplest one, 1M, being the most cation deficient. The presence of a significant (∼30%) 10Å phase component in the mica suggests that the 10Å is a phase bridge for subduction of H2O to deep-mantle depths.

Furthermore, in contrast to many existing studies, Proyer et al. (2009) have suggested that the lamellae of SiO2 and amphibole in CPx are no ultrahigh-pressure feature, but formed due to diffusional re-equilibration accompanied by nucleation and growth. They considered, for example, that SiO2-rods together with amphibole inclusions in clinopyroxene from the metabasic granulite of the Kimi UHP complex in the Greek Rhodope are products of open system precipitation formed during eclogite–granulite–amphibolite facies transition. Although thin amphibole crystals following the pyroxene cleavage planes may form during retrogression, open system precipitation cannot be the case for topotactically oriented quartz lamellae in pyroxene from UHPM rocks containing diamonds, and it also contradicts thermodynamic and kinetic rules. If one agrees with the Proyer et al. (2009) model, this would mean that the diffusion must be sufficiently fast to supply reactants for the inclusion growth, but, at the same time, it must be slow enough to conserve compositional gradients in clinopyroxene. The authors also suggested that amphibole, quartz, and titaniferous phases could be formed by external addition of Mg²+, Si⁴+, and H+ and removal of Ca²+. This proposed concept contains many vague considerations related to where the elements diffuse, and why they simply do not facilitate clinopyroxene equilibration but rather cause nucleation of new phases. The most controversial aspect of this concept is that it cannot explain why elongated lamellae of SiO2 have topotactic relationships with their host-pyroxene. The coherent crystallographic orientation of the SiO2 lamellar-inclusions in regard to their host-pyroxene can hardly be expected to have formed during any chemical processes, be they nucleation through diffusions or nucleation from a fluid/melt incorporated inside of the host mineral. Numerous high-resolution electron microscopy studies have clearly documented topotactic relationships between host mineral–SiO2 lamellae, or host mineral–phlogopite lamellae and many others, suggesting in almost all cases the exsolution mechanism (Katayama et al., 2000, Tsai and Liou, 2000, Dobrzhinetskaya et al.,